Showing papers in "Zeitschrift Fur Kristallographie-new Crystal Structures in 1999"

Crystal structure of sodium aluminium (monohydrogenmonophosphate-dihydrogenmonoborate-monophosphate, NaAl[BP2O7(OH)3]

Abstract: AlBH3NaOioP2, monoclinic, C12/cl (No. 15), a = 10.497(2) Ä, b = 7.993(2) Ä, c = 9.077(2) Ä, β = 117.26(3)°, V = 677.0 Ä, Ζ = 4, Rst(F) = 0.049, wR(F) = 0.077, T = 293 K. Table 3. Atomic coordinates and displacement parameters (in Ä). Atom Site χ y ζ Atom Site χ y ζ CAso H(l) 8/ 0.478(7) 0.170(9) 1.071(8) 0.02 H(2) Ad 1/4 1/4 1/2 0.02 t/11 U22 U33 U12 U13 Un Na 4e 1/2 0.3659(5) 3/4 0.020(2) 0.020(2) 0.026(2) 0 0.010(2) 0 Al 4c 1/4 1/4 0 0.008(1) 0.007(1) 0.010(1) 0.0009(9) 0.0043(9) -0.0001(9) Β 4e 1/2 0.033(1) 1/4 0.004(3) 0.005(4) 0.009(3) 0 0.005(3) 0 Ρ 8/ 0.2255(1) 0.0656(2) 0.6822(2) 0.0075(6) 0.0062(7) 0.0075(6) 0.0007(6) 0.0040(5) 0.0000(6) 0(1) 8/ 0.4323(4) 0.1365(5) 1.1000(4) 0.007(2) 0.012(2) 0.008(2) 0.001(2) 0.003(2) 0.004(1) 0(2) 8/ 0.3919(4) 0.0796(5) 0.7579(4) 0.010(2) 0.006(2) 0.014(2) 0.000(2) 0.006(2) -0.002(2) 0(3) 8/ 0.1805(4) 0.0961(5) 0.8163(4) 0.007(2) 0.009(2) 0.011(2) 0.000(2) 0.006(1) -0.000(2) 0(4) 8/ 0.1783(4) -0.1085(5) 0.6098(4) 0.011(2) 0.007(2) 0.014(2) -0.003(1) 0.007(1) -0.003(1) 0(5) 8/ 0.1611(4) 0.2010(5) 0.5462(4) 0.012(2) 0.014(2) 0.012(2) -0.002(2) 0.005(2) 0.005(2) Correspondence author (e-mail: koch@cpfs.mpg.de) 442 NaAl[BP207(0H)3] References 1. Kniep, R.; Engelhardt, Η.; Häuf, C.: A First Approach to Borophosphate Structural Chemistry. Chem. Mater. 10 (1998) 2930-2934. 2. Hauf, C.; Boy, I.; Kniep, R.: Oligomere Tetraeder-Anionen in Borophosphaten: Darstellung und Kristallstrukturen von NaFe[BP207(0H)3] und K2Fe2[B2P40i6(0H)2]. Z. Naturforsch. 53b (1998) 165-170. 3. Sheldrick, G. M.: SHELXL-97, a program for refining crystal structures. University of Göttingen, Germany 1997. 4. Brandenburg, K: DIAMOND. Visual information system for crystal structures. University of Bonn, Germany 1996.

Crystal structure of bis(benzylammonium) lead tetrachloride, (C7H7NH3)2PbCl4

Abstract: Ci4H2oCl4N2Pb, orthorhombic, Cmc2\\ (No. 36), a =33.619(7) Â, b =7.820(l)Ä,c =7.728(1) A, V=2031.6 Â, Z= 4, Rgí(F) = 0.021, RW(F) = 0.054, Τ = 293 Κ. Source of material The colorless crystals were grown from solution of lead chloride and benzylammonium chloride (1:2) in dimethylformamide by slowly evaporation of the solvent. Benzylamine was obtained from Merck. The adjunct chloride salt was prepared by addition of a stoichiometric amount of 37% concentrated HCl. Discussion The crystal is a network of alternating inorganic and organic layers (Fig. 1). The molecules forming the organic layer are bound via their ammonium anchor to the inorganic layers which consist of corner-sharing lead chloride octahedra (Fig. 2). There is evidence for ionic interaction between the ammonium ion and the chloride (N-Cl distance 3.22 Â and 3.25 Â). The energetic triplet state of the molecular layer is isoenergetic to the exciton band of the lead chloride which leads to a resonant energy transfer between the organic and inorganic layers [1]. V e 2 r J JT Fig. 2. Plot of the organic cation and the [PbClö] octahedron. Table 1. Data collection and handling. Crystal: colorless plate, size 0.01 χ 0.35 χ 1.1 mm Wavelength: Mo Ka radiation (0.71073 À) μ: 88.25 cm\" Diffractometer, scan mode: Nicolet P3, Wyckoff 20max 55° N(hkl)measured, N(hkl)u„iquc: 1136, 1120 Criterion for /0bs, N(hkl)gc. Us > 2 cjf/obs), 1083 N(param)rcfmei: 101 Programs: SHELXS-86 [2], SHELXL-93 [3] Table 2. Atomic coordinates and displacement parameters (in Â). Atom Site X y ζ C/iso H(1A) 8 b 0.5490(2) 0.6818(7) -0.0448(9) 0.071 H(1B) 8 b 0.5780(2) 0.6960(7) 0.0936(9) 0.071 H(1C) 8 b 0.5818(2) 0.5611(7) -0.0347(9) 0.071 H(1D) 8 b 0.5954(3) 0.758(1) -0.251(2) 0.075 H(1E) 8 b 0.5914(3) 0.904(1) -0.112(2) 0.075 H(3) 8 b 0.6454(4) 0.958(1) 0.089(2) 0.105 H(4) 8 b 0.7113(4) 0.937(2) 0.146(3) 0.152 H(5) 8 b 0.7488(5) 0.725(2) 0.020(3) 0.134 H(6) 8 b 0.7203(3) 0.546(2) -0.170(3) 0.154 H(7) 8 b 0.6533(3) 0.571(1) -0.247(2) 0.107 332 Bis(benzylammonium) lead tetrachloride Table 3. Atomic coordinates and displacement parameters (in Â). Atom Site X y ζ Un Un ί/33 Un Un 1/23 Pb(l ) 4 a 1/2 0.76140(3) 0.41354(8) 0.0383(2) 0.0250(1) 0.0292(2) 0 0 -0.0011(5) Cl( l ) 86 0.58510(6) 0.7289(2) 0.3926(9) 0.0479(7) 0.0473(6) 0.049(2) -0.0054(5) -0.001(1) 0.003(1) Cl(2) 4 a 1/2 0.9149(3) 0.0803(6) 0.060(2) 0.040(1) 0.048(1) 0 0 0.013(1) Cl(3) 4 a 1/2 0.4445(3) 0.2221(6) 0.050(1) 0.0365(9) 0.039(1) 0 0 -0.0070(8) N( l ) 8 b 0.5745(2) 0.6692(7) -0.0173(9) 0.048(4) 0.044(3) 0.052(3) -0.002(2) 0.005(3) -0.005(2) C( l ) 8 b 0.5997(3) 0.787(1) -0.130(2) 0.055(4) 0.060(3) 0.072(9) -0.006(3) -0.005(4) 0.013(4) C(2) 8 b 0.6421(3) 0.7710(8) -0.090(8) 0.049(3) 0.059(4) 0.060(5) -0.010(3) 0.00(1) 0.01(1) C(3) 8 b 0.6604(4) 0.876(1) 0.032(2) 0.079(8) 0.084(7) 0.100(8) -0.006(5) -0.011(7) -0.032(6) C(4) 8 b 0.6995(4) 0.861(2) 0.069(3) 0.067(8) 0.13(1) 0.19(2) -0.026(7) -0.04(1) -0.01(1) C(5) 8 b 0.7220(5) 0.736(2) -0.007(3) 0.046(6) 0.14(2) 0.15(2) -0.009(6) 0.004(8) 0.022(9) C(6) 8 b 0.7050(3) 0.632(2) -0.120(3) 0.058(6) 0.112(8) 0.21(2) 0.002(6) 0.05(1) -0.03(1) C(7) 8 b 0.6645(3) 0.645(1) -0.166(2) 0.071(6) 0.085(6) 0.113(9) -0.007(5) 0.034(6) -0.027(6) Acknowledgment. We thank W. Tuffentsammer for the preparation of the crystal samples.

Redetermination of the crystal structure of dipotassium dialuminum borate, K2AI2B2O7, a new non-linear optical material

Abstract: AI2B2K2O7, trigonal, P321 (No. 150), a = 8.5657(9) A, c = 8.463(2) A, F = 537.8 A, Z = 3, R#(F) = 0.018, wR(F) = 0 . 0 6 0 , T= 2 9 7 K . Source of material The K2AI2B2O7 (KAB) crystals were obtained by the top-seeded solution growth (TSSG) method with K2CO3 B2O3 LiCl flux. The starting materials K2CO3, B2O3, AI2O3 and LiCl were mixed thoroughly in the appropriate ratio and then heated in a platinum crucible until they were completely melted by using a vertical cylindrical electric furnace. Crystal growth was carried out at a cooling rate of0.3~0.5 Kd from the saturation temperature. The large crystal was grown in 25 days, and was cut for X-ray determination. Discussion The phase K2 AI2B2O7 was studied by Kaduk and Satek [ 1 ]. They provided X-ray evidence of the K2AI2B2O7 compound, and the material crystallizes in the hexagonal space group P321 with a = 8.55800(2) A, c = 8.45576(3) A. FWHM = 0.08° at 30° TT, Ä-factor: 0.145. However, the crystal class was a mistake as hexagonal insted of trigonal [1]. In fact we found that K2AI2B2O7 (KAB) is a new non-linear optical (NLO) crystal [2]. In this study, the K2AI2B2O7 crystal structure is redetermined by X-ray analysis. The basic structural features of KAB crystal contains Κ cations, BO3 groups and AIO4 groups. The planes of all the BO3 groups are approximately parallel to the c axis. The whole atomic arrangement can be described as being formed from layers of AIO4 tetrahedra and BO3 triangles having a composition Αΐ2(Βθ3)2θ. By condensation via the \"free\" oxygen corners of the AIO4 tetrahedra, a three dimensional Ab(B03)20 framework is formed which houses the Κ ions. The B-O bond lengths in the BO3 groups range from 1,372( 1) A to 1,368( 1) A, with the O B O angles range from 120.6(1)° to 119.18(8)°. These B 0 bond lengths and O-B-O bond angles are quite typical for BO3 group. Likewise, the A l 0 bond lengths in the distorted tetrahedral AIO4 groups range from 1.7557(8) A to 1.6995(4) A, with the 0 A 1 0 bond angles range from 110.64(3)° to 108.28(3)°. The Al 0 Λ1 bond angle between the Al2(B03)20 layers is 180°, with the A l 0 bond lengths are shorter than the Al-O bond lengths within the layers. KAB possesses a space arrangement similar to Sr2B2Be207 (SBBO) [3]. In the SBBO structure, the nearly planar (Be3B306)oo network with all BO3 groups perpendicular to the c axis, and the three terminal oxygen atoms of the BO3 are linked with Be atoms. The second harmonic generation (SHG) coefficient come from BO3 groups. Compared with SBBO, the major NLO active group of KAB is also the BO3 group with its three terminal oxygen atom of BO3 group to be linked with Al atoms. Because the orientation of BO3 between the adjacent layers is not identical, the SHG coefficient of KAB is expected to be weaker than that of SBBO. Table 1. Data collection and handling. Crystal: Wavelength: μ; Diffractometer, scan mode:

Redetermination of the crystal structure of tertrasodium tetrahedro-tetrastannide, Na4Sn4 and tetrapotassium tetrahedro-tetrastannide, K4Sn4.

Abstract: Na4Sn4, tetragonal, IA\\lacd (No. 142), a = 10.475(1) A, c = 17.412(2) A, V= 1910.5 Ä , Ζ = 8, Rgt(F) = 0.058, wR(F) = 0.058, T= 295 K. K4Sn4, tetragonal, IA\\lacd (No. 142), a = 11.409(1) Ä, c = 18.649(2) Ä, V = 2427.5 Ä , Ζ = 8, Rgt(F) = 0.036, wR(F) = 0.036, T= 295 K. Source of material Stoichiometric mixtures of the elements were heated up to 1273 Κ for 1 day and annealed at 673 Κ for one week (Nb container welded at 30 kPa Ar). Single phases (by X-ray diffraction) with silvery grey crystals were formed. The compounds are very sensitive against oxidation and hydrolysis and have to be handled under inert conditions. Lattice parameters were determined from Guinier-Simon powder patterns [1] with Si standard (X(CuÄai) = 1.54051 A ; a(Si) = 5.4305 A). Discussion Both compounds form the i/64 structure of NaPb [2] as shown by Hewaidy et al. [3] for K4Sn4 and by Müller et al. [4] for Na4Sn4 from single crystal structure analysis. In order to compare several NaPb-type structures in detail, both crystal structures were redeterminated. The lattice parameters are slightly different to the former values while the da ratios are almost unchanged. Two interpenetrating 3D frameworks of condensed M 4 Sn 4 (M = Na, K) stellae quadrangulae (distorted heterocubanes [5]) are formed, hierarchically related to the CU2O structure [6]. The tetrahedranide anions Sn*~ M(Sn-Sn) = 2.978(2) A (Na4Sn4); d(Sn-Sn) = 2.949(1) A (K4Sn4)) are connected via twofold μ-bridging M l atoms to ^,(Ml4/2[Sn4]) substructures which are interconnected by 'interstitial' μ-bridging M2 atoms. In total, 16 Μ atoms form cages around the tetrahedra with 3.350(2) A < rf(Na-Sn) < 3.539(2) A and 3.682(1) A < d(K-Sn) < 3.850(2) A, respectively. 1. Tetrasodium tetrahedro-tetrastsumide, Na4Sn4 Table 1. Data collection and handling. Crystal: silvery grey, irregular, size 0.1 χ 0.1 χ 0.1 mm Wavelength: Mo Ka radiation (0.71069 A) μ: 52.3 cm\" Diffractometer, scan mode: Stoe STADI4, ω/20 29max 65° N(hkl)mcasured, N(hkl)unique: 1793,872 Criterion for Fobs, N(hkl)gc. fobs > 6 o(FobS), 395 N(param) refined: 20 Programs: CSD [7], ATOMS [8] * Correspondence author (e-mail: baiti@vsibml.mpi-stuttgart.mpg.de) 4 5 4 Na4SiH and K4S114 Table 2. Atomic coordinates and displacement parameters (in Ä, origin choice 2). Atom Site V11 U22 U33 f/12 f/l3 1/23 Na(l) I6e Na(2) 16/ Sn 32g 0.875(2) 0 0.375(1) jc+1/4 0.0695(2) 0.1261(2) 1/4 0.034(7) 0.030(7) 1/8 0.039(5) i /n 0.93525(9) 0.0263(8) 0.0302(9) 0.044(7) 0 0 -0.007(7) 0.043(8) -0.001(9) -0.005(5) -U13 0.0276(7) -0.0007(8) -0.0088(8) 0.0114(8) 2. Tetrapotassium tetrahedro-tetrastannide, K4S114 Table 3. Data collection and handling.

Crystal structure of dilithiumsulfíde, Li2S

Abstract: Li2S, cubic, Fiiβm (No. 225), a = 5.7158(1) A, V= 186.7 A3, Z = 4, REi(F) = 0.009, Rv.(F) = 0.009, T= 293 K.

Crystal structure of dilithium (nitridolithiate/ferrate(I)), Li2[(Li1-xFex)N], x = 0,63

Abstract: Feo.63Li2.37N, hexagonal, P6/mmm (No. 191), a = 3.724(2) A, c = 3.630(1) Ä, V= 43.6 Ä, Z = 1, R&(F) = 0.030, wR(F) = 0.072, T= 293 K. Source of material Single crystals of Li2[(Lii_JFex)N] (x = 0.63) were obtained by thermal treatment of mixtures of Li3[FeN2] [1] and an alkali metal (Li, Na) with molar ratios of 1:1 in Fe crucibles under Ar (1 atm). The mixtures were first heated to 523 Κ (1.3 K/min, 12 h) and then heated to 1173 Κ (3 K/min). After reaching the maximum temperature the reaction products were cooled down (3 K/min) to ambient temperature. Table 2. Atomic coordinates and displacement parameters (in A). Discussion Li2[(Lio.37Feo.63)N] is a member of a substitution series Li2[(Lii_^Fe^)N] which crystallizes in the Li2[LiN] crystal structure [2]. This general type of substitution series is already known, since the early work of Robert Juza et al. [3], who first reported the existence of ternary compounds LhlXLii-ZTE^N] (TE =Co, Ni, Cu) from X-ray powder investigations. Reinvestigations in these systems [4, 5] based on single crystal data confirmed the early observation, that the bond lenghts (Lii-xTEJ-N decrease with increasing χ parameter. In case of the title compound the bond length (Lii (x = 0.63) within the infinite chains is shortened from 193.8(l)pm forLi2[LiN] (x=0) [2] to 181.5(l)pm. Table 1. Data collection and handling. Crystal: black plate, size 0.2 χ 0.2 χ 0.4 mm Wavelength: Mo Ka radiation (0.71070 Ä) μ: 48.61 cm\" Diffractometer, scan mode: Siemens P4, ω/2θ 20max: 59.22° M/Vasured^i MOunique: 360, 42 Criterion for /0bs, N(hkl)g. /0bs > 2 a(/0bs), 42 N(param),trmaf. 9 Programs: SHELXL-97 [6], DIAMOND [7] Atom Site Occ. X y ζ Un U22 U33 Un U13 U23 Fe(l) lb 0.63(2) 0 0 1/2 0.036(1) Uu 0.016(1) 0.0180(5) 0 0 Li(l) 1 b 0.37 0 0 1/2 0.036(1) Un 0.016(1) 0.0180(5) 0 0 Ν 1 a 0 0 0 0.033(3) Un 0.021(3) 0.017(1) 0 0 Li(2) 2c 1/3 2/3 0 0.082(8) Un 0.06(1) 0.041(4) 0 0 * Correspondence author (e-mail: klatyk@cpfs.mpg.de) 4 4 8 Li2[(Lii-xFe.i)N], χ = 0 .63 Acknowledgment. We thank the Deutsche Forschungsgemeinschaft (Schwerpunktprogramm \"Reaktivität von Festkörpern\") for supporting this work.

Crystal structure of caesium iron(III) catena-[monohydrogenmonoborate-bis(monophosphate], CsFe[BP2O8(OH)]

Abstract: BCsFeH09P2, monoclinic, P\\2\\!c\\ (No. 14), a = 9.351(2) A, b = 8.631 (4) Ä, c = 9.763(2) Ä, β = 102.58(2)°, V = 769.0 Ä, Z = 4, R&(F) = 0.024, wR(F) = 0.083, T= 293 K. Source of material CsFe[BP2C>8(OH)] was prepared by hydrothermal reaction of 2.78 g of a 50 wt.% aqueous solution of CsOH, 2.51 g FeCl3 · 6H20,0.57 g H3BO3 and 2.14 g H3PO4 (85%) (molar ratio 1:1:1:2,conc. solution, pH 1) in teflon autoclaves at Τ = 433 K 443 Κ for six days. Discussion The crystal structure of CsFe[BP20s(0H)] (hydrated borophosphate, B:P < 1; [1]) contains open-branched vierer-einfach chains [BP20s(0H)]~, which are formed by alternating hydrogenborate and phosphate tetrahedra sharing common corners. The caesium-iron(III) compound is an isotype of RbFe[BP20s(0H)][2]. Fe is in an octahedral coordination (FeOs(OH)) by oxygen sites of three neighbouring tetrahedral chains, while Cs is irregularly coordinated by ten oxygen sites. Bond lengths and angles within the anionic partial structure are consistent with related borophosphates (see [1, 2] and refs. therein). Table 1. Data collection and handling. Crystal: amethyst-like (pale-violet), monoclinic prism, size 0.04 χ 0.03 χ 0.25 mm Wavelength: Mo Ka radiation (0.71073 A) μ: 70.68 cm\" 1 Diffractometer, scan mode: Siemens P4 , ω 20rnax! 60° N(hkl) measured, Wi&Oumque: 5058, 2237 Criterion for /0bs, N(hkl)$: /obs > 2 a(/0bsj, 2056 N(param) refined: 131 Programs: SHELXS-97 [3], SHELXL-97 [4] Table 2. Atomic coordinates and displacement parameters (in Ä). Atom Site χ y ζ U is0 H(l) 4e 0.382(9) 0.592(7) 0.025(8) 0.05(2) * Correspondence author (e-mail: engelhar@cpfs.mpg.de) 444 C s F e [ B P 2 O g ( O H ) ] Table 3. Atomic coordinates and displacement parameters (in A). Atom Site X y ζ U π Ü22 ί/33 U12 t/13 Ü23 Cs 4e 0.19523(2) 0.61015(3) 0.55238(2) 0.0247(2) 0.0199(2) 0.0218(2) -0.00106(7) 0.0020(1) -0.00393(7) Fe 4e 0.20561(5) 0.15542(5) 0.42773(4) 0.0096(2) 0.0107(2) 0.0095(2) -0.0003(1) 0.0014(2) 0.0004(1) Β 4e 0.3413(4) 0.5433(4) 0.1948(4) 0.010(1) 0.011(1) 0.014(1) 0.000(1) -0.002(1) -0.000(1) P(l) 4e 0.07373(8) 0.42853(9) 0.20068(8) 0.0087(3) 0.0102(3) 0.0094(3) 0.0005(2) 0.0013(2) 0.0007(2) P(2) 4e 0.41972(8) 0.23297(9) 0.21319(8) 0.0083(3) 0.0098(3) 0.0111(3) 0.0007(2) 0.0013(2) 0.0005(2) 0(1) 4e 0.0748(2) 0.0050(3) 0.3137(2) 0.0097(9) 0.018(1) 0.018(1) -0.0038(8) 0.0020(8) -0.0053(8) 0(2) 4e 0.0863(3) 0.3325(3) 0.0735(2) 0.017(1) 0.018(1) 0.0102(9) -0.0022(8) 0.0073(8) -0.0029(8) 0(3) 4e 0.1011(3) 0.3333(3) 0.3358(2) 0.015(1) 0.014(1) 0.014(1) 0.0041(8) 0.0017(8) 0.0038(8) 0(4) 4e 0.1940(2) 0.5588(3) 0.2225(2) 0.0104(9) 0.013(1) 0.017(1) -0.0010(7) 0.0040(8) -0.0023(8) 0(5) 4e 0.3236(3) 0.5373(3) 0.0406(2) 0.018(1) 0.015(1) 0.0098(9) -0.0040(8) 0.0018(8) -0.0004(8) 0(6) 4e 0.3411(3) 0.1310(3) 0.2992(3) 0.016(1) 0.0123(9) 0.021(1) -0.0012(8) 0.0085(9) -0.0002(8) 0(7) 4e 0.3601(3) 0.2182(3) 0.0566(2) 0.019(1) 0.016(1) 0.0084(9) 0.0041(9) -0.0005(8) -0.0008(8) 0(8) 4e 0.4206(3) 0.4056(2) 0.2620(2) 0.016(1) 0.0098(9) 0.014(1) 0.0023(8) -0.0008(8) 0.0004(7) 0(9) 4e 0.5845(2) 0.1857(3) 0.2455(3) 0.0092(9) 0.0114(9) 0.020(1) 0.0010(7) 0.0012(8) 0.0034(8) Acknowledgments. We thank the Pinguin-Stiftung (Düsseldorf) and the Fonds der Chemischen Industrie for supporting this work. References 1. Kniep, R.; Engelhardt, Η.; Häuf, C.: A First Approach to Borophosphate Structural Chemistry. Chem. Mater. 10 (1998) 2930-2934. 2. Kniep, R.; Boy, I.; Engelhardt, Η.: RbFe[BP20g(0H)]: Ein neues Borophosphat mit offen-verzweigten Vierer-Einfach-Tetraederketten. Ζ. anorg. allg. Chem., in press. 3. Sheldrick, G. M.: SHELXS-97 Program for the Solution of Crystal Structures. University of Göttingen, Germany 1997. 4. Sheldrick, G. M.: SHELXL-97 Program for Crystal Structure Refinement. University of Göttingen, Germany 1997.

Crystal structure of tetrarubidium tetrahedro-tetrastannide, Rb4Sn4 and of tetracaesium tetrahedro-tetrastannide, Cs4Sn4

Abstract: Rb4Sn4, tetragonal, I4\\/acd (No. 142), a = 11.757(1) A, c= 19.215(2) Ä, V = 2656.0 Ä, Ζ = 8, Rgt(F) = 0.053, wR(F) = 0.053, Γ =295 Κ. Cs4Sn4, tetragonal, IA\\/acd (No. 142), a = 12.122(1) A, c= 19.820(2) Ä, V= 2912.4 Ä, Z = 8, Rst(F) = 0.067, wR(F) = 0.067, 7 = 295 K. Source of material Stoichiometric mixtures of the elements were heated up to 1273 Κ for 1 day and annealed at 673 Κ for one week (Nb container, welded at 30kPa Ar). Single phases (by X-ray diffraction) with silvery grey crystals were formed. The compounds are very sensitive against oxidation and hydrolysis and have to be handled under inert conditions. Lattice parameters were determined from Guinier-Simon powder patterns [ 1 ] with Si standard (λ(Οι/Γαι) = 1.54051 A ; a(Si) = 5.4305 Ä). Table 1. Data collection and handling. Crystal: silvery grey, irregular, size 0.1 χ 0.1 χ 0.2 mm Wavelength: Mo Ka radiation (0.71069 Ä) μ: 227.5 cm 1 Diffractometer, scan mode: Stoe STADI4, ω/20 2örriax • 55° N(hkl)measured, N(hkl)Umqw· 1593,778 Criterion for fobs, N(hkl)gc. Fobs > 4 o(Fobs), 574 N(param) refined: 20 Programs: CSD [6], ATOMS [7] Table 2. Atomic coordinates and displacement parameters (in Ä , origin choice 2). Atom Site U11 U22 i/33 U12 U13 1/23 Rb(l) I6e 0.8582(2) 0 1/4 0.033(1) 0.037(1) 0.038(1) 0 0 -0.009(1) Rb(2) 16/ 0.3798(2) x+1/4 1/8 0.0382(8) Un 0.038(1) 0.002(1) -0.0003(8) -U13 Sn 32g 0.06304(1) 0.14176(1) 0.92908(6) 0.0287(6) 0.0296(6) 0.0284(5) 0.0003(5) -0.0053(5) 0.0074(5) Cs1(Rb1) * Correspondence author (e-mail: baiti@vsibml.mpi-stuttgart.mpg.de) 458 Rb4Sn4 and CS4S114 2. Tetracaesium tetrahedro-tetrastannide, CS4S114 Table 3. Data collection and handling.

Crystal structure of alkaline earth dilithium bis(nitridolithiate/ferrate(I)), Ca{Li2[(Li1-xFex)N]2}, x = 0,30 and Sr{Li2[(Li1-xFex)N]2}, x = 0,46

Abstract: CaFeo.6iLi3.39N2, tetragonal, IA\lamd (No. 141), a = 3.7637(3) Ä, c = 26.168(3) Ä, V = 370.7 Ä, Ζ = 4, Rgt(F) = 0.018, wR(F) = 0.050, T= 293 K. Feo.92Li3.o8N2Sr, tetragonal, IAilamd (No. 141), a = 3.7909(2) Ä, c = 27.719(3) A, V= 398.3 Ä, Z = 4, Rgt(F) = 0.019, wR(F) = 0.048, T= 293 K. Source of material Single crystals of the isotypic compounds Ca{Li2[(Lii jFe'A-)N]2) (x = 0.30) and Sr{ Li2[(Lil_xFeJ)N]2} (jc = 0.46) were obtained by reaction of mixtures of Li2r(Lii-xFe'x)N] [1] (χ = 0.33, determined by atomic absoφtion spectroscopy), Li and Ca3N2 (molar ratio 9:16:4) and Li2[(Lio.66Feo.33)N], Li and Sr2N (molar ratio 6:7:4), respectively. The reactions were carried out under Ar (1 atm). The mixtures were first heated to 523 Κ (1.3 K/min, 12h) and then heated to 923 Κ (2.2 K/min). After a period of 48 h at the maximum temperature the reaction products were cooled down (2 K/min) to ambient temperature. Discussion Ca{Li2[(Lio.7oFeo.3oN)]2} and Sr{Li2[(Lio.54Feo.46N)]2} are isotypes of SrLi2[LiN]2 [2], SrLi2[LiN]2 contains extended layered fragments 2 {Li[LiN]~| of the Li2[LiN] type structure [3]. The anionic layers are stacked along the tetragonal c axis direction alternatingly rotated by 90° to each other. Alkaline earth cations occupy tetrahedral holes between neighbouring nitrogen layers along [001 ]. In this way, every nitrogen function completes its coordination sphere to give a pentagonal bipyramidal arrangement (N[EA2/4Li3/3Li2/2]). Nitrogen together with the axial Li positions form infinite chains [(L1N2/2)] with Li-N distances in the ternary compound of 191.3(2) pm. It was already shown [4-6] that lithium within the linear chains 1 [(L1N2/2)] can partially be substituted by Cu and Ni, an observation which is now extended to respective ferrate systems [1], Shortening of the ( L i ^ F e ^ N distance with increasing χ parameter is also found for the quaternary title compounds. Ca: (Lio.7oFeo.3o)-N: 188.31(2) pm; Sr: (Lio.54Feo.46)-N: 189.59(2) pm. The enlargement of ionic radii of the alkaline earth species in the quaternary phases (Ca Sr) is consistent with a "spacer" function. 1. Calcium dilithium bis(nitridolithiate/ferrate(I)), Ca{Li2[(Lio.7oFeo.3oN]2} Table 1. Data collection and handling. Correspondence author (e-mail: klatyk@cpfs.mpg.de) Crystal: black plate, size 0.3 χ 0.6 χ 0.9 mm Wavelength: M o Ka radiation (0 .71070 Ä) μ: 37.31 cm" Diffractometer, scan mode: Siemens P4, ω/2θ 29max: 59 .76° JVfAWjmeasured, N(hkl)uaique· 501, 178 Criterion for /0bs, N(hkl)gt: lob·, > 2 a(!ohs), 141 N(param) refined: 17 Programs: S H E L X S 9 7 [7], S H E L X L 9 7 [8], DIAMOND [9] 450 Ca{Li2[(Lio.7oFeo.3oN]2} and Sr{Li2[(Lio.54Feo.46N]2} Table 2. Atomic coordinates and displacement parameters (in Ä). Atom Site Occ. χ y ζ Uu U22 C/33 i /12 i/13 Uli Ca( l ) 4 a 0.0 3/4 1/8 0.0185(3) Uu 0.0172(3) 0 0 0 Fe( l ) 8e 0.302 (2) 0 1/4 0.30796(4) 0.0177(6) 0.0113(5) 0.0242(6) 0 0 0 Li( l ) 8e 0.698 0 1/4 0.30796 0.0177 0.0113 0.0242 0 0 0 Li(2) 8e 0 1/4 0.7719(2) 0.021(2) 0.034(3) 0.026(2) 0 0 0 N( l ) 8e 0 1/4 0.06058(7) 0.015(1) 0.019(1) 0.0181(8) 0 0 0 2. Strontium dilithium bis(nitridolithiate/ferrate(I)), Table 3. Data collection and handling. Crystal: black plate, size 0.3 χ 0.6 χ 0.9 mm Wavelength: Mo Ka radiation (0.71070 Ä) μ: 165.43 cm" 1 Diffractometer, scan mode: Siemens P4, ω/20 26max: 59.76° /V(M/)nieasured· N(hkl)„„iqUe: 530, 189 Criterion for /0bS, N(hkl)t(. /o b s > 2 a(70bsλ 163 N(param)KHnti'· 17 Programs: SHELXS-97 [7], SHELXL-97 [8], DIAMOND [9] Table 4. Atomic coordinates and displacement parameters (in Ä). Atom Site Occ. X y ζ Uu U22 i/33 U,2 i/13 U21 Sr(!) 4 a 0 3/4 1/8 0.0140(3) Uu 0.0136(3) 0 0 0 Fe( l ) 8e 0.462(3) 0 1/4 0.30507(4) 0.0161(6) 0.0090(6) 0.0170(6) 0 0 0 Li( l ) 8e 0.538 0 1/4 0.30507 0.0161 0.0090 0.0170 0 0 0 Li(2) 8e 0 1 /4 0.7721(2) 0.014(3) 0.033(4) 0.018(3) 0 0 0 N ( l ) 8e 0 1 /4 0.0566(1) 0.011(1) 0.013(2) 0.016(1) 0 0 0 Acknowledgment. W e thank the Deutsche Forschungsgemeinschaf t (Schwerpunktprogramm "Reaktivität von Festkörpern") for supporting this work.

Crystal structure of dilithium (nitridolithiate/manganate(I)), Li2[(Li1-xMnx)N], x = 0,73

Abstract: Li2.27Mno.73N, hexagonal, P6/mmm (No. 191), a = 3.7263(4) Ä, c = 3.8281(4) Ä, V= 46.0 Ä, Z = 1, R&(F) = 0.025, wR(F) = 0.063, Τ = 293 Κ. Source of material Single crystals of I^IXLii-jMnViN] (x = 0.73) were obtained by thermal treatment of mixtures of Li7[MnN4] [ 1 ] and Li with molar ratios of 1:1 in Ta crucibles under Ar (1 atm). The mixtures were first heated to 523 Κ (1.3 K/min, 12h) and then heated to 1173K (3 K/min). After reaching the maximum temperature the reaction products were cooled down (3 K/min) to ambient temperature. Discussion Li2[(Lio.27Mno.73)N] is a member of a substitution series Li2[(Lii-xMn'x)N] which crystallizes in the Li2[LiN] structure type [2], This general type of substitution series is already known, since the early work of Robert Juza et al. [3], who first reported the existence of ternary compounds Li2[(Lii_/TE.t)N] (TE = Co, Ni, Cu) from X-ray powder investigations. Reinvestigations in these systems [4, 5], based on single crystal data confirmed the early observation, that the bond lenghts (Lii-jTE^-N decrease with increasing χ parameter. In case of the title compound the bond length (Lii-xMnJ-N (x = 0.73) within the infinite chains is shortened from 193.8(1) pm in Li2[LiN] (x = 0) [2] to 191.4(2) pm. It is interesting to note that the decrease of the bond lengths of (Lii-jMnJ-N with increasing χ parameter is much smaller compared with the isotypic phases Li2[(Lii-xTE'x)N] (TE = Fe [6], Co, Ni, Cu [3-5]). Table 1. Data collection and handling. Crystal: brass plate, size 0.2 χ 0.2 χ 0.4 mm Wavelength: Mo Ka radiation (0.71070 A) μ: 48.43 cm\" 1 Diffractometer, scan mode: Siemens P4, ω/2θ 28max: 59.6° N(hkl)measured, N(hkl)miquc: 257,44 Cri ter ion fo r /0bs, N(hkl)gt: /obs > 2 cf/obs), 44 N(param),er,ned'· 8 Programs: SHELXL-97 [7], DIAMOND [8] Table 2. Atomic coordinates and displacement parameters (in Ä). Atom Site X y ζ t/ll U22 U33 Un Un Un Mn lb 0.73(2) 0 0 1/2 0.0305(6) Un 0.0081(6) 0.0153(3) 0 0 Li(l) lb 0.27 0 0 1/2 0.0305 Uu 0.0081 0.0153 0 0 Ν la 0 0 0 0.019(2) U\\i 0.009(2) 0.0094(8) 0 0 Li(2) 2c 1/3 2/3 0 0.047(4) Uu 0.040(6) 0.024(2) 0 0 * Correspondence author (e-mail: klatyk@cpfs.mpg.de) 446 Dilithium (nitridolithiate/manganate(I)) Acknowledgment. We thank the Deutsche Forschungsgemeinschaft (Schwerpunktprogramm \"Reaktivität von Festkörpern\") for supporting this work.

Crystal structure of pentastrontium trigermanide, Sr5Ge3

Abstract: Ge3Sr5, tetragonal, iAl mem (No. 140), a = 8.134(4) Â, c = 15.771(8) A, V= 1043.4 Â , Z = 4, Re{F) = 0.045, AwfF) = 0.116, T = 298 K. Table 2. Atomic coordinates and displacement parameters (in Â). Atom Site X y ζ Sr(l) 4c 0 0 0 Sr(2) 16/ 0.1739(1) x+l/2 0.14441(7) Ge(l) 4a 0 0 1/4 Ge(2) Sh 0.3874(2) x+l/2 0 Acknowledgment. This work was supported by the Swiss National Founda- tion. References 1. Eisenmann, Β.; Schafer, Η.: Die Kristallstruktur der Verbindungen CasSI3 und Ca5Ge3. Z. Naturforsch. 29b (1974) 460-463. 2. Dorscheids W.; Widera, Α.; Schafer, H.: Darstellung und Kristallstruktur von SrsSn3 und Ba5Sn3. Z. Naturforsch. 32b (1977) 1097-1099. 3. Biuzzone, G.; Franceschi, E.; Merlo, F.: M5X3 Intermediate Phases Formed by Ca, Sr and Ba. J. Less-Common Met. 60 (1978) 59-63. Source of material Sr5Ge3 was prepared in a two-step synthesis. A stoichiometric mixture of the elements was heated at 1073 Κ (1 d, cooling down within 16 h). The product obtained was ground and then tempered at 1473 Κ (4 h, cooling down within 2 d). SrsGe3 f o r m s grey-black, plate-l ike crystals with a metall ic lustre. It is exceptionally air and moisture sensitive. Discussion Sr5Ge3 crystallises with the CrsB3 structure type, like other M5X3 compounds (M = EA; X = Si, Ge, Sn, Pb) [1-4]. It contains Ge i 6 " dumb-bells and isolated G e 4 Zintl anions. Therefore, S rsGej can be described, according to the Zintl-Klemm concept, by the formulation (Sr )5[Ge2 ][Ge~]. The G e G e bond distance in the dumb-bell is 2.59 Â. Sri is coordinated by four equatorial Ge2 dumb-bells and two axial G e l atoms forming a very elongated octahedron. This may be the reason for the large I/33 displacement parameter of S r i . Table 1. Data collection and handling. Crystal: black piece, size 0.10 χ 0.20 χ 0.30 mm Wavelength: Mo Ka radiation (0.71073 Â) μ: 337.90 cm* Diffractometer, scan mode: Stoe STADI4, ω/θ 28max: 59.94° N(hkl)measured, JVf/ji/Jimique: 4288,435 Criterion for /0bs, N(hkl)gc U s > 2 a(/obs), 390 N(param) ref,ned: 15 Programs: SHELXS-96 [5], SHELXL-96 [6], ORTEPII [7] 4. Sands, D. E.; Wood, D. H.; Ramsey, W. J.: The Structures of BasPb3, BaPb and BaPb3. Acta Crystallogr. 17 (1964) 986-989. 5. Sheldrick, G. M.: SHELXS-96. Program for the solution of crystal structu- res. University of Gottingen, Germany 1996. 6. Sheldrick, G. M.: SHELXL-96. Program for refining crystal structures. University of Gottingen, Germany 1996. 7. Larson. A.C.; Lee, F. L.; Le Page Y.; Webster, M.; Charland, J. P.; Gabe, E. J.: NRCVAX Crystal Structure System with interactive version of ORTEP II, NRC, Ottawa, Canada 1986. U11 U22 I/33 U12 Un Un 0.0201(6) t/11 0.048(2) 0 0 0 0.0242(4) Un 0.0185(5) 0.0002(4) -0.0036(3) ί/13 0.0251(7) Un 0.018(1) 0 0 0 0.0186(5) Un 0.0139(7) -0.0003(6) 0 0 Unauthenticated Download Date | 3/9/16 10:07 AM

Crystal structure of L-cysteine L-tartarte monohydrate, C7H15NO9S

Abstract: C7H15NO9S, monoclinic, P\2u (No. 4), a = 7.9152(8) Â, b = 7.7166(6)A, c — 10.4111(9) Â, β= 111.0°, V=593.7 Â3,

Crystal structure of 2,2'-bipyridine-(η4-cycloocta-1,5-diene)rhodium(I) hexafluorophosphate, (C18H20N2)RhPF6

Abstract: Ci8H2oF6N2PRh,monoclinic,P12i/nl (No. 14),a =9.0375(7)Ä, b= 11.5621(9) A,c= 17.714(1) Ä, β = 98.262(1)°, V = 1831.8 Ä, Ζ = 4, Rgt(F) = 0.035, wR(F) = 0.037, T= 296 Κ. Source of material The title compound was prepared from the reaction of chloro(r | 4 -cyclooctal ,5-diene)rhodium(I) dimer with 2,2'-bipyridine in ethanol in the presence of sodium hexafluorophosphate. Analytically pure single crystals were obtained by slow evapration of the the solution. Discussion The crystal lattice of the title compound consists of the 2,2'-bipyridine-(r|-cycloocta-l,5-diene)rhodium(I) cations and hexafluorophosphate anions. The latter have a normal octahedral structure and warrants no further discussion. The organometallic cation features slightly distorted square-planar coordination around the Rh center. The mean deviation of the least-squares plane formed by Nl, N2, Rh and the centers of C11-C12 and C15-C16 is 0.025(2) Ä. The Rh atom is situated 0.052(4) Ä above this plane. The least-squares plane formed by the 2,2'-bipyridine ligand has a mean deviation of 0.051(4) A. Crystal: red platelet, size 0.15 χ 0.33 χ 0.33 mm Wavelength: Mo Ka radiation (0.7107 Ä) μ: 10.83 cm" 1 Diffractometer, scan mode: Bruker CCD, ω, Δω = 1.0° 20max: 54.14° /V(fcW)measured N(hkl)umqae9654, 3826 Criterion for I0bs, N(hkl)gt: U s > 2.5 2335 N(param)ref[ned'· 253 Programs: teXsan [1], SIR92 [2] Table 2. Atomic coordinates and displacement parameters (in Ä). Atom Site X y ζ Uis ο H(l) 4e 0.4371 0.1322 0.3326 0.052 H(2) 4e 0.6362 -0.0256 0.3737 0.052 H(3) 4e 0.7928 0.0154 0.5047 0.052 H(4) 4e 0.7160 0.1659 0.5836 0.052 H(5) 4e 0.6695 0.3107 0.6318 0.052 H(6) 4e 0.5802 0.4735 0.7026 0.052 H(7) 4e 0.3611 0.5779 0.6486 0.052 H(8) 4e 0.2232 0.5102 0.5331 0.052 H(9) 4e 0.1811 0.0990 0.3477 0.052 H(10) 4e 0.2938 0.2505 0.2776 0.052 H( l l ) 4e 0.1552 0.3973 0.2209 0.075 H(12) 4e 0.0098 0.3305 0.2296 0.075 H(13) 4e 0.0968 0.5279 0.2897 0.078 H(14) 4e -0.0535 0.4650 0.2938 0.078 H(15) 4e 0.1491 0.5174 0.4239 0.052 H(16) 4e 0.0459 0.3578 0.4890 0.052 H(17) 4e -0.1188 0.2398 0.4411 0.098 H(18) 4e -0.1526 0.3134 0.3674 0.098 H(19) 4e -0.0427 0.1100 0.3832 0.099 H(20) 4e -0.0926 0.1785 0.3086 0.099 * Correspondence author (e-mail: shuangl @kent.edu)

Crystal structure of methylammonium sulfanilate, (CH3NH3)H2NC6H4SO3

Abstract: C7H12N2O3S, monoclinic, P\\2\\lc\\ (No. 14), a = 11.100(2) A, è = 7.448(1) Â, c = 24.228(5) À, β = 95.69(3)°, V= 1993.1 À, Z = 8, Rgt(F) = 0.043, RW(F) = 0.107, Τ = 293 Κ. Source of material Large single crystals were obtained from aqueous solutions of the title compound by controlled lowering of temperature and by slow evaporation in the range between 315 Κ and 290 Κ [1]. Discussion The_structure can be described as a sequence of layers parallel (102) which consist alternately of methylammonium cations and sulfanilic anions. One hydrogen atom of each amine group and all Η-atoms of the ammonium groups are involved in a 3-dimensional network of hydrogen bonds with donor-acceptor distances between 2.738 Â and 3.050 Â and D-H-A angles of about 155°. The relatively large and highly anisotropic thermal vibrations of the oxygen atoms of the SO3 groups may be a hint on the structural instability which causes the first order phase transition at 313 Κ [1], Table 1. Data collection and handling. Crystal: colorless prism, size 0.3 χ 0.3 χ 0.35 mm Wavelength: Mo Ka radiation (0.71073 Â) μ: 3.04 cm\" 1 Diffractometer, scan mode: Nonius CAD4, ω/2θ 29max: 49.94° N(hkl)measured, N(hkl)unique: 3688, 3496 Criterion for /0bs. N(hkl)gt: Us > 2 af/obs), 2740 N(param)Kr¡T¡a¡: 332 Programs: PARST95 [2], SHELXS-97 [3], SHELXL-97 [4], ATOMS [5] a3 Table 2. Atomic coordinates and displacement parameters (in Â). * Correspondence author (e-mail: schreuer@kristall.erdw.ethz.ch) Atom Site X y ζ t/iso H(1S1) 4e 0.523(3) 0.307(4) 0.709(1) 0.052(8) H(2S1) 4e 0.412(3) 0.312(4) 0.785(1) 0.060(9) H(3S1) 4e 0.672(3) 0.037(4) 0.871(1) 0.062(9) H(4S1) 4e 0.774(3) 0.010(4) 0.795(1) 0.046(8) H(5S1) 4e 0.436(3) 0.271(5) 0.885(2) 0.07(1) H(6S1) 4e 0.513(4) 0.157(6) 0.911(2) 0.09(2) H(1S2) 4e 0.915(3) 0.788(4) 0.951(1) 0.056(9) H(2S2) 4e 0.994(3) 0.700(4) 0.872(1) 0.07(1) H(3S2) 4e 0.676(3) 0.526(4) 0.812(1) 0.063(9) H(4S2) 4e 0.592(3) 0.602(4) 0.890(1) 0.061(9) H(5S2) 4e 0.967(3) 0.565(5) 0.788(2) 0.07(1) H(6S2) 4e 0.858(3) 0.487(5) 0.765(2) 0.08(1) H(1M1) 4e 0.382(3) 0.660(6) 0.480(2) 0.08(1) H(2M 1 ) 4e 0.351(3) 0.772(5) 0.435(2) 0.07(1) H(3M1) 4e 0.394(3) 0.843(5) 0.483(2) 0.08(1) H(4M1) 4e 0.189(3) 0.891(6) 0.472(2) 0.09(1) H(5M1) 4e 0.177(4) 0.683(6) 0.472(2) 0.10(2) H(6M1) 4e 0.229(4) 0.774(6) 0.526(2) 0.11(2) H(1M2) 4e 0.183(3) 0.229(5) 0.341(1) 0.06(1) H(2M2) 4e 0.192(3) 0.416(6) 0.343(2) 0.08(1) H(3M2) 4e 0.195(3) 0.311(5) 0.392(2) 0.09(1) H(4M2) 4e -0.002(5) 0.237(7) 0.378(2) 0.13(2) H(5M2) 4e -0.003(4) 0.348(7) 0.323(2) 0.12(2) H(6M2) 4e 0.011(4) 0.430(6) 0.377(2) 0.10(2) 318 Methylammonium sulfanilate Table 3. Atomic coordinates and displacement parameters (in Â). Atom Site χ y ζ Un U22 ί/33 U12 U13 Í/23 S(1S1) 4e 0.74392(6) 0.15262(9) 0.68597(3) 0.0513(4) 0.0459(4) 0.0390(4) -0.0043(3) 0.0133(3) -0.0009(3) O( lSl ) 4e 0.6584(2) 0.1037(5) 0.63964(9) 0.092(2) 0.154(3) 0.041(1) -0.041(2) 0.015(1) -0.014(2) 0(2S 1 ) 4e 0.8335(2) 0.0115(3) 0.6966(1) 0.084(2) 0.058(1) 0.087(2) 0.018(1) 0.042(1) 0.001(1) 0(3S 1 ) 4e 0.7985(2) 0.3236(3) 0.6799(1) 0.109(2) 0.047(1) 0.093(2) -0.010(1) 0.054(2) 0.002(1) C(1S1) 4e 0.6628(2) 0.1609(3) 0.7444(1) 0.041(1) 0.034(1) 0.034(1) -0.001(1) 0.003(1) -0.001(1) C(2S 1 ) 4e 0.5527(3) 0.2496(4) 0.7417(1) 0.051(2) 0.040(2) 0.044(2) 0.007(1) 0.001(1) 0.005(1) C(3S1) 4e 0.4886(3) 0.2563(4) 0.7872(1) 0.046(2) 0.047(2) 0.063(2) 0.008(1) 0.016(1) -0.002(1) C(4S 1 ) 4e 0.5333(3) 0.1771(4) 0.8370(1) 0.057(2) 0.044(2) 0.045(2) -0.010(1) 0.016(1) -0.009(1) C(5S 1 ) 4e 0.6424(3) 0.0859(4) 0.8392(1) 0.060(2) 0.050(2) 0.034(1) -0.006(1) 0.003(1) 0.006(1) C(6S1) 4e 0.7066(2) 0.0770(4) 0.7935(1) 0.041(1) 0.040(2) 0.045(2) 0.004(1) 0.001(1) 0.002(1) NCI S1 ) 4e 0.4662(4) 0.1835(6) 0.8825(2) 0.087(3) 0.083(3) 0.064(2) -0.007(2) 0.037(2) -0.011(2) S(1S2) 4e 0.68256(6) 0.77524(9) 0.98913(3) 0.0468(4) 0.0444(4) 0.0400(4) 0.0005(3) 0.0112(3) -0.0023(3) 0(1 S2) 4e 0.6037(2) 0.6332(3) 1.00475(9) 0.070(1) 0.051(1) 0.077(1) -0.003(1) 0.035(1) 0.006(1) 0(2S2) 4e 0.6129(2) 0.9351(3) 0.97332(8) 0.079(1) 0.045(1) 0.058(1) 0.016(1) 0.019(1) -0.0040(9) 0(3S2) 4e 0.7818(2) 0.8130(4) 1.03065(8) 0.060(1) 0.122(2) 0.044(1) -0.002(1) 0.004(1) -0.018(1) C(1S2) 4e 0.7478(2) 0.7017(3) 0.9299(1) 0.041(1) 0.034(1) 0.039(1) -0.000(1) 0.007(1) -0.003(1) C(2S2) 4e 0.8687(2) 0.7319(4) 0.9239(1) 0.040(1) 0.062(2) 0.045(2) -0.008(1) 0.003(1) -0.013(1) C(3S2) 4e 0.9168(3) 0.6823(5) 0.8761(1) 0.043(2) 0.069(2) 0.055(2) -0.008(2) 0.013(1) -0.010(2) C(4S2) 4e 0.8457(3) 0.6019(4) 0.8326(1) 0.058(2) 0.042(2) 0.040(1) 0.006(1) 0.007(1) -0.002(1) C(5S2) 4e 0.7244(3) 0.5712(4) 0.8392(1) 0.053(2) 0.053(2) 0.045(2) -0.003(1) -0.003(1) -0.013(1) C(6S2) 4e 0.6766(3) 0.6204(4) 0.8870(1) 0.040(2) 0.049(2) 0.054(2) -0.004(1) 0.004(1) -0.009(1) N(1S2) 4e 0.8927(4) 0.5594(5) 0.7835(1) 0.075(2) 0.078(2) 0.050(2) 0.000(2) 0.016(2) -0.014(2) N(1M1) 4e 0.3475(3) 0.7640(4) 0.4688(1) 0.061(2) 0.049(2) 0.053(2) -0.005(1) 0.005(1) 0.008(1) C(1M1) 4e 0.2229(4) 0.7837(7) 0.4823(2) 0.071(3) 0.060(3) 0.114(4) -0.001(2) 0.022(2) 0.003(2) N(1M2) 4e 0.1614(3) 0.3237(4) 0.3568(1) 0.063(2) 0.042(2) 0.049(2) 0.001(1) 0.004(1) -0.000(1) C(1M2) 4e 0.0309(4) 0.3359(7) 0.3569(2) 0.063(2) 0.083(3) 0.086(3) 0.006(2) 0.007(2) -0.010(3) Acknowledgment. The author is gratefully indebted to Prof. S. Haussiihl for providing large single crystals of methylammonium sulfanilate.

Crystal structure of bis(2-naphthylmethylammonium) lead tetrachloride, (C11H9NH3)2PbCl4

Abstract: C22H24Cl4N2Pb, orthorhombic, Pbam (No. 55), a = 7.749(2) Â, b = 7.790(2) Á, c = 20.859(3) À, V= 1259.1 Á, Z = 2, Rgt(F) = 0.048, R„(F) = 0.111, 7\"=293 K. Source of material The colourless crystals were grown from solution of lead chloride and 2-naphthylmethyl-ammonium chloride with the ratio 1:2 in dimethylformamide by slowly evaporation of the solvent. 3 3 4 Bis(2-naphthylmethylammoniuin) lead tetrachloride Table 3. Atomic coordinates and displacement parameters (in Â). Atom Site Occ. X y ζ U H t /22 t/33 t / 1 2 U13 t/23 Pb(l) 2 a 0 0 0 0.0863(8) 0.0348(5) 0.0340(5) 0.0211(5) 0 0 Cl(l) 4e 0 0 0.1367(2) 0.054(2) 0.068(3) 0.044(2) -0.001(2) 0 0 Cl(2) 4 g 0.1778(6) 0.3211(6) 0 0.053(2) 0.058(2) 0.053(2) 0.004(2) 0 0 C(l) 4/ -1/2 0 0.2306(8) 0.08(1) 0.052(9) 0.041(9) 0.01(1) 0 0 C(1 A) 4 / -1/2 0 0.160(1) 0.07(1) 0.17(3) 0.05(1) -0.04(2) 0 0 N(l) 8 0.5 -0.396(2) -0.079(2) 0.1206(8) 0.05(1) 0.039(9) 0.04(1) 0.001(8) 0.019(9) 0.001(8) C(2) 8 0.369(2) 0.084(2) 0.2617(7) 0.14(2) 0.065(9) 0.059(9) 0.03(1) 0.02(1) 0.010(8) C(3) 8 0.5 0.303(3) 0.052(3) 0.326(1) 0.05(2) 0.05(2) 0.05(1) 0.01(1) 0.00(1) 0.02(1) C(4) 8 0.5 0.419(4) 0.050(3) 0.361(1) 0.07(2) 0.07(2) 0.04(1) 0.01(1) 0.02(1) 0.01(1) C(5) 8 0.5 0.385(5) 0.077(5) 0.427(1) 0.10(3) 0.09(2) 0.04(2) 0.00(2) 0.01(2) 0.01(2) C(6) 8 0.5 0.249(6) 0.008(5) 0.456(1) 0.13(3) 0.11(3) 0.05(1) 0.02(3) 0.01(2) 0.00(2) C(7) 8 0.5 0.143(5) 0.099(5) 0.421(2) 0.09(2) 0.12(3) 0.07(2) 0.00(2) 0.04(2) 0.02(2) C(8) 8 0.5 0.166(3) 0.129(3) 0.356(1) 0.08(2) 0.10(3) 0.07(2) 0.01(2) 0.02(2) 0.01(2) C(3A) 8 0.5 0.431(3) 0.121(3) 0.329(1) 0.11(3) 0.07(2) 0.05(2) 0.03(2) 0.01(2) 0.00(2) Acknowledgment. We thank W. Tuffentsammer for the preparation of the crystal samples.

Crystal Structure Of Europium Cobalt Aluminide (1/2/9), EuCo2Al9

Abstract: Discussion EUC02AI9 is a new compound, which is isotypic with BaFe2Al9 [1]. The europium atoms are coordinated by 12 Al(2) atoms at 349.2 pm, two Eu atoms at 389.8 pm, and six Al( 1) atoms at 393.2 pm. The cobalt atoms have 9 aluminum neighbors at distances of 227.0 pm (3x) and 254.9 pm (6x) in the form of a tricapped trigonal prism. Both aluminum atoms have two Eu and two Co neighbors. In addition, the Al( 1) atoms have eight Al(2) neighbors at 281.5 pm, and the Al(2) atoms have 4A1( 1) (281.5 pm), 2 Al(2) (284.5 pm), and 2 Al(2) (289.8 pm) neighbors. Other isotypic compounds are CaCo2Al9 [2] and SrNi2Al9, SrCo2Al9, BaNi2Al9, B a C o 2 A l 9 [ l ] .

Crystal structure of 1,3-dimethylbenzimidazole-2-selenone, C9H10N2Se

Abstract: C9HioN2Se, monoclinic, P\\2\\!n\\ (No. 14), a = 7.414(1) Ä, b = 14.339(1) Ä, c = 9.225(1) Ä, β = 107.70(1)°, V= 934.2 Ä, Ζ = 4, RgiF) = 0.038, Rv4F) = 0 .115 ,T= 293 K. Source of material Selenium (0.56 g; 7.16 mmol) was added to a solution of bis(l,3dimethylbenzimidazolidine-2-ylidene) (0.95 g; 3.25 mmol) in toluene (25 cm) and heated under reflux for 4 h. Then the solution was filtered while hot to remove excess of selenium. After cooling the solution to apprpx. 323 Κ pentane (15 cm) was added. Upon cooling the solution to 243 Κ white crystalls of the title compound were obtained (1.4 g; 96%, mp = 433 Κ 434 Κ). All reactions were performed under an argon or nitrogen atmosphere with use of schlenk techniques [1]. The solvents were deoxygenated and dried by standard methods [2], Discussion Electron-rich olefins are powerful reducing agents [3]. It is known that the ultimade oxidation product of electron-rich olefins [3-5] with air is urea; sulphur, selenium and tellurium react similarly to form the corresponding anologues [6,7], The oxidation rate is strongly dependent on the availability of electrons and hence on the substituents on the nitrogen. There are extensive studies about cyclic ureas having imidazolidine moiety including their X-ray crystal structure [8]. Less attention has been paid to the cyclic urea which contains benzimidazole moiety and there is no example known for the X-ray crystal structure determination. The aim of this study was to elucidate crystal structure of previously synthesised cyclic urea having benzimidazole moiety [9] and compare with imidazole analogues. In the compound, Nl-Cl and N2-C1 bond lengths resemble almost with Nl -Cl and N2-C1 bond lengths in the bis( 1 -methyl3-ethylbenzimidazolidine-2-ylium) tetrafluoroborate [10]. The Nl -Cl bond length is 1.377(8) Ä and N2-C1 bond length is 1.382(8) Ä. Table 1. Data collection and handling. Crystal: cream, prismatic, size 0.35 χ 0.40 χ 0.40 mm Wavelength: Mo Ka radiation (0.71073 A) μ: 39.64 cm\" 1 Diffractometer, scan mode: Enraf-Nonius CAD4, oV20 20max: 45.38° NfMijmeasured, N(hkl)unique: 1157,1157 Criterion for /0bs, N(hkl)gc /obs > 2 o(/0bs), 1026 N(param)Te fined: 110 Programs: SHELXS-86 [11], SHELXL-97 [12], ORTEPII [13] Table 2. Atomic coordinates and displacement parameters (in A). Atom Site X y ζ Ui so H(3) 4e 0.1576 0.152 1.2302 0.092 H(4) 4e 0.2295 0.0226 1.369 0.114 H(5) 4e 0.3157 -0.1175 1.2765 0.117 H(6) 4e 0.3176 -0.1237 1.0178 0.095 H(8A) 4e 0.0854 0.2875 0.8401 0.133 H(8B) 4e 0.1888 0.2899 1.0157 0.133 H(8C) 4e -0.022 0.2561 0.9543 0.133 H(9A) 4e 0.2934 -0.0941 0.773 0.117 H(9B) 4e 0.3509 -0.0162 0.6763 0.117 H(9C) 4e 0.1376 -0.0443 0.6419 0.117 * Correspondence author (e-mail: bgunes@sirius.gazi.edu.tr) 296 l,3-Dimethylbenzimidazole-2-selenone Table 3. Atomic coordinates and displacement parameters (in A). Atom Site X y ζ Uu U22 t/33 U,2 Uu t/23 Se(l) 4e 0.1494(1) 0.18246(5) 0.61588(8) 0.109(1) 0.089(1) 0.068(1) -0.0027(3) 0.0302(6) 0.0128(3) N(l) 4e 0.1634(8) 0.1610(4) 0.9286(7) 0.078(3) 0.068(3) 0.068(4) -0.005(3) 0.030(3) -0.009(3) N(2) 4e 0.2334(7) 0.0346(3) 0.8287(5) 0.069(3) 0.071(3) 0.048(3) -0.001(2) 0.013(2) -0.002(2) C(l) 4e 0.1830(8) 0.1230(5) 0.7971(7) 0.061(3) 0.063(4) 0.076(4) -0.014(3) 0.022(3) -0.008(3) C(2) 4e 0.1993(8) 0.0968(4) 1.0414(7) 0.058(3) 0.073(4) 0.054(4) -0.007(3) 0.015(3) -0.007(3) C(3) 4e 0.192(1) 0.0981(6) 1.1888(8) 0.083(4) 0.094(5) 0.054(4) -0.013(4) 0.023(3) -0.006(4) C(4) 4e 0.233(1) 0.0210(8) 1.269(1) 0.079(5) 0.146(8) 0.059(5) -0.019(5) 0.018(3) -0.002(5) C(5) 4e 0.285(1) -0.0654(6) 1.214(1) 0.083(5) 0.124(7) 0.081(5) -0.015(4) 0.016(4) 0.037(5) C(6) 4e 0.288(1) -0.0694(5) 1.0606(9) 0.080(4) 0.070(4) 0.080(5) -0.008(3) 0.015(4) 0.013(4) C(7) 4e 0.2431(8) 0.0131(5) 0.9794(7) 0.061(3) 0.087(4) 0.062(4) -0.012(3) 0.023(3) -0.002(3) C(8) 4e 0.098(1) 0.2569(6) 0.9352(9) 0.092(5) 0.078(5) 0.099(5) -0.001(4) 0.034(4) -0.014(4) C(9) 4e 0.256(1) -0.0361(5) 0.7206(9) 0.091(5) 0.076(4) 0.075(5) 0.009(3) 0.036(4) -0.003(4) Acknowledgments. The authors wish to acknowledge the purchase of CAD4 diffractometer under. Grand DPT/TBAG1 of The Scientific and Technical Research Concil of Turkey.

Crystal structure of hexaaquadi(μ3-hydroxo)tetra(μ2-hydroxo)tetrakis-(μ3-{1-[2-(6-methylpyridyl)]ethanone oximato})hexakis(μ2-{1-[2-(6-methylpyridyl)] ethanone oximato)nonanickel(II) Perchlorate hydrate, [Ni9(C7H7N2O)10(OH)6(H2O)6](ClO4)2 ∙ 10H2O

Abstract: C70Hi08Cl2N20Ni9O40, triclinic, PI (No. 2), a = 15.920(7) Ä, b = 16.673(8) Ä, c = 20.58(1) Ä, α = 77.80(6)°, β = 81.00(6)°, γ = 72.60(4)°, V = 5070.1 Ä , Ζ = 2, R%{F) = 0.108, Rv/fF) = 0.263, T= 193 K. Source of material The preparation of the pyridine oxime ligand HL has been described in [1]. Favourable conditions for the formation of the polynuclear complex were obtained when the pH of the aqueous solution containing nickel(II) chloride and the ligand in molar ratio 1:1 was adjusted to 8 with NaOH. Attempts to isolate a crystalline complex from such solutions were unsuccessful, but when the counter ion was changed to Perchlorate ion, a l ight green crysta l l ine c o m p l e x of c o m p o s i t i o n [Ni9Li0(OH)6(H2O)6](ClO4)2 · 1 0 H 2 0 was obtained [2], Discussion The metallacrown [3] structure contains an octahedral NiOö central core and four different octahedral N1O4N2 and N1O2N4 environments. All the oxime groups are deprotonated and the nine nickel atoms are linked together via several bior trifurcated oximato and hydroxo bridges. Hydrogen atom positions of the water molecules and OH groups were not found. Water oxygen atoms 0 2 6 W and 0 2 8 W are disordered. * Correspondence author (e-mail: aarne.pajunen@helsinki.fi) 1.1 X 0.2x0.3 mm 73 A)

Crystal structure of dysprosium hydroxide carbonate, DyOHCO3

Abstract: CHDyCM, orthorhombic, P2i2i2i (No 19), α = 4835(1) Â, b = 6984(1) Â, c = 8449(1) A, V = 2853 Â, Ζ = 4, R%{F) = 0038, Rv/F) = 0095, T= 293 K Crystal: Wavelength: μ: Diffractometer, scan mode: 2Omax: N(hkl)measarei· N(hkl)unique: Criterion for /0bs, N(hkl)g 2 a(Iobi) 1 7 5 6 56 SHELXS-86 [8], SHELXL-93 [9], DIAMOND [10] Unauthenticated Download Date | 3/9/16 11:07 AM 12 Dysprosium hydroxide carbonate Table 2 Atomic coordinates and displacement parameters (in Â) Atom Site X y ζ Un t/22 f/33 Un Un t/23 Dy 4a 000745(3) 011386(3) 016386(2) 001555(9) 001453(9) 00194(1) 000038(6) -000041(6) -000102(4) C(l) 4 a 05037(8) 04513(6) 01727(4) 0013(1) 0017(1) 0019(1) 0001(1) 0004(1) -00008(9) O(l) 4a 02829(7) 03969(7) 00986(4) 0017(1) 0020(1) 0022(1) -0001(1) -0003(1) 0002(1) 0(2) 4a 04904(8) 05505(5) 02973(4) 0018(1) 0024(1) 0023(1) 0001(1) 0000(1) -0007(1) 0(3) 4a 07405(7) 04129(5) 01130(5) 0015(1) 0017(1) 0025(2) 0002(1) 00022(9) -0000(1) 0(4) 4a 00035(9) 07942(5) 01134(4) 0027(2) 0015(1) 0022(1) -0001(1) -0001(1) 00026(9)

Crystal structure of tetrarubidium tetrahedro-tetraplumbide, Rb4Pb4 and of tetracaesium tetrahedro-tetraplumbide, Cs4Pb4

Abstract: Pb4Rb4, tetragonal, lA\\lacd (No. 142), a = 11,892( 1) Ä, c = 19.429(2) k,V= 2747.6 Ä, Ζ = 8, Rgt(F) = 0.035, wR(F) = 0.035, T= 295 K. Cs4Pb4, tetragonal, lA\\lacd (No. 142), a = 12.244(1) Ä, c = 20.001(2) A,V= 2998.5 Ä, Ζ = 8, Rgl(F) = 0.084, wR(F) = 0.074, T= 293 K. Source of material Stoichiometric mixtures of the elements were heated up to 1273 Κ for 1 day and annealed at 573 Κ for one week (Nb container, welded at 30kPa Ar). Single phases (by X-ray diffraction) with silvery grey crystals were formed. The compounds are very sensitive against oxidation and hydrolysis and have to be handled under inert conditions. Lattice parameters were determined from Guinier-Simon powder patterns [1] with Si standard (X(CuiCai) = 1.54051 A ; a(Si) = 5.4305 Ä). Discussion Both compounds form the ?/64 structure of NaPb [2] as shown by Hewaidy et al. [3] from powder pattern, but detailed parameters were missing. The well-known structure type is characterized by two interpenetrating 3D frameworks of condensed M4Pb4 (M = Rb, Cs) stellae quadrangulae (distorted heterocubanes [4]), hierarchically related to the CU2O structure [5]. The tetrahedranide anions Pb* J(Pb-Pb) = 3.098(4) A (Rb4Pb4) rf(Pb-Pb) = 3.090(2) A (Cs4Pb4)) are connected via twofold μ -bridging Μ1 atoms to 3 (Ml4/2[Pb4]) substructures which are interconnected by 'interstitial' μ -bridging M2 atoms. In total, 16 Μ atoms form cages around the tetrahedra with 3.824(3) d(Rb-Pb) 3.981(4) and 3.969(1) d{Cs-Pb) 4.133(2), respectively. 1. Tetrarubidium tetrahedro-tetraplumbide, Rb4Pb4 Table 1. Data collection and handling. Crystal: silvery grey, irregular, size 0.1 χ 0.1 χ 0.1 mm Wavelength: Ag Ka radiation (0.56088 A) μ: 352.1 cm\" 1 Diffractometer, scan mode: Stoe IPDS, 400 exposures, Δφ = 0.5° 2Gmax: 61° N(hkl)measured, N(hkl)unique: 4391,2155 Criterion for Fobs, N(hkl)gt: Fobs > 4 a(Fobs), 288 N(pa ram)refined: 21 Programs: CSD [6], ATOMS [8] * Correspondence author (e-mail: baiti@vsibml.mpi-stuttgart.mpg.de) 4 5 6 Rb4Pb4 and Cs4Pb4 Table 2. Atomic coordinates and displacement parameters (in A, origin choice 2). Atom Site X y ζ Un U22 t/33 Un U13 t/23 Rb(l) 16e 0.8630(9) 0 1/4 0.038(5) 0.041(5) 0.041(4) 0 0 -0.010(5) Rb(2) 16/ 0.3798(6) x+1/4 1/8 0.042(3) Uu 0.042(4) 0.009(5) -0.003(3) -Un Pb 32g 0.0610(2) 0.1352(2) 0.93160(1) 0.032(1) 0.031(1) 0.032(1) 0.003(1) -0.008(1) 0.009(1) 2. T e t r a c a e s i u m f e i r a / i e r f r o t e t r a p l u m b i d e , Cs4Pb4 Table 3. Data collection and handling. Crystal: Wavelength: μ: Diffractometer, scan mode: 20ma*: /VfftWjmeasured, N(hkl)amnue. Criterion for fobs, N(hkl)gt: N(param)refined'· Programs: dark plate, size 0.16 χ 0.16 χ 0.06 mm Mo K a radiation (0.71073 A) 400.00 cm\" Siemens-Nicolet, Wyckoff 50° 1550, 864 fobs > 4 of Fobs), 631 25 SHELXTL-plus [7], ATOMS [8] Table 4. Atomic coordinates and displacement parameters (in Ä , origin choice 2). Atom Site l /n Ü22 t/33 U12 t/13 t/23 Cs(l) 16e Cs(2) 16/ Pb(l) 32g 0.8570(2) 0 1/4 0.032(1) 0.038(1) 0.045(1) 0.3817(2) jc+1/4 1/8 0.0384(9) U\\\\ 0.043(1) 0.06114(8) 0.13984(8) 0.92974(5) 0.0306(6) 0.0298(6) 0.0344(6) 0 0 -0.010(1) O . O O H D 0 . 0 0 0 0 ( 7 ) -υ η 0.0020(4) -0.0060(4) 0.0082(4)

Crystal structure of betaine potassium iodide dihydrate, (C5H11NO2)2KI·2H2O

Abstract: C10H26KN2O6, triclinic, PI (No. 2), a = 5.653(2) Â, b = 5.894(2) Â, c = 14.02(1) Â, α = 82.23(4)°, β = 82.16(4)°, y=73.22(2)°, V = 440.7 Â, Ζ = 1, Rg{F) = 0.021, Rvj(F ) = 0.050, Τ = 293 Κ. Source of material The compound was synthesized from a saturated water solution of ionic potassium iodide and betaine. A small grain selected from the polycrystalline precipitate obtained was used as a seed for the growth of a larger single crystal. Discussion The structure was solved by direct methods. Hydrogen atoms participating in C-Η bonds were placed at calculated positions and refined as riding using the SHELXL-97 defaults [1]. The hydrogen atoms of the water molecules were located as a result of a Fourier difference synthesis and refined as riding. Table 1. Data collection and handling. Crystal: colorless, transparent prism, size 0.07x0.1 χ 0.2 mm Wavelength: Mo Ka radiation ( 0 . 7 0 9 3 0 Â ) μ: 2 0 . 7 5 c m \" 1 Diffractometer, scan mode: Enraf-Nonius CAD4, ω/2θ 2Θ„ Ι 3Χ: 6 9 . 7 6 ° WlWjmeasured, N(hkl)unique: 5 6 8 0 , 2 7 2 0 Criterion for /0bs, N(hkl): /obs > 2 a(Iobs), 2554 N(param)K fined: 1 0 4 Programs: SHELXL-97 [1], XCAD4 [9], SDP [10], ORTEPII [11] 84 Betaine potassium iodide dihydrate Table 2. Atomic coordinates and displacement parameters (in À). Atom Site χ y ζ Uis 0 H(4A) li 1.2130 0.8449 0.2997 0.054 H(4B) li 1.2693 0.6800 0.2165 0.054 H(1 A) 2 i 0.9665 0.7316 0.1018 0.062 H(IB) li 0.7285 0.9492 0.1033 0.062 H(1C) 21 0.7453 0.7316 0.1825 0.062 H(2A) 2 i 0.9756 1.2237 0.1052 0.069 H(2B) li 1.2153 1.0086 0.0995 0.069 Table 2. Continued. Atom Site X y ζ t/iso H(2C) li 1.1658 1.1762 0.1822 0.069 H(3A) li 0.8244 1.1714 0.3099 0.074 H(3B) li 0.6588 0.9995 0.3090 0.074 H(3C) li 0.6423 1.2173 0.2300 0.074 H(31) li 0.797(7) -0.147(4) 0.567(2) 0.123 H(32) li 0.660(6) -0.041(8) 0.495(3) 0.123 Table 3. Atomic coordinates and displacement parameters (in Â). Atom Site X y ζ U H U22 ί/33 U12 U13 ί/23 1 \\e 1/2 1/2 0 0.03520(9) 0.03927(9) 0.03897(9) -0.00180(5) -0.00183(5) -0.00254(5) Κ \\h 1/2 1/2 1/2 0.0424(2) 0.0552(3) 0.0364(2) -0.0163(2) -0.0028(2) 0.0043(2) 0(1) li 0.8284(3) 0.5803(3) 0.3481(1) 0.0499(7) 0.0637(8) 0.0548(7) -0.0252(6) 0.0054(5) 0.0096(6) Ν li 0.9517(2) 0.9456(2) 0.20571(8) 0.0298(5) 0.0316(5) 0.0310(5) -0.0074(4) -0.0009(4) -0.0023(4) C(4) li 1.1386(2) 0.7616(2) 0.2624(1) 0.0320(6) 0.0392(6) 0.0361(6) -0.0119(5) -0.0057(5) 0.0043(5) C(5) li 1.0503(3) 0.5715(3) 0.3320(1) 0.0466(7) 0.0397(6) 0.0296(6) -0.0170(6) -0.0029(5) 0.0004(5) C(l) li 0.8378(3) 0.8291(3) 0.1427(1) 0.0391(7) 0.0472(7) 0.0385(7) -0.0107(6) -0.0091(5) -0.0077(6) C(2) li 1.0895(3) 1.1027(3) 0.1425(1) 0.0445(7) 0.0423(7) 0.0487(8) -0.0157(6) -0.0044(6) 0.0116(6) C(3) li 0.7514(3) 1.0969(3) 0.2694(1) 0.0504(8) 0.0411(7) 0.0499(8) -0.0041(6) 0.0087(7) -0.0158(6) 0(3) li 0.7477(5) 0.0040(3) 0.5345(1) 0.122(2) 0.0479(8) 0.066(1) -0.0112(9) -0.015(1) 0.0110(7) 0(2) li 1.2294(3) 0.4164(3) 0.3656(1) 0.0619(8) 0.0505(7) 0.0645(8) -0.0155(6) -0.0169(6) 0.0201(6) Acknowledgments. We thank gratefully Dr. J. Albers for his collaboration in the study of betaine compounds. We are indebted to the Cultural Service of the German Federal Republic Embassy, the Deutscher Akademischer Austauschdienst (DAAD) and the German Agency for Technical Cooperation (GTZ) for the offer of a CAD-4 automatic diffractometer which enabled the experimental work to be carried out. This work was supported by Fundaçào para Ciência e Tecnologia and by PRAXIS/2/2. l/FIS/26/94. J. Agostinho Moreira thanks the Project PRAXIS XXI for his grant (DB/3192/94).

Crystal structure of anilinium Perchlorate, C6H5NH3+ClO4-

Abstract: C6HgClN04, orthorhombic, P2\\2\\2\\ (No. 19), a = 5.895(3) Â, b = 7.505(5) À, c = 18.909(7) k , V = 836.6 Â, Ζ = 4, Rè{F) = 0.039, RJF) = 0.092, Γ= 293 Κ.

Crystal structure of praseodym gallate, Pr4Ga2O9

Abstract: G a 2 0 9 P r 4 , m o n o c l i n i c , P\\2\\!c\\ ( N o . 14) , a = 7 . 8 2 5 6 ( 4 ) Ä , b = 1 1 . 0 3 2 2 ( 5 ) Ä , c = 1 1 . 4 9 5 9 ( 7 ) Ä , β = 1 0 9 . 1 8 7 ( 3 ) ° , V = 9 3 7 . 4 Ä 3 , Ζ = 4 , R ( P ) = 0 . 0 2 6 , wR(P) = 0 . 0 3 4 , R(I) = 0 . 0 3 3 , Τ = 2 9 5 Κ. Source of material Pr4Ga2Ü9 w a s s y n t h e s i z e d b y so l id state react ion o f the o x i d e s o f 4 N and 5 N qual i ty c o n t a i n i n g P n C b and Ga2Ü3 in a m o l a r ratio o f 2:1 . T h e s a m p l e w a s s intered in air in a c l o s e d Pt c r u c i b l e up to 1 7 5 3 Κ for 2 0 h. T h i s react ion l e d to a h o m o g e n e o u s product w h i c h w a s o f l ight green c o l o r after grinding. B e c a u s e o f the incongruent m e l t i n g o f SrPrGaC>4 o n e o f the m o s t f a v o u r e d candi dates f o r substrates f o r h i g h T c superconductors a shi f t in the me l t c o m p o s i t i o n during the g r o w t h p r o c e s s takes p l a c e . In c o n s e q u e n c e , Pr4Ga2Ü9 is f o r m e d in the mul t iphase res idual m e l t [ 1 ]. Starting a t o m i c coord ina te s for the r e f i n e m e n t w e r e taken f r o m E U 4 A I 2 O 9 [2], T h e d i s p l a c e m e n t parameters o f all a t o m s w e r e fixed to re l iable v a l u e s . Powder: light-green Wavelength: CuATa radiation (1.54059 A) μ: 1629.9 cm\"' Diffractometer: Stoe Stadi Ρ Scan mode: transmission Debye-Scherrer mode 26max, stepwidth: 89.98°, 0.02 N(points)meXuTti 4000 NfAWjmeasured 765 N(param) refined: 79 Program: RIETAN-97 [3] Table 2. Atomic coordinates and displacement parameters (in Ä). Atom Site X y ζ Ciso Pr(l) 4e 0.520(2) 0.100(2) 0.782(1) 0.006 Pr(2) 4e 0.027(2) 0.091(2) 0.806(1) 0.006 Pr(3) 4e 0.332(3) 0.122(2) 0.424(2) 0.006 Pr(4) 4e 0.834(3) 0.121(2) 0.419(2) 0.006 Ga(l ) 4e 0.215(5) 0.190(3) 0.137(3) 0.009 Ga(2) 4e 0.660(4) 0.184(3) 0.117(3) 0.009 0(1) 4e 0.761(9) 0.146(5) 0.804(5) 0.012 0(2) 4e 0.202(7) 0.236(4) 0.797(4) 0.012 0(3) 4e 0.176(9) 0.018(7) 0.190(7) 0.012 0(4) 4e 0.030(9) 0.219(7) 0.940(7) 0.012 0(5) 4e 0.404(8) 0.226(4) 0.083(5) 0.012 0(6) 4e 0.64(1) 0.224(8) 0.950(8) 0.012 0(7) 4e 0.737(7) 0.009(5) 0.173(4) 0.012 0(8) 4e 0.03(1) 0.020(5) 0.374(5) 0.012 0(9) 4e 0.613(9) 0.991(6) 0.390(6) 0.012

Crystal structure of dimagnesium (monohydrogenmonophosphate-dihydrogenmonoborate-monophosphate), Mg2[BP2O7(OH)3]

Abstract: B2H6Mg4O20P4, triclinic, P I (No. 1), a = 6.452(1) À, b = 6.455(2) À, c = 8.360(2) Â, α = 82.50(1)°, β = 82.56(2)°, γ = 80.98(2)°, V= 338.8 Â ,Z= 1, Rè{F) = 0.042, RW(F) = 0.108, Τ = 293 Κ. Source of material Mg2[BP207(0H)3] was prepared by hydrothermal reaction of H3BO3, MgHPCU • 3H20, and MgCh · 6H2O (molar ratio 1:1:2; conc. solution, pH = 0.5, (HCl)) at 433 K. Discussion The crystal structure of Mg2[BP2C>7(OH)3] contains two crystallographically independent trinuclear anions [(0H)02P0i/20ι/2Β(0Η)20ι/2-0ι/2Ρ03] of corner sharing tetrahedra. This type of oligomeric tetrahedral anion is also present in the crystal structure of NaFe[BP2C>7(OH)3][l]. Magnesium is in an octahedral coordination by O and OH corners of the oligomeric units. The octahedra share common edges to form infinite octahedral chains (figure) which are arranged in layers perpendicular to [111] and which are separated by layers containing the oligomeric tetrahedral anions (in the figure light: BO4, dark: PO4). Hydrogen positions could not be determined. According to geometrical aspects (short interatomic OO contacts) hydrogen bridges are supposed to be located between 0 1 Ό 1 4 (257 pm) and 02--02 (276 pm) or 016—019 (275 pm), respectively. Based on general principles of borophosphate structural chemistry [2] the terminal corners of the BO4 groups are assumed to be protonated. The metrical transformation by applying matrix (-1 -1 0,1 -1 0,0 0 1 ) results in a pseudo monoclinic space group C2lm, in which the structure can not be refined. The existence of a centre of symmetry was also excluded. Table 1. Data collection and handling. Crystal: Wavelength: μ: Diffractometer, scan mode: 20max: N(hkl)measmed, N(hkl)u„ique: Criterion for /0bs, N(hkl)gv N(param),e fined: Programs: colorless platelet, size 0.1 χ 0.2 χ 0.3 mm Mo Ka radiation (0.71070 Â) 8.76 cm\" Siemens P4, ω 72.2° 1535,1535 U s > 2 o(/obs), 1469 161 SHELXS-97 [3], SHELXL-97 [4] Table 2. Atomic coordinates and displacement parameters (in Â). Atom Site X y ζ U\\,o B(l) la 0.603(2) 0.741(1) 1.189(1) 0.020(2) B(2) la 0.160(2) 0.295(1) 0.236(1) 0.020(2) 0(1) 1 a 0.4083(9) 0.5385(8) 0.8587(6) 0.014(1) 0(2) la -0.276(1) -0.4114(9) 0.5458(7) 0.014(1) 0(3) la 0.008(1) -0.1337(9) 0.5272(7) 0.014(1) 0(4) la 0.0358(9) 0.2106(8) 0.6268(6) 0.012(1) 0(5) la 0.689(1) -0.1362(8) 0.7991(6) 0.012(1) 0(6) la 0.355(1) -0.0722(8) 0.6127(7) 0.014(1) 0(7) la 0.784(1) -0.3291(9) 1.0663(7) 0.017(1) 0(8) la 0.229(1) 0.1157(8) 0.3580(7) 0.016(1) 0(9) la 0.9718(9) -0.4552(8) 0.8128(6) 0.013(1) O(10) la -0.336(1) -0.1022(9) 0.2841(7) 0.025(1) 0(11) la 0.084(1) -0.513(1) 0.3145(7) 0.026(1) 0(12) la 0.002(1) 0.2358(9) 1.1410(7) 0.025(1) 0(13) la 0.414(1) 0.817(1) 1.1109(7) 0.027(1) 0(14) la -0.6397(9) -0.5067(8) 0.5666(6) 0.016(1) 0(15) la 0.672(1) 0.227(1) 0.9384(8) 0.032(2) 0(16) la 0.312(1) 0.1768(9) 0.8787(7) 0.015(1) 0(17) la -0.427(1) -0.4577(9) 0.2960(7) 0.024(1) 0(18) la 0.360(1) 0.3276(9) 1.1297(7) 0.023(1) 0(19) la 1.035(1) -0.1080(9) 0.8971(7) 0.013(1) 0(20) la -0.327(1) -0.7708(9) 0.4864(8) 0.029(1)

Crystal structure of bis(triethylammonium) hexachlororhenate(IV), (C6H16N)2ReCl6

Abstract: Discuss ion The structure is similar to reported structures earlier [3], The ReClé\" anion is nearly perfect octahedral. HN(C2Hs)3 is tetrahedraly as expected. T w o triethylammonium ions are linked with t h e R e C l ô a n i o n b y h y d r o g e n b o n d s f o r m i n g d i s c r e t e [HN(C2H5)3]2ReCl6 units ; symmetry operators o f C12 and C13 are 1/2+*, 3 / 2 y , 1/2+z and 1 /2-* , 1/2+y, 3 /2 -z , respectively.

Crystal structure of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine dioxouranium nitrate, C48H84N6O20P2U2

Abstract: C48H84N6O20P2U2, orthorhombic, Pna2\\ (No. 33), a = 19.7821(3) Ä, b = 10.6352(2) Ä, c = 31.4217(4) Ä, V = 6610.7 Ä, Ζ = 4, Rgt(F) =0.062, wR(F) = 0.148, Γ= 243 K. Source of material The complexe was prepared by addition of 0.8 mmol of CMPO to 1 mmol ofU02(N03)2 · 6H20 in ethanol and chloroforme (V/V). The mixture was heated at 343 Κ during one hour. Crystals were grown by slow evaporation from this solution. Analytically found: %C = 34.6, %N = 4.7, %H = 4.9; calculated: %C = 35.9, %N = 5.2, %H = 5.2. Discussion The carbamoyl methyl phosphine oxide derivatives represent an important class of ligands for the TRUEX (Trans Uranium Extraction) process : it removes both the actinide and lanthanide elements from strongly acidic nuclear waste solutions [1], The ligand used in this process is the octyl(phenyl)-./V,jV-diisobutylcarbamoylmethylphosphine oxide, called CMPO: its properties are similar to the other CMPO which are subsequently called CMPO like. A previous work suggested that in solution CMPO like [2] and CMPO in more recent works [3,4] act as bidentate extractants in a 1:1 ratio. In solid state, several structural studies concerning CMPO like-uranyl complexes show a ratio 1:1 [5-8]. * Correspondence author (e-mail: nier l ich@drecam.cea.fr) However only one study concerns a CMPO like : uranyl 2:1 ratio [9] in which the CMPO like act as monodentate ligand. The structure of the free CMPO was reported by Rogers [10]. We report here the first structure involving the CMPO and the uranyl nitrate. The structure contains two independant but similar molecules in the asymmetric unit. A view of one of these is shown in the figure together with the atomic numbering. Η atoms were not indroduced. The linear uranyl group is equatorially surrounded by six oxygen atoms provided by two adjacent and bidentate nitrates and one bidentate CMPO with a cis orientation of the C 0 and P-O groups. The six equatorial oxygen form a nearly planar hexagon (+0.08 Ä) around the U atom. In the structure of the free CMPO [10], the carbonyl and the phosphoryl groups are trans to each other whereas in the uranyl complex they are cis orientated. Rogers compares the C 0 and P-O bond distance in the complexed and uncomplexed CMPO like: they are significantly shorter for the uncomplexed ligand. It is confirmed for the CMPO: 1.232(7) Ä and 1.478(3) Ä for the C-O and P-O bond distances in the free CMPO and 1.31(8) Ä and 1.53(5) Ä in the complexed CMPO. Table 1. Data collection and handling. Crystal: yellow-green, irregular, size 0.15 x 0.20 x 0.25 mm Wavelength: Mo Ka radiation (0.71073 Ä) μ: 50.10 cm\" Diffractometer, scan mode: Siemens SMART CCD, ω rotation scans with narrow frames (30 exposures, Δφ = 1.0°) 29max: 49.3° N(hkl)measured, N(hkl)amq 2 a(/obs), 7213 N(param)re fined: 703 Programs: SHELXS-86 [11], SHELXL-93 [12]

Crystal structure of anhydrous tetraethylammonium chloride, [(CH3CH2)4N]Cl

Abstract: CgH2oClN, monoclinic, P\\2\\tn\\ (No. 14), a = 11.8207(2) Ä, b = 20.4092(4) Ä, c = 12.4290(1) Ä, β = 108.173(3)°, V = 2849.0 Ä, Ζ = 12, %(F) = 0.053, R^F) = 0.116, T= 213 K. Source of material The compound was isolated from acetonitrile as a side product. The crystals were grown in anhydrous acetonitrile in a dry atmosphere.

Crystal structure of trans-bis[2-hydroxy-5-methyl-phenonethanoneoximato- N,O]nickel(II), C18H20N2NiO4

Abstract: C18H20N2NÌO4, triclinic, P\\ (No. 2), a = 6.296(5) Â, b = 8.204(7) À, c = 8.653(8) Â, α = 71.92(6)°, β = 80.61(7)°, γ = 83.84(6)°, V = 4 1 8 . 4 À 3 , Z = 1, p m = 1.536 g-crrT3, Rg{F) = 0.045, RV/(F1) = 0 .115, 7 = 2 9 3 K.

Crystal structure of bis(aza-15-crown-5-dithiocarbamato)platinum(II)—dichloromethane(1/2),((CH2CH2OCH2CH2OCH2CH2OCH2CH2OCH2CH2)NCS2)2Pt·2CH2Cl2

Abstract: C24H44Cl4N208PtS4, triclinic, PI (No. 2), a = 11.822(3) Ä, b = 10.004(4) Ä, c = 8.412(4) Ä, α = 94.83(3)°, β = 107.29(4)°, γ = 109.82(4)°, V= 874.5 Ä, Z = 1, R&(F) = 0.089, wR(F) = 0.089, 7 = 2 9 3 K. Source of material Samples of the complex were kindly supplied by Dr. Fracasso. The compound was prepared in heterogeneous phase by adding PtCb to the dithiocarbamate ligand in CH2CI2. Orange-yellow crystals were separated slowly from the CH2CI2 solution after addition of n-hexane. Discussion The square planar complex consists of discrete centrosymmetric PtL2 molecules, where the bidentate ligand forms a bite S-Pt-S angle of 75.1 (1)°. Relevant bond distances are: Pt-S 2.311(4) A and 2.299(5) Ä, C-S 1.72(2) Ä and 1.69(2) Ä, N-C(l) (partial double) 1.33(2) Ä, N-C(2) and N C ( l l ) (single covalent) 1.46(2) Ä and 1.47(2) Ä, respectively. Bond lengths in the crown ring are normal. Two CH2CI2 molecules are associated to each complex molecule as clathrate solvent. The high fraction of unobserved or low intensities seems to indicate a poor crystal quality, which could also explain the relatively high standard deviations at Table 2. Atomic coordinates and displacement parameters (in Ä). Atom Site X y ζ i/iso H(2A) 21 0.169(2) -0.091(2) 0.712(2) 0.08 H(2B) 2 i 0.036(2) -0.178(2) 0.522(2) 0.08 H(3A) 2i 0.306(2) -0.171(2) 0.607(2) 0.08 H(3B) 2 i 0.205(2) -0.205(2) 0.393(2) 0.08 H(4A) 2 i 0.114(2) -0.563(2) 0.459(2) 0.08 H(4B) 2 i 0.139(2) -0.451(2) 0.311(2) 0.08 H(5A) 21 0.361(2) -0.328(2) 0.494(2) 0.08 H(5B) 2i 0.320(2) -0.515(2) 0.427(2) 0.08 H(6A) 2i 0.497(2) -0.478(2) 0.842(2) 0.08 H(6B) 2 / 0.524(2) -0.409(2) 0.664(2) 0.08 H(7A) 2 i 0.643(2) -0.229(2) 0.923(2) 0.08 H(7B) 2/ 0.499(2) -0.244(2) 0.955(2) 0.08 H(8A) 21 0.595(2) -0.014(2) 0.969(2) 0.08 H(8B) 2i 0.706(2) 0.018(2) 0.867(2) 0.08 H(9A) 2 i 0.571(2) 0.069(2) 0.617(2) 0.08 H(9B) 2 i 0.630(2) 0.205(2) 0.802(2) 0.08 H(10A) 21 0.463(2) 0.288(2) 0.704(2) 0.08 H(10B) 2 i 0.404(2) 0.163(2) 0.510(2) 0.08 H(11A) 2 i 0.243(2) 0.242(2) 0.579(2) 0.08 H(11B) 2 i 0.261(2) 0.151(2) 0.750(2) 0.08 H(12A) 2i 0.059(2) 0.438(2) -0.194(2) 0.08 H(12B) 2 i 0.195(2) 0.567(2) -0.218(2) 0.08 * Correspondence author (e-mail: graziani@chim02.chin.unipd.it) 4 9 6 ( ( C H 2 C H 2 0 C H 2 C H 2 0 C H 2 C H 2 0 C H 2 C H 2 0 C H 2 C H 2 ) N C S 2 ) 2 P t · 2 C H 2 C 1 2 Table 3. Atomic coordinates and displacement parameters (in Ä). Atom Site X y ι Un t/22 i/33 Un Un t/23 Pt( l ) la 0 0 0 0.0399(6) 0.0281(5) 0.0138(5) 0.0150(4) 0.0003(4) -0.0039(3) S( l ) 2 i 0.1431(4) 0.1604(5) 0.2502(5) 0.045(3) 0.031(2) 0.022(2) 0.013(2) -0.002(2) -0.003(2) S(2) 2 i -0.0041(4) -0.1360(5) 0.2069(5) 0.044(3) 0.040(2) 0.020(2) 0.013(2) -0.002(2) -0.003(2) CCD 2 i 0.113(2) 0.014(2) 0.347(2) 0.05(1) 0.026(8) 0.032(9) 0.022(7) 0.008(7) 0.003(7) N( l ) 2 i 0.168(1) 0.017(2) 0.510(2) 0.048(9) 0.042(8) 0.012(6) 0.028(7) 0.003(6) 0.006(5) C(2) 2i 0.138(2) -0.117(2) 0.574(2) 0.05(1) 0.05(1) 0.024(8) 0.02(1) 0.012(8) 0.009(8) C(3) 2 i 0.207(2) -0.210(2) 0.522(2) 0.06(1) 0.030(9) 0.04(1) 0.019(9) 0.017(9) 0.006(8) O( l ) 2 i 0.140(1) -0.353(1) 0.535(2) 0.050(8) 0.034(6) 0.033(6) 0.017(6) 0.012(6) 0.006(5) C(4) 2 i 0.168(2) -0.457(2) 0.444(2) 0.04(1) 0.029(8) 0.034(9) 0.009(7) -0.001(8) -0.003(7) C(5) 2i 0.306(2) -0.436(2) 0.504(2) 0.05(1) 0.04(1) 0.024(8) 0.016(8) 0.006(8) 0.001(7) 0 (2 ) 2 i 0.346(1) -0.450(2) 0.677(1) 0.059(9) 0.059(8) 0.022(6) 0.024(7) 0.010(6) 0.008(6) C(6) 2 i 0.481(2) -0.404(2) 0.760(2) 0.06(1) 0.05(1) 0.030(9) 0.024(9) 0.002(8) -0.003(8) C(7) 2 i 0.543(2) -0.253(2) 0.861(2) 0.05(1) 0.07(1) 0.018(8) 0.03(1) -0.006(8) -0.002(9) 0 (3 ) 2 i 0.530(1) -0.151(1) 0.757(1) 0.057(8) 0.043(7) 0.019(6) 0.018(6) -0.002(5) -0.002(5) C(8) 2/ 0.606(2) -0.003(2) 0.847(2) 0.04(1) 0.04(1) 0.030(9) 0.016(8) -0.007(8) -0.015(8) C(9) 2i 0.566(2) 0.094(2) 0.742(2) 0.05(1) 0.04(1) 0.04(1) 0.016(9) -0.004(8) -0.039(8) 0 (4 ) 2 i 0.439(1) 0.078(1) 0.726(1) 0.039(7) 0.046(7) 0.025(6) 0.014(6) -0.000(5) 0.003(5) C(10) 2 i 0.400(2) 0.179(2) 0.637(2) 0.04(1) 0.05(1) 0.023(8) 0.016(8) 0.000(7) -0.000(8) C(1I) 2 i 0.266(1) 0.153(2) 0.624(2) 0.04(1) 0.05(1) 0.012(7) 0.022(8) -0.003(7) -0.007(7) Cl( l ) 21 0.2471(6) 0.4777(7) 0.0339(7) 0.073(4) 0.076(4) 0.039(3) 0.039(3) -0.004(3) 0.009(3) Cl(2) 2 i 0.1106(5) 0.6707(6) -0.0447(7) 0.056(3) 0.050(3) 0.050(3) 0.024(2) 0.001(2) -0.014(2) C(12) 2 i 0.148(2) 0.531(2) -0.129(2) 0.07(1) 0.06(1) 0.023(9) 0.04(1) 0.004(9) 0.003(8)