Showing papers in "Zeitschrift Fur Kristallographie-new Crystal Structures in 2008"

Refinement of the crystal structure of dipalladium gallium, Pd2Ga

Abstract: GaPd2, orthorhombic, Pnma (no. 62), a = 5.4829(8) A, b = 4.0560(4) A, c = 7.7863(8) A, V = 173.2 A, Z = 4, Rgt(F) = 0.022, wRref(F) = 0.029, T = 295 K. Source of material Starting from powder of Pd (99.9 %, Chempur) and granules of Ga (99.9999%, Chempur) in a ratio of 2:1 and 1.5 mg/ml GaI3 as transport agent (99.999%, Chempur), needle-shaped single crystals of Pd2Ga were synthesized by an exothermal chemical transport reaction in a temperature gradient from 673 K (source) to 873 K (sink) [1]. Experimental details Lattice parameters of the title compound were determined by least-squares fitting of 24 reflections from powder X-ray diffraction data obtained from ground single crystals (Huber Image Plate Guinier camera G670, CuK41 radiation, , = 1.54056 A, LaB6 as internal standard, a = 4.15692 A). Due to the significant homogeneity range reported for Pd2+xGa1–x [2], the occupancy values together with the anisotropic displacement parameters were allowed to vary in separate series of the structure refinement while the overall scale factor was fixed. The resulting occupancies were equal to unity within one e.s.d. 0.998(4), 1.003(4) and 1.006(5) for Pd1, Pd2 and Ga sites, respectively, confirming the 2:1 composition of the investigated specimen. In the final refinement series full occupancies were assumed for all positions. Discussion The crystal structure of Pd2Ga adopts an atomic arrangement of theCo2Si type of structure [3]. The present investigation provides a more precise refinement of the atomic as well as the displacement parameters of the previously reportedmodel obtained on the basis of photographic single crystal data [4] and X-ray powder diffraction [2]. The title compound represents the stoichiometric (x = 0) composition of Pd2+xGa1–x and thus falls into the reported homogeneity range of –0.04 ( x ( 0.02 at 873 K [2,4]. All atoms in the crystal structure of Pd2Ga are situated on one of the two mirror planes perpendicular to [010]. A clear gap at !3.00 A separates the first coordination sphere of each atom in the structure of Pd2Ga. Each Pd1 atom has distorted tetrahedral coordination by four Ga atoms with distances varying between 2.54 A and 2.56 A. One additional Ga atom is quite far away at a distance of 2.96 A. The environment of Pd2 is different: nonplanar trigonal coordination by three Ga atomswith d(Pd—Ga) = 2.56A – 2.62A and two other Ga atoms at a considerably longer distance of 2.84 A. The closest Pd—Ga contacts are comparable with the sum of the single bond radii of Pd (1.28 A) and Ga (1.25 A) [5]. The coordination sphere of each palladium site is completed by eight Pd atomswith d(Pd—Pd) between 2.82A and 2.99A, thus increasing the coordination number of both positions to 13. These contacts are slightly longer than the interatomic distance of 2.75A in ccpPdmetal [6]. Gallium atoms are surrounded exclusively by ten palladium species. The shortest Ga···Ga distance of 3.43 A is significantly longer than the average interatomic distance of 2.70 A in the 4-modification of Ga [6]. The environment of gallium atoms is formed by seven Pd atoms in the range of 2.54 A – 2.62 A and three Pd atoms at distances 2.84 A (2×) and 2.96 A (1×). Z. Kristallogr. NCS 223 (2008) 7-8 / DOI 10.1524/ncrs.2008.0004 7 © by Oldenbourg Wissenschaftsverlag, Munchen

Crystal structure of 2,4-dihydroxybenzoic acid [1-(3,5-dichloro-2-hydroxy phenyl)methylidene]hydrazide, C14H10Cl2N2O4

Abstract: C14H10Cl2N2O4, monoclinic, P121/c1 (no. 14), a = 11.874(2) Å, b = 12.672(3) Å, c = 9.640(2) Å, 5 = 107.47(3)°, V = 1383.6 Å, Z = 4, Rgt(F) = 0.038, wRref(F ) = 0.097, T = 298 K. Source of material 3,5-Dichlorosalicylaldehyde (0.1 mmol, 19.0 mg) and 2,4dihydroxybenzoic acid hydrazide (0.1 mmol, 16.8 mg) were dissolved in a 95% ethanol solution (10 ml). The mixture was stirred at room temperature to give a clear colorless solution. Crystals of the title compound were formed by gradual evaporation of the solvent for five days at room temperature. Experimental Details Atom H2 was located in a difference Fourier map and refined isotropically, with N—H distance restrained to 0.90(1) Å. Other H atoms were placed in idealized positions and constrained to ride on their parent atoms, with O—H distances of 0.82 Å, C—H distances of 0.93 Å, and with Uiso(H) = 1.2 Ueq(C) and 1.5 Ueq(O). Discussion Schiff base compounds have been of great interest for a long time. These compounds play an important role in the development of coordination chemistry [1-3]. Some of the complexes derived from Schiff bases have been found to have pharmacological and antitumor properties [4-6]. Recently, we have reported several Schiff base compounds [7-9]. The molecule of the title compound, C14H10Cl2N2O4, displays a trans configuration with respect to the C=N and C—N bonds. All the bond lengths are within normal ranges and comparable to the values observed in the similar compounds [10-12]. The dihedral angle between the two benzene rings is 6.6(2)°. Z. Kristallogr. NCS 223 (2008) 165-166 / DOI 10.1524/ncrs.2008.0067 165 © by Oldenbourg Wissenschaftsverlag, München Crystal: colorless block, size 0.13 × 0.15 × 0.17 mm Wavelength: Mo K7 radiation (0.71073 Å) *: 4.89 cm−1 Diffractometer, scan mode: Siemens P4, 8 2%max: 54° N(hkl)measured, N(hkl)unique: 8297, 3025 N(param)refined: 205 Programs: SHELXS-97 [13], SHELXL-97 [14], SHELXTL [15] Table 1. Data collection and handling. H(1) 4e 0.1815 0.3522 1.1643 0.059 H(3) 4e −0.0033 −0.0400 0.7379 0.063 H(4) 4e −0.2960 0.0293 0.3222 0.086 H(4A) 4e 0.4917 0.3354 1.6508 0.042 H(6) 4e 0.3686 0.0768 1.4135 0.042 H(7) 4e 0.2103 0.0883 1.1777 0.041 H(11) 4e −0.1582 −0.0203 0.5341 0.044 H(14) 4e −0.1606 0.3297 0.6620 0.046 H(13) 4e −0.2913 0.2719 0.4499 0.051 H(2) 4e 0.069(2) 0.1044(9) 0.951(3) 0.080 Table 2. Atomic coordinates and displacement parameters (in Å). Atom Site x y z Uiso

Determination of residual stress at weld interruptions by neutron diffraction

Abstract: All too often those making welding stress measurements fail to consider what length scales and types of residual stress are important from a materials or component performance viewpoint. Unwittingly this can lead to inappropriate measurements and interpretations. Traditionally neutron diffraction has been used to infer macro (type I)-residual stresses, but type II and type III residual stress information is also contained within the diffraction peak shifts and widths. In this paper we examine the residual stresses generated at different scale levels within an austenitic stainless steel welded plate containing weld stop-start features such as those typically encountered in industry. Significant increases in the macro-stresses are found at these locations. In addition, calibration samples that were free of macro-stress but had undergone known amounts of plastic strain were also measured, allowing diffraction peak broadening measurements to be discussed in terms of plastic strain (type III stress). Finally, an analysis of the individual diffraction peaks allowed the level of type II intergranular stresses to be determined and thereby the extent of plastic strain inferred and related to the welding process. This stresses can be important as weld metal itself is anisotropic in nature and weld measurements based on single diffraction peak measurements can be significantly affected by type II intergranular stresses, leading to stress levels deviating significantly from the underlying macrostress.

Crystal structure of dysprosium meta-oxoborate, β-Dy(BO2)3, via normal-pressure synthesis

Abstract: B3DyO6, orthorhombic, Pnma (no. 62), a = 15.9431(9) A, b = 7.4036(4) A, c = 12.2618(7) A, V = 1447.3 A, Z = 16, Rgt(F) = 0.026, wRref(F) = 0.053, T = 293 K. Source of material Single crystals of -Dy(BO2)3 have been obtained by the reaction of Dy2O3 and B2O3 in the stoichiometric ratio 1 : 3 with a slight excess of fluxing DyCl3 in gas tightly sealed platinum crucibles within three weeks at 900 °C. The compound appears as colourless, thin, airand water-resistant needles which tend to severe growth-twinning due to their fibrous habit. Discussion In the range of the lanthanidemeta-oxoboratesM(BO2)3 (M = La Lu) there are meanwhile four modifications known of which three are realized for the light representatives. The -type compounds could be obtained under normal-pressure hightemperature conditions for M = La Nd, Sm Tb and crystallize monoclinically with space group I2/a (C2/c), e.g. [1]. Two highpressure high-temperature modifications were recently synthesized: the orthorhombic -M(BO2)3-type (M = La – Nd, Pca21) [2] and the monoclinic -La(BO2)3-type compounds (P21/c) [3]. For the first time, an example of the fourth known phase ofmetaoxoborates, -Tb(BO2)3 was obtained under normal-pressure high-temperature conditions [4], whereas single crystals of M(BO2)3 with M = Dy Lu [5] were accessible under highpressure high-temperature conditions exclusively. Only the here presented compound can be additionally synthesized under normal pressure. In the crystal structure, vertex-linked [BO4] tetrahedra [d(B—O) = 143 – 153 pm] are connected to strongly corrugated oxoborate layers running parallel to (100). Between these layers the four crystallographically independent Dy cations are located, each surrounded by eight oxide anions [d(Dy—O) = 226 – 283 pm]. Z. Kristallogr. NCS 223 (2008) 177-178 / DOI 10.1524/ncrs.2008.0073 177 © by Oldenbourg Wissenschaftsverlag, Munchen Crystal: colourless needle, size 0.02 × 0.04 × 0.09 mm Wavelength: Mo K radiation (0.71069 A) : 205.78 cm−1 Diffractometer: Bruker-Nonius -CCD 2 max: 54.96° N(hkl)measured, N(hkl)unique: 18898, 1789 Criterion for Iobs, N(hkl)gt: Iobs > 2 (Iobs), 1680 N(param)refined: 197 Programs: SHELXS-97 [6], SHELXL-97 [7], DIAMOND [8] Table 1. Data collection and handling.

Crystal structure of lanthanum triiodate iodic acid, La(IO3)3(HIO3)

Abstract: HI4LaO12, monoclinic, P121/c1 (no. 14), a = 10.685(1) Å, b = 7.626(1) Å, c = 14.314(1) Å, = 110.23(1)°, V = 1094.4 Å, Z = 4,Rgt(F) = 0.019, wRref(F) = 0.040, T = 293 K. Source of material 0.5 mmol of anhydrous lanthanum chloride and 2.5 mmol of lithium iodate were dissolved in 40 ml of 7 M nitric acid . The solution was evaporated slowly at 323 K. After six days, transparent and colourless prismatic crystals suitable for X-ray crystal structure analysis were obtained. They were filtered, washed with deionised water and dried at room temperature (yield 0.33 g, 78 %). Experimental details Hydrogen atom from iodic acid molecule could not be located by difference Fourier analysis.

Crystal structure of 3,5-dihydroxybenzoic acid [1-(2-hydroxy-3- methoxyphenyl)methylidene]hydrazide — methanol — water (1:1:1), (C15H14N2O) · CH3OH · H2O

Abstract: C16H20N2O7, monoclinic, P121/c1 (no. 14), a = 8.023(2) Å, b = 9.714(2) Å, c = 11.583(2) Å, 5 = 99.36(3)°, V = 842.8 Å, Z = 4, Rgt(F) = 0.046, wRref(F) = 0.132, T = 298 K. Source of material 3-Methoxysalicylaldehyde (0.1 mmol, 15.2 mg) and 3,5dihydroxybenzoic acid hydrazide (0.1 mmol, 16.8 mg) were dissolved in a methanol solution (10 ml). The mixture was stirred at room temperature for 1 hour and filtered. After keeping the filtrate in air for three days, colorless block-like crystals were formed. Discussion Schiff base compounds have been of great interest for a long time. These compounds play an important role in the development of coordination chemistry [1-3]. Some of the complexes derived from Schiff bases have been found to have pharmacological and antitumor properties [4-6]. Recently, we have reported a few Schiff base compounds [7-9]. The crystal structure of the title compound consists of a Schiff base molecule, water and one methanol molecule. The Schiff base molecule displays a trans configuration with respect to the C=N and C—N bonds. All the bond lengths are within normal ranges and comparable to the values observed in the similar compounds [10-12]. The dihedral angle between the two benzene rings is 8.0(2)°. Z. Kristallogr. NCS 223 (2008) 167-168 / DOI 10.1524/ncrs.2008.0068 167 © by Oldenbourg Wissenschaftsverlag, München Crystal: colorless block, size 0.20 × 0.23 × 0.23 mm Wavelength: Mo K7 radiation (0.71073 Å) *: 1.10 cm−1 Diffractometer, scan mode: Siemens P4, 8 2%max: 55° N(hkl)measured, N(hkl)unique: 5334, 3726 N(param)refined: 242 Programs: SHELXS-97 [13], SHELXL-97 [14] SHELXTL [15] Table 1. Data collection and handling.

Crystal structure of tetrakis(μ-thiocyanato)bis(μ-(bis(diphenylphosphino) methane-P,P′))tetrasilver(I), Ag4(SCN)4(C25H22P2)2

Abstract: C54H44Ag4N4P4S4, monoclinic, P121/n1 (no. 14), a = 12.4531(4) Å, b = 16.7286(5) Å, c = 13.6948(4) Å, 3 = 98.722(2)°, V = 2820.0 Å, Z = 2, Rgt(F) = 0.031, wRref(F) = 0.062, T = 273 K. Source of material Synthesis of the title compoundwas carried out by stirring the solution of AgSCN (silver thiocyanate) (0.0489 g, 0.3 mmol), bis(diphenylphosphino)methane (dppm; 0.0577g, 0.15 mmol), and quinoline (0.0194 g, 0.15 mmol) in N,N-dimethylformamide (10 ml) for 24 hours at room temperature. After filtration, the filtrate was allowed to stand at room temperature. Slow evaporation of the colorless solvent yielded white crystals. Discussion Some studies have been made on silver(I) cluster blending both a sulfur containing ligand and phosphine [1]. The compounds [Ag2Cl2(PPh3)2(C4H5N3)]& [2] and [Ag2Br2(PPh3)2(C4H5N3)]& [3] have been prepared by us. Further clusters with dppm bridges were reported, e.g. the luminescent tetranuclear silver(I) clusters [Ag4(*-dppm)4(*4-E)] (E = S, Se or Te) with mixed dppm and chalcogen [4] and the tetranuclear cluster [Ag4(*-dppm)4(*4-imnt)2] (i-mnt = 2,2-dicyano-1,1-ethylenedithiolate) [5]. The diphosphine groups (e.g. of dppm) adoptmonodentate, chelating or edge-bridging coordination modes on the cluster surface[6]. In polynuclear complexes, the dppm ligand has a greater tendency to act either as a monodentate or as a bridging bidentate ligand than as a chelating ligand because of the four-membered ring being strained [6]. The crystal structure determination of the title compound revealed a tetranuclear silver(I) cluster. Because of all the thiocyanato ligands are almost linear, each two thiocyanates and two silver atoms form a distorted hexagon. Each silver atom is coordinated by one nitrogen atom of the thiocyanate, one sulfur atom of the other thiocyanate and the phosphorus atom of the dppm ligand. Ag(1,1A,2,2A) atoms form a tetragon whose edges are bridged by two dppm ligands and two *-thiocyanates. The edges of the tetragon are not equivalent and the distance of the two silver atoms in different hexagons (3.0635(3) Å) is 0.14 Å longer than the sum of the covalent radii (2.88 Å) [7], which indicates that there is a weak Ag···Ag interaction. The bond length of S1—Ag1 (2.5683(7) Å) is slightly shorter than that of S2—Ag2 (2.6054(6) Å). The bond lengths of N1—Ag2 and N2—Ag1 are 2.231(2) Å and 2.214(2) Å, respectively. The bond lengths of P1—Ag1 and P2—Ag2 are 2.3891(6)Å and 2.4087(6)Å, respectively, the average Ag—P bond length of 2.399 Å is 0.12 Å shorter than that reported for [Ag4(*-dppm)4(*4-i-mnt)2] [5]. The angles of N–Ag–P are 127.38(6)° and 139.00(5)°, while the angles of P–Ag–S are 130.36(2)° and 110.93(2)°. However, the range of the angles of N–Ag–S is very small, being between 102.24(6)° and 102.35(5)°. Z. Kristallogr. NCS 223 (2008) 79-81 / DOI 10.1524/ncrs.2008.0035 79 © by Oldenbourg Wissenschaftsverlag, München

Crystal structure of bis(1,3-diisopropyl-4,5-dimethylimidazolium) heptaiodopentaargentate, [C11H21N2]2[Ag5I7]

Abstract: C22H42Ag5I7N4, orthorhombic, Pbcn (no. 60), a = 18.3099(2) Å, b = 12.1757(3) Å, c = 18.1450(3) Å, V = 4045.2 Å, Z = 4, Rgt(F) = 0.037, wRref(F) = 0.077, T = 173 K. Source of material The title compound was prepared according to published procedures [1]. Experimental deatils The H atoms were positioned geometrically (C—H = 0.93 Å for Csp, 0.97 Å for Csp in CH3 and 0.98 Å for Csp in CH2) and treated as riding on their respective C atom, with Uiso(H) = 1.2 Ueq(Csp) and 1.5 Ueq(Csp). Discussion The structure of the Ag5I7-ion in the title compound shows the same structure as those from the ammonium, phosphonium and arsonium salts in which the AgI4 tetrahedra are linked by common faces, edges and corners, exclusively [2]. The anion, however, consists of two AgI4 tetrahedra (Ag3, Ag3; symmetry code i: −x,y,1/2−z) sharing a common I3 face (I2, I3, I3). The additional silver (Ag1, Ag2, Ag2) tetrahedra are connected via edge to form, over all, a central Ag5I7 core which is connected to the neighboured ones via common I1−I1 edges (symmetry code ii: − x,−y,1−z). The central distance of the silver atoms [d(Ag3···Ag3) = 2.8852(9) Å] in the face shared tetrahedra is clear inside the van der Waals contact and characteristic of d10/d10 close-shell interactions. The further Ag−Ag contacts (3.03 3.11 Å) and Ag—I bond lengths (2.89 3.02 Å) are in the expected range. An interesting feature of this structure is, that we found C−H···I distances in a range of 2.8 to 3.4 Å. A view in the unit cell down c shows Ag5I7 polymers along the edges and in the center of the cell. The cations shared around these columnes and the methyl-groups are orientated in direction of the iodid. It seems, that week interactions of C−H···I are important for the solid state structure. A different structural type consisting also of face-shared AgI4 tetrahedra has been found for the Ag3I6 anion [3]. The influence of the cation linked to the anion by a weak hydrogen bond [d(C1···I4) = 4.009 Å] is not established, and the geometry of the C—H···I fragment does not differ markedly from that observed in the corresponding imidazolium iodide salt [4]. Z. Kristallogr. NCS 223 (2008) 341-342/DOI 10.1524/ncrs.2008.0148 341 © by Oldenbourg Wissenschaftsverlag, München Crystal: colorless block, size 0.17 × 0.26 × 0.29 mm Wavelength: Mo K2 radiation (0.71073 Å)

Refinement of the crystal structure of aquazinc(II) glutamate hydrate, Zn(H2O)(C5H7NO4) · H2O

Abstract: C5H11NO6Zn, orthorhombic, P212121 (no. 19), a = 7.1770(6) A, b = 10.3960(9) A, c = 11.1210(9) A, V = 829.8 A, Z = 4, Rgt(F) = 0.018, wRref(F) = 0.043, T = 173 K. Source of material Good quality colorless crystals of zinc-glutamate-MOF (MOF = metal organic framework) were obtained from a solution of Lglutamic acid potassium salt monohydrate (5.00 g, 24.61 mmol) and zinc acetate tetrahydrate (5.40 g, 24.61 mmol) in water (100 mL) by slow evaporation of water. Experimental details The H atoms bonded to the N and O atoms were located and refined due to their importance in the hydrogen bonding pattern, the otherHatomswere calculated usingC—Hdistances of 0.99A. Discussion The structure of the title compound, determined by film method, was published in 1966 (cell dimensions of a = 11.190(2) A, b = 10.463(1)A and c=7.220(2)Awith a finalR1 value of 0.032) [1]. Re-determination using image plate techniques (a = 11.121(9)A, b = 10.396(9) A and c = 7.177(6) A) let to lower R values. The quality of the data allowed the determination of the positions of H atoms of the chemisorbed water molecules. The zinc atom is coordinated in a distorted octahedral fashion. The O3 atom and the O4 atom (zinc bonded water molecules) coordinate the zinc in cisoid axial positions. The crystal structure also consists of another (chemisorbed) water molecule (O6, HO1, HO2). The water molecules give rise to hydrogen bonding. The zinc bonded water (O4, HO3, HO4) is coordinated in a trigonal planar fashion by Zn1 (d(Zn1—O4) = 2.059 A) and two hydrogen bonds to two chemisorbed water molecules with O4···O6 distances of 2.704 A and 2.745A, respectively. The chemisorbed water is coordinated furthermore via hydrogen bonding byO1 andO2 from the carboxylic groups of two different symmetry-relatedmolecules in a tetrahedral fashion.Another group that gives rise to hydrogen bonding is the amino group. It forms a hydrogen bondwith the O3 atom of a neighboring molecule (d(Namino···O3) = 2.942 A). Z. Kristallogr. NCS 223 (2008) 55-56 / DOI 10.1524/ncrs.2008.0026 55 © by Oldenbourg Wissenschaftsverlag, Munchen Crystal: colorless prism, size 0.21 × 0.29 × 0.38 mm Wavelength: Mo K4 radiation (0.71069 A) *: 29.59 cm−1 Diffractometer, scan mode: Stoe IPDS II, ./6 2%max: 51.18° N(hkl)measured, N(hkl)unique: 11307, 1564 Criterion for Iobs, N(hkl)gt: Iobs > 2 #(Iobs), 1520 N(param)refined: 138 Programs: SIR97 [2], SHELXL-97 [3] Table 1. Data collection and handling. H(2A) 4a 0.2121 0.8764 0.1806 0.024 H(2B) 4a 0.3481 0.9968 0.1980 0.024 H(3A) 4a 0.3797 0.7597 0.3257 0.021 H(3B) 4a 0.5123 0.8808 0.3487 0.021 H(5) 4a 0.6584 0.7229 0.2277 0.018 HN(1) 4a 0.687(4) 0.959(3) 0.184(2) 0.030(8) HN(2) 4a 0.801(5) 0.871(3) 0.134(2) 0.025(7) HO(1) 4a 0.405(5) 0.882(3) 0.549(3) 0.040 HO(2) 4a 0.477(5) 0.879(3) 0.643(3) 0.040 HO(3) 4a 0.779(5) 1.143(3) 0.011(3) 0.040 HO(4) 4a 0.652(4) 1.178(3) −0.051(3) 0.040 Table 2. Atomic coordinates and displacement parameters (in A). Atom Site x y z Uiso

Crystal structure of tri-O-propyl-cis-inositol-1,3,5-orthobenzoate, C22H32O6

Abstract: C22H32O6, monoclinic, P121/n1 (no. 14), a = 8.8485(5) Å, b = 11.4397(6) Å, c = 21.342(1) Å, 0 = 98.442(3)°, V = 2136.9 Å, Z = 4, Rgt(F) = 0.066, wRref(F) = 0.205, T = 100 K. Source of material The title compound was obtained from cis-inositol-1,3,5orthobenzoate [1,2] by alkylation with iodopropane in a DMSO solution containing solid KOH. After extraction with dichloromethane, single crystals were grown from a MeOH solution by slow evaporation. The NMR spectroscopic data (showing a total of 10 resonances in the C NMR spectrum) are in agreement with the molecular structure following from the single crystal X-ray analysis reported here. Experimental details All positions of the C—H-hydrogen atoms were calculated (riding model) with Uiso fixed at 1.2 Ueq(CH, CH2) or 1.5 Ueq(CH3) of the corresponding carbon atoms. The propyl groups of the three ether residues all showed some disorder as indicated by large displacement parameters of the outer carbon atoms. For one of these groups, the disorder could be explicitly resolved, using two distinct positions for C62 and C63 having site occupancies of each 50 %. An additional data set, collected at 200 K (a = 8.991(2) Å, b = 11.553(2) Å, c = 21.447(4) Å, 0 = 98.53(3)°) revealed the same type of disorder. The two most intense peaks of the residual electron density with maxima of 0.83 eÅ−3 and 0.64 eÅ−3 are located in proximity of C61 and in-between C22 and C23, respectively. They must obviously be regarded as artifacts of the disorder problem. In the Figure, the displacement ellipsoids of the nonhydrogen atoms are drawn at the 30 % probability level, whereas the hydrogen atoms are depicted as spheres of arbitrary size. Only one set (C62B and C63B) of the split positions is shown. Discussion Metal binding to cis-inositol is possible via the 1,3,5-triaxial or via a 1,2,3-axial-equatorial-axial coordination mode [1,3]. To support selective formation of the metalla-trioxa-adamantane structure of the 1,3,5-triaxial mode, the remaining hydroxy groups in the 2, 4, and 6 position can be blocked by alkylation [4]. Moreover, the choice of the alkyl groups allows a systematic variation of the lipophilicity of the resulting ligand. The title compound was obtained as an intermediate within the synthesis of such chelators. It exhibits the characteristic trioxa-adamantane cage [2,4,5] with the four six-membered rings all exhibiting a slightly distorted chair conformation. Z. Kristallogr. NCS 223 (2008) 363-364 / DOI 10.1524/ncrs.2008.0158 363 © by Oldenbourg Wissenschaftsverlag, München Crystal: colorless needle, size 0.20 × 0.35 × 0.80 mm Wavelength: Mo K2 radiation (0.71073 Å) ': 0.88 cm−1 Diffractometer, scan mode: Bruker X8 Apex, Nonius Kappa CCD, +/3 2#max: 52° N(hkl)measured, N(hkl)unique: 20005, 4163 Criterion for Iobs, N(hkl)gt: Iobs > 2 \"(Iobs), 3080 N(param)refined: 263 Programs: SHELXS-97 [6], SHELXL-97 [7], SHELXTL [8] Table 1. Data collection and handling. H(5) 4e 0.9461 0.7135 0.2614 0.051 H(1) 4e 0.6871 0.6111 0.0953 0.054 H(2) 4e 0.5335 0.6166 0.1794 0.059 H(3) 4e 0.5978 0.4777 0.2647 0.054 H(4) 4e 0.6878 0.6762 0.2788 0.056 H(6) 4e 0.7385 0.7550 0.1784 0.058 H(13) 4e 1.1064 0.3661 0.2869 0.054 H(9) 4e 0.9431 0.3190 0.1016 0.057 H(10) 4e 1.1034 0.1572 0.0996 0.072 H(12) 4e 1.2677 0.2050 0.2835 0.064 H(11) 4e 1.2624 0.0992 0.1906 0.069 H(41A) 4e 0.8175 0.7306 0.3742 0.081 H(41B) 4e 0.9845 0.6843 0.3663 0.081 H(43A) 4e 0.9952 0.6776 0.5328 0.169 H(43B) 4e 0.9118 0.7801 0.4899 0.169 H(43C) 4e 1.0780 0.7368 0.4790 0.169 H(42A) 4e 0.9737 0.5530 0.4470 0.129 Table 2. Atomic coordinates and displacement parameters (in Å). Atom Site Occ. x y z Uiso

Crystal structure of cis-inositol-1,3,5-orthobenzoate hemihydrate, C13H14O6 · 0.5H2O

Abstract: C13H15O6.50, orthorhombic, Iba2 (no. 45), a = 11.959(2) Å, b = 23.201(7) Å, c = 8.642(2) Å, V = 2397.7 Å, Z = 8, Rgt(F) = 0.052, wRref(F) = 0.117, T = 200 K. Source of material The title compound was obtained from cis-inositol as described in [1]. Single crystals were grown from a mixture of methanol and water. Experimental details All hydrogen atomic positions were located in a difference Fourier map. They were refined using variable isotropic displacement parameters. Discussion Orthoesters such as the title compound or the corresponding ethanoate [2] represent versatile synthons for the preparation of selectively alkylated cis-inositol derivatives such as the trimethyl or tripropyl ether [3,4]. These compounds represent interesting complexing agents for hard, highly charged metal cations [1,5]. The crystal structure of the title compound can be described in terms of a three dimensional hydrogen bonding system. Two types of hydrogen bonding are observed: Two of the equatorial hydroxy groups are involved in a two dimensional sheet structure parallel to (010), consisting of intermolecular O3−H3O···O1 and O1−H1O···O3 interactions. The remaining hydroxy group and the water of crystallization are aligned to chains parallel to [001] via O5−H5O···O1W and O1W−H1OW···O5 interactions. The axial ether oxygen atoms of the ortho-ester moiety do not participate in any hydrogen bonding. Z. Kristallogr. NCS 223 (2008) 361-362 / DOI 10.1524/ncrs.2008.0157 361 © by Oldenbourg Wissenschaftsverlag, München Crystal: colorless prism, size 0.2 × 0.3 × 0.4 mm Wavelength: Mo K2 radiation (0.71073 Å) ': 1.23 cm−1 Diffractometer, scan mode: Stoe IPDS, + 2#max: 48° N(hkl)measured, N(hkl)unique: 8209, 1843 Criterion for Iobs, N(hkl)gt: Iobs > 2 "(Iobs), 1763 N(param)refined: 237 Programs: SHELXS-97 [6], SHELXL-97 [7] Table 1. Data collection and handling. H(1OW) 8c 0.953(4) 0.981(2) 0.759(6) 0.06(1) H(1O) 8c 0.602(4) 0.782(2) 1.054(6) 0.05(1) H(3O) 8c 1.031(4) 0.738(2) 0.786(5) 0.04(1) H(5O) 8c 0.928(3) 0.954(2) 1.048(5) 0.04(1) H(1) 8c 0.768(3) 0.793(2) 1.070(4) 0.015(8) H(2) 8c 0.779(3) 0.737(2) 0.823(4) 0.026(9) H(3) 8c 0.944(2) 0.777(1) 0.949(4) 0.010(7) H(4) 8c 1.020(3) 0.862(1) 0.827(4) 0.012(7) H(5) 8c 0.913(3) 0.869(2) 1.061(4) 0.012(7) H(6) 8c 0.721(3) 0.892(2) 1.035(4) 0.024(9) H(9) 8c 0.574(3) 0.840(2) 0.547(5) 0.04(1) H(10) 8c 0.488(4) 0.887(2) 0.339(5) 0.025(9) H(11) 8c 0.576(3) 0.959(1) 0.201(4) 0.017(8) H(12) 8c 0.760(4) 0.986(2) 0.268(5) 0.04(1) H(13) 8c 0.848(3) 0.940(1) 0.485(4) 0.015(8) Table 2. Atomic coordinates and displacement parameters (in Å). Atom Site x y z Uiso

Crystal structure of 2,2'-[1,2-diethanediyl-bis(thio)]bis(1,3,4-thiadiazole) copper(II) diperchlorate, [Cu(C6H6N4S4)4][ClO4]2

Abstract: C24H24Cl2CuN16O8S16, triclinic, P1 (no. 2), a = 10.449(2) Å, b = 10.474(2) Å, c = 12.705(2) Å, = 68.694(2)°, = 76.439(2)°, = 74.924(2)°, V = 1235.6 Å, Z = 1, Rgt(F) = 0.040, wRref(F) = 0.107, T = 291 K. Source of material The reaction of 2,2'-[1,2-ethanediyl-bis(thio)]bis(1,3,4thiadiazole) (0.2 mmol) with Cu(ClO4)2 (0.1 mmol) in MeOH (10 ml) for a few minutes afforded a light blue solid, which was filtered, washed with acetone, and dried on air. The single crystals suitable for X-ray analysis were obtained by slow diffusion of Et2O into the acetonitrile solution of the solid. Discussion In constructing metal-organic frameworks, flexible ligands are usually selected because the flexibility and conformation restrainability offers the new possibilities for the arrangement of diverse frameworks [1-3]. Meanwhile, thiadiazoles have attracted increasing attention because of their potential applications in pharmaceutical, agricultural, industrial, coordination and polymer chemistry [4-6]. In this sense, flexible bisthiadiazole alkanes, like 2,2'-[1,2-ethanediyl-bis(thio)]bis(1,3,4-thiadiazole), show up as good candidates to generate one-dimensional, twodimensional and three-dimensional network designs [7]. In the title crystal structure, the copper atom is coordinated by six N atoms of six symmetry-related thiadiazole ligands in a slightly distorted octahedral environment, with Cu—N distances ranging from 2.030(2) to 2.430(3) Å, and N−Cu−N angles ranging from 87.3(1)° to 180.0°. All six Cu—N bond distances are within the range expected for such coordination bonds [8,9]. Obviously, only the N atoms of the thiadiazole ligands coordinate the Cu centers. It is worthwhile to note that the thiadiazole ligands adopt two kinds of coordination modes in the crystal structure. One N,Nbidentate bridging mode in trans configuration for bridging the copper atom into one-dimensional infinite stranded chain of loops, with the bridged Cu-Cu distance of 10.474(2) Å. The centroid separation and dihedral angle of thiadiazole rings are 7.816(1) Å and 81.72°, respectively. The other thiadiazole ligands adopt monodentate coordination mode and serve to complete the octahedral coordination sphere of the copper atom. The corresponding centroid separation and dihedral angle are 7.6299(9) Å and 67.3°, respectively. However, two thiadiazole rings are almost coplanar with the centroid separation of 7.8596(8) Å in the crystal structure of the thiadiazole ligand [7]. Apparently, incorporation as a bridging ligand into metal-organic frameworks imparts its significant conformation changes mainly ascribed to the interaction within metal coordination. The region between the chains is taken up by uncoordinated perchlorate ions. Among numerous known structures containing flexible ligands, such as 1,3-bis(4-pyridyl)propane(bpp), the similar infinite onedimensional chains have been found in [Co(bpp)2H2O]2[ClO4]2 · 3bpp · H2O, [Co(bpp)2(H2O)2][ClO4]2 · bpp · H2O, [Co(bpp)2 (NO3)2] · 2C6H6 and [Co(bpp)2(H2O)2][NO3]2 · bpp · H2O [1013]. Z. Kristallogr. NCS 223 (2008) 225-227 / DOI 10.1524/ncrs.2008.0095 225 © by Oldenbourg Wissenschaftsverlag, München Crystal: blue block, size 0.11 × 0.37 × 0.50 mm Wavelength: Mo K radiation (0.71073 Å) : 12.88 cm−1 Diffractometer, scan mode: Bruker SMART CCD, / 2 max: 50.98° N(hkl)measured, N(hkl)unique: 9463, 4562 Criterion for Iobs, N(hkl)gt: Iobs > 2 (Iobs), 3666 N(param)refined: 304 Programs: SHELXS-97 [14], SHELXL-97 [15], SHELXTL [16] Table 1. Data collection and handling.

Crystal structure of lithium hexachlorotungstate(V), LiWCl6

Abstract: Cl6LiW, trigonal, R3 (no. 146), a = 12.457(1) Å, c = 17.308(2) Å, V = 2325.9 Å, Z = 12, Rgt(F) = 0.039, wRref(F) = 0.109, T = 293 K. Source of material WCl6 and Li2CN2 were thoroughly mixed in a 2:1 molar ratio. About 65 mg of the mixture were pressed into a pellet. This was sealed in an evacuated silica ampule and annealed in a tube furnace for 14 days at 523 K. After cooling down to room temperature LiWCl6was obtained as a dark green crystalline powder and dark green plate-like crystals. The powder turned out to be single phase LiWCl6without any detectable side phases according toXray powder diffraction results. Due to the sensitivity of starting materials and product against air and moisture all handling was done under argon atmosphere. Experimental details The crystal structure was refined as a racemic twin in the noncentrosymmetric space group R3. Discussion The crystal structure of LiWCl6 corresponds to that of 4-WCl6 with lithium ions occupying octahedral holes. 4-WCl6 [1] crystallizes trigonal with unit cell parameters of a = 6.088(8) Å and c=16.68(5)Å in the space groupR3. The arrangement of chlorine atoms follows themotif of a hexagonal closest packing. Tungsten atoms occupy 1/3 of the octahedral voids in every second layer. LiWCl6 crystallizes in the space group R3. Tungsten atoms and lithium ions occupy 2/3 of the octahedral voids in every second layer of the slightly distorted hexagonal closest packing of the chlorine atoms. Therefore, the lattice parameter a is about twice the lattice parameter a of 4-WCl6. The lattice parameter c is slightly longer than that of4-WCl6. TheW—Cl distance inWCl6 (2.235(9) Å) is shorter than in LiWCl6 (2.235(9) Å – 2.50(1) Å). The Li—Cl distances of 2.38(4)Å – 2.69(6)Å are slightly longer than the W—Cl distances in LiWCl6. Thus, the Cl-metal-Cl layers in LiWCl6 arewidened. This yields the enlargement of the lattice parameters referring to 4-WCl6. Z. Kristallogr. NCS 223 (2008) 5-6 / DOI 10.1524/ncrs.2008.0003 5 © by Oldenbourg Wissenschaftsverlag, München Crystal: green plate, size 0.08 × 0.20 × 0.24 mm Wavelength: Mo K4 radiation (0.71073 Å) *: 168.56 cm−1 Diffractometer, scan mode: Stoe IPDS, . 2%max: 51.38° N(hkl)measured, N(hkl)unique: 9388, 1952 Criterion for Iobs, N(hkl)gt: Iobs > 2 #(Iobs), 1752 N(param)refined: 98 Programs: SHELXS-97 [2], SHELXL-97 [3], DIAMOND [4] Table 1. Data collection and handling.

Crystal structure of diaqua-bis(4,4'-dipyridyldisulfide)cadmium(II) dinitrate —methanol —water (1:2:2), [Cd(C10H8N2S2)2(H2O)2][NO3]2 ·2CH3OH·2H2O

Abstract: C22H32CdN6O12S4, monoclinic, P121/n1 (no. 14), a = 9.502(1) Å, b = 19.628(2) Å, c = 9.753(1) Å, 0 = 110.245(2)°, V = 1706.5 Å, Z = 2, Rgt(F) = 0.032, wRref(F ) = 0.079, T = 298 K. Source of material An methanol solution (10 ml) of 4,4'-dipyridyldisulfide (dpds, 0.02 g, 0.1 mmol) and maleic acid (0.01 g, 0.1 mmol) were slowly diffused into an aqueous solution (10 ml) of Cd(NO3)2 · 4H2O (0.031 g, 0.1 mmol) with stirring for 40 minutes at room temperature. Colorless block crystals were obtained in one week. Experimental details While the hydrogen atoms of all water molecules were located from Fourier difference maps, the other H atoms were fixed at calculated positions. Discussion Recently, the dpds ligand, characterized by the twisted-S−Sbridge, has been employed for the construction of coordination polymers showing topologically interesting assemblies. In most of the cases the dpds ligand coordinates metals in a double bridged fashion and, thanks to the flexible heterocyclic rings, sometimes stabilizes the structure through strong %-% interactions [1,2]. The structure of the title compound is described as a onedimensional double-stranded chain-like cadmium(II) complex with two nitrate ions, two methanol as well as two water molecules. Although the skeleton of the complex is similar to earlier reported [3], there is something different in detail. The cadmium has a distorted elongated octahedral environment with two water oxygens in the axial sites and four pyridine nitrogen donors in the basal plane. The trans ∠N−Cd−N and ∠O−Cd−O bond angles are 180°. On the other hand, cis ∠N−Cd−O and ∠N−Cd−N bond angles range from 88° to 92°, indicating distortion of octahedral environment. Each dpds ligands acts as a single bridge to link two cadmium(II) ions through its two pyridine nitrogen atoms, and each cadmium(II) ions connects four dpds ligands to form an infinite one-dimensional framework along [001]. The assembled structure of the complex is filled with guest methanol molecules. Oxygen atoms of the methanol molecules, uncoordinated water molecules and nitrate counter anions are hydrogen bonded to the coordinated water molecules [d(O1···O5) = 2.683 Å, d(O1···O6) = 2.633 Å, d(O6···O3) = 2.753 Å, d(O5···O3) = 2.836 Å], and a 8membered ring with a chair conformation is formed, which is positioned above or below the one-dimensional chains. Z. Kristallogr. NCS 223 (2008) 533-534 / DOI 10.1524/ncrs.2008.0233 533 © by Oldenbourg Wissenschaftsverlag, München Crystal: colorless block, size 0.19 × 0.21 × 0.29 mm Wavelength: Mo K2 radiation (0.71073 Å) ': 9.48 cm−1 Diffractometer, scan mode: Bruker SMART CCD, +/3 2#max: 50.02° N(hkl)measured, N(hkl)unique: 7353, 2990 Criterion for Iobs, N(hkl)gt: Iobs > 2 \"(Iobs), 2369 N(param)refined: 205 Programs: SHELXS-97 [4], SHELXL-97 [5] Table 1. Data collection and handling. H(1A) 4e 1.0975 0.5725 0.7923 0.064 H(1B) 4e 1.1642 0.5101 0.7931 0.064 H(5A) 4e 0.1432 0.6914 0.7435 0.108 H(5B) 4e 0.0265 0.6669 0.6247 0.108 H(6) 4e 0.2670 0.4317 0.6844 0.254 H(1) 4e 0.8160 0.5633 0.6941 0.055 H(2) 4e 0.6349 0.6399 0.5708 0.051 H(4) 4e 0.5717 0.6817 0.9469 0.051 H(5) 4e 0.7547 0.6038 1.0589 0.053 H(6A) 4e 0.2099 0.6287 0.0199 0.055 H(7) 4e 0.3684 0.7064 0.1699 0.052 H(9) 4e 0.2417 0.6386 0.4964 0.054 H(10) 4e 0.0854 0.5632 0.3352 0.056 H(11A) 4e 0.4302 0.5344 0.7172 0.250 H(11B) 4e 0.4386 0.4660 0.6374 0.250 H(11C) 4e 0.4890 0.4680 0.8083 0.250 Table 2. Atomic coordinates and displacement parameters (in Å). Atom Site x y z Uiso

Crystal structure of bis-(N,N'-bis-(trimethylsilyl)-pyridine-2-amine-6- amido)-(N,N'-bis-(trimethylsilyl)-pyridine-2,6-diamido)-di-cobalt(II), Co2(C11H22N3Si2)2(C11H21N3Si2)

Abstract: C33H65Co2N9Si6, orthorhombic, Pbca (no. 61), a = 21.616(2) Å, b = 18.239(2) Å, c = 23.861(2) Å, V = 9407.3 Å, Z = 8, Rgt(F) = 0.062, wRref(F) = 0.107, T = 133 K. Source of material One equivalent of N,N'-bis-(trimethylsilyl)-pyridine-2,6diamine dissolved in Et2O was treated with two equivalents of nbutyllithium at 0 °C. This solution was added to a suspension of one equivalent CoCl2 in THF. After removal of the solvent the residue was extracted twice with hexane and filtered. Deep blue crystals suitable for X-ray analysis were obtained after concentration of the mother liquid. Experimental details The H atoms bonded to the N atoms were located and refined due to their importance in the hydrogen bonding pattern. The remaining H atoms were accounted at the calculated positions. Discussion N,N'-bis-(trimethylsilyl)-pyridine-2,6-amine is known for years [1,2]. To our best knowledge there are no known metal complexes which contain this ligand in its neutral, deprotonated or double deprotonated form. Only few examples of metal complexes are described in the literature which contain ligands which are similar to N,N'-bis-(trimethylsilyl)-pyridine-2,6-amine but they were not characterized by X-ray single crystal structure analysis [3]. The dinuclear cobalt(II) complex is stabilized by two single deprotonated ligands and one double deprotonated ligand. The Co—Co distance is 2.618 Å. Each cobalt is coordinated by a Npyridine and a Namido belonging to the double deprotonated ligand and furthermore a Npyridine and a Namido belonging to a single deprotonated ligand [d(Co— Npyridine) = 2.269 Å (Co1—N2), 2.284 Å (Co2—N2), 2.024 Å (Co1—N5) and 2.016 Å (Co2—N8); d(Co—Namido) = 1.963 Å (Co1—N1), 1.959 Å (Co2—N3), 1.928 Å (Co1—N7) and 1.938 Å (Co2—N4)]. The orientation of the amino H atoms indicates a weak hydrogen bond to the adjacent Namido atoms [d(H9N···N3) = 2.291 Å; d(H6N···N1) = 2.460 Å]. Z. Kristallogr. NCS 223 (2008) 313-315 / DOI 10.1524/ncrs.2008.0135 313 © by Oldenbourg Wissenschaftsverlag, München Crystal: blue needle-like, size 0.05 × 0.07 × 0.29 mm Wavelength: Mo K radiation (0.71069 Å) : 8.91 cm−1 Diffractometer, scan mode: STOE-IPDSII, 2 max: 51.66° N(hkl)measured, N(hkl)unique: 12359, 9037 Criterion for Iobs, N(hkl)gt: Iobs > 2 (Iobs), 5263 N(param)refined: 477 Programs: SIR-97 [4], SHELXL-97 [5] Table 1. Data collection and handling. H(2) 8c 0.1358 0.1846 −0.0637 0.043 H(3) 8c 0.0689 0.2140 0.0082 0.050 H(4) 8c 0.0957 0.1927 0.1008 0.042 H(7) 8c 0.4552 0.1452 0.1515 0.039 H(8) 8c 0.5074 0.2315 0.0984 0.041 H(9) 8c 0.4691 0.2668 0.0117 0.035 H(12) 8c 0.2904 −0.1704 0.0058 0.034 H(13) 8c 0.2127 −0.2340 0.0507 0.037 H(14) 8c 0.1420 −0.1725 0.1074 0.037 H(16A) 8c 0.4002 0.0512 −0.0615 0.061 H(16B) 8c 0.4606 0.0005 −0.0622 0.061 H(16C) 8c 0.4406 0.0415 −0.0058 0.061 H(17A) 8c 0.4371 −0.0879 0.0613 0.061 H(17B) 8c 0.4576 −0.1414 0.0115 0.061 H(17C) 8c 0.3956 −0.1578 0.0460 0.061 H(18A) 8c 0.1474 0.1541 −0.1576 0.072 H(18B) 8c 0.2044 0.1597 −0.2002 0.072 H(18C) 8c 0.2012 0.2128 −0.1469 0.072 H(19A) 8c 0.2996 0.2117 0.1876 0.062 H(19B) 8c 0.2681 0.2508 0.2404 0.062 H(19C) 8c 0.2533 0.2790 0.1783 0.062 H(20A) 8c 0.3457 −0.1659 −0.0731 0.061 H(20B) 8c 0.3988 −0.1222 −0.1059 0.061 Table 2. Atomic coordinates and displacement parameters (in Å). Atom Site x y z Uiso

Crystal structure of sodium strontium monothiophosphate nonahydrate, NaSr[PO3S] · 9H2O

Abstract: H18NaO12PSSr, cubic, P213 (no. 198), a = 10.917(1) Å, V = 1301.1 Å, Z = 4, Rgt(F) = 0.041, wRref(F) = 0.087, T = 223 K. Source of material Trisodium monothiophosphate, Na3[PO3S], was synthesized from aqueous solutions of NaOH and PSCl3 according to [1]. A solution of sodium strontium monothiophosphate nonahydrate was obtained by adding SrCl2 · 6H2O (1.50 g, 5.626 mmol) to a solution of Na3[PO3S] (1.01 g, 5.626 mmol) in 40 mL distilled water at 40 °C. Slowly cooling at room temperature yielded cubeshaped colorless crystals of the title compoundwithin somedays. Experimental details The H atom parameters were refined freely except those which did not converge. The latter ones were fixed, positional parameters at the parameters found from Fourier difference maps and Uiso at 0.05 Å.

Crystal structure of triaqua-1,10-phenanthroline-nickel(II) maleate dihydrate, Ni(H2O)3(C12H8N2)(C4H2O4) · 2H2O

Abstract: C16H20N2NiO9, triclinic, P1 (no. 2), a = 8.938(1) Å, b = 9.3363(9) Å, c = 13.214(1) Å, 4 = 99.734(8)°, 3 = 100.846(9)°, 2 = 113.31(1)°, V = 957.7 Å, Z = 2, Rgt(F) = 0.025, wRref(F) = 0.070, T = 293 K. Source of material [Ni(phen)(male)(H2O)3] · 2H2O,with phen = 1,10-phenanthroline (C12H8N2) and H2male = maleic acid (C4H4O4), was synthesized according to the procedure described in the literature for the chemically related [Mn(male)(phen)(H2O)2]n · 2nH2O [1]. Stoichiometric amounts (3 mmol each) of maleic acid and nickel dichloride hexahydrate (NiCl2 · 6H2O)were dissolved separately in ethanol/watermixtures (1:1, v/v). Themaleic acid solutionwas then added slowly to the NiCl2 solution under continuous stirring at 273 K. An ethanolic solution of an equal amount (3 mmol) of 1,10-phenanthroline was then added dropwise. The pH of the mixture was adjusted to 6.3 with sodium hydroxide and the solution filtered. All raw materials were commercial products. By slow evaporation of the solvent at 273 K in an ice bath, light-blue crystals emerged. Discussion The crystal structure of the title compound consists of neutral [Ni(phen)(male)(H2O)3] complexes and additional water molecules, which are linked by a two-dimensional network of hydrogen bonds and Coulomb interactions. The Ni cation is nearly octahedrally coordinated by two nitrogen atoms from a phenanthroline molecule, one oxygen atom (O1M) from the maleate anion and the oxygen atoms of three water molecules (figure, top). The maleate anion is considerably twisted compared to the normally flat conformation. Two of the maleate oxygen atoms (O2M, O3M) are linked via hydrogen bonds to two water molecules (O3W, O2W) of the same complex, the last one (O4M) accepts a hydrogen bond from awater molecule (O1W) of the neighboring complex translated by 1,0,0. Pairs of Ni complexes, related by an inversion center, are connected by hydrogen bonds from thewatermoleculesO2WandO3Wof one of the complexes to the maleate oxygen atom O3M of the other complex and vice versa. These pairs are further connected by hydrogen bonds of type O1W–H11W···O4M into double chains along [100]. The planar phenanthroline molecules are pointing outwards, in two opposite directions, and their planes are all parallel (cf. the projection of the cell packing along [100], where the numbers denote thewatermoleculesO1W toO5W).A zipper-like'-' stacking of the phenanthroline molecules from neighboring chains provides the three-dimensional connectivity of the crystal structure (figure, bottom). The molecular packing creates channels along [100], where the crystalwatermoleculesO4WandO5Wreside. They are arranged in a zig-zag rowwithO···O distances between 2.736Å and 2.767Å, which are characteristic for hydrogen bonding betweenwatermolecules. The inversion centers in every secondO···O contact require a certain amount of disorder as indicated by the large isotropic displacement parameters of the H atoms located on these centers. However, due to the small scattering factor of hydrogen theX-ray data do not allow the unambiguous identification of the positions of the disordered H atoms in the vicinity of O4W and O5W. The water rows are interconnectedwith the Ni octahedra double chains by hydrogen bonds O4W–H14W···O2M, O4W···H21W–O1W 82 Z. Kristallogr. NCS 223 (2008) 82-84 / DOI 10.1524/ncrs.2008.0036 © by Oldenbourg Wissenschaftsverlag, München

Refinement of the crystal structures of scandium nickel boride, Sc2Ni21B6 and zirconium nickel boride, Zr2Ni21B6

Abstract: B6Ni21Sc2, cubic, Fm3m (no. 225), a = 10.5940(3) Å, V = 1189.0 Å, Z = 4, Rgt(F) = 0.018, wRref(F) = 0.041, T = 293 K. B6Ni21Zr2, cubic, Fm3m (no. 225), a = 10.6223(4) Å, V = 1198.6 Å, Z = 4, Rgt(F) = 0.018, wRref(F) = 0.039, T = 293 K. Source of material Samples with stoichiometric compositions were synthesized by arc-melting of mixtures of elements: Zr foil (99.99 %, Alfa, Johnson Matthey), Sc pieces (99.95 %, Ames), Ni foil (99.99 %, Alfa Aesar), and crystalline B powder (99.995 %, Chempur). The obtained reguli were sealed in Ta containers and annealed in evacuated silica tubes at 950 °C for 14 days. Needle-like single crystals were separated from well-crystallized ingots by mechanical fragmentation. The magnetization of polycrystalline sample pieces was measured in a SQUID magnetometer (MPMS XL-7, Quantum Design) in external fields between 20 Oe and 70 kOe and temperatures of 1.8 400 K. Experimental details Refinement of lattice parameters for each compound was performed on 30 reflections by least-squares fitting of powder diffraction data (HUBER G670 Imaging Plate Guinier Camera, CuK21 radiation, ) = 1.54056 Å) with LaB6 as internal standard (a = 4.1569 Å).

Crystal structure of songorine chloride trihydrate, [C22H32NO3]Cl · 3H2O

Abstract: C22H38ClNO6, trigonal, R3 (no. 146), a = 28.293(2) A, c = 7.4204(7) A, V = 5144.3 A, Z = 9, Rgt(F) = 0.051, wRref(F ) = 0.137, T = 296 K. Source of material Songorine, a C20-diterpenoid alkaloid is isolated from the chloroform extract of the roots ofAconitum szechenyianumGay, wetted by 10%ammoniumhydroxide solution before. The purified compound is dissolved in a 1% hydrochloric acid solution at first. Then the solution is adjusted to pH 6.5 with a 10% NaOH solution. Colorless single crystals were obtained at room temperature for days by slowly volatilizing the solvent. Experimental details Water H atoms were located in a difference Fourier map and refined with restrained O—H bond lengths (0.85(1) A) and fixed isotropic displacement parameters (0.08A). OtherH atomswere placed at calculated positions and refined using a riding model with O—H distances restrained to 0.82 A, C—H distances restrained to 0.93 A and N—H distance restrained to 0.91 A. Discussion Songorine belongs to the class of C20-diterpenoid alkaloids, a large group of biologically active compounds of naturally occurrence. As a diterpenoid alkaloid, songorine has been found to enhance both the orthodromic population spike and field excitatory postsynaptic potential (EPSP) in CA1 region of hippocampal slices [1]. Recently, it was indicated that songorine can enhance the excitatory synaptic transmission in rat hippocampus, and was proved that songorine is a novel non-competitive antagonist at the GABAA receptor in rat brain [2]. In the title crystal structure, there are one songorine cation, one chloride ion and 3 crystal water molecules (figure top). The bond length of C12—O2 is 1.202 A, and the angles of O2−C12−C11, O2−C12−C13 and C11−C12−C13 are 121.8(4)°, 122.8(4)° and 115.4(3)°, respectively, which indicates that the C12 and O2 are sp hybridized, and C11, C12, C13 and O2 atoms are in a plane. The bond length of C17—C16 is 1.322(6)A. The angles of C13− C16−C15, C17−C16−C15 and C17−C16−C13 are 108.0(3)°, 126.2(4)° and 125.5(4)°, respectively, which show an exomethylene attached to C16. The songorine cations are interlinked by hydrogen bonds (figure bottom). Intra-molecular hydrogen bonds O6W−H6WA···Cl1 and O5W−H5WA···Cl1 link the Cl−, crystal water O5W and O6W together. The hydrogen bonds C2−H2A···O4W, O1− H1···O4W, N1−H1N···O4W fix the crystal water O4W to songorine. The intermolecular hydrogen bonds O6W− H6WB···O5W (symmetric code: x,y,z−1) and C21−H21A···O1, C19−H19B···O1, C15−H15···O2 (symmetric code: x,y,z+1), link the songorinemolecules along [001]. The hydrogen bondsO5W− Z. Kristallogr. NCS 223 (2008) 111-113 / DOI 10.1524/ncrs.2008.0047 111 © by Oldenbourg Wissenschaftsverlag, Munchen

Crystal structure of 4,5,9,10-tetrathiocino[1,2-b;5,6-b']diimidazolyl- 1,3,6,8-tetraphenyl-2,7-dithione — dichloromethane (1:1), C30H20N4S6 · CH2Cl2

Abstract: C31H22Cl2N4S6, monoclinic, C12/c1 (no. 15), a = 21.9970(5) Å, b = 13.6104(5) Å, c = 23.1275(9) Å, = 92.525(2)°, V = 6917.4 Å, Z = 8, Rgt(F) = 0.054, wRref(F ) = 0.163, T = 233 K. Source of material The title compound was obtained by reaction of 1,3-diphenyl4,5-imidazolidine-4,5-dione with Lawesson’s reagent and nickel chloride in refluxing toluene. Experimental details Hydrogen atoms were calculated and refined using a riding model and were not established for the disordered solvent molecules. Discussion In the asymmetric unit is one solvent dichloromethane distributed over two positions. One in a general position with an occupancy factor of around 0.6 and the other disordered nearby a two-fold rotation axis with an ocupancy of 0.4. Nearby the general position are higher rest-electron density peaks with partial overlying positions to the solvent, which could not be reasonably refined. This is probably the reason for the relatively high R-value and the standard deviation for the C—C distances of 0.005Å. The conformation of the 8-membered ring will be influenced by two factors: first, the minimisation of the ring tension and second, the conjugation between the two attached imidazole rings. The well known conformation of a S8-ring like in orthorhombic sulfur has averaged bond distances, bond and torsion angels of 2.045 Å, 108.5° and 99.5°, respectively. Because of the shorter C4-chain with bond distances C2—C3, C3—C4 and C4—C5 of 1.358(5), 1.449(4) and 1.350(4) Å, the bond angles decrease for the angles at the sulfur atoms to an averaged value of 104.0° and increase at the carbon atoms to a value of 128.4° (ideal for a chain attached with two 5-membered rings is a value around 126.5°). The distorted conformation of the 8-membered ring can also be seen by two torsion angles, S1−S2−S3−S4 and C2−C3−C4−C5 with values of -77.08(7)° and 69.1(5)°, respectively. The twisting of the two imidazole rings of 69.1°, which decreases the electronic conjugation between them, is caused by the ring tension and the steric hindrance between the phenyl sustituents at N2 and N4. The hindrance can also be seen by the lower thermal ellipsoids of C13C15 and C25-C27 in comparison to the other carbon atoms of the phenyl groups. The distance between C13-C25 and C14-C26 are 3.493 Å and 3.485 Å and prevent a higher thermal motion. Remarkable is the dihedral angle of 59.1(2)° between these phenyl rings, maybe caused by a week interaction between the hydrogen atom at C14 with the system of the phenyl ring with a centroidhydrogen distance of 3.242 Å. A similar compound with two etyhl groups at N1 and N3 instead of phenyl groups is known from the literature [1]. The conformation of the 8-membered ring is nearly the same and the two imidazole rings are twisted 72° about the C3—C4 bond, only the two phenyl groups show a parallel orientiation. Z. Kristallogr. NCS 223 (2008) 231-232 / DOI 10.1524/ncrs.2008.0097 231 © by Oldenbourg Wissenschaftsverlag, München Crystal: colorless plate, size 0.06 × 0.15 × 0.25 mm Wavelength: Mo K radiation (0.71073 Å) : 5.78 cm−1 Diffractometer, scan mode: Nonius Kappa CCD, 2 max: 48° N(hkl)measured, N(hkl)unique: 16562, 5401 Criterion for Iobs, N(hkl)gt: Iobs > 2 (Iobs), 3970 N(param)refined: 411 Programs: SHELXS97 [2], SHELXL-97 [3], SHELXTL [4] Table 1. Data collection and handling.