Showing papers in "Journal of Chemical Crystallography in 2007"

Crystal structures of (−)-( S S , 1R , 2S , 5R )-menthyl p -tolyl sulfinate and (+)-( S S ) - [( p -tolyl)sulfinyl]ferrocene

Abstract: The absolute configuration at the chiral sulfurs centers of (−)-(S S , 1R, 2S, 5R)-menthyl-p-tolylsulfinate (1) and (S S )-[(p-tolyl)sulfinyl]ferrocene (2) were determined by single crystal X-ray diffraction with anomalous dispersion effects and the corresponding calculation of Flack’s absolute structure parameters. Both compounds crystallize in the monoclinic crystal system in space group P21 (no. 4); chiral sulfinate ester 1: a = 8.2868(6), b = 6.1399(3), c = 16.366(2) A, β = 91.816(6)°, V = 832.3(2) A3, Z = 2 and absolute structure parameter −0.03(7); chiral ferrocenyl sulfoxide 2: a = 5.8371(3), b = 15.390(2), c = 16.143(2) A, β = 97.748(6)°, V = 1436.9(3) A3, Z = 4 and absolute structure parameter +0.01(1). The trigonal pyramidal geometry at the chiral sulfur atom of 2 is close to expected values while the one of 1 is slightly distorted. With direct determination of the absolute configuration at the chiral sulfur centers an important gap concerning the widely used precursors 1 and 2 for the syntheses of chiral sulfoxides and 1,2-disubstituted planar chiral ferrocenyl ligands is now closed. The latter substance class is playing a key role in enantioselective catalysis.

Syntheses, characterization and crystal structures of two structurally similar Schiff bases isonicotinic acid [1-(3-methoxy-2-hydroxyphenyl)methylidene]hydrazide and isonicotinic acid [1-(4-dimethylaminophenyl)methylidene]hydrazide monohydrate

Abstract: The Schiff base compounds, isonicotinic acid [1-(3-methoxy-2-hydroxyphenyl) methylidene]hydrazide (C14H13N3O3, 1) and isonicotinic acid [1-(4-dimethylaminophenyl) methylidene]hydrazide monohydrate (C15H16N4O·H2O, 2) have been synthesized by the condensation of equimolar 3-methoxysalicylaldehyde or 4-dimethylaminobenzaldehyde with isonicotinic acid hydrazide in MeOH or EtOH. The compounds were characterized by elemental analysis, IR, 1HNMR spectra, and single crystal X-ray diffractions. Compound 1 crystallizes in the monoclinic space group P-1 with unit cell dimensions a = 7.662(1) A, b = 16.249(2) , c = 10.874(2) A, β = 110.426(3)°, V = 1268.7(3) ′3, Z = 4, R 1 = 0.0644, and wR 2 = 0.1283. Compound 2 crystallizes in the orthorhombic space group P212121 with unit cell dimensions a = 7.388(1) A, b = 11.812(1) A, c = 17.197(2) A, V = 1500.7(2) ′3, Z = 4, R 1 = 0.0585, and wR 2 = 0.1143. X-ray structure determinations revealed that the molecules of both compounds display trans configurations with respect to the C=N double bonds. In the crystal structure of 1, molecules are linked through N–H···N intermolecular hydrogen bonds, forming layers parallel to the bc plane, while in the crystal structure of 2, molecules are linked through N–H···O, O–H···O, and O–H···N intermolecular hydrogen bonds, forming a network.

Morpholinium 2,4-dinitrophenolate Aqua Salt and Ethylenediammonium 2,4-dinitrophenolate Aqua Salt

Abstract: The structures of the aqua salts of 2,4-dinitrophenolate (2,4-DNP−) with ethylenediammonium (EDA2+) and morpholinium (MP+) have been determined by X-ray diffraction, the first with 2:1 stoichiometry. The EDA2+ salt crystallizes in P21/c space group, with a = 5.887; b = 23.441; c = 7.075, β = 96.61, R1 = 0.0365 for reflections with Fo > 4sig(Fo). MP+ salt crystallizes as P–1 space group; a = 6.655; b = 9.388 c = 11.452; α = 104.82 β = 102.31 γ = 105.24, with R1 = 0.0334. Phenolates and ammonium groups interact through hydrogen bonds and the N+···O distances for MP+ and EDA2+ salts are 2.783 A and 2.812 A, respectively. There is one water molecule by asymmetric unit, interacting with phenolate and ammonium ions. The arrays of hydrogen bonds are cyclic, with six and four members alternated and the position of the units is dependent on the ability to form hydrogen bonds. The Job’s plot for ethylenediamine and 2,4 dinitrophenol shows the same 2:1 stoichiometry in ethanol for EDA2+-2,4-DNP− salt. Structures of the dinitrophenolate aqua salts of morpholinium and ethylenediammonium are described with cyclic networks of hydrogen bonds between the species.

Asymmetric base pairing in the complex 5-fluorocytosinium chloride/5-fluorocytosine monohydrate

Abstract: The structure of the complex 5-Fluorocytosinium chloride/5-Fluorocytosine monohydrate has been studied by X-ray diffraction methods. It crystallizes in the monoclinic system, space group P 21 /n, a = 7.1257 (15), b = 8.351 (3), c = 21.520 (4) A, β = 92.89 (8)°, V = 1279.0 (6) A3, Z = 4. The structure consists of triple hydrogen-bonded 5-Fluorocytosine pairs, water molecules and chloride anions. Asymmetric reversed Watson-Crick base pairing occurs between one protonated (5FcytH+) and one neutral 5-Fluorocytosine (5Fcyt) molecule.

Synthesis and structural characterization of 2,5-dihalo-3,4-dinitrothiophenes

Abstract: Using new nitration protocols, we have been able to efficiently dinitrate 2,5-dihalothiophenes with yields of ∼80–95%. The resulting products 2,5-dibromo-3,4-dinitrothiophene (1), 2,5-dichloro-3,4-dinitrothiophene (2), 2-bromo-5-chloro-3,4-dinitrothiophene (3), as well as the analogous 2-bromo-3,4-dinitrothiophene (4), all crystallize easily allowing their characterization via X-ray crystallography. Crystallization of 1 occurs in the monoclinic space group C2/c with a = 14.547(3) A, b = 7.3534(15) A, c = 10.775(2) A, β = 128.89(3)°, and Z = 4. Crystallization of 2 occurs in the tetragonal space group I-42d with a = 9.9398(14) A, b = 9.9398(14) A, c = 16.866(3) A, and Z = 8. Crystallization of 3 occurs as a pseudo-merohedral twin in the triclinic space group P-1 with a = 7.340(5) A, b = 8.094(5) A, c = 9.112(5) A, α = 82.059(5)°, β = 66.232(5)°, γ = 63.021(5)°, and Z = 2. Crystallization of 4 occurs in the triclinic space group P-1 with a = 7.1787(14) A, b = 7.4092(15) A, c = 8.3151(17) A, α = 101.67(3)°, β = 96.00(3)°, γ = 116.13(3)°, and Z = 2. The structures of all compounds exhibit the formation of interesting solid-state assemblies due to halogen-bonding interactions between the halogen and nitro groups.

Crystallographic and conformational analyses of zwitterionic form of (E)-2-methoxy-6-[(2-morpholinoethylimino)methyl]phenolate

Abstract: The single crystal X-ray diffraction analysis of the title compound, C14H20N2O3, reveals that the structure is adapted to its zwitterionic form and $$R_2^2 (12)$$ centrosymmetric dimers are formed by N+–H···O− type ionic weak hydrogen bonds in the crystal structure. The title compound crystallizes in the triclinic space group P−1 with a = 5.9255(13) A, b = 9.853(3) A, c = 12.248(3) A, α = 101.793(19)°, β = 94.941(17)°, γ = 104.36(2)°, Z = 2, Dx = 1.308 g/cm3, μ (Mo-Kα) = 0.092 mm−1. The structure was solved by direct methods and refined to a final R = 0.0371 for 2183 reflections with I > 2σ (I). The crystal structure is stabilized by N+–H···O− type intra-molecular hydrogen bonds and N+–H···O− type packing interactions referred to as weak hydrogen bonds. To elucidate conformational flexibility of the title molecule, the selected torsion angle is varied from −180° to +180° in every 10° separately and then molecular energy profile is calculated and construed. In addition, charge-population analysis of the crystallographically observed structure confirms its zwitterionic form.

X-ray diffraction, DFT, and spectroscopic study of N,N′-difluoroboryl-5-(2-thienyl)dipyrrin and fluorescence studies of related dipyrromethanes, dipyrrins and BF2-dipyrrins and DFT conformational study of 5-(2-thienyl)dipyrrin

Abstract: To explore the characteristics of potential fluorescent probes that could be used to screen prospective HDS catalysts, new 5-thienyl dipyrromethene derivatives have been prepared. 5-(2-thienyl)- (1a), 5-(3-thienyl)- (1b), and 5-(3-(2,5-dibromothienyl))-dipyrromethane (1c), were oxidized with DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) separately to give the corresponding dipyrrins 2a–2c. These were subsequently treated with F3B·OEt2 to afford the respective N,N′-difluoroboryl-5-(thienyl)dipyrrin compounds, 3a–3c; the latter two may serve as polymer precursors. Significant fluorescence signal enhancement is achieved with 3a–3c over 2a–2c. Orange fluorescence is observed for 3a whereas its isomer 3b gives green fluorescence (365 nm). An X-ray diffraction study of 3a was performed (orthorhombic, P212121, a=10.684(10) A, b=15.208(13) A, c=7.256(6) A, V=1179.0(17) A3, Z=4, R 1=0.0428, wR 2=0.0686) and its geometry was studied by way of DFT (Gaussian 03; B3LYP/6-31G*) to give a HOMO/LUMO energy level difference of 414 nm, and a 2-thienyl group rotational barrier of ∼6 kcal/mol, compared to that of ∼12 kcal/mol for the phenyl derivative. Theoretical modeling of 2a demonstrated that the [N–H⋯N] interaction is favored by ca. 10 kcal/mol, whereas [N–H⋯S] bonding is sterically unattainable.

A new dabco templated metal sulfate, (C6H14N2)[Mn (H2O)6](SO4)2. Chemical preparation, hydrogen-bonded structure and thermal decomposition

Abstract: The crystal structure of manganese sulfate templated by 1,4-diaza-bicyclo[2.2.2]octane (abbreviated dabco), (C6H14N2)[Mn(H2O)6](SO4)2, was investigated using single crystal X-ray diffraction data. It crystallises in the monoclinic system (space group P21/c) with the following unit-cell parameters: a = 12.1392(2) A, b = 12.3117(2) A, c = 12.2765(2) A, β = 104.607(1)°, V = 1775.47(5) A3 and Z = 4. The structure has been solved using direct methods and refined by least-squares analysis [R 1 = 0.0381, wR 2 = 0.1082]. The crystal structure of the title compound is built from isolated [Mn(H2O)6]2+ octahedral cations, 1,4-diaza-bicyclo[2.2.2]octandiium cations (C6H14N2)2+ and sulfate anions (SO4)2− connected by a three-dimensional hydrogen-bond network. The thermal decomposition of the precursor, studied by thermogravimetry and temperature-dependent X-ray powder diffraction, proceeds through four stages giving rise to the mixture of Mn2O3and Mn3O4.

Noncovalent supramolecular interactions in the crystal structure of 2-amino-3,5-dibromo-4,6-dimethylpyridinium tetrabromocadmate(II)

Abstract: Reaction of 2-amino-4,6-dimethylpyridine with cadmium chloride, HBr and Br2 in ethanol yeilds bis(2-amino-3,5-dibromo-4,6-dimethylpyridinium) tetrabromocadmate(II). The complex crystallizes in the monoclinic space group P21/c, with tetrahedral distortion of the $${\rm CdBr}_4^{2 - }$$ ion. The cations are arranged in a zig-zag chains that are held together via Br···Br, Br···π, π···Br···π and π-π interactions. Extensive $${\rm CdBr}_4^{2 - }$$ ···cation interactions were found and represented in different Br···HN (pyridinic and aminic) and Br···HCH2 hydrogen bonding along with Br···Br motifs.

Tri-metal Secondary Building Units: Toward the Design of Thermally Robust Crystalline Coordination Polymers

Abstract: Three new crystalline coordination polymers [Mn3(TDC)4(H2O)4](2,6-lutidine)2(H2O)3 1, P-1, a = 11.351(3), b = 11.391(3), c = 11.480(3), α = 112.838(4), β = 90.696(4), γ = 99.328(4); [Zn3(1,4-BDC)3(EtOH)2] 2, C2/c, a = 19.1308(9), b = 10.6088(5), c = 16.2221(7), β = 108.79(1); and [Zn3(1,3-BDC)3(py)2](MeOH) 3, P2(1)/c, a = 17.142(3), b = 21.544(4), c = 11.805(2), β = 106.441(3); TDC = 2,5-thiophenedicarboxylate, BDC = benzedicarboxylate, have been synthesized by linking tri-metal nodes with poly-carboxylate ligands. Single crystal x-ray analysis shows that 1 is composed of (4,4) 2-D grids with A–A stacking while 2 is comprised of (6,3) triangular networks in an A–B–C stacking pattern and 3 has formed a distorted cubic diamondoid topology. Tri-metal nodes are located at the vertexes of each network. Thermal gravimetric analysis demonstrates that 1 and 2 are thermally robust structures with network decomposition temperatures of 375 °C and 460 °C respectively. Tri-metal Secondary Building Units: Toward the Design of Thermally Robust Crystalline Coordination Polymers Brian S. Luisi, Zhenbo Ma and Brian Moulton* Tri-metal nodes are shown to be an advantageous target in the synthesis of 2-D crystalline coordination polymers with high thermal stability.

Synthesis, Characterization and Crystal Structure of a Polymeric Zinc(II) Complex Containing the Antimalarial Quinine as Ligand

Abstract: A novel polymeric zinc(II) complex of quinine, [chlorosulphato (2-ethenyl)-4-azabicyclo[2.2.2]oct-5-ylium-(6-methoxyquinolin-4-yl) methanol zinc(II)] has been synthesized and characterized. Single-crystal X-ray diffraction analysis of the complex (C20H25ClN2O6SZn) revealed that quinine forms a zigzag coordination polymeric complex with Zn(II) of extended chains –ZnCl–O–SO2–O–Zn–O–SO2–O–ZnCl–. The crystals are monoclinic, space group C2 with a = 20.5035(5), b = 9.7943(2), c = 11.7814(4) A, β = 96.578(2)°, Z = 4, V = 2350.3(1) A3. The complex exhibits a tetrahedral geometry. Each Zn(II) centre is thus coordinated to an O atom from each of two sulphate bridges, a Cl atom and quinoline atom N(4) of the quinine moiety. The second quinuclidine nitrogen in the quinine is protonated. In the crystal, there is linkage of two polymeric chains related by a twofold rotation axis, resulting in a bilayer. The linking is achieved by hydrogen bonding from the quinine cation which provides two donors (–OH, N+–H), to oxygen atoms of sulphate groups which act as acceptors. The new polymeric zinc(II) complex of quinine, [chlorosulphato (2-ethenyl)-4-azabicyclo[2.2.2]oct-5-ylium-(6-methoxy quinolin-4-yl) methanol Zinc(II)] has been synthesized and structurally characterized The compound was characterized by IR spectroscopy, elemental analysis and X-ray diffraction. X-ray analysis showed that quinine forms a zigzag coordination polymeric complex with Zn(II) of extended chains –ZnCl–O–SO2–O–Zn–O–SO2–O–ZnCl–.

Hydrogen-Bonding Networks in Heterocyclic Thioureas

Abstract: The synthesis of heterocyclic thioureas from heterocyclic amines with phenyl- or methylisothiocyanate or CS2 is described. Seven new X-ray crystal structures are reported: In N-(3-pyridyl)-N′-phenylthiourea (Pna21, a = 10.1453(3), b = 17.6183(5), c = 6.4787(2), V = 1158.02(6), Z = 4) hydrogen-bonding results in formation of a 3D network consisting of helices, which form channels parallel to the c-axis. In N-(4-pyridyl)-N′-phenylthiourea (P21/c, a = 16.9314(3), b = 10.3554(2), c = 13.5152(3), β = 106.5080(10), V = 2271.96(8), Z = 4, two independent molecules) hydrogen-bonding results in N–H···S bridged dimers and N–H···Py chains, forming a 2D sheet network. In N-(2-pyrimidyl)-N′-phenylthiourea (P21/c, a = 5.45900(10), b = 13.8559(2), c = 14.3356(3), β = 94.9800(10), V = 1080.24(3), Z = 4) and N-(2-pyrimidyl)-N′-methylthiourea (P21/c, a = 8.8159(5), b = 11.2386(5), c = 7.7156(4), β = 95.629(2), V = 760.76(7), Z = 4) pairs of intra- and intermolecular N–H···N interactions produce dimers. Dimer formation through N–H···S occurs for N-(2-thiazolyl)-N′-methylthiourea (C2/c, a = 17.9308(3), b = 7.78260(10), c = 10.8686(2), β = 105.3740(10), V = 1462.42(4), Z = 8). Two symmetrically disubstituted thioureas were examined: N,N′-bis(2-pyridyl)thiourea (Fdd2, a = 15.1859(2), b = 30.1654(3), c = 9.44130(10), V = 4324.95(8), Z = 16) forms intra- and intermolecular N–H···Py hydrogen-bonds, forming a 1D zigzag chain and N,N′-bis(3-pyridyl)thiourea (P21/c, a = 13.2461(2), b = 6.26170(10), c = 12.3503(2), β = 96.0160(10), V = 1018.73(3), Z = 4) forms intermolecular N–H···Py hydrogen-bonds, resulting in 2D sheets. Hydrogen-Bonding Networks in Heterocyclic Thioureas. Aakarsh Saxena and Robert D. Pike* The synthesis and hydrogen bonded structures of various pyridyl-, pyrimidyl-, and thiazolyl-substituted thioureas is presented.

Structural Analysis of Bisphenol-A and its Methylene, Sulfur, and Oxygen Bridged Bisphenol Analogs

Abstract: The molecular structures of bisphenol-A, C(CH3)2(p-C6H4OH)2 (monoclinic, P21/n, a = 11.1940(6) A, b = 18.738(1) A, c = 17.8623(9) A, β = 100.571(1)°), its methylene (CH2) and heteroatom (S, O) bridged analogs, CH2(p-C6H4OH)2 (monoclinic, P21/n, a = 5.4351(1) A, b = 20.7895(3) A, c = 8.8432(1) A, β = 93.419(1)°), S(p-C6H4OH)2 (monoclinic, P21/n, a = 5.5115(1) A, b = 21.0666(2) A, c = 8.6917(1) A, β = 92.962(1)°) and O(p-C6H4OH)2 (orthorhombic, Pbcn, a = 5.2745(5) A, b = 8.2724(8) A, c = 22.085(2) A), have been determined by X-ray diffraction at 115 K, revealing structural differences in the series of compounds. The results show that the Caryl–Xbridge–Caryl angles (Xbridge = C(CH3)2, CH2, S, O) span a range greater than 14°. The dihedral angle between the planes of the hydroxyphenyl groups also varies according to the identity of the bridging group, varying from 67.24(2)° in S(p-C6H4OH)2 to 85.82(4)° in C(CH3)2(p-C6H4OH)2. In addition, the pitch angle, which more accurately describes the propeller-like nature of these bisphenolic compounds, varies from 39.88(3)° in S(p-C6H4OH)2 to 59.62(7)° in C(CH3)2(p-C6H4OH)2. Ab initio electronic structure calculations predict very similar bond lengths and angles to those observed crystallographically; however, the predicted dihedral angles and pitch angles are quite different, suggesting that these features are greatly influenced by crystal packing.

Solid State Synthesis and Hierarchical Supramolecular Self-assembly of Organic Salt Cocrystals

Abstract: This paper describes the solid-state synthesis and systematic studies of versatile supramolecular self-assembly of 14 new series of organic salt cocrystals. Hierarchical self-assembly in the solid state utilizes the cooperative interaction of hydrogen bonding, electrostatic and π–π interactions. These salts are crystallized as a highly ordered self-assembly directed by intermolecular non-covalent interaction. Fourteen cocrystals of organic salt have been characterized by single crystal X-ray diffraction and their solid-state packing pattern has been compared.

The Preparation, Characterization and X-ray Structural Analysis of Tetrakis[1,3-dimethyl-2(3H)-imidazoleselone]cadmium(II) Hexafluorophosphate

Abstract: A new compound, [Cd(dmise)4][PF6]2, has been synthesized and characterized via standard solid and solution state methods including single crystal X-ray crystallography (dmise = 1,3-dimethyl-2(3H)-imidazoleselone). The title compounds crystallizes in orthorhombic space group P bcn with a = 12.783(3), b = 22.206(4), c = 13.153(3) A, V = 3733.8(13) A3, Z = 4. The complex is a high melting, yellow water soluble 2:1 electrolyte solid that state has a flattened tetrahedral CdSe4 coordination geometry. To date this is the only structural study reported for a homoleptic selenourea complex of cadmium. The Preparation, characterization and X-ray structural analysis of Tetrakis[1,3-dimethyl-2(3H)-imidazoleselone]cadmium(II) hexafluorophosphate Daniel J. Williams, Bradley J. McKinney, Ben Baker, Kevin P. Gwaltney and Donald VanDerveer Tetrakis[1,3-dimethyl-2(3H)-imidazoleselone][PF6]2 is prepared in 82% yield by direct combination of cadmium acetate dihydrate, ammonium hexafluorophosphate, and the ligand in boiling acetonitrile. X-ray crystallography shows a structure with a distorted tetrahedral coordination sphere around the cadmium. This is the first report of a structural characterization of a homoleptic cadmium selenourea complex.

X-ray Crystal Structure of Trans-UO2(N(SiMe3)2)2(THF)2: One in a Series of Uranyl(VI) Complexes Supported by Bis(trimethylsilyl)amido Ligands

Abstract: The title compound trans-UO2(N(SiMe3)2)2(THF)2 (1) was synthesized and characterized by X-ray crystallography. The complex crystallizes in the monoclinic space group C2/c (#15) with lattice parameters a = 16.0771(5) A, b = 13.1196(4) A, c = 16.9391(6) A, β = 116.853(1)°, V = 3187.61(18) A3, Z = 4, D calc = 1.532 g cm-3. The six-coordinate uranium(VI) center adopts an all-trans octahedral geometry consisting of mutually trans oxo groups, silylamido ligands, and neutral THF donors. Structural comparisons of this uranyl(VI) bis(amido) complex with a related tris(amido) derivative within the series are made based on symmetry, charge, and coordination number. The X-ray crystal structure of the title complex is reported, providing comparisons based on symmetry, charge, and coordination number with a related uranyl(VI) amido derivative within this series.

The co-crystal of iron(II) complex hydrate with hydroxybenzoic acid: [Fe(Phen) 3 ]Cl(p-hydroxybenzoate).2(p-hydroxybenzoic acid).7H 2 O

Abstract: Crystal of [Fe(Phen)3]Cl(PHB).2(PHBH).7H2O (1) is triclinic, space group P-1 with a = 12.0388(11) A, b = 15.5286(14) A, c = 15.7794(14) A, α = 89.759(2)°, β = 75.818(2)°, γ = 71.900(2)° and Z = 2, (phen = phenanthroline, PHBH = p-hydroxybenzoic acid, PHB = p-hydroxybenzoate anion). The phen in adjacent Fe(phen)3 2+ cations are π–π interacted forming offset face to face (OFF) motifs. Juxtaposition of four phen ligands from two cations encapsulate an R2 2(8) dimeric unit of H-bonded PHBH molecules within a centrosymmetric box froming a filled aryl box motif (FAB). Alternation of OFF and FAB motifs form {OFF⋯FAB}∞ strands. The Fe(phen)3 2+ cation engages its phen ligands in π–π and/or CH–π interactions with two crystalographically different PHBH molecules and one PHB anion. Seven water molecules and a chloride anion per iron(II) trisphenanthroline cation fill empty spaces in the structure forming a hydrophilic cluster. Extensive intermolecular H-bond interactions occur between water molecules, chloride anions, PHBH molecules, and PHB anions. Thermal analysis of (1) was done under N2(g). The TG, and dTG curves revealed the expected mass losses. All associated processes are endothermic as shown in the DSC curve.

Copper(II) and lead(II) complexes of 4,4′-bipyridine-N,N′-dioxide

Abstract: Cu(II) and Pb(II) complexes of 4,4′-bipyridine-N,N′-dioxide have been prepared using a solvent-layering system. [Cu2Cl4(bpdo)3(H2O)2] . 2(CH3)2SO (1) crystallises in P-1, a=8.731(2), b=8.943(2), c=14.408(3) A, α=102.85(3), β=97.49(3), γ=109.77(3)°. The Cu(II) complex is a z-shaped discrete molecule with a DMSO molecule hydrogen bonded to the host through coordinated water molecule. Crystallisation of PbCl2, PbBr2 and PbI2 with bpdo afforded isostructural 2D coordination polymers. [PbCl2(bpdo)]n is monoclinic, C2/c with a=16.3274(7), b=4.0708(1), c=18.6146(8) A, β=93.73(1)°; [PbBr2(bpdo)]n is monoclinic, C2/c with a=16.403(3), b=4.2412(8), c=18.846(4) A, β=92.59(3)° and [PbI2(bpdo)]n is monoclinic, C2/c with a=16.438(3), b=4.538(1), c=18.973(4) A, β=91.04(3)°. The adjacent metal centres of these polymers are bridged by coordinated Cl−, Br− or I− anions as well as by bpdo ligands. These polymers possess no conventional hydrogen bonds.

Crystal structure and infrared analysis of a new trinuclear platinum(II) complex with L-cysteine

Abstract: A new trinuclear platinum(II) complex with cysteine of composition [Pt(C3H6NO2S)Cl]3·(C2H6SO)3 was obtained and structurally characterized by X-ray diffraction and infrared analysis. The compound crystallizes in the trigonal system, space group R3, and is described in a hexagonal cell with a=17.739(1), c=9.531(1) and Z=3. Cysteine is coordinated to Pt(II) through the nitrogen and sulphur atoms. Each cysteine sulphur bridges between two metal atoms. A square planar coordination sphere of platinum is completed by a chlorine atom. The complex is soluble in dimethyl sulfoxide.

Hydrogen-Bonding Interactions in the Crystal Structure of Bis(N-propyl-N-(2-hydroxyethyl)dithiocarbamato-S,S′)nickel(II): Ni[S2CN(nPr)(CH2CH2OH)]2

Abstract: Two independent molecules of Ni(S2CN(Pr)CH2CH2OH)2, each located about a center of inversion, comprise the asymmetric unit. The molecules differ from each other in terms of the relative orientation of the terminal hydroxyl groups. A square planar geometry is found for each nickel atom defined by four sulfur atoms derived from two symmetrically chelating dithiocarbamate ligands. The crystal packing is dominated by O–H···O interactions that lead to extensive cross linking in all directions. The compound crystallizes in the triclinic space group P-1 with a = 6.4008(11) A, b = 11.480(2) A, c = 12.517(2) A, α = 88.021(2)°, β = 82.491(2)°, γ = 89.986(2)°, and Z = 2.

Synthesis and structure of a novel copper (II) nitrate complex of 2,4-dioxo-4-phenylbutanoic acid

Abstract: 2,4-Dioxo-4-phenylbutanoic acid, 1, was synthesized as a biproduct of the attempted synthesis of 1,6-bisphenyl-1,3,4,6-hexanetetrone. Crystals of [Cu(H2O)(bipy) (L)][Cu(bipy)(L)(NO3)] (H2O)(NO3) (L = 2,4-dioxolato-4-phenylbutanoic acid and bipy = 2,2′-bipyridine), 2, were grown by slow evaporation of a solution of Cu(NO3)2·3 H2O, 2,2′-bipyridine, and 1 in a mixture of ethanol and water. The compound crystallized in the triclinic space group P-1 and is made up of two distinct molecular units each with approximately square pyramidal geometry: a = 10.663(2) A, b = 13.275(3) A, c = 15.071(3) A, α = 80.26(3)°, β = 74.13(3)°, γ = 89.12(3)°. The copper ions are chelated by molecules of 1 and molecules of bipyridine. The molecular units are arrayed in rows held together by pi-stacking interactions and hydrogen bonding.

Crystal Structures of Hexameric and Dimeric Complexes of Lithioisobutyrophenone

Abstract: The crystal structures of two unsolvated hexameric complexes and one N,N,N′,N′-tetramethyl-1,2-ethanediamine (TMEDA)-solvated dimeric complex of the lithium enolate of 2-methyl-1-phenyl-1-propanone (lithioisobutyrophenone, LiIBP) are reported. The unsolvated LiIBP complexes crystallize from benzene-d 6 to yield two different types of crystals that have similar structures: one in the triclinic space group P-1 with a = 10.7944(7), b = 11.9350(8), c = 12.0956(8) A; α = 117.5560(10), β = 100.8090(10), γ = 92.3030(10)° and Z = 1 and a second in the monoclinic space group C2/c with a = 17.6011(11), b = 14.7389(9), c = 21.0943(13) A; β = 105.2510(10)° and Z = 4. The two LiIBP hexamers differ slightly in the conformations of the enolate moieties around the Li6O6 core. The hexamer in both the triclinic as well as the monoclinic polymorph is located on a crystallographic inversion center that each generates the other half of the cluster. The TMEDA-solvated LiIBP dimer crystallizes from hexanes in the monoclinic space group C2/c with a = 11.8472(6), b = 14.8268(7), c = 19.2719(9) A; β = 98.8480(10)° and Z = 4. The center of the dimer is located on a crystallographic C2 axis. These complexes represent only the second reported crystal structures of either an unsolvated hexamer or a solvated dimer of a lithium enolate of a simple monocarbonyl ketone. The X-ray crystal structures of two unsolvated hexameric and one N,N,N′,N′-tetramethyl-1,2-ethanediamine (TMEDA)-solvated complexes of the lithium enolate of 2-methyl-1-phenyl-1-propanone (lithioisobutyrophenone, LiIBP) are reported.

Single crystals of calcium and strontium phenylphosphonate grown via hydrothermal crystallization

Abstract: Single crystals of Ca(HO3PC6H5)2 (1) and Sr(HO3PC6H5)2 (2) have been obtained via the crystallization of their respective amorphous powders. The amorphous compounds were synthesized by traditional solution routes and were subsequently crystallized at 160°C in a Teflon-lined autoclave containing 1–3 mL distilled water. The resultant single crystals were physically isolated and their structures determined by single crystal X-ray diffraction. The two compounds are isostructural and crystallize in space group C2/c with lattice parameters of a = 31.267(3) A, b = 5.6185(6) A, c = 7.7202(8) A, β = 101.924(2)°; and a = 31.514(4) A, b = 5.8098(8) A, c = 7.8218(10) A, β = 102.063(3)° for the calcium and strontium phenylphosphonate, respectively.

Dinuclear Complexes and a One-dimensional Chain Involving Difunctional Ligands Containing the Acetylacetonate Functionality

Abstract: Systems containing two acetylacetonate (acac) ligands separated by an aromatic spacer (1–3) react with Cu(II) in the presence of bidentate nitrogen ligands to form crystalline, capped, dinuclear (zero-dimensional) structures (6–8). Noncovalent interactions between stacked aromatic ligands on adjacent molecules in 7 and 8 produce one-dimensional chains in the crystal. Molecules 1–3 fail to produce crystalline, one-dimensional chains with covalent metal-organic bonding on reaction with Cu(II) alone. System 5, which contains a single acac ligand and a pyridyl nitrogen, forms a crystalline, one-dimensional chain on reaction with Cu(II) in the presence of a bidentate nitrogen ligand (9). The covalent bonding ribbon of the chain passes from acac to Cu(II) to the pyridyl nitrogen and back to acac. The phenanthroline ligands in 9 provide noncovalent bonding with adjacent chains in the crystal to produce a two-dimensional layered structure. Dinuclear Complexes and a One-dimensional Chain Involving Difunctional Ligands Containing the Acetylacetonate Functionality Joseph B. Lambert and Zhongqiang Liu Two acetylacetonate ligands separated by an aromatic spacer react with Cu(II) in the presence of bidentate nitrogen ligands to form crystalline, capped, dinuclear (zero-dimensional) structures, whereas acetylacetonate linked to pyridine forms a crystalline, one-dimensional chain on reaction with Cu(II) with phenanthroline ligands on adjacent chains noncovalently bonded to form a two-dimensional layered structure in the crystal.

One Novel Three-dimensional Network Constructed from [Mn(4,4′-bip)2(OH2)4]2+ Cations and DBA2− Anions via Hydrogen-bonding and π–π Interactions

Abstract: One new mononuclear manganese complex of [Mn(4,4′-bip)2(OH2)4](DBA) · 4H2O (1) (4,4′-bipyridine, 4,4′-bip; H2DBA, benzene-1,3-dicarboxylic acid) has been obtained from the hydrothermal reaction of MnCl2 · 4H2O, 4,4′-bipyridine and H2DBA in the solvent of H2O at 140 °C for 3 days, characterized by X-ray analysis, spectroscopic methods, and thermal analysis. Packing diagram shows that the three-dimensional network was formed via hydrogen bonds and strong π–π interactions. One Novel Three-dimensional Network Constructed from [Mn(4,4′-bip) 2 (OH 2 ) 4 ] 2+ Cations and DBA 2− Anions via Hydrogen-bonding and π–π Interactions Ying Liu, Bao Zhang, Jian-min Dou, Da-qi Wang, Da-cheng Li, Lei Zhou One new mononuclear manganese complex of [Mn(4,4’-bip)2(OH2)4](DBA) · 4H2O (1) (4,4’-bipyridine, 4,4’-bip; H2DBA, benzene-1, 3-dicarboxylic acid) has been obtained and haracterized by X-ray analysis, spectroscopic methods, and thermal analysis. Packing diagram shows that the three-dimensional network was formed via hydrogen bonds and strong π-π interactions.

Single Crystal X-ray Diffraction Study of a Pure Natrolite Sample

Abstract: The crystal structure of a pure natrolite sample, Na2(Al2Si3O10)·2H2O, coming from Asheken, Ethiopia, has been analysed by single crystal X-ray diffraction. It crystallizes within the orthorhombic space group Fdd2, with the following cell constants: a = 18.2930(2) A; b = 18.6430(5) A; c = 6.5860(5) A; V = 2246.07(18) A3. The three-dimensional framework of this hydrated aluminosilicate zeolite is made up by chains of corner-sharing SiO4 and AlO4 tetrahedra down c; the chains are held together by sharing the external vertices of tetrahedra; water molecules and Na+ extra-framework cations fill up the resulting cavities, the latter forming irregular NaO6 octahedra. Hydrogen bonds complete the array.

Syntheses and crystal structures of an organometallic thiosemicarbazone and an organometallic enehydrazide

Abstract: Reactions of ferrocenoylacetone with thiosemicarbazide and isonicotinic acid hydrazide generate an organometallic thiosemicarbazone 1 and enehydrazide 2, respectively. The complexes 1 and 2, which can be formulated as [C5H5FeC5H4C(O)CH2C(=NNHCSNH2)CH3] and [C5H5FeC5H4C(O)CH=C(NHNHCOC5H4N-4)CH3], have been characterized by elemental analyses, IR, NMR, UV and were structurally characterized by single-crystal X-ray crystallography. Complex 1 (C15H17FeN3OS) crystallizes in the monoclinic space group P21/c, with lattice constants: a = 13.939(3) A, b = 8.2600(17) A, c = 13.176(3) A, β = 94.83(3)°, V = 1511.7(6) A3, Z = 4, D c = 1.508 g cm−3, F(000) = 712, R 1 = 0.0602, wR 2 = 0.1526. Two intermolecular hydrogen bonds N–H···S (N···S = 3.356(8) and 3.499(7) A, N–H···S = 168 and 170°) form a chain in the [010] direction. The intermolecular hydrogen bond C–H···O (C···O = 3.432(10) A, C–H···O = 151°) leads to a [010] double-chain through each unit cell. The intermolecular hydrogen bond C–H···O (C···O = 3.359(10) A, C–H···O = 173°) makes the [010] double-chain pack along the c axis to result in a two-dimensional network. Complex 2 (C20H19FeN3O2) crystallizes in the monoclinic space group P21/c, with lattice constants: a = 14.091(2) A, b = 10.024(2) A, c = 13.806(2) A, β = 112.41(2)°, V = 1802.8(6) A3, Z = 4, D c = 1.434 g cm−3, F(000) = 808, R 1 = 0.0576, wR 2 = 0.1593. The strong intramolecular hydrogen bond N–H···O from the enamine N atom and carbonyl O atom stabilizes the enehydrazide. The intermolecular hydrogen bonds N–H···O and C–H···O (N···O = 2.906(6) A, N–H···O = 155° C···O = 3.364(6) A, C–H···O = 153°) generate a [010] chain. The intermolecular hydrogen bond N–H···O (N···O = 2.989(6) A, N–H···O = 128°) forms a [010] double-chain through each unit cell. The π···π stacking interation involving the pyridyl groups makes the [010] double-chain pack along the c axis to lead to a two-dimensional network.

Distortion Isomerism of Cu(II) Chloride Adducts with Bis(2-benzimidazolyl)ethane. Synthesis, Characterization, X-ray Structures and Spectroscopy of Four Different Isomers

Abstract: 3D structures and spectroscopic properties are reported of four compounds with the ligand bis(2-benzimidazolyl)ethane (hereafter abbreviated as dbz) attached to CuCl2, all having the general formula [Cu(dbz)Cl2](Hb) x . (in which Hb = EtOH or MeOH and x = 1/2 or 1). The X-ray crystal structure has been solved from these four slightly different compounds, namely: green α-[CuCl2dbz](C2H5OH)1/2 (1), the red compound β-[CuCl2dbz](C2H5OH)1/2 (2), which both have two slightly different units in the unit cell, the red α-[CuCl2dbz](CH3OH) (3) and a blue–green compound β-[CuCl2dbz](CH3OH) (4). The geometry around the Cu(II) anion is distorted tetrahedral for all four compounds, with chromophores consisting of two nitrogen atoms of the bidentate chelating dbz molecule and two chloride anions. The unit cells of compound 1 and 2 consist of two chemically identical, but crystallographically different units, while compounds 3 and 4 each have only one independent CuCl2-(dbz) unit. The major differences are observed in the dihedral angles NCuN–ClCuCl, which vary from 29.3 to 77.1° for the four compounds. The differences are related to different packing effects, ring–ring stacking and H-bond interaction, due to the two different alcohols used. In fact these four compounds represent a new range of examples of distortion isomerism in pseudo-tetrahedrally coordinated species. Characterisation of the four compounds has been completed by IR, EPR and LF spectroscopy.

Self-Assembly of C-Methyl Calix[4]resorcinarene with 5,5′-Bipyrimidine

Abstract: The X-ray crystal structure of the complex formed between 5,5′-bipyrimidine and C-methylresorcinarene is described. The structure (C41H45N5O12) is triclinic with a = 12.8610(10), b = 13.0560(10), c = 13.6068(11)A, α = 104.0730(10), β = 104.9260(10), γ = 111.6430(10)° and space group P-1. The structure reveals that the resorcinarene adopts a boat conformation and forms a three-dimensional network through hydrogen bonding to two water molecules and one dipyrimidine ligand. A single nitromethane molecule is included in the superstructure. Self-Assembly of C-Methyl Calix[4]resorcinarene with 5,5’-Bipyrimidine Charles L. Barnes(1) and Eric Bosch(2)* The X-ray crystal structure of the complex formed between 5,5′-bipyrimidine and C-methylresorcinarene is reported.

Synthesis, Properties, and Crystal Structures of Copper(II) Di-(2-picolyl)amine Complexes Containing Inorganic Salts

Abstract: These complexes have been characterized by X-ray crystallography, spectroscopic, and cyclic voltammetry. In 1, the copper(II) ion has a distorted square-pyramidal geometry with three nitrogen atoms of the dpa ligand and two oxygen atoms of the nitrate anions. The crystal structure of 2 shows that the copper(II) ions are bridged by tp anion to form a dinuclear complex, in which each copper(II) ion exhibits a distorted square-pyramid with three nitrogen atoms of the dpa ligand, water molecule, and the oxygen atom of the bridging tp ligand. Cyclic voltammetric data indicate that 1 undergoes irreversible one-electron oxidation to the CuIII and reversible one-electron reduction to the CuI, while 2 gives one reversible oxidation and two reversible and irreversible reduced processes. The electronic spectra and redox potentials of the complexes are influenced significantly by the anionic ligands. The reaction of [Cu(dpa)Cl2] with K(NO3)2 and Na2tp yields mononuclear and dinuclear copper(II) complexes [Cu(dpa)(NO3)2] (1) and [Cu2(dpa)2(H2O)2(μ-tp)](tp)·6H2O (2) (dpa = di-(2-picolyl)amine, tp = terephthalate).