Journal of Chemical Crystallography (v.38, #5)

Synthesis, Structure and Properties of (H2NCH2CH2NH3)3 {(VO)6 [B10O16 (OH)6]2} · 11H2O by Qinghai Cai; Bin Lu; Jiawei Zhang; Yongkui Shan (321-325).
A new polyoxovanadoborate cluster (H2NCH2CH2NH3)3 {(VO)6[B10O16(OH)6]2} · 11H2O was prepared by hydrothermal technique and characterized by single crystal X-ray diffraction analysis, IR and TGA. The crystal of the new compound belongs to monoclinic system, space group C2/c with a = 20.198(1) Å, b = 13.4476(8) Å, c = 21.602(1) Å, β = 97.067(1)°, V = 5822.8(5) Å3, Z = 4, D c  = 1.956 g cm−3, M = 1714.4, μ = 1.066 mm−1, S = 1.905, R = 0.059, R w  = 0.0966.A new polyoxovanadoborate cluster (H2NCH2CH2NH3)3{(VO)6 [B10O16(OH)6]2} · 11H2O was prepared by hydrothermal technique and characterized by single crystal X-ray diffraction analysis, IR and TGA.
Keywords: Polyoxovanadoborate; Polyoxometalate cluster; Structural determination; Hydrothermal synthesis

Synthesis and Structure of Di-μ-oxo-bistripyrazolylborato Dioxo Vanadium (V) Complex with Lattice of Diacetonitrile by Yong Heng Xing; Katsuyuki Aoki; Feng Ying Bai; Yuan Hong Zhang; Bao Li Zhang (327-331).
A novel oxovanadium complex was obtained by the reaction of VOSO4 · 3H2O with tripyrazolylborate sodium in MeOH. The complex (1) was characterized by element analysis, IR spectroscopy, 1HNMR and its crystal for X-ray diffraction recrystallized from saturated CH3CN solution. The compound crystallizes in the monoclinic, space group Pbca, with cell dimensions of a = 15.531(2) Å; b = 18.007(2) Å; c = 10.725(2) Å; V = 2,999.4(8) Å3 and D calc = 1.533 g/cm3 for Z = 4. The structure was solved by direct methods and refined to an R-value of 0.0401. Structure analysis show that it is a di-μ-oxo-bistripyrazolylborato dioxo vanadium (V) complex with lattice of diacetonitrile. In addition, the electronic structure and the bonding characters of the complex were analyzed with ab initio calculations.
Keywords: Oxovanadium complex; Polypyrazolylborate; Crystal structure

Intermolecular Interactions in Crystalline Hydroxychloroquine Sulfate in Comparison with Those in Selected Antimalarial Drugs by Agata Semeniuk; Justyna Kalinowska-Tluscik; Wojciech Nitek; Barbara J. Oleksyn (333-338).
The crystal structure of hydroxychloroquine sulfate (OHClQ) was determined in order to compare its conformation and intermolecular interactions to those in the crystalline chloroquine phosphate (ClQP) and quinine salicylate (QSal) monohydrate. The crystals of OHClQ are monoclinic with the space group P21/c and unit-cell dimensions: a = 10.4966(1) Å, b = 8.8056(1) Å, c = 21.8603(3) Å, β = 101.074(1)°. The quinoline antimalarial drugs may interact with their putative receptors by formation of characteristic hydrogen-bonded rings. The protonated nitrogen atoms and/or hydroxyl groups of the drug cation are proton donors, while the oxygen atoms of anions are proton acceptors. Water molecules may intermediate in these interactions.Hydroxychloroquine sulfate is a drug used in the treatment of malaria and rheumatic diseases. The X-ray structure analysis shows an important role of intermolecular hydrogen bonds in the crystal architecture. Comparison with chloroquine phosphate and quinine salicylate indicates that the organization of the drug cations is determined by the anions.
Keywords: Hydroxychloroquine; Antimalarial drug; Crystal structure

Two isostructural dinuclear complexes [M2(Dpq)2(phth)2(H2O)4] · 2H2O [M = Zn(1), Ni(2), Dpq = dipyrido[3,2-d:2′,3′-f]quinoxaline, phth = phthalate] have been synthesized and characterized. Crystal data: (1), Mr = 1031.55, monoclinic, C2/c, a = 27.7948(11), b = 10.5196(4), c = 15.0390(5) Å, β = 110.818(1), Z = 4, V = 4110.2 Å3, R 1 = 0.0277, wR 2 = 0.0718 [I > 2σ(I)]; (2), Mr = 1018.19, monoclinic, C2/c, a = 27.675(4), b = 10.3601(15), c = 15.082(2) Å, β = 110.954(2), Z = 4, V = 4038.3 Å3, R 1 = 0.0248, wR 2 = 0.0668 [I > 2σ(I)]. The dinuclear units are connected into 2-D supramolecular net through O–H···O hydrogen bonding. Moreover, the 2-D networks are ultimately packed into a 3-D supramolecular structure via interlayer π···π stacking interaction between the aromatic rings of Dpq ligands. Furthermore, the photoluminescence property of compound 1 is also studied.Two isostructural dinuclear complexes [M2(Dpq)2(phth)2(H2O)4] · 2H2O [M = Zn(1), Ni(2), Dpq = dipyrido[3,2-d:2′,3′-f]quinoxaline, phth = phthalate] have been synthesized, and the structure study reveals that each dinuclear complex is connected with six other dinuclear units through the O–H···O hydrogen bonding to form 2-D supramolecular networks.
Keywords: Supramolecular structure; Hydrogen bond; Dinuclear; Oxygen cluster

Synthesis, Characterization and Crystal Structure of the Bis(2,4-dinitrobenzoato)tetrabutyldistannoxane(IV) Dimer by Yip Foo Win; Siang Guan Teoh; Eng Khoon Lim; Shea Lin Ng; Hoong Kun Fun (345-350).
The title compound, bis(2,4-dinitrobenzoato)tetrabutyldistannoxane(IV), was obtained from the reaction of di-n-butyltin(IV) oxide with 2,4-dinitrobenzoic acid. It crystallizes out as the usual dicarboxylatotetrabutyldistannoxane(IV) dimer. In the monoclinic system P21/c, a = 12.391(3) Å, b = 19.937(5) Å, c = 15.026(4) Å, α = γ = 90°, β = 102.857(2)°, V = 3618.95(16) Å3 and Z = 2. A crystal structure determination of the title compound reveals the presence of a centrosymmetric planar Sn2O2, with two different environments for tin atoms and two distinct carboxylate groups. Two of the carboxylate groups are bonded to the exocyclic tin atom in a bidentate bridging manner and the remaining two carboxylate groups are bonded to the tin atom in a monodentate manner. As a result, both the tin atoms moieties in the complex are five coordinate and exhibit trigonal bipyramid geometry.Synthesis, Characterization and Crystal Structure of the Bis(2,4-dinitrobenzoato)tetrabutyldistannoxane(IV) DimerYip Foo Win, Teoh Siang Guan, Lim Eng Khoon, Shea Lin Ng, Hoong Kun FunA crystal structure determination of the title compound reveals the presence of a centrosymmetric planar Sn2O2, with two different environments for tin atoms and two distinct carboxylate groups.
Keywords: Dicarboxylatotetrabutyldistannoxane(IV) dimer; Crystal structure; Centrosymmetric planar Sn2O2

The crystal structure of 4,4′-bipyridin-1-ium perchlorate dihydrate, [C10H9N2](ClO4) · 2H2O, is determined by room temperature X-ray diffraction. The compound crystallizes in the triclinic space group P-1 with a = 8.122(3) Å, b = 9.726(3) Å, c = 17.648(6) Å, α = 78.181(4)°, β = 82.797(5)°, γ = 67.439(4)°, Z = 2, V = 1258.4(7) Å3. In the compound, monoprotonated 4,4′-bipyridin-1-ium cations are self-assembled into supramolecular chains along the a-axis through N–H···N hydrogen bonds in a head-to-tail fashion. The chains are stacked via π–π stacking interactions to create two-dimensional sheets. The interlayer space is occupied by the hydrogen-bonded water chains that are linked to the organic sheets via C–H···O interactions and the perchlorate anions that are linked to the water chains and the organic sheets via O–H···O and C–H···O hydrogen bonds, respectively, thus generating a three-dimensional supramolecular architecture.Supramolecular Network via Hydrogen Bonding and π–π Stacking in 4,4′-Bipyridin-1-ium perchlorate dihydrateJian-Yong Zhang, Ai-Ling Cheng and En-Qing Gao*Monoprotonated 4,4′-bipyridin-1-ium cations are self-assembled into supramolecular chains along the a-axis through N–H···N hydrogen bonds, and these chains are stacked via π–π stacking and hydrogen bond interactions involving water molecules and perchlorate anions.
Keywords: Hydrogen bonds; π–π Stacking; 4,4′-Bipyridinium

The solid solution of Na1 + x Zr2 − x Sb x P3O12 (x = 0.1) was prepared at 1,000 °C by ceramic route. The ceramic material belonging to sodium zirconium phosphate (hereafter NZP) family crystallizes in space group R-3c with unit cell parameters: a = b = 8.77283(16) Å, c = 22.8375(7) Å, α = β = 90.0° γ = 120.0° and Z = 6. The structure of the title phase has been determined by Rietveld refinement of the powder diffraction data on GSAS software. The refinement converges to a satisfactory structure fit with R p = 0.0764, R wp = 0.1099 and RF 2 = 0.0450. The interatomic distances and bond angles are in good agreement with their standard values. The particle size along prominent reflecting planes ranges between 13 and 50 nm. The polyhedral (ZrO6 and PO4 and NaO8) distortions and valence calculations from bond strength data are also reported. The investigations show that the Sb+3 cation occupies the zirconium (AVI) site of NZP structural framework and resultant charge compensation takes place through partial occupation of M2 site by Na+ ions.Synthesis and Structure Refinement of Polycrystalline Solid Solution: Na1 + x Zr 2 − x Sb x P 3 O 12 ( x  = 0.1) O. P. Shrivastava and Rashmi Chourasia Antimony enters crystallochemically in the framework of nano ceramic sodium zirconium phosphate at the Zr site of the ZrO6 octahedra which are inter linked by PO4 tetrahedra through corner sharing of the vertical columns.
Keywords: Sb–NZP; Nano ceramic; X-ray diffraction; GSAS; Rietveld refinement

Synthesis and Characterization of Monomeric and Dimeric Structures of Calix[4]arenes Containing Amidoferrocene by Chomchai Suksai; Pannee Leeladee; Colin Jennings; Thawatchai Tuntulani; Palangpon Kongsaeree (363-368).
The reaction of 1,1′-bis(chlorocarbonyl)ferrocene with bis-aminobenzylcalix[4]arene gave amidoferrocene calix[4]arene monomer 1. Compound 1 crystallized in the monoclinic system P21/c with a = 11.196(6) Å, b = 14.971(11) Å, c = 32.007(2) Å, β = 96.413(4)° and V = 5330.9(6) Å3. X-ray diffraction analyses of 1 showed that the calix[4]arene scaffold was in cone conformation in which the intramolecular hydrogen bonding were formed through OH groups at the lower rim to stabilize the structure. Moreover, the intramolecular hydrogen bond between the amide groups of the amidoferrocene unit also presented in the crystal structure. On the other hand, the condensation of 1,1′-bis(chlorocarbonyl)ferrocene with p-tert-bis-aminobenzylcalix[4]arene resulted in the monomeric 2 and [2 + 2] dimeric compounds 3. 1H-NMR studies signified that the calix[4]arene building block in compounds 2 and 3 adopted the cone conformation.Synthesis and Characterization of Monomeric and Dimeric Structures of Calix[4]arenes Containing AmidoferroceneChomchai Suksai*, Pannee Leeladee, Colin Jennings, Thawatchai Tuntulani*, Palangpon KongsaereeThe condensation of 1,1′-bis(chlorocarbonyl)ferrocene with p-tert-bis-aminobenzylcalix[4]arene resulted in the monomeric and [2 + 2] dimeric compounds.
Keywords: Metallocene; Amidoferrocene; Calix[4]arene

Synthesis, Spectroscopic Studies and Crystal Structure of N,N′-bis((thiophene-2-carboxamido)propyl)piperazine by Ayla Balaban; Naki Çolak; Hüseyin Ünver; Birgül Erk; Tahsin Nuri Durlu; D. Mehmet Zengin (369-372).
A new multidentate ligand N,N′-bis((thiophene-2-carboxamide)propyl)piperazine has been synthesized from the reaction of thiophene-2-carbonylchloride and 1,4-bis(3-aminopropyl)piperazine. The title compound has been characterized by elemental analysis, FT-IR, 1H-NMR and 13C-NMR spectroscopic techniques. The crystal structure of the title compound (C20H30N4O2S2Cl2) has also been determined by X-ray analysis. The title compound crystallize in the monoclinic space group P21/c with a = 9.768(1), b = 12.895(1), c = 10.083(1) Å, β = 115.12(1)°, V = 1149.9(2) Å3, D x = 1.425 g cm−3 and Z = 2. The crystal structure was solved by direct methods and refined by full-matrix least squares to a find R = 0.039 [I > 2σ (I)] for 2,786 observed reflections.The (N,N’–bis((thiophene-2- carboxamido)propyl)piperazine) molecule has been synthesized and its molecule structure has been investigated by using , FT-IR, 13C NMR and 1H-NMR spectroscopic and crystallographic techniques.
Keywords: 1,4-Bis(3-aminopropyl)piperazine; Thiophene ring; NMR; Amide; Vibrational spectrum

The crystallization and structures of a triclinic (henceforth T) (C6H9N2)2[CdBr4] and a monoclinic (henceforth M) of (C6H9N2)2[CoBr4] are reported. The crystal packing of both solids is analyzed and compared: both contain parallel chains of cations and stacks of anions. In both T and M, each [MBr4]2− is hydrogen bonded non-symmetrically to surrounding cations in a ladder chains that run along b axis, with planar cations in both structures falling in parallel to the planes to anions. In T the cation chains are further involved in classical π···π stacking, while in M the cation chains show less significant stacking, with longer repeat distance.Extensive N–H···Br hydrogen bonds link both anions and cations into chains of the ladder type parallel to the crystallographic b axis. The crystal structures of bis(2-amino-5-methylpyridinium) tetrabromometallate(II): Intermolecular interactions in (C6H9N2)2[MBr4]; M = Cd and Co Rawhi Al-Far and Basem Fares Ali
Keywords: Organic–inorganic hybrids; Crystal packing; Intermolecular interactions

Synthesis, Crystal Structure, Cytotoxic and Apoptotic Activity of 2,4-Dichloro-6-methylquinoline on Human Oral Carcinoma Cell Line by R. K. Somvanshi; R. Subashini; V. Dhanasekaran; G. Arulprakash; S. N. Das; S. Dey (381-386).
The present report describes the synthesis, IR spectra, 3-dimensional structure of the compound 2,4-dichloro-6-methylquinoline and evaluation of its anti-cancer activity using propidium iodide (PI) staining and annexin binding assay techniques. This derivative of quinoline was synthesized from the mixture of p-toluidine and malonic acid and synthesis has been achieved in a one-pot reaction from an aryl amine, malonic acid and phosphorous oxychloride. Crystallographic data reveals that the crystals belong to triclinic crystal system with space group P-1 with the unit cell dimensions of a = 7.14(1) Å, b = 11.53(1) Å, c = 11.97(1) Å and α = 90.18° (10), β = 106.31° (10), γ = 91.07° (10). The in vitro anti-cancer assay indicated that compound has cytotoxic and apoptotic activity on human oral squamous carcinoma (KB) cell line, thus it could be developed as a potent anti-cancer agent.Synthesis, Crystal Structure, Cytotoxic and Apoptotic Activity of 2,4-Dichloro-6-methylquinoline on Human Oral Carcinoma Cell Line R. K. Somvanshia, R. Subashinib, V. Dhanasekaranb, G. Arulprakashb, S. N. Dasc, S. Deya
Keywords: Aryl amine; Malonic acid; 2,4-Dichloro-6-methylquinoline; Crystal structure; Flow cytometry; Apoptosis

The X-ray crystal structures of two lamotrigine derivatives (I) 3,5-diamino-6-(2-chlorophenyl)-1,2,4-triazine, C9H8ClN5, (465BL) as a hydrate, and (II) 3,5-diamino-6-(3,6-dichlorophenyl)-1,2,4-triazine, C9H7Cl2N5, (469BR) as a methanol solvate, have been carried out at liquid nitrogen temperature and room temperature, respectively. A detailed comparison of the two structures is given. Both are centrosymmetric with (I) in the orthorhombic space group Pbca, a = 12.2507(3), b = 15.7160(6), c = 21.71496(9) Å, Z = 16, and (II) in the monoclinic space group C2/c, a = 38.553(3), b = 4.9586(2), c = 14.546(2) Å, β = 111.59(1)°, Z = 8. Final R indices [I > 2sigma(I)] for (I) are R1 = 0.0670, wR2 = 0.1515 and for (II) R1 = 0.0434, wR2 = 0.1185. Structure (I) has water of crystallization in the lattice and (II) includes a solvated CH3OH. Structure (I) is characterized by having two crystallographically independent molecules, A and B, of 465BL, per asymmetric unit. Molecule B has a very unusual feature in that the 2-chlorophenyl ring is statistically disordered, occupying site (1) in 87.5% of the structure and site (2) in 12.5% of the structure. Sites (1) and (2) are related by an exact 180° pivot of the phenyl ring about the ring linkage bond. The presence of two independent molecules per asymmetric unit provides an ideal opportunity for the conformational flexibility of the molecule 465BL to be studied. Structure (I) also includes a further unusual feature in that the lattice contains one fully occupied water molecule and an additional solvated water which is only 33% occupied. Rex A. Palmer, Brian S. Potter, Michael J Leach and Babur Z. ChowdhryThe crystal structures of two lamotrigine analogues: (I) 3, 5-diamino-6-(2-chlorophenyl)-1, 2, 4-triazine, water solvate and (II) 3, 5-diamino-6-(3,6-dichlorophenyl)-1, 2, 4-triazine methanol solvate are presented. Structure (I) includes two molecules per asymmetric unit labeled A and B where molecule B is unusually disordered having Cl in either position 2 (87.5% occupied) or position 6 of the phenyl ring (12.5% occupied), the two sites being related by 180deg rotation about the ring linkage bond. Molecule I(A) on the other hand shows no disorder. The relative orientations of the two rings in I(A and B) and in II is shown to be different. Lamotrigine and analogues have been investigated for some time for their effects on the central nervous system. For example both lamotrigine and 5-(2,3,5-trichlorophenyl)-2,4-diaminopyrimidine (code name BW 1003C87) are voltage-gated sodium channel blockers as well as blocking the release of the neurotransmitter glutamate. BW 1003C87 has also been shown to reduce the release of glutamate evoked by veratrine in brain tissue, providing a therapeutic approach in both cerebral ischemia and epilepsy [B. S. Meldrum, J. H. Swan, M. J. Leach, M. H. Millan, R. Gwinn, K. Kadota, S. H Graham, J. Chen, R. P. Simon , Brain Res., 1992, 593, 1.]. This is one of a series of papers on the structures of lamotrigine analogues.
Keywords: Central nervous system drugs; Triazines; Lamotrigines; Voltage gated Na+ channel inhibitors; Crystal structures and drug design

Synthesis, Crystal Structure of a New Co(II) Complex with Pyrazine-2,3,5,6-tetracarboxylic Acid by Su-Rong Fang; Ai-Hong Yang; Yan-Ping Zhang; Hong-Ling Gao; Jian-Zhong Cui (393-396).
A new complex [Co(H2pztc)(bpy)H2O] (H4pztc = pyrazine-2,3,5,6-tetracarboxylic acid, bpy = 2,2′-bipyridine) has been synthesized by hydrothermal reactions of Co(NO3)2 · 6H2O with H4pztc and bpy and characterized by IR and X-ray diffraction single crystal structure analysis. It belongs to monoclinic system, P21/c space group with a = 13.454(2) Å, b = 12.939(2) Å, c = 11.4993(19) Å, α = 90°, β = 111.640(3)°, γ = 90°. This complex is assembled into 3D supramolecular architecture by hydrogen bonds (O–H···O, C–H···O).A new complex of cobalt(II) with pyrazine-2,3,5,6-tetracarboxylic acid and 2,2′-bipyridine is assembled by intermolecular hydrogen bonds forming 2D layer and 3D supramolecular network.
Keywords: Pyrazine-2,3,5,6-tetracarboxylic acid; Cobalt(II); Hydrothermal synthesis

Molecular Structure of [Me2Al(μ-OPh)]2: A Crystallographic and Ab initio Study by Douglas Ogrin; Simon G. Bott; Andrew R. Barron (397-401).
The molecular structure of [Me2Al(μ-OPh)]2 has been determined. The phenoxide ring is parallel to the Al2O2 ring rather than the energetically favored perpendicular configuration determined by ab initio calculations. Ab initio calculations successfully predict the structures of sterically demanding analogs. The adoption of the parallel configuration allows for an estimation of the magnitude of crystal packing forces. A discussion of the parameters controlling the structures of dialkylaluminum phenoxides is presented. Crystal data: group Pbca, a = 12.127(2), b = 8.491(2), c = 17.299(4) Å, V = 1781.3(6) Å3, Z = 4, R = 0.0695, wR 2 = 0.1390.The molecular structure of [Me2Al(μ-OPh)]2 has been determined. The phenoxide ring is parallel to the Al2O2 ring rather than the energetically favored perpendicular configuration as determined by ab initio calculations.
Keywords: Aluminum; Aryloxide; Calculations; Steric interaction