Molecular structure of thiocyanatotris (2,2′-iminodiethanoldithiocarbamato) tellurium(IV) monohydrate

The synthesis, properties, and structural characterization of the title compound, C₁₆H₃₀N₄O₄S₇Te(IV)·H₂O, are reported. The crystals are monoclinic, space groupP2₁/n, withZ=4 in a unit cell of dimensionsa=13.291(5),b=21.306(6),c=10.450(1) Å, 0=104.25(2)° and,V _c=2868 ų. The structure was solved by the heavy atom method and refined by full-matrix least squares toR=0.025 andR _w =0.027 for 2894 reflections. The dithiocarbamate groups are linked in an unequal bidentate manner with Te-S average distance 2.695(1) Å. The thiocyanate group is bonded through the sulfur atom with much larger Te-S length [2.964(2) Å].     

Crystal structure of bis(p-phenoxyphenyl) tellurium dichloride

Crystals of (p-PhOC₆H₄)₂TeCl₂ are monoclinic with space groupP2₁/c,a=8.063(2),b=21.695(5),c=12.622(2) Å,=101.57(2)°, andZ=4. The structure refined to a finalR value of 0.055 for 2135 unique observed reflections. The compound adopts a primary four-coordinate geometry based on a distorted trigonal bipyramid with an equatorial lone pair. A weak Te-Cl secondary interaction links the molecules into centrosymmetric dimers.     

Synthesis and structure of tetrakis(2,6-dichlorophenoxide) bis(THF) uranium(IV)

The reaction of UCl₄ with KO-2,6-Cl₂C₆H₃ in tetrahydrofuran results in the preparation of the title compound. The six-coordinate complex possesses pseudo-octahedral geometry about uranium, with U-O(phenoxide) bond lengths in the range 2.161(11) to 2.178(10) Å and U-O(THF) bond lengths of 2.467(10) and 2.475(11) Å. This complex crystallizes in the monoclinic space group P2₁/n (a = 11.169(2), b = 11.588(2), c = 35.119(5) Å, = 92.11(1)°, V = 4542.2(13) ų, and Z = 4).     

Synthesis,crystal structure and vibrational spectra of uranium(IV) hypophosphite

The preparation, crystal structure, and infrared spectrum are reported for the new compound U(H₂PO₂)₄. The coordination geometry of uranium is approximately described as a square antiprism. The four independent hypophosphite groups which are bonded to each uranium atom also serve as bridging groups in linking the uranium centers into a three-dimensional network. The internal H₂PO ₂ ^– vibrational modes in the infrared spectrum of U(H₂PO₂)₄ show unit-cell group couplings, particularly for the P-H stretching vibrations, making the spectrum distinctly different from that of the simple bidentate non-bridging H₂PO ₂ ^– ion in KH₂PO₂ and VO(H₂PO₂)·H₂O.     

Synthesis,properties, and molecular structure of bis(thiobenzoato-S)tellurium(II), C14H10O2S2Te(II)

The synthesis, properties, and structural characterization of the title compound, C₁₄H₁₀O₂S₂Te, are reported. The crystals are monoclinic, space groupC2/c (No. 15) witha=24.369(6),b=4.333(2),c=14.569(3) Å, and=109.56(2)°,V=1449.57 ų,M=402, andD _x =1.843 g cm^–3 forZ=4. The structure was solved by the heavy-atom method and refined by full-matrix least squares toR=0.029 andR _w =0.027 for 772 diffractometer data. Crystal structure analysis and IR spectroscopic study indicate that the tellurium is covalently bonded to sulfur. There are weak secondary interactions between tellurium and oxygen which complete an S₂O₂ coordination around tellurium.     

Synthesis,characterization and crystal structure of oxovanadium(IV) complex with tridentate o-van-gly and bidentate phenanthroline

A novel oxovanadium(IV) complex with tridentate schiff base and bidentate phenanthroline ligands, VO(o-van)(phen) 2H₂O[o-van-gly: o-vanillin-glycine; phen: phenanthroline], was synthesized and characterized by elemental analysis, IR and UV-vis spectra. The crystal structure was determined by X-ray single crystal diffraction analysis. The crystal of title complex (C₂₂H₂₁N₃O₇V, M_w = 490.36) belongs to triclinic, space group P-1 with the following crystallographic parameters: a = 9.247(3) Å, b = 10.125(4) Å, c = 13.100(5) Å, = 106.343(6), = 96.042(7), = 101.726(7), V = 1135.0(7) ų, Z = 2, D_c = 1.435 Mg m^–3, (MoK = 0.485 mm^–1, F(000) = 506, and final R₁ = 0.0779, wR₂ = 0.1598 for observed reflections 1606 (I > 2(I)). V(IV) is six-coordinate with three oxygen atoms and three nitrogen atoms in a distorted octahedral geometry. The complex forms a 3-D network via – stacking and hydrogen bonds.     

Crystal structure of tetramethylammoniuml-histidinatobis (thiocyanato) vanadyl (IV) monohydrate

The title compound, [(CH₃)₄N] [VO(l-His)(NCS)₂]·H₂O, has been prepared by the reaction of [(CH₃)₄N]₄[VO(NCS)₄]₂·H₂O with histidine in aqueous solution. The crystal is orthorhombic, space groupP2₁2₁2₁ witha=9.839(6),b=11.835(5),c=17.366(6) Å,Z=4. The structure was solved by direct methods and refined by full-matrix least-squares to anR of 0.073 for 1067 reflections. In the complex anion VO²⁺ was coordinated by two thiocyanate groups and al-histidine which functions as a tridentate chelate.     

Crystal and molecular structure of tin(IV) dithiocarbamates: III. Tris(N,N-diethyl-dithiocarbamato)n-butyltin(IV)

The crystal structure of the title compound has been determined from 1623 independent reflections measured by scintillation methods. The compound cyrstallizes in the monoclinic space groupP2₁/c witha = 10.60(2),b = 18.40(5),c = 17.05(3) Å, = 116.7(2) °, andZ = 4. The structure was solved by Patterson and Fourier techniques and was refined by full-matrix least-squares methods toR = 0.066. As in tris(N, N-diethyldithiocarbamato)-methyltin(IV) the crystal structure consists of discrete, neutral, sevencoordinated tin complexes. The distorted pentagonal bipyramidal geometry of the tin atom is almost identical to that in the methyl complex, being formed by two sulfur atoms from each dithiocarbamate and a carbon atom of the butyl group which occupies one of the axial positions. Each dithiocarbamate ligand again has one Sn-S distance significantly shorter than the other. For the equatorial ligands the average difference is 0.18 Å with the minimum Sn-S distance 2.619(7) Å and the maximum 2.860(6) Å. For the ligand which bridges axial-equatorial, the Sn-S axial distance is 2.491(6) Å, while the Sn-S equatorial distance is 2.763(8) Å. The axial S-Sn-C angle is 166.3(5) °. The results are compared with those for other seven-coordinated tin(IV) structures and seven coordinated dithiocarbamate complexes of other metals.     

Structure of dichloro[(2,4-dimethyl-5-oxo-2,3,4,5-tetrahydro-2-furyl)methyl]-(4-methoxyphenyl)tellurium(IV)

The crystal structure of TeCl₂(C₇H₇O)(C₇H₁₁O₂) has been determined from three dimensional, single crystal X-ray diffraction data. It crystallizes in the monoclinic space group C2/c with the lattice constantsa=24.551(5),b=11.435(2),c=12.368(2)Å,=97.33(1)° andZ=8,D _X=1.67 g cm^–3. Final least-squares refinement based on 3023 independent observed reflections yieldedR=0.026. The Te^iv ion is in a trigonal bipyramidal configuration with its lone pair of electrons at one of the equatorial positions. Distances and angles are: Te-Cl=2.495(1), 2.517(1); Te-C=2.134(3), 2.106(3)(aryl)Å; Cl-Te-Cl=173.45(4), Cl-Te-C=88.11(9), 88.60(9), 88.72(9), 86.06(9); C-Te-C=96.5(1)°. There are two secondary bonds to the tellurium: TeCl=3.824(1) and TeO(2)=3.006(1)Å. The methyl group to the carbonyl oxygen and the aryltelluro moiety exhibit atrans 2,4 relationship.     

The crystal and molecular structure of ammonium-bis(malonato) oxovanadium(IV) dihydrate

The title compound, (NH₄)₂[VO(C₃H₂O₄)₂]·2H₂O, crystallizes in the monoclinic space group P2₁/n, with a=7.1889(7), b=19.254(2), c=9.879(2) Å, β=108.19(1)^o, and Z=4. The VO²⁺ cation is five-fold coordinated with two malonate anions acting as bidentate ligands and a water molecule. Infrared and Raman spectra are also reported to attain a wider insight into the compound characteristics.     

Synthesis and structure of bis(dibenzoylmethane)copper(II)

Bis(dibenzoylmethane)copper Cu(dbm)₂ has been synthesized and its structure determined by x-ray diffraction. It crystallizes in the monoclinic system, space group C2/c, with a = 25.936(3), b = 5.9806(8), c = 16.4908(16) Å, = 114.998(8)°, Z = 4, and V = 2318.3(4) ų. The Cu atom is located at a symmetry center and surrounded by four O atoms from two dbm molecules to form a plane square coordination environment. On the a–c plane the molecules are orderly arranged to result in a layered structure, and parallel to crystallographic b-axis they form a molecular column due to the effect of aromatic stacking.     

Synthesis and structure of tris(N-methylaminoethanoldithiocarbamato)arsenic(III)

The title compound was synthesized by the interaction of arsenic(III)chloride with freshly prepared N-methylaminoethanoldithiocarbamic acid in methanol. The compound crystallized in the triclinic system, space groupP with two molecules per unit cell, the dimensions area=6.509(10)Å,b=14.077(3)Å,c=14.195(3)Å, =64.16(2)^o, =84.67(2)^o and =84.00(2)^o. The molecule is monomeric with three short (mean 2.320(3)Å) and three long (mean 2.927(2)Å) As-S bonds. Asymmetry in the As-S bonds is due to the presence of stereochemically active lone pair on arsenic and the coordination polyhedron deviates from the usual D₃ symmetry to C₃ symmetry. Disorder exists in one of the dithiocarbamate ligands probably due to the O...O interaction arising from the water molecule. The anisobidenticity of the As-S bond distances is as a consequence of stereochemical requirement of the ligand and the lone pair of electrons on arsenic.     

Crystal and molecular structure of tin(IV) dithiocarbamates: IV. monoclinic and triclinic bis (N,N-diethyldithiocarbamato)dimethyltin(IV), unusual six coordination

The structure of the title compound has been determined by three-dimensional X-ray diffaction techniques in two crystallographic modifications, containing a total of three symmetry-independent molecules. This has clearly established that the observed rather unusual six-coordinated geometry is not a result of crystal packing effects. The triclinic modification (P¯1) has cell dimensionsa = 10.600(3),b = 10.899(3),c = 10.585(4) Å, = 95.8(1), = 85.4(1), and = 126.2(1) °. The observed density of 1.52 g cm^–3 agrees well with the calculated density of 1.51 g cm^–3, based on two molecules per unit cell. For the structure solution and refinement 3156 reflections measured with a scintillation detector and withF ₀ ² 3(F ₀ ² ) were used and gave a final agreement factor (R) of 0.027. The monoclinic modification is described by the following:a = 27.630(1),b = 12.350(1),c = 17.777(1) Å, = 100.9(2) °, space group =C2/c,Z = 12,d ₀ = 1.48 g cm^–3,d _c = 1.489 g cm^–3. The structure was solved and refined using 3289 reflections measured with a scintillation detector and withF ₀ ² 3(F ₀ ² ). The final agreement factor was 0.065.The molecular structure involves bidentate coordination of the sulfur atoms of the two dithiocarbamate ligands and coordination of the two methyl groups to the tin(IV) atom. The bidentate coordination of each of the dithiocarbamate ligands involves one short Sn-S distance (average = 2.52 Å) and one long Sn-S distance (average = 2.95 Å). The average Sn-C distance is 2.12(1) Å, and the C-Sn-C bond angle is 141(1) °. The geometry about the tin atom is then highly distorted from octahedral and cannot be considered eithercis- ortrans-octahedral. The structure is compared with several other six-coordinated tin(IV) dithiocarbamate complexes and with spectroscopic predictions of the structure.Research scientist, University of Missouri Research Reactor Facility, University of Missouri, Columbia, Missouri 65211.     

Crystal and molecular structure of chloro(ethyl L-cysteinato-N,S) dimethyltin (IV)

Orthorhombic crystals of the title compound, C₇H₁₆ClNO₂SSn, belong to space groupP2₁2₁2₁, witha = 6.658(5),b = 10.974(3),c = 17.144(5) Å, andZ = 4. The diffractometer data, measured with CuK radiation, has been refined to anR index of 0.053 for 1110 observed terms. The geometry about the Sn atom in the monomeric complex units is distorted trigonal bipyramidal; the N and Cl atoms are in the apical positions, and the Sn lies at 0.107(1) Å from the equatorial plane. The Sn-Cl, Sn-S, and Sn-N bonds have lengths 2.523(4), 2.413(3), and 2.434(12) respectively, and the angle N-Sn is 166.9(3) °.     

Synthesis and structure of ditetrabutylammonium tetrachlorodioxoneptunium(VI)

The reaction of a stock solution of NpO₂² + in 2 M HCl with two equivalents of tetrabutylammonium chloride in 6 M HCl results in the preparation of the title compound. This compound, [NBu₄]₂[NpO₂Cl₄], is isostructural with the uranium analogue, [NBu₄]₂[UO₂Cl₄]. The anion of the complex, [NpO₂Cl₄]²–, adopts a pseudooctahedral geometry common to six-coordinate actinyl complexes in which the neptunium metal is coordinated by two trans axial oxo groups with NpO(oxo) bond lengths of 1.733(5)Å, and four equatorial chloride ligands with Np–Cl bond lengths in the range 2.637(2)–2.676(2)Å. The neptunyl ONpO bond angle is 178.6(3)°. Charge balance of the neptunyl tetrachloride anion is maintained by two tetrabutylammonium cations. This complex crystallizes in the monoclinic space group P2₁/n (a = 15.416(4), b = 15.362(4), c = 18.479(5)Å, = 108.147(6)°, V = 4158.4(19)ų, Z = 4).     

Synthesis and crystal structure of bis(benzimidazolium) tetrahalocobaltate(II)

The crystal structures of benzimidazolium tetrahalocobaltates (HBz)₂[CoX₄] (X = Cl and Br) have been determined. The chloride salt is triclinic, P-1, with a = 7.670(3) Å, b = 8.307(3) Å, c = 15.730(2) Å, and = 87.37(3)°, = 84.99(3)°, = 67.72(2)°. The bromide salt is monoclinic, C2/c, with a = 15.568(2) Å, b = 8.063(3) Å, c = 5.762(2) Å and = 91.36(3)°. The structures of the two salts are closely related. Both the compounds contain isolated tetrahedral CoX₄ ^2– anions and benzimidazolium cations. In the chloride salt, three chloride ions are involved in strong hydrogen bonding while only two bromide ions participate in the bromide salt. The greater deviation from the ideal tetrahedral geometry in CoBr₄ ^2– can be related to the less extensive hydrogen-bonding network compared to the chloro complex.     

Crystal and molecular structure of bis-tetraphenylarsonium-tris-(cis-1,2-dicyano-1,2-ethylenedithiolato)Fe(IV)

The crystal structure of bis-tetraphenylarsonium-tris-(cis-1,2-dicyano-1,2-ethylenedithiolato)Fe(IV), [(C₆H₅)₃As]₂Fe[S₂C₂(CN)₂]₃, has been determined using 3154 independent, non-zero reflexions collected by counter techniques. The substance crystallizes in the monoclinic system: space groupI2/a,a = 20·153(8),b = 13·411(5),c = 21·497(8) Å and = 95·28(8) °;D _m = 1·41(2),D _c = 1·43 g cm^–3 andZ = 4. The structure consists of Ph₄As⁺ cations in general positions and tris-(cis-1,2-dicyano-1,2-ethylenediothiolato)Fe(IV) anions on two-fold axes. Although the coordination around the arsenic atom is tetrahedral, the overall symmetry of the cation is 1 (C ₁), probably because the phenyl rings are rotated to accommodate the requirements of packing. The coordination of the six sulphur atoms about the iron atom is trigonal antiprismatic, approximating closely to an octahedron: for any pair oftrans sulphur atoms, the S-Fe-S angle is about 171 °.     

Synthesis and crystal structure of bis(2-methylbenzimidazolium) tetrahalocuprate(II)

The crystal structures of 2-methylbenzimidazolium tetrahalocuprates (H2-mebz)₂[CuX₄] (X = Cl and Br) have been detemined. The chloride salt is monoclinic, P2₁/c, with a = 8.540(2) Å, b = 16.591(2) Å, c = 14.303(3) Å, and = 98.69(2)°. The bromide salt is also monoclinic, P2₁/c, with a = 8.316(3) Å, b = 17.436(3) Å, c = 14.747(3) Å, and = 98.82(3)°. Both the compounds contain discrete distorted tetrahedral CuX₄ ^2– anions and almost planar 2-methylbenzimidazolium cations. In the chloride salt, three chloride ions are involved in hydrogen bonding instead of two bromide ions in the bromide salt.