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].     

Molecular structure of [CpRu(PPh3)2(tht)]BF4, tht=tetrahydrothiophene

The title compound [CpRu(PPh₃)₂(tht)]BF₄,1, tht=tetrahydrothiophene, is obtained by the reaction of CpRu(PPh₃)₂Cl, tht and AgBF₄ in CH₂Cl₂ solution. Yellow crystals of [CpRu(PPh₃)₂(tht)]BF₄ were grown by the slow diffusion of pentane into a CH₂Cl₂ solution of1 and have been studied by X-ray crystallography: space group is P2₁/n,a=9.507(2),b=18.336(3),c=22.372(6) Å, =94.28(2)°,V=3889(1) ų,Z=4. The tht ligand binds to the Ru atom through the sulfur atom at a distance of 2.395(2) Å. The tht ring is in the puckered configuration.     

Molecular and crystal structure of Cp2Mo(mto), mto=monothiooxalate

Compoundl, Cp₂Mo(mto) is obtained by the reaction of Cp₂MoCl₂ with methanol solutions of potassium dithiooxalate in air. Red platelike crystals of Cp₂Mo(mto) were grown by the slow diffusion of pentane into a CH₂Cl₂ solution ofl and have been studied by X-ray crystallography: space group, P2₁/n,a=7.578(1),b=10.551(2),c=14.090(3) Å, =94.38(2)°,V=1123.1(4) ų,Z=4. The mto ligand chelates to the Mo atom through one oxygen atom and the sulfur atom. The two Cp rings form dihedral angles of 24° with the least-squares plane of the mto ligand. The Mo–O and Mo–S bond distances are 2.193(5) and 2.449(2) Å, respectively.     

The structures of three trimethylarsine-boron trihalide adducts: (CH3)3AsBCl3, (CH3)3AsBBr3, and (CH3)3AsBI3

An X-ray structure analysis of three trimethylarsine-boron trihalide adducts has been undertaken. Crystals of (CH₃)₃AsBCl₃ and (CH₃)₃AsBBr₃ are monoclinic with space groupP2₁/m (No. 11) withZ=2 while those of (CH₃)₃AsBI₃ are orthorhombic with space groupPnma (No. 62) withZ=4. For (CH₃)₃AsBCl₃,a=6.497(3) Å,b=10.735(3) Å,c=7.070(2) Å,=111.8(3)°,V=458.4(3) ų,R=0.0343. For (CH₃)₃AsBBr₃,a=6.672(4) Å,b=11.135(7) Å,c=7.199(4) Å,=111.5(1)°,V=497.7(5) ų,R=0.0434. For (CH₃)₃ÅsBI₃,a=13.113(7) Å,b=11.733(5) Å,c=7.387(3) Å,V=1136.5(5) ų,R=0.0329. The As-B bond lengths are 2.065(6), 2.04(1), and 2.03(1) Å, respectively, for the chloride, bromide, and iodide. These and other structural parameters are discussed with reference to previous predictions based on vibrational spectra and previous structural studies on the trimethyl-phosphine and trimethylamine adducts.     

Crystal and molecular structure of tris-(O-isopropylxanthato)-chromium(III)

The title compound has been synthesized by the reaction of CrCl₃6H₂O with K{S₂COCH(CH₃)₂} in a 13 molar ratio in an aqueous medium. It has been characterized by elemental analysis and IR spectral studies. Crystals of Cr{S₂COCH(CH₃)₂}₃ are monoclinic, space group P2₁/n witha=10.002(2),b=10.973(1),c=18.961(6) Å,=91.78(2)°,V=2079.9 ų,Z=4,D _calc=1.46 g cm^–3, monochromatic radiation (Mo-K), =0.71069 Å,=11.2 cm^–1,F(0 0 0)=948,T=295K, finalR=0.0320 for 2641 reflections. The environment of the chromium atom is based on an octahedral geometry having six sulfur donor atoms from three symmetrically chelated ligands with average distances: Cr-S=2.396(9) Å, C-S=1.690(3) Å and C-O=1.315(3) Å. The bond distance between oxygen atom and the carbon atom of the isopropyl group (O-C_av=1.478(4) Å) suggests that the form –S ₂ ^(–) C=O⁽⁺⁾CH(CH₃)₂ contributes significantly to the structure of the isopropyl group.     

Crystal and molecular structure of rubidium azidotrimethylaluminate,Rb[Al(CH3)3N3]

The crystal structure of rubidium azidotrimethylaluminate has been determined from three-dimensional counter data, and refined by full-matrix least-squares techniques. The crystals belong to the monoclinic space groupP2₁/n, witha= 10.003(5),b=7.497(4),c= 11.806(5) Å, = 108.70(3) °, andD _c= 1.58 g cm⁼³ forZ=4. The finalR factor for 922 observed reflections is 0.049. The compound is not isostructural with its cesium analog. The aluminum atom is coordinated in a tetrahedral fashion, and the Al-N bond length is 1.944(8) Å.     

Structure of ethanoldiphenylthallium(III) dithizonate

Ethanoldiphenylthallium(III) dithizonate, (C₂₇H₂₇N₄SOTl,M _r =659.97) is monoclinic,P2₁/c,a=9.776(3),b=16.761(4),c=16.750(5) Å,=95.72(2)°,Z=4. The structure was solved by the heavy atom method, from data collected at room temperature on an Enraf-Nonius CAD4 diffractometer. The data were corrected for absorption, and the refinement, using 2329 reflections, by least squares with anisotropic temperature factors for the thallium and sulfur atoms, converged atR=0.046. The complex is monomeric and comprises a distorted trigonal bipyramid with an almost planar bidentate dithizone residue coordinating through sulfur and nitrogen. A molecule of ethanol is coordinated axially as is the nitrogen atom of the dithizone, while the carbon atoms of the phenyl rings attached to the metal and the sulfur atom of the ligand are equatorial. Tl-S and Tl-N distances are 2.648(4) and 2.62(1) Å respectively while Tl-O is 2.64(1) and Tl-C are 2.12(1) and 2.14(1) Å.IUPAC nomenclature: ethanol-(1,5-diphenylthiocarbazonato-N,S)diphenylthallium(III).     

Crystal and molecular structure of bis(o-phenylenethiourea)selenium(II)chloride dihydrate,C14H12N4S2Cl2Se·2H2O

The synthesis and crystal structure ofbis(o-phenylenethiourea)selenium(II)-chloride dihydrate, Se(C₇H₆N₂S)₂Cl₂·2H₂O are reported. The compound crystallizes in the monoclinic space group, P2₁/n, with four molecules per unit cell, the dimensions of which area=10.243(3),b=13.341(4),c=14.273(4) Å,=93.00(3)°,U=1947.76 ų. The structure was solved by direct methods and refined by full-matrix least-squares toR=0.039 andR _w =0.040 for 3314 unique reflections. Selenium displays two strong coordinations arising from the two sulfurs, Se-S(1)=2.191(1), Se-S(2)=2.206(1) Å, and S(1)-Se-S(2)=101.0(1)°, and four secondary interactions involving three chlorines and one sulfur. The complex occurs as a dimer with two sets of very weakly interacting bridging pairs S(2), S(2)^a; and Cl(2), Cl(2)^a, where a denotes the inversion related atom. Lattice stabilization is ensured by the extensive network of hydrogen bonds involving chlorines, water oxygens, and nitrogens of phenylenethiourea ligands.     

Crystal structure of tris-(2,2′,2″)-triaminoethylamino-salicylidene iron(III) complex

Tris-(2,2,2)-triaminoethylamino-salicylidene iron(III) crystallizes in the monoclinic crystal system witha=7.766(2),b=25.423(5),c=13.318(5) Å, =118.04(3)°, space group P2₁/c,V=2320.8(6) ų,Z=4, andD _x=1.464 g cm^–3. The center of the axially distorted octahedron is occupied by the Fe atom which is coordinated by six donor nitrogen and oxygen atoms infac positions. The planes of coordinated atoms (N and O) with the Fe(III) atom are almost planar and the maximum elevated atom from these planes is O(1) (–0.1065 Å).     

Synthesis and crystal structures of two copper(I) π-complexes with 1-allyloxybenzotriazole of CuBr?C6H4N3(OC3H5) and 2CuCl?C6H4N3(OC3H5) compositions

Both compounds of CuBr⋅C₆H₄N₃(OC₃H₅) (sp. gr. P1, a = 7.633(1) Å, b = 9.987(1) Å, c = 14.898(2) Å, α = 104.75(1)^∘, β = 94.76(1)^∘, γ = 106.90(1)^∘) (I) and 2CuCl⋅C₆H₄N₃(OC₃H₅) (sp. gr. Cc, a = 11.2483(4) Å, b = 16.7076(6) Å, c = 7.2948(3) Å, β = 118.612(2)^∘) (II) composition were prepared by alternating-current electrochemical synthesis. In I due to a bridging function of organic moieties 16-membered cycles appear which are combined into ribbons {Cu₂Br₂[(C₆H₄N₃(OC₃H₅)]₂}_n. Each of two crystallographically independent copper atom possesses a trigonal-pyramidal arrangement with different degree of tetrahedral distortion. Distinctive numbers of hydrogen bonds around Br1 and Br2 atoms cause rather appreciable distinctions in copper–olefinic bond interaction effectiveness for each metal atom. In II Cu₂Cl₂ rhombs are joined to infinite chains oriented along [010] direction. Each ligand molecule is also coordinated through the C=C—bond of the allylic group to copper atom of one inorganic chain and through the nitrogen atom to a metal atom belonging to another copper-halide chain. Cu1 atoms is tetrahedrally surrounded by three chlorine atoms and nitrogen one, whereas a trigonal-planar arrangement of Cu2 atom is formed by two halogen atoms and slightly disordered olefinic group.     

Crystal and molecular structures of the 4-(1H)-pyridone (=L) lanthanide complexes {[GdL(NO3)3(H2O)]·CH3OH}2 and [DyL4(NO3)2](NO3) and of L2HNO3

The crystal structures of the title compounds have been determined by single crystal diffraction methods. Crystals of the dysprosium compound are monoclinic, space groupP2₁/c witha=14.133(4),b=13.438(5),c=14.401 (4)Å,=103.98(2)°,V=2654(1)ų,Z=4,D _c =1.82 g cm^–3, finalR=0.035. The Dy atom is eight-coordinate with a distorted dodecahedral coordination geometry involving two bidentate nitrate groups and four pyridone oxygen atoms. An erbium complex with analogous stoichiometry was also prepared but not structurally characterized. Crystals of the Gd compound are monoclinic, space groupP2₁/n, witha=11.226(2),b=9.075(2),c=16.737(3)Å,=93.88(3)°,V=1701(1)ų,Z=2,D _c =1.91 g cm^–3, finalR=0.042. Each Gd atom is bonded to one pyridone oxygen atom, a water molecule and three bidentate nitrate groups. An oxygen atom of one of the bidentate nitrates additionally serves to bridge pairs of Gd atoms so as to form a dinuclear complex in which each Gd atom is nine-coordinate with a tricapped trigonal prismatic geometry. Crystals of L₂HNO₃ are monoclinic, space groupI2/a witha=12.479(4),b=6.535(2),c=14.297(6)Å,=96.07(3)°,V=1159(1)ų,Z=4,D _c =1.45 g cm^–3, finalR=0.057. The pyridones are linked in pairs by very short (2.44 Å) symmetrical OHO hydrogen bonds. Each pair is further linked via a nitrate ion by means of N-HO(nitrate)H-N hydrogen bonds, so as to form an extended chevron-like pyridone-pyridone-nitrate-pyridone-pyridone array. Adjacent chains are linked via weak C-HO(NO₃) interactions.     

Gas-solid structure differences in the donor-acceptor complex (CH3)2HN−SO2

The crystal structure of the donor — acceptor adduct (CH₃)₂HN–SO₂ is reported. Crystals of the compound are clear prisms, space group Pna2₁; at –96°C,a=9.894(1),b=6.051(2),c=16.478(3) Å,D=1.469 g/cm³,V=786.6(5) Å,Z=8. The unit cell contains two crystallographically independent adducts, with N–S bond lengths of 2.015(3) Å and 1.991(3) Å. The average value, 2.00(1) Å is 0.33(4) Å shorter than the 2.34(3) Å value previously determined from microwave spectroscopy of the gas phase species, revealing a large medium effect on the length of the donor — acceptor bond. The structural results are compared with published data for the trimethylamine — SO₂ adduct, and discussed in terms of existing experimental and theoretical results for other donor — acceptor systems.     

Crystal structure of (E)-5-hydroxypyrrolizidin-3-one and (Z)-5-thioketalpyrrolizidin-3-one

The crystal structures of (E)-5-hydroxypyrrolizidin-3-one (2) and (Z)-5-thioketalpyrrolizidin-3-one (3) have been determined by single-crystal x-ray diffraction techniques and refined by full-matrix least squares. Molecule2 crystallizes in the monoclinic space groupP2₁/a(No. 14) witha=7.887(3) Å,b=9.788(5) Å,c=9.316(4) Å,=100.6(1), andZ=4. Molecule 3 crystallizes in the monoclinic space groupP2₁/c witha=12.947(14) Å,b=10.553(14) Å,c=9.629(14) Å,=101.4(1), andZ=4. The calculated density for both molecules is 1.33 g cm^–1. FinalR-factors were 5.1% for2 and 8.59% for3. The x-ray results showed that a change in configuration occurred in the reaction going from2 to3.     

Structure of (meso-5,10,15,20-tetraphenylporphyrinato) dichlorophosphorus(V) chloride, [P(tpp)Cl2]+Cl−

The title compound [P(tpp)Cl₂]⁺Cl^– crystallizes in the space group P2₁/n witha=10.701(2),b=24.860(2),c=14.799(2), =94.24(2)°,Z=4. The phosphorus atom has an octahedral coordination geometry formed by the four nitrogen atoms (Np) of the porphyrinato group and the two chloride ions. The average phosphorus-chloride distance is 2.150(1) Å, with phosphorus situated 0.006 Å below the porphyrin ring.     

Crystal and molecular structure of 3-dimethylaminobenzoic acid

The title compound C₉H₁₁NO₂ is triclinic, space group P¯1, with the cell dimensionsa=7.022(1),b=7.476(2),c=8.957 (1) Å,=87.02(2),=110.88(1),=99.10(1)°,V=433.8(4) ų,Z=2,M _r =165.2,Do=1.27,Dx=1.26 mg/m³,F(000)=176,T=293 K,R=0.057 for 939 observed reflections. The molecules are packed as centrosymmetric hydrogen bonded dimers with an O-HO distance of 2.626(3) Å. The COOH group is rotated by 1.7(1)° about the exocyclic C(1)-C(7) bond out of the benzene ring plane. The molecules lie on (0 2-1) plane for which thed value is found to be 3.378 Å which is very close to the mean separation between the parallel packed benezene rings [3.347(4) Å]. The entire molecule is planar except for the two methyl groups attached to the nitrogen atom. The N atom is free from any binding of either type C-HN or O-HN.N. C. L. Communication No. 4699.     

Crystal structure of Co4(CO)10S2 and Co4(CO)10Se2; v(CO) vibrations of a model cluster molecule: Co4(CO)10S2

The crystal structure of Co₄(CO)₁₀S₂ has been redetermined and that of Co₄(CO)₁₀Se₂ obtained by X-ray analysis. The compounds are monoclinic and isomorphous, space groupP2₁/n,Z=2, with (S compound)a=10.42(2)Å,b=6.794(1)Å,c=12.421(2)Å,=97.27(1) and (Se compound)a=10.110(2)Å,b=6.747(2)Å,c=12.592(4)Å,=96.37(2); finalR(S)=0.029,R _w =0.032 for 1414 reflections and finalR (Se)=0.052,R _w =0.054 for 1264 reflections. The molecules, which lie on a crystallographic center of symmetry, consist of a rectangle with Co atoms at the corners, each face of the rectangle being capped by a chalcogen atom. Each Co atom is bonded to two terminal CO groups; there are two bridging CO groups, one on each member of a pair of opposite sides of the rectangle. The vibrational spectra of the sulfur compound are considered in detail. A study of the crystal structure, and recognition of an approximate spectroscopic space group, are shown to be essential for an understanding of thev(CO) infrared spectrum of polycrystalline Co₄(CO)₁₀S₂. In this molecule, intramolecular vibrational coupling in the crystal leads to extensive modifications of the infrared-activev(CO) molecular coordinates.     

The triethyl ammonium salt of O,O′-bis(o-tolyl) dithiophosphate [Et3NH]+[(2-MeC6H4O)2PS2]?

The X-ray structure of the triethyl ammonium salt of O,O′-bis(o-tolyl)dithiophosphate, [Et₃NH]⁺[(2-MeC₆H₄O)₂PS₂]⁻, has been determined. Crystal data: Monoclinic, P2₁/c, a = 15.4342(6) Å, b = 10.1913(4) Å, c = 14.0729(6) Å, β = 100.855(1)^∘, V = 2174.0(2) Å⁻³, Z = 4. The immediate environment around phosphorous is distorted tetrahedral with two sulfur and two oxygen atoms in the coordination sphere, with N–H–S bonding involving only one of the sulfur atoms.     

Crystal structure of bis-(rhodanine)copper(I) iodide,C6H6CuIN2O2S4

The structure of the polymeric rhodanine compound, C₆H₆CuIN₂O₂S₄, was determined by X-rays.M _r =456.8, monoclinic, space groupP2₁/c,a=4.1947(7),b=17.6999(12),c=17.1048(8) Å,=96.15(1)°,V _c =1262.6 ų,Z=4,D _c =2.40Mg m^–3, CuK radiation (graphite crystal monochromator, =1.54056 Å),(CuK)=278.9 cm^s-1,F(000)=872,T=290 K. Final conventionalR-factor=0.029, andR _w =0.044 for 2384 unique reflections and 153 variables. The structure was solved using Patterson methods andDirdif, and refined by full-matrix least-squares methods. The compound forms zigzag chains alonga. The copper atom is in trigonal pyramidal coordination, with two sulfur atoms of the thiocarbonyl group and two bridging iodine atoms. The copper-sulfur distances are 2.278(1) and 2.299(1) Å, and the copper-iodine distances are 2.657(1) and 2.814(1) Å.     

Crystal and molecular structure of dihydro-8b,8c-diphenyl-1H,3H,4H,5H,7H,8H,-2,6-dioxa-3a,4a,7a,8a-tetraazacyclopenta[def]fluorene-4,8-dithione

The title compound C₂₀H₁₈N₄O₂S₂ crystallizes in the monoclinic space group P2₁/n witha=8.4930(1) Å,b=11.4880(1) Å,c=20.0709(2) Å, =94.933(1)°,V=1951.01(3) ų,Z=4. The crystal structure has been solved by vector search methods and refined by fullmatrix least-squares toR=0.04 for 2888 reflections and 116 restraints. The title compound has a suitable geometry for synthesizing receptor molecules with a cleft for selective complexation.     

8-Thiatheophylline nitrato silver (I): Spectroscopic characterization and crystal structure

A new metal-theophylline derivative was synthesized from AgNO₃ and 8-thiatheophylline. The thermal stability of the Ag(C₆H₆N₄O₂S)(NO₃) complex was studied by TG and DSC techniques. The silver coordination has been discussed from IR,¹H-NMR and¹³C-NMR spectra. The crystal structure was established by X-ray diffraction. Ag(TTH)(NO₃) crystallizes in space groupP2₁2₁2₁ witha=6.198(1),b=12.576(2),c=13.422(2) Å andZ=4. The structure was refined toR=0.032. This complex reveals interesting features in the coordination mode of the TTH ligand. The sulfur atom and the carbonyl groups are not involved in the coordination. Silver tetrahedral coordination occurs through N7 and N9 of two different TTH ligands (Ag-N7=2.422(3) Å; Ag-N9=2.356(2) Å) and through two oxygen atoms of two different nitrato groups (Ag-O=2.435(4) and 2.518(4) Å) giving a polymeric structure.