Molecular structure of diphenyl sulfide in the gas phase

Gas-phase electron diffraction and quantum-chemical calculations were used to study the molecular structure of diphenyl sulfide. It is shown that the diphenyl sulfide molecule (PhS₂) possesses C ₂ symmetry. The main geometrical parameters are as follows: r _a(C-S) 1.774(2) Å, r _a(C-C)_av 1.401 Å, ∠CSC 103.4(11)°, ∠SCC 122.5 and 117.9(6)°, and ∠CCC_av 120.0°. The torsion angles about C-S bonds τ(CSCC) are ?49.6(1.4)°.     

Electron diffraction and quantum-chemical studies of the molecular structure of 2-methylbenzenesulfochloride

A combined electron diffraction and quantum-chemical (MP2/6-31G**) study of the molecular structure of 2-methylbenzenesulfochloride at 336(5) K was carried out. It was found that the gas phase contained only one conformer, C ₁. The following structural parameters were obtained: r _h1(C-H)_av = 1.095(8) Å, r _h1(C-C)_Ph = 1.402(4) Å, r _h1(C_Ph-C_meth) = 1.507(13) Å, r _h1(C_Ph-S) = 1.763(6) Å, r _h1(S=O) = 1.418(4) Å, r _h1(S-Cl) = 2.048(5) Å, ∠(H-C-H)_meth/av = 107.3(96)°, ∠(Cl-S-O)_av = 106.4(3)°, ∠C_Ph-S-Cl = 100.8(9), ∠O=S=O = 120.8(10)°. The C_C-C_S-S-Cl torsion angle that defines the position of the S-Cl bond relative to the plane of the benzene ring is 75.6(20)°. The B3LYP/6-311+G** calculated barriers of internal rotation of the methyl and sulfochloride groups are 1.2 kcal/mol and V ₀₁ = 10.2 (V ₀₂ = 4.1) kcal/mol, respectively.     

Crystal structure and luminescence and thermochromic properties of bis-1,10-phenanthrolinium hexachlorotellurate(IV)

The structure of bisphenanthrolinium hexachlorotellurate(IV) (C₁₂H₉N₂)₂TeCl₆ is determined by X-ray diffraction analysis: a = 7.6619(8), b = 8.0034(8), c = 10.959(1) Å, α = 82.680(2)°, β = 81.379(2)°, γ = 85.569(2)°; space group P \(\bar 1\), Z = 1, and ρ_calcd = 1.774 g/cm³. The crystal structure is built of the [TeCl₆]^2? anions and phenanthrolinium cations. The electronic and geometric aspects determining the spectral luminescence and thermochromic properties are discussed.     

Crystal structure of copper(II) <Emphasis Type="Italic">trans</Emphasis>-bis-(4-phenyliminopentan-2-onate)

trans-Bis-(4-phenyliminopentan-2-onato)Cu(II) (5), which is a phenyl-substituted ketoimine, was synthesized, and an X-ray study was performed for this compound. Crystal data for CuN₂O₂C₂₂H₂₄: a = 11.4557(3) Å, b = 26.6845(9) Å, c = 14.2976(5) Å, β = 113.2270(10)°; space group P2₁/n, Z = 8, d _calc = 1.363 g/cm³, R = 0.033. The structure is molecular and built of isolated trans complexes. The central copper atom is surrounded by four atoms (2O+2N) with the average distances Cu-O 1.904(3) Å and Cu-N 1.962(3) Å. The polyhedron around the copper atom is a distorted tetrahedron; the average values of the O-Cu-O and N-Cu-N trans bond angles are 147(2)° and 150(2)°, respectively. The average value of the O-Cu-N angles is 94(1)°.     

Crystal and molecular structure of (hexafluoroacetylacetonato) (pivaloylacetonato)copper(II)

The crystal structure of (hexafluoroacetylacetonato)(pivaloylacetonato)copper(II) has been determined. Crystal data for CuO₄C₁₃H₁₄F₆: a = 8.288(2) Å, b = 8.682(2) Å, c = 12.307(2) Å; α = 90.75(3)°, β = 94.29(3)°, γ = 106.60(3)°; V = 845.7(3) ų, space group \(P\overline 1 \), Z = 2, d_calc = 1.617 g/cm³. The coordination polyhedron of the copper atom is formed by four oxygen atoms of two different β-diketonate ligands with Cu-O distances within 1.874–1.946 Å; the O-Cu-O bond angles are 94.8° and 90.6°. The complexes are united into centrosymmetrical “dimers” with Cu...Cu distances of 4.365 Å.     

Synthesis,crystal structure,and kinetics of thermal decomposition of the Zn(II) complex with vanillin

A complex [Zn(C₈H₇O₃)₂(H₂O)₂] (C₈H₈O₃ is vanillin) has been synthesized and characterized by IR, elemental analysis, and X-ray diffraction single-crystal analysis. The crystals are monoclinic, space group C2/c, a = 22.236(8) Å, b = 10.594(2) Å, c = 7.8190(16) Å, α = 89.90(3)°, β = 106.87(4)°, γ = 89.99(3)°, V = 1762.6(8) ų, Z = 4, F(000) = 832, S = 1.079, ρ _c = 1.521g cm^?3, R = 0.0221, R _w = 0.0604, μ = 1.433 mm^?1. The Zn²⁺ ion is six-coordinated with a distorted octahedron geometry. The complex forms a three-dimensional network through intermolecular hydrogen bonds. The thermal decomposition kinetics of the complex for the second stage was studied under non-isothermal conditions by the TG and DTG methods. The kinetic equation can be expressed as dα/dt = Ae^?E/RT 2(1 ? α)[1 ? ln(1 ? α)]^1/2. The kinetic parameters (E, A), activation entropy ΔS ^≠, and activation free-energy ΔG ^≠ were also gained.     

Thermodynamic Properties of Polyphenylquinoxaline in the Temperature Range of <Emphasis Type="Italic">T</Emphasis> → 0 to 570 K

The thermodynamic properties of amorphous polyphenylquinoxaline in the temperature range of 6 to 570 K are studied via precision adiabatic vacuum calorimetry and differential scanning calorimetry. The thermodynamic characteristics of glass transition are determined. Standard thermodynamic functions C^°_p, H°(T) ? H°(0), S°(Т) ? S°(0), and G°(T) ? H°(0) in the range of T → 0 to 570 K and the standard entropy of formation at T = 298.15 K are calculated. The low-temperature (T ≤ 50 K) heat capacity is analyzed using a multifractal model for the processing of heat capacity, fractal dimension D values are determined, and conclusions on the topological structure of the compound are drawn.     

Molecular structure of 2-methoxy-4-pyrrolidinyl-6-trinitromethyl-1,3,5-triazine

An X-ray diffraction study of 2-methoxy-4-pyrrolidinyl-6-trinitromethyl-1,3,5-triazine was carried out. The crystals are triclinic; C₉H₁₁N₇O₇; M = 329.25; a = 8.536(1) Å, b = 9.378(2) Å, c = 9.7401(8) Å; α = 79.13(1)°, β = 73.974(8)°; γ = 72.76(1)°; V = 710.8(2) ų, d _c = 1.54 g/cm³, Z = 2, space group P1ˉ. The molecule on the whole is planar, except the pyrrolidine ring, which has a twist conformation. No significant π-π interactions and hydrogen bonds of C-H⋯N or C-H⋯O type were found in the crystal, and the molecule packing is stabilized only due to van der Waals interactions. Original Russian Text Copyright ? 2008 by V. V. Bakharev, A. A. Gidaspov, I. A. Litvinov, and E. V. Mironova __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 1, pp. 187–189, January–February, 2008.     

Structure of aluminum(III) dipivaloylmethanate AlO<Subscript>6</Subscript>C<Subscript>33</Subscript>H<Subscript>57</Subscript>

The structure of aluminum(III) tris-dipivaloylmethanate (Bruker Nonius X8 Apex diffractometer with a 4K CCD detector, λMoK _α, graphite monochromator, T = 150(2) K) is determined, and the synthetic procedure for its preparation is suggested. Crystal data are: C2/c space group, a = 28.1587(12) Å, b = 18.5170(7) Å, c = 21.5332(8) Å, β = 97.573(1)°, V = 11129.8(8) ų, Z = 12, d _x = 1.033 g/cm³, R = 6.93. The complex has a molecular structure; the aluminum atom is octahedrally surrounded by six oxygen atoms of three chelating ligands; Al-O distances are 1.860(2)–1.873(2)0A; O-Al-O angles fall within 88.08(9)–91.96(10)° and 177.93(9)–179.83(14)°. The known crystal packings of metal tris-dipivaloylmethanates are analyzed. Three types of the arrangement of the molecules in the crystals denoted as α, β, and γ are identified.     

Synthesis and structural investigation of hafnium(IV) complexes with acetylacetone and trifluoroacetylacetone

Two volatile hafnium(IV) complexes with acetylacetone and trifluoroacetylacetone (HL) have been prepared and their structures have been studied at ?30°C. Crystal data for C₂₀H₂₈HfO₈: a = 21.5493(4) Å, b = 8.36720(10) Å, c = 13.9905(3) Å; β = 116.5550(10)°, space group C2/c, Z = 4, d _calc = 1.692 g/cm³, R = 0.015. Crystal data for C₂₀H₁₆F₁₂HfO₈: a = 8.1039(12) Å, b = 11.4499(14) Å, c = 15.790(2) Å; α = 99.341(4)°, β = 103.175(4)°, γ = 108.185(4)°, space group P?1, Z = 2, d _calc = 2.003 g/cm³, R = 0.074. Both structures are molecular and comprise isolated complex molecules HfL₄. The hafnium atom is coordinated with eight oxygen atoms of four β-diketonate ligands, Hf-O distances varying from 2.153 Å to 2.191 Å. The molecules make van der Waals contacts in the structures.     

Palladium clusters Pd<Subscript>4</Subscript>(SR)<Subscript>4</Subscript>(OAc)<Subscript>4</Subscript> and Pd<Subscript>6</Subscript>(SR)<Subscript>12</Subscript> (R = Bu,Ph): Structure and properties

The structures of the Pd₄(SBu)₄(OAc)₄ (I) and Pd₆ (SBu)₁₂ (II) palladium clusters are determined by the X-ray diffraction method. For cluster I: a = 8.650(2), b = 12.314(2), c = 17.659(4) Å, α = 78.03(3)°, β = 86.71(2)°, γ = 78.13(3)°, V = 1800.8(7) ų, ρcalcd = 1.878 g/cm³, space group P \(\bar 1\), Z = 4, N = 3403, R = 0.0468; for structure II: a = 10.748(2), b = 12.840(3), c = 15.233(3) Å, α = 65.31(3)°, β = 70.10(3)°, γ = 72.91(3)°, V = 1767.4(6) ų, ρ calcd = 1.605 g/cm³, space group P \(\bar 1\), Z = 1, N = 3498, R = 0.0729. In cluster I, four Pd atoms form a planar cycle. The neighboring Pd atoms are bound by two acetate or two mercaptide bridges (Pd…Pd 2.95–3.23 Å, Pd…Pd angles 87.15°–92.85°). In cluster II, the Pd atoms form a planar six-membered cycle with Pd···Pd distances of 3.09–3.14 Å, the PdPdPd angles being 118.95°–120.80°. The Pd atoms are linked in pairs by two mercaptide bridges. The formation of clusters I and II in solution is proved by IR spectroscopy and calorimetry. Analogous clusters are formed in solution upon the reaction of palladium(II) diacetate with thiophenol.     

[H<Subscript>2</Subscript>OT][PdCl<Subscript>4</Subscript>], a salt of the protonated oxythiamine cation with the tetrachloropalladate(II) tetrachloride anion synthesis and crystal structure

The interaction of oxythiamine chloride hydrochloride with a solution of palladium chloride in hydrochloric acid affords a salt of protonated oxythiamine [H₂OT][PdCl₄] (I) (HOT is 4-methyl-3-[(2′-methyl-4′-oxo-3′,4′-dihydropyrimidinyl-5′)methyl]-5-(2-hydroxyethyl)thiazolium, C₁₂H₁₆N₃O₂S⁺). The crystal structure of salt I is determined by X-ray diffraction analysis. The crystals are monoclinic: a = 9.474(3) Å, b = 13.822(2) Å, c = 13.626(4) Å, β = 93.42(2)°, V = 1781.2(3) ų, Z = 4, space group P2₁/n. The structural units of salt I are doubly-charged cations [H₂OT]²⁺ and anions [PdCl₄]^2? joined by hydrogen bonds and electrostatic interaction into dimeric supermolecules. The thiazolium and pyrimidine rings in the cation are planar (the dihedral angle between the planes is 89.6°) and oriented relative to the linking methylene center to form torsion angles Φ _t = 64.9° and Φ _p = 49.9° characteristic of the V′ conformation.     

Synthesis and crystal structure of methylammonium dicitratoborate

Methylammonium dicitratoborate CH₃NH₃[(C₆H₆O₇)₂B] (I) was synthesized for the first time. The crystal structure of the compound was studied by X-ray crystallography. Crystals of I are triclinic, space group P \(\bar 1\), a = 8.9726(3) Å, b = 10.1039(3) Å, c = 10.7231(4) Å, α = 66.894(1)°, β = 85.347(1)°, γ = 84.991(2)°, V = 889.57(5) ų, Z = 2, ρ_calcd = 1.580 g/cm³. Crystals of I are built up from large dicitratoborate anions with a spiran structure and methylammonium cations. The crystals have a layered structure. A hydrogen-bond system is formed by seven independent contacts O(N)-H?O.     

Double helix of the coordination polymer of silver with 1,3-bis(4-pyridyl)propane: Synthesis and crystal structure of [Ag(C<Subscript>13</Subscript>H<Subscript>14</Subscript>N<Subscript>2</Subscript>)](CF<Subscript>3</Subscript>CO<Subscript>2</Subscript>)

The [Ag(Bpp)](CF₃CO₂) complex (Bpp is 1,3-bis(4-pyridyl)propane, C₁₃H₁₄N₂) is synthesized, and its structure is determined. The crystals are monoclinic, space group C2/c, a = 26.169(5), b = 10.521(2), c = 12.906(3) Å, β = 117.99(3)°, V = 3137.7(11) ų, ρ_calcd = 1.775 g/cm³, Z = 8. The structure contains double helices of-Ag-Bpp-Ag-Bpp-cationic chains with a helix period of 21.042 Å. The Ag…Ag distance between a pair of silver atoms from different chains in the helix is 3.201 Å, and the distance between the adjacent helices is 3.279 Å. The silver atom is linked with two bridging nitrogen atoms of two Bpp ligands in an almost linear coordination: Ag-N_avg 2.142 Å; NagN, 171.3(4)°. The CF₃C ₂ ^? anion has a weak contact with the silver ion (Ag…O 2.62(2) Å).     

Crystal and molecular structure of guanidinium dicitratoferrate(II)

Synthesis and X-ray investigation of a (GunH)₂[Fe(Cit)₂] single crystal are described [a = 10.327(2) Å, b = 10.414(2) Å, c = 11.267(2) Å; β = 117.25(3)°, V = 1077.2(4) ų, P2₁/n, Z = 2, R(F) = 0,0239, 1196 reflections with I > 2σ(I )], where GunH is the guanidine cation (C(NH₂)₃)⁺, and Cit is the citric acid anion (C₆H₆O₇)^2?. The structure is composed of guanidinium cations and centrosymmetrical sym-cis-octahedral complex anions [Fe(Cit)₂]^2?. The Cit^2? anion acts as a cyclic tridentate ligand and forms condensed fiveand six-membered metal-containing cycles.     

<Emphasis Type="Italic">N,N</Emphasis>-diethylanilinium complex with borodicitric acid: Synthesis and crystal structure

N,N-Diethylanilinium dicitratoborate [C₆H₅NH(C₂H₅)₂][(C₆H₆O₇)₂B] (I) has been synthesized for the first time. Single crystals has been synthesized in an aqueous solution to study the crystal structure of complex I by single-crystal X-ray diffraction. Crystals are triclinic, space group Р1 a = 9.6183(2) Å, b = 10.3153(3) Å, c = 13.7364(4) Å, α = 69.0304(12)°, β = 77.0394(13)°, γ = 89.5518(10)°, V = 1236.25(6) ų, Z = 2, ρ_calcd = 1.454 g/cm³. Structural units in a crystal of complex I are large complex dicitratoborate anions with a spirane structure and N,N-diethylanilinium cations. The crystal packing is a three-dimensional framework implemented via a system of hydrogen bonds like О–Н…О, О–Н…О, ОI, and N–Н…О.     

Synthesis,characterization, crystal and molecular structure analysis of a novel 1-benzhydryl piperazine derivative: 1-benzhydryl-4-(2-nitro-benzenesulfonyl)-piperazine

A novel 1-benzhydryl piperazine derivative 1-benzhydryl-4-(2-nitro-benzenesulfonyl)-piperazine was synthesized by the nucleophilic substitution of 1-benzhydryl piperazine with 2-nitro-benzenesulfonyl chloride. The product obtained was characterized spectroscopically and finally confirmed by X-ray diffraction study. The title compound, C₂₃H₂₃N₃O₄S crystallizes in the monoclinic space group C2/c with cell parameters a = 13.1120(9) Å, b = 21.4990(9) Å, c = 16.655(1) Å, β = 111.352(2)°, Z = 8, and V = 4372.7(4) Å. The structure reveals that the piperazine ring is in a chair conformation. The geometry around the S atom is distorted tetrahedral. There is a large discrepancy in the bond angles around the piperazine N atoms. The structure is stablized by C–H···O type intermolecular hydrogen bonding interactions.     

Synthesis and crystal structure of EnH<Superscript>2</Superscript>[IrCl<Superscript>6</Superscript>]

The preparation of EnH²[IrCl⁶] is described. Crystal data for C₂H₁₀Cl₆IrN₂ are: a = 6.8972(11) Å, b = 6.9435(16) Å, c = 7.3354(11) Å; α = 88.269(3)°, β = 65.495(2)°, γ = 60.305(2)°, V = 270.76(9) ų, space group P1, Z = 1, d_calc = 2.864 g/cm³. Crystal chemical analysis of the general motif of the structure was performed by the translation sublattice identification technique. It has been found that complex anions [IrCl₆]^2? follow the nodes of a rather regular rhombohedral subcell with the parameters a_c = 7.1 Å, α_c = 64°.     

Crystal structure and thermal investigation of bis-(1-thenoyl-4,4,4-trifluorobutan-1,3-dionato) lead(II)

Lead(II) complex with thenoyltrifluoroacetone has been prepared and characterized by IR spectroscopy, powder and single crystal X-ray diffraction. Crystal data for PbO₄S₂F₆C₁₆H₈: a = 20.457(4) Å, b = 11.292(2) Å, c = 8.409(2) Å; β = 91.37(3)°, space group C2/c, Z = 4, d _calc = 2.222 g/cm³. The molecule of the complex is non-planar, average distances Pb-O are 2.384 Å, chelate angle O-Pb-O is 75.0°. The structure is of polymeric chain nature, Pb...Pb separation in the chains being 4.311 Å. The complex Pb(ttf)₂ is stable under heating up to 250°C. The compound is less volatile than Cu(ttf)₂ or Fe(ttf)₃.     

Crystallochemical study of ruthenium(III) tris-dipivaloylmethanate

The structure of ruthenium(III) dipivaloylmethanate is determined by single crystal X-ray diffraction at temperature of 150 K. The crystallographic data for C₃₃H₅₇O₆Ru are as follows: a = 9.6119(11) Å, b = 17.4603(19) Å, c = 21.519(2) Å, β = 95.187(2)°, C2/c space group, V = 3596.7(7) ų, Z = 4, d_calc = = 1.202 g/cm³, R = 0.0642. The structure is molecular, the metal atom coordinates six oxygen atoms of three ligands of β-diketone. The Ru–O distances are in the range of 1.99 Å to2.03 Å. The complexes have a distorted single layer hexagonal packing with the Ru…Ru distances being 9.84 Å within the layer, and 10.93 Å between the layers.