Crystal and molecular structure and properties of [Ni(4-NH2Py)2(iso-Bu2PS2)2] and [Co(4-NH2Py)(iso-Bu2PS2)2]

The interaction of the Co(iso-Bu₂PS₂)₂ chelate with 4-NH₂Py afforded a paramagnetic complex [Co(4-NH₂Py)(iso-Bu₂PS₂)₂] (μ_eff = 4.53 BM). Single crystals of [Ni(4-NH₂Py)₂(iso-Bu₂PS₂)₂] (I) and [Co(4-NH₂Py)(iso-Bu₂PS₂)₂] (II) were grown and used for X-ray diffraction investigation (X8 APEX diffractometer, MoK _α radiation). Crystals I are monoclinic with unit cell parameters a = 12.5336(5) Å, b = 9.4356(4) Å, c = 16.4095(6) Å; β = 111.351(1)°; V = 1807.4(1) ų; Z = 2, ρ = 1.223 g/cm³, space group P2₁/n. Crystals II are triclinic with unit cell parameters a = 8.7572(4) Å, b = 9.6934(6) Å, c = 18.665(1) Å; α = 79.374(2)°, β = 87.049(2)°, γ = 75.640(2)°; V = 1508.6(1) ų; Z = 2, ρ = 1.259 g/cm³; space group . The structures of I and II are formed by isolated mononuclear molecules. The coordination unit is NiN₂S₄ (octahedron) in I and CoNS₄ (tetragonal pyramid) in II. The 4-NH₂Py molecule is coordinated through the N atom of the heterocycle. Electronic spectroscopy data for II agree with the symmetry of the NS₄ polyhedron found by X-ray diffraction (XRD) analysis. The noncoordinated amine groups link the complex molecules via N-H...S hydrogen bonds. __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 6, pp.1072–1080, November–December, 2005. Original Russian Text Copyright ? 2005 by T. E. Kokina, L. A. Glinskaya, E. A. Sankova, R. F. Klevtsova, and S. V. Larionov     

Synthesis and crystal and molecular structure of CdPhen( iso -C4H9OCS2)2 and CdPhen( n -C4H9OCS2)2 mixed-ligand complexes

Mixed-ligand complexes CdPhen(i-BuOCS₂)₂ (I) and CdPhen(n-BuOCS₂)₂ (II) have been synthesized. Their structures were solved using X-ray diffraction data (X8 APEX diffractometer, MoK _α radiation, 1641 and 2497 F _hkl , R = 0.0359 and 0.0389). Crystals I are orthorhombic with unit cell parameters a = 6.5883(3) Å, b = 19.7123(10) Å, c = 20.1936(11) Å, V = 2622.6(2) ų; Z = 4, space group Pbcn; crystals II are monoclinic, a = 6.5845(2) Å, b = 19.1522(6) Å, c = 20.7091(7) Å, β = 97.106(1), V = 2591.5(1) ų, Z = 4, space group C2/c. The structures consist of discrete mononuclear molecules in which the coordination polyhedron of the Cd atom is a distorted N₂S₄ octahedron. Molecular packing and interactions in the structures are discussed. Original Russian Text Copyright ? 2007 by R. F. Klevtsova, T. G. Leonova, L. A. Glinskaya, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No. 2, pp. 274–281, March–April, 2007.     

Stereoselective Synthesis of (7aS)-1-Methylenehexahydro-1H-pyrrolizine and (?)-Heliotridane from N-Diphenylmethyl-(S)-proline Ethyl Ester

Alkaloid (7aS)-1-methylenehexahydro-1H-pyrrolizine was synthesized from N-diphenylmethyl-(S)-proline ethyl ester by cyclopropanation of the ester group with ethylmagnesium bromide in the presence of titanium tetraisopropoxide, replacement of the protecting group on the nitrogen atom, and cationic cyclopropylallyl isomerization of (S)-1-(1-ethoxycarbonylpyrrolidin-2-yl)cyclopropyl sulfonate into the corresponding allyl bromide. Stereoselective reduction of (7aS)-1-methylenehexahydro-1H-pyrrolizine with sodium tetrahydridoborate in the presence of nickel chloride afforded (−)-heliotridane [(1S,7aS]-1-methylhexahydro-1H-pyrrolizine] in high yield.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 73–77.Original Russian Text Copyright © 2005 by Lysenko, Kulinkovich.     

Synthesis and crystal and molecular structure of mixed-ligand complexes Cd(2,2′-Bipy)(i-PrOCS2)2 and (2,2′-Bipy)(i-BuOCS2)2

Mixed-ligand complexes Cd(2,2′-Bipy)(i-PrOCS₂)₂ (I) and Cd(2,2′-Bipy)(i-BuOCS₂)₂ (II) have been prepared. Their structures were solved using the X-ray diffraction technique (X8 APEX diffractometer, MoK _α radiation, 1941 and 4244 F _hkl , R = 0.0188 and 0.0379). The crystals are orthorhombic with unit cell parameters a = 18.1404(4) Å, b = 6.9513(1) Å, c = 17.5835(4) Å; V = 2217.27(8) ų, Z = 4, space group Pccn (for complex I) and a = 11.7890(3) Å, b = 12.1859(3) Å, c = 17.5335(5) Å; V = 2518.9(1) ų, Z = 4, space group P2₁2₁2₁ (for complex II). The structures consist of isolated mononuclear molecules. The cadmium atoms have distorted octahedral N₂S₄ environments. Molecular packings and intermolecular interactions in the structures are considered. __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 6, pp.1064–1071, November–December, 2005. Original Russian Text Copyright ? 2005 by S. V. Larionov, L. A. Glinskaya, T. G. Leonova, and R. F. Klevtsova     

The stereochemistry of the dichlorocobalt(III) complexes with (2S,5S,9S)- and (2S,5R,9S)-trimethyltriethylenetetraamines

Dichlorocobalt(III) complexes of (2S,5S,9S)-trimethyltriethylenetetraamine (L₁) and (2S,5R,9S)-trimethyltriethylenetetraamine (L₂) have been prepared. Both L₁ and L₂ coordinate to the cobalt(III) ion to give three isomers: Λ-cis-α, Δ-cis-β, trans isomers for L₁ and Δ-cis-α, Δ-cis-β, trans isomers for L₂. Each of the trans-dichloro complexes of the two ligands have been isomerized stereospecifically to the cis-α-dichloro complex in methanol, and each of the cis-α-dichloro complexes stereospecifically to the trans-diaqua complex in water. Both the geometrical and optical inversions took place at the same time in the observed stereospecific isomerizations.     

三有机锡(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸酯的合成、结构和体外抗癌活性

利用三有机锡氢氧化物和手性配体(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸(HL)反应合成了3个三有机锡(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸酯R3SnL[1,R=c-C6H11(a),C6H5(b),C6H5C(CH3)2CH2(c)],通过元素分析、IR、1H NMR和X-射线单晶衍射表征了其结构。化合物1a属正交晶系,P212121空间群;化合物1b属单斜晶系,P21空间群。二者均为由羧基氧和内酰胺羰基氧桥联配位形成的右螺旋链状有机锡配位聚合物,锡原子具有五配位[SnC3O2]畸变三角双锥构型。化合物1a和1b对体外2种人癌细胞Colo205和Bcap37增殖均有强的抑制作用,其活性为1b1a。     

Crystal and molecular structure of the [Y(Phen){( i -C4H9)2PS2}2NO3] mixed-ligand compound

The [Y(Phen){(i-C₄H₉)₂PS₂}₂NO₃] mixed-ligand compound (I) was synthesized. Its structure was determined by X-ray diffraction analysis (X8 APEX diffractometer, λMoK _α , 3788 F _hkl , R = 0.0677). Crystals I are orthorhombic: a = 10.6495(8) Å, b = 20.006(2) Å, c = 35.317(4) Å, V = 7524.4(13) ų, Z = 8, ρ_calc = 1.324 g/cm³, space group Pbca. The structure is built of mononuclear discrete molecules. The N₂O₂S₄ coordination polyhedron of the Y atom is a distorted dodecahedron. Original Russian Text Copyright ? 2008 by V. L. Varand, L. A. Glinskaya, R. F. Klevtsova, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 1, pp. 182–186, January–February, 2008.     

三有机锡（4R）-3-[[（2S）-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸酯的合成、结构和体外抗癌活性

利用三有机锡氢氧化物和手性配体（4R）-3-[[（2S）-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸（HL）反应合成了3个三有机锡（4R）-3-[[（2S）-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸酯R₃SnL[1,R=c-C₆H₁₁（a）,C₆H₅（b）,C₆H₅C（CH₃）₂CH₂（c）],通过元素分析、IR、¹H NMR和X-射线单晶衍射表征了其结构。化合物1a属正交晶系,P2₁2₁2₁空间群;化合物1b属单斜晶系,P2₁空间群。二者均为由羧基氧和内酰胺羰基氧桥联配位形成的右螺旋链状有机锡配位聚合物,锡原子具有五配位[SnC₃O₂]畸变三角双锥构型。化合物1a和1b对体外2种人癌细胞Colo205和Bcap37增殖均有强的抑制作用,其活性为1b >1a。     

Y型分子筛固载(1S,2S)-DPEN-Ru(TPP)2催化苯乙酮不对称加氢

采用自由配体法将(1S,2S)-DPEN(1,2-diphenyl-1,2-ethylene-diamine)-Ru(TPP)2(TPP=三苯基膦,triphenylphosphine)配合物封装于NaY沸石分子筛超笼中,制备了(1S,2S)-DPEN-Ru(TPP)2/Y主客体材料(1S,2S)-DPEN=1,2-二苯基-1,2-乙二胺).采用等离子体发射光谱ICP、粉末X射线衍射(XRD)、紫外光谱(UV-Vis)、氮吸附等物理化学手段对所制备材料进行了表征.结果表明,(1S,2S)-DPEN-Ru(TPP)2配合物封装于Y型分子筛超笼中保持了原有的物理化学性能;作为苯乙酮不对称加氢催化剂,在优化条件下,苯乙酮的转化率可达100%,(R)-苯乙醇的对映体过量值(ee值)可达61.0%.该催化剂具有良好的稳定性和重复使用性.     

Crystal and molecular structures of the Rh[(C2H5O)2PS2]3 and Co[(C6H5O)2PS2]3 chelate compounds

The crystal structures of the Rh[(EtO)₂PS₂]₃ (I) and Co[(PhO)₂PS₂]₃ (II) chelate compounds were determined from X-ray diffraction (XRD) data (CAD-4 diffractometer, MoK _β radiation, 1193 F _hkl , R = 0.0516 for I and 513 F _hkl , R = 0.0305 for II). Crystals I are monoclinic: a = 14.233(3) Å, b = 13.570(3) Å, c = 14.272(3) Å; β = 90.66(3)°, V = 2756.3(10) ų, Z = 4, ρ_calc = 1.587 g/cm³, space group C2/c. Crystals II are trigonal: a = 15.149(2) Å, c = 30.306(6) Å; V = 6023.2(16) ų, Z = 6, ρ_calc = 1.493 g/cm³, space group R3ˉ. Structures I and II consist of discrete mononuclear molecules. The coordination polyhedra of the M atoms (M = Rh, Co) are distorted octahedra formed by six sulfur atoms of three cyclic bidentate (RO)₂ PS₂⁻ ligands. Original Russian Text Copyright ? 2008 by R. F. Klevtsova, L. A. Glinskaya, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 2, pp. 330–334, March–April, 2008.     

Crystal and molecular structures of Ni[(iso-C4H9)2PS2]2 and Pd[(iso-C4H9)2PS2]2 chelates

Crystal structures of chelate compounds Ni[(iso-C₄H₉)₂PS₂]₂ (I) and Pd[(iso-C₄H₉)₂PS₂]₂ (II) have been determined by X-ray diffraction: diffractometer X8-APEX, MoK _α∔ -radiation, 1048 F _hkl , R = 0.0544 for I and CAD-4 diffractometer, MoK _α∔ -radiation, 1283 F _hkl , R = 0.0347 for II. The crystals are rhombic: a = 12.921(5) Å, b = 17.094(5) Å, c = 22.971(5) Å; V = 5074(3) ų, Z = 8, calc = 1.250 g/cm³, space group Pbca for I and a = 13.312(3) Å, b = 16.130(7) Å, c = 23.171(5) Å; V = 4975(3) ų, Z = 8, ρ_calc = 1. 208 g/cm³, space group Pbca for II. The structures of I and II are formed by discrete mononuclear molecules. Coordination cores MS₄ (M = Ni, Pd) approach planar square configurations. Original Russian Text Copyright ? 2005 by L. A. Glinskaya, T. G. Leonova, T. E. Kokina, R. F. Klevtsova, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 4, pp. 715–720, July–August, 2005.     

Pseudohexagonal motif of the arrangement of compex anions in the structure of [Ru(NH3)5Cl]2[Re6S8(CN)6]·3H2O

The [Ru(NH₃)₅Cl]₂[Re₆S₈(CN)₆]·3H₂O salt was obtained; its crystal structure was analyzed: a = 10.7713(9) Å, b = 13.9602(11) Å, c = 14.7956(11) Å, α = 91.961(3)°, β = 109.985(3)°, γ = 110.030(3)°, V = 1935.3(3) ų, space group P1ˉ, Z = 2, d _calc = 3.441 g/cm³. In the cluster anion, the Re-Re distances lie in the range from 2.594 Å to 2.612 Å. For two crystallographically independent complex cations, Ru-N_av is 2.105 Å, and Ru-Cl_av 2.329 Å. A pseudohexagonal motif of the structure was found. Original Russian Text Copyright ? 2008 by K. V. Yusenko, I. A. Baidina, E. A. Shusharina, and S. A. Gromilov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 1, pp. 178–181, January–February, 2008.     

(R)-4-menthen-3-one in the synthesis of (3S)-methylundecand (2S)-methyldec-1-ylbromides, key synthons for (S,S,S)-diprionylacetate

New capabilities for the synthetic use of (R)-4-menthen-3-one were demonstrated using as examples (3S)-methylundec- and (2S)-methyldec-1-ylbromides, key synthons for (S,S,S)-diprionylacetate (sex pheromone of pine sawflies of genera Diprion and Neodiprion).     

Molecular and crystal structure of 4-trifluoro-2-[2-(4-fluorophenyl)hydrazine-1-ylidene]-1-(thiophen -2-yl)butane-1,3-dione

Single crystal X-ray diffraction is used to determine the crystal and molecular structure of 4-trifluoro-2-[2-(4-fluorophenyl)hydrazine-1-ylidene]-1-(thiophen-2-yl)butane-1,3-dione. Crystallographic data for C₁₄H₈F₄N₂O₂S are as follows: a = 8.2723(6) ?, b = 9.3009(7) ?, c = 9.9895(7) ?; α = 79.224(2)°, β = 75.851(2)°, γ = 72.337(2)°. Triclinic crystal system, P-1 space group, d _x = 1.622 g/cm³, V = 704.83(9) ?³, μ = 0.286 mm⁻¹, crystal size 0.30×0.20×0.20 mm, R1 = 0.0891, wR2 = 0.1989.     

Investigation of the structure and energy of β-diketonates. XIV. Composition of overheated vapors and the molecular structure of monomeric yttrium tris-hexafluoroacetylacetonate Y(C5O2HF6)3

Simultaneous electron diffraction and mass spectrometry along with a quantum chemical (DFT/B3LYP) calculation are applied to study the molecular structure of yttrium tris-hexafluoroacetylacetonate Y(hfa)₃. The superheating of the vapor in a double two-temperature effusion cell shows that up to a temperature of ∼200°C ions containing from one to three metal atoms are formed, and the most intensive ion has the stoichiometry of (Y₂L₅)⁺ at a temperature below ∼120°C. The monomer starts to noticeably decompose at temperatures above 330°C.The electron diffraction patterns of monomers are obtained at T _exp = 208(5)°C. According to the results of theoretical and experimental investigations, Y(hfa)₃ molecule has D ₃-symmetry. The rotation angle of triangular O-O-O faces with respect to their position in the regular prism is equal to 14.4(1)°C. The values of internuclear distances and valence angles (r _h1-geometry) are: r(Y-O) = 2.259(6) Å, r(C-O) = 1.263(6) Å, r(C-C_r) = 1.413(4) Å, r(C-C_F) = 1.531(4) Å, r(C-F) = 1.344(3) Å, O-Y-O = 75.2(2)°, O-C-C_F = 113.8(2)°, C-C_F-F = 112.4(2)°. The results of quantum chemical calculations are well consistent with the experimental data. Original Russian Text Copyright ? 2007 by G. V. Girichev, V. V. Rybkin, N. V. Tverdova, S. A. Shlykov, N. P. Kuz’mina, and I. G. Zaitseva __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No. 5, pp. 871–879, September–October, 2007.     

Crystal structure of 2-(6-chloro-4-P-tolylamino)pyrido[3,2-d]pyrimidin-1-ium-1-yl)acetate oxonium bromide

The crystals of 2-(6-chloro-4-(p-tolylamino)pyrido[3,2-d]pyrimidin-1-ium-1-yl)acetate (zwitterionic form) oxonium bromide, C₁₆H₁₃ClN₄O₂·Br⁻·H₃O⁺ (I) were prepared and studied by single-crystal X-ray diffraction method. The compound crystallizes in the triclinic space group P-1 with a = 8.3121(8) ?, b = 9.3885(8) ?, c = 13.2903(12)?, α = 106.788(2)°, β = 95.204(3)°, γ = 110.871(2)°, V = 905.81(14) ?³, Z = 2; final R = 0.053, wR2 = 0.150. It is interesting that methylene C in the BrCH₂COOH molecule binds to the N1 of the pyrimidine ring. In the crystal studied, two neighboring organic molecules are connected by hydrogen bonds through carboxylate oxygen, oxonium and bromide ions to form a dimer.     

Synthesis and structure of [Ni(dien)2]3[W4S4(CN)2]·20H2O and [Cu(dien)(Hdien)]2[W4S4(CN)12]·8H2O

[Ni(dien)₂]₃[W₄S₄(CN)₁₂]·20H₂O and [Cu(dien)(Hdien)]₂[W₄S₄(CN)₁₂]·8H₂O were obtained by evaporating water-ammonia solutions containing K₆[W₄S₄(CN)₁₂]·2H₂O·2CH₃OH, diethylene triamine, and NiCl₂·6H₂O or CuCl₂·6H₂O. The crystals of the complex compounds were obtained within 3 days. The complex compounds were characterized by IR spectroscopy and by XRD and elemental analysis. XRD data for the complex [Ni(dien)₂]₃[W₄S₄(CN)₁₂]·20H₂O are: triclinic system, , a = 14.671(2) Å, b = 16.448(3) Å, c = 19.814(3) Å, α = 67.841(3)°, β = 68.996(3)°, γ = 67.527(3)°, V = 3961.6(11) ų, Z = 2; for the complex [Cu(dien)(Hdien)]₂[W₄S₄(CN)₁₂]·8H₂O: monoclinic system, C2/c, a = 37.4290(1) Å, b = 17.7370(1) Å, c = 25.7370(2) Å, β = 105.3840(2)°, V = 16474.02(16) ų, Z = 12. Original Russian Text Copyright ? 2005 by I. V. Kalinina, D. G. Samsonenko, Z. A. Starikova, A. A. Korlyukov, J. Lipkowski, V. P. Fedin, and M. Yu. Antipin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 1, pp. 139–148, January–February, 2005.     

Zinc(II) complex of the edta bis(tyrosine) chelating agent

The synthesis and results of X-ray structural analysis for a novel zinc(II) compound, Zn(O₁₂N₄C₂₈H₃₂)·₆H₂O, are reported. The compound is triclinic, P1, with unit cell parameters a = 11.0906(3) Å, b = 13.1404(3) Å, c = 14.0725(3) Å; β = 89.910(1)°. In contrast to the analogous Cu(II) complex, the unit cell contains two independent molecules of the Zn(II) complex and twelve independent molecules of water. The text was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 48, No. 4, pp. 760–763, July–August, 2007.     

Crystal structure of a new mononuclear complex of Mn(II) with a bbbi ligand (bbbi = 1,4-bis(benzimidazol-1-yl)-2-butene)

A new mononuclear complex Mn(bbbi)₂(H₂O)₄(ClO₄)₂·(bbbi)₂·(H₂O)₂ 1 (bbbi = 1,4-bis(benzimidazol-1-yl)-2-butene) is synthesized under hydrothermal conditions and characterized by IR spectroscopy, elemental analysis, and single crystal X-ray structural analysis. Crystal data for 1: triclinic, , a = 8.8478(7) ?, b = 15.0550(11) ?, c = 16.4310(12) ?, α = 108.657(7)°, β = 104.044(7)°, Γ = 99.317(7)°, V = 1942.2(3) ?³, Z = 1, final R = 0.0621. Each manganese atom is octahedrally coordinated by four aqua ligands and two nitrogen atoms of two distinct bbbi ligands. The molecule is stabilized by hydrogen bonding and π…π interactions.