Volatile ZnPhen(S2CNEt2)2 and MnPhen(S2CNEt2)2 complexes and the MnZn2Phen3(S2CNEt2)6 phase: Thermal behavior and crystal and molecular structures of two modifications of ZnPhen(S2CNEt2)2

Two crystal modifications, I and II, of the ZnPhen(S₂CNEt₂)₂ complex have been isolated. According to XRD data, the single crystals of I are triclinic with a=9.745(2), b=10.252(2), c=14.331(3) Å, α=99.18(2), β=91.01(2), γ=113.28(2)°, V=1293.2(4) ų, space group P1, Z=2, d_calc=1.401 g/cm³. The crystals of II are monoclinic with a=7.220(6), b=18.095(2), c=19.050(4) Å, β=95.85(2)°, V=2475.8(7) ų, space group C2/c, Z=4, d_calc=1.461 g/cm³. In both modifications, the structure is formed by monomer molecules with a distorted octahedral environment of the zinc atom. All atoms in I are in the general position; in II, the atoms are linked by the twofold rotation axis. It is shown by X-ray phase analysis (XRPA) that the MnPhen(S₂CNEt₂)₂ complexes (III) are isostructural to modification I of the ZnPhen(S₂CNEt₂)₂ complex, which underlies the synthesis of a solid solution of these complexes, MnZn₂Phen₃(S₂CNEt₂)₆ (phase IV). It is found that MPhen(S₂CNEt₂)₂ (M=Zn²⁺, Mn²⁺) and phase IV quantitatively sublime when heated in vacuum. Thermolysis of III in argon yields manganese(II) sulfide of cubic modification; the main product of thermolysis of phase IV is a solid solution of Zn_xMn_1?xS of hexagonal modification.     

Molecular Packing in the Crystal Structures of the Mixed-Ligand Complexes [CdPhen{(i-C4H9)2PS2}2] and [Cd(2,2′-Bipy){(i-C4H9)2PS2}2]

Single crystals of the mixed-ligand complex compounds of Cd(i-Bu₂PS₂)₂ with Phen and 2,2-Bipy have been obtained. The crystal structures of the complexes [CdPhen{(i-C₄H₉)₂PS₂}₂] (I) and [Cd(2,2-Bipy){(i-C₄H₉)₂PS₂}₂] (II) were determined by X-ray diffraction (CAD-4 diffractometer, MoK radiation, 1739 F _{F hkl} , R = 0.0417 for I and 2612 F _hkl , R = 0.0442 for II). Monoclinic crystals with unit cell parameters a = 15.640(3), b = 20.797(4), c = 11.559(2) , = 111.21(3)°, V = 3505(1) ³, Z = 4, d _calc = 1.348 g/cm³, space group (I); a = 14.737(3), b = 20.918(4), c = 11.517(2) , = 105.53(3)°, V = 3421(1) ³, Z = 4, d _calc = 1.334 g/cm³, space group (II). The structures consist of discrete monomer molecules. The coordination polyhedra of the Cd atoms are distorted octahedra formed by four S atoms of two cyclic bidentate ligands i-Bu₂ and two N atoms of the cyclic bidentate ligands — Phen or 2, -Bipy molecules. The interaction between molecules I and II in the structures and the packing modes are considered.     

Crystal Structure of Ternary Molybdate Rb5FeHf(MoO4)6 — a New Phase in the Rb2MoO4-Fe2(MoO4)3-Hf(MoO4)2 System

Physicochemical analysis (XRPA, DTA) was used to study phase equilibria in a ternary salt system Rb₂MoO₄-Fe₂(MoO₄)₃-Hf(MoO₄)₂ in the subsolidus region. Ternary molybdates with compositions 5:1:3, 5:1:2, and 1:1:1 have been found and synthesized. Crystal and thermal characteristics have been determined. Single crystals of the ternary molybdate Rb₅FeHf(MoO₄)₆ with a composition of 5:1:2 were grown. The crystal structure of the compound was solved using X-ray diffractometry (CAD-4 automatic diffractometer, MoK _α radiation, 1766 F(hkl), R = 0.0298). Hexagonal crystals with unit cell dimensions: a = b = 10.124(1) Å, c =15.135(3) Å, V = 1343.4(4) ų, Z = 2, ρ_calc = 4.008 g/cm³, space group P6₃. The mixed three-dimensional framework of the structure is formed from two sorts of MoO₄ tetrahedra and Fe and Hf octahedra linked through their common O-vertices. Rubidium atoms of three varieties occupy the large voids of the framework.Original Russian Text Copyright © 2004 by B. G. Bazarov, R. F. Klevtsova, A. D. Tsyrendorzhieva, L. A. Glinaskaya, and Zh. G. Bazarova__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1038–1043, November–December, 2004.     

Monodentate and Bridging Bidentate Functions of 4,4′-Bipyridine in the Crystal Structures of [Zn(4,4′-Bipy){(n-C3H7)2NCS2}2] and [Zn2(4,4′-Bipy){(n-C3H7)2NCS2}4]

The structures of the mixed-ligand complexes Zn(4,4-Bipy){(n-C₃H₇)₂NCS₂}₂ (I) and Zn₂(4,4-Bipy){(n-C₃H₇)₂NCS₂}₄ (II) were determined by single crystal X-ray diffractometry (CAD-4 diffractometer, MoK radiation, 2479 and 1616 F_hkl, R = 0.0550 and 0.0523). The crystals are monoclinic with cell parameters a = 16.560(2), b = 11.423(1), c = 15.319(2) , = 94.27(1)°, V = 2889.8(6) ³, Z = 4, space group P2₁/c (for I) and a = 8.515(1), b = 10.965(1), c = 27.816(3) , = 95.860(1)°, V = 2583.5(5) ³, Z = 2, space group P2₁/n (for II). The structure of I is composed of discrete mononuclear molecules; the structure of II consists of discrete centrosymmetric binuclear molecules. The coordination polyhedra of the Zn atoms (c.n. 5) are formed by four S atoms of the two cyclic bidentate dithiocarbamate ligands and the N atom of the 4,4-Bipy ligand, which is monodentate in I and bridging bidentate in II. Molecular packings and interactions in the structures are considered.     

Molecular Packing in the Crystal Structures of Mixed-Ligand Complexes [ZnPhen{(i-C4H9)2PS2}2] and [Zn(2,2′-Bipy){(i-C4H9)2PS2}2]

Volatile mixed-ligand complexes of Zn(i-Bu₂PS₂)₂ with Phen and 2,2-Bipy have been synthesized. The crystal structures of the complexes ZnPhen{(i-C₄H₉)₂PS₂}₂ and Zn(2,2-Bipy){(i-C₄H₉)₂PS₂}₂ were determined by single crystal X-ray diffractometry (CAD-4 diffractometer, MoK radiation, 2100 F_hkl, R = 0.0423 for the first complex and 2003 F_hkl, R = 0.0486 for the second). The crystals are monoclinic with cell dimensions a = 17.580(4), b = 9.969(2), c = 19.175(4) , = 90.33(3)°, V = 3360(1) ³, Z = 4, d _calc = 1.313 g/cm³, space group P2/n (for the Phen complex); a = 24.219(5), b = 11.386(2), c = 24.916(5) , = 97.70(3)°, V = 6809(2) ³, Z = 8, d _calc = 1.249 g/cm³, space group C2/c (for the 2,2-Bipy complex). The complexes are constructed from discrete monomer molecules. The coordination polyhedra of the Zn atoms are distorted tetrahedra formed by two S atoms of the two monodentate i-Bu₂PS ₂ ^- ligands and two N atoms of the cyclic bidentate Phen or 2,2-Bipy molecules. Intermolecular interactions and packings in the structures are analyzed.     

Synthesis and crystal structure of a molybdovanadate with a Keggin-type anion

Institute of Inorganic Chemistry, Academy of Sciences of the USSR, Siberian Branch. Institute of Chemical Sciences, Academy of Sciences of the Kazakh SSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 31, No. 6, pp. 97–103, November–December, 1990.     

Synthesis and crystal structural study of ternary molybdate NaMg3In(MoO4)5

We have synthesized single crystals of a temary molybdate NaMg₃In(MoO₄)₅ and cam'ed out an X-ray structural study (a KM-4 automatic difiactometer, MoK, radiation, 4503 F, R = 0.047). The triclinic unit cell dimensions are a = 7.0476(7), b = 17.935(2), c = 6.9849(7)Å, = 87.650(9), = 100.980(8), = 92.510(9)°, V= 865.5(2) A³, Z = 2, and space group P^–1. The crystal structure involves MoO₄ tetrahedra and (Mg, In)0₆ octahedra forming a three-dimensional framework with Na atoms located in its cavities. The compound melts at 990°C with decomposition.Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Institute of Physics, Siberian Branch, Russian Academy of Sciences. Buryatian Institute of Natural Sciences, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 5, pp. 147–151, September–October, 1993.Translated by T. Yudanova     

Synthesis and crystal structure of ternary molybdate compound K<Subscript>5</Subscript>Pb<Subscript>0.5</Subscript>Hf<Subscript>1.5</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>6</Subscript>

Single crystals of triple molybdate of composition 5:1:3 K₅Pb_0.5Hf_1.5(MoO₄)₆ have been grown and their crystal structure has been solved from X-ray diffraction data (an automated diffractometer X8 APEX, MoK _α -radiation, 2173 F(hkl), R = 0.0321). Trigonal unit cell parameters are: a = b = 10.739(2) Å, c = 37.933(9) Å; V = 3789(1) ų, Z = 6, ρ_calc = 4.014 g/cm³, space group \(R\bar 3\). Three-dimensional mixed framework of the structure is formed by two types of MoO₄ tetrahedra and Pb and Hf octahedra linking via common O-vertices. Potassium atoms of three types occupy large vacancies in the framework.     

Synthesis and Structure of Copper(II) Complexes with Methyl [(Pyrazolo-1-carbothioyl)-amino]propionate Derivatives

Methyl 3-[(3,5-dimethylpyrazole-1-carbothioyl)-amino]propionate (L¹) and the optically active derivative of natural monoterpene (+)-3-carene, (3bS,4aR)-3-[(3,4,4-trimethyl-3b,4,4a,5-tetrahydro-cyclopropa[3,4]cyclopenta[1,2-c]pyrazole-1-carbothioyl)-amino]propionate (L²), are synthesized. The paramagnetic CuL¹Cl₂ (I) and [Cu₂L² ₂Cl₄] (II) complexes are obtained. According to the X-ray diffraction data, in mononuclear complex I, the L¹ molecule performs a bidentate-cyclic function due to the coordination of the S atom of the C=S group and the N atom of the pyrazole cycle. The CuCl₂NS coordination polyhedron is a distorted tetrahedron. Two molecules of complex I form an associate due to weak Cu···S interactions. Compound II is binuclear due to the bridging function of two Cl^- ions, and analogous functions of the L¹ and L² ligands. The coordination polyhedron in complex II is CuCl₃NS. The _eff values for compounds I and II are equal to 1.81 and 1.79 _B, respectively, and are constant in the interval from 78 to 300 K, indicating that noticeable exchange interactions between unpaired electrons of the Cu²⁺ ions are absent. The EPR spectra of the complexes in the solid phase are examined.