A. V. Virovets

Triangular M3Se74+ and M3Se44+ complexes (M = Mo, W). An X-ray study of Mo3Se7(Et2NCS2)4 and W3Se7(Et2NCS2)4

Abstract New methods for the synthesis of triangular M 3 Se 7 4+ and M 3 Se 4 4+ complexes soluble in organic solvents have been developed which proceed from polymeric M 3 Se 7 X 4 (M = Mo, W; X = Cl, Br). Heating of Mo 3 Se 7 Cl 4 in a PPh 4 Cl melt has produced the (PPh 4 ) 2 Mo 3 Se 7 Cl 6 salt. Selenobromide complexes of molybdenum and tungsten are less stable and have been converted to M 3 Se 7 (dtc) 4 complexes by reacting them with NaS 2 NCEt 2 ·3H 2 O (Nadtc·3H 2 O) in CH 3 CN. The structure of M 3 Se 7 (dtc) 4 (M = Mo, W) has been determined by X-ray structural analysis: a = 16.728(5), b =18.604(7), c =13.324(3) A, β=99.12(3)°, Z =4, P 2 1 / c , R F =0.1344 for W 3 Se 7 (dtc) 4 ; a =16.652(5), b =18.614(8), c =13.337(3) A, β=99.11(2)°, Z =4, P 2 1 / c , R F =0.0628 for Mo 3 Se 7 (dtc) 4 . Heating of M 3 Se 7 X 4 in a melt of 1,10- phenanthroline (phen) produces salts containing M 3 Se 7 (phen) 3 4+ with different anions (Cl − , Br − , ZnCl 4 2− , ZnBr 4 2− ). The action of phosphines on M 3 Se 7 4+ complexes gave M 3 Se 7 4+ complexes Mo 3 Se 4 (dtc) 4 (PPh 3 ) and Mo 3 Se 4 (dppe) 3 Cl 4 (dppe is Ph 2 PCH 2 CH 2 PPh 2 ).

Primitive cubic packing of anions in Cs4[Re6Te8(CN)6]· 2H2O and Ba2[Re6Te8(CN)6] · 12H2O crystals

Crystal structures of Cs4[Re6Te8(CN)6]·2H2O (1) and Ba2[Re6Te8(CN)6]· 12H2O (2) are determined. Crystals 1 are orthorhombic, a = 14,282(1), b = 12.910(1), c = 18.040(1) Å, Vcell = 3326.3(8) Å3, space group Pbcn, Z = 4, dcalc = 5.715 g/cm3, R(F) = 0.0482 for 3193 Fhkl > 4σ(F). Crystals 2 are triclinic, a = 9.671(3), b = 9.697(4), c = 11.039(4) Å, α = 89.86(3), β = 72.34(3), γ = 82.46(3)∘, Vcell = 977.2(6) Å3, space group P1, Z = 1, dcalc = 4.733 g/cm3, R(F) = 0.0490 for 3226 Fhkl > 4σ(F). In both structures, the [Re6Te8(CN)6]4− anions form a distorted primitive cubic packing with distances between the centers 9.02-9.63 Å in 1 and 9.70-11.04 Å in 2. The Cs+ cations in 1 lie near the face centers of the cubes formed by the onions. In 2, cation pairs (Ba2+)2 bonded to two solvate water molecules are formed; the pairs lie at the centers of the anion cubes. In structures 1 and 2, there are shortened contacts between the tellurium atoms belonging to the neighboring anions (3.75-4.09 and 3.95-4.22 Å, respectively).

Diethyldithiocarbamate triangular thio complexes of molybdenum : synthesis and an X-ray structural study of [Mo3S7(S2CNEt2)3]Cl

Abstract Heating of Mo3S7(S2CNEt2)4 (1) in 1,2-dichloroethane has afforded the [Mo3S7(S2CNEt2)3]Cl (2) complex which was characterized by elemental analysis, IR, Raman and PMR data. The structure of 2 was established by X-ray structural analysis. The average MoMo distance is 2.721(2) A, and the S-S distance of the μ2-S2 ligand is 2.041(6) A. The outer sphere chlorine atom is separated from the axial sulfurs of the μ2-S2 ligands by 2.97–3.05 A. Complexes 1 and 2 are 1:1 electrolytes in DMF (1) and in 1,2-dichloroethane (2).

Coordination-Induced Condensation of [Ta6O19]8–: Synthesis and Structure of [{(C6H6)Ru}2Ta6O19]4– and [{(C6H6)RuTa6O18}2(μ-O)]10−

Reaction of [(C6H6)RuCl2]2 and Na8[Ta6O19] gives two new hybrid organometallic POM complexes, Na10[{(C6H6)RuTa6O18}2(μ-O)]·39.4H2O (Na10-1) and Na4(trans-[{(C6H6)Ru}2Ta6O19]·20H2O (Na4-2). In both cases the half-sandwich fragments {(C6H6)Ru}(2+) are coordinated as additional vertices to the {Ta3(μ2-O)3} triangles of the hexatantalate. According to NMR and ESI-MS data, the dimeric complex [{(C6H6)RuTa6O18}2(μ-O)](10-) dissociates in water with the formation of monomeric [(C6H6)RuTa6O19](6-) species (1a). X-ray structural characterization and aqueous speciation of the complexes by (13)C, (1)H, and DOSY NMR; ESI-MS; and capillary electrophoresis (CE) have been carried out.

23-Electron Re6 metal clusters: syntheses and crystal structures of (Ph4P)3[Re6S8(CN)6], (Ph4P)2(H)[Re6Se8(CN)6]·8H2O, and (Et4N)2(H)[Re6Te8(CN)6]·2H2O

The cluster anions [Re6X8(CN)6]34– (X = S, Se, or Te) containing 23 cluster valence electrons in the Re6 octahedron were synthesized and isolated as salts with organic cations. The crystal structures of the (Ph4P)3[Re6S8(CN)6], (Ph4P)2(H)[Re6Se8(CN)6]·8H2O, and (Et4N)2(H)[Re6Te8(CN)6]·2H2O clusters were solved by X-ray diffraction analysis. Removal of one electron has virtually no effect on the geometry and interatomic distances in the cluster anion but leads to a substantial change in the electronic spectrum and to an increase in stretching vibration frequencies νCN compared to those of the [Re6X8(CN)6]4– anions.

Crystal Structure of the Ca2+ Supramolecular Complex with Cucurbituryl {[Ca(H2O)3(HSO4)(CH3OH)]2(C36N24O12H36)}(HSO4)2 · 4H2O

AbstractThe calcium(II) supramolecular complex with cucurbituryl of composition {[Ca(H2O)3(HSO4)(CH3OH)]2(C36N24O12H36)}(HSO4)2 · 4H2O is obtained by slow diffusion of methanol into a calcium(II) solution in 2 M H2SO4; its crystal structure is determined by X-ray diffraction analysis. The crystals are triclinic, a = 10.4030(9) Å, b = 11.936(1) Å, c = 15.119(1) Å, α = 69.829(6)°, β = 72.019(5)°, γ = 70.171(7)°, V = 1618.1(2) Å3, space group P

Synthesis and crystal structures of [UO2(C6H4NO2)2(C6H5NO2)] and [UO2SO4(C6H5NO2)(H2O)] · H2O

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Syntheses and X-ray structures of a series of V2S4(RCS2)4 (R=alkoxy, dialkylamino) complexes

, Z = 1, ρcalcd = 1.754 g/cm3. The crystal structure is a pseudohexagonal packing of {[Ca(H2O)3(HSO4)(CH3OH)]2(C36N24O12H36)}2+∞ cylinders shifted by half translation along the a axis. The cylinders are linked via hydrogen bonds, with the crystallization water molecules and HSO–4 anions arranged in the channels.