Synthesis, structure, and thermal decomposition of [H2(4,4′-Bipy)][In(H2O)2(NCS)4]2 and [HUr]2[In(H2O)(NCS)5] · 2H2O

The reaction of indium thiocyanate with bipyridine (4,4-Bipy) and urotropine (Ur) gave [H₂(4,4′-Bipy)][In(H₂O)₂(NCS)₄]₂ (I) and [HUr]₂[In(H₂O)(NCS)₅] · 2H₂O (II), which were identified using elemental analysis, IR spectra, and thermogravimetric analysis. The thermal decomposition of compound I and II ends at 650 and 640°C, respectively, and gives In₂O₃. X-Ray diffraction analysis of compound I showed that complex anions in the crystal form chains through O-H…S hydrogen bonds. The anion chains form a close packing of columns with bipyridine cations located in the voids. Original Russian Text ? S.P. Petrosyants, A.B. Ilyukhin, V.A. Ketsko, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 6, pp. 951–955.     

[COH(NH2)2]2[Cu(pic)2(ClO4)2]的合成与晶体结构

The title compound was synthesized by reaction of Cu(ClO₄)₂， picolinic acid and carbamide in C₂H₅OH/CH₃CN solution， and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system， space group Pbca with a=14.0481(8)， b=9.0130(5)， c=18.626(1)?， V=2358.3(2)?³， Z=4， D_x=1.771g·cm^-3， μ=1.235mm^-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane， while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances， resulting in a 4+2 elongated octahedral environment. In the compound， there also exist two protonated carbamide cations for charge balance. CCDC： 195354.     

Self-assembly and crystal structures of two heteronuclear complexes with [Ag2(μ-dppm)2(MeCN)2](SbF6)2 and [Bu4N]2[M(mnt)3] (M=Mo, W) as components

Two heteronuclear complexes Mo₂Ag₄(μ-dppm)₄(mnt)₆ · 6MeCN (1) and WAg₂(μ-dppm)₂(mnt)₃ · MeCN (2) were synthesized by self-assembly with [Ag₂(μ-dppm)₂(MeCN)₂](SbF₆)₂ and [Bu₄N]₂[Mmnt)₃] (M=Mo or W, dppm=bis(diphenylphosphino)methane, mnt²⁻ = cis-1,2-dicyanoethylene-1,2-dithiolate) as components and characterized by IR spectra, elemental analysis, ¹H NMR spectra, ³¹P NMR spectra and u.v.–vis spectra. The crystal structures of the two complexes were determined by X-ray analysis.     

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.     

Crystal structure of [Pd(NH3)4]3[Ir(NO2)6]2·H2O

A single crystal of [Pd(NH₃)₄]₃[Ir(NO₂)₆]₂·H₂O double complex salt is studied by X-ray diffraction. Crystallographic characteristics are as follows: a = 21.0335(5) ?, b = 8.0592(2) ?, c = 21.3452(5) ?, β = 91.254(1)°, V = 3617.43(15) ?³, P2₁/c space group, Z = 4, d _x = 2.714 g/cm³. Single-layer pseudohexagonal packing of complex anions is determined along the [−1 0 1] direction in the structure. Complex cations and crystallization water molecules are located between the mentioned layers.     

Structure and synthesis of nitrosoruthenium trans -diammines [Ru(NO)(NH3)2Cl3] and [Ru(NO)(NH3)2(H2O)Cl2]Cl·H2O

A DTA study of thermal decomposition of (NH₄)₂[Ru(NO)Cl₅] in helium atmosphere has been carried out, a synthetic procedure for preparation of the trans-diammine complex mer-[Ru(NO)(NH₃)₂Cl₃] (I) with yield ∼70% has been developed. On re-crystallization of I from aqueous solution a trans-aquanitroso complex [Ru(NO)(NH₃)₂Cl₂(H2O)]Cl·H₂O (II) has been isolated. The structures of the compounds have been determined by single crystal X-ray diffraction: space group Pbcn, a = 6.607(1) ? b = 11.255(2) ? c = 9.878(2) ? (I) and space group Ima2, a = 8.3032(3) ?, b = 8.0890(2) ?, c = 15.9192(5) ? II). Original Russian Text Copyright ? 2008 by M. A. Il’in, V. A. Emel’yanov, and I. A. Baidina __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 6, pp. 1128–1136, November–December, 2008.     

Stepwise addition of CuBr at [(dtc)2Mo2(S)2(μ-S)2] (dtc=diethyldithiocarbamate): syntheses and crystal structures of two Mo/Cu/S clusters [(dtc)2Mo2(μ3-S)(μ-S)3(CuBr)] and [(dtc)2Mo2(μ3-S)4(CuBr)2]

Reactions of [(dtc)₂Mo₂(S)₂(μ-S)₂] with one or two equivalents of CuBr in CH₂Cl₂ afforded two new heterobimetallic sulfide clusters, [(dtc)₂Mo₂(μ₃-S)(μ-S)₃(CuBr)] (1) and [(dtc)₂Mo₂(μ₃-S)₄(CuBr)₂] (2). Both compounds were characterized by elemental analysis, IR, UV-vis and X-ray analysis. Compound 1 contains a butterfly-shaped Mo₂S₄Cu core in which one CuBr unit is coordinated by one bridging S and two terminal S atoms of the [(dtc)₂Mo₂(S)₂(μ-S)₂] moiety. In the structure of 2, one [(dtc)₂Mo₂(S)₂(μ-S)₂] moiety and two CuBr units are held together by six Cu-μ₃-S bonds, forming a cubane-like Mo₂S₄Cu₂ core.     

Pyridine-2-thione (pySH) derivatives of silver(I): Synthesis and crystal structures of dinuclear [Ag2Cl2(μ-S-pySH)2(PPh3)2] and [Ag2Br2(μ-S-pySH)2(PPh3)2] complexes

Reaction of silver(I) halides with PPh₃ in acetonitrile and then with pyridine-2-thione (pySH) chloroform (1:1:1 molar ratio) has yielded sulfur bridged dimers of general formula, [Ag₂X₂(μ-S-pySH)₂(PPh₃)₂] (X = Cl, 1, Br, 2). Both these complexes have been characterized using analytical data, NMR spectroscopy and single crystal X-crystallography. The central Ag₂S₂ cores form parallelograms with unequal Ag–S bond distances (2.5832(8), 2.7208(11) Å) in 1 and (2.6306(4), 2.6950(7) Å) in 2, respectively. The Ag?Ag contacts of compounds 1 and 2 are 3.8425(8) and 3.8211(4) Å, respectively. The angles around Ag (in the range 87.19(2)–121.71(2)° in 1 and 87.81(2)–121.53(2)° in 2) reveal highly distorted tetrahedral geometry. There are inter dimer π–π stacking interactions between pyridyl rings (inter ring distances of 3.498 and 3.510 Å in complexes 1 and 2, respectively). The solution state ³¹P NMR spectroscopy has shown the existence of both monomers and dimers. The studies reveal relatively weaker intramolecular –NH?Cl hydrogen bonding in case of AgCl vis-à-vis that in CuCl which favored both a monomer and a dimer with AgCl, and only a monomer with CuCl.     

Synthesis and structures of nine-coordinate K[SmIII (Edta)(H2O)3] · 2H2O and Ten-Coordinate K2[SmIII(Pdta)(H2O)2]2 · 4.5H2O complexes

The title complexes, K[Sm^III(Edta)(H₂O)₃] · 2H₂O(I)(H₄Edta = ethylenediamine-N,N,N′,N′-tetraacetic acid) and K₂[Sm^III(Pdta)(H₂O)₂]₂ · 4.5H₂O (II) (H₄Pdta = propylenediamine-N,N,N′,N′-tetraacetic acid), were prepared and their compositions and structures were determined by elemental analyses and single-crystal X-ray diffraction techniques, respectively. Complex I has a mononuclear structure, and the Sm³⁺ ion is nine-coordinated by an Edta ligand and three water molecules, yielding a pseudo-monocapped square antiprismatic conformation, and the complex crystallizes in the orthorhombic crystal system with space group Fdd2. The crystal data are as follows: a = 19.84(5), b = 35.58(9), c = 12.15(3) ?, V = 8580(38) ?³, Z = 16, ρ _c = 1.925 g/cm³, μ = 3.010 mm⁻¹, F(000) = 4976, R = 0.0252, and wR = 0.0560 for 3510 observed reflections with I ≥ 2σ(I). Complex II has a binuclear structure and the Sm³⁺ ion is ten-coordinated by a Pdta ligand, two oxygen atoms from a carboxylic group of adjacent Pdta ligand and two water molecules, yielding a distorted bicapped square antiprismatic prism. The complex crystallizes in the triclinic crystal system with space group P $ \bar 1 $ \bar 1 . The crystal data are as follows: a = 8.9523(15), b = 10.7106(15), c = 11.6900(19) ?, α = 80.613(5)°, β = 80.397(5)°, γ = 76.530(4)°, V = 1065.7(3) ?³, Z = 1, ρc = 1.970 g/cm³, μ = 2.532 mm⁻¹, F(000) = 1620, R = 0.0332 and wR = 0.0924 for 5390 observed reflections with I ≥ 2σ(I).     

Double complex salts [Pd(NH3)4]3[Rh(NO2)6]2, [Pd(NH3)4]3[Rh(NO2)6]2·H2O as promising precursors to prepare Pd-Rh nanoalloys

Two new double complex salts [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂ (I) and [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂·H₂O (II) are synthesized and characterized. The techniques to produce one-phase residues of the salts are developed. The crystallographic data for I: a = 18.915(2) ?, V = 6767.4 ?³, F-43c space group, Z = 8, d _x = 2.548 g/cm³; II: a = 21.160(6) ?, b = 8.085(7) ?, c = 21.363(4) ?, β = 91.71(4)°, V = 3661.1(6) ?³, P2₁/c space group, d _x = 2.357 g/cm³. Thermal properties of the obtained compounds in the hydrogen and helium atmosphere are studied. It is shown that the final product of their decomposition both in the inert and reducing atmosphere is a powder consisting of bimetallic nanosized particles (nanoalloy) of Pd_0.59Rh_0.41 (Fm-3m space group, a = 3.856(2) ?, crystallite size of 8–11 nm).     

Relativistic scalar and spin-orbit density functional calculations of the electronic structure, NICS index and ELF function of the [Re2(CO)8(μ-BiPh)2] and [Re2(CO)8(μ-BiPh2)2] clusters

Relativistic scalar and spin-orbit density functional calculations of the electronic structure, Nucleus-Independent Chemical Shift (NICS) index and ELF function of the [Re₂(CO)₈(μ-BiPh)₂] and [Re₂(CO)₈(μ-BiPh₂)₂] clusters are reported. We show here that the [Re₂(CO)₈(μ-BiPh)₂] cluster has large negative NICS values in the region defined by the Re-Bi-Re-Bi four-membered ring and the ELF function shows significant electron delocalization density in the center of the metallic ring, thus indicating an aromatic cluster. In contrast the Re-Bi-Re-Bi four-membered ring in the [Re₂(CO)₈(μ-BiPh₂)₂] cluster has negligible paratropic ring currents and the ELF function shows a low-density region within the metallic ring indicating that aromaticity is switched off. However, the phenyl ligands in both clusters show the expected aromatic character.     

trans-dinitro- and trans-dinitratoruthenium complexes [RuNO(NH3)2(NO2)2(OH)] and [RuNO(NH3)2(H2O)(NO3)2]NO3·H2O

Methods for the synthesis of trans-diammino complexes [RuNO(NH₃)₂(NO₂)₂(OH)] (I) and [RuNO(NH₃)₂(H₂O)(NO₃)₂](NO₃)·H₂O (II) are suggested. The compounds were studied by IR spectroscopy and X-ray phase and X-ray structural analyses. Crystal data: space group P-1; a = 6.2328(2) ?, b = 11.0488(3) ?, c = 11.0981(4) ?, α = 71.942(1)°, β = 83.291(1)°, γ = 86.877(1)° (I); space group P2₁; a = 6.6290(2) ?, b = 13.4389(5) ?, c = 7.0180(2) ?, β 114.281(1)° (II). Complex II readily lost some part of crystal water on storage in open air. Original Russian Text Copyright ? 2009 by M. A. Il’in, E. V. Kabin, V. A. Emel’yanov, I. A. Baidina, and V. A. Vorob’yov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 2, pp. 341–348, March–April, 2009.     

Two new cyanide-bridged complexes, {[Cu(men)2][Ni(CN)4]}n and [Mn(bpy)2]4[Mo(CN)8]2·0.5MeOH·0.75H2O: Syntheses and crystal structures

Two novel cyano-bridged complexes, {[Cu(men)₂][Ni(CN)₄] _n (1) (men = N,N′-dimethyl-ethylenediamine) and [Mn(bpy)₂]₄[Mo(CN)₈]₂·0.5MeOH·0.75H₂O (2) (bpy = 2,2′-bipyridine) have been synthesized and structurally characterized by IR spectroscopy and X-ray crystallography. The complex 1 has onedimensional zigzag chain structure in which the Ni atom is coordinated by four cyanide groups, and the Cu atom is surrounded by four nitrogen atoms of the two men ligands in equatorial plane and two nitrogen atoms of the bridging cyanide in axial positions; the Cu centre is in a distorted octahedral environment. Owing to weak interactions, complex 1 is self-assembled into two-dimensional network via N-H...N hydrogen bonds. In 2, the basic structural unit is centrosymmetric and contains four Mn centers connected by two octacyanomolybdates via eight cyanide bridges. Each Mo atom is linked via four cyanide groups to four Mn, and the other four cyanide groups are terminal. From X-ray single crystal analysis (room temperature), 1 crystallizes in monoclinic space group P2₁/n with a = 6.7332(7) ?, b = 13.9248(15) ?, c = 9.0869(10) ?, β = 98.4030(10)°, V = 843.05(16) ?³, Z = 2; 2 crystallizes in monoclinic space group P2₁/n with a = 13.886(6) ?, b = 24.116(11) ?, c = 15.263(7) ?, β = 90.175(6)°, V = 5111(4) ?³, Z = 2. Original Russian Text Copyright ? 2009 by X. Chen, P. Yang, S.-L. Ma, S. Ren, M.-Y. Tang, Y. Yang, Z.-J. Guo, and L.-Z. Liu The text was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 50, No. 3, pp. 518–521, May–June, 2009.     

Syntheses,spectral, thermal and structural characterization of dinuclear and polynuclear copper(II) orotate complexes, [Cu2(HOr)2(H2O)4] and [Cu(μ-HOr)(ba)2]n

The novel catena-poly-μ-orotatobis(butylamine)copper(II), [Cu(μ-HOr)(ba)₂]_n (1), and diaqua(orotato)copper(II), [Cu₂(HOr)₂(H₂O)₄] (2), complexes have been prepared and characterized by elemental analysis, magnetic measurements, FT-IR spectroscopy, EPR spectroscopy, thermal analysis and X-ray diffraction. Both complexes crystallize in the monoclinic space group, C2/c in 1 and P2₁/n in 2. In the complexes, the copper(II) ion is chelated by a deprotonated pyrimidine nitrogen atom and a carboxylate oxygen atom of the orotate. While the coordination sphere around Cu(II) is completed by two N atoms from butylamine groups and a carboxylic O atom in the axial position from a neighboring molecule in 1, the square-planar environment of Cu(II) is completed by two water atoms and one axial position is occupied by the carbonyl oxygen atom from the symmetry related molecule in 2. The coordination sphere should be described as a square pyramid and (4+1)-geometry in 1 and 2, respectively. While complex 1 shows a polymeric arrangement, compound 2 has a dimeric arrangement. The non-covalent Cu(II)-π binding force is very important for stabilizing the crystal structure of 2. The thermal decomposition of the complexes has been predicted by the help of thermal analysis (TG, DTG and DTA).     

Synthesis and structures of Cs4[(UO2)2(C2O4)(SO4)2(NCS)2] · 4H2O and (NH4)4[(UO2)2(C2O4)(SO4)2(NCS)2] · 6H2O

Single crystals of Cs₄[(UO₂)₂(C₂O₄)(SO₄)₂(NCS)₂] · 4H₂O (I) and (NH₄)₄[(UO₂)₂(C₂O₄)(SO₄)₂(NCS)₂] · 6H₂O (II) have been synthesized and studied by X-ray diffraction. The crystals of both compounds are orthorhombic with the space group Pbam, Z = 2, and unit cell parameters a = 12.0177(3) ?, b = 18.6182(5) ?, c = 6.7573(10) ?, R = 0.0376 (I); a = 11.6539(9) ?, b = 18.3791(13) ?, c = 6.7216(5) ?, R = 0.0179 (II). The main structural units of crystals I and II are [(UO₂)₂(C₂O₄)(SO₄)₂(NCS)₂]⁴⁻ chains belonging to the crystal-chemical group A₂K⁰²B₂²M₂¹ (A = UO₂²⁺, K⁰² = C₂O₄²⁻, B² = SO₄²⁻, M¹ = NCS⁻) of the uranyl complexes. The uranium-containing chains are joined into a three-dimensional framework due to a system of electrostatic interactions with the cesium or ammonium ions in the structure of I. In the structure of II, this framework is additionally stabilized by hydrogen bonds involving the outer-sphere water molecules and ammonium ions. Original Russian Text ? I.V. Medrish, A.V. Virovets, E.V. Peresypkina, L.B. Serezhkina, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 7, pp. 1115–1120.     

[Ni(dien)2]2[Mn(NCS)6]·H2O的合成、晶体结构

The crystal of [Ni(dien)₂]₂[Mn(NCS)₆]·H₂O was synthesized and the structure of its single crystal was determined by X-ray diffraction. The crystal is monoclinic system, space group P2₁/c with a=16.544(3),b=15.137(2), c=17.334(3)?, β=99.90(1)°, V=4276.3(12)?³, Z=4, D_c=1.479g·cm^-3, M_r=951.55, F(000)=1998, μ=1.489mm^-1, R=0.0399, R_w=0.0958. IR was also determined.     

Syntheses of the eight-coordinate NH4[ErIII(Cydta)(H2O)2] · 4.5H2O and (NH4)2[Er 2III (Pdta)2(H2O)2] · 2H2O complexes and their structural investigation

In this work, the title complexes, NH₄[Er^III(Cydta)(H₂O)₂] · 4.5H₂O (I) (H₄Cydta = trans-1,2-cyclo-hexanediamine-N,N,N′,N′-tetraacetic acid) and (NH₄)₂[Er₂^III(Pdta)₂(H₂O)₂] · 2H₂O (II) (H₄Pdta= propylene-diamine-N,N,N′,N′-tetraacetic acid), were prepared, respectively, and their composition and structures were determined by elemental analyses and single-crystal X-ray diffraction techniques. Complex I selects a mononu-clear structure with pseudosquare antiprismatic geometry crystallized in the triclinic crystal system with space group $ P\bar 1 $ P\bar 1 and the central Er³⁺ ion is eight-coordinated by the hexadentate Cydta ligand and two water molecules. The crystal data are as follows: a = 8.568(3), b = 10.024(3), c = 14.377(4) ?, α = 88.404(4)°, β = 75.411(4)°, γ = 88.332(4)°, V = 1194.2(6) ?³, Z = 1, ρ _c = 1.793 g/cm³, μ = 3.586 mm⁻¹, F(000) = 648, R = 0.0257, and wR = 0.0667 for 4169 observed reflections with I ≥ 2σ(I). Complex II is eight-coordinated as well, which selects a binuclear structure with two pseudosquare antiprismatic geometry and crystallizes in the monoclinic crystal system with space group P2₁/n. The central Er³⁺ ion is coordinated by two nitrogens and four oxygens from one hexadentate Pdta ligand. Besides, two oxygens come from one carboxylic group of the neighboring Pdta ligand and one water molecule, respectively. The crystal data are as follows: a = 12.7576(8), b = 9.3151(6), c = 14.3278(9) ?, β = 96.1380(10)°, V = 1692.93(19) ?³, Z = 4, ρ _c = 2.054 g/cm³, μ = 5.015 mm⁻¹, F(000) = 1028, R= 0.0228, and wR = 0.0534 for 2984 observed reflections with I ≥ 2σ(I).     

对自旋交叉化合物[Fe(dpq)(py)2(NCS)2]·H2O·py和[Fe(dpq)(py)2(NCSe)2]·1.5H2O的研究

为了研究配体修饰对自旋交叉现象的影响,我们合成了两个Fe(Ⅱ)自旋交叉的配合物[Fe(dpq)(py)₂(NCS)₂]·H₂O·py和[Fe(dpq)(py)₂(NCSe)₂]·1.5H₂O,(dpq=二吡嗪[2,3-f:2′3′-h]喹喔啉,py=吡啶)。通过对这两个配合物磁性质和穆斯堡尔谱的研究,发现和用邻啡咯啉配体合成的配合物比较,配体的修饰对自旋交叉性质以及其临界温度     

Crystal structure of metal-organic coordination polymers [Cu(bpy)2(H2O)2](NO3)2·4.5C2H5OH and [Cu2(bpy)(H2O)(L-pha)2](NO3)2·H2O

Two metal-organic coordination polymers [Cu(bpy)₂(H₂O)₂](NO₃)₂·4.5C₂H₅OH (1) and [Cu₂(bpy)(H₂O)(L-pha) ₂](NO₃)₂·H₂O (2) (L-Hpha = L-phenylalanine, bpy = 4,4′-bipyridyl) are prepared by slow evaporation of an aqueous alcoholic solution of copper nitrate, L-phenylalanine, and 4,4′-bipyridyl. The structure and composition of the obtained compounds are determined by single crystal XRD. The framework of compound 1 is positively charged and forms two types of intersecting channels. Compound 2 is a homochiral metal-organic coordination polymer whose structure contains L-phenylalanine anions.