Tl2SnS3 — ein Thiostannat mit 1 ∞ -[SnS 3 2− ]-Ketten

Black, fibre-like crystals of Tl₂SnS₃ were obtained from the melt using high-purity elements. Tl₂SnS₃ is monoclinic, space group C 2/m witha=23.03 (1),b=3.834 (1),c=7.379 (3) Å, =94.07 (5)°;Z=4. The crystal structure was determined from single crystal diffractometer intensity data and refined to a conventionalR of 0.127 for 724 observed reflections. The crystal structure is of a new type. It is characterized by infinite chains, ₁ -[SnS ₃ ^2– ], formed by cornersharing SnS₄-tetrahedra. These chains run along [010], their translation period comprises one tetrahedron (Einerketten). The average Sn — S-distance is 2.397 Å. The Tl⁺-ions separating the thiostannate-chains have different sulfur coordination. The coordination figure of Tl(1) is a bicapped trigonal prism, Tl(2) is in the center of an irregular cube. A comparison of the thiostannate-chains with other simple chains built-up by corner-sharing tetrahedra is given.

Herrn Prof. Dr.Karl Schlögl zum 60. Geburtstag gewidmet.     

Synthesis and Properties of Rb6Mn2O6

Rb₆Mn₂O₆ was prepared via the azide/nitrate route. Stoichiometric mixtures of the precursors (Mn₃O₄, RbN₃ and RbNO₃) were heated in a special regime up to 500 °C and annealed at this temperature for 75 h in silver crucibles. Single crystals have been grown by annealing a mixture with a slight excess of rubidium components at 450 °C for 500 h. According to the single crystal structure analysis, Rb₆Mn₂O₆ is isotypic to K₆Mn₂O₆, and crystallizes in the monoclinic space group P2₁/c with a = 6.924(1) Å, b = 11.765(2) Å, c = 7.066(1) Å, β = 99.21(3)°, 2296 independent reflections, R₁ = 5.23 % (all data). Manganese is tetrahedrally coordinated and two tetrahedra are linked by sharing a common edge, forming a dimer [Mn₂O₆]⁶⁻. The magnetic behavior has been investigated.     

Re-investigation of Barium-Gold(I)-Tetra-Thiostannate(IV), Ba[Au2SnS4], with Short AuI···AuI Separation Showing Luminescence Properties

New investigations combining single crystal- and synchrotron-based powder X-ray diffraction data revealed that Ba[Au₂SnS₄] crystallizes in the orthorhombic crystal system in space group C222₁ instead of P2₁2₁2 as reported earlier. While the principle crystal structure is not altered, there are significant differences of the interatomic distances Au-S and Sn-S. A salient property of this crystal structure is the partial framework composed of AuS₂ dumbbells and SnS₄ tetrahedra to form chains [(Au₂SnS₄)^2–]_∞ propagating in the [100] direction. Within the chains a short Au ··· Au separation of 2.9538(13) Å is observed, while the interchain Au ··· Au separation is longer at 3.383 Å. The Ba²⁺ cation is eightfold coordinated by S^2– anions in a distorted bicapped trigonal prismatic environment BaS₈. These polyhedra share all S^2– anions thus generating a three-dimensional network. This connection Scheme generates voids along [100] hosting [(Au₂SnS₄)^2–]_∞ chains. In addition, the compound has been shown to be luminescent at the blue-green spectral range with emission maximum at approximately 21000 cm^–1.     

Beiträge zum Koordinationsverhalten von Oxidionen in anorganischen Feststoffen. III [1] Mn2P2O7, Mn2P4O12 und Mn2Si(P2O7)2 — Kristallzüchtung,Strukturverfeinerungen und Elektronenspektren von Mangan(II)‐Phosphaten

Contributions on the Bonding Behaviour of Oxygen in Inorganic Solids. III [1] Mn₂P₂O₇, Mn₂P₄O₁₂ und Mn₂Si(P₂O₇)₂ — Crystal Growth, Structure Refinements and Electronic Spectra of Manganese(II) Phosphates By chemical vapour transport reactions in a temperature gradient single crystals of Mn₂P₂O₇ (1050 → 950 °C) and Mn₂P₄O₁₂ (850 → 750 °C) have been obtained using P/I mixtures as transport agent. Mn₂Si(P₂O₇)₂ was crystallized by isothermal heating (850 °C, 8d; NH₄Cl as mineralizer) of Mn₂P₄O₁₂ und SiO₂. In Mn₂Si(P₂O₇)₂ [C 2/c, a = 17.072(1)Å, b = 5.0450(4)Å, c = 12.3880(9)Å, β = 103.55(9)°, 1052 independent reflections, 97 variables, R1 = 0.023, wR2 = 0.061] the Mn²⁺ ions show compressed octahedral coordination (d¯_Mn—O = 2.19Å). The mean distance d¯_Mn—O = 2.18Å was found for the radially distorted octahedra [MnO₆] in Mn₂P₄O₁₂ [C 2/c, Z = 4, a = 12.065(1)Å, b = 8.468(1)Å, c = 10.170(1)Å, β = 119.29(1)°, 2811 independent reflections, 85 variables, R1 = 0.025, wR2 = 0.072]. Powder reflectance spectra of the three pink coloured manganese(II) phosphates have been measured. The spectra show clearly the influence of the low‐symmetry ligand fields around Mn²⁺. Observed d—d electronic transition energies and the results of calculations within the framework of the angular overlap model (AOM) are in good agreement. Bonding parameters for the manganese‐oxygen interaction in [Mn²⁺O₆] chromophors as obtained from the AOM treatment (B, C, Trees correction α, e_σ, e_π) are discussed.     

Crystal structures of seven-coordinate (NH4)2[MnII(edta)(H2O)]·3H2O, (NH4)2[MnII(cydta)(H2O)]·4H2O and K2[MNII(hdtpa)]·3.5H2O complexes

The title compounds, (NH₄)₂[Mn^II(edta)(H₂O)]·3H₂O (H₄edta = ethylenediamine-N,N,N′,N′-tetraacetic acid), (NH₄)₂[Mn^II(cydta)(H₂O)]·4H₂O (H₄cydta = trans-1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid) and K₂[Mn^II(Hdtpa)]·3.5H₂O (H₅dtpa = diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid), were prepared; their compositions and structures were determined by elemental analysis and single-crystal X-ray diffraction technique. In these three complexes, the Mn²⁺ ions are all seven-coordinated and have a pseudomonocapped trigonal prismatic configuration. All the three complexes crystallize in triclinic system in P-1 space group. Crystal data: (NH₄)₂[Mn^II(edta)(H₂O)]·3H₂O complex, a = 8.774(3) ?, b = 9.007(3) ?, c = 13.483(4) ?, α = 80.095(4)°, β = 80.708(4)°, γ = 68.770(4)°, V = 972.6(5) ?³, Z = 2, D _c = 1.541 g/cm³, μ = 0.745 mm⁻¹, R = 0.033 and wR = 0.099 for 3406 observed reflections with I ≥ 2σ(I); (NH₄)₂[Mn^II(cydta)(H₂O)]·4H₂O complex, a = 8.9720(18) ?, b = 9.4380(19) ?, c = 14.931(3) ?, α = 76.99(3)°, β = 83.27(3)°, γ = 75.62(3)°, V = 1190.8(4)?³, Z = 2, D _c = 1.426 g/cm³, μ = 0.625 mm⁻¹, R = 0.061 and wR = 0.197 for 3240 observed reflections with I ≥ 2σ(I); K₂[Mn^II(Hdtpa)]·3.5H₂O complex, a = 8.672(3) ?, b = 9.059(3) ?, c = 15.074(6) ?, α = 95.813(6)°, β = 96.665(6)°, γ = 99.212(6)°, V = 1152.4(7) ?³, Z = 2, D _c = 1.687 g/cm³, μ = 1.006 mm⁻¹, R = 0.037 and wR = 0.090 for 4654 observed reflections with I ≥ 2σ(I). Original Russian Text Copyright ? 2008 by X. F. Wang, J. Gao, J. Wang, Zh. H. Zhang, Y. F. Wang, L. J. Chen, W. Sun, and X. D. Zhang The text was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 49, No. 4, pp. 753–759, July–August, 2008.     

Synthesis and Crystal Structures of Manganese(II) and ­Cobalt(II) Complexes with 2, 6‐Dimethoxybenzoic Acid and Additional N‐Donor Ligands

Three coordination compounds [Mn₃(dmb)₆(H₂O)₄(4, 4′‐bpy)₃(EtOH)]_n ( 1 ) and [M(dmb)₂(pyz)₂ (H₂O)₂] [M^II = Co ( 2 ), Mn ( 3 )] (Hdmb = 2, 6‐dimethoxybenzoic acid, 4, 4′‐bpy = 4, 4′‐bipyridine, pyz = pyrazine) were synthesized and characterized by single‐crystal X‐ray diffraction analysis. Compound 1 consists of infinite 1D polymeric chains, in which the metal entities are bridged by 4, 4′‐bpy ligands. There are four crystallographically independent Mn^II atoms in the linear chain with different coordination modes, which is only scarcely reported for linear polymers. The isostructural crystals of 2 and 3 are composed of neutral mononuclear complexes. In crystal the complexes are combined into chains by intermolecular O–H ··· N hydrogen bonds and π–π interactions between antiparallel pyrazine molecules.     

Characterization of Mixed Crystals in the System Cu2MnxCo1−xGeS4 and Investigations of the Tetrahedra Volumes

In a series of investigations on normal tetrahedral compounds we present mixed crystals in the system Cu₂Mn_xCo_1?xGeS₄ (0 < x < 1) and an inspection of their tetrahedra volumes. Cu₂CoGeS₄ crystallizes tetragonal in a stannite type structure, Cu₂MnGeS₄ crystallizes orthorhombic in the wurtzstannite structure type. The crystal structures of Cu₂CoGeS₄ and Cu₂Mn_0.68Co_0.32GeS₄ were refined from single crystal diffraction data. The refinement of Cu₂CoGeS₄ converged to R = 0.0547 and wR2 = 0.0847 for 299 unique reflections. The refinement of Cu₂Mn_0.68Co_0.32GeS₄ converged to R = 0.0481 and wR2 = 0.0877 for 1556 unique reflections. From these data the tetrahedra volumes of the end members and of Cu₂Mn_0.68Co_0.32GeS₄ are calculated. In Cu₂CoGeS₄ tetrahedra [MS₄] are similar in size. In contrast, the differences of the volumes of the polyhedra [MS₄] in the orthorhombic wurtzite superstructure type compounds Cu₂MnGeS₄ and Cu₂Mn_0.68Co_0.32GeS₄ are significant (M = Cu, Mn, (Mn_0.68Co_0.32), Co, Ge). From x = 0 to x = 0.5 the tetragonal structure type dominates while from x = 0.7 to the Cu₂MnGeS₄ end member the products crystallize in the orthorhombic structure type. Melting points of the mixed crystals decrease linearly with increasing manganese content.     

STRUCTURAL,MAGNETOCHEMICAL, SPECTRAL AND THERMAL PROPERTIES OF TRANS-TETRAKIS(1,2-DIAZOLE) BISBROMOMANGANESE(II)

Abstract

The crystal structure of trans-tetrakis(1,2-diazole)bisbromomanganese(II) was solved by direct methods using single-crystal X-ray (Mo-Kα) diffractometer data and refined to R = 0.054 for 1270 unique reflections with I > 2Δ(I). The compound crystallized from water as almost colourless, monoclinic prisms in space group C2/c (No. 15) with unit cell dimensions a = 14.208(2), b = 9.454(1), c = 15.015(3)Å,β = 118.68(1)°, Z = 4. The structure is formed from [(C₃H₄N₂)₄(Br)₂Mn] molecular units held together through stacking of the 1.2-diazole rings approximately in the b-direction and weak van der Waals forces and hydrogen bonds. The coordination sphere around the Mn²⁺ ion is weakly distorted octahedral with two pairs of trans-positioned 1,2-diazole molecules at distances Mn-N(1) = 2.246(7) and Mn-N(3) = 2.229(6) Å, respectively, in the basal plane and the Br^? ions occupying the apical positions at a distance Mn-Br(1) = 2.729(1)Å. The angles Br(1)-Mn-N(1), Br(1)-Mn-N(3) and N(1)-Mn-N(3) are 91.2(1). 89.6(1) and 87.8(2)°. respectively. The 1,2-diazole rings are practically planar, but slightly tilted (N(1) and N(3) containing rings are at angles of 89.9(3) and 86.4(3)° with respect to the basal coordination plane). The molecular units form columns in the b-direction. The molar magnetic susceptibilities, corrected for diamagnetism by Pascals constants, at 93–303 K show the compound to be of high-spin complex type with a Curie-Weiss equation X'_M = 4.30/(T-3.3) and the reflectance spectrum in accordance with this shows only a very weak shoulder at 23500 cm^?1 corresponding to the ⁶A_1g ± ⁴T_2g transition for the Mn²⁺ ion. The infrared spectrum shows an Mn-Br band at 715 and Mn-N bands at 680, 600 and 580 cm^?1. The thermogravimetric (TG) curve shows the complex to release the 1,2-diazole molecules in two steps in accordance with the structure.     

Das erste Oxomanganat(II): Na14Mn2O9 = Nal4[MnO14]2O

The First Oxomanganate(II): Na₁₄Mn₂O₉ = Na₁₄[MnO₄]₂O Na₁₄Mn₂O₉ crystallizes trigonal, space group P3 , a = b = 6.66₉, c = 9.35₃ Å. The crystal structure han been refined by diffractometer data (1124 undependent reflections) to R = 0.050. Mn²⁺ is surrounded tetrahedrally (Mn? O = 2.09 Å). Effective Coordination Numbers, ECoN, and the Madelung Part of Lattice Energy, MAPLE, are calculated. Na₁₄Mn₂O₉ represents the most kation-rich ternary oxid of the alkali metals.     

Synthesis,crystal structure and properties of a tetrametallic 3-ferrocenyl-2-crotonic acid-bridged manganese(II) complex [Mn2(phen)4(FCA)2](ClO4)2·H2O

The title complex [Mn₂(phen)₄(FCA)₂](ClO₄)₂·H₂O (1) (FCA = dianion of 3-ferrocenyl-2-crotonic acid, phen = 1,10-phenanthroline) has been prepared, and its structure determined by single crystal X-ray diffraction analysis. The structure consists of a dinuclear cation [Mn₂(phen)₄(FCA)₂]²⁺, non-coordinated perchlorate anions and a water molecule. The two Mn^II ions are separated by 4.374 Å in the cation and are dicarboxylate-bridged by carboxylate ligands containing ferrocenyl units. Each FCA is bound to two Mn^II ions through carboxylate oxygens with the syn–anti bridging mode. The Mn^II ion is coordinated in an octahedral N₄O₂ geometry by two chelate phen ligands and two -carboxylate oxygen atoms. Electrochemical properties of (1) are discussed.     

Gossypol clathrates: Structure and thermal behavior of gossypol solvates with two picoline isomers

Gossypol forms stable solvates with 4- and 2-picolines at room temperature. The solvates are investigated by single crystal X-ray diffraction and thermal analysis. Solvate crystals of gossypol with 4-picoline (1) have the 1:3 composition (gossypol:4-picoline) and crystallize in the P2₁/c space group. This substance is isostructural to a trisolvate of gossypol with pyridine. Solvate crystals of gossypol with 2-picoline (2) have the 1:4 composition (gossypol:2-picoline) and crystallize in the P-1 space group. The unit cell parameters for the investigated structures are as follows: 1 monoclinic crystals, C₃₀H₃₀O₈·3C₆H₇N, a = 10.7530(1) ?, b = 20.7834(3) ?, c = 19.1166(2) ?, β = 95.537(1)°, V = 4252.32(9) ?³, M = 797.92, Z = 4, d _x = 1.246 g/cm³, and R = 0.0489 for 4102 reflections; 2 triclinic crystals, C₃₀H₃₀O₈·4C₆H₇N, a = 11.467(1) ? b = 14.962(2) ?, c = 15.570(3) ?, α = 75.62(1)°, β = 69.83(1)°, γ = 79.58(1)°, V = 2414.6(7) ?³, M = 891.04, Z = 2, d _x = 1.226 g/cm³, and R = 0.0528 for 3779 reflections. The results of the single crystal XRD and thermal analysis confirm that gossypol with 4-picoline forms a trisolvat, and a tetrasolvate with 2-picoline. The transition from 4-picoline to 2-picoline proves to change the type of the host-guest association from one-dimensional to zero-dimensional, i.e., to lead to a new crystal structure. Desolvation of compound 2 begins at a lower temperature than that for compound 1, which is explained by their different crystal structures. Keywords: gossypol, 4-picoline, 2-picoline, clathrate formation, crystal structure.     

Synthesis,spectra and crystal structure of a dinuclear manganese(χ) complex [(NTB)Mn(μ-O)]2(ClO4)4 · 2H2O

A novel dinuclear manganese(χ) complex [(NTB)Mn(μ-O)]₂(ClO₄)₄?·?2H₂O (1) (NTB?=?tris(2-benzimidazolylmethyl) amine) has been synthesized and characterized. The crystal structure is determined by single crystal X-ray diffraction. The compound crystallizes in the monoclinic system, space group C2/c with a?=?18.3461(1), b?=?15.4170(1), c?=?21.0141(1)?Å, β?=?90.5290(1)°, V?=?5943.4(8)?ų, Z?=?4 and R ₁?=?0.0789 for 5729 observed reflections. Two manganese atoms are bridged by two oxygen atoms forming a dinuclear complex. The results of interaction between 1 and H₂O₂ indicated that hydrogen peroxide destroyed the Mn₂O₂ unit of 1.     

The molecular structure of high‐spin (S = ) manganese(II) phthalocyanine in tetrabutylammonium bromido(phthalocyaninato)manganese(II)

The title complex salt, (C₁₆H₃₆N)[MnBr(C₃₂H₁₆N₈)] or (TBA)[Mn^IIBr(Pc)] (TBA is tetrabutylammonium and Pc is phthalocyaninate), has been obtained as single crystals by the diffusion technique and its crystal structure was determined using X‐ray diffraction. The high‐spin (S = ) [Mn^IIBr(Pc)]⁻ macrocycle has a concave conformation, with an average equatorial Mn—N(Pc) bond length of 2.1187 (19) Å, an axial Mn—Br bond length of 2.5493 (7) Å and with the Mn^II cation displaced out of the 24‐atom Pc plane by 0.894 (2) Å. The geometry of the Mn^IIN₄ fragment in [Mn^IIBr(Pc)]⁻ is similar to that of the high‐spin (S = ) manganese(II) tetraphenylporphyrin (TPP) in [Mn^II(1‐MeIm)(TPP)] (1‐MeIm is 1‐methylimidazole).     

Synthesis,Crystal Structure,and Thermal Properties of Na5[SnS4]Cl·13H2O

Reaction of Na₂S with SnCl₄ · 5H₂O in aqueous alkaline sodium hydroxide solution leads to the formation of Na₅[SnS₄]Cl · 13H₂O ( 1 ). The compound crystallizes monoclinic in space group P2₁/m with two formula units in the unit cell. In the crystal structure the Na⁺ cations are octahedrally coordinated and are linked into layers by bridging water molecules, μ₃ bridging Cl^– anions and μ_1,1 bridging S atoms of [SnS₄]^4– anions. Extended hydrogen bonding interactions generate a three‐dimensional network. Investigations using differential thermoanalysis, thermogravimetry, and differential scanning calorimetry shows that upon heating in open crucibles the water can be removed leading to the formation of the anhydrate that is stable at room temperature and does not transform back into compound 1 . Storage of the anhydrate in a desiccator over a water atmosphere leads first to formation of Na₄SnS₄ · 14H₂O followed by crystallization of the title compound. After longer storage times NaCl appears as a second crystalline phase. If the thermal measurements are performed in a self‐produced atmosphere, compound 1 transforms partly into Na₄SnS₄ · 14H₂O with an increasing amount of this phase with increasing temperature. Synthetic investigations reveal that crystallization of compound 1 sensitively depends on the water content of acetone, which is used for precipitation of 1 . Reacting Na₄SnS₄ · 14H₂O directly with NaCl afforded formation of complex mixtures.     

Assembly and Crystal Structure of a Novel 1—D Coordination Polymer of Copper（Ⅱ）with Thiocyanate and 4—Cyanopyridine

A novel one‐dimensional coordination polymer, Catena‐poly [bis(4‐cyano‐pyridyl) copper(II)‐di‐thiocyanate], ¹_∞ [Cu^II‐(cypy)₂(μ_N.S‐SCN)₂] (cypy = 4‐cyano‐pyridyl), was synthesized in a solution reaction of Cu(NO₃)₂·3H₂O, 4‐cyano‐pyridine and KSCN in mole ratio of 1:2:2 at room temperature. Its crystal structure was determined by single‐crystal X‐ray diffraction. The crystal belongs to monoclinic crystal system, space group P2₁/c with cell parameters a = 1.0719(2), b = 1.8441(4), c =0.9144(2) nm, β = 110.49(3)° and Z = 4. A full‐matrix least‐squares refinement gave R₁ = 0. 0393 and wR₂= 0.0916 for 1554 reflections having 1 >2σ(I). The crystal is thermally stable up to approximately 170 °C.     

Preparation and Structure Determination of SrMn2(PO4)2 and Redetermination of b ′‐Mn3(PO4)2

Pale rose single crystals of SrMn₂(PO₄)₂ were obtained from a mixture of SrCl₂ · 6 H₂O, Mn(CH₃COO)₂, and (NH₄)₂HPO₄ after thermal decomposition and finally melting at 1100 °C. The new crystal structure of strontium manganese orthophosphate [P‐1, Z = 4, a = 8.860(6) Å, b = 9.054(6) Å, c = 10.260(7) Å, α = 124.27(5)°, β = 90.23(5)°, γ = 90.26(6)°, 4220 independent reflections, R1 = 0.034, wR2 = 0.046] might be described as hexagonal close‐packing of phosphate groups. The octahedral, tetrahedral and trigonal‐bipyramidal voids within this [PO₄] packing provide different positions for 8‐ and 10‐fold [SrO_x] and distorted octahedral [MnO₆] coordination according to a formulation Mn Mn Mn Sr (PO₄)₄. Single crystals of β′‐Mn₃(PO₄)₂ (pale rose) were grown by chemical vapour transport (850 °C → 800 °C, P/I mixtures as transport agent). The unit cell of β′‐Mn₃(PO₄)₂ [P2₁/c, Z = 12, a = 8.948(2) Å, b = 10.050(2) Å, c = 24.084(2) Å, β = 120.50°, 2953 independent reflections, R1 = 0.0314, wR2 = 0.095] contains 9 independent Mn²⁺. The reinvestigation of the crystal structure led to distinctly better agreement factors and significantly reduced standard deviations for the interatomic distances.     

Etude de la tétracoordination de l'etain dans deux orthothiostannates: Na4SnS4 et Ba2SnS4 (α)

The crystal structure of Na₄SnS₄ and Ba₂SnS₄ (α) were determined.Na₄SnS₄ crystallizes in tetragonal system, space group $\text{P}\text{4}\text{2}{}_1\text{c}$ with parameters a = 7.837 Å, c = 6.950 Å, Z = 2 and Ba₂SnS₄ (α) in the monoclinic system, space group $\text{P2}{}_1\text{c}$ with a = 8.481 Å, b = 8.526 Å, c = 12.280 Å, β = 112.97° and Z = 4.In these compounds, the crystal structure is built up from discrete orthothiostannate tetrahedra SnS₄. The structure of Ba₂SnS₄ (α) is modified K₂SO₄β type.     

Studies On Rare-Earth Complexes with Crown Ethers. Part XXV. Synthesis,characterization, and structure of the complexes of lanthanide nitrates with 13-crown-4

The lanthanide nitrate complexes with 13-crown-4(13-C-4) have been prepared in AcOEt. These new complexes with the general formula Ln(NO₃)₃.(13-c-4) (Ln = La–Nd, Sm–Lu) have been characterized by means of elemental analysis, IR and ¹H-NMR spectra, conductivity measurements, and TG-DTA techniques. The crystal and molecular structure of Nd(No₃)₃. (13-c-4) has been determined by single crystal X-ray diffraction. It crystallizes in the monoclinic space group P2₁/a with Z = 8. Lattice parameters are a = 15.393(1), b = 12.578(1), c = 19.279(2) Å, β = 113.05(1)°, V = 3435 ų, D_c = 2.01 g cm^?3, μ = 31.0 cm^?1 (Mok₂), F(000) = 2056. The structure was solved by Patterson and Fourier techniques and refined by least-squares to a final conventional R value of 0.032 for 5218 independent reflections with I ? 3σ(I). There are two independent Nd(No₃)₃ · (13-C-4) monomers in one asymmetrical unit. The coordination numbers are ten in these two independent monomers.     

Solvothermal Syntheses and Characterization of Thiostannates [M(en)3]2Sn2S6 (M = Mn,Co, Zn), the Influence of Metal Ions on the Crystal Structure

Three new thiostannates [M(en)₃]₂Sn₂S₆ (en = ethylenediamine, M = Mn( 1 ), Co( 2 ) and Zn( 3 )) were synthesized by solvothermal method. The crystals were grown up in a Teflon‐lined steel autoclave at temperature about 180 °C. All the three compounds consist of discrete [Sn₂S₆]^4— anions, which are dimer of two tetrahedral SnS₄ sharing a common edge. The transition metal cations are six‐coordinated by three ethylenediamine molecules forming octahedral complex ions. Although the synthetic procedures, the mole ratio of the reactants and the solvent are essentially the same, the compound of Mn^II is quite different in structure from that of compounds of Co^II and Zn^II. Compound 1 crystallizes in monoclinic crystal system, C2/c, whereas compounds 2 and 3 crystallize in the orthorhombic crystal system, Pbca. Unlike compound 1 , the [M(en)₃]²⁺ cations in 2 and 3 are disordered. The difference of molecular packing between 1 and 2 ‐ 3 is considered due to the influence of the entities of the metal ions, such as radii and the coordination properties. The thermal chemical behaviors of the compounds 1 ‐ 3 were discussed and the results are also related to the property of the metal ions.