Influence of the counterions on the structures of ternary Zn/Sn/Se anions: Synthesis and properties of [Rb-10(H2O)(14.5)][Zn-4(mu(4)-Se)(2)(SnSe4)(4)] and [Ba-5(H2O)(32)][Zn5Sn(mu(3)-Se)(4)(SnSe4)(4)]

Ruzin E; Dehnen S

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Influence of the counterions on the structures of ternary Zn/Sn/Se anions: Synthesis and properties of [Rb-10(H2O)(14.5)][Zn-4(mu(4)-Se)(2)(SnSe4)(4)] and [Ba-5(H2O)(32)][Zn5Sn(mu(3)-Se)(4)(SnSe4)(4)]

机译：抗衡离子对三价Zn / Sn / Se阴离子结构的影响：[Rb-10（H2O）（14.5）] [Zn-4（mu（4）-Se）（2）（SnSe4）（ 4）]和[Ba-5（H2O）（32）] [Zn5Sn（mu（3）-Se）（4）（SnSe4）（4）]

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Reactions of rubidium or barium salts of the ortho-selenostannate anion, [Rb-4(H2O)(4)][SnSe4] (1) or [Ba-2(H2O)(5)][SnSe4] (2) with Zn(OAc)(2) or ZnCl2 in aqueous solution yielded two novel compounds with different ternary Zn/Sn/Se anions, [Rb-10(H2O)(14.5)][Zn-4(mu(4)-Se)(2)(SnSe4)(4)] (3) and [Ba-5(H2O)(32)][Zn5Sn(mu(3)-Se)(4)(SnSe4)(4)] (4). 1 - 4 have been determined by means of single crystal X-ray diffraction: 1: triclinic space group P (1) over bar; lattice dimensions at 203 K: a = 8.2582(17) angstrom, b = 10.634(2) angstrom, c = 10.922(2) angstrom, alpha = 110.16(3)degrees, beta = 91.74(3)degrees, gamma = 97.86(3)degrees, V = 888.8(3) angstrom(3); R-1 [I > 2 sigma(I)] = 0.0669; wR(2) = 0.1619; 2: orthorhombic space group Pnma; lattice dimensions at 203 K: a = 17.828(4) angstrom, b 11.101 (2) angstrom, c = 6.7784(14) angstrom, V = 1341.5(5) angstrom(3); R-1 [I > 2 sigma(I)] 0.0561; wR(2) = 0.1523; 3: triclinic space group P (1) over bar; lattice dimension at 203 K: a = 17.43](4) angstrom, b = 17.459(4) angstrom, c = 22.730(5) angstrom, alpha = 105.82(3)degrees, beta = 99.17(3)degrees, gamma = 90.06(3)degrees, V = 6563.1(2) angstrom(3); R-1 [I > 2 sigma(I)] = 0.0822 wR(2) = 0.1782; 4: monoclinic space group P2(1)/c; lattice dimensions at 203 K: a = 25.23](5) angstrom, b = 24.776(5) angstrom, c = 25.396(5) angstrom, beta = 106.59(3)degrees, V = 15215.0(5) angstrom(3); R-1 [I > 2 sigma r(I)] = 0.0767; wR(2) = 0.1734. The results serve to underline the crucial role of the counterion for the type of ternary anion to be observed in the crystal. Whereas Rb+(aq) stabilizes a PI-type Zn/Sn/Se supertetrahedron in 3 like K+, the Ba2+(aq) ions better fit to an anionic T3-type Zn/Sn/Se cluster arrangement as do Na+ ions. It is possible to estimate a radius:charge ratio for the stabilization of the two structural motifs.

机译：邻硒锡锡酸根阴离子，或[Rb-4（H2O）（4）] [SnSe4]（1）或[Ba-2（H2O）（5）] [SnSe4]（2）的salts盐或钡盐与锌的反应（OAc）（2）或ZnCl2在水溶液中产生两种具有不同三元Zn / Sn / Se阴离子的新型化合物，[Rb-10（H2O）（14.5）] [Zn-4（mu（4）-Se）（2 ）（SnSe4）（4）]（3）和[Ba-5（H2O）（32）] [Zn5Sn（mu（3）-Se）（4）（SnSe4）（4）]（4）。已经通过单晶X射线衍射确定了1-4：1：棒上的三斜空间群P（1）; 203 K时的晶格尺寸：a = 8.2582（17）埃，b = 10.634（2）埃，c = 10.922（2）埃，alpha = 110.16（3）度，beta = 91.74（3）度，gamma = 97.86（ 3）度，V = 888.8（3）埃（3）; R-1 [I> 2 sigma（I）] = 0.0669; wR（2）= 0.1619; 2：正交空间群Pnma; 203 K时的晶格尺寸：a = 17.828（4）埃，b 11.101（2）埃，c = 6.7784（14）埃，V = 1341.5（5）埃（3）; R-1 [I> 2 sigma（I）] 0.0561; wR（2）= 0.1523; 3：三边形空间群P（1）超过bar; 203 K时的晶格尺寸：a = 17.43]（4）埃，b = 17.459（4）埃，c = 22.730（5）埃，alpha = 105.82（3）度，beta = 99.17（3）度，γ= 90.06 （3）度，V = 6563.1（2）埃（3）; R-1 [I> 2 sigma（I）] = 0.0822 wR（2）= 0.1782; 4：单斜空间群P2（1）/ c; 203 K时的晶格尺寸：a = 25.23]（5）埃，b = 24.776（5）埃，c = 25.396（5）埃，beta = 106.59（3）度，V = 15215.0（5）埃（3）; R-1 [I> 2 sigma r（I）] = 0.0767; wR（2）= 0.1734。结果有助于强调抗衡离子对于晶体中要观察到的三元阴离子类型的关键作用。 Rb +（aq）使PI型Zn / Sn / Se超四面体像K +一样稳定在3中，而Ba2 +（aq）离子与Na +离子更适合阴离子T3型Zn / Sn / Se簇结构。可以估计半径：电荷比以稳定两个结构图案。

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《Zeitschrift fur Anorganische und Allgemeine Chemie》 |2006年第5期|共7页
作者
Ruzin E; Dehnen S;
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正文语种 eng
中图分类化学;
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barium; rubidium; selenostannates; ternary anions; crystal structure; zinc; ELECTRONIC-PROPERTIES; CHALCOGENIDE CLUSTERS; CRYSTAL-STRUCTURES; ZN; DISCRETE; MN; CO; REACTIVITY; COMPOUND; LIGANDS;

机译：钡;rub;硒酸锡;三价阴离子;晶体结构;锌;电子特性;缩醛类;晶体结构;ZN;离散;MN;CO;反应性;化合物;配体;

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1. Influence of the counterions on the structures of ternary Zn/Sn/Se anions: Synthesis and properties of [Rb-10(H2O)(14.5)][Zn-4(mu(4)-Se)(2)(SnSe4)(4)] and [Ba-5(H2O)(32)][Zn5Sn(mu(3)-Se)(4)(SnSe4)(4)] [J] . Ruzin E, Dehnen S Zeitschrift fur Anorganische und Allgemeine Chemie . 2006,第5期

机译：抗衡离子对三价Zn / Sn / Se阴离子结构的影响：[Rb-10（H2O）（14.5）] [Zn-4（mu（4）-Se）（2）（SnSe4）（ 4）]和[Ba-5（H2O）（32）] [Zn5Sn（mu（3）-Se）（4）（SnSe4）（4）]
2. [K-36(mu(6)-Cl)(2)(H2O)(11)(MeOH)(32)][SuSe(4)][CO4(mu(4)-Se)(SnSe4)(4)](3 ): Synthesis and crystal structure of a novel compound containing ternary [CO4(mu(4)-Se)(SnSe4)(4)](10-) anions and a novel [(mu(6)-Cl)(2)K-9](7+) coordination aggregate [J] . Melullis M., Zimmermann C., Anson CE., Zeitschrift fur Anorganische und Allgemeine Chemie . 2003,第12a13期

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3. Ortho-chalcogenostannates as ligands: Syntheses, crystal structures, electronic properties, and magnetism of novel compounds containing ternary anionic substructures [M-4(mu(4)-Se)(SnSe4)(4)](10-) (M = Mn, Zn, Cd, Hg), (3)(infinity)[Hg-4(mu Se-4)(SnS [J] . Brandmayer MK, Clerac R, Weigend F, Chemistry: A European journal . 2004,第20期

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4. A Novel Hybrid Compound Based on Polyoxometalate, Synthesis and Crystal Structure ofSm(NMP)4(H2O)4 HSiMo12O40·2NMP·H2O [C] . International symposium on solid state chemistry in China amp; 8th Chinese national conference on solid state chemistry and inorganic synthesis : Book of abstracts . 2002

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Influence of the counterions on the structures of ternary Zn/Sn/Se anions: Synthesis and properties of [Rb-10(H2O)(14.5)][Zn-4(mu(4)-Se)(2)(SnSe4)(4)] and [Ba-5(H2O)(32)][Zn5Sn(mu(3)-Se)(4)(SnSe4)(4)]

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