Synthesis and Molecular and Crystal Structure of K4.5{[Mo3(mu_3-Te)(mu_2-Te2)3(CN)6]I}I1.5cdot3H2O and Cs3{[Mo3(mu_3-Te)(mu_2-Te2)3(CN)6]I}cdot2H2O

Author: Pervukhina N.V.   Podberezskaya N.V.   Kalinina I.V.   Fedin V.P.  

Publisher: Springer Publishing Company

ISSN: 0022-4766

Source: Journal of Structural Chemistry, Vol.41, Iss.5, 2000-09, pp. : 843-850

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Abstract

Crystal structures of two new compounds containing trigonal tellurium-bridged cluster fragments [Mo_3(mu_3-Te)(mu_2-Te_2)_3]^4+ were investigated. Crystal data for K_4.5{[Mo_3(mu_3-Te)(mu_2-Te_2)_3(CN)_6]I}I_1.5cdot3H_2O: space group P bar3 c 1, Z = 4, a = 13.280(1), c = 23.800(3) Å, V = 3635.0(6) Å^3, d_calc = 3.432 g/cm^3, R_1 = 0.0335, wR_2 = 0.0912 for 1378 I_{hkl} ge 2 sigma_I from 3545 measured I_{hkl}; for Cs_3{[Mo_3(mu_3-Te)(mu_2-Te_2)_3(CN)_6]I}cdot2H_2O: space group P2_1 /n, Z = 2, a = 9.650(2), b = 22.297(5), c = 27.446(7) Å, beta = 94.10(2)°, V = 5890(2) Å^3, d_calc = 4.273 g/cm^3, R_1 = 0.0384, wR_2 = 0.0744 for 957 I_{hkl} ge 2 sigma_I from 3758 measured I_{hkl} (Enraf-Nonius CAD-4 diffractometer, lambdaMoK_{alpha}, graphite monochromator). In both compounds, ionic pairs {[Mo_3Te_7(CN)_6]I}^3– with Te_ax...I^– distances of 3.358-3.676 Å are formed. In the potassium salt, the {[Mo_3Te_7(CN)_6]I}^3– anion pairs are linked by the additional Te_eqcdotsI^– short contacts of 3.460 Å into two-dimensional corrugated layers perpendicular to the c axis of the unit cell. The structure of the cesium salt is ionic with interstitial H_2O molecules and double-layer closest packing of anions.

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