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Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Polyoxometalate Derivatives with Multiple Organic Groups. 2. Synthesis and Structures of Tris(organotin) alpha,
Feibo Xin1, Michael T. Pope, Gary J. Long
1Dipartemento di Chimica Inorganica Metallorganica ed Analytica, Universita di Padova, I-35131 Padova, Italy.
Abstract:
Eight tris(organotin)-substituted Keggin tungstosilicate heteropolyanions have been synthesized and characterized by elemental analysis, infrared and Mössbauer spectroscopy, multinuclear NMR, and X-ray crystallography. The new anions contain alpha- or beta-SiW(9)O(34)(10)(-) moieties and are of two structural types, [(RSn)(3)(SiW(9)O(37))](7)(-) (R, isomer: Ph, alpha-, 1; n-Bu, alpha-, 2; Ph, beta-, 3; n-Bu, beta-, 4) and [(RSnOH)(3)(SiW(9)O(34))(2)](14)(-) (Ph, alpha-, 5; n-Bu, alpha-, 6; Ph, beta-, 7; n-Bu, beta-, 8). Crystals of Cs(4)H(3)[(PhSn)(3)(SiW(9)O(37))].8H(2)O (anion 3) are monoclinic, space group C2/c, with lattice constants a = 48.91(2) Å, b = 12.111(3) Å, c = 20.334(9) Å, beta = 102.30 degrees, and Z = 8. The anion has nominal C(3)(v)() symmetry and has a structure with three corner-shared WO(6) octahedra of the beta-Keggin anion replaced by three PhSnO(5) groups. Crystals of Cs(9)H(5)[(BuSnOH)(3)(SiW(9)O(34))(2)].36H(2)O (anion 6) are tetragonal, space group P&fourmacr;2(1)m, with lattice constants a = b = 29.005(4) Å, c = 13.412(4) Å, and Z = 4. The anion has the anticipated D(3)(h)() symmetry and contains three BuSnOH groups sandwiched between A,alpha-SiW(9)O(34)(10)(-) anions.
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