ic061191v_si_002.cif (32.28 kB)

Hybrid Organic−Inorganic Assemblies Based on Molybdates and Dimethyltin Linkers

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posted on 30.10.2006, 00:00 by Santiago Reinoso, Michael H. Dickman, Markus Reicke, Ulrich Kortz
Reaction of (CH3)2SnCl2 with Na2MoO4 in an aqueous medium results in three different compounds depending on the pH:  [{(CH3)2Sn}(MoO4)] (1), [{(CH3)2Sn}4O2(MoO4)2] (2), and [{(CH3)2Sn}{Mo2O7(H2O)2}]·H2O (3). All three species have been characterized in the solid state by means of elemental analysis, infrared spectroscopy, thermogravimetry, and single-crystal X-ray diffraction. Compounds 13 all show hybrid organic−inorganic extended lattices based on molybdate anions linked by (CH3)2Sn2+ moieties, and the coordination numbers of the Sn(IV) centers range from 5 to 7. Compound 1 crystallizes in the orthorhombic space group Pnma with cell parameters a = 13.2035(4) Å, b = 7.2634(2) Å, c = 7.1458(2) Å, and Z = 4. 1 exhibits a complex, 3-dimensional network structure constructed of corner-shared, tetrahedral orthomolybdate oxoanions and distorted octahedral trans-(CH3)2SnO4 groups. Compound 2 crystallizes in the monoclinic space group P21/n with cell parameters a = 8.2330(1) Å, b = 11.4033(2) Å, c = 12.1529(2) Å, β = 91.566(1)°, and Z = 2. Its 2-dimensional layered structure contains dimeric tetramethyldistannoxane [{(CH3)2Sn}4O2]2+ subunits built up of edge-sharing cis-(CH3)2SnO4 distorted trigonal bipyramids and connected in the (1,0,1̄) plane by tetrahedral orthomolybdate oxoanions, the layers packing along the crystallographic a axis with the methyl groups pointing to the interlamellar space. Compound 3 crystallizes in the orthorhombic space group Pbcm with cell parameters a = 6.5594(4) Å, b = 14.2465(11) Å, c = 11.3892(8) Å, and Z = 4. It shows dimeric [Mo2O8(H2O)2] units sharing corners to form zigzagging polymeric {[Mo2O7(H2O)2]2-} polyanions along the [001] direction; these chains are further linked by trans-(CH3)2SnO5 distorted pentagonal bipyramids to give layers parallel to the (010) plane, the interlamellar space being occupied by hydrogen-bonded hydration water molecules.