Reaction of (CH3)(2)SnCl2 with Na2MoO4 in an aqueous medium results in three different compounds depending on the pH: [{(CH3)(2)Sn}(MoO4)] (1), [{(CH3)(2)Sn}(4)O-2(MoO4)(2)] (2), and [{(CH3)(2)Sn}{Mo2O7(H2O)(2)}]center dot 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 1-3 all show hybrid organic-inorganic extended lattices based on molybdate anions linked by (CH3)(2)Sn2+ 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) angstrom, b = 7.2634(2) angstrom, c = 7.1458(2) angstrom, and Z = 4.1 exhibits a complex, 3-dimensional network structure constructed of corner-shared, tetrahedral orthomolybdate oxoanions and distorted octahedral trans-(CH3)(2)SnO4 groups. Compound 2 crystallizes in the monoclinic space group P2(1)/n with cell parameters a = 8.2330(1) angstrom, b = 11.4033(2) angstrom, c = 12.1529(2) angstrom, beta = 91.566(1)degrees, and Z = 2. Its 2-dimensional layered structure contains dimeric tetramethyldistannoxane [{(CH3)(2)Sn}(4)O-2](2+) subunits built up of edge-sharing cis-(CH3)(2)SnO4 distorted trigonal bipyramids and connected in the (1,0,(1) over cap) 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) angstrom, b = 14.2465(11) angstrom, c = 11.3892(8) angstrom, and Z = 4. It shows dimeric [Mo2O8(H2O)(2)] units sharing corners to form zigzagging polymeric {[Mo2O7(H2O)(2)](2-)}(infinity) polyanions along the [001] direction; these chains are further linked by trans-(CH3)(2)SnO5 distorted pentagonal bipyramids to give layers parallel to the (010) plane, the interlamellar space being occupied by hydrogen-bonded hydration water molecules.