Reactions of the tin precursors, R2Sn(OMe)OSO2Me (R = n-Pr, n-Bu), with an equimolar quantity of 2-quinoline/ 4-methoxy-2-quinoline/1-isoquinoline carboxylic acid in acetonitrile proceed under mild conditions (rt,12-15 h) via selective Sn-OMe bond cleavage to afford the corresponding mixed-ligand diorganotin derivatives [R2Sn(O2CR')-OSO2Me](2) [R' = C9H6N-2, R = n-Pr (1), n-Bu (2); R' = 4-OMe-C9H5N-2, R = n-Pr (3), n-Bu (4); R, = C9H6N-1, R = n-Pr (5), n-Bu (6)]. These have been characterized by FAB mass, IR, and multinuclear (H-1, C-11, Sn-119) NMR spectral data and X-ray crystallography (for 4 and 6). The molecular structure of 4 (C20H29NO6SSn, monoclinic, P2(1)/n, a = 14.1(13) Angstrom, b = 16.7(18) Angstrom, c = 20.3(19) Angstrom, = 107(4)degrees, Z = 8) comprises distorted octahedral geometry around each tin atom by virtue of weakly bridging methanesulfonate [Sn(1A)-O(3B) = 3.010, Sn(1B)-O(3A) = 2.984 Angstrom] and {N,O} chelation of the carboxylate ligands. The spectral data of 1-4 suggest a similar structural motif in solution. The molecular structure of 6 (C38H53N2O10S2Sn2, monoclinic, P-2/c, a = 11.339(2) Angstrom, b = 14.806(3) Angstrom, c = 24.929(5) Angstrom, beta = 100.537(3)degrees, Z = 4) reveals varying bonding preferences with monomeric units being held together by a bridging methanesulfonate [Sn(2)-O(5) = 2.312(2) Angstrom] and a carboxylate group bonded to Sn(1) and Sn(2) atoms, respectively. Slow hydrolysis of compound 2 derived from 2-quinoline carboxylic acid in moist CH3CN affords the asymmetric distannoxane, [BU2Sn(O2CC9H6N-2)-O-Sn(OSO2Me)Bu-2](2) (7) (C27H45NO6SSn2, monoclinic, C2/c, a = 21.152(3) Angstrom, b = 13.307(2) Angstrom, c = 26.060(4) Angstrom, = 110.02(10)degrees, Z = 8) featuring ladder type structural motif by virtue of unique mu(2)-coordination of covalently bonded oxygen atoms [0(6), O(6)#1] of the methanesulfonate groups.