Density functional theory calculations on complexes of C-4(1), C-1(4) and (2)So ring conformations of methyl beta-D-xylopyranoside 1 with divalent metal cations, M = Mg2+, Ca2+, Zn2+, and Cd2+, are presented. Bridging and pendant cationic, [M(H2O)(4)1](2+) and [M(H2O)(5)1](2+), as well as neutral complexes, [M(OH)(2)(H2O)(2)1] and [M(OH)(2)(H2O)(3)1], and neutral complexes involving a doubly deprotonated sugar, [M(H2O)(4)1(2-)], are considered. In aqueous and chloroform solution the stability of cationic and pendant neutral complexes is greatly diminished compared with gas-phase results. In contrast, bridging neutral complexes [M(OH)(2)(H2O)(2)1] and those of type [M(H2O)(4)1(2-)], are stabilized with increasing solvent polarity. Solvation also profoundly influences the preferred binding position and ring conformation. Compared with complexes of bare metal cations, additional ligands, e.g., H2O or OH-, significantly reduce the stability of C-1(4) ring complexes. Irrespective of the cation, the most stable structure of bridging complexes [M(H2O)(4)1](2+) results from coordination of the metal to O3 and O4 of methyl beta-D-xylopyranoside in its C-4(1) ring conformation.