Crystal structures and variable magnetism of PbCu2(XO3)2Cl2 with X = Se, Te

Novel Cu2+-based compounds PbCu2(SeO3)(2)Cl-2 (space group C2/c; a = 13.056(1) angstrom; b = 9.5567(9) angstrom; c = 6.9006(6) angstrom; beta = 90.529(7)degrees; R-I = 0.0371) and PbCu2(TeO3)(2)Cl-2 (space group P21; a = 7.2401(2) angstrom; b = 7.2688(2) angstrom; c = 8.2846(2) angstrom; beta = 96.416(2)degrees; R-I = 0.0570) have been obtained by solid-state synthesis. Their crystal structures are remarkably dissimilar and underlie a very different magnetic behavior. While PbCu2(SeO3)(2)Cl-2 can be well described by a spin-chain model with an exchange coupling of J(1)similar or equal to 160 K, PbCu2(TeO3)(2)Cl-2 is a spin-dimer system that, however, features a comparable magnetic nearest-neighbor coupling of J. 213 K. PbCu2(SeO3)(2)Cl-2 orders antiferromagnetically below 12 K, whereas PbCu2(TeO3)(2)Cl-2 lacks long-range magnetic order down to at least 2 K, owing to the strong dimerization of the Cu2+ spins. Crystal structures of both compounds are rationalized in terms of relevant magnetic exchange pathways, and the implications for a broader range of Cu2+ compounds are discussed.