PbMSeO6 (M = Mo and W): new quaternary mixed metal selenites with asymmetric cationic coordination environments

Two new isostructural mixed metal selenites, PbMSeO(6) (M = Mo(6+) or W(6+)), that are only composed of second-order Jahn-Teller (SOJT) distortive cations have been synthesized by standard solid-state reaction techniques using PbO, SeO(2), and MoO(3) (or WO(3)) as reagents. The structures of the reported materials were determined by single-crystal and powder X-ray diffraction. The materials show a three-dimensional framework structure consisting of chains of corner-shared MO(6) octahedra connected by SeO(3) and PbO(8) polyhedra. All of the constituent cations (M(6+), Se(4+), and Pb(2+)) are in distorted environments attributable to second-order Jahn-Teller (SOJT) effects. While the Mo(6+) cations undergo a C(2)-type intraoctahedral distortion toward an edge, the Se(4+) and Pb(2+) cations are in asymmetric coordination environments attributable to their lone pairs. The SeO(3) polyhedra strongly influence the direction of the Mo(6+) intraoctahedral distortion. Infrared spectroscopy, thermogravimetric analysis, the magnitudes of out-of-center distortions, and dipole moment calculations are also presented. Crystal data: PbMoSeO(6), triclinic, space group P-1 (No. 2), with a = 6.8944(6) Å, b = 7.2219(6) Å, c = 10.8294(9) Å, α = 99.751(2)°, β = 99.996(2)°, γ = 90.041(2)°, V = 523.09(8) Å(3), and Z = 2; PbWSeO(6), triclinic, space group P-1 (No. 2), with a = 6.8689(2) Å, b = 7.2398(2) Å, c = 10.9037(3) Å, α = 99.699(4)°, β = 100.348(3)°, γ = 90.139(4)°, V = 525.50(3) Å(3), and Z = 2.