Structures of Novel R2Mo5O18 and R6Mo12O45 (R = Eu and Gd) Prepared by Thermal Decomposition of Polyoxomolybdate Precursor [R2(H2O)12Mo8O27]·nH2O

Abstract

Single crystals of R(2)Mo(5)O(18) and R(6)Mo(12)O(45) (R = Eu and Gd), which are novel compounds in the R(2)O(3)-MoO(3) system, have been obtained by thermal decomposition of [R(2)(H(2)O)(12)Mo(8)O(27)].nH(2)O in air at 750 degrees C for 2 h. TG-DTA and X-ray diffractometry showed that R(2)Mo(5)O(18) crystallizes in a melt of the dehydrated precursor (R(2)Mo(8)O(27)), and R(2)Mo(5)O(18) is transformed to R(6)Mo(12)O(45) in the solid state, both occurring with the loss of MoO(3). R(2)Mo(5)O(18) species crystallize isostructurallyas orthorhombic, Pbcn, Z = 4, with lattice constants of a = 19.2612(7) and 19.246(1) A, b = 9.4618(3) and 9.4414(5) A, c = 9.3779(3) and 9.3446(4) A for R = Eu and Gd, respectively. R(6)Mo(12)O(45) crystallize isostructurally as triclinic P1, Z = 1, with lattice constants of a = 9.3867(4) and 9.3409(3) A, b = 10.9408(5) and 10.8826(5) A, c = 11.4817(5) and 11.4377(5) A, alpha = 104.194(2) degrees and 104.170(1) degrees, beta = 109.567(3) degrees and 109.288(4) degrees, gamma = 108.998(2) degrees and 109.266(2) degrees for R = Eu and Gd, respectively. Both structures consist of [RO(8)] square-antiprisms and [MoO(n)] polyhedra. In R(2)Mo(5)O(18), an [RO(8)] polyhedron is attached by only molybdate groups, being isolated from adjacent [RO(8)] groups. The 12 nearest R atoms surrounding an R atom with R...R distances of 6.0735(4)-7.0389(4) A form an approximate cuboctahedron. All the [RO(8)] square-antiprisms in R(6)Mo(12)O(45) are connected to each other by face-sharing to form dimeric [R(2)O(13)] and [R(2)O(12)] groups. The latter unusual [R(2)O(12)] group is achieved by sharing a square-face via four bridging O atoms with a very short R...R separation (3.4741(7) and 3.4502(6) A for R = Eu and Gd, respectively).