Crystal structure and phase transitions in Sr3WO6

The crystal structures of the beta and gamma polymorphs of Sr(3)WO(6) and the gamma<-->beta phase transition have been investigated using electron diffraction, synchrotron X-ray powder diffraction, and neutron powder diffraction. The gamma-Sr(3)WO(6) polymorph is stable above T(c) approximately 470 K and adopts a monoclinically distorted double perovskite A(2)BB'O(6) = Sr(2)SrWO(6) structure (space group Cc, a = 10.2363(1)A, b = 17.9007(1)A, c = 11.9717(1)A, beta = 125.585(1)(o) at T = 1373 K, Z = 12, corresponding to a = a(p) + 1/2b(p) - 1/2c(p), b = 3/2b(p) + 3/2c(p), c = -b(p) + c(p), a(p),b(p), c(p), lattice vectors of the parent Fm3m double perovskite structure). Upon cooling it undergoes a continuous phase transition into the triclinically distorted beta-Sr(3)WO(6) phase (space group C1, a = 10.09497(3)A, b = 17.64748(5)A, c = 11.81400(3)A, alpha = 89.5470(2)(o), beta = 125.4529(2)(o), gamma = 90.2889(2)(o) at T = 300 K). Both crystal structures of Sr(3)WO(6) belong to a family of double perovskites with broken corner sharing connectivity of the octahedral framework. A remarkable feature of the gamma-Sr(3)WO(6) structure is a non-cooperative rotation of the WO(6) octahedra. One third of the WO(6) octahedra are rotated by approximately 45 degrees about either the b(p) or the c(p) axis of the parent double perovskite structure. As a result, the WO(6) octahedra do not share corners but instead share edges with the coordination polyhedra of the Sr cations at the B positions increasing their coordination number from 6 to 7 or 8. The crystal structure of the beta-phase is very close to the structure of the gamma-phase; decreasing symmetry upon the gamma-->beta transformation occurs because of unequal octahedral rotation angles about the b(p) and c(p) axes and increasing distortions of the WO(6) octahedra.