Phase formation in the systems Ag2MoO4-MO-MoO3 (M=Ca, Sr, Ba, Pb, Cd, Ni, Co, Mn) and crystal structures of Ag2M2(MoO4)3 (M=Co, Mn)

Phase equilibria in the systems Ag2MoO4-MMoO4 (M=Ca, Sr, Ba, Pb, Ni, Co, Mn) and subsolidus phase relations in the systems Ag2MoO4-MO-MoO3 (M=Ca, Pb, Cd, Mn, Co, Ni) were investigated using XRD and thermal analysis. The systems Ag2MoO4-MMoO4 (M=Ca, Sr, Ba, Pb, Ni) belong to the simple eutectic type whereas in the systems Ag2MoO4-MMoO4 (M=Co, Mn) incongruently melting Ag2M2(MoO4)3 (M=Co, Mn) were formed. In the ternary oxide systems studied no other compounds were found. Low-temperature LT-Ag2Mn2(MoO4)3 reversibly converts into the high-temperature form of a similar structure at 450-500 deg. C. The single crystals of Ag2Co2(MoO4)3 and LT-Ag2Mn2(MoO4)3 were grown and their structures determined (space group P1-bar, Z=2; lattice parameters are a=6.989(1) A, b=8.738(2) A, c=10.295(2) A, α=107.67(2) deg., β=105.28(2) deg., γ=103.87(2) deg. and a=7.093(1) A, b=8.878(2) A, c=10.415(2) A, α=106.86(2) deg., β=105.84(2) deg., γ=103.77(2) deg, respectively) and refined to R(F)=0.0313 and 0.0368, respectively. The both compounds are isotypical to Ag2Zn2(MoO4)3 and contain mixed frameworks of MoO4 tetrahedra and pairs of M2+O6 octahedra sharing common edges. The Ag+ ions are disordered and located in the voids forming infinite channels running along the a direction. The peculiarities of the silver disorder in the structures of Ag2M2(MoO4)3 (M=Zn, Mg, Co, Mn) are discussed as well as their relations with analogous sodium-containing compounds of the structural family of Na2Mg5(MoO4)6. The phase transitions in Ag2M2(MoO4)3 (M=Mg, Mn) of distortive or order-disorder type are suggested to have superionic character