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The title compound was prepared in well-crystallized form by thermal decomposition of Ca 5 Re 2 O 12 . Its structure was determined from single-crystal X-ray diffractometer data: I4 1 , a = 1107.0(1), c = 1609.3(1) pm, Z = 4, R = 0.056 for 4565 structure factors and 119 variable parameters. The calcium atoms occupy seven different sites with 8, 9, or 10 oxygen neighbors. The two different rhenium atoms are octahedrally coordinated by oxygen atoms with average Re-O distances of 193.1 and 187.7 pm for the six- and seven-valent rhenium atoms, respectively. The compound shows Curie-Weiss behavior with a magnetic moment of μ exp  = 1.15(±0.10) μ B  per Re(VI) atom. The structure is closely related to that of Sr 11 Os 4 O 24  which, however, crystallizes in the space group I2/a. The difference between the two structures arises through the higher coordination numbers of the strontium atoms. It is suggested that at high temperature both compounds crystallize in the common higher symmetry space group I4/a. Since Ca 11 Re 4 O 24  crystallizes in the pyroelectric class 4 this compound is expected to be ferroelectric.

The Crystal Structure of the Potential Ferroelectric Calcium Rhenate(VI, VII) Ca 11 Re 4 O 24 and its Relation to the Structure of Sr 11 Os 4 O 24