Abstract
A new calcium thallate, Ca 3Tl 2O 6 has been synthesized. It crystallizes in the space group Pbam with a = 11.248(2)Å, b = 16.513(2) Å, and c = 3.3329(3) Å. The ab initio determination of its structure from powder X-ray data shows that it consists of zigzag rock-salt-type layers [Ca 4Tl 4O 14] ∞ parallel to (010), built up from quadruple ribbons of TlO 6 octahedra running along c, interconnected with single and double ribbons of CaO 6 octahedra. Along b, these rock-salt-type layers share the corners of their octahedra forming tunnels approximately similar to those observed in CaTi 2O 4, where calcium ions are located with a monocapped trigonal prismatic coordination. This oxide represents the third member of the series Ca n Tl 2O n+3 ; its relationships with the two n = 1 and 2 members CaTl 2O 4 and Ca 2Tl 2O 5, that correspond to a chemical twinning of the rock salt structure, are discussed. In fact Ca 3Tl 2O 6 is isostructural with Ca 3In 2O 6.
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