Oxocentered Units in Three Novel Rb‐Containing Copper Compounds Prepared by CVT Reaction Method

Three novel copper compounds, Rb 4 Cu 4 OCl 10 ( I ), Rb[Cu 3 O](SeO 3 ) 2 Cl ( II ), and RbCu 3 (OH)(SeO 3 )Cl 4 (H 2 O) 3 ( III ) were prepared by chemical vapor transport (CVT) reactions method from mixtures of CuO, SeO 2 , RbCl, and CuCl 2 . The crystal structures of the three compounds were determined by direct methods. Compound I is a Rb analogue of ponomarevite, K 4 Cu 4 OCl 10 . Its crystal structure contains {[OCu 4 ]Cl 10 } 4– clusters with oxocentered [OCu 4 ] 6+ tetrahedra as cores. The clusters are linked by the Rb + cations. The crystal structure of II contains complex {[O 2 Cu 6 ](SeO 3 ) 4 Cl 2 } 2– layers formed by dimers of edge‐sharing [OCu 4 ] 6+ tetrahedra interlinked via selenite groups and Cl – anions. The crystal structure of III is based upon {[(OH)Cu 3 ](SeO 3 )} 3+ layers formed by the [(OH)Cu 3 ] 5+ tetrahedra attached to (SeO 3 ) 2– groups. The layers are linked via Cl – anions and via hydrogen bonds to H 2 O molecules.