Synthesis and modular structural architectures of mineralogically inspired novel complex Pb oxyhalides

Oleg I Siidra; Diana O Zinyakhina; Anastasiya I Zadoya; Sergey V Krivovichev; Rick W Turner

doi:10.1021/ic402066h

Synthesis and modular structural architectures of mineralogically inspired novel complex Pb oxyhalides

Inorg Chem. 2013 Nov 4;52(21):12799-805. doi: 10.1021/ic402066h. Epub 2013 Oct 11.

Authors

Oleg I Siidra¹, Diana O Zinyakhina, Anastasiya I Zadoya, Sergey V Krivovichev, Rick W Turner

Affiliation

¹ Department of Crystallography, Saint-Petersburg State University , University emb. 7/9, St. Petersburg, 199034 Russia.

PMID: 24116382
DOI: 10.1021/ic402066h

Abstract

Three novel Pb oxyhalides, Pb3[O10Pb20](GeO4)4Cl10 (1), [O16Pb22][OPb](OH)I10(I,Br)(H2O) (2), and Pb5.5Si0.5O6Cl (3), have been prepared by high-temperature solid-state reactions (1 and 3) and hydrothermal method (2). The structure of 1 is based upon novel [O10Pb20](20+) layers of edge- and corner-sharing oxocentered OPb4 tetrahedra with cavities occupied by the GeO4 tetrahedral anions. The interlayer space contains low-occupied Pb sites and Cl(-) anions. The structure of 2 contains unique [O16Pb22][12+] layers of edge-sharing OPb4 tetrahedra with X(-) ions (X = I, Br) in and in between the layers. The structure of 3 is the first example of the Pb oxyhalide with the 3:1 ratio between the O-Pb and X sheets (X = halide). The unprecedented structure topologies and architectures observed in the title compounds are closely related to those observed in rare natural Pb oxyhalides that have no synthetic analogues to date.