New metal-rich sulfides Ni(6)SnS(2) and Ni(9)Sn(2)S(2) with a 2D metal framework: synthesis, crystal structure, and bonding

A I Baranov; A A Isaeva; L Kloo; B A Popovkin

doi:10.1021/ic034349+

New metal-rich sulfides Ni(6)SnS(2) and Ni(9)Sn(2)S(2) with a 2D metal framework: synthesis, crystal structure, and bonding

Inorg Chem. 2003 Oct 20;42(21):6667-72. doi: 10.1021/ic034349+.

Authors

A I Baranov¹, A A Isaeva, L Kloo, B A Popovkin

Affiliation

¹ Department of Materials Science, Moscow State University, Leninskie Gory, Moscow, 119992 Russia.

PMID: 14552618
DOI: 10.1021/ic034349+

Abstract

Two new, metal-rich nickel-tin sulfides Ni(6)SnS(2) and Ni(9)Sn(2)S(2) were found by establishing phase relations in the ternary Ni-Sn-S system at 540 degrees C. Their single crystals were prepared by means of chemical vapor transport reactions. Single crystal X-ray diffraction was used for the determination of their crystal structures. Both compounds crystallize in a tetragonal system (I4/mmm, No. 139, Z = 2, a = 3.646(1) A, c = 18.151(8) A for Ni(6)SnS(2), and a = 3.678(1) A, c = 25.527(8) A for Ni(9)Sn(2)S(2)). Their crystal structures represent a new structure type and can be considered as assembled from bimetallic nickel-tin and nickel-sulfide slabs alternating along the crystallographic c axis. DFT band structure calculations showed the bonding within the bimetallic slabs to have a delocalized, multicenter nature, typical for metallic systems, and predominantly classical, pairwise bonding between nickel and sulfur.