title: 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.
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.
authors.affiliation: Department of Materials Science, Moscow State University, Leninskie Gory, Moscow, 119992 Russia.
authors.forename: A I
authors.initials: AI
authors.lastname: Baranov
authors.forename: A A
authors.initials: AA
authors.lastname: Isaeva
authors.forename: L
authors.initials: L
authors.lastname: Kloo
authors.forename: B A
authors.initials: BA
authors.lastname: Popovkin