Synthesis, {sup 77}Se and {sup 119}Sn NMR study, and X-ray crystal structure of the Sn{sub 4}Se{sub 10}{sup 4-} anion and Raman spectra of SnSe{sub 4}{sup 4-} and Sn{sub 4}Se{sub 10}{sup 4-}
- McMaster Univ., Hamilton, Ontario (Canada); and others
The novel selenostannate(IV) anion, Sn{sub 4}Se{sub 10}{sup 4-}, has been obtained by extracting the ternary alloy KSn{sub 0.67}Se{sub 1.93} in ethylenediamine (en) and liquid NH{sub 3} in the presence of 2, 2, 2-crypt (4, 7, 13, 16, 21, 24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) and characterized in solution by {sup 77}Se and {sup 119}Sn NMR spectroscopy and in the solid state by X-ray crystallography and Raman spectroscopy. The scalar couplings, {sup 1}J({sup 119}Sn-{sup 77}Se) and {sup 2}J({sup 119}Sn-{sup 77}Sn), have been determined and compared with those of related systems. The salt, (2, 2, 2-crypt-K{sup +}){sub 4}Sn{sub 4}Se{sub 10}{sup 4-}, crystallizes in the triclinic system, space group P{bar 1}, with Z = 2 and a = 14.769(2) {Angstrom}, b = 15.580(1) {Angstrom}, c = 26.275(4) {Angstrom}, {alpha} = 79.19(1){degrees}, {beta} = 85.65(1){degrees}, and {gamma} = 85.870(8){degrees} at 24 {degrees}C. The solid state and solution anion geometry is of the adamantanoid type where the Sn{sup IV} atoms occupy the bridgehead positions and the Se atoms occupy the bridging and terminal sites. The terminal [average, 2.425(2) {Angstrom}] and bridging [average, 2.425(2){Angstrom}] and bridging [average, 2.548(2) {Angstrom}] Sn-Se bond distances were found to correlate with their respective {sup 1}J({sup 119}Sn-{sup 77}Se) coupling constants. The Raman spectrum of the Sn{sub 4}Se{sub 10}{sup 4-} anion has been assigned and compared to those of related adamantanoid systems and SnSe{sub 4}{sup -4}.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 457080
- Journal Information:
- Inorganic Chemistry, Vol. 34, Issue 25; Other Information: PBD: 6 Dec 1995
- Country of Publication:
- United States
- Language:
- English
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