Syntheses, Vibrational Spectra, and Theoretical Studies of the Adamantanoid Sn4Ch104- (Ch = Se, Te) Anions: X-ray Crystal Structures of [18-Crown-6-K]4[Sn4Se10]·5en and [18-Crown-6-K]4[Sn4Te10]·3en·2THF
- 7 August 2001
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 40 (19) , 4823-4829
- https://doi.org/10.1021/ic010242f
Abstract
The salts [18-crown-6-K]4[Sn4Se10]·5en and [18-crown-6-K]4[Sn4Te10]·3en·2THF were isolated upon addition of THF to the ethylenediamine (en) extracts of the alloys KSn0.90Se1.93 and K4Sn4Te10 that had been extracted in the presence of 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane). The Sn4Te104- anion has been structurally characterized for the first time by a single-crystal X-ray diffraction study of [18-crown-6-K]4[Sn4Te10]·3en·2THF: P21/n, a = 22.420(5) Å, b = 19.570(4) Å, c = 24.680(5) Å, β = 96.90(3)o, Z = 4, and R1 = 0.0468 at −183 °C. In addition to Si4Te104- and Ge4Te104-, the Sn4Te104- anion represents the only other known group 14 adamantanoid telluride. The X-ray crystal structure determination of the related [18-crown-6-K]4[Sn4Se10]·5en salt has also been determined: P21/n, a = 22.003(2) Å, b = 18.966(2) Å, c = 24.393(2) Å, β = 97.548(8)o, Z = 4, and R1 = 0.0843 at −123 °C. The anion geometries are of the adamantanoid type where the SnIV atoms occupy the bridgehead positions and the chalcogen atoms occupy the bridging and terminal sites. The energy minimized geometries of Sn4Ch104- have also been determined using density functional theory (DFT). Mayer bond order analyses, Mayer valencies, and empirical bond valencies indicate that the terminal Sn−Ch bonds have significant multiple bond character, with the terminal Sn−Se bond having more multiple bond character than the terminal Sn−Te bond. The vibrational frequencies of the Sn4Se104- and Sn4Te104- anions have been calculated using DFT methods, allowing the Raman spectrum of Sn4Se104- to be fully assigned.Keywords
This publication has 45 references indexed in Scilit:
- Trigonal Bipyramidal M2Ch32- (M = Sn, Pb; Ch = S, Se, Te) and TlMTe33- Anions: Multinuclear Magnetic Resonance, Raman Spectroscopic, and Theoretical Studies, and the X-ray Crystal Structures of (2,2,2-crypt-K+)3TlPbTe33-·2en and (2,2,2-crypt-K+)2Pb2Ch32-·0.5en (Ch = S, Se)Inorganic Chemistry, 1998
- Tl2Ch22- (Ch = Se and/or Te) Anions: X-ray Crystal Structures and Raman Spectra of (2,2,2-crypt-K+)2Tl2Se22- and (2,2,2-crypt-K+)2Tl2Te22- and Solution 77Se, 203Tl, and 205Tl NMR Spectroscopic and Theoretical Studies of Tl2Ch22-, In2Se22-, and In2Te22- †Inorganic Chemistry, 1998
- Chalcogen Diimides: Relative Stabilities of Monomeric and Dimeric Structures, [E(NMe)2]n (E = S, Se, Te; n = 1, 2)Inorganic Chemistry, 1998
- X-ray structure of 18-crown-6-KClO4 at room temperature and 20 KActa crystallographica Section B, Structural science, crystal engineering and materials, 1992
- Optimization of Gaussian-type basis sets for local spin density functional calculations. Part I. Boron through neon, optimization technique and validationCanadian Journal of Chemistry, 1992
- Approximate density functional theory as a practical tool in molecular energetics and dynamicsChemical Reviews, 1991
- Homo- and heteropolychalcogenide anions Ch2-, HCh-, Ch22-, Ch32-, and Ch42- (Ch = selenium and/or tellurium): solution proton, selenium-77, tellurium-123 and -125 NMR studyInorganic Chemistry, 1991
- Crystal and molecular structures of the copper(II) and copper(III) dithiooxalate complexes (18-crown-6)2K2Cu(S2C2O2)2 and ([C6H5)3P]2N)Cu(S2C2O2)2Inorganic Chemistry, 1985
- K4Si4Te10, das erste Tellurosilicat mit Adamantan‐analogen Si4Te104−‐AnionenZeitschrift für anorganische und allgemeine Chemie, 1982
- Spectroscopic studies of As4O6, Sb4O6, P4S10, Ge4S104− and organometallic compounds containing the M4X6 cage. The Raman and i.r. spectrum of Ge4S104−Spectrochimica Acta Part A: Molecular Spectroscopy, 1976