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Bis(triphenylsulfonium) tetrachloridomanganate(II), (C18H15S)2[MnCl4] (I), triphenylsulfonium tetrachloridoferrate(III), (C18H15S)[FeCl4] (II), and bis(triphenylsulfonium) tetrachloridocobaltate(II), (C18H15S)2[CoCl4] (III), crystallize in the monoclinic space groupsP21/n[(I) and (III)] andP21/c[(II)]. Compounds (I) and (III) each contain two crystallographically independent triphenylsulfonium (TPS+) cations in the asymmetric unit, whereas (II) has one. In all three compounds, the sulfonium centers adopt distorted trigonal–pyramidal geometries, with S—C bond lengths falling roughly in the 1.78–1.79 Å range and C—S—C angles observed at about 101 to 106°. The [MCl4]n−anions (M= Mn2+, Fe3+, Co2+;n= 2,1,2) adopt slightly distorted tetrahedral geometries, withM—Cl bond lengths in the 2.19–2.38 Å range and Cl—M—Cl angles of approximately 104–113°. Hirshfeld surface analyses shows that H...H and H...C contacts dominate the TPS+cation environments, whereas H...Cl and shortM—S interactions link each [MCl4]n−anion to the surrounding cations. In (I) and (III), inversion-centered π–π stacking further consolidates the crystal packing, while in (II) no π–π interactions are observed.
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Syntheses and crystal structures of three triphenylsulfonium halometallate salts of zinc, cadmium and mercury
Bis(triphenylsulfonium) tetrachloridozinc(II), (C18H15S)2[ZnCl4] (I), bis(triphenylsulfonium) tetrachloridocadmium(II), (C18H15S)2[CdCl4] (II), and bis(triphenylsulfonium) tetrachloridomercury(II) methanol monosolvate, (C18H15S)2[HgCl4]·CH3OH (III), each crystallize in the monoclinic space groupP21/n. In all three structures, there are two crystallographically independent triphenylsulfonium (TPS) cations per asymmetric unit, each adopting a distorted trigonal–pyramidal geometry about the S atom (S—C bond lengths in the 1.77–1.80 Å range and C—S—C angles of 100–107°). The [MCl4]2–anions (M= Zn2+, Cd2+, Hg2+) are tetrahedral; their M—Cl bond lengths systematically increase from Zn2+to Hg2+, consistent with the larger ionic radius of the heavier metal. Hirshfeld surface analyses show that H...H and H...C contacts dominate the TPS cation environments, whereas H...Cl and S...Minteractions anchor each [MCl4]2–anion to two surrounding TPS cations. Weak C—H...Cl hydrogen bonds, as well as inversion-centered π–π stacking, generate layers in (I) and (II) and dimeric [(TPS)2–HgCl4]2assemblies in (III).
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- Award ID(s):
- 2215812
- PAR ID:
- 10626458
- Publisher / Repository:
- International Union of Crystallography
- Date Published:
- Journal Name:
- Acta Crystallographica Section E Crystallographic Communications
- Volume:
- 81
- Issue:
- 4
- ISSN:
- 2056-9890
- Page Range / eLocation ID:
- 358 to 363
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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