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. 2025 Mar 27;81(Pt 4):358-363.
doi: 10.1107/S2056989025002245. eCollection 2025 Apr 1.

Syntheses and crystal structures of three tri-phenyl-sulfonium halometallate salts of zinc, cadmium and mercury

Rylan Artis  1 , Elizabeth Heyward  1 , Naomi Reyes  1 , Kaitlyn Van Ostenbridge  1 , Will E Lynch  1 , Clifford W Padgett  1
Affiliations

Syntheses and crystal structures of three tri-phenyl-sulfonium halometallate salts of zinc, cadmium and mercury

Rylan Artis et al. Acta Crystallogr E Crystallogr Commun. .

Abstract

Bis(tri-phenyl-sulfonium) tetra-chlorido-zinc(II), (C18H15S)2[ZnCl4] (I), bis-(tri-phenyl-sulfonium) tetra-chlorido-cadmium(II), (C18H15S)2[CdCl4] (II), and bis-(tri-phenyl-sulfonium) tetra-chlorido-mercury(II) methanol monosolvate, (C18H15S)2[HgCl4]·CH3OH (III), each crystallize in the monoclinic space group P21/n. In all three structures, there are two crystallographically independent tri-phenyl-sulfonium (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 tetra-hedral; 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⋯M inter-actions 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]2 assemblies in (III).

Keywords: crystal structure; salts; tri­phenyl­sulfonium ion.

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Figures

Figure 1
Figure 1
The mol­ecular structure of (I) with displacement ellipsoids drawn at the 50% probability level.
Figure 2
Figure 2
The mol­ecular structure of (II) with displacement ellipsoids drawn at the 50% probability level.
Figure 3
Figure 3
The mol­ecular structure of (III) with displacement ellipsoids drawn at the 50% probability level.
Figure 4
Figure 4
A view along the a-axis direction of the crystal packing of (I) with close contacts shown as red dashed lines.
Figure 5
Figure 5
A view along the a-axis direction of the crystal packing of (II) with close contacts shown as red dashed lines.
Figure 6
Figure 6
A view along the a-axis direction of the crystal packing of (III) with close contacts shown as red dashed lines.
See this image and copyright information in PMC

References

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