HgI₂⋅As₄S₄: An Adduct from HgI₂ Molecules and Undistorted As₄S₄ Cages

Abstract

Unrattled cage: From the reaction of HgI2, As, and S, an adduct of linear HgI2 units and undistorted As4S4 cages is formed with only weak intermolecular interactions (see picture; Hg gray, I violet, S yellow, As blue). For the first time in this class of compounds, no polycationic network of Hg and S atoms is obtained. The optimization of the total energy prevents the formation of HgS bonds and the cleavage of the As4S4 cage.

Silver Coordination Chemistry of the Weakly Basic Cage As4S4

“…The distortion of the realgar cage is very small, but the different splitting pattern and intensities in the measured Raman spectra of 1 and 2 as well as the calculated bond valences underline the strong interactions of the ligand with the metal cation. This is a notable difference compared to the adducts of the mercury halides (Table ), where the Raman spectra are best described as a superposition of the spectra of the halide HgX 2 (X = Br, I) with the non‐coordinated realgar cluster, which proves their weak binding to the sulfur atoms , …”

“…Thus, a charge controlled complexation of the realgar cage should always proceed via the sulfur atoms. Until now, all complexes of intact realgar molecules proceeded via the sulfur atoms like in the weak complexes HgI 2 (As 4 S 4 ), (HgBr 2 ) 3 (As 4 S 4 ) 2 and CuI 3 (As 4 S 4 )(PAs 3 S 3 ), where the sulfur atoms coordinate via undistorted as well as distorted η 2 (S; S) and η 1 (S) coordination modes . However, the HOMO and HOMO–1 (Figure ) that are only 0.07 eV apart in energy show that an orbital controlled coordination of the realgar cage could proceed through both, an η 2 (S; S) coordination as well as an η 1 (As) coordination, depending on the acceptor needs.…”

“…When As 4 S 4 is exposed to strongly oxidizing environments, cage degradation towards the cation [As 3 S 4 ] + can occur . In 2006 Pfitzner et al synthesized HgI 2 (As 4 S 4 ) through a solid state reaction with stoichiometric amounts of sulfur and arsenic and disproved the common belief that realgar features no coordination chemistry of the intact cage . In this complex, the realgar molecules are rather weakly bound to the HgI 2 dumbbells in a distorted η 2 (S, S) fashion through sulfur atoms [ d HgS = 298.3(4) and 323.6(3) pm].…”

The Unexpected Versatility of P4S3 as a Building Block in Polymeric Copper Halide Networks: 2,3‐P, 1,2,3‐P and all‐P Coordination

“…In this context it may be of interest that the assembly of As 4 S 4 ·HgI 2 dimers by melting together As, S and HgI 2 occurs through sulfur lone pairs. [20] Experimental Section General: All manipulations were carried out under nitrogen by using Schlenk techniques. Diffusion experiments were usually carried out in Schlenk tubes of 3.0 cm diameter unless described otherwise.…”

Partial Geometric Frustration in Inorganic Supramolecular Spin Systems with One-Dimensional Trigonally Aligned Magnetic Chains ∞1(MCl4)2− (M = Fe2+, Co2+)

“…Although lots of metal chalcohalides have been found181920, rare work on magnetic assemblies has been reported in such systems, except MnPnQ 2 X (Pn = Sb, Bi; Q = S, Se; X = Cl, Br, I)21, Ce 53 Fe 12 S 90 × 3 (X = Cl, Br, I)22, Ba 4 Fe 2 I 5 S 4 23, and (Hg 3 Te 2 )(UCl 6 )13.…”