Plasticity of Cl−Te−Cl Fragments. Synthesis, Single-Crystal X-ray, and NBO Study of (1-Thia-2-tellura-1-phenyl-4-chloro)cyclopentane 2,2,2-Trichloride

Abstract

Tellurium tetrachloride and allylphenyl sulfide react to form (1-thia-2-tellura-1-phenyl-4-chloro)cyclopentane 2,2,2-trichloride. The crystal and molecular structure were determined by single-crystal X-ray techniques. The crystals belong to the monoclinic system, space group P2(1)/c (No. 14) with a = 6.020(3) Å, b = 11.46(1) Å, c = 20.156(2) Å, beta = 97.53(2) degrees, V = 1379(1) Å(3), and Z = 4. The structure was refined to the final R value of 0.036. The coordination around Te(IV) is distorted psi octahedral with three Cl atoms in the equatorial positions. The axial Te(1)-C(1) bond opposite to the lone pair of electrons at the Te(IV) atom completes the coordination polyhedron. The intramolecular Te-S distance is 2.903(3) Å. Symmetric and asymmetric deformation modes were established to describe the plasticity of the Cl-Te-Cl fragments extracted from the Cambridge Structural Database. The hypervalency of Te(IV) manifests itself as plasticity in the equatorial plane of the coordination sphere. The NBO calculations show that all of the equatorial Te-Cl bonds are highly polarized and the electrons reside mainly on the Cl atoms.

Theoretical investigation on sulfur‐containing chelating resin‐divalent metal complexes

“…Second‐order perturbation theory analysis of the Fock matrix in NBO basis was carried out to evaluate the donor–acceptor interactions 65–67. The interactions result in a loss of occupancy from a localized NBO of the idealized Lewis structure into an empty non‐Lewis orbital.…”

Tellurium⋯π-aryl interactions: a new bonding motif for supramolecular self-assembly and crystal engineering

“…Another compound in which tellurium is part of a heterocycle formed through a dative bond (Te-S 2.902 A ˚), 1-thia-2tellura-1-phenyl-2,2,2,4-tetrachlorocyclopentane, 81 [SAQGOG], forms supramolecular helical chains parallel to the x axis, via intermolecular Te … p interactions between tellurium and phenyl rings of adjacent molecules (Fig. 38).…”

Supramolecular Aggregation Patterns and Stereochemical Consequences of Tellurium(Lone Pair)…π(Aryl) Interactions

“…After manual sorting, a total of eight tellurium(IV) structures were found to exhibit Te(lone pair)···π (aryl) interactions; data are summarised in Table 12.1 and chemical diagrams of the interacting species are shown in Scheme 12.2 [18][19][20][21][22][23][24][25]. Two supramolecular aggregation patterns are noted in this series.…”