The reactions between diphenyl ditelluride, (PhTe)2, or di(β‐naphtyl)ditelluride, (β‐naphtylTe)2, with equivalent amounts of iodine have been reinvestigated and the crystal and molecular structures of iodophenyltellurium(II), (PhTeI)4, and diiododi‐(β‐naphtyl)tellurium(IV), (β‐naphtyl)2TeI2, have been determined. The structure of iodophenyltellurium(II) (space group Cc, a = 13.850(5) Å, b = 13.852(3) Å, c = 16.494(6) Å and β = 101.69(2)°, Z = 4) is built up by four PhTeI units which are linked by weak Te–Te interactions with Te–Te distances between 3.152(5) Å and 3.182(4) Å. The angles between the tellurium atoms are approximately 90° giving an almost perfect square. Long range secondary bonds (Te–I: about 4.2 Å) link the tetrameric units to give an infinite two‐dimensional network. Iodo(β‐naphtyl)tellurium(II) is less stable than the phenyl derivative. Solutions of this compound decompose under formation of elemental tellurium and (β‐naphtyl)2TeI2. (β‐Naphtyl)2TeI2 crystallises in the monoclinic space group C 2/c (a = 21.198(6) Å, b = 5.8921(8) Å, c = 16.651(5) Å, β = 114.77(2)°). The tellurium atom is situated on a two‐fold crystallographic axis and Te–I and Te–C bond lengths of 2.899(1) and 2.108(7) Å have been determined.

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The direct reaction between PhTeCl3 and CsCl in methanol affords {Cs[PhTeCl4]·CH3OH}. Cs[PhTeBr4] was prepared by refluxing [2‐Br‐C5NH5][PhTeBr4] and CsCl in ethanol in the presence of an excess of HBr. In {Cs[PhTeCl4]·CH3OH} the [PhTeCl4]— units form dimers by secondary Te···Cl bonds with methanol molecules bridging adjacent Cs+ cations. In both compounds, the alkali metal cation interacts secondarily with the chlorine and bromine Te‐ligands, achieving singular coordination polyhedrons and holding the lattices in supramolecular tridimensional assemblies. The new complexes, {Cs[PhTeCl4]·CH3OH} and Cs[PhTeBr4], crystallize in the space groups P21/c and P21/n, respectively. Only one such structure has been reported before.

The reaction of tellurium(IV) tetrahalides with hydrochloric and hydrobromic acid leads to the formation of (H3O)2[TeX6], which reacts subsequently with (2‐Br‐C5NH5)+X‐ to afford (2‐Br‐C5NH5)2[TeCl6] (1) and (2‐Br‐C5NH5)2[TeBr6] (2). The structure of the complex salts were analysed by X‐ray diffractometry affording the centrosymmetric space groups P21/n (monoclinic, 1) and P1¯ (triclinic, 2). Interionic hydrogen bondings hold their lattices in bidimensional supramolecular arrays not yet described in the literature. The lone electron pair of the AX6E‐system of the hexahalotellurates [TeX6]2‐ (X = Cl, Br) seems to be fully delocalized since only small octahedral deviations were observed for the anionic species. The structures of the title compounds were refined with the Te atoms occupying sites with full point symmetry, approximately m3¯m. In both cases the Te atoms enclose centers of inversion and the octahedrally dynamic structures are enforced and stabilized along the supramolecular lattices by the crystal field of the 2‐Br‐pyridinium cations.

The title compound, [Au(4,6‐Me2pymS)(PPh3)] or [Au(C6H7N2S)(C18H15P)], exhibits a linear Au atom S—Au—P geometry, with Au—P = 2.247 (2) Å, Au—S = 2.289 (2) Å and P—Au—S = 178.19 (11)°. There is an intramolecular interaction between one N atom of the 4,6‐Me2pymS ligand and the Au atom, with an Au⋯N distance of 3.154 (8) Å.