Syntheses and crystal structures of phenyltrimethylammonium salts of hexachlorotellurate(IV), [C6H5(CH3)(3)N](2)[TeCl6], catena-poly[(di-mu-chlorobis{tetrachlorotellurate(IV)})-mu-bromine], [C6H5(CH3)(3)N](2n)[Te2Cl10 center dot Br-2](n), and di-mu-chlorobis{tetrachlorotellurate(IV) catena-poly[(mu-chlorobis{pentachlorotellurate(IV)})-mu-iodine(I)], [C6H5(CH3)(3)N](4n)[Te2Cl10](n)[Te2Cl11 center dot I](n)

The title compounds were prepared from tellurium tetrachloride, phenyltrimethylammonium chloride and halogens. The crystal structures of [C6H5(CH3)(3)N](2)[TeCl6] (1), [C6H5(CH3)(3)N](2n)[Te2Cl10. Br-2](n) (2) and [C6H5(CH3)(3)N](4n) [Te2Cl10](n)[Te2Cl11. I](n) (3) have been determined by X-ray methods and refined to R=0.018, 0.029 and 0.032 for 2648, 3025 and 1883 observed reflections, respectively. Crystals of 1 are monoclinic, space group P2(1)/a with Z=2 and a=13.965(3), b=10.292(2), c=8.608(2) Angstrom, beta=104.51(2)degrees. Crystals of 2 are triclinic, space group <P(1)over bar> with Z=1 and a=8.672(1), b=8.785(1), c=11.565(1) Angstrom, alpha=95.93(2)degrees, beta=103.27(2)degrees, gamma=90.44(2)degrees. Crystals of 3 are orthorhombic, space group Pnnm with Z=2 and a=11.952(1), b=16.475(2), c=16.923(2) Angstrom. The [TeCl6](2-) of 1 is a centrosymmetric and nearly perfect octahedron. The dimeric, centrosymmetric [Te2Cl10](2-) anion of 3 consists of two edge-sharing distorted TeCl6 octahedra. The same dimeric unit occurs in 2, but here one of the axial Cl atoms in each TeCl6 octahedron is linked to an equivalent Cl atom by a Br-2 molecule, and so forming a polymeric chain, [Te2Cl10. Br-2](2n-)(n). The [Te2Cl11. I](2-) anion of 3 consists of a distorted TeCl6 octahedron with one Cl atom on a centre of symmetry and one Cl atom (cis to the central Cl atom) bonded to an I+ ion, also situated on a centre of symmetry, and so forming a polymeric chain, [Te2Cl11. I](2n-)(n).