The reactions of tellurium tetrahalides and triphenylphosphine in tetrahydrofuran have been carried out under ambient conditions and afford [(Ph(3)PO)(2)H](2)[Te(2)X(10)] [X = Cl (1), Br (2)] and [(Ph(3)PO)(3)(OH(3)])(2)[TeI(6)] (4). The X-ray structures of 1 and 2 show that they are isostructural and contain discrete [Te(2)X(10)](2-) anions exhibiting octahedral coordination around both tellurium atoms with one shared edge and [Ph(3)POH...OPPh(3)](+) cations that show strong hydrogen bonds (the O...O distances are 2.399 and 2.404 A for 1 and 2, respectively). The compound 4 is built up with discrete octahedral hexaiodotellurate anions and [(Ph(3)PO)(3)(OH(3))](+) cations. The reaction of TeBr(4) and PPh(3) also results in the formation of formally zwitterionic Ph(3)PO(CH(2))(4)TeBr(4) (3). This reaction involves an unprecedented THF ring opening in which the oxygen atom becomes bonded to the phosphorus atom of triphenylphosphine and the carbon atom at the other end of the five-atomic chain becomes bonded to the tellurium atom of TeBr(4). The ring opening of the solvent THF is also taking place in the reaction involving tellurium tetraiodide, as indicated by the formation of C(4)H(8)TeI(2) (5). The reaction may initially lead to Ph(3)PI(2) that reacts with THF yielding Ph(3)PO and ICH(2)(CH(2))(2)CH(2)I. The latter species reacts with elemental tellurium producing 5. Depending on the conditions upon crystallization, two polymorphs of C(4)H(8)TeI(2) (5a and 5b) are observed. While the molecular structures of the two forms are virtually identical, their packing and intermolecular contacts are different. Two further minor products (6a and 6b) were isolated in the reaction of TeI(4) and PPh(3): Both are formally 1:1 adducts of 5 and TeI(4), but they differ considerably in their structures. 6a can be formulated as [C(4)H(8)TeI(+)](2)[Te(2)I(10)(2-)] and 6b as [C(4)H(8)TeI(+)](2)(TeI(3)(+))(2)(I(-))(4). The latter compound exhibits framework similar to that of the tetramers in gamma- and delta-TeI(4).

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Laitinen, R. (2014). Identification of mixed bromidochloridotellurate anions in disordered crystal structures of (bdmim)2[TeX2Y4] (X, Y = Br, Cl; bdmim = 1-butyl-2,3 -dimethylimidazolium) by combined application of Raman spectroscopy and solidstate DFT calculations. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 117, 728-738. doi:10.1016/j.saa.2013 1.Introduction.X-ray crystallography provides the most definite means to elucidate structures of different types of materials at the molecular level. However, successful routine structure determinations require crystalline material, which contains well-defined single crystals with ordered, periodically repeating structures. In many cases this is not a case. For instance, disorder and twinning are common occurrences, and the number of modular structures is continually growing. Various techniques have been developed to deal with some of these problems, as exemplified in refs. 1-5, though some types of disorder cannot be resolved by X-ray crystallography alone.Spectroscopic methods have often been evoked to resolve the crystallographic disorder. For instance, crystalline eight-membered SenS8-n ring molecules [6] or [TiCp2SenS5-n] complexes [7] are solid solutions of 30 and 20 molecular species, respectively, taking the presence of isomers into account. Consequently, each chalcogen-atom sites in both compounds are partially occupied by sulfur and selenium atoms. In both cases, individual molecules have been identified by dissolving the crystalline samples, and recording and assigning their 77 Se NMR spectra [6,7].Vibrational spectroscopy is useful in the identification of individual species in disordered crystal

The asymmetric unit of the title compound, 2C18H15Te+·2Br−·C3H6O or Ph3TeBr·0.5Me2CO, contains two crystallographically independent tri­phenyl­telluronium cations, two bromide anions, and one disordered [site-occupancy ratio = 0.581 (7):0.419 (7)] solvent mol­ecule. Inter­ionic Te⋯Br inter­actions connect the cations and anions into a tetra­meric step-like structure. The primary coordination spheres of both Te atoms are TeC3 trigonal pyramids: three short secondary tellurium–bromine inter­actions expand the coordination geometry of one of the Te atoms to an octa­hedron. While the other Te atom shows only two Te⋯Br secondary bonding inter­actions, it is also six-coordinated due to a Te⋯π inter­action [3.769 (2) Å] with one of the phenyl rings of the adjacent cation.

The asymmetric unit of the title salt, [C22H20O2P]2 +[TeI6]2−, consists of one triphenyl(5-oxooxolan-3-yl)phosphanium cation and one half of a hexa­iodido­tellurate(IV) dianion. The Te atom is located at an inversion centre and is octa­hedrally coordinated by six I atoms. The Te—I bond lengths range from 2.9255 (9) to 2.9439 (10) Å. The I—Te—I angles between cis-iodide ligands are in the range 87.85 (3)–92.15 (3)°. In the crystal, the components are connected by C—H⋯I inter­actions. In the final refinement of the compound a void of 32 Å3 was observed.

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2-ethylenediammonium dichloride (1) and dibromide (2) were prepared by the reaction of N,N,N ,N -tetramethyl-1,2-ethylenediamine and the corresponding 1-halopropane. The structures of the compounds were characterized by single-crystal X-ray diffraction. 1 · 2H 2 O crystallizes in the triclinic crystal system, space group P1, with Z = 1, and 2 in the monoclinic crystal system, space group P2 1 /c, with Z = 2. The crystal structures of the salts consist of discrete dications and halide anions. The packing in 1 · 2H 2 O consists of layers of cations with the chloride anions and water molecules forming hydrogen-bonded chains between the cation layers. In 2, the strongest H···Br hydrogen bonds of 2.8138(6) and 2.8187(7)Å link the cations and anions into doublestranded chains. In both salts, cations and anions are also linked together by a further weak C-H···Cl/Br hydrogen bonding network.

The asymmetric unit of the title compound, (C14H34N2)[Fe2Cl6O], contains one complete cation, two half-cations and two anions. The two half-cations are completed by crystallographic inversion symmetry. The FeIII atoms adopt fairly regular FeCl3O tetra­hedral geometries, although the bridging Fe—O—Fe bond angles differ significantly in the two anions, which both adopt an eclipsed conformation. In the crystal, the components are linked by C—H⋯Cl and C—H⋯O inter­actions.