Syntheses and Structures of Two Selenite Chloride Hydrates: Co(HSeO3)Cl · 3 H2O and Cu(HSeO3)Cl · 2 H2O

The first selenite chloride hydrates, Co(HSeO₃)Cl · 3 H₂O and Cu(HSeO₃)Cl · 2 H₂O, have been prepared from solution and characterised by single‐crystal X‐ray diffraction. The cobalt phase adopts an unusual “one‐dimensional” structure built up from vertex‐sharing pyramidal [HSeO₃]^2–, and octahedral [CoO₂(H₂O)₄]^2– and [CoO₂(H₂O)₂Cl₂]^4– units. Inter‐chain bonding is by way of hydrogen bonds or van der Waals' interactions. The atomic arrangement of the copper phase involves [HSeO₃]^2– pyramids and Jahn‐Teller distorted [CuCl₂(H₂O)₄] and [CuO₄Cl₂]^8– octahedra, sharing vertices by way of Cu–O–Se and Cu–Cl–Cu bonds. Crystal data: Co(HSeO₃)Cl · 3 H₂O, M_r = 276.40, triclinic, space group P 1 (No. 2), a = 7.1657(5) Å, b = 7.3714(5) Å, c = 7.7064(5) Å, α = 64.934(1)°, β = 68.894(1)°, γ = 71.795(1)°, V = 337.78(7) ų, Z = 2, R(F) = 0.036, wR(F) = 0.049. Cu(HSeO₃)Cl · 2 H₂O, M_r = 263.00, orthorhombic, space group Pnma (No. 62), a = 9.1488(3) Å, b = 17.8351(7) Å, c = 7.2293(3) Å, V = 1179.6(2) ų, Z = 8, R(F) = 0.021, wR(F) = 0.024.     

Compounds with Cluster Cations together with Cluster Anions [(M6X12)(EtOH)6]2+ besides [(Mo6Cl8)Cl4X2]2– (M = Nb,Ta; X = Cl,Br) – Synthesis and Crystal Structures

Compounds consisting of both cluster cations and cluster anions of the composition [(M₆X₁₂)(EtOH)₆][(Mo₆Cl₈)Cl₄X₂] · n EtOH · m Et₂O (M = Nb, Ta; X = Cl, Br) have been prepared by the reaction of (M₆X₁₂)X₂ · 6 EtOH with (Mo₆Cl₈)Cl₄. IR data are given for three compounds. The structures of [(Nb₆Cl₁₂)(EtOH)₆][(Mo₆Cl₈)Cl₆] · 3 EtOH · 3 Et₂O 1 and [(Ta₆Cl₁₂)(EtOH)₆][(Mo₆Cl₈)Cl₆] · 6 EtOH 2 have been solved in the triclinic space group P1 (No. 2). Crystal data: 1 , a = 10.641(2) Å, b = 13.947(2) Å, c = 15.460(3) Å, α = 65.71(2)°, β = 73.61(2)°, γ = 85.11(2)°, V = 2005.1(8) ų and Z = 1; 2 , a = 11.218(2) Å, b = 12.723(3) Å, c = 14.134(3) Å, α = 108.06(2)°, β = 101.13(2)°, γ = 91.18(2)°, V = 1874.8(7) ų and Z = 1. Both structures are built of octahedral [(M₆Cl₁₂)(EtOH)₆]²⁺ cluster cations and [(Mo₆Cl₈)Cl₆]^2– cluster anions, forming distorted CsCl structure types. The Nb–Nb and Ta–Ta bond lengths of 2.904 Å and 2.872 Å (mean values), respectively, are rather short, indicating weak M–O bonds. All O atoms of coordinated EtOH molecules are involved in H bridges. The Mo–Mo distances of 2.603 Å and 2.609 Å (on average) are characteristic for the [(Mo₆Cl₈)Cl₆]^2– anion, but there is a clear correlation between the number of hydrogen bridges to the terminal Cl and the corresponding Mo–Cl distances.     

Chloro- und Polyselenoselenate(II) Darstellung,Struktur und Eigenschaften von [Ph3(C2H4OH)P]2[SeCl4] · MeCN, [Ph4P]2[Se2Cl6] und [Ph4P]2[Se(Se5)2]

Chloro- and Polyselenoselenates(II): Synthesis, Structure, and Properties of [Ph₃(C₂H₄OH)P]₂[SeCl₄] · MeCN, [Ph₄P]₂[Se₂Cl₆], and [Ph₄P]₂[Se(Se₅)₂] By symproportionation of elemental selenium and SeCl₄ in polar protic solvents the novel chloroselenates(+II), [SeCl₄]^2? and [Se₂Cl₆]^2?, could be stabilized; they were crystallized with voluminous organic cations. They were characterized from complete X-ray structure analysis. Yellow-orange [Ph₃(C₂H₄OH)P]₂[SeCl₄] · MeCN (space group P1 , a = 10.535(4), b = 12.204(5), c = 16.845(6) Å, α = 77.09(3)°, β = 76.40(3)°, γ = 82.75(3)° at 140 K) contains in its crystal structure monomeric [SeCl₄]^2? anions with square-planar coordination of Se(+II). The mean Se? Cl bond length is 2.441 Å. In yellow [Ph₄P]₂[Se₂Cl₆] (space group P1 , a = 10.269(3), b = 10.836(4), c = 10.872(3) Å, α = 80.26(3)°, β = 79.84(2)°, γ = 72.21(3)° at 140 K) a dinuclear centrosymmetric [Se₂Cl₆]^2? anion, also with square-planar coordinated Se(+II), is observed. The average terminal and bridging Se? Cl bond distances are 2.273 and 2.680 Å, respectively. From redox reactions of elemental Se with boranate/thiolate in ethanol/DMF the bis(pentaselenido)selenate(+II) anion [Se(Se₅)₂]^2? was prepared as a novel type of a mixed-valent chalcogenide. In dark-red-brown [Ph₄P]₂[Se(Se₅)₂] (space group P2₁/n, a = 12.748(4), b = 14.659(5), c = 14.036(5) Å, β = 108.53(3)° at 140 K) centrosymmetric molecular [Se(Se₅)₂]^2? anions with square-planar coordination of the central Se(+II) by two bidentate pentaselenide ligands is observed (mean Se? Se bond lengths: 2.658 Å at Se(+II), 2.322 Å in [Se₅]_2?). The resulting six-membered chelate rings with chair conformation are spirocyclically linked through the central Se(+II). The vibrational spectra of the new anions are reported.     

A long Nb=O double bond in bis(pyridinium) tetra­chlorooxo(pyridine‐κN)niobate(V) chloride

The asymmetric unit of the title compound, (C₅H₆N)₂[NbCl₄O(C₅H₅N)]Cl or (pyH)₂[O=NbCl₄(py)]Cl (py is pyridine), contains a discrete anionic niobium(V) complex, [O=NbCl₄(py)]⁻, and two protonated pyridine mol­ecules, which form medium–strong hydrogen bonds with the Cl⁻ counter‐ion. The Nb=O distance of 1.7643 (17) Å is the longest among those in congener niobium complexes reported to date. Extensive density functional theory studies of conformations of [O=NbCl₄(py)]⁻ and structural data mining raise doubts regarding the reliability of the length of this Nb=O double bond.     

Two Novel CuII Phenanthroline Adipato Complexes with π‐π Stacking Interactions: [Cu(phen)2(C6H8O4)] · 4.5 H2O and [(Cu2(phen)2Cl2)(C6H8O4)] · 4 H2O

The blue copper complex compounds [Cu(phen)₂(C₆H₈O₄)] · 4.5 H₂O ( 1 ) and [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)] · 4 H₂O ( 2 ) were synthesized from CuCl₂, 1,10‐phenanthroline (phen) and adipic acid in CH₃OH/H₂O solutions. [Cu(phen)₂‐ (C₆H₈O₄)] complexes and hydrogen bonded H₂O molecules form the crystal structure of ( 1 ) (P1 (no. 2), a = 10.086(2) Å, b = 11.470(2) Å, c = 16.523(3) Å, α = 99.80(1)°, β = 115.13(1)°, γ = 115.13(1)°, V = 1617.5(5) ų, Z = 2). The Cu atoms are square‐pyramidally coordinated by four N atoms of the phen ligands and one O atom of the adipate anion (d(Cu–O) = 1.989 Å, d(Cu–N) = 2.032–2.040 Å, axial d(Cu–N) = 2.235 Å). π‐π stacking interactions between phen ligands are responsible for the formation of supramolecular assemblies of [Cu(phen)₂(C₆H₈O₄)] complex molecules into 1 D chains along [111]. The crystal structure of ( 2 ) shows polymeric [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)_2/2] chains (P1 (no. 2), a = 7.013(1) Å, b = 10.376(1) Å, c = 11.372(3) Å, α = 73.64(1)°, β = 78.15(2)°, γ = 81.44(1)°, V = 773.5(2) ų, Z = 1). The Cu atoms are fivefold coordinated by two Cl atoms, two N atoms of phen ligands and one O atom of the adipate anion, forming [CuCl₂N₂O] square pyramids with an axial Cl atom (d(Cu–O) = 1.958 Å, d(Cu–N) = 2.017–2.033 Å, d(Cu–Cl) = 2.281 Å; axial d(Cu–Cl) = 2.724 Å). Two square pyramids are condensed via the common Cl–Cl edge to centrosymmetric [Cu₂Cl₂N₄O₂] dimers, which are connected via the adipate anions to form the [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)_2/2] chains. The supramolecular 3 D network results from π‐π stacking interactions between the chains. H₂O molecules are located in tunnels.     

Chloroselenate mit zwei- und vierwertigem Selen: 77Se-NMR-Spektren,Synthese und Kristallstrukturen von (PPh4)2SeCl6 · 2 CH2Cl2, (NMe3Ph)2SeCl6, (K-18-Krone-6)2SeCl6 · 2 CH3CN,PPh4Se2Cl9, (NEt4)2Se2Cl10, (PPh4)2Se3Cl8 · CH2Cl2 und (PPh4)2Se4Cl12 · CH2Cl2

Chloroselenates with Di- and Tetravalent Selenium: ⁷⁷Se-NMR-Spectra, Syntheses, and Crystal Structures of (PPh₄)₂SeCl₆ · 2 CH₂Cl₂, (NMe₃Ph)₂SeCl₆, (K-18-crown-6)₂SeCl₆ · 2 CH₃CN, PPh₄Se₂Cl₉, (NEt₄)₂Se₂Cl₁₀, (PPh₄)₂Se₃Cl₈ · CH₂Cl₂, and (PPh₄)₂Se₄Cl₁₂ · CH₂Cl₂ The title compounds were obtained from reactions of selenium and selenium tetrachloride with PPh₄Cl, NEt₄Cl, NMe₃PhCl, or (K-18-crown-6)Cl in dichloromethane or acetonitrile. (PPh₄)₂Se₃Cl₈ · CH₂Cl₂ was also formed from GeSe, PPh₄Cl and chlorine in acetonitrile. The ⁷⁷Se-NMR spectra of the solutions show the presence of dynamical equilibria which, depending on composition, mainly contain SeCl₂, SeCl₄, Se₂Cl₂, SeCl₆^2–, Se₂Cl₆^2–, and/or Se₂Cl₁₀^2–. Solutions of AsCl₃ and (PPh₄)₂Se₄ in acetonitrile upon chlorination with Cl₂ or PPh₄AsCl₆ yielded (PPh₄)₂Se₂Cl₆, while (PPh₄)₂As₂Se₄Cl₁₂ was the product after chlorination with SOCl₂. According to the X-ray crystal structure analyses the ions SeCl₆^2–, Se₂Cl₉^–, and Se₂Cl₁₀^2– have the known structures with octahedral coordination of the Se atoms. The structure of the Se₃Cl₈^2– ion corresponds to that of Se₃Br₈^2– consisting of three SeCl₂ molecules associated via two Cl^– ions. (PPh₄)₂Se₄Cl₁₂ · CH₂Cl₂ is isotypic with the corresponding bromoselenate and contains anions in which three SeCl₂ molecules are attached to a SeCl₆^2– ion; there is a peculiar Se–Se interaction.     

catena‐Poly­[[tetrakis(2‐allyl­tetrazole‐κN4)‐tetra‐μ‐chloro‐tricopper(II)]‐di‐μ‐chloro]

In the crystal structure of the title compound, [Cu₃Cl₆(C₄H₆N₄)₄]_n, there are three Cu atoms, six Cl atoms and four 2‐allyl­tetrazole ligands in the asymmetric unit. The polyhedron of one Cu atom adopts a flattened octahedral geometry, with two 2‐allyl­tetrazole ligands in the axial positions [Cu—N4 = 1.990 (2) and 1.991 (2) Å] and four Cl atoms in the equatorial positions [Cu—Cl = 2.4331 (9)–2.5426 (9) Å]. The polyhedra of the other two Cu atoms have a square‐pyramidal geometry, with three basal sites occupied by Cl atoms [Cu—Cl = 2.2487 (9)–2.3163 (8) and 2.2569 (9)–2.3034 (9) Å] and one basal site occupied by a 2‐allyl­tetrazole ligand [Cu—N4 = 2.028 (2) and 2.013 (2) Å]. A Cl atom lies in the apical position of either pyramid [Cu—Cl = 2.8360 (10) and 2.8046 (9) Å]. The possibility of including the tetrazole N3 atoms in the coordination sphere of the two Cu atoms is discussed. Neighbouring copper polyhedra share their edges with Cl atoms to form one‐dimensional polymeric chains running along the a axis.     

Die Chlorooxoarsenate(III) (PPh4)2[As4O2Cl10] · 2 CH3CN und (PPh4)2[As2OCl6] · 3 CH3CN

The Chlorooxoarsenates(III) (PPh₄)₂[As₄O₂Cl₁₀] · 2 CH₃CN and (PPh₄)₂[As₂OCl₆] · 3 CH₃CN (PPh₄)₂[As₂Cl₈] can be prepared from As₂O₃, SOCl₂ and PPh₄Cl in acetonitrile. Its oxidation with chlorine yields PPh₄[AsCl₆]. This was also obtained directly from arsenic, chlorine and PPh₄Cl, (PPh₄)₂[As₄O₂Cl₁₀] · 2 CH₃CN being a side product; the latter was obtained with high yield from AsCl₃, As₂O₃ and PPh₄Cl in acetonitrile. By addition of PPh₄Cl it was converted to (PPh₄)₂[As₂OCl₆] · 3 CH₃CN. According to their X-ray crystal structure analyses, both crystallize in the triclinic space group P 1. The [As₄O₂Cl₁₀]^2– ion can be regarded as a centrosymmetric association product of two Cl₂AsOAsCl₂ molecules and two Cl^– ions, each Cl^– ion being coordinated with all four As atoms. In the [As₂OCl₆]^2– ion the As atoms are linked via the O atom and two Cl atoms.     

Crystal Structure of Tl<Subscript>2</Subscript>[NbCl<Subscript>6</Subscript>] and Tl<Subscript>2</Subscript>[NbBr<Subscript>6</Subscript>]

Single crystals of Tl₂[NbCl₆] (1) and Tl₂ [NbBr₆] (2) are obtained as black needles on heating TlCl, Nb, S₂Cl₂ (1) and Tl, Nb, and Br₂ at 400°C (2). Tl₂NbBr₆ also forms in the reaction of TlBr, Nb, Br₂, and S at 500°C. Both compounds crystallize in the K₂[PtCl₆] structure type to form non-distorted octahedral [NbХ₆]^2– anions (Nb–Cl 2.397(4) Å and Nb–Br 2.516(2) Å). The magnetic properties of Tl₂[NbBr₆] in a range 5-300 K indicate an antiferromagnetic interaction between Nb⁴⁺ ion spins (d¹, S = 1/2). On cooling, the compound becomes a noncollinear ferromagnet with T_c = 23 K.     

Die Oxochlorotantalate (PPh4)2[Ta2OCl9]2 · 2 CH2Cl2, (PPh4)2[Ta2OCl10] · 2 CH3CN und (K-18-Krone-6)4[Ta4O6Cl12] · 12 CH2Cl2

The Oxochlorotantalates (PPh₄)₂[Ta₂OCl₉]₂ · 2 CH₂Cl₂, (PPh₄)₂[Ta₂OCl₁₀] · 2 CH₃CN, and (K-18-crown-6)₄[Ta₄O₆Cl₁₂] · 12 CH₂Cl₂ (K-18-crown-6)₄[Ta₄O₆Cl₁₂] · 12 CH₂Cl₂ was obtained from a reaction of tantalum pentachloride, K₂S₅ and 18-crwon-6 in dichlormethane. According to its crystal structure analysis it is tetragonal (space group I 4 2d) and contains [Ta₄O₆Cl₁₂]^4– ions that have an adamantane-like Ta₄O₆ skeleton. Each K⁺ ion is coordinated by the oxygen atoms of the crown ether molecule from one side and with three Cl atoms of one [Ta₄O₆Cl₁₂]^4– ion from the opposite side. (PPh₄)₂[Ta₂OCl₁₀] · 2 CH₃CN was a product from PPh₄Cl and TaCl₅ in acetonitrile in the presence of Na₂S₄. Its crystals are monoclinic (space group P2₁/c) and contain centrosymmetric [Ta₂OCl₁₀]^2– ions having a linear Ta–O–Ta grouping with short bonds (Ta–O 189 pm). TaCl₅ and H₂S formed a solid substance (TaSCl₃) from which a small amount of (PPh₄)₂[Ta₂OCl₉]₂ · 2 CH₂Cl₂ was obtained by the reaction with PPh₄Cl in CH₂Cl₂. The anions in the monoclinic crystals (space group P2₁/n) consist of two Ta₂OCl₉^– units which are joined by chloro bridges; each Ta₂OCl₉^– unit has a nearly linear Ta–O–Ta group with differing bond lengths (179 and 202 pm). The oxygen in the compounds probably was introduced by traces of water in the crown ether, acetonitrile or H₂S, respectively.     

Synthesis and Thermal Behaviour of Compounds in the System [Ph4P]Cl/BiCl3 and the Crystal Structures of [Ph4P]3[Bi2Cl9] · 2 CH2Cl2 and [Ph4P]2[Bi2Cl8] · 2 CH3COCH3

Six polynuclear chlorobismuthates are formed in the reaction between BiCl₃ and Ph₄PCl by variation of the molar ratio of the educts, the solvents and the crystallisation methods: [Ph₄P]₃[Bi₂Cl₉] · 2 CH₂Cl₂, [Ph₄P]₃[Bi₂Cl₉] · CH₃COCH₃, [Ph₄P]₂[Bi₂Cl₈] · 2 CH₃COCH₃, [Ph₄P]₄[Bi₄Cl₁₆] · 3 CH₃CN, [Ph₄P]₄[Bi₆Cl₂₂], and [Ph₄P]₄[Bi₈Cl₂₈]. We report the crystal structure of [Ph₄P]₃[Bi₂Cl₉] · 2 CH₂Cl₂ which crystallises with triclinic symmetry in the S. G. P1 No. 2, with the lattice parameters a = 13.080(3) Å, b = 14.369(3) Å, c = 21.397(4) Å, α = 96.83(1)°, β = 95.96(1)°, γ = 95.94(2)°, V = 3943.9(1) ų, Z = 2. The anion is formed from two face‐sharing BiCl₆‐octahedra. [Ph₄P]₂[Bi₂Cl₈] · 2 CH₃COCH₃ crystallises with monoclinic symmetry in the S. G. P2₁/n, No. 14, with the lattice parameters a = 14.045(5) Å, b = 12.921(4) Å, c = 17.098(3) Å, β = 111.10(2)°, V = 2894.8(2) ų, Z = 2. The anion is a bi‐octahedron of two square‐pyramids, joined by a common edge. The octahedral coordination is achieved with two acetone ligands. [Ph₄P]₄[Bi₄Cl₁₆] · 3 CH₃CN crystallises in the triclinic S. G., P1, No. 2, with the lattice parameters a = 14.245(9) Å, b = 17.318(6) Å, c = 24.475(8) Å, α = 104.66(3)°, β = 95.93(3)°, γ = 106.90(4)°, V = 5486(4) ų, Z = 2. Two Bi₂Cl₈ dimers in syn‐position form the cubic anion. Lattice parameters of [Ph₄P]₃[Bi₂Cl₉] · CH₃COCH₃ are also given. The solvated compounds are desolvated at approximately 100 °C. [Ph₄P]₃[Bi₂Cl₉] · 2 CH₂Cl₂ and [Ph₄P]₃[Bi₂Cl₉] · CH₃COCH₃ show the same sequence of phase transitions after desolvation. All compounds melt into a liquid in which some order is observed and transform on cooling into the glassy state.     

Phosphaniminato-Trichloroselenate(II): Synthese und Kristallstrukturen von [SeCl(NPPh3)2]+SeCl3− und [Me3SiN(H)PMe3]2+[Se2Cl6]2−

Phosphorane Iminato-Trichloroselenates(II): Syntheses and Crystal Structures of [SeCl(NPPh₃)₂]⁺SeCl₃^? and [Me₃SiN(H)PMe₃]₂⁺[Se₂Cl₆]^2? [SeCl(NPPh₃)₂]⁺SeCl₃^? has been synthesized by the reaction of Se₂Cl₂ with Me₃SiNPPh₃ in acetonitrile solution, forming orangered crystals, whereas red crystals of [Me₃SiN(H)PMe₃]₂⁺[Se₂Cl₆]^2? were obtained by the reaction of Me₃SiNPMe₃ with SeOCl₂ in acetonitrile solution. Both complexes were characterized by X-ray structure determinations. [SeCl(NPPh₃)₂]⁺SeCl₃^?: Space group P2₁/n, Z = 4, structure solution with 7 489 observed unique reflections, R = 0.057. Lattice dimensions at ?60°C: a = 1 117.0; b = 2 241, c = 1 407.5 pm, β = 95.61°. In the cation [SeCl(NPPh₃)₂]⁺ the selenium atom is φ-tetrahedrally coordinated by the chlorine atom and by the nitrogen atoms of the phosphorane iminato ligands, whereas the anion SeCl₃^? has a T-shaped structure with φ-trigonal-bipyramidale surrounding of the selenium atom. [Me₃SiN(H)PMe₃]₂⁺[Se₂Cl₆]^2?: Space group P2₁/c, Z = 4, structure solution with 2 093 observed unique reflections, R = 0.080. Lattice dimensions at ?70°C: a = 956, b = 828, c = 1 973 pm, β = 93.80°. The structure consists of [Me₃SiN(H)PMe₃]⁺ ions and planar [Se₂Cl₆]^2? anions, in which the selenium atoms are bridged nearly symmetrically by two chlorine atoms.     

Synthesis and Crystal Structures of the Novel Tetrameric Nitrido Complexes [{cyclo-ReN}4(S2CNEt2)6(MeOH)2(PPh3)2][BPh4]2 · CH2Cl2 · 2 H2O and [{cyclo-ReN}4(S2CNEt2)4Cl4(PMe2Ph)4] · 2 acetone

Novel tetrameric rhenium(V) complexes have been prepared from [ReNCl₂(PPh₃)₂] and [ReN(PMe₂Ph)(S₂CNEt)₂], respectively. [ReNCl₂(PPh₃)₂] reacts with 1.5 equivalents of KS₂CNEt₂ in methanol to yield the unusual dark red species [{cyclo-ReN}₄(S₂CNEt₂)₆(MeOH)₂(PPh₃)₂][BPh₄]₂ · CH₂Cl₂ · 2 H₂O ( 1 ). The crystal structure of the tetramer (triclinic, space group P1, a = 13.842(2), b = 15.213(2), c = 16.796(3) Å, α = 67.88(1), β = 70.90(1), γ = 88.05(1)°, U = 3080.2(8) ų, Z = 1) shows four rhenium atoms in a square configuration which are bridged via linear asymmetric Re≡N–Re groups with bond lengths of about 169 and 203 pm. The molecule contains a centre of symmetry with two distinct octahedral rhenium environments. The first rhenium environment contains two bidentate dithiocarbamate ligands which complete the octahedral geometry and the second contains a bidentate dithiocarbamate ligand, coordinated methanol and has retained a single phosphine coligand. A symmetric compound containing the {cyclo-ReN}₄ core is obtained from the reaction of [ReN(PMe₂Ph)(S₂CNEt₂)₂] with Al₂Cl₆ in acetone. [{cyclo-ReN}₄(S₂CNEt₂)₄Cl₄(PMe₂Ph)₄] · 2 acetone ( 2 ) forms red crystals (monoclinic, space group C2/c, a = 21.432(6), b = 13.700(3), c = 28.060(9) Å, β = 102.37(1)°, U = 8048(4) Å3, Z = 4) with each rhenium atom coordinated by a bidentate dithiocarbamato, a phosphine and a chloro ligand. The non-planar 8-membered {ReN}₄ ring contains asymmetric Re≡N–Re bridges (mean values: 1.69 Å and 2.029 Å, respectively). In contrast, reaction of [ReNCl(S₂CNEt₂)(PMe₂Ph)₂] with one equivalent of K[S₂CN(Me)CH₂CH₂NMe₃]I gave the mixed dithiocarbamato-cation [ReN(S₂CNEt₂)(S₂CN(Me)CH₂CH₂NMe₃)(PMe₂Ph)]⁺ ( 3 ) which was isolated as a tetraphenylborate salt.     

Zur Strukturchemie der Alkyl- und Arylhalogenoarsenate(III), [Me2As2Cl5]–, [RAsCl3]–, [R2As2Br6]2– (R = Me,Et, Ph) und [Ph2AsX2]– (X = Cl,Br)

Structural Chemistry of the Alkyl- and Arylhaloarsenates(III) [Me₂As₂Cl₅]^–, [RAsCl₃]^–, [R₂As₂Br₆]^2– (R = Me, Et, Ph) and [Ph₂AsX₂]^– (X = Cl, Br) The alkyl- and arylhaloarsenates(III) [Ph₄P][Me₂As₂Cl₅] ( 1 ), [Ph₄P][RAsCl₃] (R = Me, Et, Ph, 2 – 4 ), [Me₃PhN][PhAsCl₃] ( 5 ), [Ph₄P]₂[R₂As₂Br₆] (R = Me, Et, Ph, 6 – 8 ), [n-Pr₄N][Ph₂AsCl₂] ( 9 ) and [n-Bu₄N][Ph₂AsBr₂] ( 10 ) have been prepared and their structures established by X-ray diffraction. In contrast to the chloroarsenates(III) 2 – 5 , which all contain isolated ψ-trigonal bipyramidal anions [RAsCl₃]^–, the analogous bromoarsenates(III) 6 – 8 exhibit dimeric structures. Whereas the trans sited As–Cl distances in 2 and 3 are very similar a pronounced degree of asymmetry is apparent for the Cl–As–Cl three-centre bonds in 4 and 5 [2.396(1) and 2.602(1) Å in 5]. In 6 and 7 C_i symmetry related RAsBr₂ units are connected through long As…Br bonds [2.926(1) and 3.116(2) Å in 6 ]. The bromophenylarsenate(III) anion of 8 which contains two effectively undistorted ψ-trigonal bipyramids [PhAsBr₃]^– associated by weak As…Br interactions [3.117(2) Å]. In view of its very long bridging As…Cl distances the [Me₂As₂Cl₅]^– anion in 1 can, as 6 an 7 , be regarded as two MeAsCl₂ molecules weakly linked through a chloride ion.     

Transformations of the chameleon ligand 1,10‐phenanthroline‐5,6‐dione/diol: cis‐dichlorido(1,10‐phenanthroline‐5,6‐dione‐κ2N,N′)‐trans‐dipyridinecobalt(II) pyridine disolvate prepared from the diol

The title compound, [CoCl₂(C₅H₅N)₂(C₁₂H₆N₂O₂)]·2C₅H₅N, is a neutral Co^II complex with two chloride anions coordinated in a cis fashion, two pyridine ligands in trans positions and a chelating 1,10‐phenanthroline‐5,6‐dione ligand that completes the octahedral coordination geometry. Two pyridine solvent molecules reside in channels (about 7 × 4 Å wide; the closest atom–atom distance within the channel is 10 Å). The three‐dimensional structure supporting these channels is held together by C—H...Cl [3.466 (8)–3.670 (9) Å] and C—H...O [3.014 (9)–3.285 (8) Å] hydrogen bonds, and can be viewed as a CsCl or bcu (body‐centred cubic) net.     

Phosphor‐Chalkogen‐Moleküle als Komplexliganden – Reaktionen mit NbCl5

Phosphorus Chalcogen Molecules as Complex Ligands – Reactions with NbCl₅ The reaction of P₄E₃ (E = S, Se) with NbCl₅ yields [β‐P₄S₄(NbCl₅)₂] and [P₄Se₃(NbCl₅)]. [β‐P₄S₄(NbCl₅)₂] crystallizes in the monoclinic space group P2₁/n with the lattice parameters a = 6.226(1), b = 12.971(2), c = 26.380(2) Å, β = 93.7(1) (Z = 4). In this compound a sulfur atom is introduced into the basal P₃‐ring and the resulting β‐P₄S₄ is central unit of the complex. [P₄Se₃(NbCl₅)] crystallizes in the same space group type with the lattice parameters a = 11.939(1), b = 18.603(2), c = 12.763(4) Å, β = 90.16(2)° (Z = 8). In both compounds the ligands are coordinated to basal phosphorus atoms.     

Synthesis and Crystal Structures of Cs5Nb2S4X9 – Double Salts Containing New Cluster Anions [Nb2(μ-S2)2X8]4– (X = Cl,Br)

Bis(disulfide)bridged Nb(+4) cluster halide complexes [Nb₂S₄X₈]^4– (X = Cl, Br) were prepared by acid hydrolysis of [Nb₂S₄(NCS)₈]^4– in concentrated aqueous HCl or HBr, solution from which they can be isolated as double salts Cs₅[Nb₂S₄X₈]X (X = Cl, 1 ; X = Br, 2 ). The crystal structures of 1 and 2 were determined. The isolation and X-ray structure of oxonium salt (H₃O)₅ [Nb₂S₄Cl₈]Cl ( 3 ) is also reported. 1 – 3 contain new [Nb₂S₄X₈]^4– anions which can also be viewed as excised building blocks of polymeric solids NbS₂X₂. The extra halogen resides in the center of octahedron formed by six Cs⁺ or H₃O⁺ ions. All the three salts are isostructural and crystallize in tetragonal space group Immm with the following parameters: a = 10.269(2), b = 16.343(2), c = 7.220(1) Å for 1 , a = 10.934(1), b = 16.613(2), c = 7.470(1) Å for 2 , a = 9.639(1), b = 16.031(1), c = 7.071(1) Å for 3 . The parameters of the Nb₂S₄ core are only slightly affected by the change from Cl to Br.     

catena‐Poly­[[bis­[μ‐1,2‐bis(1‐methyl­tetrazol‐5‐yl)­ethane‐κ2N4:N4′]bis[chloro­copper(II)]]‐di‐μ‐chloro]

In the title compound, [Cu₂Cl₄(C₆H₁₀N₈)₂]_n, the ligand has C₂ symmetry, and the Cu and Cl atoms lie on a mirror plane. The coordination polyhedron of the Cu atom is a distorted square pyramid, with the basal positions occupied by two N atoms from two different ligands [Cu—N = 2.0407 (18) Å] and by the two Cl atoms [Cu—Cl = 2.2705 (8) and 2.2499 (9) Å], and the apical position occupied by a Cl atom [Cu—Cl = 2.8154 (9) Å] that belongs to the basal plane of a neighbouring Cu atom. The [CuCl₂(C₆H₁₀N₈)]₂ units form infinite chains extending along the a axis via the Cl atoms. Intermolecular C—H⃛Cl contacts [C⃛Cl = 3.484 (2) Å] are also present in the chains. The chains are linked together by intermolecular C—H⃛N interactions [C⃛N = 3.314 (3) Å].     

Di‐μ‐chlorido‐bis[dichloridobis(methylamido‐κN)bis(methylamine‐κN)titanium(IV)]

The title compound, [Ti₂Cl₆(C₂H₆N)₂(C₂H₇N)₂], is a binuclear octahedral complex lying about an inversion centre. There are four different chloride environments, two terminal [Ti—Cl = 2.2847 (5) and 2.3371 (5) Å] and two bridging [Ti—Cl = 2.4414 (5) and 2.6759 (5) Å], with the Ti—Cl distances being strongly influenced by both the ligand trans to the chloride and whether or not the chloride anion is bridging between the two Ti^IV centres. The compound forms a two‐dimensional network in the solid state, with weak intermolecular C—H...Cl interactions giving rise to a planar network in the (10) plane.     

Acetonyl­di­chloro­[(Z)‐2‐chloro‐2‐phenyl­vinyl]­tellurium(IV), helical chains of metal complexes

The primary geometry about the Te^IV atom in the title compound, [TeCl₂(C₈H₆Cl)(C₃H₅O)] or C₁₁H₁₁Cl₃OTe, is a pseudo‐trigonal‐bipyramidal arrangement, with two Cl atoms in apical positions, and the lone pair of electrons and C atoms in the equatorial plane. The Te^IV atom is involved in three secondary interactions, two intramolecular [Te?O = 2.842 (3) Å and Te?Cl3 = 3.209 (1) Å] and one intermolecular [Te?Cl = 3.637 (1) Å], the latter giving rise to a helical chain. These helices are linked by C—H?O interchain interactions.