Ferrocene compounds: methyl 1′‐aminoferrocene‐1‐carboxylate

The title compund, [Fe(C₅H₆N)(C₇H₇O₂)], features one strong intermolecular hydrogen bond of the type N—H...O=C [N...O = 3.028 (2) Å] between the amine group and the carbonyl group of a neighbouring molecule, and vice versa, to form a centrosymmetric dimer. Furthermore, the carbonyl group acts as a double H‐atom acceptor in the formation of a second, weaker, hydrogen bond of the type C—H...O=C [C...O = 3.283 (2) Å] with the methyl group of the ester group of a second neighbouring molecule at (x, −y − , z − ). The methyl group also acts as a weak hydrogen‐bond donor, symmetry‐related to the latter described C—H...O=C interaction, to a third molecule at (x, −y − , z + ) to form a two‐dimensional network. The cyclopentadienyl rings of the ferrocene unit are parallel to each other within 0.33 (3)° and show an almost eclipsed 1,1′‐conformation, with a relative twist angle of 9.32 (12)°. The ester group is twisted slightly [11.33 (8)°] relative to the cylopentadienyl plane due to the above‐mentioned intermolecular hydrogen bonds of the carbonyl group. The N atom shows pyramidal coordination geometry, with the sum of the X—N—Y angles being 340 (3)°.     

Crystal Structures of {[Cd(phen)](C6H8O4)3/3} and {[Cd(phen)](C7H10O4)3/3} · 2H2O with C6H10O4 = Adipic Acid and C7H12O4 = Pimelic Acid

Two coordination polymers {[Cd(phen)](C₆H₈O₄)_3/3} ( 1 ) and {[Cd(phen)](C₇H₁₀O₄)_3/3} · 2H₂O ( 2 ) were structurally characterized by single crystal X‐ray diffraction methods. In 1 (C2/c (no. 15), a = 16.169(2)Å, b = 15.485(2)Å, c = 14.044(2)Å, β = 112.701(8)°, U = 3243.9(7)ų, Z = 8), the Cd atoms are coordinated by two N atoms of one phen ligand and five O atoms of three adipato ligands to form mono‐capped trigonal prisms with d(Cd‐O) = 2.271‐2.583Å and d(Cd‐N) = 2.309, 2.390Å. The [Cd(phen)] moieties are bridged by adipato ligands to generate {[Cd(phen)](C₆H₈O₄)_3/3} chains, which, via interchain π—π stacking interactions, are assembled into layers. Complex 2 (P1¯(no. 2), a = 9.986(1)Å, b = 10.230(3)Å, c = 11.243(1)Å, α = 66.06(1)°, β = 87.20(1)°, γ = 66.71(1)°, U = 955.7(2)ų, Z = 2) consists of {[Cd(phen)](C₇H₁₀O₄)_3/3} chains and hydrogen bonded H₂O molecules. The Cd atoms are pentagonal bipyramidally coordinated by two N atoms of one phen ligand and five O atoms of three pimelato ligands with d(Cd‐O) = 2.213—2.721Å and d(Cd‐N) = 2.329, 2.372Å. Through interchain π—π stacking interactions, the {[Cd(phen)](C₇H₁₀O₄)_3/3} chains resulting from [Cd(phen)] moieties bridged by pimelato ligands are assembled in to layers, between which the hydrogen bonded H₂O molecules are sandwiched.     

Synthesis and Structures of [Mo12E16(PEt3)10] (E = S,Se)

Dodecanuclcar cluster complexes [Mo₁₂S₁₆(PEt₃)₁₀] 1 and [Mo₁₂Se₁₆(PEt₃)₁₀] 2 have been prepared by the reactions of [Mo₆S₈(PEt₃)₆] with sulfur or [Mo₆Se₈(PEt₃)₆] with Cp₂TiSe₅, respectively, in toluene at refluxing temperature. The structures have been determined at 173 K by X-ray crystallography. The compound 1 ·3CHCl₃ crystallizes in the triclinic space group $ {\rm P}\bar 1 $, with a = 14.859(5) Å, b = 15.868(4) Å, c = 14.200(7) Å, α = 100.58(3)°, β = 117.58(3)°, γ = 79.53(2)°, V = 2899(1) ų, and Z = 1. Full-matrix least-squares refinement using 9016 observed reflections (I_o > 2σ(I_o)) gave R = 0.056, and R_w = 0.045. The data for 2 ·2CHCl₃ are: triclinic, $ {\rm P}\bar 1 $, a = 15.737(4) Å, b = 18.763(9) Å, c = 13.062(4) Å, α = 102.45(3)°, β = 128.54(2)°, γ = 69.49(3)°, V = 2825 ų, Z = 1, R = 0.096, and R_w = 0.120 for 5922 reflections (I_o > 2σ(I_o)). The cluster complexes 1 and 2 have two octahedral molybdenum cluster units linked by the rhomboidal intercluster Mo₂(μ₄-E)₂ bonding. The intercluster Mo—Mo distances in 1 are 3.419 Å and 2 3.551 Å. The cyclic voltammetry of 1 and 2 shows two oxidation and two reduction steps separated as large as 380–490 mV. The UV-Vis spectra of the dodecanuclear cluster complexes 1 and 2 have an extra weak band at around 744 nm which is absent in the starting octahedral cluster complexes.     

Syntheses,Crystal Structures,and Thermal Behaviors of Two New Metallo‐Organically Templated Pentaborates

Two new cadmium borates, [Cd(en)₃][B₅O₆(OH)₄]₂ · 2H₂O (en = ethylenediamine) ( 1 ) and [Cd(DETA)₂][B₅O₆(OH)₄]₂ (DETA = diethylenetriamine) ( 2 ) were synthesized in a novel procedure under mild solvothermal conditions and characterized by single‐crystal X‐ray diffraction, IR spectroscopy, elemental analysis, and TG–DTA. The compound 1 crystallizes in monoclinic system, space group P2₁/c (No. 14) with a = 8.526(2) Å, b = 23.127(6) Å, c = 15.438(4) Å, β = 94.320(3) °, V = 3035.5(13) Å³, Z = 4. Compound 2 is triclinic, space group P$\bar{1}$ (No. 2), a = 8.632(5) Å, b = 9.418(6) Å, c = 27.856(18) Å, α = 95.415(8) °, β = 91.891(7) °, γ = 93.563 (7) °, V = 2248(2) Å³, Z = 3. The anionic units of the both structures, [B₅O₆(OH)₄]^– are linked by hydrogen bonds to form a three‐dimensional framework with large channels, in which the templating cadmium complex cations are located. The thermal decomposition performance of compound 1 requires three steps, whereas only two steps are needed for compound 2 , which all lead to amorphous phases. These processes are well explained considering the structure and the change in the Cd²⁺ coordination during heating.     

Structural Investigations and Thermal Behavior of (EMIm)[Cr(C2O4)2]·2H2O [1‐Ethyl‐3‐methylimidazolium Chromium(III) Dioxalate Dihydrate]

The crystal structure of EMIm diaquobis(μ‐oxalato)chromate(III) (1‐ethyl‐3‐methylimidazolium chromium(III) dioxalate dihydrate) was determined from X‐ray single crystal diffraction studies. A pale violet crystal of good optical quality was used for the structure determination at –100(2) and 25(2) °C. The basic crystallographic data for the low temperature structure are as follows: triclinic symmetry, space group P$\bar{1}$ , a = 7.6202(8) Å, b = 9.7668(9) Å, c = 10.7171(11) Å, α = 109.257(9)°, β = 90.494(8)°, γ = 105.685(8)°, V = 720.75(1) Å³. The crystal structure was solved by direct methods and refined (using anisotropic displacement parameters for all non‐hydrogen atoms) to a final residual of R₁ = 0.039 for 2062 independent observed reflections [I > 2σ(I)]. The compound is built up from alternating layers parallel to (010) containing (EMIm)⁺ cations or Cr(C₂O₄)₂(H₂O)₂^– anions, respectively. The two crystallographically independent Cr(C₂O₄)₂(H₂O)₂ octahedra reside on centers of symmetry (Wyckoff sites 1a and 1f). The corners of the octahedra consist of four oxygen atoms from two oxalate groups and two additional water molecules. EMIm⁺ cations provide linkage between different octahedral layers by hydrogen bridging. The water molecules in turn form hydrogen bonds with adjacent octahedra within the same layer. According to DTA/TG experiments the present compound shows several thermal processes in the range between room temperature and 1000 °C. However, pyrolysis is reproducibly yielding pure inorganic composites, qualifying this novel organic‐inorganic hybrid salt also as a stable precursor for nanoscalar ceramic materials. The final product consists of a distinct mixture of Cr₂O₃ and Cr₃C₂ in the molar ratio of 1:1. Concomittant oxide and carbide formation is an unprecedented disintegration pathway of the thermal treatment of oxalatochromates without reducing atmosphere.     

NaSc3[HPO3]2[HPO2(OH)]6: Synthesis,Crystal Structure,and Thermal Decomposition

NaSc₃[HPO₃]₂[HPO₂(OH)]₆ was prepared by use of a phosphorus acid flux route. The crystal structure was determined from single‐crystal X‐ray diffraction data: triclinic, space group P$\bar{1}$ (No. 2), a = 7.4507(11) Å, b = 9.6253(17) Å, c = 9.6141(16) Å, α = 115.798(4)°, β = 101.395(4)°, γ = 101.136(3)°, V = 577.29(16) Å³ and Z = 1. The crystal structure of NaSc₃[HPO₃]₂[HPO₂(OH)]₆ contains two kinds of phosphate(III) groups: HPO₃^2– and HPO₂(OH)^–. Phosphate(III)‐tetrahedra, NaO₆ and ScO₆ octahedra together form a (3,6)‐connected net. During heating hydrogen and water are released and Sc[PO₃]₃ is formed as the main crystalline decomposition product.     

Crystal Structure,Synthesis, and Properties of tri‐Calcium di‐Citrate tetra‐Hydrate [Ca3(C6H5O7)2(H2O)2]·2H2O

From hydrothermal synthesis needle‐shaped crystals of [Ca₃(C₆H₅O₇)₂(H₂O)₂] · 2H₂O were obtained. The crystal structure was determined by single‐crystal X‐ray experiments and confirmed by powder data (P$\bar{1}$ (no. 2) a = 5.9466(4), b = 10.2247(8), c = 16.6496(13) Å, α = 72.213(7)°, β = 79.718(7)°, γ = 89.791(6)°, V = 947.06(13) Å³, Z = 2, R1 = 0.0426, wR2 = 0.1037). The structure was obtained from pseudo merohedrically polysynthetic twinned crystals using a combined data collection approach and refinement processes. The observed three‐dimensional network is dominated by eightfold coordinated Ca²⁺ cations linked by citrate anions and hydrogen bonds between two non‐coordinating crystal water molecules and two coordinating water molecules.     

Synthesis and crystal structure of 10a‐oxo‐1‐phenylimino‐ 10‐propyl‐3,4,10,10a‐tetrahydro‐1H‐ 2‐thia‐4a,10‐diaza‐10aλ5‐ phospha‐phenanthren‐9‐one

The title novel fused tricyclic phosphoroheterocycle, C₁₉H₂₀N₃O₂PS, was synthesized in an excellent yield of 88.5% via the reac‐ tion of 1‐(2‐bromoethyl)‐2,3‐dihydro‐3‐propyl‐1,3,2‐benzodiazaphosphorin‐4(1H)‐one 2‐oxide with phenyl isothiocyanate, which contains the proximate imino and phosphoryl groups in the fused heterocycle. The crystallographic data analysis reveals that the title compound crystallizes into triclinic space group P with unit cell parameters: a = 9.159(3) Å, b = 10.463(4) Å, c = 10.698(4) Å, α = 88.090(6)°, β = 86.921(6)°, γ = 70.528(6)°, V = 965.0(6) ų for Z = 2 and there is a fused three‐ring in the molecule. The structure has been solved by direct methods and refined to R = 0.0424 for 2451 observed reflections with I >2 σ(I). The proximate imino and phosphoryl groups are not coplanar because both are jointly located in the fused heterocycle, thus having ring tension and this then destroys the conjugation between the CN and the PO moieties. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:671–676, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20169     

New Thioantimonates(III) with Different Sb:S Ratios: Solvothermal Syntheses and Crystal Structures of [(C3H10NO)(C3H10N)][Sb8S13], [(C2H8NO)(C2H8N)(CH5N)][Sb8S13], [(C6H16N2)(C6H14N2)][Sb6S10], and [C8H22N2][Sb4S7]

Four new thioantimonates(III) with compositions [(C₃H₁₀NO)(C₃H₁₀N)][Sb₈S₁₃] ( 1 ) (C₃H₉NO = 1‐amino‐3‐propanol, C₃H₉N = propylamine), [(C₂H₈NO)(C₂H₈N)(CH₅N)][Sb₈S₁₃] ( 2 ) (C₂H₇NO = ethanolamine, C₂H₇N = ethylamine, CH₅N = methylamine), [(C₆H₁₆N₂)(C₆H₁₄N₂)][Sb₆S₁₀] ( 3 ) (C₆H₁₄N₂ = 1,2‐diaminocyclohexane) and [C₈H₂₂N₂][Sb₄S₇] ( 4 ) (C₈H₂₀N₂ = 1,8‐diaminooctane) were synthesized under solvothermal conditions. Compound 1 : triclinic space group P$\bar{1}$ , a = 6.9695(6) Å, b = 13.8095(12) Å, c = 18.0354(17) Å, α = 98.367(11), β = 96.097(11) and γ = 101.281(11)°; compound 2 : monoclinic space group P2₁/m, a = 7.1668(5), b = 25.8986(14), c = 16.0436(11) Å, β = 96.847(8)°; compound 3 : monoclinic space group P2₁/n, a = 11.6194(9), b = 10.2445(5) Å, c = 27.3590(18) Å, β = 91.909(6)°; compound 4 : triclinic space group P$\bar{1}$ , a = 7.0743(6), b = 12.0846(11), c = 13.9933(14) Å, α = 114.723(10), β = 97.595(11), γ = 93.272(11)°. The main structural feature of the two atoms thick layered [Sb₈S₁₃]^2– anion in 1 are large nearly rectangular pores with dimensions 11.2 × 11.7 Å. The layers are stacked perpendicular to [100] to form tunnels being directed along [100]. In contrast to 1 the structure of 2 contains a [Sb₈S₁₃]^2– chain anion with Sb₁₂S₁₂ pores measuring about 8.9 × 11.5 Å. Only if longer Sb–S distances are considered as bonding interactions a layered anion is formed. The chain anion [Sb₆S₁₀]^2– in compound 3 is unique and is constructed by corner‐sharing SbS₃ pyramids. Two symmetry‐related single chains consisting of alternating SbS₃ units and Sb₃S₃ rings are bound to Sb₄S₄ rings in chair conformation. Finally, in the structure of 4 the SbS₃ and SbS₄ moieties are joined corner‐linked to form a chain of alternating SbS₄ units and (SbS₃)₃ blocks. Neighboring chains are connected into sheets that contain relatively large Sb₁₀S₁₀ heterorings. The sheets are further connected by sulfur atoms generating four atoms thick double sheets.     

Template Syntheses of Two Open‐framework Zinc Phosphites

Two new open‐framework zincophosphites, Zn(H₆C₄N₂S)(HPO₃) (TJPU‐4) and [C₆N₂H₁₄]·[Zn₃(HPO₃)₄] (TJPU‐5) have been hydrothermally synthesized by using 2‐mercapto‐1‐methylimidazole [MMI] and 1,4‐diazabicyclo[2.2.2]octane [DABCO] as templates. TJPU‐4 crystallizes in monoclinic space group P2₁/c with the cell parameters a = 8.787(4) Å, b = 9.732(4) Å, c = 10.515(4) Å, β = 105.316(6)°, V = 867.3(6) ų. The structure of TJPU‐4 is constructed by ZnO₃S tetrahedron and HPO₃ pseudo‐pyramid to generate a layer of 4, 8‐network in bc plane. The organic template locates on the both sides of the 8‐membered rings and bonds to zinc atom through Zn–S bond. TJPU‐5 crystallizes in the triclinic space group with cell parameters a = 9.294 (5) Å, b = 9.976 (5) Å, c = 9.986 (5) Å, α = 85.692 (7)°, β = 82.010 (7)° and γ = 80.184 (7)°, V = 902.1 (8) ų. A novel 4⁴8⁸ cage is found in TJPU‐5. The connections of Zn(1)O₄, Zn(3)O₄ and HPO₃ groups give rise to an infinite corner‐shared four‐ring chain. Using Zn(2)O₄ as four connected bridges, linkages of these chains produce a 3‐D framework with intersecting 8‐ring channels running along [100], [010], [001], [011] and [111] directions.     

Das Lanthaniodidethanid o‐La5I9(C2) – Die orthorhombische Hochtemperaturmodifikation

The Lanthanumiodideethanide o‐La₅I₉(C₂) – The Orthorhombic High Temperature Modification o‐La₅I₉(C₂) is synthesized by reaction of LaI₃, La metal and graphite powder in sealed Ta containers at 850 °C < T < 900 °C. It crystallizes in the orthorhombic space group Pbca with a = 8.0247(16) Å, b = 16.887(3) Å, c = 35.886(7) Å. o‐Ce₅I₉(C₂) is isotypic with the lattice parameters a = 7.9284(4) Å, b = 16.714(1) Å, c = 35.530(3) Å. o‐La₅I₉(C₂) transforms at 800 °C to the triclinic low temperature modification t‐La₅I₉(C₂). The transformation is reversible. The La atoms form trigonal bipyramids centered by C₂ groups. These units are connected by iodine atoms above the faces (f), edges (e) and corners according to La₅(C₂)I(f)ⁱI(e)^i?i_2/2I(e)^i?a_7/2I(e)^a?i_7/2. The C‐C distance in the C₂ unit is 1.45(2) Å. The crystals with greenish luster are moisture sensitive.     

Adducts of 1,1,1‐tris(4‐hydroxyphenyl)ethane with diamines: three‐dimensional hydrogen‐bonded frameworks formed with 1,6‐diaminohexane and 2,2′‐bipyridyl

The adduct 1,6‐di­amino­hexane–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2) is a salt {hexane‐1,6‐diyldiammonium–4‐[1,1‐bis(4‐hydroxyphenyl)ethyl]phenolate (1/2)}, C₆H₁₈N₂²⁺·2C₂₀H₁₇O₃^?, in which the cation lies across a centre of inversion in space group P. The anions are linked by two short O—H?O hydrogen bonds [H?O 1.74 and 1.76 Å, O?O 2.5702 (12) and 2.5855 (12) Å, and O—H?O 168 and 169°] into a chain containing two types of R(24) ring. Each cation is linked to four different anion chains by three N—H?O hydrogen bonds [H?O 1.76–2.06 Å, N?O 2.6749 (14)–2.9159 (14) Å and N—H?O 156–172°]. In the adduct 2,2′‐bipyridyl–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2), C₁₀H₈N₂·2C₂₀H₁₈O₃, the neutral di­amine lies across a centre of inversion in space group P2₁/n. The tris­(phenol) mol­ecules are linked by two O—H?O hydrogen bonds [H?O both 1.90 Å, O?O 2.7303 (14) and 2.7415 (15) Å, and O—H?O 173 and 176°] into sheets built from R(38) rings. Pairs of tris­(phenol) sheets are linked via the di­amine by means of a single O—H?N hydrogen bond [H?N 1.97 Å, O?N 2.7833 (16) Å and O—H?N 163°].     

CuBrSe2: a Metastable Compound in the System CuBr / Se

Metastable CuBrSe₂ was prepared by the fast cooling of a melt (T ≥ 400°C) of copper(I) bromide and selenium in the ratio 1:2 to room temperature. The crystal structure was determined from single crystals separated from the solidified melt. The compound crystallizes isotypic to CuXTe₂ (X = Cl, Br, I) and CuClSe₂, space group P2₁/n (No. 14) with a = 7.8838(9) Å, b = 4.6439(4) Å, c = 11.183(1) Å, β = 103.44(1)°, V = 398.2(1) ų, and Z = 4. The refinement converged to R = 0.0424 and wR = 0.0851 (all reflections), respectively. In the crystal structure formally neutral one‐dimensional selenium chains [Se] are coordinated to copper(I) bromide. Slow cooling of the melt or heating of solid CuBrSe₂ to 250°C for some hours results in the decomposition of the compound, and a mixture of CuBrSe₃ and CuBr is formed. DSC measurements indicate, that this decomposition starts at about 200°C. Nevertheless, a melting point of 342°C can be determined. In Raman spectra of CuBrSe₂, selenium‐selenium stretching modes are found at ν_Se–Se = 241 and 219 cm^–1.     

Three Copper(II) Coordination Polymers Constructed by Both Rigid and Flexible Ligands

Three new Copper(II) polymers coordinated by both rigid and flexible ligands, [Cu(bpy)(C₅H₆O₄)]_n ( 1 ), [Cu(bpy)(C₆H₈O₄)]_n ( 2 ), and [Cu₂(bpy)₂(C₆H₈O₄)₂]_n ( 3 ) (bpy = 4,4′‐bipyridine), have been hydrothermally synthesized and structurally characterized. Complex 1 features a box‐like bilayer motif of (4, 4) net. It crystallizes in triclinic space group with cell parameters: a = 8.1395(6) Å, b = 9.43 12(8) Å, c = 10.5473(8) Å, α = 112.1830(1)°, β = 92.423(2)°, γ = 104.752(2)°, V = 716.31(1) ų, Z = 2. Complex 2 crystallizes in triclinic space group with a = 8.8652(4) Å, b = 8.9429(4) Å, c = 10.6390(4) Å, α = 89.520(2)°, β = 69.123(2)°, γ = 75.2440(1)°, V = 758.92(6) ų, Z = 2. Complex 3 crystallizes in monoclinic space group Cc with a = 11.1521(1) Å, b = 15.3961(1) Å, c = 17.7419(1) Å, β = 105.715(3)°, V = 2932.4(5) ų, Z = 4. Complexes 2 and 3 are isomeric with different coordination modes of adipato ligand. Both of them possess the two‐fold interpenetrated 3‐D pcu topological net.     

A Highly Stable 3D Porous Lanthanum Metal‐organic Framework Constructed From A New Flexible Bis(benzoic acid) Ligand Produced in Situ

By employing diethyl 1,3‐propylidenebis(4‐oxybenzoate) as a precursor, the new three‐dimensional metal‐organic framework [La₂L₂(HL)₂]_n [L = 1,3‐propylidenebis(4‐oxybenzoate)] was prepared and characterized by single‐crystal X‐ray diffraction analysis, elemental analysis, infrared spectroscopy, and thermogravimetric analysis. The compound crystallizes in the triclinic space group P , with cell parameters: a = 8.299 (2) Å, b = 14.127 (3) Å, c = 14.520 (3) Å, α = 112.43 (3) °, β = 103.10 (3) °, γ = 95.28 (3)°, V = 1502.2 (5) Å³, and Z = 1. Under hydrothermal reaction conditions, two ester groups of the ligand hydrolyzed into carboxylate groups. The carboxylate groups coordinated in situ to metal ions to form the 3D coordination polymer. It exhibits a 10.4 × 10.6 Å rhombic channel along the [011] direction. On the basis of the results of TG analysis, the structure is thermally stable up to ≈? 400 °C.     

Adipato‐Bridged Mixed Ligand catena Complexes: ${_{\infty}^1}${[M(phen)(H2O)]L2/2} with M = NiII,CuII, ZnII; H2L = Adipic Acid

Three adipato bridged mixed ligand catena complexes {[M(phen)(H₂O)]‐(C₆H₈O₄)_2/2} with M = Ni^II ( 1 ), Cu^II ( 2 ), Zn^II ( 3 ) were synthesized. Structure determination based on X‐ray diffraction shows that they crystallize isostructurally in the monoclinic space group C2/c (no. 15) with cell dimensions of: 1 a = 22.451(4)Å, b = 9.041(1)Å, c = 17.440(2)Å, β = 103.41(1)°, U = 3443.4(9)ų, Z = 8; 2 a = 22.479(2)Å, b = 9.067(1)Å, c = 17.494(3)Å, β = 103.67(1)°, U = 3464.6(8)ų, Z = 8; 3 a = 22.635(3)Å, b = 9.052(1)Å, c = 17.571(3)Å, β = 103.24(1)°, U = 3504.5(9)ų, Z = 8. The crystal structure consists of 1D {[M(phen)(H₂O)]‐(C₆H₈O₄)_2/2} zigzag chains, in which the metal atoms are all octahedrally coordinated by two N atoms of one phen ligands and four O atoms of one H₂O molecule and two adipato ligands. The zigzag chains are held together by interchain π‐π stacking interactions and interchain hydrogen bonds.     

1,2‐Dithioquadratato‐ und 1,2‐Dithiooxalatoindate(III)

Indium(III) chloride forms in water with potassium 1,2‐dithiooxalate (dto) and potassium 1,2‐dithiosquarate (dtsq) stable coordination compounds. Due to the higher bridging ability of the 1,2‐dithiooxalate ligand in all cases only thiooxalate bridged binuclear complexes were found. From 1,2‐dithioquadratate with an identical donor atom set mononuclear trischelates could be isolated. Five crystalline complexes, (BzlMe₃N)₄[(dto)₂In(dto)In(dto)₂] ( 1 ), (BzlPh₃P)₄[(dto)₂In(dto)In(dto)₂] ( 2 ), (BzlMe₃N)₃[In(dtsq)₃] ( 3 ), (Bu₄N)₃[In(dtsq)₃] ( 4 ) and (Ph₄P)[In(dtsq)₂(DMF)₂] ( 5 ), have been isolated and characterized by X‐ray analyses. Due to the type of the complex and the cations involved these compounds crystallize in different space groups with the following parameters: 1 , monoclinic in P2₁/c with a = 14.4035(5) Å, b = 10.8141(5) Å, c = 23.3698(9) Å, β = 124.664(2)°, and Z = 2; 2 , triclinic in P with a = 11.3872(7) Å, b = 13.6669(9) Å, c = 17.4296(10) Å, α = 88.883(5)°, β = 96.763(1)°, γ = 74.587(5)°, and Z = 1; 3 , hexagonal in R3 with a = 20.6501(16) Å, b = 20.6501(16) Å, c = 19.0706(13) Å and Z = 6; 4 , monoclinic in P2₁/c with a = 22.7650(15) Å, b = 20.4656(10) Å, c = 14.4770(9) Å, β = 101.095(5)°, and Z = 4; 5 , triclinic in P with a = 9.2227(6) Å, b = 15.3876(9) Å, c = 15.5298(9) Å, α = 110.526(1)°, β = 100.138(1)°, γ = 101.003(1)°, and Z = 2.     

Synthesis and Crystal Structure of Bis(tetraphenylphosphonium) Hexabromo‐diselenate(II)‐bis{dibromodiselenate(I)}, [PPh4]2[Se2Br6(Se2Br2)2], the Salt of a Mixed‐valence Bromoselenate(II,I) Anion

The Red crystals of [PPh₄]₂[Se₂Br₆(Se₂Br₂)₂] ( 1 ) were obtained when selenium and bromine reacted in the solution of acetonitrile in the presence of tetraphenylphosphonium bromide. The crystal structure of 1 has been determined by X‐ray diffraction and refined to R = 0.0201 for 4024 reflections. The crystals are triclinic, space group with Z = 2 and a = 11.2757(4) Å, b = 12.3347(5) Å, c = 12.4948(5) Å, α = 113.152(4)°, β = 114.745(4)°, γ = 91.208(3)° (120(2) K). In the solid state the anion of 1 is built up of the Se₂Br₆ core and two Se₂Br₂ molecules each of which is linked to one of the trans‐positioned terminal Br_t atoms of the Se₂Br₆ core. The central Se₂Br₆ part consists of a nearly planar arrangement of two planar SeBr₄ units sharing a common edge through two μ₂‐bridging Br atoms. The contact between the Br_t and the Se^I atom of the Se₂Br₂ molecule is 3.0872(5) Å and can be interpreted as a bond of the donor‐acceptor type with the Br_t as donor and the Se₂Br₂ molecule as acceptor. The terminal Se^II–Br and μ₂Br–Se^II bond lengths are 2.3654(4), 2.6699(5) Å and 2.5482(5), 3.0265(5) Å, respectively. The bond lengths in the coordinated Se₂Br₂ molecule are: Se^I–Se^I = 2.2686(5) Å, Se^I–Br = 2.3779(5) and 2.3810(5) Å.     

One‐Dimensional Zinc Selenophosphates: A2ZnP2Se6 (A = K,Rb, Cs)

The new compounds A₂ZnP₂Se₆ (A = K, Rb, Cs) were synthesized via molten salt flux syntheses. The crystals feature one‐dimensional ¹/_∞[ZnP₂Se₆]^2– chains charge balanced by alkali metal ions between the chains. K₂ZnP₂Se₆ crystallizes in the monoclinic space group P2₁/c; cell parameters a = 12.537(3) Å, b = 7.2742(14) Å, c = 14.164(3) Å, β = 109.63(3)°, Z = 4, and V = 1216.7(4) ų. Rb₂ZnP₂Se₆ and Cs₂ZnP₂Se₆ are isotypic, crystallizing in the triclinic space group P$\bar{1}$ . Rb₂ZnP₂Se₆ has cell parameters of a = 7.4944(15) Å, b = 7.6013(15) Å, c = 12.729(3) Å, α = 96.57(3)°, β = 105.52(3)°, γ = 110.54(3)°, Z = 2, and V = 636.6(2) ų. Cs₂ZnP₂Se₆ has cell parameters of a = 7.6543(6) Å, b = 7.7006(6) Å, c = 12.7373(11) Å, α = 97.007(7)°, β = 104.335(7)°, γ = 109.241(6)°, Z = 2, and V = 669.54(10) ų.