The Crystal Structure of Ba2CuAlF9: a New Structure Type in Copper Fluoride Chemistry

Ba₂CuAlF₉ is monoclinic: a = 5.374(2) Å, b = 7.312(2) Å, c = 9.371(3) Å, β = 90.20(1)°, Z = 2, space group P2₁/c (n° 14). The crystal structure was solved from X-ray single crystal data using 1071 unique reflections (900 with F_o/σ(F_o) > 4, R factor = 0.075). It is built up from infinite isolated cis chains of [MF₆] mixed occupied fluorine octahedra sharing each, one edge and one vertex (M is randomly Cu or Al). An analogous kind of linkage was already observed for two other compounds from the ternary system BaF₂/CuF₂/AlF₃. Close structural relationships exist between the cationic subnetworks of γ-BaAlF₅ and Ba₂CuAlF₉.     

Rhenium(V) Complexes of N,N′-Ethylenebis(2-mercaptopropanamide). Synthesis,Characterization, and X-ray Crystal Structures

The preparation of benzoyl-protectcd N,N′-ethylenebis(2-mercaptopropanamide) (H₄emp) and its ligand-exchange reaction with ReO₂(en)₂Cl are described. Three diastereomers, [syn-ReO(meso-emp)]; [anti-ReO(meso-emp)]-, and a pair of cnantiomers, [ReO(rac-emp)]-, were formed due to syn and anti orientation of the two methyl groups of the ligand relative to the ReO core. The diastereomers were separated by reverse phase C₁₈ semipreparative HPLC and isolated as salts of [Ph₄As][ReO-(emp)]. The structures of [Ph₄ As][ReO(meso-emp)] were determined by single-crystal X-ray analyses. [Ph₄As][syn-ReO(mesocmp)]H₂O crystallizes in triclinic space group Pl with a = 10.326(3) Å, b = 13.672(4) A, c = 14.023(5) Å, α = 61.20(2)°, β =74.74(3)°, γ= 75.68(2)° V = 1656.6(8) ų, Z = 2, Dc = 1.676 gmL^?1, F(000) = 824 and R = 0.0329 for 5877 unique reflections. For (he complex [Ph₄As][anti-ReO(meso-emp)], the crystal data are: monoclinic, space group P2₁/n, a = 9.128(2) Å, b = 24.284(7) Å, c = 14.112(4) Å, β = 93.41(2)° V = 3122.5(15) À³, Z = 4, Dc = 1.740 gmL^?1, F(000) = 1608 and R = 0.0361 for 5487 unique reflections. In both structures the rhenium atom is penta-coordinated and in an approximately square pyramidal environment.     

Preparation and Crystal Structure of La3ReO8

The crystal structure of La₃ReO₈, prepared at 1425°C, is reported to be different from a previous result on a preparation at 900°C (BAUD et al., 1979). The high temperature modification crystallizes in the monoclinic space group P2₁/m with a = 7.757(1), b = 7.777(1), c = 5.928(1) Å, γ = 111.1°, Z = 2. The structure was solved by Patterson and Fourier methods from single crystal diffractometer data and refined to final R(F) = 0,073. The structure consists of isolated, distorted ReO₆ octahedra and double chains of edge-shared La₄O tetrahedra.     

Single Crystal Growth and Crystal Structure of Anhydrous Mercury(I) Nitrate,Hg2(NO3)2

Polycrystalline anhydrous Hg₂(NO₃)₂ was prepared by drying Hg₂(NO₃)₂·2H₂O over concentrated sulphuric acid. Evaporation of a concentrated and slightly acidified mercury(I) nitrate solution to which the same volumetric amount of pyridine was added, led to the growth of colourless rod‐like single crystals of Hg₂(NO₃)₂. Besides the title compound, crystals of hydrous Hg₂(NO₃)₂·2H₂O and the basic (Hg₂)₂(OH)(NO₃)₃ were formed as by‐products after a crystallization period of about 2 to 4 days at room temperature. The crystal structure was determined from two single crystal diffractometer data sets collected at —100°C and at room temperature: space group P2₁, Z = 4, —100°C [room temperature]: a = 6.2051(10) [6.2038(7)]Å, b = 8.3444(14) [8.3875(10)]Å, c = 11.7028(1) [11.7620(14)]Å, ß = 93.564(3) [93.415(2)]°, 3018 [3202] structure factors, 182 [182] parameters, R[Fμ² > 2σ(Fμ²)] = 0.0266 [0.0313]. The structure is built up of two crystallographically inequivalent Hg₂²⁺ dumbbells and four NO₃^— groups which form molecular [O₂N‐O‐Hg‐Hg‐O‐NO₂] units with short Hg‐O bonds. Via long Hg‐O bonds to adjacent nitrate groups the crystal packing is achieved. The Hg‐Hg distances with an average of d(Hg‐Hg) = 2.5072Å are in the typical range for mercurous oxo compounds. The oxygen coordination around the mercury dumbbells is asymmetric with four and six oxygen atoms as ligands for the two mercury atoms of each dumbbell. The nitrate groups deviate slightly from the geometry of an equilateral triangle with an average distance of d(N‐O) = 1.255Å.     

The Crystal Structure of Tl2Te3 – a Reinvestigation

Crystals of the title compound were obtained by annealing a powder of Tl₂Te₃ in a vertical temperature gradient (230 °C–240 °C, 4 weeks). Tl₂Te₃ crystallizes in space group C2/c with lattice parameters of a = 13.275(1) Å, b = 6.562(1) Å, c = 7.918(1) Å, and β = 107.14°(2). The tellurium atoms form chains [Te₃^2–], consisting of interconnected linear triatomic · Te–^Te–Te · groups which are isosteric with XeF₂. The Te–Te distances of the XeF₂-like units are 3.02 Å, the connecting ones 2.83 Å.     

Crystal Structure and Vibrational Spectra of ClSO2NHC(O)F

The reaction of chlorosulfonyl isocyanate (ClSO₂NCO) with anhydrous hydrogen fluoride (aHF) leads to the formation of ClSO₂NHC(O)F. The title compound with a melting point of –38 °C is characterized by vibrational spectroscopy and a single crystal structure analysis. It crystallizes in the tetragonal space group I4₁/a with 16 formula units per unit cell. a = 11.1115(2) Å, c = 16.5654(6) Å. The experimental data are supported by quantum‐chemical calculations on the PBE1PBE/6‐311G(3pd,3df) level of theory.     

Synthesis and Crystal Structure of (PCl4)[Re2Cl9]

The reaction between PCl₃ and ReCl₅ yielded at 200 °C the ionic tetrachlorophosphonium dirhenium nonachloride, (PCl₄)[Re₂Cl₉]. Single crystal X-ray diffraction analysis revealed a monoclinic unit cell: a = 8.616(3) Å, b = 10.449(4) Å, c = 9.397(3) Å, β = 99.72(3)°, V = 833.9(5) ų, Z = 2, sp. gr. P2₁/m, wR₂ = 0.1083 and R₁ = 0.0527. The ionic compound is built from tetrahedra PCl₄⁺ and face-sharing bioctahedra Re₂Cl₉^–. The Re–Re distance, 2.724 Å, indicates the presence of direct Re-Re interaction.     

Crystal Structure of Ni(NH3)Cl2 and Ni(NH3)Br2

Ni(NH₃)Cl₂ and Ni(NH₃)Br₂ were prepared by the reaction of Ni(NH₃)₂X₂ with NiX₂ at 350 °C in a steel autoclave. The crystal structures were determined by X‐ray powder diffraction using synchrotron radiation and refined by Rietveld methods. Ni(NH₃)Cl₂ and Ni(NH₃)Br₂ are isotypic and crystallize in the space group I2/m with Z = 8 and for Ni(NH₃)Cl₂: a = 14.8976(3) Å, b = 3.56251(6) Å, c = 13.9229(3) Å, β = 106.301(1)°; Ni(NH₃)Br₂: a = 15.5764(1) Å, b = 3.74346(3) Å, c = 14.4224(1) Å, β = 105.894(1)°. The crystal structures are built up by two crystallographically distinct but chemically mostly equivalent polymeric octahedra double chains [NiX_3/3X_2/2(NH₃)] (X = Cl, Br) running along the short b‐axis. The octahedra NiX₅NH₃ share common edges therein. The crystal structures of the ammines Ni(NH₃)_mX₂ with m = 1, 2, 6 can be derived from that of the halides NiX₂ (X = Cl, Br) by successive fragmentation of its CdCl₂ like layers by NH₃.     

Synthesis and Crystal Structure of SrFe[BP2O8(OH)2]

SrFe[BP₂O₈(OH)₂] was synthesised under mild hydrothermal conditions. The crystal structure was determined from single–crystal X–ray diffraction data: triclinic, space group P (No. 2), a = 6.6704(12) Å, b = 6.6927(13) Å, c = 9.3891(19) Å, α = 109.829(5)°, β = 102.068(6)°, γ = 103.151(3)°, V = 364.74(12) ų and Z = 2. The crystal structure of SrFe[BP₂O₈(OH)₂] contains isolated borophosphate oligomers, [BP₂O₈(OH)₂]^5–, which are interconnected by Fe^IIIO₄(OH)₂ coordination octahedra. The resulting three–dimensional framework is characterised by elliptical channels running along [011]. Strontium takes positions inside the channels.     

The Crystal Structure of MnF3 Revisited

We correct the crystal structure of MnF₃, of which the space group was reported as monoclinic C2/c (no. 15) with a = 8.9202, b = 5.0472, c = 13.4748 Å, β = 92.64°, V = 606.02 ų, Z = 12, mS48, T not given, likely 298 K. In the structure model proposed here, we use a unit cell of one third of the former volume. The ruby red crystals of MnF₃ were synthesized by a high-pressure/high-temperature method, where MnF₄ was used as a starting material. As determined on a single crystal, MnF₃ crystallizes in the monoclinic space group I2/a (no. 15) with a = 5.4964(11), b = 5.0084(10), c = 7.2411(14) Å, β = 93.00(3)°, V = 199.06(7) ų, Z = 4, mS16, T = 183(2) K. The crystal structure of MnF₃ is related by a direct group-subgroup transition to the VF₃ structure-type. We performed quantum chemical calculations on the crystal structure to allow the assignment of bands of the obtained vibrational spectra.     

Crystal Structure of Cesium Dihydrotrifluoride,CsH2F3. Refinement of the Crystal Structures of NMe4HF2 and NMe4H2F3

Single crystals of (NMe₄)(HF₂) were obtained during attempted recrystallization of NMe₄F from fluoroolefin. X‐ray diffraction data show that (NMe₄)(HF₂) crystallizes in the orthorhombic space group Pmmn with unit cell dimensions a = 6.535(2), b = 8.688(3), and c = 5.333(2) Å. The symmetric and virtually linear HF₂ anions exhibit a short F···F distance of 2.256(2) Å. The both crystal structures of (NMe₄)(H₂F₃) (orthorhombic, Pbca, a = 8.509(1), b = 11.273(2), and c = 14.880(2) Å) and CsH₂F₃ (orthorhombic, P2₁2₁2₁, a = 7.345(3), b = 9.126(4), and c = 11.444(4) Å) contain dihydrogentrifluoride anions, H₂F₃^?, which have a bent shape and F···F distances of 2.30‐2.34Å.     

Two Modifications of NH4HPO3F: Synthesis and Crystal Structure

The α and β modifications of NH₄HPO₃F were synthesized and characterized with single crystal X‐ray diffraction. The crystal structure of α‐NH₄HPO₃F determined at 180 K is monoclinic, space group P2₁/n, with a = 7.4650(1), b = 15.586(2), c = 7.5785(9) Å, β = 108.769(9)°, V = 834.9(2) ų, Z = 8, and R₁ = 0.0376 and wR₂ = 0.0818. β‐NH₄HPO₃F measured at 310 K crystallizes in the triclinic space group, P 1, with a = 7.481(1), b = 7.511(1), c = 7.782(1) Å, α = 84.31(1), β = 84.20(1), γ = 68.67(2)°, V = 404.31(9) ų, Z = 4, and R₁ = 0.0254 and wR₂ = 0.0735. A phase transition was not observed between 180 and 310 K for β‐NH₄HPO₃F. Both modifications of NH₄HPO₄F consist of HPO₃F^– and NH₄⁺ units. Two pairs of two unique anions are linked to each other by O–H…O hydrogen bonds to form cyclic tetramers held together by N–H…O bonds. No O–H…F or N–H…F bonds were observed.     

Crystal Structure of a New Cation-ordered Fluorite-related Phase: Bi2Te2WO10

Bi₂Te₂WO₁₀ crystallises in the monoclinic system (space group C2/c, Z = 4) with a = 12.4972(7) Å, b = 5.6414(3) Å, c = 12.2705(6) Å and β = 91.38(3)°. The structure has been solved by means of single crystal X-ray diffraction data analysis. The reliability factors are R1 = 0.030 and wR2 = 0.065 for 1258 structure factors and 70 parameters. The Bi₂Te₂WO₁₀ crystal structure can be described as a regular stacking along the Ox axis of polyhedral layers with the stereochemically active lone pairs E of the Bi^III and Te^IV atoms all located between these layers. The cohesion of the three-dimensional network is therefore only ensured between succesive layers by weak Bi? O(5) bonds.     

The Crystal Structure of Disodium Phosphonate,Na2HPO3

Anhydrous disodium phosphonate, Na₂HPO₃, was prepared by dehydration of its pentahydrate. The crystal structure of Na₂HPO₃ was solved from high resolution X‐ray powder diffraction data (P2₁/n; Z = 4; a = 9.6987(1), b = 6.9795(1), c = 5.0561(1) Å, β = 92.37(1)°; V = 341.97(1) ų). The crystal structure consists of two types of sodium‐oxygen polyhedra, which are connected via common edges and vertices forming layers perpendicular to [100]. These Na(1)‐ and Na(2)‐layers are interlinked via common edges, forming in a 3D‐framework. The resulting topology is providing oxygen arrangements that please the coordinative requirement of phosphorus(III).     

Crystal Structure of the Coordinatively Unsaturated 2-Pyridylphosphine Pd(0) Complex Pd(PPh2Py)3

The three-coordinate tris(2-pyridylphosphine)palladium(0) complex is the first example of a group 10 metal complex bearing pyridine substituted phosphine ligand, whose crystal structure is determined. Pd(PPh₂py)₃ crystallizes in the triclinic space group $ {\rm P}\bar 1 $, with a = 12.874(4) Å, b = 14.162(3) Å, c = 14.912(3) Å, α = 87.76(2)°, β = 66.50(2)°, γ = 63.17(2)°, Z = 2, and V = 2191(1) ų. Full-matrix least-squares refinement of 523 variables using 4911 data (F²_o > 3σF²_o) gave R = 0.033 and R_w = 0.033. The pyridine ring is disordered. Possible weak interactions among Ph rings or Py rings and Pd center are discussed. Close approach of the ortho hydrogen on phenyl rings to the Pd center may imply facile ortho metallation.     

Synthesis and X-Ray Crystal Structure of the TiMgCl6(CH3COOC2H5)4 Adduct

The molecular and crystal structure of TiMgCl₆(CH₃COOC₂H₅)₄, obtained by reacting TiCl₄ with a solution of MgCl₂ in dry CH₃COOC₂H₅, have been determined by x-ray diffraction. The structure was solved by direct and Fourier methods and refined by least-squares techniques to R = 0.052 for 2722 independent observed reflections. Unit-cell dimensions are a = 17.122(7), b = 9.833(3), c = 9.646(3) Å, α = 111.10(7)°, β = 107.22(6)°, γ = 103.11(6)° with Z = 2 for P1 . The titanium(IV) atom is octahedrally coordinated by six chlorine atoms (Ti? Cl_t = 2.293(2) Å, Ti? Cl_b = 2.480(2) Å) and magnesium by two chlorine atoms (Mg? Cl_b = 2.528(2) Å) and the carbonyl oxygen atoms of the four CH₃COOC₂H₅ residues (Mg? O = 2.038(5) Å). The octahedra share an edge by a double chlorine bridge between the magnesium and titanium atoms. Changes in the configurations and dimensions of the free acceptor and donor molecules on adduct formation are discussed. One of the ethylacetate residues shows positional disorder, eventually with Bonding through its ethereal oxygen.     

Synthesis,Crystal Structure and Thermal Decomposition Process of Complex [Sm(BA)3phen]2

A binuclear samarium(III) complex with benzoic acid and 1,10‐phenanthroline, [Sm(BA)₃phen]₂ was synthesized and characterized by elemental analysis, UV, IR and TG‐DTG techniques. The structure of the title complex was established by single crystal X‐ray diffraction. The crystal is triclinic, space group P1 with a = 10.8216(11) Å, b = 11.9129(13) Å, c = 12.425(2) Å, α = 105.007(2)°, β = 93.652(2)°, γ = 113.2630(10)°, Z = 1, D_c = 1.650 mg·m^?3, F(000) = 690. The carboxylate groups are bonded to the samarium ion in three modes: bidentate chelating, bidentate bridging, and tridentate chelating‐bridging. Each Sm³⁺ ion is coordinated to one bidentate chelating carboxylate group, two bidentate bridging and two tridentate chelating‐bridging carboxylate groups, as well as one 1,10‐phenanthroline molecule, forming a nine‐coordinate metal ion. Based on thermal analysis, the thermal decomposition process of [Sm(BA)₃phen]₂ has been derived.     

Preparation and Crystal Structure of MnBiSe2I

Black single crystals of MnBiSe₂I were obtained by the reaction of stoichiometric amounts of Mn, Bi, BiI₃, and Se at 600 °C for 7 days. The compound crystallizes in the monoclinic system, space group C2/m, with a = 13.428(2), b = 4.112(1), c = 10.130(2) Å, β = 90.97(2)°, and Z = 4. The crystal structure refinement based on 849 reflections converged at R = 0.0380 and wR2 = 0.0916, respectively. MnBiSe₂I forms a layer structure consisting of MnSe₆ octahedra, MnSe₂I₄ octahedra, and BiSe₃₊₂ pyramids.     

Crystal Structure and Thermal Behaviour of K2[CrF5·H2O]

K₂[CrF₅·H₂O] is monoclinic: a = 9.6835(3) Å, b = 7.7359(2) Å, c = 7.9564(3) Å, β = 95.94(1)°, Z = 4, space group C2/c (n^o 15). Its crystal structure was solved from its X‐ray powder pattern recorded on a powder diffractometer, using for the refinement the Rietveld method. It is built up from isolated octahedral [CrF₅·OH₂]^2? anions separated by potassium cations. The dehydration of K₂[CrF₅·H₂O] leads to anhydrous orthorhombic K₂CrF₅: a = 7.334(2) Å, b = 12.804(4) Å, c = 20.151(5) Å, Z = 16, space group Pbcn (n^o 60), isostructural with K₂FeF₅.     

Syntheses and X-Ray Crystal Structures of 2-Aminoindenes and Aminocymantrenes

Substituted 2-aminoindenes have been synthesized in almost quantitative yields by reactions of amines such as methylpiperazine, trimethylethylenediamine, 1,4-diaza-cycloheptane and N,N′-dimethylethylenediamine with 2-indanone. The 2-aminoindenes can be deprotonated and reacted with BrMn(CO)₃(Py)₂ to produce the respective aminoindenyl-cymantrenes in yields between 55–70%. The X-ray crystal structures of 2-(methylpiperazine)indenyl-cymantrene 5 (P1 , a = 12.667(3) Å, b = 16.630(3) Å, c = 17.382(3) Å, α = 72.70(3)°, β = 74.59(3)°, γ = 88.66(3)°, V = 3364.1(12) Å ³, Z = 8, R1(2σ(I)) = 4.02%, wR2(2σ(I)) = 10.30%) and the HClO₄ adduct of 2-(trimethylethylenediamine)-indenyl-cymantrene 6 (Cc, a = 23.722(5) Å, b = 6.9080 Å, c = 13.264 Å, β = 111.77(3)°, V = 2018.6(7) Å 3, Z = 4, R1(2σ(I)) = 2.94%, wR2(2σ(I)) = 7.90%) were determined. In both complexes the indenyl-carbon bonded to nitrogen displays significantly longer bonds to manganese [223.5(3)–225.8(3) pm] than the other four carbon atoms [213.3(3)–219.1(3) pm]. The short indenyl-nitrogen bonds of 136.2(4) and 137.8(4) pm are indicative of a substantial multiple bond character. The complexation of Zn²⁺ by the nitrogen atoms of 6 results in significant shifts of the CO stretching frequencies.