Synthesis and Crystal Structure of Copper(II) Trifluoroacetates,Cu2(CF3COO)4 · 2 CH3CN and Cu(CF3COO)2(H2O)4

Cu₂(CF₃COO)₄ · 2 CH₃CN ( I ) and Cu(CF₃COO)₂(H₂O)₄ ( II ) have been prepared by concentrating of acetonitrile and aqueous solutions respectively. According to X-ray data, the complex I consists of binuclear molecules with Cu–O 1.969 Å, Cu–N 2.114 Å. The Cu…Cu distance was found to be 2.766 Å, one of the longest for dimeric structures, apparently, due to the high acidity of trifluoroacetic acid. The coordination environment of Cu atom in II can be described as 4 + 2: 2 Cu–O (H₂O) 1.937 Å, 2 Cu–O (CF₃COO) 1.985 Å, 2 Cu–O (H₂O) 2.447 Å. The mononuclear structure is stabilized by formation of two intra- and six intermolecular hydrogen bonds.     

Bis­(triethanol­amine‐O,O′)­nickel(II) di­acetate

The title compound, [Ni{N(CH₂CH₂OH)₃}₂](CH₃COO)₂, was prepared and the structure determined. It is isostructural with the copper(II) analogue.     

Synthesis and crystal structure of New Amminecopper(II) Nitrates: [Cu(NH3)2](NO3)2 and [Cu(NH3)](NO3)2

[Cu(NH₃)₂](NO₃)₂ ( I ) and [Cu(NH₃](NO₃)₂ ( II ) were synthesized by interaction of molten NH₄NO₃ with [Cu(NH₃)₄](NO₃)₂ and Cu(NO₃)₂ · 3 H₂O, respectively, at 180 to 195°C for 24 hr. According to X-Ray single crystal analysis, I is orthorhombic (sp. gr. Pbca) with a = 5.678(1), b = 9.765(2), c = 11.596(2) Å, Z = 4, R = 0.060; II is monoclinic (sp. gr. P2₁/c) with a = 6.670(1), b = 8.658(2), c = 9.661(2) Å, β = 101.78(2)°, Z = 4, R = 0.027. In both structures, the nearest coordination environment of Cu is a slightly distorted square formed by N (from NH₃) and O atoms (from NO₃ groups). The structure of I consists of centrosymmetrical [Cu(NH₃)₂](NO₃)₂ molecules linked by hydrogen bonds. The Cu? N and Cu? O distances are 1.98 and 2.01 Å, respectively. In II , the Cu? N distance is 1.95 Å, the Cu? O distances are 1.96, 2.02, and 2.03 Å. The [CuO₃NH₃] squares are connected by NO₃ bridges into zigzag chains, which are linked into layers by longer Cu? O interactions (2.31 Å). Obviously, the layers are additionally strengthened and held together by hydrogen bonds.     

Synthesis and Crystal Structure of Hexakis(N—allylthiourea)tetracopper(I) Tetratrifluoromethanesulfonate, [Cu4{CH2=CHCH2NHC(S)NH2}6](SO3CF3)4

Hexakis(N—allylthiourea)tetracopper(I) Tetratrifluoromethanesulfonate, [Cu₄{CH₂=CHCH₂NHC(S)NH₂}₆](CF₃SO₃)₄ (sp.gr.P2₁/n, a = 13.5463(8), b = 24.129(2), c = 19.128(1)Å, β = 108.053(6)°, Z = 4, R = 0.0440 for 13548 unique reflections) was obtained by reduction of Cu(CF₃SO₃)₂ with excess of N—allylthiocarbamide in benzene medium. Four crystallographical independent Cu atoms possess trigonal environment of three S atoms of CH₂=CHCH₂NHC(S)NH₂ moiety and form Cu₄S₆⁴⁺ adamantane—like fragments. The latteres are connected with CF₃SO₃^— anions via (C)—H···F hydrogen bonds.     

Ternäre Acetate der Lanthanide mit Caesium: Dimere und Trimere in CsLu(CH3COO)4 bzw. Cs2[Lu3(CH3COO)10(OH)(H2O)]. Synthese,Kristallstrukturen und Thermolyse

Ternary Acetates of the Lanthanides with Cesium: Dimers in CsLu(CH₃COO)₄ and Trimers in Cs₂[Lu₃(CH₃COO)₁₀(OH)(H₂O)]. Synthesis, Crystal Structures, Thermolysis Single crystals of CsLu(CH₃COO)₄ and Cs₂[Lu₃(CH₃COO)₁₀(OH)(H₂O)] were obtained from an aqueous solution of lutetium and cesium acetate in a 1:1 molar ratio. The crystal structures (CsLu(CH₃COO)₄: monoclinic, P2₁/n (no. 14), Z = 8, a = 1 293.1(2), b = 1 323.8(2), c = 1 622.5(3) pm, β = 92.01(2)°, V_m = 208.97(6) cm³/mol, R = 0.056, R_w = 0.034; Cs₂[Lu₃(CH₃COO)₁₀(OH)(H₂O)]: monoclinic, C2/c (no.15), Z = 4, a = 2 138.5(6), b = 1 378.0(3), C = 1 482.9(4) pm, β = 106.15(2)°, V_m = 632.0(3) cm³/mol, R = 0.049, R_w = 0.036) were determined from four-circle-diffractometer data. The structures consist of dimers and trimers, respectively, that are built by bridging acetate groups. These units are fragments of the infinite chains of the Ho(CH₃COO)₃ type of structure. The isotypic compounds CsM(CH₃COO)₄ with M=Eu? Lu were synthesized and characterized by the X-ray Guinier technique. The thermal decomposition of CsLu(CH₃COO)₄ was examined with thermoanalytical methods (TG/DSC with coupled gas analysis) and the Guinier-Simon technique: it decomposes at 260°C in an endothermic reaction to Lu₂O₃ and Cs₂CO₃.     

Gemischtligandkomplexe des Rheniums. V. Die Bildung von Nitrenkomplexen durch Kondensation von Aceton an koordinierten Nitridoliganden. Darstellung und Strukturen von fac-[Re{NC(CH3)2CH2C(O)CH3}X3(Me2PhP)2]-Komplexen (X = Cl,Br)

Mixed-ligand Complexes of Rhenium. V. The Formation of Nitrene Complexes by Condensation of Acetone at Coordinated Nitrido Ligands. Syntheses and Structures of fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}X₃(Me₂PhP)₂] Complexes (X = Cl, Br) The reaction of rhenium(V)-mixed-ligand complexes of the general formula [ReN(Cl)(Me₂PhP)₂(R₂tcb)] (HR₂tcb = N? (N,N-dialkylthiocarbamoyl)benzamidine) with HCl or HBr in acetone initializes a condensation of the solvent and results in nitrene-like compounds as a consequence of a nucleophilic attack of the coordinated nitrido ligand on the condensed acetone. The chelate ligands are removed during this reaction and complexes of the type fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}X₃(Me₂PhP)₂] (X = Cl, Br) are formed. fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Cl₃(Me₂PhP)₂] crystallizes triclinic in the space group P1, a = 8.575(4); b = 9.088(3); c = 18.389(9) Å; α = 75.67(3)°, β = 85.30(3)°, γ = 70.58(4)°; Z = 2. A final R value of 0.031 was obtained on the basis of 6011 independent reflections with I ≥ 2σ(I). Rhenium is coordinated in a distorted octahedral environment with the three chloro ligands in facial positions. The rhenium-nitrogen bond (1,68(1) Å) is only slightly longer than typical Re? N bonding distances in nitrido complexes. fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Br₃(Me₂PhP)₂] is isomorphous with the chloro complex. Triclinic cell with a = 8.625(4); b = 9.198(3); c = 18.581(5) Å; α = 75.62(3)°, β = 85.40(3)°, γ = 70.91(3)°; Z = 2. The R value converged at 0.049 on the basis of 3644 independent reflections with I ≥ 2σ(I). fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Cl₃(Me₂PhP)₂] as well as fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Br₃(Me₂PhP)₂] crystallizes in the noncentrosymmetric space group P1.     

Syntheses and structural study of trinuclear iron acetates [Fe3O(CH3COO)6(H2O)3]Cl· 6H2O and [Fe3O(CH3COO)6(H2O)3] [FeCl4]· 2CH3COOH

The structure of two trinuclear iron acetates [Fe₃O(CH₃COO)₆(H₂O)₃]Cl· 6H₂O (I) and [Fe₃O(CH₃COO)₆(H_2O)₃][FeCl₄] · 2CH₃COOH (II) was determined by X-ray diffraction analysis. Crystals I and II are ionic and belong to the orthorhombic system with parameters a = 13.704(3), b = 23.332(5), c = 9.167(2) Å, R = 0.0355, space goup P2₁2₁2 for I and a = 10.145(4), b = 15.323(6), c = 22.999(8) Å, R = 0.0752, space group Pbc2₁ for II. The complex cation [Fe₃O(CH₃COO)₆(H₂O)₃]⁺ has a μ₃-O-bridged structure typical for trinuclear iron (III) compounds. As shown by Mössbauer spectroscopy, the iron(III) ions are in the high-spin state. In trinuclear cations, antiferromagnetic exchange interaction takes place between the Fe(III) ions with the exchange parameter J = -26.69 cm^?1 for II (Heisenberg-Dirac-Van Vleck model for D_3h, symmetry).     

Syntheses and Crystal Structures of Copper(II) and Copper(I) dpp Complexes, [Cu(dpp)Br2] and [Cu(dpp)2][CuBr2] (dpp = 2,9‐diphenyl‐1,10‐phenanthroline)

The complexes [Cu(dpp)Br₂] ( 1 ) and [Cu(dpp)₂][CuBr₂] ( 2 ) (dpp = 2,9‐diphenyl‐1,10‐phenanthroline) were synthesized and characterized by single‐crystal X‐ray diffraction methods. Reaction of copper(II) bromide with the dpp ligand in dichloromethane at room temperature afforded 1 , which is a rare example of non‐square planar four‐coordinate copper(II) complexes. Complex 1 crystallizes in the monoclinic space group C2/c with a = 15.352(3), b = 13.192(3), c = 11.358(2) Å, β = 120.61(3)°, V = 1979.6(7) ų, Z = 4, D_calc = 1.865 g cm^?3. The coordination geometry about the copper center is distorted about halfway between square planar and tetrahedral. The Cu‐N distance is 2.032(2) Å and the Cu‐Br distance 2.3521(5) Å. Heating a CH₂Cl₂ or acetone solution of 1 resulted in complex 2 , which consists of a slightly distorted tetrahedral [Cu(dpp)₂]⁺ cation and a linear two‐coordinate [CuBr₂]^? anion. 2 crystallizes in the triclinic space group with a = 10.445(2), b = 11.009(2), c = 18.458(4) Å, α = 104.72(3), β = 94.71(3), γ = 103.50(3)°, V = 1973.3(7) ų, Z = 2, D_calc = 1.602 g cm^?3. The four Cu(1)‐N distances are between 2.042(3) and 2.067(3) Å, the distance of Cu(2)‐Br(1) 2.2268(8) Å, and the disordered Cu(3)‐Br(2) distances are 2.139(7) and 2.237(4) Å, respectively. Complex 2 could also be prepared by directly reacting CuBr with dpp in CH₂Cl₂.     

Darstellung und Kristallstrukturen von Ag[N(CN)2](PPh3)2, Cu[N(CN)2](PPh3)2 und Ag[N(CN)2](PPh3)3

Preparation and Crystal Structures of Ag[N(CN)₂](PPh₃)₂, Cu[N(CN)₂](PPh₃)₂, and Ag[N(CN)₂](PPh₃)₃ The coordination compounds Ag[N(CN)₂](PPh₃)₂ ( 1 ), Cu[N(CN)₂](PPh₃)₂ ( 2 ), and Ag[N(CN)₂](PPh₃)₃ ( 3 ) are obtained by the reaction of AgN(CN)₂ or CuN(CN)₂ with triphenylphosphane in CH₂Cl₂. X‐ray structure determinations were performed on single crystals of 1 , 2 , and 3 · C₆H₅Cl. The three compounds crystallize monoclinic in the space group P2₁/n with the following unit cell parameters. 1 : a = 1216.07(9), b = 1299.5(2), c = 2148.4(3) pm, β = 99.689(13)°, Z = 4; 2 : a = 1369.22(10), b = 1257.29(5), c = 1888.04(15) pm, β = 94.395(7)°, Z = 4; 3 · C₆H₅Cl: a = 1276.6(4), b = 1971.7(3), c = 2141.3(5) pm, β = 98.50(3)°, Z = 4. In all structures the metal atoms have a distorted tetrahedral coordination. The crystal structure of 3 · C₆H₅Cl shows monomeric molecular units with terminal coordinated dicyanamide. The crystal structure of 1 is built up by dinuclear units, which are bridged by dicyanamide ligands. However, the crystal structure of 2 corresponds to a onedimensional coordination polymer, bridged by dicyanamide anions.     

Copper(II)-assisted thorough hydrolysis of 2,4,6-tris(2-pyridyl)1,3,5-triazine (tptz). Crystal structures of bis(2-pyridylcarboxylato)-copper(II) dihydrate and bis(2-pyridylcarbonyl)-amido-2,4,6-tris(2-pyridyl)-1,3,5-triazine-copper(II) dicyanamide heptahydrate

2,4,6-Tris(2-pyridyl)-1,3,5-triazine (tptz) undergoes hydrolysis in the presence of copper(II) acetate affording bis(2-pyridylcarbonyl)amido-copper(II) and free 2-pyridylcarboxylic anion. Two compounds of formulas [Cu(NC₅H₄COO)₂]·2H₂O (1) and [Cu(NC₅H₄CO)₂N(tptz)](N(CN)₂)·7H₂O (2), where NC₅H₄COO^? and (NC₅H₄CO)₂N^? are 2-pyridylcarboxylate and bis(2-pyridylcarbonyl)amido-anion, respectively, were obtained from methanol/ethanol solution of tptz with copper acetate; they were characterized by element analysis and single crystal X-ray diffraction method. Single crystal XRD analysis shows that in complex 1 coordination number around Cu atom is 4 with distorted square-planar coordination geometry and in complex 2 coordination number around Cu atom is 6 with distorted octahedral geometry. Crystal data for 1: a = 5.1359(10) Å, b = 7.6471(15) Å, c = 9.2303(18) Å, α = 74.90(3)°, β = 84.36(3)°, γ = 71.37(3)°, space group P1, crystal system triclinic, Z = 1, V = 331.6(1) ų, d _calc = 1.721 g/cm³. Crystallographic data for 2: space group C2/c, crystal system monoclinic, a = 23.976(5) Å, b = 15.465(3) Å, c = 18.649(4) Å, β = 92.66(3)°, V = 6907(2) ų, d _calc = 1.0448 g/cm³, Z = 4.     

Cs2(H3O)Pr(CH3COO)6 und Cs2Pr(CH3COO)5: Synthese,Kristallstrukturen und Thermolyse. Über die analogen Acetate mit Lanthan bis Terbium

Cs₂(H₃O)Pr(CH₃COO)₆ and Cs₂Pr(CH₃COO)₅: Synthesis, Crystal Structures and Thermolysis. Analogous Acetates with Lanthanum through Terbium Single crystals of Cs₂(H₃O)Pr(CH₃COO)₆ are obtained as green plates from an acetic acid solution (≈50%) of Cs₂CO₃ and Pr(CH₃COO)₃ · 1,5 H₂O. The crystal structure monoclinic, Cm, Z = 2, a = 1 540.4(4), b = 691.3(2), c = 1 221.5(4) pm, β = 104.60(5)°, V_m = 379.1(2) cm³/mol, R = 0.040, R_w = 0.035 was determined from four-circle-diffractometer data. The structure consists of monomeric Pr(CH₃COO)₃ units, in which Pr³⁺ is surrounded by nine oxygen atoms. These monomers are linked together to infinite layers parallel (001) by common acetate oxygen atoms with two ?molecules”? of Cs(CH₃COO). Together with an additional acetate ion coordinated to one of the Cs⁺ ions the composition of the layers is [Cs₂Pr(CH₃COO)₆]^?. Between these layers H₃O⁺ is located for electroneutrality. Thermal decomposition of Cs₂(H₃O)Pr(CH₃COO)₆ was examined with thermoanalytical methods (TG/DTA with coupled gas analysis), Guinier-Simon technique and IR spectroscopy: beginning at 70°C the compound looses water and acetic acid. It decomposes topotactically to Cs₂Pr(CH₃COO)₅. At 270°C this acetate decomposes to Cs₂CO₃ and Pr₂O₂CO₃ which emits CO₂ at 600°C form ing Pr₂O₃or PrO_2?x Single crystals of Cs₂Pr(CH₃COO)₅ were obtained from Pr(CH₃COO)₃, in molten Cs(CH₃COO) at about 200°C. The crystal structure tetragonal, P4₃, Z = 4, a = 1 174,5(2), c = 1 480,5(3) pm, V_m = pin,307,5(1) cm³/mol, R = 0,061, R_w= 0,031 again consists of Pr(CH₃COO)₃, monomers where Pr³⁺ has 9 oxygen ligands in its first coordination sphere. They are linked together by two ”molecules“ of cesium acetate to infinite chains along [00l] around the 4, screw axis. There are also acetate bridges between these chains. Isotypic compounds Cs₂(H₃O)M(CH₃COO)₆ and Cs₂M(CH₃COO)₅, and Cs₂M(CH₃COO)₅with M = La? Tb, were obtained from acetic acid solutions or thermal decomposition and were characterized by X-ray Guinier techniques.     

Monosubstituted Trinuclear and Tetranuclear VIB Metal Carbonyl Complexes: Syntheses of [{M(CO)5}3(Pf-Pf-Pf)] [Pf-Pf-Pf = PhP(CH2CH2PPh2)2] and [{M(CO)5}4(P-Pf3)] [P-Pf3 = P(CH2CH2PPh2)3] (M = Cr,Mo) and Crystal Structures of the Latter Three

The triligate trimetallic complexes, [{M(CO)₅}₃(Pf-Pf-Pf)] and tetraligate tetrametallic complexes, [{M(CO)₅}₄(P-Pf₃)] (M = Cr and Mo), were prepared from [M(CO) ₆] and the corresponding ligands in MeCN/CH₂Cl₂ promoted by Me₃NO at 0 °C. Crystals of trimer lb are monoclinic, space group P 2₁/n, with a = 13.407(3), b = 15.002(5), c = 26.52(1) Å, β = 90.65(2)°, Z = 4, and R = 0.060 for 2760 observed reflections. Crystals of tetramer 2a are monoclinic, space group P 2₁/c, with a – 14.183(8), b = 29.880(4), c = 16.103(2) Å, β = 94.98(3)°, Z = 4, and R = 0.039 for 5014 observed reflections. Crystals of 2b are monoclinic, space group C 2/c, with a = 42.120(8), b = 13.679(1), c = 23.486(2) Å, β = 92.14(1)°, Z = 8, and R = 0.032 for 6897 observed reflections. Each phosphorus atom of the ligands is coordinated to the M(CO)₅ moiety in each title compounds. The geometry of the four metals is a distorted tetrahedron for the tetramers.     

A novel mononuclear gold(I) complex: Synthesis and x-ray structure of [Au{P(C6H5)3}3][SiF5] · 1.5 CH2Cl2

Tris(triphenylphosphine)gold(I)-pentafluorosilicate(IV) ([Au{P(C₆H₅)₃}₃][SiF₅]) was prepared and the structure was determined by single crystal x-ray diffraction. The complex crystallizes in the triclinic space group P1 (No. 2). The lattice constants are a = 14.634(2) Å, b = 17.180(2) Å, c = 22.212(3) Å, α = 86.48(1)°, β = 78.95(1)°, γ = 83.99(1)°. Number of molecules per cell: Z = 4. The gold atoms are coordinated to three triphenylphosphine ligands to form the trigonal planar cation [Au{P(C₆H₅)₃}₃]⁺. Separated from the cation is the [SiF₅]^? anion which is regular trigonal bipyramidal coordinated. No interactions between the fluorine atoms and the gold atoms were observed.     

Structural Relationships obtained from the Coordination of α‐Picolinamide to the (Iminodiacetato)copper(II) Chelate: Synthesis,Crystal Structure,and Properties of (α‐Picolinamide)(iminodiacetato)copper(II) Dihydrate

The stoichiometric reaction of copper(II) hydroxycarbonate, iminodiacetic acid (H₂IDA = HN(CH₂CO₂H)₂) and α‐picolinamide (pya) in water yields crystalline samples of (α‐picolinamide)(iminodiacetato)copper(II) dihydrate, [Cu(IDA)(pya)] · 2 H₂O ( 1 ). The compound was characterised by thermal (TG analysis with FT‐IR study of the evolved gasses), spectral (IR, electronic and ESR spectra), magnetic and single crystal X‐ray diffraction methods. It crystallises in the triclinic system, space group P1, a = 8.8737(4), b = 10.23203(5), c = 15.7167(11) Å, α = 77.61(1)°, β = 103.89(1)°, γ = 80.32(1)°, Z = 4, final R1 = 0.056. The asymmetric unit contains two crystallographic independent molecules but chemically very similar ones. The Cu^II atom exhibits a square base pyramidal coordination (type 4 + 1). pya acts as N,O‐bidentate ligand supplying two among the four closest donor atoms of the metal [averaged bond distances (Å): Cu–N = 1.982(2), Cu–O(amide) = 1.972(2)]. IDA plays a N,O,O′‐terdentate chelating role [averaged bond distances (Å): Cu–N = 2.004(3), Cu–O = 1.941(2) and Cu–O = 2.242(2)]. The coordinating behaviour of pya in 1 is discussed on the basis of its N,O‐bidentate chelating role and the preference of the ‘Cu‐iminodiacetato' moiety [Cu(IDA)] to link the N‐heterocyclic donor of pya in trans versus the Cu–N(IDA) bond. Consistently the ligand pya is able to impose a fac‐chelating configuration to IDA one around the copper(II) as previously has been reported to mixed‐ligand complexes having a 1/1/2 Cu^II/IDA/N(heterocyclic) donor ratio or a closely related 1/1/1/1 Cu^II/IDA/N(heterocyclic)/N(aliphatic) one.     

Wasserfreie Selten-Erd-Acetate,M(CH3COO)3 (M = Sm?Lu,Y) mit Kettenstruktur. Kristallstrukturen von Lu(CH3COO)3 und Ho(CH3COO)3

Anhydrous Rare-Earth Acetates, M(CH₃COO)₃ (M = Sm? Lu, Y) with Chain Structures. Crystal Structures of Lu(CH₃COO)₃ and Ho(CH₃COO)₃ Single crystals of the anhydrous rare-earth acetates containing lutetium (type 1) and holmium (type 2) were obtained by crystallisation at 120°C from diluted acetic acid solutions of their oxides and cesium acetate. The crystal structures [Lu(CH₃COO)₃: orthorhombic, a = 825.85(8), b = 1 398.1(2), c = 823.9(1) pm, V_m = 143.24(3) cm³/mol, space group Ccm2₁ (No. 36), Z = 4, R = 0.035, R_w = 0.030; Ho(CH₃COO)₃: monoclinic, a = 1 109.1(3), b = 2 916.3(10), c = 786.8(2) pm, β = 131.90(1)°, V_m = 142.58(8) cm³/mol, space group C2/c (No. 15), Z = 8, R = 0.039, R_w = 0.039, R_w = 0.026] were determined from four-circle diffractometer data sets. The structures consist of one-dimensional infinite chains built up by bridging acetate ions. Ho³⁺ is coordinated by 8 oxygen atoms, whereas Lu³⁺ has only 7 nearest oxygen neighbours. The chains are stacked parallel to the [001] direction. Isotypic compounds with Tm? Lu (type 1) and Sm? Er, Y (type 2) were prepared as powders and characterized by X-ray powder patterns. Thermoanalytical investigations (DTA, Guinier-Simon technique) of all compounds have shown that there is a first-order phase transition at 180°C (type 2) and in the range of 230–255°C (type 1). The high-temperature phase crystallizes with the known Sc(CH₃COO)₃ structure (type 0) where the rare earth cations are surrounded by 6 oxygen atoms. In the case of the type 1 compounds the phase transition is reversible.     

Formation of a rhenium(III) carbonyl complex by electrophilic attack on rhenium isocyanides. Synthesis and molecular structure of {Re[N(CH2CH2S) 3][CNC(CH3) 3]} and {Re[N(CH2CH2) 3](CO)}

Treatment of the trigonal-bipyramidal complex {Re[N(CH₂CH₂S)₃](CNCH₂COOEt)} (1a) with LiOH in THF leads to ester hydrolysis and yields the complex {Re[N(CH₂CH₂S)₃](CNCH₂COOH)} (2). Attempts to hydrolyze the ester in 1a in the two-phase system toluene/concentrated hydrochloric acid proceeded under electrophilic attack at the isocyanide nitrogen atom and formation of the carbonyl complex {Re[N(CH₂CH₂S)₃](CO)} (3). Complex 3 was also obtained by treatment of {Re[N(CH₂CH₂S)₃][CNC(CH₃)₃]} (1b) with toluene/hydrochloric acid. The molecular structures of 1b and 3 were established by X-ray structure analysis.     

On Verdigris,Part III: Crystal Structure,Magnetic and Spectral Properties of Anhydrous Copper(II) Acetate,a Paddle Wheel Chain

Pure anhydrous Cu(CH₃COO)₂ was obtained both, by thermal dehydration of Cu(CH₃COO)₂ · H₂O and by drying a commercially purchased mixture of Cu(CH₃COO)₂ · H₂O and Cu(CH₃COO)₂ in a nitrogen atmosphere using P₂O₅ as drying agent. The crystal structure was solved ab initio from synchrotron X‐ray powder diffraction (XRPD) data at 150 °C and from laboratory XRPD data at ambient conditions and found to be isotypic to anhydrous chromium(II), molybdenum(II) and rhodium(II) acetate. Cu(CH₃COO)₂ crystallizes in space group P1 (no. 2) with lattice parameters of a = 5.1486(3) Å, b = 7.5856(6) Å, c = 8.2832(6) Å, α = 77.984(4)°, β = 75.911(8)°, γ = 84.256(6)° at ambient conditions. Cu₂(CH₃COO)₄ paddle wheels with short (2.6 Å) Cu–Cu distances form chains in a direction, which is the main motif in the crystal structure. Due to their identical structural main motif Cu(CH₃COO)₂ · H₂O and Cu(CH₃COO)₂ exhibit a similar bluish‐green color, almost identical UV/Vis spectra and comparable magnetic properties. The temperature dependent magnetic susceptibility also indicates only weak inter‐dimer spin exchange between neighbouring Cu₂(CH₃COO)₄ paddle wheels.     

Synthesis and X-ray crystal structure of oxamido-bridged heterobinuclear Ni(Ⅱ)-Cu(Ⅱ) complexes

The two complexes [Ni(oxen)Cu(L)2](ClO4)2.xH2O (L=2,2'-bipyridyl(bpy), 1,10-phenanthroline(phen)) have been synthesized, where oxen is N,N'-bis(2-aminoethyl)oxamido di-anion. The crystal structure of [Ni(oxen)Cu(bpy)2](ClO4)2.CH3OH has been determined by X-ray diffraction method. The crystal is triclinic system, space group P1 with a=12.179(1),b=12.298(2), c=11.476(2) A, a=97.57(1), B=97.52(1), 7=80.29(2), V=1669.04(67) A3, Z=2, Dcalcd=1.667 g/cm3. The structure has been refined to final R of 0.076 and Rw of 0.080, respectively. The complexes have an extended oxamido-bridged structure and consist of Ni(Ⅱ) ion in a square planar environment and Cu(Ⅱ) ion in a distorted octahedral environment.     

Structure and characterization of a 1d double chain copper(II) complex {[Cu(BIX)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>](PhCOO)<Subscript>2</Subscript>}<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>

A novel copper(II) complex {[Cu(BIX)₂(H₂O)₂](PhCOO)₂} _n (1) (BIX = 1,4-bis(imidazole-1-methyl))-benzene) is synthesized and characterized by elemental analysis, IR, TG, and single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic crystal system with the P-1 space group, Z = 1, a = 9.465(2) Å, b = 9.703(2) Å, c = 12.060(2) Å, α = 77.26(3)°, β = 70.37(3)°, γ = 67.14(3)°, and V = 956.1(3) ų. The crystal structural analysis of complex 1 shows that the copper center is six-coordinated in an elongated octahedral geometry by four N atoms from four different BIX and two O atoms from two water molecules; two neighboring Cu(II) cations are bridged by two BIX extending into an infinite 1D double chain structure.     

Di‐μ‐hydroxo‐bis{(aceto­nitrile)dibenzyl(6‐methyl‐2‐pyridylmethyl)amine‐κ2N,N]copper(II)} bis(perchlorate)

The title compound corresponds to a copper(II) dimer, [Cu₂(OH)₂(C₂H₃N)₂(C₂₁H₂₂N₂)₂](ClO₄)₂, where the metal centres are μ₂‐bridged by hydroxo groups. The coordination of each copper(II) centre is a slightly distorted square‐based pyramid, with two N atoms from dibenzyl(6‐methyl‐2‐pyridylmethyl)amine (BiBzMePMA) and two hydroxo O atoms occupying the basal positions, and the aceto­nitrile N atom at the apical position. The dimer is centrosymmetric, with a crystallographic inversion centre midway between the two Cu atoms [Cu⋯Cu = 2.9522 (9) Å]