Effects on Coordination of Thioether Sites. 4. Structural Analysis of η3-Tripodal Ligand Manganese(I) Complexes

Crystal structures of a series of manganese(I) complexes containing tripodal ligands were determined. For [η³-{CH₃C(CH₂PPh₂)₂(CH₂SPh)-P,P′,S}Mn(CO)₃]PF₆ ( 1 ): a = 10.856(3) Å, b = 19.698(3) Å, c = 17.596(5) Å, β = 96.17(2)°, monoclinic, Z = 4, P2₁/c, R(F_o) = 0.068, R_w(F_o) = 0.055 for 3617 reflections with I_o > 2σ(I_o). For [η³-{CH₃C(CH₂PPh₂)(CH₂SPh)₂-P,P′,S}Mn(CO)₃]PF₆ ( 2 ): a = 9.890(2) Å, b = 20.403(4) Å, c = 10.269(3) Å, β = 117.44(2)°, monoclinic, Z = 2, P2_l, R(F_o) = 0.050, R_w(F_o) = 0.037 for 1760 reflections with I_o > 2σ(I_o). For [η³-{CH₃C(CH₂PPh₂)₂(CH₂S)-P,P′,S}Mn(CO)₃] ( 4 ): a = 8.191(7) Å, b = 10.495(3) Å, c = 19.858(6) Å, α = 99.61(2)°, β = 96.17(2)°, γ = 92.70(4)°, triclinic, Z = 2, P-I, R(F_o) = 0.048, R_w(F_o) = 0.039 for 2973 reflections with I_o > 2σ(I_o). There is no significant difference in the bond lengths of Mn-S bonds among three species in their crystal structures [2.325(2) Å in 1; 2.358(4) in 2; 2.380(2) in 4], but the better donating ability of thiolate in complex 4 appears on the lower frequencies of its carbonyl stretching absorptions.     

The Syntheses and crystal structures of trans-dichlorobis (10-thiabenzo-15-crown-5)-palladium(Ⅱ)and trans-dichlorobis-(10-selenabenzo-15-crown-5)palladium(Ⅱ)

The preparation and X-ray crystal structures of the adducts of 10-thiabenzo-15-crown-5 and 10-selenabenzo-15-crown-5 with PdCl2 are reported. [PdCl2(C14H20O4S)2] (1): or-thorhombic, space group Pbca with cell dimensions of a=17.285(5), 6=8.354(3), c=21.689(4) A, K=3131.9 A3, Z=4;R=0.0330 for 2301 reflections with I > 3o(I), [PdCl2(C14H2oO4Se)2] (2): monoclinic, space group P21/n with cell dimensions of a=18.928(4), b=8.912(3), c=9.813(2) A, β=96.90(2)0, V=1643.4 A3, Z=2; R=0.0289 for 2617 reflections with I> 3σ(I), Both complexes are monomeric, square-planar palladiurn(Ⅱ) compounds with the Pd(Ⅱ) ion situating on a crystal-lographic inversion centre, and the crown ligands all adopt the axial coordination with the Pd-S bond of 2.3233(7) A and the Pd-Se bond of 2.4357(3) A. Their complexing characteristics are discussed in brief.     

A Novel Dinuclear Copper(II) Complex Molecule: Synthesis and Crystal Structure of Cu2(phen)2(H2O)2(C5H6O4)2 with phen = 1,10‐phenanthroline

Blue crystals of Cu₂(phen)₂(H₂O)₂(C₅H₆O₄)₂ were obtained from a CH₃OH–H₂O solution containing CuCl₂, 1,10‐phenanthroline (phen), glutaric acid and Na₂CO₃. The crystal structure (monoclinic, P2₁/c (no. 14), a = 10.271(1), b = 10.595(1), c = 15.585(1) Å, β = 107.105(3)°, Z = 2, R = 0.0328, wR² = 0.1027 for 3376 observed reflections (F ≥ 2σ(F ) out of 3728 unique reflections) is built up of dinuclear Cu₂(phen)₂(H₂O)₂(C₅H₆O₄)₂ complex molecules centered at inversion centers. The Cu atoms are square‐pyramidally coordinated by two nitrogen atoms of one bidentate chelating phen ligand and three oxygen atoms from two bridging glutarate anions and one axial water molecule (d(Cu–N) = 2.018(2), 2.024(2) Å; basal d(Cu–O) = 1.949(2), 1.956(2) Å; axial d(Cu–O) = 2.382(2) Å). Through the π‐π stacking interactions extending in a direction, the complex molecules are interlinked into 2 D layers parallel to the ac plane. The resultant 2 D layers are held together by hydrogen bonds between water molecules and uncoordinated carboxyl oxygen atoms.     

Mononuclear Complexes of Cr(II) and Fe(II) with Terminal -SH Groups. Synthesis and X-Ray Crystal Structures of trans-M(SH)2(dmpe)2 (M = Cr,Fe; dmpe = 1,2-Bis(Dimethylphosphino)Ethane)

Abstract

The reaction of two equivalents of NaSH with MCl₂(dmpe)₂ (M = Cr, Fe,) at—78°C gives trans-M(SH)₂(dmpe)₂ (M = Cr, (1), 30%; Fe, (2) 98%). The complexes have been characterized spectroscopically, and the trans geometry has been confirmed by single crystal X-ray diffraction studies. Crystal data (1): C₁₂H₃₄CrP₄S₂, M= 418.42, monoclinic, P2₁/n, a = 8.857 (I), b= 12.719 (2), c = 9.648 (I) Å, β = 92.14(1)°, U= 1086.2 (5)Å, D _c = 1.279gcm^?3, Z = 2, λ(MoK_a) = 0.71073 Å, (graphite mono-chromator), μ(MoK_a) = 9.80cm^?1. Methods: MULTAN, difference Fourier, full-matrix least-squares. Refinement of 1149 reflections (I > 3σ(I)) out of 1901 unique observed reflections (3.0° < 29 < 48.0°) gave R and R _w values of 0.092 and 0.096, respectively. Crystal data (2): C₁₂H₃₄FeP₄S₂, M = 422.28, monoclinic, P2₁/n, a = 8.834 (2), b = 12.594 (2), c = 9.532 (2) Å, β = 90.66 (2)°, U = 1060.3 (5) ų, D _c = 1.323 g cm^?3, Z = 2, γ(MoK_a) = 0.71073 Å, (graphite monochromator), μ(MoK_a) = 11.87 cm^?1. Methods: same as for (1). Refinement of 1178 reflections (I > 3σ (I)) out of 2086 unique observed reflections (2.0° < 20 < 50.0°) gave R and R _w values of 0.056 and 0.059, respectively.     

SYNTHESIS AND STRUCTURE OF A NOVEL MONONUCLEAR TUNGSTEN (VI) CITRATO COMPLEX, (NH4)3[Li(H2O)3WO3(C6 H4O7)]

Abstract

The first mononuclear tungsten-citrato complex, (NH₄)₃[Li (H₂O)₃WO₃(C₆H₄O₇)] (1), has been prepared by the reaction of ammonium tetrathio tungstate and lithium citrate in CH₃OH-H₂O solution at pH 8.2. There are two crystallographically independent anions in the asymmetric crystallographic unit. The crystal structure of the title compound (triclinic, space group P1, a = 6.901(1), b = 15.136(3), c = 16.107(3) Å, α = 75.85(3), β = 89.89(3), γ = 89.97(3), V = 1631.4(6) ų, R = 0.068, R _W = 0.1674 for 3878 reflections with I > 2σ(I)), reveals that in the compound a tungsten atom is coordinated to a fully deprotonated citrate as a tridentate ligand and three terminal oxygen atoms to form a distorted coordination octahedron.     

Ground state conformation of diphenylvinylphosphine sulfide and selenide

Single-crystal X-ray diffraction experiments have been performed on diphenylvinylphosphine sulfide ( 1 ): C₁₄H₁₃PS, space group P 2₁/c, a = 10.186(1) Ǎ, b = 11.918(1) Å, c = 11.426 Å, β = 112.22(2)°, V = 1284.1(2) ų, Z = 4, and diphenylvinylphosphine selenide ( 2 ): C₁₄H₁₃PSe, space group Pbca, a = 9.141 (3) Å, b = 16.458 (1) Å, c = 17.451 (1) Å, V = 2625.4 (9) ų, Z = 8. The structures were solved by direct methods and were refined by full matrix least-squares calculations to R = 0.046 and R_w = 0.058 using 2554 unique reflections with I > 3σ(I) in the case of 1 , and to R = 0.052 and R_w = 0.065 using 1953 unique reflections with I > 3σ(I) in the case of 2 . In close analogy to the previously studied vinyl phosphine oxides both 1 and 2 were found to exist in the s-cis conformation with the pertinent CC PX dihedral angles equal to 12.5° and 2.9° for 1 and 2 , respectively.     

Structure of Perchlorato(2,5,8,11-Tetraazadodecane)Copper (II) Perchlorate Monohydrate

[Cu(C₈H₂₂N₄)]·(ClO₄)₂.H₂O, M_r= 454.80, orthorhombic C222₁, a = 15.481(5), b = 7.404(1), c = 14.827(3)Å, V = 1699.5(8)ų, Z = 4, D_x = 1.78 g/cm³, λ(MoKα) = 0.71073Å, μ = 16.5 cm^?1. F(000) = 940, T = 22°C, R = 6.86%, R_w = 7.66% for 820 observed reflections (I > 2.5σ (I)). The coordination number for the copper(II) ion is five, and the coordination geometry about copper(II) ion is a buckled square pyramid with the tetraamine equatorial and a perchlorate ion axial. The tetraamine is coordinated in a square-plannar manner with slight tetrahedral distortions. The four Cu-N distances span a very narrow range, 1.990(10) ?1.994(14)Å.     

Hydrothermal Synthesis,Crystal Structures and Characterization of Two Hydrogen Phosphates Templated by 4-Amino-2,2,6,6-tetramethylpiperidine

Abstract

Chemical preparations, crystal structures, thermal analyses, and IR spectroscopic studies are given for two new hydrogen phosphates templated by 4-amino-2,2,6,6-tetramethylpiperidine: (C₉H₂₂N₂)₂·(H₂PO₄)·(HPO₄)·(F)·H₂O (I) and (C₉H₂₂N₂)·(H₂PO₄)₂(II). The structures are determined by single crystal X-ray diffraction. Both compounds crystallize in the P2₁/c (N°14) monoclinic space group with the unit cell parameters: a = 14.856 (1) Å, b = 14.092 (2) Å, c = 14.7166 (9) Å, β = 118.434 (7)°, V = 2709.2 (4) Å ³, and Z = 4 for (I) and a = 9.803 (2) Å, c = 0.466 (2) Å, c = 15.640 (8) Å, β = 94.990 (4), V = 1598.68 (7) ų, and Z = 4 for (II).

The structure of I, refined to R = 0.042 and R_w = 0.067 for 6009 reflections (I ≥ 2σ (I)), exhibits infinite inorganic chains _∞((H₂PO₄)·(HPO₄)·(F)·H₂O)^4? linked together through weak hydrogen bonds to form layers onto which the diprotonated [C₉H₂₂N₂]^{2 +} amine molecules are anchored.

The structure of II, refined to R = 0.060 and R_w = 0.086 for 1435 reflections (I ≥ 2σ (I)), consists of _∞(H₂PO₄)^? (100) layers between which [C₉H₂₂N₂]²⁺ cations are inserted. A network of hydrogen bonds connects the different components. IR spectra of I and II show the characteristic bands of amine groups and phosphate anions.     

The Role of Chloro Substituents in Solid Inclusion Formation. Crystal Structures Formed by a Bulky Hydroxy Host with Ethyl Acetate (2:1) and Cyclohexylamine (1:2) as Guest

Abstract

Two inclusion compounds of the 11-[bis(p‐chlorophenyl)hydroxymethyl]-9,10-dihydro-9,10-ethanoanthracene host (1) have been studied by X-ray diffraction in order to find an explanation of the exceptional clathrate formation ability of the present chloro-containing host as compared with that of closely related chlorine-free host analogues. Crystal data: 1·ethyl acetate (2:1), C₂₇H₂₂OCl₂·½(C₄H₈O₂), M_w = 501.45, P2_1/c, a = 8.9060(5), b = 11.1109(6), c = 25.642(1) Å, β = 99.03(1)°, Z = 4, R = 0.047 for 2029 F values with I>2σ(I); 1·cyclohexylamine (1:2), 2[C₂₉H₂₂OCI₂·2(C₆H₁₃N)], M_w = 1311.50, Pc, a = 12.144(2), b = 12.689(3), c =23.119(8) Å, β = 91.68(1)°, Z = 2, R = 0.054 for 3073 F values with I>2σ(I). Although the two solid inclusion compounds differ in host‐guest stoichiometry, space group symmetry and also in host‐guest recognition mode, both co-crystals are held together by numerous C?H…X (X = O, N or Cl) interactions, in which the chloro-substituents of 1 play a very active role. The observed frequent participation of chlorine in intermolecular interactions in these compounds suggests an ability of the (C?)Cl substituents to effectively enhance the crystal formation in the absence of more dominant forces.     

Crystal and Molecular Structure of the Macrocyclic Nickel (II) Complex Ni(C22H22H4): Dibenzo[b,i][5, 7, 12, 14] Tetramethyl [1, 4, 8, 11] Tetraazacyclotetradeca-2, 4, 7, 9, 12, 14-Hexaeneatonickel (II)

The crystal and molecular structure of the four-coordinate complex Ni(C₂₂H₂₂N₄) containing the tetramethyldibenzotetraaza[14] annulene ligand has been determined from three-dimensional X-ray diffraction data. The complex crystallized in the monoclinic space group C_2h⁵-P2₁/n with cell dimensions a=14.7967(10), b=11.2169(6), c=11.4510(6) Å, and β=98.467(5)° with Z=4. The final agreement indices from the least-square refinement of 245 variables with 3111 observations F>3σ(F), are R=0.050, R_w=0.037. The structure has a pronounced saddle-shaped conformation with Ni atom at the saddle point coordinated to four nitrogen atoms. The average Ni-N distance is 1.866(3) Å. The delocalized propane-1,3-diiminato chelate rings and the benzene rings are linked by nominally single C-N bonds.     

Deprotonierte Dithiocarbaminsäureester als Thiolat-S-Donor-Liganden. Strukturen von Ph(H)NC(S)SMe,Co(PhNC(S)SMe)3 und Cu6(PhNC(S)SMe)6

Deprotonated Dithiocarbamic Acid Esters as Thiolate S-Donor Ligands. Structures of Ph(H)NC(S)SMe, Co(PhNC(S)SMe)₃, and Cu₆(PhNC(S)SMe)₆ The reaction of N-phenyl-S-methyldithiocarbamate, PhN(H)C(?S)SMe, ( 1 ) with cobalt(II) and copper(II) salts yields the monomeric compound Co^III(PhNC(S)SMe)₃ ( 2 ) and the hexameric compound Cu₆^I(PhNC(S)SMe)₆ ( 3 ). These complexes contain the negatively charged imino-thiolate ligand PhN?C(? S)SMe, which has been formed by deprotonation of 1 . The crystal structures of 1 – 3 have been determined. 1 forms centrosymmetrical dimers through N? H …? S bridge bonds, the conformation in the solid state and in solution is Z,E′. Co^III shows in 2 a trigonal-antiprismatic coordination, with the ligands acting as N,S-chelates. 3 contains an octahedral Cu₆-core with Cu …? Cu-distances ranging from 276.3(5) to 305.7(4) pm. Each copper center is trigonally coordinated to one nitrogen and two sulfur atoms of three different ligands. Crystal data: 1 , triclinic, space group P1 , a = 590.5(6), b = 869.0(1), c = 968.5(9) pm, α = 67.29(8), β = 78.44(8), γ = 81.64(9)°, Z = 2, 1 775 reflections, R(R_w) = 0.0317(0.032). 2 , orthorhombic, space group Pbca, a = 978.0(2), b = 1 842.9(4), c = 3 059.7(6) pm, Z = 8, 1 129 reflections, R(R_w) = 0.0997(0.0886). 3 , monoclinic, space group P2₁/c, a = 1 363.1(3), b = 1 342.8(3), c = 1 671.9(3) pm, β = 103.48°, Z = 2, 1 374 reflections, R(R_w) = 0.0708(0.0617).     

SYNTHESES,CHARACTERIZATION AND CRYSTAL STRUCTURE OF TETRAMETHYLDIBENZOTETRAAZA[14]-ANNULENE ZINC(II) COMPLEXES CONTAINING AN AXIAL BASE

Abstract

The complexes of Zn(tmtaa) and Zn(tmtaa)L [H₂tmtaa = tetramethyldibenzotetraaza[14]-annulene; L = triethylamine, pyridine (Py) and p-dimethylaminopyridine (p-N(CH₃)₂Py)] were synthesized and characterized by IR, LTV, mass and NMR spectra as well as DSC measurements. The effects of different axial ligands (L) on the spectral properties of the complexes have been studied. The crystal structure of Zn(tmtaa)N(C₂H₅)3 was determined by X-ray diffraction. The crystal belongs to a monoclinic system and the space group is P2₁/n. The cell parameters are a = 11.134(2)A, b = 17.453(4)Å, c= 13.784(3)Å, ? = 106.19(3)°, Z = 4, R₁, =0.0336 and wR₂= 0.0805 for 4539 independent reflections with I <2σ(I). The zinc(II) is coordinated through four nitrogen atoms of tmtaa and a nitrogen of triethylamine to form a five-coordinate square-pyramidal structure. The average bond length of Zn for the four nitrogens of tmtaa is 2.050(2)Å and for a nitrogen of triethylamine is 2.188(2)Å. The displacement of the zinc to the plane of four nitrogens of tmtaa is 0.563(2)Å.     

Crystal Structure of frans-Dichloro(c-Meso-3,5,7,7,10,12,14,14-Octamethyl-1,4,8,11 -Tetraaza Cyclotetradeca-4,11-Diene)Cobalt(lll) Perchlorate

The crystal structure of the title compound has been solved by X-ray diffraction. [CO(Cl)₂(N₄C₁₈H₃₆)]-(ClO₄), M_r = 537.79, triclinic, P1, a = 6.974(4), b = 8.530(1), c = 11.061(2) Å, α = 98.47(1), β = 106.56(3), γ = 93.02(3)°, V = 620.8(4) ų, Z = 1, Dx = 1.439 Mg m^?3, λ(MoKα) = 0.7093 Å, μ = 0.96 mm^?1, F(000) = 291.93, T = 297(3) K, R = 0.072, R_w = 0.085 for 2121 observed reflections. The Co(III) is six-coordinate with the four N atoms of the macrocyclic ligand equatorial and two Cl ions axial, thereby resulting in a tetragonally distorted octahedral geometry. Aside from the perchlorate group, there exists a non-crystallographic inversion center at the Co(III) ion for the macrocyclic ligand and the two Cl ions which are bonded to the Co(III) ion.     

Ru(II) COMPLEXES CONTAINING CHELATING PHOSPHINE LIGANDS. SYNTHESIS,CHARACTERIZATION, AND X-RAY CRYSTAL STRUCTURES OF DICHLOROBIS(1,2-BIS(DIPHENYLPHOSPHINO)ETHANE)Ru(II) AND THE COORDINATIVELY UNSATURATED TRIGONAL-BIPYRAMIDAL CATION,CHLOROBIS-(1,2-BIS(DIPHENYLPHOSPHINO)ETHANE)Ru(II)

Abstract

The reaction of trans-RuCl₂(dppe)₂ (1), with AgBF₄ in tetrahydrofuran leads to abstraction of one of the halide ligands to produce the trigonal-bipyrimidal complex, [RuCl(dppe)₂]BF₄ (2). Both products are characterized by ³¹P NMR spectroscopy and their crystal structures determined. For the coordinatively unsaturated trigonal-bipyramidal complex (2), we found no evidence for the presence of more than one species or fluxional behaviour at room temperature in the ³¹P NMR spectrum. This complex was found to possess a trigonal-bipyramidal geometry in the solid state. Crystals of 1 are monoclinic, space group P2₁/c with a = 23.713(4)Å, b=11.156(1)Å, c = 17.595(2)Å, β=103.23(1) and v=4531(1)ų. Convergence to conventional R values of R=0.043 and R_w = 0.042 was obtained for 416 variable parameters and 2746 reflections with I>3σ(I). Compound 2 in triclinic, P1, a=12.482(3)Å, b=12.543(3)Å, c=17.582(3)Å, α = 87.52(2)°, β= 72.70(2)° γ = 74.35(2)° and V= 2529(1)ų. Values of R = 0.072 and R_w = 0.097 were obtained for 487 variable parameters and 3242 reflections with I>3σ(I)     

[C10N2H10][ZnCl(HPO4)]2: A New Templated Zincophosphate Containing Tetrahedral Nets with 63 Topology

The crystal structure of [C₁₀N₂H₁₀][ZnCl(HPO₄)]₂ contains corrugated tetrahedral layers with 6³ topology. Charge balance is achieved by insertion of diprotonated 4,4′‐bipyridine between the layers. Crystal data: monoclinic, P2₁/n (no. 14), a = 4.8832(2) Å, b = 22.673(2) Å, c = 8.1643(4) Å, β = 104.02(1)°; V = 877.0(1) ų; Z = 4; R1 = 0.041 and wR2 = 0.088 for 1836 reflections [I > 2σ(I)]. Tetrahedral layers are also observed in other organo‐ammonium templated compounds. However, their topologies are characterized by 4.8² nets. With the title compound a layered tetrahedral net with 6³‐topology is reported for the first time.     

Tetranuclear cobalt(II) complex and trinuclear copper(II) complex with the ligand 2-hydroxy-3-[(2-sulfoethylimino)-methyl]-benzoic acid: synthesis,structure and properties

A cobalt(II) compound, [Co₄(L)₂(OH)₂(phen)₂(H₂O)₄] · 6H₂O (1), and a copper(II) compound, [Cu₂(L)₂(H₂O)₂][Cu(H₂O)₆] · 6H₂O (2) [where H₃L is 2-hydroxy-3-[(2-sulfoethylimino)-methyl]-benzoic acid and phen is O-phenanthroline], were prepared and characterized. The tetranuclear cobalt complex 1, C₄₄H₆₂N₆O₂₈S₂Co₄, crystallizes in the monoclinic space group P2₁/c, with a = 11.847(10) Å, b = 19.061(15) Å, c = 12.635(10) Å, β = 105.483(9)°, and Z = 2; R ₁ for 4821 observed reflections [I > 2σ(I)] was 0.0679. Complex 1 is a centrosymmetric tetranuclear cobalt complex with all cobalts having distorted octahedral geometry. The molecule can be viewed as two planar [Co₂(OH)(L)(Phen)H₂O] units tied together by two terminal water molecules. The framework of 1 has the appearance of two connected face-sharing cubes, each with one vertex missing. The trinuclear copper complex 2, C₂₀H₄₄Cu₃N₂O₂₆S₂, crystallizes in the triclinic space group P1, with a = 7.524(1) Å, b = 7.902(2) Å, c = 16.885(4) Å, α = 88.993(6)°, β = 80.725(7)°, γ = 66.725(4)° and Z = 1; R ₁ for 4298 observed reflections [I > 2σ (I)] was 0.0360. Complex 2 is an ionic compound, in which the three Cu(II) centers have two coordination modes. The molecule has a centrosymmetric dinuclear copper coordinated anion and a hexa-aqua-copper cation. The sulfonic acid group has less coordination ability than carboxylate oxygen.     

Rhenium(I) Tellurolate,Telluroether and Bidentate-Telluroether Complexes: Crystal Structures of Re(CO)3Br(PhTe(CH2)3TePh), PhTeRe(CO)5 Re2(μ-SePh)2(CO)8 and [(PhTeMe)Re(CO)5][BF4]

The monomeric rhenium(I) complex with bidentate telluroether ligand Re(CO)₃Br(PhTe(CH₂)₃TePh) (1) was accessible via reaction of the PhTe(CH₂)₃TePh with Re(CO)₅Br. This chelate complex crystallized in triclinic space group $ {\rm P}\bar 1 $ with a = 9.390(5) Å, b = 10.961(3) Å, c = 11.849(4) Å a = 63.30(3)°, β = 87.49(4)° γ = 69.31(4)°, V = 1009.5(7) ų Z = 2, R = 0.033, and R_w = 0.034. Reaction of Re(CO)₅Cl with NaTePh yielded the Re(I) specics PhTeRe(CO)₅ (2). This complex crystallized in triclinic space group $ {\rm P}\bar 1 $ with a = 7.085(1) Å, b = 9.203(1) Å, c = 11.341(1) Å, α = 107.24(1)°, β = 100.56(1)°, γ = 96.47(1)°, V = 683.2(2) ų, Z = 2, R = 0.027, R_w = 0.022. Reaction of PhTeRe(CO)₅ and (PhSe)₂ in THF at 65 °C yielded a product that was confirmed crystallographically to be the known species Re₂(μ-SePh)₂(CO)₈ (3), in which two phenylselenolate ligands bridge the two Re(I). Compound 3 crystallized in monoclinic space group P2₁/n with a = 7.210(2) Å, b = 18.862(6) Å, c = 9.083(3) Å, β = 107.48(3)° V = 1178.2(7) ų, Z = 2, R = 0.046, and R_w = 0.051. Methylation of PhTeRe(CO)₅ with [Me₃O][BF₄] afforded Re(I) product [(PhTeMe)Re(CO)₅][BF₄] (4). This monodentate telluroether species crystallized in monoclinic space group P2₁/n with a = 8.405(1) Å, b = 13.438(3) Å, c = 15.560(2) Å, β = 92.59(1)° V = 1755.5(5) ų, Z = 4, R = 0.035, and R_w = 0.035.     

Bildung oktaedrischer Komplexe durch cis-Addition an planar-quadratisches Bis(oxamidoximato)nickel(II): drei Strukturbeispiele

Formation of Octahedral Complexes via cis-Addition to Square Planar Bis (oxamideoximato)nickel(II): Three Structure Examples In the reaction of orange square planar bis(oxamide oximato)nickel(II) with acids, blue to blue-green octahedral complexes are formed with neutral oxamide oximide ligands and two acid anions in cis-positions. Three compounds are described: cis-dichlorobis(oxamide oxime)nickel(II) ( 1 ), NiCl₂(C₂H₆N₄O₂)₂, M_r = 365.81, monoclinic P2₁/n, a = 6.641(2), b = 14.086(4), c = 13.473(3) Å, β = 96.26(2)°, V = 1 252.8 ų, Z = 4, d_c = 1.94 gcm^?3, final R_w = 0.031 for 4090 reflections. In cis-di(sulfanilato)bis(oxamide oxime)nickel(II) dihydrate ( 2 ) one sulfanilic anion coordinates via the sulfonic acid group, the other one via the amino group; Ni(C₆H₆NO₃S)₂(C₂H₆N₄O₂)₂ · 2 H₂O, M_r = 675.30, monoclinic P2₁, a = 6.879(3), b = 14.305(5), c = 13.930(5) Å, β = 103.62(4)°, V = 1332 Å, Z = 2, d_c = 1.68 gcm^?3, R = 0.067 for 2693 reflections. In catena-μ-(phthalato)bis(oxamide oxime)nickel(II) tetrahydrate ( 3 ) bidentate bridging phthalate anions lead to chain formation; Ni(C₈H₄O₄)(C₂H₆N₄O₂)₂ · 4H₂O, M_r = 531.09, monoclinic P2₁/c, a = 10.633(8), b = 11.324(5), c = 17.680(14) Å, β = 98.25(7)°, V = 2107 ų, Z = 4, d_c = 1.67 gcm^?3. Final R = 0.110 for 3290 reflections.     

Cobalt(II) Complexes with Dicyanamide — from Binuclear Entities to Chains

One binuclear complex [Co(bpm*)₂(dca)]₂(ClO₄)₂ ( 1 ) and two 1D chain Co^II complexes, {[Co(bpm)₂(dca)](ClO₄)}_n ( 2 ) and [Co(dmf)₂(dca)₂]_n ( 3 ), (bpm*: bis[(3, 5‐dimethyl)pyrazolyl]methane; bpm: bis(pyrazolyl)methane; dca: dicyanamide; dmf: N, N‐dimethyl formamide) have been prepared and structurally characterized. The cobalt atoms are hexa‐coordinated forming a slightly distorted octahedral coordination. Compound 1 crystallizes in the monoclinic system, space group P2₁/c, a = 9.849(3)Å, b = 21.944(7)Å, c = 13.814(5)Å, β = 94.824(6), Z = 4, R₁ = 0.0672, wR₂ = 0.1395. 1 is a binuclear complex linked by two dca ligands, and each Co^II ion is coordinated by two terminal bpm* ligands. Compound 2 crystallizes in the orthorhombic system, space group Cmcm, a = 10.377(4)Å, b = 13.594(5)Å, c = 15.999(6)Å, Z = 4, R₁ = 0.0609, wR₂ = 0.1328. The structure of 2 can be described as a one‐dimensional zigzag chain of Co^II ions bridged by one dca ligand. Each Co^II ion in the chain is coordinated by two bpm ligands. Compound 3 crystallizes in the monoclinic system, space group C₂, a = 13.559(15)Å, b = 7.393(8)Å, c = 8.110(9)Å, β = 112.228(15), Z = 2, R₁ = 0.0260, wR₂ = 0.0760. 3 has a one‐dimensional linear chain of Co^II ions bridged by two dca ligands, in which each Co^II ion is coordinated with two dmf molecules.     

Synthese und Struktur der Cobalt(III)-Komplexe 14gliedriger cis- und trans-N2S2-Dibenzomakrocyclen mit zwei koordinierenden Acetatogruppen

Synthesis and Structure of Cobalt(III) Complexes of 14-Membered cis- and trans-N₂S₂ Dibenzo Macrocycles with two Pendant Acetato Groups The isomeric fourteen membered macrocyclic ligands 6,7,9,15,16,18-hexahydrodibenzo[f,m][1,8]dithia[4,11]diazacyclotetradecine-8,17-diacetic acid-0.5-hydrate (H₂L³), C₂₂H₂₆N₂O₄S₂ · 0.5 H₂O and 6,7,13,15,16,18-hexahydrodibenzo-[e,m][1,4]dithia[8,11]diazacyclotetradecine-14,17-diacetic acid-1.5-hydrate (H₂L⁶), C₂₂H₂₆N₂O₄S₂ · 1.5 H₂O with cis- and trans-N₂S₂ donorsets and two pendant acetato groups form the stable complexes [Co(L³)]ClO₄ · 2 H₂O ( 1 ) and [Co(L⁶)]ClO₄ · H₂O ( 2 ). Co(III) is octahedrally coordinated herein to all six donor centers of the respective ligand. The macrocyclic rings are folded. The metal ions are located outside the macrocyclic cavity. The mean Co? N, Co? O and Co? S distances are 196, 190 and 224 pm, respectively. Crystal data: 1 , monoclinic, space group C2/c, a = 3 797.7(9), b = 763.8(3), c = 2 207.0(7) pm, β = 123.17(2), Z = 8, 3 445 reflections, R(R_w) = 0.072(0.070); 2 , monoclinic, space group C2/c, a = 3 197.1(6), b = 880.4(2), c = 1 890.6(4) pm, β = 112,19(3)°, Z = 8, 4 415 reflections, R(R_w) = 0.062(0.064).