Crystal and molecular structure of bis(N,N-di-n-butyldithiocarbamato)copper(III) triiodide

The crystal and molecular structure of bis(N,N-di-n-butyldithiocarbamato)-copper (III) triiodide, Cu(S₂CN(C₄H₉)₂)₂ ⁺I₃ ^–, has been determined from a single-crystal X-ray diffraction study. The monoclinic unit cell, space groupP2₁/c,a = 14·026(6),b = 8·62(1),c = 25·015(9) Å, = 95·35(5) °, contains four formulaentities. Three-dimensional intensity data were obtained from Weissenberg photographs. Atomic parameters were refined by full-matrix least-squares methods to a conventionalR value of 0·083 for 950 independent non-zero reflexions. The structure contains two symmetry-independent cations. In both cations, the copper atom is in planar coordination with four sulphur atoms, the mean Cu(III)-S bond length being 2·22(2) Å. Cu(III)-S distances are about 0·08 Å less than Cu(II)-S distances in comparable complexes.     

Crystal and molecular structure of bis(N,N-di-n-butyldithiocarbamato)gold(III) dibromoargentate(I)

The crystal and molecular structure of bis(N,N-di-n-butyldithiocarbamato)gold(III)dibromoargentate(I), Au(S₂CN(C₄H₉)₂)₂AgBr₂, has been determined by three-dimensional X-ray methods. The compound crystallizes in the monoclinic space groupC2/c with unit cell dimensions:a= 17·39(1)b = 18·65(1);c = 9·199(6) Å; = 93·9(1)°;Z=4. Intensities were collected on an automatic diffractometer. The structural parameters were refined by least-squares methods to a conventionalR factor of 0·048 for 854 non-zero observed reflexions. The structure consists of Au(S₂CN(C₄H₉)₂)2⁺ and AgBr₂ ^– ions. The gold is in planar coordination with four sulphur atoms, the two crystallographically non-equivalent Au-S bond lengths being 2·357(8) and 2·324(8) Å. The silver is linearly coordinated, the Ag-Br bond lengths being 2·450(5) Å. The ionic packing in the structure differs from that in the analogous Au(S₂CN(C₄H₉)₂)₂AuBr₂ complex.The authors are grateful to Professor J. J. Steggerda for his continuous interest and to Mr. W. P. J. Bosman and Mr J. M. M. Smits for valuable assistance. Authors of contributions from the Department of Inorganic Chemistry and Crystallography of this University will no longer be listed in alphabetical order.     

Crystal structure of bis(morpholino)-disulphide

The crystal structure of bis(morpholino)-disulphide C₈H₁₆N₂O₂S₂, has been solved by the symbolic addition procedure using three-dimensional CuK diffractometer data. The system is monoclinic,a = 5·717(4),b = 8·880(7),c = 23·080(20) Å, = 107·8(1) ° andZ = 4. The structure was refined by fullmatrix least-squares methods to a conventional, unweightedR of 0·039 for 1441 observed reflexions. All hydrogen positions have been determined. The molecule possesses a pseudo-diad axis, the morpholine rings being in the chair conformation. Bonds at nitrogen are distorted pyramidal with the attached sulphur equatorial.     

Copper(II) complexes 1-phenylpropane-1,2-dione- and benzil bis(3-piperidylthiosemicarbazone): A structural study

The crystal and molecular structure of copper(II) complexes of benzil bis(3-piperidylthiosemicarbazone), [Cu(Bnzpip)] and 1-phenylpropane-1,2-dione bis(3-piperidylthiosemicarbazone), [Cu(Pmpip)] have been determined. [Cu(Bnzpip)] is monoclinic, space group P2₁/n with a = 13.9375(10) Å, b = 11.6621(4) Å, c = 16.4710(10) Å, = 100.667(2)°, and V = 2630.9(3) ų with Z = 4, for d _calc = 1.399 g/cm³. [Cu(Pmpip)] is also monoclinic, space group P2₁/n with a = 11.292(6) Å, b = 10.219(5) Å, c = 20.292(6) Å, = 101.50(3)°, and V = 2295(2) ų with Z = 4, for d _calc = 1.525 g/cm³. Both complexes involve N₂S₂ coordination, are relatively planar except for the phenyl rings and have similar bond distances and angles to copper(II) complexes of other 3-piperidylthiosemicarbazones.     

Crystal and molecular structure of bis(N,N-diethyldithiocarbamato)palladium(II)

The crystal and molecular structure of bis(N,N-diethyldithiocarbamato)palladium(II), Pd(S₂CN(C₂H₅)₂)₂, has been determined by a three-dimensional X-ray analysis. The compound crystallizes in the tetragonal space groupP4₂/n with unit cell dimensionsa = 16·439(8) Å andc = 6·247(3) Å. The crystals are isomorphous with bis(N,N-diethyldithiocarbamato)platinum(II). Intensities were obtained with an automatic diffractometer. The structural parameters were refined by least-squares methods to a conventionalR factor of 0·038 for 600 non-zero observed reflections. The palladium is in planar coordination with four sulphur atoms, the two non-equivalent Pd-S bond lengths being 2·317(3) and 2·315(3) Å.The authors are grateful to Mr J. G. M. van Rens for providing the crystals and measuring the unit cell dimensions, to Professor J.J. Steggerda for his continuous interest and to Mr W.P.J.H. Bosman, Mr J.M.M. Smits and Mr J.A.B.C. Wolf for valuable assistance.     

The crystal structures of p-iodo-N-(p-cyanobenzylidene)aniline and p-cyano-N-(p-iodobenzylidene)aniline

The crystal structures of the isomers NC–C₆H₄–CH=N–C₆H₄–I (CN/I) and I–C₆H₄–CH=N–C₆H₄–CN (I/CN) have been determined. CN/I is triclinic, space group P1¯ with a = 7.504(3), b = 11.936(4), c = 7.304(2) Å, = 93.09(2), = 110.49(2), = 99.04(2)°, V = 601.1(3) ų, Z = 2, and D _x = 1.818(1) g cm^–3. In both compounds there are chains of molecules held together by CN···I interactions, with N···I distances of 3.15 and 3.26 Å, respectively. The chains form similar two-dimensional sheets, which, however, stack differently in the two compounds.     

A dinuclear cyano-bridged complex based on hexacyanoferrate(III) and samarium(III) nitrate: synthesis and crystal structure

A new complex, [Sm(DMF)₄(H₂O)₄Fe(CN)₆]·H₂O (DMF = N, N-dimethylformamide), has been synthesized and characterized by X-ray single crystal structure and thermogravimetric analyses. The complex crystallizes in the P2₁/n space group, with lattice parameters a = 17.583(4) Å, b = 8.870(2) Å, c = 19.845(6) Å, = 95.98(3)°, V = 3078(1) ų, D _x = 1.679 Mg m^–3, D _m = 1.65(1) Mg m^–3, Z = 4. The molecular structure shows that a cyano-bridged bimetallic structure is obtained. The Sm atom is coordinated by eight oxygen atoms of four water molecules and four DMF molecules and one nitrogen atom of the bridging cyanide ligand. The iron atom assumes approximately an octahedral environment surrounded by six CN ligands. The hydrate water molecule is hydrogen-bonded to one of the O atoms bound to Sm. Each terminal CN ligand of the Fe(CN) ₆ ^3– entity is hydrogen-bonded to some O atoms of water molecules. An infrared spectrum is also reported.     

The structure of bis(trimethylammonium) undecachlorotriantimonate(III) [(CH3)3NH]2Sb3Cl11 containing a novel antimony(III) anion

The structure of [(CH₃)₃NH]₂Sb₃Cl₁₁ (space group P2₁/n; a = 10.374(2), b = 23.723(5), c = 11.884(2) Å, = 113.46(3)°; V = 2682.9(9) ų) consists of a structurally novel [Sb₃Cl^2– ₁₁] anion and two crystallographically nonequivalent trimethylammonium cations. The anion is composed of three deformed octahedra in the asymmetric part of the unit cell. The octahedra are connected with each other by edges and corners forming a characteristic polyanionic layer. Trimethylammonium cations, one ordered and one disordered, are connected to the inorganic sublattice by N—H···Cl hydrogen bonds.     

Preparation and characterization of a bidentate carboxylate-bridged dinuclear cadmium(II) complex with bis(2-pyridylmethyl)amino-3-propionic acid

The carboxylate-bridged dinuclear complex [Cd(-pmpa)(H₂O)](ClO₄)·H₂O (1) (Hpmpa = bis(2-pyridylmethyl)amino-3-propionic acid) has been synthesized and structurally characterized by X-ray diffraction method. It crystallizes in the monoclinic system P2 ₁/n with a = 7.9678(6) Å, b = 17.5103(9) Å, c = 14.3147(9) Å, = 94.1030(10)°, V = 1992.0(2) ų, Z = 4. The carboxylate group of the pmpa ligand adopts a bidentate bridging coordination mode, and the ligand acts as -bridge linking two cadmium(II) ions to form a dinuclear complex. Each cadmium atom is seven-coordinate, with a distorted pentagonal bipyramidal geometry. The cyclic voltammogram of 1 undergoes irreversible one-electron oxidation to the Cd(III) and reversible one-electron reduction to the Cd(I).     

Crystal and molecular structure of triphenylphosphine (N,N-diethyldithiocarbamato)gold(I)

The crystal and molecular structure of triphenylphosphine (N,N-diethyldithio-carbamato) gold(I), (C₆H₅)₃PAuSSCN(C₂H₅)₂, has been determined by three-dimensional X-ray methods. The compound crystallizes in the monoclinic space groupP2₁/c witha = 13·547(1),b = 12·277(1),c = 14·013(1) Å, = 90·81(1) ° andZ = 4. Three-dimensional intensity data were collected on an automatic diffracto-meter. Atomic parameters were refined by full-matrix least-squares methods to a conventionalR value of 0·04 for 2318 non-zero observed reflexions.In this complex the diethyldithiocarbamate moiety acts as a monodentate ligand, the double-bond distance being 1·68(1) Å and the bond involving the sulphur atom that is coordinated to the gold atom being 1·75(1) Å. The gold atom is linearly coordinated, the angle being 175·7(1) ° and the and distances being 2·338(3) and 2·251(3) Å, respectively.     

Crystal structure of chloritopentamminecobalt(III) tetracyanopalladate(II)

The X-ray crystal structure of [(NH₃)₅Co(ClO₂)][Pd(CN)₄]·H₂O consists of two discrete complex ions and a water of hydration. The red crystals are triclinic, P , with lattice parameters a = 7.1992(5), b = 9.4873(7), c = 11.7752(8) Å. = 66.680(1), = 75.784(1), = 82.203(1)°, and Z = 2 giving a cell volume of 715.27(9) ų and a calculated density of 2.043 g/cm³ at 293°. The chlorite ion is O-bonded to the cobalt atom with amine N—Co distances all equal. The chlorite ion is bent with a O—Cl—O angle of 110.8(2)° and the Cl—O distances being 1.601(3) and 1.558(3) Å, the longer value for the O atom also coordinated to Co. The Pd(CN)^–2 ₄ ions are planar, C-coordinated and stack along the x-axis, separated by 3.599(1) Å and alternatively rotated by 29.9(5)°.     

Crystal and molecular structure of bis(acetylacetonato) nickel(II)diethanol

The title compound, Ni(C₅H₇O₂)₂· (C₂H₅OH)₂, crystallizes in the triclinic system with unit cell dimensionsa = 8·923,b = 5·283,c = 9·522 Å, = 81·4, = 106·1 and = 103·3 °;Z= 1, space groupP¯1. The structure was solved by Fourier methods, and the 1557 three-dimensional counter diffraction intensity data (CuK) were used in a least-squares refinement to a conventional unweightedR of 0·053. The nickel atom is surrounded by the four oxygen atoms of the two acetylacetone ligands and the two oxygen atoms of the ethanol molecules, forming a tetragonally-distorted octahedron with acetylacetone oxygen atoms at 1·997 and 2·026 Å and ethanol oxygen atoms at 2·140 Å. Parallel molecules are linked into columns along theb-axis by hydrogen bonds between the ethanol oxygen atom of one molecule and an acetylacetone oxygen atom of a neighboring molecule.Presented at the Amer. Cryst. Ass'n. Summer Meeting, Ames, Iowa, Aug. 1971.Taken in part from the M.S. Thesis in Physics of T. S. Burke, Syracuse University, 1971.     

Crystal structure of [Mn2(III)(salpa)2Cl2(H2O)2] (H2salpa = 1-(salicylaldeneamino)-3-hydroxypropane)

The manganese complex, (Mn₂(III)(salpa)₂Cl₂(H₂O)₂], has been prepared and its structure determined using x-ray crystallography. The dimer is a di-₂-alkoxo complex which is a six-coordinate manganese dimer with unsupported alkoxide bridges and a rare example of a chloride- and water-containing manganese dimer. The complex crystallizes in the monoclinic space group P2₁/c with a = 9.315(5), b = 11.130(4), c = 11.637(5) Å, = 104.33(3)°, V = 1169.0(9) ų, and Z = 2. The structure comprises discrete binuclear clusters in which the metal atoms are bridged by two alkoxo oxygens of the salpa^2– ligands. The Mn—O and Mn—N distances are in good agreement with those found for other manganese(III) Schiff base complexes. The Mn—Cl and Mn—O3 distances are 2.585(2) and 2.371(2) Å, respectively, and the Mn ··· Mn distance is 3.001(1) Å. In the crystal, there are two types of hydrogen bonding between the H₂O molecule and the Cl atom with Cl ··· H(H₂O) distance of 2.33(6) (intramolecule: –1 + x, y, –1 + z) and 2.68(6) Å (intermolecule: –1 + x, 0.5–y, –0.5 + z).     

Crystal and molecular structure of bis[pyridine-2-(N-cyanocarboxamidato)]aquocopper(II), Cu(C5H4NCONCN)2(OH2)

Bis[pyridine-2-(N-cyanocarboxamidato)]aquocopper(II), Cu(C₅H₄NCONCN)₂(OH₂), has been prepared and its i.r. spectrum and crystal structure have been determined. The crystals are triclinic (P¯1):a = 11·45(1),b = 10·35(1),c = 7·48(1) Å, = 110·9(1), = 102·2(2), = 108·9(1)°,Z = 2. The X-ray analysis, carried out using three-dimensional Patterson, Fourier and least-squares methods (finalR = 5·7%), showed copper(II) to be pentacoordinated, with two organic ligands chelating through their pyridine [Cu-N = 1·997(4), 1·989(4) Å] and amide nitrogen atoms [Cu-N = 1·980(7), 2·006(6) Å], and with one water molecule at a distance [Cu-OH₂ = 2·335(4) Å] sensibly longer than the usual Cu-O(2·0 Å) coordinate bonds. The coordination polyhedron can be described either as a distorted tetrahedron formed by the nitrogen atoms with an extra position occupied by water or as a trigonal bipyramid having water and two nitrogen atoms in the equatorial plane. The packing determining interactions are the hydrogen bonds formed by water, and a long Cu...N (3·420 Å) contact between the metal and a nitrogen atom from an adjacent molecule.The authors are indebted to Prof. Immirzi who kindly supplied his computer programmes.     

Substituted phenols as ligands III: Crystal and molecular structure of bis(4-formyl-2-methoxyphenolato)bis(pyridine)copper(II) monohydrate

Bis(4-formyl-2-methoxyphenolato)bis(pyridine)copper(II) monohydrate crystallizes in the triclinic system:a = 10·432,b = 9·342,c = 13·799 Å, = 103·75, = 100·53, = 100·81 °,Z = 2, space groupP¯1.The structure was determined by Fourier methods with Cuk diffractometer data, and refined by a combination of block-diagonal and full-matrix least squares toR = 0·068 for 2430 observed reflexions.The copper atoms occupy the special positions 0, 0, 0 and 0,1/2, 1/2; hence, both molecules are centrosymmetric. Both the methoxy and phenolic oxygen atoms of the phenolate ions coordinate to the metal. These, together with coordinated nitrogen atoms from the pyridine molecules, give the copper atoms a six-fold coordination.Hydrogen bonding between a water molecule and the phenolic oxygen atoms of adjacent molecules results in chains of molecules linked approximately along [011].     

Crystal and molecular structure of bis-tetraphenylarsonium-tris-(cis-1,2-dicyano-1,2-ethylenedithiolato)Fe(IV)

The crystal structure of bis-tetraphenylarsonium-tris-(cis-1,2-dicyano-1,2-ethylenedithiolato)Fe(IV), [(C₆H₅)₃As]₂Fe[S₂C₂(CN)₂]₃, has been determined using 3154 independent, non-zero reflexions collected by counter techniques. The substance crystallizes in the monoclinic system: space groupI2/a,a = 20·153(8),b = 13·411(5),c = 21·497(8) Å and = 95·28(8) °;D _m = 1·41(2),D _c = 1·43 g cm^–3 andZ = 4. The structure consists of Ph₄As⁺ cations in general positions and tris-(cis-1,2-dicyano-1,2-ethylenediothiolato)Fe(IV) anions on two-fold axes. Although the coordination around the arsenic atom is tetrahedral, the overall symmetry of the cation is 1 (C ₁), probably because the phenyl rings are rotated to accommodate the requirements of packing. The coordination of the six sulphur atoms about the iron atom is trigonal antiprismatic, approximating closely to an octahedron: for any pair oftrans sulphur atoms, the S-Fe-S angle is about 171 °.     

Diammonium μ-oxobis[trichloroferrate(III)] salts. Crystal and molecular structure of bis(benzyldimethylphenylammonium) μ-oxobis(trichloroferrate)

Several alkyl-, aralkyl-, and aryl-substituted diammonium-oxobis[trichloroferrate(III)] salts, of potential interest as model compounds for the study of certain electrophysical and biological processes, are synthesized via the corresponding tetrachloroferrate(III) salts and are characterized by IR and Raman spectroscopy. A structure analysis is performed on the representative bis(benzyldimethylphenylammonium)-oxobis(trichloroferrate). The (tetracoordinate) iron atoms in the oxo-bridged dinuclear anion of the salt each possess an ever so slightly distorted tetrahedral ligand environment; the bridge geometry [Fe-O distances 1.757(5) and 1.775(5) Å, Fe-O-Fe angle 147.7(3)°] compares well with that of other salts containing the [Cl₃Fe-O-FeCl₃]^2- anion. Crystallographic Data:a=26.392(5) Å,b=14.015(3) Å,c=9.638(2) Å,=92.65(2)°, andZ=4; space groupP2₁/n.R(F)=0.070,R _W (F)=0.078 for 4447 observed reflections.     

Crystal structure of 3-methylrhodaninecopper(I) iodide

The crystal structure of the copper(I) complex has been determined by a three-dimensional X-ray analysis. The monoclinic unit cell, space groupP2₁/c,a = 4·195(1),b = 15·581(2),c = 13·885(2) Å and = 114·9(1) °, contains four formula-units. Intensities were collected on an automatic diffractometer. The structural parameters were refined by full-matrix least-squares methods to a conventionalR value of 0·07 for 1809 non-zero observed reflexions.In this complex, the copper atom is in tetrahedral coordination with three iodine atoms and the sulphur atom of the thiocarbonyl group of the ligand. The iodine atom is coordinated with three copper atoms. The distances are 2·683(2), 2·627(2) and 2·665(2) Å. The distances between neighbouring copper atoms are 3·008(3) and 2·960(3) Å and the corresponding angles are 68·44(6) and 68·02(6) °, suggesting weak copper-copper interactions in this complex.     

Crystal and molecular structure of bis(cyclopentadienyl)tungsten tetrasulphide

The crystal and molecular structure of bis(cyclopentadienyl)tungsten tetrasulphide, (C₅H₅)₂WS₄, has been determined from three-dimensional X-ray data collected by counter techniques. The coordination about the tungsten atom, consisting of the two terminal sulfur atoms of the tetrasulphide chain and the ring centroids of the two cyclopentadienyl rings, may be described as a distorted tetrahedron. The inner S-S bond distance is found to be somewhat shorter than the outer two S-S bond distances in the tetrasulphide chain. The substance crystallizes in the monoclinic space groupP2₁/n witha = 11·242(3),b = 12·154(5),c = 8·790(2) Å and = 92·93(3) °. The structure was refined by least-squares techniques using 1581 independent reflections for whichFsk0/2 > 2(Fsk0/2), and the refinement converged at a conventionalR factor (onF) of 4·5 %.We wish to thank Dr. H. Köpf (Würzburg) for the gift of the crystals and the U.S. Atomic Energy Commission for financial support.     

Crystal structure of copper bis(tenuazonate) monohydrate

The crystal structure of copper bis(tenuazonate) monohydrate has been determined by X-ray diffraction from 968 counter-measured intensities. The thin flat crystals are monoclinic,P2₁, witha = 13.77(1),b = 15.51(1),c = 11.14(1) Å, = 109.5(2) °, and two formula units, C₂₀H₂₆CuN₂O₆·H₂O, per asymmetric unit. The structure was refined by full-matrix least squares toR = 0.056. Because of the dimerization one copper ion is four- and the other five-coordinate. The dimers are hydrogenbonded into sheets by water molecules.NIM Applied Structural Chemistry Research Group