Crystal and molecular structure of 1-(2-aminoethyl)biguanide-isothiocyanato-copper(II) thiocyanate

The crystal structure of 1-(2-aminoethyl)biguanide-isothiocyanato-copper(II)thiocyanate, [Cu(aebg)(NCS)] (SCN) (aebg = NH₂. CH₂. CH₂. N=C(NH₂). NH. C(NH). NH₂) has been determined and refined by Fourier methods using three-dimensional X-ray data collected on a Weissenberg automatic diffractometer. The unit cell parameters are:a = 11·41(2),b = 8·81(2),c = 7·45(2) Å; = 87·6° (2); = 67·2° (2); = 70·1° (2);Z = 2.Assuming space group P¯1, the structure was refined down toR = 8·5 %. The coordination around Cu is slightly distorted square planar and concerns three N atoms from the aebg ligand (Cu-N = 1·988(8), 2·019(7), 1·963(5) Å) and the terminal N of an isothiocyanate group (Cu-N = 1·941(5) Å). Two unsymmetrical, long interactions (Cu-N = 3·367(7) and 2·947(7) Å), with the N atoms belonging to two NCS groupstrans with respect to the coordination plane, complete the coordination to a distorted octahedron. In the aebg ligand the double bonds are localized on the C-N groups, whose nitrogen atoms coordinate to the metal.This work was carried out with the aid of financial support from the Consiglio Nazionale delle Ricerche, Roma.     

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.     

Pentacoordination in dichloro-N-2-methylthiophenyl-2′-pyridylmethyleneiminecopper(II)

Dichloro-N-2-methylthiophenyl-2-pyridylmethyleneiminecopper(II) is monoclinic:P2₁/c;a = 8·49(1),b = 10·80(1),c = 15·67(1) Å, = 92·0(3)·,Z = 4. The crystal structure has been determined at room temperature from three-dimensional X-ray photographic data and refined by differential methods with anisotropic thermal parameters to a finalR value of 8·1%. Cu(II) coordinates to two chlorine atoms (Cu-Cl = 2·255,2·443 Å) and to one sulphur (Cu-S = 2·341 Å) and to two nitrogen atoms (Cu-N = 2·011, 2·014 Å) from methylthiophenylpyridylmethyleneimine; this represents a distorted tetragonal pyramid with the organic molecule behaving as a tridentate ligand. Packing is determined by normal van der Waals contacts.     

Crystal and molecular structure of tetrakis(N,N′-diallylthiourea)nickel(II) iodide

Summary The crystal structure of tetrakis(N,N-diallylthiourea)nickel(II) iodide [Ni(C₇H₁₂N₂S)₄I₂] has been determined by a three-dimensional X-ray analysis. FinalR, after anisotropic least-squares refinement, is 8·8%. The crystals are tetragonal (P4/n):a = 11·24(1),c = 15·43(1) Å,Z = 2. Ni(II) is on a 4-fold axis; the coordination around it is flattened pyramidal and involves four sulphur atoms from four diallylthiourea molecules (Ni-S = 2·221 Å). Ni(II) is out of the plane through the sulphur atoms by 0·40 Å. Two I^- ions lie on opposite sides with respect to the nickel atom along the 4-fold axis, at distances Ni...I(1) = 3·74 Å, Ni...I(2) = 6·64 Å. The orientation of the allylthiourea molecules is determined mainly by a hydrogen bond formed by one nitrogen (N(1)) with the iodine which is nearer to the nickel.The authors are indebted to Prof. C. Furlani who kindly supplied the crystals of the compound.     

Crystal and molecular structure of di-μ-chloro(dicyandiamide)cadmium(II)

The crystal structure of di--chloro(dicyandiamide)cadmium(II) has been determined and refined by Fourier and least-squares methods toR = 0·037 using three-dimensional X-ray data collected at room-temperature on a single-crystal automated diffractometer. Crystal data are as follows:a = 10·796(7),b = 8·933(5),c = 6·847(3) Å, = 99·9(1) °,Z = 4; space groupP2₁/n. The cadmium atom is surrounded by four chlorine (Cu-Cl = 2·572, 2·607, 2·630, 2·647 Å) and two nitrogen atoms (Cd-N (nitrilic) = 2·358 Å; Cd-N (guanidic) = 2·430 Å) so that the whole polyhedron appears as a slightly distorted octahedron. The chlorine atoms form bridges between adjacent metal atoms so that the coordination octahedra are linked in chains running along [001]. These chains are joined together by dicyandiamide bridges.The authors wish to thank Dr. A. Immirzi (Politecnico di Milano) for the use of his compter programmes.     

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[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.     

Crystal and molecular structures of two polymeric organotin carboxylates,C5H12O2Sn and C5H9F3O2Sn

The crystal and molecular structures of trimethyltin(IV) acetate and trimethyltin(IV) trifluoroacetate have been determined from three-dimensional X-ray data collected by counter methods using MoK radiation. Both compounds crystallize in the orthorhombic space groupPnma withZ = 4. The acetate hasa = 10·516,b = 8·013,c = 9·706 Å and the trifluoroacetate hasa = 10·567,b = 9·237,c = 9·985 Å. ConventionalR-factors for the two compounds following least squares refinement are, for the acetate, 0·018 (for 731 reflexions) and, for the trifluoroacetate, 0·055 (for 460 reflexions) respectively. The compounds are isostructural and are polymeric with tin atoms linked by carboxylate bridges which are exactly planar. The tin atoms are in five-fold trigonal bipyramidal coordination with the methyl groups in the basal plane and oxygen atoms at the apices. Sn-O interatomic distances are, for the acetate, 2·205(3) and 2·391(4) Å, and for the trifluoroacetate, 2·18(1) and 2·46(2) Å.     

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 structure and EPR spectra of glycilglycilglycinocopper(II)bromide sesquihydrate

The title compound, Cu(glyglygly)Br·1·5H₂O, crystallizes in the space group C2/c, with a = 21.468(7), b = 6.716(5), c = 16.166(6) Å, = 98.39°, and Z = 8. The tripeptide is bonded to one Cu(II) ion through the nitrogen [Cu–N=1.97(1)Å] and oxygen [Cu–O=2.019(8)Å] atoms of the amino end glycine residue and to another Cu(II) through one oxygen atom [Cu–O=1.931(9)Å] of the terminal carboxyl group. This give rise to covalently bonded and infinite ···–Cu–tripeptide–Cu–··· chains. These chains are linked to one another by a network of H-bonds involving the water molecules and bromide ions. The Cu(II) ion is in a distorted tetragonal pyramidal coordination polyhedron. At the corner of the base of the pyramid are the terminal glycine nitrogen and oxygen atoms of one tripeptide, a carboxylic oxygen of another tripeptide and a bromide ion. The fivefold coordination is completed with a water molecule at the top of the pyramid [Cu–Ow=2.286(9)Å]. For all orientations of the applied magnetic field the single crystal EPR spectra display a single anisotropic exchange collapsed resonance without hyperfine structure. Its position was measured in three perpendicular planes and the crystal g-tensor evaluated from the data. This tensor is interpreted in terms of the contributing Cu(II) complexes in the unit cell to deduce the principal values g₁ = 2.273, g₂ = 2.050 and g₃ = 2.131 for the molecular gyromagnetic tensor. We also discuss the magnitude of the exchange interaction between neighboring copper ions in the lattice on the basis of the features in the EPR spectra and the structural information.     

Stereochemistry of racemic hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-dienenickel(II) thiocyanate,C16H32N4Ni(SCN)2 · H2O

The diamagnetictrans-diene thiocyanate salt of the macrocyclic hexamethyl-1,4,8,11-tetraazacyclotetradecadienenickel(II) complex crystallizes in the triclinic system with unit cell dimensions:a = 7·334(4),b = 8·808(6),c = 21·04(2) Å; = 63·7(0·9), = 103·8(1·4), = 110·2(1·3) °; space groupP¯1;Z = 2. The positions of all 62 atoms of the formula unit C₁₆H₃₂N₄Ni(SCN)₂.H₂O have been determined and refined by least-squares methods toR= 0·071 for 3536 X-ray diffractometric reflections. The optical activity of the two amine groups yields a racemic isomer. The only local symmetry element of the macrocyclic complex is the twofold rotation axis with the N-H bonds oriented on the same side of the approximate ligand plane. Both the C(CH₃)₂ and the imine groups are in atrans-configuration in the ring. The space group ensures that the crystal is a racemate, containing equal numbers of both enantiomers. One of the (SCN)^– groups is at a distance Ni-S 3·28 Å, the other one is 4·65 Å. No rotational disorder of the CH₃ groups has been observed. The three C-H bonds of the CH₃ groups are in approximately antiprismatic orientations with respect to the three -bonds in the case of bonding to a C(sp³) atom. The average of the C(sp³)-C(sp²) bond lengths is 1·53 Å, and the mean value for the C(sp³)-C(sp²) bonds is 1·50 Å, with 3 = 0·03 to 0·04 Å. The distances N(sp²)-C(sp³) 1·47 Å and 1·48 Å are significantly longer than the bond lengths N(sp²)=C(sp²) of 1·28 and 1·30 Å.     

An oxovanadium(IV) complex containing a pentacoordinate Schiff-base ligand: synthesis and crystal and molecular structure of N,N′-(3,3′-dipropylamine)bis (3-methoxysalicylideneiminato)oxovanadium(IV) dihydrate

Crystals ofN,N-(3,3-dipropylamine)bis(3-methoxysalicylideneiminato) oxovanadium(IV) dihydrate are monoclinic, space groupP2₁/n (No. 14) with four molecules in the unit cell of dimensionsa=8.667(4),b=20.617(4),c=12.744(3) Å,=91.48(3)°. The structure was solved by the heavy-atom method and refined by block diagonal least-squares calculations with anisotropic thermal parameters for nonhydrogen atoms.R=0.038 for 1457 reflections withI>3(I). This structure is the first reported for an oxovanadium(IV) complex involving complexation of a pentacoordinate Schiff-base ligand. The coordination polyhedron is based on a distorted octahedron. Three nitrogen and one oxygen atom from the ligand form an equatorial plane around vanadium with V-N(1) 2.096(4), V-N(2) 2.180(4), V-N(3) 2.088(4), V-O(2) 1.961(3) Å, and octahedral coordination is completed by the vanadyl oxygen [V-O(1) 1.617(3) Å] and the remaining ligand oxygen [V-O(3) 2,098(3) Å]. The relatively long V-O(1) distance correlates well with the low value ofv(V=O) of 919 cm^–1. The molecules of the complex are linked by water molecules of crystallization to form infinite hydrogen-bonded chains parallel toa.     

Crystal structure of dicyanatobis(pyridinato)-copper(II)

The crystal structure of dicyanatobis(pyridinato)copper(II), C₁₂H₅CuN₄O₂, was determined from 658 X-ray diffraction data obtained by the -2 scanning technique with MoK radiation on a SYNTEX P2₁ four-circle diffractometer. The blue crystals are tetragonal:I4₁/a,a = 15.649(3),c = 9.917(3) Å, andZ = 8. The structure was determined by the heavy-atom method and refined by full-matrix least squares toR = 7.1%. Nonhydrogen atoms were refined anisotropically, and the positional parameters of hydrogen atoms were calculated from geometrical considerations. The copper atom is planarlytrans coordinated by two nitrogen atoms from the NCO groups and two nitrogen atoms from the pyridine molecules. The oxygen atoms from two of the approximately linear NCO groups complete the Cu(II) coordination as a distorted octahedron. Through their oxygen and nitrogen atoms, the NCO groups link the metal atoms to the skeleton structure. The bond lengths are 1.15 and 1.18 Å for N-C and C-O, respectively, the N-C-O bond angle being 176.8 °. The bond lengths Cu-N in square-planar coordination are 1.95 and 2.05 Å, while the Cu-O bonds are out of plane and 2.61 Å in length.Part XVIII in the seriesCyanatocopper(II) complexes with organic ligands; Part XVII: J. Kohout, A. Malejova and J. Gazo, Chem. Zvesti, in press.     

Molecular structures of M(tfac)3 (M=Al, Co) and Cu(H2O)(fod)2: Examples of unusual supramolecular architecture

The molecular structures of Al(tfac)₃ (1), Co(tfac)₃ (2) (H-tfac = 1,1,1-trifluoroacetylacetone) and Cu(H₂O)(fod)₂ (3) (H-fod = 1,1,1,2,2,3,3-hepta-fluoro-7,7-dimethyloctane-4,6-dione) have been determined. The metal coordination spheres in compounds 1 and 2 are essentially the same as the respective M(acac)₃ derivatives. Despite the isomorphous nature of the structures of compounds 1 and 2, the identity of the nearest intermolecular van der Waals contacts are altered by minor changes in the metal coordination sphere. The geometry about copper in compound 3 is close to that of an ideal square bipyramid with the -diketonate ligands occupying the basal plane. The water ligand in each molecule of compound 3 is hydrogen bonded to an oxygen of a -diketonate ligand on an adjacent molecule resulting in the formation of dimers, which form rods along the y-axis due to weak C–F···Cu interactions. Crystal data: (1) orthorhombic, Pca2₁, a = 14.949(3), b = 19.806(4), c = 13.624(3) Å, V = 4033(1) ų, and Z = 8, and (2) orthorhombic, Pca2₁, a = 14.930(3), b = 19.620(4), c = 13.540(3) Å, V = 3966(1) ų, and Z = 8,; (3) monoclinic, P2₁/c, a = 12.447(3), b = 10.486(2) c = 21.980(4) Å, = 102.65(3)°, V = 2799(1) ų, and Z = 4.     

Metal-betaine interactions. II. Crystal structures of catena-dichloro(betaine)cadmium(II) and dimeric diaquabis(betaine)tetrachlorodicadmium(II)

Two cadmium(II) complexes of betaine (BET) have been prepared and characterized by X-ray crystallography. [Cd(BET) (–Cl)₂] (1), is a one-dimensional polymer in which each cadmium atom is coordinated by two pairs of bridging chlorine atoms [Cd-Cl=2.631(2), 2.614(2) Å] and two oxygen atoms from different bridging carboxylate groups [Cd-O=2.291(6), 2.329(6) Å] in the form of a compressed octahedron. [Cd(BET)(H₂O)Cl(–Cl)]₂ (2) is a dimer with each cadmium atom in a distorted octahedral coordination environment, being surrounded by a chelating bidentate carboxylate group [2.480(2), 2.332(3) Å], one aqua ligand [2.364(3) Å], two bridging chlorine atoms [2.659(1), 2.557(1) Å], and one terminal chlorine atom [2.480(1) Å].     

Synthesis and crystal structure of a new dysprosium(III) complex with 2-fluorobenzoato and 1,10-phenanthroline

The dysprosium complex with 2-fluorobenzoato (2-FBA) and 1,10-phenanthroline (phen) was synthesized and characterized by X-ray diffraction. The complex crystallizes in the triclinic system with space group , lattice parameters: a = 11.233(7)  Å, b = 12.598(8)  Å, c = 22.718(14)  Å, α = 81.045(13)°, β = 78.213(12)°, γ = 80.506(11)°, V = 3079(3) ų, Z= 2, Dcalc = 1.689 Mg/m³. The complex contains two independent binuclear molecules, namely, [Dy(2-FBA)₃·phen·CH₃CH₂OH]₂ (I) and [Dy(2-FBA)₃·phen]₂ (II). In molecule (I), Dy1³⁺ ion is coordinated by eight atoms, five O atoms from five 2-FBA groups, one O atom from an ethanol molecule and two N atoms from the phen ligand. The 2-FBA groups adopt monodentate and bridging two-coordination modes. In molecule (II), the Dy2³⁺ ion is coordinated by nine atoms, seven O atoms from five 2-FBA groups and two N atoms from the phen ligand. The 2-FBA groups adopt chelating, bridging and chelating-bridging three-coordination modes.Supplementary material CCDC-257186 for the compound contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK; fax: (44(0) 1223-336033; email: deposit@ccdc.cam.ac.uk.     

Crystal and molecular structure of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) aquodysprosium(III), Dy(thd)3H2O

The crystal structure of Dy(thd)₃H₂O has been solved by three-dimensional X-ray methods at room temperature. The space group isP¯1 and the cell dimensions area = 14·21(1),b = 14·88(2),c = 11·60(2) Å, = 99·76(3), = 109·91(1), = 114·08(1) °.Z = 2,D _m = l·24 andD _x = 1·238 gcm^–3, respectively. Full-matrix least-squares refinement of atomic and individual isotropic thermal parameters, using 3015 intensities obtained by counter methods, terminated with a conventionalR of 0·058. The oxygen polyhedron around dysprosium has pure seven-coordination geometry, the seventh ligand being the water molecule. The water is hydrogen bonded to two oxygen atoms of a centre of symmetry related formula unit so that two formula units are in fact held together by hydrogen bonds in a dimer.Supported by National Institute for Metallurgy, Johannesburg.     

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 the ethanol adduct of tris(oxinato)indium(III)

The ethanol adduct of tris(oxinato)indium(III), prepared in aqueous ethanol, crystallizes in the monoclinic space groupP2₁/n (Nr.14) witha=11.343(2),b=13.477(3),c=16.845(2)Å, -94.71(1)°,V=2566.4(8)ų andZ=4. The structure was solved by direct methods and refined by full-matrix least-squares methods toR=0.032 for 3374 observed reflections withI>2 (I). Three bidentate oxinato ligands (or 8-quinolinolato) coordinate to indium atom leading to an approximately octahedral coordination of the metal(III) ion. One ethanol molecule per mole of metal complex is occluded in the crystal lattice and forms a hydrogen bond with the O(3) oxygen atom of one oxinato ligand [O(3) ... O(4) =2.715(3) Å]. The two other oxinato ligands of the same unit are not involved in hydrogen bonding.     

Crystal and molecular structure of chlorotris(monomethylthiourea)silver(I)

The crystal and molecular structure of chlorotris(monomethylthiourea)silver(I) has been solved and refined by full-matrix least-squares methods to a finalR of 0·039 from 1150 reflections measured by counter techniques at ambient room temperature. The crystals are orthorhombic:Pmcn, a = 14·824(2),b = 8·524(1),c = 12·671(1) Å,Z = 4,D _m = 1·68,D _c = 1·72 gcm^–3. The structure consists of independent, distorted tetrahedral Ag(I) moieties with only weak hydrogen bonds and/or van der Waals interactions between molecules. These molecules are packed in such a way that Ag, Cl and one entire monomethylthiourea ligand all lie in a crystallographic mirror plane, and the other two ligands are related by this mirror. This arrangement, plus the alternation of the Ag-Cl bond direction, leads to a non-polar sheet of Ag, Cl and monomethylthiourea groups with other monomethylthiourea groups protruding from either side of the sheet. Only N-HCl hydrogen bonds and van der Waals interactions exist between sheets. The Ag-S distance is somewhat long at 2·649(3) Å, as is one of the Ag-S distances at 2·665(3) Å. The other two Ag-S distances are 2·520(2) Å. The geometry of the complex makes it clear that the Ag-S bond is formed by donation of an electron pair from a sulfur sp² orbital.