Coordination of Schiff bases derived from pyrrole-2-carboxaldehyde and triamines to copper(II) and nickel(II) ions. Crystal structures of [Cu(C15H20N5)]NO3 and [Ni(C15H20N5)]ClO4

The Schiffbases 1,9-bis(2-pyrrolyl)-2,5,8-triazanona-1,8-diene (H₂L¹), 1,10-bis(2-pyrrolyl)-2,5,9-triazaundeca-l,9-diene (H₂L²), and 1,11-bis(2-pyrrolyl)-6-methyl-2,6,10-triazaundeca-l,10-diene (H₂L⁴) react with copper(II) nitrate or nickel(II) perchlorate in the presence of triethylamine to give new complexes [Cu(HL^1,2,4)]NO₃ and [Ni(HL^1,2,4)]ClO₄. The crystal structures of [Cu(HL²)]NO₃ and [Ni(HL²)]CIO₄ have been determined from single crystal diffractometer data and refined to finalR factors of 5.09 and 5.3%, respectively. Crystallographic data: [Cu(HL²)]NO₃: monoclinic,P2₁/c,a=10.036(2),b=14.500(2),c=13.317(2) Å,=108.14(1)°,Z=4, andd _c =11.427 Mg m^–3; [Ni(HL²)]ClO₄: monoclinic,P2₁/n,a=10.578(3),b=13.953(3),c=12.394(4) Å,=93.78(2)°,Z=4, andd _c =1.549 Mg m^–3. In both the structures the potentially pentadentate ligand (HL²)^– acts as a tetradentate one leaving one pyrrole group uncoordinated. Interesting is the metal dependent sequence of the three chelate rings. While the Ni (II) ion coordinates the (HL²)^– ligand to form a 5-5-6-membered ring system, the ring arrangement in the copper complex is of the 5-6-5 type.     

Structure of trans-aqua-bis(pyridine)dibenzoatocopper(II)

Crystals oftrans-aqua-bis(pyridine)dibenzoatocopper(II), Cu(NC₅H₅)₂(C₇H₅O₂)₂(H₂O), are monoclinic,P2₁/n, witha=5.9847(10),b=18.874(5),c=19.728(10)A,=92.97(4)°,Z=4, andV=2225.5(13)A³. The full-matrix least-squares refinement used 3030 reflections withI> 2.5(I) and converged toR=0.067. The benzoate ions bond as monodentate ligands in this five-coordinate complex. The copper ion is in a square pyrimidal environment with trans pyridine groups and benzoate ions in a slightly distorted square planar arrangement and a water ligand in the axial position. The Cu-O distance to the water molecule is significantly longer (2.273(4) Å) than the distances to the O atoms of the carboxyl groups (1.934(3) and 1.930(4)Å).     

Structure of (1,2-diaminoethane) (1-[[2-[(2-aminoethyl)imino]propyl]thio]-2-propanone)nickel(II) nitrate

A single crystal X-ray investigation of the purple nickel (II) complex Ni[L(en)](NO₃)2, produced by condensation of 1,2-diaminoethane (en) with the thiodiketone S(CH₂COCH₃)2 in the presence of nickel (II) nitrate (L is NH₂(CH₂)₂N=C(CH₃)CH₂SCH₂COCH₃), shows that the metal ions are six coordinate. The new ligand L is tetradentate, with the N,N and S donor atoms arranged meridionally, and the coordination shell completed by the carbonyl oxygen atom of L and the nitrogen atoms of 1,2-diaminoethane. Metal-ligand bond distances are Ni-N: 2.08 av. (en), 2.10 and 2.05 (NH₂ and N=C respectively of L); Ni-O, 2.16; Ni-S, 2.45 Å. There is considerable angular distortion from regular octahedral values of the bond angles at nickel. The crystals are monoclinic,P2₁/c (No. 14),a=12.433(2),b=11.709(1),c=13.150(2) Å,=103.93(1)°,V _c=1858.2(4) ų. The structure was solved by the heavy-atom method and refined by full-matrix least squares to anR value of 0.055 for 3633 reflections.     

Crystal structures of difluoro[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]boron(III), [BF2(C16H13O3)], and bis[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]copper(II), [Cu(C16H13O3)2]

The crystal structures of difluoro[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]boron(III), [BF₂(C₁₆H₁₃O₃)], and bis[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]copper(II), [Cu(C₁₆H₁₃O₃)₂], have been determined by single-crystal X-ray diffraction methods. The structures were solved by direct methods and electron density calculations and were refined by the full-matrix least-squares method. Difluoro[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]-boron(III) crystallizes as yellow rhombs in the monoclinic space groupP2₁/c witha=11.429(3),b=11.364(4),c=11.412(4) Å,=92.19(2)°,V=1481.0(8) ų andZ=4. A total of 2754 unique reflections were collected. Of these 1342 were considered observed [I>3(I)] leading to a finalR-value of 0.045. Boron is tetrahedrally coordinated to the two fluorine atoms and to two oxygen atoms of the bidentate 2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato ligand, C₁₆H₁₃O ₃ ^– . Average bond distances: C-C (aromatic) 1.378(10) Å, B-O 1.473(7) Å and B-F 1.343(4) Å. bis[2-(4-Methoxyphenyl)-3-oxo-3-phenylpropanalato]copper(II) crystallizes as dark yellow-green plates in the monoclinic space groupC2/c witha=23.410(7),b=13.856(3),c=8.039(3) Å,=101.79(2)°,V=2553(1) ų andZ=4. Of the unique set of 3076 scanned reflections 2401 hadI>3(I) for whichR became 0.040. Copper is coordinated to four oxygen atoms, two from each of the two bidentate 2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato ligands, in a distorted square planar manner. The molecule hasC ₂ symmetry. Average bond distances: C-C (aromatic) 1.383(6) Å and Cu-O 1.896(8) Å. The crystals of both compounds consist of monomeric molecular complexes held together by van der Waals forces.     

Synthesis and Structure of a Copper Complex of a Macrocyclic Ligand with Dissimilar HN+N(Amino)O2 and N2(Imino)O2 Inners

Abstract The copper complex [Cu(C₂₃H₂₇Br₂N₄O₂)(H₂O)(NO₃)]₂ was synthesized and characterized by X-ray diffraction. The complex crystallizes in the triclinic system with space group P-1, lattice parameters: a = 13.2293(18) (?), b = 14.184(20) (?), c = 16.522(23) (?), α = 91.923(2)°, β = 111.777(2)°, γ = 111.259(2)°, V = 2632.0(6) ?³, Z = 4, D _c = 0.88 Mg m⁻³. In the title compound [Cu(C₂₃H₂₇Br₂N₄O₂)(H₂O)(NO₃)]₂, the coordination polyhedron of the Cu atom is a square-planar environment. The structure consists of mononuclear units in which the copper(II) ions are linked in the plane by N, N′ iminato and O, O′ phenoxo atoms. In addition the crystal lattice contains one water molecule per unit. Graphical Abstract Dissymmetric ligand was efficiently synthesized and used to prepfsare a copper(II) complex which was characterized by X-ray diffraction      

Crystal and molecular structure of tetrapyridyl-copper(II)-bis-nitrato-bis-pyridine

The crystal and molecular structure of a pyridine complex of anhydrous copper(II)nitrate is described. The structure has been solved by vector search methods and refined by least-squares methods to R₁=0.049 [I>2(I)]. The complex lies on a twofold axis parallel toa, and two solvent pyridine molecules lie on twofold axes parallel toc. The copper atom is coordinated by four pyridyl groups and two monodentate NO₃ groups. Crystal data: C₃₀H₃₀N₈O₆Cu, orthorhombic, space group Pnna(52),a=14.446(7),b=12.154(5),c=16.881(4) Å,V=2964(2) ų,Z=4.     

Crystal structure of dinitratotris(pyridine)nickel(II), Ni(NC5H5)3(NO3)2

Ni(NC₅H₅)₃(NO₃)₂ crystallizes in the triclinic space group P¯1 witha=8.432(2),b=9.993(2),c=12.181(3)Å, =69.78(2),=83.16(2), =67.73(1), andD _c =1.57 g cm^–3 forZ=2. The Ni²⁺ ion is six-coordinate with one bidentate and one monodentate nitrato ligand.     

Self-assembly in transition metal complexes: structural characterization of a copper histamine nitrate [Cu(II)(him)2(NO3)2]

A new monomeric copper (II) complex with histamine (him), [Cu(II)(him)₂(No₃)₂], has been prepared by the reaction of Cu(NO₃)₂ with histaminium dichloride and its structure was determined by x-ray crystallography. The complex crystallizes in the triclinic system, space group with a = 5.7238(4), b = 8.7094(7), c = 9.2481(11) Å, = 69.693(8), = 73.242(7), = 71.050(7)°, V = 400.84(6) ų, and Z = 1. The structure consists of discrete [Cu(II)(him)₂(NO₃)₂] molecules in which the metal atom is centrosymmetrically coordinated by two histamine ligands forming an equatorial plane with Cu–N(imidazole ring) being 2.032(2) and Cu–N(NH₂ group) being 2.023(2) Å. Two O atoms from nitrate anions coordinate on the elongated axial positions with Cu–O being 2.549(2) Å. In the crystal structure, the molecules are organized by hydrogen bonds forming a two-dimensional network.     

Crystal structure and spectroscopic study oftrans-diaquabis(2-benzoylpyridine)copper(II) nitrate

trans-Diaquabis(2-benzoylpyridine)copper(II) nitrate has been prepared and characterized by spectroscopic methods and X-ray crystallography. The complex exhibits strong infrared carbonyl absorption at 1655 cm^–1 and a broad d-d band centered about 14,090 cm^–1. The crystals are monoclinic, space groupP2₁/c witha=7.872(1),b=14.573(3),c=11.132(1) Å,=102.79(1)°,Z=2, andR _F =0.049 for 2440 observedMo-K reflections. The crystal structure consists of a packing of centrosymmetric [Cu(2-benzoylpyridine)₂(H₂O)₂]²⁺ cations and nitrate ions, which are interlinked by hydrogen bonds to form thick layers corresponding to the (100) family of planes. The coordination geometry about the copper atom is an elongated octahedron with aqua ligands occupying the axial positions. The measured bond distances are: Cu-O(aqua)=2.256(3), Cu-O(L)=2.068(2), and Cu-N=1.965(2) Å.Mr. Wang is on leave from Central Laboratory, Nankai University, Tianjin, China.     

Synthesis, Crystal Structures and Properties of Two Copper (II) Complexes with Pyridazine Derivative Ligand

Abstract  Two new complexes, [Cu(L)₂(CH₃OH)] · (ClO₄)₂ (1) and [Cu(L)₂(H₂O)] · (NO₃)₂ (2), have been synthesized and their crystal structures have been determined by X-ray analysis, where L = 3-(3,5-bimethylpyrazole-yl)-6-chloro-pyridazine]. The complex 1 crystallizes in the monoclinic, space group C2/c, and the coordination configuration of copper (II) is better described as trigonal pyramidal geometry with four N atoms from L and one O_methanol^. The coordination configuration of 2 is quite similar to that of 1 except O_water instead of O_methanol^. The intermolecular hydrogen bonds link the repeat units and extend the molecules to multinuclear structures in both compounds. The spectral properties of the title compounds have been studied and discussed. Furthermore, the antibacterial activities of the title compounds have been detected, the results indicate that the ligands and two copper(II) complexes exhibit certain fungicidal activities again several bacteria. Index Abstract  Two new complexes, [Cu(L)2(CH3OH)]·(ClO4)2 (1) and [Cu(L)2(H2O)]·(NO3)2 (2), have been synthesized and their crystal structures have been determined by X-ray analysis, where L= 3-(3,5-bimethylpyrazole-yl)-6-chloro-pyridazine. The intermolecular hydrogen bonds extend the molecules to multinuclear structures in both compounds.      

Di-2-pyridylketone semicarbazone as ligand in metal complexes: synthesis and X-ray crystal structure

A series of complexes of di-2-pyridylketone semicarbazone (Hdips) and Mn(II), Co(II), Co(III), Ni(II) and Cu(II) nitrates were synthesized and characterized by means of IR spectroscopy and for cobalt and nickel by X-ray crystal structures. The results are in agreement with the formulae: Mn(Hdips)₂(NO₃)₂·2H₂O, [Co(Hdips)₂](NO₃)₂·H₂O (I), [Ni(Hdips)₂](NO₃)₂·H₂O (II), Cu(Hdips)(NO₃)₂·2H₂O, [Co(dips)₂](NO₃)·2H₂O (III). The structure of I and II are monoclinic, space groupP2₁/c, with, I,a=15.980(4),b=11.531(2),c=16.170(2)Å;=104.20(2)°,Z=4,R=0.032; II,a=16.109(5),b=11.480(3),c=16.135(6)Å;=104.15(2)°,Z=4,R=0.069. Compound III is also monoclinic, space groupP2₁/c witha=12.173(5),b=15.619(5),c=15.338(8)Å;=111.40(4)°,Z=4,R=0.059. In these complexes the ligand is tridentate via carbonylic oxygen, semicarbazone and pyridine nitrogens forming each two five membered chelate rings with the metal in a distorted octahedral geometry.     

Crystal structure of mixed-ligand copper(II) complexes. Bis(2,2′-bipyridyl)monophenylphos-phatocopper(II)monophenylphosphate monohydrate, [Cu(C10H8N2)2(C6H5OPO3)]-(C6H5OPO3H2)(H2O)

The title mixed-ligand copper(II) complex has been synthesized and its crystal structure at room temperature solved. The crystals are monoclinic:P2₁/c,a=12.004(3),b=19.402(5),c=14.192(4) Å,=108.80(3)°,Z=4. The structure was solved by direct methods, and refined to anR value of 0.041 for 4457 nonzero independent reflections. The crystal structure consists of discrete [Cu(bipy) (MPhP)] units, noncoordinated MPhPH₂, and H₂O molecules. Each [Cu(bipy)₂(MPhP)] unit involves a five coordinate CuN₄O chromophore with a distorted trigonal-bipyramidal stereochemistry. The phosphate groups are linked together by short hydrogen bonds of (P)-O-H--O-P type.     

A Novel Coordination Structure of Dichromates Bonding to Copper (II): [Cu(bipy)2(Cr2O7)] · 2 H2O

Dark-green multimetal compound crystal [Cu(bipy)₂(Cr₂O₇)]· 2 H₂O was obtained from aqueous solution of Cu(NO₃)₂, K₂Cr₂O₇ and bipyridine. The crystal structure was determined by X-ray crystallography: triclinic P1 , a = 7.716(3) Å, b = 9.656(3) Å, c = 15.517(5)Å, α = 77.41(3)°, β = 81.04(3)°, γ = 82.33(3)°, Z = 2. In this compound, two chromium atoms and a copper atom are linked by two oxo bridges (Cu(II) O Cr(VI) O Cr(VI)). The copper coordination polyhedron corresponds to a five-coordinated distorted trigonal bipyramid.     

Characterization of metal complexes of 2,6-diacetylpyridinebis(imines). Preparation and crystal structure of tetrafluoroborato-2,2′-bipyridyl{2,6-bis[1-(p-ethylphenylimino)ethyl]pyridine}-copper(II) tetrafluoroborate

X-ray analysis has established the semicoordination bonding mode for one tetrafluoroborate anion in tetrafluoroborato-2,2-bipyridyl{2,6-bis[1-(p-ethylphenylimino)ethyl]pyridine}copper(II) tetrafluoroborate, [Cu(bipy) (C₂₅H₂₇N₃)(FBF₃)]BF₄. Crystals of the title compound are monoclinic, space group P2₁/n with four molecules in the unit cell ofa=14.991(3),b=14.989(3),c=16.933(4) Å,=109.33(2)°. The structure was solved by the heavy-atom method and refined by blocked full-matrix least squares calculations with anisotropic thermal parameters for nonhydrogen atoms toR=0.049 andR _w=0.051 for 3311 reflections withI>3(I). The copper atom coordination is pseudo-octahedral, with one nitrogen atom of the bipyridyl ligand [Cu-N(2)1.985(4) Å] and three nitrogen atoms of the terdentate NNN donor ligand [Cu-N(3) 1.923(4), Cu-N(4) 2.073(4), Cu-N(5) 2.073(4) Å] forming the equatorial plane. The axial sites are occupied by the second nitrogen atom of the bipyridyl ligand [Cu-N(1) 2.186(5) Å] and a loosely bound fluorine atom [Cu-F(21) 2.692(5) Å] of the semicoordinated tetrafluoroborate group. The other BF ₄ ^– anion is ionic. Electronic and vibrational spectral data for the complex are discussed in terms of the geometry of the cation.     

Synthesis and crystal structures of nitratocobaltates Na2[Co(NO3)4], K2[Co(NO3)4], and Ag[Co(NO3)3] and potassium nitratonickelate K2[Ni(NO3)4]

The cobalt(II) and nickel(II) nitrate complexes with an island structure (Na₂[Co(NO₃)₄] (I) and K₂[Co(NO₃)₄] (II)] and a chain structure [Ag[Co(NO₃)₃] (III) and K₂[Ni(NO₃)₄] (IV)] are synthesized and investigated using X-ray diffraction. In the anionic complex [Co(NO₃)₄]^2? of the crystal structure of compound I, the Co coordination polyhedron is a twisted tetragonal prism formed by the O atoms of four asymmetric bidentate nitrate groups. In the anion [Co(NO₃)₄]^2? of the crystal structure of compound II, one of the four NO₃ groups is monodentate and the other NO₃ groups are bidentate (the coordination number of the cobalt atom is equal to seven, and the cobalt coordination polyhedron is a monocapped trigonal prism). The crystal structures of compounds III and IV contain infinite chains of the compositions [Co(NO₃)₂(NO₃)_2/2]^? and [Ni(NO₃)₃(NO₃)_2/2]^2?, respectively. In the crystal structure of compound III, seven oxygen atoms of one monodentate and three bidentate nitrate groups form a dodecahedron with an unoccupied vertex of the A type around the Co atom. In the crystal structure of compound IV, the octahedral polyhedron of the Ni atom is formed by five nitrate groups, one of which is terminal bidentate. The data on the structure of Co(II) coordination polyhedra in the known nitratocobaltates are generalized.     

Synthesis and structure of bis(2,6-dimethylpyrazine)(THF)copper(II) nitrate

Attempts to crystallize Cu(2,6-dmpz)(NO₃)₂ (2,6-dmpz = 2,6-dimethylpyrazine) by reaction of 2,6-dmpz with Cu(NO₃)₂·3H₂O in THF resulted in the synthesis of Cu(2,6-dmpz)₂(NO₃)₂·THF. The compound crystallized in the monoclinic space group C2/c and exists as isolated molecules with distorted square pyramidal geometry: a = 11.609(4) Å, b = 10.415(3) Å, c = 18.256(6) Å, = 108.332(4)°. The 2,6-dmpz molecules coordinate to the Cu ions through the distal (remote from the methyl) nitrogens. The molecules are arrayed in stacks parallel to the b-axis.     

Synthesis and characterization of taurine Schiff base derivatives and their Cu(II) complexes: Crystal and molecular structure of 5-NO2 salicylaldimine ethylene sulfonic acid complex of Cu(II)

Spectroscopic analysis of eight copper(II) complexes of Schiff bases derived from taurine and eight different salicylaldehydes and naphthaldehydes are reported. X-ray structural analysis of the copper(II) complex of the 5-NO₂-sali-cylaldehyde imine of taurine (5-NO₂-salicylaldimine ethylene sulfonic acid) as the tetran-butylammonium salt [Cu(C₉H₈N₂O₆S)₂]^2–2[(C₄H₉)₄N]⁺ (CUTAU-TBA) has been carried out. The space group isP¯1, witha=8.761(4),b=10.410(3),c=16.528(4) Å,=77.85(3),=86.53(4), =79.15(3)°, andZ=1. The structure was solved by the heavy-atom method and refined by least-squares techniques to anR factor of 0.068 for 2807 observed reflections. The CUTAU cation is centrosymmetric, with the Cu atom sitting on a crystal-lographic centre of symmetry. The copper atom has a square-planar environment, coordinated by the potentially tridentate Schiff base only through the imino nitrogen and the phenolate oxygen with the deprotonated sulfonic group directed away from the coordination sphere of the Cu(II).     

Synthesis and Crystal Structures of Copper(II) Complexes Derived from 5-Methoxy-2-[(2-morpholin-4-ylethylimino)methyl]phenolate and (2-Morpholin-4-ylethyl)-(1-pyridin-2-ylethylidene)amine

Abstract  

A pair of copper(II) complexes, [CuL¹(ONO₂)(OH₂)] 1 and [CuBrL²N₃] 2, where L¹ is 5-methoxy-2-[(2-morpholin-4-ylethylimino)methyl]phenolate, and L² is (2-morpholin-4-ylethyl)-(1-pyridin-2-ylethylidene)amine, have been synthesized and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic space group P2₁/c, with a = 10.496(2), b = 19.113(3), c = 8.586(2) ?, β = 105.186(10)°. Complex 2 crystallizes in the monoclinic space group C2/c, with a = 16.606(3), b = 7.357(2), c = 26.043(5) ?, β = 94.996(2)°. The Cu atom in each complex is five-coordinate in a square pyramidal geometry.     

Structure of dichloroethanolaminecopper(II) and dibromoethanolaminecopper(II)

CuCl₂(NH₂CH₂CH₂OH) is monoclinic, space group C2/c, witha+11.092(2),b+10.012(2),c+6.401(1) Å, =121.71(1)°, andV=604.8(2)ų withZ+4. The structure was refined to a final value ofR+0.27 for 518 unique observed reflections with |F|>3. The ethanolamine and halide ions coordinate to the copper(II) ion forming a pseudoplanar four-coordinate monomeric CuCl₂L² complex (L²+bidentate ligand). The copper ion also interacts with the halides of neighboring complexes through the formation of semi-coordinate Cu-Cl linkages (2.926(1) Å) between oligomers. The copper thus attains a 4+2 elongated octahedral coordination geometry. In this space group, the ligand is statisticallydisordered The Cu-Cl distance is 2.267(1)Å while the Cu-N/O distances are 2.025(2)Å. The dibromide structure is isomorphous with the dichloride structure, with space group C2/c, anda+11.285(2),b+10.218(2),c+6.715(1) Å, =121.65(1)°, andV=659.2(2)ų.     

Crystal and molecular structures of trichloro (π-cis-but-2-en- 1,4-diammonium) platinum(II) chloride and trichloro(π-cis-pent-2-enylammonium) platinum(II)

The structures of the olefinic complexes of platinum(II) withcis-but-2-en-1,4-diammonium, [PtCl₃(C₄H₁₂N₂)]⁺, and withcis-pent-2-enylammonium, [PtCl₃(C₅H₁₂N)], the first one as its chloride, have been determined by single-crystal X-ray methods. The compounds form yellow monoclinic crystals, witha=11.238(3),b=12.234(4),c=7.769(1) Å, = 112.99(2) ° anda= 11.530(3),b=9.037(3),c= 10.067(3) Å, =105.50(2) °, respectively; both crystallize in the space groupP2₁/c withZ=4. The structures, solved by standard methods, have been refined anisotropically by full-matrix least-squares methods, both toR=0.040, on, respectively, 1808 and 1849 independent reflections collected by counter methods.In both complexes, platinum is four-coordinate to the three chlorine atoms and the double bond of the olefinic ligand. The structures are discussed, and comparison with the analogous platinum(II)-olefin complexes with the trans isomers of the olefinic ligands is made.