Crystal structures of copper(II) chloride,copper(II) bromide,and copper(II) nitrate complexes with pyridine-2-carbaldehyde thiosemicarbazone

The crystal structures of chloro-(2-formylpyridinethiosemicarbazono)copper dimethyl sulfoxide solvate (I), bromo-(2-formylpyridinethiosemicarbazono)copper (II), and (2-formylpyridinethiosemicarbazono)copper(II) nitrate dimethyl sulfoxide solvate (III) are determined using X-ray diffraction. In the crystals, complexes I and II form centrosymmetric dimers in which the thiosemicarbazone sulfur atom serves as a bridge and occupies the fifth coordination site of the copper atom of the neighboring complex related to the initial complex through the center of symmetry. In both cases, the coordination polyhedron of the complexing ion is a distorted tetragonal bipyramid. Complex III in the crystal structure forms polymer chains in which the copper atom of one complex forms the coordination bond with the thicarbamide nitrogen atom of the neighboring complex. In this structure, the coordination polyhedron of the central atom is an elongated tetragonal bipyramid. It is established that complexes I–III at a concentration of 10^?5 mol/l selectively inhibit the growth of 60 to 90 percent of the cancer tumor cells of the human myeloid leukemia (HL-60).     

Crystal structures of thetrans-cyclooctene complexes of copper(I) chloride and silver nitrate

The crystal and molecular structures of the title compounds CuCl·C₈H₁₄ and AgNO₃·C₈H₁₄, have been determined by single-crystal X-ray diffraction techniques, and refined by full-matrix least squares. Both compounds crystallize in the orthorhombic space groupPbca witha=6.191(7),b=12.456(2),c=23.272(4) Å for CuCl·C₈H₁₄, anda=7.383(2),b=9.825(2),c=26.980(5) Å for AgNO₃·C₈H₁₄;Z=8 in both cases. FinalR factors are 0.047 and 0.029 respectively. The cyclooctene ring has the twist chair-chair (TCC) conformation, with approximateD ₂ symmetry, in both compounds, and the torsion angles around the double bonds are –134.2(4) and –137.0(4)° respectively. Slight lengthening of the metal-complexed double bond is attributed to enhanced olefin metal -donation of thetrans bond.     

Crystal structures of copper(II) and nickel(II) nitrate and chloride complexes with 4-bromo-2-[(2-hydroxyethylimino)-methyl]phenol

The crystal structures of {4-bromo-2-[(2-hydroxyethylimino)-methyl]phenolo}aquacopper(II) nitrate hemihydrate (I), chloro-{4-bromo-2-[(2-hydroxyethylimino)-methyl]phenolo}copper hemihydrate (II), and chloro-{4-bromo-2-[(2-hydroxyethylimino)-methyl]phenolo}aquanickel (III) are determined using X-ray diffraction. Crystals of compound I are formed by cationic complexes, nitrate ions, and solvate water molecules. In the cation, the copper atom coordinates the singly deprotonated molecule of tridentate azomethine and the water molecule. The copper complexes are joined into centrosymmetric dimers by the O _w -H···O hydrogen bonds. The crystal structure of compound II is composed of binuclear copper complexes and solvate water molecules. The copper atom coordinates the O,N,O ligand molecule and the chlorine ion, which fulfills a bridging function. The coordination polyhedron of the metal atom is a distorted tetragonal bipyramid in which the vertex is occupied by the chlorine atom of the neighboring complex in the dimer. Compound III is a centrosymmetric dimer complex. The coordination polyhedra of two nickel atoms related via the inversion center are distorted octahedra shared by the edge.     

Crystal structures of salicylideneguanylhydrazinium chloride and its copper(II) and cobalt(III) chloride complexes

The crystal structures of salicylideneguanylhydrazinium chloride hydrate hemiethanol solvate (I), salicylideneguanylhydrazinium trichloroaquacuprate(II) (II), and bis(salicylideneguanylhydrazino)cobalt(III) chloride trihydrate (III) are determined using X-ray diffraction. The structures of compounds I, II, and III are solved by direct methods and refined using the least-squares procedure in the anisotropic approximation for the non-hydrogen atoms to the final factors R = 0.0597, 0.0212, and 0.0283, respectively. In the structure of compound I, the monoprotonated molecules and chlorine ions linked by hydrogen bonds form layers aligned parallel to the (010) plane. In the structure of compound II, the salicylaldehyde guanylhydrazone cations and polymer chains consisting of trichloroaquacuprate(II) anions are joined by an extended three-dimensional network of hydrogen bonds. In the structure of compound III, the [Co(LH)₂]⁺ cations, chloride ions, and molecules of crystallization water are linked together by a similar network.     

Crystal structures of 6-[(2-hydroxy-1,1-bishydroxymethylethylamino)methylene]-2,4-dinitrocyclohexa-2,4-dienone hydrate and complexes of copper(II) chloride and copper(II) nitrate with this ligand

The crystal structures of 6-[(2-hydroxy-1,1-bishydroxymethylethylamino)methylene]-2,4-dinitrocyclohexa-2,4-dienone hydrate L · H₂O (I), chloro-(2-hydroxymethyl-2-methylpropane-1,3-diol-2-iminomethyl-4,6-dinitrophenolo)aquacopper hydrate [Cu(H₂O)(L-H)Cl] · H₂O (II), and (2-hydroxymethyl-2-methylpropane-1,3-diol-2-iminomethyl-4,6-dinitrophenolo)aquacopper nitrate [Cu(H₂O)(L-H)]NO₃ (III) are determined using X-ray diffraction. It is established that the salicylidene fragment of azomethine L in the structure of compound I is in a quinoid tautomeric form. In the crystal, molecules L and water molecules are joined together by hydrogen bonds into two-dimensional layers aligned parallel to the (010) plane. The copper atom in the structure of compound II coordinates the singly deprotonated tridentate molecule L (whose salicylidene fragment is in a benzenoid form), the chlorine ion, and the water molecule. The coordination polyhedron of the central copper atom is a distorted tetragonal pyramid. In the structure of compound III, the polymer chains are formed through the coordination bonds of the copper atom with two oxygen atoms of the amino alcohol fragment of azomethine L of the neighboring complex, which is related to the initial complex by the translation along the x axis. The coordination polyhedron of the central atom is an elongated tetragonal bipyramid. Polymers and nitro groups form a three-dimensional framework through hydrogen bonds.     

Crystal structures and magnetic properties of bipyridine copper(II) complexes

The synthesis, structure and magnetic properties of [Cu(diMe-bipy)Br₂] are reported (diMe-bipy=4,4-dimethyl 2,2-bipyridine). The complex has a polymeric structure composed of [Cu(diMebipy)Br₂] subunits linked via bridging bromine atoms. Each copper atom is hexacoordinated in a distorted octahedral coordination environment. Crystallographic data: monoclinic, space groupC2/c,Z=4, unit cell of dimensionsa=18.312(7),b=9.818(2),c=7.486(2)Å,=107.750(0)° at 293 K. The best fit of the magnetic susceptibility data by the uniform Heisenberg chain model forS=1/2 ions yields values for the exchange coupling constant of –0.46 cm^–1. The magnetic susceptibility of the dimeric [Cu(diMe-bipy)Cl₂]₂·0.5H₂O exhibits a maximum near 12 K that is indicative of an antiferromagnetic interaction between the two metal centers. The best fit of the experimental data by the Bleaney-Bowers equation was obtained withg=1.95 andJ=–6.99 cm^–1.     

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.     

Crystal structures of three methylmercury(II) complexes with thiazolidine-2-thione

The crystal structures of three CH₃Hg⁺ complexes with 1,3-thiazolidine-2-thione (HT) are reported. The cationic [(CH₃Hg)HT]NO₃ complex is monoclinic, space group P2₁/c,a=7.158(14),b=10.156(7),c=13.472(12) Å,=108.21(4)°,Z=4. The structure was refined toR=0.045. The [(CH₃Hg)HT]⁺ cation contains a CH₃Hg⁺ group bonded to the exocyclic S atom of the ligand retaining its N-H proton. This proton is lost and the CH₃Hg⁺ group remains bonded to sulfur in the neutral [(CH₃Hg)T] compound (hexagonal, P6₃,a=13.502(8),c=6.984(7) Å,Z=6,R=0.027). The [(CH₃Hg)₂T]NO₃ compound (monoclinic, C2/c,a=25.200(10),b=7.029(6),c=17.946(8),=128.99(3)°,Z=8,R=0.047) contains complex cations in which the CH3Hg⁺ groups are bonded to N and the exocyclic S atom. This series of compounds shows that the exocyclic S atom is always the first target for the CH₃Hg⁺ group, which is also found to bind to nitrogen in the 2:1 compound. No coordination is observed with the endocyclic S site, which does not even participate in intermolecular H-bonding or HgS contacts in the solids.     

Crystal structures of copper(II) compounds with racemic threonine

Crystals structures of two modifications of the copper(II) compound with racemic threonine Cu(D-Tre)(L-Tre) are determined by the electron diffraction technique. The unit cell parameters, space group, and number of formula units per unit cell for the crystals of two modifications are as follows: a = 11.10(3) Å b = 9.56(2) Å, c = 5.11(2) Å, γ = 92.6(2)°, space group P2₁/b, and Z = 2 (I); and a = 22.20(3) Å, b = 9.56(2) Å, c = 5.11(2) Å, γ = 92.6(2)°, space group C2₁/b, and Z = 4 (II). The structures are polytypic modifications of the same compound.     

Crystal structures and spectroscopic properties of copper(II) and zinc(II) complexes with the macrocycle 1,4,7-tris(2-pyridylmethyl)-1,4,7-triazacyclononane

Two novel transition-metal copper and zinc complexes [(CuL)₂]·(ClO₄) (1) and [(ZnL)]·(ClO₄)₂ (2) (L = 1,4,7-tris(2-pyridylmethyl)-1,4,7-triazacyclononane) have been synthesized and structurally determined. The two complexes are both crystallized in monoclinic space group P2(1)/c with a = 14.318(4), b = 17.214(5), c = 22.403(7) Å, = 93.096(6)°, V = 5522(3) ų, and Z = 4 for 1 and a = 9.371(2), b = 17.615(4), c = 17.579(4) Å, =104.070(4)°, V = 2814.6(11) ų, and Z = 4 for 2. The center metal ions are coordinated to six nitrogen atoms, three of which are from triazacyclononane and other three from the pendant-arms 2-pyridylmethyl, forming a slightly distorted octahedral geometry. Two complexes have been characterized by element analysis, infrared spectroscopy, and the UV–Vis and ESR spectra for 1 have also been determined.     

Crystal and molecular structures of trans-bis(acetonitrile)bis(bipyridine)ruthenium(II) perchlorate and trans-diamminebis(bipyridine)ruthenium(II) perchlorate

The structures of trans-[(MeCN)₂(bpy)₂Ru](ClO₄)₂(I) andtrans-[(NH₃)₂(bpy)₂Ru](ClO₄)₂(II) have been determined by single crystal X-ray diffraction methods. (I) forms monoclinic crystals in the space groupP2₁/c witha=8.399(2),b=10.406(2),c=15.590(3) Å,=93.78(2)° andZ=2 atT=293 K. The final refinement gaveR=0.040 for 2448 reflections withF _o ² >3(F _o ² ). (II) crystallizes in the triclinic space groupP¯1 witha=1.702(1),b=8.439(2),c=10.525(2) Å,=107.56(2),=104.63(1), =100.89(2)° andZ=1 atT=293 K. Refinement using 1878 reflections withF _o ² >3(F _o ² ) produced a finalR value of 0.036. Both of these structures have the ruthenium atom located on a crystallographic inversion center. The bipyridine ligands in both structures are in the bowed conformation as a means of circumventing the steric problems associated with the trans arrangement of the bipyridine ligands. The Ru-N(monodentate) distance is longer for the ammonia complex (2.106(3) Å) than for the acetonitrile complex (2.008(4) Å); there are no significant differences in the distances and angles of the two Ru(bpy)₂ frameworks.     

Nickel(II) and cobalt(II) nitrate and chloride networks with 2-aminopyrimidine

The coordination chemistry of 2-aminopyrimidine (PymNH₂) with nickel(II) and cobalt(II) nitrate and chloride is reported, including seven new X-ray crystal structures. Two [Ni(NO₃)₂(PymNH₂)₂(OH₂)] isomers were found (A: C2/c, a=13.3006(5), b=7.9727(3), c=28.5453(11), β=101.758(2), V=2963.48(19), Z=8 and B·1/2 acetone: P2₁/c, a=7.66060(10), b=10.6792(2), c=20.6790(3), β=100.2970(10), 1664.48(5), Z=4). In both cases one nitrate is monodentate and the other is chelating and the PymNH₂ ligands coordinate through ring nitrogen atoms. Hydrogen bonding results in double sheet structure for isomer A, and a three dimensional channeled network for isomer B. [Co(NO₃)₂(PymNH₂)₂(OH₂)] (C2/c, a=13.3507(2), b=7.99520(10), c=28.6734(3), β=102.3540(10), V=2989.77(7), Z=8) is isostructural to Ni isomer A. [CoCl₂(PymNH₂)] (Cmcm, a=3.6139(2), b=14.3170(7), c=12.9986(7), V=672.55(6), Z=4) is a sheet coordination network, consisting of corner-sharing chains of Co₂(μ-Cl)₂ bridged by PymNH₂ through ring nitrogen atoms; [CoCl₂(PymNH₂)₂] (C2/c, a=11.2774(6), b=6.5947(4), c=16.5687(9), β=92.269(3), V=1231.27(12), Z=4) is a tetrahedral molecule knit into a ribbon structures through pairs of hydrogen bonds. Isostructural trans-[NiCl₂(PymNH₂)₄] (C2/c, a=7.67760(10), b=18.7224(3), c=15.0418(2), β=99.6740(10), V=2131.41(5), Z=4) and trans-[CoCl₂(PymNH₂)₄] (C2/c, a=7.69120(10), b=18.5957(2), c=15.1091(2), β=99.5280(10), V=2131.14(5), Z=4) are simple octahedral molecules, with hydrogen-bonding producing sheet structures.     

Crystal structures of polymeric complexes of zinc(II) bromide and perchlorate with 1,4-diazoniabicyclo [2.2.2]octane-1,4-diacetate

Two zinc(II) complexes containing a flexible double betaine, namely [{Zn(L)Br₂}_n]·nH₂O (1) and [{Zn(L)₂(H₂O)₂}_n](ClO₄)_2n·4nH₂O (2) [L=1,4-diazoniabicyclo [2.2.2]octane-1,4-diacetate,⁻O₂CCH₂N⁺(CH₂CH₂)₃N⁺CH₂CO₂ ⁻], have been prepared and shown to have polymeric structures by single-crystal X-ray analysis. Complex (1) exhibits an infinite zigzag chain in which each zinc(II) atom is coordinated by two unidentate carboxylate oxygen atoms and two bromide ligands in a distorted tetrahedral geometry. Complex (2) consists of an assembly of catonic Zn(L)₂(H₂O)₂ ²⁺ moieties and discrete perchlorate anions as well as lattice water molecules. In (2) each zinc(II) atom is coordinated by two pairs of unidentate carboxylate oxygen atoms and two aqua ligands in a distorted octahedral geometry and cross-linked by skeletons of double betaine ligands to form a corrugated layer structure corresponding to the plane (100).     

Crystal structures of polymeric complexes of zinc(II) bromide and perchlorate with 1,4-diazoniabicyclo [2.2.2]octane-1,4-diacetate

Two zinc(II) complexes containing a flexible double betaine, namely [{Zn(L)Br₂}_n]·nH₂O (1) and [{Zn(L)₂(H₂O)₂}_n](ClO₄)_2n·4nH₂O (2) [L=1,4-diazoniabicyclo [2.2.2]octane-1,4-diacetate,^?O₂CCH₂N⁺(CH₂CH₂)₃N⁺CH₂CO₂ ^?], have been prepared and shown to have polymeric structures by single-crystal X-ray analysis. Complex (1) exhibits an infinite zigzag chain in which each zinc(II) atom is coordinated by two unidentate carboxylate oxygen atoms and two bromide ligands in a distorted tetrahedral geometry. Complex (2) consists of an assembly of catonic Zn(L)₂(H₂O)₂ ²⁺ moieties and discrete perchlorate anions as well as lattice water molecules. In (2) each zinc(II) atom is coordinated by two pairs of unidentate carboxylate oxygen atoms and two aqua ligands in a distorted octahedral geometry and cross-linked by skeletons of double betaine ligands to form a corrugated layer structure corresponding to the plane (100).     

Crystal and molecular structures of several tetrakis (nitrile)copper(I) complexes

The crystal structures of several [Cu(RCN)₄]X salts (R = Me, X = SO₃CF₃ ^–; R = Ph, X = BF₄ ^–, ClO₄ ^–, and PF₆ ^–) were determined using single crystal X-ray diffraction. All of the compounds contain distorted tetrahedral Cu(I) centers and noncoordinating anions, with the acetonitrile and benzonitrile structures containing three and one unique CuL₄ ⁺ complex in their respective asymmetric units. One important distortion is observed in the benzonitrile-Cu bonds, which are bent up to 23° away from linearity. The result is a flattened complex that maximizes the – tacking of the aromatic rings and is the dominant packing interactions between the complexes.     

Crystal structures of the cobalt(III), nickel(II), copper(II), and zinc(II) complexes of 2-thio-6-picoline N-oxide

Structures of the following compounds have been solved: tris(2-thio-6-picoline N-oxide)cobalt(III), [Co(6MOS)₃], orthorhombic, Pca2₁, a = 17.871(3), b = 14.061(2), c = 15.964(2) Å, V = 4011(1) ų, Z = 8, and = 1.193 mm^–1; bis (2-thio-6-picoline N-oxide)nickel(II), [Ni(6MOS)₂], orthorhombic, Pbca, a = 15.602(8), b = 13.606(4), c = 13.348(8) Å, V = 2833(4) ų, Z = 8, and = 1.655 mm^–1; bis(2-thio-6-picoline N-oxide)copper(II), [Cu(6MOS)₂], orthorhombic, Pbca, a = 13.914(5), b = 12.984(5), c = 15.663(6) Å, V = 2830(2) ų, Z = 8, and = 1.836 mm^–1; and bis(2-thio-6-picoline N-oxide)zinc(II), [Zn(6MOS)₂], triclinic, P – 1, a = 7.9737(8), b = 11.7786(9), c = 7.9206(8) Å, = 104.502(7), = 104.495(8), = 93.445(8)°, V = 691.3(1) ų, Z = 2, and = 2.106 mm^–1. The steric effect of the methyl group in the six-position of the N-oxide ring is considered in comparing these structures to complexes of 2-thiopyridine N-oxide.     

The conformation of pentaazamacrocyclics. I. Crystal structures of nickel (II) and copper (II) complexes of 1,4,7,11,14-pentaazacycloheptadecane

The crystal structures of [Ni(17-aneN₅)H₂O]Br₂·3H₂O (17-aneN₅=1,4,7,11,14-pentaazacycloheptadecane) and of [Cu(17-aneN₅)]CuBr₄ are reported. Diffraction data using MoK radiation were measured with a CAD-4 diffractometer and the structures refined by full-matrix least squares. The nickel compound has regular octahedral coordination with coordinated water completing the octahedron. The copper is approximately square-pyramidal with an apical Cu-N bond of 2.29(4) Å, compared to a mean bond length of 2.06(2) Å in the basal plane. As a result, the folding of the 17-membered macrocyclic rings is completely different in the two compounds.     

Crystal structures of 2-formyl-6-methyl- and 6-bromo-2-formylpyridine 4-phenylthiosemicarbazones

New thiosemicarbazones—2-formyl-6-methylpyridine 4-phenylthiosemicarbazone (I) and 6-bromo-2-formylpyridine 4-phenylthiosemicarbazone hydrate (II)—were synthesized and their structures were determined. Molecules I and II are nonplanar, the phenyl moiety at the terminal nitrogen atom being rotated by 19.9° and 39.5°, respectively. The water molecule is the main factor determining the crystal packing of molecules II.     

Crystal structures of four complexes produced by reaction of copper(I) cyanide with imidazoles

Four complexes of CuCN with imidazoles have been prepared by adding the ligand to a solution of CuCN in aqueous sodium thiosulfate. The imidazole ligands used were 2-methylimidazole (mim), 1,2-dimethylimidazole (dmim), 5-chloro-1-methylimidazole (clmim), and 2-phenylimidazole (phim). Complex 1, (CuCN)(mim) is monoclinic, C2/c, a = 9.565(3), b = 7.764(5), c = 8.983(8) Å, = 96.76(3)°, Z, = 4, Complex 2, (CuCN)(dmim) is monoclinic, P2₁/c, a = 8.120(2), b = 11.796(4), c = 16.375(9) Å, , = 100.87(4)°, Z = 8. Complex 3, (CuCN) (clmim) is monoclinic, C2/c, a = 24.907(4), b = 6.894(5), c = 18.259(4) Å, = 102.79(2)°, Z = 16. Complex 4, (CuCN)(phim) is orthorhombic, Pca2₁, a = 9.204(4), b = 8.125(2), c = 26.304(6) Å, Z, = 8. Complexes 1, 2, and 4 have one-dimensional chains –Cu–CN–Cu– with an imidazole bonded to each Cu. Complex 3 has a two-dimensional sheet of CuCN, again with an imidazole bonded to each Cu. In 1 the imidazole group is disordered by a two-fold rotation approximately around the N···N direction in the imidazole group. In 3 one of the imidazole groups has a disorder involving exchange of the Cl and CH₃.