Electron crystallography of inorganic compounds. Direct determination of the basic copper chloride structure CuCl2·3Cu(OH)2

Experimental electron diffraction intensity data from basic copper chloride CuCl₂·3Cu(OH)₂ in its metastable form have been used for a direct structure analysis based on the evaluation of three and four phase structure invariants. The resultant electrostatic potential maps clearly show the correct atomic positions which correspond to those determined earlier by Voronova and Vainshtein (1958) from their interpretation of Patterson maps, and also to the X-ray analysis of the isostructural CuBr₂·3Cu(OH)₂ carried out by Aebi in 1948.     

Crystal and molecular structure of nitrato-1,4,10-trioxa-7,13-diazacyclopentadecanecopper(II) nitrate,C10H22N2O3·Cu(NO3)2

The copper(II) dinitrate complex of the title heteromacrocycle has been investigated by X-ray diffraction. The structure was solved by direct methods and refined by a full-matrix least-squares, givingR=0.0318 with 1778 unique reflections. The Cu(II) cation is coordinated inside the N(7), N(13)-folded macrocycle. The coordination sphere of Cu(II) is a distorted square pyramid with N(7), O(10), N(13) of the macrocycle and O(1a) of the nitrate anion atoms occupying the corners of the base of the pyramid and the O(1) macrocycle atom in the apical position. The other nitrate group was found in a remote position with respect to the Cu(II) cation.     

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 structure ofcis-diaqua bis(2,2′-bipyridyl)chromium(III) nitrate, [Cr(bipy)2(H2O)2] (NO3)3

cis-Diaquabis(2,2-bipyridyl)chromium(III) nitrate crystallizes in the mono-clinic system, space groupP2₁/c, witha=16.102(6),b=10.792(5),c=15.076(6) Å,=112.90(5)°, andZ=4. The saltlike structure was determined from X-ray crystallography and refined toR=7.5% for 3342 observed reflections. The Cr atom is octahedrally surrounded by twocis water molecules and by two chelated 2,2-bypiridyl ligands forming two nearly orthogonal planes. Selected bond distances are: Cr-O, 2.00(1) and 1.98(1) Å, Cr-N, 2.04 Å (mean).     

Crystal structure of the basic erbium tetramethyl-heptanedionate,Er8O(thd)10(OH)12

The crystal structure of the basic erbium diketonate, Er₈O(thd)₁₀(OH)₁₂, which occurs as a minor by-product in the synthesis of tris(2,2,6,6-tetramethylheptane-2, 5-dionato)erbium(III), Er(thd)₃, has been studied at room temperature by X-ray diffraction. The space group isPbcn and the crystal data area = 18·376(19),b = 31·625(35),c = 27·914(28) Å,Z = 4,D _c = 1·38 gcm^–3,D _m = 1·37 gcm^–3. Full-matrix least-squares refinement of atomic and isotropic thermal parameters, using 3103 non-zero intensities obtained by counter methods, terminated with a conventionalR of 0·116. The Er atoms were found to be chelated by one thd group each and to cluster around a central oxygen atom. An inner sphere of four erbium atoms which surround the oxygen in a distorted tetrahedral fashion are bonded to five hydroxyl groups each and are eight-coordinate. An outer sphere of four erbiums which formally complete a dodecahedron around the central oxygen are bonded to four hydroxyl groups each and are seven-coordinate. The seventh ligand atom belongs to a non-chelating thd group which is bonded through oxygen to two different erbium atoms. Each hydroxyl group is bonded to three erbium atoms, two of which belong to either the inner or the outer sphere. The coordination geometries of the erbium ions are all related to capped trigonal prisms and thet-butyl groups are directed outwards. As a consequence the material behaves as a typical non-polar substance and sublimes together with Er(thd)₃, apparently without decomposition.     

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 of copper(II)mellitate, [Cu3.5C6(COO)5(COOH)(OH)2(H2O)8.5]·4.5H2O

The crystal structure of copper(II)mellitate, Cu_3.5C₁₂H₂₉O₂₇, has been determined by X-ray analysis. The complex crystallizes in the orthorhombic space groupIba2, with unit-cell dimensionsa=19.274(3),b=21.054(7),c=12.956(4) Å. The structure was deduced by the direct method with the help of the Patterson method and refined by the block-diagonal least-squares technique to a finalR value of 0.037 for 2995 observed reflections. Among six carboxyl groups of mellitic acid, five groups lose protons and form coordinate bonds to four copper atoms, and the remaining group forms hydrogen bonds to the water of crystallization and coordinated water. The configuration around copper is distorted-pyramidal, with the Cu-O bond distances of 1.896(7) to 2.425(7) Å.     

Crystal structures of copper(II) nitrate,copper(II) chloride,and copper(II) perchlorate complexes with 2-formylpyridine semicarbazone

Compounds dinitrato(2-formylpyridinesemicarbazone)copper (I), dichloro(2-formylpyridinesemicarbazone) copper hemihydrate (II), and bis(2-formylpyridinesemicarbazone)copper(2+) perchlorate hydrate (III) are synthesized and their crystal structures are determined. In compounds I–III, the neutral 2-formylpyridine semicarbazone molecule (L) is tridentately attached to the copper atom via the N,N,O set of donor atoms. In compounds I and II, the Cu: L ratio is equal to 1: 1, whereas, in III, it is 1: 2. In complex I, the coordination sphere of the copper atom includes two nitrate ions with different structural functions in addition to the L ligand. The structure is built as a one-dimensional polymer in which the NO₃ bidentate group fulfills a bridging function. The coordination polyhedron of the copper(2+) atom can be considered a distorted tetragonal bipyramid (4 + 1 + 1). Compound II has an ionic structure in which the main element is the [CuLCl₂ · Cu(H₂O)LCl]⁺ dimer. In the dimer, the copper atoms are linked via one of the μ₂-bridging chlorine atoms. The coordination polyhedra of the central atoms of the Cu(H₂)LCl and CuLCl₂ complex fragments are tetragonal bipyramid and tetragonal pyramid, respectively. In compound III, the copper atom is octahedrally surrounded by two L ligands in the mer configuration.     

Crystal and molecular structure of diaquobis(1,1′-dimethyl-2,2′-diimidazolylsulfide)copper(II) methylsulfate, (C8H10N4S)2Cu(II)(OH2)2(CH3OS03)2

The crystal and molecular structure of the title complex has been determined. The space group isP2₁/n, witha=8.460(3),b=8.503(3),c=20.341 (8) Å,=98.41(3) andZ=2. The ligand molecules chelate the Cu^II such that the metal has a tetragonally distorted octahedral geometry; four N atoms occupy the equatorial plane and two H₂O molecules occupy the axial positions. The average Cu-N and Cu-O distances are 2.005(6) and 2.47(1) Å, respectively. The novel ligand, 1,1-dimethyl-2,2-diimidazolylsulfide was formedin situ from a methanolic solution of copper(II) sulfate pentahydrate and 1-methylimidazole-2-thiol. The measured spectral parameters (visible, EPR, and photoelectron spectroscopy) correlate well with the molecular structure.     

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 and molecular structure of tetrakisthiourea cobalt (II) nitrate monohydrate,C4H16CoN8S4 2+,2NO 3 − ,H2O

The crystal structure of tetrakisthiourea cobalt(II) nitrate monohydrate has been solved and refined by full-matrix least squares, including anisotropic temperature factors, to a finalR of 0.066. The structure is made up of discrete tetrakisthiourea Co(II) molecular ions and NO ₃ ^– ions bound together by hydrogen bonds with water molecules as well as ionic and van der Waals interactions. The local configuration of the cobalt(II) and its four bonded nearest sulfur neighbors is that of a distorted tetrahedron with an average Co-S distance of 2.30 Å. Three of the Co-S bonds appear to be made with sulfur sp² orbitals and lone pairs whereas the remaining Co-S bond involves the S-C molecular orbital as the electron donor. The thiourea groups appear to be normal. Tetrakisthiourea cobalt(II) nitrate monohydrate: orthorhombic,Pbca,a = 33.704(8),b = 11.734(2),c = 10.253(2) Å,Z = 8,D _m = 1.68(2),D _e = 1.66 g cm^–3.     

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.     

Crystal and molecular structure of di(perchlorato)(1,4,8,11-tetraazacyclotetradecane)copper (II). Cu(cyclam) (ClO4)2

The title compound, Cu(C₁₀H₂₄N₄)(ClO₄)₂, crystallizes in the triclinic system with unit cell dimensionsa= 8.744,b= 8.022,c= 8.677 Å, α = 118.7, β = 56.9, γ = 113.5 °,Z= 1, space group P¯1. The structure was solved by Fourier methods and refined by least-squares techniques using the 1545 nonzero three-dimensional counter-diffraction intensity data (CuKα) to give a conventionalR factor of 0.056. The coordination sphere of the copper ion is defined by a planar arrangement of the four nitrogen donors in the macrocyclic ligand with oxygen atoms from the perchlorate groups lying above and below this plane. The resulting tetragonally distorted octahedron of donor atoms gives interatomic distances Cu?N = 2.02(4) Å and 2.02(3) Å, and Cu?N = 2.57(4) Å.     

Crystal and molecular structure of triethanolammonium nitrate (TEAN)

The crystal and molecular structure of crystalline triethanolammonium nitrate (TEAN) was determined. TEAN is monoclinic with space groupP2₁/c and has lattice parametersa=6.592(1),b=16.358(1),c=9.3850(8)Å and=90.87(1)°. Based on four formula weights of TEAN per unit cell, the computed density is 1.393 g/cm^–3. The structure is a three-dimensional hydrogen bonded network of cations and anions. An interesting feature of the cation conformation is the presence of intramolecular trifurcated hydrogen bonding of the proton.     

Synthesis and characterization of single crystals of the layered copper hydroxide acetate Cu2(OH)3(CH3COO)·H2O

Single‐crystals of the layered copper hydroxide acetate Cu₂(OH)₃(CH₃COO)·H₂O were synthesized by heating copper acetate solution at 60 °C. The standard synthesis of the title compound based on slow titration of copper acetate solution with NaOH yielded materials with worse morphology and an additional phase present. The obtained products were characterized with powder X‐ray diffraction, high temperature powder X‐ray diffraction, scanning electron microscopy and infrared spectroscopy. The crystal structure was determined from single‐crystal X‐ray diffraction data, collected both at 120 K and at 293 K. The title compound crystallizes in the monoclinic botallackite‐type layered structure, space group P 2₁, with the lattice parameters a = 5.5776(3) Å, b = 6.0733(2) Å, c = 18.5134(8) Å, β = 91.802(4)° and a = 5.5875(4)Å, b = 6.0987(4) Å, c = 18.6801(10)Å, β = 91.934(5)° for 120 K and for 293 K, respectively. Acetate groups and water molecules are interlayered between corrugated sheets of edge‐sharing CuO6 octahedra exhibiting strong distortion resulted from the Jahn‐Teller effect. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Synthesis and crystal structure of the copper(II) complex with novel Schiff base ligand: Cu(C8H7O2N)2(OH2)

The title complex Cu(C₈H₇O₂N)₂(OH₂) crystallized in the orthorhombic space group, Pbca with unit cell parameters: a = 15.242(2), b = 11.782(4), c = 17.946(4) Å, and Z = 8. Two nitrogen atoms, two phenolic oxygen atoms of the ligand, and one water molecule are coordinated with copper to form a distorted tetragonal pyramidal polyhedron.