Crystal structure of [Cu2(II)(dmpa)2(p-Cl-C6H5COO)2] (Hdmpa = N,N-dimethyl-3-amino-1-propanol)

The copper complex, [Cu₂(II)(dmpa)₂(p-Cl-C₆H₅COO)₂], has been prepared and its structure determined using X-ray crystallography. The dimer is a di-₂-alkoxo complex which is a five-coordinate copper dimer with unsupported alkoxo bridges. The complex crystallizes in the triclinic space group P-1 with a = 11.384(2), b = 14.636(5), c = 9.609(2) Å, = 100.07(2), = 104.33(3), = 72.79(2)°, V = 1471.8(7) ų, and Z = 2. The structure is comprised of discrete binuclear clusters in which the metal atoms are bridged by two alkoxo oxygens of the dmpa^– ligands. The Cu-O and Cu-N distances are in good agreement with those found for other copper(II) aminoalcoholato complexes. The Cu···Cu distance is 2.9765(6) Å. In the crystal, every two dimeric coordination molecules are combined together by the recognition through intermolecular hydrogen-bonding interactions between the apical water molecule and the non-coordinated O atom from the p-chlorobenzoato ligand, forminga tetramer.     

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)     

The Crystal Structure of [La(NO3)6{Cu(2,2′-bipy)2}2][La(NO3)6Cu(2,2′-bipy)2]CH3CN with the Most Profuse Modes of Nitrate Coordination

The title compound [La(NO₃)₆{Cu(2,2′-bipy)₂}₂][La(NO₃)₆Cu(2,2′-bipy)₂] CH₃CN was synthesized, the crystal and molecular structures were determined at room temperature. The complex formed monoclinic crystals, space group P21/n (No.14), a = 10.354 (3) A, b = 23.440 (9) A, c = 32.817 (9) A, b = 90.39 (2)°, Z = 4. The crystal structure consisted of a discrete [La(NO₃)₆{Cu(2,2′-bipy)₂}₂]⁺ cation and [La(NO₃)₆Cu(2,2′-bipy)₂]^- anion and a non-coordinated CH₃CN molecule. Each La(III) ion was 12-coordinate with twelve oxygen atoms from six chelating nitrate ligands. There were four modes of nitrate coordination and the coordination geometry of all three copper ions was different in the crystal structure.     

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 Study of the Complex [Cu2 (μ–C2O4) (C10H8N2)2(H2O)2] (C6H4COSO2N)2 Crystal Structure Containing Cu (II) Bipy Oxalato and Saccharin

The title compound has been synthesized and its crystal structure determined at room temperature. MW = 927.86, monoclinic, space group P2₁/c, Z = 2, a = 9.283(1) Å, b = 16.239(2) Å, c = 12.209(1) Å, β = 99.848(9)°. The crystal structure consists of repeated [Cu₂(μ–C₂O₄)(C₁₀H₈N₂)₂ · (H₂O)₂]₂ cations and non-coordinated saccharin anions. Each copper ion is in a square pyrimidal environment with two oxalate oxygen and two bipyridine nitrogen atoms as a base and one water molecule at the apex. The two copper ions are bridged by oxalato and the distance is 5.138 Å.     

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.     

Synthesis and crystal structure of a terephthalato-bridged copper(II) complex [Cu2(tpt)(bpy)2(H2O)4] [Cu2(tpt)3 (bpy)2(H2O)2]

A terephthalato-bridged copper(II) complex [Cu₂(tpt)(bpy)₂(H₂O)₄][Cu₂(tpt)₃(bpy)₂ (H₂O)₂] (1) (tpt = terephthalate, bpy =; 2,2'-bipyridine) was synthesized by the reaction of Cu(ClO₄)₂ 6H₂O and terephthalic acid in the presence of 2,2'-bipyridine in H₂O solution. Crystal structure of 1 was determined by X-ray diffraction analysis in the triclinic space group P , with a = 10.7327(10) Å, b = 11.1658(11) Å, c = 17.3768(16) Å, = 108.063(2), = 91.064(2), = 116.721(2), V = 1737.5(3) ų, and Z = 2. Both the anion and the countercation in 1 are copper(II) complexes linked by terephthalate bridges in the bis(monodentate) (syn–anti) mode. The anion and the countercation are also linked by two hydrogen bonds between coordinating water molecules and terephthalate ligand.     

Crystal structure of the orthorhombic basic copper nitrate,Cu2(OH)3NO3

The crystal structure of the orthorhombic copper salt Cu₂(OH)₃NO₃ (natural gerhardtite) has been determined from X-ray diffractometer data by means of three-dimensional Patterson and Fourier syntheses, and refined by difference Fourier syntheses and least-squares methods to a finalR index of 0.097 for 532 reflections. Crystals of Cu₂(OH)₃NO₃ are orthorhombic:a=6.087(2),b=13.813(4),c=5.597(2) Å,Z=4, space groupP2₁2₁2₁. The Cu atoms form deformed hexagonal pseudocells (010). Each Cu(1) ion is surrounded by an approximately square planar arrangement of four OH ions at 1.929, 1.952, 1.993 and 1.998 Å and by two O (of NO₃ ions) at 2.359 and 2.480 Å, completing a deformed coordination octahedron; each Cu(2) ion is similarly coordinated by four OH at 1.989, 1.997, 2.009 and 2.018 Å, one OH at 2.309 Å, and one O at 2.384 Å. The structure involves layers of such deformed octahedra, of theC6-type, linked together by hydrogen bonds through the NO₃ ions. Similarities to and differences from the structure of the monoclinic polymorphous form are discussed.     

Polymeric copper(II)-orotato complexes, [(C5H2N2O4)Cu(H2O)2]n

The compound [(C₅H₂N₂O₄)Cu(H₂O)₂]_n has been synthesized and its structure determined at room temperature. The primary coordination sphere at the Cu ion is square planar with the orotate dianion coordinating at the metal through heterocyclic nitrogen atom and adjacent oxygen of the carboxylate group, the remaining coordination sites are occupied by two water molecules. The orotate dianion is tricoordinated to one copper via N₁ and one oxygen of the carboxylato group and to another copper atom via the other oxygen of the carboxylato group. The coordination at copper is extended to five by the other oxygen of the carboxylate group of another orotate molecule. Thus, the molecules are associated to form chains, the carboxylato group acting as a bridge between the metal ions, the orotato-group being tridentate. The title compound crystallizes in the monoclinic space group. P2₁/n₁ with a = 9.515(5), b = 6.925(2), c = 11.861(6) Å, = 95.285(9)°, D _calc = 2.17 g cm^–3, and z = 4.     

Microwave Synthesis and Crystal Structure of 2-Hydroxy-3-iodo-benzaldehyde-copper (II)

Abstract  

One new complex, 2-hydroxy-3-iodo-benzaldehyde-copper (II) has been designed and microwave synthesized. The structure was determined by UV, IR and single X-ray crystallography study. The title complex C₁₄H₈CuI₂O₄ crystallizes in the orthorhombic space group Pna2₁ with the cell parameters a = 12.7897(12) ?, b = 6.1132(8) ?, c = 19.5114(18) ?, V = 1525.5(3) ?³ and Z = 4. The central copper (II) is four-coordinated by four oxygen atoms from two 3-iodosalicylaldehyde. The complex is linked into rhombic crystals by weak intermolecular interactions.     

Metal complexes of chiral pyridine ligands. X-ray structure of nitratobis {2-(2S)-2-pyrrolidinyl]pyridine} copper (II) nitrate

Cobalt(II), nickel(II), and copper(II) complexes of 2-[(2S)-2-pyrrolidinyllpyridine (L) have been synthesized and characterized. The crystal structure of the complex [Cu(L)₂(NO₃)]NO₃ has been determined by X-ray diffraction. Crystals are monoclinic, space groupP2+, witha=10.766(3).b=7.525(2),c=13.447(4) Å. =104.64(2)°. and Z=2. The structure consists of [Cu(L)₂(NO₃)]⁺ cations and NO ₃ ^t- anions. The copper atom has a distorted trigonal bipyramidal coordination geometry with the two pyrrolidine nitrogens and one nitrate oxygen occupying the equatorial positions and the two pyridine nitrogens at the apices. The crystalline cohesion is ensured by a network of hydrogen bonds involving the pyrrolidine groups as donors and both coordinate and uncoordinate nitrates as acceptors.     

Crystal structure investigation of [Mn(3-CH3C5H4N)2(N3)2(H2O)2]

The crystal structure of the title compound has been determined by single crystal X-ray diffraction methods. [Mn(3-CH₃C₅H₄N)₂(N₃)₂(H₂O)₂] crystallizes in the space group P 1 with a = 7.444(2) Å, b = 7.691(2) Å, c = 8.926(3) Å, α = 99.82(3)°, β = 108.80(2)°, γ = 114.99(2)° and Z = 1. Least squares refinement gave a R value of R_w = 0.046 for 1414 observed reflections. The manganese atom in the title complex is octahedrally coordinated by two oxygen atoms of the water molecules and four nitrogen atoms; two N-atoms are the end atoms of azide groups and the other two nitrogen atoms belong to the 3-methylpyridine molecules. The polyhedra are linked via hydrogen bonds between the water molecules and the azide groups.     

A Unique Example of a Co-crystal of [Co(AMTTO)2(H2O)2](NO3)2 and [Co(AMTTO)2(CH3CN)2](NO3)2 (AMTTO = 4-amino-5-methyl-1,2,4-triazol-3(2H)-thione)

A co-crystal of cobalt(II) complexes, Co(AMTTO)₂(CH₃CN)₂]²⁺(NO₃)₂. [Co(AMTTO)₂(H₂O)₂]²⁺(NO₃)₂, compound (1) was isolated from the reaction of Co(NO₃)₂?6H₂O and 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine (AMTTO) in acetonitrile as solvent. Isolated crystals were characterized by elemental analyses, IR spectroscopy as well as X-ray diffraction studies. Crystal data for 1 at 95 K revealed a monoclinic space group P2₁/n, a?=?11.7903(5), b?=?12.1279(5), c?=?14.1443(6) Å, β?=?99.244(4)°, Z?=?2, R₁?=?0.0339. Compound 1 consists of two co-crystallized Co(II) complexes [Co(AMTTO)₂(CH₃CN)₂]²⁺ and [Co(AMTTO)₂(H₂O)₂]²⁺ and four nitrate counter anions In both complexes, cobalt(II) ions are in an octahedral arrangement. Two S, N bidentate AMTTO ligands are coordinated to both Co(II) ions. The coordination sphere of Co1 is completed by two acetonitrile molecules, and these positions are occupied by water molecules for Co2.

Graphic Abstract

A co-crystal of cobalt(II) compound was isolated from the reaction of Co(NO₃)₂?6H₂O and 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine in acetonitrile as solvent.

     

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.     

Synthesis and Crystal Structure of One-Dimensional Carboxylate-Bridged Copper(II) Complex with 2-Pyridylmethylamino-3-butyric acid

Abstract The tridentate Schiff base carboxylate-containing ligand 2-pyridylmethylamino-3-butyric acid (Hpaba) reacts with copper(II) perchlorate to give the one-dimensional chain complex {[Cu(μ-paba)](ClO₄)·H₂O} _n (1). The coordination geometry of each copper(II) ion is best described as a square-plane with two nitrogen atoms and one carboxylate oxygen atom of the ligand, and one carboxylate oxygen atom belong to another ligand. It crystallizes in the monoclinic system P2₁/c with a = 12.717(2), b = 7.9163(15), c = 14.981(2) ?, β = 111.14(1)°, V = 1406.8(4) ?³, Z = 4. Cyclic voltammogram of 1 undergoes the reversible one-electron oxidation to the Cu(III) and the reversible one-electron reduction to the Cu(I) state. Graphical Abstract Crystal structure of 1 reveals a syn-anti carboxylate-bridged one dimensional chain complex in which the coordination environment around each copper(II) ion exhibits a distorted square plane.      

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.     

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 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 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.     

X-ray determination of thermal lattice expansion of CuSi2 + xP3 (x = 1, 2) at elevated temperatures

CuSi₂P₃ is a semiconductor having sphalerite structure with the space group F3 3m with random distribution of the copper and silicon atoms on the cation sites. Silicon is soluble in CuSi₂P₃ upto 3 moles to form CuSi_{2 + x}P₃ (x = 1, 2, 3) compounds in single phase. In continuation of our work on thermal expansion of ternary semiconductors, CuSi₃P₃ crystals have been grown by a modified Bridgman method. Using a Unicam high temperature camera, the precision lattice parameter and the coefficient of thermal expansion (CTE) of CuSi₃P₃ at various high temperatures have been evaluated from X-ray diffraction data. It has been found that the lattice parameter increases non-linearly while the coefficient of thermal expansion increases linearly with temperature. The results on thermal expansion of various semiconductors have been discussed in terms of their ionicities.