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.     

Electronic Structure of [Cu(C7H4NO3S)2(H2O)4] · 2H2O Crystal

The electronic absorption spectrum and ESR spectrum of the crystal of the title compound [Cu(C₇H₄NO₃S)₂(H₂O)₄] · 2 H₂O, are measured. The experimental results are discussed quantitatively by using the ligand field theory and the radial wave function of non-free Cu(II). The electronic structure of the compound is in agreement with its crystal structure.     

Molecular structure of (tBu)3Al[O=C(OPh)2]

The molecular structure of (^tBu)₃Al[O=C(OPh)₂] has been determined. The increase in the C=O bond distance [1.258(4) Å] when compared to free O=C(OPh)₂ [1.191(3) Å], is presented in respect to the activating ability of aluminum Lewis acids. Crystal data: monoclinic, P2₁/n, a = 10.653(2), b = 18.486(4), c = 14.551(3) Å, = 108.07(3)°, and V = 2724.3(9) ų for Z = 4.     

Crystal and molecular structure of [Cu(pyrimidine)4]2BF4

The crystal structure of [Cu(pyrimidine)₄]2BF₄ was determined using single crystal X-ray diffraction. The compound crystallizes in the monoclinic space groupP2₁/n, with lattice parametersa=9.9736(8),b=13.872(1),c=16.568(1) Å. β=98.002(1), andZ=8, yielding a calculated density of 1.857 g/cm³. The Jahn-Teller distorted copper coordination sphere is composed of the four pyrimidine ligands in the equatorial positions (ave. Cu?N=2.02 Å) and the longer axial bonds from the copper to one fluorine (ave Cu?F=2.39 Å) on each of the BF ₄ ^? anions. The crystal structure features layers of molecules having interleaved pyrimidine rings: the layers are connected through intermolecular H … F hydrogen bonds.     

Hydrogen-bonded coordination network in crystal structures of [Cu(3-PM)4Cl2] and [Cu(4-PM)4Cl]Cl, (PM = pyridylmethanol)

The crystal and molecular structures of [Cu(3-PM)₄Cl₂] (1) and [Cu(4-PM)₄Cl]Cl (2) have been determinated by X-ray crystallography. Complex 1 crystallizes in the triclinic system, space group P–1, with lattice parameters a = 7.972(2) Å, b = 8.293(2) Å, c = 10.707(2) Å, = 105.73(3)°, = 90.04(3)°, = 110.38(3)°, and Z = 1 at 100 K. The coordination geometry of each Cu atom is approximately octahedral formed by four nitrogen atoms of pyridine rings of 3-pyridylmethanol molecules in the equatorial plane and two chlorine atoms occupying the axial positions. The O—HsO, C—HsCl, and O—HsCl intermolecular hydrogen bonds and s stacking link the molecules in 3-D hydrogen-bonded coordination network. Complex 2 crystallizes in the tetragonal system, space group P4/n, with lattice parameters a = 10.464(1) Å, c = 11.339(2) Å, and Z = 2 at 217 K and a = 10.352(1) Å, c = 11.201(2) Å, and Z = 2 at 293 K. The coordination geometry of Cu atom in the [Cu(4-PM)₄Cl]⁺ ion is approximately square pyramidal formed by four nitrogen atoms of pyridine rings of 4-pyridylmethanol molecules in equatorial plane and one chlorine atom in axial position. The O—HsCl and C—HsCl intermolecular hydrogen bonds link the molecules in 2-D hydrogen-bonded coordination network.     

Synthesis and crystal structure of [Nd(H2O)2]2(C2O4)3

Some crystals of [Nd(H₂O)₂]₂(C₂O₄)₃ were synthesized hydrothermally by heating at 200°C for 8 days an aqueous suspension of neodymium oxalate decahydrate in presence of terephthallic acid and guanidinium carbonate. They crystallize in the orthorhombic system, space group P2₁2₁2₁, with a = 8.6702(7) Å, b = 9.558(2) Å, and c = 17.009(2) Å. The structure of this complex is built up by two independent neodymium atoms, three bischelating oxalate ligands, and four water molecules forming a rectangle building unit of 6-membered ring, [Ln(H₂O)₂(C₂O₄)]₆. The packing of these units leads to a layer parallel to the plane (001). However, the neodymium atoms of two neighbor layers share an edge of oxalato oxygen atoms thus giving a double-layer. The three dimensionality between these double-layers is insured by hydrogen bonds of water molecules which are bound to the neodymium atoms. There is no zeolitic water molecule. The two neodymium atoms are nine-coordinated. In both cases, the coordination polyhedron can be described as a distorted tricapped trigonal prism.     

Synthesis and molecular structure of [Al(CH3)2]2[C10H22N4] [Al(CH3)3]2: Condensation product of trimethylaluminum and a multidentate open-chain amine

The crystalline condensation product [Al(CH₃)₂]₂[C₁₀H₂₂N₄][Al(CH₃)₃]₂ is prepared from reaction of the multidentate open-chain amine 1,4-bis(3-aminopropyl)piperazine with trimethylaluminum in methylene chloride. The compound crystallized in the monoclinic space groupC2/c with unit cell parametersa=25.166(12),b=7.268(4),c=17.316(4) Å,=115.3(4)°, andD _c =1.06 g cm^–3 forZ=4. Least-squares refinement based on 1054 observed reflections with intensitiesI 3(I) in the range 2<2<45° led to a finalR factor of 0.053 (R _w =0.064). The title compound resides on a crystallographic center of symmetry with independent Al-N distances of 1.889(5), 2.058(5), and 2.030(5) Å.     

Synthesis and crystal structure of [Cu2(NO3)4L2(BIPY)2 (H2O)3]·H2O (L = N,N′-bis(4-pyridylmethyl) isophthalamide

The synthesis and molecular structure of the title compound is reported. There are two different Cu atoms in separate chains which are linked to form double-stranded chains. Each Cu has a distorted octahedral coordination geometry. The structure has a triclinic space group P-1 with a = 11.0764(5), b = 15.9276(7), c = 18.2000(7) Å, V = 3197.9(2) ų, and Z = 2.     

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.     

Structural features of a new [Fe(nicotinamide)2(H2O)4]·[Fe(H2O)6]·(SO4)2·2H2O complex

A new nicotinamide complex of Fe(II) cation was prepared by reaction between ferrous sulfate and nicotinamide in aqueous solution. The complex was characterized on the basis of elemental analysis, FT IR and UV–VIS spectroscopy, electrochemistry (cyclic voltammetry) and X–ray crystallography. The complex consists of the molecular composition of [Fe(nicotinamide)₂(H₂O)₄]· [Fe(H₂O)₆]·(SO₄)₂·2H₂O. The complex crystallizes in the monoclinic space group P 2₁/c [a = 12.862(3), b = 7.110(3), c = 16.382(3) Å; β = 95.79(2)°]. It has been proven that nicotinamide is coordinated to Fe(II) through the nitrogen atom of its heterocyclic ring. © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

Crystal Growth,Thermal and Linear Optical Properties of the Non‐Centrosymmetric Hydrated Tetraborates Na2[B4O5(OH)4] . 3H2O (Tincalconite) and K2[B4O5(OH)4] . 2H2O

Large single crystals of the non‐centrosymmetric hydrated tetraborates Na₂[B₄O₅(OH)₄] . 3H₂O (Tincalconite) (point group 32) and K₂[B₄O₅(OH)₄] . 2H₂O(point group 222) were grown from aqueous solutions and the linear optical properties (refractive indices between 365 nm and 1530 nm and unpolarized absorption spectra) as a basis for nonlinear optical investigations were determined. The uniaxial positive sodium salt is not phase matchable; in the orthorhombic potassium compound type I phase matching is possible in the near infrared region. Thermal investigations indicate a phase transition at ≈285 K for Na₂[B₄O₅(OH)₄] . 3H₂O.     

Cluster self-organization of TR,Ge-containing crystal-forming systems: Suprapolyhedral precursors and self-assembly of La3Ga[6]Ga 4 [4] Ge[4]O14 (langasite) and La3Ge[6]Ge 2 [5] Ge 2 [4] Ga[4]O16 gallogermanates

A combinatorial-topological analysis of the La₃Ga^[6]Ga ₄ ^[4] Ge^[4]O₁₄ and La₃Ge^[6]Ge ₂ ^[5] Ge ₂ ^[4] Ga^[4]O₁₆ gallogermanates, which have MT and MPT microporous frameworks composed of M octahedra (GeO₆, GaO₆), T tetrahedra (GeO₄, GaO₄), and P pyramids (GeO₅), is performed using the method of coordination sequences with the TOPOS 3.2 program package. It is established that the La₃Ga^[6]Ga ₄ ^[4] Ge^[4]O₁₄ gallogermanate is characterized by a crystal-forming net 6 6 6 (of the graphite type). A new type of the binodal net 6 10 1 0 + 6 10 (2: 1) is revealed in the La₃Ge^[6]Ge ₂ ^[5] Ge ₂ ^[4] Ga^[4]O₁₆ gallogermanate. The cyclic cluster precursors composed of six polyhedra with a lanthanum template atom at the center of the LaMT ₅ and LaMP ₃ T ₃ clusters are identified by the two-color decomposition of the nets in the structures of the La₃Ga^[6]Ga ₄ ^[4] Ge^[4]O₁₄ and La₃Ge^[6]Ge ₂ ^[5] Ge ₂ ^[4] Ga^[4]O₁₆ gallogermanates. The coordination numbers of the cluster precursors in these structures are found to be equal to 6 and 4 for two-dimensional nets and 8 and 6 for three-dimensional nets, respectively.     

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.     

Synthesis and crystal structure of [Tb4(H2O)2](C2O4)2(C5H6O4)4

A terbium complex associating two ligands, oxalate and glutarate, was prepared under hydrothermal conditions at 200°C by treating an aqueous suspension of terbium oxalate decahydrate with glutaric acid and guanidinium carbonate. Its structure was solved by X-ray diffraction on a single crystal. It crystallizes in the monoclinic space group P2₁ with lattice constants, a = 9.514(1) Å, b = 9.0681(8) Å, c = 19.702(2) Å, and = 97.90(1)°. The terbium atoms and the oxalate ligands build dense chains which are connected by one side of the carboxylic group of some glutarate ligands, thus forming a sheet at the c level 0 and 1/2. These sheets are bridged by glutarate groups. The terbium atoms are ninefold coordinate with nine oxygen atoms of the ligands or with one water molecule and eight oxygen atoms of the ligands. Each polyhedron of the terbium atoms share one edge and one face of oxygen atoms with the two neighboring ones. The oxalate ligands are bischelating and bismonodentate. The coordination scheme of glutarate differs: either they are bismonodentate from one side and chelating and monodentate from the other side or they are chelating and monodentate from both sides.     

Solvent-controlled structures. Synthesis and characterization of complexes Cu(L)2(CH3COO)2 and [Cu2(μ-CH3COO)4(L)2](L)2 [L = N-(4′-methylaniline)-4-pyridinecarboxamide]

Two complexes Cu(L)₂(CH₃COO)₂ (1) and [Cu₂(μ-CH₃COO)₄(L)₂](L)₂ (2) (L = N-(4′-methylaniline)-4-pyridinecarboxamide) have been prepared and their crystal structures have been determined by single-crystal X-ray diffraction. The complexes are obtained by using the same raw materials and reaction conditions except solvents. The presence or absence of water controls the coordination mode to give rise to different structures. The structure of 1 has a triclinic space group P-1 with a = 8.381(3) ?, b = 8.545(4) ?, c = 11.357(5) ?, α = 110.654(6)°, β = 102.388(7)°, γ = 97.889(7)°, V = 722.9(5) ?³, and Z = 1. The structure of 2 has a triclinic space group P-1 with a = 9.121(3) ?, b = 9.454(3) ?, c = 17.233(5) ?, α = 77.374(5)°, β = 89.827(6)°, γ = 74.342(6)°, V = 1393.8(7) ?³, and Z = 1. Supramolecular assemblies have also been found via noncovalent bonds such as hydrogen bonds, π–π stacking interactions.     

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.