Synthesis, properties, and X-ray structure of [Cu(dpa)Cl2] (dpa = di-(2-picolyl)amine)

The mono(dpa)copper(II) complex [Cu(dpa)Cl₂] (1) (dpa = di-(2-picolyl)amine) has been synthesized and structurally characterized. It crystallizes in the monoclinic system P2₁/n with a = 8.155(1), b = 12.560(1), c = 12.817(2) Å, = 91.64(2)°, V = 1312.3(2) ų, Z = 4. The copper atom is coordinated by three nitrogen atoms from the dpa ligand and two chlorides in a distorted square-pyramidal environment. Cyclic voltammetric data show that 1 undergoes the reversible one-electron oxidation to the Cu(III) and the reversible one-electron reduction to the Cu(I) state.     

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.     

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 crystal structure of a 2D (6,3) coordination network, {[Ag(L)1.5]NO3} n [L = 1,3-bis(benzylthio)propane]

A new dithioether silver(I) complex, {[Ag(L)_1.5]NO₃} _n (1) has been prepared by the reaction of AgNO₃ with 1,3-bis(benzylthio)propane (L) in methanol/chloroform. The structure was characterized by single-crystal X-ray diffraction analysis: rhombohedral system, space group R –3c, with a =b = 15.651(7), c = 39.26(4) Å, V = 8328(1) ų, and Z = 6. The crystal structure consists of [Ag(L)_1.5]⁺ cations and NO₃ ^– anions. In 1, each silver(I) center is coordinated equivalently to three sulfur donors from three different ligands to give a trigonal-planar coordination geometry. Each L links two adjacent silver(I) centers in bis-monodentate bridging mode to form a 2D (6,3) network sheet. Furthermore, these 2D sheets are linked by the weak coordination interactions between nitrate ions and silver(I) atoms to form a 3D brick-wall framework.     

Synthesis and crystallographic characterization of a six coordinate Cu(II) complex based on hexamethylenetetramine ligand

The title compound, Cu(H₂O)₆]Cl₂.2{(CH₂)₆N₄}.4H₂O ( 1 ), has been prepared under mild hydrothermal conditions. Each Cu^II atom, located on a centre of symmetry, is coordinated by six water molecules in distorted octahedral coordination geometry. The hexamethylenetetramine molecule does not coordinate to the Cu atom but links with the Cu complex via three O—H…N hydrogen bonds. The remaining N atom of the hexamethylenetetramine is hydrogen‐bonded to the solvent water molecule. In the crystal structure, intermolecular O—H…O, O—H…N and O—H…Cl hydrogen bonds link the components into a three‐dimensional network. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Synthesis,crystal structure and characterization of new transition metal compounds of bromophenols: Bis(2,4,6‐tribromophenolato) di(N‐methylimidazole)M(II) (M=Co,Cu)

Bis(2,4,6‐tribromophenolato)di(N‐methyl imidazole)M(II), where M stands for cobalt and copper metals, was synthesized via reaction of the corresponding metal sulphate and 2,4,6‐tribromophenolate in aqueous media in the presence of N‐methyl imidazole and sodium hydroxide. Although various crystallization procedures were applied only cobalt complex was obtained as single crystals. The Co(II) ion has a distorted octahedral enviroment involving two O atoms and two N atoms of the Bis(2,4,6‐tribromophenolato)di(N‐methyl imidazole) ligand. Powder x‐ray diffraction pattern of copper compound was used for cooper complex. For characterizations of complexes carbon, hydrogen and nitrogen elemental analysis, FTIR and UV spectroscopy, DSC thermal analysis and magnetic susceptibility measurements at room temperature were performed. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Crystal of catena-(μ2-terephthalato)-bis (N-methylimidazole)-copper(II)

A new one-dimensional chain complex [Cu(ta) (N-MeIm)₂]n (where ta = terephthalic acid dianion,N-MeIm =N-methylimidazole) has been synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the Monoclinic space groupP2₁/c with the parameters:a = 5.2930(11)Å,b = 14.679(3)Å,c = 11.007(3)Å, β = 104.84(3)^°,V = 826.7(3)ų, withZ = 4 formula units. In the structure, each Cu atom is coordinated by a pair ofN-methylimidazole ligands and a pair of monodentate carboxylate groups, affording a square planar N₂O₂ geometry. Both carboxylate groups of the terephthalate dianion coordinate in a monodentate mode bridging two Cu(II) ions with formation of 1D zigzag chain along thec axis. This supramolecular compound exhibits a three-dimensional solid state structure constituted by hydrogen bonds and C–H–π stacking interactions.     

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.     

Synthesis and crystal structure of a new two-dimensional chromium(III) network through hydrogen bonds

A new chromium(III) complex, [Cr(ox)(bdmpza)(H₂O)], (ox = oxalate dianion and bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate, respectively), has been synthesized and characterized by X-ray crystallography. This compound crystallizes in the monoclinic space group P2₁/c, with a = 7.008(3) Å, b = 14.229(5) Å, c = 16.497(7) Å, = 101.588(7)°, V = 1611.5(11) ų, Z = 4. The chromium atom has a distorted octahedral environment with different coordination atoms. Bis(3,5-dimethylpyrazol-1-yl)acetate anion is a tridentate ligand, and the oxalate group acts as a chelating bidentate ligand. This compound also forms an infinite two-dimensional network through O–H O hydrogen bonds. The lengths of the hydrogen bonds are 2.765(5) and 2.733(5) Å, respectively.     

The structure of [Co(H-tptz)Cl3]·H2O (tptz=2,4,6-tri(2-pyridyl)-1,3,5-triazine) prepared by crystallization from the ionic liquid, N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide

The structure of tris-chloro[2,6-bis(2′-pyridyl)-4-(2′-pyridinium)-1,3,5-triazine]cobalt(II) monohydrate, [Co(C₁₈H₁₃N₆)Cl₃]·H₂O (C2/c (No. 15), a=7.783(11), b=22.42(3), c=11.001(15) ?, β=90.05(2)°), crystallized from the open air reaction of CoCl₂ and 2,4,6-tri(2-pyridyl)-1,3,5-triazine in the ionic liquid, N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide is reported. The structure consists of six coordinate cobalt in an octahedral geometry bonded to the tridentate tptz ligand and three chlorines. The non-coordinating pyridyl group in the tptz ligand is protonated (with the protonated nitrogen crystallographically disordered over two possible sites), providing overall charge neutrality for the complex.     

Crystal and molecular structure of [5,10,15,20-tetrakisphenyl-2-ethoxy-3-oxa-chlorinato]Ag(II)

The silver(II) complex of the chlorin-like derivativev [5,10,15,20-tetrakisphenyl-2-ethoxy-3-oxa-chlorinato]Ag(II) (1Ag), formally formed by substitution of one pyrrolic subunit in silvermeso-tetraphenylporphyrin by one ethoxy-substituted hydrooxazole moiety, crystallizes in the tetragonal space groupI4/m witha = 13.4811(10) Å,c = 9.7361(13) Å, andZ = 2. The molecule, which is asymmetric, accommodates the high-symmetry space group by rotational disorder with the silver atom located on the four-fold axis.     

The preparation and crystal structures of [Ru(bpy) (η2-tpy)(CO)CH2OAc]PF6 and [Ru(η3-tpy)(CO)CH2OAc] PF6 (bpy = 2,2′-bipyridine; tpy = 2,2′:6′,2″ terpyridine)

The first titled compound, 1, was obtained by treating [Ru(bpy)(η²-tpy)(CO)CH₂OH]PF₆ with acetic anhydride. Heating 1 in acetonitrile afforded 2, [Ru((η³-tpy)(MeCN)(CO) CH₂OAc]PF₆. Allowing 2 to stand in CH₂Cl₂ followed by concentration and precipitation afforded the second titled compound, 3 ([Ru((η³-tpy)(CO)–CH₂OAc]PF₆), in which the acetoxymethyl group had become bidentate. Crystal data for 1, monoclinic crystal system, space group C2/c, a=26.001(4) ?, b=13.0395(18) ?, c=20.718(3) ?, β=107.700(2)°, V=6691.7(16) ?³, Z=8; for 3, monoclinic crystal system, space group P2₁/n, a=10.864(2) ?, b=16.922(4) ?, c=11.127(2) ?, β=90.907(3)°, V=2045.4(8) ?³, Z=4.     

Crystal structure and properties ofcatena-poly[manganese(II)-μ-dichloro-μ-L-proline-k 2 o,o′] monohydrate

The crystal structure and some physico-chemical properties of MnCl₂·Pro·H₂O (Pro=L-proline) were studied. This compound is stable up to approximately 313 K. Upon heating the complex loses a molecule of water and is transformed into the oxide in two steps. The IR spectrum was recorded. The compound crystallizes in the orthorhombic space groupP2₁2₁2₁ witha=7.112(2) Å,b=10.196(2) Å,c=13.249(3) Å andZ=4. The manganese atoms in the polymeric chain are bridged by two chlorine atoms and oxygen atoms from the carboxylate group of L-proline. The Mn?Cl bond distances range from 2.535(1) Å to 2.581(1) Å, the Mn?O bond distances range from 2.135(2) Å to 2.153(2) Å and Mn?Mn bond distances are 3.556(1) Å. One molecule of water is hydrogen-bonded with a nitrogen atom of the L-proline ring.     

Synthesis,crystal structure and photophysical studies on a ruthenium(II) carbonyl hydrido compound based on 2,2′‐bipyridyl‐5,5′‐dicarboxylic acid (H2bpdc)

A novel complex, namely [Ru^II(PPh₃)(CO)(H)(Hbpdc)]·2MeOH ( 1 ) (H₂bpdc = 2,2′‐bipyridyl‐5,5′‐dicarboxylic acid), has been synthesized from the reaction of H₂bpdc with [Ru^II(PPh₃)₃(CO)(H)₂] in methanol under mild condition and characterized by elemental analysis, IR spectrum, ESI mass spectrometry, and single crystal X‐ray diffraction. The structure shows that the complex crystallizes in the monoclinic space group P2₁/c with unit cell parameters a = 11.8984(13) Å, b = 16.5180(18) Å, c = 25.5322(19) Å, β = 115.302(4)°, V = 4536.6(8) ų, Z = 4. This compound features a 1‐D supramolecular chain constructed via hydrogen bonds. Its photophysical properties have been investigated in MeOH solution and in the solid state at room temperature.     

Structure and characterization of hexakis(imidazole) cobalt(II) complexes: [Co(Im)6(OBz)2] and [Co(Im)6(mB)2] (Im = imidazole, OBz = benzoate, mB = p-methoxybenzoate)

The crystal and molecular structures of the complexes of [Co(Im)₆(OBz)₂] and [Co(Im)₆(mB)₂] (Im = imidazole, OBz = benzoate, mB = p-methoxybenzoate) have been determined by X-ray crystallography. The crystal structures are very similar and consist of discrete molecules of [Co(Im)₆(OBz)₂] and [Co(Im)₆(mB)₂], respectively. They both crystallize in the triclinic system, space group the former with lattice parameters a = 7.6934(3), b = 10.4518(5), c = 11.6088(5) Å, = 73.920(1), = 79.023(1), = 73.681(1)°, and Z = 1; the latter with a = 9.8336(3), b = 10.5509(2), c = 10.8889(3) Å, = 61.450(1), = 76.832(1), = 71.157(1)°, and Z = 1. The cobalt(II) ions have octahedral geometry with a CoN₆ chromophore. In the solid state, the complexes all form a three-dimensional network through N—H···O hydrogen bonds. The electronic spectra and IR spectra data are in agreement with the structural data.     

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.     

Crystal structure of [Mn2(III)(salpa)2Cl2(H2O)2] (H2salpa = 1-(salicylaldeneamino)-3-hydroxypropane)

The manganese complex, (Mn₂(III)(salpa)₂Cl₂(H₂O)₂], has been prepared and its structure determined using x-ray crystallography. The dimer is a di-₂-alkoxo complex which is a six-coordinate manganese dimer with unsupported alkoxide bridges and a rare example of a chloride- and water-containing manganese dimer. The complex crystallizes in the monoclinic space group P2₁/c with a = 9.315(5), b = 11.130(4), c = 11.637(5) Å, = 104.33(3)°, V = 1169.0(9) ų, and Z = 2. The structure comprises discrete binuclear clusters in which the metal atoms are bridged by two alkoxo oxygens of the salpa^2– ligands. The Mn—O and Mn—N distances are in good agreement with those found for other manganese(III) Schiff base complexes. The Mn—Cl and Mn—O3 distances are 2.585(2) and 2.371(2) Å, respectively, and the Mn ··· Mn distance is 3.001(1) Å. In the crystal, there are two types of hydrogen bonding between the H₂O molecule and the Cl atom with Cl ··· H(H₂O) distance of 2.33(6) (intramolecule: –1 + x, y, –1 + z) and 2.68(6) Å (intermolecule: –1 + x, 0.5–y, –0.5 + z).     

Crystal structures of [WI2(CO)3{Ph2P(CH2) n PPh2}] (n = 2 or 3)

[WI₂(CO)₃{Ph₂P(CH₂)₂PPh₂}] (1) crystallizes out in the monoclinic space group P2₁/n, with a = 13.852(7) Å, b = 14.789(19) Å, c = 14.915(19) Å, = 102.86(1)°, Z = 4. [WI₂(CO)₃{Ph₂P(CH₂)₃PPh₂}] (2) crystallizes out in the monoclinic space group P2₁/n, with a = 10.499(15) Å, b = 14.58(2) Å, c = 20.75(3) Å, = 103.59(1)°, Z = 4. Both structures show the metal in a seven-coordinate environment with a carbonyl in the unique capping position, two further carbonyls and a phosphorus in the capped face, and two iodides and the second phosphorus in the uncapped face.