Bis­(dicyan­amido)(diethyl­enetri­amine‐κ3N)copper(II) and (dicyan­amido)(tri­ethyl­enetetr­amine‐κ4N)copper(II) dicyan­amide

Two new complexes, [Cu(C₂N₃)₂(dien)] (dien is diethyl­ene­tri­amine, C₄H₁₃N₃), (I), and [Cu(C₂N₃)(trien)](C₂N₃) (trien is triethyl­ene­tetr­amine, C₆H₁₈N₄), (II), have been characterized by single‐crystal X‐ray diffraction. Both complexes display a distorted tetragonal–pyramidal geometry. In (I), the Cu atom is coordinated in the basal plane by three diethyl­ene­tri­amine N atoms [Cu—N = 2.000 (2), 2.004 (2) and 2.025 (2) Å] and one terminal N atom [Cu—N = 1.974 (2) Å] from one monodentate dicyan­amide group, and in the apical position by one terminal N atom [Cu—N = 2.280 (2) Å] from the other monodentate dicyan­amide group. In (II), the Cu atom is surrounded by four triethyl­ene­tetr­amine N atoms [Cu—N = 2.012 (2), 2.014 (2), 2.019 (2) and 2.031 (2) Å in the basal plane] and a terminal N atom [Cu—N = 2.130 (2) Å in the apical site] from one monodentate dicyan­amide group. The other dicyan­amide anion is not directly coordinated to the metal atom. In both (I) and (II), hydro­gen‐bond interactions between the uncoordinated terminal N atoms of two dicyan­amide ions and the amine H atoms lead to the formation of three‐dimensional networks.     

Low‐dimensional compounds containing cyano groups. II. catena‐Poly[[(2,2′‐bipyridine‐κ2N:N′)(dicyanamido‐κN)copper(II)]‐μ‐dicyanamido‐κ2N:N′]

The crystal structure of the title compound, [Cu(C₂N₃)₂(C₁₀H₈N₂)]_n, is formed by neutral zigzag chains of the [–NC–N–CN–Cu{(bpy)N(CN)₂}–NC–N–CN–] type run­ning along the c axis (bpy is 2,2′‐bi­pyridine). The Cu atoms in the chains are pentacoordinated in the form of a distorted tetragonal pyramid, with a CuN₅ chromophore. The coordination sites are occupied by two N atoms of one bpy mol­ecule in the basal plane [Cu—N 2.018 (4) and 2.025 (2) Å] and by three terminal N atoms of two dicyan­amide ligands. One of the dicyan­amide ligands is coordinated in a monodentate fashion through a nitrile N atom in the basal plane [Cu—N 1.963 (4) Å]. The second acts as an end‐to‐end bridging ligand to a neighbouring Cu atom and is coordinated by one nitrile N atom in the basal plane [Cu—N 2.001 (2) Å], while the second nitrile N atom occupies the apical position [Cu—N 2.159 (2) Å] and originates from the bridge connecting another Cu atom. The shortest intrachain Cu?Cu distance is 8.212 (1) Å, as a consequence of the large bridging ligand, whereas the minimum interchain distance between Cu atoms is only 5.77 (7) Å, because of the interdigitation of the chains.     

(Azido‐κN)bis­(di‐2‐pyridylamine)­copper(II) hexa­fluoro­phosphate and (azido‐κN)bis­(di‐2‐pyridylamine)­copper(II) chloride tetra­hydrate

The two new title complexes, [Cu(N₃)(dpyam)₂]PF₆ (dpyam is di‐2‐pyridylamine, C₁₀H₁₁N₃), (I), and [Cu(N₃)(dpyam)₂]Cl·4H₂O, (II), respectively, have been characterized by single‐crystal X‐ray diffraction. Both complexes display a distorted square‐pyramidal geometry. Each Cu atom is coordinated in the basal plane by three dpyam N atoms and one azide N atom in equatorial positions, and by another N atom from the dpyam group in the apical position. In complex (I), the one‐dimensional supra­molecular architecture is assembled via hydrogen‐bonding inter­actions between the amine N atom and terminal azide N atoms and the F atoms of the PF₆⁻ anion. For complex (II), hydrogen‐bonding inter­actions between the amine N atom, the Cl⁻ anion and water O atoms result in a two‐dimensional lattice.     

(2‐Methyl­quinolin‐8‐olato)­iron(III) and ‐copper(II) complexes

The crystal structures of tris(2‐methyl­quinolin‐8‐olato‐N,O)­iron(III), [Fe­(C₁₀­H₈­NO)₃], (I), and aqua­bis(2‐methyl­quinolin‐8‐olato‐N,O)­copper(II), [Cu­(C₁₀­H₈NO)₂­(H₂O)], (II), have been determined. Compound (I) has a distorted octahedral configuration, in which the central Fe atom is coordinated by three N atoms and three O atoms from three 2‐methylquinolin‐8‐olate ligands. The three Fe—O bond distances are in the range 1.934 (2)–1.947 (2) Å, while the three Fe—N bond distances range from 2.204 (2) to 2.405 (2) Å. In compound (II), the central Cu^II atom and H₂O group lie on the crystallographic twofold axis and the coordination geometry of the Cu^II atom is close to trigonal bipyramidal, with the three O atoms in the basal plane and the two N atoms in apical positions. The Cu—N bond length is 2.018 (5) Å. The Cu—O bond length in the basal positions is 1.991 (4) Å, while the Cu—O bond length in the apical position is 2.273 (6) Å. There is an intermolecular OW—H?O hydrogen bond which links the mol­ecules into a linear chain along the b axis.     

Coordination polyhedron and chemical vapor deposition of Cu(hfacac)2(t-BuNH2)

A new pentacoordinate Cu(II) complex, Cu(hfacac)(2)(t-BuNH(2)) [hfacac = CF(3)C(O)CHC(O)CF(3)(-), t-BuNH(2) = tert-butylamine], has been synthesized and structurally characterized. Interestingly, the structure of a single crystal occurred as square pyramidal with one O atom at the apical position and one N and three O atoms at the basal positions, showing a serious degree of distortion. This contrasts with the square-pyramidal structure of Cu(hfacac)(2)L (L = H(2)O and pyrazine), which has the L ligand at the axial position. In the Cu(hfacac)(2)(t-BuNH(2)) complex, the t-BuNH(2) ligand is placed at an equatorial position with a lowered angle by 19.9(2) degrees from the basal plane. This distortion seems to reduce sigma influence and steric hindrance and so stabilizes the square-pyramidal geometry. This precursor has a lower melting point and superior stability to air, moisture, and heat than the Cu(hfacac)(2)(xH(2)O) precursor. The deposition rate of copper oxide film on a Pt layer above 450 degrees C was nearly constant with increasing temperature, indicating a mass transport limited reaction. Therefore it would be a useful metal organic chemical vapor deposition precursor for the fabrication of copper oxide film or superconducting materials. Crystal data for Cu(hfacac)(2)(t-BuNH(2)): 293(2) K, a = 9.6699(4) A, b = 18.0831(10) A, c = 12.8864(11) A, beta = 111.839(5) degrees, monoclinic, space group P2(1)/c, Z = 4.     

Synthesis,crystal structures,and antimicrobial activity of two thiocyanato-bridged dinuclear copper(II) complexes derived from 2,4-dibromo-6-[(2-diethylaminoethylimino)methyl]phenol and 4-nitro-2-[(2-ethylaminoethylimino)methyl]phenol

A pair of structurally similar thiocyanato-bridged dinuclear Cu(II) complexes derived from the Schiff bases 2,4-dibromo-6-[(2-diethylaminoethylimino)methyl]phenol and 4-nitro-2-[(2-ethylaminoethylimino)methyl]phenol has been prepared and characterized by physico-chemical and spectroscopic methods. Each Cu atom is five-coordinate in a square-pyramidal geometry, with one O and two N atoms of one Schiff base ligand and one N atom of a bridging thiocyanate ligand defining the basal plane, and with one terminal S atom of another bridging thiocyanate ligand occupying the apical position. Antimicrobial activities of the Schiff bases and the two complexes have been tested. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Chloro(2,9-dimethyl-1,10-phenanthroline-N,N′)(isoquinoline-1-carboxylato-O,N)copper(II)

The asymmetric unit of the title compound, [CuCl(C₁₀H₆NO₂)(C₁₄H₁₂N₂)], contains two monomeric copper mol­ecules, A and B. Each Cu atom is coordinated to one 2,9-di­methyl-1,10-phenanthroline (neocuproine) ligand via both N atoms, to one iso­quinoline-1-carboxyl­ate anion (IQC⁻) via the N and one O atom, and to one Cl⁻ anion. The environment of the Cu atom is approximately square pyramidal, with the apical position occupied by an N atom of neocuproine. In mol­ecule A, the Cu atom is 0.301 (1) Å above the basal plane; this distance is 0.316 (1) Å in mol­ecule B. The crystal packing is characterized by several hydrogen bonds.     

Synthesis and Crystal Structure of a Copper(II) Complex with α-Hydroxylated Acid, [Cu(C_(14)H_8O_3)(C_5H_(13)NO)(H_2O)].0.5H_2O

1 INTRODUCTION There has been considerable interest of copper(II) -hydroxylate complexes in the structural chemistry and biochemistry. There are two structural types in copper(II) -hydroxylate com- plexes: mononuclear[1~6] and dinuclear structure[7~9]. The present work is a part of our study on the copper complexes of -hydroxylated acid and reports the synthesis and structure of a mononuclear copper(II) complex with 9-hydroxy- fluorene-9-carboxylato acid, [Cu(C14H8O3)(C5H13- NO)(H…     

Crystal structure and spectroscopic properties of isothiocyanato[(3,14-dimethyl-2,6,13,17-tetraazatricyclo(16.4.0.0<Superscript>7,12</Superscript>)docosane)]copper(II) thiocyanate

A new complex [Cu(L¹)(NCS)]SCN, where L¹ = 3,14-dimethyl-2,6,13,17-tetraazatricyclo( 16.4.0.0^7,12)docosane is prepared and characterized by single crystal X-ray crystallographic analysis. The complex crystallizes in the triclinic space group P1? with two mononuclear formula units in a cell of dimensions a = 7.9681(2) Å, b = 8.8644(2) Å, c = 18.8165(5) Å, α = 76.758(70)°, β = 78.490(2)° and γ = 77.679(2)°. The Cu(II) ion is five-coordinate in an axially elongated square pyramidal environment, with the four amine N atoms at the equatorial positions and the N atom of one thiocyanate at an apical site. The macrocyclic cyclam moiety adopts a stable trans-III configuration. The Cu–N basal plane bond length has a mean value of 2.037(2) Å. The coordinated Cu–NCS bond length is 2.322(3) Å. The N atom of the thiocyanate anion is connected to the macrocyclic ligand of the cation via an NH…N(CS) hydrogen bond. The UV-visible absorption and IR spectral properties are also discussed.     

三(3,5-二甲基吡唑)氢合硼酸钾及双[三(3,5-二甲基吡唑)]氢合硼酸根合铜(II)的合成和晶体结构

为研究吡唑硼类配体的配位行为, 合成了三(3,5-二甲基吡唑氢合硼酸钾[KHB(C~5H~7N~2)~3], 简称(KL)和双[三(3,5-二甲基吡唑)氢合硼酸根]合铜(II){Cu[HB(C~5H~7N~2)~3]~2}, 简称(CuL~2), 并测定了它们的晶体结构。化合物KL属空间群P2~1/n。a=1.0527(8), b=0.9464(3), c=1.7730(9)nm, β=94.51(5)°,Z=4, D~c=1.268g.cm~-~3, R=0.079。化合物CuL~2属空间群PI, a=0.8768(1),b=1.0170(2), c=1.0859(1)nm, α=62.45(1),β=83.78(1), γ=78.52(1)°, Z=2,D~c=1.298 g.cm~-~3, R=0.062。晶体结构测定结果表明: 化合物KL由钾离子和配体负离子组成, K~+与配体L中的B原子相距0.3634nm, 在配体负离子中B原子与三个吡唑环的N原子及H原子形成四面体构型。化合物CuL~2由孤立分子组成, 铜离子处于分子的对称中心且与两个配体分子中的六个N原子形成六配位的八面体构型, 并表现出明显的Jahn-Teller效应。     

catena‐Poly[[dicyanamido(5,5′‐dimethyl‐2,2′‐bipyridine‐κ2N,N′)copper(II)]‐μ‐dicyanamido‐κ2N1:N5]

In the crystal structure of the title compound, [Cu(C₂N₃)₂(C₁₂H₁₂N₂)]_n, the Cu^II atom adopts a distorted square‐pyramidal geometry, the basal plane of which is formed by two N atoms of the bi­pyridine ligand, one N atom of a bidentate dicyan­amide anion and one N atom of a monodentate dicyan­amide anion [Cu—N = 1.9760 (15)–2.0157 (15) Å]. The apical position is occupied by an N atom of a bidentate dicyan­amide anion, located 2.2468 (16) Å from the Cu atom, thus forming a one‐dimensional polymeric chain.     

Poly­[[(pyridazine-κN)copper(I)]-μ3-thio­cyanato-κ3N:S:S]

In the crystal structure of the title compound, [Cu(NCS)(C₄H₄N₂)]_n, each Cu atom is coordinated by one N atom of one pyridazine ligand and by one N and two S atoms of three symmetry-related thio­cyanate anions within a distorted tetrahedron. Only one N atom of the pyridazine ligand is involved in Cu coordination. The Cu atoms are connected via the thio­cyanate anions, forming layers parallel to the ab plane.     

Cu(II)-氨基酸-核苷酸三元配合物的合成和表征

合成和表征Na~2[Cu(L-Ala)~2(5'-GMP)].2H~2O、Na~2[Cu(L-Ala)~2(5'-IMP)].6H~2O、Na~2[Cu(L-His)(5'-GMP)Cl~2^2.2H~2O和Na~2[Cu(L-His)(5'-IMP)Cl~2].H~2O四个新的三元配合物, 其中两个L-Ala分子通过羧基O和α-氨基N与Cu(II)成反式配位, 一个L-His分子通过羧基O和咪唑环上的N与Cu(II)配位; 一个5'-GMP或5'-IMP分子嘌呤环上的N(7)与Cu(II)配位; 5'-GMP的磷酸根上可能存在强氢键, 而5'-IMP的磷酸根上不存在强氢键; 在含L-Ala三元配合物中, 5'-GMP的C(6)=0可能参与配位或形成强氢键, 而5'-IMP的C(6)=0不参与配位或形成配位或形成强氢键; 在含L-His三元配合物中, 5'-IMP的C(6)=0的表现则相反。     

catena‐Poly­[[bis­[μ‐1,2‐bis(1‐methyl­tetrazol‐5‐yl)­ethane‐κ2N4:N4′]bis[chloro­copper(II)]]‐di‐μ‐chloro]

In the title compound, [Cu₂Cl₄(C₆H₁₀N₈)₂]_n, the ligand has C₂ symmetry, and the Cu and Cl atoms lie on a mirror plane. The coordination polyhedron of the Cu atom is a distorted square pyramid, with the basal positions occupied by two N atoms from two different ligands [Cu—N = 2.0407 (18) Å] and by the two Cl atoms [Cu—Cl = 2.2705 (8) and 2.2499 (9) Å], and the apical position occupied by a Cl atom [Cu—Cl = 2.8154 (9) Å] that belongs to the basal plane of a neighbouring Cu atom. The [CuCl₂(C₆H₁₀N₈)]₂ units form infinite chains extending along the a axis via the Cl atoms. Intermolecular C—H⃛Cl contacts [C⃛Cl = 3.484 (2) Å] are also present in the chains. The chains are linked together by intermolecular C—H⃛N interactions [C⃛N = 3.314 (3) Å].     

[N‐(2‐Hydroxy­ethyl)ethyl­enediamine‐κ3N,N′,O]‐cis‐bis(isothio­cyanato‐κN)copper(II)

In the novel transition metal isothio­cyanate complex of N‐(2‐hydroxy­ethyl)ethyl­enediamine (hydet‐en) with copper, [Cu(NCS)₂(C₄H₁₂N₂O)], the Cu atom lies in a distorted square‐pyramidal environment, coordinated by four N atoms in the basal plane and an apical O atom. The hydet‐en ligand is N,N,O‐tridentate, in contrast to the disposition in previously studied complexes, while the isothio­cyanate ions act as N‐atom donor ligands. The monomeric units are linked to one another by hydrogen bonds.     

A three‐dimensional supramolecular network built with the zigzag chain complex bis(5‐carboxy‐1H‐imidazole‐4‐carboxyl­ato)copper(II)

In the title complex, poly[copper(II)‐di‐μ‐5‐carboxy‐1H‐imidazole‐4‐carboxyl­ato], [Cu(C₅H₃N₂O₄)₂]_n or [Cu(H₂Imda)₂]_n, each imidazole moiety is bonded to the Cu atom via O and N atoms to give a square‐planar coordination [Cu—O = 2.014 (2) and 2.016 (2) Å, and Cu—N = 1.982 (3) and 1.992 (2) Å]. The distorted square‐pyramidal geometry at the Cu atom results from coordination to an adjacent O atom [Cu—O = 2.305 (2) Å], which generates zigzag chains. There is a sixth, weaker, octahedral coordination to the Cu atom from an inversion‐related O atom [Cu—O = 3.090 (2) Å], which links the chains into sheets in the (100) plane. Imidazole moieties in the sheets are linked in the [100] direction by pairs of N—H⋯O and C—H⋯O hydrogen bonds, thus generating a three‐dimensional network.     

Bis­[bis­(pyrimidin‐2‐yl‐κN)­amine](dicyan­amido‐κN1)(tri­fluoro­methanesulfonato‐κO)copper(II) ethanol hemisolvate forms a hydrogen‐bonded chain

In the crystal structure of [Cu(CF₃SO₃)(C₂N₃)(C₈H₇N₅)₂]·0.5C₂H₆O, the Cu^II atom adopts a distorted octahedral geometry, with the basal plane formed by two N atoms of one dipyrimidinyl­amine ligand, one N atom of the second pyrimidine ligand and a nitrile N atom of the dicyan­amide anion [Cu—N = 1.972 (2)–2.021 (2) Å]. The apical positions are occupied by an N atom of the second ligand [Cu—N = 2.208 (2) Å], and an O atom of the tri­fluoro­methane­sulfonate anion [Cu—O = 2.747 (2) Å] at a semi‐coordination distance. Pairs of inversion‐related N—H⋯N hydrogen bonds of the so‐called Watson–Crick type, augmented by two C—H⋯N contacts, link adjacent complexes into an infinite one‐dimensional chain running in the [101] direction.     

由己二酸根桥联的新颖双U形四核铜配合物: [Cu4(phen)4(NO3)2(H2O)2(adip)4/4(Hadip)4/2](NO3)2&#8226;2H2O

邻菲罗啉、己二酸和硝酸铜在水溶液中反应得到一种新颖的四核铜配合物[Cu4(phen)4(NO3)2(H2O)2- (adip)4/4(Hadip)4/2](NO3)2&#8226;2H2O (其中H2adip＝己二酸), 并经元素分析, IR, UV, TG和X射线单晶衍射分析表征. 该配合物晶体属三斜晶系, 空间群, a＝1.0146(2) nm, b＝1.0261(2) nm, c＝1.8285(4) nm, α＝91.66(3)°, β＝92.19(3)°, γ＝112.76(3)°, V＝1.7520(6) nm3, Z＝1, Dc＝1.639 g/cm3, C66H66Cu4N12O28, Mr＝1729.47, F(000)＝886, μ＝1.294 mm－1, R1和wR2分别为0.0447和0.1141. 己二酸根通过4个羧基O将两个U形双核亚单元联接成具有一个对称中心的双U形四核结构, 其中每个U型亚单元包含晶体学上不对称的2个Cu(II)原子. 每个Cu(II)离子均处于畸变的四方锥配位环境, 除与己二酸氢根(Hadip)、己二酸根(adip)和邻菲罗啉(Phen)的N, O配位形成锥底平面外, 其中的1个Cu(II)与水配位, 而另一个Cu(II)则与硝酸根配位. 配合物晶体结构中存在着广泛的氢键和p×××p作用.     

The copper(II) acetate complex with 2-(2-Hydroxyphenyl)-4,4-diphenyl-1,2-dihydro-4H-3,1-benzoxazine

The Cu(II) acetate complex with 2-(2-hydroxyphenyl)-4,4-diphenyl-1,2-dihydro-4H-3,1-benzoxazine (L) was synthesized for the first time and structurally studied by X-ray diffraction. The complex crystallizes as two crystallographically independent centrosymmetric binuclear molecules [Cu₂(μ-L)₂Ac₂] of similar structure, where L occurs as azomethin tautomeric form. The ligand performs tridentate chelate-bridging function. Each Cu atom exhibits extended tetragonal-pyramidal coordination by two O atoms and the N atom of one ligand L in the equatorial plane and by the O atom of the second ligand L in the axial position. The fourth equatorial position in the metal coordination polyhedron is occupied by the O atom of monodentate terminal acetate group.     

Crystal structure of [[mu-bis(salicylidene)-1,3-propanediaminato]copper(II)]dibromozinc(II).

The title compound is a double oxygen-bridged dimeric heteronuclear metal complex. The coordination around the Cu atom is distorted square-planar involving two O and two N atoms from the bis(salicylidene)-1,3-propanediamine ligand. The Zn atom in the molecule has a distorted tetrahedral coordination sphere consisting of the two O atoms of the ligand and the two Br atoms. The bridging plane between the metal atoms is not planar.