CuII Atom Research Articles

Bis[2-(hydroxyimino)cyclohexan-1-one oximato-κ2N,N′]copper(II)

In the title compound, [Cu(C6H9N2O2)2], the CuII atom is located on an inversion center and has a square-planar environment. Two 2-(hy­droxy­imino)­cyclo­hexan-1-one oxim­ate monoanions chelate to the CuII atom and the Cu—N distances are 1.920 (3) and 1.930 (3) Å. There are two short intra­molecular O—H⋯O hydrogen bonds between the ligands. The complex mol­ecules stack into columns extended along the c axis, with a Cu⋯Cu distance between adjacent mol­ecules of 3.3060 (3) Å.

Catena-Poly[[copper(I)-μ-2,6-bis[4-(pyridin-2-yl)thiazol-2-yl]pyridine] hexafluoridophosphate acetonitrile monosolvate] from single-crystal synchrotron data

The title complex, {[Cu(C21H13N5S2)]PF6·CH3CN}n, was formed immediately on adding together a methanol solution containing copper(I) ions and a methanol solution of 2,6-bis­[4-(pyridin-2-yl)thia­zol-2-yl]pyridine. Crystallographic studies of the complex reveal a coordination polymer with the ligand acting as a bis­(bidentate) ligand with the pyridine N atom not coordinating a metal centre. The CuI atom is four-coordinate with approximately tetra­hedral stereochemistry: the N4 donor set is provided by bipyridine-like moieties of the two heterocyclic ligands. Parallel chains of the coordination polymer run along the b-axis direction with the disordered (0.50:0.50 occupancy ratio) PF6 − anions and acetonitrile solvent mol­ecules located between the chains.

Dichloridobis(1,3-diisopropyl-4,5-dimethyl-1H-imidazol-3-ium-2-thiolate-κS)copper(II)

The mol­ecular structure of the title compound, [CuCl2(C11H20N2S)2], shows the CuII atom with a distorted tetra­hedral geometry from two Cl atoms [Cu—Cl = 2.2182 (6) Å] and two thione S atoms [Cu—S = 2.3199 (6) Å]. The angles at the copper cation, which lies on a twofold rotation axis, are Cl—Cu—Cl = 142.84 (4)°, Cl—Cu—S = 94.80 (2) and 99.97 (2)°, and S—Cu—S = 132.46 (4)°. The planes of the two imidazolium rings make a dihedral angle of 76.92 (8)°.

Poly[[diaquabis{μ-4-[6-(4-carboxyphenyl)-4,4′-bipyridin-2-yl]benzoato-κ2O:N1′}copper(II)] dimethylformamide tetrasolvate

In the title compound, {[Cu(C24H15N2O4)2(H2O)2]·4C3H7NO}n, the CuII ion, lying on an inversion center, is six-coordinated by two N atoms from two 4-[6-(4-carb­oxy­phen­yl)-4,4′-bipyridin-2-yl]benzoate (L) ligands, two deprotonated carboxyl­ate O atoms from two other symmetry-related L ligands and two water mol­ecules in a slightly distorted octa­hedral geometry. The CuII atoms are linked by the bridging ligands into a layer parallel to (101). The presence of intra­layer O—H⋯O hydrogen bonds and π–π inter­actions between the pyridine and benzene rings [centroid–centroid distances = 3.808 (2) and 3.927 (2) Å] stabilizes the layer. Further O—H⋯O hydrogen bonds link the layers and the dimethyl­formamide solvent mol­ecules.

Trans-Dibromidobis(3-methyl-pyridine-κN)copper(II).

The asymmetric unit of the title compound, [CuBr2(C6H7N)2], contains one half-mol­ecule, the whole mol­ecule being generated by inversion through a center located at the CuII atom. The geometry around the CuII atom is square planar. Semicoordinate Cu⋯Br bonds [3.269 (1) Å] and nonclassical C—H⋯Br hydrogen bonds connect the mol­ecules, forming chains running parallel to the a axis. These chains are further linked via additional C—H⋯Br hydrogen bonds into a three-dimensional network.

Four New Three-Dimensional Polyoxometalate-Based Metal–Organic Frameworks Constructed From [Mo6O18(O3AsPh)2]4– Polyoxoanions and Copper(I)-Organic Fragments: Syntheses, Structures, Electrochemistry, and Photocatalysis Properties

Four novel polyoxometalate-based copper(I)-organic frameworks, namely, [Cu(I)(2)(cis-L1)(2)][Cu(I)(2)(trans-L1)(2)Mo(6)O(18)(O(3)AsPh)(2)] (1), [Cu(I)(4)(L2)(4)Mo(6)O(18)(O(3)AsPh)(2)] (2), [Cu(I)(4)(L3)(4)Mo(6)O(18)(O(3)AsPh)(2)] (3), and [Cu(I)(4)(L4)(2)Mo(6)O(18)(O(3)AsPh)(2)] (4) (L1 = 1,3-bis(1,2,4-triazol-1-yl)propane, L2 = 1,4-bis(1,2,4-triazol-1-yl)butane, L3 = 1,5-bis(1,2,4-triazol-1-yl)pentane, and L4 = 1,6-bis(1,2,4-triazol-1-yl)hexane), have been successfully synthesized under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, infrared spectra (IR), UV-vis spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Compound 1 is composed of two crystallographically independent and distinct polymeric motifs: one-dimensional (1D) S-shaped chain and two-dimensional (2D) undulated layer. The S-shaped chains penetrated into the 2D parallel layers to generate an unusual 1D + 2D → three-dimensional (3D) polypseudo-rotaxane framework. In 2, the As(2)Mo(6) polyoxoanions in tetradentate modes link four neighboring -L2-Cu-L2- chains to produce a rare 3D trinodal (3,4)-connected self-penetrated framework with Point Symbol of (8(3))(2)(8(2)·12(4)). In 3, adjacent Cu(I) atoms are linked by As(2)Mo(6) polyoxoanions and L3 ligands into a 2D layer. The layers are further interlocked by the two nearest neighboring ones to form a 3D polycatenated framework. In 4, L4 ligands bridge four Cu(I) atoms to yield 2D wavelike layers, which are further linked by the octadentate As(2)Mo(6) polyoxoanions to form a 3D tetranodal (3,4,6)-connected framework with Point Symbol of (6(3))(4·6(3)·8(2))(6(4)·8(2))(4(2)·6(2)·8(10)·10). In addition, the photocatalytic activities of compounds 1, 3, and 4 for decomposition of methylene blue (MB) under UV light have been investigated. Moreover, their electrochemical properties have also been studied in 1 M H(2)SO(4) aqueous solution.

μ-N1,N2-Bis(pyridin-2-yl)hydrazine-1,2-dicarbothioamidato]bis[chloridocopper(II)

The binuclear title compound, [Cu2(C12H10N6S2)Cl2], possesses twofold rotational symmetry. The CuII atom occupies a four-coordinate pseudo-tetra­hedral environment bound to one S atom, one imine N atom and one pyridine N atom from the N 1,N 2-bis­(pyridin-2-yl)hydrazine-1,2-dicarbo­thio­amidate ligand, and one Cl− anion. The metal atoms are connected via the bis-tridentate ligand into a binuclear structure. The mol­ecule is bow-shaped with the pyridine rings inclined to one another by 51.56 (14)°. In the crystal, N—H⋯Cl hydrogen bonds lead to the formation of ribbons propagating along [001]. These ribbons are connected via C—H⋯Cl, C—H⋯S and π–π inter­actions [centroid–centroid distance = 3.6146 (19) Å], leading to the formation of a three-dimensional structure.

Tetra-kis[μ-2-(meth-oxy-carbon-yl)benzoato-κ(2) O (1):O (1')]bis-[(acetonitrile-κN)copper(II)](Cu-Cu).

In the binuclear copper(II) title complex, [Cu2(C9H7O4)4(C2H3N)2], an inversion centre is situtated at the mid-point of the Cu—Cu bond. The CuII atom together with its four coordinated O atoms are in a distorted planar square arrangement while the nitro­gen and the other CuII atom are located in apical positions. The whole mol­ecule looks like a paddle-wheel. In the crystal, chains are assembled along the b axis through C—H⋯O hydrogen bonds and slipped π–π inter­actions between the benzene rings of neighbouring mol­ecules [centroid–centroid distance = 3.6929 (3) Å and slippage = 0.641 (1) Å].

(Nitrato-κ2O,O′)bis(1,10-phenanthroline-κ2N,N′)copper(II) tricyanomethanide

The title compound, [Cu(NO3)(C12H8N2)2][C(CN)3], is formed of discrete [Cu(NO3)(phen)2]+ complex cations (phen is 1,10-phenanthroline) and C(CN)3 − counter-anions. The CuII atom has an asymmetric tetragonal–bipyramidal (4 + 1+1) stereochemistry with a pseudo-C 2 symmetry axis bis­ecting the nitrate ligand and passing through the CuII atom between the two phen ligands. The four N atoms of the phen ligands coordinate to the CuII atom with Cu—N distances in the range 1.974 (2)–2.126 (2) Å, while the two O atoms coordinate at substanti­ally different distances [2.154 (2) and 2.586 (2) Å]. The structure is stabilized by C—H⋯O hydrogen bonds and weak π–π inter­actions between nearly parallel benzene and pyridine rings of two adjacent phen mol­ecules, with centroid–centroid distances of 3.684 (2) and 3.6111 (2) Å, and between π-electrons of the tricyano­methanide anion and the pyridine or benzene rings [N⋯(ring centroid) distances = 3.553 (3)–3.875 (3) Å].

Chlorido(4-methylpyridin-2-amine-κN1)(2-{[(4-methylpyridin-2-yl)imino-κN]methyl}phenolato-κO)copper(II)

In the title complex, [Cu(C13H11N2O)Cl(C6H8N2)], the CuII atom adopts a distorted tetra­hedral geometry being coordinated by the phenolic O atom and the azomethine N atom of the Schiff base ligand N-salicyl­idene 2-amino­pyridine, and by the 2-amino­pyridine N atom and a Cl atom. The pyridyl N atom of the Schiff base and the imino N atom of the 4-methyl-pyridine-2-yl­imino ligand are not involved in the coordination. There is an intra­molecular N—H⋯N hydrogen bond involving the pyridine N atom and the amino group of the 2-amino­pyridine ligand. In the crystal, mol­ecules are linked via N—H⋯Cl hydrogen bonds, forming chains propagating along [001].

CunXn]‐Based Coordination Polymers with Bis(4‐iodo‐1H‐pyrazol‐1‐yl)methane and Bis(4‐iodo‐3, 5‐dimethyl‐1H‐pyrazol‐1‐yl)methane: Solvothermal Syntheses, Crystal Structures, and Luminescent Properties

AbstractSolvothermal reactions of CuX (X = Cl, Br, I, CN) with bis(4‐iodo‐1H‐pyrazol‐1‐yl)methane (ipzm) or its methyl‐substituted derivative bis(4‐iodo‐3, 5‐dimethyl‐1H‐pyrazol‐1‐yl)methane (idmpzm) resulted in the formation of three 2D [Cu2X2]n‐based coordination polymers [{Cu(μ‐X)}2(μ‐ipzm)]n [X = Cl (1), Br (2), I (3)], four 1D [CuX]n‐based coordination polymers [{Cu(μ‐CN)}2(μ‐ipzm)]n (4), [{(idmpzm)Cu}(μ‐Cl)]n (5), [{(idmpzm)Cu}(μ‐Br)·MeCN]n (6), [{(idmpzm)Cu}(μ‐I)·0.5MeCN]n (7), and one 1D [Cu6(CN)6]n‐based coordination polymer [{Cu(μ‐CN)}6(idmpzm)3]n (8). Compounds 1–8 were characterized by elemental analysis, IR spectra, and single‐crystal X‐ray diffraction. Compounds 1–3 consist of an unique 2D layer structure, in which the 1D staircase [Cu2X2]n chains are linked by ipzm ligands via the μ‐η1(N)‐η1(N) coordination mode. In 4, two 1D zigzag [CuCN]n chains are linked by μ‐ipzm ligands to form a 1D double chain. Compounds 5–7 have a 1D split‐stair chain derived from connecting [Cu(idmpzm)] fragments via μ‐X (X = Cl, Br, I) bridges, whereas 8 exhibits a 1D scolopendra‐like chain assembled from a 1D [Cu6(CN)6]n chain with idmpzm ligands chelating on the outer central CuI atoms. The luminescence properties of 1–8 along with free ipzm and idmpzm ligands at ambient temperature were also investigated.

Catena-Poly[[[diaquacopper(II)]-bis[μ-1,5-bis(1H-imidazol-1-yl)pentane-κ2N3:N3′]] naphthalene-1,5-disulfonate

In the title complex, {[Cu(C11H16N4)2(H2O)2](C10H6O6S2)}n, the CuII atom, lying on an inversion center, is six-coordinated by two water mol­ecules and four N atoms from four 1,5-bis­(1H-imidazol-1-yl)pentane (biim-5) ligands in a distorted octa­hedral geometry. Adjacent CuII atoms are linked by two biim-5 ligands, forming a chain along [111]. Two atoms of the pentane group are disordered over two sets of sites, with an occupancy ratio of 0.554 (18):0.446 (18). Inter­molecular O—H⋯O hydrogen bonds link the chains and the centrosymmetric naphthalene-1,5-disulfonate anions into a layer structure parallel to (0-11).

Poly[[μ-aqua-diaquabis(μ-furan-2,5-dicarboxylato-κ2O2:O5)bis(1,10-phenanthroline-κ2N,N′)dicopper(II)]N,N-dimethylformamide monosolvate

The asymmetric unit of the title compound, {[Cu2(C6H2O5)2(C12H8N2)2(H2O)3]·C3H7NO}n, contains two CuII atoms, two furan-2,5-dicarboxyl­ate (L) ligands, two 1,10-phenanthroline (phen) ligands, three coordinating water mol­ecules and one N,N-dimethyl­formamide solvent mol­ecule. Each CuII atom is coordinated by two N atoms from one phen ligand, two O atoms from two L ligands and two water mol­ecules in a distorted octa­hedral geometry. The main difference between the environments of the two independent Cu atoms is in the Cu—Owater distances, which are 2.415 (2) and 2.639 (2) Å for one CuII atom and 2.3560 (19) and 2.911 (4) Å for the other. Ligands L and one independent water mol­ecule bridge the CuII atoms, forming corrugated polymeric layers parallel to the ab plane. Inter­molecular O—H⋯O and C—H⋯O hydrogen bonds consolidate the crystal packing.

Bis(2-{[bis-(dimethyl-amino)-methyl-idene]amino-κN}benzene-sulfonato-κN)copper(II).

The mol­ecular structure of the title compound, [Cu(C11H16N3O3S)2], shows the CuII atom with a distorted square-planar coordination geometry from the N2O2 donor set of the two chelating 2-{[bis­(dimethyl­amino)­methyl­idene]amino}­benzene­sulfonate ligands. The CuII atom lies 0.065 (1) Å above the N2O2 plane and the Cu—O [2 × 1.945 (2) Å] and Cu—N bond lengths [1.968 (3) and 1.962 (3) Å] lie in expected ranges. The two aromatic ring planes make a dihedral angle of 85.48 (1)°.

{6,6′-Dimethoxy-2,2′-[cyclohexane-1,2-diylbis(nitrilomethanylylidene)]diphenolato}copper(II) monohydrate

In the title compound, [Cu(C22H24N2O4)]·H2O, the CuII atom is four-coordinated in a distorted planar geometry with a mean deviation of 0.1164 (2) Å for the plane generated by the ligating atoms of the salen-type Schiff base ligand. In the crystal, O(water)—H⋯O and C—H⋯O hydrogen bonds form a three-dimensional-network.

Di-μ2-acetato-1:2κ2O:O′;2:3κ2O:O′-bis{μ2-4,4′-dichloro-2,2′-[2,2-dimethylpropane-1,3-diylbis(nitrilomethanylylidene)]diphenolato}-1:2κ6O,N,N′,O′:O,O′;2:3κ6O,O′:O,N,N′,O′-tricopper(II)

The title compound, [Cu3(C19H18Cl2N2O2)2(CH3CO2)2], is a linear homo-trinuclear CuII complex. The central CuII atom is located on a centre of inversion and has a distorted octa­hedral coordination environment formed by six O atoms from two tetra­dentate Schiff base ligands and two bridging acetate ligands. The coordination geometry of the terminal CuII atom is square-pyramidal with a tetra­dentate ligand in the basal plane. The apical site is occupied by one O atom from an acetate ligand. The acetate-bridged Cu⋯Cu distance is 3.0910 (5) Å. An intra­molecular C—H⋯O hydrogen bond forms an S(6) ring motif. The crystal of the trinuclear complex is stabilized by C—H⋯O hydrogen bonds.

Catena-Poly[[[aqua(2,2′-bipyridine-κ2N,N′)copper(II)]-μ-furan-2,5-dicarboxylato-κ2O2:O5] dihydrate

In the crystal structure of the title compound, {[Cu(C6H2O5)(C10H8N2)(H2O)]·2H2O}n, an infinite chain parallel to [110] is formed by the linking of Cu(H2O)(2,2′-bipyridine) units through a furan-2,5-dicarboxyl­ate bridge. The CuII atom shows a square-pyramidal geometry, with one furan-2,5-dicarboxyl­ate O atom in the apical position. The dihedral angle between the planes of the furan ring and the bipyridine mol­ecule is 83.88 (7)°. Owater—H⋯O hydrogen bonds connect adjacent chains, generating a layer motif parallel to (001).

Hexa-kis-(μ(3)-1-methyl-thio-urea-κ(3)S:S:S)hexa-kis-[iodidocopper(I)

The title compound, [Cu6I6(C2H6N2S)6], was obtained from the reaction of copper(I) iodide with N-methyl­thio­urea (Metu) in equimolar amounts in acetonitile. The complex consists of two six-membered trinuclear Cu3S3I3 cores that combine through triply bridging Metu, forming a hexa­nuclear core which has -3 symmetry. The CuII atom is coordinated by three S atoms of Metu and one iodide ion in a distorted tetra­hedral geometry. The crystal structure is stabilized by N—H⋯I hydrogen bonds and cuprophilic inter­actions [Cu⋯Cu = 3.0264 (9) Å].

Bis[μ-(3-acetyl-2-hy-droxy-6-methyl-4H-pyran-4-one-κ(3)O:O',O'')]diaqua-tetra-kis-(pyridine-κN)dicopper(II) diperchlorate.

In the centrosymmetric binuclear cation of the title compound, [Cu(C8H7O4)(H2O)(C5H5N)2]2(ClO4)2, the CuII atoms are bridged by a pair of two dehydro­acetate anions in a bis-/monodentate mode. The distorted octa­hedral N2O4 coordination sphere of the metal cation is completed by two pyridine N atoms and one O atom of a water mol­ecule. The complex cations and the perchlorate counter anions are arranged in layers parallel to (100). O—H⋯O hydrogen bonds between the coordinating water mol­ecules and the perchlorate anions constitute ribbons parallel to [10-1]. C—H⋯O hydrogen bonds are also observed.

Bis(diphenyl-p-tolylphosphane-κP)(2-hydroxy-3,5,7-bromocyclohepta-2,4,6-trienonato-κ2O,O′)copper(I)

The CuI atom in the title compund, [Cu(C7H2Br3O2)(C19H17P)2], is located on a twofold rotation axis; the 3,5,7-tribromo­tropolonate anion coordinates as a bidentate ligand with a bite angle of 76.42 (9)°. An intra­molecular C—H⋯O inter­action occurs. Within the crystal, extensive weak C—H⋯π inter­actions contribute to the herringbone pattern observed in the packing of the mol­ecules.