Crystal structure and magnetic properties of bis(2,2′-bipyridine) azido copper(II) perchlorate

The title compound has been synthesized and its crystal structure has been solved at room temperature. It crystallizes in the triclinic system, space groupP, witha=7.853(1) Å,b=10.177(1) Å,c=13.651(4) Å,=74.57(1)°,=88.49(1)°, =80.675(4)°, andZ=2. The structure consists of isolated [Cu(bipy)₂N₃]⁺ cations (bipy=2,2-bipyridine) and perchlorate anions. The metallic cation environment has a distorted trigonal-bipyramidal geometry. The EPR spectrum is rhombic, which indicates that the distortion with respect to the perfect trigonal bipyramid is sufficiently pronounced to mixz ²- andx ²–y ²-type orbitals in the ground state. The temperature dependence of the molar magnetic susceptibility has been investigated in the 300-2.2 K temperature range.     

Crystal and molecular structure of aqua(2,2′-bipyridine)bis(betaine)copper(II) perchlorate monohydrate

A new monomeric copper(II) complex with 2,2-bipyridine (bpy) and betaine (bet), [Cu(byy)(bet)₂(H₂O)](ClO₄)₂ · H₂O, has been prepared and characterized by X-ray crystallography. The complex crystallizes in the triclinic space groupP-1 witha=8.859(2),b=11.191(2),c=14.850(3) Å, =91.41(1), =97.19(1), =91.97(1)°,V=1459.2(7) ų, andZ=2. The structure comprises discrete cations [Cu(bpy)(bet)₂(H₂O)]²⁺ in which the metal atom is coordinated in a distorted square-pyramidal environment by two oxygen atoms from a pair of monodentate carboxylato ligands [Cu–O=1.950(2) Å] and two nitrogen atoms of a bidentate bpy ligand [Cu–N=1.997(3)–2.005(3) Å] on the basal plane, and one aqua [Cu–O=2.267(3) Å] ligand at the apical position.     

Synthesis and crystal structure of bis(2,2′-bipyridyl)mononitritozinc(II) perchlorate. An example of a six-coordinate cis-octahedral ZnN4O2 chromophore

The crystal structure of bis(2,2-bipyridyl)mononitritozinc(II) perchlorate, [Zn(bipy)₂ (ONO)][ClO₄] (1) has been determined. The complex is monoclinic, with a = 10.9195(4) Å, b = 12.2320(5) Å, c = 16.5477(8) Å, = 105.6150(10), P2₁/n space group, with final R1 = 0.0657 and wR2 = 0.1630. The complex involves a [Zn(bipy)₂ (ONO)]⁺ cation and a [ClO₄]^– anion. The ZnN₄O₂ chromophore is six-coordinate, with a cis-distortion of the two oxygens of the nitrite, O(1) and O(2), at distances 2.216(5) and 2.197(5) Å from the zinc (Zn– O _mean = 2.206(5) Å, O = 0.019(5) Å) and two out of plane Zn–N bonds, Zn–N(2) and Zn–N(3), at 2.129(4) and 2.135(4) Å (Zn–n _mean/out = 2.132(4) Å, n _2,3 = 0.006(4) Å). The two inplane nitrogens, N(1) and N(4), at distances Zn–N(1) = 2.090(4) and Zn–N(4) = 2.085(4) Å (Zn–n _mean/in = 2.087(4) Å, n _1,4 = 0.005(4) Å) are greater than 2.0 Å, but slightly shorter than the axial bonds. The inplane angles ₁, ₂, and ₃ in 1 have values 150.33(18), 108.98(17), and 99.73(18) respectively. The stereochemistry is cis-distorted octahedral, with an ₃ = 99.37(18), which is lower than ₃ = 103.4(1) observed in [Zn(bipy)₂(ONO)][NO₃] (5). Comparison with the corresponding [Cu(bipy)₂(ONO)][Y] complexes suggested that the cis-distortion of the CuN₄O₂ chromophore in the copper(II) series does not originate in the Jahn–Teller or pseudo-Jahn–Teller effect.     

Synthesis and characterization of ternary L-histidine complexes. Crystal structure of (2,2′-dipyridyl)-(L-histidinato-N,N′,O)copper(II) perchlorate 1.5 hydrate

A series of ternary complexes of copper(II), cobalt(II) and zinc(II) with L-histidine, 1,10-phenanthroline, 2,2-dipyridyl or imidazole having perchlorate or acetate as counterions were synthesized and characterized by conventional methods and for [Cu(bipy)(L-hist)]ClO₄·1.5H₂O and X-ray crystal structure was determined. The crystals belong to the monoclinic space groupC2 witha=18.843(3),b=10.582(2),c=11.020(2), =115.20(10)°,Z=4,R=0.0535. The structure is consistent of [Cu(bipy)(L-hist)]⁺ cations, perchlorate ions and water molecules. The geometry around copper is trigonal bipyramidal with one N,N,O tridentate L-histidine molecule and one 2,2-dipyridyl ligand, the apical sites are occupied by the -amino nitrogen [Cu–N(71) 1.995(8)] and by N(11) of 2,2-dipyridyl [Cu–N(11) 1.983(7)], the equatorial plane is formed by the N(3) imidazole -nitrogen [Cu–N(3) 2.140(6)], O(82) carboxylic oxygen [Cu–O(82) 2.009(5)] and N(22) [Cu–N(22) 2.010(7)].     

Synthesis, spectroscopy, and X-ray structure of the polymer catena-[bis(azido-N)-copper(II)-μ-bis(2-benzimidazolyl)butane]

The title compound, catena-[bis(azido-N)-copper(II)-(bis(2-benzimidazolyl)butane), [Cu(C₁₈H₁₈N₄)(N₃)₂]_n, was obtained from the reaction of the ligand bis(2-benzimidazolyl)butane and Cu(N₃)₂. The x-ray crystal structure is reported. The compound crystallizes in the monoclinic space group P2₁/c with a = 8.2524(10), b = 12.765(5), c = 9.1125(15) Å, = 106.423(12)°, Z = 2. The Cu(II) ions are square-planar coordinated with trans-oriented end-on binding azido ligands. The structure is a polynuclear chain with the benzimidazole bridging at each end. In addition a N_(ligand)-H···N_(azido) H-bridge [N_(ligand)···N_(azido) = 2.994(7) Å] is present, resulting in a pseudo 2-dimensional lattice. The characteristic azido infrared vibrations are found at 2060 and 2077 cm^–1 (_as(N₃)) and 1284 and 1297 cm^–1 ((N₃)).     

Synthesis and crystal structure of 1,1′-di(ethylpropionato)-2,2′-biimidazole, a macromolecular precursor

1,1,-Di(ethylpropionato)-2,2-biimidazole, C₁₆H₂₂N₄O₄, crystallizes from ice-cold ethanol in the space group P , with a = 4.6742(9), b = 9.1119(13), c = 10.175(2) Å, = 96.22(1), = 96.29(2), = 97.53(1)°, and Z = 1. The molecule crystallizes with coplanar rings and the substituents assume a trans conformation with a center of inversion between the bridging carbon atoms.     

Synthesis and crystal structure of the perchlorate salt of diprotonated N,N′-bis(1-methylimidazole-2-methyl)1,5-diazacyclooctane

The diprotonated perchlorate salt of a new 1,5-diazacyclooctane (DACO) mesocycle functionalized by two imidazole pendants, N,N-bis(1-methylimidazole-2-methyl)-1,5-diazacyclo-octane (C₁₆H₂₈N₆Cl₂O₈), has been synthesized and the structure determined by X-ray diffraction analysis. The title compound crystallizes in the monoclinic system, space group P2₁/c with a = 11.964(2), b = 13.251(3), c = 14.741(3) Å, = 106.00(3)°, Mr = 503.34, V = 2246(1) ų, Z = 4. The crystal structure of the title compound reveals that the DACO ring is also folded up into the chair/boat configuration, which is consistent with the configuration in most of the transition metal complexes of DACO and its derivatives. The two imidazole pendants of the compound are in cis position with a dihedral angle of 16.0(4)°.     

Synthesis, spectral, and single crystal X-ray structural studies on (2,2′-bipyridyl)bis(dimethyldithiocarbamato) zinc(II) and (1,10-phenanthroline) bis(dimethyldithiocarbamato)zinc(II)

Synthesis, spectral, and single crystal X-ray structural studies on (2,2-bipyridyl)bis (dimethyldithiocarbamato)zinc(II) (1) and (l,10-phenanthroline)bis(dimethyldithiocarbamato)zinc(II) (2) complexes are reported in this paper. The complex (1) crystallizes in the orthorhombic lattice, space group Pcca, a = 18.456(3), b = 6.529(2), and c = 17.092(2) Å. The complex (2) crystallizes in the monoclinic space group C2/c, a = 13.372(2), b = 13.850(2), c = 24.680(3) Å, and = 102.71(4)°. IR spectra of the complexes (1) and (2) show the thioureide (C-N) bands at 1489 and 1510 cm^–1, respectively, which are lower than the value observed for the parent bisdithiocarbamate. Reduction in the thioureide stretching frequency is due to the increase in coordination around the zinc ion and the resultant increase in electron density. Thermal studies indicate that the 1,10-phenanthroline adduct is marginally more stable than the other complex. X-ray crystal structures of the two adducts show them to be octahedrally coordinated and monomeric in nature. The Zn-S distances are longer than those observed in the parent bisdithiocarbamate. The thioureide C-N bond distances in (1) and in (2) indicate the partial double bond character. The most important structural changes as a result of the adduct formation are observed in the Zn-S bond distances and S-Zn-S bond angles, in terms of very significant increases in Zn-S bond distances and reductions in S-Zn-S angles, compared to the parent bisdithiocarbamate. The observed changes are indicative of a strong steric force in operation in the adducts rather than electronic effects.     

Synthesis and structure of [(nitrito-O,O′) bis(di-2-pyridylamine)copper(II)] nitrite

The synthesis and molecular structure of the title compound, [(nitrito-O,O) (dpa)₂Cu(II)] (NO₂), 1, is reported. Compound 1 crystallized in the orthorhombic space group Pccn with a = 11.397(5) Å, b = 12.256(6) Å, c = 14.876(8) Å, and V = 2077.9(17) ų with Z = 4. The distorted octahedral copper(II) cations are linked through a hydrogen-bonded polymer network. The polymer network is formed through the amine N–H of the cations and hydrogen bonded to the N–HO nitrite anions.     

X-ray crystal structure of the copper(II)bis(2,2′-dipyridyl)dithiocarbamate,produced by an unusual reaction of CS2 with Cu−N bonds

The title compound was obtained from a CS₂ solution of bis(2,2-dipyridylamido)copper(II), by insertion of solvent into this complex. In the structure of the dithiocarbamate the metal atom is approximately square-planar coordinated by four S atoms from two chelating ligands. Considering the long interactions between the metal center and the S(2) atom from a centrosymmetrically related complex [Cu(1)...S(2)=3.230 Å], double bridged dimers are formed with the copper atoms in an elongated square-pyramidal coordination. The crystals are monoclinic, space groupP2 ₁/n witha=14.549(3),b=11.662(3)c=15.329(4) Å and =114.79(2)°.     

The synthesis and crystal structure of one novel ternary complex of 2,2′-bipyridine N-salicylidenetyrosinatocopper(II)

The crystal structure of copper(II)—salicylidene-aminoacidate Schiff base—nitrogen-donor chelating ligand, [Cu(sal-tyr)(bipy)] (sal-tyr: N-salicylidenetyrosinato; bipy: 2,2-bipyridine) which is obtained by means of one-step synthesis, is presented. It crystallizes in space group P2₁2₁2₁ with a = 9.0356(18) Å, b = 11.992(2) Å, c = 20.618(4) Å. The Cu^II ion is five coordinated by one oxygen atom of carboxylate, the imine nitrogen atom, and the hydroxyl oxygen atom of the salicylidene in the Schiff base anion as well as two nitrogen atoms of bipy, resulting in a seriously distorted square pyramid coordination polyhedron. The phenol group and the apical coordination bond Cu(1)–N(2) are in the same side of the Schiff base chelating plane which could be attributed to the intramolecular C–H s interaction between the H(17) of the bipy and the benzene ring of the phenol. The hydrogen bond between the hydroxyl hydrogen atom of the phenol group and the coordinated oxygen atom of the carboxylate from neighboring molecule is helpful to stabilize the crystal.     

Synthesis and crystal structure of iodo-1-(2′-aminophenyl)-2,6-diaza-6-methyl-9-amino-1-noneno copper(II) iodide

Reaction of equimolar amounts of 2-aminobenzaldehyde and 3,3-diamino-N-methyldipropyl-amine in methanol affords a novel 11 condensation product, abaMedpt, which has been isolated as the copper(II) complex, [Cu(abaMedpt)I]I. The crystal structure of the complex has been determined from single crystal diffractometer data and refined to a finalR factor of 0.0353 with 2492 unique observations and 206 variables. The complex crystallizes in the monoclinic space group P2₁/c (N° 14) witha=9.263(2),b=18.189(3),c=11.740(3) Å,=92.97(4)°,Z=4,D _c =1.902 g cm^–3. The structure involves a five-coordinate square-pyramid CuN₄I chromophore and an uncoordinated iodide anion. Nitrogen atoms constitute the basal plane, while the bonded iodine occupies the apical position. The structure contrasts with the more usual distorted trigonal-bipyramidal stereochemistries of CuN₄I chromophores reported so far.     

The crystal structure and IR spectra of μ-(bipyrimidine-N1,N1′,N5,N5′)-bis[(azido-N1)(methanol)(bipyrimidine-N1,N1′)copper(II)] bis(triflate) bis(methanol)

The structure of the title compound [Cu₂(bipym)₃(N₃)₂(CH₃OH)₂](CF₃SO₃)₂(CH₃OH)₂ has been determined by X-ray diffraction. The crystals are triclinic, space group P1, with a = 8.1844(5), b = 11.0253(6), c = 12.9089(7) Å, = 80.249(4), , = 74.933(5), = 74.001(4)°, and Z = 1. The structure consists of a dinuclear Cu(II) unit formed of two didentate bipym ligands, one bis-didentate bipym ligand, two azido anions, and two coordinating methanol molecules. The Cu(II) atom is elongated tetragonally surrounded by two nitrogens of the didentate bipym ligand, one nitrogen of the bis-didentate ligand, and one nitrogen of the azido anion forming the equatorial plane with one nitrogen of the bis-didentate ligand and an oxygen atom of the methanol molecule as the axial atoms. A noncoordinating triflate anion and an additional methanol molecule are also in the crystal lattice and have a hydrogen bond distance of 2.801(3) Å with an angle of 157(4)°. The cations link by O – H ··· N bonds into infinite chains running in the c-direction.     

Synthesis and crystal structure of N,N′-dicyclohexylimidazolium hexafluorophosphate

N,N-dicyclohexylimidazolium hexafluorophosphate was prepared and its structure was determined by X-ray diffraction. The compound crystallizes in the orthorhombic space group Pbca, with the cell dimensions of a = 14.620(3) Å, b = 15.097(3) Å, c = 16.128(3) Å, V = 3559.4(12) ų, and D _calc. = 1.412 mg/m³ for Z = 8. The structure was solved by direct methods and refined to R value of 0.041. In the solid state, PF₆ ^– anion and imidazolium cation form strong hydrogen bonds, which fix the relative orientation between cations and anions.     

Synthesis and crystal structure of Nd(III)–Zn(II) complex

A novel heteronuclear complex, [NdZn₂L₆(NO ₃)(phen)₂] (HL = -methylacrylic acid, phen = 1,10-phenanthroline), was synthesized and characterized by elemental analysis, infrared absorption spectra (IR) and its molecular structure was also determined by X-ray structure analysis. The title complex contains a discrete trinuclear ZnNdZn molecule bridged by carboxylate groups between Zn and Nd ions and crystallizes in space group P¯1 with the cell dimensions: a = 13.601(3) Å, b = 16.859(2) Å, c = 12.575(2) Å, = 110.09(1), = 112.21(1), = 81.10(2).     

The X-ray crystal structures of bis(l-α-alaninehydroxamato)nickel(II) and bis(l-α-alaninehydroxamato)copper(II)

The structure of twol--alaninehydroxamato (-Alaha) complexes of Ni(II) and Cu(II) have been determined by single-crystal X-ray diffraction methods. The crystals of Ni(-Alaha)₂·2H₂O (I) are monoclinic witha=12.267(4),b=4.798(2),c=10.017(4)Å,=95.48(3)°,Z=2, and space groupP2₁. The crystals of Cu(-Alaha)₂·2H₂O (II) are monoclinic witha=5.073(2),b=11.463(3),c=20.198(5) Å,Z=4 and space groupP2₁2₁2₁. The values of the final residualsR for Ni(-Alaha)₂·2H₂O and Cu(-Alaha)₂·2H₂O are 0.06 and 0.03, respectively. The molecular structures of Ni(-Alaha)₂ and Cu(-Alaha)₂ consist of a square planar and a pentanuclear piramidal, respectively, with the-alaninehydroxamato, (CH₃CH₂(NH₂)CONOH^–), ligands coordinating to metal ion via the N(amino) and the hydroxamic N^– donors.     

Structure of the adduct of bis(2,2′biimidazole)copper(II) perchlorate with 4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidine-7-one

The crystal structure of the compound [Cu(biim)₂](ClO₄)₂(7HtpO)₂ (where 7HtpO is 4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidine-7-one and biim is 2,2'biimidazole) has been determined at room temperature. The dark green crystals are monoclinic, space group C2/c with unit dimensions a = 19.666(2) Å, b = 11.7586(8) Å, c = 13.4808(9) Å, = 103.690(8)°, Z = 4, and Dx = 1.761 Mg-m^–3. The structure was refined by a full-matrix least-squares procedure on F ² to final R = 0.0806 using 4407 reflections. The cation is slightly distorted square planar and 7HtpO is not directly linked to the metal, the interaction between the cation and the triazolopyrimidine moiety taking place via stacking.     

5(2′Carboxy)phenylazo barbiturate diaqua copper(II) trihydrate: Characterization and crystal structure

The title compound has been synthesized and characterized by standard spectroscopic techniques and magnetic susceptibility measurements and its structure has been determined by monocrystal X-ray diffraction. The complex crystallizes in the monoclinic space groupP2₁/c in a cell of dimensionsa=11.432(3),b=6.927(2),c=21.289(8)Å,=106.54(4)°,V=1616.1(9)ų,D _c =1.758 Mg m^–3,D(flotation)=1.76 Mg m^–3,M _w =427.8, (CuK)=2.47 mm^–1,F(000)=876. The structure refined to a finalR of 0.041 for 1290 observed independent reflections. The copper atom is coordinated by the nitrogen atom of the azo group next to the phenyl ring, the oxygen atom of one of the carbonyl groups of the barbituric moiety and one of the oxygen atoms of the carboxylate, closing two six-member chelate rings. Two water molecules complete a typical 4+1 square-based pyramidal environment.     

Synthesis and crystal structure of 7-ethoxyl-4′-hydroxyisoflavone

7-Ethoxyl-4-hydroxyisoflavone was prepared and its crystal structure was examined by X-ray diffraction. Crystallization of the title compound occurs in the monoclinic, space group P2(1)/c with a = 11.144(2) Å, b = 10.209(1) Å, c = 13.191(2) Å, = 113.43(1) and Z = 4. The molecular structure of title compound consists of a benzopyranone moiety, a phenyl moiety, a hydroxyl and an ethoxyl group. The benzopyranone ring is not coplanar with the phenyl ring, the dihedral angle being 46.75. The ethoxyl group is nearly coplanar with its corresponding ring with the torsion angle 175.23(2). Three kinds of hydrogen bond and two kinds of aromatic stacking interaction link the title compounds into a three-dimensional networking structure.     

Crystal and molecular structure,and infrared study of bis(2,2′-bipyridine) [N-(toluene-p-sulfonyl)glycinato-NO] cadmium(II) complex and related compounds

A series of complexes of formula [M(II)(bpy)₂(ArSO₂-N-aminoacidato-NO)]·3H₂O [bpy=2,2-bipyridine, M(II)=Zn(II), ArSO₂-N-aminoacidato-NO=N(toluene-p-sulfonyl)- and N(benzenesulfonyl)-glycinate-NO dianion, hereafter abbreviated as tsgly-NO and bsgly-NO, respectively, M(II)=Cd(II), ArSO₂-N-aminoacidato-NO=tsgly-NO] was separated and investigated by spectroscopic and X-ray methods. The crystal structure of [Cd(bpy)₂(tsgly-NO)]·3H₂O was determined. The compound crystallizes in the monoclinic space groupP2/n,Z=4,a=15.427(4),b=13.580(2),c=15.546(4)Å, =110.97(3),R=0.041,R _w =0.043. The structure consists of monomeric, approximately octahedral [Cd(bpy)₂(tsgly-NO)] units with a N₅O donor atom set, which gives rise to three almost orthogonal five-membered chelate rings. The IR spectra suggest similar environments for all the complexes.