Complexes in the Ni2+-imidazole-RN(CH2COO−)2 systems. The crystal structures of tris(imidazole)iminodiacetatonickel(II) monohydrate, hexa(imidazole)nickel(II) bis(N-methyliminodiacetato)nickelate(II) hexahydrate, and tetra(aqua)bis(imidazole)nickel(II) bis(N-benzyliminodiacetato)nickelate(II)

Crystals of different compositions, namely, [Ni(Ida)(Im)₃] ? H₂O (I), [Ni(Im)₆][Ni(Mida)₂] ? 6H₂O (II), and [Ni(Im)₂(H₂O)₄][Ni(Bida)₂] (III), have been precipitated from aqueous solutions of the Ni²⁺-Lig ^2?-Im systems, where Lig ^2? is Ida, Mida, and Bida, respectively. The crystal structures of I–III are determined by X-ray diffraction analysis (R = 0.0307, 0.0348, and 0.0302 for 3061, 4706, and 2882 reflections, respectively). Crystals I are built of monomeric mixed-ligand complexes and molecules of crystallization water, which are interlinked by hydrogen bonds into a three-dimensional framework. In II and III, the ligands Lig ^2? and Im form charged complexes separately. In II, the cationic and anionic layers of the complexes alternate along the c-axis. Numerous hydrogen bonds involving molecules of crystallization water link the layers into a three-dimensional framework. In III, the cationic and anionic complexes, which serve as proton donors and acceptors, respectively, are bound into layers parallel to the xy plane.     

Bis(2,2′-biimidazoline)bis(isothiocyanato)Metal(II) compounds. Synthesis,characterization and lattice hydrogen bonding for Metal = Mn(II) and Ni(II)

The synthesis, characterization and X-ray structures of two compounds with the general formula trans-M(biz)₂(NCS)₂ (in which biz = 2,2′-biimidazoline and M = Mn(II) for compound 1 and Ni(II) for compound 2) are reported. Both compounds crystallize in the triclinic space group P-1 with a = 8.393(5), b = 8.946(5), c = 7.659(5) Å, α = 104.440(5), β = 106.880(5), γ = 66.180(5)^∘, V = 497.7(5) ų, Z = 1 for compound 1 and a = 8.155(2), b = 8.8190(10), c = 7.480(2) Å, α = 102.259(15), β = 106.135(13), γ = 67.706(14)^∘, V = 474.7(2) ų, Z = 1 for compound 2.Both metal ions show octahedral coordination with the four nitrogen atoms of two biz ligands in the equatorial plane and the two nitrogen atoms of two isothiocyanate anions in the axial positions. The M–N≡C angles are 166.5(2) and 167.7(2) for compounds 1 and 2, respectively. These values are in the usually obtained range for trans-isothiocyanate coordinated compounds. The sulfur atom of each isothiocyanate anion acts as acceptor for the hydrogen bond with the NH group of the biz ligands. In the IR spectrum the vibrations of the thiocyanate anion are observed at 2090 and 776 cm⁻¹ for compound 1 and at 2108 and 778 cm⁻¹ for compound 2, and these values are typical for linear-bond isothiocyanate complexes of transition metals.     

Structural comparisons between Cu(II) and Ni(II) diaza-coupled quasi-aromatic α-amineoxime complexes

Reaction of NioylH and CuoylH with the diazonium salt of sulfanilic acid quantitatively produces diaza complexes by coupling at the C-12 position. X-ray structural study: [Nioyl–N=N–C₆H₄SO₃H]·H₂O; C₁₉H₂₈O₆N₆S₁Ni₁ M _r = 527.23, monoclinic P2₁/c, a = 12.752(3), b = 10.795(3), c = 16.609(3) Å, = 92.46(3)°, V = 2284.2(9) ų, Z = 4, D _x = 1.533(2) mg m^–3 [Cuoyl–N=N–C₆H₄SO₃H]· HCl ·3H₂O; C₁₉H₃₃O₈N₆S₁Cu₁Cl₁, M _r = 604.56, triclinic, , a = 8.4019(8), b = 11.2266(99), c = 14.9370(20) Å, = 84.264(7), = 75.309(8), = 73.024(8)°, V = 1303.0(2) ų, Z = 2, D _x = 1.541(2) mg m^–3. The complexes were isolated from about 0.2 M HCl and had different formulas due to differing protonation. The sulfonic acid proton resides on the diaza nitrogen attached to the C₆H₄ ring and with the copper(II) analogue, protonation also occurs on the intramolecular hydrogen-bond oxygen. Bond distance and angle comparisons are made and related to potential electron delocalization between aromatic rings.     

Structure,magnetic and IR studies of copper(II) diphenylphosphate dihydrate,Cu(DPhP)2·(H2O)2

The title compound has been synthesized, and characterized by means of X-ray, magnetic, and IR-spectroscopic measurements.The crystals of Cu(DPhP)₂(H₂O)₂(DPhP=diphenylphosphate) are monoclinic, space groupI2/c witha=24.126(6),b=8.510(2),c=12.333(3) Å,=90.73(5)° andZ=4. The structure was solved by the heavy-atom technique, and refined by full-matrix least-squares calculations to a finalR of 0.040 for 1494 reflections.The complex is centrosymmetric, and the Cu atom at a center of symmetry is four-fold coordinated with two oxygen atoms from two phosphate groups and two water molecules. The coordination about the Cu atom is square-planar, with Cu-O and Cu-O(W) distances 1.926(3) and 1.912(3) Å, respectively.The O(2) phosphate oxygen is an acceptor of two H bonds; one of them is an intramolecular O(W)-H(2)O(2) of 2.714(4) Å, and the other is an intermolecularO(W)-H(1)O(2ⁱ) of 2.667(4) Å. Their presence is also deduced from the IR spectrum of this compound at 3250 and 3000 cm^–1, respectively.The calculated magnetic moment value of 1.92 B.M. corresponds to that of the monomeric copper(II) complexes including those of some alkyl phosphates.     

Structural study of nitrovinylindoles: (I) 2-methyl-3-(2′-methyl-2′-nitrovinyl)indole and (II) 3-(2′-nitrovinyl)indole

Compound (I) is 2-methyl-3-(2-methyl-2-nitrovinyl)indole, C₁₂H₁₂N₂O₂,M _r=216.24, monoclinic,P2₁/n,a=16.710(1),b=7.627(1),c=17.646(1) Å,=104.8(1)°,V=2174.7(1) ų,Z=8.D _x=1.321 g cm^–3, MoK, =0.71073 Å,=0.858 cm^–1,F(OOO)=912, room temperature,R=0.061 for 1956 observed reflections. Compound (II) is 3-(2-nitrovinyl)indole, C₁₀H₈N₂O₂,M _r=188.18, monoclinic,P2₁/n,a=10.178(1),b=10.608(1),c=8.411(1) Å,=105.5(2)°,V=875.0(1) ų,Z=4,D _x=1.4284 g cm^–3, CuK, =1.5418 Å,=8.068 cm^–1,F(000)=392, room temperature,R=0.040 for 1330 observed reflections. Compounds (I) and (II) have a similar geometry, the only significant difference lying in the rotation of the nitrovinyl chain. This feature could be responsible for the difference in biological activity. In both compounds, the molecules are associated, forming charge-transfer complexes.     

Syntheses and Crystal Structures of Two New Cadmium(II) and Nickel(II) Complexes with 1,4-Phenylenediacetate and 2,2′-Bipyridyl-Like Ligands

Abstract  

Two new complexes, namely [Cd(PDA)_0.5(2,2′-bpy)Cl](H₂PDA) (1) and [Ni(PDA)(phen)(H₂O)]₂ (2) (H₂PDA = 1,4-phenylenediacetic acid, 2,2′-bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline), have been synthesized and characterized by elemental analysis, IR spectra and X-ray crystal diffraction. Single-crystal X-ray diffraction analysis shows that complex 1 crystallizes in the triclinic space group P-1 with unit cell dimensions a = 8.760 (4) ?, b = 11.190 (5) ?, c = 13.917 (7) ?, α = 110.383 (5)°, β = 101.736 (5)°, γ = 100.612 (5)°, V = 1202.8 (10) ?³, Z = 2, R ₁ = 0.0314 and wR ₂ = 0.0898. Complex 2 crystallizes in the monoclinic space group P2(1)/n with unit cell dimensions a = 9.911 (3) ?, b = 17.924 (6) ?, c = 10.638 (4) ?, β = 94.998 (5)°, V = 1882.7 (11) ?³, Z = 2, R ₁ = 0.0397 and wR ₂ = 0.1150. In complex 1, Cd(II) ions are alternately bridged by PDA ligands and chloride ions into 1D chains and the PDA ligands display trans-configuration. Complex 2 is a dimer and two Ni(II) ions are linked by two PDA ligands with cis-configuration, resulting in a cyclic structure. In spite of these differences, both in complexes 1 and 2 there are π–π stacking interactions and hydrogen bonding to make them 3D supramolecular frameworks.     

Differential metathesis reactions of 2,2′-bipyridine and 1,10-phenanthroline complexes of cobalt(II) and nickel(II): cocrystallization of ionization isomers {[cis-Ni(phen)2(H2O)2][cis-Ni(phen)2(H2O)Cl]} (PF6)3⋅4.5H2O, and a synthetic route to asymmetric tris-substituted complexes

Addition of ammonium hexafluorophosphate to aqueous solutions of M(chelate)Cl₂ [chelate = 2,2-bipyridine and 1,10-phenanthroline, M = Co(II) and Ni(II)] produce different metathesis products. Tris-substituted chelate complexes are produced in the case of bipyridine; however {[cis-M(phen)₂Cl(H₂O)][ cis-M(phen)₂(H₂O)₂]}(PF₆)₃4.5H₂O, a unique example of cocrystallized ionization isomers, is produced with phenanthroline. Extended hydrogen bonding interactions connect [M(phen)₂Cl(H₂O)]⁺ and [M(phen)₂(H₂O)₂]²⁺ cations in the crystal lattice. Because metathesis reactions using phenanthroline produce disubstituted complexes, the convenient synthesis of symmetric [Ni(phen)₃]²⁺ and asymmetric [Ni(phen)₂(5-nitrophenanthroline)]²⁺ is described.     

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.     

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.     

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.     

Synthesis and Structure of bis(β-Diketiminate) Chromium(II) Complexes

Abstract  

The new ligand 2,4-N,N′-bis(napthylamino)-pent-2-ene (L^napth) (1) has been synthesized and crystallizes in space group P2₁2₁2₁ with crystal cell parameters a = 8.196(3) ?, b = 9.119(3) ?, c = 25.746(10) ?, V = 1924.3(12) ?³ and Z = 4. The complexes bis[2,4-pentane-N,N′-bis(napthyl)ketiminato] chromium(II) (2), bis[2,4-pentane-N,N′-bis(isopropylphenyl)ketiminato] chromium(II) (3), and bis[2,4-pentane-N,N′-bis(tertbutylphenyl)ketiminato] chromium(II) (4) were synthesized and structurally characterized. Complex 2, the first complex reported with a bis(napthyl) β-diketiminate ligand, crystallizes in space group P − 1 with crystal cell parameters a = 12.0824(15) ?, b = 12.2462(16) ?, c = 14.8975(19) ?, α = 87.035(2)°, β = 80.615(2)°, γ = 62.756(2)°, V = 1932.9(4) ?³ and Z = 2. Complex 3 crystallizes in space group P2₁/n with crystal cell parameters a = 13.088(3) ?, b = 22.222(5) ?, c = 14.206(3) ?, β = 102.310(4)°, V = 4036.6(17) ?³ and Z = 4. Complex 4 crystallizes in space group P2₁/n with crystal cell parameters a = 20.831(6) ?, b = 11.575(4) ?, c = 21.373(7) ?, β = 107.241(5)°, V = 4922(3) ?³ and Z = 4. The degree of twist between the ligand planes is dependent on the steric bulk of the ligand.     

Self-assemblies of Ni(II) with phenanthroline and maleate anions: [Ni(H2O)3(phen)L] ⋅ H2O (1) and [Ni(H2O)2(phen)L] ⋅ 2H2O (2) with H2L = maleic acid

The complex [Ni(H₂O)₃(phen)(C₄H₂O₄)] H₂O (1), which was obtained by reaction of phenanthroline, Ni(NO₃)₂ 6H₂O, and maleic acid in CH₃OH/H₂O at pH = 7.05, crystallized in the monoclinic space group P2₁ (no. 4) with cell dimensions: a = 9.350(1) Å, b = 7.631(1) Å, c = 12.821(1) Å, = 106.25(1), and D _calc = 1.607 g/cm³ for Z = 2. The Ni atoms are each octahe drally coordinated by one chelating phen ligand, three H₂O molecules and one monodentate maleato ligand to form [Ni(H₂O)₃(phen)(C₄H₂O₄)] complex molecules with d(Ni–O) = 2.038–2.090 Å, d(Ni–N) = 2.066, 2.089 Å. The formed complex molecules are, via the intermolecular hydrogen bonds, assembled into columnar 1D chains. Interdigitation of the chelating phen ligands of the neighboring chains leads to 2D layers and the crystal H₂O molecules are hydrogen bonded to the oxygen atoms of the maleate not coordinated to the Ni atom. However, reaction of NiCO₃, phen, and maleic acid in CH₃OH/H₂O at pH = 6.33 afforded [Ni(H₂O)₂(phen)(C₄H₂O₄)] 2H₂O (2), which crystallized in the triclinic space group (no. 2) with cell dimensions: a = 7.971(1) Å, b = 8.237(1) Å, c = 13.304(1) Å, = 81.005(6)°, = 87.877(8)°, = 78.322(8)°, and D _calc = 1.671 g/cm³ for Z = 2. The Ni atoms are each octahedrally coordinated by two N atoms of one phen ligand and four O atoms of two H₂O molecules and two bis–monodentate maleato ligands with d(Ni–O) = 2.041–2.120 Å and d(Ni–N) = 2.095 Å. The Ni atoms are bridged by the maleato ligands to generate 1D ¹ [Ni(H₂O)₂(phen)(C₄H₂O₄)_2/2] chains along [100]. The supramolecular assemblies of the 1D chains via – stacking inter- actions result in thick 2D layers parallel to (001), between which the noncoordinating H₂O molecules are sandwiched. The paramagnetic [Ni(H₂O)₂(phen)(C₄H₂O₄)_2/2] 2H₂O (2) obeys the Curie–Weiss law _m(T-) = 1.139cm³ mol^–1 K with the Weiss constant = –0.95 K.     

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 Crystal Structure and Magnetic Susceptibility of Tetrakis-(μ2-phenylacetato-O,O′)-bis(caprolactam-O)copper(II)

Abstract  

Tetrakis-(μ₂-phenylacetato-O,O′)-bis(caprolactam-O)copper(II) (1) was synthesized and characterized by X-ray crystallography, magnetic susceptibility and FT-IR spectroscopy. The title compound (1) crystallized in the monoclinic space group P2₁/n with unit cell parameters a = 18.2242(4) ?, b = 10.0994(2) ?, c = 23.0696(5) ?, β = 101.117(2)°; V = 4166.37(15) ?³; Z = 4. The molecular structure of (1) consists of a copper dimer bridged by four phenylacetate ligands in the paddlewheel geometry with caprolactam coordinated in both axial sites. The copper dimers of (1) are organized into one-dimensional columns by N–H···O interactions between bound caprolactam ligands. Magnetic susceptibility studies indicate antiferromagnetic coupling between the Cu⁺² ions with a singlet ground-state and triplet excited-state separated by |2J = 319(1) cm⁻¹ |.     

Crystal structure of chloro(dicarbonyl) bis(acetonitrile) (π-2-methallyl) molybdenum(II)

The title compound crystallizes in the monoclinic spacegroup P2₁/m with a = 6.796(9), b = 12.145(14), c = 7.749(8)Å, = 101.86(1)°, and Z = 2. The crystal structure consists of molecules of [MoCl(CO)₂(NCMe)₂(³-C₃H₄Me-2)] with crystallographically imposed C_s symmetry and has a pseudo-octahedral geometry, with the -allyl group trans- to the chloro group and the two cis-carbonyl and acetonitrile groups occupying the equatorial plane.     

Hydrogen Bonding Patterns of Coordinated Ligands in Hybrid Materials: Crystal Structures of Hydronium Tetra(Thiocyanato-κN)-Zinc(II): Tris(2-Amino-4,6-Dimethylpyrimidinium) (2-amino-4,6-dimethylpyrimidine) Dinitrate and Bis(2-Amino-4,6-Dimethylpyrimidinium) Tetrachlorocobaltate(II) Monohydrate

Abstract  

Hydronium tetra(thiocyanato-κN)-zinc (II) tri (2-amino-4,6-dimethylpyrimidinium) 2-amino-4,6-dimethylpyrimidine dinitrate [H₃O⁺ Zn(NCS)₄ 3(C₆H₁₀N₃ ⁺) C₆H₉N₃ 2(NO₃)⁻] and bis(2-amino-4,6-dimethylpyrimidinium) tetrachlorocobaltate(II) monohydrate [2(C₆H₁₀N₃ ⁺)] CoCl₄ H₂O have been synthesized and characterized by X-ray diffraction analysis and spectroscopic studies. In compound 1, the coordination geometry around zinc is distorted tetrahedral, Zn being bonded to four N atoms from the thiocyanate anions. In compound 2, the anion [CoCl₄]²⁻ displays distortion from ideal tetrahedral geometry. The 2-amino-4,6-dimethylpyrimidine cations are not directly coordinated to zinc/cobalt, but are hydrogen bonded to the thiocyanate/chloride ions. In both the compounds the protonated nitrogen N1 and the 2-amino group are hydrogen bonded to the nitro group/chloride ions/water molecule through N–H···O and N–H···Cl hydrogen bonds to form R₂²(8) motifs. In both the compounds, the pyrimidine cations also form base pairs via a pair of N–H···N hydrogen bonds involving the amino group and the unprotonated ring N atom. The crystal structures are further stabilized by N–H···S, O–H···O, C–H···O and C–H···Cl hydrogen bonds.     

Crystal structures and properties of catena-μ-nitrato (7-amino-5-aza-4-methyl-3-hepten-2-onato) copper(II) and μ3-hydrox-otris(μ-8-amino-5-aza-4-methyl-3-octen-2-onato) tricopper(II) dinitrate

The products of monocondensation of penta-2,4,-dione with 1,2-diaminoethane, HAE, and with 1,3-diaminopropane, HAT, react with copper nitrate hemipentahydrate to give catena--nitrato (7-amino-5-aza-4-methyl-3-hepten-2-onato) copper(II), [Cu(AE)NO₃]_n and a mixture of ₃-hydroxo-tris (-8-amino-5-aza-4-methyl-3-octen-2-onato) tricopper(II) dinitrate [Cu₃(AT)₃OH]-(NO₃)₂ and [Cu(AT)NO₃]_x, respectively. The structure of [Cu(AE)NO₃]_n has been determined from 1601 diffractometer data and refined by least squares methods toR=0.0306. The compound crystallizes in the monoclinic space groupP2₁/a witha=16.856(3)Å,b=8.109(4)Å,c=7.518(3)Å,=90.15(2)°,D _c =1.725 g cm^–3,D _o=1.72 g cm^–3 andZ=4. Copper atoms in [Cu(AE)NO₃]_n are in a 4+1+1^* environment and are linked by the pseudobidentate and bridging nitrato group into infinite chains. The structure of [Cu₃(AT)₃OH](NO₃)₂ has been determined from 3178 diffractometer data and refined toR=0.0544. The compound crystallizes in the triclinic space groupP¯1 witha=11.918(2)Å,b=14.478(2)Å,c=11.501(3)Å,=98.04(2)°,=117.72(2)°, =99.80(1)°,D _c =1.580 g cm^–3,D _o=1.59 g cm^–3 andZ=2. The compound is associated in hexanuclear clusters due to hydrogen bonding interactions. Coordination about Cu is best described as square pyramidal. Magnetic susceptibility data indicate a weak antiferromagnetic exchange within the trinuclear core withJ=–14 cm^–1.     

Synthesis and structure of (H2O)(12-crown-4)-Co(II)(Co(II)Cl3)(μ-Cl) isolated from a liquid clathrate medium

The crystal structure of (H₂O)(12-crown-4)Co(II)(Co(II)Cl₃)(μ-Cl)1 is reported. Crystal data for1: monoclinic, space groupP2 ₁/m, a=7.958(8) Å,b=12.006(1) Å,c=69.017(9) Å, β=107.896(2)⁰, D_c=1.84 g cm^?3,Z=2,R1=0.025,wR2=0.059. The crown ether acts as a tetradentate ligand and partially completes the binding sphere of the Co(II) ion which also includes one water oxygen atom and a bridging chloride ligand, the latter of which may be regarded to originate from a [CoCl₄]^2? ion.     

Zn(II) and Cd(II) Complexes Extended Structures Sustained by Hydrogen Bonding, π–π and C–H···π Interactions

Abstract  

Two new complexes [Zn(sal)₂(tpt)]·H₂O(1), [Cd(sal)₂(tpt)(H₂O)]·H₂O(2), have been obtained through ligands tpt and Hsal, where Hsal is salicylic acid and tpt is 2,4,6-tripyridyl-1,3,5-triazine, reacting with Zn(II) and Cd(II) salts. Their structures are fully characterized by IR spectroscopy, elemental analysis, single crystal X-ray diffraction. In complex 1, Zn(II) is coordinated by three N atoms and two O atom with a distorted square pyramidal coordination geometry. In 2, Each Cd(II) atom is seven-coordinated with a distorted pentagonal bipyramidal coordination geometry. The structural differences between two complexes show the influence of the coordinating orientation of metal ions. These two mononuclear complexes are further extended into three-dimensional structure via π–π, C–H···π and hydrogen bonding interactions. The solid state luminescent properties of complex 1, 2 are also reported.     

Novel Assembly of a Cyanide-Bridged Copper(II)–Nickel(II) Binuclear Complex with a Copper(II) Macrocyclic Ligand

Abstract  

A mononuclear fragment [Cu(L)Cl]ClO₄ (1) and a cyano-bridged Cu^II–Ni^II binuclear complex [CuL][Ni(CN)₄]·0.25H₂O (2) (L = 1,3,6,8,11,14-hexaazatricyclo[12.2.1.18,11]-octadecane), have been prepared and characterized. X-ray single crystal analyses indicate that the both complexes crystallize in the monoclinic crystalline system. The complex of 1 in P1n1 space group with unit cell constants a = 6.1176(6) ?, b = 11.9147(10) ?, c = 12.2041(12) ?, β = 98.816(5)° and 2 in the P2₁/n space group with unit cell constants a = 8.1419(13) ?, b = 14.695(2) ?, c = 16.863(3) ?, β = 98.375(2)° have been revealed. The complex 2 assumes a binuclear structure in which the nickel(II) ion is in a square planar environment and the copper(II) is in a square-prism geometry environment.