Crystal structures of two polymeric 1,5-naphthalenedisulfonate-coordinated transition metal complexes

Two 1,5-naphthalenedisulfonate(1,5-nds)-coordinated polymeric complexes [Cu(1,5-nds) (H₂O)₄]_n and [Cd(1,5-nds)(H₂O)₂]_n were synthesized and their structures characterized by single-crystal structure analysis. The Cu(II) complex [Cu(1,5-nds)(H₂O)₄]_n is obtained both from CuCl or CuCl₂ reacting with 1,5-naphthalenedisulfonic acid at 80^∘C. It is a one-dimensional polymer in which Cu(II) is coordinated by four water molecules and two sulfonate oxygen atoms in the trans positions. The interaction between sulfonate and Cu(II) is different in complexes obtained from different reaction temperature. While the three-dimensional Cd(II) complex [Cd(1,5-nds)(H₂O)₂]_n is a polymorph of the reported two-dimensional layer structure, in which Cd(II) is coordinated by two water molecules in the trans positions and four different sulfonate groups, the same as that observed in the two-dimensional polymorph. However, the 1,5-nds ligands connect Cd(II) centers belonging to different layers, resulting in the three-dimensional framework.     

Synthesis and crystal structure of macrocyclic nickel(II) complex bridged by chromate

A novel compound catena-(-CrO₄-O,O)[Ni(L¹)Ni(L²)] 3H₂O (1) (L¹ = 3,5,10,12-tetramethyl-1,4,8,11-tetraazacyclotetradecane and L² = 2,5,9,12-tetramethyl-1,4,8,11-tetraazacyclotetradecane) has been synthesized for the first time and structurally characterized. 1 crystallizes in the triclinic space group P with a = 9.623(1), b = 10.084(1), c = 12.723 (3) Å, = 66.74(2), = 75.20(1), = 72.02(1)°, V = 1066.2(3) ų, and Z = 2. The coordination environment around the Ni(II) ions is an axially elongated octahedron with the secondary amines of the isomeric ligands and two oxygen atoms of [CrO₄]^2–.     

X-ray crystal structure of trans-bis(monoethanolamine) bis(saccharinato)nickel(II)

The crystal structure of trans-bis(monoethanolamine)bis(saccharinato)nickel(II), [Ni(C₇H₄NO₃S)₂(C₂H₇NO)₂], has been determined from X-ray diffraction data. The metal complex is monoclinic, with a = 11.0555(5), b = 8.9103(4), c = 11.3890(5) Å, = 105.0230(10)°, Z = 2, and space group P2_1/c . The structure consists of individual molecules. Two monoethanolamine molecules and two saccharinate anions coordinate the nickel atom forming a distorted octahedron. The monoethanolamine molecules act as a bidentate ligand and form five-membered trans chelate rings, which constitute the plane of the coordination octahedron, while two saccharinate ions behave as a monodentate ligand occupying the axial positions. Intermolecular hydrogen bonds link the molecules to form a three-dimensional infinite structure.     

Synthesis and crystal structures of complexes of Ni (II) to chiral Schiff bases of (R)- and (S)-serine with (S)- and (R)-2-N-(N′-benzylprolyl)-aminobenzophenone

The three-dimensional molecular and crystal structures of a pair of enantiopure mirror complexes of Ni (II) to chiral Schiff bases of (R)- and (S)-serine with (S)- and (R)-2-N-(N′-benzylprolyl)-aminobenzophenone (BPB), denoted as (S,R)-BPB-Ser-Ni and (R,S)-BPB-Ser-Ni, respectively, have been determined by X-ray diffraction. The complexes crystallize in the orthorhombic space group P2 ₁ 2 ₁ 2 ₁ with unit cell parameters: a = 10.050(2) Å, b = 10.100(2) Å, c = 26.514(5) Å, V = 2691.3(9) ų, and Z = 4 for (S,R)-BPB-Ser-Ni; and a = 9.878(2) Å, b = 10.130(2) Å, c = 26.304(5) Å, V = 2632.1(9) ų, and Z = 4 for (R,S)-BPB-Ser-Ni. The Ni atom is square-planar-coordinated to N(1), N(2), O(4), and N(3) of the Schiff base with minor distortion. The hydroxymethyl group on the serine moiety is axial to the coordination plane and parallel to the neighboring phenyl group.     

Synthesis and crystal structure of a nickel(II) complex involving imino nitroxide radicals

A new complex of formula [Ni(im2-py)₂(SCN)₂]CH₃OH (im2-py = 2-(2-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl) has been synthesized and the crystal structure determined by X-ray diffraction methods. The complex crystallizes in the monoclinic space group P2₁/n with a = 15.525(5) Å, b = 13.405(4) Å, c = 16.167(5) Å, = 113.324(5)°, V = 3089.6(16) ų, and Z = 4. The structure of this complex is mononuclear with the nickel(II) ion octahedrally coordinated and bound to the imino nitroxide radicals through the imino nitrogen atoms. The thiocyanate groups are coordinated to the metal by the nitrogen atoms.     

Crystal structures of the cobalt(III), nickel(II), copper(II), and zinc(II) complexes of 2-thio-6-picoline N-oxide

Structures of the following compounds have been solved: tris(2-thio-6-picoline N-oxide)cobalt(III), [Co(6MOS)₃], orthorhombic, Pca2₁, a = 17.871(3), b = 14.061(2), c = 15.964(2) Å, V = 4011(1) ų, Z = 8, and = 1.193 mm^–1; bis (2-thio-6-picoline N-oxide)nickel(II), [Ni(6MOS)₂], orthorhombic, Pbca, a = 15.602(8), b = 13.606(4), c = 13.348(8) Å, V = 2833(4) ų, Z = 8, and = 1.655 mm^–1; bis(2-thio-6-picoline N-oxide)copper(II), [Cu(6MOS)₂], orthorhombic, Pbca, a = 13.914(5), b = 12.984(5), c = 15.663(6) Å, V = 2830(2) ų, Z = 8, and = 1.836 mm^–1; and bis(2-thio-6-picoline N-oxide)zinc(II), [Zn(6MOS)₂], triclinic, P – 1, a = 7.9737(8), b = 11.7786(9), c = 7.9206(8) Å, = 104.502(7), = 104.495(8), = 93.445(8)°, V = 691.3(1) ų, Z = 2, and = 2.106 mm^–1. The steric effect of the methyl group in the six-position of the N-oxide ring is considered in comparing these structures to complexes of 2-thiopyridine N-oxide.     

X-ray crystal structure of tetraaquabis (xanthosinato)nickel(II) hexahydrate

The complex [Ni(XsH_–1)₂(H₂O)₄]·6H₂O (XsH_–1: xanthosinate) was isolated from the reaction of nickel carbonate with xanthosine in aqueous solution. The octahedral coordination is supported by the reflectance measurements. Single-crystal X-ray diffraction studies show that the crystals belong to the triclinic P1 space group, with a = 7.152(1), b = 8.830(1),c = 13.783(1) Å, = 82.024(1)°, = 86.155(1)°, = 70.900(1)°, and D = 1.643 mg/m³, forZ = 1. Nickel is six coordinate with four water molecules, and two N7 atoms from xanthosinato ligands. A complicated hydrogen-bonding network is present, all possible donors taking part in it.     

Crystal structure of a novel tertiary phosphine coordination complex: dichlorobis(tribenzylphosphine)nickel(II)

The title compound dichlorobis(tribenzylphosphine)nickel(II), Ni[P(CH₂C₆H₅)₃]₂Cl₂, belongs to a type of tertiary phosphine coordination complex, M(PR₃)₂X₂. There are two molecules in the unit cell which do not appear to interact chemically. Both molecules have a trans-square planar configuration with each nickel atom on a center of symmetry. Three benzyl groups are bonded to each phosphorus atom as rotors in a propeller, and the threefold axis is along the P—Ni bond, which has a mean length of 2.23(1) Å. Crystal data: C₄₂H₄₂Cl₂NiP₂, Triclinic, space group , a = 10.4892(15) b = 10.5249(12) c = 19.453(2) Å, = 83.872(8), = 76.839(9), = 62.241(8)°, V = 1850.5(4) ų, Z = 2. There is an intramolecular hydrogen bond between the C3 and C11 atoms.     

Synthesis and crystal structure of a cobalt(II) complex with tris(1-pyrazolylmethyl)amine

The synthesis of a cobalt(II) complex of tris(1-pyrazolylmethyl)amine (amtp) is reported. The complex [Co(amtp)Cl](BPh₄) crystallizes in the space group P-1, with a = 8.979(2), b = 19.329(3), c = 20.251(3) Å, = 93.321(2), = 93.685(3), = 98.930(2)°, and Z = 4. The Co(II) atom is nearly tetrahedrally coordinated by three pyrazole N-atoms and one Cl^–. The tertiary amine N-atom of amtp is only weakly coordinated to Co(II) atom at a Co—N(amine) distance of ca 2.40 Å.     

X-ray crystal structure of a macrocyclic tetraamine nitrito nickel(II) complex

The compound [Ni(L)(²-NO₂)]ClO₄ (L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) has been synthesized and structurally characterized. It crystallizes in the monoclinic system, space group P2₁/c with a = 26.899(5), b = 8.476(2), c = 23.633(5) Å, = 115.12(13)°, V = 4878.6(17) ų, and Z = 4. Each nickel(II) ion has a six-coordinated bicapped square-pyramidal geometry with four secondary amines of the macrocycle and two oxygen atoms of the bidentate nitrito group. Electronic spectra and effective magnetic moment of the complex also exhibit a high-spin six-coordinated geometry.     

Synthetic and structural studies of the trans bis(2-N-H-pyrrolylcarbaldimine) complexes of nickel(II) and palladium(II)

The molecular bis(2-N-H-pyrrolylcarbaldimine)nickel(II) and palladium(II) complexes are isolated in moderate yield (30–35%) from in situ assembly of the Schiff base with metal(II) salt, base, and pyrrole-2-carbaldehyde in aqueous ammonia solution. The nickel(II) complex, 1, is monoclinic, space group P2₁/c, with a=11.289(6) ?, b=5.611(3) ?, c=8.287(5) ?, β=111.620(6)°, and V=488.0(5) ?³ with Z=2, for d _calc=1.667 Mg/m³. The palladium analog, 2, is isomorphous, space group P2₁/c, with a=11.481(3) ?, b=5.5738(10) ?, c=8.276(2) ?, β=110.923(12)°, and V=494.7(2) ?³ with Z=2, for d _calc=1.965 Mg/m³. In both crystal structures, the metal resides on an inversion center. In the IR spectra, ν(C=N) appears at 1561 cm⁻¹ in 1, and 1557 cm⁻¹ in 2, while ν(N–H) shows at 3345 cm⁻¹ and 3335 cm⁻¹, respectively. The ¹H-nmr spectra reveal the C–H and N–H protons of the imine group as sharp and broad doublets, respectively, at 7.62 and 8.38 δ in 1 and at 7.92 and 9.73 δ in 2.     

Synthesis and crystal structure of tetraiminediphenolate diiron(II) macrocyclic complex

The crystal structure of the binuclear tetraiminediphenolate diiron(II) macrocyclic complex [Fe₂(tidf)(CH₃OH)₄](ClO₄)₂ (tidf = tetraiminediphenolate ligand) is presented. The molecular structure (monoclinic, space group C2/c, Z = 4, a = 20.6903(14)Å, b = 11.0827(11) Å, c = 16.0494(15) Å, = 99.911(6) shows two iron(II) cores occupying distorted octahedral geometries with four methanol molecules bound axially. Main equatorial bond distances are 2.050(3) Å for Fe—O1 and 2.067(4) Å for Fe—N1 with a Fe Fe distance of 3.108(1) Å. Contrasting to the monoiron complex the macrocycle does not adopt a bent conformation being nearly coplanar with the maximum deviation from the least-squares plane of 0.18 Å.     

Synthesis and X-ray structure of dichlorobis(8-(diphenylphosphinyl)quinoline)nickel(II)

Dichlorobis(8-(diphenylphosphinyl)quinoline)nickel(II) was formed in the reaction of 8-(diphenylphosphino)quinoline with nickel chloride in air. The title complex crystallized in P1 with the following cell dimensions: a = 8.5685(3) Å, b = 10.7736(2) Å, c = 13.4391(5) Å, and = 110.447(2)°, = 94.577(2)°; = 111.138(2)°, giving a volume of 1053.75(6) ų. The trans-dichlorobis(8-(diphenylphosphinyl)quinoline) nickel(II) adapts a central symmetric distorted octahedron. The structure is compared to other nickel(II) cation complexes, and possible reasons for the bonding states are discussed.     

Synthesis, crystal structures, and properties of two manganese(II)-nitroprusside complexes

Two new manganese(II)-1,10-phenanthroline-nitroprusside complexes, [Mn(phen)₃][Fe (CN)₅(NO)]⋯2H₂O⋯0.25CH₃OH (1) and [Mn(phen)₂(H₂O)₂][Fe(CN)₅(NO)]⋯H₂O (2) (where phen is 1,10-phenanthroline) have been synthesized and characterized by X-ray diffraction, electronic paramagnetic resonance (E.P.R.) and IR analyses. Complex 1 crystallizes in the monoclinic space group P2₁/n, with lattice parameters a = 10.0441(15) Å, b = 19.668(2) Å, c = 19.938(3) Å,  β =100.427(14)°, V = 3873.7(10) ų, Z = 4; complex (2) crystallizes in the monoclinic space group C2/c, with a = 17.120(2) Å, b = 13.7925(19) Å, c = 14.4362(17) Å, β = 107.962(12)°, V = 3242.6(7) ų, Z = 4. In the two compounds, three phen ligands 1, or two phen ligands and two cis-related aqua molecules 2, are in a distorted octahedral arrangement around the Mn(II) ion. The nitroprusside anion, [Fe(CN)₅(NO)]²⁻, acts as a counterion. It is intriguing that in complex 2 no cyano bridges are present with two water molecules coordinated to the Mn(II) ion considering that usually the cyano nitrogen atoms are strong donors and could readily replace the coordinating solvent water molecules. Abundant hydrogen bond interactions and π–π stacking between the phen rings in two complexes lead to three-dimensional supramolecular networks.     

Synthesis,crystal and molecular structure of trans‐bis(2‐pyridinepropanol)bis(saccharinato)nickel(II)

Trans‐bis(2‐pyridinepropanol)bis(saccharinato)nickel(II), [Ni(sac)₂(pypr)₂], where sac and pypr are the saccharinate anion and the 2‐pyridinepropanol molecule, respectively, crystallizes in the triclinic space group P (No. 2) with a = 8.1981(8), b = 9.9680(10), c = 10.4956(10) Å, α = 90.740(3)° β = 108.142(3)°, γ = 111.025(3)°, Z = 1, V = 1.537 ų. The structure of the nickel(II) complex consists of neutral molecules in which the nickel(II) ion sits on a center of symmetry and is octahedrally coordinated by two sac ligands, and two neutral pypr ligands. The pypr acts as a bidentate N‐ and O‐donor ligand forming a seven‐membered chelate ring, while sac behaves as a monodentate O‐donor ligand via the carbonyl O atom. The Ni‐N bond distance is 2.1016(15) Å, whereas the Ni‐O_pypr and Ni‐O_sac bond distances are 2.1280(12) and 2.0792(11) Å, respectively. The individual molecules are held together with a strong hydrogen bond between the hydroxyl O atom of pypr and N atom of sac and the C‐H…O type weak hydrogen bonds between some ring hydrogen atoms of pypr and sac, and the carbonyl and sulfonyl O atoms of sac in the neighbouring molecules. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis, crystal structure and properties of square-planar acetato{[(4-methylimidazol-5-yl)methylene]histamine} copper(II) perchlorate

The square-planar complex [Cu(MIMH)(CH₃CO₂)](ClO₄) (1) (MIMH = [(4-methylimidazol-5-yl)methylene]histamine) was prepared and structurally characterized. Complex 1 crystallizes in the monoclinic space group P2₁/n with a = 10.5331(10), b = 12.6177(10), c = 12.9773(10) Å, = 107.710(10)°, V = 1643.0(2) ų, and Z = 4. Single-crystal X-ray analysis reveals that the copper(II) atom in 1 has a distorted square-planar environment defined by three nitrogen atoms from the Schiff base ligand and one oxygen atom from the acetate group. The Cu—N bond lengths range from 1.950(3) to 2.015(3) Å and the Cu—O(1) bond length is 1.952(2) Å. The electronic spectra of 1 in aqueous solutions indicates that 1 forms adducts of square-pyramidal geometry with H₂O. Cyclic voltammetry of 1 in DMF solution shows that there is some degradation of 1 upon reduction.     

Synthesis and crystal structure of copper(II) complex with 1,9-diamino-5-methyl-5-nitro-3,7-diazanonane

Condensation of bis(ethanediamine)copper(II) perchlorate with formaldehyde and nitroethane in basic methanol was found to generate (1,9-diamino-5-methyl-5-nitro-3,7-diazanonane)copper(II) perchlorate, [Cu(L₁)](ClO₄)₂. The copper(II) complex was characterized by elemental analysis and infrared and electronic spectra studies. The structure of [Cu(L₁)](ClO₄)₂ was determined by X-ray diffraction. The crystal structure revealed that the copper ion is in an elongated octahedral coordination with four nitrogens at the equational position and perchlorate anions at the axial positions and that one of the perchlorate anions bridges two copper ions, leading to a linear polymeric structure in the crystal.     

Synthesis and structural characterization of the dinuclear bis(glutarato)bis(urea)copper(II)complex, dihydrate

The complex [Cu(OOC-(CH₂)₃-COO)(O=C(NH₂)₂]₂·2H₂O has been synthesized and characterized by X-ray crystallography. It crystallizes in the triclinic system P-1 with a = 8.003(2) ?, b = 8.611(2) ?, c = 8.620(2) ?, α = 96.14(3)°, β = 116.66(2)°, γ = 105.66(4)° and V = 492.9(3) ?³. The structure consists of discrete centrosymmetric binuclear units and water molecules. The Cu(II) ions adopt a square-pyramidal coordination with four oxygen atoms of four bridging carboxylate and one carbonyl oxygen of the monodentate urea ligand. There is a very strong interaction between the two copper centers in binuclear entities (CuCu: 2.6266(15) ?).     

Crystal structure of a nickel(II) complex with macrocyclic tetraamine

A new compound [Ni(cyclen)(²-CH₃CO₂)]BF₄ (cyclen = 1,4,7,10-tetraazacyclodode- cane) has been synthesized and characterized structurally. It crystallizes in the orthorhombic system, space group Pnnm with a =12.045(5), b =14.906(6), c =8.913(4) Å, V =1600.4(12) ų, and Z =4. The nickel(II) ion has a distorted octahedral geometry with four secondary amines of the macrocycle and two oxygen atoms of the bidentate acetate group. TGA curve shows its thermal stability is up to 280°C.     

Synthesis and crystal structure of a binuclear maleatocopper(II) complex with phenanthroline

The title copper(II) complex [Cu₂(C₄H₂O₄)₂(phen)₂]⋅4H₂O (phen = 1,10-phenanthroline) was prepared and its crystal structure was determined by X-ray diffraction method. The crystal belongs to space group C2/c with cell of a = 18.136(5), b = 12.505(5), and c = 14.617(5) Å, β = 103.440(5)^∘ and Z = 4. The Cu(II) atom assumes a square pyramidal coordination geometry with a longer Cu–O3 coordination distance [2.308(3) Å] in the apical direction. The carboxyl O3 atoms from two maleate dianion bridges two Cu(II) atoms to form the binuclear complex with a shorter Cu⋅sCu separation of 3.349(1) Å. The separations of 3.39(1) and 3.41(1) Å between parallel phen rings indicate the existence of aromatic stacking.