Structure and conformation of a nickel complex: {2‐Hydroxo‐3‐piperidine‐1‐yl‐methyl‐N,N′(bis‐5‐bromobenzylpropylenediimine)nickel(II)perchlorate}

The title compound, a nickel complex [C₂₃H₂₆N₃O₂Br₂Ni.(ClO₄)] (CCDC 199520) crystallizes in triclinic space group P with the cell parameters a = 10.2560(4), b = 10.8231(4), c = 12.0888(5)Å, α = 99.404(1), β = 99.780(1), γ = 92.252(1)° and V = 1301.49(9)ų. The structure was solved by Patterson method and refined by full‐matrix least‐squares procedures to a final R = 0.0497 using 6287 observed reflections. In the complex, the piperidine ring takes chair conformation and the geometry around the Ni ion is slightly distorted square planar. The dihedral angle between the planes [N‐Ni‐N and O‐Ni‐O] is 9.4(1)°. The chelate ring containing both the nitrogen atoms adopts twisted boat conformation. The molecules in the crystal are stabilized by N‐H…O and C‐H…O types of hydrogen bonds in addition to a C‐H…π interaction. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural analysis of bis{(N,N′–dimethylformamide) (μ‐formato)[μ‐bis(salicylidene)–1,3‐propanediaminato] nickel(II)} copper(II) and zinc(II) monohydrate hetero‐trinuclear complexes

The two linear hetero‐trinuclear metallic complexes with Cu²⁺, Ni²⁺ and Zn²⁺ ions, [CuNi₂ {(CHO₂)(SALPD)[(CH₃)₂NCHO]}₂],(I) and [ZnNi₂{(CHO₂)(SALPD)[(CH₃)₂NCHO]}₂],(II), form crystals which belong to the monoclinic system, space group P2₁/c, with unit cell dimensions a=10.537(4), b=16.612(5), c=13.837(3) Å, β=111.09(5)°, V=2259.8(12) ų in (I) and a=10.525(4), b=16.658(5), c=13.826(3) Å, β=111.11(5) °, V=2261.4(8) ų in (II), respectively. The coordinations around the M (Ni²⁺, Cu²⁺, Zn²⁺) ions in the title complexes are distorted octahedrals. The stereochemistries of the bridge ligands, linking to the metal ions each other, are changed between Ni…M (Cu²⁺, Zn²⁺) distances. The Ni…M (Cu²⁺, Zn²⁺) distances are 3.0469(13) and 3.0645(14), respectively. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,crystal structure and spectral analysis of diaquatetrakis(N‐methylimidazole)Ni(II)(2,4,6‐tribromophenol)

Diaquatetrakis(N‐methylimidazole)Ni(II)(2,4,6‐tribromophenol), Ni(H₂O)₂(C₃N₂(CH₃))₄^.2(C₆H₃Br₃O), was synthesized via reaction of nickel sulphate and 2,4,6‐tribromophenolate in aqueous media in the presence of N‐methyl imidazole and sodium hydroxide. The complex crystalizes in the triclinic space group P1 with one formula unit of Ni(C₃H₃N₂(CH₃))₄(H₂O)₂.2(C₆H₃Br₃O) in the cell. The coordination around the Ni(II) ion is a slightly distorted octahedron, involving four N atoms from four different di(N‐methyl imidazole) ligand in the basal plane. The two oxygen atoms of the water molecules located at the apical positions result in an octahedral coordination. The two tribomophenol groups in the unit cell are connected via hydrogen‐bonds to the atoms of the coordination sphere, to build one dimensional chains along the a‐axis. For characterization of complex FTIR, UV spectroscopy, DSC and TGA thermal analysis were performed. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure analysis of N,N′‐bis(salicylidene)‐2‐methyl‐1,2‐propanediaminato‐nickel(II)

In the title compound, N,N′‐Bis(salicylidene)‐2‐methyl‐1,2‐propanediaminato‐nickel(II), [NiC₁₈H₁₈N₂O₂], (CCDC 235278), the Ni^II atom is coordinated by two iminic N and two phenolic O atoms of the N,N′‐Bis(salicylidene)‐2‐methyl‐1,2‐propanediaminate (SALPD^2‐) ligand. The geometry of the coordination sphere around the Ni atom is distorted square‐planar. Ni(II) ion, forms crystals which belong to the orthorhombic system, space group P cab, with unit cell dimensions a=11.5531(1), b=15.985(4), c=17.418(1) Å, V=3210.5(9) ų. The cell contains eight molecules. The contact distance Ni...Ni^a between the neighbouring molecules is 4.4704(8) Å. © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

Crystal structure analysis of {[μ‐N,N′‐Bis(salicylidene)‐1,3‐propanediaminato]nickel(II)}dichloromercury(II)

The title compound, a hetero‐dinuclear complex with Ni(II) and Hg(II) ions, forms crystals which belong to the triclinic system, space group P1, with unit cell dimensions a = 8.9620(12), b = 9.2370(11), c = 12.0810(13) Å, α = 92.100(3)° , β = 105.317(5)°, γ = 110.502(3)°, V = 894.2(2) ų. The cell contains two molecules. The Ni…Hg distance is 3.4859(7) Å. The distance Hg...Hg^a (symmetry code: ‐x,‐y,‐z) between the neighbouring molecules is 4.7514(7) Å. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal Structure Analysis of {[μ‐N,N′‐Bis(salicylidene)‐2,2′‐dimethyl‐1,3‐propanediaminato](dimethylformamide) zinc(II)}diiodomercury(II)

The title compound, a hetero‐dinuclear complex with Zn^II and Hg^II ions, forms crystals which belong to the monoclinic system, space group P2₁/n, with unit cell dimensions a = 11.2217(12), b = 17.7493(11), c = 13.9293(13) Å, β = 94.830(3)°, V = 2764.5(4) ų. The cell contains four molecules. The Zn…Hg distance is 3.5362(15) Å.     

Synthesis and crystallographic characterization of a chiral complex of (R)‐2‐(pyridin‐2‐ylmethylene)amino‐2′‐hydroxy‐1,1′‐binaphthyl(L) with hydrated nickel(II) acetate

A chiral complex of (R)‐2‐((pyridin‐2‐ylmethylene)amino)‐2′‐hydroxy‐1,1′‐binaphthyl ( L ) with hydrated nickel (II) acetate has been synthesized and spectroscopically characterized. The crystal structure of [NiL₂(CH₃OH)(CH₃COO)]CH₃COO·CH₃OH has been determined by single‐crystal X‐ray diffraction. The complex crystallizes in the orthorhombic space group P 2(1) 2(1) 2(1) with cell constants a = 15.1035 (19), b = 17.836 (2), c = 18.730 (2)Å, α = β = γ = 90.00°, Z = 4. The structure was solved by direct methods and refined to R = 0.0346 (wR₂ = 0.0863). The analytical result of the crystal structure indicates that a pair of L ligands chelate to a Ni (II) atom in an asymmetric fashion with one Ni‐N bond being longer than the other, the Ni (II) atom is further coordinated by one methanol molecule and one acetate anion to form a distorted octahedral geometry. In the crystal of the complex, the coordination cation [NiL₂(CH₃OH)(CH₃COO)]⁺, the uncoordinated methanol molecule and uncoordinated acetate anion are further assembled into one‐dimensional chain structure via intermolecular hydrogen bonds along the a‐axis. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,crystal structure and third order nonlinear optical properties of bis(tetra‐n‐propylammonium) bis(2‐thioxo‐1,3‐dithiole‐4,5‐dithiolato)cuprate(II)

A novel bis (dmit) complex of copper (II), [(C₃H₇)₄N]₂[Cu(dmit)₂] ( 1 ), where dmit is 2‐thioxo‐1,3‐dithiole‐4,5‐dithiolate, was prepared and structurally characterized by X‐ray single crystal diffraction. The copper (II) atom is tetracoordinated by four dmit S atoms, forming a nearly square planar arrangement. The [Cu(dmit)₂]^2‐ anions and the [(C₃H₇)₄N]⁺ counter‐cations form a three‐dimensional solid‐state structure by C–H…S hydrogen bonds. The third‐order nonlinear optical properties of the complex were determined by picosecond Z‐scan technique at a wavelength of 1064 nm. The results indicate the compound exhibits reverse saturation absorption and self‐defocusing performance. The molecular second‐order hyperpolarizability γ is calculated to be as high as (1.8±0.2)×10^‐30 esu. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure of N‐(3,4‐dichlorophenyl)‐N′‐hydroxy‐2‐oxo‐2‐phenylacetamidine

The title compound (C₁₄H₁₀N₂O₂Cl₂) crystallizes in the monoclinic space group P2₁/a with a=10.042(1) Å, b=10.317(1) Å, c=13.877(2) Å, β=97.36(2)°, V=1425.8(3) ų, Z=4, D_x=1.44 g.cm^‐3. The structure was solved by direct methods and refined by full‐matrix least‐squares method (R = 0.0457). The title molecule consists of 3,4‐dichlorophenylamino and 2‐phenyl‐1,2‐ethanedione‐1‐oxime groups. The intermolecular O‐H…N and N‐H…O hydrogen bonds [O…N 2.760(6) and 3.087(5) Å] are highly effective in forming the polymeric chains. The oxime group has an E configuration. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,crystal structure and photophysical studies on a ruthenium(II) carbonyl hydrido compound based on 2,2′‐bipyridyl‐5,5′‐dicarboxylic acid (H2bpdc)

A novel complex, namely [Ru^II(PPh₃)(CO)(H)(Hbpdc)]·2MeOH ( 1 ) (H₂bpdc = 2,2′‐bipyridyl‐5,5′‐dicarboxylic acid), has been synthesized from the reaction of H₂bpdc with [Ru^II(PPh₃)₃(CO)(H)₂] in methanol under mild condition and characterized by elemental analysis, IR spectrum, ESI mass spectrometry, and single crystal X‐ray diffraction. The structure shows that the complex crystallizes in the monoclinic space group P2₁/c with unit cell parameters a = 11.8984(13) Å, b = 16.5180(18) Å, c = 25.5322(19) Å, β = 115.302(4)°, V = 4536.6(8) ų, Z = 4. This compound features a 1‐D supramolecular chain constructed via hydrogen bonds. Its photophysical properties have been investigated in MeOH solution and in the solid state at room temperature.     

Crystal and molecular structure of tetrakis(N,N′-diallylthiourea)nickel(II) iodide

Summary The crystal structure of tetrakis(N,N-diallylthiourea)nickel(II) iodide [Ni(C₇H₁₂N₂S)₄I₂] has been determined by a three-dimensional X-ray analysis. FinalR, after anisotropic least-squares refinement, is 8·8%. The crystals are tetragonal (P4/n):a = 11·24(1),c = 15·43(1) Å,Z = 2. Ni(II) is on a 4-fold axis; the coordination around it is flattened pyramidal and involves four sulphur atoms from four diallylthiourea molecules (Ni-S = 2·221 Å). Ni(II) is out of the plane through the sulphur atoms by 0·40 Å. Two I^- ions lie on opposite sides with respect to the nickel atom along the 4-fold axis, at distances Ni...I(1) = 3·74 Å, Ni...I(2) = 6·64 Å. The orientation of the allylthiourea molecules is determined mainly by a hydrogen bond formed by one nitrogen (N(1)) with the iodine which is nearer to the nickel.The authors are indebted to Prof. C. Furlani who kindly supplied the crystals of the compound.     

Synthesis,characterization and crystal structure of a novel Ni(II) coordination polymer with dipyrido[3,2‐a:2′,3′‐c]phenazine and 4,4′‐oxy(bisbenzoate)

A novel coordination polymer, [Ni(dppz)(oba)(H₂O)]·0.5H₂O (dppz = dipyrido[3,2‐a:2′,3′‐c]phenazine and oba = 4,4′‐oxy(bisbenzoate)) has been synthesized through hydrothermal method and characterized by IR, and single‐crystal X‐ray diffraction. It crystallizes in monoclinic, space group C2/c with a = 23.163(5), b = 18.211(4), c = 14.460(3) Å, α = γ = 90°, β = 100.45(3)°, V = 5998(2) ų, Z = 2. The structure was solved by direct methods and refined to R = 0.0866 (wR₂ = 0.1836). The compound exhibits interesting one‐dimensional chain structures, which are further stacked through π‐π interactions to form supramolecular double chains. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

New selective nickel(II)-N3 nitrogen bond in adenine: Synthesis and structure of [(tren) (adenine) (monochloro)nickel(II)] chloride and [(tren)(imidazole)(monoaqua)nickel(II)] dichloride

With the aim to obtain further insight into the nature of the Ni(II)-nitrogen bond in complexes with nucleobases, we have synthesized two novel Ni(II) ternary complexes constituted by Ni(II), tris(2-aminoethyl)amine (tren) and neutral adenine (AdH) or imidazole (ImH). The reaction of NiCl₂·6H₂O with tren and imidazole yields the ternary [Ni(tren)(ImH)(H₂O)]Cl₂·H₂O complex and the same reaction with adenine instead of imidazole gives the ternary [Ni(tren)(AdH)Cl]Cl complex. The complexes have been studied by spectrophotometric and spectroscopic measurements and by X-ray diffraction. The ternary complex of adenine is monoclinic, space groupC2/c, and exhibits a pseudo-octahedral geometry, being Ni(II) coordinated to the four nitrogen atoms of the tetradentate tren ligand, to a Cl^– ion and to the pyrimidine N3 site of a neutral adenine. Such an exclusive Ni-N3 bonding [2.081(4)Å] is now reported for the first time. The ternary complex of imidazole is monoclinic, space groupP2₁/n. Its pseudo-octahedral geometry is similar to that found in the above adenine complex although a water molecule instead of a Cl^– ion is now present in the coordination sphere. In fact, Ni(II) is coordinated to tetradentate tren, to the imidazole N1 nitrogen and to a water molecule. Electronic and¹H NMR spectra in solution indicate that the octahedral structures found in the solid state are substantially maintained in solution. Furthermore, the present investigation suggests that the adenine Ni-N3 and imidazole Ni-N1 bonds have the same chemical nature, involving mainly - and only partially-bonding. The Ni-N3 bonding is discussed in connection with biological implications and possible applications.     

Crystal and Molecular Structure of N‐methyl‐N‐3‐(sulfonato)propyl‐3‐[tris(trimethylsiloxanyl)3‐silyl]pyrrolinium Sulfobetaine Hydrate at Room Temperature and 163 K

2 (C₁₇H₄₁NO₆SSi₄) . H₂O. M_r=1017.88, triclinic, space group P‐1. The molecules are arranged in bilayers. The molecules in each bilayer are held together by electrostatic forces, i.e., O‐N⁺ contacts, and hydrogen bonds. The asymmetric unit consists of two partly disordered siloxane molecules and one water molecule. The structure of the bilayers is virtually the same at 163 K and room temperature, but the stacking of the bilayers is different. The Si‐O‐Si bond angles at low temperature are significiantly smaller than at room temperature.     

The Crystal and Molecular Structure of (μ‐terephthlato) bis [(N‐Salicylidene ‐N'‐(2‐hydroxyethyl) ethylenediamine) Copper(II)]

The title compound [[Cu(shen)]₂(tp)], {[Cu(C₁₅H₁₇O₄N₂)]2}, where tp = dianion of terephthalic acid and shen = (N‐salicylidene‐N'‐(2‐hydroxyethyl ethylene‐diamine)) has been prepared and its crystal structure determined by single crystal X‐ray diffraction at room temperature. The complex crystallizes in the orthorhombic space group Pbca with four formula units in a unit cell of dimensions a = 12.298(2), b = 14.214(2) and c = 16.436(2)Å. The structure consists of binuclear units with Cu(II) ion bridged by the tp ligand in a bis‐unidentate fashion. The five coordinate Cu(II) complex adopts a distorted square‐based pyramid. A crystallographic inversion center has been located at the center of the benzene ring of the tp bridging ligand. The Cu … Cu distance inside a same binuclear entity is 11.069Å. Intermolecular aromatic ring stacking interactions were observed with the shortest atom to atom contact being 3.423Å.     

Crystal structure of N‐[(1Z)‐1‐(3‐methyl‐3‐phenylcyclobutyl)‐2‐thiomorpholin‐4‐ylethylidene] thiourea

The crystal structure of N‐[(1Z)‐1‐(3‐methyl‐3‐phenylcyclobutyl)‐2‐thiomorpholin‐4‐ylethylidene] thiourea (C₁₈H₂₆N₄S₂) has been determined by X‐ray crystallographic techniques. The compound crystallizes in the orthorhombic space group Pbca, with unit cell parameters: a = 15.692(3), b = 20.803(8), c = 11.979(6)Å, Z = 8, V = 3911(7)ų. The crystal structure was solved by direct methods and refined by full‐matrix least squares to a final R‐value of 0.084 for 1447 observed reflections [I > 2σ ( I ) ]. In the thiosemicarbazide moiety, the S = C bond length is 1.656(6), N‐C‐N angle is 115.6(5)°. The crystal structure is stabilized by the intermolecular N‐H...S hydrogen bonds. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,crystal structure and vibrational characterization of bis‐μ‐peroxo‐hexacarbonatodicerate(IV) complexes of rubidium and cesium

The new compounds Rb₈[Ce(O₂)(CO₃)₃]₂ · 12 H₂O (1) and Cs₈[Ce(O₂)(CO₃)₃]₂ · 10 H₂O (2) were obtained from the reaction of hydrogen peroxide and Ce(III) in saturated alkali carbonate solutions. The crystal structures and the unit cell parameters of (1) triclinic, P‐1 with a = 8.973(2) Å, b = 10.815(2) Å, c = 11.130(3) Å, α = 66.992(2)°, β = 68.337(2)°, γ = 74.639(2)°, V_EZ = 914.7(4) ų, Z = 2, and (2) orthorhombic, Pbca, a = 19.3840(16) Å, b = 18.528(2) Å, c = 10.487(3) Å, V_EZ = 3766.4(13) ų, Z = 8, were determined. Both compounds contain the bis‐µ‐peroxo‐hexacarbonatodicerate(IV)‐ion, [(CO₃)₃Ce(O₂)₂Ce(CO₃)₃]^8‐. IR and Raman spectra were measured and discussed. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and crystal structure of thiosemicarbazide complexes of nickel(II) and copper(II)

Thiosemicarbazide complexes of nickel(II) [Ni(TSC)₂](HSal)₂ (I) and copper(II) [Cu(TSC)₂](HSal)₂ (Ia) (TSC is thiosemicarbazide and HSal is a salycilate anion), as well as complexes [Ni(TSC)₂](SO₄) · 2H₂O (II) and [Ni(TSC)₃]Cl₂ · H₂O (III), are synthesized and characterized by IR spectroscopy and X-ray diffraction. Monoclinic crystals I and Ia are isostructural; space group P2₁/n, Z = 2. Crystals II are monoclinic, space group P2₁/m, Z = 2. Crystals III are orthorhombic, space group Pbca, Z = 8. In I and Ia, two planar salycilate anions sandwich a planar centrosymmetric [Ni(TSC)₂]²⁺ cation to form a supermolecule. The cation and anions are additionally bound by hydrogen bonds. Other hydrogen bonds connect supermolecules into planar layers. In structure II, centrosymmetric [Ni(TSC)₂]²⁺ cations are connected by ??-stacking interactions into supramolecular ensembles of a specific type. The ensembles, water molecules, and (SO₄)^2? anions are bound in the crystal via hydrogen bonds. In the [Ni(TSC)₃]²⁺ cation of structure III, ligands coordinate the Ni atom by the bidentate chelate pattern with the formation of five-membered metallocycles. These metallocycles have an envelope conformation unlike those in I and II, which are planar. In III (unlike in analogous complexes), a meridional isomer of the coordination octahedron of the Ni atom is formed. Together with Cl1^? and Cl2^? anions, cations form supermolecules, which are packed into planar layers with a square-cellular structure. The layers are linked by hydrogen bonds formed by crystallization water molecules that are located between the layers.     

Crystal Structure of N,N'‐Bis(3‐(o‐dimethylaminoimino‐ethyl) ‐2‐hydroxy‐5‐methyl)‐benzylpiperazine

The structure of the synthesized title compound, C₃₀H₄₆N₆O₂ , was solved by using X‐ray diffraction techniques. The compound crystallized in monoclinic space group P2₁/n with cell dimensions a = 14.0629(7), b = 6.5696(3), c = 17.7948(8)Å, β = 111.35(2)°, V = 1531.2(1)ų, Z = 2, D_cal = 1.134 Mgm^‐3 and T = 293(2)K. The molecule possesses a center of symmetry, and hence, there is half a molecule in the asymmetric unit. The piperazine ring adopts chair conformation with the substituents at the equatorial position, subtending a dihedral angle of 88.87(1)° with the phenyl ring. The phenyloxy hydrogen is involved in an intramolecular O‐H...N type of hydrogen bond.     

1,6‐Hexanediammonium Dihydrogendecavanadate Dihydrate, (H3N—(CH2)6—NH3)2H2V10O28 · 2 H2O

The crystal structure of (H₃N—(CH₂)₆—NH₃)₂H₂V₁₀O₂₈ � 2 H₂O consists of dihydrogendecavanadate anion with C_i symmetry, two 1,6‐hexanediammonium cations and two water molecules. The structure has a P space group symmetry with one of the cations in special position; this cation is disordered. The polyanion of most usual protonation type is similar as formed in other known dihydrogendecavanadates.