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.     

Crystal structures of bis(cyanido)bis(N,N′-diethylthiourea-κS) mercury(II) and bis(cyanido)bis(N,N′-dipropylthiourea-κS) mercury(II)

Two mercury(II) complexes containing cyanide and, N,N′-diethylthiourea (detu) and N,N′-dipropylthiourea (dprtu) ligands, [(detu)₂Hg(CN)₂] (1) and [(dprtu)₂Hg(CN)₂] (2), respectively, have been prepared and characterized by X-ray crystallography. In the both complexes Hg atom lies on a 2-fold rotation axis, and is coordinated to the sulfur atoms of two thiourea ligands and to two cyanide carbon atoms. Both have a distorted tetrahedral environment with bond angles about the Hg atoms in the range of 93.41(4)°–146.75(19)°. In the crystal structures symmetry related molecules are linked via N-H-N hydrogen bonds resulting in the formation of a two-dimensional network in 1, while in 2 a double stranded one-dimensional chain is formed.     

Synthesis, crystal structure, and properties of the adduct of bis(O,O′-diisopropyl dithiophosphato)nickel(II) with pyridine [Ni(i-Pr2dtp)2(py)2]

A new adduct bis(pyridine)-bis(O,O-diisopropyl dithiophosphato-S,S)nickel(II), [Ni(i-Pr₂dtp)₂(py)₂] (dtp = dithiophosphate, py = pyridine) has been obtained by re-crystallization from CH₃COCH₃. The crystal and molecular structure of the title complex has been determined by X-ray crystallography. It crystallizes in the monoclinic system, space group P2₁/c, with lattice parameters a = 6.4890(13) Å, b = 16.386(3) Å, c = 14.830(3) Å, = 99.74(3)°, V = 1554.1(5) ų, and Z = 2. The crystal structure consists of discrete molecules of [Ni(i-Pr₂dtp)₂(py)₂], which displays a slightly distorted octahedral geometry for the NiS₄N₂ chromophore. Two O,O-diisopropyl dithiophosphate ions act as bidentate ligands with their S atoms coordinated to Ni atom. Each forms a four-membered chelate ring in the equatorial plane. The N atoms from two pyridine ligands are axially coordinated to the Ni atom. The Ni S bond distances are 2.4492(8) Å and 2.5711(9) Å, and the Ni bond distances are 2.127(3) Å. Thermal analyses show that the thermal decomposition of this adduct is so unstable that loss of two pyridine ligands begins at about 65°C. Electronic and IR spectra data is in agreement with the structural data.     

Synthesis and crystal structure of trans-bis(O, O′-diisopropylthiophosphoryl-1H-imidazole-N3) bis(O,O′-diisopropyldithiophosphato) nickel(II) complex: Ni[N3-ImSP(OiPr)2]2[S2P(OiPr)2]2 (Im = imidazole; iPr = isopropyl)

The mononuclear complex, Ni[N³-ImSP(OiPr)₂]₂[S₂P(OiPr)₂]₂ (Im = imidazole; iPr = isopropyl), was unexpectedly obtained in a reaction of bis(O,O-diisopropyl-dithiophosphato) nickel(II) complex with imidazole ligand, and its structure was determined by X-ray crystallography. It crystallizes in the triclinic system, space group P , with lattice parameters a = 12.437(3) Å, b = 13.181(3) Å, c = 8.4580(17) Å, = 93.16(3)°, = 101.93(3)°, = 65.26(3)°, and Z = 1. The Ni atom has almost perfect octahedral coordination geometry and is coordinated by two N atoms of imidazole from two O,O-diisopropylthiophosphoryl-1H-imidazole ligands in axial positions and four S atoms from two (O,O-diisopropyldithiophosphato) anions which act as bidentate ligands forming a four-membered chelate ring in the equatorial plane. The Ni—S bond distances are 2.469(1) and 2.507(1) Å, and the Ni—N bond distances are 2.097(2) Å. The IR spectra data are in agreement with the structural data.     

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.     

Bis(2,6-(2′,6′-diisoproylanil)diformyl-4-chloro-phenolate) nickel(II)

Bis(2,6-(2,6-diisoproylanil)diformyl-4-chloro-phenolate) nickel(II) was prepared by the reaction of 2,6-(2,6-diisoproylanil)diformyl-4-chloro-phenol with nickel chloride. The title complex crystallized in P2₁/c, with cell dimensions a = 9.962(2) Å, b = 12.087(3) Å, c = 24.445(6) Å, and = 97.032(5), giving a volume of 2921.4(13) ų. The bis(2,6-(2,6-diisoproylanil)diformyl-4-chloro-phenolate) nickel(II) adapts an ideal parallelogram, in which the Ni atom is coordinated with two phenolic oxygen atoms [O(1), O(1A)] and two imino nitrogen atoms [N(1), N(1A)].     

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.     

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.     

Structure of bis(O,O′-diisopropyldithiophosphato-S,S′) (1,10-phenanthroline-N1,N10)zinc(II) complex, [Zn(phen)(S2P(OiPr)2)2]

The crystal and molecular structure of [Zn(phen)(S₂P(OiPr)₂)₂] (Phen = 1,10-phenanthroline) has been determined by X-ray crystallography. It crystallizes in the Monoclinic system, space group C2/c, with lattice parameters a = 19.315(4), b = 10.438(2), c = 16.567(3)Å, = 102.89 (3)°, and Z = 4. The complex has C₂ symmetry. The coordination geometry of each Zn atom, by two S atoms from two (O,O-diisopropyldithiophosphato) anions and by two N atoms from phenanthroline ligand, is that of a slightly distorted tetrahedron [Zn—S 2.2914(8)Å Zn—N 2.111(2)Å]. The Zn···S distances to the noncoordinated S atoms are long: 3.5276 Å, which are indicated that there are much weaker interactions between them.     

Synthesis, crystal structure, and spectroscopy of (azido-N1)bis(2,2′-bi-imidazoline)copper(II) perchlorate

The compound [Cu(biz)₂(N₃)](ClO₄) (biz = 2,2-bi-imidazoline) has been synthesized and characterized by X-ray crystallography and infrared spectroscopy. In addition, EPR and magnetic measurements have been performed. The compound crystallizes in the monoclinic space group P2₁/c, with a = 9.2716(2), b = 27.6454(4), c = 7.4285(1) Å, = 102.1417(6)°, V = 1861.46(5) ų, and Z = 4. The coordination geometry around the Cu(II) ion is distorted square pyrimidal, with 4 nitrogen atoms of 2 bis-chelating ligand molecules in the basal plane and one nitrogen of the azide molecule in the apical position. The perchlorate ion is noncoordinating. In the infrared the vibrations of the coordinated azide anion are observed at 2050, 1286, and 620 cm^–1, while the vibrations of the free perchlorate anion are observed at 1071, 1035, and 919 cm^–1; Cu—N vibrations are observed at 418 and 336 cm^–1. The molecules are connected in the lattice via relatively strong hydrogen bonding between the N—H groups at the back of the biz ligand and the N1 and N3 atoms of the azide ligand forming layers. No intermolecular magnetic interaction was observed for this compound.     

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.     

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.     

Synthesis, Characterization and X-Ray Structure of Bis(O-propyldithiocarbonato-κ2S,S′)bis(4-cyanopyridine-κN)nickel(II)

Abstract  

The [Ni(S₂COCH₂CH₂CH₃)₂(C₆H₄N₂)₂] adduct of 4-cyanopyridine with [Ni(S₂COCH₂CH₂CH₃)₂] was synthesized and characterized by elemental analysis, magnetic susceptibility measurement, IR, electronic spectral data, Thermogravimetric analysis/DTA techniques and X-ray diffraction analysis. The Ni atom in the title complex is octahedrally coordinated within a trans-N₂S₄ donor set, with the Ni atom located on a centre of inversion. The title complex crystallizes in the monoclinic space group P2 ₁ /c with unit cell parameters a = 11.75(4), b = 11.62(3), c = 9.20(2) ?, β = 104.99(3)°. Crystal structure was solved by direct methods and refined by full matrix least squares procedures to a final R-value of 0.0294 for 1895 observed reflections. The packing of layers of molecules is stabilized by weak C–H···N and C–H···π interactions.     

Structure,bonding, and magnetic behavior of bis(μ-chloro)-and (μ-bromo)-bridged Cu(II) dimers

It has been previously reported that dimeric compounds of the general formula [L₃Cu(II)]₂(-Cl)₂ exhibit a correlation between their magnetic coupling constantJ and the bridging Cu-Cl-Cu angle. A full survey of the published structural and magnetic data on these compounds confirms this correlation but leads to the conclusion that its physical significance is questionable. EHMO calculations on Cu₂Cl ₈ ^4– and its bromo analog show that the molecular orbitals responsible for the magnetic behavior of the dimers are not the orbitals responsible for the bonding interactions in these dimers. Therefore, they are very weakly affected by variations of the molecular structure, and no significant correlation betweenJ and any of the structural parameters is theoretically predicted. However, this situation changes when the coordination around the Cu atoms is strongly and dissymmetrically pyramidalized.     

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,Structure, and Properties of the Tris(ethylendiamine)nickel(II) Dichloride Dihydrate [Ni(H2NCH2CH2NH2)3]Cl2 ⋅ 2H2O Crystals

Crystallography Reports - The conditions for synthesis of [Ni(H2NCH2CH2NH2)3]Cl2 ⋅ 2H2O ([Ni(en)3]Cl2 ⋅ 2H2O) crystals from aqueous solutions have been considered. The synthesized...     

Synthesis,Spectral, Thermal and Structural Study of Monoaquabis(Acetylsalicylato-κO)bis(Nicotinamide-κN)Copper(II)

Abstract  

The compound has been formed by mononuclear [Cu(C₉H₇O₄)₂(C₆H₆N₂O)₂(H₂O)] units in which the metal ion as well as the water ligand lies on a twofold symmetry axis, so that only one acetylsalicylate ligand and one nicotinamide ligand are independent. The distortion from ideal five-coordinate geometries can be described best by the degree of trigonality τ. For a regular square-pyramidal (SQP) geometry the trigonality parameter is 0 and for a trigonal–bipyramidal (TBP) structure it increases to 1. The copper coordination geometry is that of a square pyramid (τ = 0.23), with the N atoms from nicotinamide ligands and the bonded carboxylate O atoms from acetylsalicylate ligands defining the quasi-planar square base. The apical site is occupied by the aqua ligand, a bond which coincides with the twofold symmetry axis and is thus exactly perpendicular to the basal plane. The thermal decomposition takes place in four steps: removing of moisture, dehydration of aqua ligand, the elimination of the nicotinamide (na) ligand and the decomposition of acetyl-groups and oxidation of salicylate ion ligands. In complex, all ligands are coordinated to the metal ion as monodendate. The IR spectra of the intermediate products showed similar results.     

Synthesis and structural characterization of a (N,N′-bis[2(S)-pyrrolidylmethyl]-propane-1,3-diamine) nickel (II) complex

The nickel(II) complex [Ni(C₄H₃NCH=N–(CH₂)₃–N=CHC₄H₃N)], (1) containing the symmetrical N₄ tetradentate Schiff base ligand, which is the 2:1 condensation product of pyrrole-2-carboxaldehyde and 1,3-diaminopropane respectively, was prepared. Structural investigation shows that it is monomeric, having space group P2₁/c, a = 7.989(7), b = 17.406(14), c = 9.193(5) Å, = 90, = 100.39(6), = 90, and Z = 4. The coordination geometry around the nickel atom is slightly distorted square planar and the conformation of the six-membered ring containing the metal,azomethine nitrogens and three carbon atoms of the connecting 1,3-diaminopropane is a symmetric boat.     

Structure of hexakis(imidazole)cadmium(II) carbonate trihydrate: [Cd(Im)6]CO3 ⋅ 3H2O

The crystal and molecular structure of the title compound [Cd(Im)₆]CO₃ 3H₂O, where Im = imidazole, has been determined by X-ray crystallography. The crystal structure consists of discrete Cd(Im)₆ ²⁺ cations, CO₃ ^2– anions and three uncoordinated water molecules. It crystallizes in the hexagonal system, space group P6₃/m, with lattice parameters a = 9.0552(l) Å, c = 21.745(l) Å, and Z = 2; The Cd(II) ion assumes centrosymmetric octahedron geometry. The bond distance of Cd–N is 2.361(l) Å. A three-dimensional intermolecular hydrogen bond network is formed between the free carbonate anions, the imidazole ligands, and the free water molecules.