Synthesis, spectroscopic studies, and crystal structure of tris(tetra-n-butylammonium) hexakisisothiocyanatoindate(III)

The reaction of a 1:10 molar ratio between indium chloride and tetra-n-butylammonium thiocyanate in ethanol affords the complex [(n-C₄H₉)₄N]₃[In(NCS)₆] (1), the structure of which has been established by X-ray diffraction. This compound crystallizes in the cubic space group Pa3¯ with eight formula units in the unit cell. The formula unit consists of three separate cationic tetra-n-butylammonium groups and an independent hexakisisothiocyanatoindium anionic group. The six near linear thiocyanate ligands coordinate octahedrally through the nitrogen atom to the indium metal center. The coordination of the n-butyl groups to the ammonium-nitrogen atom is tetrahedral. The complex has also been characterized by IR, ¹H and ¹³C NMR, physical properties, and X-ray powder analysis.     

A dinuclear cyano-bridged complex based on hexacyanoferrate(III) and samarium(III) nitrate: synthesis and crystal structure

A new complex, [Sm(DMF)₄(H₂O)₄Fe(CN)₆]·H₂O (DMF = N, N-dimethylformamide), has been synthesized and characterized by X-ray single crystal structure and thermogravimetric analyses. The complex crystallizes in the P2₁/n space group, with lattice parameters a = 17.583(4) Å, b = 8.870(2) Å, c = 19.845(6) Å, = 95.98(3)°, V = 3078(1) ų, D _x = 1.679 Mg m^–3, D _m = 1.65(1) Mg m^–3, Z = 4. The molecular structure shows that a cyano-bridged bimetallic structure is obtained. The Sm atom is coordinated by eight oxygen atoms of four water molecules and four DMF molecules and one nitrogen atom of the bridging cyanide ligand. The iron atom assumes approximately an octahedral environment surrounded by six CN ligands. The hydrate water molecule is hydrogen-bonded to one of the O atoms bound to Sm. Each terminal CN ligand of the Fe(CN) ₆ ^3– entity is hydrogen-bonded to some O atoms of water molecules. An infrared spectrum is also reported.     

Cobaloxime derivatives: synthesis and spectroscopic studies of alpha-furilglyoximate of cobalt (III), X-ray structure of bis(thiourea)bis(alpha-furilglyoximato)cobalt(III) nitrate

-Furilglyoxime (H₂afdo) complexes of cobalt(III) were used to synthesize H₂afdo-cobaloximes with thiourea, triphenylphosphine, and aniline astrans-axial ligands. Encapsulation of the H-bonded species with BF₃OEt₂ resulted in stable BF₂-capped macrocycles which mimic the central metal core of the biological molecules such as vitamin B₁₂ etc. Solution chemistry and spectroscopic measurements of the BF₂-macrocycles as well as H-bonded cobaloximes revealed six-coordinated cobalt(III) as the central atom and a short hydrogen bond in the case of latter. X-Ray structure of a representative complex [Co(Hafdo)₂(thiourea)₂]NO₃ (Haldo=-furilglyoxime anion) confirmed a pseudo-octahedral geometry around cobait(III) with thiourea bonded to axial positions. The oxygen atoms of furyl groups are not involved in any kind of bonding and the overall structure of the complex differs from that of the H₂dmg-cobaloximes (H₂dmg=dimethylglyoxime).     

Synthesis,spectral, X-ray diffraction and DFT studies on 1-(2-methyl-2-propenyl)-3-(2,3,4,5,6-pentamethylbenzyl)benzimidazolium chloride hydrate

A new benzimidazole based N-heterocyclic carbene (NHC) salt (1) was synthesized by the reaction of benzimidazole precursor with alkyl halide. The structure of 1 was determined by elemental analysis, FT-IR, ¹H NMR and ¹³C NMR spectroscopy tecniques and X-ray crystallography. The compound crystallized in the triclinic space group P-1 with two molecules in the unit cell. The optimization of 1 was firstly performed at B3LYP/6-311G++(d,p) level, then the theoretical spectral studies performed and compared with the experimental values. Besides the frontier molecular orbital energies and chemical reactivity analysis of 1, together with the electrostatic potential and molecular electrostatic potential analyses were performed at the same level of theory.     

A new copper(II) coordination compound with 2,2′-bipyridine-N-oxide as a ligand: Crystal structure, synthesis and spectroscopy

A new copper(II) coordination compound with the ligand 2,2′-bipyridine-N-oxide (abbreviated as bpyNO), Cu(bpyNO)₂(CF₃SO₃)₂, is described. This compound is investigated in detail by spectroscopy, EPR and X-ray crystal structure analysis. The compound crystallizes in the monoclinic space group P2₁/n with a = 6.554(1) ?, b = 13.681(3) ?, c = 14.935(3) ?, β = 98.77(3)°, Z = 2. The copper has an axial elongated octahedral geometry with the basal plane formed by two trans-orientated bpyNO molecules with Cu_N distance of 2.008(2) ? and a Cu_O distance of 1.950(2) ?. The axial positions are occupied by oxygen atoms of two trans-oriented triflate anions with a Cu_O distance of 2.397(2) ?.     

Synthesis,crystal structure and characterization of new transition metal compounds of bromophenols: Bis(2,4,6‐tribromophenolato) di(N‐methylimidazole)M(II) (M=Co,Cu)

Bis(2,4,6‐tribromophenolato)di(N‐methyl imidazole)M(II), where M stands for cobalt and copper metals, was synthesized via reaction of the corresponding metal sulphate and 2,4,6‐tribromophenolate in aqueous media in the presence of N‐methyl imidazole and sodium hydroxide. Although various crystallization procedures were applied only cobalt complex was obtained as single crystals. The Co(II) ion has a distorted octahedral enviroment involving two O atoms and two N atoms of the Bis(2,4,6‐tribromophenolato)di(N‐methyl imidazole) ligand. Powder x‐ray diffraction pattern of copper compound was used for cooper complex. For characterizations of complexes carbon, hydrogen and nitrogen elemental analysis, FTIR and UV spectroscopy, DSC thermal analysis and magnetic susceptibility measurements at room temperature were performed. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis, spectroscopy, and X-ray structures of fac-(CO)3(dppe)MnSC(S)H, fac-(CO)3(dppe)ReSC(S)H, fac-(CO)3(dppp)ReSC(S)H, and fac-(CO)3(dppb)ReSC(S)H

The monodentate dithioformato complexes, fac-(CO)₃(dppe)MnSC(S)H (1), fac- (CO)₃(dppe)ReSC(S)H (2), fac-(CO)₃(dppp)ReSC(S)H (3), and fac-(CO)₃ (dppb)ReSC(S)H (4), where dppe is 1,2-bis(diphenylphosphino)ethane, dppp is 1,3-bis(diphenylphosphino)propane, and dppb is 1,4-bis(diphenylphosphino)butane, were synthesized from the treatment of the corresponding hydrides, fac-(CO)₃ (P-P)MSC(S)H with CS₂. Compounds 1–4 crystallize in the monoclinic crystal system: for 1, space group = P2₁/c, a = 15.3139(3) Å, b = 9.7297(4) Å, c = 19.0991(6) Å, = 105.928(1), V = 2736.5 ų, Z = 4; for 2, space group = P2₁/c, a = 15.6395(8) Å, b = 9.8182(5) Å, c = 19.4153(11) Å, = 106.741(1), V = 2854.9(3) ų, Z = 4; for 3, space group = P2₁/n, a = 11.3570(10) Å, b = 19.465(2) Å, c = 15.5702(14) Å, = 104.776(2), V = 3328.3(5) ų, Z = 4; and for 4, space group = C2/c, a = 32.078(2) Å, b = 10.4741(6) Å, c = 19.0608(9) Å, = 94.315(2), V = 6386.1(6) ų, Z = 8.     

Synthesis and structural characterization of a novel polymeric praseodymium(III) complex with a new flexible double betaine

A novel polymeric Pr(III) complex with a new double betaine, namely [{Pr(L¹)_1.5(H₂O)₂} _n ][ClOli4]3 _n ·nH₂O (1) (L¹ = 1,4-diazoniobicyclo[2,2,2]octane-1,4-dipropionate), has been synthesized and characterized by X-ray analysis. In the title complex, the Pr(III) atom is nine-coordinated by seven oxygen atoms from five L¹ ligands and two aqua ligands. Each pair of adjacent praseodymium(III) atoms is linked by a pair of ³ chelating and bridging carboxylate groups, thus forming an infinite metal···metal chain running parallel to the a direction, and such chains are cross-linked by flexible backbones of L¹ ligands into a three-dimensional network with the perchlorate anions and lattice water molecules accommodated in the interstitial space. The title complex crystallizes in the monoclinic space group P2₁/n with a = 8.085(2), b = 14.316(3), c = 29.775(6) Å, = 103.04(3)° and Z = 4.     

Synthesis, spectroscopic characterization and X-ray structure determination of tetrabutylammonium trans-diamminetetranitrocobaltate(III)

The cobalt(III) complex salt [(C₄H₉)₄N][trans-Co(NH₃)₂(NO₂)₄] has been synthesized in high yield by reacting equimolar quantities of [(C₄H₉)₄N]Br and K[trans-Co(NH₃)₂(NO₂)₄] in aqueous medium at room temperature. The product thus formed has been re-crystallised from acetone-water mixture, in the monoclinic space group P 2₁/n, with cell dimensions a=11.651(3) ?, b=19.005(4) ?, c=11.733(5) ?, β=90.28(3)°. The X-ray structure determination revealed the presence of discrete ions, [(C₄H₉)₄N]⁺ and [trans-Co(NH₃)₂(NO₂)₄]⁻. The central metal ion cobalt(III) in the anion is found in octahedral environment, in trans geometry, while the organic counterion is a quaternary alkylammonium cation. The crystal lattice is stabilized by electrostatic interactions between the cations and anions.Supplementary material Crystallographic data (excluding structure factors) for the structure(s) reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 291300. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (44) 1223 336-033; e-mail: deposit@ccdc.cam.ac.uk.     

Synthesis, properties, and X-ray structure of [Cu(dpa)Cl2] (dpa = di-(2-picolyl)amine)

The mono(dpa)copper(II) complex [Cu(dpa)Cl₂] (1) (dpa = di-(2-picolyl)amine) has been synthesized and structurally characterized. It crystallizes in the monoclinic system P2₁/n with a = 8.155(1), b = 12.560(1), c = 12.817(2) Å, = 91.64(2)°, V = 1312.3(2) ų, Z = 4. The copper atom is coordinated by three nitrogen atoms from the dpa ligand and two chlorides in a distorted square-pyramidal environment. Cyclic voltammetric data show that 1 undergoes the reversible one-electron oxidation to the Cu(III) and the reversible one-electron reduction to the Cu(I) state.     

Tris-(thiocyanato)-bis-(hexamethylenetetramine)-nona-(aquo) lanthanum(III): synthesis, crystal structure, IR and Raman characterization

The title compound (LaC₁₅H₄₂N₁₁O₉S₃) was prepared and characterized by means of X-ray, IR and Raman measurements. The crystals are orthorhombic: Pnma (No. 62), a = 21.117(2), b = 14.736(2), c = 10.082(1) Å, and Z = 4. The structure consists of polyhedra with a La(III) ion in the center of them and hexamethylene molecules, which link these polyhedra. Each La(III) ion coordinates seven molecules of water and two thiocyanate ions via nitrogen atoms. The IR and Raman spectra, which have been obtained and interpreted, are in good agreement with X-ray results.     

Synthesis, characterization, and X-ray crystal structure of di-(2,4-imidazolidinedione-5-ethyl)disulfide, C10H14N4O4S2

Di-(2,4-imidazolidinedione-5-ethyl)disulfide or homocystine hydantoin, C₁₀H₁₄N₄O₄S₂ (I), crystallizes in the non-centrosymmetric space group P2₁ (No. 4) with two molecules in the unit cell with a = 7.132(1), b = 9.282(2), c = 10.770(2) Å and = 105.68(1)°. The two imidazolidinedione rings are planar with a dihedral angle of 46.9°. The rings are joined by a diethyl disulfide bridge at chiral centers on the rings. The C-S-S-C torsion angle is –80°(–sc). The absolute stereochemistry of the chiral centers was determined to be (5S, 5S), = + 0.92 (11). Important bond distances include: S-S = 2.022(4); S-C (mean) = 1.809(8); and C=O (mean) = 1.224(7) Å. The compound is stabilized by a network of intermolecular carbonyl-to-amine hydrogen bonding and van der Waals cohesive forces.     

Preparation,crystal structure,spectrographic characterization,thermal and third order nonlinear optical properties of benzyltriethylamine bis(2-thioxo-1,3-dithiole-4,5-dithiolato)nickel(III)

The preparation and crystal structure of a novel nonlinear optical organometallic crystal, benzyltriethylamine bis(2-thioxo-1,3-dithiole-4,5-dithiolato)nickel(III) (BTEANDT), are described. The crystal was characterized by elemental analyses, infrared and X-ray powder diffraction spectroscopy, thermal analysis and optical absorption. The third order nonlinear optical properties of crystal were investigated by using the Z-scan technique at 1064 nm with 20 ps. A self-focusing effect and a saturable absorption were observed. The nonlinear refraction coefficient (n₂) and the nonlinear absorption coefficient (β) have been found to be 7.311×10⁻¹⁸ m²/W and −6.064×10⁻¹¹ m/W when the on-axis irradiance at focus (I₀) is 3.025 GW/cm². The relationship between β and I₀ was studied, which has revealed that the former is proportional to the latter. The result has been explained with the theory of absorption cross-section.     

Distortion Isomerism of Cu(II) Chloride Adducts with Bis(2-benzimidazolyl)ethane. Synthesis,Characterization, X-ray Structures and Spectroscopy of Four Different Isomers

3D structures and spectroscopic properties are reported of four compounds with the ligand bis(2-benzimidazolyl)ethane (hereafter abbreviated as dbz) attached to CuCl₂, all having the general formula [Cu(dbz)Cl₂](Hb) _x . (in which Hb = EtOH or MeOH and x = 1/2 or 1). The X-ray crystal structure has been solved from these four slightly different compounds, namely: green α-[CuCl₂dbz](C₂H₅OH)_1/2 (1), the red compound β-[CuCl₂dbz](C₂H₅OH)_1/2 (2), which both have two slightly different units in the unit cell, the red α-[CuCl₂dbz](CH₃OH) (3) and a blue–green compound β-[CuCl₂dbz](CH₃OH) (4). The geometry around the Cu(II) anion is distorted tetrahedral for all four compounds, with chromophores consisting of two nitrogen atoms of the bidentate chelating dbz molecule and two chloride anions. The unit cells of compound 1 and 2 consist of two chemically identical, but crystallographically different units, while compounds 3 and 4 each have only one independent CuCl₂-(dbz) unit. The major differences are observed in the dihedral angles NCuN–ClCuCl, which vary from 29.3 to 77.1° for the four compounds. The differences are related to different packing effects, ring–ring stacking and H-bond interaction, due to the two different alcohols used. In fact these four compounds represent a new range of examples of distortion isomerism in pseudo-tetrahedrally coordinated species. Characterisation of the four compounds has been completed by IR, EPR and LF spectroscopy.     

Synthesis,characterization and photoluminescence studies of new Cu(II) complex

In the current work, a new coordination complex, [Cu(HL)₂], 1 [H₂L = 2–((E)–(2–hydroxypropylimino)methyl)–4–nitrophenol] was successfully synthesized and characterized by IR, UV-vis and photoluminescence spectroscopic techniques, single crystal and powder X-ray diffraction measurements. In the crystalline structure of complex 1, the aliphatic –OH group of the ligand is not coordinated and points away from the metal coordination zone, and also actively participates in intermolecular bifurcated O?H···O hydrogen bonds which link the molecules to form hydrogen-bonded linear chains. C?H···π and π···π contacts also connect the molecules in the structure which form to 3D structure. This hydrogen bonded polymeric networks lie in the bc-plane and stacks along to the a-axis. Furthermore, complex 1 and its ligand H₂L display an intense navy-blue emission and blue emission in the solid state at room temperature, respectively, when they are excited under UV light.     

Synthesis and structural characterization of 2-mercapto-1-tert-butylimidazole and its Group 12 metal derivatives (HmimtBu)2MBr2 (M = Zn, Cd, Hg)

2-Mercapto-1-tert-butylimidazole (Hmim^tBu) and its Group 12 metal complexes (Hmim^tBu)₂ MBr₂ (M = Zn, Cd, Hg) have been readily prepared and structurally characterized. Whereas the former displays a dimeric structure in the solid state with two S H–N interactions linking each pair of molecules, the four-coordinate complexes exhibit distorted tetrahedral geometries with the S–M–S angles in the range 103.2–135.2. The average M–Br bond lengths are 2.401, 2.567, and 2.688 Å for M = Zn, Cd, and Hg, respectively, and the corresponding average M–S bond distances are 2.350, 2.540, and 2.467 Å. The average C–S bond length for all the complexes (1.72 Å) is only ca. 0.02 Å longer than the corresponding value in the free ligand. Hmim^tBu is orthorhombic, space group Pbca, a = 10.1571(5) Å, b = 9.7906(5) Å, c = 17.6616(9) Å, V = 1756.34(15) ų, Z = 8; (Hmim^tBu)₂ZnBr₂ is monoclinic, space group C2/c, a = 17.187(3) Å, b = 8.9908(17) Å, c = 15.560(3) Å, = 117.206(3), V = 2138.3(7) ų, Z = 4; (Hmim^tBu)₂CdBr₂ is triclinic, space group P , a = 7.4625(6) Å, b = 9.6149(9) Å, c = 31.020(3) Å, = 93.485(2), = 94.579(2), = 103.872(2), V = 2146.6(3) ų, Z = 4; (Hmim^tBu)₂HgBr₂ is monoclinic, space group P2₁/c, a = 6.8908(6) Å, b = 10.2397(9) Å, c = 29.859(3) Å, = 94.364(2), V = 2100.7(3) ų, Z = 4.     

Crystal structure of 5-(p-methoxyphenylamino)indane and AM1 calculations on N-arylamines derivatives, precursors of phenothiazine drugs

The structural determination by X-ray crystallography of the titled N-arylamine 4a, as well as AM₁ calculations on a series of derivatives (4b–c, 5a–c), are reported. The compound 4a is monoclinic P2₁/c with a = 7.656(3), b = 23.655(5), c = 7.686(9) Å, = 112.59(6)°, V = 1285.2(2) ų and Z = 4. This structure has been used as a template for the building of some others derivatives used for AM₁ calculations. The results show that the cyclization position on the aromatic rings, which can lead to two regioisomers, depends on the nature of the benzylic substituants.     

Novel Complexes of Zinc(II) with Different Proton Transfer Ion Pairs Obtained from Dipicolinic Acid: Synthesis, Characterization and X-ray Crystal Structure

Abstract  Three new complexes of zinc(II) with three different proton transfer compounds, obtained from pyridine-2,6-dicarboxylic acid (dipicolinic acid) and different Lewis bases, were synthesized and characterized using IR, ¹H NMR and ¹³C NMR spectroscopy and single crystal X-ray diffraction. The chemical formulae and space groups of the complexes are (pipzH₂)[Zn(pydc)₂] · 4H₂O, P2₁/n (1), (EDGnH₂)[Zn(pydc)₂] · 3H₂O, P2₁/c (2) and (pdaH₂)[Zn(pydc)₂] · 4H₂O, (3) where pydc, pipz, EDGn and pda are standing for dipicolinic acid, piperazine, ethylenediguanidine and 1,3-propanediamine respectively. Cell parameters of the complexes are a = 7.9493(4) ?, b = 13.4386(7) ?, c = 21.0557(11) ?, β = 90.415(5)° for 1; a = 9.785(3) ?, b = 25.671(4) ?, c = 9.3402(16) ?, β = 90.790(17)° for 2 and a = 8.411(5) ?, b = 11.650(7) ?, c = 12.793(8) ?, α = 115.534(9)°, β = 92.791(10)°, γ = 97.778(10)° for 3. The three crystal structures illustrate that the metal ion is six-coordinated by two pydc’s. In all three compounds a large number of O–H⋯O, N–H⋯O and C–H⋯O hydrogen bonds are observed. These interactions as well as other noncovalent interactions such as ion–pairing and π–π stacking play an important role in the formation and stabilization of supramolecular systems in the crystal lattices. Index Abstract  The main purpose of this paper is to report and discuss about the synthesis, characterization, crystal structure and non-covalent interactions of three supramolecular frameworks of six-coordinated Zn(II) complexes, obtained by the reaction of different proton transfer compounds, i.e. (pipzH₂)(pydc), (EDGnH₂) (pydc) · 3H₂O and (pdaH₂)(pydc) · (pydcH₂) · 2.5H₂O with corresponding metallic salts.      

1,3-Bis(4-Pyridinylcarbonyl)-2-Imidazolidinethione and Its First Cluster Complex: Synthesis,Crystal Structure and Luminescence Properties

Abstract  The first cluster complex of 1,3-bis(4-pyridinylcarbonyl)-2-imidazolidinethione (4-bpit) with CuI was prepared and characterized. Single crystal X-ray diffraction analysis established that the compound crystallizes in the monoclinic system, space group C2/m, with a = 15.601(3), b = 12.438(3), c = 12.570(3)?, β = 110.02(3), Z = 4, V = 2291.8(8)?³. This compound is also a coordination polymer with one-dimensional double-ribbon structure containing the adaptable rhomboid Cu₂I₂ cluster unit. The solution-state luminescence spectra showed that the high-energy emission may be associated with a ligand-to-ligand charge-transfer excited state. Graphical Abstract  The first cluster complex of 1,3-bis(4-pyridinylcarbonyl)-2-imidazolidinethione (4-bpit) with CuI was prepared and characterized. This compound is also a coordination polymer with one-dimensional double-ribbon structure containing the adaptable rhomboid Cu₂I₂ cluster unit. The solution-state luminescence spectra showed that the high-energy emission may be associated with a ligand-to-ligand charge-transfer excited state.