Synthesis and Crystal Structure of Bis(<Emphasis Type="Italic">N</Emphasis>-alkyl-<Emphasis Type="Italic">N</Emphasis>-phenyl dithiocarbamato)mercury(II)

Abstract  

The mixed ligand dithiocarbamate complex was synthesized by the reaction between the ammonium salt of the dithiocarbamate ligands with mercury salt. There are two mercury complexes in the asymmetric unit with a compositional disorder between an ethyl group and a methyl group. A distorted tetrahedral geometry is found for each mercury atom defined by four sulphur atoms derived from two asymmetrically chelating dithiocarbamate ligands. IR spectra show thioureide υ(C–N) bands at 1491 cm⁻¹ which is higher than observed in the simple complexes of the same ligands. The effect of alkyl substituents were observed in the magnetic unequivalence of the thioureide and phenyl units in the NMR spectroscopy. The molecules are related to each other by virtue of the compositional disorder which exists at three positions in the alkyl group across the unit. The compound crystallizes in the triclinic space group P-1 with a = 10.4764(10) ?, b = 11.0433(10) ?, c = 18.5566(17) ?, α = 97.8980(10)^°, β = 95.3340(10)^°, γ = 110.3010(10)^°, and Z = 2.     

Synthesis,Crystal Structure,and Spectroscopy of <Emphasis Type="Italic">cis</Emphasis>-Dichlorotetrakis(2,6-Dimethylphenyl Isocyanide)Iron(II)

Abstract  

The compound cis-FeCl₂(DMPI)₄ (DMPI = 2,6-dimethylphenyl isocyanide) was synthesized and characterized by X-ray crystallography, IR spectroscopy, and ¹H-NMR. The structure of the hexanes solvate was solved in space group C2/c with a = 16.4160(2), b = 15.8028(2), c = 14.1263(2) ?, β = 92.345(1), V = 3661.56(8) ?³, Z = 4, with R = 0.0385. The coordination geometry about the Fe(II) center was octahedral with the two chlorides cis disposed. This is the first crystal structure of a cis-dihalotetrakis(isocyanide)iron(II) complex, and the isocyanide ligands trans to the chlorides are shown to participate in π-backbonding while those cis to the chlorides do not. IR spectroscopy confirms these observations, and ¹H-NMR is consistent with the presence of two different types of isocyanide ligands.     

Synthesis and Characterization of [(1-benzylpyrazole) [<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-bis(2-aminoethyl)-1,2-ethanediamine]copper(II)] Diperchlorate,a Structure with a Sterically Strained,Distorted-Trigonal-Bipyramidal Cation

Abstract  The synthesis, characterization, and molecular structure of the title compound, [(1-benzylpyrazole)[N,N-bis(2-aminoethyl)-1,2-ethanediamine]copper(II)] diperchlorate, [(nbp)(tren)Cu(II)](ClO₄)₂, 2  · 2ClO₄, is reported. The salt crystallized in the monoclinic space group P2₁/n with a = 10.1453(5) ?, b = 17.5250(8) ?, c = 13.6021(6) ?, β = 100.737(19)° and V = 2376.06(19) ?³ with Z = 4. The structure contains copper(II) (nbp)(tren) cations, each with a distorted-trigonal-bipyramidal CuN₅ coordination geometry, separated by perchlorate anions. The cations exhibit steric strain associated primarily with close contacts between the methylene protons of the nbp ligand and one of the amine groups of the tren ligand. The strain has a noticeable effect on the coordination geometry and certain physical properties of the complex. Graphical Abstract  In the title structure, steric strain in the (nbp)(tren)Cu(II) cations, associated with close contacts between protons of the nbp ligand and two of the amine groups of the tren ligand (dashed lines in the figure below) affects certain physical properties of the cation and is consistent with an anomalously long Cu(II)–N(pyrazole) distance (Cu–N41) and an unusually large axial–equatorial angle, N41–Cu–N12.      

Synthesis and Structural Characterization of <Emphasis Type="Italic">N</Emphasis>-(2-Pyridylmethyl)-3-Methoxysalicylaldiminato Copper(II) Chloride

Abstract  The copper(II) complex [Cu(C₅H₄NCH₂−N=CH–C₆H₃OCH₃–O)Cl], (1) containing a new tridentate Schiff base ligand (LH), which is the 1:1 condensation product of 2-(aminomethyl)pyridine and o-vaniline, has been synthesised and characterized by IR and UV–Vis spectra. Structural investigation shows that 1 crystallizes to a monoclinic system, having space group P2(1)/c, a = 6.9634(7), b = 18.1209(19), c = 10.3448(11) ?, α = 90°, β = 103.97(2)°, γ = 90° and Z = 4. The coordination geometry around the copper atom is slightly distorted square planar, formed by the N₂O donor set of the Schiff base and one Cl atom. The Cu–N(1), Cu–N(2), Cu–O(1) and Cu–Cl bond distances are 2.0114(14), 1.9414(14), 1.9147(12) and 2.2520(5) ?, respectively. Index Abstract  The copper(II) complex [Cu(C₅H₄NCH₂−N=CH–C₆H₃OCH₃–O)Cl], (1) containing a tridentate Schiff base ligand (LH), synthesised and characterized by IR and UV–Vis spectra. The central copper ion possesses a distorted square-planar geometry.      

Microwave Synthesis and Crystal Structure of 2-(<Emphasis Type="Italic">p</Emphasis>-Tolylimino-methyl)-phenol-copper (II)

Abstract  

2-(p-Tolylimino-methyl)-phenol-copper (II) has been synthesized and its structure determined by X-ray diffraction. It crystallizes in the monoclinic system, space group P2(1)/c, with the cell parameters a = 12.0266 (15) ?, b = 27.714 (2) ?, c = 11.0043 (11) ?, α = γ = 90.00°, β = 107.7510 (10)°, V = 3493.1 (6) ?³ and Z = 6. The Cu atom is surrounded by two O atoms and two N atoms from two 2-(p-Tolylimino-methyl)-phenol molecules to form a tetrahedron coordination environment. The complex is linked into a column by weak intermolecular interactions.     

Synthesis,Characterization and Crystal Structure of Iridium(III)bis(2-<Emphasis Type="Italic">p</Emphasis>-tolyl-benzothiazolato-N,C<Superscript>2</Superscript>)(acetylacetonate)

Abstract  A novel thiazole-based iridium (III) complex (iridium(III)bis(2-p-tolyl-benzothiazolato-N,C²)(acetylacetonate)) has been prepared and fully characterized by EA, IR, ¹H-NMR and MS. The molecular structure of the complex has been determined by single crystal X-ray diffraction analysis. The iridium (III) center adopts a distorted octahedral geometry with cis-O–O, cis-C–C, and trans-N–N chelate disposition. The complex crystallizes in the orthorhombic Pbca space group with cell parameters a = 10.1388(7) ?, b = 18.3565(12) ?, c = 31.021(2) ?, α = β = γ = 90 ° and Z = 8. The electronic absorption and emission spectra of this complex have been investigated. Index Abstract  A novel thiazole-based phosphorescent iridium (III) complex (iridium(III) bis (2-p-tolyl-benzothiazolato-N,C²)(acetylacetonate)) has been prepared and fully characterized by EA, IR, ¹H-NMR, MS and X-ray diffraction analysis.     

Synthesis and Crystal Structure of 7,8,9,10-Tetrahydro-2-bromo-cyclohepta[<Emphasis Type="Italic">b</Emphasis>]indol-6(5<Emphasis Type="Italic">H</Emphasis>)-one

The title compound, C₁₃H₁₂BrNO, was synthesized and characterised by IR, ¹H and ¹³C NMR spectroscopy. The proposed structure was confirmed by single crystal X-ray diffraction. The single crystal data revealed that the compound crystallizes in the triclinic system, sp. gr. P1, with Z = 2. The sevenmembered ring exhibits a slightly distorted envelope conformation. N–H···O hydrogen bonds form a centrosymmetric dimer, these interactions create a stair-like chain of molecules that interacts only loosely with neighbouring chains via van der Waals interactions, and C–H···π contacts are found in the crystal structure.     

Synthesis and structural studies of <Emphasis Type="Italic">tris</Emphasis>-2-chlorobenzylamine and <Emphasis Type="Italic">tris</Emphasis>-2-bromobenzylamine

The tris-2-chloro and 2-bromotribenzylamines are prepared from aqueous ammonia and 2-chlorobenzyl chloride and 2-bromobenzyl bromide, respectively, in ethanol. Recrystallization yielded colorless cubes of each product. The crystal structures are each solved in space group P , and are isostructural. The tris-2-chloro compound, 1, has a = 7.4226(5) Å, b = 9.0825(7) Å, c = 14.529(1) Å, = 78.279(1), = 82.389(1), = 84.661(1), and V = 948.41(12) ų with Z = 2, and d_calc = 1.368 Mg/m³. The tris-2-bromo analog, 2, has a = 7.6569(11) Å, b = 9.0922(13) Å, c = 14.614(2) Å, = 79.286(2), = 81.777(2), = 85.401(2), and V = 987.9(2) ų with Z = 2, and d_calc = 1.762 Mg/m³. Lithium–halogen exchange experiments conducted in tetrahydrofuran at –78C using n-butyl lithium revealed that no exchange occurred for the tris-2-chloro compound, but did occur for the tris-2-bromo analog to yield tribenzylamine upon quench and work-up.     

Synthesis and Crystal Structure of (5-Methyl-3-phenyl-1<Emphasis Type="Italic">H</Emphasis>-pyrazol-1-yl)-[5-(<Emphasis Type="Italic">p</Emphasis>-tolylamino)-2<Emphasis Type="Italic">H</Emphasis>-1,2,3-triazol-4-yl]methanone

Abstract  

(5-Methyl-3-phenyl-1H-pyrazol-1-yl)-[5-(p-tolylamino)-2H-1,2,3-triazol-4-yl]methanone was synthesized and characterized by ¹H NMR, MS and IR spectra data. The structure of title compound was identified by X-ray diffraction. Compound, C₂₀H₁₈N₆O, Mr = 358.40, crystallizes in the triclinic space group P-1 with unit cell parameters a = 10.303(6), b = 12.489(7), c = 15.305(9) ?, α = 108.489(12), β = 101.920(11), γ = 96.971(13)°, V = 1790.0(17) ?³, Z = 4, Dx = 1.330 mg/cm³. The final R was 0.0520.     

Synthesis and crystal structure of mixed-ligand Cu(II) complex of <Emphasis Type="Italic">N</Emphasis>-(1-phenyl-3-methyl-4-benzylidene- 5-pyrazolone) <Emphasis Type="Italic">p</Emphasis>-nitrobezoylhydrazide and pyridine

A new mixed-ligand copper(II) complex, [Cu(PMBP-PNH)Py], (PMBP-PNH = N-(1-phenyl-3-methyl-4-benzylidene-5-pyrazolone) p-nitrobezoylhydrazide; Py = pyridine), has been synthesized by solvothermal method and characterized by elemental analysis, IR spectrum, thermal analysis and single crystal X-ray diffraction: monoclinic, space group Cc with a = 6.0422(8) Å, b = 22.796(3) Å, c = 18.353(3) Å, β = 93.199(3)^∘, Mr = 582.08, V = 2524.0(6) ų, Z = 4. The copper(II) ion in the title complex is in a slightly distorted square-planar arrangement of the ONO donor atoms of primary ligand PMBP-PNH and one N-donor atom in the secondary ligand pyridine.     

Synthesis and Crystal Structure of Bis[<Emphasis Type="Italic">N</Emphasis>-{(<Emphasis Type="Italic">S</Emphasis>)-1-Phenylethyl}-<Emphasis Type="Italic">N</Emphasis>-{1-(2-Pyridinyl)Methyl}Amine] Zinc(II) Perchlorate

Abstract  

The reaction of N-[(S)-1-phenylethyl]-N-[1-(2-pyridinyl)methyl]amine (PEPMA) with Zn(ClO₄)₂ affords (PEPMA)₂Zn(ClO₄)₂ at room temperature. The complex is characterized by elemental analysis, ¹H-MNR and X-ray crystallography. The crystal system is orthorhombic with space group of P2₁2₁2₁ and unit cell parameters: a = 8.6911(4), b = 9.7755(7), c = 37.275(2) ?, V = 3166.9(3) ?³, Z = 4, D _x  = 1.445 Mg/m³. The crystal structure reveals that zinc metal is ligated by two PEPMA ligands in a distorted tetrahedral fashion. Interestingly, both nitrogen atoms of amine at PEPMA to the central zinc metal exhibit (R)-configuration.     

Crystal Structure of Two <Emphasis Type="Italic">V</Emphasis>-shaped Ligands with <Emphasis Type="Italic">N</Emphasis>-Heterocycles

Two V-shaped ligands with N-heterocycles, bis(4-(1H-imidazol-1-yl) phenyl)methanone (1), and bis(4-(1H-benzo[d]imidazol-1-yl)phenyl)methanone (2) have been synthesized and characterized by elemental analyses, IR and 1H NMR spectroscopy. Crystal structures of 1 and 2 have been determined by X-ray diffraction. The crystal of 1 is monoclinic, sp. gr. P2₁/c, Z = 4. The crystal of 2 is orthorhombic, sp. gr. Fdd2, Z = 8. X-ray diffraction analyses show that the V-shaped angles of 1 and 2 are 122.72(15)° and 120.7(4)°, respectively. Intermolecular C–H···O, C–H···N, C–H···π, and π···π interactions link the components into three-dimensional networks in the crystal structures.     

Synthesis and Characterization of <Emphasis Type="Italic">N,N</Emphasis>-di(prop-2-ynyl)-<Emphasis Type="Italic">p</Emphasis>-toluidine

Abstract  

In order to investigate the intramolecular [4 + 2] cycloaddition, we prepared some new tertiary N-(5-substituted-2-furfuryl)-N-prop-2-ynyl-p-toluidines [Hergold-Brundić et al., Acta Cryst C56:e520, 2000; Mance and Jakopčić, Mol Divers 9:229, 2005; Mance, “unpublished results”] by the alkylation of secondary N-(5-substituted-2-furfuryl)-p-toluidines with the propargyl-bromide [Mance and Šindler-Kulyk, Synth Commun 26:923, 1996]. In the course of preparation of N-(5-methoxy-2-furfuryl)-N-prop-2-ynyl-p-toluidine [Mance, “unpublished results”], besides the main product (compound 1) (Scheme 1) we obtained N,N-di(prop-2-ynyl)-p-toluidine (compound 2) as the colourless crystals. The title compound 2, N,N-di(prop-2-ynyl)-p-toluidine, C₁₃H₁₃N, crystallizes in monoclinic C 2/c space group with unit cell parameters: a = 19.5319(9) ?, b = 7.5230(3) ?, c = 15.9000(7) ?, β = 112.554(5)°, V = 2157.64(18) ?³, Z = 8. The crystal structure is dominated by van der Waals forces only. The bond distances around amine N atom correspond to σ dominated bonds (1.467(2), 1.462(2) and 1.419(2) ?). The angles sum around amine N atom is in accord with sp³ hybridization (343°).     

Synthesis of <Emphasis Type="Italic">E</Emphasis> Isomer and Crystal Structures of <Emphasis Type="Italic">E</Emphasis> and <Emphasis Type="Italic">Z</Emphasis> Isomers of 3-(2,5-Dimethoxyphenyl)-2-(4-methoxyphenyl)acrylonitrile

Abstract Details of the synthesis of the E isomer of 3-(2,5-dimethoxyphenyl)-2-(4-methoxyphenyl)acrylonitrile, and the X-ray crystal structures of both the E and Z isomers of this compound are presented. The E isomer crystallizes in the P2₁/c space group with cell parameters, a = 8.5659(17) ?, b = 16.399(3) ?, c = 11.224(2) ?, α = 90°, β = 95.27(3)°, γ = 90°and Z = 4. The Z isomer crystallizes in the Pca2₁ space group with cell parameters, a = 4.1223(8) ?, b = 19.113(4) ?, c = 19.453(4) ?, α = 90°, β = 90°, γ = 90° and Z = 4. Index Abstract Synthesis of E isomer and X-ray crystal structure determination of both E and Z isomers of 3-(2,5-dimethoxyphenyl)-2-(4-methoxyphenyl)acrylonitrile are presented.      

Structure of 6,13-bis(<Emphasis Type="Italic">N</Emphasis>, <Emphasis Type="Italic">N</Emphasis>-dimethylcarbamoyl) thioquinanthrene

The crystal structure of 6,13-bis-(N,N-dimethylcarbamoyl)thioquinanthrene 3 has been determined as monoclinic, with space group P2(1)/c with lattice parameters a = 10.044(2) Å, b = 21.385(4) Å, c = 10.889(3) Å, = 102.92(3)°, Z = 4 and D_calc = 1.342 Mg/m³. The middle 1,4-dithiin ring in the title compound 3, C₂₄H₂₀N₄O₂S₂ is in a boat conformation with the dihedral angle between the planes of the aromatic rings 132.45(8)°.     

Crystal structure of (2<Emphasis Type="Italic">Z</Emphasis>)-(3,3-dimethyl-3,4-dihydroisoquinolin- 1(2<Emphasis Type="Italic">H</Emphasis>)-ylidene)nitrosoacetonitrile

The crystal structure of (2Z)-(3,3-dimethyl-3,4-dihydroisoquinolin-1(2Н)-ylidene)nitrosoacetonitrile is determined (T = 150 K, R1 = 0.0435). The compound crystallizes as the E-cis and Z-cis isomers of the nitroso tautomer. Two independent molecules differ in the rotation of the nitroso group about the С–С bond between the dihydroisoquinoline group and the substituent. Analysis of bond lengths reveals their conjugation and prevailing contribution of the zwitter-ionic structures with the positive charge located on the isoquinoline fragment and the negative charge located on the substituent. Molecules having E and Z conformations are connected by the N–H···O hydrogen bond (N···O 2.922(3) Å) into dimers. The N–H group of the other molecule forms the intramolecular N–H···O hydrogen bond (N···O 2.544(3) Å) which closes a sixmembered cycle. Electronic absorption spectra are studied, and quantum-chemical modeling of the compound is performed.     

Crystal Structure and Conformational Analysis of 4-[(<Emphasis Type="Italic">p</Emphasis>-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-Dimethylamino)Benzylidene]-2-Phenyloxazole-5-One

Abstract  

Molecular and crystal structure of 4-[(p-N,N-dimethylamino)benzylidene]-2-phenyloxazol-5-one, C₁₈H₁₆N₂O₂, have been determined by single crystal X-ray diffraction study. The title compound is monoclinic, with a = 12.1704(23) ?, b = 3.9810(5) ?, c = 30.9603(56) ?, β = 101.176(15)°, Z = 4, D _x = 1.32 g/cm³, μ(Mo Kα) = 0.087 mm⁻¹, and space group is P12₁/c1. The structure was solved by direct methods and refined to a final R = 0.047 for 3166 reflections with I > 2σ(I). The crystal structure is stabilized by C–H⋯O and C–H⋯N type intra-molecular, C–H⋯O type inter-molecular interactions. To enlighten the flexibility and the geometric isomerism (E or Z) of the title compound, the selected torsion angle is varied from −180 to 180° in every 10° separately and molecular energy profile is calculated and analyzed.     

Synthesis and Structure of the Dimeric Copper(II) Complex Tetrakis[<Emphasis Type="Italic">N</Emphasis>-thiazol-2-yl-(4-methylphenyl)sulfonamidate]dicopper(II)

Abstract The coordination chemistry of the ligand N-thiazol-2-yl-toluenesulfonamidate towards the copper(II) ion has been investigated using an electrochemical synthesis method. The X-ray structure of this complex was elucidated and is discussed. The compound crystallised in the monoclinic crystal system, P2₁/c space group with a = 17.3888(9), b = 16.3003(9), c = 18.3679(9) ? and β = 114.3640(10)°. Four bidentate sulfathiazolato anions bridge two metal centers in a paddle-wheel fashion, with the nitrogen atoms as donors to give a dimeric species with a Cu···Cu distance of 2.7859(5) ?. Graphical Abstract The coordination chemistry of the ligand N-thiazol-2-yl-toluenesulfonamidate towards the copper(II) ion has been investigated using an electrochemical synthesis method. The X-ray structure of the product has been elucidated and is discussed. Sulfathiazolato anions act as bridging ligands to give a dimeric species with a Cu···Cu distance of 2.7859(5) ?.      

Synthesis and structure of oxovanadium(IV) complexes [VO(<Emphasis Type="Italic">Acac</Emphasis>)<Subscript>2</Subscript>] and [VO(<Emphasis Type="Italic">Sal</Emphasis>: <Emphasis Type="Italic">L</Emphasis>-alanine)(H<Subscript>2</Subscript>O)]

Bis(acetylacetonato)oxovanadium C₁₀H₁₄O₅V (I) and (S)-[2-(N-salicylidene)aminopropionate]oxovanadium monohydrate C₁₀H₉NO₅V (II) are synthesized. The crystal structures of compounds I and II are determined using single-crystal X-ray diffraction. Crystals of compound I are triclinic, a = 7.4997(19) Å, b = 8.2015(15) Å, c = 11.339(3) Å, α = 91.37(2)°, β = 110.36(2)°, γ = 113.33(2)°, Z = 2, and space group \(P\bar 1\). Crystals of compound II are monoclinic, a = 8.5106(16) Å, b = 7.373(2) Å, c = 9.1941(16) Å, β = 101.88(1)°, Z = 2, and space group P2₁. The structures of compounds I and II are solved by direct methods and refined to R₁ = 0.0382 and 0.0386, respectively. The oxovanadium complexes synthesized are investigated by vibrational spectroscopy.     

Synthesis,Characterization, Crystal Structure,and Hirshfeld Surface Analysis of Ethyl 2-(4-bromophenyl)-1-cyclohexyl-1<Emphasis Type="Italic">H</Emphasis>-benzo[<Emphasis Type="Italic">d</Emphasis>]imidazole-5-carboxylate

The title compound, C₂₂H₂₃N₂BrO₂ was synthesized via one-pot reductive cyclization method and characterized by CNH analysis, FT-IR, UV-visible, mass, ¹H and ¹³C NMR spectra, thermogravimetric analysis (TGA) and single crystal X-ray diffraction method. The compound crystallizes in monoclinic crystal system: sp. gr. P2₁/c, Z = 4. The crystal data reveals that the intermolecular interactions of the C–H···π and π···π type connect the molecules which was also visualized with the help of Hirshfeld surface analysis.