Synthesis and Crystal Structure of (E)-1-(2,3-Dihydroxybenzlidene)-4,4-Dimethythiosemicarbazide

Abstract  

The Schiff base C₁₀H₁₃N₃O₂S is monoclinic, having unit cell parameters a = 9.788(1) ?, b = 9.615(1) ?, c = 12.605(1) ?, β = 108.41(1)° and V = 1125.56(2) ?³ and belongs to P2_1/n space group. The molecule is almost planar. The two hydroxyl groups present on the phenyl ring are involved in intermolecular H-bonding, which results in the stacking of molecules in the anti-parallel fashion leading an interesting network of channels. Besides this C–H⋯π and π–π (edge to edge) interactions appear to provide stability to the crystal lattice.     

Two Crystal Forms of 4-{(2<Emphasis Type="Italic">E</Emphasis>)-2-[1-(4-Methoxyphenyl)ethylidene] hydrazinyl}-8-(trifluoromethyl)quinoline

Abstract  

The Schiff base, 4-{(2E)-2-[1-(4-methoxyphenyl)ethylidene] hydrazinyl}-8-(trifluoromethyl)quinoline, crystallizes in two polymorphic forms depending on the solvent. One of these forms is monoclinic (1M), space group P2₁/c with a = 10.2906(10) ?, b = 8.9211(7) ?, c = 18.4838(15), β = 97.271(8)°, and the other is orthorhombic (1O), space group Pbca, unit-cell parameters: a = 13.6485(12) ?, b = 9.0588(9) ?, c = 27.400(2) ?. The molecules in either crystalline form have similar bond lengths and angles, but one is nearly planar while the other has a significant twist. In monoclinic form the dihedral angle between terminal ring planes is 17.26(8)° while in the orthorhombic one it is 26.11(5)°, and in this latter case the central chain is almost coplanar with the quinoline ring system while in the former these two planes are significantly twisted. The crystal structures of both forms are determined by the interplay of van der Waals forces and weak directional interactions C–H···F, π···π stacking, and—in the case of 1M—short intermolecular C–F···N contact. The crystals of 1M decomposes slowly into the powder while the other form is stable. The powder diffraction pattern of the product of decomposition of 1M is similar to that calculated for 1O. This suggests that the decomposition is a consequence of the phase transition of the less stable monoclinic into more stable orthorhombic form.     

The Structure and Characterization of [1,11-Bis(2-Hydroxybenzyl)-1,4,8,11-Tetraazaundecane]Iron(III) Perchlorate

Abstract  The structure of an Fe(III) complex of reduced Schiff base is reported. The title compound, C₂₁H₃₀ClFeN₄O₆ (I), crystallizes in the monoclinic space group P2₁/n with cell constants: a = 9.988(2) ?, b = 20.430(5) ?, c = 11.415(3) ?, β = 105.480(4)°. It contains a six-coordinate FeN₄O₂ cation where the ligand is a reduced Schiff base resulting from the NaBH₄ reduction of the condensation product between salicylaldehyde and 1,4,8,11-tetraazaundecane. Due to the increased flexibility of the saturated backbone of the ligand compared to the Schiff base from which it was synthesized, the complex adopts a trans-FeN₄O₂ conformation. There is extensive hydrogen bonding between the amine H atoms and the anion O atoms. Index Abstract  The structure of an Fe(III) complex of reduced Schiff base is reported which adopts a trans-FeN₄O₂ conformation where the ligand is a reduced hexadentate Schiff base resulting from the NaBH₄ reduction of the condensation product between salicylaldehyde and 1,4,8,11-tetraazaundecane.      

Synthesis and Crystal Structure of 2,4-Diiodo-6-[(2-morpholin-4-yl-ethylimino)-methyl]-phenolato-zinc(II)

Abstract  

One new complex, 2,4-Diiodo-6-[(2-morpholin-4-yl-ethylimino)- methyl]- phenolato-zinc(II) has been designed and synthesized. The structure was determined by UV, IR and single X-ray crystallography study. The title complex C₂₆H₃₀O₄N₄I₄Zn crystallizes in the triclinic space group P − 1 with the cell parameters a = 9.938(2) ?, b = 11.937(2) ?, c = 14.527(3) ?, α = 87.14(3)°, β = 79.03(3)°, γ = 76.20(3)°, V = 1565.1(5) ?³ and Z = 2. The central zinc(II) is four coordinate and bonds to two nitrogen atoms and two oxygen atoms from two 3,5-diiodosalicylaldehyde-2- morpholinoethylamine Schiff bases. The complex is linked into a column by weak intermolecular interactions.     

Synthesis and Crystal Structures of Two Novel Complexes with <Emphasis Type="Italic">N</Emphasis>-[2-(5-Bromo-2-Hydroxybenzylideneamino)Ethyl]-4-Methylbenzenesulfonamide as Ligand

Abstract  

Two novel complexes constructed from the sulfonamide Schiff base ligand H ₂ L, N-[2-(5-bromo-2-hydroxybenzylideneamino)ethyl]-4-methylbenzene-sulfonamide, [Cu(HL)₂] (1) and [CuL(H₂O)] (2) are synthesized and characterized via X-ray single-crystal diffraction, elemental analysis, FT-IR and UV–Vis. 1 and 2 both form 1-D supramolecular architectures by π–π stacking interactions. 1 and 2 both crystallize in monoclinic, with space group C2/c and P2/c for 1 and 2, with unit cell parameters a = 27.640(18) ?, b = 7.907(5) ?, c = 17.945(14) ?, β = 118.27(2)°, V = 3454(4) ?³, Z = 4 for 1, and a = 16.758(5) ?, b = 7.272(2) ?, c = 15.080(4) ?, β = 106.334(5)°, V = 1763.6(9) ?³, Z = 4 for 2.     

Synthesis,Characterization and X-Ray Crystal Structure of the Tri Aqua (3-Hydroxy-5-Hydroxymethyl-2-Methylpyridine-4-Carboxaldehyde-3-Methylisotiosemicarbazone: k<Superscript>3</Superscript>, O<Superscript>3</Superscript>, N<Superscript>7</Superscript>, N<Superscript>10</Superscript>) Ni(II) Nitrate

Abstract  

The title complex triaqua (3-hydroxy-5-hydroxymethyl-2-methylpyridine-4-carboxaldehyde-3-methylisothiosemicarbazone-k³,O³,N⁷,N¹⁰)Ni(II) nitrate ([Ni(PLITSC)(H₂O)₃](NO₃)₂, 1) represents the second transition metal complex incorporating an isothiosemicarbazide-pyridoxal based Schiff base that has been crystallographically characterized. Complex 1 crystallizes in a P21/n space group, with lattice constants: a = 11.2254(1) ?, b = 12.9941(2) ?, c = 12.8663(2), β = 96,7713(5)°, V = 1863.64(4) ?³, Z = 4, F(000) = 1016, R ₁ = 0.0681, wR ₂ = 0.1201. The central Ni(II) cation is found in a six-coordinate octahedral geometry formed by the tridentate Schiff base ligand PLITSC and three water molecules. The identity of 1 was further confirmed by elemental analysis, IR spectra, and conductometric and magnetochemical measurements.     

Synthesis and Crystal Structure of 1,7-Bis(4-methoxyphenyl)-4-(1,3-dithiolan-2-ylidene)-1,6-heptadiene-3,5-dione

Abstract  

The synthesis and crystal structure of 1,7-bis(4-methoxyphenyl)-4-(1,3-dithiolan-2-ylidene)-1,6-heptadiene-3,5-dione is described. This compound crystallizes in the space group P2₁ with unit cell parameters a = 14.207 ?, b = 7.752(1) ?, c = 19.473(1) ?, β = 91.00(3)°, with two molecules in the asymmetric unit. The ketenedithioacetal functionality present between the carbonyl groups prevents the possibility of keto-enol tautomerization in this compound. The cinnamoyl groups are organized parallel to each other due to the push–pull nature of the ketenedithioacetal functionality.     

Spectroscopic Studies and Crystal Structure of 4-(2-Hydroxy-3-Methoxybenzylideneamino)-<Emphasis Type="Italic">N</Emphasis>-(5-Methylisoxazol-3-yl) Benzenesulfonamide

Abstract  

Schiff base 4-[(2-hydroxy-3-methoxybenzylideneamino)-N-(5-methylisoxazol-3-yl)benzene-sulfonamide has been synthesized from the reaction of 4-amino-N-(5-methylisoxazol-3-yl)benzenesulfonamide(sulfamethoxazole) with 2-hydroxy-3-methoxybenzaldehyde. It has been characterized by elemental analysis, MS, IR, ¹H NMR, ¹³C NMR, HETCOR and UV–Visible techniques. The structure of it also has been examined crystallographically. For the compound exist as dominant form of enol-imines in both the solid state and the solutions. It crystallizes in the monoclinic space group P2₁/c with a = 8.2694(7), b = 8.3453(5), c = 26.260(2) ?, β = 97.142(7) °, V = 1798.1(2) ?³, D _x  = 1.431 g cm⁻³, R ₁ = 0.0529 and wR ₂ = 0.1370 [I > 2σ(I)], respectively.     

Synthesis,Crystal Structure and Thermal Properties of <Emphasis Type="Italic">N</Emphasis>-Acetyl-3-(2-furyl)-5-ferrocenyl-2-pyrazoline and <Emphasis Type="Italic">N</Emphasis>-Acetyl-3-(2-thienyl)-5-ferrocenyl-2-pyrazoline

Abstract  

Two novel ferrocenyl substituted N-acetyl-2-pyrazolines, N-acetyl-3-(2-furyl)-5-ferrocenyl-2-pyrazoline (3) and N-acetyl-3-(2-thienyl)-5-ferrocenyl-2-pyrazoline (4), have been synthesized and characterized by FTIR, ¹H-NMR, ¹³C-NMR techniques, elemental analysis and X-ray structure analysis. Thermal properties of these compounds have been determined by TGA, DTA and DSC analysis. Compound 3 (C₁₉H₁₈N₂O₂Fe) crystallizes in the monoclinic space group P21/c and Z = 4, with a = 8.6970(4) ?, b = 18.4725(9) ?, c = 11.0041(5) ?, β = 110.942(3)°. Compound 4 (C₁₉H₁₈N₂OSFe) crystallizes in the orthorhombic space group Fdd2 and Z = 16, with a = 84.242(2) ?, b = 13.5416(5) ?, c = 5.9405(2) ?, β = 90°. In terms of crystal packing, each compound shows different molecular arrangement, which are stabilized by C–H···O intermolecular weak hydrogen bonds, and/or C–H···π interactions.     

Synthesis and Crystal Structure of (<Emphasis Type="Italic">S</Emphasis>)-2-((<Emphasis Type="Italic">S</Emphasis>)-2-(<Emphasis Type="Italic">N</Emphasis>-Ts-Amino)-3-methylbutanoyl)-3-(1H-indol-3-yl)-6-phenyl-3,4-dihydro-1,2,4-triazin-5(2H)-one

Abstract  

The diastereoselective synthesis, NMR and X-ray structure of (S)-2-((S)-2-(N-Ts-amino)-3-methylbutanoyl)-3-(1H-indol-3-yl)-6-phenyl-3,4-dihydro-1,2,4-triazin-5(2H)-one—a potential antivirus agent are reported. The compound crystallizes in the triclinic space group P1 with unit cell parameters: a = 5.9259(6) ?, b = 9.6370(12) ?, c = 12.9541(9) ?, α = 109.210(9)°, β = 90.804(7)°, γ = 105.074(10)° and Z = 1.     

The Crystal Structures of (Z)-Ethyl 2-(4-chlorophenyl)-3-(2,4-difluorophenyl-amino)acrylate and its Analogues

Abstract  

The title compound, C₁₇H₁₄ClF₂NO₂, crystallizes in monoclinic space group P2₁/c with unit cell dimension of a = 16.276(3) ?, b = 7.5030(15) ?, c = 13.812(3) ?, α = 90°, β = 111.11(3)°, γ = 90° and Z = 4. The structure of the title compound reveals a Z configuration with respect to the C=C double bond in aminoacrylate fragment. The molecule is stabilized by intramolecular N–H···F and N–H···O hydrogen bonds. In the ethyl 2-aryl-3-arylaminoacrylates, electronic properties of the substituents in the aniline motif clearly affected the attached C–N bond length, and such effect is very little relative to Z-/E-configuration with respect to the C=C double bond.     

Structural Studies of (Pyridine)<Subscript>3</Subscript>ZnFe(CO)<Subscript>4</Subscript> and (Pyridine)(Neocuproin)CdFe(CO)<Subscript>4</Subscript>

Abstract  

The structure of the previously reported (py)₃ZnFe(CO)₄ (py = pyridine) has been determined, confirming the monomeric nature of this species. The complex has average Zn–N and Zn–Fe bond lengths of 2.0970(7) and 2.4017(3) ?, and features a coordination geometry about Fe which is intermediate between trigonal bipyramidal and face monocapped tetrahedral. The space group is P2₁/c, with a = 8.22080(10) ?, b = 16.1668(3) ?, c = 15.4669(3) ?, β = 102.5869(11)°, V = 2006.21(6) ?³, D_calc. = 1.558 g/cm³ at 150(1) K. A monomeric cadmium analogue, (pyridine)(neocuproin)CdFe(CO)₄, has also been synthesized, and found to possess a similar geometry, with average Cd–N and Cd–Fe bond lengths of 2.352(2) and 2.5380(5) ?. The space group is P[`1] P\overline{1} with a = 10.8900(2) ?, b = 11.3042(3) ?, c = 15.5488(4) ?, α = 85.1251(10)°, β = 84.3468(14)°, γ = 72.0377(15)°, V = 1808.93(7) ?³, D_calc. = 1.478 g/cm³ at 150(1) K.     

Synthesis and Crystal Structures of a Pair of Isostructural Azido-Bridged Polynuclear Schiff Base Zinc(II) Complexes

Abstract  

A pair of novel isostructural azido-bridged polynuclear zinc(II) complexes, [Zn₂(L1)₂(μ_1,1-N₃)(μ_1,3-N₃)] _n (1) and [Zn₂(L2)₂(μ_1,1-N₃)(μ_1,3-N₃)] _n (2) (HL1 = 2-bromo-4-chloro-6-[(2-isopropylaminoethylimino)methyl]phenol, HL2 = 2,4-dibromo-6-[(2-isopropylaminoethylimino)methyl]phenol), have been synthesized and structurally characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Both complexes crystallize in the orthorhombic space group Pcca. Crystal data for (1): a = 22.567(4) ?, b = 8.414(2) ?, c = 17.268(3) ?, V = 3279.0(11) ?³, Z = 8, R ₁ = 0.0441, and wR ₂ = 0.0846. Crystal data for (2): a = 22.536(4) ?, b = 8.409(2) ?, c = 17.531(3) ?, V = 3322.2(11) ?³, Z = 8, R ₁ = 0.0538, and wR ₂ = 0.0906. X-ray structure determination revealed that each zinc(II) atom in the complexes is in a trigonal–bipyramidal coordination, with one imine N atom of a Schiff base ligand and two N atoms from two bridging azide ligands defining the basal plane, and one phenolate O and one amine N atoms of the Schiff base ligand occupying the two axial positions.     

Structural Characterization of New Compound from the Ring-Opening Reaction of 3-(1H-1,2,4-triazol-1-yl)-1,5-Benzothiazepine with Phenylonitrile Oxide

Abstract  

The crystal structure of the product (Z)-2-((Z)-((Z)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allylidene)amino)phenyl N-hydroxybenzimidothioate (4) was obtained by single crystal X-ray diffraction. The title compound, C₃₀H₂₃N₅OS (4), crystallizes in the triclinic space group, P-1, with unit cell parameters a = 8.3306(17) ?, b = 11.394(2) ?, c = 14.560(3) ?, α = 78.75(3)o, β = 89.96(3)o, γ = 70.56(3)o, Z = 2. In the crystal structure, adjacent molecules are linked by O–H···N hydrogen bonds. H-bonds and π–π stacking are the main non-bonding interactions in the molecular structure and give support to molecular packing stability. In addition, the structure is supported by a weak intermolecular C–H···Cg π-ring interaction. Detail of the synthesis, structures, and spectroscopic properties of the title compound is discussed.     

Crystal Structures of N-(4-butyryl-3-hydroxyphenyl)acetamide Monohydrate and 4-(4-Chlorophenyl)-2-methyl-4-oxobutanoic Acid: Possibilities of Yang Photocyclization

Abstract  

N-(4-butyryl-3-hydroxyphenyl)acetamide monohydrate, (I), and 4-(4-chlorophenyl)-2-methyl-4-oxobutanoic acid, (II), are photochemically inert, which is a result of their conformation. The geometrical parameters describing the molecular conformation and possibilities of the Yang photocyclization in crystals have been calculated and discussed. Compound (I) forms double ribbons along the a axis, stabilized by hydrogen bonds and π⋯π interactions. Compound (II) forms dimers. (I): triclinic, space group \textP[`1] {\text{P}}\bar{1} , a = 6.9291(12) ?, b = 7.5736(16) ?, c = 13.0528(18) ?, α = 79.643(17)°, β = 85.818(15)°, γ = 63.97(2)°, Z = 2. (II): monoclinic, space group P2₁/c, a = 11.904(2) ?, b = 9.6508(12) ?, c = 10.666(2) ?, β = 110.64(2)°, Z = 4.     

Synthesis, Crystal Structure and Density Functional Theory Study of (2-(2-Hydroxyphenyl)benzimidazolate-based Al(III) Complex Cocrystallized by DMF Solvate and Neutral (2-(2-Hydroxyphenyl)benzimidazole

Abstract  

The aluminium(III) complex with 2-(2-hydroxyphenyl)benzimidazole, namely [Al₂(μ-OH)₂L₄)]·6DMF·2HL (1·6DMF·2HL) (HL = 2-(2-hydroxyphenyl)benzimidazole), has been synthesized and characterized by X-ray crystallography. It crystallizes in monoclinic space group C2/c with cell parameters a = 23.6752(13) ?, b = 20.8253(12) ?, c = 18.1645(10) ?, α = 90°, β = 91.929(1)°, γ = 90°, Z = 4, V = 8950.8(9) ?³. The dimeric structure of 1, featuring [Al₂(μ-OH)₂] core has been studied with the density functional theory level (DFT) calculation and molecular orbital analyses.     

Synthesis,Characterisation and Biological Activities of 2-Methylbenzyl 2-(dipyridin-2-yl methylene)hydrazinecarbodithioate

Abstract  

A new tridentate nitrogen–sulphur Schiff base has been synthesised from the condensation of di-2-pyridylketone and a novel dithiocarbazate, S-2-methylbenzyl-dithiocarbazate (S2MBDTC). The Schiff base was characterized using various physico-chemical and spectroscopic techniques. The X-ray crystallographic analysis of the Schiff base is reported. The Schiff base crystallized in a monoclinic system with a space group of P 2₁/n, with crystal cell parameters a = 10.8128 (2) ?, b = 9.3832 (2) ?, c = 18.0352 (4) ?, β = 97.1311 (9)°. The Schiff base was found to be inactive against selected microbes and two breast cancer cell lines (MCF-7 = Human breast cancer cell line with positive estrogen receptor and MDA-MB-231 = Human breast cancer cell line with negative estrogen receptor).     

Synthesis,Crystal Structure and Thermodynamic Calculations of 1,3-Diethyl-5-(diethylaminium)methylene-2-thiobarbituric Acid Adduct

Abstract  

5-[(Diethylammonio)methyl]-1,3-diethyl-6-oxo-2-thioxo-1,2,3,6-tetrahydro-4-pyrimidinolate (3) was obtained in good yield from the reaction of 1,3-diethyl-6-oxo-5-(1-pyridiniumylmethyl)-2-thioxo-1,2,3,6-tetrahydro-4-pyrimidinolate (2) and diethylamine. The crystal structure of 3 and thermodynamic calculations pertaining to that structure are discussed. The obtained product was characterized using different techniques including single crystal X-ray diffraction, NMR spectroscopy and uni (bi)-molecular systems in gaseous phase. Compound 3 crystallizes in the monoclinic space group P2₁/c with unit cell dimensions a = 13.3701(11) ?, b = 10.9983(7) ?, c = 20.8855(15) ?, β = 105.448(6)°, V = 2960.2(15) ?, Z = 8.     

Synthesis, Crystal and Molecular Structure of 1-(2-Chlorobenzyl)-2-methylthio-1H-benzimidazole

Abstract  

1-(2-Chlorobenzyl)-2-methylthio-1H-benzimidazole compound has been synthesized and characterized by elemental analysis, IR and ¹H-NMR spectroscopy and single crystal X-ray diffraction. The compound crystallizes in the triclinic space group P-1 with unit cell parameters a = 17.201 ?, b = 5.873 ?, c = 24.791 ?, α = 67.410(10)°, β = 74.083(11)°, γ = 81.858(12)°. In the crystal packing, no classic hydrogen bonds are founded, but C–H···π interactions are being between the molecules. The molecular geometry and vibrational frequencies of (C₁₅H₁₃ClN₂S) in the ground state have been calculated by using Hartree–Fock (HF) and Density Functional Method (DFT/B3LYP) with 6-31G(d) basis set. The optimized geometric bond lengths and bond angles obtained by using HF and DFT (B3LYP) show the best agreement with the experimental data.     

An X-ray Crystallographic Study of 1,4-Di[(<Emphasis Type="Italic">E</Emphasis>)-2-(<Emphasis Type="Italic">p</Emphasis>-tolyl)-1-diazenyl]piperazine

Abstract  

The crystal structure of methyl 1,4-di[(E)-2-(p-tolyl)-1-diazenyl]piperazine (4) has been determined by single crystal X-ray diffraction analysis. The bis-triazene (4) adopts a normal chair conformation in the piperazine ring, with puckering parameters : φ₂ = −29(5)°, Q_T = 0.534(2) ? and θ₂ = 177.0(2)°. The crystal structure of 4 is compared with the structure of the triazene (2a) and the closely related bis-triazenes (3 and 5a). The piperazine ring of 2a and 4 adopt a typical chair conformation, whereas the piperazine ring of 3 adopts an unusual pseudo-boat conformation. Crystal data: 4 C₁₈H₂₂N₆, triclinic, space group P[`1] P\overline{1} , a = 6.8925(2) ?, b = 7.8574(3) ?, c = 16.8856(8) ?, α = 103.103(2)°, β = 90.528(2)°, γ = 101.776(2)° and V = 870.44 (6) ?³, for Z = 2.