Synthesis and Crystal Structures of N′-3,5-Dibromo-2-Hydroxybenzylidene)-2-Hydroxy-3-Methylbenzohydrazide and its Oxovanadium(V) Complex [N′-(3,5-Dibromo-2-Oxidobenzylidene-κO)-2-Hydroxy-3-Methylbenzohydrazidato-κ2N′,O](Methanol-κO)(Methanolato-κO)Oxidovanadium(V)

Abstract  

A new hydrazine ligand N′-3,5-dibromo-2-hydroxybenzylidene)-2-hydroxy-3-methylbenzohydrazide (1) and its oxovanadium(V) complex [N′-(3,5-dibromo-2-oxidobenzylidene-κO)-2-hydroxy-3-methylbenzohydrazidato-κ ² N′,O](methanol-κO)(methanolato-κO)oxidovanadium(V) (2), were prepared and were structurally characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic space group P−1, with unit cell dimensions a = 7.813(2) ?, b = 8.748(2), c = 26.071(6) ?, α = 85.763(2)°, β = 81.521(2)°, γ = 89.358(3)°, V = 1757.6(7) ?³, Z = 4, R ₁ = 0.0587, and wR ₂ = 0.1054. Compound 2 crystallizes in the triclinic space group P-1, with unit cell dimensions a = 7.777(3) ?, b = 11.594(3), c = 12.363(3) ?, α = 107.965(3)°, β = 103.190(2)°, γ = 96.656(2)°, V = 1011.3(5) ?³, Z = 2, R ₁ = 0.0634, and wR ₂ = 0.1480. The hydrazine ligand coordinates to the V atom through the phenolic O, imino N, and ethanolic O atoms. The V atom in the complex is in an octahedral coordination, with the three donor atoms of the hydrazine ligand and one methanolato O atom defining the equatorial plane, and with one methanol O and one oxo O atoms occupying the axial positions. The displacement of the V atom from the equatorial plane towards the axial oxo O atom is 0.305(2) ?.     

Crystal and molecular structure of 2-(2′-chloro-5′-nitrostyryl)benzoselenazole

The title compound C₁₅H₉ClN₂O₂Se (nsbse) is orthorhombic, witha=6.823(2),b=7.860(2),c=26.349(5) Å,Z=4,D _x =1.709,(MoK)=28.3 cm^–1,F(000)=720,T=298K in space groupP2₁2₁2₁. The structure was solved by heavy atom and Fourier methods and refined toR=0.045 for 1095 unique observed reflections. The molecule is almost planar, with a dihedral angle of 4.8(2)° between the benzoselenazole and phenyl rings. The C-Se-C angle in the selenazole ring is very small, 84.6(4)°, while the C-N-C angle in that ring is 113.7(7)°.     

Synthesis,Characterization and Crystal Structures of <Emphasis Type=Italic>N</Emphasis>′-(5-Bromo-2-hydroxybenzylidene)-2-fluorobenzohydrazide in Unsolvated and Monohydrate Forms

Abstract  

A new hydrazone derivative, N′-(5-bromo-2-hydroxybenzylidene)-2-fluorobenzohydrazide (BFBH), has been prepared and crystallized from absolute methanol and 95% ethanol, respectively, yielding unsolvated and monohydrate forms of the compound, viz. BFBH (1) and BFBH·H₂O (2). The two forms of the compound were characterized by elemental analysis, IR spectra, ¹HNMR spectra, and X-ray single crystal structural determination. The unsolvated form of the compound crystallizes in the monoclinic space group P2₁/c with unit cell dimensions a = 6.879(1) ?, b = 28.911(2) ?, c = 8.724(1) ?, β = 127.685(2)o, V = 1373.1(3) Ǻ³, Z = 4, R ₁ = 0.0569, and wR ₂ = 0.1352. The monohydrate forms of the compound crystallizes in the monoclinic space group P2₁/c with unit cell dimensions a = 14.873(3) ?, b = 7.265(1) ?, c = 13.043(2) ?, β = 96.281(2)o, V = 1400.9(4) Ǻ³, Z = 4, R ₁ = 0.0402, and wR ₂ = 0.0890. The two structures are similar to each other, except for the presence of a water molecule in (2).     

Synthesis, Characterization and Crystal Structure of N,N′-Bis(2,3-Dimethoxybenzylidene)-1,2-Diaminoethane

Abstract  

Synthesis and characterization of single crystals of a new organic Schiff-base derivative, N,N′-bis(2,3-dimethoxybenzylidene)-1,2-diaminoethane is reported. Good quality single crystals with size 10 mm × 1 mm × 1 mm were grown by slow evaporation technique from a methanol solution at room temperature. The grown crystals have been characterized by elemental analyses and functional groups were identified using FT-IR and ¹H-NMR spectroscopy. Crystal structure of the title compound has been determined by single crystal X-ray diffraction. The title compound has a monoclinic symmetry, space group P2₁/c, lattice parameters are a = 4.4159(3) ?, b = 14.2333(9) ?, c = 15.0601(10) ?, β = 97.755(5)°, Z = 2, V = 937.91(11) ?³.     

Synthesis and Crystal Structures of α-Phenyl- and α-Trifluoromethyl-α-(2-pyridyl-N-oxide)ethanols and α-Phenyl-α-(2-pyridyl-N-oxide)ethylene

Abstract  

The X-ray structures of two α-substituted α-(2-pyridyl-N-oxide)ethanols, the α-phenyl- (3a) and α-trifluoromethyl- (3b) derivatives, were determined. On dehydration of 3a, compound 4a was obtained. This study brought a clear proof that the α-(2-pyridyl-N-oxide)ethanols are formed following oxidation with peroxides of their corresponding pyridines. A different molecular packing was observed for the α-trifluoromethyl derivative due to an additional hydrogen bonding. Compound 3a crystallized in the monoclinic space group P 2₁/n with unit cell parameters a = 5.7416(1) ?, b = 14.3841(4) ?, c = 13.2821(3) ?, β = 94.918(2)°, V = 1092.90(4) ?³, Z = 4, D = 1.308 Mg/m³. Compound 3b crystallized in the triclinic space group P −1 with unit cell parameters a = 6.1209(2) ?, b = 8.1938(4) ?, c = 9.4675(4) ?, α = 73.363(3)°, β = 73.166(3)°, γ = 71.659(3)°, V = 421.32(3) ?³, Z = 2, D = 1.633 Mg/m³. Compound 4a crystallized in the monoclinic space group P 2₁/n with unit cell parameters a = 9.3579(3) ?, b = 12.7340(3) ?, c = 9.8579(3) ?, β = 117.3249(15)°, V = 1043.63(5) ?³, Z = 4, D = 1.255 Mg/m³.     

Synthesis, Characterization, and Crystal Structures of 3-bromo-N′-(2-methoxybenzylidene)benzohydrazide and N′-(2-methoxybenzylidene)-3,4-methylenedioxybenzohydrazide

Abstract  

Two new hydrazone compounds, 3-bromo-N′-(2-methoxybenzylidene)benzohydrazide (1) and N′-(2-methoxybenzylidene)-3,4-methylenedioxybenzohydrazide (2), have been synthesized and characterized by elemental analysis, IR, and single crystal X-ray diffractions. Compound (1) crystallizes in the triclinic space group P1 with unit cell dimensions a = 8.4088(5) ?, b = 8.5398(5) ?, c = 10.6572(6) ?, α = 90.356(3)°, β = 102.868(3)°, γ = 97.987(3)°, V = 738.28(7) Ǻ³, Z = 2, R ₁ = 0.0406, and wR ₂ = 0.0804. Compound (2) crystallizes in the tetragonal space group P4₁ with unit cell dimensions a = b = 9.792(4) ?, c = 15.788(6) ?, V = 1513.8(10) Ǻ³, Z = 4, R ₁ = 0.0415, and wR ₂ = 0.0818. The molecules of both compounds display E configurations with respect to the C=N double bonds. In the crystal structure of (1), molecules are linked through N–H···O hydrogen bonds, forming chains running along the b axis. In the crystal structure of (2), molecules are linked through N–H···O hydrogen bonds, forming chains running along the c axis.     

Synthesis,Crystal Structures,and Antibacterial Activity of Two Hydrazone Derivatives 3-Methoxy-<Emphasis Type="Italic">N</Emphasis>′-(3,5-Dibromo-2-Hydroxybenzylidene)Benzohydrazide Methanol Solvate and 3-Methoxy-<Emphasis Type="Italic">N</Emphasis>′-(2,4-Diclorobenzylidene)Benzohydrazide

Abstract  

Two new hydrazone compounds with the formulae C₁₅H₁₂Br₂N₂O₃·CH₃OH (1) and C₁₅H₁₂Cl₂N₂O₂ (2), were prepared and characterized by elemental analysis, IR spectra and single-crystal X-ray determination. Compound (1) crystallizes in the triclinic space group P-1 with unit cell dimensions a = 7.654(1) ?, b = 13.801(2) ?, c = 16.904(2) ?, α = 90.772(2)^o, β = 101.721(2)^o, γ = 95.891(2)^o, V = 1738.1(4) Ǻ³, Z = 4, R ₁ = 0.0495 and wR ₂ = 0.1161. Compound (2) crystallizes in the triclinic space group P-1 with unit cell dimensions a = 8.296(1) ?, b = 12.987(2) ?, c = 14.121(2) ?, α = 88.922(2)^o, β = 87.960(2)^o, γ = 84.130(2)^o, V = 1512.3(4) Ǻ³, Z = 4, R ₁ = 0.0526 and wR ₂ = 0.1220. The single crystal structure analysis indicates that compound (1) consists of two nearly coplanar hydrazone molecules and two methanol molecules which link to the hydrazone molecules through O–H···O hydrogen bonds, while compound (2) consists of two independent distorted hydrazone molecules. In the crystal structure of (1), adjacent two hydrazone molecules are linked with methanol molecules through intermolecular hydrogen bonds of O–H···O and N–H···O, forming a dimer. In the crystal structure of (2), molecules are linked through intermolecular N–H···O hydrogen bonds, forming chains running along the a axis.     

Syntheses and Crystal Structures of Two New Cadmium(II) and Nickel(II) Complexes with 1,4-Phenylenediacetate and 2,2′-Bipyridyl-Like Ligands

Abstract  

Two new complexes, namely [Cd(PDA)_0.5(2,2′-bpy)Cl](H₂PDA) (1) and [Ni(PDA)(phen)(H₂O)]₂ (2) (H₂PDA = 1,4-phenylenediacetic acid, 2,2′-bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline), have been synthesized and characterized by elemental analysis, IR spectra and X-ray crystal diffraction. Single-crystal X-ray diffraction analysis shows that complex 1 crystallizes in the triclinic space group P-1 with unit cell dimensions a = 8.760 (4) ?, b = 11.190 (5) ?, c = 13.917 (7) ?, α = 110.383 (5)°, β = 101.736 (5)°, γ = 100.612 (5)°, V = 1202.8 (10) ?³, Z = 2, R ₁ = 0.0314 and wR ₂ = 0.0898. Complex 2 crystallizes in the monoclinic space group P2(1)/n with unit cell dimensions a = 9.911 (3) ?, b = 17.924 (6) ?, c = 10.638 (4) ?, β = 94.998 (5)°, V = 1882.7 (11) ?³, Z = 2, R ₁ = 0.0397 and wR ₂ = 0.1150. In complex 1, Cd(II) ions are alternately bridged by PDA ligands and chloride ions into 1D chains and the PDA ligands display trans-configuration. Complex 2 is a dimer and two Ni(II) ions are linked by two PDA ligands with cis-configuration, resulting in a cyclic structure. In spite of these differences, both in complexes 1 and 2 there are π–π stacking interactions and hydrogen bonding to make them 3D supramolecular frameworks.     

Synthesis,Crystal Structure and Characterization of (Z)-2-N′-hydroxyisonicotinamidine

The compound (Z)-2-N′-hydroxyisonicotinamidine, (2) was synthesized and characterized by ¹H NMR, FT-IR, FAB-Mass, UV-Visible Spectra, and elemental Analysis. Its molecular structure was solved by single crystal X-ray diffraction method. The title molecule, C₆H₇N₃O is crystallized in the orthorhombic crystal system with the space group Pna2₁ and with unit cell parameters a = 12.5664(8) Å, b = 8.8622(6) Å, c = 5.7953(4) Å, α = 90°, β = 90°, γ = 90°, and Z = 4. The molecular and crystal structure of the title molecule is stabilized by an intramolecular interaction of the type N—H···O, and the intermolecular interactions of types N—H···N and O—H···N.     

Crystal Structure of 3′-(4-Methoxyphenyl)-2-Phenyl-4′-(4-Ethoxyphenyl)-1,2-Dihydro-4H,4′H-Spiro [Isoquinoline-3,5′-Isoxazol]-4-One

The title compound, 3′-(4-methoxyphenyl)-2-phenyl-4′-(4-ethoxyphenyl)-1,2-dihydro-4H,4′H-spiro[isoquinoline-3,5′-isoxazol]-4-one was synthesized from the reaction of dipolarophile with p-methoxybenzadoxime in the presence of sodium hypochlorite in chloroform solution. The structure of the synthesized compound was determined by IR, ¹H NMR, mass spectroscopic data, ¹³C NMR spectroscopy, elemental analysis and X-ray crystallography. The structure was solved in monoclinic, space group C2/c with a = 21.941 (4), b = 17.233 (3), c = 15.404 (3) Å, β = 122.193 (2), V = 4928.9 (16) Å³, Z = 8 and with R_int = 0.154. The geometry of the title compound showed that the piperidine ring adopts a half-chair conformation. In the crystal structure, molecules are linked by C–H···O and C–H···N contacts. Weak C–H···π interactions plays an important role in stabilizing the supramolecular structure.     

Crystal and Molecular Structures of Two 1:1 Adducts of bis(O-ethyl dithiocarbonato-S,S′)manganese(II): Mn(S2COCH2CH3)2 (1,10-phenanthroline) and Mn(S2COCH2CH3)2 (2,2′-bipyridyl)

Abstract  

Distorted octahedral coordination geometries based on a N₂S₄ donor set are found in each of the molecular structures of the title complexes Mn(S₂COCH₂CH₃)₂ (1,10-phenanthroline) (1) and Mn(S₂COCH₂CH₃)₂ (2,2′-bipyridyl) (2). Analyses of the geometric parameters indicate that the five-membered ring in (1) has significantly more aromatic character than the analogous ring in (2). In terms of coordination of the xanthate ligands, one ligand in (1) is considerably more aromatic than the remaining ligands. This latter feature allows for the formation of C−H···π (S₂C) interactions leading to a supramolecular chain in (1). By contrast, in (2), the crystal packing is dominated by C−H···O contacts, which lead to a supramolecular chain with 4₁ symmetry, which combine with C−H···S contacts to consolidate the three-dimensional architecture. Unit cell data for (1): hexagonal, space group R ^ˉ3, a = 35.228(5) and c = 9.0086(13) ?; and for (2): tetragonal, space group I4₁/a, a = 31.120(7) and c = 8.306(2) ?.     

Crystal Structure of Cis-Dichloro-Bis-{[2-(Diphenylphosphino-κ-P) Methyl]Diphenylphosphine Oxide}Palladium(II) Ethanol Solvate

Abstract  

The title compound cis-Cl₂Pd [P(Ph)₂PCH₂P(O)Ph₂]₂ crystallizes in the monoclinic space group, P2₁/c with crystal cell parameters a = 13.076(5) ?, b = 12.931(5) ?, c = 27.465(9) ?, β = 92.661(6)^o, V = 4639(3) ?³, Z = 4. The bulk of the phenyl groups prohibits the molecule from assuming a conformation that would permit both P=O groups to coordinate another metal ion.     

Synthesis and crystal structures of cis- and trans-1-(3′-N, N-dimethylthiocarbamoyl-4′-methoxy)-2-(3″, 4″, 5″trimethoxyphenyl) ethene

The combretastatin A-4 analogue cis-1-(3-N,N-dimethylthiocarbamoyl-4-methoxy)-2-(3,4, 5-trimethoxyphenyl) ethene (1) and its trans stereoisomer (2) were synthesized. The molecular structures of these compounds were obtained by single-crystal X-ray diffraction. Crystallization of 1 occurs in the centrosymmetric monoclinic space group C2/c (No. 15) with a = 21.468(5), b = 7.932(1), c = 23.949(3); and = 100.75(1) and Z = 8. Crystallization of 2 occurs in the centrosymmetric monoclinic space group P2₁/n (No. 14) with a = 11.7825(7), b = 11.562(1), c = 14.911(1) and = 93.294(6); and Z = 4. Details of the synthesis and the structural characterization of the title compounds are presented and discussed.     

Syntheses,Characterization and Crystal Structures of <Emphasis Type="Italic">N′</Emphasis>-(5-Chloro-2-Hydroxybenzylidene)-4-Dimethylaminobenzohydrazide and <Emphasis Type="Italic">N′</Emphasis>-(2,4-Dichlorobenzylidene)-4-Dimethylaminobenzohydrazide

Abstract  

The hydrazone compounds, N′-(5-chloro-2-hydroxybenzylidene)-4-dimethylaminobenzohydrazide (1) and N′-(2,4-dichlorobenzylidene)-4-dimethylaminobenzohydrazide (2), have been synthesized by the condensation reaction of equimolar quantities of 4-dimethylaminobenzohydrazide with 5-chlorosalicylaldehyde and 2,4-dichlorobenzaldehyde, respectively, in methanol. The compounds were characterized by elemental analysis, IR, ¹HNMR spectra, and single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 35.014(3) ?, b = 10.407(2) ?, c = 18.505(2) ?, β = 112.046(2)°, V = 6250.0(15) Ǻ³, Z = 16, R ₁ = 0.0624, and wR ₂ = 0.1187. Compound 2 crystallizes in the triclinic space group P-1 with unit cell dimensions a = 12.625(2) ?, b = 12.688(3) ?, c = 13.005(2) ?, α = 101.271(2)°, β = 112.945(1)°, γ = 104.966(2)°, V = 1747.6(6) Ǻ³, Z = 2, R ₁ = 0.0523, and wR ₂ = 0.1138. In the asymmetric unit of each compound, there exists two hydrazone molecules linking together by an N–H⋯O hydrogen bond. Furthermore, compound (2) contains one methanol molecule and one water molecule of crystallization.     

Synthesis and Crystal Structure of Bis-(N,N′-dibenzylethane-1,2-diamine) cobalt(II) acetate

Abstract  

Bis-(N,N′-dibenzylethane-1,2-diamine) cobalt(II) acetate has been synthesized and the crystal structure determined. The compound crystallizes in the space group P2₁/c, a = 8.3212(6) ?, b = 11.8774(8) ?, c = 17.3643(12) ?, β = 98.1850(10)°, V = 1698.7(2) ?³, Z = 2. The complex occupies a crystallographic inversion center. The cobalt is in a distorted octahedral environment likely due to steric influences of the acetate groups.     

Crystal Structures of Two Palladacycles from the C–H Activation of 2-(Thiophen-2-yl)pyridine

Abstract  

A C,N-bound palladacycle dimer has been synthesised by reaction of 2-(thiophen-2-yl)pyridine, LH, with palladium acetate in acetic acid. Characterisation by single crystal X-ray diffraction showed the palladacycle dimer, [(L)Pd(OAc)]₂, to crystallise in the monoclinic space group P2₁/n with cell parameters a = 9.5853(1) ?, b = 19.1332(3) ?, c = 12.3889(2) ?, β = 103.732(1)°. Reaction of [(L)Pd(OAc)]₂ with triphenylphosphine afforded a trans-substituted monomeric complex, [(L)PdPPh₃(OAc)] which was also analysed using single crystal X-ray diffraction. [(L)PdPPh₃(OAc)] crystallises in the monoclinic space group P2₁/c with cell parameters a = 9.4839(1) ?, b = 11.0427(2) ?, c = 26.0770(4) ?, β = 95.022(1)°.     

Crystal Structures and Thermal Properties of Two Transition-Metal Compounds {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O and Pb(DNI)2(H2O)4 (DNI?=?2,4-Dinitroimidazolate)

Abstract  

Two transition-metal compounds derived from 2,4-dinitroimidazole, {[Ni(DNI)₂(H₂O)₃][Ni(DNI)₂(H₂O)₄]}·6H₂O, 1, and Pb(DNI)₂(H₂O)₄, 2, were characterized by elemental analysis, FT-IR, TG-DSC and X-ray single-crystal diffraction analysis. Crystal data for 1: monoclinic, space group C2/c, a = 26.826(3), b = 7.7199(10), c = 18.579(2) ?, β = 111.241(2)° and Z = 4; 2: monoclinic, space group C2/c, a = 6.5347(6), b = 17.1727(17), c = 14.1011(14) ?, β = 97.7248(10) and Z = 4. Compound 1 contains two isolated nickel centers in its structure, one being six-coordinate and another five-coordinate. The structure of 2 contains a lead (II) center surrounded by two chelating DNI ligands and four water molecules in distorted square-antiprism geometry. The abundant hydrogen bonds in two compounds link the molecules into three-dimensional network and stabilize the molecules. The TG-DSC analysis reveals that the first step is the loss of water molecules and the final residue is the corresponding metal oxides and carbon.     

Structure of Methyl N-(4-methoxyphenylmethyl)-N′-cyano-carbamimidothioate and Methyl N-[1-(phenylmethyl)-4-piperidinyl]-N′-cyanocarbamimidothioate

Abstract  

The title compounds, Methyl N-(4-methoxyphenylmethyl)-N′-cyanocarbamimidothioate, I, and Methyl N-[1-(phenylmethyl)-4-piperidinyl]-N′-cyanocarbamimidothioate, II, have been designed and synthesized for use as new potential organic molecular electronic materials. The crystal structure of I and II were determined with crystal data (I: Monoclinic, P2₁/c, a = 4.746(2) ?, b = 5.737(3) ?, c = 17.399(7) ?, β = 91.667(7)o, R _all = 0.0703; II: Orthorhombic, Pna2₁, a = 18.209(8) ?, b = 11.463(5) ?, c = 7.539(3) ?, β = 90.00 o, R _all = 0.0481). N–H···N hydrogen bonds were responsible for the formation of one-dimensional zigzag molecular chains of I, and trifurcated hydrogen-bonded molecular chains were indicated in structure of II. C–H···π and C–H···N hydrogen bonds were found in both structures. All these types of interaction together form an extended three-dimensional network and stabilize the title crystals.