Solvothermal syntheses and crystal structures of two 4‐heterocyclic acylpyrazolone complexes

Many explorations of transition metal (M)‐L system under solvothermal condition, have led to the syntheses of two new 4‐heterocyclic acylpyrazolone complexes [Co(L)₂(CH₃OH)₂] (HL = 1‐phenyl‐3‐methyl‐4‐(2‐furoyl)‐5‐pyrazolone) ( 1 ) and [Cr(L)₃] ( 2 ). Single‐crystal X‐ray analyses reveal that crystal structures of compound 1 and 2 are respectively orthorhombic, Pbca, a = 15.0378(6) Å, b = 9.8405(4) Å, c = 20.7321(8) Å, V = 3067.9(2) ų, Z = 8 and triclinic, P‐1, a = 10.7966(18) Å, b = 13.023(2) Å, c = 15.520(3) Å, α = 73.011(4)°, β = 84.884(4)°, γ = 70.267(4)°, V = 1964.3(6) ų, Z = 2. Complex 1 has a two‐dimensional (2D) network structure that is formed by O–H···N H‐bonding interactions. Complex 2 makes a one‐dimensional (1D) zigzag chain structure by intermolecular π···π interactions, which is further interlinked via C–H···N H‐bonding interactions to generate a 2D sheet, and then a three‐dimensional (3D) supramolecular network structure is further linked by intermolecular C–H···π interactions. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,spectroscopic studies and ab‐initio structure determination from X‐ray powder diffraction of bis‐(N‐3‐acetophenylsalicylaldiminato)copper(II)

The synthesis, spectroscopic studies and crystal structure determination from X‐ray powder diffraction have been carried out for bis‐(N‐3‐acetophenylsalicylaldiminato)copper(II). The structure is triclinic, space group P1 with unit cell dimensions a = 11.817(1) Å, b = 12.087(1) Å, c = 9.210(1) Å, α = 102.62(1)°, β = 111.16(1)°, γ = 86.15(1)°, V = 1197.0(2)ų, Z = 2. The structure has been solved by Monte Carlo simulated annealing approach and refined by GSAS package. The final Rp value was 8.68%. The coordination geometry around the copper atom in the complex is intermediate between square‐planar and tetrahedral with two salicylaldimine ligands in trans arrangement. Intermolecular C–H…O hydrogen bonds between molecules related by translation generate infinite chains along [010] direction. The molecular chains are linked via additional C–H…O hydrogen bonds to form a three‐dimensional supramolecular network. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal and molecular structure of 1‐allyl‐5‐(4‐methylbenzoyl)‐4‐(4‐methylphenyl)pyrimidine‐2(1H)‐thione

The crystal structure of 1‐allyl‐5‐(4‐methylbenzoyl)‐4‐(4‐methylphenyl)pyrimidine‐2(1H)‐thione (C₂₂H₂₀N₂OS) has been determined from three dimensional single crystal X‐ray diffraction data. The title compound crystallizes in the monoclinic space group P 2₁/c, with a = 10.6674(13), b = 10.1077(7), c = 17.9467(19) Å, β = 98.460(9)°, V = 1914.0(3) ų, D_calc = 1.251 g cm^–3, Z = 4. In the title compound, the allyl group shows positional disorder. Molecules are linked by C‐H···O, C‐H···N and C‐H···S intermolecular interactions forming two‐dimensional network. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal growth,characterization and Density functional theory computations of supramolecular N‐carbamothioyl acetamide

Single crystals of N‐carbamothioylacetamide (NCTA) were grown by slow evaporation technique at constant temperature. The structure is elucidated by single crystal XRD analysis. The studies reveal that the molecule is associated with accommodating weak C–O···H, N–H···O, N–H···S, C–H···N, C···C and H···H stacking interactions which are responsible for the formation and strengthening of supramolecular assembly. Inter‐ and intramolecular hydrogen bonding interactions exhibit supramolecular architecture in the crystal packing. Two different types of architecture, i.e., a column like packing, and cluster network type of infrastructure are observed. Hirshfeld surfaces and Fingerprint plots were used to locate and analyze the percentage of hydrogen bonding interactions. The various functional groups present in the molecule are confirmed by FT‐IR analysis. Density functional theory computations of the vibrational spectrum, molecular geometry, HOMO‐LUMO energy gaps, NBO and hyperpolarizability (β) were successfully evaluated. Facts concerning with the size, shape, charge density distribution and site of chemical reactivity of the molecule have been obtained by mapping electron density with electrostatic potential (ESP).     

Crystal structure of N‐(3,4‐dichlorophenyl)‐N′‐hydroxy‐2‐oxo‐2‐phenylacetamidine

The title compound (C₁₄H₁₀N₂O₂Cl₂) crystallizes in the monoclinic space group P2₁/a with a=10.042(1) Å, b=10.317(1) Å, c=13.877(2) Å, β=97.36(2)°, V=1425.8(3) ų, Z=4, D_x=1.44 g.cm^‐3. The structure was solved by direct methods and refined by full‐matrix least‐squares method (R = 0.0457). The title molecule consists of 3,4‐dichlorophenylamino and 2‐phenyl‐1,2‐ethanedione‐1‐oxime groups. The intermolecular O‐H…N and N‐H…O hydrogen bonds [O…N 2.760(6) and 3.087(5) Å] are highly effective in forming the polymeric chains. The oxime group has an E configuration. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure analysis of {bis‐2,6‐(3,5‐dimethylprazolyl) pyridine‐dicyanato}copper(II)monohydrate

A mononuclear copper(II) complex, [Cu(dmpp)(OCN)₂(H₂O)], was synthesized using 2,6‐bis (3,5‐dimethylpyrazolyl) pyridine (dmpp) and cyanate anion (OCN), and characterized by single crystal X‐ray diffraction. The coordination around the Cu atom is a distorted square‐pyramid involving three N atoms from the dmpp ligand and one N atom from OCN at the basal plane. The O atom of the OCN group is located at the apical position. The Cu atom is located 0.2782(1) Å above the basal plane. The Cu atom is coordinated by different donor atoms of the OCN groups. The complex crystalizes in monoclinic space group P2₁/n, with unit cell dimensions a= 12.4413(12), b=11.1457(13), c=14.2203(12) Å, β=108.817(3)°, V= 1866.5(3) ų. The cell containes 4 molecules. In the crystal, there are three intermolcular and three intramolecular hydrogen bonds interactions. The Cu atom and crystal water O interactions is 5.574 Å. © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

Synthesis,Characterization, and Crystal Structures of 4,6-Dimethoxy-2-hydroxy-3-methylbenzoic Acid and 2,4-Dimethoxy-6-hydroxy-3-methylbenzoic Acid

A synthetic route involving 4,6-dimethoxy-2-hydroxy-3-methylbenzoic acid (10) and 2,4-dimethoxy-6-hydroxy-3-methylbenzoic acid (11) has been investigated in the process of synthesis of the natural lichen substance namely, crocynol. Crystal structures of 10 and 11 were determined to confirm the ambiguous structures of the two isomers. Crystals 10 are monoclinic, sp. gr. P2₁/m, Z = 2. Crystals 11 are monoclinic, sp. gr. P2₁/c, Z = 4. In the crystal packing of 10, the molecules are arranged into chains along the a-axis formed only by van der Waals interactions, whereas in 11, the molecules are linked by O–H···O and C–H···O hydrogen bonds into chains along the b-axis and further stacked by π···π interactions with the centroid ···centroid distance of 3.6863(8) Å.     

Hydrothermal synthesis and structure of a 2D supramolecular framework with right‐ and left‐helices based on mixed ligands

An exploration of the cobalt‐OH‐BDC‐bpp system under hydrothermal conditions, has led to the isolation of a novel framework [Co(OH‐BDC)(bpp)_0.5(H₂O)]_n (OH‐BDC = 5‐hydroxyisophthalic acid, bpp = 1,3‐bi(4‐pyridyl)propane). Single‐crystal X‐ray analysis reveals that it crystallizes in the monoclinic space group P2₁/n. a = 10.235(8) Å, b =17.882(14) Å, c = 14.291(11) Å, β = 92.107(9)°.The cobalt ions are linked into an extended helical chain via OH‐BDC and mono‐coordinated bpp ligands through hydrogen‐bonding interactions. Further these helical chains are united together through the bridging bpp to form a 2D layer and the adjacent chains possess the opposite chirality. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure of (dimethyl sulfoxide‐S){glyoxylic acid thiosemicarbazonato(2–)‐O,N,S }platinum(II)

A crystal of the title complex [Pt(DMSO)(GT)] ( 1a ), where H₂GT = glyoxylic acid thiosemicarbazone, has been characterized by X‐ray crystallography and its structure has been compared with that of the recently described cytotoxic complex [Pt(DMSO)(GT)]·DMSO (1). The crystal of 1a is monoclinic; space group P 2₁/n; unit cell dimensions: a = 7.3270(10), b = 10.313(2), c = 13.706(3) Å, β = 101.92(3)°; V = 1013.3(3) ų; Z = 4. The Pt(II) ion is approximately planar tetragonal coordinated by the carboxylato oxygen, azomethine nitrogen and thiolato sulfur atom of the doubly deprotonated H₂GT molecule, and the sulfur atom of DMSO. The two five membered chelate rings are almost coplanar. In distinct with 1 , the sulfoxide oxygen atom and thiolato sulfur atom are in gauche position. A system of hydrogen bonds of the type N–H···O involving the amino, carboxylato and sulfoxide groups links the complex molecules within the unit cells. The π ‐π stacking pattern between the chelate rings in 1a involves centrosymmetric pairs of complex molecules and differs from that in 1 . (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Syntheses and crystal structures of two new coordination polymers constructed from 2‐bromo‐1,4‐benzenedicarboxylate

To explore the possibility of obtaining the metal‐organic frameworks (MOFs) bearing the 2‐bromo‐1,4‐benzenedicarboxylate ligand, one new Mn(II) and one Co(II) coordination polymers, [Mn(HL)₂(bipy)₂·2H₂O]·bipy ( 1 ) and [Co(L)(bpe)] ( 2 ) (bipy=4,4′‐bipyridine; bpe=1,2‐bis(4‐pyridyl)ethene) were synthesized and characterized by elemental analysis and X‐ray diffraction analysis. Compounds 1 exhibits one‐dimensional coordination chains, which are further connected to form two dimensional supramolecular networks through hydrogen bonding interactions. Compound 2 presents a two‐fold interpenetrating two‐dimensional layer structure. The 2‐bromo‐1,4‐benzenedicarboxylate anion exhibits different coordination modes in the two complexes. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure of 2‐(2'‐hydroxyphenyl)‐6‐tributylstannyl‐4‐(3H )‐quinazolinone and 2‐(2'‐hydroxyphenyl)‐6‐iodo‐4‐(3H)‐quinazolinone

The structures of the title compounds C₂₆H₃₇N₂O₂Sn ( I ) and C₁₄H₉IN₂O₂ ( II ) were determined by single‐crystal X‐ray diffraction technique. Compound I crystallizes in the triclinic space group P1 with a = 9.560(3) Å, b = 16.899(6) Å, c = 17.872(5) Å, α = 65.957(7)°, β = 83.603(5)°, γ ( = 75.242(5)°, V = 2549.8(13) ų, Z = 4, and D =1.374 g/cm³. The compound consists of a quinazolinone ring with phenol and tributylstannyl moieties. Compound II crystallizes in the monoclinic space group P2₁/c with a = 7.6454(12) Å, b = 5.9270(9) Å, c = 27.975(4) Å; α = 90°, β = 95.081(3)°, γ = 90°, V = 1262.7(3) ų, Z = 4, and D = 1.915 g/cm³. The compound consists of a quinazolinone ring with phenol and iodine substituents. For both I and II , the short intramolecular O–H…N and two long intermolecular N–H…O hydrogen bonds are highly effective in holding the molecular system in a stable state. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural studies of crystalline oligosaccharides VI: Crystal structure and conformation of benzyl‐4,6‐O‐benzylidene‐3‐O‐benzoyl‐β‐D‐galactoside

Monsaccharides are the building blocks of polysaccharides and hence are the simplest sugar molecules to study the conformation and molecular structures of sugars. Benzyl‐4,6‐O‐benzylidene‐3‐O‐benzoyl‐β‐D‐galactoside is a key intermediate in the synthesis of polysaccharides. Crystal structural investigation of the title compound was undertaken to establish their chemical structure as well as to study their solid state conformation. Crystals of the title compound, obtained from water/methanol, are orthorhombic, space group P2₁2₁2₁, with cell dimensions a=11.290 (4), b=9.941 (1), c= 21.442(2)Å, V= 2406ų, Z=4, D_obs= 1.42 gm/cm³, D_calc=1.423 g/cm³, 2886 reflections were collected on a CAD‐4 diffractometer. The structure was solved by direct methods and refined to a final reliability index of 4.7%. The galactoside sugar has the chair conformation with C2' and C5' deviating from the mean plane of the other atoms of the sugar. The 4,6‐O‐benzylidene ring also has a chair conformation with the benzoyl group proximal to O6'. The crystal structure is stabilized by O‐H…O hydrogen bonds involving O2' as donor and three C‐H…O hydrogen bond interactions. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A new photoluminescent supramolecular inorganic‐organic hybrid zincophosphate complex pillared by carboxylate ligand through hydrogen bonding interactions

A new inorganic‐organic hybrid zincophosphate, [Zn(H₂O)₂(H₂PO₄)₂]·2PABA ( 1 ) (PABA = p‐aminobenzoic acid), pillared by PABA ligands through hydrogen bonding interactions, has been synthesized and characterized. Single‐crystal X‐ray diffraction reveals that 1 crystallizes in the monoclinic P 2₁/c space group. The geometric feature in 1 is the 3D supramolecular structure constructed from alternately arranged organic and inorganic layers that consist of infinite parallel inorganic chains. These chains are extended to a 2D inorganic layer through intermolecule hydrogen bonding interactions between N atoms (from PABA ligand) and two O atoms (from adjacent inorganic chains). 1 was characterized by IR spectroscopy, XRD, DSC/TGA. The fluorescent property for 1 in solid state was also investigated at room temperature. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structures of N1, N5‐dibenzoyltetrahydro‐4‐methyl‐1, 5‐benzodiazepin‐2‐one (DBTBO) and tetrahydro‐4‐methyl‐1, 5‐benzodiazepin‐2‐one (TBO)

Adducing structural analogies between the two fused systems, N1, N5‐Dibenzoyltetrahydro‐4‐methyl‐1,5‐benzodiazepin‐2‐one, C₂₄H₂₀N₂O₃ (DBTBO CCDC 200341) and Tetrahydro‐4‐methyl‐1,5‐benzodiazepin‐2‐one, C₁₀H₁₂ N₂O (TBO CCDC 200342) helps to find the pharmacological differences from the view point of variant hetero atom substitutions in the hetero cycle. Both the diazepines crystallized in identical monoclinic space group P2₁/n with a = 14.1134(1) Å, b = 9.2444(1) Å, c = 16.3812(1) Å; β = 107.11(1)º, V = 2042.7(3) ų for DBTBO and a = 9.3363(7) Å, b = 10.4895(8) Å, c = 9.9852(7) Å, β = 91.314(1)º, V = 977.62(1) ų for TBO, respectively. The two structures were solved by direct methods and refined by full‐matrix least‐squares procedure to final R‐values of R1 = 0.0575(DBTBO) and R1 = 0.0984(TBO). Structural differences include non‐identical boat conformations of these seven‐membered rings and the different non‐bonding interactions in the benzodiazepine pair.     

Synthesis,crystal and molecular structure of trans‐bis(2‐pyridinepropanol)bis(saccharinato)nickel(II)

Trans‐bis(2‐pyridinepropanol)bis(saccharinato)nickel(II), [Ni(sac)₂(pypr)₂], where sac and pypr are the saccharinate anion and the 2‐pyridinepropanol molecule, respectively, crystallizes in the triclinic space group P (No. 2) with a = 8.1981(8), b = 9.9680(10), c = 10.4956(10) Å, α = 90.740(3)° β = 108.142(3)°, γ = 111.025(3)°, Z = 1, V = 1.537 ų. The structure of the nickel(II) complex consists of neutral molecules in which the nickel(II) ion sits on a center of symmetry and is octahedrally coordinated by two sac ligands, and two neutral pypr ligands. The pypr acts as a bidentate N‐ and O‐donor ligand forming a seven‐membered chelate ring, while sac behaves as a monodentate O‐donor ligand via the carbonyl O atom. The Ni‐N bond distance is 2.1016(15) Å, whereas the Ni‐O_pypr and Ni‐O_sac bond distances are 2.1280(12) and 2.0792(11) Å, respectively. The individual molecules are held together with a strong hydrogen bond between the hydroxyl O atom of pypr and N atom of sac and the C‐H…O type weak hydrogen bonds between some ring hydrogen atoms of pypr and sac, and the carbonyl and sulfonyl O atoms of sac in the neighbouring molecules. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Three‐Dimensional Structure Constructed via Hydrogen Bonds and π‐π Stacking Interaction. Crystal Structure of [Cu(AFO)2(H2O)2](ClO4)2.2(AFO).2H2O (AFO = 4,5‐Diazafluoren‐9‐one)

The structure of the title complexes [Cu(AFO)₂(H₂O)₂](ClO₄)₂.2(AFO).2H₂O (AFO = 4,5‐Diazafluoren‐9‐one)has been established by single‐crystal X‐ray diffraction. The complex crystallizes in the triclinic space group P‐1 with cell constants a = 7.659(3) Å, b = 11.066(3) Å, c = 14.203(5) Å, alpha = 75.16(3)°, β = 79.87(3)°, gamma = 85.71(3)°, Z = 1. The structure was solved by direct methods and refined to R₁ = 0.0595 (wR₂ = 0.1164). The X‐ray analysis reveals that a pair of AFO ligands chelate to a Cu(II) atom in an asymmetric fashion with one Cu‐N bond being much longer than the other, the Cu(II) atom is further coordinated by a pair of aqua ligands to form an elongated octahedral geometry. In the crystal of the complex, the mononuclear complex cations [Cu(AFO)₂(H₂O)₂]²⁺, uncoordinated AFO molecules, lattice water molecules and perchlorate anions are assembled into 3‐D structure via hydrogen bonds and π‐π stacking interaction.     

Synthesis,characterization and crystal structure of a novel Ni(II) coordination polymer with dipyrido[3,2‐a:2′,3′‐c]phenazine and 4,4′‐oxy(bisbenzoate)

A novel coordination polymer, [Ni(dppz)(oba)(H₂O)]·0.5H₂O (dppz = dipyrido[3,2‐a:2′,3′‐c]phenazine and oba = 4,4′‐oxy(bisbenzoate)) has been synthesized through hydrothermal method and characterized by IR, and single‐crystal X‐ray diffraction. It crystallizes in monoclinic, space group C2/c with a = 23.163(5), b = 18.211(4), c = 14.460(3) Å, α = γ = 90°, β = 100.45(3)°, V = 5998(2) ų, Z = 2. The structure was solved by direct methods and refined to R = 0.0866 (wR₂ = 0.1836). The compound exhibits interesting one‐dimensional chain structures, which are further stacked through π‐π interactions to form supramolecular double chains. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal and Molecular Structure of bis[diaaqua(1H‐cyclopenta(2,1‐b:3,4‐b')(dipyridine ‐2,5‐dione))N ickel(II)]dihydrate

The title compound [Ni(CPDD)(H₂O)₂]₂(H ₂O )₂, {]Ni₂(C₄₄H₂₈N₈O₁₂)] (H₂O)₂ }, where CPDD = 1H‐cyclopenta(2,1‐b:3,4‐b')(dipyridine‐2,5‐dione) has been prepared and its crystal structure determined by single crystal X‐ray diffraction at room temperature. The complex crystallizes in the triclinic space group P1 w ith two molecules in the asymmetric unit. The cell dimensions are a=10.452(1),b=14.098(1) & c=16.023 Å; D=110.13(1), E=100.63(1) & J=100.85(1)°. The two independent molecules in the asymmertic unit are related by pseudo two fold symmetry. In both the molecules the coordination environment around the Ni(II) may be best described as a distorted octahedral. Due to some delocalization of charge towards one of the oxygens(O1a) from the O2a atom some degree of bond localization has been observed. The individual diones of both the molecules are almost right angles at the metal atom. A long the y‐axis inversion related molecules are forming pseudo‐dimers through hydrogen bonding.     

Structure and conformation of n‐ (t‐butoxycarbonyl)‐l‐valine‐l‐phenylalanine‐methyl ester (Boc‐Val‐Phe‐OMe)

The crystal structure of N‐ (t‐butoxycarbonyl) ‐ L‐valine‐L‐phenylalanine‐methyl ester (Boc‐Val‐Phe‐OMe), C₂₀H₃₀N₂O₅ was determined by X‐ray diffraction methods. The dipeptide crystallizes in orthorhombic space group P2₁2₁2₁, with cell parameters a = 5.0680(1) Å, b = 13.8650(1) Å and c = 28.2630(1) Å, V = 2143.8(5) ų, F.W. = 378.46, Z = 4, D_calc = 1.173 Mg/m³, μ = 0.687 mm^‐1, F₀₀₀ = 816, CuKα = 1.5418 Å. The structure was solved by direct methods and final R1 and wR2 are 0.0659 and 0.1654, respectively. The peptide unit is in trans conformation [ω = 177.4(9)°]. The conformation angles ϕ₁, ψ₁, ϕ₂ and ψ₂ for the peptide backbone are: ‐96.5(13)°, 101.2(13)°, ‐123.9(12)° and 34.0(15)°. The N‐H…O and C‐H…O hydrogen bondings influence the packing of the molecules in the dipeptide crystal. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal Structure of 4-Amino-3-(thiophen-2-ylmethyl)-1H-1,2,4-triazole-5(4H)one Monohydrate

The molecular structure of the 4-amino-3-(thiophen-2-ylmethyl)-1H-1,2,4-triazole-5(4H)one monohydrate was determined by X-ray diffraction. The compound crystallizes in the monoclinic sp. gr. C2/c with Z = 4 in the unit cell. The title compound is not planar. The dihedral angle between the thiophene and 1,2,4-triazole rings is 73.4(5)°. In the crystal structure, the molecules are connected by intermolecular N–H···O, N–H···N, O–H···O, and C–H···N type hydrogen bonds. The N–H···N and C–H···N hydrogen bonds link the molecules into infinite chains along the c axis.