The Synthesis and Crystal Structure of 5-(4-Bromophenylamino)-2-methylsulfanylmethyl-2<Emphasis Type="Italic">H</Emphasis>-1,2,3-triazol-4-carboxylic Acid Ethyl Ester

Abstract  The 5-(4-bromophenylamino)-2-methylsulfanylmethyl-2H-1,2,3-triazol-4-carboxylic acid ethyl ester 6 was synthesized from p-bromoaniline. The yielded product 6 was investigated with X-ray crystallographic, NMR, MS, and IR techniques. Compound 6, C₁₃H₁₅BrN₄O₂S, Mr = 371.26, crystallizes in the monoclinic space group P2₁/n with unit cell parameters a = 5.5220(1), b = 26.996(5), c = 10.596(2) ?, β = 103.83(3). V = 1533.8(5) ?³, Z = 4, Dx = 1.608 mg m⁻³. The final R ₁ was 0.0844; wR ₂ was 0.1560. H-bond is discussed. Index Abstract  The structure of 5-(4-bromophenylamino)-2-methylsulfanylmethyl-2H-1,2,3-triazol-4-carboxylic acid ethyl ester from 5-amino-1-(4-bromophenyl)-1,2,3-triazol-4-carboxylic acid ethyl ester is studied. H-bond is discussed.      

Solvent-controlled structures. Synthesis and characterization of complexes Cu(L)2(CH3COO)2 and [Cu2(μ-CH3COO)4(L)2](L)2 [L = N-(4′-methylaniline)-4-pyridinecarboxamide]

Two complexes Cu(L)₂(CH₃COO)₂ (1) and [Cu₂(μ-CH₃COO)₄(L)₂](L)₂ (2) (L = N-(4′-methylaniline)-4-pyridinecarboxamide) have been prepared and their crystal structures have been determined by single-crystal X-ray diffraction. The complexes are obtained by using the same raw materials and reaction conditions except solvents. The presence or absence of water controls the coordination mode to give rise to different structures. The structure of 1 has a triclinic space group P-1 with a = 8.381(3) ?, b = 8.545(4) ?, c = 11.357(5) ?, α = 110.654(6)°, β = 102.388(7)°, γ = 97.889(7)°, V = 722.9(5) ?³, and Z = 1. The structure of 2 has a triclinic space group P-1 with a = 9.121(3) ?, b = 9.454(3) ?, c = 17.233(5) ?, α = 77.374(5)°, β = 89.827(6)°, γ = 74.342(6)°, V = 1393.8(7) ?³, and Z = 1. Supramolecular assemblies have also been found via noncovalent bonds such as hydrogen bonds, π–π stacking interactions.     

Crystal structure of 3H-1,2-benzodithiol-3-one 1-oxide

The compound 3H-1,2-benzodithiol-3-one 1-oxide (2) has proven useful in modeling the reactivity of the novel antitumor antibiotic leinamycin (1). The crystal structure of this unusual sulfur heterocycle is reported here. The molecule crystallizes in the P-1 space group with cell parameters a = 7.168(4), b = 7.670(3), c = 7.922(3)Å, = 68.34(4), = 83.86(3), = 65.50(3),° and U = 367.8 ų.     

The crystallographic structure of 4-hydroxy-3-methylene-4-(p-nitrophenyl)butan-2-one

The crystallographic structure of 4-hydroxy-3-methylene-4-(p-nitrophenyl)butan-2-one 1 is disclosed by x-ray analysis. It crystallized in the space group C2/c (#15) with a = 19.958(4), b = 10.486(3), c = 15.009(3) Å, = 137.553(6)°, V = 2120.0(9) Å,³ Dcalc = 1.386 g/cm³, and Z = 8.     

Variable Ag—O bonding patterns in silver cyclic amide tri-aryl-phosphine complexes

The solid-state structures of five new tri-arylphosphine silver cyclic amide complexes having a systematic variation in the ring structures have been resolved. Normal Ag—N bonding and variable, weaker Ag—O bonding interactions, which can be attributed to the ring modifications, form the basis of the bonding patterns. Reported here are the solid-state structures of silver complexes of tri-arylphosphine derivatives of silver 1(2H)-phthalazinone, silver phthalimide, silver 1,2,3-benzotriazin-4(3H)-one, silver 2H-1,3-benzoxazine-2,4(3H)-dione and silver 2,3-dihydro-1,4-phthalazine- dione. The unit cell parameters are: P-1, a = 11.179(2) ?, b = 15.508(3) ?, c = 22.636(5) ?, α = 104.30(3)°, β = 95.39(3)°, γ = 94.62(3)°; C2/c, a = 17.3600(8) ?, b = 15.4930(8) ?, c = 15.0760(7) ?, β = 113.911(2)°; P-1, a = 11.0656(2) ?, b = 11.9447(2) ?, c = 17.4764(3) ?, α = 79.5254(9)°, β = 80.2877(9)°, γ = 68.9136(7)°; P-1, a = 10.5743(4) ?, b = 11.8439(4) ?, c = 19.0110(8) ?, α = 102.4280(13)°, β = 104.0330(12)°, γ = 100.2520(18)°, P-1, a = 13.6908(3) ?, b = 16.2230(4) ?, c = 18.3678(7) ?, α = 86.8920(10)°, β = 69.5290(10)°, γ = 70.7840(10)°, respectively. Four of the complexes include ligand chelation by Ag—O bonding to the adjacent carbonyl in addition to the main Ag—N connection.     

Synthesis and Crystal Structures of 3,3,6,6-tetramethyl-9-(2,4-dichlorophenyl)-3,4,6,7,9,10-hexahydro-2H,5H-acridine-1,8-dione and 3,3,6,6-tetramethyl-9,10-di(4-methoxyphenyl)-3,4,6,7,9,10-hexahydro-2H,5H-acridine-1,8-dione

The title compounds 3,3,6,6-tetramethyl-9-(2,4-dichlorophenyl)-3,4,6,7,9,10-hexahydro-2H,5H-acridine-1,8-dione 1 (C₂₃H₂₅Cl₂NO₂, Mr = 418.34) and 3,3,6,6-tetramethyl-9,10-di(4-methoxy-phenyl)-3,4,6,7,9,10-hexahydro-2H,5H-acridine-1,8-dione 2 (C₃₁H₃₅NO₄, Mr = 485.60) were synthesized and crystallized. The crystals of compound 1 are monoclinic, space group P2₁/c, a = 9.826(3), b = 19.866(5), c = 11.471(3) ?, β = 111.929(4)°, Z = 4, V = 2077(1) ?³; The compound 2 crystallizes in space group P2₁/c, with cell parameters a = 12.089(2), b = 11.447(2), c = 19.742(3) ?, β = 101.00(1)°, V = 2681.8(8) ?³ and D _calc = 1.203 g/cm³ for Z = 4. X-ray analysis reveals that atoms C(1), C(6), C(7), C(8), C(13) and N(1) form a 1,4-dihydropyridine ring in compound 1, which adopts half-chair conformation. In compound 2 the atoms C(1), C(6), C(7), C(8), C(13) and N form a 1,4-dihydropyridine ring which adopts boat conformation. In addition, the two outer six-membered rings display half-chair conformations in the crystal structures 1 and 2.     

Crystal structure oftrans-tetrachlorobis[2-(2-1H-imidazolyl)-1H-imidazolium]cadmium(II), [Cd(H3biim)2Cl4]

The reaction between cadmium(II) chloride and 2,2'-bi-1H-imidazole (H₂biim) in an acidic solution affords [Cd(H₃biim)₂Cl₄] (H₃biim=2-(2-1H-imidazolyl)-1H-imidazolium) in 63% yield. The compound crystallizes in the triclinic space groupP1, wherea=8.072(2),b=8.100(2),c=8.593(2) Å, =75.89(2), =62.94(2), =63.29(1)°,V=446.4(2) ų, andZ=1. The central Cd atom exhibits an octahedral geometry composed of a Cl₄N₂ core. The Cd-N bond distance is 2.392(2) Å. Cd–Cl distances are 2.5919(9) and 2.671(1) Å.     

Separation of 4-aminobenzoic acid by cocrystallization: Crystal structure of the complex of 4-aminobenzoic acid with (2R,3R)-tartaric acid

4-Aminobenzoic acid (PABA) has been successfully separated from a mixture containing 2-aminobenzoic acid and (2R,3R)-tartaric acid. X-ray structure analysis confirms the separating result. The molecular complex formed by PABA and tartaric acid in 1:1 molar ratio crystallizes in the orthorhombic space group P2₁2₁2₁ with cell dimensions of a = 7.329(1) Å, b = 12.095(2) Å, c = 15.231(3) Å, V = 1350.1(4) ų, Z = 4. The crystal structure comprises protonated PABA, monoanion of tartaric acid, and crystalline water. The extensive H-bonding network exists in the crystal structure. H bonding between tartaric acid and both terminal groups on para position of PABA is considered as a possible reason for the successful separation.     

Structure of 4-(2-chloro-4,5-dimethoxybenzylidene)-2-methyl-5-oxazolone. X-ray and NMR study

The azlactone of 6-chloroveratraldehyde 3 (4-(2-chloro-4,5-dimethoxybenzylidene)-2-methyl-5-oxazolone) was synthesized from 6-chloroveratraldehyde 2 and its structure investigated using X-ray crystallographic and nuclear magnetic resonance methods. Compound 3 crystallized in the P2₁/c (#14) space group (Z = 4) with cell dimensions a = 9.148(2), b = 22.938(2), c = 6.707(1) Å, and = 111.50(2)°. The X-ray study shows that azlactone 3 exists as the Z-isomer and crystallizes as a planar structure, i.e., both the phenyl and azlactone ring systems, as well as the functional groups attached to them, lie in the same plane. The ¹H and ¹³C NMR spectral values also support the formation of the Z-isomer only, during the synthesis of 4-(2-chloro-4,5-dimethoxybenzylidene)-2-methyl-5-oxazolone.     

Crystal Structure of 2, 8, 14, 20-<Emphasis Type="Italic">tert</Emphasis>-Butylpyrogallol[4]arene

Abstract  The aromatic derivative 2, 8, 14, 20-tert-butylpyrogallol[4]arene was synthesized by the acid catalyzed condensation of pivalaldehyde and pyrogallol in refluxing aqueous ethanol. Single crystal X-ray analysis revealed that the molecule crystallizes in the monoclinic crystal system; space group: P2₁/c. Unit cell dimensions: a = 11.1175(7) ?, α = 90°, b = 23.4525(15) ?, β = 101.6720(10)°, c = 21.9595(14) ?, γ = 90°, D_calc = 1.205 Mg/m³ g/m³ for Z = 4. In the solid state, the macrocycle is found to adopt a crown structure that is unique for the rcct conformation. Graphical abstract   Crystal Structure of 2, 8, 14, 20- tert -Butylpyrogallol[4]arene Eric E. Dueno, Allen D. Hunter, Matthias Zeller, Thomas A. Ray, Ralph N. Salvatore, Cesar H. Zambrano Acid catalyzed condensation of pyrogallol and pivalaldehyde in refluxing aqueous ethanol afforded a pyrogallol[4]arene derivative in good yield. Single crystal X-ray diffraction analysis revealed that a new calyx-like structure was formed under the reaction conditions. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

Synthesis and Photocatalytic Properties of TiO2 Intercalated H4Nb6O17

Abstract

TiO₂ intercalated H₄Nb₆O₁₇ has been synthesized by the reactions of H₄Nb₆O₁₇ with a titanyl acylate complex followed by UV irradiation. The gallery height, specific surface area and Ti content of the sample synthesized by using titanyl acylate complex were larger than that using TiO₂ sol solution. Furthermore, the photocatalytic activity of the TiO₂ pillared H₄Nb₆O₁₇ prepared using a titanyl acylate precursor was twice larger than that fabricated using a TiO₂ sol solution.     

A crystallographic study of 2-hydroxyacetophenone N(4)-cyclohexyl thiosemicarbazone

The crystal structure of 2-hydroxyacetophenone N(4)-cyclohexyl thiosemicarbazone is described. The compound crystallizes in the triclinic crystal system, space group , Z = 4, V = 1569.6(3) ?³ with unit cell parameters a = 6.9436(8) ?, b = 12.4762(15) ?, c = 18.588(2) ?, α = 100.187(2)°, β = 97.069(2)° and γ = 92.340(2)°. There are two independent molecules in the asymmetric unit. The crystal structure reveals that the compound exists in the thione form and S1 and N1 are at E configuration to each other with respect to N2-C8 bond. Similarly, S2 and N4 are trans to each other with respect to N5-C23 bond in the second molecule of the asymmetric unit. The packing of the molecules in the crystal lattice is stabilized by intermolecular hydrogen bonds.     

Redetermination of the crystal structure of [Na4(H2O)14]SnS4: a compound containing a novel chain of aquated sodium ions

[Na₄(H₂O)₁₄]SnS₄ is obtained by the reaction of Na₂S·9H₂O with SnCl₄·5H₂O in aqueous solution at 21°C. It crystallizes in the space group Cc with a = 8.621(2) Å, b = 23.543(5) Å, c = 11.358(2) Å, = 110.58(3)° and V = 2158.2 ų with Z = 2. Refinement of 3826 unique reflections from a racemically twinned crystal yielded a final value of R₁ = 0.0464 (|F| > 4) and wR₂ = 0.104 and a goodness of fit of 1.125. The structure consists of a Na⁺/H₂O network supporting the tetrahedral SnS₄ ^4– anions. Water molecules or sulfide ions octahedrally coordinate each of the four crystallographically independent Na⁺ ions. The dominant feature of the structure is the existence of zigzag chains of edgeshared Na octahedra. These chains are tied together into a three-dimensional network by bridging Na(H₂O)₆ octahedra and individual H₂O molecules.     

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

Abstract  The synthesis and crystal structure of 1,7-bis(4-chlorophenyl)-4-(1,3-dithiolan-2-ylidene)-1,6-heptadiene-3,5-dione is described. This compound is a curcuminoid analogue, configurationally symmetric about the C4–C5 atoms and also retains the two fold axis in the crystal phase. This compound crystallizes in the space group C2/c with unit cell parameters a = 19.203(1) ?, b = 13.147(1) ?, c = 8.801(1) ?, β = 112.99(1)°, with half a molecule in the asymmetric unit. The ketenedithioacetal functionality present between the carbonyl groups prevents the possibility of keto-enol tautomerization in this compound. The push-pull nature of the ketenedithioacetal functionality organizes the cinnamoyl groups parallel to each other. Index Abstract  The details regarding synthesis and crystal structure of the title compound which is a curcuminoid analogue is reported in this paper.      

Synthesis, Crystal Structure and Properties of the Binuclear Complex [Sm2(C10H9N2O4)2(C10H8N2O4)2(H2O)4]

Abstract  A novel binuclear Smarium (III) complex with N-(2-propionic acid)-salicyloyl hydrazone (C₁₀H₁₀N₂O₄, H₃L) was prepared and characterized. The crystal structure of [Sm₂(H₂L)₂(HL)₂(H₂O)₄] (1) was determined by X-ray single crystal diffractometry. 1 crystallizes in the monoclinic systerm, space group P2(1)/c, with a = 0.10229(2), c = 31.549(7), b = 0.70599(15) nm, and Z = 4. In the structure, Sm(III) is nine-coordinated by carboxyl O and acyl O atoms and imido N atoms of two ligands (H₂L and HL forms) and O atoms from two water molecules. H₂L and HL act as tridentate ligands which form two stable five-numbered chelating rings sharing one edge in the keto form for each ligand, and the carboxyl groups of two ligands were coordinated via bidentated bridging form. The coordination polyhedron around Sm (III) was described as a monocapped square antiprism. The inter- and intramolecular hydrogen bonds resulted in a three-dimensional network and provided extra stability for the structure. The complex was researched the interaction with calf thymus DNA by electronic absorption titration and emission titration. The results show that the complex is bound to calf thymus DNA mainly by intercalation .The complex also shows good fluorescence property. Index Abstract  The title compound, [Sm₂(H₂L)₂(HL)₂(H₂O)₄] was synthesized by the treatment of N-(2-propionic acid)-salicyloyl hydrazone (C₁₀H₁₀N₂O₄, H₃L) and Sm(NO₃) · 4H₂O and its crystal structure determined. Single crystal X-ray diffraction analysis reveals that Sm (III) is nine-coordinated by carboxyl O and acyl O atoms and imido N atoms of two ligands (H₂L and HL forms) and O atoms from two water molecules. The carboxyl groups of two ligands were coordinated via bidentated bridging form. The coordination polyhedron around Sm (III) was described as a monocapped square antiprism. The inter- and intramolecular hydrogen bonds resulted in a three-dimensional network and provided extra stability for the structure.      

Triethyl ammonium salt of O,O′-bis(p-tolyl)dithiophosphate, [Et3NH]+[(4-MeC6H4O)2PS2]−

Triethyl ammonium Salt of O,O′-bis(p-tolyl)dithiophosphate and O,O′-bis(m-tolyl)dithiophosphate have been obtained by reaction of p- and m-cresol, respectively with P₂S₅ in toluene and have been characterized by elemental analysis, IR, ¹H and ³¹P NMR spectroscopy. The molecular structure of O,O′-bis(p-tolyl)dithiophosphate has been determined. Crystal data: [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻: Monoclinic, P2₁/c, a=15.2441(9) ?, b=10.415(2) ?, c=3.9726(9) ?, β=91.709(7)°, V=2217.5(1) ?⁻³, Z=4.Supplementary materials Additional material available from the Cambridge Crystallographic Data Centre (CCDC no. 600927 for [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻ comprises the final atomic coordinates for all atoms, thermal parameters, and a complete listing of bond distances and angles. Copies of this information may be obtained free of charge on application to The Director, 12 Union Road, Cambridge CB2 2EZ, UK (fax: +44-1223-336033; email: deposit@ccdc.cam.ac.uk or www:http://www.ccdc.cam.ac.uk).     

Investigation of 4-acetyl-2,6-dibenzyl-1,5-dihydroxy-2-methylcyclohexa-4,6-dien-3-one by X-ray crystallography and 1H-NMR spectroscopy

Benzylation of 3-methylphloracetophenone [1-(2,4,6-trihydroxy-3-methylphenyl)ethanone] (3) with benzyl chloride gave 4-acetyl-2,6-dibenzyl-1,5-dihydroxy-2-methylcyclohexa-4,6-dien-3-one (5). Compound 5 crystallizes in the orthorhombic space group Fdd2 with a = 17.586(2), b = 42.891(5), c = 10.279(2) Å, V = 7753(2) Å,³ and Z = 16. When crystals of 5 were dissolved in [D₆]acetone the compound underwent tautomerization and a mixture of 5 and its keto form 4 was obtained (keto form/enol form ratio 1:4).     

Synthesis, characterization, and structural analysis of ethyl (2Z)-3-(4-chlorophenyl)-2-cyano-3-(methoxyamino)prop-2-enoate

Ethyl (2Z)-3-(4-chlorophenyl)-2-cyano-3-(methoxyamino)prop-2-enoate was prepared by reacting the lithium salt of ethyl cyanoacetate with (Z)-O-methyl-4-chloroben-zohydroximoyl fluoride. This compound crystallizes in space group Pbca,with lattice constants a=7.5740(15) ?, b=11.337(2) ?, and c=30.424(5) ? at 110 K. Characterizations include spectrometric identifications employing IR, UV, and ¹H and ¹³C NMR. The compound exists in the solid as the enamine tautomer, with the cyano group cis to the 4-chlorophenyl group (the Z configuration). The C=C and C–N bond distances are 1.3930(16) ? and 1.3278(16) ?, respectively. The N–H group forms a bifurcated hydrogen bond with acceptors C=O (intramolecular) and C≡N (intermolecular).Supplementary material CCDC-289444 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, by e-mailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44(0)1223-336033.     

O-benzyl-N-(2-furoyl)thiocarbamate

The O-benzyl-N-(2-furoyl)thiocarbamate (1) was obtained by direct reaction between furoyl isothiocyanate and benzyl alcohol. The X-ray diffraction analysis of 1 showed an orthorhombic system, with a = 7.811(4) Å, b = 9.685(4) Å, c = 33.562(15) Å, and space group P2₁2₁2₁. This compound showed two different arrays of structure, corresponding to two conformers in the same crystal unit. In one conformer the carbonyl and thiocarbonyl groups are in a syn arrangement while in the other the groups are anti. Both structures present a non-restricted conformation and show NH—OC hydrogen bonding between them.     

Structure of 2-{2-[3-methyl-3-(2,4,6-trimethylphenyl) cyclobutyl]-2-oxoethyl}isoindole-1,3-dione

2-{2-[3-Methyl-3-(2,4,6-trimethylphenyl)cyclobutyl]-2-oxoethyl}isoindole-1,3-dione (C₂₄ H₂₅NO₃) was synthesized, and its crystal structure was determined by X-ray crystallographic techniques. The compound crystallizes in the triclinic space group P-1, with unit cell parameters: a = 14.109(9) Å, b = 14.130(8) Å, c = 12.152(6) Å, = 105.62(5)°, = 113.75(4)°, = 98.78(5)°, V = 2039.8(19) ų, D _c= 1.223 g/cm³, and Z = 4. The crystal structure has two crystallographically independent molecules, I and II. These molecules are held together by weak intermolecular C—H···O interactions, forming a continuous chain. The dihedral angles between the N-substituted phthalimide moiety and cyclobutane ring in molecules I and II are 60.37(14) and 68.18(18)°, respectively.