Crystal structures of difluoro[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]boron(III), [BF2(C16H13O3)], and bis[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]copper(II), [Cu(C16H13O3)2]

The crystal structures of difluoro[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]boron(III), [BF₂(C₁₆H₁₃O₃)], and bis[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]copper(II), [Cu(C₁₆H₁₃O₃)₂], have been determined by single-crystal X-ray diffraction methods. The structures were solved by direct methods and electron density calculations and were refined by the full-matrix least-squares method. Difluoro[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]-boron(III) crystallizes as yellow rhombs in the monoclinic space groupP2₁/c witha=11.429(3),b=11.364(4),c=11.412(4) Å,=92.19(2)°,V=1481.0(8) ų andZ=4. A total of 2754 unique reflections were collected. Of these 1342 were considered observed [I>3(I)] leading to a finalR-value of 0.045. Boron is tetrahedrally coordinated to the two fluorine atoms and to two oxygen atoms of the bidentate 2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato ligand, C₁₆H₁₃O ₃ ^– . Average bond distances: C-C (aromatic) 1.378(10) Å, B-O 1.473(7) Å and B-F 1.343(4) Å. bis[2-(4-Methoxyphenyl)-3-oxo-3-phenylpropanalato]copper(II) crystallizes as dark yellow-green plates in the monoclinic space groupC2/c witha=23.410(7),b=13.856(3),c=8.039(3) Å,=101.79(2)°,V=2553(1) ų andZ=4. Of the unique set of 3076 scanned reflections 2401 hadI>3(I) for whichR became 0.040. Copper is coordinated to four oxygen atoms, two from each of the two bidentate 2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato ligands, in a distorted square planar manner. The molecule hasC ₂ symmetry. Average bond distances: C-C (aromatic) 1.383(6) Å and Cu-O 1.896(8) Å. The crystals of both compounds consist of monomeric molecular complexes held together by van der Waals forces.     

Alkylation of tellurium tetrachloride by trimethylaluminum. Synthesis and molecular structure of [Te(CH3)3][Al(CH3)2Cl2]: A novel organotelluronium-aluminum oligomer

Reaction of TeCl₄ with A1(CH₃)₃ in toluene affords the crystalline product [Te(CH₃)₃][Al(CH₃)₂Cl₂]. The title compound crystallized in the monoclinic space group P2₁/n with unit cell parametersa=11.630(3),b=12.595(4),c=8.409(2) Å,=89.97(2)°, andD _c =1.62 g cm^–3 forZ=4. Least-squares refinement based on 1354 observed reflectionsI3 (I) in the range 3.5<2<45.0° led to a finalR factor of 0.046 (R _w =0.067). The compound does not exist as discrete cations and anions but may be described as an organotelluronium-aluminum oligomer. The mean Te-C bond distance is 2.130(11) Å while the mean Al-Cl bond distance is 2.221(4) Å.     

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.     

Crystal structures of two azo compounds, 2-methyl-2-(4-bromphenylazo)-1,3-indandione and 2-methyl-2-(4-ethoxyphenylazo)-1,3-indandione

In the two title compounds, the 2-methyl-1,3-dioxoindan-2-yl and 4-(brom; ethoxy) phenyl groups aretrans with respect to one another. The phenyl ring and the azo group are not coplanar in the two molecules. The five-membered rings of the two compounds adopt an envelope conformation. The crystallographic parameters are as follows: 2-Methyl-2-(4-bromphenylazo)-1,3-indandione (I): monoclinic, P2₁/a witha=8.098(2),b=14.442(2),c=12.554(1)Å, =100.55(2)^o, andD _calc=1.58 g cm^–3 forZ=4; 2-methyl-2-(4-ethoxyphenylazo)-1, 3-indandione (II): monoclinic, P2₁/a witha=8.258(2),b=14.449(1),c=13.559(2)Å, =101.19(1)^o, andD _calc=1.29 g cm^–3 forZ=4.     

Crystal and molecular structure of 1-phenyl-3-(2-hydroxyphenylamino)-2-buten-1-one,C16H15NO2

Orange, yellow, and colorless crystals were obtained for the title compound. The orange crystals are triclinic, space groupP¯1,a=9.181(2),b=10.734(2),c=15.245(3) Å,=73.06(2),=79.21(2), =67.83(2)°,V=1325.9(5) ų,Z=4. Two different symmetry-independent molecules (moleculeA andB) were determined in the crystal unit. The conformation ofA is stabilized by an intramolecular H bond from the amino NH to the keto and phenolic O atoms [1.89(2) and 2.38(2) Å, respectively]. The conformation ofB is stabilized by only one intramolecular H bond, from the amino NH to the keto O atom [1.925(2) Å]. The colorless crystals (moleculeC) are monoclinic, space groupP2₁/n,a=11.883(3),b=11.004(3),c=10.053(3) Å,=95.93(3)°,V=1307.5(6) ų,Z=4. This conformation is stabilized by one intramolecular H bond, the same as in B, with N-HO, 1.84(3) Å. An intermolecular H bond is observed forA,B, and C, O-HO, 2.634(2), 2.640(2), and 2.697(2) Å, respectively. The yellow crystals are adducts with ethanol (¹H NMR, infrared and GC measurements).     

Synthesis, characterization, and crystal structure of 1-(4-chloro-benzoyl)-3-naphthalen-1-yl-thiourea

1-(4-Chloro-benzoyl)-3-naphthalen-1-yl-thiourea has been synthesized and characterized by elemental analysis, IR spectroscopy, and mass spectrometry. The crystal and molecular structure of the title compound has been determined from single crystal X-ray diffraction data. It crystallizes in the triclinic space group P-1, with a = 6.962(1) Å, b = 10.770(3) Å, c = 11.738(2) Å, = 65.76(2)°, = 80.03(1)°, = 84.86(2)°, and D _calc= 1.432 g cm^–1 for Z = 2. The thermal behavior of the compound has been studied by DTA and TG. The antibacterial activities of the title compound were investigated for three Gram (+) and two Gram (–) bacteria by employing broth microdilution method and subsequently, inhibitory activity against yeast-like fungi was also determined.     

Crystal structures of 4-amino-1,2,4-triazolidine-3,5-dione (urazine) (C2H4N4O2) and dichlorobis (4-amino-1,2,4-triazolidine-3,5-dione-N,O) copper (II) (C4H8Cl2CuN8O4)

Crystal structure analyses of urazine and of its adduct with CuCl₂ show that this ligand can exchange interactions of stacking that cannot be defined as simple - interactions. The copper atoms are octahedrally coordinated by two oxygen atoms and two aminic nitrogen from chelating uraxines and two chlorine atoms. The crystals of urazine are monoclinicP2₁ c:a=6.741(1),b=5.815(1),c=11.141(2) Å,/gb=92.13(1)°,V _c=436.4(1) ų,Z=4,R=0.0402 for 714 independent observed reflections; the crystals of [CuCl₂(urazine)₂] are triclinicP¯1:a=5.236(1),b=6.662(1),c=8.411(1) Å,=93.00(1),=104.87(1), =105.69(1)°,V _c=270.66(8) ų,Z=1,R=0.0380 for 875 independent observed reflections.     

Synthesis and structure of 1-(2-amino)phenyl-2-phenyl-12H-indolo[3,2-c]carbazole ethylacetate solvate,a new indolocarbazole compound

The structure of a new indolo-carbazole compound, unique in having two indole rings with NH groupstrans-fused to a phenyl ring, has been determined by X-ray crystallography. The crystals are monoclinic, space groupP2₁/n,a=25.548(7),b=8.532(3),c=12.594(4) Å,=93.50(2)°,V _c=2740.1(2) ų,Z=4,D _k=1.240 g cm^–3, (CuK)=1.54178 Å,=5.79 cm^–1,F(000)=1080,R=0.071,R _w=0.080 for 2939 unique significant reflections measured at 298 K. The crystals retain one mole of ethyl acetate per molecule, which shows disorder. Restricted rotation of the phenyl and aminophenyl groups was detected by¹³C nmr. The title Indolo-carbazoles are easily obtained by reaction of 3-bromoindoles with 2,3-biindolyls and show an interesting planar structure which could be investigated for anticancer properties.     

Studies of systemic acylanilide fungicides. Part I. Crystal structure and molecular conformation ofdl-methyl-N-(2,6-dimethylphenyl)-N-(2-methoxyacetyl) alaninate

The crystal structure of metalaxyl (C₁₅H₂₁NO₄) was determined by three-dimensional X-ray analysis from diffractometer data. The crystals are monoclinic,P2₁/c,a=7.851(3) Å,b=13.119(10) Å,c=15.107(7) Å,=101.71(6)°,Z=4,D _x=1.218 g cm^–3, (MoKa)=0.095 mm^–1. FinalR=0.079 for 1203 observed reflections. The dimethylphenyl ring is almost perpendicular to the amidic plane of the molecule.     

Refinements of the crystal structures of 1,4-diphenylbutadiyne and its complex with two moles of Co2(CO)6

1,4-diphenylbutadiyne, C₁₆H₁₀, crystallizes in monoclinic space group P2₁/n witha=6.6152(6),b=6.0768(7),c=14.634(1) Å, =100.981(8)⁰,V=577.5(2) ų,Z=2. The structure was refined toR=0.077 andR _w=0.069 for 1007 observed reflections with CuK radiation. The molecule lies on an inversion center. Our determination represents and increase in precision of a factor of approximately three over the original determination. The 21 cobalt complex, C₁₆H₁₀[Co₂(CO)₆]₂, also crystallizes in monoclinic space group P2₁/n witha=8.9568(12),b=17.7057(10),c=18.5671(12) Å, =90.606(12)^o,V=2944.3(5) ų,Z=4. The structure was refined toR=0.032 andR _w=0.031 for 4312 observed reflections. The diphenylbutadiyne triple bonds elongate to 1.346(3) Å and the angles at the diyne C atoms decrease to 134.1(3)–144.9(3)^o upon complexation. The Co-Co distance is 2.4580(4)Å. Our data represent an increase in precision by a factor of 2–3 over the original determination.     

Synthesis and crystal structure of 4,5-(cis-cyclohexylenedithio)-1,3-dithiole-2-one

The x-ray crystal structure of 4,5-(cis-cyclohexylenedithio)-1,3-dithiole-2-one has been determined. Yellow block shaped crystals of C₉H₁₀OS₄ crystallize in the space group P with cell dimensions a = 8.872(4), b = 9.330(8), c = 14.333(12) Å, = 95.23(7), = 91.09(5), = 107.60(5)°, V = 1124.8(14) ų, and Z = 4. This compound has two S---S contacts [3.574, 3.610 Å] shorter than 3.70 Å and the usual disordered ethylene moiety [C(3)—C(8)] of the six-membered ring is fixed by the cis-cyclohexylene subsitituent. This means that it may be a new precursor for conducting and strong near-IR absorbing nickel-dithiolenes. Also, it provides the first example of polymorphism of the dmit derivatives and contains two independent molecules I and II in the asymmetric unit.     

Studies of substituted quinoxaline-di-N-oxides. Part 1. Crystal structure and molecular conformation of 2-[N-(2-hydroxyethyl)carboxamide]-3-methylquinoxaline 1,4-dioxide

A single crystal X-ray investigation of the yellow 2-[N-(2-hydroxyethyl) carboxamide]-3-methylquinoxaline 1,4-dioxide, a commercially available growth promoter used in agricultural stock farming, shows that the molecule is planar. The dihedral angle between the benzene and heterocyclic rings is 0.5°. The N(1)-O(1) and N(2)-O(2) distances are: 1.286(1) and 1.304(1) Å. The C(1)-C(2) bond of the pyrazine ring is not lengthened by substitution at the C(1) and C(2) atoms and is 1.421(2) Å. The atoms O(1) and O(2) deviate by 0.036(2) and 0.123(2) Å from the least-squares plane through the heterocyclic ring. The deviation of the C(12) atom is –0.012(2) Å. The plane through the atoms C(1), C(9), N(3), and O(3) makes an angle of 100.5(2)° with the heterocyclic ring plane. Intermolecular hydrogen bonds O(4)-HO(4)O(3) between the hydroxyl and carbonyl groups generated alternating, antiparalled chains extending in thea direction. The crystals are triclinic,P¯1 (No. 2), witha=7.469(2),b=8.111(2),c=10.357(3) Å,=80.11(2),=88.90(2), =67.73(2)°, andV=571.3(2) ų. The structure was solved by direct phase determination guided by negative quartets and refined by full-matrix least squares to anR value of 0.041 for 2159 observed reflections.Commercially known asOlaquindox.     

Crystal and molecular structures of 1-phenyl-4,6-dimethylpyrimidine-2-thionetetraaquacobalt(II) dinitrate complex and of two pyrimidine thiones

The crystal structures of 1-phenyl-4,6-dimethylpyrimidine-2-thionetetraaquacobalt(II) dinitrate (I)a=9.032(2),b=12.458(2),c=18.067(3)Å,=103.25(3)°,Z=4;P2₁/c,R=0.049; 1-phenyl-4,6-dimethylpyrimidine-2-thione (II)a=12.005(3),b=10.090(2),c=9.649(2)Å,=104.4(1)°,Z=4;P2₁/n,R=0.038; and 4,6-dimethylpyrimidine-2-thione (III)a=15.485(3),b=13.255(3),c=7.127(2)Å,=104.3(1)°,Z=8,C2/c,R=0.041 are reported. In (I) the coordination around the cobalt(II) is distorted octahedral involving one ligand moleculevia sulphur and nitrogen atoms and four water molecules. It is relevant that the parameters in the complexed ligand are not different from those found in the uncomplexed one (II), excepting the distances on the nitrogen atom directly involved in the coordination. Bond distances and angles in compound (III) agree with those found in (II).     

Crystal and molecular structure of 3-(2-(1,10-phenanthrolyl))-5,6-diphenyl-1,2,4-triazine-chloroaquotriphenyltin(IV) (1:1)

3-(2-(1,10-Phenanthrolyl))-5,6-diphenyl-1,2,4-triazine-chloroaquotriphenyl-tin(IV) (1:1) crystallizes in the orthorhombic system:a=19.195,b=9.144,c=21.642 Å,Z=4, space groupPca2₁ (No. 29). The structure was determined using the procedure for difference structures (Dirdir) with CuK diffractometer data, and refined by block-diagonal least squares toR=0.031 for 3287 observed reflections. The tin atom is 5-coordinate with the three phenyl groups forming the equatorial plane. A chlorine atom and a water molecule complete the coordination. The triazine moiety does not coordinate directly to the metal atom. The only interaction is due to two N H-O hydrogen bonds formed between two nitrogen atoms from the ligand and the water molecule.     

Crystal and molecular structure of palladium(II), copper(II) and zinc(II) complexes of 1-methyl-3-(4-methyl)phenyltriazen-1-oxide

The structures of palladium(II), copper(II) and zinc(II) bis(chelates) of 1-methyl-3-(4-methyl)phenyltriazen-1-oxide have been determined by single-crystal X-ray methods. The crystals of [Pd(OMeN₃C₆H₄Me-4)₂] (I) are triclinic witha=7.410(3),b=7.806(3),c=8.371(2) Å, =65.80(2), =88.73(3), =81.04(3)°,Z=1, space group . The crystals of [Cu(OMeN₃C₆H₄Me-4)₂] (II) are monoclinic,a=14.934(5),b=10.111(4),c=11.762(3) Å, =96.00(2)°,Z=4, space group P2₁/c. The crystals of [Zn(OMeN₃C₆H₄Me-4)₂] (III) are triclinic witha=7.912(2),b=10.056(2),c=11.600(2) Å, =87.31(3), =74.96(3), =74.02(3)°,Z=2, space group . The structures of (I), (II), and (III) were solved to final values ofR=0.029, 0.043 and 0.034, respectively. A planar structure has been found for (I), (II) exhibits a tetrahedrally distorted square planar structure, whereas (III) is tetrahedral. The crystals of all three complexes are held by networks of stacking interactions.     

Crystal structures of (I) 2-(9,9-dipropylfluorene-2-yl)-9,9- dipropylfluorene and (II) 2-(1,1-dimethylpropyl)-7- {4-[(1,1-dimethylpropyl)-9,9-diethylfluoren-2-yl]phenyl}-9,9-diethylfluorene and (III) 2-(4-ethylphenyl) -7-[7-(ethylphenyl)-9,9-dipropylfluoren-2-yl]-9,9-dipropylfluorene

The crystal structures of the three fluorene related molecules, (I) 2-(9,9-dipropylfluorene-2-yl)-9,9-dipropylfluorene, [Exalite 384, C₃₈H₄₂], (II) 2-(1,1-dimethylpropyl)-7-{4-[(1,1-dimethylpropyl)-9,9-diethylfluoren-2-yl] phenyl}-9,9-diethylfluorene, [Exalite 404, C₅₀ H₅₈], and (III) 2-(4-ethylphenyl)-7-[7-(ethylphenyl)-9,9-dipropylfluoren-2-yl]-9,9-dipropylfluorene, [Exalite 416, C₅₄H₅₈], have been determined. Structural details reveal a novel new bonding arrangement at the C2 atoms of symmetry-related fluorene moieties in all three molecules producing a linear type array with an inversion center connecting adjacent asymmetric units within each molecule. Exalite 384 is monoclinic, space group P2₁/c with a = 9.002(2) Å, b = 16.275(4) Å, c = 10.525(1) Å, = 103.05(1), and V = 1502.1(5) ų with Z = 4, for d _calc = 1.103 g/cm³. Exalite 404 is triclinic, space group P1 with a = 10.383(1) Å, b = 13.404(2) Å, c = 7.7007(9) Å, = 105.296(9), = 104.23(1), = 73.707(9), and V = 974.9(2) ų with Z = 2, for d _calc = 1.141. Exalite 416 is monoclinic, space group P2₁/c with a = 15.99(10) Å, b = 11.178(8) Å, c = 23.766(4) Å, = 104.21(4), and V = 4117(4) ų with Z = 4, for d _calc = 1.141 g/cm³.     

Molecular structure of 3-(3-oxo-bicyclo[2.2.1]hept-5-en-2-yl)-oxirane-2-carboxylic acid methyl ester

The crystal and molecular structure of an epoxy ester is described. The structure has been solved by vector search methods and refined by least squares methods toR ₁=0.0372 [I>2(I)]. The structure consists of two independent molecules in the asymmetric unit. These molecules are chemically the same. Crystal data: C₁₁H₁₂O₄, triclinic, space group ,a=10.324(3),b=10.553(7),c=10.869(5)Å, =61.77(4), =88.64(4), =88.16(6)°,V=1042.7(9)ų,Z=4.     

Structure of (Z)-1-p-methoxyphenyltelluro-1,4-diphenyl but-1-en-3-yne

C₂₃H₁₈TeO,M _r=437.97, ,a=9.940(2),b=13.664(3),c=7.895(2) Å, =80.60(1), =69.71(2), =75.95(1)°,V=972.0(4) ų,Z=2,R=0.041 for 2668 observed reflections. The Te–C bond distances are 2.109(5)Å and the C–Te–C angle is 96.0(2)°. The phenyl rings are planar to within experimental accuracy, making dihedral angles of 64.6(2), 65.3(2) and 31.1(3)°.     

On the organoaluminum chemistry of multidentate phosphine ligands. Reaction of trimethylaluminum with bis(diphenylphosphino)methane: Synthesis and molecular structure of [Al(CH3)3]2[(C6H5)2PCH2P(C6H5)2]

Reaction of an excess of trimethylaluminum with bis(diphenylphosphino)-methane in heptane affords the crystalline complex [A1(CH₃)₃]₂[(C₆H₅)₂PCH₂P(C₆H₅)₂]. The title compound crystallizes in the triclinic space group P¯1 with unit cell parametersa=10.053(6),b=11.017(6),c=15.908(8) Å,=85.58(4),=71.80(4), =77.49(4)°,V=1634(1) ų, andD _c=1.07 g cm^–3 forZ=2. Least-squares refinement based on 2924 observed reflection with intensitiesI3I) in the range 2.00245.0° converged atR=0.050 (R _w=0.067). The Al-P distances are 2.585(2) and 2.521(2) Å, and the P-C-P angle is 121.4(2)°.     

Molecular structure and some reactivity aspects of 2,6-diamino-4(3H)-pyrimidinone monohydrate

Crystals of C₄H₆N₄O·H₂O are orthorhombic:Pbca,a=16.721(2),b=4.242(1),c=18.293(2)Å,Z=8. The structure has been solved by direct methods and refined by full-matrix least-squares techniques toR=0.046 for 1252 unique reflections. The structure consists of approximately planar molecules of the 3(H)4-one tautomer. Delocalization of the ring and the C=O-electrons, and conjugation of the lone-pair electrons of the amine groups with the pyrimidinone nucleus are observed. The molecules are connected by O-HO, N-HN, and N-HO hydrogen bonds. The molecular structure clarifies the chemical properties of the compound.