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).     

Structure of methylphenylhydrazone form of 2-(2-methylphenylazo)-1,3-indandione

The molecule crystallizes in a ketohydrazone tautomeric form. The tautomeric form is stabilized by a strong intramolecular hydrogen bond of 2.709(2) Å binding the 3-oxo to the nearest nitrogen atom in the azine chain. The compound crystallizes in the monoclinic space group P2_l/c witha=7.0470(4),b=11.3090(9),c=16.2250(4) Å, =90.310(3)°, V=1293.0(1) ų, Z=4,Dx=1.3576 g cm^–3 and (Cu-K)=7.03 cm^–1. The molecule is nearly planar not regarding the methyl group; the small deviations from planarity are indicative of intramolecular interactions between the phenylazo group and indandione group. Some of the bond lengths and angles found in the molecule are distorted due to resonance, -electron delocalization and strain. The relation between these chemical effects and structural results are discussed.     

Crystal and molecular structures of O,O-propan-1,3-dithionobenzoate (2TBZ-A), O,O-2,2-dimethylpropan-1,3-dithionobenzoate (2TBZ-B), and O,O,O,O-pentaerythritoltetrathionobenzoate (4TBZ)

The crystal and molecular structures of three thionobenzoates have been determined: O,O-propan-1,3-dithionobenzoate (2TBZ-A) is tetragonal witha=13.086(2),c=19.048(2) Å, space groupI4₁/a,Z=8; O,O-2,2-dimethylpropan-1,3-dithionobenzoate (2TBZ-B) is monoclinic witha=13.851(5),b=12.428(3),c=10.996(4) Å,=104.01(4)°, space groupP2₁/c,Z=4; and O,O,O,O-pentaerythritol-tetrathionobenzoate (4TBZ) is triclinic witha=15.423(4),b=10.924(3),c=10.698(2) Å,=112.43(2),=100.64(2), =104.57(2)°,Z=2, space groupP¯1. The structures were all solved by direct methods and refined by least squares toR=0.046 for 886 reflections (2TBZ-A),R=0.075 for 1458 reflections (2TBZ-B) andR=0.075 for 2975 reflections (4TBZ),I>3(I) in each case, CuK radiation, =1.5418 Å. The minimum S---CH₂ intramolecular distances in these three structures are significantly larger than the minimum corresponding distance in O,O,O-propan-1,2,3-trithionobenzoate (3TBZ) (Moore and Palmer, 1990), thus providing a possible explanation of why 2TBZ-A, 2TBZ-B, and 4-TBZ are inert with respect to pyrolitic solid-state isomerization; whereas 3TBZ readily undergoes thermally induced rearrangement (Das, 1978; Hedgley, 1981).     

Crystal structure of 1-(2-hydroxyphenyl)-3-(2-thiomethoxyphenyl)-1,3-propanedione,C16H14O3S

The crystal structure of the enol tautomer of 1-(2-hydroxphenyl)-3-(2-thiomethoxyphenyl)-1,3-propanedione C₁₆H₁₄O₃S, was determined from X-ray crystallography. The finalR value was 5.99% based on 1945 unique observed reflections. The crystals are monoclinic,P2₁/c, witha=7.406(6),b=8.585(6),c=21.992(4) Å,=93.42(2),D _c =1.36 g cm^–3 forz=4. The compound is present in the solid state as a unique enol tautomer.There are two short, intramolecular OO contacts of 2.553(4) and 2.577(4) Å. Both the phenol and the enol H atoms are asymmetrically located with respect to the O atoms.     

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)°.     

Crystal structure of dicyclohexylammonium 2-mercaptobenzoatotriphenylstannate

Dicyclohexylammonium 2-mercaptobenzoatotriphenylstannate crystallizes in the monoclinicP2₁/n space group (a=11.171(2),b=17.891(5),c=17.190(3)Å;=105.08(2)°). The asymmetric unit consists of a [(cyclo-C₆H₁₁)₂NH₂]⁺ cation hydrogen bonded (NO1=2.803(4) Å) to the stannate anion; the [(C₆H₅)₃Sn]⁺ group is covalently linked to the sulfur end (Sn-S=2.427(1)Å) of the [SC₆H₄C(O2)O1]^–2 moiety. The tin is five-coordinate in a distortedcis-trigonal bipyramidal environment in which the carboxyl O2 atom (Sn-O2=2.704(3)Å) and theipso-carbon of a phenyl ring occupy apical positions (O2-Sn-C1=168.7(1)°); the Sn-C_axial bond (Sn-C1=2.179(3)Å) is longer than the Sn-C_equatorial bonds (2.136(4), 2.139(3)Å). The stannate anion is linked to an adjacent cation (NO1=2.880(4)Å) to form a tightly held three-dimensional network structure.     

Structural characterization of oxidized lumiflavin hydrochloride hydrate: Comparison with the hydrogen bonding at the cofactor of flavoproteins

In order to examine the possibility of hydrogen bonding around the flavin ring, an X-ray diffraction study of the title compound was undertaken. Crystals of lumiflavin hydrochloride hydrate [2(C₁₃H₁₂N₄O₂) 4 HCl 7 H₂O] are triclinic, space group ,Z=2,a=11.064(1),b=17.903(1),c=9.891(1)Å, =111.9(6), -96.4(8), =91.6(7)°. We present the crystal structure of this compound and compare it with other flavin derivatives and with the structure of the active site of some flavoproteins.     

Aromatic amines and their derivatives,Part 2. Synthesis,spectroscopic properties,and molecular and crystal structure ofN-acetyl-4,N-dimethyl-6-(N-acetyl-p-toluidinomethyl)aniline

The synthesis and selected aspects of the UV, IR, and¹H NMR spectra of the title compound are described. The crystals of the title compound are triclinic witha=12.999(9),b=8.911(4),c=9.199(5) Å;=105.56(3),=113.50(4), =92.53(3)°;Z=2; space groupP¯1. Its X-ray crystal structure analysis provides information regarding the conformational features of the amide linkage when no intermolecular hydrogen bonding involving this group is present. The X-ray study shows that the C-N bond is longer [1.363(4) Å] than that found normally in peptide molecules. The compound shows a peculiar disorder involving one of the two amide groups present in the molecule. The conformation of theN-methyl acetanilide moiety and its relation to the¹H NMR spectrum of the compound are discussed.     

Crystal and molecular structure of 1-(2-aminoethyl)biguanide-isothiocyanato-copper(II) thiocyanate

The crystal structure of 1-(2-aminoethyl)biguanide-isothiocyanato-copper(II)thiocyanate, [Cu(aebg)(NCS)] (SCN) (aebg = NH₂. CH₂. CH₂. N=C(NH₂). NH. C(NH). NH₂) has been determined and refined by Fourier methods using three-dimensional X-ray data collected on a Weissenberg automatic diffractometer. The unit cell parameters are:a = 11·41(2),b = 8·81(2),c = 7·45(2) Å; = 87·6° (2); = 67·2° (2); = 70·1° (2);Z = 2.Assuming space group P¯1, the structure was refined down toR = 8·5 %. The coordination around Cu is slightly distorted square planar and concerns three N atoms from the aebg ligand (Cu-N = 1·988(8), 2·019(7), 1·963(5) Å) and the terminal N of an isothiocyanate group (Cu-N = 1·941(5) Å). Two unsymmetrical, long interactions (Cu-N = 3·367(7) and 2·947(7) Å), with the N atoms belonging to two NCS groupstrans with respect to the coordination plane, complete the coordination to a distorted octahedron. In the aebg ligand the double bonds are localized on the C-N groups, whose nitrogen atoms coordinate to the metal.This work was carried out with the aid of financial support from the Consiglio Nazionale delle Ricerche, Roma.     

Crystal and molecular structure of 3-(4-chlorobenzoylimino)-5,6-dihydro-3H-imidazo[2,1-c]-1,2,4-dithiazole

Crystal structure of the title compound belonging to the group of-acylimino derivatives of sulfur(II) compounds has been determined by X-ray structure analysis. The crystals are monoclinic, P2₁/c,a=11.210(2),b=8.197(1),c=13.659(2) Å,=102.36(2)°,V=1226.0(3) ų,Z=4,D _x =1.61 g cm^–3, (MoK)=0.71069 Å,=6.3 cm^–1. The structure has been refined to a finalR value of 0.035 for 1401 observed reflexions.The molecule is nearly planar with symmetrym. The title compound contains a very short intramolecular C=OS contact of 2.328(3) Å, suggesting a bond-non-bond resonance interaction.     

Molecular structures of two conjugated ene-ynes derived from thiophene

The crystal structures of two conjugated ene-yne derivatives of thiophene are described, 2,5-di-(trimethylsilylethynyl)-3,4-dibromothiophene (1), is triclinic P witha=6.3281(4)Å,b=9.7421(6)Å,c=16.3669(9)Å; =80.516(5)°, =84.810(5)°, =74.072(5)°,Z=2,R=0.054; 2,3,4,5-tetra(trimethylsilylethynyl)thiophene (2), is monoclinic, P2₁/c with a=20.928(2)Å b=5.852(1)Å,c=23.907(2)Å; =100.245(6)°,Z=4,R=0.049. The ethynylic C atoms of both compounds lie near the thiophene plane, with deviations in the range 0.010(3)–0.455(4)Å. The phenyl groups of2 form a dihedral angle of 13.0(4)°.     

Synthesis and crystal structure of 1-(1′,3′-dimethyl-5′-chloropyrazol-4′-carbonyl′-3-(2′-chlorophenyl)-5-amino-4-cyanopyrazole

The title compound 1-(1,3-dimethyl-5-chloropyrazol-4-carbonyl)-3-(2-chlorophenyl)-5-amino-4-cyanopyrazole (C₁₆H₁₂Cl₂N₆O) has been synthesized and characterized by X-ray diffraction: Triclinic, space group P1, with a = 8.6712(8) Å, b = 9.5091(10) Å, c = 11.2170(11) Å = 71.531(2)°, = 84.683(2)°, = 74.099(2)° Z = 2; V = 843.7(14) ų. C(10), O(1), C(11), and N(2) atoms are coplanar with the average deviation of 0.0071 Å, which form 11.03° and 43.93° dihedral angles with pyrazole planes (I) and (II), respectively.     

Crystal structures of two therapeutically active 2-imidazolines: naphazoline nitrate and tymazoline hydrochloride monohydrate

Naphazoline·HNO₃ (1): C₁₄H₁₅N₃O₃,M _r =273.3, crystallizes in the orthorhombic space group Pbca(Z=8) witha=12.028(1),b=14.408(2) andc=15.894(2) Å,V=2754.4 ų,D _x =1.318 g cm^–3,=0.70 mm^–1, (CuK)=1.54178 Å,F(000)=1152. FinalR=0.092 andwR=0.088 for 1348 observed reflections collected on a diffractometer. The structure was solved with direct methods, it shows two distinct positions of the naphthyl group with populations about 0.5, which differ by a 180 rotation. As in other arylmethyl-2-imidazolines, the imidazoline ring is approximately perpendicular to the aromatic ring. The molecules are linked by two hydrogen bonds N(3)-HO (nitrate anion)H-N(1) into infinite chains running along the 2₁ axis in the [100] direction. Tymazoline·HC1·H₂O (2): C₁₄H₂₃ClN₂O₂,M _r =286.8, crystallizes in the monoclinic space groupP2₁/n (Z=4) witha=8.136(1),b=10.015(1),c=18.601(1) Å and,=97.20(1)°,V=1503.7 ų D _x =1.266 g cm^–3,=2.27 mm^–1, (CuK)=1.54178 Å,F(000)=636. FinalR=0.115 andwR=0.119 for 3073 observed reflections collected on a diffractometer. The structure was solved with direct methods. Unlike other aryloxymethyl-2-imidazolines, the molecule is almost planar with an angle of 12.8(2)° between the two rings. Hydrogen bonding networks consist of N(1)-HO (water)Cl^–H-N(3) chains joined by an additional link O(water)-HCl^– between chains running in opposite directions.     

Schiff bases and their complexes with metal ions. Part II. Structures of N-n-butyl-2-hydroxy-1-naphthaldimine and bis[N-n-pentyl-2-hydroxy-1-naphthaldiminato]nickel(II)

The Schiff base ligand (1), [C₁₅H₁₇NO] crystallizes in the monoclinic space group P2₁/c witha=10.054(3),b=10.313(3), c=13.173(4)Å, =107.42(4)°,V=1303.2(7)ų,Z=4,Dx=1.159 g cm^–3, and (MoK)=0.674 cm^–1. The C2-O[1.23(1)Å] and C3–C4 [1.33(2)Å] bond lengths are short, due to its quinoidal structure. In the Schiff base nickel complex (2), [Ni(C₁₆H₁₈NO)₂] the asymmetric unit is comprised of two half-complexes. It crystallizes in the triclinic space group witha=5.124(3),b=16.227(3),c=16.886(4)Å, =95.47(8), =96.00(1), =90.71(4)°,V=1389.6(9) ų,Z=2,Dx=1.289 g cm^–3, and (MoK) =12.1 cm^–1. The coordination of the Ni(II) ions are square planar with bond angles between 87.9(1) and 92.1(1)°. The Ni–O and Ni–N distances are 1.819(2), 1.922(2) and 1.823(2), 1.914(3)Å in these two complexes.     

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)°.     

Structure of a binuclear silver(I) complex [Ph3PAg(O2CCH2Ph)]2

The reaction of [Ph₃PAgI]₄ with sodium phenylacetate in MeOH and CH₂Cl₂ at room temperature gave rise to a binuclear silver complex with triphenylphosphine and phenylacetate mixed ligands, [Ph₃PAg(O₂CCH₂Ph)]₂. The crystal and molecular structure of the complex has been determined by single crystal X-ray diffraction analysis. The space group is witha=9.198(2),b=9.516(2),c=13.842(3) Å, =102.00(3), =108.34(3), =93.58(3)°,Z=1, andDc=1.506 g cm^–3. The silver atoms are each coordinated by one phosphorus atom from triphenylphosphine and two oxygen atoms from the carboxylate groups in a T-shape. The complex is further characterized by its IR,¹H, and³¹P NMR spectra.     

Crystal and molecular structure of: 5-(1-oxoethyl)-1-methyl-2-(5-bromo-6-methoxy-2-naphthyl)-6-oxabicyclo[3.2.1]octan-7-one and 5-(1-oxoethyl)-1-methyl-2-(5-bromo-6-methoxy-2-naphthyl)-6-oxabicyclo[3.2.1]octane

X-ray crystallographic studies of the two title compounds have shown that the molecules crystallize in the same triclinic space group, , with very similar cell dimensions. For C₂₁H₂₁BrO₄,a=12.056(5),b=13.206(5),c=7.595(3)Å, =90.38(3), =106.07(3) and =124.42(3)° and for C₂₁H₂₃BrO₃,a=12.076(6),b=13.090(5),c=7.490(3)Å, =92.65(5), =104.90(5) and =124.55(5)°. Both compounds possess the oxabicyclo[3.2.1]octane bridged ring system and differ only at the carbon to the ring oxygen where the Csp³ in the ether is replaced by Csp²=O in the lactone. Both cyclohexane rings adopt distorted chair conformations and the lactone and ether rings approximate closely to the envelope conformation. The bromine substituent at C(4) results in distortion of the naphthalene ring. Both molecules pack with the naphthalene rings parallel to each other with interplanar spacings of 3.71 Å in the ether and 3.66Å in the lactone.     

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.     

Crystal structures of twoN-substituted 2-thioxo-1,3-dithiole-4-carboxamides

The two closely related compoundsN,N-dimethyl 5-(methylthio)-2-thioxo-1,3-dithiole-4-carboxamide1 andN-(p-methoxy-phenyl)-N-methyl 5-(methylthio)-2-thioxo-1,3-dithiole-4-carboxamide2 have been characterized by X-ray crystal structure determination. Crystal data for1: triclinic, ,a=6.767(1),b=12.594(2),c=6.648(1) Å, =101.38(1), =93.37(2), =79.62(1)°,V=546.2 ų,Z=2. Crystal data for2: monoclinic, Cc,a=19.836(4),b=6.057(1),c=15.860(3) Å, =127.61(3)°,V=1509.5ų,Z=4. The molecular structures of1 and2 show remarkable differences concerning the conformational behavior. These differences are related to the nature of the substituents at the nitrogen atom. The presence of an aromatic system in2 leads to an almost planar arrangement of the -oxoketene dithioacetal moiety. This effect is accompanied by a short intramolecular S...O contact of 2.648(2) Å. In the absence of an aromatic system, as is the case for compound1, neither a resonance effect along the -oxoketene dithioacetal fragment nor a short S...O distance is observed.     

Crystal structure ofcis-diaqua bis(2,2′-bipyridyl)chromium(III) nitrate, [Cr(bipy)2(H2O)2] (NO3)3

cis-Diaquabis(2,2-bipyridyl)chromium(III) nitrate crystallizes in the mono-clinic system, space groupP2₁/c, witha=16.102(6),b=10.792(5),c=15.076(6) Å,=112.90(5)°, andZ=4. The saltlike structure was determined from X-ray crystallography and refined toR=7.5% for 3342 observed reflections. The Cr atom is octahedrally surrounded by twocis water molecules and by two chelated 2,2-bypiridyl ligands forming two nearly orthogonal planes. Selected bond distances are: Cr-O, 2.00(1) and 1.98(1) Å, Cr-N, 2.04 Å (mean).