Synthesis,X-ray structure determination and analysis of packing interactions in 9-(1,2-propenyl)-6-carboethoxy-2-methyl-2,3-dihydrofuro[2,3-h]-benzopyran-5H-one

Claisen rearrangement of ethyl-2,4-diallyloxy--carbethoxycinnamate (1) in refluxing DMA afforded ethyl-9-allyl-2-methyl-2,3-dihydrofuro(2,3-h)benzopyran-5H-one-6-carboxylate (2) in a single step. Dehydrogenation with Pd/C (10%) in DPE furnished an unexpected isomeric compound, 9-(1,2-propenyl)-6-carbethoxy-2-methyl-2,3-dihydrofuro[2,3-h]-benzopyran-5H-one (3). This compound, C₁₈H₁₈O₅, crystallizes in the monoclinic space group P2₁/n with unit cell parameters, a = 7.346(1), b = 16.482(3), c = 12.653(2),Å, and = 92.71(1)°. The structure has been solved by direct methods and refined to R = 0.056 for 1719 observed reflections. The coumarin nucleus is planar. The five-membered ring is in envelope-conformation. The crystal structure is stabilized by intra- and intermolecular CHO hydrogen bonds.     

Synthesis and crystal structure of 2-anilino-6<Emphasis Type="Italic">H</Emphasis>-5-(1-phenyl-3-methyl-5-pyrazolone-4-ylene)-1,3,4-thiadiazine

A novel pyrazolone derivative 2-anilino-6H-5-(1-phenyl-3-methyl-5-pyrazolone-4-ylene)-1,3,4-thiadiazine (PMCP-PTSC) containing NNS hexa-atomic heterocycle has been obtained and characterized by means of single crystal X-ray diffraction, IR and ¹H NMR spectroscopies. It is interesting that when grown from two different solvents, two different crystalline structures are formed. The monoclinic crystal A belongs to a P2₁/c space group. The unit cell parameters are a = 16.414(4) Å, b = 12.530(3) Å, c = 8.432(1) Å, = 91.75(2) Å, and Z = 4. The triclinic crystal B belongs to a P space group. The unit cell parameters are a = 11.386(2) Å, b = 12.326(2) Å, c = 12.411(3) Å, = 83.07(1)°, = 87.76(2)°, = 86.52(2)°, and Z = 4. The structure analyses show the title compound is the keto-form. Dimers in crystal packing of A and supramolecular one-dimensional (B) concatenate structures were assembled by the intermolecular hydrogen bonds.     

The structure of 1-(p-fluorophenylmethyl)-2-(4-methyl-1-piperazinyl)-1H-benzimidazole hydrogen fumarate

The crystal and molecular structure of the title compound has been determined by X-ray analysis. The 1-(p-fluorophenylmethyl)-2-(4-methyl-1-piperazinyl)-1H-benzimidazole ion cocrystallizes with fumaric acid, (C₁₉H₂₂N₄F⁺·C₄H₃O ₄ ^– ), in space group P-1 with cell dimensions a = 9.938(1), b = 10.131(1), c = 12.712(1) Å, = 86.57(1), = 69.41(2), and = 67.22(2)°. The piperazine N4 atom is protonated and contacts the deprotonated O atom of the fumarate anion through a hydrogen bond. The benzimidazole ring is nearly planar and makes a dihedral angle of 111.25(12)° with the fluorophenyl ring. The piperazine ring adopts a chair conformation.     

Synthesis and crystal structures of 2-amino-3-cyano-4-(2-chlorophenyl)-1,4-dihydro-2H-pyrano[3, 2-h]quinoline and 2-amino-3-cyano-4-(2-chlorophenyl)-8-(2-chlorobenzylidene)-1,4,5,6,7,8-hexahydrobenzo[b]pyran

The title compounds 2-amino-3-cyano-4-(2-chlorophenyl)-1,4-dihydro-2H-pyrano[3, 2-h]quinoline 1 (C₁₉H₁₂ClN₃O, M _r = 333.77) and 2-amino-3-cyano-4-(2-chlorophenyl)-8-(2-chlorobenzylidene)-1,4,5,6,7,8-hexahydrobenzo[b]pyran 2 were synthesized and crystallized. The crystals of compound 1 are triclinic, space group P-1, a = 7.488(2), b = 9.127(3), c = 12.252(3) Å, = 73.58(2), = 78.38(2)°, = 75.39(2), Z = 2, V = 769.5(4) ų; The compound 2 crystallizes in space group P2₁/n, with cell parameters a = 13.582(2), b = 8.974(1), c = 16.960(2) Å, = 103.34(1)° and D _calc = 1.352 g/cm^–3 for Z = 4. X-ray analysis reveals that atoms C(1)—C(5) and O form a pyran ring in compound 1, which adopts half-chair conformation. In compound 2 the atoms C(12)—C(16) and O form a pyran ring which adopts boat conformation, another six-membered ring (C(8)—C(13)) adopts a half-chair conformation. In addition, there are intermolecular hydrogen bonds in the crystal structures 1 and 2.     

Interaction of N-(4-methoxyphenyl)-2,4,6-trinitroaniline with tris(triphenylphosphinegold)oxonium tetrafluoroborate; X-ray structure of salt [O(AuPPh3)3]2 2{(4-MeO)C6H4-N-C6H2-[2,4,6-(NO2)3]}

The structure of the auration product of N-(5-methoxybenzene)-2,4,6-trinitroaniline is determined. The compound of composition C₆₇H₅₄Au₃N₄O₈P₃ (3) crystallizes in triclinic space group P with a = 13.8280(4), b = 14.7641(4), c = 17.4531(5) Å, α = 111.550(1), β = 102.779(1), γ = 103.040(1)^∘, Z = 2. The compound represents a salt tris(triphenylphosphinegold) oxonium N-(4-methoxyphenyl)-2,4,6-trinitroanilinate, with a hexanuclear dimeric structure of the cation and a para-quinoid form of the anion that is responsible for the dark-red color of the compound.     

4- and 5-nitroindane

Mononitration of indane produces a mixture of 4- and 5- nitroindanes. Crystallization from mixtures occurs after distillation improves composition of a major component to above 80%. 4-Nitroindane: triclinic, space group (#2),a=7.332(4) Å,b=8.304(4) Å,c=8.358(4) Å, =61.43(4)°, =67.60(4)°, =70.15(4)°,V=405.4(4) ų,Z=2. Non-H-atoms are nearly planar, aliphatic H's are eclipsed. 5-Nitroindane: monoclinic, space groupP2₁/c (#14),a=10.946(8) Å,b=15.643(10) Å,c=9.415(6) Å, =92.34(5)°,V=1611(2) ų,Z=8. Non-H-atoms in the two molecules differ in torsion of the nitro group with respect to indane and fold of the nonbenzylic methylene group. Semiempirical calculations (PM3) suggest that distorsion from planarity may be associated with the two lowest energy vibrational modes. Uv, ir, ms, proton, and¹³C-nmr spectra are correlated with the solid state structures.     

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.     

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.     

The preparation, characterization, and X-ray structural analysis of dichlorobis[1-methyl-3-(2-propyl) -2(3H)-imidazolethione]mercury(II)

A new compound of mercury(II) chloride complexed to 1-methyl-3-(2-propyl) -2(3H)-imidazolethione (mipit) has been prepared and characterized via standard methods and X-ray crystallography. The structural significance of this study is that it shows one of the few monomeric examples of a mercury(II) chloride thione complex reported to date. The compound crystallizes in space group P2₁/c with a = 17.143(6) Å, b = 17.047(6) Å, c = 14.759(5) Å, = 105.899(5)°, V = 4148(2) ų, Z = 8. The coordination sphere is distorted tetrahedral with Hg–S bonds and Hg–Cl bond distances falling within the normally expected ranges. Bond angles ranged from 108.11(4)° to 115.51(4)° with the widest angle being observed for the S–Hg–S linkage. Ligand bond distances and angles including the C=S distance are within the normally expected values observed for this compound.     

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.     

Synthesis and structure of 4-R,5-R-[5-(hydroxy-diphenyl-methyl)-2, 2-dimethyl-[1,3]dioxolan-4-yl]-phenyl-methanone, a chiral ligand building block

A triphenyl analog of taddol, 4-R,5-R-[5-(hydroxy-diphenyl-methyl)-2,2-dimethyl-[1,3]dioxolan-4-yl]-phenyl-methanone, has been synthesized and structurally characterized. This molecule could act as a chiral ligand building block in the creation of tuned taddol analogs. Structural analysis of the title compound reveals that the hydroxyl group is involved in an intramolecular hydrogen bond and does not take part in any intermolecular interaction. Crystal packing is influenced by C–H O hydrogen bonding and phenyl phenyl interactions. Crystal data: Triclinic, P1 (No. 1), a = 5.9343(4) Å, b = 8.2367(17) Å, c = 10.987(2) Å, = 88.290(6), = 75.442(4), = 80.655(6), V = 512.86(15) ų, Z = 1, D _calc = 1.258 mg/m³. Final residual values were R ₁ = 0.0407 for 3022 observed data (I > 2s(I) ) and wR ₂ = 0.0941 for all 3524 unique data.     

Crystal structure and conformation of the antimalarial drug 5,7-methoxy-8-(3-methyl-1-buten-3-ol)-coumarin

The crystal and molecular structure of the antimalarial compound 5,7-methoxy-8-(3-methyl-1-buten-3-ol)-coumarin, C₁₆H₁₈O₅, M _r = 290.3 Da, has been determined from X-ray diffraction data. The material crystallizes in the monoclinic space group P2₁/c with 4 molecules per unit cell of dimensions a = 8.9044(9), b = 17.623(1), c = 10.175(1) Å, = 113.97(1)°, crystal density D _c = 1.322 g/cm³. The structure was determined using direct methods and refined by full-matrix least squares to a conventional R index of 0.066 for 2416 measured reflections and 206 parameters.The coumarin ring system is almost planar with the methoxy C atoms rotated slightly out of the coumarin mean plane. Apart from the terminal CH₃ groups C(12) and C(13), which are 1.184(3) Å above and –1.315(3) Å below the plane, the 3-methyl-1-buten-3-ol substituent is planar (rms deviation 0.009 Å) making an angle of 6.31(7)° with the phenyl ring. One intermolecular hydrogen bond is present in the crystal structure between O(5)–HO(5) and the symmetry related O(2) oxygen, generated by the symmetry operation (x, 1/2 – y, –1/2 + z).     

Structure and spectroscopic properties of 2-(N,N-dimethylaminomethyl)-4-nitrophenol

The crystal structure of 2-(N,N-dimethylaminomethyl)-4-nitrophenol, C₉H₁₂N₂O₃ has been determined by X-ray diffraction methods. The crystals are monoclinic;C2/c (No. 15),a=23.437(6),b=5.334(2),c=17.444(4) Å,=119.90(5)°,Z=8. The structure was solved by direct methods, and refined to anR value of 0.032 for 1095 nonzero independent amplitudes. Molecules of the title compound are found to exist in a zwitterionic form. Differences in hydrogen bonding in solution and in the solid phase are discussed. In nonpolar and weakly polar solvents, intramolecular O-HN hydrogen bonding is predominating. In the solid state, two N⁺-HO^– bonds related through an inversion center form a cyclic dimer.     

Crystal and molecular structure of 2-bromo-5,6-dihydro-6-methyl-4H,8H-pyrido [3,2,1-de]phenanthridin-8-one

Crystals of the title compound, C₁₇H₁₄BrNO, are monoclinic, with space groupP2₁/a,a = 14.314(5),b = 15.009(11),c = 6.596(3) Å, and = 102.39(3) °. Diffraction data were collected with CuK radiation to a Bragg angle of 77 °. The structure was solved by the heavy-atom method and refined to anR index of 0.059 for 2129 reflections. In agreement with NMR results, the C=O group is orientedanti to the benzene ring, and the methyl group at C(6) is axial. Unlike 1-(p-bromobenzoyl)-2-methyl-1,2,3,4-tetrahydroquinoline, the heterocyclic ring assumes a well defined half-chair conformation. Except for C(5) and the methyl group at C(6), the whole molecule is very nearly planar.     

Anticancer agent development. 4. X-ray crystal structure and intermolecular crystal lattice interactions of methyltrans-4,5-dihydro-4-acetoxymethyl-5-(3,4,5-trimethoxyphenyl)-2-(3,4-methylenedioxyphenyl)-3-furancarboxylate

The title compound, C₂₅H₂₆O₁₀,M ^r=486.48, crystallized from methanol in the acentric space group P2₁,2₁2₁, witha=7.617(3),b, 12.703(3),c=24.408(3) Å,V=2362 ų,D ^calc=1.37 g cm^–3 and=0.66 cm^–1 forZ=4. Least-squares refinement of 1417 observed [F ^o5(F ^o)] reflections led to the final agreement index ofR=0.044. The observed structure reveals atrans relationship for the 4-acetoxymethyl and 5-aryl substituents. The 4,5-dihydrofuran ring system assumes a slight envelope conformation. Several intermolecular van der Waals interactions of note occur in this compound.     

4- and 5-nitro-2-benzoylbenzoic acid

The structures of two isomeric nitro 2-benzoylbenzoic acids have been determined. 4-Nitro-2-benzoylbenzoic acid, C₁₄H₉NO₅, monoclinic, P2₁/c, a = 9.455(5), b = 6.632(2), c = 21.333(7)Å, = 107.96(3)°, Z = 4, V = 1270.6(9)ų, 5-nitro-2-benzoylbenzoic acid, C₁₄H₉NO₅, monoclinic, P2₁/c, a = 10.201(6), b = 8.515(4), c = 14.573(7)Å, = 101.35(4)°, Z = 4, V = 1241.1(11)ų. Both carboxylic acids form the usual H-bonded dimers across crystallographic centers of inversion. The nitro groups are essentially in the ring planes, and the interplanar angle between the mean planes described by the atoms of the benzoyl substituents and those of the benzoic acid aryl rings are 69(1)° and 84(1)°, respectively. The lower cell volume, higher density, and lower solubility in ethyl ethanoate correlates with the greater packing efficiency in 5-nitro-2-benzoylbenzoic acid.     

Synthesis and X-ray structure of 3-(4-methyl phenyl)-2-(4-biphenyl)-1,3-thiazolidin-4-one

The title compound (C₂₂H₁₉NOS) was synthesized, characterized and structure was determined by X-ray diffraction method. It crystallizes in the monoclinic space group P2₁/c with cell parameters a = 22.181(2) Å, b = 6.0760(4) Å, c = 13.349(3) Å, = 95.615(3)^, and {Z = 4}. The final residual factor is 0.0625 for 1724 reflections with I > 2(I). 4-thiazolidinone ring moiety shows twisted conformation.     

Synthesis and crystal structure of N-(1-phenyl-3-methyl-4-benzal-pyrazolone-5)- N′-salicylidene hydrazine

A novel Schiff base compound, N-(1-phenyl-3-methyl-4-benzal-pyrazolone-5)-salicylidene hydrazine (PMBP-SAH), has been synthesized and characterized by X-ray diffraction: monoclinic, space group C2/c with a = 21.796(5) Å, b = 18.370(3) Å, c = 20.843(3) Å, = 95.440(10)°, V = 8308(3) ų, and Z = 16. The title compound contains two kinds of tautomers: the red compound is the keto form and the other is the enol form. Changes in color are due to the isomerization of the enol and keto forms by the intramolecular proton transfer.     

Structures of 2-, 3-, and 4-methyl-9-oxothioxanthenes

The structures of 2-, 3-, and 4-methyl-9-oxothioxanthenes (2-, 3-, and 4-TX, respectively) were determined by single crystal x-ray methods. The molecules are folded by 2–3° about their SC=O lines. Bond distances and angles vary only slightly as a function of the methyl substitution position, and reveal no inherent structural reason for the long-range nmr couplings observed between the ring and methyl protons. The molecular packings exhibit interesting similarities as well as subtle differences that result from variation of the methyl position. Crystals of 2-TX are orthorhombic, space groupPn2₁ a,a=10.807(1),b=4.024(2),c=24.827(3) Å,Z=4,R=0.059 for 715 observed reflections. Crystals of 3-TX are orthorhombic, space groupPbc2₁,a=3.999(1),b=25.051(2),c=10.758(1)Å,Z=4,R=0.041 for 1382 observed reflections. Crystals of 4-TX are triclinic, space groupP¯1,a=7.118(1),b=7.907(2),c=10.415(2) Å,=77.74(1),=74.35(1), =73.96(1)°,Z=2,R=0.043 for 1542 observed reflections.Deceased.     

The synthesis and crystal structure of new 3,6-bis[1-(4-ethoxyphenyl)-5-methyl-1,2,3- triazol-4-yl]-<Emphasis Type="Italic">s</Emphasis>-triazolo[3,4-b]-1,3,4-thiadiazole

The 3,6-bis[1-(4-ethoxyphenyl)-5-methyl-1,2,3-triazol-4-yl]-s-triazolo[3,4-b]-1,3,4-thiad- iazole was synthesized from p-ethoxyaniline to 8 with 1-(4-ethoxyphenyl)-5-methyl-1,2,3-triazol-4-caroxylic acid. The yielded product 9 was investigated with X-ray crystallographic, NMR, MS, and IR techniques. Compound 9, C₂₅H₂₄N₁₀O₂S, Mr = 528.60, crystallizes in the triclinic space group P < eqid1 > . V = 1276.6(4) ų, Z = 2, Dx = 1.375 Mgm^–3. The final R was 0.0589.