5-(thien-2-yl) uracil analogs: 5-(5-methylthien-2-yl)-2′-deoxyuridine, 5-(5-thien-2-yl)-2′-deoxyuridine,and 5-(5-bromothien-2-yl)-2′-deoxyuridine

Crystal structures of 5-(5-methylthien-2-yl)-2-deoxyuridine (I), 5-(5-thien-2-yl)-2-deoxyuridine (II) and 5-(5-bromothien-2-yl)-2-deoxyuridine (III) have been obtained from data collected on a four-circle Enraf-Nonius diffractometer (CAD-4 system). Space group, unit/cell parameters and finalR indices are:I, monoclinic,P2₁,a=9.105(2),b=20.819(2),c=7.932(2) Å, =98.79(2)°,R=5.7%;II, monoclinic,P2₁,a=8.720(4),b=20.793(4),c=7.884(4) Å, =95.06(2)°,R=5.8%;III, monoclinic,P2₁,a=9.260(2),b=41.655(7),c=7.926(2) Å, =97.996(13)°,R=9.4%. Structural properties of the title compounds are compared with those of 5-(5-chlorothien-2-yl)-2-deoxyuridine (IV) previously reported in order to explain their affinity for HSV-1 thymidine kinase and their eventual interaction with viral DNA polymerase. The main structural features observed are the coplanarity of the uracil and thienyl cycles stabilized by a S–O intramolecular interaction and the formation of dimeric intermolecular H bonds between two uracil moieties.     

Synthesis and structure analysis of 2-(2′-propanonylthio)-3-(o-methyl phenyl) quinazol-4(3H)-one

The three-dimensional molecular and crystal structure of 2-(2'-propanonylthio)3-(o-methyl phenyl)quinazol-4(3H)-one has been determined by X-ray crystallographic methods. This compound crystallizes in the orthorhombic space group P_bca with unit cell parameters: a=9.649(5), b=30.102(10), c=11.403(9)Å. It has been solved by direct methods and refined to a residual index of 0.054. The magnitude of torsion along C16— C11— N3— C4 bond is 93.5(4)°. The dihedral angle between the plane comprising all the ring atoms of quinazoline moiety and the atoms of the methyl substituted phenyl ring is 94.12(1)°. The crystal structure is stabilized by one intramolecular C— HsO interaction and three intermolecular C— HsN contacts.     

Structural study of nitrovinylindoles: (I) 2-methyl-3-(2′-methyl-2′-nitrovinyl)indole and (II) 3-(2′-nitrovinyl)indole

Compound (I) is 2-methyl-3-(2-methyl-2-nitrovinyl)indole, C₁₂H₁₂N₂O₂,M _r=216.24, monoclinic,P2₁/n,a=16.710(1),b=7.627(1),c=17.646(1) Å,=104.8(1)°,V=2174.7(1) ų,Z=8.D _x=1.321 g cm^–3, MoK, =0.71073 Å,=0.858 cm^–1,F(OOO)=912, room temperature,R=0.061 for 1956 observed reflections. Compound (II) is 3-(2-nitrovinyl)indole, C₁₀H₈N₂O₂,M _r=188.18, monoclinic,P2₁/n,a=10.178(1),b=10.608(1),c=8.411(1) Å,=105.5(2)°,V=875.0(1) ų,Z=4,D _x=1.4284 g cm^–3, CuK, =1.5418 Å,=8.068 cm^–1,F(000)=392, room temperature,R=0.040 for 1330 observed reflections. Compounds (I) and (II) have a similar geometry, the only significant difference lying in the rotation of the nitrovinyl chain. This feature could be responsible for the difference in biological activity. In both compounds, the molecules are associated, forming charge-transfer complexes.     

2-甲基4-(4-(吡啶-3-乙炔基)苯基)-3-丁炔-2-醇的合成及晶体结构

由1,4-二碘代苯出发,经过两步Sonogashira偶联反应合成了标题配合物2-甲基4.(4-(吡啶-3-乙炔基)苯基)-3-丁炔-2-醇.通过1H NMR、13C NMR核磁共振、Ⅹ-射线单晶衍射等手段对化合物的结构进行了表征.结果表明,该化合物晶体属于单斜晶系,空间群为P21/c.晶体学参数:a=3.3321 (4) nm,b=1.00539(11) nm,c=0.89158(10) nm,α =90.00°,β=92.442(2)°,y=90.00°,V=2984.2(6) nm3,Z =4.     

Structural studies of N-2-(3-picolyl)- and N-2-(4-picolyl)-N′-tolylthioureas

Reactions of 2-aminopicolines with 2- and 4-tolyl isothiocyanates yielded N-2-(4-picolyl)-N-4-tolylthiourea, 1, N-2-(3-picolyl)-N-4-tolylthiourea, 2, and N-2-(4-picolyl)-N-2-tolylthiourea, 3. Compound 1 is monoclinic, of space group P2₁/c with a = 7.456(1) Å, b = 13.135(3) Å, c = 13.959(3) Å, = 104.99(3)°, and V = 1320.5(5) ų with Z = 4, for d _calc = 1.294 g/cm³. Compound 2 is triclinic, of space group with a = 6.877(3) Å, b = 7.590(5) Å, c = 13.213(9) Å, = 78.38(2)°, = 77.96(4)°, = 86.36(4)°, and V = 660.5(7) ų with Z = 2, for d _calc = 1.294 g/cm³. Compound 3 is monoclinic, of space group P2₁/c with a = 12.604(2) Å, b = 15.592(3) Å, c = 6.875(2) Å, = 91.05(2)°, and V = 1350.9(2) ų with Z = 4, for d _calc = 1.265 g/cm³. The three thioureas are found in both solid state and solution in a conformation resulting from intramolecular hydrogen bonding. Compounds 1 and 3 present an intermolecular hydrogen bond involving the thione sulfur and the NH hydrogen, which is not present in 2 owing to the steric hindrance of the methyl group in the phenyl ring. The geometry of the molecule is affected by the position of the methyl groups on the pyridine and aryl rings.     

Crystal structure of chloro(dicarbonyl) bis(acetonitrile) (π-2-methallyl) molybdenum(II)

The title compound crystallizes in the monoclinic spacegroup P2₁/m with a = 6.796(9), b = 12.145(14), c = 7.749(8)Å, = 101.86(1)°, and Z = 2. The crystal structure consists of molecules of [MoCl(CO)₂(NCMe)₂(³-C₃H₄Me-2)] with crystallographically imposed C_s symmetry and has a pseudo-octahedral geometry, with the -allyl group trans- to the chloro group and the two cis-carbonyl and acetonitrile groups occupying the equatorial plane.     

Crystal structure of 5-(2′-aminophenyl)-2-dimethylamino-1,3,4-thiadiazole

The crystal structure of 5-(2′-Aminophenyl)-2-dimethylamino-1,3,4-thiazole is determined by X-ray diffraction. The compound is prepared by an unusual recyclization of 3-N, N-dimethylthioureidoquinazolin-4(3H)-one. The crystal is monoclinic, space group P2₁/c, a = 7.420(2) Å, b = 10.466(5) Å, c = 14.752(9) Å, β = 109.2(4)°, ρ_calcd = 1.359 g/cm³, and Z = 4 for the C₁₀H₁₂N₄S composition. The molecule consists of the thiadiazole and phenyl rings and the dimethylamine N(CH₃)₂ and amine NH₂ groups attached to the rings. The molecule as a whole is planar. The dihedral angle between the rings is 8.9°. The N(1) and N(4) atoms in the molecule are bound through the intramolecular interaction (2.76 Å). Molecules, which are linked in pairs by antiparallel hydrogen bonds, form a framework structure.     

Crystal structure of trans-W2(CO)6(PPh2H)2(μ2-PPh2)2

The molecular structure of trans-W²(CO)₆(PPh²H)²(₂-PPh²)² was determined by X-ray diffraction analysis. The two tungsten centers, bridged by two diphenylphosphido ligands, are separated by 3.0667(6) Å with W–P–W angles of 77.10(5) and 77.08(5). Average tungsten–phosphorus bond distances are 2.461(17) and 2.4576(21) Å for bridging and terminal phosphorus groups, respectively, with a range of 0.037 Å for the former and 0.001 Å for the latter. The complex crystallizes in the monoclinic space group P2₁/c with a = 19.282(4) Å, b = 12.158(2) Å, c = 21.294(9) Å, = 92.821(4), and Z = 4.     

Bis(2,6-(2′,6′-diisoproylanil)diformyl-4-chloro-phenolate) nickel(II)

Bis(2,6-(2,6-diisoproylanil)diformyl-4-chloro-phenolate) nickel(II) was prepared by the reaction of 2,6-(2,6-diisoproylanil)diformyl-4-chloro-phenol with nickel chloride. The title complex crystallized in P2₁/c, with cell dimensions a = 9.962(2) Å, b = 12.087(3) Å, c = 24.445(6) Å, and = 97.032(5), giving a volume of 2921.4(13) ų. The bis(2,6-(2,6-diisoproylanil)diformyl-4-chloro-phenolate) nickel(II) adapts an ideal parallelogram, in which the Ni atom is coordinated with two phenolic oxygen atoms [O(1), O(1A)] and two imino nitrogen atoms [N(1), N(1A)].     

Novel manganese(III) oxidation chemistry: X-ray crystal structures of (1α,2α,4β)-1,2-diacetoxy-4-(4-methoxyphenyl)-6-methoxy-1,2,3,4-tetrahydronaphthalene (compound A) and (1α,2α,4β)-1,2-diacetoxy-4-(2-methoxyphenyl)-8-methoxy-1,2,3,4-tetrahydronaphthalene (compound B)

CompoundA is (1,2,4)-1,2-diacetoxy-4-(4-methoxyphenyl)-6-methoxy-l,2,3,4-tetrahydronaphthalene, C₂₂H₂₄O₆,M _r=384.43, monoclinic, P2₁/n, witha=11.074(3),b=10.353(4),c=17.616(4)Å,=94.96(2)°,V=2012.1ų,D _calc=1.27 g cm^–3 and=0.55 cm^–1 forZ=4. Least-squares refinement of 1371 observed [F ₀5 (F ⁰)] reflections led to the final agreement index ofR=0.052. A twofold disorder was observed for the 1-acetoxy group whereas the 2-acetoxy group was ordered. CompoundB, (1,2,4)-1,2-diacetoxy-4-(2-methoxyphenyl)-8-methoxy-l,2,3,4-tetrahydronaphthalene, C₂₂H₂₄O₆,M _r=384.43, crystallizes in the monoclinic space group, P2₁/c, witha=16.209(2),b=10.076(1),c=13.357(4)Å,=111.41(2)°,V=2030.9ų,D _calc=1.26 g cm^–3 and=0.54 cm^–1 forZ=4. A final agreement index ofR=0.045 was realized by least-squares refinement of 1486 observed [F _o5 (F _o)] reflections. Intermolecular interactions in the cell lattices of compoundsA andB are noted. The title compoundsA andB were prepared by manganese(III) acetate oxidative dimerization of two molecules of 4-methoxystyrene and 2-methoxystyrene, respectively.     

The structure of β-(2)-nitrophenyl acrylonitrile

The structure of an important intermediate, IUPAC name: 2-(2-nitrophenyl) acrylonitrile has been studied by X-ray crystallography. C₉H₆N₂O₂ is monoclinic, space groupP2_1/c with cell dimensionsa=7.045(1),b=10.011(1),c=12.016(1) Å,=97.88(1)°,V=839.5(2) ų,Z=4,M _r =174.30,D ₀=1-38(1),D _x =1.39(1) g cm^–3,F(000)=360,T=293 K, (CuK)=1.5418 Å,=8.00 cm^–1,R=0.034 for 987 observed reflections. The aromatic ring is nearly planar. The Nitro group is rotated out of the aromatic plane by 26.5(1)°. There are three C-HO[3.469(3), 3.245(3), and 3.440(3) Å] and one C-HN[3.561(3) Å] intermolecular interaction.N.C.L. Communication No. 4847.     

Crystal structure of (4α,4aα,8aα)-(±)-octahydro-2-(phenylmethyl)-2H-1,2-benzoxazin-4-ol, 4-methylbenzenesulfonate(ester)

The title compound, a bicyclic tetrahydro-1,2-oxazine, crystallizes in a monoclinic lattice, space group P2₁/c, with a = 12.9809(18)Å, b = 12.920(2)Å, c = 13.631(2)Å, = 110.713(12)°, and Z = 4. The structure found in the solid state for this conformationally mobile molecule shows the tosyl group in an axial position and a benzyl group in an equatorial position of the bicyclic system.     

Structure of 2-(2′-bromo-5′-nitrostyryl)benzothiazole

The title compound C₁₅H₉BrN₂O₂S (brnsb) is monoclinic, witha=7.730(2),b=26.847(5),c=7.773(2) Å,=117.48(1)°,V=1431(1) ų,Z=4,D _x=1.677,(MoK)=29.9 cm^–1,F(000)=720,T=298K in space groupP2₁/c. The structure was solved by heavy atom and Fourier methods and refined toR=0.034 for 1776 unique observed reflections. The molecule is nearly planar, with a dihedral angle of only 3.8(1.1)° between the benzothiazole and phenyl rings. The C-S-C angle in the thiazole ring is 89.0°, while the C-N-C angle in that ring is 111.5(3)°.     

Synthesis and Structural Characterization of [2-(2-1H-Imidazoly)-1H-imidazolium nitrate] and [2-(2-1H-Imidazoly)-2H-imidazolium phthalyl glycinate] Based on the 2,2′-bi-1H-Imidazole Molecule

Abstract  

Two new compounds (H₃biim)(NO₃)(1) and (H₄biim)(phthgly)₂ (2) (H₂biim=biimidazole; Hphthgly=N-phthaloylglycine) have been synthesized and characterized by luminescence and single crystal X-ray diffraction study. Compound 1 crystallizes in the monoclinic space group C2/c, where a = 14.8078(15), b = 5.9233(6), c = 20.028(2) ?, β = 92.7910(10)°, V = 1754.6(3) ?³ and Z = 8. Compound 2 crystallizes in the monoclinic space group P2(1)/n, where a = 15.3775(14), b = 5.3200(6), c = 6.4689(18)?, β = 115.418(2)° V = 1216.9(2)?³ and Z = 4. In 1, the N–H groups of H₃biim⁺ and the oxygen atoms of NO₃ ⁻ are linked by hydrogen bonds leading to H₃biim⁺(N,N)–R₂²(10) and N–H···O interactions forming infinite 1D helical chains along the b-axis. Compound 2 consists of a planar diprotonated biimidazole moiety and two phthgly anions which connect to the dication by hydrogen bonds phthgly⁻(O,O)–R₂²(9).     

Structures and crystallization behavior of cis-α-[Co(trien)(NO2)2]·ClO4 (I), cis-β-[Co(trien)(NO2)2]Br·2H2O (II), and cis-β-[Co(trien)(NO2)2]·ClO3 (III)

Structures, conformations, and crystallization behavior of compounds cis--[Co(trien)(NO₂)₂]·ClO₄ (I), cis--[Co(trien)(NO₂)₂]Br·2H₂O (II), and cis--[Co(trien)(NO₂)₂]·ClO₃ (III) are reported. Compound (I) crystallized in space group Pbca, with a = 12.3323(9), b = 13.0265(9) and c = 18.1597(13) Å; compound (II) crystallized in space group Pca2₁, with a = 8.1844(7), b = 14.7011(14) and c = 12.4875(12) Å, while compound (III) also crystallized in space group Pca2₁, with a = 12.4897(8), b = 8.8499(6) and c = 12.6500(8) Å. In all three cases, the Co(III) ions were six-coordinated with nitrogens from trien and two nitrates. Inter- and intramolecular hydrogen bonding interactions are discussed to explain the conglomerate versus racemate crystallization behavior adopted by these three compounds, with comparison of their known analogue compounds of cis-/-[Co(trien)(NO₂)₂]X, where X = halide and NO^– ₃. For the cis--[Co(trien)(NO₂)₂]⁺ cation, the conformation of the cation itself determines the intramolecular hydrogen bonding pattern, and the interaction of counteranions can be ignored, while in cis--[Co(trien)(NO₂)₂]·ClO₄, the perchlorate interrupts the intramolecular hydrogen bonding pattern observed in the halide analog.     

The molecular structure of acetato[2-(pyridin-2′-yl)phenyl]mercury(II)

The crystal structure of the title compound was determined by X-ray crystallography. The compound crystallizes in the monoclinic crystal system witha=8.152(4),b=17.994(7),c=8.634(9) Å, =108.92(5)°, space group P2₁/c (N:14),V=1198.02 ų,Z=4. The mercuryl(II) atom forms two strong, almost colinear bonds (bond angle 176.1(4)°) with a carbon of the phenyl ring (Hg–C=1.99(1) Å) and one of the acetate oxygen atoms (Hg–O(1)=2.005(7) Å). These primary bonds are supplemented by secondary intramolecular interactions with the pyridine nitrogen (Hg...N=2.727(9) Å) and the other acetate oxygen (Hg...O(2)=2.925(8) Å), although the latter is very weak and the acetate anion therefore practically monodentate. Weak additional intermolecular Hg–C and Hg–O(1)interactions contribute to the lattice structure.     

Synthesis and crystal structure of a coordinatively unsaturated organomercury iridium complex (PCP) Ir(HgPh) Cl (PCP = η3-2,6-( t Bu2PCH2)2C6H3)

The title compound (PCP) Ir(HgPh) Cl (1), (PCP = ³-2,6-( ^t Bu₂PCH₂)₂C₆H₃), is obtained by the reaction of (PCP) IrHCl and Ph₂Hg in toluene solution. Purple crystals of 1 were grown by slow evaporation of benzene solution of 1 and have been studied by X-ray crystallography. The space group is P2₁/n, a = 13.9384(8) Å, b = 15.1095(8) Å, c = 15.8148(9) Å, = 111.005(1)°, V = 3109.3(3) ų, Z = 4. The geometry at the iridium center is quasi-square pyramidal with Hg at the apical position; the Cl–Ir–C(PCP) angle is 175.87(8)°. The Ir–Hg–C(Ph) angle is 175.90(9)°. The Hg–Ir bond is unusually short: 2.5251(2) Å. This short distance is likely attributable to the absence of a ligand trans to the phenylmercury group. The resulting strong metal–mercury bond may explain the unusual stability of the complex and the failure to eliminate mercury as is commonly observed with organomercury–transition-metal complexes.     

Structure of 1-(2′-tosyloxyethoxy)-8-tosyloxy-9,10-anthraquinone

The title compound crystallizes in the monoclinic space group, P2₁/c;a=12.938(1),b=11.041(1),c=19.285(2) Å, =104.314(8)°,Z=4. Refinement based on 1660 unique observed reflections converged toR=0.054. The anthraquinone moiety is distorted due to intramolecular steric hindrance from the tosylate groups.     

Crystal structure of triethylentetraammonium bis monohydrogen-monophosphate dihydrate β-NH3(CH2)2NH2(CH2)2NH2(CH2)2NH3(HPO4)2·2H2O

The salt triethylentetraammonium bis monohydrogen-monophosphate dihydrate is orthorhombic Pbca with unit cell dimensions a = 8.963(2), b = 10.326(2), c = 17.381(4)Å; Z = 4; D_m = 1.540 g cm^–3; D _x = 1.562 g cm^–3. The examination of the structure shows a layer arrangement parallel to the axis: planes of [HPO₄]^2– tetrahedra alternate with planes of [(NH₃(CH₂)₂NH₂CH₂)₂]⁴⁺. The [HPO₄]^2– tetrahedra are connected through O(W)s--H···O hydrogen bonds, so that infinite chains of the composition [HPO₄(H₂O)]_n ^2n– are formed in the structure parallel to the axis. The structure of this compound is built from [HPO₄]^2– anions, [(NH₃(CH₂)₂NH₂CH₂)₂]⁴⁺ cations and zeolitic water molecules connected by hydrogen bonds.     

Crystal and molecular structures of 1,4-dihydro-6-methyl-5-N,N-diethylcarbamoyl-4-phenyl-2(3H)-pyrimidinethione (1) and 1,4-dihydro-6-methyl-5-N-methyl carbamoyl-4-(2′-nitrophenyl)-2(3H)-pyrimidinethione hemihydrate (2)

The crystal structure of 1,4-dihydro-6-methyl-5-N,N-diethylcarbamoyl-4-phenyl-2(3H)-pyrimidinethione, C₁₆ H ₂₁ N ₃OS (1), is monoclinic, space group P2₁/n, a = 6.818(1), b = 13.211(2), c = 18.807(3) Å, = 99.53(1)°, V = 1670.6(4) ų, Z = 4 and d _cal = 1.206 Mg/m³, R = 0.042 (wR = 0.119) for 190 parameters and 2560 observations with I 2(I) and 1,4-dihydro-6-methyl-5-N-methyl carbamoyl-4-(2-nitrophenyl)-2(3H)-pyrimidinethione hemihydrate, C₁₃ H ₁₄N₄O₃S 0.5H₂O, (2), is triclinic, space group P1, a = 7.513(1), b = 14.381(2), c = 15.506(2)Å, = 114.95(2), = 98.11(1), = 93.55(1)°, V = 1490.0(3) ų, Z = 4 and d _cal = 1.406 Mg/m³, R = 0.062 (wR = 0.165) for 388 parameters and 3094 observations with I 2(I).The compound 2 crystallized having two molecules in the asymmetric unit, which can be regarded as monohydrated dimers, and forming a hydrate. The conformation of the central heterocyclic ring (1,4-dihydropyrimidine) in both compounds was found to be close to a half-chair conformation. The 2-nitrophenyl substituent in 2 is in the axial synperiplanar orientation. In both compounds, the conformation of the 3-substituted carbamoyl group appears to be influenced by hydrogen bonding with anticlinal orientation observed for carbonyl groups serving as hydrogen bonding acceptors.