Crystal and molecular structure of 5-bromo-pentacyclo[4.3.0.02,5.03,8.04,7]nonane-4-carboxylic acid,C10H9BrO2

The structure of the title compound, C₁₀H₉BrO₂, was determined by X-rays.M _r =241.08, triclinic, space groupP¯1,a=5.800(1),b=6.441(1),c=12.030(1) Å,=92.90(1)°,=95.65(2)°, =95.69(2)°,V _c =444.2 ų,Z=2,D _x =1.80 Mg m^–3, MoK radiation (graphite crystal monochromator, =0.71069 Å),(MoK)=48.58 cm^–1,T=290 K. Final conventionalR-factor=0.037,R _w =0.044 for 1863 observed reflections and 145 variables. The structure was solved usingMultan andDirdif. The results show that the 5-bromo substituent has a marked effect on the geometry of the homocubane skeleton. Its presence prevents a complete release of geometrical strain and induces a shortening of the bond distances to the apex carbon atom.     

Crystal and molecular structure of binuclear copper acetate mono-α-picoline

Green, needle-shaped crystals of copper acetate mono--picoline, Cu(ac)₂-(-pic), crystallize in space groupP2₁/c with cell dimensionsa=7.675(4),b=20.008(6),c=8.207(4)Å, and =115.99(3) °. The crystal structure has been solved by the heavy-atom method and refined with the three-dimensional x-ray photographic data to anR factor of 9.2%. The structure consists of binuclear units Cu₂(ac)₄(-pic)₂. The Cu-Cu distance is 2.671 Å. The bond length Cu-N (2.24 Å) is significantly longer than the corresponding distance in analogous complexes.     

Crystal and molecular structure of OC(CoC5H5)3(CF3CCCF3)

The structure of the title compound has been confirmed by an X-ray diffraction analysis, and refined by full-matrix least squares. The crystals are mono-clinic:a=9.171(3),b=25.176(15)c=9.192(3) Å,=117.08(3)°,Z=4,D _x =1.976g cm^–3,=2.66mm^¯1, space groupP2₁/n (No. 14). The finalR value is 5.7%. Interatomic distances and bond angles are compared with those reported in related molecules.The preferred name of this compound according to the IUPAC rules is ₃-[11–2-bis(trifluoromethyl)vinylene]- ₃-carbonyl-tris (-cyclopentadienyl)-triangulo-tricobalt.     

Studies of systemic acylanilide fungicides. Part IV. Crystal structure and molecular conformation ofN-(2-methoxyacetyl)-N-(2,6-xylyl)-α-amino-γ-butyrolactone

The crystal structure of the title compound (C₁₅H₁₉NO₄, MW 277.3 amu) was determined by three-dimensional X-ray analysis from diffractometer data. Crystal data are: monoclinic,P2₁/n,a=9.600(3) Å,b=11.964(6) Å,c=12.802(4) Å,=101.25(3)°,V=1442.1(16) ų,Z=4;D _x =1.277 Mg m^–3;(MoK)=0.10 mm^–1. FinalR=0.055 for 1686 observed reflections having 2 (MoK)<50° andI>2.5 (I). The compound is isostructural withN-(2-methoxyacetyl)-N-(2,6-xylyl)-3-amino-1,3-oxazolidin-2-one. The dimethylphenyl ring is almost perpendicular to the amidic plane of the molecule (dihedral angle 81.9°); the butyrolactone ring is in the typical envelope conformation.     

Crystal and molecular structure of (exo)-1-methoxycarbonyl-5-ethoxycarbonyl-4, 5,6,11b-tetrahydroisoxazolidino-[2,3-a]-β-carboline,C18H20N2O5

The structure of the title compound, C₁₈H₂₀N₂O₅, was determined by X-rays atT=290 K.M _r =344.366, orthprombic, space groupP2₁2₁2₁,a=9.350(5),b=11.954(2),c=15.455(3) Å,V _c =1727.3 ų,Z=4,D _c =1.324 Mg m^–3. CuK. radiation (graphite crystal monochromator, =1.54178 Å),(CuK)=7.70 cm^–1. Final conventionalR-factor=0.065,R _w =0.086 for 2887 observed reflections and 265 variables. The structure was solved usingMultan.     

Two acetylamino derivatives of 2,4-bis(trichloromethyl)-1,3-benzdioxin showing different types of hydrogen bonding: (a) (C13C)CH⋯O=C and (b) N-H⋯O=C

8-Acetylamino-6-methyl-2,4-bis(trichloromethyl)-1,3-benzdioxin, (I), is monoclinic,P2₁/c,a=15.174(4),b=11.977(7),c=9.911(3)Å,=99.72(2)°. 6-Acetylamino-2,4-bis(trichloromethyl)-1,3-benzdioxin, (II), is monoclinic,P2₁/_n,a=5.927(4),b=40.623(1),c =7.120(3)Å,=91.39(4)°. In compound (I) the imino hydrogen atom is locked in an intramolecular hydrogen bond to the proximate oxygen atom of the heterocyclic ring and is not available for intermolecular hydrogen bonding. Instead the weakly acidic hydrogen atom [Cl₃C-C(2)]H takes part in a hydrogen bond to the carbonyl oxygen atom in another molecule. In compound (II) a normal intermolecular hydrogen bond of the type N-HO=C occurs. The 6-acetylam-ino group is twisted about the (C_Ar-N) bond such that the angles NHO=C, C_ArH_ArO=C, NHOH_ArC_Ar, at the carbonyl oxygen group total 360° (where NH is in the related molecule). The packing in both compounds takes the form of infinite chains and in compound (II) partial overlap of the aromatic ring and the acetylamino group, with very little offset, also occurs.     

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 751-1751-1751-1751-2751-2751-2

The title compound crystallizes in the centrosymmetric triclinic space group (No. 2) witha=10.818(1)Å,b=10.876(1)Å,c=11.072(2)Å, =98.74(1)°, =98.83(1)°, =96.61(1)°,V=125906(3)ų andZ=2. Interatomic distances include Fe–P=2.243(2)Å, Fe–CO=1.771(6)–1.781(5)Å, Fe–C(C₅H₅)=2.074(6)–2.103(5)Å and P–F=1.511(6)–1.571(4)Å.     

Hydrogen bonding in 2-hydroxy((di)thio)benzoates. I. X-ray structures of 2,6-dimethylpiperidinium salts

X-ray structural data are reported for 2,6-dimethyl-piperidinium-2-hydroxybenzoate (C₁₄H₂₁NO₃, orthorhombic,P2₁2₁,2₁, (19);a=7.983(1)Å,b=12.680(2)Å,c=13.838(2)Å;Z=4;R=0.042) and for two polymorphs of 2,6-dimethylpiperidinium-2-hydroxythiobenzoate (C₁₄H₂₁NO₂S), an-form (monoclinic,P2₁/n (14);a=8.005(4)Å,b=22.150(2)Å,c=8.672(4)Å,=101.91(6)°;Z=4;R=0.059) with an intramolecular O-HS hydrogen bond, and a-form (orthorhombic,P2₁2₁2₁ (19);a=8.188(1)Å,b=14.781(2)Å,c=24.163(4)Å;Z=8;R=0.15) with an intramolecular O-HO hydrogen bond. The intra-and intermolecular hydrogen bond patterns are discussed, including the literature data of 2,6-dimethylpiperidinium-2-hydroxydithiobenzoate.     

Conformational study on aryl ketones: The structure of 2,6-dimethyl-1,5-di-(2-methyl)-propanoylnaphthalene

C₂₀H₂₄O₂ (M _r =296.4) crystallizes in the monoclinic system, space groupC2/c witha=24.154(4),b=8.001(2),c=12.751(3) Å;=136.8(1)°;V=1686.9 ų,Z=4,D _c =1.17 g cm^–3,(Cu-)=5.4 cm^–1,=1.5418 Å,F(000)=640. The molecule in the solid state adopts a centrosymmetric geometry with the molecular center of symmetry coincident with a crystallographic center of symmetry. This fact forces the molecule to themeso conformation.     

Complexation with diol host compounds. Part 3. Molecular inclusion of 4-methylcyclohexanone and 2-methylcyclohexanone by the host,trans-9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene

The structures of the 12 molecular complexes oftrans-9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with 4-methylcyclohexanone (1) and with 2-methylcyclohexanone (2) have been determined by X-ray crystallography. The crystal data are as follows: Compound (1):P2₂/c,a=8.838(2) Å,b=8.92(1) Å,c=20.879(8)=Å,=98.67(2)°,V=1627(2) ų,Z=2 andR=0.062 for 2201 unique MoK reflections; Compound (2):P¯1,a=8.917(3) Å,b=9.900(2) Å,c=11.250(4) Å,a=68.72(2)°,=64.39(3)°, =74.86(2)°,V=828.1(5) ų,Z=1 andR=0.098 for 2563 unique reflections. Both inclusion compounds exhibit O-HO=C hydrogen bonding interactions. The thermal properties of these compounds have been characterized by DTA and TGA thermograms.     

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.     

Crystal and molecular structure of 3-methoxy-6-nor-6,7-secooestra-1,3,5(10),9(11), 14-penten-17-one-8β-ethyl carboxylate

C₂₀H₂₂O₄,M _r =326.39, triclinic,P¯1,a=10.365(2),b=11.383(2),c=8.461(1) Å, =103.60(1),=104.44(1), =105.23(1)°,Z=2, (CuK)=1.54178 Å;R=0.0633 for 1940 reflections. The results of the X-ray analysis have shown that the ethyl carboxylate substituent is oriented. The geometry of the main skeleton of the molecule has not revealed any significant differences in the present compound and in the case of the epimeric molecule.     

Crystal structures of five policyclic compounds related to the natural product forskolin

(3(Z),4,6a,9a,9b)-(±)-3a,4,6a,7,8,9,9a,9b-octahydro-4,7,7, 9b-tetramethyl-3a-[3-(methoxymethyloxy)-3-methyl-1-butenyl]-5H-naphto[1,8-de]-1,3-dioxin-6-one (I), C₂₂H₃₆O₅,M _r=378.51, monoclinic,P2₁/n,a=6.330(1),b=14.576(2),c=22.837(2)Å,=93.04(1)°,V=2104.1(2)ų,Z=4,D _c=1.19 Mg/m³, (MoK)=0.71069Å,=0.8 cm^–1,F(000)=832,T=298 K,R=0.054 for 1971 observed reflections; (7a,10a,10b,12)-(±)-7a,9, 10,10a,10b,11,12,12a-octahydro-2,2,10,10,10b,12a-hexamethyl-2H,8H-1-benzopyrano[4a,5,6,-de][1,3,2]-benzodioxin-11-one (II), C₂₀H₂₉O₄,M _r=334.5, triclinic,P-1,a=10.595(2),b=12.152(1),c=8.073(1)Å,=106.53(1),=105.65(1), =66.29(1)°,V=897.9(2)ų,Z=2,D _c=1.24 Mg/m³, (MoK)=0.71069Å,=0.8 cm^–1,F(000)=362,T=298 K,R=0.046 for 2848 observed reflections; (7a,10a,10b,12, 12a)-(±)-7a,9,10,10a,10b,11,12,12a-octahydro-2,2,10,10,10b,12a-hexamethyl-2H,8H-1-benzopyrano[4a,5,6-de][1,3,2]-benzodioxin-11, 12-diol (III), C₂₀H₃₂O₅ (two molecules in the asymmetric unit),M _r=352.2, triclinic,P-1,a=12.948(3),b=13.615(3),c=12.197(4)Å,=101.16(2),=111.88(2), =69.48(2)°,V=1863.8(9)ų,Z=2,D _C=1.26 Mg/m³,(MoK)=0.71069 Å,=0.8 cm^–1,F(000)=768,T=298 K,R=0.060 for 4570 observed reflections; 4-acetoxy-4-[[(4a,5,8a)-(±)-hexahydro-4a,6,6-trimethyl-4H-1,3-benzodioxin-4-one]-5-yl]butan-2-one (IV), C₁₇H₂₆O₆,M _r=326.4, monoclinic,P2₁/c,a=10.495(2),b=12.050(2),c=14.216(2)Å,=108.51(1)°,V=1704.8(5)ų,Z=4,D _c=1.27 Mg/m³,(MoK)=0.71069 Å,=0.9 cm^–1,F(000)=704,T=298 K,R=0.049 for2455 observed reflections; (3a,4,5,6,6a,9a,9b)-(±)-4,5-epoxy-decahydro-3, 3a-dihydroxy-2-ethoxy-4,7,7,9b-tetramethyl-naphto-[1,8-bc]-pyran-6-ol-acetate (V), C₂₀H₃₂O₇,M _r=383.5, monoclinic,C2/c,a=10.353(2),b=17.975(3),c=21.188(3)Å,=91.29(1)°,V=3942(1)ų,Z=8,D _c=1.29 Mg/m³,(MoK)=0.71069 Å,=0.8 cm^–1,F(000)=1664,T=298 K,R=0.051 for 2120 observed reflections. We report here the complete structures of four decalin derivatives (compoundsI, II, III, V) and one related compound (compoundIV) synthetized in order to find an efficient synthetic approach for the natural productforskolin.     

Molecular complexes of sulfonamides. 3. Structure of 5-methoxysulfadiazine (form II) and its 1∶1 complex with acetylsalicylic acid

The X-ray structure of the biologically most active polymorph (Form II) of 5-methoxysulfadiazine (1) and that of the 11 complex between this sulfonamide and acetylsalicylic acid (2) are reported. The polymorph1 is monoclinic, space groupP2₁/c witha=13.086(2) Å,b=5.583(1) Å,c=17.222(3) Å, =99.98(1)°,Z=4 and occurs as centrosymmetric hydrogen bonded (N–H...N) dimers in the crystal. This arrangement differs from that observed in other polymorphs of the drug. Complex2 is triclinic, ,a=8.102(1)Å,b=12.033(1) Å,c=12.170(2) Å, =111.67(1)°, =93.77(1)°, =103.82(1)°,Z=2. Complexation involves linear intermolecular hydrogen bonds, N–H...O=C and N...O–H, between the amide group and pyrimidinyl N atom of the sulfonamide and the carboxylic group of the acetylsalicylic acid. On complexation to form2, neither molecular component undergoes any major structural change.     

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.     

Structure oftrans-difluorobis(1,3-propanediamine)chromium(III) perchlorate,trans-[Cr(N2C3H10)2F2](C104)

The title compound is monoclinic,M _r =337.8,P2₁/c-C _2h ⁵ (No. 14),a=5.508(2),b=13.944(6),c=18.238(5) Å,=95.99(3)°,V=1393.1(9) ų,Z=4,D _x =1.61 g cm^–3, (MoK)=0.71073 Å,F(000)=660.0,=10.3 cm^–1, finalR=0.051 for 2122 observed [I>3(I)] reflections. The two six-membered rings resulting from the coordination of the 1,3-propanediamine ligands to the chromium atom are in the chair conformation. The Cr-N and Cr-F distances average 2.085(4) and 1.876(3) Å, respectively.     

Pentacoordinated tin(II); crystal structure of dichloro-[2,2′∶6′,2″-terpyridyl]-tin(II)

The crystal structure of a well-defined 5-coordinate complex, dichloro-(2,26, 2-terpyridyl)-tin(II), is described. The stereochemistry of this complex is strongly influenced by the stereochemically active pair of electrons, illustrating clearly the potential donor capabilities of this molecule. The complex (C₁₅H₁₁Cl₂N₃Sn) crystallizes in the monoclinic space groupC2/c (No. 15) witha=15.770(5),b=9.450(2),c=10.482(2) Å,=97.53(2)°,Z=4. The finalR value is 0.029 for 1085 observed reflections.     

Crystal structures of the new diphosphates,K2NiP2O7 and K6Sr2Ni5(P2O7)5

Crystalline K₂NiP₂O₇ (I): monoclinic, P2₁,a=9.230(2),b=17.540(8),c=8.319(9)Å, =91.44(2)°,Z=8,d _calc=3.067 g cm^–3, MoK =0.71069Å,R/R _w=6.5/9.4%, is characterized by the existence of face sharing NiO₆ octahedra with Ni–Ni separation of 2.827 Å (Ni–O; 1.93(2)–2.17(2)Å). K⁺ is seen in sites of seven, six, and fivefold coordination (K–O, averages; 2.83(2), 2.81(2), and 2.77(2)Å, respectively) P₂O₇ ^4– groups are observed in semieclipsed conformation. K₆Sr₂Ni₅(P₂O₇)₅ (II) crystallizes in monoclinic space group P2₁/c;a=11.038(7),b=9.533(13),c=7.438(2)Å, =100.13(4)°,D _calc=3.309 g cm^–3,Z=2,R/R _w=6.4/8.1%. Nickel atoms are distributed on planes parallel to the crystallographic (100) plane at =0 and =0.5. On the planes, =0, Ni²⁺ ions form successive linked trimers of edge sharing NiO₆ octahedra (Ni–Ni, 3.018(1), 3.008(1)Å; Ni–O, av 2.07(2)Å). The intermediate planes (=0.5) contain isolated and six coordinate Ni²⁺ ions (Ni–O av. 2.09(2)Å). Seven-coordinate potassium ions (K–O, av. 2.74(2)Å) are located on intermediate planes at =0.25 and 0.75. P₂O₇ ^4– groups are found in eclipsed conformation. Strontium atoms are located between nickel and potassium planes and are surrounded by seven oxygen atoms (Sr–O, av. 2.586(2)Å).     

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.