The molecular and crystal structure of endo-2-methyl-7-hydroxy-7-oxo-N-phenyl-7-phosphabicyclo-[2.2.1] hept-2-ene-5,6-dicarboximide

The structure of the title compound1 has been determined by X-ray crystallography analysis. The following crystal data were found: orthorhombic,Pca2_l,a=9.60691),b=16.356(1),c=8.686(1) . Both the phospholane and phospholene rings involved in the 7-phosphabicyclo-[2.2.1] hept-2-ene system have almost regular envelope conformations, and the cyclohexene ring has a significantly deformed boat conformation. The low value of the C–P–C angle, 84.2(2)°, reflects the steric strain around the phosphorus bridge and may be responsible for the reactivity of esters and amides derived from1 in the O-insertion reaction with m-chloro-perbenzoic acid. The dihedral angle between the plane of the benzene and succinimide rings is 82.4(2)°.     

X-ray structures of 1,3-dithiolo[4,5-c]quinoline and 2,3-dihydro-1,4-dithiino[5,6-c]quinoline

The title compound I (C₁₀H₇NS₂) is orthorhombic: Pbca,a=16.223(6),b=15.065(5),c=7.356(4) Å. The conformation of 1,3-dithiol ring is of an envelope-type. A very short intramolecular sulfur-sulfur distance of 2.94 Å was observed. The compoundII (C₁₁H₉NS₂) is monoclinic: P2₁/c,a=5.113(2),b=11.978(4),c=16.444(5) Å, =98.00(5) deg. The conformation of the 1,4-dithiin rings is a half-chair. As compared to other 3,4-quinolinediyl bis-sulfides an elongated intramolecular sulfur-sulfur distance of 3.437(4) Å in dihydrodithiinoquinolineII was observed.Part XXXI in the series of Azinyl Sulfides.     

Crystal and molecular structure of 3-mesityl-4-methyl-5-(3′-mesityl-5′-methyl-Δ2′-isoxazolin-4′-yl)-Δ2-isoxazoline,C26H32N2O2

The crystal structure of the title compound, C₂₆H₃₂N₂O₂, has been determined by three-dimensional X-ray diffraction methods. The crystals are monoclinic:P2₁/c,a=13.338(9),b=17.364(12),c=10.320(8) Å,=99.84(6)°,Z=4. The structure was solved by direct methods, and refined to anR value of 0.069 for 2258 observed reflections. Bond lengths and angles have normal values. The isoxazoline rings are in an envelope conformation and their best planes are twisted by 77.8°; the mesityl groups are inclined to the heterocyclic rings (63.3 and 69.0°). No significant conjugation is evident within the molecule.     

Crystal structures of 3,5,5′-trichloro-2,2′-bithiophene and 3,3′,5,5′-tetrachloro-2,2′-bithiophene

The crystal structures of 3,5,5-trichloro-2,2-bithiophene (I) and 3,3,5,5-tetrachloro-2,2-bithiophene (II) have been determined by single crystal X-ray diffraction techniques. BothI andII crystallize in the monoclinic crystal system. ForI,a=3.895(2),b=11.928(2),c=10.701(2)Å,=97.70(1)°, space groupP2₁,Z=2 and forII,a=8.942(2),b=3.900(2),c=15.180(2)Å,=92.30(1)°, space groupP2₁/n,Z=2. The structures have been solved by direct methods and all nonhydrogen atoms refined with anisotropic thermal parameters. ForI the final residual is 0.035 (all 1185 independent reflections, MoK radiation) and forII, 0.034 (all 1209 independent reflections, MoK radiation). BothI andII have theanti conformation butI has a torsion angle of 3.4(5)° between the two thiophene rings whileII is completely planar.     

Molecular structure and hydrogen bonding of 4-dimethylaminopyridinioacetate in its crystalline dihydrate and hydrochloride trihydrate,L·2H2O and [L2H]Cl·3H2O (L=p-Me2NC5H4N+CH2CO2 −)

The crystalline dihydrate and hydrochloride trihydrate of a new betaine, namely, L·2H₂O (1) and [L₂H]Cl·3H₂O(2) (L=p-Me₂NC₅H₄N⁺CH₂CO₂), have been synthesized and characterized by X-ray crystallography. Molecule L in compound1 [space groupPbcn, witha=15.732(3),b=7.894(2),c=18.304(4) Å, andZ=8] possesses approximateC _s symmetry. The formation of hydrogen bonds by water molecules bridging neighboring carboxy oxygen atoms leads to an infinite two-dimensional network composed of a packing of two different kinds of 12-membered rings. In compound2 [space group PT witha=7.341(2),b=9.543(2),c=17.010(4) Å, =82.43(2)°, =80.34(2)°, =74.05(2)°, andZ=2], the carboxylate groups of a pair of betaine molecules are bridged by a proton to form a dimeric cation L₂H⁺ with a very strong asymmetric hydrogen bond of length 2.464(7) Å. The crystal structure features a hydrogen-bonded corrugated ribbon comprising an alternate arrangement of edge-sharing centrosymmetric (H₂O)₄(Cl^–)₂ and (H₂O)₄ rings running parallel to thea axis.     

Synthesis of 3,4-dihydro-3,3-dimethyl-1(2H)-acridinone

The acridinone derivative 3,4-dihydro-3,3-dimethyl-1(2H)-acridinone (4) has been prepared in a two step fashion and the molecular structure confirmed by X-ray diffraction. Compound4 crystallizes in the space group P2_l/n witha=6.022(2),b=21.111(2),c=9.604(2) Å, =99.97(2)°, andZ=4. The single crystal analysis showed the acridinone tricyclic ring is virtually planar except in the gem-dimethyl position of C(3) which presented a half-chair conformation.     

X-ray crystal structure analysis of nitroxazepine: 10-(3-dimethylaminopropyl)-2-nitro-10,11-dihydrodibenz [b,f][l,4]oxazepin-11-one

The title compound, C₁₈H₁₉O₄N₃,M _r=341, the base (I) of the dibenzoxazepine anti-depressant drug Sintamil, crystallizes in the orthorhombic space group,Pbca withZ=8 in a cella=8.636(2),b=23.687(3),c=16.787(3)Å,V _c=3434 ų. The structure was solved by direct methods and refined toR=0.102 (R _w=0.093) with 1348 observed CuK reflections. The tricyclic framework takes up a saddle shape with the heterocyclic ring in boat conformation; the flanking planar aromatic rings make angles 148.2(3), 150.8(3)° with the central ring plane, compared with 143.5(5), 158.1(5)° in Sintamil monohydrate (II). BothI andII have extended-CNMe₂ side chains (with appreciable thermal motion); this conformation, and the distances of the -N(CH₃)₃ nitrogen to the centers of aromatic rings (6.4 and 7.8 Å inI), are consistent with inhibition of uptake mechanisms underlying the pharmacological action.     

Crystal and molecular structure of 3a,6a-dihydro-3-phenylthiolan [2,3-d]isoxazole-4-oxide,C11H11NO2S

The crystal and molecular structure of the title compound, C₁₁H₁₁NO₂S, has been determined by X-ray analysis from diffractometric data. The crystals are monoclinic:P2₁/n, a=17.186(4),b=10.848(2),c=5.588(1) Å,=91.96(1)°,Z=4. The structure was solved by direct methods, and refined by full-matrix least-squares toR=0.043 for 1551 observed reflections. Bond lengths and angles have normal values. The isoxazoline and the thiolane rings are in an intermediate envelope/twist conformation, with a dihedral angle of 109.7(1)° between their best planes, whereas the phenyl ring is rotated 4.1(1)° from the isoxazoline ring, thus allowing extensive conjugation within this moiety.     

Annulated bicyclo[2.2.2]octenones: 9-hydroxy-9-chloromethyl-endo-tricyclo[5.2.2.02,6]undeca-4,10-diene-3-spiro(1′-cyclopropane)-8-one and 12-hydroxy-12-chloromethyl-endo-tricyclo [8.2.2.02,9]tetradeca-13-en-11-one

A single crystal X-ray diffraction study of two annulated bicyclo[2.2.2]octenones has been carried out to establish their precise stereostructures. The compounds, with their crystal data, are:1, 9-hydroxy-9-chloromethyl-endo-tricyclo[5.2.2.0^2,6]undeca-4,10-diene-3-spiro(1-cyclopropane)-8-one, C₁₄H₁₅O₂Cl, space group P2₁/c,a=10.540(2),b=9.668(1),c=11.841(4)Å, =95.67(2)°,Z=4, and2, 12-hydroxy-12-chloromethyl-endo-tricyclo[8.2.2.0^2,9]tetradeca-13-en-11-one, C₁₅H₂₁O₂Cl, space group C2/c,a=20.747(8),b=6.498(1),c=20.525(3)Å, =93.04(3)°,Z=8. The molecule of1 has endo stereochemistry at the ring junction and the spirocyclopropane ring is proximal to the hydroxyl group. In2, the eight membered ring deviates from a chair conformation and one ring atom is disordered. Crystals of1 and2 contain centrosymmetric dimers formed by C=O...O–H hydrogen bonds.     

X-ray crystal and molecular structure of upper rim monoformylated calix[4]arene system

Selective formylation under controlled conditions leads to the formation of a monoformylated compound 11-formyl-25,27-bis(ethoxycarbonylmethoxy)-calix[4]arene (1). The spectroscopic results indicated that the calix[4]arene is present in a cone conformation. The crystal and molecular structure of (1) has been determined by X-ray diffraction methods. The crystal data are monoclinic, space group P2 ₁/c, M= 624.66, a= 10.341(1), b=15.176(1), c= 20.121(1) Å, = 91.90°(1), V= 3156.0(4) ų, Z= 4, D _c = 1.315 g cm^–3. The structure confirms the cone conformation for the molecule in the solid state as well.     

X-ray crystallographic determination of the structure and conformation of new metabolites from microbial hydroxylation by Absidia blakesleeana ATCC 10148

The crystal structure and conformation of 10R-hydroxy-1,4,4-trimethyltricyclo[5.4.0.0^3.5]undec-7-en-9-one (II) and 10S-hydroxy-1,4,4-trimethyltricyclo[5.4.0.0^3.5]undec-7-en-9-one (III) have been determined by X-ray diffraction. In both cases the crystals were monoclinic, P2₁,a=12.907 (4),b=7.484(3),c=14.179(4) Å,=110.65 (3)°,Z=4, (II);a=16.351 (5),b=7.468 (3),c=20.917 (6) Å,=91.83 (4)°,Z=8 (III). The structure was solved by direct methods, and refined to anR _w value of 0.034 for 2483 (II) and 0.053 for 3810 (III) independent reflections, withI3.0(I). There were two crystallographically independent molecules in the case ofII and four in the case ofIII. In all independent forms of both compounds the ring substituted by a carbonyl group had the distorted³E sofa conformation; whereas the second one possessed the slightly deformed^7.10B boat conformation. The crystal structures ofII andIII are stabilized by two and four intermolecular hydrogen bonds, respectively.The nomenclature of IUPAC was applied for the names of compounds, However, for simplicity, numbering of atoms was according to Figs, 1a and 1b.     

Crystal and molecular structures of trans-bis(acetonitrile)bis(bipyridine)ruthenium(II) perchlorate and trans-diamminebis(bipyridine)ruthenium(II) perchlorate

The structures of trans-[(MeCN)₂(bpy)₂Ru](ClO₄)₂(I) andtrans-[(NH₃)₂(bpy)₂Ru](ClO₄)₂(II) have been determined by single crystal X-ray diffraction methods. (I) forms monoclinic crystals in the space groupP2₁/c witha=8.399(2),b=10.406(2),c=15.590(3) Å,=93.78(2)° andZ=2 atT=293 K. The final refinement gaveR=0.040 for 2448 reflections withF _o ² >3(F _o ² ). (II) crystallizes in the triclinic space groupP¯1 witha=1.702(1),b=8.439(2),c=10.525(2) Å,=107.56(2),=104.63(1), =100.89(2)° andZ=1 atT=293 K. Refinement using 1878 reflections withF _o ² >3(F _o ² ) produced a finalR value of 0.036. Both of these structures have the ruthenium atom located on a crystallographic inversion center. The bipyridine ligands in both structures are in the bowed conformation as a means of circumventing the steric problems associated with the trans arrangement of the bipyridine ligands. The Ru-N(monodentate) distance is longer for the ammonia complex (2.106(3) Å) than for the acetonitrile complex (2.008(4) Å); there are no significant differences in the distances and angles of the two Ru(bpy)₂ frameworks.     

Crystal and molecular structures of 1-(2-iso butylylcarbamoyl propan-2-ylamino) 3-(1-naphthyloxy)propan-2-ol hydrochloride (1) (C21H31N2O3Cl) and 1-(2-isobutyloxycarbonylo propan-2-ylamino) 3-(1-naphthyloxy)propan-2-ol hydrochloride (2) (C21H30NO4Cl)

This paper shows the crystal structures of two new-adrenergic antagonists, derivatives of propranolol, which were determined with three-dimensional x-ray diffraction data. The space groups and unit-cell parameters are: compound1 (C₂₁H₃₁N₂O₃Cl) monoclinic space groupP2₁/c,a=20.523(4),b=6.909(2),c=15.950(2) Å,=105.03(1)°; compound2 (C₂₁H₃₁NO₄Cl) monoclinic space groupP2₁/c,a=6.364(2),b=36.043(8),c=10.149(1) Å,=104.48(2)°. The structures were solved with direct methods, and refined with full-matrix least-squares techniques toR indices of 0.059 and 0.067, respectively. The-CH(OH)-CH₂-NH-sections of the side chains show the conformation approximate togauche.     

Structure of 6,13-bis(<Emphasis Type="Italic">N</Emphasis>, <Emphasis Type="Italic">N</Emphasis>-dimethylcarbamoyl) thioquinanthrene

The crystal structure of 6,13-bis-(N,N-dimethylcarbamoyl)thioquinanthrene 3 has been determined as monoclinic, with space group P2(1)/c with lattice parameters a = 10.044(2) Å, b = 21.385(4) Å, c = 10.889(3) Å, = 102.92(3)°, Z = 4 and D_calc = 1.342 Mg/m³. The middle 1,4-dithiin ring in the title compound 3, C₂₄H₂₀N₄O₂S₂ is in a boat conformation with the dihedral angle between the planes of the aromatic rings 132.45(8)°.     

Crystal and molecular structures of 1-(2-carboxypropan-2-ylamino)-3-(1-naphthyloxy) propan-2-ol (1) (C17H21NO4) and 1-(2-carbamoyl propan-2-ylamino)-3-(1-naphthyloxy) propan-2-ol (2) (C17H22N2O3)

The crystal structures of two new-adrenergic antagonists, derivatives of propranolol containing 2-methylalanine fragment are described in this paper. The space groups and unit-cell parameters are: compound1 (C₁₇H₂₁NO₄): monoclinic, space groupP2₁/n,a=5.787(1),b=18.703(4),c=23.526(5)Å,=96.49(2)°; compound2 (C₁₇H₂₂N₂O₃): triclinic, space groupP¯1,a=8.321(1),b=10.121(1),c=10.368(1)Å,=109.49(1)°,=90.49(1)°, =103.48(1)°. The structures were solved by direct methods and refined with full matrix least-squares techniques toR indices of 0.055 and 0.049, respectively. The molecules of compound1 exist in the crystal as dual ions. The molecules of compound2 are compact and their external chain is twisted in a characteristic way (similar to that found in peptides).     

Solid state conformational parameters in dibenzo[b,f]heteroepin drugs: Crystal structures of 3-methoxy-10-methyl-11-phenyldibenzo[b,f]thiepine and 3-allyloxy-10-ethyl-11-phenyldibenzo[b,f]oxepine

The structures of 3-methoxy-10-methyl-11-phenyldibenzo[b, f]thiepine (I) [C₂₂H₁₈OS, tetragonal,I4₁/a, witha=33.81(1),c=6.065(5)Å,Z=16] and 3-allyloxy-10-ethyl-11-phenyldibenzo[b,f]oxepine (II) [C₂₅H₂₂O₂, mono-clinic,P2₁/c,a=12.115(7),b=16.316(9),c=10.136(7)Å,=105.05(9)°,Z=4] have been determined by the symbolic addition procedure and refined by least-squares method to anR of 0.090 for 784 diffractometer-measured reflections (I) and to anR of 0.083 for 442 reflections (II). The dihedral angle between the phenyl-ring mean planes is 111.3° in (I) and 121.1° in (II), the middle seven-membered ring has the boat conformation, and the tricyclic moiety has twist and skew values of 6° and 0.42 Å in (I) and 0.3° and 0.79 Å in (II). The overall conformational characteristic for the tricyclic (6, 7, 6)-dibenzo[b,f]heteroepin derivatives have been reviewed to gain a better understanding of what requirements may be important for interaction of drugs of this class at the receptor site.     

Synthesis and crystal structure of 1-vinyl-cis-2,3-diphenylaziridine

1-Vinyl-cis-2,3-diphenylaziridine, C₁₆H₁₅N, has been synthesized and characterized by spectroscopic methods and single crystal X-ray analysis. The structure was studied at room temperature (2a) (18°C) and at low temperature (2b) (–70°C). The title compound crystallizes in the space group Cm with Z=2 showing no phase transformation between the two temperatures. The cell parameters area=8.258(3),b=15.880(3),c=5.827(2)Å, =122.32(2)° for (2a) anda=8.188(2),b=15.762(3),c=5.724(1)Å, =121.57(2)° for (2b). Both the studies show nearly the same conformation. With the exception of the vinyl group, the molecule hasm symmetry, so, the asymmetric unit is half a molecule. The mirror plane of the space group cuts the aziridine ring through the N atom. The vinyl group is distributed on two symmetrical positions by means of the same mirror plane. In this way, the crystal is built with the two diastereoisomers of the title compound.     

X-ray structural and spectroscopic investigation of 1-piperidine-2,4-dinitrobenzene

The crystal structure of the title compound (C₁₁H₁₃N₃O₄) has been determined by single-crystal X-ray diffraction. The compound is monoclinic, space group P2₁/n, witha=9.968(2),b=9.156(2),c=13.249(2)Å, =102.05(2)°, andD _x=1.563 gcm^–3 forZ=4. The aromatic ring shows a slight boat deformation. Theo- andp-NO₂ groups are twisted out of the plane of the phenyl ring by 39.0(2)° and 4.4(1)°, respectively. The piperidine ring exhibits a slightly deformed chair conformation. Short C–H...O intermolecular contacts stabilize the three dimensional structure. UV and NMR data indicate that the molecule in solution presents a conformation similar to that of the the solid state.     

Structure of 1,1,3(RS),6,6,8(RS)-hexamethyl-cis-10b(SR),10c(SR)-perhydro-1H,6H-3a(SR), 5a(SR) 8a(SR), 10a(SR)-tetraazapyrene determined by X-ray diffraction methods. A semiempirical method of structure solution

The crystal and molecular structure of the title compound hexamethyl-perhy-drotetraazapyrene (I) has been determined by X-ray diffraction methods. The compound crystallizes in the triclinic system, space groupP¯1, with cell dimensionsa=7.715(1),b=10.580(2),c=11.926(2) Å, and=94.37(1)°,=104.87(1)°, and =107.27(1)°. Since the usual direct methods failed, the structure was solved by a semiempirical optimization of packing a model ofI in the unit cell, in terms of the van der Waals' intermolecular energy. The atomic parameters at the most energetically favored position were then refined by least squares against 2396 observed unique reflections, giving a finalR of 0.067. The semiempirical solution used here seems to be limited to particular cases. The molecule ofI consists of two fused piperazine and two fused hexahydropyrimidine rings, having slightly distorted chair conformations. The rings form a foldedcis-10b,10c system of almost exactC ₂ point group symmetry. The lone methyl groups in positions 3 and 8 (at the folding) are found to be axially attached. The geminal methyl groups in positions 1 and 6 are situated away from the folding.     

Crystal and molecular structure of 2,6-di (o-chloro)phenyl-3,5-dimethyl-N-nitrosopiperidin-4-one(NOCDMPO)

The title compound (C₁₉H₁₈O₂N₂Cl₂) crystallized in the monoclinic space groupP2₁/n witha=13.062(2),b=10.931(2),c=13.120(2)Å, and=104.57(1)°. The structure was solved by direct methods and refined toR=0.047 for 2776 reflections. The piperidine ring assumes a distorted boat conformation. The angle between phenyl rings is 78.98(7)°. The nitroso group is oriented by 138.22(7)° to the best plane of the piperidine ring. The interaction between the molecules are van der Waals in nature.DCB Contribution No. 814.