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.     

2-(1-Methyl-1H-indol-3-ylmethylene)-1-aza-bicyclo[2.2.2] octan-3-one: Acid-catalyzed isomerization of the Z isomer to the E isomer

Crystals of (Z)-2-(1-methyl-1H-indol-3-ylmethylene)-1-aza-bicyclo[2.2.2]octan-3-one (I) were obtained from a condensation reaction of 1-methyl-1H-indole-3-carboxaldehyde with 1-aza-bicyclo[2.2.2]octan-3-one and subsequent crystallization of the product from methanol. The isomeric (E)-2-(1-methyl-1H-indol-3-ylmethylene)-1-aza-bicyclo[2.2.2] octan-3-one hydrochloride (II) was obtained by treating a methanolic solution of I with a 1M solution of hydrogen chloride diethyl ether, followed by crystallization of resultant product from methanol. Crystal data: I, is monoclinic, P2₁, a = 5.7440(10), b = 11.102(2), c = 10.708(2) Å, = 91.751(10)°, and V = 682.5(2) ų with Z = 2, for D _cal= 1.296 mg/m³ and II, is monoclinic, P2₁/c, a = 8.8510(2), b = 17.4990(5), c = 20.4300(5) Å, = 101.3620(12)°, V = 3102.26(14) with Z = 8, for D _cal= 1.316 mg/m³.     

X-ray crystal structures ofcis-bis(diphenylphosphinamide)tetracarbonylmolybdenum(0) andtrans-bis(N-methyl diphenylphosphinamide)tetracarbonylmolybdenum(0)

The X-ray crystal structures ofcis-Mo(CO)₄(Ph₂PNH₂)₂,I, andtrans-Mo(CO)₄(Ph₂PNHMe)₂,II, are presented. ComplexI crystallizes in the monoclinic space groupP2₁/c(a=13.433(1),b=12.2719(8),c=17.318(2)Å;=109.79(1)°;V=2686.1(8)ų;Z=4). ComplexII crystallizes in the triclinic space groupP¯1 (a=6.9986(8),b=10.328(1),c=11.241(2)Å,=107.58(1)°,=91.76(1)°, =101.28(1)°,V=756.1(4)ų,Z=1). The molybdenum coordination geometry in each complex is a slightly distorted octahedron. The molybdenum-carbon bond lengths for the carbonyls trans to phosphorus in complexI are shorter than those the carbonyls trans to other carbonyls. The average molybdenum-phosphorus distance inI (2.525(5)Å) is similar to those in other diphenylphosphinamide complexes and longer than the molybdenum-phosphorus distance inII in 2.4585(7)Å). The distance between two nitrogen atoms incis Mo(CO)₄(Ph₂PNH₂)₂ (3.74(3)Å) is significantly larger than the sum of their van der Waals radii (3.10 Å) indicating that the two nitrogens are not hydrogen bonded.     

The crystal and molecular structures of 2-hydroxy-1-naphthalenecarboxaldehyde and 3-hydroxy-2-naphthalenecarboxaldehyde

The crystal and molecular structures of 2-Hydroxy-1-naphthalenecarboxaldehyde (I) and 3-Hydroxy-2-naphthalenecarboxaldehyde (II) were determined. Compound (I) crystallizes in the space groupP2 ₁/n witha+5.589(2),b+9.352(2), andc+15.490(3) Å, =98.14(3)°, andZ+4. Compound (II) crystallizes inP2 ₁/n witha+16.831(11),b+5.936(3), andc+8.295(3) Å =97.24(5)°. andZ+4. The structures were solved by direct methods, and refined by fullmatrix least squares toR+0.071 andR _w+0.083 forI, andR+0.047 andR _w+0.061 forII.     

The structural and spectroscopic properties of 2,4,6-trinitro-diphenylamine and 2,4,6-trinitro-N-methyl-diphenylamine

The structural properties of 2,4,6-trinitro-diphenylamine (I) and 2,4,6-trinitro-N-methyl-diphenylamine (II) are determined by single crystal diffractometry and refined toR factors of 0.0282 for (I) and 0.04213 for (II). (I) crystallizes in the monoclinic space groupP2₁/n,Z=4, witha=11.436(5),b=7.674(2),c=15.083(4) Å,=106.47(2)°, and (II) inP2₁/c,Z=4, witha=12.654(5),b=7.371(1),c=15.083(4) Å,=101.76(2)°. The amino nitrogens show in both cases bond distances and angles typical of an sp² character. The presence of the proton on the amino nitrogen constrains ano-nitro group into a more planar geometry than that of the methyl derivative, uv/visible spectral data of both compounds are discussed. The methyl group on the amino nitrogen, of derivative (II) compared with that of (I) produces a relevant red shift which cannot be related to the simple differences in the geometry of the two molecules.     

X-ray crystallographic determination of the structure and conformation of 1,4,4-trimethyltricyclo[5.4.0.03,5]-undec-7-en-9-one and 1,4,4,8-tetramethyltricyclo[5.4.0.03,5]-undec-T-en-9-one

The crystal structure and conformation of 1,4,4-trimethyltricyclo[5.4.0.0^3,5]undec-7-en-9-one (I) and 1,4,4,8-tetramethyltricyclo[5.4.0.0^3,5]undec-7-en-9-one (II) have been determined by X-ray diffraction. In both cases the crystals are orthorhombic, P2₁2₁2₁,a=6.194 (2) (I); 7.499 (2) (II),b=7.486 (3) (I); 12.855 (3) (II),c=26.283 (7) (I); 13.928 (4) (II) Å,Z=4. The structure was solved by direct methods, and refined to anR value of 0.048 for 1534 (I) and 0.054 for 1357 (II) withI>3.0 (I). In both compounds substituted by carbonyl group ring has the distorted³E sofa conformation whereas the second one possesses the slightly deformed^7.10B boat conformation.The nomenclature of IUPAC for the name of compounds in the title is applied. However, for simplicity the numbering of the atoms in the paper follow Fig. 1a and 1b.     

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.     

Synthesis and structural characterization of bismuth complexes with sulphur-containing ligands: The crystal and molecular structures of two derivatives of BiBr3 and Bi2(SO4)3 with imidazolidine-2-thione

The paper reports the structural and spectroscopic properties of two complexes between BiBr₃, Bi₂(SO₄)₃ and imidazolidine-2-thione (etu) having formulae BiBr₃·3etu (I) and [Bi(etu)₄]₂(SO₄)₃·2H₂O (II). ComplexI is monoclinic, space groupP2₁/n,Z=4, witha=8.142(2),b=15.611(3),c=16.316(3) Å,=97.38(3)°,R=0.041.II is orthorhombic, space groupPbcn,a=10.930(1),b=16.795(1),c=27.890(1) Å,Z=4 andR=0.052. In both structures bismuth is octahedrally coordinated, inI three bromines and three sulphurs from etu molecules are present and the coordinated polyhedron is only moderately deformed, while inII four sulphurs of etu ligands and two oxygen sulphate with very different Bi-O distances [2.413(12) and 2.715(13) Å] are present.     

Synthesis and structural characterization of 5,6,15,16-tetradehydrobenzo[a]phenanthro[9, 10-e]cyclooctene,C24H12

A benzo-phenanthro-fused planar cyclooctatetraene derivative, namely, 5,6,15,16-tetradehydrobenzo[a]phenanthro[9, 10-e]cyclooctene (5) was synthesized in two steps from the known benzo[a]phenanthro[9, 10-e]cyclooctene (6). Compound5 crystallizes in space groupPbam witha=9.828(2),b=19.466(4),c=15.901(3) Å, and Z=8. X-Ray analysis (MoK radiation,R=0.060 for 1233 observed data) has shown that both independent molecules have the same planarC _2v configuration with averaged bond lengths of 1.381(7) and 1.208(7) Å for the phenanthrene C_6a–C_14b bond and the acetylenic CC bond, respectively.¹H and¹³C NMR spectral results of 5 and 5,6,15,16-tetrabromo-5,6,15,16-tetrahydrobenzo[a]phenanthro[9, 10-e]cyclooctene (7) are also presented.     

Structures of three halo(tetramethylethylenediamine)copper(I) complexes

The X-ray crystal structures of three halo(tetramethylethylenediamine)copper(I) complexes have been determined. (TMED)₂Cu⁺CuCl ₂ ^– (I) crystallizes in monoclinic space groupP2₁/n with lattice constantsa=9.332(9),b=15.126(7),c=14.49(1) Å,=96.95(7)°. (TMEDCuBr)₂ (II) crystallizes in monoclinic space groupP2₁/c with lattice constantsa=12.064(5),b=11.888(6),c=15.841(6) Å,=113.97(3)°. (TMED CuI)₂ (III) crystallizes in monoclinic space groupP2₁/c with lattice constantsa=12.401(6),b=12.159(6),c=15.412(9) Å,=109.12(4)°. Compound (I) is a molecule exhibiting two discrete environments for copper(I). The cation is a pseudotetrahedral monomer and the anion a linear monomer. Both (II) and (III) are dimers with asymmetrically bridging bromine and iodine atoms, respectively. Distortions from tetrahedral geometry are observed about the copper atoms in (II) and (III).     

The crystal and molecular structure of 6,8,15,16b,16c,17-hexahydro-16b,16c-diphenyl-7H,16H-6a,7a,15a,16a-tetraazanaphtho[5,6]azulano[2,1,8-ij]naptho[f]azulene-7,16-dione

The crystal and molecular structure of a clip containing molecule is described. The structure was solved by vector search methods and refined by least squares methods toR _l=0.0768 [I>2(I)]. Crystal data: C₄₀H₃₀N₄O₂·HCCl₃, triclinic, space group ,a=9.302(2),b=12.981(2),c=15.765(2)Å, =65.91(2)°, =76.40(2)°, =80.15(1)°,V=1682.9(4)ų, Z=2.     

Structural studies of some o-substituted S-phenyl thiobenzoates. I. Crystal structure of S-phenyl o-chlorothiobenzoate and S-phenyl o-bromothiobenzoate

Structural characteristics ofS-phenylo-chlorothiobenzoate (I) andS-phenylo-bromothiobenzoate (II) have been investigated by single crystal X-ray diffraction. It was shown that the crystals are isomorphous and crystallize in the monoclinic space groupP2₁ withZ=2. The unit cell parameters are:a=10.150(3),b=7.672(2),c=7.595(2) Å,=91.28(1)° for C₁₃H₉ClOS (compoundI) anda=10.141(3),b=7.764(2),c=7.653(2) Å,=90.14(3)° for C₁₃H₉BrOS (compoundII). The structures were solved by heavy-atom methods and refined by full-matrix least-squares, from room-temperature data collected with a Philips PW 1100 diifractometer, to conventionalR factors of 0.056 forI and 0.044 forII. The structures consist of independent molecules held together by intermolecular interactions. Molecular packing is influenced by the presence ofo-substituted Cl or Br atoms. The Cl atoms in structureI as well as the Br ones in structureII are directed to the centers of the pi-electronic system of theo-substituted phenyl rings belonging to the neighboring molecules. The six ClC and BrC distances range from 3.651(10) to 3.869(9) Å and from 3.644(6) to 3.890(6) Å, respectively. The C1 (or Br) atom is additionally directed towards the two carbon atoms (C3 and C4) in anothero-substituted phenyl ring, the C1lC and BrC distances being 3.786(9) and 3.849(10) Å inI and 3.727(6) and 3.881(6) Å inII. The torsion angle C6-C7-S-C8 is-170.2(7)° inI and 168.6(4)° inII. The angles between the planar O-C7-S central fragment of the molecule, on the one hand, and theo-substituted phenyl ring, on the other, are 113.9(3)° in I and 110.9(2)° inII. The corresponding values for the angles between the O-C7-S fragment and the nonsubstituted phenyl ring are 115.8(3)° and 114.3(2)° in compoundsI andII, respectively.     

Synthesis and molecular structure of [Al(CH3)2]2[C10H22N4] [Al(CH3)3]2: Condensation product of trimethylaluminum and a multidentate open-chain amine

The crystalline condensation product [Al(CH₃)₂]₂[C₁₀H₂₂N₄][Al(CH₃)₃]₂ is prepared from reaction of the multidentate open-chain amine 1,4-bis(3-aminopropyl)piperazine with trimethylaluminum in methylene chloride. The compound crystallized in the monoclinic space groupC2/c with unit cell parametersa=25.166(12),b=7.268(4),c=17.316(4) Å,=115.3(4)°, andD _c =1.06 g cm^–3 forZ=4. Least-squares refinement based on 1054 observed reflections with intensitiesI 3(I) in the range 2<2<45° led to a finalR factor of 0.053 (R _w =0.064). The title compound resides on a crystallographic center of symmetry with independent Al-N distances of 1.889(5), 2.058(5), and 2.030(5) Å.     

X-ray structures of two methoxybenzo[b]thiophenes

The crystal and molecular structures of two methoxybenzo[b]thiophenes have been determined by three-dimensional, single-crystal X-ray diffractometry. Both 3-(4-hydroxy-3, 5-dimethoxybenzoyl)-2-(4-methoxyphenyl)-6-methoxybenzo[b]thiophene and 3-(2,6-dimethoxybenzoyl)-2-(4-methoxyphenyl)-6-methoxybenzo[b]thiophene (hereafter referred to asI andII, respectively) crystallize in the monoclinic centrosymmetric space groupP2₁/n (No. 14, C _2h ⁵ ) with four formula units-per cell witha=6.866(1),b=28.638(2),c=11.830(2) Å, and =105.52(1)° anda=9.328(1),b=7.977(1),c=29.650(4) Å, and =97.87(1)°, respectively. The phase problems were solved by direct methods and the respective final full-matrix least-squares refinements converged toR=0.046 and 0.031. The structures differ in the positioning of the dimethoxy groups of the benzoyl ligands and the addition of a hydroxyl group inI. The molecules in the crystal lattice are held together by van der Waals forces plus the addition of hydrogen bonding in compoundI. Selected bond distances and angles and torsion angles are tabularized.     

The synthesis and structure of 1,2,3,4-tetrahydro-2,4,4-trimethyl-8-nitroimidazo[1,5-d] [1,2,4]triazin-1-one,C8H11N5O3: A heterocycle with a rare ring system

The title compound (IV) was isolated as a by-product during the course of purification of 4-nitroimidazol-5-(N-methyl)hydrazide (II) by silica gel flash chromatography, employing chloroform-acetone (4:1) as the eluting solvent. The crystals are monoclinic, space groupP2₁/c,a=7.425(1),b=13.615(2),c=10.359(2) Å,=97.66(1)°,d _caled=1.44 g cm^–3, (MoK)=1.06 mm^–1,T=298 K. The number of unique reflections=2401, reflections withI3 (I)=1773;R=0.051,R _w =0.061. The bond distances inIV are: N-N, 1.419(3); N-C(=0), 1.359(3); N(H)-C(CH₃), 1.457(3); N(C)-C(CH₃), 1.501(3); N=C, 1.316(3); C=C, 1.368(3), N-C(=N), 1.353(3); N-C(=C), 1.367(2) Å.     

Crystal and molecular structures of 1-phenyl-4,6-dimethylpyrimidine-2-thionetetraaquacobalt(II) dinitrate complex and of two pyrimidine thiones

The crystal structures of 1-phenyl-4,6-dimethylpyrimidine-2-thionetetraaquacobalt(II) dinitrate (I)a=9.032(2),b=12.458(2),c=18.067(3)Å,=103.25(3)°,Z=4;P2₁/c,R=0.049; 1-phenyl-4,6-dimethylpyrimidine-2-thione (II)a=12.005(3),b=10.090(2),c=9.649(2)Å,=104.4(1)°,Z=4;P2₁/n,R=0.038; and 4,6-dimethylpyrimidine-2-thione (III)a=15.485(3),b=13.255(3),c=7.127(2)Å,=104.3(1)°,Z=8,C2/c,R=0.041 are reported. In (I) the coordination around the cobalt(II) is distorted octahedral involving one ligand moleculevia sulphur and nitrogen atoms and four water molecules. It is relevant that the parameters in the complexed ligand are not different from those found in the uncomplexed one (II), excepting the distances on the nitrogen atom directly involved in the coordination. Bond distances and angles in compound (III) agree with those found in (II).     

Crystal and molecular structures oftrans-dichloro-(ethylene) (4-methylpyridine)platinum(II) andtrans-dichloro(ethylene) (2,4,6-trimethylpyridine)platinum(II)

The crystal and molecular structures oftrans-[PtCl₂(C₂H₄)(4-MeC₅H₄N)] (I) andtrans-[PtCl₂(C₂H₄)(2,4,6-Me₃C₅H₂N)] (II) have been determined by single-crystal x-ray methods.I crystallizes in space groupP2₁/c witha= 4.991(1), b=21.658(3), c=10.675(3) Å, =110.17(2) °,Z=4;II is orthorhombic (Pbca) witha=10.295(6),b=12.393(8),c=20.370(10) Å,Z=8.Full-matrix least-squares refinements have given finalR factors of 0.053 (1520 reflections) forI and 0.042. (1412 reflections) forII. The intensities were recorded by counter methods, and only those reflections havingI>3(I) were used in the analyses.In both complexes, platinum is four-coordinate with the two chlorine atoms, the double bond of the ethylene, and the nitrogen atom of the substituted pyridine. The two structures are discussed in terms of the arrangement of the pyridine ligand with respect to the PtCl₂(C₂H₄) moiety.     

Crystal structures of difluoro[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]boron(III), [BF2(C16H13O3)], and bis[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]copper(II), [Cu(C16H13O3)2]

The crystal structures of difluoro[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]boron(III), [BF₂(C₁₆H₁₃O₃)], and bis[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]copper(II), [Cu(C₁₆H₁₃O₃)₂], have been determined by single-crystal X-ray diffraction methods. The structures were solved by direct methods and electron density calculations and were refined by the full-matrix least-squares method. Difluoro[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]-boron(III) crystallizes as yellow rhombs in the monoclinic space groupP2₁/c witha=11.429(3),b=11.364(4),c=11.412(4) Å,=92.19(2)°,V=1481.0(8) ų andZ=4. A total of 2754 unique reflections were collected. Of these 1342 were considered observed [I>3(I)] leading to a finalR-value of 0.045. Boron is tetrahedrally coordinated to the two fluorine atoms and to two oxygen atoms of the bidentate 2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato ligand, C₁₆H₁₃O ₃ ^– . Average bond distances: C-C (aromatic) 1.378(10) Å, B-O 1.473(7) Å and B-F 1.343(4) Å. bis[2-(4-Methoxyphenyl)-3-oxo-3-phenylpropanalato]copper(II) crystallizes as dark yellow-green plates in the monoclinic space groupC2/c witha=23.410(7),b=13.856(3),c=8.039(3) Å,=101.79(2)°,V=2553(1) ų andZ=4. Of the unique set of 3076 scanned reflections 2401 hadI>3(I) for whichR became 0.040. Copper is coordinated to four oxygen atoms, two from each of the two bidentate 2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato ligands, in a distorted square planar manner. The molecule hasC ₂ symmetry. Average bond distances: C-C (aromatic) 1.383(6) Å and Cu-O 1.896(8) Å. The crystals of both compounds consist of monomeric molecular complexes held together by van der Waals forces.     

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.     

X-ray structural investigation of N-epimeric 1,8-cis- and 1,8-trans-5,12-dimethyl-1,4,8,11-tetraazacyclotetradeca-4,11-dienenickel(II) diperchlorates,C12H24N4Ni(ClO4)2

The structures of 1,8-cis- and 1,8-trans-5, 12-dimethyl-1,4,8,11-tetra-azacyclotetradeca-4,11-dienenickel(II) diperchlorates (I andII, respectively) have been investigated by X-ray diffracto-metric methods. CompoundI crystallizes in a monoclinic system, space group P2₁/n, with cell dimensionsa=13.732(2),b=13.526(2),c=10.658(2) Å,=99.20(2)°; compoundII crystallizes in a monoclinic system, space group C2/c, with cell dimensionsa=15.776(2),b=9.919(1),c=12.451(1) Å,=102.27(1)°. The structures were solved by heavy atommethods and refined by a full-matrix least-squares method to giveR=0.0601 and 0.0575 forIandII, respectively. Both N-epimers show the square planar Ni(II) coordination arrangements. The ligand ofI has approximate twofold symmetry (C₂ perpendicular to the coordination plane), the moleculeII is crystallographically centrosymmetric (C_i).