Synthesis and structural characterization of 2,6-bis-(N-methylenemorpholino)-4-ter-butylphenol

The crystal and molecular structure of the title compound, C₂₀H₃₂N₂O₃, has been determined from X-ray diffraction data using CuK radiation (=1.5418 Å). The compound crystallizes in triclinic space groupP1^¯ with a=8.828(1),b=18.680(1),c=6.272(2)Å, =93.42(1), =0.24(2), =77.93(1)°,V=1009.4(2)ų, andZ=2. The structure was solved by direct methods and the full-matrix least-squares refinement leads the finalR-factor to 0.065 for 3481 observed reflections withI3(I). The phenyl ring is planar and the morpholino rings assume perfect chair conformation. The molecules are held together by van der Waals forces.DCB Contribution No. 810.     

Structural characterization of 2,6-bis(N-methylenepiperidino)-4-nitrophenol (MPN) and 2,6-bis-(N-methylenemorpholino)-4-nitrophenol (MMN)3

MPN: C₁₈H₂₇N₃O₃,M _r=333.43, monoclinic,P2₁/n. a=6.207(2),b=21.893(6),c=13.693(3) Å; =96.12(2)^o,V=1850.1(8) ų.,Z=4,D _cal=1.20 mg/m³,F(000)=720, (CuK)=1.5418 Å, andT=298K.R=0.042 andwR=0.049 for 1675 observed reflections. MMN: C₁₆H₂₃N₃O₅,M _r=337.38, triclinic,P,a=9.642(1) Å,b=10.123(5) Å,c=9.341(2) Å, =93.00(3)^o, =90.96(1)^o, =110.46(1)^o, V=852.5(5) ų,D _cal=1.31 mg m^–3.F(000)=360,Z=2, (CuK)=1.5418 Å,R=0.054 andwR=0.074 for 2804 observed reflections. The piperidine and morpholino rings assumechair conformation and orient each other at an angle of 44.8(1)^o (MPN) and 47.1(1)^o (MMN), respectively.Contribution No. 827 from DCB.     

The crystal structure of a cyclodecabis[1,2,3]selenadiazole

4,5,6,10,11,12-hexahydrocyclodeca[1,2-d6,7-d]bis[1,2,3]selenadiazole, C₁₀H₁₂N₄Se₂, crystallizes in triclinic space group P witha=5.4625(3),b=7.2091(4),c=8.3122(6) , =65.313(5), =77.476(5), =77.442(5)°,V=287.35(4) ³,Z=1. The structure was refined toR=0.031 andR _w=0.030 for 2018 observed reflections. The molecule lies on an inversion center. The cyclodecadiene ring adopts an elongated chair conformation. The near-zero torsion angle of the elongated chair lies at the ring-fusion bonds, with a magnitude of 2.9(3)°. The five atoms of the selenadiazole ring exhibit maximum deviation 0.005(2) from planarity, with the adjacent carbon atoms lying respectively 0.020(2) and 0.059(2) to the same side of this plane. The torsion angles about the bonds comprising the sides of the elongated chair vary in magnitude from 61.0(2)° to 55.7(2)°. The cyclodecadiene C=C bond lengths are 1.368(2) . The selenium-carbon bond length is 1.850(2) . The Se–N distance is quite long, 1.888(2) .     

Crystal and molecular structures of tri(o-tolyl)phosphinegold(I) purine-6-thiolate ethanol solvate (1/1) and tri(c-hexyl)phosphinegold(I) 6-methyl-2-thiouracilate

The crystal and molecular structures of the title compounds, [(o-tol)₃PAu(6-MP)]·EtOH and [(c-hexyl)₃PAu(6-Me-2-TU)], have been determined and each show the presence of a linear geometry about the Au atom; both of the thionucleobases function as thiolate ligands. Important interatomic parameters for [(o-tol)₃PAu(6-MP)] are Au–S 2.266(2), Au–P 2.239(2) and S–Au–P 177.03(8)° and for [(c-hexyl)₃PAu(6-Me-2-TU)]: Au–S 2.299(3), Au–P 2.244(3) and S–Au–P 176.1(1)°. Crystals of [(o-tol)₃PAu(6-MP)]·EtOH are monoclinic with space groupP2₁/n, and unit cell dimensionsa=10.067(2),b=10.518(2),c=25.416(4) , =98.42(2)°,Z=4. The structure was refined to finalR=0.040 for 4183 data withI3.0(I). Crystals of [(c-hexyl)₃PAu(6-Me-2-TU)] are monoclinic with space groupP2₁/c, and unit cell dimensionsa=9.692(4),b=15.822(4),c=15.775(3) , =94.00(2)°,Z=4,R=0.033 for 2666 data.     

Antimony(III) fluoride: inclusion complexes with crown ethers

Four crystalline molecular complexes between antimony(III) fluoride and 18-membered crown ethers have been obtained and their structures investigated by single crystal X-ray diffraction techniques: [18-crown-6·SbF₃], C₁₂H₂₄F₃O₆Sb,P2₁2₁2₁,a=8.328(4),b=11.573(4),c=18.094(4),V=1744(1)³,Z=4; [benzo-18-crown-6·SbF₃], C₁₆H₂₄F₃O₆Sb,P2₁/n,a=10.490(2),b=13.714(1),c=13.442(2), =101.94(1)°,V=1892(1)³,Z=4; [cis-syn-cis-dicyclohexano-18-crown-6·SbF₃·CH₃OH], C₂₁H₄₀F₃O₇Sb,P2₁/n,a=8.270(4),b=23.386(3),c=12.772(1), =96.31(2)°,V=2455(1)³,Z=4; [cis-anti-cis-dicyclohexano-18-crown-6·SbF₃], C₂₀H₃₆F₃O₆Sb,Pna2₁,a=21.091(8),b=12.829(5),c=8.437(3),V=2283(2)³,Z=4. All species are the perching-type complexes with the antimony fluoride above the cavity and the metal lone pair pointed toward the center of the crown ring. The antimony atom interacts with all six crown oxygen atoms with Sb–O distances of 2.837(2)–3.344(2) . The antimony atom is displaced from the least square plane of the crown oxygen atoms at the distances of 1.288–1.383 .     

Crystal structure of 14, α-hydroxy,sandarocopimar-7, 15-diene-19-oic acid

C₂₀H₃₀O₃, M _r =318.46, Monoclinic,P2₁,a=12.232(2) ,b=11.491(2) ,c=14.160(3) , =115.2°(3),V=1800.3(7) ³,Z=4,D _x =1.18 Mg m^–3, (CuK)=1.5418 , =5.3 cm^–1,F(000)=696,T=298 K. FinalR=0.044 for 2645 reflections withI>2. The two crystallographically independent molecules in the unit cell adopt essentially similar conformations. The structure reveals atrans relationship between the hydrogen at C(9) and the methyl group at C(20). The stereochemistry at C(13) is S. Apart from van der Waals forces the structure is stabilized by hydrogen bonds.     

Structure of bis(2-pyridine-N-oxide) diselenide and its formation from tetraphenylantimony(V)selenopyridine-N-oxide

The structure of bis(2-pyridine-N-oxide) diselenide was determined by single crystal X-ray diffraction. The compound crystallized in the triclinic system and the structure was solved in the space group . The lattice constants were determined to bea=7.174(2),b=7.176(2),c=11.070(2) , =87.67(2)°, =73.68(2)°, and =89.57(2)°;Z=2,D _x=1.906 Mg m^–3. The final least squares refinement based on 1942 independent observed reflections yieldedR=0.033,wR=0.044. The Se–Se bond length is 2.326(1) and each Se is coordinated to the O atom of the corresponding N-oxide moiety at a distance of about 2.6 .     

Crystal structures of two modifications oftrans-1,3-bis(3,4-dimethoxyphenyl)-2,3-epoxy-1-propanone

trans-1,3-Bis(3,4-dimethoxyphenyl)-2,3-epoxy-1-propanone exhibits dimorphism and crystallizes in a monoclinic form from ethanol and in a trigonal form from chloroform/hexane. The crystal structures of the two modifications were determined by single-crystal X-ray diffraction methods. The monoclinic form crystallizes in space groupP2_t/c with ,b=7.986(1),c=25.223(4) , =94.83(2)°,V=1747.9(6) andZ=4.R=0.052 for 1236 reflections [I>3(I)]. The trigonal form crystallizes in space group witha=36.048(6),c=8.313(5) ,V=9355(6) andZ=18 (hexagonal axes).R=0.101 for 1216 reflections [I>3(I)]. In the trigonal crystals there are channels in thec-direction with a diameter of approximately 10 . Possible explanations for the comparatively highR-value are discussed.     

Reaction of trimethylaluminum and trimethylgallium with bifunctional amines: Syntheses and molecular structures of [Me2Al−N(CH2CH2)2−C−(OCH2)2]2 and [Me2Ga−N(Si(H)Me2)2]2

The crystalline products [Me₂Al–N(CH₂CH₂)₂–C–(OCH₂)₂]₂ (I) and [Me₂Ga–N(Si(H)Me₂)₂]₂ (II) were prepared from reactions of trimethylaluminum and trimethylgallium with 1,4-dioxa-8-azaspiro[4.5]-decane and 1,1,3,3-tetramethyldisilazane, respectively, in toluene. The organoaluminum dimer crystallizes in the monoclinic space groupP2₁/c with unit cell parametersa=8.970(2) ,b=9.683(2) ,c=12.833(3) , =103.18(2)°,V=1085.3(3) ³, andD _calcd=1.22 g cm^–3 forZ=2. Least-squares refinement based on 935 observed reflectionsI>3(I) in the range 3.5°<2<45.0° led to a finalR factor of 0.033 (R _w =0.041). The dimeric organosilazagallium crystallizes in the triclinic space group with unit cell parametersa=7.636(2) ,b=9.168(2) ,c=9.466(3), =72.81(2)°, =87.94(2)°, =69.90(2)°,V=593.0(3) ³, andD _calcd=1.30 g cm^–3 forZ=1. Least-squares refinement based on 1661 observed reflectionsI>3(I) in the range 3.5°<2<48.0° led to a finalR factor of 0.055 (R _w =0.070). Both compoundsI andII reside about a crystallographic center of symmetry and contain a planar M₂N₂ (M=Al forI, Ga forII) four-membered ring withI having an Al...Al contact of 2.801 .     

Synthesis and characterization of ternary L-histidine complexes. Crystal structure of (2,2′-dipyridyl)-(L-histidinato-N,N′,O)copper(II) perchlorate 1.5 hydrate

A series of ternary complexes of copper(II), cobalt(II) and zinc(II) with L-histidine, 1,10-phenanthroline, 2,2-dipyridyl or imidazole having perchlorate or acetate as counterions were synthesized and characterized by conventional methods and for [Cu(bipy)(L-hist)]ClO₄·1.5H₂O and X-ray crystal structure was determined. The crystals belong to the monoclinic space groupC2 witha=18.843(3),b=10.582(2),c=11.020(2), =115.20(10)°,Z=4,R=0.0535. The structure is consistent of [Cu(bipy)(L-hist)]⁺ cations, perchlorate ions and water molecules. The geometry around copper is trigonal bipyramidal with one N,N,O tridentate L-histidine molecule and one 2,2-dipyridyl ligand, the apical sites are occupied by the -amino nitrogen [Cu–N(71) 1.995(8)] and by N(11) of 2,2-dipyridyl [Cu–N(11) 1.983(7)], the equatorial plane is formed by the N(3) imidazole -nitrogen [Cu–N(3) 2.140(6)], O(82) carboxylic oxygen [Cu–O(82) 2.009(5)] and N(22) [Cu–N(22) 2.010(7)].     

Molecular structure of 4-(3,5-dimethylpyrazol-1-yl)benzoic acid trifluoroacetate

The crystal and molecular structure of the title compound has been determined by X-ray analysis. 4-(3,5-Dimethylpyrazol-l-yl)benzoic acid trifluoroacetate crystallizes in the 12/a space group witha=20.6584(13),b=9.9068(3),c=14.9467(6) , =106.195(4),V=2937.6(2) ų, Dc=1.494 g/cm³ andZ=8. The ions pack in chains parallel to thea axis through O–HO and N–HO hydrogen bond interactions. Solid-state¹³C CPMASNMR spectroscopy has been used to compare the structure of the trifluoracetate with that of the neutral molecule [4-(3,5-dimethylpyrazol-l-yl)benzoic acid].     

Molecular structure of [(tBu)2Al(μ-NHtBu)]2

The crystal and molecular structure of [(^tBu)₂Al(-NH^tBu)]₂ has been determined. The unit cell contains two independent molecules with only slight variation in the orientation of thetert-butyl ligands. Crystal data: Triclinic, ,a=9.0138(6),b=10.2944(8),c=15.791(1) , =91.262(6), =89.822(6), =106.141(6)°,V=1407.2(2) ų,Z=2,R=0.039,R _w=0.041.     

Crystal structure of cesium sodium hexathiocyanatobismuthate Cs2Na[Bi(SCN)6] and characterization of Cs2Na[Bi(SCN)6−x Cl x ] and Cs2Na[Bi2(SCN)9−x Cl x ] complexes by X-ray powder diffraction

Cs₂Na[Bi(SCN)₆] crystallizes in the trigonal space group with one formal molecule per unit cell.M=846.25,a=7.189(1),c=10.580(2) ,V=473.5(1) ,D _x =2.967 g cm^–3, (MoK)=13.70 mm^–1,F(000)=378. FinalR=0.029 for 917 absorption-corrected reflections. The structure consists of infinite[Bi(SCN)₆Na] ^2– anionic chains along thec axis with slightly distorted octahedral Bi–6S and Na–6N coordination and Cs⁺ ions surrounded by three anionic chains with irregular coordination by six N and three S atoms. X-ray powder diffractograms of three complexes, Cs₂Na[Bi(SCN)_6–x Cl _x ] withx=2, 3 and 4, indicate that the mixed complexes are not isostructural and can be indexed in different orthorombic unit cells witha=14.617(8),b=12.32(1),c=10.769(6) forx=2;a=15.37(1),b=10.81(1),c=10.287(6) forx=3 anda=14.662(7),b=14.366(7),c=7.932(4) forx=4. The two dinuclear complexes Cs₂Na[Bi₂(SCN)_9–x Cl _x ] withx=2 and 3, despite the large similarity of their diffractograms, are not isostructural and can be indexed in different orthorombic unit cells witha=14.79(1),b=13.72(1),c=10.591(5) forx=2 anda=18.423(8),b=15.657(7),c=7.410(7) forx=3.     

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.     

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.     

Crystal structures of (I) 2-(9,9-dipropylfluorene-2-yl)-9,9- dipropylfluorene and (II) 2-(1,1-dimethylpropyl)-7- {4-[(1,1-dimethylpropyl)-9,9-diethylfluoren-2-yl]phenyl}-9,9-diethylfluorene and (III) 2-(4-ethylphenyl) -7-[7-(ethylphenyl)-9,9-dipropylfluoren-2-yl]-9,9-dipropylfluorene

The crystal structures of the three fluorene related molecules, (I) 2-(9,9-dipropylfluorene-2-yl)-9,9-dipropylfluorene, [Exalite 384, C₃₈H₄₂], (II) 2-(1,1-dimethylpropyl)-7-{4-[(1,1-dimethylpropyl)-9,9-diethylfluoren-2-yl] phenyl}-9,9-diethylfluorene, [Exalite 404, C₅₀ H₅₈], and (III) 2-(4-ethylphenyl)-7-[7-(ethylphenyl)-9,9-dipropylfluoren-2-yl]-9,9-dipropylfluorene, [Exalite 416, C₅₄H₅₈], have been determined. Structural details reveal a novel new bonding arrangement at the C2 atoms of symmetry-related fluorene moieties in all three molecules producing a linear type array with an inversion center connecting adjacent asymmetric units within each molecule. Exalite 384 is monoclinic, space group P2₁/c with a = 9.002(2) Å, b = 16.275(4) Å, c = 10.525(1) Å, = 103.05(1), and V = 1502.1(5) ų with Z = 4, for d _calc = 1.103 g/cm³. Exalite 404 is triclinic, space group P1 with a = 10.383(1) Å, b = 13.404(2) Å, c = 7.7007(9) Å, = 105.296(9), = 104.23(1), = 73.707(9), and V = 974.9(2) ų with Z = 2, for d _calc = 1.141. Exalite 416 is monoclinic, space group P2₁/c with a = 15.99(10) Å, b = 11.178(8) Å, c = 23.766(4) Å, = 104.21(4), and V = 4117(4) ų with Z = 4, for d _calc = 1.141 g/cm³.     

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.     

Polymorphism of N-(2,6-dioxo-3-piperidyl)pthalimide (thalidomide): Structural characterization of a second monoclinic racemic modification

The X-ray crystal structure of the drug N-(2,6-dioxo-3-piperidyl)pthalimide (thalidomide), C₁₃H₁₀N₂O₄, obtained from 11 dimethyformamide-ethanol solution, is reported. This species is monoclinic, space groupC2/c, witha=20.679(5),b=8.042(2),c=14.162(5) , =102.86(3)°,Z=8,R=0.051 for 1674 unique reflections. crystal packing is determined by intermolecular N–H... O hydrogen bonding which is more extensive than that reported in the literature for a racemate of thalidomide crystallizing in space groupP2₁/n. Comparison of the melting behavior and X-ray powder diffractograms of the two racemic polymorphs shows that they are distinctly different, allowing easy identification of these species. By comparing experimental X-ray powder patterns with those calculated from single crystal data, it was concluded that neither of these polymorphs undergoes a phase change on trituration.     

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 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.