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.     

Crystal structure and spectroscopic study of 4-(N-acetyl) cysteinyl-6,7-dimethoxy-2,2-dimethyl-3-hydroxybenzo-1H-pyran,a potential metabolite of glutathione conjugation of precocene II 3,4-epoxide

The X-ray crystal structure of the title compound has been determined. The crystals are monoclinic:P2₁/a, a=9.804(7),b=20.544(4),c=13.288(3) Å,=105.94(4)°,V _c=2561.9 ų,Z=4,D _x=1.39Mg m^–3, (MoK)=0.71069 Å. The structure was solved by direct methods and refined with 2147 reflections to a finalR value of 0.072. The 1h-pyran ring departs from ideal symmetry towards a half-chair conformation. Mass, IR, and¹H NMR spectra are also reported.     

Structures of 355-1355-1355-1tricarbonyl: structural evidence for the near-electroneutrality of the dialkylacetal substituent

The structures of the (benzene dialkylacetal)tricarbonyl chromium complexes [⁶-C₆H₅-CH(OR)₂]Cr(CO)₆ (R=Me,1; Et,2), are reported. The compounds were examined as part of a study of the conformations of the tripodal tricarbonylchromium group. For [⁶-C₆H₅-CH(OMe)₂]Cr(CO)₃,1, monoclinic,P2₁/c (# 14),a=15.235(1) Å,b=6.5304(5) Å,c=12.702 Å, =103.197(1)^o,Z=4. For [⁶-C₆H₅-CH(OEt)₂]Cr(CO)₃,2, monoclinic,P2₁/c (# 14),a=9.859(3) Å,b=10.547(3) Å,c=15.138(3) Å, =108.42(2)^o,Z=4. The data show that the molecules adopt the expected three-legged piano stool structure. The carbonyl ligands in1 adopt an eclipsed arrangement with respect to the arene ring and its substituent, while those in2 are staggered. These conformations are consistent with the notion that the acetal substituent behaves largely as an electroneutral group, or at most as a weak electronic acceptor.     

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.     

Structure of 4-thioethyl-4-cholesten-3-one,C29H48OS

The crystal structure of 4-thioethyl-4-cholesten-3-one, C₂₉H₄₈OS, has been determined by X-ray methods. The compound is orthorhombic:P2₁2₁2₁,a=7.787(2),b=12.586(4),c=27.960(6) Å,V=2740(3) ų,M _r =444.8,Z=4,D _x =1.08 Mg m^–3, CuK radiation (=1.5418 Å),=11.2 cm^–1,F(000)=984. FinalR=0.073 andR _w =0.057 for 1562 reflections. A comparison with other 4-substituted 4-en-3-ore steroids suggests that theA ring conformation and its relative orientation can be influenced by the thioethyl substituent. The C4 side chain is turned under the steroid skeleton. The cholesterol side chain is fully extended, with atrans, +gauche conformation of the terminal C26 and C27 methyl groups.     

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.     

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 and molecular structure of tris-(O-isopropylxanthato)-chromium(III)

The title compound has been synthesized by the reaction of CrCl₃6H₂O with K{S₂COCH(CH₃)₂} in a 13 molar ratio in an aqueous medium. It has been characterized by elemental analysis and IR spectral studies. Crystals of Cr{S₂COCH(CH₃)₂}₃ are monoclinic, space group P2₁/n witha=10.002(2),b=10.973(1),c=18.961(6) Å,=91.78(2)°,V=2079.9 ų,Z=4,D _calc=1.46 g cm^–3, monochromatic radiation (Mo-K), =0.71069 Å,=11.2 cm^–1,F(0 0 0)=948,T=295K, finalR=0.0320 for 2641 reflections. The environment of the chromium atom is based on an octahedral geometry having six sulfur donor atoms from three symmetrically chelated ligands with average distances: Cr-S=2.396(9) Å, C-S=1.690(3) Å and C-O=1.315(3) Å. The bond distance between oxygen atom and the carbon atom of the isopropyl group (O-C_av=1.478(4) Å) suggests that the form –S ₂ ^(–) C=O⁽⁺⁾CH(CH₃)₂ contributes significantly to the structure of the isopropyl group.     

Crystal and molecular structure of [CpRu(PPh3)2(t-C4H9SH)]BF4

The structure of the [CpRu(PPh₃)₂(t-C₄H₉SH)]BF₄ complex was determined by X-ray diffraction techniques: monoclinic space groupP2₁/c,a=14.662(9),b=18.515(7),c=15.368(6)Å,=101.88(5)°,V=4082(6)ų,Z=4,R=0.049,R _w=0.057. The Ru is attached to two triphenylphosphine ligands, a cyclopentadienyl and thet-butylmercaptan. The Ru-S distance is 2.396(2)Å and the S-H distance is 1.289(2)Å.     

Crystal and molecular structure of 12(S)-acetoxy-4(S),8(R)-dimethyl-3-oxo-1(R)-5(S)-9(S)-2-oxatricyclo[4.4.7.01,9.3.4.8.01,5]tridecane

The structure of the title compound, a cyclic ether acetate lactone, has been established uniquely by X-ray crystallography. C₁₆H₂₄O₄ is orthorhombic, space groupP2₁2₁2₁, with the cell dimensionsa=7.524(2),b=10.686(2),c=19.472(2) Å,V=1565.6(4) ų,Z=4,M _r=280.4,D _x=1.19 g cm^–3,D _o=1.20 g cm^–3,F(000)=608,T=293 K, finalR=0.050. The two cyclohexane ring junction iscis while the lactone ring junction istrans. Both the cyclohexane rings have the chair conformation and the -lactone ring has an envelope conformation with C(7) being at the tip of the flap. The acetoxy side chain is-equatorial. There is an intramolecular C-H---O interaction C(4)O(4)=2.666(4) Å.N. C. L. Communication No. 5064.     

Structure of 9-oxa-2,3-(4′-methoxy)-benzo bicyclo[4,3,0]non-1(6)-ene-7,8-dione: C13H10O4

The crystal and molecular structure of the title compound: C₁₃H₁₀O₄,M _r=230.22, determined by single crystal X-ray diffraction is reported. Crystals are monoclinic, space groupP2_l/c,a=3.991(3),b=21.381(4),c=12.289(4)Å,b=91.15(1)°,V=1048(1)Å₃,z=4,D _x=1.46Mg m^–3, (MoK)=0.7107 Å,m=0.87 mm^–1,F(000)=480,T=298 K. The structure was solved by direct methods and the finalR value is 0.071 (wR=0.055) for 795 independent observed reflections. The cyclohexadienic moiety of the molecule adopt a twist conformation.     

Crystal structures of anhydro-bases of 1- and 2-(ethoxycarbonylmethylo)-4-hydroxycinnolinium hydroxides

C₁₂H₁₂N₂O₃,M _r=232.24. (1): C2/c,Z=8,a=14.658(1),b=4.9375(4),c=31.859(4) Å, =91.710(6)°. (2): P2₁/c,Z=4,a=11.422(2),b=4.8864(2),c=21.176(3)Å, =103.29(3)°. The study confirms significant contribution of quinoid diazine ring form in anhydrobase of 1-substituted 4-hydroxycinnolinium hydroxides. The phenomenon corresponds with a negative net charge at formerly positively charged N(1) atom, with fewer hydrogen contacts of less negatively charged O(4) and with increased stacking in 1-substituted derivative, in comparison with 2-substituted structure.     

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.     

Synthesis and structure of bisiodobis(diisopropyldithiocarbamato)tellurium(IV)

The title mixed ligand complex was synthesized by the controlled oxidative displacement reaction of TeL ₄ by iodine (L is diisopropyldithiocarbamate ion). Its crystals are monoclinic, space group P2₁ withZ=2 in a unit cell of dimensionsa=8.344(4),b=14.113(8),c=10.647(5) Å,=99.884(2)°, andV=1235.15 ų, finalR=0.043 andR _w =0.047 for 3553 unique reflections. The central tellurium atom shows a S₄I₂ six coordination with the two dithiocarbamate groups almost isobidentate, the average Te-S and the Te-I distances being 2.571(3) and 3.011(1) Å, respectively. The structure is monomeric in the solid state. No intermolecular short contacts are observed.     

Structural and spectroscopic properties of the 1∶1 complex of Δ2, 2′-bis-1,3-dithiole (TTF) and 1,2,4,5-tetracyanobenzene (TCNB)

{2,2-bis-1,3-dithiole-1,2,4,5-tetracyanobenzene}, (TTF-TCNB), C₆H₄S₄-C₁₀H₂N₄,M=382.3, monoclinic,P2₁/a,a=9.194(3),b=12.342(3),c=7.426(2) Å,=95.12(3)°,Z=2,D _x =1.52 Mg m^–3, (MoK)=0.71069 Å,=0.51 mm^–1,F(000)=776,T=293 K, finalR=0.039 for 1480 unique observed [F _o >4(F _o ² )] reflections. The complex represents a member of the series of crystal structures of molecular complexes containing TTF as an electron donor and TCNB as an electron acceptor. The structure was solved by direct methods and has been refined by full matrix least-squares calculations. The constituent molecules are stacked alternatively in infinite columns along thec axis. The mean separation of the molecular planes, which are inclined at the angle of 4.4°, is 3.48 Å. There are no unusually short intermolecular contacts. Bond lengths and angles in the component molecules agree with values for neutral species; also the infrared and Raman spectra indicate a very slight degree of ionicity.     

Crystal structure and spectroscopic study of methyl (Z)-6-anilino-4-cyano-2,3-dimethoxy-6-azapentafulvene-1-carboxylate

The molecular and crystal structures of the title compound have been determined. The crystals are monoclinic: C2/c (15),a=21.787(7),b=7.025(6),c=20.165(8) Å,=96.03(2)°,V _c =3069 ų,Z=8,D _x=1.36 mg m^–3, =(Mo K)=0.71069 Å. The structure was solved by direct methods and refined with 1484 reflections to a finalR value of 0.057. Mass and spectral data (ir, uv,¹H and¹³C nmr) are also reported. The structure appears to be polyolefinic having two independent push-pull systems on the fulvenic ring.     

Synthesis and structure of tris(N-methylaminoethanoldithiocarbamato)arsenic(III)

The title compound was synthesized by the interaction of arsenic(III)chloride with freshly prepared N-methylaminoethanoldithiocarbamic acid in methanol. The compound crystallized in the triclinic system, space groupP with two molecules per unit cell, the dimensions area=6.509(10)Å,b=14.077(3)Å,c=14.195(3)Å, =64.16(2)^o, =84.67(2)^o and =84.00(2)^o. The molecule is monomeric with three short (mean 2.320(3)Å) and three long (mean 2.927(2)Å) As-S bonds. Asymmetry in the As-S bonds is due to the presence of stereochemically active lone pair on arsenic and the coordination polyhedron deviates from the usual D₃ symmetry to C₃ symmetry. Disorder exists in one of the dithiocarbamate ligands probably due to the O...O interaction arising from the water molecule. The anisobidenticity of the As-S bond distances is as a consequence of stereochemical requirement of the ligand and the lone pair of electrons on arsenic.     

Syntheses and structures of N-phenylmaleimidetriazoles and by-products

The syntheses, properties, and structures of N-phenylmaleimidetriazole derivatives are described. Intermediates and by-products are also discussed. 1b. a = 43.997(7) Å, 5.7610(9) Å, 8.245(1) Å, = 99.339(4), C₂/c; 2a. a = 13.646(4) Å, b = 7.744(2) Å, c = 10.612(3) Å, = 91.979(6), P2₁/c. 3a. a = 22.245(1) Å, b = 22.245(1) Å, 10.010(1) Å, P42/n. 3a. a = 11.727(2) Å, b = 14.075(3) Å, c = 16.080(3) Å, = 105.859(3), = 105.331(3), = 98.187(3), P-1. 3b. a = 8.561(3) Å, b = 14.755(5) Å, c = 22.771(7) Å, = 97.006(5), P2₁/c. 3c. a = 10.500(2) Å, b = 12.189(2) Å, c = 13.040(2) Å, = 109.091(3), = 106.089(3), = 101.022(3), P-1. 8a. a = 16.389(8) Å, b = 5.749(3) Å, c = 19.316(3) Å, = 97.467(9), P2₁/n. 8b. a = 5.822(2) Å, b = 10.114(3) Å, c = 16.705(4) Å, = 84.681(5), = 82.840(5), = 75.769(4), P-1. 9b. a = 11.251(1) Å, 13.335(3) Å, 13.376(3) Å, = 102.456(4), P2₁/n. 9c. a = 15.836(3) Å, b = 8.236(2) Å, c = 5.447(3) Å, = 92.551(3), P2₁/c. 10a. a = 13.177(2) Å, b = 14.597(2) Å, c = 5.5505(8) Å, = 110.979(2), Cc. 11a. a = 14.720(2) Å, b = 13.995(2) Å, c = 38.245(6) Å, = 94.430(3), P2₁/n. 12b. a = 15.067(5) Å, b = 20.378(6) Å, c = 8.669(5) Å, = 99.16(4), = 99.32(3), = 105.23(3), P-1. 13b. a = 8.2824(6) Å, b = 10.5245(7) Å, c = 15.518(1) Å, = 92.305(1), = 100.473(1), = 100.124(1), P-1. 15a. a = 15.357(3) Å, b = 7.778(2) Å, c = 22.957(2) Å, Pbca. 16b. a = 18.0384(4) Å, b = 12.474(3) Å, c = 20.078(5) Å, Pbca.     

The crystal and molecule structure of tetraphenylphthalic anhydride,C32H20O3

Tetraphenylphthalic anhydride has been structurally characterized by X-ray crystallography: triclinic,P¯1,a=13.386(4),b=13.563(4),c=16.185(6) Å,=71.70(3),=109.32(3), =116.17(3)°,V=2439(1) ų,Z=4,D _x=1.23 g cm^–3,=0.73 cm^–1,T=295 K, andR=0.065 for 3910 observed reflections. The asymmetric unit consists of two crystallographically independent molecules of tetraphenylphthalic anhydride (TPPA). Crowding from four adjacent phenyl substituents produces large average displacements of the substituents from the central ring (av. ~0.08 Å, max. 0.17 Å) and distortions in the central aromatic ring. The torsion angles relating the plane of the substituent phenyl rings to the central ring plane (av. 62°) is consistent with other polyphenylated aromatic structures.     

The crystal structure of tris(4-methylpyridine) tricarbonylmolybdenum(0)

The title compound, Mo(4-CH₃C₅H₄N)₃(CO)₃, is monoclinic, P2₁/c, with cell dimensionsa=10.385(1),b=13.572(2),c=15.522(2) Å, =105.08(1)°,Z=4. The complex isfac-octahedral with approximate three-fold symmetry. The Mo–C bond lengths are 1.901–1.904(7) Å, distinctly shorter than in the parent Mo(CO)₆, and the Mo–N bond lengths are 2.297–2.331(5) Å.