Structures of 2-, 3-, and 4-methyl-9-oxothioxanthenes

The structures of 2-, 3-, and 4-methyl-9-oxothioxanthenes (2-, 3-, and 4-TX, respectively) were determined by single crystal x-ray methods. The molecules are folded by 2–3° about their SC=O lines. Bond distances and angles vary only slightly as a function of the methyl substitution position, and reveal no inherent structural reason for the long-range nmr couplings observed between the ring and methyl protons. The molecular packings exhibit interesting similarities as well as subtle differences that result from variation of the methyl position. Crystals of 2-TX are orthorhombic, space groupPn2₁ a,a=10.807(1),b=4.024(2),c=24.827(3) Å,Z=4,R=0.059 for 715 observed reflections. Crystals of 3-TX are orthorhombic, space groupPbc2₁,a=3.999(1),b=25.051(2),c=10.758(1)Å,Z=4,R=0.041 for 1382 observed reflections. Crystals of 4-TX are triclinic, space groupP¯1,a=7.118(1),b=7.907(2),c=10.415(2) Å,=77.74(1),=74.35(1), =73.96(1)°,Z=2,R=0.043 for 1542 observed reflections.Deceased.     

Crystal structures of 4-amino-1,2,4-triazolidine-3,5-dione (urazine) (C2H4N4O2) and dichlorobis (4-amino-1,2,4-triazolidine-3,5-dione-N,O) copper (II) (C4H8Cl2CuN8O4)

Crystal structure analyses of urazine and of its adduct with CuCl₂ show that this ligand can exchange interactions of stacking that cannot be defined as simple - interactions. The copper atoms are octahedrally coordinated by two oxygen atoms and two aminic nitrogen from chelating uraxines and two chlorine atoms. The crystals of urazine are monoclinicP2₁ c:a=6.741(1),b=5.815(1),c=11.141(2) Å,/gb=92.13(1)°,V _c=436.4(1) ų,Z=4,R=0.0402 for 714 independent observed reflections; the crystals of [CuCl₂(urazine)₂] are triclinicP¯1:a=5.236(1),b=6.662(1),c=8.411(1) Å,=93.00(1),=104.87(1), =105.69(1)°,V _c=270.66(8) ų,Z=1,R=0.0380 for 875 independent observed reflections.     

Structural study of nitrovinylindoles: (I) 2-methyl-3-(2′-methyl-2′-nitrovinyl)indole and (II) 3-(2′-nitrovinyl)indole

Compound (I) is 2-methyl-3-(2-methyl-2-nitrovinyl)indole, C₁₂H₁₂N₂O₂,M _r=216.24, monoclinic,P2₁/n,a=16.710(1),b=7.627(1),c=17.646(1) Å,=104.8(1)°,V=2174.7(1) ų,Z=8.D _x=1.321 g cm^–3, MoK, =0.71073 Å,=0.858 cm^–1,F(OOO)=912, room temperature,R=0.061 for 1956 observed reflections. Compound (II) is 3-(2-nitrovinyl)indole, C₁₀H₈N₂O₂,M _r=188.18, monoclinic,P2₁/n,a=10.178(1),b=10.608(1),c=8.411(1) Å,=105.5(2)°,V=875.0(1) ų,Z=4,D _x=1.4284 g cm^–3, CuK, =1.5418 Å,=8.068 cm^–1,F(000)=392, room temperature,R=0.040 for 1330 observed reflections. Compounds (I) and (II) have a similar geometry, the only significant difference lying in the rotation of the nitrovinyl chain. This feature could be responsible for the difference in biological activity. In both compounds, the molecules are associated, forming charge-transfer complexes.     

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.     

Refinements of the crystal structures of 1,4-diphenylbutadiyne and its complex with two moles of Co2(CO)6

1,4-diphenylbutadiyne, C₁₆H₁₀, crystallizes in monoclinic space group P2₁/n witha=6.6152(6),b=6.0768(7),c=14.634(1) Å, =100.981(8)⁰,V=577.5(2) ų,Z=2. The structure was refined toR=0.077 andR _w=0.069 for 1007 observed reflections with CuK radiation. The molecule lies on an inversion center. Our determination represents and increase in precision of a factor of approximately three over the original determination. The 21 cobalt complex, C₁₆H₁₀[Co₂(CO)₆]₂, also crystallizes in monoclinic space group P2₁/n witha=8.9568(12),b=17.7057(10),c=18.5671(12) Å, =90.606(12)^o,V=2944.3(5) ų,Z=4. The structure was refined toR=0.032 andR _w=0.031 for 4312 observed reflections. The diphenylbutadiyne triple bonds elongate to 1.346(3) Å and the angles at the diyne C atoms decrease to 134.1(3)–144.9(3)^o upon complexation. The Co-Co distance is 2.4580(4)Å. Our data represent an increase in precision by a factor of 2–3 over the original determination.     

Crystal structures of two allotropic forms of Na2CoP2O7

Na₂CoP₂O₇ may be prepared in two allotropie forms:I, rose,M _r =278.85, triclinic, P1,a=9.735(2),b=10.940(3),c=12.289(4) Å,=148.78,=121.76(1), =68.38(2)°,V=566.8(2) ų,Z=4,D _meas=3.28(5) g cm^–3,D _calc=3.267 g cm^–3, (MoK)=0.71069 Å,=37.12 cm^–1, F(000)=540,T=298 K,R=5.4% for 2911 observed reflections; andII, blue,M _r =278.85, orthorhombic, P2₁cn,a=7.713(2) Å,b=10.271(4),c=15.378(6)°,V=1218.2(8) ų,Z=8,D _meas=3.06(5) g cm^–3,D _calc=3.040 g cm^–1, (MoK ) Å,=34.55 cm^–1, F(000)=1080,T=298 K,R=9.9% for 1450 observed reflections. Cobalt displays octahedral coordination to six oxygen atoms in the rose form whereas the metal coordination is tetrahedral in the blue form.     

Gold(I)-selenium bond: synthesis and x-ray structure of chloro(triphenylphosphine selenide)gold(I)

The crystal and molecular structures of chloro(triphenylphosphineselenide)gold(I), [(C₆H₅)₃PSe]AuCl, have been determined from three-dimensional X-ray intensity data collected on a CAD4 diffractometer. The compound crystallizes in the triclinic space groupPl witha=9.322(3),b=10.639(5),c=9.252(3) Å, =104.74(4), =99.52(3), =76.97(3)°, andZ=2. Atomic parameters were refined by full-matrix least-squares to anR value of 5.7% for 2591 observed reflections. This is one of the few known examples of linear gold(I) complexes having an Au-Se linkage. The Se-Au-Cl angle is 178.6(1)°, and the Au-Se and Au-Cl distances are 2.371(2) and 2.277(6) Å, respectively. As expected, the Au-Se bond length is 0.10–0.18 Å longer than the Au-S bond length observed in similar two-coordinate linear gold(I) complexes.     

Structure of (Z)-1-p-methoxyphenyltelluro-1,4-diphenyl but-1-en-3-yne

C₂₃H₁₈TeO,M _r=437.97, ,a=9.940(2),b=13.664(3),c=7.895(2) Å, =80.60(1), =69.71(2), =75.95(1)°,V=972.0(4) ų,Z=2,R=0.041 for 2668 observed reflections. The Te–C bond distances are 2.109(5)Å and the C–Te–C angle is 96.0(2)°. The phenyl rings are planar to within experimental accuracy, making dihedral angles of 64.6(2), 65.3(2) and 31.1(3)°.     

Structures of 8α-(2′-methylbutyryloxy)-9α-hydroxymontahibisciolide,a new skeletal type of sesquiterpene lactone,and of its precursor 8α-isobutyryloxy-9-oxo-germacra-4E, 1(10)Z-dien-6β,12-olide

The structures of a new skeletal type of sesquiterpene lactone, containing a seven, five, fivering system, and of its putative precursor, a 9-oxo-melampolide, have been confirmed by single crystal X-ray structure determination. The central 5-membered ring of the new skeleton istrans-fused to the cycloheptene ring andcis-fused to the lactone ring. Transannular interactions and the geometry of thetrans carbon-carbon double bond of the oxo-melampolide and the keto-group at C9, suggest that the new seven, five, five tricyclic skeleton-type of montahibisciolide can easily be reached by a transannular cyclization process. The isobutyrloxy group of the oxo-melampolide is disordered into two partially populated conformations. 8-(2-Methylbutyryloxy)-9-hydroxymontahibisciolide,3, C₂₀H₂₈O₅, crystallizes in orthorhombic space groupP2₁2₁2₁ witha=8.294(2),b=9.740(2),c=22.675(1) Å,V=1832(1)ų,Z=4. The structure was refined toR=0.043 andR _w=0.048 for 2898 observed reflections with CuK radiation. 8-isobutyryloxy-9-oxo-germacra-4E, 1(10)Z-dien-6, 12-olide,4, C₁₉H₂₄O₅, crystallizes in monoclinic space groupC2 witha=32.879(7),b=5.793(2),c=9.884(4)Å, =99.01(3)°,V=1859.5(9)å³,Z=4. The structure was refined toR=0.054 andR _w=0.064 for 1010 observed reflections with MoK radiation.     

Crystal structure of 20ζ-hydroxy-3β-pyrrolidino-5-pregnene-16α-carbonitrile (HS1175): A novel design for neuromuscular blocking drugs

The structure of the title compound C₂₆H₃₈N₂OH has been determined by direct methods from diffractometer data and refined by full-matrix least-squares. Crystals are monoclinicP2₁,a=6.237(1),b=10.295(2),c=18.485(2) Å, =98.76(1)^o,Z=2,D _c=1.12 g cm^–3,R=0.055 for 1059 observed reflections. The structure has two N-containing functional groups, one each in the pyrrolidine ring and carbonitrile groups, with interatomic separation of 11.527 Å. The 16-carbonitrile group is -oriented. All steroid rings are trans-connected, A and C being in chair conformations and B and D half-charis. N(23) in the carbonitrile side-chair forms a weak tail-tail hydrogen-bond network by linking with the neighboring OH(20) hydroxy group at 1–x, 1/2+y, 1–z.     

Novel manganese(III) oxidation chemistry: X-ray crystal structures of (1α,2α,4β)-1,2-diacetoxy-4-(4-methoxyphenyl)-6-methoxy-1,2,3,4-tetrahydronaphthalene (compound A) and (1α,2α,4β)-1,2-diacetoxy-4-(2-methoxyphenyl)-8-methoxy-1,2,3,4-tetrahydronaphthalene (compound B)

CompoundA is (1,2,4)-1,2-diacetoxy-4-(4-methoxyphenyl)-6-methoxy-l,2,3,4-tetrahydronaphthalene, C₂₂H₂₄O₆,M _r=384.43, monoclinic, P2₁/n, witha=11.074(3),b=10.353(4),c=17.616(4)Å,=94.96(2)°,V=2012.1ų,D _calc=1.27 g cm^–3 and=0.55 cm^–1 forZ=4. Least-squares refinement of 1371 observed [F ₀5 (F ⁰)] reflections led to the final agreement index ofR=0.052. A twofold disorder was observed for the 1-acetoxy group whereas the 2-acetoxy group was ordered. CompoundB, (1,2,4)-1,2-diacetoxy-4-(2-methoxyphenyl)-8-methoxy-l,2,3,4-tetrahydronaphthalene, C₂₂H₂₄O₆,M _r=384.43, crystallizes in the monoclinic space group, P2₁/c, witha=16.209(2),b=10.076(1),c=13.357(4)Å,=111.41(2)°,V=2030.9ų,D _calc=1.26 g cm^–3 and=0.54 cm^–1 forZ=4. A final agreement index ofR=0.045 was realized by least-squares refinement of 1486 observed [F _o5 (F _o)] reflections. Intermolecular interactions in the cell lattices of compoundsA andB are noted. The title compoundsA andB were prepared by manganese(III) acetate oxidative dimerization of two molecules of 4-methoxystyrene and 2-methoxystyrene, respectively.     

Structure of 2-(2′-bromo-5′-nitrostyryl)benzothiazole

The title compound C₁₅H₉BrN₂O₂S (brnsb) is monoclinic, witha=7.730(2),b=26.847(5),c=7.773(2) Å,=117.48(1)°,V=1431(1) ų,Z=4,D _x=1.677,(MoK)=29.9 cm^–1,F(000)=720,T=298K in space groupP2₁/c. The structure was solved by heavy atom and Fourier methods and refined toR=0.034 for 1776 unique observed reflections. The molecule is nearly planar, with a dihedral angle of only 3.8(1.1)° between the benzothiazole and phenyl rings. The C-S-C angle in the thiazole ring is 89.0°, while the C-N-C angle in that ring is 111.5(3)°.     

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.     

Synthesis and structural characterization of 2,6-bis-(N-methylenemorpholino)-4-methylphenol (MMP) and 2,6-bis-(N-methylenemorpholino)-4-bromophenol (MBrP)

MMP: C₁₇H₂₆N₂O₃,M _r =306.40, monoclinic, space groupP2₁/c,a=10.927(2),b=10.777(2),c=14.197(2) , =94.04(2)°,V=1667.7(5) ³,D _cal=1.22 Mgm^–3,Z=4,F(000)=664, =5.93 cm^–1,T=293K. FinalR=0.049 andwR=0.063 for 2724 observed reflections. MBrP; C₁₆H₂₃N₂O₃Br,M _r =371.27, monoclinic, space groupP2₁/c,a=10.955(1),b=10.785(1),c=14.213(1) , =94.54(2)°,V=1674.0(4) ³,D _cal=1.48 Mgm^–3,Z=4,F(000)=768, =32.35 cm^–1,T=293K. FinalR=0.055 andwR=0.069 for 2886 observed reflections. MMP and MBrP are isostructural and in both the molecules the morpholino rings assume a chair conformation.DCB Contribution No. 824.     

Crystal structures of bis-11-aminoundecanoic chlorocuprate and bis-11-aminoundecanoic-Cu(II) sulfate trihydrate

Bis-11-aminoundecanoic chlorocuprate: (I),M _r =609.5, triclinic,P¯1 (No. 2),a=7.237(1),b=7.536(1),c=27.605(2) Å, =97.98(8),=92.45(8), =90.02(8)°,V _c =1492 ų,Z=2,D _x =1.357 g cm^–3,D _m =1.35(1) g cm^–3 (flotation), =43.85 cm^–1, CuK radiation=1.5418 Å,F(000)=642,T=23 °C,R=0.065 for 4121 observed reflections. Bis-11-aminoun-decanoic sulfate Cu(II) trihydrate: (II),M _r =616.4, triclinic,P¯1,a=7.745(2),b=9.553(4),c=20.343(5) Å, =80.91(3),=79.28(2), =87.58(3)°,V _c =1460 ų,Z=2,D _x =1.40(1) g cm^–3,D _m =1.38(2) g cm^–3 (flotation),=8.16 cm^–1, MoK radiation=0.71069 Å,F(000)=658,T=23°C,R=0.064 for 3384 observed reflections. In (I) the two copper ions are in special positions 0, 0, 0 and 1/2, 1/2, 0 octahedrally coordinated to Cl^–. The CuCl ₂ ^2– ions make square planes with the short bonds of mean values 2.289 and 2.295 Å. The carbonyls are hydrogen bonded, and the conformation of the amino acid chains ist for whole chain except at C(11) of chainA and N of chainB where it isg. In (II) Cu²⁺ shows a very distorted octahedral coordination with a mean value of 1.959 Å for the short bonds Cu-O and 2.512 Å for the long bonds. TheB amino acid chain presents a similar conformation change at C(11) as in theA chain of complex (I).     

Crystal structures of 3-(4-pyridinyl)-5,6,7,8-tetrahydro-1,2,4-triazolo[4,3-a]pyrimidine and its 6-hydroxy derivative

(1): C₁₀H₁₁N₅,M _r=201.23, from water, P ,a=6.913(1),b=8.198(2),c=9.212(2) Å, =72.36(2), =109.03(2) and =88.13(1)^o,D _x=1.436 g/cm³,Z=2. FinalR=0.043 for 1477 observed reflections. (2): C₁₀H₁₁N₅O,M _r=217.23, from methanol/water solution. P2₁/c,a=9.291(2),b=11.263(3),c=10.454(3) Å, and =114.05(1)^o,D _x=1.444, g/cm³,Z=4. FinalR 0.056 for 1587 observed reflections. The data were collected on a diffractometer at room temperature. Structures were solved by direct methods and refined by anisotropic full-matrix least-squares method. In the solid state both molecules have the same conformation and are packed in similar manner. The planarity of the condensed triazole ring and its electrons conjugation with a lone pair at N8 impose C6 sofa conformation of the saturated diazine rings. Hydroxy group in2 is in an energetically unfavorable axial position. Both in1 and2, N8–H ... N34 hydrogen bonds join molecules into infinite chains, and O6–H ... N1 hydrogen bonds in2 span the chains into two-dimensional net. The molecules in hydrogen bonded chains and sheets have the same chirality.     

Structure oftrans-dichlorooxobis(triphenylphosphine)rhenium(V), ReCl2O(OEt)(Ph3P)2

C₃₈H₃₅Cl₂O₂P₂Re,M _r=842, triclinic,P¯1,a=17.71(2),b=11.33(1),c=9.82(1) Å,=114.60(3),=90.84(3), =78.05(3),V=1747(2) ų,D _m(flotation)=1.60,D _x=1.60 Mg m^–3 forZ=2, MoK, =0.7107 Å,=41.6 cm^–1,F(000)=836, room temperature. The structure was solved by standard methods from diffractometer data and refined to a conventionalR of 3.4% for 5412 observed reflections. The Re atom is six coordinate octahedral withtrans-Cl atoms andtrans-Ph₃P groups. Relevant bond distances are: Re-P 2.533(1) and 2.535(1) Å, Re-O(ethoxo) 1.888(4) Å, and Re-O(oxide) 1.699(4) Å. The ethyl chain is partially disordered.     

Crystal structures of dimethylsuccinate and dimethyloxalate: Carbonyl group orientation for C13 chemical shielding tensor studies

The crystal structures of dimethylsuccinate (DMS) and dimethyloxalate (DMO) have been determined to facilitate the determination of the C-13 chemical shielding tensors of the carbonyl carbon in esters. Crystals of DMS are monoclinic, space groupC2/c,Z=4,a=13.154(4),b=6.156(1),c=9.363(4)Å,=98.53(3)°. The structure was solved by direct methods and refined by leastsquares procedures to giveR=0.071 for 932 observed data. Crystals of DMO are monoclinic space group,P2₁/n,Z=2, witha=3.891(1),b=11.879(2),c=6.213(2) Å,=103.32(2)°. The structure is the same (within experimental error) as that reported by Dougill and Jeffrey (1953) and refined to giveR=0.074 for 395 observed data.     

Structure of (chloranilato)bis(tri-n-butylphosphine)palladium(II)

(Chloranilato)bis(tri-n-butylphosphine)palladium(II), [Pd(C₆Cl₂O₄){P(C₄H₉)₃}₂] (chloranilic acid=2,5-dichloro-3,6-dihydroxy-p-benzoquinone): FW=718.02,P2₁/c,a=21.729(6),b=17.293(5),c=21.010(9) Å,=112.62(3)°,V=7287.42 ų,Z=8,D _c=1.309mg m^–3, Mo, =0.710730 Å,=0.76 mm^–1,F(000)=3008, finalR=0.087, 2594 observed reflections. Palladium is ligated by a distorted square planar P₂O₂ coordination sphere in the title compound. The two molecules per asymmetric unit differ in the arrangement of phosphine n-butyl chains, yielding two unique metal centers.     

Crystal and molecular structure of 2,3,6,7-tetramethoxy-9-trichloromethyl-10-carboxymethyl-9,10-dihydroanthracene

Cl₃O₆C₂₁H₂₁,M _r =475.75, orthorhombic,P2₁2₁2₁,a=21.895(3),b=12.101(2), andc=8.237(2) Å,V=2182.4(7) ų,D _x =1.45 g cm^–3 forZ=4, (MoK)=0.71069 Å=3.99 cm^–1,F(000) 984, room temperature,R=0.035 for 1877 observed reflections. The molecule exhibits a folded conformation: the dihedral angle between the benzene rings is 28.3(1)°. The central ring is characterized by acis diaxal configuration of hydrogen atoms in the 9, 10 positions, confirming the 13-C NMR results.