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.     

Crystal and molecular structure of 1,1′,3,3′-tetraphenyloxaldiamidrazone

1,1,3,3-Tetraphenyloxaldiamidrazone, C₂₆H₂₄N₆, crystallizes in the monoclinic system: space groupP2₁/c,a= 13.946(1) Å,b= 5.706(1) Å,c= 17.109(1) Å, = 125.31(1) °,D _m = 1.254,D _c = 1.259 gcm^–3 andZ= 2. Intensities were obtained from –2 scans with a Syntex automated diffractometer using graphite-monochromated MoK radiation. The structure was solved by direct methods. Full-matrix least-squares refinement of all positional and thermal (anisotropic for the nonhydrogen atoms and isotropic for the hydrogen atoms) parameters using 2022 reflections [I>2(itI)] converged at a conventionalR of 0.041. The molecule is characterized by a conjugated pi system which includes the central N=C–C=N moiety and two of the four aniline groups. No intermolecular and only weak intramolecular hydrogen bonds are present.     

Hydrogen bonding in 2-hydroxy((di)thio)benzoates. I. X-ray structures of 2,6-dimethylpiperidinium salts

X-ray structural data are reported for 2,6-dimethyl-piperidinium-2-hydroxybenzoate (C₁₄H₂₁NO₃, orthorhombic,P2₁2₁,2₁, (19);a=7.983(1)Å,b=12.680(2)Å,c=13.838(2)Å;Z=4;R=0.042) and for two polymorphs of 2,6-dimethylpiperidinium-2-hydroxythiobenzoate (C₁₄H₂₁NO₂S), an-form (monoclinic,P2₁/n (14);a=8.005(4)Å,b=22.150(2)Å,c=8.672(4)Å,=101.91(6)°;Z=4;R=0.059) with an intramolecular O-HS hydrogen bond, and a-form (orthorhombic,P2₁2₁2₁ (19);a=8.188(1)Å,b=14.781(2)Å,c=24.163(4)Å;Z=8;R=0.15) with an intramolecular O-HO hydrogen bond. The intra-and intermolecular hydrogen bond patterns are discussed, including the literature data of 2,6-dimethylpiperidinium-2-hydroxydithiobenzoate.     

Crystal structure of 751-1751-1751-1751-2751-2751-2

The title compound crystallizes in the centrosymmetric triclinic space group (No. 2) witha=10.818(1)Å,b=10.876(1)Å,c=11.072(2)Å, =98.74(1)°, =98.83(1)°, =96.61(1)°,V=125906(3)ų andZ=2. Interatomic distances include Fe–P=2.243(2)Å, Fe–CO=1.771(6)–1.781(5)Å, Fe–C(C₅H₅)=2.074(6)–2.103(5)Å and P–F=1.511(6)–1.571(4)Å.     

A comparison of the coordination preferences of Zn, Co, and Cd(II) with the heteroscorpionate ligand (2-hydroxy-3-t-butyl-methylphenyl)bis (3,5-dimethylpyrazolyl)methane

Reaction of the Zn, Cd, or Co nitrate salts with the deprotonated ligand (2-hydroxy-3-t-butyl-methylphenyl)bis(3,5-dimethylpyrazolyl)methane (L1O^–) in methanol produced the following complexes: [(L1OH)Zn(NO₃)₂] in two isomorphs, a = 40.983(8) Å, b = 9.571(2) Å, c = 15.667(8) Å, = 90, = 106.38(1), = 90, C2/c, and a = 13.027(3) Å, b = 14.781(4) Å, c = 16.107(3) Å, = 90, = 105.30(1), = 90, P2₁/n; [(L1OH)Cd(pz)(NO₃)₂] a = 14.7476(2) Å, b = 13.5411(2) Å, c = 16.7223(2) Å, = 90, = 110.3840(10), = 90, P2₁/c; and [(L1O)Co(pz)(NO₃)] a = 11.4240(2) Å, b = 13.4498(2) Å, c = 13.8056(2) Å, = 105.2080(10), = 105.8130(10), = 112.7470(10), P . The Zn adopts a pseudotetrahedral four-coordinate geometry where the potentially tridentate ligand is actually bidentate with a protonated and uncoordinated phenoxy arm. The Co complex is pseudooctahedral six-coordinate where the phenoxy arm is deprotonated and coordinated. Finally the Cd complex is seven-coordinate but the metal is not coordinated through the phenoxy group that is again protonated.     

Crystal structure of tylophorine methiodide monohydrate,C25H30NO 4 + I−·H2O

The crystal structure of tylophorine (Chemical name 2,3,6,7 tetramethoxy phenanthro [9,10:6, 7] indolizidine. Contribution No. 0871.) methiodide monohydrate has been determined. C₂₅H₃₀NO ₄ ⁺ I^–·H₂0, triclinic, P,a=8.831(1)Å, b=10.842(2),c=13.902(2), =105.0(1)^o, =104.7(1), =97.3(1),V=1210.22ų, Z=2,D _x =1.428 g./cm^–3, (CuK)=1.54184Å, (CUK)=107.2 cm^–1, F(000)=544,T=295^oK,R=0.038,Rw=0.046, for 2331 observed reflections withI2(I). Apart from van der Waals forces, the structure is stabilized by two hydrogen bonds of the type Ow(H) ... O and Ow(H) ... I^– involving the water molecule as the donor and atom O4 of the methoxy group and I^– as acceptors.     

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.     

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.     

Structure of bis(2-amino-5-methylpyridinium) tetrachlorozincate at 298 and 150 K

Reaction of 2-amino-5-methylpyridine with zinc chloride and HCl in aqueous solution yields bis(2-amino-5-methylpyridinium) tetrachlorozincate. The complex crystallizes in the monoclinic space group P2₁/c, with minimal tetrahedral distortion of the ZnCl₄ ^2– ion at both 298 and 150 K; at 298 K, a = 8.090(2) Å, b = 14.795(6) Å, c = 15.850(4) Å, = 101.93 (2); at 150 K, a = 8.0986(2) Å, b = 14.7190(5) Å, c = 15.7684(7) Å, = 102.862(2). The anisotropic cell contraction results in significant changes in nonbonding Cl Cl contacts.     

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.     

X-ray diffraction structure of the 1,1′-bis(diphenylphosphino)ferrocene (dppf)-bridged complex [(dppf)AgCl]2: An unexpected product from the reaction betweencis-(bpy)2RuCl2 and dppf in the presence of AgBF4

The reaction betweencis-Ru(bpy)₂Cl₂ (where bpy=bipyridine) and the diphosphine ligand 1,1-bis(diphenylphosphino)ferrocene (dppf) in the presence of AgBF₄ has led to the isolation of the title compound [Ag(dppf)Cl]₂. [Ag(dppf)Cl]₂ has been structurally characterized by X-ray diffraction analysis, which confirms the bridging mode adopted by the ancillary dppf ligand and the centrosymmetric nature of this molecule. Dimeric [Ag(dppf)Cl]₂ crystallizes in the triclinic space group ,a=11.426(1) Å,b=11.509(1) Å,c=12.786(1) Å, =68.96(2)°, =70.66(2)°, =71.24(2)°,V=1441(1) ų,Z=1,d _calc=1.608 g·cm^–3;R=0.0445,R _w=0.0566 for 4486 observed reflections withl>3(l)     

Crystal and molecular structure of (exo)-2-methoxycarbonyl-5-ethoxycarbonyl-4,5,6,11b-tetrahydroisoxazolidino-[2,3-a]-β-carboline,C18H20N2O5

The structure of the title compound, C₁₈H₂₀N₂O₅, was determined by X-rays atT=290 K.M _r =344.366, monoclinic, space groupP2₁/c,a=13.7850(8),b=8.8951(7),c=15.1603(11) Å, =111.410(6)°,V _c =1730.7 ų,Z=4,D _x =1.322 Mgm^–3. Cu K radiation (graphite crystal monochromator, =1.54178 Å),(Cu K)=7.69 cm^–1. Final conventionalR-factor=0.057,R _w =0.076 for 2160 observed reflections and 271 variables. The structure was solved usingMultan.     

Hydrogen-bond networks in the mono- and diprotonated cyclic diamine [9]aneN2S

The hydrogen-bond networks in the mono- and diprotonated cyclic diamine, 1-thia-4,7-diazacyclononane, [9]aneN₂S, have been examined. Crystals of the monoprotonated, form [9]aneN₂S HCl, contain a ribbon-like network of alternating strong and weak intermolecular N H Cl hydrogen bonds and weak intramolecular N H N hydrogen bonds. Crystal data for [9]aneN₂S HCl: monoclinic, a = 6.6640(6) Å, b = 10.3493(9) Å, c = 6.9807(6) Å, = 108.847(1)°, V = 455.63(7) ų, space group P2₁, Z = 2. In the di-protonated form, [9]aneN₂S 2HBr, the ribbon-like network comprises strong intermolecular and weak intramolecular N H Br hydrogen bonds. Crystal data for [9]aneN₂S 2HBr: orthorhombic, a = 12.5918(13) Å, b = 8.0753(9) Å, c = 10.6856(11) Å, V = 1086.5(2) ų, space group Pnma, Z = 4. The chloride anions of [9]aneN₂S HCl align in interlocking columns in the a- and c-direction whereas the bromide anions in [9]aneN₂S 2HBr occupy channels in the b-direction.     

Preparation and crystal structures of the Ce(IV) β-diketonates, [Ce(tmhd)4] and [Ce(pmhd)4] (tmhd =2,2,6,6-tetramethylheptane-3,5-dionate and pmhd = 1-phenyl-5-methylhexane-1,3-dionate)

The cerium(IV) -diketonate compounds [Ce(-diket)₄] [where -diket = tmhd (2,2,6,6-tetramethylheptane-3,5-dionate) 1, pmhd (1-phenyl-5-methylhexane-1,3-dionate) 2] were prepared by reacting cerium(IV) ammonium nitrate [CAN; Ce(NH₄)₂(NO₃)₆] with the respective Na(-diket) compound in ethanol, and structurally characterized by single crystal X-ray diffraction. Compound 1 crystallizes in the triclinic space group with a = 12.472(4), b = 19.972(5), c = 21.436(3) Å, = 97.05(7), = 90.16(2), = 106.55(3)°, V = 5076(2) ų, Z = 4, T = 150(2) K. Compound 2 crystallizes in the monoclinic space group P2₁/n. with a = 14.817(6), b = 17.123(6), c = 19.146(3) Å, = 105.46(4)°, V = 4682(3) ų, Z = 4, T = 150(2) K. Crystals of 1 contain two independent [Ce(tmhd)₄] molecules, with four chelating tmhd ligands bonded to each metal in a distorted dodecahedral arrangement; the cerium atom in 2 is also bonded to four chelating pmhd ligands but in this case the coordination geometry is closer to square antiprism. Both complexes are air and moisture stable. Sublimation studies reveal that 1 sublimes almost quantitatively, while 2 is comparatively involatile.     

Synthesis,characterization and crystal structure of oxovanadium(IV) complex with tridentate o-van-gly and bidentate phenanthroline

A novel oxovanadium(IV) complex with tridentate schiff base and bidentate phenanthroline ligands, VO(o-van)(phen) 2H₂O[o-van-gly: o-vanillin-glycine; phen: phenanthroline], was synthesized and characterized by elemental analysis, IR and UV-vis spectra. The crystal structure was determined by X-ray single crystal diffraction analysis. The crystal of title complex (C₂₂H₂₁N₃O₇V, M_w = 490.36) belongs to triclinic, space group P-1 with the following crystallographic parameters: a = 9.247(3) Å, b = 10.125(4) Å, c = 13.100(5) Å, = 106.343(6), = 96.042(7), = 101.726(7), V = 1135.0(7) ų, Z = 2, D_c = 1.435 Mg m^–3, (MoK = 0.485 mm^–1, F(000) = 506, and final R₁ = 0.0779, wR₂ = 0.1598 for observed reflections 1606 (I > 2(I)). V(IV) is six-coordinate with three oxygen atoms and three nitrogen atoms in a distorted octahedral geometry. The complex forms a 3-D network via – stacking and hydrogen bonds.     

Structure of 3α,12β-dihydroxy-2β-morpholino-5α-pregnan-20-one,C25H41O4N

The crystal and molecular structure of 3,12-dihydroxy-2-morpholino-5-pregnan-20-one, C₂₅H₄₁O₄N, has been determined:M _r =419.6,P2₁,a=13.5778(8),b=14.4340(8),c=5.8943(5) Å,=94.32(1)°,V _c =1151.9(3) ų,Z=2,D _x =1.21 g cm^–3, (CuK) = 1.5418 Å, =5.6 cm^–1,F(000)=460,R=0.039,R _w =0.040 for 2421 unique observed reflections. All six-membered rings have chair conformations, and theD ring has a 13-envelope conformation. The progesterone side chain has an unusual conformation, and the C16-C17-C20-O20 torsion angle, which defines the conformation, is –152.6(3)°. The unusual conformation seems to be forced by the intramolecular hydrogen bond between the hydroxyl group at C12 and the O20 atom from the side-chain.     

Structure of 6β-acetoxyprogesterone,C23H32O4

The X-ray crystal structure of 6-acetoxyprogesterone, C₂₃H₃₂O₄, has been determined. This compound crystallizes in space groupP2₁2₁2₁ witha=13.195(3),b=15.035(4),c=10.705(3) Å,V=2139.8(9) ų,M _r=372.5,Z=4,D _x=1.156g cm^–3; MoK radiation (=0.7107 Å),=0.72 cm^–1,F(000)=808;R=0.069, andR _w=0.052 for 1292 reflections. RingA adopts a normal 1,2-half-chair conformation. The side chain is typical for a 20-ketosteroid conformation.     

Crystal structures of five policyclic compounds related to the natural product forskolin

(3(Z),4,6a,9a,9b)-(±)-3a,4,6a,7,8,9,9a,9b-octahydro-4,7,7, 9b-tetramethyl-3a-[3-(methoxymethyloxy)-3-methyl-1-butenyl]-5H-naphto[1,8-de]-1,3-dioxin-6-one (I), C₂₂H₃₆O₅,M _r=378.51, monoclinic,P2₁/n,a=6.330(1),b=14.576(2),c=22.837(2)Å,=93.04(1)°,V=2104.1(2)ų,Z=4,D _c=1.19 Mg/m³, (MoK)=0.71069Å,=0.8 cm^–1,F(000)=832,T=298 K,R=0.054 for 1971 observed reflections; (7a,10a,10b,12)-(±)-7a,9, 10,10a,10b,11,12,12a-octahydro-2,2,10,10,10b,12a-hexamethyl-2H,8H-1-benzopyrano[4a,5,6,-de][1,3,2]-benzodioxin-11-one (II), C₂₀H₂₉O₄,M _r=334.5, triclinic,P-1,a=10.595(2),b=12.152(1),c=8.073(1)Å,=106.53(1),=105.65(1), =66.29(1)°,V=897.9(2)ų,Z=2,D _c=1.24 Mg/m³, (MoK)=0.71069Å,=0.8 cm^–1,F(000)=362,T=298 K,R=0.046 for 2848 observed reflections; (7a,10a,10b,12, 12a)-(±)-7a,9,10,10a,10b,11,12,12a-octahydro-2,2,10,10,10b,12a-hexamethyl-2H,8H-1-benzopyrano[4a,5,6-de][1,3,2]-benzodioxin-11, 12-diol (III), C₂₀H₃₂O₅ (two molecules in the asymmetric unit),M _r=352.2, triclinic,P-1,a=12.948(3),b=13.615(3),c=12.197(4)Å,=101.16(2),=111.88(2), =69.48(2)°,V=1863.8(9)ų,Z=2,D _C=1.26 Mg/m³,(MoK)=0.71069 Å,=0.8 cm^–1,F(000)=768,T=298 K,R=0.060 for 4570 observed reflections; 4-acetoxy-4-[[(4a,5,8a)-(±)-hexahydro-4a,6,6-trimethyl-4H-1,3-benzodioxin-4-one]-5-yl]butan-2-one (IV), C₁₇H₂₆O₆,M _r=326.4, monoclinic,P2₁/c,a=10.495(2),b=12.050(2),c=14.216(2)Å,=108.51(1)°,V=1704.8(5)ų,Z=4,D _c=1.27 Mg/m³,(MoK)=0.71069 Å,=0.9 cm^–1,F(000)=704,T=298 K,R=0.049 for2455 observed reflections; (3a,4,5,6,6a,9a,9b)-(±)-4,5-epoxy-decahydro-3, 3a-dihydroxy-2-ethoxy-4,7,7,9b-tetramethyl-naphto-[1,8-bc]-pyran-6-ol-acetate (V), C₂₀H₃₂O₇,M _r=383.5, monoclinic,C2/c,a=10.353(2),b=17.975(3),c=21.188(3)Å,=91.29(1)°,V=3942(1)ų,Z=8,D _c=1.29 Mg/m³,(MoK)=0.71069 Å,=0.8 cm^–1,F(000)=1664,T=298 K,R=0.051 for 2120 observed reflections. We report here the complete structures of four decalin derivatives (compoundsI, II, III, V) and one related compound (compoundIV) synthetized in order to find an efficient synthetic approach for the natural productforskolin.     

Molecular structure of 3-(3-oxo-bicyclo[2.2.1]hept-5-en-2-yl)-oxirane-2-carboxylic acid methyl ester

The crystal and molecular structure of an epoxy ester is described. The structure has been solved by vector search methods and refined by least squares methods toR ₁=0.0372 [I>2(I)]. The structure consists of two independent molecules in the asymmetric unit. These molecules are chemically the same. Crystal data: C₁₁H₁₂O₄, triclinic, space group ,a=10.324(3),b=10.553(7),c=10.869(5)Å, =61.77(4), =88.64(4), =88.16(6)°,V=1042.7(9)ų,Z=4.     

Anticancer agent development. 5. X-ray structure and1H nmr spectral analysis of (1α,2α,5α,6α)-2,6-bis(3,4-methylenedioxyphenyl)-3,7-dioxabicyclo[3.3.0]octane-4,8-dione

The title compound, C₂₀H₁₄O₈, Mr=382.3, crystallized from chloroform in the centric space group P¯1 witha=6.516(4),b=6.798(3),c=9.545(7) Å,=85.31(5),=73.87(5), =79.59(4)°,V=399.2 ų, and D_calc=1.59 g cm^–3 forZ=1. Least-squares refinement of 1035 observed [F_o5(F_o)] reflections led to the final agreement index ofR=0.074. The molecule resides on a crystallographic center of inversion and is disordered into two different conformations. This manifests itself as a 50/50 disorder at O(4), C(2), and C(3). The observed structure reveals acis relationship between the bridgehead hydrogen atoms and the aryl rings. The 90 MHz¹H nmr spectrum of the title compound exhibits an AAXX spin system with a H(1)C(2) to H(1)C(3) and H(1)C(2) to H(1)C(3) coupling constant of 2.8 Hz. Computer spectral simulation and Karplus equation analysis are utilized to illustrate a relaxation of the torsion angles between H(1)C(2) and H(1)C(3), and H(1)C(2) and H(1)C(3) is solution.