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.     

Crystal and molecular structure of [rac-1S,2S,-3S,4R]methyl 2-benzoyl-3,4-dimethyl-4-phenylcyclobutane-1-carboxylate,C21H22O3

The structure of the title compound C₂₁H₂₂O₃, was determined by X-rays.Minr=322.4, monoclinic, space groupP2₁/a,a=11.960(2),b=14.275(3),c=10.858(2) Å,=103.20(2)°,V _c =1804.8 ų,Z=4,D _x =1.223 Mg m^–3. CuK radiation (graphite crystal monochromator,=1.54184 Å),(CuK)=6.53 cm^–1,F(000)=688, T=290 K. Final conventionalR factor=0.050,R _w =0.069 for 1679 unique reflections and 284 variables. The structure was solved usingMultan.     

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.     

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.     

Crystal and molecular structure ofendo-5-acetoxy-4-(p-tolylsulfonyl)methyl-exo-10-oxatricyclo-[5,2,1,02,6]deca-3,8-diene,C19H20O5S

The structure of the title compound, C₁₉H₂₀O₅S, was determined by X-rays.M _r =360.42, monoclinic, space groupP2₁/c, a=8.517(2),b=31.107(2),c=20.517(4) Å,=96.205(18)°,V _c =5403.9 ų,Z=12,D _x =1.45 Mg m^–3. CuK radiation (graphite crystal monochromator, =1.54178 Å),(CuK)=1.777 mm^–1,F(000)=2280T=295 K. Final conventionalR-factor=0.058,R _w =0.060 for 3476 observed reflections and 552 variables. The structure was solved usingMultan andDirdif (direct methods applied to difference structures). The configurations of three crystallographically independent molecules in the asymmetric unit of the crystal are reported.     

Crystal and molecular structure of 3-methoxy-6-nor-6,7-secooestra-1,3,5(10),9(11), 14-penten-17-one-8β-ethyl carboxylate

C₂₀H₂₂O₄,M _r =326.39, triclinic,P¯1,a=10.365(2),b=11.383(2),c=8.461(1) Å, =103.60(1),=104.44(1), =105.23(1)°,Z=2, (CuK)=1.54178 Å;R=0.0633 for 1940 reflections. The results of the X-ray analysis have shown that the ethyl carboxylate substituent is oriented. The geometry of the main skeleton of the molecule has not revealed any significant differences in the present compound and in the case of the epimeric molecule.     

Crystal and molecular structure of nitrito-bis(1,3-propanediamine) nickel(II) tetraphenylborate

The title compound is orthorhombic,M _r =590.2,P2₁2₁2₁ (No. 19),a=9.865(2),b=9.924(2),c=31.202(7) Å,V=3055(2) ų,Z=4,D _x =1.283 g cm^–3, (MoK );F(000)=1256; (MoK )=6.76 cm^–1, finalR=0.052 for 1441 reflections I2.5(I). The nitrite group is chelated via the two oxygen atoms; the two six-membered rings resulting from the coordination of the 1,3-propanediamine ligands to the nickel(II) atom are in the chair conformation. The Ni-N and Ni-O distances average 2.07(1) and 2.14(2) Å respectively. The two Ni-O distances are nearly equivalent.     

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.     

Crystal and molecular structure of 5-ethoxy-4-methylene-exo-10-oxatricyclo[5.2.1.02,6]-deca-8-ene-3-ol,C12H16O3

The structure of the title compound, C₁₂H₁₆O₃, was determined by X-rays.M _r =208.26, triclinic, space groupP¯1,a=7.802(2),b=8.449(2),c=9.069(1) Å,=90.79(1)°,=105.57(1)°, =106.07(1)°,Z=2,D _x =1.26 Mg m^–3; MoK radiation (graphite crystal monochromator, =0.71069 Å),(MoK)=0.96 cm^–1,T=290 K. Final conventionalR-factor=0.046,R _w =0.067 for 3009 observed reflections and 184 variables. The structure was solved using Patterson methods andDirdif, and the resulting all cis-endo configuration of the alcohol group on C(3) and the ethoxy group on C(5) shows that the stereochemistry of the metal-mediated addition reaction involved is solely determined by steric factors.     

Crystal and molecular structure of 1,6-dimethyl-3,6-dimethoxy-3-[(N-methylindol-3-yl)methyl] piperazine-2,5-dione,C18H23N3O4

The structure of the title compound, C₁₈H₂₃N₃O₄, was determined by X-rays.M _r =344.40, triclinic, space groupP¯1,a=8.163(4),b=9.230(2),c=13.297(2) Å,=102.70(2),=103.58(3)°,=102.50(3)°,V=911.3 ų,Z=2,D _c =1.26 Mg m^–3. CuK radiation (graphite crystal monochromator,=1.54178 Å),(CuK)=7.50 cm^–1,T=290 K. Final conventionalR-factor=0.068,R _w =0.079 for 1912 unique reflections and 295 variables. The structure was solved usingMultan andDirdif. The title compound is the first example of a 3,6-tetrasubstituted dioxopiperazine adopting a folded conformation, owing to a direct interaction between the dioxopiperazine ring and the aromatic side chain.     

Crystal and molecular structure of rac(1R,5S,6S,7R)-1-oxy-7-benzoyl-5-methyl-8-azabicyclo-[4.3.0]nonane-4,9-dione,C16H17NO4 (perhydroindole)

The structure of the title compound (perhydroindole) was determined by X-rays, using CuK radiation (graphite-crystal monochromator,=1.54184 Å): T=290 K., C₁₆H₁₇NO₄,M _r =287.31 monoclinic, space groupC2/c,a= 14.471(1),b=6.169(2),c=32.065(2) Å,=92.192(6)V _c =2860,6 ų,Z=8,D inx=1.338 Mg m^–3, (CuK)=7.54 cm^–1. Final conventionalR-factor=0.048, (R _w =0.072) for 2513 unique reflections and 258 variables. The structure was solved usingMultan. The six-membered ring of the molecule is in the chair configuration. The molecules are connected by hydrogen bonds.     

Crystal and molecular structure of 2′,4′-dimethoxyflavone

C₁₇H₁₄O₄,M _r =282.3, triclinic,P-1,a=8.469(3),b=8.516(2),c=20.425(8)Å,=84.95(3),=81.98(3), =70.47(2)°,V=1373(13)ų,Z=4,D _x =1.365 g cm^–3, (MoK )=0.71069 Å,=0.91 cm^–1,F(000)=592,T=294K,R=0.038 for 3577 observed reflections (F>3 (F)). The asymmetric unit is composed of two molecules. These two molecules, which are in planar conformations, differ in 4-methoxyl group orientation. Short intramolecular contacts are found between the -benzopyran portion and the dimethoxyphenyl ring.     

Molecular structure of N-(2-phenylethyl)amide of α-(1,1-ethylenedioxy)-ethyl γ-hydroxybutyric acid (I) and1H NMR spectra of (I) and N-(p-methoxybenzyl)derivative (III)

The spectroscopic and X-ray investigation of the N-(2-phenylethyl) amide of -(1,1-ethylenedioxy)-ethyl--hydroxybutyric acid are reported. The¹H NMR spectra for the title structure and for the N-(p-methoxybenzyl) amide of -(1,1-ethylenedioxy)-ethyl--hydroxybutyric acid are given. The N-(2-phenylethyl)amide of -(1,1-ethylenedioxy)-ethyl--hydroxybutyric acid, C₁₆H₂₃O₄N, crustallizes in the monoclinic space groupP2 ₁/c witha=21.547(5),b=6.333(2),c=11.822(3) Å and =101.01(2)°. The dioxolane ring has a half-chair conformation with C₂(O3)=2.4° and ||_av=18.2°. The inconsiderable deviations from planarity of the six atoms of the amide group are caused mainly by twist around the C4–N1 bond and out-of-plane bending at the N1 atom ((C4–N1)=4°, X_N =7°, X_c =0.4° ). The amide group plane is nearly coplanar with the phenyl ring. The molecules are connected by two intermolecular hydrogen bonds.     

Preparation,spectral studies,and X-ray crystal structures of (16S, 17R, 20S)-3-oxo-16-hydroxy-25-nor-lanostan-24-oic lactone (II) and (16S, 17R, 20S)-4,16-dihydroxy-25-nor-3,4-seco-lanostan-3,24-dioic acid dilactone (III)

The crystal and molecular structures of the title compounds have been determined by direct methods, and refined to a finalR of 0.059 forII and 0.046 forIII. Both molecules crystallize in space group P2₁2₁2₁. The cell dimensions forII area=10.096(5),b=11.255(3),c=20.300(7) Å;Z=4,D _x=1.188 g cm^–3, (MoK)=0.70 cm^–1, while the cell dimensions forIII area=7.346(1),b=10.470(3),c=30.546(5) Å;Z=4,D _x=1.212 g cm^–3, (MoK)=0.74 cm^–1. The rings of the triterpene skeletons aretrans-cis-trans-cis connected. The conformations of both molecules are discussed. Also the preparation and the spectral data of (17R, 20S)-3,16-dioxo-25-nor-lanostan-24-oic acid (V) and (17R, 20S)-3,16,24-trioxo-25-hydroxy-16,24-seco-lanostan-25-acetate (VI) are given.     

Crystal and molecular structure of rac (1R,5R,6S,7R)-1-oxy-7-benzoyl-5-methyl-8-azabicyclo-[4.3.0]-nonane-4,9-dione, C16H17NO4 (perhydroisoindole)

The structure of the title compound (perhydroisoindole) was determined by X-rays, using CuK radiation (graphite-crystal monochromator, =1.54184 Å):T=290 K, C₁₆H₁₇NO₄,M _r =287.31, orthorhombic, space groupPbcn,a=18.732(1),b=10.663(1),c=14.074(1) 0A,V _c =2811.2 ų,Z=8,D _x =1.361 Mg m^–3 and (CuK)=8.19 cm^–1. The final conventionalR-factor=0.036, (R _w =0.046) for 1951 unique reflections and 241 variables. The structure was solved usingMultan. The six-membered ring of the molecule is in the chair configuration. The molecules are connected by hydrogen bonds.     

C−Cl...π(Ar)...Cl−C,Cl...Cl and other interactions in the structures of two 6-substituted-2,4-bis(trichloromethyl)-1,3-benzdioxin's: (I) 6-carboxymethyl; (II) 6-propionyl,an antimethanogenesis food additive

C₁₂H₃Cl₆O₄, (I),M _r=428.91, triclinic, ,a=9.197(1),b=9.336(2),c=9.830(1) Å, =79.29(1), =83.33(1), =85.38(1)°,V=822.16,Z=2,D _x=1.73 Mg m^–3,F(000)=428, (MoK)=0.71069 Å, =10.62 cm^–1, room temperature, finalR=0.033 for 2573 unique counter reflections withF _o>4(F _o). C₁₃H₁₀Cl₆O₃, (II),M _r=426.94, triclinic, ,a=9.374(2),b=9.503(1),c=9.888(4) Å, =79.26(2), =82.10(3), =84.43(1)°,V=854.88,Z=2,D _c=1.66 Mg m^–3,F(000)=428, =0.71069 Å, =10.17 cm^–1, room temperature, finalR=0.030 for 2609 unique counter reflections withF _o>4(F _o). Compounds I and II are isostructural. Centrosymmetric dimers are formed by hydrogen bonds from the two methine hydrogen atoms to the carbonyl oxygen atom. The dimers are linked by Cl...(Ar)...Cl, Cl...O and Cl...Cl interactions to form a three-dimensional pattern. The geometry associated with these interactions is discussed in terms of the electrophile: nucleophile model.     

Structure oftrans-difluorobis(1,3-propanediamine)chromium(III) perchlorate,trans-[Cr(N2C3H10)2F2](C104)

The title compound is monoclinic,M _r =337.8,P2₁/c-C _2h ⁵ (No. 14),a=5.508(2),b=13.944(6),c=18.238(5) Å,=95.99(3)°,V=1393.1(9) ų,Z=4,D _x =1.61 g cm^–3, (MoK)=0.71073 Å,F(000)=660.0,=10.3 cm^–1, finalR=0.051 for 2122 observed [I>3(I)] reflections. The two six-membered rings resulting from the coordination of the 1,3-propanediamine ligands to the chromium atom are in the chair conformation. The Cr-N and Cr-F distances average 2.085(4) and 1.876(3) Å, respectively.     

Crystal and molecular structure of 1-methyl-2,3,5,6-tetraphenylpiperidin-4-ol,C30H29NO

The structure of the the title compound, C₃₀H₂₉NO, was determined by X-rays.M _r =419.57, triclinic, space groupP1,a=5.8922(12),b=8.5855(11),c=12.2216(20) Å,=78.145(12)°,=79.181(15)°, =76.108(14)°,V _c =581.1(1) ų,Z=1,D _x =1.199 Mg m^–3. CuK radiation (graphite crystal monochromator, =1.54184 Å),(CuK)=5.17 cm^–1,T=290K. Final conventionalR-factor=0.039,R _w =0.042 for 2795 observed reflections and 377 variables. The structure was solved usingMultan andDirdif. With a view to determining the conformational preference of the piperidine ring when it is highly sustituted with a bulky group like the phenyl group, the present X-ray investigation was undertaken.     

Structure and absolute configuration of 10-chloro-10-sulfinylcamphor,C10H13ClO2S

The structure of the title compound, C₁₀H₁₃ClO₂S, was determined by X-rays:M _r =232.72, monoclinic, space groupP2₁,a=6.4902(6),b=12.022(1),c=14.130(3) Å,=103.11(1)°,V _c =1073.7 ų,Z=4,D _x =1.44 Mg m^–3. MoK radiation (graphite crystal monochromator, =0.71069 Å),(MoK)=4.9 cm^–1,F(000)=342,T=293 K. Final conventionalR-factor=0.035 for 2221 observed reflections and 252 variables. The structure was solved usingDirdif. The absolute configuration of the structure is reported. The two independent molecules differ primarily in the orientation of the sulfine group with respect to the camphor moiety.On leave from the Department of Chemistry, University of Colorado, Boulder, Colorado 80309.     

Synthesis and X-ray crystal structure of three polyazamacrocycles having sulfonate pendant groups: Piperazinyl-monomethanesulfonic acid,sodium hydrogen 1,4,7-triazacyclononane-N,N′-di(methanesulfonate) and 1,4,7,10-tetraazacyclododecane-N,N′-di(methanesulfonic acid)

C₅H₁₀N₂O₃S,1, monoclinicC2/c,a=17.545(5),b=6.822(8),c=13.928(2),=108.36(7),Z=8, MoK, =0.7107 Å,=3.56cm^–1,R=0.061,R _w =0.099. C₈H₁₆N₃O₆S₂Na·2H₂O,2, orthorhombicPna2₁,a=17.964(8),b=10.157(1),c=8.263(4),Z=4, MoK, =0.7107 Å,=4.07 cm^–1,R=0.040,R _w =0.043. C₁₀H₂₀N₄O₆S₂·2H₂O,3, monoclinicP2₁/n,a=9.142(9),b=13.576(7),c=14.028(8),=94.096(8),Z=4, MoK, =0.7107 Å,=3.37 cm^–1,R=0.063,R _w =0.074. Compounds1, 2, and3 were prepared from the pH-dependent sulfomethylation of the di- and polyazamacrocycles.