Structure of 11α-hydroxy-progesterone,C21H30O3

The structure of the title compound, C₂₁H₃₀O₃, was determined by X-rays.M _r =330.5, orthorhombic,P2₁2₁2₁,a=8.4451(9),b=10.7074(8),c=20.1525(40) Å,V=1822(8) ų,Z=4,D _x =1.205 mg m^–3. CuK radiation (1.54184 Å),(CuK)=5.85 cm^–1,F(000)=720. FinalR=0.054R _w =0.049 for 1774 unique reflections. The structure was solved usingMultan. TheA ring adopts an intermediate sofa-half-chair conformation and is bent toward the face of the steroid skeleton. RingsB andC have typical chair conformations, and theD ring has a slightly distorted half-chair conformation. The progesterone side chain has a typical conformation, and the C16-C17-C20-O20 torsion angle is –17.9°. An intermolecular hydrogen bond is formed between the hydroxyl group and the progesterone side chain.     

Molecular and crystal structure of bis-quinolizidine immonium salts,V: Δ11(16)-dehydrolupaninium perchlorate monohydrate

¹¹⁽¹⁶⁾-Dehydrolupaninium perchlorate monohydrate, [C₁₅H₂₃N₂O]⁺ClO₄·H₂O, was obtained from ¹²-dehydrolupanine, the product of mercuric acetate dehydrogenation of lupanine. It forms orthorhombic crystals, space groupp2₁2₁2₁,a=8.528(1),b=12.335(1),c=32.928(3) Å,V _c=3463.8 ų,Z=8,D _m=1.34,D _x=1.34 g cm^–3, (CuK)=20.7 cm^–1.F(OOO)=1472, mp=458 K; the finalR=0.086 for 2363 observed counter reflections. Two independent perchlorate anions and two independent cations are disordered. The conformations of the independent cations are similar: sofa (ringA), chair (ringB), intermediate between sofa and half-chair (ringC), and half-chair (ringD). The two lactam oxygens of the two independent cations are each hydrogen bonded to a different water molecule. From X-ray analysis and IR spectra in the condensed phase and¹³C-NMR measurements in DMSO-²H₆ and²H₂O it is evident that in the crystalline state as well as in solution, the immoniumlactam molecular structure is present in the compound studied.     

Molecular and crystal structure of bis-quinolizidine immonium salts,III: Δ1(6)-dehydrosparteinium diperchlorate

¹⁽⁶⁾-Dehydrosparteinium diperchlorate, [C₁₅H₂₆N₂]²⁺·2ClO ₄ ^– , is tetragonal; space groupP4₃,a=9.368(1),c=21.719(3) Å,Z=4,V _c =1906.1(5) ų,D _x =1.51g cm^–3,(CuK)=35.0 cm^–1. The finalR=0.055 for 1259 independent reflections. Atoms C(3) and C(4), which are trans-annular to the immonium bond in ringA, are disordered, as was observed for other bis-quinolizidine immonium salts. RingsB, C, andD have sofa, chair and chair conformations, respectively. The quinolizidinium and quinolizidine moieties have planar and cis configurations. The title compound was obtained by mercuric acetate dehydrogenation of sparteine to ⁵-dehydrosparteine and protonation of the latter with methanolic solution of perchloric acid to pH=2.0. From¹³C NMR measurements in DMSO-²H₆ and in²H₂O it is evident that in solution the chair/chair cis-ring fusion is present within the protonated quinolizidine moiety-identical to that found in the crystalline state by X-ray analysis.     

Synthesis,crystal and molecular structure ofN-(p-chlorobenzylamide) ofα-(1,1-ethylenedioxy)-ethyl-γ-hydroxybutyric acid

N-(p-chlorobenzylamide) derivative of-(1, 1-ethylenedioxy)-ethyl--hydroxybutyric acid has been synthesized and the its crystal structure was solved. The dioxolane ring adopts a half-chair conformation, with asymmetry parameter C₂(13)=5.4°. Deformation of the amide group is caused mainly by twist around the C4-N bond.     

Crystal and molecular structure of delsoline

The crystal and molecular structure of the diterpenoid alkaloid delsoline (1) C₂₅H₄₁NO₇, M_r 467.61, has been determined by an X-ray analysis. The X-ray crystal structure which could not be solved earlier withMultan, has now been solved using the SIR 88 analysis program. The compound crystallizes in the space groupP2₁2₁2₁ with cell parameters:a=12.529(2),b=13.118(1),c=14.231(6)Å,V=2339(1)ų,Z=4,D _calc=1.33 g/cm^–3, (CuK)=1.54184 Å,(CuK )=7.4 cm^–1,R/R _w =0.068/0.040 for 2539 reflections. The A ring of delsoline exists in the boat conformation stabilized by an intramolecular N---H-O hydrogen bond. Ring D also is in a boat form. Unambiguous proton and carbon-13 nmr assignments have been made by a detailed analysis of the DEPT, COSY, NOESY, and HETCOR nmr spectra.     

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.     

Stereochemistry and hydrogen bonding of cytokinins: Crystal and molecular structure of 6-(4-hydroxy-3-methyl-cis-2-butenyl) aminopurine (cis-zeatin)

The title compound is C₁₀H₁₃N₅O, monoclinic,P2₁/a,a=13.829 (7),b=7.834 (7),c=20.138 (9) Å, and =100.75 (6)°. The structure was solved by direct methods and refined by least-squares techniques to anR factor of 0.079 for 1581 observed reflections. There are two crystallographically independent molecules (I andI). The N⁶-substituent is distal to the imidazole ring of the adenine moiety. It is interesting to note that the conformation of the N⁶-substituent relative to the adenine ring base in these two crystallographically independent molecules shows considerable resemblance with the preferred one usually adopted in other cytokinins. The angles between the mean planes of the adenine base and the N⁶-substituent are 65.6 and 63.3° for theI andI molecules, respectively. The molecules are linked by pairs of N(9)-H·N(3) hydrogen bonds. The dimer-like structures are stabilized by a three-dimensional network of O-H·O, O-H·N, N-H·O, and C-H·N hydrogen bonds.     

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.     

The pseudoguaianolide isoconfertiflorin

The sesquiterpene lactone isoconfertiflorin, C₁₇H₂₂O₅, 1, crystallizes in trigonal space group P3₁ with a = 10.4498(5), c = 12.7516(8) Å, V = 1205.9(2) ų, and Z = 3. It differs from confertiflorin in having an endocyclic C=C bond in the lactone ring, which carries an exocyclic methyl group. The seven-membered ring adopts an approximate twist-chair conformation with C10 lying in the local two-fold axis, and asymmetry parameter C₂ = 5.8°. The cyclopentanone ring has the half-chair conformation with C4 on the local two-fold axis, and C₂ = 0.9°. The lactone ring is almost planar with maximum deviation 0.014(2) Å. Both methyl groups on the 7-membered ring are –oriented. The acetyl group at C8 has an orientation.     

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.     

X-ray structure of thioquinanthrenediinium dichloride

The title compound (C₁₈H₁₂N₂S₂)²⁺ 2Cl^– is monoclinic:a=8.632(2),b=13.292(3),c=14.345(3) Å,Z=4,P2₁2₁2₁. The structure was solved by direct methods, and refined by weighted full-matrix least squares. The refinement, based on 1918 reflections withI3.0(I), converged to a finalR of 0.036 (R _w =0.042). The conformation of 1,4-dithiino ring is a boat. The linear hydrogen bond distance N-HCl is 2.980(3) Å.Part XII in the series of Azinyl Sulfides. Part XI. S. Boryczka, A. Malankiewicz, M. Wyszomirski, submitted to Recl. Trav. Chim. Pays-Bas.     

Crystal structure of a (25R)-2α,3α-epoxy-5α-spirostan-6, 23-dione hemi-ethyl acetate solvate

The compound (25R)-2,3-epoxy-5-spirostan-6,23-dione, crystallizes as a hemi-ethyl acetate solvate, having two host molecules of similar conformation per molecule of ethyl acetate, in the asymmetric unit. The O atom of the epoxy group is -oriented. The presence of the epoxy group disturbs the chair conformation in the ring A of the steroidal nucleus. Ring A has a C5,C10 half-chair conformation. The six-membered rings B, C, and F have chair conformation as expected. The D ring adopts a C14-envelope conformation and the E ring is midway between a C22,O3 half-chair and a C22-envelope conformations. The A/B, B/C, and C/D ring junctions are trans. Crystal data: C₂₇H₃₈O₅·1/2C₄H₈O₂, Monoclinic, space group P2₁, a = 7.7363(18) b = 28.769(12) c = 12.038(6) Å, = 90.88(5), V = 2679.0(10) ų, Z = 4. The packing of the molecules is assumed to be dictated by van der Waals interactions and by intermolecular C—H ··· O hydrogen bonds.     

Steroids and related studies,part 66: Crystal and molecular structure of 17a-(2-acetoxyethyl)-17a-aza-d-homo-5-androsten-3β-yl-acetate methiodide (HS465), a monoquaternary azasteroid incorporating an acetylcholine-like moiety

The crystal stucture of a synthetic monoquaternary azasteroid containig an acetylcholine-like moiety, 17a-(2-acetoxyethyl)-17a-aza-d-homo-5 androsten-3-yl-acetate methiodide (HS465) (C₂₆H₄₂NO₄)⁺I^–, has been determined by the heavy-atom method and refined by full-matrix least squares toR=0.0410 for 2462 reflections, using MoK radiation (=0.7114 Å). The crystals are monoclinic:P2₁,a=15.244(4),b=9.009(6),c=9.886(3) Å,=104.26°(3),Z=2. RingsA andC have distorted-chair conformations, ring d-homo is a symmetrical chair, and ringB is a half-chair. The acetoxyethyl side-group appended to N(17a) simulates an acetylcholine-like moiety, and exhibits a conformation similar to that frequently adopted by acetylcholine itself in the presence of heavy anions.     

Structure of 5-benzoylamino-5-methyl-4-oxo-1,3-dioxane

The crystals of the title compound (C₁₂H₁₃NO₄) are orthorhombic,P2₁2₁2₁ witha=8.541(3),b=10.988(1), andc=11.912(1) Å.M _r =235.24, mp 427 K,Z=4,D _x =1.348 Mg m^–3, (MoK=0.71069 Å, =0.11 mm^–1,T=293 K. The structure was solved by direct methods and refined by full-matrixs least squares to a finalR=0.028 for 1180 observed reflections. The molecules are connected by N-HO (ring carbonyl) intermolecular HO hydrogen bonds of 2.24(2) Å. The 4-oxo-1,3-dioxane ring is in a slightly distorted sofa conformation with a C _s ¹ asymmetry parameter of 3.6(2)° and the 5-methyl substituent in a pseudoaxial position. The benzoyl oxygen is turned toward the ring, resulting in a close OH(C6) contact of 2.45(2) Å.     

Crystal and molecular structure of inner-chelatetrans-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane-7,16-diacetatozinc(II), C16H28N2O8Zn

The molecular structure of trans-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane-7,16-diacetatozinc(II), complex (I), has been investigated by X-ray diffraction methods. It crystallizes in the monoclinic space groupP2₁/c, witha=16.229(2),b=12.001(1),c=9.778(1) Å,=95.59(1)°, andZ=4. The structure was solved by direct methods, and refined by full-matrix least-squares toR=0.048. The zinc cation, placed asymmetrically in the macro-ring cavity, is six-coordinated to 2 N- and 2 O-atoms of the macrocycle, and to 2 O-atoms of two acetate groups, thus forming an irregular octahedral coordination sphere. The 18-diaza-crown-6 ring reveals approximate twofold symmetry (s=0.1 Å), with the axis through C2-C3 and C11-C12 midpoints.     

Synthesis,spectroscopic studies,and x-ray crystallographic analysis of the organotin carbohydrate: 1,2∶3,4-di-O-isopropylidene-6-O-triphenylstannylmethyl-α-D-galactopyranose

The title organotin carbohydrate, C₃₁H₃₆O₆Sn, has been synthesized and its molecular structure has been determined in solution and in the solid state. NMR, infrared, mass and X-ray crystallographic techniques were used. The chiral molecules crystallize in the monoclinic space group P2₁ withZ=2. The triphenyltin and carbohydrate moieties are linked by a trans methylene-oxygen-methylene arrangement. The pyranosyl ring adopts a twist-boat conformation and the isopropylidene rings adopt different (half-chair and envelope) forms. Solution and solid-state conformations are similar as only three ¹³C shift values are greater than 2ppm; the ¹¹⁹Sn value is 12 ppm.     

Structure of 1,2,3,4,9,9a-hexahydro-6,9a-diphenyl-1H-pyrimido[2,1-c][1,4]thiazine

The title compound C₁₈H₂₀N₂S is monoclinic, witha=10.256(2),b=7.470(4),c=21.377(4) Å,=101.52(2)°,z=4 and space groupP2₁/n. The structure was solved by direct methods, and refined by weighted full-matrix least squares. The refinement, based on 1373 reflections withI2.5 (I), converged to a finalR of 0.062 (R _w=0.060). The conformation of the thiazine ring is a distorted half chair, and that of the pyrimidine ring is a distorted chair. All nonhydrogen intermolecular distances are greater than 3.5 Å.     

Synthesis and absolute configuration of (+) α-hydroxymethyltyrosine by X-ray analysis of its N-benzoyl derivative

-Hydroxymethyltyrosine has been synthesized by a route involving-hydroxymethylation. Dextrorotatory N-benzoyl--hydroxymethyltyrosine4 crystallizes in space group P2₁2₁2₁ with cell parameters:a=13.2266(9),b=16.1099(9),c=7.4475(5) Å,V=15.86.9(2) ų,Z=4. The structure was solved by direct methods and refined toR=0.047 andR _w =0.066 with 1549 independent and 956 reflections. The absolute configuration of 1 was determined asR by the application of Hamilton test and by the estimation of the Bijvoet coefficientB. Just as in N-benzoyl--methylcysteine (Wieczorek et al., 1989), the-amino acid residue adopts the C⁵ ring conformation similar to the fully extended form. The two side chains also adopt an extended conformation around the C atom.     

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.     

Structure of 6α-methyl-17α-hydroxyprogesterone butanoate,C26H38O4

The title compound crystallizes in space groupP2₁2₁2₁ with lattice constantsa=16.253(3),b=17.107(3), andc=8.486(2) Å. The A ring has 1,2-half-chair conformation. The calculated steric energy of a 6-methyl-17-ester progesterone molecule is lower by about 4 kJ/mol for the normal A-ring conformation. The progesterone side chain has typical conformation for 17-ester steroids; the C(16)-C(17)-C(20)-O(20) torsion angle is –24.9(4)°.