Startseite Crystal structure of bis(dimethylammonium) poly[(μ4-1,1′-(1,4-phenylenebis(methylene))bis(1H-pyrazole-3,5-dicarboxylato))-κ6O1, N2:O2:O3:O1′,N2′]nickel (II)], C22H26N6NiO8
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Crystal structure of bis(dimethylammonium) poly[(μ4-1,1′-(1,4-phenylenebis(methylene))bis(1H-pyrazole-3,5-dicarboxylato))-κ6O1, N2:O2:O3:O1′,N2′]nickel (II)], C22H26N6NiO8

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Veröffentlicht/Copyright: 15. September 2023

Abstract

C22H26N6NiO8, monoclinic, P21/n (no. 14), a = 10.9372(7) Å, b = 10.4567(6) Å, c = 11.7618(7) Å, β = 116.5552(19)°, V = 1203.25(13) Å3, Z = 2, R gt (F) = 0.0406, wR ref (F2) = 0.1089, T = 297(2) K.

CCDC no.: 1923319

Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal: Green block
Size: 0.15 × 0.10 × 0.10 mm
Wavelength: Mo Kα radiation (0.71073 Å)
μ: 0.87 mm−1
Diffractometer, scan mode: Bruker APEX-II, φ and ω
θmax, completeness: 25.0°, >99 %
N(hkl)measured, N(hkl)unique, Rint: 8833, 2113, 0.038
Criterion for Iobs, N(hkl)gt: Iobs > 2 σ(Iobs), 1744
N(param)refined: 172
Programs: Bruker [1], SHELX [2], [3], [4]
Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

Atom x y z Uiso*/Ueq
Ni1 0.5000 0.5000 0.0000 0.0177 (2)
O1 0.5908 (2) 0.3932 (2) 0.1646 (2) 0.0281 (5)
O2 0.4348 (3) 0.3483 (3) 0.2317 (3) 0.0672 (11)
O3 0.8762 (2) −0.0936 (2) 0.5639 (2) 0.0250 (5)
O4 0.6731 (3) −0.0846 (3) 0.5641 (3) 0.0454 (7)
N1 0.7751 (3) 0.2178 (2) 0.3484 (2) 0.0217 (6)
N2 0.8274 (3) 0.1169 (2) 0.4248 (2) 0.0205 (6)
C1 0.7262 (3) 0.0684 (3) 0.4468 (3) 0.0231 (7)
C2 0.6078 (3) 0.1396 (3) 0.3832 (3) 0.0288 (8)
H2 0.5235 0.1256 0.3826 0.035*
C3 0.6406 (3) 0.2353 (3) 0.3212 (3) 0.0257 (7)
C4 0.8675 (3) 0.2956 (3) 0.3171 (3) 0.0251 (7)
H4A 0.8163 0.3326 0.2333 0.030*
H4B 0.9377 0.2409 0.3142 0.030*
C5 0.9352 (3) 0.4021 (3) 0.4119 (3) 0.0260 (7)
C6 1.0686 (4) 0.3876 (3) 0.5069 (4) 0.0360 (9)
H6 1.1156 0.3121 0.5119 0.043*
C7 0.8682 (4) 0.5159 (3) 0.4063 (3) 0.0352 (9)
H7 0.7793 0.5276 0.3432 0.042*
C8 0.7603 (3) −0.0458 (3) 0.5310 (3) 0.0257 (7)
C9 0.5479 (4) 0.3355 (3) 0.2314 (3) 0.0318 (8)
C10 0.0973 (8) 0.2709 (9) 0.1756 (8) 0.123 (3)
H10A 0.0849 0.3310 0.1096 0.184*
H10B 0.1088 0.3163 0.2507 0.184*
H10C 0.0186 0.2164 0.1480 0.184*
N3 0.2193 (5) 0.1928 (5) 0.2041 (5) 0.0853 (17)
H3A 0.2520 0.1588 0.2845 0.128*
H3B 0.2827 0.2498 0.2028 0.128*
C11 0.2124 (12) 0.0857 (9) 0.1203 (8) 0.157 (4)
H11A 0.1378 0.0305 0.1095 0.236*
H11B 0.2964 0.0384 0.1577 0.236*
H11C 0.1983 0.1183 0.0391 0.236*

1 Source of material

All chemicals were of analytical reagent grade and used without further purification. A mixture of Ni(NO3)2·6H2O (47.4 mg), 1,1′-(1,4-phenylenebis(methylene))bis-(1H-pyrazole-3,5-dicarboxylic acid) (20.7 mg) and acetonitrile/DMF/water (10 mL, 3/3/4, v/v/v) was placed in a 15 mL of Teflon-lined stainless steel autoclave. The mixture was heated under autogenous pressure at 433 K for 72 h and then cooled to room temperature. Green block crystals were collected by filtration, washed with H2O, and dried in air with 72 % yield.

2 Experimental details

The Multi-scan program SADABS [1] was used for absorption correction. The structures were solved by Direct Methods and refined using the SHELXS-97 [2,3] and SHELXL-2014/7, respectively [4]. Hydrogen atoms attached to C atoms were placed geometrically and refined using a riding model approximation, with C–H = 0.96 Å and Uiso (H) = 1.2 Ueq (C).

3 Comment

Polycarboxylate based pyrazoles have great benefits for the formation 2D or 3D metal–organic frameworks [5,6]. Among them, flexible multicarboxylate ligands have remarkable advantages because their conformational freedom and flexibility can be fine-tuned by themselves to match with the coordination preference of metal ions and lower the energetic arrangement in the self-assembly process. Many tetracarboxylate ligands have been utilized to create coordination polymers [7,8]. We recently studied the self-assembly reaction of 1,1′-(1,4-phenylenebis(methylene))bis(1H-pyrazole-3,5-dicarboxylate).

The asymmetric unit of the title complex 1, consists of a half Ni2+ ion, a half of a fully deprotonated 1,1′-(1,4-phenylenebis(methylene))bis-(1H-pyrazole-3,5-dicar-boxylate) anion, one noncoordinated dimethylammonium cation by hydrolysis of DMF. As can be deduced from the charge balance, the framework is anionic having a (−2) charge, and the electroneutrality is achieved by the incorporation of the protonated amine in the voids of the net. In 1, the Ni (II) ion is surrounded by four oxygen atoms from four 1,1′-(1,4-phenylenebis(methylene))bis-(1H-pyrazole-3,5-dicarboxylate) ligands and two nitrogen atoms of two ligands to present an octahedral geometry with separate cis and trans angles at the metal being 79.39(8)°–180.0°. The Ni–O and Ni–N bond lengths are in the range of 2.064(2)–2.0648(2) Å and 2.085(2) Å, respectively. These values are within the normal ranges [9,10] and close to those reported in other Ni(II) complexes [11]. In the polymer 1, two carboxyl groups of pyrazole are fully deprotonated, each ligand bridges two Ni (II) ions through chelating N, O atoms of the pyrazole ring and monodentate O atom of the same pyrazole ring, forming ⋯Ni–L–Ni–L⋯ chains parallel to the crystallographic b direction. The Ni⋯Ni distance separated by a μ-pyrazole-carboxylate bridge is 7.942(1) Å. The dihedral angle between the planes of the benzene ring and pyrazole rings is 71.07(3)°. The one-dimensional chains intersect to form an infinite two-dimensional network which contain nearly square [Ni4(L)4] units. For each unit, four 1,1′-(1,4-phenylenebis(methylene))bis-(1H-pyrazole-3,5-dicarboxylate anions act as the four edges, and four Ni (II) ions represent the four vertices. The lengths of the diagonals are 10.457 Å and 11.956 Å, and the interior angles are 82.68° and 97.32°. The ligand 1,1′-(1,4-phenylenebis(methylene))bis(1H-pyrazole-3,5-dicarboxylate)) is the same as the Cd compound {[Cd2L(H2O)2]·DMF·H2O}n [12], however, it exhibits different coordination mode.


Corresponding author: Fenfang Li, College of Chemistry and Chemical Engineering, Jinzhong University, Jinzhong, Shanxi 030619, People’s Republic of China, E-mail:

Acknowledgements

This work was supported by the Startup Fund of Doctors of Jinzhong University.

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: Startup Fund of Doctors of Jinzhong University.

  3. Conflict of interest statement: The author declares no conflicts of interest regarding this article.

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Received: 2023-03-15
Accepted: 2023-08-30
Published Online: 2023-09-15
Published in Print: 2023-12-15

© 2023 the author(s), published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 International License.

Artikel in diesem Heft

  1. Frontmatter
  2. New Crystal Structures
  3. Crystal structure of bis(dimethylammonium) poly[(μ4-1,1′-(1,4-phenylenebis(methylene))bis(1H-pyrazole-3,5-dicarboxylato))-κ6O1, N2:O2:O3:O1′,N2′]nickel (II)], C22H26N6NiO8
  4. Hydrothermal synthesis and crystal structure of catena-poly[diaqua-bis(μ2-4-((pyridin-4-ylmethyl)amino)benzoato-κ2N:O)cobalt(II)] 4,4′-bipyridine – water (1/2/2)
  5. Crystal structure of (2S,3S,4S,5S, Z)-2,3,5,6-tetrakis(benzyloxy)-4-hydroxyhexanal oxime, C34H37NO6
  6. The crystal structure of hexakis(3-thiophenecarboxylato-κ2O,O″)-bis(1,10-phenanthroline-κ2N,N′) trimanganese(II), C54H34N4O12S6Mn3
  7. Crystal structure of catena-poly[(μ2-1,4-di(pyridin-4-yl)benzene-κ2N:N′)-(4-bromobenzoate-κ2O:O′)-(μ-2-bromobenzoate-κ2O,O′)nickel(II)] – water (2/1), C30H21Br2N2NiO4.5
  8. The crystal structure of poly[(μ3-1,3-phenylenedioxydiacetate-κ5O,O,O′,O″,O‴)-bis(4′-(4-(1H-imidazol-1-yl)phenyl)-4,2′:6′,4″-terpyridine-kN) cadmium(II)], C58H42CdN10O6
  9. The crystal structure of 5-chloro-6′-methyl-3-(4-(methylsulfonyl)phenyl)-[2,3′-bipyridin]-1′-ium 4-methylbenzenesulfonate
  10. Crystal structure of poly[(μ-benzoato)-(μ-cis-4–hydroxy-D-proline)lithium], C12H14LiNO5
  11. The crystal structure of catena-poly[aqua-(4-iodopyridine-2,6-dicarboxylato-κ3N,O,O)-copper(II)] monohydrate, C7H6NO6ICu
  12. The crystal structure of catena-[diaqua-(4-acetylphenoxyacetato-κ2O,O)-bis(4-acetylphenoxyacetato-κ3O,O:O)-dihydrate-lanthanum(III)]–4,4′-bipyridine (2/1), C35H35NO14La
  13. The crystal structure of catena-poly[(4-iodopyridine-2,6-dicarboxylato-κ4 O,N,O′,O′′)(4-imidazol-1-yl-pyridine-κN)copper(II)], C15H9N4O4ICu
  14. Crystal structure of polybis(μ 4-3,5-dicarboxylatopyrazol-1-yl)-bis(N,N-dimethylformamide)tri-copper(II)–acetonitrile (1/2), C20H22Cu3N8O10
  15. Crystal structure of poly[(μ2-5-hydroxy-isophthalato-κ4O,O′:O″,O‴)-(μ2-1,5-bis(imidazol-2-methyl)pentane-κ2N:N′)cadmium(II)], C21H24CdN4O5
  16. The crystal structure of poly[bis(μ2-1,4-bi(1-imidazolyl)benzene-κ2N:N′)bis(μ2-4,4′-methylenebis(3-hydroxy-2-naphthoate)-κ2O:O′)cobalt(II)], C35H24CoN4O6
  17. The crystal structure of a cobalt-vanadium-oxido hydrate
  18. The crystal structure of catena-poly[(μ 2-2H-1,2,3-triazole-4,5-dicarboxylato-κ 2 O, O′)-(μ 2-1,3-bis((1H-imidazol-1-yl)methyl)benzene-κ 2 N,N′) zinc(II)], C18H15N7O4Zn
  19. Crystal structure of poly[diaqua-(bis(m2-1,4-bis(imidazol-1-ylmethyl)benzene)-κ2N,N′-manganese] dichloride, C28H32MnN8O2Cl2
  20. The crystal structure of 9,10-dimethoxy-5,6-dihydro-[1,3]dioxolo[4,5-g]isoquinolino [3,2-a]isoquinolin-7-ium (E)-3-(4-nitrophenyl)acrylate pentahydrate, C29H34N2O13
  21. Crystal structure of poly[(μ6-ammoniotris(methylene))tris(hydrogen phosphonato)cadmium(II)], C3H10CdNO9P3
  22. Crystal structure of Zn2[(1,1′-(hexane-1,6-diyl)bis(3-(pyridin-3-yl)urea))·(H2O)2·(DMF)2·(SO4)2], C24H50N8O18S2Zn2
  23. The crystal structure of 2-anilino-1,4-naphthoquinone, C10H11NO2
  24. Crystal structure of (E)-2-(2-(4-(diethylamino)styryl)-1-ethyl-1,4-dihydroquinolin-4-yl) malononitrile, C26H26N4
  25. Crystal structure of ethyl 2-((2,6-dichloro-4-(cyanomethyl)phenyl) amino)benzoate, C17H14Cl2N2O2
  26. Synthesis and crystal structure of 2-(3-oxo-3-phenylpropyl)isoindoline-1,3-dione, C17H13NO3
  27. The crystal structure of bis(acetonitrile-κ1N)tetrakis(μ2-2,6-difluorobenzoato-κ2O:O′)rhodium(II) (Rh–Rh), C32H18F8O8N2Rh2
  28. The crystal structure of a new polymorph of 6-hydroxy-2-naphthoic acid, C11H8O3
  29. The crystal structure of [(8-carboxymethoxy-quinoline-2-carboxylate-κ4N,O,O,O)-2,2′-bipyridine-κ2N-copper(II)] tetrahydrate, C22H23N3O9Cu
  30. The crystal structure of ethyl 4-hydroxy-2-(4-methoxyphenyl)-5-oxo-1-(2-oxo-2H-chromen-6-yl)-2,5-dihydro-1H-pyrrole-3-carboxylate, C23H19NO7
  31. Crystal structure of 7-hydroxy-3,4-dihydronaphthalen-1(2H)-one, C10H10O2
  32. Crystal structure of bis(tetrapropylammonium) dodecacarbonyltetratelluridotetraferrate(2-), (Pr4N)2[Fe4Te4(CO)12]
  33. The crystal structure of poly[bis(μ2−3−aminopyridine−4−carboxylatoκ2N:O)Zinc(II)], [Zn(C6H5N2O2)2] n
  34. The crystal structure of methyl 5-nitro-2-(tosyloxy)benzoate, C15H13NO7S
  35. The crystal structure of 18-crown-6 ― tetraaqua-dichlorido-di-μ2-chloridodicopper(II) (2/1), C12H32O10Cu2Cl4
  36. Crystal structure of 6,6a,7,8,9,10-hexahydro-5H-pyrazino [2,3-e]pyrido[1,2-a]pyrazine, C10H14N4
  37. Crystal structure of catena-poly-{diaqua-bis[μ-(((4-chlorophenyl)sulfonyl)glycinato-κO)](μ2-4, 4′-bipyridine-κ2N:N′)cobalt(II)} dihydrate, C26H30Cl2CoN4O12S2
  38. Crystal structure of bis{N′-[1,3-diphenylprop-2-en-1-ylidene]-N-phenylcarbamohydrazonothioato}zinc(II), C44H36N6S2Zn
  39. Crystal structure of tetraaqua-bis(((4-chlorophenyl)sulfonyl)glycinato-κO)cobalt(II) dihydrate, C16H26Cl2CoN2O14S2
  40. Crystal structure of 2-(5-phenyl-1-(quinolin-2-yl)-4,5-dihydro-1H-pyrazol-3-yl)phenol, C24H19N3O
  41. Crystal structure of 2-((2-fluoro-4-(trifluoromethyl)phenyl)(hydroxy)methyl)-7-methoxy-3,4-dihydronaphthalen-1((2H))-one, C19H16F4O3
  42. Crystal structure of 2-amino-4-(2-fluoro-3-(trifluoromethyl)phenyl)-9-methoxy-1,4,5,6-tetrahydrobenzo[h]quinazolin-3-ium chloride, C20H18ClF4N3O
  43. Crystal structure of (2-phenylimino methylquinoline-κ 2 N,N′)-bis(1–phenylpyrazole-κ 2 C,N)-iridium(III) hexafluorophosphate, C34H26F6IrN6P
  44. Crystal structure of (3-hydroxy-4-methoxyphenyl)(pyrrolidin-1-yl)methanone, C12H15NO3
  45. The crystal structure of bis(trimethylsulfoxonium) catena-poly[µ2-hexabromido-indium(III)sodium(I)] C6H18O2S2NaInBr6
  46. Crystal structure of N-cyclopropyl-3-hydroxy-4-methoxybenzamide, C11H13NO3
  47. The crystal structure of (bis(benzimidazol-2-yl-methyl)amine-κ3N,N,N )-(dihydrogen L-malate-κ2O,O )copper(II) perchlorate dihydrate, CuC20H24ClN5O12
  48. Crystal structure of (1E,1′E)-4,4′-(9,9-diethyl-9H-fluorene-2,7-diyl)dibenzaldehyde dioxime, C31H28N2O2
  49. Crystal structure of diethyl 1,9-bis(4-fluorophenyl)-4,6-diphenylhexahydro-3H-2,7,3,5-(epimethanetriyliminomethanetriyl)cyclopenta [b]pyridine-3,7(2H)-dicarboxylate, C40H36F2N2O4
  50. Crystal structure of bis(benzene-1 carboxylato-O 3,5-carboxyl-κ1O)-[(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ4N,N′,N′′,N′′′)nickel(II) ─ benzene-1,3,5-tricarboxylic acid ─ water (1/2/4), C52H66N4NiO28
  51. Crystal structure of 1,4-dibromo-2,5-bis(2-methoxyethoxy)benzene-1,4-diol, C12H16Br2O4
  52. Crystal structure of dicarbonyl[N,N′-(1,2-dimethyl-1,2-ethanediylidene)bis[2,6-bis(1-methylethyl)benzenamine]-N,N′]nickel(0), C30H40N2NiO2
  53. Crystal structure of 1,4-dibromo-2,5-bis(prop-2-yn-1-yloxy)benzene, C12H8Br2O2
  54. Crystal structure of O-(3-(benzo[d]thiazol-2-yl)naphthalen-2-yl) O-phenyl carbonothioate, C24H15NO2S2
  55. The crystal structure of (E)-4-fluoro-N′-(1-(4-hydroxyphenyl)propylidene)benzohydrazide, C16H15FN2O2
  56. Crystal structure of (E)-1-(benzo[d]thiazol-2-yl)-N-(4,5-dihydropyren-2-yl)methanimine, C24H16N2S
  57. Crystal structure of 3-((4-bromophenyl)thio)-1H-indole, C14H10BrNS
  58. Synthesis and crystal structure of 1-((7-hydroxy-3-(4-hydroxy-3-nitrophenyl)-4-oxo-4H-chromen-8-yl)methyl)piperidin-1-ium-4-carboxylate monohydrate, C22H22N2O9
  59. Synthesis and crystal structure of (3E,5S,10S,13S,14S,17Z)-17-ethylidene-10,13-dimethylhexadecahydro-3H-cyclopenta[α]phenanthren-3-one O-(methacryloyl) oxime, C50H74N2O4
  60. Crystal structure of the hydrogen storage active phase La12Mg46LiMn
  61. The crystal structure of the salt: 4-((1,3-dioxoisoindolin-2-yl)carbamoyl)pyridine-1-ium 2-carboxybenzoate, C14H10N3O3·C8H5O4
  62. Crystal structure of (2-(2-pyridine)-benzimidazole-κ2 N,N′)-bis(1-phenylpyrazole-κ2 C,N)iridium(III) hexafluorophosphate, C30H22F6IrN7P
  63. Crystal structure of dichlorido-bis[2-(2,4-difluorophenyl)pyridine-κ1N]platinum(II), C22H14Cl2F4N2Pt
  64. Crystal structure of (5R,8R,9R,10R,12R,13R,14R, 17S,17Z)-2-((3-fluoropyridin-4-yl)methylene)-12-hydroxy-4,4,8,10,14-pentamethyl-17-((R)-2,6,6-trimethyltetrahydro-2H-pyran-2-yl)hexadecahydro-3H-cyclopenta[a]phenanthren-3-one, C36H52FNO3
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