17-Deoxoestrone [estra-1,3,5(10)-trien-3-ol]–methanol (3/1)

Three independent molecules of the title estrone derivative and a molecule of methanol comprise the asymmetric unit of the title compound [systematic name: 13-methyl-6,7,8,9,11,12,13,14,15,16-decahydrocyclopenta[a]phenanthren-3-ol–methanol (3/1)], 3C18H24O·CH3OH. Two of the estrone molecules exhibit 50:50 disorder (one displays whole-molecule disorder and the other partial disorder in the fused five- and six-membered rings) so that five (partial) molecular conformations are discernable. The conformation of the six-membered ring abutting the aromatic ring is close to a half-chair in all five components. The conformation of the six-membered ring fused to the five-membered ring is based on a chair with varying degrees of distortion ranging from minor to significant. Two distinct conformations are found for the five-membered ring: in four molecules, the five-membered ring is twisted about the bond linking it to the six-membered ring, and in the other, the five-membered ring is an envelope with the quaternary C atom being the flap atom. The crystal packing features O—H⋯O hydrogen bonding whereby the four molecules comprising the asymmetric unit are linked into a supramolecular chain along the b axis.

Three independent molecules of the title estrone derivative and a molecule of methanol comprise the asymmetric unit of the title compound [systematic name: 13-methyl-6,7,8,9,11,12,-13,14,15,16-decahydrocyclopenta[a]phenanthren-3-ol-methanol (3/1)], 3C 18 H 24 OÁCH 3 OH. Two of the estrone molecules exhibit 50:50 disorder (one displays whole-molecule disorder and the other partial disorder in the fused five-and sixmembered rings) so that five (partial) molecular conformations are discernable. The conformation of the six-membered ring abutting the aromatic ring is close to a half-chair in all five components. The conformation of the six-membered ring fused to the five-membered ring is based on a chair with varying degrees of distortion ranging from minor to significant. Two distinct conformations are found for the five-membered ring: in four molecules, the five-membered ring is twisted about the bond linking it to the six-membered ring, and in the other, the five-membered ring is an envelope with the quaternary C atom being the flap atom. The crystal packing features O-HÁ Á ÁO hydrogen bonding whereby the four molecules comprising the asymmetric unit are linked into a supramolecular chain along the b axis.
The first independent molecule exhibits whole molecule disorder pivoted on the O1 atom. As seen from the overlay diagram, Fig. 4, the two components of equal weight, i.e. shown as red and green, have almost identical conformations. Referring to the Scheme for numbering of the rings, the six-membered ring B, being fused to an aromatic ring, has an half-chair conformation, six-membered ring C has a slightly twisted chair conformation, and five-membered ring C is twisted on the bond linking it to the six-membered ring. Disorder is also evident in the second independent molecule. In this case, the 50:50 disorder is restricted to rings C and D. As shown in pink and blue in Fig. 4, the rings have distinct conformations.
For the molecule illustrated in pink, ring B is an half-chair and the conformation of ring C is that of a twisted chair. Ring D is an envelope on the quaternary-C29 atom. In the second disordered conformation, ring B is an half-chair and ring C is a slightly twisted chair. Ring D is distinct from that in the first orientation in that is adopts a twisted conformation about the C25-C29 bond. The third independent molecule, shown as light-blue in Fig. 4, is different from the other molecules in that ring B is a slightly twisted half-chair, ring C is a slightly twisted chair, and ring C is twisted about the C43-C47 bond.
In the crystal packing, the four independent molecules are connected via a sequence of O-H···O hydrogen bonds, Table   1. These link molecules into a supramolecular chain along the b axis, Fig. 5.

Experimental
The title compound (I) was prepared by a modified procedure from Huang-Minlon (1949) Estrone (1.5 g) was dissolved in diethylene glycol (40 ml), with heating and stirring in an oil bath at 388-393 K. Hydrazine hydrate (98-100%) was added in four 3 ml portions at 15 min intervals. During this time stirring and heating was continued and the flask connected to a drying tube. While the temperature was raised to 423 K, nitrogen was bubbled through the reaction mixture to remove excess reagent and water as by-product. When most of the reagent had been evaporated, KOH pellets (9.6 g) were added.
The flask was then fitted with a 50 cm air condenser (with a drying tube), and the reaction mixture was refluxed for 2 h under nitrogen. The cooled basic reaction mixture was diluted with water and extracted three times with ether, and each extract was washed five times with water. The ether extracts were dried under vacuum and the residue crystallized from MeOH/water, yielding colourless crystals (1.305 g, 91%), M.pt. 401-403 K. This product was recrystallized three times from MeOH/water, yielding (I). M.pt. 407-408 K, (Lit. 407-407.5 K (Huang-Minlon, 1949)).
supplementary materials sup-2 Refinement Carbon-bound H-atoms were placed in calculated positions (C-H 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation, with U iso (H) set to 1.2 to 1.5U eq (C). The hydroxy H-atoms were similarly placed (O-H 0.84 Å) and their U iso (H) similarly tied. Of the three independent molecules, one (with O1) is whole-molecule disordered and another (with O2) is partially disordered. The disorder was assumed to be a 1:1 disorder as the occupancy could not be refined. The aromatic C-C distances were restrained to 1.39±0.01 Å and the aliphatic ones to 1.54±0.01 Å; for the aliphatic arbon atoms, the 1,3-related distances were restrained to 2.52±0.01 Å. The anisotropic displacement factors of the primed atoms were restrained to be equal to those of the unprimed ones, and the anisotropic displacement factors of the disordered carbon atoms were restrained to be nearly isotropic. In the absence of significant anomalous scattering effects, 2199 Friedel pairs were averaged in the final refinement. However, the absolute configuration was assigned on the basis of the known chirality of the estrone starting material. Fig. 1. The molecular structures of the first independent molecule comprising the asymmetric unit of (I) showing displacement ellipsoids at the 50% probability level.    supplementary materials sup-3 13-methyl-6,7,8,9,11,12,13,14,15,16-decahydrocyclopenta[a]phenanthren-3-ol-methanol (3/1)  108.9 C31-C29-C25 111.9 (6) C7-C6-H6 108.9 C31-C29-C28 114.0 (7) C15-C6-H6 108.9 C25-C29-C28 98.7 (8)