Two androst-5-ene derivatives: 16-[4-(3-chloropropoxy)-3-methoxybenzylidene]-17-oxoandrost-5-en-3[beta]-ol and 16-[3-methoxy-4-(2-pyrrolidin-1-ylethoxy)benzylidene]-3[beta]-pyrrolidinoandrost-5-en-17[beta]-ol monohydrate

In the steroidal nucleus of 16-[4-(3-chloro­propoxy)-3-methoxy­benzyl­idene]-17-oxoandrost-5-en-3[beta]-ol, C₃₀H₂₉ClO₄, (I), the outer two six-membered rings are in chair conformations, while the five-membered ring and the central six-membered ring of the steroidal nucleus adopt half-chair and envelope conformations, respectively. In 16-[3-methoxy-4-(2-pyrrolidin-1-yl­ethoxy)­benzyl­idene]-3[beta]-pyrrolidinoandrost-5-en-17[beta]-ol monohydrate, C₃₇H₅₄N₂O₃·H₂O, (II), one C atom of one of the outer six-membered rings of the steroid nucleus and the four C atoms of the ethoxy­pyrrolidine ring are disordered over two sites. The five-membered ring, and the central and one of the outer six-membered rings of the steroidal nucleus exhibit distorted half-chair, chair and envelope conformations, respectively. In (I), intermolecular O-H...O hydrogen bonds link the mol­ecules into chains via a co-operative O-H...O-H...O-H pattern. In (II), intermolecular O-H...O and O-H...N hydrogen bonds link the steroid and water mol­ecules alternately into extended chains.

S1. Comment

It is well known that minor changes in the basic composition of steroids significantly alter their chemical and biological activities (Duax & Norton, 1975). The present crystallographic analyses of 16-[4-(3-chloropropoxy)-3-methoxybenzylidene]-17-oxoandrost-5-en-3β-ol, (I), and 16-[3-methoxy-4-(2-pyrrolidin-1-ylethoxy)benzylidene]- 3β-pyrrolidinoandrost-5-en-17β-ol monohydrate, (II), have been carried out to study the influence of different functionalities on the steroid skeleton, in particular substituents at the C3, C16 and C17 positions. This study extends ongoing investigations into a series of similar synthetic androstene derivatives (Thamotharan et al., 2002, and references therein; Hema et al., 2003). \sch

Compounds (I) and (II) are androstene steroid derivatives in which rings A, B and C are essentially rigid, whereas ring D has a flexible conformation with respect to the side chain. Both compounds have the normal 8β,9α,10β,13β,14α configuration and the B/C and C/D ring junctions have the trans configuration (Figs. 1 and 2). The crystals of (I) are enantiomerically pure and the absolute configuration of the molecule has been confirmed independently by the X-ray diffraction experiment. In (II), the absence of any significant anomalous scatterers in the compound prevented the determination of the absolute configuration and the enantiomer used in the refinement was assigned to correspond with the known chiral centres in a precursor molecule, which remained unchanged during the synthesis of (II).

In compound (I) (Fig. 1), rings A and C are in chair conformations, as shown by the Cremer & Pople (1975) puckering parameters [ring A: Q = 0.550 (3) Å, q₂ = 0.078 (3) Å, q₃ = 0.545 (3) Å, θ = 7.9 (3)° and ϕ₂ = 107 (2)° for the atom sequence C1—C5/C10; ring C: Q = 0.577 (3) Å, q₂ = 0.053 (3) Å, q₃ = 0.575 (3) Å, θ = 5.2 (3)° and ϕ₂ = 269 (3)° for the atom sequence C8/C9/C11—C14]. Thus, the presence of a hydroxy group at C3 has not disturbed the usual chair conformation of ring A of the steroid nucleus. The C3—O3 bond is oriented equatorially and (-)synclinal to the C3—C4 bond. In contrast, it lies (+)antiperiplanar to the C3—C4 bond in a related structure reported from our laboratory (Hema et al., 2003). In ring B, the C5═C6 (Csp²—Csp²) distance of 1.324 (3) Å confirms the localization of a double bond at this position. This double bond imposes a 8β,9α-half-chair conformation on ring B, with puckering parameters of Q = 0.468 (3) Å, q₂ = 0.365 (3) Å, q₃ = 0.292 (3) Å, θ = 51.5 (3)° and ϕ₂ = 211.4 (4)° for the atom sequence C5—C10. Similar observations on the conformation of ring B in related structures have been reported by Caira et al. (1995), Hema et al. (2002), Vasuki et al. (2002) and Thamotharan et al. (2002). Ring D has a 14α-envelope conformation, with a pseudo-rotation angle of 12.4 (2)° and a maximum torsion angle of 42.5 (1)° (Rao et al., 1981) for the atom sequence C13—C17. Atom C14 is 0.142 (2) Å from the plane containing the four remaining atoms.

In compound (II) (Fig. 2), atom C4 in ring A of the steroid nucleus is disordered over two sites, so that ring A adopts two alternate conformations with the major conformation existing in 78.8 (7)% of the molecules. As seen from the puckering parameters, the major disordered component has a chair conformation [Q = 0.558 (3) Å, q₂ = 0.087 (3) Å, q₃ = 0.551 (3) Å, θ = 9.0 (3)° and ϕ₂ = 113 (2)° for the atom sequence C1—C4A/C5/C10], while the minor disordered component has a boat conformation distorted towards that of a screw-boat [Q = 0.569 (5) Å, q₂ = 0.556 (6) Å, q₃ = 0.120 (5) Å, θ = 77.8 (5)° and ϕ₂ = 8.8 (3)° for the atom sequence C1—C4B/C5/C10]. Ring B exhibits a slightly flattened half-chair conformation [Q = 0.454 (3) Å, q₂ = 0.281 (3) Å, q₃ = 0.356 (3) Å, θ = 38.3 (4)° and ϕ₂ = 208.7 (6)° for the atom sequence C5—C10], while ring C adopts a chair conformation [Q = 0.581 (3) Å, q₂ = 0.084 (3) Å, q₃ = 0.574 (3) Å, θ = 8.7 (3)° and ϕ₂ = 268.4 (18)° for the atom sequence C8/C9/C11—C14]. Ring D of the steroid exhibits an envelope conformation, as is evident from the pseudo-rotation angle of 345.0 (2)° and maximum torsion angle of 45.4 (1)° for the atom sequence C13—C17.

In (II), the four ring C atoms of the ethoxypyrrolidine ring are disordered over two almost equally occupied conformations. Both disordered components exhibit envelope conformations, as can be seen from the pseudo-rotation angles of 344.8 (8) and 346.8 (8)° and maximum torsion angles of 44.2 (6) and 44.3 (5)° for the atom sequences N30/C31A/C32A/C33A/C34A and N30/C31B/C32B/C33B/C34B, respectively. The pyrrolidine-ring substituent at C3 has an envelope conformation, with a pseudo-rotation angle of 348.0 (3)° and a maximum torsion angle of 42.7 (2)° for the atom sequence N37/C38—C41.

The C17—C16—C20—C21 torsion angles of −173.5 (2)° in (I) and 179.2 (2)° in (II) indicate that the benzylidene moiety has an E configuration with respect to the carbonyl or hydroxy substituted atom, C17. The chloropropoxy group in (I) projects in a planar zigzag fashion slightly away from the plane of the methoxybenzylidene ring [C25—C24—O28—C29 6.9 (4)°].

The pseudo-torsion angle C19—C10···C13—C18, which gives a quantitative measure of the molecular twist, is 13.84 (18) in (I) and 11.34 (19)° in (II). These values are comparable with those of related structures with bulky substitutions at C3 and C16 (Hema et al., 2002; Thamotharan et al., 2002). The C16—C20—C21—C22 torsion angles of 160.8 (3) in (I) and 5.7 (4)° in (II) indicate that the benzylidene moiety has been flipped by almost 180° about the C20—C21 bond in (II) with respect to its orientation in (I), thus bringing the methoxy group to the other side of the molecule. The A/B/C/D ring systems of both (I) and (II) could be superimposed on each other with a small r.m.s. deviation of the atoms of 0.084 Å.

In (I), the hydroxy substituent on atom C3 forms an intermolecular hydrogen bond with the hydroxy atom O3 of a symmetry-related molecule (Table 1). This interaction leads cooperatively to an O—H···O—H···O—H pattern, producing a chain which runs parallel to the [001] direction and has a graph-set motif of C(2) (Bernstein et al., 1995). As can be seen from Table 2, the hydroxy substituent on atom C17 in (II) forms an intermolecular O—H···O hydrogen bond with the O atom of the water molecule. In turn, the water molecule forms two intermolecular O—H···O and one intermolecular O—H···N hydrogen bonds with the methoxy, ethoxy and ethoxypyrrolidine O and N atoms, respectively, of a single adjacent steroid molecule. These three acceptor atoms form a pocket into which the water molecule is bound. The combination of all these interactions links the steroid and water molecules alternately into extended chains which run in the [101] direction. Binary graph-set motifs (Bernstein et al., 1995) of C₂²(11), C₂²(12) and C₂²(15) are present for the chain routes through acceptor atoms O37, O25 and N30, respectively. Ring motifs of R₁²(5), R₂²(7) and R₂²(10) are also formed by the various combinations of donor-acceptor interactions between the water molecule and the single acceptor steroid molecule.

S2. Experimental

To a stirred suspension of 16-[3-methoxy-4-(2-pyrrolidin-1-ylethoxy)benzylidene]-3-pyrrolidino- 3,5-androstadien-17-one (0.5 g, 0.871 mmol) in methanol (75 ml), sodium borohydride (1.0 g) was added in small amounts over a period of 2 h at room temperature. Stirring was continued for a further 4 h. Excess solvent was removed under vacuum and the reaction mixture was poured into ice-cold water (100 ml). The precipitate obtained was filtered, washed with water, dried and crystallized from methanol-acetone (Ratio?) to afford (I) (institution code: DPJ-RG-1122; yield: 0.38 g, 75.54%; m.p. 469–472 K). To a solution of dehydroepiandrosterone (0.75 g, 2.60 mmol) in methanol (10 ml), sodium hydroxide pellets (1.5 g) were added and dissolved. 4-(3-chloro)-propoxy-3-methoxybenzaldehyde (1 g, 4.373 mmol) was added dropwise and stirred for 2 h. The completion of the reaction was monitored using thin-layer chromatography. Ice-cold water was added to the reaction mixture and the precipitate obtained was filtered, washed, dried and crystallized from acetone to afford (II) (institution code: DPJ-RG-1150; yield: 1.5 g, 86.7%; m.p. 483–485 K).

S3. Refinement

For compound (II), atom C4 on ring A of the steroid nucleus is disordered over two sites. The four ring C atoms of the ethoxypyrrolidine moiety are also disordered over two conformations and two sets of positions were defined for pyrrolidine ring atoms C31—C34. Constrained refinement of the site-occupation factors for the two disordered regions led to values of 0.788 (7) and 0.510 (13), respectively, for the major conformations. The chemically equivalent bonds involving the disordered C atoms were restrained to have similar lengths and the 1,3 distances within each conformation of the pyrrolidine ring were also restrained to be similar. Neighbouring disordered atoms within and between each conformation of the disordered region were also restrained to have similar atomic displacement parameters. The position of the hydroxy H atom in (I) was determined from a difference Fourier map and refined freely along with its isotropic displacement parameters. The positions of the water H atoms in (II) were also determined from a difference Fourier map and were refined along with their isotropic displacement parameters, while restraining the O—H bond length to 0.82 Å. The methyl H atoms in both compounds were constrained to an ideal geometry (C—H = 0.98 Å), with U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about the C—C bonds. All remaining H atoms were placed in geometrically idealized positions (C—H = 0.95–1.00 Å) and were constrained ride on their parent atoms. The presence of Cl in compound (I) permitted the determination of the absolute configuration of the molecule by refining the Flack parameter [−0.21 (7); Flack, 1983; Flack & Bernardinelli, 2000]. How many Friedel pairs? Due to the absence of any significant anomalous scatterers in (II), attempts to confirm the absolute structure by refinement of the Flack parameter in the presence of 3177 sets of Friedel equivalents led to an inconclusive value of 0.0 (8). Therefore, the Friedel pairs were merged before the final refinement and the absolute configuration was assigned to correspond with the known chiral centres in a precursor molecule, which remained unchanged during the synthesis of (II). Reflections 1 1 2, 0 1 2 and 1 1 1 in (I), and 0 2 1, 0 1 1 and 0 4 0 in (II), were partially obscured by the beam stop and were omitted.

Computing details

For both compounds, data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1999); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures

	Fig. 1. A view of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. For clarity, all H atoms of the disordered rings have been omitted. The other H atoms are shown as small circles of arbitrary radii.
	Fig. 2. A view of the molecule of (II) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small circles of arbitrary radii.

(I) 16-[4-(3-chloropropoxy)-3-methoxybenzylidene]-17-oxoandrost-5-en-3β-ol

Crystal data

C30H39ClO4	Dx = 1.266 Mg m^−3
Mr = 499.09	Melting point: 469 K
Trigonal, R3	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: R 3	Cell parameters from 19304 reflections
a = 34.3749 (8) Å	θ = 2.0–27.5°
c = 5.7585 (1) Å	µ = 0.18 mm^−1
V = 5892.8 (2) Å^3	T = 160 K
Z = 9	Prism, colourless
F(000) = 2412	0.30 × 0.12 × 0.10 mm

Data collection

Nonius KappaCCD area-detector diffractometer	5990 independent reflections
Radiation source: Nonius FR591 sealed tube generator	5077 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.062
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 2.1°
ϕ and ω scans with κ offsets	h = −44→41
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −44→44
Tmin = 0.909, Tmax = 0.984	l = −7→7
29761 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.049	w = 1/[σ^2(Fo^2) + (0.0672P)^2 + 7.0766P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.127	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.60 e Å^−3
5987 reflections	Δρmin = −0.34 e Å^−3
324 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.00078 (19)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack & Bernardinelli (2000)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.21 (7)

Special details

Experimental. Solvent used: methnol-acetone mixture Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.464 (1) Frames collected: 222 Seconds exposure per frame: 120 Degrees rotation per frame: 2.0 Crystal-Detector distance (mm): 30.0

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	−0.06166 (3)	−0.00522 (3)	−0.34802 (14)	0.0493 (2)
O3	0.34998 (6)	0.03704 (6)	0.4690 (3)	0.0290 (4)
H3A	0.3353 (9)	0.0203 (9)	0.377 (5)	0.013 (7)*
O17	0.22766 (6)	0.26738 (7)	0.8851 (3)	0.0358 (4)
O23	−0.01387 (6)	0.15520 (7)	0.5467 (3)	0.0382 (5)
O28	−0.02007 (6)	0.10901 (7)	0.1773 (4)	0.0400 (5)
C1	0.34027 (8)	0.13116 (8)	0.7416 (4)	0.0241 (5)
H1A	0.3624	0.1575	0.8319	0.029*
H1B	0.3142	0.1131	0.8442	0.029*
C2	0.36165 (8)	0.10263 (9)	0.6755 (4)	0.0260 (5)
H2A	0.3898	0.1213	0.5878	0.031*
H2B	0.3693	0.0918	0.8182	0.031*
C3	0.32981 (8)	0.06328 (8)	0.5301 (4)	0.0248 (5)
H3	0.3018	0.0442	0.6214	0.030*
C4	0.31764 (9)	0.07993 (8)	0.3105 (4)	0.0254 (5)
H4A	0.3450	0.0977	0.2159	0.030*
H4B	0.2961	0.0539	0.2167	0.030*
C5	0.29703 (8)	0.10863 (8)	0.3712 (4)	0.0222 (5)
C6	0.25712 (8)	0.09782 (8)	0.2857 (4)	0.0255 (5)
H6	0.2425	0.0718	0.1906	0.031*
C7	0.23348 (8)	0.12370 (8)	0.3282 (4)	0.0265 (5)
H7A	0.2076	0.1061	0.4325	0.032*
H7B	0.2217	0.1278	0.1790	0.032*
C8	0.26414 (8)	0.16971 (8)	0.4371 (4)	0.0200 (5)
H8	0.2837	0.1909	0.3133	0.024*
C9	0.29420 (8)	0.16681 (8)	0.6278 (4)	0.0204 (4)
H9	0.2735	0.1446	0.7447	0.025*
C10	0.32422 (8)	0.14817 (7)	0.5334 (4)	0.0199 (4)
C11	0.32102 (8)	0.21191 (8)	0.7566 (4)	0.0240 (5)
H11A	0.3438	0.2342	0.6496	0.029*
H11B	0.3371	0.2078	0.8885	0.029*
C12	0.29172 (8)	0.23087 (8)	0.8496 (4)	0.0243 (5)
H12A	0.2716	0.2109	0.9729	0.029*
H12B	0.3112	0.2609	0.9181	0.029*
C13	0.26382 (8)	0.23446 (8)	0.6540 (4)	0.0214 (5)
C14	0.23609 (8)	0.18781 (7)	0.5438 (4)	0.0212 (5)
H14	0.2196	0.1671	0.6756	0.025*
C15	0.19985 (8)	0.19076 (8)	0.4008 (4)	0.0230 (5)
H15A	0.2119	0.2061	0.2505	0.028*
H15B	0.1736	0.1606	0.3721	0.028*
C16	0.18793 (8)	0.21839 (8)	0.5595 (4)	0.0233 (5)
C17	0.22647 (8)	0.24382 (8)	0.7243 (4)	0.0245 (5)
C18	0.29329 (8)	0.27166 (8)	0.4783 (4)	0.0255 (5)
H18A	0.3075	0.3009	0.5562	0.038*
H18B	0.2745	0.2717	0.3502	0.038*
H18C	0.3166	0.2660	0.4171	0.038*
C19	0.36533 (8)	0.18453 (8)	0.4001 (4)	0.0274 (5)
H19A	0.3811	0.1708	0.3250	0.041*
H19B	0.3857	0.2078	0.5088	0.041*
H19C	0.3553	0.1981	0.2818	0.041*
C20	0.14950 (8)	0.21898 (8)	0.5840 (4)	0.0259 (5)
H20	0.1497	0.2388	0.6997	0.031*
C21	0.10732 (8)	0.19336 (8)	0.4574 (4)	0.0261 (5)
C22	0.06748 (9)	0.18875 (9)	0.5571 (4)	0.0284 (5)
H22	0.0695	0.2048	0.6952	0.034*
C23	0.02602 (8)	0.16171 (9)	0.4593 (4)	0.0293 (5)
C24	0.02237 (9)	0.13695 (9)	0.2560 (5)	0.0306 (6)
C25	0.06123 (9)	0.14357 (9)	0.1482 (4)	0.0310 (6)
H25	0.0593	0.1288	0.0056	0.037*
C26	0.10314 (9)	0.17170 (9)	0.2474 (4)	0.0287 (5)
H26	0.1294	0.1762	0.1696	0.034*
C27	−0.01146 (10)	0.18450 (11)	0.7261 (5)	0.0405 (7)
H27A	0.0013	0.1789	0.8660	0.061*
H27B	−0.0417	0.1792	0.7603	0.061*
H27C	0.0077	0.2157	0.6763	0.061*
C29	−0.02468 (9)	0.08087 (11)	−0.0190 (5)	0.0388 (6)
H29A	−0.0118	0.0615	0.0178	0.047*
H29B	−0.0087	0.0996	−0.1556	0.047*
C30	−0.07440 (10)	0.05247 (13)	−0.0691 (6)	0.0527 (9)
H30A	−0.0883	0.0288	0.0510	0.063*
H30B	−0.0883	0.0716	−0.0577	0.063*
C31	−0.08459 (12)	0.03056 (13)	−0.3051 (7)	0.0545 (9)
H31A	−0.0725	0.0543	−0.4256	0.065*
H31B	−0.1176	0.0128	−0.3255	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0498 (5)	0.0436 (4)	0.0585 (5)	0.0262 (4)	−0.0040 (4)	−0.0074 (3)
O3	0.0324 (10)	0.0271 (9)	0.0341 (9)	0.0199 (8)	−0.0076 (8)	−0.0053 (8)
O17	0.0365 (10)	0.0395 (11)	0.0372 (10)	0.0233 (9)	−0.0040 (8)	−0.0156 (8)
O23	0.0255 (10)	0.0541 (13)	0.0387 (10)	0.0227 (9)	−0.0008 (8)	−0.0096 (9)
O28	0.0263 (10)	0.0507 (12)	0.0422 (11)	0.0186 (9)	−0.0065 (8)	−0.0158 (9)
C1	0.0279 (12)	0.0280 (12)	0.0195 (11)	0.0163 (10)	−0.0044 (9)	−0.0016 (9)
C2	0.0284 (12)	0.0307 (13)	0.0247 (11)	0.0190 (11)	−0.0033 (9)	−0.0008 (9)
C3	0.0246 (12)	0.0244 (12)	0.0289 (12)	0.0149 (10)	−0.0023 (9)	0.0013 (9)
C4	0.0308 (13)	0.0262 (12)	0.0232 (11)	0.0173 (11)	−0.0045 (9)	−0.0037 (9)
C5	0.0282 (12)	0.0208 (11)	0.0184 (10)	0.0128 (10)	−0.0019 (9)	−0.0005 (8)
C6	0.0298 (13)	0.0226 (12)	0.0261 (11)	0.0146 (10)	−0.0065 (9)	−0.0048 (9)
C7	0.0252 (12)	0.0240 (12)	0.0308 (12)	0.0127 (10)	−0.0089 (9)	−0.0075 (10)
C8	0.0198 (11)	0.0198 (11)	0.0206 (10)	0.0101 (9)	−0.0030 (8)	−0.0008 (8)
C9	0.0225 (11)	0.0219 (11)	0.0191 (10)	0.0128 (10)	−0.0023 (8)	−0.0002 (8)
C10	0.0214 (11)	0.0192 (11)	0.0185 (10)	0.0097 (9)	−0.0009 (8)	0.0004 (8)
C11	0.0246 (12)	0.0251 (12)	0.0246 (11)	0.0140 (10)	−0.0077 (9)	−0.0052 (9)
C12	0.0286 (12)	0.0241 (12)	0.0212 (11)	0.0139 (10)	−0.0043 (9)	−0.0034 (9)
C13	0.0237 (12)	0.0192 (11)	0.0215 (11)	0.0109 (9)	0.0001 (9)	−0.0012 (8)
C14	0.0216 (11)	0.0189 (11)	0.0215 (10)	0.0089 (9)	−0.0016 (8)	0.0010 (8)
C15	0.0211 (11)	0.0254 (12)	0.0244 (11)	0.0129 (10)	−0.0029 (9)	−0.0010 (9)
C16	0.0247 (12)	0.0206 (11)	0.0240 (11)	0.0110 (10)	0.0003 (9)	0.0011 (9)
C17	0.0267 (12)	0.0225 (12)	0.0251 (12)	0.0130 (10)	0.0007 (9)	0.0007 (9)
C18	0.0252 (12)	0.0213 (12)	0.0281 (12)	0.0102 (10)	−0.0007 (9)	0.0001 (9)
C19	0.0246 (12)	0.0274 (13)	0.0288 (12)	0.0120 (11)	0.0019 (10)	0.0015 (10)
C20	0.0276 (12)	0.0245 (12)	0.0285 (12)	0.0151 (10)	−0.0007 (10)	−0.0016 (9)
C21	0.0270 (13)	0.0267 (12)	0.0293 (12)	0.0169 (11)	−0.0001 (10)	0.0036 (10)
C22	0.0287 (13)	0.0323 (13)	0.0297 (12)	0.0195 (11)	0.0008 (10)	−0.0006 (10)
C23	0.0246 (12)	0.0375 (14)	0.0318 (13)	0.0200 (11)	0.0014 (10)	0.0003 (11)
C24	0.0260 (13)	0.0328 (14)	0.0334 (13)	0.0150 (11)	−0.0046 (10)	−0.0014 (10)
C25	0.0272 (13)	0.0388 (15)	0.0287 (13)	0.0178 (12)	−0.0023 (10)	−0.0034 (10)
C26	0.0263 (12)	0.0356 (14)	0.0284 (12)	0.0186 (11)	0.0017 (10)	0.0016 (10)
C27	0.0358 (15)	0.0527 (18)	0.0419 (15)	0.0288 (14)	0.0038 (12)	−0.0058 (13)
C29	0.0302 (14)	0.0447 (17)	0.0413 (15)	0.0185 (13)	−0.0046 (12)	−0.0122 (13)
C30	0.0304 (16)	0.064 (2)	0.061 (2)	0.0218 (16)	−0.0073 (14)	−0.0238 (17)
C31	0.050 (2)	0.061 (2)	0.064 (2)	0.0370 (18)	−0.0215 (16)	−0.0246 (18)

Geometric parameters (Å, º)

Cl1—C31	1.779 (3)	C12—H12B	0.9900
O3—C3	1.430 (3)	C13—C17	1.526 (3)
O3—H3A	0.76 (3)	C13—C14	1.534 (3)
O17—C17	1.218 (3)	C13—C18	1.546 (3)
O23—C23	1.370 (3)	C14—C15	1.538 (3)
O23—C27	1.416 (3)	C14—H14	1.0000
O28—C24	1.362 (3)	C15—C16	1.514 (3)
O28—C29	1.444 (3)	C15—H15A	0.9900
C1—C2	1.539 (3)	C15—H15B	0.9900
C1—C10	1.551 (3)	C16—C20	1.339 (3)
C1—H1A	0.9900	C16—C17	1.504 (3)
C1—H1B	0.9900	C18—H18A	0.9800
C2—C3	1.499 (3)	C18—H18B	0.9800
C2—H2A	0.9900	C18—H18C	0.9800
C2—H2B	0.9900	C19—H19A	0.9800
C3—C4	1.530 (3)	C19—H19B	0.9800
C3—H3	1.0000	C19—H19C	0.9800
C4—C5	1.515 (3)	C20—C21	1.460 (3)
C4—H4A	0.9900	C20—H20	0.9500
C4—H4B	0.9900	C21—C26	1.389 (4)
C5—C6	1.324 (3)	C21—C22	1.419 (3)
C5—C10	1.524 (3)	C22—C23	1.374 (4)
C6—C7	1.495 (3)	C22—H22	0.9500
C6—H6	0.9500	C23—C24	1.415 (4)
C7—C8	1.529 (3)	C24—C25	1.385 (4)
C7—H7A	0.9900	C25—C26	1.394 (4)
C7—H7B	0.9900	C25—H25	0.9500
C8—C14	1.515 (3)	C26—H26	0.9500
C8—C9	1.545 (3)	C27—H27A	0.9800
C8—H8	1.0000	C27—H27B	0.9800
C9—C11	1.541 (3)	C27—H27C	0.9800
C9—C10	1.560 (3)	C29—C30	1.513 (4)
C9—H9	1.0000	C29—H29A	0.9900
C10—C19	1.543 (3)	C29—H29B	0.9900
C11—C12	1.544 (3)	C30—C31	1.507 (5)
C11—H11A	0.9900	C30—H30A	0.9900
C11—H11B	0.9900	C30—H30B	0.9900
C12—C13	1.523 (3)	C31—H31A	0.9900
C12—H12A	0.9900	C31—H31B	0.9900
C3—O3—H3A	108 (2)	C8—C14—C13	113.99 (18)
C23—O23—C27	117.0 (2)	C8—C14—C15	120.86 (19)
C24—O28—C29	116.9 (2)	C13—C14—C15	104.66 (19)
C2—C1—C10	114.97 (18)	C8—C14—H14	105.4
C2—C1—H1A	108.5	C13—C14—H14	105.4
C10—C1—H1A	108.5	C15—C14—H14	105.4
C2—C1—H1B	108.5	C16—C15—C14	101.56 (18)
C10—C1—H1B	108.5	C16—C15—H15A	111.5
H1A—C1—H1B	107.5	C14—C15—H15A	111.5
C3—C2—C1	110.31 (19)	C16—C15—H15B	111.5
C3—C2—H2A	109.6	C14—C15—H15B	111.5
C1—C2—H2A	109.6	H15A—C15—H15B	109.3
C3—C2—H2B	109.6	C20—C16—C17	120.9 (2)
C1—C2—H2B	109.6	C20—C16—C15	130.6 (2)
H2A—C2—H2B	108.1	C17—C16—C15	108.02 (19)
O3—C3—C2	109.94 (19)	O17—C17—C16	126.4 (2)
O3—C3—C4	110.0 (2)	O17—C17—C13	126.1 (2)
C2—C3—C4	109.7 (2)	C16—C17—C13	107.44 (19)
O3—C3—H3	109.1	C13—C18—H18A	109.5
C2—C3—H3	109.1	C13—C18—H18B	109.5
C4—C3—H3	109.1	H18A—C18—H18B	109.5
C5—C4—C3	110.92 (19)	C13—C18—H18C	109.5
C5—C4—H4A	109.5	H18A—C18—H18C	109.5
C3—C4—H4A	109.5	H18B—C18—H18C	109.5
C5—C4—H4B	109.5	C10—C19—H19A	109.5
C3—C4—H4B	109.5	C10—C19—H19B	109.5
H4A—C4—H4B	108.0	H19A—C19—H19B	109.5
C6—C5—C4	119.2 (2)	C10—C19—H19C	109.5
C6—C5—C10	124.4 (2)	H19A—C19—H19C	109.5
C4—C5—C10	116.36 (19)	H19B—C19—H19C	109.5
C5—C6—C7	124.6 (2)	C16—C20—C21	128.9 (2)
C5—C6—H6	117.7	C16—C20—H20	115.5
C7—C6—H6	117.7	C21—C20—H20	115.5
C6—C7—C8	112.6 (2)	C26—C21—C22	117.2 (2)
C6—C7—H7A	109.1	C26—C21—C20	124.3 (2)
C8—C7—H7A	109.1	C22—C21—C20	118.5 (2)
C6—C7—H7B	109.1	C23—C22—C21	121.8 (2)
C8—C7—H7B	109.1	C23—C22—H22	119.1
H7A—C7—H7B	107.8	C21—C22—H22	119.1
C14—C8—C7	109.88 (19)	O23—C23—C22	125.1 (2)
C14—C8—C9	108.77 (17)	O23—C23—C24	115.2 (2)
C7—C8—C9	111.24 (19)	C22—C23—C24	119.7 (2)
C14—C8—H8	109.0	O28—C24—C25	124.9 (2)
C7—C8—H8	109.0	O28—C24—C23	116.2 (2)
C9—C8—H8	109.0	C25—C24—C23	118.9 (2)
C11—C9—C8	111.12 (18)	C24—C25—C26	120.5 (2)
C11—C9—C10	113.27 (18)	C24—C25—H25	119.8
C8—C9—C10	112.32 (17)	C26—C25—H25	119.8
C11—C9—H9	106.5	C21—C26—C25	121.5 (2)
C8—C9—H9	106.5	C21—C26—H26	119.2
C10—C9—H9	106.5	C25—C26—H26	119.2
C5—C10—C19	108.81 (18)	O23—C27—H27A	109.5
C5—C10—C1	108.22 (18)	O23—C27—H27B	109.5
C19—C10—C1	109.60 (19)	H27A—C27—H27B	109.5
C5—C10—C9	110.07 (18)	O23—C27—H27C	109.5
C19—C10—C9	111.52 (18)	H27A—C27—H27C	109.5
C1—C10—C9	108.56 (17)	H27B—C27—H27C	109.5
C9—C11—C12	113.79 (19)	O28—C29—C30	107.0 (2)
C9—C11—H11A	108.8	O28—C29—H29A	110.3
C12—C11—H11A	108.8	C30—C29—H29A	110.3
C9—C11—H11B	108.8	O28—C29—H29B	110.3
C12—C11—H11B	108.8	C30—C29—H29B	110.3
H11A—C11—H11B	107.7	H29A—C29—H29B	108.6
C13—C12—C11	110.34 (18)	C31—C30—C29	113.5 (3)
C13—C12—H12A	109.6	C31—C30—H30A	108.9
C11—C12—H12A	109.6	C29—C30—H30A	108.9
C13—C12—H12B	109.6	C31—C30—H30B	108.9
C11—C12—H12B	109.6	C29—C30—H30B	108.9
H12A—C12—H12B	108.1	H30A—C30—H30B	107.7
C12—C13—C17	116.82 (19)	C30—C31—Cl1	113.5 (2)
C12—C13—C14	107.98 (18)	C30—C31—H31A	108.9
C17—C13—C14	100.45 (18)	Cl1—C31—H31A	108.9
C12—C13—C18	111.84 (19)	C30—C31—H31B	108.9
C17—C13—C18	105.76 (19)	Cl1—C31—H31B	108.9
C14—C13—C18	113.66 (18)	H31A—C31—H31B	107.7
C10—C1—C2—C3	−56.0 (3)	C18—C13—C14—C8	63.2 (3)
C1—C2—C3—O3	179.85 (19)	C12—C13—C14—C15	164.34 (18)
C1—C2—C3—C4	58.8 (3)	C17—C13—C14—C15	41.5 (2)
O3—C3—C4—C5	−178.87 (19)	C18—C13—C14—C15	−71.0 (2)
C2—C3—C4—C5	−57.8 (3)	C8—C14—C15—C16	−169.5 (2)
C3—C4—C5—C6	−124.9 (2)	C13—C14—C15—C16	−39.2 (2)
C3—C4—C5—C10	54.0 (3)	C14—C15—C16—C20	−151.3 (3)
C4—C5—C6—C7	−178.8 (2)	C14—C15—C16—C17	21.2 (2)
C10—C5—C6—C7	2.3 (4)	C20—C16—C17—O17	−2.0 (4)
C5—C6—C7—C8	12.5 (3)	C15—C16—C17—O17	−175.4 (2)
C6—C7—C8—C14	−162.4 (2)	C20—C16—C17—C13	177.6 (2)
C6—C7—C8—C9	−41.9 (3)	C15—C16—C17—C13	4.3 (3)
C14—C8—C9—C11	−52.2 (2)	C12—C13—C17—O17	35.3 (3)
C7—C8—C9—C11	−173.4 (2)	C14—C13—C17—O17	151.8 (2)
C14—C8—C9—C10	179.71 (18)	C18—C13—C17—O17	−89.8 (3)
C7—C8—C9—C10	58.6 (2)	C12—C13—C17—C16	−144.3 (2)
C6—C5—C10—C19	−109.5 (3)	C14—C13—C17—C16	−27.9 (2)
C4—C5—C10—C19	71.6 (2)	C18—C13—C17—C16	90.5 (2)
C6—C5—C10—C1	131.5 (2)	C17—C16—C20—C21	−173.5 (2)
C4—C5—C10—C1	−47.4 (3)	C15—C16—C20—C21	−1.9 (4)
C6—C5—C10—C9	13.0 (3)	C16—C20—C21—C26	−16.9 (4)
C4—C5—C10—C9	−165.90 (19)	C16—C20—C21—C22	160.8 (3)
C2—C1—C10—C5	48.0 (3)	C26—C21—C22—C23	4.2 (4)
C2—C1—C10—C19	−70.6 (3)	C20—C21—C22—C23	−173.8 (2)
C2—C1—C10—C9	167.4 (2)	C27—O23—C23—C22	11.9 (4)
C11—C9—C10—C5	−169.45 (18)	C27—O23—C23—C24	−169.9 (2)
C8—C9—C10—C5	−42.5 (2)	C21—C22—C23—O23	179.2 (2)
C11—C9—C10—C19	−48.6 (2)	C21—C22—C23—C24	1.2 (4)
C8—C9—C10—C19	78.3 (2)	C29—O28—C24—C25	6.9 (4)
C11—C9—C10—C1	72.3 (2)	C29—O28—C24—C23	−175.3 (2)
C8—C9—C10—C1	−160.81 (18)	O23—C23—C24—O28	−1.8 (4)
C8—C9—C11—C12	52.1 (3)	C22—C23—C24—O28	176.4 (2)
C10—C9—C11—C12	179.63 (18)	O23—C23—C24—C25	176.2 (2)
C9—C11—C12—C13	−54.5 (3)	C22—C23—C24—C25	−5.6 (4)
C11—C12—C13—C17	168.4 (2)	O28—C24—C25—C26	−177.6 (2)
C11—C12—C13—C14	56.2 (2)	C23—C24—C25—C26	4.6 (4)
C11—C12—C13—C18	−69.6 (2)	C22—C21—C26—C25	−5.2 (4)
C7—C8—C14—C13	−178.88 (19)	C20—C21—C26—C25	172.6 (2)
C9—C8—C14—C13	59.1 (2)	C24—C25—C26—C21	0.9 (4)
C7—C8—C14—C15	−52.8 (3)	C24—O28—C29—C30	178.6 (3)
C9—C8—C14—C15	−174.8 (2)	O28—C29—C30—C31	164.3 (3)
C12—C13—C14—C8	−61.5 (2)	C29—C30—C31—Cl1	58.9 (4)
C17—C13—C14—C8	175.67 (18)	C19—C10—C13—C18	13.84 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O3^i	0.76 (3)	1.95 (3)	2.710 (2)	177 (3)

Symmetry code: (i) −y+1/3, x−y−1/3, z−1/3.

(II) 16-[3-methoxy-4-(2-pyrrolidin-1-ylethoxy)benzylidene]- 3β-pyrrolidinoandrost-5-en-17β-ol monohydrate

Crystal data

C37H54N2O3·H2O	F(000) = 648
Mr = 592.86	Dx = 1.185 Mg m^−3
Monoclinic, P21	Melting point: 483 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 6.4219 (1) Å	Cell parameters from 3313 reflections
b = 32.4115 (5) Å	θ = 2.0–26.0°
c = 8.0981 (1) Å	µ = 0.08 mm^−1
β = 99.6510 (7)°	T = 160 K
V = 1661.71 (4) Å^3	Prism, colourless
Z = 2	0.28 × 0.18 × 0.15 mm

Data collection

Nonius KappaCCD area-detector diffractometer	2865 reflections with I > 2σ(I)
Radiation source: Nonius FR591 sealed tube generator	Rint = 0.052
Horizontally mounted graphite crystal monochromator	θmax = 26.0°, θmin = 2.6°
Detector resolution: 9 pixels mm^-1	h = −7→7
ϕ and ω scans with κ offsets	k = −39→39
36139 measured reflections	l = −9→9
3302 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.092	w = 1/[σ^2(Fo^2) + (0.050P)^2 + 0.1844P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
3299 reflections	Δρmax = 0.23 e Å^−3
451 parameters	Δρmin = −0.22 e Å^−3
120 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.017 (5)

Special details

Experimental. Solvent used: acetone Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.464 (1) Frames collected: 1976 Seconds exposure per frame: 91 Degrees rotation per frame: 0.76 Crystal-Detector distance (mm): 50.0

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	−0.4812 (4)	0.11425 (9)	0.2016 (3)	0.0411 (6)
H1A	−0.5098	0.1087	0.3160	0.049*
H1B	−0.5649	0.1388	0.1584	0.049*
C2	−0.5581 (4)	0.07741 (9)	0.0906 (3)	0.0436 (7)
H2A	−0.4861	0.0521	0.1391	0.052*
H2B	−0.7117	0.0738	0.0875	0.052*
C3	−0.5150 (5)	0.08320 (9)	−0.0859 (3)	0.0473 (7)
H3A	−0.5895	0.1085	−0.1359	0.057*	0.788 (7)
H3B	−0.6420	0.1006	−0.1265	0.057*	0.212 (7)
C4A	−0.2713 (6)	0.08913 (12)	−0.0720 (4)	0.0441 (11)	0.788 (7)
H4A	−0.1983	0.0638	−0.0246	0.053*	0.788 (7)
H4B	−0.2365	0.0934	−0.1853	0.053*	0.788 (7)
C4B	−0.3505 (13)	0.1154 (3)	−0.1141 (9)	0.037 (3)	0.212 (7)
H4C	−0.2751	0.1053	−0.2034	0.044*	0.212 (7)
H4D	−0.4246	0.1412	−0.1546	0.044*	0.212 (7)
C5	−0.1939 (4)	0.12490 (8)	0.0354 (3)	0.0380 (6)
C6	−0.0589 (5)	0.15179 (9)	−0.0151 (3)	0.0472 (7)
H6	−0.0102	0.1463	−0.1174	0.057*
C7	0.0195 (4)	0.18975 (8)	0.0791 (3)	0.0350 (5)
H7A	−0.0685	0.2135	0.0333	0.042*
H7B	0.1663	0.1952	0.0627	0.042*
C8	0.0142 (4)	0.18601 (7)	0.2657 (3)	0.0312 (5)
H8	0.1309	0.1672	0.3171	0.037*
C9	−0.1988 (4)	0.16764 (7)	0.2954 (3)	0.0320 (5)
H9	−0.3110	0.1865	0.2376	0.038*
C10	−0.2450 (4)	0.12454 (8)	0.2131 (3)	0.0340 (5)
C11	−0.2203 (4)	0.16805 (8)	0.4822 (3)	0.0362 (6)
H11A	−0.1243	0.1470	0.5418	0.043*
H11B	−0.3666	0.1601	0.4923	0.043*
C12	−0.1696 (4)	0.21018 (8)	0.5693 (3)	0.0341 (5)
H12A	−0.2787	0.2306	0.5228	0.041*
H12B	−0.1721	0.2074	0.6906	0.041*
C13	0.0473 (4)	0.22550 (8)	0.5432 (3)	0.0310 (5)
C14	0.0437 (4)	0.22780 (7)	0.3529 (3)	0.0303 (5)
H14	−0.0838	0.2445	0.3066	0.036*
C15	0.2353 (4)	0.25440 (7)	0.3320 (3)	0.0332 (5)
H15A	0.3626	0.2372	0.3321	0.040*
H15B	0.2077	0.2704	0.2265	0.040*
C16	0.2619 (4)	0.28275 (7)	0.4838 (3)	0.0318 (5)
C17	0.0949 (4)	0.27104 (8)	0.5896 (3)	0.0332 (5)
H17	−0.0352	0.2877	0.5511	0.040*
O17	0.1562 (3)	0.27666 (7)	0.7643 (2)	0.0426 (4)
H17A	0.139 (5)	0.3019 (12)	0.786 (4)	0.062 (11)*
C18	0.2270 (4)	0.19869 (8)	0.6355 (3)	0.0373 (6)
H18A	0.2285	0.2005	0.7565	0.056*
H18B	0.3623	0.2085	0.6097	0.056*
H18C	0.2050	0.1699	0.5993	0.056*
C19	−0.1098 (5)	0.09070 (8)	0.3131 (4)	0.0469 (7)
H19A	−0.1224	0.0650	0.2482	0.070*
H19B	−0.1594	0.0861	0.4197	0.070*
H19C	0.0384	0.0994	0.3351	0.070*
C20	0.4024 (4)	0.31267 (7)	0.5286 (3)	0.0336 (5)
H20	0.3888	0.3263	0.6302	0.040*
C21	0.5748 (4)	0.32813 (7)	0.4469 (3)	0.0322 (5)
C22	0.6113 (4)	0.31484 (7)	0.2886 (3)	0.0318 (5)
H22	0.5210	0.2947	0.2289	0.038*
C23	0.7762 (4)	0.33061 (7)	0.2191 (3)	0.0318 (5)
C24	0.9123 (4)	0.36041 (7)	0.3045 (3)	0.0333 (5)
C25	0.8775 (4)	0.37374 (8)	0.4601 (3)	0.0374 (6)
H25	0.9679	0.3939	0.5197	0.045*
C26	0.7108 (4)	0.35774 (8)	0.5291 (3)	0.0350 (6)
H26	0.6890	0.3673	0.6358	0.042*
O27	1.0729 (3)	0.37382 (5)	0.2248 (2)	0.0371 (4)
C28	1.1991 (4)	0.40731 (8)	0.3026 (3)	0.0400 (6)
H28A	1.2599	0.3999	0.4193	0.048*
H28B	1.1100	0.4321	0.3055	0.048*
C29	1.3735 (4)	0.41640 (8)	0.2055 (3)	0.0392 (6)
H29A	1.4526	0.4408	0.2560	0.047*
H29B	1.4724	0.3927	0.2179	0.047*
O35	0.8209 (3)	0.31898 (5)	0.0657 (2)	0.0393 (4)
C36	0.6711 (4)	0.29305 (9)	−0.0370 (3)	0.0436 (6)
H36A	0.6596	0.2667	0.0201	0.065*
H36B	0.7183	0.2881	−0.1442	0.065*
H36C	0.5329	0.3067	−0.0571	0.065*
N37	−0.5787 (3)	0.04787 (7)	−0.1941 (3)	0.0416 (5)
C38	−0.8023 (5)	0.03839 (10)	−0.2159 (4)	0.0517 (7)
H38A	−0.8881	0.0636	−0.2427	0.062*
H38B	−0.8389	0.0258	−0.1131	0.062*
C39	−0.8393 (5)	0.00809 (10)	−0.3610 (4)	0.0539 (7)
H39A	−0.9826	0.0115	−0.4271	0.065*
H39B	−0.8223	−0.0207	−0.3202	0.065*
C40	−0.6695 (5)	0.01924 (9)	−0.4658 (4)	0.0511 (7)
H40A	−0.5811	−0.0050	−0.4809	0.061*
H40B	−0.7344	0.0298	−0.5773	0.061*
C41	−0.5402 (6)	0.05229 (12)	−0.3652 (4)	0.0635 (9)
H41A	−0.3882	0.0486	−0.3699	0.076*
H41B	−0.5842	0.0800	−0.4095	0.076*
C31A	1.1844 (18)	0.4617 (3)	−0.0278 (11)	0.064 (2)	0.510 (13)
H31A	1.2430	0.4861	0.0373	0.077*	0.510 (13)
H31B	1.0339	0.4585	−0.0172	0.077*	0.510 (13)
C32A	1.211 (2)	0.4655 (3)	−0.2121 (9)	0.069 (3)	0.510 (13)
H32A	1.0936	0.4514	−0.2863	0.083*	0.510 (13)
H32B	1.2147	0.4948	−0.2459	0.083*	0.510 (13)
C33A	1.4219 (19)	0.4441 (3)	−0.2191 (9)	0.077 (2)	0.510 (13)
H33A	1.5240	0.4640	−0.2531	0.093*	0.510 (13)
H33B	1.4022	0.4211	−0.3007	0.093*	0.510 (13)
C34A	1.5028 (10)	0.4277 (4)	−0.0419 (11)	0.060 (2)	0.510 (13)
H34A	1.5725	0.4006	−0.0455	0.072*	0.510 (13)
H34B	1.6027	0.4473	0.0233	0.072*	0.510 (13)
N30	1.3057 (3)	0.42420 (7)	0.0287 (3)	0.0452 (6)
C31B	1.1416 (15)	0.4567 (3)	0.0084 (11)	0.057 (2)	0.490 (13)
H31C	1.1905	0.4813	0.0763	0.068*	0.490 (13)
H31D	1.0095	0.4464	0.0418	0.068*	0.490 (13)
C32B	1.1081 (18)	0.4667 (3)	−0.1796 (10)	0.071 (2)	0.490 (13)
H32C	0.9949	0.4494	−0.2427	0.086*	0.490 (13)
H32D	1.0715	0.4962	−0.1999	0.086*	0.490 (13)
C33B	1.3228 (18)	0.4567 (3)	−0.2288 (9)	0.070 (3)	0.490 (13)
H33C	1.3874	0.4820	−0.2669	0.084*	0.490 (13)
H33D	1.3059	0.4362	−0.3208	0.084*	0.490 (13)
C34B	1.4621 (12)	0.4391 (4)	−0.0720 (11)	0.064 (2)	0.490 (13)
H34C	1.5514	0.4162	−0.1012	0.077*	0.490 (13)
H34D	1.5538	0.4607	−0.0116	0.077*	0.490 (13)
O1W	0.0923 (4)	0.35589 (7)	0.8658 (3)	0.0610 (6)
H1W	0.169 (6)	0.3746 (11)	0.924 (5)	0.098 (14)*
H2W	0.010 (6)	0.3471 (12)	0.935 (4)	0.098 (15)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0412 (15)	0.0476 (15)	0.0378 (13)	−0.0062 (12)	0.0164 (11)	−0.0051 (11)
C2	0.0434 (16)	0.0482 (16)	0.0427 (15)	−0.0089 (12)	0.0178 (12)	−0.0041 (12)
C3	0.0608 (18)	0.0465 (15)	0.0382 (14)	−0.0161 (13)	0.0184 (13)	−0.0068 (12)
C4A	0.048 (2)	0.049 (2)	0.0389 (19)	−0.0111 (17)	0.0183 (16)	−0.0069 (16)
C4B	0.045 (6)	0.025 (6)	0.040 (6)	0.017 (5)	0.007 (5)	0.003 (5)
C5	0.0445 (15)	0.0362 (13)	0.0368 (13)	−0.0026 (11)	0.0170 (11)	−0.0028 (11)
C6	0.0634 (19)	0.0514 (16)	0.0304 (13)	−0.0179 (14)	0.0178 (12)	−0.0058 (12)
C7	0.0394 (14)	0.0361 (13)	0.0321 (13)	−0.0026 (11)	0.0133 (10)	0.0015 (10)
C8	0.0315 (12)	0.0338 (12)	0.0299 (12)	0.0023 (10)	0.0092 (10)	0.0036 (10)
C9	0.0337 (13)	0.0324 (12)	0.0309 (12)	−0.0007 (10)	0.0084 (10)	0.0017 (10)
C10	0.0366 (13)	0.0338 (12)	0.0336 (12)	−0.0013 (11)	0.0114 (10)	0.0016 (10)
C11	0.0380 (14)	0.0390 (13)	0.0341 (13)	−0.0036 (11)	0.0131 (11)	0.0020 (10)
C12	0.0355 (13)	0.0387 (13)	0.0300 (12)	−0.0006 (11)	0.0110 (10)	0.0011 (10)
C13	0.0294 (12)	0.0371 (12)	0.0275 (11)	0.0008 (10)	0.0076 (9)	0.0021 (10)
C14	0.0296 (12)	0.0329 (12)	0.0292 (11)	0.0002 (10)	0.0074 (9)	0.0033 (10)
C15	0.0370 (13)	0.0361 (13)	0.0279 (12)	0.0001 (11)	0.0093 (10)	0.0008 (10)
C16	0.0303 (13)	0.0356 (13)	0.0299 (12)	0.0018 (10)	0.0062 (10)	0.0012 (10)
C17	0.0329 (13)	0.0409 (13)	0.0264 (11)	0.0006 (10)	0.0066 (10)	0.0003 (10)
O17	0.0489 (11)	0.0517 (12)	0.0281 (9)	−0.0046 (9)	0.0089 (8)	−0.0051 (8)
C18	0.0365 (14)	0.0435 (14)	0.0329 (12)	0.0040 (11)	0.0086 (10)	0.0057 (11)
C19	0.0522 (17)	0.0344 (14)	0.0540 (16)	0.0006 (12)	0.0087 (13)	0.0042 (12)
C20	0.0341 (13)	0.0379 (13)	0.0295 (11)	0.0013 (11)	0.0080 (10)	−0.0010 (10)
C21	0.0310 (12)	0.0340 (12)	0.0314 (12)	0.0033 (10)	0.0044 (10)	0.0012 (10)
C22	0.0315 (12)	0.0334 (12)	0.0297 (12)	−0.0024 (10)	0.0030 (10)	−0.0021 (10)
C23	0.0355 (13)	0.0328 (12)	0.0276 (11)	0.0001 (10)	0.0063 (10)	−0.0030 (10)
C24	0.0307 (13)	0.0339 (12)	0.0353 (13)	−0.0029 (10)	0.0055 (10)	−0.0014 (10)
C25	0.0378 (14)	0.0395 (13)	0.0348 (13)	−0.0031 (11)	0.0060 (11)	−0.0072 (11)
C26	0.0367 (14)	0.0393 (13)	0.0291 (12)	0.0002 (11)	0.0055 (10)	−0.0045 (10)
O27	0.0345 (9)	0.0420 (9)	0.0360 (9)	−0.0100 (8)	0.0093 (7)	−0.0052 (8)
C28	0.0382 (14)	0.0390 (14)	0.0426 (14)	−0.0115 (11)	0.0061 (12)	−0.0086 (11)
C29	0.0360 (14)	0.0412 (14)	0.0405 (14)	−0.0075 (12)	0.0070 (11)	−0.0024 (11)
O35	0.0404 (10)	0.0465 (10)	0.0326 (9)	−0.0116 (8)	0.0106 (7)	−0.0100 (8)
C36	0.0477 (16)	0.0504 (16)	0.0318 (13)	−0.0090 (13)	0.0038 (11)	−0.0097 (12)
N37	0.0387 (12)	0.0486 (13)	0.0394 (12)	−0.0070 (10)	0.0124 (9)	−0.0063 (10)
C38	0.0414 (16)	0.0587 (19)	0.0557 (18)	−0.0085 (14)	0.0100 (13)	−0.0086 (14)
C39	0.0499 (17)	0.0570 (18)	0.0519 (17)	−0.0078 (15)	0.0000 (13)	−0.0051 (14)
C40	0.0585 (19)	0.0520 (17)	0.0419 (15)	−0.0007 (14)	0.0056 (13)	−0.0061 (13)
C41	0.074 (2)	0.077 (2)	0.0438 (16)	−0.0248 (18)	0.0224 (15)	−0.0134 (16)
C31A	0.108 (5)	0.032 (3)	0.046 (4)	−0.001 (4)	−0.006 (4)	0.016 (3)
C32A	0.109 (6)	0.047 (3)	0.048 (4)	−0.008 (5)	0.001 (5)	0.007 (3)
C33A	0.109 (5)	0.071 (4)	0.051 (3)	−0.004 (4)	0.010 (4)	0.018 (3)
C34A	0.088 (4)	0.056 (5)	0.037 (4)	−0.028 (3)	0.012 (3)	0.014 (3)
N30	0.0581 (15)	0.0384 (12)	0.0387 (12)	−0.0108 (11)	0.0067 (11)	0.0000 (10)
C31B	0.098 (5)	0.031 (3)	0.034 (4)	−0.009 (4)	−0.007 (3)	0.015 (3)
C32B	0.115 (6)	0.049 (3)	0.048 (4)	−0.014 (4)	0.009 (4)	0.015 (3)
C33B	0.104 (6)	0.063 (5)	0.042 (3)	−0.018 (5)	0.009 (5)	0.010 (3)
C34B	0.093 (5)	0.067 (6)	0.037 (4)	−0.040 (4)	0.025 (4)	0.008 (3)
O1W	0.0891 (17)	0.0559 (13)	0.0429 (11)	−0.0309 (12)	0.0258 (11)	−0.0160 (10)

Geometric parameters (Å, º)

C1—C2	1.526 (4)	C22—C23	1.378 (3)
C1—C10	1.541 (3)	C22—H22	0.9500
C1—H1A	0.9900	C23—O35	1.374 (3)
C1—H1B	0.9900	C23—C24	1.404 (3)
C2—C3	1.512 (3)	C24—O27	1.376 (3)
C2—H2A	0.9900	C24—C25	1.385 (3)
C2—H2B	0.9900	C25—C26	1.389 (3)
C3—N37	1.458 (3)	C25—H25	0.9500
C3—C4B	1.529 (6)	C26—H26	0.9500
C3—C4A	1.562 (4)	O27—C28	1.436 (3)
C3—H3A	1.0000	C28—C29	1.501 (4)
C3—H3B	1.0000	C28—H28A	0.9900
C4A—C5	1.484 (4)	C28—H28B	0.9900
C4A—H4A	0.9900	C29—N30	1.447 (3)
C4A—H4B	0.9900	C29—H29A	0.9900
C4B—C5	1.471 (6)	C29—H29B	0.9900
C4B—H4C	0.9900	O35—C36	1.433 (3)
C4B—H4D	0.9900	C36—H36A	0.9800
C5—C6	1.341 (4)	C36—H36B	0.9800
C5—C10	1.528 (3)	C36—H36C	0.9800
C6—C7	1.490 (4)	N37—C38	1.450 (4)
C6—H6	0.9500	N37—C41	1.455 (3)
C7—C8	1.522 (3)	C38—C39	1.519 (4)
C7—H7A	0.9900	C38—H38A	0.9900
C7—H7B	0.9900	C38—H38B	0.9900
C8—C14	1.524 (3)	C39—C40	1.533 (4)
C8—C9	1.548 (3)	C39—H39A	0.9900
C8—H8	1.0000	C39—H39B	0.9900
C9—C11	1.542 (3)	C40—C41	1.508 (4)
C9—C10	1.555 (3)	C40—H40A	0.9900
C9—H9	1.0000	C40—H40B	0.9900
C10—C19	1.542 (4)	C41—H41A	0.9900
C11—C12	1.546 (3)	C41—H41B	0.9900
C11—H11A	0.9900	C31A—N30	1.474 (4)
C11—H11B	0.9900	C31A—C32A	1.535 (5)
C12—C13	1.526 (3)	C31A—H31A	0.9900
C12—H12A	0.9900	C31A—H31B	0.9900
C12—H12B	0.9900	C32A—C33A	1.532 (5)
C13—C18	1.535 (3)	C32A—H32A	0.9900
C13—C14	1.539 (3)	C32A—H32B	0.9900
C13—C17	1.541 (3)	C33A—C34A	1.536 (5)
C14—C15	1.535 (3)	C33A—H33A	0.9900
C14—H14	1.0000	C33A—H33B	0.9900
C15—C16	1.521 (3)	C34A—N30	1.478 (4)
C15—H15A	0.9900	C34A—H34A	0.9900
C15—H15B	0.9900	C34A—H34B	0.9900
C16—C20	1.333 (3)	N30—C34B	1.478 (4)
C16—C17	1.528 (3)	N30—C31B	1.479 (4)
C17—O17	1.415 (3)	C31B—C32B	1.536 (5)
C17—H17	1.0000	C31B—H31C	0.9900
O17—H17A	0.85 (4)	C31B—H31D	0.9900
C18—H18A	0.9800	C32B—C33B	1.533 (5)
C18—H18B	0.9800	C32B—H32C	0.9900
C18—H18C	0.9800	C32B—H32D	0.9900
C19—H19A	0.9800	C33B—C34B	1.535 (5)
C19—H19B	0.9800	C33B—H33C	0.9900
C19—H19C	0.9800	C33B—H33D	0.9900
C20—C21	1.470 (3)	C34B—H34C	0.9900
C20—H20	0.9500	C34B—H34D	0.9900
C21—C26	1.390 (3)	O1W—H1W	0.87 (2)
C21—C22	1.408 (3)	O1W—H2W	0.88 (2)
C2—C1—C10	115.0 (2)	C21—C20—H20	114.7
C2—C1—H1A	108.5	C26—C21—C22	117.4 (2)
C10—C1—H1A	108.5	C26—C21—C20	118.7 (2)
C2—C1—H1B	108.5	C22—C21—C20	123.9 (2)
C10—C1—H1B	108.5	C23—C22—C21	121.0 (2)
H1A—C1—H1B	107.5	C23—C22—H22	119.5
C3—C2—C1	111.6 (2)	C21—C22—H22	119.5
C3—C2—H2A	109.3	O35—C23—C22	124.0 (2)
C1—C2—H2A	109.3	O35—C23—C24	115.3 (2)
C3—C2—H2B	109.3	C22—C23—C24	120.7 (2)
C1—C2—H2B	109.3	O27—C24—C25	125.2 (2)
H2A—C2—H2B	108.0	O27—C24—C23	116.1 (2)
N37—C3—C2	113.2 (2)	C25—C24—C23	118.7 (2)
N37—C3—C4B	125.2 (4)	C24—C25—C26	120.2 (2)
C2—C3—C4B	117.8 (4)	C24—C25—H25	119.9
N37—C3—C4A	108.5 (2)	C26—C25—H25	119.9
C2—C3—C4A	106.7 (2)	C25—C26—C21	122.0 (2)
N37—C3—H3A	109.5	C25—C26—H26	119.0
C2—C3—H3A	109.5	C21—C26—H26	119.0
C4A—C3—H3A	109.5	C24—O27—C28	116.45 (18)
N37—C3—H3B	96.5	O27—C28—C29	109.5 (2)
C2—C3—H3B	96.5	O27—C28—H28A	109.8
C4B—C3—H3B	96.5	C29—C28—H28A	109.8
C5—C4A—C3	111.8 (3)	O27—C28—H28B	109.8
C5—C4A—H4A	109.3	C29—C28—H28B	109.8
C3—C4A—H4A	109.3	H28A—C28—H28B	108.2
C5—C4A—H4B	109.3	N30—C29—C28	115.1 (2)
C3—C4A—H4B	109.3	N30—C29—H29A	108.5
H4A—C4A—H4B	107.9	C28—C29—H29A	108.5
C5—C4B—C3	114.5 (4)	N30—C29—H29B	108.5
C5—C4B—H4C	108.6	C28—C29—H29B	108.5
C3—C4B—H4C	108.6	H29A—C29—H29B	107.5
C5—C4B—H4D	108.6	C23—O35—C36	117.64 (18)
C3—C4B—H4D	108.6	O35—C36—H36A	109.5
H4C—C4B—H4D	107.6	O35—C36—H36B	109.5
C6—C5—C4B	105.8 (3)	H36A—C36—H36B	109.5
C6—C5—C4A	120.0 (2)	O35—C36—H36C	109.5
C6—C5—C10	123.0 (2)	H36A—C36—H36C	109.5
C4B—C5—C10	123.2 (4)	H36B—C36—H36C	109.5
C4A—C5—C10	116.2 (2)	C38—N37—C41	103.2 (2)
C5—C6—C7	124.1 (2)	C38—N37—C3	114.3 (2)
C5—C6—H6	117.9	C41—N37—C3	114.8 (2)
C7—C6—H6	117.9	N37—C38—C39	104.7 (2)
C6—C7—C8	112.4 (2)	N37—C38—H38A	110.8
C6—C7—H7A	109.1	C39—C38—H38A	110.8
C8—C7—H7A	109.1	N37—C38—H38B	110.8
C6—C7—H7B	109.1	C39—C38—H38B	110.8
C8—C7—H7B	109.1	H38A—C38—H38B	108.9
H7A—C7—H7B	107.9	C38—C39—C40	104.0 (2)
C7—C8—C14	111.55 (18)	C38—C39—H39A	111.0
C7—C8—C9	110.64 (19)	C40—C39—H39A	111.0
C14—C8—C9	108.31 (18)	C38—C39—H39B	111.0
C7—C8—H8	108.8	C40—C39—H39B	111.0
C14—C8—H8	108.8	H39A—C39—H39B	109.0
C9—C8—H8	108.8	C41—C40—C39	104.3 (2)
C11—C9—C8	112.09 (19)	C41—C40—H40A	110.9
C11—C9—C10	112.76 (19)	C39—C40—H40A	110.9
C8—C9—C10	112.89 (19)	C41—C40—H40B	110.9
C11—C9—H9	106.1	C39—C40—H40B	110.9
C8—C9—H9	106.1	H40A—C40—H40B	108.9
C10—C9—H9	106.1	N37—C41—C40	106.1 (2)
C5—C10—C1	108.0 (2)	N37—C41—H41A	110.5
C5—C10—C19	108.0 (2)	C40—C41—H41A	110.5
C1—C10—C19	109.9 (2)	N37—C41—H41B	110.5
C5—C10—C9	109.97 (19)	C40—C41—H41B	110.5
C1—C10—C9	109.6 (2)	H41A—C41—H41B	108.7
C19—C10—C9	111.3 (2)	N30—C31A—C32A	103.3 (4)
C9—C11—C12	114.10 (19)	N30—C31A—H31A	111.1
C9—C11—H11A	108.7	C32A—C31A—H31A	111.1
C12—C11—H11A	108.7	N30—C31A—H31B	111.1
C9—C11—H11B	108.7	C32A—C31A—H31B	111.1
C12—C11—H11B	108.7	H31A—C31A—H31B	109.1
H11A—C11—H11B	107.6	C33A—C32A—C31A	104.0 (5)
C13—C12—C11	110.58 (19)	C33A—C32A—H32A	111.0
C13—C12—H12A	109.5	C31A—C32A—H32A	111.0
C11—C12—H12A	109.5	C33A—C32A—H32B	111.0
C13—C12—H12B	109.5	C31A—C32A—H32B	111.0
C11—C12—H12B	109.5	H32A—C32A—H32B	109.0
H12A—C12—H12B	108.1	C32A—C33A—C34A	106.5 (5)
C12—C13—C18	112.2 (2)	C32A—C33A—H33A	110.4
C12—C13—C14	107.07 (18)	C34A—C33A—H33A	110.4
C18—C13—C14	113.51 (19)	C32A—C33A—H33B	110.4
C12—C13—C17	115.2 (2)	C34A—C33A—H33B	110.4
C18—C13—C17	108.71 (19)	H33A—C33A—H33B	108.6
C14—C13—C17	99.61 (18)	N30—C34A—C33A	102.2 (4)
C8—C14—C15	119.17 (19)	N30—C34A—H34A	111.3
C8—C14—C13	113.62 (19)	C33A—C34A—H34A	111.3
C15—C14—C13	105.09 (18)	N30—C34A—H34B	111.3
C8—C14—H14	106.0	C33A—C34A—H34B	111.3
C15—C14—H14	106.0	H34A—C34A—H34B	109.2
C13—C14—H14	106.0	C29—N30—C31A	120.5 (4)
C16—C15—C14	103.49 (19)	C29—N30—C34B	118.9 (4)
C16—C15—H15A	111.1	C29—N30—C34A	105.1 (4)
C14—C15—H15A	111.1	C31A—N30—C34A	105.0 (5)
C16—C15—H15B	111.1	C29—N30—C31B	109.0 (4)
C14—C15—H15B	111.1	C34B—N30—C31B	104.1 (5)
H15A—C15—H15B	109.0	N30—C31B—C32B	103.9 (4)
C20—C16—C15	129.7 (2)	N30—C31B—H31C	111.0
C20—C16—C17	122.3 (2)	C32B—C31B—H31C	111.0
C15—C16—C17	108.00 (19)	N30—C31B—H31D	111.0
O17—C17—C16	115.2 (2)	C32B—C31B—H31D	111.0
O17—C17—C13	112.19 (19)	H31C—C31B—H31D	109.0
C16—C17—C13	103.31 (18)	C33B—C32B—C31B	103.3 (5)
O17—C17—H17	108.6	C33B—C32B—H32C	111.1
C16—C17—H17	108.6	C31B—C32B—H32C	111.1
C13—C17—H17	108.6	C33B—C32B—H32D	111.1
C17—O17—H17A	108 (2)	C31B—C32B—H32D	111.1
C13—C18—H18A	109.5	H32C—C32B—H32D	109.1
C13—C18—H18B	109.5	C32B—C33B—C34B	106.8 (5)
H18A—C18—H18B	109.5	C32B—C33B—H33C	110.4
C13—C18—H18C	109.5	C34B—C33B—H33C	110.4
H18A—C18—H18C	109.5	C32B—C33B—H33D	110.4
H18B—C18—H18C	109.5	C34B—C33B—H33D	110.4
C10—C19—H19A	109.5	H33C—C33B—H33D	108.6
C10—C19—H19B	109.5	N30—C34B—C33B	102.8 (4)
H19A—C19—H19B	109.5	N30—C34B—H34C	111.2
C10—C19—H19C	109.5	C33B—C34B—H34C	111.2
H19A—C19—H19C	109.5	N30—C34B—H34D	111.2
H19B—C19—H19C	109.5	C33B—C34B—H34D	111.2
C16—C20—C21	130.7 (2)	H34C—C34B—H34D	109.1
C16—C20—H20	114.7	H1W—O1W—H2W	103 (4)
C10—C1—C2—C3	−56.9 (3)	C20—C16—C17—C13	−153.8 (2)
C1—C2—C3—N37	177.7 (2)	C15—C16—C17—C13	25.2 (2)
C1—C2—C3—C4B	18.5 (6)	C12—C13—C17—O17	79.6 (3)
C1—C2—C3—C4A	58.5 (3)	C18—C13—C17—O17	−47.2 (3)
N37—C3—C4A—C5	179.5 (3)	C14—C13—C17—O17	−166.21 (19)
C2—C3—C4A—C5	−58.3 (3)	C12—C13—C17—C16	−155.72 (18)
C4B—C3—C4A—C5	55.6 (5)	C18—C13—C17—C16	77.4 (2)
N37—C3—C4B—C5	−132.8 (6)	C14—C13—C17—C16	−41.6 (2)
C2—C3—C4B—C5	23.7 (10)	C15—C16—C20—C21	0.4 (4)
C4A—C3—C4B—C5	−58.1 (5)	C17—C16—C20—C21	179.2 (2)
C3—C4B—C5—C6	177.1 (6)	C16—C20—C21—C26	−174.5 (2)
C3—C4B—C5—C10	−33.4 (10)	C16—C20—C21—C22	5.7 (4)
C3—C4A—C5—C6	−134.5 (3)	C26—C21—C22—C23	0.2 (3)
C3—C4A—C5—C10	55.8 (4)	C20—C21—C22—C23	−180.0 (2)
C4B—C5—C6—C7	135.4 (5)	C21—C22—C23—O35	179.9 (2)
C4A—C5—C6—C7	176.8 (3)	C21—C22—C23—C24	0.0 (4)
C10—C5—C6—C7	−14.2 (5)	O35—C23—C24—O27	−0.5 (3)
C5—C6—C7—C8	25.4 (4)	C22—C23—C24—O27	179.4 (2)
C6—C7—C8—C14	−166.4 (2)	O35—C23—C24—C25	180.0 (2)
C6—C7—C8—C9	−45.7 (3)	C22—C23—C24—C25	−0.1 (4)
C7—C8—C9—C11	−173.4 (2)	O27—C24—C25—C26	−179.5 (2)
C14—C8—C9—C11	−50.8 (3)	C23—C24—C25—C26	0.0 (4)
C7—C8—C9—C10	58.0 (3)	C24—C25—C26—C21	0.2 (4)
C14—C8—C9—C10	−179.46 (18)	C22—C21—C26—C25	−0.3 (3)
C6—C5—C10—C1	142.7 (3)	C20—C21—C26—C25	179.9 (2)
C4B—C5—C10—C1	−1.8 (6)	C25—C24—O27—C28	−6.8 (3)
C4A—C5—C10—C1	−48.0 (3)	C23—C24—O27—C28	173.7 (2)
C6—C5—C10—C19	−98.6 (3)	C24—O27—C28—C29	176.8 (2)
C4B—C5—C10—C19	117.0 (5)	O27—C28—C29—N30	54.2 (3)
C4A—C5—C10—C19	70.8 (3)	C22—C23—O35—C36	8.5 (3)
C6—C5—C10—C9	23.1 (4)	C24—C23—O35—C36	−171.6 (2)
C4B—C5—C10—C9	−121.4 (5)	C2—C3—N37—C38	60.9 (3)
C4A—C5—C10—C9	−167.5 (3)	C4B—C3—N37—C38	−141.7 (5)
C2—C1—C10—C5	47.7 (3)	C4A—C3—N37—C38	179.0 (3)
C2—C1—C10—C19	−69.9 (3)	C2—C3—N37—C41	179.9 (3)
C2—C1—C10—C9	167.5 (2)	C4B—C3—N37—C41	−22.7 (6)
C11—C9—C10—C5	−172.9 (2)	C4A—C3—N37—C41	−62.0 (3)
C8—C9—C10—C5	−44.6 (3)	C41—N37—C38—C39	41.8 (3)
C11—C9—C10—C1	68.5 (3)	C3—N37—C38—C39	167.2 (2)
C8—C9—C10—C1	−163.2 (2)	N37—C38—C39—C40	−28.3 (3)
C11—C9—C10—C19	−53.2 (3)	C38—C39—C40—C41	4.4 (3)
C8—C9—C10—C19	75.1 (2)	C38—N37—C41—C40	−39.3 (3)
C8—C9—C11—C12	49.7 (3)	C3—N37—C41—C40	−164.3 (3)
C10—C9—C11—C12	178.4 (2)	C39—C40—C41—N37	20.9 (3)
C9—C11—C12—C13	−53.3 (3)	N30—C31A—C32A—C33A	−27.1 (10)
C11—C12—C13—C18	−67.9 (2)	C31A—C32A—C33A—C34A	2.1 (10)
C11—C12—C13—C14	57.3 (2)	C32A—C33A—C34A—N30	23.4 (9)
C11—C12—C13—C17	167.04 (19)	C28—C29—N30—C31A	68.0 (7)
C7—C8—C14—C15	−53.3 (3)	C28—C29—N30—C34B	171.5 (6)
C9—C8—C14—C15	−175.30 (19)	C28—C29—N30—C34A	−174.0 (5)
C7—C8—C14—C13	−178.00 (19)	C28—C29—N30—C31B	52.6 (6)
C9—C8—C14—C13	60.0 (2)	C32A—C31A—N30—C29	161.6 (5)
C12—C13—C14—C8	−63.7 (2)	C32A—C31A—N30—C34A	43.5 (8)
C18—C13—C14—C8	60.6 (3)	C33A—C34A—N30—C29	−169.5 (5)
C17—C13—C14—C8	175.99 (19)	C33A—C34A—N30—C31A	−41.4 (7)
C12—C13—C14—C15	164.31 (19)	C29—N30—C31B—C32B	171.6 (5)
C18—C13—C14—C15	−71.3 (3)	C34B—N30—C31B—C32B	43.8 (7)
C17—C13—C14—C15	44.0 (2)	N30—C31B—C32B—C33B	−28.2 (9)
C8—C14—C15—C16	−157.7 (2)	C31B—C32B—C33B—C34B	3.4 (10)
C13—C14—C15—C16	−29.0 (2)	C29—N30—C34B—C33B	−162.2 (5)
C14—C15—C16—C20	−179.0 (2)	C31B—N30—C34B—C33B	−40.7 (8)
C14—C15—C16—C17	2.1 (2)	C32B—C33B—C34B—N30	22.4 (10)
C20—C16—C17—O17	−31.1 (3)	C19—C10—C13—C18	11.34 (19)
C15—C16—C17—O17	147.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O17—H17A···O1W	0.85 (4)	1.90 (4)	2.748 (3)	172 (3)
O1W—H1W···N30^i	0.87 (2)	1.95 (2)	2.813 (3)	169 (4)
O1W—H2W···O35^i	0.88 (2)	1.96 (2)	2.835 (3)	170 (4)
O1W—H2W···O27^i	0.88 (2)	2.47 (4)	2.987 (3)	118 (3)

Symmetry code: (i) x−1, y, z+1.