Chloro–formyl steroids as precursors for hybrid heterosteroids: synthesis, spectroscopic characterization, and mol­ecular and supra­molecular structures

Two new functionalized steroids containing both chloro and formyl substituents in ring A, and intended as precursors for the synthesis of hybrid systems, have been synthesized from ketosteroid precursors. 3-Chloro-2-formyl-17,17-dimethyl-18-nor-5α-androstane-2,13-diene, (I), and methyl 3-chloro-4-formyl-12-oxo-5β-cholan-3-ene-24-oate, C₂₆H₃₇ClO₄, (IV), have been synthesized using Vilsmeier reactions with 17β-hy­droxy-17α-methyl-5α-androstan-3-one and methyl 3,13-dioxo-5β-cholan-24-oate, respectively. These products have been fully characterized using IR spectroscopy, ¹H and ¹³C NMR spectroscopy, and high-resolution mass spectrometry, and in the case of (IV), a single-crystal X-ray diffraction study. Crystal structures have also been determined for the known analogues 3-chloro-2-formyl-17-oxo-5α-androst-2-ene, C₂₀H₂₇ClO₂, (II), 3-chloro-2-formyl-5α-cholest-2-ene, C₂₈H₄₅ClO, (III), and the absolute and relative configurations are assigned for all four compounds (I)–(IV): when the fusion between rings A and B is trans, 3-chloro-2-formyl products are formed, but when this ring fusion is cis, a 3-chloro-4-formyl product results. The formation of (I) involves not only chloro­formyl­ation at ring A, but also dehydration and the 1,2 migration of a methyl group at ring D. In each of (II), (III) and (IV), rings B and C adopt almost perfect chair conformations, while ring A adopts a half-chair conformation. Ring D adopts an envelope conformation in each of (II) and (III), albeit differently folded in the two compounds, while in (IV), it adopts a half-chair conformation. A single C—H...O hydrogen bond links the mol­ecules of (II) into C(6) chains which are linked into sheets by means of carbon­yl–carbonyl inter­actions. The mol­ecules of (IV) are linked into simple C(7) chains, again by a single C—H...O hydrogen bond, but there are no direction-specific inter­actions in (III) that are structurally significant.

Computing details

For all structures, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

(5S,8R,9S,10S,13S,14S)-3-Chloro-10,13-dimethyl-17-oxo-4,5,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthrene-2-carbaldehyde (II)

Crystal data

C20H27ClO2	F(000) = 720
Mr = 334.87	Dx = 1.283 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
a = 12.984 (2) Å	Cell parameters from 3974 reflections
b = 6.2961 (11) Å	θ = 2.9–27.6°
c = 21.265 (4) Å	µ = 0.23 mm^−1
β = 94.306 (5)°	T = 100 K
V = 1733.5 (5) Å^3	Plate, colourless
Z = 4	0.32 × 0.20 × 0.06 mm

Data collection

Bruker D8 Venture diffractometer	3974 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	3403 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.049
φ and ω scans	θmax = 27.6°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −16→15
Tmin = 0.822, Tmax = 0.986	k = −8→8
13049 measured reflections	l = −27→27

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.042	w = 1/[σ^2(Fo^2) + (0.0441P)^2 + 0.2448P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.090	(Δ/σ)max = 0.001
S = 1.06	Δρmax = 0.26 e Å^−3
3974 reflections	Δρmin = −0.34 e Å^−3
210 parameters	Absolute structure: Flack x determined using 1322 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) 249-259)
1 restraint	Absolute structure parameter: −0.01 (3)

Special details

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

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

	x	y	z	Uiso*/Ueq
C1	0.1905 (2)	0.2520 (5)	0.33169 (12)	0.0159 (6)
H1A	0.1284	0.3421	0.3237	0.019*
H1B	0.1778	0.1167	0.3087	0.019*
C2	0.2059 (2)	0.2058 (5)	0.40168 (12)	0.0158 (6)
C3	0.30165 (19)	0.1936 (5)	0.42961 (11)	0.0164 (6)
Cl3	0.32422 (5)	0.16447 (12)	0.51120 (3)	0.02248 (19)
C4	0.3994 (2)	0.2162 (5)	0.39716 (12)	0.0187 (7)
H4A	0.4445	0.0928	0.4080	0.022*
H4B	0.4361	0.3457	0.4129	0.022*
C5	0.38051 (19)	0.2307 (4)	0.32553 (12)	0.0160 (6)
H5	0.3674	0.0833	0.3094	0.019*
C6	0.4778 (2)	0.3118 (5)	0.29700 (12)	0.0189 (6)
H6A	0.4966	0.4523	0.3153	0.023*
H6B	0.5356	0.2129	0.3082	0.023*
C7	0.4630 (2)	0.3318 (5)	0.22532 (12)	0.0184 (6)
H7A	0.5250	0.3988	0.2095	0.022*
H7B	0.4556	0.1882	0.2065	0.022*
C8	0.36794 (19)	0.4639 (5)	0.20447 (12)	0.0142 (6)
H8	0.3782	0.6111	0.2215	0.017*
C9	0.2710 (2)	0.3673 (4)	0.23195 (12)	0.0135 (6)
H9	0.2689	0.2151	0.2185	0.016*
C10	0.2835 (2)	0.3647 (4)	0.30555 (12)	0.0123 (6)
C11	0.16828 (19)	0.4659 (5)	0.20491 (12)	0.0166 (6)
H11A	0.1105	0.3772	0.2177	0.020*
H11B	0.1609	0.6086	0.2236	0.020*
C12	0.1595 (2)	0.4868 (5)	0.13282 (12)	0.0177 (6)
H12A	0.1547	0.3439	0.1134	0.021*
H12B	0.0960	0.5665	0.1190	0.021*
C13	0.2532 (2)	0.6024 (4)	0.11135 (12)	0.0138 (6)
C14	0.35096 (19)	0.4767 (5)	0.13319 (12)	0.0142 (6)
H14	0.3397	0.3279	0.1177	0.017*
C15	0.4357 (2)	0.5720 (5)	0.09515 (12)	0.0207 (7)
H15A	0.4936	0.4710	0.0921	0.025*
H15B	0.4627	0.7059	0.1144	0.025*
C16	0.3792 (2)	0.6125 (5)	0.03012 (12)	0.0198 (7)
H16A	0.4004	0.7505	0.0129	0.024*
H16B	0.3951	0.4988	0.0002	0.024*
C17	0.2648 (2)	0.6140 (4)	0.04041 (12)	0.0165 (6)
O17	0.19486 (14)	0.6244 (3)	−0.00046 (8)	0.0212 (5)
C18	0.2915 (2)	0.5910 (4)	0.33273 (12)	0.0150 (6)
H18A	0.2314	0.6741	0.3167	0.022*
H18B	0.3547	0.6587	0.3200	0.022*
H18C	0.2937	0.5845	0.3789	0.022*
C19	0.2566 (2)	0.8358 (5)	0.13349 (13)	0.0195 (6)
H19A	0.3151	0.9081	0.1162	0.029*
H19B	0.2648	0.8406	0.1797	0.029*
H19C	0.1922	0.9070	0.1187	0.029*
C211	0.1127 (2)	0.1891 (5)	0.43676 (12)	0.0188 (6)
H211	0.1211	0.1582	0.4806	0.023*
O211	0.02595 (14)	0.2128 (3)	0.41273 (8)	0.0223 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0110 (13)	0.0199 (16)	0.0168 (13)	−0.0015 (11)	0.0006 (10)	0.0021 (11)
C2	0.0167 (13)	0.0129 (16)	0.0182 (13)	−0.0003 (12)	0.0035 (10)	0.0020 (11)
C3	0.0182 (13)	0.0156 (16)	0.0154 (12)	−0.0014 (13)	0.0021 (10)	0.0031 (12)
Cl3	0.0211 (3)	0.0281 (4)	0.0180 (3)	−0.0013 (3)	−0.0005 (2)	0.0070 (3)
C4	0.0131 (13)	0.0228 (18)	0.0199 (14)	0.0030 (12)	−0.0011 (10)	0.0043 (12)
C5	0.0117 (13)	0.0168 (16)	0.0196 (13)	0.0035 (11)	0.0027 (10)	0.0009 (11)
C6	0.0089 (13)	0.0266 (17)	0.0213 (14)	0.0064 (12)	0.0022 (11)	0.0017 (12)
C7	0.0092 (13)	0.0262 (18)	0.0202 (14)	0.0064 (12)	0.0045 (11)	0.0020 (12)
C8	0.0092 (13)	0.0174 (15)	0.0164 (13)	0.0013 (11)	0.0032 (10)	−0.0014 (11)
C9	0.0111 (12)	0.0134 (15)	0.0160 (13)	0.0000 (11)	0.0013 (10)	−0.0001 (10)
C10	0.0080 (12)	0.0132 (15)	0.0158 (13)	0.0012 (11)	0.0015 (10)	0.0004 (10)
C11	0.0084 (13)	0.0240 (17)	0.0174 (13)	−0.0003 (12)	0.0023 (10)	0.0021 (12)
C12	0.0125 (14)	0.0250 (17)	0.0153 (14)	0.0011 (13)	0.0002 (11)	0.0014 (12)
C13	0.0119 (12)	0.0147 (15)	0.0149 (12)	0.0021 (11)	0.0018 (10)	−0.0005 (11)
C14	0.0109 (13)	0.0163 (15)	0.0157 (13)	0.0019 (11)	0.0023 (10)	−0.0026 (11)
C15	0.0124 (13)	0.0314 (18)	0.0190 (14)	−0.0004 (13)	0.0052 (11)	0.0034 (12)
C16	0.0173 (13)	0.0244 (19)	0.0183 (13)	−0.0001 (12)	0.0057 (10)	0.0007 (12)
C17	0.0195 (13)	0.0138 (17)	0.0165 (12)	−0.0009 (12)	0.0034 (11)	−0.0008 (11)
O17	0.0197 (10)	0.0267 (14)	0.0169 (9)	0.0009 (9)	−0.0003 (8)	−0.0011 (8)
C18	0.0124 (13)	0.0161 (15)	0.0165 (13)	0.0009 (11)	0.0021 (10)	0.0005 (11)
C19	0.0217 (15)	0.0171 (16)	0.0201 (15)	0.0030 (13)	0.0031 (12)	−0.0012 (12)
C211	0.0203 (13)	0.0178 (16)	0.0186 (12)	−0.0040 (14)	0.0044 (10)	−0.0001 (13)
O211	0.0129 (9)	0.0298 (14)	0.0244 (10)	−0.0033 (9)	0.0025 (8)	−0.0011 (9)

Geometric parameters (Å, º)

C1—C2	1.515 (3)	C11—C12	1.534 (3)
C1—C10	1.540 (4)	C11—H11A	0.9900
C1—H1A	0.9900	C11—H11B	0.9900
C1—H1B	0.9900	C12—C13	1.518 (4)
C2—C3	1.339 (4)	C12—H12A	0.9900
C2—C211	1.472 (4)	C12—H12B	0.9900
C3—C4	1.496 (4)	C13—C17	1.529 (3)
C3—Cl3	1.747 (2)	C13—C14	1.538 (4)
C4—C5	1.527 (3)	C13—C19	1.543 (4)
C4—H4A	0.9900	C14—C15	1.536 (4)
C4—H4B	0.9900	C14—H14	1.0000
C5—C6	1.530 (4)	C15—C16	1.537 (4)
C5—C10	1.549 (3)	C15—H15A	0.9900
C5—H5	1.0000	C15—H15B	0.9900
C6—C7	1.527 (4)	C16—C17	1.518 (4)
C6—H6A	0.9900	C16—H16A	0.9900
C6—H6B	0.9900	C16—H16B	0.9900
C7—C8	1.526 (4)	C17—O17	1.211 (3)
C7—H7A	0.9900	C18—H18A	0.9800
C7—H7B	0.9900	C18—H18B	0.9800
C8—C14	1.517 (3)	C18—H18C	0.9800
C8—C9	1.551 (4)	C19—H19A	0.9800
C8—H8	1.0000	C19—H19B	0.9800
C9—C11	1.543 (3)	C19—H19C	0.9800
C9—C10	1.561 (3)	C211—O211	1.211 (3)
C9—H9	1.0000	C211—H211	0.9500
C10—C18	1.538 (4)
C2—C1—C10	113.2 (2)	C12—C11—C9	113.8 (2)
C2—C1—H1A	108.9	C12—C11—H11A	108.8
C10—C1—H1A	108.9	C9—C11—H11A	108.8
C2—C1—H1B	108.9	C12—C11—H11B	108.8
C10—C1—H1B	108.9	C9—C11—H11B	108.8
H1A—C1—H1B	107.8	H11A—C11—H11B	107.7
C3—C2—C211	122.8 (2)	C13—C12—C11	109.9 (2)
C3—C2—C1	119.8 (2)	C13—C12—H12A	109.7
C211—C2—C1	117.3 (2)	C11—C12—H12A	109.7
C2—C3—C4	125.5 (2)	C13—C12—H12B	109.7
C2—C3—Cl3	121.8 (2)	C11—C12—H12B	109.7
C4—C3—Cl3	112.53 (17)	H12A—C12—H12B	108.2
C3—C4—C5	112.8 (2)	C12—C13—C17	117.4 (2)
C3—C4—H4A	109.0	C12—C13—C14	109.0 (2)
C5—C4—H4A	109.0	C17—C13—C14	100.5 (2)
C3—C4—H4B	109.0	C12—C13—C19	111.7 (2)
C5—C4—H4B	109.0	C17—C13—C19	104.6 (2)
H4A—C4—H4B	107.8	C14—C13—C19	113.2 (2)
C4—C5—C6	109.9 (2)	C8—C14—C15	119.4 (2)
C4—C5—C10	111.9 (2)	C8—C14—C13	112.6 (2)
C6—C5—C10	112.9 (2)	C15—C14—C13	104.3 (2)
C4—C5—H5	107.3	C8—C14—H14	106.6
C6—C5—H5	107.3	C15—C14—H14	106.6
C10—C5—H5	107.3	C13—C14—H14	106.6
C7—C6—C5	112.1 (2)	C14—C15—C16	103.1 (2)
C7—C6—H6A	109.2	C14—C15—H15A	111.2
C5—C6—H6A	109.2	C16—C15—H15A	111.2
C7—C6—H6B	109.2	C14—C15—H15B	111.2
C5—C6—H6B	109.2	C16—C15—H15B	111.2
H6A—C6—H6B	107.9	H15A—C15—H15B	109.1
C8—C7—C6	112.0 (2)	C17—C16—C15	106.1 (2)
C8—C7—H7A	109.2	C17—C16—H16A	110.5
C6—C7—H7A	109.2	C15—C16—H16A	110.5
C8—C7—H7B	109.2	C17—C16—H16B	110.5
C6—C7—H7B	109.2	C15—C16—H16B	110.5
H7A—C7—H7B	107.9	H16A—C16—H16B	108.7
C14—C8—C7	111.9 (2)	O17—C17—C16	125.9 (2)
C14—C8—C9	109.6 (2)	O17—C17—C13	125.9 (2)
C7—C8—C9	109.8 (2)	C16—C17—C13	108.2 (2)
C14—C8—H8	108.5	C10—C18—H18A	109.5
C7—C8—H8	108.5	C10—C18—H18B	109.5
C9—C8—H8	108.5	H18A—C18—H18B	109.5
C11—C9—C8	113.9 (2)	C10—C18—H18C	109.5
C11—C9—C10	113.5 (2)	H18A—C18—H18C	109.5
C8—C9—C10	110.8 (2)	H18B—C18—H18C	109.5
C11—C9—H9	105.9	C13—C19—H19A	109.5
C8—C9—H9	105.9	C13—C19—H19B	109.5
C10—C9—H9	105.9	H19A—C19—H19B	109.5
C18—C10—C1	108.9 (2)	C13—C19—H19C	109.5
C18—C10—C5	111.8 (2)	H19A—C19—H19C	109.5
C1—C10—C5	107.1 (2)	H19B—C19—H19C	109.5
C18—C10—C9	111.5 (2)	O211—C211—C2	123.5 (2)
C1—C10—C9	110.0 (2)	O211—C211—H211	118.3
C5—C10—C9	107.6 (2)	C2—C211—H211	118.3
C10—C1—C2—C3	−22.7 (4)	C11—C9—C10—C5	171.1 (2)
C10—C1—C2—C211	153.6 (3)	C8—C9—C10—C5	−59.2 (3)
C211—C2—C3—C4	−177.9 (3)	C8—C9—C11—C12	46.8 (3)
C1—C2—C3—C4	−1.7 (5)	C10—C9—C11—C12	175.0 (2)
C211—C2—C3—Cl3	−2.0 (4)	C9—C11—C12—C13	−52.5 (3)
C1—C2—C3—Cl3	174.2 (2)	C11—C12—C13—C17	172.6 (2)
C2—C3—C4—C5	−6.6 (4)	C11—C12—C13—C14	59.3 (3)
Cl3—C3—C4—C5	177.2 (2)	C11—C12—C13—C19	−66.6 (3)
C3—C4—C5—C6	165.0 (3)	C7—C8—C14—C15	−59.3 (4)
C3—C4—C5—C10	38.8 (3)	C9—C8—C14—C15	178.7 (2)
C4—C5—C6—C7	−179.4 (2)	C7—C8—C14—C13	177.9 (2)
C10—C5—C6—C7	−53.8 (3)	C9—C8—C14—C13	55.9 (3)
C5—C6—C7—C8	52.9 (3)	C12—C13—C14—C8	−63.4 (3)
C6—C7—C8—C14	−177.9 (2)	C17—C13—C14—C8	172.6 (2)
C6—C7—C8—C9	−55.9 (3)	C19—C13—C14—C8	61.6 (3)
C14—C8—C9—C11	−47.1 (3)	C12—C13—C14—C15	165.7 (2)
C7—C8—C9—C11	−170.4 (2)	C17—C13—C14—C15	41.7 (3)
C14—C8—C9—C10	−176.6 (2)	C19—C13—C14—C15	−69.3 (3)
C7—C8—C9—C10	60.1 (3)	C8—C14—C15—C16	−165.1 (2)
C2—C1—C10—C18	−68.5 (3)	C13—C14—C15—C16	−38.3 (3)
C2—C1—C10—C5	52.5 (3)	C14—C15—C16—C17	19.2 (3)
C2—C1—C10—C9	169.1 (2)	C15—C16—C17—O17	−173.7 (3)
C4—C5—C10—C18	57.9 (3)	C15—C16—C17—C13	6.8 (3)
C6—C5—C10—C18	−66.7 (3)	C12—C13—C17—O17	32.9 (4)
C4—C5—C10—C1	−61.4 (3)	C14—C13—C17—O17	150.8 (3)
C6—C5—C10—C1	174.1 (2)	C19—C13—C17—O17	−91.6 (3)
C4—C5—C10—C9	−179.5 (2)	C12—C13—C17—C16	−147.7 (2)
C6—C5—C10—C9	56.0 (3)	C14—C13—C17—C16	−29.7 (3)
C11—C9—C10—C18	−66.0 (3)	C19—C13—C17—C16	87.8 (3)
C8—C9—C10—C18	63.7 (3)	C3—C2—C211—O211	175.3 (3)
C11—C9—C10—C1	54.9 (3)	C1—C2—C211—O211	−0.9 (5)
C8—C9—C10—C1	−175.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···O211^i	0.99	2.59	3.536 (4)	160

Symmetry code: (i) x+1/2, y+1/2, z.

(5S,8R,9S,10S,13R,14S,17R)-3-Chloro-10,13-dimethyl-17-[(R)-6-methylheptan-2-yl)-4,5,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthrene-2-carbaldehyde (III)

Crystal data

C28H45ClO	Dx = 1.176 Mg m^−3
Mr = 433.09	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 5635 reflections
a = 8.0097 (6) Å	θ = 2.4–27.6°
b = 14.8313 (12) Å	µ = 0.17 mm^−1
c = 20.5873 (15) Å	T = 100 K
V = 2445.7 (3) Å^3	Block, colourless
Z = 4	0.19 × 0.14 × 0.09 mm
F(000) = 952

Data collection

Bruker D8 Venture diffractometer	5635 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	4720 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.078
φ and ω scans	θmax = 27.6°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −10→10
Tmin = 0.894, Tmax = 0.985	k = −19→19
38330 measured reflections	l = −26→26

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.040	w = 1/[σ^2(Fo^2) + (0.0409P)^2 + 0.4094P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.085	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.24 e Å^−3
5635 reflections	Δρmin = −0.29 e Å^−3
276 parameters	Absolute structure: Flack x determined using 1808 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.04 (2)

Special details

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

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

	x	y	z	Uiso*/Ueq
C1	0.3946 (3)	0.37423 (16)	0.62938 (10)	0.0114 (5)
H1A	0.3036	0.4182	0.6220	0.014*
H1B	0.3598	0.3164	0.6096	0.014*
C2	0.4146 (3)	0.36048 (15)	0.70179 (10)	0.0113 (5)
C3	0.5655 (3)	0.35620 (16)	0.72862 (10)	0.0123 (5)
Cl3	0.59060 (7)	0.34128 (5)	0.81264 (3)	0.01992 (15)
C4	0.7271 (3)	0.36442 (17)	0.69295 (11)	0.0128 (5)
H4A	0.8058	0.3179	0.7089	0.015*
H4B	0.7767	0.4243	0.7017	0.015*
C5	0.7021 (3)	0.35292 (16)	0.61979 (10)	0.0097 (5)
H5	0.6761	0.2879	0.6120	0.012*
C6	0.8637 (3)	0.37360 (16)	0.58332 (11)	0.0126 (5)
H6A	0.9539	0.3341	0.5998	0.015*
H6B	0.8964	0.4369	0.5916	0.015*
C7	0.8435 (3)	0.35902 (16)	0.51029 (11)	0.0125 (5)
H7A	0.9466	0.3791	0.4880	0.015*
H7B	0.8298	0.2937	0.5018	0.015*
C8	0.6947 (3)	0.40949 (16)	0.48155 (11)	0.0106 (5)
H8	0.7155	0.4759	0.4840	0.013*
C9	0.5355 (3)	0.38609 (17)	0.52033 (11)	0.0100 (5)
H9	0.5231	0.3191	0.5174	0.012*
C10	0.5523 (3)	0.40785 (15)	0.59403 (11)	0.0097 (5)
C11	0.3787 (3)	0.42577 (17)	0.48847 (11)	0.0131 (5)
H11A	0.3832	0.4924	0.4913	0.016*
H11B	0.2789	0.4052	0.5127	0.016*
C12	0.3613 (3)	0.39800 (17)	0.41669 (11)	0.0126 (5)
H12A	0.3448	0.3319	0.4141	0.015*
H12B	0.2614	0.4275	0.3980	0.015*
C13	0.5151 (3)	0.42415 (16)	0.37670 (11)	0.0111 (5)
C14	0.6679 (3)	0.38241 (16)	0.41112 (11)	0.0111 (5)
H14	0.6469	0.3159	0.4119	0.013*
C15	0.8108 (3)	0.39641 (17)	0.36278 (11)	0.0137 (5)
H15A	0.8989	0.3504	0.3687	0.016*
H15B	0.8608	0.4571	0.3677	0.016*
C16	0.7254 (3)	0.38625 (17)	0.29598 (11)	0.0137 (5)
H16A	0.7663	0.3314	0.2736	0.016*
H16B	0.7497	0.4392	0.2683	0.016*
C17	0.5341 (3)	0.37888 (16)	0.30914 (11)	0.0118 (5)
H17	0.5095	0.3134	0.3155	0.014*
C18	0.5741 (3)	0.50918 (15)	0.60708 (11)	0.0136 (5)
H18A	0.4833	0.5426	0.5862	0.020*
H18B	0.6814	0.5294	0.5894	0.020*
H18C	0.5715	0.5202	0.6540	0.020*
C19	0.5272 (3)	0.52730 (16)	0.37066 (12)	0.0153 (5)
H19A	0.4249	0.5507	0.3507	0.023*
H19B	0.6234	0.5431	0.3435	0.023*
H19C	0.5409	0.5539	0.4139	0.023*
C20	0.4293 (3)	0.40971 (16)	0.25049 (11)	0.0144 (5)
H20	0.4655	0.4721	0.2385	0.017*
C21	0.2411 (3)	0.41219 (18)	0.26484 (12)	0.0179 (6)
H21A	0.1802	0.4279	0.2251	0.027*
H21B	0.2185	0.4574	0.2984	0.027*
H21C	0.2046	0.3528	0.2801	0.027*
C22	0.4665 (3)	0.34723 (17)	0.19262 (11)	0.0156 (5)
H22A	0.5889	0.3454	0.1862	0.019*
H22B	0.4302	0.2855	0.2043	0.019*
C23	0.3855 (3)	0.37213 (16)	0.12797 (11)	0.0167 (5)
H23A	0.2626	0.3731	0.1332	0.020*
H23B	0.4218	0.4334	0.1151	0.020*
C24	0.4319 (3)	0.30539 (17)	0.07462 (11)	0.0159 (5)
H24A	0.3862	0.2456	0.0865	0.019*
H24B	0.5550	0.2998	0.0736	0.019*
C25	0.3716 (3)	0.32867 (16)	0.00602 (10)	0.0135 (5)
H25	0.2496	0.3426	0.0084	0.016*
C26	0.3949 (4)	0.24852 (17)	−0.03940 (12)	0.0201 (5)
H26A	0.3481	0.2630	−0.0821	0.030*
H26B	0.3373	0.1958	−0.0215	0.030*
H26C	0.5142	0.2352	−0.0438	0.030*
C27	0.4607 (3)	0.41110 (17)	−0.02127 (12)	0.0180 (6)
H27A	0.4476	0.4618	0.0088	0.027*
H27B	0.4122	0.4269	−0.0635	0.027*
H27C	0.5797	0.3976	−0.0267	0.027*
C211	0.2603 (3)	0.35088 (17)	0.73942 (11)	0.0139 (5)
H211	0.2689	0.3399	0.7848	0.017*
O211	0.12204 (19)	0.35625 (12)	0.71551 (8)	0.0178 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0075 (11)	0.0139 (12)	0.0127 (11)	0.0004 (9)	−0.0019 (10)	−0.0005 (9)
C2	0.0128 (11)	0.0094 (11)	0.0118 (11)	0.0006 (10)	0.0007 (10)	−0.0010 (8)
C3	0.0149 (12)	0.0130 (12)	0.0090 (10)	−0.0004 (11)	0.0006 (9)	0.0004 (9)
Cl3	0.0148 (3)	0.0355 (4)	0.0095 (2)	−0.0017 (3)	−0.0011 (2)	0.0001 (3)
C4	0.0092 (10)	0.0168 (13)	0.0123 (11)	−0.0001 (9)	−0.0007 (10)	−0.0009 (10)
C5	0.0073 (10)	0.0104 (11)	0.0114 (10)	−0.0006 (9)	0.0002 (9)	−0.0009 (10)
C6	0.0085 (11)	0.0166 (13)	0.0128 (11)	−0.0001 (9)	−0.0001 (9)	0.0006 (9)
C7	0.0089 (10)	0.0146 (13)	0.0139 (11)	0.0012 (10)	0.0012 (9)	−0.0003 (10)
C8	0.0095 (11)	0.0095 (12)	0.0129 (11)	−0.0002 (9)	−0.0004 (9)	0.0011 (9)
C9	0.0075 (11)	0.0099 (12)	0.0126 (11)	0.0005 (9)	−0.0011 (9)	0.0015 (9)
C10	0.0078 (11)	0.0093 (12)	0.0118 (11)	0.0012 (9)	−0.0004 (9)	−0.0008 (9)
C11	0.0086 (12)	0.0163 (13)	0.0145 (11)	0.0013 (10)	−0.0005 (10)	−0.0006 (10)
C12	0.0096 (11)	0.0174 (13)	0.0109 (11)	0.0004 (10)	−0.0013 (9)	0.0017 (10)
C13	0.0099 (11)	0.0109 (12)	0.0126 (11)	0.0005 (9)	−0.0005 (10)	0.0007 (10)
C14	0.0103 (11)	0.0099 (12)	0.0132 (11)	−0.0005 (9)	0.0001 (10)	0.0019 (9)
C15	0.0109 (12)	0.0168 (13)	0.0135 (11)	−0.0001 (10)	0.0014 (10)	0.0013 (10)
C16	0.0145 (12)	0.0139 (12)	0.0129 (11)	0.0009 (10)	0.0004 (10)	0.0016 (10)
C17	0.0135 (11)	0.0117 (12)	0.0102 (10)	−0.0005 (9)	−0.0001 (10)	0.0002 (10)
C18	0.0143 (12)	0.0118 (12)	0.0146 (11)	0.0003 (10)	0.0007 (10)	−0.0010 (9)
C19	0.0196 (12)	0.0111 (12)	0.0151 (12)	0.0010 (10)	−0.0001 (11)	0.0009 (10)
C20	0.0176 (13)	0.0142 (12)	0.0113 (11)	0.0018 (11)	−0.0014 (10)	0.0015 (9)
C21	0.0190 (14)	0.0207 (14)	0.0141 (12)	0.0046 (11)	−0.0018 (11)	0.0005 (10)
C22	0.0170 (11)	0.0164 (13)	0.0135 (11)	0.0034 (10)	−0.0014 (10)	0.0003 (11)
C23	0.0189 (13)	0.0188 (13)	0.0125 (11)	0.0010 (11)	−0.0008 (11)	0.0003 (10)
C24	0.0173 (13)	0.0151 (13)	0.0154 (12)	0.0012 (11)	0.0000 (11)	0.0001 (10)
C25	0.0110 (12)	0.0154 (13)	0.0140 (11)	−0.0001 (10)	−0.0002 (9)	−0.0004 (9)
C26	0.0208 (13)	0.0203 (14)	0.0191 (12)	−0.0016 (12)	−0.0002 (12)	−0.0020 (11)
C27	0.0218 (14)	0.0179 (14)	0.0143 (12)	−0.0015 (11)	0.0000 (11)	0.0022 (10)
C211	0.0152 (12)	0.0139 (12)	0.0128 (11)	−0.0016 (11)	0.0015 (10)	−0.0018 (10)
O211	0.0093 (9)	0.0234 (10)	0.0207 (8)	−0.0012 (8)	−0.0005 (7)	−0.0005 (8)

Geometric parameters (Å, º)

C1—C2	1.513 (3)	C15—H15A	0.9900
C1—C10	1.540 (3)	C15—H15B	0.9900
C1—H1A	0.9900	C16—C17	1.560 (3)
C1—H1B	0.9900	C16—H16A	0.9900
C2—C3	1.331 (3)	C16—H16B	0.9900
C2—C211	1.465 (3)	C17—C20	1.540 (3)
C3—C4	1.493 (3)	C17—H17	1.0000
C3—Cl3	1.755 (2)	C18—H18A	0.9800
C4—C5	1.529 (3)	C18—H18B	0.9800
C4—H4A	0.9900	C18—H18C	0.9800
C4—H4B	0.9900	C19—H19A	0.9800
C5—C6	1.527 (3)	C19—H19B	0.9800
C5—C10	1.545 (3)	C19—H19C	0.9800
C5—H5	1.0000	C20—C21	1.536 (3)
C6—C7	1.527 (3)	C20—C22	1.539 (3)
C6—H6A	0.9900	C20—H20	1.0000
C6—H6B	0.9900	C21—H21A	0.9800
C7—C8	1.527 (3)	C21—H21B	0.9800
C7—H7A	0.9900	C21—H21C	0.9800
C7—H7B	0.9900	C22—C23	1.526 (3)
C8—C14	1.520 (3)	C22—H22A	0.9900
C8—C9	1.544 (3)	C22—H22B	0.9900
C8—H8	1.0000	C23—C24	1.525 (3)
C9—C11	1.534 (3)	C23—H23A	0.9900
C9—C10	1.557 (3)	C23—H23B	0.9900
C9—H9	1.0000	C24—C25	1.532 (3)
C10—C18	1.537 (3)	C24—H24A	0.9900
C11—C12	1.540 (3)	C24—H24B	0.9900
C11—H11A	0.9900	C25—C27	1.523 (3)
C11—H11B	0.9900	C25—C26	1.524 (3)
C12—C13	1.531 (3)	C25—H25	1.0000
C12—H12A	0.9900	C26—H26A	0.9800
C12—H12B	0.9900	C26—H26B	0.9800
C13—C19	1.538 (3)	C26—H26C	0.9800
C13—C14	1.544 (3)	C27—H27A	0.9800
C13—C17	1.552 (3)	C27—H27B	0.9800
C14—C15	1.531 (3)	C27—H27C	0.9800
C14—H14	1.0000	C211—O211	1.215 (3)
C15—C16	1.543 (3)	C211—H211	0.9500
C2—C1—C10	115.01 (19)	C16—C15—H15A	111.0
C2—C1—H1A	108.5	C14—C15—H15B	111.0
C10—C1—H1A	108.5	C16—C15—H15B	111.0
C2—C1—H1B	108.5	H15A—C15—H15B	109.0
C10—C1—H1B	108.5	C15—C16—C17	106.70 (18)
H1A—C1—H1B	107.5	C15—C16—H16A	110.4
C3—C2—C211	122.8 (2)	C17—C16—H16A	110.4
C3—C2—C1	120.7 (2)	C15—C16—H16B	110.4
C211—C2—C1	116.4 (2)	C17—C16—H16B	110.4
C2—C3—C4	125.4 (2)	H16A—C16—H16B	108.6
C2—C3—Cl3	121.26 (17)	C20—C17—C13	121.38 (19)
C4—C3—Cl3	113.32 (16)	C20—C17—C16	112.24 (19)
C3—C4—C5	111.23 (18)	C13—C17—C16	102.80 (18)
C3—C4—H4A	109.4	C20—C17—H17	106.5
C5—C4—H4A	109.4	C13—C17—H17	106.5
C3—C4—H4B	109.4	C16—C17—H17	106.5
C5—C4—H4B	109.4	C10—C18—H18A	109.5
H4A—C4—H4B	108.0	C10—C18—H18B	109.5
C6—C5—C4	110.56 (18)	H18A—C18—H18B	109.5
C6—C5—C10	112.56 (18)	C10—C18—H18C	109.5
C4—C5—C10	112.40 (18)	H18A—C18—H18C	109.5
C6—C5—H5	107.0	H18B—C18—H18C	109.5
C4—C5—H5	107.0	C13—C19—H19A	109.5
C10—C5—H5	107.0	C13—C19—H19B	109.5
C5—C6—C7	111.46 (18)	H19A—C19—H19B	109.5
C5—C6—H6A	109.3	C13—C19—H19C	109.5
C7—C6—H6A	109.3	H19A—C19—H19C	109.5
C5—C6—H6B	109.3	H19B—C19—H19C	109.5
C7—C6—H6B	109.3	C21—C20—C22	110.7 (2)
H6A—C6—H6B	108.0	C21—C20—C17	113.03 (19)
C8—C7—C6	113.24 (19)	C22—C20—C17	108.83 (19)
C8—C7—H7A	108.9	C21—C20—H20	108.0
C6—C7—H7A	108.9	C22—C20—H20	108.0
C8—C7—H7B	108.9	C17—C20—H20	108.0
C6—C7—H7B	108.9	C20—C21—H21A	109.5
H7A—C7—H7B	107.7	C20—C21—H21B	109.5
C14—C8—C7	110.51 (19)	H21A—C21—H21B	109.5
C14—C8—C9	108.50 (18)	C20—C21—H21C	109.5
C7—C8—C9	109.52 (18)	H21A—C21—H21C	109.5
C14—C8—H8	109.4	H21B—C21—H21C	109.5
C7—C8—H8	109.4	C23—C22—C20	116.6 (2)
C9—C8—H8	109.4	C23—C22—H22A	108.2
C11—C9—C8	111.64 (18)	C20—C22—H22A	108.1
C11—C9—C10	114.05 (18)	C23—C22—H22B	108.1
C8—C9—C10	112.72 (18)	C20—C22—H22B	108.2
C11—C9—H9	105.9	H22A—C22—H22B	107.3
C8—C9—H9	105.9	C24—C23—C22	111.5 (2)
C10—C9—H9	105.9	C24—C23—H23A	109.3
C18—C10—C1	109.10 (19)	C22—C23—H23A	109.3
C18—C10—C5	111.55 (19)	C24—C23—H23B	109.3
C1—C10—C5	107.70 (18)	C22—C23—H23B	109.3
C18—C10—C9	112.52 (19)	H23A—C23—H23B	108.0
C1—C10—C9	108.84 (18)	C23—C24—C25	116.2 (2)
C5—C10—C9	106.99 (18)	C23—C24—H24A	108.2
C9—C11—C12	112.43 (19)	C25—C24—H24A	108.2
C9—C11—H11A	109.1	C23—C24—H24B	108.2
C12—C11—H11A	109.1	C25—C24—H24B	108.2
C9—C11—H11B	109.1	H24A—C24—H24B	107.4
C12—C11—H11B	109.1	C27—C25—C26	110.02 (19)
H11A—C11—H11B	107.8	C27—C25—C24	111.9 (2)
C13—C12—C11	112.04 (19)	C26—C25—C24	110.6 (2)
C13—C12—H12A	109.2	C27—C25—H25	108.1
C11—C12—H12A	109.2	C26—C25—H25	108.1
C13—C12—H12B	109.2	C24—C25—H25	108.1
C11—C12—H12B	109.2	C25—C26—H26A	109.5
H12A—C12—H12B	107.9	C25—C26—H26B	109.5
C12—C13—C19	110.2 (2)	H26A—C26—H26B	109.5
C12—C13—C14	106.81 (18)	C25—C26—H26C	109.5
C19—C13—C14	112.72 (19)	H26A—C26—H26C	109.5
C12—C13—C17	116.81 (19)	H26B—C26—H26C	109.5
C19—C13—C17	110.60 (19)	C25—C27—H27A	109.5
C14—C13—C17	99.22 (18)	C25—C27—H27B	109.5
C8—C14—C15	118.61 (19)	H27A—C27—H27B	109.5
C8—C14—C13	116.36 (19)	C25—C27—H27C	109.5
C15—C14—C13	103.88 (18)	H27A—C27—H27C	109.5
C8—C14—H14	105.6	H27B—C27—H27C	109.5
C15—C14—H14	105.6	O211—C211—C2	123.3 (2)
C13—C14—H14	105.6	O211—C211—H211	118.4
C14—C15—C16	103.58 (18)	C2—C211—H211	118.4
C14—C15—H15A	111.0
C10—C1—C2—C3	−15.9 (3)	C11—C12—C13—C19	−68.1 (3)
C10—C1—C2—C211	165.1 (2)	C11—C12—C13—C14	54.6 (3)
C211—C2—C3—C4	179.3 (2)	C11—C12—C13—C17	164.54 (19)
C1—C2—C3—C4	0.3 (4)	C7—C8—C14—C15	−58.2 (3)
C211—C2—C3—Cl3	−1.6 (3)	C9—C8—C14—C15	−178.3 (2)
C1—C2—C3—Cl3	179.42 (17)	C7—C8—C14—C13	176.66 (19)
C2—C3—C4—C5	−15.5 (3)	C9—C8—C14—C13	56.6 (3)
Cl3—C3—C4—C5	165.39 (16)	C12—C13—C14—C8	−57.5 (3)
C3—C4—C5—C6	172.6 (2)	C19—C13—C14—C8	63.7 (3)
C3—C4—C5—C10	45.9 (3)	C17—C13—C14—C8	−179.27 (19)
C4—C5—C6—C7	177.80 (19)	C12—C13—C14—C15	170.21 (19)
C10—C5—C6—C7	−55.6 (3)	C19—C13—C14—C15	−68.6 (2)
C5—C6—C7—C8	52.8 (3)	C17—C13—C14—C15	48.4 (2)
C6—C7—C8—C14	−172.44 (19)	C8—C14—C15—C16	−165.5 (2)
C6—C7—C8—C9	−53.0 (3)	C13—C14—C15—C16	−34.5 (2)
C14—C8—C9—C11	−52.3 (3)	C14—C15—C16—C17	6.9 (2)
C7—C8—C9—C11	−173.00 (19)	C12—C13—C17—C20	76.6 (3)
C14—C8—C9—C10	177.81 (19)	C19—C13—C17—C20	−50.6 (3)
C7—C8—C9—C10	57.1 (2)	C14—C13—C17—C20	−169.2 (2)
C2—C1—C10—C18	−77.1 (2)	C12—C13—C17—C16	−157.0 (2)
C2—C1—C10—C5	44.1 (3)	C19—C13—C17—C16	75.8 (2)
C2—C1—C10—C9	159.76 (18)	C14—C13—C17—C16	−42.8 (2)
C6—C5—C10—C18	−66.1 (2)	C15—C16—C17—C20	154.84 (19)
C4—C5—C10—C18	59.5 (2)	C15—C16—C17—C13	22.8 (2)
C6—C5—C10—C1	174.20 (18)	C13—C17—C20—C21	−52.1 (3)
C4—C5—C10—C1	−60.2 (2)	C16—C17—C20—C21	−174.1 (2)
C6—C5—C10—C9	57.3 (2)	C13—C17—C20—C22	−175.5 (2)
C4—C5—C10—C9	−177.04 (18)	C16—C17—C20—C22	62.5 (3)
C11—C9—C10—C18	−64.5 (3)	C21—C20—C22—C23	60.4 (3)
C8—C9—C10—C18	64.2 (2)	C17—C20—C22—C23	−174.8 (2)
C11—C9—C10—C1	56.6 (3)	C20—C22—C23—C24	179.9 (2)
C8—C9—C10—C1	−174.79 (19)	C22—C23—C24—C25	−174.3 (2)
C11—C9—C10—C5	172.66 (19)	C23—C24—C25—C27	68.5 (3)
C8—C9—C10—C5	−58.7 (2)	C23—C24—C25—C26	−168.5 (2)
C8—C9—C11—C12	54.2 (3)	C3—C2—C211—O211	178.7 (2)
C10—C9—C11—C12	−176.54 (19)	C1—C2—C211—O211	−2.3 (4)
C9—C11—C12—C13	−56.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O211^i	0.99	2.60	3.200 (3)	119

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

Methyl (R)-4-[(5S,8R,9S,10R,13R,14S,17R)-3-chloro-4-formyl-10,13-dimethyl-12-oxo-2,5,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl]pentanoate (IV)

Crystal data

C26H37ClO4	Dx = 1.277 Mg m^−3
Mr = 449.01	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 5558 reflections
a = 7.0444 (3) Å	θ = 2.3–27.9°
b = 10.8756 (6) Å	µ = 0.19 mm^−1
c = 30.4910 (14) Å	T = 100 K
V = 2335.98 (19) Å^3	Block, colourless
Z = 4	0.28 × 0.17 × 0.12 mm
F(000) = 968

Data collection

Bruker D8 Venture diffractometer	5558 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	4513 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.074
φ and ω scans	θmax = 27.9°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −8→9
Tmin = 0.929, Tmax = 0.977	k = −14→14
23212 measured reflections	l = −39→39

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.048	w = 1/[σ^2(Fo^2) + (0.0362P)^2 + 0.4052P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.090	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.28 e Å^−3
5558 reflections	Δρmin = −0.27 e Å^−3
284 parameters	Absolute structure: Flack x determined using 1650 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.05 (3)

Special details

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

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

	x	y	z	Uiso*/Ueq
C1	−0.0310 (4)	0.7208 (2)	0.73259 (9)	0.0129 (6)
H1A	−0.0624	0.8010	0.7461	0.015*
H1B	−0.1509	0.6828	0.7225	0.015*
C2	0.0607 (4)	0.6380 (3)	0.76699 (9)	0.0137 (6)
H2A	−0.0179	0.6372	0.7939	0.016*
H2B	0.0690	0.5528	0.7557	0.016*
C3	0.2541 (4)	0.6844 (3)	0.77745 (9)	0.0123 (6)
Cl3	0.34195 (11)	0.62817 (7)	0.82729 (2)	0.02031 (17)
C4	0.3526 (4)	0.7653 (2)	0.75318 (9)	0.0109 (5)
C5	0.2769 (4)	0.8138 (3)	0.70954 (8)	0.0110 (6)
H5	0.2344	0.9002	0.7150	0.013*
C6	0.4318 (4)	0.8204 (3)	0.67408 (9)	0.0135 (6)
H6A	0.3873	0.8744	0.6501	0.016*
H6B	0.5469	0.8582	0.6869	0.016*
C7	0.4842 (4)	0.6951 (3)	0.65496 (9)	0.0124 (6)
H7A	0.5408	0.6433	0.6782	0.015*
H7B	0.5805	0.7062	0.6316	0.015*
C8	0.3100 (4)	0.6300 (3)	0.63585 (8)	0.0101 (5)
H8	0.2559	0.6808	0.6115	0.012*
C9	0.1618 (4)	0.6174 (2)	0.67272 (8)	0.0090 (5)
H9	0.2264	0.5713	0.6969	0.011*
C10	0.0998 (4)	0.7421 (2)	0.69297 (9)	0.0103 (6)
C11	−0.0090 (4)	0.5365 (2)	0.65852 (9)	0.0132 (6)
H11A	−0.0925	0.5208	0.6840	0.016*
H11B	−0.0841	0.5799	0.6359	0.016*
C12	0.0635 (4)	0.4162 (3)	0.64043 (9)	0.0104 (6)
O12	0.0436 (3)	0.32029 (18)	0.66042 (6)	0.0207 (5)
C13	0.1888 (4)	0.4287 (2)	0.60019 (8)	0.0085 (5)
C14	0.3611 (4)	0.5034 (2)	0.61849 (8)	0.0101 (5)
H14	0.4120	0.4557	0.6439	0.012*
C15	0.5072 (4)	0.4918 (3)	0.58173 (9)	0.0163 (6)
H15A	0.6379	0.4998	0.5933	0.020*
H15B	0.4867	0.5556	0.5590	0.020*
C16	0.4733 (4)	0.3614 (3)	0.56270 (9)	0.0154 (6)
H16A	0.4585	0.3654	0.5304	0.018*
H16B	0.5822	0.3071	0.5696	0.018*
C17	0.2895 (3)	0.3111 (3)	0.58418 (9)	0.0102 (5)
H17	0.3272	0.2626	0.6106	0.012*
C18	−0.0067 (4)	0.8232 (3)	0.65961 (9)	0.0157 (6)
H18A	−0.1237	0.7817	0.6505	0.024*
H18B	0.0741	0.8373	0.6339	0.024*
H18C	−0.0384	0.9022	0.6732	0.024*
C19	0.0862 (4)	0.4956 (3)	0.56255 (9)	0.0130 (6)
H19A	−0.0317	0.4521	0.5555	0.019*
H19B	0.1684	0.4974	0.5366	0.019*
H19C	0.0566	0.5800	0.5716	0.019*
C20	0.1789 (4)	0.2245 (2)	0.55331 (9)	0.0108 (6)
H20	0.1457	0.2733	0.5266	0.013*
C21	−0.0078 (4)	0.1785 (3)	0.57286 (10)	0.0188 (6)
H21A	0.0175	0.1370	0.6008	0.028*
H21B	−0.0677	0.1206	0.5525	0.028*
H21C	−0.0930	0.2483	0.5779	0.028*
C22	0.3021 (4)	0.1157 (3)	0.53795 (8)	0.0119 (6)
H22A	0.2262	0.0641	0.5178	0.014*
H22B	0.4114	0.1483	0.5212	0.014*
C23	0.3773 (5)	0.0346 (3)	0.57512 (9)	0.0215 (7)
H23A	0.4700	0.0819	0.5928	0.026*
H23B	0.2709	0.0108	0.5946	0.026*
C24	0.4711 (4)	−0.0790 (3)	0.55754 (9)	0.0182 (7)
O24	0.3881 (3)	−0.1685 (2)	0.54457 (8)	0.0319 (6)
O25	0.6600 (3)	−0.06945 (18)	0.55754 (7)	0.0231 (5)
C25	0.7633 (5)	−0.1731 (3)	0.54004 (11)	0.0298 (8)
H25A	0.7255	−0.1868	0.5095	0.045*
H25B	0.7348	−0.2466	0.5574	0.045*
H25C	0.8998	−0.1561	0.5413	0.045*
C411	0.5238 (4)	0.8238 (3)	0.77134 (9)	0.0163 (6)
H411	0.5919	0.7813	0.7935	0.020*
O411	0.5829 (3)	0.9233 (2)	0.75964 (7)	0.0235 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0101 (13)	0.0125 (14)	0.0160 (14)	−0.0012 (11)	−0.0002 (12)	−0.0066 (12)
C2	0.0164 (14)	0.0135 (14)	0.0111 (13)	−0.0011 (12)	0.0044 (11)	−0.0032 (12)
C3	0.0176 (14)	0.0093 (13)	0.0100 (14)	0.0035 (12)	−0.0012 (11)	−0.0029 (12)
Cl3	0.0300 (4)	0.0193 (4)	0.0116 (3)	0.0030 (3)	−0.0043 (3)	0.0029 (3)
C4	0.0125 (13)	0.0082 (13)	0.0122 (13)	0.0029 (11)	−0.0021 (12)	−0.0036 (11)
C5	0.0128 (13)	0.0074 (13)	0.0128 (14)	−0.0027 (11)	−0.0020 (11)	0.0002 (11)
C6	0.0153 (13)	0.0122 (14)	0.0130 (13)	−0.0062 (11)	−0.0019 (12)	−0.0014 (12)
C7	0.0090 (13)	0.0144 (14)	0.0137 (14)	−0.0048 (11)	0.0018 (11)	−0.0030 (12)
C8	0.0106 (13)	0.0099 (13)	0.0097 (13)	−0.0003 (11)	−0.0006 (10)	0.0006 (11)
C9	0.0080 (11)	0.0093 (12)	0.0097 (11)	−0.0001 (11)	−0.0011 (11)	−0.0004 (11)
C10	0.0096 (13)	0.0097 (14)	0.0116 (13)	0.0005 (10)	−0.0031 (11)	−0.0010 (11)
C11	0.0100 (13)	0.0143 (15)	0.0153 (14)	−0.0015 (11)	0.0021 (11)	−0.0048 (11)
C12	0.0067 (12)	0.0123 (14)	0.0122 (13)	−0.0039 (11)	−0.0017 (11)	−0.0029 (11)
O12	0.0322 (11)	0.0125 (10)	0.0173 (11)	−0.0066 (9)	0.0088 (9)	0.0001 (9)
C13	0.0084 (13)	0.0084 (13)	0.0088 (12)	−0.0011 (10)	−0.0011 (10)	−0.0019 (11)
C14	0.0084 (12)	0.0117 (14)	0.0102 (13)	−0.0006 (11)	−0.0021 (11)	−0.0002 (11)
C15	0.0113 (14)	0.0192 (15)	0.0183 (15)	−0.0052 (12)	0.0041 (12)	−0.0047 (13)
C16	0.0105 (13)	0.0179 (15)	0.0178 (15)	−0.0014 (12)	0.0048 (11)	−0.0079 (12)
C17	0.0098 (12)	0.0124 (14)	0.0084 (13)	0.0015 (11)	−0.0002 (10)	−0.0008 (11)
C18	0.0165 (14)	0.0108 (13)	0.0198 (15)	0.0006 (12)	−0.0056 (12)	−0.0037 (12)
C19	0.0171 (14)	0.0097 (14)	0.0122 (14)	0.0012 (11)	−0.0038 (12)	−0.0009 (12)
C20	0.0111 (13)	0.0103 (13)	0.0110 (13)	0.0016 (11)	−0.0008 (11)	−0.0005 (11)
C21	0.0135 (14)	0.0172 (15)	0.0258 (17)	−0.0021 (13)	0.0032 (12)	−0.0075 (14)
C22	0.0160 (14)	0.0102 (14)	0.0096 (13)	−0.0015 (11)	−0.0005 (11)	−0.0018 (11)
C23	0.0327 (18)	0.0177 (16)	0.0141 (15)	0.0096 (13)	−0.0046 (13)	−0.0028 (12)
C24	0.0279 (17)	0.0143 (15)	0.0126 (15)	0.0059 (13)	−0.0037 (13)	0.0010 (12)
O24	0.0348 (13)	0.0214 (13)	0.0396 (14)	0.0013 (10)	−0.0092 (11)	−0.0107 (11)
O25	0.0243 (11)	0.0164 (11)	0.0286 (12)	0.0021 (10)	0.0028 (11)	−0.0023 (9)
C25	0.0313 (18)	0.0246 (18)	0.0336 (19)	0.0101 (15)	0.0064 (15)	0.0009 (16)
C411	0.0160 (14)	0.0197 (15)	0.0132 (14)	−0.0001 (13)	−0.0031 (12)	−0.0044 (13)
O411	0.0255 (11)	0.0219 (12)	0.0231 (12)	−0.0101 (10)	−0.0041 (9)	−0.0058 (10)

Geometric parameters (Å, º)

C1—C2	1.526 (4)	C14—H14	1.0000
C1—C10	1.537 (4)	C15—C16	1.552 (4)
C1—H1A	0.9900	C15—H15A	0.9900
C1—H1B	0.9900	C15—H15B	0.9900
C2—C3	1.487 (4)	C16—C17	1.551 (4)
C2—H2A	0.9900	C16—H16A	0.9900
C2—H2B	0.9900	C16—H16B	0.9900
C3—C4	1.342 (4)	C17—C20	1.543 (4)
C3—Cl3	1.751 (3)	C17—H17	1.0000
C4—C411	1.472 (4)	C18—H18A	0.9800
C4—C5	1.527 (4)	C18—H18B	0.9800
C5—C6	1.538 (4)	C18—H18C	0.9800
C5—C10	1.556 (4)	C19—H19A	0.9800
C5—H5	1.0000	C19—H19B	0.9800
C6—C7	1.527 (4)	C19—H19C	0.9800
C6—H6A	0.9900	C20—C21	1.528 (4)
C6—H6B	0.9900	C20—C22	1.541 (4)
C7—C8	1.532 (4)	C20—H20	1.0000
C7—H7A	0.9900	C21—H21A	0.9800
C7—H7B	0.9900	C21—H21B	0.9800
C8—C14	1.519 (4)	C21—H21C	0.9800
C8—C9	1.540 (3)	C22—C23	1.531 (4)
C8—H8	1.0000	C22—H22A	0.9900
C9—C11	1.552 (4)	C22—H22B	0.9900
C9—C10	1.553 (4)	C23—C24	1.500 (4)
C9—H9	1.0000	C23—H23A	0.9900
C10—C18	1.542 (4)	C23—H23B	0.9900
C11—C12	1.509 (4)	C24—O24	1.202 (4)
C11—H11A	0.9900	C24—O25	1.335 (4)
C11—H11B	0.9900	O25—C25	1.444 (4)
C12—O12	1.216 (3)	C25—H25A	0.9800
C12—C13	1.518 (4)	C25—H25B	0.9800
C13—C19	1.540 (4)	C25—H25C	0.9800
C13—C17	1.541 (4)	C411—O411	1.213 (4)
C13—C14	1.564 (3)	C411—H411	0.9500
C14—C15	1.527 (4)
C2—C1—C10	112.0 (2)	C15—C14—C13	102.6 (2)
C2—C1—H1A	109.2	C8—C14—H14	106.6
C10—C1—H1A	109.2	C15—C14—H14	106.6
C2—C1—H1B	109.2	C13—C14—H14	106.6
C10—C1—H1B	109.2	C14—C15—C16	104.2 (2)
H1A—C1—H1B	107.9	C14—C15—H15A	110.9
C3—C2—C1	109.6 (2)	C16—C15—H15A	110.9
C3—C2—H2A	109.8	C14—C15—H15B	110.9
C1—C2—H2A	109.8	C16—C15—H15B	110.9
C3—C2—H2B	109.8	H15A—C15—H15B	108.9
C1—C2—H2B	109.8	C17—C16—C15	107.0 (2)
H2A—C2—H2B	108.2	C17—C16—H16A	110.3
C4—C3—C2	125.3 (2)	C15—C16—H16A	110.3
C4—C3—Cl3	121.7 (2)	C17—C16—H16B	110.3
C2—C3—Cl3	113.0 (2)	C15—C16—H16B	110.3
C3—C4—C411	119.9 (2)	H16A—C16—H16B	108.6
C3—C4—C5	121.7 (2)	C13—C17—C20	117.9 (2)
C411—C4—C5	117.7 (2)	C13—C17—C16	103.0 (2)
C4—C5—C6	112.4 (2)	C20—C17—C16	112.3 (2)
C4—C5—C10	113.0 (2)	C13—C17—H17	107.7
C6—C5—C10	111.3 (2)	C20—C17—H17	107.7
C4—C5—H5	106.6	C16—C17—H17	107.7
C6—C5—H5	106.6	C10—C18—H18A	109.5
C10—C5—H5	106.6	C10—C18—H18B	109.5
C7—C6—C5	113.5 (2)	H18A—C18—H18B	109.5
C7—C6—H6A	108.9	C10—C18—H18C	109.5
C5—C6—H6A	108.9	H18A—C18—H18C	109.5
C7—C6—H6B	108.9	H18B—C18—H18C	109.5
C5—C6—H6B	108.9	C13—C19—H19A	109.5
H6A—C6—H6B	107.7	C13—C19—H19B	109.5
C6—C7—C8	111.3 (2)	H19A—C19—H19B	109.5
C6—C7—H7A	109.4	C13—C19—H19C	109.5
C8—C7—H7A	109.4	H19A—C19—H19C	109.5
C6—C7—H7B	109.4	H19B—C19—H19C	109.5
C8—C7—H7B	109.4	C21—C20—C22	110.6 (2)
H7A—C7—H7B	108.0	C21—C20—C17	113.4 (2)
C14—C8—C7	111.2 (2)	C22—C20—C17	111.7 (2)
C14—C8—C9	109.5 (2)	C21—C20—H20	106.9
C7—C8—C9	107.9 (2)	C22—C20—H20	106.9
C14—C8—H8	109.4	C17—C20—H20	106.9
C7—C8—H8	109.4	C20—C21—H21A	109.5
C9—C8—H8	109.4	C20—C21—H21B	109.5
C8—C9—C11	111.9 (2)	H21A—C21—H21B	109.5
C8—C9—C10	113.8 (2)	C20—C21—H21C	109.5
C11—C9—C10	112.8 (2)	H21A—C21—H21C	109.5
C8—C9—H9	105.9	H21B—C21—H21C	109.5
C11—C9—H9	105.9	C23—C22—C20	114.4 (2)
C10—C9—H9	105.9	C23—C22—H22A	108.7
C1—C10—C18	108.2 (2)	C20—C22—H22A	108.7
C1—C10—C9	110.5 (2)	C23—C22—H22B	108.7
C18—C10—C9	112.0 (2)	C20—C22—H22B	108.7
C1—C10—C5	107.5 (2)	H22A—C22—H22B	107.6
C18—C10—C5	108.5 (2)	C24—C23—C22	111.2 (2)
C9—C10—C5	110.0 (2)	C24—C23—H23A	109.4
C12—C11—C9	109.3 (2)	C22—C23—H23A	109.4
C12—C11—H11A	109.8	C24—C23—H23B	109.4
C9—C11—H11A	109.8	C22—C23—H23B	109.4
C12—C11—H11B	109.8	H23A—C23—H23B	108.0
C9—C11—H11B	109.8	O24—C24—O25	123.2 (3)
H11A—C11—H11B	108.3	O24—C24—C23	124.8 (3)
O12—C12—C11	121.4 (2)	O25—C24—C23	112.0 (3)
O12—C12—C13	123.3 (2)	C24—O25—C25	116.2 (2)
C11—C12—C13	114.5 (2)	O25—C25—H25A	109.5
C12—C13—C19	111.8 (2)	O25—C25—H25B	109.5
C12—C13—C17	116.7 (2)	H25A—C25—H25B	109.5
C19—C13—C17	111.9 (2)	O25—C25—H25C	109.5
C12—C13—C14	102.09 (19)	H25A—C25—H25C	109.5
C19—C13—C14	112.6 (2)	H25B—C25—H25C	109.5
C17—C13—C14	100.8 (2)	O411—C411—C4	123.8 (3)
C8—C14—C15	119.4 (2)	O411—C411—H411	118.1
C8—C14—C13	114.3 (2)	C4—C411—H411	118.1
C10—C1—C2—C3	50.4 (3)	C11—C12—C13—C19	−57.7 (3)
C1—C2—C3—C4	−15.9 (4)	O12—C12—C13—C17	1.6 (4)
C1—C2—C3—Cl3	161.28 (18)	C11—C12—C13—C17	171.7 (2)
C2—C3—C4—C411	167.1 (2)	O12—C12—C13—C14	−107.2 (3)
Cl3—C3—C4—C411	−9.8 (4)	C11—C12—C13—C14	62.9 (3)
C2—C3—C4—C5	−3.5 (4)	C7—C8—C14—C15	−60.5 (3)
Cl3—C3—C4—C5	179.6 (2)	C9—C8—C14—C15	−179.6 (2)
C3—C4—C5—C6	−138.0 (3)	C7—C8—C14—C13	177.6 (2)
C411—C4—C5—C6	51.1 (3)	C9—C8—C14—C13	58.5 (3)
C3—C4—C5—C10	−11.0 (4)	C12—C13—C14—C8	−61.5 (3)
C411—C4—C5—C10	178.1 (2)	C19—C13—C14—C8	58.6 (3)
C4—C5—C6—C7	75.6 (3)	C17—C13—C14—C8	177.9 (2)
C10—C5—C6—C7	−52.3 (3)	C12—C13—C14—C15	167.7 (2)
C5—C6—C7—C8	56.8 (3)	C19—C13—C14—C15	−72.2 (3)
C6—C7—C8—C14	−177.7 (2)	C17—C13—C14—C15	47.2 (2)
C6—C7—C8—C9	−57.6 (3)	C8—C14—C15—C16	−161.8 (2)
C14—C8—C9—C11	−50.9 (3)	C13—C14—C15—C16	−34.2 (3)
C7—C8—C9—C11	−172.0 (2)	C14—C15—C16—C17	8.7 (3)
C14—C8—C9—C10	179.8 (2)	C12—C13—C17—C20	85.3 (3)
C7—C8—C9—C10	58.7 (3)	C19—C13—C17—C20	−45.3 (3)
C2—C1—C10—C18	178.4 (2)	C14—C13—C17—C20	−165.2 (2)
C2—C1—C10—C9	55.4 (3)	C12—C13—C17—C16	−150.5 (2)
C2—C1—C10—C5	−64.6 (3)	C19—C13—C17—C16	78.9 (3)
C8—C9—C10—C1	−173.9 (2)	C14—C13—C17—C16	−41.0 (2)
C11—C9—C10—C1	57.3 (3)	C15—C16—C17—C13	20.5 (3)
C8—C9—C10—C18	65.4 (3)	C15—C16—C17—C20	148.3 (2)
C11—C9—C10—C18	−63.4 (3)	C13—C17—C20—C21	−57.8 (3)
C8—C9—C10—C5	−55.4 (3)	C16—C17—C20—C21	−177.3 (2)
C11—C9—C10—C5	175.8 (2)	C13—C17—C20—C22	176.5 (2)
C4—C5—C10—C1	42.8 (3)	C16—C17—C20—C22	57.0 (3)
C6—C5—C10—C1	170.3 (2)	C21—C20—C22—C23	−67.6 (3)
C4—C5—C10—C18	159.6 (2)	C17—C20—C22—C23	59.7 (3)
C6—C5—C10—C18	−72.8 (3)	C20—C22—C23—C24	171.6 (2)
C4—C5—C10—C9	−77.5 (3)	C22—C23—C24—O24	−78.6 (4)
C6—C5—C10—C9	50.0 (3)	C22—C23—C24—O25	101.0 (3)
C8—C9—C11—C12	51.8 (3)	O24—C24—O25—C25	1.2 (4)
C10—C9—C11—C12	−178.5 (2)	C23—C24—O25—C25	−178.3 (2)
C9—C11—C12—O12	109.1 (3)	C3—C4—C411—O411	−153.8 (3)
C9—C11—C12—C13	−61.2 (3)	C5—C4—C411—O411	17.2 (4)
O12—C12—C13—C19	132.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O12^i	0.99	2.44	3.061 (4)	121
C9—H9···O411^ii	1.00	2.48	3.456 (3)	165
C25—H25A···O24^iii	0.99	2.55	3.224 (4)	126

Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2; (iii) x+1/2, −y−1/2, −z+1.