(9S,13R,14S)-7,8-Didehydro-4-(4-fluoro­benz­yloxy)-3,7-dimeth­oxy-17-methyl­morphinan-6-one sesquihydrate

Zheng, X.-L.; Jiang, N.-F.; Luo, D.; Gao, H.-S.; Ding, A.-S.

doi:10.1107/S1600536811026183

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1988

doi:10.1107/S1600536811026183

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(9S,13R,14S)-7,8-Didehydro-4-(4-fluorobenzyloxy)-3,7-dimethoxy-17-methylmorphinan-6-one sesquihydrate

Xing-Liang Zheng,^a ^* Ning-Fei Jiang,^a Dan Luo,^a Hong-Sheng Gao ^a and Ai-Shun Ding ^a

^aSchool of Chemistry and Biological Engineering, Changsha University of Science & Technology, Changsha 410114, People's Republic of China
^*Correspondence e-mail: xingliangzheng@163.com

(Received 3 June 2011; accepted 1 July 2011; online 9 July 2011)

In the title sinomenine derivative, C₂₆H₂₈FNO₄·1.5H₂O, the dihedral angle between the two aromatic rings is 55.32 (6)°. The N-containing ring has an approximate chair conformation, while other two rings have approximate envelope and half-chair conformations. One water molecule is located on a twofold symmetry axis. In the crystal, the water molecules form O—H⋯O and O—H⋯N hydrogen bonds, bridging symmetry-related main molecules.

Related literature

For background to the biological activity of sinomenine derivatives and other related compounds, see: Liu et al. (1994 , 1996 , 1997 ); Mark et al. (2003 ); Ye et al. (2004 ). For the synthesis of the title compound, see: Mitsunobu (1981 ). For related structures, see: Li et al. (2009 ); Batterham et al. (1965 ); Zheng & Jiang (2010 ); Zheng et al. (2011 ).

Experimental

Crystal data

C₂₆H₂₈FNO₄·1.5H₂O
M_r = 464.52
Monoclinic, C 2
a = 18.0155 (3) Å
b = 7.6776 (1) Å
c = 18.1506 (4) Å
β = 109.324 (1)°
V = 2369.08 (7) Å³
Z = 4
Cu Kα radiation
μ = 0.79 mm⁻¹
T = 133 K
0.25 × 0.15 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.826, T_max = 0.925
7232 measured reflections
3415 independent reflections
3402 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.081
S = 1.04
3415 reflections
312 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ), 1359 Friedel pairs
Flack parameter: 0.05 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2S—H22S⋯O4	0.91	2.33	2.9805 (16)	128
O2S—H22S⋯O3	0.91	2.54	3.417 (2)	164
O1S—H11S⋯O2S	0.90 (3)	1.94 (3)	2.8342 (19)	172 (2)
O2S—H21S⋯N1ⁱ	0.97	1.81	2.7736 (19)	170
Symmetry code: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811026183/bh2361sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811026183/bh2361Isup2.hkl

checkCIF report

Comment top

We synthesized a new sinomenine derivative sesquihydrate. Herein, its crystal structure is reported. Biological effects of sinomenine derivatives and related compounds have been described (Liu et al., 1994, 1996, 1997; Mark et al., 2003; Ye et al., 2004).

The molecular structure of the title compound is shown in Fig. 1. The crystal structure is stabilized by O—H···O and O—H···N hydrogen bonds linking the sinomenine derivative and the water molecules, and weak C—H···O hydrogen bonds between molecules (Fig. 2). Significant aromatic stacking interactions were not found. There exist two planes in the molecule of the title compound: atoms C1···C6 form the benzene plane (I), and atoms C21···C26 form the benzene plane substituted by fluorine (II). The angle between the two planes (I) and (II) is 55.32 (6)°. Rings C [C7/C8/C11/C12/C13/C14] and B [C5···C10] in the molecule approximate envelope and half-chair conformations, respectively. In contrast, ring D [C9/N1/C16/C15/C7/C8] exhibits an almost regular chair conformation. Similar features have been described in related compounds (Zheng & Jiang, 2010; Zheng et al., 2011; Li et al., 2009; Batterham et al., 1965).

Related literature top

For background to biological activity of sinomenine derivatives and other related compounds, see: Liu et al. (1994, 1996, 1997); Mark et al. (2003); Ye et al. (2004). For the synthesis of the title compound, see: Mitsunobu (1981). For related structures, see: Li et al. (2009); Batterham et al. (1965); Zheng & Jiang (2010); Zheng et al. (2011).

Experimental top

The title compound was obtained according to the method of Mitsunobu (1981). Colorless blocks were grown from an acetic ether solution.

Computing details top

Data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids.
	Fig. 2. A part of the crystal structure of the title compound.

(9S,13R,14S)-7,8-Didehydro-4-(4-fluorobenzyloxy)-3,7- dimethoxy-17-methylmorphinan-6-one sesquihydrate top

Crystal data top

C₂₆H₂₈FNO₄·1.5H₂O	F(000) = 988
M_r = 464.52	D_x = 1.302 Mg m⁻³
Monoclinic, C2	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: C 2y	Cell parameters from 6582 reflections
a = 18.0155 (3) Å	θ = 2.6–64.7°
b = 7.6776 (1) Å	µ = 0.79 mm⁻¹
c = 18.1506 (4) Å	T = 133 K
β = 109.324 (1)°	Block, colourless
V = 2369.08 (7) Å³	0.25 × 0.15 × 0.10 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3415 independent reflections
Radiation source: fine-focus sealed tube	3402 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 65.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −20→21
T_min = 0.826, T_max = 0.925	k = −9→9
7232 measured reflections	l = −18→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0555P)² + 0.6114P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3415 reflections	Δρ_max = 0.20 e Å⁻³
312 parameters	Δρ_min = −0.18 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1359 Friedel pairs
0 constraints	Absolute structure parameter: 0.05 (12)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₂₆H₂₈FNO₄·1.5H₂O	V = 2369.08 (7) Å³
M_r = 464.52	Z = 4
Monoclinic, C2	Cu Kα radiation
a = 18.0155 (3) Å	µ = 0.79 mm⁻¹
b = 7.6776 (1) Å	T = 133 K
c = 18.1506 (4) Å	0.25 × 0.15 × 0.10 mm
β = 109.324 (1)°

Data collection top

Bruker APEXII CCD diffractometer	3415 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3402 reflections with I > 2σ(I)
T_min = 0.826, T_max = 0.925	R_int = 0.024
7232 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.081	Δρ_max = 0.20 e Å⁻³
S = 1.04	Δρ_min = −0.18 e Å⁻³
3415 reflections	Absolute structure: Flack (1983), 1359 Friedel pairs
312 parameters	Absolute structure parameter: 0.05 (12)
1 restraint

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

	x	y	z	U_iso*/U_eq
F1	0.49485 (7)	−0.26627 (16)	0.40332 (8)	0.0571 (3)
N1	−0.03356 (8)	0.4513 (2)	0.15607 (8)	0.0314 (3)
O1	0.26142 (6)	0.36402 (13)	0.34083 (6)	0.0237 (2)
O2	0.29280 (6)	0.57951 (14)	0.46321 (6)	0.0268 (2)
O3	0.32140 (7)	0.48228 (18)	0.15878 (7)	0.0392 (3)
O4	0.24651 (6)	0.74481 (15)	0.07306 (7)	0.0307 (3)
C1	0.21885 (8)	0.51681 (19)	0.33202 (9)	0.0217 (3)
C2	0.23288 (8)	0.6279 (2)	0.39717 (9)	0.0233 (3)
C3	0.18682 (9)	0.7742 (2)	0.39246 (9)	0.0265 (3)
H3	0.1968	0.8511	0.4357	0.032*
C4	0.12611 (8)	0.80691 (19)	0.32395 (9)	0.0253 (3)
H4	0.0943	0.9072	0.3209	0.030*
C5	0.10990 (8)	0.6993 (2)	0.25971 (9)	0.0239 (3)
C6	0.15775 (8)	0.55115 (19)	0.26184 (9)	0.0220 (3)
C7	0.13574 (8)	0.4223 (2)	0.19297 (9)	0.0254 (3)
C8	0.08177 (8)	0.5102 (2)	0.11800 (9)	0.0264 (3)
H8	0.0620	0.4171	0.0777	0.032*
C9	0.01057 (9)	0.5906 (2)	0.13270 (9)	0.0285 (3)
H9	−0.0244	0.6395	0.0820	0.034*
C10	0.03877 (8)	0.7424 (2)	0.18927 (9)	0.0279 (3)
H10A	0.0520	0.8416	0.1610	0.033*
H10B	−0.0048	0.7799	0.2075	0.033*
C11	0.20578 (9)	0.3494 (2)	0.17160 (9)	0.0275 (3)
H11A	0.2421	0.2888	0.2176	0.033*
H11B	0.1861	0.2628	0.1292	0.033*
C12	0.25034 (9)	0.4894 (2)	0.14564 (9)	0.0281 (3)
C13	0.20238 (9)	0.6325 (2)	0.09902 (9)	0.0266 (3)
C14	0.12457 (9)	0.6423 (2)	0.08562 (9)	0.0259 (3)
H14	0.0957	0.7353	0.0548	0.031*
C15	0.08761 (10)	0.2737 (2)	0.21185 (10)	0.0316 (4)
H15A	0.0736	0.1877	0.1688	0.038*
H15B	0.1198	0.2137	0.2601	0.038*
C16	0.01249 (10)	0.3444 (2)	0.22285 (10)	0.0330 (4)
H16A	−0.0202	0.2457	0.2293	0.040*
H16B	0.0267	0.4156	0.2710	0.040*
C17	0.31222 (10)	0.6993 (2)	0.52708 (9)	0.0332 (4)
H17A	0.3228	0.8142	0.5092	0.050*
H17B	0.3590	0.6580	0.5686	0.050*
H17C	0.2681	0.7079	0.5471	0.050*
C18	0.20598 (10)	0.8932 (2)	0.03173 (10)	0.0355 (4)
H18A	0.1646	0.8552	−0.0158	0.053*
H18B	0.2431	0.9685	0.0177	0.053*
H18C	0.1823	0.9579	0.0649	0.053*
C19	−0.10438 (10)	0.5180 (3)	0.16953 (12)	0.0392 (4)
H19A	−0.1362	0.4201	0.1767	0.059*
H19B	−0.1352	0.5874	0.1245	0.059*
H19C	−0.0890	0.5911	0.2164	0.059*
C20	0.34415 (9)	0.3842 (2)	0.35220 (9)	0.0273 (3)
H20A	0.3687	0.4621	0.3971	0.033*
H20B	0.3512	0.4367	0.3051	0.033*
C21	0.38241 (9)	0.2075 (2)	0.36728 (9)	0.0262 (3)
C22	0.46433 (10)	0.1988 (2)	0.39458 (10)	0.0323 (4)
H22	0.4942	0.3033	0.4049	0.039*
C23	0.50269 (10)	0.0401 (3)	0.40683 (11)	0.0394 (4)
H23	0.5585	0.0343	0.4250	0.047*
C24	0.45800 (11)	−0.1091 (3)	0.39200 (12)	0.0398 (4)
C25	0.37742 (11)	−0.1056 (2)	0.36530 (12)	0.0397 (4)
H25	0.3480	−0.2107	0.3556	0.048*
C26	0.33978 (10)	0.0545 (2)	0.35278 (11)	0.0335 (4)
H26	0.2839	0.0590	0.3340	0.040*
O2S	0.39668 (7)	0.7129 (2)	0.03873 (8)	0.0485 (4)
H21S	0.4268	0.7898	0.0802	0.043 (6)*
H22S	0.3668	0.6573	0.0628	0.131 (15)*
O1S	0.5000	0.4796 (3)	0.0000	0.0471 (5)
H11S	0.4712 (14)	0.555 (4)	0.0168 (15)	0.059 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0562 (6)	0.0372 (6)	0.0885 (9)	0.0217 (5)	0.0383 (6)	0.0200 (6)
N1	0.0288 (6)	0.0374 (8)	0.0294 (8)	−0.0071 (6)	0.0115 (5)	−0.0058 (6)
O1	0.0254 (5)	0.0206 (5)	0.0261 (6)	0.0017 (4)	0.0101 (4)	0.0017 (4)
O2	0.0308 (5)	0.0273 (5)	0.0195 (6)	0.0014 (4)	0.0045 (4)	−0.0017 (4)
O3	0.0355 (6)	0.0483 (8)	0.0397 (7)	0.0102 (5)	0.0205 (5)	0.0108 (6)
O4	0.0313 (5)	0.0316 (6)	0.0331 (6)	−0.0011 (5)	0.0158 (4)	0.0059 (5)
C1	0.0241 (6)	0.0198 (7)	0.0241 (8)	−0.0004 (5)	0.0117 (5)	0.0022 (6)
C2	0.0244 (7)	0.0244 (7)	0.0219 (8)	−0.0044 (6)	0.0088 (6)	0.0001 (6)
C3	0.0298 (7)	0.0260 (8)	0.0253 (8)	−0.0044 (6)	0.0113 (6)	−0.0051 (6)
C4	0.0258 (7)	0.0220 (7)	0.0299 (9)	0.0000 (6)	0.0117 (6)	−0.0004 (6)
C5	0.0223 (6)	0.0252 (8)	0.0251 (8)	−0.0033 (6)	0.0091 (6)	0.0035 (6)
C6	0.0248 (7)	0.0221 (7)	0.0215 (8)	−0.0046 (6)	0.0110 (6)	0.0005 (6)
C7	0.0310 (7)	0.0261 (8)	0.0194 (8)	−0.0040 (6)	0.0086 (6)	−0.0019 (6)
C8	0.0290 (7)	0.0287 (8)	0.0208 (8)	−0.0043 (6)	0.0072 (6)	−0.0022 (6)
C9	0.0263 (7)	0.0342 (9)	0.0230 (9)	−0.0044 (7)	0.0056 (6)	−0.0004 (7)
C10	0.0259 (7)	0.0294 (8)	0.0271 (9)	0.0014 (6)	0.0070 (6)	0.0018 (6)
C11	0.0398 (8)	0.0236 (8)	0.0207 (8)	0.0012 (6)	0.0120 (6)	−0.0038 (6)
C12	0.0346 (8)	0.0314 (9)	0.0214 (8)	0.0022 (7)	0.0138 (6)	−0.0038 (6)
C13	0.0330 (7)	0.0301 (8)	0.0188 (8)	−0.0025 (6)	0.0113 (6)	−0.0019 (6)
C14	0.0311 (7)	0.0286 (8)	0.0165 (8)	−0.0042 (6)	0.0060 (6)	−0.0013 (6)
C15	0.0391 (8)	0.0270 (8)	0.0289 (9)	−0.0083 (7)	0.0115 (7)	−0.0035 (7)
C16	0.0371 (8)	0.0350 (9)	0.0296 (9)	−0.0130 (7)	0.0145 (6)	−0.0028 (7)
C17	0.0426 (9)	0.0300 (8)	0.0216 (9)	−0.0040 (7)	0.0034 (6)	−0.0033 (6)
C18	0.0374 (8)	0.0350 (9)	0.0336 (10)	−0.0049 (8)	0.0109 (7)	0.0074 (7)
C19	0.0319 (8)	0.0491 (11)	0.0393 (10)	−0.0082 (8)	0.0154 (7)	−0.0081 (8)
C20	0.0284 (7)	0.0261 (8)	0.0310 (9)	−0.0007 (6)	0.0146 (6)	0.0020 (7)
C21	0.0332 (7)	0.0289 (8)	0.0215 (8)	0.0050 (6)	0.0156 (6)	0.0034 (6)
C22	0.0334 (8)	0.0355 (9)	0.0283 (9)	−0.0011 (7)	0.0104 (6)	−0.0009 (7)
C23	0.0343 (9)	0.0478 (11)	0.0369 (10)	0.0089 (8)	0.0128 (7)	0.0037 (8)
C24	0.0459 (9)	0.0355 (9)	0.0466 (11)	0.0143 (8)	0.0267 (8)	0.0149 (8)
C25	0.0448 (9)	0.0258 (8)	0.0596 (12)	0.0024 (8)	0.0322 (9)	0.0078 (8)
C26	0.0318 (8)	0.0301 (9)	0.0446 (10)	0.0029 (7)	0.0208 (7)	0.0054 (7)
O2S	0.0406 (6)	0.0605 (9)	0.0520 (8)	−0.0194 (7)	0.0256 (6)	−0.0300 (7)
O1S	0.0402 (10)	0.0401 (11)	0.0665 (14)	0.000	0.0251 (10)	0.000

Geometric parameters (Å, º) top

F1—C24	1.360 (2)	C12—C13	1.479 (2)
N1—C19	1.469 (2)	C13—C14	1.343 (2)
N1—C16	1.471 (2)	C14—H14	0.9500
N1—C9	1.476 (2)	C15—C16	1.531 (2)
O1—C1	1.3815 (18)	C15—H15A	0.9900
O1—C20	1.4438 (17)	C15—H15B	0.9900
O2—C2	1.3725 (18)	C16—H16A	0.9900
O2—C17	1.430 (2)	C16—H16B	0.9900
O3—C12	1.2233 (19)	C17—H17A	0.9800
O4—C13	1.3585 (19)	C17—H17B	0.9800
O4—C18	1.425 (2)	C17—H17C	0.9800
C1—C6	1.406 (2)	C18—H18A	0.9800
C1—C2	1.411 (2)	C18—H18B	0.9800
C2—C3	1.383 (2)	C18—H18C	0.9800
C3—C4	1.380 (2)	C19—H19A	0.9800
C3—H3	0.9500	C19—H19B	0.9800
C4—C5	1.379 (2)	C19—H19C	0.9800
C4—H4	0.9500	C20—C21	1.505 (2)
C5—C6	1.420 (2)	C20—H20A	0.9900
C5—C10	1.517 (2)	C20—H20B	0.9900
C6—C7	1.540 (2)	C21—C26	1.381 (2)
C7—C15	1.539 (2)	C21—C22	1.394 (2)
C7—C8	1.542 (2)	C22—C23	1.381 (3)
C7—C11	1.543 (2)	C22—H22	0.9500
C8—C14	1.506 (2)	C23—C24	1.375 (3)
C8—C9	1.525 (2)	C23—H23	0.9500
C8—H8	1.0000	C24—C25	1.370 (3)
C9—C10	1.525 (2)	C25—C26	1.386 (3)
C9—H9	1.0000	C25—H25	0.9500
C10—H10A	0.9900	C26—H26	0.9500
C10—H10B	0.9900	O2S—H21S	0.9694
C11—C12	1.507 (2)	O2S—H22S	0.9051
C11—H11A	0.9900	O1S—H11S	0.90 (3)
C11—H11B	0.9900

C19—N1—C16	109.97 (14)	O4—C13—C12	111.83 (13)
C19—N1—C9	112.02 (14)	C13—C14—C8	122.02 (15)
C16—N1—C9	115.49 (12)	C13—C14—H14	119.0
C1—O1—C20	115.64 (11)	C8—C14—H14	119.0
C2—O2—C17	116.41 (12)	C16—C15—C7	110.70 (13)
C13—O4—C18	115.67 (12)	C16—C15—H15A	109.5
O1—C1—C6	120.15 (13)	C7—C15—H15A	109.5
O1—C1—C2	118.52 (12)	C16—C15—H15B	109.5
C6—C1—C2	121.03 (14)	C7—C15—H15B	109.5
O2—C2—C3	123.80 (14)	H15A—C15—H15B	108.1
O2—C2—C1	116.07 (13)	N1—C16—C15	111.84 (13)
C3—C2—C1	120.13 (13)	N1—C16—H16A	109.2
C4—C3—C2	118.93 (14)	C15—C16—H16A	109.2
C4—C3—H3	120.5	N1—C16—H16B	109.2
C2—C3—H3	120.5	C15—C16—H16B	109.2
C5—C4—C3	122.39 (14)	H16A—C16—H16B	107.9
C5—C4—H4	118.8	O2—C17—H17A	109.5
C3—C4—H4	118.8	O2—C17—H17B	109.5
C4—C5—C6	120.01 (13)	H17A—C17—H17B	109.5
C4—C5—C10	117.71 (14)	O2—C17—H17C	109.5
C6—C5—C10	122.25 (14)	H17A—C17—H17C	109.5
C1—C6—C5	117.47 (13)	H17B—C17—H17C	109.5
C1—C6—C7	121.96 (13)	O4—C18—H18A	109.5
C5—C6—C7	120.11 (13)	O4—C18—H18B	109.5
C15—C7—C6	107.95 (12)	H18A—C18—H18B	109.5
C15—C7—C8	106.49 (12)	O4—C18—H18C	109.5
C6—C7—C8	110.68 (13)	H18A—C18—H18C	109.5
C15—C7—C11	110.81 (13)	H18B—C18—H18C	109.5
C6—C7—C11	115.14 (12)	N1—C19—H19A	109.5
C8—C7—C11	105.44 (12)	N1—C19—H19B	109.5
C14—C8—C9	111.39 (13)	H19A—C19—H19B	109.5
C14—C8—C7	112.60 (12)	N1—C19—H19C	109.5
C9—C8—C7	110.14 (12)	H19A—C19—H19C	109.5
C14—C8—H8	107.5	H19B—C19—H19C	109.5
C9—C8—H8	107.5	O1—C20—C21	108.57 (12)
C7—C8—H8	107.5	O1—C20—H20A	110.0
N1—C9—C8	108.72 (13)	C21—C20—H20A	110.0
N1—C9—C10	116.85 (14)	O1—C20—H20B	110.0
C8—C9—C10	108.37 (12)	C21—C20—H20B	110.0
N1—C9—H9	107.5	H20A—C20—H20B	108.4
C8—C9—H9	107.5	C26—C21—C22	118.90 (15)
C10—C9—H9	107.5	C26—C21—C20	122.68 (13)
C5—C10—C9	113.63 (14)	C22—C21—C20	118.39 (15)
C5—C10—H10A	108.8	C23—C22—C21	120.94 (16)
C9—C10—H10A	108.8	C23—C22—H22	119.5
C5—C10—H10B	108.8	C21—C22—H22	119.5
C9—C10—H10B	108.8	C24—C23—C22	118.28 (15)
H10A—C10—H10B	107.7	C24—C23—H23	120.9
C12—C11—C7	112.63 (13)	C22—C23—H23	120.9
C12—C11—H11A	109.1	F1—C24—C25	118.55 (17)
C7—C11—H11A	109.1	F1—C24—C23	119.01 (15)
C12—C11—H11B	109.1	C25—C24—C23	122.44 (17)
C7—C11—H11B	109.1	C24—C25—C26	118.62 (17)
H11A—C11—H11B	107.8	C24—C25—H25	120.7
O3—C12—C13	121.36 (15)	C26—C25—H25	120.7
O3—C12—C11	122.58 (15)	C21—C26—C25	120.83 (15)
C13—C12—C11	115.97 (13)	C21—C26—H26	119.6
C14—C13—O4	126.68 (15)	C25—C26—H26	119.6
C14—C13—C12	121.49 (14)	H21S—O2S—H22S	100.4

C20—O1—C1—C6	117.00 (14)	C7—C8—C9—C10	67.54 (17)
C20—O1—C1—C2	−69.19 (16)	C4—C5—C10—C9	−161.88 (13)
C17—O2—C2—C3	−6.5 (2)	C6—C5—C10—C9	16.3 (2)
C17—O2—C2—C1	174.39 (13)	N1—C9—C10—C5	76.09 (17)
O1—C1—C2—O2	4.70 (18)	C8—C9—C10—C5	−47.08 (17)
C6—C1—C2—O2	178.46 (12)	C15—C7—C11—C12	174.84 (13)
O1—C1—C2—C3	−174.47 (12)	C6—C7—C11—C12	−62.30 (18)
C6—C1—C2—C3	−0.7 (2)	C8—C7—C11—C12	59.99 (16)
O2—C2—C3—C4	−177.53 (14)	C7—C11—C12—O3	146.72 (15)
C1—C2—C3—C4	1.6 (2)	C7—C11—C12—C13	−36.64 (19)
C2—C3—C4—C5	−0.4 (2)	C18—O4—C13—C14	4.3 (2)
C3—C4—C5—C6	−1.7 (2)	C18—O4—C13—C12	−176.15 (14)
C3—C4—C5—C10	176.50 (14)	O3—C12—C13—C14	−178.85 (14)
O1—C1—C6—C5	172.34 (12)	C11—C12—C13—C14	4.5 (2)
C2—C1—C6—C5	−1.31 (19)	O3—C12—C13—O4	1.6 (2)
O1—C1—C6—C7	0.16 (19)	C11—C12—C13—O4	−175.12 (12)
C2—C1—C6—C7	−173.49 (13)	O4—C13—C14—C8	−179.60 (15)
C4—C5—C6—C1	2.50 (19)	C12—C13—C14—C8	0.9 (2)
C10—C5—C6—C1	−175.63 (13)	C9—C8—C14—C13	150.28 (14)
C4—C5—C6—C7	174.83 (13)	C7—C8—C14—C13	26.0 (2)
C10—C5—C6—C7	−3.3 (2)	C6—C7—C15—C16	60.26 (16)
C1—C6—C7—C15	77.55 (16)	C8—C7—C15—C16	−58.62 (17)
C5—C6—C7—C15	−94.43 (16)	C11—C7—C15—C16	−172.80 (13)
C1—C6—C7—C8	−166.27 (12)	C19—N1—C16—C15	−179.28 (13)
C5—C6—C7—C8	21.76 (18)	C9—N1—C16—C15	−51.32 (19)
C1—C6—C7—C11	−46.83 (19)	C7—C15—C16—N1	52.98 (18)
C5—C6—C7—C11	141.20 (14)	C1—O1—C20—C21	175.38 (12)
C15—C7—C8—C14	−171.75 (13)	O1—C20—C21—C26	14.3 (2)
C6—C7—C8—C14	71.16 (16)	O1—C20—C21—C22	−167.91 (13)
C11—C7—C8—C14	−53.97 (17)	C26—C21—C22—C23	0.2 (2)
C15—C7—C8—C9	63.25 (16)	C20—C21—C22—C23	−177.70 (16)
C6—C7—C8—C9	−53.84 (16)	C21—C22—C23—C24	−0.5 (3)
C11—C7—C8—C9	−178.96 (12)	C22—C23—C24—F1	179.61 (18)
C19—N1—C9—C8	−178.64 (13)	C22—C23—C24—C25	0.4 (3)
C16—N1—C9—C8	54.42 (18)	F1—C24—C25—C26	−179.18 (17)
C19—N1—C9—C10	58.37 (18)	C23—C24—C25—C26	0.0 (3)
C16—N1—C9—C10	−68.57 (18)	C22—C21—C26—C25	0.2 (3)
C14—C8—C9—N1	173.90 (13)	C20—C21—C26—C25	178.05 (17)
C7—C8—C9—N1	−60.41 (17)	C24—C25—C26—C21	−0.4 (3)
C14—C8—C9—C10	−58.15 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2S—H22S···O4	0.91	2.33	2.9805 (16)	128
O2S—H22S···O3	0.91	2.54	3.417 (2)	164
O1S—H11S···O2S	0.90 (3)	1.94 (3)	2.8342 (19)	172 (2)
O2S—H21S···N1ⁱ	0.97	1.81	2.7736 (19)	170

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

Experimental details

Crystal data
Chemical formula	C₂₆H₂₈FNO₄·1.5H₂O
M_r	464.52
Crystal system, space group	Monoclinic, C2
Temperature (K)	133
a, b, c (Å)	18.0155 (3), 7.6776 (1), 18.1506 (4)
β (°)	109.324 (1)
V (Å³)	2369.08 (7)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.79
Crystal size (mm)	0.25 × 0.15 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.826, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	7232, 3415, 3402
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.588

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.081, 1.04
No. of reflections	3415
No. of parameters	312
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.18
Absolute structure	Flack (1983), 1359 Friedel pairs
Absolute structure parameter	0.05 (12)

Computer programs: APEX2 (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2S—H22S···O4	0.91	2.33	2.9805 (16)	128
O2S—H22S···O3	0.91	2.54	3.417 (2)	164
O1S—H11S···O2S	0.90 (3)	1.94 (3)	2.8342 (19)	172 (2)
O2S—H21S···N1ⁱ	0.97	1.81	2.7736 (19)	170

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

Acknowledgements

The project was supported by the National Natural Science Foundation of China (No. 20976017) and the Scientific Research Fund of the Hunan Provincial Science and Technology Department, China (No. 2009 C K3070).

References

Batterham, T. J., Bell, K. H. & Weis, U. (1965). Aust. J. Chem. 18, 1799–1806. CrossRef CAS Web of Science Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ye, X. R., Yan, K. X., Wu, K. M., Feng, X. Z., Huang, Y. M. & Qiu, P. (2004). Acta Pharmacol. Sin. 39, 180–183. CAS Google Scholar
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Volume 67| Part 8| August 2011| Page o1988

doi:10.1107/S1600536811026183

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(9S,13R,14S)-7,8-Dide­hydro-4-(4-fluoro­benz­yl­oxy)-3,7-dimeth­­oxy-17-methyl­morphinan-6-one sesquihydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

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References

organic compounds

(9S,13R,14S)-7,8-Didehydro-4-(4-fluorobenzyloxy)-3,7-dimethoxy-17-methylmorphinan-6-one sesquihydrate