(8S,9S,10R)-4-(4-Chloro­benz­yloxy)-7,8-didehydro-3,7-dimeth­oxy-17-methyl­morphinan-6-one monohydrate

Zheng, X.-L.; Chen, S.-J.; Jiang, N.-F.; Zhan, S.-H.

doi:10.1107/S1600536811013973

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1190

doi:10.1107/S1600536811013973

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(8S,9S,10R)-4-(4-Chlorobenzyloxy)-7,8-didehydro-3,7-dimethoxy-17-methylmorphinan-6-one monohydrate

Xing-Liang Zheng,^a ^* Shu-Jun Chen,^a Ning-Fei Jiang ^a and Sue-Hui Zhan ^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 4 April 2011; accepted 13 April 2011; online 22 April 2011)

In the title compound, C₂₆H₂₈Cl_NO₄·H₂O, the dihedral angle betwene the two aromatic rings is 69.73 (6)°. The N-containing ring exhibits a chair conformation, while the other non-aromatic rings are in approximate envelope conformations. In the crystal, the water molecule forms O—H⋯O and O—H⋯N hydrogen bonds and a C—H⋯O link also occurs.

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 ).

Experimental

Crystal data

C₂₆H₂₈ClNO₄·H₂O
M_r = 471.96
Monoclinic, P 2₁
a = 8.8866 (4) Å
b = 14.6386 (7) Å
c = 9.1860 (4) Å
β = 91.618 (1)°
V = 1194.51 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 296 K
0.45 × 0.36 × 0.32 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.917, T_max = 0.940
13795 measured reflections
4185 independent reflections
3974 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.082
S = 1.05
4185 reflections
303 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack (1983 ), 1991 Friedel pairs
Flack parameter: −0.02 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O1ⁱ	0.98	2.56	3.469 (2)	155
O1W—H1WB⋯O4ⁱⁱ	0.85	2.04	2.879 (2)	169
O1W—H1WA⋯N1	0.85	2.16	2.899 (2)	146
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z]$ .

Data collection: SMART (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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811013973/kp2320sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811013973/kp2320Isup2.hkl

checkCIF report

Comment top

We synthesised a new sinomenine derivative (8S,9S,10R)-7,8-didehydro-4-(4'-chlorobenzyloxy)-3,7-δimethoxy-17-methyl-morphinan-6-one monohydrate. 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 (I) is shown in Fig. 1. The angle between the two benzene planes is 69.736°. Rings C [C9/C10/C11/C12/C13/C14] and B [C5···.C10], both, are in an envelope conformation. In contrast, ring D [C8/N1/C15/C16/C10/C9] exhibits an almost regular chair conformation. Similar features have been described in related compounds (Li et al., 2009; Batterham et al., 1965). The crystal structure is stabilised by O—H···O and O—H···N hydrogen bonds linking sinomenine derivative and the water molecule; weak C—H···O hydrogen bonds (Table 1 and Fig. 2) also occurred.

Related literature top

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).

Experimental top

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

Computing details top

Data collection: SMART (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 (I) showing 50% probability displacement ellipsoids [Symmetry codes: (i) 1 - x, 2 - y, 2 - z].
	Fig. 2. Crystal packing of (I) with hydrogen bond interactions (dashed lines).

(8S,9S,10R)-4-(4-Chlorobenzyloxy)-7,8-didehydro-3,7- dimethoxy-17-methylmorphinan-6-one monohydrate top

Crystal data top

C₂₆H₂₈ClNO₄·H₂O	F(000) = 500
M_r = 471.96	D_x = 1.312 Mg m⁻³
Monoclinic, P2₁	Melting point: 383 K
a = 8.8866 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.6386 (7) Å	µ = 0.20 mm⁻¹
c = 9.1860 (4) Å	T = 296 K
β = 91.618 (1)°	Block, colourless
V = 1194.51 (9) Å³	0.45 × 0.36 × 0.32 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	4185 independent reflections
Radiation source: fine-focus sealed tube	3974 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
T_min = 0.917, T_max = 0.940	k = −17→17
13795 measured reflections	l = −10→10

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)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.0458P)² + 0.1696P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
4185 reflections	Δρ_max = 0.20 e Å⁻³
303 parameters	Δρ_min = −0.21 e Å⁻³
3 restraints	Absolute structure: Flack (1983), 1991 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (6)

Crystal data top

C₂₆H₂₈ClNO₄·H₂O	V = 1194.51 (9) Å³
M_r = 471.96	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 8.8866 (4) Å	µ = 0.20 mm⁻¹
b = 14.6386 (7) Å	T = 296 K
c = 9.1860 (4) Å	0.45 × 0.36 × 0.32 mm
β = 91.618 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4185 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3974 reflections with I > 2σ(I)
T_min = 0.917, T_max = 0.940	R_int = 0.022
13795 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.082	Δρ_max = 0.20 e Å⁻³
S = 1.05	Δρ_min = −0.21 e Å⁻³
4185 reflections	Absolute structure: Flack (1983), 1991 Friedel pairs
303 parameters	Absolute structure parameter: −0.02 (6)
3 restraints

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.52194 (7)	0.27734 (5)	0.40802 (7)	0.07659 (19)
O1	−0.15952 (17)	−0.04761 (10)	0.27652 (16)	0.0553 (4)
O2	0.12278 (13)	−0.08829 (9)	0.21247 (13)	0.0412 (3)
O3	0.07164 (16)	−0.20241 (10)	−0.34261 (14)	0.0524 (3)
O4	0.23766 (16)	−0.08573 (9)	−0.18937 (17)	0.0563 (4)
N1	0.22663 (19)	−0.45473 (11)	0.17465 (19)	0.0501 (4)
C1	−0.2087 (2)	−0.28319 (15)	0.1494 (2)	0.0487 (4)
H1A	−0.2839	−0.3269	0.1371	0.058*
C2	−0.2467 (2)	−0.19781 (15)	0.1984 (2)	0.0510 (5)
H2A	−0.3467	−0.1835	0.2153	0.061*
C3	−0.1356 (2)	−0.13375 (13)	0.22213 (19)	0.0427 (4)
C4	0.01413 (18)	−0.15522 (11)	0.18989 (17)	0.0355 (3)
C5	0.05174 (17)	−0.23996 (11)	0.13104 (16)	0.0337 (3)
C6	−0.06217 (19)	−0.30630 (12)	0.11783 (19)	0.0393 (4)
C7	−0.0312 (2)	−0.40384 (13)	0.0731 (2)	0.0473 (4)
H7A	−0.0893	−0.4167	−0.0155	0.057*
H7B	−0.0674	−0.4441	0.1483	0.057*
C8	0.1333 (2)	−0.42725 (12)	0.0471 (2)	0.0441 (4)
H8A	0.1348	−0.4775	−0.0234	0.053*
C9	0.2069 (2)	−0.34492 (11)	−0.02251 (19)	0.0383 (4)
H9A	0.3110	−0.3617	−0.0430	0.046*
C10	0.21264 (18)	−0.26412 (11)	0.08633 (18)	0.0355 (3)
C11	0.29450 (18)	−0.18780 (12)	0.00569 (19)	0.0392 (4)
H11A	0.2997	−0.1342	0.0678	0.047*
H11B	0.3968	−0.2074	−0.0110	0.047*
C12	0.22199 (18)	−0.16152 (12)	−0.1371 (2)	0.0400 (4)
C13	0.13513 (19)	−0.23343 (13)	−0.21620 (18)	0.0411 (4)
C14	0.1311 (2)	−0.31859 (13)	−0.16395 (19)	0.0419 (4)
H14A	0.0794	−0.3631	−0.2174	0.050*
C15	0.2405 (2)	−0.38269 (15)	0.2849 (2)	0.0516 (5)
H15A	0.3056	−0.4035	0.3647	0.062*
H15B	0.1422	−0.3698	0.3234	0.062*
C16	0.3050 (2)	−0.29596 (13)	0.2203 (2)	0.0441 (4)
H16A	0.4080	−0.3071	0.1929	0.053*
H16B	0.3062	−0.2481	0.2933	0.053*
C17	0.1749 (4)	−0.54114 (17)	0.2379 (3)	0.0758 (7)
H17A	0.2381	−0.5566	0.3208	0.114*
H17B	0.1799	−0.5888	0.1664	0.114*
H17C	0.0729	−0.5344	0.2679	0.114*
C18	0.2921 (2)	0.05280 (14)	0.5062 (2)	0.0491 (5)
H18A	0.2597	0.0239	0.5899	0.059*
C19	0.3747 (2)	0.13208 (15)	0.5183 (2)	0.0515 (5)
H19A	0.3979	0.1569	0.6094	0.062*
C20	0.4226 (2)	0.17419 (14)	0.3939 (2)	0.0472 (4)
C21	0.3920 (2)	0.13761 (14)	0.2589 (2)	0.0468 (4)
H21A	0.4261	0.1662	0.1756	0.056*
C22	0.3096 (2)	0.05773 (13)	0.2481 (2)	0.0433 (4)
H22A	0.2897	0.0322	0.1569	0.052*
C23	0.25623 (19)	0.01518 (13)	0.37027 (19)	0.0394 (4)
C24	−0.3108 (3)	−0.02259 (19)	0.3035 (3)	0.0779 (8)
H24A	−0.3131	0.0386	0.3410	0.117*
H24B	−0.3517	−0.0637	0.3735	0.117*
H24C	−0.3696	−0.0257	0.2144	0.117*
C25	−0.0249 (3)	−0.2642 (2)	−0.4189 (2)	0.0710 (7)
H25A	−0.0639	−0.2355	−0.5061	0.106*
H25B	−0.1067	−0.2809	−0.3583	0.106*
H25C	0.0306	−0.3179	−0.4440	0.106*
C26	0.15968 (16)	−0.06997 (10)	0.36153 (16)	0.0480 (4)
H26A	0.2140	−0.1213	0.4042	0.058*
H26B	0.0684	−0.0609	0.4152	0.058*
O1W	0.53363 (16)	−0.46331 (10)	0.07692 (16)	0.0895 (6)
H1WB	0.592 (4)	−0.502 (2)	0.118 (4)	0.121 (13)*
H1WA	0.4437 (18)	−0.481 (3)	0.084 (4)	0.116 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0763 (4)	0.0731 (4)	0.0804 (4)	−0.0350 (3)	0.0019 (3)	−0.0121 (3)
O1	0.0574 (8)	0.0452 (8)	0.0640 (9)	0.0130 (6)	0.0149 (6)	−0.0006 (6)
O2	0.0484 (7)	0.0366 (6)	0.0386 (6)	−0.0066 (5)	0.0034 (5)	−0.0041 (5)
O3	0.0583 (8)	0.0525 (8)	0.0461 (7)	−0.0059 (6)	−0.0052 (6)	0.0095 (6)
O4	0.0588 (8)	0.0376 (8)	0.0724 (9)	−0.0072 (6)	0.0007 (7)	0.0089 (7)
N1	0.0532 (9)	0.0424 (9)	0.0548 (9)	0.0022 (7)	0.0011 (7)	0.0092 (7)
C1	0.0357 (9)	0.0530 (12)	0.0576 (11)	−0.0082 (8)	0.0053 (8)	0.0031 (9)
C2	0.0348 (9)	0.0597 (13)	0.0589 (12)	0.0038 (8)	0.0082 (8)	0.0071 (9)
C3	0.0454 (9)	0.0412 (10)	0.0419 (9)	0.0072 (8)	0.0072 (8)	0.0052 (8)
C4	0.0370 (8)	0.0349 (9)	0.0345 (8)	−0.0023 (7)	0.0009 (6)	0.0031 (7)
C5	0.0327 (8)	0.0360 (9)	0.0322 (7)	−0.0021 (6)	−0.0009 (6)	0.0026 (7)
C6	0.0377 (8)	0.0406 (10)	0.0396 (8)	−0.0063 (7)	0.0013 (7)	0.0028 (7)
C7	0.0485 (10)	0.0398 (10)	0.0536 (10)	−0.0117 (8)	−0.0007 (8)	−0.0022 (8)
C8	0.0542 (10)	0.0316 (9)	0.0464 (10)	−0.0030 (8)	0.0027 (8)	−0.0013 (8)
C9	0.0405 (9)	0.0320 (9)	0.0426 (9)	0.0009 (7)	0.0059 (7)	−0.0025 (7)
C10	0.0338 (8)	0.0332 (8)	0.0396 (8)	−0.0025 (6)	0.0017 (7)	−0.0033 (7)
C11	0.0329 (8)	0.0380 (9)	0.0470 (9)	−0.0060 (7)	0.0069 (7)	−0.0063 (7)
C12	0.0339 (8)	0.0326 (9)	0.0540 (10)	−0.0007 (7)	0.0124 (7)	0.0030 (8)
C13	0.0403 (9)	0.0417 (10)	0.0415 (9)	−0.0016 (8)	0.0055 (7)	0.0003 (8)
C14	0.0483 (9)	0.0371 (9)	0.0403 (9)	−0.0048 (7)	0.0034 (7)	−0.0059 (7)
C15	0.0498 (10)	0.0588 (13)	0.0461 (10)	0.0044 (9)	−0.0010 (8)	0.0094 (9)
C16	0.0380 (8)	0.0461 (10)	0.0480 (10)	0.0018 (8)	−0.0044 (7)	−0.0040 (8)
C17	0.0948 (18)	0.0526 (14)	0.0798 (16)	−0.0033 (13)	−0.0015 (14)	0.0272 (12)
C18	0.0534 (11)	0.0556 (12)	0.0380 (9)	−0.0021 (9)	−0.0005 (8)	0.0007 (8)
C19	0.0499 (10)	0.0632 (13)	0.0410 (10)	−0.0067 (9)	−0.0045 (8)	−0.0142 (9)
C20	0.0345 (8)	0.0515 (11)	0.0556 (11)	−0.0050 (8)	0.0009 (7)	−0.0091 (9)
C21	0.0415 (9)	0.0541 (11)	0.0450 (10)	−0.0039 (8)	0.0055 (8)	0.0027 (9)
C22	0.0412 (9)	0.0494 (10)	0.0391 (9)	−0.0006 (8)	−0.0016 (7)	−0.0052 (8)
C23	0.0389 (9)	0.0396 (9)	0.0395 (9)	0.0036 (7)	−0.0008 (7)	−0.0029 (7)
C24	0.0695 (15)	0.0659 (16)	0.1001 (19)	0.0209 (13)	0.0321 (14)	−0.0023 (14)
C25	0.0798 (16)	0.0815 (17)	0.0508 (12)	−0.0221 (13)	−0.0132 (11)	0.0118 (12)
C26	0.0613 (12)	0.0406 (11)	0.0418 (9)	−0.0037 (8)	−0.0030 (8)	0.0013 (8)
O1W	0.0715 (13)	0.0886 (15)	0.1095 (15)	0.0265 (11)	0.0246 (11)	0.0396 (12)

Geometric parameters (Å, º) top

Cl1—C20	1.752 (2)	C11—H11B	0.9700
O1—C3	1.375 (2)	C12—C13	1.483 (3)
O1—C24	1.422 (3)	C13—C14	1.337 (3)
O2—C4	1.387 (2)	C14—H14A	0.9300
O2—C26	1.4244 (19)	C15—C16	1.521 (3)
O3—C13	1.355 (2)	C15—H15A	0.9700
O3—C25	1.418 (3)	C15—H15B	0.9700
O4—C12	1.218 (2)	C16—H16A	0.9700
N1—C15	1.465 (3)	C16—H16B	0.9700
N1—C17	1.471 (3)	C17—H17A	0.9600
N1—C8	1.473 (2)	C17—H17B	0.9600
C1—C2	1.374 (3)	C17—H17C	0.9600
C1—C6	1.384 (3)	C18—C19	1.376 (3)
C1—H1A	0.9300	C18—C23	1.393 (3)
C2—C3	1.375 (3)	C18—H18A	0.9300
C2—H2A	0.9300	C19—C20	1.377 (3)
C3—C4	1.407 (2)	C19—H19A	0.9300
C4—C5	1.397 (2)	C20—C21	1.371 (3)
C5—C6	1.406 (2)	C21—C22	1.382 (3)
C5—C10	1.540 (2)	C21—H21A	0.9300
C6—C7	1.513 (3)	C22—C23	1.379 (3)
C7—C8	1.526 (3)	C22—H22A	0.9300
C7—H7A	0.9700	C23—C26	1.514 (2)
C7—H7B	0.9700	C24—H24A	0.9600
C8—C9	1.521 (2)	C24—H24B	0.9600
C8—H8A	0.9800	C24—H24C	0.9600
C9—C14	1.497 (2)	C25—H25A	0.9600
C9—C10	1.549 (2)	C25—H25B	0.9600
C9—H9A	0.9800	C25—H25C	0.9600
C10—C16	1.532 (2)	C26—H26A	0.9700
C10—C11	1.535 (2)	C26—H26B	0.9700
C11—C12	1.495 (3)	O1W—H1WB	0.851 (10)
C11—H11A	0.9700	O1W—H1WA	0.846 (10)

C3—O1—C24	117.17 (18)	O3—C13—C12	112.34 (16)
C4—O2—C26	114.65 (12)	C13—C14—C9	122.41 (16)
C13—O3—C25	116.20 (16)	C13—C14—H14A	118.8
C15—N1—C17	111.53 (18)	C9—C14—H14A	118.8
C15—N1—C8	112.83 (15)	N1—C15—C16	110.88 (15)
C17—N1—C8	111.96 (18)	N1—C15—H15A	109.5
C2—C1—C6	122.20 (18)	C16—C15—H15A	109.5
C2—C1—H1A	118.9	N1—C15—H15B	109.5
C6—C1—H1A	118.9	C16—C15—H15B	109.5
C1—C2—C3	119.34 (17)	H15A—C15—H15B	108.1
C1—C2—H2A	120.3	C15—C16—C10	111.60 (14)
C3—C2—H2A	120.3	C15—C16—H16A	109.3
C2—C3—O1	124.42 (16)	C10—C16—H16A	109.3
C2—C3—C4	119.58 (17)	C15—C16—H16B	109.3
O1—C3—C4	116.00 (16)	C10—C16—H16B	109.3
O2—C4—C5	120.78 (14)	H16A—C16—H16B	108.0
O2—C4—C3	117.98 (15)	N1—C17—H17A	109.5
C5—C4—C3	121.18 (15)	N1—C17—H17B	109.5
C4—C5—C6	117.85 (15)	H17A—C17—H17B	109.5
C4—C5—C10	122.76 (14)	N1—C17—H17C	109.5
C6—C5—C10	119.35 (15)	H17A—C17—H17C	109.5
C1—C6—C5	119.51 (17)	H17B—C17—H17C	109.5
C1—C6—C7	117.85 (16)	C19—C18—C23	120.93 (18)
C5—C6—C7	122.62 (15)	C19—C18—H18A	119.5
C6—C7—C8	115.91 (15)	C23—C18—H18A	119.5
C6—C7—H7A	108.3	C18—C19—C20	119.15 (17)
C8—C7—H7A	108.3	C18—C19—H19A	120.4
C6—C7—H7B	108.3	C20—C19—H19A	120.4
C8—C7—H7B	108.3	C21—C20—C19	121.19 (18)
H7A—C7—H7B	107.4	C21—C20—Cl1	119.39 (16)
N1—C8—C9	108.14 (15)	C19—C20—Cl1	119.42 (15)
N1—C8—C7	117.17 (16)	C20—C21—C22	119.11 (18)
C9—C8—C7	108.27 (15)	C20—C21—H21A	120.4
N1—C8—H8A	107.6	C22—C21—H21A	120.4
C9—C8—H8A	107.6	C23—C22—C21	121.18 (17)
C7—C8—H8A	107.6	C23—C22—H22A	119.4
C14—C9—C8	112.35 (15)	C21—C22—H22A	119.4
C14—C9—C10	111.68 (14)	C22—C23—C18	118.39 (18)
C8—C9—C10	109.92 (14)	C22—C23—C26	122.41 (15)
C14—C9—H9A	107.6	C18—C23—C26	119.20 (16)
C8—C9—H9A	107.6	O1—C24—H24A	109.5
C10—C9—H9A	107.6	O1—C24—H24B	109.5
C16—C10—C11	111.01 (14)	H24A—C24—H24B	109.5
C16—C10—C5	109.63 (13)	O1—C24—H24C	109.5
C11—C10—C5	114.69 (14)	H24A—C24—H24C	109.5
C16—C10—C9	107.05 (14)	H24B—C24—H24C	109.5
C11—C10—C9	104.58 (13)	O3—C25—H25A	109.5
C5—C10—C9	109.50 (13)	O3—C25—H25B	109.5
C12—C11—C10	114.34 (13)	H25A—C25—H25B	109.5
C12—C11—H11A	108.7	O3—C25—H25C	109.5
C10—C11—H11A	108.7	H25A—C25—H25C	109.5
C12—C11—H11B	108.7	H25B—C25—H25C	109.5
C10—C11—H11B	108.7	O2—C26—C23	108.70 (12)
H11A—C11—H11B	107.6	O2—C26—H26A	109.9
O4—C12—C13	121.13 (17)	C23—C26—H26A	109.9
O4—C12—C11	121.91 (17)	O2—C26—H26B	109.9
C13—C12—C11	116.90 (15)	C23—C26—H26B	109.9
C14—C13—O3	127.28 (17)	H26A—C26—H26B	108.3
C14—C13—C12	120.32 (16)	H1WB—O1W—H1WA	109 (4)

C6—C1—C2—C3	−2.4 (3)	C8—C9—C10—C16	59.88 (18)
C1—C2—C3—O1	−177.22 (17)	C14—C9—C10—C11	−56.88 (17)
C1—C2—C3—C4	2.8 (3)	C8—C9—C10—C11	177.73 (14)
C24—O1—C3—C2	−2.9 (3)	C14—C9—C10—C5	66.49 (17)
C24—O1—C3—C4	177.09 (19)	C8—C9—C10—C5	−58.90 (18)
C26—O2—C4—C5	−110.58 (16)	C16—C10—C11—C12	172.20 (15)
C26—O2—C4—C3	72.10 (18)	C5—C10—C11—C12	−62.86 (19)
C2—C3—C4—O2	178.72 (15)	C9—C10—C11—C12	57.09 (18)
O1—C3—C4—O2	−1.3 (2)	C10—C11—C12—O4	154.14 (17)
C2—C3—C4—C5	1.4 (2)	C10—C11—C12—C13	−28.5 (2)
O1—C3—C4—C5	−178.57 (14)	C25—O3—C13—C14	8.4 (3)
O2—C4—C5—C6	176.86 (14)	C25—O3—C13—C12	−174.43 (18)
C3—C4—C5—C6	−5.9 (2)	O4—C12—C13—C14	173.55 (17)
O2—C4—C5—C10	−0.7 (2)	C11—C12—C13—C14	−3.8 (2)
C3—C4—C5—C10	176.50 (15)	O4—C12—C13—O3	−3.8 (2)
C2—C1—C6—C5	−2.2 (3)	C11—C12—C13—O3	178.80 (14)
C2—C1—C6—C7	176.47 (18)	O3—C13—C14—C9	179.57 (15)
C4—C5—C6—C1	6.2 (2)	C12—C13—C14—C9	2.6 (3)
C10—C5—C6—C1	−176.07 (16)	C8—C9—C14—C13	154.08 (17)
C4—C5—C6—C7	−172.38 (15)	C10—C9—C14—C13	30.0 (2)
C10—C5—C6—C7	5.3 (2)	C17—N1—C15—C16	175.80 (18)
C1—C6—C7—C8	−176.95 (16)	C8—N1—C15—C16	−57.2 (2)
C5—C6—C7—C8	1.7 (3)	N1—C15—C16—C10	54.9 (2)
C15—N1—C8—C9	60.6 (2)	C11—C10—C16—C15	−169.38 (15)
C17—N1—C8—C9	−172.57 (18)	C5—C10—C16—C15	62.88 (19)
C15—N1—C8—C7	−62.0 (2)	C9—C10—C16—C15	−55.82 (18)
C17—N1—C8—C7	64.8 (2)	C23—C18—C19—C20	−0.2 (3)
C6—C7—C8—N1	86.1 (2)	C18—C19—C20—C21	−1.3 (3)
C6—C7—C8—C9	−36.5 (2)	C18—C19—C20—Cl1	177.68 (16)
N1—C8—C9—C14	172.93 (14)	C19—C20—C21—C22	0.9 (3)
C7—C8—C9—C14	−59.18 (19)	Cl1—C20—C21—C22	−178.01 (15)
N1—C8—C9—C10	−62.06 (18)	C20—C21—C22—C23	0.9 (3)
C7—C8—C9—C10	65.83 (18)	C21—C22—C23—C18	−2.4 (3)
C4—C5—C10—C16	83.19 (19)	C21—C22—C23—C26	177.14 (16)
C6—C5—C10—C16	−94.37 (18)	C19—C18—C23—C22	2.0 (3)
C4—C5—C10—C11	−42.5 (2)	C19—C18—C23—C26	−177.50 (16)
C6—C5—C10—C11	139.97 (15)	C4—O2—C26—C23	−169.61 (13)
C4—C5—C10—C9	−159.65 (14)	C22—C23—C26—O2	−6.9 (2)
C6—C5—C10—C9	22.8 (2)	C18—C23—C26—O2	172.64 (16)
C14—C9—C10—C16	−174.73 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1ⁱ	0.98	2.56	3.469 (2)	155
O1W—H1WB···O4ⁱⁱ	0.85	2.04	2.879 (2)	169
O1W—H1WA···N1	0.85	2.16	2.899 (2)	146

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

Experimental details

Crystal data
Chemical formula	C₂₆H₂₈ClNO₄·H₂O
M_r	471.96
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	8.8866 (4), 14.6386 (7), 9.1860 (4)
β (°)	91.618 (1)
V (Å³)	1194.51 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.45 × 0.36 × 0.32

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.917, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	13795, 4185, 3974
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.082, 1.05
No. of reflections	4185
No. of parameters	303
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.21
Absolute structure	Flack (1983), 1991 Friedel pairs
Absolute structure parameter	−0.02 (6)

Computer programs: SMART (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
C8—H8A···O1ⁱ	0.98	2.557	3.469 (2)	155
O1W—H1WB···O4ⁱⁱ	0.85	2.040	2.879 (2)	169
O1W—H1WA···N1	0.85	2.157	2.899 (2)	146

Symmetry codes: (i) −x, y−1/2, −z; (ii) −x+1, 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 Hunan Provincial Science and Technology Department of 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
Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Li, Y.-F., Qian, Y., Yin, L.-H., Lv, R. & Zhu, H.-J. (2009). Acta Cryst. E65, o689. CSD CrossRef IUCr Journals Google Scholar
Liu, L., Buchner, E., Beitze, D., Schmidt-Weber, C. B., Kaever, V. & Emmricinne, R. W. (1996). Int. J. Immunopharmacol. 18, 529–543. CrossRef CAS PubMed Web of Science Google Scholar
Liu, L., Riese, J., Resch, K. & Kaever, V. (1994). Arzneim. Forsch. 44, 1223–1226. CAS Google Scholar
Liu, Q., Zhou, L. L. & Li, R. (1997). Chin. Trad. Herbal Drugs, 28, 247–249. Google Scholar
Mark, W., Schneeberger, S., Seiler, R., Stroka, D. M., Amberger, A., Offner, F., Candinas, D. & Margreiter, R. (2003). Transplantation, 75, 940–945. Web of Science CrossRef PubMed CAS Google Scholar
Mitsunobu, O. (1981). Synthesis, pp. 1–28. CrossRef Web of Science Google Scholar
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 5| May 2011| Page o1190

doi:10.1107/S1600536811013973

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

(8S,9S,10R)-4-(4-Chloro­benz­yl­oxy)-7,8-dide­hydro-3,7-dimeth­­oxy-17-methyl­morphinan-6-one monohydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

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References

organic compounds

(8S,9S,10R)-4-(4-Chlorobenzyloxy)-7,8-didehydro-3,7-dimethoxy-17-methylmorphinan-6-one monohydrate