Dihydro-allocryptopine.

IN THE TITLE COMPOUND [SYSTEMATIC NAME: 7,8-dimeth-oxy-11-methyl-17,19-dioxa-11-aza-tetra-cyclo-[12.7.0.0(4,9).0(16,20)]henicosa-1(21),4,6,8,14,16 (20)-hexaen-2-ol], C(21)H(25)NO(5), the benzene rings are inclined at a dihedral angle of 23.16 (5)°. One of the meth-oxy C atoms is close to coplanar with its attached ring [deviation = 0.129 (3) Å], whereas the other is orientated away from the ring [deviation = -1.124 (2) Å]. The 10-membered ring is highly puckered, and the OH and CH(3) substituents project to the same side of the ring. In the crystal, O-H⋯O hydrogen bonds link the mol-ecules into [010] chains and C-H⋯O and C-H⋯π inter-actions consolidate the packing.

Related literature

For the synthesis of the title compound, see: Wada et al. (2007 ▶). For the biological activity of allocryptopine derivatives, see: Morteza et al. (2003 ▶); Yan et al. (2009 ▶); Capasso et al. (1997 ▶); Jeong et al. (2009 ▶); Zhao et al. (2008 ▶). For a related structure, see: Valpuesta et al. (2006 ▶).

Experimental

Crystal data

C21H25NO5

M = 371.42

Monoclinic,

a = 14.2557 (19) Å

b = 9.3705 (13) Å

c = 15.278 (2) Å

β = 106.601 (2)°

V = 1955.8 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 296 K

0.45 × 0.24 × 0.21 mm

Data collection

Bruker SMART APEX II CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.961, T max = 0.981

14189 measured reflections

3646 independent reflections

2766 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.110

S = 1.02

3646 reflections

248 parameters

H-atom parameters constrained

Δρmax = 0.18 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811052172/hb6507sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811052172/hb6507Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811052172/hb6507Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H25NO5	F(000) = 792
Mr = 371.42	Dx = 1.261 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.2557 (19) Å	Cell parameters from 3665 reflections
b = 9.3705 (13) Å	θ = 2.6–22.6°
c = 15.278 (2) Å	µ = 0.09 mm−1
β = 106.601 (2)°	T = 296 K
V = 1955.8 (5) Å3	Block, colourless
Z = 4	0.45 × 0.24 × 0.21 mm

Bruker SMART APEX II CCD diffractometer	3646 independent reflections
Radiation source: fine-focus sealed tube	2766 reflections with I > 2σ(I)
graphite	Rint = 0.026
phi and ω scans	θmax = 25.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
Tmin = 0.961, Tmax = 0.981	k = −11→11
14189 measured reflections	l = −18→18

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0526P)2 + 0.4075P] where P = (Fo2 + 2Fc2)/3
3646 reflections	(Δ/σ)max = 0.001
248 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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 andgoodness of fit S are based on F2, conventional R-factors R are basedon F, with F set to zero for negative F2. The threshold expression ofF2 > σ(F2) is used only for calculating R-factors(gt) etc. and isnot relevant to the choice of reflections for refinement. R-factors basedon F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
C1	0.27622 (11)	0.13752 (17)	0.24521 (10)	0.0402 (4)
C2	0.32459 (11)	0.17612 (18)	0.18061 (11)	0.0460 (4)
H2	0.2954	0.1612	0.1186	0.055*
C3	0.41532 (12)	0.2359 (2)	0.21064 (13)	0.0528 (4)
C4	0.46009 (13)	0.2568 (2)	0.30202 (14)	0.0592 (5)
C5	0.41615 (12)	0.2188 (2)	0.36684 (13)	0.0588 (5)
H5	0.4478	0.2329	0.4285	0.071*
C6	0.32187 (11)	0.15767 (19)	0.33900 (11)	0.0464 (4)
C7	0.55723 (15)	0.3447 (3)	0.22467 (16)	0.0776 (6)
H7A	0.6186	0.3106	0.2168	0.093*
H7B	0.5539	0.4471	0.2151	0.093*
C8	0.17251 (11)	0.08232 (16)	0.20842 (9)	0.0375 (3)
H8	0.1545	0.0280	0.2560	0.045*
C9	0.10207 (11)	0.20855 (17)	0.17812 (11)	0.0410 (4)
H9A	0.1234	0.2850	0.2221	0.049*
H9B	0.1079	0.2429	0.1200	0.049*
C10	−0.00464 (11)	0.17974 (16)	0.16778 (10)	0.0381 (3)
C11	−0.04578 (11)	0.20517 (16)	0.23982 (10)	0.0381 (3)
C12	0.01951 (11)	0.25595 (18)	0.33146 (11)	0.0444 (4)
H12A	0.0477	0.3479	0.3243	0.053*
H12B	−0.0189	0.2670	0.3742	0.053*
C13	0.19042 (11)	0.2073 (2)	0.42234 (11)	0.0507 (4)
H13A	0.1902	0.2099	0.4857	0.061*
H13B	0.1988	0.3042	0.4035	0.061*
C14	0.27663 (12)	0.1155 (2)	0.41377 (11)	0.0530 (5)
H14A	0.3274	0.1183	0.4717	0.064*
H14B	0.2544	0.0174	0.4034	0.064*
C15	0.06335 (14)	0.0326 (2)	0.40923 (13)	0.0650 (5)
H15A	0.1137	−0.0388	0.4255	0.098*
H15B	0.0059	−0.0073	0.3672	0.098*
H15C	0.0478	0.0646	0.4631	0.098*
C16	−0.14540 (11)	0.18373 (17)	0.22552 (10)	0.0410 (4)
C17	−0.20575 (11)	0.13956 (18)	0.14017 (11)	0.0452 (4)
C18	−0.16472 (12)	0.11260 (18)	0.07058 (11)	0.0463 (4)
H18	−0.2036	0.0809	0.0142	0.056*
C19	−0.06541 (12)	0.13279 (17)	0.08482 (10)	0.0430 (4)
H19	−0.0385	0.1143	0.0372	0.052*
C20	−0.22408 (15)	0.0958 (2)	0.33403 (14)	0.0674 (5)
H20A	−0.2690	0.0419	0.2868	0.101*
H20B	−0.2569	0.1293	0.3769	0.101*
H20C	−0.1700	0.0361	0.3650	0.101*
C21	−0.36808 (14)	0.0889 (3)	0.04815 (15)	0.0854 (7)
H21A	−0.3646	0.1587	0.0032	0.128*
H21B	−0.4337	0.0846	0.0529	0.128*
H21C	−0.3498	−0.0028	0.0303	0.128*
N1	0.09746 (9)	0.15187 (14)	0.36674 (8)	0.0403 (3)
O1	0.55278 (10)	0.3128 (2)	0.31403 (11)	0.0870 (5)
O2	0.47711 (10)	0.27719 (17)	0.16005 (10)	0.0764 (4)
O3	0.16204 (8)	−0.00602 (12)	0.12969 (7)	0.0458 (3)
H3	0.1735	−0.0892	0.1458	0.069*
O4	−0.30345 (8)	0.12764 (16)	0.13363 (8)	0.0642 (4)
O5	−0.18857 (8)	0.21548 (12)	0.29420 (7)	0.0497 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0378 (8)	0.0418 (9)	0.0418 (9)	0.0010 (7)	0.0127 (7)	−0.0015 (7)
C2	0.0419 (9)	0.0530 (10)	0.0431 (9)	0.0002 (7)	0.0121 (7)	0.0017 (7)
C3	0.0446 (10)	0.0587 (11)	0.0594 (11)	−0.0037 (8)	0.0216 (8)	0.0003 (9)
C4	0.0407 (9)	0.0668 (12)	0.0694 (12)	−0.0113 (9)	0.0147 (9)	−0.0111 (10)
C5	0.0432 (10)	0.0793 (14)	0.0511 (10)	−0.0077 (9)	0.0089 (8)	−0.0145 (9)
C6	0.0395 (9)	0.0553 (10)	0.0428 (9)	0.0013 (7)	0.0091 (7)	−0.0051 (8)
C7	0.0530 (12)	0.0853 (16)	0.0995 (17)	−0.0185 (11)	0.0298 (12)	−0.0081 (13)
C8	0.0417 (8)	0.0422 (9)	0.0301 (7)	−0.0026 (7)	0.0125 (6)	−0.0025 (6)
C9	0.0429 (9)	0.0425 (9)	0.0389 (8)	−0.0011 (7)	0.0140 (7)	0.0029 (7)
C10	0.0408 (8)	0.0357 (8)	0.0375 (8)	0.0027 (6)	0.0111 (6)	0.0027 (6)
C11	0.0407 (8)	0.0346 (8)	0.0381 (8)	0.0007 (6)	0.0095 (7)	−0.0015 (6)
C12	0.0430 (9)	0.0473 (9)	0.0436 (9)	−0.0029 (7)	0.0136 (7)	−0.0117 (7)
C13	0.0456 (9)	0.0690 (12)	0.0369 (8)	−0.0084 (8)	0.0108 (7)	−0.0137 (8)
C14	0.0440 (9)	0.0768 (13)	0.0347 (8)	−0.0011 (9)	0.0057 (7)	−0.0011 (8)
C15	0.0613 (11)	0.0714 (13)	0.0612 (12)	−0.0116 (10)	0.0156 (9)	0.0148 (10)
C16	0.0408 (8)	0.0424 (9)	0.0413 (9)	0.0025 (7)	0.0142 (7)	−0.0021 (7)
C17	0.0376 (9)	0.0493 (10)	0.0456 (9)	0.0016 (7)	0.0069 (7)	−0.0019 (7)
C18	0.0458 (9)	0.0531 (10)	0.0350 (8)	0.0012 (8)	0.0036 (7)	−0.0040 (7)
C19	0.0478 (9)	0.0462 (9)	0.0357 (8)	0.0048 (7)	0.0130 (7)	0.0005 (7)
C20	0.0694 (13)	0.0749 (14)	0.0672 (12)	−0.0005 (11)	0.0347 (10)	0.0095 (10)
C21	0.0436 (11)	0.128 (2)	0.0719 (14)	−0.0027 (12)	−0.0039 (10)	−0.0165 (14)
N1	0.0398 (7)	0.0478 (8)	0.0326 (6)	−0.0057 (6)	0.0095 (5)	−0.0040 (6)
O1	0.0522 (8)	0.1244 (14)	0.0852 (11)	−0.0369 (9)	0.0208 (7)	−0.0178 (10)
O2	0.0563 (8)	0.1040 (12)	0.0760 (9)	−0.0229 (8)	0.0303 (7)	0.0018 (8)
O3	0.0541 (7)	0.0482 (7)	0.0363 (6)	−0.0031 (6)	0.0150 (5)	−0.0074 (5)
O4	0.0363 (6)	0.0958 (10)	0.0561 (7)	−0.0040 (6)	0.0062 (5)	−0.0098 (7)
O5	0.0496 (7)	0.0551 (7)	0.0499 (7)	−0.0007 (5)	0.0229 (5)	−0.0060 (5)

C1—C2	1.403 (2)	C12—H12B	0.9700
C1—C6	1.407 (2)	C13—N1	1.4506 (19)
C1—C8	1.515 (2)	C13—C14	1.536 (2)
C2—C3	1.363 (2)	C13—H13A	0.9700
C2—H2	0.9300	C13—H13B	0.9700
C3—C4	1.373 (3)	C14—H14A	0.9700
C3—O2	1.383 (2)	C14—H14B	0.9700
C4—C5	1.362 (3)	C15—N1	1.445 (2)
C4—O1	1.384 (2)	C15—H15A	0.9600
C5—C6	1.410 (2)	C15—H15B	0.9600
C5—H5	0.9300	C15—H15C	0.9600
C6—C14	1.516 (2)	C16—O5	1.3920 (18)
C7—O1	1.417 (3)	C16—C17	1.404 (2)
C7—O2	1.427 (2)	C17—O4	1.3720 (19)
C7—H7A	0.9700	C17—C18	1.375 (2)
C7—H7B	0.9700	C18—C19	1.383 (2)
C8—O3	1.4323 (17)	C18—H18	0.9300
C8—C9	1.535 (2)	C19—H19	0.9300
C8—H8	0.9800	C20—O5	1.435 (2)
C9—C10	1.508 (2)	C20—H20A	0.9600
C9—H9A	0.9700	C20—H20B	0.9600
C9—H9B	0.9700	C20—H20C	0.9600
C10—C19	1.387 (2)	C21—O4	1.414 (2)
C10—C11	1.407 (2)	C21—H21A	0.9600
C11—C16	1.388 (2)	C21—H21B	0.9600
C11—C12	1.519 (2)	C21—H21C	0.9600
C12—N1	1.461 (2)	O3—H3	0.8200
C12—H12A	0.9700
C2—C1—C6	120.30 (14)	N1—C13—H13A	109.3
C2—C1—C8	116.79 (13)	C14—C13—H13A	109.3
C6—C1—C8	122.82 (13)	N1—C13—H13B	109.3
C3—C2—C1	118.61 (15)	C14—C13—H13B	109.3
C3—C2—H2	120.7	H13A—C13—H13B	108.0
C1—C2—H2	120.7	C6—C14—C13	116.17 (15)
C2—C3—C4	121.44 (16)	C6—C14—H14A	108.2
C2—C3—O2	128.43 (17)	C13—C14—H14A	108.2
C4—C3—O2	110.06 (15)	C6—C14—H14B	108.2
C5—C4—C3	121.68 (16)	C13—C14—H14B	108.2
C5—C4—O1	128.52 (18)	H14A—C14—H14B	107.4
C3—C4—O1	109.74 (17)	N1—C15—H15A	109.5
C4—C5—C6	118.93 (16)	N1—C15—H15B	109.5
C4—C5—H5	120.5	H15A—C15—H15B	109.5
C6—C5—H5	120.5	N1—C15—H15C	109.5
C1—C6—C5	119.03 (15)	H15A—C15—H15C	109.5
C1—C6—C14	124.04 (14)	H15B—C15—H15C	109.5
C5—C6—C14	116.92 (14)	C11—C16—O5	120.21 (13)
O1—C7—O2	109.03 (15)	C11—C16—C17	121.11 (14)
O1—C7—H7A	109.9	O5—C16—C17	118.53 (13)
O2—C7—H7A	109.9	O4—C17—C18	125.15 (14)
O1—C7—H7B	109.9	O4—C17—C16	115.57 (14)
O2—C7—H7B	109.9	C18—C17—C16	119.28 (14)
H7A—C7—H7B	108.3	C17—C18—C19	119.72 (14)
O3—C8—C1	111.43 (12)	C17—C18—H18	120.1
O3—C8—C9	106.85 (12)	C19—C18—H18	120.1
C1—C8—C9	109.50 (13)	C18—C19—C10	122.10 (14)
O3—C8—H8	109.7	C18—C19—H19	118.9
C1—C8—H8	109.7	C10—C19—H19	118.9
C9—C8—H8	109.7	O5—C20—H20A	109.5
C10—C9—C8	116.55 (13)	O5—C20—H20B	109.5
C10—C9—H9A	108.2	H20A—C20—H20B	109.5
C8—C9—H9A	108.2	O5—C20—H20C	109.5
C10—C9—H9B	108.2	H20A—C20—H20C	109.5
C8—C9—H9B	108.2	H20B—C20—H20C	109.5
H9A—C9—H9B	107.3	O4—C21—H21A	109.5
C19—C10—C11	118.51 (14)	O4—C21—H21B	109.5
C19—C10—C9	120.04 (13)	H21A—C21—H21B	109.5
C11—C10—C9	121.40 (13)	O4—C21—H21C	109.5
C16—C11—C10	119.24 (13)	H21A—C21—H21C	109.5
C16—C11—C12	121.34 (13)	H21B—C21—H21C	109.5
C10—C11—C12	119.42 (13)	C15—N1—C13	112.48 (14)
N1—C12—C11	109.40 (12)	C15—N1—C12	111.35 (14)
N1—C12—H12A	109.8	C13—N1—C12	116.64 (13)
C11—C12—H12A	109.8	C4—O1—C7	104.83 (15)
N1—C12—H12B	109.8	C3—O2—C7	104.43 (15)
C11—C12—H12B	109.8	C8—O3—H3	109.5
H12A—C12—H12B	108.2	C17—O4—C21	117.92 (14)
N1—C13—C14	111.64 (14)	C16—O5—C20	115.97 (13)
C6—C1—C2—C3	−1.3 (2)	C1—C6—C14—C13	−71.7 (2)
C8—C1—C2—C3	175.33 (15)	C5—C6—C14—C13	109.25 (18)
C1—C2—C3—C4	0.9 (3)	N1—C13—C14—C6	90.26 (18)
C1—C2—C3—O2	177.59 (17)	C10—C11—C16—O5	−176.56 (13)
C2—C3—C4—C5	0.1 (3)	C12—C11—C16—O5	3.2 (2)
O2—C3—C4—C5	−177.16 (18)	C10—C11—C16—C17	−1.1 (2)
C2—C3—C4—O1	177.33 (17)	C12—C11—C16—C17	178.70 (15)
O2—C3—C4—O1	0.1 (2)	C11—C16—C17—O4	−177.48 (14)
C3—C4—C5—C6	−0.6 (3)	O5—C16—C17—O4	−1.9 (2)
O1—C4—C5—C6	−177.3 (2)	C11—C16—C17—C18	2.2 (2)
C2—C1—C6—C5	0.8 (3)	O5—C16—C17—C18	177.73 (14)
C8—C1—C6—C5	−175.64 (15)	O4—C17—C18—C19	177.98 (16)
C2—C1—C6—C14	−178.21 (16)	C16—C17—C18—C19	−1.7 (2)
C8—C1—C6—C14	5.3 (3)	C17—C18—C19—C10	0.1 (3)
C4—C5—C6—C1	0.2 (3)	C11—C10—C19—C18	1.0 (2)
C4—C5—C6—C14	179.25 (17)	C9—C10—C19—C18	−176.33 (15)
C2—C1—C8—O3	38.31 (19)	C14—C13—N1—C15	79.54 (18)
C6—C1—C8—O3	−145.11 (15)	C14—C13—N1—C12	−150.04 (14)
C2—C1—C8—C9	−79.68 (17)	C11—C12—N1—C15	−80.48 (17)
C6—C1—C8—C9	96.90 (17)	C11—C12—N1—C13	148.58 (13)
O3—C8—C9—C10	77.80 (16)	C5—C4—O1—C7	−174.7 (2)
C1—C8—C9—C10	−161.39 (13)	C3—C4—O1—C7	8.3 (2)
C8—C9—C10—C19	−89.37 (18)	O2—C7—O1—C4	−13.5 (2)
C8—C9—C10—C11	93.35 (17)	C2—C3—O2—C7	174.7 (2)
C19—C10—C11—C16	−0.5 (2)	C4—C3—O2—C7	−8.3 (2)
C9—C10—C11—C16	176.82 (14)	O1—C7—O2—C3	13.6 (2)
C19—C10—C11—C12	179.70 (14)	C18—C17—O4—C21	−2.1 (3)
C9—C10—C11—C12	−3.0 (2)	C16—C17—O4—C21	177.58 (18)
C16—C11—C12—N1	121.81 (15)	C11—C16—O5—C20	−112.30 (17)
C10—C11—C12—N1	−58.39 (19)	C17—C16—O5—C20	72.12 (19)

Cg2 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O5i	0.82	2.03	2.8380 (16)	168
C7—H7A···O4ii	0.97	2.57	3.405 (3)	144
C18—H18···O3iii	0.93	2.53	3.229 (2)	132
C7—H7B···Cg2iv	0.97	2.57	3.464 (3)	153

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O5i	0.82	2.03	2.8380 (16)	168
C7—H7A⋯O4ii	0.97	2.57	3.405 (3)	144
C18—H18⋯O3iii	0.93	2.53	3.229 (2)	132
C7—H7B⋯Cg2iv	0.97	2.57	3.464 (3)	153

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .