Dihydro-cryptopine.

IN THE CRYSTAL STRUCTURE OF THE TITLE COMPOUND [SYSTEMATIC NAME: 6,7-dimeth-oxy-12-methyl-16,18-dioxa-12-aza-tetra-cyclo-[12.7.0.0(4,9).0(15,19)]henicosa-1(21),4,6,8,14,19-hexaen-3-ol], C(21)H(25)NO(5), the benzene rings exhibits a dihedral angle of 14.95 (4)°. In the crystal, mol-ecules are linked by pairs of O-H⋯O hydrogen bonding into inversion dimers. These dimers are further connected by C-H⋯O inter-actions.

Related literature

For the synthesis of the title compound, see: Wada et al. (2007 ▶). For the biological activity of cryptopine derivatives, see: Morteza et al. (2003 ▶); Yang et al. (2009 ▶); Capasso et al. (1997 ▶); Jeong et al. (2009 ▶).

Experimental

Crystal data

C21H25NO5

M = 371.42

Monoclinic,

a = 9.5810 (16) Å

b = 6.7405 (12) Å

c = 28.886 (5) Å

β = 92.164 (2)°

V = 1864.2 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 296 K

0.26 × 0.21 × 0.18 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.976, T max = 0.983

13267 measured reflections

3460 independent reflections

2721 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.105

S = 1.02

3460 reflections

248 parameters

H-atom parameters constrained

Δρmax = 0.12 e Å−3

Δρmin = −0.18 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/S1600536812017588/nc2270sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812017588/nc2270Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812017588/nc2270Isup3.cml

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

C21H25NO5	F(000) = 792
Mr = 371.42	Dx = 1.323 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.5810 (16) Å	Cell parameters from 4124 reflections
b = 6.7405 (12) Å	θ = 2.5–26.5°
c = 28.886 (5) Å	µ = 0.09 mm−1
β = 92.164 (2)°	T = 296 K
V = 1864.2 (6) Å3	Block, colourless
Z = 4	0.26 × 0.21 × 0.18 mm

Bruker SMART APEXII CCD area-detector diffractometer	3460 independent reflections
Radiation source: fine-focus sealed tube	2721 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
phi and ω scans	θmax = 25.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.976, Tmax = 0.983	k = −8→8
13267 measured reflections	l = −34→34

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0533P)2 + 0.3327P] where P = (Fo2 + 2Fc2)/3
3460 reflections	(Δ/σ)max < 0.001
248 parameters	Δρmax = 0.12 e Å−3
0 restraints	Δρmin = −0.18 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 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.

	x	y	z	Uiso*/Ueq
C1	0.7221 (2)	0.5338 (3)	0.34220 (6)	0.0678 (5)
H1A	0.6576	0.6282	0.3550	0.081*
H1B	0.8016	0.5203	0.3638	0.081*
C2	0.72327 (15)	0.4630 (2)	0.26692 (5)	0.0479 (4)
C3	0.65789 (15)	0.3100 (3)	0.28885 (5)	0.0487 (4)
C4	0.60582 (15)	0.1506 (2)	0.26509 (5)	0.0487 (4)
H4	0.5641	0.0445	0.2798	0.058*
C5	0.61899 (14)	0.1562 (2)	0.21705 (5)	0.0422 (3)
H5	0.5837	0.0503	0.1996	0.051*
C6	0.68174 (13)	0.3111 (2)	0.19394 (5)	0.0377 (3)
C7	0.73928 (15)	0.4729 (2)	0.21985 (5)	0.0431 (3)
C8	0.80651 (18)	0.6541 (2)	0.19944 (5)	0.0548 (4)
H8A	0.7337	0.7419	0.1873	0.066*
H8B	0.8579	0.7244	0.2239	0.066*
C9	0.92335 (19)	0.7795 (2)	0.13244 (6)	0.0612 (5)
H9A	1.0044	0.7549	0.1141	0.073*
H9B	0.9429	0.8954	0.1515	0.073*
C10	0.79804 (19)	0.8230 (2)	0.09997 (6)	0.0576 (4)
H10A	0.7165	0.8392	0.1185	0.069*
H10B	0.8141	0.9485	0.0846	0.069*
C11	0.76530 (15)	0.6684 (2)	0.06336 (5)	0.0446 (4)
C12	0.67469 (14)	0.5083 (2)	0.06902 (5)	0.0410 (3)
C13	0.60773 (14)	0.4639 (2)	0.11475 (5)	0.0411 (3)
H13	0.6067	0.5852	0.1334	0.049*
C14	0.68894 (14)	0.3028 (2)	0.14177 (4)	0.0390 (3)
H14A	0.6543	0.1744	0.1314	0.047*
H14B	0.7863	0.3110	0.1338	0.047*
C15	1.03219 (19)	0.5291 (4)	0.18198 (7)	0.0806 (6)
H15A	1.0963	0.5089	0.1577	0.121*
H15B	1.0145	0.4048	0.1969	0.121*
H15C	1.0718	0.6208	0.2042	0.121*
C16	0.64789 (15)	0.3799 (2)	0.03173 (5)	0.0435 (3)
H16	0.5874	0.2737	0.0354	0.052*
C17	0.70861 (15)	0.4061 (2)	−0.01042 (5)	0.0450 (4)
C18	0.80076 (15)	0.5652 (2)	−0.01613 (5)	0.0462 (4)
C19	0.82693 (16)	0.6915 (2)	0.02052 (5)	0.0490 (4)
H19	0.8882	0.7967	0.0167	0.059*
C20	0.5989 (2)	0.1198 (3)	−0.04403 (6)	0.0634 (5)
H20A	0.6408	0.0319	−0.0214	0.095*
H20B	0.5888	0.0524	−0.0732	0.095*
H20C	0.5087	0.1606	−0.0342	0.095*
C21	0.95733 (18)	0.7328 (3)	−0.06464 (6)	0.0669 (5)
H21A	0.9147	0.8601	−0.0605	0.100*
H21B	0.9929	0.7246	−0.0952	0.100*
H21C	1.0326	0.7159	−0.0421	0.100*
N1	0.90152 (13)	0.60922 (19)	0.16244 (4)	0.0504 (3)
O1	0.76747 (15)	0.6038 (2)	0.29889 (4)	0.0766 (4)
O2	0.65523 (14)	0.3471 (2)	0.33582 (4)	0.0720 (4)
O3	0.46774 (10)	0.39104 (16)	0.10842 (4)	0.0531 (3)
H3	0.4165	0.4813	0.0992	0.080*
O4	0.68526 (12)	0.28907 (18)	−0.04891 (3)	0.0598 (3)
O5	0.85638 (11)	0.58148 (19)	−0.05891 (4)	0.0626 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0611 (11)	0.0995 (15)	0.0425 (9)	0.0074 (10)	0.0007 (8)	−0.0176 (9)
C2	0.0436 (8)	0.0566 (9)	0.0436 (8)	0.0013 (7)	0.0005 (6)	−0.0111 (7)
C3	0.0411 (8)	0.0690 (10)	0.0361 (8)	0.0084 (8)	0.0029 (6)	0.0023 (7)
C4	0.0416 (8)	0.0584 (10)	0.0463 (9)	0.0007 (7)	0.0048 (6)	0.0102 (7)
C5	0.0381 (7)	0.0437 (8)	0.0448 (8)	0.0007 (6)	0.0017 (6)	−0.0003 (6)
C6	0.0329 (7)	0.0396 (8)	0.0409 (7)	0.0039 (6)	0.0043 (6)	−0.0019 (6)
C7	0.0400 (8)	0.0468 (8)	0.0430 (8)	0.0008 (6)	0.0057 (6)	−0.0055 (6)
C8	0.0655 (10)	0.0488 (9)	0.0507 (9)	−0.0124 (8)	0.0105 (8)	−0.0138 (7)
C9	0.0698 (11)	0.0517 (10)	0.0631 (11)	−0.0270 (9)	0.0159 (9)	−0.0119 (8)
C10	0.0734 (11)	0.0354 (8)	0.0653 (10)	−0.0082 (8)	0.0201 (9)	0.0018 (7)
C11	0.0473 (8)	0.0383 (8)	0.0488 (8)	0.0014 (6)	0.0082 (7)	0.0079 (6)
C12	0.0406 (8)	0.0402 (8)	0.0425 (8)	0.0027 (6)	0.0071 (6)	0.0061 (6)
C13	0.0421 (8)	0.0388 (8)	0.0431 (8)	−0.0021 (6)	0.0090 (6)	0.0005 (6)
C14	0.0413 (8)	0.0360 (7)	0.0403 (8)	−0.0014 (6)	0.0076 (6)	−0.0042 (6)
C15	0.0506 (11)	0.1104 (17)	0.0806 (14)	−0.0113 (11)	−0.0011 (9)	0.0008 (12)
C16	0.0426 (8)	0.0462 (8)	0.0420 (8)	−0.0050 (6)	0.0053 (6)	0.0063 (6)
C17	0.0411 (8)	0.0558 (9)	0.0381 (8)	0.0007 (7)	0.0018 (6)	0.0054 (7)
C18	0.0405 (8)	0.0589 (10)	0.0396 (8)	−0.0001 (7)	0.0062 (6)	0.0131 (7)
C19	0.0458 (8)	0.0465 (9)	0.0553 (9)	−0.0043 (7)	0.0082 (7)	0.0147 (7)
C20	0.0755 (12)	0.0650 (11)	0.0500 (10)	−0.0126 (9)	0.0076 (8)	−0.0057 (8)
C21	0.0538 (10)	0.0878 (13)	0.0600 (10)	−0.0096 (9)	0.0150 (8)	0.0255 (10)
N1	0.0459 (7)	0.0517 (8)	0.0541 (8)	−0.0122 (6)	0.0078 (6)	−0.0070 (6)
O1	0.0940 (10)	0.0879 (9)	0.0483 (7)	−0.0248 (8)	0.0078 (6)	−0.0235 (6)
O2	0.0812 (9)	0.0981 (10)	0.0369 (6)	−0.0062 (8)	0.0049 (6)	−0.0039 (6)
O3	0.0399 (6)	0.0642 (7)	0.0555 (7)	−0.0020 (5)	0.0074 (5)	0.0149 (5)
O4	0.0663 (7)	0.0753 (8)	0.0382 (6)	−0.0172 (6)	0.0086 (5)	−0.0013 (5)
O5	0.0566 (7)	0.0870 (9)	0.0451 (6)	−0.0144 (6)	0.0139 (5)	0.0140 (6)

C1—O1	1.420 (2)	C12—C16	1.398 (2)
C1—O2	1.422 (2)	C12—C13	1.5200 (19)
C1—H1A	0.9700	C13—O3	1.4335 (17)
C1—H1B	0.9700	C13—C14	1.5322 (19)
C2—C3	1.374 (2)	C13—H13	0.9800
C2—C7	1.376 (2)	C14—H14A	0.9700
C2—O1	1.3793 (18)	C14—H14B	0.9700
C3—C4	1.360 (2)	C15—N1	1.457 (2)
C3—O2	1.3807 (17)	C15—H15A	0.9600
C4—C5	1.399 (2)	C15—H15B	0.9600
C4—H4	0.9300	C15—H15C	0.9600
C5—C6	1.388 (2)	C16—C17	1.3805 (19)
C5—H5	0.9300	C16—H16	0.9300
C6—C7	1.422 (2)	C17—O4	1.3745 (18)
C6—C14	1.5122 (18)	C17—C18	1.403 (2)
C7—C8	1.511 (2)	C18—O5	1.3685 (17)
C8—N1	1.4617 (19)	C18—C19	1.374 (2)
C8—H8A	0.9700	C19—H19	0.9300
C8—H8B	0.9700	C20—O4	1.420 (2)
C9—N1	1.458 (2)	C20—H20A	0.9600
C9—C10	1.524 (3)	C20—H20B	0.9600
C9—H9A	0.9700	C20—H20C	0.9600
C9—H9B	0.9700	C21—O5	1.419 (2)
C10—C11	1.509 (2)	C21—H21A	0.9600
C10—H10A	0.9700	C21—H21B	0.9600
C10—H10B	0.9700	C21—H21C	0.9600
C11—C19	1.400 (2)	O3—H3	0.8200
C11—C12	1.398 (2)
O1—C1—O2	109.34 (13)	O3—C13—C14	106.08 (11)
O1—C1—H1A	109.8	C12—C13—C14	111.07 (11)
O2—C1—H1A	109.8	O3—C13—H13	109.1
O1—C1—H1B	109.8	C12—C13—H13	109.1
O2—C1—H1B	109.8	C14—C13—H13	109.1
H1A—C1—H1B	108.3	C6—C14—C13	116.11 (11)
C3—C2—C7	124.18 (14)	C6—C14—H14A	108.3
C3—C2—O1	109.97 (13)	C13—C14—H14A	108.3
C7—C2—O1	125.84 (15)	C6—C14—H14B	108.3
C4—C3—C2	121.71 (14)	C13—C14—H14B	108.3
C4—C3—O2	128.23 (15)	H14A—C14—H14B	107.4
C2—C3—O2	110.07 (14)	N1—C15—H15A	109.5
C3—C4—C5	115.72 (14)	N1—C15—H15B	109.5
C3—C4—H4	122.1	H15A—C15—H15B	109.5
C5—C4—H4	122.1	N1—C15—H15C	109.5
C6—C5—C4	123.69 (14)	H15A—C15—H15C	109.5
C6—C5—H5	118.2	H15B—C15—H15C	109.5
C4—C5—H5	118.2	C17—C16—C12	121.96 (14)
C5—C6—C7	119.32 (13)	C17—C16—H16	119.0
C5—C6—C14	119.24 (12)	C12—C16—H16	119.0
C7—C6—C14	121.44 (12)	O4—C17—C16	125.38 (14)
C2—C7—C6	115.33 (13)	O4—C17—C18	115.30 (12)
C2—C7—C8	119.32 (13)	C16—C17—C18	119.31 (14)
C6—C7—C8	125.25 (13)	O5—C18—C19	125.45 (14)
N1—C8—C7	113.84 (12)	O5—C18—C17	115.85 (14)
N1—C8—H8A	108.8	C19—C18—C17	118.70 (13)
C7—C8—H8A	108.8	C18—C19—C11	122.79 (14)
N1—C8—H8B	108.8	C18—C19—H19	118.6
C7—C8—H8B	108.8	C11—C19—H19	118.6
H8A—C8—H8B	107.7	O4—C20—H20A	109.5
N1—C9—C10	112.95 (13)	O4—C20—H20B	109.5
N1—C9—H9A	109.0	H20A—C20—H20B	109.5
C10—C9—H9A	109.0	O4—C20—H20C	109.5
N1—C9—H9B	109.0	H20A—C20—H20C	109.5
C10—C9—H9B	109.0	H20B—C20—H20C	109.5
H9A—C9—H9B	107.8	O5—C21—H21A	109.5
C11—C10—C9	115.88 (14)	O5—C21—H21B	109.5
C11—C10—H10A	108.3	H21A—C21—H21B	109.5
C9—C10—H10A	108.3	O5—C21—H21C	109.5
C11—C10—H10B	108.3	H21A—C21—H21C	109.5
C9—C10—H10B	108.3	H21B—C21—H21C	109.5
H10A—C10—H10B	107.4	C9—N1—C15	112.43 (14)
C19—C11—C12	118.27 (14)	C9—N1—C8	112.27 (13)
C19—C11—C10	117.35 (13)	C15—N1—C8	110.06 (14)
C12—C11—C10	124.35 (13)	C2—O1—C1	105.37 (14)
C16—C12—C11	118.97 (13)	C3—O2—C1	105.22 (13)
C16—C12—C13	118.44 (12)	C13—O3—H3	109.5
C11—C12—C13	122.55 (13)	C17—O4—C20	117.30 (12)
O3—C13—C12	112.35 (11)	C18—O5—C21	116.96 (13)
C7—C2—C3—C4	1.7 (2)	C5—C6—C14—C13	115.88 (14)
O1—C2—C3—C4	−179.25 (14)	C7—C6—C14—C13	−64.86 (17)
C7—C2—C3—O2	−178.17 (14)	O3—C13—C14—C6	−86.03 (14)
O1—C2—C3—O2	0.91 (18)	C12—C13—C14—C6	151.62 (12)
C2—C3—C4—C5	−2.1 (2)	C11—C12—C16—C17	0.2 (2)
O2—C3—C4—C5	177.69 (14)	C13—C12—C16—C17	−177.67 (13)
C3—C4—C5—C6	0.6 (2)	C12—C16—C17—O4	−178.53 (13)
C4—C5—C6—C7	1.4 (2)	C12—C16—C17—C18	0.4 (2)
C4—C5—C6—C14	−179.36 (13)	O4—C17—C18—O5	−0.76 (19)
C3—C2—C7—C6	0.4 (2)	C16—C17—C18—O5	−179.84 (13)
O1—C2—C7—C6	−178.53 (14)	O4—C17—C18—C19	178.58 (13)
C3—C2—C7—C8	176.81 (15)	C16—C17—C18—C19	−0.5 (2)
O1—C2—C7—C8	−2.1 (2)	O5—C18—C19—C11	179.15 (14)
C5—C6—C7—C2	−1.82 (19)	C17—C18—C19—C11	−0.1 (2)
C14—C6—C7—C2	178.92 (13)	C12—C11—C19—C18	0.8 (2)
C5—C6—C7—C8	−177.99 (14)	C10—C11—C19—C18	−177.30 (15)
C14—C6—C7—C8	2.8 (2)	C10—C9—N1—C15	161.30 (15)
C2—C7—C8—N1	139.97 (14)	C10—C9—N1—C8	−73.96 (17)
C6—C7—C8—N1	−44.0 (2)	C7—C8—N1—C9	158.57 (14)
N1—C9—C10—C11	−66.69 (18)	C7—C8—N1—C15	−75.39 (18)
C9—C10—C11—C19	−91.15 (17)	C3—C2—O1—C1	−1.83 (18)
C9—C10—C11—C12	90.89 (19)	C7—C2—O1—C1	177.23 (16)
C19—C11—C12—C16	−0.8 (2)	O2—C1—O1—C2	2.09 (18)
C10—C11—C12—C16	177.11 (14)	C4—C3—O2—C1	−179.40 (16)
C19—C11—C12—C13	176.99 (13)	C2—C3—O2—C1	0.42 (17)
C10—C11—C12—C13	−5.1 (2)	O1—C1—O2—C3	−1.56 (18)
C16—C12—C13—O3	−38.64 (17)	C16—C17—O4—C20	−4.4 (2)
C11—C12—C13—O3	143.52 (14)	C18—C17—O4—C20	176.55 (14)
C16—C12—C13—C14	79.99 (16)	C19—C18—O5—C21	5.0 (2)
C11—C12—C13—C14	−97.85 (15)	C17—C18—O5—C21	−175.74 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4i	0.82	2.31	3.0924 (16)	159
C1—H1A···O3ii	0.97	2.41	3.367 (2)	170

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O4i	0.82	2.31	3.0924 (16)	159
C1—H1A⋯O3ii	0.97	2.41	3.367 (2)	170

Symmetry codes: (i) ; (ii) .