8-Meth-oxy-3,3,5-trimethyl-3,11-dihydro-pyrano[3,2-a]carbazole.

In the title compound, C(19)H(19)NO(2), commonly called koenimbine, the pyran ring adopts a sofa conformation. The carbazole ring system is planar [r.m.s. deviation = 0.063 (1) Å]. A C(10) zigzag chain running along the b axis is formed through inter-molecular C-H⋯O hydrogen bonds. The chains are linked via weak C-H⋯π and N-H⋯π inter-actions.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For the bio­logical activity of carbazole derivatives, see: Kong et al. (1986 ▶); Ito (2000 ▶); Ramsewak et al. (1999 ▶); Chowdhury et al. (2001 ▶); Fiebi et al. (1985 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For asymmetry parameters, see: Nardelli (1983 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C19H19NO2

M = 293.35

Monoclinic,

a = 8.290 (5) Å

b = 8.693 (5) Å

c = 21.326 (5) Å

β = 90.742 (5)°

V = 1536.7 (13) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 293 K

0.20 × 0.17 × 0.16 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.984, T max = 0.987

14325 measured reflections

3803 independent reflections

3050 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.137

S = 1.05

3803 reflections

207 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681002074X/sj5011sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681002074X/sj5011Isup2.hkl

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

C19H19NO2	F(000) = 624
Mr = 293.35	Dx = 1.268 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1546 reflections
a = 8.290 (5) Å	θ = 1.9–28.3°
b = 8.693 (5) Å	µ = 0.08 mm−1
c = 21.326 (5) Å	T = 293 K
β = 90.742 (5)°	Block, colorless
V = 1536.7 (13) Å3	0.20 × 0.17 × 0.16 mm
Z = 4

Bruker SMART APEXII area-detector diffractometer	3803 independent reflections
Radiation source: fine-focus sealed tube	3050 reflections with I > 2σ(I)
graphite	Rint = 0.026
ω and φ scans	θmax = 28.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→11
Tmin = 0.984, Tmax = 0.987	k = −9→11
14325 measured reflections	l = −28→28

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0713P)2 + 0.2629P] where P = (Fo2 + 2Fc2)/3
3803 reflections	(Δ/σ)max = 0.004
207 parameters	Δρmax = 0.24 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

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.

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
O1	1.12605 (11)	0.25969 (10)	0.57699 (4)	0.0444 (2)
O2	0.32475 (14)	0.26609 (14)	0.86787 (5)	0.0676 (3)
N1	0.93165 (14)	0.40700 (14)	0.78439 (5)	0.0436 (3)
C2	0.78388 (15)	0.37981 (14)	0.81195 (6)	0.0396 (3)
C3	0.72718 (17)	0.42649 (16)	0.87003 (6)	0.0468 (3)
H3	0.7911	0.4851	0.8971	0.056*
C4	0.57398 (18)	0.38336 (16)	0.88612 (6)	0.0487 (3)
H4	0.5338	0.4134	0.9248	0.058*
C5	0.47677 (16)	0.29541 (15)	0.84589 (6)	0.0451 (3)
C6	0.53268 (16)	0.24753 (14)	0.78823 (6)	0.0407 (3)
H6	0.4684	0.1883	0.7616	0.049*
C7	0.68785 (15)	0.29046 (14)	0.77121 (5)	0.0368 (3)
C8	0.78297 (14)	0.26342 (13)	0.71591 (5)	0.0360 (3)
C9	0.75455 (14)	0.18608 (15)	0.65939 (6)	0.0381 (3)
H9	0.6579	0.1337	0.6532	0.046*
C10	0.86873 (15)	0.18656 (14)	0.61251 (5)	0.0381 (3)
C11	1.01461 (15)	0.26595 (13)	0.62376 (6)	0.0364 (3)
C12	1.25668 (16)	0.37274 (16)	0.57659 (7)	0.0472 (3)
C13	1.31224 (18)	0.40802 (18)	0.64208 (8)	0.0561 (4)
H13	1.4190	0.4368	0.6492	0.067*
C14	1.21332 (16)	0.39936 (17)	0.69017 (7)	0.0493 (3)
H14	1.2471	0.4319	0.7298	0.059*
C15	1.05153 (14)	0.33853 (14)	0.68064 (6)	0.0377 (3)
C16	0.93148 (14)	0.33859 (14)	0.72584 (5)	0.0369 (3)
C17	0.23594 (19)	0.1452 (2)	0.84007 (8)	0.0625 (4)
H17A	0.2161	0.1681	0.7966	0.094*
H17B	0.1350	0.1338	0.8611	0.094*
H17C	0.2963	0.0512	0.8435	0.094*
C18	0.83971 (18)	0.10395 (18)	0.55133 (6)	0.0512 (3)
H18A	0.8971	0.0081	0.5517	0.077*
H18B	0.8771	0.1665	0.5174	0.077*
H18C	0.7264	0.0846	0.5459	0.077*
C19	1.38727 (19)	0.2969 (2)	0.53819 (8)	0.0624 (4)
H19A	1.4205	0.2029	0.5582	0.094*
H19B	1.4780	0.3650	0.5352	0.094*
H19C	1.3459	0.2747	0.4969	0.094*
C20	1.1956 (2)	0.5186 (2)	0.54519 (9)	0.0694 (5)
H20A	1.1633	0.4962	0.5028	0.104*
H20B	1.2800	0.5943	0.5452	0.104*
H20C	1.1049	0.5577	0.5678	0.104*
H1	1.005 (2)	0.469 (2)	0.7994 (8)	0.063 (5)*

	U11	U22	U33	U12	U13	U23
O1	0.0402 (5)	0.0453 (5)	0.0480 (5)	−0.0053 (4)	0.0115 (4)	−0.0031 (4)
O2	0.0550 (7)	0.0727 (8)	0.0759 (7)	−0.0199 (5)	0.0296 (6)	−0.0240 (6)
N1	0.0379 (6)	0.0484 (6)	0.0446 (6)	−0.0083 (5)	0.0010 (4)	−0.0095 (5)
C2	0.0392 (7)	0.0376 (6)	0.0421 (6)	−0.0015 (5)	0.0011 (5)	−0.0026 (5)
C3	0.0519 (8)	0.0456 (7)	0.0431 (6)	−0.0064 (6)	0.0028 (5)	−0.0091 (5)
C4	0.0566 (8)	0.0456 (7)	0.0443 (6)	−0.0036 (6)	0.0118 (6)	−0.0081 (5)
C5	0.0427 (7)	0.0412 (7)	0.0516 (7)	−0.0026 (5)	0.0115 (6)	−0.0022 (5)
C6	0.0379 (7)	0.0389 (6)	0.0454 (6)	−0.0027 (5)	0.0032 (5)	−0.0035 (5)
C7	0.0363 (6)	0.0348 (6)	0.0392 (6)	0.0008 (5)	0.0012 (5)	−0.0017 (5)
C8	0.0325 (6)	0.0352 (6)	0.0402 (6)	−0.0010 (4)	0.0010 (4)	0.0000 (4)
C9	0.0320 (6)	0.0406 (6)	0.0419 (6)	−0.0044 (5)	0.0003 (5)	−0.0033 (5)
C10	0.0371 (6)	0.0372 (6)	0.0400 (6)	−0.0011 (5)	0.0007 (5)	−0.0031 (5)
C11	0.0335 (6)	0.0343 (6)	0.0416 (6)	0.0012 (4)	0.0049 (5)	0.0017 (5)
C12	0.0375 (7)	0.0454 (7)	0.0589 (8)	−0.0043 (5)	0.0118 (6)	0.0042 (6)
C13	0.0379 (7)	0.0620 (9)	0.0686 (9)	−0.0139 (6)	0.0062 (6)	−0.0086 (7)
C14	0.0383 (7)	0.0537 (8)	0.0558 (7)	−0.0093 (6)	0.0009 (6)	−0.0077 (6)
C15	0.0331 (6)	0.0359 (6)	0.0443 (6)	−0.0015 (5)	0.0004 (5)	−0.0009 (5)
C16	0.0343 (6)	0.0356 (6)	0.0409 (6)	−0.0012 (4)	−0.0012 (5)	−0.0016 (5)
C17	0.0472 (9)	0.0626 (10)	0.0781 (11)	−0.0123 (7)	0.0114 (7)	−0.0048 (8)
C18	0.0496 (8)	0.0590 (9)	0.0450 (7)	−0.0091 (6)	0.0049 (6)	−0.0127 (6)
C19	0.0458 (8)	0.0706 (10)	0.0714 (10)	0.0002 (7)	0.0205 (7)	0.0012 (8)
C20	0.0619 (10)	0.0536 (9)	0.0931 (12)	−0.0001 (8)	0.0121 (9)	0.0182 (9)

O1—C11	1.3693 (15)	C10—C18	1.5059 (17)
O1—C12	1.4625 (17)	C11—C15	1.3977 (17)
O2—C5	1.3741 (18)	C12—C13	1.497 (2)
O2—C17	1.410 (2)	C12—C19	1.517 (2)
N1—C16	1.3830 (16)	C12—C20	1.518 (2)
N1—C2	1.3859 (18)	C13—C14	1.323 (2)
N1—H1	0.872 (18)	C13—H13	0.9300
C2—C3	1.3911 (18)	C14—C15	1.4535 (19)
C2—C7	1.4050 (17)	C14—H14	0.9300
C3—C4	1.372 (2)	C15—C16	1.3945 (18)
C3—H3	0.9300	C17—H17A	0.9600
C4—C5	1.397 (2)	C17—H17B	0.9600
C4—H4	0.9300	C17—H17C	0.9600
C5—C6	1.3838 (18)	C18—H18A	0.9600
C6—C7	1.3920 (19)	C18—H18B	0.9600
C6—H6	0.9300	C18—H18C	0.9600
C7—C8	1.4463 (17)	C19—H19A	0.9600
C8—C9	1.3975 (16)	C19—H19B	0.9600
C8—C16	1.4075 (18)	C19—H19C	0.9600
C9—C10	1.3856 (17)	C20—H20A	0.9600
C9—H9	0.9300	C20—H20B	0.9600
C10—C11	1.4102 (18)	C20—H20C	0.9600
C11—O1—C12	118.95 (10)	C13—C12—C20	109.71 (14)
C5—O2—C17	118.11 (12)	C19—C12—C20	111.18 (13)
C16—N1—C2	108.60 (10)	C14—C13—C12	121.68 (13)
C16—N1—H1	126.3 (11)	C14—C13—H13	119.2
C2—N1—H1	124.4 (11)	C12—C13—H13	119.2
N1—C2—C3	129.69 (12)	C13—C14—C15	119.48 (13)
N1—C2—C7	109.20 (11)	C13—C14—H14	120.3
C3—C2—C7	121.11 (12)	C15—C14—H14	120.3
C4—C3—C2	117.87 (12)	C16—C15—C11	116.73 (11)
C4—C3—H3	121.1	C16—C15—C14	124.66 (12)
C2—C3—H3	121.1	C11—C15—C14	118.49 (11)
C3—C4—C5	121.62 (12)	N1—C16—C15	129.19 (11)
C3—C4—H4	119.2	N1—C16—C8	109.03 (11)
C5—C4—H4	119.2	C15—C16—C8	121.78 (11)
O2—C5—C6	124.51 (13)	O2—C17—H17A	109.5
O2—C5—C4	114.60 (12)	O2—C17—H17B	109.5
C6—C5—C4	120.87 (13)	H17A—C17—H17B	109.5
C5—C6—C7	118.19 (12)	O2—C17—H17C	109.5
C5—C6—H6	120.9	H17A—C17—H17C	109.5
C7—C6—H6	120.9	H17B—C17—H17C	109.5
C6—C7—C2	120.34 (12)	C10—C18—H18A	109.5
C6—C7—C8	133.19 (11)	C10—C18—H18B	109.5
C2—C7—C8	106.47 (11)	H18A—C18—H18B	109.5
C9—C8—C16	119.37 (11)	C10—C18—H18C	109.5
C9—C8—C7	133.94 (11)	H18A—C18—H18C	109.5
C16—C8—C7	106.68 (10)	H18B—C18—H18C	109.5
C10—C9—C8	120.78 (11)	C12—C19—H19A	109.5
C10—C9—H9	119.6	C12—C19—H19B	109.5
C8—C9—H9	119.6	H19A—C19—H19B	109.5
C9—C10—C11	118.11 (11)	C12—C19—H19C	109.5
C9—C10—C18	121.38 (11)	H19A—C19—H19C	109.5
C11—C10—C18	120.51 (11)	H19B—C19—H19C	109.5
O1—C11—C15	120.52 (11)	C12—C20—H20A	109.5
O1—C11—C10	116.22 (11)	C12—C20—H20B	109.5
C15—C11—C10	123.10 (11)	H20A—C20—H20B	109.5
O1—C12—C13	110.56 (11)	C12—C20—H20C	109.5
O1—C12—C19	104.16 (12)	H20A—C20—H20C	109.5
C13—C12—C19	112.32 (13)	H20B—C20—H20C	109.5
O1—C12—C20	108.74 (12)
C16—N1—C2—C3	−179.35 (13)	C9—C10—C11—O1	178.11 (11)
C16—N1—C2—C7	1.02 (15)	C18—C10—C11—O1	−1.39 (17)
N1—C2—C3—C4	179.97 (14)	C9—C10—C11—C15	2.60 (19)
C7—C2—C3—C4	−0.4 (2)	C18—C10—C11—C15	−176.90 (12)
C2—C3—C4—C5	0.0 (2)	C11—O1—C12—C13	36.86 (16)
C17—O2—C5—C6	19.3 (2)	C11—O1—C12—C19	157.72 (12)
C17—O2—C5—C4	−162.32 (14)	C11—O1—C12—C20	−83.65 (15)
C3—C4—C5—O2	−177.91 (13)	O1—C12—C13—C14	−29.5 (2)
C3—C4—C5—C6	0.5 (2)	C19—C12—C13—C14	−145.39 (16)
O2—C5—C6—C7	177.72 (13)	C20—C12—C13—C14	90.42 (18)
C4—C5—C6—C7	−0.5 (2)	C12—C13—C14—C15	6.7 (2)
C5—C6—C7—C2	0.09 (19)	O1—C11—C15—C16	−179.54 (10)
C5—C6—C7—C8	−179.29 (13)	C10—C11—C15—C16	−4.22 (18)
N1—C2—C7—C6	−179.94 (11)	O1—C11—C15—C14	−3.37 (18)
C3—C2—C7—C6	0.4 (2)	C10—C11—C15—C14	171.96 (12)
N1—C2—C7—C8	−0.40 (14)	C13—C14—C15—C16	−172.97 (14)
C3—C2—C7—C8	179.92 (12)	C13—C14—C15—C11	11.2 (2)
C6—C7—C8—C9	0.6 (2)	C2—N1—C16—C15	178.26 (13)
C2—C7—C8—C9	−178.84 (13)	C2—N1—C16—C8	−1.24 (14)
C6—C7—C8—C16	179.10 (13)	C11—C15—C16—N1	−176.68 (12)
C2—C7—C8—C16	−0.34 (13)	C14—C15—C16—N1	7.4 (2)
C16—C8—C9—C10	−1.93 (18)	C11—C15—C16—C8	2.77 (18)
C7—C8—C9—C10	176.42 (12)	C14—C15—C16—C8	−173.14 (12)
C8—C9—C10—C11	0.59 (18)	C9—C8—C16—N1	179.73 (11)
C8—C9—C10—C18	−179.91 (12)	C7—C8—C16—N1	0.97 (14)
C12—O1—C11—C15	−22.17 (17)	C9—C8—C16—C15	0.18 (18)
C12—O1—C11—C10	162.20 (11)	C7—C8—C16—C15	−178.58 (11)

Cg1 is the centroid of the N1/C2/C7/C8/C16 ring and Cg4 is the centroid of the C8–C11/C15/C16 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1i	0.93	2.54	3.333 (2)	143
N1—H1···Cg4ii	0.872 (18)	2.744 (17)	3.528 (2)	149.7 (14)
C17—H17C···Cg1iii	0.96	3.08	3.489 (3)	107
C17—H17C···Cg4iii	0.96	3.00	3.514 (3)	115

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N1/C2/C7/C8/C16 ring and Cg4 is the centroid of the C8–C11/C15/C16 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1i	0.93	2.54	3.333 (2)	143
N1—H1⋯Cg4ii	0.872 (18)	2.744 (17)	3.528 (2)	149.7 (14)
C17—H17C⋯Cg1iii	0.96	3.08	3.489 (3)	107
C17—H17C⋯Cg4iii	0.96	3.00	3.514 (3)	115

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