cis-6-Bromo-4-(1-methyl-1H-indol-3-yl)-10,10a-dihydro-1H,4H-2,9-dioxa-3-aza-benz[f]azulene.

In the title compound, C(20)H(17)BrN(2)O(2), the seven-membered oxepine ring adopts a chair conformation. The indole moiety is essentially planar with a maximum deviation of 0.031 (3)Å. The indole ring system forms a dihedral angle of 21.87 (8)° with the mean plane of the 10-membered heterobicycle. The crystal packing is stabilized by inter-molecular C-H⋯O and C-H⋯π inter-actions.

Related literature

For the chemistry of 4,5-dihydro­isoxazole, see: Caramella & Grunanger (1984 ▶). For the uses of isoxazoline derivatives, see: Ichiba & Scheuer (1993 ▶). For intra­molecular nitrile oxide cyclo­addition (INOC) reactions, see: Scott et al. (2006 ▶); Mukaiyama & Hoshino (1960 ▶). For a related structure, see: Trigunait et al. (2010 ▶). For puckering and asymmetry parameters, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶). For bond-length distortions, see: Allen (1981 ▶).

Experimental

Crystal data

C20H17BrN2O2

M = 397.26

Monoclinic,

a = 12.5772 (4) Å

b = 14.7746 (5) Å

c = 9.2168 (3) Å

β = 97.193 (2)°

V = 1699.22 (10) Å3

Z = 4

Mo Kα radiation

μ = 2.44 mm−1

T = 295 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

21255 measured reflections

4461 independent reflections

2831 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.099

S = 1.00

4461 reflections

227 parameters

H-atom parameters constrained

Δρmax = 0.45 e Å−3

Δρmin = −0.38 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: 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/S1600536811003084/rk2253sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811003084/rk2253Isup2.hkl

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

C20H17BrN2O2	F(000) = 808
Mr = 397.26	Dx = 1.553 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4461 reflections
a = 12.5772 (4) Å	θ = 1.0–28.9°
b = 14.7746 (5) Å	µ = 2.44 mm−1
c = 9.2168 (3) Å	T = 295 K
β = 97.193 (2)°	Block, yellow
V = 1699.22 (10) Å3	0.30 × 0.20 × 0.20 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	2831 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.041
graphite	θmax = 28.9°, θmin = 2.6°
ω scans	h = −16→17
21255 measured reflections	k = −19→20
4461 independent reflections	l = −12→12

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0406P)2 + 0.6061P] where P = (Fo2 + 2Fc2)/3
4461 reflections	(Δ/σ)max = 0.005
227 parameters	Δρmax = 0.45 e Å−3
0 restraints	Δρmin = −0.38 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	0.55355 (16)	0.06019 (14)	0.8437 (2)	0.0372 (5)
C2	0.49922 (18)	0.02980 (16)	0.7116 (2)	0.0488 (6)
H2	0.5295	−0.0140	0.6571	0.059*
C3	0.4004 (2)	0.06538 (19)	0.6630 (3)	0.0590 (7)
H3	0.3635	0.0448	0.5756	0.071*
C4	0.35459 (19)	0.13168 (18)	0.7423 (3)	0.0577 (6)
H4	0.2876	0.1547	0.7065	0.069*
C5	0.40554 (19)	0.16370 (16)	0.8712 (3)	0.0501 (6)
H5	0.3748	0.2084	0.9235	0.060*
C6	0.50518 (17)	0.12714 (14)	0.9219 (2)	0.0403 (5)
C7	0.5531 (2)	0.20897 (19)	1.1594 (3)	0.0710 (8)
H7A	0.5497	0.2692	1.1201	0.107*
H7B	0.6102	0.2053	1.2387	0.107*
H7C	0.4864	0.1945	1.1945	0.107*
C8	0.66164 (18)	0.09158 (15)	1.0478 (2)	0.0432 (5)
H8	0.7191	0.0912	1.1218	0.052*
C9	0.65405 (16)	0.03903 (13)	0.9262 (2)	0.0360 (4)
C10	0.73020 (16)	−0.03183 (13)	0.8837 (2)	0.0361 (5)
H10	0.6881	−0.0875	0.8665	0.043*
C11	0.82340 (16)	−0.05514 (14)	0.9955 (2)	0.0391 (5)
C12	0.9709 (3)	−0.12919 (19)	1.1159 (3)	0.0701 (8)
H12A	0.9722	−0.1753	1.1911	0.084*
H12B	1.0386	−0.1306	1.0759	0.084*
C13	0.8786 (2)	−0.14544 (15)	0.9967 (3)	0.0513 (6)
H13	0.8316	−0.1930	1.0265	0.062*
C14	0.9178 (2)	−0.17035 (18)	0.8540 (3)	0.0606 (7)
H14A	0.9755	−0.1298	0.8368	0.073*
H14B	0.9466	−0.2313	0.8614	0.073*
C15	0.82539 (17)	−0.07968 (15)	0.6713 (2)	0.0428 (5)
C16	0.86662 (18)	−0.06373 (18)	0.5428 (2)	0.0532 (6)
H16	0.8988	−0.1106	0.4971	0.064*
C17	0.86065 (18)	0.0213 (2)	0.4810 (2)	0.0547 (6)
H17	0.8874	0.0322	0.3930	0.066*
C18	0.81440 (17)	0.08935 (17)	0.5523 (2)	0.0456 (5)
C19	0.77092 (16)	0.07430 (14)	0.6800 (2)	0.0375 (5)
H19	0.7387	0.1215	0.7251	0.045*
C20	0.77544 (15)	−0.01140 (14)	0.7409 (2)	0.0351 (4)
N1	0.57283 (15)	0.14517 (12)	1.0459 (2)	0.0453 (4)
N2	0.86495 (15)	−0.00096 (15)	1.0909 (2)	0.0554 (5)
O1	0.95362 (15)	−0.04308 (15)	1.17437 (19)	0.0769 (6)
O2	0.83522 (14)	−0.16586 (11)	0.73157 (18)	0.0571 (4)
Br1	0.80960 (3)	0.20837 (2)	0.47468 (3)	0.07806 (14)

	U11	U22	U33	U12	U13	U23
C1	0.0354 (11)	0.0388 (11)	0.0401 (11)	−0.0033 (9)	0.0158 (9)	0.0016 (9)
C2	0.0451 (13)	0.0560 (14)	0.0472 (12)	−0.0074 (11)	0.0133 (11)	−0.0055 (10)
C3	0.0435 (14)	0.0775 (18)	0.0559 (14)	−0.0078 (13)	0.0055 (11)	−0.0018 (13)
C4	0.0366 (13)	0.0696 (17)	0.0678 (16)	0.0011 (12)	0.0101 (12)	0.0145 (14)
C5	0.0419 (13)	0.0494 (13)	0.0634 (15)	0.0022 (11)	0.0233 (12)	0.0084 (11)
C6	0.0380 (12)	0.0398 (11)	0.0460 (12)	−0.0036 (9)	0.0167 (10)	0.0026 (9)
C7	0.0712 (19)	0.0711 (18)	0.0731 (18)	0.0136 (14)	0.0177 (15)	−0.0307 (14)
C8	0.0414 (12)	0.0468 (12)	0.0428 (11)	0.0006 (10)	0.0108 (9)	−0.0070 (9)
C9	0.0380 (11)	0.0338 (10)	0.0386 (10)	−0.0034 (9)	0.0147 (9)	−0.0006 (8)
C10	0.0404 (11)	0.0326 (10)	0.0373 (10)	−0.0035 (9)	0.0123 (9)	−0.0023 (8)
C11	0.0416 (12)	0.0413 (12)	0.0369 (11)	−0.0009 (9)	0.0155 (9)	0.0031 (9)
C12	0.080 (2)	0.0640 (18)	0.0634 (16)	0.0128 (15)	−0.0033 (15)	0.0193 (14)
C13	0.0583 (15)	0.0387 (12)	0.0571 (14)	0.0024 (11)	0.0079 (12)	0.0104 (10)
C14	0.0653 (17)	0.0479 (14)	0.0683 (16)	0.0204 (13)	0.0070 (14)	−0.0012 (12)
C15	0.0377 (12)	0.0474 (13)	0.0429 (11)	0.0012 (10)	0.0038 (9)	−0.0121 (10)
C16	0.0411 (13)	0.0760 (18)	0.0442 (12)	0.0020 (12)	0.0116 (10)	−0.0231 (12)
C17	0.0385 (13)	0.094 (2)	0.0334 (11)	−0.0071 (13)	0.0114 (9)	−0.0054 (12)
C18	0.0342 (12)	0.0657 (15)	0.0368 (11)	−0.0094 (10)	0.0048 (9)	0.0049 (10)
C19	0.0333 (11)	0.0456 (12)	0.0341 (10)	−0.0025 (9)	0.0065 (8)	−0.0032 (9)
C20	0.0304 (10)	0.0428 (11)	0.0325 (10)	−0.0022 (9)	0.0057 (8)	−0.0069 (8)
N1	0.0453 (11)	0.0444 (10)	0.0488 (10)	0.0039 (8)	0.0158 (9)	−0.0110 (8)
N2	0.0421 (11)	0.0735 (14)	0.0504 (11)	0.0127 (10)	0.0054 (9)	−0.0159 (10)
O1	0.0582 (11)	0.1117 (16)	0.0574 (10)	0.0313 (11)	−0.0067 (9)	−0.0287 (11)
O2	0.0644 (11)	0.0422 (9)	0.0642 (10)	0.0073 (8)	0.0056 (9)	−0.0151 (8)
Br1	0.0801 (2)	0.0842 (2)	0.0702 (2)	−0.01674 (16)	0.01064 (15)	0.03257 (15)

C1—C2	1.394 (3)	C11—N2	1.254 (3)
C1—C6	1.407 (3)	C11—C13	1.503 (3)
C1—C9	1.426 (3)	C12—O1	1.409 (3)
C2—C3	1.371 (3)	C12—C13	1.514 (4)
C2—H2	0.9300	C12—H12A	0.9700
C3—C4	1.390 (4)	C12—H12B	0.9700
C3—H3	0.9300	C13—C14	1.507 (3)
C4—C5	1.362 (4)	C13—H13	0.9800
C4—H4	0.9300	C14—O2	1.436 (3)
C5—C6	1.391 (3)	C14—H14A	0.9700
C5—H5	0.9300	C14—H14B	0.9700
C6—N1	1.363 (3)	C15—C16	1.371 (3)
C7—N1	1.453 (3)	C15—C20	1.388 (3)
C7—H7A	0.9600	C15—O2	1.389 (3)
C7—H7B	0.9600	C16—C17	1.378 (4)
C7—H7C	0.9600	C16—H16	0.9300
C8—C9	1.356 (3)	C17—C18	1.370 (3)
C8—N1	1.367 (3)	C17—H17	0.9300
C8—H8	0.9300	C18—C19	1.377 (3)
C9—C10	1.504 (3)	C18—Br1	1.897 (2)
C10—C11	1.501 (3)	C19—C20	1.383 (3)
C10—C20	1.528 (3)	C19—H19	0.9300
C10—H10	0.9800	N2—O1	1.417 (3)
C2—C1—C6	118.6 (2)	C13—C12—H12A	110.5
C2—C1—C9	134.5 (2)	O1—C12—H12B	110.5
C6—C1—C9	106.97 (18)	C13—C12—H12B	110.5
C3—C2—C1	119.1 (2)	H12A—C12—H12B	108.7
C3—C2—H2	120.4	C11—C13—C14	114.31 (19)
C1—C2—H2	120.4	C11—C13—C12	100.1 (2)
C2—C3—C4	121.1 (2)	C14—C13—C12	111.6 (2)
C2—C3—H3	119.4	C11—C13—H13	110.2
C4—C3—H3	119.4	C14—C13—H13	110.2
C5—C4—C3	121.5 (2)	C12—C13—H13	110.2
C5—C4—H4	119.2	O2—C14—C13	113.0 (2)
C3—C4—H4	119.2	O2—C14—H14A	109.0
C4—C5—C6	117.6 (2)	C13—C14—H14A	109.0
C4—C5—H5	121.2	O2—C14—H14B	109.0
C6—C5—H5	121.2	C13—C14—H14B	109.0
N1—C6—C5	130.4 (2)	H14A—C14—H14B	107.8
N1—C6—C1	107.61 (18)	C16—C15—C20	121.1 (2)
C5—C6—C1	122.0 (2)	C16—C15—O2	118.6 (2)
N1—C7—H7A	109.5	C20—C15—O2	120.29 (19)
N1—C7—H7B	109.5	C15—C16—C17	120.5 (2)
H7A—C7—H7B	109.5	C15—C16—H16	119.8
N1—C7—H7C	109.5	C17—C16—H16	119.8
H7A—C7—H7C	109.5	C18—C17—C16	118.4 (2)
H7B—C7—H7C	109.5	C18—C17—H17	120.8
C9—C8—N1	110.37 (19)	C16—C17—H17	120.8
C9—C8—H8	124.8	C17—C18—C19	122.0 (2)
N1—C8—H8	124.8	C17—C18—Br1	119.66 (16)
C8—C9—C1	106.33 (18)	C19—C18—Br1	118.37 (18)
C8—C9—C10	129.23 (19)	C18—C19—C20	119.6 (2)
C1—C9—C10	124.37 (18)	C18—C19—H19	120.2
C11—C10—C9	116.69 (17)	C20—C19—H19	120.2
C11—C10—C20	107.08 (16)	C19—C20—C15	118.41 (18)
C9—C10—C20	113.88 (16)	C19—C20—C10	121.97 (17)
C11—C10—H10	106.1	C15—C20—C10	119.59 (18)
C9—C10—H10	106.1	C6—N1—C8	108.71 (17)
C20—C10—H10	106.1	C6—N1—C7	125.9 (2)
N2—C11—C10	123.8 (2)	C8—N1—C7	125.4 (2)
N2—C11—C13	114.2 (2)	C11—N2—O1	109.3 (2)
C10—C11—C13	121.93 (19)	C12—O1—N2	109.74 (18)
O1—C12—C13	106.2 (2)	C15—O2—C14	112.10 (18)
O1—C12—H12A	110.5
C6—C1—C2—C3	−0.6 (3)	C12—C13—C14—O2	−166.5 (2)
C9—C1—C2—C3	179.6 (2)	C20—C15—C16—C17	1.0 (3)
C1—C2—C3—C4	0.8 (4)	O2—C15—C16—C17	−178.6 (2)
C2—C3—C4—C5	−0.2 (4)	C15—C16—C17—C18	1.1 (3)
C3—C4—C5—C6	−0.5 (3)	C16—C17—C18—C19	−2.3 (3)
C4—C5—C6—N1	−179.3 (2)	C16—C17—C18—Br1	177.58 (17)
C4—C5—C6—C1	0.7 (3)	C17—C18—C19—C20	1.3 (3)
C2—C1—C6—N1	179.84 (18)	Br1—C18—C19—C20	−178.55 (15)
C9—C1—C6—N1	−0.3 (2)	C18—C19—C20—C15	0.8 (3)
C2—C1—C6—C5	−0.2 (3)	C18—C19—C20—C10	178.98 (18)
C9—C1—C6—C5	179.70 (19)	C16—C15—C20—C19	−1.9 (3)
N1—C8—C9—C1	−0.7 (2)	O2—C15—C20—C19	177.61 (18)
N1—C8—C9—C10	−177.85 (19)	C16—C15—C20—C10	179.84 (19)
C2—C1—C9—C8	−179.5 (2)	O2—C15—C20—C10	−0.6 (3)
C6—C1—C9—C8	0.6 (2)	C11—C10—C20—C19	−113.4 (2)
C2—C1—C9—C10	−2.2 (4)	C9—C10—C20—C19	17.1 (3)
C6—C1—C9—C10	177.92 (17)	C11—C10—C20—C15	64.8 (2)
C8—C9—C10—C11	6.3 (3)	C9—C10—C20—C15	−164.68 (18)
C1—C9—C10—C11	−170.40 (18)	C5—C6—N1—C8	179.9 (2)
C8—C9—C10—C20	−119.3 (2)	C1—C6—N1—C8	−0.1 (2)
C1—C9—C10—C20	64.0 (2)	C5—C6—N1—C7	1.3 (4)
C9—C10—C11—N2	−28.3 (3)	C1—C6—N1—C7	−178.7 (2)
C20—C10—C11—N2	100.7 (2)	C9—C8—N1—C6	0.5 (2)
C9—C10—C11—C13	154.99 (18)	C9—C8—N1—C7	179.1 (2)
C20—C10—C11—C13	−76.1 (2)	C10—C11—N2—O1	−177.52 (18)
N2—C11—C13—C14	−122.5 (2)	C13—C11—N2—O1	−0.6 (3)
C10—C11—C13—C14	54.6 (3)	C13—C12—O1—N2	−6.2 (3)
N2—C11—C13—C12	−3.1 (3)	C11—N2—O1—C12	4.4 (3)
C10—C11—C13—C12	173.93 (19)	C16—C15—O2—C14	103.6 (2)
O1—C12—C13—C11	5.4 (3)	C20—C15—O2—C14	−75.9 (3)
O1—C12—C13—C14	126.8 (2)	C13—C14—O2—C15	87.0 (3)
C11—C13—C14—O2	−53.8 (3)

Cg1and Cg2 are the centroids of the C1–C6 and C15–C20 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···O1i	0.93	2.53	3.329 (3)	144
C3—H3···Cg2ii	0.93	2.79	3.653 (3)	155
C7—H7A···Cg1iii	0.96	2.92	3.427 (3)	114

Table 1

Hydrogen-bond geometry (Å, °)

Cg1and Cg2 are the centroids of the C1–C6 and C15–C20 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯O1i	0.93	2.53	3.329 (3)	144
C3—H3⋯Cg2ii	0.93	2.79	3.653 (3)	155
C7—H7A⋯Cg1iii	0.96	2.92	3.427 (3)	114

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