(3aR*,5R*)-5-(4-Chloro-phen-yl)-1,2,3,3a-tetra-hydro-benzo[e]pyrrolo-[2,1-b][1,3]ox-azepin-10(5H)-one.

The title compound, C(18)H(16)ClNO(2), is the main product of a photoreaction. The two benzene rings make a dihedral angle of 86.40 (2)° with each other. The 1,3-oxazepine C atom to which the 4-chloro-phenyl group is attached and the C atom of the 4-chloro-phenyl group attached to the 1,3-oxazepine ring are chiral C atoms, but the crystal is a racemate in which the enanti-omers are linked by a pair of weak inter-molecular C-H⋯O hydrogen bond, forming an inversion dimer.

Related literature

For general background to asymmetric photochemical reactions, see: Gratzel (2001 ▶); Korzeniewski & Zoladz (2001 ▶); Aubert et al. (2000 ▶). For photo-induced cyclizations, see Griesbeck et al. (2002 ▶); Henz et al. (1995 ▶). For related structures, see: Griesbeck et al. (1997 ▶, 1999 ▶); Basarić et al. (2008 ▶).

Experimental

Crystal data

C18H16ClNO2

M = 313.77

Monoclinic,

a = 8.1764 (6) Å

b = 16.9030 (11) Å

c = 11.1564 (8) Å

β = 98.224 (6)°

V = 1526.02 (19) Å3

Z = 4

Mo Kα radiation

μ = 0.26 mm−1

T = 296 K

0.22 × 0.18 × 0.15 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.676, T max = 1.000

12942 measured reflections

3478 independent reflections

2393 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.181

S = 1.04

3478 reflections

199 parameters

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.37 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2004 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811020265/ff2014sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811020265/ff2014Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811020265/ff2014Isup3.cml

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

C18H16ClNO2	F(000) = 656
Mr = 313.77	Dx = 1.366 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3950 reflections
a = 8.1764 (6) Å	θ = 2.2–27.5°
b = 16.9030 (11) Å	µ = 0.26 mm−1
c = 11.1564 (8) Å	T = 296 K
β = 98.224 (6)°	Prism, colourless
V = 1526.02 (19) Å3	0.22 × 0.18 × 0.15 mm
Z = 4

Bruker APEXII area-detector diffractometer	3478 independent reflections
Radiation source: fine-focus sealed tube	2393 reflections with I > 2σ(I)
graphite	Rint = 0.039
ω scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.676, Tmax = 1.000	k = −21→19
12942 measured reflections	l = −14→14

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.181	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.092P)2] where P = (Fo2 + 2Fc2)/3
3478 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.37 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 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.

	x	y	z	Uiso*/Ueq
Cl1	0.03682 (9)	−0.29821 (4)	−0.05399 (7)	0.0622 (3)
N1	0.4690 (3)	0.10862 (13)	0.34094 (18)	0.0480 (5)
C1	0.5968 (3)	−0.03368 (14)	0.2353 (2)	0.0413 (6)
O1	0.6417 (2)	0.07672 (14)	0.51050 (16)	0.0688 (6)
O2	0.3452 (2)	0.04181 (10)	0.16210 (15)	0.0489 (5)
C2	0.6842 (3)	−0.08243 (15)	0.1681 (2)	0.0499 (6)
H2A	0.6277	−0.1146	0.1084	0.060*
C3	0.8560 (3)	−0.08382 (18)	0.1887 (3)	0.0651 (8)
H3A	0.9132	−0.1165	0.1420	0.078*
C4	0.9415 (3)	−0.03783 (18)	0.2764 (3)	0.0683 (9)
H4A	1.0564	−0.0392	0.2897	0.082*
C5	0.8567 (3)	0.01065 (17)	0.3453 (3)	0.0574 (7)
H5A	0.9148	0.0415	0.4060	0.069*
C6	0.6849 (3)	0.01392 (15)	0.3250 (2)	0.0445 (6)
C7	0.5983 (3)	0.06870 (16)	0.4016 (2)	0.0501 (6)
C8	0.3617 (4)	0.16033 (19)	0.4019 (3)	0.0692 (9)
H8A	0.4206	0.2071	0.4349	0.083*
H8B	0.3182	0.1325	0.4665	0.083*
C9	0.2247 (4)	0.1818 (2)	0.2998 (3)	0.0719 (9)
H9A	0.1359	0.1433	0.2931	0.086*
H9B	0.1801	0.2338	0.3121	0.086*
C10	0.3120 (4)	0.18035 (17)	0.1886 (3)	0.0631 (8)
H10A	0.2336	0.1728	0.1157	0.076*
H10B	0.3719	0.2293	0.1814	0.076*
C11	0.4297 (3)	0.11097 (15)	0.2095 (2)	0.0461 (6)
H11A	0.5292	0.1201	0.1718	0.055*
C12	0.4073 (3)	−0.03092 (14)	0.2181 (2)	0.0413 (5)
H12A	0.3737	−0.0326	0.2989	0.050*
C13	0.3216 (3)	−0.09805 (14)	0.1466 (2)	0.0415 (5)
C14	0.2537 (3)	−0.08971 (16)	0.0260 (2)	0.0541 (7)
H14A	0.2660	−0.0423	−0.0140	0.065*
C15	0.1679 (3)	−0.15155 (16)	−0.0348 (2)	0.0545 (7)
H15A	0.1214	−0.1451	−0.1153	0.065*
C16	0.1508 (3)	−0.22169 (14)	0.0218 (2)	0.0456 (6)
C17	0.2183 (3)	−0.23170 (16)	0.1421 (2)	0.0500 (6)
H17A	0.2075	−0.2797	0.1809	0.060*
C18	0.3018 (3)	−0.16948 (16)	0.2039 (2)	0.0488 (6)
H18A	0.3454	−0.1756	0.2850	0.059*

	U11	U22	U33	U12	U13	U23
Cl1	0.0607 (4)	0.0489 (4)	0.0745 (5)	−0.0033 (3)	0.0014 (4)	−0.0117 (3)
N1	0.0496 (12)	0.0520 (12)	0.0433 (11)	−0.0005 (10)	0.0095 (9)	−0.0059 (9)
C1	0.0387 (12)	0.0429 (13)	0.0426 (13)	0.0014 (10)	0.0065 (10)	0.0107 (10)
O1	0.0684 (13)	0.0907 (16)	0.0452 (11)	−0.0246 (11)	0.0010 (9)	−0.0051 (10)
O2	0.0487 (10)	0.0453 (10)	0.0494 (10)	0.0068 (8)	−0.0042 (8)	−0.0017 (8)
C2	0.0471 (13)	0.0444 (13)	0.0594 (16)	0.0057 (11)	0.0119 (12)	0.0081 (11)
C3	0.0515 (15)	0.0518 (16)	0.096 (2)	0.0119 (13)	0.0243 (16)	0.0092 (16)
C4	0.0383 (13)	0.0613 (18)	0.104 (3)	0.0062 (13)	0.0070 (15)	0.0223 (17)
C5	0.0412 (13)	0.0593 (17)	0.0688 (18)	−0.0024 (12)	−0.0019 (13)	0.0132 (14)
C6	0.0417 (12)	0.0508 (14)	0.0398 (13)	−0.0027 (11)	0.0012 (10)	0.0109 (10)
C7	0.0473 (13)	0.0552 (16)	0.0476 (14)	−0.0167 (12)	0.0064 (12)	−0.0008 (12)
C8	0.0699 (19)	0.068 (2)	0.074 (2)	−0.0016 (16)	0.0257 (16)	−0.0235 (16)
C9	0.0612 (17)	0.0620 (19)	0.095 (2)	0.0130 (15)	0.0202 (17)	−0.0128 (17)
C10	0.0603 (17)	0.0490 (15)	0.079 (2)	0.0093 (13)	0.0079 (15)	0.0013 (14)
C11	0.0473 (13)	0.0464 (14)	0.0444 (14)	0.0010 (11)	0.0057 (11)	−0.0002 (11)
C12	0.0390 (11)	0.0472 (13)	0.0383 (12)	0.0004 (10)	0.0070 (10)	0.0011 (10)
C13	0.0373 (11)	0.0466 (13)	0.0408 (12)	0.0008 (10)	0.0066 (10)	0.0007 (10)
C14	0.0646 (16)	0.0526 (15)	0.0444 (14)	−0.0120 (13)	0.0053 (13)	0.0066 (11)
C15	0.0674 (17)	0.0589 (17)	0.0353 (13)	−0.0085 (13)	0.0003 (12)	−0.0006 (11)
C16	0.0412 (12)	0.0443 (13)	0.0514 (14)	0.0013 (10)	0.0066 (11)	−0.0060 (11)
C17	0.0543 (14)	0.0441 (13)	0.0507 (14)	0.0039 (12)	0.0042 (12)	0.0053 (11)
C18	0.0464 (13)	0.0511 (14)	0.0471 (14)	0.0048 (11)	0.0000 (11)	0.0055 (11)

Cl1—C16	1.741 (2)	C8—H8B	0.9700
N1—C7	1.351 (3)	C9—C10	1.517 (4)
N1—C11	1.456 (3)	C9—H9A	0.9700
N1—C8	1.472 (3)	C9—H9B	0.9700
C1—C2	1.381 (4)	C10—C11	1.514 (4)
C1—C6	1.400 (3)	C10—H10A	0.9700
C1—C12	1.534 (3)	C10—H10B	0.9700
O1—C7	1.223 (3)	C11—H11A	0.9800
O2—C11	1.421 (3)	C12—C13	1.502 (3)
O2—C12	1.438 (3)	C12—H12A	0.9800
C2—C3	1.390 (3)	C13—C18	1.386 (3)
C2—H2A	0.9300	C13—C14	1.387 (3)
C3—C4	1.362 (4)	C14—C15	1.382 (3)
C3—H3A	0.9300	C14—H14A	0.9300
C4—C5	1.377 (4)	C15—C16	1.360 (4)
C4—H4A	0.9300	C15—H15A	0.9300
C5—C6	1.392 (3)	C16—C17	1.386 (3)
C5—H5A	0.9300	C17—C18	1.383 (4)
C6—C7	1.505 (4)	C17—H17A	0.9300
C8—C9	1.523 (4)	C18—H18A	0.9300
C8—H8A	0.9700
C7—N1—C11	124.2 (2)	C11—C10—C9	104.4 (2)
C7—N1—C8	122.7 (2)	C11—C10—H10A	110.9
C11—N1—C8	112.9 (2)	C9—C10—H10A	110.9
C2—C1—C6	118.5 (2)	C11—C10—H10B	110.9
C2—C1—C12	122.8 (2)	C9—C10—H10B	110.9
C6—C1—C12	118.6 (2)	H10A—C10—H10B	108.9
C11—O2—C12	114.74 (15)	O2—C11—N1	112.2 (2)
C1—C2—C3	120.6 (3)	O2—C11—C10	108.37 (19)
C1—C2—H2A	119.7	N1—C11—C10	102.7 (2)
C3—C2—H2A	119.7	O2—C11—H11A	111.1
C4—C3—C2	120.8 (3)	N1—C11—H11A	111.1
C4—C3—H3A	119.6	C10—C11—H11A	111.1
C2—C3—H3A	119.6	O2—C12—C13	107.83 (17)
C3—C4—C5	119.5 (3)	O2—C12—C1	111.60 (19)
C3—C4—H4A	120.2	C13—C12—C1	115.5 (2)
C5—C4—H4A	120.2	O2—C12—H12A	107.2
C4—C5—C6	120.7 (3)	C13—C12—H12A	107.2
C4—C5—H5A	119.7	C1—C12—H12A	107.2
C6—C5—H5A	119.7	C18—C13—C14	118.6 (2)
C5—C6—C1	119.9 (3)	C18—C13—C12	119.3 (2)
C5—C6—C7	118.6 (2)	C14—C13—C12	122.0 (2)
C1—C6—C7	121.6 (2)	C15—C14—C13	120.3 (2)
O1—C7—N1	122.5 (3)	C15—C14—H14A	119.9
O1—C7—C6	122.6 (2)	C13—C14—H14A	119.9
N1—C7—C6	114.9 (2)	C16—C15—C14	120.7 (2)
N1—C8—C9	102.7 (2)	C16—C15—H15A	119.7
N1—C8—H8A	111.2	C14—C15—H15A	119.7
C9—C8—H8A	111.2	C15—C16—C17	120.2 (2)
N1—C8—H8B	111.2	C15—C16—Cl1	120.34 (19)
C9—C8—H8B	111.2	C17—C16—Cl1	119.4 (2)
H8A—C8—H8B	109.1	C18—C17—C16	119.3 (2)
C10—C9—C8	103.0 (2)	C18—C17—H17A	120.4
C10—C9—H9A	111.2	C16—C17—H17A	120.4
C8—C9—H9A	111.2	C17—C18—C13	121.0 (2)
C10—C9—H9B	111.2	C17—C18—H18A	119.5
C8—C9—H9B	111.2	C13—C18—H18A	119.5
H9A—C9—H9B	109.1

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···O1i	0.98	2.27	3.206 (3)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯O1i	0.98	2.27	3.206 (3)	159

Symmetry code: (i) .