7-Bromo-4b-methyl-7,8-dihydro-4bH-9-thia-8a-aza-fluorene 9,9-dioxide.

The title compound, C(12)H(12)BrNO(2)S, was isolated after direct irradiation (hν 350 nm, hexa-ne) of a mixture of stereoisomeric sulfonamides containing a vicinal dibromide and a conjugated diene. This product is one of a group of substrates that has contributed to our understanding of the photoreactivity patterns of non-bridged sulfonamides. The crystal structure was determined from a non-merohedrally twinned data set, where the twin law corresponded to a 180° rotation about the a* axis. The minor twin component refined to a value of 0.176 (3). The conformation of the mol-ecule is planar at one end, as the benzene ring and the adjacent fused five-membered ring are coplanar, and U-shaped at the other end, where the five-membered ring is fused to the heterocyclic six-membered ring containing an allyl bromide group.

Related literature

For related chemistry, see: Dura & Paquette (2006 ▶); Paquette et al. (2004 ▶, 2006 ▶). For related literature, see: Cooper et al. (2002 ▶).

Experimental

Crystal data

C12H12BrNO2S

M = 314.2

Monoclinic,

a = 14.3970 (3) Å

b = 7.8912 (1) Å

c = 11.4652 (2) Å

β = 103.009 (1)°

V = 1269.13 (4) Å3

Z = 4

Mo Kα radiation

μ = 3.39 mm−1

T = 293 (2) K

0.38 × 0.27 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T min = 0.650, T max = 0.873

18122 measured reflections

2835 independent reflections

2401 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.115

S = 1.49

1509 reflections

156 parameters

H-atom parameters constrained

Δρmax = 0.62 e Å−3

Δρmin = −0.29 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808017972/rt2018sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808017972/rt2018Isup2.hkl

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

C12H12Br1N1O2S1	F000 = 632
Mr = 314.2	Dx = 1.644 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2393 reflections
a = 14.3970 (3) Å	θ = 2.0–25.0º
b = 7.8912 (1) Å	µ = 3.39 mm−1
c = 11.4652 (2) Å	T = 293 (2) K
β = 103.009 (1)º	Plate, colorless
V = 1269.13 (4) Å3	0.38 × 0.27 × 0.04 mm
Z = 4

Nonius KappaCCD diffractometer	2835 independent reflections
Monochromator: graphite	2401 reflections with I > 2σ(I)
Detector resolution: 9 pixels mm-1	Rint = 0.055
T = 293(2) K	θmax = 25.0º
φ and ω scans	θmin = 2.9º
Absorption correction: multi-scan(SCALEPACK; Otwinowski & Minor, 1997)	h = −17→16
Tmin = 0.650, Tmax = 0.873	k = −9→9
18122 measured reflections	l = −13→13

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044	H-atom parameters constrained
wR(F2) = 0.115	w = 1/[σ2(Fo2) + (0.0519P)2 + 1.4699P] where P = (Fo2 + 2Fc2)/3
S = 1.49	(Δ/σ)max = 0.001
1509 reflections	Δρmax = 0.62 e Å−3
156 parameters	Δρmin = −0.29 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Experimental. Examination of the diffraction pattern on a Nonius Kappa CCD diffractometer indicated a monoclinic crystal system. All work was done at room temperature. The data collection strategy was set up to measure a quadrant of reciprocal space with a redundancy factor of 3.7, which means that 90% of the reflections were measured at least 3.7 times. Phi and omega scans with a frame width of 1.0 degree were used for data collection. Data integration was done with DENZO (Otwinowski & Minor, 1997) and scaling and merging of the data was done with SCALEPACK (Otwinowski & Minor, 1997).Structure solution was done by a combination of the Patterson method and the direct methods procedure in SHELXS97 (Sheldrick, 2008). Full-matrix least-squares refinements based on F2 were performed in SHELXL97 (Sheldrick, 2008), as incorporated in the WinGX package (Farrugia, 1999).

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. For the methyl group, the hydrogen atoms were added at calculated positions using a riding model with C—H=0.96 Å and U(H)=1.5*Ueq(bonded carbon atom). The torsion angle, which defines the orientation of the methyl group about the C—C bond, was refined. The remaining hydrogen atoms were included in the model at calculated positions using a riding model with a range of C—H distances from 0.93 to 0.98 Å and U(H)=1.2*Ueq(bonded carbon atom).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	0.5240 (3)	0.5539 (6)	0.6801 (5)	0.0531 (12)
H1	0.5027	0.4792	0.7312	0.064*
C2	0.4619 (4)	0.6615 (7)	0.6053 (6)	0.0591 (14)
H2	0.3973	0.6590	0.6052	0.071*
C3	0.4949 (4)	0.7726 (6)	0.5310 (5)	0.0605 (14)
H3	0.4518	0.8430	0.4806	0.073*
C4	0.5905 (4)	0.7819 (6)	0.5296 (5)	0.0528 (12)
H4	0.6120	0.8597	0.4807	0.063*
C4A	0.6539 (3)	0.6727 (5)	0.6026 (4)	0.0419 (11)
C4B	0.7600 (3)	0.6587 (6)	0.6089 (4)	0.0431 (11)
C5	0.7758 (3)	0.5980 (6)	0.4897 (4)	0.0465 (11)
H5	0.7546	0.6673	0.4234	0.056*
C6	0.8171 (3)	0.4552 (6)	0.4730 (5)	0.0522 (12)
H6	0.8219	0.4270	0.3958	0.063*
C7	0.8568 (3)	0.3362 (6)	0.5723 (5)	0.0509 (12)
H7	0.8103	0.2461	0.5740	0.061*
C8	0.8773 (3)	0.4279 (6)	0.6908 (5)	0.0494 (12)
H8A	0.8925	0.3461	0.7554	0.059*
H8B	0.9321	0.5013	0.6960	0.059*
N8A	0.7945 (3)	0.5296 (5)	0.7036 (3)	0.0438 (9)
C9A	0.6193 (3)	0.5621 (5)	0.6755 (4)	0.0445 (11)
C10	0.8122 (4)	0.8269 (6)	0.6448 (5)	0.0585 (14)
H10A	0.7957	0.8700	0.7158	0.088*
H10B	0.7939	0.9074	0.5810	0.088*
H10C	0.8798	0.8085	0.6601	0.088*
O1	0.6992 (3)	0.2591 (4)	0.7125 (3)	0.0559 (9)
O2	0.7235 (3)	0.4530 (5)	0.8805 (3)	0.0643 (10)
S9	0.70986 (9)	0.43152 (14)	0.75307 (11)	0.0450 (3)
Br	0.97557 (5)	0.23461 (9)	0.54940 (6)	0.0811 (3)

	U11	U22	U33	U12	U13	U23
C1	0.055 (3)	0.050 (3)	0.061 (3)	−0.002 (2)	0.027 (3)	−0.008 (2)
C2	0.048 (3)	0.053 (3)	0.080 (4)	0.004 (2)	0.023 (3)	−0.015 (3)
C3	0.062 (4)	0.049 (3)	0.069 (3)	0.017 (2)	0.010 (3)	−0.008 (3)
C4	0.065 (4)	0.040 (2)	0.055 (3)	0.006 (2)	0.017 (2)	0.002 (2)
C4A	0.054 (3)	0.034 (2)	0.041 (3)	0.000 (2)	0.017 (2)	−0.0063 (19)
C4B	0.052 (3)	0.039 (2)	0.040 (3)	−0.001 (2)	0.016 (2)	0.001 (2)
C5	0.052 (3)	0.052 (3)	0.039 (3)	0.000 (2)	0.016 (2)	0.004 (2)
C6	0.054 (3)	0.060 (3)	0.045 (3)	−0.003 (2)	0.015 (2)	−0.008 (2)
C7	0.050 (3)	0.046 (3)	0.062 (3)	0.001 (2)	0.024 (2)	−0.001 (2)
C8	0.042 (3)	0.053 (3)	0.052 (3)	0.001 (2)	0.008 (2)	0.007 (2)
N8A	0.047 (2)	0.045 (2)	0.041 (2)	−0.0008 (17)	0.0129 (18)	0.0024 (17)
C9A	0.051 (3)	0.041 (2)	0.044 (3)	0.001 (2)	0.017 (2)	−0.004 (2)
C10	0.069 (4)	0.043 (3)	0.063 (4)	−0.012 (3)	0.014 (3)	−0.004 (2)
O1	0.063 (2)	0.0424 (19)	0.066 (2)	0.0003 (15)	0.0238 (16)	0.0028 (18)
O2	0.079 (3)	0.080 (3)	0.038 (2)	0.003 (2)	0.0223 (18)	0.0037 (17)
S9	0.0546 (7)	0.0438 (6)	0.0403 (7)	0.0009 (5)	0.0187 (5)	0.0036 (5)
Br	0.0675 (5)	0.0895 (5)	0.0925 (5)	0.0267 (3)	0.0314 (3)	−0.0027 (4)

C1—C2	1.382 (8)	C6—C7	1.487 (7)
C1—C9A	1.387 (7)	C6—H6	0.9300
C1—H1	0.9300	C7—C8	1.508 (7)
C2—C3	1.380 (8)	C7—Br	1.959 (5)
C2—H2	0.9300	C7—H7	0.9800
C3—C4	1.382 (8)	C8—N8A	1.472 (6)
C3—H3	0.9300	C8—H8A	0.9700
C4—C4A	1.390 (7)	C8—H8B	0.9700
C4—H4	0.9300	N8A—S9	1.648 (4)
C4A—C9A	1.377 (6)	C9A—S9	1.741 (5)
C4A—C4B	1.517 (6)	C10—H10A	0.9600
C4B—N8A	1.490 (6)	C10—H10B	0.9600
C4B—C5	1.513 (7)	C10—H10C	0.9600
C4B—C10	1.535 (7)	O1—S9	1.435 (3)
C5—C6	1.308 (7)	O2—S9	1.440 (4)
C5—H5	0.9300
C2—C1—C9A	117.1 (5)	C8—C7—Br	108.5 (3)
C2—C1—H1	121.5	C6—C7—H7	109.1
C9A—C1—H1	121.5	C8—C7—H7	109.1
C3—C2—C1	120.6 (5)	Br—C7—H7	109.1
C3—C2—H2	119.7	N8A—C8—C7	110.7 (4)
C1—C2—H2	119.7	N8A—C8—H8A	109.5
C2—C3—C4	121.5 (5)	C7—C8—H8A	109.5
C2—C3—H3	119.2	N8A—C8—H8B	109.5
C4—C3—H3	119.2	C7—C8—H8B	109.5
C3—C4—C4A	118.8 (5)	H8A—C8—H8B	108.1
C3—C4—H4	120.6	C8—N8A—C4B	116.4 (4)
C4A—C4—H4	120.6	C8—N8A—S9	117.2 (3)
C9A—C4A—C4	118.7 (5)	C4B—N8A—S9	114.9 (3)
C9A—C4A—C4B	115.0 (4)	C4A—C9A—C1	123.3 (5)
C4—C4A—C4B	126.3 (4)	C4A—C9A—S9	110.7 (4)
N8A—C4B—C5	110.4 (4)	C1—C9A—S9	125.9 (4)
N8A—C4B—C4A	104.5 (4)	C4B—C10—H10A	109.5
C5—C4B—C4A	109.6 (4)	C4B—C10—H10B	109.5
N8A—C4B—C10	109.4 (4)	H10A—C10—H10B	109.5
C5—C4B—C10	110.6 (4)	C4B—C10—H10C	109.5
C4A—C4B—C10	112.1 (4)	H10A—C10—H10C	109.5
C6—C5—C4B	124.8 (5)	H10B—C10—H10C	109.5
C6—C5—H5	117.6	O1—S9—O2	114.9 (2)
C4B—C5—H5	117.6	O1—S9—N8A	111.5 (2)
C5—C6—C7	122.7 (5)	O2—S9—N8A	110.6 (2)
C5—C6—H6	118.6	O1—S9—C9A	112.5 (2)
C7—C6—H6	118.6	O2—S9—C9A	111.4 (2)
C6—C7—C8	110.5 (4)	N8A—S9—C9A	94.2 (2)
C6—C7—Br	110.6 (3)
C9A—C1—C2—C3	−0.7 (8)	C10—C4B—N8A—C8	−89.4 (5)
C1—C2—C3—C4	−0.8 (8)	C5—C4B—N8A—S9	−109.8 (4)
C2—C3—C4—C4A	1.9 (7)	C4A—C4B—N8A—S9	7.9 (4)
C3—C4—C4A—C9A	−1.4 (7)	C10—C4B—N8A—S9	128.2 (4)
C3—C4—C4A—C4B	177.0 (4)	C4—C4A—C9A—C1	−0.1 (7)
C9A—C4A—C4B—N8A	−3.8 (5)	C4B—C4A—C9A—C1	−178.7 (4)
C4—C4A—C4B—N8A	177.8 (4)	C4—C4A—C9A—S9	177.2 (3)
C9A—C4A—C4B—C5	114.5 (4)	C4B—C4A—C9A—S9	−1.4 (5)
C4—C4A—C4B—C5	−63.9 (6)	C2—C1—C9A—C4A	1.2 (7)
C9A—C4A—C4B—C10	−122.3 (5)	C2—C1—C9A—S9	−175.7 (4)
C4—C4A—C4B—C10	59.3 (6)	C8—N8A—S9—O1	−33.8 (4)
N8A—C4B—C5—C6	−2.3 (7)	C4B—N8A—S9—O1	108.2 (3)
C4A—C4B—C5—C6	−117.0 (5)	C8—N8A—S9—O2	95.3 (4)
C10—C4B—C5—C6	118.9 (5)	C4B—N8A—S9—O2	−122.7 (3)
C4B—C5—C6—C7	−2.0 (8)	C8—N8A—S9—C9A	−150.0 (3)
C5—C6—C7—C8	−21.9 (7)	C4B—N8A—S9—C9A	−8.0 (3)
C5—C6—C7—Br	−142.1 (4)	C4A—C9A—S9—O1	−110.0 (3)
C6—C7—C8—N8A	49.3 (5)	C1—C9A—S9—O1	67.2 (5)
Br—C7—C8—N8A	170.7 (3)	C4A—C9A—S9—O2	119.3 (4)
C7—C8—N8A—C4B	−57.5 (5)	C1—C9A—S9—O2	−63.5 (5)
C7—C8—N8A—S9	84.0 (4)	C4A—C9A—S9—N8A	5.3 (4)
C5—C4B—N8A—C8	32.5 (5)	C1—C9A—S9—N8A	−177.5 (4)
C4A—C4B—N8A—C8	150.3 (4)