7-Bromo-3,3-dibutyl-8-meth-oxy-2,3-di-hydro-1,5-benzothia-zepin-4(5H)-one.

In the title compound C18H26BrNO2S, the thia-zepine ring adopts a boat conformation. The dihedral angle between the mean planes through the benzene ring and the four C atoms making up the basal plane of the boat is 35.8 (2)°. In the crystal, inversion dimers linked by pairs of N-H⋯O hydrogen bonds generate R 2 (2)(8) loops.

Related literature

For reference bond lengths, see: Allen et al. (1987 ▶). For background to the uses of this class of compounds, see: Fedi et al. (2008 ▶); Ganesh et al. (2011 ▶); Riedel et al. (2007 ▶).

Experimental

Crystal data

C18H26BrNO2S

M = 400.30

Monoclinic,

a = 7.7844 (18) Å

b = 11.251 (2) Å

c = 22.039 (6) Å

β = 98.199 (8)°

V = 1910.5 (8) Å3

Z = 4

Mo Kα radiation

μ = 2.27 mm−1

T = 100 K

0.32 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer

16056 measured reflections

4662 independent reflections

2750 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.141

S = 1.03

4662 reflections

212 parameters

H-atom parameters constrained

Δρmax = 0.63 e Å−3

Δρmin = −0.49 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: Mercury.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813013238/hb7081sup1.cif

Structure factors: contains datablock(s) mm. DOI: 10.1107/S1600536813013238/hb7081Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813013238/hb7081Isup3.cml

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

C18H26BrNO2S	F(000) = 832
Mr = 400.30	Dx = 1.392 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4662 reflections
a = 7.7844 (18) Å	θ = 2.0–28.3°
b = 11.251 (2) Å	µ = 2.27 mm−1
c = 22.039 (6) Å	T = 100 K
β = 98.199 (8)°	Block, light brown
V = 1910.5 (8) Å3	0.32 × 0.20 × 0.20 mm
Z = 4

Oxford Diffraction Xcalibur Eos diffractometer	2750 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.054
Graphite monochromator	θmax = 28.3°, θmin = 2.0°
Detector resolution: 16.0839 pixels mm-1	h = −10→8
ω scans	k = −14→9
16056 measured reflections	l = −29→29
4662 independent reflections

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.1275P)2 + 0.4493P] where P = (Fo2 + 2Fc2)/3
4662 reflections	(Δ/σ)max = 0.001
212 parameters	Δρmax = 0.63 e Å−3
0 restraints	Δρmin = −0.49 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > 2sigma(F2) is used only for calculating -R-factor-obs 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
Br9	0.72841 (5)	0.01588 (4)	0.86915 (2)	0.0731 (2)
S10	0.09376 (11)	0.21269 (7)	0.99530 (4)	0.0494 (3)
O2	0.4327 (3)	−0.12202 (18)	0.90398 (11)	0.0548 (8)
O15	0.2816 (3)	0.53731 (17)	0.97428 (10)	0.0420 (7)
N14	0.3916 (3)	0.35886 (16)	0.95950 (10)	0.0418 (8)
C1	0.3047 (3)	−0.20519 (16)	0.91627 (10)	0.0621 (15)
C3	0.4122 (4)	−0.0060 (2)	0.91890 (15)	0.0399 (10)
C4	0.2747 (4)	0.0385 (3)	0.94491 (15)	0.0412 (10)
C5	0.2640 (4)	0.1590 (2)	0.95831 (14)	0.0383 (10)
C6	0.3919 (3)	0.2370 (2)	0.94450 (14)	0.0377 (9)
C7	0.5283 (4)	0.1922 (3)	0.91780 (15)	0.0424 (10)
C8	0.5387 (4)	0.0733 (3)	0.90492 (15)	0.0435 (10)
C11	−0.0156 (4)	0.3122 (3)	0.93772 (15)	0.0460 (10)
C12	0.0909 (4)	0.4072 (3)	0.90861 (14)	0.0386 (9)
C13	0.2596 (3)	0.4382 (2)	0.95076 (14)	0.0353 (9)
C16	−0.0182 (4)	0.5206 (3)	0.89941 (17)	0.0481 (11)
C17	−0.1953 (5)	0.5099 (3)	0.8591 (2)	0.0743 (16)
C18	−0.2889 (6)	0.6281 (5)	0.8496 (2)	0.0915 (19)
C19	−0.2269 (11)	0.7005 (6)	0.8047 (4)	0.165 (4)
C20	0.1333 (4)	0.3605 (3)	0.84640 (14)	0.0467 (11)
C21	0.2456 (6)	0.4427 (4)	0.81384 (18)	0.0743 (16)
C22	0.2854 (7)	0.3940 (6)	0.7533 (2)	0.105 (2)
C23	0.3966 (11)	0.4756 (7)	0.7214 (3)	0.165 (4)
H1A	0.30480	−0.21090	0.95970	0.0940*
H1B	0.33020	−0.28160	0.90040	0.0940*
H1C	0.19260	−0.17920	0.89700	0.0940*
H4	0.18770	−0.01270	0.95360	0.0490*
H7	0.61460	0.24340	0.90840	0.0510*
H11A	−0.07390	0.26350	0.90470	0.0550*
H11B	−0.10520	0.35340	0.95590	0.076 (12)*
H14	0.48930	0.38680	0.97670	0.061 (10)*
H16A	0.04900	0.58050	0.88150	0.0580*
H16B	−0.03720	0.54940	0.93940	0.053 (10)*
H17A	−0.17880	0.47760	0.81960	0.0890*
H17B	−0.26710	0.45470	0.87810	0.0890*
H18A	−0.41170	0.61340	0.83740	0.1100*
H18B	−0.27580	0.67080	0.88820	0.1100*
H19A	−0.12380	0.74130	0.82270	0.2470*
H19B	−0.31420	0.75760	0.78950	0.2470*
H19C	−0.20070	0.65160	0.77150	0.2470*
H20A	0.19210	0.28460	0.85320	0.0560*
H20B	0.02520	0.34660	0.81960	0.0560*
H21A	0.18690	0.51850	0.80660	0.0890*
H21B	0.35400	0.45680	0.84050	0.0890*
H22A	0.34410	0.31820	0.76050	0.1260*
H22B	0.17710	0.38000	0.72660	0.1260*
H23A	0.32730	0.54030	0.70310	0.2480*
H23B	0.44400	0.43230	0.69000	0.2480*
H23C	0.48940	0.50610	0.75050	0.2480*

	U11	U22	U33	U12	U13	U23
Br9	0.0585 (3)	0.0543 (3)	0.1145 (4)	0.0039 (2)	0.0399 (2)	−0.0172 (2)
S10	0.0463 (5)	0.0452 (5)	0.0608 (6)	−0.0023 (3)	0.0220 (4)	−0.0027 (4)
O2	0.0634 (15)	0.0289 (11)	0.0748 (16)	−0.0011 (10)	0.0188 (12)	−0.0065 (11)
O15	0.0329 (11)	0.0317 (11)	0.0600 (14)	−0.0040 (8)	0.0020 (10)	−0.0114 (10)
N14	0.0289 (13)	0.0310 (13)	0.0642 (17)	−0.0052 (10)	0.0019 (12)	−0.0106 (12)
C1	0.077 (3)	0.0328 (18)	0.076 (3)	−0.0101 (17)	0.009 (2)	−0.0023 (17)
C3	0.0439 (17)	0.0286 (15)	0.0460 (19)	−0.0026 (12)	0.0022 (14)	−0.0037 (13)
C4	0.0390 (16)	0.0333 (16)	0.052 (2)	−0.0074 (12)	0.0092 (14)	−0.0011 (14)
C5	0.0352 (16)	0.0348 (16)	0.0456 (18)	−0.0019 (12)	0.0082 (13)	−0.0042 (13)
C6	0.0296 (14)	0.0308 (15)	0.0513 (19)	−0.0023 (11)	0.0010 (13)	−0.0054 (13)
C7	0.0292 (15)	0.0367 (16)	0.062 (2)	−0.0051 (12)	0.0090 (14)	−0.0041 (15)
C8	0.0360 (16)	0.0391 (17)	0.057 (2)	0.0014 (13)	0.0125 (14)	−0.0067 (15)
C11	0.0302 (15)	0.0442 (17)	0.064 (2)	−0.0063 (13)	0.0080 (15)	−0.0109 (16)
C12	0.0308 (15)	0.0375 (16)	0.0469 (18)	−0.0047 (12)	0.0033 (13)	−0.0078 (14)
C13	0.0297 (14)	0.0309 (15)	0.0464 (18)	−0.0038 (11)	0.0097 (13)	−0.0034 (13)
C16	0.0361 (17)	0.0452 (18)	0.061 (2)	−0.0002 (13)	−0.0003 (16)	−0.0098 (16)
C17	0.050 (2)	0.064 (3)	0.099 (3)	0.0067 (18)	−0.023 (2)	−0.008 (2)
C18	0.072 (3)	0.098 (4)	0.093 (3)	0.040 (3)	−0.028 (3)	−0.029 (3)
C19	0.200 (8)	0.089 (4)	0.193 (8)	0.039 (5)	−0.013 (7)	0.019 (5)
C20	0.0398 (17)	0.0490 (19)	0.050 (2)	−0.0056 (14)	0.0020 (14)	−0.0106 (15)
C21	0.083 (3)	0.088 (3)	0.055 (2)	−0.022 (2)	0.021 (2)	−0.006 (2)
C22	0.108 (4)	0.159 (5)	0.052 (3)	−0.046 (4)	0.026 (3)	−0.017 (3)
C23	0.151 (7)	0.270 (10)	0.081 (4)	−0.078 (6)	0.037 (4)	−0.028 (5)

Br9—C8	1.885 (3)	C1—H1A	0.9600
S10—C5	1.759 (3)	C1—H1B	0.9600
S10—C11	1.811 (3)	C1—H1C	0.9600
O2—C1	1.421 (3)	C4—H4	0.9300
O2—C3	1.361 (3)	C7—H7	0.9300
O15—C13	1.231 (3)	C11—H11A	0.9700
N14—C6	1.410 (3)	C11—H11B	0.9700
N14—C13	1.354 (3)	C16—H16A	0.9700
N14—H14	0.8600	C16—H16B	0.9700
C3—C4	1.378 (4)	C17—H17A	0.9700
C3—C8	1.395 (4)	C17—H17B	0.9700
C4—C5	1.393 (4)	C18—H18A	0.9700
C5—C6	1.393 (4)	C18—H18B	0.9700
C6—C7	1.381 (4)	C19—H19A	0.9600
C7—C8	1.372 (5)	C19—H19B	0.9600
C11—C12	1.547 (5)	C19—H19C	0.9600
C12—C13	1.537 (4)	C20—H20A	0.9700
C12—C16	1.530 (5)	C20—H20B	0.9700
C12—C20	1.547 (4)	C21—H21A	0.9700
C16—C17	1.535 (5)	C21—H21B	0.9700
C17—C18	1.517 (6)	C22—H22A	0.9700
C18—C19	1.418 (9)	C22—H22B	0.9700
C20—C21	1.521 (6)	C23—H23A	0.9600
C21—C22	1.515 (6)	C23—H23B	0.9600
C22—C23	1.503 (10)	C23—H23C	0.9600
C5—S10—C11	101.39 (14)	S10—C11—H11B	107.00
C1—O2—C3	118.4 (2)	C12—C11—H11A	107.00
C6—N14—C13	129.4 (2)	C12—C11—H11B	107.00
C13—N14—H14	115.00	H11A—C11—H11B	107.00
C6—N14—H14	115.00	C12—C16—H16A	108.00
C4—C3—C8	118.3 (3)	C12—C16—H16B	108.00
O2—C3—C4	125.0 (3)	C17—C16—H16A	108.00
O2—C3—C8	116.7 (3)	C17—C16—H16B	108.00
C3—C4—C5	121.0 (3)	H16A—C16—H16B	107.00
S10—C5—C4	120.3 (2)	C16—C17—H17A	109.00
S10—C5—C6	119.61 (18)	C16—C17—H17B	109.00
C4—C5—C6	120.1 (3)	C18—C17—H17A	109.00
N14—C6—C5	122.4 (2)	C18—C17—H17B	109.00
C5—C6—C7	118.7 (2)	H17A—C17—H17B	108.00
N14—C6—C7	118.8 (2)	C17—C18—H18A	109.00
C6—C7—C8	121.1 (3)	C17—C18—H18B	109.00
Br9—C8—C3	119.5 (2)	C19—C18—H18A	109.00
Br9—C8—C7	119.6 (2)	C19—C18—H18B	109.00
C3—C8—C7	120.9 (3)	H18A—C18—H18B	108.00
S10—C11—C12	119.4 (2)	C18—C19—H19A	110.00
C11—C12—C20	109.1 (3)	C18—C19—H19B	109.00
C13—C12—C16	107.5 (3)	C18—C19—H19C	109.00
C13—C12—C20	109.9 (2)	H19A—C19—H19B	109.00
C16—C12—C20	110.5 (3)	H19A—C19—H19C	109.00
C11—C12—C16	108.1 (3)	H19B—C19—H19C	110.00
C11—C12—C13	111.6 (2)	C12—C20—H20A	109.00
O15—C13—C12	121.0 (2)	C12—C20—H20B	109.00
O15—C13—N14	118.7 (2)	C21—C20—H20A	109.00
N14—C13—C12	120.1 (2)	C21—C20—H20B	109.00
C12—C16—C17	116.6 (3)	H20A—C20—H20B	108.00
C16—C17—C18	112.7 (3)	C20—C21—H21A	109.00
C17—C18—C19	113.3 (5)	C20—C21—H21B	109.00
C12—C20—C21	114.9 (3)	C22—C21—H21A	109.00
C20—C21—C22	113.5 (4)	C22—C21—H21B	109.00
C21—C22—C23	113.3 (5)	H21A—C21—H21B	108.00
O2—C1—H1A	109.00	C21—C22—H22A	109.00
O2—C1—H1B	109.00	C21—C22—H22B	109.00
O2—C1—H1C	109.00	C23—C22—H22A	109.00
H1A—C1—H1B	109.00	C23—C22—H22B	109.00
H1A—C1—H1C	109.00	H22A—C22—H22B	108.00
H1B—C1—H1C	110.00	C22—C23—H23A	109.00
C3—C4—H4	119.00	C22—C23—H23B	109.00
C5—C4—H4	119.00	C22—C23—H23C	110.00
C6—C7—H7	120.00	H23A—C23—H23B	109.00
C8—C7—H7	119.00	H23A—C23—H23C	110.00
S10—C11—H11A	107.00	H23B—C23—H23C	109.00
C11—S10—C5—C4	−117.4 (3)	C5—C6—C7—C8	0.0 (5)
C11—S10—C5—C6	65.0 (3)	C6—C7—C8—Br9	−179.4 (2)
C5—S10—C11—C12	−51.1 (3)	C6—C7—C8—C3	−0.5 (5)
C1—O2—C3—C4	−0.6 (5)	S10—C11—C12—C13	−23.9 (4)
C1—O2—C3—C8	−178.7 (3)	S10—C11—C12—C16	−142.0 (2)
C13—N14—C6—C5	−47.0 (4)	S10—C11—C12—C20	97.8 (3)
C13—N14—C6—C7	136.2 (3)	C11—C12—C13—O15	−113.0 (3)
C6—N14—C13—O15	170.9 (3)	C11—C12—C13—N14	71.2 (3)
C6—N14—C13—C12	−13.2 (4)	C16—C12—C13—O15	5.4 (4)
O2—C3—C4—C5	−179.6 (3)	C16—C12—C13—N14	−170.4 (3)
C8—C3—C4—C5	−1.5 (5)	C20—C12—C13—O15	125.7 (3)
O2—C3—C8—Br9	−1.6 (4)	C20—C12—C13—N14	−50.0 (4)
O2—C3—C8—C7	179.5 (3)	C11—C12—C16—C17	−58.6 (4)
C4—C3—C8—Br9	−179.9 (2)	C13—C12—C16—C17	−179.2 (3)
C4—C3—C8—C7	1.2 (5)	C20—C12—C16—C17	60.8 (4)
C3—C4—C5—S10	−176.5 (3)	C11—C12—C20—C21	−177.2 (3)
C3—C4—C5—C6	1.1 (5)	C13—C12—C20—C21	−54.5 (4)
S10—C5—C6—N14	0.5 (4)	C16—C12—C20—C21	64.1 (4)
S10—C5—C6—C7	177.3 (2)	C12—C16—C17—C18	−176.6 (3)
C4—C5—C6—N14	−177.2 (3)	C16—C17—C18—C19	79.1 (6)
C4—C5—C6—C7	−0.3 (5)	C12—C20—C21—C22	179.7 (3)
N14—C6—C7—C8	177.0 (3)	C20—C21—C22—C23	−179.9 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N14—H14···O15i	0.86	2.13	2.985 (3)	175
C11—H11B···O15ii	0.97	2.52	3.473 (4)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N14—H14⋯O15i	0.86	2.13	2.985 (3)	175

Symmetry code: (i) .