{2-[(2-Bromo-5-meth-oxy-benzyl-idene)amino]-4,5,6,7-tetra-hydro-benzo[b]thiophen-3-yl}(phen-yl)methanone.

In the title compound, C23H20BrNO2S, disorder was modeled for the outer two C atoms of the cyclo-hexene ring over two sets of sites with an occupancy ratio of 0.580 (11):0.420 (11). Both rings have a half-chair conformation. The dihedral angles between the mean plane of the thio-phene ring and the benzene and phenyl rings are 9.2 (2) and 66.1 (2)°, respectively. The benzene and phenyl rings are inclined to each other by 74.8 (8)°. In the crystal, mol-ecules are linked by pairs of C-H⋯O hydrogen bonds, forming inversion dimers.

Related literature

For applications of 2-amino­thio­phene derivatives, see: Sabnis et al. (1999 ▶); Puterová et al. (2010 ▶). For the biological and industrial importance of Schiff bases, see: Desai et al. (2001 ▶); Karia & Parsania (1999 ▶); Samadhiya & Halve (2001 ▶); Singh & Dash (1988 ▶); Aydogan et al. (2001 ▶); Taggi et al. (2002 ▶). For a related structure, see: Kubicki et al. (2012 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C23H20BrNO2S

M = 454.37

Monoclinic,

a = 8.84813 (17) Å

b = 12.5563 (2) Å

c = 18.4384 (4) Å

β = 102.363 (2)°

V = 2001.00 (7) Å3

Z = 4

Cu Kα radiation

μ = 3.92 mm−1

T = 173 K

0.26 × 0.22 × 0.14 mm

Data collection

Agilent Eos Gemini diffractometer

Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T min = 0.725, T max = 1.000

12404 measured reflections

3853 independent reflections

3440 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.087

S = 1.05

3853 reflections

273 parameters

H-atom parameters constrained

Δρmax = 0.56 e Å−3

Δρmin = −0.31 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012 ▶); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009 ▶) and PLATON.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814008290/su2721sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814008290/su2721Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814008290/su2721Isup3.cml

CCDC reference: 997010

Additional supporting information: crystallographic information; 3D view; checkCIF report

C23H20BrNO2S	F(000) = 928
Mr = 454.37	Dx = 1.508 Mg m−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
a = 8.84813 (17) Å	Cell parameters from 5917 reflections
b = 12.5563 (2) Å	θ = 4.3–71.4°
c = 18.4384 (4) Å	µ = 3.92 mm−1
β = 102.363 (2)°	T = 173 K
V = 2001.00 (7) Å3	Irregular, yellow
Z = 4	0.26 × 0.22 × 0.14 mm

Agilent Eos Gemini diffractometer	3440 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray Source	Rint = 0.034
ω scans	θmax = 71.3°, θmin = 4.3°
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	h = −10→10
Tmin = 0.725, Tmax = 1.000	k = −15→13
12404 measured reflections	l = −22→22
3853 independent reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032	H-atom parameters constrained
wR(F2) = 0.087	w = 1/[σ2(Fo2) + (0.0539P)2 + 0.1502P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
3853 reflections	Δρmax = 0.56 e Å−3
273 parameters	Δρmin = −0.31 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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	0.09686 (3)	0.02458 (2)	0.60828 (2)	0.03755 (10)
S1	0.37522 (6)	−0.13254 (4)	0.41239 (3)	0.02972 (12)
O1	0.3841 (2)	0.10568 (12)	0.20797 (8)	0.0407 (4)
O2	0.17717 (19)	0.45920 (12)	0.48309 (10)	0.0405 (4)
N1	0.31360 (18)	0.08489 (13)	0.41394 (9)	0.0273 (3)
C1	0.4306 (2)	0.10714 (15)	0.27533 (11)	0.0277 (4)
C2	0.4297 (2)	0.00672 (15)	0.31824 (11)	0.0252 (4)
C3	0.4776 (2)	−0.09409 (15)	0.29439 (10)	0.0260 (4)
C4	0.5456 (2)	−0.11311 (16)	0.22707 (12)	0.0326 (4)
H4AA	0.4632	−0.1074	0.1815	0.039*	0.580 (11)
H4AB	0.6246	−0.0581	0.2247	0.039*	0.580 (11)
H4BC	0.6560	−0.0922	0.2382	0.039*	0.420 (11)
H4BD	0.4906	−0.0689	0.1852	0.039*	0.420 (11)
C5A	0.6185 (8)	−0.2219 (3)	0.2307 (3)	0.0388 (14)	0.580 (11)
H5AA	0.7174	−0.2213	0.2680	0.047*	0.580 (11)
H5AB	0.6418	−0.2394	0.1819	0.047*	0.580 (11)
C6A	0.5129 (10)	−0.3069 (3)	0.2513 (3)	0.0427 (14)	0.580 (11)
H6AA	0.5568	−0.3783	0.2462	0.051*	0.580 (11)
H6AB	0.4100	−0.3028	0.2173	0.051*	0.580 (11)
C5B	0.5303 (11)	−0.2343 (5)	0.2047 (4)	0.0386 (18)	0.420 (11)
H5BA	0.4198	−0.2524	0.1865	0.046*	0.420 (11)
H5BB	0.5848	−0.2476	0.1639	0.046*	0.420 (11)
C6B	0.5977 (12)	−0.3033 (5)	0.2695 (4)	0.0411 (17)	0.420 (11)
H6BA	0.7060	−0.2820	0.2904	0.049*	0.420 (11)
H6BB	0.5974	−0.3786	0.2536	0.049*	0.420 (11)
C7	0.4959 (3)	−0.29043 (15)	0.33123 (12)	0.0353 (4)
H7AA	0.4128	−0.3367	0.3419	0.042*	0.580 (11)
H7AB	0.5938	−0.3089	0.3662	0.042*	0.580 (11)
H7BC	0.3994	−0.3322	0.3165	0.042*	0.420 (11)
H7BD	0.5543	−0.3186	0.3793	0.042*	0.420 (11)
C8	0.4568 (2)	−0.17526 (15)	0.34010 (11)	0.0269 (4)
C9	0.3723 (2)	−0.00049 (15)	0.38167 (11)	0.0255 (4)
C10	0.4899 (2)	0.20856 (15)	0.31299 (10)	0.0267 (4)
C11	0.5983 (2)	0.20984 (17)	0.38015 (12)	0.0346 (4)
H11	0.6293	0.1451	0.4057	0.041*
C12	0.6606 (3)	0.3059 (2)	0.40951 (14)	0.0441 (5)
H12	0.7362	0.3069	0.4547	0.053*
C13	0.6125 (3)	0.40071 (19)	0.37281 (15)	0.0483 (6)
H13	0.6558	0.4664	0.3928	0.058*
C14	0.5021 (3)	0.39969 (18)	0.30749 (14)	0.0444 (5)
H14	0.4674	0.4647	0.2832	0.053*
C15	0.4416 (3)	0.30354 (16)	0.27719 (12)	0.0345 (4)
H15	0.3668	0.3029	0.2318	0.041*
C16	0.2623 (2)	0.07449 (15)	0.47319 (11)	0.0277 (4)
H16	0.2647	0.0067	0.4964	0.033*
C17	0.1995 (2)	0.16678 (16)	0.50565 (11)	0.0281 (4)
C18	0.1202 (2)	0.15806 (16)	0.56306 (11)	0.0299 (4)
C19	0.0562 (2)	0.24697 (18)	0.58977 (12)	0.0348 (4)
H19	−0.0009	0.2392	0.6276	0.042*
C20	0.0754 (2)	0.34625 (17)	0.56152 (12)	0.0358 (5)
H20	0.0319	0.4071	0.5799	0.043*
C21	0.1592 (2)	0.35725 (16)	0.50552 (12)	0.0319 (4)
C22	0.2189 (2)	0.26847 (16)	0.47765 (11)	0.0299 (4)
H22	0.2739	0.2763	0.4390	0.036*
C23	0.2887 (3)	0.47572 (17)	0.43904 (14)	0.0413 (5)
H23A	0.2536	0.4414	0.3906	0.062*
H23B	0.3879	0.4449	0.4642	0.062*
H23C	0.3015	0.5523	0.4320	0.062*

	U11	U22	U33	U12	U13	U23
Br1	0.04351 (15)	0.03807 (15)	0.03571 (15)	−0.00469 (8)	0.01879 (10)	0.00195 (8)
S1	0.0388 (3)	0.0250 (2)	0.0288 (2)	−0.00344 (17)	0.0148 (2)	0.00060 (17)
O1	0.0647 (10)	0.0314 (7)	0.0247 (7)	0.0017 (7)	0.0063 (7)	−0.0007 (6)
O2	0.0448 (9)	0.0312 (7)	0.0485 (9)	0.0077 (6)	0.0168 (7)	0.0049 (7)
N1	0.0286 (8)	0.0273 (8)	0.0282 (8)	−0.0024 (6)	0.0107 (6)	−0.0035 (6)
C1	0.0306 (9)	0.0271 (9)	0.0278 (10)	0.0021 (7)	0.0116 (7)	0.0006 (7)
C2	0.0252 (9)	0.0253 (9)	0.0259 (9)	−0.0015 (7)	0.0075 (7)	−0.0021 (7)
C3	0.0256 (8)	0.0259 (9)	0.0270 (9)	−0.0015 (7)	0.0070 (7)	−0.0027 (7)
C4	0.0370 (10)	0.0313 (10)	0.0336 (11)	0.0019 (8)	0.0167 (8)	−0.0013 (8)
C5A	0.046 (3)	0.031 (2)	0.046 (3)	0.0047 (19)	0.027 (3)	−0.0045 (17)
C6A	0.058 (4)	0.028 (2)	0.051 (3)	−0.003 (2)	0.030 (3)	−0.0095 (18)
C5B	0.044 (4)	0.038 (3)	0.037 (3)	−0.001 (3)	0.016 (3)	−0.010 (2)
C6B	0.047 (4)	0.033 (3)	0.047 (4)	0.005 (3)	0.017 (3)	−0.011 (2)
C7	0.0453 (11)	0.0235 (10)	0.0386 (11)	−0.0014 (8)	0.0125 (9)	−0.0031 (8)
C8	0.0262 (9)	0.0260 (9)	0.0291 (10)	−0.0018 (7)	0.0073 (7)	−0.0033 (7)
C9	0.0272 (9)	0.0231 (8)	0.0278 (9)	−0.0023 (7)	0.0092 (7)	0.0002 (7)
C10	0.0308 (9)	0.0267 (9)	0.0267 (9)	−0.0021 (7)	0.0154 (7)	−0.0011 (7)
C11	0.0352 (10)	0.0351 (11)	0.0354 (11)	−0.0033 (8)	0.0119 (8)	−0.0009 (8)
C12	0.0424 (12)	0.0498 (14)	0.0425 (13)	−0.0135 (10)	0.0144 (10)	−0.0113 (10)
C13	0.0623 (15)	0.0338 (12)	0.0562 (15)	−0.0214 (11)	0.0295 (12)	−0.0137 (11)
C14	0.0671 (15)	0.0253 (10)	0.0479 (13)	−0.0045 (10)	0.0279 (12)	0.0012 (9)
C15	0.0463 (12)	0.0289 (10)	0.0323 (11)	−0.0002 (8)	0.0169 (9)	0.0023 (8)
C16	0.0282 (9)	0.0281 (9)	0.0279 (9)	−0.0009 (7)	0.0086 (7)	−0.0006 (7)
C17	0.0256 (9)	0.0311 (10)	0.0288 (10)	0.0003 (7)	0.0085 (7)	−0.0031 (8)
C18	0.0289 (9)	0.0342 (10)	0.0286 (10)	−0.0008 (7)	0.0107 (8)	0.0012 (8)
C19	0.0290 (9)	0.0471 (12)	0.0318 (10)	0.0034 (8)	0.0140 (8)	−0.0043 (9)
C20	0.0329 (10)	0.0377 (11)	0.0387 (11)	0.0095 (8)	0.0123 (9)	−0.0047 (9)
C21	0.0297 (9)	0.0304 (10)	0.0352 (11)	0.0042 (7)	0.0061 (8)	0.0004 (8)
C22	0.0291 (9)	0.0356 (10)	0.0270 (9)	0.0015 (7)	0.0105 (8)	−0.0007 (8)
C23	0.0443 (12)	0.0361 (12)	0.0447 (13)	−0.0001 (9)	0.0121 (10)	0.0061 (9)

Br1—C18	1.903 (2)	C6B—C7	1.603 (7)
S1—C8	1.7314 (19)	C7—H7AA	0.9900
S1—C9	1.7506 (19)	C7—H7AB	0.9900
O1—C1	1.222 (2)	C7—H7BC	0.9900
O2—C21	1.365 (3)	C7—H7BD	0.9900
O2—C23	1.421 (3)	C7—C8	1.504 (3)
N1—C9	1.380 (3)	C10—C11	1.395 (3)
N1—C16	1.277 (2)	C10—C15	1.386 (3)
C1—C2	1.489 (3)	C11—H11	0.9500
C1—C10	1.491 (3)	C11—C12	1.387 (3)
C2—C3	1.433 (3)	C12—H12	0.9500
C2—C9	1.374 (3)	C12—C13	1.391 (4)
C3—C4	1.510 (3)	C13—H13	0.9500
C3—C8	1.360 (3)	C13—C14	1.379 (4)
C4—H4AA	0.9900	C14—H14	0.9500
C4—H4AB	0.9900	C14—C15	1.389 (3)
C4—H4BC	0.9900	C15—H15	0.9500
C4—H4BD	0.9900	C16—H16	0.9500
C4—C5A	1.506 (4)	C16—C17	1.467 (3)
C4—C5B	1.575 (6)	C17—C18	1.394 (3)
C5A—H5AA	0.9900	C17—C22	1.402 (3)
C5A—H5AB	0.9900	C18—C19	1.389 (3)
C5A—C6A	1.519 (8)	C19—H19	0.9500
C6A—H6AA	0.9900	C19—C20	1.375 (3)
C6A—H6AB	0.9900	C20—H20	0.9500
C6A—C7	1.526 (5)	C20—C21	1.401 (3)
C5B—H5BA	0.9900	C21—C22	1.379 (3)
C5B—H5BB	0.9900	C22—H22	0.9500
C5B—C6B	1.494 (12)	C23—H23A	0.9800
C6B—H6BA	0.9900	C23—H23B	0.9800
C6B—H6BB	0.9900	C23—H23C	0.9800
C8—S1—C9	91.38 (9)	C8—C7—H7AA	110.1
C21—O2—C23	116.75 (16)	C8—C7—H7AB	110.1
C16—N1—C9	121.68 (17)	C8—C7—H7BC	109.5
O1—C1—C2	119.22 (18)	C8—C7—H7BD	109.5
O1—C1—C10	119.64 (18)	C3—C8—S1	112.26 (14)
C2—C1—C10	121.13 (17)	C3—C8—C7	126.05 (18)
C3—C2—C1	123.31 (17)	C7—C8—S1	121.68 (15)
C9—C2—C1	123.55 (17)	N1—C9—S1	125.24 (14)
C9—C2—C3	112.97 (17)	C2—C9—S1	110.80 (15)
C2—C3—C4	126.00 (17)	C2—C9—N1	123.88 (18)
C8—C3—C2	112.57 (17)	C11—C10—C1	122.00 (18)
C8—C3—C4	121.43 (17)	C15—C10—C1	118.12 (18)
C3—C4—H4AA	109.6	C15—C10—C11	119.77 (19)
C3—C4—H4AB	109.6	C10—C11—H11	120.1
C3—C4—H4BC	109.7	C12—C11—C10	119.8 (2)
C3—C4—H4BD	109.7	C12—C11—H11	120.1
C3—C4—C5B	110.0 (3)	C11—C12—H12	120.0
H4AA—C4—H4AB	108.1	C11—C12—C13	120.0 (2)
H4BC—C4—H4BD	108.2	C13—C12—H12	120.0
C5A—C4—C3	110.4 (2)	C12—C13—H13	119.9
C5A—C4—H4AA	109.6	C14—C13—C12	120.2 (2)
C5A—C4—H4AB	109.6	C14—C13—H13	119.9
C5B—C4—H4BC	109.7	C13—C14—H14	120.0
C5B—C4—H4BD	109.7	C13—C14—C15	120.0 (2)
C4—C5A—H5AA	109.3	C15—C14—H14	120.0
C4—C5A—H5AB	109.3	C10—C15—C14	120.2 (2)
C4—C5A—C6A	111.6 (5)	C10—C15—H15	119.9
H5AA—C5A—H5AB	108.0	C14—C15—H15	119.9
C6A—C5A—H5AA	109.3	N1—C16—H16	119.9
C6A—C5A—H5AB	109.3	N1—C16—C17	120.24 (18)
C5A—C6A—H6AA	109.7	C17—C16—H16	119.9
C5A—C6A—H6AB	109.7	C18—C17—C16	122.95 (18)
C5A—C6A—C7	109.8 (5)	C18—C17—C22	118.20 (18)
H6AA—C6A—H6AB	108.2	C22—C17—C16	118.85 (17)
C7—C6A—H6AA	109.7	C17—C18—Br1	121.43 (15)
C7—C6A—H6AB	109.7	C19—C18—Br1	117.50 (15)
C4—C5B—H5BA	109.5	C19—C18—C17	121.06 (19)
C4—C5B—H5BB	109.5	C18—C19—H19	120.0
H5BA—C5B—H5BB	108.1	C20—C19—C18	120.08 (19)
C6B—C5B—C4	110.7 (6)	C20—C19—H19	120.0
C6B—C5B—H5BA	109.5	C19—C20—H20	120.1
C6B—C5B—H5BB	109.5	C19—C20—C21	119.75 (19)
C5B—C6B—H6BA	109.9	C21—C20—H20	120.1
C5B—C6B—H6BB	109.9	O2—C21—C20	115.47 (18)
C5B—C6B—C7	108.8 (6)	O2—C21—C22	124.50 (19)
H6BA—C6B—H6BB	108.3	C22—C21—C20	120.02 (19)
C7—C6B—H6BA	109.9	C17—C22—H22	119.6
C7—C6B—H6BB	109.9	C21—C22—C17	120.81 (18)
C6A—C7—H7AA	110.1	C21—C22—H22	119.6
C6A—C7—H7AB	110.1	O2—C23—H23A	109.5
C6B—C7—H7BC	109.5	O2—C23—H23B	109.5
C6B—C7—H7BD	109.5	O2—C23—H23C	109.5
H7AA—C7—H7AB	108.4	H23A—C23—H23B	109.5
H7BC—C7—H7BD	108.1	H23A—C23—H23C	109.5
C8—C7—C6A	107.9 (2)	H23B—C23—H23C	109.5
C8—C7—C6B	110.6 (3)
Br1—C18—C19—C20	177.08 (17)	C5B—C6B—C7—C8	−43.3 (8)
O1—C1—C2—C3	42.7 (3)	C6B—C7—C8—S1	−169.4 (4)
O1—C1—C2—C9	−132.2 (2)	C6B—C7—C8—C3	11.4 (5)
O1—C1—C10—C11	−153.30 (19)	C8—S1—C9—N1	177.94 (17)
O1—C1—C10—C15	22.8 (3)	C8—S1—C9—C2	0.96 (15)
O2—C21—C22—C17	177.79 (19)	C8—C3—C4—C5A	−13.9 (4)
N1—C16—C17—C18	169.70 (19)	C8—C3—C4—C5B	19.7 (5)
N1—C16—C17—C22	−9.9 (3)	C9—S1—C8—C3	−1.23 (15)
C1—C2—C3—C4	4.7 (3)	C9—S1—C8—C7	179.49 (17)
C1—C2—C3—C8	−175.86 (17)	C9—N1—C16—C17	−179.50 (17)
C1—C2—C9—S1	174.92 (15)	C9—C2—C3—C4	−179.91 (18)
C1—C2—C9—N1	−2.1 (3)	C9—C2—C3—C8	−0.4 (2)
C1—C10—C11—C12	174.01 (19)	C10—C1—C2—C3	−136.11 (19)
C1—C10—C15—C14	−175.38 (19)	C10—C1—C2—C9	48.9 (3)
C2—C1—C10—C11	25.5 (3)	C10—C11—C12—C13	1.4 (3)
C2—C1—C10—C15	−158.38 (18)	C11—C10—C15—C14	0.8 (3)
C2—C3—C4—C5A	165.5 (3)	C11—C12—C13—C14	0.5 (4)
C2—C3—C4—C5B	−160.9 (4)	C12—C13—C14—C15	−1.7 (4)
C2—C3—C8—S1	1.2 (2)	C13—C14—C15—C10	1.1 (3)
C2—C3—C8—C7	−179.59 (18)	C15—C10—C11—C12	−2.0 (3)
C3—C2—C9—S1	−0.5 (2)	C16—N1—C9—S1	3.8 (3)
C3—C2—C9—N1	−177.51 (17)	C16—N1—C9—C2	−179.59 (19)
C3—C4—C5A—C6A	46.7 (7)	C16—C17—C18—Br1	3.6 (3)
C3—C4—C5B—C6B	−53.2 (8)	C16—C17—C18—C19	−176.87 (19)
C4—C3—C8—S1	−179.33 (15)	C16—C17—C22—C21	178.74 (18)
C4—C3—C8—C7	−0.1 (3)	C17—C18—C19—C20	−2.4 (3)
C4—C5A—C6A—C7	−67.6 (8)	C18—C17—C22—C21	−0.9 (3)
C4—C5B—C6B—C7	65.5 (9)	C18—C19—C20—C21	0.2 (3)
C5A—C4—C5B—C6B	43.5 (7)	C19—C20—C21—O2	−177.5 (2)
C5A—C6A—C7—C6B	−51.1 (7)	C19—C20—C21—C22	1.6 (3)
C5A—C6A—C7—C8	49.3 (7)	C20—C21—C22—C17	−1.3 (3)
C6A—C7—C8—S1	161.2 (4)	C22—C17—C18—Br1	−176.77 (14)
C6A—C7—C8—C3	−17.9 (4)	C22—C17—C18—C19	2.7 (3)
C5B—C4—C5A—C6A	−48.4 (6)	C23—O2—C21—C20	166.49 (19)
C5B—C6B—C7—C6A	46.2 (7)	C23—O2—C21—C22	−12.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20···O2i	0.95	2.58	3.294 (3)	132

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C20—H20⋯O2i	0.95	2.58	3.294 (3)	132

Symmetry code: (i) .