4-(Thio-phen-2-yl)-2-[4-(tri-fluoro-meth-yl)phen-yl]-2,3-di-hydro-1,5-benzo-thia-zepine.

In the title compound, C20H14F3NS2, the seven-membered thia-zepine ring adopts a slightly distorted twist-boat conformation. The mean plane of the five-membered thio-phene ring fused to the thia-zepine ring is twisted by 32.3 (3) and 55.6 (4)° from the benzene and phenyl rings, respectively. In the crystal, inversion dimers linked by pairs of weak C-H⋯N inter-actions are observed.

Related literature

For the biological activity of 1, 4-thia­zepines, see: Skiles et al. (1986 ▶); Zeng & Alper (2010 ▶). For a related structure, see: Manjula et al. (2013 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C20H14F3NS2

M = 389.46

Orthorhombic,

a = 9.847 (2) Å

b = 10.492 (3) Å

c = 17.819 (4) Å

V = 1841.0 (8) Å3

Z = 4

Cu Kα radiation

μ = 2.92 mm−1

T = 296 K

0.20 × 0.19 × 0.18 mm

Data collection

Bruker X8 Proteum diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2013 ▶ T min = 0.593, T max = 0.622

12103 measured reflections

3028 independent reflections

2547 reflections with I > 2σ(I)

R int = 0.056

Refinement

R[F 2 > 2σ(F 2)] = 0.085

wR(F 2) = 0.239

S = 1.03

3028 reflections

237 parameters

H-atom parameters constrained

Δρmax = 0.94 e Å−3

Δρmin = −0.51 e Å−3

Absolute structure: Flack (1983 ▶), 1270 Friedel pairs

Absolute structure parameter: 0.0 (3)

Data collection: APEX2 (Bruker, 2013 ▶); cell refinement: SAINT (Bruker, 2013 ▶); data reduction: SAINT; 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/S1600536814002529/jj2182sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814002529/jj2182Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814002529/jj2182Isup3.cml

CCDC reference:

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

C20H14F3NS2	F(000) = 800
Mr = 389.46	Dx = 1.405 Mg m−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 12103 reflections
a = 9.847 (2) Å	θ = 4.9–64.8°
b = 10.492 (3) Å	µ = 2.92 mm−1
c = 17.819 (4) Å	T = 296 K
V = 1841.0 (8) Å3	Needle, light yellow
Z = 4	0.20 × 0.19 × 0.18 mm

Bruker X8 Proteum diffractometer	3028 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	2547 reflections with I > 2σ(I)
Helios multilayer optics monochromator	Rint = 0.056
Detector resolution: 10.7 pixels mm-1	θmax = 64.8°, θmin = 4.9°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2013	k = −8→12
Tmin = 0.593, Tmax = 0.622	l = −20→20
12103 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.085	w = 1/[σ2(Fo2) + (0.1979P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.239	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.94 e Å−3
3028 reflections	Δρmin = −0.51 e Å−3
237 parameters	Extinction correction: SHELXL, FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4
0 restraints	Extinction coefficient: 0.017 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1270 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.0 (3)

Experimental. m.p. 405 K, 1H NMR (CDCl3): δ 2.0 (d, 2H, C3—H), 3.80 (t, 1H, C2—H), 7.24 (dd, 2H, Ar—H), 7.58 (dd, 2H, Ar—H), 7.18 (t, 1H, C4—H 5 m ring), 7.46 (d, 1H, C3—H 5 m ring), 7.72 (d, 1H, C5—H 5 m ring), 7.32–7.46 (m, 4H, Ar—H). Anal. Calcd. for C20H14F3NS2: C 62.14, H 3.56, N 3.58°; Found C 61.68, H 3.62, N 3.60°. Mass FAB+ (NBA): 390 (M + 1, 100°).

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 e.s.d.'s 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 > σ(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
S1	0.3240 (2)	0.99443 (19)	0.41340 (10)	0.0841 (7)
S9	−0.00510 (15)	0.88544 (12)	0.20297 (9)	0.0608 (5)
F24	0.2469 (9)	0.4640 (10)	−0.1093 (6)	0.257 (6)
F25	0.0847 (19)	0.5559 (8)	−0.1388 (4)	0.289 (10)
F26	0.0674 (7)	0.3951 (6)	−0.0787 (3)	0.139 (3)
N12	0.1053 (5)	0.8288 (4)	0.3632 (3)	0.0550 (16)
C2	0.4905 (8)	1.0319 (9)	0.4023 (6)	0.104 (4)
C3	0.5488 (8)	0.9699 (9)	0.3449 (7)	0.101 (4)
C4	0.4592 (6)	0.8887 (6)	0.3089 (4)	0.0650 (19)
C5	0.3308 (5)	0.8882 (5)	0.3403 (3)	0.0533 (17)
C6	0.2105 (5)	0.8181 (5)	0.3202 (3)	0.0500 (16)
C7	0.2105 (5)	0.7370 (5)	0.2509 (3)	0.0477 (16)
C8	0.1595 (5)	0.8108 (4)	0.1818 (3)	0.0510 (16)
C10	−0.0758 (6)	0.7848 (5)	0.2719 (3)	0.0523 (16)
C11	−0.0168 (5)	0.7715 (5)	0.3428 (3)	0.0517 (14)
C13	−0.2004 (6)	0.7269 (6)	0.2580 (4)	0.0680 (19)
C14	−0.2705 (6)	0.6610 (6)	0.3132 (5)	0.071 (2)
C15	−0.2116 (7)	0.6511 (6)	0.3834 (5)	0.073 (2)
C16	−0.0877 (7)	0.7058 (6)	0.3996 (4)	0.0653 (19)
C17	0.1511 (5)	0.7293 (4)	0.1124 (3)	0.0447 (12)
C18	0.2330 (6)	0.7568 (5)	0.0509 (3)	0.0503 (16)
C19	0.2279 (6)	0.6822 (5)	−0.0137 (3)	0.0557 (17)
C20	0.1419 (5)	0.5784 (5)	−0.0162 (3)	0.0493 (16)
C21	0.0616 (6)	0.5477 (5)	0.0452 (3)	0.0580 (17)
C22	0.0667 (6)	0.6223 (5)	0.1088 (3)	0.0580 (17)
C23	0.1334 (7)	0.4983 (7)	−0.0842 (3)	0.071 (2)
H2	0.53640	1.08950	0.43280	0.1250*
H3	0.63920	0.98020	0.33100	0.1210*
H4	0.48310	0.83940	0.26760	0.0780*
H7A	0.15280	0.66340	0.25910	0.0570*
H7B	0.30190	0.70660	0.24150	0.0570*
H8	0.22470	0.87940	0.17180	0.0610*
H13	−0.23780	0.73260	0.21020	0.0820*
H14	−0.35470	0.62440	0.30330	0.0850*
H15	−0.25690	0.60620	0.42080	0.0880*
H16	−0.05120	0.69950	0.44760	0.0790*
H18	0.29200	0.82590	0.05300	0.0600*
H19	0.28190	0.70230	−0.05490	0.0660*
H21	0.00450	0.47720	0.04340	0.0700*
H22	0.01320	0.60120	0.14990	0.0700*

	U11	U22	U33	U12	U13	U23
S1	0.0843 (11)	0.0942 (13)	0.0738 (11)	−0.0174 (9)	−0.0048 (8)	−0.0297 (9)
S9	0.0687 (9)	0.0503 (7)	0.0634 (9)	0.0168 (6)	0.0018 (7)	0.0040 (5)
F24	0.190 (8)	0.307 (12)	0.275 (12)	−0.134 (8)	0.144 (8)	−0.238 (11)
F25	0.64 (3)	0.152 (6)	0.076 (4)	0.034 (12)	−0.127 (9)	−0.021 (4)
F26	0.200 (7)	0.123 (4)	0.093 (4)	−0.086 (4)	0.037 (4)	−0.050 (3)
N12	0.063 (3)	0.050 (2)	0.052 (3)	−0.002 (2)	0.010 (2)	−0.0088 (18)
C2	0.073 (4)	0.106 (6)	0.133 (8)	−0.017 (4)	−0.026 (5)	−0.019 (6)
C3	0.067 (4)	0.104 (6)	0.132 (8)	−0.018 (4)	0.003 (5)	−0.001 (6)
C4	0.051 (3)	0.070 (3)	0.074 (4)	−0.003 (2)	0.011 (3)	0.004 (3)
C5	0.053 (3)	0.050 (3)	0.057 (3)	0.004 (2)	−0.001 (2)	0.003 (2)
C6	0.054 (3)	0.046 (2)	0.050 (3)	0.008 (2)	0.005 (2)	0.002 (2)
C7	0.055 (3)	0.042 (2)	0.046 (3)	0.004 (2)	0.004 (2)	−0.005 (2)
C8	0.064 (3)	0.045 (2)	0.044 (3)	0.004 (2)	0.001 (2)	−0.0035 (19)
C10	0.057 (3)	0.040 (2)	0.060 (3)	0.008 (2)	0.000 (2)	−0.005 (2)
C11	0.050 (2)	0.050 (2)	0.055 (3)	−0.002 (2)	0.012 (2)	−0.010 (2)
C13	0.049 (3)	0.067 (3)	0.088 (4)	0.005 (3)	−0.008 (3)	−0.008 (3)
C14	0.054 (3)	0.064 (3)	0.095 (5)	−0.010 (3)	0.002 (3)	−0.002 (3)
C15	0.063 (3)	0.067 (4)	0.089 (5)	−0.005 (3)	0.017 (4)	0.003 (3)
C16	0.075 (4)	0.064 (3)	0.057 (3)	−0.007 (3)	0.018 (3)	−0.001 (3)
C17	0.052 (2)	0.039 (2)	0.043 (2)	−0.0020 (19)	0.0043 (19)	0.0005 (19)
C18	0.057 (3)	0.045 (2)	0.049 (3)	−0.007 (2)	0.004 (2)	0.005 (2)
C19	0.061 (3)	0.057 (3)	0.049 (3)	−0.014 (2)	0.008 (2)	0.000 (2)
C20	0.053 (3)	0.049 (2)	0.046 (3)	−0.004 (2)	0.005 (2)	0.000 (2)
C21	0.066 (3)	0.055 (3)	0.053 (3)	−0.009 (2)	0.010 (3)	−0.003 (2)
C22	0.067 (3)	0.053 (3)	0.054 (3)	−0.016 (2)	0.014 (2)	−0.005 (2)
C23	0.087 (4)	0.080 (4)	0.047 (3)	−0.026 (4)	0.018 (3)	−0.012 (3)

S1—C2	1.698 (8)	C17—C18	1.391 (8)
S1—C5	1.716 (6)	C17—C22	1.398 (7)
S9—C8	1.839 (5)	C18—C19	1.393 (8)
S9—C10	1.763 (6)	C19—C20	1.380 (8)
F24—C23	1.256 (11)	C20—C21	1.388 (8)
F25—C23	1.242 (12)	C20—C23	1.477 (8)
F26—C23	1.267 (10)	C21—C22	1.378 (8)
N12—C6	1.293 (7)	C2—H2	0.9300
N12—C11	1.393 (7)	C3—H3	0.9300
C2—C3	1.341 (15)	C4—H4	0.9300
C3—C4	1.384 (12)	C7—H7A	0.9700
C4—C5	1.383 (8)	C7—H7B	0.9700
C5—C6	1.440 (7)	C8—H8	0.9800
C6—C7	1.500 (8)	C13—H13	0.9300
C7—C8	1.539 (7)	C14—H14	0.9300
C8—C17	1.506 (7)	C15—H15	0.9300
C10—C11	1.398 (8)	C16—H16	0.9300
C10—C13	1.391 (8)	C18—H18	0.9300
C11—C16	1.410 (9)	C19—H19	0.9300
C13—C14	1.386 (10)	C21—H21	0.9300
C14—C15	1.383 (12)	C22—H22	0.9300
C15—C16	1.379 (10)
C2—S1—C5	91.4 (4)	F24—C23—F25	101.8 (10)
C8—S9—C10	103.6 (2)	F24—C23—F26	103.8 (8)
C6—N12—C11	120.0 (5)	F24—C23—C20	113.9 (7)
S1—C2—C3	113.0 (7)	F25—C23—F26	106.2 (8)
C2—C3—C4	112.3 (7)	F25—C23—C20	112.8 (7)
C3—C4—C5	113.4 (7)	F26—C23—C20	116.9 (5)
S1—C5—C4	109.9 (4)	S1—C2—H2	123.00
S1—C5—C6	119.3 (4)	C3—C2—H2	124.00
C4—C5—C6	130.8 (5)	C2—C3—H3	124.00
N12—C6—C5	117.9 (5)	C4—C3—H3	124.00
N12—C6—C7	122.5 (5)	C3—C4—H4	123.00
C5—C6—C7	119.7 (4)	C5—C4—H4	123.00
C6—C7—C8	111.9 (4)	C6—C7—H7A	109.00
S9—C8—C7	109.7 (4)	C6—C7—H7B	109.00
S9—C8—C17	111.2 (3)	C8—C7—H7A	109.00
C7—C8—C17	112.9 (4)	C8—C7—H7B	109.00
S9—C10—C11	121.7 (4)	H7A—C7—H7B	108.00
S9—C10—C13	119.1 (5)	S9—C8—H8	108.00
C11—C10—C13	118.9 (5)	C7—C8—H8	108.00
N12—C11—C10	123.5 (5)	C17—C8—H8	108.00
N12—C11—C16	116.8 (5)	C10—C13—H13	119.00
C10—C11—C16	119.5 (5)	C14—C13—H13	119.00
C10—C13—C14	122.0 (6)	C13—C14—H14	121.00
C13—C14—C15	118.1 (6)	C15—C14—H14	121.00
C14—C15—C16	122.0 (7)	C14—C15—H15	119.00
C11—C16—C15	119.4 (7)	C16—C15—H15	119.00
C8—C17—C18	119.8 (4)	C11—C16—H16	120.00
C8—C17—C22	121.8 (5)	C15—C16—H16	120.00
C18—C17—C22	118.4 (5)	C17—C18—H18	119.00
C17—C18—C19	120.9 (5)	C19—C18—H18	120.00
C18—C19—C20	119.5 (5)	C18—C19—H19	120.00
C19—C20—C21	120.5 (5)	C20—C19—H19	120.00
C19—C20—C23	120.7 (5)	C20—C21—H21	120.00
C21—C20—C23	118.8 (5)	C22—C21—H21	120.00
C20—C21—C22	119.7 (5)	C17—C22—H22	119.00
C17—C22—C21	121.0 (5)	C21—C22—H22	119.00
C5—S1—C2—C3	1.5 (8)	S9—C10—C11—C16	170.3 (4)
C2—S1—C5—C4	−1.9 (5)	C13—C10—C11—N12	−177.9 (5)
C2—S1—C5—C6	179.5 (5)	S9—C10—C13—C14	−171.0 (5)
C10—S9—C8—C7	−27.7 (4)	C11—C10—C13—C14	2.8 (9)
C10—S9—C8—C17	97.9 (4)	C13—C10—C11—C16	−3.3 (8)
C8—S9—C10—C11	65.2 (5)	S9—C10—C11—N12	−4.3 (8)
C8—S9—C10—C13	−121.2 (5)	N12—C11—C16—C15	177.7 (5)
C6—N12—C11—C16	135.8 (6)	C10—C11—C16—C15	2.7 (9)
C11—N12—C6—C5	174.6 (5)	C10—C13—C14—C15	−1.5 (10)
C11—N12—C6—C7	−4.9 (8)	C13—C14—C15—C16	0.8 (10)
C6—N12—C11—C10	−49.5 (7)	C14—C15—C16—C11	−1.5 (10)
S1—C2—C3—C4	−0.7 (11)	C8—C17—C18—C19	179.5 (5)
C2—C3—C4—C5	−0.7 (11)	C22—C17—C18—C19	2.1 (8)
C3—C4—C5—S1	1.8 (8)	C8—C17—C22—C21	−179.1 (5)
C3—C4—C5—C6	−179.8 (7)	C18—C17—C22—C21	−1.8 (8)
S1—C5—C6—N12	−6.9 (7)	C17—C18—C19—C20	−1.0 (8)
C4—C5—C6—N12	174.9 (6)	C18—C19—C20—C21	−0.4 (8)
C4—C5—C6—C7	−5.6 (9)	C18—C19—C20—C23	179.4 (5)
S1—C5—C6—C7	172.7 (4)	C19—C20—C21—C22	0.7 (8)
N12—C6—C7—C8	87.7 (6)	C23—C20—C21—C22	−179.1 (5)
C5—C6—C7—C8	−91.8 (6)	C19—C20—C23—F24	49.1 (9)
C6—C7—C8—C17	−176.8 (4)	C19—C20—C23—F25	−66.2 (11)
C6—C7—C8—S9	−52.1 (5)	C19—C20—C23—F26	170.3 (6)
C7—C8—C17—C18	−116.1 (5)	C21—C20—C23—F24	−131.0 (8)
S9—C8—C17—C18	120.0 (5)	C21—C20—C23—F25	113.6 (11)
S9—C8—C17—C22	−62.8 (5)	C21—C20—C23—F26	−9.9 (9)
C7—C8—C17—C22	61.1 (6)	C20—C21—C22—C17	0.4 (8)

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21···N12i	0.93	2.52	3.262 (7)	137

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C21—H21⋯N12i	0.93	2.52	3.262 (7)	137

Symmetry code: (i) .