2-(4-Fluoro-phen-yl)-4-(thio-phen-2-yl)-2,3-di-hydro-1,5-benzothia-zepine.

In the title compound, C19H14FNS2, the seven-membered thia-zepine ring adopts a slightly distorted twist boat conformation. The dihedral angle between the benzene rings is 53.6 (1)°. The mean plane of the thia-zepine ring is twisted by 34.3 (7)° and 36.6 (7)° from the benezene rings. A C-H⋯F interaction generates stacking of molecules along the ab plane.

Related literature

For heterocycles containing the 1,4-thia­zepine ring used as pharmaceutical agents as well as for biologically active compounds, see: Shi et al. (2012 ▶). For the pharmacological activity of benzo­thia­zepine and its derivatives, see: Sanjeeva et al. (2008 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C19H14FNS2

M = 339.43

Monoclinic,

a = 26.1463 (17) Å

b = 12.3091 (8) Å

c = 10.1776 (7) Å

β = 101.383 (4)°

V = 3211.1 (4) Å3

Z = 8

Cu Kα radiation

μ = 3.07 mm−1

T = 293 K

0.24 × 0.22 × 0.16 mm

Data collection

Bruker X8 Proteum diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2013 ▶) T min = 0.502, T max = 0.612

11355 measured reflections

2647 independent reflections

2037 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.134

S = 1.05

2647 reflections

209 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.29 e Å−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: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813025889/jj2176sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813025889/jj2176Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536813025889/jj2176Isup3.cml

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

C19H14FNS2	F(000) = 1408
Mr = 339.43	Dx = 1.404 Mg m−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
a = 26.1463 (17) Å	Cell parameters from 11356 reflections
b = 12.3091 (8) Å	θ = 64.7–4.0°
c = 10.1776 (7) Å	µ = 3.07 mm−1
β = 101.383 (4)°	T = 293 K
V = 3211.1 (4) Å3	Needle, light yellow
Z = 8	0.24 × 0.22 × 0.16 mm

Bruker X8 Proteum diffractometer	2647 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	2037 reflections with I > 2σ(I)
Helios multilayer optics monochromator	Rint = 0.054
Detector resolution: 10.7 pixels mm-1	θmax = 64.7°, θmin = 4.0°
φ and ω scans	h = −30→30
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −13→14
Tmin = 0.502, Tmax = 0.612	l = −9→11
11355 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.047	w = 1/[σ2(Fo2) + (0.071P)2 + 1.8964P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.134	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.24 e Å−3
2647 reflections	Δρmin = −0.29 e Å−3
209 parameters	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.00022 (8)
Primary atom site location: structure-invariant direct methods

Experimental. 1H NMR (CDCl3): δ1.82 (d, 1H, C3—H), 2.12 (d, 1H, C3—H), 3.80 (d, 1H, C2—H), 7.20 (dd, 2H, Ar—H), 7.28 (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).

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.

	x	y	z	Uiso*/Ueq
S1	0.42843 (3)	0.03004 (6)	0.65079 (8)	0.0534 (3)
S2	0.22949 (3)	−0.03765 (7)	0.72781 (9)	0.0592 (3)
F1	0.45335 (9)	0.47959 (17)	0.3082 (2)	0.0811 (6)
N1	0.31778 (8)	−0.09171 (18)	0.5962 (2)	0.0434 (5)
C1	0.30635 (10)	0.0103 (2)	0.5851 (3)	0.0421 (6)
C2	0.33154 (10)	0.0903 (2)	0.5056 (3)	0.0446 (7)
H2A	0.3072	0.1485	0.4743	0.054*
H2B	0.3398	0.0541	0.4278	0.054*
C3	0.38127 (10)	0.1381 (2)	0.5894 (3)	0.0434 (6)
H3	0.3716	0.1717	0.6683	0.052*
C4	0.40778 (10)	−0.0855 (2)	0.5505 (3)	0.0423 (6)
C5	0.35838 (10)	−0.1337 (2)	0.5390 (3)	0.0409 (6)
C6	0.34956 (11)	−0.2345 (2)	0.4772 (3)	0.0471 (7)
H6	0.3170	−0.2671	0.4692	0.056*
C7	0.38840 (12)	−0.2870 (3)	0.4272 (3)	0.0543 (8)
H7	0.3818	−0.3545	0.3862	0.065*
C8	0.43681 (13)	−0.2397 (3)	0.4380 (3)	0.0588 (8)
H8	0.4630	−0.2755	0.4053	0.071*
C9	0.44617 (11)	−0.1395 (3)	0.4974 (3)	0.0515 (8)
H9	0.4786	−0.1070	0.5024	0.062*
C10	0.26577 (10)	0.0500 (2)	0.6544 (3)	0.0448 (7)
C11	0.25218 (11)	0.1577 (2)	0.6726 (3)	0.0499 (7)
H11	0.2670	0.2175	0.6384	0.060*
C12	0.21274 (13)	0.1639 (3)	0.7503 (4)	0.0642 (9)
H12	0.1992	0.2290	0.7748	0.077*
C13	0.19709 (12)	0.0656 (3)	0.7849 (4)	0.0641 (9)
H13	0.1713	0.0555	0.8348	0.077*
C14	0.40372 (10)	0.2271 (2)	0.5150 (3)	0.0406 (6)
C15	0.41640 (11)	0.2101 (2)	0.3910 (3)	0.0473 (7)
H15	0.4136	0.1406	0.3544	0.057*
C16	0.43319 (11)	0.2941 (3)	0.3206 (3)	0.0515 (7)
H16	0.4410	0.2823	0.2365	0.062*
C17	0.43805 (12)	0.3947 (3)	0.3772 (3)	0.0526 (7)
C18	0.42809 (14)	0.4155 (3)	0.5015 (3)	0.0601 (8)
H18	0.4329	0.4845	0.5391	0.072*
C19	0.41050 (13)	0.3301 (2)	0.5697 (3)	0.0533 (8)
H19	0.4031	0.3424	0.6542	0.064*

	U11	U22	U33	U12	U13	U23
S1	0.0529 (4)	0.0427 (5)	0.0573 (5)	−0.0034 (3)	−0.0069 (3)	0.0079 (3)
S2	0.0529 (4)	0.0507 (5)	0.0772 (6)	−0.0008 (3)	0.0207 (4)	−0.0009 (4)
F1	0.1102 (16)	0.0648 (13)	0.0754 (14)	−0.0166 (12)	0.0354 (12)	0.0212 (11)
N1	0.0461 (11)	0.0348 (12)	0.0509 (14)	−0.0007 (10)	0.0135 (10)	−0.0027 (11)
C1	0.0417 (13)	0.0372 (15)	0.0453 (16)	−0.0003 (11)	0.0037 (12)	−0.0011 (12)
C2	0.0483 (14)	0.0363 (15)	0.0489 (17)	0.0018 (12)	0.0088 (12)	0.0056 (13)
C3	0.0528 (14)	0.0342 (14)	0.0423 (16)	−0.0060 (12)	0.0079 (12)	−0.0003 (12)
C4	0.0449 (13)	0.0376 (15)	0.0438 (16)	0.0026 (11)	0.0070 (12)	0.0097 (12)
C5	0.0471 (14)	0.0360 (14)	0.0404 (15)	0.0039 (11)	0.0105 (12)	0.0024 (12)
C6	0.0557 (15)	0.0402 (16)	0.0463 (17)	0.0018 (12)	0.0126 (13)	0.0008 (13)
C7	0.0741 (19)	0.0447 (17)	0.0452 (18)	0.0089 (15)	0.0144 (15)	−0.0012 (14)
C8	0.0629 (18)	0.063 (2)	0.054 (2)	0.0211 (16)	0.0197 (15)	0.0065 (16)
C9	0.0466 (14)	0.0549 (19)	0.0554 (19)	0.0096 (13)	0.0159 (13)	0.0145 (15)
C10	0.0413 (13)	0.0436 (16)	0.0481 (17)	0.0001 (11)	0.0049 (12)	−0.0010 (13)
C11	0.0539 (15)	0.0378 (16)	0.0606 (19)	0.0079 (12)	0.0174 (14)	−0.0045 (14)
C12	0.0676 (19)	0.054 (2)	0.073 (2)	0.0165 (16)	0.0189 (17)	−0.0071 (18)
C13	0.0509 (16)	0.073 (2)	0.072 (2)	0.0084 (16)	0.0213 (16)	−0.0012 (18)
C14	0.0483 (14)	0.0358 (14)	0.0369 (15)	0.0002 (11)	0.0067 (11)	0.0007 (12)
C15	0.0564 (15)	0.0418 (16)	0.0452 (17)	−0.0005 (13)	0.0139 (13)	−0.0077 (13)
C16	0.0557 (16)	0.057 (2)	0.0441 (17)	−0.0006 (14)	0.0145 (13)	0.0015 (15)
C17	0.0604 (16)	0.0483 (17)	0.0502 (18)	−0.0065 (14)	0.0138 (14)	0.0156 (15)
C18	0.089 (2)	0.0377 (17)	0.055 (2)	−0.0076 (16)	0.0177 (17)	−0.0019 (14)
C19	0.082 (2)	0.0397 (17)	0.0418 (16)	−0.0034 (14)	0.0202 (15)	−0.0008 (13)

S1—C3	1.837 (3)	C7—C8	1.378 (5)
S1—C4	1.772 (3)	C8—H8	0.9300
S2—C10	1.704 (3)	C8—C9	1.374 (5)
S2—C13	1.693 (3)	C9—H9	0.9300
F1—C17	1.362 (3)	C10—C11	1.394 (4)
N1—C1	1.290 (3)	C11—H11	0.9300
N1—C5	1.406 (3)	C11—C12	1.420 (4)
C1—C2	1.506 (4)	C12—H12	0.9300
C1—C10	1.469 (4)	C12—C13	1.346 (5)
C2—H2A	0.9700	C13—H13	0.9300
C2—H2B	0.9700	C14—C15	1.382 (4)
C2—C3	1.525 (4)	C14—C19	1.382 (4)
C3—H3	0.9800	C15—H15	0.9300
C3—C14	1.515 (4)	C15—C16	1.378 (4)
C4—C5	1.405 (4)	C16—H16	0.9300
C4—C9	1.398 (4)	C16—C17	1.362 (4)
C5—C6	1.389 (4)	C17—C18	1.365 (5)
C6—H6	0.9300	C18—H18	0.9300
C6—C7	1.383 (4)	C18—C19	1.388 (4)
C7—H7	0.9300	C19—H19	0.9300
C4—S1—C3	106.11 (12)	C4—C9—H9	119.4
C13—S2—C10	91.98 (16)	C8—C9—C4	121.2 (3)
C1—N1—C5	120.2 (2)	C8—C9—H9	119.4
N1—C1—C2	124.4 (2)	C1—C10—S2	121.1 (2)
N1—C1—C10	117.3 (2)	C11—C10—S2	111.4 (2)
C10—C1—C2	118.3 (2)	C11—C10—C1	127.4 (3)
C1—C2—H2A	109.3	C10—C11—H11	124.5
C1—C2—H2B	109.3	C10—C11—C12	110.9 (3)
C1—C2—C3	111.5 (2)	C12—C11—H11	124.5
H2A—C2—H2B	108.0	C11—C12—H12	123.6
C3—C2—H2A	109.3	C13—C12—C11	112.9 (3)
C3—C2—H2B	109.3	C13—C12—H12	123.6
S1—C3—H3	107.0	S2—C13—H13	123.6
C2—C3—S1	110.59 (18)	C12—C13—S2	112.7 (2)
C2—C3—H3	107.0	C12—C13—H13	123.6
C14—C3—S1	113.15 (18)	C15—C14—C3	122.3 (2)
C14—C3—C2	111.8 (2)	C15—C14—C19	118.1 (3)
C14—C3—H3	107.0	C19—C14—C3	119.6 (2)
C5—C4—S1	123.9 (2)	C14—C15—H15	119.3
C9—C4—S1	116.3 (2)	C16—C15—C14	121.3 (3)
C9—C4—C5	119.0 (3)	C16—C15—H15	119.3
C4—C5—N1	124.6 (2)	C15—C16—H16	120.8
C6—C5—N1	116.4 (2)	C17—C16—C15	118.3 (3)
C6—C5—C4	118.8 (2)	C17—C16—H16	120.8
C5—C6—H6	119.5	F1—C17—C18	117.6 (3)
C7—C6—C5	121.1 (3)	C16—C17—F1	119.5 (3)
C7—C6—H6	119.5	C16—C17—C18	123.0 (3)
C6—C7—H7	119.9	C17—C18—H18	121.2
C8—C7—C6	120.2 (3)	C17—C18—C19	117.6 (3)
C8—C7—H7	119.9	C19—C18—H18	121.2
C7—C8—H8	120.1	C14—C19—C18	121.5 (3)
C9—C8—C7	119.7 (3)	C14—C19—H19	119.3
C9—C8—H8	120.1	C18—C19—H19	119.3
S1—C3—C14—C15	69.3 (3)	C4—S1—C3—C2	17.3 (2)
S1—C3—C14—C19	−112.7 (3)	C4—S1—C3—C14	−109.0 (2)
S1—C4—C5—N1	5.5 (4)	C4—C5—C6—C7	−0.1 (4)
S1—C4—C5—C6	−168.7 (2)	C5—N1—C1—C2	4.2 (4)
S1—C4—C9—C8	168.7 (2)	C5—N1—C1—C10	−176.2 (2)
S2—C10—C11—C12	1.5 (3)	C5—C4—C9—C8	−1.8 (4)
F1—C17—C18—C19	177.5 (3)	C5—C6—C7—C8	−0.1 (5)
N1—C1—C2—C3	−87.2 (3)	C6—C7—C8—C9	−0.7 (5)
N1—C1—C10—S2	−8.3 (4)	C7—C8—C9—C4	1.7 (5)
N1—C1—C10—C11	170.2 (3)	C9—C4—C5—N1	175.3 (3)
N1—C5—C6—C7	−174.8 (3)	C9—C4—C5—C6	1.0 (4)
C1—N1—C5—C4	45.9 (4)	C10—S2—C13—C12	0.0 (3)
C1—N1—C5—C6	−139.7 (3)	C10—C1—C2—C3	93.2 (3)
C1—C2—C3—S1	58.9 (3)	C10—C11—C12—C13	−1.5 (4)
C1—C2—C3—C14	−174.0 (2)	C11—C12—C13—S2	0.8 (4)
C1—C10—C11—C12	−177.2 (3)	C13—S2—C10—C1	177.9 (2)
C2—C1—C10—S2	171.3 (2)	C13—S2—C10—C11	−0.9 (2)
C2—C1—C10—C11	−10.1 (4)	C14—C15—C16—C17	1.3 (4)
C2—C3—C14—C15	−56.3 (3)	C15—C14—C19—C18	1.8 (5)
C2—C3—C14—C19	121.6 (3)	C15—C16—C17—F1	−178.4 (3)
C3—S1—C4—C5	−58.1 (3)	C15—C16—C17—C18	1.4 (5)
C3—S1—C4—C9	131.9 (2)	C16—C17—C18—C19	−2.3 (5)
C3—C14—C15—C16	175.2 (3)	C17—C18—C19—C14	0.7 (5)
C3—C14—C19—C18	−176.2 (3)	C19—C14—C15—C16	−2.8 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···F1i	0.93	2.72	3.322 (4)	123

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18—H18⋯F1i	0.93	2.72	3.322 (4)	123

Symmetry code: (i) .