Crystal structure of (Z)-3-(4-meth-oxy-benzyl-idene)-2,3-di-hydro-benzo[b][1,4]thia-zepin-4(5H)-one.

In the title compound, C17H15NO2S, the two C atoms linking the S and carbonyl C atoms of the seven-membered thia-zepine ring are disordered over two sites, with occupancies of 0.511 (4) and 0.489 (4); both disorder components adopt distorted twist-boat conformations. In the crystal, N-H⋯O and C-H⋯O hydrogen bonds link inverted-related mol-ecules into dimers, incorporating R 1 (2)(6) and R 2 (2)(8) ring motifs; the acceptor carbonyl O atom is bifurcated. These dimers are further linked by C-H⋯O hydrogen bonds, forming supra-molecular tapes running along the a axis.

Related literature

For the pharmaceutical properties of thia­zepin derivatives, see: Lončar-Tomascovic et al. (2000 ▸); Rajsner et al. (1971 ▸); Metys & Metysová (1965 ▸). For related structures, see: Lakshmanan et al. (2012 ▸); Selvakumar et al. (2012 ▸).

Experimental

Crystal data

C17H15NO2S

M = 297.36

Monoclinic,

a = 21.434 (5) Å

b = 5.715 (4) Å

c = 23.870 (5) Å

β = 101.091 (4)°

V = 2869 (2) Å3

Z = 8

Mo Kα radiation

μ = 0.23 mm−1

T = 293 K

0.30 × 0.30 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▸) T min = 0.934, T max = 0.944

17286 measured reflections

4099 independent reflections

2744 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.139

S = 1.03

4099 reflections

210 parameters

4 restraints

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.34 e Å−3

Data collection: APEX2 (Bruker, 2004 ▸); cell refinement: APEX2 and SAINT (Bruker, 2004 ▸); data reduction: SAINT and XPREP (Bruker, 2004 ▸); 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, 2012 ▸); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989014026267/tk5350sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014026267/tk5350Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989014026267/tk5350Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989014026267/tk5350fig1.tif

Mol­ecular structure of the title compound showing displacement ellipsoids at the 30% probability level. H atoms are presented as a small spheres of arbitrary radii.

Click here for additional data file.

via a -x, −y, −z x, 1+y, z . DOI: 10.1107/S2056989014026267/tk5350fig2.tif

Supra­molecular tape formation in the crystal packing of the title compound whereby bifurcated hydrogen bonds link inverted mol­ecules into dimers sustained by N—H⋯O and C—H⋯O (red dashed lines) contacts are linked via C—H⋯O contacts (blue dashed lines) along a axis. [Symmetry code: (i) -x, −y, −z; (ii) x, 1+y, z].

CCDC reference: 1036763

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

C17H15NO2S	F(000) = 1248
Mr = 297.36	Dx = 1.377 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4132 reflections
a = 21.434 (5) Å	θ = 1.7–29.9°
b = 5.715 (4) Å	µ = 0.23 mm−1
c = 23.870 (5) Å	T = 293 K
β = 101.091 (4)°	Block, colourless
V = 2869 (2) Å3	0.30 × 0.30 × 0.25 mm
Z = 8

Bruker APEXII CCD diffractometer	4099 independent reflections
Radiation source: fine-focus sealed tube	2744 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 10.0 pixels mm-1	θmax = 29.9°, θmin = 1.7°
ω scans	h = −30→24
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −7→8
Tmin = 0.934, Tmax = 0.944	l = −33→32
17286 measured 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0647P)2 + 1.1615P] where P = (Fo2 + 2Fc2)/3
4099 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.25 e Å−3
4 restraints	Δρmin = −0.34 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.

Refinement. 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 > 2sigma(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	Occ. (<1)
C2	−0.05513 (8)	0.5769 (3)	0.10567 (7)	0.0516 (4)
C3	−0.09963 (11)	0.7568 (3)	0.10107 (9)	0.0689 (5)
H3	−0.1001	0.8512	0.1327	0.083*
C4	−0.14266 (12)	0.8004 (4)	0.05193 (10)	0.0790 (6)
H4	−0.1718	0.9219	0.0503	0.095*
C5	−0.14211 (10)	0.6629 (4)	0.00527 (10)	0.0722 (5)
H5	−0.1708	0.6906	−0.0286	0.087*
C6	−0.09941 (10)	0.4851 (4)	0.00854 (9)	0.0691 (5)
H6	−0.0996	0.3927	−0.0236	0.083*
C7	−0.05515 (8)	0.4357 (3)	0.05837 (8)	0.0525 (4)
C8	0.03347 (9)	0.1194 (3)	0.08459 (7)	0.0549 (4)
C10	0.10676 (9)	0.0681 (3)	0.17287 (7)	0.0528 (4)
H10A	0.1284	−0.0130	0.1487	0.063*	0.489 (4)
H10B	0.1093	−0.0785	0.1566	0.063*	0.511 (4)
C11	0.14272 (8)	0.0921 (3)	0.23129 (7)	0.0474 (4)
C12	0.13743 (8)	0.2801 (3)	0.26731 (7)	0.0534 (4)
H12	0.1074	0.3957	0.2549	0.064*
C13	0.17552 (8)	0.2999 (3)	0.32082 (7)	0.0525 (4)
H13	0.1710	0.4276	0.3439	0.063*
C14	0.22010 (8)	0.1302 (3)	0.33987 (7)	0.0492 (4)
C15	0.22513 (8)	−0.0627 (3)	0.30585 (8)	0.0551 (4)
H15	0.2542	−0.1806	0.3190	0.066*
C16	0.18736 (8)	−0.0793 (3)	0.25292 (8)	0.0533 (4)
H16	0.1915	−0.2093	0.2305	0.064*
C17	0.26254 (13)	0.3437 (5)	0.42387 (10)	0.0895 (7)
H17A	0.2716	0.4752	0.4017	0.134*
H17B	0.2950	0.3305	0.4576	0.134*
H17C	0.2220	0.3656	0.4346	0.134*
N1	−0.01563 (7)	0.2418 (3)	0.05307 (6)	0.0610 (4)
H1	−0.0258	0.1826	0.0194	0.073*
O1	0.05465 (6)	−0.0461 (2)	0.06174 (5)	0.0605 (3)
O2	0.26115 (6)	0.1372 (2)	0.39107 (6)	0.0691 (4)
S1	−0.00374 (3)	0.55138 (8)	0.17212 (2)	0.06381 (18)
C1A	0.00694 (16)	0.2393 (5)	0.18212 (13)	0.0438 (8)	0.489 (4)
H1A	0.0222	0.2080	0.2224	0.053*	0.489 (4)
H1B	−0.0340	0.1629	0.1710	0.053*	0.489 (4)
C9A	0.05207 (17)	0.1363 (7)	0.14902 (14)	0.0425 (8)	0.489 (4)
C1B	0.06528 (16)	0.4832 (6)	0.14859 (14)	0.0529 (9)	0.511 (4)
H1C	0.0661	0.5669	0.1134	0.063*	0.511 (4)
H1D	0.1016	0.5338	0.1768	0.063*	0.511 (4)
C9B	0.07040 (18)	0.2265 (6)	0.13852 (15)	0.0467 (8)	0.511 (4)

	U11	U22	U33	U12	U13	U23
C2	0.0612 (10)	0.0418 (8)	0.0559 (9)	−0.0078 (7)	0.0218 (8)	−0.0015 (7)
C3	0.0945 (15)	0.0501 (10)	0.0679 (12)	0.0085 (10)	0.0301 (11)	0.0005 (9)
C4	0.0937 (16)	0.0612 (12)	0.0861 (15)	0.0218 (11)	0.0275 (13)	0.0105 (11)
C5	0.0695 (12)	0.0685 (13)	0.0761 (13)	0.0072 (10)	0.0079 (10)	0.0050 (11)
C6	0.0674 (12)	0.0676 (12)	0.0677 (12)	0.0064 (10)	0.0018 (9)	−0.0141 (10)
C7	0.0505 (9)	0.0505 (9)	0.0570 (9)	−0.0039 (7)	0.0117 (7)	−0.0085 (7)
C8	0.0606 (10)	0.0570 (10)	0.0470 (9)	0.0012 (8)	0.0105 (8)	−0.0085 (7)
C10	0.0680 (11)	0.0419 (8)	0.0494 (9)	−0.0073 (8)	0.0134 (8)	−0.0044 (7)
C11	0.0530 (9)	0.0431 (8)	0.0481 (8)	−0.0056 (7)	0.0147 (7)	−0.0008 (6)
C12	0.0564 (10)	0.0456 (9)	0.0562 (9)	0.0089 (7)	0.0060 (8)	−0.0005 (7)
C13	0.0556 (10)	0.0487 (9)	0.0530 (9)	0.0055 (7)	0.0097 (7)	−0.0071 (7)
C14	0.0464 (8)	0.0509 (9)	0.0514 (9)	0.0014 (7)	0.0122 (7)	0.0047 (7)
C15	0.0538 (10)	0.0464 (9)	0.0658 (11)	0.0106 (7)	0.0135 (8)	0.0047 (8)
C16	0.0601 (10)	0.0418 (8)	0.0614 (10)	0.0026 (7)	0.0200 (8)	−0.0054 (7)
C17	0.1079 (18)	0.0866 (16)	0.0624 (12)	0.0135 (14)	−0.0125 (12)	−0.0123 (12)
N1	0.0660 (9)	0.0634 (9)	0.0499 (8)	0.0091 (7)	0.0020 (7)	−0.0183 (7)
O1	0.0781 (8)	0.0546 (7)	0.0481 (7)	0.0079 (6)	0.0104 (6)	−0.0085 (5)
O2	0.0680 (8)	0.0720 (9)	0.0597 (8)	0.0116 (7)	−0.0064 (6)	0.0002 (7)
S1	0.0906 (4)	0.0514 (3)	0.0512 (3)	−0.0002 (2)	0.0179 (2)	−0.00693 (19)
C1A	0.0543 (18)	0.0415 (16)	0.0383 (15)	−0.0025 (13)	0.0156 (13)	−0.0022 (12)
C9A	0.048 (2)	0.0385 (18)	0.0434 (17)	−0.0072 (15)	0.0143 (15)	−0.0046 (14)
C1B	0.063 (2)	0.0443 (17)	0.0482 (17)	−0.0116 (14)	0.0023 (15)	0.0032 (13)
C9B	0.0474 (19)	0.0451 (19)	0.0477 (18)	−0.0094 (15)	0.0093 (15)	−0.0068 (15)

C2—C7	1.388 (2)	C12—C13	1.382 (2)
C2—C3	1.392 (3)	C12—H12	0.9300
C2—S1	1.7545 (19)	C13—C14	1.376 (2)
C3—C4	1.368 (3)	C13—H13	0.9300
C3—H3	0.9300	C14—O2	1.362 (2)
C4—C5	1.365 (3)	C14—C15	1.386 (2)
C4—H4	0.9300	C15—C16	1.367 (2)
C5—C6	1.360 (3)	C15—H15	0.9300
C5—H5	0.9300	C16—H16	0.9300
C6—C7	1.400 (3)	C17—O2	1.413 (3)
C6—H6	0.9300	C17—H17A	0.9600
C7—N1	1.415 (2)	C17—H17B	0.9600
C8—O1	1.222 (2)	C17—H17C	0.9600
C8—N1	1.363 (2)	N1—H1	0.8600
C8—C9B	1.505 (4)	S1—C1B	1.725 (3)
C8—C9A	1.516 (4)	S1—C1A	1.808 (3)
C10—C9A	1.262 (4)	C1A—C9A	1.484 (4)
C10—C9B	1.361 (4)	C1A—H1A	0.9700
C10—C11	1.464 (2)	C1A—H1B	0.9700
C10—H10A	0.9300	C1B—C9B	1.494 (4)
C10—H10B	0.9300	C1B—H1C	0.9700
C11—C12	1.395 (2)	C1B—H1D	0.9700
C11—C16	1.397 (2)
C7—C2—C3	118.18 (18)	C12—C13—H13	120.1
C7—C2—S1	126.08 (14)	O2—C14—C13	124.28 (16)
C3—C2—S1	115.74 (14)	O2—C14—C15	116.08 (15)
C4—C3—C2	122.73 (19)	C13—C14—C15	119.64 (16)
C4—C3—H3	118.6	C16—C15—C14	119.87 (15)
C2—C3—H3	118.6	C16—C15—H15	120.1
C5—C4—C3	119.0 (2)	C14—C15—H15	120.1
C5—C4—H4	120.5	C15—C16—C11	122.34 (16)
C3—C4—H4	120.5	C15—C16—H16	118.8
C6—C5—C4	119.7 (2)	C11—C16—H16	118.8
C6—C5—H5	120.2	O2—C17—H17A	109.5
C4—C5—H5	120.2	O2—C17—H17B	109.5
C5—C6—C7	122.6 (2)	H17A—C17—H17B	109.5
C5—C6—H6	118.7	O2—C17—H17C	109.5
C7—C6—H6	118.7	H17A—C17—H17C	109.5
C2—C7—C6	117.89 (17)	H17B—C17—H17C	109.5
C2—C7—N1	128.43 (17)	C8—N1—C7	139.85 (15)
C6—C7—N1	113.67 (16)	C8—N1—H1	110.1
O1—C8—N1	117.68 (15)	C7—N1—H1	110.1
O1—C8—C9B	121.1 (2)	C14—O2—C17	117.57 (15)
N1—C8—C9B	119.10 (19)	C1B—S1—C2	98.80 (12)
O1—C8—C9A	117.03 (19)	C1B—S1—C1A	74.06 (15)
N1—C8—C9A	123.48 (18)	C2—S1—C1A	104.06 (12)
C9B—C8—C9A	27.63 (14)	C9A—C1A—S1	113.6 (2)
C9A—C10—C9B	31.63 (17)	C9A—C1A—H1A	108.8
C9A—C10—C11	132.4 (2)	S1—C1A—H1A	108.8
C9B—C10—C11	130.31 (19)	C9A—C1A—H1B	108.8
C9A—C10—H10A	113.8	S1—C1A—H1B	108.8
C9B—C10—H10A	104.7	H1A—C1A—H1B	107.7
C11—C10—H10A	113.8	C10—C9A—C1A	121.8 (3)
C9A—C10—H10B	102.4	C10—C9A—C8	118.6 (2)
C9B—C10—H10B	114.8	C1A—C9A—C8	119.6 (3)
C11—C10—H10B	114.9	C9B—C1B—S1	111.6 (2)
H10A—C10—H10B	38.2	C9B—C1B—H1C	109.3
C12—C11—C16	116.35 (16)	S1—C1B—H1C	109.3
C12—C11—C10	124.67 (15)	C9B—C1B—H1D	109.3
C16—C11—C10	118.94 (15)	S1—C1B—H1D	109.3
C13—C12—C11	121.95 (16)	H1C—C1B—H1D	108.0
C13—C12—H12	119.0	C10—C9B—C1B	127.4 (3)
C11—C12—H12	119.0	C10—C9B—C8	113.0 (2)
C14—C13—C12	119.80 (16)	C1B—C9B—C8	119.6 (3)
C14—C13—H13	120.1
C7—C2—C3—C4	−0.6 (3)	C7—C2—S1—C1B	39.04 (18)
S1—C2—C3—C4	179.50 (17)	C3—C2—S1—C1B	−141.03 (17)
C2—C3—C4—C5	−0.1 (3)	C7—C2—S1—C1A	−36.62 (18)
C3—C4—C5—C6	0.5 (3)	C3—C2—S1—C1A	143.31 (16)
C4—C5—C6—C7	−0.1 (4)	C1B—S1—C1A—C9A	−17.3 (2)
C3—C2—C7—C6	0.9 (3)	C2—S1—C1A—C9A	78.0 (2)
S1—C2—C7—C6	−179.14 (14)	C9B—C10—C9A—C1A	−109.5 (6)
C3—C2—C7—N1	−178.87 (18)	C11—C10—C9A—C1A	−8.6 (6)
S1—C2—C7—N1	1.1 (3)	C9B—C10—C9A—C8	68.3 (4)
C5—C6—C7—C2	−0.6 (3)	C11—C10—C9A—C8	169.3 (2)
C5—C6—C7—N1	179.2 (2)	S1—C1A—C9A—C10	107.7 (4)
C9A—C10—C11—C12	−30.8 (4)	S1—C1A—C9A—C8	−70.1 (4)
C9B—C10—C11—C12	11.7 (4)	O1—C8—C9A—C10	34.1 (4)
C9A—C10—C11—C16	151.4 (3)	N1—C8—C9A—C10	−161.6 (3)
C9B—C10—C11—C16	−166.1 (3)	C9B—C8—C9A—C10	−71.9 (4)
C16—C11—C12—C13	1.9 (2)	O1—C8—C9A—C1A	−148.0 (3)
C10—C11—C12—C13	−175.93 (16)	N1—C8—C9A—C1A	16.3 (4)
C11—C12—C13—C14	−0.2 (3)	C9B—C8—C9A—C1A	105.9 (6)
C12—C13—C14—O2	177.88 (16)	C2—S1—C1B—C9B	−85.8 (2)
C12—C13—C14—C15	−1.9 (3)	C1A—S1—C1B—C9B	16.4 (2)
O2—C14—C15—C16	−177.57 (15)	C9A—C10—C9B—C1B	118.0 (6)
C13—C14—C15—C16	2.2 (3)	C11—C10—C9B—C1B	10.1 (6)
C14—C15—C16—C11	−0.4 (3)	C9A—C10—C9B—C8	−63.2 (4)
C12—C11—C16—C15	−1.6 (2)	C11—C10—C9B—C8	−171.13 (19)
C10—C11—C16—C15	176.40 (16)	S1—C1B—C9B—C10	−102.3 (4)
O1—C8—N1—C7	−179.9 (2)	S1—C1B—C9B—C8	79.0 (4)
C9B—C8—N1—C7	−16.1 (4)	O1—C8—C9B—C10	−32.2 (4)
C9A—C8—N1—C7	15.9 (4)	N1—C8—C9B—C10	164.6 (2)
C2—C7—N1—C8	−1.1 (4)	C9A—C8—C9B—C10	57.2 (4)
C6—C7—N1—C8	179.1 (2)	O1—C8—C9B—C1B	146.6 (3)
C13—C14—O2—C17	−7.0 (3)	N1—C8—C9B—C1B	−16.6 (4)
C15—C14—O2—C17	172.7 (2)	C9A—C8—C9B—C1B	−123.9 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.86	2.07	2.9291 (18)	177
C6—H6···O1i	0.93	2.45	3.263 (3)	146
C1B—H1C···O1ii	0.97	2.52	3.377 (4)	147

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1O1i	0.86	2.07	2.9291(18)	177
C6H6O1i	0.93	2.45	3.263(3)	146
C1BH1CO1ii	0.97	2.52	3.377(4)	147

Symmetry codes: (i) ; (ii) .