(Z)-3-(3,4-Dimeth-oxy-benzyl-idene)-2,3-dihydro-1,5-benzothia-zepin-4(5H)-one.

In the title compound, C18H17NO3S, the seven-membered thia-zepine ring adopts a slightly distorted sofa conformation. The dihedral angle between the mean plane of the benzothia-zepine ring system and the benzene ring is 5.9 (1)°. The mol-ecular conformation is stabilized by an intra-molecular C-H⋯S hydrogen bond, which generates an S(7) ring motif. In the crystal, N-H⋯O and C-H⋯O hydrogen bonds link inversion-related mol-ecules into dimers, incorporating R 1 (2)(6) and R 2 (2)(8) ring motifs; the acceptor O atom is bifurcated. These dimers are further linked by C-H⋯O hydrogen bonds, forming supra-molecular tapes running along the a axis. These are connected into the three-dimensional architecture by C-H⋯π inter-actions.

Related literature

For the pharmaceutical properties of thia­zepine derivatives, see: Tomascovic et al. (2000 ▶); Rajsner et al. (1971 ▶); Metys et al. (1965 ▶). For related structures, see: Lakshmanan et al. (2012 ▶); Selvakumar et al. (2012 ▶); Murugavel et al. (2013 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C18H17NO3S

M = 327.39

Triclinic,

a = 7.0249 (4) Å

b = 10.7949 (7) Å

c = 10.8826 (7) Å

α = 91.783 (3)°

β = 97.562 (2)°

γ = 108.512 (2)°

V = 773.42 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.22 mm−1

T = 293 K

0.23 × 0.21 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.950, T max = 0.967

14052 measured reflections

3082 independent reflections

2545 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.121

S = 1.06

3082 reflections

210 parameters

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.27 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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813007423/tk5207sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007423/tk5207Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813007423/tk5207Isup3.cml

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

C18H17NO3S	Z = 2
Mr = 327.39	F(000) = 344
Triclinic, P1	Dx = 1.406 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0249 (4) Å	Cell parameters from 3172 reflections
b = 10.7949 (7) Å	θ = 2.0–26.4°
c = 10.8826 (7) Å	µ = 0.22 mm−1
α = 91.783 (3)°	T = 293 K
β = 97.562 (2)°	Block, colourless
γ = 108.512 (2)°	0.23 × 0.21 × 0.15 mm
V = 773.42 (8) Å3

Bruker APEXII CCD diffractometer	3082 independent reflections
Radiation source: fine-focus sealed tube	2545 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
Detector resolution: 10.0 pixels mm-1	θmax = 26.4°, θmin = 2.0°
ω scans	h = −7→8
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −13→13
Tmin = 0.950, Tmax = 0.967	l = −13→13
14052 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0639P)2 + 0.2592P] where P = (Fo2 + 2Fc2)/3
3082 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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.

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 > σ(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
C1	0.4597 (3)	0.39262 (18)	0.80434 (17)	0.0376 (4)
H1A	0.4148	0.3283	0.8637	0.045*
H1B	0.6026	0.4069	0.8021	0.045*
C2	0.0821 (3)	0.24463 (18)	0.69445 (17)	0.0380 (4)
C3	−0.0277 (3)	0.1295 (2)	0.6198 (2)	0.0540 (6)
H3	0.0283	0.1052	0.5540	0.065*
C4	−0.2145 (4)	0.0518 (2)	0.6406 (2)	0.0652 (7)
H4	−0.2850	−0.0234	0.5888	0.078*
C5	−0.2977 (3)	0.0860 (2)	0.7392 (2)	0.0570 (6)
H5	−0.4239	0.0335	0.7550	0.068*
C6	−0.1924 (3)	0.19819 (19)	0.81356 (19)	0.0431 (5)
H6	−0.2490	0.2197	0.8803	0.052*
C7	−0.0035 (3)	0.28146 (16)	0.79304 (16)	0.0329 (4)
C8	0.2416 (2)	0.50716 (17)	0.89652 (15)	0.0301 (4)
C9	0.4315 (2)	0.51723 (17)	0.84463 (15)	0.0313 (4)
C10	0.5649 (3)	0.63650 (18)	0.83993 (16)	0.0353 (4)
H10	0.5326	0.7063	0.8735	0.042*
C11	0.7565 (3)	0.67060 (18)	0.78813 (16)	0.0355 (4)
C12	0.7840 (3)	0.6025 (2)	0.68579 (18)	0.0456 (5)
H12	0.6776	0.5306	0.6474	0.055*
C13	0.9667 (3)	0.6391 (2)	0.63934 (18)	0.0452 (5)
H13	0.9814	0.5914	0.5706	0.054*
C14	1.1265 (3)	0.74520 (18)	0.69391 (17)	0.0364 (4)
C15	1.1008 (3)	0.81763 (18)	0.79546 (18)	0.0385 (4)
C16	0.9179 (3)	0.78086 (18)	0.84029 (18)	0.0387 (4)
H16	0.9014	0.8306	0.9069	0.046*
C17	1.3474 (3)	0.7111 (2)	0.5578 (2)	0.0515 (5)
H17A	1.3216	0.6227	0.5804	0.077*
H17B	1.4859	0.7470	0.5441	0.077*
H17C	1.2584	0.7119	0.4831	0.077*
C18	1.2396 (4)	1.0180 (2)	0.9218 (2)	0.0565 (6)
H18A	1.1360	1.0494	0.8811	0.085*
H18B	1.3648	1.0894	0.9407	0.085*
H18C	1.1998	0.9813	0.9973	0.085*
N1	0.0766 (2)	0.39577 (14)	0.87516 (14)	0.0350 (3)
H1	−0.0038	0.3951	0.9285	0.042*
O1	0.23130 (18)	0.59672 (12)	0.96500 (12)	0.0388 (3)
O2	1.31183 (19)	0.78823 (14)	0.65586 (13)	0.0472 (4)
O3	1.2663 (2)	0.92142 (15)	0.84312 (17)	0.0639 (5)
S1	0.31690 (7)	0.33116 (5)	0.65216 (5)	0.04745 (18)

	U11	U22	U33	U12	U13	U23
C1	0.0290 (9)	0.0432 (10)	0.0405 (10)	0.0104 (8)	0.0101 (7)	−0.0031 (8)
C2	0.0332 (9)	0.0374 (9)	0.0402 (10)	0.0048 (8)	0.0125 (7)	−0.0046 (8)
C3	0.0504 (12)	0.0454 (11)	0.0578 (13)	0.0012 (9)	0.0200 (10)	−0.0176 (10)
C4	0.0557 (14)	0.0474 (13)	0.0768 (17)	−0.0076 (10)	0.0229 (12)	−0.0235 (11)
C5	0.0394 (11)	0.0432 (11)	0.0765 (16)	−0.0072 (9)	0.0224 (10)	−0.0082 (10)
C6	0.0354 (10)	0.0397 (10)	0.0529 (12)	0.0059 (8)	0.0189 (8)	−0.0014 (8)
C7	0.0286 (9)	0.0314 (9)	0.0375 (9)	0.0070 (7)	0.0084 (7)	−0.0007 (7)
C8	0.0266 (8)	0.0357 (9)	0.0274 (8)	0.0078 (7)	0.0075 (6)	0.0004 (7)
C9	0.0253 (8)	0.0399 (9)	0.0274 (8)	0.0082 (7)	0.0066 (6)	−0.0016 (7)
C10	0.0294 (9)	0.0417 (10)	0.0324 (9)	0.0075 (7)	0.0086 (7)	−0.0038 (7)
C11	0.0293 (9)	0.0406 (10)	0.0351 (9)	0.0072 (7)	0.0102 (7)	0.0014 (7)
C12	0.0316 (10)	0.0527 (12)	0.0405 (10)	−0.0037 (8)	0.0099 (8)	−0.0100 (9)
C13	0.0381 (10)	0.0542 (12)	0.0366 (10)	0.0033 (9)	0.0148 (8)	−0.0115 (8)
C14	0.0284 (9)	0.0411 (10)	0.0388 (10)	0.0065 (7)	0.0142 (7)	0.0015 (8)
C15	0.0304 (9)	0.0337 (9)	0.0481 (11)	0.0034 (7)	0.0141 (8)	−0.0038 (8)
C16	0.0356 (10)	0.0360 (9)	0.0435 (10)	0.0066 (8)	0.0175 (8)	−0.0052 (8)
C17	0.0429 (11)	0.0603 (13)	0.0533 (13)	0.0135 (10)	0.0249 (9)	−0.0065 (10)
C18	0.0549 (13)	0.0365 (10)	0.0703 (15)	0.0005 (9)	0.0220 (11)	−0.0138 (10)
N1	0.0284 (7)	0.0387 (8)	0.0366 (8)	0.0058 (6)	0.0151 (6)	−0.0049 (6)
O1	0.0323 (6)	0.0386 (7)	0.0436 (7)	0.0058 (5)	0.0156 (5)	−0.0079 (5)
O2	0.0335 (7)	0.0492 (8)	0.0555 (9)	0.0030 (6)	0.0238 (6)	−0.0091 (6)
O3	0.0391 (8)	0.0495 (8)	0.0898 (12)	−0.0093 (6)	0.0316 (8)	−0.0320 (8)
S1	0.0377 (3)	0.0537 (3)	0.0418 (3)	−0.0013 (2)	0.0190 (2)	−0.0143 (2)

C1—C9	1.482 (2)	C10—H10	0.9300
C1—S1	1.8058 (19)	C11—C12	1.384 (3)
C1—H1A	0.9700	C11—C16	1.399 (3)
C1—H1B	0.9700	C12—C13	1.386 (3)
C2—C3	1.401 (3)	C12—H12	0.9300
C2—C7	1.402 (2)	C13—C14	1.375 (3)
C2—S1	1.7471 (18)	C13—H13	0.9300
C3—C4	1.367 (3)	C14—O2	1.361 (2)
C3—H3	0.9300	C14—C15	1.398 (3)
C4—C5	1.381 (3)	C15—O3	1.361 (2)
C4—H4	0.9300	C15—C16	1.379 (2)
C5—C6	1.372 (3)	C16—H16	0.9300
C5—H5	0.9300	C17—O2	1.428 (2)
C6—C7	1.397 (2)	C17—H17A	0.9600
C6—H6	0.9300	C17—H17B	0.9600
C7—N1	1.413 (2)	C17—H17C	0.9600
C8—O1	1.229 (2)	C18—O3	1.402 (2)
C8—N1	1.368 (2)	C18—H18A	0.9600
C8—C9	1.490 (2)	C18—H18B	0.9600
C9—C10	1.337 (2)	C18—H18C	0.9600
C10—C11	1.470 (2)	N1—H1	0.8600
C9—C1—S1	110.58 (13)	C16—C11—C10	119.12 (16)
C9—C1—H1A	109.5	C11—C12—C13	121.42 (18)
S1—C1—H1A	109.5	C11—C12—H12	119.3
C9—C1—H1B	109.5	C13—C12—H12	119.3
S1—C1—H1B	109.5	C14—C13—C12	120.63 (17)
H1A—C1—H1B	108.1	C14—C13—H13	119.7
C3—C2—C7	118.76 (17)	C12—C13—H13	119.7
C3—C2—S1	115.26 (14)	O2—C14—C13	125.04 (16)
C7—C2—S1	125.97 (14)	O2—C14—C15	115.91 (16)
C4—C3—C2	122.1 (2)	C13—C14—C15	119.05 (16)
C4—C3—H3	118.9	O3—C15—C16	125.11 (17)
C2—C3—H3	118.9	O3—C15—C14	115.09 (15)
C3—C4—C5	119.4 (2)	C16—C15—C14	119.80 (17)
C3—C4—H4	120.3	C15—C16—C11	121.66 (17)
C5—C4—H4	120.3	C15—C16—H16	119.2
C6—C5—C4	119.4 (2)	C11—C16—H16	119.2
C6—C5—H5	120.3	O2—C17—H17A	109.5
C4—C5—H5	120.3	O2—C17—H17B	109.5
C5—C6—C7	122.66 (18)	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
C6—C7—C2	117.63 (16)	H17B—C17—H17C	109.5
C6—C7—N1	114.53 (15)	O3—C18—H18A	109.5
C2—C7—N1	127.83 (16)	O3—C18—H18B	109.5
O1—C8—N1	117.55 (14)	H18A—C18—H18B	109.5
O1—C8—C9	120.94 (15)	O3—C18—H18C	109.5
N1—C8—C9	121.42 (15)	H18A—C18—H18C	109.5
C10—C9—C1	124.92 (16)	H18B—C18—H18C	109.5
C10—C9—C8	118.22 (16)	C8—N1—C7	139.93 (14)
C1—C9—C8	116.85 (15)	C8—N1—H1	110.0
C9—C10—C11	127.81 (17)	C7—N1—H1	110.0
C9—C10—H10	116.1	C14—O2—C17	117.20 (15)
C11—C10—H10	116.1	C15—O3—C18	118.52 (15)
C12—C11—C16	117.39 (16)	C2—S1—C1	99.66 (9)
C12—C11—C10	123.42 (17)
C7—C2—C3—C4	−0.5 (4)	C11—C12—C13—C14	−0.2 (3)
S1—C2—C3—C4	−179.5 (2)	C12—C13—C14—O2	179.52 (19)
C2—C3—C4—C5	−1.0 (4)	C12—C13—C14—C15	−1.4 (3)
C3—C4—C5—C6	0.8 (4)	O2—C14—C15—O3	−0.4 (3)
C4—C5—C6—C7	0.8 (4)	C13—C14—C15—O3	−179.59 (19)
C5—C6—C7—C2	−2.2 (3)	O2—C14—C15—C16	−179.92 (17)
C5—C6—C7—N1	176.7 (2)	C13—C14—C15—C16	0.9 (3)
C3—C2—C7—C6	2.0 (3)	O3—C15—C16—C11	−178.25 (19)
S1—C2—C7—C6	−179.12 (15)	C14—C15—C16—C11	1.2 (3)
C3—C2—C7—N1	−176.80 (19)	C12—C11—C16—C15	−2.7 (3)
S1—C2—C7—N1	2.1 (3)	C10—C11—C16—C15	−179.90 (18)
S1—C1—C9—C10	−100.97 (18)	O1—C8—N1—C7	165.2 (2)
S1—C1—C9—C8	80.36 (17)	C9—C8—N1—C7	−18.2 (3)
O1—C8—C9—C10	−21.0 (2)	C6—C7—N1—C8	−177.9 (2)
N1—C8—C9—C10	162.49 (16)	C2—C7—N1—C8	0.9 (4)
O1—C8—C9—C1	157.79 (16)	C13—C14—O2—C17	−5.1 (3)
N1—C8—C9—C1	−18.8 (2)	C15—C14—O2—C17	175.83 (18)
C1—C9—C10—C11	4.2 (3)	C16—C15—O3—C18	−17.0 (3)
C8—C9—C10—C11	−177.11 (16)	C14—C15—O3—C18	163.5 (2)
C9—C10—C11—C12	34.0 (3)	C3—C2—S1—C1	−145.03 (17)
C9—C10—C11—C16	−149.01 (19)	C7—C2—S1—C1	36.02 (19)
C16—C11—C12—C13	2.2 (3)	C9—C1—S1—C2	−85.92 (14)
C10—C11—C12—C13	179.28 (19)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···S1	0.93	2.76	3.605 (2)	151
N1—H1···O1i	0.86	2.12	2.967 (2)	170
C6—H6···O1i	0.93	2.52	3.318 (2)	144
C5—H5···O3ii	0.93	2.46	3.377 (3)	167
C17—H17C···Cg1iii	0.96	2.84	3.724 (2)	154
C18—H18A···Cg1iv	0.96	2.90	3.841 (3)	166

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯S1	0.93	2.76	3.605 (2)	151
N1—H1⋯O1i	0.86	2.12	2.967 (2)	170
C6—H6⋯O1i	0.93	2.52	3.318 (2)	144
C5—H5⋯O3ii	0.93	2.46	3.377 (3)	167
C17—H17C⋯Cg1iii	0.96	2.84	3.724 (2)	154
C18—H18A⋯Cg1iv	0.96	2.90	3.841 (3)	166

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .