rac-(3S,4Z)-3-Chloro-4-[2-(3-fluoro-benzyl-idene)hydrazinyl-idene]-1-methyl-3,4-dihydro-1H-2λ(6),1-benzothia-zine-2,2-dione.

In the title compound, C(16)H(13)ClFN(3)O(2)S, the dihedral angle between the benzene rings is 4.47 (3)°. The conformation of the thia-zine ring is a half-chair and the Cl atom is in an axial orientation. In the crystal, mol-ecules are linked by C-H⋯F inter-actions, generating C(12) chains propagating in [011]. Aromatic π-π stacking inter-actions [centroid-centroid separations = 3.753 (2) and 3.758 (2) Å] also occur.

Related literature

For a related structure and background references, see: Shafiq et al. (2012 ▶). For further synthetic details, see: Shafiq et al. (2011 ▶). For ring conformations, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C16H13ClFN3O2S

M = 365.80

Triclinic,

a = 7.0072 (3) Å

b = 8.9402 (4) Å

c = 13.3438 (6) Å

α = 98.184 (3)°

β = 90.510 (2)°

γ = 98.389 (3)°

V = 818.19 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.39 mm−1

T = 296 K

0.26 × 0.18 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.930, T max = 0.960

11874 measured reflections

2941 independent reflections

1744 reflections with I > 2σ(I)

R int = 0.065

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.120

S = 1.00

2941 reflections

218 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.32 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; 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, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812021654/hb6778sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812021654/hb6778Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812021654/hb6778Isup3.cml

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

C16H13ClFN3O2S	Z = 2
Mr = 365.80	F(000) = 376
Triclinic, P1	Dx = 1.485 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0072 (3) Å	Cell parameters from 1744 reflections
b = 8.9402 (4) Å	θ = 2.3–25.3°
c = 13.3438 (6) Å	µ = 0.39 mm−1
α = 98.184 (3)°	T = 296 K
β = 90.510 (2)°	Needle, yellow
γ = 98.389 (3)°	0.26 × 0.18 × 0.12 mm
V = 818.19 (6) Å3

Bruker Kappa APEXII CCD diffractometer	2941 independent reflections
Radiation source: fine-focus sealed tube	1744 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
Detector resolution: 8.10 pixels mm-1	θmax = 25.3°, θmin = 2.3°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −10→10
Tmin = 0.930, Tmax = 0.960	l = −16→16
11874 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0478P)2 + 0.0889P] where P = (Fo2 + 2Fc2)/3
2941 reflections	(Δ/σ)max < 0.001
218 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.32 e Å−3

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 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
Cl1	0.49246 (13)	0.08066 (10)	0.23725 (7)	0.0532 (4)
S1	0.86510 (13)	0.02559 (10)	0.15593 (7)	0.0428 (3)
F1	0.8027 (4)	0.4684 (3)	0.88468 (18)	0.0894 (11)
O1	1.0538 (3)	0.0163 (3)	0.19335 (18)	0.0532 (9)
O2	0.8416 (4)	0.1283 (3)	0.08580 (18)	0.0561 (10)
N1	0.7533 (4)	−0.1425 (3)	0.1110 (2)	0.0426 (10)
N2	0.7629 (4)	−0.0292 (3)	0.4293 (2)	0.0459 (11)
N3	0.7744 (4)	0.1263 (3)	0.4676 (2)	0.0483 (11)
C1	0.7272 (4)	−0.2167 (3)	0.2815 (3)	0.0336 (11)
C2	0.7020 (5)	−0.3359 (4)	0.3404 (3)	0.0450 (12)
C3	0.6839 (5)	−0.4857 (4)	0.2968 (3)	0.0516 (16)
C4	0.6917 (5)	−0.5215 (4)	0.1934 (3)	0.0523 (16)
C5	0.7157 (5)	−0.4082 (4)	0.1340 (3)	0.0478 (12)
C6	0.7322 (4)	−0.2558 (4)	0.1761 (3)	0.0365 (12)
C7	0.7362 (4)	0.0683 (4)	0.2675 (2)	0.0369 (12)
C8	0.7431 (4)	−0.0574 (3)	0.3326 (3)	0.0349 (11)
C9	0.7800 (5)	0.1472 (4)	0.5641 (3)	0.0460 (14)
C10	0.7926 (5)	0.2996 (4)	0.6232 (3)	0.0403 (12)
C11	0.7939 (5)	0.3134 (4)	0.7280 (3)	0.0446 (12)
C12	0.8044 (5)	0.4569 (5)	0.7816 (3)	0.0509 (14)
C13	0.8143 (5)	0.5861 (4)	0.7388 (3)	0.0555 (16)
C14	0.8139 (6)	0.5733 (5)	0.6347 (3)	0.0616 (17)
C15	0.8029 (5)	0.4312 (4)	0.5773 (3)	0.0520 (16)
C16	0.6640 (7)	−0.1733 (4)	0.0094 (3)	0.0738 (19)
H2	0.69751	−0.31273	0.41045	0.0537*
H3	0.66630	−0.56307	0.33701	0.0617*
H4	0.68056	−0.62314	0.16378	0.0630*
H5	0.72107	−0.43369	0.06412	0.0575*
H7	0.79712	0.16603	0.30513	0.0445*
H9	0.77593	0.06299	0.59809	0.0550*
H11	0.78773	0.22787	0.76088	0.0531*
H13	0.82112	0.68101	0.77869	0.0670*
H14	0.82110	0.66031	0.60328	0.0737*
H15	0.80241	0.42290	0.50700	0.0627*
H16A	0.73119	−0.24304	−0.03305	0.1104*
H16B	0.67065	−0.07948	−0.01841	0.1104*
H16C	0.53138	−0.21768	0.01300	0.1104*

	U11	U22	U33	U12	U13	U23
Cl1	0.0468 (6)	0.0544 (6)	0.0638 (7)	0.0169 (5)	0.0014 (5)	0.0171 (5)
S1	0.0479 (6)	0.0375 (6)	0.0431 (6)	0.0047 (4)	0.0054 (4)	0.0072 (4)
F1	0.118 (2)	0.096 (2)	0.0487 (17)	0.0188 (16)	0.0047 (15)	−0.0117 (13)
O1	0.0366 (14)	0.0522 (16)	0.0688 (18)	0.0026 (12)	0.0021 (13)	0.0062 (14)
O2	0.0778 (19)	0.0452 (16)	0.0494 (17)	0.0094 (13)	0.0105 (14)	0.0197 (13)
N1	0.0589 (19)	0.0380 (18)	0.0290 (17)	0.0038 (14)	−0.0007 (14)	0.0021 (14)
N2	0.062 (2)	0.0408 (19)	0.0339 (19)	0.0118 (15)	−0.0019 (15)	−0.0016 (14)
N3	0.070 (2)	0.0406 (19)	0.0321 (19)	0.0104 (16)	−0.0009 (16)	−0.0043 (14)
C1	0.0342 (19)	0.031 (2)	0.035 (2)	0.0057 (15)	−0.0041 (16)	0.0025 (16)
C2	0.049 (2)	0.044 (2)	0.042 (2)	0.0071 (18)	−0.0016 (18)	0.0060 (19)
C3	0.059 (3)	0.038 (2)	0.059 (3)	0.0051 (19)	−0.007 (2)	0.014 (2)
C4	0.064 (3)	0.032 (2)	0.059 (3)	0.0044 (19)	−0.007 (2)	0.004 (2)
C5	0.057 (2)	0.044 (2)	0.040 (2)	0.0084 (19)	0.0006 (19)	−0.0031 (19)
C6	0.038 (2)	0.036 (2)	0.035 (2)	0.0062 (16)	−0.0027 (16)	0.0032 (17)
C7	0.040 (2)	0.034 (2)	0.034 (2)	0.0038 (16)	0.0010 (16)	−0.0024 (16)
C8	0.0325 (19)	0.035 (2)	0.036 (2)	0.0037 (15)	−0.0034 (16)	0.0025 (16)
C9	0.048 (2)	0.047 (2)	0.043 (3)	0.0120 (18)	0.0026 (19)	0.0019 (19)
C10	0.041 (2)	0.046 (2)	0.032 (2)	0.0069 (17)	0.0038 (16)	−0.0009 (18)
C11	0.049 (2)	0.047 (2)	0.036 (2)	0.0043 (18)	0.0045 (18)	0.0031 (18)
C12	0.054 (2)	0.066 (3)	0.027 (2)	0.006 (2)	0.0025 (18)	−0.010 (2)
C13	0.055 (3)	0.042 (2)	0.065 (3)	0.007 (2)	0.006 (2)	−0.008 (2)
C14	0.071 (3)	0.056 (3)	0.056 (3)	0.007 (2)	0.003 (2)	0.005 (2)
C15	0.062 (3)	0.053 (3)	0.039 (2)	0.006 (2)	0.0028 (19)	0.002 (2)
C16	0.123 (4)	0.056 (3)	0.039 (3)	0.002 (3)	−0.016 (3)	0.008 (2)

Cl1—C7	1.774 (3)	C10—C11	1.386 (6)
S1—O1	1.427 (2)	C10—C15	1.395 (5)
S1—O2	1.426 (3)	C11—C12	1.369 (6)
S1—N1	1.620 (3)	C12—C13	1.353 (6)
S1—C7	1.772 (3)	C13—C14	1.377 (6)
F1—C12	1.365 (5)	C14—C15	1.378 (6)
N1—C6	1.418 (5)	C2—H2	0.9300
N1—C16	1.461 (5)	C3—H3	0.9300
N2—N3	1.402 (4)	C4—H4	0.9300
N2—C8	1.281 (5)	C5—H5	0.9300
N3—C9	1.274 (5)	C7—H7	0.9800
C1—C2	1.404 (5)	C9—H9	0.9300
C1—C6	1.402 (6)	C11—H11	0.9300
C1—C8	1.477 (4)	C13—H13	0.9300
C2—C3	1.370 (5)	C14—H14	0.9300
C3—C4	1.375 (6)	C15—H15	0.9300
C4—C5	1.365 (5)	C16—H16A	0.9600
C5—C6	1.386 (5)	C16—H16B	0.9600
C7—C8	1.521 (5)	C16—H16C	0.9600
C9—C10	1.464 (5)
O1—S1—O2	119.60 (17)	F1—C12—C13	118.7 (4)
O1—S1—N1	110.77 (16)	C11—C12—C13	124.2 (4)
O1—S1—C7	103.50 (14)	C12—C13—C14	118.3 (4)
O2—S1—N1	108.96 (15)	C13—C14—C15	119.8 (4)
O2—S1—C7	111.18 (16)	C10—C15—C14	120.9 (4)
N1—S1—C7	101.18 (15)	C1—C2—H2	119.00
S1—N1—C6	117.9 (2)	C3—C2—H2	119.00
S1—N1—C16	121.1 (2)	C2—C3—H3	120.00
C6—N1—C16	120.9 (3)	C4—C3—H3	120.00
N3—N2—C8	113.5 (3)	C3—C4—H4	120.00
N2—N3—C9	111.1 (3)	C5—C4—H4	120.00
C2—C1—C6	117.8 (3)	C4—C5—H5	119.00
C2—C1—C8	118.9 (3)	C6—C5—H5	119.00
C6—C1—C8	123.2 (3)	Cl1—C7—H7	109.00
C1—C2—C3	121.3 (4)	S1—C7—H7	109.00
C2—C3—C4	119.9 (3)	C8—C7—H7	109.00
C3—C4—C5	120.2 (3)	N3—C9—H9	119.00
C4—C5—C6	121.1 (4)	C10—C9—H9	119.00
N1—C6—C1	121.4 (3)	C10—C11—H11	121.00
N1—C6—C5	118.9 (3)	C12—C11—H11	121.00
C1—C6—C5	119.7 (3)	C12—C13—H13	121.00
Cl1—C7—S1	110.70 (15)	C14—C13—H13	121.00
Cl1—C7—C8	109.6 (2)	C13—C14—H14	120.00
S1—C7—C8	108.8 (2)	C15—C14—H14	120.00
N2—C8—C1	119.6 (3)	C10—C15—H15	120.00
N2—C8—C7	122.2 (3)	C14—C15—H15	120.00
C1—C8—C7	118.2 (3)	N1—C16—H16A	109.00
N3—C9—C10	122.1 (3)	N1—C16—H16B	109.00
C9—C10—C11	118.9 (3)	N1—C16—H16C	109.00
C9—C10—C15	122.0 (4)	H16A—C16—H16B	110.00
C11—C10—C15	119.0 (3)	H16A—C16—H16C	109.00
C10—C11—C12	117.9 (3)	H16B—C16—H16C	109.00
F1—C12—C11	117.2 (4)
O1—S1—N1—C6	56.5 (3)	C2—C1—C8—C7	−169.8 (3)
O2—S1—N1—C6	−170.0 (2)	C8—C1—C2—C3	179.1 (3)
C7—S1—N1—C6	−52.8 (3)	C6—C1—C2—C3	0.4 (5)
O1—S1—N1—C16	−128.2 (3)	C6—C1—C8—N2	−170.9 (3)
O2—S1—N1—C16	5.4 (3)	C1—C2—C3—C4	0.5 (5)
C7—S1—N1—C16	122.6 (3)	C2—C3—C4—C5	−0.6 (5)
N1—S1—C7—Cl1	−63.9 (2)	C3—C4—C5—C6	−0.1 (5)
O1—S1—C7—C8	−58.3 (2)	C4—C5—C6—N1	−178.8 (3)
O2—S1—C7—C8	172.1 (2)	C4—C5—C6—C1	1.0 (5)
N1—S1—C7—C8	56.5 (2)	Cl1—C7—C8—N2	−97.9 (3)
O1—S1—C7—Cl1	−178.68 (18)	Cl1—C7—C8—C1	82.4 (3)
O2—S1—C7—Cl1	51.7 (2)	S1—C7—C8—N2	141.0 (3)
C16—N1—C6—C5	31.8 (5)	S1—C7—C8—C1	−38.7 (3)
S1—N1—C6—C5	−152.9 (3)	N3—C9—C10—C11	178.6 (3)
S1—N1—C6—C1	27.3 (4)	N3—C9—C10—C15	−1.2 (5)
C16—N1—C6—C1	−148.0 (3)	C9—C10—C11—C12	−179.6 (3)
C8—N2—N3—C9	175.3 (3)	C15—C10—C11—C12	0.3 (5)
N3—N2—C8—C1	−179.5 (3)	C9—C10—C15—C14	179.7 (4)
N3—N2—C8—C7	0.9 (4)	C11—C10—C15—C14	−0.1 (5)
N2—N3—C9—C10	179.9 (3)	C10—C11—C12—F1	179.1 (3)
C2—C1—C6—N1	178.7 (3)	C10—C11—C12—C13	−0.3 (6)
C2—C1—C6—C5	−1.1 (4)	F1—C12—C13—C14	−179.3 (3)
C8—C1—C6—N1	0.0 (4)	C11—C12—C13—C14	0.0 (6)
C8—C1—C6—C5	−179.8 (3)	C12—C13—C14—C15	0.2 (6)
C6—C1—C8—C7	8.9 (4)	C13—C14—C15—C10	−0.2 (6)
C2—C1—C8—N2	10.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···F1i	0.93	2.53	3.442 (5)	167

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯F1i	0.93	2.53	3.442 (5)	167

Symmetry code: (i) .