rac-(3S,4Z)-3-Chloro-4-[2-(3-fluoro­benzyl­idene)hydrazinyl­idene]-1-methyl-3,4-dihydro-1H-2λ⁶,1-benzothia­zine-2,2-dione

Abstract

In the title compound, C₁₆H₁₃ClFN₃O₂S, the dihedral angle between the benzene rings is 4.47 (3)°. The conformation of the thia­zine ring is a half-chair and the Cl atom is in an axial orientation. In the crystal, mol­ecules are linked by C—H⋯F inter­actions, generating C(12) chains propagating in [011]. Aromatic π–π stacking inter­actions [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. (2011a ▶,b ▶). For ring conformations, see: Cremer & Pople (1975 ▶).

Experimental  

Crystal data  

• C₁₆H₁₃ClFN₃O₂S

• M _r = 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) ų

• 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

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −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.

Supplementary Material

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

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

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) .

supplementary crystallographic information

Comment

As part of our ongoing synthetic and structural studies of thiazine derivatives (Shafiq et al., 2012), we now describe the title compound, (I), (Fig. 1).

In (I), the benzene rings A (C1—C6) and B (C10—C15) are planar with r. m. s. deviation of 0.0040 and 0.0012 Å, respectively. The dihedral angle between A/B is 4.47 (3)°. The central group C (N2/N3/C9) is of course planar. The dihedral angle between A/C and B/C is 5.87 (7) and 1.48 (8)°, respectively. The thiazine ring D (C1/C6/N1/S1/C7/C8) is in the half-chair form, with the maximum puckering amplitude (Cremer & Pople, 1975), Q = 0.563 (3) Å. In the crystal, the molecules form chains due to H-bonding of C—H···F type (Table 1, Fig. 2). There exist π–π interactions between CgA···CgBⁱ [i = 1 - x, -y, 1 - z] and CgB···CgAⁱⁱ [ii = 2 - x, -y, 1 - z] at a distance of 3.758 (2) and 3.753 (2) Å, where CgA and CgB are the centroids of benzene rings A and B, respectively.

Experimental

The Schiff base derivative of (4Z)-4-hydrazinylidene-1-methyl-3,4-dihydro -1H-2,1-benzothiazine 2,2-dioxide and 3-flourobenzaldehyde was prepared using the method reported previously (Shafiq et al. 2011b). The chlorination of the schiff base was undertaken using N-chloro succinimide and dibenzoylperoxide (Shafiq et al., 2011a). The crude product of (I) was re-crystallized in ethyl acetate to obtain yellow needles of the title compound.

Refinement

The H-atoms were positioned geometrically (C–H = 0.93–0.96 Å) and refined as riding with U_iso(H) = xU_eq(C), where x = 1.5 for methyl and x = 1.2 for aryl H-atoms.

Figures

Fig. 1.

View of the title compound with displacement ellipsoids drawn at the 50% probability level.

Fig. 2.

Partial packing diagram showing polymeric chains.

Crystal data

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

Data collection

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

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

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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) x, y−1, z−1.