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

In the title compound, C16H13Cl2N3O2S, the dihedral angle between the aromatic rings is 6.62 (2)° and the C=N-N=C torsion angle is 176.2 (4)°. The thia-zine ring shows an envelope conformation, with the S atom displaced by 0.633 (6) Å from the mean plane of the other five atoms (r.m.s. deviation = 0.037 Å). The Cl atom is an an axial conformation and is displaced by 2.015 (6) Å from the thia-zine ring plane. In the crystal, mol-ecules are linked by C-H⋯O inter-actions, generating a three-dimensional network. Very weak aromatic π-π stacking inter-actions [centroid-centroid separations = 3.928 (2) Å] are also observed.

Related literature

For background to benzothia­zines, see: Misu & Togo (2003 ▶); Harmata et al. (2006 ▶). For the synthesis and biological activity of the title compound and related materials, see: Ahmad et al. (2010a ▶); Shafiq et al. (2011a ▶). For further synthetic details, see: Shafiq et al. (2011b ▶). For related structures, see: Ahmad et al. (2010b ▶); Shafiq et al. (2011c ▶, 2013 ▶).

Experimental

Crystal data

C16H13Cl2N3O2S

M = 382.25

Monoclinic,

a = 12.309 (2) Å

b = 17.189 (3) Å

c = 8.1837 (13) Å

β = 101.632 (8)°

V = 1695.9 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.52 mm−1

T = 296 K

0.28 × 0.16 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.868, T max = 0.931

13580 measured reflections

3319 independent reflections

1736 reflections with I > 2σ(I)

R int = 0.076

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.140

S = 1.00

3319 reflections

218 parameters

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.33 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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, 2012 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813004443/im2417sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813004443/im2417Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813004443/im2417Isup3.cml

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

C16H13Cl2N3O2S	F(000) = 784
Mr = 382.25	Dx = 1.497 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 225 reflections
a = 12.309 (2) Å	θ = 3.7–22.3°
b = 17.189 (3) Å	µ = 0.52 mm−1
c = 8.1837 (13) Å	T = 296 K
β = 101.632 (8)°	Block, yellow
V = 1695.9 (5) Å3	0.28 × 0.16 × 0.14 mm
Z = 4

Bruker APEXII CCD diffractometer	3319 independent reflections
Radiation source: fine-focus sealed tube	1736 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.076
ω scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −15→15
Tmin = 0.868, Tmax = 0.931	k = −21→21
13580 measured reflections	l = −10→9

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.047P)2 + 0.7016P] where P = (Fo2 + 2Fc2)/3
3319 reflections	(Δ/σ)max < 0.001
218 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.33 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	0.2793 (4)	0.0825 (2)	0.2790 (5)	0.0443 (10)
C2	0.3546 (4)	0.0531 (2)	0.4159 (5)	0.0562 (12)
H2	0.4291	0.0496	0.4103	0.067*
C3	0.3216 (5)	0.0291 (3)	0.5591 (6)	0.0754 (16)
H3	0.3733	0.0100	0.6489	0.090*
C4	0.2111 (6)	0.0339 (3)	0.5677 (6)	0.0820 (18)
H4	0.1879	0.0176	0.6635	0.098*
C5	0.1353 (5)	0.0624 (3)	0.4352 (7)	0.0736 (15)
H5	0.0609	0.0652	0.4421	0.088*
C6	0.1678 (4)	0.0875 (2)	0.2903 (5)	0.0534 (11)
C7	−0.0133 (4)	0.1564 (3)	0.1866 (7)	0.0877 (17)
H7A	−0.0670	0.1177	0.2001	0.132*
H7B	−0.0435	0.1892	0.0936	0.132*
H7C	0.0046	0.1874	0.2861	0.132*
C8	0.2436 (3)	0.1500 (2)	−0.0046 (5)	0.0456 (10)
H8	0.2703	0.1445	−0.1090	0.055*
C9	0.3205 (3)	0.1070 (2)	0.1305 (4)	0.0402 (9)
C10	0.5527 (3)	0.1066 (2)	−0.0255 (5)	0.0460 (10)
H10	0.5968	0.0836	0.0677	0.055*
C11	0.6032 (3)	0.1273 (2)	−0.1647 (5)	0.0404 (9)
C12	0.7137 (3)	0.1108 (2)	−0.1598 (5)	0.0511 (11)
H12	0.7557	0.0875	−0.0653	0.061*
C13	0.7630 (3)	0.1285 (2)	−0.2933 (6)	0.0551 (12)
H13	0.8374	0.1172	−0.2886	0.066*
C14	0.7011 (4)	0.1626 (2)	−0.4315 (5)	0.0508 (11)
C15	0.5919 (4)	0.1809 (2)	−0.4393 (5)	0.0550 (11)
H15	0.5509	0.2047	−0.5341	0.066*
C16	0.5430 (3)	0.1640 (2)	−0.3062 (5)	0.0498 (11)
H16	0.4691	0.1772	−0.3108	0.060*
S1	0.10908 (9)	0.10838 (7)	−0.03153 (14)	0.0548 (3)
N1	0.0871 (3)	0.1183 (2)	0.1564 (5)	0.0598 (10)
N2	0.4212 (3)	0.09167 (19)	0.1225 (4)	0.0493 (9)
N3	0.4512 (3)	0.11839 (19)	−0.0247 (4)	0.0504 (9)
O1	0.0296 (2)	0.1538 (2)	−0.1431 (4)	0.0787 (10)
O2	0.1256 (2)	0.02920 (17)	−0.0680 (3)	0.0573 (8)
Cl1	0.23868 (10)	0.25052 (6)	0.04375 (17)	0.0757 (4)
Cl2	0.76214 (12)	0.18282 (8)	−0.60081 (17)	0.0859 (5)

	U11	U22	U33	U12	U13	U23
C1	0.059 (3)	0.038 (2)	0.039 (2)	−0.009 (2)	0.015 (2)	−0.0026 (18)
C2	0.076 (3)	0.053 (3)	0.040 (2)	−0.012 (2)	0.013 (2)	−0.004 (2)
C3	0.120 (5)	0.067 (3)	0.039 (3)	−0.023 (3)	0.016 (3)	0.000 (2)
C4	0.151 (6)	0.056 (3)	0.051 (3)	−0.026 (4)	0.050 (4)	−0.009 (3)
C5	0.100 (4)	0.058 (3)	0.080 (4)	−0.017 (3)	0.057 (3)	−0.011 (3)
C6	0.072 (3)	0.038 (2)	0.057 (3)	−0.012 (2)	0.030 (3)	−0.011 (2)
C7	0.062 (3)	0.093 (4)	0.115 (4)	0.006 (3)	0.036 (3)	−0.032 (3)
C8	0.045 (3)	0.046 (2)	0.047 (2)	−0.0027 (19)	0.012 (2)	0.0048 (19)
C9	0.048 (3)	0.035 (2)	0.039 (2)	−0.006 (2)	0.0107 (19)	−0.0015 (18)
C10	0.048 (3)	0.044 (2)	0.046 (2)	0.008 (2)	0.009 (2)	0.0055 (19)
C11	0.036 (2)	0.040 (2)	0.045 (2)	−0.0033 (18)	0.0075 (19)	−0.0003 (18)
C12	0.041 (2)	0.053 (3)	0.058 (3)	0.005 (2)	0.005 (2)	0.001 (2)
C13	0.034 (2)	0.051 (3)	0.082 (3)	−0.001 (2)	0.016 (2)	−0.008 (2)
C14	0.057 (3)	0.040 (2)	0.061 (3)	−0.004 (2)	0.026 (2)	−0.001 (2)
C15	0.055 (3)	0.054 (3)	0.058 (3)	0.004 (2)	0.018 (2)	0.010 (2)
C16	0.037 (2)	0.055 (3)	0.058 (3)	0.000 (2)	0.012 (2)	0.004 (2)
S1	0.0448 (7)	0.0606 (7)	0.0593 (7)	−0.0038 (6)	0.0111 (5)	0.0011 (6)
N1	0.053 (2)	0.064 (2)	0.071 (2)	0.002 (2)	0.032 (2)	−0.003 (2)
N2	0.053 (2)	0.058 (2)	0.0383 (19)	0.0034 (18)	0.0119 (17)	0.0118 (16)
N3	0.045 (2)	0.063 (2)	0.045 (2)	0.0035 (18)	0.0116 (16)	0.0084 (18)
O1	0.0463 (19)	0.094 (3)	0.088 (2)	0.0067 (18)	−0.0040 (18)	0.017 (2)
O2	0.0593 (19)	0.0633 (19)	0.0498 (17)	−0.0074 (16)	0.0119 (15)	−0.0139 (15)
Cl1	0.0765 (9)	0.0449 (6)	0.1015 (10)	−0.0031 (6)	0.0077 (7)	0.0103 (6)
Cl2	0.1003 (11)	0.0762 (9)	0.1001 (10)	0.0026 (8)	0.0653 (9)	0.0138 (8)

C1—C6	1.396 (6)	C9—N2	1.281 (5)
C1—C2	1.397 (5)	C10—N3	1.267 (5)
C1—C9	1.470 (5)	C10—C11	1.448 (5)
C2—C3	1.378 (6)	C10—H10	0.9300
C2—H2	0.9300	C11—C12	1.381 (5)
C3—C4	1.379 (7)	C11—C16	1.394 (5)
C3—H3	0.9300	C12—C13	1.387 (6)
C4—C5	1.371 (7)	C12—H12	0.9300
C4—H4	0.9300	C13—C14	1.363 (5)
C5—C6	1.394 (6)	C13—H13	0.9300
C5—H5	0.9300	C14—C15	1.369 (5)
C6—N1	1.425 (5)	C14—Cl2	1.739 (4)
C7—N1	1.464 (5)	C15—C16	1.378 (5)
C7—H7A	0.9600	C15—H15	0.9300
C7—H7B	0.9600	C16—H16	0.9300
C7—H7C	0.9600	S1—O2	1.417 (3)
C8—C9	1.498 (5)	S1—O1	1.428 (3)
C8—Cl1	1.776 (4)	S1—N1	1.623 (4)
C8—S1	1.776 (4)	N2—N3	1.406 (4)
C8—H8	0.9800
C6—C1—C2	118.1 (4)	N3—C10—C11	123.0 (4)
C6—C1—C9	123.0 (4)	N3—C10—H10	118.5
C2—C1—C9	118.9 (4)	C11—C10—H10	118.5
C3—C2—C1	121.9 (5)	C12—C11—C16	118.2 (4)
C3—C2—H2	119.0	C12—C11—C10	120.2 (4)
C1—C2—H2	119.0	C16—C11—C10	121.6 (4)
C2—C3—C4	119.2 (5)	C11—C12—C13	121.1 (4)
C2—C3—H3	120.4	C11—C12—H12	119.4
C4—C3—H3	120.4	C13—C12—H12	119.4
C5—C4—C3	120.1 (5)	C14—C13—C12	119.2 (4)
C5—C4—H4	119.9	C14—C13—H13	120.4
C3—C4—H4	119.9	C12—C13—H13	120.4
C4—C5—C6	121.2 (5)	C13—C14—C15	121.1 (4)
C4—C5—H5	119.4	C13—C14—Cl2	119.2 (3)
C6—C5—H5	119.4	C15—C14—Cl2	119.6 (4)
C5—C6—C1	119.5 (5)	C14—C15—C16	119.7 (4)
C5—C6—N1	119.6 (4)	C14—C15—H15	120.1
C1—C6—N1	120.9 (4)	C16—C15—H15	120.1
N1—C7—H7A	109.5	C15—C16—C11	120.6 (4)
N1—C7—H7B	109.5	C15—C16—H16	119.7
H7A—C7—H7B	109.5	C11—C16—H16	119.7
N1—C7—H7C	109.5	O2—S1—O1	119.9 (2)
H7A—C7—H7C	109.5	O2—S1—N1	111.05 (18)
H7B—C7—H7C	109.5	O1—S1—N1	108.9 (2)
C9—C8—Cl1	111.1 (3)	O2—S1—C8	104.09 (18)
C9—C8—S1	109.1 (3)	O1—S1—C8	111.11 (19)
Cl1—C8—S1	110.3 (2)	N1—S1—C8	99.76 (19)
C9—C8—H8	108.7	C6—N1—C7	121.2 (4)
Cl1—C8—H8	108.7	C6—N1—S1	117.8 (3)
S1—C8—H8	108.7	C7—N1—S1	121.0 (3)
N2—C9—C1	118.8 (4)	C9—N2—N3	113.6 (3)
N2—C9—C8	122.5 (3)	C10—N3—N2	112.4 (3)
C1—C9—C8	118.6 (4)
C6—C1—C2—C3	0.1 (6)	C13—C14—C15—C16	−0.6 (6)
C9—C1—C2—C3	−180.0 (4)	Cl2—C14—C15—C16	179.1 (3)
C1—C2—C3—C4	0.3 (7)	C14—C15—C16—C11	−1.0 (6)
C2—C3—C4—C5	−0.3 (7)	C12—C11—C16—C15	2.1 (6)
C3—C4—C5—C6	−0.3 (7)	C10—C11—C16—C15	−178.0 (4)
C4—C5—C6—C1	0.7 (6)	C9—C8—S1—O2	−57.3 (3)
C4—C5—C6—N1	−178.7 (4)	Cl1—C8—S1—O2	−179.68 (19)
C2—C1—C6—C5	−0.6 (6)	C9—C8—S1—O1	172.3 (3)
C9—C1—C6—C5	179.5 (4)	Cl1—C8—S1—O1	49.9 (3)
C2—C1—C6—N1	178.8 (3)	C9—C8—S1—N1	57.4 (3)
C9—C1—C6—N1	−1.1 (6)	Cl1—C8—S1—N1	−64.9 (2)
C6—C1—C9—N2	−171.5 (4)	C5—C6—N1—C7	27.6 (6)
C2—C1—C9—N2	8.6 (5)	C1—C6—N1—C7	−151.8 (4)
C6—C1—C9—C8	9.5 (5)	C5—C6—N1—S1	−151.3 (3)
C2—C1—C9—C8	−170.4 (3)	C1—C6—N1—S1	29.3 (5)
Cl1—C8—C9—N2	−96.8 (4)	O2—S1—N1—C6	55.3 (3)
S1—C8—C9—N2	141.3 (3)	O1—S1—N1—C6	−170.5 (3)
Cl1—C8—C9—C1	82.1 (4)	C8—S1—N1—C6	−54.0 (3)
S1—C8—C9—C1	−39.7 (4)	O2—S1—N1—C7	−123.6 (4)
N3—C10—C11—C12	−178.1 (4)	O1—S1—N1—C7	10.6 (4)
N3—C10—C11—C16	1.9 (6)	C8—S1—N1—C7	127.1 (4)
C16—C11—C12—C13	−1.6 (6)	C1—C9—N2—N3	−179.5 (3)
C10—C11—C12—C13	178.5 (4)	C8—C9—N2—N3	−0.6 (5)
C11—C12—C13—C14	0.0 (6)	C11—C10—N3—N2	178.6 (3)
C12—C13—C14—C15	1.2 (6)	C9—N2—N3—C10	176.2 (4)
C12—C13—C14—Cl2	−178.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2i	0.93	2.48	3.356 (6)	158
C12—H12···O2ii	0.93	2.59	3.419 (5)	149
C13—H13···O1iii	0.93	2.50	3.293 (5)	143

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O2i	0.93	2.48	3.356 (6)	158
C12—H12⋯O2ii	0.93	2.59	3.419 (5)	149
C13—H13⋯O1iii	0.93	2.50	3.293 (5)	143

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