6-Bromo-1-methyl-4-[2-(4-nitro-benzyl-idene)hydrazin-1-yl-idene]-2,2-dioxo-3,4-dihydro-1H-2λ(6),1-benzothia-zine.

In the title compound, C(16)H(13)BrN(4)O(4)S, the dihedral angle between the aromatic rings is 4.1 (2)° and the C=N-N=C torsion angle is 175.5 (3)°. The nitro group is almost coplanar with the benzene ring to which it is attached [dihedral angle = 2.9 (7)°]. The thia-zine ring has an S-envelope conformation with the S atom displaced by 0.819 (3) Å from the mean plane of the other five atoms (r.m.s. deviation = 0.017 Å). In the crystal, C-H⋯O inter-actions link the mol-ecules and weak aromatic π-π stacking [centroid-centroid separation = 3.874 (2) Å] is also observed.

Related literature

For the synthesis and biological activity of the title compound and related materials, see: Shafiq, Zia-ur-Rehman et al. (2011 ▶). For related structures, see: Shafiq, Khan et al. (2011 ▶); Shafiq, Harrison et al. (2012 ▶).

Experimental

Crystal data

C16H13BrN4O4S

M = 437.27

Triclinic,

a = 8.2772 (4) Å

b = 9.0572 (4) Å

c = 12.6868 (6) Å

α = 87.132 (4)°

β = 70.976 (3)°

γ = 75.098 (2)°

V = 868.32 (7) Å3

Z = 2

Mo Kα radiation

μ = 2.52 mm−1

T = 296 K

0.36 × 0.09 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.464, T max = 0.843

17474 measured reflections

4251 independent reflections

2484 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.106

S = 1.00

4251 reflections

236 parameters

H-atom parameters constrained

Δρmax = 0.58 e Å−3

Δρmin = −0.40 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 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812035374/pv2578sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812035374/pv2578Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812035374/pv2578Isup3.cml

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

C16H13BrN4O4S	Z = 2
Mr = 437.27	F(000) = 440
Triclinic, P1	Dx = 1.672 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2772 (4) Å	Cell parameters from 4062 reflections
b = 9.0572 (4) Å	θ = 2.3–22.1°
c = 12.6868 (6) Å	µ = 2.52 mm−1
α = 87.132 (4)°	T = 296 K
β = 70.976 (3)°	Needle, yellow
γ = 75.098 (2)°	0.36 × 0.09 × 0.07 mm
V = 868.32 (7) Å3

Bruker APEXII CCD diffractometer	4251 independent reflections
Radiation source: fine-focus sealed tube	2484 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
ω scans	θmax = 28.4°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −11→11
Tmin = 0.464, Tmax = 0.843	k = −12→12
17474 measured reflections	l = −16→16

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0415P)2 + 0.5116P] where P = (Fo2 + 2Fc2)/3
4251 reflections	(Δ/σ)max = 0.001
236 parameters	Δρmax = 0.58 e Å−3
0 restraints	Δρmin = −0.40 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	0.8000 (4)	0.2966 (4)	0.3910 (3)	0.0429 (8)
C2	0.8376 (5)	0.4239 (4)	0.4267 (3)	0.0591 (10)
H2	0.8240	0.4365	0.5017	0.071*
C3	0.8940 (5)	0.5298 (4)	0.3531 (3)	0.0516 (9)
H3	0.9165	0.6146	0.3784	0.062*
C4	0.9175 (4)	0.5116 (3)	0.2422 (3)	0.0443 (8)
C5	0.8801 (4)	0.3880 (3)	0.2041 (3)	0.0385 (7)
H5	0.8956	0.3769	0.1287	0.046*
C6	0.8192 (4)	0.2795 (3)	0.2783 (2)	0.0371 (7)
C7	0.7760 (4)	0.1511 (3)	0.2351 (2)	0.0336 (7)
C8	0.7034 (4)	0.0381 (4)	0.3145 (2)	0.0438 (8)
H8A	0.7315	−0.0590	0.2750	0.053*
H8B	0.5757	0.0744	0.3446	0.053*
C9	0.6400 (6)	0.2323 (5)	0.5848 (3)	0.0799 (13)
H9A	0.7166	0.2499	0.6229	0.120*
H9B	0.5874	0.1518	0.6195	0.120*
H9C	0.5488	0.3242	0.5886	0.120*
C10	0.7637 (4)	0.0248 (3)	−0.0055 (3)	0.0390 (7)
H10	0.8022	0.1039	−0.0472	0.047*
C11	0.7208 (4)	−0.0903 (3)	−0.0607 (2)	0.0362 (7)
C12	0.6593 (4)	−0.2102 (4)	−0.0032 (2)	0.0413 (7)
H12	0.6451	−0.2187	0.0724	0.050*
C13	0.6194 (4)	−0.3163 (4)	−0.0580 (3)	0.0454 (8)
H13	0.5775	−0.3964	−0.0199	0.054*
C14	0.6428 (4)	−0.3016 (4)	−0.1703 (3)	0.0404 (7)
C15	0.7034 (4)	−0.1855 (4)	−0.2294 (3)	0.0431 (8)
H15	0.7184	−0.1782	−0.3052	0.052*
C16	0.7415 (4)	−0.0794 (4)	−0.1731 (2)	0.0414 (8)
H16	0.7820	0.0010	−0.2116	0.050*
S1	0.79259 (11)	0.01247 (9)	0.42342 (6)	0.0432 (2)
O1	0.9788 (3)	−0.0430 (3)	0.37576 (19)	0.0558 (6)
O2	0.7010 (3)	−0.0721 (3)	0.50933 (18)	0.0569 (6)
O3	0.6135 (4)	−0.3959 (3)	−0.3268 (2)	0.0759 (8)
O4	0.5483 (5)	−0.5195 (3)	−0.1767 (3)	0.0898 (10)
N1	0.7408 (4)	0.1889 (3)	0.4696 (2)	0.0498 (7)
N2	0.7990 (3)	0.1447 (3)	0.1299 (2)	0.0404 (6)
N3	0.7509 (3)	0.0216 (3)	0.0964 (2)	0.0396 (6)
N4	0.5998 (4)	−0.4145 (4)	−0.2289 (3)	0.0559 (8)
Br1	1.00058 (6)	0.65482 (4)	0.13996 (3)	0.06700 (17)

	U11	U22	U33	U12	U13	U23
C1	0.048 (2)	0.0466 (19)	0.0369 (18)	−0.0160 (15)	−0.0144 (15)	−0.0020 (15)
C2	0.076 (3)	0.063 (2)	0.046 (2)	−0.022 (2)	−0.0239 (19)	−0.0153 (18)
C3	0.069 (2)	0.0375 (18)	0.058 (2)	−0.0180 (17)	−0.0296 (18)	−0.0092 (16)
C4	0.051 (2)	0.0363 (17)	0.052 (2)	−0.0126 (15)	−0.0240 (16)	0.0005 (15)
C5	0.0415 (19)	0.0375 (16)	0.0399 (18)	−0.0096 (14)	−0.0175 (14)	−0.0018 (14)
C6	0.0370 (18)	0.0389 (17)	0.0387 (17)	−0.0117 (14)	−0.0143 (13)	−0.0046 (13)
C7	0.0338 (17)	0.0365 (16)	0.0320 (17)	−0.0101 (13)	−0.0115 (13)	−0.0018 (13)
C8	0.050 (2)	0.0496 (19)	0.0379 (18)	−0.0230 (16)	−0.0139 (15)	0.0011 (15)
C9	0.094 (3)	0.081 (3)	0.046 (2)	−0.023 (2)	0.006 (2)	−0.013 (2)
C10	0.0408 (19)	0.0436 (17)	0.0361 (18)	−0.0185 (14)	−0.0109 (14)	0.0002 (14)
C11	0.0338 (17)	0.0423 (17)	0.0352 (17)	−0.0125 (13)	−0.0121 (13)	−0.0018 (13)
C12	0.049 (2)	0.0495 (19)	0.0304 (17)	−0.0177 (15)	−0.0161 (14)	0.0016 (14)
C13	0.056 (2)	0.0424 (18)	0.046 (2)	−0.0217 (16)	−0.0201 (16)	0.0032 (15)
C14	0.0412 (19)	0.0451 (18)	0.0381 (18)	−0.0107 (15)	−0.0158 (14)	−0.0079 (14)
C15	0.0395 (19)	0.060 (2)	0.0315 (17)	−0.0118 (16)	−0.0128 (14)	−0.0055 (15)
C16	0.0431 (19)	0.0498 (19)	0.0353 (18)	−0.0197 (15)	−0.0123 (14)	0.0032 (14)
S1	0.0471 (5)	0.0504 (5)	0.0333 (4)	−0.0180 (4)	−0.0110 (3)	0.0065 (4)
O1	0.0443 (15)	0.0642 (15)	0.0522 (14)	−0.0085 (11)	−0.0126 (11)	0.0132 (12)
O2	0.0661 (17)	0.0680 (16)	0.0400 (13)	−0.0306 (13)	−0.0132 (11)	0.0155 (11)
O3	0.100 (2)	0.091 (2)	0.0488 (17)	−0.0368 (17)	−0.0284 (15)	−0.0191 (15)
O4	0.143 (3)	0.076 (2)	0.085 (2)	−0.063 (2)	−0.055 (2)	0.0059 (17)
N1	0.064 (2)	0.0584 (18)	0.0280 (14)	−0.0241 (15)	−0.0083 (12)	−0.0028 (12)
N2	0.0479 (17)	0.0391 (14)	0.0405 (16)	−0.0188 (12)	−0.0163 (12)	−0.0023 (12)
N3	0.0482 (16)	0.0375 (14)	0.0382 (16)	−0.0167 (12)	−0.0157 (12)	−0.0036 (11)
N4	0.058 (2)	0.060 (2)	0.057 (2)	−0.0167 (16)	−0.0241 (15)	−0.0144 (16)
Br1	0.0932 (4)	0.0392 (2)	0.0830 (3)	−0.0297 (2)	−0.0394 (2)	0.01409 (18)

C1—C6	1.398 (4)	C10—N3	1.262 (4)
C1—C2	1.400 (4)	C10—C11	1.459 (4)
C1—N1	1.420 (4)	C10—H10	0.9300
C2—C3	1.367 (5)	C11—C16	1.380 (4)
C2—H2	0.9300	C11—C12	1.391 (4)
C3—C4	1.368 (4)	C12—C13	1.376 (4)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.382 (4)	C13—C14	1.379 (4)
C4—Br1	1.884 (3)	C13—H13	0.9300
C5—C6	1.400 (4)	C14—C15	1.366 (4)
C5—H5	0.9300	C14—N4	1.470 (4)
C6—C7	1.478 (4)	C15—C16	1.381 (4)
C7—N2	1.288 (4)	C15—H15	0.9300
C7—C8	1.497 (4)	C16—H16	0.9300
C8—S1	1.748 (3)	S1—O1	1.420 (2)
C8—H8A	0.9700	S1—O2	1.423 (2)
C8—H8B	0.9700	S1—N1	1.631 (3)
C9—N1	1.443 (4)	O3—N4	1.217 (4)
C9—H9A	0.9600	O4—N4	1.219 (4)
C9—H9B	0.9600	N2—N3	1.402 (3)
C9—H9C	0.9600
C6—C1—C2	119.1 (3)	N3—C10—H10	118.6
C6—C1—N1	121.3 (3)	C11—C10—H10	118.6
C2—C1—N1	119.7 (3)	C16—C11—C12	119.2 (3)
C3—C2—C1	121.0 (3)	C16—C11—C10	119.0 (3)
C3—C2—H2	119.5	C12—C11—C10	121.8 (3)
C1—C2—H2	119.5	C13—C12—C11	120.2 (3)
C2—C3—C4	120.2 (3)	C13—C12—H12	119.9
C2—C3—H3	119.9	C11—C12—H12	119.9
C4—C3—H3	119.9	C12—C13—C14	118.7 (3)
C3—C4—C5	120.3 (3)	C12—C13—H13	120.6
C3—C4—Br1	120.3 (2)	C14—C13—H13	120.6
C5—C4—Br1	119.3 (2)	C15—C14—C13	122.6 (3)
C4—C5—C6	120.4 (3)	C15—C14—N4	118.6 (3)
C4—C5—H5	119.8	C13—C14—N4	118.8 (3)
C6—C5—H5	119.8	C14—C15—C16	117.9 (3)
C1—C6—C5	118.9 (3)	C14—C15—H15	121.0
C1—C6—C7	122.2 (3)	C16—C15—H15	121.0
C5—C6—C7	118.9 (3)	C11—C16—C15	121.3 (3)
N2—C7—C6	117.6 (3)	C11—C16—H16	119.3
N2—C7—C8	123.0 (2)	C15—C16—H16	119.3
C6—C7—C8	119.4 (2)	O1—S1—O2	118.22 (15)
C7—C8—S1	110.5 (2)	O1—S1—N1	110.53 (15)
C7—C8—H8A	109.6	O2—S1—N1	108.09 (14)
S1—C8—H8A	109.6	O1—S1—C8	107.65 (15)
C7—C8—H8B	109.6	O2—S1—C8	110.70 (14)
S1—C8—H8B	109.6	N1—S1—C8	100.17 (15)
H8A—C8—H8B	108.1	C1—N1—C9	122.1 (3)
N1—C9—H9A	109.5	C1—N1—S1	116.7 (2)
N1—C9—H9B	109.5	C9—N1—S1	121.3 (2)
H9A—C9—H9B	109.5	C7—N2—N3	113.8 (2)
N1—C9—H9C	109.5	C10—N3—N2	112.1 (2)
H9A—C9—H9C	109.5	O3—N4—O4	123.4 (3)
H9B—C9—H9C	109.5	O3—N4—C14	117.9 (3)
N3—C10—C11	122.9 (3)	O4—N4—C14	118.7 (3)
C6—C1—C2—C3	−0.6 (5)	C13—C14—C15—C16	−0.2 (5)
N1—C1—C2—C3	−179.7 (3)	N4—C14—C15—C16	179.3 (3)
C1—C2—C3—C4	−1.1 (6)	C12—C11—C16—C15	−0.3 (5)
C2—C3—C4—C5	1.7 (5)	C10—C11—C16—C15	179.8 (3)
C2—C3—C4—Br1	−178.5 (3)	C14—C15—C16—C11	0.5 (5)
C3—C4—C5—C6	−0.5 (5)	C7—C8—S1—O1	−60.1 (3)
Br1—C4—C5—C6	179.6 (2)	C7—C8—S1—O2	169.3 (2)
C2—C1—C6—C5	1.7 (5)	C7—C8—S1—N1	55.4 (2)
N1—C1—C6—C5	−179.2 (3)	C6—C1—N1—C9	−149.0 (4)
C2—C1—C6—C7	−177.8 (3)	C2—C1—N1—C9	30.0 (5)
N1—C1—C6—C7	1.2 (5)	C6—C1—N1—S1	31.0 (4)
C4—C5—C6—C1	−1.2 (5)	C2—C1—N1—S1	−149.9 (3)
C4—C5—C6—C7	178.4 (3)	O1—S1—N1—C1	57.5 (3)
C1—C6—C7—N2	−179.6 (3)	O2—S1—N1—C1	−171.7 (2)
C5—C6—C7—N2	0.8 (4)	C8—S1—N1—C1	−55.9 (3)
C1—C6—C7—C8	2.2 (4)	O1—S1—N1—C9	−122.5 (3)
C5—C6—C7—C8	−177.4 (3)	O2—S1—N1—C9	8.3 (4)
N2—C7—C8—S1	148.6 (3)	C8—S1—N1—C9	124.2 (3)
C6—C7—C8—S1	−33.3 (4)	C6—C7—N2—N3	−178.5 (3)
N3—C10—C11—C16	−178.9 (3)	C8—C7—N2—N3	−0.4 (4)
N3—C10—C11—C12	1.2 (5)	C11—C10—N3—N2	−179.8 (3)
C16—C11—C12—C13	−0.1 (5)	C7—N2—N3—C10	175.5 (3)
C10—C11—C12—C13	179.7 (3)	C15—C14—N4—O3	−2.8 (5)
C11—C12—C13—C14	0.4 (5)	C13—C14—N4—O3	176.7 (3)
C12—C13—C14—C15	−0.3 (5)	C15—C14—N4—O4	178.9 (3)
C12—C13—C14—N4	−179.8 (3)	C13—C14—N4—O4	−1.6 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O3i	0.93	2.56	3.325 (4)	139
C8—H8B···O2ii	0.97	2.44	3.310 (4)	150
C13—H13···O4iii	0.93	2.53	3.306 (5)	141
C15—H15···O2iv	0.93	2.53	3.426 (4)	162
C16—H16···O1v	0.93	2.45	3.218 (4)	139

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O3i	0.93	2.56	3.325 (4)	139
C8—H8B⋯O2ii	0.97	2.44	3.310 (4)	150
C13—H13⋯O4iii	0.93	2.53	3.306 (5)	141
C15—H15⋯O2iv	0.93	2.53	3.426 (4)	162
C16—H16⋯O1v	0.93	2.45	3.218 (4)	139

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