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

In the title compound, C(16)H(13)BrFN(3)O(2)S, the dihedral angle between the aromatic rings is 2.55 (19)° and the C=N-N=C torsion angle is 178.9 (3)°. The conformation of the thia-zine ring is an envelope, with the S atom displaced by -0.811 (3) Å from the mean plane of the other five atoms (r.m.s. deviation = 0.042 Å). In the crystal, C-H⋯O inter-actions link the mol-ecules and weak aromatic π-π stacking between the fluoro-benzene and bromo-benzene rings [centroid-centroid separation = 3.720 (2) Å and inter-planar angle = 2.6 (2)°] is also observed.

Related literature

For the synthesis and for the biological activity of related materials, see: Shafiq, Zia-Ur-Rehman et al. (2011 ▶). For a related structure, see: Shafiq, Khan et al. (2011 ▶)

Experimental

Crystal data

C16H13BrFN3O2S

M = 410.26

Triclinic,

a = 7.8996 (4) Å

b = 9.0070 (4) Å

c = 13.5057 (7) Å

α = 104.176 (3)°

β = 90.977 (3)°

γ = 113.466 (3)°

V = 847.51 (7) Å3

Z = 2

Mo Kα radiation

μ = 2.57 mm−1

T = 296 K

0.37 × 0.16 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.450, T max = 0.715

17622 measured reflections

4186 independent reflections

2331 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.118

S = 0.99

4186 reflections

218 parameters

H-atom parameters constrained

Δρmax = 0.58 e Å−3

Δρmin = −0.78 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/S1600536812037403/kj2209sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812037403/kj2209Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812037403/kj2209Isup3.cml

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

C16H13BrFN3O2S	Z = 2
Mr = 410.26	F(000) = 412
Triclinic, P1	Dx = 1.608 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8996 (4) Å	Cell parameters from 4416 reflections
b = 9.0070 (4) Å	θ = 2.6–22.8°
c = 13.5057 (7) Å	µ = 2.57 mm−1
α = 104.176 (3)°	T = 296 K
β = 90.977 (3)°	Needle, yellow
γ = 113.466 (3)°	0.37 × 0.16 × 0.14 mm
V = 847.51 (7) Å3

Bruker APEXII CCD diffractometer	4186 independent reflections
Radiation source: fine-focus sealed tube	2331 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ω scans	θmax = 28.3°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −10→10
Tmin = 0.450, Tmax = 0.715	k = −12→12
17622 measured reflections	l = −17→17

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118	H-atom parameters constrained
S = 0.99	w = 1/[σ2(Fo2) + (0.0479P)2 + 0.5245P] where P = (Fo2 + 2Fc2)/3
4186 reflections	(Δ/σ)max = 0.001
218 parameters	Δρmax = 0.58 e Å−3
0 restraints	Δρmin = −0.78 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	0.9739 (4)	0.8291 (4)	0.2392 (2)	0.0408 (7)
C2	1.0591 (5)	0.8914 (4)	0.3410 (2)	0.0515 (8)
H2	1.0804	0.8194	0.3734	0.062*
C3	1.1121 (5)	1.0568 (4)	0.3941 (2)	0.0535 (9)
H3	1.1720	1.0973	0.4612	0.064*
C4	1.0757 (5)	1.1622 (4)	0.3472 (2)	0.0512 (8)
C5	0.9894 (4)	1.1042 (4)	0.2476 (2)	0.0432 (7)
H5	0.9654	1.1771	0.2172	0.052*
C6	0.9377 (4)	0.9379 (3)	0.1919 (2)	0.0354 (6)
C7	0.8470 (4)	0.8820 (3)	0.0850 (2)	0.0345 (6)
C8	0.8201 (5)	0.7111 (3)	0.0194 (2)	0.0458 (8)
H8A	0.9351	0.7173	−0.0075	0.055*
H8B	0.7248	0.6743	−0.0384	0.055*
C9	0.6595 (4)	1.0158 (4)	−0.0800 (2)	0.0379 (7)
H9	0.6818	1.1194	−0.0344	0.045*
C10	0.5657 (4)	0.9726 (4)	−0.1840 (2)	0.0409 (7)
C11	0.5109 (5)	0.8138 (4)	−0.2507 (2)	0.0552 (9)
H11	0.5309	0.7307	−0.2296	0.066*
C12	0.4260 (5)	0.7788 (6)	−0.3493 (3)	0.0735 (12)
H12	0.3877	0.6722	−0.3948	0.088*
C13	0.3996 (5)	0.9026 (7)	−0.3781 (3)	0.0741 (13)
C14	0.4504 (5)	1.0597 (6)	−0.3152 (3)	0.0725 (12)
H14	0.4300	1.1416	−0.3377	0.087*
C15	0.5335 (5)	1.0944 (5)	−0.2165 (3)	0.0564 (9)
H15	0.5682	1.2009	−0.1713	0.068*
C16	0.9850 (6)	0.5539 (5)	0.2319 (3)	0.0817 (13)
H16A	1.1167	0.6067	0.2535	0.122*
H16B	0.9531	0.4469	0.1827	0.122*
H16C	0.9202	0.5378	0.2906	0.122*
S1	0.75433 (14)	0.56638 (10)	0.09239 (7)	0.0548 (3)
N1	0.9317 (4)	0.6609 (3)	0.1849 (2)	0.0542 (7)
N2	0.7961 (3)	0.9817 (3)	0.05209 (17)	0.0383 (6)
N3	0.7109 (3)	0.9153 (3)	−0.05055 (17)	0.0407 (6)
O1	0.7609 (4)	0.4128 (3)	0.0372 (2)	0.0824 (9)
O2	0.5862 (3)	0.5604 (3)	0.1320 (2)	0.0672 (7)
F1	0.3170 (4)	0.8672 (4)	−0.47568 (18)	0.1185 (11)
Br1	1.14956 (8)	1.39006 (5)	0.42019 (3)	0.0926 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0408 (18)	0.0441 (16)	0.0416 (17)	0.0197 (15)	0.0030 (14)	0.0151 (13)
C2	0.054 (2)	0.064 (2)	0.0436 (18)	0.0272 (18)	−0.0006 (15)	0.0233 (16)
C3	0.057 (2)	0.069 (2)	0.0319 (17)	0.0243 (18)	−0.0045 (15)	0.0115 (15)
C4	0.060 (2)	0.0507 (18)	0.0361 (17)	0.0231 (17)	−0.0059 (15)	0.0009 (14)
C5	0.0503 (19)	0.0433 (16)	0.0337 (15)	0.0197 (15)	−0.0039 (14)	0.0066 (13)
C6	0.0375 (17)	0.0377 (14)	0.0306 (14)	0.0149 (13)	0.0023 (12)	0.0099 (12)
C7	0.0352 (16)	0.0314 (13)	0.0329 (15)	0.0100 (13)	0.0015 (12)	0.0086 (11)
C8	0.056 (2)	0.0360 (15)	0.0395 (17)	0.0171 (15)	−0.0020 (15)	0.0041 (13)
C9	0.0393 (17)	0.0373 (15)	0.0335 (15)	0.0142 (13)	0.0010 (13)	0.0068 (12)
C10	0.0352 (17)	0.0536 (18)	0.0359 (16)	0.0182 (15)	0.0000 (13)	0.0164 (13)
C11	0.056 (2)	0.057 (2)	0.0431 (19)	0.0166 (18)	−0.0090 (16)	0.0091 (15)
C12	0.064 (3)	0.089 (3)	0.041 (2)	0.015 (2)	−0.0131 (18)	0.004 (2)
C13	0.050 (2)	0.129 (4)	0.043 (2)	0.031 (3)	−0.0069 (17)	0.034 (2)
C14	0.065 (3)	0.116 (4)	0.065 (3)	0.050 (3)	0.009 (2)	0.052 (3)
C15	0.054 (2)	0.075 (2)	0.052 (2)	0.0337 (19)	0.0086 (17)	0.0260 (18)
C16	0.102 (3)	0.059 (2)	0.096 (3)	0.042 (2)	−0.015 (3)	0.030 (2)
S1	0.0655 (6)	0.0316 (4)	0.0608 (5)	0.0150 (4)	−0.0081 (4)	0.0115 (4)
N1	0.0662 (19)	0.0447 (15)	0.0571 (17)	0.0273 (14)	−0.0093 (14)	0.0170 (13)
N2	0.0437 (15)	0.0375 (12)	0.0291 (12)	0.0151 (12)	−0.0052 (10)	0.0048 (10)
N3	0.0495 (15)	0.0401 (13)	0.0294 (12)	0.0173 (12)	−0.0045 (11)	0.0070 (10)
O1	0.113 (2)	0.0376 (13)	0.090 (2)	0.0338 (14)	−0.0166 (17)	0.0037 (12)
O2	0.0524 (16)	0.0561 (15)	0.0801 (18)	0.0050 (12)	0.0048 (13)	0.0266 (13)
F1	0.0919 (18)	0.199 (3)	0.0528 (14)	0.043 (2)	−0.0233 (13)	0.0460 (18)
Br1	0.1381 (5)	0.0639 (3)	0.0568 (3)	0.0455 (3)	−0.0405 (3)	−0.01902 (18)

C1—C2	1.395 (4)	C10—C11	1.381 (4)
C1—C6	1.405 (4)	C10—C15	1.385 (4)
C1—N1	1.411 (4)	C11—C12	1.384 (5)
C2—C3	1.370 (5)	C11—H11	0.9300
C2—H2	0.9300	C12—C13	1.355 (6)
C3—C4	1.375 (5)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.354 (6)
C4—C5	1.373 (4)	C13—F1	1.365 (4)
C4—Br1	1.887 (3)	C14—C15	1.382 (5)
C5—C6	1.388 (4)	C14—H14	0.9300
C5—H5	0.9300	C15—H15	0.9300
C6—C7	1.475 (4)	C16—N1	1.457 (4)
C7—N2	1.281 (3)	C16—H16A	0.9600
C7—C8	1.505 (4)	C16—H16B	0.9600
C8—S1	1.746 (3)	C16—H16C	0.9600
C8—H8A	0.9700	S1—O1	1.423 (3)
C8—H8B	0.9700	S1—O2	1.426 (3)
C9—N3	1.268 (3)	S1—N1	1.649 (3)
C9—C10	1.463 (4)	N2—N3	1.405 (3)
C9—H9	0.9300
C2—C1—C6	118.9 (3)	C10—C11—C12	119.8 (3)
C2—C1—N1	119.7 (3)	C10—C11—H11	120.1
C6—C1—N1	121.3 (3)	C12—C11—H11	120.1
C3—C2—C1	121.3 (3)	C13—C12—C11	118.8 (4)
C3—C2—H2	119.4	C13—C12—H12	120.6
C1—C2—H2	119.4	C11—C12—H12	120.6
C2—C3—C4	119.4 (3)	C14—C13—C12	123.5 (3)
C2—C3—H3	120.3	C14—C13—F1	118.2 (4)
C4—C3—H3	120.3	C12—C13—F1	118.4 (4)
C5—C4—C3	120.8 (3)	C13—C14—C15	117.8 (4)
C5—C4—Br1	119.9 (2)	C13—C14—H14	121.1
C3—C4—Br1	119.3 (2)	C15—C14—H14	121.1
C4—C5—C6	120.7 (3)	C14—C15—C10	120.8 (4)
C4—C5—H5	119.7	C14—C15—H15	119.6
C6—C5—H5	119.7	C10—C15—H15	119.6
C5—C6—C1	118.9 (3)	N1—C16—H16A	109.5
C5—C6—C7	118.7 (2)	N1—C16—H16B	109.5
C1—C6—C7	122.4 (2)	H16A—C16—H16B	109.5
N2—C7—C6	118.5 (2)	N1—C16—H16C	109.5
N2—C7—C8	123.1 (2)	H16A—C16—H16C	109.5
C6—C7—C8	118.4 (2)	H16B—C16—H16C	109.5
C7—C8—S1	110.0 (2)	O1—S1—O2	118.54 (17)
C7—C8—H8A	109.7	O1—S1—N1	107.04 (16)
S1—C8—H8A	109.7	O2—S1—N1	110.83 (16)
C7—C8—H8B	109.7	O1—S1—C8	110.49 (17)
S1—C8—H8B	109.7	O2—S1—C8	108.71 (16)
H8A—C8—H8B	108.2	N1—S1—C8	99.57 (14)
N3—C9—C10	121.5 (3)	C1—N1—C16	120.7 (3)
N3—C9—H9	119.2	C1—N1—S1	117.5 (2)
C10—C9—H9	119.2	C16—N1—S1	117.2 (2)
C11—C10—C15	119.4 (3)	C7—N2—N3	113.6 (2)
C11—C10—C9	121.5 (3)	C9—N3—N2	111.9 (2)
C15—C10—C9	119.1 (3)
C6—C1—C2—C3	−1.7 (5)	C11—C12—C13—C14	−0.7 (6)
N1—C1—C2—C3	176.1 (3)	C11—C12—C13—F1	179.5 (3)
C1—C2—C3—C4	1.9 (5)	C12—C13—C14—C15	0.0 (6)
C2—C3—C4—C5	−0.9 (5)	F1—C13—C14—C15	179.8 (3)
C2—C3—C4—Br1	−179.8 (3)	C13—C14—C15—C10	0.9 (6)
C3—C4—C5—C6	−0.3 (5)	C11—C10—C15—C14	−1.2 (5)
Br1—C4—C5—C6	178.6 (2)	C9—C10—C15—C14	178.1 (3)
C4—C5—C6—C1	0.4 (5)	C7—C8—S1—O1	−169.6 (2)
C4—C5—C6—C7	−179.4 (3)	C7—C8—S1—O2	58.7 (3)
C2—C1—C6—C5	0.6 (4)	C7—C8—S1—N1	−57.2 (2)
N1—C1—C6—C5	−177.2 (3)	C2—C1—N1—C16	−3.3 (5)
C2—C1—C6—C7	−179.6 (3)	C6—C1—N1—C16	174.5 (3)
N1—C1—C6—C7	2.6 (5)	C2—C1—N1—S1	152.0 (3)
C5—C6—C7—N2	−9.5 (4)	C6—C1—N1—S1	−30.2 (4)
C1—C6—C7—N2	170.6 (3)	O1—S1—N1—C1	169.3 (3)
C5—C6—C7—C8	170.0 (3)	O2—S1—N1—C1	−60.1 (3)
C1—C6—C7—C8	−9.8 (4)	C8—S1—N1—C1	54.3 (3)
N2—C7—C8—S1	−140.5 (3)	O1—S1—N1—C16	−34.5 (3)
C6—C7—C8—S1	40.0 (3)	O2—S1—N1—C16	96.1 (3)
N3—C9—C10—C11	7.3 (5)	C8—S1—N1—C16	−149.5 (3)
N3—C9—C10—C15	−171.9 (3)	C6—C7—N2—N3	−179.8 (2)
C15—C10—C11—C12	0.5 (5)	C8—C7—N2—N3	0.7 (4)
C9—C10—C11—C12	−178.7 (3)	C10—C9—N3—N2	−179.4 (3)
C10—C11—C12—C13	0.4 (6)	C7—N2—N3—C9	178.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O2i	0.97	2.56	3.397 (4)	145
C9—H9···O1ii	0.93	2.39	3.292 (4)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯O2i	0.97	2.56	3.397 (4)	145
C9—H9⋯O1ii	0.93	2.39	3.292 (4)	163

Symmetry codes: (i) ; (ii) .