Benzyl (E)-3-(2-bromo-5-meth-oxy-benzyl-idene)dithio-carbazate.

The title compound, C(16)H(15)BrN(2)OS(2), was obtained from the condensation reaction of benzyl dithio-carbazate and 2-bromo-5-meth-oxy-lbenzaldehyde. In the mol-ecule, the bromo-meth-oxy-phenyl ring and dithio-carbazate fragment are located on the opposite sides of the C=N double bond, showing the E conformation. The dithio-carbazate fragment is approximately planar (r.m.s deviation 0.0187 Å); its mean plane is oriented with respect to the bromo-meth-oxy-phenyl and phenyl rings at 7.60 (12) and 60.08 (9)°, respectively. In the crystal, inversion dimers linked by pairs of N-H⋯S hydrogen bonds occur. A short Br⋯Br contact of 3.5526 (12) Å is observed in the crystal structure.

Related literature

For the potential application of hydrazone and its derivatives in the biological field, see: Okabe et al. (1993 ▶); Hu et al. (2001 ▶). For related structures, see: Shan et al. (2008a ▶,b ▶). For the synthesis, see: Hu et al. (2001 ▶).

Experimental

Crystal data

C16H15BrN2OS2

M = 395.33

Triclinic,

a = 6.260 (3) Å

b = 11.889 (5) Å

c = 12.235 (5) Å

α = 111.931 (5)°

β = 91.725 (4)°

γ = 99.771 (4)°

V = 828.1 (6) Å3

Z = 2

Mo Kα radiation

μ = 2.74 mm−1

T = 294 K

0.32 × 0.28 × 0.19 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.56, T max = 0.72

5637 measured reflections

2988 independent reflections

2379 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.069

S = 1.02

2988 reflections

201 parameters

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.30 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811042826/xu5353sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811042826/xu5353Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811042826/xu5353Isup3.cml

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

C16H15BrN2OS2	Z = 2
Mr = 395.33	F(000) = 400
Triclinic, P1	Dx = 1.586 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.260 (3) Å	Cell parameters from 2988 reflections
b = 11.889 (5) Å	θ = 3.3–25.2°
c = 12.235 (5) Å	µ = 2.74 mm−1
α = 111.931 (5)°	T = 294 K
β = 91.725 (4)°	Block, yellow
γ = 99.771 (4)°	0.32 × 0.28 × 0.19 mm
V = 828.1 (6) Å3

Rigaku R-AXIS RAPID IP diffractometer	2988 independent reflections
Radiation source: fine-focus sealed tube	2379 reflections with I > 2σ(I)
graphite	Rint = 0.028
Detector resolution: 10.0 pixels mm-1	θmax = 25.2°, θmin = 3.3°
ω scans	h = −5→7
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −14→11
Tmin = 0.56, Tmax = 0.72	l = −14→14
5637 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034	H-atom parameters constrained
wR(F2) = 0.069	w = 1/[σ2(Fo2) + (0.0276P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
2988 reflections	Δρmax = 0.25 e Å−3
201 parameters	Δρmin = −0.30 e Å−3
0 restraints	Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0123 (11)

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
Br	0.33444 (5)	0.11365 (3)	0.04397 (2)	0.05700 (14)
S1	1.10460 (10)	0.70610 (6)	0.10224 (6)	0.0458 (2)
S2	0.72189 (10)	0.76733 (6)	0.24288 (6)	0.0423 (2)
N1	0.5742 (3)	0.51783 (19)	0.15272 (15)	0.0336 (5)
N2	0.7654 (3)	0.54749 (19)	0.10904 (16)	0.0356 (5)
H2	0.8197	0.4905	0.0580	0.043*
O1	−0.0891 (3)	0.51964 (18)	0.35686 (15)	0.0501 (5)
C1	0.1988 (4)	0.2431 (2)	0.13964 (19)	0.0366 (6)
C2	0.0116 (5)	0.2108 (3)	0.1861 (2)	0.0487 (8)
H2A	−0.0459	0.1278	0.1682	0.058*
C3	−0.0907 (4)	0.2999 (3)	0.2586 (2)	0.0465 (7)
H3	−0.2169	0.2778	0.2900	0.056*
C4	−0.0045 (4)	0.4226 (3)	0.2843 (2)	0.0370 (6)
C5	0.1811 (4)	0.4548 (2)	0.23569 (19)	0.0341 (6)
H5	0.2356	0.5378	0.2518	0.041*
C6	0.2875 (4)	0.3660 (2)	0.16346 (19)	0.0314 (6)
C7	0.4884 (4)	0.4042 (2)	0.11732 (19)	0.0356 (6)
H7	0.5525	0.3453	0.0623	0.043*
C8	0.8663 (4)	0.6654 (2)	0.14642 (18)	0.0319 (6)
C9	0.8899 (4)	0.9158 (2)	0.2670 (2)	0.0414 (7)
H9A	1.0306	0.9241	0.3078	0.050*
H9B	0.9132	0.9233	0.1918	0.050*
C10	0.7736 (4)	1.0146 (2)	0.3410 (2)	0.0380 (6)
C11	0.5706 (5)	1.0236 (3)	0.3006 (2)	0.0489 (8)
H11	0.5048	0.9677	0.2267	0.059*
C12	0.4647 (5)	1.1145 (3)	0.3690 (3)	0.0587 (8)
H12	0.3299	1.1210	0.3404	0.070*
C13	0.5599 (6)	1.1955 (3)	0.4797 (3)	0.0624 (9)
H13	0.4869	1.2552	0.5269	0.075*
C14	0.7606 (6)	1.1886 (3)	0.5205 (2)	0.0636 (9)
H14	0.8250	1.2441	0.5948	0.076*
C15	0.8682 (5)	1.0989 (3)	0.4509 (2)	0.0487 (7)
H15	1.0059	1.0953	0.4786	0.058*
C16	−0.2653 (5)	0.4938 (3)	0.4202 (2)	0.0604 (9)
H16A	−0.3916	0.4475	0.3655	0.091*
H16B	−0.2973	0.5700	0.4744	0.091*
H16C	−0.2260	0.4464	0.4636	0.091*

	U11	U22	U33	U12	U13	U23
Br	0.0715 (2)	0.03141 (19)	0.0601 (2)	0.01393 (14)	0.01395 (15)	0.00643 (14)
S1	0.0383 (4)	0.0355 (4)	0.0532 (4)	0.0005 (3)	0.0211 (3)	0.0069 (3)
S2	0.0413 (4)	0.0289 (4)	0.0511 (4)	0.0051 (3)	0.0214 (3)	0.0084 (3)
N1	0.0292 (10)	0.0319 (13)	0.0367 (10)	0.0026 (9)	0.0078 (9)	0.0109 (9)
N2	0.0333 (11)	0.0297 (13)	0.0390 (11)	0.0034 (9)	0.0146 (9)	0.0083 (9)
O1	0.0423 (11)	0.0511 (13)	0.0580 (11)	0.0155 (9)	0.0225 (9)	0.0181 (9)
C1	0.0422 (15)	0.0286 (15)	0.0355 (13)	0.0030 (12)	0.0031 (11)	0.0101 (11)
C2	0.0553 (17)	0.0332 (17)	0.0505 (15)	−0.0061 (14)	0.0095 (14)	0.0140 (13)
C3	0.0389 (15)	0.0474 (19)	0.0507 (15)	−0.0051 (13)	0.0116 (13)	0.0214 (14)
C4	0.0309 (13)	0.0432 (17)	0.0362 (13)	0.0080 (12)	0.0038 (11)	0.0142 (12)
C5	0.0311 (13)	0.0265 (14)	0.0412 (13)	0.0006 (11)	0.0028 (11)	0.0113 (11)
C6	0.0302 (13)	0.0300 (15)	0.0313 (11)	0.0030 (11)	0.0013 (10)	0.0102 (10)
C7	0.0378 (14)	0.0294 (15)	0.0347 (12)	0.0050 (11)	0.0092 (11)	0.0070 (11)
C8	0.0327 (13)	0.0329 (15)	0.0276 (11)	0.0047 (11)	0.0044 (10)	0.0096 (10)
C9	0.0414 (15)	0.0293 (15)	0.0476 (14)	0.0016 (12)	0.0134 (12)	0.0097 (12)
C10	0.0443 (15)	0.0262 (15)	0.0444 (14)	0.0047 (12)	0.0165 (12)	0.0146 (12)
C11	0.0441 (16)	0.0421 (18)	0.0547 (16)	0.0045 (13)	0.0117 (13)	0.0133 (13)
C12	0.0470 (17)	0.054 (2)	0.084 (2)	0.0160 (15)	0.0236 (17)	0.0319 (18)
C13	0.085 (2)	0.043 (2)	0.068 (2)	0.0282 (17)	0.0390 (19)	0.0228 (16)
C14	0.102 (3)	0.0402 (19)	0.0437 (16)	0.0218 (18)	0.0107 (17)	0.0072 (14)
C15	0.0603 (18)	0.0353 (17)	0.0466 (15)	0.0094 (14)	0.0060 (14)	0.0113 (13)
C16	0.0449 (16)	0.085 (3)	0.0553 (16)	0.0222 (16)	0.0221 (14)	0.0258 (16)

Br—C1	1.902 (3)	C6—C7	1.465 (3)
S1—C8	1.658 (3)	C7—H7	0.9300
S2—C8	1.745 (2)	C9—C10	1.505 (4)
S2—C9	1.808 (3)	C9—H9A	0.9700
N1—C7	1.267 (3)	C9—H9B	0.9700
N1—N2	1.370 (3)	C10—C15	1.381 (3)
N2—C8	1.333 (3)	C10—C11	1.385 (4)
N2—H2	0.8600	C11—C12	1.382 (4)
O1—C4	1.368 (3)	C11—H11	0.9300
O1—C16	1.424 (3)	C12—C13	1.378 (4)
C1—C2	1.377 (4)	C12—H12	0.9300
C1—C6	1.387 (4)	C13—C14	1.365 (5)
C2—C3	1.372 (4)	C13—H13	0.9300
C2—H2A	0.9300	C14—C15	1.384 (4)
C3—C4	1.378 (4)	C14—H14	0.9300
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.382 (3)	C16—H16A	0.9600
C5—C6	1.385 (3)	C16—H16B	0.9600
C5—H5	0.9300	C16—H16C	0.9600
C8—S2—C9	101.87 (12)	C10—C9—S2	107.86 (17)
C7—N1—N2	116.98 (19)	C10—C9—H9A	110.1
C8—N2—N1	119.40 (18)	S2—C9—H9A	110.1
C8—N2—H2	120.3	C10—C9—H9B	110.1
N1—N2—H2	120.3	S2—C9—H9B	110.1
C4—O1—C16	118.1 (2)	H9A—C9—H9B	108.4
C2—C1—C6	121.2 (2)	C15—C10—C11	118.5 (2)
C2—C1—Br	117.7 (2)	C15—C10—C9	120.4 (2)
C6—C1—Br	121.16 (18)	C11—C10—C9	121.0 (2)
C3—C2—C1	120.6 (3)	C12—C11—C10	120.8 (3)
C3—C2—H2A	119.7	C12—C11—H11	119.6
C1—C2—H2A	119.7	C10—C11—H11	119.6
C2—C3—C4	119.3 (2)	C13—C12—C11	119.7 (3)
C2—C3—H3	120.3	C13—C12—H12	120.2
C4—C3—H3	120.3	C11—C12—H12	120.2
O1—C4—C3	124.7 (2)	C14—C13—C12	120.3 (3)
O1—C4—C5	115.2 (2)	C14—C13—H13	119.8
C3—C4—C5	120.0 (2)	C12—C13—H13	119.8
C4—C5—C6	121.3 (2)	C13—C14—C15	119.9 (3)
C4—C5—H5	119.3	C13—C14—H14	120.1
C6—C5—H5	119.3	C15—C14—H14	120.1
C5—C6—C1	117.6 (2)	C10—C15—C14	120.8 (3)
C5—C6—C7	119.6 (2)	C10—C15—H15	119.6
C1—C6—C7	122.8 (2)	C14—C15—H15	119.6
N1—C7—C6	119.7 (2)	O1—C16—H16A	109.5
N1—C7—H7	120.1	O1—C16—H16B	109.5
C6—C7—H7	120.1	H16A—C16—H16B	109.5
N2—C8—S1	121.55 (17)	O1—C16—H16C	109.5
N2—C8—S2	113.22 (17)	H16A—C16—H16C	109.5
S1—C8—S2	125.23 (15)	H16B—C16—H16C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1i	0.86	2.56	3.402 (3)	167

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S1i	0.86	2.56	3.402 (3)	167

Symmetry code: (i) .