Benzyl 3-[(E)-2-nitro­benzyl­idene]dithio­carbazate

Shan, S.; Huang, Y.-L.; Guo, H.-Q.; Li, D.-F.; Sun, J.

doi:10.1107/S1600536811028686

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2107

doi:10.1107/S1600536811028686

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Benzyl 3-[(E)-2-nitrobenzylidene]dithiocarbazate

Shang Shan,^a ^* Yan-Lan Huang,^a Han-Qi Guo,^a Deng-Feng Li ^a and Jian Sun ^a

^aCollege of Chemical Engineering and Materials Science, Zhejiang University of Technology, People's Republic of China
^*Correspondence e-mail: shanshang@mail.hz.zj.cn

(Received 9 July 2011; accepted 17 July 2011; online 23 July 2011)

The title compound, C₁₅H₁₃N₃O₂S₂, was obtained from a condensation reaction of benzyl dithiocarbazate and 2-nitrobenzaldehyde. In the molecule, the nearly planar dithiocarbazate fragment [r.m.s deviation = 0.0264 Å] is oriented at dihedral angles of 7.25 (17) and 74.09 (9)°with respect to the two benzene rings. The nitro group is twisted by a dihedral angle of 22.4 (7)° to the attached benzene ring. The nitrobenzene ring and dithiocarbazate fragment are located on the opposite sides of the C=N bond, showing an E configuration. In the crystal, molecules are linked via intermolecular N—H⋯S hydrogen bonds, forming centrosymmetric supramolecular dimers. Weak C—H⋯π interaction is also observed in the crystal structure.

Related literature

For applications 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. (2006 , 2008a ,b , 2011 ). For the synthesis, see: Hu et al. (2001).

Experimental

Crystal data

C₁₅H₁₃N₃O₂S₂
M_r = 331.40
Monoclinic, P 2₁ /c
a = 4.673 (2) Å
b = 28.498 (6) Å
c = 11.735 (5) Å
β = 94.070 (4)°
V = 1558.8 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 294 K
0.38 × 0.25 × 0.23 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.87, T_max = 0.94
6957 measured reflections
2814 independent reflections
1925 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.147
S = 1.05
2814 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C10–C15 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S1ⁱ	0.86	2.51	3.359 (3)	171
C9—H9B⋯Cgⁱⁱ	0.97	2.50	3.410 (4)	156
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x+1, y, z.

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811028686/xu5268sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028686/xu5268Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811028686/xu5268Isup3.cml

checkCIF report

Comment top

Hydrazone and its derivatives have shown the potential application in the biological field (Okabe et al., 1993; Hu et al., 2001). As part of the ongoing investigation on anti-cancer compounds, the title compound has recently been prepared in our laboratory and its crystal structure is presented here.

The molecular structure of the title compound is shown in Fig. 1. In the molecule the nearly planar dithiocarbazate fragment [r.m.s deviation 0.0264 Å] is oriented with respect to the two benzene rings at 7.25 (17) and 74.09 (9)°, respectively. The nitro group is twisted to the attached-benzene ring with a dihedral angle of 22.4 (7)°. The N1—C7 bond length of 1.272 (4) Å indicates a typical C═N double bonds. The nitrobenzene ring and dithiocarbazate fragment are located on the opposite positions of the C═N bonds, showing the E-configuration, which agrees with those found in related compounds (Shan et al., 2006; Shan et al., 2008a,b); Shan et al. 2011). In the crystal the molecules are linked to each other via intermolecular N—H···S hydrogen bonding to form the centro-symmetric supramolecular dimer (Table 1). Weak C—H···π interaction is also observed in the crystal structure.

Related literature top

For applications 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. (2006, 2008a,b, 2011). For the synthesis, see: Hu et al. (2001).

Experimental top

Benzyl dithiocarbazate was synthesized as described previously (Hu et al., 2001). Benzyl dithiocarbazate (0.4 g, 2 mmol) and 2-nitrobenzaldehyde (0.3 g, 2 mmol) were dissolved in ethanol (20 ml), then acetic acid (0.2 ml) was added to the ethanol solution with stirring. The mixture solution was refluxed for 6 h. After cooling to room temperature, yellow microcrystals appeared. The microcrystals were separated from the solution and washed with cold water three times. Recrystallization was performed twice with absolute methanol to obtain single crystals of the title compound.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); 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).

Figures top

Fig. 1. The molecular structure of the title compound with 40% probability displacement (arbitrary spheres for H atoms).

Benzyl 3-[(E)-2-nitrobenzylidene]dithiocarbazate top

Crystal data top

C₁₅H₁₃N₃O₂S₂	F(000) = 688
M_r = 331.40	D_x = 1.412 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2814 reflections
a = 4.673 (2) Å	θ = 2.7–25.2°
b = 28.498 (6) Å	µ = 0.35 mm⁻¹
c = 11.735 (5) Å	T = 294 K
β = 94.070 (4)°	Needle, yellow
V = 1558.8 (10) Å³	0.38 × 0.25 × 0.23 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2814 independent reflections
Radiation source: fine-focus sealed tube	1925 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 10.0 pixels mm^-1	θ_max = 25.2°, θ_min = 2.8°
ω scans	h = −5→5
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −34→33
T_min = 0.87, T_max = 0.94	l = −10→14
6957 measured reflections

Refinement top

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0677P)² + 0.3832P] where P = (F_o² + 2F_c²)/3
2814 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

C₁₅H₁₃N₃O₂S₂	V = 1558.8 (10) Å³
M_r = 331.40	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.673 (2) Å	µ = 0.35 mm⁻¹
b = 28.498 (6) Å	T = 294 K
c = 11.735 (5) Å	0.38 × 0.25 × 0.23 mm
β = 94.070 (4)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2814 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1925 reflections with I > 2σ(I)
T_min = 0.87, T_max = 0.94	R_int = 0.041
6957 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.147	H-atom parameters constrained
S = 1.05	Δρ_max = 0.63 e Å⁻³
2814 reflections	Δρ_min = −0.47 e Å⁻³
199 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.1945 (2)	0.55533 (3)	0.40002 (8)	0.0502 (3)
S2	0.53350 (19)	0.50159 (3)	0.23425 (8)	0.0520 (3)
N1	0.3569 (6)	0.42391 (8)	0.3495 (2)	0.0448 (7)
N2	0.2412 (6)	0.46411 (8)	0.3892 (2)	0.0462 (7)
H2	0.1235	0.4627	0.4423	0.055*
N3	0.2496 (8)	0.29447 (12)	0.5248 (3)	0.0760 (10)
O1	0.1632 (9)	0.25714 (11)	0.5505 (3)	0.1173 (13)
O2	0.2227 (15)	0.32692 (14)	0.5852 (5)	0.201 (3)
C1	0.4074 (7)	0.29939 (11)	0.4221 (3)	0.0513 (9)
C2	0.5231 (9)	0.25869 (11)	0.3821 (4)	0.0663 (11)
H2A	0.4958	0.2303	0.4190	0.080*
C3	0.6797 (9)	0.26018 (13)	0.2870 (4)	0.0725 (12)
H3	0.7596	0.2329	0.2595	0.087*
C4	0.7165 (8)	0.30232 (13)	0.2332 (4)	0.0659 (11)
H4	0.8221	0.3036	0.1691	0.079*
C5	0.5979 (8)	0.34250 (11)	0.2739 (3)	0.0539 (9)
H5	0.6260	0.3707	0.2364	0.065*
C6	0.4374 (7)	0.34259 (10)	0.3691 (3)	0.0452 (8)
C7	0.3121 (7)	0.38673 (10)	0.4055 (3)	0.0495 (9)
H7	0.2018	0.3876	0.4684	0.059*
C8	0.3103 (7)	0.50609 (10)	0.3458 (3)	0.0406 (7)
C9	0.5817 (7)	0.56211 (11)	0.1951 (3)	0.0499 (9)
H9A	0.6092	0.5805	0.2646	0.060*
H9B	0.7566	0.5645	0.1556	0.060*
C10	0.3412 (6)	0.58388 (11)	0.1207 (3)	0.0422 (8)
C11	0.2337 (8)	0.56274 (14)	0.0219 (3)	0.0620 (10)
H11	0.3021	0.5334	0.0021	0.074*
C12	0.0259 (9)	0.58440 (18)	−0.0482 (4)	0.0754 (12)
H12	−0.0452	0.5698	−0.1151	0.091*
C13	−0.0762 (9)	0.62724 (17)	−0.0198 (4)	0.0783 (14)
H13	−0.2157	0.6419	−0.0677	0.094*
C14	0.0259 (8)	0.64873 (13)	0.0791 (4)	0.0731 (13)
H14	−0.0454	0.6778	0.0992	0.088*
C15	0.2341 (7)	0.62698 (11)	0.1483 (4)	0.0560 (10)
H15	0.3044	0.6417	0.2152	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0721 (6)	0.0349 (4)	0.0446 (5)	0.0042 (4)	0.0116 (4)	0.0001 (4)
S2	0.0618 (6)	0.0402 (4)	0.0561 (6)	0.0052 (4)	0.0197 (5)	0.0039 (4)
N1	0.0575 (16)	0.0352 (14)	0.0415 (16)	0.0028 (12)	0.0008 (14)	0.0020 (13)
N2	0.0601 (16)	0.0347 (14)	0.0451 (17)	0.0064 (12)	0.0132 (14)	0.0034 (13)
N3	0.107 (3)	0.0466 (19)	0.076 (3)	0.0025 (19)	0.019 (2)	0.0149 (19)
O1	0.170 (4)	0.076 (2)	0.110 (3)	−0.038 (2)	0.042 (3)	0.023 (2)
O2	0.406 (9)	0.068 (2)	0.152 (4)	0.020 (4)	0.178 (5)	0.029 (3)
C1	0.059 (2)	0.0388 (18)	0.055 (2)	−0.0062 (15)	−0.0015 (18)	0.0084 (17)
C2	0.080 (3)	0.0318 (17)	0.085 (3)	−0.0018 (17)	−0.009 (2)	0.008 (2)
C3	0.088 (3)	0.041 (2)	0.088 (3)	0.0135 (19)	0.006 (3)	−0.006 (2)
C4	0.081 (3)	0.055 (2)	0.063 (3)	0.0091 (19)	0.012 (2)	−0.002 (2)
C5	0.068 (2)	0.0364 (17)	0.057 (2)	0.0012 (16)	0.005 (2)	0.0052 (17)
C6	0.0516 (19)	0.0356 (16)	0.047 (2)	−0.0011 (14)	−0.0061 (17)	0.0048 (15)
C7	0.066 (2)	0.0368 (17)	0.046 (2)	−0.0010 (16)	0.0056 (18)	0.0076 (16)
C8	0.0456 (17)	0.0395 (16)	0.0358 (18)	0.0000 (13)	−0.0041 (15)	0.0037 (14)
C9	0.0454 (18)	0.0479 (18)	0.057 (2)	−0.0060 (15)	0.0100 (17)	0.0089 (17)
C10	0.0396 (17)	0.0466 (18)	0.041 (2)	−0.0072 (14)	0.0089 (15)	0.0093 (16)
C11	0.064 (2)	0.075 (2)	0.048 (2)	−0.001 (2)	0.014 (2)	−0.007 (2)
C12	0.073 (3)	0.111 (4)	0.041 (2)	−0.020 (3)	−0.001 (2)	0.003 (2)
C13	0.057 (2)	0.090 (3)	0.085 (4)	−0.010 (2)	−0.009 (2)	0.048 (3)
C14	0.067 (3)	0.047 (2)	0.103 (4)	−0.0021 (19)	−0.009 (3)	0.018 (2)
C15	0.060 (2)	0.0395 (18)	0.067 (3)	−0.0069 (16)	−0.006 (2)	0.0060 (18)

Geometric parameters (Å, º) top

S1—C8	1.648 (3)	C5—C6	1.389 (5)
S2—C8	1.735 (3)	C5—H5	0.9300
S2—C9	1.803 (3)	C6—C7	1.464 (4)
N1—C7	1.272 (4)	C7—H7	0.9300
N1—N2	1.363 (3)	C9—C10	1.507 (5)
N2—C8	1.349 (4)	C9—H9A	0.9700
N2—H2	0.8600	C9—H9B	0.9700
N3—O2	1.178 (5)	C10—C11	1.370 (5)
N3—O1	1.185 (4)	C10—C15	1.374 (5)
N3—C1	1.464 (5)	C11—C12	1.374 (6)
C1—C2	1.376 (5)	C11—H11	0.9300
C1—C6	1.390 (4)	C12—C13	1.361 (6)
C2—C3	1.377 (6)	C12—H12	0.9300
C2—H2A	0.9300	C13—C14	1.368 (6)
C3—C4	1.373 (5)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.370 (5)
C4—C5	1.373 (5)	C14—H14	0.9300
C4—H4	0.9300	C15—H15	0.9300

C8—S2—C9	102.38 (15)	C6—C7—H7	120.6
C7—N1—N2	116.1 (3)	N2—C8—S1	121.0 (2)
C8—N2—N1	120.3 (3)	N2—C8—S2	113.1 (2)
C8—N2—H2	119.8	S1—C8—S2	125.83 (18)
N1—N2—H2	119.8	C10—C9—S2	116.1 (2)
O2—N3—O1	119.9 (4)	C10—C9—H9A	108.3
O2—N3—C1	120.2 (4)	S2—C9—H9A	108.3
O1—N3—C1	119.8 (4)	C10—C9—H9B	108.3
C2—C1—C6	122.6 (4)	S2—C9—H9B	108.3
C2—C1—N3	115.7 (3)	H9A—C9—H9B	107.4
C6—C1—N3	121.7 (3)	C11—C10—C15	118.3 (3)
C1—C2—C3	119.6 (4)	C11—C10—C9	121.5 (3)
C1—C2—H2A	120.2	C15—C10—C9	120.1 (3)
C3—C2—H2A	120.2	C10—C11—C12	120.7 (4)
C4—C3—C2	119.4 (4)	C10—C11—H11	119.7
C4—C3—H3	120.3	C12—C11—H11	119.7
C2—C3—H3	120.3	C13—C12—C11	120.1 (4)
C5—C4—C3	120.2 (4)	C13—C12—H12	119.9
C5—C4—H4	119.9	C11—C12—H12	119.9
C3—C4—H4	119.9	C12—C13—C14	120.2 (4)
C4—C5—C6	122.4 (3)	C12—C13—H13	119.9
C4—C5—H5	118.8	C14—C13—H13	119.9
C6—C5—H5	118.8	C13—C14—C15	119.4 (4)
C5—C6—C1	115.8 (3)	C13—C14—H14	120.3
C5—C6—C7	119.1 (3)	C15—C14—H14	120.3
C1—C6—C7	125.1 (3)	C14—C15—C10	121.3 (4)
N1—C7—C6	118.8 (3)	C14—C15—H15	119.3
N1—C7—H7	120.6	C10—C15—H15	119.3

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C10–C15 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.86	2.51	3.359 (3)	171
C9—H9B···Cgⁱⁱ	0.97	2.50	3.410 (4)	156

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃N₃O₂S₂
M_r	331.40
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	4.673 (2), 28.498 (6), 11.735 (5)
β (°)	94.070 (4)
V (Å³)	1558.8 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.38 × 0.25 × 0.23

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.87, 0.94
No. of measured, independent and observed [I > 2σ(I)] reflections	6957, 2814, 1925
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.147, 1.05
No. of reflections	2814
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.47

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C10–C15 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.86	2.51	3.359 (3)	171
C9—H9B···Cgⁱⁱ	0.97	2.50	3.410 (4)	156

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x+1, y, z.

Acknowledgements

The work was supported by the Natural Science Foundation of Zhejiang Province, China (No. M203027).

References

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