1-[1-(4-Nitro­phen­yl)ethyl­idene]thio­semicarbazide

Wang, J.-G.; Jian, F.-F.; Ding, Y.-F.

doi:10.1107/S1600536808025105

organic compounds

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Volume 64| Part 9| September 2008| Page o1730

doi:10.1107/S1600536808025105

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1-[1-(4-Nitrophenyl)ethylidene]thiosemicarbazide

Jian-Gang Wang,^a Fang-Fang Jian ^b ^* and Yu-Feng Ding ^c

^aMicroscale Science Institute, Bioengineering School, Weifang University, Weifang 261061, People's Republic of China, ^bMicroscale Science Institute, Weifang University, Weifang 261061, People's Republic of China, and ^cNumber Seven Middle School, Weifang 261061, People's Republic of China
^*Correspondence e-mail: ffjian2008@163.com

(Received 14 July 2008; accepted 5 August 2008; online 9 August 2008)

The title compound, C₉H₁₀N₄O₂S, was prepared by the reaction of 1-(4-nitrophenyl)ethanone and thiosemicarbazide in ethanol at 367 K. There are weak intermolecular N—H⋯S and N—H⋯O hydrogen-bonding interactions in the crystal structure involving the amine and nitrile groups, respectively, as donors.

Related literature

For related literature, see: Jian et al. (2006 ); Qin et al. (2006 ); Rozwadowski et al. (1999 ).

Experimental

Crystal data

C₉H₁₀N₄O₂S
M_r = 238.27
Triclinic, $[P \overline 1]$
a = 7.4450 (15) Å
b = 9.3180 (19) Å
c = 9.4050 (19) Å
α = 62.08 (3)°
β = 76.41 (3)°
γ = 69.02 (3)°
V = 536.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 293 (2) K
0.20 × 0.15 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
2493 measured reflections
2307 independent reflections
1776 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.140
S = 1.08
2307 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯S1ⁱ	0.86	2.74	3.581 (2)	166
N4—H4A⋯O1ⁱⁱ	0.86	2.35	3.101 (3)	146
N4—H4B⋯O2ⁱⁱⁱ	0.86	2.29	3.133 (3)	166
Symmetry codes: (i) -x, -y+2, -z+1; (ii) -x, -y, -z+2; (iii) x-1, y+1, z-1.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808025105/at2598sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808025105/at2598Isup2.hkl

checkCIF report

Comment top

Schiff bases have been used extensively as ligands in the field of coordination chemistry (Jian et al., 2006). Schiff bases show biochemical and pharmacological applications. The growing interest in Schiff bases lately is also due to their ability to form intramolecular hydrogen bonds by electron coupling between acid-base centers (Rozwadowski et al.,1999). The title compound (I), was synthesized and we report here its crystal structure

In the crystal structure of (I) (Fig. 1). The C6–C9/N2/N3/S1 plane makes a dihedral angle of 19.78 (127)° with the benzene ring (C1—C6). The C═N bond length [1.281 (3) Å] and C═S bond length [1.685 (2) Å] are in agreement with those observed before (Jian et al., 2006; Qin et al., 2006). There are intermolecular N–H···S and N–H···O hydrogen-bond interactions to stabilize the crystal structure (Table 1).

Related literature top

For related literature, see: Jian et al. (2006); Qin et al. (2006); Rozwadowski et al. (1999).

Experimental top

A mixture of hydrochloric acid 0.6 mL (0.02 mol) and thiosemicarbazide 1.8 g (0.02 mol) was stirred with ethanol (50 mL) at 293 K for 2 h, then add 1-(4-nitrophenyl)ethanone 3.3 g (0.02 mol), then afford the title compound [4.17 g, yield: 87.6%]. Single crystals suitable for X-ray measurements were obtained by recrystallization from acetone and ethanol(1:1) at room temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.

1-[1-(4-Nitrophenyl)ethylidene]thiosemicarbazide top

Crystal data top

C₉H₁₀N₄O₂S	Z = 2
M_r = 238.27	F(000) = 248
Triclinic, P1	D_x = 1.475 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4450 (15) Å	Cell parameters from 1776 reflections
b = 9.3180 (19) Å	θ = 2.5–27.0°
c = 9.4050 (19) Å	µ = 0.29 mm⁻¹
α = 62.08 (3)°	T = 293 K
β = 76.41 (3)°	Block, yellow
γ = 69.02 (3)°	0.20 × 0.15 × 0.10 mm
V = 536.5 (3) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1776 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
Graphite monochromator	θ_max = 27.0°, θ_min = 2.5°
ϕ and ω scans	h = 0→8
2493 measured reflections	k = −11→11
2307 independent reflections	l = −11→11

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0802P)² + 0.1605P] where P = (F_o² + 2F_c²)/3
2307 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₉H₁₀N₄O₂S	γ = 69.02 (3)°
M_r = 238.27	V = 536.5 (3) Å³
Triclinic, P1	Z = 2
a = 7.4450 (15) Å	Mo Kα radiation
b = 9.3180 (19) Å	µ = 0.29 mm⁻¹
c = 9.4050 (19) Å	T = 293 K
α = 62.08 (3)°	0.20 × 0.15 × 0.10 mm
β = 76.41 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1776 reflections with I > 2σ(I)
2493 measured reflections	R_int = 0.026
2307 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.08	Δρ_max = 0.39 e Å⁻³
2307 reflections	Δρ_min = −0.38 e Å⁻³
145 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	−0.18728 (10)	0.97254 (7)	0.38617 (7)	0.0483 (2)
O1	0.2761 (3)	−0.3046 (2)	1.2287 (3)	0.0697 (6)
O2	0.4183 (3)	−0.2729 (2)	1.3830 (2)	0.0680 (6)
N1	0.3337 (3)	−0.2167 (2)	1.2626 (2)	0.0472 (5)
N2	0.0574 (3)	0.5445 (2)	0.7336 (2)	0.0373 (4)
N3	0.0128 (3)	0.7117 (2)	0.6222 (2)	0.0394 (4)
H3A	0.0744	0.7778	0.6144	0.047*
N4	−0.2206 (3)	0.6599 (2)	0.5464 (2)	0.0521 (5)
H4A	−0.1876	0.5573	0.6190	0.063*
H4B	−0.3121	0.6918	0.4873	0.063*
C1	0.1766 (3)	0.1958 (3)	0.9090 (3)	0.0392 (5)
H1A	0.1182	0.2381	0.8145	0.047*
C2	0.2135 (3)	0.0244 (3)	1.0120 (3)	0.0410 (5)
H2B	0.1813	−0.0485	0.9871	0.049*
C3	0.2990 (3)	−0.0353 (2)	1.1521 (3)	0.0364 (5)
C4	0.3527 (3)	0.0684 (3)	1.1924 (3)	0.0415 (5)
H4C	0.4109	0.0249	1.2873	0.050*
C5	0.3167 (3)	0.2400 (3)	1.0864 (3)	0.0397 (5)
H5A	0.3537	0.3112	1.1100	0.048*
C6	0.2260 (3)	0.3065 (2)	0.9453 (2)	0.0337 (4)
C7	0.1848 (3)	0.4909 (2)	0.8317 (3)	0.0371 (5)
C8	0.2907 (4)	0.5977 (3)	0.8389 (4)	0.0631 (8)
H8A	0.2478	0.7120	0.7589	0.095*
H8B	0.4268	0.5521	0.8185	0.095*
H8C	0.2649	0.5972	0.9441	0.095*
C9	−0.1299 (3)	0.7696 (3)	0.5255 (3)	0.0384 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0686 (4)	0.0278 (3)	0.0474 (4)	−0.0157 (3)	−0.0254 (3)	−0.0044 (2)
O1	0.0890 (15)	0.0312 (9)	0.0844 (14)	−0.0239 (9)	−0.0267 (11)	−0.0073 (9)
O2	0.0795 (14)	0.0444 (10)	0.0588 (11)	−0.0168 (9)	−0.0295 (10)	0.0051 (9)
N1	0.0442 (11)	0.0309 (9)	0.0534 (12)	−0.0102 (8)	−0.0077 (9)	−0.0062 (8)
N2	0.0450 (10)	0.0227 (8)	0.0400 (9)	−0.0076 (7)	−0.0105 (8)	−0.0084 (7)
N3	0.0478 (10)	0.0242 (8)	0.0446 (10)	−0.0109 (7)	−0.0151 (8)	−0.0078 (7)
N4	0.0678 (14)	0.0332 (10)	0.0558 (12)	−0.0205 (9)	−0.0276 (10)	−0.0047 (9)
C1	0.0448 (12)	0.0296 (10)	0.0433 (11)	−0.0090 (8)	−0.0139 (9)	−0.0120 (9)
C2	0.0468 (12)	0.0285 (10)	0.0513 (13)	−0.0119 (9)	−0.0106 (10)	−0.0158 (9)
C3	0.0352 (11)	0.0254 (9)	0.0404 (11)	−0.0070 (8)	−0.0027 (8)	−0.0088 (8)
C4	0.0462 (12)	0.0361 (11)	0.0392 (11)	−0.0105 (9)	−0.0112 (9)	−0.0109 (9)
C5	0.0481 (12)	0.0296 (10)	0.0444 (12)	−0.0100 (9)	−0.0119 (9)	−0.0152 (9)
C6	0.0347 (10)	0.0242 (9)	0.0400 (11)	−0.0063 (8)	−0.0064 (8)	−0.0119 (8)
C7	0.0404 (11)	0.0249 (9)	0.0442 (11)	−0.0068 (8)	−0.0093 (9)	−0.0124 (9)
C8	0.0745 (18)	0.0316 (11)	0.0821 (19)	−0.0198 (12)	−0.0407 (15)	−0.0044 (12)
C9	0.0481 (12)	0.0284 (10)	0.0379 (11)	−0.0111 (9)	−0.0093 (9)	−0.0108 (8)

Geometric parameters (Å, º) top

S1—C9	1.685 (2)	C1—H1A	0.9300
O1—N1	1.231 (3)	C2—C3	1.381 (3)
O2—N1	1.224 (3)	C2—H2B	0.9300
N1—C3	1.473 (3)	C3—C4	1.389 (3)
N2—C7	1.281 (3)	C4—C5	1.395 (3)
N2—N3	1.379 (2)	C4—H4C	0.9300
N3—C9	1.353 (3)	C5—C6	1.397 (3)
N3—H3A	0.8600	C5—H5A	0.9300
N4—C9	1.336 (3)	C6—C7	1.498 (3)
N4—H4A	0.8600	C7—C8	1.506 (3)
N4—H4B	0.8600	C8—H8A	0.9600
C1—C2	1.388 (3)	C8—H8B	0.9600
C1—C6	1.406 (3)	C8—H8C	0.9600

O2—N1—O1	123.1 (2)	C3—C4—H4C	121.0
O2—N1—C3	118.7 (2)	C5—C4—H4C	121.0
O1—N1—C3	118.15 (19)	C4—C5—C6	121.2 (2)
C7—N2—N3	119.08 (18)	C4—C5—H5A	119.4
C9—N3—N2	118.64 (17)	C6—C5—H5A	119.4
C9—N3—H3A	120.7	C5—C6—C1	118.60 (18)
N2—N3—H3A	120.7	C5—C6—C7	121.53 (18)
C9—N4—H4A	120.0	C1—C6—C7	119.86 (18)
C9—N4—H4B	120.0	N2—C7—C6	114.93 (18)
H4A—N4—H4B	120.0	N2—C7—C8	125.16 (19)
C2—C1—C6	121.03 (19)	C6—C7—C8	119.91 (18)
C2—C1—H1A	119.5	C7—C8—H8A	109.5
C6—C1—H1A	119.5	C7—C8—H8B	109.5
C3—C2—C1	118.5 (2)	H8A—C8—H8B	109.5
C3—C2—H2B	120.8	C7—C8—H8C	109.5
C1—C2—H2B	120.8	H8A—C8—H8C	109.5
C2—C3—C4	122.67 (19)	H8B—C8—H8C	109.5
C2—C3—N1	118.13 (19)	N4—C9—N3	117.19 (18)
C4—C3—N1	119.20 (19)	N4—C9—S1	122.63 (17)
C3—C4—C5	118.0 (2)	N3—C9—S1	120.19 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···S1ⁱ	0.86	2.74	3.581 (2)	166
N4—H4A···O1ⁱⁱ	0.86	2.35	3.101 (3)	146
N4—H4B···O2ⁱⁱⁱ	0.86	2.29	3.133 (3)	166

Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x, −y, −z+2; (iii) x−1, y+1, z−1.

Experimental details

Crystal data
Chemical formula	C₉H₁₀N₄O₂S
M_r	238.27
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.4450 (15), 9.3180 (19), 9.4050 (19)
α, β, γ (°)	62.08 (3), 76.41 (3), 69.02 (3)
V (Å³)	536.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2493, 2307, 1776
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.140, 1.08
No. of reflections	2307
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.38

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···S1ⁱ	0.86	2.74	3.581 (2)	166.4
N4—H4A···O1ⁱⁱ	0.86	2.35	3.101 (3)	145.5
N4—H4B···O2ⁱⁱⁱ	0.86	2.29	3.133 (3)	166.2

Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x, −y, −z+2; (iii) x−1, y+1, z−1.

References

Bruker (1997). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Jian, F.-F., Zhuang, R.-R., Wang, K.-F., Zhao, P.-S. & Xiao, H.-L. (2006). Acta Cryst. E62, o3198–o3199. Web of Science CSD CrossRef IUCr Journals Google Scholar
Qin, Y.-Q., Ren, X.-Y., Liang, T.-L. & Jian, F.-F. (2006). Acta Cryst. E62, o5215–o5216. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rozwadowski, Z., Majewski, E., Dziembowska, T. & Hansen, P. E. (1999). J. Chem. Soc. Perkin Trans. 2, pp. 2809–2817. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1730

doi:10.1107/S1600536808025105

Open

access