N-(2-Nitro­phenyl­carbamothio­yl)acetamide

Shahwar, D.; Tahir, M.N.; Chohan, M.M.; Khan, M.A.; Ahmad, N.

doi:10.1107/S1600536812016947

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1578

doi:10.1107/S1600536812016947

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N-(2-Nitrophenylcarbamothioyl)acetamide

Durre Shahwar,^a M. Nawaz Tahir,^b ^* Muhammad Mansha Chohan,^a Muhammad Akmal Khan ^a and Nadeem Ahmad ^c

^aDepartment of Chemistry, Government College University, Lahore, Pakistan, ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan, and ^cDepartment of Chemistry, University of Engineering and Technology, Lahore 54000, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 17 April 2012; accepted 18 April 2012; online 28 April 2012)

In the title compound, C₉H₉N₃O₃S, the benzene ring and the N-carbamothioylacetamide unit are oriented at a dihedral angle of 54.82 (4)°. The dihedral angle between the ring and its attached nitro group is 28.54 (12)°. An intramolecular, bifurcated N—H⋯(O,O) hydrogen bond generates two S(6) rings. In the crystal, inversion dimers linked by pairs of N—H⋯S hydrogen bonds generate R₂²(8) loops. Weak C—H⋯O interactions link the dimers.

Related literature

For related structures, see: Shahwar et al. (2012a ,b ,c ). For graph–set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₉H₉N₃O₃S
M_r = 239.25
Monoclinic, P 2₁ /n
a = 4.1992 (1) Å
b = 11.6081 (3) Å
c = 22.1035 (6) Å
β = 94.815 (1)°
V = 1073.63 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 296 K
0.35 × 0.15 × 0.13 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.945, T_max = 0.965
10065 measured reflections
2711 independent reflections
1969 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.105
S = 1.01
2711 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1	0.86	2.23	2.661 (2)	111
N2—H2⋯O3	0.86	1.93	2.630 (2)	137
N3—H3A⋯S1ⁱ	0.86	2.59	3.4371 (14)	168
C9—H9C⋯O2ⁱⁱ	0.96	2.51	3.428 (3)	161
Symmetry codes: (i) -x+2, -y, -z; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); 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 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812016947/hb6744sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812016947/hb6744Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812016947/hb6744Isup3.cml

checkCIF report

Comment top

The title compound I (Fig. 1) is in continuation to synthesize different derivatives of N-carbamothioylacetamide.

We have reported the crystal structures of N-(2-methylphenylcarbamothioyl)acetamide (Shahwar et al., 2012a), N-(3-chlorophenylcarbamothioyl)acetamide (Shahwar et al., 2012b) and N-(phenylcarbamothioyl)acetamide (Shahwar et al., 2012c) which are related to the (I).

In (I), the phenyl ring A (C1–C6) and the N-carbamothioylacetamide moiety B (N2/C7/S1/N3/C8/O3/C9) are planar with r. m. s. deviation of 0.0028 Å and 0.0181 Å, respectively. The dihedral angle between A/B is 54.82 (4)°. The nitro group C (O1/N1/O2) is of course planar. The dihedral angle between A/C and B/C are 28.68 (18) and 66.59 (12)°, respectively. There exist intramolecular H–bonding of N—H···O type (Table 1, Fig. 1) with two S(6) ring motifs (Bernstein et al., 1995). The molecules are dimerized due to N—H···S type of hydrogen bonds with R₂²(8) ring motifs (Table 1, Fig. 2). The dimers are interlinked from CH₃ groups due to C—H···O H–bondings (Table 1, Fig. 2) with nitro groups.

Related literature top

For related structures, see: Shahwar et al. (2012a,b,c). For graph–set notation, see: Bernstein et al. (1995).

Experimental top

Acetylchloride (0.1 mol, 7.13 ml) was added dropwise to a stirred solution of KSCN (0.11 mol) in dry acetone (50 ml), followed by slow addition of 2-nitroaniline (0.1 mol) in dry acetone (25 ml). The mixture was refluxed for 5–10 min, then poured on ice cooled water, which resulted in crude precipitate. Recrystallization of the precipitate from ethylacetate yielded colourless needles.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level. The dotted lines represent the intra-molecular H-bondings.
	Fig. 2. Partial packing diagram showing inversion dimers linked by pairs of N—H···S hydrogen bonds with R₂²(8) ring motifs.

N-(2-Nitrophenylcarbamothioyl)acetamide top

Crystal data top

C₉H₉N₃O₃S	F(000) = 496
M_r = 239.25	D_x = 1.480 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1969 reflections
a = 4.1992 (1) Å	θ = 1.9–28.4°
b = 11.6081 (3) Å	µ = 0.30 mm⁻¹
c = 22.1035 (6) Å	T = 296 K
β = 94.815 (1)°	Needle, colourless
V = 1073.63 (5) Å³	0.35 × 0.15 × 0.13 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2711 independent reflections
Radiation source: fine-focus sealed tube	1969 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 7.50 pixels mm^-1	θ_max = 28.4°, θ_min = 1.9°
ω scans	h = −5→5
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −15→15
T_min = 0.945, T_max = 0.965	l = −29→29
10065 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0428P)² + 0.3324P] where P = (F_o² + 2F_c²)/3
2711 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₉H₉N₃O₃S	V = 1073.63 (5) Å³
M_r = 239.25	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.1992 (1) Å	µ = 0.30 mm⁻¹
b = 11.6081 (3) Å	T = 296 K
c = 22.1035 (6) Å	0.35 × 0.15 × 0.13 mm
β = 94.815 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2711 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1969 reflections with I > 2σ(I)
T_min = 0.945, T_max = 0.965	R_int = 0.029
10065 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.01	Δρ_max = 0.22 e Å⁻³
2711 reflections	Δρ_min = −0.22 e Å⁻³
146 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	1.09141 (12)	0.18209 (4)	0.01646 (2)	0.0470 (2)
O1	1.0422 (5)	0.23102 (15)	0.24000 (7)	0.0772 (7)
O2	1.4312 (4)	0.3495 (2)	0.25974 (8)	0.1053 (8)
O3	0.5502 (4)	0.04876 (12)	0.17207 (6)	0.0676 (5)
N1	1.1962 (4)	0.31649 (18)	0.22843 (7)	0.0608 (6)
N2	0.8449 (4)	0.22014 (12)	0.12253 (6)	0.0441 (5)
N3	0.7962 (3)	0.03702 (12)	0.08415 (6)	0.0405 (4)
C1	0.9181 (4)	0.33887 (14)	0.12522 (7)	0.0402 (5)
C2	1.0856 (4)	0.38734 (16)	0.17587 (8)	0.0465 (6)
C3	1.1536 (5)	0.50364 (19)	0.17923 (11)	0.0654 (8)
C4	1.0529 (6)	0.57302 (19)	0.13141 (12)	0.0763 (9)
C5	0.8855 (6)	0.52747 (18)	0.08093 (11)	0.0678 (8)
C6	0.8168 (5)	0.41127 (16)	0.07781 (9)	0.0537 (7)
C7	0.9000 (4)	0.14835 (14)	0.07749 (7)	0.0369 (5)
C8	0.6239 (4)	−0.00808 (16)	0.12923 (8)	0.0449 (6)
C9	0.5378 (5)	−0.13221 (17)	0.12095 (8)	0.0522 (6)
H2	0.75624	0.19142	0.15281	0.0529*
H3	1.26623	0.53434	0.21351	0.0785*
H3A	0.84485	−0.01078	0.05666	0.0485*
H4	1.09789	0.65145	0.13307	0.0915*
H5	0.81794	0.57530	0.04862	0.0814*
H6	0.70161	0.38146	0.04358	0.0645*
H9A	0.72667	−0.17858	0.12780	0.0784*
H9B	0.44403	−0.14442	0.08033	0.0784*
H9C	0.38729	−0.15343	0.14937	0.0784*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0619 (3)	0.0391 (2)	0.0416 (3)	−0.0060 (2)	0.0135 (2)	−0.0040 (2)
O1	0.1231 (15)	0.0614 (10)	0.0455 (9)	0.0175 (10)	−0.0028 (9)	0.0020 (7)
O2	0.0672 (11)	0.177 (2)	0.0673 (11)	0.0072 (12)	−0.0204 (9)	−0.0075 (12)
O3	0.0970 (11)	0.0569 (9)	0.0533 (8)	−0.0117 (8)	0.0325 (8)	−0.0063 (7)
N1	0.0646 (11)	0.0792 (13)	0.0381 (9)	0.0208 (10)	0.0014 (8)	−0.0132 (9)
N2	0.0628 (9)	0.0352 (7)	0.0350 (8)	0.0011 (7)	0.0087 (7)	−0.0019 (6)
N3	0.0512 (8)	0.0335 (7)	0.0371 (7)	0.0002 (6)	0.0064 (6)	−0.0022 (6)
C1	0.0491 (10)	0.0345 (9)	0.0375 (9)	0.0039 (7)	0.0063 (7)	−0.0051 (7)
C2	0.0500 (10)	0.0498 (10)	0.0401 (9)	0.0066 (8)	0.0066 (8)	−0.0085 (8)
C3	0.0704 (14)	0.0558 (13)	0.0700 (14)	−0.0081 (11)	0.0060 (11)	−0.0250 (11)
C4	0.0957 (18)	0.0385 (11)	0.0970 (19)	−0.0106 (11)	0.0224 (15)	−0.0133 (12)
C5	0.0949 (17)	0.0420 (11)	0.0676 (14)	0.0081 (11)	0.0134 (13)	0.0081 (10)
C6	0.0704 (13)	0.0411 (10)	0.0488 (11)	0.0069 (9)	−0.0004 (9)	−0.0004 (8)
C7	0.0411 (9)	0.0341 (8)	0.0345 (8)	0.0033 (7)	−0.0026 (7)	−0.0017 (6)
C8	0.0503 (10)	0.0454 (10)	0.0390 (9)	−0.0017 (8)	0.0033 (8)	0.0036 (8)
C9	0.0594 (12)	0.0500 (11)	0.0470 (10)	−0.0126 (9)	0.0031 (9)	0.0041 (8)

Geometric parameters (Å, º) top

S1—C7	1.6737 (17)	C2—C3	1.381 (3)
O1—N1	1.223 (3)	C3—C4	1.367 (3)
O2—N1	1.219 (2)	C4—C5	1.374 (4)
O3—C8	1.215 (2)	C5—C6	1.380 (3)
N1—C2	1.467 (2)	C8—C9	1.493 (3)
N2—C1	1.412 (2)	C3—H3	0.9300
N2—C7	1.333 (2)	C4—H4	0.9300
N3—C7	1.376 (2)	C5—H5	0.9300
N3—C8	1.383 (2)	C6—H6	0.9300
N2—H2	0.8600	C9—H9A	0.9600
N3—H3A	0.8600	C9—H9B	0.9600
C1—C6	1.382 (3)	C9—H9C	0.9600
C1—C2	1.390 (2)

O1—N1—O2	123.61 (19)	S1—C7—N3	118.95 (12)
O1—N1—C2	118.86 (16)	N2—C7—N3	115.52 (14)
O2—N1—C2	117.45 (19)	O3—C8—C9	123.00 (17)
C1—N2—C7	126.20 (14)	N3—C8—C9	114.40 (15)
C7—N3—C8	128.50 (14)	O3—C8—N3	122.61 (17)
C1—N2—H2	117.00	C2—C3—H3	120.00
C7—N2—H2	117.00	C4—C3—H3	120.00
C7—N3—H3A	116.00	C3—C4—H4	120.00
C8—N3—H3A	116.00	C5—C4—H4	120.00
N2—C1—C2	121.50 (15)	C4—C5—H5	120.00
N2—C1—C6	120.62 (15)	C6—C5—H5	120.00
C2—C1—C6	117.85 (16)	C1—C6—H6	120.00
C1—C2—C3	121.84 (18)	C5—C6—H6	120.00
N1—C2—C1	121.07 (16)	C8—C9—H9A	109.00
N1—C2—C3	117.09 (17)	C8—C9—H9B	109.00
C2—C3—C4	119.0 (2)	C8—C9—H9C	109.00
C3—C4—C5	120.3 (2)	H9A—C9—H9B	109.00
C4—C5—C6	120.5 (2)	H9A—C9—H9C	109.00
C1—C6—C5	120.45 (19)	H9B—C9—H9C	109.00
S1—C7—N2	125.50 (13)

O1—N1—C2—C3	149.7 (2)	C6—C1—C2—N1	178.95 (17)
O1—N1—C2—C1	−30.0 (3)	C6—C1—C2—C3	−0.7 (3)
O2—N1—C2—C1	153.06 (19)	N2—C1—C6—C5	179.21 (19)
O2—N1—C2—C3	−27.3 (3)	C2—C1—C6—C5	0.9 (3)
C7—N2—C1—C2	−129.53 (19)	N2—C1—C2—N1	0.7 (3)
C7—N2—C1—C6	52.2 (3)	N2—C1—C2—C3	−178.95 (17)
C1—N2—C7—S1	4.5 (3)	N1—C2—C3—C4	−179.54 (19)
C1—N2—C7—N3	−177.62 (15)	C1—C2—C3—C4	0.1 (3)
C8—N3—C7—N2	4.8 (2)	C2—C3—C4—C5	0.3 (3)
C7—N3—C8—O3	−2.9 (3)	C3—C4—C5—C6	0.0 (4)
C7—N3—C8—C9	177.33 (16)	C4—C5—C6—C1	−0.6 (3)
C8—N3—C7—S1	−177.15 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	2.23	2.661 (2)	111
N2—H2···O3	0.86	1.93	2.630 (2)	137
N3—H3A···S1ⁱ	0.86	2.59	3.4371 (14)	168
C9—H9C···O2ⁱⁱ	0.96	2.51	3.428 (3)	161

Symmetry codes: (i) −x+2, −y, −z; (ii) −x+3/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₉N₃O₃S
M_r	239.25
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	4.1992 (1), 11.6081 (3), 22.1035 (6)
β (°)	94.815 (1)
V (Å³)	1073.63 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.35 × 0.15 × 0.13

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.945, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	10065, 2711, 1969
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.105, 1.01
No. of reflections	2711
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.22

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	2.23	2.661 (2)	111
N2—H2···O3	0.86	1.93	2.630 (2)	137
N3—H3A···S1ⁱ	0.86	2.59	3.4371 (14)	168
C9—H9C···O2ⁱⁱ	0.96	2.51	3.428 (3)	161

Symmetry codes: (i) −x+2, −y, −z; (ii) −x+3/2, y−1/2, −z+1/2.

Acknowledgements

The authors acknowledge the provision of funds for the purchase of a diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. The authors also acknowledge the technical support provided by Syed Muhammad Hussain Rizvi of Bana International, Karachi, Pakistan.

References

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