N-(3-Nitro­phen­yl)-N′-pivaloylthio­urea

Yusof, M.S.M.; Muharam, S.H.; Kassim, M.B.; Yamin, B.M.

doi:10.1107/S1600536808014530

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1137

doi:10.1107/S1600536808014530

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N-(3-Nitrophenyl)-N′-pivaloylthiourea

M. Sukeri M. Yusof,^a ^* Siti Hajar Muharam,^a M. B. Kassim ^b and Bohari M. Yamin ^b

^aDepartment of Chemical Sciences, Faculty of Science and Technology, Universiti Malaysia Terengganu, Mengabang Telipot, 21030 Kuala Terengganu, Malaysia, and ^bSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
^*Correspondence e-mail: mohdsukeri@umt.edu.my

(Received 23 April 2008; accepted 14 May 2008; online 21 May 2008)

In the title compound, C₁₂H₁₅N₃O₃S, there is an intramolecular N—H⋯O hydrogen bond. The crystal structure is stabilized by intermolecular N—H⋯O, N—H⋯S and C—H⋯S hydrogen bonds, forming a two-dimensional network parallel to the ac plane.

Related literature

For related crystal structures, see: Saeed & Flörke (2007 ); Sultana et al. (2007 ).

Experimental

Crystal data

C₁₂H₁₅N₃O₃S
M_r = 281.33
Orthorhombic, P n a 2₁
a = 20.400 (5) Å
b = 10.886 (3) Å
c = 6.2120 (15) Å
V = 1379.5 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 273 (2) K
0.48 × 0.18 × 0.12 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.893, T_max = 0.972
8152 measured reflections
3020 independent reflections
2321 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.103
S = 0.91
3020 reflections
172 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.14 e Å⁻³
Absolute structure: Flack (1983 ), 1296 Friedel pairs
Flack parameter: 0.07 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.86	1.92	2.605 (3)	135
N1—H1A⋯S1ⁱ	0.86	2.76	3.582 (2)	160
C3—H3A⋯S1ⁱ	0.96	2.83	3.742 (3)	159
N2—H2A⋯O2ⁱⁱ	0.86	2.52	3.197 (3)	137
Symmetry codes: (i) $[-x+2, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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, PARST (Nardelli, 1995 ) and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808014530/sg2240sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014530/sg2240Isup2.hkl

checkCIF report

Comment top

Two isomers of N-nitrophenyl-N'-pivaloylthiourea were reported by Saeed & Flörke, (2007) (nitro group at ortho position) and Sultana et al., (2007) (nitro group at para position). Here, the molecule with a nitro group in the meta position, (I), has been successfully synthesized (Fig. 1). The molecule displays similar bond distances and angles to the related compounds.

The carbonylthiourea (S1/N1/N2/O1/C4–C7) and 3-nitrophenyl fragments are essentially planar, with maximum deviation of 0.077Å for atom O2 from the least square plane. The carbonylthiourea fragment makes a dihedral angle of 85.64 (7)° to the nitrophenyl fragment. There is an intramolecular hydrogen bond, N2—H2···O1 leading to a pseudo-six membered ring (O1···H2—N2—C6—N1—C5—O1). In the crystal structure, the molecules are linked by intermolecular interactions, N—H···O, N—H···S and C—H···S (symmetry codes as in Table 1) forming a two dimensional network along the ac plane (Fig.2).

Related literature top

For related crystal structures, see: Saeed & Flörke (2007); Sultana et al. (2007); Flack (1983).

Experimental top

To a stirring acetone solution (75 ml) of pivaloyl chloride (5.0 g, 0.04 mol) and ammonium thiocyanate (3.15 g, 0.04 mol), 3-nitroaniline (5.73 g, 0.04 mol) in 40 ml of acetone was added dropwise. The solution mixture was refluxed for 1 h. The resulting solution was poured into a beaker containing some ice blocks. The white precipitate was filtered off and washed with distilled water and cold ethanol before being dried under vacuum. Good quality crystals were obtained by recrystallization from THF.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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), PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures top

	Fig. 1. : The molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate intramolecular hydrogen bond.
	Fig. 2. : Packing diagram of compound,(I), viewed down the b axis. The dashed lines denote the N—H···O, N—H···S and C—H···S hydrogen bonds.

N-(3-Nitrophenyl)-N'-pivaloylthiourea top

Crystal data top

C₁₂H₁₅N₃O₃S	F(000) = 592
M_r = 281.33	D_x = 1.355 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 925 reflections
a = 20.400 (5) Å	θ = 2.0–27.5°
b = 10.886 (3) Å	µ = 0.24 mm⁻¹
c = 6.2120 (15) Å	T = 273 K
V = 1379.5 (6) Å³	Block, colourless
Z = 4	0.48 × 0.18 × 0.12 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3020 independent reflections
Radiation source: fine-focus sealed tube	2321 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 83.66 pixels mm^-1	θ_max = 27.5°, θ_min = 2.0°
ω scans	h = −21→26
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −13→14
T_min = 0.893, T_max = 0.972	l = −7→7
8152 measured reflections

Refinement top

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)] = 0.042	H-atom parameters constrained
wR(F²) = 0.103	w = 1/[σ²(F_o²) + (0.0642P)² + 0.0515P] where P = (F_o² + 2F_c²)/3
S = 0.91	(Δ/σ)_max < 0.001
3020 reflections	Δρ_max = 0.28 e Å⁻³
172 parameters	Δρ_min = −0.15 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1296 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.07 (9)

Crystal data top

C₁₂H₁₅N₃O₃S	V = 1379.5 (6) Å³
M_r = 281.33	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 20.400 (5) Å	µ = 0.24 mm⁻¹
b = 10.886 (3) Å	T = 273 K
c = 6.2120 (15) Å	0.48 × 0.18 × 0.12 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3020 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2321 reflections with I > 2σ(I)
T_min = 0.893, T_max = 0.972	R_int = 0.032
8152 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.103	Δρ_max = 0.28 e Å⁻³
S = 0.91	Δρ_min = −0.15 e Å⁻³
3020 reflections	Absolute structure: Flack (1983), 1296 Friedel pairs
172 parameters	Absolute structure parameter: 0.07 (9)
1 restraint

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	0.97040 (3)	0.39600 (5)	0.62603 (13)	0.04412 (17)
O3	0.72971 (13)	0.0240 (2)	0.9230 (4)	0.0936 (8)
O2	0.73374 (10)	0.13216 (17)	0.6346 (5)	0.0791 (6)
O1	0.84682 (10)	0.73243 (15)	0.7556 (4)	0.0694 (6)
N2	0.86872 (9)	0.49974 (16)	0.8218 (3)	0.0422 (5)
H2A	0.8456	0.5640	0.8480	0.051*
N1	0.92866 (9)	0.62483 (14)	0.5965 (3)	0.0394 (5)
H1A	0.9603	0.6304	0.5055	0.047*
C11	0.79218 (11)	0.2008 (2)	0.9299 (4)	0.0414 (5)
C10	0.81336 (11)	0.1747 (2)	1.1350 (5)	0.0490 (6)
H10A	0.7999	0.1035	1.2052	0.059*
C9	0.85486 (13)	0.2563 (2)	1.2331 (5)	0.0521 (6)
H9A	0.8704	0.2395	1.3708	0.062*
C8	0.87392 (11)	0.36328 (19)	1.1304 (5)	0.0463 (5)
H8A	0.9018	0.4187	1.1985	0.056*
C7	0.85101 (11)	0.38661 (19)	0.9253 (4)	0.0387 (5)
C12	0.80979 (11)	0.3062 (2)	0.8226 (4)	0.0413 (5)
H12A	0.7942	0.3224	0.6848	0.050*
N3	0.74809 (11)	0.11334 (19)	0.8218 (5)	0.0557 (6)
C6	0.91904 (11)	0.50999 (19)	0.6876 (4)	0.0375 (5)
C5	0.89385 (11)	0.73105 (18)	0.6338 (5)	0.0421 (5)
C4	0.91691 (13)	0.8460 (2)	0.5166 (4)	0.0451 (6)
C3	0.90038 (15)	0.8322 (3)	0.2772 (5)	0.0635 (8)
H3A	0.9239	0.7634	0.2189	0.095*
H3B	0.9128	0.9056	0.2019	0.095*
H3C	0.8541	0.8188	0.2610	0.095*
C2	0.87985 (15)	0.9559 (2)	0.6113 (7)	0.0733 (8)
H2B	0.8905	0.9641	0.7611	0.110*
H2C	0.8335	0.9430	0.5958	0.110*
H2D	0.8923	1.0294	0.5363	0.110*
C1	0.99039 (14)	0.8627 (2)	0.5451 (6)	0.0625 (8)
H1B	1.0130	0.7938	0.4834	0.094*
H1C	1.0005	0.8681	0.6957	0.094*
H1D	1.0041	0.9368	0.4742	0.094*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0528 (3)	0.0349 (3)	0.0446 (3)	0.0050 (2)	0.0020 (3)	0.0025 (3)
O3	0.124 (2)	0.0680 (13)	0.0885 (16)	−0.0522 (13)	0.0132 (15)	−0.0002 (13)
O2	0.0909 (15)	0.0660 (12)	0.0804 (15)	−0.0173 (10)	−0.0336 (15)	0.0052 (14)
O1	0.0707 (13)	0.0443 (10)	0.0930 (16)	0.0126 (9)	0.0308 (12)	0.0156 (10)
N2	0.0457 (10)	0.0311 (9)	0.0497 (11)	0.0041 (8)	0.0075 (10)	0.0086 (8)
N1	0.0440 (10)	0.0325 (9)	0.0416 (13)	−0.0003 (7)	0.0044 (10)	0.0064 (8)
C11	0.0378 (12)	0.0376 (12)	0.0488 (14)	−0.0003 (10)	0.0062 (11)	0.0013 (11)
C10	0.0557 (14)	0.0387 (11)	0.0526 (14)	−0.0019 (10)	0.0128 (15)	0.0136 (15)
C9	0.0650 (16)	0.0508 (14)	0.0404 (13)	0.0030 (13)	−0.0015 (12)	0.0109 (12)
C8	0.0488 (12)	0.0427 (11)	0.0474 (13)	−0.0016 (9)	−0.0003 (15)	−0.0004 (14)
C7	0.0396 (13)	0.0366 (12)	0.0399 (13)	0.0020 (9)	0.0051 (10)	0.0043 (10)
C12	0.0423 (13)	0.0409 (12)	0.0409 (13)	0.0024 (10)	0.0016 (11)	0.0056 (11)
N3	0.0540 (13)	0.0435 (12)	0.0695 (16)	−0.0055 (10)	0.0068 (12)	−0.0009 (11)
C6	0.0391 (11)	0.0367 (12)	0.0366 (14)	−0.0034 (10)	−0.0084 (9)	0.0029 (9)
C5	0.0441 (12)	0.0350 (10)	0.0471 (12)	0.0004 (9)	0.0006 (13)	0.0067 (13)
C4	0.0520 (15)	0.0313 (11)	0.0519 (15)	−0.0003 (11)	0.0008 (12)	0.0078 (10)
C3	0.0761 (19)	0.0570 (16)	0.0575 (19)	−0.0034 (14)	−0.0070 (15)	0.0183 (14)
C2	0.093 (2)	0.0359 (12)	0.091 (2)	0.0162 (13)	0.020 (2)	0.0097 (18)
C1	0.0643 (18)	0.0414 (14)	0.082 (2)	−0.0118 (13)	−0.0026 (15)	0.0018 (13)

Geometric parameters (Å, º) top

S1—C6	1.668 (2)	C8—C7	1.381 (4)
O3—N3	1.217 (3)	C8—H8A	0.9300
O2—N3	1.216 (3)	C7—C12	1.371 (3)
O1—C5	1.222 (3)	C12—H12A	0.9300
N2—C6	1.327 (3)	C5—C4	1.523 (3)
N2—C7	1.435 (3)	C4—C1	1.520 (4)
N2—H2A	0.8600	C4—C3	1.532 (4)
N1—C5	1.377 (3)	C4—C2	1.532 (4)
N1—C6	1.386 (3)	C3—H3A	0.9600
N1—H1A	0.8600	C3—H3B	0.9600
C11—C10	1.375 (4)	C3—H3C	0.9600
C11—C12	1.375 (3)	C2—H2B	0.9600
C11—N3	1.472 (3)	C2—H2C	0.9600
C10—C9	1.370 (4)	C2—H2D	0.9600
C10—H10A	0.9300	C1—H1B	0.9600
C9—C8	1.384 (3)	C1—H1C	0.9600
C9—H9A	0.9300	C1—H1D	0.9600

C6—N2—C7	123.23 (18)	N1—C6—S1	119.22 (17)
C6—N2—H2A	118.4	O1—C5—N1	121.3 (2)
C7—N2—H2A	118.4	O1—C5—C4	121.9 (2)
C5—N1—C6	128.0 (2)	N1—C5—C4	116.8 (2)
C5—N1—H1A	116.0	C1—C4—C5	110.3 (2)
C6—N1—H1A	116.0	C1—C4—C3	110.0 (2)
C10—C11—C12	122.7 (2)	C5—C4—C3	108.4 (2)
C10—C11—N3	118.8 (2)	C1—C4—C2	110.4 (2)
C12—C11—N3	118.6 (2)	C5—C4—C2	107.8 (2)
C9—C10—C11	118.2 (2)	C3—C4—C2	109.9 (3)
C9—C10—H10A	120.9	C4—C3—H3A	109.5
C11—C10—H10A	120.9	C4—C3—H3B	109.5
C10—C9—C8	120.9 (3)	H3A—C3—H3B	109.5
C10—C9—H9A	119.5	C4—C3—H3C	109.5
C8—C9—H9A	119.5	H3A—C3—H3C	109.5
C7—C8—C9	119.0 (2)	H3B—C3—H3C	109.5
C7—C8—H8A	120.5	C4—C2—H2B	109.5
C9—C8—H8A	120.5	C4—C2—H2C	109.5
C12—C7—C8	121.3 (2)	H2B—C2—H2C	109.5
C12—C7—N2	119.6 (2)	C4—C2—H2D	109.5
C8—C7—N2	119.1 (2)	H2B—C2—H2D	109.5
C7—C12—C11	117.9 (2)	H2C—C2—H2D	109.5
C7—C12—H12A	121.1	C4—C1—H1B	109.5
C11—C12—H12A	121.1	C4—C1—H1C	109.5
O2—N3—O3	123.7 (3)	H1B—C1—H1C	109.5
O2—N3—C11	118.3 (2)	C4—C1—H1D	109.5
O3—N3—C11	118.0 (3)	H1B—C1—H1D	109.5
N2—C6—N1	116.21 (19)	H1C—C1—H1D	109.5
N2—C6—S1	124.57 (17)

C12—C11—C10—C9	−1.5 (4)	C10—C11—N3—O3	3.4 (3)
N3—C11—C10—C9	179.4 (2)	C12—C11—N3—O3	−175.7 (2)
C11—C10—C9—C8	1.2 (4)	C7—N2—C6—N1	178.4 (2)
C10—C9—C8—C7	−0.6 (4)	C7—N2—C6—S1	−2.2 (3)
C9—C8—C7—C12	0.2 (4)	C5—N1—C6—N2	2.6 (4)
C9—C8—C7—N2	177.6 (2)	C5—N1—C6—S1	−176.9 (2)
C6—N2—C7—C12	−87.3 (3)	C6—N1—C5—O1	−2.1 (4)
C6—N2—C7—C8	95.2 (3)	C6—N1—C5—C4	177.8 (2)
C8—C7—C12—C11	−0.4 (3)	O1—C5—C4—C1	130.5 (3)
N2—C7—C12—C11	−177.81 (19)	N1—C5—C4—C1	−49.4 (3)
C10—C11—C12—C7	1.0 (3)	O1—C5—C4—C3	−109.0 (3)
N3—C11—C12—C7	−179.9 (2)	N1—C5—C4—C3	71.1 (3)
C10—C11—N3—O2	−174.3 (2)	O1—C5—C4—C2	9.9 (4)
C12—C11—N3—O2	6.6 (3)	N1—C5—C4—C2	−170.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	1.92	2.605 (3)	135
N1—H1A···S1ⁱ	0.86	2.76	3.582 (2)	160
C3—H3A···S1ⁱ	0.96	2.83	3.742 (3)	159
N2—H2A···O2ⁱⁱ	0.86	2.52	3.197 (3)	137

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₅N₃O₃S
M_r	281.33
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	273
a, b, c (Å)	20.400 (5), 10.886 (3), 6.2120 (15)
V (Å³)	1379.5 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.48 × 0.18 × 0.12

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.893, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	8152, 3020, 2321
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.103, 0.91
No. of reflections	3020
No. of parameters	172
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.15
Absolute structure	Flack (1983), 1296 Friedel pairs
Absolute structure parameter	0.07 (9)

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	1.92	2.605 (3)	135
N1—H1A···S1ⁱ	0.86	2.76	3.582 (2)	160
C3—H3A···S1ⁱ	0.96	2.83	3.742 (3)	159
N2—H2A···O2ⁱⁱ	0.86	2.52	3.197 (3)	137

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

Acknowledgements

The authors thank the Malaysian Government, Universiti Kebangsaan Malaysia, Universiti Malaysia Terengganu and the Ministry of Higher Education, Malaysia, for research grants OUP UKM OUP-BIT-28/20076 and UMT-FRGS-59001.

References

Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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