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

Abstract

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,

• a = 20.400 (5) Å

• b = 10.886 (3) Å

• c = 6.2120 (15) Å

• V = 1379.5 (6) ų

• 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[F ² > 2σ(F ²)] = 0.042

• wR(F ²) = 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)

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 ▶).

Supplementary Material

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

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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

After their location in the difference map, all H-atoms were fixed geometrically at ideal positions and allowed to ride on the parent C or N atoms with C—H = 0.93–0.97Å and N—H = 0.86Å with U_iso(H)= 1.2 (CH₂ and NH) or 1.5U_eq(C)(CH₃).

Figures

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.

Crystal data

C12H15N3O3S	F000 = 592
Mr = 281.33	Dx = 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 = 2.0–27.5º
b = 10.886 (3) Å	µ = 0.24 mm−1
c = 6.2120 (15) Å	T = 273 (2) K
V = 1379.5 (6) Å3	Block, colourless
Z = 4	0.48 × 0.18 × 0.12 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3020 independent reflections
Radiation source: fine-focus sealed tube	2321 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.032
Detector resolution: 83.66 pixels mm-1	θmax = 27.5º
T = 298(2) K	θmin = 2.0º
ω scans	h = −21→26
Absorption correction: multi-scan(SADABS; Bruker, 2000)	k = −13→14
Tmin = 0.893, Tmax = 0.972	l = −7→7
8152 measured reflections

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.042	w = 1/[σ2(Fo2) + (0.0642P)2 + 0.0515P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.103	(Δ/σ)max < 0.001
S = 0.91	Δρmax = 0.28 e Å−3
3020 reflections	Δρmin = −0.14 e Å−3
172 parameters	Extinction correction: none
1 restraint	Absolute structure: Flack (1983), 1296 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.07 (9)
Secondary atom site location: difference Fourier map

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.