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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808014530/sg2240sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536808014530/sg2240Isup2.hkl
Contains datablock I

CCDC reference: 691006

Key indicators

  • Single-crystal X-ray study
  • T = 273 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.042
  • wR factor = 0.103
  • Data-to-parameter ratio = 17.6

checkCIF/PLATON results

No syntax errors found



Alert level C SHFSU01_ALERT_2_C Test not performed. _refine_ls_shift/su_max and _refine_ls_shift/esd_max not present. Absolute value of the parameter shift to su ratio given 0.001 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N3 PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.48 From the CIF: _reflns_number_total 3020 Count of symmetry unique reflns 1724 Completeness (_total/calc) 175.17% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1296 Fraction of Friedel pairs measured 0.752 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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.

Refinement top

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 Uiso(H)= 1.2 (CH2 and NH) or 1.5Ueq(C)(CH3).

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
[Figure 1] 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.
[Figure 2] 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
C12H15N3O3SF(000) = 592
Mr = 281.33Dx = 1.355 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 925 reflections
a = 20.400 (5) Åθ = 2.0–27.5°
b = 10.886 (3) ŵ = 0.24 mm1
c = 6.2120 (15) ÅT = 273 K
V = 1379.5 (6) Å3Block, colourless
Z = 40.48 × 0.18 × 0.12 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3020 independent reflections
Radiation source: fine-focus sealed tube2321 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
Detector resolution: 83.66 pixels mm-1θmax = 27.5°, θmin = 2.0°
ω scansh = 2126
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
k = 1314
Tmin = 0.893, Tmax = 0.972l = 77
8152 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.103 w = 1/[σ2(Fo2) + (0.0642P)2 + 0.0515P]
where P = (Fo2 + 2Fc2)/3
S = 0.91(Δ/σ)max < 0.001
3020 reflectionsΔρmax = 0.28 e Å3
172 parametersΔρmin = 0.15 e Å3
1 restraintAbsolute structure: Flack (1983), 1296 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.07 (9)
Crystal data top
C12H15N3O3SV = 1379.5 (6) Å3
Mr = 281.33Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 20.400 (5) ŵ = 0.24 mm1
b = 10.886 (3) ÅT = 273 K
c = 6.2120 (15) Å0.48 × 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)
Tmin = 0.893, Tmax = 0.972Rint = 0.032
8152 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.103Δρmax = 0.28 e Å3
S = 0.91Δρmin = 0.15 e Å3
3020 reflectionsAbsolute structure: Flack (1983), 1296 Friedel pairs
172 parametersAbsolute 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
xyzUiso*/Ueq
S10.97040 (3)0.39600 (5)0.62603 (13)0.04412 (17)
O30.72971 (13)0.0240 (2)0.9230 (4)0.0936 (8)
O20.73374 (10)0.13216 (17)0.6346 (5)0.0791 (6)
O10.84682 (10)0.73243 (15)0.7556 (4)0.0694 (6)
N20.86872 (9)0.49974 (16)0.8218 (3)0.0422 (5)
H2A0.84560.56400.84800.051*
N10.92866 (9)0.62483 (14)0.5965 (3)0.0394 (5)
H1A0.96030.63040.50550.047*
C110.79218 (11)0.2008 (2)0.9299 (4)0.0414 (5)
C100.81336 (11)0.1747 (2)1.1350 (5)0.0490 (6)
H10A0.79990.10351.20520.059*
C90.85486 (13)0.2563 (2)1.2331 (5)0.0521 (6)
H9A0.87040.23951.37080.062*
C80.87392 (11)0.36328 (19)1.1304 (5)0.0463 (5)
H8A0.90180.41871.19850.056*
C70.85101 (11)0.38661 (19)0.9253 (4)0.0387 (5)
C120.80979 (11)0.3062 (2)0.8226 (4)0.0413 (5)
H12A0.79420.32240.68480.050*
N30.74809 (11)0.11334 (19)0.8218 (5)0.0557 (6)
C60.91904 (11)0.50999 (19)0.6876 (4)0.0375 (5)
C50.89385 (11)0.73105 (18)0.6338 (5)0.0421 (5)
C40.91691 (13)0.8460 (2)0.5166 (4)0.0451 (6)
C30.90038 (15)0.8322 (3)0.2772 (5)0.0635 (8)
H3A0.92390.76340.21890.095*
H3B0.91280.90560.20190.095*
H3C0.85410.81880.26100.095*
C20.87985 (15)0.9559 (2)0.6113 (7)0.0733 (8)
H2B0.89050.96410.76110.110*
H2C0.83350.94300.59580.110*
H2D0.89231.02940.53630.110*
C10.99039 (14)0.8627 (2)0.5451 (6)0.0625 (8)
H1B1.01300.79380.48340.094*
H1C1.00050.86810.69570.094*
H1D1.00410.93680.47420.094*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0528 (3)0.0349 (3)0.0446 (3)0.0050 (2)0.0020 (3)0.0025 (3)
O30.124 (2)0.0680 (13)0.0885 (16)0.0522 (13)0.0132 (15)0.0002 (13)
O20.0909 (15)0.0660 (12)0.0804 (15)0.0173 (10)0.0336 (15)0.0052 (14)
O10.0707 (13)0.0443 (10)0.0930 (16)0.0126 (9)0.0308 (12)0.0156 (10)
N20.0457 (10)0.0311 (9)0.0497 (11)0.0041 (8)0.0075 (10)0.0086 (8)
N10.0440 (10)0.0325 (9)0.0416 (13)0.0003 (7)0.0044 (10)0.0064 (8)
C110.0378 (12)0.0376 (12)0.0488 (14)0.0003 (10)0.0062 (11)0.0013 (11)
C100.0557 (14)0.0387 (11)0.0526 (14)0.0019 (10)0.0128 (15)0.0136 (15)
C90.0650 (16)0.0508 (14)0.0404 (13)0.0030 (13)0.0015 (12)0.0109 (12)
C80.0488 (12)0.0427 (11)0.0474 (13)0.0016 (9)0.0003 (15)0.0004 (14)
C70.0396 (13)0.0366 (12)0.0399 (13)0.0020 (9)0.0051 (10)0.0043 (10)
C120.0423 (13)0.0409 (12)0.0409 (13)0.0024 (10)0.0016 (11)0.0056 (11)
N30.0540 (13)0.0435 (12)0.0695 (16)0.0055 (10)0.0068 (12)0.0009 (11)
C60.0391 (11)0.0367 (12)0.0366 (14)0.0034 (10)0.0084 (9)0.0029 (9)
C50.0441 (12)0.0350 (10)0.0471 (12)0.0004 (9)0.0006 (13)0.0067 (13)
C40.0520 (15)0.0313 (11)0.0519 (15)0.0003 (11)0.0008 (12)0.0078 (10)
C30.0761 (19)0.0570 (16)0.0575 (19)0.0034 (14)0.0070 (15)0.0183 (14)
C20.093 (2)0.0359 (12)0.091 (2)0.0162 (13)0.020 (2)0.0097 (18)
C10.0643 (18)0.0414 (14)0.082 (2)0.0118 (13)0.0026 (15)0.0018 (13)
Geometric parameters (Å, º) top
S1—C61.668 (2)C8—C71.381 (4)
O3—N31.217 (3)C8—H8A0.9300
O2—N31.216 (3)C7—C121.371 (3)
O1—C51.222 (3)C12—H12A0.9300
N2—C61.327 (3)C5—C41.523 (3)
N2—C71.435 (3)C4—C11.520 (4)
N2—H2A0.8600C4—C31.532 (4)
N1—C51.377 (3)C4—C21.532 (4)
N1—C61.386 (3)C3—H3A0.9600
N1—H1A0.8600C3—H3B0.9600
C11—C101.375 (4)C3—H3C0.9600
C11—C121.375 (3)C2—H2B0.9600
C11—N31.472 (3)C2—H2C0.9600
C10—C91.370 (4)C2—H2D0.9600
C10—H10A0.9300C1—H1B0.9600
C9—C81.384 (3)C1—H1C0.9600
C9—H9A0.9300C1—H1D0.9600
C6—N2—C7123.23 (18)N1—C6—S1119.22 (17)
C6—N2—H2A118.4O1—C5—N1121.3 (2)
C7—N2—H2A118.4O1—C5—C4121.9 (2)
C5—N1—C6128.0 (2)N1—C5—C4116.8 (2)
C5—N1—H1A116.0C1—C4—C5110.3 (2)
C6—N1—H1A116.0C1—C4—C3110.0 (2)
C10—C11—C12122.7 (2)C5—C4—C3108.4 (2)
C10—C11—N3118.8 (2)C1—C4—C2110.4 (2)
C12—C11—N3118.6 (2)C5—C4—C2107.8 (2)
C9—C10—C11118.2 (2)C3—C4—C2109.9 (3)
C9—C10—H10A120.9C4—C3—H3A109.5
C11—C10—H10A120.9C4—C3—H3B109.5
C10—C9—C8120.9 (3)H3A—C3—H3B109.5
C10—C9—H9A119.5C4—C3—H3C109.5
C8—C9—H9A119.5H3A—C3—H3C109.5
C7—C8—C9119.0 (2)H3B—C3—H3C109.5
C7—C8—H8A120.5C4—C2—H2B109.5
C9—C8—H8A120.5C4—C2—H2C109.5
C12—C7—C8121.3 (2)H2B—C2—H2C109.5
C12—C7—N2119.6 (2)C4—C2—H2D109.5
C8—C7—N2119.1 (2)H2B—C2—H2D109.5
C7—C12—C11117.9 (2)H2C—C2—H2D109.5
C7—C12—H12A121.1C4—C1—H1B109.5
C11—C12—H12A121.1C4—C1—H1C109.5
O2—N3—O3123.7 (3)H1B—C1—H1C109.5
O2—N3—C11118.3 (2)C4—C1—H1D109.5
O3—N3—C11118.0 (3)H1B—C1—H1D109.5
N2—C6—N1116.21 (19)H1C—C1—H1D109.5
N2—C6—S1124.57 (17)
C12—C11—C10—C91.5 (4)C10—C11—N3—O33.4 (3)
N3—C11—C10—C9179.4 (2)C12—C11—N3—O3175.7 (2)
C11—C10—C9—C81.2 (4)C7—N2—C6—N1178.4 (2)
C10—C9—C8—C70.6 (4)C7—N2—C6—S12.2 (3)
C9—C8—C7—C120.2 (4)C5—N1—C6—N22.6 (4)
C9—C8—C7—N2177.6 (2)C5—N1—C6—S1176.9 (2)
C6—N2—C7—C1287.3 (3)C6—N1—C5—O12.1 (4)
C6—N2—C7—C895.2 (3)C6—N1—C5—C4177.8 (2)
C8—C7—C12—C110.4 (3)O1—C5—C4—C1130.5 (3)
N2—C7—C12—C11177.81 (19)N1—C5—C4—C149.4 (3)
C10—C11—C12—C71.0 (3)O1—C5—C4—C3109.0 (3)
N3—C11—C12—C7179.9 (2)N1—C5—C4—C371.1 (3)
C10—C11—N3—O2174.3 (2)O1—C5—C4—C29.9 (4)
C12—C11—N3—O26.6 (3)N1—C5—C4—C2170.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.861.922.605 (3)135
N1—H1A···S1i0.862.763.582 (2)160
C3—H3A···S1i0.962.833.742 (3)159
N2—H2A···O2ii0.862.523.197 (3)137
Symmetry codes: (i) x+2, y+1, z1/2; (ii) x+3/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC12H15N3O3S
Mr281.33
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)273
a, b, c (Å)20.400 (5), 10.886 (3), 6.2120 (15)
V3)1379.5 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.24
Crystal size (mm)0.48 × 0.18 × 0.12
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.893, 0.972
No. of measured, independent and
observed [I > 2σ(I)] reflections
8152, 3020, 2321
Rint0.032
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.103, 0.91
No. of reflections3020
No. of parameters172
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.28, 0.15
Absolute structureFlack (1983), 1296 Friedel pairs
Absolute structure parameter0.07 (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···AD—HH···AD···AD—H···A
N2—H2A···O10.861.922.605 (3)135
N1—H1A···S1i0.862.763.582 (2)160
C3—H3A···S1i0.962.833.742 (3)159
N2—H2A···O2ii0.862.523.197 (3)137
Symmetry codes: (i) x+2, y+1, z1/2; (ii) x+3/2, y+1/2, z+1/2.
 

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