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In the structure of the title compound, C12H15N3O3S, the thio­amide and amide groups are almost coplanar with the benzene ring. The planes of the NO2 group and the benzene ring form a dihedral angle of 40.8 (2)°. The crystal packing shows inter­molecular N—H...S hydrogen bonds, forming centrosymmetric dimers which are stacked along [001].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704593X/zl2060sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680704593X/zl2060Isup2.hkl
Contains datablock I

CCDC reference: 667310

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.039
  • wR factor = 0.104
  • Data-to-parameter ratio = 19.4

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.05 PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 - C6 .. 5.18 su
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 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 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The coplanarity of thioamide and amide groups with the phenyl ring are reflected by the torsion angles C6–N1–C1–O1 of -6.1 (2)° and C8–N2–C6–N2 of 1.4 (2)°. This is a common feature for this type of compounds (Saeed & Flörke, 2006) as well as the intermolecular N–H···S hydrogen bonds (Table 2, Fig. 2), forming centrosymmetric dimers which are stacked along [001]. Two intermolecular C–H···S interactions with somewhat longer H···S distances are also present (see the hydrogen bonding table). Additionally, the typical (Saeed & Flörke, 2006) intramolecular N–H···O hydrogen bond is formed with the carbonyl function.

Related literature top

For related literature, see: Saeed & Flörke (2006, 2007).

Experimental top

A solution of freshly distilled pivaloyl chloride (1.20 g, 10 mmol) in acetone (50 ml) was added dropwise to a suspension of potassium thiocyanate (0.97 g,10 mmol) in acetone (30 ml) and the reaction mixture was refluxed for 30 min. After cooling to room temperature, a solution of 3-methoxyaniline (10 mmol) in acetone (10 ml) was added and the resulting mixture refluxed for 2.0 h. The reaction mixture was poured into cold water and the resulting precipitate was isolated by filtration followed by recrystallization from ethanol to afford the title thiourea compound as colourless crystals (2.33 g, 83.0 mmol, 83%). m.p. 352 K. IR (KBr) cm-1: 3351 (free NH), 3200 (assoc. NH), 1667 (CO), 1610 (arom.), 1529, 1325, 1160, 744, 762; 1H NMR (CDCl3) 1.27 (9H, s, pivaloyl), 3.89 (3H, s, ArOCH3), 7.31–7.75 (aromatic), 9.19 (1H, s, broad, NH); 12.76 (1H, s, broad, NH); EIMS m/e: 281, 283, 149, 119, 91, 64.9; Analysis calculated for C12H15N3O3S C, 51.23; H, 5.37; N, 14.94; S, 11.40 found C, 64.01; H, 5.32; N, 9..10; O, S, 10.65.

Refinement top

Hydrogen atoms were located in difference syntheses, refined at idealized positions riding on the C (C–H = 0.95–0.99 Å) or N (N–H = 0.88 Å) atoms with isotropic displacement parameters Uiso(H) = 1.2U(Ceq / Neq) and 1.5(methyl-C). Methyl H atoms were refined on the basis of rigid groups allowed to rotate but not tip.

Structure description top

The coplanarity of thioamide and amide groups with the phenyl ring are reflected by the torsion angles C6–N1–C1–O1 of -6.1 (2)° and C8–N2–C6–N2 of 1.4 (2)°. This is a common feature for this type of compounds (Saeed & Flörke, 2006) as well as the intermolecular N–H···S hydrogen bonds (Table 2, Fig. 2), forming centrosymmetric dimers which are stacked along [001]. Two intermolecular C–H···S interactions with somewhat longer H···S distances are also present (see the hydrogen bonding table). Additionally, the typical (Saeed & Flörke, 2006) intramolecular N–H···O hydrogen bond is formed with the carbonyl function.

For related literature, see: Saeed & Flörke (2006, 2007).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Bruker, 2002); program(s) used to refine structure: SHELXTL (Bruker, 2002); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL (Bruker, 2002).

Figures top
[Figure 1] Fig. 1. Molecular structure of title compound. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Crystal packing viewed along [001] with the intra- and N–H···S intermolecular hydrogen bonding pattern indicated as dashed lines. H-atoms not involved in hydrogen bonding are omitted.
1-(2-Nitrophenyl)-3-pivaloylthiourea top
Crystal data top
C12H15N3O3SF(000) = 592
Mr = 281.33Dx = 1.341 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 981 reflections
a = 10.8491 (14) Åθ = 2.5–28.2°
b = 11.8882 (16) ŵ = 0.24 mm1
c = 11.1206 (15) ÅT = 120 K
β = 103.723 (3)°Block, yellow
V = 1393.4 (3) Å30.50 × 0.41 × 0.25 mm
Z = 4
Data collection top
Bruker SMART APEX
diffractometer
3329 independent reflections
Radiation source: sealed tube2954 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
φ and ω scansθmax = 27.9°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 1412
Tmin = 0.890, Tmax = 0.933k = 1515
11932 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: difference Fourier map
wR(F2) = 0.104H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0528P)2 + 0.5774P]
where P = (Fo2 + 2Fc2)/3
3329 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C12H15N3O3SV = 1393.4 (3) Å3
Mr = 281.33Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.8491 (14) ŵ = 0.24 mm1
b = 11.8882 (16) ÅT = 120 K
c = 11.1206 (15) Å0.50 × 0.41 × 0.25 mm
β = 103.723 (3)°
Data collection top
Bruker SMART APEX
diffractometer
3329 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
2954 reflections with I > 2σ(I)
Tmin = 0.890, Tmax = 0.933Rint = 0.025
11932 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.104H-atom parameters constrained
S = 1.05Δρmax = 0.42 e Å3
3329 reflectionsΔρmin = 0.20 e Å3
172 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
xyzUiso*/Ueq
S10.99549 (3)0.16750 (3)0.98065 (4)0.02415 (12)
O10.57778 (10)0.08899 (9)0.84219 (10)0.0276 (2)
O20.76929 (17)0.45204 (15)1.14489 (13)0.0606 (4)
O30.63077 (16)0.34998 (13)1.02002 (15)0.0545 (4)
N10.78505 (11)0.04492 (9)0.92321 (10)0.0190 (2)
H1A0.83650.01040.95490.023*
N20.76148 (11)0.23423 (10)0.87778 (11)0.0215 (2)
H2A0.67950.22090.85440.026*
N30.72498 (15)0.40959 (12)1.04339 (13)0.0347 (3)
C10.65778 (13)0.01695 (12)0.87845 (12)0.0195 (3)
C20.62599 (13)0.10813 (12)0.87869 (13)0.0221 (3)
C30.48233 (15)0.12139 (14)0.83176 (17)0.0346 (4)
H3A0.43940.08160.88740.052*
H3B0.46010.20140.82960.052*
H3C0.45550.08970.74830.052*
C40.66637 (15)0.15607 (13)1.01035 (14)0.0264 (3)
H4A0.62260.11531.06460.040*
H4B0.75830.14751.04130.040*
H4C0.64400.23601.00920.040*
C50.69320 (16)0.17063 (13)0.79120 (15)0.0307 (3)
H5A0.66600.13910.70770.046*
H5B0.67110.25070.78920.046*
H5C0.78520.16200.82100.046*
C60.83936 (13)0.14998 (11)0.92322 (12)0.0181 (3)
C70.80631 (13)0.34525 (11)0.86576 (13)0.0205 (3)
C80.86926 (14)0.36909 (12)0.77407 (14)0.0248 (3)
H8A0.88190.31130.71920.030*
C90.91413 (15)0.47677 (13)0.76166 (14)0.0278 (3)
H9A0.95630.49260.69780.033*
C100.89742 (15)0.56134 (13)0.84252 (15)0.0303 (3)
H10A0.92810.63500.83360.036*
C110.83692 (16)0.53913 (13)0.93514 (15)0.0298 (3)
H11A0.82700.59640.99170.036*
C120.79046 (14)0.43159 (12)0.94491 (13)0.0236 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.01774 (18)0.01579 (18)0.0359 (2)0.00065 (12)0.00039 (14)0.00073 (13)
O10.0191 (5)0.0235 (5)0.0392 (6)0.0015 (4)0.0049 (4)0.0041 (4)
O20.0804 (12)0.0730 (11)0.0350 (7)0.0148 (9)0.0270 (7)0.0147 (7)
O30.0623 (10)0.0499 (8)0.0642 (10)0.0193 (7)0.0408 (8)0.0105 (7)
N10.0188 (5)0.0144 (5)0.0227 (6)0.0003 (4)0.0026 (4)0.0016 (4)
N20.0180 (5)0.0168 (6)0.0286 (6)0.0003 (4)0.0035 (5)0.0026 (4)
N30.0458 (9)0.0285 (7)0.0348 (7)0.0016 (6)0.0194 (6)0.0027 (6)
C10.0194 (6)0.0208 (6)0.0186 (6)0.0017 (5)0.0048 (5)0.0001 (5)
C20.0210 (7)0.0191 (7)0.0245 (7)0.0039 (5)0.0022 (5)0.0002 (5)
C30.0248 (8)0.0289 (8)0.0443 (9)0.0091 (6)0.0034 (7)0.0035 (7)
C40.0259 (7)0.0250 (7)0.0280 (7)0.0023 (5)0.0057 (6)0.0055 (6)
C50.0396 (9)0.0231 (7)0.0287 (8)0.0025 (6)0.0066 (6)0.0062 (6)
C60.0201 (6)0.0168 (6)0.0176 (6)0.0004 (5)0.0053 (5)0.0007 (5)
C70.0190 (6)0.0171 (6)0.0234 (7)0.0019 (5)0.0012 (5)0.0031 (5)
C80.0271 (7)0.0223 (7)0.0249 (7)0.0014 (6)0.0057 (6)0.0008 (6)
C90.0286 (8)0.0278 (7)0.0278 (7)0.0008 (6)0.0082 (6)0.0067 (6)
C100.0340 (8)0.0190 (7)0.0361 (8)0.0040 (6)0.0049 (6)0.0060 (6)
C110.0363 (8)0.0192 (7)0.0334 (8)0.0002 (6)0.0073 (6)0.0026 (6)
C120.0256 (7)0.0216 (7)0.0236 (7)0.0010 (5)0.0059 (5)0.0018 (5)
Geometric parameters (Å, º) top
S1—C61.6754 (14)C3—H3C0.9800
O1—C11.2180 (17)C4—H4A0.9800
O2—N31.226 (2)C4—H4B0.9800
O3—N31.220 (2)C4—H4C0.9800
N1—C61.3809 (17)C5—H5A0.9800
N1—C11.3924 (17)C5—H5B0.9800
N1—H1A0.8800C5—H5C0.9800
N2—C61.3304 (17)C7—C81.385 (2)
N2—C71.4238 (17)C7—C121.389 (2)
N2—H2A0.8800C8—C91.388 (2)
N3—C121.4634 (19)C8—H8A0.9500
C1—C21.5266 (19)C9—C101.389 (2)
C2—C31.530 (2)C9—H9A0.9500
C2—C41.535 (2)C10—C111.372 (2)
C2—C51.539 (2)C10—H10A0.9500
C3—H3A0.9800C11—C121.388 (2)
C3—H3B0.9800C11—H11A0.9500
C6—N1—C1127.08 (11)H4B—C4—H4C109.5
C6—N1—H1A116.5C2—C5—H5A109.5
C1—N1—H1A116.5C2—C5—H5B109.5
C6—N2—C7122.22 (12)H5A—C5—H5B109.5
C6—N2—H2A118.9C2—C5—H5C109.5
C7—N2—H2A118.9H5A—C5—H5C109.5
O3—N3—O2124.13 (15)H5B—C5—H5C109.5
O3—N3—C12118.38 (14)N2—C6—N1116.64 (12)
O2—N3—C12117.49 (15)N2—C6—S1123.01 (10)
O1—C1—N1121.25 (13)N1—C6—S1120.35 (10)
O1—C1—C2122.81 (12)C8—C7—C12118.18 (13)
N1—C1—C2115.93 (12)C8—C7—N2119.87 (13)
C1—C2—C3108.19 (12)C12—C7—N2121.95 (13)
C1—C2—C4110.48 (11)C7—C8—C9120.52 (14)
C3—C2—C4108.92 (12)C7—C8—H8A119.7
C1—C2—C5109.15 (12)C9—C8—H8A119.7
C3—C2—C5109.38 (13)C8—C9—C10120.03 (14)
C4—C2—C5110.68 (12)C8—C9—H9A120.0
C2—C3—H3A109.5C10—C9—H9A120.0
C2—C3—H3B109.5C11—C10—C9120.38 (14)
H3A—C3—H3B109.5C11—C10—H10A119.8
C2—C3—H3C109.5C9—C10—H10A119.8
H3A—C3—H3C109.5C10—C11—C12118.91 (14)
H3B—C3—H3C109.5C10—C11—H11A120.5
C2—C4—H4A109.5C12—C11—H11A120.5
C2—C4—H4B109.5C11—C12—C7121.95 (14)
H4A—C4—H4B109.5C11—C12—N3118.23 (13)
C2—C4—H4C109.5C7—C12—N3119.81 (13)
H4A—C4—H4C109.5
C6—N1—C1—O16.1 (2)N2—C7—C8—C9179.64 (13)
C6—N1—C1—C2174.25 (12)C7—C8—C9—C100.8 (2)
O1—C1—C2—C31.98 (19)C8—C9—C10—C110.2 (2)
N1—C1—C2—C3177.68 (12)C9—C10—C11—C121.4 (2)
O1—C1—C2—C4121.13 (15)C10—C11—C12—C71.7 (2)
N1—C1—C2—C458.53 (16)C10—C11—C12—N3179.36 (14)
O1—C1—C2—C5116.95 (15)C8—C7—C12—C110.8 (2)
N1—C1—C2—C563.38 (15)N2—C7—C12—C11178.37 (13)
C7—N2—C6—N1176.23 (12)C8—C7—C12—N3179.70 (13)
C7—N2—C6—S14.82 (19)N2—C7—C12—N30.6 (2)
C1—N1—C6—N21.4 (2)O3—N3—C12—C11140.14 (17)
C1—N1—C6—S1179.60 (10)O2—N3—C12—C1140.3 (2)
C6—N2—C7—C873.24 (18)O3—N3—C12—C740.9 (2)
C6—N2—C7—C12105.88 (16)O2—N3—C12—C7138.65 (17)
C12—C7—C8—C90.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.881.902.5953 (16)134
N1—H1A···S1i0.882.593.4614 (12)171
C4—H4B···S1i0.982.753.6486 (18)153
C5—H5C···S1i0.982.843.7121 (18)149
Symmetry code: (i) x+2, y, z+2.

Experimental details

Crystal data
Chemical formulaC12H15N3O3S
Mr281.33
Crystal system, space groupMonoclinic, P21/c
Temperature (K)120
a, b, c (Å)10.8491 (14), 11.8882 (16), 11.1206 (15)
β (°) 103.723 (3)
V3)1393.4 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.24
Crystal size (mm)0.50 × 0.41 × 0.25
Data collection
DiffractometerBruker SMART APEX
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.890, 0.933
No. of measured, independent and
observed [I > 2σ(I)] reflections
11932, 3329, 2954
Rint0.025
(sin θ/λ)max1)0.658
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.104, 1.05
No. of reflections3329
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.42, 0.20

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXTL (Bruker, 2002).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.881.902.5953 (16)134
N1—H1A···S1i0.882.593.4614 (12)171
C4—H4B···S1i0.982.753.6486 (18)153
C5—H5C···S1i0.982.843.7121 (18)149
Symmetry code: (i) x+2, y, z+2.
 

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