Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808014530/sg2240sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536808014530/sg2240Isup2.hkl |
CCDC reference: 691006
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (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
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.
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).
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).
C12H15N3O3S | F(000) = 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 = 2.0–27.5° |
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 |
Bruker SMART APEX CCD area-detector diffractometer | 3020 independent reflections |
Radiation source: fine-focus sealed tube | 2321 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
Detector resolution: 83.66 pixels mm-1 | θmax = 27.5°, θmin = 2.0° |
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 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(Fo2) + (0.0642P)2 + 0.0515P] where P = (Fo2 + 2Fc2)/3 |
S = 0.91 | (Δ/σ)max < 0.001 |
3020 reflections | Δρmax = 0.28 e Å−3 |
172 parameters | Δρmin = −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) |
C12H15N3O3S | V = 1379.5 (6) Å3 |
Mr = 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 |
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 = 0.972 | Rint = 0.032 |
8152 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.103 | Δρmax = 0.28 e Å−3 |
S = 0.91 | Δρmin = −0.15 e Å−3 |
3020 reflections | Absolute structure: Flack (1983), 1296 Friedel pairs |
172 parameters | Absolute structure parameter: 0.07 (9) |
1 restraint |
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. |
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* |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.893, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8152, 3020, 2321 |
Rint | 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 |
Δρmax, Δρmin (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).
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. |
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).