Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037531/cs2042sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037531/cs2042Isup2.hkl |
CCDC reference: 660201
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.003 Å
- R factor = 0.045
- wR factor = 0.115
- Data-to-parameter ratio = 18.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT420_ALERT_2_C D-H Without Acceptor N2 - H2 ... ? PLAT480_ALERT_4_C Long H...A H-Bond Reported H2 .. S1 .. 2.89 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 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
A solution of 4-methylbenzoyl chloride (1.75 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 when the thiourea was precipitated as a solid. Recrystallized from ethanol as colourless crystals (2.4 g, 8.0 mmol, 80%). m.p. 79°C. IR (KBr) cm-1: 3351 (free NH), 3200 (assoc. NH), 1667 (CO), 1610 (arom.), 1529 (thioureido I) 1325 II, 1160 III, 744, 762; 1H NMR (CDCl3) ?: 3.89 (3H, s, ArOCH3), 7.31–7.75 (aromatic), 9.19 (1H, s, broad, NH); 12.76 (1H, s, broad, NH); 13 C NMR (CDCl3) ? 55.6 (OCH3), 126.2 (4 CH), 129.0 (2 CH), 129.20 (2CH), 130.7 (C), 132.1 (C),134.8 (C) 142.3 (C), 168.1 (C=O), 178.4 (C=S). EIMS m/e: 300, 168.9,149, 119, 91, 64.9; Analysis calculated for C16H16N2O2S C, 63.98; H, 5.37; N, 9.33; S, 10.67 found C, 64.01; H, 5.32; N, 9.10; S, 10.65
Hydrogen atoms were located in difference syntheses, constrained 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.
The background to this study has been set out in the previous paper (Saeed & Flörke, 2007). In the molecular structure of the title compound, (I), (Fig. 1) the torsion angles C8—N2—C9—O1 of -5.4 (4)° and C9—N2—C8—N1 of 4.8 (3)° reflect the almost planar conformation of I with respect to the thiocarbonyl and carbonyl parts. The two aromatic rings form a dihedral angle of 48.30 (8)°, the associated N2—C9—C10—C15 torsion angle is -17.5 (3)°. All other bond parameters (Table 1) are typical for these thiourea compounds (Saeed & Flörke, 2006). Also typical is the intramolecular N1—H···O hydrogen bond. The crystal packing is determined by intermolecular N2—H···S hydrogen bonds, forming centrosymmetric dimers which are stacked along [100].
For related literature, see: Saeed & Flörke (2006, 2007).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2002); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C16H16N2O2S | F(000) = 632 |
Mr = 300.37 | Dx = 1.339 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1407 reflections |
a = 5.3031 (6) Å | θ = 2.5–21.2° |
b = 21.159 (2) Å | µ = 0.22 mm−1 |
c = 13.2837 (14) Å | T = 120 K |
β = 90.027 (15)° | Needle, colourless |
V = 1490.5 (3) Å3 | 0.52 × 0.10 × 0.09 mm |
Z = 4 |
Bruker SMART APEX diffractometer | 3535 independent reflections |
Radiation source: sealed tube | 2050 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.091 |
φ and ω scans | θmax = 27.9°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −6→6 |
Tmin = 0.893, Tmax = 0.980 | k = −27→27 |
12383 measured reflections | l = −17→16 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 0.88 | w = 1/[σ2(Fo2) + (0.0434P)2] where P = (Fo2 + 2Fc2)/3 |
3535 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
C16H16N2O2S | V = 1490.5 (3) Å3 |
Mr = 300.37 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.3031 (6) Å | µ = 0.22 mm−1 |
b = 21.159 (2) Å | T = 120 K |
c = 13.2837 (14) Å | 0.52 × 0.10 × 0.09 mm |
β = 90.027 (15)° |
Bruker SMART APEX diffractometer | 3535 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 2050 reflections with I > 2σ(I) |
Tmin = 0.893, Tmax = 0.980 | Rint = 0.091 |
12383 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 0.88 | Δρmax = 0.32 e Å−3 |
3535 reflections | Δρmin = −0.33 e Å−3 |
190 parameters |
x | y | z | Uiso*/Ueq | ||
S1 | 0.32324 (14) | 1.01213 (3) | 0.85607 (5) | 0.0443 (2) | |
O1 | 0.6061 (3) | 0.81054 (7) | 0.82493 (11) | 0.0427 (5) | |
O2 | 0.0758 (3) | 0.86111 (8) | 0.42661 (12) | 0.0484 (5) | |
N1 | 0.3031 (3) | 0.90015 (8) | 0.76221 (13) | 0.0325 (5) | |
H1 | 0.3542 | 0.8606 | 0.7636 | 0.039* | |
N2 | 0.5727 (3) | 0.90797 (8) | 0.89643 (13) | 0.0326 (5) | |
H2 | 0.6253 | 0.9309 | 0.9476 | 0.039* | |
C1 | 0.1346 (4) | 0.91542 (10) | 0.68283 (16) | 0.0302 (5) | |
C2 | −0.0701 (5) | 0.95549 (10) | 0.69401 (18) | 0.0371 (6) | |
H2A | −0.1001 | 0.9767 | 0.7559 | 0.044* | |
C3 | −0.2299 (5) | 0.96387 (11) | 0.6126 (2) | 0.0447 (7) | |
H3A | −0.3706 | 0.9913 | 0.6194 | 0.054* | |
C4 | −0.1907 (5) | 0.93341 (11) | 0.52169 (19) | 0.0421 (7) | |
H4A | −0.3028 | 0.9398 | 0.4668 | 0.050* | |
C5 | 0.0128 (5) | 0.89387 (10) | 0.51231 (17) | 0.0348 (6) | |
C6 | 0.1752 (4) | 0.88476 (9) | 0.59290 (17) | 0.0321 (6) | |
H6A | 0.3154 | 0.8572 | 0.5860 | 0.039* | |
C7 | −0.0996 (5) | 0.86212 (13) | 0.34504 (18) | 0.0579 (8) | |
H7A | −0.2651 | 0.8480 | 0.3689 | 0.087* | |
H7B | −0.0407 | 0.8338 | 0.2916 | 0.087* | |
H7C | −0.1132 | 0.9052 | 0.3187 | 0.087* | |
C8 | 0.3948 (4) | 0.93659 (10) | 0.83449 (16) | 0.0304 (5) | |
C9 | 0.6782 (5) | 0.84850 (10) | 0.88869 (16) | 0.0322 (5) | |
C10 | 0.8808 (4) | 0.83358 (9) | 0.96113 (15) | 0.0278 (5) | |
C11 | 0.9470 (5) | 0.77047 (10) | 0.97489 (16) | 0.0360 (6) | |
H11A | 0.8625 | 0.7384 | 0.9378 | 0.043* | |
C12 | 1.1343 (5) | 0.75421 (10) | 1.04196 (16) | 0.0362 (6) | |
H12A | 1.1783 | 0.7110 | 1.0500 | 0.043* | |
C13 | 1.2603 (4) | 0.79982 (10) | 1.09818 (15) | 0.0317 (5) | |
C14 | 1.1956 (5) | 0.86231 (10) | 1.08289 (17) | 0.0381 (6) | |
H14A | 1.2806 | 0.8943 | 1.1198 | 0.046* | |
C15 | 1.0105 (4) | 0.87923 (10) | 1.01519 (16) | 0.0342 (6) | |
H15A | 0.9714 | 0.9226 | 1.0055 | 0.041* | |
C16 | 1.4626 (5) | 0.78203 (11) | 1.17233 (17) | 0.0431 (6) | |
H16A | 1.6214 | 0.8024 | 1.1532 | 0.065* | |
H16B | 1.4848 | 0.7360 | 1.1722 | 0.065* | |
H16C | 1.4133 | 0.7960 | 1.2398 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0624 (5) | 0.0291 (3) | 0.0416 (4) | 0.0117 (3) | −0.0172 (3) | −0.0020 (3) |
O1 | 0.0533 (12) | 0.0361 (9) | 0.0387 (10) | 0.0122 (8) | −0.0175 (9) | −0.0076 (7) |
O2 | 0.0523 (13) | 0.0539 (11) | 0.0390 (10) | 0.0027 (9) | −0.0230 (9) | −0.0015 (8) |
N1 | 0.0388 (13) | 0.0261 (9) | 0.0327 (11) | 0.0039 (9) | −0.0077 (9) | 0.0008 (8) |
N2 | 0.0410 (13) | 0.0304 (10) | 0.0264 (10) | 0.0067 (9) | −0.0094 (9) | −0.0023 (8) |
C1 | 0.0281 (14) | 0.0267 (11) | 0.0357 (13) | −0.0049 (10) | −0.0084 (11) | 0.0077 (10) |
C2 | 0.0311 (15) | 0.0371 (13) | 0.0429 (15) | −0.0004 (11) | −0.0023 (12) | 0.0045 (11) |
C3 | 0.0281 (16) | 0.0392 (14) | 0.0667 (19) | 0.0018 (12) | −0.0078 (14) | 0.0118 (13) |
C4 | 0.0345 (16) | 0.0438 (14) | 0.0479 (17) | −0.0037 (12) | −0.0199 (13) | 0.0147 (12) |
C5 | 0.0366 (16) | 0.0316 (12) | 0.0362 (15) | −0.0092 (11) | −0.0106 (12) | 0.0068 (10) |
C6 | 0.0306 (15) | 0.0281 (11) | 0.0376 (14) | 0.0010 (10) | −0.0091 (11) | 0.0036 (10) |
C7 | 0.060 (2) | 0.076 (2) | 0.0387 (16) | −0.0074 (15) | −0.0272 (15) | 0.0082 (13) |
C8 | 0.0335 (15) | 0.0318 (12) | 0.0259 (12) | 0.0034 (10) | −0.0014 (11) | 0.0029 (9) |
C9 | 0.0377 (15) | 0.0315 (12) | 0.0274 (13) | 0.0043 (11) | −0.0006 (11) | −0.0007 (10) |
C10 | 0.0300 (14) | 0.0309 (12) | 0.0224 (12) | 0.0049 (10) | −0.0026 (10) | 0.0005 (9) |
C11 | 0.0426 (16) | 0.0319 (12) | 0.0337 (14) | 0.0029 (11) | −0.0105 (12) | −0.0056 (10) |
C12 | 0.0409 (16) | 0.0303 (12) | 0.0375 (14) | 0.0075 (11) | −0.0073 (12) | 0.0016 (10) |
C13 | 0.0291 (14) | 0.0442 (13) | 0.0217 (12) | 0.0018 (11) | 0.0011 (10) | 0.0008 (10) |
C14 | 0.0402 (16) | 0.0358 (13) | 0.0382 (14) | −0.0041 (11) | −0.0054 (12) | −0.0068 (11) |
C15 | 0.0390 (16) | 0.0270 (12) | 0.0366 (14) | 0.0007 (10) | −0.0030 (12) | −0.0003 (10) |
C16 | 0.0375 (16) | 0.0543 (16) | 0.0374 (15) | 0.0000 (12) | −0.0074 (12) | 0.0000 (12) |
S1—C8 | 1.668 (2) | C6—H6A | 0.9500 |
O1—C9 | 1.228 (2) | C7—H7A | 0.9800 |
O2—C5 | 1.374 (3) | C7—H7B | 0.9800 |
O2—C7 | 1.428 (3) | C7—H7C | 0.9800 |
N1—C8 | 1.324 (3) | C9—C10 | 1.477 (3) |
N1—C1 | 1.419 (3) | C10—C15 | 1.386 (3) |
N1—H1 | 0.8800 | C10—C11 | 1.393 (3) |
N2—C9 | 1.381 (3) | C11—C12 | 1.378 (3) |
N2—C8 | 1.391 (3) | C11—H11A | 0.9500 |
N2—H2 | 0.8800 | C12—C13 | 1.391 (3) |
C1—C6 | 1.376 (3) | C12—H12A | 0.9500 |
C1—C2 | 1.385 (3) | C13—C14 | 1.381 (3) |
C2—C3 | 1.385 (3) | C13—C16 | 1.504 (3) |
C2—H2A | 0.9500 | C14—C15 | 1.379 (3) |
C3—C4 | 1.385 (3) | C14—H14A | 0.9500 |
C3—H3A | 0.9500 | C15—H15A | 0.9500 |
C4—C5 | 1.371 (3) | C16—H16A | 0.9800 |
C4—H4A | 0.9500 | C16—H16B | 0.9800 |
C5—C6 | 1.387 (3) | C16—H16C | 0.9800 |
C5—O2—C7 | 117.6 (2) | N1—C8—N2 | 115.12 (18) |
C8—N1—C1 | 129.59 (18) | N1—C8—S1 | 126.83 (17) |
C8—N1—H1 | 115.2 | N2—C8—S1 | 118.03 (16) |
C1—N1—H1 | 115.2 | O1—C9—N2 | 121.4 (2) |
C9—N2—C8 | 128.87 (18) | O1—C9—C10 | 122.4 (2) |
C9—N2—H2 | 115.6 | N2—C9—C10 | 116.18 (19) |
C8—N2—H2 | 115.6 | C15—C10—C11 | 118.4 (2) |
C6—C1—C2 | 120.3 (2) | C15—C10—C9 | 123.34 (19) |
C6—C1—N1 | 116.0 (2) | C11—C10—C9 | 118.28 (19) |
C2—C1—N1 | 123.6 (2) | C12—C11—C10 | 120.4 (2) |
C3—C2—C1 | 118.3 (2) | C12—C11—H11A | 119.8 |
C3—C2—H2A | 120.9 | C10—C11—H11A | 119.8 |
C1—C2—H2A | 120.9 | C11—C12—C13 | 121.3 (2) |
C2—C3—C4 | 122.0 (2) | C11—C12—H12A | 119.3 |
C2—C3—H3A | 119.0 | C13—C12—H12A | 119.3 |
C4—C3—H3A | 119.0 | C14—C13—C12 | 117.8 (2) |
C5—C4—C3 | 118.8 (2) | C14—C13—C16 | 120.9 (2) |
C5—C4—H4A | 120.6 | C12—C13—C16 | 121.4 (2) |
C3—C4—H4A | 120.6 | C15—C14—C13 | 121.4 (2) |
C4—C5—O2 | 125.0 (2) | C15—C14—H14A | 119.3 |
C4—C5—C6 | 120.2 (2) | C13—C14—H14A | 119.3 |
O2—C5—C6 | 114.7 (2) | C14—C15—C10 | 120.7 (2) |
C1—C6—C5 | 120.5 (2) | C14—C15—H15A | 119.7 |
C1—C6—H6A | 119.8 | C10—C15—H15A | 119.7 |
C5—C6—H6A | 119.8 | C13—C16—H16A | 109.5 |
O2—C7—H7A | 109.5 | C13—C16—H16B | 109.5 |
O2—C7—H7B | 109.5 | H16A—C16—H16B | 109.5 |
H7A—C7—H7B | 109.5 | C13—C16—H16C | 109.5 |
O2—C7—H7C | 109.5 | H16A—C16—H16C | 109.5 |
H7A—C7—H7C | 109.5 | H16B—C16—H16C | 109.5 |
H7B—C7—H7C | 109.5 | ||
C8—N1—C1—C6 | 144.9 (2) | C9—N2—C8—S1 | −173.97 (18) |
C8—N1—C1—C2 | −39.0 (3) | C8—N2—C9—O1 | −5.4 (4) |
C6—C1—C2—C3 | −0.3 (3) | C8—N2—C9—C10 | 174.6 (2) |
N1—C1—C2—C3 | −176.2 (2) | O1—C9—C10—C15 | 162.5 (2) |
C1—C2—C3—C4 | 0.2 (3) | N2—C9—C10—C15 | −17.5 (3) |
C2—C3—C4—C5 | −0.1 (4) | O1—C9—C10—C11 | −16.7 (3) |
C3—C4—C5—O2 | −179.4 (2) | N2—C9—C10—C11 | 163.3 (2) |
C3—C4—C5—C6 | 0.1 (3) | C15—C10—C11—C12 | 1.0 (3) |
C7—O2—C5—C4 | −8.0 (3) | C9—C10—C11—C12 | −179.7 (2) |
C7—O2—C5—C6 | 172.4 (2) | C10—C11—C12—C13 | 0.6 (4) |
C2—C1—C6—C5 | 0.4 (3) | C11—C12—C13—C14 | −1.5 (4) |
N1—C1—C6—C5 | 176.56 (19) | C11—C12—C13—C16 | 179.2 (2) |
C4—C5—C6—C1 | −0.3 (3) | C12—C13—C14—C15 | 0.8 (4) |
O2—C5—C6—C1 | 179.32 (18) | C16—C13—C14—C15 | −180.0 (2) |
C1—N1—C8—N2 | −175.1 (2) | C13—C14—C15—C10 | 0.9 (4) |
C1—N1—C8—S1 | 3.5 (4) | C11—C10—C15—C14 | −1.7 (3) |
C9—N2—C8—N1 | 4.8 (3) | C9—C10—C15—C14 | 179.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···S1i | 0.88 | 2.89 | 3.7376 (19) | 163 |
N1—H1···O1 | 0.88 | 1.89 | 2.621 (2) | 140 |
Symmetry code: (i) −x+1, −y+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C16H16N2O2S |
Mr | 300.37 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 120 |
a, b, c (Å) | 5.3031 (6), 21.159 (2), 13.2837 (14) |
β (°) | 90.027 (15) |
V (Å3) | 1490.5 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.22 |
Crystal size (mm) | 0.52 × 0.10 × 0.09 |
Data collection | |
Diffractometer | Bruker SMART APEX |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.893, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12383, 3535, 2050 |
Rint | 0.091 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.115, 0.88 |
No. of reflections | 3535 |
No. of parameters | 190 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.33 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXTL (Bruker, 2002), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···S1i | 0.88 | 2.89 | 3.7376 (19) | 163.3 |
N1—H1···O1 | 0.88 | 1.89 | 2.621 (2) | 139.5 |
Symmetry code: (i) −x+1, −y+2, −z+2. |
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The background to this study has been set out in the previous paper (Saeed & Flörke, 2007). In the molecular structure of the title compound, (I), (Fig. 1) the torsion angles C8—N2—C9—O1 of -5.4 (4)° and C9—N2—C8—N1 of 4.8 (3)° reflect the almost planar conformation of I with respect to the thiocarbonyl and carbonyl parts. The two aromatic rings form a dihedral angle of 48.30 (8)°, the associated N2—C9—C10—C15 torsion angle is -17.5 (3)°. All other bond parameters (Table 1) are typical for these thiourea compounds (Saeed & Flörke, 2006). Also typical is the intramolecular N1—H···O hydrogen bond. The crystal packing is determined by intermolecular N2—H···S hydrogen bonds, forming centrosymmetric dimers which are stacked along [100].