Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049720/bq2038sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049720/bq2038Isup2.hkl |
CCDC reference: 667414
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.056
- wR factor = 0.142
- Data-to-parameter ratio = 15.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 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 0 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
For related crystal structures, see: Yusof, Hamid et al. (2006); Yusof, Rahim & Yamin (2006).
To a stirring acetone solution (75 ml) of 4-methylbenzoyl chloride (2.0 g, 13 mmol) and ammoniumthiocyanate (0.98 g, 13 mmol), o-toluidine (1.39 g, 13 mmol) 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 dried under vacuum. Good quality crystals were obtained by recrystallization from acetone.
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 = 0.93–0.97 Å and N—H = 0.86 Å with Uiso(H)= 1.2 (CH2 and NH) or 1.5Ueq(C)(CH3).
The title compound, (I), is isostructural to N-(4-methylbenzoyl)-N'-(4-nitrophenyl)thiourea (II), (Yusof, Hamid et al., 2006), except that the nitro group at the phenyl ring is replaced by methyl group (Fig.1). The molecule maintains its trans-cis configuration with respect to the position of the 4-methylbenzoyl and 4-methylphenyl groups relative to the thiono S1 atom across their C—N bonds, respectively. The bond lengths and angles are in normal ranges and comparable to those in (II) and other thiourea derivatives (Yusof, Rahim & Yamin, 2006). The central carbonylthiourea (S1/N1/N2/C8/O1/C9) and both 4-methylphenyl groups [(C1—C6/C7) and (C10—C15/C16)] are all planar separately, with a maximum deviation of 0.039 (2) Å for atom N1 from the least-squares plane. The central carbonylthiourea fragment makes dihedral angles of 22.15 (8)° and 10.36 (8)° [24.67 (10) and 6.65 (10)° in (II)] with two rings [(C1—C6/C7) and (C10—C15/C16)], respectively. The two aryl rings are inclined to each other at an angle of 32.18 (10)° is larger compared in (II), 28.12 (12)°.
There are two intramolecular hydrogen bond, N2—H2···O1 and C11—H11···S1 (Table 1), forming two pseudo-six-membered rings, O1···H2—N2—C9—N1—C8—O1 and S1···H11—C11—C10—N2—C9—S1. In the crystal structure, the molecules are linked by intermolecular interaction, N—H···S (symmetry codes as in Table 1) to form dimers (Fig.2).
For related crystal structures, see: Yusof, Hamid et al. (2006); Yusof, Rahim & Yamin (2006).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b), PARST (Nardelli, 1995) and PLATON (Spek, 2003).
C16H16N2OS | F(000) = 600 |
Mr = 284.37 | Dx = 1.296 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 693 reflections |
a = 12.191 (2) Å | θ = 1.7–25.9° |
b = 6.4315 (12) Å | µ = 0.22 mm−1 |
c = 18.911 (4) Å | T = 298 K |
β = 100.713 (3)° | Block, colourless |
V = 1456.9 (5) Å3 | 0.25 × 0.22 × 0.16 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 2838 independent reflections |
Radiation source: fine-focus sealed tube | 1942 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
Detector resolution: 83.66 pixels mm-1 | θmax = 25.9°, θmin = 1.7° |
ω scans | h = −12→15 |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | k = −7→7 |
Tmin = 0.947, Tmax = 0.966 | l = −22→23 |
7857 measured reflections |
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.142 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.067P)2 + 0.2946P] where P = (Fo2 + 2Fc2)/3 |
2838 reflections | (Δ/σ)max < 0.001 |
183 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.13 e Å−3 |
C16H16N2OS | V = 1456.9 (5) Å3 |
Mr = 284.37 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.191 (2) Å | µ = 0.22 mm−1 |
b = 6.4315 (12) Å | T = 298 K |
c = 18.911 (4) Å | 0.25 × 0.22 × 0.16 mm |
β = 100.713 (3)° |
Bruker SMART APEX CCD area-detector diffractometer | 2838 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1942 reflections with I > 2σ(I) |
Tmin = 0.947, Tmax = 0.966 | Rint = 0.034 |
7857 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.142 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.19 e Å−3 |
2838 reflections | Δρmin = −0.13 e Å−3 |
183 parameters |
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 | 0.59737 (6) | 0.13899 (12) | 1.08812 (4) | 0.0657 (3) | |
O1 | 0.84014 (16) | −0.0690 (3) | 0.94662 (11) | 0.0680 (6) | |
N1 | 0.68101 (17) | −0.0707 (3) | 0.99280 (11) | 0.0490 (5) | |
H1 | 0.6181 | −0.1338 | 0.9895 | 0.059* | |
N2 | 0.79159 (16) | 0.1988 (3) | 1.04329 (11) | 0.0486 (5) | |
H2 | 0.8354 | 0.1463 | 1.0172 | 0.058* | |
C1 | 0.7480 (2) | −0.3785 (4) | 0.84506 (15) | 0.0565 (7) | |
H1A | 0.8003 | −0.2902 | 0.8309 | 0.068* | |
C2 | 0.7117 (2) | −0.5499 (4) | 0.80403 (15) | 0.0597 (7) | |
H2A | 0.7399 | −0.5759 | 0.7625 | 0.072* | |
C3 | 0.6340 (2) | −0.6845 (4) | 0.82327 (13) | 0.0495 (6) | |
C4 | 0.5938 (2) | −0.6419 (4) | 0.88529 (14) | 0.0534 (7) | |
H4 | 0.5412 | −0.7303 | 0.8991 | 0.064* | |
C5 | 0.6303 (2) | −0.4701 (4) | 0.92731 (13) | 0.0501 (7) | |
H5 | 0.6027 | −0.4448 | 0.9692 | 0.060* | |
C6 | 0.7078 (2) | −0.3359 (4) | 0.90707 (13) | 0.0448 (6) | |
C7 | 0.5932 (3) | −0.8713 (4) | 0.77817 (15) | 0.0727 (9) | |
H7A | 0.5510 | −0.9595 | 0.8042 | 0.109* | |
H7B | 0.6560 | −0.9470 | 0.7674 | 0.109* | |
H7C | 0.5466 | −0.8268 | 0.7341 | 0.109* | |
C8 | 0.7503 (2) | −0.1490 (4) | 0.94979 (13) | 0.0473 (6) | |
C9 | 0.6967 (2) | 0.0950 (4) | 1.04097 (13) | 0.0449 (6) | |
C10 | 0.8334 (2) | 0.3817 (4) | 1.08134 (13) | 0.0449 (6) | |
C11 | 0.7742 (2) | 0.5094 (4) | 1.11914 (15) | 0.0584 (7) | |
H11 | 0.7009 | 0.4773 | 1.1222 | 0.070* | |
C12 | 0.8244 (2) | 0.6855 (4) | 1.15247 (15) | 0.0602 (7) | |
H12 | 0.7840 | 0.7690 | 1.1786 | 0.072* | |
C13 | 0.9316 (2) | 0.7415 (4) | 1.14847 (14) | 0.0544 (7) | |
C14 | 0.9888 (2) | 0.6136 (4) | 1.11015 (15) | 0.0617 (8) | |
H14 | 1.0617 | 0.6476 | 1.1065 | 0.074* | |
C15 | 0.9414 (2) | 0.4356 (4) | 1.07668 (14) | 0.0548 (7) | |
H15 | 0.9823 | 0.3519 | 1.0510 | 0.066* | |
C16 | 0.9857 (3) | 0.9309 (5) | 1.18721 (17) | 0.0805 (10) | |
H16A | 0.9300 | 1.0352 | 1.1891 | 0.121* | |
H16B | 1.0409 | 0.9848 | 1.1619 | 0.121* | |
H16C | 1.0206 | 0.8933 | 1.2353 | 0.121* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0614 (5) | 0.0779 (6) | 0.0643 (5) | −0.0172 (4) | 0.0283 (4) | −0.0237 (4) |
O1 | 0.0564 (12) | 0.0650 (12) | 0.0889 (14) | −0.0144 (10) | 0.0302 (11) | −0.0285 (11) |
N1 | 0.0489 (13) | 0.0450 (12) | 0.0554 (13) | −0.0083 (10) | 0.0156 (10) | −0.0085 (10) |
N2 | 0.0452 (12) | 0.0474 (12) | 0.0553 (13) | −0.0022 (10) | 0.0149 (10) | −0.0120 (10) |
C1 | 0.0582 (17) | 0.0533 (16) | 0.0614 (17) | −0.0063 (13) | 0.0202 (14) | −0.0059 (14) |
C2 | 0.073 (2) | 0.0571 (17) | 0.0522 (16) | −0.0044 (15) | 0.0188 (14) | −0.0098 (14) |
C3 | 0.0616 (17) | 0.0395 (14) | 0.0446 (14) | 0.0017 (12) | 0.0025 (12) | 0.0025 (11) |
C4 | 0.0641 (18) | 0.0410 (14) | 0.0561 (16) | −0.0064 (13) | 0.0132 (14) | 0.0040 (13) |
C5 | 0.0627 (18) | 0.0434 (15) | 0.0464 (14) | 0.0010 (12) | 0.0162 (13) | 0.0008 (12) |
C6 | 0.0471 (15) | 0.0398 (13) | 0.0473 (14) | 0.0032 (11) | 0.0085 (11) | −0.0018 (11) |
C7 | 0.103 (3) | 0.0542 (18) | 0.0598 (18) | −0.0137 (16) | 0.0113 (17) | −0.0091 (14) |
C8 | 0.0473 (15) | 0.0448 (14) | 0.0506 (15) | −0.0025 (12) | 0.0114 (12) | −0.0041 (12) |
C9 | 0.0471 (15) | 0.0428 (14) | 0.0438 (14) | −0.0023 (11) | 0.0060 (11) | −0.0021 (11) |
C10 | 0.0488 (15) | 0.0422 (14) | 0.0422 (14) | −0.0004 (11) | 0.0044 (11) | −0.0028 (11) |
C11 | 0.0535 (17) | 0.0552 (17) | 0.0682 (18) | 0.0002 (13) | 0.0160 (14) | −0.0141 (14) |
C12 | 0.070 (2) | 0.0499 (16) | 0.0617 (18) | 0.0018 (14) | 0.0150 (15) | −0.0135 (14) |
C13 | 0.071 (2) | 0.0419 (15) | 0.0456 (15) | −0.0040 (14) | −0.0004 (13) | 0.0008 (12) |
C14 | 0.0545 (17) | 0.0600 (18) | 0.0694 (19) | −0.0130 (14) | 0.0080 (15) | −0.0029 (15) |
C15 | 0.0545 (17) | 0.0492 (16) | 0.0624 (17) | −0.0016 (13) | 0.0156 (14) | −0.0079 (13) |
C16 | 0.102 (3) | 0.0566 (19) | 0.077 (2) | −0.0188 (17) | 0.0010 (19) | −0.0088 (16) |
S1—C9 | 1.656 (2) | C6—C8 | 1.487 (3) |
O1—C8 | 1.222 (3) | C7—H7A | 0.9600 |
N1—C8 | 1.372 (3) | C7—H7B | 0.9600 |
N1—C9 | 1.392 (3) | C7—H7C | 0.9600 |
N1—H1 | 0.8600 | C10—C11 | 1.377 (3) |
N2—C9 | 1.329 (3) | C10—C15 | 1.380 (3) |
N2—C10 | 1.423 (3) | C11—C12 | 1.382 (4) |
N2—H2 | 0.8600 | C11—H11 | 0.9300 |
C1—C2 | 1.373 (4) | C12—C13 | 1.371 (4) |
C1—C6 | 1.380 (3) | C12—H12 | 0.9300 |
C1—H1A | 0.9300 | C13—C14 | 1.370 (4) |
C2—C3 | 1.381 (4) | C13—C16 | 1.509 (4) |
C2—H2A | 0.9300 | C14—C15 | 1.382 (4) |
C3—C4 | 1.380 (3) | C14—H14 | 0.9300 |
C3—C7 | 1.503 (3) | C15—H15 | 0.9300 |
C4—C5 | 1.385 (3) | C16—H16A | 0.9600 |
C4—H4 | 0.9300 | C16—H16B | 0.9600 |
C5—C6 | 1.385 (3) | C16—H16C | 0.9600 |
C5—H5 | 0.9300 | ||
C8—N1—C9 | 130.1 (2) | O1—C8—N1 | 122.1 (2) |
C8—N1—H1 | 115.0 | O1—C8—C6 | 122.6 (2) |
C9—N1—H1 | 115.0 | N1—C8—C6 | 115.4 (2) |
C9—N2—C10 | 131.3 (2) | N2—C9—N1 | 114.8 (2) |
C9—N2—H2 | 114.4 | N2—C9—S1 | 127.98 (19) |
C10—N2—H2 | 114.4 | N1—C9—S1 | 117.23 (18) |
C2—C1—C6 | 120.7 (2) | C11—C10—C15 | 118.8 (2) |
C2—C1—H1A | 119.6 | C11—C10—N2 | 125.6 (2) |
C6—C1—H1A | 119.6 | C15—C10—N2 | 115.6 (2) |
C1—C2—C3 | 121.3 (3) | C10—C11—C12 | 119.7 (3) |
C1—C2—H2A | 119.4 | C10—C11—H11 | 120.2 |
C3—C2—H2A | 119.4 | C12—C11—H11 | 120.2 |
C4—C3—C2 | 118.0 (2) | C13—C12—C11 | 122.4 (3) |
C4—C3—C7 | 120.6 (2) | C13—C12—H12 | 118.8 |
C2—C3—C7 | 121.5 (2) | C11—C12—H12 | 118.8 |
C3—C4—C5 | 121.3 (2) | C14—C13—C12 | 117.1 (3) |
C3—C4—H4 | 119.4 | C14—C13—C16 | 121.5 (3) |
C5—C4—H4 | 119.4 | C12—C13—C16 | 121.4 (3) |
C4—C5—C6 | 120.1 (2) | C13—C14—C15 | 121.9 (3) |
C4—C5—H5 | 120.0 | C13—C14—H14 | 119.0 |
C6—C5—H5 | 120.0 | C15—C14—H14 | 119.0 |
C1—C6—C5 | 118.7 (2) | C10—C15—C14 | 120.1 (2) |
C1—C6—C8 | 118.6 (2) | C10—C15—H15 | 119.9 |
C5—C6—C8 | 122.7 (2) | C14—C15—H15 | 119.9 |
C3—C7—H7A | 109.5 | C13—C16—H16A | 109.5 |
C3—C7—H7B | 109.5 | C13—C16—H16B | 109.5 |
H7A—C7—H7B | 109.5 | H16A—C16—H16B | 109.5 |
C3—C7—H7C | 109.5 | C13—C16—H16C | 109.5 |
H7A—C7—H7C | 109.5 | H16A—C16—H16C | 109.5 |
H7B—C7—H7C | 109.5 | H16B—C16—H16C | 109.5 |
C6—C1—C2—C3 | 0.1 (4) | C10—N2—C9—N1 | 175.3 (2) |
C1—C2—C3—C4 | −0.1 (4) | C10—N2—C9—S1 | −4.9 (4) |
C1—C2—C3—C7 | 179.5 (3) | C8—N1—C9—N2 | 3.3 (4) |
C2—C3—C4—C5 | −0.2 (4) | C8—N1—C9—S1 | −176.5 (2) |
C7—C3—C4—C5 | −179.8 (2) | C9—N2—C10—C11 | −8.7 (4) |
C3—C4—C5—C6 | 0.6 (4) | C9—N2—C10—C15 | 173.8 (2) |
C2—C1—C6—C5 | 0.3 (4) | C15—C10—C11—C12 | −1.2 (4) |
C2—C1—C6—C8 | 179.7 (2) | N2—C10—C11—C12 | −178.6 (2) |
C4—C5—C6—C1 | −0.6 (4) | C10—C11—C12—C13 | 1.2 (4) |
C4—C5—C6—C8 | −180.0 (2) | C11—C12—C13—C14 | −0.6 (4) |
C9—N1—C8—O1 | −3.3 (4) | C11—C12—C13—C16 | −178.1 (3) |
C9—N1—C8—C6 | 177.2 (2) | C12—C13—C14—C15 | 0.1 (4) |
C1—C6—C8—O1 | −23.2 (4) | C16—C13—C14—C15 | 177.6 (3) |
C5—C6—C8—O1 | 156.2 (3) | C11—C10—C15—C14 | 0.7 (4) |
C1—C6—C8—N1 | 156.3 (2) | N2—C10—C15—C14 | 178.3 (2) |
C5—C6—C8—N1 | −24.3 (3) | C13—C14—C15—C10 | −0.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1 | 0.86 | 1.93 | 2.657 (3) | 141 |
C11—H11···S1 | 0.93 | 2.54 | 3.193 (3) | 128 |
N1—H1···S1i | 0.86 | 2.76 | 3.482 (2) | 142 |
Symmetry code: (i) −x+1, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C16H16N2OS |
Mr | 284.37 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 12.191 (2), 6.4315 (12), 18.911 (4) |
β (°) | 100.713 (3) |
V (Å3) | 1456.9 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.22 |
Crystal size (mm) | 0.25 × 0.22 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.947, 0.966 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7857, 2838, 1942 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.615 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.142, 1.03 |
No. of reflections | 2838 |
No. of parameters | 183 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.13 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), PARST (Nardelli, 1995) and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1 | 0.86 | 1.93 | 2.657 (3) | 141 |
C11—H11···S1 | 0.93 | 2.54 | 3.193 (3) | 128 |
N1—H1···S1i | 0.86 | 2.76 | 3.482 (2) | 142 |
Symmetry code: (i) −x+1, −y, −z+2. |
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The title compound, (I), is isostructural to N-(4-methylbenzoyl)-N'-(4-nitrophenyl)thiourea (II), (Yusof, Hamid et al., 2006), except that the nitro group at the phenyl ring is replaced by methyl group (Fig.1). The molecule maintains its trans-cis configuration with respect to the position of the 4-methylbenzoyl and 4-methylphenyl groups relative to the thiono S1 atom across their C—N bonds, respectively. The bond lengths and angles are in normal ranges and comparable to those in (II) and other thiourea derivatives (Yusof, Rahim & Yamin, 2006). The central carbonylthiourea (S1/N1/N2/C8/O1/C9) and both 4-methylphenyl groups [(C1—C6/C7) and (C10—C15/C16)] are all planar separately, with a maximum deviation of 0.039 (2) Å for atom N1 from the least-squares plane. The central carbonylthiourea fragment makes dihedral angles of 22.15 (8)° and 10.36 (8)° [24.67 (10) and 6.65 (10)° in (II)] with two rings [(C1—C6/C7) and (C10—C15/C16)], respectively. The two aryl rings are inclined to each other at an angle of 32.18 (10)° is larger compared in (II), 28.12 (12)°.
There are two intramolecular hydrogen bond, N2—H2···O1 and C11—H11···S1 (Table 1), forming two pseudo-six-membered rings, O1···H2—N2—C9—N1—C8—O1 and S1···H11—C11—C10—N2—C9—S1. In the crystal structure, the molecules are linked by intermolecular interaction, N—H···S (symmetry codes as in Table 1) to form dimers (Fig.2).