Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047551/bt2523sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047551/bt2523Isup2.hkl |
CCDC reference: 667286
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.050
- wR factor = 0.123
- Data-to-parameter ratio = 14.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C15
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 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 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
To a stirring acetone solution (75 ml) of 4-methylbenzoyl, chloride (2.0 g, 13 mmol) and ammoniumthiocyanate (0.98 g, 13 mmol), o-anisidine (1.59 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 chloroform.
After their location in a difference map, all H-atoms were fixed geometrically at ideal positions and allowed to ride on their 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 is similar to 1-(3-methoxyphenyl)-3-(4-methylbenzoyl)thiourea, (Saeed & Flörke, 2007), except that the methoxy group at the para possition of the phenyl ring (Fig.1). The molecule maintains its trans-cis configuration with respect to the position of the 4-methylbenzoyl and 4-methoxyphenyl groups relative to the thiono S1 atom across their C—N bonds, respectively. The bond lengths and angles are in normal ranges (Allen et al., 1987) and comparable with other thiourea derivatives (Yusof et al., 2006). The central carbonylthiourea (S1/N1/N2/C7/O1/C8), 4-methylphenyl (C1—C6/C15) and 4-methoxyphenyl (C9—C14/C16/O2) groups are all planar, with a maximum deviation of 0.060 (2) Å for atom O2 from the least-squares plane of the 4-methoxyphenyl fragment. The central carbonylthiourea fragment makes dihedral angles of 29.21 (9)° and 56.21 (8)° with the 4-methylphenyl and 4-methoxyphenyl fragments, respectively. The two aryl rings are inclined to each other at an angle of 83.69 (9)°.
There is an intramolecular hydrogen bond, N2—H2A···O1 (Table 1), forming a six-membered ring (O1···H2A—N2—C8—N1—C7). In the crystal structure, the molecules are linked by intermolecular interactions, N—H···S and C—H···O (symmetry codes as in Table 1) forming chains parallel to the a axis (Fig. 2).
For related crystal structures of the title compound, see: Saeed & Flörke (2007); Yusof et al. (2006).
For related literature, see: Allen et al. (1987).
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, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
C16H16N2O2S | F(000) = 632 |
Mr = 300.37 | Dx = 1.327 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 830 reflections |
a = 13.102 (3) Å | θ = 1.5–25.5° |
b = 6.4224 (17) Å | µ = 0.22 mm−1 |
c = 18.292 (5) Å | T = 298 K |
β = 102.340 (4)° | Slab, colourless |
V = 1503.6 (7) Å3 | 0.28 × 0.23 × 0.12 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 2794 independent reflections |
Radiation source: fine-focus sealed tube | 2040 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 83.66 pixels mm-1 | θmax = 25.5°, θmin = 1.5° |
ω scans | h = −15→15 |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | k = −7→7 |
Tmin = 0.941, Tmax = 0.974 | l = −22→14 |
7756 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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0537P)2 + 0.4385P] where P = (Fo2 + 2Fc2)/3 |
2794 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C16H16N2O2S | V = 1503.6 (7) Å3 |
Mr = 300.37 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.102 (3) Å | µ = 0.22 mm−1 |
b = 6.4224 (17) Å | T = 298 K |
c = 18.292 (5) Å | 0.28 × 0.23 × 0.12 mm |
β = 102.340 (4)° |
Bruker SMART APEX CCD area-detector diffractometer | 2794 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2040 reflections with I > 2σ(I) |
Tmin = 0.941, Tmax = 0.974 | Rint = 0.027 |
7756 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.24 e Å−3 |
2794 reflections | Δρmin = −0.17 e Å−3 |
190 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 | 0.90844 (5) | 0.64639 (12) | 1.06464 (4) | 0.0595 (2) | |
O1 | 0.67323 (13) | 0.3771 (3) | 0.86865 (10) | 0.0631 (5) | |
N2 | 0.71400 (15) | 0.6322 (3) | 0.98468 (11) | 0.0521 (5) | |
H2A | 0.6708 | 0.5810 | 0.9469 | 0.063* | |
N1 | 0.83275 (14) | 0.4150 (3) | 0.94654 (10) | 0.0457 (5) | |
H1A | 0.8969 | 0.3762 | 0.9529 | 0.055* | |
C7 | 0.76414 (18) | 0.3186 (4) | 0.88890 (13) | 0.0465 (6) | |
O2 | 0.54055 (14) | 1.2210 (3) | 1.14528 (11) | 0.0659 (5) | |
C2 | 0.91657 (19) | −0.1598 (4) | 0.85870 (13) | 0.0501 (6) | |
H2B | 0.9703 | −0.2417 | 0.8855 | 0.060* | |
C6 | 0.80534 (17) | 0.1382 (4) | 0.85390 (12) | 0.0426 (5) | |
C1 | 0.88511 (18) | 0.0138 (4) | 0.89214 (13) | 0.0477 (6) | |
H1B | 0.9179 | 0.0476 | 0.9410 | 0.057* | |
C8 | 0.81242 (18) | 0.5665 (4) | 0.99596 (13) | 0.0453 (6) | |
C11 | 0.54404 (18) | 0.8662 (4) | 1.09945 (14) | 0.0523 (6) | |
H11A | 0.4877 | 0.8266 | 1.1197 | 0.063* | |
C9 | 0.67315 (17) | 0.7806 (4) | 1.02962 (13) | 0.0456 (6) | |
C12 | 0.58214 (18) | 1.0657 (4) | 1.10923 (13) | 0.0493 (6) | |
C3 | 0.8703 (2) | −0.2148 (4) | 0.78647 (14) | 0.0522 (6) | |
C14 | 0.7128 (2) | 0.9803 (4) | 1.04053 (15) | 0.0569 (7) | |
H14A | 0.7697 | 1.0191 | 1.0206 | 0.068* | |
C10 | 0.58969 (17) | 0.7242 (4) | 1.05940 (14) | 0.0511 (6) | |
H10A | 0.5635 | 0.5894 | 1.0526 | 0.061* | |
C13 | 0.6682 (2) | 1.1218 (4) | 1.08078 (15) | 0.0571 (7) | |
H13A | 0.6958 | 1.2553 | 1.0889 | 0.069* | |
C4 | 0.7899 (2) | −0.0895 (4) | 0.74823 (14) | 0.0586 (7) | |
H4A | 0.7573 | −0.1236 | 0.6994 | 0.070* | |
C5 | 0.75776 (19) | 0.0834 (4) | 0.78101 (14) | 0.0538 (6) | |
H5A | 0.7037 | 0.1647 | 0.7543 | 0.065* | |
C16 | 0.4569 (2) | 1.1650 (5) | 1.18001 (16) | 0.0692 (8) | |
H16A | 0.4344 | 1.2854 | 1.2034 | 0.104* | |
H16B | 0.4803 | 1.0599 | 1.2171 | 0.104* | |
H16C | 0.3997 | 1.1119 | 1.1429 | 0.104* | |
C15 | 0.9056 (3) | −0.4045 (4) | 0.75038 (16) | 0.0740 (9) | |
H15A | 0.8649 | −0.4184 | 0.7003 | 0.111* | |
H15B | 0.8963 | −0.5259 | 0.7789 | 0.111* | |
H15C | 0.9781 | −0.3902 | 0.7489 | 0.111* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0489 (4) | 0.0750 (5) | 0.0519 (4) | 0.0112 (3) | 0.0043 (3) | −0.0143 (3) |
O1 | 0.0453 (10) | 0.0689 (12) | 0.0716 (12) | 0.0082 (9) | 0.0046 (9) | −0.0141 (10) |
N2 | 0.0422 (11) | 0.0587 (13) | 0.0542 (12) | 0.0071 (10) | 0.0075 (9) | −0.0106 (10) |
N1 | 0.0384 (10) | 0.0489 (12) | 0.0501 (12) | 0.0053 (9) | 0.0100 (9) | −0.0046 (9) |
C7 | 0.0428 (14) | 0.0485 (15) | 0.0486 (14) | 0.0007 (11) | 0.0106 (11) | 0.0032 (11) |
O2 | 0.0657 (12) | 0.0576 (11) | 0.0799 (13) | 0.0010 (9) | 0.0282 (10) | −0.0156 (10) |
C2 | 0.0573 (15) | 0.0431 (15) | 0.0508 (15) | 0.0046 (11) | 0.0138 (12) | 0.0058 (12) |
C6 | 0.0416 (12) | 0.0457 (13) | 0.0416 (13) | −0.0036 (11) | 0.0114 (10) | −0.0012 (11) |
C1 | 0.0539 (14) | 0.0458 (14) | 0.0431 (13) | −0.0016 (12) | 0.0096 (11) | 0.0006 (11) |
C8 | 0.0463 (14) | 0.0447 (13) | 0.0463 (14) | 0.0060 (11) | 0.0131 (11) | 0.0034 (11) |
C11 | 0.0416 (13) | 0.0561 (16) | 0.0601 (16) | −0.0023 (12) | 0.0128 (11) | −0.0063 (13) |
C9 | 0.0408 (13) | 0.0489 (14) | 0.0457 (13) | 0.0076 (11) | 0.0065 (10) | −0.0019 (11) |
C12 | 0.0477 (14) | 0.0489 (15) | 0.0501 (14) | 0.0065 (11) | 0.0078 (11) | −0.0053 (12) |
C3 | 0.0679 (17) | 0.0464 (14) | 0.0473 (14) | −0.0030 (12) | 0.0235 (13) | 0.0021 (12) |
C14 | 0.0540 (15) | 0.0521 (16) | 0.0707 (18) | 0.0034 (13) | 0.0269 (13) | 0.0072 (13) |
C10 | 0.0400 (13) | 0.0488 (14) | 0.0633 (16) | −0.0016 (11) | 0.0080 (12) | −0.0078 (12) |
C13 | 0.0571 (16) | 0.0434 (15) | 0.0734 (18) | −0.0009 (12) | 0.0198 (14) | −0.0014 (13) |
C4 | 0.0664 (17) | 0.0686 (18) | 0.0409 (14) | −0.0049 (14) | 0.0113 (13) | −0.0101 (13) |
C5 | 0.0491 (14) | 0.0628 (17) | 0.0472 (14) | 0.0044 (12) | 0.0049 (11) | 0.0007 (12) |
C16 | 0.0666 (18) | 0.0727 (19) | 0.0731 (19) | 0.0172 (15) | 0.0256 (15) | −0.0053 (15) |
C15 | 0.110 (2) | 0.0560 (18) | 0.0621 (18) | 0.0064 (16) | 0.0318 (17) | −0.0060 (14) |
S1—C8 | 1.658 (2) | C11—H11A | 0.9300 |
O1—C7 | 1.228 (3) | C9—C10 | 1.370 (3) |
N2—C8 | 1.330 (3) | C9—C14 | 1.382 (3) |
N2—C9 | 1.434 (3) | C12—C13 | 1.387 (3) |
N2—H2A | 0.8600 | C3—C4 | 1.390 (4) |
N1—C7 | 1.377 (3) | C3—C15 | 1.505 (3) |
N1—C8 | 1.392 (3) | C14—C13 | 1.376 (3) |
N1—H1A | 0.8600 | C14—H14A | 0.9300 |
C7—C6 | 1.480 (3) | C10—H10A | 0.9300 |
O2—C12 | 1.372 (3) | C13—H13A | 0.9300 |
O2—C16 | 1.425 (3) | C4—C5 | 1.370 (3) |
C2—C1 | 1.376 (3) | C4—H4A | 0.9300 |
C2—C3 | 1.377 (3) | C5—H5A | 0.9300 |
C2—H2B | 0.9300 | C16—H16A | 0.9600 |
C6—C1 | 1.381 (3) | C16—H16B | 0.9600 |
C6—C5 | 1.391 (3) | C16—H16C | 0.9600 |
C1—H1B | 0.9300 | C15—H15A | 0.9600 |
C11—C12 | 1.373 (3) | C15—H15B | 0.9600 |
C11—C10 | 1.383 (3) | C15—H15C | 0.9600 |
C8—N2—C9 | 126.2 (2) | C2—C3—C4 | 117.7 (2) |
C8—N2—H2A | 116.9 | C2—C3—C15 | 121.0 (2) |
C9—N2—H2A | 116.9 | C4—C3—C15 | 121.3 (2) |
C7—N1—C8 | 128.82 (19) | C13—C14—C9 | 120.0 (2) |
C7—N1—H1A | 115.6 | C13—C14—H14A | 120.0 |
C8—N1—H1A | 115.6 | C9—C14—H14A | 120.0 |
O1—C7—N1 | 121.7 (2) | C9—C10—C11 | 120.6 (2) |
O1—C7—C6 | 121.9 (2) | C9—C10—H10A | 119.7 |
N1—C7—C6 | 116.4 (2) | C11—C10—H10A | 119.7 |
C12—O2—C16 | 116.9 (2) | C14—C13—C12 | 120.1 (2) |
C1—C2—C3 | 121.5 (2) | C14—C13—H13A | 119.9 |
C1—C2—H2B | 119.3 | C12—C13—H13A | 119.9 |
C3—C2—H2B | 119.3 | C5—C4—C3 | 121.3 (2) |
C1—C6—C5 | 118.3 (2) | C5—C4—H4A | 119.3 |
C1—C6—C7 | 122.7 (2) | C3—C4—H4A | 119.3 |
C5—C6—C7 | 118.9 (2) | C4—C5—C6 | 120.5 (2) |
C2—C1—C6 | 120.6 (2) | C4—C5—H5A | 119.7 |
C2—C1—H1B | 119.7 | C6—C5—H5A | 119.7 |
C6—C1—H1B | 119.7 | O2—C16—H16A | 109.5 |
N2—C8—N1 | 115.8 (2) | O2—C16—H16B | 109.5 |
N2—C8—S1 | 124.93 (18) | H16A—C16—H16B | 109.5 |
N1—C8—S1 | 119.27 (17) | O2—C16—H16C | 109.5 |
C12—C11—C10 | 119.9 (2) | H16A—C16—H16C | 109.5 |
C12—C11—H11A | 120.1 | H16B—C16—H16C | 109.5 |
C10—C11—H11A | 120.1 | C3—C15—H15A | 109.5 |
C10—C9—C14 | 119.7 (2) | C3—C15—H15B | 109.5 |
C10—C9—N2 | 118.7 (2) | H15A—C15—H15B | 109.5 |
C14—C9—N2 | 121.6 (2) | C3—C15—H15C | 109.5 |
O2—C12—C11 | 124.8 (2) | H15A—C15—H15C | 109.5 |
O2—C12—C13 | 115.5 (2) | H15B—C15—H15C | 109.5 |
C11—C12—C13 | 119.7 (2) | ||
C8—N1—C7—O1 | 8.6 (4) | C10—C11—C12—O2 | 177.3 (2) |
C8—N1—C7—C6 | −170.1 (2) | C10—C11—C12—C13 | −1.9 (4) |
O1—C7—C6—C1 | −150.9 (2) | C1—C2—C3—C4 | −0.4 (4) |
N1—C7—C6—C1 | 27.8 (3) | C1—C2—C3—C15 | 179.8 (2) |
O1—C7—C6—C5 | 25.0 (3) | C10—C9—C14—C13 | −0.3 (4) |
N1—C7—C6—C5 | −156.3 (2) | N2—C9—C14—C13 | 176.7 (2) |
C3—C2—C1—C6 | 0.2 (4) | C14—C9—C10—C11 | 0.8 (4) |
C5—C6—C1—C2 | 0.1 (3) | N2—C9—C10—C11 | −176.3 (2) |
C7—C6—C1—C2 | 176.0 (2) | C12—C11—C10—C9 | 0.3 (4) |
C9—N2—C8—N1 | 177.5 (2) | C9—C14—C13—C12 | −1.3 (4) |
C9—N2—C8—S1 | −0.7 (3) | O2—C12—C13—C14 | −176.9 (2) |
C7—N1—C8—N2 | −2.3 (3) | C11—C12—C13—C14 | 2.4 (4) |
C7—N1—C8—S1 | 175.92 (18) | C2—C3—C4—C5 | 0.2 (4) |
C8—N2—C9—C10 | −124.5 (3) | C15—C3—C4—C5 | −180.0 (2) |
C8—N2—C9—C14 | 58.5 (3) | C3—C4—C5—C6 | 0.1 (4) |
C16—O2—C12—C11 | 5.2 (4) | C1—C6—C5—C4 | −0.3 (4) |
C16—O2—C12—C13 | −175.5 (2) | C7—C6—C5—C4 | −176.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1 | 0.86 | 1.95 | 2.644 (3) | 138 |
N1—H1A···S1i | 0.86 | 2.64 | 3.463 (2) | 160 |
C11—H11A···O1ii | 0.93 | 2.53 | 3.405 (3) | 157 |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C16H16N2O2S |
Mr | 300.37 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 13.102 (3), 6.4224 (17), 18.292 (5) |
β (°) | 102.340 (4) |
V (Å3) | 1503.6 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.22 |
Crystal size (mm) | 0.28 × 0.23 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.941, 0.974 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7756, 2794, 2040 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.123, 1.03 |
No. of reflections | 2794 |
No. of parameters | 190 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.17 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1 | 0.86 | 1.95 | 2.644 (3) | 138 |
N1—H1A···S1i | 0.86 | 2.64 | 3.463 (2) | 160 |
C11—H11A···O1ii | 0.93 | 2.53 | 3.405 (3) | 157 |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+1, −y+1, −z+2. |
The title compound is similar to 1-(3-methoxyphenyl)-3-(4-methylbenzoyl)thiourea, (Saeed & Flörke, 2007), except that the methoxy group at the para possition of the phenyl ring (Fig.1). The molecule maintains its trans-cis configuration with respect to the position of the 4-methylbenzoyl and 4-methoxyphenyl groups relative to the thiono S1 atom across their C—N bonds, respectively. The bond lengths and angles are in normal ranges (Allen et al., 1987) and comparable with other thiourea derivatives (Yusof et al., 2006). The central carbonylthiourea (S1/N1/N2/C7/O1/C8), 4-methylphenyl (C1—C6/C15) and 4-methoxyphenyl (C9—C14/C16/O2) groups are all planar, with a maximum deviation of 0.060 (2) Å for atom O2 from the least-squares plane of the 4-methoxyphenyl fragment. The central carbonylthiourea fragment makes dihedral angles of 29.21 (9)° and 56.21 (8)° with the 4-methylphenyl and 4-methoxyphenyl fragments, respectively. The two aryl rings are inclined to each other at an angle of 83.69 (9)°.
There is an intramolecular hydrogen bond, N2—H2A···O1 (Table 1), forming a six-membered ring (O1···H2A—N2—C8—N1—C7). In the crystal structure, the molecules are linked by intermolecular interactions, N—H···S and C—H···O (symmetry codes as in Table 1) forming chains parallel to the a axis (Fig. 2).