Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035088/cv2280sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035088/cv2280Isup2.hkl |
CCDC reference: 657829
An equimolar amount of glycine (1.0 g, 0.01 mol) in 20 ml acetone was added dropwise into a stirring acetone solution (75 ml) containing 4-methylbenzoyl chloride (2.36 g, 0.01 mol) and ammonium thiocyanate (0.98 g, 0.01 mol). The solution mixture was refluxed for 6 h. The resulting solution was poured into a beaker containing some ice blocks. The white precipitate was filtered and washed with distilled water and cold ethanol before dried under vacuum. Good quality crystals were obtained by recrystallization from methanol. Yield 77% (2.05 g). MP 375.2–376.4 K.
After their location in the difference map, all H-atoms were fixed geometrically at ideal positions (O—H, N—H and C—H of 0.82, 0.86 and 0.93–0.96 Å, respectively) and allowed to ride on the parent atoms with Uiso(H)= 1.2–1.5Ueq of the parent atom.
The title compound, (I), is analogous to N-(4-Methylbenzoyl)-N'-(4-nitrophenyl)thiourea, (II) (Yusof et al., 2006), except that the 4-nitrophenyl group is replaced by amino-acetic acid group (Fig. 1). The molecule of (I) maintains its trans-cis configuration with respect to the position of the 4-methylbenzoyl and acetic acid groups relative to the thiono S1 atom across the C8—N1 and C9—N2 bonds, respectively. The bond lengths and angles are in normal ranges (Allen et al., 1987) and are comparable to those in (II). The central thiourea, (S1/C9/N1/N2), phenyl ring (C1—C6) and amino-acetic acid (C10/C11/O2/O3/N2) fragments are essentially planar each with maximum deviation of 0.031 (2)° for atom C10 from the least square planes. The dihedral angles between the central thiourea and phenyl ring fragments is 8.23 (8)°. There are two intramolecular hydrogen bonds, N2—H2···O1 and C10—H10···S1 (Table 1), and as a result, a pseudo-six- and five-membered rings (O1···H2—N2—C9—N1—C8—O1 and H10B···S1—C9—N2—C10—H10B) are formed. The crystal packing exhibits extensive network formed by intermolecular O—H···S, N—H···O and C—H···O hydrogen bonds (Table 1).
For a related crystal structure, see: Yusof et al. (2006). For normal ranges of molecular bond lengths, see: Allen et al. (1987).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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).
Fig. 1. Molecular structure of the title compound, (I), with the 50% probability displacement ellipsoids. The dashed line indicates intramolecular N—H···O and C—H···S hydrogen bonds. |
C11H12N2O3S | F(000) = 528 |
Mr = 252.29 | Dx = 1.412 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.664 (3) Å | Cell parameters from 3055 reflections |
b = 8.590 (2) Å | θ = 1.9–26.0° |
c = 12.962 (3) Å | µ = 0.27 mm−1 |
β = 113.917 (4)° | T = 298 K |
V = 1187.2 (5) Å3 | Block, colourless |
Z = 4 | 0.50 × 0.48 × 0.21 mm |
Bruker SMART APEX CCD area-detector diffractometer | 2322 independent reflections |
Radiation source: fine-focus sealed tube | 2018 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
Detector resolution: 83.66 pixels mm-1 | θmax = 26.0°, θmin = 2.0° |
ω scans | h = −14→8 |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | k = −10→10 |
Tmin = 0.877, Tmax = 0.945 | l = −15→15 |
6388 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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0613P)2 + 0.2581P] where P = (Fo2 + 2Fc2)/3 |
2322 reflections | (Δ/σ)max < 0.001 |
156 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C11H12N2O3S | V = 1187.2 (5) Å3 |
Mr = 252.29 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.664 (3) Å | µ = 0.27 mm−1 |
b = 8.590 (2) Å | T = 298 K |
c = 12.962 (3) Å | 0.50 × 0.48 × 0.21 mm |
β = 113.917 (4)° |
Bruker SMART APEX CCD area-detector diffractometer | 2322 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2018 reflections with I > 2σ(I) |
Tmin = 0.877, Tmax = 0.945 | Rint = 0.017 |
6388 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.20 e Å−3 |
2322 reflections | Δρmin = −0.22 e Å−3 |
156 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 | 0.01912 (5) | 0.77866 (6) | 1.17790 (4) | 0.05108 (18) | |
O1 | 0.23600 (14) | 0.50912 (19) | 1.01638 (11) | 0.0661 (4) | |
O2 | 0.29873 (13) | 0.54526 (17) | 1.48607 (9) | 0.0601 (4) | |
H2A | 0.3527 | 0.5997 | 1.5328 | 0.090* | |
O3 | 0.34152 (12) | 0.69059 (14) | 1.36404 (10) | 0.0477 (3) | |
N1 | 0.08679 (13) | 0.67815 (16) | 1.01690 (11) | 0.0402 (3) | |
H1A | 0.0310 | 0.7432 | 0.9756 | 0.048* | |
N2 | 0.16263 (13) | 0.53866 (15) | 1.18306 (10) | 0.0399 (3) | |
H2B | 0.2001 | 0.4820 | 1.1515 | 0.048* | |
C1 | 0.17221 (17) | 0.5590 (2) | 0.78550 (15) | 0.0505 (4) | |
H1 | 0.2181 | 0.4699 | 0.8178 | 0.061* | |
C2 | 0.14413 (19) | 0.5940 (2) | 0.67371 (16) | 0.0564 (5) | |
H2 | 0.1723 | 0.5281 | 0.6320 | 0.068* | |
C3 | 0.07530 (18) | 0.7243 (2) | 0.62259 (15) | 0.0492 (4) | |
C4 | 0.03829 (19) | 0.8234 (2) | 0.68810 (15) | 0.0501 (4) | |
H4 | −0.0063 | 0.9134 | 0.6560 | 0.060* | |
C5 | 0.06646 (17) | 0.79070 (19) | 0.79981 (14) | 0.0441 (4) | |
H5 | 0.0413 | 0.8591 | 0.8423 | 0.053* | |
C6 | 0.13205 (15) | 0.6564 (2) | 0.84968 (13) | 0.0405 (4) | |
C7 | 0.0398 (3) | 0.7588 (3) | 0.49940 (18) | 0.0707 (6) | |
H7A | 0.1037 | 0.8216 | 0.4914 | 0.106* | |
H7B | −0.0386 | 0.8137 | 0.4694 | 0.106* | |
H7C | 0.0316 | 0.6628 | 0.4590 | 0.106* | |
C8 | 0.15811 (15) | 0.6075 (2) | 0.96716 (14) | 0.0426 (4) | |
C9 | 0.09453 (15) | 0.65652 (18) | 1.12535 (13) | 0.0369 (4) | |
C10 | 0.17812 (16) | 0.49900 (18) | 1.29587 (13) | 0.0399 (4) | |
H10A | 0.1966 | 0.3888 | 1.3083 | 0.048* | |
H10B | 0.1002 | 0.5187 | 1.3037 | 0.048* | |
C11 | 0.28158 (15) | 0.59043 (18) | 1.38379 (12) | 0.0371 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0641 (3) | 0.0556 (3) | 0.0328 (2) | 0.0194 (2) | 0.0189 (2) | 0.00378 (18) |
O1 | 0.0655 (8) | 0.0874 (10) | 0.0461 (7) | 0.0351 (8) | 0.0232 (7) | 0.0126 (7) |
O2 | 0.0708 (9) | 0.0704 (9) | 0.0297 (6) | −0.0245 (7) | 0.0105 (6) | 0.0026 (6) |
O3 | 0.0497 (7) | 0.0497 (7) | 0.0377 (6) | −0.0116 (6) | 0.0117 (5) | 0.0022 (5) |
N1 | 0.0445 (8) | 0.0444 (7) | 0.0285 (6) | 0.0070 (6) | 0.0117 (6) | 0.0026 (6) |
N2 | 0.0455 (8) | 0.0389 (7) | 0.0300 (7) | 0.0043 (6) | 0.0098 (6) | −0.0009 (5) |
C1 | 0.0518 (11) | 0.0563 (10) | 0.0470 (10) | 0.0065 (8) | 0.0238 (8) | −0.0004 (8) |
C2 | 0.0664 (12) | 0.0646 (12) | 0.0499 (10) | −0.0028 (10) | 0.0355 (10) | −0.0094 (9) |
C3 | 0.0551 (11) | 0.0573 (11) | 0.0389 (9) | −0.0155 (9) | 0.0227 (8) | −0.0042 (8) |
C4 | 0.0576 (11) | 0.0488 (10) | 0.0458 (10) | −0.0041 (8) | 0.0230 (9) | 0.0053 (8) |
C5 | 0.0515 (10) | 0.0435 (9) | 0.0411 (9) | −0.0051 (7) | 0.0227 (8) | −0.0039 (7) |
C6 | 0.0369 (8) | 0.0485 (9) | 0.0349 (8) | −0.0053 (7) | 0.0132 (7) | −0.0030 (7) |
C7 | 0.0918 (17) | 0.0805 (15) | 0.0445 (11) | −0.0150 (13) | 0.0325 (12) | −0.0004 (10) |
C8 | 0.0386 (9) | 0.0497 (9) | 0.0368 (9) | 0.0018 (7) | 0.0125 (7) | −0.0024 (7) |
C9 | 0.0380 (8) | 0.0381 (8) | 0.0293 (7) | −0.0035 (7) | 0.0081 (6) | −0.0025 (6) |
C10 | 0.0447 (9) | 0.0377 (8) | 0.0318 (8) | −0.0024 (7) | 0.0100 (7) | 0.0030 (6) |
C11 | 0.0396 (8) | 0.0369 (8) | 0.0314 (8) | 0.0033 (7) | 0.0109 (7) | 0.0029 (6) |
S1—C9 | 1.6806 (17) | C2—H2 | 0.9300 |
O1—C8 | 1.215 (2) | C3—C4 | 1.389 (3) |
O2—C11 | 1.3164 (19) | C3—C7 | 1.507 (3) |
O2—H2A | 0.8200 | C4—C5 | 1.378 (2) |
O3—C11 | 1.200 (2) | C4—H4 | 0.9300 |
N1—C8 | 1.382 (2) | C5—C6 | 1.390 (2) |
N1—C9 | 1.384 (2) | C5—H5 | 0.9300 |
N1—H1A | 0.8600 | C6—C8 | 1.488 (2) |
N2—C9 | 1.317 (2) | C7—H7A | 0.9600 |
N2—C10 | 1.440 (2) | C7—H7B | 0.9600 |
N2—H2B | 0.8600 | C7—H7C | 0.9600 |
C1—C2 | 1.383 (3) | C10—C11 | 1.502 (2) |
C1—C6 | 1.389 (2) | C10—H10A | 0.9700 |
C1—H1 | 0.9300 | C10—H10B | 0.9700 |
C2—C3 | 1.381 (3) | ||
C11—O2—H2A | 109.5 | C1—C6—C8 | 117.67 (16) |
C8—N1—C9 | 127.66 (14) | C5—C6—C8 | 123.78 (15) |
C8—N1—H1A | 116.2 | C3—C7—H7A | 109.5 |
C9—N1—H1A | 116.2 | C3—C7—H7B | 109.5 |
C9—N2—C10 | 123.87 (14) | H7A—C7—H7B | 109.5 |
C9—N2—H2B | 118.1 | C3—C7—H7C | 109.5 |
C10—N2—H2B | 118.1 | H7A—C7—H7C | 109.5 |
C2—C1—C6 | 120.17 (18) | H7B—C7—H7C | 109.5 |
C2—C1—H1 | 119.9 | O1—C8—N1 | 121.58 (15) |
C6—C1—H1 | 119.9 | O1—C8—C6 | 122.21 (15) |
C3—C2—C1 | 121.59 (17) | N1—C8—C6 | 116.20 (14) |
C3—C2—H2 | 119.2 | N2—C9—N1 | 117.14 (14) |
C1—C2—H2 | 119.2 | N2—C9—S1 | 122.96 (12) |
C2—C3—C4 | 117.90 (17) | N1—C9—S1 | 119.90 (12) |
C2—C3—C7 | 121.61 (18) | N2—C10—C11 | 112.22 (13) |
C4—C3—C7 | 120.49 (19) | N2—C10—H10A | 109.2 |
C5—C4—C3 | 121.12 (18) | C11—C10—H10A | 109.2 |
C5—C4—H4 | 119.4 | N2—C10—H10B | 109.2 |
C3—C4—H4 | 119.4 | C11—C10—H10B | 109.2 |
C4—C5—C6 | 120.65 (16) | H10A—C10—H10B | 107.9 |
C4—C5—H5 | 119.7 | O3—C11—O2 | 124.22 (15) |
C6—C5—H5 | 119.7 | O3—C11—C10 | 124.84 (14) |
C1—C6—C5 | 118.52 (16) | O2—C11—C10 | 110.93 (14) |
C6—C1—C2—C3 | −0.6 (3) | C1—C6—C8—O1 | 17.6 (3) |
C1—C2—C3—C4 | 2.2 (3) | C5—C6—C8—O1 | −164.65 (18) |
C1—C2—C3—C7 | −177.24 (19) | C1—C6—C8—N1 | −161.14 (16) |
C2—C3—C4—C5 | −1.7 (3) | C5—C6—C8—N1 | 16.6 (2) |
C7—C3—C4—C5 | 177.80 (18) | C10—N2—C9—N1 | −178.83 (14) |
C3—C4—C5—C6 | −0.5 (3) | C10—N2—C9—S1 | 1.4 (2) |
C2—C1—C6—C5 | −1.7 (3) | C8—N1—C9—N2 | −11.8 (2) |
C2—C1—C6—C8 | 176.21 (16) | C8—N1—C9—S1 | 168.04 (14) |
C4—C5—C6—C1 | 2.2 (3) | C9—N2—C10—C11 | −84.95 (19) |
C4—C5—C6—C8 | −175.53 (16) | N2—C10—C11—O3 | 3.3 (2) |
C9—N1—C8—O1 | 3.0 (3) | N2—C10—C11—O2 | −176.19 (14) |
C9—N1—C8—C6 | −178.23 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O1 | 0.86 | 1.97 | 2.639 (2) | 133 |
C10—H10B···S1 | 0.97 | 2.70 | 3.0413 (19) | 101 |
O2—H2A···S1i | 0.82 | 2.33 | 3.1458 (16) | 172 |
N1—H1A···O3ii | 0.86 | 2.17 | 2.964 (2) | 153 |
N2—H2B···O3iii | 0.86 | 2.54 | 3.0481 (19) | 119 |
C5—H5···O3ii | 0.93 | 2.49 | 3.062 (3) | 119 |
C7—H7A···O1iv | 0.96 | 2.50 | 3.455 (4) | 173 |
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) x−1/2, −y+3/2, z−1/2; (iii) −x+1/2, y−1/2, −z+5/2; (iv) −x+1/2, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C11H12N2O3S |
Mr | 252.29 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 11.664 (3), 8.590 (2), 12.962 (3) |
β (°) | 113.917 (4) |
V (Å3) | 1187.2 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.27 |
Crystal size (mm) | 0.50 × 0.48 × 0.21 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.877, 0.945 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6388, 2322, 2018 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.107, 1.06 |
No. of reflections | 2322 |
No. of parameters | 156 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.22 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, 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—H2B···O1 | 0.86 | 1.97 | 2.639 (2) | 133 |
C10—H10B···S1 | 0.97 | 2.70 | 3.0413 (19) | 101 |
O2—H2A···S1i | 0.82 | 2.33 | 3.1458 (16) | 172 |
N1—H1A···O3ii | 0.86 | 2.17 | 2.964 (2) | 153 |
N2—H2B···O3iii | 0.86 | 2.54 | 3.0481 (19) | 119 |
C7—H7A···O1iv | 0.96 | 2.50 | 3.455 (4) | 173 |
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) x−1/2, −y+3/2, z−1/2; (iii) −x+1/2, y−1/2, −z+5/2; (iv) −x+1/2, y+1/2, −z+3/2. |
The title compound, (I), is analogous to N-(4-Methylbenzoyl)-N'-(4-nitrophenyl)thiourea, (II) (Yusof et al., 2006), except that the 4-nitrophenyl group is replaced by amino-acetic acid group (Fig. 1). The molecule of (I) maintains its trans-cis configuration with respect to the position of the 4-methylbenzoyl and acetic acid groups relative to the thiono S1 atom across the C8—N1 and C9—N2 bonds, respectively. The bond lengths and angles are in normal ranges (Allen et al., 1987) and are comparable to those in (II). The central thiourea, (S1/C9/N1/N2), phenyl ring (C1—C6) and amino-acetic acid (C10/C11/O2/O3/N2) fragments are essentially planar each with maximum deviation of 0.031 (2)° for atom C10 from the least square planes. The dihedral angles between the central thiourea and phenyl ring fragments is 8.23 (8)°. There are two intramolecular hydrogen bonds, N2—H2···O1 and C10—H10···S1 (Table 1), and as a result, a pseudo-six- and five-membered rings (O1···H2—N2—C9—N1—C8—O1 and H10B···S1—C9—N2—C10—H10B) are formed. The crystal packing exhibits extensive network formed by intermolecular O—H···S, N—H···O and C—H···O hydrogen bonds (Table 1).