


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811049208/gk2435sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536811049208/gk2435Isup2.hkl |
![]() | Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536811049208/gk2435Isup3.cml |
CCDC reference: 858483
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean
(C-C) = 0.003 Å
- R factor = 0.042
- wR factor = 0.132
- Data-to-parameter ratio = 15.6
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW .gt. 10 Outliers . 1
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.976 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 31 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 31
Alert level G PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF .... ?
0 ALERT level A = Most likely a serious problem - resolve or explain 1 ALERT level B = A potentially serious problem, consider carefully 3 ALERT level C = Check. Ensure it is not caused by an omission or oversight 1 ALERT level G = General information/check it is not something unexpected 0 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 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
A solution of benzoyl chloride (10 mmol) in acetone was added slowly to an equimolar solution of ammonium thiocyanate in acetone. The reaction mixture was stirred at room temperature before adding diethylamine (10 mmol) slowly and the mixture was left stirring at room temperature for 2–3 h. The mixture was poured onto a water-ice, filtered and the residue was recrystallized from ethaaol/acetone solution to give colourless crystals, suitable for X-ray crystallography (yield 85%).
The hydrogen atom positions were calculated geometrically and refined in a riding model approximation with C–H bond lengths in the range 0.93–0.97 Å and N-H= 0.86 Å with Uiso(H) = 1.2Ueq(C, N) for N-H, aromatic C-H and CH2 groups, and Uiso(H) = 1.5Ueq(C) for methyl group.
The title compound (I) has been used as a ligand to form stable complexes with Ni and Co (Mohamadou et al., 1994). Compund I and other similar derivatives act as a bidentate (O,S) chelate forming square planar and tetrahedral complexes with NiII and CoIII, respectively.
In the structure of I, the 4-methoxybenzamide moiety [O2/N1/C1/C2/C3/C4/C5/C6/C7/C8/C13] (A) and the thiourea fragment [S1/N1/N2/C8] (B) are essentially planar with maximum deviations from the mean planes 0.057 (2) Å for C13 and -0.031 (2) Å N1. The dihedral angle between the A and B planes is 86.62 (6)°, which is slightly smaller than the analogous dihedral angle [87.99 (11)°] in 1-benzoyl-3-ethyl-3-phenylthiourea (II) (Al-abbasi & Kassim, 2011).
The C=O [1.237 (2) Å] and C=S [1.658 (3) Å] bond lengths are slightly longer than those in II [1.207 (3) and 1.666 (2) Å, respectively].
In the crystal, the molecules are stabilized by intermolecular N1—H1A···O1 hydrogen bonds forming a one-dimensional polymeric network along the b axis (Figure 2).
For structural parameters and chemical properties of 1,1 disubstituted 3-benzoylthioureas, see: Al-abbasi et al. (2010, 2011); Al-abbasi & Kassim (2011); Mohamadou et al. (1994).
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); 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), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
C13H18N2O2S | Dx = 1.314 Mg m−3 |
Mr = 266.35 | Melting point = 407.15–408.15 K |
Orthorhombic, Pbca | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 5648 reflections |
a = 12.9024 (5) Å | θ = 4.2–71.1° |
b = 10.0095 (4) Å | µ = 2.11 mm−1 |
c = 20.8585 (11) Å | T = 150 K |
V = 2693.8 (2) Å3 | Plate, colourless |
Z = 8 | 0.24 × 0.10 × 0.05 mm |
F(000) = 1136 |
Oxford Diffraction Gemini diffractometer | 2548 independent reflections |
Radiation source: fine-focus sealed tube | 2214 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω/2θ scans | θmax = 71.1°, θmin = 4.2° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | h = −13→15 |
Tmin = 0.810, Tmax = 0.900 | k = −12→12 |
12046 measured reflections | l = −23→25 |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0835P)2 + 0.6035P] where P = (Fo2 + 2Fc2)/3 |
2548 reflections | (Δ/σ)max < 0.001 |
163 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C13H18N2O2S | V = 2693.8 (2) Å3 |
Mr = 266.35 | Z = 8 |
Orthorhombic, Pbca | Cu Kα radiation |
a = 12.9024 (5) Å | µ = 2.11 mm−1 |
b = 10.0095 (4) Å | T = 150 K |
c = 20.8585 (11) Å | 0.24 × 0.10 × 0.05 mm |
Oxford Diffraction Gemini diffractometer | 2548 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | 2214 reflections with I > 2σ(I) |
Tmin = 0.810, Tmax = 0.900 | Rint = 0.030 |
12046 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.43 e Å−3 |
2548 reflections | Δρmin = −0.32 e Å−3 |
163 parameters |
Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1 K. Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105 107. |
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 | 0.96773 (4) | 0.08865 (5) | 0.60731 (2) | 0.0302 (2) | |
O1 | 0.72174 (10) | 0.27396 (13) | 0.63046 (7) | 0.0282 (3) | |
O2 | 0.29590 (10) | 0.00839 (15) | 0.54492 (7) | 0.0327 (4) | |
N1 | 0.76759 (11) | 0.05775 (15) | 0.63691 (7) | 0.0210 (3) | |
H1A | 0.7495 | −0.0246 | 0.6332 | 0.025* | |
N2 | 0.87609 (11) | 0.11414 (15) | 0.72156 (7) | 0.0215 (3) | |
C1 | 0.52575 (14) | 0.21406 (19) | 0.58056 (9) | 0.0242 (4) | |
H1B | 0.5472 | 0.3028 | 0.5811 | 0.029* | |
C2 | 0.42448 (15) | 0.1834 (2) | 0.56253 (9) | 0.0271 (4) | |
H2A | 0.3785 | 0.2510 | 0.5513 | 0.033* | |
C3 | 0.39293 (14) | 0.0509 (2) | 0.56149 (8) | 0.0246 (4) | |
C4 | 0.46228 (14) | −0.05050 (19) | 0.57806 (9) | 0.0236 (4) | |
H4A | 0.4410 | −0.1393 | 0.5771 | 0.028* | |
C5 | 0.56228 (14) | −0.01898 (19) | 0.59584 (8) | 0.0220 (4) | |
H5A | 0.6082 | −0.0870 | 0.6067 | 0.026* | |
C6 | 0.59545 (14) | 0.11370 (18) | 0.59775 (8) | 0.0201 (4) | |
C7 | 0.69945 (13) | 0.15522 (17) | 0.62164 (8) | 0.0202 (4) | |
C8 | 0.86948 (13) | 0.08980 (16) | 0.65915 (9) | 0.0213 (4) | |
C9 | 0.78567 (13) | 0.11498 (19) | 0.76513 (9) | 0.0236 (4) | |
H9A | 0.7265 | 0.1524 | 0.7427 | 0.028* | |
H9B | 0.8007 | 0.1721 | 0.8015 | 0.028* | |
C10 | 0.75793 (15) | −0.0231 (2) | 0.78918 (10) | 0.0298 (4) | |
H10A | 0.6989 | −0.0174 | 0.8171 | 0.045* | |
H10B | 0.8156 | −0.0599 | 0.8123 | 0.045* | |
H10C | 0.7417 | −0.0798 | 0.7534 | 0.045* | |
C11 | 0.97664 (13) | 0.14064 (18) | 0.75210 (9) | 0.0246 (4) | |
H11A | 1.0310 | 0.0973 | 0.7277 | 0.029* | |
H11B | 0.9768 | 0.1028 | 0.7949 | 0.029* | |
C12 | 0.99913 (15) | 0.28917 (19) | 0.75623 (10) | 0.0296 (5) | |
H12A | 1.0650 | 0.3028 | 0.7766 | 0.044* | |
H12B | 0.9459 | 0.3322 | 0.7808 | 0.044* | |
H12C | 1.0008 | 0.3265 | 0.7138 | 0.044* | |
C13 | 0.22137 (16) | 0.1077 (3) | 0.52797 (11) | 0.0401 (5) | |
H13A | 0.1567 | 0.0654 | 0.5177 | 0.060* | |
H13B | 0.2457 | 0.1569 | 0.4914 | 0.060* | |
H13C | 0.2116 | 0.1676 | 0.5634 | 0.060* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0251 (3) | 0.0307 (3) | 0.0347 (3) | −0.00535 (18) | 0.00843 (18) | −0.00309 (18) |
O1 | 0.0258 (7) | 0.0211 (7) | 0.0378 (8) | −0.0015 (5) | −0.0037 (6) | 0.0012 (5) |
O2 | 0.0193 (7) | 0.0438 (9) | 0.0351 (8) | −0.0006 (6) | −0.0042 (5) | 0.0002 (6) |
N1 | 0.0196 (7) | 0.0170 (8) | 0.0265 (8) | −0.0021 (5) | −0.0025 (6) | −0.0007 (6) |
N2 | 0.0188 (7) | 0.0181 (7) | 0.0275 (8) | −0.0002 (5) | −0.0016 (6) | 0.0003 (6) |
C1 | 0.0273 (10) | 0.0215 (10) | 0.0238 (10) | 0.0017 (7) | 0.0004 (7) | 0.0011 (7) |
C2 | 0.0255 (9) | 0.0315 (11) | 0.0244 (9) | 0.0085 (8) | −0.0015 (7) | 0.0035 (7) |
C3 | 0.0207 (9) | 0.0348 (11) | 0.0184 (9) | 0.0003 (7) | 0.0004 (6) | −0.0014 (7) |
C4 | 0.0242 (9) | 0.0227 (9) | 0.0239 (10) | −0.0025 (7) | 0.0016 (7) | −0.0026 (7) |
C5 | 0.0209 (9) | 0.0240 (9) | 0.0212 (9) | 0.0018 (7) | 0.0021 (6) | 0.0005 (7) |
C6 | 0.0210 (9) | 0.0206 (9) | 0.0187 (8) | 0.0009 (7) | 0.0016 (6) | −0.0006 (6) |
C7 | 0.0226 (9) | 0.0184 (9) | 0.0197 (8) | −0.0012 (7) | 0.0022 (6) | 0.0008 (6) |
C8 | 0.0194 (9) | 0.0149 (9) | 0.0295 (10) | 0.0000 (6) | −0.0012 (7) | 0.0010 (6) |
C9 | 0.0220 (9) | 0.0222 (9) | 0.0265 (10) | 0.0007 (7) | 0.0001 (7) | −0.0027 (7) |
C10 | 0.0261 (10) | 0.0314 (11) | 0.0318 (10) | −0.0026 (8) | 0.0028 (8) | 0.0030 (8) |
C11 | 0.0204 (9) | 0.0211 (10) | 0.0323 (10) | 0.0008 (7) | −0.0066 (7) | 0.0002 (7) |
C12 | 0.0252 (9) | 0.0268 (11) | 0.0367 (11) | −0.0050 (7) | −0.0082 (8) | 0.0024 (8) |
C13 | 0.0229 (10) | 0.0591 (15) | 0.0384 (12) | 0.0080 (9) | −0.0058 (8) | 0.0033 (10) |
S1—C8 | 1.6663 (18) | C5—C6 | 1.396 (3) |
O1—C7 | 1.237 (2) | C5—H5A | 0.9300 |
O2—C3 | 1.367 (2) | C6—C7 | 1.490 (2) |
O2—C13 | 1.428 (3) | C9—C10 | 1.514 (3) |
N1—C7 | 1.351 (2) | C9—H9A | 0.9700 |
N1—C8 | 1.431 (2) | C9—H9B | 0.9700 |
N1—H1A | 0.8600 | C10—H10A | 0.9600 |
N2—C8 | 1.327 (2) | C10—H10B | 0.9600 |
N2—C11 | 1.470 (2) | C10—H10C | 0.9600 |
N2—C9 | 1.479 (2) | C11—C12 | 1.517 (3) |
C1—C2 | 1.394 (3) | C11—H11A | 0.9700 |
C1—C6 | 1.395 (3) | C11—H11B | 0.9700 |
C1—H1B | 0.9300 | C12—H12A | 0.9600 |
C2—C3 | 1.387 (3) | C12—H12B | 0.9600 |
C2—H2A | 0.9300 | C12—H12C | 0.9600 |
C3—C4 | 1.397 (3) | C13—H13A | 0.9600 |
C4—C5 | 1.379 (3) | C13—H13B | 0.9600 |
C4—H4A | 0.9300 | C13—H13C | 0.9600 |
C3—O2—C13 | 117.56 (17) | N2—C9—C10 | 112.64 (15) |
C7—N1—C8 | 120.83 (15) | N2—C9—H9A | 109.1 |
C7—N1—H1A | 119.6 | C10—C9—H9A | 109.1 |
C8—N1—H1A | 119.6 | N2—C9—H9B | 109.1 |
C8—N2—C11 | 121.01 (15) | C10—C9—H9B | 109.1 |
C8—N2—C9 | 123.58 (14) | H9A—C9—H9B | 107.8 |
C11—N2—C9 | 115.40 (14) | C9—C10—H10A | 109.5 |
C2—C1—C6 | 121.00 (17) | C9—C10—H10B | 109.5 |
C2—C1—H1B | 119.5 | H10A—C10—H10B | 109.5 |
C6—C1—H1B | 119.5 | C9—C10—H10C | 109.5 |
C3—C2—C1 | 119.34 (17) | H10A—C10—H10C | 109.5 |
C3—C2—H2A | 120.3 | H10B—C10—H10C | 109.5 |
C1—C2—H2A | 120.3 | N2—C11—C12 | 111.73 (14) |
O2—C3—C2 | 124.80 (17) | N2—C11—H11A | 109.3 |
O2—C3—C4 | 115.01 (17) | C12—C11—H11A | 109.3 |
C2—C3—C4 | 120.19 (17) | N2—C11—H11B | 109.3 |
C5—C4—C3 | 119.97 (18) | C12—C11—H11B | 109.3 |
C5—C4—H4A | 120.0 | H11A—C11—H11B | 107.9 |
C3—C4—H4A | 120.0 | C11—C12—H12A | 109.5 |
C4—C5—C6 | 120.81 (17) | C11—C12—H12B | 109.5 |
C4—C5—H5A | 119.6 | H12A—C12—H12B | 109.5 |
C6—C5—H5A | 119.6 | C11—C12—H12C | 109.5 |
C1—C6—C5 | 118.69 (17) | H12A—C12—H12C | 109.5 |
C1—C6—C7 | 117.74 (16) | H12B—C12—H12C | 109.5 |
C5—C6—C7 | 123.43 (16) | O2—C13—H13A | 109.5 |
O1—C7—N1 | 120.50 (16) | O2—C13—H13B | 109.5 |
O1—C7—C6 | 121.81 (16) | H13A—C13—H13B | 109.5 |
N1—C7—C6 | 117.60 (15) | O2—C13—H13C | 109.5 |
N2—C8—N1 | 114.73 (15) | H13A—C13—H13C | 109.5 |
N2—C8—S1 | 126.08 (14) | H13B—C13—H13C | 109.5 |
N1—C8—S1 | 119.16 (13) | ||
C6—C1—C2—C3 | −0.2 (3) | C1—C6—C7—O1 | 5.0 (3) |
C13—O2—C3—C2 | −0.6 (3) | C5—C6—C7—O1 | −170.57 (16) |
C13—O2—C3—C4 | 179.54 (17) | C1—C6—C7—N1 | −178.57 (16) |
C1—C2—C3—O2 | 179.78 (17) | C5—C6—C7—N1 | 5.9 (2) |
C1—C2—C3—C4 | −0.3 (3) | C11—N2—C8—N1 | 176.34 (14) |
O2—C3—C4—C5 | −179.75 (16) | C9—N2—C8—N1 | −2.8 (2) |
C2—C3—C4—C5 | 0.3 (3) | C11—N2—C8—S1 | −1.5 (2) |
C3—C4—C5—C6 | 0.2 (3) | C9—N2—C8—S1 | 179.41 (13) |
C2—C1—C6—C5 | 0.8 (3) | C7—N1—C8—N2 | 84.6 (2) |
C2—C1—C6—C7 | −175.01 (16) | C7—N1—C8—S1 | −97.46 (17) |
C4—C5—C6—C1 | −0.8 (3) | C8—N2—C9—C10 | 84.7 (2) |
C4—C5—C6—C7 | 174.78 (16) | C11—N2—C9—C10 | −94.45 (18) |
C8—N1—C7—O1 | −4.6 (3) | C8—N2—C11—C12 | 94.1 (2) |
C8—N1—C7—C6 | 178.96 (15) | C9—N2—C11—C12 | −86.69 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.86 | 2.05 | 2.847 (2) | 154 |
Symmetry code: (i) −x+3/2, y−1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C13H18N2O2S |
Mr | 266.35 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 150 |
a, b, c (Å) | 12.9024 (5), 10.0095 (4), 20.8585 (11) |
V (Å3) | 2693.8 (2) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 2.11 |
Crystal size (mm) | 0.24 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Oxford Diffraction Gemini |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.810, 0.900 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12046, 2548, 2214 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.614 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.132, 1.12 |
No. of reflections | 2548 |
No. of parameters | 163 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.32 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.86 | 2.05 | 2.847 (2) | 154 |
Symmetry code: (i) −x+3/2, y−1/2, z. |
The title compound (I) has been used as a ligand to form stable complexes with Ni and Co (Mohamadou et al., 1994). Compund I and other similar derivatives act as a bidentate (O,S) chelate forming square planar and tetrahedral complexes with NiII and CoIII, respectively.
In the structure of I, the 4-methoxybenzamide moiety [O2/N1/C1/C2/C3/C4/C5/C6/C7/C8/C13] (A) and the thiourea fragment [S1/N1/N2/C8] (B) are essentially planar with maximum deviations from the mean planes 0.057 (2) Å for C13 and -0.031 (2) Å N1. The dihedral angle between the A and B planes is 86.62 (6)°, which is slightly smaller than the analogous dihedral angle [87.99 (11)°] in 1-benzoyl-3-ethyl-3-phenylthiourea (II) (Al-abbasi & Kassim, 2011).
The C=O [1.237 (2) Å] and C=S [1.658 (3) Å] bond lengths are slightly longer than those in II [1.207 (3) and 1.666 (2) Å, respectively].
In the crystal, the molecules are stabilized by intermolecular N1—H1A···O1 hydrogen bonds forming a one-dimensional polymeric network along the b axis (Figure 2).