Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805040031/is6164sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805040031/is6164Isup2.hkl |
CCDC reference: 296590
To a solution of 2-(methylthio)aniline (2.778 g, 19.95 mmol) in absolute ethanol (50 ml) in a 100 ml round-bottomed flask equipped with a reflux condensor, o-vanillin was added (3.061 g, 20.12 mmol). The mixture was heated to reflux for 1.5 h, cooled to room temperature and placed in a freezer at 233 K for 14 h. The reaction was filtered, washed with cold ethanol and dried in vacuo to yield 4.700 g (86%) of the title compound as an orange solid. Crystals of (I) were grown by slow evaporation of an ethanol solution (m.p. 384–386 K). Spectroscopic analysis: 1H NMR (CDCl3, 400 MHz, δ, p.p.m.): 13.35 (s, 1H, OH), 8.65 (s, 1H, N═CH), 7.27 (m, 2H, arom), 7.21 (m, 2H, arom), 7.05 (dd, 1H, arom), 7.01 (dd, 1H, arom), 6.89 (t, 1H, arom), 3.90 (s, 3H, OCH3), 2.48 (s, 3H, SCH3); 13C NMR (CDCl3, 400 MHz, δ, p.p.m.): 162.4, 151.9, 149.0, 145.6, 135.5, 128.0, 125.8, 125.6, 124.4, 119.8, 119.0, 117.6, 115.9, 56.7, 15.3; IR (Medium?, ν, cm−1): 1610 (C═ N); UV–vis (CH2Cl2): λmax (ε) 361 nm (8230 M−1 cm−1), 273 nm (19,100 M−1 cm−1). Analysis calculated (found) for C15H15NO2S: C 65.91 (65.76), H 5.53 (5.46), N 5.12 (5.17)%.
The H atom of the hydroxyl group was found in a difference Fourier map and refined isotropically. The other H atoms were treated as riding atoms, with C—H distances of 0.95 Å (aromatic) or 0.98 Å (aliphatic), and with Uiso(H) = 1.2Ueq(C) for the aromatic and CH2 H atoms or 1.5Ueq(C) for the CH3 H atoms.
Data collection: SMART (Bruker, 2002); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. A view of (I), showing the atom-numbering scheme and with 50% probability displacement ellipsoids. |
C15H15NO2S | F(000) = 576 |
Mr = 273.34 | Dx = 1.391 Mg m−3 |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 7027 reflections |
a = 6.5559 (4) Å | θ = 3.0–30.5° |
b = 13.7147 (7) Å | µ = 0.25 mm−1 |
c = 14.5200 (8) Å | T = 100 K |
V = 1305.53 (13) Å3 | Block, orange-yellow |
Z = 4 | 0.59 × 0.33 × 0.32 mm |
Bruker SMART APEX CCD area-detector diffractometer | 3900 independent reflections |
Radiation source: fine-focus sealed tube | 3875 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ϕ and ω scans | θmax = 30.5°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −9→9 |
Tmin = 0.841, Tmax = 0.930 | k = −19→19 |
14274 measured reflections | l = −20→20 |
Refinement on F2 | H atoms treated by a mixture of independent and constrained refinement |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0364P)2 + 0.4174P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.030 | (Δ/σ)max < 0.001 |
wR(F2) = 0.079 | Δρmax = 0.30 e Å−3 |
S = 1.13 | Δρmin = −0.22 e Å−3 |
3900 reflections | Absolute structure: Flack (1983), with 1831 Friedel pairs |
176 parameters | Absolute structure parameter: 0.06 (5) |
1 restraint |
C15H15NO2S | V = 1305.53 (13) Å3 |
Mr = 273.34 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 6.5559 (4) Å | µ = 0.25 mm−1 |
b = 13.7147 (7) Å | T = 100 K |
c = 14.5200 (8) Å | 0.59 × 0.33 × 0.32 mm |
Bruker SMART APEX CCD area-detector diffractometer | 3900 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 3875 reflections with I > 2σ(I) |
Tmin = 0.841, Tmax = 0.930 | Rint = 0.020 |
14274 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.079 | Δρmax = 0.30 e Å−3 |
S = 1.13 | Δρmin = −0.22 e Å−3 |
3900 reflections | Absolute structure: Flack (1983), with 1831 Friedel pairs |
176 parameters | Absolute structure parameter: 0.06 (5) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 1.0270 (2) | 0.90390 (13) | 0.58287 (11) | 0.0293 (3) | |
H1A | 0.9965 | 0.9038 | 0.6489 | 0.044* | |
H1B | 1.0581 | 0.9705 | 0.5629 | 0.044* | |
H1C | 1.1449 | 0.8618 | 0.5709 | 0.044* | |
C11 | 0.8955 (2) | 0.86534 (9) | 0.40546 (9) | 0.0157 (2) | |
C12 | 1.06672 (19) | 0.91808 (9) | 0.37733 (9) | 0.0184 (2) | |
H12 | 1.1441 | 0.9537 | 0.4213 | 0.022* | |
C13 | 1.1243 (2) | 0.91865 (10) | 0.28521 (10) | 0.0204 (2) | |
H13 | 1.2398 | 0.9553 | 0.2663 | 0.024* | |
C14 | 1.0131 (2) | 0.86557 (10) | 0.22048 (10) | 0.0207 (3) | |
H14 | 1.0544 | 0.8649 | 0.1578 | 0.025* | |
C15 | 0.8418 (2) | 0.81371 (9) | 0.24793 (9) | 0.0183 (2) | |
H15 | 0.7669 | 0.7772 | 0.2038 | 0.022* | |
C16 | 0.77864 (18) | 0.81464 (9) | 0.33978 (8) | 0.0154 (2) | |
C20 | 0.46858 (19) | 0.72829 (9) | 0.32072 (9) | 0.0163 (2) | |
H20 | 0.4825 | 0.7356 | 0.256 | 0.02* | |
C21 | 0.29351 (18) | 0.67619 (9) | 0.35701 (9) | 0.0160 (2) | |
C22 | 0.2565 (2) | 0.67077 (9) | 0.45218 (9) | 0.0162 (2) | |
C23 | 0.0801 (2) | 0.62239 (10) | 0.48438 (10) | 0.0177 (2) | |
C24 | −0.0506 (2) | 0.57793 (10) | 0.42205 (10) | 0.0194 (3) | |
H24 | −0.1682 | 0.5446 | 0.4438 | 0.023* | |
C25 | −0.0107 (2) | 0.58169 (10) | 0.32718 (10) | 0.0208 (2) | |
H25 | −0.1001 | 0.5501 | 0.2852 | 0.025* | |
C26 | 0.1581 (2) | 0.63112 (9) | 0.29469 (10) | 0.0184 (2) | |
H26 | 0.183 | 0.6348 | 0.2303 | 0.022* | |
C30 | −0.1198 (2) | 0.57256 (12) | 0.61210 (11) | 0.0278 (3) | |
H30A | −0.1218 | 0.5764 | 0.6795 | 0.042* | |
H30B | −0.1154 | 0.504 | 0.5931 | 0.042* | |
H30C | −0.2431 | 0.6033 | 0.5872 | 0.042* | |
N | 0.60549 (16) | 0.76485 (8) | 0.37401 (8) | 0.0164 (2) | |
O1 | 0.05566 (16) | 0.62189 (8) | 0.57788 (7) | 0.0217 (2) | |
O2 | 0.38302 (14) | 0.71055 (7) | 0.51535 (8) | 0.02124 (18) | |
S | 0.81038 (4) | 0.85925 (2) | 0.52030 (2) | 0.01842 (7) | |
H2 | 0.471 (4) | 0.7359 (16) | 0.4864 (17) | 0.040 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0287 (7) | 0.0389 (8) | 0.0203 (6) | −0.0137 (6) | −0.0024 (6) | −0.0037 (6) |
C11 | 0.0154 (5) | 0.0165 (5) | 0.0154 (5) | 0.0017 (4) | 0.0013 (4) | 0.0009 (4) |
C12 | 0.0159 (5) | 0.0189 (5) | 0.0205 (6) | −0.0013 (4) | 0.0003 (4) | −0.0001 (4) |
C13 | 0.0165 (5) | 0.0213 (6) | 0.0233 (6) | −0.0015 (4) | 0.0035 (5) | 0.0017 (5) |
C14 | 0.0198 (6) | 0.0240 (6) | 0.0183 (6) | −0.0004 (5) | 0.0044 (5) | 0.0017 (5) |
C15 | 0.0176 (5) | 0.0197 (5) | 0.0177 (5) | 0.0008 (4) | 0.0003 (4) | 0.0001 (4) |
C16 | 0.0132 (5) | 0.0158 (5) | 0.0171 (5) | 0.0003 (4) | 0.0003 (4) | 0.0011 (4) |
C20 | 0.0152 (5) | 0.0165 (5) | 0.0172 (5) | 0.0005 (4) | 0.0007 (4) | 0.0002 (4) |
C21 | 0.0147 (5) | 0.0147 (5) | 0.0185 (5) | 0.0008 (4) | −0.0008 (4) | 0.0000 (4) |
C22 | 0.0143 (5) | 0.0161 (5) | 0.0183 (6) | −0.0010 (4) | −0.0010 (4) | 0.0002 (4) |
C23 | 0.0146 (5) | 0.0169 (5) | 0.0216 (6) | −0.0002 (4) | 0.0013 (5) | 0.0005 (5) |
C24 | 0.0158 (5) | 0.0169 (6) | 0.0257 (7) | −0.0012 (4) | −0.0013 (5) | 0.0028 (4) |
C25 | 0.0175 (5) | 0.0193 (6) | 0.0256 (6) | −0.0023 (4) | −0.0043 (5) | −0.0007 (5) |
C26 | 0.0179 (6) | 0.0183 (6) | 0.0191 (6) | 0.0009 (4) | −0.0023 (5) | −0.0012 (4) |
C30 | 0.0237 (7) | 0.0329 (8) | 0.0268 (7) | −0.0078 (6) | 0.0066 (6) | 0.0052 (6) |
N | 0.0141 (5) | 0.0167 (5) | 0.0184 (5) | −0.0011 (4) | 0.0016 (4) | 0.0006 (4) |
O1 | 0.0186 (4) | 0.0256 (5) | 0.0207 (5) | −0.0050 (4) | 0.0014 (4) | 0.0036 (4) |
O2 | 0.0181 (4) | 0.0282 (4) | 0.0175 (4) | −0.0081 (3) | −0.0001 (4) | −0.0002 (4) |
S | 0.01643 (13) | 0.02338 (14) | 0.01544 (13) | −0.00177 (10) | 0.00058 (12) | −0.00074 (13) |
C1—S | 1.7939 (15) | C20—H20 | 0.95 |
C1—H1A | 0.98 | C21—C22 | 1.4051 (18) |
C1—H1B | 0.98 | C21—C26 | 1.4103 (18) |
C1—H1C | 0.98 | C22—O2 | 1.3517 (16) |
C11—C12 | 1.3963 (18) | C22—C23 | 1.4128 (18) |
C11—C16 | 1.4072 (17) | C23—O1 | 1.3670 (18) |
C11—S | 1.7605 (13) | C23—C24 | 1.3873 (18) |
C12—C13 | 1.3898 (19) | C24—C25 | 1.403 (2) |
C12—H12 | 0.95 | C24—H24 | 0.95 |
C13—C14 | 1.395 (2) | C25—C26 | 1.3811 (19) |
C13—H13 | 0.95 | C25—H25 | 0.95 |
C14—C15 | 1.3873 (18) | C26—H26 | 0.95 |
C14—H14 | 0.95 | C30—O1 | 1.4243 (17) |
C15—C16 | 1.3965 (18) | C30—H30A | 0.98 |
C15—H15 | 0.95 | C30—H30B | 0.98 |
C16—N | 1.4150 (16) | C30—H30C | 0.98 |
C20—N | 1.2868 (16) | O2—H2 | 0.79 (2) |
C20—C21 | 1.4510 (17) | ||
S—C1—H1A | 109.5 | C22—C21—C20 | 121.32 (12) |
S—C1—H1B | 109.5 | C26—C21—C20 | 118.73 (12) |
H1A—C1—H1B | 109.5 | O2—C22—C21 | 122.68 (12) |
S—C1—H1C | 109.5 | O2—C22—C23 | 117.87 (11) |
H1A—C1—H1C | 109.5 | C21—C22—C23 | 119.46 (12) |
H1B—C1—H1C | 109.5 | O1—C23—C24 | 124.98 (13) |
C12—C11—C16 | 119.70 (12) | O1—C23—C22 | 115.27 (12) |
C12—C11—S | 123.81 (10) | C24—C23—C22 | 119.73 (13) |
C16—C11—S | 116.48 (10) | C23—C24—C25 | 120.62 (12) |
C13—C12—C11 | 120.17 (12) | C23—C24—H24 | 119.7 |
C13—C12—H12 | 119.9 | C25—C24—H24 | 119.7 |
C11—C12—H12 | 119.9 | C26—C25—C24 | 120.19 (13) |
C12—C13—C14 | 120.25 (12) | C26—C25—H25 | 119.9 |
C12—C13—H13 | 119.9 | C24—C25—H25 | 119.9 |
C14—C13—H13 | 119.9 | C25—C26—C21 | 120.02 (13) |
C15—C14—C13 | 119.79 (12) | C25—C26—H26 | 120 |
C15—C14—H14 | 120.1 | C21—C26—H26 | 120 |
C13—C14—H14 | 120.1 | O1—C30—H30A | 109.5 |
C14—C15—C16 | 120.65 (12) | O1—C30—H30B | 109.5 |
C14—C15—H15 | 119.7 | H30A—C30—H30B | 109.5 |
C16—C15—H15 | 119.7 | O1—C30—H30C | 109.5 |
C15—C16—C11 | 119.35 (11) | H30A—C30—H30C | 109.5 |
C15—C16—N | 124.69 (11) | H30B—C30—H30C | 109.5 |
C11—C16—N | 115.93 (11) | C20—N—C16 | 122.44 (11) |
N—C20—C21 | 121.69 (11) | C23—O1—C30 | 116.32 (12) |
N—C20—H20 | 119.2 | C22—O2—H2 | 105.3 (17) |
C21—C20—H20 | 119.2 | C11—S—C1 | 102.27 (7) |
C22—C21—C26 | 119.94 (12) | ||
C16—C11—C12—C13 | −1.52 (18) | O2—C22—C23—O1 | 0.53 (18) |
S—C11—C12—C13 | 179.66 (10) | C21—C22—C23—O1 | −179.22 (13) |
C11—C12—C13—C14 | −0.8 (2) | O2—C22—C23—C24 | −178.01 (12) |
C12—C13—C14—C15 | 1.4 (2) | C21—C22—C23—C24 | 2.23 (19) |
C13—C14—C15—C16 | 0.5 (2) | O1—C23—C24—C25 | −179.26 (14) |
C14—C15—C16—C11 | −2.79 (19) | C22—C23—C24—C25 | −0.9 (2) |
C14—C15—C16—N | 179.43 (12) | C23—C24—C25—C26 | −1.0 (2) |
C12—C11—C16—C15 | 3.31 (18) | C24—C25—C26—C21 | 1.4 (2) |
S—C11—C16—C15 | −177.79 (9) | C22—C21—C26—C25 | −0.01 (19) |
C12—C11—C16—N | −178.72 (11) | C20—C21—C26—C25 | −179.48 (12) |
S—C11—C16—N | 0.19 (15) | C21—C20—N—C16 | 179.07 (11) |
N—C20—C21—C22 | 5.67 (19) | C15—C16—N—C20 | −13.02 (19) |
N—C20—C21—C26 | −174.88 (12) | C11—C16—N—C20 | 169.13 (11) |
C26—C21—C22—O2 | 178.46 (12) | C24—C23—O1—C30 | −0.8 (2) |
C20—C21—C22—O2 | −2.09 (19) | C22—C23—O1—C30 | −179.29 (12) |
C26—C21—C22—C23 | −1.80 (19) | C12—C11—S—C1 | −15.22 (13) |
C20—C21—C22—C23 | 177.65 (11) | C16—C11—S—C1 | 165.92 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N | 0.79 (2) | 1.90 (3) | 2.6255 (15) | 152 (2) |
Experimental details
Crystal data | |
Chemical formula | C15H15NO2S |
Mr | 273.34 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 100 |
a, b, c (Å) | 6.5559 (4), 13.7147 (7), 14.5200 (8) |
V (Å3) | 1305.53 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.59 × 0.33 × 0.32 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.841, 0.930 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14274, 3900, 3875 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.714 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.079, 1.13 |
No. of reflections | 3900 |
No. of parameters | 176 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.22 |
Absolute structure | Flack (1983), with 1831 Friedel pairs |
Absolute structure parameter | 0.06 (5) |
Computer programs: SMART (Bruker, 2002), SAINT-Plus (Bruker, 2003), SAINT-Plus, SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
C16—N | 1.4150 (16) | C20—N | 1.2868 (16) |
N—C20—C21 | 121.69 (11) | C20—N—C16 | 122.44 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N | 0.79 (2) | 1.90 (3) | 2.6255 (15) | 152 (2) |
Schiff base ligands are common in coordination chemistry (Che & Huang, 2003). Our group is interested in the sythesis and coordination chemistry of novel sulfur-containing mixed-donor ligands (Hamaker & Halbach, 2005). As part of these ongoing studies, we report here the synthesis and molecular structure of the title compound, (I).
The molecule of compound (I) (Fig. 1) is nearly planar, with a dihedral angle between the two aromatic rings of 6.78 (7)° and a C21—C20—N—C16 torsion angle of 179.07 (11)°. The planarity of (I) is stabilized by an intramolecular O2—H2···N hydrogen bond (Table 2). The bond lengths and angles (Table 1) are similar to those of related Schiff base compounds (Singh et al., 2003; Yeap et al., 2003; Francis et al., 2003).