Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807054463/at2450sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807054463/at2450Isup2.hkl |
CCDC reference: 672850
Key indicators
- Single-crystal X-ray study
- T = 113 K
- Mean (C-C) = 0.003 Å
- R factor = 0.045
- wR factor = 0.097
- Data-to-parameter ratio = 18.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C11 - C14 ... 1.44 Ang. PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 21 C10 -C11 -C14 -N1 -58.00 11.00 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 22 C12 -C11 -C14 -N1 121.00 11.00 1.555 1.555 1.555 1.555
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.88 From the CIF: _reflns_number_total 2670 Count of symmetry unique reflns 1553 Completeness (_total/calc) 171.93% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1117 Fraction of Friedel pairs measured 0.719 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 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 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Gans et al. (1990); Khanna et al. (2000); Robbins et al. (2003).
A mixture of 3-methylthiophenylboronic acid (1.327 mmol), 4-bromobenzonitrile (0.8845 mmol), K2CO3 (2.657 mmol) and POPd (0.00177 mmol, 0.2 mol %) was stirred and refluxed in 2 ml of dioxane for 3 h. The reaction mixture was allowed to cool to room temperature, quenched with water, and extracted with EtOAc. The combined organic layers were washed with brine and dried over MgSO4, and the solvents were removed under vacuum. The residue was purified by chromatography on silica gel eluting with hexane/EtOAc (60:1 v/v) to give the target product as white acicular crystal in 99.7% yield (m.p.337 K). Spectroscopic analysis: IR (KBr): 2230 cm-1. 1H NMR (500 MHz, Chloroform-d1, TMS): δ 2.54 (s, 3H), 7.31 (d, 1H, J= 7.8 Hz), 7.34 (d, 1H, J= 7.8 Hz), 7.39–7.42 (t, 1H, J= 7.8 Hz), 7.45 (s, 1H), 7.67 (d, 2H, J= 8.4 Hz), 7.73 (d, 2H, J= 8.3 Hz). 13C NMR (125 MHz, TMS): δ 15.8, 124., 125.4, 126.7, 127.9, 129.6, 139.5, 139.9, 147.2, 147.3; HRMS (EI): M+, found 225.0616. C14H11NS requires 225.0612. Crystals of (I) suitable for single-crystal X-ray analysis were grown by slow evaporation of a solution in chloroform-ethanol (1:1 v/v).
All H atoms were positioned geometrically and refined using a riding on their parent atoms, with C—H = 0.95–0.98 Å and Uiso(H) = 1.2 or 1.5Ueq(C).
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CrystalStructure (Rigaku/MSC, 2004); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004).
Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level. |
C14H11NS | Dx = 1.340 Mg m−3 |
Mr = 225.30 | Melting point: 337 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3597 reflections |
a = 7.2200 (14) Å | θ = 2.3–27.8° |
b = 11.961 (2) Å | µ = 0.26 mm−1 |
c = 12.936 (3) Å | T = 113 K |
V = 1117.2 (4) Å3 | Prism, colourless |
Z = 4 | 0.14 × 0.12 × 0.08 mm |
F(000) = 472 |
Rigaku Saturn diffractometer | 2670 independent reflections |
Radiation source: rotating anode | 2539 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.046 |
Detector resolution: 7.31 pixels mm-1 | θmax = 27.9°, θmin = 2.3° |
ω and ϕ scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −15→15 |
Tmin = 0.965, Tmax = 0.980 | l = −16→17 |
14124 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0426P)2 + 0.3196P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
2670 reflections | Δρmax = 0.22 e Å−3 |
146 parameters | Δρmin = −0.25 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1118 Friedel Pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.04 (10) |
C14H11NS | V = 1117.2 (4) Å3 |
Mr = 225.30 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.2200 (14) Å | µ = 0.26 mm−1 |
b = 11.961 (2) Å | T = 113 K |
c = 12.936 (3) Å | 0.14 × 0.12 × 0.08 mm |
Rigaku Saturn diffractometer | 2670 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2539 reflections with I > 2σ(I) |
Tmin = 0.965, Tmax = 0.980 | Rint = 0.046 |
14124 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.097 | Δρmax = 0.22 e Å−3 |
S = 1.09 | Δρmin = −0.25 e Å−3 |
2670 reflections | Absolute structure: Flack (1983), 1118 Friedel Pairs |
146 parameters | Absolute structure parameter: 0.04 (10) |
0 restraints |
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 | 0.24370 (8) | 0.21096 (4) | 0.38537 (4) | 0.02390 (14) | |
C6 | 0.1139 (2) | 0.30649 (16) | 0.09659 (14) | 0.0174 (4) | |
C2 | 0.1735 (3) | 0.29709 (17) | 0.28158 (15) | 0.0190 (4) | |
N1 | 0.1321 (3) | 0.04988 (16) | −0.37872 (15) | 0.0304 (4) | |
C13 | 0.1450 (3) | 0.31419 (16) | −0.09653 (15) | 0.0209 (4) | |
H13 | 0.1649 | 0.3925 | −0.0914 | 0.025* | |
C11 | 0.1171 (3) | 0.14894 (18) | −0.20058 (15) | 0.0203 (4) | |
C8 | 0.1125 (3) | 0.25204 (17) | −0.00672 (16) | 0.0179 (4) | |
C12 | 0.1485 (3) | 0.26366 (17) | −0.19279 (16) | 0.0218 (4) | |
H12 | 0.1721 | 0.3068 | −0.2530 | 0.026* | |
C5 | 0.0609 (3) | 0.41861 (16) | 0.10827 (16) | 0.0211 (4) | |
H5 | 0.0211 | 0.4604 | 0.0499 | 0.025* | |
C9 | 0.0812 (3) | 0.13761 (17) | −0.01641 (16) | 0.0199 (4) | |
H9 | 0.0587 | 0.0942 | 0.0438 | 0.024* | |
C1 | 0.2520 (4) | 0.30445 (16) | 0.49421 (15) | 0.0274 (4) | |
H1A | 0.3363 | 0.3665 | 0.4789 | 0.041* | |
H1B | 0.2966 | 0.2639 | 0.5552 | 0.041* | |
H1C | 0.1277 | 0.3338 | 0.5079 | 0.041* | |
C4 | 0.0664 (3) | 0.46838 (17) | 0.20489 (16) | 0.0243 (5) | |
H4 | 0.0320 | 0.5447 | 0.2119 | 0.029* | |
C7 | 0.1708 (3) | 0.24753 (16) | 0.18386 (15) | 0.0184 (4) | |
H7 | 0.2086 | 0.1719 | 0.1767 | 0.022* | |
C14 | 0.1240 (3) | 0.09457 (18) | −0.30001 (16) | 0.0231 (4) | |
C10 | 0.0824 (3) | 0.08612 (16) | −0.11220 (16) | 0.0219 (4) | |
H10 | 0.0595 | 0.0081 | −0.1176 | 0.026* | |
C3 | 0.1214 (3) | 0.40857 (17) | 0.29177 (16) | 0.0219 (4) | |
H3 | 0.1234 | 0.4436 | 0.3577 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0307 (3) | 0.0233 (2) | 0.0177 (2) | 0.0006 (2) | −0.0026 (2) | −0.00141 (19) |
C6 | 0.0115 (9) | 0.0194 (9) | 0.0211 (10) | −0.0031 (7) | 0.0002 (7) | −0.0002 (8) |
C2 | 0.0162 (9) | 0.0209 (9) | 0.0199 (9) | −0.0020 (8) | 0.0001 (7) | −0.0022 (8) |
N1 | 0.0353 (11) | 0.0311 (10) | 0.0248 (10) | 0.0022 (8) | −0.0014 (9) | −0.0029 (8) |
C13 | 0.0210 (10) | 0.0188 (10) | 0.0230 (11) | −0.0006 (8) | −0.0012 (8) | −0.0001 (8) |
C11 | 0.0157 (10) | 0.0247 (10) | 0.0203 (10) | 0.0027 (8) | −0.0020 (8) | −0.0014 (8) |
C8 | 0.0145 (9) | 0.0210 (9) | 0.0181 (10) | 0.0003 (7) | −0.0015 (8) | −0.0010 (8) |
C12 | 0.0205 (11) | 0.0238 (10) | 0.0210 (10) | 0.0004 (8) | −0.0017 (8) | 0.0032 (8) |
C5 | 0.0192 (10) | 0.0195 (9) | 0.0247 (10) | 0.0005 (8) | 0.0001 (9) | 0.0012 (9) |
C9 | 0.0196 (10) | 0.0203 (10) | 0.0199 (10) | 0.0005 (8) | 0.0002 (8) | 0.0014 (8) |
C1 | 0.0327 (11) | 0.0308 (11) | 0.0186 (9) | −0.0034 (11) | 0.0009 (10) | −0.0038 (8) |
C4 | 0.0222 (11) | 0.0191 (10) | 0.0315 (12) | 0.0024 (9) | −0.0004 (9) | −0.0038 (9) |
C7 | 0.0146 (9) | 0.0208 (9) | 0.0198 (10) | −0.0017 (8) | 0.0016 (7) | −0.0012 (8) |
C14 | 0.0205 (10) | 0.0247 (10) | 0.0241 (11) | 0.0032 (8) | −0.0030 (8) | 0.0009 (9) |
C10 | 0.0231 (10) | 0.0182 (9) | 0.0243 (10) | 0.0019 (8) | −0.0005 (9) | −0.0019 (9) |
C3 | 0.0211 (10) | 0.0224 (10) | 0.0221 (10) | 0.0020 (8) | 0.0011 (8) | −0.0055 (8) |
S1—C2 | 1.767 (2) | C8—C9 | 1.393 (3) |
S1—C1 | 1.7991 (19) | C12—H12 | 0.9500 |
C6—C7 | 1.393 (3) | C5—C4 | 1.385 (3) |
C6—C5 | 1.403 (3) | C5—H5 | 0.9500 |
C6—C8 | 1.487 (3) | C9—C10 | 1.384 (3) |
C2—C3 | 1.392 (3) | C9—H9 | 0.9500 |
C2—C7 | 1.396 (3) | C1—H1A | 0.9800 |
N1—C14 | 1.151 (3) | C1—H1B | 0.9800 |
C13—C12 | 1.384 (3) | C1—H1C | 0.9800 |
C13—C8 | 1.399 (3) | C4—C3 | 1.390 (3) |
C13—H13 | 0.9500 | C4—H4 | 0.9500 |
C11—C10 | 1.391 (3) | C7—H7 | 0.9500 |
C11—C12 | 1.394 (3) | C10—H10 | 0.9500 |
C11—C14 | 1.442 (3) | C3—H3 | 0.9500 |
C2—S1—C1 | 104.00 (10) | C10—C9—C8 | 121.13 (19) |
C7—C6—C5 | 118.50 (18) | C10—C9—H9 | 119.4 |
C7—C6—C8 | 120.58 (17) | C8—C9—H9 | 119.4 |
C5—C6—C8 | 120.91 (18) | S1—C1—H1A | 109.5 |
C3—C2—C7 | 119.26 (19) | S1—C1—H1B | 109.5 |
C3—C2—S1 | 124.36 (15) | H1A—C1—H1B | 109.5 |
C7—C2—S1 | 116.39 (15) | S1—C1—H1C | 109.5 |
C12—C13—C8 | 121.20 (18) | H1A—C1—H1C | 109.5 |
C12—C13—H13 | 119.4 | H1B—C1—H1C | 109.5 |
C8—C13—H13 | 119.4 | C5—C4—C3 | 121.11 (19) |
C10—C11—C12 | 120.09 (19) | C5—C4—H4 | 119.4 |
C10—C11—C14 | 119.72 (19) | C3—C4—H4 | 119.4 |
C12—C11—C14 | 120.18 (19) | C6—C7—C2 | 121.52 (18) |
C9—C8—C13 | 118.33 (19) | C6—C7—H7 | 119.2 |
C9—C8—C6 | 120.83 (18) | C2—C7—H7 | 119.2 |
C13—C8—C6 | 120.83 (17) | N1—C14—C11 | 178.7 (2) |
C13—C12—C11 | 119.45 (19) | C9—C10—C11 | 119.78 (18) |
C13—C12—H12 | 120.3 | C9—C10—H10 | 120.1 |
C11—C12—H12 | 120.3 | C11—C10—H10 | 120.1 |
C4—C5—C6 | 120.01 (19) | C4—C3—C2 | 119.58 (19) |
C4—C5—H5 | 120.0 | C4—C3—H3 | 120.2 |
C6—C5—H5 | 120.0 | C2—C3—H3 | 120.2 |
C1—S1—C2—C3 | −5.6 (2) | C6—C8—C9—C10 | −179.06 (18) |
C1—S1—C2—C7 | 174.60 (15) | C6—C5—C4—C3 | −1.0 (3) |
C12—C13—C8—C9 | −0.8 (3) | C5—C6—C7—C2 | 0.8 (3) |
C12—C13—C8—C6 | 178.35 (19) | C8—C6—C7—C2 | 179.90 (17) |
C7—C6—C8—C9 | 30.4 (3) | C3—C2—C7—C6 | −1.2 (3) |
C5—C6—C8—C9 | −150.53 (19) | S1—C2—C7—C6 | 178.57 (15) |
C7—C6—C8—C13 | −148.74 (19) | C10—C11—C14—N1 | −58 (11) |
C5—C6—C8—C13 | 30.3 (3) | C12—C11—C14—N1 | 121 (11) |
C8—C13—C12—C11 | 0.7 (3) | C8—C9—C10—C11 | 0.7 (3) |
C10—C11—C12—C13 | 0.1 (3) | C12—C11—C10—C9 | −0.8 (3) |
C14—C11—C12—C13 | −178.76 (19) | C14—C11—C10—C9 | 178.1 (2) |
C7—C6—C5—C4 | 0.3 (3) | C5—C4—C3—C2 | 0.6 (3) |
C8—C6—C5—C4 | −178.81 (18) | C7—C2—C3—C4 | 0.5 (3) |
C13—C8—C9—C10 | 0.1 (3) | S1—C2—C3—C4 | −179.27 (16) |
Experimental details
Crystal data | |
Chemical formula | C14H11NS |
Mr | 225.30 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 113 |
a, b, c (Å) | 7.2200 (14), 11.961 (2), 12.936 (3) |
V (Å3) | 1117.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.14 × 0.12 × 0.08 |
Data collection | |
Diffractometer | Rigaku Saturn diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.965, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14124, 2670, 2539 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.097, 1.09 |
No. of reflections | 2670 |
No. of parameters | 146 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.25 |
Absolute structure | Flack (1983), 1118 Friedel Pairs |
Absolute structure parameter | 0.04 (10) |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), CrystalStructure (Rigaku/MSC, 2004).
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Aryl compounds with a methylthio group are of interest as pesticide and synthetic intermediates used in the preparation of many pharmaceuticals (Robbins, et al., 2003). The methylthio group can be easily oxidized to form sulfinyl or sulfonyl groups, which are useful groups in pharmaceuticals (Gans, et al., 1990; Khanna, et al., 2000). Here, we report the synthesis and crystal structure of the title compound, (I).
The title compound of (I), contains two benzene rings and they make a dihedral angle of 22.0 (2)°. the torsion angles of C1—S1—C2—C3 and C1—S1—C2—C7 are 5.6 (2) and 174.60 (15)°, respectively, indicating that S atom don't significantly deviate from the benzene ring plane (C2—C7). The p-π conjugation of S atom with the benzene ring affect the bond distance S1—C2 [1.767 (2) Å] which is shorter than S1—C1 [1.7991 (19) Å].