Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680706045X/bg2139sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680706045X/bg2139Isup2.hkl |
CCDC reference: 673049
The title compound was synthesized by the reaction of pyridine-2-thiol with p-tolylcarbamic chloride in refluxing ethanol. Crystals of (I) suitable for single-crystal X-ray analysis were grown by slow evaporation of a solution in chloroform/acetone.
The H atom attached to N atom was located in a difference density map and the atomic coordinates allowed to refine freely. Other H atoms attached to carbon were positioned geometrically and refined as riding (C—H = 0.93–0.97%A). For the CH and CH2 groups, Uiso(H) values were set equal to 1.2Ueq(C) and for the methyl groups they were set equal to 1.5Ueq(C).
Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level. |
C14H14N2OS | Dx = 1.281 Mg m−3 |
Mr = 258.33 | Melting point: 403 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 2537 reflections |
a = 9.348 (2) Å | θ = 2.8–22.6° |
b = 12.361 (3) Å | µ = 0.23 mm−1 |
c = 23.184 (6) Å | T = 294 K |
V = 2678.9 (11) Å3 | Plate, colourless |
Z = 8 | 0.20 × 0.18 × 0.14 mm |
F(000) = 1088 |
Bruker SMART CCD area-detector diffractometer | 2366 independent reflections |
Radiation source: fine-focus sealed tube | 1535 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→11 |
Tmin = 0.95, Tmax = 0.97 | k = −14→14 |
12855 measured reflections | l = −27→15 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0661P)2 + 0.6597P] where P = (Fo2 + 2Fc2)/3 |
2366 reflections | (Δ/σ)max = 0.001 |
168 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C14H14N2OS | V = 2678.9 (11) Å3 |
Mr = 258.33 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.348 (2) Å | µ = 0.23 mm−1 |
b = 12.361 (3) Å | T = 294 K |
c = 23.184 (6) Å | 0.20 × 0.18 × 0.14 mm |
Bruker SMART CCD area-detector diffractometer | 2366 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1535 reflections with I > 2σ(I) |
Tmin = 0.95, Tmax = 0.97 | Rint = 0.066 |
12855 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.25 e Å−3 |
2366 reflections | Δρmin = −0.26 e Å−3 |
168 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 | 0.15494 (7) | 0.53279 (5) | 0.32262 (3) | 0.0510 (3) | |
O1 | 0.09884 (17) | 0.36599 (16) | 0.22875 (8) | 0.0607 (6) | |
N1 | 0.1009 (3) | 0.4497 (2) | 0.42221 (10) | 0.0619 (7) | |
N2 | 0.3332 (2) | 0.33742 (17) | 0.20810 (9) | 0.0453 (5) | |
C1 | 0.1150 (4) | 0.3798 (3) | 0.46624 (14) | 0.0786 (10) | |
H1 | 0.0559 | 0.3888 | 0.4981 | 0.094* | |
C2 | 0.2108 (4) | 0.2963 (3) | 0.46715 (14) | 0.0789 (10) | |
H2 | 0.2156 | 0.2494 | 0.4984 | 0.095* | |
C3 | 0.3000 (4) | 0.2838 (3) | 0.42029 (13) | 0.0691 (9) | |
H3 | 0.3672 | 0.2283 | 0.4198 | 0.083* | |
C4 | 0.2894 (3) | 0.3536 (2) | 0.37423 (12) | 0.0538 (7) | |
H4 | 0.3489 | 0.3464 | 0.3423 | 0.065* | |
C5 | 0.1877 (3) | 0.4347 (2) | 0.37679 (11) | 0.0439 (6) | |
C6 | 0.2722 (3) | 0.4933 (2) | 0.26470 (11) | 0.0479 (7) | |
H6A | 0.2788 | 0.5525 | 0.2374 | 0.057* | |
H6B | 0.3671 | 0.4811 | 0.2803 | 0.057* | |
C7 | 0.2246 (2) | 0.39226 (19) | 0.23277 (10) | 0.0407 (6) | |
C8 | 0.3274 (2) | 0.24390 (19) | 0.17239 (10) | 0.0408 (6) | |
C9 | 0.4569 (3) | 0.1969 (2) | 0.15700 (12) | 0.0554 (7) | |
H9 | 0.5421 | 0.2262 | 0.1705 | 0.067* | |
C10 | 0.4597 (3) | 0.1067 (2) | 0.12164 (13) | 0.0625 (8) | |
H10 | 0.5475 | 0.0775 | 0.1110 | 0.075* | |
C11 | 0.3352 (3) | 0.0589 (2) | 0.10166 (12) | 0.0517 (7) | |
C12 | 0.2078 (3) | 0.1059 (2) | 0.11785 (11) | 0.0523 (7) | |
H12 | 0.1227 | 0.0754 | 0.1049 | 0.063* | |
C13 | 0.2016 (3) | 0.1970 (2) | 0.15273 (11) | 0.0480 (6) | |
H13 | 0.1137 | 0.2265 | 0.1629 | 0.058* | |
C14 | 0.3383 (3) | −0.0406 (2) | 0.06350 (15) | 0.0742 (9) | |
H14A | 0.2519 | −0.0813 | 0.0689 | 0.111* | |
H14B | 0.4191 | −0.0846 | 0.0735 | 0.111* | |
H14C | 0.3458 | −0.0188 | 0.0239 | 0.111* | |
H2A | 0.420 (3) | 0.3602 (19) | 0.2169 (10) | 0.050 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0496 (4) | 0.0530 (4) | 0.0504 (4) | 0.0121 (3) | 0.0049 (3) | 0.0018 (3) |
O1 | 0.0300 (10) | 0.0814 (14) | 0.0706 (13) | −0.0041 (9) | 0.0053 (9) | −0.0170 (10) |
N1 | 0.0601 (14) | 0.0777 (17) | 0.0479 (14) | 0.0104 (13) | 0.0075 (12) | −0.0002 (12) |
N2 | 0.0268 (11) | 0.0523 (13) | 0.0567 (14) | −0.0019 (10) | 0.0002 (10) | −0.0017 (11) |
C1 | 0.092 (2) | 0.095 (3) | 0.0492 (19) | 0.004 (2) | 0.0129 (17) | 0.0102 (18) |
C2 | 0.111 (3) | 0.074 (2) | 0.052 (2) | 0.000 (2) | −0.005 (2) | 0.0160 (17) |
C3 | 0.086 (2) | 0.0578 (18) | 0.064 (2) | 0.0111 (17) | −0.0137 (18) | −0.0023 (16) |
C4 | 0.0583 (16) | 0.0549 (16) | 0.0481 (16) | 0.0061 (14) | −0.0032 (13) | −0.0012 (13) |
C5 | 0.0413 (14) | 0.0496 (15) | 0.0406 (14) | −0.0019 (12) | −0.0018 (11) | −0.0055 (12) |
C6 | 0.0440 (15) | 0.0504 (15) | 0.0494 (16) | −0.0016 (12) | 0.0052 (12) | 0.0055 (12) |
C7 | 0.0331 (13) | 0.0514 (15) | 0.0375 (14) | −0.0019 (11) | 0.0016 (11) | 0.0098 (11) |
C8 | 0.0323 (13) | 0.0427 (13) | 0.0474 (15) | −0.0009 (11) | 0.0024 (11) | 0.0071 (12) |
C9 | 0.0356 (14) | 0.0513 (16) | 0.079 (2) | −0.0003 (12) | −0.0004 (13) | −0.0028 (15) |
C10 | 0.0449 (16) | 0.0543 (17) | 0.088 (2) | 0.0103 (14) | 0.0033 (15) | −0.0050 (16) |
C11 | 0.0544 (17) | 0.0455 (15) | 0.0552 (17) | 0.0018 (13) | −0.0038 (13) | 0.0054 (13) |
C12 | 0.0449 (15) | 0.0626 (18) | 0.0494 (16) | −0.0110 (13) | −0.0046 (12) | 0.0009 (14) |
C13 | 0.0339 (13) | 0.0624 (17) | 0.0477 (15) | 0.0010 (12) | 0.0011 (11) | 0.0013 (14) |
C14 | 0.081 (2) | 0.0598 (19) | 0.082 (2) | 0.0022 (17) | −0.0014 (17) | −0.0118 (17) |
S1—C5 | 1.772 (3) | C6—H6A | 0.9700 |
S1—C6 | 1.801 (2) | C6—H6B | 0.9700 |
O1—C7 | 1.224 (3) | C8—C13 | 1.388 (3) |
N1—C5 | 1.342 (3) | C8—C9 | 1.389 (3) |
N1—C1 | 1.344 (4) | C9—C10 | 1.384 (4) |
N2—C7 | 1.347 (3) | C9—H9 | 0.9300 |
N2—C8 | 1.423 (3) | C10—C11 | 1.385 (4) |
N2—H2A | 0.89 (3) | C10—H10 | 0.9300 |
C1—C2 | 1.366 (5) | C11—C12 | 1.377 (4) |
C1—H1 | 0.9300 | C11—C14 | 1.515 (4) |
C2—C3 | 1.378 (4) | C12—C13 | 1.388 (4) |
C2—H2 | 0.9300 | C12—H12 | 0.9300 |
C3—C4 | 1.376 (4) | C13—H13 | 0.9300 |
C3—H3 | 0.9300 | C14—H14A | 0.9600 |
C4—C5 | 1.384 (3) | C14—H14B | 0.9600 |
C4—H4 | 0.9300 | C14—H14C | 0.9600 |
C6—C7 | 1.518 (3) | ||
C5—S1—C6 | 103.77 (12) | O1—C7—C6 | 122.4 (2) |
C5—N1—C1 | 116.6 (3) | N2—C7—C6 | 113.6 (2) |
C7—N2—C8 | 128.8 (2) | C13—C8—C9 | 118.6 (2) |
C7—N2—H2A | 115.8 (16) | C13—C8—N2 | 124.2 (2) |
C8—N2—H2A | 115.2 (16) | C9—C8—N2 | 117.2 (2) |
N1—C1—C2 | 124.2 (3) | C10—C9—C8 | 120.4 (2) |
N1—C1—H1 | 117.9 | C10—C9—H9 | 119.8 |
C2—C1—H1 | 117.9 | C8—C9—H9 | 119.8 |
C1—C2—C3 | 118.0 (3) | C9—C10—C11 | 121.7 (2) |
C1—C2—H2 | 121.0 | C9—C10—H10 | 119.1 |
C3—C2—H2 | 121.0 | C11—C10—H10 | 119.1 |
C4—C3—C2 | 119.8 (3) | C12—C11—C10 | 117.1 (2) |
C4—C3—H3 | 120.1 | C12—C11—C14 | 121.2 (2) |
C2—C3—H3 | 120.1 | C10—C11—C14 | 121.7 (2) |
C3—C4—C5 | 118.1 (3) | C11—C12—C13 | 122.5 (2) |
C3—C4—H4 | 121.0 | C11—C12—H12 | 118.8 |
C5—C4—H4 | 121.0 | C13—C12—H12 | 118.8 |
N1—C5—C4 | 123.3 (3) | C12—C13—C8 | 119.7 (2) |
N1—C5—S1 | 110.94 (19) | C12—C13—H13 | 120.2 |
C4—C5—S1 | 125.7 (2) | C8—C13—H13 | 120.2 |
C7—C6—S1 | 114.11 (17) | C11—C14—H14A | 109.5 |
C7—C6—H6A | 108.7 | C11—C14—H14B | 109.5 |
S1—C6—H6A | 108.7 | H14A—C14—H14B | 109.5 |
C7—C6—H6B | 108.7 | C11—C14—H14C | 109.5 |
S1—C6—H6B | 108.7 | H14A—C14—H14C | 109.5 |
H6A—C6—H6B | 107.6 | H14B—C14—H14C | 109.5 |
O1—C7—N2 | 123.9 (2) | ||
C5—N1—C1—C2 | 0.0 (5) | S1—C6—C7—N2 | −153.34 (18) |
N1—C1—C2—C3 | 0.9 (6) | C7—N2—C8—C13 | 5.5 (4) |
C1—C2—C3—C4 | −0.8 (5) | C7—N2—C8—C9 | −173.9 (2) |
C2—C3—C4—C5 | −0.1 (4) | C13—C8—C9—C10 | 1.6 (4) |
C1—N1—C5—C4 | −1.0 (4) | N2—C8—C9—C10 | −179.0 (2) |
C1—N1—C5—S1 | 179.7 (2) | C8—C9—C10—C11 | −1.6 (4) |
C3—C4—C5—N1 | 1.1 (4) | C9—C10—C11—C12 | 0.9 (4) |
C3—C4—C5—S1 | −179.8 (2) | C9—C10—C11—C14 | −179.3 (3) |
C6—S1—C5—N1 | −176.38 (19) | C10—C11—C12—C13 | −0.2 (4) |
C6—S1—C5—C4 | 4.4 (3) | C14—C11—C12—C13 | −180.0 (3) |
C5—S1—C6—C7 | 72.68 (19) | C11—C12—C13—C8 | 0.1 (4) |
C8—N2—C7—O1 | 2.0 (4) | C9—C8—C13—C12 | −0.8 (4) |
C8—N2—C7—C6 | −175.9 (2) | N2—C8—C13—C12 | 179.8 (2) |
S1—C6—C7—O1 | 28.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.89 (3) | 2.09 (3) | 2.904 (3) | 152 (2) |
Symmetry code: (i) x+1/2, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C14H14N2OS |
Mr | 258.33 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 294 |
a, b, c (Å) | 9.348 (2), 12.361 (3), 23.184 (6) |
V (Å3) | 2678.9 (11) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.20 × 0.18 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.95, 0.97 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12855, 2366, 1535 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.130, 1.01 |
No. of reflections | 2366 |
No. of parameters | 168 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.25, −0.26 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.89 (3) | 2.09 (3) | 2.904 (3) | 152 (2) |
Symmetry code: (i) x+1/2, y, −z+1/2. |
2-Mercaptopyridine is an important class of medical intermediate. Recently, many biological copmpounds (Koike et al.,1999) have been prepared having 2-mercaptopyridine as raw material. We have synthesized the title compound, C14H14N2 O S, (I), from 2-mercaptopyridine with p-tolylcarbamic chloride, and we are reporing herein its crystal structure.
The molecular structure of (I) contains a pyridinyl and a benzene rings, almost perpendicular to each other, subtending a dihedral angle of 91.8 (2)%. The methyl carbon is coplanar to the benzene ring (r.m.s deviation: 0.0075 (3) Å). Due to the π–π conjugation bwtween the S atom and pyridinyl ring, the S1—C5 bond distance [1.772 (3) Å] is slightly shorter than the S1—C6 one [1.801 (2) Å]. Intermolecular hydrogen bonds between adjacent N—H groups and carbonyl O atoms link molecules together into chains parallel to [100], the shortest axis direction.