Acta Cryst. (2008). E64, o1704 [ doi:10.1107/S1600536808024628 ]
Molecules of the title compound, C12H7NOS, with one half-molecule in the asymmetric unit, are disordered about a crystallographic centre of inversion. Refinement showed that the C=O group is disordered with the S atom and the N atom is disordered over four positions. Adjacent molecules are connected through C-H
O hydrogen bonds and ![[pi]](/logos/entities/pi_rmgif.gif)
interactions (centroid-centroid distances of 3.635 and 3.858 Å).
A mixture of 2-chloronicotinic acid (1.57 g, 10 mmol) and thiophenol (2 ml) was heated under reflux for two hours to produce 2-(phenylsulfanyl) pyridine-3-carboxylic acid (Mann & Reid, 1952). The pollyphosforic acid (PPA) (Hidetoshi, 1997) was used to obtain 5H-benzothiopyrano[2,3-b]pyridin-5-one after cyclization. Crystals suitable for X-ray diffraction were obtained by cooling the saturated solution of the title compound in chloroform.
For the molecule is disordered, during refinement EXYZ and EADP were used for N1A, C3B and N1B, C3A. The occupancy factors for N1A and N1B refined to 0.231 (4) and 0.269 (4), respectively. Thus, they were fixed to 0.25 whereas for C3A and C3B the site occupation factors were fixed to 0.75.
The H atoms were positioned geometrically, with C—H = 0.93 Å, Uiso(H) = 1.2Ueq(C) and constrained to ride on their parent atoms.
Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
![[Figure 1]](./bt2756fig1thm.gif)
| Fig. 1. ORTEP-3 for Windows (Farrugia, 1997) drawing of the title compound. The symmetry related atoms are shown by putting ' on the names. The displacement ellipsoids are drawn at the 50% probability level. H-atoms are shown by small circles of arbitrary radii. |
| C12H7NOS | F000 = 220 |
| Mr = 213.26 | Dx = 1.525 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1189 reflections |
| a = 7.7308 (18) Å | θ = 2.6–28.7º |
| b = 3.8585 (9) Å | µ = 0.31 mm−1 |
| c = 15.771 (3) Å | T = 296 (2) K |
| β = 99.333 (9)º | Needle, light yellow |
| V = 464.20 (18) Å3 | 0.25 × 0.06 × 0.04 mm |
| Z = 2 |
| Bruker Kappa APEXII CCD diffractometer | 1189 independent reflections |
| Radiation source: fine-focus sealed tube | 822 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.034 |
| Detector resolution: 7.5 pixels mm-1 | θmax = 28.7º |
| T = 296(2) K | θmin = 2.6º |
| ω scans | h = −10→10 |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −5→3 |
| Tmin = 0.977, Tmax = 0.987 | l = −21→21 |
| 5384 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)] = 0.070 | H-atom parameters constrained |
| wR(F2) = 0.179 | w = 1/[σ2(Fo2) + (0.064P)2 + 0.435P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.17 | (Δ/σ)max < 0.001 |
| 1189 reflections | Δρmax = 0.62 e Å−3 |
| 83 parameters | Δρmin = −0.26 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C12H7NOS | V = 464.20 (18) Å3 |
| Mr = 213.26 | Z = 2 |
| Monoclinic, P21/c | Mo Kα |
| a = 7.7308 (18) Å | µ = 0.31 mm−1 |
| b = 3.8585 (9) Å | T = 296 (2) K |
| c = 15.771 (3) Å | 0.25 × 0.06 × 0.04 mm |
| β = 99.333 (9)º |
| Bruker Kappa APEXII CCD diffractometer | 1189 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 822 reflections with I > 2σ(I) |
| Tmin = 0.977, Tmax = 0.987 | Rint = 0.034 |
| 5384 measured reflections |
| R[F2 > 2σ(F2)] = 0.070 | 83 parameters |
| wR(F2) = 0.179 | H-atom parameters constrained |
| S = 1.17 | Δρmax = 0.62 e Å−3 |
| 1189 reflections | Δρmin = −0.26 e Å−3 |
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 | Occ. (<1) | |
| C6 | 0.3852 (15) | 0.001 (3) | 0.0576 (7) | 0.044 (2) | 0.50 |
| O1 | 0.2856 (9) | −0.006 (2) | 0.1093 (4) | 0.083 (3) | 0.50 |
| C3B | 0.1527 (4) | −0.2668 (8) | −0.05322 (19) | 0.0508 (7) | 0.75 |
| H3B | 0.0739 | −0.2649 | −0.0145 | 0.061* | 0.75 |
| N1B | 0.3839 (4) | −0.2689 (8) | −0.17028 (19) | 0.0530 (8) | 0.25 |
| S1 | 0.6613 (4) | −0.0009 (10) | −0.08029 (19) | 0.0481 (6) | 0.50 |
| C3A | 0.3839 (4) | −0.2689 (8) | −0.17028 (19) | 0.0530 (8) | 0.75 |
| H3A | 0.4605 | −0.2676 | −0.2100 | 0.064* | 0.75 |
| N1A | 0.1527 (4) | −0.2668 (8) | −0.05322 (19) | 0.0508 (7) | 0.25 |
| C1 | 0.4368 (4) | −0.1412 (8) | −0.08724 (19) | 0.0444 (7) | |
| C2 | 0.3204 (4) | −0.1406 (8) | −0.02885 (17) | 0.0437 (7) | |
| C4 | 0.1027 (4) | −0.3937 (9) | −0.1335 (2) | 0.0577 (9) | |
| H4 | −0.0102 | −0.4803 | −0.1495 | 0.069* | |
| C5 | 0.2178 (5) | −0.3955 (9) | −0.1919 (2) | 0.0570 (9) | |
| H5 | 0.1816 | −0.4842 | −0.2467 | 0.068* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C6 | 0.045 (6) | 0.038 (3) | 0.047 (6) | 0.002 (4) | 0.002 (3) | 0.008 (4) |
| O1 | 0.073 (4) | 0.134 (6) | 0.053 (4) | −0.023 (4) | 0.047 (3) | −0.015 (4) |
| C3B | 0.0496 (16) | 0.0468 (16) | 0.0563 (17) | −0.0002 (13) | 0.0099 (13) | 0.0016 (13) |
| N1B | 0.0632 (19) | 0.0482 (17) | 0.0476 (15) | 0.0023 (14) | 0.0090 (13) | −0.0010 (13) |
| S1 | 0.0438 (17) | 0.0620 (11) | 0.0411 (16) | −0.0040 (13) | 0.0145 (8) | −0.0032 (13) |
| C3A | 0.0632 (19) | 0.0482 (17) | 0.0476 (15) | 0.0023 (14) | 0.0090 (13) | −0.0010 (13) |
| N1A | 0.0496 (16) | 0.0468 (16) | 0.0563 (17) | −0.0002 (13) | 0.0099 (13) | 0.0016 (13) |
| C1 | 0.0434 (14) | 0.0371 (14) | 0.0512 (16) | 0.0028 (12) | 0.0031 (12) | 0.0058 (12) |
| C2 | 0.0522 (16) | 0.0361 (14) | 0.0420 (14) | 0.0059 (12) | 0.0049 (12) | 0.0037 (11) |
| C4 | 0.0501 (18) | 0.0507 (19) | 0.066 (2) | −0.0058 (14) | −0.0082 (15) | 0.0034 (15) |
| C5 | 0.069 (2) | 0.0495 (18) | 0.0474 (17) | 0.0000 (16) | −0.0075 (15) | −0.0048 (14) |
| C6—O1 | 1.209 (9) | S1—C2i | 1.791 (4) |
| C6—C2 | 1.480 (13) | S1—C1 | 1.803 (4) |
| C6—C1i | 1.481 (13) | C1—C2 | 1.388 (4) |
| C3B—C4 | 1.355 (4) | C1—C6i | 1.481 (13) |
| C3B—C2 | 1.380 (4) | C2—S1i | 1.791 (4) |
| C3B—H3B | 0.9300 | C4—C5 | 1.380 (5) |
| N1B—C5 | 1.364 (5) | C4—H4 | 0.9300 |
| N1B—C1 | 1.398 (4) | C5—H5 | 0.9300 |
| O1—C6—C2 | 117.2 (11) | C6i—C1—S1 | 15.5 (4) |
| O1—C6—C1i | 117.1 (11) | C3B—C2—C1 | 119.7 (3) |
| C2—C6—C1i | 125.7 (7) | C3B—C2—C6 | 123.3 (5) |
| C4—C3B—C2 | 120.0 (3) | C1—C2—C6 | 117.0 (5) |
| C4—C3B—H3B | 120.0 | C3B—C2—S1i | 107.4 (2) |
| C2—C3B—H3B | 120.0 | C1—C2—S1i | 132.9 (3) |
| C5—N1B—C1 | 118.7 (3) | C6—C2—S1i | 15.9 (4) |
| C2i—S1—C1 | 94.30 (18) | C3B—C4—C5 | 120.6 (3) |
| C2—C1—N1B | 120.0 (3) | C3B—C4—H4 | 119.7 |
| C2—C1—C6i | 117.3 (5) | C5—C4—H4 | 119.7 |
| N1B—C1—C6i | 122.7 (5) | N1B—C5—C4 | 120.9 (3) |
| C2—C1—S1 | 132.8 (3) | N1B—C5—H5 | 119.6 |
| N1B—C1—S1 | 107.2 (2) | C4—C5—H5 | 119.6 |
| C5—N1B—C1—C2 | −0.8 (5) | S1—C1—C2—C6 | 0.2 (6) |
| C5—N1B—C1—C6i | 179.5 (6) | N1B—C1—C2—S1i | −179.5 (3) |
| C5—N1B—C1—S1 | 179.4 (3) | C6i—C1—C2—S1i | 0.2 (6) |
| C2i—S1—C1—C2 | −0.2 (4) | S1—C1—C2—S1i | 0.2 (6) |
| C2i—S1—C1—N1B | 179.6 (2) | O1—C6—C2—C3B | 2.2 (15) |
| C2i—S1—C1—C6i | 0(2) | C1i—C6—C2—C3B | −179.7 (7) |
| C4—C3B—C2—C1 | 0.6 (5) | O1—C6—C2—C1 | −178.2 (10) |
| C4—C3B—C2—C6 | −179.8 (6) | C1i—C6—C2—C1 | −0.1 (12) |
| C4—C3B—C2—S1i | −179.7 (3) | O1—C6—C2—S1i | 2.0 (11) |
| N1B—C1—C2—C3B | 0.1 (4) | C1i—C6—C2—S1i | −180 (3) |
| C6i—C1—C2—C3B | 179.7 (6) | C2—C3B—C4—C5 | −0.5 (5) |
| S1—C1—C2—C3B | 179.8 (3) | C1—N1B—C5—C4 | 0.9 (5) |
| N1B—C1—C2—C6 | −179.6 (6) | C3B—C4—C5—N1B | −0.2 (5) |
| C6i—C1—C2—C6 | 0.1 (11) |
| Symmetry codes: (i) −x+1, −y, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C5—H5···O1ii | 0.93 | 2.53 | 3.286 (7) | 139 |
| Symmetry codes: (ii) x, −y−1/2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C5—H5···O1i | 0.93 | 2.53 | 3.286 (7) | 139 |
| Symmetry codes: (i) x, −y−1/2, z−1/2. |
The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, for funding the purchase of the diffractometer at GCU, Lahore.
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In continuation of our studies of pyridine containing heterocyclic compounds (Khan, et al., 2008), the title compound has been synthesized. As the molecule is located on a centre of inversion the thio (S1) and carbonyl group (C6=O1) are disordered over two sites with 50% occupancy. For the N atom four different positions were found with an occupancy factor of 0.25. Adjacent molecules are linked to each other through intermolecular H-bonding of C—H···O type (Table 1). In addition, there are π···π-interactions between the the adjacent molecules. The centroid of the ring composed by C1, C2, C3A, C4, C5, and N1B is at 3.635Å from the centroid of the central ring and at 3.858Å from the centroid of its symmetry equivalent (symmetry operator for both centroids: x, y-1, z)