organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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5H-1-Benzo­thio­pyrano[2,3-b]pyridin-5-one

aApplied Chemistry Research Center, PCSIR Laboratories Complex, Lahore 54600, Pakistan, and PhD Scholar, Department of Chemistry, Islamia University, Bahawalpur, Pakistan, bUniversity of Sargodha, Department of Physics, Sargodha, Pakistan, cDepartment of Chemistry, Islamia University, Bahawalpur, Pakistan, and dGovernment College University, Department of Chemistry, Lahore, Pakistan
*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 23 July 2008; accepted 31 July 2008; online 6 August 2008)

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 ππ inter­actions (centroid–centroid distances of 3.635 and 3.858 Å).

Related literature

For related literature, see: Hidetoshi (1997[Hidetoshi, F. (1997). Heterocycles, 45, 119-127.]); Khan et al. (2008[Khan, M. N., Tahir, M. N., Khan, M. A., Khan, I. U. & Arshad, M. N. (2008). Acta Cryst. E64, o730.]); Mann & Reid (1952[Mann, F. G. & Reid, J. A. (1952). J. Chem. Soc. pp. 2057-2062.]).

[Scheme 1]

Experimental

Crystal data
  • C12H7NOS

  • Mr = 213.26

  • Monoclinic, P 21 /c

  • a = 7.7308 (18) Å

  • b = 3.8585 (9) Å

  • c = 15.771 (3) Å

  • β = 99.333 (9)°

  • V = 464.20 (18) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.31 mm−1

  • T = 296 (2) K

  • 0.25 × 0.06 × 0.04 mm

Data collection
  • Bruker Kappa APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2005[Bruker (2005). SADABS. Bruker AXS Inc. Madison, Wisconsin, USA.]) Tmin = 0.977, Tmax = 0.987

  • 5384 measured reflections

  • 1189 independent reflections

  • 822 reflections with I > 2σ(I)

  • Rint = 0.034

Refinement
  • R[F2 > 2σ(F2)] = 0.070

  • wR(F2) = 0.179

  • S = 1.17

  • 1189 reflections

  • 83 parameters

  • H-atom parameters constrained

  • Δρmax = 0.62 e Å−3

  • Δρmin = −0.26 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C5—H5⋯O1i 0.93 2.53 3.286 (7) 139
Symmetry code: (i) [x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc. Madison, Wisconsin, USA.]); cell refinement: APEX2; data reduction: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc. Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]) and PLATON.

Supporting information


Comment top

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)

Related literature top

For related literature, see: Hidetoshi (1997); Khan et al. (2008); Mann & Reid (1952).

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] 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.
5H-1-Benzothiopyrano[2,3-b]pyridin-5-one top
Crystal data top
C12H7NOSF(000) = 220
Mr = 213.26Dx = 1.525 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1189 reflections
a = 7.7308 (18) Åθ = 2.6–28.7°
b = 3.8585 (9) ŵ = 0.31 mm1
c = 15.771 (3) ÅT = 296 K
β = 99.333 (9)°Needle, light yellow
V = 464.20 (18) Å30.25 × 0.06 × 0.04 mm
Z = 2
Data collection top
Bruker Kappa APEXII CCD
diffractometer
1189 independent reflections
Radiation source: fine-focus sealed tube822 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
Detector resolution: 7.5 pixels mm-1θmax = 28.7°, θmin = 2.6°
ω scansh = 1010
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
k = 53
Tmin = 0.977, Tmax = 0.987l = 2121
5384 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.070Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.179H-atom parameters constrained
S = 1.17 w = 1/[σ2(Fo2) + (0.064P)2 + 0.435P]
where P = (Fo2 + 2Fc2)/3
1189 reflections(Δ/σ)max < 0.001
83 parametersΔρmax = 0.62 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C12H7NOSV = 464.20 (18) Å3
Mr = 213.26Z = 2
Monoclinic, P21/cMo Kα radiation
a = 7.7308 (18) ŵ = 0.31 mm1
b = 3.8585 (9) ÅT = 296 K
c = 15.771 (3) Å0.25 × 0.06 × 0.04 mm
β = 99.333 (9)°
Data collection top
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 = 0.987Rint = 0.034
5384 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0700 restraints
wR(F2) = 0.179H-atom parameters constrained
S = 1.17Δρmax = 0.62 e Å3
1189 reflectionsΔρmin = 0.26 e Å3
83 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C60.3852 (15)0.001 (3)0.0576 (7)0.044 (2)0.50
O10.2856 (9)0.006 (2)0.1093 (4)0.083 (3)0.50
C3B0.1527 (4)0.2668 (8)0.05322 (19)0.0508 (7)0.75
H3B0.07390.26490.01450.061*0.75
N1B0.3839 (4)0.2689 (8)0.17028 (19)0.0530 (8)0.25
S10.6613 (4)0.0009 (10)0.08029 (19)0.0481 (6)0.50
C3A0.3839 (4)0.2689 (8)0.17028 (19)0.0530 (8)0.75
H3A0.46050.26760.21000.064*0.75
N1A0.1527 (4)0.2668 (8)0.05322 (19)0.0508 (7)0.25
C10.4368 (4)0.1412 (8)0.08724 (19)0.0444 (7)
C20.3204 (4)0.1406 (8)0.02885 (17)0.0437 (7)
C40.1027 (4)0.3937 (9)0.1335 (2)0.0577 (9)
H40.01020.48030.14950.069*
C50.2178 (5)0.3955 (9)0.1919 (2)0.0570 (9)
H50.18160.48420.24670.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C60.045 (6)0.038 (3)0.047 (6)0.002 (4)0.002 (3)0.008 (4)
O10.073 (4)0.134 (6)0.053 (4)0.023 (4)0.047 (3)0.015 (4)
C3B0.0496 (16)0.0468 (16)0.0563 (17)0.0002 (13)0.0099 (13)0.0016 (13)
N1B0.0632 (19)0.0482 (17)0.0476 (15)0.0023 (14)0.0090 (13)0.0010 (13)
S10.0438 (17)0.0620 (11)0.0411 (16)0.0040 (13)0.0145 (8)0.0032 (13)
C3A0.0632 (19)0.0482 (17)0.0476 (15)0.0023 (14)0.0090 (13)0.0010 (13)
N1A0.0496 (16)0.0468 (16)0.0563 (17)0.0002 (13)0.0099 (13)0.0016 (13)
C10.0434 (14)0.0371 (14)0.0512 (16)0.0028 (12)0.0031 (12)0.0058 (12)
C20.0522 (16)0.0361 (14)0.0420 (14)0.0059 (12)0.0049 (12)0.0037 (11)
C40.0501 (18)0.0507 (19)0.066 (2)0.0058 (14)0.0082 (15)0.0034 (15)
C50.069 (2)0.0495 (18)0.0474 (17)0.0000 (16)0.0075 (15)0.0048 (14)
Geometric parameters (Å, º) top
C6—O11.209 (9)S1—C2i1.791 (4)
C6—C21.480 (13)S1—C11.803 (4)
C6—C1i1.481 (13)C1—C21.388 (4)
C3B—C41.355 (4)C1—C6i1.481 (13)
C3B—C21.380 (4)C2—S1i1.791 (4)
C3B—H3B0.9300C4—C51.380 (5)
N1B—C51.364 (5)C4—H40.9300
N1B—C11.398 (4)C5—H50.9300
O1—C6—C2117.2 (11)C6i—C1—S115.5 (4)
O1—C6—C1i117.1 (11)C3B—C2—C1119.7 (3)
C2—C6—C1i125.7 (7)C3B—C2—C6123.3 (5)
C4—C3B—C2120.0 (3)C1—C2—C6117.0 (5)
C4—C3B—H3B120.0C3B—C2—S1i107.4 (2)
C2—C3B—H3B120.0C1—C2—S1i132.9 (3)
C5—N1B—C1118.7 (3)C6—C2—S1i15.9 (4)
C2i—S1—C194.30 (18)C3B—C4—C5120.6 (3)
C2—C1—N1B120.0 (3)C3B—C4—H4119.7
C2—C1—C6i117.3 (5)C5—C4—H4119.7
N1B—C1—C6i122.7 (5)N1B—C5—C4120.9 (3)
C2—C1—S1132.8 (3)N1B—C5—H5119.6
N1B—C1—S1107.2 (2)C4—C5—H5119.6
C5—N1B—C1—C20.8 (5)S1—C1—C2—C60.2 (6)
C5—N1B—C1—C6i179.5 (6)N1B—C1—C2—S1i179.5 (3)
C5—N1B—C1—S1179.4 (3)C6i—C1—C2—S1i0.2 (6)
C2i—S1—C1—C20.2 (4)S1—C1—C2—S1i0.2 (6)
C2i—S1—C1—N1B179.6 (2)O1—C6—C2—C3B2.2 (15)
C2i—S1—C1—C6i0 (2)C1i—C6—C2—C3B179.7 (7)
C4—C3B—C2—C10.6 (5)O1—C6—C2—C1178.2 (10)
C4—C3B—C2—C6179.8 (6)C1i—C6—C2—C10.1 (12)
C4—C3B—C2—S1i179.7 (3)O1—C6—C2—S1i2.0 (11)
N1B—C1—C2—C3B0.1 (4)C1i—C6—C2—S1i180 (3)
C6i—C1—C2—C3B179.7 (6)C2—C3B—C4—C50.5 (5)
S1—C1—C2—C3B179.8 (3)C1—N1B—C5—C40.9 (5)
N1B—C1—C2—C6179.6 (6)C3B—C4—C5—N1B0.2 (5)
C6i—C1—C2—C60.1 (11)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O1ii0.932.533.286 (7)139
Symmetry code: (ii) x, y1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC12H7NOS
Mr213.26
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)7.7308 (18), 3.8585 (9), 15.771 (3)
β (°) 99.333 (9)
V3)464.20 (18)
Z2
Radiation typeMo Kα
µ (mm1)0.31
Crystal size (mm)0.25 × 0.06 × 0.04
Data collection
DiffractometerBruker Kappa APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.977, 0.987
No. of measured, independent and
observed [I > 2σ(I)] reflections
5384, 1189, 822
Rint0.034
(sin θ/λ)max1)0.676
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.070, 0.179, 1.17
No. of reflections1189
No. of parameters83
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.62, 0.26

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O1i0.93002.53003.286 (7)139.00
Symmetry code: (i) x, y1/2, z1/2.
 

Acknowledgements

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, for funding the purchase of the diffractometer at GCU, Lahore.

References

First citationBruker (2005). SADABS. Bruker AXS Inc. Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc. Madison, Wisconsin, USA.  Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
First citationHidetoshi, F. (1997). Heterocycles, 45, 119–127.  Google Scholar
First citationKhan, M. N., Tahir, M. N., Khan, M. A., Khan, I. U. & Arshad, M. N. (2008). Acta Cryst. E64, o730.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationMann, F. G. & Reid, J. A. (1952). J. Chem. Soc. pp. 2057–2062.  CrossRef Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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