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

Khan, M.N.; Tahir, M.N.; Khan, M.A.; Khan, I.U.; Arshad, M.N.

doi:10.1107/S1600536808024628

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1704

doi:10.1107/S1600536808024628

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

Muhammad Naeem Khan,^a M. Nawaz Tahir,^b ^* Misbahul Ain Khan,^c Islam Ullah Khan ^d and Muhammad Nadeem Arshad ^d

^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 π⋯π interactions (centroid–centroid distances of 3.635 and 3.858 Å).

Related literature

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

Experimental

Crystal data

C₁₂H₇NOS
M_r = 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 ) T_min = 0.977, T_max = 0.987
5384 measured reflections
1189 independent reflections
822 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.070
wR(F²) = 0.179
S = 1.17
1189 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: APEX2; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808024628/bt2756sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024628/bt2756Isup2.hkl

checkCIF report

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.

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

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

C₁₂H₇NOS	F(000) = 220
M_r = 213.26	D_x = 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 = 2.6–28.7°
b = 3.8585 (9) Å	µ = 0.31 mm⁻¹
c = 15.771 (3) Å	T = 296 K
β = 99.333 (9)°	Needle, light yellow
V = 464.20 (18) Å³	0.25 × 0.06 × 0.04 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD diffractometer	1189 independent reflections
Radiation source: fine-focus sealed tube	822 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 7.5 pixels mm^-1	θ_max = 28.7°, θ_min = 2.6°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −5→3
T_min = 0.977, T_max = 0.987	l = −21→21
5384 measured reflections

Refinement top

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)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.179	H-atom parameters constrained
S = 1.17	w = 1/[σ²(F_o²) + (0.064P)² + 0.435P] where P = (F_o² + 2F_c²)/3
1189 reflections	(Δ/σ)_max < 0.001
83 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₂H₇NOS	V = 464.20 (18) Å³
M_r = 213.26	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7308 (18) Å	µ = 0.31 mm⁻¹
b = 3.8585 (9) Å	T = 296 K
c = 15.771 (3) Å	0.25 × 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)
T_min = 0.977, T_max = 0.987	R_int = 0.034
5384 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.070	0 restraints
wR(F²) = 0.179	H-atom parameters constrained
S = 1.17	Δρ_max = 0.62 e Å⁻³
1189 reflections	Δρ_min = −0.26 e Å⁻³
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

	x	y	z	U_iso*/U_eq	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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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 code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1ⁱⁱ	0.93	2.53	3.286 (7)	139

Symmetry code: (ii) x, −y−1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₇NOS
M_r	213.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.7308 (18), 3.8585 (9), 15.771 (3)
β (°)	99.333 (9)
V (Å³)	464.20 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.25 × 0.06 × 0.04

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.977, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	5384, 1189, 822
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.070, 0.179, 1.17
No. of reflections	1189
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
C5—H5···O1ⁱ	0.9300	2.5300	3.286 (7)	139.00

Symmetry code: (i) x, −y−1/2, z−1/2.

Acknowledgements

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

References

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