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

Abstract

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,

• a = 7.7308 (18) Å

• b = 3.8585 (9) Å

• c = 15.771 (3) Å

• β = 99.333 (9)°

• V = 464.20 (18) ų

• 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[F ² > 2σ(F ²)] = 0.070

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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)

Experimental

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

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, U_iso(H) = 1.2U_eq(C) and constrained to ride on their parent atoms.

Figures

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.

Crystal data

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

Data collection

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

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

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	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, °)

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.

Hydrogen-bond geometry (Å, °)

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.