Diethyl 2-{[(5-oxo-5H-thio­chromeno[2,3-b]pyridin-7-yl)amino]­methyl­idene}propane­dioate

Muhammad Naeem Khan; M Nawaz Tahir; Misbahul Ain Khan; Munawar Ali Munawar; Abdul Qayyum Ather

doi:10.1107/S1600536811016291

. 2011 May 7;67(Pt 6):o1348. doi: 10.1107/S1600536811016291

Diethyl 2-{[(5-oxo-5H-thiochromeno[2,3-b]pyridin-7-yl)amino]methylidene}propanedioate

Muhammad Naeem Khan ^a,^b, M Nawaz Tahir ^c,^*, Misbahul Ain Khan ^a, Munawar Ali Munawar ^d, Abdul Qayyum Ather ^b

PMCID: PMC3120616 PMID: 21754742

Abstract

In the title compound, C₁₅H₁₄O₂S, the three fused rings are roughly coplanar, the largest deviation from the mean plane being 0.1285 (13) Å for the S atom. An intramolecular N—H⋯O hydrogen bond generates an S6 ring. In the crystal, intermolecular C—H⋯O hydrogen bonds form R ₂ ²(14), R₂ ²(13) and R ₃ ²(17) ring motifs, building a layer parallel to (100).

Related literature

For related structures, see: Khan et al. (2008a ▶,b ▶); Lokaj et al. (1994 ▶); Lynch & McClenaghan (2003 ▶); For graph-set notation, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₀H₁₈N₂O₅S
M _r = 398.42
Monoclinic,
a = 13.8013 (7) Å
b = 7.5180 (3) Å
c = 36.2743 (15) Å
β = 94.330 (3)°
V = 3753.0 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 296 K
0.35 × 0.18 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.968, T _max = 0.985
13274 measured reflections
3314 independent reflections
1776 reflections with I > 2σ(I)
R _int = 0.077

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.130
S = 0.97
3314 reflections
269 parameters
10 restraints
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶)’; software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811016291/dn2678sup1.cif

e-67-o1348-sup1.cif^{(31KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811016291/dn2678Isup2.hkl

e-67-o1348-Isup2.hkl^{(162.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811016291/dn2678Isup3.cml

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
N2—H2⋯O3	0.86	2.06	2.683 (3)	129
C11—H11⋯O5ⁱ	0.93	2.49	3.403 (4)	167
C12—H12⋯O1ⁱ	0.93	2.45	3.322 (4)	157
C17A—H17C⋯O3ⁱⁱ	0.96	2.58	3.516 (8)	165
C19A—H19B⋯O3ⁱⁱⁱ	0.97	2.47	3.231 (11)	135

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Ex-Vice Chancellor, University of Sargodha, Pakistan.

supplementary crystallographic information

Comment

We reported the crystal structures of (II) i.e. 7-nitro-5H-thiochromeno[2,3-b]pyridin-5-one (Khan et al., 2008a) and (III) i.e. 5H-thiochromeno[2,3-b]pyridin-5-one (Khan et al., 2008b). The title compound (Fig. 1) is in continuation of our work to synthesize the derivatives of 5H-thiochromeno[2,3-b]pyridin-5-one. The crystal structures of (IV) i.e., diethyl 2-(2,3-diphenylquinoxalin-6-ylaminomethylene)malonate (Lokaj et al., 1994) and (V) i.e., diethyl (4-tert-butyl-1,3-thiazol-2-ylaminomethylene)malonate (Lynch & McClenaghan, 2003) have been published. Both contain the diethyl (aminomethylidene)propanedioate moiety which is also present in (I).

In (I), the central heterocyclic ring A (C1/C2/C6/S1/C7/C8), the pyridinic group B (C2/C3/C4/C5/N1/C6) and benzene ring C (C7—C12) are planar with r. m. s. deviation of 0.0388, 0.0053 and 0.0049 Å, respectively. The carbonyl O-atom is at a distance of 0.1532 (35) Å from its parent ring A. The dihedral angle between A/B, A/C and B/C is 3.68 (12), 3.50 (9) and 7.19 (12)°, respectively. A strong intramolecular H-bonding of N—H···O type completes an S(6) (Etter et al., 1990; Bernstein et al., 1995) ring motif. Intermolecular C—H···O hydrogen bonds complete R₂²(14), R₂²(13) and R₃²(17) ring motifs building a layer parallel to the (1 0 0) plane (Table 1, Fig 2).

Experimental

Diethyl (ethoxymethylene)malonate (0.473 g, 2.1 mmol), 7-amino-5H-thiochromeno[2,3-b]pyridin-5-one (500 mg, 2.1 mmol) and 8.0 ml of ethyl alcohol was heated under reflux on water bath for 3 h. Completion of reaction was monitored by TLC. The product precipitated by the addition of n-hexane was filtered, washed, dried and recrystallized from chloroform to give the yellow needles of (I).