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

Khan, M.N.; Tahir, M.N.; Khan, M.A.; Munawar, M.A.; Ather, A.Q.

doi:10.1107/S1600536811016291

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1348

doi:10.1107/S1600536811016291

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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 and Abdul Qayyum Ather ^b

^aDepartment of Chemistry, Islamia University, Bahawalpur, Pakistan, ^bApplied Chemistry Research Center, PCSIR Laboratories complex, Lahore 54600, Pakistan, ^cUniversity of Sargodha, Department of Physics, Sargodha, Pakistan, and ^dInstitute of Chemistry, University of the Punjab, Lahore, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 17 April 2011; accepted 29 April 2011; online 7 May 2011)

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 R₂²(14), R₂²(13) and R₃²(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, C 2/c
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[F² > 2σ(F²)] = 0.054
wR(F²) = 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

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
Symmetry codes: (i) x, y-1, z; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y+1, z.

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.

Supporting information

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

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

Supporting information file. DOI: 10.1107/S1600536811016291/dn2678Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. View of the title compound with the atom numbering scheme. The thermal displacements are drawn at the 50% probability level. H-atoms are shown as small spheres of arbitrary radii. The disordered miniority ethyl groups are omitted for clarity.
	Fig. 2. Partial packing view showing the formation of different ring motifs through C-H···O hydrogen bonds. Only the major component of the disordered moieties are represented and H atoms not involved in hydrogen bondings have been omitted for clarity. [Symmetry code: (i) x, y-1, z.]

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

Crystal data top

C₂₀H₁₈N₂O₅S	F(000) = 1664
M_r = 398.42	D_x = 1.410 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1789 reflections
a = 13.8013 (7) Å	θ = 2.3–25.3°
b = 7.5180 (3) Å	µ = 0.21 mm⁻¹
c = 36.2743 (15) Å	T = 296 K
β = 94.330 (3)°	Needle, yellow
V = 3753.0 (3) Å³	0.35 × 0.18 × 0.15 mm
Z = 8

Data collection top

Bruker Kappa APEXII CCD diffractometer	3314 independent reflections
Radiation source: fine-focus sealed tube	1776 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.077
Detector resolution: 8.10 pixels mm^-1	θ_max = 25.0°, θ_min = 2.3°
ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = 0→8
T_min = 0.968, T_max = 0.985	l = 0→42
13274 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0533P)²] where P = (F_o² + 2F_c²)/3
3314 reflections	(Δ/σ)_max = 0.001
269 parameters	Δρ_max = 0.20 e Å⁻³
10 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₀H₁₈N₂O₅S	V = 3753.0 (3) Å³
M_r = 398.42	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 13.8013 (7) Å	µ = 0.21 mm⁻¹
b = 7.5180 (3) Å	T = 296 K
c = 36.2743 (15) Å	0.35 × 0.18 × 0.15 mm
β = 94.330 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	3314 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1776 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.985	R_int = 0.077
13274 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	10 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 0.97	Δρ_max = 0.20 e Å⁻³
3314 reflections	Δρ_min = −0.18 e Å⁻³
269 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)
S1	0.10364 (6)	−0.08366 (11)	−0.04024 (2)	0.0529 (3)
O1	0.11162 (17)	0.4807 (3)	−0.00428 (6)	0.0604 (7)
O2	0.3194 (2)	0.3243 (3)	0.21973 (6)	0.0911 (9)
C16A	0.3217 (7)	0.1867 (9)	0.24963 (15)	0.1062 (19)	0.75
H16A	0.2563	0.1492	0.2540	0.127*	0.75
H16B	0.3585	0.0834	0.2428	0.127*	0.75
C17A	0.3688 (6)	0.2726 (9)	0.28278 (13)	0.1062 (19)	0.75
H17A	0.4333	0.3086	0.2780	0.159*	0.75
H17B	0.3718	0.1901	0.3030	0.159*	0.75
H17C	0.3318	0.3751	0.2890	0.159*	0.75
C16B	0.2928 (14)	0.259 (3)	0.2569 (5)	0.122 (7)	0.25
H16C	0.2441	0.1659	0.2556	0.147*	0.25
H16D	0.2762	0.3534	0.2736	0.147*	0.25
C17B	0.3965 (14)	0.192 (3)	0.2636 (8)	0.122 (7)	0.25
H17D	0.4131	0.1221	0.2429	0.184*	0.25
H17E	0.4019	0.1198	0.2855	0.184*	0.25
H17F	0.4401	0.2912	0.2668	0.184*	0.25
O3	0.2852 (2)	0.0944 (4)	0.18250 (6)	0.0853 (9)
O4	0.40074 (19)	0.5902 (3)	0.18304 (7)	0.0793 (8)
C19A	0.4388 (7)	0.7695 (14)	0.1889 (4)	0.105 (3)	0.53
H19A	0.4366	0.8060	0.2145	0.126*	0.53
H19B	0.4031	0.8548	0.1730	0.126*	0.53
C20A	0.5401 (7)	0.7499 (13)	0.1787 (3)	0.105 (3)	0.53
H20A	0.5726	0.6611	0.1941	0.157*	0.53
H20B	0.5734	0.8614	0.1822	0.157*	0.53
H20C	0.5399	0.7146	0.1533	0.157*	0.53
C19B	0.4500 (8)	0.7644 (17)	0.1791 (5)	0.108 (4)	0.47
H19C	0.4098	0.8599	0.1874	0.130*	0.47
H19D	0.4615	0.7854	0.1534	0.130*	0.47
C20B	0.5450 (7)	0.7572 (16)	0.2024 (3)	0.108 (4)	0.47
H20D	0.5325	0.7451	0.2280	0.163*	0.47
H20E	0.5808	0.8647	0.1990	0.163*	0.47
H20F	0.5822	0.6571	0.1950	0.163*	0.47
O5	0.2939 (2)	0.6807 (4)	0.13788 (7)	0.0874 (9)
N1	0.0155 (2)	0.0557 (4)	−0.09743 (7)	0.0591 (8)
N2	0.23819 (19)	0.1593 (4)	0.11064 (7)	0.0544 (8)
H2	0.2432	0.0765	0.1270	0.065*
C1	0.1051 (2)	0.3242 (5)	−0.01327 (8)	0.0440 (8)
C2	0.0601 (2)	0.2734 (4)	−0.05003 (8)	0.0446 (8)
C3	0.0182 (2)	0.4052 (5)	−0.07279 (9)	0.0618 (10)
H3	0.0195	0.5229	−0.0649	0.074*
C4	−0.0251 (3)	0.3623 (6)	−0.10695 (10)	0.0737 (12)
H4	−0.0542	0.4491	−0.1223	0.088*
C5	−0.0242 (3)	0.1861 (6)	−0.11782 (9)	0.0719 (11)
H5	−0.0533	0.1574	−0.1410	0.086*
C6	0.0558 (2)	0.1015 (4)	−0.06379 (8)	0.0460 (8)
C7	0.1410 (2)	0.0021 (4)	0.00313 (8)	0.0407 (8)
C8	0.1395 (2)	0.1820 (4)	0.01247 (8)	0.0390 (8)
C9	0.1711 (2)	0.2333 (4)	0.04837 (8)	0.0452 (8)
H9	0.1691	0.3528	0.0549	0.054*
C10	0.2052 (2)	0.1102 (5)	0.07425 (8)	0.0448 (8)
C11	0.2065 (2)	−0.0693 (4)	0.06457 (8)	0.0507 (9)
H11	0.2294	−0.1534	0.0819	0.061*
C12	0.1743 (2)	−0.1219 (4)	0.02973 (8)	0.0468 (8)
H12	0.1746	−0.2421	0.0237	0.056*
C13	0.2620 (2)	0.3227 (5)	0.12156 (8)	0.0525 (9)
H13	0.2555	0.4106	0.1035	0.063*
C14	0.2949 (2)	0.3776 (4)	0.15601 (8)	0.0503 (9)
C15	0.3008 (3)	0.2515 (6)	0.18640 (9)	0.0634 (10)
C18	0.3268 (3)	0.5646 (5)	0.15800 (9)	0.0608 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0609 (6)	0.0445 (6)	0.0529 (5)	0.0014 (5)	0.0003 (4)	−0.0085 (4)
O1	0.0728 (18)	0.0357 (15)	0.0714 (15)	0.0011 (13)	−0.0036 (12)	−0.0025 (12)
O2	0.150 (3)	0.077 (2)	0.0444 (14)	−0.0195 (18)	−0.0106 (15)	0.0048 (13)
C16A	0.175 (6)	0.088 (4)	0.050 (2)	0.010 (4)	−0.023 (3)	0.004 (2)
C17A	0.175 (6)	0.088 (4)	0.050 (2)	0.010 (4)	−0.023 (3)	0.004 (2)
C16B	0.20 (2)	0.056 (13)	0.107 (13)	−0.034 (13)	0.004 (15)	0.009 (9)
C17B	0.20 (2)	0.056 (13)	0.107 (13)	−0.034 (13)	0.004 (15)	0.009 (9)
O3	0.135 (3)	0.0529 (19)	0.0666 (16)	−0.0019 (18)	0.0001 (15)	0.0044 (14)
O4	0.085 (2)	0.0608 (19)	0.0880 (18)	−0.0109 (15)	−0.0233 (15)	−0.0001 (14)
C19A	0.127 (9)	0.055 (5)	0.129 (7)	−0.022 (5)	−0.010 (6)	0.006 (4)
C20A	0.127 (9)	0.055 (5)	0.129 (7)	−0.022 (5)	−0.010 (6)	0.006 (4)
C19B	0.080 (8)	0.102 (8)	0.138 (8)	−0.009 (5)	−0.026 (5)	−0.044 (6)
C20B	0.080 (8)	0.102 (8)	0.138 (8)	−0.009 (5)	−0.026 (5)	−0.044 (6)
O5	0.115 (2)	0.063 (2)	0.0792 (18)	0.0021 (16)	−0.0280 (16)	0.0106 (15)
N1	0.058 (2)	0.072 (2)	0.0474 (17)	−0.0035 (16)	0.0008 (14)	−0.0064 (15)
N2	0.065 (2)	0.053 (2)	0.0452 (16)	−0.0068 (16)	0.0044 (13)	0.0012 (13)
C1	0.034 (2)	0.044 (2)	0.054 (2)	−0.0031 (17)	0.0088 (15)	0.0006 (17)
C2	0.038 (2)	0.046 (2)	0.0496 (19)	0.0001 (16)	0.0032 (15)	0.0073 (16)
C3	0.060 (2)	0.059 (3)	0.065 (2)	0.003 (2)	0.0019 (19)	0.003 (2)
C4	0.075 (3)	0.081 (3)	0.063 (3)	0.007 (2)	−0.008 (2)	0.016 (2)
C5	0.075 (3)	0.091 (4)	0.049 (2)	−0.001 (3)	−0.0056 (19)	0.000 (2)
C6	0.039 (2)	0.054 (2)	0.0446 (18)	−0.0004 (17)	0.0057 (15)	0.0009 (17)
C7	0.035 (2)	0.039 (2)	0.0479 (18)	−0.0044 (16)	0.0062 (15)	0.0002 (15)
C8	0.0351 (19)	0.037 (2)	0.0452 (18)	−0.0044 (15)	0.0061 (14)	−0.0006 (15)
C9	0.044 (2)	0.042 (2)	0.0507 (19)	−0.0033 (16)	0.0073 (16)	−0.0075 (16)
C10	0.047 (2)	0.050 (2)	0.0386 (17)	−0.0050 (17)	0.0066 (14)	0.0010 (16)
C11	0.053 (2)	0.046 (2)	0.053 (2)	−0.0014 (18)	0.0071 (17)	0.0101 (17)
C12	0.051 (2)	0.037 (2)	0.052 (2)	−0.0022 (16)	0.0077 (16)	−0.0007 (15)
C13	0.051 (2)	0.060 (3)	0.047 (2)	−0.0038 (19)	0.0060 (16)	0.0018 (17)
C14	0.059 (2)	0.049 (2)	0.0430 (18)	−0.0047 (18)	0.0061 (16)	0.0007 (16)
C15	0.072 (3)	0.066 (3)	0.051 (2)	0.003 (2)	−0.0017 (19)	−0.005 (2)
C18	0.067 (3)	0.064 (3)	0.050 (2)	0.001 (2)	−0.0044 (19)	−0.0032 (19)

Geometric parameters (Å, º) top

S1—C6	1.737 (3)	C20B—H20D	0.9600
S1—C7	1.742 (3)	C20B—H20E	0.9600
O1—C1	1.222 (3)	C20B—H20F	0.9600
O2—C15	1.334 (4)	O5—C18	1.204 (4)
O2—C16A	1.497 (6)	N1—C5	1.321 (4)
O2—C16B	1.506 (14)	N1—C6	1.347 (4)
C16A—C17A	1.472 (7)	N2—C13	1.324 (4)
C16A—H16A	0.9700	N2—C10	1.413 (4)
C16A—H16B	0.9700	N2—H2	0.8600
C17A—H17A	0.9600	C1—C8	1.474 (4)
C17A—H17B	0.9600	C1—C2	1.478 (4)
C17A—H17C	0.9600	C2—C6	1.385 (4)
C16B—C17B	1.520 (10)	C2—C3	1.388 (4)
C16B—H16C	0.9700	C3—C4	1.373 (4)
C16B—H16D	0.9700	C3—H3	0.9300
C17B—H17D	0.9600	C4—C5	1.382 (5)
C17B—H17E	0.9600	C4—H4	0.9300
C17B—H17F	0.9600	C5—H5	0.9300
O3—C15	1.206 (4)	C7—C12	1.395 (4)
O4—C18	1.328 (4)	C7—C8	1.395 (4)
O4—C19A	1.457 (10)	C8—C9	1.396 (4)
O4—C19B	1.487 (12)	C9—C10	1.375 (4)
C19A—C20A	1.480 (9)	C9—H9	0.9300
C19A—H19A	0.9700	C10—C11	1.395 (4)
C19A—H19B	0.9700	C11—C12	1.366 (4)
C20A—H20A	0.9600	C11—H11	0.9300
C20A—H20B	0.9600	C12—H12	0.9300
C20A—H20C	0.9600	C13—C14	1.361 (4)
C19B—C20B	1.506 (10)	C13—H13	0.9300
C19B—H19C	0.9700	C14—C15	1.452 (4)
C19B—H19D	0.9700	C14—C18	1.473 (4)

C6—S1—C7	102.90 (15)	C6—C2—C1	124.7 (3)
C15—O2—C16A	111.4 (4)	C3—C2—C1	118.7 (3)
C15—O2—C16B	129.4 (11)	C4—C3—C2	120.2 (3)
C16A—O2—C16B	28.4 (8)	C4—C3—H3	119.9
C17A—C16A—O2	105.8 (5)	C2—C3—H3	119.9
C17A—C16A—H16A	110.6	C3—C4—C5	118.0 (4)
O2—C16A—H16A	110.6	C3—C4—H4	121.0
C17A—C16A—H16B	110.6	C5—C4—H4	121.0
O2—C16A—H16B	110.6	N1—C5—C4	124.3 (4)
H16A—C16A—H16B	108.7	N1—C5—H5	117.9
O2—C16B—C17B	87.8 (14)	C4—C5—H5	117.9
O2—C16B—H16C	114.0	N1—C6—C2	124.6 (3)
C17B—C16B—H16C	114.0	N1—C6—S1	110.9 (3)
O2—C16B—H16D	114.0	C2—C6—S1	124.5 (2)
C17B—C16B—H16D	114.0	C12—C7—C8	119.4 (3)
H16C—C16B—H16D	111.2	C12—C7—S1	115.9 (2)
C16B—C17B—H17D	109.5	C8—C7—S1	124.7 (2)
C16B—C17B—H17E	109.5	C7—C8—C9	119.0 (3)
H17D—C17B—H17E	109.5	C7—C8—C1	124.0 (3)
C16B—C17B—H17F	109.5	C9—C8—C1	117.0 (3)
H17D—C17B—H17F	109.5	C10—C9—C8	121.2 (3)
H17E—C17B—H17F	109.5	C10—C9—H9	119.4
C18—O4—C19A	118.9 (6)	C8—C9—H9	119.4
C18—O4—C19B	113.3 (6)	C9—C10—C11	119.3 (3)
C19A—O4—C19B	15.6 (11)	C9—C10—N2	122.1 (3)
O4—C19A—C20A	102.0 (8)	C11—C10—N2	118.6 (3)
O4—C19A—H19A	111.4	C12—C11—C10	120.2 (3)
C20A—C19A—H19A	111.4	C12—C11—H11	119.9
O4—C19A—H19B	111.4	C10—C11—H11	119.9
C20A—C19A—H19B	111.4	C11—C12—C7	120.9 (3)
H19A—C19A—H19B	109.2	C11—C12—H12	119.5
O4—C19B—C20B	107.4 (10)	C7—C12—H12	119.5
O4—C19B—H19C	110.2	N2—C13—C14	127.9 (3)
C20B—C19B—H19C	110.2	N2—C13—H13	116.1
O4—C19B—H19D	110.2	C14—C13—H13	116.1
C20B—C19B—H19D	110.2	C13—C14—C15	119.7 (3)
H19C—C19B—H19D	108.5	C13—C14—C18	114.3 (3)
C5—N1—C6	116.3 (3)	C15—C14—C18	125.9 (3)
C13—N2—C10	125.3 (3)	O3—C15—O2	121.9 (3)
C13—N2—H2	117.4	O3—C15—C14	123.4 (3)
C10—N2—H2	117.4	O2—C15—C14	114.6 (4)
O1—C1—C8	121.0 (3)	O5—C18—O4	123.0 (4)
O1—C1—C2	120.4 (3)	O5—C18—C14	124.4 (4)
C8—C1—C2	118.5 (3)	O4—C18—C14	112.5 (3)
C6—C2—C3	116.6 (3)

C15—O2—C16A—C17A	164.6 (6)	O1—C1—C8—C9	5.8 (4)
C16B—O2—C16A—C17A	−60.2 (19)	C2—C1—C8—C9	−172.7 (2)
C15—O2—C16B—C17B	101.0 (17)	C7—C8—C9—C10	1.2 (4)
C16A—O2—C16B—C17B	42.9 (14)	C1—C8—C9—C10	−179.5 (3)
C18—O4—C19A—C20A	−118.4 (9)	C8—C9—C10—C11	−1.1 (4)
C19B—O4—C19A—C20A	−46 (3)	C8—C9—C10—N2	179.5 (3)
C18—O4—C19B—C20B	−166.4 (9)	C13—N2—C10—C9	−16.8 (5)
C19A—O4—C19B—C20B	79 (3)	C13—N2—C10—C11	163.8 (3)
O1—C1—C2—C6	174.9 (3)	C9—C10—C11—C12	0.0 (4)
C8—C1—C2—C6	−6.5 (4)	N2—C10—C11—C12	179.4 (3)
O1—C1—C2—C3	−5.4 (4)	C10—C11—C12—C7	1.0 (4)
C8—C1—C2—C3	173.2 (3)	C8—C7—C12—C11	−0.9 (4)
C6—C2—C3—C4	0.4 (5)	S1—C7—C12—C11	179.2 (2)
C1—C2—C3—C4	−179.3 (3)	C10—N2—C13—C14	−179.4 (3)
C2—C3—C4—C5	−0.9 (5)	N2—C13—C14—C15	−4.2 (5)
C6—N1—C5—C4	0.9 (5)	N2—C13—C14—C18	172.5 (3)
C3—C4—C5—N1	0.2 (6)	C16A—O2—C15—O3	2.2 (6)
C5—N1—C6—C2	−1.5 (5)	C16B—O2—C15—O3	−23.5 (11)
C5—N1—C6—S1	179.4 (2)	C16A—O2—C15—C14	178.4 (5)
C3—C2—C6—N1	0.9 (4)	C16B—O2—C15—C14	152.7 (10)
C1—C2—C6—N1	−179.4 (3)	C13—C14—C15—O3	6.0 (5)
C3—C2—C6—S1	179.8 (2)	C18—C14—C15—O3	−170.3 (4)
C1—C2—C6—S1	−0.5 (4)	C13—C14—C15—O2	−170.2 (3)
C7—S1—C6—N1	−174.8 (2)	C18—C14—C15—O2	13.5 (5)
C7—S1—C6—C2	6.2 (3)	C19A—O4—C18—O5	5.6 (8)
C6—S1—C7—C12	173.8 (2)	C19B—O4—C18—O5	−10.6 (8)
C6—S1—C7—C8	−6.1 (3)	C19A—O4—C18—C14	−178.4 (6)
C12—C7—C8—C9	−0.2 (4)	C19B—O4—C18—C14	165.4 (7)
S1—C7—C8—C9	179.7 (2)	C13—C14—C18—O5	29.7 (5)
C12—C7—C8—C1	−179.4 (3)	C15—C14—C18—O5	−153.8 (4)
S1—C7—C8—C1	0.5 (4)	C13—C14—C18—O4	−146.2 (3)
O1—C1—C8—C7	−175.0 (3)	C15—C14—C18—O4	30.3 (5)
C2—C1—C8—C7	6.5 (4)

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₈N₂O₅S
M_r	398.42
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	13.8013 (7), 7.5180 (3), 36.2743 (15)
β (°)	94.330 (3)
V (Å³)	3753.0 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.35 × 0.18 × 0.15

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.968, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	13274, 3314, 1776
R_int	0.077
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.130, 0.97
No. of reflections	3314
No. of parameters	269
No. of restraints	10
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.18

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009)'.

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x, y+1, z.

Acknowledgements

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.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
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Khan, M. N., Tahir, M. N., Khan, M. A., Khan, I. U. & Arshad, M. N. (2008b). Acta Cryst. E64, o1704. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Lynch, D. E. & McClenaghan, I. (2003). Acta Cryst. E59, o242–o243. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Volume 67| Part 6| June 2011| Page o1348

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

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

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

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