Diethyl 2-{[(5-oxo-5H-thio-chromeno[2,3-b]pyridin-7-yl)amino]-methyl-idene}propane-dioate.

In the title compound, C(15)H(14)O(2)S, the three fused rings are roughly coplanar, the largest deviation from the mean plane being 0.1285 (13) Å for the S atom. An intra-molecular N-H⋯O hydrogen bond generates an S6 ring. In the crystal, inter-molecular C-H⋯O hydrogen bonds form R(2) (2)(14), R(2) (2)(13) and R(3) (2)(17) ring motifs, building a layer parallel to (100).

Related literature

For related structures, see: Khan et al. (2008 ▶); 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 = 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

Δρmax = 0.20 e Å−3

Δρmin = −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.

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

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

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

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

C20H18N2O5S	F(000) = 1664
Mr = 398.42	Dx = 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

Bruker Kappa APEXII CCD diffractometer	3314 independent reflections
Radiation source: fine-focus sealed tube	1776 reflections with I > 2σ(I)
graphite	Rint = 0.077
Detector resolution: 8.10 pixels mm-1	θmax = 25.0°, θmin = 2.3°
ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = 0→8
Tmin = 0.968, Tmax = 0.985	l = 0→42
13274 measured reflections

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(Fo2) + (0.0533P)2] where P = (Fo2 + 2Fc2)/3
3314 reflections	(Δ/σ)max = 0.001
269 parameters	Δρmax = 0.20 e Å−3
10 restraints	Δρmin = −0.18 e Å−3

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.

	x	y	z	Uiso*/Ueq	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)

	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)

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)

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

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) ; (ii) ; (iii) .