Crystal structure of 1-methyl-2-methyl­amino-3-nitro-1H-chromeno[2,3-b]pyridin-5(10aH)-one

Raja, R.; Poomathi, N.; Perumal, P.T.; SubbiahPandi, A.

doi:10.1107/S2056989015018241

Crystal structure of 1-methyl-2-methylamino-3-nitro-1H-chromeno[2,3-b]pyridin-5(10aH)-one

R. Raja, N. Poomathi, P. T. Perumal and A. SubbiahPandi

In the title compound, C₁₄H₁₃N₃O₄, the pyran ring adopts an envelope conformation with the methine C atom as the flap. The dihedral angle between the benzene and hydropyridine rings is 29.33 (3)°. The methylamine C atom deviates from the plane of its attached ring by 0.380 (5) Å and an intramolecular N—H

O hydrogen bond closes an S(6) ring. In the crystal, weak C—H

O hydrogen bonds and aromatic π–π stacking interactions [centroid–centroid distances vary from 3.6529 (10) to 3.6872 (10) Å] link the molecules, generating a three-dimensional network.

Keywords: crystal structure; chromene; hydrogen bonding; π–π stacking.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015018241/hb7515sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989015018241/hb7515Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989015018241/hb7515Isup3.cml Supplementary material

CCDC reference: 1421106

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.002 Å
R factor = 0.030
wR factor = 0.076
Data-to-parameter ratio = 11.8

checkCIF/PLATON results

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Alert level C
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax < 18) ........       6.35 Note

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Report
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT093_ALERT_1_G No su's on H-positions, refinement reported as .      mixed Check
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT792_ALERT_1_G The Model has Chirality at C7      (Polar  SPGR)          S Verify
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          81 %

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   9 ALERT level G = General information/check it is not something unexpected

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
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Comment top

Chromene derivatives are very important heterocyclic compounds that have a variety of industrial, biological and chemical synthesis applications (Geen et al., 1996; Ercole et al., 2009). They exhibit a number of pharmacological activities such as anti-HIV, anti-inflammatory, anti-bacterial, anti-allergic, anti-cancer etc. (Khan et al., 2010; Raj et al., 2010). Against this backround, X-ray analysis of the title compound has been carried out to study its structural aspects.

The molecular structure of the title molecule is shown in Fig. 1. The pyran ring (C1-C7-O4-C8-C13-C14) adopts a envelope conformation with the deviation of atoms O4 and C14 from the mean plane through atoms (C1-C7-C8-C13) being 0.475 and -0.095Å, respectively. The smallest displacement asymmetry parameters q₂ and q₃ are 0.421 (17) and -0.219 (17)Å. The ring parameters Q and phase angle θ are 0.475 (16)Å and 117.5 (2)°, respectively. The dihedral angle between the mean planes of the chromeno ring system (fusion of benzene and pyran rings) and the pyridine ring is 29.37 (7)°. The pyridine ring mean planes forms a dihedral angle of 31.22 (8)° with phenyl ring (C8-C13). The atoms O3 deviates by -0.295Å from the chromeno ring mean plane (O4/C1-C7).

An intramolecular N—H···O and N—H···N interaction occurs. In the crystal, molecules are linked by C—H···O hydrogen bonds, forming inversion dimers with an R₂²(8) ring motif. The molecules are linked via C—H···O hydrogen bonds, forming ribbons along [110] dirction. There are a number of π—π interactions present linking the ribbons and forming a three dimensional structure [ Cg2-Cg3ⁱ =3.6529 (10)Å, Cg2-Cg3ⁱⁱ = 3.6871 (10)Å and Cg3-Cg2ⁱⁱⁱ = 3.6528 (10)Å; where Cg2 and Cg3 are the centroids of the N3/C4/C3/C2/C1/C7 and C8/C13 rings, respectively; symmetry codes: (i) -x,-y,-z; (ii) 1/4+x,1/4-y, 1/4+z; (iii) -1/4+x,1/4-y,-1/4+z].

Related literature top

For the uses and biological importance of chromenes, see: Ercole et al. (2009); Geen et al. (1996); Khan et al. (2010); Raj et al. (2010).

Experimental top

A mixture of 3-formylchromone (1 mmol), N,N'-dimethyl-2-nitroethene-1, 1-diamine (1 mmol) in ethanol (3 ml) and a catalytic amount (0.050 mmol) of In(OTf)₃ was added and refluxed for about 30 minutes. The product was purified by column chromatography (5/95 % Ethylacetate/petether) to afford the pure product in 94 % yield. The purified compound was recrystalised from DMSO-D₆ by using slow evaporation method to yield colourless blocks.

Structure description top

For the uses and biological importance of chromenes, see: Ercole et al. (2009); Geen et al. (1996); Khan et al. (2010); Raj et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Viewed down the c axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1 for details)

1-Methyl-2-methylamino-3-nitro-1H-chromeno[2,3-b]pyridin-5(10aH)-one top

Crystal data top

C₁₄H₁₃N₃O₄	F(000) = 2400
M_r = 287.27	D_x = 1.496 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 2096 reflections
a = 24.0182 (13) Å	θ = 2.3–25.0°
b = 26.8445 (14) Å	µ = 0.11 mm⁻¹
c = 7.9140 (4) Å	T = 293 K
V = 5102.6 (5) Å³	Block, colourless
Z = 16	0.35 × 0.30 × 0.25 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	2261 independent reflections
Radiation source: fine-focus sealed tube	2096 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω and φ scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −27→28
T_min = 0.962, T_max = 0.972	k = −31→31
12952 measured reflections	l = −9→9

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0468P)² + 1.3678P] where P = (F_o² + 2F_c²)/3
2261 reflections	(Δ/σ)_max < 0.001
192 parameters	Δρ_max = 0.11 e Å⁻³
1 restraint	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₄H₁₃N₃O₄	V = 5102.6 (5) Å³
M_r = 287.27	Z = 16
Orthorhombic, Fdd2	Mo Kα radiation
a = 24.0182 (13) Å	µ = 0.11 mm⁻¹
b = 26.8445 (14) Å	T = 293 K
c = 7.9140 (4) Å	0.35 × 0.30 × 0.25 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	2261 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2096 reflections with I > 2σ(I)
T_min = 0.962, T_max = 0.972	R_int = 0.021
12952 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	1 restraint
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.11 e Å⁻³
2261 reflections	Δρ_min = −0.14 e Å⁻³
192 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 > 2sigma(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
C1	0.03152 (7)	0.07119 (6)	0.5103 (2)	0.0316 (4)
C2	0.07422 (7)	0.05817 (6)	0.6093 (2)	0.0348 (4)
H2	0.0673	0.0483	0.7200	0.042*
C3	0.12950 (7)	0.05908 (6)	0.5492 (2)	0.0348 (4)
C4	0.14101 (7)	0.07284 (6)	0.3758 (2)	0.0323 (4)
C5	0.21801 (8)	0.07230 (9)	0.1521 (3)	0.0562 (6)
H5A	0.1937	0.0565	0.0723	0.084*
H5B	0.2531	0.0551	0.1543	0.084*
H5C	0.2239	0.1063	0.1193	0.084*
C6	0.10471 (8)	0.10996 (8)	0.1107 (2)	0.0514 (5)
H6A	0.1378	0.1300	0.1095	0.077*
H6B	0.0731	0.1305	0.0853	0.077*
H6C	0.1078	0.0841	0.0275	0.077*
C7	0.04068 (6)	0.08867 (6)	0.33547 (19)	0.0305 (4)
H7	0.0273	0.1231	0.3273	0.037*
C8	−0.04681 (7)	0.05675 (6)	0.2547 (2)	0.0315 (4)
C9	−0.08276 (7)	0.04527 (7)	0.1229 (2)	0.0400 (4)
H9	−0.0692	0.0389	0.0149	0.048*
C10	−0.13915 (8)	0.04360 (7)	0.1563 (3)	0.0439 (5)
H10	−0.1637	0.0361	0.0691	0.053*
C11	−0.16010 (8)	0.05281 (7)	0.3162 (3)	0.0428 (5)
H11	−0.1983	0.0528	0.3352	0.051*
C12	−0.12390 (8)	0.06192 (7)	0.4459 (3)	0.0403 (4)
H12	−0.1377	0.0669	0.5543	0.048*
C13	−0.06647 (7)	0.06394 (6)	0.4184 (2)	0.0333 (4)
C14	−0.02720 (8)	0.06748 (6)	0.5610 (2)	0.0353 (4)
O1	0.22180 (6)	0.04252 (6)	0.6136 (2)	0.0619 (4)
O2	0.15774 (6)	0.02632 (7)	0.79971 (18)	0.0710 (5)
O3	−0.04181 (6)	0.06418 (6)	0.70928 (16)	0.0523 (4)
O4	0.00911 (5)	0.05848 (4)	0.21703 (15)	0.0356 (3)
N1	0.17083 (7)	0.04246 (6)	0.6569 (2)	0.0458 (4)
N2	0.19283 (6)	0.07078 (5)	0.3198 (2)	0.0409 (4)
H2A	0.2169	0.0679	0.3996	0.049*
N3	0.09766 (5)	0.08753 (5)	0.27888 (17)	0.0339 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0321 (9)	0.0326 (9)	0.0300 (9)	0.0013 (7)	−0.0007 (7)	−0.0038 (7)
C2	0.0399 (10)	0.0385 (9)	0.0262 (9)	−0.0023 (7)	−0.0043 (7)	−0.0041 (7)
C3	0.0317 (9)	0.0351 (9)	0.0376 (9)	0.0000 (7)	−0.0096 (8)	−0.0021 (7)
C4	0.0279 (9)	0.0299 (8)	0.0392 (9)	−0.0020 (7)	−0.0050 (8)	−0.0021 (8)
C5	0.0371 (11)	0.0692 (14)	0.0622 (13)	0.0076 (9)	0.0087 (10)	0.0000 (12)
C6	0.0379 (10)	0.0763 (14)	0.0399 (10)	0.0030 (9)	0.0018 (9)	0.0174 (10)
C7	0.0282 (9)	0.0317 (8)	0.0315 (8)	0.0012 (6)	−0.0022 (7)	−0.0017 (7)
C8	0.0280 (9)	0.0310 (9)	0.0356 (9)	0.0027 (6)	−0.0001 (7)	0.0029 (7)
C9	0.0395 (10)	0.0425 (10)	0.0378 (9)	−0.0006 (8)	−0.0079 (8)	−0.0006 (8)
C10	0.0364 (10)	0.0426 (10)	0.0527 (12)	−0.0032 (8)	−0.0143 (9)	0.0029 (9)
C11	0.0283 (10)	0.0424 (10)	0.0577 (12)	0.0009 (8)	−0.0010 (9)	0.0047 (9)
C12	0.0334 (9)	0.0393 (10)	0.0483 (11)	0.0010 (8)	0.0041 (9)	0.0015 (8)
C13	0.0318 (9)	0.0304 (8)	0.0376 (9)	0.0028 (7)	0.0014 (8)	0.0007 (7)
C14	0.0376 (10)	0.0344 (9)	0.0338 (10)	0.0029 (7)	0.0032 (8)	−0.0027 (8)
O1	0.0335 (8)	0.0824 (10)	0.0697 (11)	0.0039 (7)	−0.0197 (7)	0.0028 (9)
O2	0.0627 (10)	0.1090 (14)	0.0414 (8)	0.0052 (9)	−0.0172 (7)	0.0141 (9)
O3	0.0468 (8)	0.0771 (11)	0.0330 (7)	0.0008 (7)	0.0074 (6)	−0.0042 (7)
O4	0.0274 (7)	0.0480 (7)	0.0315 (6)	−0.0005 (5)	−0.0014 (5)	−0.0065 (5)
N1	0.0422 (10)	0.0525 (10)	0.0427 (10)	0.0006 (7)	−0.0168 (8)	−0.0015 (8)
N2	0.0252 (8)	0.0485 (9)	0.0492 (9)	−0.0011 (6)	−0.0038 (7)	−0.0018 (8)
N3	0.0263 (7)	0.0419 (8)	0.0334 (8)	0.0003 (6)	−0.0005 (6)	0.0026 (6)

Geometric parameters (Å, º) top

C1—C2	1.337 (2)	C7—O4	1.4527 (19)
C1—C14	1.470 (2)	C7—H7	0.9800
C1—C7	1.478 (2)	C8—O4	1.3767 (19)
C2—C3	1.410 (2)	C8—C9	1.389 (2)
C2—H2	0.9300	C8—C13	1.392 (2)
C3—N1	1.383 (2)	C9—C10	1.381 (3)
C3—C4	1.448 (3)	C9—H9	0.9300
C4—N2	1.322 (2)	C10—C11	1.384 (3)
C4—N3	1.352 (2)	C10—H10	0.9300
C5—N2	1.459 (3)	C11—C12	1.367 (3)
C5—H5A	0.9600	C11—H11	0.9300
C5—H5B	0.9600	C12—C13	1.398 (2)
C5—H5C	0.9600	C12—H12	0.9300
C6—N3	1.471 (2)	C13—C14	1.474 (2)
C6—H6A	0.9600	C14—O3	1.228 (2)
C6—H6B	0.9600	O1—N1	1.271 (2)
C6—H6C	0.9600	O2—N1	1.250 (2)
C7—N3	1.440 (2)	N2—H2A	0.8600

C2—C1—C14	123.98 (15)	O4—C8—C13	121.86 (15)
C2—C1—C7	121.15 (15)	C9—C8—C13	121.26 (16)
C14—C1—C7	114.82 (14)	C10—C9—C8	118.23 (18)
C1—C2—C3	121.34 (16)	C10—C9—H9	120.9
C1—C2—H2	119.3	C8—C9—H9	120.9
C3—C2—H2	119.3	C9—C10—C11	121.74 (18)
N1—C3—C2	117.53 (16)	C9—C10—H10	119.1
N1—C3—C4	121.99 (16)	C11—C10—H10	119.1
C2—C3—C4	120.25 (15)	C12—C11—C10	119.15 (17)
N2—C4—N3	123.19 (16)	C12—C11—H11	120.4
N2—C4—C3	119.11 (15)	C10—C11—H11	120.4
N3—C4—C3	117.71 (15)	C11—C12—C13	121.18 (18)
N2—C5—H5A	109.5	C11—C12—H12	119.4
N2—C5—H5B	109.5	C13—C12—H12	119.4
H5A—C5—H5B	109.5	C8—C13—C12	118.32 (16)
N2—C5—H5C	109.5	C8—C13—C14	120.29 (15)
H5A—C5—H5C	109.5	C12—C13—C14	120.99 (16)
H5B—C5—H5C	109.5	O3—C14—C1	122.65 (16)
N3—C6—H6A	109.5	O3—C14—C13	122.98 (17)
N3—C6—H6B	109.5	C1—C14—C13	114.19 (15)
H6A—C6—H6B	109.5	C8—O4—C7	112.85 (13)
N3—C6—H6C	109.5	O2—N1—O1	119.09 (16)
H6A—C6—H6C	109.5	O2—N1—C3	119.25 (16)
H6B—C6—H6C	109.5	O1—N1—C3	121.65 (16)
N3—C7—O4	106.47 (12)	C4—N2—C5	133.91 (16)
N3—C7—C1	115.21 (13)	C4—N2—H2A	113.0
O4—C7—C1	110.46 (13)	C5—N2—H2A	113.0
N3—C7—H7	108.2	C4—N3—C7	124.17 (14)
O4—C7—H7	108.2	C4—N3—C6	122.96 (15)
C1—C7—H7	108.2	C7—N3—C6	112.47 (13)
O4—C8—C9	116.82 (15)

C14—C1—C2—C3	175.22 (15)	C2—C1—C14—C13	−156.47 (16)
C7—C1—C2—C3	−2.0 (3)	C7—C1—C14—C13	20.9 (2)
C1—C2—C3—N1	−176.57 (17)	C8—C13—C14—O3	−165.56 (17)
C1—C2—C3—C4	−1.9 (2)	C12—C13—C14—O3	7.0 (3)
N1—C3—C4—N2	−1.9 (2)	C8—C13—C14—C1	9.7 (2)
C2—C3—C4—N2	−176.32 (15)	C12—C13—C14—C1	−177.78 (15)
N1—C3—C4—N3	178.45 (15)	C9—C8—O4—C7	157.13 (15)
C2—C3—C4—N3	4.0 (2)	C13—C8—O4—C7	−25.6 (2)
C2—C1—C7—N3	3.6 (2)	N3—C7—O4—C8	−179.19 (12)
C14—C1—C7—N3	−173.86 (14)	C1—C7—O4—C8	55.05 (17)
C2—C1—C7—O4	124.28 (17)	C2—C3—N1—O2	1.8 (3)
C14—C1—C7—O4	−53.19 (18)	C4—C3—N1—O2	−172.78 (17)
O4—C8—C9—C10	−179.54 (16)	C2—C3—N1—O1	−179.23 (17)
C13—C8—C9—C10	3.2 (2)	C4—C3—N1—O1	6.2 (3)
C8—C9—C10—C11	−0.2 (3)	N3—C4—N2—C5	−14.2 (3)
C9—C10—C11—C12	−2.6 (3)	C3—C4—N2—C5	166.2 (2)
C10—C11—C12—C13	2.5 (3)	N2—C4—N3—C7	178.08 (15)
O4—C8—C13—C12	179.59 (16)	C3—C4—N3—C7	−2.3 (2)
C9—C8—C13—C12	−3.3 (2)	N2—C4—N3—C6	−9.7 (2)
O4—C8—C13—C14	−7.7 (2)	C3—C4—N3—C6	169.90 (16)
C9—C8—C13—C14	169.44 (16)	O4—C7—N3—C4	−124.20 (15)
C11—C12—C13—C8	0.4 (3)	C1—C7—N3—C4	−1.4 (2)
C11—C12—C13—C14	−172.27 (16)	O4—C7—N3—C6	62.89 (17)
C2—C1—C14—O3	18.8 (3)	C1—C7—N3—C6	−174.29 (15)
C7—C1—C14—O3	−163.82 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	1.83	2.543 (2)	139
C5—H5A···O2ⁱ	0.96	2.46	3.376 (3)	159
C5—H5C···O3ⁱⁱ	0.96	2.51	3.416 (3)	157
C6—H6A···O3ⁱⁱ	0.96	2.55	3.429 (2)	152
C9—H9···O3ⁱ	0.93	2.60	3.455 (2)	154

Symmetry codes: (i) x, y, z−1; (ii) x+1/4, −y+1/4, z−3/4.