(4S*)-2-Methyl­amino-3-nitro-4-(4-nitro­phen­yl)-5,6,7,8-tetra­hydro-4H-chromen-5-one

P Narayanan; Jayabal Kamalraja; Paramasivam T Perumal; K Sethusankar

doi:10.1107/S1600536813021181

. 2013 Aug 3;69(Pt 9):o1380–o1381. doi: 10.1107/S1600536813021181

(4S*)-2-Methylamino-3-nitro-4-(4-nitrophenyl)-5,6,7,8-tetrahydro-4H-chromen-5-one

P Narayanan ^a, Jayabal Kamalraja ^b, Paramasivam T Perumal ^b, K Sethusankar ^a,^*

PMCID: PMC3884480 PMID: 24427023

Abstract

The title compound, C₁₆H₁₅N₃O₆, is asymmetric with a chiral centre located in the pyran ring and crystallizes as a racemate. The six-membered carbocyclic ring adopts an envelope conformation with the central CH₂ C atom as the flap. The amine N atom deviates from the mean plane of the pyran ring by 0.1365 (15) Å. The nitrophenyl ring is almost orthogonal to the pyran ring and the mean plane of the six-membered carbocyclic ring, the dihedral angle between their mean planes being 88.30 (7) and 87.61 (8)°, respectively. The molecular structure is stabilized by an intramolecular N—H⋯O hydrogen bond, which generates an S(6) ring motif. In the crystal, molecules are linked via C—H⋯O hydrogen bonds, forming infinite bands lying parallel to (-110) and composed of alternate R ₂ ²(24) and R ₂ ⁴(12) graph-set ring motifs. The crystal structure is further stabilized by C—H⋯π interactions, forming a three-dimensional structure.

Related literature

For the uses and biological importance of chromene, see: Ercole et al. (2009 ▶); Geen et al. (1996 ▶); Khan et al. (2010 ▶); Raj et al. (2010 ▶). For related structures, see: Narayanan et al. (2013a ▶,b ▶). For graph-set notation, see: Bernstein et al. (1995 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₁₆H₁₅N₃O₆
M _r = 345.31
Triclinic,
a = 8.2587 (3) Å
b = 8.7679 (4) Å
c = 10.9346 (5) Å
α = 101.616 (2)°
β = 90.426 (2)°
γ = 91.930 (2)°
V = 775.05 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.966, T _max = 0.977
10840 measured reflections
3161 independent reflections
2633 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.126
S = 1.04
3161 reflections
230 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.31 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813021181/su2627sup1.cif

e-69-o1380-sup1.cif^{(20KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813021181/su2627Isup2.hkl

e-69-o1380-Isup2.hkl^{(151.9KB, hkl)}

Click here for additional data file.^{(6.4KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813021181/su2627Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3	0.90 (3)	1.89 (3)	2.601 (2)	134 (2)
C11—H11A⋯O6ⁱ	0.97	2.54	3.352 (2)	141
C11—H11B⋯O5ⁱⁱ	0.97	2.54	3.186 (2)	124
C10—H10A⋯Cg1ⁱⁱⁱ	0.97	2.90	3.515 (2)	135
C16—H16B⋯Cg1^iv	0.96	2.90	3.577 (3)	142

Open in a new tab

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

Acknowledgments

The authors thank Mr T. Srinivasan and Dr D. Velmurugan, Head of the CAS in Crystallography and Biophysics, University of Madras, Chennai, India, for the data collection.

supplementary crystallographic information

1. Comment

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 (Khan et al., 2010; Raj et al., 2010). Against this background, the X-ray analysis of the title compound has been carried out to study its structural aspects.

The title compound, Fig. 1, consists of a chromene moiety attached to a nitrophenyl ring, a nitro group and a methylamine group. The molecular structure is stabilized by an intra molecular N1—H1A···O3 interaction, which generates an S(6) ring motif (Table 1 and Fig. 1). The pyran ring (C7/C8/C13-C15/O1) mean plane is almost orthogonal to the nitrophenyl ring (C1–C6), with a dihedral angle of 88.30 (7) °.

The pyran ring is almost coplanar with the mean plane of the nitro group (N2/O3/O4), with a dihedral angle of 3.99 (11)°. The mean plane of the six membered carbocyclic ring (C8–C13) makes a dihedral angle of 87.61 (8) ° with the nitrophenyl ring (C1–C6), again they are almost perpendicular to each other.

The six membered carbocyclic rings (C8–C13) of the chromene moiety adopts an envelope conformation on atom C11 with puckering parameters (Cremer & Pople, 1975): Q₂ = 0.4018 (17) Å, Q₃ = -0.2465 (18) Å and φ₂ = 358.1 (3). Atom C11 deviates from the mean plane of the rest of the ring atoms by 0.3325 (18) Å. The amine group nitrogen atom N1 deviates by -0.1365 (15) Å from the mean plane of the pyran ring. The title compound exhibits structural similarities with already reported related structures (Narayanan et al., 2013a,b).

In the crystal, molecules are linked via C-H···O hydrogen bonds (Table 1 and Fig. 2), which form infinite bands lying parallel to plane (-1 1 0), and which enclose alternate R₂²(24) and R₂⁴(12) graph-set ring motifs (Bernstein et al., 1995). The crystal structure is further stabilized by C-H···\p interactions (Table 1) forming a three-dimensional structure.

2. Experimental

A solution of the requisite aldehyde (0.151 g, 1.0 mmol), cyclic 1,3-dicarbonyl compound (0.112 g, 1.0 mmol), NMSM (0.148 g, 1.0 mmol) and piperidine (0.2 equiv) in EtOH (2 ml) was stirred for 1.5 hrs. After the reaction was complete as indicated by TLC, the product was filtered and washed with EtOH (2 ml) to remove the excess base and other impurities. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in ethanol at room temperature.