7,7-Dimethyl-2-methyl­amino-4-(4-methyl­phenyl)-3-nitro-7,8-di­hydro-4H-chromen-5(6H)-one

S Antony Inglebert; Jayabal Kamalraja; K Sethusankar; Paramasivam T Perumal

doi:10.1107/S1600536814010794

. 2014 May 24;70(Pt 6):o710–o711. doi: 10.1107/S1600536814010794

7,7-Dimethyl-2-methylamino-4-(4-methylphenyl)-3-nitro-7,8-dihydro-4H-chromen-5(6H)-one

S Antony Inglebert ^a, Jayabal Kamalraja ^b, K Sethusankar ^c,^*, Paramasivam T Perumal ^b

PMCID: PMC4051056 PMID: 24940281

Abstract

In the title compound, C₁₉H₂₂N₂O₄, the six-membered cyclohexenone ring of the chromene unit adopts an envelope conformation, with the dimethyl-substituted C atom as the flap, while the pyran ring has a boat conformation. These two mean planes are inclined to one another by 6.65 (13)°·The benzene ring is normal to the 4H-chromene moiety mean plane, making a dihedral angle of 89.18 (5)°. The methylamine and nitro groups are slightly twisted from the chromene moiety mean plane, with torsion angles C—N—C—O = 1.70 (18) and O—N—C—C = 0.15 (18)°. The molecular structure is characterized by an intramolecular N—H⋯O hydrogen bond, which generates an S(6) ring motif. In the crystal, molecules are linked via pairs of weak C—H⋯O hydrogen bonds, forming inversion dimers. These dimers are connected by further C—H⋯O hydrogen bonds, forming sheets lying parallel to (10-1).

Related literature

For the biological and pharmacological properties of chromenes and their derivatives, see: Zonouzi et al. (2013 ▶). For related structures, see: Narayanan et al. (2013 ▶); Inglebert et al. (2014 ▶).

Experimental

Crystal data

C₁₉H₂₂N₂O₄
M _r = 342.39
Monoclinic,
a = 9.4373 (5) Å
b = 15.8487 (8) Å
c = 12.1414 (6) Å
β = 105.122 (1)°
V = 1753.09 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.968, T _max = 0.968
22747 measured reflections
4023 independent reflections
3290 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.129
S = 1.04
4023 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.27 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 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814010794/su2733sup1.cif

e-70-0o710-sup1.cif^{(21KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814010794/su2733Isup2.hkl

e-70-0o710-Isup2.hkl^{(197.2KB, hkl)}

Click here for additional data file.^{(7.1KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814010794/su2733Isup3.cml

CCDC reference: 1002204

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3	0.86	1.98	2.6024 (15)	129
C5—H5⋯O3ⁱ	0.93	2.58	3.0685 (17)	113
C10—H10A⋯O4ⁱⁱ	0.96	2.54	3.4335 (19)	154

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

Acknowledgments

The authors are grateful to Dr Babu Varghese, SAIF, IIT, Chennai, India, for the X-ray intensity data collection.

supplementary crystallographic information

1. Comment

4H-Chromene derivatives are important scaffolds in organic and medicinal chemistry. 4H-Chromene and their derivatives exhibit a wide spectrum of biological applications, such as antiallergic, anti-proliferative, anticancer, antibacterial, antiviral and potent apoptosis (Zonouzi et al., 2013).

The title compound, Fig. 1, consists of a chromene unit connected to a toluene ring at C11, a nitro group at C12, a methyl amine group at C13, dimethyl group at C16 and an oxygen atom at C18. The benzene ring (C1-C6) is normal to the mean plane of chromene unit (O1/C11–C19) with a dihedral angle of 89.18 (5)°. The nitro and methylamine groups are inclined to the mean plane of chromene unit by 6.51 (8) and 5.42 (6)°, respectively.

The six membered carbocyclic ring (C14–C19) of the chromene moiety adopts an envelope conformation with atom C16 as the flap: puckering amplitude (Q) = 0.4584 (15) Å, θ = 58.54 (17)° φ = 120.3 (2)°. Atom C16 deviates by 0.3234 (15) Å from the mean plane passing through the rest of the ring atoms. This conformation is similar to that in related structures (Narayanan et al., 2013; Inglebert et al., 2014).

The amine group nitrogen atoms, N1 and N2, deviate by -0.2044 (11) and -0.1338 (11) Å from the mean plane of the chromene moiety. The methyl amine group attached to C13 is coplanar with the chromene moiety as indicated by the torsion angle C8–N1–C13–O1 = 1.70 (18)°. The nitro group is also coplanar to the chromene moiety mean plane, as indicated by the torsion angles C13–C12–N2–O3 = 0.15 (18)° and C11–C12–N2–O4 = -4.82 (16)°. The molecular structure is characterized by an intramolecular N—H···O hydrogen bond, generates an S(6) ring motif (Fig. 1 and Table 1).

In the crystal, molecules are linked via pairs of C—H···O hydrogen bonds forming inversion dimers (Fig. 2 and Table 1). These dimers are connected by further C-H···O hydrogen bonds forming sheets lying parallel to (10-1) [Table 1 and Fig. 2]. The nitro atom O3 is involved in both intra- and inter-molecular hydrogen bonding, having a bifurcated character.

2. Experimental

A solution of 4-methylbenzaldehyde (1.0 mmol), 5,5-dimethylcyclohexane-1,3-dione (1.0 mmol), NMSM (1.0 mmol), and piperidine (0.2 equiv) in ethanol (2 ml) was stirred for 3.5 h. After the reaction was complete, as indicated by TLC, the product was filtered and washed with 2 ml of ethanol, to remove the excess base and other impurities. Finally, the product was recrystallized from ethanol yielding colourless block-like crystals.