6,8-Dichloro-N-methyl-3-nitro-4-nitro­methyl-4H-chromen-2-amine

J Muthukumaran; A Parthiban; M Kannan; H Surya Prakash Rao; R Krishna

doi:10.1107/S1600536811009366

. 2011 Mar 15;67(Pt 4):o898–o899. doi: 10.1107/S1600536811009366

6,8-Dichloro-N-methyl-3-nitro-4-nitromethyl-4H-chromen-2-amine

J Muthukumaran ^a, A Parthiban ^b, M Kannan ^a, H Surya Prakash Rao ^b,^‡, R Krishna ^a,^*

PMCID: PMC3099939 PMID: 21754173

Abstract

In the title compound, C₁₁H₉Cl₂N₃O₅, the dihydropyran ring adopts a near-half-chair conformation. The benzene ring makes a torsion angle of 5.02 (5)° with the dihydropyran ring. Adjacent molecules are interlinked through intermolecular C—H⋯O, N—H⋯O and C—Cl⋯π [3.4743 (9) Å] interactions. The intermolecular N—H⋯O hydrogen bond generates an R ₂ ²(12) motif, which is observed to contribute to the crystal packing stability. Moreover, the molecular structure displays an S(6) motif formed by intramolecular N—H⋯O hydrogen bonding.

Related literature

For related structures, see: Gayathri et al. (2006 ▶); Bhaskaran et al. (2006 ▶). For the biological importance of 4H-chromene derivatives, see: Cai (2007 ▶, 2008 ▶); Cai et al. (2006 ▶); Gabor (1988 ▶); Brooks (1998 ▶); Valenti et al. (1993 ▶); Hyana & Saimoto (1987 ▶); Tang et al. (2007 ▶). For ring-puckering analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₁₁H₉Cl₂N₃O₅
M _r = 334.11
Triclinic,
a = 8.7426 (7) Å
b = 9.2727 (7) Å
c = 9.3420 (7) Å
α = 70.017 (7)°
β = 72.609 (7)°
γ = 87.579 (6)°
V = 677.68 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.50 mm⁻¹
T = 293 K
0.4 × 0.35 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.792, T _max = 1.000
15150 measured reflections
2385 independent reflections
2072 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.110
S = 1.01
2385 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; 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, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811009366/zq2089sup1.cif

e-67-0o898-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009366/zq2089Isup2.hkl

e-67-0o898-Isup2.hkl^{(117.2KB, hkl)}

Additional supplementary materials: 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⋯O2	0.86	2.00	2.613 (2)	128
N1—H1⋯O2ⁱ	0.86	2.12	2.881 (2)	147
C7—H7⋯O3ⁱⁱ	0.98	2.50	3.1944 (19)	128
C11—H11B⋯O3ⁱⁱ	0.97	2.54	3.103 (2)	117

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

Acknowledgments

RK, JM and MK thank the Centre for Bioinformatics (funded by the Department of Biotechnology and the Department of Information Technology, New Delhi, India), Pondicherry University for providing the computational facilities to carry out this research work. MK also thanks the University Grants Commission (UGC) for a Rajiv Gandhi National Fellowship. AP thanks Pondicherry University for a fellowship. HSPR thanks UGC for the SAP and the Department of Science and Technology (DST) for the FIST.

supplementary crystallographic information

Comment

4H-Chromenes are biologically important compounds used as synthetic ligands for drug designing and discovery process. They exhibit numerous biological and pharmacological properties such as anti-viral, anti-fungal, anti-inflammatory, anti-diabetic, cardionthonic, anti-anaphylactic and anti-cancer activity (Cai, 2008; Cai, 2007; Cai et al., 2006; Gabor et al., 1988; Brooks, 1998; Valenti et al., 1993; Hyana & Saimoto, 1987; Tang et al., 2007). In view of the growing medicinal importance of 4H-chromene derivatives, a single-crystal X-ray diffraction study on the title compound was carried out and analyzed.

The title compound (Fig. 1) contains the 4H-chromene moiety with four different substituents [–Cl₂, –NO₂, –CH₂NO₂ and –NHCH₃]. The Cl1 group attached to C2 by an (+) anti-periplanar conformation with the torsion angle (Cl1/C2/C3/C4) of 178.76 (14) °, whereas another chlorine attached to C4 with the torsion angle (Cl2/C4/C3/C2) of -176.94 (14) °, which oriented in (-) anti-periplanar conformations. From the puckering analysis (Cremer & Pople, 1975), the fused dihydropyran ring (O1/C1/C6/C7/C8/C9) of 4H-chromene is very similar to half chair (H form) conformation with puckering parameters of Q = 0.1772 (17) Å, θ = 104.5 (5) ° and Φ = 11.6 (6) °. The molecular structure is stabilized by intramolecular N—H···O and C—H···O interactions. The intramolecular N1—H1···O2 interaction generates a graph-set motif S (6) (Fig. 2) with a D···A bond distance of 2.613 (2) Å. The crystal packing of the molecule (Fig. 3) is stabilized by intermolecular N1—H1···O2 (symmetry code: -x + 2, -y + 1, -z + 1), C7—H7···O3 (symmetry code: -x + 2, -y + 2, -z), C11—H11B···O3 (symmetry code:-x + 2, -y + 2, -z) and C—Cl··· π (symmetry code: 1 - x, 1 - y, -z) interactions (Fig. 4). The intermolecular N1—H1···O2 interaction generates a ring of graph-set R²₂ (12) with the bond distance of 2.881 (2) Å (Fig. 5).

Experimental

(E)-2,4-Dichloro-6-(2-nitrovinyl)phenol (100 mg, 0.427 mmol) was taken in a 25 ml round bottom flask in methanol (4 ml). To this solution, 1,8-diazabicyclo[5.4.0] undec-7-ene (DBU) (8 mg, 0.042 mmol) was added and stirred thoroughly for 10 minutes at room temperature. To this stirred solution, NMSM ((E) N-methyl-1-(methylthio)-2-nitroethenamine) was added and stirred for 10 h for completion (TLC, hexane: EtoAc, 3:2, R_f of I = 0.3). The reaction mixture was then kept in a refrigerator for 2 h to afford racemic mixture of the product (I), white precipitate, which was filtered. Good crystals were obtained by recrystallization with a solution of dichloromethane: hexane (9:3 v/v).