6-Meth­oxy-N-methyl-3-nitro-4-nitro­methyl-4H-chromen-2-amine

J Muthukumaran; A Parthiban; P Manivel; H Surya Prakash Rao; R Krishna

doi:10.1107/S1600536811015595

. 2011 Apr 29;67(Pt 5):o1276–o1277. doi: 10.1107/S1600536811015595

6-Methoxy-N-methyl-3-nitro-4-nitromethyl-4H-chromen-2-amine

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

PMCID: PMC3089089 PMID: 21754559

Abstract

In the title compound, C₁₂H₁₃N₃O₆, the dihydropyran ring adopts a near screw-boat conformation. The dihedral angle between the mean planes of the benzene and dihydropyran rings is 6.35 (5)°. An intramolecular N—H⋯O hydrogen bond generates an S(6) motif, which stabilizes the molecular conformation. In the crystal, weak intermolecular C—H⋯O, N—H⋯O and C—H⋯π hydrogen bonds contribute to the stabilization of the packing.

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 et al. (1988 ▶); Brooks (1998 ▶); Valenti et al. (1993 ▶); Hyana & Saimoto (1987 ▶); Tang et al. (2007 ▶); Wang et al. (2000 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶). For C—H⋯π interactions, see: Desiraju & Steiner (1999 ▶).

Experimental

Crystal data

C₁₂H₁₃N₃O₆
M _r = 295.25
Monoclinic,
a = 6.8354 (2) Å
b = 9.4363 (2) Å
c = 19.9332 (4) Å
β = 90.777 (2)°
V = 1285.59 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.4 × 0.4 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.966, T _max = 1.000
13856 measured reflections
2256 independent reflections
1804 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.116
S = 1.01
2256 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.36 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/S1600536811015595/hq2002sup1.cif

e-67-o1276-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015595/hq2002Isup2.hkl

e-67-o1276-Isup2.hkl^{(110.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811015595/hq2002Isup3.cml

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

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

Cg is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	2.01	2.6169 (17)	127
N1—H1⋯O3ⁱ	0.86	2.26	2.9808 (18)	142
C11—H11A⋯O2ⁱⁱ	0.97	2.49	3.4366 (19)	165
C10—H10A⋯Cgⁱⁱⁱ	0.96	2.61	3.548 (2)	164
C10—H10C⋯Cg^iv	0.96	2.86	3.706 (2)	148

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

Acknowledgments

RK, JM, and PM thank the Centre for Bioinformatics (funded by the Department of Biotechnology and the Department of Information Technology, New Delhi, India) and Pondicherry University for providing computational facilities. AP thanks Pondicherry University for a fellowship and PM thanks the University Grants Commission (UGC) for a fellowship. HSP thanks the UGC for the SAP and the Department of Science and Technology (DST) for the FIST.

supplementary crystallographic information

Comment

4H-Chromene derivatives exhibit 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). Functionally substituted 4H-Chromene derivatives are a new class of compound that binds to Bcl-2 protein and induces apoptosis or programmed cell death in cancer cells (Wang et al., 2000). In order to examine the activity relationship between their molecular structure and biology, a single-crystal of the title compound was prepared for X-ray diffraction studies.

In the title compound (Fig. 1), the methoxy substituent at the C4 atom forms the torsion angle of -180 (14) ° [(-) anti-periplanar conformation] with the atom set O6/C4/C3/C2. From the puckering analysis (Cremer & Pople, 1975), the dihydropyran ring (O1/C1/C6/C7/C8/C9) is very similar to the screw-boat conformation (S form) with puckering parameters of Q = 0.1798 (15) Å, θ = 100.8 (5)° and Φ = 20.1 (5)°. Three intramolecular interactions N1—H1···O2 (symmetry code: x, y, z), N1—H1···N2 and C11—H11A···O3 are observed to contribute to the stability of the title compound, in which an N1—H1···O2 interaction generates a characteristic intramolecular S (6) motif with an N···O distance of 2.617 (17) Å (Fig. 2). The stabilization of crystal packing (Fig. 3) is influenced by intermolecular hydrogen bonding such as N1—H1···O3 (symmetry code: -x + 1/2, y - 1/2, -z + 1/2) and C11—H11A···O2 (symmetry code: -x + 1/2, y + 1/2, -z + 1/2). The C—H···pi interactions (Fig. 4) observed between C10—H10A···Cg (symmetry code:-x, 1 - y,-z, Cg is the centroid of the benzene ring C1—C6, C···Cg distance: 3.548 (2) Å, H-Perp: -2.56 Å) and C10—H10C···Cg (symmetry code: 1 - x,1 - y,-z, C···Cg distance: 3.706 (2) Å, H-Perp: 2.65 Å) also contribute to the crystal packing. The bond distances of the C—H···π interactions agree with those described by Desiraju & Steiner (1999). An intermolecular N1—H1···O3 interaction generates a C (6) motif with an N···O distance of 2.981 (18) Å (Fig. 5).

Experimental

(E)-4-Methoxy-2-(2-nitrovinyl)phenol (200 mg, 1.024 mmol) was taken in a 25 ml round bottom flask in methanol (5 ml). To this solution, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (15 mg, 0.102 mmol) was added and stirred thoroughly for 10 minutes at room temperature. To this stirred solution, ((E) N-methyl-1-(methylthio)-2-nitroethenamine) (NMSM) was added and stirred for 8 h for completion (TLC, hexane:ethyl acetate, 3:2, R_f of I = 1/2). The reaction mixture was then kept in a refrigerator for 3 h to afford racemic mixture of the product (I)as a white precipitate, which was filtered. Good crystals were obtained by recrystallization with a solution of dichloromethane:hexane (9:3 v/v).