Crystal structure of 4-(6-chloro-4-oxo-4H-chromen-3-yl)-2-methyl­amino-3-nitro-4H,5H-pyrano[3,2-c]chromen-5-one chloro­form monosolvate

Rajamani Raja; Subramani Kandhasamy; Paramasivam T Perumal; A SubbiahPandi

doi:10.1107/S2056989015011810

. 2015 Jun 27;71(Pt 7):o512–o513. doi: 10.1107/S2056989015011810

Crystal structure of 4-(6-chloro-4-oxo-4H-chromen-3-yl)-2-methylamino-3-nitro-4H,5H-pyrano[3,2-c]chromen-5-one chloroform monosolvate

Rajamani Raja ^a, Subramani Kandhasamy ^b, Paramasivam T Perumal ^b, A SubbiahPandi ^a,^*

PMCID: PMC4518942 PMID: 26279937

Abstract

In the title compound, C₂₃H₁₄Cl₄N₂O₇, the pyran ring has an envelope conformation with the methine C atom as the flap. The chromene rings are almost planar (r.m.s. deviations of 0.027 and 0.018 Å) and their mean planes are inclined to one another by 85.61 (10)°. The mean planes of the pyran ring and the chromene ring fused to it are inclined to one another by 7.41 (13)°. The molecular structure is stabilized by an intramolecular N—H⋯O hydrogen bond, generating an S(6) ring motif. In the crystal, molecules are linked by pairs of N—H⋯O hydrogen bonds, forming inversion dimers with an R ² ₂(12) ring motif. The dimers are linked by pairs of C—H⋯O hydrogen bonds, enclosing R ² ₂(18) ring motifs, forming chains along [010]. Within the chains there are C—H⋯π interactions. The chains are linked via slipped parallel π–π interactions, forming a three-dimensional structure [the shortest inter-centroid distance is 3.7229 (19) Å].

Keywords: crystal structure, chromene, chromones, pyran, hydrogen bonding, C—H⋯π interactions, π–π interactions, inversion dimers

Related literature

For the uses and biological importance of chromones, see: Miao & Yang (2000 ▸); Lin et al. (2000 ▸); Larget et al. (2000 ▸); Groweiss et al. (2000 ▸); Deng et al. (2000 ▸); Pietta (2000 ▸); Mori et al. (1998 ▸); Montaña et al. (2007 ▸); Hsu et al. (2006 ▸); Beecher (2003 ▸). For a related structure, see: Narayanan et al. (2013 ▸). graphic file with name e-71-0o512-scheme1.jpg

Experimental

Crystal data

C₂₂H₁₃ClN₂O₇·CHCl₃
M _r = 572.16
Triclinic,
a = 8.3716 (2) Å
b = 11.6435 (3) Å
c = 13.1018 (4) Å
α = 86.455 (1)°
β = 88.251 (1)°
γ = 69.841 (1)°
V = 1196.51 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.54 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T _min = 0.878, T _max = 0.897
15560 measured reflections
4208 independent reflections
3451 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.154
S = 1.03
4208 reflections
325 parameters
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.89 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: PLATON (Spek, 2009 ▸); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015011810/su5158sup1.cif

e-71-0o512-sup1.cif^{(23.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015011810/su5158Isup2.hkl

e-71-0o512-Isup2.hkl^{(206.2KB, hkl)}

Click here for additional data file.^{(7.6KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015011810/su5158Isup3.cml

Click here for additional data file.^{(1.4MB, tif)}

. DOI: 10.1107/S2056989015011810/su5158fig1.tif

The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The intramolecular N—H⋯O hydrogen bond is shown as a dashed line (see Table 1 for details)

Click here for additional data file.^{(1.9MB, tif)}

a . DOI: 10.1107/S2056989015011810/su5158fig2.tif

The crystal packing of the title compound, viewed along the a axis. The hydrogen bonds are shown as dashed lines (see Table 1 for details). H atoms not involved in these interactions have been omitted for clarity.

CCDC reference: 1055442

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

Table 1. Hydrogen-bond geometry (, ).

Cg4 is the centroid of the C2C7 ring.

DHA	DH	HA	D A	DHA
N2H2O6	0.86	1.00	2.604(3)	127
N2H2O6ⁱ	0.86	2.17	2.910(3)	144
C6H6O2ⁱⁱ	0.96	2.49	3.186(4)	132
C10H10B Cg4ⁱⁱ	0.98	2.98	3.719(4)	134

Open in a new tab

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

Acknowledgments

The authors thank the Department of Chemistry, IIT, Chennai, India, for the X-ray intensity data collection.

supplementary crystallographic information

S1. Structural commentary

\ Chromones constitute a major class of naturally occurring compounds and interest in their chemistry continues unabated because of their usefulness as biologically active agents (Miao & Yang, 2000). Some of the biological activities attributed to chromone derivatives include cytotoxic anticancer (Lim et al., 2000), neuroprotective (Larget et al., 2000), HIV-inhibitory (Groweiss et al., 2000), antimicrobial (Deng et al., 2000), antifungal (Mori et al., 1998) and antioxidant activities (Pietta, 2000). Chromone derivatives are present in large amounts in the human diet (Beecher, 2003), due to their abundance in plants and their low mammalian toxicity. They are known to exhibit antioxidant (Montaña et al., 2007), anti-inflammatory, antimicrobial, antihypertensive, antiplatelet, gastroprotective, antitumour (Hsu et al., 2006) and antiallergic activities.

The molecular structure of the title compound is illustrated in Fig. 1. It exhibits structural similarities with a related chromenone derivative, 4-(4-Bromophenyl)-2-methylamino-3-nitro-5,6,7,8-tetrahydro-4H-chromen-\ 5-one (Narayanan et al., 2013). The chromene rings (A = O4/C1—C8/C13) and (B = O1/C14—C22) are almost planar (r.m.s. deviations of 0.027 and 0.018 Å, respectively) and normal to one another with a dihedral angle of 85.61 (10) ° between their mean planes. The pyran ring (C = O5/C8/C9/C11—C13) has an envelope conformation with atom C12 as the flap. Its mean plane is inclined to the mean plane of the chromene ring A, to which it is fused, by 7.41 (13) °. The nitro group is almost coplanar to the pyran ring, as indicated by torsion angles C12—C11—N1—O7 = 1.2 (4) \% and C9—C11—N1—O6 = 2.5 (5) °. The molecular structure is stabilized by an intramolecular N—H···O hydrogen bond, which generates an S(6) ring motif (Table 1 and Fig. 1).

In the crystal, molecules are linked by a pair of N—H···O hydrogen bonds forming inversion dimers with an R²₂(12) ring motif; Table 1 and Fig. 2. The dimers are linked by a pair of C—H···O hydrogen bonds, enclosing R²₂((18) ring motifs, and forming chains along [010]. Within the chains there are C—H···π interactions (Table 1). The chains are linked via slipped parallel π-π interactions forming a three-dimensional structure [Cg2···Cg2ⁱ = 3.9337 (16) Å, inter-planar distance = 3.5746 (12) Å, slippage 1.642 Å; Cg5···Cg5ⁱⁱ = 3.7229 (19) Å, inter-planar distance = 3.4023 (14) Å, slippage = 1.511 Å; symmetry codes: (i) -x-1, -y+1, -z; (ii) -x, -y+1, -z+1].

S2. Synthesis and crystallization

A three component coupling reaction, involving 4-hydroxycoumarin (0.81 g, 5 mmol), 6-chloro-4-oxo-4H-chromene-3-carbaldehyde (0.87 g, 5 mmol) and NMSM (0.74 g, 5 mmol), was carried out in EtOH at room temperature (3 h) in the presence of triethylamine (0.1eq) as catalyst. Upon completion of the reaction, the mixture was filtered, and washed with ethanol to obtain the desired product as a white solid. Using this combination of ethanol and triethylamine gave an excellent result with a shorter than normal reaction time and an overall yield of 83 %. The title compound was recrystallized from chloroform giving colourless block-like crystals.

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The N and C-bound H atoms were positioned geometrically and allowed to ride on their parent atoms: N—H = 0.86 Å, C–H = 0.93–0.98 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(N,C) for all other H atoms.