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

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

doi:10.1107/S2056989015014553

. 2015 Aug 6;71(Pt 9):o648–o649. doi: 10.1107/S2056989015014553

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

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

PMCID: PMC4555410 PMID: 26396884

Abstract

In the title compound, C₂₂H₁₃BrN₂O₇·CHCl₃, the pyran ring adopts a shallow sofa conformation with the C atom bearing the bromochromene system as the flap [deviation = 0.291 (3) Å]. The dihedral angle between the pyran fused-ring system (all atoms; r.m.s. deviation = 0.032 Å) and the bromochromene ring system (r.m.s. deviation = 0.027 Å) is 87.56 (9)°. An intramolecular N—H⋯O hydrogen bond closes an S(6) ring. The Cl atoms of the solvent molecule are disordered over two sets of sites in a 0.515 (6):0.485 (6) ratio. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds generate R ₂ ²(12) loops. The packing also features C—H⋯O and very weak π–π [centroid–centroid separation = 3.960 (2) Å] interactions, which link the dimers into a three-dimensional network.

Keywords: crystal structure, chromenone, hydrogen bonding

Related literature

For background to chromene derivatives, see: Ercole et al. (2009 ▸); Geen et al. (1996 ▸) Khan et al. (2010 ▸); Raj et al. (2010 ▸). For a related structure, see: Raja et al. (2015 ▸). graphic file with name e-71-0o648-scheme1.jpg

Experimental

Crystal data

C₂₂H₁₃BrN₂O₇·CHCl₃
M _r = 616.62
Triclinic,
a = 9.8816 (2) Å
b = 11.9237 (3) Å
c = 12.0616 (3) Å
α = 80.804 (1)°
β = 68.422 (1)°
γ = 70.735 (1)°
V = 1246.36 (5) Å³
Z = 2
Mo Kα radiation
μ = 2.02 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T _min = 0.539, T _max = 0.632
17277 measured reflections
4389 independent reflections
3672 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.120
S = 1.04
4389 reflections
353 parameters
114 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.53 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/S2056989015014553/hb7473sup1.cif

e-71-0o648-sup1.cif^{(24.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014553/hb7473Isup2.hkl

e-71-0o648-Isup2.hkl^{(215KB, hkl)}

Click here for additional data file.^{(8.3KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015014553/hb7473Isup3.cml

Click here for additional data file.^{(1.5MB, tif)}

S . DOI: 10.1107/S2056989015014553/hb7473fig1.tif

The molecular structure of the title molecule, with displacement ellipsoids drawn at 30% probability level. The intramolecular hydrogen bond, which generates an S(6) ring motif, is shown as a dashed line.

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

. DOI: 10.1107/S2056989015014553/hb7473fig2.tif

Packing diagram showing the chain motif Inline graphic (12) along the [100] direction.

CCDC reference: 1416576

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N2H2O5	0.86	2.00	2.622(5)	128
N2H2O5ⁱ	0.86	2.37	3.063(5)	138
C4H4O7ⁱⁱ	0.93	2.59	3.383(6)	144
C15H15O4ⁱⁱⁱ	0.93	2.36	3.221(4)	153

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

Acknowledgments

The authors the thank Department of Chemistry, IIT, Chennai, India, for the data collection.

supplementary crystallographic information

S1. Comment

Chromene derivatives are 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, etc. (Khan et al., 2010; Raj et al., 2010). Against this background an X-ray diffraction study of the title compound and its structural aspects are presented herein.

The asymmetric unit of the title compound is shown in Fig.1. The six-membered central pyran ring is very similar to a screw boat conformation as evidenced by the puckering parameters q₂ = 0.204 (4) Å, θ = 112.7 (11) and φ = 6.7 (12)°, respectively. The atoms C10 and O3 are deviating from the mean plane of C8—C9—C11—C12 by -0.266 and -0.644 Å, respectively. The chromene ring (O2/C1—C9) and (O7/C14—C22) are almost planar and normal to one another with a dihedral angle of 88.20 (2)° between their mean planes. The nitro group is bonded to the pyran ring at CC with the torsion angle C12—C11—N1—O5 0f 3.5 (5)°, indicating a (+) syn-periplanar conformation for this group. The chromene ring attached to the pyran ring at C10 with torsion angle C11—C10—C14—C15 of 117.6 (4)°, indicating a (+) anti-clinal conformation for this group. The title compound exhibits structural similarities with already reported related structure (Raja et al., 2015).

In the crystal structure, the molecules are linked to form an infinite chain along [100], through N2—H···O5 hydrogen bonds, generating graph set motifs R₂²(12) (Fig.2). In addition, there is a N—H···O intramolecular interaction.

S2. Experimental

4-Hydroxycoumarin (0.81 g, 5 mmol), 6-bromo-4-oxo-4H-chromene-3-carbaldehyde (0.78 g, 5 mmol) and NMSM (0.74 g, 5 mmol) were mixed in ethanol at room temperature (3 h) in the presence of TEA (triethylamine 0.1 eq), as a catalyst. Upon completion of the reaction, the mixture was filtered, and washed with ethanol to obtained desired white product in 93% yield. Colourless blocks of the title compound were recrystallised from chloroform solution.