10-Methyl-2-oxo-4-phenyl-2,11-di­hydro­pyrano[2,3-a]carbazole-3-carbo­nitrile

A Thiruvalluvar; E Yamuna; R Archana; K J Rajendra Prasad; R J Butcher

doi:10.1107/S1600536813011823

. 2013 May 4;69(Pt 6):o831. doi: 10.1107/S1600536813011823

10-Methyl-2-oxo-4-phenyl-2,11-dihydropyrano[2,3-a]carbazole-3-carbonitrile

A Thiruvalluvar ^a,^*, E Yamuna ^b, R Archana ^a, K J Rajendra Prasad ^c, R J Butcher ^d

PMCID: PMC3684919 PMID: 23795021

Abstract

In the title molecule, C₂₃H₁₄N₂O₂, the atoms in the carbazole unit deviate from planarity [maximum deviation from mean plane = 0.1018 (8) Å]. The pyrrole ring makes dihedral angles of 4.44 (5), 3.84 (5), 2.18 (5) and 56.44 (5)° with the pyran, fused benzene rings and phenyl ring, respectively. In the crystal, pairs of N—H⋯O hydrogen bonds generate R ₂ ²(14) loops and a C—H⋯N interaction is also found. Molecules are further linked by a number of π–π interactions [centroid–centroid distances vary from 3.5702 (5) to 3.7068 (6) Å], forming a three-dimensional network.

Related literature

For a related structure, see: Sridharan et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₃H₁₄N₂O₂
M _r = 350.36
Monoclinic,
a = 7.8659 (1) Å
b = 8.5151 (1) Å
c = 25.1137 (4) Å
β = 98.133 (2)°
V = 1665.17 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 123 K
0.46 × 0.41 × 0.29 mm

Data collection

Agilent Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.978, T _max = 1.000
27185 measured reflections
8485 independent reflections
7184 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.154
S = 1.16
8485 reflections
249 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL2013 and PLATON.

Supplementary Material

Click here for additional data file.^{(20.9KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813011823/sj5318sup1.cif

e-69-0o831-sup1.cif^{(20.9KB, cif)}

Click here for additional data file.^{(464.8KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813011823/sj5318Isup2.hkl

e-69-0o831-Isup2.hkl^{(464.8KB, hkl)}

Click here for additional data file.^{(4.7KB, cdx)}

Supplementary material file. DOI: 10.1107/S1600536813011823/sj5318Isup3.cdx

Click here for additional data file.^{(6.7KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813011823/sj5318Isup4.cml

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
N11—H11⋯O2ⁱ	0.874 (18)	2.095 (19)	2.9561 (11)	168.2 (15)
C43—H43⋯N31ⁱⁱ	0.95	2.56	3.3130 (17)	136

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

Acknowledgments

RJB acknowledges the NSF–MRI program (grant No. CHE0619278) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

Comment

The title compound has been analysed as part of our crystallographic studies on pyranocarbazoles. Sridharan et al. (2009), have reported the synthesis and X-ray crystal structure of a related pyranocarbazole.

In the title molecule (Scheme I, Fig. 1), C₂₃H₁₄N₂O₂, the atoms in the carbazole unit deviate from planarity [maximum deviation from mean plane = -0.1018 (8) Å for atom C4A]. The pyrrole ring makes dihedral angles of 4.44 (5), 3.84 (5), 2.18 (5) and 56.44 (5)° with the pyran, fused benzene rings and phenyl ring, respectively.

Intermolecular N11—H11···O2 hydrogen bonds form a R²₂(14) (Bernstein et al., 1995) ring in the crystal structure and a C43—H43···N31 interaction is also found (Table 1, Fig. 2). Molecules are further linked by five π-π [Cg1—Cg4ⁱ = 3.7068 (6), Cg2—Cg4ⁱⁱ = Cg4—Cg2ⁱⁱⁱ = 3.5702 (5), Cg4—Cg1ⁱ = 3.7067 (6) and Cg4—Cg4ⁱ = 3.5927 (6) Å, symmetry code (i): 1 - x, 2 - y, - z, (ii): 1 + x, y, z, (iii): - 1 + x, y, z where Cg1, Cg2 and Cg4 are the centroids of the pyrrole (N11/C11A/C6A/C6B/C10A), pyran (O1/C2/C3/C4/C4A/C11B) and benzene (C6B/C7—C10/C10A) rings, respectively (Fig. 3)] interactions to form a three-dimensional network.

Experimental

A mixture of benzaldehyde (0.106 g, 1 mmol), malononitrile (0.080 g, 1.2 mmol), 8-methyl-9H-carbazol-1-ol (0.197 g, 1 mmol) and NaHCO₃ (0.084 g, 2 mmol) was ground at room temperature with the mortar and pestle. The reaction was monitored by TLC. After the completion of the reaction, the mixture was poured into water and then filtered. The obtained crude product was purified by silica gel column chromatography using petroleum ether: ethyl acetate (98:2) yielded the title compound (0.308 g, 88%). Then this pure compound was recrystallized from EtOAc.