Crystal structure of 4-bromo­phenyl-2-oxo-2H-chromene-3-carboxyl­ate

H C Devarajegowda; P A Suchetan; H T Srinivasa; S Sreenivasa; B S Palakshamurthy

doi:10.1107/S2056989015006738

. 2015 Apr 22;71(Pt 5):o326–o327. doi: 10.1107/S2056989015006738

Crystal structure of 4-bromophenyl-2-oxo-2H-chromene-3-carboxylate

H C Devarajegowda ^a, P A Suchetan ^b, H T Srinivasa ^c, S Sreenivasa ^d, B S Palakshamurthy ^a,^*

PMCID: PMC4420041 PMID: 25995930

Abstract

In the title compound, C₁₆H₉BrO₄, the coumarin ring system is approximately planar, with an r.m.s deviation of the ten fitted non-H atoms of 0.031 Å, and forms a dihedral angle of 25.85 (10)° with the bromobenzene ring. The carbonyl atoms are syn. In the crystal, molecules are connected along [001] via C—H⋯O interactions, forming C(6) chains. Neighbouring C(6) chains are connected via several π–π interactions [range of centroid–centroid distances = 3.7254 (15)–3.7716 (16) Å], leading to sheets propagating in the bc plane.

Keywords: crystal structure, 2-oxo-2H-chromene, hydrogen bonding, π–π interactions

Related literature

For related structures, see: Sreenivasa et al. (2013 ▸); Palakshamurthy, Sreenivasa et al. (2013 ▸); Palakshamurthy, Devarajegowda et al. (2013 ▸); Devarajegowda et al. (2013 ▸). For the biological activity and other applications of 2-oxo-2H-chromene derivatives, see: Abdel-Aziz et al. (2013 ▸); Kostova (2006 ▸); Chandrasekharan & Kelly (2002 ▸).

Experimental

Crystal data

C₁₆H₉BrO₄
M _r = 345.14
Monoclinic,
a = 16.0782 (10) Å
b = 7.2618 (4) Å
c = 12.7396 (8) Å
β = 113.311 (4)°
V = 1366.01 (15) Å³
Z = 4
Mo Kα radiation
μ = 3.02 mm⁻¹
T = 296 K
0.24 × 0.18 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ▸) T _min = 0.526, T _max = 0.617
20483 measured reflections
2395 independent reflections
1831 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.079
S = 1.01
2395 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: APEX2 (Bruker, 2013 ▸); cell refinement: SAINT (Bruker, 2013 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL2014.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015006738/tk5362sup1.cif

e-71-0o326-sup1.cif^{(732KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015006738/tk5362Isup2.hkl

e-71-0o326-Isup2.hkl^{(131.7KB, hkl)}

Click here for additional data file.^{(4.9KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015006738/tk5362Isup3.cml

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989015006738/tk5362fig1.tif

The molecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.^{(1.1MB, tif)}

via . DOI: 10.1107/S2056989015006738/tk5362fig2.tif

The crystal packing of the title compound via C—H⋯O interactions along [001]. Hydrogen bonds are shown as dashed lines.

Click here for additional data file.^{(2MB, tif)}

. DOI: 10.1107/S2056989015006738/tk5362fig3.tif

Various π–π interactions observed in the crystal packing

CCDC reference: 1057743

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C12H12O3ⁱ	0.93	2.40	3.124(3)	134

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Symmetry code: (i) Inline graphic .

Acknowledgments

BSPM thanks the UGC–India for financial support under its Minor Research Project Scheme, and also acknowledges Mr Biraj, Tezpur University, Tezpur, for his help with the data collection.

supplementary crystallographic information

S1. Chemical context

Hetero cyclic compounds of 2-oxo-2H-chromenes display wide range of biological activities such as anti-HIV (Kostova, et al., 2006), anti-cancer (Abdel-Aziz et al.,2013), etc. They also play a significant role as chemical sensors, fluorescent probes and laser dyes (Chandrasekharan et al., 2002). In continuation of our work on 2-oxo-2H-chromene derivatives (Sreenivasa et al., 2013; Palakshamurthy, Sreenivasa et al., 2013; Palakshamurthy, Devarajegowda et al., 2013; Devarajegowda, et al.,2013), in the present work we report the synthesis and crystal structure of 4-bromophenyl-2-oxo-2H-chromene-3-carboxylate (I), an intermediate compound obtained during synthesis of coumarin–based Liquid Crystals (LCs).

S2. Structural commentary

The dihedral angle between the coumarin ring and the bromobenzene ring in (I) is 25.85 (10)°. Compared to this, the dihedral angle is 22.95 (11)° in 4'-cyanobiphenyl-4-yl-7-diethylamino-2-oxo-2H-chromene-3-carboxylate (II) (Sreenivasa et al., 2013), 62.97 (2)° in 4-(decyloxy)phenyl 2-oxo-7-trifluoromethyl-2H-chromene-3-carboxylate (III) (Palakshamurthy, Sreenivasa et al., 2013), 21.00 (1)° in 4-(octyloxy)phenyl 2-oxo-2H-chromene-3-carboxylate (IV) (Palakshamurthy, Devarajegowda et al., 2013) and 54.46 (17)° in 4-[4-(heptyloxy)benzoyloxy] phenyl 2-oxo-7-trifluoromethyl-2H-chromene-3-carboxylate (V) (Devarajegowda, et al., 2013). Further, in (I), the torsions C9—C8—C10—O3, O3—C10—O4—C11 and C12—C11—O4—C10 have values 27.6 (4), 6.3 (3) and 124.6 (2)°, respectively.

S3. Supramolecular features

In the crystal structure, the molecules are connected along [001] via C12—H12···O3 interactions forming C(6) chains (Fig 2., Table 2). Further, neighbouring C(6) chains are interlocked via π···π interactions (Fig. 3), namely, Cg1··· Cg3ⁱ [3.7254 (15) Å, i: 1-x, 1/2+y, 1/2-z] and Cg2··· Cg3^i,ii [3.7303 (16) and 3.7716 (16) Å, ii: 1-x, 1/2+y, 1/2-z], where Cg1, Cg2 and Cg3 are the centroids of the C6/C7/C8/C9/O1/C1, C1–C6 and C11–C16 rings, respectively). Overall, a two-dimensional architecture is observed in the bc plane.

S4. Synthesis and crystallization

Coumarin 3-carboxylic acid (1.0 mmol), 4-bromophenol (1.0 mmol) and a catalytic amount of N,N-dimethylaminopyrimidine (DMAP) were dissolved in anhydrous CH₂Cl₂. To this solution, a solution of dicyclohexylcarbodimide (DCC) in dried CH₂Cl₂ was added and stirred. After 24 h of stirring, dicyclohexylurea was filtered off and the solution was concentrated. The solid residue obtained was purified by column chromatography on silica gel using CHCl₃ as the eluent. Single crystals suitable for X-ray studies were grown by slow evaporation technique at room temperature using ethanol as the solvent.

S5. Refinement

The H atoms were positioned with idealized geometry using a riding model with C—H = 0.93Å, and with 1.2U_eq(C). Owing to poor agreement, several reflections, i.e. (0 2 5), (-1 0 2), (-2 0 8), (7 0 0) and (-7 2 5), were omitted from the final cycles of refinement.