4-(Dec­yloxy)phenyl 2-oxo-7-trifluoro­methyl-2H-chromene-3-carboxyl­ate

B S Palakshamurthy; H C Devarajegowda; H T Srinivasa; S Sreenivasa; Vijithkumar

doi:10.1107/S1600536813008222

. 2013 Mar 28;69(Pt 4):o621–o622. doi: 10.1107/S1600536813008222

4-(Decyloxy)phenyl 2-oxo-7-trifluoromethyl-2H-chromene-3-carboxylate

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

PMCID: PMC3629656 PMID: 23634143

Abstract

The title compound, C₂₇H₂₉F₃O₅, is a liquid crystal (LC) and exhibits enantiotropic SmA phase transitions. In the crystal, the dihedral angle between the 2H-chromene ring system and the benzene ring is 62.97 (2)°. The three F atoms of the –CF₃ group are disordered over two sets of sites with occupancy factors 0.71 (4):0.29 (4). In the crystal, pairs of C—H⋯O hydrogen bonds form inversion dimers and generate R ₂ ²(10) rings. The structure also features C—H⋯F and C—H⋯π interactions along [100] and [010], respectively.

Related literature

For the synthesis and liquid crystal behaviour of the title compound, see: Mahadevan et al. (2013 ▶). For the biological activity of coumarins and their derivatives, see: Borges et al. (2005 ▶); Kontogiorgis & Hadjipavlou-Litina (2005 ▶) and for their industrial applications, see: Hejchman et al. (2011 ▶). For the structure of 4-(octyloxy)phenyl 2-oxo-2H-chromene-3-carboxylate, see: Palakshamurthy et al. (2013 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₇H₂₉F₃O₅
M _r = 490.50
Monoclinic,
a = 27.85 (3) Å
b = 9.281 (10) Å
c = 9.981 (11) Å
β = 94.849 (18)°
V = 2571 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 99 K
0.52 × 0.42 × 0.40 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T _min = 0.950, T _max = 0.961
21163 measured reflections
4448 independent reflections
2547 reflections with I > 2σ(I)
R _int = 0.073

Refinement

R[F ² > 2σ(F ²)] = 0.084
wR(F ²) = 0.221
S = 1.07
4448 reflections
344 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: APEX2 and SAINT-Plus (Bruker, 2009 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2009 ▶); 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 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Click here for additional data file.^{(31.1KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813008222/sj5309sup1.cif

e-69-0o621-sup1.cif^{(31.1KB, cif)}

Click here for additional data file.^{(217.9KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813008222/sj5309Isup2.hkl

e-69-0o621-Isup2.hkl^{(217.9KB, hkl)}

Click here for additional data file.^{(9.3KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813008222/sj5309Isup3.cml

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

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

Cg1 and Cg2 are the centroids of the C2–C7 and C12–C17 rings respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O3ⁱ	0.95	2.56	3.396 (5)	146
C27—H27C⋯F1ⁱⁱ	0.98	2.52	3.432 (13)	154
C6—H6⋯Cg2ⁱ	0.95	3.09	3.899	144
C16—H16⋯Cg2ⁱⁱⁱ	0.95	3.33	4.120	142
C3—H3⋯Cg1^iv	0.95	3.43	4.325	163

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

Acknowledgments

The authors thank Professor T. N. Guru Row, Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore, and G. B. Sadananda, Department of Studies and Research in Physics, U·C.S. Tumkur University, Tumkur.

supplementary crystallographic information

Comment

The title compound is a liquid crystal (LC) exhibiting enantiotropic SmA phase transitions at 203.9(22.64) on heating and at 135.1(47.57) on cooling [The transition temperature in °C and the associated enthalpy values in kJ mol^-1 (in italics)] (Mahadevan et al., 2013).

Organic compounds with a 2H-chromene ring system and their derivatives display a wide range of biological activities such as antiviral (Borges et al.., 2005) and anti-inflammatory (Kontogiorgis et al., 2005) activity. They also display photochemical and photophysical properties, acting as molecular fluorescent sensors, laser dyes and have many industrial applications (Hejchman et al., 2011). Keeping this in mind we report here the structure of the 4-(decyloxy)phenyl 7-(trifluoromethyl)-2-oxo-2H-chromene-3-carboxylate(I), and its comparision with 4-(octyloxy)phenyl 2-oxo-2H-chromene-3 –carboxylate(II) (Palakshamurthy et al., 2013).

The asymmetric unit of 4-(decyloxy)phenyl 7-(trifluoromethyl)-2-oxo-2H-chromene-3-carboxylate is shown in Fig.1. The three F atoms of the –CF₃ group are disordered over two sets of sites with occupancy factors 0.71 (4):0.29 (4). The dihedral angles between the 2H-chromene ring and the benzene ring are 62.97 (2)^o and 21.11 (1)° in the compounds I and II respectively. The crystal structure is characterized by intermolecular C10—H10···O3 hydrogen bonds that form inversion dimers and generate a R²₂(10) ring pattern (Bernstein et al., 1995). C27—H27···F1 hydrogen bonds then link the dimers into chains along a . The structure is further stabilized by C3—H3···Cg1, C6—H6···Cg2 and C16—H16···Cg2 interactions, Table 1.

Experimental

A mixture of 7-(trifluoromethyl)-2-oxo-2H-chromene-3-carboxylic acid (0.100 g, 0.1 mmol), 4-(decyloxy) phenol (0.100 g, 0.1 mmol) dicyclohexylcarbodiimide (DCC) (0.100 g, 0.1 mmol) and catalytic quantity of DMAP (N,N-dimethyl amino pyridine) were stirred at room temperature for 48hrs in dry dichloromethane. Progress of the reaction was monitored by TLC (ethyl acetate: pet ether 2:8). After the completion of the reaction, the reaction mass was diluted with water and extracted into dichloromethane (25 ml). The organic layer was washed with water and dried over anhydrous sodium sulfate. The crude product thus obtained was purified by column chromatography using ethyl acetate: petroleum ether (2:8) as eluent followed by recrystallization from ethanol. A single crystal suitable for X-ray diffraction was grown from ethanol.