4-(Dec-yloxy)phenyl 2-oxo-7-trifluoro-methyl-2H-chromene-3-carboxyl-ate.

The title compound, C27H29F3O5, is a liquid crystal (LC) and exhibits enanti-otropic 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 inter-actions 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 = 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

Δρmax = 0.18 e Å−3

Δρmin = −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.

Click here for additional data file.

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

Click here for additional data file.

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

Click here for additional data file.

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

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

C27H29F3O5	prism
Mr = 490.50	Dx = 1.267 Mg m−3
Monoclinic, P21/c	Melting point: 418 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 27.85 (3) Å	Cell parameters from 2547 reflections
b = 9.281 (10) Å	θ = 2.2–25°
c = 9.981 (11) Å	µ = 0.10 mm−1
β = 94.849 (18)°	T = 99 K
V = 2571 (5) Å3	Prism, colourless
Z = 4	0.52 × 0.42 × 0.40 mm
F(000) = 1032

Bruker APEXII diffractometer	4448 independent reflections
Radiation source: fine-focus sealed tube	2547 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.073
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −33→33
Tmin = 0.950, Tmax = 0.961	k = −11→11
21163 measured reflections	l = −11→11

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.084	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.221	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0928P)2 + 0.7006P] where P = (Fo2 + 2Fc2)/3
4448 reflections	(Δ/σ)max = 0.004
344 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.17 e Å−3
0 constraints

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq	Occ. (<1)
C25	1.0692 (2)	0.6151 (7)	−0.3351 (7)	0.150 (2)
H25A	1.0867	0.6580	−0.2543	0.179*
H25B	1.0716	0.5093	−0.3241	0.179*
C24	1.0184 (2)	0.6518 (7)	−0.3292 (7)	0.153 (2)
H24A	1.0162	0.7579	−0.3381	0.184*
H24B	1.0012	0.6110	−0.4113	0.184*
C2	0.31670 (15)	0.6261 (4)	0.2849 (4)	0.0741 (11)
C1	0.26593 (19)	0.6458 (7)	0.3228 (6)	0.0935 (13)
C27	1.1456 (2)	0.6184 (9)	−0.4560 (9)	0.208 (4)
H27A	1.1556	0.6545	−0.5417	0.312*
H27B	1.1502	0.5138	−0.4514	0.312*
H27C	1.1652	0.6643	−0.3816	0.312*
C26	1.0960 (3)	0.6514 (10)	−0.4462 (8)	0.213 (4)
H26A	1.0783	0.6082	−0.5265	0.256*
H26B	1.0931	0.7571	−0.4572	0.256*
F1	0.2363 (3)	0.694 (2)	0.2215 (10)	0.137 (6)	0.71 (4)
F2	0.2468 (5)	0.5236 (12)	0.361 (3)	0.159 (9)	0.71 (4)
F3	0.2620 (2)	0.739 (2)	0.4226 (19)	0.145 (8)	0.71 (4)
F1A	0.2625 (6)	0.621 (7)	0.450 (2)	0.154 (19)	0.29 (4)
F2A	0.2343 (8)	0.556 (5)	0.269 (5)	0.147 (17)	0.29 (4)
F3A	0.2475 (14)	0.766 (3)	0.303 (7)	0.18 (3)	0.29 (4)
O1	0.43973 (9)	0.6693 (2)	0.4333 (2)	0.0641 (7)
O4	0.57932 (9)	0.6725 (3)	0.2856 (2)	0.0709 (7)
C10	0.46005 (13)	0.5620 (3)	0.1853 (3)	0.0632 (10)
H10	0.4667	0.5224	0.1011	0.076*
C5	0.41071 (13)	0.5803 (3)	0.2142 (3)	0.0589 (9)
O2	0.51778 (10)	0.6830 (3)	0.4977 (2)	0.0840 (8)
C3	0.35544 (15)	0.6606 (4)	0.3744 (4)	0.0694 (10)
H3	0.3503	0.7004	0.4597	0.083*
C8	0.48791 (14)	0.6551 (3)	0.4068 (3)	0.0577 (9)
C4	0.40217 (13)	0.6371 (3)	0.3396 (3)	0.0576 (9)
C9	0.49690 (13)	0.5990 (3)	0.2735 (3)	0.0551 (8)
O3	0.55682 (9)	0.4843 (3)	0.1529 (3)	0.0868 (9)
C6	0.37051 (14)	0.5468 (4)	0.1238 (4)	0.0765 (11)
H6	0.3755	0.5086	0.0378	0.092*
C11	0.54679 (13)	0.5768 (4)	0.2315 (3)	0.0611 (9)
C7	0.32407 (15)	0.5687 (4)	0.1581 (4)	0.0843 (12)
H7	0.2973	0.5451	0.0965	0.101*
C12	0.62703 (14)	0.6568 (4)	0.2462 (4)	0.0668 (10)
C17	0.64238 (15)	0.7362 (4)	0.1429 (4)	0.0784 (11)
H17	0.6206	0.8001	0.0944	0.094*
C15	0.72109 (15)	0.6315 (5)	0.1777 (5)	0.0847 (12)
C16	0.68960 (15)	0.7248 (4)	0.1077 (4)	0.0831 (12)
H16	0.7000	0.7809	0.0360	0.100*
O5	0.76854 (11)	0.6082 (4)	0.1512 (4)	0.1166 (11)
C13	0.65845 (18)	0.5638 (5)	0.3158 (4)	0.0971 (14)
H13	0.6480	0.5083	0.3878	0.117*
C14	0.70536 (18)	0.5511 (6)	0.2811 (5)	0.1108 (16)
H14	0.7269	0.4863	0.3292	0.133*
C19	0.83692 (17)	0.6115 (6)	0.0247 (5)	0.1171 (17)
H19A	0.8573	0.6386	0.1070	0.141*
H19B	0.8350	0.5050	0.0225	0.141*
C18	0.78703 (16)	0.6698 (5)	0.0363 (5)	0.1025 (15)
H18A	0.7882	0.7760	0.0450	0.123*
H18B	0.7659	0.6451	−0.0453	0.123*
C20	0.86150 (18)	0.6598 (6)	−0.0933 (6)	0.1232 (18)
H20A	0.8609	0.7665	−0.0952	0.148*
H20B	0.8425	0.6257	−0.1754	0.148*
C23	0.99056 (18)	0.6129 (7)	−0.2183 (6)	0.134 (2)
H23A	1.0081	0.6518	−0.1357	0.161*
H23B	0.9920	0.5066	−0.2107	0.161*
C21	0.91271 (18)	0.6116 (7)	−0.1003 (6)	0.1294 (19)
H21A	0.9313	0.6457	−0.0174	0.155*
H21B	0.9128	0.5050	−0.0969	0.155*
C22	0.9393 (2)	0.6543 (7)	−0.2135 (6)	0.137 (2)
H22A	0.9377	0.7607	−0.2197	0.165*
H22B	0.9216	0.6160	−0.2960	0.165*

	U11	U22	U33	U12	U13	U23
C25	0.088 (4)	0.175 (6)	0.191 (6)	0.014 (4)	0.044 (4)	0.019 (5)
C24	0.103 (4)	0.190 (6)	0.172 (6)	0.028 (4)	0.051 (4)	0.016 (5)
C2	0.076 (3)	0.068 (2)	0.081 (3)	0.002 (2)	0.025 (2)	0.011 (2)
C1	0.090 (4)	0.099 (4)	0.095 (4)	0.004 (3)	0.026 (3)	0.011 (3)
C27	0.108 (5)	0.243 (9)	0.282 (10)	0.012 (5)	0.066 (6)	0.009 (8)
C26	0.137 (7)	0.279 (10)	0.235 (9)	0.037 (6)	0.088 (6)	0.023 (8)
F1	0.097 (4)	0.197 (15)	0.118 (6)	0.045 (6)	0.021 (4)	0.027 (6)
F2	0.103 (8)	0.120 (6)	0.26 (2)	0.014 (5)	0.083 (12)	0.075 (10)
F3	0.094 (4)	0.190 (15)	0.158 (11)	0.008 (6)	0.043 (5)	−0.069 (11)
F1A	0.106 (11)	0.25 (5)	0.117 (13)	0.009 (18)	0.061 (9)	0.032 (18)
F2A	0.083 (10)	0.15 (3)	0.21 (3)	−0.011 (12)	0.038 (14)	−0.03 (2)
F3A	0.18 (2)	0.12 (2)	0.27 (6)	0.079 (18)	0.10 (4)	0.07 (3)
O1	0.0811 (17)	0.0674 (15)	0.0456 (13)	0.0026 (12)	0.0160 (12)	−0.0070 (11)
O4	0.0756 (17)	0.0752 (16)	0.0639 (15)	−0.0077 (13)	0.0181 (12)	−0.0240 (13)
C10	0.083 (3)	0.067 (2)	0.0423 (19)	−0.0066 (18)	0.0218 (19)	−0.0059 (16)
C5	0.072 (2)	0.059 (2)	0.0467 (19)	−0.0125 (17)	0.0157 (18)	−0.0017 (15)
O2	0.089 (2)	0.115 (2)	0.0480 (14)	0.0021 (16)	0.0037 (14)	−0.0223 (14)
C3	0.086 (3)	0.064 (2)	0.061 (2)	0.004 (2)	0.025 (2)	0.0030 (17)
C8	0.078 (3)	0.0537 (19)	0.0421 (19)	0.0018 (17)	0.0112 (18)	−0.0019 (15)
C4	0.076 (2)	0.0484 (18)	0.050 (2)	−0.0019 (16)	0.0143 (18)	0.0045 (15)
C9	0.077 (2)	0.0517 (18)	0.0377 (18)	−0.0050 (16)	0.0124 (17)	−0.0009 (14)
O3	0.0876 (19)	0.0923 (19)	0.0828 (18)	−0.0046 (15)	0.0212 (15)	−0.0405 (15)
C6	0.081 (3)	0.091 (3)	0.060 (2)	−0.017 (2)	0.019 (2)	−0.006 (2)
C11	0.080 (3)	0.062 (2)	0.0414 (18)	−0.0022 (19)	0.0086 (17)	−0.0041 (16)
C7	0.078 (3)	0.102 (3)	0.074 (3)	−0.013 (2)	0.011 (2)	−0.001 (2)
C12	0.071 (2)	0.070 (2)	0.059 (2)	0.002 (2)	0.0062 (19)	−0.0184 (19)
C17	0.078 (3)	0.072 (2)	0.086 (3)	0.002 (2)	0.011 (2)	0.004 (2)
C15	0.069 (3)	0.096 (3)	0.090 (3)	0.002 (2)	0.012 (2)	−0.013 (3)
C16	0.070 (3)	0.081 (3)	0.100 (3)	−0.005 (2)	0.017 (2)	0.005 (2)
O5	0.076 (2)	0.146 (3)	0.129 (3)	0.0163 (19)	0.013 (2)	0.006 (2)
C13	0.105 (4)	0.118 (4)	0.070 (3)	0.015 (3)	0.019 (2)	0.016 (3)
C14	0.094 (4)	0.144 (4)	0.096 (3)	0.037 (3)	0.011 (3)	0.018 (3)
C19	0.067 (3)	0.150 (5)	0.135 (4)	0.004 (3)	0.016 (3)	0.000 (4)
C18	0.077 (3)	0.105 (3)	0.128 (4)	−0.007 (3)	0.026 (3)	−0.015 (3)
C20	0.085 (3)	0.138 (4)	0.151 (5)	0.009 (3)	0.035 (3)	−0.007 (4)
C23	0.077 (3)	0.161 (5)	0.166 (5)	0.012 (3)	0.028 (3)	0.015 (4)
C21	0.076 (3)	0.160 (5)	0.154 (5)	0.011 (3)	0.022 (3)	0.013 (4)
C22	0.091 (4)	0.171 (5)	0.154 (5)	0.020 (4)	0.036 (4)	0.003 (4)

C25—C26	1.429 (8)	C9—C11	1.499 (5)
C25—C24	1.460 (8)	O3—C11	1.212 (4)
C25—H25A	0.9900	C6—C7	1.381 (5)
C25—H25B	0.9900	C6—H6	0.9500
C24—C23	1.451 (7)	C7—H7	0.9500
C24—H24A	0.9900	C12—C17	1.365 (5)
C24—H24B	0.9900	C12—C13	1.375 (5)
C2—C3	1.379 (5)	C17—C16	1.394 (5)
C2—C7	1.404 (5)	C17—H17	0.9500
C2—C1	1.506 (6)	C15—C14	1.375 (6)
C1—F3A	1.234 (17)	C15—C16	1.380 (6)
C1—F1A	1.300 (18)	C15—O5	1.387 (5)
C1—F2A	1.30 (2)	C16—H16	0.9500
C1—F2	1.323 (11)	O5—C18	1.417 (5)
C1—F1	1.329 (9)	C13—C14	1.385 (6)
C1—F3	1.332 (9)	C13—H13	0.9500
C27—C26	1.426 (9)	C14—H14	0.9500
C27—H27A	0.9800	C19—C20	1.481 (7)
C27—H27B	0.9800	C19—C18	1.505 (6)
C27—H27C	0.9800	C19—H19A	0.9900
C26—H26A	0.9900	C19—H19B	0.9900
C26—H26B	0.9900	C18—H18A	0.9900
O1—C4	1.376 (4)	C18—H18B	0.9900
O1—C8	1.396 (4)	C20—C21	1.502 (7)
O4—C11	1.349 (4)	C20—H20A	0.9900
O4—C12	1.425 (4)	C20—H20B	0.9900
C10—C9	1.339 (5)	C23—C22	1.482 (7)
C10—C5	1.438 (5)	C23—H23A	0.9900
C10—H10	0.9500	C23—H23B	0.9900
C5—C4	1.397 (4)	C21—C22	1.458 (7)
C5—C6	1.412 (5)	C21—H21A	0.9900
O2—C8	1.206 (4)	C21—H21B	0.9900
C3—C4	1.392 (5)	C22—H22A	0.9900
C3—H3	0.9500	C22—H22B	0.9900
C8—C9	1.469 (4)
C26—C25—C24	123.3 (7)	C10—C9—C11	117.2 (3)
C26—C25—H25A	106.5	C8—C9—C11	122.3 (3)
C24—C25—H25A	106.5	C7—C6—C5	121.2 (4)
C26—C25—H25B	106.5	C7—C6—H6	119.4
C24—C25—H25B	106.5	C5—C6—H6	119.4
H25A—C25—H25B	106.5	O3—C11—O4	122.8 (3)
C23—C24—C25	123.7 (6)	O3—C11—C9	123.3 (3)
C23—C24—H24A	106.4	O4—C11—C9	113.9 (3)
C25—C24—H24A	106.4	C6—C7—C2	119.4 (4)
C23—C24—H24B	106.4	C6—C7—H7	120.3
C25—C24—H24B	106.4	C2—C7—H7	120.3
H24A—C24—H24B	106.5	C17—C12—C13	119.6 (4)
C3—C2—C7	120.4 (4)	C17—C12—O4	120.8 (3)
C3—C2—C1	120.6 (4)	C13—C12—O4	119.6 (4)
C7—C2—C1	119.0 (4)	C12—C17—C16	120.8 (4)
F3A—C1—F1A	104.7 (15)	C12—C17—H17	119.6
F3A—C1—F2A	104.9 (19)	C16—C17—H17	119.6
F1A—C1—F2A	100.8 (14)	C14—C15—C16	119.4 (4)
F3A—C1—F2	130.3 (12)	C14—C15—O5	115.4 (4)
F1A—C1—F2	60.1 (18)	C16—C15—O5	125.2 (4)
F2A—C1—F2	44.9 (18)	C15—C16—C17	119.5 (4)
F3A—C1—F1	50 (3)	C15—C16—H16	120.2
F1A—C1—F1	135.3 (10)	C17—C16—H16	120.2
F2A—C1—F1	63 (2)	C15—O5—C18	120.6 (4)
F2—C1—F1	105.6 (10)	C12—C13—C14	120.1 (4)
F3A—C1—F3	58 (3)	C12—C13—H13	120.0
F1A—C1—F3	51 (2)	C14—C13—H13	120.0
F2A—C1—F3	129.4 (10)	C15—C14—C13	120.6 (4)
F2—C1—F3	106.4 (8)	C15—C14—H14	119.7
F1—C1—F3	105.3 (7)	C13—C14—H14	119.7
F3A—C1—C2	117.1 (10)	C20—C19—C18	116.3 (5)
F1A—C1—C2	111.8 (10)	C20—C19—H19A	108.2
F2A—C1—C2	115.8 (9)	C18—C19—H19A	108.2
F2—C1—C2	112.2 (6)	C20—C19—H19B	108.2
F1—C1—C2	112.7 (5)	C18—C19—H19B	108.2
F3—C1—C2	113.9 (6)	H19A—C19—H19B	107.4
C26—C27—H27A	109.5	O5—C18—C19	108.5 (4)
C26—C27—H27B	109.5	O5—C18—H18A	110.0
H27A—C27—H27B	109.5	C19—C18—H18A	110.0
C26—C27—H27C	109.5	O5—C18—H18B	110.0
H27A—C27—H27C	109.5	C19—C18—H18B	110.0
H27B—C27—H27C	109.5	H18A—C18—H18B	108.4
C27—C26—C25	125.2 (8)	C19—C20—C21	116.8 (5)
C27—C26—H26A	106.0	C19—C20—H20A	108.1
C25—C26—H26A	106.0	C21—C20—H20A	108.1
C27—C26—H26B	106.0	C19—C20—H20B	108.1
C25—C26—H26B	106.0	C21—C20—H20B	108.1
H26A—C26—H26B	106.3	H20A—C20—H20B	107.3
C4—O1—C8	122.6 (3)	C24—C23—C22	122.6 (5)
C11—O4—C12	115.6 (3)	C24—C23—H23A	106.7
C9—C10—C5	122.1 (3)	C22—C23—H23A	106.7
C9—C10—H10	119.0	C24—C23—H23B	106.7
C5—C10—H10	119.0	C22—C23—H23B	106.7
C4—C5—C6	118.0 (3)	H23A—C23—H23B	106.6
C4—C5—C10	117.5 (3)	C22—C21—C20	120.2 (5)
C6—C5—C10	124.5 (3)	C22—C21—H21A	107.3
C2—C3—C4	119.9 (3)	C20—C21—H21A	107.3
C2—C3—H3	120.0	C22—C21—H21B	107.3
C4—C3—H3	120.0	C20—C21—H21B	107.3
O2—C8—O1	116.8 (3)	H21A—C21—H21B	106.9
O2—C8—C9	126.7 (3)	C21—C22—C23	120.6 (5)
O1—C8—C9	116.4 (3)	C21—C22—H22A	107.2
O1—C4—C3	118.0 (3)	C23—C22—H22A	107.2
O1—C4—C5	120.9 (3)	C21—C22—H22B	107.2
C3—C4—C5	121.1 (4)	C23—C22—H22B	107.2
C10—C9—C8	120.4 (3)	H22A—C22—H22B	106.8

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···Cg1iv	0.95	3.43	4.325	163

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⋯Cg1iv	0.95	3.43	4.325	163

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