Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805041917/ci6729sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805041917/ci6729Isup2.hkl |
CCDC reference: 296544
1-Bromopentane (4.53 g, 0.03 mol) in ethanol (30 ml) was added dropwise to a solution of 3-(4-hydroxy-3-methoxyphenyl)acrylic acid (1.94 g, 0.01 mol) in 17.0% KOH solution (10 ml). The mixture was refluxed for 24 h and extra KOH solution was added to remove the additional products. The mixture was then acidified to give a white precipitate, which was filtered and recrystallized from ethanol to obtain 3-(4-pentyloxyphenyl)acrylic acid. 3-(4-pentyloxyphenyl)acrylic acid (0.79 g) and 1,3-dicyclohexylcarbodiimide (0.62 g) were dissolved in tetrahydrofuran (THF, 20 ml) and a solution of 2-fluoro-4-hydroxybenzonitrile (0.68 g) and 4-dimethylaminopyridine (0.01 g) in THF (20 ml) was added. The mixture was stirred at room temperature for 24 h and then filtered. Colourless single crystals of (I) suitable for X-ray diffraction study were obtained by slow evaporation of a THF/ethanol (1:4 v/v) solution over a period of 2 d.
In both independent molecules, the F atom was found to be disordered over two positions, suggesting two different orientations for the 4-cyano-3-fluorobenzene ring. The occupancies of the disordered positions F1/F1' (and F2/F2') were refined to 0.791 (4)/0.209 (4). The C—F distances were restrained to be equal and the Uij components of the disordered atoms were approximated to isotropic behaviour. H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å and with Uiso(H) = 1.2–1.5Ueq(C).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
C22H22FNO4 | Z = 4 |
Mr = 383.41 | F(000) = 808 |
Triclinic, P1 | Dx = 1.255 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 12.193 (4) Å | Cell parameters from 1724 reflections |
b = 12.506 (4) Å | θ = 2.3–22.6° |
c = 14.449 (5) Å | µ = 0.09 mm−1 |
α = 82.348 (7)° | T = 293 K |
β = 68.816 (6)° | Plate, colourless |
γ = 83.036 (7)° | 0.41 × 0.18 × 0.09 mm |
V = 2029.7 (12) Å3 |
Simens SMART 1000 CCD area-detector diffractometer | 7827 independent reflections |
Radiation source: fine-focus sealed tube | 3944 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 8.33 pixels mm-1 | θmax = 26.1°, θmin = 1.5° |
ω scans | h = −13→15 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −15→14 |
Tmin = 0.963, Tmax = 0.992 | l = −9→17 |
11493 measured reflections |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.173 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0777P)2] where P = (Fo2 + 2Fc2)/3 |
7827 reflections | (Δ/σ)max = 0.001 |
524 parameters | Δρmax = 0.21 e Å−3 |
30 restraints | Δρmin = −0.18 e Å−3 |
C22H22FNO4 | γ = 83.036 (7)° |
Mr = 383.41 | V = 2029.7 (12) Å3 |
Triclinic, P1 | Z = 4 |
a = 12.193 (4) Å | Mo Kα radiation |
b = 12.506 (4) Å | µ = 0.09 mm−1 |
c = 14.449 (5) Å | T = 293 K |
α = 82.348 (7)° | 0.41 × 0.18 × 0.09 mm |
β = 68.816 (6)° |
Simens SMART 1000 CCD area-detector diffractometer | 7827 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3944 reflections with I > 2σ(I) |
Tmin = 0.963, Tmax = 0.992 | Rint = 0.020 |
11493 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 30 restraints |
wR(F2) = 0.173 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.21 e Å−3 |
7827 reflections | Δρmin = −0.18 e Å−3 |
524 parameters |
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) | |
F1 | −0.52447 (19) | 0.7156 (2) | 0.48049 (19) | 0.1228 (11) | 0.791 (4) |
F2 | 0.94123 (17) | 0.62599 (18) | −0.52135 (16) | 0.0909 (9) | 0.791 (4) |
F1' | −0.2424 (11) | 0.9091 (10) | 0.5023 (9) | 0.162 (5) | 0.209 (4) |
F2' | 0.6731 (8) | 0.3841 (7) | −0.4855 (7) | 0.105 (4) | 0.209 (4) |
O1 | −0.14351 (17) | 0.68708 (14) | 0.24252 (14) | 0.0765 (6) | |
O2 | −0.14778 (18) | 0.83171 (16) | 0.13515 (15) | 0.0866 (7) | |
O3 | 0.39423 (16) | 0.32152 (14) | −0.15097 (14) | 0.0718 (6) | |
O4 | 0.33680 (15) | 0.50914 (14) | −0.22390 (13) | 0.0696 (5) | |
O5 | 0.58363 (16) | 0.63792 (14) | −0.25299 (14) | 0.0755 (6) | |
O6 | 0.60108 (18) | 0.49287 (16) | −0.14967 (14) | 0.0854 (7) | |
O7 | 0.04807 (14) | 0.96600 (13) | 0.17973 (13) | 0.0639 (5) | |
O8 | 0.12322 (15) | 0.77764 (13) | 0.23663 (13) | 0.0642 (5) | |
N1 | −0.5416 (3) | 0.9028 (3) | 0.6432 (2) | 0.1282 (12) | |
N2 | 0.9559 (2) | 0.4219 (2) | −0.66425 (19) | 0.0937 (9) | |
C1 | −0.4744 (3) | 0.8693 (3) | 0.5734 (3) | 0.0881 (10) | |
C2 | −0.3888 (3) | 0.8262 (2) | 0.4865 (2) | 0.0698 (8) | |
C3 | −0.4164 (3) | 0.7495 (3) | 0.4403 (2) | 0.0768 (9) | |
H3 | −0.4925 | 0.7269 | 0.4661 | 0.092* | 0.209 (4) |
C4 | −0.3375 (3) | 0.7051 (2) | 0.3581 (2) | 0.0741 (8) | |
H4 | −0.3589 | 0.6533 | 0.3286 | 0.089* | |
C5 | −0.2264 (2) | 0.7390 (2) | 0.3207 (2) | 0.0622 (7) | |
C6 | −0.1935 (3) | 0.8152 (2) | 0.3630 (2) | 0.0816 (9) | |
H6 | −0.1174 | 0.8378 | 0.3366 | 0.098* | |
C7 | −0.2755 (3) | 0.8575 (3) | 0.4453 (3) | 0.0866 (10) | |
H7 | −0.2537 | 0.9093 | 0.4745 | 0.104* | 0.791 (4) |
C8 | −0.1052 (2) | 0.7432 (2) | 0.1501 (2) | 0.0609 (7) | |
C9 | −0.0117 (2) | 0.6812 (2) | 0.0793 (2) | 0.0623 (7) | |
H9 | 0.0206 | 0.7134 | 0.0145 | 0.075* | |
C10 | 0.0312 (2) | 0.5828 (2) | 0.09986 (19) | 0.0574 (7) | |
H10 | −0.0039 | 0.5519 | 0.1648 | 0.069* | |
C11 | 0.1264 (2) | 0.5158 (2) | 0.0343 (2) | 0.0572 (7) | |
C12 | 0.1855 (2) | 0.5483 (2) | −0.0660 (2) | 0.0566 (7) | |
H12 | 0.1643 | 0.6158 | −0.0931 | 0.068* | |
C13 | 0.2742 (2) | 0.4830 (2) | −0.1254 (2) | 0.0566 (7) | |
C14 | 0.3070 (2) | 0.3811 (2) | −0.0857 (2) | 0.0603 (7) | |
C15 | 0.2496 (2) | 0.3486 (2) | 0.0127 (2) | 0.0705 (8) | |
H15 | 0.2709 | 0.2811 | 0.0397 | 0.085* | |
C16 | 0.1602 (2) | 0.4152 (2) | 0.0724 (2) | 0.0701 (8) | |
H16 | 0.1223 | 0.3918 | 0.1391 | 0.084* | |
C17 | 0.4311 (2) | 0.2164 (2) | −0.1142 (2) | 0.0736 (8) | |
H17A | 0.3644 | 0.1723 | −0.0866 | 0.088* | |
H17B | 0.4612 | 0.2230 | −0.0618 | 0.088* | |
C18 | 0.5247 (3) | 0.1642 (2) | −0.1974 (2) | 0.0792 (9) | |
H18A | 0.5892 | 0.2108 | −0.2267 | 0.095* | |
H18B | 0.4930 | 0.1564 | −0.2486 | 0.095* | |
C19 | 0.5718 (2) | 0.0543 (2) | −0.1640 (2) | 0.0800 (9) | |
H19A | 0.5077 | 0.0071 | −0.1374 | 0.096* | |
H19B | 0.5996 | 0.0620 | −0.1104 | 0.096* | |
C20 | 0.6712 (3) | 0.0012 (3) | −0.2459 (3) | 0.1021 (12) | |
H20A | 0.6449 | −0.0029 | −0.3011 | 0.123* | |
H20B | 0.7372 | 0.0463 | −0.2699 | 0.123* | |
C21 | 0.7124 (3) | −0.1093 (3) | −0.2136 (4) | 0.1384 (18) | |
H21A | 0.7754 | −0.1384 | −0.2686 | 0.208* | |
H21B | 0.6482 | −0.1551 | −0.1914 | 0.208* | |
H21C | 0.7402 | −0.1058 | −0.1599 | 0.208* | |
C22 | 0.3033 (3) | 0.6103 (2) | −0.2692 (2) | 0.0785 (9) | |
H22A | 0.3533 | 0.6192 | −0.3381 | 0.118* | |
H22B | 0.3115 | 0.6682 | −0.2353 | 0.118* | |
H22C | 0.2227 | 0.6113 | −0.2648 | 0.118* | |
C23 | 0.8910 (3) | 0.4571 (2) | −0.5942 (2) | 0.0686 (8) | |
C24 | 0.8103 (2) | 0.5010 (2) | −0.50500 (18) | 0.0574 (7) | |
C25 | 0.8389 (2) | 0.5862 (2) | −0.4692 (2) | 0.0648 (8) | |
H25 | 0.9110 | 0.6152 | −0.5040 | 0.078* | 0.209 (4) |
C26 | 0.7662 (2) | 0.6297 (2) | −0.3852 (2) | 0.0682 (8) | |
H26 | 0.7879 | 0.6873 | −0.3626 | 0.082* | |
C27 | 0.6603 (2) | 0.5870 (2) | −0.33438 (19) | 0.0615 (7) | |
C28 | 0.6282 (2) | 0.5011 (2) | −0.3659 (2) | 0.0667 (8) | |
H28 | 0.5564 | 0.4722 | −0.3301 | 0.080* | |
C29 | 0.7032 (2) | 0.4584 (3) | −0.4510 (2) | 0.0687 (8) | |
H29 | 0.6820 | 0.4000 | −0.4727 | 0.082* | 0.791 (4) |
C30 | 0.5550 (2) | 0.5810 (2) | −0.1603 (2) | 0.0610 (7) | |
C31 | 0.4653 (2) | 0.6389 (2) | −0.0839 (2) | 0.0595 (7) | |
H31 | 0.4415 | 0.6058 | −0.0189 | 0.071* | |
C32 | 0.4146 (2) | 0.7361 (2) | −0.10010 (18) | 0.0533 (6) | |
H32 | 0.4424 | 0.7692 | −0.1649 | 0.064* | |
C33 | 0.3200 (2) | 0.79674 (19) | −0.02741 (18) | 0.0484 (6) | |
C34 | 0.26920 (19) | 0.75488 (18) | 0.07238 (18) | 0.0492 (6) | |
H34 | 0.2970 | 0.6870 | 0.0935 | 0.059* | |
C35 | 0.1793 (2) | 0.81224 (19) | 0.13930 (18) | 0.0496 (6) | |
C36 | 0.1371 (2) | 0.91545 (19) | 0.1079 (2) | 0.0518 (6) | |
C37 | 0.1868 (2) | 0.9575 (2) | 0.0103 (2) | 0.0601 (7) | |
H37 | 0.1601 | 1.0259 | −0.0108 | 0.072* | |
C38 | 0.2768 (2) | 0.8977 (2) | −0.05636 (19) | 0.0567 (7) | |
H38 | 0.3090 | 0.9264 | −0.1224 | 0.068* | |
C39 | −0.0018 (2) | 1.0693 (2) | 0.1512 (2) | 0.0745 (9) | |
H39A | −0.0302 | 1.0635 | 0.0975 | 0.089* | |
H39B | 0.0572 | 1.1216 | 0.1283 | 0.089* | |
C40 | −0.1019 (3) | 1.1042 (2) | 0.2411 (3) | 0.0863 (10) | |
H40A | −0.1604 | 1.0514 | 0.2618 | 0.104* | |
H40B | −0.1389 | 1.1727 | 0.2227 | 0.104* | |
C41 | −0.0657 (3) | 1.1170 (3) | 0.3290 (3) | 0.0978 (11) | |
H41A | −0.0297 | 1.0481 | 0.3478 | 0.117* | |
H41B | −0.0062 | 1.1688 | 0.3077 | 0.117* | |
C42 | −0.1646 (4) | 1.1536 (3) | 0.4192 (3) | 0.1199 (14) | |
H42A | −0.2268 | 1.1047 | 0.4387 | 0.144* | |
H42B | −0.1970 | 1.2252 | 0.4025 | 0.144* | |
C43 | −0.1239 (5) | 1.1571 (4) | 0.5065 (3) | 0.181 (2) | |
H43A | −0.1893 | 1.1815 | 0.5624 | 0.272* | |
H43B | −0.0629 | 1.2061 | 0.4877 | 0.272* | |
H43C | −0.0937 | 1.0860 | 0.5245 | 0.272* | |
C44 | 0.1620 (2) | 0.6734 (2) | 0.2716 (2) | 0.0725 (8) | |
H44A | 0.1165 | 0.6580 | 0.3410 | 0.109* | |
H44B | 0.2439 | 0.6720 | 0.2633 | 0.109* | |
H44C | 0.1517 | 0.6198 | 0.2342 | 0.109* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0607 (15) | 0.191 (3) | 0.106 (2) | −0.0397 (15) | 0.0060 (14) | −0.0493 (18) |
F2 | 0.0645 (14) | 0.1103 (17) | 0.0782 (16) | −0.0234 (11) | 0.0041 (11) | −0.0103 (13) |
F1' | 0.151 (8) | 0.156 (8) | 0.167 (9) | −0.047 (6) | −0.020 (7) | −0.044 (7) |
F2' | 0.102 (6) | 0.114 (6) | 0.088 (6) | −0.034 (5) | 0.000 (5) | −0.046 (5) |
O1 | 0.0819 (13) | 0.0599 (11) | 0.0585 (13) | 0.0139 (10) | 0.0017 (10) | 0.0016 (10) |
O2 | 0.0985 (15) | 0.0685 (13) | 0.0706 (14) | 0.0216 (11) | −0.0160 (12) | 0.0050 (11) |
O3 | 0.0666 (12) | 0.0677 (12) | 0.0683 (13) | 0.0103 (9) | −0.0118 (10) | −0.0112 (10) |
O4 | 0.0664 (12) | 0.0688 (12) | 0.0549 (12) | 0.0009 (9) | −0.0012 (10) | −0.0047 (10) |
O5 | 0.0777 (13) | 0.0683 (12) | 0.0495 (12) | 0.0123 (10) | 0.0078 (10) | −0.0024 (10) |
O6 | 0.0950 (15) | 0.0813 (14) | 0.0571 (13) | 0.0334 (12) | −0.0122 (11) | −0.0066 (11) |
O7 | 0.0600 (11) | 0.0568 (11) | 0.0645 (12) | 0.0152 (8) | −0.0133 (9) | −0.0123 (9) |
O8 | 0.0635 (11) | 0.0619 (11) | 0.0457 (11) | 0.0096 (9) | 0.0009 (9) | −0.0023 (9) |
N1 | 0.115 (3) | 0.154 (3) | 0.088 (2) | 0.018 (2) | −0.001 (2) | −0.040 (2) |
N2 | 0.0887 (19) | 0.116 (2) | 0.0536 (16) | 0.0006 (16) | 0.0039 (14) | −0.0191 (16) |
C1 | 0.087 (2) | 0.095 (2) | 0.064 (2) | 0.0111 (18) | −0.0086 (19) | −0.0137 (19) |
C2 | 0.067 (2) | 0.0685 (19) | 0.0610 (19) | 0.0070 (15) | −0.0122 (16) | −0.0039 (16) |
C3 | 0.0605 (19) | 0.099 (2) | 0.061 (2) | −0.0088 (17) | −0.0086 (16) | −0.0082 (18) |
C4 | 0.070 (2) | 0.088 (2) | 0.0605 (19) | −0.0057 (16) | −0.0158 (16) | −0.0158 (17) |
C5 | 0.0624 (18) | 0.0529 (16) | 0.0543 (17) | 0.0092 (13) | −0.0066 (14) | 0.0001 (14) |
C6 | 0.0660 (19) | 0.072 (2) | 0.086 (2) | −0.0110 (16) | 0.0017 (17) | −0.0111 (19) |
C7 | 0.088 (2) | 0.074 (2) | 0.089 (3) | −0.0131 (18) | −0.012 (2) | −0.0248 (19) |
C8 | 0.0592 (17) | 0.0611 (18) | 0.0551 (18) | −0.0030 (14) | −0.0133 (14) | −0.0020 (15) |
C9 | 0.0598 (17) | 0.0643 (17) | 0.0554 (18) | −0.0058 (14) | −0.0119 (14) | −0.0031 (14) |
C10 | 0.0528 (15) | 0.0654 (18) | 0.0492 (16) | −0.0085 (13) | −0.0108 (13) | −0.0058 (14) |
C11 | 0.0536 (16) | 0.0626 (17) | 0.0527 (17) | −0.0048 (13) | −0.0137 (14) | −0.0108 (14) |
C12 | 0.0506 (15) | 0.0573 (15) | 0.0581 (18) | −0.0056 (12) | −0.0141 (13) | −0.0062 (14) |
C13 | 0.0487 (15) | 0.0623 (17) | 0.0524 (17) | −0.0101 (13) | −0.0080 (13) | −0.0059 (14) |
C14 | 0.0507 (15) | 0.0664 (18) | 0.0592 (19) | −0.0002 (13) | −0.0126 (14) | −0.0132 (15) |
C15 | 0.0690 (19) | 0.0682 (18) | 0.064 (2) | 0.0073 (15) | −0.0159 (16) | −0.0042 (16) |
C16 | 0.0679 (18) | 0.078 (2) | 0.0530 (18) | 0.0012 (15) | −0.0108 (15) | −0.0012 (15) |
C17 | 0.0654 (18) | 0.074 (2) | 0.077 (2) | 0.0067 (15) | −0.0202 (16) | −0.0146 (17) |
C18 | 0.0689 (19) | 0.080 (2) | 0.083 (2) | 0.0107 (16) | −0.0210 (17) | −0.0211 (18) |
C19 | 0.0638 (18) | 0.0681 (19) | 0.105 (3) | 0.0021 (15) | −0.0259 (18) | −0.0160 (18) |
C20 | 0.093 (2) | 0.083 (2) | 0.128 (3) | 0.0194 (19) | −0.035 (2) | −0.036 (2) |
C21 | 0.098 (3) | 0.085 (3) | 0.229 (6) | 0.012 (2) | −0.050 (3) | −0.043 (3) |
C22 | 0.074 (2) | 0.087 (2) | 0.0597 (19) | 0.0043 (16) | −0.0133 (16) | 0.0053 (17) |
C23 | 0.0643 (18) | 0.084 (2) | 0.0468 (17) | −0.0026 (15) | −0.0084 (15) | −0.0026 (16) |
C24 | 0.0532 (16) | 0.0701 (18) | 0.0394 (15) | 0.0036 (13) | −0.0085 (13) | −0.0026 (14) |
C25 | 0.0489 (16) | 0.0770 (19) | 0.0499 (17) | −0.0066 (14) | 0.0018 (14) | 0.0044 (15) |
C26 | 0.0663 (18) | 0.0696 (18) | 0.0551 (18) | −0.0037 (14) | −0.0047 (15) | −0.0083 (15) |
C27 | 0.0585 (17) | 0.0623 (17) | 0.0437 (16) | 0.0081 (14) | −0.0015 (13) | 0.0045 (14) |
C28 | 0.0500 (16) | 0.078 (2) | 0.0571 (18) | −0.0044 (14) | −0.0038 (14) | −0.0004 (16) |
C29 | 0.0587 (18) | 0.084 (2) | 0.0514 (18) | −0.0009 (15) | −0.0071 (15) | −0.0043 (16) |
C30 | 0.0580 (16) | 0.0652 (18) | 0.0475 (17) | 0.0028 (14) | −0.0068 (13) | −0.0045 (14) |
C31 | 0.0561 (16) | 0.0659 (17) | 0.0461 (16) | 0.0034 (13) | −0.0082 (13) | −0.0055 (13) |
C32 | 0.0479 (14) | 0.0627 (16) | 0.0429 (15) | −0.0071 (12) | −0.0081 (12) | −0.0029 (13) |
C33 | 0.0447 (13) | 0.0511 (15) | 0.0467 (15) | −0.0036 (11) | −0.0119 (12) | −0.0072 (12) |
C34 | 0.0467 (14) | 0.0456 (14) | 0.0501 (16) | −0.0010 (11) | −0.0110 (12) | −0.0062 (12) |
C35 | 0.0457 (14) | 0.0517 (15) | 0.0456 (15) | −0.0006 (11) | −0.0092 (12) | −0.0076 (12) |
C36 | 0.0469 (14) | 0.0509 (15) | 0.0566 (17) | 0.0029 (11) | −0.0167 (13) | −0.0120 (13) |
C37 | 0.0638 (17) | 0.0516 (15) | 0.0613 (19) | 0.0047 (13) | −0.0218 (15) | −0.0024 (14) |
C38 | 0.0587 (16) | 0.0590 (16) | 0.0472 (16) | −0.0040 (13) | −0.0148 (13) | 0.0014 (13) |
C39 | 0.0765 (19) | 0.0641 (18) | 0.080 (2) | 0.0253 (15) | −0.0316 (17) | −0.0147 (16) |
C40 | 0.078 (2) | 0.074 (2) | 0.098 (3) | 0.0247 (16) | −0.025 (2) | −0.0232 (19) |
C41 | 0.100 (3) | 0.091 (2) | 0.094 (3) | 0.0089 (19) | −0.020 (2) | −0.035 (2) |
C42 | 0.145 (4) | 0.075 (2) | 0.104 (3) | 0.002 (2) | 0.001 (3) | −0.023 (2) |
C43 | 0.309 (7) | 0.137 (4) | 0.083 (3) | −0.008 (4) | −0.051 (4) | −0.024 (3) |
C44 | 0.0756 (19) | 0.0661 (18) | 0.0531 (18) | 0.0090 (15) | −0.0052 (15) | 0.0087 (14) |
F1—C3 | 1.330 (3) | C19—H19B | 0.97 |
F2—C25 | 1.320 (3) | C20—C21 | 1.487 (4) |
F1'—C7 | 1.305 (8) | C20—H20A | 0.97 |
F2'—C29 | 1.259 (6) | C20—H20B | 0.97 |
O1—C8 | 1.369 (3) | C21—H21A | 0.96 |
O1—C5 | 1.390 (3) | C21—H21B | 0.96 |
O2—C8 | 1.191 (3) | C21—H21C | 0.96 |
O3—C14 | 1.358 (3) | C22—H22A | 0.96 |
O3—C17 | 1.434 (3) | C22—H22B | 0.96 |
O4—C13 | 1.367 (3) | C22—H22C | 0.96 |
O4—C22 | 1.429 (3) | C23—C24 | 1.439 (4) |
O5—C30 | 1.375 (3) | C24—C25 | 1.376 (4) |
O5—C27 | 1.387 (3) | C24—C29 | 1.386 (4) |
O6—C30 | 1.192 (3) | C25—C26 | 1.355 (4) |
O7—C36 | 1.360 (3) | C25—H25 | 0.93 |
O7—C39 | 1.434 (3) | C26—C27 | 1.367 (4) |
O8—C35 | 1.359 (3) | C26—H26 | 0.93 |
O8—C44 | 1.424 (3) | C27—C28 | 1.370 (4) |
N1—C1 | 1.139 (4) | C28—C29 | 1.370 (4) |
N2—C23 | 1.140 (3) | C28—H28 | 0.93 |
C1—C2 | 1.432 (4) | C29—H29 | 0.93 |
C2—C3 | 1.375 (4) | C30—C31 | 1.445 (3) |
C2—C7 | 1.375 (4) | C31—C32 | 1.327 (3) |
C3—C4 | 1.366 (4) | C31—H31 | 0.93 |
C3—H3 | 0.93 | C32—C33 | 1.461 (3) |
C4—C5 | 1.362 (4) | C32—H32 | 0.93 |
C4—H4 | 0.93 | C33—C38 | 1.380 (3) |
C5—C6 | 1.367 (4) | C33—C34 | 1.403 (3) |
C6—C7 | 1.368 (4) | C34—C35 | 1.371 (3) |
C6—H6 | 0.93 | C34—H34 | 0.93 |
C7—H7 | 0.93 | C35—C36 | 1.410 (3) |
C8—C9 | 1.450 (3) | C36—C37 | 1.376 (4) |
C9—C10 | 1.318 (3) | C37—C38 | 1.386 (3) |
C9—H9 | 0.93 | C37—H37 | 0.93 |
C10—C11 | 1.458 (3) | C38—H38 | 0.93 |
C10—H10 | 0.93 | C39—C40 | 1.498 (4) |
C11—C16 | 1.383 (3) | C39—H39A | 0.97 |
C11—C12 | 1.394 (3) | C39—H39B | 0.97 |
C12—C13 | 1.369 (3) | C40—C41 | 1.520 (4) |
C12—H12 | 0.93 | C40—H40A | 0.97 |
C13—C14 | 1.400 (3) | C40—H40B | 0.97 |
C14—C15 | 1.368 (4) | C41—C42 | 1.501 (4) |
C15—C16 | 1.385 (3) | C41—H41A | 0.97 |
C15—H15 | 0.93 | C41—H41B | 0.97 |
C16—H16 | 0.93 | C42—C43 | 1.520 (6) |
C17—C18 | 1.487 (4) | C42—H42A | 0.97 |
C17—H17A | 0.97 | C42—H42B | 0.97 |
C17—H17B | 0.97 | C43—H43A | 0.96 |
C18—C19 | 1.511 (4) | C43—H43B | 0.96 |
C18—H18A | 0.97 | C43—H43C | 0.96 |
C18—H18B | 0.97 | C44—H44A | 0.96 |
C19—C20 | 1.513 (4) | C44—H44B | 0.96 |
C19—H19A | 0.97 | C44—H44C | 0.96 |
C8—O1—C5 | 118.4 (2) | O4—C22—H22C | 109.5 |
C14—O3—C17 | 117.9 (2) | H22A—C22—H22C | 109.5 |
C13—O4—C22 | 117.3 (2) | H22B—C22—H22C | 109.5 |
C30—O5—C27 | 118.3 (2) | N2—C23—C24 | 179.2 (3) |
C36—O7—C39 | 117.8 (2) | C25—C24—C29 | 117.6 (3) |
C35—O8—C44 | 116.97 (18) | C25—C24—C23 | 120.5 (3) |
N1—C1—C2 | 179.1 (4) | C29—C24—C23 | 121.9 (3) |
C3—C2—C7 | 116.3 (3) | F2—C25—C26 | 120.5 (3) |
C3—C2—C1 | 121.0 (3) | F2—C25—C24 | 116.9 (3) |
C7—C2—C1 | 122.7 (3) | C26—C25—C24 | 122.6 (3) |
F1—C3—C4 | 119.4 (3) | C26—C25—H25 | 118.7 |
F1—C3—C2 | 117.4 (3) | C24—C25—H25 | 118.7 |
C4—C3—C2 | 123.1 (3) | C25—C26—C27 | 118.5 (3) |
C4—C3—H3 | 118.4 | C25—C26—H26 | 120.8 |
C2—C3—H3 | 118.4 | C27—C26—H26 | 120.8 |
C5—C4—C3 | 117.9 (3) | C26—C27—C28 | 121.4 (3) |
C5—C4—H4 | 121.0 | C26—C27—O5 | 117.4 (3) |
C3—C4—H4 | 121.0 | C28—C27—O5 | 121.1 (3) |
C4—C5—C6 | 121.8 (3) | C29—C28—C27 | 119.1 (3) |
C4—C5—O1 | 117.7 (3) | C29—C28—H28 | 120.4 |
C6—C5—O1 | 120.2 (3) | C27—C28—H28 | 120.4 |
C5—C6—C7 | 118.2 (3) | F2'—C29—C28 | 120.7 (5) |
C5—C6—H6 | 120.9 | F2'—C29—C24 | 118.3 (5) |
C7—C6—H6 | 120.9 | C28—C29—C24 | 120.9 (3) |
F1'—C7—C6 | 120.3 (7) | C28—C29—H29 | 119.6 |
F1'—C7—C2 | 115.2 (6) | C24—C29—H29 | 119.6 |
C6—C7—C2 | 122.6 (3) | O6—C30—O5 | 120.6 (2) |
C6—C7—H7 | 118.7 | O6—C30—C31 | 126.8 (3) |
C2—C7—H7 | 118.7 | O5—C30—C31 | 112.6 (2) |
O2—C8—O1 | 120.9 (2) | C32—C31—C30 | 124.4 (3) |
O2—C8—C9 | 127.6 (3) | C32—C31—H31 | 117.8 |
O1—C8—C9 | 111.4 (2) | C30—C31—H31 | 117.8 |
C10—C9—C8 | 125.0 (3) | C31—C32—C33 | 127.2 (2) |
C10—C9—H9 | 117.5 | C31—C32—H32 | 116.4 |
C8—C9—H9 | 117.5 | C33—C32—H32 | 116.4 |
C9—C10—C11 | 128.5 (3) | C38—C33—C34 | 118.0 (2) |
C9—C10—H10 | 115.7 | C38—C33—C32 | 120.1 (2) |
C11—C10—H10 | 115.7 | C34—C33—C32 | 121.9 (2) |
C16—C11—C12 | 117.9 (2) | C35—C34—C33 | 121.2 (2) |
C16—C11—C10 | 119.0 (2) | C35—C34—H34 | 119.4 |
C12—C11—C10 | 123.1 (2) | C33—C34—H34 | 119.4 |
C13—C12—C11 | 121.4 (3) | O8—C35—C34 | 125.4 (2) |
C13—C12—H12 | 119.3 | O8—C35—C36 | 114.9 (2) |
C11—C12—H12 | 119.3 | C34—C35—C36 | 119.7 (2) |
O4—C13—C12 | 125.0 (2) | O7—C36—C37 | 125.1 (2) |
O4—C13—C14 | 115.0 (2) | O7—C36—C35 | 115.3 (2) |
C12—C13—C14 | 120.0 (2) | C37—C36—C35 | 119.6 (2) |
O3—C14—C15 | 125.4 (3) | C36—C37—C38 | 119.8 (2) |
O3—C14—C13 | 115.6 (2) | C36—C37—H37 | 120.1 |
C15—C14—C13 | 119.0 (2) | C38—C37—H37 | 120.1 |
C14—C15—C16 | 120.7 (3) | C33—C38—C37 | 121.7 (2) |
C14—C15—H15 | 119.7 | C33—C38—H38 | 119.1 |
C16—C15—H15 | 119.7 | C37—C38—H38 | 119.1 |
C11—C16—C15 | 121.0 (3) | O7—C39—C40 | 107.4 (2) |
C11—C16—H16 | 119.5 | O7—C39—H39A | 110.2 |
C15—C16—H16 | 119.5 | C40—C39—H39A | 110.2 |
O3—C17—C18 | 109.3 (2) | O7—C39—H39B | 110.2 |
O3—C17—H17A | 109.8 | C40—C39—H39B | 110.2 |
C18—C17—H17A | 109.8 | H39A—C39—H39B | 108.5 |
O3—C17—H17B | 109.8 | C39—C40—C41 | 114.1 (3) |
C18—C17—H17B | 109.8 | C39—C40—H40A | 108.7 |
H17A—C17—H17B | 108.3 | C41—C40—H40A | 108.7 |
C17—C18—C19 | 112.6 (3) | C39—C40—H40B | 108.7 |
C17—C18—H18A | 109.1 | C41—C40—H40B | 108.7 |
C19—C18—H18A | 109.1 | H40A—C40—H40B | 107.6 |
C17—C18—H18B | 109.1 | C42—C41—C40 | 114.8 (3) |
C19—C18—H18B | 109.1 | C42—C41—H41A | 108.6 |
H18A—C18—H18B | 107.8 | C40—C41—H41A | 108.6 |
C18—C19—C20 | 113.9 (3) | C42—C41—H41B | 108.6 |
C18—C19—H19A | 108.8 | C40—C41—H41B | 108.6 |
C20—C19—H19A | 108.8 | H41A—C41—H41B | 107.5 |
C18—C19—H19B | 108.8 | C41—C42—C43 | 112.0 (4) |
C20—C19—H19B | 108.8 | C41—C42—H42A | 109.2 |
H19A—C19—H19B | 107.7 | C43—C42—H42A | 109.2 |
C21—C20—C19 | 113.5 (3) | C41—C42—H42B | 109.2 |
C21—C20—H20A | 108.9 | C43—C42—H42B | 109.2 |
C19—C20—H20A | 108.9 | H42A—C42—H42B | 107.9 |
C21—C20—H20B | 108.9 | C42—C43—H43A | 109.5 |
C19—C20—H20B | 108.9 | C42—C43—H43B | 109.5 |
H20A—C20—H20B | 107.7 | H43A—C43—H43B | 109.5 |
C20—C21—H21A | 109.5 | C42—C43—H43C | 109.5 |
C20—C21—H21B | 109.5 | H43A—C43—H43C | 109.5 |
H21A—C21—H21B | 109.5 | H43B—C43—H43C | 109.5 |
C20—C21—H21C | 109.5 | O8—C44—H44A | 109.5 |
H21A—C21—H21C | 109.5 | O8—C44—H44B | 109.5 |
H21B—C21—H21C | 109.5 | H44A—C44—H44B | 109.5 |
O4—C22—H22A | 109.5 | O8—C44—H44C | 109.5 |
O4—C22—H22B | 109.5 | H44A—C44—H44C | 109.5 |
H22A—C22—H22B | 109.5 | H44B—C44—H44C | 109.5 |
C7—C2—C3—F1 | 178.0 (3) | C29—C24—C25—F2 | 180.0 (2) |
C1—C2—C3—F1 | −1.4 (4) | C23—C24—C25—F2 | 1.4 (4) |
C7—C2—C3—C4 | 0.3 (5) | C29—C24—C25—C26 | −0.9 (4) |
C1—C2—C3—C4 | −179.2 (3) | C23—C24—C25—C26 | −179.5 (3) |
F1—C3—C4—C5 | −177.9 (3) | F2—C25—C26—C27 | 179.0 (2) |
C2—C3—C4—C5 | −0.1 (5) | C24—C25—C26—C27 | −0.1 (4) |
C3—C4—C5—C6 | −0.1 (4) | C25—C26—C27—C28 | 1.1 (4) |
C3—C4—C5—O1 | 174.6 (2) | C25—C26—C27—O5 | −175.2 (2) |
C8—O1—C5—C4 | 110.4 (3) | C30—O5—C27—C26 | −116.5 (3) |
C8—O1—C5—C6 | −74.8 (3) | C30—O5—C27—C28 | 67.2 (3) |
C4—C5—C6—C7 | 0.2 (5) | C26—C27—C28—C29 | −1.0 (4) |
O1—C5—C6—C7 | −174.4 (3) | O5—C27—C28—C29 | 175.2 (2) |
C5—C6—C7—F1' | 163.2 (8) | C27—C28—C29—F2' | −175.4 (6) |
C5—C6—C7—C2 | 0.0 (5) | C27—C28—C29—C24 | −0.1 (4) |
C3—C2—C7—F1' | −164.2 (7) | C25—C24—C29—F2' | 176.4 (6) |
C1—C2—C7—F1' | 15.2 (8) | C23—C24—C29—F2' | −5.0 (7) |
C3—C2—C7—C6 | −0.2 (5) | C25—C24—C29—C28 | 1.0 (4) |
C1—C2—C7—C6 | 179.2 (3) | C23—C24—C29—C28 | 179.6 (2) |
C5—O1—C8—O2 | −5.3 (4) | C27—O5—C30—O6 | 4.9 (4) |
C5—O1—C8—C9 | 174.8 (2) | C27—O5—C30—C31 | −173.9 (2) |
O2—C8—C9—C10 | −179.2 (3) | O6—C30—C31—C32 | −178.3 (3) |
O1—C8—C9—C10 | 0.7 (4) | O5—C30—C31—C32 | 0.5 (4) |
C8—C9—C10—C11 | −178.5 (3) | C30—C31—C32—C33 | 176.9 (2) |
C9—C10—C11—C16 | 177.9 (3) | C31—C32—C33—C38 | 179.8 (2) |
C9—C10—C11—C12 | −2.3 (4) | C31—C32—C33—C34 | −1.1 (4) |
C16—C11—C12—C13 | 0.1 (4) | C38—C33—C34—C35 | 0.1 (4) |
C10—C11—C12—C13 | −179.7 (2) | C32—C33—C34—C35 | −179.1 (2) |
C22—O4—C13—C12 | −3.1 (4) | C44—O8—C35—C34 | 0.4 (4) |
C22—O4—C13—C14 | 177.3 (2) | C44—O8—C35—C36 | 179.4 (2) |
C11—C12—C13—O4 | −179.5 (2) | C33—C34—C35—O8 | 178.7 (2) |
C11—C12—C13—C14 | 0.1 (4) | C33—C34—C35—C36 | −0.3 (4) |
C17—O3—C14—C15 | −0.9 (4) | C39—O7—C36—C37 | 2.8 (4) |
C17—O3—C14—C13 | −179.9 (2) | C39—O7—C36—C35 | −177.4 (2) |
O4—C13—C14—O3 | −1.5 (3) | O8—C35—C36—O7 | 1.1 (3) |
C12—C13—C14—O3 | 178.8 (2) | C34—C35—C36—O7 | −179.8 (2) |
O4—C13—C14—C15 | 179.4 (3) | O8—C35—C36—C37 | −179.2 (2) |
C12—C13—C14—C15 | −0.3 (4) | C34—C35—C36—C37 | −0.1 (4) |
O3—C14—C15—C16 | −178.9 (2) | O7—C36—C37—C38 | −179.5 (2) |
C13—C14—C15—C16 | 0.2 (4) | C35—C36—C37—C38 | 0.8 (4) |
C12—C11—C16—C15 | −0.3 (4) | C34—C33—C38—C37 | 0.6 (4) |
C10—C11—C16—C15 | 179.6 (3) | C32—C33—C38—C37 | 179.7 (2) |
C14—C15—C16—C11 | 0.1 (5) | C36—C37—C38—C33 | −1.0 (4) |
C14—O3—C17—C18 | 178.7 (2) | C36—O7—C39—C40 | 176.5 (2) |
O3—C17—C18—C19 | 177.8 (2) | O7—C39—C40—C41 | 60.7 (3) |
C17—C18—C19—C20 | −177.3 (3) | C39—C40—C41—C42 | 179.1 (3) |
C18—C19—C20—C21 | −176.8 (3) | C40—C41—C42—C43 | 176.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C28—H28···O4 | 0.93 | 2.58 | 3.398 (3) | 147 |
C31—H31···O6i | 0.93 | 2.48 | 3.410 (3) | 174 |
C37—H37···O2ii | 0.93 | 2.39 | 3.246 (3) | 153 |
C44—H44A···F2iii | 0.96 | 2.37 | 3.262 (4) | 155 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+2, −z; (iii) x−1, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C22H22FNO4 |
Mr | 383.41 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 12.193 (4), 12.506 (4), 14.449 (5) |
α, β, γ (°) | 82.348 (7), 68.816 (6), 83.036 (7) |
V (Å3) | 2029.7 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.41 × 0.18 × 0.09 |
Data collection | |
Diffractometer | Simens SMART 1000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.963, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11493, 7827, 3944 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.619 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.173, 0.98 |
No. of reflections | 7827 |
No. of parameters | 524 |
No. of restraints | 30 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.18 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
O1—C8 | 1.369 (3) | N2—C23 | 1.140 (3) |
O1—C5 | 1.390 (3) | C1—C2 | 1.432 (4) |
O2—C8 | 1.191 (3) | C8—C9 | 1.450 (3) |
O5—C30 | 1.375 (3) | C9—C10 | 1.318 (3) |
O5—C27 | 1.387 (3) | C23—C24 | 1.439 (4) |
O6—C30 | 1.192 (3) | C30—C31 | 1.445 (3) |
N1—C1 | 1.139 (4) | C31—C32 | 1.327 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C28—H28···O4 | 0.93 | 2.58 | 3.398 (3) | 147 |
C31—H31···O6i | 0.93 | 2.48 | 3.410 (3) | 174 |
C37—H37···O2ii | 0.93 | 2.39 | 3.246 (3) | 153 |
C44—H44A···F2iii | 0.96 | 2.37 | 3.262 (4) | 155 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+2, −z; (iii) x−1, y, z+1. |
The nematic isotropic transition temperature of compounds containing a fluoro atom at the ortho- or meta- position with respect to the cyano-group on a phenyl ring are only slightly lower than the corresponding esters with an F atom (Kelly et al., 1984). However, the viscosity and driving voltage needed for the new esters are remarkably higher than those of the analogous non-fluoro-substituted phenyl esters. In order to obtain liquid-crystal materials with excellent properties (Sung et al., 2004), the title compound, (I), was synthesized. We report here the crystal structure of (I).
The asymmetric unit of (I) contains two crystallographically independent molecules. The corresponding bond lengths and angles of these two molecules agree with each other (Table 1) but they differ in the orientation of the 4-cyano-3-fluorobenzene ring with respect to the acrylate linkage (Fig. 1). The dihedral angle between C2–C7 and O1/O2/C8–C10 planes is 74.93 (9)° and that between C24–C29 and O5/O6/C30–C32 planes is 68.28 (8)°. Also, the torsion angles O3—C17—C18—C19 [177.8 (2)°] and O7—C39—C40—C41 [60.7 (3)°] indicate that in one of the molecules the pentyloxy chain is in an extended configuration and in the other it is folded. In both the molecules, the methoxybenzene ring is nearly coplanar with the acrylate linkage. The torsion angles C8—C9—C10—C11 [−178.5 (3)°] and C30—C31—C32—C33 [176.9 (2)°] indicate the trans configuration of the double bonds.
In the crystal structure, molecules are linked into a three-dimensional framework by C—H···O and C—H···F hydrogen bonds (Table 2). The packing is further stabilized by π–π interactions involving the C2–C7 and C24–C29 benzene rings at (x, y, z) and (x − 1, y, 1 + z), respectively, with a centroid–centroid distance of 3.788 (2) Å.