Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020582/rz2134sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020582/rz2134Isup2.hkl |
CCDC reference: 651396
The title compound is synthesized according to the method reported in the literature (Furniss et al., 1989) with a yield of 75–80%. The compound is purified by recrystallization from ethanol. The crystal growth is done in acetone solvent by slow evaporation technique (m.p.333–37 K). Analysis for C18H16O: Found (Calculated): C: 87.50 (87.06%); H: 6.31 (6.49%).
H atoms were placed at calculated positions and refined as riding on the respective carrier atoms, with C—H = 0.93–0.96 Å and Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C) for methyl H atoms.
The title compound, (I), C18H16O, 1-(4-methylphenyl)-5-phenylpenta-2,4-dien-1-one is an optically active molecule. The present-day demand is for large and high quality ferroelectric, piezoelectric single crystals with minimum defects and inhomogenities. The important goal of crystal growth is the improvement of microscopic and macroscopic homogeneity, which is a necessity for any application. Different types of crystals being used are semiconductor crystals, oxide crystals, alkali halide crystals, and nonlinear optical (NLO) crystals. The NLO effect in organic molecules originates from a strong donor–acceptor intermolecular interaction, a delocalized π-electron system, and also the ability to crystallize in noncentrosymmetric space groups. Substitution on either of the phenyl rings greatly influences non-centrosymmetric crystal packing. It is speculated that in order to improve the activity, more bulky substituents should be introduced to increase the spontaneous polarization of non-centrosymmetric crystals (Fichou et al., 1988). The molecular hyperpolarizability is strongly influenced not only by the electronic effect but also by the steric effect of the substituent (Cho et al., 1996). Among several organic compounds reported for NLO properties, chalcone derivatives are notable materials for their excellent blue light transmittance and good crystallizability. They provide a necessary configuration to show an NLO property with two planar rings connected through a conjugated double bond (Goto et al., 1991; Uchida et al., 1998; Tam et al., 1989; Indira et al., 2002, Sarojini et al., 2006). The crystal structures of 1,5-bis(4-chlorophenyl)penta-1,4-dien-3-one (Butcher et al., 2006), 5-phenyl-1-(2-thienyl)penta-2,4-dien-1-one (Yathirajan et al., 2007) and 1,5-bis(4-methoxyphenyl)penta-1,4-dien-3-one (Harrison et al., 2006) have been reported. The paper reports crystal structure of the title compound. Fig. 1 shows the molecular structure. The geometry is unexceptional.
For related structures, see: Butcher et al. (2006), Yathirajan et al. (2007), Harrison et al. (2006). For non-linear optical crystals, see: Fichour et al. (1988), Cho et al. (1996), Goto et al. (1991), Uchida et al. (1998), Tam et al. (1989), Indira et al. (2002), Sarojini et al. (2006).
For related literature, see: Fichou et al. (1988); Furniss et al. (1989).
Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg, 1992); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2007).
Fig. 1. : The molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level. |
C18H16O | F(000) = 528 |
Mr = 248.33 | Dx = 1.170 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 31 reflections |
a = 7.7215 (12) Å | θ = 5.8–19.2° |
b = 10.6985 (12) Å | µ = 0.07 mm−1 |
c = 17.331 (3) Å | T = 298 K |
β = 99.550 (13)° | Block, colourless |
V = 1411.9 (4) Å3 | 0.46 × 0.44 × 0.16 mm |
Z = 4 |
Bruker-Nonius KappaCCD diffractometer | Rint = 0.083 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 4.5° |
φ and ω scans | h = −9→9 |
12654 measured reflections | k = −12→12 |
2465 independent reflections | l = −20→20 |
1411 reflections with I > 2σ(I) |
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)] = 0.068 | H-atom parameters constrained |
wR(F2) = 0.162 | w = 1/[σ2(Fo2) + (0.0454P)2 + 0.599P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max < 0.001 |
2465 reflections | Δρmax = 0.23 e Å−3 |
172 parameters | Δρmin = −0.14 e Å−3 |
0 restraints |
C18H16O | V = 1411.9 (4) Å3 |
Mr = 248.33 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.7215 (12) Å | µ = 0.07 mm−1 |
b = 10.6985 (12) Å | T = 298 K |
c = 17.331 (3) Å | 0.46 × 0.44 × 0.16 mm |
β = 99.550 (13)° |
Bruker-Nonius KappaCCD diffractometer | 1411 reflections with I > 2σ(I) |
12654 measured reflections | Rint = 0.083 |
2465 independent reflections |
R[F2 > 2σ(F2)] = 0.068 | 0 restraints |
wR(F2) = 0.162 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.23 e Å−3 |
2465 reflections | Δρmin = −0.14 e Å−3 |
172 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 | ||
C1 | 0.8540 (4) | 0.4877 (3) | 0.58254 (18) | 0.0693 (9) | |
C2 | 0.9516 (5) | 0.4357 (3) | 0.6484 (2) | 0.0797 (10) | |
C3 | 0.9547 (5) | 0.4901 (4) | 0.7199 (2) | 0.0812 (10) | |
C4 | 0.8622 (5) | 0.5971 (4) | 0.72512 (19) | 0.0854 (11) | |
C5 | 0.7655 (4) | 0.6509 (3) | 0.65946 (17) | 0.0696 (9) | |
C6 | 0.7598 (4) | 0.5958 (3) | 0.58691 (15) | 0.0555 (7) | |
C7 | 0.6567 (4) | 0.6560 (3) | 0.51811 (17) | 0.0654 (8) | |
C8 | 0.6335 (4) | 0.6166 (3) | 0.44402 (16) | 0.0639 (8) | |
C9 | 0.5317 (4) | 0.6825 (3) | 0.38073 (17) | 0.0632 (8) | |
C10 | 0.5010 (4) | 0.6488 (3) | 0.30626 (16) | 0.0605 (8) | |
C11 | 0.3920 (4) | 0.7267 (3) | 0.24737 (17) | 0.0578 (8) | |
C12 | 0.3346 (4) | 0.6776 (3) | 0.16667 (15) | 0.0510 (7) | |
C13 | 0.3969 (4) | 0.5667 (3) | 0.13931 (16) | 0.0622 (8) | |
C14 | 0.3401 (4) | 0.5283 (3) | 0.06311 (17) | 0.0674 (9) | |
C15 | 0.2203 (4) | 0.5965 (3) | 0.01268 (16) | 0.0601 (8) | |
C16 | 0.1533 (4) | 0.7044 (3) | 0.04084 (18) | 0.0681 (9) | |
C17 | 0.2110 (4) | 0.7453 (3) | 0.11586 (18) | 0.0656 (8) | |
C18 | 0.1592 (5) | 0.5536 (4) | −0.07059 (17) | 0.0819 (11) | |
O1 | 0.3463 (3) | 0.8317 (2) | 0.26439 (12) | 0.0830 (7) | |
H1 | 0.8520 | 0.4490 | 0.5344 | 0.083* | |
H2 | 1.0158 | 0.3631 | 0.6442 | 0.096* | |
H3 | 1.0192 | 0.4543 | 0.7644 | 0.097* | |
H4 | 0.8640 | 0.6347 | 0.7736 | 0.102* | |
H5 | 0.7039 | 0.7246 | 0.6640 | 0.084* | |
H7 | 0.6010 | 0.7305 | 0.5272 | 0.078* | |
H8 | 0.6866 | 0.5420 | 0.4331 | 0.077* | |
H9 | 0.4814 | 0.7574 | 0.3931 | 0.076* | |
H10 | 0.5490 | 0.5747 | 0.2910 | 0.073* | |
H13 | 0.4771 | 0.5181 | 0.1723 | 0.075* | |
H14 | 0.3842 | 0.4544 | 0.0457 | 0.081* | |
H16 | 0.0678 | 0.7500 | 0.0085 | 0.082* | |
H17 | 0.1666 | 0.8194 | 0.1328 | 0.079* | |
H18A | 0.2329 | 0.5901 | −0.1042 | 0.123* | |
H18B | 0.0396 | 0.5795 | −0.0872 | 0.123* | |
H18C | 0.1664 | 0.4641 | −0.0731 | 0.123* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.084 (2) | 0.069 (2) | 0.0520 (19) | 0.0019 (18) | 0.0018 (16) | −0.0047 (16) |
C2 | 0.091 (3) | 0.072 (2) | 0.074 (2) | 0.0115 (19) | 0.0060 (19) | 0.0054 (19) |
C3 | 0.081 (2) | 0.100 (3) | 0.057 (2) | 0.000 (2) | −0.0065 (17) | 0.014 (2) |
C4 | 0.094 (3) | 0.113 (3) | 0.046 (2) | −0.001 (2) | 0.0017 (18) | −0.005 (2) |
C5 | 0.070 (2) | 0.087 (2) | 0.0516 (19) | 0.0044 (18) | 0.0093 (15) | −0.0084 (17) |
C6 | 0.0551 (17) | 0.0655 (19) | 0.0453 (17) | −0.0020 (15) | 0.0061 (13) | −0.0011 (15) |
C7 | 0.070 (2) | 0.070 (2) | 0.0549 (19) | 0.0020 (17) | 0.0052 (15) | −0.0034 (16) |
C8 | 0.068 (2) | 0.068 (2) | 0.0533 (19) | 0.0007 (16) | 0.0040 (15) | −0.0024 (16) |
C9 | 0.0635 (19) | 0.068 (2) | 0.0554 (19) | −0.0002 (15) | 0.0019 (15) | 0.0007 (16) |
C10 | 0.0664 (19) | 0.065 (2) | 0.0477 (17) | 0.0007 (16) | 0.0025 (14) | −0.0029 (15) |
C11 | 0.0599 (18) | 0.061 (2) | 0.0532 (19) | −0.0036 (15) | 0.0103 (14) | 0.0016 (15) |
C12 | 0.0543 (17) | 0.0542 (17) | 0.0452 (16) | −0.0035 (14) | 0.0101 (13) | 0.0066 (13) |
C13 | 0.0660 (19) | 0.073 (2) | 0.0466 (17) | 0.0136 (16) | 0.0053 (14) | 0.0071 (15) |
C14 | 0.082 (2) | 0.068 (2) | 0.0519 (19) | 0.0115 (17) | 0.0086 (16) | −0.0052 (16) |
C15 | 0.0641 (19) | 0.070 (2) | 0.0457 (17) | −0.0134 (16) | 0.0091 (14) | 0.0078 (16) |
C16 | 0.076 (2) | 0.068 (2) | 0.055 (2) | −0.0005 (17) | −0.0041 (16) | 0.0149 (16) |
C17 | 0.075 (2) | 0.0575 (19) | 0.062 (2) | 0.0062 (16) | 0.0050 (17) | 0.0089 (15) |
C18 | 0.087 (2) | 0.104 (3) | 0.0521 (19) | −0.018 (2) | 0.0022 (17) | 0.0051 (18) |
O1 | 0.1052 (19) | 0.0669 (15) | 0.0716 (15) | 0.0141 (13) | −0.0017 (13) | −0.0121 (12) |
C1—C6 | 1.373 (4) | C15—C18 | 1.516 (4) |
C1—C2 | 1.379 (4) | C16—C17 | 1.377 (4) |
C2—C3 | 1.367 (4) | C1—H1 | 0.9300 |
C3—C4 | 1.358 (5) | C2—H2 | 0.9300 |
C4—C5 | 1.381 (4) | C3—H3 | 0.9300 |
C5—C6 | 1.384 (4) | C4—H4 | 0.9300 |
C6—C7 | 1.471 (4) | C5—H5 | 0.9300 |
C7—C8 | 1.337 (4) | C7—H7 | 0.9300 |
C8—C9 | 1.427 (4) | C8—H8 | 0.9300 |
C9—C10 | 1.325 (4) | C9—H9 | 0.9300 |
C10—C11 | 1.471 (4) | C10—H10 | 0.9300 |
C11—O1 | 1.227 (3) | C13—H13 | 0.9300 |
C11—C12 | 1.494 (4) | C14—H14 | 0.9300 |
C12—C17 | 1.391 (4) | C16—H16 | 0.9300 |
C12—C13 | 1.391 (4) | C17—H17 | 0.9300 |
C13—C14 | 1.386 (4) | C18—H18A | 0.9600 |
C14—C15 | 1.373 (4) | C18—H18B | 0.9600 |
C15—C16 | 1.385 (4) | C18—H18C | 0.9600 |
C6—C1—C2 | 121.0 (3) | C4—C3—H3 | 120.4 |
C3—C2—C1 | 120.5 (3) | C2—C3—H3 | 120.4 |
C4—C3—C2 | 119.1 (3) | C3—C4—H4 | 119.5 |
C3—C4—C5 | 120.9 (3) | C5—C4—H4 | 119.5 |
C4—C5—C6 | 120.4 (3) | C4—C5—H5 | 119.8 |
C1—C6—C5 | 118.0 (3) | C6—C5—H5 | 119.8 |
C1—C6—C7 | 123.0 (3) | C8—C7—H7 | 116.1 |
C5—C6—C7 | 119.0 (3) | C6—C7—H7 | 116.1 |
C8—C7—C6 | 127.8 (3) | C7—C8—H8 | 118.1 |
C7—C8—C9 | 123.7 (3) | C9—C8—H8 | 118.1 |
C10—C9—C8 | 127.2 (3) | C10—C9—H9 | 116.4 |
C9—C10—C11 | 121.0 (3) | C8—C9—H9 | 116.4 |
O1—C11—C10 | 120.3 (3) | C9—C10—H10 | 119.5 |
O1—C11—C12 | 119.6 (3) | C11—C10—H10 | 119.5 |
C10—C11—C12 | 120.1 (3) | C14—C13—H13 | 119.8 |
C17—C12—C13 | 117.8 (3) | C12—C13—H13 | 119.8 |
C17—C12—C11 | 118.6 (3) | C15—C14—H14 | 119.1 |
C13—C12—C11 | 123.6 (3) | C13—C14—H14 | 119.1 |
C14—C13—C12 | 120.4 (3) | C17—C16—H16 | 119.4 |
C15—C14—C13 | 121.7 (3) | C15—C16—H16 | 119.4 |
C14—C15—C16 | 117.9 (3) | C16—C17—H17 | 119.4 |
C14—C15—C18 | 121.3 (3) | C12—C17—H17 | 119.4 |
C16—C15—C18 | 120.8 (3) | C15—C18—H18A | 109.5 |
C17—C16—C15 | 121.1 (3) | C15—C18—H18B | 109.5 |
C16—C17—C12 | 121.1 (3) | H18A—C18—H18B | 109.5 |
C6—C1—H1 | 119.5 | C15—C18—H18C | 109.5 |
C2—C1—H1 | 119.5 | H18A—C18—H18C | 109.5 |
C3—C2—H2 | 119.7 | H18B—C18—H18C | 109.5 |
C1—C2—H2 | 119.7 |
Experimental details
Crystal data | |
Chemical formula | C18H16O |
Mr | 248.33 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 7.7215 (12), 10.6985 (12), 17.331 (3) |
β (°) | 99.550 (13) |
V (Å3) | 1411.9 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.46 × 0.44 × 0.16 |
Data collection | |
Diffractometer | Bruker-Nonius KappaCCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12654, 2465, 1411 |
Rint | 0.083 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.162, 1.12 |
No. of reflections | 2465 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.14 |
Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg, 1992), EVALCCD (Duisenberg et al., 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2007).
The title compound, (I), C18H16O, 1-(4-methylphenyl)-5-phenylpenta-2,4-dien-1-one is an optically active molecule. The present-day demand is for large and high quality ferroelectric, piezoelectric single crystals with minimum defects and inhomogenities. The important goal of crystal growth is the improvement of microscopic and macroscopic homogeneity, which is a necessity for any application. Different types of crystals being used are semiconductor crystals, oxide crystals, alkali halide crystals, and nonlinear optical (NLO) crystals. The NLO effect in organic molecules originates from a strong donor–acceptor intermolecular interaction, a delocalized π-electron system, and also the ability to crystallize in noncentrosymmetric space groups. Substitution on either of the phenyl rings greatly influences non-centrosymmetric crystal packing. It is speculated that in order to improve the activity, more bulky substituents should be introduced to increase the spontaneous polarization of non-centrosymmetric crystals (Fichou et al., 1988). The molecular hyperpolarizability is strongly influenced not only by the electronic effect but also by the steric effect of the substituent (Cho et al., 1996). Among several organic compounds reported for NLO properties, chalcone derivatives are notable materials for their excellent blue light transmittance and good crystallizability. They provide a necessary configuration to show an NLO property with two planar rings connected through a conjugated double bond (Goto et al., 1991; Uchida et al., 1998; Tam et al., 1989; Indira et al., 2002, Sarojini et al., 2006). The crystal structures of 1,5-bis(4-chlorophenyl)penta-1,4-dien-3-one (Butcher et al., 2006), 5-phenyl-1-(2-thienyl)penta-2,4-dien-1-one (Yathirajan et al., 2007) and 1,5-bis(4-methoxyphenyl)penta-1,4-dien-3-one (Harrison et al., 2006) have been reported. The paper reports crystal structure of the title compound. Fig. 1 shows the molecular structure. The geometry is unexceptional.