Synthesis, structure, growth and characterization of an organic crystal: 1,5-diphenylpenta-2,4-dien-1-one

1,5-Diphenylpenta-2,4-dien-1-one (DDO) chalcone single crystals, synthesized by a base-catalysed aldol condensation reaction between cinnamaldehyde and acetophenone, have been grown by the slow evaporation of an ethanol solution. The crystals belong to the orthorhombic system with centrosymmetric space group Pbca. The DDO crystals are transparent in the visible region and have a lower optical cut-off at ∼445 nm with a band-gap energy of 2.87 eV. Thermogravimetry/differential scanning calorimetry thermal analysis shows that the crystal is stable up to 375 K and it has a good chemical stability. The vibrational patterns of the chalcone have been investigated by Fourier transform IR and Fourier transform Raman spectroscopy. Microhardness studies were also carried out to elucidate the mechanical behaviour. Theoretical calculations were performed using the Hartree–Fock method with 6-31G(d,p) as the basis set, and the first-order hyperpolarizability is 7.077 × 10⁻³⁰ electrostatic units, which is >25 times that of urea. The crystalline perfection evaluated by high-resolution X-ray diffraction analysis reveals multiple peaks. The molecular packing leads to a centrosymmetric arrangement, resulting in zero second harmonic generation [χ⁽²⁾ = 0] efficiency. Interestingly, the bromo- and chloro-substituted chalcones are good nonlinear optical materials.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2/SAINT (Bruker, 2004); data reduction: SAINT/XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altornare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

(I)

Crystal data

C17H14O	Dx = 1.197 Mg m^−3
Mr = 234.28	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 2996 reflections
a = 15.4307 (9) Å	θ = 2.5–23.1°
b = 10.2659 (5) Å	µ = 0.07 mm^−1
c = 16.4124 (9) Å	T = 293 K
V = 2599.9 (2) Å^3	Block, colourless
Z = 8	0.30 × 0.20 × 0.20 mm
F(000) = 992

Data collection

Bruker axs kappa apex2 CCD Diffractometer	2041 independent reflections
Radiation source: fine-focus sealed tube	1430 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω and φ scan	θmax = 24.1°, θmin = 2.5°
Absorption correction: multi-scan SADABS (Bruker, 1999)	h = −13→17
Tmin = 0.961, Tmax = 0.992	k = −11→11
11155 measured reflections	l = −18→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.130	w = 1/[σ^2(Fo^2) + (0.062P)^2 + 0.4186P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
2041 reflections	Δρmax = 0.31 e Å^−3
164 parameters	Δρmin = −0.12 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0025 (8)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.65266 (13)	0.14890 (19)	0.61284 (12)	0.0630 (5)
H1	0.6542	0.0589	0.6193	0.076*
C2	0.69425 (14)	0.2049 (2)	0.54790 (13)	0.0757 (6)
H2	0.7238	0.1529	0.5108	0.091*
C3	0.69250 (14)	0.3374 (2)	0.53742 (13)	0.0772 (7)
H3	0.7201	0.3752	0.4929	0.093*
C4	0.64976 (14)	0.4139 (2)	0.59307 (13)	0.0722 (6)
H4	0.6493	0.5039	0.5866	0.087*
C5	0.60759 (12)	0.35819 (17)	0.65836 (11)	0.0581 (5)
H5	0.5784	0.4108	0.6955	0.070*
C6	0.60837 (11)	0.22454 (16)	0.66904 (10)	0.0488 (5)
C7	0.56664 (12)	0.15942 (16)	0.74004 (11)	0.0548 (5)
C8	0.52131 (12)	0.23788 (17)	0.80105 (11)	0.0580 (5)
H8	0.5039	0.3217	0.7871	0.070*
C9	0.50403 (12)	0.19458 (18)	0.87556 (11)	0.0572 (5)
H9	0.5218	0.1104	0.8882	0.069*
C10	0.46067 (12)	0.26582 (17)	0.93781 (11)	0.0583 (5)
H10	0.4440	0.3508	0.9260	0.070*
C11	0.44226 (12)	0.21989 (18)	1.01173 (11)	0.0592 (5)
H11	0.4608	0.1356	1.0228	0.071*
C12	0.39641 (11)	0.28646 (18)	1.07716 (10)	0.0542 (5)
C13	0.38653 (13)	0.42074 (19)	1.07965 (11)	0.0633 (6)
H13	0.4122	0.4717	1.0395	0.076*
C14	0.33945 (15)	0.4797 (2)	1.14036 (13)	0.0748 (6)
H14	0.3331	0.5698	1.1407	0.090*
C15	0.30184 (15)	0.4064 (2)	1.20029 (13)	0.0801 (7)
H15	0.2693	0.4462	1.2409	0.096*
C16	0.31232 (15)	0.2744 (2)	1.20010 (13)	0.0802 (7)
H16	0.2873	0.2245	1.2411	0.096*
C17	0.35956 (14)	0.2149 (2)	1.13985 (11)	0.0687 (6)
H17	0.3670	0.1251	1.1411	0.082*
O1	0.57175 (11)	0.04065 (12)	0.74720 (8)	0.0832 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0654 (14)	0.0573 (11)	0.0663 (12)	0.0012 (10)	0.0040 (10)	−0.0042 (9)
C2	0.0732 (15)	0.0849 (15)	0.0689 (13)	0.0057 (12)	0.0193 (12)	−0.0076 (11)
C3	0.0649 (15)	0.0946 (17)	0.0720 (14)	−0.0033 (13)	0.0172 (11)	0.0164 (12)
C4	0.0711 (15)	0.0625 (12)	0.0830 (14)	−0.0038 (11)	0.0126 (12)	0.0156 (11)
C5	0.0599 (13)	0.0535 (11)	0.0608 (11)	0.0000 (9)	0.0062 (10)	0.0003 (8)
C6	0.0462 (11)	0.0502 (10)	0.0500 (10)	−0.0015 (8)	−0.0035 (8)	−0.0006 (8)
C7	0.0582 (12)	0.0478 (10)	0.0584 (11)	−0.0011 (9)	−0.0024 (9)	0.0025 (8)
C8	0.0630 (13)	0.0505 (10)	0.0605 (12)	0.0026 (9)	0.0051 (10)	0.0045 (9)
C9	0.0596 (13)	0.0544 (10)	0.0575 (11)	0.0029 (9)	0.0014 (10)	0.0038 (9)
C10	0.0601 (12)	0.0545 (10)	0.0601 (11)	0.0021 (9)	0.0012 (10)	0.0032 (9)
C11	0.0580 (13)	0.0641 (11)	0.0554 (11)	0.0060 (9)	−0.0024 (10)	0.0031 (9)
C12	0.0479 (11)	0.0645 (11)	0.0502 (10)	−0.0009 (9)	−0.0073 (9)	0.0008 (9)
C13	0.0614 (13)	0.0689 (13)	0.0595 (12)	−0.0100 (10)	0.0010 (10)	−0.0046 (9)
C14	0.0771 (16)	0.0704 (13)	0.0770 (14)	−0.0064 (11)	0.0002 (12)	−0.0184 (11)
C15	0.0726 (16)	0.0987 (17)	0.0689 (14)	−0.0072 (13)	0.0082 (12)	−0.0234 (12)
C16	0.0808 (17)	0.0996 (18)	0.0601 (13)	−0.0126 (14)	0.0123 (12)	0.0007 (12)
C17	0.0769 (15)	0.0701 (12)	0.0592 (12)	0.0017 (11)	0.0032 (11)	0.0063 (10)
O1	0.1140 (13)	0.0524 (8)	0.0832 (10)	0.0011 (8)	0.0189 (9)	0.0061 (7)

Geometric parameters (Å, º)

C1—C2	1.371 (3)	C9—H9	0.9300
C1—C6	1.386 (2)	C10—C11	1.332 (2)
C1—H1	0.9300	C10—H10	0.9300
C2—C3	1.371 (3)	C11—C12	1.456 (2)
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.373 (3)	C12—C17	1.386 (3)
C3—H3	0.9300	C12—C13	1.388 (3)
C4—C5	1.378 (3)	C13—C14	1.374 (3)
C4—H4	0.9300	C13—H13	0.9300
C5—C6	1.383 (2)	C14—C15	1.368 (3)
C5—H5	0.9300	C14—H14	0.9300
C6—C7	1.490 (2)	C15—C16	1.364 (3)
C7—O1	1.2275 (19)	C15—H15	0.9300
C7—C8	1.463 (2)	C16—C17	1.372 (3)
C8—C9	1.328 (2)	C16—H16	0.9300
C8—H8	0.9300	C17—H17	0.9300
C9—C10	1.423 (2)
C2—C1—C6	120.88 (18)	C10—C9—H9	117.2
C2—C1—H1	119.6	C11—C10—C9	124.89 (17)
C6—C1—H1	119.6	C11—C10—H10	117.6
C1—C2—C3	120.3 (2)	C9—C10—H10	117.6
C1—C2—H2	119.8	C10—C11—C12	127.52 (18)
C3—C2—H2	119.8	C10—C11—H11	116.2
C2—C3—C4	119.54 (19)	C12—C11—H11	116.2
C2—C3—H3	120.2	C17—C12—C13	117.35 (18)
C4—C3—H3	120.2	C17—C12—C11	119.88 (18)
C3—C4—C5	120.48 (19)	C13—C12—C11	122.77 (17)
C3—C4—H4	119.8	C14—C13—C12	121.16 (19)
C5—C4—H4	119.8	C14—C13—H13	119.4
C4—C5—C6	120.39 (18)	C12—C13—H13	119.4
C4—C5—H5	119.8	C15—C14—C13	120.2 (2)
C6—C5—H5	119.8	C15—C14—H14	119.9
C5—C6—C1	118.40 (17)	C13—C14—H14	119.9
C5—C6—C7	122.72 (16)	C16—C15—C14	119.6 (2)
C1—C6—C7	118.83 (16)	C16—C15—H15	120.2
O1—C7—C8	120.80 (16)	C14—C15—H15	120.2
O1—C7—C6	119.53 (16)	C15—C16—C17	120.5 (2)
C8—C7—C6	119.66 (14)	C15—C16—H16	119.8
C9—C8—C7	122.81 (16)	C17—C16—H16	119.8
C9—C8—H8	118.6	C16—C17—C12	121.1 (2)
C7—C8—H8	118.6	C16—C17—H17	119.4
C8—C9—C10	125.68 (17)	C12—C17—H17	119.4
C8—C9—H9	117.2
C6—C1—C2—C3	−0.1 (3)	C7—C8—C9—C10	179.67 (17)
C1—C2—C3—C4	0.9 (4)	C8—C9—C10—C11	178.5 (2)
C2—C3—C4—C5	−1.1 (3)	C9—C10—C11—C12	−178.39 (18)
C3—C4—C5—C6	0.5 (3)	C10—C11—C12—C17	160.3 (2)
C4—C5—C6—C1	0.2 (3)	C10—C11—C12—C13	−18.9 (3)
C4—C5—C6—C7	177.74 (17)	C17—C12—C13—C14	−2.2 (3)
C2—C1—C6—C5	−0.4 (3)	C11—C12—C13—C14	176.97 (18)
C2—C1—C6—C7	−178.03 (18)	C12—C13—C14—C15	0.6 (3)
C5—C6—C7—O1	−177.93 (18)	C13—C14—C15—C16	0.9 (3)
C1—C6—C7—O1	−0.4 (3)	C14—C15—C16—C17	−0.6 (4)
C5—C6—C7—C8	1.1 (3)	C15—C16—C17—C12	−1.1 (3)
C1—C6—C7—C8	178.58 (16)	C13—C12—C17—C16	2.5 (3)
O1—C7—C8—C9	18.4 (3)	C11—C12—C17—C16	−176.72 (18)
C6—C7—C8—C9	−160.63 (18)