A second polymorph of (2E)-1-(4-fluoro-phen-yl)-3-(3,4,5-trimethoxy-phen-yl)prop-2-en-1-one.

The crystal structure of the title compound, C(18)H(17)FO(4), reported here is a polymorph of the structure first reported by Patil et al. [Mol. Cryst. Liq. Cryst. Sci. Technol. Sect. A (2007), 461, 123-130]. It is a chalcone analog and consists of substituted phenyl rings bonded at the opposite ends of a propenone group, the biologically active region. The dihedral angle between the mean planes of the aromatic rings within the 4-fluoro-phenyl and trimethoxy-phenyl groups is 28.7 (1)° compared to 20.8 (6)° in the published structure. The angles between the mean plane of the prop-2-ene-1-one group and the mean plane of aromatic rings within the 4-fluoro-phenyl and trimethoxy-phenyl groups are 30.3 (4) and 7.4 (7)°, respectively, in contast to 10.7 (3) and 12.36° for the polymorph. While the two 3-meth-oxy groups are in the plane of the trimeth-oxy-substituted ring, the 4-meth-oxy group is in a synclinical [-sc = -78.1 (2)°] or anti-clinical [+ac = 104.0 (4)°] position, compared to a +sc [53.0 (4)°] or -ac [-132.4 (7)°] position. While no classical hydrogen bonds are present, weak inter-molecular C-H⋯π-ring inter-actions are observed which contribute to the stability of the crystal packing. The two polymorphs crystallize in the same space group, P2(1)/c, but have different cell parameters for the a, b and c axes and the β angle. A comparison of the mol-ecular geometries of both polymorphs to a geometry optimized density functional theory (DFT) calculation at the B3-LYP/6-311+G(d,p) level for each structure provides additional support to these observations.

Related literature

For general background to the biological activity of similar compounds, see: Dimmock et al. (1999 ▶); Lin et al. (2002 ▶); Nakamura et al. (2002 ▶); Nowakowska (2007 ▶); Opletalova & Sedivy (1999 ▶). For related structures, see: Butcher et al. (2006 ▶, 2007 ▶); Chopra et al. (2007 ▶); Fun et al. (2008 ▶); Jasinski et al. (2009 ▶); Patil et al. (2007 ▶); Qiu et al. (2006 ▶); Teh et al. (2007 ▶). For density functional theory (DFT), see: Becke (1988 ▶, 1993 ▶); Hehre et al. (1986 ▶); Lee et al. (1988 ▶); Schmidt & Polik (2007 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). For the GAUSSIAN03 program package, see: Frisch et al. (2004 ▶).

Experimental

Crystal data

C18H17FO4

M = 316.32

Monoclinic,

a = 12.4250 (2) Å

b = 8.6280 (1) Å

c = 14.9038 (2) Å

β = 98.3217 (12)°

V = 1580.91 (4) Å3

Z = 4

Cu Kα radiation

μ = 0.85 mm−1

T = 295 K

0.47 × 0.40 × 0.22 mm

Data collection

Oxford Diffraction Gemini R diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T min = 0.557, T max = 0.830

8137 measured reflections

3216 independent reflections

2396 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.126

S = 1.10

3216 reflections

211 parameters

H-atom parameters constrained

Δρmax = 0.13 e Å−3

Δρmin = −0.18 e Å−3

Data collection: CrysAlis Pro (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028517/sj2632sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028517/sj2632Isup2.hkl

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

C18H17FO4	F(000) = 664
Mr = 316.32	Dx = 1.329 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 4493 reflections
a = 12.4250 (2) Å	θ = 4.3–77.3°
b = 8.6280 (1) Å	µ = 0.85 mm−1
c = 14.9038 (2) Å	T = 295 K
β = 98.3217 (12)°	Prism, colorless
V = 1580.91 (4) Å3	0.47 × 0.40 × 0.22 mm
Z = 4

Oxford Diffraction Gemini R diffractometer	3216 independent reflections
Radiation source: fine-focus sealed tube	2396 reflections with I > 2σ(I)
graphite	Rint = 0.018
Detector resolution: 10.5081 pixels mm-1	θmax = 77.9°, θmin = 5.9°
φ and ω scans	h = −14→15
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −10→9
Tmin = 0.557, Tmax = 0.830	l = −18→18
8137 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.0683P)2 + 0.1035P] where P = (Fo2 + 2Fc2)/3
3216 reflections	(Δ/σ)max < 0.001
211 parameters	Δρmax = 0.13 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

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
O4	0.54332 (9)	0.78663 (17)	0.56646 (8)	0.0813 (4)
F	0.12194 (11)	0.38071 (16)	−0.04098 (8)	0.0982 (4)
O1	0.01131 (9)	0.41222 (15)	0.35678 (8)	0.0737 (3)
O2	0.33800 (9)	0.64264 (16)	0.79007 (7)	0.0751 (3)
O3	0.51516 (9)	0.76879 (15)	0.74012 (8)	0.0716 (3)
C1	0.10184 (11)	0.43862 (16)	0.22896 (11)	0.0576 (3)
C2	0.16144 (13)	0.54012 (19)	0.18363 (12)	0.0684 (4)
H2A	0.1980	0.6219	0.2152	0.082*
C3	0.16769 (15)	0.5225 (2)	0.09261 (12)	0.0745 (4)
H3A	0.2071	0.5920	0.0625	0.089*
C4	0.11452 (13)	0.4002 (2)	0.04776 (12)	0.0698 (4)
C5	0.05441 (14)	0.2970 (2)	0.08954 (14)	0.0765 (5)
H5A	0.0189	0.2149	0.0574	0.092*
C6	0.04768 (13)	0.31760 (19)	0.17996 (13)	0.0695 (4)
H6A	0.0061	0.2493	0.2090	0.083*
C7	0.09279 (11)	0.45582 (16)	0.32705 (11)	0.0591 (3)
C8	0.18590 (12)	0.52523 (19)	0.38636 (11)	0.0633 (4)
H8A	0.2441	0.5643	0.3605	0.076*
C9	0.18866 (11)	0.53327 (18)	0.47527 (11)	0.0612 (4)
H9A	0.1275	0.4964	0.4978	0.073*
C10	0.27643 (11)	0.59319 (17)	0.54241 (10)	0.0572 (3)
C11	0.26418 (11)	0.58419 (18)	0.63367 (10)	0.0605 (4)
H11A	0.2019	0.5398	0.6505	0.073*
C12	0.34453 (11)	0.64123 (18)	0.69953 (10)	0.0587 (3)
C13	0.43756 (12)	0.70811 (18)	0.67455 (10)	0.0591 (3)
C14	0.44971 (11)	0.71778 (19)	0.58304 (10)	0.0611 (4)
C15	0.36992 (12)	0.66065 (19)	0.51690 (10)	0.0611 (4)
H15A	0.3783	0.6670	0.4560	0.073*
C16	0.25626 (17)	0.5508 (3)	0.82150 (13)	0.0855 (5)
H16A	0.1858	0.5875	0.7950	0.128*
H16B	0.2630	0.5581	0.8863	0.128*
H16C	0.2647	0.4448	0.8044	0.128*
C17	0.60831 (14)	0.6733 (3)	0.75995 (13)	0.0836 (5)
H17A	0.5874	0.5746	0.7817	0.125*
H17B	0.6597	0.7219	0.8056	0.125*
H17C	0.6410	0.6586	0.7060	0.125*
C18	0.56292 (15)	0.7943 (3)	0.47481 (13)	0.0864 (6)
H18A	0.5608	0.6918	0.4496	0.130*
H18B	0.6332	0.8392	0.4727	0.130*
H18C	0.5080	0.8571	0.4403	0.130*

	U11	U22	U33	U12	U13	U23
O4	0.0623 (7)	0.1152 (10)	0.0677 (7)	−0.0271 (7)	0.0134 (5)	−0.0012 (6)
F	0.1049 (8)	0.1062 (9)	0.0868 (7)	−0.0161 (7)	0.0246 (6)	−0.0256 (6)
O1	0.0523 (6)	0.0813 (8)	0.0886 (8)	−0.0117 (5)	0.0137 (5)	0.0053 (6)
O2	0.0684 (7)	0.0970 (8)	0.0630 (6)	−0.0017 (6)	0.0201 (5)	0.0015 (6)
O3	0.0601 (6)	0.0861 (8)	0.0679 (6)	−0.0012 (5)	0.0075 (5)	−0.0097 (5)
C1	0.0414 (6)	0.0491 (7)	0.0814 (9)	−0.0007 (6)	0.0063 (6)	−0.0042 (6)
C2	0.0646 (9)	0.0594 (9)	0.0810 (10)	−0.0177 (7)	0.0099 (7)	−0.0098 (7)
C3	0.0732 (10)	0.0666 (10)	0.0854 (11)	−0.0157 (8)	0.0173 (8)	−0.0035 (8)
C4	0.0600 (8)	0.0715 (10)	0.0785 (10)	−0.0014 (7)	0.0121 (7)	−0.0144 (8)
C5	0.0625 (9)	0.0657 (10)	0.1020 (13)	−0.0142 (8)	0.0148 (8)	−0.0260 (9)
C6	0.0559 (8)	0.0569 (8)	0.0981 (12)	−0.0121 (7)	0.0188 (8)	−0.0114 (8)
C7	0.0456 (7)	0.0498 (7)	0.0817 (9)	0.0004 (6)	0.0092 (6)	0.0014 (6)
C8	0.0479 (7)	0.0645 (9)	0.0787 (10)	−0.0036 (6)	0.0135 (6)	−0.0061 (7)
C9	0.0474 (7)	0.0602 (8)	0.0763 (9)	0.0007 (6)	0.0098 (6)	0.0070 (7)
C10	0.0474 (7)	0.0563 (8)	0.0683 (8)	0.0046 (6)	0.0094 (6)	0.0031 (6)
C11	0.0493 (7)	0.0617 (8)	0.0728 (9)	0.0039 (6)	0.0167 (6)	0.0076 (7)
C12	0.0522 (7)	0.0622 (8)	0.0633 (8)	0.0106 (6)	0.0137 (6)	0.0038 (6)
C13	0.0511 (7)	0.0624 (8)	0.0645 (8)	0.0053 (6)	0.0103 (6)	−0.0023 (6)
C14	0.0486 (7)	0.0690 (9)	0.0670 (9)	−0.0016 (6)	0.0128 (6)	0.0014 (7)
C15	0.0527 (7)	0.0716 (9)	0.0600 (8)	0.0002 (7)	0.0113 (6)	0.0022 (7)
C16	0.0891 (12)	0.0958 (13)	0.0777 (11)	−0.0033 (10)	0.0325 (9)	0.0095 (9)
C17	0.0593 (9)	0.1147 (15)	0.0747 (11)	0.0075 (10)	0.0026 (8)	−0.0003 (10)
C18	0.0681 (10)	0.1196 (16)	0.0749 (11)	−0.0239 (11)	0.0224 (8)	0.0043 (10)

O4—C14	1.3602 (18)	C8—H8A	0.9300
O4—C18	1.423 (2)	C9—C10	1.463 (2)
F—C4	1.350 (2)	C9—H9A	0.9300
O1—C7	1.2218 (18)	C10—C11	1.393 (2)
O2—C12	1.3635 (18)	C10—C15	1.400 (2)
O2—C16	1.420 (2)	C11—C12	1.385 (2)
O3—C13	1.3734 (19)	C11—H11A	0.9300
O3—C17	1.417 (2)	C12—C13	1.390 (2)
C1—C2	1.384 (2)	C13—C14	1.396 (2)
C1—C6	1.391 (2)	C14—C15	1.384 (2)
C1—C7	1.490 (2)	C15—H15A	0.9300
C2—C3	1.378 (2)	C16—H16A	0.9600
C2—H2A	0.9300	C16—H16B	0.9600
C3—C4	1.367 (2)	C16—H16C	0.9600
C3—H3A	0.9300	C17—H17A	0.9600
C4—C5	1.368 (3)	C17—H17B	0.9600
C5—C6	1.374 (3)	C17—H17C	0.9600
C5—H5A	0.9300	C18—H18A	0.9600
C6—H6A	0.9300	C18—H18B	0.9600
C7—C8	1.477 (2)	C18—H18C	0.9600
C8—C9	1.322 (2)
C14—O4—C18	117.66 (13)	C12—C11—C10	120.19 (13)
C12—O2—C16	117.99 (14)	C12—C11—H11A	119.9
C13—O3—C17	113.25 (13)	C10—C11—H11A	119.9
C2—C1—C6	118.10 (15)	O2—C12—C11	124.36 (13)
C2—C1—C7	122.51 (13)	O2—C12—C13	115.61 (13)
C6—C1—C7	119.38 (13)	C11—C12—C13	119.98 (13)
C3—C2—C1	121.37 (15)	O3—C13—C12	119.54 (13)
C3—C2—H2A	119.3	O3—C13—C14	120.55 (13)
C1—C2—H2A	119.3	C12—C13—C14	119.88 (14)
C4—C3—C2	118.33 (16)	O4—C14—C15	124.71 (14)
C4—C3—H3A	120.8	O4—C14—C13	114.82 (13)
C2—C3—H3A	120.8	C15—C14—C13	120.47 (13)
F—C4—C3	118.60 (16)	C14—C15—C10	119.45 (14)
F—C4—C5	118.96 (15)	C14—C15—H15A	120.3
C3—C4—C5	122.45 (16)	C10—C15—H15A	120.3
C4—C5—C6	118.50 (15)	O2—C16—H16A	109.5
C4—C5—H5A	120.8	O2—C16—H16B	109.5
C6—C5—H5A	120.8	H16A—C16—H16B	109.5
C5—C6—C1	121.24 (15)	O2—C16—H16C	109.5
C5—C6—H6A	119.4	H16A—C16—H16C	109.5
C1—C6—H6A	119.4	H16B—C16—H16C	109.5
O1—C7—C8	121.74 (15)	O3—C17—H17A	109.5
O1—C7—C1	120.62 (13)	O3—C17—H17B	109.5
C8—C7—C1	117.64 (12)	H17A—C17—H17B	109.5
C9—C8—C7	121.69 (14)	O3—C17—H17C	109.5
C9—C8—H8A	119.2	H17A—C17—H17C	109.5
C7—C8—H8A	119.2	H17B—C17—H17C	109.5
C8—C9—C10	127.76 (14)	O4—C18—H18A	109.5
C8—C9—H9A	116.1	O4—C18—H18B	109.5
C10—C9—H9A	116.1	H18A—C18—H18B	109.5
C11—C10—C15	120.04 (13)	O4—C18—H18C	109.5
C11—C10—C9	118.17 (13)	H18A—C18—H18C	109.5
C15—C10—C9	121.77 (13)	H18B—C18—H18C	109.5
C6—C1—C2—C3	−0.2 (2)	C16—O2—C12—C11	14.4 (2)
C7—C1—C2—C3	−179.40 (14)	C16—O2—C12—C13	−168.15 (15)
C1—C2—C3—C4	−0.9 (3)	C10—C11—C12—O2	177.51 (14)
C2—C3—C4—F	−178.84 (16)	C10—C11—C12—C13	0.2 (2)
C2—C3—C4—C5	1.0 (3)	C17—O3—C13—C12	104.04 (17)
F—C4—C5—C6	179.78 (15)	C17—O3—C13—C14	−78.13 (19)
C3—C4—C5—C6	−0.1 (3)	O2—C12—C13—O3	0.4 (2)
C4—C5—C6—C1	−1.0 (3)	C11—C12—C13—O3	177.92 (13)
C2—C1—C6—C5	1.2 (2)	O2—C12—C13—C14	−177.47 (13)
C7—C1—C6—C5	−179.61 (15)	C11—C12—C13—C14	0.1 (2)
C2—C1—C7—O1	149.90 (16)	C18—O4—C14—C15	−2.9 (3)
C6—C1—C7—O1	−29.3 (2)	C18—O4—C14—C13	177.40 (16)
C2—C1—C7—C8	−30.8 (2)	O3—C13—C14—O4	1.6 (2)
C6—C1—C7—C8	150.00 (14)	C12—C13—C14—O4	179.41 (14)
O1—C7—C8—C9	4.9 (2)	O3—C13—C14—C15	−178.09 (15)
C1—C7—C8—C9	−174.35 (14)	C12—C13—C14—C15	−0.3 (2)
C7—C8—C9—C10	177.60 (14)	O4—C14—C15—C10	−179.47 (15)
C8—C9—C10—C11	−177.15 (15)	C13—C14—C15—C10	0.2 (2)
C8—C9—C10—C15	4.0 (2)	C11—C10—C15—C14	0.1 (2)
C15—C10—C11—C12	−0.3 (2)	C9—C10—C15—C14	178.96 (14)
C9—C10—C11—C12	−179.18 (14)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···Cg2i	0.93	2.91	3.6571 (19)	138

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯Cg2i	0.93	2.91	3.6571 (19)	138

Symmetry code: (i) . Cg2 is the centroid of the C10–C15 ring.