A redetermination of 1,5-bis­(4-methoxy­phen­yl)penta-1,4-dien-3-one at 120 (2) K

Harrison, W.T.A.; Sarojini, B.K.; Vijaya Raj, K.K.; Yathirajan, H.S.; Narayana, B.

doi:10.1107/S1600536806009640

organic compounds

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ISSN: 2056-9890

Volume 62| Part 4| April 2006| Pages o1522-o1523

https://doi.org/10.1107/S1600536806009640

A redetermination of 1,5-bis(4-methoxyphenyl)penta-1,4-dien-3-one at 120 (2) K

William T. A. Harrison,^a ^* B. K. Sarojini,^b K. K. Vijaya Raj,^c H. S. Yathirajan ^d and B. Narayana ^c

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, ^bDepartment of Chemistry, P. A. College of Engineering, Nadupadavu, Mangalore 574 153, India, ^cDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, India, and ^dDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 14 March 2006; accepted 14 March 2006; online 22 March 2006)

The title compound, C₁₉H₁₈O₃, is confirmed to crystallize with orthorhombic symmetry [Shan et al. (1999 ). Z. Kristallogr. New Cryst. Struct. 214, 381–382; Marsh (2004 ). Acta Cryst. B60, 252–253]. The molecule has crystallographically imposed twofold symmetry and the only possible intermolecular interaction is a weak C—H⋯O bond.

Comment

Although the title compound (common name bischalcone), (I), was first prepared over 100 years ago (von Baeyer & Villiger, 1902 ), it was not until 1999 that its single-crystal structure was determined (Shan et al., 1999). These workers described its structure as monoclinic (space group Cc), with all atoms occupying general positions. Later, Marsh (2004) noted that the crystal symmetry of (I) is better described as orthorhombic (space group Aba2), as confirmed by the present study. This compound is of interest to us on account of its substantial second harmonic generation (SHG) response (six times that of urea) to red light. The current structure determination at 120 (2) K represents a significant improvement in precision compared with the structure determined from room-temperature data.

The geometric parameters for (I) are normal. The complete molecule is generated from the asymmetric unit by twofold symmetry, with atoms C1 and O1 lying on the rotation axis (Fig. 1). The dihedral angle between the two benzene rings in (I) is 56.92 (9)°. A short H3⋯H3ⁱ [symmetry code: (i) 1 − x, 1 − y, z] intramolecular contact of 2.18 Å is present, which may help to explain the twisted conformation of the molecule about the central ketone group [pseudo-torsion angle C3—C2⋯C2ⁱ—C3ⁱ = −45.1 (4)°]. Atoms C3, O2 and C10 are displaced from the mean plane of the C4–C9 benzene ring by 0.111 (5), 0.024 (4) and 0.128 (6) Å, respectively.

The packing in (I), shown in Fig. 2, results in head-to-tail columns of molecules which all propagate along [001] in the same sense; the large SHG signal of (I) could be correlated with this lining-up effect. A PLATON (Spek, 2003 ) analysis of (I) identified a possible C—H⋯O interaction (Table 1) that might help to crosslink these molecular columns. There are no π–π stacking interactions in (I).

Figure 1
View of (I)

, showing 50% displacement ellipsoids, with arbitrary spheres for H atoms. [Symmetry code: (i) 1 − x, 1 − y, z.]

Figure 2
The molecular packing in (I)

, viewed along [100], with H atoms omitted for clarity.

Experimental

Compound (I) was prepared according to a literature method (Vogel, 1999 ) and recrystallized from acetone by slow evaporation (m.p. 378–381 K). Elemental analysis, found: C 77.25, H 6.02%; calculated for C₁₉H₁₈O₃: C 77.55, H 6.12%.

Crystal data

C₁₉H₁₈O₃
M_r = 294.33
Orthorhombic, A b a 2
a = 7.2756 (9) Å
b = 33.5830 (6) Å
c = 6.132 (5) Å
V = 1498.3 (12) Å³
Z = 4
D_x = 1.305 Mg m⁻³
Mo Kα radiation
Cell parameters from 1686 reflections
θ = 1.0–27.5°
μ = 0.09 mm⁻¹
T = 120 (2) K
Lath, pale yellow
0.52 × 0.22 × 0.04 mm

Data collection

Bruker-Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.956, T_max = 0.997
8103 measured reflections
942 independent reflections
632 reflections with I > 2σ(I)
R_int = 0.093
θ_max = 27.8°
h = −9 → 8
k = −43 → 43
l = −6 → 7

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.127
S = 1.10
942 reflections
102 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0604P)² + 0.238P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯O2ⁱ	0.98	2.53	3.442 (4)	154
Symmetry code: (i) $[-x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

In the absence of significant anomalous scattering effects, Friedel pairs were merged prior to refinement. The H atoms were positioned geometrically (C—H = 0.95–0.98 Å) and refined as riding, with U_iso(H) = 1.2U_eq(carrier) or 1.5U_eq(methyl carrier). The methyl group was rotated to fit the electron density.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK, DENZO (Otwinowski & Minor, 1997) and SORTAV (Blessing, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536806009640/lh2026sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806009640/lh2026Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO(Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

1,5-bis(4-methoxyphenyl)penta-1,4-dien-3-one top

Crystal data top

C₁₉H₁₈O₃	F(000) = 624
M_r = 294.33	D_x = 1.305 Mg m⁻³
Orthorhombic, Aba2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: A 2 -2ac	Cell parameters from 1686 reflections
a = 7.2756 (9) Å	θ = 1.0–27.5°
b = 33.5830 (6) Å	µ = 0.09 mm⁻¹
c = 6.132 (5) Å	T = 120 K
V = 1498.3 (12) Å³	Lath, pale yellow
Z = 4	0.52 × 0.22 × 0.04 mm

Data collection top

Bruker-Nonius KappaCCD diffractometer	942 independent reflections
Radiation source: fine-focus sealed tube	632 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.093
φ and ω scans	θ_max = 27.8°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −9→8
T_min = 0.956, T_max = 0.997	k = −43→43
8103 measured reflections	l = −6→7

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: none
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0604P)² + 0.238P] where P = (F_o² + 2F_c²)/3
942 reflections	(Δ/σ)_max < 0.001
102 parameters	Δρ_max = 0.22 e Å⁻³
1 restraint	Δρ_min = −0.24 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.5000	0.5000	0.3446 (9)	0.0326 (13)
C2	0.4564 (4)	0.46240 (9)	0.4579 (6)	0.0331 (9)
H2	0.3791	0.4441	0.3832	0.040*
C3	0.5145 (5)	0.45178 (10)	0.6529 (6)	0.0302 (9)
H3	0.5728	0.4717	0.7381	0.036*
C4	0.4981 (4)	0.41190 (9)	0.7517 (6)	0.0262 (8)
C5	0.4102 (4)	0.38001 (10)	0.6492 (6)	0.0299 (8)
H5	0.3505	0.3842	0.5134	0.036*
C6	0.4086 (4)	0.34238 (9)	0.7415 (6)	0.0288 (8)
H6	0.3473	0.3212	0.6690	0.035*
C7	0.4957 (4)	0.33534 (10)	0.9389 (5)	0.0262 (8)
C8	0.5818 (4)	0.36670 (9)	1.0448 (6)	0.0270 (8)
H8	0.6417	0.3624	1.1804	0.032*
C9	0.5801 (4)	0.40439 (9)	0.9520 (5)	0.0284 (8)
H9	0.6369	0.4257	1.0280	0.034*
C10	0.5861 (5)	0.28785 (10)	1.2094 (5)	0.0413 (10)
H10A	0.5660	0.2599	1.2480	0.062*
H10B	0.5414	0.3049	1.3277	0.062*
H10C	0.7177	0.2925	1.1870	0.062*
O1	0.5000	0.5000	0.1441 (6)	0.0465 (11)
O2	0.4879 (3)	0.29697 (6)	1.0122 (5)	0.0323 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.036 (3)	0.033 (3)	0.029 (4)	0.003 (2)	0.000	0.000
C2	0.0354 (18)	0.034 (2)	0.030 (2)	0.0011 (15)	−0.0052 (19)	−0.0039 (18)
C3	0.0305 (19)	0.034 (2)	0.026 (2)	0.0038 (15)	0.0008 (19)	−0.0055 (17)
C4	0.0258 (16)	0.0304 (17)	0.0225 (18)	0.0024 (15)	0.0025 (17)	−0.0029 (16)
C5	0.0272 (19)	0.043 (2)	0.0193 (15)	0.0021 (15)	−0.0021 (16)	−0.0035 (17)
C6	0.0275 (17)	0.0335 (18)	0.0254 (18)	−0.0029 (15)	0.0008 (18)	−0.0045 (17)
C7	0.0273 (16)	0.0272 (16)	0.024 (2)	0.0012 (14)	0.0050 (19)	−0.0007 (14)
C8	0.0266 (17)	0.0331 (18)	0.0212 (17)	0.0019 (15)	−0.0022 (15)	−0.0016 (16)
C9	0.0273 (16)	0.0267 (17)	0.031 (2)	0.0017 (14)	−0.0018 (19)	−0.0024 (18)
C10	0.057 (2)	0.032 (2)	0.034 (2)	0.0021 (18)	−0.009 (2)	0.0054 (19)
O1	0.071 (3)	0.034 (2)	0.034 (2)	−0.0016 (18)	0.000	0.000
O2	0.0397 (13)	0.0251 (11)	0.0320 (14)	−0.0027 (11)	−0.0040 (13)	0.0013 (11)

Geometric parameters (Å, º) top

C1—O1	1.230 (6)	C6—C7	1.386 (5)
C1—C2ⁱ	1.476 (4)	C6—H6	0.9500
C1—C2	1.476 (4)	C7—O2	1.366 (4)
C2—C3	1.318 (5)	C7—C8	1.387 (4)
C2—H2	0.9500	C8—C9	1.388 (4)
C3—C4	1.475 (4)	C8—H8	0.9500
C3—H3	0.9500	C9—H9	0.9500
C4—C9	1.389 (5)	C10—O2	1.438 (4)
C4—C5	1.397 (5)	C10—H10A	0.9800
C5—C6	1.385 (4)	C10—H10B	0.9800
C5—H5	0.9500	C10—H10C	0.9800

O1—C1—C2ⁱ	118.1 (2)	C7—C6—H6	119.7
O1—C1—C2	118.1 (2)	O2—C7—C6	115.4 (3)
C2ⁱ—C1—C2	123.8 (5)	O2—C7—C8	125.5 (3)
C3—C2—C1	126.1 (3)	C6—C7—C8	119.1 (3)
C3—C2—H2	116.9	C7—C8—C9	119.8 (3)
C1—C2—H2	116.9	C7—C8—H8	120.1
C2—C3—C4	126.4 (4)	C9—C8—H8	120.1
C2—C3—H3	116.8	C8—C9—C4	122.2 (3)
C4—C3—H3	116.8	C8—C9—H9	118.9
C9—C4—C5	117.1 (3)	C4—C9—H9	118.9
C9—C4—C3	119.6 (3)	O2—C10—H10A	109.5
C5—C4—C3	123.3 (4)	O2—C10—H10B	109.5
C6—C5—C4	121.3 (3)	H10A—C10—H10B	109.5
C6—C5—H5	119.4	O2—C10—H10C	109.5
C4—C5—H5	119.4	H10A—C10—H10C	109.5
C5—C6—C7	120.6 (3)	H10B—C10—H10C	109.5
C5—C6—H6	119.7	C7—O2—C10	117.2 (2)

O1—C1—C2—C3	152.1 (3)	C5—C6—C7—C8	1.2 (4)
C2ⁱ—C1—C2—C3	−27.9 (3)	O2—C7—C8—C9	179.8 (3)
C1—C2—C3—C4	−168.9 (3)	C6—C7—C8—C9	−0.2 (5)
C2—C3—C4—C9	174.6 (3)	C7—C8—C9—C4	−1.6 (5)
C2—C3—C4—C5	−2.3 (5)	C5—C4—C9—C8	2.3 (4)
C9—C4—C5—C6	−1.3 (5)	C3—C4—C9—C8	−174.8 (3)
C3—C4—C5—C6	175.6 (3)	C6—C7—O2—C10	176.3 (3)
C4—C5—C6—C7	−0.4 (5)	C8—C7—O2—C10	−3.8 (4)
C5—C6—C7—O2	−178.9 (3)

Symmetry code: (i) −x+1, −y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O2ⁱⁱ	0.98	2.53	3.442 (4)	154

Symmetry code: (ii) −x+1, −y+1/2, z+1/2.

Acknowledgements

We thank the EPSRC National Crystallography Service (University of Southampton, England) for data collection. One of the authors (BKS) thanks AICTE, Government of India, New Delhi, for financial assistance under the Career Award for Young Teachers (CAYT) scheme.

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