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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): o2678.
Published online 2010 September 30. doi:  10.1107/S1600536810037141
PMCID: PMC2983339

(1E,3E)-1,4-Bis(4-meth­oxy­phen­yl)buta-1,3-diene

Abstract

The title compound, C18H18O2, which exhibits blue emission in the solid state, is an inter­mediate in the preparation of liquid crystals and polymers. The mol­ecule is located on an inversion centre. In the crystal, mol­ecules are arranged in a herringbone motif.

Related literature

For related structures, see: George et al. (1998 [triangle]); Vishnumurthy et al. (2002 [triangle]); Davis et al. (2004 [triangle], 2008 [triangle]); Kumar et al. (2009 [triangle]); Ono et al. (2009 [triangle]). For the synthesis and the use of the title compound in the preparation of polymers and chiral liquid crystals, see: Rotarski (1908 [triangle]); Wang et al. (2003 [triangle]); Das et al. (2008 [triangle]). For mol­ecules with a herringbone arrangement, see: Koren et al. (2003 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2678-scheme1.jpg

Experimental

Crystal data

  • C18H18O2
  • M r = 266.32
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2678-efi1.jpg
  • a = 7.3543 (3) Å
  • b = 6.2617 (3) Å
  • c = 31.3872 (13) Å
  • V = 1445.39 (11) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 293 K
  • 0.25 × 0.22 × 0.22 mm

Data collection

  • Bruker X8 APEXII CCD area-detector diffractometer
  • Absorption correction: numerical (SADABS; Sheldrick, 2006 [triangle]) T min = 0.981, T max = 0.983
  • 40427 measured reflections
  • 1658 independent reflections
  • 1287 reflections with I > 2σ(I)
  • R int = 0.036

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.110
  • S = 1.08
  • 1658 reflections
  • 92 parameters
  • H-atom parameters constrained
  • Δρmax = 0.13 e Å−3
  • Δρmin = −0.13 e Å−3

Data collection: APEX2 (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037141/is2575sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037141/is2575Isup2.hkl

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

Acknowledgments

Research grants from the Department of Science and Technology (DST), Government of India, are gratefully acknowledged. This is contribution No. PPS-300 from PPS-NIIST. GN is grateful to the Council of Scientific and Industrial Research (CSIR) for a research fellowship. Funding from the National Science Foundation (MRI,CHE-0420497) for purchase of the APEXII diffractometer is also acknowledged.

supplementary crystallographic information

Comment

Although the crystal structures of a number of butadiene molecules have been reported (George et al., 1998; Vishnumurthy et al., 2002; Davis et al., 2004, 2008; Kumar et al., 2009; Ono et al., 2009), that of the title compound, C18H18O2, (I), has not been determined and the structure is reported here (Fig. 1). There are four molecules of (I) per unit cell. The symmetrical molecules are arranged in a herringbone fashion (Koren et al., 2003) in which the molecules are packed in an edge-to-face orientation (Fig. 2).

Thermal properties: On heating, crystals of (I) melted at 237 °C, which on further heating sublimed at 246 °C. The sublimed-condensed crystals were chemically unaltered as evidenced by NMR and MS analyses.

Experimental

A mixture of diethyl-4-methoxybenzylphosphonate (1 equiv) and potassium tert-butoxide (5 equiv) were stirred in dry DMF at room temperature and cooled to 273 K. 4-Methoxycinnamaldehyde (1 equiv) dissolved in dry DMF was slowly added into the solution. The reaction mixture was allowed to stir for 12 h at room temperature. TLC analysis indicated completion of reaction. Reaction mixture was poured into ice water, extracted with dichloromethane and concentrated under reduced pressure. The residue was washed with ethyl acetate and filtered. The compound being insoluble in ethyl acetate remained in the residue. This was repeatedly washed with ethyl acetate (small quantities) to obtain pure title compound. The small amount of compound which remained in the filtrate was recovered by column chromatography through silica gel (100–200 mesh), using 5% ethyl acetate/hexane as the mobile phase. Single crystals obtained from ethylacetate at room temperature were of poor quality (high R value) and the structure determination was carried out at 100 K. Fresh crystals were grown from chloroform/hexanes at room temperature which were of higher quality to permit X-ray analysis at 293 K. The data presented herein are from the latter determination.

Refinement

H atoms bonded to N and O atoms were located in a difference map and refined with distance restraints of O—H = 0.84 (2) and N—H = 0.87 (2) Å, and with Uiso(H) = 1.2Ueq(N,O). Other H atoms were positioned geometrically and refined using a riding model (including free rotation about the ethanol C—C bond), with C—H = 0.95–0.99 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).

Figures

Fig. 1.
The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
Fig. 2.
The herringbone packing of (I) in the crystal structure.

Crystal data

C18H18O2F(000) = 568
Mr = 266.32Dx = 1.224 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 7512 reflections
a = 7.3543 (3) Åθ = 2.6–23.6°
b = 6.2617 (3) ŵ = 0.08 mm1
c = 31.3872 (13) ÅT = 293 K
V = 1445.39 (11) Å3Pyramidal, colourless
Z = 40.25 × 0.22 × 0.22 mm

Data collection

Bruker X8 APEXII CCD area-detector diffractometer1658 independent reflections
Radiation source: fine-focus sealed tube1287 reflections with I > 2σ(I)
graphiteRint = 0.036
[var phi] and ω scansθmax = 27.5°, θmin = 1.3°
Absorption correction: numerical (SADABS; Sheldrick, 2006)h = −8→9
Tmin = 0.981, Tmax = 0.983k = −8→8
40427 measured reflectionsl = −40→37

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H-atom parameters constrained
S = 1.08w = 1/[σ2(Fo2) + (0.0429P)2 + 0.3178P] where P = (Fo2 + 2Fc2)/3
1658 reflections(Δ/σ)max < 0.001
92 parametersΔρmax = 0.13 e Å3
0 restraintsΔρmin = −0.13 e Å3

Special details

Experimental. 2010–02-01 # Formatted by publCIF
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)

xyzUiso*/Ueq
O1−0.01884 (15)0.42509 (16)0.19955 (3)0.0584 (3)
C1−0.00667 (17)0.4944 (2)0.15818 (4)0.0420 (3)
C20.07908 (18)0.3855 (2)0.12580 (4)0.0458 (3)
H20.13410.25430.13100.055*
C30.08211 (18)0.4740 (2)0.08547 (4)0.0441 (3)
H30.13860.39880.06360.053*
C40.00422 (16)0.6707 (2)0.07623 (4)0.0396 (3)
C5−0.08465 (17)0.7752 (2)0.10963 (4)0.0440 (3)
H5−0.14110.90560.10460.053*
C6−0.09002 (18)0.6884 (2)0.14980 (4)0.0455 (3)
H6−0.15010.76050.17160.055*
C70.02594 (18)0.7620 (2)0.03382 (4)0.0452 (3)
H70.07690.67290.01330.054*
C8−0.01863 (18)0.9584 (2)0.02086 (4)0.0461 (3)
H8−0.07771.04720.04020.055*
C90.0738 (3)0.2339 (3)0.21039 (5)0.0789 (6)
H9A0.02540.11760.19400.118*
H9B0.05770.20500.24020.118*
H9C0.20100.24970.20430.118*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0773 (7)0.0568 (6)0.0410 (6)0.0056 (6)0.0018 (5)0.0061 (5)
C10.0447 (7)0.0442 (7)0.0371 (7)−0.0047 (6)−0.0013 (5)0.0012 (6)
C20.0485 (8)0.0395 (7)0.0495 (8)0.0068 (6)0.0004 (6)0.0015 (6)
C30.0454 (7)0.0431 (7)0.0439 (7)0.0041 (6)0.0049 (6)−0.0034 (6)
C40.0366 (6)0.0405 (7)0.0416 (7)−0.0029 (5)−0.0018 (5)−0.0007 (5)
C50.0446 (7)0.0395 (7)0.0479 (8)0.0056 (6)0.0001 (6)−0.0005 (6)
C60.0485 (8)0.0439 (7)0.0441 (7)0.0043 (6)0.0036 (6)−0.0047 (6)
C70.0464 (7)0.0484 (8)0.0407 (7)−0.0010 (6)−0.0012 (6)−0.0009 (6)
C80.0463 (7)0.0488 (8)0.0430 (7)−0.0031 (6)−0.0036 (6)0.0015 (6)
C90.1102 (16)0.0692 (11)0.0574 (10)0.0158 (11)−0.0010 (10)0.0204 (9)

Geometric parameters (Å, °)

O1—C11.3721 (15)C5—C61.3735 (18)
O1—C91.4190 (19)C5—H50.9300
C1—C21.3768 (18)C6—H60.9300
C1—C61.3860 (18)C7—C81.3367 (19)
C2—C31.3820 (18)C7—H70.9300
C2—H20.9300C8—C8i1.435 (3)
C3—C41.3890 (18)C8—H80.9300
C3—H30.9300C9—H9A0.9600
C4—C51.3978 (18)C9—H9B0.9600
C4—C71.4573 (18)C9—H9C0.9600
C1—O1—C9117.55 (12)C5—C6—C1120.54 (12)
O1—C1—C2124.87 (12)C5—C6—H6119.7
O1—C1—C6115.34 (12)C1—C6—H6119.7
C2—C1—C6119.78 (12)C8—C7—C4127.73 (13)
C1—C2—C3119.00 (12)C8—C7—H7116.1
C1—C2—H2120.5C4—C7—H7116.1
C3—C2—H2120.5C7—C8—C8i124.37 (17)
C2—C3—C4122.70 (12)C7—C8—H8117.8
C2—C3—H3118.6C8i—C8—H8117.8
C4—C3—H3118.6O1—C9—H9A109.5
C3—C4—C5116.82 (12)O1—C9—H9B109.5
C3—C4—C7119.55 (12)H9A—C9—H9B109.5
C5—C4—C7123.56 (12)O1—C9—H9C109.5
C6—C5—C4121.12 (12)H9A—C9—H9C109.5
C6—C5—H5119.4H9B—C9—H9C109.5
C4—C5—H5119.4
C9—O1—C1—C24.3 (2)C7—C4—C5—C6−175.32 (12)
C9—O1—C1—C6−176.19 (14)C4—C5—C6—C10.1 (2)
O1—C1—C2—C3−179.72 (12)O1—C1—C6—C5179.15 (12)
C6—C1—C2—C30.81 (19)C2—C1—C6—C5−1.33 (19)
C1—C2—C3—C40.9 (2)C3—C4—C7—C8−170.76 (13)
C2—C3—C4—C5−2.09 (19)C5—C4—C7—C86.0 (2)
C2—C3—C4—C7174.90 (13)C4—C7—C8—C8i175.49 (15)
C3—C4—C5—C61.54 (18)

Symmetry codes: (i) −x, −y+2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2575).

References

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