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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o123.
Published online 2007 December 6. doi:  10.1107/S1600536807063398
PMCID: PMC2915193

2,3-Bis[(2-methyl­phen­oxy)meth­yl]buta-1,3-diene

Abstract

The mol­ecule of the title compound, C20H22O2, a symmetrically 2-methyl­phenol-substituted divinyl analog, exhibits crystallographically imposed C 2 symmetry. The mol­ecular structure is essentially planar. The structure is stabilized by a short inter­molecular C—H(...)O contact. Cooperative C—H(...)π inter­actions generate an infinite one-dimensional chain of mol­ecules along the a axis.

Related literature

The crystal structures of three analogous compounds have been published thus far (Alcock et al., 2006 [triangle]; Sathiyanarayanan et al., 2007 [triangle], 2008 [triangle]). For mol­ecular and crystal symmetry, see Yao et al. (2002 [triangle]); Pidcock et al. (2003 [triangle]); Narasegowda et al. (2005 [triangle]); Schmidt et al. (2006 [triangle]).

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Object name is e-64-0o123-scheme1.jpg

Experimental

Crystal data

  • C20H22O2
  • M r = 294.38
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o123-efi1.jpg
  • a = 5.2241 (5) Å
  • b = 21.6274 (19) Å
  • c = 7.5101 (7) Å
  • β = 102.044 (4)°
  • V = 829.84 (13) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.07 mm−1
  • T = 295 (2) K
  • 0.22 × 0.18 × 0.16 mm

Data collection

  • Bruker Kappa APEXII diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2004 [triangle]) T min = 0.973, T max = 0.980
  • 7281 measured reflections
  • 1632 independent reflections
  • 1352 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.060
  • wR(F 2) = 0.141
  • S = 1.15
  • 1632 reflections
  • 143 parameters
  • All H-atom parameters refined
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.15 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: APEX2 and SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807063398/bx2123sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063398/bx2123Isup2.hkl

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

Acknowledgments

We thank the DRDO, India, for financial support (grant No. ERIP/ER/0403461/M/01). RSR acknowledges the Science & Engineering Research Council (DST), Government of India, for providing a Fast-Track grant and the Bioinformatics Center of the School of Biotechnology, Devi Ahilya University, Indore, India, for the use of the computational facilities.

supplementary crystallographic information

Comment

We had previously reported a benzenethiol-substituted divinyl analog, ({2-methylidene-3-[(phenylsulfanyl)methyl]but-3-en-1-yl}sulfanyl)benzene, (I), possessing a C2 point-group symmetry at the center of divinyl group. In this series, the title compound 1-methyl-2-({2-methylidene-3-[(2-methylphenoxy)methyl] but-3-en-1-yl}oxy)benzene, (II), is a symmetrically 2-methylphenol-substituted divinyl analog. The present discussion is concerned with the structure of (II). The molecular structure with atom numbering scheme is shown in Fig 1. Three similar compounds have been reported so far. They are: (a) (I) in space group Pbca (Sathiyanarayanan et al., 2007); (b) phenol-substituted divinyl analog i.e., {[2-methylidene-3-(phenoxymethyl)but-3-en-1-yl]oxy}benzene, (III), in space group P21/c (Sathiyanarayanan et al., 2008); and (c) 4-(3-hydroxy-3-methoxypropyl)phenol-substituted analog, namely, 2,3-bis(4-(2-(methoxycarbonyl)ethyl)phenoxymethyl)buta-1,3-diene, (IV), in space group P 21/c (Alcock et al. 2006; CCDC 277599, private communication).

The molecular symmetry (C2) is retained in the crystal of (II) and the asymmetric unit is composed of one-half of the molecule (Z' = 1/2) as observed in (I), (III) and (IV). The database analysis has revealed that among organic molecules, there is a persistent tendency for molecular symmetry to be retained in the crystal (Yao et al., 2002), although exceptions to this trend have also been reported even in case of inversion center that is mostly conserved in the crystal (Narasegowda et al., 2005; Schmidt et al., 2006). Recent work (Pidcock et al., 2003) has led to the conclusion that the C2 point group symmetry is conserved in about 60% of the reported cases.

Selected bond distances, angles and conformational parameters are provided in Table. 1. 2-methylphenol (O1/C1—C7) and divinyl [C8/C9/C10/C8i/C9i/C10i; symmetry code (i): 2 - x, -y, -z] units are coplanar, giving rise to essentially a planar structure of (II). All the three torsion angles describing molecular conformation i.e., C1—C6—O1—C8, C9—C8—O1—C6 and O1—C8—C9—C9i are trans. The corresponding angles in (IV) are also trans, while in (I) and (III) these angles are [trans, trans and (gauche- or gauche+)] and [trans, gauche- and trans], respectively. Among other differences, the analog (I) exhibits a flip-flop disorder of divinyl group (Sathiyanarayanan et al., 2007)

An intra-molecular C10—H10B···O1 hydrogen bond stabilize the structure of (I). Hydrogen bond parameters are provided in Table 2. Crystal packing is purely governed by weak intermolecular forces. The molecular association via cooperative C8—H8B ··· Cg1(ii) interactions [symmetry code (ii): 1 + x, y, z] give rise to one-dimensional chain of molecules along a axis. Cg1 is the centroid of (C1—C6) ring. Crystal packing view is diplayed in Fig. 2.

Experimental

One mole of 2,3-bis(iodomethyl)buta-1,3-diene in DMF was added to two moles of sodium phenoxide in DMF dropwise with cooling. The reaction mixture was stirred overnight at room temperature and poured into crushed ice. The solids were filtered and dissolved in ether. The ether extract was washed with sodium thiosulfate and 10% sodium hydroxide and finally with water. The solid product was obtained by removal of ether after drying, which was recrystallized from hexane at room temperature (m.p. 346° K).

Refinement

The positions of all H atoms were freely refined. The distances with H-atoms are in ranges:- Caromatic—H = 0.97 (2)–1.02 (3); Csp2—H = 0.95 (3)–1.02 (3); Cmethyl—H = 0.99 (4)–1.02 (3) and Cmethylene—H = 1.00 (2)–1.01 (2) Å.

Figures

Fig. 1.
A view of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at 30% probability level.
Fig. 2.
Projection of the crystal packing down the c axis showing cooperative C—H···π interactions forming one-dimensional chain of molecular along a axis. Cg1 is the centroid of (C1—C6) ring. Only selected hydrogen ...

Crystal data

C20H22O2F000 = 316
Mr = 294.38Dx = 1.178 Mg m3
Monoclinic, P21/nMelting point: 346 K
Hall symbol: -P 2ynMo Kα radiation λ = 0.71073 Å
a = 5.2241 (5) ÅCell parameters from 4455 reflections
b = 21.6274 (19) Åθ = 2.8–31.0º
c = 7.5101 (7) ŵ = 0.07 mm1
β = 102.044 (4)ºT = 295 (2) K
V = 829.84 (13) Å3Prism, colourless
Z = 20.22 × 0.18 × 0.16 mm

Data collection

BrukerKkappa diffractometer1632 independent reflections
Radiation source: fine-focus sealed tube1352 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.025
T = 295(2) Kθmax = 26.0º
ω and [var phi]–scanθmin = 2.9º
Absorption correction: multi-scan(SADABS; Bruker, 2004)h = −6→6
Tmin = 0.973, Tmax = 0.980k = −25→26
7281 measured reflectionsl = −9→9

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060All H-atom parameters refined
wR(F2) = 0.141  w = 1/[σ2(Fo2) + (0.0254P)2 + 0.7904P] where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max = 0.001
1632 reflectionsΔρmax = 0.20 e Å3
143 parametersΔρmin = −0.15 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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.Weighted least-squares planes through the starred atoms (Nardelli, Musatti, Domiano & Andreetti Ric.Sci.(1965),15(II—A),807). Equation of the plane: m1*X+m2*Y+m3*Z=dPlane 1 m1 = -0.65734(0.00051) m2 = -0.66742(0.00044) m3 = -0.34994(0.00085) D = -3.59801(0.00113) Atom d s d/s (d/s)**2 O1 * 0.0138 0.0018 7.856 61.715 C1 * -0.0049 0.0023 - 2.109 4.447 C2 * 0.0165 0.0026 6.321 39.959 C3 * 0.0134 0.0027 4.955 24.548 C4 * -0.0055 0.0027 - 2.046 4.184 C5 * -0.0199 0.0026 - 7.572 57.329 C6 * -0.0077 0.0022 - 3.472 12.052 C7 * -0.0354 0.0037 - 9.660 93.324 C8 0.0645 0.0024 26.886 722.869 C9 0.1395 0.0021 64.912 4213.542 C10 0.1687 0.0030 56.080 3144.964 ============ Sum((d/s)**2) for starred atoms 297.558 Chi-squared at 95% for 5 degrees of freedom: 11.10 The group of atoms deviates significantly from planarityPlane 2 m1 = -0.68850(0.00264) m2 = -0.62945(0.00157) m3 = -0.36022(0.00316) D = -3.60224(0.00936) Atom d s d/s (d/s)**2 C8 * 0.0000 0.0024 0.000 0.000 C9 * 0.0000 0.0021 0.000 0.000 C10 * 0.0000 0.0030 0.000 0.000 O1 - 0.0218 0.0018 - 12.401 153.784 ============ Sum((d/s)**2) for starred atoms 0.000Plane 3 m1 = -0.67385(0.00031) m2 = -0.65235(0.00031) m3 = -0.34694(0.00075) D = -3.56623(0.00074) Atom d s d/s (d/s)**2 O1 * -0.0381 0.0018 - 21.735 472.397 C1 * -0.0064 0.0023 - 2.735 7.482 C2 * 0.0453 0.0026 17.389 302.387 C3 * 0.0520 0.0027 19.220 369.400 C4 * 0.0123 0.0027 4.532 20.540 C5 * -0.0327 0.0026 - 12.442 154.803 C6 * -0.0301 0.0022 - 13.569 184.128 C7 * -0.0475 0.0037 - 12.943 167.509 C8 * -0.0100 0.0024 - 4.185 17.517 C9 * 0.0345 0.0021 16.077 258.455 C10 * 0.0611 0.0030 20.305 412.299 ============ Sum((d/s)**2) for starred atoms 2366.918 Chi-squared at 95% for 8 degrees of freedom: 15.50 The group of atoms deviates significantly from planarityDihedral angles formed by LSQ-planes Plane - plane angle (s.u.) angle (s.u.) 1 2 2.88 (0.12) 177.12 (0.12) 1 3 1.29 (0.03) 178.71 (0.03) 2 3 1.73 (0.13) 178.27 (0.13)
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
C10.3342 (4)0.14009 (11)0.2814 (3)0.0386 (5)
C20.1449 (5)0.18556 (12)0.2633 (4)0.0464 (6)
H20.055 (5)0.1937 (12)0.369 (4)0.056*
C30.0729 (5)0.21981 (12)0.1049 (4)0.0501 (7)
H3−0.070 (5)0.2516 (13)0.098 (4)0.059 (8)*
C40.1911 (5)0.20830 (12)−0.0385 (4)0.0504 (7)
H40.151 (6)0.2322 (14)−0.150 (4)0.071 (9)*
C50.3809 (5)0.16273 (12)−0.0253 (3)0.0459 (6)
H50.466 (5)0.1542 (11)−0.125 (3)0.045 (7)*
C60.4503 (4)0.12846 (10)0.1331 (3)0.0368 (5)
C70.4171 (7)0.10395 (17)0.4548 (4)0.0592 (8)
H7A0.416 (6)0.0576 (17)0.432 (4)0.081 (10)*
H7B0.297 (7)0.1125 (16)0.537 (5)0.095 (12)*
H7C0.601 (8)0.1140 (18)0.512 (5)0.108 (14)*
C80.7492 (5)0.06522 (11)0.0126 (3)0.0378 (5)
C90.9288 (4)0.01133 (10)0.0684 (3)0.0354 (5)
C100.9538 (6)−0.01399 (14)0.2310 (4)0.0532 (7)
O10.6296 (3)0.08156 (8)0.1591 (2)0.0478 (5)
H8A0.608 (5)0.0526 (10)−0.094 (3)0.037 (6)*
H8B0.848 (5)0.1015 (12)−0.019 (3)0.044 (7)*
H10A1.075 (5)−0.0505 (13)0.270 (4)0.058 (8)*
H10B0.863 (5)0.0022 (12)0.318 (4)0.053 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0386 (12)0.0410 (13)0.0358 (12)−0.0014 (10)0.0069 (9)−0.0044 (10)
C20.0435 (14)0.0495 (15)0.0480 (14)0.0027 (11)0.0135 (11)−0.0113 (11)
C30.0456 (14)0.0426 (15)0.0612 (17)0.0109 (12)0.0089 (12)−0.0008 (12)
C40.0504 (15)0.0459 (15)0.0548 (16)0.0070 (12)0.0106 (12)0.0122 (12)
C50.0493 (14)0.0476 (15)0.0439 (14)0.0086 (11)0.0166 (11)0.0087 (11)
C60.0341 (11)0.0344 (12)0.0422 (12)0.0028 (9)0.0085 (9)−0.0006 (10)
C70.072 (2)0.069 (2)0.0381 (14)0.0117 (17)0.0150 (14)0.0041 (13)
C80.0373 (12)0.0397 (13)0.0365 (12)0.0060 (10)0.0085 (10)0.0012 (10)
C90.0299 (11)0.0389 (12)0.0362 (12)0.0012 (9)0.0042 (9)−0.0009 (9)
C100.0617 (17)0.0565 (17)0.0434 (14)0.0210 (14)0.0156 (12)0.0080 (12)
O10.0539 (11)0.0516 (11)0.0405 (9)0.0211 (8)0.0158 (8)0.0076 (8)

Geometric parameters (Å, °)

C1—C21.381 (3)C7—H7A1.02 (3)
C1—C61.397 (3)C7—H7B0.99 (4)
C1—C71.504 (4)C7—H7C0.99 (4)
C2—C31.385 (4)C8—O11.418 (3)
C2—H21.02 (3)C8—C91.500 (3)
C3—C41.372 (4)C8—H8A1.01 (2)
C3—H31.01 (3)C8—H8B1.00 (2)
C4—C51.387 (3)C9—C101.320 (3)
C4—H40.97 (3)C9—C9i1.472 (4)
C5—C61.384 (3)C10—H10A1.02 (3)
C5—H50.97 (2)C10—H10B0.95 (3)
C6—O11.367 (3)
C2—C1—C6118.1 (2)C1—C7—H7B110 (2)
C2—C1—C7121.8 (2)H7A—C7—H7B108 (3)
C6—C1—C7120.1 (2)C1—C7—H7C110 (2)
C1—C2—C3121.7 (2)H7A—C7—H7C105 (3)
C1—C2—H2119.0 (15)H7B—C7—H7C112 (3)
C3—C2—H2119.3 (15)O1—C8—C9109.15 (18)
C4—C3—C2119.4 (2)O1—C8—H8A108.4 (13)
C4—C3—H3122.2 (16)C9—C8—H8A108.9 (13)
C2—C3—H3118.3 (16)O1—C8—H8B109.0 (14)
C3—C4—C5120.3 (2)C9—C8—H8B110.8 (14)
C3—C4—H4122.0 (18)H8A—C8—H8B110.6 (19)
C5—C4—H4117.7 (18)C10—C9—C9i122.7 (3)
C6—C5—C4119.8 (2)C10—C9—C8121.1 (2)
C6—C5—H5119.1 (15)C9i—C9—C8116.2 (2)
C4—C5—H5121.1 (15)C9—C10—H10A121.5 (15)
O1—C6—C5124.7 (2)C9—C10—H10B120.9 (16)
O1—C6—C1114.7 (2)H10A—C10—H10B118 (2)
C5—C6—C1120.6 (2)C6—O1—C8118.28 (17)
C1—C7—H7A112.0 (18)
C6—C1—C2—C3−1.0 (4)C7—C1—C6—O12.4 (3)
C7—C1—C2—C3178.5 (3)C2—C1—C6—C51.5 (3)
C1—C2—C3—C40.3 (4)C7—C1—C6—C5−178.1 (3)
C2—C3—C4—C50.1 (4)O1—C8—C9—C100.9 (3)
C3—C4—C5—C60.4 (4)C5—C6—O1—C8−1.8 (3)
C4—C5—C6—O1178.3 (2)C1—C6—O1—C8177.6 (2)
C4—C5—C6—C1−1.1 (4)C9—C8—O1—C6−177.60 (19)
C2—C1—C6—O1−178.0 (2)O1—C8—C9—C9i−179.5 (2)

Symmetry codes: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C10—H10B···O10.95 (3)2.29 (3)2.655 (4)102 (2)
C8—H8B···Cg1ii1.00 (2)2.70 (3)3.534 (3)141 (2)

Symmetry codes: (ii) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BX2123).

References

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