[4-(All­yloxy)phen­yl](phen­yl)methanone

Richard F D’Vries; Carlos D Grande; Manuel N Chaur; Javier A Ellena; Rigoberto C Advincula

doi:10.1107/S1600536814014342

. 2014 Jun 25;70(Pt 7):o814–o815. doi: 10.1107/S1600536814014342

[4-(Allyloxy)phenyl](phenyl)methanone

Richard F D’Vries ^a,^*, Carlos D Grande ^b, Manuel N Chaur ^c, Javier A Ellena ^a, Rigoberto C Advincula ^d

PMCID: PMC4120571 PMID: 25161593

Abstract

The structure of the title compound, C₁₆H₁₄O₂, features a dihedral angle of 54.4 (3)° between the aromatic rings. The allyl group is rotated by 37.4 (4)° relative to the adjacent benzene ring. The crystal packing is characterized by numerous C—H⋯O and C—H⋯π interactions. Most of these interactions occur in layers along (011). The layers are linked by C—H⋯π interactions along [100], forming a three-dimensional network.

Keywords: crystal structure

Related literature

For more details of the synthesis, see: Prucker et al. (1999 ▶). For photoreactive properties of benzophenone derivates, see: Shirahata & Kishimoto (1984 ▶); Dorman & Prestwich (1994 ▶); Beckett & Porter (1963 ▶); Kubo et al. (2010 ▶); Balakirev et al. (2005 ▶); Ferreira et al. (1995 ▶); Matsushita et al. (1992 ▶). For related structures, see: Schlemper (1982 ▶); Norment & Karle (1962 ▶); Guo et al. (1992 ▶). graphic file with name e-70-0o814-scheme1.jpg

Experimental

Crystal data

C₁₆H₁₄O₂
M _r = 238.27
Monoclinic,
a = 6.0141 (5) Å
b = 7.8839 (8) Å
c = 13.5992 (14) Å
β = 94.442 (6)°
V = 642.86 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.12 × 0.08 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer
1609 measured reflections
1603 independent reflections
1021 reflections with I > 2σ(I)
R _int = 0.065

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.133
S = 1.01
1603 reflections
167 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶), DIAMOND (Brandenburg, 2006 ▶), Mercury (Macrae et al., 2008 ▶) and PARST (Nardelli, 1995 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814014342/ld2129sup1.cif

e-70-0o814-sup1.cif^{(19KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814014342/ld2129Isup2.hkl

e-70-0o814-Isup2.hkl^{(88.4KB, hkl)}

Click here for additional data file.^{(4.8KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814014342/ld2129Isup3.cml

CCDC reference: 1009057

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯Cg1ⁱ	0.93	2.83	3.651 (3)	147
C14—H14B⋯Cg2ⁱⁱ	0.97	2.96	3.630 (3)	127
C10—H10⋯O2ⁱⁱ	0.93	2.89	3.528 (4)	127
C2—H2⋯O1ⁱⁱⁱ	0.93	2.85	3.698 (4)	152
C14—H14B⋯O1^iv	0.97	2.85	3.596 (4)	134

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

RFD acknowledges a CAPES/PNPD scholarship from the Brazilian Ministry of Education (MEC) and the Crystallography Group of the Instituto de Física de São Carlos, Universidade de São Paulo. MNC acknowledges the Centro en Excelencia en Nuevos Materiales (CENM), the Vicerrectoría de Investigaciones of Universidad del Valle, Banco de la República and Colciencias from Colombia for partial financial support. CDG acnowledges the Universidad de San Buenaventura Cali for partial financial support.

supplementary crystallographic information

S1. Introduction

The title compound C₁₆H₁₄O₂, is based on a photoreactive benzophenone derivative that can be bound to SiO₂ surfaces via a silane anchor. This substrate is a compound that has a benzophenone moiety which exhibits a known photoreactivity and is particularly useful in photopolymerizable organopolysiloxane and silicone resins Prucker et al., (1999); Shirahata & Kishimoto, (1984); Dorman & Prestwich, (1994); Beckett & Porter, (1963). When triggered by UV light (λ = 365 nm), a biradical triplet state is formed, which is able of abstracting a proton from any neighboring aliphatic C—H group to form a C—C bond (Ferreira et al., (1995); Balakirev et al., (2005); Kubo et al. (2010)) and as a result of the photochemical reaction, a thin layer of the polymer is covalently bound to the surface (Prucker et al. (1999); Shirahata & Kishimoto, (1984); Dorman & Prestwich, (1994); Matsushita et al. (1992)). This molecule can be also copolymerized with other polymer molecules and will not migrate out through its double bond.

S2. Experimental

Synthesis of (4-Allyloxy-phenyl)-phenyl-methanone. This compound was synthesized by a procedure already reported. A mixture of 4-hydroxybenzophenone (39.6 g, 0.2 mol) and allyl bromide (26.6 g, 0.22 mol) were dissolved in 120 mL of acetone and 28 g of potassium carbonate. The mixture was heated to reflux for 8 h and then cooled down to room temperature. Water (80 mL) was added and the resulting solution was extracted twice with 100 mL of diethyl ether. The combined organic phases were washed with 100 mL of aqueous NaOH (10%) and dried over Na₂SO₄, and the solvent was evaporated. The resulting yellowish product was purified from methanol to yield 40 g (89%) of pure product as confirmed by NMR. FTIR (KBr): 3081, 3059, 3022, 2939, 2865, 1650, 1600 cm^-1. ¹H NMR (CDCl₃, δ(ppm): 4.6 (m, 2H, OCH₂), 5.3-5.5 (m, 2H, CH₂=), 6.1 (m, 1H,=CH-), 7.21 (2H, m); 7.44 (2H, m); 7.56 (1H, m); 7.77 (2H, m); 7.88 (2H, m). ¹³C NMR: δ(ppm) in CDCl₃: 195.13 (C=O), 162.14 (OCarom), 149.12, 137.60, 135.94, 132.78, 131.93, 130.19, 128.35, 118.29, 115.91, 69.34 (OCH₂).

S2.1. Refinement

All H atoms were placed in idealized positions, with C—H bond lengths fixed to 0.93 (aromatic C—H) or 0.97 Å (terminal methylene), and refined as riding with displacement parameters calculated as Uiso(H) = xUeq(carrier C) where x = 1.2.

S3. Results and discussion

The compound C₁₆H₁₄O₂ is a benzophenone derivate formed by two aromatic rings linked by a ketone funtion. The presence of the ketone funtion and an allyloxy group make of this molecule particularly useful in photopolymerizable organopolysiloxane and silicone resins, and a excellent substrate for selective catalysis. The rings are twisted with a torsion angle formed between C6—C1—C7—C8 of 136.59 (31)°. The allyloxy group presents a torsion angle of -7.99 (42)° (C10—C11—O2—C14) relative to the aromatic ring. The molecules interact via supramolecular weak interactions C5—H5···π = 3.651 (3) , C14—H14B···O1 = 3.596 (4) and C10—H10··O2 = 3.528 (4) Å giving rise to supramolecular layers in the plane (011). C14—H14B···π = 3.698 (2) Å interaction join the layers along [100] to obtain the supramolecular crystal packing.