Crystal structure of 4-(prop-2-yn-1-yl­oxy)benzo­nitrile

Mayu Kanagawa; Tsunehisa Okuno

doi:10.1107/S2056989014028035

. 2015 Jan 10;71(Pt 2):o97–o98. doi: 10.1107/S2056989014028035

Crystal structure of 4-(prop-2-yn-1-yloxy)benzonitrile

Mayu Kanagawa ^a, Tsunehisa Okuno ^a,^*

PMCID: PMC4384594 PMID: 25878891

Abstract

In the title compound, C₁₀H₇NO, the dihedral angle between the aromatic ring and the prop-2-yn-1-yloxy grouping is 9.47 (10)°. The bond lengths indicate electronic conjugation between the cyano group, the benzene ring and the propynyloxy oxygen atom. In the crystal, a hydrogen bond between the acetylenic C—H atom and the cyano nitrogen atom link the molecules into wave-like [30-1] C(11) chains. These chains are connected by Csp ²—H⋯π_ac (π_ac is the acetylinic C—C triple bond) close contacts [2.794 (1) Å], resulting in a rolling sheet structure parallel to the ac plane and aromatic π–π stacking interactions between the sheets [centroid–centroid distance = 3.593 (2) Å] generate a three-dimensional network.

Keywords: crystal structure, prop-2-yn-1-yloxy, hydrogen bonding, C—H⋯π interactions, π–π stacking interactions

Related literature

The title compound is an aryl propargyl ether derivative which attracts interest with regard to Claisen rearrangement (Kenny et al. 2006 ▸; Wang et al. 2012 ▸) or cleavage of the O–CH₂ bond by boron reagents (Yao et al. 2009 ▸). For related structures of 4-(prop-2-yn-1-yloxy)benzenes, see: Lindeman et al. (1993 ▸); Zhu et al. (2006 ▸); Zhang et al. (2008 ▸); Marsh (2009 ▸); Ranjith et al. (2010 ▸); Li et al. (2009 ▸); Ao et al. (2011 ▸); Al-Mehana et al. (2011 ▸); Belay et al. (2012 ▸); Doi & Okuno (2013 ▸). graphic file with name e-71-00o97-scheme1.jpg

Experimental

Crystal data

C₁₀H₇NO
M _r = 157.17
Monoclinic,
a = 6.033 (4) Å
b = 7.393 (5) Å
c = 17.527 (11) Å
β = 90.836 (11)°
V = 781.7 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 93 K
0.20 × 0.07 × 0.03 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: numerical (NUMABS; Rigaku, 1999 ▸) T _min = 0.986, T _max = 0.997
6174 measured reflections
1795 independent reflections
1457 reflections with F ² > 2.0σ(F ²)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.120
S = 1.08
1795 reflections
113 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008 ▸); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXD2013 (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: CrystalStructure (Rigaku, 2014 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989014028035/hb7326sup1.cif

e-71-00o97-sup1.cif^{(13KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014028035/hb7326Isup2.hkl

e-71-00o97-Isup2.hkl^{(98.9KB, hkl)}

Click here for additional data file.^{(3.1KB, cml)}

Supporting information file. DOI: 10.1107/S2056989014028035/hb7326Isup3.cml

Click here for additional data file.^{(965.1KB, tif)}

. DOI: 10.1107/S2056989014028035/hb7326fig1.tif

The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level and H atoms are shown as small spheres.

Click here for additional data file.^{(1MB, tif)}

x y z x y z x y z x y z . DOI: 10.1107/S2056989014028035/hb7326fig2.tif

Part of the crystal structure showing the rolling sheet structure formed by the C–H⋯N and C–H⋯π hydrogen bonds [Symmetry codes: (i) x − Inline graphic , −y + , z + ; (ii) x + , −y + , z − ; (iii) x + , −y + , z − ; (iv) x − , −y + , z + ].

Click here for additional data file.^{(1.3MB, tif)}

x y z x y z . DOI: 10.1107/S2056989014028035/hb7326fig3.tif

Part of the crystal structure showing the intersheet π⋯π stacking interactions and the weak C–H⋯O hydrogen bonds [Symmetry codes: (v) −x + 2, −y + 1, −z; (vi) −x + 1, −y + 1, −z].

CCDC reference: 1041123

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C10H1N1ⁱ	0.94(2)	2.41(2)	3.300(3)	158.18(11)
C6H6C10ⁱⁱ	0.95	2.79	3.616(3)	145

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

Acknowledgments

This work was supported by Research for Promoting Technological Seeds from the Japan Science and Technology Agency (JST).

supplementary crystallographic information

S1. Comment

The title compound, C₁₀H₇N₁O₁, is an aryl propargyl ether derivative which attracts interest from viewpoints of Claisen rearrangement (Kenny et al. 2006; Wang et al. 2012) or cleavage of O–CH₂ bond by boron reagents (Yao et al. 2009). In these reactions, a direction of the lone pair of the oxygen has large influence upon reactivity.

The molecule has an almost planar structure (atoms C1—C10/N1/O1 are essentailly co-planar with r.m.s. deviation = 0.0862 Å), indicating an effective conjugation of the cyano group, the C1—C6 benzene ring and the lone pair of the O1 (Fig. 1). This is presumably because push-pull effect between an electron donating alkyloxy group and an electron withdrawing cyano group (Zhu et al. 2006; Marsh 2009; Ranjith et al. 2010; Ao et al. 2011; Al-Mehana et al. 2011; Belay et al. 2012; Doi & Okuno 2013).

In the crystal, C10–H1···N1ⁱ hydrogen bonds [Symmetry code: (i) x - 3/2, -y + 3/2, z + 1/2] connect the molecules to make a one-dimensional wavy chain. Intermolecular C6–H6···C10ⁱⁱ interaction [Symmetry code: (ii) x + 1/2, -y + 3/2, z - 1/2], whose distance is 2.794 (1) Å, binds the chains to form a rolling sheet structure as shown in Fig. 2.

Fig. 3 shows π···π stacking interactions between the sheets, where the centroid to centroid distance is 3.593 (2) Å and the C3···C5^v is 3.387 (3) Å [Symmetry code: (v) -x + 2, -y + 1, -z]. The molecules also form weak intersheet C5–H5···O1^vi bonds whose distance is 2.690 (1) Å [Symmetry code: (vi) -x + 1, -y + 1, -z]. In this crystal, the intermolecular hydrogen bonds, the C–H···π interactions and the π···π stacking interactions are found to make a three-dimensional molecular network.

S2. Experimental

The title compound is commercially available. Colourless platelets of sufficient quality for diffraction measurements were prepared by sublimation at room temperature.