4-(6-Quinolyl­oxymeth­yl)benzonitrile

Zhao, M.M.; Li, Y.H.; Wu, D.H.; Wan, Q.

doi:10.1107/S1600536809016560

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1261

doi:10.1107/S1600536809016560

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4-(6-Quinolyloxymethyl)benzonitrile

Min Min Zhao,^a Yong Hua Li,^a ^* De Hong Wu ^a and Qing Wan ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: liyhnju@hotmail.com

(Received 2 April 2009; accepted 4 May 2009; online 14 May 2009)

The title compound, C₁₇H₁₂N₂O, was synthesized by an ether synthesis from quinolin-6-ol and 4-(bromomethyl)benzonitrile. The phenyl ring of the benzonitrile group makes a dihedral angle of 47.52 (6)° with the plane of the quinoline fragment. The crystal structure is stabilized by intermolecular C—H⋯π interactions between a benzene H atom of the benzonitrile group and the benzene ring of the quinoline fragment. In addition, the crystal structure also exhibits a weak intermolecular C—H⋯N hydrogen bond.

Related literature

For general background to nitrile compounds, see: Jin et al. (1994 ); Brewis et al. (2003 ). For related structures, see: Fu & Zhao (2007 ); Zhao (2008 ).

Experimental

Crystal data

C₁₇H₁₂N₂O
M_r = 260.29
Monoclinic, P 2₁ /n
a = 9.466 (2) Å
b = 13.078 (3) Å
c = 10.857 (2) Å
β = 90.81 (3)°
V = 1343.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.30 × 0.26 × 0.24 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.976, T_max = 0.981
12007 measured reflections
2622 independent reflections
1956 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.120
S = 1.06
2622 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯Cgⁱ	0.93	2.83	3.613 (2)	142
C13—H13⋯N1ⁱⁱ	0.93	2.60	3.398 (2)	145
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y+1, z. Cg is the centroid of the C1–C4/C8/C9 benzene ring.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809016560/lx2099sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016560/lx2099Isup2.hkl

checkCIF report

Comment top

The synthesis of new azoles has been a very active area of research and one important aspect has been the incorporation of functional units. Nitrile derivatives have found many industrial applications. For example, phthalonitriles have been used as starting materials for phthalocyanines (Jin et al., 1994), which are important components for dyes, pigments, gas sensors, optical limiters and liquid crystals, and which are also used in medicine, as singlet oxygen photosensitisers for photodynamic therapy (PDT; Brewis et al., 2003). Recently, we have reported a few benzonitrile compounds (Fu & Zhao, 2007; Zhao, 2008). As an extension of our work on the structural characterization, Here we present the synthesis and crystal structure of the title compound 4-[(quinolin-6-yloxy)methyl]benzonitrile (Fig. 1).

The phenyl ring (C11–C16) make a dihedral angle of 47.44 (1)° with the plane of the quinoline fragment. The molecular packing (Fig. 2) is stabilized by intermolecular C—H···π interactions between the benzene H atom of benzonitrile group and the benzene ring of the quinoline fragment from an adjacent molecule, with a C12—H12···Cgⁱ separation of 2.83 Å (Fig. 2 and Table 1; Cg is the centroid of the C1–C4/C8/C9 benzene ring, symmetry code as in Fig. 2). Additionally, a weak intermolecular C—H···N hydrogen bond in the structure is observed (Fig. 2 and Table 1).

Related literature top

For general background on nitrile compounds, see: Jin et al. (1994); Brewis et al. (2003). For related structures, see: Fu & Zhao (2007); Zhao (2008).Cg is the centroid of the C1–C4/C8/C9 benzene ring

Experimental top

Quinolin-6-ol (1 g, 0.0069 mol) was added to a solution of sodium hydroxide (0.276 g, 0.0069 mol) in 15 ml of methanol and stirred for one hour. Then 4-(bromomethyl)benzonitrile (1.352 g, 0.0069 mol) was added to the above solution. The mixture was stirred at room temperature for 1 d. The title compound was isolated using column chromatography (petroleum ether:ethyl acetate = 2:1). Single crystals suitable for X-ray diffraction analysis were obtained from slow evaporation of ethyl acetate and tetrahydrofuran solution.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. The C—H···π and C—H···N interactions (dotted lines) in the title compound. Cg denotes the ring centroid. [Symmetry codes: (i) -x + 1/2, y + 1/2, -z + 1/2; (ii) x, y + 1, z; (iii) x, y - 1, z; (iv) -x + 1/2, y - 1/2, -z + 1/2.]

4-(6-Quinolyloxymethyl)benzonitrile top

Crystal data top

C₁₇H₁₂N₂O	F(000) = 544
M_r = 260.29	D_x = 1.286 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 10916 reflections
a = 9.466 (2) Å	θ = 6.2–55.5°
b = 13.078 (3) Å	µ = 0.08 mm⁻¹
c = 10.857 (2) Å	T = 293 K
β = 90.81 (3)°	Prism, colourless
V = 1343.9 (5) Å³	0.30 × 0.26 × 0.24 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2622 independent reflections
Radiation source: fine-focus sealed tube	1956 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.0°, θ_min = 3.1°
ω scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −16→16
T_min = 0.976, T_max = 0.981	l = −13→13
12007 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.120	w = 1/[σ²(F_o²) + (0.050P)² + 0.1913P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2622 reflections	Δρ_max = 0.15 e Å⁻³
182 parameters	Δρ_min = −0.13 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.018 (4)

Crystal data top

C₁₇H₁₂N₂O	V = 1343.9 (5) Å³
M_r = 260.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.466 (2) Å	µ = 0.08 mm⁻¹
b = 13.078 (3) Å	T = 293 K
c = 10.857 (2) Å	0.30 × 0.26 × 0.24 mm
β = 90.81 (3)°

Data collection top

Rigaku SCXmini diffractometer	2622 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1956 reflections with I > 2σ(I)
T_min = 0.976, T_max = 0.981	R_int = 0.054
12007 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.06	Δρ_max = 0.15 e Å⁻³
2622 reflections	Δρ_min = −0.13 e Å⁻³
182 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
O1	0.48772 (13)	0.46617 (8)	0.29375 (10)	0.0598 (4)
N1	0.40388 (17)	0.05815 (11)	0.18437 (15)	0.0620 (4)
N2	0.7214 (2)	0.99565 (14)	0.44097 (18)	0.0841 (6)
C1	0.46122 (17)	0.36816 (12)	0.25614 (16)	0.0484 (4)
C2	0.49253 (18)	0.29346 (13)	0.34606 (16)	0.0538 (5)
H2	0.5251	0.3134	0.4236	0.065*
C3	0.47550 (19)	0.19262 (13)	0.32018 (16)	0.0547 (5)
H3	0.4984	0.1441	0.3798	0.066*
C4	0.42364 (17)	0.16054 (12)	0.20416 (16)	0.0478 (4)
C5	0.3504 (2)	0.03171 (15)	0.07708 (19)	0.0701 (6)
H5	0.3356	−0.0376	0.0624	0.084*
C6	0.3139 (2)	0.10024 (15)	−0.01687 (19)	0.0691 (6)
H6	0.2764	0.0765	−0.0912	0.083*
C7	0.33370 (19)	0.20151 (13)	0.00168 (16)	0.0570 (5)
H7	0.3103	0.2482	−0.0599	0.068*
C8	0.39011 (16)	0.23550 (12)	0.11523 (15)	0.0451 (4)
C9	0.40997 (17)	0.34014 (12)	0.14319 (15)	0.0474 (4)
H9	0.3881	0.3898	0.0846	0.057*
C10	0.45964 (19)	0.54615 (12)	0.20742 (16)	0.0526 (4)
H10A	0.3588	0.5517	0.1918	0.063*
H10B	0.5056	0.5316	0.1301	0.063*
C11	0.51542 (17)	0.64433 (12)	0.26109 (15)	0.0478 (4)
C12	0.43628 (18)	0.73295 (12)	0.25445 (17)	0.0531 (5)
H12	0.3466	0.7310	0.2185	0.064*
C13	0.48752 (18)	0.82412 (13)	0.30002 (17)	0.0552 (5)
H13	0.4330	0.8831	0.2948	0.066*
C14	0.62108 (18)	0.82714 (12)	0.35366 (15)	0.0494 (4)
C15	0.70261 (19)	0.73897 (13)	0.35993 (17)	0.0576 (5)
H15	0.7927	0.7410	0.3951	0.069*
C16	0.64942 (19)	0.64883 (13)	0.31393 (17)	0.0574 (5)
H16	0.7042	0.5899	0.3183	0.069*
C17	0.6764 (2)	0.92132 (15)	0.40205 (17)	0.0607 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0811 (9)	0.0411 (7)	0.0567 (8)	−0.0085 (6)	−0.0115 (6)	0.0033 (5)
N1	0.0743 (11)	0.0411 (9)	0.0705 (11)	0.0007 (7)	0.0028 (8)	0.0007 (7)
N2	0.0966 (13)	0.0606 (11)	0.0946 (13)	−0.0189 (10)	−0.0163 (10)	−0.0113 (10)
C1	0.0489 (9)	0.0409 (9)	0.0551 (10)	−0.0042 (7)	−0.0015 (8)	0.0030 (8)
C2	0.0596 (11)	0.0524 (11)	0.0494 (10)	−0.0030 (8)	−0.0063 (8)	0.0048 (8)
C3	0.0610 (11)	0.0479 (11)	0.0553 (11)	0.0019 (8)	−0.0030 (8)	0.0128 (8)
C4	0.0455 (9)	0.0412 (10)	0.0569 (11)	0.0011 (7)	0.0043 (8)	0.0037 (8)
C5	0.0847 (15)	0.0449 (11)	0.0808 (15)	−0.0049 (9)	0.0041 (11)	−0.0085 (10)
C6	0.0842 (14)	0.0584 (12)	0.0646 (12)	−0.0103 (10)	−0.0065 (10)	−0.0105 (10)
C7	0.0635 (12)	0.0526 (11)	0.0546 (11)	−0.0049 (8)	−0.0053 (9)	0.0016 (8)
C8	0.0396 (9)	0.0439 (9)	0.0516 (10)	−0.0019 (7)	0.0007 (7)	0.0025 (7)
C9	0.0502 (10)	0.0433 (9)	0.0485 (10)	−0.0011 (7)	−0.0052 (7)	0.0089 (7)
C10	0.0589 (11)	0.0427 (10)	0.0562 (11)	−0.0010 (8)	−0.0035 (8)	0.0040 (8)
C11	0.0489 (10)	0.0431 (10)	0.0514 (10)	−0.0033 (7)	0.0032 (7)	0.0030 (7)
C12	0.0439 (10)	0.0472 (10)	0.0681 (12)	−0.0011 (7)	−0.0023 (8)	0.0004 (8)
C13	0.0534 (11)	0.0418 (10)	0.0706 (12)	0.0031 (8)	0.0033 (9)	0.0025 (8)
C14	0.0543 (11)	0.0434 (9)	0.0506 (10)	−0.0084 (7)	0.0036 (8)	0.0015 (7)
C15	0.0499 (10)	0.0553 (11)	0.0673 (12)	−0.0016 (8)	−0.0093 (9)	0.0009 (9)
C16	0.0559 (11)	0.0442 (10)	0.0718 (12)	0.0069 (8)	−0.0075 (9)	0.0004 (8)
C17	0.0664 (12)	0.0532 (11)	0.0626 (12)	−0.0073 (9)	−0.0030 (9)	0.0002 (9)

Geometric parameters (Å, º) top

O1—C1	1.3674 (19)	C7—H7	0.9300
O1—C10	1.4269 (19)	C8—C9	1.414 (2)
N1—C5	1.310 (2)	C9—H9	0.9300
N1—C4	1.369 (2)	C10—C11	1.503 (2)
N2—C17	1.140 (2)	C10—H10A	0.9700
C1—C9	1.363 (2)	C10—H10B	0.9700
C1—C2	1.410 (2)	C11—C12	1.381 (2)
C2—C3	1.358 (2)	C11—C16	1.386 (2)
C2—H2	0.9300	C12—C13	1.377 (2)
C3—C4	1.409 (2)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.385 (2)
C4—C8	1.409 (2)	C13—H13	0.9300
C5—C6	1.398 (3)	C14—C15	1.389 (2)
C5—H5	0.9300	C14—C17	1.435 (2)
C6—C7	1.352 (3)	C15—C16	1.373 (2)
C6—H6	0.9300	C15—H15	0.9300
C7—C8	1.408 (2)	C16—H16	0.9300

C1—O1—C10	117.34 (12)	C1—C9—H9	120.1
C5—N1—C4	116.62 (16)	C8—C9—H9	120.1
C9—C1—O1	125.61 (15)	O1—C10—C11	108.09 (13)
C9—C1—C2	120.38 (15)	O1—C10—H10A	110.1
O1—C1—C2	114.01 (14)	C11—C10—H10A	110.1
C3—C2—C1	120.44 (16)	O1—C10—H10B	110.1
C3—C2—H2	119.8	C11—C10—H10B	110.1
C1—C2—H2	119.8	H10A—C10—H10B	108.4
C2—C3—C4	120.86 (16)	C12—C11—C16	118.59 (15)
C2—C3—H3	119.6	C12—C11—C10	120.62 (15)
C4—C3—H3	119.6	C16—C11—C10	120.74 (15)
N1—C4—C8	122.97 (16)	C13—C12—C11	121.32 (16)
N1—C4—C3	118.47 (15)	C13—C12—H12	119.3
C8—C4—C3	118.53 (15)	C11—C12—H12	119.3
N1—C5—C6	124.62 (18)	C12—C13—C14	119.39 (16)
N1—C5—H5	117.7	C12—C13—H13	120.3
C6—C5—H5	117.7	C14—C13—H13	120.3
C7—C6—C5	119.14 (18)	C13—C14—C15	120.02 (15)
C7—C6—H6	120.4	C13—C14—C17	120.32 (16)
C5—C6—H6	120.4	C15—C14—C17	119.67 (16)
C6—C7—C8	119.31 (17)	C16—C15—C14	119.63 (16)
C6—C7—H7	120.3	C16—C15—H15	120.2
C8—C7—H7	120.3	C14—C15—H15	120.2
C7—C8—C4	117.33 (15)	C15—C16—C11	121.04 (16)
C7—C8—C9	122.75 (15)	C15—C16—H16	119.5
C4—C8—C9	119.89 (15)	C11—C16—H16	119.5
C1—C9—C8	119.88 (15)	N2—C17—C14	179.4 (2)

C10—O1—C1—C9	−0.1 (2)	O1—C1—C9—C8	178.66 (15)
C10—O1—C1—C2	179.55 (14)	C2—C1—C9—C8	−1.0 (2)
C9—C1—C2—C3	1.7 (3)	C7—C8—C9—C1	178.09 (16)
O1—C1—C2—C3	−177.98 (16)	C4—C8—C9—C1	−0.1 (2)
C1—C2—C3—C4	−1.3 (3)	C1—O1—C10—C11	−171.97 (14)
C5—N1—C4—C8	−0.4 (3)	O1—C10—C11—C12	−135.85 (16)
C5—N1—C4—C3	177.42 (17)	O1—C10—C11—C16	46.7 (2)
C2—C3—C4—N1	−177.77 (16)	C16—C11—C12—C13	−0.6 (3)
C2—C3—C4—C8	0.2 (3)	C10—C11—C12—C13	−178.12 (16)
C4—N1—C5—C6	0.5 (3)	C11—C12—C13—C14	0.0 (3)
N1—C5—C6—C7	−0.1 (3)	C12—C13—C14—C15	0.7 (3)
C5—C6—C7—C8	−0.2 (3)	C12—C13—C14—C17	−179.84 (16)
C6—C7—C8—C4	0.3 (2)	C13—C14—C15—C16	−0.7 (3)
C6—C7—C8—C9	−178.00 (17)	C17—C14—C15—C16	179.81 (17)
N1—C4—C8—C7	0.1 (2)	C14—C15—C16—C11	0.1 (3)
C3—C4—C8—C7	−177.76 (16)	C12—C11—C16—C15	0.6 (3)
N1—C4—C8—C9	178.39 (15)	C10—C11—C16—C15	178.10 (16)
C3—C4—C8—C9	0.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cgⁱ	0.93	2.83	3.613 (2)	142
C13—H13···N1ⁱⁱ	0.93	2.60	3.398 (2)	145

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₂N₂O
M_r	260.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.466 (2), 13.078 (3), 10.857 (2)
β (°)	90.81 (3)
V (Å³)	1343.9 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.26 × 0.24

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.976, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	12007, 2622, 1956
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.120, 1.06
No. of reflections	2622
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.13

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cgⁱ	0.93	2.83	3.613 (2)	142.4
C13—H13···N1ⁱⁱ	0.93	2.60	3.398 (2)	144.6

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x, y+1, z.

Acknowledgements

This work was supported by a Start-up Grant (No. 4007041028) and a Science Technology Grant (No. KJ2009375) from Southeast University to YHL.

References

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