4,4′-(Oxydimethyl­ene)dibenzonitrile

Xiao, J.; Zhao, H.

doi:10.1107/S1600536808020527

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1436

doi:10.1107/S1600536808020527

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4,4′-(Oxydimethylene)dibenzonitrile

Jie Xiao ^a and Hong Zhao ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: zhaohong@seu.edu.cn

(Received 19 June 2008; accepted 3 July 2008; online 9 July 2008)

The title compound, C₁₆H₁₂N₂O, was accidentally synthesized by the reaction of 4-(bromomethyl)benzonitrile and pentaerythritol. The dihedral angle between the benzene rings is 57.39 (9)°. In the crystal structure, molecules are linked by intermolecular C—H⋯N hydrogen-bonding interactions to form chains running parallel to the b axis.

Related literature

For applications of nitrile derivatives in the synthesis of some heterocyclic molecules, see: Radl et al. (2000 ); Jin et al. (1994 ). For the crystal structure of a related compound, see: Fu & Zhao (2007 ).

Experimental

Crystal data

C₁₆H₁₂N₂O
M_r = 248.28
Monoclinic, P 2₁ /c
a = 14.444 (3) Å
b = 7.6674 (13) Å
c = 11.897 (2) Å
β = 96.326 (14)°
V = 1309.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 (2) K
0.35 × 0.30 × 0.30 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.939, T_max = 0.978
13064 measured reflections
3007 independent reflections
1498 reflections with I > 2σ(I)
R_int = 0.071

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.149
S = 1.01
3007 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯N2ⁱ	0.93	2.60	3.490 (3)	162
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{5\over 2}}]$ .

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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808020527/rz2229sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808020527/rz2229Isup2.hkl

checkCIF report

Comment top

Nitrile derivatives are an important class of compounds used in the chemical industry. For example, nitrile derivatives are employed in the synthesis of some heterocyclic molecules (Radl et al., 2000), and have been used as starting materials for the synthesis of phthalocyanines (Jin et al., 1994). Recently, we have reported the crystal structure of a benzonitrile compound (Fu & Zhao, 2007). The title compound was unexpectedly obtained during our work on nitrile compounds, and its crystal structure is reported here.

In the title compound (Fig. 1), bond lengths and angles have normal values. The planes through the C2—C7 and C10—C15 benzene rings form a dihedral angle of 57.39 (9)°. The crystal structure is stabilized by an intermolecular C—H···N hydrogen bond forming chains of molecules along the b-axis (Table 1).

Related literature top

For applications of nitrile derivatives in the synthesis of some heterocyclic molecules, see: Radl et al. (2000); Jin et al. (1994). For the crystal structure of a related compound, see: Fu & Zhao (2007).

Experimental top

Pentaerythritol (0.136 g, 1 mmol) and 4-(bromomethyl)benzonitrile (0.658 g, 4 mmol) were dissolved in water in the presence of sodium hydroxide (0.160 g, 4 mmol) and heated under reflux for 2 days. After the mixture was cooled to room temperature, the solvent was removed in vacuum to afford a white precipitate of the title compound. Colourless crystals suitable for X-ray diffraction were obtained from a solution of 100 mg in 15 ml diethylether by slow evaporation after 5 days.

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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

4,4'-(Oxydimethylene)dibenzonitrile top

Crystal data top

C₁₆H₁₂N₂O	F(000) = 520
M_r = 248.28	D_x = 1.259 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1930 reflections
a = 14.444 (3) Å	θ = 2.8–27.5°
b = 7.6674 (13) Å	µ = 0.08 mm⁻¹
c = 11.897 (2) Å	T = 293 K
β = 96.326 (14)°	Block, colourless
V = 1309.6 (4) Å³	0.35 × 0.30 × 0.30 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	3007 independent reflections
Radiation source: fine-focus sealed tube	1498 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.072
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.8°
ω scans	h = −18→18
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
T_min = 0.939, T_max = 0.978	l = −15→15
13064 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.149	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0573P)²] where P = (F_o² + 2F_c²)/3
3007 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.11 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₆H₁₂N₂O	V = 1309.6 (4) Å³
M_r = 248.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.444 (3) Å	µ = 0.08 mm⁻¹
b = 7.6674 (13) Å	T = 293 K
c = 11.897 (2) Å	0.35 × 0.30 × 0.30 mm
β = 96.326 (14)°

Data collection top

Rigaku Mercury2 diffractometer	3007 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1498 reflections with I > 2σ(I)
T_min = 0.939, T_max = 0.978	R_int = 0.072
13064 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 1.01	Δρ_max = 0.11 e Å⁻³
3007 reflections	Δρ_min = −0.16 e Å⁻³
172 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
O1	0.21121 (10)	0.2174 (2)	0.82830 (14)	0.0632 (5)
C13	0.40291 (15)	0.6678 (3)	1.0392 (2)	0.0543 (6)
C5	−0.05516 (16)	0.2145 (3)	0.5362 (2)	0.0530 (6)
C1	0.17453 (17)	0.0647 (3)	0.7737 (2)	0.0610 (7)
H1A	0.1547	−0.0163	0.8289	0.073*
H1B	0.2218	0.0082	0.7346	0.073*
C16	0.43912 (17)	0.8289 (4)	1.0896 (2)	0.0647 (7)
C3	0.10674 (17)	0.2247 (3)	0.6017 (2)	0.0616 (7)
H3	0.1662	0.2664	0.5941	0.074*
C2	0.09330 (16)	0.1156 (3)	0.69105 (19)	0.0505 (6)
C11	0.33163 (17)	0.5062 (3)	0.8811 (2)	0.0608 (7)
H11	0.3073	0.5020	0.8054	0.073*
C7	0.00448 (17)	0.0575 (3)	0.7016 (2)	0.0592 (7)
H7	−0.0057	−0.0156	0.7614	0.071*
C4	0.03367 (17)	0.2726 (3)	0.5241 (2)	0.0624 (7)
H4	0.0440	0.3439	0.4635	0.075*
C10	0.33245 (15)	0.3570 (3)	0.9471 (2)	0.0539 (6)
C6	−0.06975 (17)	0.1060 (3)	0.6249 (2)	0.0618 (7)
H6	−0.1294	0.0657	0.6331	0.074*
C9	0.29580 (16)	0.1870 (3)	0.8972 (2)	0.0659 (7)
H9A	0.3410	0.1358	0.8524	0.079*
H9B	0.2855	0.1062	0.9572	0.079*
C12	0.36687 (17)	0.6610 (3)	0.9274 (2)	0.0625 (7)
H12	0.3662	0.7608	0.8828	0.075*
C14	0.40499 (17)	0.5201 (3)	1.1048 (2)	0.0619 (7)
H14	0.4302	0.5241	1.1801	0.074*
C15	0.36940 (16)	0.3653 (3)	1.0584 (2)	0.0625 (7)
H15	0.3705	0.2657	1.1031	0.075*
C8	−0.13138 (19)	0.2686 (3)	0.4553 (2)	0.0640 (7)
N2	0.46806 (17)	0.9545 (3)	1.1316 (2)	0.0850 (8)
N1	−0.19108 (17)	0.3162 (3)	0.3912 (2)	0.0883 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0528 (10)	0.0591 (10)	0.0733 (11)	0.0012 (8)	−0.0121 (8)	−0.0152 (8)
C13	0.0438 (13)	0.0670 (16)	0.0511 (15)	−0.0015 (11)	0.0004 (11)	−0.0064 (12)
C5	0.0529 (15)	0.0533 (14)	0.0521 (15)	0.0004 (11)	0.0024 (12)	−0.0107 (11)
C1	0.0591 (16)	0.0546 (15)	0.0677 (17)	−0.0037 (12)	0.0000 (13)	−0.0063 (12)
C16	0.0568 (16)	0.0752 (19)	0.0604 (17)	−0.0035 (13)	−0.0009 (13)	−0.0087 (14)
C3	0.0477 (15)	0.0689 (17)	0.0690 (17)	−0.0086 (12)	0.0107 (13)	0.0035 (13)
C2	0.0524 (14)	0.0463 (13)	0.0527 (15)	−0.0039 (11)	0.0050 (11)	−0.0096 (11)
C11	0.0572 (16)	0.0742 (18)	0.0479 (15)	−0.0013 (12)	−0.0078 (12)	−0.0039 (13)
C7	0.0594 (16)	0.0601 (16)	0.0586 (16)	−0.0125 (12)	0.0082 (13)	−0.0004 (12)
C4	0.0607 (17)	0.0676 (17)	0.0600 (16)	−0.0025 (13)	0.0117 (13)	0.0057 (12)
C10	0.0405 (13)	0.0632 (16)	0.0567 (15)	0.0052 (11)	−0.0002 (11)	−0.0076 (12)
C6	0.0525 (15)	0.0656 (17)	0.0678 (17)	−0.0138 (12)	0.0086 (13)	−0.0060 (13)
C9	0.0538 (15)	0.0664 (17)	0.0743 (18)	0.0051 (12)	−0.0065 (13)	−0.0083 (13)
C12	0.0646 (16)	0.0652 (17)	0.0558 (16)	−0.0057 (13)	−0.0020 (13)	0.0029 (12)
C14	0.0548 (16)	0.0772 (19)	0.0508 (15)	0.0023 (13)	−0.0072 (12)	−0.0038 (13)
C15	0.0580 (15)	0.0650 (17)	0.0619 (17)	0.0042 (12)	−0.0044 (13)	0.0063 (13)
C8	0.0621 (17)	0.0638 (17)	0.0654 (18)	−0.0015 (13)	0.0041 (14)	−0.0083 (13)
N2	0.0928 (19)	0.0813 (18)	0.0772 (17)	−0.0108 (14)	−0.0071 (14)	−0.0135 (14)
N1	0.0732 (16)	0.0958 (18)	0.0919 (19)	0.0035 (14)	−0.0094 (14)	0.0044 (15)

Geometric parameters (Å, º) top

O1—C9	1.414 (3)	C11—C12	1.382 (3)
O1—C1	1.414 (2)	C11—C10	1.387 (3)
C13—C14	1.374 (3)	C11—H11	0.9300
C13—C12	1.375 (3)	C7—C6	1.380 (3)
C13—C16	1.445 (3)	C7—H7	0.9300
C5—C6	1.379 (3)	C4—H4	0.9300
C5—C4	1.380 (3)	C10—C15	1.373 (3)
C5—C8	1.441 (3)	C10—C9	1.504 (3)
C1—C2	1.497 (3)	C6—H6	0.9300
C1—H1A	0.9700	C9—H9A	0.9700
C1—H1B	0.9700	C9—H9B	0.9700
C16—N2	1.142 (3)	C12—H12	0.9300
C3—C4	1.374 (3)	C14—C15	1.384 (3)
C3—C2	1.384 (3)	C14—H14	0.9300
C3—H3	0.9300	C15—H15	0.9300
C2—C7	1.377 (3)	C8—N1	1.145 (3)

C9—O1—C1	112.70 (17)	C3—C4—C5	119.9 (2)
C14—C13—C12	120.0 (2)	C3—C4—H4	120.1
C14—C13—C16	119.0 (2)	C5—C4—H4	120.1
C12—C13—C16	121.0 (2)	C15—C10—C11	119.1 (2)
C6—C5—C4	119.8 (2)	C15—C10—C9	120.2 (2)
C6—C5—C8	121.0 (2)	C11—C10—C9	120.7 (2)
C4—C5—C8	119.2 (2)	C5—C6—C7	119.7 (2)
O1—C1—C2	108.22 (18)	C5—C6—H6	120.1
O1—C1—H1A	110.1	C7—C6—H6	120.1
C2—C1—H1A	110.1	O1—C9—C10	109.29 (19)
O1—C1—H1B	110.1	O1—C9—H9A	109.8
C2—C1—H1B	110.1	C10—C9—H9A	109.8
H1A—C1—H1B	108.4	O1—C9—H9B	109.8
N2—C16—C13	178.5 (3)	C10—C9—H9B	109.8
C4—C3—C2	121.0 (2)	H9A—C9—H9B	108.3
C4—C3—H3	119.5	C13—C12—C11	120.1 (2)
C2—C3—H3	119.5	C13—C12—H12	119.9
C7—C2—C3	118.5 (2)	C11—C12—H12	119.9
C7—C2—C1	121.8 (2)	C13—C14—C15	119.8 (2)
C3—C2—C1	119.7 (2)	C13—C14—H14	120.1
C12—C11—C10	120.2 (2)	C15—C14—H14	120.1
C12—C11—H11	119.9	C10—C15—C14	120.8 (2)
C10—C11—H11	119.9	C10—C15—H15	119.6
C2—C7—C6	121.1 (2)	C14—C15—H15	119.6
C2—C7—H7	119.4	N1—C8—C5	178.1 (3)
C6—C7—H7	119.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···N2ⁱ	0.93	2.60	3.490 (3)	162

Symmetry code: (i) −x+1, y−1/2, −z+5/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂N₂O
M_r	248.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	14.444 (3), 7.6674 (13), 11.897 (2)
β (°)	96.326 (14)
V (Å³)	1309.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.35 × 0.30 × 0.30

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.939, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	13064, 3007, 1498
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.149, 1.01
No. of reflections	3007
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.16

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
C14—H14···N2ⁱ	0.93	2.60	3.490 (3)	161.7

Symmetry code: (i) −x+1, y−1/2, −z+5/2.

Acknowledgements

This work was supported by a Start-up Grant from Southeast University to HZ.

References

Fu, D.-W. & Zhao, H. (2007). Acta Cryst. E63, o3206. Web of Science CSD CrossRef IUCr Journals Google Scholar
Jin, Z., Nolan, K., McArthur, C. R., Lever, A. B. P. & Leznoff, C. C. (1994). J. Organomet. Chem. 468, 205–212. CrossRef CAS Web of Science Google Scholar
Radl, S., Hezky, P., Konvicka, P. & Krejgi, J. (2000). Collect. Czech. Chem. Commun. 65, 1093–1108. Web of Science CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar