4,4′-({[(Pyridine-2,6-di­yl)bis­(methyl­ene)]bis­(­oxy)}bis­(methyl­ene))dibenzo­nitrile

Yamin, B.M.; Kamalulazmy, N.A.; Hassan, N.I.

doi:10.1107/S1600536814000245

organic compounds

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Volume 70| Part 2| February 2014| Page o132

doi:10.1107/S1600536814000245

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4,4′-({[(Pyridine-2,6-diyl)bis(methylene)]bis(oxy)}bis(methylene))dibenzonitrile

Bohari M. Yamin,^a Nurul A. Kamalulazmy ^a and Nurul I. Hassan ^a ^*

^aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
^*Correspondence e-mail: n_izzaty@ukm.my

(Received 3 January 2014; accepted 6 January 2014; online 11 January 2014)

The complete title molecule, C₂₃H₁₉N₃O₂, is generated by a twofold axis passing through the central ring. The two oxymethylbenzonitrile arms are attached at the meta positions of the central pyridine ring. The dihedral angle between the pyridine ring and benzene ring of both arms is 84.55 (6)° while the benzene rings make a dihedral angle of 46.07 (7)°. In the crystal, weak C—H⋯π interactions link the molecules sheets parallel to the ac plane.

CCDC reference: 979689

Related literature

For bond-length data, see: Allen et al. (1987 ). For related structures, see: Lima et al. (2011 ); Wang & Zhao (2008 ): Zhao (2008 ); Xiao & Zhao (2008 ).

Experimental

Crystal data

C₂₃H₁₉N₃O₂
M_r = 369.41
Monoclinic, C 2/c
a = 14.1838 (7) Å
b = 7.5493 (4) Å
c = 18.4619 (12) Å
β = 107.837 (2)°
V = 1881.83 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.49 × 0.44 × 0.34 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.960, T_max = 0.972
21611 measured reflections
1846 independent reflections
1519 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.106
S = 1.05
1846 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.10 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the N1/C1–C3/C2′/C3′ ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯Cgⁱ	0.93	2.87	3.7180 (15)	152
Symmetry code: (i) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: SMART (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 979689

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814000245/hg5373sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814000245/hg5373Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814000245/hg5373Isup3.cml

checkCIF report

Comment top

Despite the wide application of dibenzonitrile compounds in the area of chemical synthesis and industrial, the structural study of dibenzonitrile derivatives are less reported. Thiadiazole dibenzonitrile (Wang & Zhao, 2008) and naphthalene dibenzonitrile (Lima et al., 2011) are some examples of dibenzonitrile derivatives. On the other hand, 4,4'-{[1,1'-Methylenebis (naphthalene-2,1-diyl)]bis(oxymethylene)}dibenzonitrile (Zhao, 2008) and 4,4'-(Oxydimethylene)dibenzonitrile (Xiao & Zhao, 2008) are few examples of bis(oxymethylene)dibenzonitriles. The title compound is a bis(methylene)bis(oxy) bis(methylene)dibenzonitrile in which the oxymtheylenedibenzonitrile arms are connected by 2,6-pyridine linkager at meta position (Figure 1) making the whole molecule, a bird like structure. The dihedral angle between the two benzene rings [(C6/C7/C8/C9/C10/C11), (C6a/C7a/C8a/C9a/C10a/C11a)] and the central pyridine (C1/C2/C3/C2a/C3a/N1) is 84.55 (6)°. The maximum deviation of the two planes is 0.005 (1) Å for C2 atom from the least square plane of the pyridine ring. The bond lengths are in normal ranges (Allen et al.,1987). In the structure, no intermolecular hydrogen bonds were observed except the presence of C8—H8···π bonds with the pyridine ring (H8—centroid Cg distance of 2.87 Å, and X—H···centroid angle = 152°).

Related literature top

For bond-length data, see: Allen et al. (1987). For related structures, see: Lima et al. (2011); Wang & Zhao (2008): Zhao (2008); Xiao & Zhao (2008).

Experimental top

NaH (10.72 g, 17.8 mmol) was carefully added to a solution of 2,6-pyridine dimethanol (1.0 g, 7.2 mmol) in dry THF (35 ml). The resulting mixture was refluxed for 1.5 h and allowed to cool to room temperature. Next, 4-bromomethyl benzonitrile (3.0 g, 15.3 mmol) was added and continued to reflux for another 24 h at 75°C. Water was slowly added to quench the reaction. The organic layers were extracted into ethyl acetate. The combined organic layers were dried over magnesium sulfate, filtered and concentrated under reduced pressure. The resulting residue was purified using column chromatography (Hexane:Ethyl acetate) to furnish a colorless powder. Single crystals were obtained from the solution of Hexane:Ethyl acetate after one day of evaporation (yield 87%, m.p 378.8–380 K). ¹H NMR (300.1 MHz, CDCl₃): 7.75 (1H, t, 3J_HH 7.7 Hz; ArH), 7.65 (4H, d, 3J_HH 8.4 Hz;4 x ArH),7.49 (4H, d, 3J_HH 8.6 Hz; 4 x ArH), 7.40 (2H, d, 3J_HH 7.8 Hz; 2 x ArH), 4.71 (4H, s; 2 x CH₂), 4.70 (4H, s; 2 x CH₂);¹³C NMR (75.5 MHz, CDCl₃):C 157.6 (ArC), 143.6 (ArC), 137.6 (ArCH), 132.4 (ArCH), 127.9 (ArCH), 120.4 (ArCH), 118.9 (CN), 111.6 (ArC),73.7 (CH₂), 72.1 (CH₂); MS (CI⁺) m/z 239.0 (27), 370.2 ([M+H]⁺, 100); HRMS (CI⁺) m/z calculated for C₂₃H₂₀N₃O₂ [M+H]⁺ 370.1556, found 370.1563.

Structure description top

For bond-length data, see: Allen et al. (1987). For related structures, see: Lima et al. (2011); Wang & Zhao (2008): Zhao (2008); Xiao & Zhao (2008).

Computing details top

Data collection: SMART (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. : Molecular structure of (I) with 50% probability displacement ellipsoids. Symmetry code A: (-x + 2, y, -z + 1/2).

4,4'-({[(Pyridine-2,6-diyl)bis(methylene)]bis(oxy)}bis(methylene))dibenzonitrile top

Crystal data top

C₂₃H₁₉N₃O₂	F(000) = 776
M_r = 369.41	D_x = 1.304 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8925 reflections
a = 14.1838 (7) Å	θ = 3.0–26.0°
b = 7.5493 (4) Å	µ = 0.09 mm⁻¹
c = 18.4619 (12) Å	T = 296 K
β = 107.837 (2)°	Block, colourless
V = 1881.83 (18) Å³	0.49 × 0.44 × 0.34 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1846 independent reflections
Radiation source: fine-focus sealed tube	1519 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 83.66 pixels mm^-1	θ_max = 26.0°, θ_min = 3.1°
ω scan	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −9→9
T_min = 0.960, T_max = 0.972	l = −22→22
21611 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0485P)² + 0.9538P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1846 reflections	Δρ_max = 0.10 e Å⁻³
129 parameters	Δρ_min = −0.12 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: 0.0196 (14)

Crystal data top

C₂₃H₁₉N₃O₂	V = 1881.83 (18) Å³
M_r = 369.41	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.1838 (7) Å	µ = 0.09 mm⁻¹
b = 7.5493 (4) Å	T = 296 K
c = 18.4619 (12) Å	0.49 × 0.44 × 0.34 mm
β = 107.837 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1846 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1519 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.972	R_int = 0.040
21611 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.05	Δρ_max = 0.10 e Å⁻³
1846 reflections	Δρ_min = −0.12 e Å⁻³
129 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	0.73355 (7)	0.39554 (16)	0.18488 (6)	0.0547 (3)
N1	1.0000	0.4615 (2)	0.2500	0.0416 (4)
N2	0.25164 (10)	0.0851 (2)	−0.08574 (9)	0.0706 (5)
C1	1.0000	0.0946 (3)	0.2500	0.0530 (6)
H1	1.0000	−0.0286	0.2500	0.064*
C2	0.91206 (10)	0.1866 (2)	0.23419 (8)	0.0495 (4)
H2	0.8519	0.1269	0.2230	0.059*
C3	0.91523 (9)	0.3697 (2)	0.23533 (7)	0.0415 (4)
C4	0.82379 (10)	0.4813 (2)	0.22471 (10)	0.0560 (4)
H4A	0.8206	0.5169	0.2744	0.067*
H4B	0.8300	0.5880	0.1973	0.067*
C5	0.71745 (10)	0.3882 (2)	0.10575 (8)	0.0463 (4)
H5A	0.7659	0.3102	0.0951	0.056*
H5B	0.7257	0.5054	0.0870	0.056*
C6	0.61510 (9)	0.32139 (17)	0.06575 (8)	0.0369 (3)
C7	0.58164 (10)	0.3218 (2)	−0.01320 (8)	0.0429 (4)
H7	0.6225	0.3645	−0.0402	0.052*
C8	0.48871 (11)	0.2599 (2)	−0.05204 (8)	0.0452 (4)
H8	0.4672	0.2599	−0.1050	0.054*
C9	0.42703 (10)	0.19725 (18)	−0.01217 (8)	0.0403 (3)
C10	0.45942 (10)	0.19748 (19)	0.06662 (8)	0.0443 (4)
H10	0.4182	0.1562	0.0936	0.053*
C11	0.55300 (10)	0.25913 (19)	0.10512 (8)	0.0422 (4)
H11	0.5746	0.2588	0.1580	0.051*
C12	0.32950 (11)	0.1331 (2)	−0.05269 (9)	0.0496 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0282 (5)	0.0835 (9)	0.0491 (6)	−0.0047 (5)	0.0069 (4)	−0.0156 (5)
N1	0.0293 (8)	0.0550 (10)	0.0369 (8)	0.000	0.0050 (6)	0.000
N2	0.0447 (8)	0.0701 (10)	0.0859 (11)	−0.0081 (7)	0.0035 (7)	−0.0136 (8)
C1	0.0554 (13)	0.0502 (13)	0.0511 (12)	0.000	0.0130 (10)	0.000
C2	0.0393 (8)	0.0624 (10)	0.0446 (8)	−0.0113 (7)	0.0095 (6)	−0.0047 (7)
C3	0.0302 (7)	0.0592 (9)	0.0329 (7)	−0.0029 (6)	0.0063 (5)	−0.0071 (6)
C4	0.0297 (7)	0.0736 (11)	0.0599 (9)	−0.0005 (7)	0.0065 (6)	−0.0220 (8)
C5	0.0327 (7)	0.0542 (9)	0.0498 (8)	0.0018 (6)	0.0095 (6)	−0.0016 (7)
C6	0.0302 (6)	0.0342 (7)	0.0442 (7)	0.0066 (5)	0.0084 (5)	−0.0003 (6)
C7	0.0403 (7)	0.0467 (8)	0.0441 (8)	0.0014 (6)	0.0164 (6)	−0.0001 (6)
C8	0.0469 (8)	0.0485 (8)	0.0368 (7)	0.0028 (7)	0.0080 (6)	−0.0030 (6)
C9	0.0343 (7)	0.0344 (7)	0.0478 (8)	0.0030 (5)	0.0061 (6)	−0.0013 (6)
C10	0.0368 (7)	0.0469 (8)	0.0500 (8)	0.0009 (6)	0.0142 (6)	0.0073 (6)
C11	0.0381 (7)	0.0480 (8)	0.0376 (7)	0.0046 (6)	0.0071 (6)	0.0040 (6)
C12	0.0419 (8)	0.0432 (8)	0.0588 (9)	0.0025 (7)	0.0080 (7)	−0.0039 (7)

Geometric parameters (Å, º) top

O1—C5	1.4088 (18)	C5—H5A	0.9700
O1—C4	1.4217 (17)	C5—H5B	0.9700
N1—C3ⁱ	1.3417 (16)	C6—C11	1.3846 (19)
N1—C3	1.3417 (16)	C6—C7	1.3879 (19)
N2—C12	1.1449 (19)	C7—C8	1.3751 (19)
C1—C2	1.3786 (19)	C7—H7	0.9300
C1—C2ⁱ	1.3786 (19)	C8—C9	1.387 (2)
C1—H1	0.9300	C8—H8	0.9300
C2—C3	1.382 (2)	C9—C10	1.3847 (19)
C2—H2	0.9300	C9—C12	1.4400 (19)
C3—C4	1.508 (2)	C10—C11	1.3804 (19)
C4—H4A	0.9700	C10—H10	0.9300
C4—H4B	0.9700	C11—H11	0.9300
C5—C6	1.5001 (18)

C5—O1—C4	112.87 (12)	C6—C5—H5B	109.6
C3ⁱ—N1—C3	117.77 (18)	H5A—C5—H5B	108.1
C2—C1—C2ⁱ	119.5 (2)	C11—C6—C7	118.96 (12)
C2—C1—H1	120.3	C11—C6—C5	122.07 (12)
C2ⁱ—C1—H1	120.3	C7—C6—C5	118.97 (12)
C1—C2—C3	118.50 (14)	C8—C7—C6	120.77 (13)
C1—C2—H2	120.8	C8—C7—H7	119.6
C3—C2—H2	120.8	C6—C7—H7	119.6
N1—C3—C2	122.86 (14)	C7—C8—C9	119.92 (13)
N1—C3—C4	114.79 (14)	C7—C8—H8	120.0
C2—C3—C4	122.25 (13)	C9—C8—H8	120.0
O1—C4—C3	114.53 (13)	C10—C9—C8	119.77 (12)
O1—C4—H4A	108.6	C10—C9—C12	120.20 (13)
C3—C4—H4A	108.6	C8—C9—C12	120.03 (13)
O1—C4—H4B	108.6	C11—C10—C9	119.91 (13)
C3—C4—H4B	108.6	C11—C10—H10	120.0
H4A—C4—H4B	107.6	C9—C10—H10	120.0
O1—C5—C6	110.41 (11)	C10—C11—C6	120.67 (13)
O1—C5—H5A	109.6	C10—C11—H11	119.7
C6—C5—H5A	109.6	C6—C11—H11	119.7
O1—C5—H5B	109.6	N2—C12—C9	178.67 (19)

C2ⁱ—C1—C2—C3	−0.50 (9)	C11—C6—C7—C8	−0.7 (2)
C3ⁱ—N1—C3—C2	−0.54 (10)	C5—C6—C7—C8	179.27 (13)
C3ⁱ—N1—C3—C4	175.99 (14)	C6—C7—C8—C9	0.5 (2)
C1—C2—C3—N1	1.1 (2)	C7—C8—C9—C10	0.0 (2)
C1—C2—C3—C4	−175.22 (11)	C7—C8—C9—C12	179.68 (14)
C5—O1—C4—C3	−76.99 (18)	C8—C9—C10—C11	−0.3 (2)
N1—C3—C4—O1	159.71 (12)	C12—C9—C10—C11	180.00 (13)
C2—C3—C4—O1	−23.7 (2)	C9—C10—C11—C6	0.1 (2)
C4—O1—C5—C6	−171.60 (12)	C7—C6—C11—C10	0.3 (2)
O1—C5—C6—C11	−6.58 (19)	C5—C6—C11—C10	−179.59 (13)
O1—C5—C6—C7	173.49 (12)

Symmetry code: (i) −x+2, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the N1/C1–C3/C2'/C3' ring.

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1	0.93	2.39	2.735 (2)	102
C8—H8···Cgⁱⁱ	0.93	2.87	3.7180 (15)	152

Symmetry code: (ii) −x+3/2, −y+1/2, −z.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the N1/C1–C3/C2'/C3' ring.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···Cgⁱ	0.93	2.87	3.7180 (15)	152

Symmetry code: (i) −x+3/2, −y+1/2, −z.

Acknowledgements

The authors would like to thank Universiti Kebangsaan Malaysia and the Ministry of Higher Education, Malaysia, for research grants GGPM-2012–016 and DIP-2012–11, respectively. Research facilities provided by the Centre of Research and Instrumentation (CRIM) are very much appreciated.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bruker (2009). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Lima, C. F., Gomes, L. R., Santos, L. M. N. B. F. & Low, J. N. (2011). Acta Cryst. E67, o66. Web of Science CSD CrossRef IUCr Journals Google Scholar
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doi:10.1107/S1600536814000245

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4,4′-({[(Pyridine-2,6-di­yl)bis­­(methyl­ene)]bis­­(­­oxy)}bis­­(methyl­ene))dibenzo­nitrile

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4,4′-({[(Pyridine-2,6-diyl)bis(methylene)]bis(oxy)}bis(methylene))dibenzonitrile