organic compounds
4,4′-({[(Pyridine-2,6-diyl)bis(methylene)]bis(oxy)}bis(methylene))dibenzonitrile
aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
*Correspondence e-mail: n_izzaty@ukm.my
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
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Data collection: SMART (Bruker, 2009); cell 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
10.1107/S1600536814000245/hg5373sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814000245/hg5373Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814000245/hg5373Isup3.cml
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
(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, 3JHH 7.7 Hz; ArH), 7.65 (4H, d, 3JHH 8.4 Hz;4 x ArH),7.49 (4H, d, 3JHH 8.6 Hz; 4 x ArH), 7.40 (2H, d, 3JHH 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.After their location in the difference map, the H-atoms attached to the C and N atoms were fixed geometrically at ideal positions and allowed to ride on the parent atoms with C—H = 0.93 Å, with Uiso(H)=1.2Ueq(C).
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°).
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).
Data collection: SMART (Bruker, 2009); cell
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).Fig. 1. : Molecular structure of (I) with 50% probability displacement ellipsoids. Symmetry code A: (-x + 2, y, -z + 1/2). |
C23H19N3O2 | F(000) = 776 |
Mr = 369.41 | Dx = 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 |
Bruker SMART APEX CCD area-detector diffractometer | 1846 independent reflections |
Radiation source: fine-focus sealed tube | 1519 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
Detector resolution: 83.66 pixels mm-1 | θmax = 26.0°, θmin = 3.1° |
ω scan | h = −17→17 |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | k = −9→9 |
Tmin = 0.960, Tmax = 0.972 | l = −22→22 |
21611 measured reflections |
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(Fo2) + (0.0485P)2 + 0.9538P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
1846 reflections | Δρmax = 0.10 e Å−3 |
129 parameters | Δρmin = −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) |
C23H19N3O2 | V = 1881.83 (18) Å3 |
Mr = 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)° |
Bruker SMART APEX CCD area-detector diffractometer | 1846 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 1519 reflections with I > 2σ(I) |
Tmin = 0.960, Tmax = 0.972 | Rint = 0.040 |
21611 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.10 e Å−3 |
1846 reflections | Δρmin = −0.12 e Å−3 |
129 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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. |
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. |
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
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, W. & Zhao, H. (2008). Acta Cryst. E64, o1599. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xiao, J. & Zhao, H. (2008). Acta Cryst. E64, o1436. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhao, Y.-Y. (2008). Acta Cryst. E64, o761. Web of Science CSD CrossRef IUCr Journals Google Scholar
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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°).