5,5′-Bis(naphthalen-2-yl)-2,2′-bi(1,3,4-oxadiazole)

Wang, H.; Jia, X.; Qu, S.; Bai, B.; Li, M.

doi:10.1107/S1600536811048513

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3360

https://doi.org/10.1107/S1600536811048513

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5,5′-Bis(naphthalen-2-yl)-2,2′-bi(1,3,4-oxadiazole)

Haitao Wang,^a Xiaoshi Jia,^a Songnan Qu,^b Binglian Bai ^c and Min Li ^a ^*

^aKey Laboratory of Automobile Materials (MOE), College of Materials Science and Engineering, Jilin University, Changchun 130012, People's Republic of China, ^bKey Laboratory of Excited State Processes, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, Changchun 130033, People's Republic of China, and ^cCollege of Physics, Jilin University, Changchun 130012, People's Republic of China
^*Correspondence e-mail: minli@jlu.edu.cn

(Received 10 November 2011; accepted 15 November 2011; online 19 November 2011)

The title molecule, C₂₄H₁₄N₄O₂, lies on an inversion centre and the asymmetric unit containg one half-molecule. The naphthalene ring systems are twisted slightly with respect to the oxadiazole rings, making a dihedral angle of 1.36 (6)°. These molecules are π-stacked along the crystallographic a axis, with an interplanar distance of 3.337 (1) Å. Adjacent molecules are slipped from the `ideal' cofacial π-stack in both the long and short molecular axis (the long molecular axis is defined as the line through the naphthalene C atom in the 6-position and the molecular center, the short molecular axis is in the molecular plane perpendicular to it). The slip distance along the long molecular axis (S₁) is 7.064 (1) Å, nearly a two-ring-length displacement. The side slip (S₂, along the short molecular axis) is 1.159 (8) Å.

Related literature

For the synthesis of 1,3,4-oxadiazole derivatives: see Schulz et al. (1997 ). For related structures: see Schulz et al. (2005 ); Qu et al. (2008 ); Landis et al. (2008 ).

Experimental

Crystal data

C₂₄H₁₄N₄O₂
M_r = 390.39
Monoclinic, P 2₁ /c
a = 7.8982 (16) Å
b = 5.7107 (11) Å
c = 21.503 (5) Å
β = 109.82 (3)°
V = 912.4 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.18 × 0.14 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.983, T_max = 0.989
8518 measured reflections
2091 independent reflections
1468 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.106
S = 1.07
2091 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ) and CrystalStructure (Rigaku/MSC, 2002 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811048513/vm2137sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811048513/vm2137Isup2.hkl

checkCIF report

Comment top

Aromatic heterocycles, such as 1,3,4-oxadiazole and thiophene rings, which are conjugatable to phenyl rings, are often directly connected to the phenyl ring to obtain a large π-conjugated system or to tune the electronic structure. These compounds are of interest as charge transport materials or emitting layers in electroluminescent diodes (Schulz et al., 1997, Schulz et al., 2005). Comparing to thiophene derivatives, 1,3,4-oxadiazole derivatives are more likely to form π-stacked molecular packing (Schulz et al., 2005, Qu et al., 2008, Landis et al., 2008).

As shown in Fig. 1, both 1,3,4-oxadiazole rings are in a trans-conformation, which yields a linear molecular shape. These molecules are π-stacked along the crystallographic a-axis (Fig. 2). The molecules in the stacks are canted relative to the stacking axis by 26.57 (1)°. Adjacent molecules are slipped off each other in both long and short molecular axis to avoid unfavorable electrostatic interactions in the "ideal" cofacial stacks (Fig. 3).

Related literature top

For the synthesis of 1,3,4-oxadiazole derivatives: see Schulz et al. (1997). For related structures: see Schulz et al. (2005); Qu et al. (2008); Landis et al. (2008).

Experimental top

The tile compound was synthesized through a two-step reaction. Firstly, naphthylacyl hydrazide was reacted with oxalyl chloride in THF at room temperature for 8 h, yielding the product, oxalyl acid N',N'-di-naphthylacyl hydrazide. Secondly, the title compound was derived by intramolecular cyclization of this dihydrazide derivative with POCl₃ under reflux conditions, and the coarse product was further purified by washing with DMSO for the 1H NMR FT—IR spectroscopic characterization and elemental analysis. Yield >70%. Crystals of the title compound suitable for X-ray diffraction were obtained by a slow diffusion method (diethyl ether was diffused into chloroform solution).

Structure description top

For the synthesis of 1,3,4-oxadiazole derivatives: see Schulz et al. (1997). For related structures: see Schulz et al. (2005); Qu et al. (2008); Landis et al. (2008).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipoids drawn at the 50% probability level. The asymmetric unit only contains a half molecule, the second half is generated by symmetry code -x, -y+1, -z+2. The line through C8 and the molecular center is defined as the long molecular axis.
	Fig. 2. Molecular packing as viewed down the crystallographic a axis.
	Fig. 3. Two adjacent molecules in the molecular stacks as viewed perpendicular to the molecular plane. The slip distances along the long molecular axis (S₁) and short axis (S₂) are 7.064 (1)Å and 1.159 (8) Å, respectively.

5,5'-Bis(naphthalen-2-yl)-2,2'-bi(1,3,4-oxadiazole) top

Crystal data top

C₂₄H₁₄N₄O₂	Z = 2
M_r = 390.39	F(000) = 404
Monoclinic, P2₁/c	D_x = 1.421 Mg m⁻³
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.8982 (16) Å	µ = 0.09 mm⁻¹
b = 5.7107 (11) Å	T = 293 K
c = 21.503 (5) Å	Block, colourless
β = 109.82 (3)°	0.18 × 0.14 × 0.12 mm
V = 912.4 (3) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	2091 independent reflections
Radiation source: fine-focus sealed tube	1468 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 27.5°, θ_min = 3.7°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→10
T_min = 0.983, T_max = 0.989	k = −7→7
8518 measured reflections	l = −27→27

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0577P)²] where P = (F_o² + 2F_c²)/3
2091 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₄H₁₄N₄O₂	V = 912.4 (3) Å³
M_r = 390.39	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.8982 (16) Å	µ = 0.09 mm⁻¹
b = 5.7107 (11) Å	T = 293 K
c = 21.503 (5) Å	0.18 × 0.14 × 0.12 mm
β = 109.82 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2091 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1468 reflections with I > 2σ(I)
T_min = 0.983, T_max = 0.989	R_int = 0.030
8518 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.07	Δρ_max = 0.16 e Å⁻³
2091 reflections	Δρ_min = −0.18 e Å⁻³
136 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	0.18040 (11)	0.40921 (16)	0.97102 (4)	0.0412 (2)
N1	0.01904 (14)	0.7350 (2)	0.94532 (6)	0.0482 (3)
N2	0.14392 (14)	0.7347 (2)	0.91193 (6)	0.0479 (3)
C1	0.04644 (15)	0.5425 (2)	0.97855 (6)	0.0407 (3)
C2	0.23461 (16)	0.5413 (2)	0.92839 (6)	0.0388 (3)
C3	0.38061 (15)	0.4564 (2)	0.90721 (6)	0.0373 (3)
C4	0.46713 (17)	0.2407 (2)	0.93102 (6)	0.0448 (3)
H4	0.4287	0.1499	0.9596	0.054*
C5	0.60641 (17)	0.1660 (2)	0.91221 (7)	0.0453 (3)
H5	0.6637	0.0256	0.9288	0.054*
C6	0.66520 (15)	0.2993 (2)	0.86777 (6)	0.0389 (3)
C7	0.80712 (17)	0.2254 (3)	0.84590 (7)	0.0506 (4)
H7	0.8681	0.0868	0.8621	0.061*
C8	0.85466 (18)	0.3556 (3)	0.80150 (8)	0.0586 (4)
H8	0.9466	0.3037	0.7870	0.070*
C9	0.76681 (19)	0.5674 (3)	0.77722 (8)	0.0565 (4)
H9	0.8008	0.6543	0.7468	0.068*
C10	0.63230 (17)	0.6463 (3)	0.79789 (6)	0.0459 (3)
H10	0.5763	0.7881	0.7821	0.055*
C11	0.57699 (15)	0.5144 (2)	0.84322 (6)	0.0364 (3)
C12	0.43475 (15)	0.5888 (2)	0.86414 (6)	0.0379 (3)
H12	0.3768	0.7297	0.8485	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0390 (4)	0.0454 (6)	0.0423 (5)	0.0017 (4)	0.0180 (4)	0.0038 (4)
N1	0.0447 (6)	0.0538 (7)	0.0506 (6)	0.0060 (5)	0.0222 (5)	0.0051 (6)
N2	0.0464 (6)	0.0498 (7)	0.0518 (6)	0.0059 (5)	0.0225 (5)	0.0066 (5)
C1	0.0343 (6)	0.0481 (8)	0.0402 (6)	0.0009 (5)	0.0133 (5)	−0.0021 (6)
C2	0.0392 (6)	0.0417 (7)	0.0358 (6)	−0.0030 (5)	0.0131 (5)	0.0017 (5)
C3	0.0363 (6)	0.0379 (7)	0.0371 (6)	−0.0013 (5)	0.0115 (5)	−0.0009 (5)
C4	0.0512 (7)	0.0399 (7)	0.0453 (7)	0.0005 (6)	0.0190 (6)	0.0083 (6)
C5	0.0481 (7)	0.0357 (7)	0.0495 (7)	0.0050 (5)	0.0130 (6)	0.0036 (6)
C6	0.0366 (6)	0.0377 (7)	0.0403 (6)	0.0001 (5)	0.0103 (5)	−0.0054 (5)
C7	0.0433 (7)	0.0485 (9)	0.0588 (8)	0.0042 (6)	0.0156 (6)	−0.0084 (7)
C8	0.0438 (7)	0.0718 (11)	0.0680 (9)	−0.0010 (7)	0.0290 (7)	−0.0128 (8)
C9	0.0522 (8)	0.0680 (11)	0.0569 (8)	−0.0083 (7)	0.0285 (7)	0.0018 (8)
C10	0.0450 (7)	0.0465 (8)	0.0472 (7)	−0.0033 (6)	0.0168 (6)	0.0036 (6)
C11	0.0363 (6)	0.0366 (7)	0.0355 (6)	−0.0036 (5)	0.0110 (5)	−0.0029 (5)
C12	0.0395 (6)	0.0340 (7)	0.0391 (6)	0.0019 (5)	0.0118 (5)	0.0026 (5)

Geometric parameters (Å, º) top

O1—C1	1.3568 (15)	C6—C7	1.4190 (17)
O1—C2	1.3636 (15)	C6—C11	1.4228 (18)
N1—C1	1.2889 (18)	C7—C8	1.360 (2)
N1—N2	1.4031 (16)	C7—H7	0.9300
N2—C2	1.2986 (17)	C8—C9	1.404 (2)
C1—C1ⁱ	1.443 (3)	C8—H8	0.9300
C2—C3	1.4588 (17)	C9—C10	1.3600 (19)
C3—C12	1.3714 (17)	C9—H9	0.9300
C3—C4	1.4175 (18)	C10—C11	1.4130 (18)
C4—C5	1.3629 (19)	C10—H10	0.9300
C4—H4	0.9300	C11—C12	1.4098 (17)
C5—C6	1.4173 (19)	C12—H12	0.9300
C5—H5	0.9300

C1—O1—C2	101.84 (10)	C7—C6—C11	118.45 (12)
C1—N1—N2	105.54 (11)	C8—C7—C6	120.48 (14)
C2—N2—N1	106.25 (11)	C8—C7—H7	119.8
N1—C1—O1	113.78 (11)	C6—C7—H7	119.8
N1—C1—C1ⁱ	127.93 (15)	C7—C8—C9	120.87 (14)
O1—C1—C1ⁱ	118.28 (15)	C7—C8—H8	119.6
N2—C2—O1	112.58 (11)	C9—C8—H8	119.6
N2—C2—C3	128.24 (12)	C10—C9—C8	120.39 (14)
O1—C2—C3	119.18 (12)	C10—C9—H9	119.8
C12—C3—C4	120.03 (11)	C8—C9—H9	119.8
C12—C3—C2	119.22 (12)	C9—C10—C11	120.50 (14)
C4—C3—C2	120.75 (12)	C9—C10—H10	119.8
C5—C4—C3	120.24 (12)	C11—C10—H10	119.8
C5—C4—H4	119.9	C12—C11—C10	121.71 (12)
C3—C4—H4	119.9	C12—C11—C6	119.00 (11)
C4—C5—C6	120.93 (13)	C10—C11—C6	119.29 (11)
C4—C5—H5	119.5	C3—C12—C11	120.93 (12)
C6—C5—H5	119.5	C3—C12—H12	119.5
C5—C6—C7	122.68 (13)	C11—C12—H12	119.5
C5—C6—C11	118.86 (11)

C1—N1—N2—C2	0.01 (14)	C4—C5—C6—C11	0.41 (19)
N2—N1—C1—O1	0.15 (15)	C5—C6—C7—C8	177.78 (13)
N2—N1—C1—C1ⁱ	179.92 (16)	C11—C6—C7—C8	−1.28 (19)
C2—O1—C1—N1	−0.23 (14)	C6—C7—C8—C9	1.1 (2)
C2—O1—C1—C1ⁱ	179.97 (14)	C7—C8—C9—C10	0.1 (2)
N1—N2—C2—O1	−0.16 (14)	C8—C9—C10—C11	−1.1 (2)
N1—N2—C2—C3	−179.98 (12)	C9—C10—C11—C12	−178.28 (12)
C1—O1—C2—N2	0.24 (13)	C9—C10—C11—C6	0.84 (19)
C1—O1—C2—C3	−179.92 (11)	C5—C6—C11—C12	0.36 (17)
N2—C2—C3—C12	−0.4 (2)	C7—C6—C11—C12	179.46 (11)
O1—C2—C3—C12	179.76 (10)	C5—C6—C11—C10	−178.78 (11)
N2—C2—C3—C4	179.09 (12)	C7—C6—C11—C10	0.33 (17)
O1—C2—C3—C4	−0.72 (18)	C4—C3—C12—C11	−0.42 (18)
C12—C3—C4—C5	1.19 (19)	C2—C3—C12—C11	179.11 (11)
C2—C3—C4—C5	−178.33 (12)	C10—C11—C12—C3	178.77 (11)
C3—C4—C5—C6	−1.2 (2)	C6—C11—C12—C3	−0.35 (18)
C4—C5—C6—C7	−178.66 (12)

Symmetry code: (i) −x, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₄H₁₄N₄O₂
M_r	390.39
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.8982 (16), 5.7107 (11), 21.503 (5)
β (°)	109.82 (3)
V (Å³)	912.4 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.18 × 0.14 × 0.12

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.983, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	8518, 2091, 1468
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.106, 1.07
No. of reflections	2091
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.18

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Acknowledgements

We would like to thank Mrs Ye Ling and Dr Li Bao of Jilin University for the crystal structure analysis. This work was supported by the National Science Foundation of China (50873044, 51073071, 51103057, and 21072076) and Jilin University (200903014).

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