5,5′-Di-4-pyridyl-2,2′-(p-phenyl­ene)di-1,3,4-oxadiazole

Zhou, R.-S.; Song, J.-F.

doi:10.1107/S1600536809050557

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3273

doi:10.1107/S1600536809050557

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5,5′-Di-4-pyridyl-2,2′-(p-phenylene)di-1,3,4-oxadiazole

Rui-Sha Zhou ^a and Jiang-Feng Song ^a ^*

^aDepartment of Chemistry, College of Science, North University of China, Taiyuan, Shanxi 030051, People's Republic of China
^*Correspondence e-mail: jfsong0129@gmail.com

(Received 6 November 2009; accepted 24 November 2009; online 28 November 2009)

In the crystal structure of the title compound, C₂₀H₁₂N₆O₂, the molecules are located on centres of inversion. The complete molecule is almost planar, with a maximum deviation from the mean plane of 0.0657 (1) Å for the O atom. In the crystal, molecules are stacked into columns elongated in the a axis direction. The centroid–centroid distances between the aromatic rings of the molecules within the columns are 3.6406 (1) and 3.6287 (2) Å. Molecules are additionally connected via weak intermolecular C—H⋯N hydrogen bonding.

Related literature

For the potential uses of oxadiazoles, see: Bentiss et al. (2000 ); Navidpour et al. (2006 ). For related studies on oxadiazoles, see: Wang et al. (2005 ); Zhang et al. (2007 ). For the synthesis of bis-1,3,4-oxadiazol, see: Al-Talib et al. (1990 ).

Experimental

Crystal data

C₂₀H₁₂N₆O₂
M_r = 368.36
Monoclinic, P 2₁ /n
a = 6.2424 (6) Å
b = 7.6969 (7) Å
c = 17.7321 (16) Å
β = 96.635 (2)°
V = 846.27 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 183 K
0.30 × 0.18 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.971, T_max = 0.985
4541 measured reflections
1665 independent reflections
1114 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.112
S = 1.01
1665 reflections
151 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 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
C3—H2⋯N3ⁱ	0.94 (2)	2.52 (2)	3.407 (3)	158.7 (16)
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 1999); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050557/nc2169sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809050557/nc2169Isup2.hkl

checkCIF report

Comment top

The interest in 1, 3, 4-oxadiazole systems originate from their biological activity and their wide application in medicine, industry and coordination chemistry (Bentiss et al., 2000; Navidpour et al., 2006; Wang et al., 2005). Substituted 1, 3, 4-oxadiazole compounds containing pyridyl group displays good coordination activities, but the related study mainly focus on mono-1,3,4 substituted oxadiazole compounds (Wang et al., 2005; Zhang et al., 2007). The synthesis of bis-1,3,4-oxadiazole was reported by Al-Talib et al., 1990, but we have used a modified procedure. In few of the importance of oxadiazole derivatives its crystal structure is reported here.

In the crystal structure of the title compound the molecules are located on centres of inversion and are nearly coplanar. Thus, the asymmetric unit contains half a molecule (Fig. 1). In the crystal structure the molecules are stacked into columns with a centroid-centroid distances of 3.6406 (1) Å] and and 3.6287 (2) Å (Fig. 2). The columns elongate in the direction of the a axis and are connected via weak C-H···N hydrogen bonding (Table 1).

Related literature top

For the potential uses of oxadiazoles, see: Bentiss et al. (2000); Navidpour et al. (2006). For related studies on oxadiazoles, see: Wang et al. (2005); Zhang et al. (2007). For the synthesis of bis-1,3,4-oxadiazol, see: Al-Talib et al. (1990).

Experimental top

1, 4-bis[(4-pydiyl)hydrozide]phenylene (1.58 g) was added into 70 ml phosphorous oxychloride (POCl₃) and refluxed for about 24 h. After cooling to room temperature, the mixture was poured into 500 ml water. The yellow precipitate was filtered off, washed with water, and dried. Yellow single crystals were obtained by recrystallization of the precipitate from DMF.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLEASE PROVIDE; software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Crystal structure of the title compound showing the atom labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. [symmetry code: A = x, y, z].
	Fig. 2. The molecular packing for the title compound along the a axis. The intermolecular C—H···N hydrogen-bonds are shown as dashed lines.

5,5'-Di-4-pyridyl-2,2'-(p-phenylene)di-1,3,4-oxadiazole top

Crystal data top

C₂₀H₁₂N₆O₂	F(000) = 380
M_r = 368.36	D_x = 1.446 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.2424 (6) Å	θ = 2.3–26.1°
b = 7.6969 (7) Å	µ = 0.10 mm⁻¹
c = 17.7321 (16) Å	T = 183 K
β = 96.635 (2)°	Needle, yellow
V = 846.27 (14) Å³	0.30 × 0.18 × 0.15 mm
Z = 2

Data collection top

Bruker SMART APEX CCD diffractometer	1665 independent reflections
Radiation source: fine-focus sealed tube	1114 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 26.1°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −5→7
T_min = 0.971, T_max = 0.985	k = −9→6
4541 measured reflections	l = −21→20

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0489P)² + 0.1652P] where P = (F_o² + 2F_c²)/3
1665 reflections	(Δ/σ)_max = 0.001
151 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₂₀H₁₂N₆O₂	V = 846.27 (14) Å³
M_r = 368.36	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.2424 (6) Å	µ = 0.10 mm⁻¹
b = 7.6969 (7) Å	T = 183 K
c = 17.7321 (16) Å	0.30 × 0.18 × 0.15 mm
β = 96.635 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	1665 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1114 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.985	R_int = 0.028
4541 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.18 e Å⁻³
1665 reflections	Δρ_min = −0.13 e Å⁻³
151 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	1.0105 (2)	0.26943 (17)	0.91503 (7)	0.0455 (4)
N1	1.0141 (3)	0.2372 (2)	1.03852 (9)	0.0481 (5)
N2	0.8290 (3)	0.1534 (2)	1.00208 (9)	0.0490 (5)
C2	1.3123 (3)	0.4031 (2)	0.99232 (11)	0.0393 (5)
C6	0.6794 (3)	0.1193 (3)	0.86751 (11)	0.0427 (5)
C4	1.1139 (3)	0.3024 (2)	0.98550 (10)	0.0406 (5)
C5	0.8350 (3)	0.1759 (2)	0.93029 (11)	0.0419 (5)
C1	1.4231 (3)	0.4324 (3)	1.06365 (12)	0.0445 (5)
C3	1.3910 (3)	0.4712 (3)	0.92850 (11)	0.0436 (5)
N3	0.3677 (3)	0.0203 (3)	0.75019 (11)	0.0710 (6)
C10	0.5034 (4)	0.0236 (3)	0.88153 (14)	0.0559 (6)
C7	0.6983 (4)	0.1636 (3)	0.79320 (13)	0.0578 (6)
C8	0.5402 (4)	0.1127 (4)	0.73749 (14)	0.0672 (7)
C9	0.3534 (4)	−0.0212 (4)	0.82157 (14)	0.0673 (7)
H2	1.316 (3)	0.452 (2)	0.8803 (12)	0.048 (5)*
H1	1.365 (3)	0.390 (2)	1.1064 (12)	0.046 (6)*
H3	0.483 (3)	−0.009 (3)	0.9316 (13)	0.063 (7)*
H6	0.550 (4)	0.142 (3)	0.6864 (15)	0.085 (8)*
H5	0.812 (4)	0.222 (3)	0.7800 (13)	0.069 (8)*
H4	0.234 (4)	−0.079 (3)	0.8314 (14)	0.086 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0404 (8)	0.0544 (9)	0.0408 (8)	−0.0085 (6)	0.0005 (6)	−0.0010 (6)
N1	0.0434 (10)	0.0573 (11)	0.0424 (9)	−0.0076 (8)	−0.0004 (8)	−0.0024 (8)
N2	0.0453 (10)	0.0571 (11)	0.0434 (10)	−0.0091 (8)	0.0001 (8)	−0.0006 (8)
C2	0.0336 (10)	0.0411 (11)	0.0419 (11)	0.0023 (8)	−0.0017 (8)	−0.0022 (8)
C6	0.0395 (11)	0.0451 (12)	0.0425 (11)	−0.0004 (9)	0.0001 (9)	−0.0044 (9)
C4	0.0389 (11)	0.0445 (12)	0.0367 (10)	0.0018 (9)	−0.0027 (9)	−0.0033 (9)
C5	0.0362 (11)	0.0428 (11)	0.0463 (12)	−0.0027 (9)	0.0026 (9)	−0.0004 (9)
C1	0.0423 (12)	0.0521 (13)	0.0383 (11)	−0.0018 (10)	0.0012 (9)	0.0029 (10)
C3	0.0399 (12)	0.0509 (12)	0.0377 (11)	0.0003 (9)	−0.0054 (9)	−0.0013 (9)
N3	0.0657 (14)	0.0925 (16)	0.0512 (12)	−0.0132 (12)	−0.0083 (10)	−0.0080 (11)
C10	0.0573 (14)	0.0641 (15)	0.0452 (13)	−0.0159 (11)	0.0012 (11)	0.0002 (11)
C7	0.0552 (14)	0.0711 (16)	0.0464 (13)	−0.0106 (12)	0.0028 (11)	0.0003 (11)
C8	0.0718 (17)	0.0867 (19)	0.0414 (13)	−0.0059 (14)	−0.0007 (12)	0.0022 (12)
C9	0.0559 (16)	0.088 (2)	0.0559 (16)	−0.0232 (14)	−0.0020 (12)	−0.0079 (13)

Geometric parameters (Å, º) top

O1—C4	1.362 (2)	C1—H1	0.94 (2)
O1—C5	1.364 (2)	C3—C1ⁱ	1.371 (3)
N1—C4	1.288 (2)	C3—H2	0.94 (2)
N1—N2	1.413 (2)	N3—C9	1.319 (3)
N2—C5	1.290 (2)	N3—C8	1.331 (3)
C2—C3	1.387 (3)	C10—C9	1.377 (3)
C2—C1	1.388 (3)	C10—H3	0.95 (2)
C2—C4	1.454 (3)	C7—C8	1.370 (3)
C6—C10	1.369 (3)	C7—H5	0.89 (2)
C6—C7	1.379 (3)	C8—H6	0.94 (3)
C6—C5	1.457 (3)	C9—H4	0.90 (3)
C1—C3ⁱ	1.371 (3)

C4—O1—C5	102.87 (14)	C2—C1—H1	118.9 (13)
C4—N1—N2	106.44 (15)	C1ⁱ—C3—C2	119.80 (18)
C5—N2—N1	105.93 (16)	C1ⁱ—C3—H2	120.2 (12)
C3—C2—C1	119.71 (18)	C2—C3—H2	120.0 (12)
C3—C2—C4	120.80 (17)	C9—N3—C8	116.0 (2)
C1—C2—C4	119.48 (18)	C6—C10—C9	118.9 (2)
C10—C6—C7	117.7 (2)	C6—C10—H3	120.6 (14)
C10—C6—C5	120.01 (18)	C9—C10—H3	120.5 (14)
C7—C6—C5	122.2 (2)	C8—C7—C6	119.0 (2)
N1—C4—O1	112.27 (16)	C8—C7—H5	118.8 (15)
N1—C4—C2	128.76 (17)	C6—C7—H5	122.3 (15)
O1—C4—C2	118.96 (16)	N3—C8—C7	124.1 (2)
N2—C5—O1	112.49 (16)	N3—C8—H6	115.6 (16)
N2—C5—C6	128.40 (18)	C7—C8—H6	120.3 (16)
O1—C5—C6	119.09 (17)	N3—C9—C10	124.4 (2)
C3ⁱ—C1—C2	120.48 (19)	N3—C9—H4	117.0 (17)
C3ⁱ—C1—H1	120.5 (12)	C10—C9—H4	118.5 (17)

Symmetry code: (i) −x+3, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H2···N3ⁱⁱ	0.94 (2)	2.52 (2)	3.407 (3)	158.7 (16)

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

Experimental details

Crystal data
Chemical formula	C₂₀H₁₂N₆O₂
M_r	368.36
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	183
a, b, c (Å)	6.2424 (6), 7.6969 (7), 17.7321 (16)
β (°)	96.635 (2)
V (Å³)	846.27 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.18 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.971, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	4541, 1665, 1114
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.112, 1.01
No. of reflections	1665
No. of parameters	151
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.13

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLEASE PROVIDE.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H2···N3ⁱ	0.94 (2)	2.52 (2)	3.407 (3)	158.7 (16)

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

Acknowledgements

This work was supported by the Doctoral Foundation of North University of China.

References

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