1,3-Bis{[5-(pyridin-2-yl)-1,3,4-oxadiazol-2-yl]sulfan­yl}propan-2-one

Xia, C.-H.; Mao, C.-B.; Wu, B.-L.

doi:10.1107/S1600536811001140

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o413

doi:10.1107/S1600536811001140

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1,3-Bis{[5-(pyridin-2-yl)-1,3,4-oxadiazol-2-yl]sulfanyl}propan-2-one

Chao-Hui Xia,^a,^b Chun-Bo Mao ^a and Ben-Lai Wu ^a ^*

^aDepartment of Chemistry, Zhengzhou University, Zhengzhou 450052, People's Republic of China, and ^bHenan Vocational College of Chemical Technology, Zhengzhou 450052, People's Republic of China
^*Correspondence e-mail: wbl@zzu.edu.cn

(Received 1 January 2011; accepted 8 January 2011; online 15 January 2011)

In the distorted W-shaped molecule of the title compound, C₁₇H₁₂N₆O₃S₂, a twofold axis passes through the carbonyl group. The molecules stack in the crystal through π–π interactions [centroid—centroid distance = 3.883 Å] and weak C—H⋯N hydrogen-bonding interactions, forming a three-dimensional architecture.

Related literature

For the use of oxadiazole-containing compounds with symmetrical or asymmetrical structures in coordination chemistry, see: Du et al. (2006 ); Fang et al. (2002 ); Wu et al. (2010 ); Ye et al. (2007 ). For a similar propanone-bridged dithioether compound, see: Wu et al. (2005 ).

Experimental

Crystal data

C₁₇H₁₂N₆O₃S₂
M_r = 412.45
Monoclinic, C 2/c
a = 14.266 (3) Å
b = 7.8342 (16) Å
c = 16.703 (3) Å
β = 100.25 (3)°
V = 1837.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.913, T_max = 1.000
8929 measured reflections
1607 independent reflections
1448 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.076
wR(F²) = 0.134
S = 1.24
1607 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯N3ⁱ	0.99	2.51	3.388 (4)	148
C9—H9⋯N1ⁱⁱ	0.95	2.54	3.449 (5)	161
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1994 ); 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/S1600536811001140/hg2787sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811001140/hg2787Isup2.hkl

checkCIF report

Comment top

1,3,4-Oxadiazole and its derivatives exhibits good luminous properties, biological activity, and as well as flexibility in crystal engineering. So far, a great deal of oxadiazole-containing compounds with symmetrical or asymmetrical structures has been prepared and especially used in coordination chemistry (Du et al., 2006; Fang, et al., 2002; Ye, et al., 2007; Wu, et al., 2010). We herein describe the structure of the title compound, (I), which is a new oxadiazole-containing thioethers ligand with a propan-2-one moiety at the linkage.

In (I), there is a twofold rotation axis passing through the C1—O1 carbonyl group of the propanone moiety (Fig. 1). Two 5-(pyridin-2-yl)-1,3,4-oxadiazole-2-thio groups are oriented anti to bind the propanone moiety, and thus form the compound (I) with a distorted "W-shaped" configuration, being similar to another propanone-bridged dithioether compound ( Wu, et al., 2005). The S1 atom deviates from the least-squares plane of C2/C2ⁱ/C1/O1 by 0.387 (7) Å [(i) 1 - x, y, -z + 1/2]. The dihedral angle of pyridin-2-yl and oxadiazole group is 2.8 (1)°, indicating that pyridin-2-yl and oxadiazole group are almost coplanar in 5-(pyridin-2-yl)-1,3,4-oxadiazole-2-thio group.The dihedral angle of two 5-(pyridin-2-yl)-1,3,4-oxadiazole-2-thio is 68.8 (1)°, while that of the propanone moiety and the pyrimidine ring is 70.7 (1)°. Notably, the molecules stack in the crystal lattice through intermolecular π–π interactions of pyridyl and oxadiazole groups with center-to-center distance of 3.883 Å and weaker C—H···N hydrogen-bonding interactions to form a three-dimensional architecture (Fig. 2).

Related literature top

For the use of oxadiazole-containing compounds with symmetrical or asymmetrical structures in coordination chemistry, see: Du et al. (2006); Fang et al. (2002); Wu et al. (2010); Ye et al. (2007). For a similar propanone-bridged dithioether compound, see: Wu et al. (2005).

Experimental top

Sodium methylate (0.540 g, 10 mmol) and 5-(2-pyridyl)-2-mercapto-1,3,4- oxadiazole (1.79 g, 10 mmol) were vigorously stirred in MeOH (50 ml) for 1 h, before quantitative 1,3-dichloro-2-propanone (0.635 g, 5 mmol) was added. The resulting solution was heated at 373 K for 12 h and then filtered after cooled to room temperature. Removal of the solvent from the yellow filtrate created yellow powder which was washed with water and recrystallized from methanol to produce yellow crystals of (I) (yield 2.572 g, 64%; m.p. 174–175 °C). Slow evaporation of methanol solution of (I) for two weeks created block yellow crystals suitable for X-ray diffraction.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. Perspective view of (I) with atom numbering scheme. Atom displacement ellipsoids are shown at 30% probability level. Symmetry codes, as in Table 1.
	Fig. 2. Packing diagram of (I), showing intermolecular π–π interactions and weaker C—H···N hydrogen-bonding interactions.

1,3-Bis{[5-(pyridin-2-yl)-1,3,4-oxadiazol-2-yl]sulfanyl}propan-2-one top

Crystal data top

C₁₇H₁₂N₆O₃S₂	F(000) = 848
M_r = 412.45	D_x = 1.491 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2643 reflections
a = 14.266 (3) Å	θ = 2.5–29.1°
b = 7.8342 (16) Å	µ = 0.32 mm⁻¹
c = 16.703 (3) Å	T = 293 K
β = 100.25 (3)°	Block, yellow
V = 1837.0 (6) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Siemens SMART CCD diffractometer	1607 independent reflections
Radiation source: fine-focus sealed tube	1448 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
T_min = 0.913, T_max = 1.000	k = −9→9
8929 measured reflections	l = −19→19

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters constrained
S = 1.24	w = 1/[σ²(F_o²) + (0.0357P)² + 3.0521P] where P = (F_o² + 2F_c²)/3
1607 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₇H₁₂N₆O₃S₂	V = 1837.0 (6) Å³
M_r = 412.45	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.266 (3) Å	µ = 0.32 mm⁻¹
b = 7.8342 (16) Å	T = 293 K
c = 16.703 (3) Å	0.20 × 0.20 × 0.20 mm
β = 100.25 (3)°

Data collection top

Siemens SMART CCD diffractometer	1607 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1448 reflections with I > 2σ(I)
T_min = 0.913, T_max = 1.000	R_int = 0.050
8929 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.076	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.24	Δρ_max = 0.33 e Å⁻³
1607 reflections	Δρ_min = −0.21 e Å⁻³
128 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
S1	0.19304 (8)	0.68102 (19)	0.24214 (6)	0.0785 (5)
O1	0.0000	0.5351 (5)	0.2500	0.0640 (11)
O2	0.28820 (16)	0.5281 (3)	0.37180 (14)	0.0525 (7)
N1	0.1587 (2)	0.6557 (4)	0.39768 (17)	0.0485 (8)
N2	0.2056 (2)	0.5752 (4)	0.46924 (17)	0.0488 (8)
N3	0.4202 (2)	0.3330 (4)	0.46674 (18)	0.0549 (8)
C1	0.0000	0.6876 (7)	0.2500	0.0453 (12)
C2	0.0834 (2)	0.7944 (5)	0.2358 (2)	0.0531 (10)
H2A	0.0928	0.8879	0.2763	0.064*
H2B	0.0675	0.8471	0.1812	0.064*
C3	0.2100 (2)	0.6238 (5)	0.3439 (2)	0.0472 (9)
C4	0.2798 (2)	0.5024 (4)	0.45132 (19)	0.0394 (8)
C5	0.3528 (2)	0.4016 (4)	0.5029 (2)	0.0431 (8)
C6	0.3488 (3)	0.3797 (5)	0.5839 (2)	0.0500 (9)
H6	0.2993	0.4304	0.6070	0.060*
C7	0.4183 (3)	0.2824 (5)	0.6308 (2)	0.0587 (10)
H7	0.4172	0.2635	0.6868	0.070*
C8	0.4890 (3)	0.2137 (5)	0.5952 (3)	0.0610 (11)
H8	0.5382	0.1475	0.6263	0.073*
C9	0.4878 (3)	0.2419 (5)	0.5144 (3)	0.0637 (11)
H9	0.5375	0.1942	0.4905	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0624 (7)	0.1289 (11)	0.0478 (6)	0.0273 (7)	0.0196 (5)	0.0245 (7)
O1	0.076 (3)	0.053 (3)	0.056 (2)	0.000	−0.0065 (19)	0.000
O2	0.0435 (14)	0.0728 (18)	0.0427 (14)	0.0122 (12)	0.0115 (11)	0.0052 (12)
N1	0.0445 (17)	0.059 (2)	0.0407 (16)	0.0085 (14)	0.0045 (13)	−0.0009 (14)
N2	0.0510 (18)	0.058 (2)	0.0365 (16)	0.0064 (15)	0.0064 (13)	−0.0037 (14)
N3	0.0491 (18)	0.066 (2)	0.0516 (18)	0.0100 (16)	0.0151 (15)	0.0038 (16)
C1	0.060 (3)	0.047 (3)	0.024 (2)	0.000	−0.006 (2)	0.000
C2	0.052 (2)	0.064 (3)	0.041 (2)	0.0022 (19)	0.0029 (16)	0.0107 (18)
C3	0.0380 (19)	0.059 (2)	0.044 (2)	0.0037 (17)	0.0061 (16)	0.0031 (18)
C4	0.0417 (19)	0.044 (2)	0.0327 (17)	−0.0036 (15)	0.0077 (14)	−0.0048 (15)
C5	0.0433 (19)	0.042 (2)	0.0431 (19)	−0.0034 (16)	0.0068 (16)	−0.0051 (16)
C6	0.054 (2)	0.054 (2)	0.042 (2)	0.0065 (18)	0.0084 (17)	−0.0068 (18)
C7	0.067 (3)	0.060 (3)	0.047 (2)	0.005 (2)	0.0047 (19)	0.0036 (19)
C8	0.054 (2)	0.058 (3)	0.067 (3)	0.006 (2)	0.000 (2)	0.017 (2)
C9	0.049 (2)	0.070 (3)	0.074 (3)	0.015 (2)	0.017 (2)	0.012 (2)

Geometric parameters (Å, º) top

S1—C3	1.732 (4)	C2—H2A	0.9900
S1—C2	1.785 (4)	C2—H2B	0.9900
O1—C1	1.195 (6)	C4—C5	1.460 (5)
O2—C3	1.356 (4)	C5—C6	1.374 (5)
O2—C4	1.369 (4)	C6—C7	1.379 (5)
N1—C3	1.281 (4)	C6—H6	0.9500
N1—N2	1.411 (4)	C7—C8	1.369 (5)
N2—C4	1.283 (4)	C7—H7	0.9500
N3—C5	1.336 (4)	C8—C9	1.365 (6)
N3—C9	1.341 (5)	C8—H8	0.9500
C1—C2	1.507 (5)	C9—H9	0.9500
C1—C2ⁱ	1.507 (5)

C3—S1—C2	98.92 (17)	N2—C4—C5	129.3 (3)
C3—O2—C4	101.9 (2)	O2—C4—C5	118.4 (3)
C3—N1—N2	105.2 (3)	N3—C5—C6	123.6 (3)
C4—N2—N1	106.7 (3)	N3—C5—C4	116.5 (3)
C5—N3—C9	116.4 (3)	C6—C5—C4	119.9 (3)
O1—C1—C2	123.7 (2)	C5—C6—C7	118.5 (3)
O1—C1—C2ⁱ	123.7 (2)	C5—C6—H6	120.8
C2—C1—C2ⁱ	112.6 (5)	C7—C6—H6	120.8
C1—C2—S1	115.0 (3)	C8—C7—C6	118.8 (4)
C1—C2—H2A	108.5	C8—C7—H7	120.6
S1—C2—H2A	108.5	C6—C7—H7	120.6
C1—C2—H2B	108.5	C9—C8—C7	119.0 (4)
S1—C2—H2B	108.5	C9—C8—H8	120.5
H2A—C2—H2B	107.5	C7—C8—H8	120.5
N1—C3—O2	113.9 (3)	N3—C9—C8	123.7 (4)
N1—C3—S1	129.8 (3)	N3—C9—H9	118.2
O2—C3—S1	116.3 (2)	C8—C9—H9	118.2
N2—C4—O2	112.3 (3)

C3—N1—N2—C4	−0.3 (4)	C3—O2—C4—C5	179.9 (3)
O1—C1—C2—S1	−13.9 (3)	C9—N3—C5—C6	−1.6 (5)
C2ⁱ—C1—C2—S1	166.1 (3)	C9—N3—C5—C4	179.3 (3)
C3—S1—C2—C1	−64.4 (3)	N2—C4—C5—N3	176.6 (3)
N2—N1—C3—O2	0.1 (4)	O2—C4—C5—N3	−3.8 (5)
N2—N1—C3—S1	178.8 (3)	N2—C4—C5—C6	−2.5 (6)
C4—O2—C3—N1	0.2 (4)	O2—C4—C5—C6	177.1 (3)
C4—O2—C3—S1	−178.8 (2)	N3—C5—C6—C7	0.4 (6)
C2—S1—C3—N1	−0.5 (4)	C4—C5—C6—C7	179.4 (3)
C2—S1—C3—O2	178.3 (3)	C5—C6—C7—C8	0.9 (6)
N1—N2—C4—O2	0.5 (4)	C6—C7—C8—C9	−0.8 (6)
N1—N2—C4—C5	−179.8 (3)	C5—N3—C9—C8	1.7 (6)
C3—O2—C4—N2	−0.4 (4)	C7—C8—C9—N3	−0.5 (7)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···N3ⁱⁱ	0.99	2.51	3.388 (4)	148
C9—H9···N1ⁱⁱⁱ	0.95	2.54	3.449 (5)	161

Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₂N₆O₃S₂
M_r	412.45
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	14.266 (3), 7.8342 (16), 16.703 (3)
β (°)	100.25 (3)
V (Å³)	1837.0 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Siemens SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.913, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8929, 1607, 1448
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.076, 0.134, 1.24
No. of reflections	1607
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.21

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···N3ⁱ	0.99	2.51	3.388 (4)	148
C9—H9···N1ⁱⁱ	0.95	2.54	3.449 (5)	161

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x+1/2, y−1/2, z.

Acknowledgements

This work was supported by the Natural Science Foundation of China.

References

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