2,2′-[Ethane-1,2-diylbis(sulfanedi­yl)]bis­(pyridine N-oxide)

Wang, H.-H.; Zhang, C.-Y.; Cui, Y.; Xie, Y.-B.

doi:10.1107/S1600536809050788

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3268

doi:10.1107/S1600536809050788

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2,2′-[Ethane-1,2-diylbis(sulfanediyl)]bis(pyridine N-oxide)

Huan-Huan Wang,^a Chao-Yan Zhang,^a Yue Cui ^a and Ya-Bo Xie ^a ^*

^aCollege of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, People's Republic of China
^*Correspondence e-mail: xieyabo@bjut.edu.cn

(Received 16 November 2009; accepted 25 November 2009; online 28 November 2009)

The tile compound, C₁₂H₁₂N₂O₂S₂, lies on an inversion center. The two pyridyl rings are parallel to each other. The structure is devoid of any classical hydrogen bonds due to lack of appropriate donors and acceptors for such bonds. However, non-classical hydrogen bonds of the types C—H⋯O and C—H⋯S stabilize the structure.

Related literature

For thioether-type complexes, see: Xie et al. (2006 ). For a related structure, see: Zhang et al. (2009 ).

Experimental

Crystal data

C₁₂H₁₂N₂O₂S₂
M_r = 280.36
Monoclinic, P 2₁ /c
a = 8.2776 (17) Å
b = 6.9790 (14) Å
c = 10.791 (2) Å
β = 93.52 (3)°
V = 622.2 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 293 K
0.28 × 0.26 × 0.24 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.889, T_max = 0.904
3068 measured reflections
1098 independent reflections
1007 reflections with I > 2(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.070
S = 1.07
1098 reflections
82 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O1ⁱ	0.96	2.30	3.225 (2)	161
C4—H4A⋯S1ⁱⁱ	0.96	2.85	3.599 (2)	135
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: XSCANS (Bruker, 1998); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 2008 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050788/pv2239sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809050788/pv2239Isup2.hkl

checkCIF report

Comment top

In the past decades, there were many reports about the thioether-type compounds with their flexibility and conformation freedoms (Xie et al., 2006). As a continuation of our series of research on thioether-type compounds (Zhang et al., 2009), we report herein the crystal structure of the title compound.

The title compound (Fig.1) was obtained by the reaction of 2-mercaptopyridine N-oxide and 1,2-dibromoethane. There exits a symmetrical center located at the midpoint of the two methylenes and the pyridyl rings of the title compound are parallel to each other. Thestructure is stabilized by non-classical hydrogen bonds of the types C—H···O and C—H···S.

Related literature top

For thioether-type complexes, see: Xie et al. (2006). For a related structure, see: Zhang et al. (2009).

Experimental top

2-Mercaptopyridine N-oxide (1.2719 g, 10.0 mmol) was added to a stirred and heated solution of KOH (0.5837 g, 10.4 mmol) in ethanol (50 ml). After 30 min, 1,2-dibromoethane (0.9917 g, 5.3 mmol) was added and reacted for 10 h. The mixture was cooled to room temperature and the precipitate was filtered off and washed with water, giving a white powder. After slow diffusion of ether into the solution of the powder in CHCl₃/CH₃CH₂OH, colorless block single crystals suitable for X-ray diffraction were collected.

Computing details top

Data collection: XSCANS (Bruker, 1998); cell refinement: XSCANS (Bruker, 1998); data reduction: SHELXTL (Sheldrick, 2008); 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).

Figures top

Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level for non-hydrogen atoms.

2,2'-[Ethane-1,2-diylbis(sulfanediyl)]bis(pyridine N-oxide) top

Crystal data top

C₁₂H₁₂N₂O₂S₂	F(000) = 292
M_r = 280.36	D_x = 1.496 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3720 reflections
a = 8.2776 (17) Å	θ = 2.5–27.9°
b = 6.9790 (14) Å	µ = 0.42 mm⁻¹
c = 10.791 (2) Å	T = 293 K
β = 93.52 (3)°	Block, colorless
V = 622.2 (2) Å³	0.28 × 0.26 × 0.24 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	1098 independent reflections
Radiation source: fine-focus sealed tube	1007 reflections with I > 2(I)
Graphite monochromator	R_int = 0.013
ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −9→7
T_min = 0.889, T_max = 0.904	k = −8→8
3068 measured reflections	l = −12→12

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.070	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0387P)² + 0.1633P] where P = (F_o² + 2F_c²)/3
1098 reflections	(Δ/σ)_max = 0.006
82 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₂H₁₂N₂O₂S₂	V = 622.2 (2) Å³
M_r = 280.36	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.2776 (17) Å	µ = 0.42 mm⁻¹
b = 6.9790 (14) Å	T = 293 K
c = 10.791 (2) Å	0.28 × 0.26 × 0.24 mm
β = 93.52 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1098 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1007 reflections with I > 2(I)
T_min = 0.889, T_max = 0.904	R_int = 0.013
3068 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.070	H-atom parameters constrained
S = 1.07	Δρ_max = 0.14 e Å⁻³
1098 reflections	Δρ_min = −0.22 e Å⁻³
82 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	0.15370 (5)	0.18793 (5)	0.61401 (3)	0.03644 (16)
N1	0.32129 (13)	0.50095 (17)	0.63713 (10)	0.0304 (3)
O1	0.33935 (13)	0.43441 (16)	0.75096 (9)	0.0434 (3)
C5	0.22742 (15)	0.39913 (19)	0.55220 (12)	0.0285 (3)
C6	0.04101 (17)	0.0906 (2)	0.47863 (13)	0.0336 (3)
H7B	−0.0423	0.1793	0.4512	0.050*
H7C	0.1130	0.0708	0.4134	0.050*
C1	0.39499 (18)	0.6652 (2)	0.60369 (16)	0.0377 (4)
H1A	0.4632	0.7341	0.6635	0.045*
C4	0.20326 (17)	0.4676 (2)	0.43202 (13)	0.0353 (3)
H4A	0.1378	0.3962	0.3718	0.042*
C2	0.37221 (18)	0.7344 (2)	0.48487 (15)	0.0417 (4)
H6A	0.4235	0.8516	0.4622	0.050*
C3	0.27461 (19)	0.6363 (2)	0.39827 (15)	0.0415 (4)
H5A	0.2573	0.6851	0.3153	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0473 (3)	0.0327 (2)	0.0285 (2)	−0.00976 (16)	−0.00380 (16)	0.00374 (14)
N1	0.0298 (6)	0.0312 (6)	0.0300 (6)	0.0024 (5)	0.0001 (5)	−0.0051 (5)
O1	0.0515 (6)	0.0479 (7)	0.0295 (6)	−0.0003 (5)	−0.0092 (5)	−0.0024 (5)
C5	0.0278 (7)	0.0285 (7)	0.0292 (7)	−0.0003 (5)	0.0019 (5)	−0.0023 (6)
C6	0.0378 (8)	0.0320 (8)	0.0308 (7)	−0.0061 (6)	0.0008 (6)	−0.0004 (6)
C1	0.0319 (7)	0.0320 (7)	0.0494 (9)	−0.0040 (6)	0.0038 (6)	−0.0119 (7)
C4	0.0386 (8)	0.0382 (8)	0.0290 (7)	−0.0056 (6)	0.0011 (6)	0.0003 (6)
C2	0.0412 (9)	0.0325 (8)	0.0528 (10)	−0.0052 (7)	0.0132 (7)	−0.0007 (7)
C3	0.0469 (9)	0.0408 (8)	0.0375 (8)	−0.0029 (7)	0.0081 (7)	0.0068 (7)

Geometric parameters (Å, º) top

S1—C5	1.7436 (14)	C6—H7C	0.9600
S1—C6	1.8160 (15)	C1—C2	1.372 (2)
N1—O1	1.3131 (16)	C1—H1A	0.9600
N1—C1	1.3578 (19)	C4—C3	1.377 (2)
N1—C5	1.3642 (18)	C4—H4A	0.9600
C5—C4	1.385 (2)	C2—C3	1.379 (2)
C6—C6ⁱ	1.521 (3)	C2—H6A	0.9601
C6—H7B	0.9600	C3—H5A	0.9601

C5—S1—C6	100.54 (6)	N1—C1—C2	120.48 (14)
O1—N1—C1	121.33 (12)	N1—C1—H1A	120.0
O1—N1—C5	118.14 (12)	C2—C1—H1A	119.5
C1—N1—C5	120.52 (12)	C3—C4—C5	120.21 (14)
N1—C5—C4	119.53 (13)	C3—C4—H4A	119.9
N1—C5—S1	112.44 (10)	C5—C4—H4A	119.9
C4—C5—S1	128.02 (11)	C1—C2—C3	119.98 (15)
C6ⁱ—C6—S1	106.50 (13)	C1—C2—H6A	120.0
C6ⁱ—C6—H7B	107.7	C3—C2—H6A	120.0
S1—C6—H7B	109.3	C4—C3—C2	119.23 (15)
C6ⁱ—C6—H7C	114.3	C4—C3—H5A	120.5
S1—C6—H7C	109.4	C2—C3—H5A	120.3
H7B—C6—H7C	109.5

O1—N1—C5—C4	178.66 (12)	O1—N1—C1—C2	−178.76 (13)
C1—N1—C5—C4	−2.06 (19)	C5—N1—C1—C2	2.0 (2)
O1—N1—C5—S1	−2.27 (15)	N1—C5—C4—C3	0.6 (2)
C1—N1—C5—S1	177.01 (10)	S1—C5—C4—C3	−178.35 (12)
C6—S1—C5—N1	−178.99 (10)	N1—C1—C2—C3	−0.4 (2)
C6—S1—C5—C4	−0.02 (15)	C5—C4—C3—C2	1.0 (2)
C5—S1—C6—C6ⁱ	−176.25 (13)	C1—C2—C3—C4	−1.1 (2)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1ⁱⁱ	0.96	2.30	3.225 (2)	161
C4—H4A···S1ⁱⁱⁱ	0.96	2.85	3.599 (2)	135

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₂O₂S₂
M_r	280.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.2776 (17), 6.9790 (14), 10.791 (2)
β (°)	93.52 (3)
V (Å³)	622.2 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.42
Crystal size (mm)	0.28 × 0.26 × 0.24

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.889, 0.904
No. of measured, independent and observed [I > 2(I)] reflections	3068, 1098, 1007
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.070, 1.07
No. of reflections	1098
No. of parameters	82
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.22

Computer programs: XSCANS (Bruker, 1998), SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1ⁱ	0.96	2.30	3.225 (2)	161
C4—H4A···S1ⁱⁱ	0.96	2.85	3.599 (2)	135

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

Acknowledgements

This work was supported by the Beijing Municipal Natural Science Foundation (No. 2082004) and the Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality (PHR 200907105).

References

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