2,2′-[o-Phenylenebis(methylenethio)]bis(pyridine N-oxide)

Chao-Yan Zhang; Qian Gao; Yue Cui; Ya-Bo Xie

doi:10.1107/S160053680902073X

. 2009 Jun 6;65(Pt 7):o1482. doi: 10.1107/S160053680902073X

2,2′-[o-Phenylenebis(methylenethio)]bis(pyridine N-oxide)

Chao-Yan Zhang ^a, Qian Gao ^a, Yue Cui ^a, Ya-Bo Xie ^a,^*

PMCID: PMC2969296 PMID: 21582784

Abstract

In the title compound, C₁₈H₁₆N₂O₂S₂, the benzene ring makes dihedral angles of 7.41 and 86.59° with the two outer pyridine N-oxygen rings. Two short intramolecular C—H⋯S contacts occur. The crystal packing is stabilized by C—H⋯O hydrogen bonds, C—H⋯π interactions and weak π–π staking interactions [centroid–centroid distance 3.7596 (7) Å].

Related literature

For a related stucture, see: Han et al. (2005 ▶). For thioether compounds, see: Xie et al. (2005 ▶).

Experimental

Crystal data

C₁₈H₁₆N₂O₂S₂
M _r = 356.47
Monoclinic,
a = 7.5075 (15) Å
b = 17.810 (4) Å
c = 12.480 (3) Å
β = 105.20 (3)°
V = 1610.3 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 293 K
0.34 × 0.28 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
9681 measured reflections
3782 independent reflections
3145 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.083
S = 1.02
3782 reflections
225 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); 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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680902073X/at2798sup1.cif

e-65-o1482-sup1.cif^{(19.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902073X/at2798Isup2.hkl

e-65-o1482-Isup2.hkl^{(185.4KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1ⁱ	0.93	2.42	3.133 (2)	134
C5—H5A⋯O1ⁱⁱ	0.93	2.38	3.253 (2)	155
C8—H8A⋯S1	0.93	2.67	3.1105 (18)	110
C11—H11A⋯S2	0.93	2.47	2.9322 (18)	111
C15—H15A⋯O2ⁱⁱⁱ	0.93	2.58	3.461 (2)	158
C9—H9A⋯Cg2^iv	0.93	2.90	3.645 (2)	138

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg2 is the centroid of the N2/C1–C5 ring.

Acknowledgments

This work was supported Beijing Municipal Natural Science Foundation (grant No. 2082004).

supplementary crystallographic information

Comment

Thioether-type ligands are attracting great attention as the conformational freedom, flexible multidentate bridging ligands (Xie et al., 2005). In continuation of the structural study of thioether-type ligands (Han et al., 2005), herein, we report the crystal sructure of the title compound.

The title compound (Fig. 1) was obtained by the reaction of 2-mercaptopyridine N-oxide and o-xylylene dibromide. In the asymmetric unit, the central benzene ring makes dihedral angles of 7.44 and 86.52° with the two outer pyridine N-oxygen rings and the crystal packing is stabilized by C—H···O and C—H..S hydrogen bonding, C—H···π interactions (Table 1) and weak π-π staking interactions [centroid-to-centroid distance 3.7596 (7) Å].

Experimental

2-Mercaptopyridine N-oxide (1.2719 g, 10.00 mmol) was added to a stirred solution of KOH (0.6091 g, 10.85 mmol) in ethanol (50 ml). After 30 min, o-xylylene dibromide (1.3206 g, 5.00 mmol) was added and the mixture was heated to 343 K for 6 h with vigorous stirring. The mixture was cooled to room temperature and the precipitate was filtered off and washed with ethanol and water, giving a white powder in 66.0% yield. Then, a solution of the powder in CHCl₃/CH₃CN with a molar ratio of 1:1 was filtered. Slow diffusion of ether into the filtrate yielded colourless prism crystals.