Crystal structure of 3,3′-diisopropyl-1,1′-(pyridine-2,6-di­yl)bis­[1H-imidazole-2(3H)-thione]

Ying Sun; Hui Wang; Wei-Guo Jia

doi:10.1107/S2056989015005642

. 2015 Mar 25;71(Pt 4):o255. doi: 10.1107/S2056989015005642

Crystal structure of 3,3′-diisopropyl-1,1′-(pyridine-2,6-diyl)bis[1H-imidazole-2(3H)-thione]

Ying Sun ^a,^*, Hui Wang ^a, Wei-Guo Jia ^a

PMCID: PMC4438837 PMID: 26029442

Abstract

In the title compound, C₁₇H₂₁N₅S₂, the dihedral angles between the central pyridine ring and its pendant imidazole rings are 29.40 (9) and 40.77 (9)°; the pendant rings are twisted in an opposite sense with respect to the central ring. In each case, the S atom is approximately anti to the N atom of the pyridine ring. For both substituents, the H atom attached to the central C atom of the isopropyl group is approximately syn to the S atom in the attached ring. In the crystal, molecules are linked by weak C—H⋯S interactions, generating C(5) chains propagating along [001].

Keywords: crystal structure, organochalcogen ligand, conformation, C—H⋯S interactions

Related literature

For applications of organochalcogen compounds in chemistry, see: Owen (2012 ▸). For the synthesis of the starting reagent, 2,6-bis(1-isopropylimidazolium)pyridine dibromide, see: McGuinness et al. (2004 ▸). For the synthesis of the title compound, see: Jia et al. (2009a ▸). For the crystal structure of a similar coumpound, see: Jia et al. (2009b ▸)

Experimental

Crystal data

C₁₇H₂₁N₅S₂
M _r = 359.51
Monoclinic,
a = 14.7942 (11) Å
b = 8.9398 (7) Å
c = 13.8194 (11) Å
β = 101.675 (1)°
V = 1789.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 293 K
0.20 × 0.19 × 0.19 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T _min = 0.941, T _max = 0.944
14858 measured reflections
4083 independent reflections
3131 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.111
S = 1.02
4083 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.31 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015005642/hb7387sup1.cif

e-71-0o255-sup1.cif^{(16.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015005642/hb7387Isup2.hkl

e-71-0o255-Isup2.hkl^{(200.1KB, hkl)}

Click here for additional data file.^{(2.9KB, cdx)}

Supporting information file. DOI: 10.1107/S2056989015005642/hb7387Isup3.cdx

Click here for additional data file.^{(6.4KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015005642/hb7387Isup4.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015005642/hb7387fig1.tif

The molecular structure of title molecule showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. All hydrogen atoms are omitted for clarity.

CCDC reference: 1054528

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C13H13AS2ⁱ	0.93	2.81	3.7214(18)	166

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the National Natural Science Foundation of China (21102004)

supplementary crystallographic information

S1. Introduction

The title compound (Fig. 1)was prepared as an intermediate in our ongoing search (Jia et al., 2009a) for organochalcogen ligands. The title compound was thermally stable and inert toward air and moisture in the solid state, and was soluble in common organic solvents such as CH₂Cl₂, CHCl₃ and THF.

The bond lengths and angles are normal and correspond to those observed in the related 2,6-bis(1-tert-butylimidazole-2-thione)pyridine (Jia et al., 2009b).

S2. Experimental

S2.1. Synthesis and crystallization

The title compound was prepared following the known procedure (Jia et al., 2009a). In a 100 mL round-bottomed flask fitted with reflux condenser were placed 2,6-bis(1-isopropylimidazolium)pyridine dibromide (4.65 g, 10 mmol), S (0.64 g, 20 mmol) and 2.8 g K₂CO₃ and 50 mL methanol as solvent. The mixture was allowed to reflux for 8 h after which the methanol was removed with a rotary evaporator. The remaining solid was shaken with 2 × 30 mL CH₂Cl₂ which was then filtered and rotary evaporated. The product was recrystallized from CH₂Cl₂/MeOH to give colorless solid, Yield: (2.80 g 78%).

S2.2. Refinement

All hydrogen atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93–0.97 Å and U_iso(H) = 1.2–1.5U_eq.