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

Sun, Y.; Wang, H.; Jia, W.-G.

doi:10.1107/S2056989015005642

organic compounds

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doi:10.1107/S2056989015005642

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

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

^aAnhui Normal University, Wuhu, 241000, People's Republic of China
^*Correspondence e-mail: syw963@mail.ahnu.edu.cn

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 18 March 2015; accepted 19 March 2015; online 25 March 2015)

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.

CCDC reference: 1054528

1. 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 )

2. Experimental

2.1. Crystal data

C₁₇H₂₁N₅S₂
M_r = 359.51
Monoclinic, P 2₁ /c
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

2.2. 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

2.3. Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯S2ⁱ	0.93	2.81	3.7214 (18)	166
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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.

Supporting information

CCDC reference: 1054528

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S2056989015005642/hb7387sup1.cif

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

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

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

checkCIF report

Introduction top

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).

Experimental top

Synthesis and crystallization top

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%).

Refinement top

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.

Related literature top

For applications of organothalcogen 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)

Structure description top

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).

Synthesis and crystallization top

Refinement details top

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.

Computing details top

Data collection: SMART (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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 title molecule showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. All hydrogen atoms are omitted for clarity.

3,3'-Diisopropyl-1,1'-(pyridine-2,6-diyl)bis[1H-imidazole-2(3H)-thione] top

Crystal data top

C₁₇H₂₁N₅S₂	F(000) = 760
M_r = 359.51	D_x = 1.334 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.7942 (11) Å	Cell parameters from 5873 reflections
b = 8.9398 (7) Å	θ = 2.3–27.4°
c = 13.8194 (11) Å	µ = 0.31 mm⁻¹
β = 101.675 (1)°	T = 293 K
V = 1789.9 (2) Å³	Prism, colorless
Z = 4	0.20 × 0.19 × 0.19 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	4083 independent reflections
Radiation source: fine-focus sealed tube	3131 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
phi and ω scans	θ_max = 27.5°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −19→19
T_min = 0.941, T_max = 0.944	k = −10→11
14858 measured reflections	l = −16→17

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0574P)² + 0.4683P] where P = (F_o² + 2F_c²)/3
4083 reflections	(Δ/σ)_max = 0.001
217 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₇H₂₁N₅S₂	V = 1789.9 (2) Å³
M_r = 359.51	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.7942 (11) Å	µ = 0.31 mm⁻¹
b = 8.9398 (7) Å	T = 293 K
c = 13.8194 (11) Å	0.20 × 0.19 × 0.19 mm
β = 101.675 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4083 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	3131 reflections with I > 2σ(I)
T_min = 0.941, T_max = 0.944	R_int = 0.028
14858 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.02	Δρ_max = 0.27 e Å⁻³
4083 reflections	Δρ_min = −0.31 e Å⁻³
217 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	0.98780 (3)	0.42684 (7)	0.26709 (4)	0.05246 (17)
N1	0.70991 (9)	0.27508 (16)	0.09090 (10)	0.0329 (3)
C1	0.62838 (10)	0.28936 (19)	0.11628 (12)	0.0328 (4)
N2	0.86809 (8)	0.25912 (16)	0.12935 (10)	0.0317 (3)
C2	0.61678 (12)	0.3113 (2)	0.21163 (13)	0.0392 (4)
H2A	0.5585	0.3252	0.2259	0.047*
C3	0.69534 (12)	0.3118 (2)	0.28522 (13)	0.0412 (4)
H3A	0.6904	0.3248	0.3507	0.049*
N4	0.55290 (9)	0.28823 (17)	0.03416 (10)	0.0338 (3)
C4	0.78119 (11)	0.2932 (2)	0.26209 (13)	0.0381 (4)
H4A	0.8346	0.2907	0.3110	0.046*
N5	0.42350 (9)	0.24388 (18)	−0.06671 (11)	0.0381 (3)
C5	0.78467 (10)	0.27858 (18)	0.16342 (12)	0.0320 (3)
C6	0.87118 (11)	0.1809 (2)	0.04339 (12)	0.0364 (4)
H6A	0.8219	0.1327	0.0029	0.044*
C7	0.95753 (11)	0.1872 (2)	0.02932 (13)	0.0370 (4)
H7A	0.9795	0.1438	−0.0226	0.044*
C8	0.95469 (10)	0.31641 (18)	0.16853 (12)	0.0321 (4)
C9	1.15933 (12)	0.1751 (2)	0.08642 (16)	0.0503 (5)
H9A	1.1498	0.0880	0.1237	0.075*
H9B	1.2240	0.1981	0.0981	0.075*
H9C	1.1371	0.1562	0.0173	0.075*
C10	1.10746 (11)	0.3058 (2)	0.11811 (14)	0.0376 (4)
H10A	1.1317	0.3230	0.1886	0.045*
C11	1.11964 (14)	0.4489 (3)	0.06389 (19)	0.0612 (6)
H11A	1.0858	0.5280	0.0873	0.092*
H11B	1.0970	0.4348	−0.0057	0.092*
H11C	1.1839	0.4746	0.0756	0.092*
C12	0.55688 (12)	0.3554 (2)	−0.05536 (13)	0.0412 (4)
H12A	0.6063	0.4095	−0.0696	0.049*
C13	0.47749 (12)	0.3283 (2)	−0.11682 (13)	0.0429 (4)
H13A	0.4610	0.3604	−0.1820	0.052*
C14	0.46937 (11)	0.2156 (2)	0.02667 (12)	0.0343 (4)
C15	0.33079 (16)	0.0985 (3)	−0.20167 (18)	0.0644 (6)
H15A	0.3733	0.0167	−0.1858	0.097*
H15B	0.3496	0.1609	−0.2505	0.097*
H15C	0.2700	0.0600	−0.2271	0.097*
C16	0.32985 (12)	0.1895 (2)	−0.10926 (14)	0.0461 (5)
H16A	0.3102	0.1238	−0.0606	0.055*
C17	0.26378 (14)	0.3198 (3)	−0.12819 (18)	0.0624 (6)
H17A	0.2647	0.3725	−0.0675	0.094*
H17B	0.2025	0.2835	−0.1538	0.094*
H17C	0.2821	0.3862	−0.1753	0.094*
S2	0.43238 (3)	0.11047 (6)	0.11128 (3)	0.04734 (15)
N3	1.00857 (9)	0.26980 (15)	0.10570 (10)	0.0320 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0442 (3)	0.0663 (4)	0.0481 (3)	−0.0154 (2)	0.0122 (2)	−0.0280 (2)
N1	0.0281 (6)	0.0399 (8)	0.0307 (7)	−0.0005 (6)	0.0055 (5)	−0.0020 (6)
C1	0.0289 (7)	0.0370 (9)	0.0321 (9)	−0.0014 (6)	0.0052 (6)	−0.0018 (7)
N2	0.0271 (6)	0.0376 (8)	0.0295 (7)	0.0002 (5)	0.0033 (5)	−0.0056 (6)
C2	0.0333 (8)	0.0507 (11)	0.0350 (9)	−0.0015 (7)	0.0103 (7)	−0.0051 (8)
C3	0.0415 (9)	0.0539 (11)	0.0287 (9)	−0.0068 (8)	0.0084 (7)	−0.0052 (8)
N4	0.0273 (6)	0.0459 (8)	0.0279 (7)	0.0001 (6)	0.0052 (5)	0.0013 (6)
C4	0.0343 (8)	0.0471 (10)	0.0311 (9)	−0.0035 (7)	0.0019 (7)	−0.0015 (7)
N5	0.0317 (7)	0.0496 (9)	0.0307 (7)	−0.0029 (6)	0.0011 (6)	0.0035 (7)
C5	0.0294 (7)	0.0333 (9)	0.0328 (9)	−0.0013 (6)	0.0052 (6)	−0.0024 (7)
C6	0.0332 (8)	0.0427 (10)	0.0308 (9)	0.0003 (7)	0.0008 (7)	−0.0088 (7)
C7	0.0355 (8)	0.0447 (10)	0.0299 (9)	0.0041 (7)	0.0040 (7)	−0.0070 (7)
C8	0.0293 (7)	0.0348 (9)	0.0311 (9)	0.0004 (6)	0.0034 (6)	−0.0014 (7)
C9	0.0335 (9)	0.0548 (12)	0.0640 (13)	0.0066 (8)	0.0131 (9)	−0.0002 (10)
C10	0.0257 (7)	0.0468 (10)	0.0390 (10)	−0.0017 (7)	0.0034 (7)	−0.0015 (8)
C11	0.0445 (11)	0.0536 (13)	0.0861 (17)	−0.0055 (9)	0.0149 (11)	0.0126 (12)
C12	0.0363 (9)	0.0543 (11)	0.0342 (9)	−0.0048 (8)	0.0103 (7)	0.0044 (8)
C13	0.0413 (9)	0.0568 (12)	0.0300 (9)	−0.0008 (8)	0.0055 (7)	0.0078 (8)
C14	0.0276 (7)	0.0439 (10)	0.0310 (9)	0.0014 (7)	0.0047 (6)	0.0007 (7)
C15	0.0577 (13)	0.0512 (13)	0.0718 (16)	0.0040 (10)	−0.0162 (11)	−0.0118 (11)
C16	0.0344 (9)	0.0589 (12)	0.0396 (10)	−0.0094 (8)	−0.0050 (7)	0.0097 (9)
C17	0.0375 (10)	0.0818 (17)	0.0643 (14)	0.0058 (10)	0.0019 (10)	−0.0163 (13)
S2	0.0384 (2)	0.0678 (4)	0.0345 (3)	−0.0096 (2)	0.00434 (18)	0.0117 (2)
N3	0.0275 (6)	0.0369 (7)	0.0304 (7)	0.0015 (5)	0.0026 (5)	−0.0021 (6)

Geometric parameters (Å, º) top

S1—C8	1.6732 (17)	N5—C14	1.355 (2)
N1—C1	1.329 (2)	N5—C13	1.382 (2)
N1—C5	1.334 (2)	N5—C16	1.474 (2)
C1—C2	1.377 (2)	C6—C7	1.332 (2)
C1—N4	1.422 (2)	C7—N3	1.381 (2)
N2—C6	1.387 (2)	C8—N3	1.358 (2)
N2—C8	1.384 (2)	C9—C10	1.511 (3)
N2—C5	1.418 (2)	C10—N3	1.474 (2)
C2—C3	1.381 (2)	C10—C11	1.511 (3)
C3—C4	1.381 (2)	C12—C13	1.325 (2)
N4—C12	1.387 (2)	C14—S2	1.6759 (18)
N4—C14	1.381 (2)	C15—C16	1.517 (3)
C4—C5	1.381 (2)	C16—C17	1.508 (3)

C1—N1—C5	117.28 (14)	C7—C6—N2	107.61 (14)
N1—C1—C2	124.19 (15)	C6—C7—N3	107.66 (15)
N1—C1—N4	113.38 (14)	N3—C8—N2	104.65 (13)
C2—C1—N4	122.34 (14)	N3—C8—S1	126.06 (12)
C6—N2—C8	109.47 (13)	N2—C8—S1	129.20 (12)
C6—N2—C5	121.87 (13)	N3—C10—C11	110.02 (14)
C8—N2—C5	128.58 (14)	N3—C10—C9	110.36 (15)
C3—C2—C1	117.12 (15)	C11—C10—C9	113.10 (16)
C2—C3—C4	120.37 (16)	C13—C12—N4	107.49 (15)
C12—N4—C14	109.60 (14)	C12—C13—N5	107.80 (16)
C12—N4—C1	122.72 (13)	N5—C14—N4	104.58 (14)
C14—N4—C1	127.55 (14)	N5—C14—S2	126.72 (13)
C5—C4—C3	117.37 (15)	N4—C14—S2	128.67 (13)
C14—N5—C13	110.50 (14)	N5—C16—C15	110.17 (16)
C14—N5—C16	124.60 (15)	N5—C16—C17	109.80 (17)
C13—N5—C16	124.89 (15)	C15—C16—C17	112.60 (16)
N1—C5—C4	123.57 (14)	C8—N3—C7	110.61 (13)
N1—C5—N2	113.12 (14)	C8—N3—C10	123.79 (14)
C4—C5—N2	123.25 (14)	C7—N3—C10	125.60 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···S2ⁱ	0.93	2.81	3.7214 (18)	166

Symmetry code: (i) x, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···S2ⁱ	0.93	2.81	3.7214 (18)	166

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

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

References

Bruker (2008). SMART, SAINT and SADABS. Bruker AXS Inc, Madision, Wisconsin, USA. Google Scholar
Jia, W.-G., Huang, Y.-B. & Jin, G.-X. (2009a). J. Organomet. Chem. 694, 4008–4013. CSD CrossRef CAS Google Scholar
Jia, W.-G., Huang, Y.-B. & Jin, G.-X. (2009b). J. Organomet. Chem. 694, 3376–3380. CSD CrossRef CAS Google Scholar
McGuinness, D. S., Gibson, V. C. & Steed, J. W. (2004). Organometallics, 23, 6288–6292. CSD CrossRef CAS Google Scholar
Owen, G. R. (2012). Chem. Soc. Rev. 41, 3535–3546. CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S2056989015005642

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

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

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