(E)-2-[(2,3-Di­bromo­all­yl)sulfan­yl]-1-methyl-1H-imidazol-3-ium bromide

Oberparleiter, S.; Laus, G.; Wurst, K.; Schottenberger, H.

doi:10.1107/S2414314616014991

organic compounds

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ISSN: 2414-3146

Volume 1| Part 9| September 2016| x161499

doi:10.1107/S2414314616014991

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(E)-2-[(2,3-Dibromoallyl)sulfanyl]-1-methyl-1H-imidazol-3-ium bromide

Stefan Oberparleiter,^a Gerhard Laus,^a ^* Klaus Wurst ^a and Herwig Schottenberger ^a

^aUniversity of Innsbruck, Faculty of Chemistry and Pharmacy, Innrain 80, 6020 Innsbruck, Austria
^*Correspondence e-mail: gerhard.laus@uibk.ac.at

Edited by J. Simpson, University of Otago, New Zealand (Received 20 September 2016; accepted 22 September 2016; online 27 September 2016)

The title salt, C₇H₉Br₂N₂S⁺·Br⁻, was obtained from methimazole (1-methyl-3H-imidazole-2-thione) by S-allylation using 1,2,3-tribromopropene. A positional disorder of the bromine atoms at the allyl chain was observed, with each Br atom equally disordered over two positions. N—H⋯Br and C—H⋯Br interactions were identified.

Keywords: crystal structure; imidazole; methimazole; S-allylation.

CCDC reference: 1505734

Structure description

The imidazolium ring in the title compound is almost perfectly planar [maximum deviation = 0.004 (2) Å for N2, and the S-allyl chain is positioned perpendicularly to the ring system, making a dihedral angle of 88.95 (13)° (Fig. 1). Atom C5 is displaced from the ring plane by 1.481 (2) Å. The cation acts as a multiple donor of hydrogen-bond contacts. Each bromide ion accepts four hydrogen bonds from four neighbouring cations (Table 1). A classical N1—H⋯Br3 hydrogen bond and a quite short C3—H⋯Br3 contact are observed. The hydrogen atoms of the allyl group are engaged in C5—H⋯Br and C7—H⋯Br interactions (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br3	0.85 (2)	2.37 (2)	3.215 (2)	170 (2)
C3—H3⋯Br3ⁱ	0.95	2.64	3.584 (3)	170
C5—H5A⋯Br3ⁱⁱ	0.99	2.89	3.669 (2)	136
C7—H7⋯Br3ⁱⁱⁱ	0.95	2.87	3.772 (2)	159
Symmetry codes: (i) x, y-1, z; (ii) x-1, y, z; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the ion pair of the title compound, showing the atom labels and 50% probability displacement ellipsoids for the non-H atoms.

Figure 2
Crystal packing of the title compound, with hydrogen bonds drawn as dashed lines.

A related structure without bromine atoms at the allyl chain has been reported (Gaitor et al., 2015 ).

Synthesis and crystallization

1,2,3-Tribromopropene (0.50 g, 1.8 mmol; Kodomari et al., 1989 ) was added to a solution of methimazole (0.25 g, 2.2 mmol) in CH₂Cl₂ (3 ml). The mixture was stirred at room temperature for 18 h. The colorless product was collected by filtration, washed with CH₂Cl₂ and dried under reduced pressure (0.47 g, 67%), m.p. 442 K. Suitable crystals were obtained by slow evaporation of a solution in EtOH. The PXRD (Mo Kα radiation) of the bulk material was identical to the one calculated from the single-crystal diffraction data (Fig. 3), indicating phase purity. ¹H NMR (300 MHz, DMSO-d₆): δ 3.88 (s, 3H), 4.22 (s, 2H), 7.06 (s, 1H), 7.87 (d, J = 1.6 Hz, 1H), 7.97 (d, J = 1.6 Hz, 1H) p.p.m. ¹³C NMR (75 MHz, DMSO-d₆): δ 35.4, 41.9, 108.4, 119.6, 122.0, 126.3, 136.7 p.p.m. IR (neat): ν 3157 (w), 3071 (w), 3025 (m), 2890 (w), 2779 (m), 1572 (m), 1480 (m), 1293 (m), 1018 (m), 907 (m), 835 (m), 770 (s), 698 (m), 673 (m) cm⁻¹.

Figure 3
Pawley fit (R_wp = 2.77%, R_exp = 3.33%, R_p = 2.21%, goodness-of-fit = 0.83) of the PXRD data with a model calculated from the structural data of the single-crystal structure determination. Black dots indicate raw data, while the red line indicates the calculated model. The difference curve is shown in blue.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Atoms Br1 and Br2 showed extreme temperature factors and were split over two positions with a 1:1 ratio for each.

Table 2
Experimental details

Crystal data
Chemical formula	C₇H₉Br₂N₂S⁺·Br⁻
M_r	392.95
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	203
a, b, c (Å)	7.2101 (3), 8.2105 (3), 20.5363 (8)
β (°)	90.619 (1)
V (Å³)	1215.65 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	10.09
Crystal size (mm)	0.18 × 0.14 × 0.12

Data collection
Diffractometer	Bruker D8 QUEST PHOTON 100
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.208, 0.333
No. of measured, independent and observed [I > 2σ(I)] reflections	22243, 2513, 2228
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.052, 1.04
No. of reflections	2513
No. of parameters	142
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.50
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1505734

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616014991/sj4057sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616014991/sj4057Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616014991/sj4057Isup3.mol

Supporting information file. DOI: 10.1107/S2414314616014991/sj4057Isup4.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: Mercury (Macrae et al., 2008).

(E)-2-[(2,3-Dibromoallyl)sulfanyl]-1-methyl-1H-imidazol-3-ium bromide top

Crystal data top

C₇H₉Br₂N₂S⁺·Br⁻	D_x = 2.147 Mg m⁻³
M_r = 392.95	Melting point: 442 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.2101 (3) Å	Cell parameters from 9903 reflections
b = 8.2105 (3) Å	θ = 2.7–26.7°
c = 20.5363 (8) Å	µ = 10.09 mm⁻¹
β = 90.619 (1)°	T = 203 K
V = 1215.65 (8) Å³	Prism, colourless
Z = 4	0.18 × 0.14 × 0.12 mm
F(000) = 744

Data collection top

Bruker D8 QUEST PHOTON 100 diffractometer	2513 independent reflections
Radiation source: Incoatec Microfocus	2228 reflections with I > 2σ(I)
Multi layered optics monochromator	R_int = 0.043
Detector resolution: 10.4 pixels mm^-1	θ_max = 26.5°, θ_min = 2.7°
φ and ω scans	h = −9→8
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −10→10
T_min = 0.208, T_max = 0.333	l = −25→24
22243 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.021	w = 1/[σ²(F_o²) + (0.0234P)² + 0.5418P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.052	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 0.67 e Å⁻³
2513 reflections	Δρ_min = −0.50 e Å⁻³
142 parameters	Extinction correction: SHELXL2014 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0054 (4)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Hydrogen at N1 found and refined isotropically with bond restraints (d=87 pm). The two Br-Atoms Br1 and shows extremly cigarlikes temperature factors and were split in two position with ratio of 1:1 for each.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.17108 (7)	0.46260 (6)	0.42687 (2)	0.03705 (13)
N1	0.5433 (3)	0.3906 (2)	0.42723 (9)	0.0423 (4)
H1	0.588 (3)	0.487 (2)	0.4262 (12)	0.047 (7)*
N2	0.3706 (3)	0.1773 (2)	0.42235 (9)	0.0424 (4)
C1	0.3676 (3)	0.3405 (2)	0.42357 (9)	0.0355 (5)
C2	0.6586 (4)	0.2590 (3)	0.42872 (13)	0.0546 (7)
H2	0.7902	0.2612	0.4312	0.066*
C3	0.5518 (4)	0.1265 (3)	0.42602 (12)	0.0542 (6)
H3	0.5935	0.0167	0.4266	0.065*
C4	0.2091 (4)	0.0698 (3)	0.42008 (14)	0.0593 (7)
H4A	0.1409	0.0790	0.4609	0.089*
H4B	0.2501	−0.0430	0.4142	0.089*
H4C	0.1281	0.1013	0.3836	0.089*
C5	0.1903 (3)	0.5685 (3)	0.34904 (10)	0.0387 (5)
H5A	0.0911	0.6516	0.3462	0.046*
H5B	0.3107	0.6263	0.3482	0.046*
C6	0.1770 (3)	0.4618 (3)	0.29077 (10)	0.0391 (5)
C7	0.2959 (3)	0.4451 (3)	0.24341 (11)	0.0482 (6)
H7	0.2764	0.3655	0.2105	0.058*
Br1	−0.0306 (4)	0.3200 (3)	0.28492 (17)	0.0617 (5)	0.5
Br2	0.5085 (3)	0.58268 (18)	0.24163 (10)	0.0641 (3)	0.5
Br1A	−0.0598 (5)	0.3638 (3)	0.27945 (17)	0.0629 (5)	0.5
Br2A	0.5379 (3)	0.5213 (2)	0.24649 (11)	0.0788 (5)	0.5
Br3	0.76128 (4)	0.73127 (3)	0.41814 (2)	0.04785 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0432 (3)	0.0407 (3)	0.0273 (3)	0.0116 (2)	0.0008 (2)	−0.0028 (2)
N1	0.0437 (11)	0.0469 (11)	0.0364 (10)	0.0067 (9)	0.0020 (8)	0.0030 (8)
N2	0.0560 (12)	0.0365 (9)	0.0346 (10)	0.0114 (9)	0.0038 (8)	−0.0037 (8)
C1	0.0436 (12)	0.0391 (11)	0.0238 (10)	0.0077 (9)	0.0006 (8)	−0.0013 (8)
C2	0.0477 (14)	0.0711 (18)	0.0452 (14)	0.0241 (13)	0.0046 (11)	0.0029 (12)
C3	0.0664 (16)	0.0520 (14)	0.0442 (14)	0.0275 (13)	0.0067 (11)	0.0003 (11)
C4	0.0742 (18)	0.0436 (14)	0.0601 (17)	−0.0037 (12)	0.0025 (13)	−0.0073 (11)
C5	0.0520 (13)	0.0351 (11)	0.0289 (10)	0.0094 (9)	−0.0022 (9)	−0.0022 (8)
C6	0.0468 (12)	0.0402 (11)	0.0301 (11)	0.0079 (9)	−0.0058 (9)	−0.0013 (9)
C7	0.0531 (14)	0.0583 (14)	0.0332 (12)	0.0081 (11)	−0.0031 (10)	−0.0075 (10)
Br1	0.0635 (11)	0.0797 (12)	0.0418 (5)	−0.0244 (8)	−0.0079 (7)	−0.0081 (8)
Br2	0.0551 (7)	0.0919 (9)	0.0454 (4)	−0.0165 (6)	0.0079 (4)	−0.0053 (6)
Br1A	0.0572 (7)	0.0840 (13)	0.0472 (9)	−0.0074 (7)	−0.0048 (5)	−0.0183 (9)
Br2A	0.0574 (6)	0.1289 (14)	0.0501 (6)	−0.0017 (8)	0.0080 (4)	−0.0115 (9)
Br3	0.07191 (18)	0.03746 (13)	0.03436 (14)	0.01620 (10)	0.00936 (10)	0.00275 (9)

Geometric parameters (Å, º) top

S1—C1	1.738 (2)	C4—H4B	0.9800
S1—C5	1.826 (2)	C4—H4C	0.9800
N1—C1	1.333 (3)	C5—C6	1.485 (3)
N1—C2	1.364 (3)	C5—H5A	0.9900
N1—H1	0.852 (16)	C5—H5B	0.9900
N2—C1	1.340 (3)	C6—C7	1.311 (3)
N2—C3	1.372 (3)	C6—Br1A	1.899 (4)
N2—C4	1.462 (3)	C6—Br1	1.899 (4)
C2—C3	1.334 (4)	C7—Br2A	1.854 (3)
C2—H2	0.9500	C7—Br2	1.905 (3)
C3—H3	0.9500	C7—H7	0.9500
C4—H4A	0.9800

C1—S1—C5	99.84 (10)	N2—C4—H4C	109.5
C1—N1—C2	109.6 (2)	H4A—C4—H4C	109.5
C1—N1—H1	130.1 (17)	H4B—C4—H4C	109.5
C2—N1—H1	120.2 (17)	C6—C5—S1	114.81 (15)
C1—N2—C3	108.6 (2)	C6—C5—H5A	108.6
C1—N2—C4	126.3 (2)	S1—C5—H5A	108.6
C3—N2—C4	125.1 (2)	C6—C5—H5B	108.6
N1—C1—N2	107.10 (18)	S1—C5—H5B	108.6
N1—C1—S1	126.47 (16)	H5A—C5—H5B	107.5
N2—C1—S1	126.21 (17)	C7—C6—C5	128.5 (2)
C3—C2—N1	107.1 (2)	C7—C6—Br1A	117.3 (2)
C3—C2—H2	126.5	C5—C6—Br1A	113.50 (19)
N1—C2—H2	126.5	C7—C6—Br1	114.2 (2)
C2—C3—N2	107.6 (2)	C5—C6—Br1	117.17 (19)
C2—C3—H3	126.2	C6—C7—Br2A	124.2 (2)
N2—C3—H3	126.2	C6—C7—Br2	119.02 (19)
N2—C4—H4A	109.5	C6—C7—H7	120.5
N2—C4—H4B	109.5	Br2—C7—H7	120.5
H4A—C4—H4B	109.5

C2—N1—C1—N2	−0.3 (2)	C1—N2—C3—C2	−0.7 (3)
C2—N1—C1—S1	174.60 (17)	C4—N2—C3—C2	−178.5 (2)
C3—N2—C1—N1	0.6 (2)	C1—S1—C5—C6	63.61 (18)
C4—N2—C1—N1	178.4 (2)	S1—C5—C6—C7	−123.8 (2)
C3—N2—C1—S1	−174.33 (16)	S1—C5—C6—Br1A	66.0 (2)
C4—N2—C1—S1	3.5 (3)	S1—C5—C6—Br1	52.2 (2)
C5—S1—C1—N1	69.29 (19)	C5—C6—C7—Br2A	13.5 (4)
C5—S1—C1—N2	−116.71 (18)	Br1A—C6—C7—Br2A	−176.56 (15)
C1—N1—C2—C3	−0.1 (3)	C5—C6—C7—Br2	−5.4 (3)
N1—C2—C3—N2	0.5 (3)	Br1—C6—C7—Br2	178.56 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br3	0.85 (2)	2.37 (2)	3.215 (2)	170 (2)
C3—H3···Br3ⁱ	0.95	2.64	3.584 (3)	170
C5—H5A···Br3ⁱⁱ	0.99	2.89	3.669 (2)	136
C7—H7···Br3ⁱⁱⁱ	0.95	2.87	3.772 (2)	159

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

Acknowledgements

The authors are grateful to Martin Lamb for the PXRD measurements.

References

Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gaitor, J. C., Zayas, M. S., Myrthil, D. J., White, F., Hendrich, J. M., Sykora, R. E., O'Brien, R. A., Reilly, J. T. & Mirjafari, A. (2015). Acta Cryst. E71, o1008–o1009. CrossRef IUCr Journals Google Scholar
Kodomari, M., Sakamoto, T. & Yoshitomi, S. (1989). Bull. Chem. Soc. Jpn, 62, 4053–4054. CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

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