2,3-Dimethyl-1H-imidazol-3-ium chloride

Anderson, G.; Mirjafari, A.; Zeller, M.; Hillesheim, P.C.

doi:10.1107/S2414314620006604

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 5| May 2020| x200660

https://doi.org/10.1107/S2414314620006604

Open

access

2,3-Dimethyl-1H-imidazol-3-ium chloride

Grace Anderson,^a Arsalan Mirjafari,^a Matthias Zeller ^b and Patrick C. Hillesheim ^c ^*

^aDepartment of Chemistry and Physics, Florida Gulf Coast University, 10501 FGCU Blvd. South, Fort Myers, FL, 33965, USA, ^bPurdue University, Department of Chemistry, 560 Oval Drive, West Lafayette, Indiana, 47907, USA, and ^cAve Maria University, Department of Chemistry and Physics, 5050 Ave Maria Blvd, Ave Maria FL, 34142, USA
^*Correspondence e-mail: Patrick.Hillesheim@avemaria.edu

Edited by R. J. Butcher, Howard University, USA (Received 30 March 2020; accepted 16 May 2020; online 19 May 2020)

The title salt, C₅H₉N₂⁺·Cl⁻, exhibits multiple hydrogen-bonding interactions between the cationic imidazole moiety and the chloride anion. The protonated aromatic nitrogen moiety displays the shortest hydrogen-bonding interactions while weaker hydrogen bonding is observed between the aromatic H atoms and the chloride anion. The crystal studied was refined as a two-component inversion twin with a twin ratio of 0.71 (5) to 0.29 (5).

Keywords: crystal structure; imidazolium; ionic; hydrogen bonding.

CCDC reference: 2004253

Structure description

The title structure, 2,3-dimethyl-1H-imidazol-3-ium chloride (Fig. 1), crystallizes in the P2₁2₁2₁ orthorhombic space group with a single cation–anion pair in the asymmetric unit. The acidic hydrogen, H1, exhibits a strong hydrogen bond to the chloride anion with a distance of 2.122 (19) Å. Longer hydrogen bonds between the chloride anion and H atoms on both methyl groups on the imidazolium ring as well as to the aromatic H atoms on adjacent cations form the dominant intermolecular interactions in the overall network (see Table 1). The positioning of the cations, likely to facilitate hydrogen bonding, also precludes any possible long-distance π–π interactions given the canted angles of the rings with respect to each other (see Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1	0.923 (19)	2.122 (19)	3.0396 (10)	172.3 (17)
C2—H2⋯Cl1ⁱ	0.955 (17)	2.695 (17)	3.6084 (11)	160.2 (13)
C4—H4C⋯Cl1ⁱⁱ	1.005 (19)	2.85 (2)	3.6601 (12)	138.3 (14)
C5—H5A⋯Cl1ⁱⁱ	0.94 (2)	2.887 (19)	3.6415 (13)	138.0 (14)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ .

Figure 1
The title compound shown with 50% probability ellipsoids. Carbon (grey), hydrogen (white), nitrogen (blue), chlorine (green).

Figure 2
Packing diagram of the title compound showing a zigzag network of ion pairs held together through hydrogen bonds.

Synthesis and crystallization

1,2-Dimethylimidazole (0.2568 g, 2.662 mmol) and trityl chloride (0.7439 g, 2.668 mmol) were dissolved in separate 50 mL beakers with toluene. The reactants were then combined in a single-necked 100 mL round-bottom flask equipped with a magnetic stir bar and left to stir for 2 d at room temperature. The solvent was removed under vacuum leaving a white solid residue. This solid was washed twice with tetrahydrofuran and recovered via vacuum filtration. Crystals were grown at room temperature by vapor diffusion with acetonitrile as the solvent and tetrahydrofuran as the anti-solvent. Colorless crystals of the hydrolyzed byproduct (2,3-dimethyl-1H-imidazol-3-ium chloride) were observed within one week.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The crystal studied was refined as a two-component inversion twin with a twin ratio of 0.71 (5) to 0.29 (5).

Table 2
Experimental details

Crystal data
Chemical formula	C₅H₉N₂⁺·Cl⁻
M_r	132.59
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	150
a, b, c (Å)	6.3076 (4), 9.5490 (6), 11.3951 (8)
V (Å³)	686.34 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.46
Crystal size (mm)	0.53 × 0.49 × 0.42

Data collection
Diffractometer	Bruker AXS D8 Quest CMOS
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.713, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	13899, 2602, 2499
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.768

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.050, 1.11
No. of reflections	2602
No. of parameters	111
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.15
Absolute structure	Refined as an inversion twin
Absolute structure parameter	0.29 (5)
Computer programs: APEX3 (Bruker, 2018 ), SAINT (Bruker, 2018), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), shelXle (Hübschle et al., 2011 ), OLEX2 (Dolomanov et al., 2009 ), publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2004253

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314620006604/bv4030sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620006604/bv4030Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314620006604/bv4030Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015), shelXle (Hübschle et al., 2011); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

2,3-Dimethyl-1H-imidazol-3-ium chloride top

Crystal data top

C₅H₉N₂⁺·Cl⁻	D_x = 1.283 Mg m⁻³
M_r = 132.59	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 9928 reflections
a = 6.3076 (4) Å	θ = 2.8–33.1°
b = 9.5490 (6) Å	µ = 0.46 mm⁻¹
c = 11.3951 (8) Å	T = 150 K
V = 686.34 (8) Å³	Prism, colourless
Z = 4	0.53 × 0.49 × 0.42 mm
F(000) = 280

Data collection top

Bruker AXS D8 Quest CMOS diffractometer	2499 reflections with I > 2σ(I)
Detector resolution: 10.4167 pixels mm^-1	R_int = 0.029
ω and phi scans	θ_max = 33.1°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −7→9
T_min = 0.713, T_max = 0.747	k = −14→12
13899 measured reflections	l = −15→17
2602 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F² > 2σ(F²)] = 0.019	w = 1/[σ²(F_o²) + (0.0228P)² + 0.0624P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.050	(Δ/σ)_max < 0.001
S = 1.11	Δρ_max = 0.21 e Å⁻³
2602 reflections	Δρ_min = −0.14 e Å⁻³
111 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.034 (6)
Primary atom site location: structure-invariant direct methods	Absolute structure: Refined as an inversion twin
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.29 (5)

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. Refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq
Cl1	0.23376 (4)	0.42563 (3)	0.59746 (2)	0.02230 (7)
N1	0.57372 (15)	0.53197 (10)	0.43072 (8)	0.02210 (18)
H1	0.481 (3)	0.497 (2)	0.4861 (17)	0.046 (5)*
N2	0.70984 (13)	0.65758 (9)	0.29255 (7)	0.01820 (16)
C1	0.75982 (19)	0.46689 (11)	0.39763 (10)	0.0272 (2)
H1A	0.814 (3)	0.3832 (18)	0.4356 (15)	0.034 (4)*
C2	0.84515 (17)	0.54576 (12)	0.31046 (10)	0.0244 (2)
H2	0.975 (3)	0.5379 (16)	0.2678 (15)	0.030 (4)*
C3	0.54531 (15)	0.64734 (11)	0.36651 (9)	0.01807 (17)
C4	0.73381 (19)	0.76456 (11)	0.20131 (9)	0.0250 (2)
H4A	0.872 (3)	0.7478 (19)	0.1651 (14)	0.030 (4)*
H4B	0.715 (3)	0.8557 (16)	0.2354 (13)	0.029 (4)*
H4C	0.619 (3)	0.753 (2)	0.1407 (17)	0.043 (5)*
C5	0.36645 (18)	0.74662 (14)	0.37712 (11)	0.0272 (2)
H5A	0.296 (3)	0.7479 (19)	0.3043 (18)	0.049 (5)*
H5B	0.418 (3)	0.834 (2)	0.3930 (19)	0.063 (6)*
H5C	0.271 (3)	0.713 (2)	0.4340 (17)	0.054 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02118 (10)	0.02475 (11)	0.02096 (11)	−0.00241 (8)	0.00199 (8)	0.00210 (8)
N1	0.0232 (4)	0.0225 (4)	0.0205 (4)	−0.0032 (3)	0.0033 (3)	0.0009 (3)
N2	0.0171 (4)	0.0185 (3)	0.0191 (3)	−0.0025 (3)	0.0016 (3)	−0.0015 (3)
C1	0.0284 (5)	0.0239 (4)	0.0294 (5)	0.0040 (4)	0.0037 (5)	0.0045 (4)
C2	0.0204 (4)	0.0250 (5)	0.0277 (5)	0.0025 (4)	0.0038 (4)	0.0007 (4)
C3	0.0170 (4)	0.0199 (4)	0.0173 (4)	−0.0033 (3)	0.0009 (3)	−0.0035 (3)
C4	0.0286 (5)	0.0219 (4)	0.0245 (4)	−0.0042 (4)	0.0042 (4)	0.0045 (4)
C5	0.0228 (4)	0.0294 (5)	0.0295 (6)	0.0044 (4)	0.0033 (4)	−0.0041 (4)

Geometric parameters (Å, º) top

N1—H1	0.923 (19)	C2—H2	0.955 (17)
N1—C1	1.3806 (14)	C3—C5	1.4786 (15)
N1—C3	1.3346 (14)	C4—H4A	0.980 (17)
N2—C2	1.3821 (14)	C4—H4B	0.960 (15)
N2—C3	1.3405 (12)	C4—H4C	1.005 (19)
N2—C4	1.4654 (13)	C5—H5A	0.94 (2)
C1—H1A	0.971 (17)	C5—H5B	0.92 (2)
C1—C2	1.3578 (16)	C5—H5C	0.94 (2)

C1—N1—H1	124.4 (11)	N2—C3—C5	126.54 (10)
C3—N1—H1	125.8 (11)	N2—C4—H4A	106.1 (10)
C3—N1—C1	109.63 (9)	N2—C4—H4B	109.4 (9)
C2—N2—C4	125.43 (9)	N2—C4—H4C	109.6 (11)
C3—N2—C2	109.20 (9)	H4A—C4—H4B	115.3 (15)
C3—N2—C4	125.23 (9)	H4A—C4—H4C	109.4 (13)
N1—C1—H1A	123.3 (10)	H4B—C4—H4C	107.0 (15)
C2—C1—N1	106.69 (10)	C3—C5—H5A	107.2 (12)
C2—C1—H1A	129.9 (10)	C3—C5—H5B	109.3 (14)
N2—C2—H2	121.0 (10)	C3—C5—H5C	108.9 (12)
C1—C2—N2	106.96 (10)	H5A—C5—H5B	109.3 (18)
C1—C2—H2	131.9 (10)	H5A—C5—H5C	108.1 (16)
N1—C3—N2	107.52 (9)	H5B—C5—H5C	113.8 (18)
N1—C3—C5	125.94 (10)

N1—C1—C2—N2	0.25 (13)	C3—N1—C1—C2	−0.20 (13)
C1—N1—C3—N2	0.06 (12)	C3—N2—C2—C1	−0.22 (12)
C1—N1—C3—C5	−178.91 (10)	C4—N2—C2—C1	−175.97 (10)
C2—N2—C3—N1	0.10 (11)	C4—N2—C3—N1	175.86 (9)
C2—N2—C3—C5	179.06 (10)	C4—N2—C3—C5	−5.17 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.923 (19)	2.122 (19)	3.0396 (10)	172.3 (17)
C2—H2···Cl1ⁱ	0.955 (17)	2.695 (17)	3.6084 (11)	160.2 (13)
C4—H4C···Cl1ⁱⁱ	1.005 (19)	2.85 (2)	3.6601 (12)	138.3 (14)
C5—H5A···Cl1ⁱⁱ	0.94 (2)	2.887 (19)	3.6415 (13)	138.0 (14)

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

Acknowledgements

This material is based upon work supported by the National Science Foundation through the Major Research Instrumentation Program under grant No. CHE 1625543 (funding for the single-crystal X-ray diffractometer). Acknowledgment is made to the donors of the American Chemical Society Petroleum Research Fund for support of this research. The authors gratefully acknowledge the Communities in Transition Initiative for the generous support.

Funding information

Funding for this research was provided by: National Science Foundation (grant No. CHE 11625543); American Chemical Society Petroleum Research Fund (grant No. PRF 58975-UR4); Ave Maria University Department of Chemistry and Physics .

References

Bruker (2018). APEX3 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281–1284. Web of Science CrossRef IUCr Journals Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar