organic compounds
2,3-Dimethyl-1H-imidazol-3-ium chloride
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
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 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 with a single cation–anion pair in the 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).
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 . The crystal studied was refined as a two-component with a twin ratio of 0.71 (5) to 0.29 (5).
details are summarized in Table 2Structural data
CCDC reference: 2004253
https://doi.org/10.1107/S2414314620006604/bv4030sup1.cif
contains datablock I. DOI: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
Data collection: APEX3 (Bruker, 2018); cell
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).C5H9N2+·Cl− | Dx = 1.283 Mg m−3 |
Mr = 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 |
Bruker AXS D8 Quest CMOS diffractometer | 2499 reflections with I > 2σ(I) |
Detector resolution: 10.4167 pixels mm-1 | Rint = 0.029 |
ω and phi scans | θmax = 33.1°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −7→9 |
Tmin = 0.713, Tmax = 0.747 | k = −14→12 |
13899 measured reflections | l = −15→17 |
2602 independent reflections |
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(Fo2) + (0.0228P)2 + 0.0624P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.050 | (Δ/σ)max < 0.001 |
S = 1.11 | Δρmax = 0.21 e Å−3 |
2602 reflections | Δρmin = −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) |
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. |
x | y | z | Uiso*/Ueq | ||
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)* |
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) |
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) |
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 .
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