organic compounds
1,3-Diprop-2-ynyl-1H-imidazol-3-ium bromide
aInstitute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475001, Henan, People's Republic of China, and bCollege of Chemistry and Chemical Engineering, Henan University, Kaifeng 475001, Henan, People's Republic of China
*Correspondence e-mail: zhw@henu.edu.cn
In the title salt, C9H9N2+·Br−, the ethynyl groups are nearly antiparallel to each other [the angle between the two ethynyl groups is179.7 (2)°]. No classical hydrogen bonds or π–π interactions are observed. The molecules are linked by C—H⋯Br hydrogen bonds. The bromide anions are involved in interactions with three H atoms.
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: APEX2 (Bruker, 2005); cell APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536808010726/fb2094sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808010726/fb2094Isup2.hkl
A mixture of imidazole (0.6808 g, 0.01 mol) and propargyl bromide (2.379 g, 0.02 mol) in toluene was refluxed and stirred at room temperature for one day. The resulting solid was filtered, washed with diethyl ether and dried under vacuum for two days. X-ray-quality block-like crystals were grown by slow diffusion of N,N-dimethylformamide into a methyl alcohol solution of the title compound. Average size of the crystals was about 0.15 mm in each direction.
All the H atoms could be detected in the difference electron density maps. Nevertheless, they were situated into the idealized positions and refined using a riding model. C—H = 0.97 Å for the methylene groups and C—H = 0.93 Å for the remaining H atoms. Uiso(H) = 1.2Ueq(C) for all the H atoms.
Data collection: APEX2 (Bruker, 2005); cell
APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C9H9N2+·Br− | F(000) = 448 |
Mr = 225.09 | Dx = 1.593 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4175 reflections |
a = 8.3439 (8) Å | θ = 2.7–28.3° |
b = 12.1069 (11) Å | µ = 4.32 mm−1 |
c = 10.0413 (9) Å | T = 273 K |
β = 112.263 (2)° | Block, colourless |
V = 938.74 (15) Å3 | 0.18 × 0.16 × 0.15 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 1580 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 25.0°, θmin = 2.8° |
ϕ and ω scans | h = −9→7 |
4482 measured reflections | k = −14→14 |
1650 independent reflections | l = −11→11 |
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)] = 0.019 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0259P)2 + 0.4349P] where P = (Fo2 + 2Fc2)/3 |
1650 reflections | (Δ/σ)max = 0.002 |
109 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
36 constraints |
C9H9N2+·Br− | V = 938.74 (15) Å3 |
Mr = 225.09 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.3439 (8) Å | µ = 4.32 mm−1 |
b = 12.1069 (11) Å | T = 273 K |
c = 10.0413 (9) Å | 0.18 × 0.16 × 0.15 mm |
β = 112.263 (2)° |
Bruker SMART CCD area-detector diffractometer | 1580 reflections with I > 2σ(I) |
4482 measured reflections | Rint = 0.020 |
1650 independent reflections |
R[F2 > 2σ(F2)] = 0.019 | 0 restraints |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.49 e Å−3 |
1650 reflections | Δρmin = −0.37 e Å−3 |
109 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.32729 (2) | 0.540752 (13) | 0.108115 (17) | 0.01767 (9) | |
N1 | 1.03714 (18) | 0.71725 (12) | 0.30495 (15) | 0.0155 (3) | |
C2 | 0.9295 (2) | 0.77650 (14) | 0.34460 (18) | 0.0161 (3) | |
H2 | 0.9582 | 0.8386 | 0.4034 | 0.019* | |
N3 | 0.77349 (18) | 0.73157 (12) | 0.28557 (15) | 0.0161 (3) | |
C4 | 0.7818 (2) | 0.64081 (14) | 0.20458 (18) | 0.0184 (4) | |
H4 | 0.6906 | 0.5948 | 0.1518 | 0.022* | |
C5 | 0.9476 (2) | 0.63230 (14) | 0.21711 (19) | 0.0173 (4) | |
H5 | 0.9932 | 0.5791 | 0.1745 | 0.021* | |
C6 | 1.2230 (2) | 0.73953 (14) | 0.34599 (19) | 0.0176 (4) | |
H6A | 1.2538 | 0.7292 | 0.2629 | 0.021* | |
H6B | 1.2468 | 0.8158 | 0.3768 | 0.021* | |
C7 | 1.3294 (2) | 0.66665 (14) | 0.46228 (19) | 0.0184 (4) | |
C8 | 1.4191 (2) | 0.60767 (15) | 0.55419 (19) | 0.0210 (4) | |
H8 | 1.4897 | 0.5613 | 0.6265 | 0.025* | |
C9 | 0.6171 (2) | 0.77060 (16) | 0.3052 (2) | 0.0208 (4) | |
H9A | 0.5493 | 0.7074 | 0.3123 | 0.025* | |
H9B | 0.6507 | 0.8116 | 0.3946 | 0.025* | |
C10 | 0.5102 (2) | 0.84122 (15) | 0.1865 (2) | 0.0215 (4) | |
C11 | 0.4197 (3) | 0.89966 (16) | 0.0955 (2) | 0.0300 (4) | |
H11 | 0.3482 | 0.9459 | 0.0235 | 0.036* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.01860 (13) | 0.01479 (12) | 0.01818 (13) | 0.00031 (6) | 0.00534 (9) | −0.00054 (6) |
N1 | 0.0148 (7) | 0.0148 (7) | 0.0148 (7) | 0.0009 (6) | 0.0032 (6) | 0.0016 (6) |
C2 | 0.0166 (8) | 0.0155 (8) | 0.0138 (8) | 0.0005 (7) | 0.0030 (7) | 0.0007 (7) |
N3 | 0.0145 (7) | 0.0164 (7) | 0.0162 (7) | 0.0005 (6) | 0.0044 (6) | 0.0005 (6) |
C4 | 0.0208 (9) | 0.0144 (8) | 0.0168 (9) | −0.0019 (7) | 0.0034 (7) | −0.0011 (7) |
C5 | 0.0211 (9) | 0.0121 (8) | 0.0178 (9) | 0.0013 (7) | 0.0062 (7) | −0.0002 (7) |
C6 | 0.0133 (8) | 0.0182 (8) | 0.0202 (9) | 0.0006 (7) | 0.0051 (7) | 0.0006 (7) |
C7 | 0.0160 (8) | 0.0179 (8) | 0.0206 (9) | −0.0014 (7) | 0.0063 (7) | −0.0050 (7) |
C8 | 0.0201 (9) | 0.0193 (9) | 0.0196 (9) | 0.0025 (7) | 0.0030 (7) | −0.0028 (8) |
C9 | 0.0162 (8) | 0.0241 (9) | 0.0227 (9) | −0.0005 (7) | 0.0080 (7) | −0.0025 (7) |
C10 | 0.0173 (9) | 0.0196 (9) | 0.0272 (10) | −0.0023 (7) | 0.0078 (8) | −0.0081 (8) |
C11 | 0.0279 (10) | 0.0232 (10) | 0.0318 (11) | 0.0052 (9) | 0.0033 (9) | −0.0038 (9) |
N1—C2 | 1.323 (2) | C6—C7 | 1.464 (2) |
N1—C5 | 1.376 (2) | C6—H6A | 0.9700 |
N1—C6 | 1.471 (2) | C6—H6B | 0.9700 |
C2—N3 | 1.326 (2) | C7—C8 | 1.183 (3) |
C2—H2 | 0.9300 | C8—H8 | 0.9300 |
N3—C4 | 1.384 (2) | C9—C10 | 1.463 (3) |
N3—C9 | 1.470 (2) | C9—H9A | 0.9700 |
C4—C5 | 1.345 (3) | C9—H9B | 0.9700 |
C4—H4 | 0.9300 | C10—C11 | 1.176 (3) |
C5—H5 | 0.9300 | C11—H11 | 0.9300 |
C2—N1—C5 | 109.43 (14) | C7—C6—H6A | 109.3 |
C2—N1—C6 | 125.46 (14) | N1—C6—H6A | 109.3 |
C5—N1—C6 | 125.09 (14) | C7—C6—H6B | 109.3 |
N1—C2—N3 | 107.86 (15) | N1—C6—H6B | 109.3 |
N1—C2—H2 | 126.1 | H6A—C6—H6B | 108.0 |
N3—C2—H2 | 126.1 | C8—C7—C6 | 177.89 (19) |
C2—N3—C4 | 109.20 (15) | C7—C8—H8 | 180.0 |
C2—N3—C9 | 125.44 (15) | C10—C9—N3 | 112.18 (15) |
C4—N3—C9 | 125.35 (15) | C10—C9—H9A | 109.2 |
C5—C4—N3 | 106.54 (15) | N3—C9—H9A | 109.2 |
C5—C4—H4 | 126.7 | C10—C9—H9B | 109.2 |
N3—C4—H4 | 126.7 | N3—C9—H9B | 109.2 |
C4—C5—N1 | 106.97 (15) | H9A—C9—H9B | 107.9 |
C4—C5—H5 | 126.5 | C11—C10—C9 | 176.6 (2) |
N1—C5—H5 | 126.5 | C10—C11—H11 | 180.0 |
C7—C6—N1 | 111.66 (14) | ||
C5—N1—C2—N3 | 0.45 (18) | C2—N1—C5—C4 | −0.31 (19) |
C6—N1—C2—N3 | 179.45 (15) | C6—N1—C5—C4 | −179.32 (15) |
N1—C2—N3—C4 | −0.41 (19) | C2—N1—C6—C7 | 101.28 (18) |
N1—C2—N3—C9 | 178.53 (15) | C5—N1—C6—C7 | −79.9 (2) |
C2—N3—C4—C5 | 0.22 (19) | C2—N3—C9—C10 | 97.5 (2) |
C9—N3—C4—C5 | −178.72 (15) | C4—N3—C9—C10 | −83.8 (2) |
N3—C4—C5—N1 | 0.06 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9B···Br1i | 0.97 | 2.75 | 3.6748 (19) | 159 |
C8—H8···Br1ii | 0.93 | 2.81 | 3.7105 (19) | 164 |
C6—H6B···Br1iii | 0.97 | 2.81 | 3.7196 (18) | 157 |
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+2, −y+1, −z+1; (iii) −x+3/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C9H9N2+·Br− |
Mr | 225.09 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 273 |
a, b, c (Å) | 8.3439 (8), 12.1069 (11), 10.0413 (9) |
β (°) | 112.263 (2) |
V (Å3) | 938.74 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.32 |
Crystal size (mm) | 0.18 × 0.16 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4482, 1650, 1580 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.019, 0.051, 1.08 |
No. of reflections | 1650 |
No. of parameters | 109 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.37 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9B···Br1i | 0.97 | 2.75 | 3.6748 (19) | 159.3 |
C8—H8···Br1ii | 0.93 | 2.81 | 3.7105 (19) | 164.3 |
C6—H6B···Br1iii | 0.97 | 2.81 | 3.7196 (18) | 156.5 |
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+2, −y+1, −z+1; (iii) −x+3/2, y+1/2, −z+1/2. |
Acknowledgements
The authors are grateful for financial support from the Henan Administration of Science and Technology (grant No. 0111030700).
References
Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fei, Z., Zhao, D., Scopelliti, R. & Dyson, P. J. (2004). Organometallics, 23, 1622–1628. Web of Science CSD CrossRef CAS Google Scholar
Rajesh, G. G., Mohan, M. B. & Mysore, S. S. (2008). CrystEngComm, 10, 288–296. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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The constituing molecule of the title compound is shown in Fig. 1. Both ethynyls in the title molecule are nearly antiparallel to each other [the angle equals to 179.7 (2)°]. Except for each ethinyl, all the remaining non-H atoms are almost coplanar, with a mean deviation from the least-square plane to be 0.006 (1)Å. The angles between each ethinyl and this plane are about equal [26.8 (1) and 26.3 (1)°]. The bond lengths and angles are normal.
The molecules are linked by C—H···Br hydrogen bonds. Each Br atoms is involved in the C—H···Br interaction with three hydrogens. One of these hydrogens is the ethinyl hydrogen while the remaining two stem from the methylene groups (Fig. 2). There are intermolecular C—H···Br hydrogen bonds in the structure (Fig. 3). No conventional hydrogen bond or π-π electron interactions have been observed.