1,3-Diprop-2-ynyl-1H-imidazol-3-ium bromide

Li, H.; Jin, L.-Y.; Tao, R.-J.

doi:10.1107/S1600536808010726

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o900

doi:10.1107/S1600536808010726

Open

access

1,3-Diprop-2-ynyl-1H-imidazol-3-ium bromide

Hui Li,^a Lin-Yu Jin ^b and Ruo-Jie Tao ^a ^*

^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

(Received 2 April 2008; accepted 17 April 2008; online 23 April 2008)

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.

Related literature

For related literature, see: Fei et al. (2004 ); Rajesh et al. (2008 ).

Experimental

Crystal data

C₉H₉N₂⁺·Br⁻
M_r = 225.09
Monoclinic, P 2₁ /n
a = 8.3439 (8) Å
b = 12.1069 (11) Å
c = 10.0413 (9) Å
β = 112.263 (2)°
V = 938.74 (15) Å³
Z = 4
Mo Kα radiation
μ = 4.32 mm⁻¹
T = 273 (2) K
0.18 × 0.16 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: none
4482 measured reflections
1650 independent reflections
1580 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.051
S = 1.08
1650 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z+1; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808010726/fb2094sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808010726/fb2094Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

For related literature, see: Fei et al. (2004); Rajesh et al. (2008).

Experimental top

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.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: 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).

Figures top

	Fig. 1. The title molecule with the atom-labelling scheme. The displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal structure of the title compound. The C—H···Br hydrogen bonds are indicated by the dashed lines.
	Fig. 3. The molecular packing of the title compound viewed along the a axis. The hydrogen bonds are indicated by dashed lines.

1,3-Diprop-2-ynyl-1H-imidazol-3-ium bromide top

Crystal data top

C₉H₉N₂⁺·Br⁻	F(000) = 448
M_r = 225.09	D_x = 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

Data collection top

Bruker SMART CCD area-detector diffractometer	1580 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.020
Graphite monochromator	θ_max = 25.0°, θ_min = 2.8°
ϕ and ω scans	h = −9→7
4482 measured reflections	k = −14→14
1650 independent reflections	l = −11→11

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)] = 0.019	Hydrogen site location: difference Fourier map
wR(F²) = 0.051	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0259P)² + 0.4349P] where P = (F_o² + 2F_c²)/3
1650 reflections	(Δ/σ)_max = 0.002
109 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³
36 constraints

Crystal data top

C₉H₉N₂⁺·Br⁻	V = 938.74 (15) Å³
M_r = 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)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1580 reflections with I > 2σ(I)
4482 measured reflections	R_int = 0.020
1650 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	0 restraints
wR(F²) = 0.051	H-atom parameters constrained
S = 1.08	Δρ_max = 0.49 e Å⁻³
1650 reflections	Δρ_min = −0.37 e Å⁻³
109 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
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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⁻
M_r	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
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.37

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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