2-Trifluoro­methyl-1H-benzimidazol-3-ium hydrogen sulfate

Liu, M.-L.

doi:10.1107/S1600536811048811

organic compounds

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Volume 67| Part 12| December 2011| Page o3473

https://doi.org/10.1107/S1600536811048811

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2-Trifluoromethyl-1H-benzimidazol-3-ium hydrogen sulfate

Ming-Liang Liu ^a ^*

^aCollege of Chemistryand Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: jgsdxlml@163.com

(Received 4 November 2011; accepted 16 November 2011; online 30 November 2011)

In the crystal of the title molecular salt, C₈H₆F₃N₂⁺·HSO₄⁻, cation-to-anion N—H⋯O hydrogen bonds generate [100] chains. Anion-to-anion O—H⋯O hydrogen bonds generate [001] helices and cross-link the chains into a three-dimensional network.

Related literature

For a related structure and background to molecular salts, see: Liu (2011 ).

Experimental

Crystal data

C₈H₆F₃N₂⁺·HSO₄⁻
M_r = 284.22
Hexagonal, P 6₅
a = 9.4119 (13) Å
c = 21.960 (4) Å
V = 1684.7 (5) Å³
Z = 6
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury2 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.935, T_max = 0.935
14287 measured reflections
1977 independent reflections
1941 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.134
S = 1.11
1977 reflections
167 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ), 957 Friedel pairs
Flack parameter: 0.03 (16)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3ⁱ	0.86	1.85	2.707 (5)	173
N1—H1A⋯O4	0.86	1.88	2.740 (7)	174
O1—H1⋯O2ⁱⁱ	0.86 (2)	1.86 (6)	2.608 (7)	145 (9)
Symmetry codes: (i) x+1, y, z; (ii) $[y-1, -x+y, z+{\script{1\over 6}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: https://doi.org/10.1107/S1600536811048811/hb6491sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811048811/hb6491Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811048811/hb6491Isup3.cml

checkCIF report

Related literature top

For a related structure and background to molecular salts, see: Liu (2011).

Experimental top

0.144 g(1 mmol) of 2-Trifluoromethl-1H-benzimidazole was firstly dissolved in 30 ml me thanol, to which 0.1 g (1 mmol) of sulfuric acid was then added to afford the solution without any precipitation under stirring at the ambient temperature. Colourless blocks of the title compound were obtained by the slow evaporation of the above solution after 2 days in air.

The dielectric constant of the compound as a function of temperature indicates that the permittivity is basically temperature-independent (ε = C/(T–T₀)), suggesting that this compound is not ferroelectric or there may be no distinct phase transition occurring within the measured temperature within the measured temperature (below the melting point).

Structure description top

For a related structure and background to molecular salts, see: Liu (2011).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 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 molecular structure of the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. A view of the packing of the title compound, stacking along the a axis. Dashed lines indicate hydrogen bonds.

2-Trifluoromethyl-1H-benzimidazol-3-ium hydrogen sulfate top

Crystal data top

C₈H₆F₃N₂⁺·HSO₄⁻	F(000) = 864
M_r = 284.22	D_x = 1.681 Mg m⁻³
Hexagonal, P6₅	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 65	θ = 3.1–27.6°
a = 9.4119 (13) Å	µ = 0.34 mm⁻¹
c = 21.960 (4) Å	T = 293 K
V = 1684.7 (5) Å³	Block, colorless
Z = 6	0.20 × 0.20 × 0.20 mm

Data collection top

Rigaku Mercury2 CCD diffractometer	1977 independent reflections
Radiation source: fine-focus sealed tube	1941 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
CCD_Profile_fitting scans	θ_max = 25.0°, θ_min = 3.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −11→11
T_min = 0.935, T_max = 0.935	k = −11→11
14287 measured reflections	l = −26→26

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.134	w = 1/[σ²(F_o²) + (0.0593P)² + 1.9666P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
1977 reflections	Δρ_max = 0.53 e Å⁻³
167 parameters	Δρ_min = −0.25 e Å⁻³
8 restraints	Absolute structure: Flack (1983), 957 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (16)

Crystal data top

C₈H₆F₃N₂⁺·HSO₄⁻	Z = 6
M_r = 284.22	Mo Kα radiation
Hexagonal, P6₅	µ = 0.34 mm⁻¹
a = 9.4119 (13) Å	T = 293 K
c = 21.960 (4) Å	0.20 × 0.20 × 0.20 mm
V = 1684.7 (5) Å³

Data collection top

Rigaku Mercury2 CCD diffractometer	1977 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1941 reflections with I > 2σ(I)
T_min = 0.935, T_max = 0.935	R_int = 0.038
14287 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.134	Δρ_max = 0.53 e Å⁻³
S = 1.11	Δρ_min = −0.25 e Å⁻³
1977 reflections	Absolute structure: Flack (1983), 957 Friedel pairs
167 parameters	Absolute structure parameter: 0.03 (16)
8 restraints

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
S1	0.09970 (14)	0.72553 (17)	0.16867 (6)	0.0442 (3)
N1	0.4873 (5)	0.7391 (5)	0.1735 (2)	0.0418 (9)
H1A	0.3843	0.7058	0.1770	0.050*
N2	0.7169 (4)	0.7349 (5)	0.16388 (17)	0.0348 (8)
H2A	0.7835	0.6981	0.1596	0.042*
C3	0.6124 (6)	0.9017 (6)	0.1722 (2)	0.0418 (11)
C8	0.7613 (5)	0.9011 (6)	0.1675 (2)	0.0371 (10)
C4	0.6126 (7)	1.0512 (7)	0.1762 (3)	0.0508 (13)
H4	0.5152	1.0535	0.1792	0.061*
O3	−0.0637 (4)	0.6347 (5)	0.14218 (18)	0.0558 (11)
F3	0.5450 (5)	0.4034 (5)	0.1391 (3)	0.0928 (15)
C6	0.9082 (7)	1.1891 (7)	0.1712 (3)	0.0527 (13)
H6	1.0066	1.2883	0.1710	0.063*
O1	0.0866 (5)	0.8248 (5)	0.2230 (2)	0.0627 (11)
C5	0.7592 (8)	1.1907 (7)	0.1755 (3)	0.0589 (15)
H5	0.7623	1.2909	0.1780	0.071*
F1	0.3262 (5)	0.4077 (6)	0.1346 (3)	0.116 (2)
F2	0.4211 (10)	0.3991 (6)	0.2195 (2)	0.157 (3)
O4	0.1589 (5)	0.6207 (5)	0.19150 (19)	0.0571 (11)
C7	0.9120 (6)	1.0455 (7)	0.1670 (3)	0.0456 (11)
H7	1.0103	1.0448	0.1641	0.055*
C1	0.4609 (6)	0.4596 (7)	0.1670 (3)	0.0520 (13)
O2	0.2184 (6)	0.8507 (9)	0.1300 (3)	0.110 (2)
C2	0.5531 (5)	0.6434 (6)	0.1683 (2)	0.0373 (9)
H1	0.041 (10)	0.754 (9)	0.251 (3)	0.10 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0252 (5)	0.0626 (9)	0.0458 (6)	0.0227 (5)	0.0080 (5)	0.0144 (6)
N1	0.0295 (19)	0.051 (2)	0.051 (2)	0.0252 (19)	−0.0012 (18)	−0.0049 (19)
N2	0.0243 (17)	0.044 (2)	0.040 (2)	0.0205 (16)	0.0009 (16)	−0.0062 (18)
C3	0.037 (2)	0.050 (3)	0.043 (3)	0.025 (2)	0.001 (2)	−0.002 (2)
C8	0.037 (2)	0.043 (3)	0.037 (2)	0.024 (2)	−0.006 (2)	−0.005 (2)
C4	0.057 (3)	0.058 (3)	0.059 (3)	0.044 (3)	−0.002 (3)	0.003 (3)
O3	0.0362 (19)	0.087 (3)	0.059 (2)	0.042 (2)	−0.0057 (16)	−0.015 (2)
F3	0.070 (2)	0.058 (2)	0.158 (4)	0.038 (2)	0.018 (3)	−0.012 (3)
C6	0.044 (3)	0.045 (3)	0.062 (3)	0.017 (2)	0.006 (3)	0.009 (3)
O1	0.056 (3)	0.048 (2)	0.079 (3)	0.022 (2)	−0.009 (2)	−0.012 (2)
C5	0.073 (4)	0.052 (3)	0.070 (4)	0.045 (3)	−0.005 (3)	0.005 (3)
F1	0.047 (2)	0.070 (3)	0.213 (6)	0.0161 (19)	−0.039 (3)	−0.044 (3)
F2	0.246 (6)	0.055 (3)	0.072 (3)	0.002 (3)	0.038 (4)	0.009 (2)
O4	0.0403 (19)	0.074 (3)	0.072 (3)	0.039 (2)	0.0007 (17)	0.007 (2)
C7	0.030 (2)	0.055 (3)	0.050 (3)	0.020 (2)	−0.002 (2)	0.003 (2)
C1	0.036 (3)	0.043 (3)	0.067 (3)	0.012 (2)	0.014 (3)	−0.001 (3)
O2	0.057 (3)	0.155 (5)	0.108 (4)	0.045 (3)	0.032 (3)	0.093 (4)
C2	0.030 (2)	0.040 (2)	0.042 (2)	0.0176 (19)	0.0001 (19)	−0.010 (2)

Geometric parameters (Å, º) top

S1—O2	1.429 (5)	C4—C5	1.348 (9)
S1—O4	1.444 (4)	C4—H4	0.9300
S1—O3	1.456 (4)	F3—C1	1.304 (6)
S1—O1	1.558 (5)	C6—C7	1.373 (8)
N1—C2	1.329 (6)	C6—C5	1.414 (8)
N1—C3	1.388 (6)	C6—H6	0.9300
N1—H1A	0.8600	O1—H1	0.86 (2)
N2—C2	1.341 (6)	C5—H5	0.9300
N2—C8	1.405 (6)	F1—C1	1.317 (8)
N2—H2A	0.8600	F2—C1	1.258 (8)
C3—C8	1.407 (6)	C7—H7	0.9300
C3—C4	1.409 (7)	C1—C2	1.499 (7)
C8—C7	1.390 (7)

O2—S1—O4	111.1 (3)	C3—C4—H4	121.2
O2—S1—O3	114.0 (3)	C7—C6—C5	122.0 (5)
O4—S1—O3	113.1 (3)	C7—C6—H6	119.0
O2—S1—O1	103.0 (4)	C5—C6—H6	119.0
O4—S1—O1	108.5 (3)	S1—O1—H1	104 (7)
O3—S1—O1	106.3 (2)	C4—C5—C6	121.9 (5)
C2—N1—C3	108.6 (4)	C4—C5—H5	119.1
C2—N1—H1A	125.7	C6—C5—H5	119.1
C3—N1—H1A	125.7	C6—C7—C8	116.5 (4)
C2—N2—C8	108.5 (3)	C6—C7—H7	121.8
C2—N2—H2A	125.8	C8—C7—H7	121.8
C8—N2—H2A	125.8	F2—C1—F3	110.5 (7)
N1—C3—C8	107.2 (4)	F2—C1—F1	108.3 (6)
N1—C3—C4	132.5 (4)	F3—C1—F1	105.2 (5)
C8—C3—C4	120.3 (5)	F2—C1—C2	112.0 (5)
C7—C8—N2	132.7 (4)	F3—C1—C2	111.0 (4)
C7—C8—C3	121.9 (4)	F1—C1—C2	109.5 (5)
N2—C8—C3	105.4 (4)	N1—C2—N2	110.3 (4)
C5—C4—C3	117.5 (5)	N1—C2—C1	125.9 (4)
C5—C4—H4	121.2	N2—C2—C1	123.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3ⁱ	0.86	1.85	2.707 (5)	173
N1—H1A···O4	0.86	1.88	2.740 (7)	174
O1—H1···O2ⁱⁱ	0.86 (2)	1.86 (6)	2.608 (7)	145 (9)

Symmetry codes: (i) x+1, y, z; (ii) y−1, −x+y, z+1/6.

Experimental details

Crystal data
Chemical formula	C₈H₆F₃N₂⁺·HSO₄⁻
M_r	284.22
Crystal system, space group	Hexagonal, P6₅
Temperature (K)	293
a, c (Å)	9.4119 (13), 21.960 (4)
V (Å³)	1684.7 (5)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 CCD
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.935, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	14287, 1977, 1941
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.134, 1.11
No. of reflections	1977
No. of parameters	167
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.25
Absolute structure	Flack (1983), 957 Friedel pairs
Absolute structure parameter	0.03 (16)

Computer programs: CrystalClear (Rigaku, 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
N2—H2A···O3ⁱ	0.86	1.85	2.707 (5)	173
N1—H1A···O4	0.86	1.88	2.740 (7)	174
O1—H1···O2ⁱⁱ	0.86 (2)	1.86 (6)	2.608 (7)	145 (9)

Symmetry codes: (i) x+1, y, z; (ii) y−1, −x+y, z+1/6.

Acknowledgements

The author thanks an anonymous reader from the Ordered Matter Science Research Centre, Southeast University, for great help in the revision of this paper.

References

Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Liu, M.-L. (2011). Acta Cryst. E67, o2821. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar