2-(Chloro­meth­yl)benzimidazolium chloride

Wang, G.; Qu, Z.-R.

doi:10.1107/S1600536809015359

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1167

doi:10.1107/S1600536809015359

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2-(Chloromethyl)benzimidazolium chloride

Gang Wang ^a and Zhi-Rong Qu ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: quzr@seu.edu.cn

(Received 17 April 2009; accepted 24 April 2009; online 30 April 2009)

The structure of title compound, C₈H₈ClN₂⁺·Cl⁻, comprises discrete ions which are interconnected by N—H⋯Cl hydrogen bonds, leading to a neutral one-dimensional network in [001]. This hydrogen bonding appears to complement π–π stacking interactions [centroid–centroid distances 3.768 (2) and 3.551 (2) Å] and helps to stabilize the structure further.

Related literature

For details of the preparation of imidazole compounds, see: Ikezaki & Nakamura (2002 ). For the chemistry of 2-(chloromethyl)-1H-benzo[d]imidazolium chloride, see: Jian et al. (2003 ).

Experimental

Crystal data

C₈H₈ClN₂⁺·Cl⁻
M_r = 203.06
Monoclinic, P 2₁ /c
a = 7.1972 (14) Å
b = 9.4507 (19) Å
c = 14.046 (3) Å
β = 102.51 (3)°
V = 932.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.64 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.867, T_max = 0.882
9462 measured reflections
2141 independent reflections
1212 reflections with I > 2σ(I)
R_int = 0.083
Standard reflections: ?

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.180
S = 0.84
2141 reflections
109 parameters
.
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.86	2.25	3.066 (2)	158
N2—H2A⋯Cl1	0.86	2.20	3.055 (2)	178
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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/PC (Sheldrick, 2008); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809015359/bx2205sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809015359/bx2205Isup2.hkl

checkCIF report

Comment top

2-(4-bromophenyl)-1-phenyl-1H-benzimidazole used as bridging ligands in coordination and metallosupramolecular chemistry are representative. In recent years, benzimidazole also was used to link different alkyl or aromatic group, which can adopt different conformations according to the different geometric requirements of metal centers when forming metal complexes (Ikezaki, et al. 2002; Jian, et al. 2003). We report here the crystal structure of the title compound. The structure of title compound, C₈H₈ClN₂.Cl^-, comprises discrete ions which are interconnected by N1—H1A···Cl1ⁱ hydrogen bond, leading to a neutral one-dimensional network in [0 0 1] direction. These hydrogen bonds appear to complement π-π stacking interactions and help to stabilize the structure further (Table 2).

Related literature top

For details of the preparation of imidazole compounds, see: Ikezaki, et al. (2002). For the chemistry of 2-(chloromethyl)-1H-benzo[d]imidazolium chloride, see: Jian et al. (2003).

Experimental top

A mixture of 1,2-diaminobenzene (0.01 mol 1.08 g) and chloroacetic acid (0.01 mol 0.95 g) in HCl (4 ml) was refluxed for 12 h and the title compound was dissolved in ethanol and HCl, after slowly volatilizing over a period of 48 h, colorless crystals of the title compound suitable for diffraction were isolated.

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/PC (Sheldrick, 2008); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999).

Figures top

Fig. 1. The molecular structure of (I), with the displacement ellipsoids were drawn at the 30% probability level.

2-(Chloromethyl)benzimidazolium chloride top

Crystal data top

C₈H₈ClN₂⁺·Cl⁻	F(000) = 416
M_r = 203.06	D_x = 1.446 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ybc	Cell parameters from 1979 reflections
a = 7.1972 (14) Å	θ = 3.1–27.5°
b = 9.4507 (19) Å	µ = 0.64 mm⁻¹
c = 14.046 (3) Å	T = 293 K
β = 102.51 (3)°	Prism, colourless
V = 932.7 (3) Å³	0.22 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2141 independent reflections
Radiation source: fine-focus sealed tube	1212 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.083
CCD_Profile_fitting scans	θ_max = 27.5°, θ_min = 3.6°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −9→9
T_min = 0.867, T_max = 0.882	k = −12→12
9462 measured reflections	l = −18→18

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.180	w = 1/[σ²(F_o²) + (0.1077P)² + 0.4199P] where P = (F_o² + 2F_c²)/3
S = 0.84	(Δ/σ)_max < 0.001
2141 reflections	Δρ_max = 0.29 e Å⁻³
109 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints

Crystal data top

C₈H₈ClN₂⁺·Cl⁻	V = 932.7 (3) Å³
M_r = 203.06	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.1972 (14) Å	µ = 0.64 mm⁻¹
b = 9.4507 (19) Å	T = 293 K
c = 14.046 (3) Å	0.22 × 0.20 × 0.20 mm
β = 102.51 (3)°

Data collection top

Rigaku SCXmini diffractometer	2141 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1212 reflections with I > 2σ(I)
T_min = 0.867, T_max = 0.882	R_int = 0.083
9462 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	109 parameters
wR(F²) = 0.180	0 restraints
S = 0.84	Δρ_max = 0.29 e Å⁻³
2141 reflections	Δρ_min = −0.31 e Å⁻³

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
Cl1	0.34571 (17)	0.59201 (10)	1.15934 (7)	0.0608 (4)
Cl2	0.11234 (16)	0.56643 (10)	0.83757 (8)	0.0654 (4)
N2	0.2890 (4)	0.8248 (3)	1.00495 (19)	0.0449 (7)
H2A	0.3032	0.7611	1.0496	0.054*
N1	0.2626 (4)	0.9234 (3)	0.86427 (19)	0.0446 (7)
H1A	0.2575	0.9338	0.8029	0.053*
C6	0.2574 (4)	0.9674 (4)	1.0180 (2)	0.0385 (8)
C1	0.2393 (5)	1.0306 (3)	0.9280 (2)	0.0388 (8)
C7	0.2936 (5)	0.8027 (4)	0.9125 (3)	0.0438 (8)
C5	0.2467 (5)	1.0453 (4)	1.1012 (3)	0.0528 (10)
H5A	0.2596	1.0028	1.1620	0.063*
C2	0.2079 (5)	1.1754 (4)	0.9153 (3)	0.0528 (10)
H2B	0.1957	1.2183	0.8546	0.063*
C4	0.2163 (6)	1.1877 (4)	1.0883 (3)	0.0588 (11)
H4A	0.2090	1.2435	1.1419	0.071*
C3	0.1961 (6)	1.2515 (4)	0.9973 (3)	0.0615 (11)
H3A	0.1738	1.3484	0.9917	0.074*
C8	0.3276 (6)	0.6648 (4)	0.8695 (3)	0.0628 (11)
H8A	0.4205	0.6114	0.9162	0.075*
H8B	0.3787	0.6801	0.8119	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0894 (8)	0.0515 (6)	0.0475 (6)	0.0166 (5)	0.0280 (5)	0.0084 (4)
Cl2	0.0670 (7)	0.0524 (6)	0.0753 (7)	−0.0038 (5)	0.0119 (5)	−0.0149 (5)
N2	0.0488 (18)	0.0411 (16)	0.0452 (17)	0.0062 (14)	0.0111 (14)	0.0093 (12)
N1	0.0527 (19)	0.0459 (17)	0.0377 (15)	0.0017 (14)	0.0154 (14)	0.0019 (13)
C6	0.0319 (18)	0.0439 (18)	0.0407 (18)	0.0021 (15)	0.0104 (14)	0.0029 (14)
C1	0.0361 (18)	0.0403 (17)	0.0409 (18)	−0.0009 (15)	0.0105 (15)	−0.0002 (15)
C7	0.0383 (19)	0.0436 (19)	0.052 (2)	0.0025 (16)	0.0157 (16)	−0.0010 (16)
C5	0.050 (2)	0.071 (3)	0.0383 (19)	0.002 (2)	0.0099 (16)	−0.0059 (17)
C2	0.058 (2)	0.046 (2)	0.054 (2)	0.0001 (18)	0.0104 (19)	0.0072 (17)
C4	0.054 (2)	0.064 (3)	0.057 (2)	0.005 (2)	0.011 (2)	−0.022 (2)
C3	0.061 (3)	0.042 (2)	0.082 (3)	0.005 (2)	0.015 (2)	−0.013 (2)
C8	0.053 (2)	0.051 (2)	0.087 (3)	0.002 (2)	0.021 (2)	−0.016 (2)

Geometric parameters (Å, º) top

C1—C6	1.381 (4)	C5—H5A	0.9300
C1—C2	1.389 (4)	C6—N2	1.385 (4)
C1—N1	1.391 (3)	C7—N2	1.320 (3)
C2—C3	1.372 (4)	C7—N1	1.322 (3)
C2—H2B	0.9300	C7—C8	1.477 (4)
C3—C4	1.395 (4)	C8—Cl2	1.781 (3)
C3—H3A	0.9300	C8—H8A	0.9700
C4—C5	1.367 (4)	C8—H8B	0.9700
C4—H4A	0.9300	N1—H1A	0.8600
C5—C6	1.392 (4)	N2—H2A	0.8600

C6—C1—C2	121.8 (3)	N2—C6—C5	132.0 (3)
C6—C1—N1	106.0 (2)	N2—C7—N1	109.3 (2)
C2—C1—N1	132.2 (3)	N2—C7—C8	125.5 (3)
C3—C2—C1	116.4 (3)	N1—C7—C8	125.2 (3)
C3—C2—H2B	121.8	C7—C8—Cl2	110.6 (2)
C1—C2—H2B	121.8	C7—C8—H8A	109.5
C2—C3—C4	121.8 (3)	Cl2—C8—H8A	109.5
C2—C3—H3A	119.1	C7—C8—H8B	109.5
C4—C3—H3A	119.1	Cl2—C8—H8B	109.5
C5—C4—C3	121.9 (3)	H8A—C8—H8B	108.1
C5—C4—H4A	119.1	C7—N1—C1	109.1 (2)
C3—C4—H4A	119.1	C7—N1—H1A	125.5
C4—C5—C6	116.5 (3)	C1—N1—H1A	125.5
C4—C5—H5A	121.7	C7—N2—C6	109.2 (2)
C6—C5—H5A	121.7	C7—N2—H2A	125.4
C1—C6—N2	106.4 (2)	C6—N2—H2A	125.4
C1—C6—C5	121.5 (3)

C6—C1—C2—C3	0.1 (5)	N2—C7—C8—Cl2	84.1 (4)
N1—C1—C2—C3	−178.5 (3)	N1—C7—C8—Cl2	−95.6 (3)
C1—C2—C3—C4	0.6 (5)	N2—C7—N1—C1	1.1 (3)
C2—C3—C4—C5	−0.7 (5)	C8—C7—N1—C1	−179.1 (3)
C3—C4—C5—C6	0.1 (5)	C6—C1—N1—C7	−0.3 (3)
C2—C1—C6—N2	−179.4 (3)	C2—C1—N1—C7	178.4 (3)
N1—C1—C6—N2	−0.5 (3)	N1—C7—N2—C6	−1.5 (3)
C2—C1—C6—C5	−0.7 (4)	C8—C7—N2—C6	178.8 (3)
N1—C1—C6—C5	178.2 (3)	C1—C6—N2—C7	1.2 (3)
C4—C5—C6—C1	0.6 (4)	C5—C6—N2—C7	−177.3 (3)
C4—C5—C6—N2	178.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.86	2.25	3.066 (2)	158
N2—H2A···Cl1	0.86	2.20	3.055 (2)	178

Symmetry code: (i) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₈H₈ClN₂⁺·Cl⁻
M_r	203.06
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.1972 (14), 9.4507 (19), 14.046 (3)
β (°)	102.51 (3)
V (Å³)	932.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.64
Crystal size (mm)	0.22 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.867, 0.882
No. of measured, independent and observed [I > 2σ(I)] reflections	9462, 2141, 1212
R_int	0.083
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.180, 0.84
No. of reflections	2141
No. of parameters	109
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.31

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.86	2.25	3.066 (2)	157.5
N2—H2A···Cl1	0.86	2.20	3.055 (2)	177.5

Symmetry code: (i) x, −y+3/2, z−1/2.

π-π interaction in (I).
α is dihedral angle between the planes, DCC is the length of the CC vector (centroid to centroid), τ is the angle(s) subtended by the plane normal(s) to CC. Cg1 is the centroid of ring N1, C1, C6, N2, C7, Cg2 of ring C1 C2 C3 C4 C5 C6. top

Group 1	Group 2	α /°	DCC /Å	τ /°
Cg1	Cg2ⁱ	1.43	3.768 (2)	21.88
Cg1	Cg2ⁱⁱ	1.43	3.551 (2)	12.47

Symmetry codes: (i) -x, 2-y, 2-z (ii) 1-x, 2-y, 2-z

Acknowledgements

This work was supported by the Technical Fund Financing Projects (No. 9207042464 and 9207041482) from Southeast University to ZRQ.

References

Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
Ikezaki, A. & Nakamura, M. (2002). Inorg. Chem. 41, 6225–6236. Web of Science CrossRef PubMed CAS Google Scholar
Jian, F. F., Yan, L., Xiao, H. L. & Sun, P. P. (2003). J. Struct. Chem. 22, 687–690. CAS 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