1-(4-Cyano­benz­yl)-4-methyl­pyridinium bromide

Chen, H.; Zhu, K.; Liu, G.-X.

doi:10.1107/S1600536809020054

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1453

doi:10.1107/S1600536809020054

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1-(4-Cyanobenzyl)-4-methylpyridinium bromide

Hong Chen,^a Kun Zhu ^a and Guang-Xiang Liu ^a ^*

^aAnhui Key Laboratory of Functional Coordination Compounds, School of Chemistry and Chemical Engineering, Anqing Normal University, Anqing 246003, People's Republic of China
^*Correspondence e-mail: liugx@live.com

(Received 1 May 2009; accepted 26 May 2009; online 6 June 2009)

In the title compound, C₁₄H₁₃N₂⁺·Br⁻, the 1-(4-cyanobenzyl)-4-methylpyridinium cation has a Λ-shaped conformation, and the dihedral angle between the benzene and pyridinium rings is 75.8 (2)°. In the crystal, two cations form a dimer through π–π interactions between pyridine rings [the centroid–centroid distance is 3.685 (1) Å].

Related literature

For cations with similar geometry, see: Liu et al. (2007 , 2008 ).

Experimental

Crystal data

C₁₄H₁₃N₂⁺·Br⁻
M_r = 289.17
Monoclinic, P 2₁ /c
a = 12.967 (5) Å
b = 8.217 (4) Å
c = 12.260 (5) Å
β = 96.900 (5)°
V = 1296.8 (10) Å³
Z = 4
Mo Kα radiation
μ = 3.15 mm⁻¹
T = 296 K
0.24 × 0.20 × 0.16 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.493, T_max = 0.601
6270 measured reflections
2298 independent reflections
1945 reflections with I > 2σ(I)
R_int = 0.106

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.204
S = 1.04
2298 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.82 e Å⁻³

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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/S1600536809020054/bq2140sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809020054/bq2140Isup2.hkl

checkCIF report

Comment top

The asymmetric unit of (I) contains one cation and one Br anion (Fig. 1). The cation has a Λ-shaped conformation, and the dihedral angles formed by the C5/C8/N2 plane with the benzene and pyridinium rings are 61.19 (2)° and 72.88 (2)°, respectively (75.8 (2)° between the benzene and pyridinium rings). The geometry of the cation is similar to the one observed in Liu et al. (2008) and Liu et al. (2007). Two cations form a dimer through π–π interaction between pyridine rings, the distance of centroid-to-centroid is 3.685Å, which further are linked into one dimensional chain by the π–π interaction between benzene ring, the distance of centroid-to-centroid is 4.242Å. A three-dimensional supramolecular structure was packed via Van der Waals forces (Fig. 2).

Related literature top

For cations with similar geometry, see: Liu et al. (2007, 2008).

Experimental top

4-cyanobenzyl bromide (10 mmol, 1.96 g) and 4-methylpyridine (20 mmol, 1.88 g) were added to 40 ml of acetone. After stirring and refluxing for 12 h, the mixture was filtered, and the clear solution was allowed to evaporate slowly under inert atmosphere. Block crystals of the title compound were obtained after 3 days. The crystals were filtered, washed by acetone and dried in air.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. One dimensional chain is formed π–π interaction along the a-axis.

1-(4-Cyanobenzyl)-4-methylpyridinium bromide top

Crystal data top

C₁₄H₁₃N₂⁺·Br⁻	F(000) = 584
M_r = 289.17	D_x = 1.481 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3626 reflections
a = 12.967 (5) Å	θ = 2.9–27.7°
b = 8.217 (4) Å	µ = 3.15 mm⁻¹
c = 12.260 (5) Å	T = 296 K
β = 96.900 (5)°	Block, colorless
V = 1296.8 (10) Å³	0.24 × 0.20 × 0.16 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2298 independent reflections
Radiation source: sealed tube	1945 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.106
ϕ and ω scans	θ_max = 25.1°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −15→15
T_min = 0.493, T_max = 0.601	k = −9→8
6270 measured reflections	l = −13→14

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.204	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.1306P)² + 1.6412P] where P = (F_o² + 2F_c²)/3
2298 reflections	(Δ/σ)_max < 0.001
155 parameters	Δρ_max = 0.84 e Å⁻³
0 restraints	Δρ_min = −0.82 e Å⁻³

Crystal data top

C₁₄H₁₃N₂⁺·Br⁻	V = 1296.8 (10) Å³
M_r = 289.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.967 (5) Å	µ = 3.15 mm⁻¹
b = 8.217 (4) Å	T = 296 K
c = 12.260 (5) Å	0.24 × 0.20 × 0.16 mm
β = 96.900 (5)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2298 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1945 reflections with I > 2σ(I)
T_min = 0.493, T_max = 0.601	R_int = 0.106
6270 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.204	H-atom parameters constrained
S = 1.04	Δρ_max = 0.84 e Å⁻³
2298 reflections	Δρ_min = −0.82 e Å⁻³
155 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	0.77449 (4)	0.08544 (6)	0.80230 (4)	0.0499 (3)
C1	0.3632 (6)	0.5777 (8)	0.3983 (7)	0.0690 (18)
C2	0.4519 (5)	0.6742 (8)	0.4207 (5)	0.0618 (15)
C3	0.5131 (6)	0.7037 (11)	0.3372 (6)	0.084 (2)
H3	0.4949	0.6579	0.2682	0.101*
C4	0.6000 (5)	0.7993 (10)	0.3554 (6)	0.0783 (19)
H4	0.6401	0.8173	0.2986	0.094*
C5	0.6291 (5)	0.8699 (8)	0.4575 (6)	0.0639 (15)
C6	0.5696 (5)	0.8356 (9)	0.5418 (5)	0.0664 (16)
H6	0.5889	0.8784	0.6115	0.080*
C7	0.4814 (5)	0.7378 (8)	0.5231 (6)	0.0672 (16)
H7	0.4425	0.7156	0.5803	0.081*
C8	0.7202 (5)	0.9829 (9)	0.4770 (6)	0.0728 (17)
H8A	0.7083	1.0755	0.4282	0.087*
H8B	0.7251	1.0231	0.5518	0.087*
C9	0.8667 (5)	0.9449 (9)	0.3689 (7)	0.0723 (18)
H9	0.8355	1.0195	0.3182	0.087*
C10	0.9583 (6)	0.8757 (9)	0.3518 (6)	0.0716 (17)
H10	0.9882	0.9006	0.2886	0.086*
C11	1.0081 (5)	0.7671 (7)	0.4288 (6)	0.0644 (16)
C12	0.9567 (5)	0.7273 (8)	0.5214 (7)	0.0741 (19)
H12	0.9871	0.6548	0.5740	0.089*
C13	0.8650 (5)	0.7938 (9)	0.5326 (6)	0.0719 (17)
H13	0.8308	0.7629	0.5918	0.086*
N1	0.2896 (5)	0.4920 (10)	0.3754 (6)	0.0880 (18)
N2	0.8195 (5)	0.9065 (5)	0.4596 (5)	0.0624 (14)
C14	1.0990 (5)	0.6989 (8)	0.4164 (6)	0.0692 (17)
H14A	1.1067	0.5998	0.4581	0.104*
H14B	1.1542	0.7724	0.4422	0.104*
H14C	1.1018	0.6753	0.3402	0.104*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0502 (4)	0.0532 (4)	0.0468 (4)	−0.00751 (19)	0.0074 (3)	−0.00020 (19)
C1	0.056 (4)	0.074 (4)	0.078 (5)	0.005 (3)	0.014 (3)	0.005 (3)
C2	0.057 (3)	0.063 (4)	0.065 (4)	0.009 (3)	0.006 (3)	0.007 (3)
C3	0.083 (5)	0.107 (6)	0.065 (4)	−0.016 (4)	0.019 (4)	−0.004 (4)
C4	0.070 (4)	0.105 (5)	0.064 (4)	−0.013 (4)	0.022 (3)	−0.003 (4)
C5	0.058 (3)	0.060 (3)	0.075 (4)	0.007 (3)	0.012 (3)	0.003 (3)
C6	0.066 (4)	0.075 (4)	0.060 (4)	−0.003 (3)	0.016 (3)	−0.006 (3)
C7	0.067 (4)	0.074 (4)	0.064 (4)	0.003 (3)	0.025 (3)	0.006 (3)
C8	0.062 (4)	0.069 (4)	0.088 (5)	0.005 (3)	0.016 (3)	−0.002 (4)
C9	0.061 (4)	0.078 (4)	0.078 (5)	−0.002 (3)	0.008 (3)	0.012 (3)
C10	0.066 (4)	0.079 (4)	0.073 (4)	0.003 (3)	0.020 (3)	0.003 (4)
C11	0.051 (3)	0.062 (4)	0.081 (4)	−0.006 (3)	0.010 (3)	−0.002 (3)
C12	0.061 (4)	0.073 (4)	0.088 (5)	0.001 (3)	0.003 (3)	0.010 (4)
C13	0.066 (4)	0.082 (4)	0.071 (4)	−0.002 (3)	0.020 (3)	0.008 (3)
N1	0.062 (3)	0.095 (5)	0.106 (5)	−0.002 (4)	0.011 (3)	−0.002 (4)
N2	0.059 (3)	0.063 (3)	0.066 (4)	0.002 (2)	0.012 (3)	0.006 (2)
C14	0.055 (3)	0.068 (4)	0.086 (5)	0.002 (3)	0.014 (3)	−0.005 (3)

Geometric parameters (Å, º) top

C1—N1	1.192 (9)	C8—H8B	0.9700
C1—C2	1.397 (10)	C9—C10	1.355 (10)
C2—C7	1.371 (9)	C9—N2	1.370 (10)
C2—C3	1.390 (10)	C9—H9	0.9300
C3—C4	1.370 (11)	C10—C11	1.399 (10)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.389 (10)	C11—C14	1.330 (9)
C4—H4	0.9300	C11—C12	1.423 (10)
C5—C6	1.392 (9)	C12—C13	1.330 (10)
C5—C8	1.499 (9)	C12—H12	0.9300
C6—C7	1.394 (9)	C13—N2	1.371 (9)
C6—H6	0.9300	C13—H13	0.9300
C7—H7	0.9300	C14—H14A	0.9600
C8—N2	1.471 (8)	C14—H14B	0.9600
C8—H8A	0.9700	C14—H14C	0.9600

N1—C1—C2	177.0 (8)	C10—C9—N2	121.0 (7)
C7—C2—C3	119.1 (6)	C10—C9—H9	119.5
C7—C2—C1	122.0 (6)	N2—C9—H9	119.5
C3—C2—C1	118.9 (7)	C9—C10—C11	120.4 (7)
C4—C3—C2	120.7 (7)	C9—C10—H10	119.8
C4—C3—H3	119.6	C11—C10—H10	119.8
C2—C3—H3	119.6	C14—C11—C10	122.4 (7)
C3—C4—C5	121.0 (6)	C14—C11—C12	120.1 (7)
C3—C4—H4	119.5	C10—C11—C12	117.5 (6)
C5—C4—H4	119.5	C13—C12—C11	119.9 (7)
C4—C5—C6	118.0 (6)	C13—C12—H12	120.0
C4—C5—C8	121.8 (6)	C11—C12—H12	120.0
C6—C5—C8	120.2 (6)	C12—C13—N2	122.0 (7)
C5—C6—C7	120.8 (6)	C12—C13—H13	119.0
C5—C6—H6	119.6	N2—C13—H13	119.0
C7—C6—H6	119.6	C9—N2—C13	119.1 (6)
C2—C7—C6	120.3 (6)	C9—N2—C8	120.3 (6)
C2—C7—H7	119.9	C13—N2—C8	120.6 (6)
C6—C7—H7	119.9	C11—C14—H14A	109.5
N2—C8—C5	113.5 (6)	C11—C14—H14B	109.5
N2—C8—H8A	108.9	H14A—C14—H14B	109.5
C5—C8—H8A	108.9	C11—C14—H14C	109.5
N2—C8—H8B	108.9	H14A—C14—H14C	109.5
C5—C8—H8B	108.9	H14B—C14—H14C	109.5
H8A—C8—H8B	107.7

C7—C2—C3—C4	−2.2 (12)	N2—C9—C10—C11	−2.0 (11)
C1—C2—C3—C4	179.2 (7)	C9—C10—C11—C14	−178.6 (7)
C2—C3—C4—C5	−0.2 (13)	C9—C10—C11—C12	2.9 (11)
C3—C4—C5—C6	2.4 (11)	C14—C11—C12—C13	−179.0 (7)
C3—C4—C5—C8	−176.3 (7)	C10—C11—C12—C13	−0.5 (11)
C4—C5—C6—C7	−2.1 (10)	C11—C12—C13—N2	−2.9 (11)
C8—C5—C6—C7	176.5 (6)	C10—C9—N2—C13	−1.4 (10)
C3—C2—C7—C6	2.4 (10)	C10—C9—N2—C8	179.9 (7)
C1—C2—C7—C6	−179.0 (6)	C12—C13—N2—C9	3.9 (11)
C5—C6—C7—C2	−0.2 (10)	C12—C13—N2—C8	−177.4 (7)
C4—C5—C8—N2	−61.6 (9)	C5—C8—N2—C9	107.0 (7)
C6—C5—C8—N2	119.8 (7)	C5—C8—N2—C13	−71.7 (8)

Experimental details

Crystal data
Chemical formula	C₁₄H₁₃N₂⁺·Br⁻
M_r	289.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	12.967 (5), 8.217 (4), 12.260 (5)
β (°)	96.900 (5)
V (Å³)	1296.8 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.15
Crystal size (mm)	0.24 × 0.20 × 0.16

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.493, 0.601
No. of measured, independent and observed [I > 2σ(I)] reflections	6270, 2298, 1945
R_int	0.106
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.204, 1.04
No. of reflections	2298
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.84, −0.82

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 20731004), the Natural Science Foundation for Outstanding Scholars of Anhui Province, China (grant No. 044-J-04011) and the Natural Science Foundation of the Education Commission of Anhui Province, China (No. KJ2008B004).

References

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liu, G.-X. (2007). Acta Cryst. E63, o704–o706. Web of Science CSD CrossRef IUCr Journals Google Scholar
Liu, G.-X., Xu, H., Ren, X.-M. & Sun, W.-Y. (2008). CrystEngComm, 10, 1574–1582. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar