1,1′-Dimethyl-4,4′-bipyridinium bis­(tetra­fluorido­borate)

Yang, F.; Deng, J.-C.; Li, Z.-G.; Xu, J.-W.

doi:10.1107/S1600536807064963

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o253

https://doi.org/10.1107/S1600536807064963

Open

access

1,1′-Dimethyl-4,4′-bipyridinium bis(tetrafluoridoborate)

Fan Yang,^a Jian-Cheng Deng,^a ^* Zhi-Gang Li ^b and Jing-Wei Xu ^b ‡

^aThe College of Chemistry, Xiangtan University, Hunan 411105, People's Republic of China, and ^bNational Analytical Research Center of Electrochemistry and Spectroscopy, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of China
^*Correspondence e-mail: djcwye@163.com

(Received 17 October 2007; accepted 1 December 2007; online 12 December 2007)

In the title compound, C₁₂H₁₄N₂²⁺·2BF₄⁻, the cation has a centre of symmetry at the mid-point of the central C—C bond. π–π interactions, with a shortest atom-to-atom distance of 3.757 (4) Å, extend the crystal structure into a one-dimensional supramolecular chain.

Related literature

For related literature, see: Dou et al. (2007 ).

Experimental

Crystal data

C₁₂H₁₄N₂²⁺·2BF₄⁻
M_r = 359.87
Monoclinic, P 2₁ /c
a = 5.824 (2) Å
b = 8.849 (3) Å
c = 14.855 (6) Å
β = 94.825 (5)°
V = 762.9 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 293 (2) K
0.26 × 0.12 × 0.07 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SAINT-Plus; Bruker, 2003 ) T_min = 0.960, T_max = 0.988
3923 measured reflections
1508 independent reflections
843 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.082
wR(F²) = 0.249
S = 1.02
1508 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807064963/kj2076sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807064963/kj2076Isup2.hkl

checkCIF report

Comment top

Dou et al. have reported a structure, synthesized by in situ reaction under hydrothermal conditions, in which pyridine nitrogen atoms are covalently bonded to methyl groups and the counterion are ClO₄^- anions (Dou et al., 2007). Here we report the structure of the title compound, which is essentially isomorphous with the perchlorate compound.

The title compound, shown in Fig. 1, consists of 1,1'-dimethyl-4,4'-bipyridinium cations and tetrafluoroborate anions. There is a centre of symmetry at the mid-point of the C—C bond linking the two pyridine rings. The two pyridine rings are exactly parallel by symmetry, and essentially coplanar.

In the crystal structure, there are π···π interactions between pyridine rings at (x, y, z) and (1 - x,1 - y, -z), with the shortest atom-to-atom distance of 3.757 (4) Å, which leads to a one-dimensional supramolecular chain running in the c-direction. (Fig. 2).

Related literature top

For related literature, see: Dou et al. (2007).

Experimental top

Compound (I) was solvothermally prepared from a reaction mixture of Cu(BF₄)₂ (0.2 mmol), 4,4'-bipyridine (0.1 mmol), methanol (3 ml) and distilled water (8 ml) in a molar ratio of 2:1:740:4444; the pH value was adjusted to 4.6 with trimethylamine and acetic acid. The mixture was stirred for 20 min at room temperature and then sealed in a Teflon-lined stainless steel autoclave with a 23 ml capacity at 423 K for 72 h. After cooling to room temperature, colourless block-shaped crystals were obtained; these were washed with deionized water, filtered, and dried in air (yield 54% based on Cu).

Structure description top

For related literature, see: Dou et al. (2007).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).

Figures top

	Fig. 1. A view of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (A) -x, 1 - y, -z].
	Fig. 2. Perspective view along the c axis of the packing of the title compound. For the sake of clarity, H atoms have been omitted. Dashed lines indicated π···π interactions.

1,1'-Dimethyl-4,4'-bipyridinium bis(tetrafluoroborate) top

Crystal data top

C₁₂H₁₄N₂²⁺·2BF₄⁻	F(000) = 364
M_r = 359.87	D_x = 1.567 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 852 reflections
a = 5.824 (2) Å	θ = 2.7–21.8°
b = 8.849 (3) Å	µ = 0.16 mm⁻¹
c = 14.855 (6) Å	T = 293 K
β = 94.825 (5)°	Block, white
V = 762.9 (5) Å³	0.26 × 0.12 × 0.07 mm
Z = 2

Data collection top

Bruker APEX CCD area-detector diffractometer	1508 independent reflections
Radiation source: fine-focus sealed tube	843 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
φ and ω scans	θ_max = 26.1°, θ_min = 2.7°
Absorption correction: multi-scan (SAINT-Plus; Bruker, 2003)	h = −7→7
T_min = 0.960, T_max = 0.988	k = −7→10
3923 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)] = 0.082	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.249	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.1212P)² + 0.6686P] where P = (F_o² + 2F_c²)/3
1508 reflections	(Δ/σ)_max = 0.027
110 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₂H₁₄N₂²⁺·2BF₄⁻	V = 762.9 (5) Å³
M_r = 359.87	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.824 (2) Å	µ = 0.16 mm⁻¹
b = 8.849 (3) Å	T = 293 K
c = 14.855 (6) Å	0.26 × 0.12 × 0.07 mm
β = 94.825 (5)°

Data collection top

Bruker APEX CCD area-detector diffractometer	1508 independent reflections
Absorption correction: multi-scan (SAINT-Plus; Bruker, 2003)	843 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.988	R_int = 0.029
3923 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.082	0 restraints
wR(F²) = 0.249	H-atom parameters constrained
S = 1.02	Δρ_max = 0.35 e Å⁻³
1508 reflections	Δρ_min = −0.23 e Å⁻³
110 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
N1	0.4587 (6)	0.7384 (4)	0.0761 (2)	0.0562 (10)
C1	0.3344 (8)	0.6666 (6)	0.1356 (3)	0.0630 (13)
H1	0.3694	0.6820	0.1972	0.076*
C2	0.1604 (8)	0.5727 (6)	0.1078 (3)	0.0595 (12)
H2	0.0809	0.5225	0.1505	0.071*
C3	0.0967 (7)	0.5493 (4)	0.0157 (2)	0.0467 (10)
C4	0.2275 (9)	0.6266 (5)	−0.0436 (3)	0.0638 (13)
H4	0.1937	0.6151	−0.1056	0.077*
C5	0.4030 (9)	0.7182 (6)	−0.0129 (3)	0.0667 (13)
H5	0.4872	0.7684	−0.0542	0.080*
C6	0.6523 (9)	0.8417 (6)	0.1092 (4)	0.0796 (15)
H6A	0.5918	0.9252	0.1411	0.119*
H6B	0.7278	0.8789	0.0587	0.119*
H6C	0.7609	0.7871	0.1491	0.119*
B	0.8454 (9)	0.5924 (6)	0.3254 (3)	0.0587 (14)
F1	0.7199 (7)	0.7234 (4)	0.3254 (3)	0.1178 (14)
F2	0.7561 (6)	0.5028 (4)	0.2566 (2)	0.0984 (12)
F3	1.0703 (5)	0.6258 (4)	0.3118 (2)	0.0984 (12)
F4	0.8324 (6)	0.5244 (5)	0.4071 (2)	0.1099 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.059 (2)	0.059 (2)	0.052 (2)	0.0147 (18)	0.0171 (17)	0.0058 (17)
C1	0.064 (3)	0.085 (3)	0.042 (2)	0.005 (3)	0.017 (2)	0.002 (2)
C2	0.067 (3)	0.077 (3)	0.037 (2)	0.003 (2)	0.022 (2)	0.012 (2)
C3	0.060 (2)	0.048 (2)	0.034 (2)	0.0214 (18)	0.0180 (17)	0.0048 (16)
C4	0.087 (3)	0.073 (3)	0.034 (2)	0.003 (3)	0.017 (2)	0.007 (2)
C5	0.090 (3)	0.070 (3)	0.044 (2)	0.005 (3)	0.026 (2)	0.010 (2)
C6	0.072 (3)	0.088 (4)	0.080 (4)	0.001 (3)	0.012 (3)	−0.002 (3)
B	0.063 (3)	0.068 (3)	0.048 (3)	−0.008 (3)	0.020 (2)	−0.007 (3)
F1	0.145 (3)	0.103 (3)	0.110 (3)	0.041 (2)	0.038 (2)	−0.007 (2)
F2	0.106 (2)	0.116 (3)	0.075 (2)	−0.028 (2)	0.0209 (17)	−0.0357 (18)
F3	0.076 (2)	0.145 (3)	0.078 (2)	−0.030 (2)	0.0309 (16)	−0.0211 (19)
F4	0.122 (3)	0.153 (3)	0.0570 (18)	−0.022 (2)	0.0204 (17)	0.0248 (19)

Geometric parameters (Å, º) top

N1—C5	1.347 (6)	C4—H4	0.9300
N1—C1	1.348 (5)	C5—H5	0.9300
N1—C6	1.502 (6)	C6—H6A	0.9600
C1—C2	1.348 (7)	C6—H6B	0.9600
C1—H1	0.9300	C6—H6C	0.9600
C2—C3	1.402 (5)	B—F4	1.361 (6)
C2—H2	0.9300	B—F2	1.362 (6)
C3—C4	1.392 (6)	B—F1	1.371 (6)
C3—C3ⁱ	1.470 (9)	B—F3	1.374 (6)
C4—C5	1.353 (7)

C5—N1—C1	118.9 (4)	N1—C5—C4	121.5 (4)
C5—N1—C6	121.0 (4)	N1—C5—H5	119.2
C1—N1—C6	120.2 (4)	C4—C5—H5	119.2
C2—C1—N1	121.4 (4)	N1—C6—H6A	109.5
C2—C1—H1	119.3	N1—C6—H6B	109.5
N1—C1—H1	119.3	H6A—C6—H6B	109.5
C1—C2—C3	121.4 (4)	N1—C6—H6C	109.5
C1—C2—H2	119.3	H6A—C6—H6C	109.5
C3—C2—H2	119.3	H6B—C6—H6C	109.5
C4—C3—C2	115.5 (4)	F4—B—F2	111.4 (4)
C4—C3—C3ⁱ	122.5 (4)	F4—B—F1	107.7 (4)
C2—C3—C3ⁱ	122.0 (4)	F2—B—F1	108.8 (4)
C5—C4—C3	121.3 (4)	F4—B—F3	110.6 (4)
C5—C4—H4	119.4	F2—B—F3	108.9 (4)
C3—C4—H4	119.4	F1—B—F3	109.4 (5)

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄N₂²⁺·2BF₄⁻
M_r	359.87
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	5.824 (2), 8.849 (3), 14.855 (6)
β (°)	94.825 (5)
V (Å³)	762.9 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.26 × 0.12 × 0.07

Data collection
Diffractometer	Bruker APEX CCD area-detector
Absorption correction	Multi-scan (SAINT-Plus; Bruker, 2003)
T_min, T_max	0.960, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	3923, 1508, 843
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.082, 0.249, 1.02
No. of reflections	1508
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.23

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998).

Footnotes

‡Additional correspondence author, email: jwxu@ciac.jl.cn.

Acknowledgements

This work is supported by the Changchun Institute of Applied Chemistry.

References

Bruker (1998). SMART (Version 5.0) and SHELXTL (Version 5.1). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2003). SAINT-Plus. Version 6. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dou, Y.-L., Li, Z.-G., Xu, J.-W. & Zhang, W.-X. (2007). Acta Cryst. E63, o1874–o1875. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar