Acta Crystallographica Section E: Structure Reports Online

Acta Crystallogr Sect E Struct Rep Online. 64(Pt 9): o1806-o1806

4,4′-Dimethyl-2,2′-bipyridinium dichloride

Urs David Eckensbergera, Hans-Wolfram Lernera, Michael Boltea*

a. Institut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany

Correspondence e-mail: bolte@chemie.uni-frankfurt.de

© Eckensberger et al. 2008

DOI: 10.1107/S1600536808026615

Published online: 23 August 2008

Abstract

In the title compound, C₁₂H₁₄N₂ ²⁺·2Cl⁻, the 4,4′-dimethyl-2,2′-bipyridinium cation is essentially planar (r.m.s. deviation for all non-H atoms = 0.004 Å) and is located on a crystallographic inversion centre. The cations and chloride anions lie in planes parallel to (111) and are connected by N—H⋯Cl and C—H⋯Cl hydrogen bonds.

Related literature

For related literature, see: Eckensberger (2006 ▶); Scheibitz et al. (2005 ▶). For structures containing the 4,4′-dimethyl-2,2′-bipyridinium cation, see: Linden et al. (1999 ▶); Willett et al. (2001 ▶).

Experimental

Crystal data

C₁₂H₁₄N₂ ²⁺·2Cl⁻

M r = 257.15

Triclinic,

a = 5.1999 (10) Å

b = 7.2705 (13) Å

c = 8.4785 (15) Å

α = 93.877 (15)°

β = 102.349 (15)°

γ = 97.759 (15)°

V = 308.71 (10) Å³

Z = 1

Mo Kα radiation

μ = 0.50 mm⁻¹

T = 173 (2) K

0.21 × 0.21 × 0.14 mm

Data collection

Stoe IPDSII two-circle diffractometer

Absorption correction: multi-scan (MULABS; Spek, 2003 ▶; Blessing, 1995 ▶) T min = 0.902, T max = 0.933

3382 measured reflections

1147 independent reflections

926 reflections with I > 2σ(I)

R int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.035

wR(F ²) = 0.079

S = 0.97

1147 reflections

78 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å⁻³

Δρmin = −0.23 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

See full table Table 1. Hydrogen-bond geometry (Å, °)

Supplementary Material

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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BI2297).

supplementary crystallographic information

Comment

Recently, we have synthesized the dimeric diferrocenylboryl cation I (see Fig. 3) (Scheibitz et al., 2005). Now we are interested to prepare the cationic dinuclear complex with a pentamethylcyclopentadienyl ring III. In an attempt to synthesize III from II (Eckensberger, 2006) and 4,4'-dimethyl-2,2'-bipyridine, we obtained the title compound as a by-product. X-ray quality crystals were grown from CD₃CN in an NMR tube at ambient temperature.

The title compound crystallizes with one formula unit in the unit cell. The cation is located on a crystallographic inversion centre. It is essentially planar (r.m.s. deviation for all non-H atoms 0.004 Å). The chloride anions deviate by just 0.072 (3) Å from this plane. These planes are parallel to the (111) plane. In a plane, cations and anions are connected by N—H···Cl and C—H···Cl hydrogen bonds (Fig. 2).

Experimental

In an attempt to synthesize complex III (Eckensberger, 2006) from II (0.156 g, 0.32 mmol) with 4,4'-dimethyl-2,2'-bipyridine (0.065 g, 0.35 mmol) in 5 ml acetonitrile, the title compound was obtained as a by-product. X-ray quality crystals were grown from CD₃CN in an NMR tube at ambient temperature after several days.

Refinement

H atoms were geometrically positioned with Caromatic—H = 0.95 Å and Cmethyl—H 0.98 Å, and refined using a riding model with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(Cmethyl)]. The methyl group was allowed to rotate about its local threefold axis. The H atom bonded to N was freely refined.

Figures

Fig. 1.View larger versionFig. 1. Perspective view of the title compound with the atom numbering scheme; displacement ellipsoids are at the 50% probability level; H atoms are drawn as small spheres of arbitrary radii. Hydrogen bonds are drawn as dashed lines. Symmetry operator for generating equivalent atoms: 1 - x, 1 - y, 1 - z.

Fig. 2.View larger versionFig. 2. Packing diagram of the title compound viewed perpendicular to the (1 1 1) plane. Hydrogen bonds are indicated as dashed lines.

Fig. 3.View larger versionFig. 3. Reaction scheme.

Crystal data

See full table

Data collection

See full table

Refinement

See full table

Special details

See full table

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)

See full table

Atomic displacement parameters (Å²)

See full table

Geometric parameters (Å, °)

See full table

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

See full table

Symmetry codes: (ii) −x+2, −y, −z+1; (i) −x+1, −y+1, −z+1.

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References

Blessing, R. H. (1995). Acta Cryst. A51, 33–38.

Eckensberger, U. D. (2006). Diploma Thesis, Frankfurt.

Linden, A., James, M. A., Millikan, M. B., Kivlighon, L. M., Petridis, A. & James, B. D. (1999). Inorg. Chim. Acta, 284, 215–222.

Scheibitz, M., Heilmann, J. B., Winter, R. F., Bolte, M., Bats, J. W. & Wagner, M. (2005). Dalton Trans. pp. 159–170.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.

Stoe & Cie (2001). X-AREA Stoe & Cie, Darmstadt, Germany.

Willett, R. D., Pon, G. & Nagy, C. (2001). Inorg. Chem.40, 4342–4352.

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Fig. 1.

Perspective view of the title compound with the atom numbering scheme; displacement ellipsoids are at the 50% probability level; H atoms are drawn as small spheres of arbitrary radii. Hydrogen bonds are drawn as dashed lines. Symmetry operator for generating equivalent atoms: 1 - x, 1 - y, 1 - z.

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Fig. 2.

Packing diagram of the title compound viewed perpendicular to the (1 1 1) plane. Hydrogen bonds are indicated as dashed lines.

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Fig. 3.

Reaction scheme.

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C₁₂H₁₄N₂²⁺·2(Cl⁻) | Z = 1
Mr = 257.15 | F(000) = 134
Triclinic, P1 | Dx = 1.383 Mg m⁻³
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å
a = 5.1999 (10) Å | Cell parameters from 3157 reflections
b = 7.2705 (13) Å | θ = 3.6–25.8°
c = 8.4785 (15) Å | µ = 0.50 mm⁻¹
α = 93.877 (15)° | T = 173 K
β = 102.349 (15)° | Block, colourless
γ = 97.759 (15)° | 0.21 × 0.21 × 0.14 mm
V = 308.71 (10) Å³ |

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Stoe IPDSII two-circle diffractometer | 1147 independent reflections
Radiation source: fine-focus sealed tube | 926 reflections with I > 2σ(I)
graphite | Rint = 0.058
ω scans | θmax = 25.6°, θmin = 3.6°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | h = −6→6
Tmin = 0.902, Tmax = 0.933 | k = −8→8
3382 measured reflections | l = −10→9

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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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079 | H atoms treated by a mixture of independent and constrained refinement
S = 0.97 | w = 1/[σ²(Fo²) + (0.0407P)²] where P = (Fo² + 2Fc²)/3
1147 reflections | (Δ/σ)max < 0.001
78 parameters | Δρmax = 0.23 e Å⁻³
0 restraints | Δρmin = −0.23 e Å⁻³

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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.

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| x | y | z | Uiso*/Ueq |
Cl1 | 0.97517 (12) | 0.22553 (7) | 0.26756 (7) | 0.02679 (18) |
N1 | 0.6763 (4) | 0.3002 (2) | 0.5264 (2) | 0.0219 (4) |
H1 | 0.749 (6) | 0.296 (4) | 0.444 (4) | 0.047 (8)* |
C1 | 0.5194 (4) | 0.4274 (2) | 0.5570 (2) | 0.0195 (4) |
C2 | 0.7255 (5) | 0.1636 (3) | 0.6223 (3) | 0.0254 (5) |
H2 | 0.8362 | 0.0774 | 0.5967 | 0.031* |
C3 | 0.6195 (5) | 0.1455 (3) | 0.7564 (3) | 0.0273 (5) |
H3 | 0.6568 | 0.0483 | 0.8232 | 0.033* |
C4 | 0.4553 (4) | 0.2725 (3) | 0.7936 (3) | 0.0223 (5) |
C5 | 0.4078 (4) | 0.4121 (3) | 0.6904 (2) | 0.0210 (5) |
H5 | 0.2957 | 0.4988 | 0.7125 | 0.025* |
C6 | 0.3345 (5) | 0.2555 (3) | 0.9383 (3) | 0.0287 (5) |
H6A | 0.2337 | 0.3585 | 0.9488 | 0.043* |
H6B | 0.4761 | 0.2605 | 1.0362 | 0.043* |
H6C | 0.2147 | 0.1365 | 0.9244 | 0.043* |

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| U ¹¹ | U ²² | U ³³ | U ¹² | U ¹³ | U ²³
Cl1 | 0.0285 (3) | 0.0269 (3) | 0.0288 (3) | 0.00927 (19) | 0.0113 (2) | 0.00399 (18)
N1 | 0.0236 (10) | 0.0228 (8) | 0.0223 (10) | 0.0070 (7) | 0.0082 (8) | 0.0064 (7)
C1 | 0.0204 (11) | 0.0195 (9) | 0.0181 (10) | 0.0029 (8) | 0.0031 (8) | 0.0028 (8)
C2 | 0.0262 (12) | 0.0238 (9) | 0.0293 (12) | 0.0086 (8) | 0.0081 (10) | 0.0084 (8)
C3 | 0.0284 (13) | 0.0244 (10) | 0.0295 (12) | 0.0066 (9) | 0.0032 (10) | 0.0110 (9)
C4 | 0.0231 (11) | 0.0217 (9) | 0.0204 (10) | −0.0012 (8) | 0.0035 (9) | 0.0039 (8)
C5 | 0.0243 (12) | 0.0196 (9) | 0.0200 (10) | 0.0061 (8) | 0.0043 (9) | 0.0049 (8)
C6 | 0.0350 (14) | 0.0301 (11) | 0.0218 (11) | 0.0040 (10) | 0.0076 (10) | 0.0075 (9)

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N1—C2 | 1.342 (3) | C3—H3 | 0.950
N1—C1 | 1.360 (2) | C4—C5 | 1.397 (3)
N1—H1 | 0.86 (3) | C4—C6 | 1.498 (3)
C1—C5 | 1.382 (3) | C5—H5 | 0.950
C1—C1i | 1.484 (4) | C6—H6A | 0.980
C2—C3 | 1.372 (3) | C6—H6B | 0.980
C2—H2 | 0.950 | C6—H6C | 0.980
C3—C4 | 1.404 (3) |  |
C2—N1—C1 | 121.9 (2) | C5—C4—C3 | 117.6 (2)
C2—N1—H1 | 113.5 (19) | C5—C4—C6 | 121.92 (17)
C1—N1—H1 | 124.6 (19) | C3—C4—C6 | 120.46 (19)
N1—C1—C5 | 118.08 (18) | C1—C5—C4 | 121.78 (17)
N1—C1—C1i | 117.0 (2) | C1—C5—H5 | 119.1
C5—C1—C1i | 124.9 (2) | C4—C5—H5 | 119.1
N1—C2—C3 | 121.46 (17) | C4—C6—H6A | 109.5
N1—C2—H2 | 119.3 | C4—C6—H6B | 109.5
C3—C2—H2 | 119.3 | H6A—C6—H6B | 109.5
C2—C3—C4 | 119.17 (19) | C4—C6—H6C | 109.5
C2—C3—H3 | 120.4 | H6A—C6—H6C | 109.5
C4—C3—H3 | 120.4 | H6B—C6—H6C | 109.5
C2—N1—C1—C5 | −0.5 (3) | C2—C3—C4—C6 | 179.4 (2)
C2—N1—C1—C1i | 179.7 (2) | N1—C1—C5—C4 | 0.9 (3)
C1—N1—C2—C3 | 0.0 (3) | C1i—C1—C5—C4 | −179.3 (2)
N1—C2—C3—C4 | 0.2 (3) | C3—C4—C5—C1 | −0.7 (3)
C2—C3—C4—C5 | 0.1 (3) | C6—C4—C5—C1 | −180.0 (2)

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D—H···A | D—H | H···A | D···A | D—H···A
N1—H1···Cl1 | 0.86 (3) | 2.17 (3) | 3.009 (2) | 165 (3)
C2—H2···Cl1ii | 0.95 | 2.75 | 3.496 (2) | 136
C5—H5···Cl1i | 0.95 | 2.62 | 3.554 (2) | 169

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Table 1. Hydrogen-bond geometry (Å, °)

D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A
N1—H1⋯Cl1 | 0.86 (3) | 2.17 (3) | 3.009 (2) | 165 (3)
C2—H2⋯Cl1i | 0.95 | 2.75 | 3.496 (2) | 136
C5—H5⋯Cl1ii | 0.95 | 2.62 | 3.554 (2) | 169

Symmetry codes: (i) ; (ii) .

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