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Acta Crystallogr Sect E Struct Rep Online. 2008 September 1; 64(Pt 9): o1806.
Published online 2008 August 23. doi:  10.1107/S1600536808026615
PMCID: PMC2960639

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

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 [triangle]); Scheibitz et al. (2005 [triangle]). For structures containing the 4,4′-dimethyl-2,2′-bipyridinium cation, see: Linden et al. (1999 [triangle]); Willett et al. (2001 [triangle]).

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Object name is e-64-o1806-scheme1.jpg

Experimental

Crystal data

  • C12H14N2 2+·2Cl
  • M r = 257.15
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1806-efi1.jpg
  • 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 [triangle]; Blessing, 1995 [triangle]) 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 [triangle]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808026615/bi2297sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808026615/bi2297Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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.
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 ...
Fig. 2.
Packing diagram of the title compound viewed perpendicular to the (1 1 1) plane. Hydrogen bonds are indicated as dashed lines.
Fig. 3.
Reaction scheme.

Crystal data

C12H14N22+·2(Cl)Z = 1
Mr = 257.15F(000) = 134
Triclinic, P1Dx = 1.383 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.1999 (10) ÅCell parameters from 3157 reflections
b = 7.2705 (13) Åθ = 3.6–25.8°
c = 8.4785 (15) ŵ = 0.50 mm1
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

Data collection

Stoe IPDSII two-circle diffractometer1147 independent reflections
Radiation source: fine-focus sealed tube926 reflections with I > 2σ(I)
graphiteRint = 0.058
ω scansθmax = 25.6°, θmin = 3.6°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)h = −6→6
Tmin = 0.902, Tmax = 0.933k = −8→8
3382 measured reflectionsl = −10→9

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H atoms treated by a mixture of independent and constrained refinement
S = 0.97w = 1/[σ2(Fo2) + (0.0407P)2] where P = (Fo2 + 2Fc2)/3
1147 reflections(Δ/σ)max < 0.001
78 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = −0.23 e Å3

Special details

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)

xyzUiso*/Ueq
Cl10.97517 (12)0.22553 (7)0.26756 (7)0.02679 (18)
N10.6763 (4)0.3002 (2)0.5264 (2)0.0219 (4)
H10.749 (6)0.296 (4)0.444 (4)0.047 (8)*
C10.5194 (4)0.4274 (2)0.5570 (2)0.0195 (4)
C20.7255 (5)0.1636 (3)0.6223 (3)0.0254 (5)
H20.83620.07740.59670.031*
C30.6195 (5)0.1455 (3)0.7564 (3)0.0273 (5)
H30.65680.04830.82320.033*
C40.4553 (4)0.2725 (3)0.7936 (3)0.0223 (5)
C50.4078 (4)0.4121 (3)0.6904 (2)0.0210 (5)
H50.29570.49880.71250.025*
C60.3345 (5)0.2555 (3)0.9383 (3)0.0287 (5)
H6A0.23370.35850.94880.043*
H6B0.47610.26051.03620.043*
H6C0.21470.13650.92440.043*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0285 (3)0.0269 (3)0.0288 (3)0.00927 (19)0.0113 (2)0.00399 (18)
N10.0236 (10)0.0228 (8)0.0223 (10)0.0070 (7)0.0082 (8)0.0064 (7)
C10.0204 (11)0.0195 (9)0.0181 (10)0.0029 (8)0.0031 (8)0.0028 (8)
C20.0262 (12)0.0238 (9)0.0293 (12)0.0086 (8)0.0081 (10)0.0084 (8)
C30.0284 (13)0.0244 (10)0.0295 (12)0.0066 (9)0.0032 (10)0.0110 (9)
C40.0231 (11)0.0217 (9)0.0204 (10)−0.0012 (8)0.0035 (9)0.0039 (8)
C50.0243 (12)0.0196 (9)0.0200 (10)0.0061 (8)0.0043 (9)0.0049 (8)
C60.0350 (14)0.0301 (11)0.0218 (11)0.0040 (10)0.0076 (10)0.0075 (9)

Geometric parameters (Å, °)

N1—C21.342 (3)C3—H30.950
N1—C11.360 (2)C4—C51.397 (3)
N1—H10.86 (3)C4—C61.498 (3)
C1—C51.382 (3)C5—H50.950
C1—C1i1.484 (4)C6—H6A0.980
C2—C31.372 (3)C6—H6B0.980
C2—H20.950C6—H6C0.980
C3—C41.404 (3)
C2—N1—C1121.9 (2)C5—C4—C3117.6 (2)
C2—N1—H1113.5 (19)C5—C4—C6121.92 (17)
C1—N1—H1124.6 (19)C3—C4—C6120.46 (19)
N1—C1—C5118.08 (18)C1—C5—C4121.78 (17)
N1—C1—C1i117.0 (2)C1—C5—H5119.1
C5—C1—C1i124.9 (2)C4—C5—H5119.1
N1—C2—C3121.46 (17)C4—C6—H6A109.5
N1—C2—H2119.3C4—C6—H6B109.5
C3—C2—H2119.3H6A—C6—H6B109.5
C2—C3—C4119.17 (19)C4—C6—H6C109.5
C2—C3—H3120.4H6A—C6—H6C109.5
C4—C3—H3120.4H6B—C6—H6C109.5
C2—N1—C1—C5−0.5 (3)C2—C3—C4—C6179.4 (2)
C2—N1—C1—C1i179.7 (2)N1—C1—C5—C40.9 (3)
C1—N1—C2—C30.0 (3)C1i—C1—C5—C4−179.3 (2)
N1—C2—C3—C40.2 (3)C3—C4—C5—C1−0.7 (3)
C2—C3—C4—C50.1 (3)C6—C4—C5—C1−180.0 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.86 (3)2.17 (3)3.009 (2)165 (3)
C2—H2···Cl1ii0.952.753.496 (2)136
C5—H5···Cl1i0.952.623.554 (2)169

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

Footnotes

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

References

  • Blessing, R. H. (1995). Acta Cryst. A51, 33–38. [PubMed]
  • 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. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • 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. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography