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

Eckensberger, U.D.; Lerner, H.-W.; Bolte, M.

doi:10.1107/S1600536808026615

organic compounds

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

Urs David Eckensberger,^a Hans-Wolfram Lerner ^a and Michael Bolte ^a ^*

^aInstitut 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

(Received 10 July 2008; accepted 18 August 2008; online 23 August 2008)

In the title compound, C₁₂H₁₄N₂²⁺·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

C₁₂H₁₄N₂²⁺·2Cl⁻
M_r = 257.15
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.079
S = 0.97
1147 reflections
78 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.23 e Å⁻³

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) -x+2, -y, -z+1; (ii) -x+1, -y+1, -z+1.

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.

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); 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 (Sheldrick, 2008).

Figures top

	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.
	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.

4,4'-Dimethyl-2,2'-bipyridinium dichloride top

Crystal data top

C₁₂H₁₄N₂²⁺·2(Cl⁻)	Z = 1
M_r = 257.15	F(000) = 134
Triclinic, P1	D_x = 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

Data collection top

Stoe IPDSII two-circle diffractometer	1147 independent reflections
Radiation source: fine-focus sealed tube	926 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
ω scans	θ_max = 25.6°, θ_min = 3.6°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	h = −6→6
T_min = 0.902, T_max = 0.933	k = −8→8
3382 measured reflections	l = −10→9

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)] = 0.035	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(F_o²) + (0.0407P)²] where P = (F_o² + 2F_c²)/3
1147 reflections	(Δ/σ)_max < 0.001
78 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₂H₁₄N₂²⁺·2(Cl⁻)	γ = 97.759 (15)°
M_r = 257.15	V = 308.71 (10) Å³
Triclinic, P1	Z = 1
a = 5.1999 (10) Å	Mo Kα radiation
b = 7.2705 (13) Å	µ = 0.50 mm⁻¹
c = 8.4785 (15) Å	T = 173 K
α = 93.877 (15)°	0.21 × 0.21 × 0.14 mm
β = 102.349 (15)°

Data collection top

Stoe IPDSII two-circle diffractometer	1147 independent reflections
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	926 reflections with I > 2σ(I)
T_min = 0.902, T_max = 0.933	R_int = 0.058
3382 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	Δρ_max = 0.23 e Å⁻³
1147 reflections	Δρ_min = −0.23 e Å⁻³
78 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
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*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

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

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄N₂²⁺·2(Cl⁻)
M_r	257.15
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	5.1999 (10), 7.2705 (13), 8.4785 (15)
α, β, γ (°)	93.877 (15), 102.349 (15), 97.759 (15)
V (Å³)	308.71 (10)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.50
Crystal size (mm)	0.21 × 0.21 × 0.14

Data collection
Diffractometer	Stoe IPDSII two-circle diffractometer
Absorption correction	Multi-scan (MULABS; Spek, 2003; Blessing, 1995)
T_min, T_max	0.902, 0.933
No. of measured, independent and observed [I > 2σ(I)] reflections	3382, 1147, 926
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.079, 0.97
No. of reflections	1147
No. of parameters	78
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.23

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL-Plus (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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) −x+2, −y, −z+1; (ii) −x+1, −y+1, −z+1.

References

Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Eckensberger, U. D. (2006). Diploma Thesis, Frankfurt. Google Scholar
Linden, A., James, M. A., Millikan, M. B., Kivlighon, L. M., Petridis, A. & James, B. D. (1999). Inorg. Chim. Acta, 284, 215–222. Web of Science CSD CrossRef CAS Google Scholar
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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1806

doi:10.1107/S1600536808026615

Open

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