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 ▶); 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) ų

• 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

• Δρ_max = 0.23 e Å⁻³

• Δρ_min = −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.

Supplementary Material

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

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) .

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 C_aromatic—H = 0.95 Å and C_methyl—H 0.98 Å, and refined using a riding model with U_iso(H) = 1.2 U_eq(C) or 1.5 U_eq(C_methyl)]. 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 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.

Crystal data

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

Data collection

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

Refinement

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

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	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, °)

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 codes: (i) −x+1, −y+1, −z+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···Cl1ii	0.95	2.75	3.496 (2)	136
C5—H5···Cl1i	0.95	2.62	3.554 (2)	169

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