2,2′-Dimethyl-4,4′-bipyridine

Ibragimov, B.; Weber, E.; Peukert, M.; Fischer, C.; Seichter, W.

doi:10.1107/S1600536808017807

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1287

doi:10.1107/S1600536808017807

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2,2′-Dimethyl-4,4′-bipyridine

Bahtier Ibragimov,^a ^* Edwin Weber,^b Max Peukert,^b Conrad Fischer ^b and Wilhelm Seichter ^b

^aInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, H. Abdullaev 83, Tashkent 100125, Uzbekistan, and ^bInstitut für Organische Chemie, TU Bergakademie Freiberg, Leipziger Strasse 29, D-09596 Freiberg/Sachsen, Germany
^*Correspondence e-mail: bahtier@academy.uzsci.net

(Received 7 May 2008; accepted 12 June 2008; online 19 June 2008)

In the crystal structure of the title compound, C₁₂H₁₂N₂, the molecule is twisted around the central C—C bond, with a dihedral angle of 8.32 (5)° between the mean planes of the pyridyl rings. The crystal structure is stabilized by arene stacking interactions, with a distance of 3.81 (1) Å between the ring centroids.

Related literature

For related literature, see: Boag et al. (1999 ); Kraft et al. (2005 ); Leighton & Sanders (1987 ); Alcade et al. (2007 ); Boghala et al. (2005 ); Braunschweig et al. (2006 ); Diskin-Posner et al. (2005 ); Kryschenko et al. (2003 ); Lynch et al. (1999 ); Yaghi et al. (1995 ).

Experimental

Crystal data

C₁₂H₁₂N₂
M_r = 184.24
Orthorhombic, P b c a
a = 11.7961 (3) Å
b = 7.6130 (2) Å
c = 21.2977 (5) Å
V = 1912.61 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 153 (2) K
0.54 × 0.24 × 0.14 mm

Data collection

Bruker X8 APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.923, T_max = 0.989
26242 measured reflections
3233 independent reflections
2262 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.139
S = 0.91
3233 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6C⋯N1ⁱ	0.98	2.73	3.6728 (16)	161
Symmetry code: (i) -x+2, -y, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-NT (Bruker, 2004); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808017807/cs2078sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808017807/cs2078Isup2.hkl

checkCIF report

Comment top

The preparation of I was carried out according to the literature procedure (Leighton & Sanders, 1987). The title compound represents a derivative of 4,4'-bipyridine, which is widely used as a bifunctional bridging element for the synthesis of supramolecular assemblies which may be based on hydrogen bond interactions (Lynch et al., 1999, Boghala et al., 2005) or metal coordination complexes (Diskin-Posner et al., 2005, Kryschenko et al., 2003), involving catenanes (Alcade et al., 2007), rotaxanes (Braunschweig et al., 2006) and metal-organic frameworks (Yaghi et al., 1995). In the crystal the title molecule adopts a slightly twisted conformation (see Figure 1), the mean planes of the hetero - aromatic rings make 8.32 (5)° dihedral angle. As there are no good hydrogen bond donors, the N1 nitrogen atom is only involved in the formation of a weak C-H···N hydrogen bond [C6-H6C···N1 distance ca. 2.73 Å]. The packing (Figure 2) is characterized by a columnar arrangement of molecules extending in the direction of the crystallographic b-axis. Within the molecular columns only one of the aromatic rings (designated as A in Fig. 1) of related molecules are involved in "face-to-face" interactions with a centroid···centroid distance of 3.81 (1) Å between such rings.

Related literature top

For related literature, see: Boag et al. (1999), Kraft et al. (2005), Leighton & Sanders,(1987); Alcade et al. (2007); Boghala et al. (2005); Braunschweig et al. (2006); Diskin-Posner, Patra & Goldberg (2005); Kryschenko et al. (2003); Lynch et al. (1999); Yaghi et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-NT (Bruker, 2004); data reduction: SAINT-NT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular presentation of the title compound with atomic labels and 50% probability displacement ellipsoids for non H-atoms.
	Fig. 2. Packing diagram as viewed down the crystallographic b axis.

2,2'-Dimethyl-4,4'-bipyridine top

Crystal data top

C₁₂H₁₂N₂	F(000) = 784
M_r = 184.24	D_x = 1.280 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5227 reflections
a = 11.7961 (3) Å	θ = 2.6–31.2°
b = 7.6130 (2) Å	µ = 0.08 mm⁻¹
c = 21.2977 (5) Å	T = 153 K
V = 1912.61 (8) Å³	Needle, colourless
Z = 8	0.54 × 0.24 × 0.14 mm

Data collection top

Bruker X8 APEXII CCD area-detector diffractometer	3233 independent reflections
Radiation source: fine-focus sealed tube	2262 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
ϕ and ω scans	θ_max = 31.7°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −17→17
T_min = 0.924, T_max = 0.989	k = −10→11
26242 measured reflections	l = −31→28

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.139	H-atom parameters constrained
S = 0.91	w = 1/[σ²(F_o²) + (0.0856P)²] where P = (F_o² + 2F_c²)/3
3233 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₂H₁₂N₂	V = 1912.61 (8) Å³
M_r = 184.24	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.7961 (3) Å	µ = 0.08 mm⁻¹
b = 7.6130 (2) Å	T = 153 K
c = 21.2977 (5) Å	0.54 × 0.24 × 0.14 mm

Data collection top

Bruker X8 APEXII CCD area-detector diffractometer	3233 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2262 reflections with I > 2σ(I)
T_min = 0.924, T_max = 0.989	R_int = 0.066
26242 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.139	H-atom parameters constrained
S = 0.91	Δρ_max = 0.37 e Å⁻³
3233 reflections	Δρ_min = −0.26 e Å⁻³
129 parameters

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

	x	y	z	U_iso*/U_eq
N1	0.83087 (7)	0.16449 (12)	0.48415 (4)	0.0253 (2)
N2	0.38746 (7)	−0.09210 (12)	0.27478 (4)	0.0235 (2)
C1	0.65454 (8)	0.06887 (12)	0.40087 (5)	0.0179 (2)
C2	0.76889 (8)	0.05080 (13)	0.38471 (5)	0.0206 (2)
H2	0.7889	0.0062	0.3446	0.025*
C3	0.85371 (8)	0.09788 (13)	0.42717 (5)	0.0215 (2)
C4	0.72102 (9)	0.18301 (15)	0.49892 (5)	0.0269 (2)
H4	0.7034	0.2310	0.5389	0.032*
C5	0.63117 (8)	0.13748 (14)	0.46021 (5)	0.0230 (2)
H5	0.5551	0.1527	0.4738	0.028*
C6	0.97634 (9)	0.07391 (15)	0.41063 (6)	0.0278 (2)
H6A	1.0152	0.1875	0.4127	0.042*
H6B	0.9825	0.0265	0.3680	0.042*
H6C	1.0115	−0.0079	0.4404	0.042*
C7	0.56279 (8)	0.01492 (12)	0.35706 (5)	0.0175 (2)
C8	0.44859 (8)	0.05087 (13)	0.36967 (5)	0.0194 (2)
H8	0.4285	0.1139	0.4065	0.023*
C9	0.36413 (8)	−0.00544 (13)	0.32832 (5)	0.0206 (2)
C10	0.49692 (8)	−0.12586 (15)	0.26316 (5)	0.0247 (2)
H10	0.5148	−0.1876	0.2257	0.030*
C11	0.58594 (8)	−0.07721 (13)	0.30182 (5)	0.0220 (2)
H11	0.6618	−0.1061	0.2909	0.026*
C12	0.24104 (9)	0.02673 (16)	0.34184 (6)	0.0288 (3)
H12A	0.2111	0.1128	0.3119	0.043*
H12B	0.2327	0.0721	0.3847	0.043*
H12C	0.1990	−0.0837	0.3378	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0222 (4)	0.0285 (5)	0.0252 (5)	0.0012 (3)	−0.0059 (4)	−0.0026 (3)
N2	0.0210 (4)	0.0277 (5)	0.0218 (5)	−0.0023 (3)	−0.0015 (3)	−0.0032 (3)
C1	0.0165 (4)	0.0192 (4)	0.0179 (5)	−0.0005 (3)	−0.0014 (3)	0.0009 (3)
C2	0.0178 (4)	0.0245 (5)	0.0196 (5)	−0.0002 (3)	−0.0006 (4)	−0.0001 (3)
C3	0.0185 (4)	0.0220 (5)	0.0241 (5)	−0.0006 (3)	−0.0034 (4)	0.0030 (4)
C4	0.0250 (5)	0.0343 (6)	0.0214 (5)	0.0027 (4)	−0.0038 (4)	−0.0068 (4)
C5	0.0198 (4)	0.0290 (5)	0.0201 (5)	0.0010 (4)	−0.0012 (4)	−0.0027 (4)
C6	0.0173 (5)	0.0353 (6)	0.0310 (6)	0.0003 (4)	−0.0031 (4)	0.0008 (4)
C7	0.0164 (4)	0.0191 (4)	0.0170 (5)	−0.0013 (3)	−0.0009 (3)	0.0021 (3)
C8	0.0172 (4)	0.0221 (5)	0.0189 (5)	0.0002 (3)	−0.0005 (3)	−0.0017 (3)
C9	0.0173 (4)	0.0230 (5)	0.0214 (5)	−0.0002 (3)	−0.0018 (4)	0.0001 (4)
C10	0.0230 (5)	0.0313 (5)	0.0197 (5)	−0.0019 (4)	0.0011 (4)	−0.0053 (4)
C11	0.0182 (4)	0.0281 (5)	0.0196 (5)	−0.0006 (3)	0.0012 (4)	−0.0025 (4)
C12	0.0176 (5)	0.0371 (6)	0.0316 (6)	0.0027 (4)	−0.0023 (4)	−0.0076 (5)

Geometric parameters (Å, º) top

N1—C4	1.3408 (13)	C6—H6B	0.9800
N1—C3	1.3426 (14)	C6—H6C	0.9800
N2—C10	1.3395 (13)	C7—C11	1.3967 (14)
N2—C9	1.3459 (13)	C7—C8	1.4006 (13)
C1—C5	1.3949 (14)	C8—C9	1.3971 (14)
C1—C2	1.3989 (13)	C8—H8	0.9500
C1—C7	1.4868 (13)	C9—C12	1.5004 (13)
C2—C3	1.3955 (14)	C10—C11	1.3848 (14)
C2—H2	0.9500	C10—H10	0.9500
C3—C6	1.5000 (14)	C11—H11	0.9500
C4—C5	1.3869 (14)	C12—H12A	0.9800
C4—H4	0.9500	C12—H12B	0.9800
C5—H5	0.9500	C12—H12C	0.9800
C6—H6A	0.9800

C4—N1—C3	116.47 (9)	H6B—C6—H6C	109.5
C10—N2—C9	116.59 (9)	C11—C7—C8	116.59 (9)
C5—C1—C2	116.77 (9)	C11—C7—C1	121.67 (9)
C5—C1—C7	121.88 (9)	C8—C7—C1	121.73 (9)
C2—C1—C7	121.35 (9)	C9—C8—C7	120.34 (9)
C3—C2—C1	120.44 (10)	C9—C8—H8	119.8
C3—C2—H2	119.8	C7—C8—H8	119.8
C1—C2—H2	119.8	N2—C9—C8	122.59 (9)
N1—C3—C2	122.61 (9)	N2—C9—C12	116.14 (9)
N1—C3—C6	116.85 (9)	C8—C9—C12	121.27 (9)
C2—C3—C6	120.53 (10)	N2—C10—C11	124.74 (10)
N1—C4—C5	124.94 (10)	N2—C10—H10	117.6
N1—C4—H4	117.5	C11—C10—H10	117.6
C5—C4—H4	117.5	C10—C11—C7	119.13 (9)
C4—C5—C1	118.76 (10)	C10—C11—H11	120.4
C4—C5—H5	120.6	C7—C11—H11	120.4
C1—C5—H5	120.6	C9—C12—H12A	109.5
C3—C6—H6A	109.5	C9—C12—H12B	109.5
C3—C6—H6B	109.5	H12A—C12—H12B	109.5
H6A—C6—H6B	109.5	C9—C12—H12C	109.5
C3—C6—H6C	109.5	H12A—C12—H12C	109.5
H6A—C6—H6C	109.5	H12B—C12—H12C	109.5

C5—C1—C2—C3	0.87 (14)	C5—C1—C7—C8	8.36 (15)
C7—C1—C2—C3	−178.28 (9)	C2—C1—C7—C8	−172.52 (9)
C4—N1—C3—C2	0.45 (15)	C11—C7—C8—C9	0.41 (14)
C4—N1—C3—C6	−179.03 (9)	C1—C7—C8—C9	−178.39 (9)
C1—C2—C3—N1	−1.18 (15)	C10—N2—C9—C8	1.31 (15)
C1—C2—C3—C6	178.28 (9)	C10—N2—C9—C12	−178.16 (9)
C3—N1—C4—C5	0.55 (16)	C7—C8—C9—N2	−1.35 (15)
N1—C4—C5—C1	−0.80 (17)	C7—C8—C9—C12	178.10 (9)
C2—C1—C5—C4	0.05 (15)	C9—N2—C10—C11	−0.42 (17)
C7—C1—C5—C4	179.20 (9)	N2—C10—C11—C7	−0.46 (17)
C5—C1—C7—C11	−170.38 (9)	C8—C7—C11—C10	0.43 (14)
C2—C1—C7—C11	8.74 (14)	C1—C7—C11—C10	179.24 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6C···N1ⁱ	0.98	2.73	3.6728 (16)	161

Symmetry code: (i) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₂
M_r	184.24
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	153
a, b, c (Å)	11.7961 (3), 7.6130 (2), 21.2977 (5)
V (Å³)	1912.61 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.54 × 0.24 × 0.14

Data collection
Diffractometer	Bruker X8 APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.924, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	26242, 3233, 2262
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.740

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.139, 0.91
No. of reflections	3233
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.26

Computer programs: APEX2 (Bruker, 2004), SAINT-NT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6C···N1ⁱ	0.98	2.73	3.6728 (16)	161

Symmetry code: (i) −x+2, −y, −z+1.

Acknowledgements

Financial support from the German Research Foundation (DFG) under grant No. We 1016-9/1 is gratefully acknowledged.

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