5,5′-Dimethyl-2,2′-bipyridine

Khoshtarkib, Z.; Ebadi, A.; Ahmadi, R.; Alizadeh, R.

doi:10.1107/S1600536809019151

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1586

doi:10.1107/S1600536809019151

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5,5′-Dimethyl-2,2′-bipyridine

Zeinab Khoshtarkib,^a Amin Ebadi,^b Roya Ahmadi ^a and Robabeh Alizadeh ^c ^*

^aIslamic Azad University, Shahr-e-Rey Branch, Tehran, Iran, ^bDepartment of Chemistry, Islamic Azad University, Kazerun Branch, Kazerun, Fars, Iran, and ^cDamghan University of Basic Sciences, School of Chemistry, Damghan, Iran
^*Correspondence e-mail: alizadeh@dubs.ac.ir

(Received 19 May 2009; accepted 20 May 2009; online 17 June 2009)

The asymmetric unit of the title compound, C₁₂H₁₂N₂, contains two half-molecules related by an inversion center, the planes of their pyridine rings being oriented at a dihedral angle of 69.62 (4)°. In the crystal structure, a π–π contact between the pyridine rings [centroid–centroid distance = 3.895 (3) Å] may stabilize the structure. A weak C—H⋯π interaction is also found.

Related literature

For related structures, see: Ahmadi et al. (2008 ); Albada et al. (2004 ); Amani et al. (2007 ); Kalateh et al. (2008 ); Khalighi et al. (2008 ); Maheshwari et al. (2007 ); Tadayon Pour et al. (2008 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₂H₁₂N₂
M_r = 184.24
Triclinic, $[P \overline 1]$
a = 6.409 (4) Å
b = 7.312 (5) Å
c = 11.533 (8) Å
α = 96.04 (5)°
β = 91.16 (4)°
γ = 105.03 (5)°
V = 518.4 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 298 K
0.50 × 0.41 × 0.29 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
6191 measured reflections
2739 independent reflections
2067 reflections with I > 2σ(I)
R_int = 0.082

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.205
S = 1.08
2739 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯Cg1ⁱ	0.93	2.78	3.669 (3)	160
Symmetry code: (i) -x+1, -y+2, -z+2. Cg1 is the centroid of the N1,C1–C4,C6 ring.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809019151/hk2693sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809019151/hk2693Isup2.hkl

checkCIF report

Comment top

5,5'-Dimethyl-2,2'-bipyridine, (5,5'-dmbipy), is a good bidentate ligand, and numerous complexes with 5,5'-dmbipy have been prepared, such as that of zinc (Khalighi et al., 2008), mercury (Tadayon Pour et al., 2008), iron (Amani et al., 2007), indium (Kalateh et al., 2008), cadmium (Ahmadi et al., 2008), copper (Albada et al., 2004) and platin (Maheshwari et al., 2007). We report herein the crystal structure of the title compound.

The asymmetric unit of the title compound (Fig.1) contains two halves molecules, in which the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (N1/C1-C4/C6) and B (N2/C7-C10/C12) are, of course, planar and they are oriented at a dihedral angle of A/B = 69.62 (4)°.

In the crystal structure (Fig. 2), the π–π contact between the pyridine rings, Cg2—Cg2ⁱ [symmetry code: (i) 1 - x, 2 - y, 2 - z, where Cg2 is centroid of the ring B (N2/C7-C10/C12)] may stabilize the structure, with a centroid-centroid distance of 3.895 (3) Å. There also exists a weak C—H···π interaction (Table 1).

Related literature top

For related structures, see: Ahmadi et al. (2008); Albada et al. (2004); Amani et al. (2007); Kalateh et al. (2008); Khalighi et al. (2008); Maheshwari et al. (2007); Tadayon Pour et al. (2008). For bond-length data, see: Allen et al. (1987). Cg1 is the centroid of the N1,C1–C4,C6 ring.

Experimental top

For the preparation of the title compound, a solution of 5,5'-dimethyl-2,2' -bipyridine (0.15 g, 0.80 mmol) in methanol (15 ml) was added to a solution of BaCl₂.2H₂O, (0.10 g, 0.40 mmol) in water (5 ml) and the resulting colorless solution was stirred for 10 min at 313 K. Then, it was left to evaporate slowly at room temperature. After one week, colorless prismatic crystals of the title compound were isolated.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [symmetry codes: (a) 1 - x, 2 - y, 1 - z, (b) -x, 2 - y, 2 - z].
	Fig. 2. A partial packing diagram of the title compound.

5,5'-Dimethyl-2,2'-bipyridine top

Crystal data top

C₁₂H₁₂N₂	Z = 2
M_r = 184.24	F(000) = 196
Triclinic, P1	D_x = 1.180 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.409 (4) Å	Cell parameters from 1133 reflections
b = 7.312 (5) Å	θ = 1.8–29.3°
c = 11.533 (8) Å	µ = 0.07 mm⁻¹
α = 96.04 (5)°	T = 298 K
β = 91.16 (4)°	Prism, colorless
γ = 105.03 (5)°	0.50 × 0.41 × 0.29 mm
V = 518.4 (6) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2067 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.082
Graphite monochromator	θ_max = 29.3°, θ_min = 1.8°
ϕ and ω scans	h = −8→8
6191 measured reflections	k = −10→10
2739 independent reflections	l = −15→15

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.205	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.1057P)² + 0.0566P] where P = (F_o² + 2F_c²)/3
2739 reflections	(Δ/σ)_max = 0.002
129 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₂H₁₂N₂	γ = 105.03 (5)°
M_r = 184.24	V = 518.4 (6) Å³
Triclinic, P1	Z = 2
a = 6.409 (4) Å	Mo Kα radiation
b = 7.312 (5) Å	µ = 0.07 mm⁻¹
c = 11.533 (8) Å	T = 298 K
α = 96.04 (5)°	0.50 × 0.41 × 0.29 mm
β = 91.16 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2067 reflections with I > 2σ(I)
6191 measured reflections	R_int = 0.082
2739 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.205	H-atom parameters constrained
S = 1.08	Δρ_max = 0.27 e Å⁻³
2739 reflections	Δρ_min = −0.24 e Å⁻³
129 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
N1	0.4778 (2)	0.76393 (19)	0.53822 (13)	0.0604 (4)
N2	0.0741 (2)	0.77876 (19)	0.99037 (14)	0.0656 (4)
C1	0.4223 (2)	0.92544 (19)	0.52837 (12)	0.0486 (3)
C2	0.2280 (2)	0.9529 (2)	0.56860 (14)	0.0579 (4)
H2	0.1916	1.0661	0.5601	0.069*
C3	0.0896 (3)	0.8105 (3)	0.62124 (16)	0.0655 (4)
H3	−0.0407	0.8276	0.6480	0.079*
C4	0.1445 (3)	0.6443 (2)	0.63387 (13)	0.0594 (4)
C5	0.0011 (4)	0.4859 (3)	0.69263 (18)	0.0797 (6)
H5C	0.0475	0.3716	0.6761	0.096*
H5B	−0.1459	0.4638	0.6637	0.096*
H5A	0.0105	0.5218	0.7755	0.096*
C6	0.3403 (3)	0.6293 (2)	0.58998 (16)	0.0641 (4)
H6	0.3793	0.5168	0.5971	0.077*
C7	0.0828 (2)	0.96057 (19)	1.02576 (12)	0.0513 (4)
C8	0.2406 (3)	1.0695 (2)	1.10747 (14)	0.0632 (4)
H8	0.2442	1.1958	1.1315	0.076*
C9	0.3905 (3)	0.9892 (3)	1.15227 (15)	0.0679 (5)
H9	0.4973	1.0614	1.2066	0.082*
C10	0.3838 (3)	0.8018 (2)	1.11714 (14)	0.0600 (4)
C11	0.5426 (3)	0.7065 (3)	1.1636 (2)	0.0793 (5)
H11C	0.5070	0.5755	1.1305	0.095*
H11B	0.5374	0.7130	1.2470	0.095*
H11A	0.6856	0.7699	1.1431	0.095*
C12	0.2214 (3)	0.7049 (2)	1.03580 (18)	0.0686 (5)
H12	0.2146	0.5782	1.0109	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0614 (8)	0.0537 (7)	0.0719 (8)	0.0235 (6)	0.0113 (6)	0.0111 (6)
N2	0.0615 (8)	0.0483 (7)	0.0819 (9)	0.0103 (6)	−0.0066 (7)	−0.0034 (6)
C1	0.0470 (7)	0.0513 (7)	0.0491 (7)	0.0170 (6)	−0.0020 (5)	0.0031 (5)
C2	0.0500 (8)	0.0626 (9)	0.0669 (9)	0.0231 (6)	0.0037 (6)	0.0129 (7)
C3	0.0508 (8)	0.0790 (11)	0.0696 (9)	0.0200 (8)	0.0091 (7)	0.0131 (8)
C4	0.0607 (9)	0.0615 (9)	0.0513 (7)	0.0076 (7)	0.0001 (6)	0.0067 (6)
C5	0.0809 (13)	0.0784 (12)	0.0723 (11)	0.0034 (10)	0.0095 (9)	0.0176 (9)
C6	0.0734 (10)	0.0539 (8)	0.0690 (9)	0.0212 (7)	0.0104 (8)	0.0125 (7)
C7	0.0527 (7)	0.0454 (7)	0.0523 (7)	0.0062 (6)	0.0075 (6)	0.0052 (5)
C8	0.0722 (10)	0.0521 (8)	0.0608 (8)	0.0129 (7)	−0.0068 (7)	−0.0031 (6)
C9	0.0727 (10)	0.0664 (10)	0.0595 (9)	0.0131 (8)	−0.0108 (7)	0.0003 (7)
C10	0.0567 (8)	0.0625 (9)	0.0620 (8)	0.0137 (7)	0.0086 (7)	0.0158 (7)
C11	0.0705 (11)	0.0809 (13)	0.0911 (13)	0.0247 (10)	−0.0004 (10)	0.0194 (10)
C12	0.0640 (10)	0.0500 (8)	0.0896 (12)	0.0137 (7)	−0.0015 (8)	0.0017 (8)

Geometric parameters (Å, º) top

C1—N1	1.334 (2)	C7—N2	1.335 (2)
C1—C2	1.393 (2)	C7—C8	1.389 (2)
C1—C1ⁱ	1.491 (3)	C7—C7ⁱⁱ	1.475 (3)
C2—C3	1.384 (3)	C8—C9	1.368 (3)
C2—H2	0.9300	C8—H8	0.9300
C3—C4	1.371 (3)	C9—C10	1.377 (3)
C3—H3	0.9300	C9—H9	0.9300
C4—C6	1.389 (3)	C10—C12	1.380 (3)
C4—C5	1.511 (3)	C10—C11	1.494 (3)
C5—H5C	0.9600	C11—H11C	0.9600
C5—H5B	0.9600	C11—H11B	0.9600
C5—H5A	0.9600	C11—H11A	0.9600
C6—N1	1.340 (2)	C12—N2	1.327 (2)
C6—H6	0.9300	C12—H12	0.9300

N1—C1—C2	121.57 (15)	N2—C7—C7ⁱⁱ	116.86 (16)
N1—C1—C1ⁱ	116.75 (16)	C8—C7—C7ⁱⁱ	121.84 (17)
C2—C1—C1ⁱ	121.68 (16)	C9—C8—C7	119.40 (16)
C3—C2—C1	119.51 (15)	C9—C8—H8	120.3
C3—C2—H2	120.2	C7—C8—H8	120.3
C1—C2—H2	120.2	C8—C9—C10	120.16 (16)
C4—C3—C2	119.99 (16)	C8—C9—H9	119.9
C4—C3—H3	120.0	C10—C9—H9	119.9
C2—C3—H3	120.0	C9—C10—C12	116.32 (17)
C3—C4—C6	116.29 (16)	C9—C10—C11	122.45 (18)
C3—C4—C5	122.09 (17)	C12—C10—C11	121.22 (17)
C6—C4—C5	121.62 (17)	C10—C11—H11C	109.5
C4—C5—H5C	109.5	C10—C11—H11B	109.5
C4—C5—H5B	109.5	H11C—C11—H11B	109.5
H5C—C5—H5B	109.5	C10—C11—H11A	109.5
C4—C5—H5A	109.5	H11C—C11—H11A	109.5
H5C—C5—H5A	109.5	H11B—C11—H11A	109.5
H5B—C5—H5A	109.5	N2—C12—C10	124.98 (16)
N1—C6—C4	125.26 (16)	N2—C12—H12	117.5
N1—C6—H6	117.4	C10—C12—H12	117.5
C4—C6—H6	117.4	C1—N1—C6	117.36 (15)
N2—C7—C8	121.30 (15)	C12—N2—C7	117.84 (15)

N1—C1—C2—C3	0.7 (2)	C8—C9—C10—C12	0.4 (3)
C1ⁱ—C1—C2—C3	−179.66 (16)	C8—C9—C10—C11	−179.67 (17)
C1—C2—C3—C4	0.3 (3)	C9—C10—C12—N2	−0.2 (3)
C2—C3—C4—C6	−0.9 (3)	C11—C10—C12—N2	179.92 (17)
C2—C3—C4—C5	178.87 (16)	C2—C1—N1—C6	−0.9 (2)
C3—C4—C6—N1	0.7 (3)	C1ⁱ—C1—N1—C6	179.44 (15)
C5—C4—C6—N1	−179.06 (16)	C4—C6—N1—C1	0.2 (3)
N2—C7—C8—C9	0.2 (3)	C10—C12—N2—C7	−0.1 (3)
C7ⁱⁱ—C7—C8—C9	−179.88 (17)	C8—C7—N2—C12	0.0 (3)
C7—C8—C9—C10	−0.5 (3)	C7ⁱⁱ—C7—N2—C12	−179.87 (17)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···Cg1ⁱⁱⁱ	0.93	2.78	3.669 (3)	160

Symmetry code: (iii) −x+1, −y+2, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₂
M_r	184.24
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	6.409 (4), 7.312 (5), 11.533 (8)
α, β, γ (°)	96.04 (5), 91.16 (4), 105.03 (5)
V (Å³)	518.4 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.50 × 0.41 × 0.29

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6191, 2739, 2067
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.688

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.205, 1.08
No. of reflections	2739
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.24

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···Cg1ⁱ	0.93	2.78	3.669 (3)	160

Symmetry code: (i) −x+1, −y+2, −z+2.

Acknowledgements

We are grateful to Damghan University of Basic Sciences for financial support.

References

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