5,5′-Bis[(trimethyl­silyl)meth­yl]-2,2′-bipyridine

Davies, M.S.; Glasson, C.R.K.; Meehan, G.V.

doi:10.1107/S1600536807052154

organic compounds

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Volume 64| Part 2| February 2008| Page o364

doi:10.1107/S1600536807052154

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5,5′-Bis[(trimethylsilyl)methyl]-2,2′-bipyridine

Murray S. Davies,^a ^* Christopher R. K. Glasson ^a and George V. Meehan ^a

^aSchool of Pharmacy and Molecular Sciences, James Cook University, Townsville, QLD 4811, Australia
^*Correspondence e-mail: murray.davies@jcu.edu.au

(Received 17 May 2007; accepted 21 October 2007; online 4 January 2008)

The molecule of the title compound, C₁₈H₂₈N₂Si₂, occupies a special position on an inversion centre. The Si—CH₂—C(ipso) plane is approximately orthogonal to the plane of the pyridine rings, the corresponding dihedral angle being 82.0 (2)°.

Related literature

For related chemistry, see: Fraser et al. (1997 ); Hochwimmer et al.(1998 ); Perkins et al. (2006 ); Schubert et al. (1998 ). For recently reported similar structures, see: Khan et al. (2004 ); Lindoy et al. (2204). For related literature, see: Lindoy et al. (2004 ).

Experimental

Crystal data

C₁₈H₂₈N₂Si₂
M_r = 328.60
Triclinic, $[P \overline 1]$
a = 6.279 (3) Å
b = 6.575 (3) Å
c = 14.030 (6) Å
α = 76.599 (7)°
β = 88.415 (7)°
γ = 64.859 (6)°
V = 508.4 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 293 (2) K
0.25 × 0.15 × 0.10 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.973, T_max = 0.974
4192 measured reflections
2057 independent reflections
1294 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.192
S = 1.04
2057 reflections
123 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT and XPREP (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807052154/ya2054sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807052154/ya2054Isup2.hkl

checkCIF report

Comment top

As a part of our work on cryptates derived from 5,5'-disubstituted-2,2'-bipyridines (Perkins et al., 2006), we have studied methyl functionalization reactions of 5,5'-dimethyl-2,2'-bipyridine as a model for similar chemistry proposed for its more complex analogue, 5,5"'-dimethyl-2,2':5',5":2",2"'-quaterpyridine. In contrast to the previous report by Schubert et al. (1998), we have been able to promote bis-lithiation of 5,5'-dimethyl-2,2'-bipyridine with lithium diisopropylamide (LDA) in THF by use of a coordinating co-solvent, hexamethylphosphoramide (HMPA). Subsequent bis-silylation with trimethylsilyl chloride afforded (I) in good yield.

The molecule of the title compound (Fig.1) occupies a special position in the inversion centre. The SiMe₃ groups are trans disposed relative to the plane of the two pyridyl rings giving the molecule a zigzag shape (Fig. 2). The dihedral angle between the plane of the bipyridyl rings, and that of trimethylsilylmethyl substituent, as defined by Si1—C6—C4, is 82.0 (2)°.

The molecules in crystal show stacking arrangement with methylenetrimethylsilyl groups of the adjacent molecules oriented in the same direction (Fig. 2).

Related literature top

For related chemistry see Fraser et al. (1997); Hochwimmer et al.(1998); Perkins et al. (2006); Schubert et al. (1998). For recently reported similar structures see Khan et al. (2004); Lindoy et al. (2204). For related literature, Lindoy et al. (2004).

Experimental top

A solution of LDA, prepared from n-BuLi (1.9 M, 1.42 ml, 2.7 mmol), and dry diisopropylamine (0.42 ml, 3.0 mmol) in dry THF (8 ml) was cooled to -78° C and a solution of 5,5'-dimethyl-2,2'-bipyridine (100 mg, 0.54 mmol) and dry HMPA (1.13 ml, 6.5 mmol) in dry THF (5 ml) was added dropwise, resulting in a deep red/brown opaque reaction mixture. This was stirred for 2 h, then trimethylsilyl chloride (217 mg, 2.0 mmol) was added, and the stirring was continued for 0.5 h more at -78° C. The resulting transparent red solution was quenched with 2 ml of absolute ethanol. Fortuitously, this solution precipitated crystals of (I) suitable for X-ray structure determination when its volume was reduced by rotary evaporation. To the remaining material, saturated NaHCO₃ (10 ml) was added and the product was extracted with ethyl acetate (3 × 40 ml). The combined organic fractions were dried over anhydrous Na₂SO₄ and the solvent removed under vacuum. The resulting solid was purified by chromatography on deactivated silica gel, affording (I) as a greasy white solid (142 mg, 80%). δH (300 MHz; CDCl₃) 0.02 (18H, s, SiMe₃) 2.12 (4H, s, CH₂), 7.45 (2H, dd, J = 7.8, 1.8 Hz, H-4,4'), 8.22 (2H, d, J = 7.8 Hz, H-3,3'), 8.34 (2H, d, 1.8 Hz, H-6,6'); δC (75 MHz; CDCl₃) 2.06 (SiMe₃), 23.92 (CH₂), 120.16, 136.11, 136.18, 148.22, 152.21.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001) and XPREP (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Burnett & Johnson (1996); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. ORTEP (Burnett and Johnson (1996), Farrugia (1997)) drawing of (I) with displacement ellipsoids shown at 50% probability level. Only the non-hydrogen atoms in the asymmetric unit are labelled; unlabelled atoms are derived from the corresponding labelled atoms by means of the (1 - x, 3 - y, -z) transformation.
	Fig. 2. Crystal packing diagram of (I) viewed down the a axis of the crystal.

5,5'-Bis[(trimethylsilyl)methyl]-2,2'-bipyridine top

Crystal data top

C₁₈H₂₈N₂Si₂	Z = 1
M_r = 328.60	F(000) = 178
Triclinic, P1	D_x = 1.073 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 6.279 (3) Å	Cell parameters from 1147 reflections
b = 6.575 (3) Å	θ = 0.9–26.4°
c = 14.030 (6) Å	µ = 0.17 mm⁻¹
α = 76.599 (7)°	T = 293 K
β = 88.415 (7)°	Prism, colourless
γ = 64.859 (6)°	0.25 × 0.15 × 0.10 mm
V = 508.4 (4) Å³

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2057 independent reflections
Radiation source: fine-focus sealed tube	1294 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ϕ and ω scans	θ_max = 26.4°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.973, T_max = 0.974	k = −8→8
4192 measured reflections	l = −17→17

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.192	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.093P)²] where P = (F_o² + 2F_c²)/3
2057 reflections	(Δ/σ)_max = 0.007
123 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₈H₂₈N₂Si₂	γ = 64.859 (6)°
M_r = 328.60	V = 508.4 (4) Å³
Triclinic, P1	Z = 1
a = 6.279 (3) Å	Mo Kα radiation
b = 6.575 (3) Å	µ = 0.17 mm⁻¹
c = 14.030 (6) Å	T = 293 K
α = 76.599 (7)°	0.25 × 0.15 × 0.10 mm
β = 88.415 (7)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2057 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1294 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.974	R_int = 0.042
4192 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.192	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.36 e Å⁻³
2057 reflections	Δρ_min = −0.16 e Å⁻³
123 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. An empirical absorption correction determined with SADABS (Sheldrick, 1996) was applied to the data. The data integration and reduction were undertaken with SAINT and XPREP (Bruker, 2001). The data reduction included the application of Lorentz and polarization corrections. The reflection data were merged including Fridel opposites. The structure was solved in the space group P-1 by direct methods with SHELXS97 (Sheldrick, 1997) within the WinG-X (Farrugia, 1999) interface and extended and refined with SHELXL97 (Sheldrick 1997). Anisotropic thermal parameters were refined for the non-hydrogen atoms. All aromatic and methylene H atoms were located and refined with isotropic thermal parameters. Methyl H atoms were constrained as riding atoms, fixed to the parent C atom with a distance of 0.96 Å. U_iso values were set to 1.5 U_eq of the parent C atom.

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
Si1	0.78941 (12)	0.61211 (12)	0.82038 (5)	0.0664 (3)
C1	0.5188 (4)	1.3836 (4)	0.52943 (15)	0.0544 (5)
N1	0.7386 (3)	1.2150 (4)	0.53910 (15)	0.0681 (6)
C4	0.6028 (4)	0.9417 (4)	0.63513 (16)	0.0594 (6)
C2	0.3355 (4)	1.3408 (5)	0.57193 (18)	0.0646 (7)
C5	0.7751 (5)	1.0028 (5)	0.59098 (19)	0.0686 (7)
C6	0.6608 (5)	0.6974 (5)	0.69012 (18)	0.0660 (7)
C3	0.3787 (5)	1.1207 (5)	0.62426 (18)	0.0673 (7)
C9	0.5840 (5)	0.8130 (5)	0.8897 (2)	0.0951 (9)
H9A	0.5359	0.9699	0.8525	0.143*
H9B	0.6620	0.7910	0.9517	0.143*
H9C	0.4478	0.7823	0.9009	0.143*
C7	0.8328 (6)	0.3086 (5)	0.8742 (2)	0.1086 (11)
H7B	0.8969	0.2606	0.9412	0.163*
H7C	0.9400	0.2082	0.8371	0.163*
H7A	0.6838	0.3008	0.8719	0.163*
C8	1.0830 (5)	0.6243 (6)	0.8206 (2)	0.1070 (11)
H8A	1.0637	0.7764	0.7865	0.160*
H8B	1.1908	0.5123	0.7882	0.160*
H8C	1.1446	0.5904	0.8871	0.160*
H6A	0.773 (4)	0.589 (4)	0.6581 (18)	0.074 (8)*
H6B	0.513 (5)	0.676 (4)	0.6947 (18)	0.087 (8)*
H5	0.923 (4)	0.883 (4)	0.5873 (17)	0.075 (7)*
H3	0.243 (5)	1.082 (4)	0.6515 (19)	0.093 (8)*
H2	0.179 (4)	1.470 (4)	0.5684 (16)	0.067 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Si1	0.0679 (5)	0.0709 (5)	0.0656 (5)	−0.0393 (4)	0.0016 (3)	−0.0070 (3)
C1	0.0476 (13)	0.0684 (14)	0.0500 (12)	−0.0274 (12)	0.0054 (10)	−0.0148 (10)
N1	0.0537 (12)	0.0677 (13)	0.0784 (14)	−0.0267 (10)	0.0164 (10)	−0.0096 (11)
C4	0.0635 (15)	0.0713 (15)	0.0509 (12)	−0.0374 (13)	0.0049 (11)	−0.0123 (11)
C2	0.0457 (13)	0.0728 (17)	0.0686 (15)	−0.0243 (13)	0.0056 (11)	−0.0077 (13)
C5	0.0546 (15)	0.0663 (16)	0.0765 (17)	−0.0221 (13)	0.0141 (12)	−0.0104 (14)
C6	0.0720 (18)	0.0705 (16)	0.0665 (16)	−0.0400 (15)	0.0085 (13)	−0.0187 (13)
C3	0.0567 (15)	0.0804 (18)	0.0696 (16)	−0.0381 (14)	0.0088 (12)	−0.0107 (13)
C9	0.108 (2)	0.116 (2)	0.0779 (19)	−0.060 (2)	0.0187 (17)	−0.0319 (18)
C7	0.127 (3)	0.084 (2)	0.110 (2)	−0.052 (2)	−0.006 (2)	−0.0014 (18)
C8	0.080 (2)	0.136 (3)	0.113 (3)	−0.061 (2)	−0.0108 (18)	−0.015 (2)

Geometric parameters (Å, º) top

Si1—C9	1.853 (3)	C5—H5	0.94 (2)
Si1—C7	1.864 (3)	C6—H6A	0.95 (2)
Si1—C6	1.878 (3)	C6—H6B	1.00 (3)
Si1—C8	1.879 (3)	C3—H3	1.03 (3)
C1—N1	1.339 (3)	C9—H9A	0.9600
C1—C2	1.385 (3)	C9—H9B	0.9600
C1—C1ⁱ	1.483 (4)	C9—H9C	0.9600
N1—C5	1.340 (3)	C7—H7B	0.9600
C4—C3	1.382 (4)	C7—H7C	0.9600
C4—C5	1.390 (3)	C7—H7A	0.9600
C4—C6	1.501 (4)	C8—H8A	0.9600
C2—C3	1.376 (3)	C8—H8B	0.9600
C2—H2	0.98 (2)	C8—H8C	0.9600

C9—Si1—C7	111.14 (16)	Si1—C6—H6B	105.3 (15)
C9—Si1—C6	109.21 (14)	H6A—C6—H6B	110 (2)
C7—Si1—C6	107.55 (14)	C2—C3—C4	120.9 (2)
C9—Si1—C8	110.33 (15)	C2—C3—H3	120.9 (15)
C7—Si1—C8	109.30 (16)	C4—C3—H3	118.1 (15)
C6—Si1—C8	109.25 (13)	Si1—C9—H9A	109.5
N1—C1—C2	121.3 (2)	Si1—C9—H9B	109.5
N1—C1—C1ⁱ	116.9 (2)	H9A—C9—H9B	109.5
C2—C1—C1ⁱ	121.8 (2)	Si1—C9—H9C	109.5
C1—N1—C5	117.7 (2)	H9A—C9—H9C	109.5
C3—C4—C5	115.2 (2)	H9B—C9—H9C	109.5
C3—C4—C6	123.4 (2)	Si1—C7—H7B	109.5
C5—C4—C6	121.4 (2)	Si1—C7—H7C	109.5
C3—C2—C1	119.6 (2)	H7B—C7—H7C	109.5
C3—C2—H2	120.8 (13)	Si1—C7—H7A	109.5
C1—C2—H2	119.5 (13)	H7B—C7—H7A	109.5
N1—C5—C4	125.4 (2)	H7C—C7—H7A	109.5
N1—C5—H5	115.7 (15)	Si1—C8—H8A	109.5
C4—C5—H5	118.0 (15)	Si1—C8—H8B	109.5
C4—C6—Si1	115.70 (17)	H8A—C8—H8B	109.5
C4—C6—H6A	111.0 (14)	Si1—C8—H8C	109.5
Si1—C6—H6A	105.7 (14)	H8A—C8—H8C	109.5
C4—C6—H6B	108.8 (15)	H8B—C8—H8C	109.5

Symmetry code: (i) −x+1, −y+3, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₈H₂₈N₂Si₂
M_r	328.60
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.279 (3), 6.575 (3), 14.030 (6)
α, β, γ (°)	76.599 (7), 88.415 (7), 64.859 (6)
V (Å³)	508.4 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.17
Crystal size (mm)	0.25 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.973, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	4192, 2057, 1294
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.192, 1.04
No. of reflections	2057
No. of parameters	123
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.16

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001) and XPREP (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and Burnett & Johnson (1996), WinGX (Farrugia, 1999).

Acknowledgements

The authors acknowledge financial support by the Australian Research Council.

References

Bruker (2001). SMART, SAINT and XPREP. Bruker Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Oak Ridge, Tennessee, U. S. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Fraser, C. L., Anastasi, N. R. & Lamba, J. J. S. (1997). J. Org. Chem. 62, 9314–9317. Web of Science CrossRef CAS Google Scholar
Hochwimmer, G., Nuyken, O. & Schubert, U. S. (1998). Macromol. Rapid Commun. 19, 309–313. CAS Google Scholar
Khan, M. S., Ahrens, B., Male, L. & Raithby, P. R. (2004). Acta Cryst. E60, o915–o916. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lindoy, L. F., McMurtrie, J. C. & Price, J. R. (2004). Acta Cryst. E60, o886–o888. CSD CrossRef IUCr Journals Google Scholar
Perkins, D. F., Lindoy, L. F., McAuley, A., Meehan, G. V. & Turner, P. (2006). Proc. Natl Acad. Sci. USA, 103, 532–537. Web of Science CSD CrossRef PubMed CAS Google Scholar
Schubert, U. S., Eschbaumer, C. & Hochwimmer, G. (1998). Tetrahedron Lett. 39, 8643–8644. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS: University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar