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access4,4′-Bis(trimethylsilyl)-2,2′-bipyridine
aSchool of Chemical and Material Engineering, Jiangnan University, 1800 Lihu Road, Wuxi, Jiangsu Province 214122, People's Republic of China
*Correspondence e-mail: cgzheng@jiangnan.edu.cn
In the molecule of title compound, C16H24N2Si2, the pyridine rings are nearly planar (r.m.s. deviation = 0.002 Å).
Related literature
For the structure of 5,5′-bis(trimethylsilyl)-2,2′-bipyridines, see: Stange et al. (2000![[Stange, A. F., Tokura, S. & Kira, M. (2000). J. Organomet. Chem. 612, 117-124.]](../../../../../../logos/arrows/e_arr.gif "Stange, A. F., Tokura, S. & Kira, M. (2000). J. Organomet. Chem. 612, 117-124.")
). For the structure of 4-trimethylsilylpyridine, see: Postigo & Rossi (2001). For synthetic procedure to obtain 4,4′-bis(methoxyl)-2,2′-bipyridine, see: Wenkert & Woodward (1983).
![[Scheme 1]](rk2303scheme1.gif)
Experimental
Crystal data
|
Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.
Supporting information
contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811043704/rk2303sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811043704/rk2303Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536811043704/rk2303Isup3.cml
All the reagents and solvents empolyed were commercially available. The title compound was synthesized by using 2,2'-bipyridine as the starting material with successive polystepreactions (Wenkert & Woodward, 1983). The final product was dissolved in the solution of methanol and methylene chloride, which diffused slowly. After seven days, colourless block-shaped crystals were obtained which were suitable for X-ray analysis.
All H atoms were placed in geometrically idealized positions. H atoms of bipyridine constrained to ride on their parent atoms with C—H = 0.94 Å and refined with Uiso(H) = 1.2Uiso(C). The H atoms of methyl groups constrained to ride on their parent atoms with C—H = 0.97 Å and refined with Uiso(H) = 1.5Uiso(C).
Derivatives of 2,2'-bipyridine have received much attention due to their potential to form polypyridyl metal complexes, particularly of ruthenium and rhenium which have diverse applications. The photochemical and redox properties of these complexes can be varied through appropriate substitution on the pyridine rings. The derivatization of a 2,2'-bipyridine ligand with electron donating/withdrawing groups in the 4,4'-positions has been a popular means of controlling the of transition metal bipyridine complexes. The 4,4'-disubstitution can also offers no steric complications on complexation. The research about synthesis and properties of pyridine rings interconnected with strong electron-donating groups, as well as trimethysilyl group, was recently reported (Stange et al., 2000; Postigo & Rossi, 2001). However, there are no reports on 4,4'-bis(trimethylsilyl)-2,2'-bipyridine. Herein, we report of the title compound.
The molecule is placed in centre of symmetry and nealy flat (Fig. 1) as the C—Si is co-planar with the aromatic rings. The torsion angle for N1—C4—C4i—C5i = 0°. In crystal, molecules are connected by weak non-classical intermolecular C3–H3···N1ii hydrogen bonds with parameters C3···N1ii = 3.626 (2) Å, H3···N1ii = 2.714 Å and angle C3–H3···N1ii = 164.3°. Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) -x + 1, y - 1/2, -z + 1/2.
For the structure of 5,5'-bis(trimethylsilyl)-2,2'-bipyridines, see: Stange et al. (2000). For the structure of 4-trimethylsilylpyridine, see: Postigo & Rossi (2001). For synthetic procedure to obtain 4,4'-bis(methoxyl)-2,2'-bipyridine, see: Wenkert & Woodward (1983).
Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./rk2303fig1thm.gif) | Fig. 1. Molecular structure of title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 40% probability level. H atoms are presented as a small spheres of arbitrary radius. Symmetry code: (i) -x + 1, -y + 1, -z. |
| C16H24N2Si2 | F(000) = 324 |
| Mr = 300.55 | Dx = 1.117 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71075 Å |
| Hall symbol: -P 2ybc | Cell parameters from 3568 reflections |
| a = 13.154 (4) Å | θ = 3.2–27.5° |
| b = 6.4599 (16) Å | µ = 0.19 mm−1 |
| c = 11.280 (3) Å | T = 223 K |
| β = 111.222 (6)° | Block, colourless |
| V = 893.5 (4) Å3 | 0.50 × 0.30 × 0.20 mm |
| Z = 2 |
| Rigaku Saturn CCD diffractometer | 1649 independent reflections |
| Radiation source: fine-focus sealed tube | 1364 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.027 |
| Detector resolution: 14.63 pixels mm-1 | θmax = 25.5° |
| ω scans | h = −13→15 |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −7→7 |
| Tmin = 0.869, Tmax = 0.963 | l = −13→12 |
| 4311 measured reflections |
| 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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.125 | H-atom parameters constrained |
| S = 1.08 | w = 1/[σ2(Fo2) + (0.0734P)2 + 0.0832P] where P = (Fo2 + 2Fc2)/3 |
| 1649 reflections | (Δ/σ)max < 0.001 |
| 95 parameters | Δρmax = 0.25 e Å−3 |
| 2 restraints | Δρmin = −0.26 e Å−3 |
| C16H24N2Si2 | V = 893.5 (4) Å3 |
| Mr = 300.55 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 13.154 (4) Å | µ = 0.19 mm−1 |
| b = 6.4599 (16) Å | T = 223 K |
| c = 11.280 (3) Å | 0.50 × 0.30 × 0.20 mm |
| β = 111.222 (6)° |
| Rigaku Saturn CCD diffractometer | 1649 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1364 reflections with I > 2σ(I) |
| Tmin = 0.869, Tmax = 0.963 | Rint = 0.027 |
| 4311 measured reflections |
| R[F2 > 2σ(F2)] = 0.046 | 2 restraints |
| wR(F2) = 0.125 | H-atom parameters constrained |
| S = 1.08 | Δρmax = 0.25 e Å−3 |
| 1649 reflections | Δρmin = −0.26 e Å−3 |
| 95 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > σF2 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. |
| x | y | z | Uiso*/Ueq | ||
| Si1 | 0.80366 (4) | 0.08423 (9) | 0.02023 (5) | 0.0405 (2) | |
| N1 | 0.49321 (13) | 0.2932 (2) | 0.10461 (14) | 0.0366 (4) | |
| C1 | 0.68120 (15) | 0.1675 (3) | 0.05735 (17) | 0.0356 (5) | |
| C2 | 0.64022 (16) | 0.0538 (3) | 0.13516 (18) | 0.0383 (5) | |
| H2 | 0.6754 | −0.0686 | 0.1740 | 0.046* | |
| C3 | 0.54791 (17) | 0.1206 (3) | 0.15535 (18) | 0.0391 (5) | |
| H3 | 0.5221 | 0.0400 | 0.2079 | 0.047* | |
| C4 | 0.53132 (15) | 0.4054 (3) | 0.02861 (17) | 0.0311 (4) | |
| C5 | 0.62411 (16) | 0.3477 (3) | 0.00480 (17) | 0.0353 (5) | |
| H5 | 0.6487 | 0.4314 | −0.0475 | 0.042* | |
| C6 | 0.8938 (2) | −0.0751 (5) | 0.1542 (3) | 0.0724 (9) | |
| H6A | 0.8573 | −0.2038 | 0.1584 | 0.109* | |
| H6B | 0.9101 | 0.0003 | 0.2333 | 0.109* | |
| H6C | 0.9611 | −0.1049 | 0.1408 | 0.109* | |
| C7 | 0.7569 (2) | −0.0682 (4) | −0.1293 (2) | 0.0576 (6) | |
| H7A | 0.8197 | −0.1205 | −0.1457 | 0.086* | |
| H7B | 0.7140 | 0.0195 | −0.1993 | 0.086* | |
| H7C | 0.7127 | −0.1834 | −0.1210 | 0.086* | |
| C8 | 0.8778 (2) | 0.3196 (4) | 0.0009 (3) | 0.0687 (7) | |
| H8A | 0.8948 | 0.4060 | 0.0760 | 0.103* | |
| H8B | 0.8323 | 0.3964 | −0.0732 | 0.103* | |
| H8C | 0.9448 | 0.2790 | −0.0101 | 0.103* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Si1 | 0.0418 (4) | 0.0433 (4) | 0.0397 (4) | 0.0085 (2) | 0.0189 (3) | 0.0001 (2) |
| N1 | 0.0437 (9) | 0.0376 (9) | 0.0332 (8) | 0.0016 (7) | 0.0195 (7) | 0.0033 (7) |
| C1 | 0.0387 (10) | 0.0352 (10) | 0.0323 (9) | 0.0035 (8) | 0.0120 (8) | −0.0037 (8) |
| C2 | 0.0451 (11) | 0.0361 (10) | 0.0339 (10) | 0.0059 (9) | 0.0144 (9) | 0.0028 (8) |
| C3 | 0.0496 (12) | 0.0373 (11) | 0.0347 (10) | −0.0001 (9) | 0.0202 (9) | 0.0051 (8) |
| C4 | 0.0368 (10) | 0.0307 (9) | 0.0277 (9) | −0.0011 (8) | 0.0139 (8) | −0.0013 (7) |
| C5 | 0.0410 (10) | 0.0377 (10) | 0.0317 (9) | 0.0005 (8) | 0.0185 (8) | −0.0008 (8) |
| C6 | 0.0688 (17) | 0.093 (2) | 0.0590 (15) | 0.0392 (15) | 0.0270 (14) | 0.0160 (14) |
| C7 | 0.0642 (15) | 0.0625 (15) | 0.0532 (13) | 0.0052 (12) | 0.0297 (12) | −0.0119 (11) |
| C8 | 0.0544 (14) | 0.0656 (16) | 0.097 (2) | −0.0045 (13) | 0.0409 (14) | −0.0089 (15) |
| Si1—C7 | 1.855 (2) | C4—C4i | 1.485 (3) |
| Si1—C6 | 1.858 (2) | C5—H5 | 0.9400 |
| Si1—C8 | 1.861 (3) | C6—H6A | 0.9700 |
| Si1—C1 | 1.884 (2) | C6—H6B | 0.9700 |
| N1—C3 | 1.338 (2) | C6—H6C | 0.9700 |
| N1—C4 | 1.350 (2) | C7—H7A | 0.9700 |
| C1—C2 | 1.394 (3) | C7—H7B | 0.9700 |
| C1—C5 | 1.396 (3) | C7—H7C | 0.9700 |
| C2—C3 | 1.383 (3) | C8—H8A | 0.9700 |
| C2—H2 | 0.9400 | C8—H8B | 0.9700 |
| C3—H3 | 0.9400 | C8—H8C | 0.9700 |
| C4—C5 | 1.392 (3) | ||
| C7—Si1—C6 | 110.44 (13) | C4—C5—H5 | 119.5 |
| C7—Si1—C8 | 110.03 (13) | C1—C5—H5 | 119.5 |
| C6—Si1—C8 | 109.91 (14) | Si1—C6—H6A | 109.5 |
| C7—Si1—C1 | 108.97 (10) | Si1—C6—H6B | 109.5 |
| C6—Si1—C1 | 108.84 (11) | H6A—C6—H6B | 109.5 |
| C8—Si1—C1 | 108.60 (10) | Si1—C6—H6C | 109.5 |
| C3—N1—C4 | 116.95 (17) | H6A—C6—H6C | 109.5 |
| C2—C1—C5 | 115.83 (18) | H6B—C6—H6C | 109.5 |
| C2—C1—Si1 | 123.10 (15) | Si1—C7—H7A | 109.5 |
| C5—C1—Si1 | 121.05 (15) | Si1—C7—H7B | 109.5 |
| C3—C2—C1 | 120.11 (18) | H7A—C7—H7B | 109.5 |
| C3—C2—H2 | 119.9 | Si1—C7—H7C | 109.5 |
| C1—C2—H2 | 119.9 | H7A—C7—H7C | 109.5 |
| N1—C3—C2 | 123.92 (18) | H7B—C7—H7C | 109.5 |
| N1—C3—H3 | 118.0 | Si1—C8—H8A | 109.5 |
| C2—C3—H3 | 118.0 | Si1—C8—H8B | 109.5 |
| N1—C4—C5 | 122.12 (17) | H8A—C8—H8B | 109.5 |
| N1—C4—C4i | 116.3 (2) | Si1—C8—H8C | 109.5 |
| C5—C4—C4i | 121.6 (2) | H8A—C8—H8C | 109.5 |
| C4—C5—C1 | 121.06 (18) | H8B—C8—H8C | 109.5 |
| C7—Si1—C1—C2 | 92.79 (18) | C4—N1—C3—C2 | 0.6 (3) |
| C6—Si1—C1—C2 | −27.7 (2) | C1—C2—C3—N1 | −0.4 (3) |
| C8—Si1—C1—C2 | −147.35 (18) | C3—N1—C4—C5 | −0.9 (3) |
| C7—Si1—C1—C5 | −85.66 (18) | C3—N1—C4—C4i | 179.05 (18) |
| C6—Si1—C1—C5 | 153.85 (17) | N1—C4—C5—C1 | 1.1 (3) |
| C8—Si1—C1—C5 | 34.20 (19) | C4i—C4—C5—C1 | −178.86 (19) |
| C5—C1—C2—C3 | 0.5 (3) | C2—C1—C5—C4 | −0.9 (3) |
| Si1—C1—C2—C3 | −178.01 (14) | Si1—C1—C5—C4 | 177.70 (14) |
| Symmetry code: (i) −x+1, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C3—H3···N1ii | 0.94 | 2.71 | 3.626 (2) | 164 |
| Symmetry code: (ii) −x+1, y−1/2, −z+1/2. |
Experimental details
| Crystal data | |
| Chemical formula | C16H24N2Si2 |
| Mr | 300.55 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 223 |
| a, b, c (Å) | 13.154 (4), 6.4599 (16), 11.280 (3) |
| β (°) | 111.222 (6) |
| V (Å3) | 893.5 (4) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.19 |
| Crystal size (mm) | 0.50 × 0.30 × 0.20 |
| Data collection | |
| Diffractometer | Rigaku Saturn CCD |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
| Tmin, Tmax | 0.869, 0.963 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 4311, 1649, 1364 |
| Rint | 0.027 |
| (sin θ/λ)max (Å−1) | 0.606 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.125, 1.08 |
| No. of reflections | 1649 |
| No. of parameters | 95 |
| No. of restraints | 2 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.25, −0.26 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
| D—H···A | D—H | H···A | D···A | D—H···A |
| C3—H3···N1i | 0.94 | 2.71 | 3.626 (2) | 164.3 |
| Symmetry code: (i) −x+1, y−1/2, −z+1/2. |
Acknowledgements
This work was supported by the Center of Analysis and Testing of Jiangnan University and the Research Institute of Elemento-Organic Chemistry of Suzhou University.
References
Postigo, A. & Rossi, R. A. (2001). Org. Lett. 3, 1197-1200. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stange, A. F., Tokura, S. & Kira, M. (2000). J. Organomet. Chem. 612, 117-124. Web of Science CrossRef CAS Google Scholar
Wenkert, D. & Woodward, R. B. (1983). J. Org. Chem. 48, 283-289. CrossRef CAS Web of Science Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Derivatives of 2,2'-bipyridine have received much attention due to their potential to form polypyridyl metal complexes, particularly of ruthenium and rhenium which have diverse applications. The photochemical and redox properties of these complexes can be varied through appropriate substitution on the pyridine rings. The derivatization of a 2,2'-bipyridine ligand with electron donating/withdrawing groups in the 4,4'-positions has been a popular means of controlling the redox potential of transition metal bipyridine complexes. The 4,4'-disubstitution can also offers no steric complications on complexation. The research about synthesis and properties of pyridine rings interconnected with strong electron-donating groups, as well as trimethysilyl group, was recently reported (Stange et al., 2000; Postigo & Rossi, 2001). However, there are no reports on 4,4'-bis(trimethylsilyl)-2,2'-bipyridine. Herein, we report crystal structure of the title compound.
The molecule is placed in centre of symmetry and nealy flat (Fig. 1) as the C—Si is co-planar with the aromatic rings. The torsion angle for N1—C4—C4i—C5i = 0°. In crystal, molecules are connected by weak non-classical intermolecular C3–H3···N1ii hydrogen bonds with parameters C3···N1ii = 3.626 (2) Å, H3···N1ii = 2.714 Å and angle C3–H3···N1ii = 164.3°. Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) -x + 1, y - 1/2, -z + 1/2.