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access1,1′-(p-Phenylenedimethylene)dipyridinium bis(hexafluoridophosphate)
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my
The title salt, C18H18N22+·2PF6−, exists as non-interacting cations and anions. In the cation, the pyridine and phenylene rings are aligned at 62.9 (1)°; the pyridine ring lies on a special position of m and the phenylene ring on a special position of 2/m The angle at the methylene C atom is 112.8 (1)°. The anion lies on a special position of m four F atoms lie on this mirror plane.
Related literature
For the tetraphenylborate salt, see: Wu et al. (2007![[Wu, Y.-J., Liu, X.-C., Du, C.-X. & Niu, Y.-Y. (2007). Acta Cryst. E63, o3457.]](../../../../../../logos/arrows/e_arr.gif "Wu, Y.-J., Liu, X.-C., Du, C.-X. & Niu, Y.-Y. (2007). Acta Cryst. E63, o3457.")
) and for the tetracyanoquinodimethanide salt, see: Ashwell et al. (1975); Hudson & Robson (2009).
![[Scheme 1]](jh2207scheme1.gif)
Experimental
Crystal data
|
Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536810037992/jh2207sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536810037992/jh2207Isup2.hkl
α,α'-Dibromo-p-xylene (5.28 g, 20 mmol) was dissolved in acetonitrile (30 ml) and to the solution was added pyridine (2.96 g, 40 mmol). The solution was heated for 2 h. The solid product was recrystallized from a methanol/ethanol mixture to afford 1,1'-(4-dimethylphenylene)dipyridinium bromide. The bromide ion was exchanged by the hexafluorophosphate ion by reaction of the salt (1 mmol) with ammonium hexafluorophosphate (2 mmol) in water. The reactants were mixed in water for 2 h to give a solid material. This was collected and recrystallized from acetonitrile.
Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the in the riding model approximation, with U(H) set to 1.2U(C).
Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
![[Figure 1]](./jh2207fig1thm.gif) | Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C18H18N22+ 2PF6- at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. |
| C18H18N22+·2PF6− | F(000) = 556 |
| Mr = 552.28 | Dx = 1.774 Mg m−3 |
| Orthorhombic, Pbam | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2 2ab | Cell parameters from 2836 reflections |
| a = 11.1013 (11) Å | θ = 2.8–28.2° |
| b = 12.6742 (12) Å | µ = 0.33 mm−1 |
| c = 7.3483 (7) Å | T = 100 K |
| V = 1033.91 (17) Å3 | Block, colorless |
| Z = 2 | 0.30 × 0.20 × 0.10 mm |
| Bruker SMART APEX diffractometer | 1280 independent reflections |
| Radiation source: fine-focus sealed tube | 1121 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.028 |
| ω scans | θmax = 27.5°, θmin = 2.4° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −14→14 |
| Tmin = 0.908, Tmax = 0.968 | k = −12→16 |
| 6200 measured reflections | l = −9→8 |
| 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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.088 | H-atom parameters constrained |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.0505P)2 + 0.3897P] where P = (Fo2 + 2Fc2)/3 |
| 1280 reflections | (Δ/σ)max < 0.001 |
| 91 parameters | Δρmax = 0.33 e Å−3 |
| 0 restraints | Δρmin = −0.44 e Å−3 |
| C18H18N22+·2PF6− | V = 1033.91 (17) Å3 |
| Mr = 552.28 | Z = 2 |
| Orthorhombic, Pbam | Mo Kα radiation |
| a = 11.1013 (11) Å | µ = 0.33 mm−1 |
| b = 12.6742 (12) Å | T = 100 K |
| c = 7.3483 (7) Å | 0.30 × 0.20 × 0.10 mm |
| Bruker SMART APEX diffractometer | 1280 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1121 reflections with I > 2σ(I) |
| Tmin = 0.908, Tmax = 0.968 | Rint = 0.028 |
| 6200 measured reflections |
| R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
| wR(F2) = 0.088 | H-atom parameters constrained |
| S = 1.05 | Δρmax = 0.33 e Å−3 |
| 1280 reflections | Δρmin = −0.44 e Å−3 |
| 91 parameters |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| P1 | 0.25173 (4) | 0.14923 (4) | 0.0000 | 0.01624 (16) | |
| F1 | 0.25218 (7) | 0.14917 (6) | 0.21872 (11) | 0.0238 (2) | |
| F2 | 0.31281 (13) | 0.26387 (9) | 0.0000 | 0.0351 (3) | |
| F3 | 0.12080 (10) | 0.20151 (10) | 0.0000 | 0.0281 (3) | |
| F4 | 0.19348 (10) | 0.03444 (8) | 0.0000 | 0.0238 (3) | |
| F5 | 0.38395 (10) | 0.09687 (10) | 0.0000 | 0.0282 (3) | |
| N1 | 0.00180 (13) | 0.29642 (11) | 0.5000 | 0.0151 (3) | |
| C1 | 0.17001 (16) | 0.45395 (14) | 0.5000 | 0.0227 (4) | |
| H1 | 0.2269 | 0.5100 | 0.5000 | 0.027* | |
| C2 | 0.12837 (12) | 0.41294 (11) | 0.3374 (2) | 0.0231 (3) | |
| H2 | 0.1579 | 0.4391 | 0.2247 | 0.028* | |
| C3 | 0.04351 (11) | 0.33362 (10) | 0.34067 (18) | 0.0192 (3) | |
| H3 | 0.0143 | 0.3050 | 0.2296 | 0.023* | |
| C4 | −0.09367 (16) | 0.21325 (14) | 0.5000 | 0.0203 (4) | |
| H4A | −0.1451 | 0.2225 | 0.3911 | 0.024* | 0.50 |
| H4B | −0.1451 | 0.2225 | 0.6089 | 0.024* | 0.50 |
| C5 | −0.04278 (15) | 0.10309 (13) | 0.5000 | 0.0153 (4) | |
| C6 | −0.02152 (11) | 0.05152 (10) | 0.66385 (17) | 0.0181 (3) | |
| H6 | −0.0364 | 0.0867 | 0.7758 | 0.022* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| P1 | 0.0184 (3) | 0.0162 (3) | 0.0141 (3) | −0.00093 (16) | 0.000 | 0.000 |
| F1 | 0.0274 (4) | 0.0300 (5) | 0.0140 (4) | −0.0014 (3) | −0.0013 (3) | −0.0022 (3) |
| F2 | 0.0502 (8) | 0.0217 (6) | 0.0333 (7) | −0.0156 (6) | 0.000 | 0.000 |
| F3 | 0.0272 (6) | 0.0346 (7) | 0.0224 (6) | 0.0125 (5) | 0.000 | 0.000 |
| F4 | 0.0309 (6) | 0.0196 (5) | 0.0210 (6) | −0.0068 (5) | 0.000 | 0.000 |
| F5 | 0.0189 (6) | 0.0400 (7) | 0.0255 (6) | 0.0042 (5) | 0.000 | 0.000 |
| N1 | 0.0150 (6) | 0.0115 (6) | 0.0187 (7) | 0.0018 (5) | 0.000 | 0.000 |
| C1 | 0.0148 (8) | 0.0134 (8) | 0.0398 (11) | 0.0014 (6) | 0.000 | 0.000 |
| C2 | 0.0222 (6) | 0.0212 (6) | 0.0260 (7) | 0.0022 (5) | 0.0048 (5) | 0.0064 (5) |
| C3 | 0.0220 (6) | 0.0197 (6) | 0.0161 (6) | 0.0030 (5) | −0.0002 (5) | 0.0003 (5) |
| C4 | 0.0148 (8) | 0.0136 (8) | 0.0323 (10) | −0.0005 (6) | 0.000 | 0.000 |
| C5 | 0.0129 (7) | 0.0130 (8) | 0.0201 (9) | −0.0020 (6) | 0.000 | 0.000 |
| C6 | 0.0215 (6) | 0.0167 (6) | 0.0159 (6) | −0.0027 (5) | 0.0021 (5) | −0.0021 (5) |
| P1—F4 | 1.5921 (11) | C1—H1 | 0.9500 |
| P1—F3 | 1.5975 (12) | C2—C3 | 1.3779 (18) |
| P1—F2 | 1.6034 (12) | C2—H2 | 0.9500 |
| P1—F1i | 1.6072 (8) | C3—H3 | 0.9500 |
| P1—F1 | 1.6072 (8) | C4—C5 | 1.506 (2) |
| P1—F5 | 1.6107 (12) | C4—H4A | 0.9900 |
| N1—C3ii | 1.3444 (15) | C4—H4B | 0.9900 |
| N1—C3 | 1.3444 (15) | C5—C6 | 1.3902 (15) |
| N1—C4 | 1.495 (2) | C5—C6ii | 1.3902 (15) |
| C1—C2 | 1.3828 (18) | C6—C6iii | 1.391 (2) |
| C1—C2ii | 1.3828 (18) | C6—H6 | 0.9500 |
| F4—P1—F3 | 90.54 (7) | C2ii—C1—H1 | 120.2 |
| F4—P1—F2 | 178.95 (7) | C3—C2—C1 | 119.18 (14) |
| F3—P1—F2 | 90.51 (7) | C3—C2—H2 | 120.4 |
| F4—P1—F1i | 90.05 (3) | C1—C2—H2 | 120.4 |
| F3—P1—F1i | 90.17 (3) | N1—C3—C2 | 120.45 (13) |
| F2—P1—F1i | 89.95 (3) | N1—C3—H3 | 119.8 |
| F4—P1—F1 | 90.05 (3) | C2—C3—H3 | 119.8 |
| F3—P1—F1 | 90.17 (3) | N1—C4—C5 | 112.81 (14) |
| F2—P1—F1 | 89.95 (3) | N1—C4—H4A | 109.0 |
| F1i—P1—F1 | 179.64 (7) | C5—C4—H4A | 109.0 |
| F4—P1—F5 | 89.64 (7) | N1—C4—H4B | 109.0 |
| F3—P1—F5 | 179.82 (7) | C5—C4—H4B | 109.0 |
| F2—P1—F5 | 89.31 (7) | H4A—C4—H4B | 107.8 |
| F1i—P1—F5 | 89.83 (3) | C6—C5—C6ii | 120.02 (16) |
| F1—P1—F5 | 89.83 (3) | C6—C5—C4 | 119.97 (8) |
| C3ii—N1—C3 | 121.11 (16) | C6ii—C5—C4 | 119.97 (8) |
| C3ii—N1—C4 | 119.44 (8) | C5—C6—C6iii | 119.99 (8) |
| C3—N1—C4 | 119.44 (8) | C5—C6—H6 | 120.0 |
| C2—C1—C2ii | 119.60 (17) | C6iii—C6—H6 | 120.0 |
| C2—C1—H1 | 120.2 | ||
| C2ii—C1—C2—C3 | 1.7 (3) | C3—N1—C4—C5 | 90.39 (12) |
| C3ii—N1—C3—C2 | −1.6 (2) | N1—C4—C5—C6 | 91.26 (13) |
| C4—N1—C3—C2 | 177.67 (13) | N1—C4—C5—C6ii | −91.26 (13) |
| C1—C2—C3—N1 | −0.1 (2) | C6ii—C5—C6—C6iii | 0.3 (3) |
| C3ii—N1—C4—C5 | −90.39 (12) | C4—C5—C6—C6iii | 177.77 (16) |
| Symmetry codes: (i) x, y, −z; (ii) x, y, −z+1; (iii) −x, −y, z. |
Experimental details
| Crystal data | |
| Chemical formula | C18H18N22+·2PF6− |
| Mr | 552.28 |
| Crystal system, space group | Orthorhombic, Pbam |
| Temperature (K) | 100 |
| a, b, c (Å) | 11.1013 (11), 12.6742 (12), 7.3483 (7) |
| V (Å3) | 1033.91 (17) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.33 |
| Crystal size (mm) | 0.30 × 0.20 × 0.10 |
| Data collection | |
| Diffractometer | Bruker SMART APEX diffractometer |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
| Tmin, Tmax | 0.908, 0.968 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 6200, 1280, 1121 |
| Rint | 0.028 |
| (sin θ/λ)max (Å−1) | 0.650 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.088, 1.05 |
| No. of reflections | 1280 |
| No. of parameters | 91 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.33, −0.44 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).
Acknowledgements
We thank the University of Malaya (grant No. TA010/2010 A) for supporting this study.
References
Ashwell, G. J., Wallwork, S. C., Baker, S. R. & Berthier, P. I. C. (1975). Acta Cryst. B31, 1174–1178. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hudson, T. A. & Robson, R. (2009). Cryst. Growth Des. 9, 1658–1662. Web of Science CSD CrossRef CAS 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
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wu, Y.-J., Liu, X.-C., Du, C.-X. & Niu, Y.-Y. (2007). Acta Cryst. E63, o3457. Web of Science CSD CrossRef IUCr Journals Google Scholar
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The structure of the 1,1'-(4-dimethylphenylene)dipyridinium cation has been reported in a number of examples (Ashwell et al., 1975; Hudson & Robson, 2009; Wu et al.,2007). We ourselves have reported other examples. The title hexafluorophosphate (Scheme I, Fig. 1) exists as non-interacting cations and anions. In the cation, the pyridyl and phenylene rings are aligned at 62.9 (1) °. The angle at the methylene C atom is 112.8 (1) °. The anion lies on a mirror plane such that four F atoms lie within the mirror plane.