In the title compound, C12H14N22+·2Cl-, the 4,4'-dimethyl-2,2'-bipyridinium cation is essentially planar (r.m.s. deviation for all non-H atoms = 0.004 Å) and is located on a crystallographic inversion centre. The cations and chloride anions lie in planes parallel to (111) and are connected by N-H...Cl and C-H...Cl hydrogen bonds. Key indicators: single-crystal X-ray study; T = 173 K; mean &#963;(C–C) = 0.003 Å; R factor = 0.036; wR factor = 0.080; data-to-parameter ratio = 14.7

Bolte, Michael

Eckensberger, Urs David

Lerner, Hans-Wolfram

English

Hochschulschriftenserver - Universität Frankfurt am Main

4,4000-Dimethyl-2,2000-bipyridiniumdichlorideUrs David Eckensberger, Hans-Wolfram Lerner andMichael Bolte*Institut fu ¨r Anorganische Chemie, J. W. Goethe-Universita ¨t Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, GermanyCorrespondence e-mail: bolte@chemie.uni-frankfurt.deReceived 10 July 2008; accepted 18 August 2008Key indicators: single-crystal X-ray study; T = 173 K; mean  (C–C) = 0.003 A ˚;R factor = 0.036; wR factor = 0.080; data-to-parameter ratio = 14.7.In the title compound, C12H14N22+ 2Cl , the 4,40-dimethyl-2,20-bipyridinium cation is essentially planar (r.m.s. deviationfor all non-H atoms = 0.004 A ˚ ) and is located on acrystallographic inversion centre. The cations and chlorideanions lie in planes parallel to (111) and are connected by N—H   Cl and C—H   Cl hydrogen bonds.Related literatureFor related literature, see: Eckensberger (2006); Scheibitz etal. (2005). For structures containing the 4,40-dimethyl-2,20-bipyridinium cation, see: Linden et al. (1999); Willett et al.(2001).ExperimentalCrystal dataC12H14N22+ 2Cl Mr = 257.15Triclinic, P1a = 5.1999 (10) A ˚b = 7.2705 (13) A ˚c = 8.4785 (15) A ˚  = 93.877 (15)   = 102.349 (15)   = 97.759 (15) V = 308.71 (10) A ˚ 3Z =1Mo K  radiation  = 0.50 mm 1T = 173 (2) K0.21   0.21   0.14 mmData collectionStoe IPDSII two-circlediffractometerAbsorption correction: multi-scan(MULABS; Spek, 2003; Blessing,1995)Tmin = 0.902, Tmax = 0.9333382 measured reﬂections1147 independent reﬂections926 reﬂections with I >2  (I)Rint = 0.058ReﬁnementR[F2 >2  (F2)] = 0.035wR(F2) = 0.079S = 0.971147 reﬂections78 parametersH atoms treated by a mixture ofindependent and constrainedreﬁnement max = 0.23 e A ˚  3 min =  0.23 e A ˚  3Table 1Hydrogen-bond geometry (A ˚ ,  ).D—H   AD —H H   AD    AD —H   AN1—H1   Cl1 0.86 (3) 2.17 (3) 3.009 (2) 165 (3)C2—H2   Cl1i 0.95 2.75 3.496 (2) 136C5—H5   Cl1ii 0.95 2.62 3.554 (2) 169Symmetry codes: (i)  x þ 2; y; z þ 1; (ii)  x þ 1; y þ 1; z þ 1.Data collection: X-AREA (Stoe & Cie, 2001); cell reﬁnement: X-AREA; data reduction: X-AREA; program(s) used to solve structure:SHELXS97 (Sheldrick, 2008); program(s) used to reﬁne structure:SHELXL97 (Sheldrick, 2008); molecular graphics: XP inSHELXTL-Plus (Sheldrick, 2008); software used to prepare materialfor publication: SHELXL97.Supplementary data and ﬁgures for this paper are available from theIUCr electronic archives (Reference: BI2297).ReferencesBlessing, R. H. (1995). Acta Cryst. A51, 33–38.Eckensberger, U. D. (2006). Diploma Thesis, Frankfurt.Linden, A., James, M. A., Millikan, M. B., Kivlighon, L. M., Petridis, A. &James, B. D. (1999). Inorg. Chim. Acta, 284, 215–222.Scheibitz, M., Heilmann, J. B., Winter, R. F., Bolte, M., Bats, J. W. & Wagner,M. (2005). Dalton Trans. pp. 159–170.Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany.Willett, R. D., Pon, G. & Nagy, C. (2001). Inorg. Chem. 40, 4342–4352.organic compoundso1806 Eckensberger et al. doi:10.1107/S1600536808026615 Acta Cryst. (2008). E64, o1806Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368supplementary materialssupplementary materialssup-1Acta Cryst. (2008). E64, o1806    [ doi:10.1107/S1600536808026615 ]4,4'-Dimethyl-2,2'-bipyridinium dichlorideU. D. Eckensberger, H.-W. Lerner and M. BolteCommentRecently, we have synthesized the dimeric diferrocenylboryl cation I (see Scheme) (Scheibitz et al., 2005). Now we areinterested to prepare the cationic dinuclear complex with a pentamethylcyclopentadienyl ring III. In an attempt to synthesizeIII from II (Eckensberger, 2006) and 4,4'-dimethyl-2,2'-bipyridine, we obtained the title compound as a by-product. X-rayquality crystals were grown from CD3CN in an NMR tube at ambient temperature.The title compound crystallizes with one formula unit in the unit cell. The cation is located on a crystallographic inversioncentre. It is essentially planar (r.m.s. deviation for all non-H atoms 0.004 Å). The chloride anions deviate by just 0.072 (3)Å from this plane. These planes are parallel to the (111) plane. In a plane, cations and anions are connected by N—H···Cland C—H···Cl hydrogen bonds (Fig. 2).ExperimentalIn an attempt to synthesize complex III (Eckensberger, 2006) from II (0.156 g, 0.32 mmol) with 4,4'-dimethyl-2,2'-bipyrid-ine (0.065 g, 0.35 mmol) in 5 ml acetonitrile, the title compound was obtained as a by-product. X-ray quality crystals weregrown from CD3CN in an NMR tube at ambient temperature after several days.RefinementH atoms were geometrically positioned with Caromatic—H = 0.95 Å and Cmethyl—H 0.98 Å, and refined using a ridingmodel with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(Cmethyl)]. The methyl group was allowed to rotate about its local threefoldaxis. The H atom bonded to N was freely refined.FiguresPerspective view of the title compound with the atom numbering scheme; displacement ellips-oids are at the 50% probability level; H atoms are drawn as small spheres of arbitrary radii.Hydrogen bonds are drawn as dashed lines. Symmetry operator for generating equivalentatoms: 1 - x, 1 - y, 1 - z.Packing diagram of the title compound viewed perpendicular to the (1 1 1) plane. Hydrogenbonds are indicated as dashed lines.supplementary materialssup-24,4'-Dimethyl-2,2'-bipyridinium dichlorideCrystal dataC12H14N22+·2(Cl–) Z = 1Mr = 257.15 F000 = 134Triclinic, P1 Dx = 1.383 Mg m−3Hall symbol: -P 1 Mo Kα radiationλ = 0.71073 Åa = 5.1999 (10) Å Cell parameters from 3157 reflectionsb = 7.2705 (13) Å θ = 3.6–25.8ºc = 8.4785 (15) Å µ = 0.50 mm−1α = 93.877 (15)º T = 173 (2) Kβ = 102.349 (15)º Block, colourlessγ = 97.759 (15)º 0.21 × 0.21 × 0.14 mmV = 308.71 (10) Å3Data collectionStoe IPDSII two-circlediffractometer 1147 independent reflectionsRadiation source: fine-focus sealed tube 926 reflections with I > 2σ(I)Monochromator: graphite Rint = 0.058T = 173(2) K θmax = 25.6ºω scans θmin = 3.6ºAbsorption correction: multi-scan(MULABS; Spek, 2003; Blessing, 1995) h = −6→6Tmin = 0.902, Tmax = 0.933 k = −8→83382 measured reflections l = −10→9RefinementRefinement on F2 Secondary atom site location: difference Fourier mapLeast-squares matrix: fullHydrogen site location: inferred from neighbouringsitesR[F2 > 2σ(F2)] = 0.035H atoms treated by a mixture ofindependent and constrained refinementsupplementary materialssup-3wR(F2) = 0.079  w = 1/[σ2(Fo2) + (0.0407P)2]where P = (Fo2 + 2Fc2)/3S = 0.97 (Δ/σ)max < 0.0011147 reflections Δρmax = 0.23 e Å−378 parameters Δρmin = −0.23 e Å−3Primary atom site location: structure-invariant directmethodsExtinction correction: noneSpecial detailsGeometry. 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 mat-rix. 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; correlationsbetween e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment ofcell 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, convention-al 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 largeas 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)x y z Uiso*/UeqCl1 0.97517 (12) 0.22553 (7) 0.26756 (7) 0.02679 (18)N1 0.6763 (4) 0.3002 (2) 0.5264 (2) 0.0219 (4)H1 0.749 (6) 0.296 (4) 0.444 (4) 0.047 (8)*C1 0.5194 (4) 0.4274 (2) 0.5570 (2) 0.0195 (4)C2 0.7255 (5) 0.1636 (3) 0.6223 (3) 0.0254 (5)H2 0.8362 0.0774 0.5967 0.031*C3 0.6195 (5) 0.1455 (3) 0.7564 (3) 0.0273 (5)H3 0.6568 0.0483 0.8232 0.033*C4 0.4553 (4) 0.2725 (3) 0.7936 (3) 0.0223 (5)C5 0.4078 (4) 0.4121 (3) 0.6904 (2) 0.0210 (5)H5 0.2957 0.4988 0.7125 0.025*C6 0.3345 (5) 0.2555 (3) 0.9383 (3) 0.0287 (5)H6A 0.2337 0.3585 0.9488 0.043*H6B 0.4761 0.2605 1.0362 0.043*H6C 0.2147 0.1365 0.9244 0.043*Atomic displacement parameters (Å2)U11 U22 U33 U12 U13 U23Cl1 0.0285 (3) 0.0269 (3) 0.0288 (3) 0.00927 (19) 0.0113 (2) 0.00399 (18)N1 0.0236 (10) 0.0228 (8) 0.0223 (10) 0.0070 (7) 0.0082 (8) 0.0064 (7)C1 0.0204 (11) 0.0195 (9) 0.0181 (10) 0.0029 (8) 0.0031 (8) 0.0028 (8)C2 0.0262 (12) 0.0238 (9) 0.0293 (12) 0.0086 (8) 0.0081 (10) 0.0084 (8)C3 0.0284 (13) 0.0244 (10) 0.0295 (12) 0.0066 (9) 0.0032 (10) 0.0110 (9)C4 0.0231 (11) 0.0217 (9) 0.0204 (10) −0.0012 (8) 0.0035 (9) 0.0039 (8)supplementary materialssup-4C5 0.0243 (12) 0.0196 (9) 0.0200 (10) 0.0061 (8) 0.0043 (9) 0.0049 (8)C6 0.0350 (14) 0.0301 (11) 0.0218 (11) 0.0040 (10) 0.0076 (10) 0.0075 (9)Geometric parameters (Å, °)N1—C2 1.342 (3) C3—H3 0.950N1—C1 1.360 (2) C4—C5 1.397 (3)N1—H1 0.86 (3) C4—C6 1.498 (3)C1—C5 1.382 (3) C5—H5 0.950C1—C1i 1.484 (4) C6—H6A 0.980C2—C3 1.372 (3) C6—H6B 0.980C2—H2 0.950 C6—H6C 0.980C3—C4 1.404 (3)C2—N1—C1 121.9 (2) C5—C4—C3 117.6 (2)C2—N1—H1 113.5 (19) C5—C4—C6 121.92 (17)C1—N1—H1 124.6 (19) C3—C4—C6 120.46 (19)N1—C1—C5 118.08 (18) C1—C5—C4 121.78 (17)N1—C1—C1i 117.0 (2) C1—C5—H5 119.1C5—C1—C1i 124.9 (2) C4—C5—H5 119.1N1—C2—C3 121.46 (17) C4—C6—H6A 109.5N1—C2—H2 119.3 C4—C6—H6B 109.5C3—C2—H2 119.3 H6A—C6—H6B 109.5C2—C3—C4 119.17 (19) C4—C6—H6C 109.5C2—C3—H3 120.4 H6A—C6—H6C 109.5C4—C3—H3 120.4 H6B—C6—H6C 109.5C2—N1—C1—C5 −0.5 (3) C2—C3—C4—C6 179.4 (2)C2—N1—C1—C1i 179.7 (2) N1—C1—C5—C4 0.9 (3)C1—N1—C2—C3 0.0 (3) C1i—C1—C5—C4 −179.3 (2)N1—C2—C3—C4 0.2 (3) C3—C4—C5—C1 −0.7 (3)C2—C3—C4—C5 0.1 (3) C6—C4—C5—C1 −180.0 (2)Symmetry codes: (i) −x+1, −y+1, −z+1.Hydrogen-bond geometry (Å, °)D—H···A D—H H···A D···A D—H···AN1—H1···Cl1 0.86 (3) 2.17 (3) 3.009 (2) 165 (3)C2—H2···Cl1ii 0.95 2.75 3.496 (2) 136C5—H5···Cl1i 0.95 2.62 3.554 (2) 169Symmetry codes: (ii) −x+2, −y, −z+1; (i) −x+1, −y+1, −z+1.supplementary materialssup-5Fig. 1supplementary materialssup-6Fig. 2supplementary materialssup-7Fig. 3

Dalton Trans.

Diploma Thesis,

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) x y z Uiso*/Ueq Cl1

organic compounds o1806 Eckensberger et al. doi:10.1107/S1600536808026615 Acta Cryst.

Packing diagram of the title compound viewed perpendicular to the (1 1 1) plane. Hydrogen bonds are indicated as dashed lines.supplementary materials sup-2 4,4'-Dimethyl-2,2'-bipyridinium dichloride Crystal data

4,4′-Di­methyl-2,2′-bipyridinium dichloride

4,40-Dimethyl-2,20-bipyridinium dichloride

4,40-Dimethyl-2,20-bipyridinium dichloride

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