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Acta Crystallogr Sect E Struct Rep Online. 2012 October 1; 68(Pt 10): o3033.
Published online 2012 September 29. doi:  10.1107/S1600536812040214
PMCID: PMC3470387

Redetermination of 2,2′-bipyridine-1,1′-diium dibromide

Abstract

In the title mol­ecular salt, C10H10N2 2+·2Br, the dihedral angle between the aromatic rings is 20.83 (14)° and the N—H groups have a transoid conformaton [N—C—C—N = 158.5 (3)°]. In the crystal, the cations are linked to the anions by two N—H(...)Br and five C—H(...)Br hydrogen bonds, generating corrugated sheets incorporating R 2 1(7), R 4 2(10), R 4 2(11) and two different R 4 2(12) loops. This structure was originally reported by Nakatsu et al. [Acta Cryst (1972), A28, S24], but no atomic coordinates are available.

Related literature  

For the previous report of this structure as a conference abstract, see: Nakatsu et al. (1972 [triangle]). For related structures of 2,2′-bipyridium dication salts, see: Ma et al. (2000 [triangle]). For structures containing dicationic 2,2′-bipyridyl derivative salts, see: Amarante et al. (2011 [triangle]); Eckensberger et al. (2008 [triangle]). For structures of monocationic 2,2′-bipyridinium salts, see: Kavitha et al. (2006 [triangle]). For ring motifs, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-68-o3033-scheme1.jpg

Experimental  

Crystal data  

  • C10H10N2 2+·2Br
  • M r = 318.00
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-o3033-efi1.jpg
  • a = 7.5568 (6) Å
  • b = 9.7747 (7) Å
  • c = 15.3533 (12) Å
  • β = 95.830 (7)°
  • V = 1128.21 (15) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 7.15 mm−1
  • T = 293 K
  • 0.20 × 0.15 × 0.10 mm

Data collection  

  • Agilent Xcalibur EOS diffractometer
  • Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 [triangle]) T min = 0.287, T max = 0.489
  • 5425 measured reflections
  • 3054 independent reflections
  • 1884 reflections with I > 2σ(I)
  • R int = 0.032

Refinement  

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.073
  • S = 1.03
  • 3054 reflections
  • 127 parameters
  • H-atom parameters constrained
  • Δρmax = 0.50 e Å−3
  • Δρmin = −0.57 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 [triangle]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812040214/hb6957sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812040214/hb6957Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812040214/hb6957Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The structure was determined at the Hamdi Mango Center for Scientific Research at the University of Jordan, Amman, Jordan. RA-F would like to thank Al-Balqa’a Applied University (Jordan) for financial support (sabbatical leave).

supplementary crystallographic information

Comment

2,2'-bipyridine can form two types of salts monocationic, see for example (Kavitha et al., 2006) or dicationic bipyridinium (see for example Ma et al., 2000). Herein we report the title salt, (I), Figure 1. This structure was reported by Nakatsu et al. (1972), but no atomic coordinates are available. The bipyridinium cation in (I) has a transoid configuration with the N—C—C—N torsion angle is 158.5 (3)°, and the C—C bond distance between the two rings being 1.464 (4) Å. Within the dication, geometrical dimensions are in normal range and agree with reported values (Ma et al., 2000; Eckensberger et al. 2008; Amarante et al. 2011).

The ions in (I) are linked by a combination of seven hydrogen bonds of the types N—H···Br and C—H···Br, Table 1, into complex corrugated sheets, Figure 2. These sheets composed of R12(7), R24(10), R24(11) and two different R24(12) graph set motifs (Bernstein et al. 1995), Figure 3. With the overall coordination around each bromide anion being 4 (three C—H···Br and one N—H···Br interactions), Figure 3.

Experimental

A solution of MnCl2 (0.1258 g, 1 mmol) dissolved in 95% EtOH (10 ml) solution was added to a mixture of 2,2'-bipyridine (0.1562 g, 1 mmol) dissolved in 95% EtOH (10 ml) and 60% HBr (2 ml). The resulting mixture was heated to few min, then treated with molecular bromine (2–3 drops), then refluxed for 1.5 hr. On slow evaporation at room temperature colourless chunks of the title salt were formed.

Refinement

All H atoms were positioned geometrically and refined using a riding model, with N—H = 0.86 Å and C—H = 0.93 Å, with the Uiso(H) were allowed at 1.2Ueq(N/C).

Figures

Fig. 1.
The molecular stucture of the title salt with displacement ellipsoids drawn at the 30% probability level.
Fig. 2.
Packing diagram of the title salt showing the sheets of cations···anions hydrogen bonded species. Interspecies C/N–H···Br hydrogen bonds are shown as dashed lines. H atoms have been omitted for clarity, ...
Fig. 3.
A view of one hydrogen bonded sheet contains the different graph-set motifs in the title salt.

Crystal data

C10H10N22+·2BrF(000) = 616
Mr = 318.00Dx = 1.872 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1832 reflections
a = 7.5568 (6) Åθ = 2.9–29.1°
b = 9.7747 (7) ŵ = 7.15 mm1
c = 15.3533 (12) ÅT = 293 K
β = 95.830 (7)°Chunk, colourless
V = 1128.21 (15) Å30.20 × 0.15 × 0.10 mm
Z = 4

Data collection

Agilent Xcalibur EOS diffractometer3054 independent reflections
Radiation source: Enhance (Mo) x-ray source1884 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
Detector resolution: 16.0534 pixels mm-1θmax = 29.2°, θmin = 3.4°
ω scansh = −7→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)k = −13→10
Tmin = 0.287, Tmax = 0.489l = −21→16
5425 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.025P)2] where P = (Fo2 + 2Fc2)/3
3054 reflections(Δ/σ)max = 0.001
127 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = −0.57 e Å3

Special details

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)

xyzUiso*/Ueq
Br10.23397 (5)0.03486 (4)0.67326 (2)0.04534 (13)
N10.4480 (4)0.4858 (3)0.63133 (16)0.0384 (7)
H1A0.53660.45800.60510.046*
C10.3257 (6)0.3947 (4)0.6491 (2)0.0507 (10)
H1B0.33690.30360.63300.061*
N20.5392 (4)0.8449 (3)0.61771 (15)0.0369 (7)
H2A0.43780.87140.63230.044*
C20.1841 (6)0.4356 (4)0.6909 (2)0.0554 (11)
H2B0.09500.37390.70130.066*
Br20.74405 (5)0.29766 (4)0.55966 (2)0.04749 (13)
C30.1749 (5)0.5695 (4)0.7175 (2)0.0532 (11)
H3A0.08220.59790.74880.064*
C40.3033 (5)0.6619 (4)0.6978 (2)0.0429 (9)
H4A0.29680.75260.71540.051*
C50.4402 (4)0.6197 (3)0.65239 (19)0.0314 (7)
C60.6477 (5)0.9395 (4)0.5912 (2)0.0446 (9)
H6A0.61411.03110.58980.054*
C70.8083 (6)0.9019 (4)0.5662 (2)0.0505 (10)
H7A0.88510.96710.54700.061*
C80.8553 (5)0.7657 (4)0.5698 (2)0.0509 (10)
H8A0.96410.73830.55240.061*
C90.7398 (5)0.6683 (4)0.5997 (2)0.0449 (9)
H9A0.77230.57650.60350.054*
C100.5767 (4)0.7105 (3)0.62330 (19)0.0324 (8)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0395 (2)0.0378 (2)0.0598 (2)0.00431 (18)0.01032 (17)−0.00318 (18)
N10.0397 (19)0.0320 (17)0.0441 (16)−0.0004 (14)0.0068 (13)0.0021 (13)
C10.058 (3)0.035 (2)0.058 (2)−0.013 (2)0.001 (2)0.0056 (18)
N20.0309 (17)0.0316 (17)0.0483 (17)−0.0033 (14)0.0055 (13)0.0014 (13)
C20.043 (3)0.056 (3)0.067 (3)−0.019 (2)0.008 (2)0.016 (2)
Br20.0500 (3)0.0356 (2)0.0580 (2)0.00351 (19)0.01070 (18)−0.00453 (16)
C30.036 (2)0.060 (3)0.067 (2)0.004 (2)0.0223 (19)0.018 (2)
C40.037 (2)0.036 (2)0.057 (2)0.0052 (17)0.0111 (18)0.0031 (17)
C50.0301 (19)0.0260 (18)0.0379 (17)−0.0007 (16)0.0022 (14)0.0036 (14)
C60.045 (3)0.037 (2)0.052 (2)−0.0067 (19)0.0020 (18)0.0054 (17)
C70.048 (3)0.052 (3)0.053 (2)−0.015 (2)0.0113 (19)0.0052 (19)
C80.034 (2)0.065 (3)0.056 (2)−0.005 (2)0.0157 (17)−0.002 (2)
C90.038 (2)0.038 (2)0.060 (2)0.0053 (18)0.0112 (18)0.0026 (17)
C100.0304 (19)0.0319 (19)0.0349 (17)0.0001 (16)0.0033 (14)0.0023 (14)

Geometric parameters (Å, º)

N1—C11.331 (4)C4—C51.369 (4)
N1—C51.351 (4)C4—H4A0.9300
N1—H1A0.8600C5—C101.464 (4)
C1—C21.363 (6)C6—C71.360 (5)
C1—H1B0.9300C6—H6A0.9300
N2—C61.326 (4)C7—C81.378 (5)
N2—C101.345 (4)C7—H7A0.9300
N2—H2A0.8600C8—C91.399 (5)
C2—C31.375 (5)C8—H8A0.9300
C2—H2B0.9300C9—C101.383 (5)
C3—C41.382 (5)C9—H9A0.9300
C3—H3A0.9300
C1—N1—C5123.5 (3)N1—C5—C4117.8 (3)
C1—N1—H1A118.3N1—C5—C10117.7 (3)
C5—N1—H1A118.3C4—C5—C10124.4 (3)
N1—C1—C2119.6 (4)N2—C6—C7119.7 (4)
N1—C1—H1B120.2N2—C6—H6A120.1
C2—C1—H1B120.2C7—C6—H6A120.1
C6—N2—C10124.6 (3)C6—C7—C8118.9 (4)
C6—N2—H2A117.7C6—C7—H7A120.6
C10—N2—H2A117.7C8—C7—H7A120.6
C1—C2—C3119.0 (4)C7—C8—C9120.3 (4)
C1—C2—H2B120.5C7—C8—H8A119.9
C3—C2—H2B120.5C9—C8—H8A119.9
C2—C3—C4119.9 (4)C10—C9—C8119.0 (3)
C2—C3—H3A120.0C10—C9—H9A120.5
C4—C3—H3A120.0C8—C9—H9A120.5
C5—C4—C3120.0 (3)N2—C10—C9117.6 (3)
C5—C4—H4A120.0N2—C10—C5117.5 (3)
C3—C4—H4A120.0C9—C10—C5125.0 (3)
C5—N1—C1—C2−0.2 (5)C6—C7—C8—C9−0.7 (5)
N1—C1—C2—C3−2.9 (6)C7—C8—C9—C101.6 (5)
C1—C2—C3—C43.3 (6)C6—N2—C10—C9−0.1 (5)
C2—C3—C4—C5−0.5 (5)C6—N2—C10—C5−178.9 (3)
C1—N1—C5—C43.0 (5)C8—C9—C10—N2−1.2 (5)
C1—N1—C5—C10−175.6 (3)C8—C9—C10—C5177.6 (3)
C3—C4—C5—N1−2.6 (5)N1—C5—C10—N2158.5 (3)
C3—C4—C5—C10175.9 (3)C4—C5—C10—N2−20.1 (5)
C10—N2—C6—C71.0 (5)N1—C5—C10—C9−20.3 (5)
N2—C6—C7—C8−0.6 (5)C4—C5—C10—C9161.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···AD—HH···AD···AD—H···A
N1—H1A···Br20.862.373.178 (3)156
N2—H2A···Br1i0.862.353.145 (3)154
C1—H1B···Br10.932.833.611 (4)143
C9—H9A···Br20.932.813.675 (4)155
C6—H6A···Br2i0.932.843.619 (4)142
C4—H4A···Br1i0.932.863.697 (4)150
C3—H3A···Br1ii0.932.853.677 (4)149

Symmetry codes: (i) x, y+1, z; (ii) −x, y+1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB6957).

References

  • Agilent (2011). CrysAlis PROAgilent Technologies, Yarnton, England.
  • Amarante, T. R., Gonçalves, I. S. & Almeida Paz, F. A. (2011). Acta Cryst. E67, o1903–o1904. [PMC free article] [PubMed]
  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.
  • Eckensberger, U. D., Lerner, H.-W. & Bolte, M. (2008). Acta Cryst. E64, o1806. [PMC free article] [PubMed]
  • Kavitha, S. J., Panchanatheswaran, K., Low, J. N., Ferguson, G. & Glidewell, C. (2006). Acta Cryst. C62, o165–o169. [PubMed]
  • Ma, G., Ilyukhin, A. & Glaser, J. (2000). Acta Cryst. C56, 1473–1475. [PubMed]
  • Nakatsu, K., Yoshioka, H., Matsui, M., Koda, S. & Ooi, S. (1972). Acta Cryst. A28, S24.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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