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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2701.
Published online 2010 October 2. doi:  10.1107/S160053681003816X
PMCID: PMC3009235

4,4′-(Ethane-1,2-diyl)dipyridinium bis­(2-hy­droxy­benzoate)

Abstract

In the crystal structure of the title compound, C12H14N2 2+·2C7H5O3 , the cations and anions are linked via N—H(...)O hydrogen bonds and weak inter­molecular C—H(...)O inter­actions also occur. π–π stacking is observed between the nearly parallel benzene and pyridine rings [dihedral angle = 6.03 (8)°], the centroid–centroid separation being 3.7546 (16) Å. The 4,4′-(ethane-1,2-diyl)dipyridinium cation is centrosymmetric and the mid-point of the ethyl­ene C—C bond is located on an inversion center. An intra­molecular O—H(...)O hydrogen bond occurs in the anion.

Related literature

For the structure of 4,4′-(ethane-1,2-diyl)dipyridinium bis­(3,5-dinitro­benzoate), see: Burchell et al. (2001 [triangle]). For the structure of 4,4′-(ethane-1,2-diyl)dipyridinium bis­(hydrogen maleate), see: Bowes et al. (2003 [triangle]). For deprotonated salicylic acid, see: Chitradevi et al. (2009 [triangle]); Fun et al. (2010 [triangle]); Quah et al. (2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2701-scheme1.jpg

Experimental

Crystal data

  • C12H14N2 2+·2C7H5O3
  • M r = 460.47
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2701-efi1.jpg
  • a = 8.622 (3) Å
  • b = 6.867 (2) Å
  • c = 19.566 (6) Å
  • β = 101.324 (6)°
  • V = 1135.9 (6) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 297 K
  • 0.42 × 0.26 × 0.17 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • 6165 measured reflections
  • 2246 independent reflections
  • 1645 reflections with I > 2σ(I)
  • R int = 0.053

Refinement

  • R[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.147
  • S = 1.05
  • 2246 reflections
  • 155 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 1999 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681003816X/xu5033sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681003816X/xu5033Isup2.hkl

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

Acknowledgments

This work was supported financially by Yuanpei University, Taiwan.

supplementary crystallographic information

Comment

There are numerous examples of saliclyic acid compounds in which the salicylic acid act as deprotonated anions (Quah et al., 2010; Fun et al., 2010; Chitradevi et al., 2009). Some 4,4-ethylenedipyridinium salts have also reported previously (Burchell et al. 2001; Bowes et al. 2003).

The crystal structure of the title proton-transfer compound of salicylic acid with 4,4'-(ethane-1,2-diyl)dipyridine consists of 4,4'-(ethane-1,2-diyl)dipyridinium cations and 2-hydroxybenzoate anionst (Fig. 1). The 4,4'-(ethane-1,2-diyl)dipyridinium cation is centro-symmetric, with the mid-point of ethylene C—C bond located on the inversion center. Two salicylate anions have intramolecular hydrogen bonding. The 4,4'-(ethane-1,2-diyl)dipyridinium cation is linked by N—H···O hydrogen bond to adjacent salicylate anions.

Intermolecular weak C—H···O hydrogen bonding is present in the crystal structure (Table 1). On the other hand, π–π ring stacking is also observed, the centroid–centroid separation between the benzene and pyridine ring, Cg1(N/C8—C12)··· Cg2iii(C2—C7), is 3.7546 (16) Å and dihedral angle between two rings is 6.03 (8)° [symmetry code: (iii) = x, 1 + y, z].

Experimental

The salicylic acid (138.0 mg, 1.0 mmol) and 4,4'-(ethane-1,2-diyl)dipyridine (184 mg, 1.0 mmol) were dissolved in 20 ml me thanol-water (1:1), the solution was refluxed for 30 min. The filtered solution was transferred to a 25 ml tube, after one week at room temperature colorless transparent crystals formed (yield 56.78%).

Refinement

H atoms bonded to O and N atoms were located in a difference Fourier map and refined with the distances constraints of O—H = 0.82, N—H = 0.86 Å, and Uiso(H) = 1.2Ueq(N) and 1.5Ueq(O). Other H atoms were positioned geometrically with C—H = 0.93 (aromatic) and 0.97 Å (methylene), and were refined using a riding model with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The structure of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. Dashed lines indicate hydrogen bonding [symmetry code: (i) -x, 2 - y, 1 - z].

Crystal data

C12H14N22+·2C7H5O3F(000) = 484
Mr = 460.47Dx = 1.346 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2343 reflections
a = 8.622 (3) Åθ = 3.6–25.9°
b = 6.867 (2) ŵ = 0.10 mm1
c = 19.566 (6) ÅT = 297 K
β = 101.324 (6)°Prism, colorless
V = 1135.9 (6) Å30.42 × 0.26 × 0.17 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer1645 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.053
graphiteθmax = 26.1°, θmin = 2.1°
Detector resolution: 9 pixels mm-1h = −5→10
ω scank = −8→8
6165 measured reflectionsl = −24→23
2246 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.147w = 1/[σ2(Fo2) + (0.0761P)2 + 0.1342P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2246 reflectionsΔρmax = 0.21 e Å3
155 parametersΔρmin = −0.25 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=KFc[1+0.001Fc2λ3/sin(2Θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.015 (3)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
N0.23112 (16)0.41868 (19)0.59247 (7)0.0507 (5)
C80.30204 (19)0.4936 (2)0.54421 (9)0.0508 (6)
C90.25306 (19)0.6652 (2)0.51103 (9)0.0502 (5)
C100.12421 (17)0.7649 (2)0.52708 (8)0.0419 (5)
C110.05191 (19)0.6837 (2)0.57748 (9)0.0504 (5)
C120.1084 (2)0.5109 (3)0.60879 (10)0.0545 (6)
C130.07080 (18)0.9519 (2)0.48984 (9)0.0483 (5)
O10.32265 (15)0.10150 (17)0.65611 (7)0.0612 (5)
O20.48925 (16)0.07561 (19)0.58403 (7)0.0689 (5)
O30.67244 (17)−0.2176 (2)0.59167 (8)0.0822 (6)
C10.43333 (19)0.0129 (2)0.63306 (9)0.0463 (5)
C20.48956 (17)−0.1735 (2)0.66799 (8)0.0425 (5)
C30.4252 (2)−0.2478 (3)0.72231 (9)0.0515 (6)
C40.4772 (2)−0.4221 (3)0.75408 (10)0.0660 (7)
C50.5946 (2)−0.5245 (3)0.73117 (11)0.0696 (7)
C60.6594 (2)−0.4550 (3)0.67733 (12)0.0670 (7)
C70.6078 (2)−0.2797 (2)0.64510 (10)0.0515 (6)
H1A0.264400.311500.612900.0610*
H80.387500.427900.532500.0610*
H90.306000.715000.477800.0600*
H11−0.034300.745200.590200.0600*
H120.058700.457400.642500.0650*
H13A0.046100.926000.440200.0580*
H13B0.158301.043200.498300.0580*
H30.34550−0.178900.737600.0620*
H3A0.62520−0.114300.582300.1230*
H40.43350−0.469800.790600.0790*
H50.63030−0.641700.752400.0830*
H60.73840−0.525500.662300.0800*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N0.0485 (8)0.0343 (7)0.0662 (9)0.0103 (6)0.0038 (7)0.0061 (6)
C80.0438 (9)0.0412 (9)0.0677 (11)0.0099 (7)0.0118 (8)0.0010 (8)
C90.0452 (9)0.0448 (9)0.0623 (10)0.0069 (7)0.0146 (7)0.0043 (8)
C100.0356 (8)0.0358 (8)0.0531 (9)0.0032 (6)0.0055 (6)0.0019 (7)
C110.0441 (9)0.0454 (9)0.0637 (10)0.0137 (7)0.0154 (8)0.0095 (8)
C120.0527 (10)0.0467 (9)0.0660 (11)0.0106 (8)0.0166 (8)0.0140 (8)
C130.0451 (9)0.0402 (9)0.0606 (10)0.0084 (7)0.0128 (7)0.0093 (8)
O10.0669 (8)0.0460 (7)0.0773 (9)0.0201 (6)0.0307 (6)0.0110 (6)
O20.0834 (10)0.0534 (8)0.0801 (9)0.0133 (7)0.0407 (8)0.0186 (7)
O30.0732 (9)0.0799 (10)0.1084 (12)0.0229 (8)0.0541 (9)0.0127 (9)
C10.0490 (9)0.0376 (8)0.0532 (10)0.0033 (7)0.0126 (7)0.0005 (7)
C20.0406 (8)0.0372 (8)0.0480 (9)0.0030 (6)0.0043 (6)−0.0019 (7)
C30.0542 (10)0.0501 (10)0.0505 (9)0.0075 (8)0.0108 (8)0.0028 (8)
C40.0771 (13)0.0583 (11)0.0598 (11)0.0060 (10)0.0067 (9)0.0159 (9)
C50.0691 (12)0.0474 (10)0.0823 (14)0.0118 (10)−0.0094 (10)0.0130 (10)
C60.0499 (11)0.0530 (11)0.0933 (15)0.0185 (9)0.0026 (10)−0.0063 (11)
C70.0415 (9)0.0474 (10)0.0657 (11)0.0045 (7)0.0111 (8)−0.0046 (8)

Geometric parameters (Å, °)

O1—C11.286 (2)C11—H110.9300
O2—C11.233 (2)C12—H120.9300
O3—C71.347 (2)C13—H13A0.9700
O3—H3A0.8200C13—H13B0.9700
N—C81.326 (2)C1—C21.487 (2)
N—C121.325 (2)C2—C71.397 (2)
N—H1A0.8600C2—C31.389 (2)
C8—C91.371 (2)C3—C41.382 (3)
C9—C101.392 (2)C4—C51.378 (3)
C10—C111.383 (2)C5—C61.371 (3)
C10—C131.503 (2)C6—C71.391 (3)
C11—C121.380 (3)C3—H30.9300
C13—C13i1.509 (2)C4—H40.9300
C8—H80.9300C5—H50.9300
C9—H90.9300C6—H60.9300
C7—O3—H3A101.00C13i—C13—H13B108.00
C8—N—C12119.22 (15)C13i—C13—H13A108.00
C8—N—H1A120.00O1—C1—C2116.34 (14)
C12—N—H1A120.00O2—C1—C2121.09 (15)
N—C8—C9121.90 (15)O1—C1—O2122.57 (14)
C8—C9—C10120.06 (15)C1—C2—C7119.65 (14)
C9—C10—C13119.52 (14)C3—C2—C7118.68 (15)
C11—C10—C13123.49 (14)C1—C2—C3121.65 (15)
C9—C10—C11116.99 (13)C2—C3—C4121.27 (16)
C10—C11—C12119.61 (15)C3—C4—C5119.33 (18)
N—C12—C11122.22 (17)C4—C5—C6120.56 (19)
C10—C13—C13i115.66 (13)C5—C6—C7120.48 (18)
N—C8—H8119.00O3—C7—C6118.79 (16)
C9—C8—H8119.00C2—C7—C6119.68 (16)
C8—C9—H9120.00O3—C7—C2121.52 (14)
C10—C9—H9120.00C2—C3—H3119.00
C12—C11—H11120.00C4—C3—H3119.00
C10—C11—H11120.00C3—C4—H4120.00
N—C12—H12119.00C5—C4—H4120.00
C11—C12—H12119.00C4—C5—H5120.00
C10—C13—H13B108.00C6—C5—H5120.00
H13A—C13—H13B107.00C5—C6—H6120.00
C10—C13—H13A108.00C7—C6—H6120.00
C12—N—C8—C90.7 (2)O2—C1—C2—C3−178.62 (16)
C8—N—C12—C11−0.4 (3)O2—C1—C2—C70.1 (2)
N—C8—C9—C10−0.8 (3)C1—C2—C3—C4179.41 (16)
C8—C9—C10—C110.6 (2)C7—C2—C3—C40.7 (3)
C8—C9—C10—C13−179.43 (15)C1—C2—C7—O3−0.2 (2)
C9—C10—C11—C12−0.4 (2)C1—C2—C7—C6−179.40 (16)
C13—C10—C11—C12179.70 (16)C3—C2—C7—O3178.52 (16)
C9—C10—C13—C13i179.34 (14)C3—C2—C7—C6−0.7 (3)
C11—C10—C13—C13i−0.7 (2)C2—C3—C4—C5−0.3 (3)
C10—C11—C12—N0.2 (3)C3—C4—C5—C6−0.1 (3)
C10—C13—C13i—C10i−179.97 (17)C4—C5—C6—C70.1 (3)
O1—C1—C2—C30.3 (2)C5—C6—C7—O3−178.96 (18)
O1—C1—C2—C7178.98 (15)C5—C6—C7—C20.3 (3)

Symmetry codes: (i) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N—H1A···O10.861.702.556 (2)177
O3—H3A···O20.821.762.545 (2)160
C11—H11···O3ii0.932.553.406 (3)154

Symmetry codes: (ii) x−1, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU5033).

References

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  • Chitradevi, A., Athimoolam, S., Sridhar, B. & Bahadur, S. A. (2009). Acta Cryst. E65, o3041–o3042. [PMC free article] [PubMed]
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