4,4'-(Ethane-1,2-diyl)dipyridinium bis-(2-hy-droxy-benzoate).

In the crystal structure of the title compound, C(12)H(14)N(2) (2+)·2C(7)H(5)O(3) (-), the cations and anions are linked via N-H⋯O hydrogen bonds and weak inter-molecular C-H⋯O inter-actions 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 ethyl-ene C-C bond is located on an inversion center. An intra-molecular 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 ▶). For the structure of 4,4′-(ethane-1,2-diyl)dipyridinium bis­(hydrogen maleate), see: Bowes et al. (2003 ▶). For deprotonated salicylic acid, see: Chitradevi et al. (2009 ▶); Fun et al. (2010 ▶); Quah et al. (2010 ▶).

Experimental

Crystal data

C12H14N2 2+·2C7H5O3 −

M = 460.47

Monoclinic,

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

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

C12H14N22+·2C7H5O3−	F(000) = 484
Mr = 460.47	Dx = 1.346 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2343 reflections
a = 8.622 (3) Å	θ = 3.6–25.9°
b = 6.867 (2) Å	µ = 0.10 mm−1
c = 19.566 (6) Å	T = 297 K
β = 101.324 (6)°	Prism, colorless
V = 1135.9 (6) Å3	0.42 × 0.26 × 0.17 mm
Z = 2

Bruker SMART CCD area-detector diffractometer	1645 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.053
graphite	θmax = 26.1°, θmin = 2.1°
Detector resolution: 9 pixels mm-1	h = −5→10
ω scan	k = −8→8
6165 measured reflections	l = −24→23
2246 independent reflections

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

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.

	x	y	z	Uiso*/Ueq
N	0.23112 (16)	0.41868 (19)	0.59247 (7)	0.0507 (5)
C8	0.30204 (19)	0.4936 (2)	0.54421 (9)	0.0508 (6)
C9	0.25306 (19)	0.6652 (2)	0.51103 (9)	0.0502 (5)
C10	0.12421 (17)	0.7649 (2)	0.52708 (8)	0.0419 (5)
C11	0.05191 (19)	0.6837 (2)	0.57748 (9)	0.0504 (5)
C12	0.1084 (2)	0.5109 (3)	0.60879 (10)	0.0545 (6)
C13	0.07080 (18)	0.9519 (2)	0.48984 (9)	0.0483 (5)
O1	0.32265 (15)	0.10150 (17)	0.65611 (7)	0.0612 (5)
O2	0.48925 (16)	0.07561 (19)	0.58403 (7)	0.0689 (5)
O3	0.67244 (17)	−0.2176 (2)	0.59167 (8)	0.0822 (6)
C1	0.43333 (19)	0.0129 (2)	0.63306 (9)	0.0463 (5)
C2	0.48956 (17)	−0.1735 (2)	0.66799 (8)	0.0425 (5)
C3	0.4252 (2)	−0.2478 (3)	0.72231 (9)	0.0515 (6)
C4	0.4772 (2)	−0.4221 (3)	0.75408 (10)	0.0660 (7)
C5	0.5946 (2)	−0.5245 (3)	0.73117 (11)	0.0696 (7)
C6	0.6594 (2)	−0.4550 (3)	0.67733 (12)	0.0670 (7)
C7	0.6078 (2)	−0.2797 (2)	0.64510 (10)	0.0515 (6)
H1A	0.26440	0.31150	0.61290	0.0610*
H8	0.38750	0.42790	0.53250	0.0610*
H9	0.30600	0.71500	0.47780	0.0600*
H11	−0.03430	0.74520	0.59020	0.0600*
H12	0.05870	0.45740	0.64250	0.0650*
H13A	0.04610	0.92600	0.44020	0.0580*
H13B	0.15830	1.04320	0.49830	0.0580*
H3	0.34550	−0.17890	0.73760	0.0620*
H3A	0.62520	−0.11430	0.58230	0.1230*
H4	0.43350	−0.46980	0.79060	0.0790*
H5	0.63030	−0.64170	0.75240	0.0830*
H6	0.73840	−0.52550	0.66230	0.0800*

	U11	U22	U33	U12	U13	U23
N	0.0485 (8)	0.0343 (7)	0.0662 (9)	0.0103 (6)	0.0038 (7)	0.0061 (6)
C8	0.0438 (9)	0.0412 (9)	0.0677 (11)	0.0099 (7)	0.0118 (8)	0.0010 (8)
C9	0.0452 (9)	0.0448 (9)	0.0623 (10)	0.0069 (7)	0.0146 (7)	0.0043 (8)
C10	0.0356 (8)	0.0358 (8)	0.0531 (9)	0.0032 (6)	0.0055 (6)	0.0019 (7)
C11	0.0441 (9)	0.0454 (9)	0.0637 (10)	0.0137 (7)	0.0154 (8)	0.0095 (8)
C12	0.0527 (10)	0.0467 (9)	0.0660 (11)	0.0106 (8)	0.0166 (8)	0.0140 (8)
C13	0.0451 (9)	0.0402 (9)	0.0606 (10)	0.0084 (7)	0.0128 (7)	0.0093 (8)
O1	0.0669 (8)	0.0460 (7)	0.0773 (9)	0.0201 (6)	0.0307 (6)	0.0110 (6)
O2	0.0834 (10)	0.0534 (8)	0.0801 (9)	0.0133 (7)	0.0407 (8)	0.0186 (7)
O3	0.0732 (9)	0.0799 (10)	0.1084 (12)	0.0229 (8)	0.0541 (9)	0.0127 (9)
C1	0.0490 (9)	0.0376 (8)	0.0532 (10)	0.0033 (7)	0.0126 (7)	0.0005 (7)
C2	0.0406 (8)	0.0372 (8)	0.0480 (9)	0.0030 (6)	0.0043 (6)	−0.0019 (7)
C3	0.0542 (10)	0.0501 (10)	0.0505 (9)	0.0075 (8)	0.0108 (8)	0.0028 (8)
C4	0.0771 (13)	0.0583 (11)	0.0598 (11)	0.0060 (10)	0.0067 (9)	0.0159 (9)
C5	0.0691 (12)	0.0474 (10)	0.0823 (14)	0.0118 (10)	−0.0094 (10)	0.0130 (10)
C6	0.0499 (11)	0.0530 (11)	0.0933 (15)	0.0185 (9)	0.0026 (10)	−0.0063 (11)
C7	0.0415 (9)	0.0474 (10)	0.0657 (11)	0.0045 (7)	0.0111 (8)	−0.0046 (8)

O1—C1	1.286 (2)	C11—H11	0.9300
O2—C1	1.233 (2)	C12—H12	0.9300
O3—C7	1.347 (2)	C13—H13A	0.9700
O3—H3A	0.8200	C13—H13B	0.9700
N—C8	1.326 (2)	C1—C2	1.487 (2)
N—C12	1.325 (2)	C2—C7	1.397 (2)
N—H1A	0.8600	C2—C3	1.389 (2)
C8—C9	1.371 (2)	C3—C4	1.382 (3)
C9—C10	1.392 (2)	C4—C5	1.378 (3)
C10—C11	1.383 (2)	C5—C6	1.371 (3)
C10—C13	1.503 (2)	C6—C7	1.391 (3)
C11—C12	1.380 (3)	C3—H3	0.9300
C13—C13i	1.509 (2)	C4—H4	0.9300
C8—H8	0.9300	C5—H5	0.9300
C9—H9	0.9300	C6—H6	0.9300
C7—O3—H3A	101.00	C13i—C13—H13B	108.00
C8—N—C12	119.22 (15)	C13i—C13—H13A	108.00
C8—N—H1A	120.00	O1—C1—C2	116.34 (14)
C12—N—H1A	120.00	O2—C1—C2	121.09 (15)
N—C8—C9	121.90 (15)	O1—C1—O2	122.57 (14)
C8—C9—C10	120.06 (15)	C1—C2—C7	119.65 (14)
C9—C10—C13	119.52 (14)	C3—C2—C7	118.68 (15)
C11—C10—C13	123.49 (14)	C1—C2—C3	121.65 (15)
C9—C10—C11	116.99 (13)	C2—C3—C4	121.27 (16)
C10—C11—C12	119.61 (15)	C3—C4—C5	119.33 (18)
N—C12—C11	122.22 (17)	C4—C5—C6	120.56 (19)
C10—C13—C13i	115.66 (13)	C5—C6—C7	120.48 (18)
N—C8—H8	119.00	O3—C7—C6	118.79 (16)
C9—C8—H8	119.00	C2—C7—C6	119.68 (16)
C8—C9—H9	120.00	O3—C7—C2	121.52 (14)
C10—C9—H9	120.00	C2—C3—H3	119.00
C12—C11—H11	120.00	C4—C3—H3	119.00
C10—C11—H11	120.00	C3—C4—H4	120.00
N—C12—H12	119.00	C5—C4—H4	120.00
C11—C12—H12	119.00	C4—C5—H5	120.00
C10—C13—H13B	108.00	C6—C5—H5	120.00
H13A—C13—H13B	107.00	C5—C6—H6	120.00
C10—C13—H13A	108.00	C7—C6—H6	120.00
C12—N—C8—C9	0.7 (2)	O2—C1—C2—C3	−178.62 (16)
C8—N—C12—C11	−0.4 (3)	O2—C1—C2—C7	0.1 (2)
N—C8—C9—C10	−0.8 (3)	C1—C2—C3—C4	179.41 (16)
C8—C9—C10—C11	0.6 (2)	C7—C2—C3—C4	0.7 (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—C12	179.70 (16)	C3—C2—C7—O3	178.52 (16)
C9—C10—C13—C13i	179.34 (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—N	0.2 (3)	C3—C4—C5—C6	−0.1 (3)
C10—C13—C13i—C10i	−179.97 (17)	C4—C5—C6—C7	0.1 (3)
O1—C1—C2—C3	0.3 (2)	C5—C6—C7—O3	−178.96 (18)
O1—C1—C2—C7	178.98 (15)	C5—C6—C7—C2	0.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N—H1A···O1	0.86	1.70	2.556 (2)	177
O3—H3A···O2	0.82	1.76	2.545 (2)	160
C11—H11···O3ii	0.93	2.55	3.406 (3)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H1A⋯O1	0.86	1.70	2.556 (2)	177
O3—H3A⋯O2	0.82	1.76	2.545 (2)	160
C11—H11⋯O3i	0.93	2.55	3.406 (3)	154

Symmetry code: (i) .