4,4'-(Ethene-1,2-diyl)dipyridinium bis-[4-(2-carboxy-benzo-yl)benzoate].

In the crystal structure of the title compound, C(12)H(12)N(2) (2+)·2C(15)H(9)O(5) (-), the cation has site symmetry with the mid-point of C=C bond located on an inversion center. The two benzene rings of the anion are oriented at a dihedral angle 85.87 (6)°. In the crystal, inter-molecular O-H⋯O and N-H⋯O hydrogen bonds link the cations and anions into supra-molecular double chains, which are further connected into a three-dimensional network through inter-molecular C-H⋯O and π-π stacking between parallel pyridine rings [centroid-centroid distance = 3.4413 (12)Å] and between parallel benzene rings [centroid-centroid distance = 3.6116 (14)Å].

Related literature

For hydrogen bonding and π–π stacking in supra­molecular systems, see: Desiraju (2000 ▶); Ma et al. (2006 ▶); Dong et al. (2008 ▶); Huang & Qian (2005 ▶).

Experimental

Crystal data

C12H12N2 2+·2C15H9O5 −

M = 722.68

Triclinic,

a = 7.1335 (13) Å

b = 9.4558 (17) Å

c = 13.206 (2) Å

α = 81.641 (2)°

β = 79.986 (2)°

γ = 71.260 (2)°

V = 826.9 (3) Å3

Z = 1

Mo Kα radiation

μ = 0.11 mm−1

T = 293 K

0.29 × 0.14 × 0.06 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.983, T max = 0.994

6357 measured reflections

3055 independent reflections

2212 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.115

S = 1.01

3055 reflections

250 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.22 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809048417/xu2637sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809048417/xu2637Isup2.hkl

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

C12H12N22+·2C15H9O5−	Z = 1
Mr = 722.68	F(000) = 376
Triclinic, P1	Dx = 1.451 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1335 (13) Å	Cell parameters from 6357 reflections
b = 9.4558 (17) Å	θ = 2.7–25.5°
c = 13.206 (2) Å	µ = 0.11 mm−1
α = 81.641 (2)°	T = 293 K
β = 79.986 (2)°	Prism, colorless
γ = 71.260 (2)°	0.29 × 0.14 × 0.06 mm
V = 826.9 (3) Å3

Bruker SMART CCD diffractometer	3055 independent reflections
Radiation source: fine-focus sealed tube	2212 reflections with I > 2σ(I)
graphite	Rint = 0.025
φ and ω scans	θmax = 25.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.983, Tmax = 0.994	k = −11→11
6357 measured reflections	l = −15→15

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0527P)2 + 0.1979P] where P = (Fo2 + 2Fc2)/3
3055 reflections	(Δ/σ)max < 0.001
250 parameters	Δρmax = 0.20 e Å−3
2 restraints	Δρmin = −0.22 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.3708 (3)	0.7481 (2)	1.06116 (15)	0.0344 (5)
H1	0.3941	0.7967	1.1118	0.041*
C2	0.2259 (3)	0.6772 (2)	1.08332 (15)	0.0336 (5)
H2	0.1539	0.6765	1.1492	0.040*
C3	0.1860 (3)	0.6061 (2)	1.00748 (14)	0.0304 (4)
C4	0.3013 (3)	0.6087 (2)	0.91086 (15)	0.0340 (5)
H4	0.2803	0.5625	0.8581	0.041*
C5	0.4460 (3)	0.6796 (2)	0.89372 (15)	0.0344 (5)
H5A	0.5229	0.6799	0.8292	0.041*
C6	0.0296 (3)	0.5327 (2)	1.03236 (15)	0.0349 (5)
H6	−0.0340	0.5320	1.1001	0.042*
C7	−0.1807 (3)	−0.1223 (2)	0.82078 (16)	0.0358 (5)
C8	−0.0337 (3)	−0.0357 (2)	0.78080 (15)	0.0312 (4)
C9	0.0829 (3)	−0.0123 (2)	0.84717 (15)	0.0347 (5)
H9	0.0702	−0.0505	0.9161	0.042*
C10	0.2171 (3)	0.0670 (2)	0.81169 (15)	0.0346 (5)
H10	0.2976	0.0787	0.8562	0.042*
C11	0.2329 (3)	0.1293 (2)	0.70999 (15)	0.0308 (4)
C12	0.1136 (3)	0.1081 (2)	0.64353 (15)	0.0348 (5)
H12	0.1210	0.1508	0.5755	0.042*
C13	−0.0158 (3)	0.0235 (2)	0.67888 (16)	0.0372 (5)
H13	−0.0910	0.0066	0.6336	0.045*
C14	0.3742 (3)	0.2184 (2)	0.67376 (15)	0.0344 (5)
C15	0.3715 (3)	0.3001 (2)	0.56687 (14)	0.0308 (4)
C16	0.4987 (3)	0.2238 (2)	0.48697 (16)	0.0392 (5)
H16	0.5756	0.1247	0.5004	0.047*
C17	0.5124 (3)	0.2935 (2)	0.38745 (16)	0.0407 (5)
H17	0.5966	0.2409	0.3343	0.049*
C18	0.4011 (3)	0.4412 (2)	0.36712 (15)	0.0388 (5)
H18	0.4115	0.4885	0.3004	0.047*
C19	0.2744 (3)	0.5186 (2)	0.44582 (14)	0.0333 (5)
H19	0.2000	0.6181	0.4318	0.040*
C20	0.2565 (3)	0.4497 (2)	0.54578 (14)	0.0306 (4)
C21	0.1207 (3)	0.5313 (2)	0.63185 (16)	0.0351 (5)
N1	0.4789 (2)	0.74805 (18)	0.96750 (13)	0.0323 (4)
H1A	0.575 (2)	0.797 (2)	0.9512 (16)	0.048*
O1	−0.2576 (2)	−0.11219 (16)	0.91455 (11)	0.0438 (4)
O2	−0.2190 (2)	−0.19672 (18)	0.76131 (12)	0.0511 (4)
O3	0.5013 (2)	0.21679 (19)	0.72479 (12)	0.0567 (5)
O4	0.1007 (3)	0.47083 (18)	0.71866 (11)	0.0581 (5)
O5	0.0256 (2)	0.67303 (16)	0.60536 (11)	0.0434 (4)
H5	−0.053 (3)	0.715 (3)	0.6618 (13)	0.065*

	U11	U22	U33	U12	U13	U23
C1	0.0388 (11)	0.0335 (11)	0.0339 (11)	−0.0137 (9)	−0.0039 (9)	−0.0075 (9)
C2	0.0361 (11)	0.0372 (11)	0.0282 (11)	−0.0141 (9)	0.0014 (8)	−0.0052 (9)
C3	0.0339 (11)	0.0290 (10)	0.0304 (11)	−0.0128 (8)	−0.0044 (8)	−0.0019 (8)
C4	0.0387 (11)	0.0370 (11)	0.0306 (11)	−0.0172 (9)	−0.0019 (9)	−0.0069 (9)
C5	0.0389 (11)	0.0386 (11)	0.0276 (11)	−0.0166 (9)	0.0011 (9)	−0.0045 (9)
C6	0.0382 (11)	0.0430 (12)	0.0274 (11)	−0.0212 (9)	0.0008 (8)	−0.0017 (9)
C7	0.0335 (11)	0.0321 (11)	0.0429 (13)	−0.0137 (9)	0.0023 (9)	−0.0080 (9)
C8	0.0278 (10)	0.0265 (10)	0.0377 (11)	−0.0080 (8)	0.0014 (8)	−0.0059 (8)
C9	0.0391 (11)	0.0334 (11)	0.0302 (11)	−0.0133 (9)	−0.0009 (9)	0.0017 (9)
C10	0.0362 (11)	0.0371 (11)	0.0328 (11)	−0.0134 (9)	−0.0081 (9)	−0.0014 (9)
C11	0.0311 (10)	0.0290 (10)	0.0324 (11)	−0.0108 (8)	−0.0033 (8)	−0.0005 (8)
C12	0.0380 (11)	0.0372 (11)	0.0312 (11)	−0.0158 (9)	−0.0046 (9)	−0.0002 (9)
C13	0.0370 (11)	0.0426 (12)	0.0367 (12)	−0.0172 (10)	−0.0068 (9)	−0.0047 (9)
C14	0.0370 (11)	0.0361 (11)	0.0334 (11)	−0.0157 (9)	−0.0055 (9)	−0.0021 (9)
C15	0.0334 (10)	0.0349 (11)	0.0300 (11)	−0.0193 (9)	−0.0035 (8)	−0.0024 (8)
C16	0.0413 (12)	0.0354 (11)	0.0429 (13)	−0.0138 (10)	−0.0047 (10)	−0.0064 (10)
C17	0.0422 (12)	0.0490 (13)	0.0324 (12)	−0.0173 (10)	0.0045 (9)	−0.0120 (10)
C18	0.0471 (12)	0.0481 (13)	0.0261 (11)	−0.0237 (11)	−0.0008 (9)	−0.0024 (9)
C19	0.0371 (11)	0.0365 (11)	0.0306 (11)	−0.0181 (9)	−0.0029 (9)	−0.0027 (9)
C20	0.0303 (10)	0.0372 (11)	0.0298 (10)	−0.0179 (9)	−0.0019 (8)	−0.0051 (8)
C21	0.0390 (11)	0.0384 (12)	0.0344 (12)	−0.0208 (10)	−0.0029 (9)	−0.0059 (9)
N1	0.0332 (9)	0.0313 (9)	0.0361 (9)	−0.0170 (7)	−0.0019 (7)	−0.0020 (7)
O1	0.0517 (9)	0.0507 (9)	0.0365 (8)	−0.0315 (8)	0.0090 (7)	−0.0094 (7)
O2	0.0518 (10)	0.0595 (10)	0.0518 (10)	−0.0337 (8)	0.0162 (7)	−0.0255 (8)
O3	0.0625 (11)	0.0779 (12)	0.0471 (10)	−0.0449 (10)	−0.0238 (8)	0.0134 (8)
O4	0.0851 (13)	0.0520 (10)	0.0288 (9)	−0.0186 (9)	0.0082 (8)	−0.0017 (7)
O5	0.0459 (9)	0.0397 (9)	0.0406 (9)	−0.0121 (7)	0.0067 (7)	−0.0084 (7)

C1—N1	1.339 (2)	C11—C12	1.398 (3)
C1—C2	1.374 (3)	C11—C14	1.488 (3)
C1—H1	0.9300	C12—C13	1.388 (3)
C2—C3	1.398 (3)	C12—H12	0.9300
C2—H2	0.9300	C13—H13	0.9300
C3—C4	1.394 (3)	C14—O3	1.215 (2)
C3—C6	1.462 (3)	C14—C15	1.508 (3)
C4—C5	1.373 (3)	C15—C16	1.387 (3)
C4—H4	0.9300	C15—C20	1.404 (3)
C5—N1	1.336 (2)	C16—C17	1.384 (3)
C5—H5A	0.9300	C16—H16	0.9300
C6—C6i	1.318 (4)	C17—C18	1.380 (3)
C6—H6	0.9300	C17—H17	0.9300
C7—O2	1.244 (2)	C18—C19	1.379 (3)
C7—O1	1.268 (2)	C18—H18	0.9300
C7—C8	1.511 (3)	C19—C20	1.388 (3)
C8—C13	1.381 (3)	C19—H19	0.9300
C8—C9	1.392 (3)	C20—C21	1.489 (3)
C9—C10	1.379 (3)	C21—O4	1.211 (2)
C9—H9	0.9300	C21—O5	1.320 (2)
C10—C11	1.387 (3)	N1—H1A	0.924 (17)
C10—H10	0.9300	O5—H5	0.91 (2)
N1—C1—C2	120.83 (18)	C13—C12—H12	119.9
N1—C1—H1	119.6	C11—C12—H12	119.9
C2—C1—H1	119.6	C8—C13—C12	120.46 (19)
C1—C2—C3	120.38 (18)	C8—C13—H13	119.8
C1—C2—H2	119.8	C12—C13—H13	119.8
C3—C2—H2	119.8	O3—C14—C11	121.52 (18)
C4—C3—C2	117.10 (17)	O3—C14—C15	119.46 (17)
C4—C3—C6	123.40 (17)	C11—C14—C15	118.76 (17)
C2—C3—C6	119.50 (17)	C16—C15—C20	119.20 (18)
C5—C4—C3	119.87 (18)	C16—C15—C14	117.15 (18)
C5—C4—H4	120.1	C20—C15—C14	123.56 (17)
C3—C4—H4	120.1	C17—C16—C15	120.7 (2)
N1—C5—C4	121.57 (18)	C17—C16—H16	119.7
N1—C5—H5A	119.2	C15—C16—H16	119.7
C4—C5—H5A	119.2	C18—C17—C16	120.02 (19)
C6i—C6—C3	126.0 (2)	C18—C17—H17	120.0
C6i—C6—H6	117.0	C16—C17—H17	120.0
C3—C6—H6	117.0	C19—C18—C17	119.91 (19)
O2—C7—O1	124.59 (18)	C19—C18—H18	120.0
O2—C7—C8	119.16 (18)	C17—C18—H18	120.0
O1—C7—C8	116.25 (18)	C18—C19—C20	120.85 (19)
C13—C8—C9	119.21 (18)	C18—C19—H19	119.6
C13—C8—C7	120.68 (18)	C20—C19—H19	119.6
C9—C8—C7	120.10 (18)	C19—C20—C15	119.32 (18)
C10—C9—C8	120.65 (18)	C19—C20—C21	121.69 (18)
C10—C9—H9	119.7	C15—C20—C21	118.99 (17)
C8—C9—H9	119.7	O4—C21—O5	123.48 (19)
C9—C10—C11	120.41 (19)	O4—C21—C20	122.0 (2)
C9—C10—H10	119.8	O5—C21—C20	114.51 (17)
C11—C10—H10	119.8	C5—N1—C1	120.23 (17)
C10—C11—C12	119.07 (17)	C5—N1—H1A	118.1 (14)
C10—C11—C14	119.72 (17)	C1—N1—H1A	121.6 (14)
C12—C11—C14	121.21 (17)	C21—O5—H5	109.1 (16)
C13—C12—C11	120.14 (18)
N1—C1—C2—C3	−1.3 (3)	C10—C11—C14—C15	−172.89 (18)
C1—C2—C3—C4	1.1 (3)	C12—C11—C14—C15	6.5 (3)
C1—C2—C3—C6	−179.33 (18)	O3—C14—C15—C16	83.1 (3)
C2—C3—C4—C5	−0.2 (3)	C11—C14—C15—C16	−91.1 (2)
C6—C3—C4—C5	−179.75 (19)	O3—C14—C15—C20	−93.4 (2)
C3—C4—C5—N1	−0.6 (3)	C11—C14—C15—C20	92.4 (2)
C4—C3—C6—C6i	−3.6 (4)	C20—C15—C16—C17	−0.1 (3)
C2—C3—C6—C6i	176.9 (3)	C14—C15—C16—C17	−176.80 (18)
O2—C7—C8—C13	31.7 (3)	C15—C16—C17—C18	1.0 (3)
O1—C7—C8—C13	−147.9 (2)	C16—C17—C18—C19	−0.8 (3)
O2—C7—C8—C9	−149.50 (19)	C17—C18—C19—C20	−0.2 (3)
O1—C7—C8—C9	30.9 (3)	C18—C19—C20—C15	1.0 (3)
C13—C8—C9—C10	−1.0 (3)	C18—C19—C20—C21	179.95 (18)
C7—C8—C9—C10	−179.80 (18)	C16—C15—C20—C19	−0.8 (3)
C8—C9—C10—C11	2.3 (3)	C14—C15—C20—C19	175.59 (17)
C9—C10—C11—C12	−1.2 (3)	C16—C15—C20—C21	−179.81 (17)
C9—C10—C11—C14	178.19 (18)	C14—C15—C20—C21	−3.4 (3)
C10—C11—C12—C13	−1.1 (3)	C19—C20—C21—O4	178.18 (19)
C14—C11—C12—C13	179.44 (18)	C15—C20—C21—O4	−2.9 (3)
C9—C8—C13—C12	−1.4 (3)	C19—C20—C21—O5	−1.8 (3)
C7—C8—C13—C12	177.40 (18)	C15—C20—C21—O5	177.15 (16)
C11—C12—C13—C8	2.5 (3)	C4—C5—N1—C1	0.4 (3)
C10—C11—C14—O3	13.1 (3)	C2—C1—N1—C5	0.5 (3)
C12—C11—C14—O3	−167.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ii	0.92 (2)	1.65 (2)	2.577 (2)	176 (2)
O5—H5···O2iii	0.91 (2)	1.72 (2)	2.629 (2)	175 (2)
C1—H1···O3iv	0.93	2.38	3.209 (3)	149
C5—H5A···O2ii	0.93	2.46	3.144 (3)	130
C6—H6···O4i	0.93	2.36	3.256 (2)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1i	0.924 (17)	1.654 (17)	2.577 (2)	176 (2)
O5—H5⋯O2ii	0.91 (2)	1.72 (2)	2.629 (2)	175 (2)
C1—H1⋯O3iii	0.93	2.38	3.209 (3)	149
C5—H5A⋯O2i	0.93	2.46	3.144 (3)	130
C6—H6⋯O4iv	0.93	2.36	3.256 (2)	163

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .