4,4'-Bipyridinium bis-(2-carboxy-pyridine-3-carboxyl-ate).

The title salt, C(10)H(10)N(2) (2+)·2C(7)H(4)NO(4) (-) or (4,4'-bpyH(2))(py-2,3-dcH)(2), prepared by the reaction between pyridine-2,3-dicarboxylic acid (py-2,3-dcH(2)) and 4,4'-bipyridine (4,4'-bpy), consists of two anions and one centrosymmetric dication. In the crystal, there are two strong O-H⋯O hydrogen bonds involving the two carboxyl-ate groups, with an O⋯O distance of 2.478 (1) Å, and an N-H⋯N hydrogen bond between the anion and cation, with an N⋯N distance of 2.743 (1) Å. These inter-actions, along with other O-H⋯O and C-H⋯O hydrogen bonds, π-π stacking [centroid-centroid distances 3.621 (7) and 3.612 (7) Å] and ion pairing, lead to the formation of the three-dimensional structure.

Related literature

For proton-transfer ion pairs, see: Seethalakshmi et al. (2007 ▶); Manteghi et al. (2007 ▶); Aghabozorg, Manteghi & Ghadermazi (2008 ▶). For the use of ion pairs for the formation of metal organic frameworks, see: Aghabozorg, Manteghi & Sheshmani (2008 ▶). For hydrogen bonding, see: Desiraju & Steiner (1999 ▶).

Experimental

Crystal data

C10H10N2 2+·2C7H4NO4 −

M = 490.42

Monoclinic,

a = 6.6675 (2) Å

b = 13.7755 (5) Å

c = 11.5887 (4) Å

β = 106.310 (2)°

V = 1021.56 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.12 mm−1

T = 120 (2) K

0.33 × 0.25 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.904, T max = 0.988

18931 measured reflections

2327 independent reflections

2053 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.105

S = 1.05

2327 reflections

163 parameters

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.28 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042220/su2083sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808042220/su2083Isup2.hkl

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

C10H10N22+·2C7H4NO4−	F(000) = 508
Mr = 490.42	Dx = 1.594 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7505 reflections
a = 6.6675 (2) Å	θ = 2.4–27.5°
b = 13.7755 (5) Å	µ = 0.12 mm−1
c = 11.5887 (4) Å	T = 120 K
β = 106.310 (2)°	Block, yellow
V = 1021.56 (6) Å3	0.33 × 0.25 × 0.10 mm
Z = 2

Bruker SMART CCD area-detector diffractometer	2327 independent reflections
Radiation source: fine-focus sealed tube	2053 reflections with I > 2σ(I)
graphite	Rint = 0.028
φ and ω scans	θmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→8
Tmin = 0.904, Tmax = 0.988	k = −17→17
18931 measured reflections	l = −14→14

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0592P)2 + 0.4079P] where P = (Fo2 + 2Fc2)/3
2327 reflections	(Δ/σ)max < 0.001
163 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.28 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
N1	0.27652 (15)	0.50895 (8)	0.56149 (9)	0.0150 (2)
N2	0.15565 (15)	0.51345 (8)	0.31494 (9)	0.0165 (2)
H2A	0.1890	0.5153	0.3913	0.020*
O1	0.38783 (15)	0.30360 (6)	0.50820 (8)	0.0223 (2)
O2	0.08964 (13)	0.29549 (6)	0.56245 (7)	0.0182 (2)
O3	0.45903 (15)	0.26665 (6)	0.77965 (8)	0.0227 (2)
O4	0.47246 (15)	0.35410 (6)	0.94390 (8)	0.0224 (2)
H4A	0.5120	0.2999	0.9777	0.027*
C1	0.31214 (17)	0.42864 (8)	0.63036 (10)	0.0135 (2)
C2	0.38515 (17)	0.43413 (8)	0.75593 (10)	0.0137 (2)
C3	0.41707 (18)	0.52530 (9)	0.80969 (11)	0.0155 (3)
H3	0.4647	0.5310	0.8947	0.019*
C4	0.37892 (18)	0.60781 (9)	0.73843 (11)	0.0166 (3)
H4	0.3994	0.6707	0.7735	0.020*
C5	0.31027 (18)	0.59644 (9)	0.61490 (11)	0.0161 (3)
H5	0.2860	0.6528	0.5658	0.019*
C6	0.26464 (18)	0.33299 (9)	0.56194 (10)	0.0151 (3)
C7	0.44097 (18)	0.34292 (8)	0.82870 (10)	0.0148 (2)
C8	0.13421 (18)	0.59568 (9)	0.25032 (11)	0.0177 (3)
H8	0.1612	0.6565	0.2904	0.021*
C9	0.07338 (19)	0.59273 (9)	0.12624 (11)	0.0170 (3)
H9	0.0595	0.6512	0.0812	0.020*
C10	0.03217 (17)	0.50302 (9)	0.06698 (10)	0.0148 (3)
C11	0.05390 (19)	0.41949 (9)	0.13730 (11)	0.0180 (3)
H11	0.0250	0.3576	0.1002	0.022*
C12	0.11771 (19)	0.42708 (9)	0.26137 (11)	0.0187 (3)
H12	0.1347	0.3699	0.3090	0.022*

	U11	U22	U33	U12	U13	U23
N1	0.0158 (5)	0.0161 (5)	0.0131 (5)	0.0009 (4)	0.0039 (4)	0.0014 (4)
N2	0.0177 (5)	0.0207 (5)	0.0106 (5)	−0.0012 (4)	0.0032 (4)	0.0010 (4)
O1	0.0308 (5)	0.0181 (5)	0.0215 (5)	0.0006 (4)	0.0130 (4)	−0.0027 (3)
O2	0.0197 (4)	0.0178 (4)	0.0156 (4)	−0.0025 (3)	0.0026 (3)	−0.0045 (3)
O3	0.0355 (5)	0.0131 (4)	0.0151 (4)	0.0017 (4)	0.0002 (4)	−0.0007 (3)
O4	0.0375 (5)	0.0165 (5)	0.0118 (4)	0.0072 (4)	0.0045 (4)	0.0034 (3)
C1	0.0128 (5)	0.0142 (5)	0.0136 (5)	0.0006 (4)	0.0038 (4)	0.0009 (4)
C2	0.0137 (5)	0.0143 (6)	0.0129 (5)	0.0005 (4)	0.0036 (4)	0.0002 (4)
C3	0.0163 (5)	0.0170 (6)	0.0128 (5)	0.0008 (4)	0.0035 (4)	−0.0006 (4)
C4	0.0183 (6)	0.0137 (6)	0.0174 (6)	0.0001 (4)	0.0045 (5)	−0.0016 (4)
C5	0.0164 (6)	0.0139 (6)	0.0180 (6)	0.0015 (4)	0.0048 (4)	0.0032 (4)
C6	0.0207 (6)	0.0143 (6)	0.0084 (5)	0.0023 (4)	0.0012 (4)	0.0020 (4)
C7	0.0147 (5)	0.0152 (6)	0.0130 (5)	−0.0013 (4)	0.0013 (4)	0.0000 (4)
C8	0.0200 (6)	0.0170 (6)	0.0163 (6)	−0.0001 (4)	0.0052 (5)	−0.0002 (4)
C9	0.0190 (6)	0.0165 (6)	0.0153 (6)	0.0009 (4)	0.0046 (4)	0.0027 (4)
C10	0.0120 (5)	0.0187 (6)	0.0135 (6)	−0.0009 (4)	0.0034 (4)	0.0016 (4)
C11	0.0218 (6)	0.0165 (6)	0.0146 (6)	−0.0036 (5)	0.0033 (5)	0.0001 (4)
C12	0.0213 (6)	0.0184 (6)	0.0156 (6)	−0.0028 (5)	0.0037 (5)	0.0035 (5)

N1—C5	1.3446 (15)	C3—C4	1.3857 (16)
N1—C1	1.3457 (15)	C3—H3	0.9500
N2—C12	1.3330 (16)	C4—C5	1.3840 (17)
N2—C8	1.3432 (16)	C4—H4	0.9500
N2—H2A	0.8501	C5—H5	0.9500
O1—C6	1.2303 (15)	C8—C9	1.3807 (17)
O2—C6	1.2775 (15)	C8—H8	0.9500
O3—C7	1.2165 (15)	C9—C10	1.4030 (17)
O4—C7	1.3009 (14)	C9—H9	0.9500
O4—H4A	0.8501	C10—C11	1.3938 (17)
C1—C2	1.4009 (16)	C10—C10i	1.492 (2)
C1—C6	1.5245 (16)	C11—C12	1.3841 (17)
C2—C3	1.3915 (16)	C11—H11	0.9500
C2—C7	1.5007 (15)	C12—H12	0.9500
C5—N1—C1	119.02 (10)	O1—C6—C1	118.49 (11)
C12—N2—C8	121.10 (10)	O2—C6—C1	113.81 (10)
C12—N2—H2A	118.2	O3—C7—O4	124.97 (11)
C8—N2—H2A	120.7	O3—C7—C2	120.13 (10)
C7—O4—H4A	108.0	O4—C7—C2	114.88 (10)
N1—C1—C2	121.58 (10)	N2—C8—C9	120.66 (11)
N1—C1—C6	115.20 (10)	N2—C8—H8	119.7
C2—C1—C6	123.21 (10)	C9—C8—H8	119.7
C3—C2—C1	118.59 (10)	C8—C9—C10	119.71 (11)
C3—C2—C7	121.43 (10)	C8—C9—H9	120.1
C1—C2—C7	119.84 (10)	C10—C9—H9	120.1
C4—C3—C2	119.61 (11)	C11—C10—C9	117.85 (11)
C4—C3—H3	120.2	C11—C10—C10i	120.96 (13)
C2—C3—H3	120.2	C9—C10—C10i	121.19 (13)
C5—C4—C3	118.40 (11)	C12—C11—C10	119.75 (11)
C5—C4—H4	120.8	C12—C11—H11	120.1
C3—C4—H4	120.8	C10—C11—H11	120.1
N1—C5—C4	122.79 (11)	N2—C12—C11	120.93 (11)
N1—C5—H5	118.6	N2—C12—H12	119.5
C4—C5—H5	118.6	C11—C12—H12	119.5
O1—C6—O2	127.57 (11)
C5—N1—C1—C2	−0.59 (17)	C2—C1—C6—O2	78.49 (14)
C5—N1—C1—C6	178.63 (10)	C3—C2—C7—O3	−162.59 (11)
N1—C1—C2—C3	1.26 (17)	C1—C2—C7—O3	13.12 (17)
C6—C1—C2—C3	−177.90 (10)	C3—C2—C7—O4	15.52 (16)
N1—C1—C2—C7	−174.57 (10)	C1—C2—C7—O4	−168.77 (11)
C6—C1—C2—C7	6.27 (17)	C12—N2—C8—C9	−0.43 (18)
C1—C2—C3—C4	−0.83 (17)	N2—C8—C9—C10	0.43 (18)
C7—C2—C3—C4	174.93 (11)	C8—C9—C10—C11	0.31 (18)
C2—C3—C4—C5	−0.21 (17)	C8—C9—C10—C10i	−179.48 (13)
C1—N1—C5—C4	−0.53 (18)	C9—C10—C11—C12	−1.05 (18)
C3—C4—C5—N1	0.93 (18)	C10i—C10—C11—C12	178.75 (13)
N1—C1—C6—O1	75.36 (14)	C8—N2—C12—C11	−0.34 (18)
C2—C1—C6—O1	−105.43 (13)	C10—C11—C12—N2	1.09 (19)
N1—C1—C6—O2	−100.72 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1	0.85	1.90	2.7430 (14)	175
O4—H4A···O2ii	0.85	1.64	2.4782 (12)	171
C3—H3···O4iii	0.95	2.40	3.2055 (15)	143
C4—H4···O2iv	0.95	2.55	3.4324 (15)	155
C9—H9···O1v	0.95	2.41	3.3405 (15)	166
C11—H11···O1vi	0.95	2.52	3.4610 (15)	170
C12—H12···O3vi	0.95	2.19	2.9004 (15)	131

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1	0.85	1.90	2.7430 (14)	175
O4—H4A⋯O2i	0.85	1.64	2.4782 (12)	171
C3—H3⋯O4ii	0.95	2.40	3.2055 (15)	143
C4—H4⋯O2iii	0.95	2.55	3.4324 (15)	155
C9—H9⋯O1iv	0.95	2.41	3.3405 (15)	166
C11—H11⋯O1v	0.95	2.52	3.4610 (15)	170
C12—H12⋯O3v	0.95	2.19	2.9004 (15)	131

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