Bis(3-hydroxy-pyridinium) fumarate.

The crystal structure of the title compound, 2C(5)H(6)NO(2) (+)·C(4)H(2)O(4) (2-), consists of 3-hydroxy-pyridinium cations and fumarate dianions. The dianion is located on an inversion center and the cation is linked to it by O-H⋯O and N-H⋯O hydrogen bonds. The cation is twisted with respect to the anion by 24.83 (5)°.

Related literature

For general background, see: Thomas et al. (2007 ▶); Fidler et al. (2003 ▶); Zhang et al. (2004 ▶). For the ionization of hydro­pyridine in the solution, see: Lezina et al. (1981 ▶). For 3-hydro­pyridinium salts, see: Aakeroy & Nieuwenhuyzen (1994 ▶); Fukunaga et al. (2004 ▶). For co-crystals of neutral pyridine derivatives and neutral fumaric acid, see: Bowes et al. (2003 ▶); Aakeroy et al. (2002 ▶); Haynes et al. (2006 ▶); Bu et al. (2007 ▶); Xu et al. (2009 ▶). For C—O bond distances in the deprotonated carboxyl groups of fumarates, see: Liu et al. (2003 ▶); Liu & Xu (2004 ▶); Xu et al. (2009 ▶).

Experimental

Crystal data

2C5H6NO+·C4H2O4 2−

M = 306.27

Monoclinic,

a = 3.8037 (5) Å

b = 10.4798 (13) Å

c = 17.423 (2) Å

β = 90.360 (5)°

V = 694.52 (15) Å3

Z = 2

Mo Kα radiation

μ = 0.12 mm−1

T = 294 K

0.32 × 0.28 × 0.24 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: none

7561 measured reflections

1359 independent reflections

1237 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.100

S = 1.07

1359 reflections

107 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.14 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023800/ng2594sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023800/ng2594Isup2.hkl

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

2C5H6NO+·C4H2O42−	F(000) = 320
Mr = 306.27	Dx = 1.465 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2322 reflections
a = 3.8037 (5) Å	θ = 2.4–24.6°
b = 10.4798 (13) Å	µ = 0.12 mm−1
c = 17.423 (2) Å	T = 294 K
β = 90.360 (5)°	Prism, colorless
V = 694.52 (15) Å3	0.32 × 0.28 × 0.24 mm
Z = 2

Rigaku R-AXIS RAPID IP diffractometer	1237 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
graphite	θmax = 26.0°, θmin = 2.3°
ω scans	h = −4→4
7561 measured reflections	k = −12→12
1359 independent reflections	l = −20→21

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)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.100	w = 1/[σ2(Fo2) + (0.0527P)2 + 0.1474P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
1359 reflections	Δρmax = 0.25 e Å−3
107 parameters	Δρmin = −0.14 e Å−3
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.116 (10)

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	0.0136 (3)	0.56088 (11)	0.76518 (6)	0.0373 (3)
O1	0.2604 (3)	0.49000 (9)	0.63451 (5)	0.0489 (3)
O2	0.4289 (3)	0.69067 (9)	0.62330 (5)	0.0568 (4)
O3	−0.2084 (3)	0.39098 (10)	0.93748 (6)	0.0559 (3)
C1	0.3982 (3)	0.58033 (12)	0.59760 (7)	0.0368 (3)
C2	0.5267 (3)	0.55371 (13)	0.51822 (7)	0.0375 (3)
H2	0.6522	0.6174	0.4933	0.045*
C3	−0.0215 (3)	0.46506 (12)	0.81483 (7)	0.0357 (3)
H3	0.0526	0.3836	0.8012	0.043*
C4	−0.1676 (3)	0.48541 (12)	0.88672 (7)	0.0366 (3)
C5	−0.2754 (3)	0.60885 (13)	0.90499 (7)	0.0410 (3)
H5	−0.3763	0.6256	0.9524	0.049*
C6	−0.2323 (4)	0.70583 (13)	0.85271 (8)	0.0431 (3)
H6	−0.3019	0.7885	0.8647	0.052*
C7	−0.0849 (4)	0.67954 (13)	0.78221 (8)	0.0418 (3)
H7	−0.0543	0.7447	0.7466	0.050*
H1	0.103 (4)	0.5407 (17)	0.7195 (6)	0.063*
H3A	−0.127 (5)	0.3217 (12)	0.9213 (10)	0.063*

	U11	U22	U33	U12	U13	U23
N1	0.0428 (6)	0.0421 (6)	0.0271 (5)	−0.0016 (5)	0.0072 (4)	0.0009 (4)
O1	0.0743 (7)	0.0392 (6)	0.0333 (5)	−0.0081 (4)	0.0207 (5)	−0.0027 (4)
O2	0.0928 (9)	0.0383 (6)	0.0397 (6)	−0.0108 (5)	0.0225 (5)	−0.0095 (4)
O3	0.0852 (8)	0.0450 (6)	0.0378 (6)	0.0079 (5)	0.0253 (5)	0.0091 (4)
C1	0.0467 (7)	0.0355 (7)	0.0283 (6)	−0.0003 (5)	0.0071 (5)	−0.0027 (5)
C2	0.0468 (7)	0.0369 (7)	0.0290 (6)	−0.0030 (5)	0.0103 (5)	0.0003 (5)
C3	0.0420 (7)	0.0342 (6)	0.0310 (6)	0.0005 (5)	0.0076 (5)	−0.0018 (5)
C4	0.0407 (7)	0.0406 (7)	0.0285 (6)	−0.0012 (5)	0.0072 (5)	0.0016 (5)
C5	0.0441 (7)	0.0472 (8)	0.0318 (6)	0.0042 (6)	0.0087 (5)	−0.0056 (6)
C6	0.0481 (7)	0.0363 (7)	0.0450 (7)	0.0055 (5)	0.0039 (6)	−0.0043 (5)
C7	0.0482 (8)	0.0386 (7)	0.0387 (7)	−0.0001 (5)	0.0044 (5)	0.0067 (5)

N1—C7	1.3327 (17)	C2—H2	0.9300
N1—C3	1.3327 (16)	C3—C4	1.3898 (17)
N1—H1	0.893 (12)	C3—H3	0.9300
O1—C1	1.2603 (15)	C4—C5	1.3945 (18)
O2—C1	1.2452 (15)	C5—C6	1.3752 (19)
O3—C4	1.3369 (15)	C5—H5	0.9300
O3—H3A	0.839 (14)	C6—C7	1.3813 (19)
C1—C2	1.4962 (16)	C6—H6	0.9300
C2—C2i	1.308 (3)	C7—H7	0.9300
C7—N1—C3	121.94 (11)	O3—C4—C3	122.09 (12)
C7—N1—H1	121.9 (12)	O3—C4—C5	120.01 (11)
C3—N1—H1	116.2 (12)	C3—C4—C5	117.90 (11)
C4—O3—H3A	111.9 (13)	C6—C5—C4	119.86 (11)
O2—C1—O1	123.54 (11)	C6—C5—H5	120.1
O2—C1—C2	118.36 (11)	C4—C5—H5	120.1
O1—C1—C2	118.10 (11)	C5—C6—C7	119.49 (12)
C2i—C2—C1	123.96 (15)	C5—C6—H6	120.3
C2i—C2—H2	118.0	C7—C6—H6	120.3
C1—C2—H2	118.0	N1—C7—C6	120.03 (12)
N1—C3—C4	120.77 (12)	N1—C7—H7	120.0
N1—C3—H3	119.6	C6—C7—H7	120.0
C4—C3—H3	119.6

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.89 (1)	1.69 (1)	2.5774 (14)	175 (2)
O3—H3A···O2ii	0.84 (1)	1.75 (2)	2.5831 (15)	172 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.893 (12)	1.687 (12)	2.5774 (14)	175.2 (18)
O3—H3A⋯O2i	0.839 (14)	1.751 (15)	2.5831 (15)	171.5 (16)

Symmetry code: (i) .