Bis(3-hydroxy­pyridinium) fumarate

Shen, L.; Li, J.-H.; Nie, J.-J.; Xu, D.-J.

doi:10.1107/S1600536809023800

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1679

doi:10.1107/S1600536809023800

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Bis(3-hydroxypyridinium) fumarate

Lan Shen,^a Jun-Hua Li,^b Jing-Jing Nie ^b and Duan-Jun Xu ^b ^*

^aDepartment of Obstetrics & Gynecology, Hangzhou Red Cross Hospital, Hangzhou 310003, People's Republic of China, and ^bDepartment of Chemistry, Zhejiang University, People's Republic of China
^*Correspondence e-mail: xudj@mail.hz.zj.cn

(Received 6 June 2009; accepted 21 June 2009; online 24 June 2009)

The crystal structure of the title compound, 2C₅H₆NO₂⁺·C₄H₂O₄²⁻, consists of 3-hydroxypyridinium 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⁺·C₄H₂O₄²⁻
M_r = 306.27
Monoclinic, P 2₁ /n
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[F² > 2σ(F²)] = 0.037
wR(F²) = 0.100
S = 1.07
1359 reflections
107 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.14 e Å⁻³

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) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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 ).

Supporting information

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

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

checkCIF report

Comment top

The hydropyridine derivatives and the fumaric acid have been extensively applied in biological and medicine fields (Zhang et al., 2004; Thomas et al., 2007; Fidler et al., 2003). Although the carboxyl group of the fumaric acid is usually deprotonated while the pyridine derivatives are protonated in the solution (Lezina et al., 1981), some crystal structures showed that they also exist as co-crystal of neutral molecules (Bowes et al. 2003; Aakeroy et al., 2002; Haynes et al. 2006; Xu et al. 2009). Herein we report the crystal structure of the title compound containing pyridine derivative and fumaric acid components.

The crystal structure of the title compond consists of fumarate anions and 3-hydroxypyridinium cations (Fig. 1). The planar fumarate anion is located in an inversion center. The C1—O1 bond distance of 1.2603 (15) Å is similar to C1—O2 bond distance of 1.2452 (15) Å, it agrees with those found in metal complexes of fumarate (Liu et al. 2003; Liu & Xu, 2004).

The 3-hydroxypyridine is protonated in the crystal structure, the geometry data is consistent with those in crystal structures of 3-hydroxypyridinium hydrogen L-malate (Aakeroy & Nieuwenhuyzen, 1994) and 3-hydroxypyridinium hydrogen tartronate (Fukunaga et al. 2004).

In the crystal structure the planar hydroxypyridinium cation is twisted respect to the planar fumarate with a dihedral angle of 24.83 (5)°, and links with the fumarate anions via N—H···O and O—H···O hydrogen bonding (Table 1 and Fig. 2).

Related literature top

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 top

Reagents and solvent were used as purchased without further purification. 3-Hydroxypyridine (2 mmol) and fumaric acid (1 mmol) were dissolved in ethanol (5 ml) at room temperature. The single crystals were obtained from the solution after one week.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); 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).

Figures top

	Fig. 1. The molecular structure of the title compound with 40% probability displacement (arbitrary spheres for H atoms). Dashed lines indicate hydrogen bonding [symmetry code: (i) 1 - x, 1 - y, 1 - z].
	Fig. 2. The unit cell packing diagram showing O—H···O and N—H···O hydrogen bonding (dashed lines) [symmetry code: (ii) -x + 1/2, y + 1/2, -z + 1/2].

Bis(3-hydroxypyridinium) fumarate top

Crystal data top

2C₅H₆NO⁺·C₄H₂O₄²⁻	F(000) = 320
M_r = 306.27	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0527P)² + 0.1474P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
1359 reflections	Δρ_max = 0.25 e Å⁻³
107 parameters	Δρ_min = −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)

Crystal data top

2C₅H₆NO⁺·C₄H₂O₄²⁻	V = 694.52 (15) Å³
M_r = 306.27	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.8037 (5) Å	µ = 0.12 mm⁻¹
b = 10.4798 (13) Å	T = 294 K
c = 17.423 (2) Å	0.32 × 0.28 × 0.24 mm
β = 90.360 (5)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1237 reflections with I > 2σ(I)
7561 measured reflections	R_int = 0.024
1359 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	2 restraints
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.25 e Å⁻³
1359 reflections	Δρ_min = −0.14 e Å⁻³
107 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

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)

Symmetry code: (ii) −x+1/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	2C₅H₆NO⁺·C₄H₂O₄²⁻
M_r	306.27
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	3.8037 (5), 10.4798 (13), 17.423 (2)
β (°)	90.360 (5)
V (Å³)	694.52 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.32 × 0.28 × 0.24

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7561, 1359, 1237
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.100, 1.07
No. of reflections	1359
No. of parameters	107
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.14

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

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) −x+1/2, y−1/2, −z+3/2.

Acknowledgements

The work was supported by the ZIJIN Project of Zhejiang University, China.

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