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Acta Cryst. (2009). E65, o614    [ doi:10.1107/S1600536809006412 ]

2-Carboxypyridinium hydrogen chloranilate

K. Gotoh, H. Nagoshi and H. Ishida

Abstract top

In the crystal structure of the title salt, C6H6NO2+·C6HCl2O4-, the pyridine ring and the mean plane of the hydrogen chloranilate anion form a dihedral angle of 77.40 (8)°. The ionic components are held together by N-H...O and O-H...O hydrogen bonds, forming a supramolecular ladder. C-H...O interactions are also present.

Comment top

The title salt, (I), was prepared in order to extend our study on D—H···A hydrogen bonding (D = N, O or C; A = N, O or Cl) in chloranilic acid – substituted-pyridine systems (Gotoh et al., 2006; Tabuchi et al., 2005).

Compound (I) comprises 2-carboxypyridinium cations and hydrogen chloranilate anions in the ratio 1:1. Ions directly connected by an N—H···O hydrogen bond, Fig. 1, form a dihedral angle between their respective mean planes of 77.40 (8)°. In the cation, the carboxy O5/O6/C12 plane forms a dihedral angle of 11.44 (6)° with the pyridine ring, which is similar to those of 2.74 (6) and 10.01 (3)° observed in 3-carboxypyridinium hydrogen chloranilate and 4-carboxypyridinium hydrogen chloranilate monohydrate, respectively (Ishida, 2009). The ions are further connected by O—H···O hydrogen bonds (Table 1) to afford a supramolecular ladder running along the c axis (Fig. 2). The ladders are linked by weaker N—H···O hydrogen bonds and C—H···O contacts to form a 3-D network (Table 1).

Related literature top

For the structures of related carboxypyridinium hydrogen chloranilates, see: Gotoh et al. (2006); Tabuchi et al. (2005); Ishida (2009).

Experimental top

Crystals were obtained by slow evaporation from a methanol solution (ca 30 ml) containing a 1:1 molar ratio of chloranilic acid (0.302 g) and picolinic acid (0.179 g).

Refinement top

The H atoms attached to O and N were located from a difference Fourier map and refined isotropically to O—H = 0.79 (3) & 0.90 (3) Å and N—H = 0.92 (4) Å. The remaining H atoms were included in the riding approximation with C—H = 0.95 Å, and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: PROCESS-AUTO (Rigaku/MSC, 2004); cell refinement: PROCESS-AUTO (Rigaku/MSC, 2004); data reduction: CrystalStructure (Rigaku/MSC, 2004); 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: CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. Molecular components of (I) showing the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Intra- and inter-molecular N—H···O hydrogen bonds are indicated by dashed lines.
[Figure 2] Fig. 2. A partial packing diagram, viewed approximately along the a axis, showing the hydrogen-bonded supramolecular ladder. Dashed lines show N—H···O and O—H···O hydrogen bonds (symmetry codes as given in Table 1).
2-Carboxypyridinium hydrogen chloranilate top
Crystal data top
C6H6NO2+·C6HCl2O4−F(000) = 672.00
Mr = 332.10Dx = 1.795 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybcCell parameters from 7392 reflections
a = 9.4166 (8) Åθ = 3.0–30.0°
b = 19.6900 (16) ŵ = 0.56 mm−1
c = 6.7089 (6) ÅT = 103 K
β = 99.043 (3)°Platelet, dark purple
V = 1228.45 (18) Å30.30 × 0.30 × 0.23 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID-II
diffractometer		2228 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm-1Rint = 0.047
ω scansθmax = 30.0°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −13→13
Tmin = 0.847, Tmax = 0.880k = −27→27
9710 measured reflectionsl = −8→9
3433 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.0659P)2 + 0.8975P]
where P = (Fo2 + 2Fc2)/3
3433 reflections(Δ/σ)max < 0.001
202 parametersΔρmax = 0.47 e Å−3
0 restraintsΔρmin = −0.92 e Å−3
Primary atom site location: structure-invariant direct methods
Crystal data top
C6H6NO2+·C6HCl2O4−V = 1228.45 (18) Å3
Mr = 332.10Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.4166 (8) ŵ = 0.56 mm−1
b = 19.6900 (16) ÅT = 103 K
c = 6.7089 (6) Å0.30 × 0.30 × 0.23 mm
β = 99.043 (3)°
Data collection top
Rigaku R-AXIS RAPID-II
diffractometer		3433 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2228 reflections with I > 2σ(I)
Tmin = 0.847, Tmax = 0.880Rint = 0.047
9710 measured reflectionsθmax = 30.0°
Refinement top
R[F2 > 2σ(F2)] = 0.045H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.144Δρmax = 0.47 e Å−3
S = 1.10Δρmin = −0.92 e Å−3
3433 reflectionsAbsolute structure: ?
202 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Cl1−0.17894 (6)0.28996 (3)0.27912 (9)0.02060 (16)
Cl20.46528 (6)0.29140 (3)0.10812 (9)0.02077 (16)
O10.00723 (19)0.40867 (8)0.2367 (3)0.0218 (4)
O20.01147 (19)0.17042 (9)0.2397 (3)0.0184 (3)
O30.27117 (18)0.17271 (8)0.1488 (3)0.0196 (4)
O40.27772 (19)0.41277 (8)0.1577 (3)0.0209 (4)
O50.12383 (18)0.45615 (9)0.6917 (3)0.0215 (4)
O60.3466 (2)0.47658 (10)0.8601 (3)0.0265 (4)
N10.1860 (2)0.52690 (11)0.3720 (3)0.0199 (4)
C10.0667 (2)0.35416 (11)0.2174 (3)0.0164 (4)
C2−0.0036 (2)0.28950 (11)0.2347 (3)0.0160 (4)
C30.0678 (2)0.23079 (11)0.2188 (3)0.0154 (4)
C40.2206 (2)0.22965 (11)0.1715 (3)0.0155 (4)
C50.2899 (2)0.29272 (11)0.1544 (4)0.0170 (4)
C60.2232 (2)0.35480 (12)0.1732 (3)0.0165 (4)
C70.2794 (3)0.52837 (12)0.5464 (4)0.0198 (5)
C80.3984 (3)0.56970 (13)0.5626 (4)0.0229 (5)
H80.46560.57080.68400.027*
C90.4194 (3)0.60996 (13)0.3987 (4)0.0262 (5)
H90.50100.63880.40770.031*
C100.3206 (3)0.60759 (13)0.2230 (4)0.0268 (5)
H100.33320.63520.11090.032*
C110.2035 (3)0.56488 (13)0.2118 (4)0.0239 (5)
H110.13570.56240.09130.029*
C120.2418 (3)0.48289 (12)0.7090 (4)0.0195 (5)
H10.109 (5)0.498 (2)0.363 (6)0.053 (11)*
H20.071 (4)0.1437 (17)0.227 (5)0.032 (9)*
H60.319 (4)0.4534 (18)0.964 (6)0.043 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0146 (3)0.0253 (3)0.0233 (3)0.0013 (2)0.0076 (2)−0.0006 (2)
Cl20.0151 (3)0.0258 (3)0.0230 (3)−0.0018 (2)0.0080 (2)−0.0011 (2)
O10.0207 (8)0.0196 (8)0.0256 (9)0.0020 (7)0.0051 (7)−0.0022 (7)
O20.0163 (8)0.0164 (7)0.0238 (9)0.0013 (7)0.0074 (7)−0.0008 (7)
O30.0176 (8)0.0201 (8)0.0220 (8)0.0016 (7)0.0063 (7)−0.0008 (7)
O40.0232 (9)0.0200 (8)0.0210 (9)−0.0027 (7)0.0083 (7)0.0019 (6)
O50.0177 (8)0.0212 (8)0.0274 (9)−0.0017 (7)0.0094 (7)0.0018 (7)
O60.0221 (9)0.0336 (10)0.0235 (9)−0.0063 (8)0.0024 (7)0.0050 (8)
N10.0145 (9)0.0229 (10)0.0229 (10)−0.0018 (8)0.0050 (8)0.0000 (8)
C10.0182 (10)0.0180 (10)0.0130 (10)0.0007 (9)0.0020 (8)0.0001 (8)
C20.0130 (10)0.0197 (10)0.0152 (10)0.0009 (8)0.0023 (8)−0.0019 (8)
C30.0154 (10)0.0183 (10)0.0132 (10)−0.0002 (8)0.0048 (8)0.0005 (8)
C40.0149 (10)0.0193 (10)0.0132 (10)0.0009 (8)0.0048 (8)0.0003 (8)
C50.0132 (10)0.0207 (10)0.0176 (10)−0.0013 (9)0.0041 (8)−0.0006 (9)
C60.0165 (10)0.0204 (10)0.0133 (10)−0.0014 (9)0.0039 (8)−0.0011 (8)
C70.0179 (11)0.0184 (11)0.0241 (12)0.0001 (9)0.0067 (9)−0.0006 (9)
C80.0188 (11)0.0236 (12)0.0272 (13)0.0000 (10)0.0066 (10)−0.0018 (10)
C90.0223 (12)0.0231 (12)0.0355 (14)−0.0031 (10)0.0118 (11)0.0023 (11)
C100.0292 (13)0.0248 (12)0.0291 (13)0.0006 (11)0.0129 (11)0.0049 (10)
C110.0229 (12)0.0270 (12)0.0221 (12)0.0049 (10)0.0051 (10)0.0028 (10)
C120.0210 (11)0.0193 (10)0.0197 (11)−0.0002 (9)0.0076 (9)−0.0021 (9)
Geometric parameters (Å, °) top
Cl1—C21.723 (2)C1—C61.548 (3)
Cl2—C51.727 (2)C2—C31.350 (3)
O1—C11.227 (3)C3—C41.521 (3)
O2—C31.318 (3)C4—C51.416 (3)
O2—H20.79 (3)C5—C61.389 (3)
O3—C41.237 (3)C7—C81.375 (3)
O4—C61.263 (3)C7—C121.497 (3)
O5—C121.218 (3)C8—C91.394 (4)
O6—C121.305 (3)C8—H80.9500
O6—H60.90 (4)C9—C101.383 (4)
N1—C111.340 (3)C9—H90.9500
N1—C71.349 (3)C10—C111.379 (4)
N1—H10.92 (4)C10—H100.9500
C1—C21.448 (3)C11—H110.9500
C3—O2—H2107 (3)O4—C6—C1115.8 (2)
C12—O6—H6112 (2)C5—C6—C1117.90 (19)
C11—N1—C7122.5 (2)N1—C7—C8119.6 (2)
C11—N1—H1119 (2)N1—C7—C12115.0 (2)
C7—N1—H1118 (2)C8—C7—C12125.4 (2)
O1—C1—C2122.6 (2)C7—C8—C9119.3 (2)
O1—C1—C6118.5 (2)C7—C8—H8120.4
C2—C1—C6118.91 (19)C9—C8—H8120.4
C3—C2—C1120.4 (2)C10—C9—C8119.5 (2)
C3—C2—Cl1121.40 (18)C10—C9—H9120.2
C1—C2—Cl1118.15 (17)C8—C9—H9120.2
O2—C3—C2123.3 (2)C11—C10—C9119.5 (2)
O2—C3—C4114.75 (19)C11—C10—H10120.3
C2—C3—C4121.9 (2)C9—C10—H10120.3
O3—C4—C5126.4 (2)N1—C11—C10119.7 (2)
O3—C4—C3115.7 (2)N1—C11—H11120.2
C5—C4—C3117.85 (19)C10—C11—H11120.2
C6—C5—C4122.9 (2)O5—C12—O6126.9 (2)
C6—C5—Cl2119.23 (17)O5—C12—C7120.4 (2)
C4—C5—Cl2117.86 (17)O6—C12—C7112.7 (2)
O4—C6—C5126.3 (2)
O1—C1—C2—C3−177.9 (2)C4—C5—C6—C10.7 (3)
C6—C1—C2—C32.1 (3)Cl2—C5—C6—C1−179.21 (16)
O1—C1—C2—Cl11.3 (3)O1—C1—C6—O4−0.9 (3)
C6—C1—C2—Cl1−178.77 (16)C2—C1—C6—O4179.2 (2)
C1—C2—C3—O2177.7 (2)O1—C1—C6—C5179.2 (2)
Cl1—C2—C3—O2−1.4 (3)C2—C1—C6—C5−0.7 (3)
C1—C2—C3—C4−3.3 (3)C11—N1—C7—C8−0.6 (4)
Cl1—C2—C3—C4177.58 (16)C11—N1—C7—C12179.6 (2)
O2—C3—C4—O33.3 (3)N1—C7—C8—C90.7 (4)
C2—C3—C4—O3−175.8 (2)C12—C7—C8—C9−179.5 (2)
O2—C3—C4—C5−177.73 (19)C7—C8—C9—C10−0.1 (4)
C2—C3—C4—C53.2 (3)C8—C9—C10—C11−0.7 (4)
O3—C4—C5—C6177.0 (2)C7—N1—C11—C10−0.2 (4)
C3—C4—C5—C6−1.8 (3)C9—C10—C11—N10.8 (4)
O3—C4—C5—Cl2−3.0 (3)N1—C7—C12—O5−11.4 (3)
C3—C4—C5—Cl2178.11 (16)C8—C7—C12—O5168.8 (2)
C4—C5—C6—O4−179.2 (2)N1—C7—C12—O6168.4 (2)
Cl2—C5—C6—O40.8 (3)C8—C7—C12—O6−11.4 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.92 (4)2.11 (3)2.932 (2)147 (3)
N1—H1···O50.92 (4)2.33 (4)2.698 (2)103 (2)
N1—H1···O5i0.92 (4)2.34 (4)2.900 (2)119 (3)
O2—H2···O30.79 (3)2.11 (3)2.612 (2)122 (3)
O2—H2···O5ii0.79 (3)2.05 (3)2.746 (2)148 (3)
O6—H6···O4iii0.90 (3)1.63 (3)2.528 (2)177.1 (15)
C8—H8···O4iv0.952.503.338 (3)147
C9—H9···O3v0.952.333.227 (3)156
C11—H11···O1vi0.952.463.374 (3)162
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, −y+1/2, z−1/2; (iii) x, y, z+1; (iv) −x+1, −y+1, −z+1; (v) −x+1, y+1/2, −z+1/2; (vi) −x, −y+1, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.92 (4)2.11 (3)2.932 (2)147 (3)
O2—H2···O5i0.79 (3)2.05 (3)2.746 (2)148 (3)
O6—H6···O4ii0.90 (3)1.63 (3)2.528 (2)177.1 (15)
C8—H8···O4iii0.952.503.338 (3)147
C9—H9···O3iv0.952.333.227 (3)156
C11—H11···O1v0.952.463.374 (3)162
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, y, z+1; (iii) −x+1, −y+1, −z+1; (iv) −x+1, y+1/2, −z+1/2; (v) −x, −y+1, −z.
Acknowledgements top

This work was supported by a Grant-in-Aid for Scientific Research (C) (No. 19550018) from the Japan Society for the Promotion of Science.

references
References top

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Tabuchi, Y., Takahashi, A., Gotoh, K., Akashi, H. & Ishida, H. (2005). Acta Cryst. E61, o4215–o4217.