2-Carboxy-pyridinium hydrogen chloranilate.

In the crystal structure of the title salt, C(6)H(6)NO(2) (+)·C(6)HCl(2)O(4) (-), 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 supra-molecular ladder. C-H⋯O inter-actions are also present.

Related literature

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

Experimental

Crystal data

C6H6NO2 +·C6HCl2O4 −

M = 332.10

Monoclinic,

a = 9.4166 (8) Å

b = 19.6900 (16) Å

c = 6.7089 (6) Å

β = 99.043 (3)°

V = 1228.45 (18) Å3

Z = 4

Mo Kα radiation

μ = 0.56 mm−1

T = 103 K

0.30 × 0.30 × 0.23 mm

Data collection

Rigaku R-AXIS RAPID-II diffractometer

Absorption correction: multi-scan (; Higashi, 1995 ▶) T min = 0.847, T max = 0.880

9710 measured reflections

3433 independent reflections

2228 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.144

S = 1.10

3433 reflections

202 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.92 e Å−3

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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809006412/tk2376sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809006412/tk2376Isup2.hkl

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

C6H6NO2+·C6HCl2O4−	F(000) = 672.00
Mr = 332.10	Dx = 1.795 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 7392 reflections
a = 9.4166 (8) Å	θ = 3.0–30.0°
b = 19.6900 (16) Å	µ = 0.56 mm−1
c = 6.7089 (6) Å	T = 103 K
β = 99.043 (3)°	Platelet, dark purple
V = 1228.45 (18) Å3	0.30 × 0.30 × 0.23 mm
Z = 4

Rigaku R-AXIS RAPID-II diffractometer	2228 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm-1	Rint = 0.047
ω scans	θmax = 30.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −13→13
Tmin = 0.847, Tmax = 0.880	k = −27→27
9710 measured reflections	l = −8→9
3433 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144	H 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 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.92 e Å−3
Primary atom site location: structure-invariant direct methods

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
Cl1	−0.17894 (6)	0.28996 (3)	0.27912 (9)	0.02060 (16)
Cl2	0.46528 (6)	0.29140 (3)	0.10812 (9)	0.02077 (16)
O1	0.00723 (19)	0.40867 (8)	0.2367 (3)	0.0218 (4)
O2	0.01147 (19)	0.17042 (9)	0.2397 (3)	0.0184 (3)
O3	0.27117 (18)	0.17271 (8)	0.1488 (3)	0.0196 (4)
O4	0.27772 (19)	0.41277 (8)	0.1577 (3)	0.0209 (4)
O5	0.12383 (18)	0.45615 (9)	0.6917 (3)	0.0215 (4)
O6	0.3466 (2)	0.47658 (10)	0.8601 (3)	0.0265 (4)
N1	0.1860 (2)	0.52690 (11)	0.3720 (3)	0.0199 (4)
C1	0.0667 (2)	0.35416 (11)	0.2174 (3)	0.0164 (4)
C2	−0.0036 (2)	0.28950 (11)	0.2347 (3)	0.0160 (4)
C3	0.0678 (2)	0.23079 (11)	0.2188 (3)	0.0154 (4)
C4	0.2206 (2)	0.22965 (11)	0.1715 (3)	0.0155 (4)
C5	0.2899 (2)	0.29272 (11)	0.1544 (4)	0.0170 (4)
C6	0.2232 (2)	0.35480 (12)	0.1732 (3)	0.0165 (4)
C7	0.2794 (3)	0.52837 (12)	0.5464 (4)	0.0198 (5)
C8	0.3984 (3)	0.56970 (13)	0.5626 (4)	0.0229 (5)
H8	0.4656	0.5708	0.6840	0.027*
C9	0.4194 (3)	0.60996 (13)	0.3987 (4)	0.0262 (5)
H9	0.5010	0.6388	0.4077	0.031*
C10	0.3206 (3)	0.60759 (13)	0.2230 (4)	0.0268 (5)
H10	0.3332	0.6352	0.1109	0.032*
C11	0.2035 (3)	0.56488 (13)	0.2118 (4)	0.0239 (5)
H11	0.1357	0.5624	0.0913	0.029*
C12	0.2418 (3)	0.48289 (12)	0.7090 (4)	0.0195 (5)
H1	0.109 (5)	0.498 (2)	0.363 (6)	0.053 (11)*
H2	0.071 (4)	0.1437 (17)	0.227 (5)	0.032 (9)*
H6	0.319 (4)	0.4534 (18)	0.964 (6)	0.043 (10)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0146 (3)	0.0253 (3)	0.0233 (3)	0.0013 (2)	0.0076 (2)	−0.0006 (2)
Cl2	0.0151 (3)	0.0258 (3)	0.0230 (3)	−0.0018 (2)	0.0080 (2)	−0.0011 (2)
O1	0.0207 (8)	0.0196 (8)	0.0256 (9)	0.0020 (7)	0.0051 (7)	−0.0022 (7)
O2	0.0163 (8)	0.0164 (7)	0.0238 (9)	0.0013 (7)	0.0074 (7)	−0.0008 (7)
O3	0.0176 (8)	0.0201 (8)	0.0220 (8)	0.0016 (7)	0.0063 (7)	−0.0008 (7)
O4	0.0232 (9)	0.0200 (8)	0.0210 (9)	−0.0027 (7)	0.0083 (7)	0.0019 (6)
O5	0.0177 (8)	0.0212 (8)	0.0274 (9)	−0.0017 (7)	0.0094 (7)	0.0018 (7)
O6	0.0221 (9)	0.0336 (10)	0.0235 (9)	−0.0063 (8)	0.0024 (7)	0.0050 (8)
N1	0.0145 (9)	0.0229 (10)	0.0229 (10)	−0.0018 (8)	0.0050 (8)	0.0000 (8)
C1	0.0182 (10)	0.0180 (10)	0.0130 (10)	0.0007 (9)	0.0020 (8)	0.0001 (8)
C2	0.0130 (10)	0.0197 (10)	0.0152 (10)	0.0009 (8)	0.0023 (8)	−0.0019 (8)
C3	0.0154 (10)	0.0183 (10)	0.0132 (10)	−0.0002 (8)	0.0048 (8)	0.0005 (8)
C4	0.0149 (10)	0.0193 (10)	0.0132 (10)	0.0009 (8)	0.0048 (8)	0.0003 (8)
C5	0.0132 (10)	0.0207 (10)	0.0176 (10)	−0.0013 (9)	0.0041 (8)	−0.0006 (9)
C6	0.0165 (10)	0.0204 (10)	0.0133 (10)	−0.0014 (9)	0.0039 (8)	−0.0011 (8)
C7	0.0179 (11)	0.0184 (11)	0.0241 (12)	0.0001 (9)	0.0067 (9)	−0.0006 (9)
C8	0.0188 (11)	0.0236 (12)	0.0272 (13)	0.0000 (10)	0.0066 (10)	−0.0018 (10)
C9	0.0223 (12)	0.0231 (12)	0.0355 (14)	−0.0031 (10)	0.0118 (11)	0.0023 (11)
C10	0.0292 (13)	0.0248 (12)	0.0291 (13)	0.0006 (11)	0.0129 (11)	0.0049 (10)
C11	0.0229 (12)	0.0270 (12)	0.0221 (12)	0.0049 (10)	0.0051 (10)	0.0028 (10)
C12	0.0210 (11)	0.0193 (10)	0.0197 (11)	−0.0002 (9)	0.0076 (9)	−0.0021 (9)

Cl1—C2	1.723 (2)	C1—C6	1.548 (3)
Cl2—C5	1.727 (2)	C2—C3	1.350 (3)
O1—C1	1.227 (3)	C3—C4	1.521 (3)
O2—C3	1.318 (3)	C4—C5	1.416 (3)
O2—H2	0.79 (3)	C5—C6	1.389 (3)
O3—C4	1.237 (3)	C7—C8	1.375 (3)
O4—C6	1.263 (3)	C7—C12	1.497 (3)
O5—C12	1.218 (3)	C8—C9	1.394 (4)
O6—C12	1.305 (3)	C8—H8	0.9500
O6—H6	0.90 (4)	C9—C10	1.383 (4)
N1—C11	1.340 (3)	C9—H9	0.9500
N1—C7	1.349 (3)	C10—C11	1.379 (4)
N1—H1	0.92 (4)	C10—H10	0.9500
C1—C2	1.448 (3)	C11—H11	0.9500
C3—O2—H2	107 (3)	O4—C6—C1	115.8 (2)
C12—O6—H6	112 (2)	C5—C6—C1	117.90 (19)
C11—N1—C7	122.5 (2)	N1—C7—C8	119.6 (2)
C11—N1—H1	119 (2)	N1—C7—C12	115.0 (2)
C7—N1—H1	118 (2)	C8—C7—C12	125.4 (2)
O1—C1—C2	122.6 (2)	C7—C8—C9	119.3 (2)
O1—C1—C6	118.5 (2)	C7—C8—H8	120.4
C2—C1—C6	118.91 (19)	C9—C8—H8	120.4
C3—C2—C1	120.4 (2)	C10—C9—C8	119.5 (2)
C3—C2—Cl1	121.40 (18)	C10—C9—H9	120.2
C1—C2—Cl1	118.15 (17)	C8—C9—H9	120.2
O2—C3—C2	123.3 (2)	C11—C10—C9	119.5 (2)
O2—C3—C4	114.75 (19)	C11—C10—H10	120.3
C2—C3—C4	121.9 (2)	C9—C10—H10	120.3
O3—C4—C5	126.4 (2)	N1—C11—C10	119.7 (2)
O3—C4—C3	115.7 (2)	N1—C11—H11	120.2
C5—C4—C3	117.85 (19)	C10—C11—H11	120.2
C6—C5—C4	122.9 (2)	O5—C12—O6	126.9 (2)
C6—C5—Cl2	119.23 (17)	O5—C12—C7	120.4 (2)
C4—C5—Cl2	117.86 (17)	O6—C12—C7	112.7 (2)
O4—C6—C5	126.3 (2)
O1—C1—C2—C3	−177.9 (2)	C4—C5—C6—C1	0.7 (3)
C6—C1—C2—C3	2.1 (3)	Cl2—C5—C6—C1	−179.21 (16)
O1—C1—C2—Cl1	1.3 (3)	O1—C1—C6—O4	−0.9 (3)
C6—C1—C2—Cl1	−178.77 (16)	C2—C1—C6—O4	179.2 (2)
C1—C2—C3—O2	177.7 (2)	O1—C1—C6—C5	179.2 (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—C4	177.58 (16)	C11—N1—C7—C12	179.6 (2)
O2—C3—C4—O3	3.3 (3)	N1—C7—C8—C9	0.7 (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—C5	3.2 (3)	C8—C9—C10—C11	−0.7 (4)
O3—C4—C5—C6	177.0 (2)	C7—N1—C11—C10	−0.2 (4)
C3—C4—C5—C6	−1.8 (3)	C9—C10—C11—N1	0.8 (4)
O3—C4—C5—Cl2	−3.0 (3)	N1—C7—C12—O5	−11.4 (3)
C3—C4—C5—Cl2	178.11 (16)	C8—C7—C12—O5	168.8 (2)
C4—C5—C6—O4	−179.2 (2)	N1—C7—C12—O6	168.4 (2)
Cl2—C5—C6—O4	0.8 (3)	C8—C7—C12—O6	−11.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.92 (4)	2.11 (3)	2.932 (2)	147 (3)
N1—H1···O5	0.92 (4)	2.33 (4)	2.698 (2)	103 (2)
N1—H1···O5i	0.92 (4)	2.34 (4)	2.900 (2)	119 (3)
O2—H2···O3	0.79 (3)	2.11 (3)	2.612 (2)	122 (3)
O2—H2···O5ii	0.79 (3)	2.05 (3)	2.746 (2)	148 (3)
O6—H6···O4iii	0.90 (3)	1.63 (3)	2.528 (2)	177.1 (15)
C8—H8···O4iv	0.95	2.50	3.338 (3)	147
C9—H9···O3v	0.95	2.33	3.227 (3)	156
C11—H11···O1vi	0.95	2.46	3.374 (3)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.92 (4)	2.11 (3)	2.932 (2)	147 (3)
O2—H2⋯O5i	0.79 (3)	2.05 (3)	2.746 (2)	148 (3)
O6—H6⋯O4ii	0.90 (3)	1.63 (3)	2.528 (2)	177.1 (15)
C8—H8⋯O4iii	0.95	2.50	3.338 (3)	147
C9—H9⋯O3iv	0.95	2.33	3.227 (3)	156
C11—H11⋯O1v	0.95	2.46	3.374 (3)	162

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