2-Carboxy­pyridinium hydrogen chloranilate

Tabuchi, Y.; Takahashi, A.; Gotoh, K.; Akashi, H.; Ishida, H.

doi:10.1107/S1600536805037591

2-Carboxypyridinium hydrogen chloranilate

Y. Tabuchi, A. Takahashi, K. Gotoh, H. Akashi and H. Ishida

The title compound, C₆H₆NO₂⁺·C₆HCl₂O₄⁻, is the salt of chloranilic acid with nicotinic acid (2-carboxypiridine), where an acid–base interaction involving a proton transfer is observed from the chloranilic acid to the pyridine group of nicotinic acid. In the crystal structure, the hydrogen chloranilate anion and the 2-carboxypridinium cation are linked by N—H

O and O—H

O hydrogen bonds to form a zigzag chain. The chains are further linked by O—H

O hydrogen bonds to form a three-dimensional hydrogen-bond network.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805037591/lh6547sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805037591/lh6547Isup2.hkl Contains datablock I

CCDC reference: 293949

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.004 Å
R factor = 0.031
wR factor = 0.072
Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.540
           From the CIF: _refine_ls_abs_structure_Flack_su    0.060
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero .......       0.54
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.11 Ratio
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.80
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.14
PLAT335_ALERT_2_C Large Benzene C-C Range          C1     -C6            0.21 Ang.
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C1     -   C6     ...       1.54 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C6 H Cl2 O4

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.46
           From the CIF: _reflns_number_total               2602
           Count of symmetry unique reflns         1502
           Completeness (_total/calc)            173.24%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1100
           Fraction of Friedel pairs measured     0.732
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: PROCESS-AUTO (Rigaku/MSC & Rigaku Corporation, 2004); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC & Rigaku Corporation, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure and PLATON (Spek, 2003).

2-Carboxypyridinium hydrogen chloranilate top

Crystal data top

C₆H₆NO₂⁺·C₆HCl₂O₄⁻	F(000) = 336.00
M_r = 332.10	D_x = 1.679 Mg m⁻³
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 2638 reflections
a = 10.7715 (10) Å	θ = 4.2–27.4°
b = 5.4301 (5) Å	µ = 0.52 mm⁻¹
c = 12.9139 (12) Å	T = 295 K
β = 119.580 (7)°	Prism, brown
V = 656.89 (11) Å³	0.25 × 0.25 × 0.20 mm
Z = 2

Data collection top

Rigaku R-AXIS IV diffractometer	2312 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.021
ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −13→13
T_min = 0.835, T_max = 0.901	k = −6→6
4509 measured reflections	l = −16→16
2602 independent reflections

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)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.0438P)² + 0.0699P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.002
2602 reflections	Δρ_max = 0.21 e Å⁻³
204 parameters	Δρ_min = −0.19 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 1100 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.54 (6)

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
Cl1	0.65297 (6)	−0.67605 (12)	0.50709 (5)	0.03847 (19)
Cl2	0.62124 (6)	0.18368 (13)	0.82718 (5)	0.0418 (2)
O1	0.4125 (2)	−0.3369 (4)	0.45245 (19)	0.0408 (5)
O2	0.8794 (2)	−0.5225 (4)	0.75417 (19)	0.0441 (6)
O3	0.8569 (2)	−0.1691 (4)	0.8795 (2)	0.0503 (6)
O4	0.3945 (2)	0.0452 (4)	0.57256 (16)	0.0372 (5)
O5	0.3162 (2)	0.5992 (5)	0.15956 (18)	0.0628 (7)
O6	0.1316 (2)	0.5075 (4)	−0.01961 (15)	0.0418 (5)
N1	0.2233 (2)	0.0776 (4)	0.33025 (19)	0.0334 (5)
C1	0.5169 (3)	−0.2961 (5)	0.5488 (2)	0.0278 (6)
C2	0.6479 (3)	−0.4426 (5)	0.5960 (2)	0.0300 (6)
C3	0.7566 (3)	−0.3968 (6)	0.7045 (2)	0.0305 (6)
C4	0.7504 (3)	−0.1950 (5)	0.7815 (3)	0.0313 (7)
C5	0.6236 (3)	−0.0505 (5)	0.7362 (2)	0.0289 (6)
C6	0.5089 (3)	−0.0822 (5)	0.6240 (2)	0.0272 (6)
C7	0.2557 (3)	0.2473 (5)	0.2722 (2)	0.0311 (5)
C8	0.1653 (2)	0.2872 (4)	0.1527 (2)	0.0290 (5)
C9	0.0409 (3)	0.1492 (6)	0.0952 (2)	0.0433 (7)
C10	0.0118 (3)	−0.0270 (6)	0.1581 (3)	0.0568 (9)
C11	0.1045 (3)	−0.0588 (6)	0.2762 (3)	0.0469 (8)
C12	0.2009 (3)	0.4771 (5)	0.0870 (2)	0.0322 (6)
H1	0.934 (4)	−0.462 (7)	0.822 (4)	0.065 (11)*
H2	0.278 (4)	0.036 (7)	0.413 (4)	0.071 (11)*
H3	0.3393	0.3383	0.3127	0.037*
H4	−0.0227	0.1748	0.0148	0.052*
H5	−0.0704	−0.1225	0.1199	0.068*
H6	0.0854	−0.1752	0.3193	0.056*
H7	0.348 (6)	0.722 (9)	0.120 (4)	0.115 (17)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0419 (4)	0.0384 (4)	0.0300 (4)	0.0098 (3)	0.0138 (3)	−0.0067 (3)
Cl2	0.0501 (4)	0.0390 (4)	0.0276 (4)	0.0095 (3)	0.0125 (3)	−0.0082 (3)
O1	0.0323 (11)	0.0448 (12)	0.0278 (12)	0.0053 (9)	0.0015 (10)	−0.0092 (8)
O2	0.0324 (11)	0.0523 (13)	0.0323 (11)	0.0148 (10)	0.0042 (9)	−0.0065 (10)
O3	0.0353 (12)	0.0614 (16)	0.0304 (13)	0.0087 (10)	−0.0019 (11)	−0.0146 (10)
O4	0.0321 (10)	0.0439 (12)	0.0256 (9)	0.0156 (9)	0.0066 (8)	−0.0027 (8)
O5	0.0608 (14)	0.0717 (15)	0.0317 (11)	−0.0433 (12)	0.0044 (10)	0.0072 (10)
O6	0.0351 (9)	0.0552 (12)	0.0235 (9)	−0.0026 (8)	0.0054 (8)	0.0075 (8)
N1	0.0332 (10)	0.0329 (11)	0.0258 (10)	−0.0034 (9)	0.0083 (9)	0.0012 (8)
C1	0.0275 (14)	0.0311 (15)	0.0184 (13)	−0.0020 (11)	0.0065 (12)	−0.0011 (10)
C2	0.0307 (14)	0.0317 (16)	0.0247 (13)	0.0039 (12)	0.0114 (12)	−0.0008 (11)
C3	0.0253 (13)	0.0343 (15)	0.0275 (14)	0.0062 (11)	0.0097 (12)	0.0014 (11)
C4	0.0280 (13)	0.0355 (17)	0.0261 (15)	0.0014 (12)	0.0099 (12)	−0.0031 (11)
C5	0.0322 (13)	0.0283 (15)	0.0234 (12)	0.0033 (12)	0.0114 (11)	−0.0031 (11)
C6	0.0293 (13)	0.0277 (14)	0.0242 (12)	0.0022 (11)	0.0129 (11)	0.0005 (10)
C7	0.0271 (11)	0.0329 (13)	0.0248 (12)	−0.0059 (10)	0.0063 (10)	−0.0040 (10)
C8	0.0237 (11)	0.0316 (12)	0.0229 (12)	−0.0064 (10)	0.0047 (9)	−0.0034 (9)
C9	0.0323 (13)	0.0560 (19)	0.0258 (14)	−0.0161 (13)	0.0023 (12)	0.0003 (12)
C10	0.0476 (17)	0.066 (2)	0.0389 (17)	−0.0374 (16)	0.0073 (15)	0.0015 (14)
C11	0.0465 (17)	0.0486 (18)	0.0385 (15)	−0.0179 (14)	0.0156 (14)	0.0062 (13)
C12	0.0310 (12)	0.0325 (14)	0.0294 (14)	−0.0059 (11)	0.0121 (11)	−0.0004 (10)

Geometric parameters (Å, º) top

Cl1—C2	1.729 (3)	C1—C6	1.544 (4)
Cl2—C5	1.740 (3)	C2—C3	1.333 (4)
O1—C1	1.217 (3)	C3—C4	1.504 (4)
O2—C3	1.337 (3)	C4—C5	1.426 (4)
O2—H1	0.84 (4)	C5—C6	1.374 (4)
O3—C4	1.227 (4)	C7—C8	1.376 (3)
O4—C6	1.277 (3)	C7—H3	0.9300
O5—C12	1.308 (3)	C8—C9	1.387 (3)
O5—H7	1.00 (5)	C8—C12	1.500 (3)
O6—C12	1.211 (3)	C9—C10	1.388 (4)
N1—C7	1.338 (3)	C9—H4	0.9300
N1—C11	1.338 (3)	C10—C11	1.360 (4)
N1—H2	0.96 (4)	C10—H5	0.9300
C1—C2	1.465 (4)	C11—H6	0.9300

Cl1···Cl2ⁱ	3.5113 (10)	O3···O6^vii	3.119 (3)
Cl1···Cl2ⁱⁱ	3.4466 (10)	O3···C9^viii	3.037 (3)
Cl1···O3ⁱ	3.438 (3)	O3···C10^viii	3.224 (4)
Cl1···C6ⁱⁱⁱ	3.445 (3)	O3···H1	2.09 (4)
Cl1···H3ⁱⁱⁱ	3.06	O3···H4^viii	2.45
Cl1···H5^iv	2.81	O3···H5^viii	2.81
Cl2···O1^v	3.458 (3)	O4···O5^vi	2.576 (3)
Cl2···O5^vi	3.138 (2)	O4···N1	2.743 (3)
Cl2···C1^v	3.606 (3)	O4···C12^vi	3.391 (4)
Cl2···C2^v	3.623 (3)	O4···H2	1.81 (4)
Cl2···H7^vi	2.88 (5)	O4···H7^vi	1.59 (5)
O1···N1	2.921 (3)	O5···O4^ix	2.576 (3)
O1···C7ⁱⁱⁱ	3.080 (3)	O5···H3	2.34
O1···H2	2.39 (4)	O6···O2^x	2.847 (3)
O1···H3ⁱⁱⁱ	2.36	O6···O3^x	3.119 (3)
O2···O6^vii	2.847 (3)	O6···H1^x	2.11 (5)
O2···C10^iv	3.362 (4)	O6···H4	2.64
O2···C11^iv	3.232 (4)	O6···H6ⁱⁱ	2.61
O2···H6^iv	2.55	C6···H7^vi	2.60 (6)
O2···H5^iv	2.82	H1···H6^iv	2.57

C3—O2—H1	108 (3)	O4—C6—C1	114.8 (2)
C12—O5—H7	114 (3)	C5—C6—C1	117.2 (3)
C7—N1—C11	122.4 (2)	N1—C7—C8	120.1 (2)
C7—N1—H2	127 (2)	N1—C7—H3	120.0
C11—N1—H2	110 (2)	C8—C7—H3	120.0
O1—C1—C2	122.7 (3)	C7—C8—C9	118.4 (2)
O1—C1—C6	118.0 (3)	C7—C8—C12	120.4 (2)
C2—C1—C6	119.3 (2)	C9—C8—C12	121.2 (2)
C3—C2—C1	120.1 (3)	C8—C9—C10	119.8 (3)
C3—C2—Cl1	122.4 (2)	C8—C9—H4	120.1
C1—C2—Cl1	117.5 (2)	C10—C9—H4	120.1
C2—C3—O2	123.8 (3)	C11—C10—C9	119.4 (3)
C2—C3—C4	121.9 (3)	C11—C10—H5	120.3
O2—C3—C4	114.2 (2)	C9—C10—H5	120.3
O3—C4—C5	125.3 (3)	N1—C11—C10	119.9 (3)
O3—C4—C3	116.2 (3)	N1—C11—H6	120.1
C5—C4—C3	118.4 (3)	C10—C11—H6	120.1
C6—C5—C4	122.9 (3)	O6—C12—O5	125.4 (2)
C6—C5—Cl2	119.9 (2)	O6—C12—C8	123.4 (2)
C4—C5—Cl2	117.1 (2)	O5—C12—C8	111.1 (2)
O4—C6—C5	128.0 (3)

O1—C1—C2—C3	−176.9 (3)	C4—C5—C6—C1	4.1 (4)
C6—C1—C2—C3	2.5 (4)	Cl2—C5—C6—C1	−179.0 (2)
O1—C1—C2—Cl1	1.9 (4)	O1—C1—C6—O4	−5.0 (4)
C6—C1—C2—Cl1	−178.7 (2)	C2—C1—C6—O4	175.6 (3)
C1—C2—C3—O2	179.7 (3)	O1—C1—C6—C5	175.2 (3)
Cl1—C2—C3—O2	1.0 (5)	C2—C1—C6—C5	−4.2 (4)
C1—C2—C3—C4	−0.6 (4)	C11—N1—C7—C8	0.2 (4)
Cl1—C2—C3—C4	−179.3 (2)	N1—C7—C8—C9	0.4 (4)
C2—C3—C4—O3	−179.7 (3)	N1—C7—C8—C12	179.9 (2)
O2—C3—C4—O3	0.0 (4)	C7—C8—C9—C10	−1.2 (4)
C2—C3—C4—C5	0.3 (4)	C12—C8—C9—C10	179.3 (3)
O2—C3—C4—C5	−180.0 (3)	C8—C9—C10—C11	1.3 (5)
O3—C4—C5—C6	177.8 (3)	C7—N1—C11—C10	−0.1 (5)
C3—C4—C5—C6	−2.2 (4)	C9—C10—C11—N1	−0.7 (6)
O3—C4—C5—Cl2	0.8 (4)	C7—C8—C12—O6	174.1 (3)
C3—C4—C5—Cl2	−179.2 (2)	C9—C8—C12—O6	−6.4 (4)
C4—C5—C6—O4	−175.7 (3)	C7—C8—C12—O5	−4.7 (4)
Cl2—C5—C6—O4	1.3 (4)	C9—C8—C12—O5	174.8 (3)

Symmetry codes: (i) x, −y−1, z−1/2; (ii) x, −y, z−1/2; (iii) x, y−1, z; (iv) x+1, −y−1, z+1/2; (v) x, −y, z+1/2; (vi) x, −y+1, z+1/2; (vii) x+1, y−1, z+1; (viii) x+1, y, z+1; (ix) x, −y+1, z−1/2; (x) x−1, y+1, z−1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1···O3	0.84 (4)	2.09 (4)	2.598 (3)	118 (4)
O2—H1···O6^vii	0.84 (4)	2.11 (5)	2.847 (3)	146 (4)
O5—H7···O4^ix	1.00 (5)	1.59 (5)	2.576 (3)	169 (5)
N1—H2···O1	0.96 (4)	2.39 (4)	2.921 (3)	114 (3)
N1—H2···O4	0.96 (4)	1.81 (4)	2.743 (3)	164 (3)
C7—H3···O1^xi	0.93	2.36	3.080 (3)	134
C9—H4···O3^xii	0.93	2.45	3.037 (3)	121
C10—H5···Cl1^xiii	0.93	2.81	3.728 (4)	168
C11—H6···O2^xiii	0.93	2.55	3.232 (4)	131

Symmetry codes: (vii) x+1, y−1, z+1; (ix) x, −y+1, z−1/2; (xi) x, y+1, z; (xii) x−1, y, z−1; (xiii) x−1, −y−1, z−1/2.

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2-Carboxy­pyridinium hydrogen chloranilate

Supporting information

Key indicators

checkCIF/PLATON results

2-Carboxypyridinium hydrogen chloranilate