The title compound, C
6H
6NO
2+·C
6HCl
2O
4−, 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.
Supporting information
CCDC reference: 293949
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
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 |
Mr = 332.10 | Dx = 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 | Rint = 0.021 |
ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −13→13 |
Tmin = 0.835, Tmax = 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(Fo2) + (0.0438P)2 + 0.0699P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.002 |
2602 reflections | Δρmax = 0.21 e Å−3 |
204 parameters | Δρmin = −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 | Uiso*/Ueq | |
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···O6vii | 3.119 (3) |
Cl1···Cl2ii | 3.4466 (10) | O3···C9viii | 3.037 (3) |
Cl1···O3i | 3.438 (3) | O3···C10viii | 3.224 (4) |
Cl1···C6iii | 3.445 (3) | O3···H1 | 2.09 (4) |
Cl1···H3iii | 3.06 | O3···H4viii | 2.45 |
Cl1···H5iv | 2.81 | O3···H5viii | 2.81 |
Cl2···O1v | 3.458 (3) | O4···O5vi | 2.576 (3) |
Cl2···O5vi | 3.138 (2) | O4···N1 | 2.743 (3) |
Cl2···C1v | 3.606 (3) | O4···C12vi | 3.391 (4) |
Cl2···C2v | 3.623 (3) | O4···H2 | 1.81 (4) |
Cl2···H7vi | 2.88 (5) | O4···H7vi | 1.59 (5) |
O1···N1 | 2.921 (3) | O5···O4ix | 2.576 (3) |
O1···C7iii | 3.080 (3) | O5···H3 | 2.34 |
O1···H2 | 2.39 (4) | O6···O2x | 2.847 (3) |
O1···H3iii | 2.36 | O6···O3x | 3.119 (3) |
O2···O6vii | 2.847 (3) | O6···H1x | 2.11 (5) |
O2···C10iv | 3.362 (4) | O6···H4 | 2.64 |
O2···C11iv | 3.232 (4) | O6···H6ii | 2.61 |
O2···H6iv | 2.55 | C6···H7vi | 2.60 (6) |
O2···H5iv | 2.82 | H1···H6iv | 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···O6vii | 0.84 (4) | 2.11 (5) | 2.847 (3) | 146 (4) |
O5—H7···O4ix | 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···O1xi | 0.93 | 2.36 | 3.080 (3) | 134 |
C9—H4···O3xii | 0.93 | 2.45 | 3.037 (3) | 121 |
C10—H5···Cl1xiii | 0.93 | 2.81 | 3.728 (4) | 168 |
C11—H6···O2xiii | 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. |