organic compounds
A triclinic polymorph of 4-cyanopyridinium hydrogen chloranilate
aDepartment of Chemistry, Faculty of Science, Okayama University, Okayama 700-8530, Japan
*Correspondence e-mail: ishidah@cc.okayama-u.ac.jp
The 6H5N2+·C6HCl2O4−, consists of two crystallographically independent cation–anion units, in each of which the cation and the anion are linked by an N—H⋯O hydrogen bond. In the units, the dihedral angles between the cation and anion rings are 78.43 (11) and 80.71 (11)°. In the crystal, each unit independently forms a chain through N—H⋯O and O—H⋯N hydrogen bonds; one chain runs along the c axis while the other runs along [011]. Weak C—H⋯O, C—H⋯N and C—H⋯Cl interactions are observed between the chains.
of the triclinic polymorph of the title compound (systematic name: 4-cyanopyridinium 2,5-dichloro-4-hydroxy-3,6-dioxocyclohexa-1,4-dien-1-olate), CRelated literature
For the monoclinic polymorph, see: Tomura & Yamashita (2008); Gotoh et al. (2008). For hydrogen-bonding patterns in chloranilic acid–organic base (1/1) systems, see: Ishida & Kashino (2002). For 35Cl nuclear quadrupole resonance studies on proton transfer in chloranilic acid–organic base systems, see: Nihei et al. (2000).
Experimental
Crystal data
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Refinement
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Data collection: PROCESS-AUTO (Rigaku/MSC, 2004); cell 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: SHELXL97 and PLATON (Spek, 2009).
Supporting information
https://doi.org/10.1107/S1600536812037221/lh5521sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812037221/lh5521Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812037221/lh5521Isup3.cml
Single crystals were obtained by slow evaporation from an acetonitrile solution (130 ml) of chloranilic acid (0.60 g) and 4-cyanopyridine (0.30 g) at room temperature.
C-bound H atoms were positioned geometrically (C—H = 0.95 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C). The O– and N-bound H atoms were found in a difference Fourier map and refined freely. The refined distances are O—H = 0.80 (4) and 0.93 (5) Å, and N—H = 0.90 (4) and 0.95 (4) Å.
The title compound was accidentally obtained in the preparation of the monoclinic polymorph of 4-cyanopyridinium chloranilate, C6H5N2+.C6HCl2O4-, which is an interesting model compound for investigating proton transfer in the hydrogen bond systems (Nihei et al., 2000). The structure of the monoclinic polymorph has been reported by Tomura & Yamashita (2008) and Gotoh et al. (2008).
The
of the triclinic polymorph of the title compound consists of two crystallographically independent cation–anion units, in each of which the cation and the anion are held together by N—H···O hydrogen bond. The dihedral angle between the N1/C13–C17 pyridine ring and the C1–C6 of the acid ring is 78.43 (11)° in one unit, while the angle between the N3/C19–C23 and C7–C12 rings is 80.71 (11)° in the other unit.In the
of the monoclinic polymorph, the acid molecule (A) and the base molecule (B) afford an centrosymmetric 2:2 (B:A:A:B) aggregate (Ishida & Kashino, 2002) through O—H···O and N···H···O hydrogen bonds and the H atom in the N···H···O hydrogen bond is disordered over two positions (Gotoh et al., 2008). In contrast to the monoclinic form, the present triclinic polymorph shows two crystallographically independent 1:1 (A:B) units of the acid and base molecules. Each unit independently forms a hydrogen-bonded (–A:B:A:B–) chain; one chain formed by N1—H1···O2 and O4—H4···N2i (symmetry code in Table 1) hydrogen bonds runs along the c axis, while the other chain formed by N3—H3···O6 and O8—H8···N4ii (symmetry code in Table 1) hydrogen bonds runs along the [011] direction. No H atom disorder is observed in these hydrogen bonds. Between the chains, C—H···O, C—H···N and C—H···Cl interactions (Table 1) are observed.For the monoclinic polymorph, see: Tomura & Yamashita (2008); Gotoh et al. (2008). For hydrogen-bonding patterns in chloranilic acid–organic base (1/1) systems, see: Ishida & Kashino (2002). For 35Cl nuclear quadrupole resonance studies on proton transfer in chloranilic acid–organic base systems, see: Nihei et al. (2000).
Data collection: PROCESS-AUTO (Rigaku/MSC, 2004); cell
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: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. The asymmetric unit of the title compound, with the atom-labeling. Displacement ellipsoids of non-H atoms are drawn at the 50% probability level. The dashed lines indicate the N—H···O hydrogen bonds. | |
Fig. 2. A packing diagram of the title compound, showing two crystallographically independent chains formed by N—H···O and O—H···N hydrogen bonds (dashed lines). H atoms not involved in the hydrogen bonds have been omitted. [Symmetry codes: (i) x, y, z - 1; (ii) x, y + 1, z + 1; (viii) x, y, z + 1; (ix) x, y - 1, z - 1.] |
C6H5N2+·C6HCl2O4− | Z = 4 |
Mr = 313.10 | F(000) = 632.00 |
Triclinic, P1 | Dx = 1.687 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71075 Å |
a = 9.3918 (7) Å | Cell parameters from 17217 reflections |
b = 10.6652 (7) Å | θ = 3.1–30.1° |
c = 13.9135 (8) Å | µ = 0.54 mm−1 |
α = 111.8033 (18)° | T = 180 K |
β = 106.258 (3)° | Platelet, brown |
γ = 90.416 (3)° | 0.36 × 0.31 × 0.09 mm |
V = 1232.50 (14) Å3 |
Rigaku R-AXIS RAPID II diffractometer | 4934 reflections with I > 2σ(I) |
ω scans | Rint = 0.108 |
Absorption correction: numerical (NUMABS; Higashi, 1999) | θmax = 30.0° |
Tmin = 0.866, Tmax = 0.953 | h = −13→13 |
21354 measured reflections | k = −14→14 |
7135 independent reflections | l = −19→19 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.066 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.164 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0762P)2] where P = (Fo2 + 2Fc2)/3 |
7135 reflections | (Δ/σ)max = 0.001 |
377 parameters | Δρmax = 0.89 e Å−3 |
0 restraints | Δρmin = −0.83 e Å−3 |
C6H5N2+·C6HCl2O4− | γ = 90.416 (3)° |
Mr = 313.10 | V = 1232.50 (14) Å3 |
Triclinic, P1 | Z = 4 |
a = 9.3918 (7) Å | Mo Kα radiation |
b = 10.6652 (7) Å | µ = 0.54 mm−1 |
c = 13.9135 (8) Å | T = 180 K |
α = 111.8033 (18)° | 0.36 × 0.31 × 0.09 mm |
β = 106.258 (3)° |
Rigaku R-AXIS RAPID II diffractometer | 7135 independent reflections |
Absorption correction: numerical (NUMABS; Higashi, 1999) | 4934 reflections with I > 2σ(I) |
Tmin = 0.866, Tmax = 0.953 | Rint = 0.108 |
21354 measured reflections |
R[F2 > 2σ(F2)] = 0.066 | 0 restraints |
wR(F2) = 0.164 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.89 e Å−3 |
7135 reflections | Δρmin = −0.83 e Å−3 |
377 parameters |
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 | 0.29193 (7) | 0.49544 (6) | −0.10659 (5) | 0.04057 (16) | |
Cl2 | 0.68163 (7) | 1.06889 (5) | 0.18401 (5) | 0.03666 (15) | |
Cl3 | 0.21149 (7) | 0.59716 (6) | 0.62343 (5) | 0.03851 (16) | |
Cl4 | −0.16421 (7) | 0.85552 (7) | 0.30375 (5) | 0.04279 (17) | |
O1 | 0.51735 (19) | 0.64141 (17) | −0.15370 (13) | 0.0396 (4) | |
O2 | 0.32328 (17) | 0.66708 (16) | 0.12870 (12) | 0.0346 (3) | |
O3 | 0.48242 (18) | 0.91360 (17) | 0.24401 (13) | 0.0363 (4) | |
O4 | 0.67459 (19) | 0.88479 (17) | −0.03878 (14) | 0.0343 (4) | |
O5 | −0.01092 (19) | 0.79448 (17) | 0.65480 (13) | 0.0384 (4) | |
O6 | 0.19311 (18) | 0.52007 (16) | 0.38448 (13) | 0.0364 (4) | |
O7 | 0.04975 (18) | 0.65162 (17) | 0.26162 (13) | 0.0370 (4) | |
O8 | −0.16121 (19) | 0.90831 (17) | 0.53085 (14) | 0.0376 (4) | |
N1 | 0.4187 (2) | 0.7224 (2) | 0.33632 (16) | 0.0344 (4) | |
N2 | 0.6554 (2) | 0.7841 (2) | 0.74522 (17) | 0.0424 (5) | |
N3 | 0.0861 (2) | 0.3707 (2) | 0.16703 (16) | 0.0341 (4) | |
N4 | −0.1526 (2) | 0.0443 (2) | −0.24595 (17) | 0.0413 (5) | |
C1 | 0.4981 (2) | 0.7009 (2) | −0.06484 (17) | 0.0298 (4) | |
C2 | 0.3989 (2) | 0.6506 (2) | −0.02287 (17) | 0.0302 (4) | |
C3 | 0.3974 (2) | 0.7129 (2) | 0.08301 (17) | 0.0296 (4) | |
C4 | 0.4895 (2) | 0.8540 (2) | 0.15269 (17) | 0.0289 (4) | |
C5 | 0.5819 (2) | 0.9100 (2) | 0.10598 (17) | 0.0296 (4) | |
C6 | 0.5880 (2) | 0.8389 (2) | 0.00544 (17) | 0.0292 (4) | |
C7 | 0.0119 (2) | 0.7548 (2) | 0.56596 (17) | 0.0301 (4) | |
C8 | 0.1100 (2) | 0.6605 (2) | 0.53026 (18) | 0.0306 (4) | |
C9 | 0.1187 (2) | 0.6129 (2) | 0.42538 (17) | 0.0292 (4) | |
C10 | 0.0303 (2) | 0.6811 (2) | 0.35009 (17) | 0.0305 (4) | |
C11 | −0.0679 (2) | 0.7803 (2) | 0.38836 (18) | 0.0319 (4) | |
C12 | −0.0762 (2) | 0.8166 (2) | 0.48929 (18) | 0.0301 (4) | |
C13 | 0.3814 (3) | 0.8248 (2) | 0.41276 (19) | 0.0354 (5) | |
H13 | 0.3173 | 0.8851 | 0.3923 | 0.042* | |
C14 | 0.4348 (3) | 0.8434 (2) | 0.52031 (19) | 0.0338 (5) | |
H14 | 0.4081 | 0.9150 | 0.5750 | 0.041* | |
C15 | 0.5302 (3) | 0.7526 (2) | 0.54595 (18) | 0.0321 (4) | |
C16 | 0.5662 (3) | 0.6461 (2) | 0.46590 (19) | 0.0378 (5) | |
H16 | 0.6298 | 0.5841 | 0.4839 | 0.045* | |
C17 | 0.5075 (3) | 0.6327 (2) | 0.3596 (2) | 0.0381 (5) | |
H17 | 0.5296 | 0.5603 | 0.3030 | 0.046* | |
C18 | 0.5972 (3) | 0.7707 (2) | 0.65759 (19) | 0.0357 (5) | |
C19 | 0.1208 (3) | 0.4009 (2) | 0.09031 (19) | 0.0359 (5) | |
H19 | 0.1878 | 0.4798 | 0.1103 | 0.043* | |
C20 | 0.0589 (3) | 0.3172 (2) | −0.01748 (18) | 0.0342 (5) | |
H20 | 0.0824 | 0.3372 | −0.0728 | 0.041* | |
C21 | −0.0390 (2) | 0.2024 (2) | −0.04369 (17) | 0.0303 (4) | |
C22 | −0.0737 (3) | 0.1742 (2) | 0.03736 (19) | 0.0355 (5) | |
H22 | −0.1409 | 0.0965 | 0.0200 | 0.043* | |
C23 | −0.0083 (3) | 0.2619 (2) | 0.14348 (19) | 0.0363 (5) | |
H23 | −0.0304 | 0.2448 | 0.2004 | 0.044* | |
C24 | −0.1034 (3) | 0.1137 (2) | −0.15641 (18) | 0.0340 (5) | |
H1 | 0.384 (3) | 0.713 (3) | 0.263 (3) | 0.063 (9)* | |
H3 | 0.121 (3) | 0.432 (3) | 0.236 (3) | 0.056 (9)* | |
H4 | 0.665 (4) | 0.833 (4) | −0.100 (3) | 0.068 (11)* | |
H8 | −0.140 (4) | 0.918 (4) | 0.603 (4) | 0.097 (13)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0498 (4) | 0.0352 (3) | 0.0327 (3) | −0.0051 (3) | 0.0117 (3) | 0.0097 (2) |
Cl2 | 0.0453 (3) | 0.0310 (3) | 0.0314 (3) | −0.0010 (2) | 0.0092 (2) | 0.0116 (2) |
Cl3 | 0.0490 (3) | 0.0387 (3) | 0.0311 (3) | 0.0160 (3) | 0.0107 (3) | 0.0180 (2) |
Cl4 | 0.0500 (4) | 0.0509 (4) | 0.0361 (3) | 0.0186 (3) | 0.0126 (3) | 0.0265 (3) |
O1 | 0.0532 (10) | 0.0367 (9) | 0.0316 (8) | 0.0031 (8) | 0.0210 (8) | 0.0102 (7) |
O2 | 0.0398 (9) | 0.0382 (8) | 0.0290 (8) | 0.0011 (7) | 0.0142 (7) | 0.0139 (7) |
O3 | 0.0433 (9) | 0.0379 (8) | 0.0292 (8) | 0.0064 (7) | 0.0169 (7) | 0.0104 (7) |
O4 | 0.0431 (9) | 0.0355 (8) | 0.0282 (8) | 0.0033 (7) | 0.0172 (7) | 0.0119 (7) |
O5 | 0.0533 (10) | 0.0417 (9) | 0.0305 (8) | 0.0177 (8) | 0.0226 (8) | 0.0181 (7) |
O6 | 0.0396 (9) | 0.0368 (8) | 0.0322 (8) | 0.0112 (7) | 0.0112 (7) | 0.0123 (7) |
O7 | 0.0490 (10) | 0.0388 (9) | 0.0289 (8) | 0.0111 (7) | 0.0183 (7) | 0.0145 (7) |
O8 | 0.0428 (9) | 0.0399 (9) | 0.0348 (9) | 0.0173 (7) | 0.0156 (8) | 0.0168 (8) |
N1 | 0.0418 (11) | 0.0349 (9) | 0.0277 (9) | 0.0021 (8) | 0.0118 (8) | 0.0127 (8) |
N2 | 0.0492 (12) | 0.0501 (12) | 0.0346 (10) | 0.0079 (10) | 0.0168 (10) | 0.0210 (10) |
N3 | 0.0393 (10) | 0.0356 (10) | 0.0286 (9) | 0.0110 (8) | 0.0114 (9) | 0.0127 (9) |
N4 | 0.0495 (12) | 0.0425 (11) | 0.0331 (10) | 0.0096 (9) | 0.0152 (10) | 0.0139 (9) |
C1 | 0.0364 (11) | 0.0292 (10) | 0.0274 (10) | 0.0085 (9) | 0.0120 (9) | 0.0132 (9) |
C2 | 0.0349 (11) | 0.0279 (10) | 0.0267 (10) | 0.0035 (9) | 0.0089 (9) | 0.0099 (9) |
C3 | 0.0318 (11) | 0.0303 (10) | 0.0281 (10) | 0.0046 (8) | 0.0080 (9) | 0.0135 (9) |
C4 | 0.0317 (10) | 0.0310 (10) | 0.0277 (10) | 0.0094 (9) | 0.0111 (9) | 0.0138 (9) |
C5 | 0.0326 (11) | 0.0284 (10) | 0.0286 (10) | 0.0042 (8) | 0.0088 (9) | 0.0123 (9) |
C6 | 0.0316 (10) | 0.0303 (10) | 0.0288 (10) | 0.0059 (8) | 0.0093 (9) | 0.0148 (9) |
C7 | 0.0332 (11) | 0.0297 (10) | 0.0286 (10) | 0.0038 (9) | 0.0080 (9) | 0.0138 (9) |
C8 | 0.0345 (11) | 0.0304 (10) | 0.0289 (10) | 0.0070 (9) | 0.0073 (9) | 0.0153 (9) |
C9 | 0.0299 (10) | 0.0291 (10) | 0.0288 (10) | 0.0049 (8) | 0.0084 (9) | 0.0118 (9) |
C10 | 0.0331 (11) | 0.0312 (10) | 0.0278 (10) | 0.0026 (9) | 0.0081 (9) | 0.0129 (9) |
C11 | 0.0346 (11) | 0.0355 (11) | 0.0291 (10) | 0.0064 (9) | 0.0078 (9) | 0.0177 (9) |
C12 | 0.0315 (11) | 0.0293 (10) | 0.0315 (11) | 0.0068 (9) | 0.0113 (9) | 0.0127 (9) |
C13 | 0.0405 (12) | 0.0333 (11) | 0.0360 (12) | 0.0060 (10) | 0.0126 (10) | 0.0166 (10) |
C14 | 0.0408 (12) | 0.0313 (10) | 0.0313 (10) | 0.0069 (9) | 0.0149 (10) | 0.0114 (9) |
C15 | 0.0367 (11) | 0.0345 (11) | 0.0284 (10) | 0.0023 (9) | 0.0116 (9) | 0.0147 (9) |
C16 | 0.0463 (13) | 0.0356 (11) | 0.0362 (12) | 0.0108 (10) | 0.0175 (11) | 0.0155 (10) |
C17 | 0.0472 (13) | 0.0363 (12) | 0.0346 (11) | 0.0093 (10) | 0.0193 (11) | 0.0128 (10) |
C18 | 0.0407 (12) | 0.0390 (12) | 0.0338 (11) | 0.0078 (10) | 0.0166 (10) | 0.0173 (10) |
C19 | 0.0383 (12) | 0.0352 (11) | 0.0371 (12) | 0.0039 (9) | 0.0138 (10) | 0.0158 (10) |
C20 | 0.0409 (12) | 0.0360 (11) | 0.0313 (11) | 0.0061 (10) | 0.0159 (10) | 0.0156 (10) |
C21 | 0.0354 (11) | 0.0322 (10) | 0.0276 (10) | 0.0093 (9) | 0.0133 (9) | 0.0136 (9) |
C22 | 0.0435 (13) | 0.0348 (11) | 0.0346 (11) | 0.0047 (10) | 0.0162 (10) | 0.0172 (10) |
C23 | 0.0465 (13) | 0.0400 (12) | 0.0311 (11) | 0.0113 (10) | 0.0170 (10) | 0.0194 (10) |
C24 | 0.0373 (12) | 0.0378 (11) | 0.0317 (11) | 0.0083 (10) | 0.0140 (10) | 0.0160 (10) |
Cl1—C2 | 1.730 (2) | C4—C5 | 1.460 (3) |
Cl2—C5 | 1.722 (2) | C5—C6 | 1.339 (3) |
Cl3—C8 | 1.736 (2) | C7—C8 | 1.416 (3) |
Cl4—C11 | 1.721 (2) | C7—C12 | 1.514 (3) |
O1—C1 | 1.228 (3) | C8—C9 | 1.382 (3) |
O2—C3 | 1.265 (2) | C9—C10 | 1.551 (3) |
O3—C4 | 1.213 (2) | C10—C11 | 1.457 (3) |
O4—C6 | 1.333 (2) | C11—C12 | 1.336 (3) |
O4—H4 | 0.80 (4) | C13—C14 | 1.374 (3) |
O5—C7 | 1.231 (2) | C13—H13 | 0.9500 |
O6—C9 | 1.267 (3) | C14—C15 | 1.399 (3) |
O7—C10 | 1.219 (2) | C14—H14 | 0.9500 |
O8—C12 | 1.334 (3) | C15—C16 | 1.386 (3) |
O8—H8 | 0.93 (4) | C15—C18 | 1.440 (3) |
N1—C13 | 1.341 (3) | C16—C17 | 1.377 (3) |
N1—C17 | 1.344 (3) | C16—H16 | 0.9500 |
N1—H1 | 0.95 (3) | C17—H17 | 0.9500 |
N2—C18 | 1.141 (3) | C19—C20 | 1.376 (3) |
N3—C23 | 1.334 (3) | C19—H19 | 0.9500 |
N3—C19 | 1.341 (3) | C20—C21 | 1.393 (3) |
N3—H3 | 0.90 (3) | C20—H20 | 0.9500 |
N4—C24 | 1.141 (3) | C21—C22 | 1.387 (3) |
C1—C2 | 1.424 (3) | C21—C24 | 1.442 (3) |
C1—C6 | 1.512 (3) | C22—C23 | 1.375 (3) |
C2—C3 | 1.377 (3) | C22—H22 | 0.9500 |
C3—C4 | 1.543 (3) | C23—H23 | 0.9500 |
C6—O4—H4 | 111 (2) | C12—C11—C10 | 120.14 (19) |
C12—O8—H8 | 105 (2) | C12—C11—Cl4 | 121.12 (18) |
C13—N1—C17 | 122.6 (2) | C10—C11—Cl4 | 118.65 (16) |
C13—N1—H1 | 120 (2) | O8—C12—C11 | 123.68 (19) |
C17—N1—H1 | 118 (2) | O8—C12—C7 | 114.58 (18) |
C23—N3—C19 | 122.6 (2) | C11—C12—C7 | 121.7 (2) |
C23—N3—H3 | 119.4 (19) | N1—C13—C14 | 120.7 (2) |
C19—N3—H3 | 118 (2) | N1—C13—H13 | 119.6 |
O1—C1—C2 | 125.5 (2) | C14—C13—H13 | 119.6 |
O1—C1—C6 | 116.86 (18) | C13—C14—C15 | 117.2 (2) |
C2—C1—C6 | 117.66 (19) | C13—C14—H14 | 121.4 |
C3—C2—C1 | 122.6 (2) | C15—C14—H14 | 121.4 |
C3—C2—Cl1 | 120.10 (16) | C16—C15—C14 | 121.4 (2) |
C1—C2—Cl1 | 116.92 (17) | C16—C15—C18 | 118.3 (2) |
O2—C3—C2 | 126.0 (2) | C14—C15—C18 | 120.2 (2) |
O2—C3—C4 | 115.97 (19) | C17—C16—C15 | 118.3 (2) |
C2—C3—C4 | 117.96 (18) | C17—C16—H16 | 120.9 |
O3—C4—C5 | 122.7 (2) | C15—C16—H16 | 120.9 |
O3—C4—C3 | 118.70 (18) | N1—C17—C16 | 119.8 (2) |
C5—C4—C3 | 118.59 (18) | N1—C17—H17 | 120.1 |
C6—C5—C4 | 120.3 (2) | C16—C17—H17 | 120.1 |
C6—C5—Cl2 | 121.68 (16) | N2—C18—C15 | 177.4 (3) |
C4—C5—Cl2 | 117.99 (16) | N3—C19—C20 | 119.8 (2) |
O4—C6—C5 | 122.1 (2) | N3—C19—H19 | 120.1 |
O4—C6—C1 | 115.73 (19) | C20—C19—H19 | 120.1 |
C5—C6—C1 | 122.17 (18) | C19—C20—C21 | 118.5 (2) |
O5—C7—C8 | 127.07 (19) | C19—C20—H20 | 120.7 |
O5—C7—C12 | 114.44 (19) | C21—C20—H20 | 120.7 |
C8—C7—C12 | 118.49 (19) | C22—C21—C20 | 120.5 (2) |
C9—C8—C7 | 122.90 (18) | C22—C21—C24 | 120.7 (2) |
C9—C8—Cl3 | 120.81 (16) | C20—C21—C24 | 118.83 (19) |
C7—C8—Cl3 | 116.14 (16) | C23—C22—C21 | 118.2 (2) |
O6—C9—C8 | 126.72 (19) | C23—C22—H22 | 120.9 |
O6—C9—C10 | 116.38 (18) | C21—C22—H22 | 120.9 |
C8—C9—C10 | 116.90 (18) | N3—C23—C22 | 120.4 (2) |
O7—C10—C11 | 122.69 (19) | N3—C23—H23 | 119.8 |
O7—C10—C9 | 117.86 (19) | C22—C23—H23 | 119.8 |
C11—C10—C9 | 119.41 (18) | N4—C24—C21 | 178.9 (3) |
O1—C1—C2—C3 | 170.6 (2) | O6—C9—C10—O7 | −7.3 (3) |
C6—C1—C2—C3 | −9.2 (3) | C8—C9—C10—O7 | 171.9 (2) |
O1—C1—C2—Cl1 | −2.5 (3) | O6—C9—C10—C11 | 174.71 (19) |
C6—C1—C2—Cl1 | 177.63 (15) | C8—C9—C10—C11 | −6.1 (3) |
C1—C2—C3—O2 | −172.6 (2) | O7—C10—C11—C12 | −174.8 (2) |
Cl1—C2—C3—O2 | 0.3 (3) | C9—C10—C11—C12 | 3.1 (3) |
C1—C2—C3—C4 | 9.6 (3) | O7—C10—C11—Cl4 | 1.7 (3) |
Cl1—C2—C3—C4 | −177.44 (15) | C9—C10—C11—Cl4 | 179.63 (15) |
O2—C3—C4—O3 | −2.2 (3) | C10—C11—C12—O8 | 178.7 (2) |
C2—C3—C4—O3 | 175.76 (19) | Cl4—C11—C12—O8 | 2.3 (3) |
O2—C3—C4—C5 | 177.69 (18) | C10—C11—C12—C7 | −1.4 (3) |
C2—C3—C4—C5 | −4.4 (3) | Cl4—C11—C12—C7 | −177.88 (16) |
O3—C4—C5—C6 | 178.8 (2) | O5—C7—C12—O8 | 2.3 (3) |
C3—C4—C5—C6 | −1.1 (3) | C8—C7—C12—O8 | −177.45 (19) |
O3—C4—C5—Cl2 | −1.2 (3) | O5—C7—C12—C11 | −177.6 (2) |
C3—C4—C5—Cl2 | 178.92 (14) | C8—C7—C12—C11 | 2.7 (3) |
C4—C5—C6—O4 | −177.88 (19) | C17—N1—C13—C14 | 0.8 (3) |
Cl2—C5—C6—O4 | 2.1 (3) | N1—C13—C14—C15 | 0.7 (3) |
C4—C5—C6—C1 | 1.6 (3) | C13—C14—C15—C16 | −1.6 (3) |
Cl2—C5—C6—C1 | −178.48 (15) | C13—C14—C15—C18 | 176.4 (2) |
O1—C1—C6—O4 | 2.9 (3) | C14—C15—C16—C17 | 1.0 (3) |
C2—C1—C6—O4 | −177.21 (18) | C18—C15—C16—C17 | −177.1 (2) |
O1—C1—C6—C5 | −176.6 (2) | C13—N1—C17—C16 | −1.4 (3) |
C2—C1—C6—C5 | 3.3 (3) | C15—C16—C17—N1 | 0.5 (3) |
O5—C7—C8—C9 | 174.2 (2) | C23—N3—C19—C20 | −0.5 (3) |
C12—C7—C8—C9 | −6.1 (3) | N3—C19—C20—C21 | 0.0 (3) |
O5—C7—C8—Cl3 | −1.5 (3) | C19—C20—C21—C22 | 0.5 (3) |
C12—C7—C8—Cl3 | 178.26 (15) | C19—C20—C21—C24 | −179.5 (2) |
C7—C8—C9—O6 | −173.2 (2) | C20—C21—C22—C23 | −0.4 (3) |
Cl3—C8—C9—O6 | 2.2 (3) | C24—C21—C22—C23 | 179.6 (2) |
C7—C8—C9—C10 | 7.6 (3) | C19—N3—C23—C22 | 0.6 (3) |
Cl3—C8—C9—C10 | −176.91 (15) | C21—C22—C23—N3 | −0.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.95 (4) | 1.67 (4) | 2.602 (2) | 170 (3) |
N3—H3···O6 | 0.90 (4) | 1.84 (4) | 2.719 (3) | 166 (3) |
O4—H4···N2i | 0.80 (4) | 1.99 (4) | 2.741 (3) | 155 (4) |
O8—H8···N4ii | 0.93 (5) | 2.07 (5) | 2.875 (3) | 144 (4) |
C13—H13···N4iii | 0.95 | 2.55 | 3.407 (3) | 150 |
C14—H14···O3iv | 0.95 | 2.42 | 3.209 (3) | 141 |
C16—H16···Cl3v | 0.95 | 2.71 | 3.431 (3) | 133 |
C17—H17···O1vi | 0.95 | 2.30 | 3.194 (3) | 157 |
C19—H19···O2 | 0.95 | 2.25 | 3.192 (3) | 170 |
C20—H20···Cl1 | 0.95 | 2.83 | 3.626 (3) | 142 |
C23—H23···O5vii | 0.95 | 2.14 | 3.040 (3) | 158 |
Symmetry codes: (i) x, y, z−1; (ii) x, y+1, z+1; (iii) −x, −y+1, −z; (iv) −x+1, −y+2, −z+1; (v) −x+1, −y+1, −z+1; (vi) −x+1, −y+1, −z; (vii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C6H5N2+·C6HCl2O4− |
Mr | 313.10 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 180 |
a, b, c (Å) | 9.3918 (7), 10.6652 (7), 13.9135 (8) |
α, β, γ (°) | 111.8033 (18), 106.258 (3), 90.416 (3) |
V (Å3) | 1232.50 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.54 |
Crystal size (mm) | 0.36 × 0.31 × 0.09 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID II |
Absorption correction | Numerical (NUMABS; Higashi, 1999) |
Tmin, Tmax | 0.866, 0.953 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21354, 7135, 4934 |
Rint | 0.108 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.066, 0.164, 0.99 |
No. of reflections | 7135 |
No. of parameters | 377 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.89, −0.83 |
Computer programs: PROCESS-AUTO (Rigaku/MSC, 2004), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.95 (4) | 1.67 (4) | 2.602 (2) | 170 (3) |
N3—H3···O6 | 0.90 (4) | 1.84 (4) | 2.719 (3) | 166 (3) |
O4—H4···N2i | 0.80 (4) | 1.99 (4) | 2.741 (3) | 155 (4) |
O8—H8···N4ii | 0.93 (5) | 2.07 (5) | 2.875 (3) | 144 (4) |
C13—H13···N4iii | 0.95 | 2.55 | 3.407 (3) | 150 |
C14—H14···O3iv | 0.95 | 2.42 | 3.209 (3) | 141 |
C16—H16···Cl3v | 0.95 | 2.71 | 3.431 (3) | 133 |
C17—H17···O1vi | 0.95 | 2.30 | 3.194 (3) | 157 |
C19—H19···O2 | 0.95 | 2.25 | 3.192 (3) | 170 |
C20—H20···Cl1 | 0.95 | 2.83 | 3.626 (3) | 142 |
C23—H23···O5vii | 0.95 | 2.14 | 3.040 (3) | 158 |
Symmetry codes: (i) x, y, z−1; (ii) x, y+1, z+1; (iii) −x, −y+1, −z; (iv) −x+1, −y+2, −z+1; (v) −x+1, −y+1, −z+1; (vi) −x+1, −y+1, −z; (vii) −x, −y+1, −z+1. |
Acknowledgements
This work was supported by a Grant-in-Aid for Scientific Research (C) (No. 22550013) from the Japan Society for the Promotion of Science.
References
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The title compound was accidentally obtained in the preparation of the monoclinic polymorph of 4-cyanopyridinium chloranilate, C6H5N2+.C6HCl2O4-, which is an interesting model compound for investigating proton transfer in the hydrogen bond systems (Nihei et al., 2000). The structure of the monoclinic polymorph has been reported by Tomura & Yamashita (2008) and Gotoh et al. (2008).
The asymmetric unit of the triclinic polymorph of the title compound consists of two crystallographically independent cation–anion units, in each of which the cation and the anion are held together by N—H···O hydrogen bond. The dihedral angle between the N1/C13–C17 pyridine ring and the C1–C6 of the acid ring is 78.43 (11)° in one unit, while the angle between the N3/C19–C23 and C7–C12 rings is 80.71 (11)° in the other unit.
In the crystal structure of the monoclinic polymorph, the acid molecule (A) and the base molecule (B) afford an centrosymmetric 2:2 (B:A:A:B) aggregate (Ishida & Kashino, 2002) through O—H···O and N···H···O hydrogen bonds and the H atom in the N···H···O hydrogen bond is disordered over two positions (Gotoh et al., 2008). In contrast to the monoclinic form, the present triclinic polymorph shows two crystallographically independent 1:1 (A:B) units of the acid and base molecules. Each unit independently forms a hydrogen-bonded (–A:B:A:B–) chain; one chain formed by N1—H1···O2 and O4—H4···N2i (symmetry code in Table 1) hydrogen bonds runs along the c axis, while the other chain formed by N3—H3···O6 and O8—H8···N4ii (symmetry code in Table 1) hydrogen bonds runs along the [011] direction. No H atom disorder is observed in these hydrogen bonds. Between the chains, C—H···O, C—H···N and C—H···Cl interactions (Table 1) are observed.