Triethyl­ammonium hydrogen chloranilate

Kazuma Gotoh; Shinpei Maruyama; Hiroyuki Ishida

doi:10.1107/S1600536810047744

. 2010 Nov 20;66(Pt 12):o3255. doi: 10.1107/S1600536810047744

Triethylammonium hydrogen chloranilate

Kazuma Gotoh ^a, Shinpei Maruyama ^a, Hiroyuki Ishida ^a,^*

PMCID: PMC3011634 PMID: 21589539

Abstract

In the crystal structure of the title compound (systematic name: triethylammonium 2,5-dichloro-4-hydroxy-3,6-dioxocyclohexa-1,4-dien-1-olate), C₆H₁₆N⁺·C₆HCl₂O₄ ⁻, two hydrogen chloranilate anions are connected by a pair of bifurcated O—H⋯O hydrogen bonds into a dimeric unit. The triethylammonium cations are linked on both sides of the dimer via bifurcated N—H⋯O hydrogen bonds into a centrosymmetric 2:2 aggregate. The 2:2 aggregates are further linked by intermolecular C—H⋯O hydrogen bonds.

Related literature

For related structures, see, for example: Gotoh et al. (2008 ▶, 2009 ▶); Gotoh & Ishida (2009 ▶); Yang (2007 ▶). For details of the double π system of chloranilic acid, see: Andersen (1967 ▶); Benchekroun & Savariault (1995 ▶).

Experimental

Crystal data

C₆H₁₆N⁺·C₆HCl₂O₄ ⁻
M _r = 310.18
Triclinic,
a = 7.6404 (5) Å
b = 9.5352 (3) Å
c = 11.2976 (5) Å
α = 99.9621 (15)°
β = 108.732 (3)°
γ = 106.536 (3)°
V = 714.84 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 180 K
0.42 × 0.35 × 0.25 mm

Data collection

Rigaku R-AXIS RAPID II diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T _min = 0.829, T _max = 0.891
14757 measured reflections
4176 independent reflections
3631 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.092
S = 1.07
4176 reflections
180 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.36 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 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810047744/hg2739sup1.cif

e-66-o3255-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810047744/hg2739Isup2.hkl

e-66-o3255-Isup2.hkl^{(204.6KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.847 (18)	2.411 (15)	2.9805 (12)	125.1 (13)
N1—H1⋯O4	0.847 (18)	2.069 (18)	2.8833 (12)	161.1 (14)
O2—H2⋯O3	0.765 (19)	2.147 (19)	2.6331 (11)	121.9 (17)
O2—H2⋯O3ⁱ	0.765 (19)	2.082 (19)	2.7089 (12)	139.4 (19)
C7—H7B⋯O2ⁱⁱ	0.99	2.47	3.2859 (15)	140
C8—H8A⋯O4ⁱⁱⁱ	0.98	2.47	3.3977 (14)	158

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

This work was supported by a Grant-in-Aid for Scientific Research (C) (No. 22550013) from the Japan Society for the Promotion of Science.

supplementary crystallographic information

Comment

The title compound, (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 amine–chloranilic acid systems (Gotoh et al., 2008,2009; Gotoh & Ishida, 2009). The crystal structure of bis(hexamethylenetetraminium) chloranilate tetrahydrate has been reported for the tertiary amine–chloranilic acid 2:1 system (Yang, 2007).

In the crystal structure of the title compound, an acid-base interaction involving proton transfer is observed between chloranilic acid and triethylamine, and two hydrogen chloranilate anions and two triethylammnoium cations are linked by bifurcated O—H···O and N—H···O hydrogen bonds (Table 1) to afford a centrosymmetric 2:2 aggregate (Fig. 1). The anion shows a characteristic structure of the double π system (Andersen, 1967; Benchekroun & Savariault, 1995) with two long C1—C6 [1.5442 (13) Å] and C3—C4 [1.5063 (13) Å] bonds. The O3—C4 and O4—C6 bonds [1.2529 (11) and 1.2510 (11) Å, respectively] in one π system are almost same and comparable to the O—C bonds in the dianion of bis(hexamethylenetetraminium) chloranilate tetrahydrate (Yang, 2007). On the other hand, the O1—C1 and O2—C3 bonds [1.2199 (12) and 1.3324 (11) Å, respectively] in the other π system correspond to double and single bonds, respectively. The 2:2 aggregates are further linked by intermolecular C—H···O hydrogen bonds, forming a three-dimensional network (Fig. 2).

Experimental

Single crystals were obtained by slow evaporation from an acetonitrile solution (25 ml) of chloranilic acid (97 mg) and triethylamine (42 mg) at room temperature.