Triethyl-ammonium hydrogen chloranilate.

IN THE CRYSTAL STRUCTURE OF THE TITLE COMPOUND (SYSTEMATIC NAME: triethyl-ammonium 2,5-dichloro-4-hy-droxy-3,6-dioxo-cyclo-hexa-1,4-dien-1-olate), C(6)H(16)N(+)·C(6)HCl(2)O(4) (-), two hydrogen chloranilate anions are connected by a pair of bifurcated O-H⋯O hydrogen bonds into a dimeric unit. The triethyl-ammonium 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 inter-molecular 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 = 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

Δρmax = 0.59 e Å−3

Δρmin = −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 ▶).

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

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

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

C6H16N+·C6HCl2O4−	Z = 2
Mr = 310.18	F(000) = 324.00
Triclinic, P1	Dx = 1.441 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 7.6404 (5) Å	Cell parameters from 12766 reflections
b = 9.5352 (3) Å	θ = 3.0–30.1°
c = 11.2976 (5) Å	µ = 0.46 mm−1
α = 99.9621 (15)°	T = 180 K
β = 108.732 (3)°	Block, brown
γ = 106.536 (3)°	0.42 × 0.35 × 0.25 mm
V = 714.84 (6) Å3

Rigaku R-AXIS RAPID II diffractometer	3631 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm-1	Rint = 0.034
ω scans	θmax = 30.0°
Absorption correction: numerical (NUMABS; Higashi, 1999)	h = −10→10
Tmin = 0.829, Tmax = 0.891	k = −13→13
14757 measured reflections	l = −15→15
4176 independent reflections

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0543P)2 + 0.1133P] where P = (Fo2 + 2Fc2)/3
4176 reflections	(Δ/σ)max = 0.001
180 parameters	Δρmax = 0.59 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

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	0.05941 (4)	0.44199 (3)	−0.17017 (2)	0.03282 (8)
Cl2	0.79265 (4)	0.85112 (3)	0.35611 (2)	0.03113 (8)
O1	0.23295 (13)	0.35023 (9)	0.06660 (8)	0.03546 (18)
O2	0.29888 (11)	0.77018 (9)	−0.10218 (8)	0.02849 (16)
O3	0.60830 (11)	0.93820 (8)	0.11497 (7)	0.02933 (16)
O4	0.53520 (12)	0.51893 (9)	0.29193 (8)	0.03090 (17)
N1	0.31226 (12)	0.21786 (9)	0.28996 (8)	0.02410 (16)
C1	0.31746 (14)	0.48352 (11)	0.07566 (9)	0.02382 (18)
C2	0.25857 (14)	0.55307 (11)	−0.02828 (9)	0.02340 (18)
C3	0.35511 (14)	0.70234 (11)	−0.01071 (9)	0.02249 (18)
C4	0.53096 (14)	0.80246 (10)	0.11283 (9)	0.02232 (17)
C5	0.59095 (14)	0.73644 (11)	0.21385 (9)	0.02326 (18)
C6	0.49384 (14)	0.58366 (11)	0.20508 (9)	0.02325 (18)
C7	0.12245 (15)	0.22545 (12)	0.29816 (11)	0.0307 (2)
H7A	0.0632	0.1399	0.3289	0.037*
H7B	0.0275	0.2125	0.2098	0.037*
C8	0.15318 (17)	0.37395 (13)	0.38885 (11)	0.0323 (2)
H8A	0.2209	0.3765	0.4795	0.048*
H8B	0.0242	0.3827	0.3768	0.048*
H8C	0.2344	0.4594	0.3693	0.048*
C9	0.27183 (18)	0.08580 (12)	0.17789 (11)	0.0320 (2)
H9A	0.3979	0.0937	0.1676	0.038*
H9B	0.1802	0.0938	0.0967	0.038*
C10	0.1828 (2)	−0.06935 (13)	0.19402 (15)	0.0435 (3)
H10A	0.2787	−0.0831	0.2686	0.065*
H10B	0.1502	−0.1493	0.1145	0.065*
H10C	0.0619	−0.0762	0.2094	0.065*
C11	0.45590 (16)	0.22080 (13)	0.41806 (11)	0.0313 (2)
H11A	0.3995	0.1271	0.4406	0.038*
H11B	0.4747	0.3098	0.4872	0.038*
C12	0.65531 (19)	0.23066 (17)	0.41462 (15)	0.0461 (3)
H12A	0.6413	0.1348	0.3574	0.069*
H12B	0.7501	0.2480	0.5031	0.069*
H12C	0.7037	0.3156	0.3811	0.069*
H1	0.365 (2)	0.2974 (19)	0.2713 (14)	0.037 (4)*
H2	0.364 (3)	0.855 (2)	−0.0717 (17)	0.055 (5)*

	U11	U22	U33	U12	U13	U23
Cl1	0.03108 (13)	0.02407 (13)	0.03098 (14)	0.00336 (10)	0.00192 (10)	0.00952 (9)
Cl2	0.03405 (14)	0.02543 (13)	0.02406 (13)	0.00126 (10)	0.00727 (10)	0.00770 (9)
O1	0.0406 (4)	0.0198 (4)	0.0355 (4)	0.0021 (3)	0.0070 (3)	0.0134 (3)
O2	0.0304 (4)	0.0204 (4)	0.0303 (4)	0.0052 (3)	0.0067 (3)	0.0140 (3)
O3	0.0342 (4)	0.0184 (3)	0.0333 (4)	0.0056 (3)	0.0114 (3)	0.0128 (3)
O4	0.0353 (4)	0.0252 (4)	0.0283 (4)	0.0050 (3)	0.0091 (3)	0.0153 (3)
N1	0.0257 (4)	0.0190 (4)	0.0277 (4)	0.0046 (3)	0.0123 (3)	0.0098 (3)
C1	0.0266 (4)	0.0192 (4)	0.0267 (4)	0.0069 (3)	0.0112 (3)	0.0101 (3)
C2	0.0235 (4)	0.0195 (4)	0.0255 (4)	0.0059 (3)	0.0079 (3)	0.0088 (3)
C3	0.0244 (4)	0.0203 (4)	0.0257 (4)	0.0082 (3)	0.0113 (3)	0.0109 (3)
C4	0.0252 (4)	0.0183 (4)	0.0262 (4)	0.0076 (3)	0.0124 (3)	0.0092 (3)
C5	0.0260 (4)	0.0193 (4)	0.0230 (4)	0.0051 (3)	0.0094 (3)	0.0083 (3)
C6	0.0261 (4)	0.0206 (4)	0.0249 (4)	0.0069 (3)	0.0117 (3)	0.0103 (3)
C7	0.0232 (4)	0.0292 (5)	0.0376 (5)	0.0063 (4)	0.0120 (4)	0.0104 (4)
C8	0.0319 (5)	0.0344 (6)	0.0357 (5)	0.0164 (4)	0.0144 (4)	0.0131 (4)
C9	0.0415 (6)	0.0214 (5)	0.0327 (5)	0.0066 (4)	0.0187 (4)	0.0070 (4)
C10	0.0536 (7)	0.0218 (5)	0.0571 (8)	0.0075 (5)	0.0306 (6)	0.0101 (5)
C11	0.0301 (5)	0.0330 (5)	0.0312 (5)	0.0120 (4)	0.0103 (4)	0.0127 (4)
C12	0.0337 (6)	0.0490 (8)	0.0561 (8)	0.0214 (5)	0.0146 (5)	0.0117 (6)

Cl1—C2	1.7133 (10)	C7—H7A	0.9900
Cl2—C5	1.7307 (10)	C7—H7B	0.9900
O1—C1	1.2199 (12)	C8—H8A	0.9800
O2—C3	1.3324 (11)	C8—H8B	0.9800
O2—H2	0.766 (18)	C8—H8C	0.9800
O3—C4	1.2529 (11)	C9—C10	1.5115 (16)
O4—C6	1.2510 (11)	C9—H9A	0.9900
N1—C11	1.4993 (13)	C9—H9B	0.9900
N1—C9	1.5033 (13)	C10—H10A	0.9800
N1—C7	1.5036 (13)	C10—H10B	0.9800
N1—H1	0.847 (16)	C10—H10C	0.9800
C1—C2	1.4564 (13)	C11—C12	1.5130 (16)
C1—C6	1.5442 (13)	C11—H11A	0.9900
C2—C3	1.3490 (13)	C11—H11B	0.9900
C3—C4	1.5063 (13)	C12—H12A	0.9800
C4—C5	1.4092 (13)	C12—H12B	0.9800
C5—C6	1.4036 (13)	C12—H12C	0.9800
C7—C8	1.5047 (16)
C3—O2—H2	106.0 (13)	C7—C8—H8A	109.5
C11—N1—C9	113.52 (8)	C7—C8—H8B	109.5
C11—N1—C7	111.98 (8)	H8A—C8—H8B	109.5
C9—N1—C7	111.23 (8)	C7—C8—H8C	109.5
C11—N1—H1	107.6 (10)	H8A—C8—H8C	109.5
C9—N1—H1	105.4 (10)	H8B—C8—H8C	109.5
C7—N1—H1	106.5 (10)	N1—C9—C10	114.04 (9)
O1—C1—C2	123.39 (9)	N1—C9—H9A	108.7
O1—C1—C6	118.01 (8)	C10—C9—H9A	108.7
C2—C1—C6	118.60 (8)	N1—C9—H9B	108.7
C3—C2—C1	120.43 (9)	C10—C9—H9B	108.7
C3—C2—Cl1	121.32 (7)	H9A—C9—H9B	107.6
C1—C2—Cl1	118.21 (7)	C9—C10—H10A	109.5
O2—C3—C2	121.58 (9)	C9—C10—H10B	109.5
O2—C3—C4	115.99 (8)	H10A—C10—H10B	109.5
C2—C3—C4	122.42 (8)	C9—C10—H10C	109.5
O3—C4—C5	126.59 (9)	H10A—C10—H10C	109.5
O3—C4—C3	115.62 (8)	H10B—C10—H10C	109.5
C5—C4—C3	117.79 (8)	N1—C11—C12	112.26 (10)
C6—C5—C4	123.24 (9)	N1—C11—H11A	109.2
C6—C5—Cl2	118.80 (7)	C12—C11—H11A	109.2
C4—C5—Cl2	117.95 (7)	N1—C11—H11B	109.2
O4—C6—C5	126.67 (9)	C12—C11—H11B	109.2
O4—C6—C1	115.87 (8)	H11A—C11—H11B	107.9
C5—C6—C1	117.46 (8)	C11—C12—H12A	109.5
N1—C7—C8	112.65 (8)	C11—C12—H12B	109.5
N1—C7—H7A	109.1	H12A—C12—H12B	109.5
C8—C7—H7A	109.1	C11—C12—H12C	109.5
N1—C7—H7B	109.1	H12A—C12—H12C	109.5
C8—C7—H7B	109.1	H12B—C12—H12C	109.5
H7A—C7—H7B	107.8
O1—C1—C2—C3	178.24 (10)	C3—C4—C5—Cl2	−179.88 (7)
C6—C1—C2—C3	−0.79 (14)	C4—C5—C6—O4	−177.80 (10)
O1—C1—C2—Cl1	0.38 (14)	Cl2—C5—C6—O4	1.38 (15)
C6—C1—C2—Cl1	−178.65 (7)	C4—C5—C6—C1	2.18 (14)
C1—C2—C3—O2	−177.16 (9)	Cl2—C5—C6—C1	−178.64 (6)
Cl1—C2—C3—O2	0.63 (14)	O1—C1—C6—O4	−0.58 (14)
C1—C2—C3—C4	2.41 (15)	C2—C1—C6—O4	178.50 (9)
Cl1—C2—C3—C4	−179.80 (7)	O1—C1—C6—C5	179.44 (9)
O2—C3—C4—O3	−1.57 (12)	C2—C1—C6—C5	−1.48 (13)
C2—C3—C4—O3	178.84 (9)	C11—N1—C7—C8	64.50 (11)
O2—C3—C4—C5	177.84 (8)	C9—N1—C7—C8	−167.30 (9)
C2—C3—C4—C5	−1.75 (14)	C11—N1—C9—C10	60.54 (13)
O3—C4—C5—C6	178.64 (9)	C7—N1—C9—C10	−66.83 (13)
C3—C4—C5—C6	−0.70 (14)	C9—N1—C11—C12	59.27 (12)
O3—C4—C5—Cl2	−0.55 (14)	C7—N1—C11—C12	−173.75 (9)

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

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

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