Bis(tri­ethyl­ammonium) chloranilate

Gotoh, K.; Maruyama, S.; Ishida, H.

doi:10.1107/S1600536813021405

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 9| September 2013| Page o1400

doi:10.1107/S1600536813021405

Open

access

Bis(triethylammonium) chloranilate

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

^aDepartment of Chemistry, Faculty of Science, Okayama University, Okayama 700-8530, Japan
^*Correspondence e-mail: ishidah@cc.okayama-u.ac.jp

(Received 19 July 2013; accepted 1 August 2013; online 10 August 2013)

In the crystal structure of the title compound [systematic name: bis(triethylammonium) 2,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,4-diolate], 2C₆H₁₆N⁺·C₆Cl₂O₄²⁻, the chloranilate anion lies on an inversion center. The triethylammonium cations are linked on both sides of the anion via bifurcated N—H⋯(O,O) and weak C—H⋯O hydrogen bonds to give a centrosymmetric 2:1 aggregate. The 2:1 aggregates are further linked by C—H⋯O hydrogen bonds into a zigzag chain running along [01-1].

Related literature

For related structures, see: Dayananda et al. (2012 ); Gotoh et al. (2009 , 2010 ); Yang (2007 ).

Experimental

Crystal data

2C₆H₁₆N⁺·C₆Cl₂O₄²⁻
M_r = 411.37
Triclinic, $[P \overline 1]$
a = 7.7347 (5) Å
b = 8.5151 (8) Å
c = 9.3913 (7) Å
α = 64.388 (4)°
β = 68.435 (3)°
γ = 79.060 (5)°
V = 518.36 (7) Å³
Z = 1
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 180 K
0.65 × 0.31 × 0.21 mm

Data collection

Rigaku R-AXIS RAPID II diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ) T_min = 0.858, T_max = 0.932
10264 measured reflections
3012 independent reflections
2561 reflections with I > 2σ(I)
R_int = 0.078

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.121
S = 1.06
3012 reflections
125 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.867 (18)	1.942 (18)	2.7601 (15)	156.9 (15)
N1—H1⋯O2ⁱ	0.867 (18)	2.339 (17)	2.9377 (14)	126.4 (14)
C5—H5C⋯O1	0.98	2.57	3.2911 (19)	131
C9—H9B⋯O1ⁱⁱ	0.98	2.55	3.5315 (17)	177
Symmetry codes: (i) -x+1, -y+2, -z; (ii) -x+1, -y+1, -z+1.

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 for Windows (Farrugia, 2012 ); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks General, I. DOI: 10.1107/S1600536813021405/lh5635sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813021405/lh5635Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813021405/lh5635Isup3.cml

checkCIF report

Comment top

The title compound 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., 2009, 2010). For the tertiary amine–chloranilic acid systems, crystal structures of bis(hexamethylenetetraminium) chloranilate tetrahydrate (Yang, 2007), triethylammonium hydrogen chloranilate (Gotoh et al., 2010) and triprolidinium dichloranilate–chloranilic acid–methanol–water (2/1/2/2) (Dayananda et al., 2012) have been reported.

In the crystal structure of the title compound, an acid-base interaction involving proton transfer is observed between chloranilic acid and triethylamine, and one chloranilate anion and two triethylammnoium cations are linked by bifurcated N—H···O and weak C—H···O hydrogen bonds (Table 1) to afford a centrosymmetric 2:1 aggregate (Fig. 1). The 2:1 aggregates are further linked by intermolecular C—H···O hydrogen bonds, forming a zigzag chain running along the [011] direction (Fig. 2).

Related literature top

For related structures, see: Dayananda et al. (2012); Gotoh et al. (2009, 2010); Yang (2007).

Experimental top

Single crystals were obtained by slow evaporation from an acetonitrile solution (100 ml) of chloranilic acid (100 mg) and triethylamine (97 mg) at room temperature.

Computing details top

Data collection: PROCESS-AUTO (Rigaku/MSC, 2004); cell refinement: 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 for Windows (Farrugia, 2012); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with the atom-labeling. Displacement ellipsoids of non-H atoms are drawn at the 30% probability level. The dashed lines indicate N—H···O and C—H···O hydrogen bonds. [Symmetry code: (i) -x + 1, -y + 2, -z.]
	Fig. 2. A partial packing diagram of the title compound. The dashed lines indicate N—H···O and C—H···O hydrogen bonds. H atoms of the ethyl groups not involved in the C—H···O hydrogen bonds have been omitted. [Symmetry codes: (i) -x + 1, -y + 2, -z; (ii) -x + 1, -y + 1, -z.]

Bis(triethylammonium) 2,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,4-diolate top

Crystal data top

2C₆H₁₆N⁺·C₆Cl₂O₄²⁻	Z = 1
M_r = 411.37	F(000) = 220.00
Triclinic, P1	D_x = 1.318 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 7.7347 (5) Å	Cell parameters from 8559 reflections
b = 8.5151 (8) Å	θ = 3.1–30.1°
c = 9.3913 (7) Å	µ = 0.34 mm⁻¹
α = 64.388 (4)°	T = 180 K
β = 68.435 (3)°	Block, brown
γ = 79.060 (5)°	0.65 × 0.31 × 0.21 mm
V = 518.36 (7) Å³

Data collection top

Rigaku R-AXIS RAPID II diffractometer	2561 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.078
ω scans	θ_max = 30.0°, θ_min = 3.1°
Absorption correction: numerical (NUMABS; Higashi, 1999)	h = −10→10
T_min = 0.858, T_max = 0.932	k = −11→11
10264 measured reflections	l = −13→13
3012 independent reflections

Refinement top

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0654P)²] where P = (F_o² + 2F_c²)/3
3012 reflections	(Δ/σ)_max = 0.001
125 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

2C₆H₁₆N⁺·C₆Cl₂O₄²⁻	γ = 79.060 (5)°
M_r = 411.37	V = 518.36 (7) Å³
Triclinic, P1	Z = 1
a = 7.7347 (5) Å	Mo Kα radiation
b = 8.5151 (8) Å	µ = 0.34 mm⁻¹
c = 9.3913 (7) Å	T = 180 K
α = 64.388 (4)°	0.65 × 0.31 × 0.21 mm
β = 68.435 (3)°

Data collection top

Rigaku R-AXIS RAPID II diffractometer	3012 independent reflections
Absorption correction: numerical (NUMABS; Higashi, 1999)	2561 reflections with I > 2σ(I)
T_min = 0.858, T_max = 0.932	R_int = 0.078
10264 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.48 e Å⁻³
3012 reflections	Δρ_min = −0.26 e Å⁻³
125 parameters

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	0.14870 (4)	0.93266 (4)	0.32667 (3)	0.03021 (13)
O1	0.44257 (12)	0.67475 (10)	0.24001 (11)	0.0322 (2)
O2	0.26077 (12)	1.26690 (10)	0.03171 (10)	0.0326 (2)
N1	0.67048 (13)	0.38363 (13)	0.23709 (12)	0.0242 (2)
C1	0.46352 (15)	0.82853 (14)	0.13459 (13)	0.0237 (2)
C2	0.34397 (15)	0.96966 (14)	0.14976 (13)	0.0235 (2)
C3	0.36699 (15)	1.13964 (14)	0.02453 (14)	0.0235 (2)
C4	0.54491 (18)	0.26759 (16)	0.40054 (15)	0.0313 (3)
H4A	0.5321	0.3103	0.4868	0.038*
H4B	0.6024	0.1485	0.4333	0.038*
C5	0.35317 (19)	0.25958 (19)	0.39536 (18)	0.0396 (3)
H5A	0.2712	0.1966	0.5086	0.059*
H5B	0.3625	0.1988	0.3247	0.059*
H5C	0.3018	0.3782	0.3494	0.059*
C6	0.69491 (17)	0.33514 (16)	0.09491 (15)	0.0297 (3)
H6A	0.7649	0.4268	−0.0105	0.036*
H6B	0.5708	0.3319	0.0884	0.036*
C7	0.7960 (2)	0.1614 (2)	0.1098 (2)	0.0435 (4)
H7A	0.8200	0.1442	0.0075	0.065*
H7B	0.7191	0.0679	0.2051	0.065*
H7C	0.9143	0.1595	0.1265	0.065*
C8	0.85542 (16)	0.39642 (17)	0.24970 (15)	0.0295 (3)
H8A	0.9018	0.2780	0.3091	0.035*
H8B	0.9459	0.4451	0.1360	0.035*
C9	0.84408 (19)	0.50912 (17)	0.34006 (17)	0.0342 (3)
H9A	0.9693	0.5226	0.3355	0.051*
H9B	0.7662	0.4542	0.4567	0.051*
H9C	0.7894	0.6239	0.2868	0.051*
H1	0.618 (2)	0.487 (2)	0.209 (2)	0.034 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02658 (19)	0.03015 (19)	0.02264 (18)	0.00392 (12)	−0.00412 (13)	−0.00561 (13)
O1	0.0340 (5)	0.0216 (4)	0.0265 (4)	0.0031 (3)	−0.0046 (4)	−0.0025 (3)
O2	0.0326 (5)	0.0247 (4)	0.0290 (5)	0.0080 (3)	−0.0055 (4)	−0.0078 (4)
N1	0.0252 (5)	0.0216 (5)	0.0220 (4)	0.0037 (3)	−0.0086 (4)	−0.0062 (4)
C1	0.0254 (5)	0.0227 (5)	0.0216 (5)	0.0019 (4)	−0.0092 (4)	−0.0072 (4)
C2	0.0235 (5)	0.0233 (5)	0.0196 (5)	0.0023 (4)	−0.0067 (4)	−0.0063 (4)
C3	0.0246 (5)	0.0219 (5)	0.0230 (5)	0.0030 (4)	−0.0094 (4)	−0.0082 (4)
C4	0.0327 (6)	0.0267 (6)	0.0254 (6)	0.0000 (4)	−0.0062 (5)	−0.0054 (5)
C5	0.0352 (7)	0.0392 (7)	0.0414 (7)	−0.0081 (5)	−0.0058 (6)	−0.0159 (6)
C6	0.0326 (6)	0.0317 (6)	0.0267 (6)	0.0028 (5)	−0.0139 (5)	−0.0114 (5)
C7	0.0479 (8)	0.0454 (8)	0.0561 (9)	0.0166 (6)	−0.0296 (7)	−0.0339 (7)
C8	0.0262 (6)	0.0355 (6)	0.0272 (6)	0.0026 (4)	−0.0106 (5)	−0.0128 (5)
C9	0.0355 (7)	0.0370 (7)	0.0330 (6)	−0.0009 (5)	−0.0120 (5)	−0.0159 (6)

Geometric parameters (Å, º) top

Cl1—C2	1.7390 (11)	C5—H5B	0.9800
O1—C1	1.2502 (13)	C5—H5C	0.9800
O2—C3	1.2403 (13)	C6—C7	1.5103 (18)
N1—C4	1.4943 (15)	C6—H6A	0.9900
N1—C6	1.5002 (15)	C6—H6B	0.9900
N1—C8	1.5056 (15)	C7—H7A	0.9800
N1—H1	0.867 (18)	C7—H7B	0.9800
C1—C2	1.3960 (15)	C7—H7C	0.9800
C1—C3ⁱ	1.5394 (16)	C8—C9	1.5054 (17)
C2—C3	1.4079 (15)	C8—H8A	0.9900
C3—C1ⁱ	1.5394 (16)	C8—H8B	0.9900
C4—C5	1.517 (2)	C9—H9A	0.9800
C4—H4A	0.9900	C9—H9B	0.9800
C4—H4B	0.9900	C9—H9C	0.9800
C5—H5A	0.9800

C4—N1—C6	113.81 (10)	H5B—C5—H5C	109.5
C4—N1—C8	111.29 (9)	N1—C6—C7	113.74 (10)
C6—N1—C8	111.25 (9)	N1—C6—H6A	108.8
C4—N1—H1	108.1 (10)	C7—C6—H6A	108.8
C6—N1—H1	103.7 (10)	N1—C6—H6B	108.8
C8—N1—H1	108.2 (10)	C7—C6—H6B	108.8
O1—C1—C2	125.01 (10)	H6A—C6—H6B	107.7
O1—C1—C3ⁱ	116.31 (9)	C6—C7—H7A	109.5
C2—C1—C3ⁱ	118.67 (9)	C6—C7—H7B	109.5
C1—C2—C3	123.37 (10)	H7A—C7—H7B	109.5
C1—C2—Cl1	118.69 (8)	C6—C7—H7C	109.5
C3—C2—Cl1	117.83 (8)	H7A—C7—H7C	109.5
O2—C3—C2	125.12 (10)	H7B—C7—H7C	109.5
O2—C3—C1ⁱ	116.95 (9)	C9—C8—N1	112.57 (10)
C2—C3—C1ⁱ	117.93 (9)	C9—C8—H8A	109.1
N1—C4—C5	112.84 (11)	N1—C8—H8A	109.1
N1—C4—H4A	109.0	C9—C8—H8B	109.1
C5—C4—H4A	109.0	N1—C8—H8B	109.1
N1—C4—H4B	109.0	H8A—C8—H8B	107.8
C5—C4—H4B	109.0	C8—C9—H9A	109.5
H4A—C4—H4B	107.8	C8—C9—H9B	109.5
C4—C5—H5A	109.5	H9A—C9—H9B	109.5
C4—C5—H5B	109.5	C8—C9—H9C	109.5
H5A—C5—H5B	109.5	H9A—C9—H9C	109.5
C4—C5—H5C	109.5	H9B—C9—H9C	109.5
H5A—C5—H5C	109.5

O1—C1—C2—C3	−176.68 (11)	Cl1—C2—C3—C1ⁱ	−178.12 (8)
C3ⁱ—C1—C2—C3	1.97 (19)	C6—N1—C4—C5	−56.62 (13)
O1—C1—C2—Cl1	−0.54 (17)	C8—N1—C4—C5	176.71 (10)
C3ⁱ—C1—C2—Cl1	178.11 (8)	C4—N1—C6—C7	−66.29 (14)
C1—C2—C3—O2	177.84 (11)	C8—N1—C6—C7	60.39 (14)
Cl1—C2—C3—O2	1.67 (17)	C4—N1—C8—C9	−74.58 (13)
C1—C2—C3—C1ⁱ	−1.95 (18)	C6—N1—C8—C9	157.36 (10)

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.867 (18)	1.942 (18)	2.7601 (15)	156.9 (15)
N1—H1···O2ⁱ	0.867 (18)	2.339 (17)	2.9377 (14)	126.4 (14)
C5—H5C···O1	0.98	2.57	3.2911 (19)	131
C9—H9B···O1ⁱⁱ	0.98	2.55	3.5315 (17)	177

Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.867 (18)	1.942 (18)	2.7601 (15)	156.9 (15)
N1—H1···O2ⁱ	0.867 (18)	2.339 (17)	2.9377 (14)	126.4 (14)
C5—H5C···O1	0.98	2.57	3.2911 (19)	131
C9—H9B···O1ⁱⁱ	0.98	2.55	3.5315 (17)	177

Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −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

Dayananda, A. S., Butcher, R. J., Akkurt, M., Yathirajan, H. S. & Narayana, B. (2012). Acta Cryst. E68, o1037–o1038. CSD CrossRef CAS IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gotoh, K., Maruyama, S. & Ishida, H. (2010). Acta Cryst. E66, o3255. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gotoh, K., Nagoshi, H. & Ishida, H. (2009). Acta Cryst. C65, o273–o277. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (1999). NUMABS. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2004). PROCESS-AUTO and CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, D.-J. (2007). Acta Cryst. E63, o2600. Web of Science CSD CrossRef IUCr Journals Google Scholar