1,2-Diazinium hydrogen chloranilate

Gotoh, K.; Ishida, H.

doi:10.1107/S1600536808031978

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2095

doi:10.1107/S1600536808031978

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1,2-Diazinium hydrogen chloranilate

Kazuma Gotoh ^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 30 September 2008; accepted 5 October 2008; online 11 October 2008)

In the crystal structure of the title compound, C₄H₅N₂⁺·C₆HCl₂O₄⁻, there are three crystallographically independent 1,2-diazinium cations and hydrogen chloranilate anions. The anions are held together by pairs of O—H⋯O hydrogen bonds to form two types of dimers, one of which is centrosymmetric. The 1,2-diazinium cations are linked on both sides of each dimer via bifurcated N—H⋯O hydrogen bonds to give two kinds of 2–2 cation–anion associations. The 2–2 associations are linked by intermolecular C—H⋯O and C—H⋯N hydrogen bonds, forming a molecular tape along the [230] direction. The tapes are further connected by C—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For general background, see: Gotoh et al. (2007 ). For related compounds, see: Gotoh et al. (2008 ); Ishida & Kashino (1999 ).

Experimental

Crystal data

C₄H₅N₂⁺·C₆HCl₂O₄⁻
M_r = 289.07
Monoclinic, P 2₁ /c
a = 25.6849 (10) Å
b = 7.0516 (2) Å
c = 18.1388 (6) Å
β = 97.5822 (13)°
V = 3256.56 (18) Å³
Z = 12
Mo Kα radiation
μ = 0.61 mm⁻¹
T = 173 (1) K
0.40 × 0.22 × 0.12 mm

Data collection

Rigaku R-AXIS RAPIDII diffractometer
Absorption correction: numerical (ABSCOR; Higashi, 1999 ) T_min = 0.855, T_max = 0.930
42942 measured reflections
9398 independent reflections
7981 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.082
S = 1.04
9398 reflections
511 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 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⋯O2	0.889 (17)	1.753 (17)	2.6138 (13)	162.2 (17)
N1—H1⋯O3	0.889 (17)	2.578 (18)	3.1583 (14)	123.7 (14)
N3—H3⋯O6	0.886 (18)	1.811 (17)	2.6621 (13)	160.4 (17)
N3—H3⋯O7	0.886 (18)	2.431 (18)	3.0066 (14)	123.0 (14)
O4—H4⋯O1	0.79 (2)	2.26 (2)	2.6619 (13)	113 (2)
O4—H4⋯O5	0.79 (2)	1.94 (2)	2.6723 (12)	155 (2)
N5—H5⋯O10	0.890 (18)	1.881 (18)	2.7450 (14)	163.2 (16)
N5—H5⋯O11	0.890 (18)	2.410 (17)	2.9659 (13)	120.7 (14)
O8—H8⋯O1	0.80 (2)	1.86 (2)	2.5930 (12)	152 (2)
O8—H8⋯O5	0.80 (2)	2.25 (2)	2.6582 (13)	112.7 (18)
O12—H12⋯O9	0.79 (2)	2.23 (2)	2.6595 (13)	115.1 (18)
O12—H12⋯O9ⁱ	0.79 (2)	2.02 (2)	2.6801 (12)	142 (2)
C20—H20⋯O2ⁱⁱ	0.95	2.57	3.1097 (15)	116
C21—H21⋯O3ⁱⁱⁱ	0.95	2.36	3.2754 (15)	162
C22—H22⋯O3	0.95	2.60	3.1913 (15)	121
C25—H25⋯O10	0.95	2.47	3.4056 (15)	169
C26—H26⋯O7	0.95	2.44	3.0363 (15)	121
C26—H26⋯N6	0.95	2.51	3.2665 (17)	137
C27—H27⋯O7	0.95	2.37	3.2765 (15)	159
C28—H28⋯O6^iv	0.95	2.47	3.1091 (15)	124
C30—H30⋯O11	0.95	2.34	2.9551 (15)	122
Symmetry codes: (i) -x, -y, -z+1; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x+2, -y+3, -z+1; (iv) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

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, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808031978/fj2158sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808031978/fj2158Isup2.hkl

checkCIF report

Comment top

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 (systematic name: 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone) systems (Gotoh et al., 2007). The crystal structure of 1,2-diazine (pyridazine)–chloranilic acid (2/1) was already reported (Ishida & Kashino, 1999; Gotoh et al., 2008).

The asymmetric unit in (I) contains three 1,2-diazinium cations and three hydrogen chloranilate anions. Hydrogen chloranilate anions are held together by O—H···O hydrogen bonds (Table 1) to form two crystallographically independent dimers. The 1,2-diazinium cations are linked on both sides of each dimer via bifurcated N—H···O hydrogen bonds to give centro- and acentrosymmetric 2:2 salts of 1,2-diazine and chloranilic acid (Fig. 1). The N···O distances [2.6138 (13)–3.1583 (14) Å] in the hydrogen bonds are longer than those [2.582 (3) Å at 299 K (Ishida & Kashino, 1999) and 2.5549 (12) Å at 110 K (Gotoh et al., 2008)] in 1,2-diazine–chloranilic acid (2/1) and the H atoms are located at the N atom sites. The dihedral angles between C1–C6 and C7–C12 rings, C1–C6 and N1/N2/C19–C22 rings, C7–C12 and N3/N4/C23–C26 rings, and C13–C18 and N5/N6/C27–C30 rings are 3.40 (5), 11.83 (5), 4.88 (6) and 11.41 (5)°, respectively. The 2:2 units are linked by intermolecular C—H···O and C—H···N hydrogen bonds, forming a molecular tape along the [230] direction. The tapes are further connected by C—H···O hydrogen bonds, forming a three-dimensional network (Table 1 and Fig. 2).

Related literature top

For general background, see: Gotoh et al. (2007). For related compounds, see: Gotoh et al. (2008); Ishida & Kashino (1999).

Experimental top

Single crystals were obtained by slow evaporation from a methanol solution (30 ml) of chloranilic acid (400 mg) and 1,2-diazine (155 mg).

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 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The structure of the 2:2 units of (I). The dashed lines indicate O—H···O, C—H···O and C—H···N hydrogen bonds (symmetry code as Table 1). Displacement ellipsoids of non-H atoms are drawn at the 50% probability level.
	Fig. 2. A partial packing diagram of (I), viewed down the b axis. The dashed lines indicate O—H···O, C—H···O and C—H···N hydrogen bonds.

1,2-Diazinium hydrogen chloranilate top

Crystal data top

C₄H₅N₂⁺·C₆HCl₂O₄⁻	F(000) = 1752.00
M_r = 289.07	D_x = 1.769 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 36292 reflections
a = 25.6849 (10) Å	θ = 3.0–30.0°
b = 7.0516 (2) Å	µ = 0.61 mm⁻¹
c = 18.1388 (6) Å	T = 173 K
β = 97.5822 (13)°	Prism, brown
V = 3256.56 (18) Å³	0.40 × 0.22 × 0.12 mm
Z = 12

Data collection top

Rigaku R-AXIS RAPIDII diffractometer	7981 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.025
ω scans	θ_max = 30.0°
Absorption correction: numerical (ABSCOR; Higashi, 1999)	h = −36→36
T_min = 0.855, T_max = 0.930	k = −9→8
42942 measured reflections	l = −24→25
9398 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0465P)² + 0.8542P] where P = (F_o² + 2F_c²)/3
9398 reflections	(Δ/σ)_max = 0.002
511 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₄H₅N₂⁺·C₆HCl₂O₄⁻	V = 3256.56 (18) Å³
M_r = 289.07	Z = 12
Monoclinic, P2₁/c	Mo Kα radiation
a = 25.6849 (10) Å	µ = 0.61 mm⁻¹
b = 7.0516 (2) Å	T = 173 K
c = 18.1388 (6) Å	0.40 × 0.22 × 0.12 mm
β = 97.5822 (13)°

Data collection top

Rigaku R-AXIS RAPIDII diffractometer	9398 independent reflections
Absorption correction: numerical (ABSCOR; Higashi, 1999)	7981 reflections with I > 2σ(I)
T_min = 0.855, T_max = 0.930	R_int = 0.025
42942 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.47 e Å⁻³
9398 reflections	Δρ_min = −0.26 e Å⁻³
511 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	0.788813 (11)	1.00777 (4)	0.695195 (15)	0.02287 (7)
Cl2	0.813873 (11)	1.33053 (4)	0.375637 (15)	0.01939 (6)
Cl3	0.546309 (11)	0.98926 (4)	0.291828 (15)	0.02164 (7)
Cl4	0.529070 (10)	0.68298 (4)	0.616552 (15)	0.01938 (6)
Cl5	0.134170 (11)	0.31600 (4)	0.406398 (15)	0.02014 (6)
Cl6	0.126530 (11)	0.00278 (4)	0.732528 (15)	0.02182 (7)
O1	0.70886 (3)	1.03911 (14)	0.56092 (5)	0.02672 (19)
O2	0.88525 (3)	1.17619 (12)	0.64597 (5)	0.02155 (17)
O3	0.89647 (3)	1.29114 (12)	0.50763 (5)	0.02036 (16)
O4	0.71996 (3)	1.15850 (13)	0.42465 (5)	0.02316 (18)
O5	0.62655 (3)	0.99280 (14)	0.42628 (5)	0.0258 (2)
O6	0.45198 (3)	0.80783 (12)	0.34672 (5)	0.02140 (17)
O7	0.44599 (3)	0.69004 (12)	0.48544 (5)	0.02138 (17)
O8	0.61970 (3)	0.86803 (14)	0.56295 (5)	0.02294 (18)
O9	0.04325 (3)	0.14786 (13)	0.47288 (5)	0.02485 (19)
O10	0.22343 (3)	0.29297 (12)	0.53149 (5)	0.02021 (17)
O11	0.21688 (3)	0.17839 (12)	0.67058 (5)	0.02290 (18)
O12	0.04124 (3)	0.00464 (13)	0.60811 (5)	0.02206 (18)
N1	0.97488 (4)	1.35579 (15)	0.65484 (6)	0.0219 (2)
N2	0.99547 (4)	1.31774 (15)	0.72462 (6)	0.0247 (2)
N3	0.36001 (4)	0.64298 (15)	0.35724 (6)	0.0212 (2)
N4	0.33565 (4)	0.66986 (16)	0.28834 (6)	0.0265 (2)
N5	0.31069 (4)	0.37842 (15)	0.63023 (6)	0.02006 (19)
N6	0.34283 (4)	0.45730 (16)	0.58711 (6)	0.0239 (2)
C1	0.75362 (4)	1.09400 (16)	0.55266 (6)	0.0170 (2)
C2	0.79706 (4)	1.09715 (16)	0.60871 (6)	0.01556 (19)
C3	0.84590 (4)	1.16825 (15)	0.59736 (6)	0.0152 (2)
C4	0.85282 (4)	1.24116 (15)	0.51915 (6)	0.01446 (19)
C5	0.80717 (4)	1.24251 (15)	0.46242 (6)	0.01550 (19)
C6	0.76101 (4)	1.16835 (15)	0.47678 (6)	0.0164 (2)
C7	0.58355 (4)	0.92184 (16)	0.43505 (6)	0.0165 (2)
C8	0.54005 (4)	0.90299 (16)	0.37928 (6)	0.0157 (2)
C9	0.49245 (4)	0.82418 (15)	0.39314 (6)	0.0155 (2)
C10	0.48814 (4)	0.75267 (15)	0.47232 (6)	0.01508 (19)
C11	0.53375 (4)	0.76601 (15)	0.52856 (6)	0.01517 (19)
C12	0.57836 (4)	0.84830 (16)	0.51193 (6)	0.0162 (2)
C13	0.08582 (4)	0.15642 (15)	0.51475 (6)	0.0164 (2)
C14	0.13318 (4)	0.23100 (15)	0.49570 (6)	0.01558 (19)
C15	0.17974 (4)	0.23689 (15)	0.54582 (6)	0.01537 (19)
C16	0.17708 (4)	0.16726 (15)	0.62576 (6)	0.0154 (2)
C17	0.12835 (4)	0.08899 (16)	0.64439 (6)	0.0159 (2)
C18	0.08570 (4)	0.07922 (15)	0.59219 (6)	0.0156 (2)
C19	1.04186 (5)	1.39362 (18)	0.74659 (7)	0.0234 (2)
H19	1.0576	1.3710	0.7962	0.028*
C20	1.06920 (5)	1.50533 (17)	0.70098 (7)	0.0232 (2)
H20	1.1027	1.5564	0.7190	0.028*
C21	1.04646 (5)	1.53937 (18)	0.62952 (7)	0.0231 (2)
H21	1.0637	1.6133	0.5962	0.028*
C22	0.99713 (5)	1.46098 (17)	0.60787 (7)	0.0228 (2)
H22	0.9795	1.4834	0.5592	0.027*
C23	0.28768 (5)	0.59892 (19)	0.27484 (7)	0.0279 (3)
H23	0.2688	0.6165	0.2266	0.034*
C24	0.26300 (5)	0.49954 (18)	0.32732 (8)	0.0250 (3)
H24	0.2286	0.4497	0.3148	0.030*
C25	0.28964 (5)	0.47601 (18)	0.39706 (7)	0.0252 (2)
H25	0.2746	0.4101	0.4347	0.030*
C26	0.33997 (5)	0.55323 (18)	0.41044 (7)	0.0247 (2)
H26	0.3599	0.5409	0.4582	0.030*
C27	0.38814 (5)	0.51986 (19)	0.62180 (7)	0.0252 (3)
H27	0.4118	0.5787	0.5928	0.030*
C28	0.40324 (5)	0.50458 (18)	0.69840 (7)	0.0242 (2)
H28	0.4363	0.5508	0.7209	0.029*
C29	0.36891 (5)	0.42094 (18)	0.74013 (7)	0.0242 (2)
H29	0.3774	0.4059	0.7924	0.029*
C30	0.32121 (5)	0.35891 (18)	0.70316 (7)	0.0238 (2)
H30	0.2961	0.3023	0.7303	0.029*
H1	0.9443 (7)	1.298 (2)	0.6418 (10)	0.040 (5)*
H4	0.6953 (9)	1.112 (3)	0.4388 (13)	0.070 (7)*
H8	0.6436 (8)	0.921 (3)	0.5477 (12)	0.064 (7)*
H3	0.3919 (7)	0.693 (2)	0.3649 (10)	0.037 (5)*
H5	0.2801 (7)	0.340 (2)	0.6060 (10)	0.040 (5)*
H12	0.0205 (8)	−0.001 (3)	0.5722 (11)	0.052 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02091 (13)	0.03338 (16)	0.01460 (12)	−0.00592 (10)	0.00337 (9)	0.00278 (11)
Cl2	0.02201 (13)	0.02140 (13)	0.01473 (12)	−0.00058 (9)	0.00235 (9)	0.00273 (10)
Cl3	0.02047 (13)	0.03130 (15)	0.01329 (12)	−0.00316 (10)	0.00276 (9)	0.00268 (10)
Cl4	0.02048 (13)	0.02307 (13)	0.01446 (12)	−0.00125 (9)	0.00187 (9)	0.00367 (10)
Cl5	0.02339 (13)	0.02148 (13)	0.01490 (12)	−0.00022 (10)	0.00008 (9)	0.00332 (10)
Cl6	0.01993 (13)	0.03180 (15)	0.01370 (12)	−0.00260 (10)	0.00209 (9)	0.00197 (10)
O1	0.0137 (4)	0.0443 (5)	0.0221 (4)	−0.0085 (3)	0.0020 (3)	0.0002 (4)
O2	0.0153 (4)	0.0311 (4)	0.0170 (4)	−0.0058 (3)	−0.0026 (3)	0.0029 (3)
O3	0.0155 (4)	0.0264 (4)	0.0195 (4)	−0.0057 (3)	0.0034 (3)	−0.0006 (3)
O4	0.0137 (4)	0.0360 (5)	0.0185 (4)	−0.0030 (3)	−0.0026 (3)	0.0037 (4)
O5	0.0148 (4)	0.0416 (5)	0.0206 (4)	−0.0087 (3)	0.0009 (3)	0.0036 (4)
O6	0.0156 (4)	0.0296 (4)	0.0177 (4)	−0.0056 (3)	−0.0028 (3)	0.0023 (3)
O7	0.0163 (4)	0.0282 (4)	0.0195 (4)	−0.0075 (3)	0.0020 (3)	0.0000 (3)
O8	0.0135 (4)	0.0372 (5)	0.0169 (4)	−0.0064 (3)	−0.0024 (3)	0.0047 (4)
O9	0.0161 (4)	0.0313 (5)	0.0248 (4)	−0.0035 (3)	−0.0062 (3)	0.0067 (4)
O10	0.0159 (4)	0.0265 (4)	0.0179 (4)	−0.0047 (3)	0.0014 (3)	0.0001 (3)
O11	0.0167 (4)	0.0305 (4)	0.0198 (4)	−0.0041 (3)	−0.0036 (3)	0.0035 (3)
O12	0.0138 (4)	0.0323 (5)	0.0196 (4)	−0.0045 (3)	0.0003 (3)	0.0014 (3)
N1	0.0144 (4)	0.0246 (5)	0.0262 (5)	−0.0023 (4)	0.0010 (4)	−0.0009 (4)
N2	0.0249 (5)	0.0260 (5)	0.0233 (5)	−0.0044 (4)	0.0041 (4)	0.0014 (4)
N3	0.0153 (4)	0.0247 (5)	0.0225 (5)	−0.0032 (4)	−0.0015 (4)	−0.0013 (4)
N4	0.0262 (5)	0.0306 (6)	0.0216 (5)	−0.0059 (4)	−0.0017 (4)	0.0021 (4)
N5	0.0151 (4)	0.0238 (5)	0.0207 (5)	−0.0023 (4)	0.0001 (3)	−0.0016 (4)
N6	0.0214 (5)	0.0310 (5)	0.0189 (5)	−0.0043 (4)	0.0017 (4)	−0.0003 (4)
C1	0.0141 (5)	0.0205 (5)	0.0164 (5)	−0.0015 (4)	0.0018 (4)	−0.0019 (4)
C2	0.0143 (5)	0.0204 (5)	0.0120 (4)	−0.0022 (4)	0.0019 (3)	0.0002 (4)
C3	0.0134 (4)	0.0169 (5)	0.0152 (5)	−0.0013 (4)	0.0012 (4)	−0.0013 (4)
C4	0.0145 (4)	0.0143 (5)	0.0144 (5)	−0.0014 (4)	0.0016 (4)	−0.0022 (4)
C5	0.0159 (5)	0.0170 (5)	0.0133 (4)	0.0005 (4)	0.0009 (4)	0.0004 (4)
C6	0.0142 (5)	0.0188 (5)	0.0155 (5)	0.0014 (4)	−0.0004 (4)	−0.0012 (4)
C7	0.0138 (5)	0.0206 (5)	0.0152 (5)	−0.0011 (4)	0.0014 (4)	0.0002 (4)
C8	0.0152 (5)	0.0195 (5)	0.0123 (4)	−0.0006 (4)	0.0012 (4)	0.0002 (4)
C9	0.0146 (5)	0.0170 (5)	0.0145 (5)	−0.0009 (4)	0.0008 (4)	0.0000 (4)
C10	0.0144 (4)	0.0154 (5)	0.0153 (5)	−0.0014 (4)	0.0013 (4)	−0.0013 (4)
C11	0.0157 (5)	0.0170 (5)	0.0127 (4)	−0.0005 (4)	0.0013 (4)	0.0014 (4)
C12	0.0134 (5)	0.0193 (5)	0.0153 (5)	0.0004 (4)	−0.0006 (4)	−0.0002 (4)
C13	0.0157 (5)	0.0155 (5)	0.0172 (5)	0.0015 (4)	−0.0007 (4)	0.0010 (4)
C14	0.0162 (5)	0.0167 (5)	0.0133 (4)	0.0001 (4)	−0.0001 (4)	0.0014 (4)
C15	0.0156 (5)	0.0143 (5)	0.0158 (5)	−0.0006 (4)	0.0005 (4)	−0.0017 (4)
C16	0.0142 (5)	0.0158 (5)	0.0156 (5)	0.0001 (4)	0.0001 (4)	−0.0010 (4)
C17	0.0151 (5)	0.0186 (5)	0.0140 (5)	0.0001 (4)	0.0016 (4)	−0.0004 (4)
C18	0.0130 (4)	0.0170 (5)	0.0169 (5)	0.0006 (4)	0.0022 (4)	−0.0014 (4)
C19	0.0229 (6)	0.0258 (6)	0.0204 (5)	−0.0011 (4)	−0.0012 (4)	−0.0004 (5)
C20	0.0164 (5)	0.0262 (6)	0.0265 (6)	−0.0046 (4)	0.0017 (4)	−0.0065 (5)
C21	0.0228 (6)	0.0233 (6)	0.0241 (6)	−0.0060 (4)	0.0065 (4)	−0.0004 (5)
C22	0.0205 (5)	0.0246 (6)	0.0224 (6)	0.0013 (4)	−0.0006 (4)	0.0009 (5)
C23	0.0265 (6)	0.0303 (6)	0.0241 (6)	−0.0045 (5)	−0.0075 (5)	0.0015 (5)
C24	0.0164 (5)	0.0265 (6)	0.0309 (6)	−0.0037 (4)	−0.0019 (4)	−0.0038 (5)
C25	0.0213 (6)	0.0293 (6)	0.0252 (6)	−0.0060 (5)	0.0034 (4)	0.0002 (5)
C26	0.0209 (6)	0.0312 (6)	0.0205 (5)	−0.0034 (5)	−0.0034 (4)	0.0011 (5)
C27	0.0204 (6)	0.0325 (6)	0.0231 (6)	−0.0072 (5)	0.0038 (4)	−0.0011 (5)
C28	0.0176 (5)	0.0300 (6)	0.0238 (6)	−0.0038 (4)	−0.0016 (4)	−0.0052 (5)
C29	0.0240 (6)	0.0303 (6)	0.0172 (5)	−0.0025 (5)	−0.0015 (4)	−0.0008 (5)
C30	0.0212 (5)	0.0284 (6)	0.0217 (6)	−0.0041 (4)	0.0030 (4)	0.0003 (5)

Geometric parameters (Å, º) top

Cl1—C2	1.7293 (11)	C3—C4	1.5412 (15)
Cl2—C5	1.7218 (11)	C4—C5	1.4545 (14)
Cl3—C8	1.7262 (11)	C5—C6	1.3522 (15)
Cl4—C11	1.7192 (11)	C7—C8	1.4110 (14)
Cl5—C14	1.7305 (11)	C7—C12	1.5102 (15)
Cl6—C17	1.7168 (11)	C8—C9	1.3958 (15)
O1—C1	1.2408 (13)	C9—C10	1.5398 (15)
O2—C3	1.2517 (13)	C10—C11	1.4515 (14)
O3—C4	1.2193 (13)	C11—C12	1.3533 (15)
O4—C6	1.3218 (13)	C13—C14	1.4096 (15)
O4—H4	0.78 (2)	C13—C18	1.5069 (15)
O5—C7	1.2417 (13)	C14—C15	1.4040 (14)
O6—C9	1.2536 (13)	C15—C16	1.5408 (15)
O7—C10	1.2213 (13)	C16—C17	1.4481 (15)
O8—C12	1.3207 (12)	C17—C18	1.3520 (14)
O8—H8	0.80 (2)	C19—C20	1.3969 (17)
O9—C13	1.2476 (13)	C19—H19	0.9500
O10—C15	1.2491 (13)	C20—C21	1.3708 (17)
O11—C16	1.2218 (13)	C20—H20	0.9500
O12—C18	1.3232 (13)	C21—C22	1.3906 (16)
O12—H12	0.79 (2)	C21—H21	0.9500
N1—C22	1.3158 (16)	C22—H22	0.9500
N1—N2	1.3331 (15)	C23—C24	1.3994 (19)
N1—H1	0.888 (18)	C23—H23	0.9500
N2—C19	1.3189 (15)	C24—C25	1.3666 (18)
N3—C26	1.3144 (16)	C24—H24	0.9500
N3—N4	1.3355 (14)	C25—C26	1.3942 (16)
N3—H3	0.886 (17)	C25—H25	0.9500
N4—C23	1.3223 (16)	C26—H26	0.9500
N5—C30	1.3221 (16)	C27—C28	1.3966 (18)
N5—N6	1.3314 (14)	C27—H27	0.9500
N5—H5	0.891 (18)	C28—C29	1.3690 (17)
N6—C27	1.3236 (15)	C28—H28	0.9500
C1—C2	1.4069 (14)	C29—C30	1.3875 (16)
C1—C6	1.5079 (15)	C29—H29	0.9500
C2—C3	1.3913 (14)	C30—H30	0.9500

C6—O4—H4	113.0 (17)	C14—C13—C18	118.12 (9)
C12—O8—H8	112.9 (16)	C15—C14—C13	122.76 (10)
C18—O12—H12	110.5 (15)	C15—C14—Cl5	118.65 (8)
C22—N1—N2	125.20 (10)	C13—C14—Cl5	118.58 (8)
C22—N1—H1	122.0 (12)	O10—C15—C14	125.90 (10)
N2—N1—H1	112.8 (12)	O10—C15—C16	116.70 (9)
C19—N2—N1	115.76 (10)	C14—C15—C16	117.40 (9)
C26—N3—N4	125.10 (10)	O11—C16—C17	122.83 (10)
C26—N3—H3	121.5 (11)	O11—C16—C15	117.95 (10)
N4—N3—H3	113.4 (11)	C17—C16—C15	119.21 (9)
C23—N4—N3	115.44 (11)	C18—C17—C16	120.10 (10)
C30—N5—N6	124.80 (10)	C18—C17—Cl6	120.99 (8)
C30—N5—H5	120.8 (12)	C16—C17—Cl6	118.88 (8)
N6—N5—H5	114.4 (12)	O12—C18—C17	120.69 (10)
C27—N6—N5	115.74 (10)	O12—C18—C13	117.06 (9)
O1—C1—C2	125.21 (10)	C17—C18—C13	122.23 (10)
O1—C1—C6	116.67 (10)	N2—C19—C20	123.68 (11)
C2—C1—C6	118.09 (9)	N2—C19—H19	118.2
C3—C2—C1	122.90 (10)	C20—C19—H19	118.2
C3—C2—Cl1	119.09 (8)	C21—C20—C19	118.28 (11)
C1—C2—Cl1	118.00 (8)	C21—C20—H20	120.9
O2—C3—C2	124.89 (10)	C19—C20—H20	120.9
O2—C3—C4	116.93 (9)	C20—C21—C22	117.14 (11)
C2—C3—C4	118.17 (9)	C20—C21—H21	121.4
O3—C4—C5	123.41 (10)	C22—C21—H21	121.4
O3—C4—C3	118.33 (9)	N1—C22—C21	119.91 (11)
C5—C4—C3	118.24 (9)	N1—C22—H22	120.0
C6—C5—C4	120.45 (10)	C21—C22—H22	120.0
C6—C5—Cl2	120.77 (8)	N4—C23—C24	123.93 (12)
C4—C5—Cl2	118.72 (8)	N4—C23—H23	118.0
O4—C6—C5	121.29 (10)	C24—C23—H23	118.0
O4—C6—C1	116.75 (10)	C25—C24—C23	118.30 (11)
C5—C6—C1	121.96 (10)	C25—C24—H24	120.8
O5—C7—C8	125.43 (10)	C23—C24—H24	120.8
O5—C7—C12	116.43 (9)	C24—C25—C26	116.95 (12)
C8—C7—C12	118.14 (9)	C24—C25—H25	121.5
C9—C8—C7	122.55 (10)	C26—C25—H25	121.5
C9—C8—Cl3	119.72 (8)	N3—C26—C25	120.28 (11)
C7—C8—Cl3	117.69 (8)	N3—C26—H26	119.9
O6—C9—C8	125.73 (10)	C25—C26—H26	119.9
O6—C9—C10	116.17 (9)	N6—C27—C28	123.96 (12)
C8—C9—C10	118.09 (9)	N6—C27—H27	118.0
O7—C10—C11	122.72 (10)	C28—C27—H27	118.0
O7—C10—C9	118.35 (9)	C29—C28—C27	117.95 (11)
C11—C10—C9	118.92 (9)	C29—C28—H28	121.0
C12—C11—C10	119.98 (10)	C27—C28—H28	121.0
C12—C11—Cl4	121.19 (8)	C28—C29—C30	117.43 (11)
C10—C11—Cl4	118.79 (8)	C28—C29—H29	121.3
O8—C12—C11	121.01 (10)	C30—C29—H29	121.3
O8—C12—C7	116.74 (9)	N5—C30—C29	120.10 (11)
C11—C12—C7	122.25 (9)	N5—C30—H30	119.9
O9—C13—C14	125.75 (10)	C29—C30—H30	119.9
O9—C13—C18	116.14 (10)

C22—N1—N2—C19	−0.02 (18)	C10—C11—C12—C7	−2.38 (17)
C26—N3—N4—C23	0.15 (19)	Cl4—C11—C12—C7	179.80 (8)
C30—N5—N6—C27	−0.32 (18)	O5—C7—C12—O8	0.75 (15)
O1—C1—C2—C3	−176.99 (12)	C8—C7—C12—O8	−179.96 (10)
C6—C1—C2—C3	1.03 (16)	O5—C7—C12—C11	−179.30 (11)
O1—C1—C2—Cl1	3.15 (17)	C8—C7—C12—C11	−0.01 (16)
C6—C1—C2—Cl1	−178.82 (8)	O9—C13—C14—C15	179.75 (11)
C1—C2—C3—O2	178.89 (11)	C18—C13—C14—C15	−0.34 (16)
Cl1—C2—C3—O2	−1.25 (16)	O9—C13—C14—Cl5	−1.12 (16)
C1—C2—C3—C4	−1.82 (16)	C18—C13—C14—Cl5	178.79 (8)
Cl1—C2—C3—C4	178.04 (8)	C13—C14—C15—O10	176.55 (11)
O2—C3—C4—O3	4.40 (15)	Cl5—C14—C15—O10	−2.58 (16)
C2—C3—C4—O3	−174.94 (10)	C13—C14—C15—C16	−3.15 (16)
O2—C3—C4—C5	−177.03 (10)	Cl5—C14—C15—C16	177.72 (7)
C2—C3—C4—C5	3.63 (14)	O10—C15—C16—O11	2.96 (15)
O3—C4—C5—C6	173.62 (11)	C14—C15—C16—O11	−177.31 (10)
C3—C4—C5—C6	−4.87 (15)	O10—C15—C16—C17	−175.99 (10)
O3—C4—C5—Cl2	−3.52 (15)	C14—C15—C16—C17	3.74 (15)
C3—C4—C5—Cl2	177.99 (8)	O11—C16—C17—C18	−179.53 (11)
C4—C5—C6—O4	−176.09 (10)	C15—C16—C17—C18	−0.63 (15)
Cl2—C5—C6—O4	1.00 (15)	O11—C16—C17—Cl6	−1.56 (15)
C4—C5—C6—C1	4.23 (16)	C15—C16—C17—Cl6	177.34 (8)
Cl2—C5—C6—C1	−178.68 (8)	C16—C17—C18—O12	178.68 (10)
O1—C1—C6—O4	−3.73 (15)	Cl6—C17—C18—O12	0.75 (15)
C2—C1—C6—O4	178.08 (10)	C16—C17—C18—C13	−3.07 (16)
O1—C1—C6—C5	175.96 (11)	Cl6—C17—C18—C13	179.00 (8)
C2—C1—C6—C5	−2.23 (16)	O9—C13—C18—O12	1.95 (15)
O5—C7—C8—C9	−179.02 (11)	C14—C13—C18—O12	−177.98 (10)
C12—C7—C8—C9	1.75 (16)	O9—C13—C18—C17	−176.36 (11)
O5—C7—C8—Cl3	−1.27 (16)	C14—C13—C18—C17	3.71 (16)
C12—C7—C8—Cl3	179.50 (8)	N1—N2—C19—C20	−0.85 (18)
C7—C8—C9—O6	178.05 (11)	N2—C19—C20—C21	0.50 (19)
Cl3—C8—C9—O6	0.34 (16)	C19—C20—C21—C22	0.68 (18)
C7—C8—C9—C10	−1.04 (16)	N2—N1—C22—C21	1.20 (19)
Cl3—C8—C9—C10	−178.74 (8)	C20—C21—C22—N1	−1.48 (18)
O6—C9—C10—O7	−1.84 (15)	N3—N4—C23—C24	−0.8 (2)
C8—C9—C10—O7	177.33 (10)	N4—C23—C24—C25	0.9 (2)
O6—C9—C10—C11	179.47 (10)	C23—C24—C25—C26	−0.24 (19)
C8—C9—C10—C11	−1.36 (15)	N4—N3—C26—C25	0.4 (2)
O7—C10—C11—C12	−175.60 (11)	C24—C25—C26—N3	−0.35 (19)
C9—C10—C11—C12	3.03 (15)	N5—N6—C27—C28	0.92 (19)
O7—C10—C11—Cl4	2.27 (15)	N6—C27—C28—C29	−0.4 (2)
C9—C10—C11—Cl4	−179.10 (8)	C27—C28—C29—C30	−0.63 (19)
C10—C11—C12—O8	177.57 (10)	N6—N5—C30—C29	−0.7 (2)
Cl4—C11—C12—O8	−0.24 (16)	C28—C29—C30—N5	1.20 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.889 (17)	1.753 (17)	2.6138 (13)	162.2 (17)
N1—H1···O3	0.889 (17)	2.578 (18)	3.1583 (14)	123.7 (14)
N3—H3···O6	0.886 (18)	1.811 (17)	2.6621 (13)	160.4 (17)
N3—H3···O7	0.886 (18)	2.431 (18)	3.0066 (14)	123.0 (14)
O4—H4···O1	0.79 (2)	2.26 (2)	2.6619 (13)	113 (2)
O4—H4···O5	0.79 (2)	1.94 (2)	2.6723 (12)	155 (2)
N5—H5···O10	0.890 (18)	1.881 (18)	2.7450 (14)	163.2 (16)
N5—H5···O11	0.890 (18)	2.410 (17)	2.9659 (13)	120.7 (14)
O8—H8···O1	0.80 (2)	1.86 (2)	2.5930 (12)	152 (2)
O8—H8···O5	0.80 (2)	2.25 (2)	2.6582 (13)	112.7 (18)
O12—H12···O9	0.79 (2)	2.23 (2)	2.6595 (13)	115.1 (18)
O12—H12···O9ⁱ	0.79 (2)	2.02 (2)	2.6801 (12)	142 (2)
C20—H20···O2ⁱⁱ	0.95	2.57	3.1097 (15)	116
C21—H21···O3ⁱⁱⁱ	0.95	2.36	3.2754 (15)	162
C22—H22···O3	0.95	2.60	3.1913 (15)	121
C25—H25···O10	0.95	2.47	3.4056 (15)	169
C26—H26···O7	0.95	2.44	3.0363 (15)	121
C26—H26···N6	0.95	2.51	3.2665 (17)	137
C27—H27···O7	0.95	2.37	3.2765 (15)	159
C28—H28···O6^iv	0.95	2.47	3.1091 (15)	124
C30—H30···O11	0.95	2.34	2.9551 (15)	122

Symmetry codes: (i) −x, −y, −z+1; (ii) −x+2, y+1/2, −z+3/2; (iii) −x+2, −y+3, −z+1; (iv) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₄H₅N₂⁺·C₆HCl₂O₄⁻
M_r	289.07
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	25.6849 (10), 7.0516 (2), 18.1388 (6)
β (°)	97.5822 (13)
V (Å³)	3256.56 (18)
Z	12
Radiation type	Mo Kα
µ (mm⁻¹)	0.61
Crystal size (mm)	0.40 × 0.22 × 0.12

Data collection
Diffractometer	Rigaku R-AXIS RAPIDII diffractometer
Absorption correction	Numerical (ABSCOR; Higashi, 1999)
T_min, T_max	0.855, 0.930
No. of measured, independent and observed [I > 2σ(I)] reflections	42942, 9398, 7981
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.082, 1.04
No. of reflections	9398
No. of parameters	511
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.26

Computer programs: PROCESS-AUTO (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.889 (17)	1.753 (17)	2.6138 (13)	162.2 (17)
N1—H1···O3	0.889 (17)	2.578 (18)	3.1583 (14)	123.7 (14)
N3—H3···O6	0.886 (18)	1.811 (17)	2.6621 (13)	160.4 (17)
N3—H3···O7	0.886 (18)	2.431 (18)	3.0066 (14)	123.0 (14)
O4—H4···O1	0.79 (2)	2.26 (2)	2.6619 (13)	113 (2)
O4—H4···O5	0.79 (2)	1.94 (2)	2.6723 (12)	155 (2)
N5—H5···O10	0.890 (18)	1.881 (18)	2.7450 (14)	163.2 (16)
N5—H5···O11	0.890 (18)	2.410 (17)	2.9659 (13)	120.7 (14)
O8—H8···O1	0.80 (2)	1.86 (2)	2.5930 (12)	152 (2)
O8—H8···O5	0.80 (2)	2.25 (2)	2.6582 (13)	112.7 (18)
O12—H12···O9	0.79 (2)	2.23 (2)	2.6595 (13)	115.1 (18)
O12—H12···O9ⁱ	0.79 (2)	2.02 (2)	2.6801 (12)	142 (2)
C20—H20···O2ⁱⁱ	0.95	2.57	3.1097 (15)	116
C21—H21···O3ⁱⁱⁱ	0.95	2.36	3.2754 (15)	162
C22—H22···O3	0.95	2.60	3.1913 (15)	121
C25—H25···O10	0.95	2.47	3.4056 (15)	169
C26—H26···O7	0.95	2.44	3.0363 (15)	121
C26—H26···N6	0.95	2.51	3.2665 (17)	137
C27—H27···O7	0.95	2.37	3.2765 (15)	159
C28—H28···O6^iv	0.95	2.47	3.1091 (15)	124
C30—H30···O11	0.95	2.34	2.9551 (15)	122

Symmetry codes: (i) −x, −y, −z+1; (ii) −x+2, y+1/2, −z+3/2; (iii) −x+2, −y+3, −z+1; (iv) x, −y+3/2, z+1/2.

Acknowledgements

This work was supported by a Grant-in-Aid for Scientific Research (C) (No. 19550018) from the Japan Society for the Promotion of Science.

References

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gotoh, K., Asaji, T. & Ishida, H. (2007). Acta Cryst. C63, o17–o20. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gotoh, K., Asaji, T. & Ishida, H. (2008). Acta Cryst. C64, o550–o553. Web of Science CSD CrossRef IUCr Journals Google Scholar
Higashi, T. (1999). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Ishida, H. & Kashino, S. (1999). Acta Cryst. C55, 1149–1152. Web of Science CSD CrossRef CAS IUCr Journals 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. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar