2-Amino­pyridinium 2-meth­oxy­carbonyl-4,6-dinitro­phenolate

Wu, D.-L.; Xiao, Z.-J.

doi:10.1107/S160053681105286X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Pages o124-o125

doi:10.1107/S160053681105286X

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2-Aminopyridinium 2-methoxycarbonyl-4,6-dinitrophenolate

Dong-Liang Wu ^a and Zi-Jing Xiao ^a ^*

^aCollege of Materials Science & Engineering, Huaqiao University, Xiamen 361021, People's Republic of China
^*Correspondence e-mail: xzj@hqu.edu.cn

(Received 18 October 2011; accepted 8 December 2011; online 14 December 2011)

In the title molecular salt, C₅H₇N₂⁺·C₈H₅N₂O₇⁻, the 2-aminopyridinium cation is essentially planar, with a maximium deviation of 0.015 (1) Å, while the 2-methoxycarbonyl-4,6-dinitrophenolate anion is slightly twisted away from planarity, with a maximium deviation of 0.187 (1) Å. Deprotonation of the hydroxy O atom was observed. The cation and anion are connected by four bifurcated N—H⋯(O,O) hydrogen bonds, forming a molecular proton-transfer adduct. The dihedral angle between the pyridinium ring in the cation and the benzene ring in the anion is 3.65 (6)°. Every adduct connects to six neighboring adducts by N—H⋯O and C—H⋯O hydrogen bonds, yielding extended layers parallel to the bc plane. There is a weak π–π interaction between the benzene rings of two neighboring anions; the interplanar spacing and the centroid–centroid separation are 3.309 (1) and 3.69 (1) Å, respectively.

Related literature

For the structures of molecular proton-transfer adducts containing substituted pyridinium and an acid anion, see Gellert & Hsu (1988 ); Smith et al. (2000 ); Jebas et al. (2006 ); Rademeyer (2007 ); Hemamalini & Fun (2010a ,b ,c ); Perpétuo & Janczak (2010 ). For comparable structures, see: Jebas et al. (2006); Perpétuo & Janczak (2010); Hemamalini & Fun (2010a). For the synthesis of 3,5-dinitromethyl salicylate, see: Bartlett & Trachten (1958 ).

Experimental

Crystal data

C₅H₇N₂⁺·C₈H₅N₂O₇⁻
M_r = 336.27
Monoclinic, P 2₁ /n
a = 7.4088 (3) Å
b = 19.1779 (6) Å
c = 9.9784 (4) Å
β = 98.2825 (15)°
V = 1403.00 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.35 × 0.35 × 0.26 mm

Data collection

Rigaku R-AXIS SPIDER IP diffractometer
Absorption correction: ψ scan (TEXRAY; Molecular Structure Corporation, 1999) T_min = 0.951, T_max = 0.969
21789 measured reflections
3200 independent reflections
2760 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.111
S = 1.09
3200 reflections
221 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H01A⋯O3	0.90	1.88	2.6864 (13)	148
N1—H01A⋯O2	0.90	2.23	2.8783 (14)	130
N2—H02A⋯O3	0.88	2.01	2.7592 (14)	142
N2—H02A⋯O4	0.88	2.45	3.2082 (15)	144
N2—H02B⋯O6ⁱ	0.87	2.24	3.0537 (14)	155
C4—H4A⋯O7ⁱⁱ	0.93	2.57	3.2052 (16)	126
C5—H5A⋯O5ⁱⁱⁱ	0.93	2.42	3.2604 (17)	151
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) x, y, z+1.

Data collection: RAPID-AUTO (Rigaku, 2008 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEX (McArdle, 1995 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681105286X/ez2268sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681105286X/ez2268Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681105286X/ez2268Isup3.cml

checkCIF report

Comment top

The structures of many molecular proton transfer adducts containing substituted pyridinium and an acid anion have been reported in the past decades (Gellert & Hsu, 1988; Smith et al., 2000; Jebas et al., 2006; Rademeyer, 2007; Hemamalini & Fun, 2010a,b, c). As a substituted pyridinium, 2-aminopyridine has attracted great attention due to its various hydrogen bonds (Gellert & Hsu, 1988; Jebas et al., 2006; Perpétuo & Janczak, 2010; Hemamalini & Fun, 2010a). We report here the synthesis and crystal structure of 2-aminopyridinium 3,5-dinitromethyl salicylate (I).

In the title compound, proton transfer has occurred from the hydroxyl group. As illustrated in Figure 1, the title molecule consists of a protonated 2-aminopyridinium cation and a 3,5-dinitromethyl salicylate anion. The cation and the anion are linked via two N—H···O(hydroxy), one N—H···O(carboxy) and one N—H···O(nitro group) hydrogen bonds to form an ion pair. The dihedral angle between the pyridinium ring in the cation and the benzene ring in the anion is 3.65 (6)°.

The bond lengths and angles in (I) are similar to those in other 2-aminopyridinium complexes (Jebas et al., 2006; Perpétuo & Janczak, 2010; Hemamalini & Fun, 2010a).

As shown in Figure 2, the adduct at (x, y, z) connects to two neighboring adducts [at (0.5-x, 0.5+y, 0.5-z) and at (0.5-x, -0.5+y, 0.5-z)] through two N2-H···O6A (symmetry code A, 0.5-x, 0.5+y, 0.5-z) hydrogen bonds, forming a spiral chain. At the same time, the adduct at (x, y, z) interacts with two neighboring adducts via two C4-H···O7B (symmetry code B, 0.5-x, 0.5+y, 1.5-z) hydrogen bonds, also resulting in a spiral chain. A further C5-H···O5D (symmetry code D, x, y, 1+z) hydrogen bond connects the adduct to another two adducts. Therefore, every adduct connects to six neighboring adducts by these N-H···O and C_aryl-H···O hydrogen bonds to yield an extended undulating two-dimensional network (Figure 2).

The benzene ring of the anion at (x, y, z) and the benzene ring in the anion at (1-x, 1-y, 1-z) are almost parallel, with a dihedral angle of 0.00 (6)° between them. The interplanar spacing is about 3.309 (1) Å, the centroid-centroid separation is 3.69 (1) Å, indicating a weak π-π interaction between these rings (Figure 3).

Related literature top

For the structures of molecular proton-transfer adducts containing substituted pyridinium and an acid anion, see Gellert & Hsu (1988); Smith et al. (2000); Jebas et al. (2006); Rademeyer (2007); Hemamalini & Fun (2010a,b,c); Perpétuo & Janczak (2010). For comparable structures, see: Jebas et al. (2006); Perpétuo & Janczak (2010); Hemamalini & Fun (2010a). For the synthesis of 3,5-dinitromethyl salicylate, see: Bartlett & Trachten (1958).

Experimental top

Reagents and solvents were used as obtained without further purification. 3,5-dinitromethyl salicylate was synthesized according to literature methods (Bartlett & Trachten, 1958). Ni(OAc)₂^.4H₂O (0.0498g, 0.2 mmol) was dissolved in 10 mL of methanol to yield solution A. 3,5-dinitromethyl salicylate (0.0484 g, 0.2 mmol) and 2-aminopyridine (0.0188 g , 0.2 mmol) were dissolved in 10 mL of acetone to yield solution B. Solution A was slowly added to solution B. The mixture was stirred for 4 h at room temperature. After filtration, the green filtrate was allowed to stand at room temperature for several days. The yellow block crystals of the title compound (I) were obtained by slow evaporation.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2008); cell refinement: RAPID-AUTO (Rigaku, 2008); data reduction: RAPID-AUTO (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular components of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines
	Fig. 2. The extended 2D network of compound (I) formed by N-H···O and C-H···O hydrogen bonds

2-Aminopyridinium 2-methoxycarbonyl-4,6-dinitrophenolate top

Crystal data top

C₅H₇N₂⁺·C₈H₅N₂O₇⁻	F(000) = 696
M_r = 336.27	D_x = 1.592 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3200 reflections
a = 7.4088 (3) Å	θ = 3.2–27.5°
b = 19.1779 (6) Å	µ = 0.13 mm⁻¹
c = 9.9784 (4) Å	T = 293 K
β = 98.2825 (15)°	Block, pale yellow
V = 1403.00 (9) Å³	0.35 × 0.35 × 0.26 mm
Z = 4

Data collection top

Rigaku R-AXIS SPIDER IP diffractometer	3200 independent reflections
Radiation source: fine-focus sealed tube	2760 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scan	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: ψ scan (TEXRAY; Molecular Structure Corporation, 1999)	h = −9→9
T_min = 0.951, T_max = 0.969	k = −24→24
21789 measured reflections	l = −12→12

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0608P)² + 0.3452P] where P = (F_o² + 2F_c²)/3
3200 reflections	(Δ/σ)_max = 0.001
221 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₅H₇N₂⁺·C₈H₅N₂O₇⁻	V = 1403.00 (9) Å³
M_r = 336.27	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.4088 (3) Å	µ = 0.13 mm⁻¹
b = 19.1779 (6) Å	T = 293 K
c = 9.9784 (4) Å	0.35 × 0.35 × 0.26 mm
β = 98.2825 (15)°

Data collection top

Rigaku R-AXIS SPIDER IP diffractometer	3200 independent reflections
Absorption correction: ψ scan (TEXRAY; Molecular Structure Corporation, 1999)	2760 reflections with I > 2σ(I)
T_min = 0.951, T_max = 0.969	R_int = 0.024
21789 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.09	Δρ_max = 0.32 e Å⁻³
3200 reflections	Δρ_min = −0.30 e Å⁻³
221 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	−0.02842 (16)	0.69774 (6)	0.60013 (13)	0.0241 (3)
C2	−0.11062 (17)	0.75222 (6)	0.66522 (14)	0.0289 (3)
H2A	−0.1639	0.7897	0.6151	0.035*
C3	−0.11154 (18)	0.74967 (7)	0.80192 (14)	0.0311 (3)
H3A	−0.1657	0.7856	0.8445	0.037*
C4	−0.03148 (18)	0.69327 (7)	0.87924 (13)	0.0307 (3)
H4A	−0.0299	0.6919	0.9726	0.037*
C5	0.04326 (17)	0.64096 (7)	0.81366 (12)	0.0267 (3)
H5A	0.0952	0.6029	0.8625	0.032*
C6	0.29417 (15)	0.45835 (6)	0.52321 (11)	0.0210 (2)
C7	0.22285 (16)	0.51541 (6)	0.43454 (12)	0.0222 (2)
C8	0.25155 (16)	0.50645 (6)	0.29470 (12)	0.0228 (2)
C9	0.34193 (16)	0.45058 (6)	0.24919 (11)	0.0232 (2)
H9A	0.3571	0.4473	0.1585	0.028*
C10	0.41023 (15)	0.39918 (6)	0.34032 (12)	0.0215 (2)
C11	0.38567 (16)	0.40290 (6)	0.47609 (12)	0.0214 (2)
H11A	0.4314	0.3676	0.5355	0.026*
C12	0.27237 (16)	0.46104 (6)	0.66889 (12)	0.0237 (2)
C13	0.3255 (2)	0.40100 (9)	0.87787 (14)	0.0451 (4)
H13A	0.3399	0.3538	0.9098	0.068*
H13B	0.2093	0.4185	0.8942	0.068*
H13C	0.4209	0.4294	0.9250	0.068*
N1	0.04300 (14)	0.64367 (5)	0.67753 (10)	0.0233 (2)
H01A	0.0871	0.6072	0.6366	0.044 (5)*
N2	−0.01983 (16)	0.69663 (6)	0.46755 (11)	0.0301 (3)
H02A	0.0212	0.6592	0.4298	0.043 (5)*
H02B	−0.0560	0.7330	0.4189	0.043 (5)*
N3	0.18614 (16)	0.55870 (6)	0.19326 (11)	0.0312 (3)
N4	0.50832 (14)	0.34132 (5)	0.29295 (10)	0.0241 (2)
O1	0.33525 (16)	0.40289 (5)	0.73434 (9)	0.0380 (3)
O2	0.20907 (15)	0.50859 (5)	0.72572 (9)	0.0361 (2)
O3	0.14378 (14)	0.56716 (5)	0.47530 (9)	0.0347 (2)
O4	0.12739 (17)	0.61428 (5)	0.22518 (11)	0.0425 (3)
O5	0.1928 (3)	0.54493 (9)	0.07588 (12)	0.1015 (8)
O6	0.52421 (14)	0.33865 (5)	0.17125 (9)	0.0329 (2)
O7	0.57286 (14)	0.29666 (5)	0.37464 (10)	0.0342 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0235 (5)	0.0210 (5)	0.0277 (6)	−0.0042 (4)	0.0030 (5)	0.0003 (4)
C2	0.0288 (6)	0.0210 (6)	0.0366 (7)	0.0003 (5)	0.0031 (5)	−0.0011 (5)
C3	0.0305 (6)	0.0267 (6)	0.0367 (7)	−0.0006 (5)	0.0073 (5)	−0.0103 (5)
C4	0.0331 (7)	0.0338 (7)	0.0255 (6)	−0.0029 (5)	0.0057 (5)	−0.0063 (5)
C5	0.0288 (6)	0.0273 (6)	0.0237 (6)	−0.0016 (5)	0.0028 (5)	−0.0001 (5)
C6	0.0221 (5)	0.0229 (6)	0.0181 (5)	−0.0014 (4)	0.0027 (4)	−0.0004 (4)
C7	0.0239 (5)	0.0221 (5)	0.0206 (5)	0.0005 (4)	0.0029 (4)	−0.0010 (4)
C8	0.0257 (6)	0.0229 (6)	0.0194 (5)	−0.0001 (4)	0.0014 (4)	0.0028 (4)
C9	0.0258 (6)	0.0264 (6)	0.0175 (5)	−0.0016 (4)	0.0034 (4)	−0.0008 (4)
C10	0.0226 (5)	0.0203 (5)	0.0219 (6)	−0.0007 (4)	0.0046 (4)	−0.0027 (4)
C11	0.0225 (5)	0.0210 (5)	0.0206 (5)	−0.0017 (4)	0.0028 (4)	0.0012 (4)
C12	0.0248 (6)	0.0258 (6)	0.0206 (5)	0.0007 (4)	0.0034 (4)	0.0004 (4)
C13	0.0604 (10)	0.0566 (10)	0.0200 (7)	0.0201 (8)	0.0117 (6)	0.0107 (6)
N1	0.0261 (5)	0.0209 (5)	0.0233 (5)	0.0003 (4)	0.0053 (4)	−0.0014 (4)
N2	0.0410 (6)	0.0236 (5)	0.0261 (5)	0.0033 (4)	0.0062 (5)	0.0037 (4)
N3	0.0399 (6)	0.0313 (6)	0.0224 (5)	0.0076 (5)	0.0046 (5)	0.0052 (4)
N4	0.0256 (5)	0.0230 (5)	0.0244 (5)	−0.0013 (4)	0.0061 (4)	−0.0022 (4)
O1	0.0586 (7)	0.0379 (5)	0.0194 (4)	0.0191 (5)	0.0117 (4)	0.0066 (4)
O2	0.0546 (6)	0.0321 (5)	0.0237 (4)	0.0117 (4)	0.0125 (4)	−0.0005 (4)
O3	0.0507 (6)	0.0296 (5)	0.0246 (5)	0.0156 (4)	0.0084 (4)	0.0011 (4)
O4	0.0678 (7)	0.0245 (5)	0.0355 (5)	0.0100 (5)	0.0088 (5)	0.0069 (4)
O5	0.1943 (19)	0.0906 (11)	0.0208 (6)	0.0938 (13)	0.0190 (8)	0.0151 (6)
O6	0.0432 (5)	0.0334 (5)	0.0237 (4)	0.0050 (4)	0.0097 (4)	−0.0060 (4)
O7	0.0433 (5)	0.0269 (5)	0.0340 (5)	0.0102 (4)	0.0117 (4)	0.0055 (4)

Geometric parameters (Å, º) top

C1—N2	1.3338 (16)	C9—C10	1.3864 (16)
C1—N1	1.3543 (16)	C9—H9A	0.9300
C1—C2	1.4136 (17)	C10—C11	1.3945 (15)
C2—C3	1.3659 (19)	C10—N4	1.4429 (15)
C2—H2A	0.9300	C11—H11A	0.9300
C3—C4	1.409 (2)	C12—O2	1.2041 (15)
C3—H3A	0.9300	C12—O1	1.3414 (15)
C4—C5	1.3586 (18)	C13—O1	1.4448 (15)
C4—H4A	0.9300	C13—H13A	0.9600
C5—N1	1.3591 (15)	C13—H13B	0.9600
C5—H5A	0.9300	C13—H13C	0.9600
C6—C11	1.3796 (16)	N1—H01A	0.8952
C6—C7	1.4578 (16)	N2—H02A	0.8838
C6—C12	1.4864 (15)	N2—H02B	0.8702
C7—O3	1.2498 (14)	N3—O5	1.2087 (16)
C7—C8	1.4516 (16)	N3—O4	1.2112 (15)
C8—C9	1.3748 (17)	N4—O7	1.2307 (14)
C8—N3	1.4568 (15)	N4—O6	1.2378 (13)

N2—C1—N1	118.87 (11)	C9—C10—N4	119.04 (10)
N2—C1—C2	123.56 (11)	C11—C10—N4	119.99 (10)
N1—C1—C2	117.56 (11)	C6—C11—C10	120.65 (10)
C3—C2—C1	119.79 (12)	C6—C11—H11A	119.7
C3—C2—H2A	120.1	C10—C11—H11A	119.7
C1—C2—H2A	120.1	O2—C12—O1	122.13 (11)
C2—C3—C4	120.81 (12)	O2—C12—C6	126.26 (11)
C2—C3—H3A	119.6	O1—C12—C6	111.61 (10)
C4—C3—H3A	119.6	O1—C13—H13A	109.5
C5—C4—C3	118.15 (12)	O1—C13—H13B	109.5
C5—C4—H4A	120.9	H13A—C13—H13B	109.5
C3—C4—H4A	120.9	O1—C13—H13C	109.5
C4—C5—N1	120.74 (12)	H13A—C13—H13C	109.5
C4—C5—H5A	119.6	H13B—C13—H13C	109.5
N1—C5—H5A	119.6	C1—N1—C5	122.92 (10)
C11—C6—C7	121.65 (10)	C1—N1—H01A	118.4
C11—C6—C12	119.21 (10)	C5—N1—H01A	118.6
C7—C6—C12	119.11 (10)	C1—N2—H02A	120.2
O3—C7—C8	123.18 (11)	C1—N2—H02B	119.0
O3—C7—C6	122.99 (10)	H02A—N2—H02B	120.7
C8—C7—C6	113.83 (10)	O5—N3—O4	120.90 (12)
C9—C8—C7	123.75 (10)	O5—N3—C8	117.84 (11)
C9—C8—N3	115.83 (10)	O4—N3—C8	121.25 (11)
C7—C8—N3	120.41 (10)	O7—N4—O6	122.57 (10)
C8—C9—C10	119.11 (10)	O7—N4—C10	118.96 (10)
C8—C9—H9A	120.4	O6—N4—C10	118.47 (10)
C10—C9—H9A	120.4	C12—O1—C13	116.11 (10)
C9—C10—C11	120.97 (10)

N2—C1—C2—C3	−179.20 (12)	C9—C10—C11—C6	−0.67 (17)
N1—C1—C2—C3	1.62 (18)	N4—C10—C11—C6	179.18 (10)
C1—C2—C3—C4	−0.03 (19)	C11—C6—C12—O2	173.68 (12)
C2—C3—C4—C5	−1.28 (19)	C7—C6—C12—O2	−4.57 (18)
C3—C4—C5—N1	0.98 (19)	C11—C6—C12—O1	−5.50 (16)
C11—C6—C7—O3	−178.03 (11)	C7—C6—C12—O1	176.25 (10)
C12—C6—C7—O3	0.17 (18)	N2—C1—N1—C5	178.80 (11)
C11—C6—C7—C8	2.18 (16)	C2—C1—N1—C5	−1.97 (17)
C12—C6—C7—C8	−179.61 (10)	C4—C5—N1—C1	0.68 (18)
O3—C7—C8—C9	178.46 (12)	C9—C8—N3—O5	10.0 (2)
C6—C7—C8—C9	−1.76 (17)	C7—C8—N3—O5	−170.96 (17)
O3—C7—C8—N3	−0.49 (18)	C9—C8—N3—O4	−169.76 (12)
C6—C7—C8—N3	179.30 (10)	C7—C8—N3—O4	9.27 (19)
C7—C8—C9—C10	0.18 (18)	C9—C10—N4—O7	178.17 (11)
N3—C8—C9—C10	179.17 (10)	C11—C10—N4—O7	−1.68 (16)
C8—C9—C10—C11	1.12 (17)	C9—C10—N4—O6	−1.80 (16)
C8—C9—C10—N4	−178.74 (10)	C11—C10—N4—O6	178.35 (10)
C7—C6—C11—C10	−1.09 (17)	O2—C12—O1—C13	−1.0 (2)
C12—C6—C11—C10	−179.29 (10)	C6—C12—O1—C13	178.21 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H01A···O3	0.90	1.88	2.6864 (13)	148
N1—H01A···O2	0.90	2.23	2.8783 (14)	130
N2—H02A···O3	0.88	2.01	2.7592 (14)	142
N2—H02A···O4	0.88	2.45	3.2082 (15)	144
N2—H02B···O6ⁱ	0.87	2.24	3.0537 (14)	155
C4—H4A···O7ⁱⁱ	0.93	2.57	3.2052 (16)	126
C5—H5A···O5ⁱⁱⁱ	0.93	2.42	3.2604 (17)	151

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

Experimental details

Crystal data
Chemical formula	C₅H₇N₂⁺·C₈H₅N₂O₇⁻
M_r	336.27
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.4088 (3), 19.1779 (6), 9.9784 (4)
β (°)	98.2825 (15)
V (Å³)	1403.00 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.35 × 0.35 × 0.26

Data collection
Diffractometer	Rigaku R-AXIS SPIDER IP diffractometer
Absorption correction	ψ scan (TEXRAY; Molecular Structure Corporation, 1999)
T_min, T_max	0.951, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	21789, 3200, 2760
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.111, 1.09
No. of reflections	3200
No. of parameters	221
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.30

Computer programs: RAPID-AUTO (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEX (McArdle, 1995).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H01A···O3	0.90	1.88	2.6864 (13)	148.1
N1—H01A···O2	0.90	2.23	2.8783 (14)	129.5
N2—H02A···O3	0.88	2.01	2.7592 (14)	142.1
N2—H02A···O4	0.88	2.45	3.2082 (15)	144.3
N2—H02B···O6ⁱ	0.87	2.24	3.0537 (14)	155.1
C4—H4A···O7ⁱⁱ	0.93	2.57	3.2052 (16)	125.9
C5—H5A···O5ⁱⁱⁱ	0.93	2.42	3.2604 (17)	150.5

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

Acknowledgements

This project was supported financially by the Natural Science Foundation of China (No. 50971063) and the Natural Science Foundation of Fujian Province (Nos. E0640006, 2003F006, 2010J01042).

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