2-Amino-pyridinium 2-meth-oxy-carbonyl-4,6-dinitro-phenolate.

In the title mol-ecular salt, C(5)H(7)N(2) (+)·C(8)H(5)N(2)O(7) (-), the 2-amino-pyridinium cation is essentially planar, with a maximium deviation of 0.015 (1) Å, while the 2-meth-oxy-carbonyl-4,6-dinitro-phenolate anion is slightly twisted away from planarity, with a maximium deviation of 0.187 (1) Å. Deprotonation of the hy-droxy O atom was observed. The cation and anion are connected by four bifurcated N-H⋯(O,O) hydrogen bonds, forming a mol-ecular 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 inter-action between the benzene rings of two neighboring anions; the inter-planar 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 = 336.27

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.111

S = 1.09

3200 reflections

221 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.30 e Å−3

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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681105286X/ez2268sup1.cif

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

Supplementary material file. DOI: 10.1107/S160053681105286X/ez2268Isup3.cml

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

C5H7N2+·C8H5N2O7−	F(000) = 696
Mr = 336.27	Dx = 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

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

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(Fo2) + (0.0608P)2 + 0.3452P] where P = (Fo2 + 2Fc2)/3
3200 reflections	(Δ/σ)max = 0.001
221 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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.

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) ; (ii) ; (iii) .