4-Amino-pyridinium picrate.

In the title compound, C(5)H(7)N(2) (+)·C(6)H(2)N(3)O(7) (-), the 4-amino-pyridinium cation is essentially planar (r.m.s. deviation = 0.002 Å). The three nitro groups in the picrate anion are twisted away from the attached benzene ring [dihedral angles = 24.1 (1), 9.3 (3) and 21.4 (1)°]. In the crystal structure, the ions are linked into a three-dimensional network by N-H⋯O and C-H⋯O hydrogen bonds.

Related literature

For general background to picrate complexes, see: In et al. (1997 ▶); Zaderenko et al. (1997 ▶); Ashwell et al. (1995 ▶); Owen & White (1976 ▶); Shakir et al. (2009 ▶).

Experimental

Crystal data

C5H7N2 +·C6H2N3O7 −

M = 323.23

Monoclinic,

a = 8.5056 (7) Å

b = 11.3338 (9) Å

c = 14.3307 (11) Å

β = 104.162 (5)°

V = 1339.50 (18) Å3

Z = 4

Mo Kα radiation

μ = 0.14 mm−1

T = 293 K

0.22 × 0.19 × 0.16 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.970, T max = 0.978

12562 measured reflections

3311 independent reflections

2637 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.108

S = 1.05

3311 reflections

221 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.18 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; 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: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810011050/ci5057sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810011050/ci5057Isup2.hkl

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

C5H7N2+·C6H2N3O7−	F(000) = 664
Mr = 323.23	Dx = 1.603 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1853 reflections
a = 8.5056 (7) Å	θ = 2.3–28.4°
b = 11.3338 (9) Å	µ = 0.14 mm−1
c = 14.3307 (11) Å	T = 293 K
β = 104.162 (5)°	Block, colourless
V = 1339.50 (18) Å3	0.22 × 0.19 × 0.16 mm
Z = 4

Bruker SMART APEXII area-detector diffractometer	3311 independent reflections
Radiation source: fine-focus sealed tube	2637 reflections with I > 2σ(I)
graphite	Rint = 0.026
ω and φ scans	θmax = 28.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→11
Tmin = 0.970, Tmax = 0.978	k = −15→14
12562 measured reflections	l = −18→19

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.108	w = 1/[σ2(Fo2) + (0.0464P)2 + 0.3813P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
3311 reflections	Δρmax = 0.24 e Å−3
221 parameters	Δρmin = −0.17 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.022 (2)

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 > 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
O1	0.87969 (13)	0.03133 (9)	0.06515 (7)	0.0445 (3)
O2	0.97300 (19)	0.02415 (13)	0.25752 (9)	0.0734 (4)
O3	1.20628 (16)	0.09976 (12)	0.31608 (8)	0.0632 (4)
O4	1.35225 (16)	0.45326 (12)	0.18781 (9)	0.0664 (4)
O5	1.23283 (19)	0.50978 (11)	0.04473 (10)	0.0700 (4)
O6	0.92217 (17)	0.22433 (12)	−0.16703 (7)	0.0654 (4)
O7	0.76429 (15)	0.11110 (13)	−0.11519 (8)	0.0686 (4)
N1	0.37289 (15)	0.09339 (12)	0.03722 (9)	0.0441 (3)
H1	0.293 (2)	0.0390 (18)	0.0159 (15)	0.068 (6)*
C2	0.46638 (18)	0.09158 (14)	0.12753 (11)	0.0463 (4)
H2	0.4515	0.0322	0.1694	0.056*
C3	0.58135 (18)	0.17420 (14)	0.15875 (11)	0.0458 (4)
H3	0.6451	0.1710	0.2215	0.055*
C4	0.60534 (17)	0.26532 (13)	0.09690 (10)	0.0396 (3)
C5	0.50530 (19)	0.26449 (15)	0.00273 (11)	0.0481 (4)
H5	0.5164	0.3226	−0.0410	0.058*
C6	0.39262 (19)	0.17818 (15)	−0.02361 (11)	0.0496 (4)
H6	0.3271	0.1781	−0.0859	0.060*
N7	0.71790 (19)	0.34716 (14)	0.12736 (12)	0.0543 (4)
H7A	0.774 (3)	0.347 (2)	0.1874 (18)	0.083 (7)*
H7B	0.721 (3)	0.404 (2)	0.0858 (16)	0.072 (6)*
C8	0.96034 (15)	0.12354 (11)	0.07454 (9)	0.0325 (3)
C9	1.06752 (16)	0.16121 (11)	0.16521 (9)	0.0338 (3)
C10	1.15984 (17)	0.26074 (12)	0.17653 (9)	0.0364 (3)
H10	1.2267	0.2793	0.2364	0.044*
C11	1.15372 (17)	0.33411 (11)	0.09862 (9)	0.0356 (3)
C12	1.05870 (16)	0.30622 (11)	0.00840 (9)	0.0346 (3)
H12	1.0567	0.3554	−0.0438	0.041*
C13	0.96746 (15)	0.20496 (11)	−0.00293 (8)	0.0327 (3)
N14	1.08227 (17)	0.08920 (11)	0.25121 (8)	0.0442 (3)
N15	1.25248 (16)	0.43901 (11)	0.11136 (9)	0.0455 (3)
N16	0.87848 (15)	0.17853 (11)	−0.10042 (8)	0.0400 (3)

	U11	U22	U33	U12	U13	U23
O1	0.0511 (6)	0.0403 (6)	0.0398 (5)	−0.0122 (5)	0.0065 (4)	0.0028 (4)
O2	0.1011 (11)	0.0720 (9)	0.0468 (7)	−0.0287 (8)	0.0177 (7)	0.0152 (6)
O3	0.0769 (8)	0.0652 (8)	0.0380 (6)	0.0098 (6)	−0.0041 (6)	0.0119 (5)
O4	0.0691 (8)	0.0613 (8)	0.0600 (7)	−0.0231 (6)	−0.0010 (6)	−0.0163 (6)
O5	0.1005 (11)	0.0484 (7)	0.0610 (8)	−0.0287 (7)	0.0195 (7)	0.0038 (6)
O6	0.0881 (9)	0.0751 (8)	0.0285 (5)	−0.0328 (7)	0.0058 (5)	0.0052 (5)
O7	0.0656 (8)	0.0859 (9)	0.0437 (6)	−0.0384 (7)	−0.0070 (5)	0.0073 (6)
N1	0.0392 (6)	0.0432 (7)	0.0462 (7)	−0.0040 (6)	0.0036 (5)	−0.0038 (5)
C2	0.0447 (8)	0.0427 (8)	0.0476 (8)	−0.0033 (7)	0.0037 (6)	0.0092 (6)
C3	0.0437 (8)	0.0485 (9)	0.0393 (7)	−0.0047 (7)	−0.0010 (6)	0.0064 (6)
C4	0.0370 (7)	0.0388 (7)	0.0434 (7)	0.0002 (6)	0.0103 (6)	−0.0004 (6)
C5	0.0498 (8)	0.0520 (9)	0.0413 (8)	−0.0002 (7)	0.0090 (6)	0.0107 (7)
C6	0.0475 (8)	0.0611 (10)	0.0363 (7)	0.0000 (7)	0.0025 (6)	0.0014 (7)
N7	0.0582 (9)	0.0496 (8)	0.0526 (8)	−0.0150 (7)	0.0087 (7)	0.0019 (7)
C8	0.0353 (6)	0.0326 (6)	0.0303 (6)	0.0013 (5)	0.0090 (5)	−0.0008 (5)
C9	0.0420 (7)	0.0331 (6)	0.0267 (6)	0.0048 (5)	0.0094 (5)	0.0013 (5)
C10	0.0440 (7)	0.0366 (7)	0.0266 (6)	0.0026 (6)	0.0046 (5)	−0.0065 (5)
C11	0.0424 (7)	0.0304 (6)	0.0344 (6)	−0.0039 (5)	0.0103 (5)	−0.0060 (5)
C12	0.0431 (7)	0.0317 (6)	0.0296 (6)	−0.0004 (5)	0.0102 (5)	0.0006 (5)
C13	0.0366 (7)	0.0342 (6)	0.0260 (6)	−0.0004 (5)	0.0053 (5)	−0.0006 (5)
N14	0.0647 (8)	0.0376 (6)	0.0309 (6)	0.0053 (6)	0.0130 (5)	0.0027 (5)
N15	0.0547 (7)	0.0380 (6)	0.0451 (7)	−0.0098 (6)	0.0147 (6)	−0.0108 (5)
N16	0.0461 (7)	0.0396 (6)	0.0306 (5)	−0.0053 (5)	0.0021 (5)	0.0023 (5)

O1—C8	1.2392 (16)	C5—C6	1.357 (2)
O2—N14	1.2069 (18)	C5—H5	0.93
O3—N14	1.2293 (17)	C6—H6	0.93
O4—N15	1.2214 (17)	N7—H7A	0.88 (2)
O5—N15	1.2267 (18)	N7—H7B	0.88 (2)
O6—N16	1.2216 (15)	C8—C13	1.4562 (17)
O7—N16	1.2130 (16)	C8—C9	1.4568 (17)
N1—C6	1.335 (2)	C9—C10	1.3613 (19)
N1—C2	1.3432 (19)	C9—N14	1.4578 (17)
N1—H1	0.91 (2)	C10—C11	1.3829 (19)
C2—C3	1.349 (2)	C10—H10	0.93
C2—H2	0.93	C11—C12	1.3832 (18)
C3—C4	1.408 (2)	C11—N15	1.4413 (17)
C3—H3	0.93	C12—C13	1.3726 (18)
C4—N7	1.328 (2)	C12—H12	0.93
C4—C5	1.408 (2)	C13—N16	1.4481 (16)
C6—N1—C2	120.05 (13)	C10—C9—C8	124.47 (11)
C6—N1—H1	118.0 (13)	C10—C9—N14	115.81 (12)
C2—N1—H1	121.9 (13)	C8—C9—N14	119.71 (12)
N1—C2—C3	121.28 (14)	C9—C10—C11	119.70 (12)
N1—C2—H2	119.4	C9—C10—H10	120.1
C3—C2—H2	119.4	C11—C10—H10	120.1
C2—C3—C4	120.36 (14)	C10—C11—C12	121.01 (12)
C2—C3—H3	119.8	C10—C11—N15	119.22 (12)
C4—C3—H3	119.8	C12—C11—N15	119.74 (12)
N7—C4—C3	120.62 (14)	C13—C12—C11	119.06 (12)
N7—C4—C5	122.52 (15)	C13—C12—H12	120.5
C3—C4—C5	116.85 (13)	C11—C12—H12	120.5
C6—C5—C4	119.43 (14)	C12—C13—N16	115.72 (11)
C6—C5—H5	120.3	C12—C13—C8	124.57 (11)
C4—C5—H5	120.3	N16—C13—C8	119.67 (11)
N1—C6—C5	122.02 (14)	O2—N14—O3	122.46 (13)
N1—C6—H6	119.0	O2—N14—C9	119.79 (13)
C5—C6—H6	119.0	O3—N14—C9	117.73 (13)
C4—N7—H7A	119.8 (16)	O4—N15—O5	122.97 (14)
C4—N7—H7B	115.0 (14)	O4—N15—C11	118.57 (13)
H7A—N7—H7B	125 (2)	O5—N15—C11	118.46 (13)
O1—C8—C13	125.23 (12)	O7—N16—O6	121.00 (12)
O1—C8—C9	123.57 (12)	O7—N16—C13	120.38 (11)
C13—C8—C9	111.14 (11)	O6—N16—C13	118.61 (11)
C6—N1—C2—C3	−0.1 (2)	C11—C12—C13—N16	−176.65 (12)
N1—C2—C3—C4	0.4 (2)	C11—C12—C13—C8	1.1 (2)
C2—C3—C4—N7	179.73 (16)	O1—C8—C13—C12	−179.30 (13)
C2—C3—C4—C5	−0.4 (2)	C9—C8—C13—C12	−2.13 (18)
N7—C4—C5—C6	−179.98 (16)	O1—C8—C13—N16	−1.6 (2)
C3—C4—C5—C6	0.2 (2)	C9—C8—C13—N16	175.54 (11)
C2—N1—C6—C5	−0.2 (2)	C10—C9—N14—O2	155.92 (14)
C4—C5—C6—N1	0.1 (2)	C8—C9—N14—O2	−24.9 (2)
O1—C8—C9—C10	178.44 (13)	C10—C9—N14—O3	−22.44 (18)
C13—C8—C9—C10	1.22 (18)	C8—C9—N14—O3	156.74 (13)
O1—C8—C9—N14	−0.7 (2)	C10—C11—N15—O4	8.1 (2)
C13—C8—C9—N14	−177.89 (11)	C12—C11—N15—O4	−169.71 (13)
C8—C9—C10—C11	0.7 (2)	C10—C11—N15—O5	−172.10 (14)
N14—C9—C10—C11	179.83 (12)	C12—C11—N15—O5	10.1 (2)
C9—C10—C11—C12	−1.9 (2)	C12—C13—N16—O7	−160.64 (14)
C9—C10—C11—N15	−179.76 (12)	C8—C13—N16—O7	21.5 (2)
C10—C11—C12—C13	1.1 (2)	C12—C13—N16—O6	20.26 (19)
N15—C11—C12—C13	178.88 (12)	C8—C13—N16—O6	−157.61 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.91 (2)	1.82 (2)	2.6877 (16)	158 (2)
N1—H1···O7i	0.91 (2)	2.34 (2)	2.9359 (19)	122 (2)
N7—H7A···O6ii	0.88 (2)	2.30 (3)	3.139 (2)	160 (2)
N7—H7B···O5iii	0.88 (2)	2.23 (2)	3.065 (2)	158 (2)
C2—H2···O4iv	0.93	2.47	3.1373 (19)	129
C2—H2···O7i	0.93	2.43	2.9980 (19)	119

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.91 (2)	1.82 (2)	2.6877 (16)	158 (2)
N1—H1⋯O7i	0.91 (2)	2.34 (2)	2.9359 (19)	122 (2)
N7—H7A⋯O6ii	0.88 (2)	2.30 (3)	3.139 (2)	160 (2)
N7—H7B⋯O5iii	0.88 (2)	2.23 (2)	3.065 (2)	158 (2)
C2—H2⋯O4iv	0.93	2.47	3.1373 (19)	129
C2—H2⋯O7i	0.93	2.43	2.9980 (19)	119

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