3-Amino-pyridinium picrate.

During the formation of the title compound, C(5)H(7)N(2) (+)·C(6)H(2)N(3)O(7) (-), a phenolic proton is transferred to the pyridine N atom. In the crystal structure, the ions are linked by inter-molecular N-H⋯O and N-H⋯(O,O) hydrogen bonds into layers running parallel to (100). These layers are connected by weak π-π stacking inter-actions between symmetry-related pyridine and picric benzene rings with a centroid-centroid distance of 3.758 (2) Å, forming a three-dimensional network.

Related literature

For applications of picric acid derivatives, see: Pascard et al. (1982 ▶); Pearson et al. (2007 ▶); Shakir et al. (2009 ▶). For a related structure, see: Harrison et al. (2007 ▶).

Experimental

Crystal data

C5H7N2 +·C6H2N3O7 −

M = 323.23

Monoclinic,

a = 8.2174 (8) Å

b = 13.5842 (13) Å

c = 11.8218 (12) Å

β = 102.117 (2)°

V = 1290.2 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.14 mm−1

T = 297 K

0.45 × 0.05 × 0.02 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.939, T max = 0.997

14192 measured reflections

2804 independent reflections

1391 reflections with I > 2σ(I)

R int = 0.072

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.162

S = 1.03

2804 reflections

217 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.24 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037190/lh5128sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037190/lh5128Isup2.hkl

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

C5H7N2+·C6H2N3O7−	F(000) = 664
Mr = 323.23	Dx = 1.664 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1100 reflections
a = 8.2174 (8) Å	θ = 2.3–20.4°
b = 13.5842 (13) Å	µ = 0.14 mm−1
c = 11.8218 (12) Å	T = 297 K
β = 102.117 (2)°	Needle, yellow
V = 1290.2 (2) Å3	0.45 × 0.05 × 0.02 mm
Z = 4

Bruker SMART CCD diffractometer	2804 independent reflections
Radiation source: fine-focus sealed tube	1391 reflections with I > 2σ(I)
graphite	Rint = 0.072
φ and ω scans	θmax = 27.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.939, Tmax = 0.997	k = −17→17
14192 measured reflections	l = −15→15

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0663P)2 + 0.0975P] where P = (Fo2 + 2Fc2)/3
2804 reflections	(Δ/σ)max < 0.001
217 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.8262 (3)	0.49045 (18)	0.2590 (2)	0.0390 (7)
C2	0.8816 (3)	0.45022 (19)	0.1686 (2)	0.0401 (7)
H2	0.8614	0.4819	0.0973	0.048*
C3	0.9673 (3)	0.36279 (18)	0.1827 (2)	0.0378 (7)
C4	1.0039 (3)	0.31637 (19)	0.2881 (2)	0.0388 (7)
H4	1.0636	0.2577	0.2967	0.047*
C5	0.9518 (3)	0.35703 (19)	0.3805 (2)	0.0388 (7)
C6	0.8524 (4)	0.4466 (2)	0.3728 (2)	0.0428 (7)
C7	0.5593 (4)	0.6203 (2)	0.7181 (2)	0.0449 (7)
C8	0.5870 (4)	0.5718 (2)	0.8241 (2)	0.0474 (8)
H8	0.5482	0.5994	0.8855	0.057*
C9	0.6702 (4)	0.4844 (2)	0.8392 (3)	0.0532 (8)
H9	0.6866	0.4527	0.9104	0.064*
C10	0.7300 (4)	0.4426 (2)	0.7507 (3)	0.0531 (8)
H10	0.7872	0.3831	0.7605	0.064*
C11	0.6221 (4)	0.5750 (2)	0.6304 (2)	0.0470 (8)
H11	0.6070	0.6043	0.5578	0.056*
N1	0.7366 (3)	0.58418 (19)	0.2352 (3)	0.0562 (7)
N2	1.0162 (3)	0.31865 (19)	0.0837 (2)	0.0498 (7)
N3	0.9978 (4)	0.3051 (2)	0.4890 (2)	0.0569 (7)
N4	0.4760 (4)	0.7061 (2)	0.7014 (3)	0.0684 (9)
N5	0.7032 (3)	0.4902 (2)	0.6502 (2)	0.0511 (7)
O1	0.6984 (4)	0.61237 (17)	0.1355 (3)	0.0962 (10)
O2	0.6942 (4)	0.6267 (2)	0.3121 (2)	0.1179 (12)
O3	0.9816 (3)	0.36138 (17)	−0.00931 (18)	0.0755 (8)
O4	1.0901 (3)	0.24022 (17)	0.09581 (19)	0.0736 (7)
O5	1.1054 (3)	0.24169 (18)	0.49917 (19)	0.0764 (8)
O6	0.9316 (3)	0.3268 (2)	0.5696 (2)	0.0916 (9)
O7	0.7949 (3)	0.48236 (16)	0.45224 (19)	0.0770 (8)
H4A	0.455 (5)	0.730 (3)	0.634 (3)	0.092*
H4B	0.436 (5)	0.731 (3)	0.757 (3)	0.092*
H5	0.749 (4)	0.465 (2)	0.592 (3)	0.092*

	U11	U22	U33	U12	U13	U23
C1	0.0361 (16)	0.0317 (15)	0.0490 (17)	0.0008 (12)	0.0087 (14)	−0.0052 (13)
C2	0.0394 (17)	0.0427 (16)	0.0376 (16)	−0.0036 (14)	0.0069 (13)	0.0015 (13)
C3	0.0414 (17)	0.0381 (16)	0.0369 (16)	−0.0046 (13)	0.0147 (13)	−0.0068 (12)
C4	0.0371 (16)	0.0341 (15)	0.0453 (16)	−0.0027 (13)	0.0085 (13)	−0.0026 (13)
C5	0.0419 (17)	0.0425 (16)	0.0319 (15)	−0.0109 (13)	0.0075 (13)	0.0019 (12)
C6	0.0417 (18)	0.0483 (17)	0.0422 (17)	−0.0090 (14)	0.0171 (14)	−0.0127 (14)
C7	0.0475 (18)	0.0477 (18)	0.0402 (17)	−0.0098 (15)	0.0106 (14)	−0.0062 (14)
C8	0.0508 (19)	0.0570 (19)	0.0380 (17)	−0.0061 (16)	0.0178 (14)	−0.0072 (14)
C9	0.056 (2)	0.065 (2)	0.0385 (17)	−0.0058 (17)	0.0098 (16)	−0.0019 (15)
C10	0.049 (2)	0.057 (2)	0.0526 (19)	−0.0070 (15)	0.0094 (16)	−0.0019 (16)
C11	0.0470 (19)	0.061 (2)	0.0333 (16)	−0.0152 (16)	0.0095 (14)	−0.0029 (14)
N1	0.0469 (16)	0.0525 (17)	0.0693 (19)	0.0071 (13)	0.0129 (15)	−0.0143 (15)
N2	0.0528 (17)	0.0548 (17)	0.0453 (16)	−0.0010 (13)	0.0183 (13)	−0.0087 (13)
N3	0.0603 (19)	0.0655 (18)	0.0432 (16)	−0.0104 (16)	0.0070 (14)	0.0083 (14)
N4	0.095 (2)	0.0606 (19)	0.0508 (18)	0.0098 (17)	0.0180 (17)	0.0020 (15)
N5	0.0461 (17)	0.0593 (17)	0.0514 (18)	−0.0099 (13)	0.0184 (13)	−0.0191 (14)
O1	0.127 (2)	0.0793 (18)	0.094 (2)	0.0456 (17)	0.0484 (19)	0.0347 (15)
O2	0.144 (3)	0.109 (2)	0.087 (2)	0.074 (2)	−0.0071 (19)	−0.0394 (17)
O3	0.100 (2)	0.0951 (18)	0.0367 (12)	0.0179 (15)	0.0255 (12)	0.0006 (12)
O4	0.0958 (19)	0.0592 (14)	0.0733 (16)	0.0264 (14)	0.0347 (14)	−0.0095 (12)
O5	0.098 (2)	0.0659 (16)	0.0572 (15)	0.0144 (15)	−0.0020 (14)	0.0129 (12)
O6	0.094 (2)	0.136 (2)	0.0549 (15)	0.0175 (17)	0.0390 (15)	0.0328 (15)
O7	0.106 (2)	0.0784 (16)	0.0612 (15)	0.0045 (14)	0.0509 (15)	−0.0147 (12)

C1—C2	1.361 (3)	C8—H8	0.9300
C1—C6	1.446 (4)	C9—C10	1.369 (4)
C1—N1	1.468 (3)	C9—H9	0.9300
C2—C3	1.373 (3)	C10—N5	1.329 (4)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.372 (4)	C11—N5	1.328 (4)
C3—N2	1.445 (3)	C11—H11	0.9300
C4—C5	1.371 (3)	N1—O2	1.190 (3)
C4—H4	0.9300	N1—O1	1.216 (3)
C5—N3	1.443 (3)	N2—O4	1.220 (3)
C5—C6	1.457 (4)	N2—O3	1.223 (3)
C6—O7	1.236 (3)	N3—O5	1.222 (3)
C7—N4	1.345 (4)	N3—O6	1.229 (3)
C7—C8	1.392 (4)	N4—H4A	0.85 (4)
C7—C11	1.394 (4)	N4—H4B	0.86 (4)
C8—C9	1.364 (4)	N5—H5	0.91 (3)
C2—C1—C6	123.8 (2)	C8—C9—C10	120.8 (3)
C2—C1—N1	115.8 (3)	C8—C9—H9	119.6
C6—C1—N1	120.4 (3)	C10—C9—H9	119.6
C1—C2—C3	120.0 (3)	N5—C10—C9	117.5 (3)
C1—C2—H2	120.0	N5—C10—H10	121.2
C3—C2—H2	120.0	C9—C10—H10	121.2
C4—C3—C2	121.1 (2)	N5—C11—C7	120.2 (3)
C4—C3—N2	120.0 (2)	N5—C11—H11	119.9
C2—C3—N2	118.9 (2)	C7—C11—H11	119.9
C5—C4—C3	119.5 (3)	O2—N1—O1	122.0 (3)
C5—C4—H4	120.2	O2—N1—C1	119.3 (3)
C3—C4—H4	120.2	O1—N1—C1	118.4 (3)
C4—C5—N3	116.4 (3)	O4—N2—O3	122.4 (2)
C4—C5—C6	123.4 (2)	O4—N2—C3	118.9 (3)
N3—C5—C6	120.2 (3)	O3—N2—C3	118.6 (3)
O7—C6—C1	122.6 (3)	O5—N3—O6	121.5 (3)
O7—C6—C5	125.4 (3)	O5—N3—C5	118.8 (3)
C1—C6—C5	112.0 (2)	O6—N3—C5	119.7 (3)
N4—C7—C8	121.6 (3)	C7—N4—H4A	118 (3)
N4—C7—C11	122.0 (3)	C7—N4—H4B	119 (3)
C8—C7—C11	116.4 (3)	H4A—N4—H4B	122 (4)
C9—C8—C7	120.8 (3)	C11—N5—C10	124.2 (3)
C9—C8—H8	119.6	C11—N5—H5	117 (2)
C7—C8—H8	119.6	C10—N5—H5	118 (2)
C6—C1—C2—C3	0.3 (4)	C7—C8—C9—C10	0.6 (4)
N1—C1—C2—C3	179.8 (2)	C8—C9—C10—N5	−0.2 (4)
C1—C2—C3—C4	−2.4 (4)	N4—C7—C11—N5	−179.8 (3)
C1—C2—C3—N2	176.4 (2)	C8—C7—C11—N5	0.0 (4)
C2—C3—C4—C5	1.1 (4)	C2—C1—N1—O2	−175.1 (3)
N2—C3—C4—C5	−177.7 (2)	C6—C1—N1—O2	4.4 (4)
C3—C4—C5—N3	−178.8 (2)	C2—C1—N1—O1	9.8 (4)
C3—C4—C5—C6	2.4 (4)	C6—C1—N1—O1	−170.7 (3)
C2—C1—C6—O7	−176.9 (3)	C4—C3—N2—O4	−0.1 (4)
N1—C1—C6—O7	3.6 (4)	C2—C3—N2—O4	−178.9 (3)
C2—C1—C6—C5	2.8 (4)	C4—C3—N2—O3	179.8 (3)
N1—C1—C6—C5	−176.7 (2)	C2—C3—N2—O3	1.0 (4)
C4—C5—C6—O7	175.5 (3)	C4—C5—N3—O5	14.6 (4)
N3—C5—C6—O7	−3.2 (4)	C6—C5—N3—O5	−166.5 (3)
C4—C5—C6—C1	−4.1 (4)	C4—C5—N3—O6	−167.1 (3)
N3—C5—C6—C1	177.1 (2)	C6—C5—N3—O6	11.8 (4)
N4—C7—C8—C9	179.3 (3)	C7—C11—N5—C10	0.4 (4)
C11—C7—C8—C9	−0.5 (4)	C9—C10—N5—C11	−0.3 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O7	0.91 (3)	1.79 (3)	2.607 (3)	148 (3)
N5—H5···O6	0.91 (3)	2.46 (3)	3.179 (4)	136 (3)
N4—H4B···O6i	0.86 (4)	2.48 (4)	3.119 (4)	132 (3)
N4—H4A···O3ii	0.85 (4)	2.44 (4)	3.172 (4)	145 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5⋯O7	0.91 (3)	1.79 (3)	2.607 (3)	148 (3)
N5—H5⋯O6	0.91 (3)	2.46 (3)	3.179 (4)	136 (3)
N4—H4B⋯O6i	0.86 (4)	2.48 (4)	3.119 (4)	132 (3)
N4—H4A⋯O3ii	0.85 (4)	2.44 (4)	3.172 (4)	145 (3)

Symmetry codes: (i) ; (ii) .