3-Amino­pyridinium picrate

Li, Y.

doi:10.1107/S1600536810037190

organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2680

doi:10.1107/S1600536810037190

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3-Aminopyridinium picrate

Yan-jun Li ^a ^*

^aCollege of Chemical Engineering and Technology, Wuhan University of Science and Technology, Wuhan 430081, People's Republic of China
^*Correspondence e-mail: yanwatercn@wust.edu.cn

(Received 5 September 2010; accepted 16 September 2010; online 30 September 2010)

During the formation of the title compound, C₅H₇N₂⁺·C₆H₂N₃O₇⁻, a phenolic proton is transferred to the pyridine N atom. In the crystal structure, the ions are linked by intermolecular 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 interactions 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_r = 323.23
Monoclinic, P 2₁ /n
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[F² > 2σ(F²)] = 0.060
wR(F²) = 0.162
S = 1.03
2804 reflections
217 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.24 e Å⁻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) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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).

Supporting information

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

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

checkCIF report

Comment top

Picric acid has been used in the characterization of organic bases because of the ease of crystallization and hence purification when picrate derivatives are produced (Pascard et al., 1982; Pearson et al., 2007; Harrison et al., 2007; Shakir et al., 2009). Here, we report the crystal structure of the title salt.

In the title compound, a hydrogen atom has been transferred from the picric acid molecule to the nitrogen atom of the pyridine ring and hence a 1:1 organic is formed salt (Fig.1). In the picric acid molecule, the geometric parameters of C6—O7 = 1.236 (3)Å and C1—C6—C5 = 112.0 (2)° confirm the transfer of the proton.

In the crystal structure, the molecular components are linked into a two dimensional zigzag-like layers (Fig.2) running parallel to (110) by intermolecular N—H···O hydrogen bonds (Table 1). These adjacent (100) layers are linked by weak π–π interaction between symmetry related pyridine and picric benzene rings (centroid-to-centroid distance = 3.758 (2) Å, symmetry code: 2 - x, 1 - y, 1 - z) into a three-dimensional network.

Related literature top

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 top

Picric acid (0.69 g, 3 mmol) and 3-aminopyridine (0.28 g, 3 mmol) were mixed in 10 ml ethanol. The mixture was kept at room temperature for two weeks. Yellow needeles suitable for single-crystal X-ray diffraction were obtained at the bottom of the vessel.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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).

Figures top

	Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines. For the sake of clarity, the H atoms not involved in the hydrogen-bonds pattern have been omitted.

3-Aminopyridinium picrate top

Crystal data top

C₅H₇N₂⁺·C₆H₂N₃O₇⁻	F(000) = 664
M_r = 323.23	D_x = 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

Data collection top

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

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)] = 0.060	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(F_o²) + (0.0663P)² + 0.0975P] where P = (F_o² + 2F_c²)/3
2804 reflections	(Δ/σ)_max < 0.001
217 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₅H₇N₂⁺·C₆H₂N₃O₇⁻	V = 1290.2 (2) Å³
M_r = 323.23	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.2174 (8) Å	µ = 0.14 mm⁻¹
b = 13.5842 (13) Å	T = 297 K
c = 11.8218 (12) Å	0.45 × 0.05 × 0.02 mm
β = 102.117 (2)°

Data collection top

Bruker SMART CCD diffractometer	2804 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1391 reflections with I > 2σ(I)
T_min = 0.939, T_max = 0.997	R_int = 0.072
14192 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.34 e Å⁻³
2804 reflections	Δρ_min = −0.24 e Å⁻³
217 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
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x+3/2, y+1/2, −z+3/2; (ii) −x+3/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₅H₇N₂⁺·C₆H₂N₃O₇⁻
M_r	323.23
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	297
a, b, c (Å)	8.2174 (8), 13.5842 (13), 11.8218 (12)
β (°)	102.117 (2)
V (Å³)	1290.2 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.45 × 0.05 × 0.02

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.939, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	14192, 2804, 1391
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.162, 1.03
No. of reflections	2804
No. of parameters	217
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.24

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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) −x+3/2, y+1/2, −z+3/2; (ii) −x+3/2, y+1/2, −z+1/2.

Acknowledgements

Wuhan University of Science and Technology is thanked for supporting this study.

References

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