2-Amino-3-nitro­pyridinium 4-hy­droxy­benzene­sulfonate

Yao-hui Lv; Wei Zhang; Hong Liu

doi:10.1107/S1600536812027651

. 2012 Jun 23;68(Pt 7):o2169. doi: 10.1107/S1600536812027651

2-Amino-3-nitropyridinium 4-hydroxybenzenesulfonate

Yao-hui Lv ^a,^*, Wei Zhang ^a, Hong Liu ^b

PMCID: PMC3393975 PMID: 22798840

Abstract

In the crystal structure of the title salt, C₅H₆N₃O₂ ⁺·C₆H₅O₄S⁻, N—H⋯O and O—H⋯O hydrogen bonds link the cations and anions. The dihedral angle between the rings of the cation and anion is 79.91 (6)°.

Related literature

For related structures, see: Nicoud et al. (1997 ▶); Akriche & Rzaigui (2009a ▶,b ▶); Toumi Akriche et al. (2010 ▶); Koshima et al. (2004 ▶). For the design of second-order non-linear optical materials, see: Fur et al. (1998 ▶); Aakeröy et al. (1998 ▶). For information on the determination of non-linear optical properties, see: Kurtz & Perry (1968 ▶).

Experimental

Crystal data

C₅H₆N₃O₂ ⁺·C₆H₅O₄S⁻
M _r = 313.29
Monoclinic,
a = 9.0683 (19) Å
b = 13.5177 (16) Å
c = 10.9203 (17) Å
β = 94.042 (14)°
V = 1335.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 293 K
0.48 × 0.31 × 0.22 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.879, T _max = 0.942
4067 measured reflections
2005 independent reflections
1989 reflections with I > 2σ(I)
R _int = 0.011

Refinement

R[F ² > 2σ(F ²)] = 0.023
wR(F ²) = 0.063
S = 1.07
2005 reflections
194 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ▶), 825 Friedel pairs
Flack parameter: 0.05 (6)

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812027651/pk2420sup1.cif

e-68-o2169-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027651/pk2420Isup2.hkl

e-68-o2169-Isup2.hkl^{(98.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812027651/pk2420Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O5	0.86	2.01	2.862 (2)	172
N1—H1B⋯O1	0.86	2.08	2.674 (2)	126
N3—H3A⋯O6	0.86	1.88	2.734 (2)	170
N1—H1B⋯O3ⁱ	0.86	2.57	3.125 (3)	123
O3—H3⋯O4ⁱⁱ	0.75 (3)	1.98 (3)	2.688 (2)	158 (3)

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The work was supported financially by the Youth Foundation of Anhui University of Technology.

supplementary crystallographic information

Comment

Research on new materials with large nonlinear optical (NLO) efficiencies has been extensively developed in the past two decades. A promising crystal-engineering strategy is to design organic cocrystals, using molecules with large macroscopic susceptibility components (Nicoud et al., 1997). As an excellent donor-acceptor system with high susceptibility, 2-amino-3-nitropyridine cation has two electron-accepting centres, namely the NH₂ amino-group and NH⁺ group in the pyridinium ring (Aakeröy et al., 1998). Therefore, it is possible to utilize the cation of 2- amino-3-nitropyridinium as a nonlinear optical component to assemble potential NLO materials. Though several crystal structures based on the 2-amino-3-nitropyridine cation had been reported (Akriche & Rzaigui, 2009a,b; Toumi Akriche et al., 2010), to the best of our knowledge, the title complex in the present work is the first example of a NLO crystal with an efficiency as large as ten times that of the KDP standard (Kurtz & Perry, 1968). The asymmetric unit contains one anion and one cation that are shown in Fig. 1. Hydrogen bonding interactions, which construct a three-dimensional network, are listed in table 1. The crystal structure is stabilized by several hydrogen-bonding interactions formed within the crystal structure. These interactions link the cations and anions together in a complex spatial geometry, displayed in Fig. 2.

Experimental

The title complex was synthesized from the mixture of 2-amino-3-nitropyridine with stoichiometric 4-hydroxybenzenesulfonic acid in ethanol solution. The reaction mixture was stirred for four hours and slowly heated to 45°C yielding a clear solution. After solvent evaporation at controlled temperature for several days, yellow block-shaped crystals were obtained in 90% yield. For second-harmonic generation (SHG) experiments (Kurtz and Perry, 1968), the polycrystalline samples were ground into powder and sieved using a series of mesh sizes in the range of 74–100 µm, and the SHG intensity was compared with KDP crystal.