Preparation of Cocrystals of 2-Amino-3-nitropyridine with Benzenesulfonic Acids for Second-Order Nonlinear Optical Materials

Abstract

Noncentrosymmetic and chiral cocrystals were prepared from 2-amino-3-nitropyridine (2A3NP) and achiral benzenesulfonic acids (Ar-SO 3 H), which were designed for second-order nonlinear optical materials. Both components are commonly crystallized in 1:1 ionic forms of 2A3NPH + ‚Ar-SO 3 -. The molecular packings of cocrystals are controlled by the aromatic-aromatic interactions as well as multidirectional ionic and hydrogen bonds between the 2A3NPH + cations and the sulfonate anions. The crystal of 2A3NP with p-toluenesulfonic acid belongs to acentric space group Pna2 1 , in which 2A3NPH + cations and anions are alternately stacked with some dihedral angle due to the large sulfonate anions to form two independent column structures in a perpendicular direction to each other. The crystal of 2A3NP with p-nitrobenzenesulfonic acid crystallizes into chiral space group P2 1 2 1 2 1 . The 2A3NPH + cations and the anions are also alternately stacked to give herringbone network of 2A3NPH + cations. The crystal of 2A3NP with 2,5-dimethylbenzenesulfonic acid belongs to acentric space group Pn, in which two independent stacking structures are formed in perpendicular directions. Second-harmonic generation (SHG) power measured with an evanescent wave technique revealed the relatively high SHG efficiency of cocrystal of 2A3NP with p-toluenesulfonic acid, 2-fold larger than that of well-known m-nitroaniline.

Temperature-induced reversible structural phase transition and X-ray diffuse scattering in 2-amino-3-nitropyridinium hydrogen sulfate

“…Despite those structural similarities, there is one important difference -the absence of the herringbone pattern, which could cause the crystallization of the selenate compound in the centrosymmetric space group. This observation is in good agreement with the assumption that the arrangement of 2-amino-3nitropyridinium cations in the herringbone motif is responsible for the formation of the non-centrosymmetric framework (Pecaut et al, 1993;Fur et al, 1998;Morel et al, 2002;Koshima et al, 2004).…”

“…2-Amino-3-nitropyridine (2A3NP) with electron donor (NH 2 ) and electron acceptor (NO 2 ) groups is a good moiety for high molecular polarizability. Several non-centrosymmetric organic-inorganic hybrid compounds, including the 2amino-3-nitropyridinium cations as nonlinear optical entities, have been discovered (Nicoud et al, 1997;Fur et al, 1998;Koshima et al, 2004;Chen et al, 2014). Furthermore, such acid-base compounds were found to undergo multiple structural phase transitions related to the dynamics of organic cations or inorganic anions (Czarnecki & Małuszyń ska, 2000;Pająk et al, 2006) and were found to possess peculiar physicochemical properties, such as high proton conductivity (Susan et al, 2003;Wojnarowska et al, 2015).…”

Discovery of Non-linear Optical Materials by Function-Based Screening of Multi-component Solids

“…14 The task of realizing efficient NLO-phores (non-linear optical chromophores with large b) 15,16 often requires multi-step synthetic processes, which, when handicapped with low yields, consume significant amounts of time and resources to generate sufficient material to screen for SHG active multi-component salts and cocrystals. [17][18][19][20][21] On the other hand, screening a large number of coformers is essential because it increases the probability of finding a suitable counterion or coformer that renders appropriate orientation of an NLO-phore to achieve optimal phase matching for large bulk SHG activity. 1,22 Further, the effect of a counterion or coformer in steering the NLO-phore into a centrosymmetric or non-centrosymmetric lattice is so unpredictable that the outcome of using a particular coformer cannot be generalized to any other structurally related molecules.…”

Hydrogen-bonded assembly of aminophosphonic anions: different 1D, 2D and 3D supramolecular architectures

“…Elemental analysis: found, %: C 23.23, H 6.85, N 13.53. Calcd for C 6 Synthesis of (APDPH 3 )$(pipH 2 ) 0.5 (5) A mixture of 0.2192 g APDPH 4 (1 mmol), 0.0971 g pip$6H 2 O (0.5 mmol) and 0.5 mL distilled water was sealed in a small centrifuge tube and then heated at 80 C for 3 d. Colourless crystals for single-crystal diffraction analysis were obtained. Yield: 52% (based on APDPH 4 ).…”