Mixed methyl-(2,4-dinitrophenyl)-aminopropanoate: 2-methyl-4-nitroaniline crystal−a new nonlinear optical material

Abstract

Single crystals of mixed methyl-(2,4-dinitrophenyl)-aminopropanoate (MAP): 2-methyl-4-nitroaniline (MNA) have been grown from solution using a 40:60 mixture of ethanol and ethyl acetate. Formation of an equimolar complex is confirmed by x-ray diffraction studies. The complex crystallizes in the monoclinic space group P21. The lattice parameters are a=6.9196(±0.005) Å; b=7.673(±0.008) Å; c=18.554(±0.001) Å; and β=92.547(±0.006)0. b axis is the unique twofold axis and there are two molecules per unit cell. The molecules stack along the b axis with MAP atop MNA atop MAP. Details of the molecular orientation are given. The Raman spectra also indicate that the parent molecules are not disturbed in the process of crystallization. The second harmonic generation efficiency of the new material for 1064 nm laser radiation is observed to be the same as that of MAP but lower than that of MNA. The latter is attributed to the absorption at 532 nm in the mixed crystal. The melting point determined by differential scanning calorimetry is 104.30 °C.

Uncovering the Intramolecular Emission and Tuning the Nonlinear Optical Properties of Organic Materials by Cocrystallization

“…Molecular cocrystals, a single‐phase material formed with different molecules through non‐covalent intermolecular interactions, exhibit unpredicted and versatile chemicophysical properties, such as high conductivity, nonlinear optics (NLO), ambipolar charge transportation, ferroelectricity, light‐driven actuator, and room‐temperature phosphorescence . In this context, cocrystallization actually provides an ideal research platform for achieving multiple functions and exploring interesting phenomena in molecular solids.…”

Reversibly Stretching Cocrystals by the Application of a Magnetic Field

“…Cocrystallization, one of the core topics of crystal engineering, is an extensively used strategy at the researcher’s disposal to acquire unpredicted structures with versatile functionalities and chemicophysical properties for self-assembled molecules in the solid state, − for their applications in such fields as organic semiconductors, nonlinear optics (NLO), , energetic materials, , ferroelectricity, − ambipolar charge transportation, long-distance proton transport, − light-driven actuators, photophysics, , conductivity, room-temperature phosphorescence, and especially the pharmaceutical industry . The self-assembly of different coformers can be directed by noncovalent supramolecular interactions, − including hydrogen bonding, halogen bonding, π–π interactions, electrostatic interactions, and van der Waals interactions.…”

Structure and crystal packing of the antibacterial drug 1-{[(5-nitro-2-furanyl)methylene]amino}-2,4-imidazolidinedione (nitrofurantoin)

“…It is significant that the powder second-harmonic generation efficiency (intensity of green light produced at 532 nm from irradiation at 1064 nn. from a pulsed Nd:YAG laser) was found in a preliminary experiment to be the same as that of MAP, but less than that of MNA (Rao, Batra, Lal, Evans, Loo, Metzger & Lee, 1991).…”