Synthesis, spectroscopic and thermal characterization of non-metal cation nmc pentaborates salts containing 2-amino-5-nitropyridine and 2-amino-6-methylpyridine as cation

Year 2015, , 91 - 96, 01.07.2015

Umit Sizir Dursun Ali Kose Omer Yurdakul

https://doi.org/10.17350/HJSE19030000014

Abstract

The pyridine derivatives, 2-amino-5-nitropyridine and 2-amino-6-methylpyridine 6-aminopicolin , were used for the synthesis of two new non-metal cation NMCs pentaborate structures. The NMCs pentaborate molecules were characterized using 11B-NMR, elemental analysis, BET, FT-IR, P-XRD and melting point technics. The thermal properties had been investigated by TGA/DTA/DTG methods. 2-amino-5nitropyridine and 2-amino-6-methyl pyridine NMC s pentaborates showed different thermal stabilities among each other, but degradation of the dehydration of the following organic both NMC pentaborate structure as part away and decomposition products of B2O3 occurs by having glassy structure. The trigonal BO3 and tetragonal BO- moities were determined in 11B NMR spectrums. According to P-XRD methods each of the compound structures are in crystalline form. The peaks of pentaborate anion [B5O6 OH 4]- were seen in FT-IR spectra. Lastly, the hydrogen storage properties of these molecules were studied. The estimated molecular formulas of the complexes are as follows: 2-amino-5-nitropyridine pentaborate: [C5H5N3O2][B5O6 OH 4]3H2O2-amino-6-methylpyridine pentaborate: C6H8N][BO OH 4]2H2O

Keywords

Boron, Non-metal Cation Borate Structure, Pentaborate, P-XRD, Thermal Investigation, 11B-NMR.

References

• 1. “Q & A: Where does the element Boron come from?”. physics. illinois.edu. Retrieved 2011-12-04.
• 2. “The tartrolons, new boron-containing antibiotics from a myxobacterium, Sorangium cellulosum.”. Retrieved 2013- 01-24.
• 3. Berger LI. Semiconductor materials. CRC Press. pp. 37–43, 1996.
• 4. Laubengayer AW, Hurd DT, Newkirk AE, Hoard JL. Boron. I. preparation and properties of pure crystalline boron. Journal of the American Chemical Society 65(10) (1943) 1924–1931.
• 5. Heller G. A survey of structural types of borates and polyborates. Topic Current Chem. 131 (1986) 39–98.
• 6. Schubert MR, Brotherton J. in: RB. King (Ed.), Encyclopedia of Inorganic Chemistry, second ed. Wiley, New York, pp. 499– 524, 2005.
• 7. Schubert M. Borates in industrial use. Struct. Bond. 105 (2003) 1–40.
• 8. Christ CL, Clark JR, A crystal-chemical classification of borate structures with emphasis on hydrated borates. Phys. Chem. Miner. 2 (1977) 59-87.
• 9. Burns PC. Borate clusters and fundamental building blocks containing four polyhedra; why few clusters are utilized as fundamental building blocks of structures. Can. Mineral. 33 (1995) 1167-1176.
• 10. (a) Wang GM, Sun YQ, Yang GY. Syntheses and crystal structures of two new pentaborates. J. Solid State Chem. 178 (2005) 729-735; (b) Wang GM, Sun YQ, Yang GY. Synthesis and characterization of a new layered lead borate, J. Solid State Chem. 179 (2006) 398-403.
• 11. Khan MdS, Prasad G, Kumar GS. Dielectric Properties of Ammonium Pentaborate Sinple Crystals. Crystal Research and Technology, 27(2) (1992) K28-K31.
• 12. Touboul M, Penin N, Nowogrocki G. Crystal Structure and Thermal Behavior of Cs2[B4O5(OH)4]3H2O. J. Solid State Chem. 143 (1999) 260-265.
• 13. Schubert DM, Alam F, Visi MZ, Knobler CB, Structural characterization and chemistry of the industrially important zinc borate, Zn[B3O4(OH)3]. Chem. Mater. 15 (2003) 866- 871.
• 14. Yu ZT, Shi Z, Jiang YS, Yuan HM, Chen JS. A chiral lead borate containing infinite and finite chains built up from BO4 and BO3 units, Chem. Mater. 14 (2002) 1314-1318.
• 15. Penin N, Touboul M, Nowogrocki G. Crystal structure of a new form of sodium octoborate E-Na2B8O13. J. Solid State Chem. 168 (2002) 316-321.
• 16. Huppertz H, von der Eltz B. Multianvil high- pressure synthesis of Dy4B6O15: The first oxoborate with edge-sharing BO4 tetrahedra. J. Am. Chem. Soc., 124 (2002) 9376-9377.
• 17. Zhang HX, Zheng ST, Yang GY. Pentaethylenehexamine manganese(II) pentaborate, Acta Cryst. C 60 (2004) m241-m243.
• 18. Schindler M, Hawthorne FC. A bond-valence approach to the structure, chemistry and paragenesis of hydroxyhydrated oxysalt minerals. II. Crystal structure and chemical composition of borate minerals. Can. Mineral. 39 (2001) 1243-1256.
• 19. Brown ID. in: O’Keeffe M, Navrotsky A. (Eds.) Structure and bonding in crystals, vol. 2, Academic Press, New York, pp. 1– 30, 1981.
• 20. Merlino S, Sartori F. Ammonioborite: new borate polyion and its structure.. Science 171 (1971) 377–379.
• 21. Merlino S, Sartori F. The crystal structure of larderellite, NH4B5O7(OH)2.H2O. Acta Crystallogr., Sect. B 25 (1969) 2264–2270.
• 22. Schubert DM, Smith RA, Visi MZ. Studies of crystalline nonmetal borates. Glass Technol. 44 (2003) 63–70.
• 23. Schubert DM, Visi MZ, Knobler CB, Guanidinium and Imidazolium Borates Containing the First Examples of an Isolated Nonaborate Oxoanion: [B9O12(OH)6]3-. Inorg. Chem. 39 (2000) 2250–2251.
• 24. Wang GM, Sun YQ, Yang GY. Syntheses and crystal structures of three new borates templated by transitionmetal complexes in situ, J. Solid State Chemistry 179 (2006) 1545-1553.
• 25. Köse DA, Beckett MA, Çolak N. Synthesis, spectroscopic and thermal characterization of non-metal cation (NMC) pentaborates salts containing cations derived from histidine and arginine. Hacettepe J. Biol. & Chem., 40(3) (2012) 219– 224.
• 26. Kamitsos EI. Infrared studies of borate glasses. Physics and Chemistry of Glasses, vol. 44(2), pp. 79–87, 2003.
• 27. Gautam C, Yadav AK, Singh AK. A review on infrared spectroscopy of borate glasses with effects of different additives. ISRN Ceramics, 2012, Article ID 428497, doi:10.5402/2012/428497.
• 28. Janda R, Heller G. IR- und raman spektren isotop markierter tetra- und pentaborate. Spectrochimica Acta 36A (1980) 997–1001.
• 29. Beckett MA, Bland CC, Coles SJ, Horton PN, Hursthouse MB. Supramolecular structures containing ‘isolated’ pentaborate anions and non-metal cations: Crystal structures of [Me3NCH2CH2OH][B5O6(OH)4] and [4-MepyH, 4-Mepy][B5O6(OH)4]. J. Organomet. Chem. 692 (2007) 2832-2838.
• 30. Salentine CG. High-field 11B NMR of alkali borates. Aqueous polyborate equilibria. Inorg. Chem. 22 (1983) 39203924.
• 31. Beckett MA, Horton PN, Hursthouse MB, Knox DA, Timmis JL. Structural (XRD) and thermal (DSC, TGA) and BET analysis of materials derived from non-metal cation pentaborate salts, Dalton Trans. 39 (2010) 3944-3951.