Abstract
Colourless crystals of a new, dicationic, hydropyrophosphate dihydrate salt, KHMgP2O7⋅ 2H2O, are formed, when a mixture of aqueous equimolar solutions of MgCl2⋅4H2O and K4P2O7, at pH 2.12, are left to stand at ambient temperature for 4 days. The new pyrophosphate salt has been characterized by single-crystal X-ray diffraction, IR and Raman spectra, and DSC-TG thermal analysis. The structure consists of alternating layers of [HP2O7]3− groups and MgO6 octahedra, joined by K+ ions and bridging hydrogen bonds. The [P2O7]4− anions exhibit a bent eclipsed conformation. The absence of coincidences for the majority of the IR and Raman bands is in accord with the centrosymmetric structure of the material. The 31P chemical shift tensor components have been determined from the solid-state MAS NMR spectra. The structural changes occurring during thermal decomposition have been examined by TG-DSC, X-ray powder diffraction (XRD) and IR spectroscopy. When the new pyrophosphate salt is heated gradually, it first becomes amorphous and then condenses to chain metaphosphates.
Similar content being viewed by others
References
(a) Jouini, A.; Gâcon, J.C.; Ferid, M.; Trabelsi-Ayadi, M. Opt. Mater. 2003, 24, 175. (b) Belharouak, I.; Parent, C.; Chaminade, J.P.; Gravereau, P.; Le Flem, G.; Moine, B.; Pedrini, C.; Aouad, H.; Mesnaoui, M.; Maazaz, M. Phosphorus Res. Bull. 1999, 10, 375.
Kitsugi, T.; Yamamuro, T.; Nakamura, T.; Oka, M. Biomaterials 1995, 16, 1101.
(a) Bian Jian-jiang; Kim Dong-Wan; Hong Kug Sun. J. Euro. Ceram. Soc. 2003, 23, 2589. (b) Kim, C.H.; Yim, H. S. Solid Stat. Commun. 1999, 110, 137.
(a) Mogus-Milankovi, A.; Santic, B.; Ray, C.S.; Day, D.E.J. Non-Cryst. Solid 2000, 263, 299. (b) Dridi, N.; Boukhari, A.; Reau, J.M.; Arbib, E.; Holt, E.M. Mater. Lett. 2001, 47, 212.
(a) Carmen, P.; Josefina, P.; Regino, S.P.; Caridad, R.V.; Natalia, S. Chem. Mater. 2003, 15, 3347. (b) Saito, T.; Terashima, T.; Azuma, M.; Takano, M.; Goto, T.; Ohta, H.; Utsumi, W.; Bordet, P.; Johnston, D.C. J. Solid-State Chem. 2000, 153, 124. (c) Le Meins, J.-M.; Grenèche, J.-M.; Courbion, G. J. Solid-State Chem. 1999, 148, 286. (d) Sanz, F.; Parada, C.; Ruiz-Valero, C. Chem. Mater. 2000, 12, 671. (e) Kruger, P.E.; Doyle, R.P.; Julve, M.; Lloret, F.; Nieuwenhuyzen, M. Inorg. Chem. 2001, 40, 1726. (f) Chippindale, A.M.; Gaslain, F.O.M.; Bond, A.D.; Powell, A.V. J. Mater. Chem. 2003, 13, 1950.
Marcu, I.C.; Millet, J.M.; Sandulescu, I. Prog. Catal. 2001, 10(1–2), 71.
(a) Hyun-Seung Ryu; Hyuk-Joon Youn; Kug Sun Hong; Bong-Sun Chang; Choon-Ki Lee; Sung-Soo Chung. Biomaterials 2002, 23, 909. (b) Macchia, M.; Antonelli, G.; Bertini, S.; Calvani, F.; Di Bussolo, V.; Minutolo, F.; Tesoro, R.; Tonetti, I.; Turriziani, O. Il Fármaco. 2000, 55, 322. (c) Vucina, L. J. Jurij. Serb. Chem. Soc. 1999, 64(5–6), 375.
Uebou, Y.; Okada, S.; Egashira, M.; Yamaki, J.I. Solid Stat. Ionic. 2002, 148, 323.
Corbridge, D.E.C. Acta Crystallogr. 1957, 10, 85.
Corbridge, D.E.C. The Structural Chemistry of Phosphorous; Elsevier: Amsterdam, 1974.
Dumas, Y.; Galigne, J.L.; Falgueirettes. J. Acta Cryst. 1973, B29, 1623.
Mathew, M.; Schroeder, L.W. Acta Crystallogr. 1977, B33, 3025.
Durif, A.; Averbuch-Pouchot, M.T. Acta Crystallogr. 1982, B38, 2883.
Haromy, T.P.; Knight, W.B.; Dunaway-Mariano, D.; Sundaralingam, M. Acta Crystallogr. 1984, C40, 223.
Effenberger, H. Acta Crystallogr. 1987, C43, 1237.
Haromy, T.P.; Linck, C.F.; Cleland, W.W.; Sundaralingam, M. Acta Crystallogr. 1990, C46, 951.
Simonov, M.A.; Karpov, O.G.; Dimitrova, O.V.; Strelkova, E.E. Kristallografiya 1991, 36, 1151.
Byrappa, K.; Umesh Dutt, B.V. J. Mater. Res. 1994, 9, 1519.
Hsu, K.F.; Wang, S.L. Acta Crystallogr. 1999, C55, 1400.
Chehimi, M.F.; Chehimi, B.H.; Ferid, D.; Trabelsi-Ayadi, M. Mater. Res. Bull. 2001, 36, 365.
Blum, M.; Thauern, H.; Glaum, R. Phosphorus Res. Bull. 2002, 13, 83.
Chehimi, M.F.; Ferid, M.; Chehimi, B.H.; Trebelsi-Ayadi, M. Solid State Sci. 2002, 4, 979.
Ivashkevich, L.; Selevich, K.A.; Lyakhov, A.S.; Selevich, A.F.; Petrusevich, Yu.I. Z. Kristallogr. 2002, 217, 73.
Assaaoudi, H.; Ennaciri, A.; Harcharras, M.; El Bali, B.; Reinauer, F.; Glaum, R.; Rulmont, A.; Spirlet, M.-R. Acta Crystallogr. 2002, C58, i79.
Harcharras, M.; Goubitz, K.; Ennaciri, A.; Assaaoudi, H.; Schenk, H. Acta Crystallogr. 2003, C59, i57.
Harcharras, M.; Assaaoudi, H.; Ennaciri, A.; Mattei, G.; D'Orazio, V.; Moliterni, A.G.G.; Capitelli, F.J. Solid State Chem. 2003, 172, 160.
Sarr, O.; Diop, L. Spectrochim. Acta 1987, A43, 999.
Harcharras, M.; Capitelli, F.; Ennaciri, A.; Brouzi, K.; Moliterni, A.G.G.; Mattei, G.; Bertolasi, V. J. Solid State Chem. 2003, 176, 27.
Herzfeld, J.; Berger, A.E. J. Chem. Phys. 1980, 73, 6021.
Dusold, S.; Kümmerlen, J.; Sebald, A. J. Phys. Chem. 1997, 101, 5895.
Fayon, F.; King, I.J.; Harris, R.K.; Gover, K.B.; Evans, J.S.O.; Massiot, D. Chem. Mater., 2003, 15, 2234.
Sheldrick, G.M. SHELXS97, Program for Crystal Structure Solution; University of Göttingen: Germany, 1997.
Sheldrick, G. M. SHELXL97, Program for Crystal Structure Refinement; University of Göttingen: Germany, 1997.
Bruker, SHELXTL. Release 5.10, The Complete Software Package for Single Crystal Structure Determination; Bruker AXS Inc.: Madison, USA, 1997.
Burnett, M.N.; Johnson, C.K. ORTEP-III, Oak Ridge National Laboratory Report ORNL-6895, 1996.
Farrugia, L.J. J. Appl. Cryst., 1997, 30, 565.
Smith, T.J. J. Mol. Graphics 1995, 13, 122.
Kobashi, D.; Kohara, S.; Yamakawa, J.; Kawahara, A. Acta Crystallogr. 1997, C53, 1523.
Kubo, A.; McDowell, C.A. J. Chem. Phys. 1990, 92, 7156.
(a) Harcharras, M.; Ennaciri, A.; Assaaoudi, H. Can. J. Anal. Sci. Spectrosc. 2001, 46(3), 83. (b) Harcharras, M.; Ennaciri, A.; Rulmont, A.; Gilbert, B. Spectrochim. Acta 1997, A53, 345.
Sarr, O.; Diop, L. Spectrochim. Acta, 1984, A40, 1011.
(a) Santha, N.; Nayar, V.U. Spectrochim. Acta 1993, A49, 47. (b) Brouzi, K.; Ennaciri, A.; Harcharras, M.; Capitelli, F.J. Raman Spect. 2004, 35, 41.
Assaaoudi, H.; Butler, I.S.; Kozinski, J.; Bélanger-Gariépy, F. J. Chem. Crystallogr. 2005, 35(1), 49.
(a) Stranford, G.T.; Condrate, Sr. R.A. J. Molec. Struct. 1981, 73, 231. (b) Cornilsen, B.C.; Condrate, Sr. R.A. J. Phys. Chem. Solids 1977, 38, 1327. (c) Cornilsen, B.C.; Condrate, Sr. R.A. J. Solid State Chem. 1978, 23, 375. (d) Cornilsen, B.C.; Condrate, Sr. R.A. J. Inorg. Nucl. Chem. 1979, 41, 602.
Rulmont, A.; Cahay, R.; Liegeois-Duykaerts, M.; Tarte, P. Eur. J. Solid State Inorg. Chem. 1991, 28, 207.
Rulmont, A.; Cahay, R.; Liegeois-Duyckaerts, M.; Tarte, P. Eur. J. Solid State Inorg. Chem. 1991, t.28, 207.
Miroshnichenko, O.Ya.; Monbelli, V.V. Russ. J. Inorg. Chem. 1979, 24, 1631.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Assaaoudi, H., Butler, I.S., Kozinski, J. et al. Crystal structure, vibrational spectra and thermal decomposition study of a new, dicationic, acidic pyrophosphate: KHMgP2O7⋅2H2O. J Chem Crystallogr 35, 809–820 (2005). https://doi.org/10.1007/s10870-005-4551-z
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/s10870-005-4551-z