International Journal of Inorganic Chemistry

International Journal of Inorganic Chemistry / 2012 / Article

Research Article | Open Access

Volume 2012 |Article ID 702471 | https://doi.org/10.1155/2012/702471

Khalil Azzaoui, Rachid Essehli, El Miloud Mejdoubi, Brahim El Bali, Michal Dusek, Karla Fejfarova, "Na3MP3O10·12H2O (M = Co, Ni): Crystal Structure and IR Spectroscopy", International Journal of Inorganic Chemistry, vol. 2012, Article ID 702471, 6 pages, 2012. https://doi.org/10.1155/2012/702471

Na3MP3O10·12H2O (M = Co, Ni): Crystal Structure and IR Spectroscopy

Academic Editor: Maurizio Peruzzini
Received05 Sep 2012
Revised03 Oct 2012
Accepted04 Oct 2012
Published27 Nov 2012

Abstract

Two new dodecahydrate trisodium triphosphates Na3MP3O10·12H2O (M = Co (1), Ni (2)) were synthesized using a wet chemistry route and characterized by X-ray diffraction and FT-IR spectroscopy. They are isotypic, monoclinic (P21/ , ), with pseudoorthorhombic unit cell parameters (Ǻ,°): ( (4), (2), (4), (2), for (1) and (3), (2), (3), (16) for (2)). Values of / are 0.0267/0.0738 and 0.0284/0.0907, respectively, for (1) and (2). Both compounds were found to be systematically twinned by 180° rotation around . Their frameworks are made by slabs parallel to plane, resulting from the cohesion of two kinds of metallic chains. IR spectrum confirms the presence of characteristic bands from P3O10 phosphate group.

1. Introduction

Phosphates containing polyanions ( and 2) have been intensively investigated during the last few decades because of their applications in different fields: solid electrolytes for energy stockage, Li-ion batteries, ceramics, luminescence, and magnetism [1]. Kanonerovite, Na3MnP3O10·12H2O, is a natural triphosphate mineral [2]; few other synthetic triphosphates have been reported in the literature: Na3CuP3O10·12H2O [3], LiZn2P3O10·8H2O [4], NaZn2P3O10·9H2O [5], and Na3CdP3O10·12H2O [6]. Anhydrous triphosphates have been also studied: LiFe2P3O10 [7], LiM2P3O10, M = Co and Ni [8, 9], RbBe2P3O10 [10], Cs2MP3O10 (M = Ga, Al, Cr) [11]. These latter ternary phosphates, with the frameworks consisting in associated [PO4] and [MO6], are efficiently used for waste storage hosts [12]. We deal in the present work with the synthesis and structural study of two new hydrated phases: Na3MP3O10·12H2O, M = Co (1) and Ni (2).

2. Experimental

2.1. Synthesis

The title compounds Na3M(P3O10)·12H2O (M = Co (1), Ni (2)) were obtained by mixing two solutions made of following reactants, each dissolved in 10 mL distilled water: Na5P3O10 (0.3219 g) and, respectively, CoCl2·6H2O (0.2378 g) (1) and NiCl2·6H2O (0.2375 g) (2). The mixtures were stirred for 1 h and then allowed to stand at room temperature. After 2 weeks pink crystals of compound (1) and light green crystals of compound (2) were collected by filtration. The crystals were washed with a water-ethanol (80 : 20 v/v) mixture.

2.2. Single Crystal Study

The X-ray diffraction data for (1) and (2) were collected in a four-circles diffractometer Gemini of Oxford Diffraction (now Agilent Technologies), using graphite monochromatized CuKα radiation (  Å) collimated by mirrors, detector Atlas. The intensity data were corrected for Lorentz and polarization effects. A numerical absorption correction based on the crystal shape was carried out with the program CrysAlis RED [13]. The structures were solved by Superflip program [14] and refined by a full-matrix least-squares technique based on with Jana2006 [15]. Both compounds were found to be systematically twinned by 180° rotation around . The refined volume fraction of the major twin domain was 0.628(1) for both samples, confirming exactly the same kind of twinning. Only the major twin domain reflections were used in the refinement, using the twinning matrix for different scaling of the fully overlapped reflections. Influence of possible partial overlaps was negligible, without any need to use hklf5 approach. All nonhydrogen atoms were refined with anisotropic displacement parameters. Positions of hydrogen atoms belonging to water molecules were found in the difference Fourier map and refined with a restrain on their distance to the parent oxygen atom. Their isotropic temperature parameters were calculated as of the parent oxygen. Table 1 reports the crystallographic data and experimental details about data collection and structure refinements, while selected bond distances are in Table 2. The structural graphics were created using DIAMOND program [16].


Structural data(1)(2)

Empirical formulaNa3CoP3O10·12H2ONa3NiP3O10·12H2O
Formula weight (g/mol)597596.8
Temperature (K)120120
Wavelength Mo (Å)1.541841.54184
Crystal system, space groupMonoclinic, P21/n Monoclinic, P21/n
Unit cell dimensions
a (Å), α (°)15.0263(3), 9014,9906(4), 90
b (Å), β (°)9.1972(2), 90.0492(16)9,1628(2), 90.098(2)
c (Å), γ (°)14.6654(3), 90
14,6660(4), 90
Volume (Å3), Z 2026.76(7), 42014.46(9), 4
(Mg/m3)1.95591.967
Absorption coefficient (mm−1)10.4995.267
F(000)12201224
Crystal size (mm)0.3416 * 0.1882 * 0.1274
0.5021 * 0.0801 * 0.0527
Crystal shape, colourPrism, pinkNeedle, colorless
Limiting indices
Reflections collected35343181
Independent reflections34563107
DiffractometerOxford Diffraction Ltd.Oxford Diffraction Ltd.
Data/restraints/parameters3534/24/3363181/24/336
Goodness-of-fit on 1.612.11
Final R indices = 0.0261, = 0.0735 = 0.0277, = 0.0904
R indices (all data) = 0.0267, = 0.0738 = 0.0284, = 0.0907

(a)

Co(1)O6 in Na3CoP3O10·12H2O
Co1O2O6O9O11O12O19

O22,061(2)90,35(8)94,87(8)91,45(8)171,96(8)91,01(8)
O690,35(8)2,141(2)90,43(8)177,32(8)85,90(8)85,98(8)
O994,87(8)90,43(8)2,060(2)91,40(8)92,27(8)173,13(8)
O1191,45(8)177,32(8)91,40(8)2,116(2)92,07(8)91,99(8)
O12171,96(8)85,90(8)92,27(8)92,07(8)2,098(2)81,64(8)
O1991,01(8)85,98(8)173,13(8)91,99(8)81,64(8)2,142(2)

d(Co–O) = 2,103(2)Å, ∠(O; Co; O)> range from 81,64(8) to 177,32(8)°.
(b)

P3O10 in Na3CoP3O10·12H2O
P1O1O2O3O4

O11,505(2)112,1(1)114,5(1)107,0(1)
O2112,1(1)1,523(2)111,7(1)107,7(1)
O3114,5(1)111,7(1)1,510(2)103,0(1)
O4107,0(1)107,7(1)103,0(1)1,619(2)

P2O4O5O6O7

O41,594(2)109,1(1)109,1(1)100,9(1)
O5109,1(1)1,479(2)120,0(1)105,5(1)
O6109,1(1)120,0(1)1,495(2)110,5(1)
O7100,9(1)105,5(1)110,5(1)1,594(2)

P3O7O8O9O10

O71,624(2)106,5(1)107,8(1)102,3(1)
O8106,5(1)1,506(2)112,2(1)113,4(1)
O9107,8(1)112,2(1)1,519(2)113,8(1)
O10102,3(1)113,4(1)113,8(1)1,521(2)

∠(P1; O4; P2) = 158,3(2)°, d(P–OINT) = 1.603 Å, d(P–OTER) = 1.500 Å, d(P–OALL) = 1,553 Å.
∠(P2; O7; P3) = 70.9(2)°, d(P–OINT) = 1.609 Å, d(P–OTER) = 1.5507 Å, d(P–OALL) = 1.5798 Å.
(c)

Ni(1)O6 in Na3NiP3O10·12H2O
Ni1O2O6O9O11O12O19

O22,046(2)90,91(9)93,51(9)90,12(9)173,7(1)91,51(9)
O690,91(9)2,081(2)91,32(9)178,45(9)86,63(9)86,27(9)
O993,51(9)91,32(9)2,052(2)89,76(9)92,41(1)174,5(1)
O1190,12(9)178,45(9)89,76(9)2,067(2)92,22(9)92,55(9)
O12173,7(1)86,63(9)92,41(1)92,22(9)2,065(3)82,5(1)
O1991,51(9)86,27(9)174,5(1)92,55(9)82,5(1)2,097(3)

d(Ni–O) = 2,0615(2) Å, ∠(O; Ni; O)> range from 82,5(1)°–178,45(9)°
(d)

P3O10 in Na3NiP3O10·12H2O
P1O1O2O3O4

O11,501(3)112,5(1)114,3(1)106,91(1)
O2112,5(1)1,524(2)111,7(1)107,7(1)
O3114,3(1)111,7(1)1,513(2)103,0(1)
O4106,91(1)107,7(1)103,0(1)1,624(3)

P2O4O5O6O7

O41,589(3)109,2(1)108,9(1)100,9(1)
O5109,2(1)1,480(2)119,5(1)106,0(1)
O6108,9(1)119,5(1)1,499(2)110,7(1)
O7100,9(1)106,0(1)110,7(1)1,592(3)

P3O7O8O9O10

O71,627(2)106,0(1)107,7(1)102,4(1)
O8106,0(1)1,508(2)112,1(1)113,2(1)
O9107,7(1)112,1(1)1,520(2)114,4(1)
O10102,4(1)113,2(1)114,4(1)1,516(2)

∠(P1; O4; P2) = 157.2(2)°, d(P–OINT) = 1.606 Å, d(P–OTER) = 1.5051 Å, d(P–OALL) = 1,553 Å.
∠(P2; O7; P3) = 71.3(2)°, d(P–OINT) =1,6095 7 Å, d(P–OTER) = 1.551 Å, d(P–OALL) = 1.5802 Å.

Supplementary tables of crystal structures and refinements, notably atomic positions, full list of bond lengths and angles, and anisotropic thermal parameters, have been deposited with the Inorganic Crystal Structure Database, FIZ, Hermann von Helmholtz Platz 1, 76344 EggensteinLeopoldshafen, Germany; fax: (+49) 7247 808 132; email: crysdata@fiz-karlsruhe.de. CCDC deposition numbers are, respectively, 884535 for Na3Co(P3O10)·12H2O and 884536 for Na3Ni(P3O10)·12H2O.

2.3. IR Measurements

The infrared measurements were performed in transmission geometry using an FTIR Biorad spectrometer FTS-40A with dynamic alignment and a spectral resolution of 2 cm−1 in the range 400–4000 cm−1. 0.2 mg sample per 200 mg KBr has been pressed into pellets.

3. Results and Discussions

Na3MP3O10·12H2O [M = Co (1), Ni (2)] are isostructural, made by slabs parallel to plane (Figure 1). A slab results from the cohesion of two kinds of metallic chains, C1 and C2 (Figure 2). The chain C1 consists of [Na(2)O6] octahedra sharing the edge O15-O16 (water molecules) with strongly deformed tetragonal pyramid [Na(3)O5]. Such dimmers share a corner O5 (oxygen of P2). In the chain C2, [Na(1)O6] and [MO6] octahedra share the face O6 (oxygen of P2), O12 (water), and O19 (water), and they are further connected by a corner O11 (water). The details of the connection between the chains C1 and C2 through O–P–O bridges from the P3O10 phosphate groups are shown in Figure 3. Two parallel sheets are connected by hydrogen bonds, the most pronounced ones are reported in Table 3. The octahedra [MO6] (M = Co, Ni) are not directly connected in the structures, the shortest Co–Co and Ni–Ni distances are almost the same, respectively, 5.069(6), and 5.068(7)  Ǻ.

(a)

(1)
D–HHAD–AD–HA

O11–H11AO8i0.82(3)1.92(3)2.741(3)174(3)
O11–H11BO3i0.82(3)1.90(3)2.707(3)169(3)
O12–H12AO2i0.82(3)1.95(3)2.763(3)169(3)
O12–H12BO20i0.823(19)1.87(2)2.685(3)171(3)
O13–H13BO10ii0.83(3)1.95(3)2.768(3)172(3)
O14–H14AO1ii0.82(2)1.95(2)2.757(3)167(3)
O14–H14BO10.83(2)1.92(2)2.735(3)169(4)
O17–H17AO3i0.82(3)1.95(3)2.756(3)171(3)
O17–H17BO1iii0.82(3)1.87(3)2.691(3)174(4)
O19–H19AO9i0.82(2)1.96(2)2.773(3)171(4)
O19–H19BO14iv0.820(19)1.91(2)2.728(3)174(3)
O20–H20BO10v0.822(14)1.893(14)2.712(3)174(4)

(i) , , ; (ii) , , ; (iii) , , ; (iii) , , ; (iv) , , ; (v) , , .
(b)

(2)
D–HHA D–AD–HA

O11–H11AO80.82(3) 1.91(3) 2.736(3) 176(3)
O12–H12AO20.82(3) 1.88(3) 2.760(3) 173(4)
O12–H12BO200.82(2) 1.88(3) 2.694(4)173(4)
O16–H16AO180.821(16) 1.965(18)2.784(4)175(4)
O18–H18AO21i0.82(3) 1.93(3) 2.748(4)170(3)
O18–H18BO10ii0.82(3) 1.96(3)2.775(3)177(4)
O19–H19AO9iii0.82(3)1.96(3) 2.775(3) 171(4)
O19–H19BO140.82(2) 1.92(3) 2.735(4) 174(4)
O22–H22BO13iv0.82(3) 2.01(3) 2.835(4) 180(4)

(i) , , ; (ii) , ; (iii) , ; (iv) , .

Phosphorous ( ) atoms occupy three symmetrically independent tetrahedrally coordinated positions. The [PO4] share an apex to build up the triphosphate polyanion P3O10. Average distances P–O in P(1)O4, P(2)O4, and P(3)O4 are, respectively, 1.5292, 1.5404, and 1.5423 Ǻ  (see Table 2 for details), which are of the same magnitude as the values reported in Na3Cu(P3O10)·12H2O [3] and Na3Cd(P3O10)·12H2O [6]. P3O10 could be viewed as a combination of two P2O7 groups, characterized by the P–O–P angle 133.61(14) and 132.02(13) in (1) and 129.08(14) and 131.36(15) in (2), which is also comparable with the already mentioned known phases. The phosphate group P3O10 acts differently towards metals, being, respectively, monodentate and tridentate with respect to the coordination of Na and M.

The Infrared spectra of (1) and (2) are almost identical, they were recorded in the spectral zone 4000–400 cm−1. Figure 4 depicts the spectrum from the Co phase. Its interpretation can be made on the basis of characteristic vibrations of PO3 group, POP bridge, and H2O molecules. Band assignments (Table 4) have been obtained by comparing the results of data reported for known compounds [1]. The asymmetric and symmetric terminal stretching vibrations of the PO3 groups usually occur in the region 1250–975 cm−1. The bands observed at 1138.75 and 1113.68 cm−1 and 1168.84 cm−1 are assigned to the asymmetric terminal stretching vibration of the PO3 group (PO3).


Frequency ν (cm−1)Assigned vibration mode

3455νO–H
1648 H–OH
1241 PO2
1204 PO2
1090 PO2
986 PO3
910 POP
690ν POP
526δ PO3

The POP bridge vibrations always occur at lower frequency than the terminal P–O stretching modes. In the IR spectra, the asymmetric mode (POP) gives rise to a band at 872.63 cm−1. Symmetric bridge vibrations (POP) appear in the IR spectra at 767.52 cm−1. The broad bands in the region (3450–3000 cm−1) are assigned to the stretching of water molecules (H2O). The bands appearing in the spectral region 2900–2000 cm−1 are assigned to the O–H vibrations. Several other weak and medium intensity bands are due to the presence of multiple hydrogen bonds and the field correlation effect. The doublet near 1630 cm−1 corresponds to the bending of water molecules (H2O).

4. Conclusion

Crystals of the title compounds have been synthesized using a wet chemistry route. Na3MP3O10·12H2O (M = Co, Ni) are isostructural and their framework can be described as two kinds of chains connected through O–P–O of P3O10 phosphate groups into slabs parallel with . The slabs are connected only by hydrogen bonds. IR spectra of the two compounds reveal typical P3O10 bands known for phosphates.

Acknowledgment

The authors would like to thank the Grant Agency of the Czech Republic, Grant P204/11/0809.

References

  1. D. E. C. Corbridge, Ed., Phosphorus, Elsevier, Amsterdam, The Netherlands, 1990.
  2. V. I. Popova, V. A. Popov, E. V. Sokolova, G. Ferraris, and N. V. Chukanov, “Kanonerovite, MnNa3P3O10·12H2O, first triphosphate mineral,” Neues Jahrbuch fur Mineralogie, Monatshefte, no. 3, pp. 117–127, 2002. View at: Google Scholar
  3. O. Jouini, M. Dabbabi, M. T. Averbuch-Pouchot, A. Durif, and J. C. Guitel, “Structure du triphosphate de cuivre(II) et de trisodium dodécahydraté, CuNa3P3O10.12H2O,” Acta Crystallographica, vol. C40, pp. 728–730, 1984. View at: Publisher Site | Google Scholar
  4. A. S. Lyakhov, V. A. Lyutsko, L. I. Prodan, and K. K. Palkina, “Crystal structure of Lithium Zinc Triphosphate Octahydrate LiZn2P3O10·8H2O,” Inorganic Materials, vol. 27, no. 5, pp. 845–849, 1991. View at: Google Scholar
  5. M. T. Averbuch-Pouchot and J. C. Guitel, “Structure cristalline du tripolyphosphate mixte zinc-sodium nonahydraté: Zn2NaP3O10.9H2O,” Acta Crystallographica, vol. B33, pp. 1427–1431, 1977. View at: Publisher Site | Google Scholar
  6. V. Lutsko and G. Johansson, “The Crystal structure of trisodium cadmium triphosphate Na3CdP3O10[H2O]12,” Acta Chemica Scandinavica, vol. A38, no. 5, pp. 415–417, 1984. View at: Google Scholar
  7. M. Kopec, C. V. Ramana, X. Zhang et al., “Synthesis, characterization and electrochemical properties of a novel triphosphate LiFe2P3O10,” Electrochimica Acta, vol. 54, no. 23, pp. 5500–5508, 2009. View at: Publisher Site | Google Scholar
  8. F. Breach, A. Boukhari, and E. M. Holt, “Lithium dicobalt tripolyphosphate and lithium dinickel tripolyphosphate,” Acta Crystallographica Section C, vol. 52, no. 8, pp. 1867–1869, 1996. View at: Google Scholar
  9. K. Rissouli, K. Benkhouja, A. sadel et al., “A new type of triphosphate group: crystal structure and magnetic properties of Co2LiP3O10,” European Journal of Solid State and Inorganic Chemistry, vol. 34, pp. 221–230, 1997. View at: Google Scholar
  10. M.-T. Averbuch-Pouchot and A. Durif, “Synthese et structure cristalline du dihydrogenodiphosphate de caesium,” Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, vol. 316, no. 2, pp. 609–617, 1993. View at: Google Scholar
  11. A. Guesdon, E. Daguts, and B. Raveau, “A series of cesium triphosphates with a layer structure: Cs2MP3O10 (M=Ga, Al, Cr),” Journal of Solid State Chemistry, vol. 167, no. 1, pp. 258–264, 2002. View at: Publisher Site | Google Scholar
  12. E. H. Oelkers and J. M. Montel, “Phosphates and nuclear waste storage,” Elements, vol. 4, no. 2, pp. 113–116, 2008. View at: Publisher Site | Google Scholar
  13. Agilent, Crysalis PRO, Agilent Technologies, Yarnton, UK, 2010.
  14. L. Palatinus and G. Chapuis, “Superflip—a computer program for the solution of crystal structures by charge flipping in arbitrary dimensions,” Journal of Applied Crystallography, vol. 40, no. 4, pp. 786–790, 2007. View at: Publisher Site | Google Scholar
  15. V. Petříček, M. Dušek, and L. Palatinus, Structure Determination Software Programs, Institute of Physics, Praha, Czech Republic, 2007.
  16. K. Brandenburg and H. Putz, Diamond Version 3, Crystal Impact GbR, Bonn, Germany, 2005.

Copyright © 2012 Khalil Azzaoui et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


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