inorganic compounds
Dilithium manganese(II) catena-tetrakis(polyphosphate), Li2Mn(PO3)4
aLaboratoire de Physico-Chimie des Matériaux Inorganiques, Faculté des Sciences Aïn Chock, Casablanca, Morocco, and bLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Batouta, BP 1014, Rabat, Morocco
*Correspondence e-mail: moutataouia_m@yahoo.fr
The poly-phosphate Li2Mn(PO3)4 was synthesized and its structure characterized from powder diffraction data by Averbuch-Pouchot & Durif [J. Appl. Cryst. (1972), 5, 307–308]. These authors showed that the structure of this phosphate is isotypic to that of Li2Cd(PO3)4, as confirmed by the present work. The structure is built from infinite zigzag polyphosphate chains, [(PO3)−]n, extending along [010]. These polyphosphate chains are connected by sharing vertices with MnO6 octahedra (site symmetry .m.) and Li2O7 polyhedra, which form also chains parallel to [010]. Adjacent chains are linked by common vertices of polyhedra in such a way as to form porous layers parallel to (100). The three-dimensional framework delimits empty channels extending along [010].
CCDC reference: 974169
Related literature
For potential applications of lithium and manganese phosphates, see: Parada et al. (2003); Jouini et al. (2003); Bian et al. (2003); Aravindan et al. (2013); Drezen et al. (2007); Bakenov & Taniguchi (2010); Adam et al. (2008). For a previous from powder data, see: Averbuch-Pouchot & Durif (1972). For the isotypic structure of Li2Cd(PO3)4, see: Averbuch-Pouchot et al. (1976).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
CCDC reference: 974169
https://doi.org/10.1107/S1600536813032388/br2233sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813032388/br2233Isup2.hkl
The synthesis of the polyphosphate Li2MnP4O12 by wet process, was made starting from the stoechiometric proportions of (LiNO3 99,9%) (I); (Mn(NO3)2,4H2O 99%) (II) and ((NH4)2HPO4 99%) (III). The starting reagents were made in distilled water solution. A drop by drop of the solution (II) was added on the solution (I), under mechanical agitation, and thereafter the solution (III). The mixture is carried to 373 K until total evaporation of the solution. The residue thus obtained was heated in air, intersected with grindings, until a final temperature of 773 K during 4 h. The final products are of violet colour.
The previous powder of the Li2MnP4O12 phase synthesized by wet process introduced into a platinum crucible, then carried gradually heated at a temperature higher than its melting point (973 K) during 2 h, followed-up by a slow cooling about 5 °K per hour until 773 K. Then, the power supply of the furnace is cut, and cooling is continued until the ambient temperature. The single crystals obtained are of violet colour.
The highest peak and the deepest hole in the final Fourier map are at 0.51 Å and 0.97 Å, from O3 and P1, respectively. The not significant bonds and angles were removed from the
file.Due to their interesting physical properties, the lithium and manganese phosphates have a wide domain of applications (Parada et al., 2003; Jouini et al., 2003; Bian et al., 2003). Among these mixed phosphates, the LiMnPO4 monophosphate is the most studied, followed by the Li2MnP2O7 diphosphate and the Li2Mn(PO3)4 polyphosphate, which is the object of this work. These phosphate materials are being extensively studied as lithium-ion battery electrodes (Aravindan et al., 2013; Drezen et al., 2007; Bakenov & Taniguchi, 2010; Adam et al., 2008).
Averbuch-Pouchot & Durif (1972) have synthesized the powder of the polyphosphate Li2Mn(PO3)4 and have shown that the structure of this phosphate is isotype to that of Li2Cd(PO3)4 (Averbuch-Pouchot et al., 1976). The present paper describes the
of the title compound from single-crystal X-ray diffraction data.The partial three-dimensional plot in Fig.1 illustrates the connection ion-oxygen polyhedra in the
of the title compound. The phosphorous atoms have a tetrahedral environment with P–O distances varying between 1.4650 (9) Å and 1.5932 (7) Å and the angles O–P–O are in the range of 95.22 (5)–119.93 (5) °. These value are within the limits generally observed in the crystal chemistry of condensed phosphate. The Mn2+ cation is surrounded by a roughly octahedral arrangement of six oxygen atoms and share one edge with Li2O7 polyhedron in which each Li is coordinated to five oxygen atoms.The structure of Li2Mn(PO3)4 consists of edge-sharing [MnO6] octahedra and [Li2O7] polyhedra forming an infinite linear chains [Mn–Li–Li–Mn] running parallel to [100], as shown in Fig.2. The (PO3)-n polyphosphate form also infinite zigzag chains propaging along b axis. Adjacent chains are linked together by common vertices of polyhedra in such a way as to form porous layers parallel to (100). The resulting 3-D framework presents empty tunnels running along [010] directions (Fig.2).
For potential applications of lithium and manganese phosphates, see: Parada et al. (2003); Jouini et al. (2003); Bian et al. (2003); Aravindan et al. (2013); Drezen et al. (2007); Bakenov & Taniguchi (2010); Adam et al. (2008). For a previous
from powder data, see: Averbuch-Pouchot & Durif (1972). For the isotypic structure of Li2Cd(PO3)4, see: Averbuch-Pouchot et al. (1976).Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).Li2Mn(PO3)4 | F(000) = 748 |
Mr = 384.70 | Dx = 2.893 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 2520 reflections |
a = 9.4295 (2) Å | θ = 3.0–38.1° |
b = 9.2755 (2) Å | µ = 2.29 mm−1 |
c = 10.0972 (2) Å | T = 296 K |
V = 883.13 (3) Å3 | Block, violet |
Z = 4 | 0.23 × 0.16 × 0.13 mm |
Bruker X8 APEX diffractometer | 2520 independent reflections |
Radiation source: fine-focus sealed tube | 2318 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
φ and ω scans | θmax = 38.1°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008) | h = −16→13 |
Tmin = 0.651, Tmax = 0.743 | k = −16→13 |
13605 measured reflections | l = −11→17 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.018 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.051 | w = 1/[σ2(Fo2) + (0.0262P)2 + 0.2295P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
2520 reflections | Δρmax = 0.52 e Å−3 |
97 parameters | Δρmin = −0.51 e Å−3 |
Li2Mn(PO3)4 | V = 883.13 (3) Å3 |
Mr = 384.70 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 9.4295 (2) Å | µ = 2.29 mm−1 |
b = 9.2755 (2) Å | T = 296 K |
c = 10.0972 (2) Å | 0.23 × 0.16 × 0.13 mm |
Bruker X8 APEX diffractometer | 2520 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008) | 2318 reflections with I > 2σ(I) |
Tmin = 0.651, Tmax = 0.743 | Rint = 0.024 |
13605 measured reflections |
R[F2 > 2σ(F2)] = 0.018 | 97 parameters |
wR(F2) = 0.051 | 0 restraints |
S = 1.09 | Δρmax = 0.52 e Å−3 |
2520 reflections | Δρmin = −0.51 e Å−3 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against all reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on all data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.012320 (17) | 0.2500 | 0.697042 (16) | 0.00824 (4) | |
P1 | 0.30533 (3) | 0.2500 | 0.39321 (3) | 0.00708 (5) | |
P2 | 0.29220 (2) | 0.03744 (2) | 0.610286 (19) | 0.00742 (4) | |
P3 | 0.22718 (3) | 0.2500 | 0.98429 (3) | 0.00661 (5) | |
O1 | 0.14967 (9) | 0.2500 | 0.37467 (9) | 0.01356 (15) | |
O2 | 0.40037 (9) | 0.2500 | 0.27630 (8) | 0.01232 (14) | |
O3 | 0.35189 (7) | 0.11634 (8) | 0.48227 (7) | 0.01946 (13) | |
O4 | 0.13548 (6) | 0.05951 (7) | 0.62027 (6) | 0.01146 (10) | |
O5 | 0.38358 (7) | 0.07235 (7) | 0.72611 (7) | 0.01537 (11) | |
O6 | 0.32753 (6) | −0.12374 (7) | 0.57702 (7) | 0.01270 (10) | |
O7 | 0.14661 (10) | 0.2500 | 0.86024 (9) | 0.01801 (18) | |
O8 | 0.38557 (9) | 0.2500 | 0.98024 (8) | 0.01291 (15) | |
Li1 | 0.0036 (2) | 0.1031 (3) | 0.3305 (3) | 0.0319 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.00776 (6) | 0.00889 (7) | 0.00807 (7) | 0.000 | −0.00102 (5) | 0.000 |
P1 | 0.00667 (10) | 0.00812 (11) | 0.00646 (10) | 0.000 | 0.00036 (7) | 0.000 |
P2 | 0.00715 (7) | 0.00576 (8) | 0.00935 (8) | −0.00010 (5) | 0.00026 (5) | −0.00046 (6) |
P3 | 0.00626 (10) | 0.00710 (11) | 0.00645 (10) | 0.000 | −0.00036 (7) | 0.000 |
O1 | 0.0071 (3) | 0.0192 (4) | 0.0144 (3) | 0.000 | −0.0017 (3) | 0.000 |
O2 | 0.0121 (3) | 0.0163 (4) | 0.0086 (3) | 0.000 | 0.0034 (3) | 0.000 |
O3 | 0.0135 (2) | 0.0205 (3) | 0.0243 (3) | 0.0064 (2) | 0.0071 (2) | 0.0153 (3) |
O4 | 0.0076 (2) | 0.0110 (2) | 0.0158 (2) | 0.00088 (18) | 0.00164 (17) | −0.0008 (2) |
O5 | 0.0134 (2) | 0.0165 (3) | 0.0162 (3) | −0.0019 (2) | −0.0040 (2) | −0.0070 (2) |
O6 | 0.0125 (2) | 0.0068 (2) | 0.0188 (3) | 0.00120 (18) | −0.0044 (2) | −0.0039 (2) |
O7 | 0.0158 (4) | 0.0279 (5) | 0.0103 (3) | 0.000 | −0.0058 (3) | 0.000 |
O8 | 0.0065 (3) | 0.0222 (4) | 0.0099 (3) | 0.000 | 0.0015 (2) | 0.000 |
Li1 | 0.0186 (8) | 0.0241 (10) | 0.0530 (14) | −0.0087 (7) | −0.0128 (8) | 0.0163 (10) |
Mn1—O7 | 2.0782 (9) | P2—O3 | 1.5885 (7) |
Mn1—O8i | 2.1523 (8) | P3—O7 | 1.4650 (9) |
Mn1—O5i | 2.1888 (6) | P3—O8 | 1.4941 (8) |
Mn1—O5ii | 2.1888 (6) | P3—O6iv | 1.5857 (6) |
Mn1—O4iii | 2.2519 (6) | P3—O6v | 1.5857 (6) |
Mn1—O4 | 2.2519 (6) | Li1—O1 | 1.988 (2) |
P1—O1 | 1.4797 (9) | Li1—O2vi | 1.992 (2) |
P1—O2 | 1.4821 (9) | Li1—O4vii | 2.060 (2) |
P1—O3iii | 1.5932 (7) | Li1—O5viii | 2.211 (3) |
P1—O3 | 1.5932 (7) | Li1—O8i | 2.598 (3) |
P2—O5 | 1.4883 (6) | Li1—Li1iii | 2.725 (5) |
P2—O4 | 1.4953 (6) | Li1—Mn1vii | 3.290 (2) |
P2—O6 | 1.5681 (6) | ||
O7—Mn1—O8i | 176.19 (4) | O5—P2—O6 | 104.64 (4) |
O7—Mn1—O5i | 93.26 (3) | O4—P2—O6 | 110.79 (4) |
O8i—Mn1—O5i | 89.25 (2) | O5—P2—O3 | 109.51 (4) |
O7—Mn1—O5ii | 93.26 (3) | O4—P2—O3 | 110.00 (4) |
O8i—Mn1—O5ii | 89.25 (2) | O6—P2—O3 | 100.93 (4) |
O5i—Mn1—O5ii | 97.67 (4) | O7—P3—O8 | 119.67 (5) |
O7—Mn1—O4iii | 87.63 (2) | O7—P3—O6iv | 109.64 (4) |
O8i—Mn1—O4iii | 90.01 (2) | O8—P3—O6iv | 109.97 (3) |
O5i—Mn1—O4iii | 177.06 (2) | O7—P3—O6v | 109.64 (4) |
O5ii—Mn1—O4iii | 79.48 (2) | O8—P3—O6v | 109.97 (3) |
O7—Mn1—O4 | 87.63 (2) | O6iv—P3—O6v | 95.22 (5) |
O8i—Mn1—O4 | 90.01 (2) | O1—Li1—O2vi | 89.50 (9) |
O5i—Mn1—O4 | 79.48 (2) | O1—Li1—O4vii | 152.74 (16) |
O5ii—Mn1—O4 | 177.06 (2) | O2vi—Li1—O4vii | 108.68 (9) |
O4iii—Mn1—O4 | 103.37 (3) | O1—Li1—O5viii | 106.16 (10) |
O1—P1—O2 | 119.93 (5) | O2vi—Li1—O5viii | 118.72 (14) |
O1—P1—O3iii | 110.17 (3) | O4vii—Li1—O5viii | 83.24 (9) |
O2—P1—O3iii | 106.43 (3) | O1—Li1—O8i | 76.84 (10) |
O1—P1—O3 | 110.17 (3) | O2vi—Li1—O8i | 80.21 (9) |
O2—P1—O3 | 106.43 (3) | O4vii—Li1—O8i | 86.20 (9) |
O3iii—P1—O3 | 102.18 (6) | O5viii—Li1—O8i | 160.51 (11) |
O5—P2—O4 | 119.30 (4) |
Symmetry codes: (i) x−1/2, y, −z+3/2; (ii) x−1/2, −y+1/2, −z+3/2; (iii) x, −y+1/2, z; (iv) −x+1/2, y+1/2, z+1/2; (v) −x+1/2, −y, z+1/2; (vi) x−1/2, y, −z+1/2; (vii) −x, −y, −z+1; (viii) −x+1/2, −y, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | Li2Mn(PO3)4 |
Mr | 384.70 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 296 |
a, b, c (Å) | 9.4295 (2), 9.2755 (2), 10.0972 (2) |
V (Å3) | 883.13 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.29 |
Crystal size (mm) | 0.23 × 0.16 × 0.13 |
Data collection | |
Diffractometer | Bruker X8 APEX |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2008) |
Tmin, Tmax | 0.651, 0.743 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13605, 2520, 2318 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.869 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.018, 0.051, 1.09 |
No. of reflections | 2520 |
No. of parameters | 97 |
Δρmax, Δρmin (e Å−3) | 0.52, −0.51 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).
Acknowledgements
The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.
References
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Due to their interesting physical properties, the lithium and manganese phosphates have a wide domain of applications (Parada et al., 2003; Jouini et al., 2003; Bian et al., 2003). Among these mixed phosphates, the LiMnPO4 monophosphate is the most studied, followed by the Li2MnP2O7 diphosphate and the Li2Mn(PO3)4 polyphosphate, which is the object of this work. These phosphate materials are being extensively studied as lithium-ion battery electrodes (Aravindan et al., 2013; Drezen et al., 2007; Bakenov & Taniguchi, 2010; Adam et al., 2008).
Averbuch-Pouchot & Durif (1972) have synthesized the powder of the polyphosphate Li2Mn(PO3)4 and have shown that the structure of this phosphate is isotype to that of Li2Cd(PO3)4 (Averbuch-Pouchot et al., 1976). The present paper describes the crystal structure of the title compound from single-crystal X-ray diffraction data.
The partial three-dimensional plot in Fig.1 illustrates the connection ion-oxygen polyhedra in the crystal structure of the title compound. The phosphorous atoms have a tetrahedral environment with P–O distances varying between 1.4650 (9) Å and 1.5932 (7) Å and the angles O–P–O are in the range of 95.22 (5)–119.93 (5) °. These value are within the limits generally observed in the crystal chemistry of condensed phosphate. The Mn2+ cation is surrounded by a roughly octahedral arrangement of six oxygen atoms and share one edge with Li2O7 polyhedron in which each Li is coordinated to five oxygen atoms.
The structure of Li2Mn(PO3)4 consists of edge-sharing [MnO6] octahedra and [Li2O7] polyhedra forming an infinite linear chains [Mn–Li–Li–Mn] running parallel to [100], as shown in Fig.2. The (PO3)-n polyphosphate form also infinite zigzag chains propaging along b axis. Adjacent chains are linked together by common vertices of polyhedra in such a way as to form porous layers parallel to (100). The resulting 3-D framework presents empty tunnels running along [010] directions (Fig.2).