Redetermination of the low-temperature polymorph of Li2MnSiO4 from single-crystal X-ray data

Sato, M.; Ishigaki, T.; Uematsu, K.; Toda, K.; Okawa, H.

doi:10.1107/S1600536812035040

Volume 68
Part 9
Pages i68-i69
September 2012

Received 5 July 2012
Accepted 8 August 2012
Online 15 August 2012

Key indicators
Single-crystal X-ray study
T = 295 K
Mean (Si-O) = 0.002 Å
R = 0.015
wR = 0.037
Data-to-parameter ratio = 9.4
Details

Redetermination of the low-temperature polymorph of Li₂MnSiO₄ from single-crystal X-ray data

Mineo Sato,^a ^* Tadashi Ishigaki,^b Kazuyoshi Uematsu,^a Kenji Toda ^c and Hirokazu Okawa ^d

^aDepartment of Chemistry and Chemical Engineering, Faculty of Engineering, Niigata University, Ikarashi 2-no-cho, Niigata City 950-2181, Japan,^bCenter for Transdiciplinary Research, Niigata University, 8050 Ikarashi 2-no-cho, Niigata 950-2181, Japan,^cGraduate School of Science and Technology, Niigata University, 8050 Ikarashi 2-nocho, Niigata 950-2181, Japan, and ^dDepartment of Earth Science and Technology, Faculty of Engineering and Resource Science, Akita University, Tegata Gakuen-machi, Akita 010-8502, Japan
Correspondence e-mail: msato@eng.niigata-u.ac.jp

Crystals of dilithium manganese(II) silicate were grown under high-temperature hydrothermal conditions in the system LiOH-MnO₂-SiO₂. The title compound crystallizes in the [beta] _II-Li₃PO₄ structure type. The coordination polyhedra of all cations are slightly distorted tetrahedra (m symmetry for MnO₄ and SiO₄), which are linked by corner-sharing to each other. The vertices of the tetrahedra point to the same direction perpendicular to the distorted hexagonal close-packed (hcp) array of O atoms within which half of the tetrahedral voids are occupied by cations. In comparison with the previous refinement from powder X-ray data [Dominko et al. (2006). Electrochem. Commun. 8, 217-222], the present reinvestigation from single-crystal X-ray data allows a more precise determination of the distribution of the Li⁺ and Mn²⁺ cations, giving a perfectly site-ordered structure model for both Li⁺ and Mn²⁺.

Related literature

For background to structural studies of Li₂MSiO₄ (M = Mn, Fe, Co) compounds, see: Islam et al. (2011); Santamaría-Pérez et al. (2012); Setoguchi (1988); Yamaguchi et al. (1979). Polymorphism of Li₂MnSiO₄ was reported by Arroyo-de Dompablo et al. (2006, 2008); Belharouak et al. (2009); Dominko et al. (2006); Kokalj et al. (2007); Politaev et al. (2007); Wu et al. (2009); Zhong et al. (2010). For notation of Li₃PO₄ polymorphs, see: West & Glasser (1972). For theoretical studies of the redox potentials and Li migration paths of Li₂MnSiO₄, see: Kuganathan & Islam (2009); Mali et al. (2010); Duncan et al. (2011), and for NMR studies of this material, see: Sirisopanaporn et al. (2011). For the bond-valence method, see: Brown & Altermatt (1985). For crystallographic background, see: Cooper et al. (2002).

Experimental

Crystal data

Li₂MnSiO₄
M_r = 160.91
Orthorhombic, P m n 2₁
a = 6.3133 (16) Å
b = 5.3677 (14) Å
c = 4.9685 (12) Å
V = 168.37 (7) Å³
Z = 2
Mo K radiation
= 4.11 mm^-1
T = 295 K
0.26 × 0.19 × 0.18 mm

Data collection

Rigaku Mercury375R diffractometer
Absorption correction: multi-scan (REQAB; Rigaku, 1998) T_min = 0.377, T_max = 0.477
1636 measured reflections
423 independent reflections
419 reflections with I > 2(I)
R_int = 0.019

Refinement

R[F² > 2(F²)] = 0.015
wR(F²) = 0.037
S = 1.14
423 reflections
45 parameters
1 restraint
_max = 0.25 e Å^-3
_min = -0.62 e Å^-3
Absolute structure: Flack (1983), 189 Friedel pairs
Flack parameter: 0.171 (15)

Table 1
Selected geometric parameters (Å, °)

Li1-O1ⁱ	1.936 (10)
Li1-O3	1.956 (6)
Li1-O3ⁱⁱ	1.99 (2)
Li1-O2ⁱⁱⁱ	2.009 (6)
Mn1-O3^iv	2.0585 (16)
Mn1-O1	2.065 (2)
Mn1-O2	2.090 (2)
Si1-O1^v	1.631 (3)
Si1-O3	1.6331 (17)
Si1-O2^vi	1.639 (2)

O1ⁱ-Li1-O3	112.0 (7)
O1ⁱ-Li1-O3ⁱⁱ	107.5 (5)
O3-Li1-O3ⁱⁱ	107.7 (7)
O1ⁱ-Li1-O2ⁱⁱⁱ	108.6 (6)
O3-Li1-O2ⁱⁱⁱ	113.9 (5)
O3ⁱⁱ-Li1-O2ⁱⁱⁱ	106.8 (6)
O3^iv-Mn1-O3	124.58 (8)
O3^iv-Mn1-O1	105.74 (5)
O3^iv-Mn1-O2	107.31 (6)
O1-Mn1-O2	104.54 (8)
O1^v-Si1-O3	109.35 (10)
O3-Si1-O3^vii	109.58 (13)
O1^v-Si1-O2^vi	108.23 (13)
O3-Si1-O2^vi	110.16 (10)
Symmetry codes: (i) x, y-1, z; (ii) $[-x+{\script{3\over 2}}, -y, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, -y, z+{\script{1\over 2}}]$ ; (iv) -x+1, y, z; (v) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (vi) $[-x+{\script{3\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (vii) -x+2, y, z.

Table 2
Bond-valence parameters derived from the present model and the previous studies.

Atom	Site	Present work	Dominko et al.¹⁾	Arroyo-de Dompablo et al.²⁾
Li	4b	1.02 (6)	1.0 (1)	0.9
Mn	2a	1.89 (5)	2.1 (1)	1.77
Si	2a	3.89 (7)	3.6 (2)	3.65
O1	2a	2.02 (9)	1.9 (3)	1.75
O2	4b	1.97 (7)	1.9 (2)	1.86
O3	2a	1.87 (7)	2.0 (2)	1.90
1) The data, referred to Dominko et al. (2006), are based on the coordinates for primary MO₄ (M = Li, Mn, Si) tetrahedra. 2) The data, referred to Arroyo-de Dompablo et al. (2008), are based on the coordinates for primary MO₄ (M = Li, Mn, Si) tetrahedra optimized by density functional theory (DFT) methods.

Data collection: CrystalClear (Rigaku, 2010); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: VESTA (Momma & Izumi, 2011); software used to prepare material for publication: WinGX (Farrugia, 1999).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2658 ).

References

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inorganic compounds