Lithium samarium polyphosphate, LiSm(PO3)4

Zhao, D.; Li, F.; Cheng, W.; Zhang, H.

doi:10.1107/S1600536809055822

inorganic compounds

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Volume 66| Part 2| February 2010| Page i3

https://doi.org/10.1107/S1600536809055822

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Lithium samarium polyphosphate, LiSm(PO₃)₄

Dan Zhao,^a ^* Feifei Li,^a Wendan Cheng ^b and Hao Zhang ^b

^aDepartment of Physics and Chemistry, Henan Polytechnic University, Jiaozuo, Henan 454000, People's Republic of China, and ^bState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China
^*Correspondence e-mail: iamzd@hpu.edu.cn

(Received 19 October 2009; accepted 30 December 2009; online 9 January 2010)

The mixed-metal rare-earth polyphosphate LiSm(PO₃)₄ consists of a three-dimensional framework in which zigzag [(PO₃)_n]ⁿ⁻ chains with a periodicity of four PO₄ tetrahedra are connected through Li⁺ and Sm³⁺ ions (both with 2. symmetry).

Related literature

For the structures, properties and applications of condensed alkaline metal–rare earth polyphosphates with the general formula MLn(PO₃)₄ (M = alkali metal, Ln = rare earth metal), see: Ferid et al. (1984 ); Ettis et al. (2003 ); Parreu et al. (2007 ); Zhu et al. (2007 ); Ben Zarkouna et al. (2007 ).

Experimental

Crystal data

LiSm(PO₃)₄
M_r = 473.17
Monoclinic, C 2/c
a = 16.379 (2) Å
b = 7.0499 (9) Å
c = 9.6936 (12) Å
β = 126.138 (2)°
V = 903.96 (19) Å³
Z = 4
Mo Kα radiation
μ = 7.27 mm⁻¹
T = 298 K
0.20 × 0.15 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.439, T_max = 1.000
2405 measured reflections
854 independent reflections
843 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.048
S = 1.09
854 reflections
84 parameters
Δρ_max = 1.02 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809055822/mg2086sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809055822/mg2086Isup2.hkl

checkCIF report

Comment top

Interest in alkali-metal rare-earth polyphosphates stems from their physical properties, such as high luminescence efficiency (Ettis et al., 2003; Parreu et al., 2007; Zhu et al., 2007). The compound LiSm(PO₃)₄ has been reported but only unit cell parameters have been refined from powder X-ray diffraction data (Ferid et al., 1984). The single-crystal structure determination performed here confirms that it is isotypic with LiLn(PO₃)₄ (Ln = Y, La, Nd, Eu, Gd, Tb, Dy, Er, Yb) (Ben Zarkouna et al., 2007). The structure features two P sites (Fig. 1) centred within PO₄ tetrahedra, which share common corners (O2 or O6) to form infinite zigzag chains (PO₃)_n^n- that are aligned parallel to the b-direction and are linked together by four-coordinate Li⁺ and eight-coordinate Sm³⁺ ions (Fig. 2).

Related literature top

For the structures, properties and applications of condensed alkaline metal–rare earth polyphosphates with the general formula MLn(PO₃)₄ (M = alkali metal, Ln = rare earth metal), see: Ferid et al. (1984); Ettis et al. (2003); Parreu et al. (2007); Zhu et al. (2007); Ben Zarkouna et al. (2007).

Experimental top

Finely ground reagents Li₂CO₃, Sm₂O₃, and NH₄H₂PO₄ were mixed in a molar ratio of Li:Sm:P = 7:1:10, placed in a Pt crucible, and heated at 673 K for 4 h. The mixture was reground and heated at 1073 K for 20 h, cooled to 873 K at a rate of 4 K h^-1, and then quenched to room temperature. A few yellow prism-shaped crystals of the title compound were obtained.

Structure description top

For the structures, properties and applications of condensed alkaline metal–rare earth polyphosphates with the general formula MLn(PO₃)₄ (M = alkali metal, Ln = rare earth metal), see: Ferid et al. (1984); Ettis et al. (2003); Parreu et al. (2007); Zhu et al. (2007); Ben Zarkouna et al. (2007).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Part of the structure of LiSm(PO₃)₄ showing the labelling of all atoms. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Projection of the structure of LiSm(PO₃)₄ down the b axis.

lithium samarium polyphosphate top

Crystal data top

LiSm(PO₃)₄	F(000) = 884
M_r = 473.17	D_x = 3.477 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 487 reflections
a = 16.379 (2) Å	θ = 2.1–23.0°
b = 7.0499 (9) Å	µ = 7.27 mm⁻¹
c = 9.6936 (12) Å	T = 298 K
β = 126.138 (2)°	Prism, yellow
V = 903.96 (19) Å³	0.20 × 0.15 × 0.05 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	854 independent reflections
Radiation source: fine-focus sealed tube	843 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
φ and ω scans	θ_max = 25.7°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −20→19
T_min = 0.439, T_max = 1.000	k = −8→8
2405 measured reflections	l = −10→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.019	w = 1/[σ²(F_o²) + (0.0274P)² + 6.0112P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.048	(Δ/σ)_max = 0.001
S = 1.09	Δρ_max = 1.02 e Å⁻³
854 reflections	Δρ_min = −0.71 e Å⁻³
84 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0069 (3)

Crystal data top

LiSm(PO₃)₄	V = 903.96 (19) Å³
M_r = 473.17	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.379 (2) Å	µ = 7.27 mm⁻¹
b = 7.0499 (9) Å	T = 298 K
c = 9.6936 (12) Å	0.20 × 0.15 × 0.05 mm
β = 126.138 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	854 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	843 reflections with I > 2σ(I)
T_min = 0.439, T_max = 1.000	R_int = 0.023
2405 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	84 parameters
wR(F²) = 0.048	0 restraints
S = 1.09	Δρ_max = 1.02 e Å⁻³
854 reflections	Δρ_min = −0.71 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Li1	0.5000	0.2975 (12)	0.7500	0.014 (2)
Sm1	0.5000	0.20102 (3)	0.2500	0.00541 (15)
P1	0.36163 (7)	0.55515 (13)	0.33744 (11)	0.0057 (2)
P2	0.35188 (7)	0.15529 (14)	0.40335 (12)	0.0056 (2)
O1	0.3857 (2)	0.7182 (4)	0.4524 (4)	0.0117 (6)
O2	0.3410 (2)	0.3787 (4)	0.4149 (3)	0.0094 (5)
O3	0.4267 (2)	0.0930 (4)	0.5830 (3)	0.0104 (5)
O4	0.3705 (2)	0.1147 (4)	0.2737 (3)	0.0104 (5)
O5	0.43430 (19)	0.5038 (4)	0.2978 (3)	0.0094 (5)
O6	0.25564 (19)	0.5836 (4)	0.1557 (3)	0.0091 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Li1	0.018 (5)	0.011 (5)	0.016 (5)	0.000	0.011 (5)	0.000
Sm1	0.00650 (19)	0.00499 (19)	0.00591 (19)	0.000	0.00431 (14)	0.000
P1	0.0060 (4)	0.0046 (4)	0.0068 (5)	0.0004 (3)	0.0040 (4)	0.0004 (3)
P2	0.0059 (4)	0.0053 (4)	0.0062 (5)	−0.0005 (3)	0.0040 (4)	0.0004 (4)
O1	0.0130 (14)	0.0093 (14)	0.0112 (15)	−0.0007 (10)	0.0063 (13)	−0.0026 (10)
O2	0.0167 (13)	0.0052 (13)	0.0133 (13)	0.0000 (10)	0.0126 (12)	0.0009 (10)
O3	0.0108 (13)	0.0076 (12)	0.0094 (13)	0.0003 (10)	0.0041 (11)	0.0016 (10)
O4	0.0127 (13)	0.0110 (13)	0.0126 (13)	−0.0019 (11)	0.0102 (11)	−0.0026 (11)
O5	0.0076 (12)	0.0107 (13)	0.0111 (13)	0.0012 (10)	0.0061 (11)	0.0021 (10)
O6	0.0083 (12)	0.0125 (13)	0.0073 (12)	0.0027 (10)	0.0049 (11)	0.0012 (10)

Geometric parameters (Å, º) top

Li1—O3	1.962 (7)	Sm1—O5^iv	2.553 (3)
Li1—O3ⁱ	1.962 (7)	P1—O1	1.483 (3)
Li1—O5ⁱⁱ	1.980 (7)	P1—O5	1.495 (3)
Li1—O5ⁱⁱⁱ	1.980 (7)	P1—O2	1.590 (3)
Li1—P2	2.927 (3)	P1—O6	1.597 (3)
Li1—P2ⁱ	2.927 (3)	P1—Li1ⁱⁱⁱ	3.033 (3)
Li1—P1ⁱⁱ	3.033 (3)	P2—O4	1.485 (3)
Li1—P1ⁱⁱⁱ	3.033 (3)	P2—O3	1.487 (3)
Sm1—O4	2.345 (3)	P2—O6^viii	1.580 (3)
Sm1—O4^iv	2.345 (3)	P2—O2	1.596 (3)
Sm1—O1ⁱⁱⁱ	2.405 (3)	O1—Sm1ⁱⁱⁱ	2.405 (3)
Sm1—O1^v	2.405 (3)	O3—Sm1^vii	2.463 (3)
Sm1—O3^vi	2.463 (3)	O5—Li1ⁱⁱⁱ	1.980 (7)
Sm1—O3^vii	2.463 (3)	O6—P2^ix	1.580 (3)
Sm1—O5	2.553 (3)

O3—Li1—O3ⁱ	85.4 (4)	O3^vi—Sm1—O3^vii	65.38 (12)
O3—Li1—O5ⁱⁱ	124.08 (11)	O4—Sm1—O5	72.34 (9)
O3ⁱ—Li1—O5ⁱⁱ	118.63 (11)	O4^iv—Sm1—O5	137.49 (9)
O3—Li1—O5ⁱⁱⁱ	118.63 (11)	O1ⁱⁱⁱ—Sm1—O5	72.38 (9)
O3ⁱ—Li1—O5ⁱⁱⁱ	124.08 (11)	O1^v—Sm1—O5	84.63 (9)
O5ⁱⁱ—Li1—O5ⁱⁱⁱ	90.0 (4)	O3^vi—Sm1—O5	136.79 (8)
O3—Li1—P2	27.29 (8)	O3^vii—Sm1—O5	132.74 (9)
O3ⁱ—Li1—P2	112.7 (3)	O4—Sm1—O5^iv	137.49 (9)
O5ⁱⁱ—Li1—P2	108.29 (11)	O4^iv—Sm1—O5^iv	72.34 (9)
O5ⁱⁱⁱ—Li1—P2	99.83 (10)	O1ⁱⁱⁱ—Sm1—O5^iv	84.63 (9)
O3—Li1—P2ⁱ	112.7 (3)	O1^v—Sm1—O5^iv	72.38 (9)
O3ⁱ—Li1—P2ⁱ	27.29 (8)	O3^vi—Sm1—O5^iv	132.74 (9)
O5ⁱⁱ—Li1—P2ⁱ	99.83 (10)	O3^vii—Sm1—O5^iv	136.79 (8)
O5ⁱⁱⁱ—Li1—P2ⁱ	108.29 (11)	O5—Sm1—O5^iv	66.51 (12)
P2—Li1—P2ⁱ	139.9 (3)	O4—Sm1—Li1^vii	74.97 (7)
O3—Li1—P1ⁱⁱ	106.74 (11)	O4^iv—Sm1—Li1^vii	74.97 (7)
O3ⁱ—Li1—P1ⁱⁱ	102.43 (10)	O1ⁱⁱⁱ—Sm1—Li1^vii	103.71 (6)
O5ⁱⁱ—Li1—P1ⁱⁱ	25.02 (8)	O1^v—Sm1—Li1^vii	103.71 (6)
O5ⁱⁱⁱ—Li1—P1ⁱⁱ	114.9 (3)	O3^vi—Sm1—Li1^vii	32.69 (6)
P2—Li1—P1ⁱⁱ	100.84 (3)	O3^vii—Sm1—Li1^vii	32.69 (6)
P2ⁱ—Li1—P1ⁱⁱ	92.67 (3)	O5—Sm1—Li1^vii	146.74 (6)
O3—Li1—P1ⁱⁱⁱ	102.43 (10)	O5^iv—Sm1—Li1^vii	146.74 (6)
O3ⁱ—Li1—P1ⁱⁱⁱ	106.74 (11)	O4—Sm1—Li1ⁱⁱⁱ	105.03 (7)
O5ⁱⁱ—Li1—P1ⁱⁱⁱ	114.9 (3)	O4^iv—Sm1—Li1ⁱⁱⁱ	105.03 (7)
O5ⁱⁱⁱ—Li1—P1ⁱⁱⁱ	25.02 (8)	O1ⁱⁱⁱ—Sm1—Li1ⁱⁱⁱ	76.29 (6)
P2—Li1—P1ⁱⁱⁱ	92.67 (3)	O1^v—Sm1—Li1ⁱⁱⁱ	76.29 (6)
P2ⁱ—Li1—P1ⁱⁱⁱ	100.84 (3)	O3^vi—Sm1—Li1ⁱⁱⁱ	147.31 (6)
P1ⁱⁱ—Li1—P1ⁱⁱⁱ	139.9 (3)	O3^vii—Sm1—Li1ⁱⁱⁱ	147.31 (6)
O3—Li1—Sm1^vii	42.70 (19)	O5—Sm1—Li1ⁱⁱⁱ	33.26 (6)
O3ⁱ—Li1—Sm1^vii	42.70 (19)	O5^iv—Sm1—Li1ⁱⁱⁱ	33.26 (6)
O5ⁱⁱ—Li1—Sm1^vii	135.01 (19)	Li1^vii—Sm1—Li1ⁱⁱⁱ	180.000 (1)
O5ⁱⁱⁱ—Li1—Sm1^vii	135.01 (19)	O1—P1—O5	118.76 (17)
P2—Li1—Sm1^vii	69.97 (16)	O1—P1—O2	106.74 (15)
P2ⁱ—Li1—Sm1^vii	69.97 (16)	O5—P1—O2	110.85 (15)
P1ⁱⁱ—Li1—Sm1^vii	110.03 (16)	O1—P1—O6	111.48 (16)
P1ⁱⁱⁱ—Li1—Sm1^vii	110.03 (16)	O5—P1—O6	105.01 (14)
O3—Li1—Sm1ⁱⁱⁱ	137.30 (19)	O2—P1—O6	102.92 (15)
O3ⁱ—Li1—Sm1ⁱⁱⁱ	137.30 (19)	O1—P1—Li1ⁱⁱⁱ	91.88 (18)
O5ⁱⁱ—Li1—Sm1ⁱⁱⁱ	44.99 (19)	O2—P1—Li1ⁱⁱⁱ	143.38 (18)
O5ⁱⁱⁱ—Li1—Sm1ⁱⁱⁱ	44.99 (19)	O6—P1—Li1ⁱⁱⁱ	98.86 (11)
P2—Li1—Sm1ⁱⁱⁱ	110.03 (16)	O4—P2—O3	119.71 (16)
P2ⁱ—Li1—Sm1ⁱⁱⁱ	110.03 (16)	O4—P2—O6^viii	111.89 (15)
P1ⁱⁱ—Li1—Sm1ⁱⁱⁱ	69.97 (16)	O3—P2—O6^viii	107.63 (15)
P1ⁱⁱⁱ—Li1—Sm1ⁱⁱⁱ	69.97 (16)	O4—P2—O2	109.68 (15)
Sm1^vii—Li1—Sm1ⁱⁱⁱ	180.0	O3—P2—O2	104.96 (15)
O4—Sm1—O4^iv	149.93 (13)	O6^viii—P2—O2	101.19 (15)
O4—Sm1—O1ⁱⁱⁱ	93.04 (10)	O4—P2—Li1	126.36 (11)
O4^iv—Sm1—O1ⁱⁱⁱ	94.01 (10)	O6^viii—P2—Li1	121.18 (11)
O4—Sm1—O1^v	94.01 (10)	O2—P2—Li1	68.45 (19)
O4^iv—Sm1—O1^v	93.04 (10)	P1—O1—Sm1ⁱⁱⁱ	139.38 (17)
O1ⁱⁱⁱ—Sm1—O1^v	152.59 (13)	P1—O2—P2	132.45 (17)
O4—Sm1—O3^vi	74.20 (9)	P2—O3—Li1	115.5 (2)
O4^iv—Sm1—O3^vi	80.54 (9)	P2—O3—Sm1^vii	139.82 (16)
O1ⁱⁱⁱ—Sm1—O3^vi	136.12 (9)	Li1—O3—Sm1^vii	104.6 (2)
O1^v—Sm1—O3^vi	71.22 (9)	P2—O4—Sm1	132.98 (16)
O4—Sm1—O3^vii	80.54 (9)	P1—O5—Li1ⁱⁱⁱ	120.9 (2)
O4^iv—Sm1—O3^vii	74.20 (9)	P1—O5—Sm1	137.19 (16)
O1ⁱⁱⁱ—Sm1—O3^vii	71.22 (9)	Li1ⁱⁱⁱ—O5—Sm1	101.8 (2)
O1^v—Sm1—O3^vii	136.12 (9)	P2^ix—O6—P1	133.96 (18)

Symmetry codes: (i) −x+1, y, −z+3/2; (ii) x, −y+1, z+1/2; (iii) −x+1, −y+1, −z+1; (iv) −x+1, y, −z+1/2; (v) x, −y+1, z−1/2; (vi) x, −y, z−1/2; (vii) −x+1, −y, −z+1; (viii) −x+1/2, y−1/2, −z+1/2; (ix) −x+1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	LiSm(PO₃)₄
M_r	473.17
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	16.379 (2), 7.0499 (9), 9.6936 (12)
β (°)	126.138 (2)
V (Å³)	903.96 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.27
Crystal size (mm)	0.20 × 0.15 × 0.05

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.439, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2405, 854, 843
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.048, 1.09
No. of reflections	854
No. of parameters	84
Δρ_max, Δρ_min (e Å⁻³)	1.02, −0.71

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

References

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