Lithium europium(III) molybdate(VI), Li3.5Eu1.5(MoO4)4

Zhao, D.; Zhu, J.; Liang, P.; Chang, H.; He, R.

doi:10.1107/S1600536812000268

inorganic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page i14

doi:10.1107/S1600536812000268

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Lithium europium(III) molybdate(VI), Li_3.5Eu_1.5(MoO₄)₄

Dan Zhao,^a ^* Jing Zhu,^b Peng Liang,^a Huan Chang ^a and Rong He ^a

^aDepartment of Physics and Chemistry, Henan Polytechnic University, Jiaozuo, Henan 454000, People's Republic of China, and ^bDepartment of Material Science and Engineering, Yunnan University, Kunming 650091, People's Republic of China
^*Correspondence e-mail: iamzd@hpu.edu.cn

(Received 23 October 2011; accepted 4 January 2012; online 11 January 2012)

The title compound, Li_3.5Eu_1.5(MoO₄)₄, was prepared by solid-state reactions. The fundamental building units of the structure are LiO₄ polyhedra (site symmetry $[\overline1]$ ), distorted LiO₆ polyhedra and MoO₄ tetrahedra, which are further interconnected via corner-sharing O atoms. One site is occupied by both Li and Eu atoms in a substituent disordered manner (0.25:0.75), and the Li/Eu atoms are coordinated by eight O atoms in a distorted square-antiprismatic manner.

Related literature

For related rare-earth molybdate compounds, see: Zhao et al. (2010 ); Ipatova et al. (1982 ). For similar Li/Eu disorder in LiEu(WO₄)₂, see: Chiu et al. (2007 ).

Experimental

Crystal data

Li_3.5Eu_1.5(MoO₄)₄
M_r = 891.99
Triclinic, $[P \overline 1]$
a = 5.2182 (11) Å
b = 6.7008 (12) Å
c = 10.3167 (5) Å
α = 100.09 (2)°
β = 100.341 (15)°
γ = 111.891 (15)°
V = 317.49 (9) Å³
Z = 1
Mo Kα radiation
μ = 11.22 mm⁻¹
T = 296 K
0.20 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury70 CCD diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.213, T_max = 0.604
2478 measured reflections
1437 independent reflections
1224 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.079
S = 1.10
1437 reflections
105 parameters
Δρ_max = 0.95 e Å⁻³
Δρ_min = −1.62 e Å⁻³

Data collection: CrystalClear (Rigaku, 2004 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2004 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812000268/ru2018sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812000268/ru2018Isup2.hkl

checkCIF report

Comment top

In recent years, alkali rare-earth molybdates have been studied mainly due to their rich structural chemistry and interesting physical and chemical properties (Zhao et al., 2010). Of them, a mixed valence alkali rare-earth double molybdate Li₇Ho₃(MoO₄)₈ (Ipatova et al., 1982) with the substituent disordered structure was reported. In order to enrich this family type of compounds, we report the single-crystal growth and structure investigation of title compound Li_3.5Eu_1.5(MoO₄)₄.

In this structure, one site is occupancied by both Li and Eu atoms in a substituent disordered manner, denoted as M atom, such case can alse be found in compound LiEu(WO₄)₂ (Chiu et al., 2007). There are two Li atom sites, two Mo atom sites and one M atom site in the asymmetric unit of title compound. Only one Li(3) atom lies on the inversion center in 1 d position, and the other atoms lie on the general positions. One the other hand, the coordination of the two crystallographic distinct Li atoms are different. Li(2) atoms are surround by six O atoms with the bond distances ranging from 1.970 (16) to 2.62 (2) Å, forming distorted LiO₆ octahedra. Li(3) atoms are surround by four O atoms with the bond distances ranging from 1.968 (4) to 2.046 (4) Å, forming nearly planar LiO₄ groups. On an over view (Fig. 2), the three-dimensional structure contains LiO₄ groups, LiO₆ groups and MoO₄ tetrahedra, which are further interconnected via corner sharing O atoms. The M atoms are located on this framework and exhibit a coordination number of eight.

Related literature top

For related rare-earth molybdate compounds, see: Zhao et al. (2010); Ipatova et al. (1982). For similar Li/Eu disorder in LiEu(WO₄)₂, see: Chiu et al. (2007).

Experimental top

The finely ground reagents Li₂CO₃, Eu₂O₃ and MoO₃ were mixed in the molar ratio Li: Eu: Mo = 5: 1: 5, and then placed in a Pt crucible to heat at 573 K for 4 h. The mixture was then re-ground and heated at 1073 K for 20 h, then cooled to 673 K at a rate of 3 K h^-1, and finally quenched to room temperature. A few colorless crystals of the title compound with prismatic shape were obtained.

Computing details top

Data collection: CrystalClear (Rigaku, 2004); cell refinement: CrystalClear (Rigaku, 2004); data reduction: CrystalClear (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. The expanded asymmetric unit of Li_3.5Eu_1.5(MoO₄)₂ showing the coordination environments of the Li, Mo and Li/Eu atoms. The displacement ellipsoids are drawn at the 50% probability level.[Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x + 1, -y + 2, -z + 1; (iii) -x + 2, -y + 2, -z + 1; (iv) x - 1, y, z; (vi) -x + 2, -y + 1, -z + 1; (viii) x, y, z - 1; (ix) x, y, z + 1; (x) -x + 3, -y + 2, -z; (xi) -x + 3, -y + 2, -z + 1].

Fig. 2. View of the crystal structure of Li_3.5Eu_1.5(MoO₄)₂ along [010]. LiO₄, LiO₆ and MoO₄ units are given in the polyhedral representation.

Lithium europium(III) molybdate(VI) top

Crystal data top

Li_3.5Eu_1.5(MoO₄)₄	Z = 1
M_r = 891.99	F(000) = 401
Triclinic, P1	D_x = 4.665 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.2182 (11) Å	Cell parameters from 791 reflections
b = 6.7008 (12) Å	θ = 2.1–27.5°
c = 10.3167 (5) Å	µ = 11.22 mm⁻¹
α = 100.09 (2)°	T = 296 K
β = 100.341 (15)°	Prism, colourless
γ = 111.891 (15)°	0.20 × 0.05 × 0.05 mm
V = 317.49 (9) Å³

Data collection top

Rigaku Mercury70 CCD diffractometer	1437 independent reflections
Radiation source: fine-focus sealed tube	1224 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
Detector resolution: 14.6306 pixels mm^-1	θ_max = 27.5°, θ_min = 3.4°
ω scans	h = −6→6
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −8→8
T_min = 0.213, T_max = 0.604	l = −12→13
2478 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.029	Secondary atom site location: difference Fourier map
wR(F²) = 0.079	w = 1/[σ²(F_o²) + (0.038P)² + 1.5273P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1437 reflections	Δρ_max = 0.95 e Å⁻³
105 parameters	Δρ_min = −1.62 e Å⁻³

Crystal data top

Li_3.5Eu_1.5(MoO₄)₄	γ = 111.891 (15)°
M_r = 891.99	V = 317.49 (9) Å³
Triclinic, P1	Z = 1
a = 5.2182 (11) Å	Mo Kα radiation
b = 6.7008 (12) Å	µ = 11.22 mm⁻¹
c = 10.3167 (5) Å	T = 296 K
α = 100.09 (2)°	0.20 × 0.05 × 0.05 mm
β = 100.341 (15)°

Data collection top

Rigaku Mercury70 CCD diffractometer	1437 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1224 reflections with I > 2σ(I)
T_min = 0.213, T_max = 0.604	R_int = 0.014
2478 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	105 parameters
wR(F²) = 0.079	0 restraints
S = 1.10	Δρ_max = 0.95 e Å⁻³
1437 reflections	Δρ_min = −1.62 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	Occ. (<1)
Li1	0.62034 (7)	0.77190 (5)	0.43965 (3)	0.00542 (13)	0.25
Eu1	0.62034 (7)	0.77190 (5)	0.43965 (3)	0.00542 (13)	0.75
Mo1	0.16529 (10)	0.70023 (7)	0.68099 (5)	0.00873 (15)
Mo2	1.08254 (11)	0.84541 (8)	0.19822 (5)	0.01044 (15)
O1	0.3065 (9)	0.5032 (7)	0.7078 (4)	0.0141 (9)
O2	0.8045 (9)	0.5637 (7)	0.5724 (4)	0.0145 (9)
O3	0.7317 (9)	0.3263 (7)	0.7745 (4)	0.0175 (9)
O4	0.7691 (10)	0.6882 (7)	0.0693 (5)	0.0213 (10)
O5	0.3812 (8)	0.8834 (6)	0.5948 (4)	0.0099 (8)
O6	1.0161 (9)	0.9568 (7)	0.3572 (4)	0.0141 (9)
O7	1.1437 (9)	0.8249 (7)	0.8386 (4)	0.0175 (9)
O8	1.3010 (9)	1.0575 (7)	0.1374 (4)	0.0167 (9)
Li2	0.669 (4)	0.593 (3)	0.869 (2)	0.060 (5)*
Li3	1.5000	1.0000	0.0000	0.049 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Li1	0.0066 (2)	0.0053 (2)	0.0037 (2)	0.00203 (15)	0.00143 (14)	0.00061 (14)
Eu1	0.0066 (2)	0.0053 (2)	0.0037 (2)	0.00203 (15)	0.00143 (14)	0.00061 (14)
Mo1	0.0097 (3)	0.0099 (3)	0.0068 (3)	0.0038 (2)	0.0029 (2)	0.00267 (19)
Mo2	0.0122 (3)	0.0133 (3)	0.0057 (2)	0.0056 (2)	0.00259 (19)	0.00134 (19)
O1	0.018 (2)	0.016 (2)	0.010 (2)	0.0090 (18)	0.0062 (17)	0.0028 (16)
O2	0.014 (2)	0.012 (2)	0.013 (2)	0.0028 (17)	0.0019 (17)	0.0010 (16)
O3	0.020 (2)	0.019 (2)	0.015 (2)	0.0112 (19)	0.0051 (18)	0.0031 (18)
O4	0.021 (2)	0.021 (2)	0.013 (2)	0.0023 (19)	0.0017 (18)	0.0031 (18)
O5	0.0110 (19)	0.0098 (19)	0.0089 (19)	0.0039 (16)	0.0032 (15)	0.0032 (15)
O6	0.0109 (19)	0.015 (2)	0.014 (2)	0.0028 (17)	0.0057 (17)	0.0009 (17)
O7	0.016 (2)	0.022 (2)	0.014 (2)	0.0081 (19)	0.0044 (17)	0.0013 (18)
O8	0.019 (2)	0.022 (2)	0.014 (2)	0.0114 (19)	0.0082 (18)	0.0083 (18)

Geometric parameters (Å, º) top

Li1—O1ⁱ	2.368 (4)	O2—Li1ⁱ	2.464 (4)
Li1—O6	2.370 (4)	O2—Eu1ⁱ	2.464 (4)
Li1—O5	2.381 (4)	O3—Mo2^vi	1.786 (4)
Li1—O5ⁱⁱ	2.400 (4)	O3—Li2	2.05 (2)
Li1—O3ⁱ	2.413 (4)	O3—Li1ⁱ	2.413 (4)
Li1—O2	2.437 (4)	O3—Eu1ⁱ	2.413 (4)
Li1—O6ⁱⁱⁱ	2.442 (4)	O4—Li2^viii	1.96 (2)
Li1—O2ⁱ	2.465 (4)	O4—Li2ⁱ	2.63 (2)
Li1—Li2ⁱ	3.35 (2)	O5—Eu1ⁱⁱ	2.400 (4)
Li1—Eu1ⁱⁱⁱ	3.8024 (13)	O5—Li1ⁱⁱ	2.400 (4)
Li1—Eu1ⁱⁱ	3.8162 (9)	O6—Eu1ⁱⁱⁱ	2.442 (4)
Li1—Eu1ⁱ	3.8915 (10)	O6—Li1ⁱⁱⁱ	2.442 (4)
Mo1—O7^iv	1.737 (4)	O7—Mo1^vii	1.737 (4)
Mo1—O1	1.772 (4)	O7—Li3^ix	2.045 (4)
Mo1—O2^iv	1.799 (4)	O7—Li2	2.50 (2)
Mo1—O5	1.811 (4)	O8—Li3	1.968 (4)
Mo1—Li3^v	3.3047 (10)	O8—Li2ⁱⁱⁱ	2.30 (2)
Mo1—Li2	3.36 (2)	Li2—O4^ix	1.96 (2)
Mo1—Eu1^iv	3.6622 (9)	Li2—O8ⁱⁱⁱ	2.30 (2)
Mo1—Eu1ⁱⁱ	3.7953 (9)	Li2—O4ⁱ	2.63 (2)
Mo1—Eu1ⁱ	3.8168 (8)	Li2—Li3^v	3.314 (19)
Mo2—O4	1.731 (5)	Li2—Li1ⁱ	3.35 (2)
Mo2—O8	1.753 (4)	Li2—Eu1ⁱ	3.35 (2)
Mo2—O3^vi	1.786 (4)	Li3—O8^x	1.968 (4)
Mo2—O6	1.827 (4)	Li3—O7^xi	2.045 (4)
Mo2—Li3	3.2648 (7)	Li3—O7^viii	2.045 (4)
Mo2—Eu1^vii	3.6433 (9)	Li3—Mo2^x	3.2648 (7)
Mo2—Eu1ⁱⁱⁱ	3.8126 (12)	Li3—Mo1ⁱⁱⁱ	3.3046 (10)
O1—Li2	2.10 (2)	Li3—Mo1^xii	3.3046 (10)
O1—Eu1ⁱ	2.368 (4)	Li3—Li2ⁱⁱⁱ	3.314 (19)
O1—Li1ⁱ	2.368 (4)	Li3—Li2^xii	3.314 (19)
O2—Mo1^vii	1.799 (4)

O1ⁱ—Li1—O6	72.17 (14)	Mo1—O1—Li1ⁱ	133.9 (2)
O1ⁱ—Li1—O5	152.17 (14)	Li2—O1—Li1ⁱ	97.0 (5)
O6—Li1—O5	135.59 (14)	Eu1ⁱ—O1—Li1ⁱ	0.000 (12)
O1ⁱ—Li1—O5ⁱⁱ	128.42 (13)	Mo1^vii—O2—Li1	118.9 (2)
O6—Li1—O5ⁱⁱ	70.23 (13)	Mo1^vii—O2—Li1ⁱ	134.1 (2)
O5—Li1—O5ⁱⁱ	74.09 (15)	Li1—O2—Li1ⁱ	105.10 (16)
O1ⁱ—Li1—O3ⁱ	75.14 (14)	Mo1^vii—O2—Eu1ⁱ	134.1 (2)
O6—Li1—O3ⁱ	94.56 (15)	Li1—O2—Eu1ⁱ	105.10 (16)
O5—Li1—O3ⁱ	100.26 (14)	Li1ⁱ—O2—Eu1ⁱ	0.00 (2)
O5ⁱⁱ—Li1—O3ⁱ	74.05 (14)	Mo2^vi—O3—Li2	143.2 (6)
O1ⁱ—Li1—O2	70.22 (14)	Mo2^vi—O3—Li1ⁱ	119.6 (2)
O6—Li1—O2	101.42 (14)	Li2—O3—Li1ⁱ	96.9 (6)
O5—Li1—O2	97.18 (13)	Mo2^vi—O3—Eu1ⁱ	119.6 (2)
O5ⁱⁱ—Li1—O2	151.16 (14)	Li2—O3—Eu1ⁱ	96.9 (6)
O3ⁱ—Li1—O2	134.77 (14)	Li1ⁱ—O3—Eu1ⁱ	0.00 (3)
O1ⁱ—Li1—O6ⁱⁱⁱ	124.00 (14)	Mo2—O4—Li2^viii	135.4 (6)
O6—Li1—O6ⁱⁱⁱ	75.58 (15)	Mo2—O4—Li2ⁱ	118.2 (5)
O5—Li1—O6ⁱⁱⁱ	71.94 (13)	Li2^viii—O4—Li2ⁱ	103.7 (6)
O5ⁱⁱ—Li1—O6ⁱⁱⁱ	78.18 (14)	Mo1—O5—Li1	123.90 (18)
O3ⁱ—Li1—O6ⁱⁱⁱ	152.23 (14)	Mo1—O5—Eu1ⁱⁱ	128.12 (19)
O2—Li1—O6ⁱⁱⁱ	72.99 (14)	Li1—O5—Eu1ⁱⁱ	105.91 (15)
O1ⁱ—Li1—O2ⁱ	79.65 (14)	Mo1—O5—Li1ⁱⁱ	128.12 (19)
O6—Li1—O2ⁱ	150.92 (14)	Li1—O5—Li1ⁱⁱ	105.91 (15)
O5—Li1—O2ⁱ	73.02 (13)	Eu1ⁱⁱ—O5—Li1ⁱⁱ	0.00 (2)
O5ⁱⁱ—Li1—O2ⁱ	125.81 (14)	Mo2—O6—Li1	125.4 (2)
O3ⁱ—Li1—O2ⁱ	70.98 (15)	Mo2—O6—Eu1ⁱⁱⁱ	126.0 (2)
O2—Li1—O2ⁱ	74.91 (16)	Li1—O6—Eu1ⁱⁱⁱ	104.42 (15)
O6ⁱⁱⁱ—Li1—O2ⁱ	128.19 (14)	Mo2—O6—Li1ⁱⁱⁱ	126.0 (2)
O1ⁱ—Li1—Li2ⁱ	38.4 (4)	Li1—O6—Li1ⁱⁱⁱ	104.42 (15)
O6—Li1—Li2ⁱ	87.0 (3)	Eu1ⁱⁱⁱ—O6—Li1ⁱⁱⁱ	0.000 (17)
O5—Li1—Li2ⁱ	128.2 (4)	Mo1^vii—O7—Li3^ix	121.6 (2)
O5ⁱⁱ—Li1—Li2ⁱ	105.7 (4)	Mo1^vii—O7—Li2	107.8 (5)
O3ⁱ—Li1—Li2ⁱ	37.4 (4)	Li3^ix—O7—Li2	122.2 (5)
O2—Li1—Li2ⁱ	101.2 (4)	Mo2—O8—Li3	122.5 (2)
O6ⁱⁱⁱ—Li1—Li2ⁱ	159.8 (3)	Mo2—O8—Li2ⁱⁱⁱ	133.5 (5)
O2ⁱ—Li1—Li2ⁱ	66.1 (3)	Li3—O8—Li2ⁱⁱⁱ	101.5 (5)
O1ⁱ—Li1—Eu1ⁱⁱⁱ	99.68 (11)	O4^ix—Li2—O3	119.8 (10)
O6—Li1—Eu1ⁱⁱⁱ	38.45 (10)	O4^ix—Li2—O1	136.5 (10)
O5—Li1—Eu1ⁱⁱⁱ	104.25 (10)	O3—Li2—O1	89.5 (8)
O5ⁱⁱ—Li1—Eu1ⁱⁱⁱ	69.98 (10)	O4^ix—Li2—O8ⁱⁱⁱ	89.3 (8)
O3ⁱ—Li1—Eu1ⁱⁱⁱ	128.14 (11)	O3—Li2—O8ⁱⁱⁱ	144.5 (10)
O2—Li1—Eu1ⁱⁱⁱ	86.31 (10)	O1—Li2—O8ⁱⁱⁱ	80.4 (7)
O6ⁱⁱⁱ—Li1—Eu1ⁱⁱⁱ	37.13 (9)	O4^ix—Li2—O7	97.9 (8)
O2ⁱ—Li1—Eu1ⁱⁱⁱ	160.33 (10)	O3—Li2—O7	85.3 (7)
Li2ⁱ—Li1—Eu1ⁱⁱⁱ	124.7 (3)	O1—Li2—O7	117.2 (9)
O1ⁱ—Li1—Eu1ⁱⁱ	160.49 (10)	O8ⁱⁱⁱ—Li2—O7	69.8 (5)
O6—Li1—Eu1ⁱⁱ	103.47 (10)	O4^ix—Li2—O4ⁱ	76.3 (6)
O5—Li1—Eu1ⁱⁱ	37.21 (9)	O3—Li2—O4ⁱ	88.5 (7)
O5ⁱⁱ—Li1—Eu1ⁱⁱ	36.87 (9)	O1—Li2—O4ⁱ	73.0 (6)
O3ⁱ—Li1—Eu1ⁱⁱ	86.47 (10)	O8ⁱⁱⁱ—Li2—O4ⁱ	120.0 (8)
O2—Li1—Eu1ⁱⁱ	128.97 (10)	O7—Li2—O4ⁱ	168.0 (9)
O6ⁱⁱⁱ—Li1—Eu1ⁱⁱ	71.20 (10)	O4^ix—Li2—Li3^v	64.3 (5)
O2ⁱ—Li1—Eu1ⁱⁱ	100.71 (10)	O3—Li2—Li3^v	174.0 (9)
Li2ⁱ—Li1—Eu1ⁱⁱ	123.8 (3)	O1—Li2—Li3^v	84.6 (6)
Eu1ⁱⁱⁱ—Li1—Eu1ⁱⁱ	86.46 (2)	O8ⁱⁱⁱ—Li2—Li3^v	35.6 (3)
O1ⁱ—Li1—Eu1ⁱ	70.99 (10)	O7—Li2—Li3^v	98.6 (6)
O6—Li1—Eu1ⁱ	132.65 (10)	O4ⁱ—Li2—Li3^v	88.4 (5)
O5—Li1—Eu1ⁱ	83.87 (9)	O4^ix—Li2—Li1ⁱ	156.0 (9)
O5ⁱⁱ—Li1—Eu1ⁱ	156.82 (9)	O3—Li2—Li1ⁱ	45.7 (4)
O3ⁱ—Li1—Eu1ⁱ	103.58 (11)	O1—Li2—Li1ⁱ	44.6 (4)
O2—Li1—Eu1ⁱ	37.69 (10)	O8ⁱⁱⁱ—Li2—Li1ⁱ	112.4 (7)
O6ⁱⁱⁱ—Li1—Eu1ⁱ	102.02 (10)	O7—Li2—Li1ⁱ	99.2 (6)
O2ⁱ—Li1—Eu1ⁱ	37.21 (10)	O4ⁱ—Li2—Li1ⁱ	83.6 (5)
Li2ⁱ—Li1—Eu1ⁱ	82.2 (3)	Li3^v—Li2—Li1ⁱ	128.7 (6)
Eu1ⁱⁱⁱ—Li1—Eu1ⁱ	123.78 (2)	O4^ix—Li2—Eu1ⁱ	156.0 (9)
Eu1ⁱⁱ—Li1—Eu1ⁱ	120.77 (2)	O3—Li2—Eu1ⁱ	45.7 (4)
O7^iv—Mo1—O1	106.9 (2)	O1—Li2—Eu1ⁱ	44.6 (4)
O7^iv—Mo1—O2^iv	106.3 (2)	O8ⁱⁱⁱ—Li2—Eu1ⁱ	112.4 (7)
O1—Mo1—O2^iv	110.91 (19)	O7—Li2—Eu1ⁱ	99.2 (6)
O7^iv—Mo1—O5	116.72 (19)	O4ⁱ—Li2—Eu1ⁱ	83.6 (5)
O1—Mo1—O5	108.58 (18)	Li3^v—Li2—Eu1ⁱ	128.7 (6)
O2^iv—Mo1—O5	107.45 (19)	Li1ⁱ—Li2—Eu1ⁱ	0.00 (2)
O7^iv—Mo1—Li3^v	31.81 (14)	O4^ix—Li2—Mo1	120.3 (8)
O1—Mo1—Li3^v	90.06 (14)	O3—Li2—Mo1	115.1 (8)
O2^iv—Mo1—Li3^v	138.06 (13)	O1—Li2—Mo1	27.1 (3)
O5—Mo1—Li3^v	98.83 (13)	O8ⁱⁱⁱ—Li2—Mo1	54.5 (4)
O7^iv—Mo1—Li2	84.1 (4)	O7—Li2—Mo1	108.3 (6)
O1—Mo1—Li2	32.6 (4)	O4ⁱ—Li2—Mo1	83.6 (5)
O2^iv—Mo1—Li2	141.4 (4)	Li3^v—Li2—Mo1	59.4 (3)
O5—Mo1—Li2	100.0 (4)	Li1ⁱ—Li2—Mo1	69.4 (4)
Li3^v—Mo1—Li2	59.6 (3)	Eu1ⁱ—Li2—Mo1	69.4 (4)
O7^iv—Mo1—Eu1^iv	102.85 (14)	O8^x—Li3—O8	180.000 (1)
O1—Mo1—Eu1^iv	141.46 (14)	O8^x—Li3—O7^xi	97.16 (17)
O2^iv—Mo1—Eu1^iv	35.65 (13)	O8—Li3—O7^xi	82.84 (17)
O5—Mo1—Eu1^iv	78.16 (13)	O8^x—Li3—O7^viii	82.84 (17)
Li3^v—Mo1—Eu1^iv	127.214 (19)	O8—Li3—O7^viii	97.16 (17)
Li2—Mo1—Eu1^iv	173.0 (3)	O7^xi—Li3—O7^viii	180.000 (1)
O7^iv—Mo1—Eu1ⁱⁱ	94.98 (15)	O8^x—Li3—Mo2^x	26.92 (13)
O1—Mo1—Eu1ⁱⁱ	137.51 (14)	O8—Li3—Mo2^x	153.08 (13)
O2^iv—Mo1—Eu1ⁱⁱ	96.59 (14)	O7^xi—Li3—Mo2^x	87.08 (12)
O5—Mo1—Eu1ⁱⁱ	29.83 (12)	O7^viii—Li3—Mo2^x	92.92 (12)
Li3^v—Mo1—Eu1ⁱⁱ	90.23 (2)	O8^x—Li3—Mo2	153.08 (13)
Li2—Mo1—Eu1ⁱⁱ	119.9 (3)	O8—Li3—Mo2	26.92 (13)
Eu1^iv—Mo1—Eu1ⁱⁱ	61.28 (2)	O7^xi—Li3—Mo2	92.92 (12)
O7^iv—Mo1—Eu1ⁱ	133.27 (15)	O7^viii—Li3—Mo2	87.08 (12)
O1—Mo1—Eu1ⁱ	26.58 (13)	Mo2^x—Li3—Mo2	180.000 (1)
O2^iv—Mo1—Eu1ⁱ	95.63 (13)	O8^x—Li3—Mo1ⁱⁱⁱ	123.62 (13)
O5—Mo1—Eu1ⁱ	94.11 (12)	O8—Li3—Mo1ⁱⁱⁱ	56.38 (13)
Li3^v—Mo1—Eu1ⁱ	114.76 (2)	O7^xi—Li3—Mo1ⁱⁱⁱ	26.59 (12)
Li2—Mo1—Eu1ⁱ	55.2 (3)	O7^viii—Li3—Mo1ⁱⁱⁱ	153.41 (12)
Eu1^iv—Mo1—Eu1ⁱ	118.02 (2)	Mo2^x—Li3—Mo1ⁱⁱⁱ	109.910 (19)
Eu1ⁱⁱ—Mo1—Eu1ⁱ	123.353 (18)	Mo2—Li3—Mo1ⁱⁱⁱ	70.09 (2)
O4—Mo2—O8	107.4 (2)	O8^x—Li3—Mo1^xii	56.38 (13)
O4—Mo2—O3^vi	108.3 (2)	O8—Li3—Mo1^xii	123.62 (13)
O8—Mo2—O3^vi	106.3 (2)	O7^xi—Li3—Mo1^xii	153.41 (12)
O4—Mo2—O6	112.4 (2)	O7^viii—Li3—Mo1^xii	26.59 (12)
O8—Mo2—O6	111.97 (19)	Mo2^x—Li3—Mo1^xii	70.090 (19)
O3^vi—Mo2—O6	110.20 (19)	Mo2—Li3—Mo1^xii	109.910 (19)
O4—Mo2—Li3	96.73 (15)	Mo1ⁱⁱⁱ—Li3—Mo1^xii	180.0
O8—Mo2—Li3	30.53 (14)	O8^x—Li3—Li2ⁱⁱⁱ	137.1 (4)
O3^vi—Mo2—Li3	83.23 (14)	O8—Li3—Li2ⁱⁱⁱ	42.9 (4)
O6—Mo2—Li3	140.59 (13)	O7^xi—Li3—Li2ⁱⁱⁱ	81.2 (4)
O4—Mo2—Eu1^vii	140.06 (16)	O7^viii—Li3—Li2ⁱⁱⁱ	98.8 (4)
O8—Mo2—Eu1^vii	100.92 (14)	Mo2^x—Li3—Li2ⁱⁱⁱ	110.9 (3)
O3^vi—Mo2—Eu1^vii	35.15 (14)	Mo2—Li3—Li2ⁱⁱⁱ	69.1 (3)
O6—Mo2—Eu1^vii	80.96 (13)	Mo1ⁱⁱⁱ—Li3—Li2ⁱⁱⁱ	61.0 (4)
Li3—Mo2—Eu1^vii	93.60 (2)	Mo1^xii—Li3—Li2ⁱⁱⁱ	119.0 (4)
O4—Mo2—Eu1ⁱⁱⁱ	143.13 (16)	O8^x—Li3—Li2^xii	42.9 (4)
O8—Mo2—Eu1ⁱⁱⁱ	90.70 (14)	O8—Li3—Li2^xii	137.1 (4)
O3^vi—Mo2—Eu1ⁱⁱⁱ	96.42 (14)	O7^xi—Li3—Li2^xii	98.8 (4)
O6—Mo2—Eu1ⁱⁱⁱ	31.22 (13)	O7^viii—Li3—Li2^xii	81.2 (4)
Li3—Mo2—Eu1ⁱⁱⁱ	113.38 (2)	Mo2^x—Li3—Li2^xii	69.1 (3)
Eu1^vii—Mo2—Eu1ⁱⁱⁱ	61.522 (18)	Mo2—Li3—Li2^xii	110.9 (3)
Mo1—O1—Li2	120.3 (6)	Mo1ⁱⁱⁱ—Li3—Li2^xii	119.0 (4)
Mo1—O1—Eu1ⁱ	133.9 (2)	Mo1^xii—Li3—Li2^xii	61.0 (4)
Li2—O1—Eu1ⁱ	97.0 (5)	Li2ⁱⁱⁱ—Li3—Li2^xii	180.000 (1)

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

Experimental details

Crystal data
Chemical formula	Li_3.5Eu_1.5(MoO₄)₄
M_r	891.99
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.2182 (11), 6.7008 (12), 10.3167 (5)
α, β, γ (°)	100.09 (2), 100.341 (15), 111.891 (15)
V (Å³)	317.49 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	11.22
Crystal size (mm)	0.20 × 0.05 × 0.05

Data collection
Diffractometer	Rigaku Mercury70 CCD diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.213, 0.604
No. of measured, independent and observed [I > 2σ(I)] reflections	2478, 1437, 1224
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.079, 1.10
No. of reflections	1437
No. of parameters	105
Δρ_max, Δρ_min (e Å⁻³)	0.95, −1.62

Computer programs: CrystalClear (Rigaku, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2004), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

The authors acknowledge the National Natural Science Foundation of China (No. 20901066).

References

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