Crystal structure and magnetic properties of LaCa0.143 (4)O0.857 (4)F0.143 (4)Bi0.857 (4)S2

Huang, R.; Zhang, H.; Wang, D.; Cai, C.; Huang, F.

doi:10.1107/S2056989016008082

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Volume 72| Part 6| June 2016| Pages 845-848

https://doi.org/10.1107/S2056989016008082

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Crystal structure and magnetic properties of LaCa_0.143 (4)O_0.857 (4)F_0.143 (4)Bi_0.857 (4)S₂

Rongtie Huang,^a,^b Hui Zhang,^a ^* Dong Wang,^b Chuanbing Cai ^b and Fuqiang Huang ^a ^*

^aState Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, People's Republic of China, and ^bDepartment of Physics, Shanghai University, Shanghai 200444, People's Republic of China
^*Correspondence e-mail: huizhangmpg@hotmail.com, huangfq@mail.sic.ac.cn

Edited by T. J. Prior, University of Hull, England (Received 7 May 2016; accepted 18 May 2016; online 24 May 2016)

The synthesis, structure, and magnetic properties of lithium dibarium calcium oxide fluoride disulfide are reported. LaCa_0.143 (4)O_0.857 (4)F_0.143 (4)Bi_0.857 (4)S₂ crystallizes in the tetragonal space group P4/nmm. The structure exhibits disorder of the Ca²⁺ and Bi³⁺ cations, and the O²⁻ and F⁻ anions. The structure is composed of a stacking of [(O,F)₂La₂] layers and double [(Bi,Ca)S₂] layers. Magnetic property measurements indicate a very small magnetization at 300 K and the existence of weak ferromagnetism at 2 K.

Keywords: crystal structure; magnetic properties; disorder.

CCDC reference: 1480636

1. Chemical context

Layered crystal structures seem to be a common stage on which to explore superconductivity (Vershinin et al., 2004 ; Kamihara et al., 2008 ; Chen et al., 2008 ; Fang et al., 2010 ). The discovery of [Fe₂An₂] (An = P, As, S, Se or Te) and [CuO₂] superconducting layers has opened a new field in physics and chemistry for the exploration of low-dimensional superconductivity. Recently, superconductivity with transition temperatures of 4.5 K was reported in the BiS₂-based compound Bi₄O₄S₃ (Singh et al., 2012 ). Soon after, LnO_1-xF_xBiS₂ (Ln = La, Ce, Pr and Nd), were reported to be superconducting with transition temperatures T_c of 3–10.6 K (Nagao et al., 2013 ; Demura et al., 2013 ). The mother BiS₂-based layered compound AeFBiS₂ (Ae = Ca, Sr or Ba; Lei et al., 2013 ; Han et al., 2008 ) is isostructural to LnOBiS₂, with the [Ln₂O₂]²⁻ layer being replaced by an isocharged [Sr₂F₂]²⁻ block. The parent phase of SrFBiS₂ shows semiconducting behavior, but electron-doped Sr_0.5La_0.5FBiS₂ has a superconducting transition of 2.8 K (Lin et al., 2013 ). Herein the synthesis, structure and magnetic properties of LaCa_0.143 (4)O_0.857 (4)F_0.143 (4)Bi_0.857 (4)S₂ are reported.

2. Structural commentary

We attempted to prepare the Ca and F double-doped compound La_1−xCa_xO_1−2xF_2xBiS₂, but the results indicate the single-crystal composition is LaCa_0.143 (4)O_0.857 (4)F_0.143 (4)Bi_0.857 (4)S₂. An SEM image shows thick plate-shaped crystals of LaCa_0.143 (4)O_0.857 (4)F_0.143 (4)Bi_0.857 (4)S₂ (Fig. 1). LaO_1−xF_xBiS₂ crystals usually show a thin-sheet shape (Fig. 2). From the EDXS analysis, we obtained the elemental components of La, Ca, Bi, S, F and O. The final composition was obtained by structure refinement (details can be seen in the Refinement section).

Figure 1
SEM image of LaCa_0.143 (4)O_0.857 (4)F_0.143 (4)Bi_0.857 (4)S₂.

Figure 2
SEM image of LaO_0.6F_0.4BiS₂.

The structure of LaCa_0.143 (4)O_0.857 (4)F_0.143 (4)Bi_0.857 (4)S₂, shown in Fig. 3, is composed of a stacking of [(O,F)₂La₂] layers and double [(Bi,Ca)S₂] layers as in LaO_1−xF_xBiS₂. The double [(Bi,Ca)S₂] layers show Bi1/Ca1—S2 distances of 2.8672 (6) Å representing equatorial bonds and Bi1/Ca1—S1 distances of 2.530 (3) Å representing axial bonds; these are a little shorter than the Bi1—S1 distance of 2.87476 (15) and Bi1—S2 distance of 2.530 (6) Å in LaO_1−xF_xBiS₂. The [(O,F)₂La₂] layers exhibit O1/F1—La1 bond lengths of 2.4414 (6) Å and La1—O1/F1—La1 bond angles of 108.08 (2) and 112.29 (4)°, which are close to the La—O/F bond length of 2.4402 (8) Å and La1—O1/F1—La1 bond angles of 107.82 (3) and 112.82 (6)° in LaO_1−xF_xBiS₂. The ionic radius of Ca²⁺ is 114 pm which is a little shorter than that of 117.2/117 pm for La³⁺/Bi³⁺. The distinct reduced Bi1/Ca1—S2 distances in the title compound reflect the fact that Ca substitutes Bi sites rather than La sites.

Figure 3
Crystal structure of LaCa_0.143 (4)O_0.857 (4)F_0.143 (4)Bi_0.857 (4)S₂, showing [(O,F)₂La₂] layers and double [BiS₂] layers (O/F in red, La in blue, Bi/Ca in pink and S in yellow; 50% probability ellipsoids).

3. Magnetic property measurements

The magnetization versus temperature under a 1 T field for the title compound is given in Fig. 4. Magnetization versus magnetic field is given in Fig. 5 for fields ranging from −5 to 5 T at 2 K and 300 K. The magnetic properties indicate weak ferromagnetism at 2 K and a very low magnetization at 300 K. The superconducting transition is not observed in the measured temperature range. This might be related to the Ca substitution of the Bi site in the title compound. For superconducting LaO_1−xF_xBiS₂ crystals, the density of states at the Fermi level is mainly directed by the Bi p orbital. [BiS₂] layers play a vital role in the transport and superconducting properties. The Ca substitution of the Bi site leads to a hole doping which changed the electronic band structure and density of state of LaO_1−xF_xBiS₂. Another reason might be the reduced F content in LaCa_0.143 (4)O_0.857 (4)F_0.143 (4)Bi_0.857 (4)S₂ compared with LaO_1−xF_xBiS₂.

Figure 4
Magnetic moment versus temperature for LaCa_0.143 (4)O_0.857 (4)F_0.143 (4)Bi_0.857 (4)S₂ under a 1 T field.

Figure 5
Magnetic moment versus field for LaCa_0.143 (4)O_0.857 (4)F_0.143 (4)Bi_0.857 (4)S₂ from −5 T to 5 T at 2 K and 300 K.

4. Database survey

LnO_1−xF_xBiS₂ (Ln = La, Ce, Pr and Nd) compounds were reported by Nagao et al. (2013) and Demura et al. (2013). AeFBiS₂ (Ae = Ca, Sr, Ba) (Lei et al., 2013; Han et al., 2008) are isostructural to LnOBiS₂. The doped Sr_0.5La_0.5FBiS₂ (Lin et al., 2013) is isostructural to AeFBiS₂.

5. Synthesis and crystallization

LaCa_0.143 (4)O_0.857 (4)F_0.143 (4)Bi_0.857 (4)S₂ was prepared using of Bi₂O₃, CaF₂, La₂S₃, Bi₂S₃ and Bi raw materials. The mixtures with a nominal composition of La_0.85Ca_0.15O_0.70F_0.30BiS₂ were ground, pressed into pellets, sealed in an evacuated quartz tube, and heated at 1073 K for 3 d. High-quality single crystals were grown by using KI as the flux. Nominal La_0.85Ca_0.15O_0.70F_0.30BiS₂ and KI in the molar ratio of 1:3 were mixed and placed in a quartz tube, which was sealed and heated to 1273 K and kept at this temperature for 1 d, then cooled to room temperature in 10 d. The product was washed with distilled water and acetone, then dried at 353 K for 12 h; finally black plate-shaped crystals were obtained.

The morphology and element compositions were investigated by a scanning electronic microscope equipped with an energy dispersive X-ray spectroscopy (EDXS, Oxford Instruments). The EDXS shows the atom % ratio for S:Ca:La:Bi to be 48.23: 6.94: 24.36: 20.48. O and F could not be determined precisely. Magnetic properties were measured on a multifunctional physical properties measurement system (PPMS, Quantum Design).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The La, Bi, S and O atoms were located in difference maps and their positions were freely refined. Ca was assumed at La sites at first, but the refinement show no reducing occupancy of La. The partial occupancy of Bi indicates a mixed occupancy with Ca. Ca and Bi were refined together later. EDXS measurements could not determine occupancies of O and F precisely. If the occupancies of F and O are refined together, the obtained composition is La₂Bi_1.859 (4)Ca_0.141 (4)O_0.48 (14)F_0.52 (14)S₄ with high standard errors for O and F. In order to keep charge neutrality, the occupancy of F was fixed to be the same as Ca so the final composition of LaCa_0.143 (4)O_0.857 (4)F_0.143 (4)Bi_0.857 (4)S₂ was obtained.

Table 1
Experimental details

Crystal data
Chemical formula	LaCa_0.143 (4)O_0.857 (4)F_0.143 (4)Bi_0.857 (4)S₂
M_r	404.26
Crystal system, space group	Tetragonal, P4/nmm
Temperature (K)	300
a, c (Å)	4.0548 (9), 13.370 (3)
V (Å³)	219.82 (11)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	44.78
Crystal size (mm)	0.05 × 0.05 × 0.02

Data collection
Diffractometer	Bruker D8 Quest
Absorption correction	Multi-scan (SADABS; Bruker, 2001 )
T_min, T_max	0.154, 0.511
No. of measured, independent and observed [I > 2σ(I)] reflections	3493, 191, 190
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.052, 1.31
No. of reflections	191
No. of parameters	17
Δρ_max, Δρ_min (e Å⁻³)	1.48, −1.53
Computer programs: APEX2 and SAINT (Bruker, 2004 ), SHELXS (Sheldrick, 2008 ), SHELXL2014 (Sheldrick 2015 ), DIAMOND (Brandenburg, 2004 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1480636

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989016008082/pj2030sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016008082/pj2030Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick 2015); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: publCIF (Westrip, 2010).

Lanthanum calcium bismuth oxide fluoride disulfide top

Crystal data top

Bi_0.857Ca_0.143F_0.143LaO_0.857S₂	D_x = 6.108 Mg m⁻³
M_r = 404.26	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/nmm	Cell parameters from 189 reflections
a = 4.0548 (9) Å	θ = 4.6–27.4°
c = 13.370 (3) Å	µ = 44.78 mm⁻¹
V = 219.82 (11) Å³	T = 300 K
Z = 2	Block, blue
F(000) = 342.3	0.05 × 0.05 × 0.02 mm

Data collection top

Bruker D8 Quest diffractometer	R_int = 0.046
Radiation source: fine-focus sealed tube	θ_max = 27.4°, θ_min = 4.6°
Profile fitted 2θ/ω scans (Clegg, 1981)	h = −5→5
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −5→4
T_min = 0.154, T_max = 0.511	l = −17→17
3493 measured reflections	3 standard reflections every 90 reflections
191 independent reflections	intensity decay: none
190 reflections with I > 2σ(I)

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0318P)² + 0.5025P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.020	(Δ/σ)_max < 0.001
wR(F²) = 0.052	Δρ_max = 1.48 e Å⁻³
S = 1.31	Δρ_min = −1.53 e Å⁻³
191 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
17 parameters	Extinction coefficient: 0.033 (3)
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
La1	0.7500	0.7500	0.89827 (6)	0.0127 (3)
Ca1	0.2500	0.2500	0.62178 (4)	0.0126 (3)	0.143 (4)
Bi1	0.2500	0.2500	0.62178 (4)	0.0126 (3)	0.857 (4)
F1	0.7500	0.2500	1.0000	0.0079 (14)	0.143 (4)
O1	0.7500	0.2500	1.0000	0.0079 (14)	0.857 (4)
S1	0.2500	0.2500	0.8110 (2)	0.0104 (6)
S2	0.7500	0.7500	0.6221 (3)	0.0236 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.0115 (4)	0.0115 (4)	0.0151 (5)	0.000	0.000	0.000
Ca1	0.0146 (3)	0.0146 (3)	0.0087 (3)	0.000	0.000	0.000
Bi1	0.0146 (3)	0.0146 (3)	0.0087 (3)	0.000	0.000	0.000
F1	0.0087 (18)	0.0087 (18)	0.006 (3)	0.000	0.000	0.000
O1	0.0087 (18)	0.0087 (18)	0.006 (3)	0.000	0.000	0.000
S1	0.0101 (7)	0.0101 (7)	0.0109 (12)	0.000	0.000	0.000
S2	0.0200 (10)	0.0200 (10)	0.0306 (18)	0.000	0.000	0.000

Geometric parameters (Å, º) top

La1—O1ⁱ	2.4414 (6)	Ca1—Ca1^v	4.0548 (9)
La1—O1ⁱⁱ	2.4414 (6)	Ca1—Ca1^viii	4.0548 (9)
La1—F1ⁱ	2.4414 (6)	Ca1—Bi1ⁱⁱ	4.0548 (9)
La1—F1ⁱⁱ	2.4414 (6)	Ca1—Bi1^viii	4.0548 (9)
La1—F1	2.4414 (6)	F1—La1ⁱ	2.4414 (6)
La1—O1ⁱⁱⁱ	2.4414 (6)	F1—La1^viii	2.4414 (6)
La1—O1	2.4414 (6)	F1—La1ⁱⁱⁱ	2.4414 (6)
La1—F1ⁱⁱⁱ	2.4414 (6)	O1—La1ⁱ	2.4414 (6)
La1—S1	3.0954 (13)	O1—La1^viii	2.4414 (6)
La1—S1^iv	3.0954 (13)	O1—La1ⁱⁱⁱ	2.4414 (6)
La1—S1ⁱⁱ	3.0954 (13)	S1—La1^vi	3.0954 (13)
La1—S1^v	3.0954 (13)	S1—La1^vii	3.0954 (13)
Ca1—S1	2.530 (3)	S1—La1^viii	3.0954 (13)
Ca1—S2	2.8672 (6)	S2—Bi1^iv	2.8672 (6)
Ca1—S2^vi	2.8672 (6)	S2—Ca1^iv	2.8672 (6)
Ca1—S2^vii	2.8672 (6)	S2—Ca1^v	2.8672 (6)
Ca1—S2^viii	2.8672 (6)	S2—Ca1ⁱⁱ	2.8672 (6)
Ca1—S2^ix	3.261 (4)	S2—Bi1ⁱⁱ	2.8672 (6)
Ca1—Ca1ⁱⁱ	4.0548 (9)	S2—Bi1^v	2.8672 (6)
Ca1—Ca1^vii	4.0548 (9)	S2—Ca1^ix	3.261 (4)

O1ⁱ—La1—O1ⁱⁱ	71.917 (18)	S2^viii—Ca1—Ca1^vii	135.0
O1ⁱ—La1—F1ⁱ	0.0	S2^ix—Ca1—Ca1^vii	90.0
O1ⁱⁱ—La1—F1ⁱ	71.917 (18)	Ca1ⁱⁱ—Ca1—Ca1^vii	90.0
O1ⁱ—La1—F1ⁱⁱ	71.917 (18)	S1—Ca1—Ca1^v	90.0
O1ⁱⁱ—La1—F1ⁱⁱ	0.0	S2—Ca1—Ca1^v	45.0
F1ⁱ—La1—F1ⁱⁱ	71.917 (18)	S2^vi—Ca1—Ca1^v	135.0
O1ⁱ—La1—F1	71.917 (18)	S2^vii—Ca1—Ca1^v	135.0
O1ⁱⁱ—La1—F1	112.29 (4)	S2^viii—Ca1—Ca1^v	45.0
F1ⁱ—La1—F1	71.917 (18)	S2^ix—Ca1—Ca1^v	90.0
F1ⁱⁱ—La1—F1	112.29 (4)	Ca1ⁱⁱ—Ca1—Ca1^v	90.0
O1ⁱ—La1—O1ⁱⁱⁱ	112.29 (4)	Ca1^vii—Ca1—Ca1^v	180.0
O1ⁱⁱ—La1—O1ⁱⁱⁱ	71.917 (18)	S1—Ca1—Ca1^viii	90.0
F1ⁱ—La1—O1ⁱⁱⁱ	112.29 (4)	S2—Ca1—Ca1^viii	135.0
F1ⁱⁱ—La1—O1ⁱⁱⁱ	71.917 (18)	S2^vi—Ca1—Ca1^viii	45.0
F1—La1—O1ⁱⁱⁱ	71.917 (18)	S2^vii—Ca1—Ca1^viii	135.0
O1ⁱ—La1—O1	71.917 (18)	S2^viii—Ca1—Ca1^viii	45.0
O1ⁱⁱ—La1—O1	112.29 (4)	S2^ix—Ca1—Ca1^viii	90.0
F1ⁱ—La1—O1	71.917 (18)	Ca1ⁱⁱ—Ca1—Ca1^viii	180.0
F1ⁱⁱ—La1—O1	112.29 (4)	Ca1^vii—Ca1—Ca1^viii	90.0
F1—La1—O1	0.0	Ca1^v—Ca1—Ca1^viii	90.0
O1ⁱⁱⁱ—La1—O1	71.917 (18)	S1—Ca1—Bi1ⁱⁱ	90.0
O1ⁱ—La1—F1ⁱⁱⁱ	112.29 (4)	S2—Ca1—Bi1ⁱⁱ	45.0
O1ⁱⁱ—La1—F1ⁱⁱⁱ	71.917 (18)	S2^vi—Ca1—Bi1ⁱⁱ	135.0
F1ⁱ—La1—F1ⁱⁱⁱ	112.29 (4)	S2^vii—Ca1—Bi1ⁱⁱ	45.0
F1ⁱⁱ—La1—F1ⁱⁱⁱ	71.917 (18)	S2^viii—Ca1—Bi1ⁱⁱ	135.0
F1—La1—F1ⁱⁱⁱ	71.917 (18)	S2^ix—Ca1—Bi1ⁱⁱ	90.0
O1ⁱⁱⁱ—La1—F1ⁱⁱⁱ	0.0	Ca1ⁱⁱ—Ca1—Bi1ⁱⁱ	0.000 (15)
O1—La1—F1ⁱⁱⁱ	71.917 (18)	Ca1^vii—Ca1—Bi1ⁱⁱ	90.0
O1ⁱ—La1—S1	138.93 (2)	Ca1^v—Ca1—Bi1ⁱⁱ	90.0
O1ⁱⁱ—La1—S1	138.93 (3)	Ca1^viii—Ca1—Bi1ⁱⁱ	180.0
F1ⁱ—La1—S1	138.93 (2)	S1—Ca1—Bi1^viii	90.0
F1ⁱⁱ—La1—S1	138.93 (3)	S2—Ca1—Bi1^viii	135.0
F1—La1—S1	70.49 (4)	S2^vi—Ca1—Bi1^viii	45.0
O1ⁱⁱⁱ—La1—S1	70.49 (4)	S2^vii—Ca1—Bi1^viii	135.0
O1—La1—S1	70.49 (4)	S2^viii—Ca1—Bi1^viii	45.0
F1ⁱⁱⁱ—La1—S1	70.49 (4)	S2^ix—Ca1—Bi1^viii	90.0
O1ⁱ—La1—S1^iv	70.49 (4)	Ca1ⁱⁱ—Ca1—Bi1^viii	180.0
O1ⁱⁱ—La1—S1^iv	70.49 (4)	Ca1^vii—Ca1—Bi1^viii	90.0
F1ⁱ—La1—S1^iv	70.49 (4)	Ca1^v—Ca1—Bi1^viii	90.0
F1ⁱⁱ—La1—S1^iv	70.49 (4)	Ca1^viii—Ca1—Bi1^viii	0.000 (15)
F1—La1—S1^iv	138.93 (3)	Bi1ⁱⁱ—Ca1—Bi1^viii	180.0
O1ⁱⁱⁱ—La1—S1^iv	138.93 (2)	La1ⁱ—F1—La1^viii	108.082 (18)
O1—La1—S1^iv	138.93 (3)	La1ⁱ—F1—La1ⁱⁱⁱ	112.29 (4)
F1ⁱⁱⁱ—La1—S1^iv	138.93 (2)	La1^viii—F1—La1ⁱⁱⁱ	108.082 (18)
S1—La1—S1^iv	135.72 (11)	La1ⁱ—F1—La1	108.082 (18)
O1ⁱ—La1—S1ⁱⁱ	138.93 (3)	La1^viii—F1—La1	112.29 (4)
O1ⁱⁱ—La1—S1ⁱⁱ	70.49 (4)	La1ⁱⁱⁱ—F1—La1	108.082 (18)
F1ⁱ—La1—S1ⁱⁱ	138.93 (3)	La1ⁱ—O1—La1^viii	108.082 (18)
F1ⁱⁱ—La1—S1ⁱⁱ	70.49 (4)	La1ⁱ—O1—La1ⁱⁱⁱ	112.29 (4)
F1—La1—S1ⁱⁱ	138.93 (3)	La1^viii—O1—La1ⁱⁱⁱ	108.082 (18)
O1ⁱⁱⁱ—La1—S1ⁱⁱ	70.49 (4)	La1ⁱ—O1—La1	108.082 (18)
O1—La1—S1ⁱⁱ	138.93 (3)	La1^viii—O1—La1	112.29 (4)
F1ⁱⁱⁱ—La1—S1ⁱⁱ	70.49 (4)	La1ⁱⁱⁱ—O1—La1	108.082 (18)
S1—La1—S1ⁱⁱ	81.84 (4)	Ca1—S1—La1	112.14 (5)
S1^iv—La1—S1ⁱⁱ	81.84 (4)	Ca1—S1—La1^vi	112.14 (5)
O1ⁱ—La1—S1^v	70.49 (4)	La1—S1—La1^vi	135.72 (11)
O1ⁱⁱ—La1—S1^v	138.93 (3)	Ca1—S1—La1^vii	112.14 (5)
F1ⁱ—La1—S1^v	70.49 (4)	La1—S1—La1^vii	81.84 (4)
F1ⁱⁱ—La1—S1^v	138.93 (3)	La1^vi—S1—La1^vii	81.84 (4)
F1—La1—S1^v	70.49 (4)	Ca1—S1—La1^viii	112.14 (5)
O1ⁱⁱⁱ—La1—S1^v	138.93 (3)	La1—S1—La1^viii	81.84 (4)
O1—La1—S1^v	70.49 (4)	La1^vi—S1—La1^viii	81.84 (4)
F1ⁱⁱⁱ—La1—S1^v	138.93 (3)	La1^vii—S1—La1^viii	135.72 (11)
S1—La1—S1^v	81.84 (4)	Ca1—S2—Bi1^iv	179.8
S1^iv—La1—S1^v	81.84 (4)	Ca1—S2—Ca1^iv	179.82 (17)
S1ⁱⁱ—La1—S1^v	135.72 (11)	Bi1^iv—S2—Ca1^iv	0.0
S1—Ca1—S2	89.91 (9)	Ca1—S2—Ca1^v	90.0
S1—Ca1—S2^vi	89.91 (9)	Bi1^iv—S2—Ca1^v	90.0
S2—Ca1—S2^vi	179.82 (17)	Ca1^iv—S2—Ca1^v	90.0
S1—Ca1—S2^vii	89.91 (9)	Ca1—S2—Ca1ⁱⁱ	90.0
S2—Ca1—S2^vii	90.000 (1)	Bi1^iv—S2—Ca1ⁱⁱ	90.0
S2^vi—Ca1—S2^vii	90.000 (1)	Ca1^iv—S2—Ca1ⁱⁱ	90.0
S1—Ca1—S2^viii	89.91 (9)	Ca1^v—S2—Ca1ⁱⁱ	179.82 (17)
S2—Ca1—S2^viii	90.000 (1)	Ca1—S2—Bi1ⁱⁱ	90.0
S2^vi—Ca1—S2^viii	90.0	Bi1^iv—S2—Bi1ⁱⁱ	90.0
S2^vii—Ca1—S2^viii	179.82 (17)	Ca1^iv—S2—Bi1ⁱⁱ	90.0
S1—Ca1—S2^ix	180.0	Ca1^v—S2—Bi1ⁱⁱ	179.82 (17)
S2—Ca1—S2^ix	90.09 (9)	Ca1ⁱⁱ—S2—Bi1ⁱⁱ	0.00 (2)
S2^vi—Ca1—S2^ix	90.09 (9)	Ca1—S2—Bi1^v	90.0
S2^vii—Ca1—S2^ix	90.09 (9)	Bi1^iv—S2—Bi1^v	90.0
S2^viii—Ca1—S2^ix	90.09 (9)	Ca1^iv—S2—Bi1^v	90.0
S1—Ca1—Ca1ⁱⁱ	90.0	Ca1^v—S2—Bi1^v	0.00 (2)
S2—Ca1—Ca1ⁱⁱ	45.0	Ca1ⁱⁱ—S2—Bi1^v	179.82 (17)
S2^vi—Ca1—Ca1ⁱⁱ	135.0	Bi1ⁱⁱ—S2—Bi1^v	179.82 (17)
S2^vii—Ca1—Ca1ⁱⁱ	45.0	Ca1—S2—Ca1^ix	89.91 (9)
S2^viii—Ca1—Ca1ⁱⁱ	135.0	Bi1^iv—S2—Ca1^ix	89.9
S2^ix—Ca1—Ca1ⁱⁱ	90.0	Ca1^iv—S2—Ca1^ix	89.91 (9)
S1—Ca1—Ca1^vii	90.0	Ca1^v—S2—Ca1^ix	89.91 (9)
S2—Ca1—Ca1^vii	135.0	Ca1ⁱⁱ—S2—Ca1^ix	89.91 (9)
S2^vi—Ca1—Ca1^vii	45.0	Bi1ⁱⁱ—S2—Ca1^ix	89.9
S2^vii—Ca1—Ca1^vii	45.0	Bi1^v—S2—Ca1^ix	89.9

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

Acknowledgements

This work was supported financially by the Strategic Priority Research Program (B) of the Chinese Academy of Sciences (grant No. XDB04040200).

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