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

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

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

LaBi_1.859 (4)Ca_0.141 (4)O_0.859 (4)F_0.141 (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.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989016008082/pj2030sup1.cif Contains datablocks I, New_Global_Publ_Block
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989016008082/pj2030Isup2.hkl Contains datablock I

CCDC reference: 1480636

checkCIF report

Key indicators

Single-crystal X-ray study
T = 300 K
Mean (La-S) = 0.001 Å
Disorder in main residue
R factor = 0.020
wR factor = 0.052
Data-to-parameter ratio = 11.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT019_ALERT_1_C _diffrn_measured_fraction_theta_full/*_max < 1.0      0.994 Report
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ     Please Check
PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms ..     Please Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3 Report
PLAT971_ALERT_2_C Check Calcd Residual Density  0.80A From      S2       1.71 eA-3
PLAT971_ALERT_2_C Check Calcd Residual Density  0.82A From      S1       1.63 eA-3

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          2 Info
PLAT045_ALERT_1_G Calculated and Reported Z Differ by a Factor ...       0.50 Check
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          2 Report
PLAT301_ALERT_3_G Main Residue  Disorder ............ Percentage =         40 Note
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          ! Info
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min)           2 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          3 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   6 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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.

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