Crystal structure, absolute configuration and characteristic tem­per­atures of SmFe₃(BO₃)₄ in the tem­per­ature range 11–400 K

The crystal structure of samarium iron borate was analyzed with regard to growth conditions and tem­per­ature. The inclusion of about 7% Bi atoms in the crystals grown using the Bi₂Mo₃O₁₂-based flux was discovered and there were no impurities in the crystals grown using the Li₂WO₄-based flux. No pronounced structural features associated with Bi inclusion were observed. The different absolute configurations of the samples grown using both fluxes were demonstrated. Below 80 K, a negative thermal expansion of the c unit-cell parameter was found. The structure of (Sm_0.93Bi_0.07)Fe₃(BO₃)₄ belongs to the trigonal space group R32 in the tem­per­ature range 90–400 K. A decrease in the (Sm,Bi)—O, Sm—B, Sm—Fe, Fe—O, Fe—B and Fe—Fe distances is observed with a lowering of the tem­per­ature, B1—O does not change, B2—O increases slightly and the B2O₃ triangles deviate from the ab plane. The strongest decrease in the equivalent isotropic atomic displacement parameters (U_eq) with decreasing tem­per­ature is observed for atoms Sm and O2, and the weakest is observed for B1. The O2 atoms have the highest U_eq values, the most elongated atomic displacement ellipsoids of all the atoms and the smallest number of allowed vibrational modes of all the O atoms. The largest number of allowed vibrational modes and the strongest inter­actions with neighbouring atoms is seen for the B atoms, and the opposite is seen for the Sm atoms. The quadrupole splitting Δ(T) of the paramagnetic Mössbauer spectra increases linearly with cooling. The Néel tem­per­ature [T_N = 31.93 (5) K] was determined from the tem­per­ature dependence of the hyperfine magnetic field B_hf(T), which has a non-Brillouin character. The easy-plane long-range magnetic ordering below T_N was confirmed.

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2018) for (90K), 200K, 293K, 400K; CrysAlis PRO (Agilent, 2014) for Sample7_1_NoBi. Cell refinement: CrysAlis PRO (Rigaku OD, 2018) for (90K), 200K, 293K, 400K; CrysAlis PRO (Agilent, 2014) for Sample7_1_NoBi. Data reduction: CrysAlis PRO (Rigaku OD, 2018) for (90K), 200K, 293K, 400K; CrysAlis PRO (Agilent, 2014) for Sample7_1_NoBi. For all structures, program(s) used to solve structure: JANA2006 (Petříček et al., 2014).

Samarium bismuth triiron tetrakis(borate) (90K)

Crystal data

Sm0.93Bi0.07Fe3(BO3)4	Dx = 4.624 Mg m^−3
Mr = 557.2	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R32	Cell parameters from 18525 reflections
Hall symbol: R 3 2"	θ = 4.3–74.0°
a = 9.5638 (1) Å	µ = 13.66 mm^−1
c = 7.5790 (1) Å	T = 90 K
V = 600.35 (1) Å^3	Sphere, light green
Z = 3	0.11 (1) mm (radius)
F(000) = 772

Data collection

Rigaku Xcalibur EosS2 with high theta cut diffractometer	2769 independent reflections
Radiation source: X-ray tube	2769 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 16.1745 pixels mm^-1	θmax = 74.3°, θmin = 3.6°
ω scans	h = −25→25
Absorption correction: for a sphere (JANA2006; Petříček et al., 2014)	k = −25→25
Tmin = 0.159, Tmax = 0.254	l = −20→20
20719 measured reflections

Refinement

Refinement on F^2	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0004I^2)
R[F^2 > 2σ(F^2)] = 0.011	(Δ/σ)max = 0.049
wR(F^2) = 0.030	Δρmax = 1.08 e Å^−3
S = 1.08	Δρmin = −0.95 e Å^−3
2769 reflections	Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
36 parameters	Extinction coefficient: 238E1 (6)
0 restraints	Absolute structure: 1253 of Friedel pairs used in the refinement
2 constraints	Absolute structure parameter: 0.028 (4)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Sm1	0	0	0	0.003087 (9)	0.93
Bi1	0	0	0	0.003087 (9)	0.07
Fe1	0.783046 (13)	0.666667	0.666667	0.002644 (17)
O1	0.85571 (6)	0.85571 (6)	0.5	0.00397 (8)
O2	0.59106 (7)	0.59106 (7)	0.5	0.00570 (10)
O3	0.97422 (5)	0.78660 (6)	0.81628 (6)	0.00461 (8)
B1	0	0	0.5	0.00371 (16)
B2	0.44717 (9)	0.44717 (9)	0.5	0.00393 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sm1	0.003186 (11)	0.003186 (11)	0.002888 (14)	0.001593 (6)	0	0
Bi1	0.003186 (11)	0.003186 (11)	0.002888 (14)	0.001593 (6)	0	0
Fe1	0.00256 (2)	0.00256 (2)	0.00281 (3)	0.001279 (12)	−0.000026 (7)	−0.000052 (14)
O1	0.00311 (8)	0.00311 (8)	0.00486 (12)	0.00094 (10)	−0.00045 (5)	0.00045 (5)
O2	0.00377 (10)	0.00377 (10)	0.00760 (16)	0.00040 (13)	−0.00164 (7)	0.00164 (7)
O3	0.00364 (9)	0.00535 (10)	0.00520 (9)	0.00253 (8)	−0.00070 (7)	−0.00078 (7)
B1	0.00352 (19)	0.00352 (19)	0.0041 (3)	0.00176 (9)	0	0
B2	0.00338 (15)	0.00338 (15)	0.00473 (17)	0.0014 (2)	−0.00011 (9)	0.00011 (9)

Geometric parameters (Å, º)

Sm1—Bi1	0	Bi1—O3^v	2.3794 (4)
Sm1—O3^i	2.3794 (5)	Bi1—O3^vi	2.3794 (7)
Sm1—O3^ii	2.3794 (4)	Fe1—O1	2.0226 (4)
Sm1—O3^iii	2.3794 (7)	Fe1—O1^vii	2.0226 (4)
Sm1—O3^iv	2.3794 (5)	Fe1—O2	2.0401 (5)
Sm1—O3^v	2.3794 (4)	Fe1—O2^vii	2.0401 (9)
Sm1—O3^vi	2.3794 (7)	Fe1—O3	1.9614 (4)
Bi1—O3^i	2.3794 (5)	Fe1—O3^viii	1.9614 (7)
Bi1—O3^ii	2.3794 (4)	O1—B1^ix	1.3800 (4)
Bi1—O3^iii	2.3794 (7)	O2—B2	1.3761 (8)
Bi1—O3^iv	2.3794 (5)	O3—B2^x	1.3715 (11)
Bi1—Sm1—O3^i	0	O3^iii—Bi1—O3^vi	142.040 (14)
Bi1—Sm1—O3^ii	0	O3^iv—Bi1—O3^v	89.217 (18)
Bi1—Sm1—O3^iii	0	O3^iv—Bi1—O3^vi	89.217 (18)
Bi1—Sm1—O3^iv	0	O3^v—Bi1—O3^vi	89.217 (18)
Bi1—Sm1—O3^v	0	O1—Fe1—O1^vii	168.13 (3)
Bi1—Sm1—O3^vi	0	O1—Fe1—O2	77.069 (19)
O3^i—Sm1—O3^ii	89.217 (18)	O1—Fe1—O2^vii	94.27 (2)
O3^i—Sm1—O3^iii	89.217 (18)	O1—Fe1—O3	92.013 (18)
O3^i—Sm1—O3^iv	122.541 (14)	O1—Fe1—O3^viii	95.57 (2)
O3^i—Sm1—O3^v	142.04 (2)	O1^vii—Fe1—O2	94.27 (2)
O3^i—Sm1—O3^vi	72.602 (18)	O1^vii—Fe1—O2^vii	77.07 (3)
O3^ii—Sm1—O3^iii	89.217 (18)	O1^vii—Fe1—O3	95.57 (2)
O3^ii—Sm1—O3^iv	142.04 (2)	O1^vii—Fe1—O3^viii	92.01 (2)
O3^ii—Sm1—O3^v	72.602 (16)	O2—Fe1—O2^vii	87.43 (3)
O3^ii—Sm1—O3^vi	122.54 (2)	O2—Fe1—O3	167.37 (3)
O3^iii—Sm1—O3^iv	72.602 (18)	O2—Fe1—O3^viii	87.08 (3)
O3^iii—Sm1—O3^v	122.54 (2)	O2^vii—Fe1—O3	87.08 (3)
O3^iii—Sm1—O3^vi	142.040 (14)	O2^vii—Fe1—O3^viii	167.37 (2)
O3^iv—Sm1—O3^v	89.217 (18)	O3—Fe1—O3^viii	100.45 (3)
O3^iv—Sm1—O3^vi	89.217 (18)	Fe1—O1—Fe1^xi	103.552 (19)
O3^v—Sm1—O3^vi	89.217 (18)	Fe1—O1—B1^ix	128.22 (3)
Sm1—Bi1—O3^i	0	Fe1^xi—O1—B1^ix	128.22 (3)
Sm1—Bi1—O3^ii	0	Fe1—O2—Fe1^xi	102.31 (2)
Sm1—Bi1—O3^iii	0	Fe1—O2—B2	128.84 (4)
Sm1—Bi1—O3^iv	0	Fe1^xi—O2—B2	128.84 (4)
Sm1—Bi1—O3^v	0	Sm1^xii—O3—Bi1^xii	0.0 (5)
Sm1—Bi1—O3^vi	0	Sm1^xii—O3—Fe1	120.43 (3)
O3^i—Bi1—O3^ii	89.217 (18)	Sm1^xii—O3—B2^x	107.20 (3)
O3^i—Bi1—O3^iii	89.217 (18)	Bi1^xii—O3—Fe1	120.43 (3)
O3^i—Bi1—O3^iv	122.541 (14)	Bi1^xii—O3—B2^x	107.20 (3)
O3^i—Bi1—O3^v	142.04 (2)	Fe1—O3—B2^x	132.24 (4)
O3^i—Bi1—O3^vi	72.602 (18)	O1^xiii—B1—O1^xiv	120.00 (4)
O3^ii—Bi1—O3^iii	89.217 (18)	O1^xiii—B1—O1^xv	120.00 (4)
O3^ii—Bi1—O3^iv	142.04 (2)	O1^xiv—B1—O1^xv	120.00 (4)
O3^ii—Bi1—O3^v	72.602 (16)	O2—B2—O3^xvi	117.75 (8)
O3^ii—Bi1—O3^vi	122.54 (2)	O2—B2—O3^xvii	117.75 (8)
O3^iii—Bi1—O3^iv	72.602 (18)	O3^xvi—B2—O3^xvii	124.51 (5)
O3^iii—Bi1—O3^v	122.54 (2)

Symmetry codes: (i) x−1, y−1, z−1; (ii) −y+1, x−y, z−1; (iii) −x+y, −x+1, z−1; (iv) y−1, x−1, −z+1; (v) x−y, −y+1, −z+1; (vi) −x+1, −x+y, −z+1; (vii) −x+y+2/3, −x+4/3, z+1/3; (viii) x−y+2/3, −y+4/3, −z+4/3; (ix) x+1, y+1, z; (x) x+2/3, y+1/3, z+1/3; (xi) −y+4/3, x−y+2/3, z−1/3; (xii) x+1, y+1, z+1; (xiii) x−1, y−1, z; (xiv) −y+1, x−y, z; (xv) −x+y, −x+1, z; (xvi) x−2/3, y−1/3, z−1/3; (xvii) y−1/3, x−2/3, −z+4/3.

Samarium bismuth triiron tetrakis(borate) (200K)

Crystal data

Sm0.93Bi0.07Fe3(BO3)4	Dx = 4.622 Mg m^−3
Mr = 557.2	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R32	Cell parameters from 18525 reflections
Hall symbol: R 3 2"	θ = 4.3–73.9°
a = 9.5635 (1) Å	µ = 13.66 mm^−1
c = 7.5823 (1) Å	T = 200 K
V = 600.57 (1) Å^3	Sphere, light green
Z = 3	0.11 (1) mm (radius)
F(000) = 772

Data collection

Rigaku Xcalibur EosS2 with high theta cut diffractometer	2770 independent reflections
Radiation source: X-ray tube	2770 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.031
Detector resolution: 16.1745 pixels mm^-1	θmax = 74.3°, θmin = 3.6°
ω scans	h = −25→25
Absorption correction: for a sphere (JANA2006; Petříček et al., 2014)	k = −25→25
Tmin = 0.159, Tmax = 0.254	l = −20→20
20756 measured reflections

Refinement

Refinement on F^2	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0004I^2)
R[F^2 > 2σ(F^2)] = 0.011	(Δ/σ)max = 0.049
wR(F^2) = 0.030	Δρmax = 0.96 e Å^−3
S = 1.04	Δρmin = −0.58 e Å^−3
2770 reflections	Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
36 parameters	Extinction coefficient: 305E1 (6)
0 restraints	Absolute structure: 1253 of Friedel pairs used in the refinement
2 constraints	Absolute structure parameter: 0.030 (4)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Sm1	0	0	0	0.005360 (10)	0.93
Bi1	0	0	0	0.005360 (10)	0.07
Fe1	0.783019 (12)	0.666667	0.666667	0.003812 (17)
O1	0.85570 (6)	0.85570 (6)	0.5	0.00513 (8)
O2	0.59079 (7)	0.59079 (7)	0.5	0.00841 (11)
O3	0.97419 (5)	0.78650 (6)	0.81627 (6)	0.00627 (8)
B1	0	0	0.5	0.00428 (15)
B2	0.44698 (9)	0.44698 (9)	0.5	0.00496 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sm1	0.005531 (13)	0.005531 (13)	0.005019 (15)	0.002766 (7)	0	0
Bi1	0.005531 (13)	0.005531 (13)	0.005019 (15)	0.002766 (7)	0	0
Fe1	0.00361 (2)	0.00370 (2)	0.00416 (3)	0.001849 (12)	−0.000047 (7)	−0.000094 (14)
O1	0.00385 (8)	0.00385 (8)	0.00644 (12)	0.00097 (10)	−0.00070 (5)	0.00070 (5)
O2	0.00512 (10)	0.00512 (10)	0.01150 (19)	−0.00008 (13)	−0.00296 (8)	0.00296 (8)
O3	0.00458 (9)	0.00759 (11)	0.00697 (9)	0.00329 (8)	−0.00106 (7)	−0.00129 (8)
B1	0.00390 (18)	0.00390 (18)	0.0050 (3)	0.00195 (9)	0	0
B2	0.00428 (15)	0.00428 (15)	0.00601 (16)	0.0019 (2)	−0.00029 (9)	0.00029 (9)

Geometric parameters (Å, º)

Sm1—Bi1	0	Bi1—O3^v	2.3805 (5)
Sm1—O3^i	2.3805 (5)	Bi1—O3^vi	2.3805 (7)
Sm1—O3^ii	2.3805 (5)	Fe1—O1	2.0228 (4)
Sm1—O3^iii	2.3805 (7)	Fe1—O1^vii	2.0228 (4)
Sm1—O3^iv	2.3805 (5)	Fe1—O2	2.0419 (5)
Sm1—O3^v	2.3805 (5)	Fe1—O2^vii	2.0418 (9)
Sm1—O3^vi	2.3805 (7)	Fe1—O3	1.9615 (4)
Bi1—O3^i	2.3805 (5)	Fe1—O3^viii	1.9615 (7)
Bi1—O3^ii	2.3805 (5)	O1—B1^ix	1.3801 (4)
Bi1—O3^iii	2.3805 (7)	O2—B2	1.3753 (8)
Bi1—O3^iv	2.3805 (5)	O3—B2^x	1.3703 (11)
Bi1—Sm1—O3^i	0	O3^iii—Bi1—O3^vi	142.046 (14)
Bi1—Sm1—O3^ii	0	O3^iv—Bi1—O3^v	89.214 (19)
Bi1—Sm1—O3^iii	0	O3^iv—Bi1—O3^vi	89.214 (19)
Bi1—Sm1—O3^iv	0	O3^v—Bi1—O3^vi	89.214 (19)
Bi1—Sm1—O3^v	0	O1—Fe1—O1^vii	168.15 (3)
Bi1—Sm1—O3^vi	0	O1—Fe1—O2	77.111 (19)
O3^i—Sm1—O3^ii	89.214 (19)	O1—Fe1—O2^vii	94.23 (2)
O3^i—Sm1—O3^iii	89.214 (19)	O1—Fe1—O3	92.048 (18)
O3^i—Sm1—O3^iv	122.538 (14)	O1—Fe1—O3^viii	95.53 (2)
O3^i—Sm1—O3^v	142.05 (2)	O1^vii—Fe1—O2	94.23 (2)
O3^i—Sm1—O3^vi	72.607 (19)	O1^vii—Fe1—O2^vii	77.11 (3)
O3^ii—Sm1—O3^iii	89.214 (19)	O1^vii—Fe1—O3	95.53 (2)
O3^ii—Sm1—O3^iv	142.05 (2)	O1^vii—Fe1—O3^viii	92.05 (2)
O3^ii—Sm1—O3^v	72.607 (16)	O2—Fe1—O2^vii	87.45 (3)
O3^ii—Sm1—O3^vi	122.54 (2)	O2—Fe1—O3	167.45 (3)
O3^iii—Sm1—O3^iv	72.607 (19)	O2—Fe1—O3^viii	87.07 (3)
O3^iii—Sm1—O3^v	122.54 (2)	O2^vii—Fe1—O3	87.07 (3)
O3^iii—Sm1—O3^vi	142.046 (14)	O2^vii—Fe1—O3^viii	167.45 (2)
O3^iv—Sm1—O3^v	89.214 (19)	O3—Fe1—O3^viii	100.42 (3)
O3^iv—Sm1—O3^vi	89.214 (19)	Fe1—O1—Fe1^xi	103.563 (18)
O3^v—Sm1—O3^vi	89.214 (19)	Fe1—O1—B1^ix	128.22 (3)
Sm1—Bi1—O3^i	0	Fe1^xi—O1—B1^ix	128.22 (3)
Sm1—Bi1—O3^ii	0	Fe1—O2—Fe1^xi	102.21 (2)
Sm1—Bi1—O3^iii	0	Fe1—O2—B2	128.89 (4)
Sm1—Bi1—O3^iv	0	Fe1^xi—O2—B2	128.89 (4)
Sm1—Bi1—O3^v	0	Sm1^xii—O3—Bi1^xii	0.0 (5)
Sm1—Bi1—O3^vi	0	Sm1^xii—O3—Fe1	120.41 (3)
O3^i—Bi1—O3^ii	89.214 (19)	Sm1^xii—O3—B2^x	107.22 (3)
O3^i—Bi1—O3^iii	89.214 (19)	Bi1^xii—O3—Fe1	120.41 (3)
O3^i—Bi1—O3^iv	122.538 (14)	Bi1^xii—O3—B2^x	107.22 (3)
O3^i—Bi1—O3^v	142.05 (2)	Fe1—O3—B2^x	132.25 (4)
O3^i—Bi1—O3^vi	72.607 (19)	O1^xiii—B1—O1^xiv	120.00 (4)
O3^ii—Bi1—O3^iii	89.214 (19)	O1^xiii—B1—O1^xv	120.00 (4)
O3^ii—Bi1—O3^iv	142.05 (2)	O1^xiv—B1—O1^xv	120.00 (4)
O3^ii—Bi1—O3^v	72.607 (16)	O2—B2—O3^xvi	117.71 (8)
O3^ii—Bi1—O3^vi	122.54 (2)	O2—B2—O3^xvii	117.71 (8)
O3^iii—Bi1—O3^iv	72.607 (19)	O3^xvi—B2—O3^xvii	124.58 (5)
O3^iii—Bi1—O3^v	122.54 (2)

Symmetry codes: (i) x−1, y−1, z−1; (ii) −y+1, x−y, z−1; (iii) −x+y, −x+1, z−1; (iv) y−1, x−1, −z+1; (v) x−y, −y+1, −z+1; (vi) −x+1, −x+y, −z+1; (vii) −x+y+2/3, −x+4/3, z+1/3; (viii) x−y+2/3, −y+4/3, −z+4/3; (ix) x+1, y+1, z; (x) x+2/3, y+1/3, z+1/3; (xi) −y+4/3, x−y+2/3, z−1/3; (xii) x+1, y+1, z+1; (xiii) x−1, y−1, z; (xiv) −y+1, x−y, z; (xv) −x+y, −x+1, z; (xvi) x−2/3, y−1/3, z−1/3; (xvii) y−1/3, x−2/3, −z+4/3.

Samarium bismuth triiron tetrakis(borate) (293K)

Crystal data

Sm0.93Bi0.07Fe3(BO3)4	Dx = 4.618 Mg m^−3
Mr = 557.2	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R32	Cell parameters from 18022 reflections
Hall symbol: R 3 2"	θ = 4.3–74°
a = 9.5642 (1) Å	µ = 13.65 mm^−1
c = 7.5883 (1) Å	T = 293 K
V = 601.14 (1) Å^3	Sphere, light green
Z = 3	0.11 (1) mm (radius)
F(000) = 772

Data collection

Rigaku Xcalibur EosS2 with high theta cut diffractometer	2774 independent reflections
Radiation source: X-ray tube	2772 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 16.1745 pixels mm^-1	θmax = 74.4°, θmin = 3.6°
ω scans	h = −25→25
Absorption correction: for a sphere (JANA2006; Petříček et al., 2014)	k = −25→25
Tmin = 0.160, Tmax = 0.255	l = −20→20
20806 measured reflections

Refinement

Refinement on F^2	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0004I^2)
R[F^2 > 2σ(F^2)] = 0.012	(Δ/σ)max = 0.047
wR(F^2) = 0.032	Δρmax = 1.02 e Å^−3
S = 1.04	Δρmin = −0.63 e Å^−3
2774 reflections	Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
36 parameters	Extinction coefficient: 328E1 (6)
0 restraints	Absolute structure: 1254 of Friedel pairs used in the refinement
2 constraints	Absolute structure parameter: 0.031 (4)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Sm1	0	0	0	0.007298 (12)	0.93
Bi1	0	0	0	0.007298 (12)	0.07
Fe1	0.783039 (13)	0.666667	0.666667	0.004945 (19)
O1	0.85574 (6)	0.85574 (6)	0.5	0.00650 (8)
O2	0.59065 (8)	0.59065 (8)	0.5	0.01089 (12)
O3	0.97414 (6)	0.78639 (7)	0.81626 (7)	0.00802 (9)
B1	0	0	0.5	0.00510 (16)
B2	0.44692 (9)	0.44692 (9)	0.5	0.00598 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sm1	0.007518 (16)	0.007518 (16)	0.006857 (18)	0.003759 (8)	0	0
Bi1	0.007518 (16)	0.007518 (16)	0.006857 (18)	0.003759 (8)	0	0
Fe1	0.00466 (2)	0.00482 (3)	0.00542 (3)	0.002408 (13)	−0.000061 (8)	−0.000123 (16)
O1	0.00480 (9)	0.00480 (9)	0.00810 (13)	0.00105 (10)	−0.00095 (6)	0.00095 (6)
O2	0.00642 (11)	0.00642 (11)	0.0150 (2)	−0.00043 (14)	−0.00422 (10)	0.00422 (10)
O3	0.00585 (10)	0.00991 (13)	0.00888 (11)	0.00437 (10)	−0.00152 (8)	−0.00181 (9)
B1	0.00467 (19)	0.00467 (19)	0.0060 (3)	0.00233 (10)	0	0
B2	0.00498 (15)	0.00498 (15)	0.00729 (17)	0.0020 (2)	−0.00035 (11)	0.00035 (11)

Geometric parameters (Å, º)

Sm1—Bi1	0	Bi1—O3^v	2.3820 (5)
Sm1—O3^i	2.3820 (6)	Bi1—O3^vi	2.3820 (8)
Sm1—O3^ii	2.3820 (5)	Fe1—O1	2.0238 (4)
Sm1—O3^iii	2.3820 (8)	Fe1—O1^vii	2.0238 (4)
Sm1—O3^iv	2.3820 (6)	Fe1—O2	2.0436 (6)
Sm1—O3^v	2.3820 (5)	Fe1—O2^vii	2.0435 (9)
Sm1—O3^vi	2.3820 (8)	Fe1—O3	1.9615 (5)
Bi1—O3^i	2.3820 (6)	Fe1—O3^viii	1.9616 (8)
Bi1—O3^ii	2.3820 (5)	O1—B1^ix	1.3797 (4)
Bi1—O3^iii	2.3820 (8)	O2—B2	1.3747 (8)
Bi1—O3^iv	2.3820 (6)	O3—B2^x	1.3701 (12)
Bi1—Sm1—O3^i	0	O3^iii—Bi1—O3^vi	142.064 (16)
Bi1—Sm1—O3^ii	0	O3^iv—Bi1—O3^v	89.20 (2)
Bi1—Sm1—O3^iii	0	O3^iv—Bi1—O3^vi	89.20 (2)
Bi1—Sm1—O3^iv	0	O3^v—Bi1—O3^vi	89.20 (2)
Bi1—Sm1—O3^v	0	O1—Fe1—O1^vii	168.15 (3)
Bi1—Sm1—O3^vi	0	O1—Fe1—O2	77.12 (2)
O3^i—Sm1—O3^ii	89.20 (2)	O1—Fe1—O2^vii	94.23 (2)
O3^i—Sm1—O3^iii	89.20 (2)	O1—Fe1—O3	92.09 (2)
O3^i—Sm1—O3^iv	122.530 (16)	O1—Fe1—O3^viii	95.48 (2)
O3^i—Sm1—O3^v	142.06 (3)	O1^vii—Fe1—O2	94.23 (2)
O3^i—Sm1—O3^vi	72.63 (2)	O1^vii—Fe1—O2^vii	77.12 (3)
O3^ii—Sm1—O3^iii	89.20 (2)	O1^vii—Fe1—O3	95.48 (2)
O3^ii—Sm1—O3^iv	142.06 (3)	O1^vii—Fe1—O3^viii	92.09 (3)
O3^ii—Sm1—O3^v	72.626 (18)	O2—Fe1—O2^vii	87.47 (3)
O3^ii—Sm1—O3^vi	122.53 (2)	O2—Fe1—O3	167.50 (3)
O3^iii—Sm1—O3^iv	72.63 (2)	O2—Fe1—O3^viii	87.04 (3)
O3^iii—Sm1—O3^v	122.53 (2)	O2^vii—Fe1—O3	87.04 (3)
O3^iii—Sm1—O3^vi	142.064 (16)	O2^vii—Fe1—O3^viii	167.50 (2)
O3^iv—Sm1—O3^v	89.20 (2)	O3—Fe1—O3^viii	100.43 (3)
O3^iv—Sm1—O3^vi	89.20 (2)	Fe1—O1—Fe1^xi	103.58 (2)
O3^v—Sm1—O3^vi	89.20 (2)	Fe1—O1—B1^ix	128.21 (3)
Sm1—Bi1—O3^i	0	Fe1^xi—O1—B1^ix	128.21 (3)
Sm1—Bi1—O3^ii	0	Fe1—O2—Fe1^xi	102.18 (2)
Sm1—Bi1—O3^iii	0	Fe1—O2—B2	128.91 (4)
Sm1—Bi1—O3^iv	0	Fe1^xi—O2—B2	128.91 (4)
Sm1—Bi1—O3^v	0	Sm1^xii—O3—Bi1^xii	0.0 (5)
Sm1—Bi1—O3^vi	0	Sm1^xii—O3—Fe1	120.41 (3)
O3^i—Bi1—O3^ii	89.20 (2)	Sm1^xii—O3—B2^x	107.19 (3)
O3^i—Bi1—O3^iii	89.20 (2)	Bi1^xii—O3—Fe1	120.41 (3)
O3^i—Bi1—O3^iv	122.530 (16)	Bi1^xii—O3—B2^x	107.19 (3)
O3^i—Bi1—O3^v	142.06 (3)	Fe1—O3—B2^x	132.27 (5)
O3^i—Bi1—O3^vi	72.63 (2)	O1^xiii—B1—O1^xiv	120.00 (4)
O3^ii—Bi1—O3^iii	89.20 (2)	O1^xiii—B1—O1^xv	120.00 (4)
O3^ii—Bi1—O3^iv	142.06 (3)	O1^xiv—B1—O1^xv	120.00 (4)
O3^ii—Bi1—O3^v	72.626 (18)	O2—B2—O3^xvi	117.73 (8)
O3^ii—Bi1—O3^vi	122.53 (2)	O2—B2—O3^xvii	117.73 (8)
O3^iii—Bi1—O3^iv	72.63 (2)	O3^xvi—B2—O3^xvii	124.54 (6)
O3^iii—Bi1—O3^v	122.53 (2)

Symmetry codes: (i) x−1, y−1, z−1; (ii) −y+1, x−y, z−1; (iii) −x+y, −x+1, z−1; (iv) y−1, x−1, −z+1; (v) x−y, −y+1, −z+1; (vi) −x+1, −x+y, −z+1; (vii) −x+y+2/3, −x+4/3, z+1/3; (viii) x−y+2/3, −y+4/3, −z+4/3; (ix) x+1, y+1, z; (x) x+2/3, y+1/3, z+1/3; (xi) −y+4/3, x−y+2/3, z−1/3; (xii) x+1, y+1, z+1; (xiii) x−1, y−1, z; (xiv) −y+1, x−y, z; (xv) −x+y, −x+1, z; (xvi) x−2/3, y−1/3, z−1/3; (xvii) y−1/3, x−2/3, −z+4/3.

Samarium bismuth triiron tetrakis(borate) (400K)

Crystal data

Sm0.93Bi0.07Fe3(BO3)4	Dx = 4.612 Mg m^−3
Mr = 557.2	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R32	Cell parameters from 17062 reflections
Hall symbol: R 3 2"	θ = 4.3–74.1°
a = 9.5650 (1) Å	µ = 13.63 mm^−1
c = 7.5972 (1) Å	T = 400 K
V = 601.94 (1) Å^3	Sphere, light green
Z = 3	0.11 (1) mm (radius)
F(000) = 772

Data collection

Rigaku Xcalibur EosS2 with high theta cut diffractometer	2781 independent reflections
Radiation source: X-ray tube	2761 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 16.1745 pixels mm^-1	θmax = 74.4°, θmin = 3.6°
ω scans	h = −25→25
Absorption correction: for a sphere (JANA2006; Petříček et al., 2014)	k = −25→25
Tmin = 0.116, Tmax = 0.215	l = −20→20
20801 measured reflections

Refinement

Refinement on F^2	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.000196I^2)
R[F^2 > 2σ(F^2)] = 0.012	(Δ/σ)max = 0.047
wR(F^2) = 0.029	Δρmax = 0.83 e Å^−3
S = 1.03	Δρmin = −0.92 e Å^−3
2781 reflections	Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
36 parameters	Extinction coefficient: 283E1 (4)
0 restraints	Absolute structure: 1259 of Friedel pairs used in the refinement
2 constraints	Absolute structure parameter: 0.028 (4)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Sm1	0	0	0	0.010045 (14)	0.93
Bi1	0	0	0	0.010045 (14)	0.07
Fe1	0.783072 (13)	0.666667	0.666667	0.006755 (19)
O1	0.85579 (6)	0.85579 (6)	0.5	0.00859 (9)
O2	0.59067 (8)	0.59067 (8)	0.5	0.01407 (14)
O3	0.97415 (6)	0.78624 (7)	0.81623 (7)	0.01053 (10)
B1	0	0	0.5	0.00660 (16)
B2	0.44683 (9)	0.44683 (9)	0.5	0.00770 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sm1	0.010342 (18)	0.010342 (18)	0.00945 (2)	0.005171 (9)	0	0
Bi1	0.010342 (18)	0.010342 (18)	0.00945 (2)	0.005171 (9)	0	0
Fe1	0.00636 (2)	0.00658 (3)	0.00740 (3)	0.003290 (13)	−0.000100 (9)	−0.000201 (18)
O1	0.00635 (9)	0.00635 (9)	0.01077 (15)	0.00145 (11)	−0.00124 (6)	0.00124 (6)
O2	0.00847 (12)	0.00847 (12)	0.0194 (3)	−0.00018 (15)	−0.00517 (11)	0.00517 (11)
O3	0.00739 (11)	0.01289 (14)	0.01184 (12)	0.00547 (11)	−0.00214 (9)	−0.00277 (10)
B1	0.00622 (19)	0.00622 (19)	0.0074 (3)	0.00311 (10)	0	0
B2	0.00669 (16)	0.00669 (16)	0.00922 (16)	0.0030 (3)	−0.00033 (11)	0.00033 (11)

Geometric parameters (Å, º)

Sm1—Bi1	0	Bi1—O3^v	2.3844 (5)
Sm1—O3^i	2.3844 (6)	Bi1—O3^vi	2.3844 (8)
Sm1—O3^ii	2.3844 (5)	Fe1—O1	2.0251 (4)
Sm1—O3^iii	2.3844 (8)	Fe1—O1^vii	2.0251 (4)
Sm1—O3^iv	2.3844 (6)	Fe1—O2	2.0447 (6)
Sm1—O3^v	2.3844 (5)	Fe1—O2^vii	2.0447 (9)
Sm1—O3^vi	2.3844 (8)	Fe1—O3	1.9619 (5)
Bi1—O3^i	2.3844 (6)	Fe1—O3^viii	1.9619 (8)
Bi1—O3^ii	2.3844 (5)	O1—B1^ix	1.3794 (4)
Bi1—O3^iii	2.3844 (8)	O2—B2	1.3759 (8)
Bi1—O3^iv	2.3844 (6)	O3—B2^x	1.3690 (11)
Bi1—Sm1—O3^i	0	O3^iii—Bi1—O3^vi	142.064 (16)
Bi1—Sm1—O3^ii	0	O3^iv—Bi1—O3^v	89.18 (2)
Bi1—Sm1—O3^iii	0	O3^iv—Bi1—O3^vi	89.18 (2)
Bi1—Sm1—O3^iv	0	O3^v—Bi1—O3^vi	89.18 (2)
Bi1—Sm1—O3^v	0	O1—Fe1—O1^vii	168.16 (3)
Bi1—Sm1—O3^vi	0	O1—Fe1—O2	77.08 (2)
O3^i—Sm1—O3^ii	89.18 (2)	O1—Fe1—O2^vii	94.27 (2)
O3^i—Sm1—O3^iii	89.18 (2)	O1—Fe1—O3	92.16 (2)
O3^i—Sm1—O3^iv	122.550 (16)	O1—Fe1—O3^viii	95.42 (2)
O3^i—Sm1—O3^v	142.06 (3)	O1^vii—Fe1—O2	94.27 (2)
O3^i—Sm1—O3^vi	72.65 (2)	O1^vii—Fe1—O2^vii	77.08 (3)
O3^ii—Sm1—O3^iii	89.18 (2)	O1^vii—Fe1—O3	95.42 (2)
O3^ii—Sm1—O3^iv	142.06 (3)	O1^vii—Fe1—O3^viii	92.16 (3)
O3^ii—Sm1—O3^v	72.653 (19)	O2—Fe1—O2^vii	87.51 (3)
O3^ii—Sm1—O3^vi	122.55 (2)	O2—Fe1—O3	167.53 (3)
O3^iii—Sm1—O3^iv	72.65 (2)	O2—Fe1—O3^viii	87.03 (3)
O3^iii—Sm1—O3^v	122.55 (2)	O2^vii—Fe1—O3	87.03 (3)
O3^iii—Sm1—O3^vi	142.064 (16)	O2^vii—Fe1—O3^viii	167.53 (2)
O3^iv—Sm1—O3^v	89.18 (2)	O3—Fe1—O3^viii	100.41 (3)
O3^iv—Sm1—O3^vi	89.18 (2)	Fe1—O1—Fe1^xi	103.609 (19)
O3^v—Sm1—O3^vi	89.18 (2)	Fe1—O1—B1^ix	128.20 (3)
Sm1—Bi1—O3^i	0	Fe1^xi—O1—B1^ix	128.20 (3)
Sm1—Bi1—O3^ii	0	Fe1—O2—Fe1^xi	102.23 (2)
Sm1—Bi1—O3^iii	0	Fe1—O2—B2	128.89 (4)
Sm1—Bi1—O3^iv	0	Fe1^xi—O2—B2	128.89 (4)
Sm1—Bi1—O3^v	0	Sm1^xii—O3—Bi1^xii	0.0 (5)
Sm1—Bi1—O3^vi	0	Sm1^xii—O3—Fe1	120.40 (3)
O3^i—Bi1—O3^ii	89.18 (2)	Sm1^xii—O3—B2^x	107.16 (3)
O3^i—Bi1—O3^iii	89.18 (2)	Bi1^xii—O3—Fe1	120.40 (3)
O3^i—Bi1—O3^iv	122.550 (16)	Bi1^xii—O3—B2^x	107.16 (3)
O3^i—Bi1—O3^v	142.06 (3)	Fe1—O3—B2^x	132.31 (5)
O3^i—Bi1—O3^vi	72.65 (2)	O1^xiii—B1—O1^xiv	120.00 (4)
O3^ii—Bi1—O3^iii	89.18 (2)	O1^xiii—B1—O1^xv	120.00 (4)
O3^ii—Bi1—O3^iv	142.06 (3)	O1^xiv—B1—O1^xv	120.00 (4)
O3^ii—Bi1—O3^v	72.653 (19)	O2—B2—O3^xvi	117.75 (8)
O3^ii—Bi1—O3^vi	122.55 (2)	O2—B2—O3^xvii	117.75 (8)
O3^iii—Bi1—O3^iv	72.65 (2)	O3^xvi—B2—O3^xvii	124.51 (5)
O3^iii—Bi1—O3^v	122.55 (2)

Symmetry codes: (i) x−1, y−1, z−1; (ii) −y+1, x−y, z−1; (iii) −x+y, −x+1, z−1; (iv) y−1, x−1, −z+1; (v) x−y, −y+1, −z+1; (vi) −x+1, −x+y, −z+1; (vii) −x+y+2/3, −x+4/3, z+1/3; (viii) x−y+2/3, −y+4/3, −z+4/3; (ix) x+1, y+1, z; (x) x+2/3, y+1/3, z+1/3; (xi) −y+4/3, x−y+2/3, z−1/3; (xii) x+1, y+1, z+1; (xiii) x−1, y−1, z; (xiv) −y+1, x−y, z; (xv) −x+y, −x+1, z; (xvi) x−2/3, y−1/3, z−1/3; (xvii) y−1/3, x−2/3, −z+4/3.

(Sample7_1_NoBi)

Crystal data

SmFe3B4O12	Dx = 4.580 Mg m^−3
Mr = 553.1	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R32	Cell parameters from 19924 reflections
Hall symbol: R 3 2"	θ = 5.6–73.7°
a = 9.5665 (1) Å	µ = 12.61 mm^−1
c = 7.5911 (1) Å	T = 293 K
V = 601.65 (1) Å^3	Sphere, light-green
Z = 3	0.13 mm (radius)
F(000) = 768

Data collection

Rigaku Xcalibur EosS2 with high theta cut diffractometer	2770 independent reflections
Radiation source: X-ray tube	2770 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 16.0628 pixels mm^-1	θmax = 74.2°, θmin = 4.3°
ω scans	h = −25→24
Absorption correction: for a sphere (JANA2006; Petříček et al., 2014)	k = −21→23
Tmin = 0.109, Tmax = 0.208	l = −19→20
20799 measured reflections

Refinement

Refinement on F^2	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0004I^2)
R[F^2 > 2σ(F^2)] = 0.009	(Δ/σ)max = 0.047
wR(F^2) = 0.026	Δρmax = 1.12 e Å^−3
S = 1.02	Δρmin = −1.32 e Å^−3
2770 reflections	Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
36 parameters	Extinction coefficient: 178E1 (5)
0 restraints	Absolute structure: 1259 of Friedel pairs used in the refinement
0 constraints	Absolute structure parameter: 0.397 (4)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Sm1	0	0	0	0.007673 (8)
Fe1	0.783035 (9)	0.666667	0.666667	0.005381 (13)
B1	0	0	0.5	0.00553 (11)
B2	0.44687 (6)	0.44687 (6)	0.5	0.00651 (10)
O1	0.85576 (4)	0.85576 (4)	0.5	0.00690 (6)
O2	0.59061 (5)	0.59061 (5)	0.5	0.01141 (9)
O3	0.97419 (4)	0.78644 (5)	0.81637 (5)	0.00849 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sm1	0.007962 (10)	0.007962 (10)	0.007095 (13)	0.003981 (5)	0	0
Fe1	0.005090 (14)	0.005267 (17)	0.00585 (2)	0.002634 (8)	−0.000060 (5)	−0.000120 (10)
B1	0.00499 (13)	0.00499 (13)	0.0066 (2)	0.00249 (6)	0	0
B2	0.00556 (10)	0.00556 (10)	0.00781 (14)	0.00234 (15)	−0.00022 (7)	0.00022 (7)
O1	0.00523 (6)	0.00523 (6)	0.00852 (11)	0.00134 (7)	−0.00100 (4)	0.00100 (4)
O2	0.00695 (7)	0.00695 (7)	0.01564 (18)	−0.00003 (10)	−0.00417 (7)	0.00417 (7)
O3	0.00625 (7)	0.01021 (9)	0.00949 (8)	0.00447 (6)	−0.00164 (6)	−0.00202 (6)

Geometric parameters (Å, º)

Sm1—O3^i	2.3819 (4)	Fe1—O2^vii	2.0444 (6)
Sm1—O3^ii	2.3819 (4)	Fe1—O3	1.9629 (3)
Sm1—O3^iii	2.3819 (6)	Fe1—O3^viii	1.9629 (5)
Sm1—O3^iv	2.3819 (4)	B1—O1^ix	1.3799 (3)
Sm1—O3^v	2.3819 (4)	B1—O1^x	1.3799 (5)
Sm1—O3^vi	2.3819 (6)	B1—O1^xi	1.3799 (5)
Fe1—O1	2.0245 (3)	B2—O2	1.3751 (6)
Fe1—O1^vii	2.0245 (3)	B2—O3^xii	1.3700 (8)
Fe1—O2	2.0444 (4)	B2—O3^xiii	1.3700 (8)
O3^i—Sm1—O3^ii	89.212 (15)	O1^vii—Fe1—O3^viii	92.094 (18)
O3^i—Sm1—O3^iii	89.212 (15)	O2—Fe1—O2^vii	87.48 (2)
O3^i—Sm1—O3^iv	122.539 (11)	O2—Fe1—O3	167.50 (2)
O3^i—Sm1—O3^v	142.046 (18)	O2—Fe1—O3^viii	87.03 (2)
O3^i—Sm1—O3^vi	72.611 (15)	O2^vii—Fe1—O3	87.025 (19)
O3^ii—Sm1—O3^iii	89.212 (15)	O2^vii—Fe1—O3^viii	167.505 (16)
O3^ii—Sm1—O3^iv	142.046 (18)	O3—Fe1—O3^viii	100.46 (2)
O3^ii—Sm1—O3^v	72.611 (13)	O1^ix—B1—O1^x	120.00 (3)
O3^ii—Sm1—O3^vi	122.539 (17)	O1^ix—B1—O1^xi	120.00 (3)
O3^iii—Sm1—O3^iv	72.611 (15)	O1^x—B1—O1^xi	120.00 (3)
O3^iii—Sm1—O3^v	122.539 (17)	O2—B2—O3^xii	117.69 (6)
O3^iii—Sm1—O3^vi	142.046 (11)	O2—B2—O3^xiii	117.69 (6)
O3^iv—Sm1—O3^v	89.212 (15)	O3^xii—B2—O3^xiii	124.61 (4)
O3^iv—Sm1—O3^vi	89.212 (15)	Fe1—O1—Fe1^xiv	103.571 (13)
O3^v—Sm1—O3^vi	89.212 (15)	Fe1—O1—B1^xv	128.21 (2)
O1—Fe1—O1^vii	168.16 (2)	Fe1^xiv—O1—B1^xv	128.21 (2)
O1—Fe1—O2	77.131 (14)	Fe1—O2—Fe1^xiv	102.166 (16)
O1—Fe1—O2^vii	94.228 (17)	Fe1—O2—B2	128.92 (3)
O1—Fe1—O3	92.095 (14)	Fe1^xiv—O2—B2	128.92 (3)
O1—Fe1—O3^viii	95.473 (16)	Sm1^xvi—O3—Fe1	120.42 (2)
O1^vii—Fe1—O2	94.228 (16)	Sm1^xvi—O3—B2^xvii	107.25 (2)
O1^vii—Fe1—O2^vii	77.131 (19)	Fe1—O3—B2^xvii	132.21 (3)
O1^vii—Fe1—O3	95.473 (15)

Symmetry codes: (i) x−1, y−1, z−1; (ii) −y+1, x−y, z−1; (iii) −x+y, −x+1, z−1; (iv) y−1, x−1, −z+1; (v) x−y, −y+1, −z+1; (vi) −x+1, −x+y, −z+1; (vii) −x+y+2/3, −x+4/3, z+1/3; (viii) x−y+2/3, −y+4/3, −z+4/3; (ix) x−1, y−1, z; (x) −y+1, x−y, z; (xi) −x+y, −x+1, z; (xii) x−2/3, y−1/3, z−1/3; (xiii) y−1/3, x−2/3, −z+4/3; (xiv) −y+4/3, x−y+2/3, z−1/3; (xv) x+1, y+1, z; (xvi) x+1, y+1, z+1; (xvii) x+2/3, y+1/3, z+1/3.