Structure evolution with Sr content of the perovskite-like materials La2−xSrxCoTiO6 (0 ≤ x ≤ 0.5)

Gómez-Pérez, A.; Pérez-Flores, J.C.; Ritter, C.; Boulahya, K.; Castro, G.R.; García-Alvarado, F.; Amador, U.

doi:10.1107/S1600576714004907

Structure evolution with Sr content of the perovskite-like materials La_2−xSr_xCoTiO₆ (0 ≤ x ≤ 0.5)

A. Gómez-Pérez, J. C. Pérez-Flores, C. Ritter, K. Boulahya, G. R. Castro, F. García-Alvarado and U. Amador

The oxide series La_2−xSr_xCoTiO₆ (0 ≤ x ≤ 1.0) belong to the perovskite family with general formula ABO₃. The evolution of the room-temperature structure as a function of the Sr content was studied using complementary techniques by applying the symmetry-adapted modes formalism (AMPLIMODES). In the compositional range presented in this article (0 ≤ x ≤ 0.5), the compounds adopt distorted perovskite structures of monoclinic (space group P2₁/n) or orthorhombic (space group Pnma) symmetry, both with octahedral tilting scheme (a⁻a⁻c⁺) (out of phase along two perovskite main directions and in phase along the third direction). The main difference between these structures is the existence of rock-salt order of B ions in the monoclinic symmetry, which is lost for x ≥ 0.30. As the Sr content increases, a better matching of the A—O and B—O distances occurs. This is produced by an elongation of the A—O distance as La³⁺ is replaced by the larger ion Sr²⁺, and the shortening of the B—O distance due to the oxidation of Co²⁺ to Co³⁺ induced by the aliovalent substitution. As a result, the cuboctahedral A-site cavity becomes less and less distorted; the A ion tends to occupy its ideal positions, increasing its coordination and giving rise to a more symmetrical structure. In the whole compositional range, the symmetry-adapted atomic displacements (modes) responsible for the out-of-phase tilting of the BO₆ octahedra remain active but those associated with the in-phase tilting become negligible, anticipating for x ≥ 0.6 a transition to a new structure with tilting scheme either (a⁰a⁰c⁻) (space group I4/mcm) or (a⁻a⁻a⁰) (space group Imma) or (a⁻a⁻a⁻) (space group R $\overline 3$ c).

Keywords: perovskites; phase transitions; neutron diffraction; synchrotron X-ray diffraction; AMPLIMODES; cobaltite.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600576714004907/rw5065sup1.cif Contains datablocks Global, LCTO_SXRD, LCTO_NPD, LSCT10_XRD, LSCT10_NPD, LSCT20_SXRD, LSCT20_NPD, LSCT30_SXRD, LSCT30_NPD, LSCT50_SXRD, LSCT50_NPD
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714004907/rw5065LCTO_NPDsup2.rtv Contains datablock NPD
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714004907/rw5065LCTO_SXRDsup3.rtv Contains datablock SXRD
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714004907/rw5065LSCT10_NPDsup4.rtv Contains datablock NPD
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714004907/rw5065LSCT10_XRDsup5.rtv Contains datablock XRD
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714004907/rw5065LSCT20_NPDsup6.rtv Contains datablock NPD
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714004907/rw5065LSCT20_SXRDsup7.rtv Contains datablock SXRD
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714004907/rw5065LSCT30_NPDsup8.rtv Contains datablock NPD
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714004907/rw5065LSCT30_SXRDsup9.rtv Contains datablock SXRD
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714004907/rw5065LSCT50_NPDsup10.rtv Contains datablock NPD
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714004907/rw5065LSCT50_SXRDsup11.rtv Contains datablock SXRD
	Portable Document Format (PDF) file https://doi.org/10.1107/S1600576714004907/rw5065sup12.pdf Additional structural tables (generated by AMPLIMODES) and figures

CCDC references: 989515; 989516; 989517; 989518; 989519; 989520; 989521; 989522; 989523; 989524

Comment top

Symmetry-adapted Rietveld refinement is a powerfull tool to understand the physical mechanism which stabilize a certain structured derived from a high simmetry parent structure within displazative-type phase transitions.

Experimental top

Samples of compositions La2-xSrxCoTiO6 (0=x=0.5) were prepared by a modified Peccini method. About 10 grams of each sample was prepared solving stoichiometric amounts of high purity Co(CH3COO)2·4H2O (Aldrich, 99.99%), La2O3 (Aldrich, 99.9%)and SrCO3 (Aldrich 99.9%) in ca 20 ml of concentrated hot nitric acid (Panreac 66%)and ca 50 ml of distillate water was added. Under heating and vigorous stirring, citric acid was added in a molar ratio citric acid to metal ions of 3:1. Then, titanium was added as anatase (Aldrich, purity 99.9%) to obtain a homogeneous suspension, since TiO2 is not soluble. When the solution was concentrated to half of its initial volume, 3 ml of diethyleneglycol was added to promote polymerization. When a solid resin is formed it is allowed to cool down to room temperature and then milled in an agate mortar; the obtained powder was burn at 1073 K to remove organic matter. After milling and homogenization the resulted powder was heated at 1773 K for 24 h and cooled down (at a rate of 2 K/min) to room temperature to obtain well crystallized materials.

Computing details top

For all compounds, program(s) used to refine structure: FULLPROF.

(LCTO_SXRD) lanthanum coblat(II) titanate(IV) oxide top

Crystal data top

Co₂La₄O₁₂Ti₂	Z = 2
M_r = 480.62	? _exptl_crystal_density_diffrn 6.556(1) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 422.0
Monoclinic, P2₁/n	Synchrotron radiation, λ = 0.621000 Å
Hall symbol: -P 2yn	µ = 7.37 mm⁻¹
a = 5.55510 (9) Å	T = 295 K
b = 5.57813 (8) Å	Particle morphology: plate-like SEM
c = 7.85718 (12) Å	black
β = 90.005 (5)°	cylinder, 15 × 20 mm
V = 243.47 (1) Å³

Data collection top

Home-made heavy-duty Theta-2theta goniometer diffractometer	Scan method: step
Radiation source: Synchrotron	Absorption correction: for a cylinder mounted on the φ axis Cromer and Liberman algorithm
Si 111 monochromator	T_min = ?, T_max = ?
Specimen mounting: Borosilicate 0.3 mm capillary	2θ_min = 7.989°, 2θ_max = 46.991°, 2θ_step = 0.010°
Data collection mode: transmission

Refinement top

Refinement on I_net	3901 data points
Least-squares matrix: full with fixed elements per cycle	Profile function: pseudo-Voigt
R_p = 0.073	40 parameters
R_wp = 0.100	0 restraints
R_exp = 0.058	Weighting scheme based on measured s.u.'s 1/[Y_i + σ(Y_i)]
R_Bragg = 0.036	(Δ/σ)_max = 0.01
χ² = 8.418	Background function: Set of experimental background points

Crystal data top

Co₂La₄O₁₂Ti₂	V = 243.47 (1) Å³
M_r = 480.62	Z = 2
Monoclinic, P2₁/n	Synchrotron radiation, λ = 0.621000 Å
a = 5.55510 (9) Å	µ = 7.37 mm⁻¹
b = 5.57813 (8) Å	T = 295 K
c = 7.85718 (12) Å	cylinder, 15 × 20 mm
β = 90.005 (5)°

Data collection top

Home-made heavy-duty Theta-2theta goniometer diffractometer	Absorption correction: for a cylinder mounted on the φ axis Cromer and Liberman algorithm
Specimen mounting: Borosilicate 0.3 mm capillary	T_min = ?, T_max = ?
Data collection mode: transmission	2θ_min = 7.989°, 2θ_max = 46.991°, 2θ_step = 0.010°
Scan method: step

Refinement top

R_p = 0.073	χ² = 8.418
R_wp = 0.100	3901 data points
R_exp = 0.058	40 parameters
R_Bragg = 0.036	0 restraints

Special details top

Experimental. Synchrotron source

Refinement. Symmetry-adapted Rietveld refinement by simulteneuos fitting of SXRD and NPD data.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
La1	0.0059 (3)	−0.03335 (16)	0.2494 (7)	0.0055 (2)*
Ti1	0.00000	0.50000	0.00000	0.0038 (8)*	0.90600
Co2	0.00000	0.50000	0.00000	0.0038 (8)*	0.09400
Co1	0.00000	0.50000	0.50000	0.0005 (8)*	0.90600
Ti2	0.00000	0.50000	0.50000	0.0005 (8)*	0.09400
O1	−0.7229 (9)	0.7041 (9)	0.0381 (9)	0.0058 (11)*
O1_2	−0.2058 (9)	0.7759 (9)	−0.0404 (9)	0.0051 (11)*
O1_3	−0.0740 (5)	0.5143 (4)	0.2473 (8)	0.0083 (5)*

Geometric parameters (Å, º) top

La1—O1ⁱ	2.678 (7)	Ti1—O1^viii	1.938 (5)
La1—O1ⁱⁱ	2.448 (7)	Ti1—O1ⁱⁱⁱ	1.938 (5)
La1—O1ⁱⁱⁱ	3.309 (7)	Ti1—O1_2	1.943 (5)
La1—O1^iv	2.769 (8)	Ti1—O1_2^vi	1.943 (5)
La1—O1_2^v	2.775 (8)	Ti1—O1_3	1.988 (6)
La1—O1_2ⁱⁱ	3.314 (7)	Ti1—O1_3^vi	1.988 (6)
La1—O1_2^vi	2.448 (7)	Co1—O1ⁱⁱ	2.085 (5)
La1—O1_2^iv	2.669 (7)	Co1—O1^ix	2.085 (5)
La1—O1_3^v	2.562 (2)	Co1—O1_2ⁱⁱ	2.082 (5)
La1—O1_3	3.087 (2)	Co1—O1_2^ix	2.082 (5)
La1—O1_3ⁱⁱ	2.414 (3)	Co1—O1_3	2.029 (6)
La1—O1_3^vii	3.167 (3)	Co1—O1_3^x	2.029 (6)

O1—Co1—O1	180.0 (4)	O1—Ti1—O1	180.0 (5)
O1—Co1—O1_2	90.7 (3)	O1—Ti1—O1_2	91.6 (4)
O1—Co1—O1_2	89.3 (3)	O1—Ti1—O1_2	88.4 (4)
O1—Co1—O1_3	90.6 (4)	O1—Ti1—O1_3	89.4 (4)
O1—Co1—O1_3	89.4 (4)	O1—Ti1—O1_3	90.6 (4)
O1—Co1—O1_2	89.3 (3)	O1—Ti1—O1_2	88.4 (4)
O1—Co1—O1_2	90.7 (3)	O1—Ti1—O1_2	91.6 (4)
O1—Co1—O1_3	89.4 (4)	O1—Ti1—O1_3	90.6 (4)
O1—Co1—O1_3	90.6 (4)	O1—Ti1—O1_3	89.4 (4)
O1_2—Co1—O1_2	180.0 (4)	O1_2—Ti1—O1_2	180.0 (5)
O1_2—Co1—O1_3	90.8 (4)	O1_2—Ti1—O1_3	90.4 (4)
O1_2—Co1—O1_3	89.2 (4)	O1_2—Ti1—O1_3	89.6 (4)
O1_2—Co1—O1_3	89.2 (4)	O1_2—Ti1—O1_3	89.6 (4)
O1_2—Co1—O1_3	90.8 (4)	O1_2—Ti1—O1_3	90.4 (4)
O1_3—Co1—O1_3	180.0 (6)	O1_3—Ti1—O1_3	180.0 (6)

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

(LCTO_NPD) Lanthanum Cobalt(II) Titanium(IV) oxide top

Crystal data top

Co₂La₄O₁₂Ti₂	Z = 2
M_r = 480.62	? _exptl_crystal_density_diffrn 6.556(1) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 100.9
Monoclinic, P2₁/n	Constant Wavelength Neutron Diffraction radiation, λ = 1.594000 Å
Hall symbol: -P 2yn	µ = 0.00 mm⁻¹
a = 5.55510 (9) Å	T = 295 K
b = 5.57813 (8) Å	Particle morphology: plate-like SEM
c = 7.85718 (12) Å	black
β = 90.005 (5)°	cylinder, 15 × 20 mm
V = 243.47 (1) Å³

Data collection top

High-resolution two-axis diffractometer	Data collection mode: transmission
Radiation source: nuclear reactor, D2B beamline ILL	Scan method: step
Ge monochromator	2θ_min = 0.239°, 2θ_max = 160.189°, 2θ_step = 0.050°
Specimen mounting: 'vanadium can'

Refinement top

Refinement on I_net	3901 data points
Least-squares matrix: full with fixed elements per cycle	Profile function: pseudo-Voigt
R_p = 0.046	40 parameters
R_wp = 0.059	0 restraints
R_exp = 0.039	Weighting scheme based on measured s.u.'s 1/[Y_i + σ(Y_i)]
R_Bragg = 0.032	(Δ/σ)_max = 0.01
χ² = 5.505	Background function: Set of experimental background points

Crystal data top

Co₂La₄O₁₂Ti₂	V = 243.47 (1) Å³
M_r = 480.62	Z = 2
Monoclinic, P2₁/n	Constant Wavelength Neutron Diffraction radiation, λ = 1.594000 Å
a = 5.55510 (9) Å	µ = 0.00 mm⁻¹
b = 5.57813 (8) Å	T = 295 K
c = 7.85718 (12) Å	cylinder, 15 × 20 mm
β = 90.005 (5)°

Data collection top

High-resolution two-axis diffractometer	Scan method: step
Specimen mounting: 'vanadium can'	2θ_min = 0.239°, 2θ_max = 160.189°, 2θ_step = 0.050°
Data collection mode: transmission

Refinement top

R_p = 0.046	χ² = 5.505
R_wp = 0.059	3901 data points
R_exp = 0.039	40 parameters
R_Bragg = 0.032	0 restraints

Special details top

Experimental. Neutron reactor

Refinement. Symmetry-adapted Rietveld refinement by simulteneuos fitting of SXRD and NPD data.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
La1	0.0059 (3)	−0.03335 (16)	0.2494 (7)	0.0055 (2)*
Ti1	0.00000	0.50000	0.00000	0.0038 (8)*	0.90600
Co2	0.00000	0.50000	0.00000	0.0038 (8)*	0.09400
Co1	0.00000	0.50000	0.50000	0.0005 (8)*	0.90600
Ti2	0.00000	0.50000	0.50000	0.0005 (8)*	0.09400
O1	−0.7229 (9)	0.7041 (9)	0.0381 (9)	0.0058 (11)*
O1_2	−0.2058 (9)	0.7759 (9)	−0.0404 (9)	0.0051 (11)*
O1_3	−0.0740 (5)	0.5143 (4)	0.2473 (8)	0.0083 (5)*

Geometric parameters (Å, º) top

La1—O1ⁱ	2.678 (7)	Ti1—O1^viii	1.938 (5)
La1—O1ⁱⁱ	2.448 (7)	Ti1—O1ⁱⁱⁱ	1.938 (5)
La1—O1ⁱⁱⁱ	3.309 (7)	Ti1—O1_2	1.943 (5)
La1—O1^iv	2.769 (8)	Ti1—O1_2^vi	1.943 (5)
La1—O1_2^v	2.775 (8)	Ti1—O1_3	1.988 (6)
La1—O1_2ⁱⁱ	3.314 (7)	Ti1—O1_3^vi	1.988 (6)
La1—O1_2^vi	2.448 (7)	Co1—O1ⁱⁱ	2.085 (5)
La1—O1_2^iv	2.669 (7)	Co1—O1^ix	2.085 (5)
La1—O1_3^v	2.562 (2)	Co1—O1_2ⁱⁱ	2.082 (5)
La1—O1_3	3.087 (2)	Co1—O1_2^ix	2.082 (5)
La1—O1_3ⁱⁱ	2.414 (3)	Co1—O1_3	2.029 (6)
La1—O1_3^vii	3.167 (3)	Co1—O1_3^x	2.029 (6)

O1—Co1—O1	180.0 (4)	O1—Ti1—O1	180.0 (5)
O1—Co1—O1_2	90.7 (3)	O1—Ti1—O1_2	91.6 (4)
O1—Co1—O1_2	89.3 (3)	O1—Ti1—O1_2	88.4 (4)
O1—Co1—O1_3	90.6 (4)	O1—Ti1—O1_3	89.4 (4)
O1—Co1—O1_3	89.4 (4)	O1—Ti1—O1_3	90.6 (4)
O1—Co1—O1_2	89.3 (3)	O1—Ti1—O1_2	88.4 (4)
O1—Co1—O1_2	90.7 (3)	O1—Ti1—O1_2	91.6 (4)
O1—Co1—O1_3	89.4 (4)	O1—Ti1—O1_3	90.6 (4)
O1—Co1—O1_3	90.6 (4)	O1—Ti1—O1_3	89.4 (4)
O1_2—Co1—O1_2	180.0 (4)	O1_2—Ti1—O1_2	180.0 (5)
O1_2—Co1—O1_3	90.8 (4)	O1_2—Ti1—O1_3	90.4 (4)
O1_2—Co1—O1_3	89.2 (4)	O1_2—Ti1—O1_3	89.6 (4)
O1_2—Co1—O1_3	89.2 (4)	O1_2—Ti1—O1_3	89.6 (4)
O1_2—Co1—O1_3	90.8 (4)	O1_2—Ti1—O1_3	90.4 (4)
O1_3—Co1—O1_3	180.0 (6)	O1_3—Ti1—O1_3	180.0 (6)

(LSCT10_XRD) Lanthanum Strontium Cobalt(II) Titanium(IV) oxide top

Crystal data top

CoLa_1.9O₆Sr_0.1Ti	Z = 2
M_r = 475.52	? _exptl_crystal_density_diffrn 6.483(1) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 418.2
Monoclinic, P2₁/n	Cu Kα₁ radiation, λ = 1.540560 Å
Hall symbol: -P 2yn	T = 295 K
a = 5.55318 (8) Å	Particle morphology: plate-like SEM
b = 5.56557 (7) Å	black
c = 7.84995 (10) Å	flat sheet, 20 × 20 mm
β = 90.007 (5)°	Specimen preparation: Cooled at 2 K min⁻¹
V = 242.62 (1) Å³

Data collection top

Bruker D8 Advance diffractometer	Data collection mode: reflexion
Radiation source: sealed X-ray tube	Scan method: step
Ge (111) monochromator	2θ_min = 19.880°, 2θ_max = 99.882°, 2θ_step = 0.020°
Specimen mounting: Aluminium Sample holder

Refinement top

Refinement on I_net	4061 data points
Least-squares matrix: full with fixed elements per cycle	Profile function: pseudo-Voigt
R_p = 0.036	34 parameters
R_wp = 0.047	0 restraints
R_exp = 0.035	Weighting scheme based on measured s.u.'s 1/[Y_i + σ(Y_i)]
R_Bragg = 0.083	(Δ/σ)_max = 0.01
χ² = 3.147	Background function: Set of experimental background points

Crystal data top

CoLa_1.9O₆Sr_0.1Ti	β = 90.007 (5)°
M_r = 475.52	V = 242.62 (1) Å³
Monoclinic, P2₁/n	Z = 2
a = 5.55318 (8) Å	Cu Kα₁ radiation, λ = 1.540560 Å
b = 5.56557 (7) Å	T = 295 K
c = 7.84995 (10) Å	flat sheet, 20 × 20 mm

Data collection top

Bruker D8 Advance diffractometer	Scan method: step
Specimen mounting: Aluminium Sample holder	2θ_min = 19.880°, 2θ_max = 99.882°, 2θ_step = 0.020°
Data collection mode: reflexion

Refinement top

R_p = 0.036	χ² = 3.147
R_wp = 0.047	4061 data points
R_exp = 0.035	34 parameters
R_Bragg = 0.083	0 restraints

Special details top

Experimental. Conventional X-Ray source

Refinement. Symmetry-adapted Rietveld refinement by simulteneuos fitting of SXRD and NPD data.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
La1	0.0056 (4)	−0.03105 (18)	0.2494 (10)	0.0066 (2)*	0.95000
Sr1	0.0056 (4)	−0.03105 (18)	0.2494 (10)	0.0066 (2)*	0.05000
Ti1	0.00000	0.50000	0.00000	0.0069 (12)*	0.82690
Co2	0.00000	0.50000	0.00000	0.0069 (12)*	0.17312
O1	−0.7234 (8)	0.7081 (8)	0.0375 (10)	0.0062 (11)*
O1_2	−0.2102 (8)	0.7757 (8)	−0.0390 (10)	0.0082 (12)*
O1_3	−0.0725 (4)	0.5128 (3)	0.2475 (3)	0.0076 (4)*
Co1	0.00000	0.50000	0.50000	0.0036 (18)*	0.82690
Ti2	0.00000	0.50000	0.50000	0.0036 (18)*	0.17312

Geometric parameters (Å, º) top

La1—O1ⁱ	2.676 (8)	Ti1—O1^viii	1.949 (5)
La1—O1ⁱⁱ	2.459 (8)	Ti1—O1ⁱⁱⁱ	1.949 (5)
La1—O1ⁱⁱⁱ	3.284 (8)	Ti1—O1_2	1.955 (5)
La1—O1^iv	2.779 (9)	Ti1—O1_2^vi	1.955 (5)
La1—O1_2^v	2.782 (9)	Ti1—O1_3	1.988 (2)
La1—O1_2ⁱⁱ	3.287 (8)	Ti1—O1_3^vi	1.988 (2)
La1—O1_2^vi	2.461 (8)	Co1—O1ⁱⁱ	2.068 (5)
La1—O1_2^iv	2.669 (8)	Co1—O1^ix	2.068 (5)
La1—O1_3^v	2.577 (2)	Co1—O1_2ⁱⁱ	2.062 (5)
La1—O1_3	3.060 (2)	Co1—O1_2^ix	2.062 (5)
La1—O1_3ⁱⁱ	2.421 (3)	Co1—O1_3	2.026 (2)
La1—O1_3^vii	3.160 (3)	Co1—O1_3^x	2.026 (2)

O1—Ti1—O1	180.0 (4)	O1—Co1—O1	180.0 (4)
O1—Ti1—O1_2	91.6 (3)	O1—Co1—O1_2	90.8 (3)
O1—Ti1—O1_2	88.4 (3)	O1—Co1—O1_2	89.2 (3)
O1—Ti1—O1_3	89.5 (3)	O1—Co1—O1_3	90.4 (3)
O1—Ti1—O1_3	90.5 (3)	O1—Co1—O1_3	89.6 (3)
O1—Ti1—O1_2	88.4 (3)	O1—Co1—O1_2	89.2 (3)
O1—Ti1—O1_2	91.6 (3)	O1—Co1—O1_2	90.8 (3)
O1—Ti1—O1_3	90.5 (3)	O1—Co1—O1_3	89.6 (3)
O1—Ti1—O1_3	89.5 (3)	O1—Co1—O1_3	90.4 (3)
O1_2—Ti1—O1_2	180.0 (4)	O1_2—Co1—O1_2	180.0 (4)
O1_2—Ti1—O1_3	90.2 (3)	O1_2—Co1—O1_3	90.7 (3)
O1_2—Ti1—O1_3	89.8 (3)	O1_2—Co1—O1_3	89.3 (3)
O1_2—Ti1—O1_3	89.8 (3)	O1_2—Co1—O1_3	89.3 (3)
O1_2—Ti1—O1_3	90.2 (3)	O1_2—Co1—O1_3	90.7 (3)
O1_3—Ti1—O1_3	180.0 (2)	O1_3—Co1—O1_3	180.0 (2)

(LSCT10_NPD) Lanthanum Strontium Cobalt(II) Titanium(IV) oxide top

Crystal data top

CoLa_1.9O₆Sr_0.1Ti	Z = 2
M_r = 475.52	? _exptl_crystal_density_diffrn 6.483(1) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 100.6
Monoclinic, P2₁/n	Constant Wavelength Neutron Diffraction radiation, λ = 1.594000 Å
Hall symbol: -P 2yn	µ = 0.00 mm⁻¹
a = 5.55318 (8) Å	T = 295 K
b = 5.56557 (7) Å	Particle morphology: plate-like SEM
c = 7.84995 (10) Å	black
β = 90.007 (5)°	cylinder, 15 × 20 mm
V = 242.62 (1) Å³

Data collection top

High-resolution two-axis diffractometer	Data collection mode: transmission
Radiation source: nuclear reactor, D2B beamline ILL	Scan method: step
Ge monochromator	2θ_min = 0.245°, 2θ_max = 160.195°, 2θ_step = 0.050°
Specimen mounting: 'vanadium can'

Refinement top

Refinement on I_net	4061 data points
Least-squares matrix: full with fixed elements per cycle	Profile function: pseudo-Voigt
R_p = 0.364	34 parameters
R_wp = 0.047	0 restraints
R_exp = 0.027	Weighting scheme based on measured s.u.'s 1/[Y_i + σ(Y_i)]
R_Bragg = 0.023	(Δ/σ)_max = 0.01
χ² = 9.624	Background function: Set of experimental background points

Crystal data top

CoLa_1.9O₆Sr_0.1Ti	V = 242.62 (1) Å³
M_r = 475.52	Z = 2
Monoclinic, P2₁/n	Constant Wavelength Neutron Diffraction radiation, λ = 1.594000 Å
a = 5.55318 (8) Å	µ = 0.00 mm⁻¹
b = 5.56557 (7) Å	T = 295 K
c = 7.84995 (10) Å	cylinder, 15 × 20 mm
β = 90.007 (5)°

Data collection top

High-resolution two-axis diffractometer	Scan method: step
Specimen mounting: 'vanadium can'	2θ_min = 0.245°, 2θ_max = 160.195°, 2θ_step = 0.050°
Data collection mode: transmission

Refinement top

R_p = 0.364	χ² = 9.624
R_wp = 0.047	4061 data points
R_exp = 0.027	34 parameters
R_Bragg = 0.023	0 restraints

Special details top

Experimental. Neutron reactor

Refinement. Symmetry-adapted Rietveld refinement by simulteneuos fitting of SXRD and NPD data.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
La1	0.0056 (4)	−0.03105 (18)	0.2494 (10)	0.0066 (2)*	0.95000
Sr1	0.0056 (4)	−0.03105 (18)	0.2494 (10)	0.0066 (2)*	0.05000
Ti1	0.00000	0.50000	0.00000	0.0069 (12)*	0.82690
Co2	0.00000	0.50000	0.00000	0.0069 (12)*	0.17312
O1	−0.7234 (8)	0.7081 (8)	0.0375 (10)	0.0062 (11)*
O1_2	−0.2102 (8)	0.7757 (8)	−0.0390 (10)	0.0082 (12)*
O1_3	−0.0725 (4)	0.5128 (3)	0.2475 (3)	0.0076 (4)*
Co1	0.00000	0.50000	0.50000	0.0036 (18)*	0.82690
Ti2	0.00000	0.50000	0.50000	0.0036 (18)*	0.17312

Geometric parameters (Å, º) top

La1—O1ⁱ	2.676 (8)	Ti1—O1^viii	1.949 (5)
La1—O1ⁱⁱ	2.459 (8)	Ti1—O1ⁱⁱⁱ	1.949 (5)
La1—O1ⁱⁱⁱ	3.284 (8)	Ti1—O1_2	1.955 (5)
La1—O1^iv	2.779 (9)	Ti1—O1_2^vi	1.955 (5)
La1—O1_2^v	2.782 (9)	Ti1—O1_3	1.988 (2)
La1—O1_2ⁱⁱ	3.287 (8)	Ti1—O1_3^vi	1.988 (2)
La1—O1_2^vi	2.461 (8)	Co1—O1ⁱⁱ	2.068 (5)
La1—O1_2^iv	2.669 (8)	Co1—O1^ix	2.068 (5)
La1—O1_3^v	2.577 (2)	Co1—O1_2ⁱⁱ	2.062 (5)
La1—O1_3	3.060 (2)	Co1—O1_2^ix	2.062 (5)
La1—O1_3ⁱⁱ	2.421 (3)	Co1—O1_3	2.026 (2)
La1—O1_3^vii	3.160 (3)	Co1—O1_3^x	2.026 (2)

O1—Ti1—O1	180.0 (4)	O1—Co1—O1	180.0 (4)
O1—Ti1—O1_2	91.6 (3)	O1—Co1—O1_2	90.8 (3)
O1—Ti1—O1_2	88.4 (3)	O1—Co1—O1_2	89.2 (3)
O1—Ti1—O1_3	89.5 (3)	O1—Co1—O1_3	90.4 (3)
O1—Ti1—O1_3	90.5 (3)	O1—Co1—O1_3	89.6 (3)
O1—Ti1—O1_2	88.4 (3)	O1—Co1—O1_2	89.2 (3)
O1—Ti1—O1_2	91.6 (3)	O1—Co1—O1_2	90.8 (3)
O1—Ti1—O1_3	90.5 (3)	O1—Co1—O1_3	89.6 (3)
O1—Ti1—O1_3	89.5 (3)	O1—Co1—O1_3	90.4 (3)
O1_2—Ti1—O1_2	180.0 (4)	O1_2—Co1—O1_2	180.0 (4)
O1_2—Ti1—O1_3	90.2 (3)	O1_2—Co1—O1_3	90.7 (3)
O1_2—Ti1—O1_3	89.8 (3)	O1_2—Co1—O1_3	89.3 (3)
O1_2—Ti1—O1_3	89.8 (3)	O1_2—Co1—O1_3	89.3 (3)
O1_2—Ti1—O1_3	90.2 (3)	O1_2—Co1—O1_3	90.7 (3)
O1_3—Ti1—O1_3	180.0 (2)	O1_3—Co1—O1_3	180.0 (2)

(LSCT20_SXRD) Lanthanum Strontium Cobalt(II) Titanium(IV) oxide top

Crystal data top

CoLa_1.8O₆Sr_0.2Ti	Z = 2
M_r = 470.39	? _exptl_crystal_density_diffrn 6.452(1) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 414.4
Monoclinic, P2₁/n	Synchrotron radiation, λ = 0.621000 Å
Hall symbol: -P 2yn	µ = 7.73 mm⁻¹
a = 5.55020 (11) Å	T = 295 K
b = 5.54838 (9) Å	Particle morphology: plate-like SEM
c = 7.83763 (10) Å	black
β = 90.014 (7)°	cylinder, 15 × 20 mm
V = 241.36 (1) Å³

Data collection top

Home-made heavy-duty Theta-2theta goniometer diffractometer	Scan method: step
Radiation source: Synchrotron	Absorption correction: for a cylinder mounted on the φ axis Cromer and Liberman algorithm
Si 111 monochromator	T_min = ?, T_max = ?
Specimen mounting: Borosilicate 0.3 mm capillary	2θ_min = 7.011°, 2θ_max = 37.302°, 2θ_step = 0.010°
Data collection mode: transmission

Refinement top

Refinement on I_net	3030 data points
Least-squares matrix: full with fixed elements per cycle	Profile function: pseudo-Voigt
R_p = 0.156	40 parameters
R_wp = 0.239	0 restraints
R_exp = 0.213	Weighting scheme based on measured s.u.'s 1/[Y_i + σ(Y_i)]
R_Bragg = 0.079	(Δ/σ)_max = 0.01
χ² = 1.573	Background function: Set of experimental background points

Crystal data top

CoLa_1.8O₆Sr_0.2Ti	V = 241.36 (1) Å³
M_r = 470.39	Z = 2
Monoclinic, P2₁/n	Synchrotron radiation, λ = 0.621000 Å
a = 5.55020 (11) Å	µ = 7.73 mm⁻¹
b = 5.54838 (9) Å	T = 295 K
c = 7.83763 (10) Å	cylinder, 15 × 20 mm
β = 90.014 (7)°

Data collection top

Home-made heavy-duty Theta-2theta goniometer diffractometer	Absorption correction: for a cylinder mounted on the φ axis Cromer and Liberman algorithm
Specimen mounting: Borosilicate 0.3 mm capillary	T_min = ?, T_max = ?
Data collection mode: transmission	2θ_min = 7.011°, 2θ_max = 37.302°, 2θ_step = 0.010°
Scan method: step

Refinement top

R_p = 0.156	χ² = 1.573
R_wp = 0.239	3030 data points
R_exp = 0.213	40 parameters
R_Bragg = 0.079	0 restraints

Special details top

Experimental. Synchrotron source

Refinement. Symmetry-adapted Rietveld refinement by simulteneuos fitting of SXRD and NPD data.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
La1	0.0048 (4)	−0.0271 (2)	0.2503 (16)	0.0075 (2)*	0.90000
Sr1	0.0048 (4)	−0.0271 (2)	0.2503 (16)	0.0075 (2)*	0.10000
Ti1	0.00000	0.50000	0.00000	0.007 (3)*	0.56308
Co2	0.00000	0.50000	0.00000	0.007 (3)*	0.43694
O1	−0.7219 (11)	0.7228 (11)	0.0387 (10)	0.014 (2)*
O1_2	−0.2173 (11)	0.7849 (11)	−0.0351 (10)	0.0049 (16)*
O1_3	−0.0689 (4)	0.51043 (5)	0.2510 (15)	0.0072 (4)*
Co1	0.00000	0.50000	0.50000	0.007 (8)*	0.56308
Ti2	0.00000	0.50000	0.50000	0.007 (8)*	0.43694

Geometric parameters (Å, º) top

La1—O1ⁱ	2.642 (11)	Ti1—O1^viii	2.001 (6)
La1—O1ⁱⁱ	2.471 (11)	Ti1—O1ⁱⁱⁱ	2.001 (6)
La1—O1ⁱⁱⁱ	3.232 (11)	Ti1—O1_2	2.007 (6)
La1—O1^iv	2.806 (12)	Ti1—O1_2^vi	2.007 (6)
La1—O1_2^v	2.759 (13)	Ti1—O1_3	2.005 (12)
La1—O1_2ⁱⁱ	3.245 (11)	Ti1—O1_3^vi	2.005 (12)
La1—O1_2^vi	2.458 (11)	Co1—O1ⁱⁱ	1.994 (6)
La1—O1_2^iv	2.693 (10)	Co1—O1^ix	1.994 (6)
La1—O1_3^v	2.5984 (12)	Co1—O1_2ⁱⁱ	1.991 (6)
La1—O1_3	3.0103 (12)	Co1—O1_2^ix	1.991 (6)
La1—O1_3ⁱⁱ	2.428 (3)	Co1—O1_3	1.989 (12)
La1—O1_3^vii	3.138 (3)	Co1—O1_3^x	1.989 (12)

O1—Ti1—O1	180.0 (6)	O1—Co1—O1	180.0 (6)
O1—Ti1—O1_2	89.9 (4)	O1—Co1—O1_2	92.6 (4)
O1—Ti1—O1_2	90.1 (4)	O1—Co1—O1_2	87.4 (4)
O1—Ti1—O1_3	88.9 (5)	O1—Co1—O1_3	89.5 (5)
O1—Ti1—O1_3	91.1 (6)	O1—Co1—O1_3	90.5 (6)
O1—Ti1—O1_2	90.1 (4)	O1—Co1—O1_2	87.4 (4)
O1—Ti1—O1_2	89.9 (4)	O1—Co1—O1_2	92.6 (4)
O1—Ti1—O1_3	91.1 (6)	O1—Co1—O1_3	90.5 (6)
O1—Ti1—O1_3	88.9 (5)	O1—Co1—O1_3	89.5 (5)
O1_2—Ti1—O1_2	180.0 (6)	O1_2—Co1—O1_2	180.0 (6)
O1_2—Ti1—O1_3	89.8 (6)	O1_2—Co1—O1_3	90.1 (6)
O1_2—Ti1—O1_3	90.2 (5)	O1_2—Co1—O1_3	89.9 (6)
O1_2—Ti1—O1_3	90.2 (5)	O1_2—Co1—O1_3	89.9 (6)
O1_2—Ti1—O1_3	89.8 (6)	O1_2—Co1—O1_3	90.1 (6)
O1_3—Ti1—O1_3	180.0 (10)	O1_3—Co1—O1_3	180.0 (11)

(LSCT20_NPD) Lanthanum Strontium Cobalt(II) Titanium(IV) oxide top

Crystal data top

CoLa_1.8O₆Sr_0.2Ti	Z = 2
M_r = 470.39	? _exptl_crystal_density_diffrn 6.452(1) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 100.4
Monoclinic, P2₁/n	Constant Wavelength Neutron Diffraction radiation, λ = 1.594000 Å
Hall symbol: -P 2yn	µ = 0.00 mm⁻¹
a = 5.55020 (11) Å	T = 295 K
b = 5.54838 (9) Å	Particle morphology: plate-like SEM
c = 7.83763 (10) Å	black
β = 90.014 (7)°	cylinder, 15 × 20 mm
V = 241.36 (1) Å³

Data collection top

High-resolution two-axis diffractometer	Data collection mode: transmission
Radiation source: nuclear reactor, D2B beamline ILL	Scan method: step
Ge monochromator	2θ_min = 0.241°, 2θ_max = 160.191°, 2θ_step = 0.050°
Specimen mounting: 'vanadium can'

Refinement top

Refinement on I_net	3901 data points
Least-squares matrix: full with fixed elements per cycle	Profile function: pseudo-Voigt
R_p = 0.035	40 parameters
R_wp = 0.045	0 restraints
R_exp = 0.026	Weighting scheme based on measured s.u.'s 1/[Y_i + σ(Y_i)]
R_Bragg = 0.025	(Δ/σ)_max = 0.01
χ² = 8.804	Background function: Set of experimental background points

Crystal data top

CoLa_1.8O₆Sr_0.2Ti	V = 241.36 (1) Å³
M_r = 470.39	Z = 2
Monoclinic, P2₁/n	Constant Wavelength Neutron Diffraction radiation, λ = 1.594000 Å
a = 5.55020 (11) Å	µ = 0.00 mm⁻¹
b = 5.54838 (9) Å	T = 295 K
c = 7.83763 (10) Å	cylinder, 15 × 20 mm
β = 90.014 (7)°

Data collection top

High-resolution two-axis diffractometer	Scan method: step
Specimen mounting: 'vanadium can'	2θ_min = 0.241°, 2θ_max = 160.191°, 2θ_step = 0.050°
Data collection mode: transmission

Refinement top

R_p = 0.035	χ² = 8.804
R_wp = 0.045	3901 data points
R_exp = 0.026	40 parameters
R_Bragg = 0.025	0 restraints

Special details top

Experimental. Neutron reactor

Refinement. Symmetry-adapted Rietveld refinement by simulteneuos fitting of SXRD and NPD data.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
La1	0.0048 (4)	−0.0271 (2)	0.2503 (16)	0.0075 (2)*	0.90000
Sr1	0.0048 (4)	−0.0271 (2)	0.2503 (16)	0.0075 (2)*	0.10000
Ti1	0.00000	0.50000	0.00000	0.007 (3)*	0.56308
Co2	0.00000	0.50000	0.00000	0.007 (3)*	0.43694
O1	−0.7219 (11)	0.7228 (11)	0.0387 (10)	0.014 (2)*
O1_2	−0.2173 (11)	0.7849 (11)	−0.0351 (10)	0.0049 (16)*
O1_3	−0.0689 (4)	0.51043 (5)	0.2510 (15)	0.0072 (4)*
Co1	0.00000	0.50000	0.50000	0.007 (8)*	0.56308
Ti2	0.00000	0.50000	0.50000	0.007 (8)*	0.43694

Geometric parameters (Å, º) top

La1—O1ⁱ	2.642 (11)	Ti1—O1^viii	2.001 (6)
La1—O1ⁱⁱ	2.471 (11)	Ti1—O1ⁱⁱⁱ	2.001 (6)
La1—O1ⁱⁱⁱ	3.232 (11)	Ti1—O1_2	2.007 (6)
La1—O1^iv	2.806 (12)	Ti1—O1_2^vi	2.007 (6)
La1—O1_2^v	2.759 (13)	Ti1—O1_3	2.005 (12)
La1—O1_2ⁱⁱ	3.245 (11)	Ti1—O1_3^vi	2.005 (12)
La1—O1_2^vi	2.458 (11)	Co1—O1ⁱⁱ	1.994 (6)
La1—O1_2^iv	2.693 (10)	Co1—O1^ix	1.994 (6)
La1—O1_3^v	2.5984 (12)	Co1—O1_2ⁱⁱ	1.991 (6)
La1—O1_3	3.0103 (12)	Co1—O1_2^ix	1.991 (6)
La1—O1_3ⁱⁱ	2.428 (3)	Co1—O1_3	1.989 (12)
La1—O1_3^vii	3.138 (3)	Co1—O1_3^x	1.989 (12)

O1—Ti1—O1	180.0 (6)	O1—Co1—O1	180.0 (6)
O1—Ti1—O1_2	89.9 (4)	O1—Co1—O1_2	92.6 (4)
O1—Ti1—O1_2	90.1 (4)	O1—Co1—O1_2	87.4 (4)
O1—Ti1—O1_3	88.9 (5)	O1—Co1—O1_3	89.5 (5)
O1—Ti1—O1_3	91.1 (6)	O1—Co1—O1_3	90.5 (6)
O1—Ti1—O1_2	90.1 (4)	O1—Co1—O1_2	87.4 (4)
O1—Ti1—O1_2	89.9 (4)	O1—Co1—O1_2	92.6 (4)
O1—Ti1—O1_3	91.1 (6)	O1—Co1—O1_3	90.5 (6)
O1—Ti1—O1_3	88.9 (5)	O1—Co1—O1_3	89.5 (5)
O1_2—Ti1—O1_2	180.0 (6)	O1_2—Co1—O1_2	180.0 (6)
O1_2—Ti1—O1_3	89.8 (6)	O1_2—Co1—O1_3	90.1 (6)
O1_2—Ti1—O1_3	90.2 (5)	O1_2—Co1—O1_3	89.9 (6)
O1_2—Ti1—O1_3	90.2 (5)	O1_2—Co1—O1_3	89.9 (6)
O1_2—Ti1—O1_3	89.8 (6)	O1_2—Co1—O1_3	90.1 (6)
O1_3—Ti1—O1_3	180.0 (10)	O1_3—Co1—O1_3	180.0 (11)

(LSCT30_SXRD) Lanthanum Strontium Cobalt(II) Titanium(IV) oxide top

Crystal data top

CoLa_1.7O₆Sr_0.3Ti	Z = 2
M_r = 465.26	? _exptl_crystal_density_diffrn 6.443(1) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 410.4
Orthorhombic, Pnma	Synchrotron radiation, λ = 0.621000 Å
Hall symbol: -P 2ac 2n	µ = 7.92 mm⁻¹
a = 5.52939 (10) Å	T = 295 K
b = 7.81873 (13) Å	Particle morphology: plate-like SEM
c = 5.54331 (9) Å	black
V = 239.65 (1) Å³	cylinder, 15 × 20 mm

Data collection top

Home-made heavy-duty Theta-2theta goniometer diffractometer	Scan method: step
Radiation source: Synchrotron	Absorption correction: for a cylinder mounted on the φ axis Cromer and Liberman algorithm
Si 111 monochromator	T_min = ?, T_max = ?
Specimen mounting: Borosilicate 0.3 mm capillary	2θ_min = 8.056°, 2θ_max = 46.996°, 2θ_step = 0.010°
Data collection mode: transmission

Refinement top

Refinement on I_net	3895 data points
Least-squares matrix: full with fixed elements per cycle	Profile function: pseudo-Voigt
R_p = 0.059	30 parameters
R_wp = 0.077	0 restraints
R_exp = 0.058	Weighting scheme based on measured s.u.'s 1/[Y_i + σ(Y_i)]
R_Bragg = 0.042	(Δ/σ)_max = 0.01
χ² = 3.082	Background function: Set of experimental background points

Crystal data top

CoLa_1.7O₆Sr_0.3Ti	V = 239.65 (1) Å³
M_r = 465.26	Z = 2
Orthorhombic, Pnma	Synchrotron radiation, λ = 0.621000 Å
a = 5.52939 (10) Å	µ = 7.92 mm⁻¹
b = 7.81873 (13) Å	T = 295 K
c = 5.54331 (9) Å	cylinder, 15 × 20 mm

Data collection top

Home-made heavy-duty Theta-2theta goniometer diffractometer	Absorption correction: for a cylinder mounted on the φ axis Cromer and Liberman algorithm
Specimen mounting: Borosilicate 0.3 mm capillary	T_min = ?, T_max = ?
Data collection mode: transmission	2θ_min = 8.056°, 2θ_max = 46.996°, 2θ_step = 0.010°
Scan method: step

Refinement top

R_p = 0.059	χ² = 3.082
R_wp = 0.077	3895 data points
R_exp = 0.058	30 parameters
R_Bragg = 0.042	0 restraints

Special details top

Experimental. Synchrotron source

Refinement. Symmetry-adapted Rietveld refinement by simulteneuos fitting of SXRD and NPD data.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.50000	0.00000	0.00000	0.0014 (5)*	0.50000
Ti1	0.50000	0.00000	0.00000	0.0014 (5)*	0.50000
La1	0.02348 (16)	0.25000	0.0037 (4)	0.00622 (17)*	0.84700
Sr1	0.02348 (16)	0.25000	0.0037 (4)	0.00622 (17)*	0.15300
O1	0.7774 (3)	0.0348 (2)	0.2228 (3)	0.0076 (3)*
O1_2	0.0084 (4)	0.75000	0.4341 (4)	0.0078 (4)*

Geometric parameters (Å, º) top

La1—O1ⁱ	2.482 (2)	La1—O1_2^x	3.121 (3)
La1—O1ⁱⁱ	2.665 (2)	La1—O1_2^xi	2.966 (2)
La1—O1ⁱⁱⁱ	2.7833 (19)	La1—O1_2^xii	2.617 (2)
La1—O1^iv	3.186 (2)	Co1—O1	1.9880 (17)
La1—O1^v	2.7833 (19)	Co1—O1^xiii	1.9875 (17)
La1—O1^vi	3.186 (2)	Co1—O1^v	1.9880 (17)
La1—O1^vii	2.482 (2)	Co1—O1^viii	1.9875 (17)
La1—O1^viii	2.665 (2)	Co1—O1_2^xiv	1.9891 (4)
La1—O1_2^ix	2.433 (3)	Co1—O1_2^xii	1.9891 (4)

O1—Co1—O1	91.22 (12)	O1—Co1—O1_2	90.40 (10)
O1—Co1—O1	180.00 (15)	O1—Co1—O1	91.22 (12)
O1—Co1—O1	88.78 (12)	O1—Co1—O1_2	89.87 (11)
O1—Co1—O1_2	90.13 (10)	O1—Co1—O1_2	90.13 (10)
O1—Co1—O1_2	89.87 (11)	O1—Co1—O1_2	90.40 (10)
O1—Co1—O1	88.78 (12)	O1—Co1—O1_2	89.60 (11)
O1—Co1—O1	180.00 (15)	O1_2—Co1—O1_2	180.00 (4)
O1—Co1—O1_2	89.60 (11)

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

(LSCT30_NPD) Lanthanum Strontium Cobalt(II) Titanium(IV) oxide top

Crystal data top

CoLa_1.7O₆Sr_0.3Ti	Z = 2
M_r = 465.26	? _exptl_crystal_density_diffrn 6.443(1) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 100.1
Orthorhombic, Pnma	Constant Wavelength Neutron Diffraction radiation, λ = 1.594000 Å
Hall symbol: -P 2ac 2n	µ = 0.00 mm⁻¹
a = 5.52939 (10) Å	T = 295 K
b = 7.81873 (13) Å	Particle morphology: plate-like SEM
c = 5.54331 (9) Å	black
V = 239.65 (1) Å³	cylinder, 15 × 20 mm

Data collection top

High-resolution two-axis diffractometer	Data collection mode: transmission
Radiation source: nuclear reactor, D2B beamline ILL	Scan method: step
Ge monochromator	2θ_min = 0.309°, 2θ_max = 160.220°, 2θ_step = 0.050°
Specimen mounting: 'vanadium can'

Refinement top

Refinement on I_net	4061 data points
Least-squares matrix: full with fixed elements per cycle	Profile function: pseudo-Voigt
R_p = 0.036	30 parameters
R_wp = 0.045	0 restraints
R_exp = 0.027	Weighting scheme based on measured s.u.'s 1/[Y_i + σ(Y_i)]
R_Bragg = 0.021	(Δ/σ)_max = 0.01
χ² = 6.965	Background function: Set of experimental background points

Crystal data top

CoLa_1.7O₆Sr_0.3Ti	V = 239.65 (1) Å³
M_r = 465.26	Z = 2
Orthorhombic, Pnma	Constant Wavelength Neutron Diffraction radiation, λ = 1.594000 Å
a = 5.52939 (10) Å	µ = 0.00 mm⁻¹
b = 7.81873 (13) Å	T = 295 K
c = 5.54331 (9) Å	cylinder, 15 × 20 mm

Data collection top

High-resolution two-axis diffractometer	Scan method: step
Specimen mounting: 'vanadium can'	2θ_min = 0.309°, 2θ_max = 160.220°, 2θ_step = 0.050°
Data collection mode: transmission

Refinement top

R_p = 0.036	χ² = 6.965
R_wp = 0.045	4061 data points
R_exp = 0.027	30 parameters
R_Bragg = 0.021	0 restraints

Special details top

Experimental. Neutron reactor

Refinement. Symmetry-adapted Rietveld refinement by simulteneuos fitting of SXRD and NPD data.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.50000	0.00000	0.00000	0.0014 (5)*	0.50000
Ti1	0.50000	0.00000	0.00000	0.0014 (5)*	0.50000
La1	0.02348 (16)	0.25000	0.0037 (4)	0.00622 (17)*	0.84700
Sr1	0.02348 (16)	0.25000	0.0037 (4)	0.00622 (17)*	0.15300
O1	0.7774 (3)	0.0348 (2)	0.2228 (3)	0.0076 (3)*
O1_2	0.0084 (4)	0.75000	0.4341 (4)	0.0078 (4)*

Geometric parameters (Å, º) top

La1—O1ⁱ	2.482 (2)	La1—O1_2^x	3.121 (3)
La1—O1ⁱⁱ	2.665 (2)	La1—O1_2^xi	2.966 (2)
La1—O1ⁱⁱⁱ	2.7833 (19)	La1—O1_2^xii	2.617 (2)
La1—O1^iv	3.186 (2)	Co1—O1	1.9880 (17)
La1—O1^v	2.7833 (19)	Co1—O1^xiii	1.9875 (17)
La1—O1^vi	3.186 (2)	Co1—O1^v	1.9880 (17)
La1—O1^vii	2.482 (2)	Co1—O1^viii	1.9875 (17)
La1—O1^viii	2.665 (2)	Co1—O1_2^xiv	1.9891 (4)
La1—O1_2^ix	2.433 (3)	Co1—O1_2^xii	1.9891 (4)

O1—Co1—O1	91.22 (12)	O1—Co1—O1_2	90.40 (10)
O1—Co1—O1	180.00 (15)	O1—Co1—O1	91.22 (12)
O1—Co1—O1	88.78 (12)	O1—Co1—O1_2	89.87 (11)
O1—Co1—O1_2	90.13 (10)	O1—Co1—O1_2	90.13 (10)
O1—Co1—O1_2	89.87 (11)	O1—Co1—O1_2	90.40 (10)
O1—Co1—O1	88.78 (12)	O1—Co1—O1_2	89.60 (11)
O1—Co1—O1	180.00 (15)	O1_2—Co1—O1_2	180.00 (4)
O1—Co1—O1_2	89.60 (11)

(LSCT50_SXRD) Lanthanum Strontium Cobalt(II) Titanium(IV) oxide top

Crystal data top

CoLa_1.5O₆Sr_0.5Ti	Z = 2
M_r = 455.00	? _exptl_crystal_density_diffrn 6.391(1) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 402.8
Orthorhombic, Pnma	Synchrotron radiation, λ = 0.621000 Å
Hall symbol: -P 2ac 2n	µ = 8.31 mm⁻¹
a = 5.49186 (7) Å	T = 295 K
b = 7.77013 (10) Å	Particle morphology: plate-like SEM
c = 5.53014 (7) Å	black
V = 235.99 (1) Å³	cylinder, 15 × 20 mm

Data collection top

Home-made heavy-duty Theta-2theta goniometer diffractometer	Scan method: step
Radiation source: Synchrotron	Absorption correction: for a cylinder mounted on the φ axis Cromer and Liberman algorithm
Si 111 monochromator	T_min = ?, T_max = ?
Specimen mounting: Borosilicate 0.3 mm capillary	2θ_min = 8.069°, 2θ_max = 47.009°, 2θ_step = 0.010°
Data collection mode: transmission

Refinement top

Refinement on I_net	3895 data points
Least-squares matrix: full with fixed elements per cycle	Profile function: pseudo-Voigt
R_p = 0.070	34 parameters
R_wp = 0.089	0 restraints
R_exp = 0.059	Weighting scheme based on measured s.u.'s 1/[Y_i + σ(Y_i)]
R_Bragg = 0.058	(Δ/σ)_max = 0.01
χ² = 5.045	Background function: Set of experimental background points

Crystal data top

CoLa_1.5O₆Sr_0.5Ti	V = 235.99 (1) Å³
M_r = 455.00	Z = 2
Orthorhombic, Pnma	Synchrotron radiation, λ = 0.621000 Å
a = 5.49186 (7) Å	µ = 8.31 mm⁻¹
b = 7.77013 (10) Å	T = 295 K
c = 5.53014 (7) Å	cylinder, 15 × 20 mm

Data collection top

Home-made heavy-duty Theta-2theta goniometer diffractometer	Absorption correction: for a cylinder mounted on the φ axis Cromer and Liberman algorithm
Specimen mounting: Borosilicate 0.3 mm capillary	T_min = ?, T_max = ?
Data collection mode: transmission	2θ_min = 8.069°, 2θ_max = 47.009°, 2θ_step = 0.010°
Scan method: step

Refinement top

R_p = 0.070	χ² = 5.045
R_wp = 0.089	3895 data points
R_exp = 0.059	34 parameters
R_Bragg = 0.058	0 restraints

Special details top

Experimental. Synchrotron source

Refinement. Symmetry-adapted Rietveld refinement by simulteneuos fitting of SXRD and NPD data.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.50000	0.00000	0.00000	0.0076 (10)*	0.50000
Ti1	0.50000	0.00000	0.00000	0.0076 (10)*	0.50000
La1	0.0092 (3)	0.25000	0.0021 (2)	0.00989 (17)*	0.74672
Sr1	0.0092 (3)	0.25000	0.0021 (2)	0.00989 (17)*	0.25328
O1	0.7631 (3)	0.03058 (11)	0.2374 (3)	0.0125 (2)*
O1_2	0.0029 (5)	0.75000	0.4426 (2)	0.0091 (3)*

Geometric parameters (Å, º) top

La1—O1ⁱ	2.5351 (17)	La1—O1_2^x	3.0716 (16)
La1—O1ⁱⁱ	2.6318 (17)	La1—O1_2^xi	2.832 (3)
La1—O1ⁱⁱⁱ	2.8409 (15)	La1—O1_2^xii	2.700 (3)
La1—O1^iv	3.0219 (16)	Co1—O1	1.9667 (16)
La1—O1^v	2.8409 (15)	Co1—O1^xiii	1.9642 (16)
La1—O1^vi	3.0219 (16)	Co1—O1^v	1.9667 (16)
La1—O1^vii	2.5351 (17)	Co1—O1^viii	1.9642 (16)
La1—O1^viii	2.6318 (17)	Co1—O1_2^xiv	1.9684 (2)
La1—O1_2^ix	2.4602 (16)	Co1—O1_2^xii	1.9684 (2)

O1—Co1—O1	91.23 (12)	O1—Co1—O1_2	90.32 (9)
O1—Co1—O1	180.00 (15)	O1—Co1—O1	91.23 (12)
O1—Co1—O1	88.77 (12)	O1—Co1—O1_2	89.68 (10)
O1—Co1—O1_2	90.32 (9)	O1—Co1—O1_2	90.32 (9)
O1—Co1—O1_2	89.68 (10)	O1—Co1—O1_2	90.32 (9)
O1—Co1—O1	88.77 (12)	O1—Co1—O1_2	89.68 (10)
O1—Co1—O1	180.00 (15)	O1_2—Co1—O1_2	180.000 (17)
O1—Co1—O1_2	89.68 (10)

(LSCT50_NPD) Lanthanum Strontium Cobalt(II) Titanium(IV) oxide top

Crystal data top

CoLa_1.5O₆Sr_0.5Ti	Z = 2
M_r = 455.00	? _exptl_crystal_density_diffrn 6.391(1) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 99.6
Orthorhombic, Pnma	Constant Wavelength Neutron Diffraction radiation, λ = 1.594000 Å
Hall symbol: -P 2ac 2n	µ = 0.00 mm⁻¹
a = 5.49186 (7) Å	T = 295 K
b = 7.77013 (10) Å	Particle morphology: plate-like SEM
c = 5.53014 (7) Å	black
V = 235.99 (1) Å³	cylinder, 15 × 20 mm

Data collection top

High-resolution two-axis diffractometer	Data collection mode: transmission
Radiation source: nuclear reactor, D2B beamline ILL	Scan method: step
Ge monochromator	2θ_min = 0.270°, 2θ_max = 160.229°, 2θ_step = 0.050°
Specimen mounting: 'vanadium can'

Refinement top

Refinement on I_net	3895 data points
Least-squares matrix: full with fixed elements per cycle	Profile function: pseudo-Voigt
R_p = 0.030	34 parameters
R_wp = 0.040	0 restraints
R_exp = 0.016	Weighting scheme based on measured s.u.'s 1/[Y_i + σ(Y_i)]
R_Bragg = 0.027	(Δ/σ)_max = 0.01
χ² = 41.290	Background function: Set of experimental background points

Crystal data top

CoLa_1.5O₆Sr_0.5Ti	V = 235.99 (1) Å³
M_r = 455.00	Z = 2
Orthorhombic, Pnma	Constant Wavelength Neutron Diffraction radiation, λ = 1.594000 Å
a = 5.49186 (7) Å	µ = 0.00 mm⁻¹
b = 7.77013 (10) Å	T = 295 K
c = 5.53014 (7) Å	cylinder, 15 × 20 mm

Data collection top

High-resolution two-axis diffractometer	Scan method: step
Specimen mounting: 'vanadium can'	2θ_min = 0.270°, 2θ_max = 160.229°, 2θ_step = 0.050°
Data collection mode: transmission

Refinement top

R_p = 0.030	χ² = 41.290
R_wp = 0.040	3895 data points
R_exp = 0.016	34 parameters
R_Bragg = 0.027	0 restraints

Special details top

Experimental. Neutron reactor

Refinement. Symmetry-adapted Rietveld refinement by simulteneuos fitting of SXRD and NPD data.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.50000	0.00000	0.00000	0.0076 (10)*	0.50000
Ti1	0.50000	0.00000	0.00000	0.0076 (10)*	0.50000
La1	0.0092 (3)	0.25000	0.0021 (2)	0.00989 (17)*	0.74672
Sr1	0.0092 (3)	0.25000	0.0021 (2)	0.00989 (17)*	0.25328
O1	0.7631 (3)	0.03058 (11)	0.2374 (3)	0.0125 (2)*
O1_2	0.0029 (5)	0.75000	0.4426 (2)	0.0091 (3)*

Geometric parameters (Å, º) top

La1—O1ⁱ	2.5351 (17)	La1—O1_2^x	3.0716 (16)
La1—O1ⁱⁱ	2.6318 (17)	La1—O1_2^xi	2.832 (3)
La1—O1ⁱⁱⁱ	2.8409 (15)	La1—O1_2^xii	2.700 (3)
La1—O1^iv	3.0219 (16)	Co1—O1	1.9667 (16)
La1—O1^v	2.8409 (15)	Co1—O1^xiii	1.9642 (16)
La1—O1^vi	3.0219 (16)	Co1—O1^v	1.9667 (16)
La1—O1^vii	2.5351 (17)	Co1—O1^viii	1.9642 (16)
La1—O1^viii	2.6318 (17)	Co1—O1_2^xiv	1.9684 (2)
La1—O1_2^ix	2.4602 (16)	Co1—O1_2^xii	1.9684 (2)

O1—Co1—O1	91.23 (12)	O1—Co1—O1_2	90.32 (9)
O1—Co1—O1	180.00 (15)	O1—Co1—O1	91.23 (12)
O1—Co1—O1	88.77 (12)	O1—Co1—O1_2	89.68 (10)
O1—Co1—O1_2	90.32 (9)	O1—Co1—O1_2	90.32 (9)
O1—Co1—O1_2	89.68 (10)	O1—Co1—O1_2	90.32 (9)
O1—Co1—O1	88.77 (12)	O1—Co1—O1_2	89.68 (10)
O1—Co1—O1	180.00 (15)	O1_2—Co1—O1_2	180.000 (17)
O1—Co1—O1_2	89.68 (10)

Experimental details

	(LCTO_SXRD)	(LCTO_NPD)	(LSCT10_XRD)	(LSCT10_NPD)
Crystal data
Chemical formula	Co₂La₄O₁₂Ti₂	Co₂La₄O₁₂Ti₂	CoLa_1.9O₆Sr_0.1Ti	CoLa_1.9O₆Sr_0.1Ti
M_r	480.62	480.62	475.52	475.52
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/n	Monoclinic, P2₁/n	Monoclinic, P2₁/n
Temperature (K)	295	295	295	295
a, b, c (Å)	5.55510 (9), 5.57813 (8), 7.85718 (12)	5.55510 (9), 5.57813 (8), 7.85718 (12)	5.55318 (8), 5.56557 (7), 7.84995 (10)	5.55318 (8), 5.56557 (7), 7.84995 (10)
α, β, γ (°)	90, 90.005 (5), 90	90, 90.005 (5), 90	90, 90.007 (5), 90	90, 90.007 (5), 90
V (Å³)	243.47 (1)	243.47 (1)	242.62 (1)	242.62 (1)
Z	2	2	2	2
Radiation type	Synchrotron, λ = 0.621000 Å	Constant Wavelength Neutron Diffraction, λ = 1.594000 Å	Cu Kα₁, λ = 1.540560 Å	Constant Wavelength Neutron Diffraction, λ = 1.594000 Å
µ (mm⁻¹)	7.37	0.00	–	0.00
Specimen shape, size (mm)	Cylinder, 15 × 20	Cylinder, 15 × 20	Flat sheet, 20 × 20	Cylinder, 15 × 20

Data collection
Diffractometer	Home-made heavy-duty Theta-2theta goniometer diffractometer	High-resolution two-axis diffractometer	Bruker D8 Advance diffractometer	High-resolution two-axis diffractometer
Specimen mounting	Borosilicate 0.3 mm capillary	'vanadium can'	Aluminium Sample holder	'vanadium can'
Data collection mode	Transmission	Transmission	Reflexion	Transmission
Scan method	Step	Step	Step	Step
Absorption correction	For a cylinder mounted on the φ axis Cromer and Liberman algorithm	–	–	–
2θ values (°)	2θ_min = 7.989 2θ_max = 46.991 2θ_step = 0.010	2θ_min = 0.239 2θ_max = 160.189 2θ_step = 0.050	2θ_min = 19.880 2θ_max = 99.882 2θ_step = 0.020	2θ_min = 0.245 2θ_max = 160.195 2θ_step = 0.050

Refinement
R factors and goodness of fit	R_p = 0.073, R_wp = 0.100, R_exp = 0.058, R_Bragg = 0.036, χ² = 8.418	R_p = 0.046, R_wp = 0.059, R_exp = 0.039, R_Bragg = 0.032, χ² = 5.505	R_p = 0.036, R_wp = 0.047, R_exp = 0.035, R_Bragg = 0.083, χ² = 3.147	R_p = 0.364, R_wp = 0.047, R_exp = 0.027, R_Bragg = 0.023, χ² = 9.624
No. of data points	3901	3901	4061	4061
No. of parameters	40	40	34	34

	(LSCT20_SXRD)	(LSCT20_NPD)	(LSCT30_SXRD)	(LSCT30_NPD)
Crystal data
Chemical formula	CoLa_1.8O₆Sr_0.2Ti	CoLa_1.8O₆Sr_0.2Ti	CoLa_1.7O₆Sr_0.3Ti	CoLa_1.7O₆Sr_0.3Ti
M_r	470.39	470.39	465.26	465.26
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/n	Orthorhombic, Pnma	Orthorhombic, Pnma
Temperature (K)	295	295	295	295
a, b, c (Å)	5.55020 (11), 5.54838 (9), 7.83763 (10)	5.55020 (11), 5.54838 (9), 7.83763 (10)	5.52939 (10), 7.81873 (13), 5.54331 (9)	5.52939 (10), 7.81873 (13), 5.54331 (9)
α, β, γ (°)	90, 90.014 (7), 90	90, 90.014 (7), 90	90, 90, 90	90, 90, 90
V (Å³)	241.36 (1)	241.36 (1)	239.65 (1)	239.65 (1)
Z	2	2	2	2
Radiation type	Synchrotron, λ = 0.621000 Å	Constant Wavelength Neutron Diffraction, λ = 1.594000 Å	Synchrotron, λ = 0.621000 Å	Constant Wavelength Neutron Diffraction, λ = 1.594000 Å
µ (mm⁻¹)	7.73	0.00	7.92	0.00
Specimen shape, size (mm)	Cylinder, 15 × 20	Cylinder, 15 × 20	Cylinder, 15 × 20	Cylinder, 15 × 20

Data collection
Diffractometer	Home-made heavy-duty Theta-2theta goniometer diffractometer	High-resolution two-axis diffractometer	Home-made heavy-duty Theta-2theta goniometer diffractometer	High-resolution two-axis diffractometer
Specimen mounting	Borosilicate 0.3 mm capillary	'vanadium can'	Borosilicate 0.3 mm capillary	'vanadium can'
Data collection mode	Transmission	Transmission	Transmission	Transmission
Scan method	Step	Step	Step	Step
Absorption correction	–	–	–	–
2θ values (°)	2θ_min = 7.011 2θ_max = 37.302 2θ_step = 0.010	2θ_min = 0.241 2θ_max = 160.191 2θ_step = 0.050	2θ_min = 8.056 2θ_max = 46.996 2θ_step = 0.010	2θ_min = 0.309 2θ_max = 160.220 2θ_step = 0.050

Refinement
R factors and goodness of fit	R_p = 0.156, R_wp = 0.239, R_exp = 0.213, R_Bragg = 0.079, χ² = 1.573	R_p = 0.035, R_wp = 0.045, R_exp = 0.026, R_Bragg = 0.025, χ² = 8.804	R_p = 0.059, R_wp = 0.077, R_exp = 0.058, R_Bragg = 0.042, χ² = 3.082	R_p = 0.036, R_wp = 0.045, R_exp = 0.027, R_Bragg = 0.021, χ² = 6.965
No. of data points	3030	3901	3895	4061
No. of parameters	40	40	30	30

	(LSCT50_SXRD)	(LSCT50_NPD)
Crystal data
Chemical formula	CoLa_1.5O₆Sr_0.5Ti	CoLa_1.5O₆Sr_0.5Ti
M_r	455.00	455.00
Crystal system, space group	Orthorhombic, Pnma	Orthorhombic, Pnma
Temperature (K)	295	295
a, b, c (Å)	5.49186 (7), 7.77013 (10), 5.53014 (7)	5.49186 (7), 7.77013 (10), 5.53014 (7)
α, β, γ (°)	90, 90, 90	90, 90, 90
V (Å³)	235.99 (1)	235.99 (1)
Z	2	2
Radiation type	Synchrotron, λ = 0.621000 Å	Constant Wavelength Neutron Diffraction, λ = 1.594000 Å
µ (mm⁻¹)	8.31	0.00
Specimen shape, size (mm)	Cylinder, 15 × 20	Cylinder, 15 × 20

Data collection
Diffractometer	Home-made heavy-duty Theta-2theta goniometer diffractometer	High-resolution two-axis diffractometer
Specimen mounting	Borosilicate 0.3 mm capillary	'vanadium can'
Data collection mode	Transmission	Transmission
Scan method	Step	Step
Absorption correction	–	–
2θ values (°)	2θ_min = 8.069 2θ_max = 47.009 2θ_step = 0.010	2θ_min = 0.270 2θ_max = 160.229 2θ_step = 0.050

Refinement
R factors and goodness of fit	R_p = 0.070, R_wp = 0.089, R_exp = 0.059, R_Bragg = 0.058, χ² = 5.045	R_p = 0.030, R_wp = 0.040, R_exp = 0.016, R_Bragg = 0.027, χ² = 41.290
No. of data points	3895	3895
No. of parameters	34	34

Computer programs: FULLPROF.

Format		BIBTeX
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Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text