Charge-ordering transition in iron oxide Fe4O5 involving competing dimer and trimer formation
Authors:Ovsyannikov, Sergei V.; Bykov, Maxim; Bykova, Elena; Kozlenko, Denis P.; Tsirlin, Alexander A.; Karkin, Alexander E.; Shchennikov, Vladimir V.; Kichanov, Sergei E.; Gou, Huiyang; Abakumov, Artem M.; Egoavil, Ricardo; Verbeeck, Johan; McCammon, Catherine; Dyadkin, Vadim; Chernyshov, Dmitry; van Smaalen, Sander; Dubrovinsky, Leonid S.
Journal:Nature Chemistry 8 501-508 (2016)
DOI:https://doi.org/10.1038/nchem.2478
B-IncStrDB ID: 11542E01ukP Entry date: 2016-02-12 Last revision: 2022-01-02
Fe4O5_4K
Chemical data
Full Name: iron (II,III) oxide [ Help ]
Formula moiety: Fe4 O5 [ Help ]
Structural Formula Sum: Fe4 O5 [ Help ]
Formula weight: 303.4 Da [ Help ]
Crystallographic data and experimental details
Crystal system: monoclinic [ Help ]
Superspace group name: C21/m(αβ0)0s [ Help ]
Symmetry operations of the superspace group: (Show/hide table) [ Help ]
| Operation code | Operation in algebraic form |
|---|---|
| 1 | x1,x2,x3,x4 |
| 2 | -x1,-x2,x3+1/2,-x4+1/2 |
| 3 | -x1,-x2,-x3,-x4 |
| 4 | x1,x2,-x3+1/2,x4+1/2 |
| 5 | x1+1/2,x2+1/2,x3,x4 |
| 6 | -x1+1/2,-x2+1/2,x3+1/2,-x4+1/2 |
| 7 | -x1+1/2,-x2+1/2,-x3,-x4 |
| 8 | x1+1/2,x2+1/2,-x3+1/2,x4+1/2 |
a: 2.861(4) Å [ Help ]
b: 9.8123(5) Å [ Help ]
c: 12.5425(11) Å [ Help ]
α: 90 ° [ Help ]
β: 90 ° [ Help ]
γ: 90 ° [ Help ]
Volume: 352.11(6) Å3 [ Help ]
Modulation dimension: 1 [ Help ]
Measured independent wave vectors: (Show/hide table) [ Help ]
| Wave vector id | q_x | q_y | q_z |
|---|---|---|---|
| 1 | 0.333333 | 0.7293 | 0 |
Z: 4 [ Help ]
Cell determination reflection Nb.: 2536 [ Help ]
θ(min) for cell determination: 1.616 ° [ Help ]
θ(max) for cell determination: 31.273 ° [ Help ]
Cell measurement temperature: 4 K [ Help ]
μ: 14.214 mm-1 [ Help ]
Absorption correction type: multi-scan [ Help ]
Absorption correction remarks: CrysAlisPro, Agilent Technologies, Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) (compiled Feb 1 2013,16:14:44) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. [ Help ]
Minimum transmission factor: 0.32722 [ Help ]
Maximum transmission factor: 1 [ Help ]
Refinement details
Total nb. of reflections: 2241 [ Help ]
Nb. of observed reflections: 1603 [ Help ]
Intense reflections threshold: I>3σ(I) [ Help ]
Refinement based on: F [ Help ]
R(obs): 0.0518 [ Help ]
wR(obs): 0.0845 [ Help ]
R(all): 0.0582 [ Help ]
wR(all): 0.085 [ Help ]
S(all): 3.62 [ Help ]
S(obs): 4.27 [ Help ]
Nb. of reflections: 2241 [ Help ]
Nb. of parameters: 59 [ Help ]
Weighting scheme: sigma [ Help ]
Weighting scheme remarks: w=1/(σ2(F)+0.0001F2) [ Help ]
Δ/σ(max): 0.0002 [ Help ]
Δ/σ(mean): 0.0000 [ Help ]
Δρ(max): 1.36 e_Å-3 [ Help ]
Δρ(min): -2.47 e_Å-3 [ Help ]
Extinction method: none [ Help ]
Structural Information
Average Structure: (Show/hide table) [ Help ]
| Atom site label | Atom symbol | x | y | z | ADP type | Uiso/equiv | Symmetry multiplicity | Occupancy | Coords from (d)iffraction or (c)alculated | Coords restraints or constraints | Disordered cluster | Disordered group |
|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Fe1 | Fe | 0.7517(3) | 0.2551(5) | 0.25 | Uani | 0.0071(2) | 4 | 1 | d | ? | ? | ? |
| Fe2 | Fe | 0.25 | 0.25 | 0 | Uani | 0.0067(2) | 4 | 1 | d | ? | ? | ? |
| Fe3 | Fe | 0.2495(2) | 0.51083(4) | 0.11781(3) | Uani | 0.0071(2) | 8 | 1 | d | ? | ? | ? |
| O1 | O | -0.261(11) | 0.39105(17) | 0.04391(15) | Uiso | 0.0063(4) | 8 | 1 | d | ? | ? | ? |
| O2 | O | 0.2337(15) | 0.4103(3) | 0.25 | Uiso | 0.0058(5) | 4 | 1 | d | ? | ? | ? |
| O3 | O | 0.2434(9) | 0.15859(18) | 0.14238(15) | Uiso | 0.007(4) | 8 | 1 | d | ? | ? | ? |
ADP components: (Show/hide table) [ Help ]
| Atom site label | Atom site symbol | U11 | U22 | U33 | U12 | U13 | U23 |
|---|---|---|---|---|---|---|---|
| Fe1 | Fe | 0.0115(6) | 0.0052(3) | 0.0048(3) | 0.0034(6) | 0 | 0 |
| Fe2 | Fe | 0.0128(5) | 0.0041(3) | 0.0032(3) | -0.0009(4) | -0.0008(4) | 0.00027(14) |
| Fe3 | Fe | 0.0133(5) | 0.0039(2) | 0.004(3) | -0.0001(4) | 0.0013(3) | 0.00029(10) |
Fourier Wave Vectors (explicit: q_x,q_y,q_z or coefficients: q_1,q_2,...): (Show/hide table) [ Help ]
| Wave vector code | q_1 |
|---|---|
| 1 | 1 |
Definition of the displacive (translational) Fourier series: (Show/hide table) [ Help ]
| Modulation code | Atom site label | Displacement axis | Wave vector code |
|---|---|---|---|
| Fex1 | Fe1 | x | 1 |
| Fey1 | Fe1 | y | 1 |
| Fez1 | Fe1 | z | 1 |
| Fex2 | Fe2 | x | 1 |
| Fey2 | Fe2 | y | 1 |
| Fez2 | Fe2 | z | 1 |
| Fex3 | Fe3 | x | 1 |
| Fey3 | Fe3 | y | 1 |
| Fez3 | Fe3 | z | 1 |
| O1x1 | O1 | x | 1 |
| O1y1 | O1 | y | 1 |
| O1z1 | O1 | z | 1 |
| O2x1 | O2 | x | 1 |
| O2y1 | O2 | y | 1 |
| O2z1 | O2 | z | 1 |
| O3x1 | O3 | x | 1 |
| O3y1 | O3 | y | 1 |
| O3z1 | O3 | z | 1 |
Displacive (translational) Fourier coefficients: (Show/hide table) [ Help ]
| Modulation code | Cosine coefficient | Sine coefficient |
|---|---|---|
| Fex1 | 0 | 0 |
| Fey1 | 0 | 0 |
| Fez1 | 0.00039(5) | -0.00052(5) |
| Fex2 | 0 | -0.0329(2) |
| Fey2 | 0 | -0.00096(5) |
| Fez2 | 0 | 0.00132(5) |
| Fex3 | -0.02293(15) | 0.00966(13) |
| Fey3 | -0.00072(4) | 0.00283(3) |
| Fez3 | 0.00024(3) | 0.001(3) |
| O1x1 | 0.0035(6) | -0.0005(6) |
| O1y1 | 0.00441(15) | 0.00345(16) |
| O1z1 | 0.00162(15) | 0.00105(15) |
| O2x1 | 0 | 0 |
| O2y1 | 0 | 0 |
| O2z1 | -0.0007(2) | -0.001(2) |
| O3x1 | 0.0027(5) | -0.0058(5) |
| O3y1 | -0.00114(15) | -0.0028(15) |
| O3z1 | 0.00072(16) | -0.00029(15) |