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The structure of synthetic YbFeMnO
4 has been refined by single-crystal X-ray diffraction. Space group
Rm,
a = 3.4580 (1),
c = 25.647 (3) Å,
V = 265.59 (3) Å
3,
Z = 3. Yb is in octahedral coordination, whereas Fe and Mn are disordered on a single crystallographic type of trigonal bipyramid, in which the cation is off-centred from the basal plane. Assuming perfect stoichiometry,
R1 = 0.0195, but the charge distribution (CD) analysis suggests incomplete occupation of the Yb site. Refinement of the occupancy lowers
R1 to 0.0175, resulting in s.o.f.(Yb) = 0.963 (3), with a significant improvement of the Fourier difference. The electroneutrality is likely preserved through incomplete occupancy of one of the two oxygen sites: the compound is thus non-stoichiometric, with the formula Yb
0.963FeMnO
3.945. Another mechanism for preserving the electroneutrality is the oxidation of a small amount of Mn
2+ to Mn
3+, which is, however, less probable because of the reduction conditions in which the sample was synthesized. Both models give a satisfactorily CD result, but they cannot be definitively distinguished by X-ray data.
Supporting information
Data collection: CAD-4 EXPRESS; cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
Crystal data top
Yb0.963FeMnO3.945 | Dx = 6.405 Mg m−3 |
Mr = 341.49 | Mo Kα radiation, λ = 0.71073 Å |
Hexagonal, R3m | Cell parameters from 18 reflections |
Hall symbol: -R 3 2" | θ = 41.0–45.3° |
a = 3.4580 (1) Å | µ = 32.64 mm−1 |
c = 25.647 (3) Å | T = 293 K |
V = 265.59 (3) Å3 | Sphere, black |
Z = 3 | 0.06 × 0.06 × 0.06 × 0.06 (radius) mm |
F(000) = 451 | |
Data collection top
Enraf Nonius CAD4 diffractometer | 528 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 59.8°, θmin = 2.4° |
ω–θ scans | h = 0→7 |
Absorption correction: for a sphere PLATON | k = 0→4 |
Tmin = 0.086, Tmax = 0.166 | l = −60→61 |
655 measured reflections | 3 standard reflections every 240 min |
577 independent reflections | intensity decay: none |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.018 | w = 1/[σ2(Fo2) + (0.0192P)2 + 1.2133P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.044 | (Δ/σ)max = 0.001 |
S = 1.18 | Δρmax = 2.55 e Å−3 |
577 reflections | Δρmin = −4.88 e Å−3 |
14 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0290 (11) |
Crystal data top
Yb0.963FeMnO3.945 | Z = 3 |
Mr = 341.49 | Mo Kα radiation |
Hexagonal, R3m | µ = 32.64 mm−1 |
a = 3.4580 (1) Å | T = 293 K |
c = 25.647 (3) Å | 0.06 × 0.06 × 0.06 × 0.06 (radius) mm |
V = 265.59 (3) Å3 | |
Data collection top
Enraf Nonius CAD4 diffractometer | 528 reflections with I > 2σ(I) |
Absorption correction: for a sphere PLATON | Rint = 0.020 |
Tmin = 0.086, Tmax = 0.166 | 3 standard reflections every 240 min |
655 measured reflections | intensity decay: none |
577 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.018 | 14 parameters |
wR(F2) = 0.044 | 0 restraints |
S = 1.18 | Δρmax = 2.55 e Å−3 |
577 reflections | Δρmin = −4.88 e Å−3 |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Yb | 0.0000 | 0.0000 | 0.0000 | 0.01184 (5) | 0.963 (3) |
Fe | 0.0000 | 0.0000 | 0.215706 (14) | 0.00728 (7) | 0.50 |
Mn | 0.0000 | 0.0000 | 0.215706 (14) | 0.00728 (7) | 0.50 |
O1 | 0.0000 | 0.0000 | 0.12826 (13) | 0.0208 (5) | 0.97 |
O2 | 0.0000 | 0.0000 | 0.29345 (8) | 0.0098 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Yb | 0.00345 (4) | 0.00345 (4) | 0.02863 (11) | 0.00172 (2) | 0.000 | 0.000 |
Fe | 0.00660 (8) | 0.00660 (8) | 0.00865 (12) | 0.00330 (4) | 0.000 | 0.000 |
Mn | 0.00660 (8) | 0.00660 (8) | 0.00865 (12) | 0.00330 (4) | 0.000 | 0.000 |
O1 | 0.0217 (8) | 0.0217 (8) | 0.0192 (10) | 0.0108 (4) | 0.000 | 0.000 |
O2 | 0.0095 (3) | 0.0095 (3) | 0.0106 (5) | 0.00474 (17) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Yb—O2i | 2.2432 (10) | Fe—O1v | 2.0150 (5) |
Yb—O2ii | 2.2432 (10) | Fe—O1 | 2.243 (3) |
Yb—O2iii | 2.2432 (10) | Fe—Ybxiii | 3.6176 (4) |
Yb—O2iv | 2.2432 (10) | Fe—Ybxiv | 3.6176 (4) |
Yb—O2v | 2.2433 (10) | Fe—Ybxv | 3.6176 (4) |
Yb—O2vi | 2.2433 (10) | O1—Mniii | 2.0150 (5) |
Yb—Ybvii | 3.4580 | O1—Feiii | 2.0150 (5) |
Yb—Ybviii | 3.4580 | O1—Mni | 2.0150 (5) |
Yb—Ybix | 3.4580 | O1—Fei | 2.0150 (5) |
Yb—Ybx | 3.4580 | O1—Mnv | 2.0150 (5) |
Yb—Ybxi | 3.4580 | O1—Fev | 2.0150 (5) |
Yb—Ybxii | 3.4580 | O2—Ybxiii | 2.2432 (10) |
Fe—O2 | 1.994 (2) | O2—Ybxiv | 2.2432 (10) |
Fe—O1iii | 2.0150 (4) | O2—Ybxv | 2.2433 (10) |
Fe—O1i | 2.0150 (5) | | |
| | | |
O2i—Yb—O2ii | 180.00 (10) | Ybvii—Yb—Ybxii | 60.0 |
O2i—Yb—O2iii | 100.84 (6) | Ybviii—Yb—Ybxii | 120.0 |
O2ii—Yb—O2iii | 79.16 (6) | Ybix—Yb—Ybxii | 180.0 |
O2i—Yb—O2iv | 79.16 (6) | Ybx—Yb—Ybxii | 120.0 |
O2ii—Yb—O2iv | 100.84 (6) | Ybxi—Yb—Ybxii | 60.0 |
O2iii—Yb—O2iv | 180.00 (10) | O2—Fe—O1iii | 97.77 (9) |
O2i—Yb—O2v | 100.84 (6) | O2—Fe—O1i | 97.77 (9) |
O2ii—Yb—O2v | 79.16 (6) | O1iii—Fe—O1i | 118.20 (4) |
O2iii—Yb—O2v | 100.84 (6) | O2—Fe—O1v | 97.77 (9) |
O2iv—Yb—O2v | 79.16 (6) | O1iii—Fe—O1v | 118.20 (4) |
O2i—Yb—O2vi | 79.16 (6) | O1i—Fe—O1v | 118.20 (4) |
O2ii—Yb—O2vi | 100.84 (6) | O2—Fe—O1 | 180.0 |
O2iii—Yb—O2vi | 79.16 (6) | O1iii—Fe—O1 | 82.23 (9) |
O2iv—Yb—O2vi | 100.84 (6) | O1i—Fe—O1 | 82.23 (9) |
O2v—Yb—O2vi | 180.00 (10) | O1v—Fe—O1 | 82.23 (9) |
O2i—Yb—Ybvii | 140.42 (3) | O2—Fe—Ybxiii | 33.496 (5) |
O2ii—Yb—Ybvii | 39.58 (3) | O1iii—Fe—Ybxiii | 112.72 (8) |
O2iii—Yb—Ybvii | 39.58 (3) | O1i—Fe—Ybxiii | 64.28 (9) |
O2iv—Yb—Ybvii | 140.42 (3) | O1v—Fe—Ybxiii | 112.72 (8) |
O2v—Yb—Ybvii | 90.0 | O1—Fe—Ybxiii | 146.504 (4) |
O2vi—Yb—Ybvii | 90.0 | O2—Fe—Ybxiv | 33.496 (4) |
O2i—Yb—Ybviii | 39.58 (3) | O1iii—Fe—Ybxiv | 64.28 (9) |
O2ii—Yb—Ybviii | 140.42 (3) | O1i—Fe—Ybxiv | 112.72 (8) |
O2iii—Yb—Ybviii | 140.42 (3) | O1v—Fe—Ybxiv | 112.72 (8) |
O2iv—Yb—Ybviii | 39.58 (3) | O1—Fe—Ybxiv | 146.504 (4) |
O2v—Yb—Ybviii | 90.0 | Ybxiii—Fe—Ybxiv | 57.102 (7) |
O2vi—Yb—Ybviii | 90.0 | O2—Fe—Ybxv | 33.496 (4) |
Ybvii—Yb—Ybviii | 180.0 | O1iii—Fe—Ybxv | 112.72 (8) |
O2i—Yb—Ybix | 90.0 | O1i—Fe—Ybxv | 112.72 (8) |
O2ii—Yb—Ybix | 90.0 | O1v—Fe—Ybxv | 64.28 (9) |
O2iii—Yb—Ybix | 140.42 (3) | O1—Fe—Ybxv | 146.504 (4) |
O2iv—Yb—Ybix | 39.58 (3) | Ybxiii—Fe—Ybxv | 57.102 (7) |
O2v—Yb—Ybix | 39.58 (3) | Ybxiv—Fe—Ybxv | 57.102 (7) |
O2vi—Yb—Ybix | 140.42 (3) | Mniii—O1—Feiii | 0.00 (2) |
Ybvii—Yb—Ybix | 120.0 | Mniii—O1—Mni | 118.20 (4) |
Ybviii—Yb—Ybix | 60.0 | Feiii—O1—Mni | 118.20 (4) |
O2i—Yb—Ybx | 140.42 (3) | Mniii—O1—Fei | 118.20 (4) |
O2ii—Yb—Ybx | 39.58 (3) | Feiii—O1—Fei | 118.20 (4) |
O2iii—Yb—Ybx | 90.0 | Mni—O1—Fei | 0.00 (2) |
O2iv—Yb—Ybx | 90.0 | Mniii—O1—Mnv | 118.20 (4) |
O2v—Yb—Ybx | 39.58 (3) | Feiii—O1—Mnv | 118.20 (4) |
O2vi—Yb—Ybx | 140.42 (3) | Mni—O1—Mnv | 118.20 (4) |
Ybvii—Yb—Ybx | 60.0 | Fei—O1—Mnv | 118.20 (4) |
Ybviii—Yb—Ybx | 120.0 | Mniii—O1—Fev | 118.20 (4) |
Ybix—Yb—Ybx | 60.0 | Feiii—O1—Fev | 118.20 (4) |
O2i—Yb—Ybxi | 39.58 (3) | Mni—O1—Fev | 118.20 (4) |
O2ii—Yb—Ybxi | 140.42 (3) | Fei—O1—Fev | 118.20 (4) |
O2iii—Yb—Ybxi | 90.0 | Mnv—O1—Fev | 0.00 (2) |
O2iv—Yb—Ybxi | 90.0 | Mniii—O1—Fe | 97.77 (9) |
O2v—Yb—Ybxi | 140.42 (3) | Feiii—O1—Fe | 97.77 (9) |
O2vi—Yb—Ybxi | 39.58 (3) | Mni—O1—Fe | 97.77 (9) |
Ybvii—Yb—Ybxi | 120.0 | Fei—O1—Fe | 97.77 (9) |
Ybviii—Yb—Ybxi | 60.0 | Mnv—O1—Fe | 97.77 (9) |
Ybix—Yb—Ybxi | 120.0 | Fev—O1—Fe | 97.77 (9) |
Ybx—Yb—Ybxi | 180.0 | Fe—O2—Ybxiii | 117.13 (5) |
O2i—Yb—Ybxii | 90.0 | Fe—O2—Ybxiv | 117.13 (5) |
O2ii—Yb—Ybxii | 90.0 | Ybxiii—O2—Ybxiv | 100.84 (6) |
O2iii—Yb—Ybxii | 39.58 (3) | Fe—O2—Ybxv | 117.13 (5) |
O2iv—Yb—Ybxii | 140.42 (3) | Ybxiii—O2—Ybxv | 100.84 (6) |
O2v—Yb—Ybxii | 140.42 (3) | Ybxiv—O2—Ybxv | 100.84 (6) |
O2vi—Yb—Ybxii | 39.58 (3) | | |
Symmetry codes: (i) −x+2/3, −y+1/3, −z+1/3; (ii) x−2/3, y−1/3, z−1/3; (iii) −x−1/3, −y−2/3, −z+1/3; (iv) x+1/3, y+2/3, z−1/3; (v) −x−1/3, −y+1/3, −z+1/3; (vi) x+1/3, y−1/3, z−1/3; (vii) x−1, y−1, z; (viii) x+1, y+1, z; (ix) x, y+1, z; (x) x−1, y, z; (xi) x+1, y, z; (xii) x, y−1, z; (xiii) x+2/3, y+1/3, z+1/3; (xiv) x−1/3, y−2/3, z+1/3; (xv) x−1/3, y+1/3, z+1/3. |
Experimental details
Crystal data |
Chemical formula | Yb0.963FeMnO3.945 |
Mr | 341.49 |
Crystal system, space group | Hexagonal, R3m |
Temperature (K) | 293 |
a, c (Å) | 3.4580 (1), 25.647 (3) |
V (Å3) | 265.59 (3) |
Z | 3 |
Radiation type | Mo Kα |
µ (mm−1) | 32.64 |
Crystal size (mm) | 0.06 × 0.06 × 0.06 × 0.06 (radius) |
|
Data collection |
Diffractometer | Enraf Nonius CAD4 diffractometer |
Absorption correction | For a sphere PLATON |
Tmin, Tmax | 0.086, 0.166 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 655, 577, 528 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 1.217 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.018, 0.044, 1.18 |
No. of reflections | 577 |
No. of parameters | 14 |
Δρmax, Δρmin (e Å−3) | 2.55, −4.88 |
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