Acta Cryst. (2007). E63, i163 [ doi:10.1107/S1600536807029686 ]
The flux-grown single crystals of tridysprosium ruthenium heptaoxide, Dy3RuO7, have a noncentrosymmetric orthorhombic structure composed of infinite single chains of corner-linked RuO6 octahedra embedded in a Dy3O matrix. Partial disorder of Dy atoms was faintly observed. Two Dy atom sites out of the six crystallographically independent Dy sites split into two positions, which are separated by approximately 0.3-0.5 Å and have different coordination environments. The investigated crystal was an inversion twin.
The refinement was carried out based on the starting parameters imported from the P21nb modification of Tb3RuO7 (Ishizawa et al., 2007), employing anisotropic atomic displacement parameters for metal atoms and isotropic ones for O atoms. The non-split atom model indicated Δρ peaks of 10 e Å-3 near Dy5 and Dy6 atom sites in a similar manner to Tb3RuO7. The peak heights are smaller than 33 e Å−3 observed in Tb3RuO7 under approximately the same resolution level of d>0.42 Å. The split pairs of Dy5a and Dy5b, and Dy6a and Dy6b were constrained to have the same anisotropic atomic displacement parameters in the further refinements. The Flack parameter of ~0.5 (Flack, 1983) suggested an existence of inversion related twins as is common for the P21nb modifications of Ln3RuO7 (Ln=Gd, Tb).
Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2; data reduction: DIFDAT, SORTRF and ADDREF in Xtal3.7 (Hall et al., 2003); program(s) used to solve structure: Xtal3.7; program(s) used to refine structure: CRYLSQ in Xtal3.7; molecular graphics: ATOMS (Dowty, 2005); software used to prepare material for publication: BONDLA and CIFIO in Xtal3.7.
![[Figure 1]](./lx2012fig1thm.gif)
| Fig. 1. The structure of Dy3RuO7 projected along a, containing Ru1O6 (blue) and Ru2O6 (purple) octahedral chains in the Tb (red) and O (light blue) matrix. The less populated Dy5b and Dy6b are drawn in yellow. The ADP ellipsoids are drawn at the 97% probability level. |
![[Figure 2]](./lx2012fig2thm.gif)
| Fig. 2. The structure of Dy3RuO7 projected along c with the same colour scheme and probability level of the ADP ellipsoid as in Fig. 1. The Dy—O bonds except for Dy5b and Dy6b are given in black thin lines. |
| Dy3RuO7 | F(000) = 2384 |
| Mr = 700.57 | Dx = 8.289 Mg m−3 |
| Orthorhombic, P21nb | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: p -2bc 21 | Cell parameters from 12 reflections |
| a = 10.516 (2) Å | θ = 23–29° |
| b = 14.560 (3) Å | µ = 42.09 mm−1 |
| c = 7.333 (2) Å | T = 295 K |
| V = 1122.8 (4) Å3 | Prism, black |
| Z = 8 | 0.06 × 0.04 × 0.03 mm |
| Bruker SMART APEX II diffractometer | 7765 reflections with F > 3σ(F) |
| Detector resolution: 67 pixels mm-1 | Rint = 0.098 |
| ω and φ scans | θmax = 61.7°, θmin = 2.8° |
| Absorption correction: numerical (SMART APEXII XPREP; Bruker, 2006) | h = −25→25 |
| Tmin = 0.272, Tmax = 0.530 | k = −35→35 |
| 158509 measured reflections | l = −16→16 |
| 17319 independent reflections |
| Refinement on F | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo)] |
| Least-squares matrix: full | (Δ/σ)max < 0.001 |
| R[F2 > 2σ(F2)] = 0.025 | Δρmax = 3.91 e Å−3 |
| wR(F2) = 0.022 | Δρmin = −3.33 e Å−3 |
| S = 1.43 | Extinction correction: Becker & Coppens (1974). Acta Cryst. A30,148–153 |
| 3980 reflections | Extinction coefficient: 196 (5) |
| 138 parameters | Absolute structure: Flack (1983), 8131 Friedel pairs |
| 0 restraints | Flack parameter: 0.51 (3) |
| 0 constraints |
| Dy3RuO7 | V = 1122.8 (4) Å3 |
| Mr = 700.57 | Z = 8 |
| Orthorhombic, P21nb | Mo Kα radiation |
| a = 10.516 (2) Å | µ = 42.09 mm−1 |
| b = 14.560 (3) Å | T = 295 K |
| c = 7.333 (2) Å | 0.06 × 0.04 × 0.03 mm |
| Bruker SMART APEX II diffractometer | 17319 independent reflections |
| Absorption correction: numerical (SMART APEXII XPREP; Bruker, 2006) | 7765 reflections with F > 3σ(F) |
| Tmin = 0.272, Tmax = 0.530 | Rint = 0.098 |
| 158509 measured reflections | θmax = 61.7° |
| R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
| wR(F2) = 0.022 | Δρmax = 3.91 e Å−3 |
| S = 1.43 | Δρmin = −3.33 e Å−3 |
| 3980 reflections | Absolute structure: Flack (1983), 8131 Friedel pairs |
| 138 parameters | Flack parameter: 0.51 (3) |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Dy1 | −0.2206 (3) | 0.02169 (10) | −0.23588 (8) | 0.0052 (2) | |
| Dy2 | −0.2325 (3) | 0.22160 (12) | 0.24493 (7) | 0.0049 (4) | |
| Dy3 | −0.2815 (3) | 0.27324 (10) | −0.25774 (7) | 0.0048 (2) | |
| Dy4 | −0.2691 (3) | −0.02693 (12) | 0.25048 (5) | 0.0047 (4) | |
| Dy5a | 0.0061 (3) | 0.38826 (8) | 0.00271 (13) | 0.00570 (17) | .970 (7) |
| Dy5b | −0.010 (3) | 0.363 (3) | −0.002 (3) | 0.00570 (17) | .030 (7) |
| Dy6a | −0.0095 (3) | 0.36200 (8) | −0.49762 (11) | 0.00519 (17) | .978 (8) |
| Dy6b | −0.010 (4) | 0.387 (4) | −0.507 (4) | 0.00519 (17) | .022 (8) |
| Ru1 | 0.00000 | 0.1261 (2) | −0.0007 (4) | 0.00357 (16) | |
| Ru2 | −0.00179 (8) | 0.1246 (2) | −0.5036 (3) | 0.00306 (17) | |
| O1 | 0.0125 (9) | 0.0843 (6) | −0.2517 (7) | 0.0047 (13)* | |
| O2 | −0.0051 (11) | 0.1712 (7) | 0.2485 (7) | 0.0067 (14)* | |
| O3 | 0.1231 (8) | 0.2211 (7) | −0.4660 (9) | 0.0052 (11)* | |
| O4 | −0.3634 (11) | 0.1056 (7) | 0.2322 (12) | 0.0061 (12)* | |
| O5 | 0.1269 (8) | 0.0327 (7) | −0.5443 (10) | 0.0065 (10)* | |
| O6 | −0.1342 (11) | 0.3808 (8) | −0.2338 (12) | 0.0070 (14)* | |
| O7 | −0.1339 (8) | 0.2192 (7) | −0.4651 (10) | 0.0067 (11)* | |
| O8 | −0.1343 (10) | −0.1446 (7) | 0.2649 (11) | 0.0054 (12)* | |
| O9 | −0.1299 (9) | 0.0309 (7) | −0.5342 (10) | 0.0072 (12)* | |
| O10 | −0.3736 (11) | 0.1313 (8) | −0.2432 (10) | 0.0067 (14)* | |
| O11 | −0.1009 (9) | 0.0138 (6) | 0.0410 (10) | 0.0073 (11)* | |
| O12 | 0.1044 (8) | 0.2378 (6) | −0.0407 (10) | 0.0071 (11)* | |
| O13 | 0.1604 (8) | 0.0652 (5) | 0.0454 (10) | 0.0094 (10)* | |
| O14 | −0.1516 (9) | 0.1925 (6) | −0.0490 (11) | 0.0112 (12)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Dy1 | 0.0045 (3) | 0.0057 (3) | 0.00540 (14) | 0.0006 (2) | 0.00020 (19) | 0.00136 (17) |
| Dy2 | 0.0045 (5) | 0.0044 (3) | 0.0058 (3) | −0.0009 (3) | −0.00010 (13) | −0.00035 (12) |
| Dy3 | 0.0044 (3) | 0.0048 (3) | 0.00531 (18) | −0.0007 (2) | 0.00082 (16) | −0.00004 (13) |
| Dy4 | 0.0050 (5) | 0.0044 (4) | 0.0046 (3) | 0.0006 (3) | −0.00046 (9) | −0.00034 (11) |
| Dy5a | 0.00470 (19) | 0.0084 (2) | 0.00403 (11) | 0.00042 (17) | −0.00019 (16) | 0.0007 (2) |
| Dy5b | 0.00470 (19) | 0.0084 (2) | 0.00403 (11) | 0.00042 (17) | −0.00019 (16) | 0.0007 (2) |
| Dy6a | 0.00399 (19) | 0.0073 (2) | 0.00427 (11) | 0.00025 (17) | −0.00004 (17) | −0.0002 (2) |
| Dy6b | 0.00399 (19) | 0.0073 (2) | 0.00427 (11) | 0.00025 (17) | −0.00004 (17) | −0.0002 (2) |
| Ru1 | 0.0029 (2) | 0.00453 (16) | 0.00325 (12) | −0.0001 (2) | 0.0000 (2) | −0.00049 (16) |
| Ru2 | 0.0033 (2) | 0.00344 (12) | 0.00242 (17) | −0.0003 (2) | −0.0003 (2) | −0.00005 (16) |
| Dy1i—O6ii | 2.25 (1) | Dy5b—O8iii | 2.18 (3) |
| Dy1i—O13iii | 2.263 (8) | Dy5b—O12 | 2.20 (4) |
| Dy1i—O10i | 2.266 (12) | Dy5b—O10i | 2.38 (3) |
| Dy1i—O9i | 2.391 (8) | Dy5b—O4viii | 2.53 (3) |
| Dy1i—O11i | 2.392 (8) | Dy5b—O9iv | 2.77 (4) |
| Dy1i—O5iv | 2.408 (8) | Dy5b—O5iv | 2.88 (4) |
| Dy1i—O1i | 2.617 (10) | Dy5b—O14 | 2.91 (4) |
| Dy2v—O4v | 2.181 (11) | Dy6aix—Dy6bix | .37 (5) |
| Dy2v—O8i | 2.206 (10) | Dy6aix—O10i | 2.301 (9) |
| Dy2v—O3iii | 2.323 (8) | Dy6aix—O4i | 2.329 (10) |
| Dy2v—O14v | 2.356 (8) | Dy6aix—O6ix | 2.353 (10) |
| Dy2v—O7ii | 2.366 (8) | Dy6aix—O8iii | 2.361 (9) |
| Dy2v—O12iii | 2.401 (8) | Dy6aix—O11iii | 2.431 (9) |
| Dy2v—O2v | 2.501 (12) | Dy6aix—O7ix | 2.468 (10) |
| Dy3ii—O6ii | 2.210 (12) | Dy6aix—O3ix | 2.492 (10) |
| Dy3ii—O10ii | 2.285 (12) | Dy6bix—O11iii | 2.10 (5) |
| Dy3ii—O7ii | 2.311 (9) | Dy6bix—O10i | 2.26 (4) |
| Dy3ii—O3iv | 2.365 (7) | Dy6bix—O8iii | 2.34 (4) |
| Dy3ii—O14ii | 2.365 (9) | Dy6bix—O4i | 2.34 (4) |
| Dy3ii—O12iii | 2.403 (8) | Dy6bix—O6ix | 2.39 (4) |
| Dy3ii—O2iii | 2.486 (11) | Dy6bix—O7ix | 2.78 (5) |
| Dy4vi—O4vi | 2.174 (11) | Dy6bix—O3ix | 2.81 (5) |
| Dy4vi—O8vi | 2.226 (11) | Ru1—O14 | 1.897 (9) |
| Dy4vi—O9vii | 2.312 (9) | Ru1—O13 | 1.935 (8) |
| Dy4vi—O13i | 2.360 (7) | Ru1—O1 | 1.943 (6) |
| Dy4vi—O11vi | 2.417 (9) | Ru1—O2 | 1.943 (7) |
| Dy4vi—O5i | 2.418 (8) | Ru1—O11 | 1.973 (9) |
| Dy4vi—O1i | 2.444 (10) | Ru1—O12 | 1.984 (9) |
| Dy5a—Dy5b | .41 (4) | Ru1—Ru2ix | 3.646 (4) |
| Dy5a—O10i | 2.270 (9) | Ru1—Ru2 | 3.688 (4) |
| Dy5a—O6 | 2.279 (10) | Ru2ix—O5ix | 1.926 (9) |
| Dy5a—O8iii | 2.305 (9) | Ru2ix—O9ix | 1.930 (10) |
| Dy5a—O4viii | 2.414 (10) | Ru2ix—O2 | 1.940 (7) |
| Dy5a—O12 | 2.442 (9) | Ru2ix—O3ix | 1.943 (10) |
| Dy5a—O5iv | 2.476 (10) | Ru2ix—O1ix | 1.944 (6) |
| Dy5a—O9iv | 2.532 (10) | Ru2ix—O7ix | 1.976 (9) |
| Dy5b—O6 | 2.16 (3) | ||
| ?···? | ? | ||
| Ru1i—O1i—Ru2i | 143.1 (5) | Ru2ii—O2v—Ru1v | 139.7 (6) |
| ?—?—?—? | ? |
| Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) x+1/2, −y+1, −z; (iii) x, y+1/2, −z+1/2; (iv) x, y+1/2, −z−1/2; (v) x+1/2, −y+1, −z+1; (vi) x+1, y+1/2, −z+1/2; (vii) x+1, y+1/2, −z−1/2; (viii) x+1/2, −y+1/2, z−1/2; (ix) x, y, z+1. |
This study was supported by Grants-in-Aid for Scientific Research No. 18206071 from the Ministry of Education, Culture, Sports, Science and Technology, Japan.
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The room temperature structure of the title compound, (I), has been confirmed as the P21nb modification of Ln3MO7 family composed of trivalent lanthanide (Ln) and pentavalent transition metal (M=Ru, Os) oxides (Figs. 1 and 2). The family is so far known to have two orthorhombic modifications Cmcm and P21nb modifications related by the phase transition (Bontchev et al., 2000, Harada & Hinatsu, 2003, Gemmill et al., 2004, 2005).
A positional disorder at two Ln atom sites, i.e., Ln5 and Ln6, was first suspected for Gd3RuO7 and confirmed in Tb3RuO7 (Ishizawa et al., 2006, 2007). A similar but faint disorder has also been detected in Dy3RuO7 in the present study using single-crystal diffraction data collected with relatively high resolution level (d>0.42 Å). The split atom sites at Dy5b and Dy6b are populated 3.0 (7) and 2.2 (8) % by the Dy atoms. The coordination numbers of Dy1, 2, 3, 4, 5a and 6a are 7 in the range 2.17–2.62 Å, whereas those of Dy5b and Dy6b are 5 in the range 2.10–2.53 Å. The mean Ru···Ru interatomic distance and Ru—O—Ru angle along the [RuO5] ∞ octahedral chain are 3.667 (4) Å and 141.4 (5)°.