The crystal structure of Tm5Re2O12, pentathulium dirhenium dodecaoxide, was determined by synchrotron diffraction on a reticular merohedral twin, revealing space group C2/m with a = 12.3717 (7), b = 5.6744 (3), c = 7.4805 (4) Å, β = 107.816 (2)° and Z = 2. Distorted ReO6 octahedra form chains with alternating rhenium–rhenium distances of 2.455 (1) and 3.219 (1) Å. Early reports on Ln2ReO5 compounds are critically reviewed in the light of our results for Tm5Re2O12.
Supporting information
| Crystallographic Information File (CIF) Contains datablocks tm5, global |
| Structure factor file (CIF format) Contains datablock tm5 |
Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
Pentathulium dirhenium dodecaoxide
top
Crystal data top
O12Re2Tm5 | F(000) = 1182 |
Mr = 1409.05 | Dx = 9.360 Mg m−3 |
Monoclinic, C2/m | Synchrotron radiation, λ = 0.42750 Å |
a = 12.3717 (7) Å | Cell parameters from 460 reflections |
b = 5.6744 (3) Å | θ = 3.4–38.9° |
c = 7.4805 (4) Å | µ = 16.59 mm−1 |
β = 107.816 (2)° | T = 293 K |
V = 499.96 (5) Å3 | Needle, black |
Z = 2 | |
Data collection top
CCD diffractometer | 4961 independent reflections |
Radiation source: synchrotron | 4165 reflections with I > 2σ(I) |
Silicon monochromator | Rint = 0.053 |
ω–scans | θmax = 38.9°, θmin = 3.4° |
Absorption correction: empirical (using intensity measurements) | h = −36→36 |
Tmin = 0.19, Tmax = 0.85 | k = −11→16 |
8671 measured reflections | l = −21→20 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.068 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.152 | w = 1/[σ2(Fo2) + (0.0103P)2 + 1.6684P] where P = (Fo2 + 2Fc2)/3 |
S = 1.25 | (Δ/σ)max < 0.001 |
4961 reflections | Δρmax = 14.23 e Å−3 |
52 parameters | Δρmin = −12.32 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 | |
Re1 | 0.0000 | 0.28367 (4) | 0.0000 | 0.00224 (3) | |
Tm1 | 0.5000 | 0.0000 | 0.5000 | 0.00381 (5) | |
Tm2 | 0.31373 (2) | 0.5000 | 0.17505 (5) | 0.00319 (4) | |
Tm3 | 0.19638 (2) | 0.0000 | 0.35973 (5) | 0.00313 (4) | |
O1 | 0.0012 (4) | 0.0000 | 0.1787 (8) | 0.0057 (5) | |
O2 | 0.4989 (5) | 0.0000 | 0.2053 (9) | 0.0076 (6) | |
O3 | 0.3459 (3) | 0.2520 (8) | 0.4265 (7) | 0.0060 (4) | |
O4 | 0.1655 (3) | 0.2461 (8) | 0.0833 (8) | 0.0063 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Re1 | 0.00213 (4) | 0.00229 (6) | 0.00191 (6) | 0.000 | 0.00005 (4) | 0.000 |
Tm1 | 0.00333 (8) | 0.00513 (11) | 0.00249 (10) | 0.000 | 0.00018 (7) | 0.000 |
Tm2 | 0.00319 (6) | 0.00324 (7) | 0.00300 (8) | 0.000 | 0.00074 (6) | 0.000 |
Tm3 | 0.00343 (6) | 0.00282 (7) | 0.00256 (8) | 0.000 | 0.00006 (6) | 0.000 |
O1 | 0.0056 (9) | 0.0044 (11) | 0.0070 (14) | 0.000 | 0.0022 (9) | 0.000 |
O2 | 0.0103 (13) | 0.0069 (14) | 0.0041 (13) | 0.000 | 0.0000 (11) | 0.000 |
O3 | 0.0082 (9) | 0.0040 (8) | 0.0055 (10) | −0.0007 (7) | 0.0017 (8) | 0.0003 (8) |
O4 | 0.0059 (7) | 0.0049 (9) | 0.0077 (12) | −0.0003 (6) | 0.0015 (8) | −0.0006 (8) |
Geometric parameters (Å, º) top
Re1—O4 | 1.961 (4) | Tm2—O4iii | 2.461 (5) |
Re1—O4i | 1.961 (4) | Tm2—O4xii | 2.461 (5) |
Re1—O2ii | 1.969 (5) | Tm2—Re1xi | 3.3857 (3) |
Re1—O2iii | 1.969 (5) | Tm2—Re1iii | 3.3857 (3) |
Re1—O1iv | 2.089 (4) | Tm2—Tm3xiii | 3.5204 (6) |
Re1—O1 | 2.089 (4) | Tm2—Tm3xiv | 3.646 (3) |
Re1—Re1v | 2.4551 (5) | Tm2—Tm3 | 3.646 (3) |
Re1—Re1iv | 3.2193 (5) | Tm3—O3 | 2.269 (4) |
Re1—Tm2vi | 3.3857 (3) | Tm3—O3viii | 2.269 (4) |
Re1—Tm2iii | 3.3857 (3) | Tm3—O3xiii | 2.307 (5) |
Re1—Tm3iv | 3.4255 (3) | Tm3—O3xv | 2.307 (5) |
Re1—Tm3 | 3.4256 (3) | Tm3—O1 | 2.380 (5) |
Tm1—O2 | 2.201 (6) | Tm3—O4viii | 2.426 (5) |
Tm1—O2vii | 2.201 (6) | Tm3—O4 | 2.426 (5) |
Tm1—O3 | 2.311 (4) | Tm3—Re1iv | 3.4256 (3) |
Tm1—O3viii | 2.311 (4) | Tm3—Tm2xiii | 3.5204 (6) |
Tm1—O3ix | 2.311 (4) | Tm3—Tm3xiii | 3.5370 (4) |
Tm1—O3vii | 2.311 (4) | Tm3—Tm3xvi | 3.5370 (4) |
Tm1—Tm3 | 3.5775 (3) | O1—Re1iv | 2.089 (4) |
Tm1—Tm3vii | 3.5775 (3) | O1—Tm2vi | 2.312 (4) |
Tm2—O4x | 2.267 (4) | O2—Re1xvii | 1.969 (5) |
Tm2—O4 | 2.267 (4) | O2—Re1iii | 1.969 (5) |
Tm2—O3x | 2.285 (5) | O3—Tm3xiii | 2.307 (5) |
Tm2—O3 | 2.285 (5) | O4—Tm2iii | 2.461 (5) |
Tm2—O1xi | 2.312 (4) | | |
| | | |
O4—Re1—O4i | 167.5 (3) | O3x—Tm2—Re1iii | 130.07 (10) |
O4—Re1—O2ii | 94.3 (2) | O3—Tm2—Re1iii | 93.32 (11) |
O4i—Re1—O2ii | 93.5 (2) | O1xi—Tm2—Re1iii | 37.36 (9) |
O4—Re1—O2iii | 93.5 (2) | O4iii—Tm2—Re1iii | 34.85 (9) |
O4i—Re1—O2iii | 94.3 (2) | O4xii—Tm2—Re1iii | 73.67 (10) |
O2ii—Re1—O2iii | 102.9 (2) | Re1xi—Tm2—Re1iii | 56.774 (9) |
O4—Re1—O1iv | 85.53 (19) | O4x—Tm2—Tm3xiii | 91.66 (15) |
O4i—Re1—O1iv | 84.84 (19) | O4—Tm2—Tm3xiii | 91.66 (15) |
O2ii—Re1—O1iv | 168.14 (17) | O3x—Tm2—Tm3xiii | 40.18 (12) |
O2iii—Re1—O1iv | 88.96 (17) | O3—Tm2—Tm3xiii | 40.18 (12) |
O4—Re1—O1 | 84.84 (19) | O1xi—Tm2—Tm3xiii | 109.12 (15) |
O4i—Re1—O1 | 85.53 (19) | O4iii—Tm2—Tm3xiii | 145.12 (12) |
O2ii—Re1—O1 | 88.96 (17) | O4xii—Tm2—Tm3xiii | 145.12 (12) |
O2iii—Re1—O1 | 168.14 (17) | Re1xi—Tm2—Tm3xiii | 128.067 (9) |
O1iv—Re1—O1 | 79.2 (2) | Re1iii—Tm2—Tm3xiii | 128.067 (9) |
O4—Re1—Re1v | 96.25 (13) | O4x—Tm2—Tm3xiv | 40.63 (14) |
O4i—Re1—Re1v | 96.25 (13) | O4—Tm2—Tm3xiv | 103.31 (12) |
O2ii—Re1—Re1v | 51.44 (12) | O3x—Tm2—Tm3xiv | 36.66 (11) |
O2iii—Re1—Re1v | 51.44 (12) | O3—Tm2—Tm3xiv | 99.01 (12) |
O1iv—Re1—Re1v | 140.40 (12) | O1xi—Tm2—Tm3xiv | 120.67 (6) |
O1—Re1—Re1v | 140.40 (12) | O4iii—Tm2—Tm3xiv | 152.69 (11) |
O4—Re1—Re1iv | 83.75 (13) | O4xii—Tm2—Tm3xiv | 90.32 (11) |
O4i—Re1—Re1iv | 83.75 (13) | Re1xi—Tm2—Tm3xiv | 99.999 (7) |
O2ii—Re1—Re1iv | 128.56 (12) | Re1iii—Tm2—Tm3xiv | 156.003 (9) |
O2iii—Re1—Re1iv | 128.56 (12) | Tm3xiii—Tm2—Tm3xiv | 59.118 (7) |
O1iv—Re1—Re1iv | 39.60 (12) | O4x—Tm2—Tm3 | 103.31 (12) |
O1—Re1—Re1iv | 39.60 (12) | O4—Tm2—Tm3 | 40.63 (14) |
Re1v—Re1—Re1iv | 180.0 | O3x—Tm2—Tm3 | 99.01 (12) |
O4—Re1—Tm2vi | 126.39 (16) | O3—Tm2—Tm3 | 36.66 (11) |
O4i—Re1—Tm2vi | 45.83 (16) | O1xi—Tm2—Tm3 | 120.67 (6) |
O2ii—Re1—Tm2vi | 80.03 (15) | O4iii—Tm2—Tm3 | 90.32 (11) |
O2iii—Re1—Tm2vi | 139.98 (17) | O4xii—Tm2—Tm3 | 152.69 (11) |
O1iv—Re1—Tm2vi | 90.49 (12) | Re1xi—Tm2—Tm3 | 156.003 (9) |
O1—Re1—Tm2vi | 42.18 (12) | Re1iii—Tm2—Tm3 | 99.999 (7) |
Re1v—Re1—Tm2vi | 118.387 (5) | Tm3xiii—Tm2—Tm3 | 59.118 (7) |
Re1iv—Re1—Tm2vi | 61.613 (5) | Tm3xiv—Tm2—Tm3 | 102.187 (13) |
O4—Re1—Tm2iii | 45.83 (16) | O3—Tm3—O3viii | 78.1 (2) |
O4i—Re1—Tm2iii | 126.39 (16) | O3—Tm3—O3xiii | 78.77 (17) |
O2ii—Re1—Tm2iii | 139.98 (17) | O3viii—Tm3—O3xiii | 125.04 (8) |
O2iii—Re1—Tm2iii | 80.03 (15) | O3—Tm3—O3xv | 125.04 (8) |
O1iv—Re1—Tm2iii | 42.18 (12) | O3viii—Tm3—O3xv | 78.77 (17) |
O1—Re1—Tm2iii | 90.48 (12) | O3xiii—Tm3—O3xv | 75.2 (2) |
Re1v—Re1—Tm2iii | 118.387 (5) | O3—Tm3—O1 | 137.90 (12) |
Re1iv—Re1—Tm2iii | 61.613 (5) | O3viii—Tm3—O1 | 137.90 (12) |
Tm2vi—Re1—Tm2iii | 123.225 (9) | O3xiii—Tm3—O1 | 89.37 (15) |
O4—Re1—Tm3iv | 128.26 (15) | O3xv—Tm3—O1 | 89.37 (15) |
O4i—Re1—Tm3iv | 43.82 (16) | O3—Tm3—O4viii | 117.10 (13) |
O2ii—Re1—Tm3iv | 137.15 (17) | O3viii—Tm3—O4viii | 74.35 (17) |
O2iii—Re1—Tm3iv | 81.53 (13) | O3xiii—Tm3—O4viii | 158.69 (15) |
O1iv—Re1—Tm3iv | 43.18 (12) | O3xv—Tm3—O4viii | 103.27 (16) |
O1—Re1—Tm3iv | 90.29 (13) | O1—Tm3—O4viii | 69.33 (14) |
Re1v—Re1—Tm3iv | 118.028 (5) | O3—Tm3—O4 | 74.35 (17) |
Re1iv—Re1—Tm3iv | 61.972 (5) | O3viii—Tm3—O4 | 117.10 (13) |
Tm2vi—Re1—Tm3iv | 71.175 (9) | O3xiii—Tm3—O4 | 103.27 (16) |
Tm2iii—Re1—Tm3iv | 82.869 (9) | O3xv—Tm3—O4 | 158.69 (15) |
O4—Re1—Tm3 | 43.82 (16) | O1—Tm3—O4 | 69.33 (14) |
O4i—Re1—Tm3 | 128.26 (15) | O4viii—Tm3—O4 | 70.3 (2) |
O2ii—Re1—Tm3 | 81.53 (13) | O3—Tm3—Re1iv | 143.46 (13) |
O2iii—Re1—Tm3 | 137.15 (17) | O3viii—Tm3—Re1iv | 102.19 (12) |
O1iv—Re1—Tm3 | 90.29 (13) | O3xiii—Tm3—Re1iv | 125.06 (10) |
O1—Re1—Tm3 | 43.18 (12) | O3xv—Tm3—Re1iv | 90.07 (11) |
Re1v—Re1—Tm3 | 118.028 (5) | O1—Tm3—Re1iv | 36.93 (9) |
Re1iv—Re1—Tm3 | 61.972 (5) | O4viii—Tm3—Re1iv | 34.02 (9) |
Tm2vi—Re1—Tm3 | 82.869 (9) | O4—Tm3—Re1iv | 73.26 (11) |
Tm2iii—Re1—Tm3 | 71.175 (9) | O3—Tm3—Re1 | 102.19 (12) |
Tm3iv—Re1—Tm3 | 123.944 (9) | O3viii—Tm3—Re1 | 143.46 (13) |
O2—Tm1—O2vii | 179.999 (1) | O3xiii—Tm3—Re1 | 90.07 (11) |
O2—Tm1—O3 | 90.57 (18) | O3xv—Tm3—Re1 | 125.06 (10) |
O2vii—Tm1—O3 | 89.43 (18) | O1—Tm3—Re1 | 36.93 (9) |
O2—Tm1—O3viii | 90.57 (18) | O4viii—Tm3—Re1 | 73.26 (11) |
O2vii—Tm1—O3viii | 89.43 (18) | O4—Tm3—Re1 | 34.02 (9) |
O3—Tm1—O3viii | 76.4 (2) | Re1iv—Tm3—Re1 | 56.055 (9) |
O2—Tm1—O3ix | 89.43 (18) | O3—Tm3—Tm2xiii | 93.18 (13) |
O2vii—Tm1—O3ix | 90.57 (18) | O3viii—Tm3—Tm2xiii | 93.18 (13) |
O3—Tm1—O3ix | 103.6 (2) | O3xiii—Tm3—Tm2xiii | 39.71 (12) |
O3viii—Tm1—O3ix | 180.00 (14) | O3xv—Tm3—Tm2xiii | 39.71 (12) |
O2—Tm1—O3vii | 89.43 (18) | O1—Tm3—Tm2xiii | 103.06 (14) |
O2vii—Tm1—O3vii | 90.57 (18) | O4viii—Tm3—Tm2xiii | 142.98 (11) |
O3—Tm1—O3vii | 180.0 (2) | O4—Tm3—Tm2xiii | 142.98 (11) |
O3viii—Tm1—O3vii | 103.6 (2) | Re1iv—Tm3—Tm2xiii | 123.051 (8) |
O3ix—Tm1—O3vii | 76.4 (2) | Re1—Tm3—Tm2xiii | 123.051 (8) |
O2—Tm1—Tm3 | 91.27 (15) | O3—Tm3—Tm3xiii | 39.78 (12) |
O2vii—Tm1—Tm3 | 88.73 (15) | O3viii—Tm3—Tm3xiii | 104.03 (11) |
O3—Tm1—Tm3 | 38.22 (11) | O3xiii—Tm3—Tm3xiii | 39.00 (10) |
O3viii—Tm1—Tm3 | 38.22 (11) | O3xv—Tm3—Tm3xiii | 101.62 (12) |
O3ix—Tm1—Tm3 | 141.78 (11) | O1—Tm3—Tm3xiii | 117.96 (6) |
O3vii—Tm1—Tm3 | 141.78 (11) | O4viii—Tm3—Tm3xiii | 154.15 (11) |
O2—Tm1—Tm3vii | 88.73 (15) | O4—Tm3—Tm3xiii | 88.67 (11) |
O2vii—Tm1—Tm3vii | 91.27 (15) | Re1iv—Tm3—Tm3xiii | 152.892 (11) |
O3—Tm1—Tm3vii | 141.78 (11) | Re1—Tm3—Tm3xiii | 97.833 (8) |
O3viii—Tm1—Tm3vii | 141.78 (11) | Tm2xiii—Tm3—Tm3xiii | 62.211 (11) |
O3ix—Tm1—Tm3vii | 38.22 (11) | O3—Tm3—Tm3xvi | 104.03 (11) |
O3vii—Tm1—Tm3vii | 38.22 (11) | O3viii—Tm3—Tm3xvi | 39.78 (12) |
Tm3—Tm1—Tm3vii | 180.0 | O3xiii—Tm3—Tm3xvi | 101.62 (12) |
O4x—Tm2—O4 | 78.9 (2) | O3xv—Tm3—Tm3xvi | 39.00 (10) |
O4x—Tm2—O3x | 77.20 (18) | O1—Tm3—Tm3xvi | 117.96 (6) |
O4—Tm2—O3x | 124.16 (14) | O4viii—Tm3—Tm3xvi | 88.67 (11) |
O4x—Tm2—O3 | 124.16 (14) | O4—Tm3—Tm3xvi | 154.15 (11) |
O4—Tm2—O3 | 77.20 (18) | Re1iv—Tm3—Tm3xvi | 97.834 (8) |
O3x—Tm2—O3 | 76.1 (2) | Re1—Tm3—Tm3xvi | 152.892 (11) |
O4x—Tm2—O1xi | 136.01 (13) | Tm2xiii—Tm3—Tm3xvi | 62.211 (11) |
O4—Tm2—O1xi | 136.01 (13) | Tm3xiii—Tm3—Tm3xvi | 106.672 (17) |
O3x—Tm2—O1xi | 93.96 (15) | Re1iv—O1—Re1 | 100.8 (2) |
O3—Tm2—O1xi | 93.96 (15) | Re1iv—O1—Tm2vi | 100.46 (15) |
O4x—Tm2—O4iii | 113.09 (9) | Re1—O1—Tm2vi | 100.46 (15) |
O4—Tm2—O4iii | 70.80 (19) | Re1iv—O1—Tm3 | 99.89 (14) |
O3x—Tm2—O4iii | 164.26 (15) | Re1—O1—Tm3 | 99.89 (14) |
O3—Tm2—O4iii | 105.28 (16) | Tm2vi—O1—Tm3 | 147.8 (3) |
O1xi—Tm2—O4iii | 70.33 (15) | Re1xvii—O2—Re1iii | 77.1 (2) |
O4x—Tm2—O4xii | 70.80 (19) | Re1xvii—O2—Tm1 | 141.43 (12) |
O4—Tm2—O4xii | 113.09 (9) | Re1iii—O2—Tm1 | 141.43 (12) |
O3x—Tm2—O4xii | 105.28 (16) | Tm3—O3—Tm2 | 106.39 (18) |
O3—Tm2—O4xii | 164.26 (15) | Tm3—O3—Tm3xiii | 101.23 (17) |
O1xi—Tm2—O4xii | 70.33 (15) | Tm2—O3—Tm3xiii | 100.12 (16) |
O4iii—Tm2—O4xii | 69.1 (2) | Tm3—O3—Tm1 | 102.71 (17) |
O4x—Tm2—Re1xi | 99.45 (12) | Tm2—O3—Tm1 | 120.0 (2) |
O4—Tm2—Re1xi | 140.21 (15) | Tm3xiii—O3—Tm1 | 123.9 (2) |
O3x—Tm2—Re1xi | 93.32 (11) | Re1—O4—Tm2 | 134.1 (2) |
O3—Tm2—Re1xi | 130.07 (10) | Re1—O4—Tm3 | 102.2 (2) |
O1xi—Tm2—Re1xi | 37.36 (9) | Tm2—O4—Tm3 | 101.88 (19) |
O4iii—Tm2—Re1xi | 73.67 (10) | Re1—O4—Tm2iii | 99.3 (2) |
O4xii—Tm2—Re1xi | 34.85 (9) | Tm2—O4—Tm2iii | 109.20 (19) |
O4x—Tm2—Re1iii | 140.21 (15) | Tm3—O4—Tm2iii | 108.40 (17) |
O4—Tm2—Re1iii | 99.45 (12) | | |
Symmetry codes: (i) −x, y, −z; (ii) x−1/2, y+1/2, z; (iii) −x+1/2, −y+1/2, −z; (iv) −x, −y, −z; (v) −x, −y+1, −z; (vi) x−1/2, y−1/2, z; (vii) −x+1, −y, −z+1; (viii) x, −y, z; (ix) −x+1, y, −z+1; (x) x, −y+1, z; (xi) x+1/2, y+1/2, z; (xii) −x+1/2, y+1/2, −z; (xiii) −x+1/2, −y+1/2, −z+1; (xiv) x, y+1, z; (xv) −x+1/2, y−1/2, −z+1; (xvi) −x+1/2, −y−1/2, −z+1; (xvii) x+1/2, y−1/2, z. |