Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801006869/bt6037sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801006869/bt6037Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (Nd-O) = 0.007 Å
- R factor = 0.024
- wR factor = 0.055
- Data-to-parameter ratio = 11.0
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry PLATON alerts of the form PLAT_7?? have been detected for an inorganic structure. These tests are under development for inorganics and comments are welcomed. It is not necessary to supply a data validation response form for these alerts at this time.
Alert Level A:
PLAT_735 Alert A D-H Calc 0.89(9), Rep 0.900(10) .... 9.00 s.u-Ratio O3W -H6W 1.555 1.555
Alert Level B:
SHFSU_01 Alert B The absolute value of parameter shift to su ratio > 0.10 Absolute value of the parameter shift to su ratio given 0.188 Additional refinement cycles may be required.
Alert Level C:
HYDTR_01 Alert C The hydrogen treatment should only be one of the following keywords * refall * refxyz * refU * noref * undef * constr * none * mixed Hydrogen treatment given as restr REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.00 From the CIF: _reflns_number_total 2144 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 2275 Completeness (_total/calc) 94.24% Alert C: < 95% complete PLAT_735 Alert C D-H Calc 0.89(3), Rep 0.900(10) .... 3.00 s.u-Ratio O1W -H1W 1.555 1.555 PLAT_735 Alert C D-H Calc 0.90(4), Rep 0.900(10) .... 4.00 s.u-Ratio O1W -H2W 1.555 1.555 PLAT_735 Alert C D-H Calc 0.90(4), Rep 0.900(10) .... 4.00 s.u-Ratio O3W -H5W 1.555 1.555 PLAT_736 Alert C H...A Calc 2.00(8), Rep 1.99(3) .... 2.67 s.u-Ratio H6W -O23 1.555 1.455 General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: H6 Nd1 O15 Re3 Atom count from _chemical_formula_moiety:Nd300 O1200 Re300
1 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
6 Alert Level C = Please check
Neodymium(III) oxide readyly reacts with a perrhenic acid, which was in situ generated by the reaction of rhenium powder and H2O2 to a colourless solution. From this solution very thin platelets can be grown within a few days at roomtemperature.
The atomic coordinates of the Hatoms were refined using O—H and H—H distance restraints. One common Uiso value for all H atoms of the water molecules has been refined.
Data collection: IPDS Software (Stoe & Cie, 1998); cell refinement: IPDS Software; data reduction: IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97.
Nd(ReO4)3(H2O)3 | F(000) = 1644 |
Mr = 948.89 | Dx = 4.879 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.550 (2) Å | Cell parameters from 5000 quasi centered reflections automatically selected from the dataset reflections |
b = 13.660 (3) Å | θ = 2.8–25.0° |
c = 12.850 (3) Å | µ = 32.05 mm−1 |
β = 102.90 (3)° | T = 293 K |
V = 1291.8 (5) Å3 | Platelet, colourless |
Z = 4 | 0.50 × 0.10 × 0.01 mm |
Stoe IPDS diffractometer | 2144 independent reflections |
Radiation source: fine-focus sealed tube | 1915 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.068 |
Detector resolution: 50 pixels mm-1 | θmax = 25.0°, θmin = 2.8° |
ω scans | h = −8→8 |
Absorption correction: numerical (X-RED; Stoe & Cie, 1998) | k = −16→15 |
Tmin = 0.026, Tmax = 0.680 | l = −14→14 |
6587 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.024 | Restr |
wR(F2) = 0.055 | w = 1/[σ2(Fo2) + (0.024P)2 + 2.40P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.188 |
2144 reflections | Δρmax = 1.14 e Å−3 |
195 parameters | Δρmin = −1.30 e Å−3 |
27 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00057 (7) |
Nd(ReO4)3(H2O)3 | V = 1291.8 (5) Å3 |
Mr = 948.89 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.550 (2) Å | µ = 32.05 mm−1 |
b = 13.660 (3) Å | T = 293 K |
c = 12.850 (3) Å | 0.50 × 0.10 × 0.01 mm |
β = 102.90 (3)° |
Stoe IPDS diffractometer | 2144 independent reflections |
Absorption correction: numerical (X-RED; Stoe & Cie, 1998) | 1915 reflections with I > 2σ(I) |
Tmin = 0.026, Tmax = 0.680 | Rint = 0.068 |
6587 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 27 restraints |
wR(F2) = 0.055 | Restr |
S = 1.02 | (Δ/σ)max = 0.188 |
2144 reflections | Δρmax = 1.14 e Å−3 |
195 parameters | Δρmin = −1.30 e Å−3 |
Experimental. 160 exposures were taken in the 0–200 ϕ range with a crystal to detector distance of 60 mm and an exposure time of four minutes. Dynamic integration profiles (11–21 pixels) without allowing overlapping was used for integration. 94.24% completeness of data has been achieved in a theta range of 2.77 - 25.00 degrees. Atomic coordinates of all H atoms at the water ligands were taken from the difference Fourier syntheses. |
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. |
x | y | z | Uiso*/Ueq | ||
Re1 | −0.20077 (4) | 0.01103 (3) | 0.11756 (3) | 0.01494 (12) | |
O11 | −0.0126 (6) | 0.0851 (5) | 0.1384 (6) | 0.0300 (16) | |
O12 | −0.2359 (8) | −0.0391 (6) | −0.0079 (5) | 0.0344 (17) | |
O13 | −0.3903 (6) | 0.0726 (5) | 0.1345 (5) | 0.0314 (17) | |
O14 | −0.1616 (10) | −0.0821 (5) | 0.2080 (6) | 0.0445 (19) | |
Re2 | 0.68415 (4) | 0.33973 (3) | 0.30242 (3) | 0.01796 (12) | |
O21 | 0.6969 (8) | 0.4628 (4) | 0.2740 (5) | 0.0263 (14) | |
O22 | 0.4764 (7) | 0.2929 (6) | 0.2399 (6) | 0.0394 (18) | |
O23 | 0.8524 (8) | 0.2752 (6) | 0.2632 (7) | 0.051 (2) | |
O24 | 0.7069 (12) | 0.3271 (6) | 0.4376 (4) | 0.052 (2) | |
Re3 | 0.71932 (4) | 0.05861 (3) | 0.43981 (3) | 0.02164 (13) | |
O31 | 0.5472 (7) | 0.1067 (5) | 0.3419 (5) | 0.0312 (16) | |
O32 | 0.7422 (10) | 0.1266 (6) | 0.5541 (5) | 0.048 (2) | |
O33 | 0.6747 (11) | −0.0609 (4) | 0.4663 (7) | 0.050 (2) | |
O34 | 0.9187 (8) | 0.0641 (8) | 0.3974 (7) | 0.056 (3) | |
Nd1 | 0.31883 (5) | 0.13703 (3) | 0.17381 (3) | 0.01229 (13) | |
O1W | 0.1077 (7) | 0.2751 (5) | 0.1112 (6) | 0.0315 (16) | |
O2W | 0.4051 (10) | 0.2280 (6) | 0.0250 (7) | 0.0430 (19) | |
O3W | 0.1900 (7) | 0.1751 (6) | 0.3297 (5) | 0.0304 (16) | |
H1W | 0.146 (4) | 0.336 (2) | 0.104 (11) | 0.064 (18)* | |
H2W | −0.0136 (15) | 0.270 (3) | 0.096 (11) | 0.064 (18)* | |
H3W | 0.419 (16) | 0.200 (3) | −0.036 (4) | 0.064 (18)* | |
H4W | 0.399 (16) | 0.2936 (10) | 0.020 (5) | 0.064 (18)* | |
H5W | 0.242 (10) | 0.157 (9) | 0.3970 (19) | 0.064 (18)* | |
H6W | 0.087 (10) | 0.208 (9) | 0.327 (3) | 0.064 (18)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Re1 | 0.01077 (15) | 0.0156 (2) | 0.0183 (2) | −0.00051 (11) | 0.00296 (12) | −0.00121 (13) |
O11 | 0.018 (3) | 0.026 (4) | 0.045 (4) | −0.010 (3) | 0.006 (3) | −0.014 (3) |
O12 | 0.033 (3) | 0.040 (5) | 0.031 (4) | −0.003 (3) | 0.007 (3) | −0.012 (3) |
O13 | 0.015 (3) | 0.046 (5) | 0.035 (4) | 0.006 (3) | 0.008 (2) | −0.003 (3) |
O14 | 0.055 (4) | 0.037 (5) | 0.040 (5) | 0.000 (4) | 0.008 (3) | 0.015 (4) |
Re2 | 0.01746 (16) | 0.01156 (19) | 0.0238 (2) | −0.00256 (12) | 0.00248 (12) | −0.00179 (14) |
O21 | 0.037 (3) | 0.014 (3) | 0.028 (4) | −0.005 (3) | 0.007 (3) | −0.002 (3) |
O22 | 0.033 (3) | 0.023 (4) | 0.056 (5) | −0.014 (3) | −0.003 (3) | 0.004 (4) |
O23 | 0.032 (3) | 0.035 (5) | 0.089 (7) | 0.008 (3) | 0.019 (4) | 0.011 (5) |
O24 | 0.096 (6) | 0.026 (4) | 0.032 (5) | −0.024 (4) | 0.012 (4) | 0.003 (4) |
Re3 | 0.01832 (17) | 0.0220 (2) | 0.0220 (2) | 0.00094 (13) | −0.00086 (13) | 0.00478 (15) |
O31 | 0.025 (3) | 0.032 (4) | 0.029 (4) | 0.002 (3) | −0.010 (2) | 0.000 (3) |
O32 | 0.063 (5) | 0.040 (5) | 0.034 (5) | −0.003 (4) | −0.002 (3) | −0.002 (4) |
O33 | 0.057 (4) | 0.021 (4) | 0.066 (6) | −0.007 (4) | −0.001 (4) | 0.008 (4) |
O34 | 0.034 (4) | 0.075 (7) | 0.064 (6) | 0.013 (4) | 0.019 (4) | 0.023 (5) |
Nd1 | 0.00989 (18) | 0.0096 (2) | 0.0170 (3) | −0.00026 (14) | 0.00219 (15) | −0.00091 (17) |
O1W | 0.023 (3) | 0.017 (3) | 0.053 (5) | 0.003 (3) | 0.005 (3) | 0.006 (3) |
O2W | 0.042 (4) | 0.036 (5) | 0.057 (5) | 0.004 (4) | 0.022 (4) | 0.016 (4) |
O3W | 0.023 (3) | 0.045 (5) | 0.022 (4) | 0.003 (3) | 0.001 (2) | −0.007 (3) |
Re1—O11 | 1.715 (5) | Nd1—O11 | 2.543 (4) |
Re1—O12 | 1.717 (5) | Nd1—O22 | 2.494 (6) |
Re1—O13 | 1.715 (5) | Nd1—O31 | 2.479 (5) |
Re1—O14 | 1.704 (5) | Nd1—O1W | 2.484 (6) |
Re2—O21 | 1.728 (5) | Nd1—O2W | 2.486 (7) |
Re2—O22 | 1.718 (5) | Nd1—O3W | 2.470 (6) |
Re2—O23 | 1.712 (5) | Nd1—O12i | 2.476 (5) |
Re2—O24 | 1.716 (5) | Nd1—O21ii | 2.483 (5) |
Re3—O31 | 1.725 (5) | Nd1—O13iii | 2.520 (4) |
Re3—O32 | 1.713 (6) | O12—Nd1i | 2.476 (5) |
Re3—O33 | 1.716 (5) | O13—Nd1iv | 2.520 (4) |
Re3—O34 | 1.713 (5) | O21—Nd1v | 2.483 (5) |
O14—Re1—O13 | 107.6 (4) | O3W—Nd1—O1W | 76.3 (2) |
O14—Re1—O11 | 108.8 (4) | O31—Nd1—O1W | 132.9 (2) |
O13—Re1—O11 | 112.1 (3) | O12i—Nd1—O1W | 96.3 (2) |
O14—Re1—O12 | 108.0 (4) | O21ii—Nd1—O1W | 138.5 (2) |
O13—Re1—O12 | 110.9 (3) | O3W—Nd1—O2W | 137.5 (3) |
O11—Re1—O12 | 109.3 (3) | O31—Nd1—O2W | 120.2 (2) |
Re1—O11—Nd1 | 160.1 (4) | O12i—Nd1—O2W | 70.5 (3) |
Re1—O12—Nd1i | 168.7 (4) | O21ii—Nd1—O2W | 136.3 (2) |
Re1—O13—Nd1iv | 170.4 (4) | O1W—Nd1—O2W | 68.3 (2) |
O23—Re2—O24 | 109.5 (4) | O3W—Nd1—O22 | 77.8 (3) |
O23—Re2—O22 | 109.3 (4) | O31—Nd1—O22 | 70.1 (2) |
O24—Re2—O22 | 108.1 (4) | O12i—Nd1—O22 | 139.8 (2) |
O23—Re2—O21 | 111.0 (4) | O21ii—Nd1—O22 | 140.7 (2) |
O24—Re2—O21 | 108.3 (4) | O1W—Nd1—O22 | 71.7 (2) |
O22—Re2—O21 | 110.6 (3) | O2W—Nd1—O22 | 69.4 (3) |
Re2—O21—Nd1v | 150.1 (4) | O3W—Nd1—O13iii | 139.0 (2) |
Re2—O22—Nd1 | 142.5 (4) | O31—Nd1—O13iii | 69.4 (2) |
O32—Re3—O34 | 108.7 (5) | O12i—Nd1—O13iii | 72.7 (2) |
O32—Re3—O33 | 109.4 (4) | O21ii—Nd1—O13iii | 79.4 (2) |
O34—Re3—O33 | 109.3 (5) | O1W—Nd1—O13iii | 136.5 (2) |
O32—Re3—O31 | 109.5 (4) | O2W—Nd1—O13iii | 68.3 (2) |
O34—Re3—O31 | 108.9 (4) | O22—Nd1—O13iii | 89.7 (2) |
O33—Re3—O31 | 111.0 (4) | O3W—Nd1—O11 | 69.7 (2) |
Re3—O31—Nd1 | 164.5 (4) | O31—Nd1—O11 | 125.1 (2) |
O3W—Nd1—O31 | 69.6 (2) | O12i—Nd1—O11 | 69.2 (2) |
O3W—Nd1—O12i | 137.9 (2) | O21ii—Nd1—O11 | 71.1 (2) |
O31—Nd1—O12i | 130.8 (2) | O1W—Nd1—O11 | 67.6 (2) |
O3W—Nd1—O21ii | 86.0 (2) | O2W—Nd1—O11 | 114.7 (2) |
O31—Nd1—O21ii | 70.8 (2) | O22—Nd1—O11 | 132.5 (2) |
O12i—Nd1—O21ii | 72.4 (2) | O13iii—Nd1—O11 | 137.2 (2) |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) x+1, y, z; (iv) x−1, y, z; (v) −x+1, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O33v | 0.90 (1) | 2.27 (6) | 3.073 (11) | 148 (10) |
O1W—H2W···O32vi | 0.90 (1) | 2.29 (3) | 3.009 (10) | 137 (3) |
O2W—H4W···O33v | 0.90 (1) | 2.08 (3) | 2.954 (10) | 163 (6) |
O3W—H5W···O33vii | 0.90 (1) | 2.17 (5) | 3.024 (11) | 158 (12) |
O3W—H6W···O23iv | 0.90 (1) | 1.99 (3) | 2.851 (9) | 159 (4) |
Symmetry codes: (iv) x−1, y, z; (v) −x+1, y+1/2, −z+1/2; (vi) x−1, −y+1/2, z−1/2; (vii) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | Nd(ReO4)3(H2O)3 |
Mr | 948.89 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.550 (2), 13.660 (3), 12.850 (3) |
β (°) | 102.90 (3) |
V (Å3) | 1291.8 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 32.05 |
Crystal size (mm) | 0.50 × 0.10 × 0.01 |
Data collection | |
Diffractometer | Stoe IPDS diffractometer |
Absorption correction | Numerical (X-RED; Stoe & Cie, 1998) |
Tmin, Tmax | 0.026, 0.680 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6587, 2144, 1915 |
Rint | 0.068 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.055, 1.02 |
No. of reflections | 2144 |
No. of parameters | 195 |
No. of restraints | 27 |
H-atom treatment | Restr |
(Δ/σ)max | 0.188 |
Δρmax, Δρmin (e Å−3) | 1.14, −1.30 |
Computer programs: IPDS Software (Stoe & Cie, 1998), IPDS Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1998), SHELXL97.
Nd1—O11 | 2.543 (4) | Nd1—O3W | 2.470 (6) |
Nd1—O22 | 2.494 (6) | Nd1—O12i | 2.476 (5) |
Nd1—O31 | 2.479 (5) | Nd1—O21ii | 2.483 (5) |
Nd1—O1W | 2.484 (6) | Nd1—O13iii | 2.520 (4) |
Nd1—O2W | 2.486 (7) |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O33iv | 0.90 (1) | 2.27 (6) | 3.073 (11) | 148 (10) |
O1W—H2W···O32v | 0.90 (1) | 2.29 (3) | 3.009 (10) | 137 (3) |
O2W—H4W···O33iv | 0.90 (1) | 2.08 (3) | 2.954 (10) | 163 (6) |
O3W—H5W···O33vi | 0.90 (1) | 2.17 (5) | 3.024 (11) | 158 (12) |
O3W—H6W···O23vii | 0.90 (1) | 1.99 (3) | 2.851 (9) | 159 (4) |
Symmetry codes: (iv) −x+1, y+1/2, −z+1/2; (v) x−1, −y+1/2, z−1/2; (vi) −x+1, −y, −z+1; (vii) x−1, y, z. |
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Rare-earth tetraoxorhenates(VII) are known as precursors for the synthesis of mixed rare-earth oxides (Mujica et al., 1999). During the course of an investigation on the reactivity of rhenium metal with oxidizing agents we found, that the in situ generated `perrhenic acid' readily reacts with neodymium(III) oxide to triaquatris[tetraoxorhenio(VII)]neodymium(III), (I). The title compound crystallizes in the centrosymmetric space group P21/c with one neodymium, three crystallographic independent tetraoxorhenate(VII) anions and three water molecules in the asymmetric unit. This compound is configurationally isotypic to the triaquatris[tetraoxorhenio(VII)]lanthanum(III) (Mujica et al., 1997).
According to that, the neodymium is ninefold coordinated by three water molecules and six tetraoxorhenate(VII) anions to form the coordination figure of a distorted tricapped trigonal prism. The positions of the trigonal prism are occupied by four O atoms of four ReO4- anions and the two O atoms of the water ligands, while the three capped positions are occupied by two ReO4- O atoms and the O atom of one water molecule (Fig. 1).
This coordination mode is comparable with those of the well known rare-earth nonaaqua complexes [Ln(H2O)9(CF3SO3)3; Ln = trivalent rare earth metal cation; Harrowfield et al., 1983] and the isotypically bismuth compound (Frank et al., 1997). Due to the high symmetry of these simple aqua complex cations the neodymium–water distances of the six symmetry equivalent water molecules occupying the positions of the trigonal prism are 2.451 (2) and 2.571 (2) Å for the three symmetry equivalent water molecules of the capped positions (Chatterjee et al., 1988).
For the structure of the title compound, there is still a coordination polyhedron of a distorted three capped trigonal prism found at the neodymium cation, with the Nd—O distances varying in the range 2.470 (6)–2.543 (4) Å. But in contrast to the pure aqua complexes discussed above there are shorter and longer Nd—O distances found for the O atoms occupying the positions of the trigonal prism as well as those of the capped positions (Tab. 1).
The three water ligands at the neodymium form five weak hydrogen bonds to four neighbouring tetraoxorhenates(VII) anions (Fig. 2 and Table 3) The three-dimensional framework built by the anions coordinating the neodymium centre is best described as Nd(ReO4)(ReO4)2/2(ReO4)3/3, while the Re—O distances of the ReO4- anions vary in the range 1.712 (5)–1.728 (5) Å (Fig. 3).