The title compound, Nd(ReO4)3(H2O)3, crystallizes isostructurally with its analogous triaquatris[tetraoxorhenato(VII)]lanthanum(III) compound. The neodymium is coordinated by three water molecules and six O atoms of six tetraoxorhenate(VII) anions. The coordination polyhedron at the Nd is that of a tricapped trigonal prism. The three coordinated water molecules form five hydrogen bonds to four tetraoxorhenate(VII) anions.
Supporting information
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.
Triaquatris[tetraoxorhenio(VII)]neodymium(III)
top
Crystal data top
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 |
Data collection top
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 top
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) |
Crystal data top
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)° | |
Data collection top
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 | |
Refinement top
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 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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)* | |
Atomic displacement parameters (Å2) top | 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) |
Geometric parameters (Å, º) top
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. |
Hydrogen-bond geometry (Å, º) top
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 |
Selected bond lengths (Å) topNd1—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. |
Hydrogen-bond geometry (Å, º) top
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. |
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).