Tri­aqua­tris­[tetraoxorhenato(VII)]­neodymium(III)

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](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

---

S1. Comment

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).

S2. Experimental

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.

S3. Refinement

The atomic coordinates of the Hatoms were refined using O—H and H—H distance restraints. One common U_iso value for all H atoms of the water molecules has been refined.

Computing details

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.

Figures

	Fig. 1. Each neodym has a coordination polyhedron of a distorted tricapped trigonal prism built by six tetraoxorhenate(VII) anions and three water molecules. The ellipsoids are drawn at the 50% probability level. Atoms used to build the polyhedron are drawn with an arbitrary radius [symmetry code; (a) 1 + x, y, z; (b) 1 - x, -0.5 + y, 0.5 - z; (c) -x, -y, -z].
	Fig. 2. Showing the coordination of the neodymium centre and the hydrogen-bonding motif of the three water ligands. The ellipsoids are drawn at the 50% probability level. Atoms used to build the polyhedron are drawn with an arbitrary radius [symmetry code: (a) -x, -y, -z; (b) 1 - x, -0.5 + y, 0.5 - z; (c) 1 + x, y, z; (d) 1 - x, -y,-1 - z; (e) 1 + x, 0.5 - y, 0.5 + z; (f) 1 - x, 0.5 + y, 0.5 - z].
	Fig. 3. Showing the packing of the title compound with a view along [100].

Triaquatris[tetraoxorhenio(VII)]neodymium(III)

Crystal data

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) Å^3	Platelet, colourless
Z = 4	0.50 × 0.10 × 0.01 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.024	Restr
wR(F^2) = 0.055	w = 1/[σ^2(Fo^2) + (0.024P)^2 + 2.40P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00057 (7)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—O12^i	2.476 (5)
Re2—O24	1.716 (5)	Nd1—O21^ii	2.483 (5)
Re3—O31	1.725 (5)	Nd1—O13^iii	2.520 (4)
Re3—O32	1.713 (6)	O12—Nd1^i	2.476 (5)
Re3—O33	1.716 (5)	O13—Nd1^iv	2.520 (4)
Re3—O34	1.713 (5)	O21—Nd1^v	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)	O12^i—Nd1—O1W	96.3 (2)
O14—Re1—O12	108.0 (4)	O21^ii—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)	O12^i—Nd1—O2W	70.5 (3)
Re1—O12—Nd1^i	168.7 (4)	O21^ii—Nd1—O2W	136.3 (2)
Re1—O13—Nd1^iv	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)	O12^i—Nd1—O22	139.8 (2)
O23—Re2—O21	111.0 (4)	O21^ii—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—Nd1^v	150.1 (4)	O3W—Nd1—O13^iii	139.0 (2)
Re2—O22—Nd1	142.5 (4)	O31—Nd1—O13^iii	69.4 (2)
O32—Re3—O34	108.7 (5)	O12^i—Nd1—O13^iii	72.7 (2)
O32—Re3—O33	109.4 (4)	O21^ii—Nd1—O13^iii	79.4 (2)
O34—Re3—O33	109.3 (5)	O1W—Nd1—O13^iii	136.5 (2)
O32—Re3—O31	109.5 (4)	O2W—Nd1—O13^iii	68.3 (2)
O34—Re3—O31	108.9 (4)	O22—Nd1—O13^iii	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)	O12^i—Nd1—O11	69.2 (2)
O3W—Nd1—O12^i	137.9 (2)	O21^ii—Nd1—O11	71.1 (2)
O31—Nd1—O12^i	130.8 (2)	O1W—Nd1—O11	67.6 (2)
O3W—Nd1—O21^ii	86.0 (2)	O2W—Nd1—O11	114.7 (2)
O31—Nd1—O21^ii	70.8 (2)	O22—Nd1—O11	132.5 (2)
O12^i—Nd1—O21^ii	72.4 (2)	O13^iii—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)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O33^v	0.90 (1)	2.27 (6)	3.073 (11)	148 (10)
O1W—H2W···O32^vi	0.90 (1)	2.29 (3)	3.009 (10)	137 (3)
O2W—H4W···O33^v	0.90 (1)	2.08 (3)	2.954 (10)	163 (6)
O3W—H5W···O33^vii	0.90 (1)	2.17 (5)	3.024 (11)	158 (12)
O3W—H6W···O23^iv	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.