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Scheelite-type sodium neodymium(III) ortho-oxidomolybdate(VI), NaNd[MoO4]2

aInstitut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
*Correspondence e-mail: hartenbach@iac.uni-stuttgart.de

(Received 3 November 2011; accepted 7 November 2011; online 9 November 2011)

Scheelite-type NaNd[MoO4]2 contains one crystallographic position (site symmetry [\overline4]) for the large cations, which is mixed-occupied by Na+ and Nd3+ cations in a 1:1 molar ratio. Thus, both are surrounded by eight O atoms in the shape of a trigonal dodeca­hedron. Furthermore, the structure consists of crystallographically unique [MoO4]2− units (site symmetry [\overline4]) surrounded by eight sodium and neodymium cations, which are all vertex-attached. The polyhedra around the Na+/Nd3+ cations are connected to four others via common edges, building up a three-dimensional network in whose tetra­hedral voids of O atoms the Mo6+ cations reside.

Related literature

For isotypic NaLn[MoO4]2 structures, see: Stevens et al. (1991[Stevens, S. B., Morrison, C. A., Allik, T. H., Rheingold, A. L. & Haggerty, B. S. (1991). Phys. Rev. B Condens. Matter, 43, 7386-7394.]) and Teller (1992[Teller, R. G. (1992). Acta Cryst. C48, 2101-2104.]) for Ln = La; Teller (1992[Teller, R. G. (1992). Acta Cryst. C48, 2101-2104.]) for Ln = Ce; Zhao et al. (2010[Zhao, D., Li, F., Cheng, W. & Zhang, H. (2010). Acta Cryst. E66, i36.]) for Ln = Er. For inter­penetrating diamond-like networks, see: Schustereit et al. (2011[Schustereit, T., Müller, S. L., Schleid, Th. & Hartenbach, I. (2011). Crystals, Submitted.]). These were also obseverd in NaTl, see: Zintl & Dullenkopf (1932[Zintl, E. & Dullenkopf, W. (1932). Z. Phys. Chem. B, 16, 195-205.]).

Experimental

Crystal data
  • NaNd[MoO4]2

  • Mr = 487.11

  • Tetragonal, I 41 /a

  • a = 5.2871 (3) Å

  • c = 11.5729 (7) Å

  • V = 323.50 (3) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 11.79 mm−1

  • T = 293 K

  • 0.11 × 0.09 × 0.07 mm

Data collection
  • Nonius KappaCCD diffractometer

  • Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1995[Stoe & Cie (1995). X-SHAPE. Stoe & Cie, Darmstadt, Germany.]) Tmin = 0.273, Tmax = 0.434

  • 1026 measured reflections

  • 196 independent reflections

  • 135 reflections with I > 2σ(I)

  • Rint = 0.058

Refinement
  • R[F2 > 2σ(F2)] = 0.020

  • wR(F2) = 0.044

  • S = 0.99

  • 196 reflections

  • 15 parameters

  • Δρmax = 0.45 e Å−3

  • Δρmin = −0.42 e Å−3

Data collection: COLLECT (Nonius, 1998[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 2006[Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Scheelite-type sodium lanthanide ortho-oxomolybdates of the formula NaLn[MoO4]2 are already known for Ln = La, Ce, and Er (see related literature). The structure features Na+ and Nd3+ cations together at the common Wyckoff position 4b, eightfold coordinated by O2– anions in the shape of trigonal dodecahedra (Fig. 1). The Na : Nd ratio was fixed at a molar ratio of 1 : 1 for maintaining electroneutrality. A similar surrounding is found for the cationic coordination around the crystallographically unique isolated ortho-oxomolybdate anions [MoO4]2– with the Mo6+ cations at the Wyckoff position 4a (Fig. 2). The polyhedra around the Na+/Nd3+ cations are interconnected to four others via common edges building up a three-dimensional network, in whose voids of oxygen the Mo6+ cations are located (Fig. 3). Both the cations at the sites 4a (Na+ and Nd3+ in a 1:1 molar ratio) and 4b (Mo6+) arrange themselves in two interpenetrating diamond-like networks (Schustereit et al., 2011) as in the case of NaTl (Zintl & Dullenkopf, 1932).

Related literature top

For isotypic NaLn[MoO4]2 structures, see: Stevens et al. (1991) and Teller (1992) for Ln = La; Teller (1992) for Ln = Ce; Zhao et al. (2010) for Ln = Er. For interpenetrating diamond-like networks, see: Schustereit et al. (2011). These were also obseverd in NaTl, see: Zintl & Dullenkopf (1932).

Experimental top

Pale violet, coarse single crystals of Scheelite-type NaNd[MoO4]2 were obtained as by-product in an unsuccessful attempt to synthesize NdF[MoO4], using a mixture of NdF3 and Na2[MoO4] in a 1:1 molar ratio, which was heated at 850 °C for 7 days in an evacuated, sealed, fused-silica ampoule.

Structure description top

Scheelite-type sodium lanthanide ortho-oxomolybdates of the formula NaLn[MoO4]2 are already known for Ln = La, Ce, and Er (see related literature). The structure features Na+ and Nd3+ cations together at the common Wyckoff position 4b, eightfold coordinated by O2– anions in the shape of trigonal dodecahedra (Fig. 1). The Na : Nd ratio was fixed at a molar ratio of 1 : 1 for maintaining electroneutrality. A similar surrounding is found for the cationic coordination around the crystallographically unique isolated ortho-oxomolybdate anions [MoO4]2– with the Mo6+ cations at the Wyckoff position 4a (Fig. 2). The polyhedra around the Na+/Nd3+ cations are interconnected to four others via common edges building up a three-dimensional network, in whose voids of oxygen the Mo6+ cations are located (Fig. 3). Both the cations at the sites 4a (Na+ and Nd3+ in a 1:1 molar ratio) and 4b (Mo6+) arrange themselves in two interpenetrating diamond-like networks (Schustereit et al., 2011) as in the case of NaTl (Zintl & Dullenkopf, 1932).

For isotypic NaLn[MoO4]2 structures, see: Stevens et al. (1991) and Teller (1992) for Ln = La; Teller (1992) for Ln = Ce; Zhao et al. (2010) for Ln = Er. For interpenetrating diamond-like networks, see: Schustereit et al. (2011). These were also obseverd in NaTl, see: Zintl & Dullenkopf (1932).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Trigonal dodecahedral oxygen environment of the Na+/Nd3+ cations in Scheelite-type NaNd[MoO4]2 (ellipsoids are drawn at 90 % probability level, symmetry codes: (i) y–1/4, –x+3/4, z+3/4;(ii) –y+1/4, x–1/4, z+3/4; (iii) x–1/2, y, –z+1/2; (iv) –x+1/2, –y+1/2, –z+1/2; (v) –y+3/4, x–1/4, –z+3/4; (vi) y–3/4, –x+3/4, –z+3/4; (vii) x–1/2, y–1/2, z+1/2; (viii) –x+1/2, –y+1, z+1/2)
[Figure 2] Fig. 2. Cationic surrounding of the isolated ortho-oxomolybdate(VI) tetrahedra [MoO4]2– in Scheelite-type NaNd[MoO4]2 (ellipsoids are drawn at 90 % probability level, symmetry codes for O: x, y, z; (xi) –y+1/4, x+1/4, –z+1/4; (xii) y–1/4, –x+1/4, z+1/4; (xiii) –x, –y+1/2, z; symmetry codes for Na/Nd: (iii) x–1/2, y, –z+1/2; (iv) –x+1/2, –y+1/2, –z+1/2; (v) –y+3/4, x–1/4, –z+3/4; (vi) y–3/4, –x+3/4, –z+3/4; (vii) x–1/2, y–1/2, z+1/2; (ix) –x, –y, –z+1; (x) –x, –y+1, –z+1; (xiv) x+1/2, y+1/2, z–1/2)
[Figure 3] Fig. 3. View at the crystal structure of Scheelite-type NaNd[MoO4]2 along [010] (slightly rotated) with special emphasis on the edge-connected oxygen polyhedra around the Na+ and Nd3+ cations, respectively.
sodium neodymium(III) ortho-oxidomolybdate(vi) top
Crystal data top
NaNd[MoO4]2Dx = 5.001 Mg m3
Mr = 487.11Mo Kα radiation, λ = 0.71069 Å
Tetragonal, I41/aCell parameters from 2325 reflections
Hall symbol: -I 4adθ = 1.0–28.3°
a = 5.2871 (3) ŵ = 11.79 mm1
c = 11.5729 (7) ÅT = 293 K
V = 323.50 (3) Å3Coarse transparent, pale violet
Z = 20.11 × 0.09 × 0.07 mm
F(000) = 438
Data collection top
Nonius KappaCCD
diffractometer
196 independent reflections
Radiation source: fine-focus sealed tube135 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.058
ω and φ scansθmax = 28.2°, θmin = 4.2°
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 1995)
h = 66
Tmin = 0.273, Tmax = 0.434k = 66
1026 measured reflectionsl = 1515
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.020 w = 1/[σ2(Fo2) + (0.0102P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.044(Δ/σ)max < 0.001
S = 0.99Δρmax = 0.45 e Å3
196 reflectionsΔρmin = 0.42 e Å3
15 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0092 (8)
Crystal data top
NaNd[MoO4]2Z = 2
Mr = 487.11Mo Kα radiation
Tetragonal, I41/aµ = 11.79 mm1
a = 5.2871 (3) ÅT = 293 K
c = 11.5729 (7) Å0.11 × 0.09 × 0.07 mm
V = 323.50 (3) Å3
Data collection top
Nonius KappaCCD
diffractometer
196 independent reflections
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 1995)
135 reflections with I > 2σ(I)
Tmin = 0.273, Tmax = 0.434Rint = 0.058
1026 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02015 parameters
wR(F2) = 0.0440 restraints
S = 0.99Δρmax = 0.45 e Å3
196 reflectionsΔρmin = 0.42 e Å3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
xyzUiso*/UeqOcc. (<1)
Na0.00000.25000.62500.0125 (2)0.50
Nd0.00000.25000.62500.0125 (2)0.50
Mo0.00000.25000.12500.0131 (2)
O0.2406 (3)0.3949 (3)0.04140 (14)0.0255 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Na0.0130 (3)0.0130 (3)0.0113 (3)0.0000.0000.000
Nd0.0130 (3)0.0130 (3)0.0113 (3)0.0000.0000.000
Mo0.0122 (3)0.0122 (3)0.0151 (3)0.0000.0000.000
O0.0298 (10)0.0227 (12)0.0239 (9)0.0002 (8)0.0022 (8)0.0008 (9)
Geometric parameters (Å, º) top
Na—Oi2.4851 (15)Na—Ndx3.9191 (2)
Na—Oii2.4851 (15)Na—Nax3.9191 (2)
Na—Oiii2.4851 (15)Mo—Oxi1.7725 (16)
Na—Oiv2.4851 (15)Mo—O1.7725 (17)
Na—Ov2.5182 (18)Mo—Oxii1.7725 (16)
Na—Ovi2.5182 (18)Mo—Oxiii1.7725 (16)
Na—Ovii2.5182 (18)O—Ndiii2.4851 (15)
Na—Oviii2.5182 (18)O—Naiii2.4851 (15)
Na—Naix3.9191 (2)O—Naxiv2.5182 (18)
Na—Ndix3.9191 (2)O—Ndxiv2.5182 (18)
Oi—Na—Oii126.90 (5)Ovi—Na—Ndix102.66 (4)
Oi—Na—Oiii126.90 (5)Ovii—Na—Ndix85.20 (3)
Oii—Na—Oiii78.41 (7)Oviii—Na—Ndix130.62 (4)
Oi—Na—Oiv78.41 (7)Naix—Na—Ndix0.0
Oii—Na—Oiv126.90 (5)Oi—Na—Ndx38.74 (4)
Oiii—Na—Oiv126.90 (5)Oii—Na—Ndx160.78 (4)
Oi—Na—Ov151.28 (7)Oiii—Na—Ndx101.53 (4)
Oii—Na—Ov68.38 (4)Oiv—Na—Ndx68.65 (4)
Oiii—Na—Ov76.88 (6)Ov—Na—Ndx130.62 (4)
Oiv—Na—Ov73.65 (3)Ovi—Na—Ndx85.20 (3)
Oi—Na—Ovi73.65 (3)Ovii—Na—Ndx38.14 (3)
Oii—Na—Ovi76.88 (6)Oviii—Na—Ndx102.66 (4)
Oiii—Na—Ovi68.38 (4)Naix—Na—Ndx123.025 (3)
Oiv—Na—Ovi151.28 (7)Ndix—Na—Ndx123.025 (3)
Ov—Na—Ovi134.81 (8)Oi—Na—Nax38.74 (4)
Oi—Na—Ovii76.88 (6)Oii—Na—Nax160.78 (4)
Oii—Na—Ovii151.28 (7)Oiii—Na—Nax101.53 (4)
Oiii—Na—Ovii73.65 (3)Oiv—Na—Nax68.65 (4)
Oiv—Na—Ovii68.38 (4)Ov—Na—Nax130.62 (4)
Ov—Na—Ovii98.49 (3)Ovi—Na—Nax85.20 (3)
Ovi—Na—Ovii98.49 (3)Ovii—Na—Nax38.14 (3)
Oi—Na—Oviii68.38 (4)Oviii—Na—Nax102.66 (4)
Oii—Na—Oviii73.65 (3)Naix—Na—Nax123.025 (3)
Oiii—Na—Oviii151.28 (7)Ndix—Na—Nax123.025 (3)
Oiv—Na—Oviii76.88 (6)Ndx—Na—Nax0.0
Ov—Na—Oviii98.49 (3)Oxi—Mo—O113.83 (11)
Ovi—Na—Oviii98.49 (3)Oxi—Mo—Oxii107.34 (5)
Ovii—Na—Oviii134.81 (8)O—Mo—Oxii107.34 (5)
Oi—Na—Naix160.78 (4)Oxi—Mo—Oxiii107.34 (5)
Oii—Na—Naix68.65 (4)O—Mo—Oxiii107.34 (5)
Oiii—Na—Naix38.74 (4)Oxii—Mo—Oxiii113.83 (11)
Oiv—Na—Naix101.53 (4)Mo—O—Ndiii133.30 (9)
Ov—Na—Naix38.14 (3)Mo—O—Naiii133.30 (9)
Ovi—Na—Naix102.66 (4)Ndiii—O—Naiii0.0
Ovii—Na—Naix85.20 (3)Mo—O—Naxiv120.23 (8)
Oviii—Na—Naix130.62 (4)Ndiii—O—Naxiv103.12 (6)
Oi—Na—Ndix160.78 (4)Naiii—O—Naxiv103.12 (6)
Oii—Na—Ndix68.65 (4)Mo—O—Ndxiv120.23 (8)
Oiii—Na—Ndix38.74 (4)Ndiii—O—Ndxiv103.12 (6)
Oiv—Na—Ndix101.53 (4)Naiii—O—Ndxiv103.12 (6)
Ov—Na—Ndix38.14 (3)Naxiv—O—Ndxiv0.0
Symmetry codes: (i) y1/4, x+3/4, z+3/4; (ii) x1/2, y, z+1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) y+1/4, x1/4, z+3/4; (v) x1/2, y1/2, z+1/2; (vi) x+1/2, y+1, z+1/2; (vii) y+3/4, x1/4, z+3/4; (viii) y3/4, x+3/4, z+3/4; (ix) x, y, z+1; (x) x+1/2, y+1/2, z+3/2; (xi) x, y+1/2, z; (xii) y+1/4, x+1/4, z+1/4; (xiii) y1/4, x+1/4, z+1/4; (xiv) x+1/2, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaNaNd[MoO4]2
Mr487.11
Crystal system, space groupTetragonal, I41/a
Temperature (K)293
a, c (Å)5.2871 (3), 11.5729 (7)
V3)323.50 (3)
Z2
Radiation typeMo Kα
µ (mm1)11.79
Crystal size (mm)0.11 × 0.09 × 0.07
Data collection
DiffractometerNonius KappaCCD
Absorption correctionNumerical
(X-SHAPE; Stoe & Cie, 1995)
Tmin, Tmax0.273, 0.434
No. of measured, independent and
observed [I > 2σ(I)] reflections
1026, 196, 135
Rint0.058
(sin θ/λ)max1)0.664
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.044, 0.99
No. of reflections196
No. of parameters15
Δρmax, Δρmin (e Å3)0.45, 0.42

Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006).

 

Acknowledgements

This work was supported by the State of Baden-Württemberg (Stuttgart) and the Deutsche Forschungsgemeinschaft (DFG; Frankfurt/Main) within the funding programme Open Access Publishing.

References

First citationBrandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationNonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.  Google Scholar
First citationSchustereit, T., Müller, S. L., Schleid, Th. & Hartenbach, I. (2011). Crystals, Submitted.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationStevens, S. B., Morrison, C. A., Allik, T. H., Rheingold, A. L. & Haggerty, B. S. (1991). Phys. Rev. B Condens. Matter, 43, 7386–7394.  CrossRef CAS PubMed Web of Science Google Scholar
First citationStoe & Cie (1995). X-SHAPE. Stoe & Cie, Darmstadt, Germany.  Google Scholar
First citationTeller, R. G. (1992). Acta Cryst. C48, 2101–2104.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationZhao, D., Li, F., Cheng, W. & Zhang, H. (2010). Acta Cryst. E66, i36.  Web of Science CrossRef IUCr Journals Google Scholar
First citationZintl, E. & Dullenkopf, W. (1932). Z. Phys. Chem. B, 16, 195–205.  Google Scholar

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