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

Schleid, T.; Hartenbach, I.

doi:10.1107/S1600536811046976

inorganic compounds

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Volume 67| Part 12| December 2011| Page i71

https://doi.org/10.1107/S1600536811046976

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

Thomas Schleid ^a and Ingo Hartenbach ^a ^*

^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 ) 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

Crystal data

NaNd[MoO₄]₂
M_r = 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 ) T_min = 0.273, T_max = 0.434
1026 measured reflections
196 independent reflections
135 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.044
S = 0.99
196 reflections
15 parameters
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.42 e Å⁻³

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811046976/hp2019sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046976/hp2019Isup2.hkl

checkCIF report

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 O^2– 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

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

	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)
	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)
	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]₂	D_x = 5.001 Mg m⁻³
M_r = 487.11	Mo Kα radiation, λ = 0.71069 Å
Tetragonal, I4₁/a	Cell parameters from 2325 reflections
Hall symbol: -I 4ad	θ = 1.0–28.3°
a = 5.2871 (3) Å	µ = 11.79 mm⁻¹
c = 11.5729 (7) Å	T = 293 K
V = 323.50 (3) Å³	Coarse transparent, pale violet
Z = 2	0.11 × 0.09 × 0.07 mm
F(000) = 438

Data collection top

Nonius KappaCCD diffractometer	196 independent reflections
Radiation source: fine-focus sealed tube	135 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
ω and φ scans	θ_max = 28.2°, θ_min = 4.2°
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1995)	h = −6→6
T_min = 0.273, T_max = 0.434	k = −6→6
1026 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.020	w = 1/[σ²(F_o²) + (0.0102P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.044	(Δ/σ)_max < 0.001
S = 0.99	Δρ_max = 0.45 e Å⁻³
196 reflections	Δρ_min = −0.42 e Å⁻³
15 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0092 (8)

Crystal data top

NaNd[MoO₄]₂	Z = 2
M_r = 487.11	Mo Kα radiation
Tetragonal, I4₁/a	µ = 11.79 mm⁻¹
a = 5.2871 (3) Å	T = 293 K
c = 11.5729 (7) Å	0.11 × 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)
T_min = 0.273, T_max = 0.434	R_int = 0.058
1026 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	15 parameters
wR(F²) = 0.044	0 restraints
S = 0.99	Δρ_max = 0.45 e Å⁻³
196 reflections	Δρ_min = −0.42 e Å⁻³

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Na	0.0000	0.2500	0.6250	0.0125 (2)	0.50
Nd	0.0000	0.2500	0.6250	0.0125 (2)	0.50
Mo	0.0000	0.2500	0.1250	0.0131 (2)
O	0.2406 (3)	0.3949 (3)	0.04140 (14)	0.0255 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Na	0.0130 (3)	0.0130 (3)	0.0113 (3)	0.000	0.000	0.000
Nd	0.0130 (3)	0.0130 (3)	0.0113 (3)	0.000	0.000	0.000
Mo	0.0122 (3)	0.0122 (3)	0.0151 (3)	0.000	0.000	0.000
O	0.0298 (10)	0.0227 (12)	0.0239 (9)	−0.0002 (8)	0.0022 (8)	−0.0008 (9)

Geometric parameters (Å, º) top

Na—Oⁱ	2.4851 (15)	Na—Nd^x	3.9191 (2)
Na—Oⁱⁱ	2.4851 (15)	Na—Na^x	3.9191 (2)
Na—Oⁱⁱⁱ	2.4851 (15)	Mo—O^xi	1.7725 (16)
Na—O^iv	2.4851 (15)	Mo—O	1.7725 (17)
Na—O^v	2.5182 (18)	Mo—O^xii	1.7725 (16)
Na—O^vi	2.5182 (18)	Mo—O^xiii	1.7725 (16)
Na—O^vii	2.5182 (18)	O—Ndⁱⁱⁱ	2.4851 (15)
Na—O^viii	2.5182 (18)	O—Naⁱⁱⁱ	2.4851 (15)
Na—Na^ix	3.9191 (2)	O—Na^xiv	2.5182 (18)
Na—Nd^ix	3.9191 (2)	O—Nd^xiv	2.5182 (18)

Oⁱ—Na—Oⁱⁱ	126.90 (5)	O^vi—Na—Nd^ix	102.66 (4)
Oⁱ—Na—Oⁱⁱⁱ	126.90 (5)	O^vii—Na—Nd^ix	85.20 (3)
Oⁱⁱ—Na—Oⁱⁱⁱ	78.41 (7)	O^viii—Na—Nd^ix	130.62 (4)
Oⁱ—Na—O^iv	78.41 (7)	Na^ix—Na—Nd^ix	0.0
Oⁱⁱ—Na—O^iv	126.90 (5)	Oⁱ—Na—Nd^x	38.74 (4)
Oⁱⁱⁱ—Na—O^iv	126.90 (5)	Oⁱⁱ—Na—Nd^x	160.78 (4)
Oⁱ—Na—O^v	151.28 (7)	Oⁱⁱⁱ—Na—Nd^x	101.53 (4)
Oⁱⁱ—Na—O^v	68.38 (4)	O^iv—Na—Nd^x	68.65 (4)
Oⁱⁱⁱ—Na—O^v	76.88 (6)	O^v—Na—Nd^x	130.62 (4)
O^iv—Na—O^v	73.65 (3)	O^vi—Na—Nd^x	85.20 (3)
Oⁱ—Na—O^vi	73.65 (3)	O^vii—Na—Nd^x	38.14 (3)
Oⁱⁱ—Na—O^vi	76.88 (6)	O^viii—Na—Nd^x	102.66 (4)
Oⁱⁱⁱ—Na—O^vi	68.38 (4)	Na^ix—Na—Nd^x	123.025 (3)
O^iv—Na—O^vi	151.28 (7)	Nd^ix—Na—Nd^x	123.025 (3)
O^v—Na—O^vi	134.81 (8)	Oⁱ—Na—Na^x	38.74 (4)
Oⁱ—Na—O^vii	76.88 (6)	Oⁱⁱ—Na—Na^x	160.78 (4)
Oⁱⁱ—Na—O^vii	151.28 (7)	Oⁱⁱⁱ—Na—Na^x	101.53 (4)
Oⁱⁱⁱ—Na—O^vii	73.65 (3)	O^iv—Na—Na^x	68.65 (4)
O^iv—Na—O^vii	68.38 (4)	O^v—Na—Na^x	130.62 (4)
O^v—Na—O^vii	98.49 (3)	O^vi—Na—Na^x	85.20 (3)
O^vi—Na—O^vii	98.49 (3)	O^vii—Na—Na^x	38.14 (3)
Oⁱ—Na—O^viii	68.38 (4)	O^viii—Na—Na^x	102.66 (4)
Oⁱⁱ—Na—O^viii	73.65 (3)	Na^ix—Na—Na^x	123.025 (3)
Oⁱⁱⁱ—Na—O^viii	151.28 (7)	Nd^ix—Na—Na^x	123.025 (3)
O^iv—Na—O^viii	76.88 (6)	Nd^x—Na—Na^x	0.0
O^v—Na—O^viii	98.49 (3)	O^xi—Mo—O	113.83 (11)
O^vi—Na—O^viii	98.49 (3)	O^xi—Mo—O^xii	107.34 (5)
O^vii—Na—O^viii	134.81 (8)	O—Mo—O^xii	107.34 (5)
Oⁱ—Na—Na^ix	160.78 (4)	O^xi—Mo—O^xiii	107.34 (5)
Oⁱⁱ—Na—Na^ix	68.65 (4)	O—Mo—O^xiii	107.34 (5)
Oⁱⁱⁱ—Na—Na^ix	38.74 (4)	O^xii—Mo—O^xiii	113.83 (11)
O^iv—Na—Na^ix	101.53 (4)	Mo—O—Ndⁱⁱⁱ	133.30 (9)
O^v—Na—Na^ix	38.14 (3)	Mo—O—Naⁱⁱⁱ	133.30 (9)
O^vi—Na—Na^ix	102.66 (4)	Ndⁱⁱⁱ—O—Naⁱⁱⁱ	0.0
O^vii—Na—Na^ix	85.20 (3)	Mo—O—Na^xiv	120.23 (8)
O^viii—Na—Na^ix	130.62 (4)	Ndⁱⁱⁱ—O—Na^xiv	103.12 (6)
Oⁱ—Na—Nd^ix	160.78 (4)	Naⁱⁱⁱ—O—Na^xiv	103.12 (6)
Oⁱⁱ—Na—Nd^ix	68.65 (4)	Mo—O—Nd^xiv	120.23 (8)
Oⁱⁱⁱ—Na—Nd^ix	38.74 (4)	Ndⁱⁱⁱ—O—Nd^xiv	103.12 (6)
O^iv—Na—Nd^ix	101.53 (4)	Naⁱⁱⁱ—O—Nd^xiv	103.12 (6)
O^v—Na—Nd^ix	38.14 (3)	Na^xiv—O—Nd^xiv	0.0

Symmetry codes: (i) y−1/4, −x+3/4, z+3/4; (ii) x−1/2, y, −z+1/2; (iii) −x+1/2, −y+1/2, −z+1/2; (iv) −y+1/4, x−1/4, z+3/4; (v) x−1/2, y−1/2, z+1/2; (vi) −x+1/2, −y+1, z+1/2; (vii) −y+3/4, x−1/4, −z+3/4; (viii) y−3/4, −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) y−1/4, −x+1/4, −z+1/4; (xiv) x+1/2, y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	NaNd[MoO₄]₂
M_r	487.11
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	293
a, c (Å)	5.2871 (3), 11.5729 (7)
V (Å³)	323.50 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	11.79
Crystal size (mm)	0.11 × 0.09 × 0.07

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Numerical (X-SHAPE; Stoe & Cie, 1995)
T_min, T_max	0.273, 0.434
No. of measured, independent and observed [I > 2σ(I)] reflections	1026, 196, 135
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.664

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.044, 0.99
No. of reflections	196
No. of parameters	15
Δρ_max, Δρ_min (e Å⁻³)	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

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