Poly[μ2-hydroxido-μ4-sulfato-neodym­ium(III)]

Tao Zhang; Jingmei Lu

doi:10.1107/S1600536808021818

. 2008 Jul 19;64(Pt 8):i49. doi: 10.1107/S1600536808021818

Poly[μ₂-hydroxido-μ₄-sulfato-neodymium(III)]

Tao Zhang ^a, Jingmei Lu ^a,^*

PMCID: PMC2961904 PMID: 21202992

Abstract

The title compound, [Nd(OH)(SO₄)]_n, was obtained hydrothermally from an aqueous solution of neodymium nitrate, 1,2-propanediamine and sulfuric acid. The structure features nonacoordinated neodymium with sulfate and hydroxide anions acting as bridging ligands. The OH group forms a weak O—H⋯O hydrogen bond with an O⋯O distance of 3.224 (5) Å.

Related literature

For related literature, see: Doran et al. (2002 ▶); Xu, Ding, Zhou & Liu (2006 ▶); Xu, Ding, Feng et al. (2006 ▶); Xu et al. (2007 ▶); Yuan et al. (2004 ▶); Zhang et al. (2004 ▶); Ding et al. (2006 ▶).

Experimental

Crystal data

[Nd(OH)(SO₄)]
M _r = 257.31
Monoclinic,
a = 4.4678 (9) Å
b = 12.432 (2) Å
c = 6.8575 (13) Å
β = 106.324 (3)°
V = 365.53 (12) Å³
Z = 4
Mo Kα radiation
μ = 14.66 mm⁻¹
T = 293 (2) K
0.10 × 0.08 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.322, T _max = 0.473 (expected range = 0.282–0.415)
1837 measured reflections
675 independent reflections
669 reflections with I > 2σ(I)
R _int = 0.013

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.056
S = 1.24
675 reflections
67 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.56 e Å⁻³
Δρ_min = −2.27 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021818/br2079sup1.cif

e-64-00i49-sup1.cif^{(14.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021818/br2079Isup2.hkl

e-64-00i49-Isup2.hkl^{(33.7KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H1⋯O1ⁱ	0.83 (3)	2.43 (3)	3.224 (5)	160 (6)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Dr Zhang for help with the structural analysis.

supplementary crystallographic information

Comment

In the last few years, the synthesis of new three dimensional lanthanide sulfates have received great attention, due to their functional applications in catalysis, ion-exchange, and optical device (Zhang et al.,2004; Yuan et al., 2004; Xu, Ding, Feng et al., 2006; Xu, Ding, Zhou & Liu, 2006; Doran et al., 2002, Xu et al., 2007). In this work, we designed and synthesized the title compound, neodymium(3+) sulfate hydroxide, which features a three–dimensional framework constructed from NdO₉ polyhedra and SO₄ tetrahedra.

Nd(SO₄)(OH) is isostructural with La(SO₄)(OH) (Zhang et al.,2004) and Eu(SO₄)(OH)(Ding et al.,2006), the framework of title compound constructed from NdO₉ polyhedra and SO₄ tetrahedra. As show in Fig. 1, the asymmetric unit contains one Nd³⁺, one SO₄^2– group and one hydroxide group. The Nd³⁺ is coordinated by six bridging sulfate ions, each S atom makes four S–O–Nd linkages by sharing the bridging O atoms. The coordination sphere of Nd is completed by three OH^- groups, which act as briding ligands between three Nd^3+^.

The O-H group is involved hydrogen bonding interactions with O1, O2 and O4, the distances of O—H···O are vary from 2.60 (2) to 2.90 (2) Å.

The Nd —O distances are between of 2.374 (4)– 2.800 (4)Å (Table 1)while the O—Nd—O angles are between 66.02 (13) and 141.55 (12)°. These bond distances and bond angles are in agreement with those found in the reported rare-earth compounds (Zhang et al.,2004; Ding et al.,2006). The bond distances of S—O and angles of O—S—O are unexceptional. Fig. 2 shows the three-dimensional arrangement in the unit cell, displaying the way the different Nd³⁺ are connected by bridging hydroxide and sulfates groups.

Experimental

Pink block crystals were synthesized hydrothermally from a mixture of Nd(NO₃)₃.6H₂O, 1,2-propane diamine, H₂SO₄ and water. In a typical synthesis, Nd(NO₃)₃.6H₂O (0.6066 g) was dissolved in a mixture of 1,2-propane diamine (0.2205 g) and water (3.2 ml) followed by the addition of H₂SO₄ (98%) (0.3093 g) with constant stirring. Finally, the mixture was kept in a 25 ml Teflon-lined steel autoclave at 180 °C for 7 days. After the autoclave was slowly cooled to room temperature, Pink block crystals of the title compound were obtained.