[(2R,3S)-Butane-1,2,3,4-tetraol-κ3 O 1,O 2,O 3](ethanol-κO)tris­(nitrato-κ2 O,O′)samarium(III)

Jun-Hui Xue; Xiao-Hui Hua; Li-Min Yang; Yi-Zhuang Xu; Jin-Guang Wu

doi:10.1107/S1600536813003255

. 2013 Mar 2;69(Pt 4):m182–m183. doi: 10.1107/S1600536813003255

[(2R,3S)-Butane-1,2,3,4-tetraol-κ³ O ¹,O ²,O ³](ethanol-κO)tris(nitrato-κ² O,O′)samarium(III)

Jun-Hui Xue ^a, Xiao-Hui Hua ^b, Li-Min Yang ^c,^*, Yi-Zhuang Xu ^b, Jin-Guang Wu ^b

PMCID: PMC3629469 PMID: 23633987

Abstract

The title Sm^III–erythritol complex, [Sm(NO₃)₃(C₂H₆O)(C₄H₁₀O₄)], is isotypic with its Nd, Eu, Y, Gd, Tb and Ho analogues. The Sm^III cation exhibits a coordination number of ten and is chelated by a tridentate erythritol ligand and three bidentate nitrate anions. It is additionally coordinated by an O atom of an ethanol molecule, completing an irregular coordination sphere. The Sm—O bond lengths range from 2.416 (2) to 2.611 (2) Å. In the crystal, extensive O—H⋯O hydrogen bonding involving all hydroxy groups and some of the nitrate O atoms links the molecules into a three-dimensional network.

Related literature

For background to the coordination behaviour of sugars to metal cations, see: Gottschaldt & Schubert (2009 ▶). For the crystal structure of free erythritol, see: Bekoe & Powell (1959 ▶). For isotypic structures of the title compound, see: Yang et al. (2003 ▶, 2004 ▶, 2012 ▶); Hua et al. (2013 ▶).

Experimental

Crystal data

[Sm(NO₃)₃(C₂H₆O)(C₄H₁₀O₄)]
M _r = 504.57
Monoclinic,
a = 7.8537 (16) Å
b = 12.875 (3) Å
c = 15.252 (3) Å
β = 100.92 (3)°
V = 1514.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 3.96 mm⁻¹
T = 173 K
0.27 × 0.21 × 0.16 mm

Data collection

Rigaku Saturn724+ CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ▶) T _min = 0.488, T _max = 1.000
10349 measured reflections
3446 independent reflections
3315 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.057
S = 1.22
3446 reflections
218 parameters
Δρ_max = 1.33 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Data collection: CrystalClear (Rigaku, 2007 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Click here for additional data file.^{(19.3KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813003255/wm2711sup1.cif

e-69-0m182-sup1.cif^{(19.3KB, cif)}

Click here for additional data file.^{(169KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813003255/wm2711Isup2.hkl

e-69-0m182-Isup2.hkl^{(169KB, hkl)}

Click here for additional data file.^{(4.9KB, cdx)}

Supplementary material file. DOI: 10.1107/S1600536813003255/wm2711Isup3.cdx

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
O1—H1⋯O4ⁱ	0.84	1.83	2.668 (3)	175
O2—H2⋯O7ⁱⁱ	0.84	1.96	2.802 (3)	174
O2—H2⋯O8ⁱⁱ	0.84	2.54	3.146 (4)	130
O3—H3⋯O12ⁱⁱⁱ	0.84	2.07	2.903 (3)	174
O4—H4⋯O8^iv	0.84	2.09	2.910 (4)	165
O4—H4⋯O6^iv	0.84	2.55	3.235 (3)	140
O5—H5⋯O11^v	0.84	2.00	2.827 (4)	167

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

This work was supported financially by the National Natural Science Foundation of China (grants Nos. 50973003 and 21001009) and the National High-Tech R&D Program of China (863 Program) of MOST (No. 2010 A A03A406). Special thanks to Drs Hao, Wang and Liang for their assistance with the data collection.

supplementary crystallographic information

Comment

Metal ions play important roles in the catalysis of numerous chemical and biological reactions. Interactions between carbohydrates (sugars) and metal ions may be involved in many biochemical processes (Gottschaldt & Schubert, 2009). Here the sugar alcohol erythritol was chosen as a model compound to study the coordination behavior of hydroxyl groups to f-block metal ions.

The molecular structure of the title complex, [Sm(C₄H₁₀O₄)(C₂H₅OH)(NO₃)₃], denoted as SmEN, where E stands for erythritol, N stands for nitrate, is shown in Fig. 1. In the title compound the Sm^III cation is 10-fold coordinated by three hydroxyl groups (O1, O2 and O3) from one erythritol molecule, by one hydroxyl group from ethanol (O5), and by three bidentate nitrate ions through O6, O7; O9, O10; O12, O13. The structure of SmEN is isotypic with its Nd, Eu, Y, Gd, Tb (Yang et al., 2003, 2004, 2012) and Ho (Hua et al., 2013) analogues. The Sm—O distances range from 2.416 (2) to 2.611 (2) Å, the average Sm—O distance being 2.499 Å. The C—C—C and the O—C–C bond angles of the central backbone in the free centrosymmetric erythritol molecule are 113° and 107°, respectively (Bekoe & Powell, 1959). After coordination, the C—C—C bond angles are 112.6 (3) and 116.7 (3)° and the O—C—C bond angles range from 104.0 (3) to 111.6 (3)° in SmEN, which indicates a subtle change of the conformation of erythritol.

The extensive hydrogen bond network in SmEN is formed by O—H···O hydrogen bonds from coordinating and uncoordinating hydroxyl groups of erythritol and ethanol and the nitrate O atoms. The coordinating hydroxyl groups O1 of erythritol forms a hydrogen bond with the uncoordinating O4 hydroxyl group of a neighbouring erythritol molecule. The coordinating O2 hydroxyl group forms a bifurcated hydrogen bonds with two oxygen atoms from a nitrate ion (O7, O8). The coordinating hydroxyl group O3 forms a hydrogen bond with an oxygen atom from another nitrate ion (O12). The non-coordinating hydroxyl group O4 is a donor of a bifurcated hydrogen bond to O8 and O6 from one nitrate ion. The ethanol hydroxy group (O5) forms a hydrogen bond with an oxygen atom from a nitrate ion (O11). Details of the hydrogen bonding are given in Table 1 and Fig. 2.

Experimental

Sm(NO₃)₃^.6H₂O (3 mmol) and erythritol (3 mmol) were dissolved in 6 ml water and 6 ml ethanol. The solution was put on a water bath, and the temperature was raised to 353 K. Small aliquots of EtOH were periodically added to the solution during the heating process to prolong the reaction time. The resulting mixture was filtered and left for crystallization at room temperature. Suitable crystals for X-ray diffraction measuraments were obtained in the course of two weeks.