Bis(μ-2-{[2-(1,3-benzothia­zol-2-yl)hydrazinyl­idene]meth­yl}-6-meth­oxy­phenolato)bis­[dinitratodysprosium(III)] methanol disolvate

Xuebin Xu; Shuai Ding; Si Shen; Jinkui Tang; Zhiliang Liu

doi:10.1107/S1600536811019118

. 2011 May 25;67(Pt 6):m796–m797. doi: 10.1107/S1600536811019118

Bis(μ-2-{[2-(1,3-benzothiazol-2-yl)hydrazinylidene]methyl}-6-methoxyphenolato)bis[dinitratodysprosium(III)] methanol disolvate

Xuebin Xu ^a, Shuai Ding ^a, Si Shen ^b, Jinkui Tang ^b, Zhiliang Liu ^a,^*

PMCID: PMC3120308 PMID: 21754674

Abstract

In the centrosymmetric dinuclear title compound, [Dy₂(C₁₅H₁₂N₃O₂S)₂(NO₃)₄]·2CH₃OH, the two Dy^III atoms are coordinated by two deprotonated 2-{[2-(1,3-benzothiazol-2-yl)hydrazinylidene]methyl}-6-methoxyphenol ligands and four nitrate ions, all of which are chelating. The crystal packing is stabilized by intermolecular N—H⋯O hydrogen bonds and weak O—H⋯O interactions, forming a two-dimensional network parallel to (010).

Related literature

For applications of dysprosium complexes in data storage and processing, see: Lin et al. (2010 ▶). For the preparation of the 2-{[2-(1,3-benzothiazol-2-yl)hydrazinylidene]methyl}-6-methoxyphenol ligand, see: Patil et al. (2009 ▶). For related structures, see: Lin & Hong (2009 ▶); Lin et al. (2008 ▶); Xu et al. (2010 ▶).

Experimental

Crystal data

[Dy₂(C₁₅H₁₂N₃O₂S)₂(NO₃)₄]·2CH₄O
M _r = 1233.82
Triclinic,
a = 9.6191 (6) Å
b = 10.1002 (7) Å
c = 11.6151 (8) Å
α = 112.045 (1)°
β = 105.065 (1)°
γ = 93.154 (1)°
V = 995.23 (12) Å³
Z = 1
Mo Kα radiation
μ = 3.92 mm⁻¹
T = 159 K
0.20 × 0.10 × 0.10 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002 ▶) T _min = 0.631, T _max = 0.676
5083 measured reflections
3502 independent reflections
3162 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.057
S = 1.07
3502 reflections
292 parameters
H-atom parameters constrained
Δρ_max = 0.83 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: CrystalClear (Rigaku, 2002 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ▶) and XP (Siemens, 1994 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811019118/jj2083sup1.cif

e-67-0m796-sup1.cif^{(26.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811019118/jj2083Isup2.hkl

e-67-0m796-Isup2.hkl^{(171.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Dy1—O2	2.280 (3)
Dy1—O2ⁱ	2.374 (2)
Dy1—O1ⁱ	2.394 (3)
Dy1—O4	2.422 (3)
Dy1—O3	2.433 (3)
Dy1—N4	2.461 (3)
Dy1—O6	2.471 (3)
Dy1—N5	2.494 (3)
Dy1—O8	2.530 (3)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9A⋯O3ⁱⁱ	0.84	2.64	3.206 (4)	126
O9—H9A⋯O8ⁱⁱⁱ	0.84	2.24	3.049 (4)	161
N9—H9⋯O9^iv	0.88	1.91	2.751 (4)	160

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

Acknowledgments

Financial support by the NSFC (20761004, 21061009) and the Inner Mongolia Autonomous Region Fund for Natural Science (2010MS0201) is gratefully acknowledged. This work was supported by the "211 project" of the postgraduate student programme of Inner Mongolia University.

supplementary crystallographic information

Comment

Dysprosium complexes continue to attract significant attention because of their potential applications in data storage and processing (Lin et al. 2010). In order to explore the relationship between these applications and their structures, a series of dinuclear dysprosium coordination compounds have been structural characterized (Lin et al. 2008; Xu et al. 2010). In support of our continued research in this area, we report here a new dinuclear dysprosium complex, [Dy₂(C₁₅H₁₂N₃O₂S)₂(NO₃)₄].CH₃OH.

In the title compound the asymmetric unit consists of one Dy^III ion, one deprotonated 2-[(benzothiazol-2-yl)hydrazonomethyl]-6-methoxyphenol ligand and two nitrate ions (Fig. 1). The centrosymmetric dinuclear complex is composed of two nine-coordinate Dy^III ions bridged by phenoxo groups (O2, O2a) from the ligands with a Dy1—O2—Dy1a angle of 106.041 (100) ° and a Dy···Dy distance equal to 3.7184 (3) Å. The central core Dy₂O₂ appears to be nearly rhombic with the two Dy—O2 distances being 2.37 Å and 2.28 Å, respectively. Crystal packing is stabiized by N—H···O hydrogen bonds and weak O—H···O intermolecular interactions forming a two-dimensional network (Fig. 2).

Experimental

A mixture of Dy(NO₃)₃.6H₂O (0.1 mmol), 2-hydrazino benzothiazole (0.1 mmol), 2-hydroxy-3-methoxy-5-((4-methoxyphenyl)diazenyl)benzaldehyde (0.1 mmol), methanol (10 ml), Et₃N (0.3 mmol) was sealed in a glass vessel (20 ml, capacity) and the solution was heated at 363 K for 1 h under autogenous pressure. After the mixture was allowed to cool to room temperature, yellow block single crystals were isolated from the vessel.