Bis(μ-adamantane-1,3-dicarboxyl­ato-κ4 O 1,O 1′:O 3,O 3′)bis­[aqua­(3-carboxy­adam­antane-1-carboxyl­ato-κO 1)(1,10-phen­an­throline-κ2 N,N′)erbium(III)] dihydrate

Hong-lin Zhu; Wen-xiang Huang; Hai-sheng Chang

doi:10.1107/S1600536811023075

. 2011 Jun 22;67(Pt 7):m959. doi: 10.1107/S1600536811023075

Bis(μ-adamantane-1,3-dicarboxylato-κ⁴ O ¹,O ^1′:O ³,O ^3′)bis[aqua(3-carboxyadamantane-1-carboxylato-κO ¹)(1,10-phenanthroline-κ² N,N′)erbium(III)] dihydrate

Hong-lin Zhu ^a,^*, Wen-xiang Huang ^a, Hai-sheng Chang ^a

PMCID: PMC3152128 PMID: 21836937

Abstract

The asymmetric unit of the binuclear centrosymmetric title compound, [Er₂(C₁₂H₁₄O₄)₂(C₁₂H₁₅O₄)₂(C₁₂H₈N₂)₂(H₂O)₂]·2H₂O, contains one Er^III atom, one coordinated water molecule, one 1,10-phenanthroline (phen) ligand, two differently coordinated adamantane-1,3-dicarboxylate (H₂L) ligands and one lattice water molecule. The Er^III ion is eight-coordinated by four O atoms from bridging L ²⁻, one O atom from HL ⁻, one O atom from the coordinated water and two N atoms from a phen ligand. Extensive O—H⋯O hydrogen-bonding interactions result in the formation of chains which are further linked into a layer-like network by π–π stacking interactions centroid–centroid distance = 3.611 (3) Å] between adjacent phen ligands belonging to neighbouring chains. The carboxy group of the HL ⁻ ligand is equally disordered over two positions.

Related literature

For 1,3-adamantanedicarboxylic acid, see: Glidewell & Ferguson (1996 ▶). For lanthanide 1,3-adamantanedicarboxylate complexes, see: Millange et al. (2004 ▶); Li et al. (2009 ▶).

Experimental

Crystal data

[Er₂(C₁₂H₁₄O₄)₂(C₁₂H₁₅O₄)₂(C₁₂H₈N₂)₂(H₂O)₂]·2H₂O
M _r = 1657.94
Triclinic,
a = 8.6164 (17) Å
b = 13.579 (3) Å
c = 14.560 (3) Å
α = 94.53 (3)°
β = 96.36 (3)°
γ = 92.22 (3)°
V = 1685.8 (6) Å³
Z = 1
Mo Kα radiation
μ = 2.55 mm⁻¹
T = 293 K
0.34 × 0.17 × 0.09 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.600, T _max = 0.795
16743 measured reflections
7645 independent reflections
6761 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.067
S = 1.07
7645 reflections
448 parameters
H-atom parameters constrained
Δρ_max = 0.77 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811023075/jh2296sup1.cif

e-67-0m959-sup1.cif^{(29.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811023075/jh2296Isup2.hkl

e-67-0m959-Isup2.hkl^{(374KB, 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
O9—H91⋯O10	0.85	1.74	2.558 (4)	161.1
O9—H92⋯O1ⁱ	0.86	1.92	2.760 (4)	166.7
O10—H101⋯O6	0.85	1.87	2.653 (4)	153.6
O10—H102⋯O4ⁱ	0.85	1.87	2.692 (4)	161.8

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Symmetry code: (i) Inline graphic .

Acknowledgments

This project was supported by the Scientific Research Fund of Zhejiang Provincial Education Department (grant No. Y201017782). Sincere thanks are also extended to the K. C. Wong Magna Fund in Ningbo University.

supplementary crystallographic information

Comment

As known, lanthanide ions have high affinity for hard donor atoms, and ligands with oxygen or hybrid oxygen-nitrogen atoms, especially multicarboxylate ligands are usually employed in construction for lanthanide complexes (Li et al., 2009). Herein, we report the crystal structure of title compound, [Er(phen)(H₂O)(HL)L]₂.2H₂O, which consist of 1,3-adamantanedicarboxylic acid (H₂L), 1,10-phenanthroline and ErCl₃.nH₂O. This structure indicates that hydrogen-bond and π–π interaction are responsible for supramolecular assemblies.

The asymmetric unit contains one Er^III, one coordination water, two type of 1,3-adamantanedicarboxylate ligands and one lattic water. As show in Fig.1, the Er^III ion is in a eight coordinated fashion by four oxygen atoms from L^2-, one oxygen from HL^1-, one oxygen from a coordination water and two nitrogen atoms from a 1,10-phenanthroline ligand. Three type kinds of hydrogen-bond are observed in title compound (Table 2). The presence of the extensive hydrogen-bond interaction results in formation of one-dimensional chains, which further grow into two-dimensional layer-like network by π–π stacking interaction between adjacent phen ligands belonging to neighboring chains (Fig. 2).

Experimental

Pink powder of ErCl₃.nH₂O was obtained by slow evaporation of a solution of Er₂O₃ (0.150 mmol, 0.0574 g) dissolved in HCl (5 ml) under water boiling condition. A mixture of 1,3-adamantanedicarboxylic acid (0.300 mmol, 0.0595 g) in water (10 ml) was stirred for 30 min, and sealed in a 23 ml Teflon-lined stainless autoclave, which was heated at 170°C for three days and thereafter cooled slowly to room temperature, and pink crystals were separated by filtering and washing.