Home Crystal structure of poly[tetraaqua-(μ4-oxalato-κ4O,O′:O′′,O′′′)-(μ8-benzene-1,2,4,5-tetracarboxylato-κ8O1:O2:O3:O4:O5:O6:O7:O8)yttrium(III)], C6H5O8Y
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Crystal structure of poly[tetraaqua-(μ4-oxalato-κ4O,O′:O′′,O′′′)-(μ8-benzene-1,2,4,5-tetracarboxylato-κ8O1:O2:O3:O4:O5:O6:O7:O8)yttrium(III)], C6H5O8Y

  • Zhi-Hui Wen EMAIL logo , Xiao-Xi Zhao and Dan Zhao
Published/Copyright: May 22, 2018

Abstract

C6H5O8Y, triclinic, P1̄ (no. 2), a = 6.2090(17) Å, b = 8.573(4) Å, c = 8.863(2) Å, α = 111.018(6)°, β = 109.850(4)°, γ = 91.866(6)°, V = 407.8(2) Å3, Z = 2, Rgt(F) = 0.0435, wRref(F2) = 0.1332, T = 296(2) K.

CCDC no.: 1817313

The crystal structure is shown in the figure. Tables 1 and 2 contain details on crystal structure and measurement conditions and a list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Colorless block
Size:0.20 × 0.15 × 0.15 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:7.18 mm−1
Diffractometer, scan mode:Bruker APEX-II, ω-scans
θmax, completeness:28.2°, >92% (up to 25.2°, 99%)
N(hkl)measured, N(hkl)unique, Rint:2579, 1846, 0.021
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 1594
N(param)refined:137
Programs:Bruker programs [11], SHELX [12]
Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

AtomxyzUiso*/Ueq
Y1−1.18996(9)0.35228(7)−0.81616(7)0.0106(2)
C1−0.3644(13)0.9862(9)−0.5977(9)0.0263(14)
H1−0.2745670.977428−0.6646760.032*
C2−0.5079(12)0.8424(9)−0.6264(9)0.0242(14)
C3−0.6474(12)0.8567(9)−0.5293(9)0.0239(14)
C4−0.8150(12)0.7052(9)−0.5612(9)0.0250(14)
C5−0.5006(11)0.6737(8)−0.7612(8)0.0218(13)
C6−1.3928(13)−0.0381(9)−1.0120(9)0.0269(15)
O1−0.8143(10)0.6751(7)−0.4332(7)0.0357(13)
O2−0.9474(9)0.6188(7)−0.7160(7)0.0343(12)
O3−0.5788(10)0.6528(8)−0.9171(7)0.0386(13)
O4−0.4014(9)0.5687(7)−0.7024(7)0.0317(12)
O5−1.2015(9)0.0589(7)−0.9381(8)0.0381(13)
O6−1.4317(10)−0.1955(7)−1.1041(7)0.0360(13)
O7−0.8120(9)0.3090(8)−0.6656(7)0.0390(13)
O8−0.9711(10)0.3167(8)−0.9924(7)0.0396(14)
H8A−1.0308430.328902−1.1026520.047*
H8B−0.8154730.295872−0.9423320.047*
H7B−0.7146030.374022−0.5439620.047*
H7A−0.6828130.311102−0.6975230.047*

Source of material

A mixture of benzenetetracarboxylic acid (H4btec, 0.10 g), oxalic acid (H2C2O4, 0.05 g), Y(NO3)3⋅6H2O (0.05 g), KOH (0.15 g) and deionized water (10 mL) was placed in a 30-mL Teflon-lined stainless steel autoclave. Then the autoclave was sealed, heated to 180 °C under autogenous pressure for 48 h. After slowly cooling to room temperature at a rate of 5 °C/h, a few colorless block shaped crystals were recovered by filtration, washed by distilled water, and air dried.

Experimental details

H atoms were located in difference Fourier maps, and then refined with a riding model, with Uiso(H) = 1.2Ueq(O).

Discussion

Coordination polymers have caught much attention in the field of crystal engineering due to the fascinating structures and potential applications in fluorescence, magnetism especially those of rare earth elements [1, 2] . It is well known that the organic ligand is a key factor that affects the crystal structures as well as physical properties. Among various ligands, 1,2,4,5-benzenetetracarboxylate has been widely used in constructing metal coordination polymers due to its multi-connectivity, i.e. from two to eight carboxylate oxygen atoms which can bridge metal ions to create chains, layers, and 3D networks [3], [4], [5], [6]. On the other hand, the oxalate anion is also an attractive small auxiliary ligand, which may construct many structures with H4btec liand and metal ions [7], [8]. Hou et al. [9] reported a series of compounds associating with Ln3+ ions, btec4− ligands and C2O42− ligands for Ln = Eu, Tb, Dy and Ho. In this study, we provide a isostructural compound C6H5O8Y by a self-assembly process through simple mixing of the starting reagents.

Single crystal X-ray diffraction (SC-XRD) analysis reveals that the title compound exhibits a three–dimensional framework in the triclinic space group P1̄. There is one unique Y3+ ion, a half btec4− ligand, half C2O42− ligand, and two coordinated aqua in the asymmetric unit. Each Y3+ is surrounded by eight O atoms. In this group, four O atoms come from carboxylate groups from four different btec4− ligands, two O atoms belongs to a two carboxylate groups of one C2O42− ligand, and two O atoms are coordinated water molecules. The Y—O bond distances fall in the range of 2.296(5)–2.429(5) Å, which is the common value comparing with other Y3+ compounds [10]. Moreover, the rationality of eight Y—O bonds can be evaluated by bond valance sum (BVS) calculation. The calculated BVS for Y3+ is 3.190, very close to 3. The four carboxylate groups of btec ligand are completely deprotonated, and each carboxylate connects with two Y3+ ions via μ2-mode. For each C2O42− ligand, it connects to two Y3+ ions via μ2-bridging mode.

Acknowledgements

This work was supported by the Science and Technology Research Project of Henan Province (No. 172102310678), and the Key research project of Henan Province Office of Education (No. 17A150013).

References

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Received: 2018-01-30
Accepted: 2018-05-03
Published Online: 2018-05-22
Published in Print: 2018-07-26

©2018 Zhi-Hui Wen et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 License.

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