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The crystal structure of poly[triaqua-bis(μ3-2,5-dihydroxyterephthalato-κ4O,O′:O′′:O′′′)-(μ4-oxalato-κ4O,O′:O′′,O′′′)cerium(III)], C9H10CeO11

December 2018
Zeitschrift für Kristallographie. New crystal structures 234(2)

December 2018
234(2)

DOI:10.1515/ncrs-2018-0300

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CC BY 4.0

Authors:

C 9 H 10 CeO 11 , triclinic, P 1̄ (no. 2), a = 6.9100(14) Å, b = 9.1700(18) Å, c = 10.720(2) Å, α = 69.53(3)°, β = 83.56(3)°, γ = 87.01(3)°, V = 632.3(2) Å ³ , Z = 2, Rgt ( F ) = 0.0265, wRref ( F² ) = 0.0487, T = 298(2) K.

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Z. Kristallogr. NCS 2019; 234(2): 259–260

Li Xue, Sun Han-Yang, Han Shuang, Wang Jia-Jun, Mao Hao-Yan, Liu Chun-Ling,

Zhang Shou-Cai and Li Chuan-Bi*

The crystal structure of poly[triaqua-bis(µ3-2,5-

dihydroxyterephthalato-κ4O,O′:O′′:O′′′)-(µ4-

oxalato-κ4O,O′:O′′,O′′′)cerium(III)], C9H10CeO11

https://doi.org/10.1515/ncrs-2018-0300

Received August 9, 2018; accepted November 18, 2018; available

online December 15, 2018

Abstract

C9H10CeO11 , triclinic, P¯

1 (no. 2), a=6.9100(14) Å,

b=9.1700(18) Å, c=10.720(2) Å, α=69.53(3)°,β=83.56(3)°,

γ=87.01(3)°,V=632.3(2) Å3,Z=2, Rgt(F)=0.0265,

wRref(F2)=0.0487, T=298(2) K.

CCDC no.: 1859216

The crystal structure is shown in the figure (i=x, y, 1 +z; ii =;

iii =−x, 1 −y, 1 −z). Tables 1 and 2 contain details on crystal

structure and measurement conditions and a list of the atoms

including atomic coordinates and displacement parameters.

*Corresponding author: Li Chuan-Bi, Key Laboratory of Preparation

and Applications of Environental Friendly, Materials (Jilin Normal

University), Ministry of Education, Changchun 130103, P.R. China;

and College of Chemistry, Jilin Normal University, Siping 136000,

P.R. China, e-mail: Chuanbl@jlnu.edu.cn

Li Xue, Sun Han-Yang, Han Shuang, Wang Jia-Jun, Mao Hao-Yan,

Liu Chun-Ling and Zhang Shou-Cai: Key Laboratory of Preparation

and Applications of Environental Friendly, Materials (Jilin Normal

University), Ministry of Education, Changchun 130103, P.R. China;

and College of Chemistry, Jilin Normal University, Siping 136000,

P.R. China

Table 1: Data collection and handling.

Crystal: Block, light pink

Size: 0.18 ×0.11 ×0.06 mm

Wavelength: Mo Kαradiation (0.71073 Å)

µ: 3.66 mm−1

Diractometer, scan mode: Bruker APEX, φand ω-scans

θmax, completeness: 26°,>99%

N(hkl)measured,N(hkl)unique,Rint: 3454, 2440, 0.040

Criterion for Iobs,N(hkl)gt :Iobs >2σ(Iobs), 2158

N(param)rened: 223

Programs: Bruker programs [1], SHELX [2, 3],

DIAMOND [4]

Table 2: Fractional atomic coordinates and isotropic or equivalent

isotropic displacement parameters (Å2).

Atom x y z Uiso*/Ueq

Ce 0.20420(4) 0.22812(3) 0.61969(2) 0.01414(7)

O1 0.1677(5) 0.4292(4) 0.4069(3) 0.0262(8)

O2 0.0915(4) 0.6697(4) 0.2791(3) 0.0224(7)

O3 0.3195(5) 0.1400(3) 0.0870(3) 0.0239(7)

O4 0.1843(5) 0.7626(4) 0.0235(3) 0.0301(8)

O5 0.3346(5) 0.2172(4) −0.1623(3) 0.0293(8)

O6 0.2945(5) 0.4591(4) −0.2940(3) 0.0292(8)

O7 0.2453(4) 0.0484(3) 0.4842(3) 0.0213(7)

O8 0.1077(4) −0.1450(4) 0.4439(3) 0.0281(8)

O9 0.4438(5) −0.0009(4) 0.7025(4) 0.0312(9)

O10 0.5377(6) 0.3029(5) 0.5097(5) 0.0370(10)

O11 0.0440(7) 0.0008(5) 0.8083(5) 0.0450(12)

C1 0.1543(6) 0.5323(5) 0.2948(4) 0.0168(9)

C2 0.2108(6) 0.4928(5) 0.1703(4) 0.0161(9)

C3 0.2176(6) 0.6083(5) 0.0414(4) 0.0168(9)

C4 0.2478(6) 0.3389(5) 0.1817(4) 0.0188(10)

H4 0.246735 0.262881 0.266246 0.023*

C5 0.2861(6) 0.2963(5) 0.0695(4) 0.0177(9)

C6 0.2541(6) 0.5651(5) −0.0705(4) 0.0190(10)

H6 0.256250 0.641202 −0.155075 0.023*

C7 0.2878(6) 0.4103(5) −0.0591(4) 0.0167(9)

C8 0.3103(6) 0.3625(5) −0.1797(4) 0.0197(10)

C9 0.1015(6) −0.0287(5) 0.4802(4) 0.0182(10)

H3 0.335(7) 0.146(6) −0.011(5) 0.050(16)*

H4A 0.165(9) 0.776(7) 0.113(5) 0.08(2)*

H11A −0.053(7) −0.028(6) 0.825(5) 0.026(17)*

H10A 0.647(8) 0.242(7) 0.540(5) 0.050(17)*

H9B 0.516(8) −0.027(6) 0.648(5) 0.047(18)*

H9A 0.501(9) −0.016(8) 0.782(6) 0.08(2)*

H11B 0.104(8) −0.058(7) 0.855(5) 0.043(19)*

H10B 0.559(11) 0.356(8) 0.453(6) 0.08(3)*

260 |Xue et al.: C9H10CeO11

Source of materials

A mixture of Ce2(C2O4)3(54.4 mg, 0.1 mmol), 2,5-

dihydroxyterephthalic acid (DHTA) (39.6 mg, 0.2 mmol) in

1:2 molar ratio was sealed in a 30 mL Teflon-lined stainless

steel containing deionized H2O (20 mL) and methanol (2 mL),

heated at 150 °C for 96 h and cooled down to room temper-

ature. Pink block crystals were isolated and washed with

deionized water.

Experimental details

Hydrogen atoms were placed in their geometrically idealized

positions and constrained to ride on their parent atoms.

Comment

Metal-organic frameworks (MOFs) have received attention

during the last decades not only due to their architectures

and topologies but also for their promising applications

[5–9]. Metal-organic frameworks are built up by lanthanide

metals and poly-functional organicligands forming 1-D chain,

2-D sheet or 3-D networks [10–13]. In this study we employed

cerium ions, with large radii and high coordination numbers,

exo-multidentate ligands like 2,5-dihydroxyterephthalate and

oxalate as the third ligand to hydrothermally synthesize

metal-organic framework compounds with interesting 2-D

structures [13].

The local geometry around Ce is a nine-coordinated

tricapped trigonal prism made up of two oxygen (O7 and

O8ii) from the same carboxylate group attached on an

oxalato ligand, four oxygen (O1, O2iii, O5i, O6i) from the 2,5-

dihydroxyterephthalato ligand, three oxygen (O9, O10, O11)

from three water molecules.

In the [Ce(OA)0.5(DHTA)(H2O)3]n, the oxalic acid

ligands chelate two different cerium ions. The 2,5-

dihydroxyterephthalates act as tetradentate linker to join

three different cerium ions, in which two oxygen atoms (O5

and O6) from a carboxylate group link one Ce3+in chelating

mode, and the O2 link the other Ce3+ions, the O1 also link

the other one Ce3+ions. The Ce3+ions are linked by oxalato

ligands into double metal centers and further joined into 2-D

layers.

Acknowledgements: We thanks the Jilin Province

Science and Technology Development Program of China

(No. 20140204080GX) and the Project of the Education

Department of Jilin Province, China (No. JJKH20180777KJ)

and the Science and Technology Development Projects of

Siping City (No. 2017057) for financial support.

Note: All authors contributed equally to this work.

References

1. Bruker: APEX3, SAINT-Plus, XPREP. Bruker AXS Inc., Madison,

WI, USA (2016).

2. Sheldrick, G. M.: SHELXT – Integrated space-group and

crystal-structure determination. Acta Crystallogr. A71 (2015)

3–8.

3. Sheldrick, G. M.: Crystal structure renement with SHELXL.

Acta Crystallogr. C71 (2015) 3–8.

4. Brandenburg, K.; Putz, H.: DIAMOND, Crystal Impact GbR,

Bonn, Germany (2012).

5. Ohmori, O.; Fujita, M.: Heterogeneous catalysis of a coor-

dination network: cyanosilylation of imines catalyzed by a

Cd(II)-(4,4′-bipyridine) square grid complex. Chem. Commun.

35 (2004) 1586–1587.

6. Zhu, X.; Zheng, H.; Wei, X.: Metal-organic framework (MOF): a

novel sensing platform for biomolecules. Chem. Commun. 49

(2013) 1276–1278.

7. Chandra, D.; Dutta, A.; Bhaumik, A.: A new organic-inorganic

hybrid supermicroporous material having luminescence

and ion-exchange property. Eur. J. Inorg. Chem. 2009 (2009)

4062–4068.

8. Puigmartí-Luis, J.; Rubio-Martínez, M.; Hartfelder, U.: Coordina-

tion polymer nanobers generated by microfluidic synthesis. J.

Am. Chem. Soc. 133 (2011) 4216–4219.

9. Nagarkar, S. S.; Joarder, B.; Chaudhari, A.-K.: Highly selective

detection of nitro explosives by a luminescent metal-organic

framework. Angew. Chem. Int. Ed. 52 (2013) 2881–2885.

10. Ockwig, N. W.; Delgadofriedrichs, O.; O’Keee, M.: Reticular

chemistry: occurrence and taxonomy of nets and grammar

for the design of frameworks. Acc. Chem. Res. 38 (2005)

176–82.

11. Wang, C. C.: Hydrothermal synthesis and crystal structure of

two novel lanthanide MOF compounds with one-dimensional

water chains. Chin. J. Inorg. Chem. 26 (2010) 1583–1589.

12. Wanga, C.; Wanga, Z.; Gua, F.: Five novel metal–organic frame-

work constructed by lanthanide metals and 2,2′-bipyridine-6,

6′-dicarboxylate: Hydrothermal synthesis, crystal structure,

and thermal properties. J. Mol. Struct. 979 (2010) 92–100.

13. Wang, C. C.; Wang, P.: A novel cerium metal-organic framework

constructed from tri-ligand: hydrothermal synthesis and crystal

structure. Asian J. Chem. 24 (2012) 425–427.

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