INORGANIC AND NANO-METAL CHEMISTRY
2017, VOL. 47, NO. 1, 153–157
A new heterometallic coordination polymer: Synthesis, structure, and
catalytic property
Qi-Feng Liua, Wei Liub, Yi-Po Caoc, Yan-Li Donga, and Hui-Min Liua
aCollege of Sciences, Agricultural University of Hebei, Baoding, P. R. China; bDepartment of Basic Medcine, logistics University of CAPF, Tianjin,
P. R. China; cTianjin Provincal Corps Hospital of Chinese People’s Armed Police Force, Tianjin, P. R. China
ABSTRACT
ARTICLE HISTORY
Received 28 December 2015
Accepted 21 February 2016
A new heterometallic-organic framework, namely [CuCa(tdc)2(DMF)]n (1 H2tdc D 2,5-thiophenedicarboxylic
acid, DMF D N,N’-dimethylformamide), has been successfully obtained through the solvothermal reactions
of CuCl2, Ca(NO3)2, and H2tdc. Single-crystal structural analysis reveals that compound 1 features a 3D
framework with the irl topology. Compound 1 has potential unsaturated metal sites after the removal of
the coordinated DMF molecules, so it exhibits excellent catalytic activity for the diethylzinc addition to
benzaldehyde.
KEYWORDS
Catalytic property;
heterometallic compound;
solvothermal reaction;
topology
Introduction
Oxford Xcalibur E diffractometer with ꢀgraphite-monochro-
mated Mo-Ka radiation (λ D 0.71073 A). Elemental analy-
ses (C, H, and N) were performed on an EA1110 CHNS-0
CE Elemental Analyzer. Powder X-ray diffraction (PXRD)
analyses were recorded on a Rigaku Dmaꢀx2500 diffractome-
ter with Cu-Ka radiation (λ D 1.54056 A) with a step size
of 0.05ꢀ. Thermogravimetric analyses were carried out on a
NetzschSTA499C integration thermal analyzer under a
nitrogen atmosphere from 30 to 800ꢀC at a heating rate of
10ꢀC/min.
Metal-organic frameworks (MOFs) have attracted much attention
of scientists, owing to not only their impressive structural diversity
but also their potential applications as functional materials in the
fields of luminescence, gas storage/separation, magnetism, and
heterogeneous catalysis.[1–5] Because the well-known HKUST-1
and MIL-101 have been successfully applied to catalyze the cyano-
silylation of benzaldehyde,[6,7] MOF-based catalysis has become a
research hotspot in recent years. According to previously reported
documents, MOFs materials as catalysts must have accessible
active metal centers in the structures.[8,9] Therefore, how to con-
struct MOFs with appropriate active metal centers is extremely
important. An effective method is to construct inorganic building
blocks with terminal coordinated solvent molecules, the removal
of which will generate coordinatively unsaturated metal sites.
Although a lot of MOFs have been successfully applied to catalyze
frameworks as heterogeneous catalysts are rarely reported.[13,14]
Based on these considerations, we successfully constructed a new
heterometallic-organic framework, namely [CuCa(tdc)2(DMF)2]n
(1 H2tdc D 2,5-thiophenedicarboxylic acid, DMF D N,N’-
dimethylformamide). In this work, we will report the synthesis,
structure, and catalytic property of this compound.
Synthesis of [CuCa(tdc)2(DMF)2]n
A mixture of CuCl2ꢁ2H2O (0.018 g, 0.1 mmol), Ca
(NO3)2ꢁ4H2O (0.024 g, 0.1 mmol), H2tdc (0.034 g,
0.2 mmol), DMF (2 mL), and CH3OH (2 mL) was placed
in a 20 mL small vial. Then the mixture was heated to
70ꢀC. The temperature was held for 60 h, then the vessel
was cooled to room temperature over 30 min, leading to
the formation of green crystals of 1 (yield: 35% based on
H2tdc). Anal. Calcd. for 1, C18H16N2O10S2CuCa: C, 36.73;
H, 2.72; N, 4.76%. Found: C, 36.73; H, 2.74, N, 4.73%. IR
(cm¡1): 3421(w), 1715(m), 1678(s), 1584(m), 1479(m), 1382
(m), 1373(m), 1109(w), 1021(w), 957(m), 892(m), 815(m),
778(w), 690(w).
Experimental
X-ray crystallography
Materials and methods
The X-ray single crystal structure analysis of 1 was per-
All chemicals were purchased commercially and used with- formed on an Oxford Xcalibur E diffractometer (Mo-Ka
ꢀ
out further purification. X-ray intensities were collected on radiation, λ D 0.71073 A, graphite monochromator) at 293
CONTACT Hui-Min Liu
College of Sciences, Agricultural University of Hebei, Baoding 071001, P. R. China.
CCDC No. 991738 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via
Cambridge CB2 1EZ, UK. Fax:C44 1223336033.
© 2017 Taylor & Francis Group, LLC
Liu, Qi-Feng
