A novel three-dimensional metal-organic interpenetrating framework constructed from mixed adipate and 4,4′-bipy ligands: [Co(OOC(CH 2)4COO)(4,4′-bipy)] (adipate = HOOC(CH 2)4COOH, 4,4′-bipy = 4,4′-bipyridine)

Article abstract of DOI:10.1016/j.inoche.2004.02.006

A novel metal-organic hybrid compound [Co(OOC(CH₂) ₄COO)(4,4^′-bipy)] 1, has been hydrothermally synthesized and structurally characterized. Compound 1 exhibits a novel three-dimensional interpenetrating network with mixed adipate and 4,4 ^′-bipy ligands constructed by covalent bonds.

Full text of DOI:10.1016/j.inoche.2004.02.006

Inorganic Chemistry Communications 7 (2004) 510–512
www.elsevier.com/locate/inoche
A novel three-dimensional metal-organic interpenetrating
framework constructed from mixed adipate and 4,40-bipy
ligands: [Co(OOC(CH2)4COO)(4,40-bipy)]
(adipate ¼ HOOC(CH2)4COOH, 4,40-bipy ¼ 4,40-bipyridine) q
*
Na Hao, Enhong Shen, Yangguang Li, Enbo Wang , Changwen Hu, Lin Xu
Institute of Polyoxometalate Chemistry, Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, P.R. China
Received 12 November 2003; accepted 7 February 2004
Published online: 4 March 2004
Abstract
A novel metal-organic hybrid compound [Co(OOC(CH2)4COO)(4,40-bipy)] 1, has been hydrothermally synthesized and struc-
turally characterized. Compound 1 exhibits a novel three-dimensional interpenetrating network with mixed adipate and 4,40-bipy
ligands constructed by covalent bonds.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Hydrothermal synthesis; Interpenetration; Metal-organic; Crystal structure
The investigation of novel metal-organic hybrid
compounds have attracted considerable interest and
importance in recent years, not only due to their in-
triguing structural motifs but also their potential appli-
cations in catalysis, medicine, host-guest chemistry and
the promising photo-, electro- and magnetic materials
[1–5]. In the various metal-organic frameworks, the en-
tangled structure, in which two or more infinite net-
works interpenetrate each other has been widely
researched [6]. In general, there are two important fac-
tors for the formation of interpenetrating structures: one
is that infinite networks contain large pores or cavities
for interpenetration; the other is that the individual two-
dimensional networks should possess some appropriate
elements of corrugation or undulation [7]. In this aspect,
organic aromatic polycarboxylate ligands have been
widely used in constructing such compounds [8]. How-
ever, complexes based on dicarboxylate ligand adipate
have rarely reported hitherto, especially in the respect of
the interpenetrating frameworks [9]. More recently, ad-
ipate has proved to be a good candidate for assembling
high dimensional metal-organic architectures owing to
its three interesting structural features. In the first place,
it contains two bridging moieties, which leads to a va-
riety of connection modes with transitional metal cen-
ters and provides abundant structural motifs. Also, it
can act not only as hydrogen bond donors but as ac-
ceptors. At last, it has six carbon atoms which may
construct high dimension and pore structures. On the
other hand, so far most of the high dimensional net-
works are not purely bridged by one ligand. They usu-
ally employ two or more ligands in the construction of
metal-organic complexes. It is noteworthy that 4,40-bi-
pyridine is an excellent rigid bridging ligand for the
construction of novel metal-organic hybrid compounds
due to its various coordinative modes with metal ions
[10]. To date, there have been a lot of reports on various
dimensional hybrid compounds assembled by 4,40-bipy
ligands [11]. Based on the above opinions, a motivation
for design and synthesis of novel metal-organic inter-
penetrating frameworks containing adipate and 4,40-
bipy ligands under hydrothermal conditions has been
q Supplementary data associated with this article can be found, in the
online version, at doi:10.1016/j.inoche.2004.02.006.
* Corresponding author. Tel.: +86-431-5268787; fax: +86-431-
5684009.
E-mail address: wangenbo@public.cc.jl.cn (E. Wang).
1387-7003/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2004.02.006

N. Hao et al. / Inorganic Chemistry Communications 7 (2004) 510–512
511
raised. In this communication, we report the hydro-
thermal synthesis and structural characterization of
[Co(OOC(CH2)4COO)(4,40-bipy)] 1, which exhibits a
novel three-dimensional interpenetrating network con-
structed by covalent bonds. To the best of our knowl-
edge, 1 represents the first metal-organic interpenetrated
framework composed of mixed adipate and rigid 4,40-
bipy ligands.
Compound 1 was prepared from a mixture of
Co(NO3)2 ꢀ 2H2O, adipate, 4,40-bipy, and H2O with the
molar ratio of 1:1:0.3:444, stirred for 1 h, sealed in a 15
ml Teflon-lined stainless steel bomb, and kept at 160 °C
under autogenous pressure for 4 days [12].
The X-ray diffraction analysis [13,14] reveals that
compound 1 exhibits a novel three-dimensional metal-
organic interpenetrating framework based on dinuclear
cobalt dimer building blocks with mixed adipate and
4,40-bipy ligands. The fundamental unit is shown in
Fig. 1. There is one crystallographically unique Co
center in the symmetric unit. The Co(1) center coordi-
nates to two oxygen atoms of one chelating bidentate
adipate anion ligand and two oxygen atoms from dif-
ferent bridging bidentate adipate anions ligands, two
nitrogen atoms (Co(1)–N(1) 2.169(2) and Co(1)–N(2)
Fig. 2. Polyhedral representation of the three-dimensional metal-
organic framework of compound 1. The light and dark colors repre-
sent two interpenetrating layers with different extending directions,
respectively.
0
ꢀ
2.160(2) A) of two different 4,4 -bipy ligands. Four dif-
ferent carboxylate groups with Co(1)–OðcarboxylÞ dis-
tances in the range 2.021(2)–2.195(2) A. The O–Co(1)–O
connected with two Co centers by covalent bonds to
form two-dimensional grid-like network with large
pores parallel to the [0 1 1] direction. The size of the
ꢀ
2
ꢀ
bond angles vary from 59.59(8) to 151.58(9)°. Therefore,
Co center displays a distorted octahedral coordination
geometry. The two {CoN2O4} octahedra are connected
together to form a linear binuclear Co dimer via the
edge-sharing mode. In addition, four carboxylate groups
of the adipate anions ligand exhibit two kinds of coor-
dination modes with Co centers. That is, two carbox-
ylate groups act as a bidentate ligand to bridge two Co
centers, while the other two exhibit chelating mode to
link with two Co centers. Thus, four adipate ligands are
cavities is about 13.148 ꢁ 10.888 A , as shown in
Fig. S3. The most important structural feature of 1 is
that two such individual two-dimensional grid-like net-
works are interconnected by 4,40-bipy ligands each other
to form an interesting three-dimensional twofold inter-
penetrating framework, illustrated in Fig. 2. To the best
of our knowledge, it is the first interpenetrating com-
posite network has hitherto been observed with mixed
adipate and 4,40-bipy ligands. It is noteworthy that both
the individual two-dimensional grid-like network and
twofold interpenetration of such three-dimensional
framework provide the feasibility to the assembly of
interpenetrating architectures. The bond valence calcu-
lations (Co, 1.90) suggest Co atom is in the +2 oxidation
state. The O(1)–O(4) have bond valence sums of 1.70,
1.70, 1.86, and 1.85, respectively, [15]. These results in-
dicate that all the oxygen atoms of adipate groups are
deprotonated [16]. These results are consistent with the
charge balance considerations of compound 1.
In this communication, we report a novel metal-
organic hybrid compound [Co(OOC(CH2)4COO)(4,40-
bipy)] 1 which features an interesting interpenetrated
framework by covalent bonds.
Supplementary materials
Crystal data and structure refinement, atomic coor-
dinates, bond lengths and angles, anisotropic displace-
Fig. 1. The ORTEP drawing of 1 showing the local coordination en-
vironment of Co(II). Hydrogen atoms are omitted for clarity.

512
N. Hao et al. / Inorganic Chemistry Communications 7 (2004) 510–512
ment parameters, the IR spectrum, the TG curve and
TG analysis, and packing diagram of individual two-
dimensional-like network of compound 1 were available
from the authors on request. CCDC reference number:
221497.
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