Poly[aqua(μ2-benzene-1,4-di-car-box-yl-ato) (μ2-4,4′-bipyridine N,N′-dioxide)cadmium(II)], a threefold inter-penetrating diamond net

Article abstract of DOI:10.1107/S0108270110023553

In the title compound, [Cd(C₈H₄O₄)(C ₁₀H₈N₂O₂)(H₂O)] n , (I), each Cd^II atom is seven-coordinated in a distorted monocapped trigonal prismatic coordination geometry, sur-rounded by four carboxyl-ate O atoms from two different benzene-1,4-dicarboxyl-ate (1,4-bdc) anions, two O atoms from two distinct 4,4′-bipyridine N,N′-dioxide (bpdo) ligands and one water O atom. The Cd^II atom and the water O atom are on a twofold rotation axis. The bpdo and 1,4-bdc ligands are on centers of inversion. Each crystallographically unique Cd^II center is bridged by the 1,4-bdc dianions and bpdo ligands to give a three-dimensional diamond framework containing large adamantanoid cages. Three identical such nets are inter-locked with each other, thus directly leading to the formation of a threefold inter-penetrated three-dimensional diamond architecture. To the best of our knowledge, (I) is the first example of a threefold inter-penetrating diamond net based on both bpdo and carboxyl-ate ligands. There are strong linear O - H...O hydrogen bonds between the water mol-ecules and carboxyl-ate O atoms within different diamond nets. Each diamond net is hydrogen bonded to its two neighbors through these hydrogen bonds, which further consolidates the threefold inter-penetrating diamond framework.

Full text of DOI:10.1107/S0108270110023553

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
chosen. It is well known that careful selection of a suitable
organic ligand with certain features is helpful for constructing
MOFs with desirable properties (Wang et al., 2006). Recently,
it has been demonstrated that 4,40-bipyridine N,N0-dioxide
(bpdo) and its derivatives show some unique features in the
construction of MOFs (Hill et al., 2005; Manna et al., 2007) and
they have been shown to have extremely versatile coordina-
tion modes compared with 4,40-bipyridine and its derivatives
(Xu et al., 2005). To date, a number of MOFs based on bpdo
ligands have been reported, including one-dimensional chain
or ladder, two-dimensional layer, and unusual five-, six-,
seven- and eight-connected frameworks (Hill et al., 2005).
However, only a few MOFs based on both bpdo and
carboxylate ligands have been documented (Manna et al.,
2006, 2007; Fabelo et al., 2007). In the new structure reported
here, bpdo assembles with cadmium benzene-1,4-dicarboxyl-
ate (1,4-bdc) to furnish a 1:1 adduct, viz. [Cd(1,4-bdc)-
(bpdo)(H2O)]n, (I), which exists as an unusual threefold
interpenetrating diamond framework.
ISSN 0108-2701
Poly[aqua(l2-benzene-1,4-dicarboxyl-
ato)(l2-4,40-bipyridine N,N0-dioxide)-
cadmium(II)], a threefold inter-
penetrating diamond net
Guohai Xu and Yongrong Xie*
Key Laboratory of Jiangxi University for Functional Materials Chemistry, Department
of Chemistry and Life Science, Gannan Normal University, Ganzhou, Jiangxi
341000, People’s Republic of China
Correspondence e-mail: xieyr@gnnu.edu.cn
Received 11 April 2010
Accepted 17 June 2010
Online 7 July 2010
In the title compound, [Cd(C8H4O4)(C10H8N2O2)(H2O)]n, (I),
each CdII atom is seven-coordinated in a distorted mono-
capped trigonal prismatic coordination geometry, surrounded
by four carboxylate O atoms from two different benzene-1,4-
dicarboxylate (1,4-bdc) anions, two O atoms from two distinct
4,40-bipyridine N,N0-dioxide (bpdo) ligands and one water O
atom. The CdII atom and the water O atom are on a twofold
rotation axis. The bpdo and 1,4-bdc ligands are on centers of
inversion. Each crystallographically unique CdII center is
bridged by the 1,4-bdc dianions and bpdo ligands to give a
three-dimensional diamond framework containing large
adamantanoid cages. Three identical such nets are interlocked
with each other, thus directly leading to the formation of a
threefold interpenetrated three-dimensional diamond archi-
tecture. To the best of our knowledge, (I) is the first example
of a threefold interpenetrating diamond net based on both
bpdo and carboxylate ligands. There are strong linear O—
Hꢀ ꢀ ꢀO hydrogen bonds between the water molecules and
carboxylate O atoms within different diamond nets. Each
diamond net is hydrogen bonded to its two neighbors through
these hydrogen bonds, which further consolidates the three-
fold interpenetrating diamond framework.
The asymmetric unit of (I) contains half a CdII atom, half a
bpdo ligand, half a 1,4-bdc anion and half a coordination water
molecule (Fig. 1). The CdII atom and the water O atom rest on
a twofold rotation axis. The bpdo and 1,4-bdc ligands are on
centers of inversion that occur at the mid-point of the C7—C7ii
bond of bpdo [symmetry code: (ii) ꢁx, ꢁy, ꢁz] and the
centroid of the arene ring of 1,4-bdc. Each CdII atom is seven-
coordinated in a distorted monocapped trigonal prismatic
coordination geometry, surrounded by four carboxylate O
atoms from two different 1,4-bdc anions [O2, O3, O2iii and
iii
1
O3 ; symmetry code: (iii) 1 ꢁ x, y, ꢁ z], two O atoms from
2
two distinct bpdo ligands (O1 and O1iii) and one water O atom
(O1W). The Cd—Ocarboxylate distances (Table 1) are compar-
able to those observed for [Cd4(bpea)4(1,4-bix)4]ꢀ4H2O [1,4-
bix is 1,4-bis(imidazol-1-ylmethyl)benzene and H2bpea is 4,40-
ethylenedibenzoic acid] (Yang et al., 2008). Each crystal-
lographically unique CdII center is bridged by the 1,4-bdc
dianions and bpdo ligands to give a three-dimensional
framework (Fig. 2). A better insight into the structure of (I)
can be achieved by the application of a topological approach,
that is, reducing multidimensional structures to simple node-
and-linker nets (Batten & Robson, 1998). According to the
simplification principle, the CdII center is defined as a four-
connected node, while the 1,4-bdc and bpdo ligands serve as
linkers. Therefore, on the basis of this concept of chemical
topology, the overall structure is a diamond framework
Comment
The synthesis of metal–organic frameworks (MOFs) has
attracted much attention, not only because of the tremendous
number of potential applications of MOFs in nonlinear optics,
catalysis, gas absorption, luminescence, magnetism, ion
exchange and zeolite-like materials for molecular selection,
but also because of the intriguing variety of architectures and
topologies (Abrahams et al., 1999; Noro et al., 2000; Spencer et
al., 2006). The topologies of MOFs can often be controlled and
modified by selecting the coordination geometry preferred by
the metal ion and the chemical structure of the organic ligand
Acta Cryst. (2010). C66, m201–m203
doi:10.1107/S0108270110023553
# 2010 International Union of Crystallography m201

metal-organic compounds
Figure 2
A view of the diamond framework of (I) (the central CdII atom and its
four neighbors are shown in pink in the electronic version of the paper).
Figure 1
A view of the local coordination of the CdII atom in (I), showing the
atom-numbering scheme. Displacement ellipsoids are drawn at the 30%
probability level. [Symmetry codes: (i) 12 ꢁ x, 21 ꢁ y, 1 ꢁ z; (ii) ꢁx, ꢁy, ꢁz;
1
2
(iii) 1 ꢁ x, y, ꢁ z.]
containing large adamantanoid cages (Fig. 2). As can be seen,
each distorted rectangular ring has six CdII centers, leading to
the formation of a hexagon which is the shortest circuit here.
In the adamantanoid cage, the Cdꢀ ꢀ ꢀCd distances bridged by
Figure 3
A view of the threefold interpenetrating three-dimensional diamond net
of (I) (the hydrogen-bonding interactions are shown as dashed lines).
˚
bpdo and 1,4-bdc are 12.624 (5) and 11.245 (4) A, respectively.
(CH3OH)(NO3)3] and [Cu(3,40-bpdc)(H2O)]ꢀDMFꢀ2H2O, whose
threefold interpenetrating diamond nets only contain single
organic ligands. In particular, [Tb(NO3)3(bpdo)(CH3OH)]
adopts a zigzag chain structure, which forms threefold inter-
penetrating diamond frameworks through interchain
hydrogen bonding between coordinated methanol and a
nitrate group on an adjacent chain. Although the reported
compound Co(d-cam)(TMDPy)ꢀ2H2O is constructed by
mixed organic ligands, it exhibits a homochiral threefold
interpenetrating diamond topology. Notably, there are only a
few previously reported examples of MOFs based on bpdo–
carboxylate mixed ligand systems (Manna et al., 2006, 2007;
Fabelo et al., 2007). The related compounds [Co(H2O)6]-
(H2bta)ꢀbpdoꢀ4H2O and {[Co2(bpdo)(H2O)4]2(bta)}ꢀ4H2O are
discrete molecular complexes (H4bta is benzene-1,2,4,5-
tetracarboxylic acid; Fabelo et al., 2007). The structure of
[Co(H2bta)(bpdo)2(H2O)2]n is constituted by uniform chains
of CoII ions bridged by the dianionic H2bta2ꢁ species (Fabelo
et al., 2007). The related compounds [Co(bta)1/2(bpdo)-
(H2O)3]n, {[Co(ox)(bpdo)]}n and [Mn(ox)(bpdo)]n display
two-dimensional layer structures (ox is the oxalate dianion;
Manna et al., 2006, 2007; Fabelo et al., 2007).
It is well known that diamond networks tend to inter-
penetrate to fill the voids within a single net. Of particular
interest, the most striking feature of (I) is that three identical
three-dimensional single nets are interlocked with each other,
thus directly leading to the formation of a threefold inter-
penetrated three-dimensional diamond architecture (Fig. 3).
In addition, there are strong linear O—Hꢀ ꢀ ꢀO hydrogen bonds
between the water molecules and carboxylate O atoms within
different diamond nets (Fig. 3). Each diamond net is hydrogen
bonded to its two neighbors through these hydrogen bonds,
which further consolidates the threefold interpenetrating
diamond framework (Table 2).
Although many diamond-related nets displaying various
interpenetration modes ranging from twofold to 11-fold have
been reported, threefold interpenetrating MOFs in the
presence of mixed organic ligands with different lengths is
relatively rare (Batten, 2001; O’Keeffe et al., 2008; Carlucci et
al., 2003). So far, only a few threefold interpenetrating MOFs,
including [Co(d-cam)(TMDPy)]ꢀ2H2O (d-H2Cam is d-cam-
phoric acid and TMDPy is 4,40-trimethylenedipyridine; Zhang
et al., 2008), [Cu2(bpy)2(Hbpy)(H2O)][PW12O40] (bpy is 4,40-
bipyridine; Yang et al., 2009), [Tb(NO3)3(bpdo)(CH3OH)]
(Long et al., 2002) and [Cu(3,40-bpdc)(H2O)]ꢀDMFꢀ2H2O
(3,40-bpdc is biphenyl-3,40-dicarboxylate and DMF is di-
methylformamide) (Feng et al., 2009), have been reported.
The structure of (I) is entirely different from that of the
related structure [Cu2(bpy)2(Hbpy)(H2O)][PW12O40], which
shows an unprecedented threefold interpenetrating diamond-
like network in polyoxometalate chemistry. The structure of
(I) is also different from those of the polymers [Tb(bpdo)-
Experimental
A mixture of CdCl2ꢀ2.5H2O (0.5 mmol), 1,4-H2bdc (0.5 mmol) and
bpdo (0.5 mmol) was dissolved in N,N-dimethylformamide (10 ml).
The resulting solution was stirred for about 1 h at room temperature,
sealed in a 23 ml Teflon-lined stainless steel autoclave and heated at
393 K for 1 d under autogenous pressure. The reaction system was
then cooled slowly to room temperature. Block-shaped crystals of (I)
ꢂ
m202 Xu and Xie [Cd(C8H4O4)(C10H8N2O2)(H2O)]
Acta Cryst. (2010). C66, m201–m203

metal-organic compounds
suitable for single-crystal X-ray diffraction analysis were collected
from the final reaction system by filtration, washed several times with
distilled water and dried in air at ambient temperature (yield: 38%,
based on CdII).
Data collection: SMART (Bruker, 1997); cell refinement: SMART;
data reduction: SAINT (Bruker, 1999); program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
SHELXTL-Plus (Sheldrick, 2008); software used to prepare material
for publication: SHELXL97.
Crystal data
3
˚
[Cd(C8H4O4)(C10H8N2O2)(H2O)]
Mr = 482.71
V = 1683.0 (3) A
Z = 4
This work was supported by the NSF of China (grant No.
20861001), the NSF of Jiangxi Province (grant No. 0620007),
and the Development Program of Science and Technology of
the Education Department of Jiangxi Province (grant No.
20060237).
Monoclinic, C2=c
a = 14.1052 (15) A
Mo Kꢁ radiation
ꢂ = 1.35 mmꢁ1
T = 293 K
0.22 ꢄ 0.18 ꢄ 0.15 mm
˚
˚
b = 16.8934 (18) A
˚
c = 8.8967 (10) A
ꢀ = 127.451 (1)ꢃ
Data collection
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SQ3245). Services for accessing these data are
described at the back of the journal.
Bruker APEX diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.64, Tmax = 0.85
4629 measured reflections
1658 independent reflections
1623 reflections with I > 2ꢃ(I)
Rint = 0.064
References
Refinement
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S = 1.07
1658 reflections
132 parameters
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independent and constrained
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ꢁ3
˚
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˚
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2.258 (3)
2.314 (2)
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2.520 (2)
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O2—Cd1—O2i
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O2i—Cd1—O1
O1i—Cd1—O1
137.26 (5)
85.48 (10)
84.84 (6)
84.98 (9)
102.69 (8)
169.67 (12)
O1W—Cd1—O3
O2—Cd1—O3
O2i—Cd1—O3
O1i—Cd1—O3
O1—Cd1—O3
O3i—Cd1—O3
84.99 (4)
53.95 (6)
135.79 (7)
87.57 (8)
91.53 (8)
169.98 (9)
1
2
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ꢃ
˚
¨
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D—Hꢀ ꢀ ꢀA
O1W—H1Wꢀ ꢀ ꢀO3ii
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D—H
Hꢀ ꢀ ꢀA
1.95 (3)
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
0.81 (3)
2.755 (2)
172 (4)
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Carbon-bound H atoms were positioned geometrically (C—H =
˚
0.93 A) and refined as riding, with Uiso(H) values fixed at 1.2Ueq(C).
The water H atom was located in a difference Fourier map and
refined freely.
ꢂ
Acta Cryst. (2010). C66, m201–m203
Xu and Xie
[Cd(C8H4O4)(C10H8N2O2)(H2O)] m203