New examples of metal coordination architectures of 4,4′- sulfonyldibenzoic acid: Syntheses, crystal structure and luminescence

Article abstract of DOI:10.1002/ejic.200700651

Seven metal-organic coordination polymers, namely [Cd(sfdb)(phen) ₂]_n·2nH₂O (1), [Cd(sfdb)(bpy) ₂]_n·nH₂O (2), [Cu(sfdb)(phen)(H ₂O)]_n·0.5nH₂O (3), [Zn(sfdb)(bpy)(H ₂O)]_n·0.5nCH₃OH (4), [Cd(sfdb)(quin)]_n (5), [Cd₃(sfdb)₂(Hsfdb) ₂-(phen)₂]_n (6), and [Cd(sfdb)(bpy)] _n (7) [H₂sfdb = 4,4′-sulfonyl-dibenzoic acid, phen = 1,10-phenanthroline, quin = 2,2′-biquinoline, bpy = 2,2′- bipyridine] have been synthesized according to the principles of crystal engineering and structurally characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction analyses. Compounds 1-3 form 1D zigzag chains. Two phen ligands chelate to one cadmium atom in 1, which is rare in similar polymers, while two 2,2′-bpy ligands coordinate one cadmium atom in 2. The zigzag chains in 3 propagate in two different directions (rotated by 75°) that are assembled by supramolecular forces into an intriguing three-dimensional network. Complexes 4 and 5 form square-wave-like 1D chains, although the results indicate a transformation of 2,2′-bpy into quin during the course of the hydrothermal synthesis of compound 5. Compound 6 is a 1D grid-chain based on a linear trinuclear unit, and compound 7 shows a 1D double chain containing 28-membered rings with sfdb^2- ligands as bridges. Weak hydrogen bonding and intra- and/or intermolecular π...π stacking contacts in compounds 3-7 link the discrete 1D chains into high-dimensional supramolecular structures. The sfdb^2- ligand displays multiple coordination modes in these seven complexes. Complexes 1, 2, and 4-7 show blue photoluminescence at room temperature. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Full text of DOI:10.1002/ejic.200700651

FULL PAPER
DOI: 10.1002/ejic.200700651
New Examples of Metal Coordination Architectures of 4,4Ј-Sulfonyldibenzoic
Acid: Syntheses, Crystal Structure and Luminescence
Xiao-Li Chen,[a,b] Lei Gou,[a] Huai-Ming Hu,*[a] Feng Fu,[b] Zhong-Xi Han,[a]
Hui-Ming Shu,[a] Meng-Lin Yang,[a] Gang-Lin Xue,[a] and Chuan-Qin Du[a]
Keywords: Coordination modes / O ligands / Materials science / Organic–inorganic hybrid composites / Luminescence
Seven metal–organic coordination polymers, namely
[Cd(sfdb)(phen)2]n·2nH2O (1), [Cd(sfdb)(bpy)2]n·nH2O (2),
[Cu(sfdb)(phen)(H2O)]n·0.5nH2O (3), [Zn(sfdb)(bpy)(H2O)]n·
0.5nCH3OH (4), [Cd(sfdb)(quin)]n (5), [Cd3(sfdb)2(Hsfdb)2-
(phen)2]n (6), and [Cd(sfdb)(bpy)]n (7) [H2sfdb = 4,4Ј-sulfonyl-
dibenzoic acid, phen = 1,10-phenanthroline, quin = 2,2Ј-bi-
into an intriguing three-dimensional network. Complexes 4
and 5 form square-wave-like 1D chains, although the results
indicate a transformation of 2,2Ј-bpy into quin during the
course of the hydrothermal synthesis of compound 5. Com-
pound 6 is a 1D grid-chain based on a linear trinuclear unit,
and compound 7 shows a 1D double chain containing 28-
quinoline, bpy = 2,2Ј-bipyridine] have been synthesized ac- membered rings with sfdb2– ligands as bridges. Weak hydro-
cording to the principles of crystal engineering and structur-
ally characterized by elemental analysis, IR spectroscopy,
and single-crystal X-ray diffraction analyses. Compounds 1–
3 form 1D zigzag chains. Two phen ligands chelate to one
cadmium atom in 1, which is rare in similar polymers, while
two 2,2Ј-bpy ligands coordinate one cadmium atom in 2. The
zigzag chains in 3 propagate in two different directions (ro-
tated by 75°) that are assembled by supramolecular forces
gen bonding and intra- and/or intermolecular π···π stacking
contacts in compounds 3–7 link the discrete 1D chains into
high-dimensional supramolecular structures. The sfdb2– li-
gand displays multiple coordination modes in these seven
complexes. Complexes 1, 2, and 4–7 show blue photolumi-
nescence at room temperature.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
have two or more carboxyl groups that can be completely
or partially deprotonated, which results in a rich variety of
coordination modes and many interesting structures with
higher dimensions. Furthermore, these ligands can act as
both hydrogen-bond acceptors and hydrogen-bond donors
to generate supramolecular topologies. In light of the above,
more and more attention has been paid to the use of flexible
di- and polycarboxylate ligands,[3] whereas studies involving
semi-rigid V-shaped dicarboxylate ligands are relatively
scarce.[4] 4,4Ј-Sulfonyldibenzoic acid (H2sfdb) is a typical
example of a semi-rigid V-shaped dicarboxylate ligand, and
to the best of our knowledge there are only a few reports
concerning its coordination compounds.[5]
4,4Ј-Sulfonyldibenzoic acid is a very versatile ligand for
the construction of novel metal–organic compounds as it
has six potential donor atoms that allow the formation of
variable structures with different topologies and dimensions
constructed in different directions. A particular feature of
the sfdb2– ligand is the number of coordination modes it
can display (Scheme 1). However, the coordination chemis-
try and structural properties of metal polymers containing
sfdb2– ligands have seldom been documented to date.[5]
With the aim of understanding the coordination chemistry
of sfdb2– and studying its influence on the framework struc-
tures of its complexes, we have recently engaged in research
Introduction
The design and synthesis of metal–organic compounds
has been flourishing in recent years because of their intri-
guing architectures[1] and potential applications in gas stor-
age, ion exchange, catalysis, and so on.[2] Although a variety
of metal coordination frameworks with beautiful topologies
and interesting properties have been synthesized to date, the
rational control of the construction of polymeric networks
remains a great challenge in crystal engineering. One of the
most efficient routes to coordination polymers is to employ
a multifunctional ligand to link metal ions into an infinite
framework. Flexible di- and polycarboxylic acids are good
candidates for the construction of novel metal–organic
compounds as the carboxyl groups can form C–O–M–O
four-membered rings with central metal ions, thereby im-
proving the stability of transition metal–organic frame-
works (MOFs). Furthermore, di- and polycarboxylic acids
[a] Department of Chemistry/Shaanxi Key Laboratory of Physical-
Inorganic Chemistry, Northwest University,
Xi’an 710069, China
Fax: +86-29-8830-3331
E-mail: chemhu1@nwu.edu.cn
[b] Department of Chemistry and Chemical Engineering, Shaanxi
Key Laboratory of Chemical Reaction Engineering, Yanan
University,
Yan’an 716000, China
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H.-M. Hu et al.
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of this kind with coordination polymers. The introduction
of N-containing auxiliary ligands, such as phen, 2,2Ј-bipyr-
idine, etc., into the M/sfdb system may lead to new struc-
tural evolution and allow fine-tuning of the structural motif
of these metal–organic compounds. We now report the syn-
thesis, structures, and luminescent properties of seven novel
complexes of 4,4Ј-sulfonyldibenzoic acid, namely [Cd(sfdb)-
(phen)2]n·2nH2O (1), [Cd(sfdb)(bpy)2]n·nH2O (2), [Cu(sfdb)-
(phen)(H2O)]n·0.5nH2O (3), [Zn(sfdb)(bpy)(H2O)]n·0.5n-
CH3OH (4), [Cd(sfdb)(quin)]n (5), [Cd3(sfdb)2(Hsfdb)2-
(phen)2]n (6), and [Cd(sfdb)(bpy)]n (7).
Results and Discussion
Description of the Structures
[Cd(sfdb)(phen)2]n·2nH2O (1)
Single-crystal X-ray diffraction analysis revealed that
compound 1 is a 1D zigzag coordination polymer. The
asymmetric unit of 1 contains one cadmium atom, one
sfdb2– ligand, two phen ligands, and two lattice water mole-
cules. As illustrated in Figure 1a, each CdII atom in 1 is
coordinated by four nitrogen atoms [Cd1–N1 2.379(2),
Cd1–N2 2.522(3), Cd1–N3 2.419(2), Cd1–N4 2.391(2) Å]
from two chelating phen ligands and four oxygen atoms
from two chelating carboxylate groups of two sfdb2– ligands
[Cd1–O1 2.316(3), Cd1–O2 2.729(3), Cd1–O5A 2.494(3),
Cd1–O6A 2.604(3) Å]. However, the Cd1–O2 distance sug-
gests a nonnegligible interaction. Thus, the CdII atom can
be regarded as a monocapped pentagonal bipyramid.
Eight-coordinate CdII is very rare[6] and the structure of 1
is different from previously reported eight-coordinate com-
plexes,[6a] which generally have a distorted tetragonal anti-
prism geometry.
Each sfdb2– ligand bridges two cadmium atoms in
a chelating/chelating bis(bidentate) coordination mode
(Scheme 1a) to form a 1D infinite zigzag chain (Figure 1b)
with a Cd···Cd distance of 13.977(3) Å. Interestingly, two
phen ligands chelate to one cadmium atom in 1, which is
rare in similar coordination polymers.[7] Two adjacent phen
Scheme 1. Coordination modes of the sfdb2– ligand.
Figure 1. (a) Coordination environment of the CdII atom in 1; (b) perspective view of the 1D zigzag chain in 1. All hydrogen atoms have
been omitted for clarity.
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Metal Coordination Architectures of 4,4Ј-Sulfonyldibenzoic Acid
ligands are almost perpendicular to each other in 1 (the are on the same side of the one-dimensional chain (Fig-
dihedral angle is 86.35°). To the best of our knowledge, only ure 2b); two adjacent bpy ligands are almost perpendicular
a few examples have been reported to date in which two to each other in 2 (the dihedral angle is 80.58°). The H2sfdb
phen ligands chelate to one cadmium atom in coordination ligands in 2 are completely deprotonated and are strongly
polymers.[7]
bent at the sulfone sulfur site [C–S–C 101.74(14), O–S–O
120.2(2)°].
[Cd(sfdb)(bpy)2]n·nH2O (2)
To further examine the influence of the auxiliary ligands
on the structure of 1, we used the smaller aromatic chelat-
ing ligand 2,2Ј-bpy instead of phen. This ligand forms a
[Cu(sfdb)(phen)(H2O)]n·0.5nH2O (3)
The asymmetric unit of 3 contains one Cu atom, one
similar 1D zigzag polymeric coordination chain. As shown sfdb2– ligand, one phen, and one coordinated and half a
in Figure 2a, the asymmetric unit of 2 contains one CdII lattice water molecule. Each CuII atom is five-coordinated
atom, one sfdb2– ligand, two 2,2Ј-bpy ligands, and one lat- by two nitrogen atoms [Cu1–N1 2.042(2), Cu1–N2
tice water molecule. Each CdII atom is six-coordinated by 2.029(2) Å] from one chelating phen ligand, two oxygen
four nitrogen atoms [Cd1–N1 2.411(2), Cd1–N2 2.419(2), atoms (O1, O5A) from two carboxylate groups of two
Cd1–N3 2.403(2), Cd1–N4 2.440(2) Å] from two chelating sfdb2– ligands, and one oxygen atom (O7) from one coordi-
2,2Ј-bpy ligands and two oxygen atoms [Cd1–O1 2.299(2), nated water molecule (Figure 3a). The CuII atom exhibits
Cd1–O6A 2.272(2) Å] from two monodentate carboxylate an approximately square-pyramidal environment with the
groups of two sfdb2– ligands. The coordination geometry of atoms N1, N2, O1, and O5A in the equatorial plane and
the CdII center can therefore be described as a distorted a water molecule in the axial position. The Cu–O7(water)
octahedron. The CdII atoms are linked into a zigzag chain distance of 2.340(2) Å is significantly longer than the
with a Cd···Cd distance of 13.089 Å, which is shorter than average Cu–O(carboxyl) distances of 1.932(2) Å. As shown
that in 1. There are some distinct differences between the in Figure 3b, each CuII atom is joined to another one by an
crystal structures of 1 and 2, although both of them exhibit sfdb2– ligand in a bis(monodentate) fashion (Scheme 1e) to
similar 1D chain structures. Thus, the sfdb2– ligand in 2 generate a 1D zigzag chain. The angle between the phen
shows a different coordination mode (Scheme 1e) from that nitrogen atoms and the metal atom is far from the ideal
of 1 and the environment of the CdII atom in 2 is modified value of 90° [N1–Cu–N2 80.98(9)°] because of the geomet-
by incorporation of a bridging bis(monodentate) sfdb2– li- rical constraints imposed by the phen ligand.
gand instead of a chelating/chelating bis(bidentate) ligand
The structure of 3 consists of 1D polymeric zigzag chains
in 1. Similar to 1, the bpy ligands in 2 are coordinated to that form a 2D undulating network (Figure 3c) due to hy-
the CdII atom in a chelating fashion and the pyridine rings drogen-bonding interactions between the lattice water mole-
Figure 2. (a) Coordination environment of the CdII atom in 2; (b) perspective view of the 1D zigzag chain in 1. All H atoms have been
omitted for clarity.
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The most peculiar structural feature of this compound is
the unique supramolecular organization of these polymeric
chains, which extend in two different directions (Figure 3d).
These polymeric chains are arranged on parallel levels in
different propagating directions, rotated by 75° on passing
from one level to the successive one, which results in an
ABAB sequence. As far as we know, the packing of 1D
polymers usually occurs with a parallel orientation of all
chains, although, less commonly, they can span two dif-
ferent directions in other alternate layers.[8]
[Zn(sfdb)(bpy)(H2O)]n. 0.5nCH3OH (4)
The ZnII atom in the structure of 4 is five-coordinate
with a distorted square-pyramidal coordination environ-
ment (Figure 4a) made up of one ZnII atom, one sfdb2–
ligand, one 2,2Ј-bpy ligand, one coordinated water mole-
cule, and half a methanol molecule. Each ZnII atom is coor-
dinated by two nitrogen atoms [Zn1–N1 2.1119(9), Zn1–N2
2.1456(9) Å] from one chelating 2,2Ј-bpy ligand and two
oxygen atoms from two monodentate carboxylate groups of
two sfdb2– ligands in the equatorial plane, with another
oxygen atom (O7) from one coordinated water molecule in
the axial position. The Zn–O distances fall in the range
1.9764(7)–2.0368(8) Å and are similar to those found in
other zinc carboxylate coordination polymers.[9] The axial
Zn–O distance is slightly longer than those of the equatorial
Zn–O bonds. As shown in Figure 4b, the ZnII atoms are
joined by an sfdb2– ligand in a bis(monodentate) fashion
(Scheme 1e), similar to that in 3, to generate a 1D square-
wave-like chain. The dihedral angle between the two phenyl
rings of the sfdb2– ligand is 87.9°.
The 1D chains are linked into a 2D layer through a hy-
drogen-bonding interaction [O7–H7B···O2 2.706(1) Å and
161.9(9)°] between the carboxylate oxygen atoms and coor-
dinated water molecules along the a axis (Figure 4c). Inter-
estingly, these layers are further packed into a 3D structure
(Figure 4d) by π···π stacking interactions, with centroid–
centroid distances of 3.564 and 3.714 Å and plane–plane
distances of 3.361 and 3.375 Å between the pyridine rings.
[Cd(sfdb)(quin)]n (5)
Compound 5 crystallizes in the monoclinic space group
P21/n, and the asymmetric unit consists of one CdII atom,
one sfdb2– anion, and one quin ligand, as shown in Fig-
ure 5a. The quin ligand is formed in situ from 2,2Ј-bpy dur-
ing the hydrothermal synthesis. Cd1 has a distorted octahe-
dral coordination environment containing two nitrogen
atoms from one chelating quin ligand and four oxygen
atoms from two chelating carboxylate groups of two sfdb2–
ligands [Cd1–O1 2.446(4), Cd1–O2 2.246(4), Cd1–O5A
Figure 3. (a) Coordination environment of the CuII ion in 3; (b)
perspective view of the 1D zigzag chain in 3; (c) perspective view
of the 2D undulating network in 3; d) polymeric chains arranged
in different propagation directions. All H atoms have been omitted
for clarity.
cule and the oxygen atoms of the coordinated water mole- 2.379(4), Cd1–O6A 2.291(3) Å]. These distances are similar
cule and sulfone (O8–H8A···O7 2.724, O8–H8B···O4 to those reported for [Cd(bdc)(phen)·dmf] (H2bdc = ben-
2.780 Å). Adjacent 2D networks are ultimately extended zene-1,4-dicarboxylic acid).[7a] As shown in Figure 5b, the
into a 3D supramolecular structure through interlayer hy- CdII centers are joined by two sfdb2– ligands to generate a
drogen-bonding interactions [O7–H7A···O3 2.938(3) Å and square-wave-like 1D chain. One sfdb2– ligand assumes
168(4)°; O7–H7B···O6 2.789(3) Å and 176(4)°].
a
chelating/chelating bis(bidentate) bonding mode
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Metal Coordination Architectures of 4,4Ј-Sulfonyldibenzoic Acid
Figure 4. (a) Coordination environment of the ZnII atom in 4; (b) a perspective view of the 1D chain in 4; (c) perspective view of the 2D
layer formed by hydrogen-bonding interactions; (d) 3D structure formed by π···π stacking interactions. H atoms have been omitted for
clarity.
(Scheme 1a), similar to that in 1, to connect two CdII atoms bridging carboxylate group of another sfdb2– ligand. The
with a Cd···Cd distance of 14.669 Å. The dihedral angle Cd1–O distances fall in the range 2.270(2)–2.605(3) Å and
between two phenyl rings of the sfdb2– ligand is 82.47°.
are similar to those found in other cadmium carboxylate
Although 2,2Ј-bpy was used as the original organic rea- coordination polymers.[10] The coordination geometry of
gent in the preparation of this compound, it was rather un- the Cd1 center can be described as a distorted pentagonal
expectedly not found in the final product, which indicates bipyramid with atoms O2, O7, O8, N1, and N2 in the equa-
a transformation of 2,2Ј-bpy into quin during the course of torial plane and another two atoms (O1 and O11A) in the
the hydrothermal treatment. This transformation of 2,2Ј- axial positions. Cd2 lies at a crystallographic inversion cen-
bpy into quin only happens during the synthesis of com- ter and coordinates to six oxygen atoms from six carboxyl-
pound 5, where the hydrothermal synthesis conditions and ate groups of four sfdb2– and two Hsfdb– ligands. Two oxy-
metal/ligand ratio are different from those used to synthe- gen atoms (O2, O2A) come from two chelating-bridging tri-
size compounds 2 and 7, although they have the same rea- dentate carboxylate groups of two Hsfdb– ligands, two oxy-
gents. Additionally, C–H···O hydrogen bonds are observed gen atoms (O8, O8B) come from two chelating-bridging tri-
between C22–H22 and C25–H25 of the quin molecule and dentate carboxylate groups of two sfdb2– ligands, and two
the other coordinated carboxylate oxygen atoms (O1) of the oxygen atoms (O12A, O12B) come from bridging bidentate
adjacent chains. The quin molecules also participate in C– carboxylate groups of two sfdb2– ligands. The Cd2–O dis-
H···π interactions with a contact distance of 2.860 Å. All tances fall in the range 2.214(2)–2.284(2) Å and are very
these interactions lead to the formation of a 3D supramo- similar to each other. Likewise, the distances to the two
lecular structure (Figure 5c).
oxygen atoms situated at the diagonals are equivalent.
An interesting feature of 6 is that it contains completely
deprotonated sfdb2– and partially deprotonated Hsfdb– li-
[Cd3(sfdb)2(Hsfdb)2(phen)2]n (6)
The X-ray crystallographic analysis revealed that 6 con- gands, which show two different coordination modes. Thus,
tains linear trinuclear cadmium units that are linked by two the completely deprotonated sfdb2– ligand acts as a bridg-
sfdb2– bridges into a 1D grid chain. The structure contains ing bidentate/chelating-bridging tridentate coordination li-
two crystallographically nonequivalent CdII atoms. As gand (Scheme 1d), while the partially deprotonated Hsfdb–
shown in Figure 6a, Cd1 is surrounded by two nitrogen ligand binds in a chelating-bridging tridentate coordination
atoms [Cd1–N1 2.364(3), Cd1–N2 2.299(3) Å] from a che- mode (Scheme 1c) and shows a significantly different coor-
lating phen ligand, two oxygen atoms (O1, O2) from one dination fashion to those ligands in compounds 1–5 and 7.
chelating carboxylate group of the Hsfdb– ligand, two oxy- Each sfdb2– ligand links four cadmium atoms and each Cd1
gen atoms (O7, O8) from a chelating carboxylate group of atom is connected to two sfdb2– ligands and one Hsfdb–
the sfdb2– ligand, and one oxygen atom (O11A) from a ligand, whereas each Cd2 atom is connected to four sfdb2–
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Figure 5. (a) Coordination environment of the CdII ion in 5; (b) perspective view of the 1D chain in 5; (c) view of the 3D supramolecular
structure. All H atoms have been omitted for clarity.
ligands in a bridging bidentate/chelating-bridging tridentate gands to form a novel {Cd6O8C20S2} 36-membered ring
coordination mode (Scheme 1d) and two Hsfdb– ligands containing a micropore with a size of around 13.7ϫ9.53 Å2
with a chelating-bridging tridentate coordination mode (based on the Cd2···Cd2 and S2···S2 distances). All the
(Scheme 1c).
rings are further linked to form a one-dimensional grid
Another interesting feature is that a novel trinuclear cad- chain (Figure 6b).
mium unit is found in 6. Three cadmium atoms (Cd1, Cd2,
The most significant feature of 6 is that adjacent chains
and Cd1A) are located in a line with Cd1···Cd1A and form a 2D rectangular grid framework along the a axis
Cd1···Cd2 distances of 7.000 and 3.499 Å, respectively. To through hydrogen-bonding interactions between the unco-
the best of our knowledge, this situation is very rare and ordinated carboxyl oxygen of the Hsfdb– ligands and the
differs from the situation in other Cd carboxylate coordina- oxygen atom of another Hsfdb– ligand [O5–H5A···O6B
tion polymers containing trinuclear cadmium units,[11] 2.623(5) Å and 176.0°; Figure 6c]. More remarkably, the hy-
where the three CdII atoms are not in line drogen bonds pass through the {Cd6O8C20S2} 36-mem-
(Cd1···Cd2···Cd1A 133.5°). Two trinuclear cadmium units bered ring of the adjacent chain to form a 2D interpen-
are connected by four carboxylate groups of two sfdb2– li- etrated framework (Figure 6d). These 2D interpenetrated
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Metal Coordination Architectures of 4,4Ј-Sulfonyldibenzoic Acid
Figure 6. (a) Coordination environment of the CdII atom in 6; (b) perspective view of the 1D chain in 6; (c) perspective view of the 2D
layer formed by hydrogen bonds; (d) perspective view of the interpenetrating 2D network formed by hydrogen bonds (phen ligands
omitted for clarity); (e) 3D structure formed by C–H···O hydrogen bonds and weak C–H···π interactions viewed along the b axis. All H
atoms have been omitted for clarity.
frameworks are found to pack on top of each other in a boxylate groups of sfdb2– ligands along the 101 direction
slipped geometry that is stabilized by C–H···O hydrogen (Figure 7b). The H2sfdb ligands in 7 are completely depro-
bonds and weak C–H···π interactions with a distance of tonated (sfdb2–) and are bent at the sulfone sulfur site [C–
3.333 Å to form a 3D architecture (Figure 6e).
S–C 105.25(14)°, O–S–O 119.2(2)°]; the dihedral angle be-
tween the two phenyl rings is 87.57°.
It is worth to note that the CdII center is connected to
three sfdb2– ligands, while one sfdb2– ligand is connected to
three CdII atoms in a bridging/chelating bis-bidentate coor-
dination fashion (Scheme 1b), which is different from the
situation in complexes 1–6. To the best of our knowledge,
only five examples of complexes containing an sfdb2– li-
gand, where each ligand binds to two metal atoms in bridg-
ing/bridging bis-bidentate and bis-monodentate modes,
have been reported to date.[5] A similar bridging/chelating
bis-bidentate coordination mode has never been described
before for metal complexes containing an sfdb2– ligand.
The most significant feature of 7 is that adjacent chains
[Cd(sfdb)(bpy)]n (7)
The crystal structure of 7 reveals that it is a one-dimen-
sional double chain containing 28-membered rings with
sfdb2– ligands as the bridges. The asymmetric unit of 7 con-
tains one CdII atom, one sfdb2– ligand, and one bpy ligand.
As shown in Figure 7a, the CdII atom is in a distorted octa-
hedral geometry and is coordinated by two nitrogen atoms
from one chelating 2,2Ј-bpy ligand and four carboxylate
oxygen atoms from three sfdb2– ligands. The Cd–O and Cd–
N bond lengths are similar to those in other Cd carboxylate
coordination polymers.[12] Each pair of CdII atoms is
bridged by six carboxylate oxygen atoms from two sfdb2– are intercalated in a zipper fashion to generate a 2D undul-
ligands to form a 28-membered ring. These dimeric Cd2 ating sheet through hydrogen bonds (C1–H1···O3 2.416 Å
units feature a 1D double chain interconnected by the car- and 134.4°; C13–H13···O3 2.533 Å and 148.4°; C17–
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Figure 7. Coordination environment of the CdII atom in 7; (b) perspective view of the 1D double chain in 7; (c) 2D layer produced by
hydrogen bonds viewed along the a axis; (d) perspective view of the 3D network viewed along the a axis. All H atoms have been omitted
for clarity.
H17···O6 2.503 Å and 134.3°; C20–H20···O4 2.621 Å and bridging bis-bidentate and bis-monodentate coordination
151.3°; C23–H23···O5 2.626 Å and 139.5°; C24–H24···O1 modes, have been reported to date,[5] and coordination
2.716 Å and 149.8°; C8–H8···π 2.770, 2.682 Å and 174.0, modes such as those shown in Scheme 1a–d have never been
144.6°; S1=O3···C1 3.318 Å and 114.9°) and π···π stacking described before in metal complexes containing an sfdb2–
interactions, with a centroid–centroid distance of 3.377 Å ligand.
between the pyridine rings and the phenyl rings of the adja-
cent chain. This 2D undulating sheet has two types of pores
with sizes of about 12.5ϫ11.3 Å2 (28-membered rings,
based on the Cd1···Cd1A and S1···S1A distances) and
5.0ϫ4.0 Å2 (eight-membered rings, based on the O2···O2A
and Cd1A···Cd1B distances; Figure 7c). The real volume of
the cavity in each pore structure is further reduced due to
significant offset stacking of adjacent metallamacrocycles.
This 2D network is further packed into a 3D structure
through C–H···π interactions (C4–H4···π 2.854 Å; Fig-
ure 7d).
Complexes 1–7 are readily synthesized under the same
hydrothermal reaction conditions in the presence of dif-
ferent auxiliary ligands (phen and 2,2Ј-bpy). Interestingly,
two complexes with different structures, different coordina-
tion modes, and different luminescence properties are ob-
tained. A comparison of the structures of 1 and 7 shows
that the size of the auxiliary ligands has a significant effect
on the formation and structures of the resulting complexes.
It should be noted that other factors, such as the pH of
the reaction mixture, the hydrothermal reaction conditions,
and the metal/ligand ratios, also affect the overall structure
obtained. A comparison of complexes 2, 5, and 7 shows
that the transformation of the 2,2Ј-bpy ligand into quin
only happens during the hydrothermal treatment of com-
Comparison of the Structures of Complexes 1–7
Seven new complexes have been obtained by self-as- plex 5, where the synthesis conditions and metal/ligand ra-
sembly with the V-shaped ligand sfdb2–, which shows five tio are different from those of 2 and 7, although they use
different coordination modes (Scheme 1). To the best of our the same reactants. Moreover, 2 and 7 are obtained accord-
knowledge, only five complexes containing an sfdb2– ligand, ing to the same procedure but at different pH. Complex 2
in which each ligand binds to two metal ions in bridging/ contains 1D zigzag chains, whereas 7 contains a one-dimen-
246
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Eur. J. Inorg. Chem. 2008, 239–250

Metal Coordination Architectures of 4,4Ј-Sulfonyldibenzoic Acid
sional double chain containing 28-membered rings. These in the complexes may be due to their rigidity. This rigidity
results suggest that an increase in pH results in a higher favors the energy transfer and reduces the loss of energy
connectivity level of the sfdb2– ligands, which in turn affects through nonradiative pathways.[6c,14] On the other hand, the
the formation of the final structure.
different redshifts of 1–2, 5–7 compared with the free sfdb2–
In addition, although 1 and 6 both contain a CdII atom, ligand may be attributed to the different coordination
an sfdb2– ligand, and phen, and are formed under the same modes (Scheme 1) of the ligands.[6c,15] The luminescence
hydrothermal reaction conditions, except for different properties of these metal–organic compounds indicate that
metal/ligand ratios, they have a remarkable structural and they may be excellent candidates for use as photolumines-
compositional diversity that is achieved due to the different cent materials.
coordination modes of the ligands and the coordination ge-
ometry of the metal center. A comparison of the structures
of 1 and 6 shows that the metal/ligand ratios are a critical
factor for the formation and structure of the resulting com-
plexes.
In order to examine the effect of metal salt and solvent
on the syntheses, hydrothermal reactions were carried out
under the same conditions with Cu(NO3)2 and Zn(NO3)2
instead of Cd(NO3)2 and ethanol instead of H2O. The re-
sulting complexes 2–4 show a similar 1D polymer chain
with the same coordination mode, which shows that the
metal salt and solvent have little influence on the reaction.
A comparison of the structures of 1–7 shows that the
formation of MOFs is influenced by many factors, such as
the organic ligands, metal/ligand ratios, solvent molecules,
hydrothermal reaction conditions, and pH of the reaction
mixture, etc. Among these factors, the size of the auxiliary
ligands, the hydrothermal reaction conditions, and the
Figure 8. Emission spectra of 1, 2, and 4–7 in the solid state at
metal/ligand ratios are the most important aspects and have room temperature.
very significant effects on the formation and structures of
the resulting complexes and their distinct supramolecular
structures.
Conclusions
We have investigated the coordination chemistry of 4,4Ј-
sulfonyldibenzoic acid with transition metal salts (Cd, Zn,
and Cu). Different auxiliary ligands lead to a series of 1D
chain structures with different coordination modes of the
bridging ligands and different coordination geometries at
the metal centers. The different structures of complexes 1–
7 indicate that the V-shaped sfdb2– dicarboxylate ligand has
the ability to adjust its coordination configuration in dif-
ferent reaction systems. Our studies also show that the size
of the auxiliary ligands, the hydrothermal reaction condi-
tions, and the metal/ligand ratios have significant effects on
the formation and structures of the resulting complexes and
result in distinct supramolecular structures. In addition,
weak hydrogen-bonding, intra- and/or intermolecular π···π
stacking contacts, and C–H···π interactions play a crucial
role in linking the discrete 1D chains into high-dimensional
supramolecular structures. Obviously, the appropriate com-
bination of bridging dicarboxylate, aromatic chelate, and
metal ion could lead to the design of metal–organic com-
pounds with novel structures and properties. Compounds 1,
2, and 4–7 show photoluminescence at room temperature.
Luminescent Properties
The emission spectra of 1, 2, and 4–7 in the solid state
at room temperature are shown in Figure 8. The ligand ex-
hibits one weak emission band at λ = 329 nm upon exci-
tation at 253 nm. Complexes 1 and 2 exhibit two similar
emission peaks at λ ≈ 380 and 396 nm upon excitation at
310 nm for 1 and at λ ≈ 365 and 388 nm upon excitation at
335 nm for 2, which is due to their similar structures. Com-
plex 6 also exhibits an emission peak at λ = 394 nm upon
excitation at 253 nm. The emission peaks in 1, 2 and 6 are
redshifted relative to that of the free ligand (λmax = 329 nm),
which might also be attributed to intraligand (π–π*) fluo-
rescence.[13] Excitation at λ = 335 nm gives intense emis-
sions at λ = 359 nm for 4, λ = 385 nm for 5, and λ = 365 nm
for 7, which are assigned to ligand-to-metal charge-transfer
(LMCT) transitions.[14] According to the ligand-field theory
of coordination compounds and previously reported molec-
ular orbital calculation for related CdII coordination poly-
mers,[6c] we can conclude that the HOMO is associated with
π-bonding orbitals from the ring and that the LUMOs are
mostly Cd–O antibonding orbitals, which are localized
more on the metal centers for complexes 4, 5, and 7. A
comparison of the emission spectra of complexes 4, 5, 7,
Experimental Section
Materials and Methods: All chemicals and reagents were used as
and the ligand shows that the enhancement of luminescence received from commercial sources without further purification. All
Eur. J. Inorg. Chem. 2008, 239–250
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
247

H.-M. Hu et al.
FULL PAPER
reactions were carried out under hydrothermal conditions. Elemen- s, 1552 s, 1439 m, 1393 s, 1296 m, 1145 w, 1069 w, 1014 w, 849 w,
tal analyses (C, H, and N) were determined with a Elementar Vario
EL III elemental analyzer. IR spectra were recorded as KBr pellets
with a Bruker EQUINOX55 spectrophotometer in the 4000–
400 cm–1 region. Fluorescence spectra were recorded with a Hitachi
F-4500 fluorescence spectrophotometer at room temperature.
746 s, 615 m cm–1.
Synthesis of [Cu(sfdb)(phen)(H2O)]n·0.5nH2O (3): This complex was
synthesized as for 1 but with Cu(CH3COO)2·H2O (20.0 mg,
0.1 mmol) instead of Cd(NO3)2·4H2O. Blue crystals. Yield: 35.1 mg
(61% based on Cu). C26H19CuN2O7.50S (575.03): calcd. C 54.30,
Synthesis of [Cd(sfdb)(phen)2]n·2nH2O (1): A mixture of Cd(NO3)2·
4H2O (30.8 mg, 0.1 mmol), 4,4Ј-sulfonyldibenzoic acid (30.6 mg,
0.1 mmol), and phen (39.6 mg, 0.2 mmol) in a 1:1:2 molar ratio
was stirred in water (10 mL) and the pH of the mixture adjusted
to 6.5 with a 0.5  NaOH solution. It was then sealed in a 25-mL
Telfon-lined stainless-steel container, which was heated to 160 °C
for 72 h and then cooled to room temperature at a rate of 5 °Ch–1.
Pale-yellow block crystals were obtained. Yield: 45.5 mg (56%
based on Cd). C38H26CdN4O8S (813.10): calcd. C 53.52, H 3.43,
H 3.33, N 4.87; found C 54.37, H 3.31, N 4.83. IR (KBr): ν = 3544
˜
m, 3070 s, 2360 w, 1641 s, 1567 m, 1427 m, 1352 s, 1295 m, 1160
m, 1101 m, 1013 w, 854 m, 777 s, 695 m, 620 s cm–1.
Synthesis of [Zn(sfdb)(bpy)(H2O)]n·0.5n(CH3OH) (4): Zn(NO3)2·
4H2O (101.2 mg, 0.4 mmol), 4,4Ј-sulfonyldibenzoic acid (30.6 mg,
0.1 mmol), and 2,2Ј-bpy (15.6 mg, 0.1 mmol) in a 4:1:1 molar ratio
were stirred in water (5 mL) and methanol (5 mL) and the pH ad-
justed to 6.5 with 0.5  NaOH solution. The hydrothermal synthe-
sis of 4 followed the same procedure as for 1. Colorless crystals.
Yield: 34.7 mg (62% based on H2sfdb). C24.5H20N2O7.50SZn
(559.85): calcd. C 52.56, H 3.60, N 5.00; found C 52.58, H 3.57, N
N 7.34; found C 53.54, H 3.40, N 7.29. IR (KBr): ν = 3442 m,
˜
2360 m, 1597 s, 1555 s, 1398 s, 1327 w, 1162 m, 1101 m, 848 m,
815 m, 745 s, 696 w, 619 m cm–1.
4.96. IR (KBr): ν = 3506 w, 2361 w, 1600 s, 1561 s, 1403 s, 1320
˜
Synthesis of [Cd(sfdb)(bpy)2]n·nH2O (2): This complex was synthe-
sized as for 1 but with 2,2Ј-bpy instead of phen (solution pH 5.5).
Colorless crystals. Yield: 43.3 mg (58% based on Cd).
C34H26CdN4O7S (747.05): calcd. C 54.66, H 3.51, N 7.50; found C
m, 1295 m, 1163 s, 1135 w, 1101 m, 1012 w, 869 w, 742 s, 693 w,
620 m cm–1.
Synthesis of [Cd(sfdb)(quin)]n (5): A mixture of Cd(NO3)2·4H2O
54.69, H 3.47, N 7.53. IR (KBr): ν = 3425 w, 3066 w, 2360 s, 1598 (30.8 mg, 0.1 mmol), 4,4Ј-sulfonyldibenzoic acid (30.6 mg,
˜
Table 1. Crystal data and structural refinement parameters for compounds 1–4.
1
2
3
4
Empirical formula
Formula mass
Space group
a [Å]
b [Å]
c [Å]
C38H28CdN4O8S
813.10
P21/c
13.9769(18)
19.184(2)
12.5471(16)
90
C34H26CdN4O7S
747.05
C2/c
23.5920(15)
13.0888(8)
22.7312(14)
90
C26H19CuN2O7.5
575.03
C2/c
22.995(5)
12.265(2)
17.901(3)
90
S
C24.50H20N2O7.50SZn
559.85
P21/n
6.8234(4)
16.4101(10)
24.0987(15)
90
α [°]
β [°]
94.410(2)
90
3354.4(7)
4
1.610
1648
115.0520(10)
90
6358.8(7)
8
1.561
3024
110.871(4)
90
4717.5(16)
8
1.619
2352
90.6350(10)
90
2698.2(3)
4
1.378
1148
γ [°]
V [Å3]
Z
Dcalcd. [Mgm–3]
F(000)
Reflections collected
16617
1.042
15617
1.011
11594
1.032
13387
1.040
S on F2
R1, wR2 [I Ͼ 2σ(I)]
R1, wR2 (all data)
0.0327, 0.0770
0.0432, 0.0825
0.0301, 0.0691
0.0382, 0.0734
0.0361, 0.0916
0.0465, 0.0982
0.0450, 0.1238
0.0697, 0.1403
Table 2. Crystal data and structural refinement parameters for compounds 5–7.
5
6
7
Empirical formula
Formula mass
Space group
a [Å]
b [Å]
c [Å]
C32H20CdN2O6S
672.96
P21/n
8.1894(9)
21.468(2)
16.5536(18)
90
101.536(2)
90
C80H50Cd3N4O24S4
1916.68
P1
C24H16CdN2O6S
572.85
P21/c
12.3570(9)
15.3292(12)
12.3221(9)
90
110.3440(10)
90
¯
10.413(2)
13.732(3)
14.915(3)
107.390(2)
108.286(2)
100.380(2)
1842.0(7)
1
α [°]
β [°]
γ [°]
V [Å3]
2851.5(5)
4
1.568
2188.5(3)
4
1.739
Z
Dcalcd. [Mgm–3]
F(000)
1.728
958
1352
1144
Reflections collected
14253
0.954
9328
1.039
10857
1.061
S on F2
R1, wR2 [I Ͼ 2σ(I)]
R1, wR2 (all data)
0.0515, 0.0796
0.1263, 0.1016
0.0325, 0.0806
0.0407, 0.0869
0.0255, 0.0610
0.0310, 0.0653
248
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Metal Coordination Architectures of 4,4Ј-Sulfonyldibenzoic Acid
0.1 mmol), and 2,2Ј-bpy (15.6 mg, 0.1 mmol) in a 1:1:1 molar ratio
was stirred in water (10 mL) and the pH adjusted to 7 with 0.5 
NaOH solution. This mixture was sealed in a 25-mL Telfon-lined
stainless-steel container, which was heated to 170 °C for 72 h. Cool-
ing to room temperature at a rate of 3 °Ch–1 gave pale-yellow crys-
tals. Yield: 23.5 mg (35% based on H2sfdb). C32H20CdN2O6S
(672.96): calcd. C 57.11, H 3.00, N 4.16; found C 57.14, H 3.02, N
0.2 mmol), phen (19.8 mg, 0.1 mmol) and NaOH (40.0 mg,
0.1 mmol), in a 1:2:1:1 molar ratio, was stirred in water (10 mL) in
air for 30 min, then sealed in a 25-mL Telfon-lined stainless-steel
container. The synthesis of compound 6 followed the same pro-
cedure as for 1 and gave colorless crystals. Yield: 42.1 mg (66%
based on Cd). C80H50Cd3N4O24S4 (638.89): calcd. C 50.17, H 2.63,
N 2.91; found C 50.14, H 2.65, N 2.93. IR (KBr): ν = 2535 w, 1696
˜
4.12. IR (KBr): ν = 1573 s, 1508 m, 1420 m, 1374 vs, 1146 w, 1098 s, 1594 s, 1556 s, 1476 w, 1397 s, 1323 s, 1291 s, 1160 m, 1146 m,
˜
w, 851 s, 815 m, 779 vs, 727 s, 664 w cm–1.
1098 m, 1013 w, 864 w, 761 s, 692 m, 616 s cm–1.
Synthesis of [Cd(sfdb)(bpy)]n (7): The synthesis of compound 7 fol-
lowed the same procedure as for 2 but with a different pH (solution
pH 7). Colorless crystals. Yield: 30.4 mg (53% based on Cd).
Synthesis of[Cd3(sfdb)2(Hsfdb)2(phen)2]n (6):A mixtureofCd(NO3)2·
4H2O (30.8 mg, 0.1 mmol), 4,4Ј-sulfonyldibenzoic acid (61.2 mg,
Table 3. Selected bond lengths [Å] and bond angles [°] for 1–4.[a]
Compound 1
Table 4. Selected bond lengths [Å] and bond angles [°] for 5–7.[a]
Compound 5
Cd(1)–O(1)
Cd(1)–O(5)#1
Cd(1)–O(6)#1
Cd(1)–N(1)
O(1)–Cd(1)–N(1)
O(1)–Cd(1)–N(2)
O(1)–Cd(1)–N(3)
O(1)–Cd(1)–N(4)
O(1)–Cd(1)–O(5)#1
O(1)–Cd(1)–O(6)#1
O(5)#1–Cd(1)–N(2)
2.316(3)
2.494(3)
2.604(3)
2.379(2)
131.85(9)
159.55(9)
88.64(9)
84.14(9)
85.51(9)
93.90(10)
77.57(8)
Cd(1)–N(2)
Cd(1)–N(3)
Cd(1)–N(4)
2.522(3)
2.419(2)
2.391(2)
Cd(1)–O(1)
2.446(4)
Cd(1)–O(6)#1
2.291(4)
Cd(1)–O(2)
2.246(4)
Cd(1)–N(1)
2.304(5)
Cd(1)–O(5)#1
2.379(4)
Cd(1)–N(2)
2.321(5)
N(1)–Cd(1)–N(2)
67.44(8)
O(2)–Cd(1)–O(1)
O(2)–Cd(1)–O(5)#1
O(2)–Cd(1)–O(6)#1
O(2)–Cd(1)–N(1)
O(2)–Cd(1)–N(2)
O(5)#1–Cd(1)–O(1)
O(6)#1–Cd(1)–N(1)
O(6)#1–Cd(1)–N(2)
55.85(15)
100.27(16)
102.08(17)
150.65(17)
104.55(18)
138.43(14)
96.59(17)
142.03(17)
O(6)#1–Cd(1)–O(5)#1
O(6)#1–Cd(1)–O(1)
N(1)–Cd(1)–O(5)#1
N(1)–Cd(1)–N(2)
N(1)–Cd(1)–O(1)
N(2)–Cd(1)–O(1)
N(2)–Cd(1)–O(5)#1
55.31(16)
93.74(16)
108.98(15)
71.98(19)
100.83(17)
123.63(15)
93.36(16)
N(1)–Cd(1)–O(6)#1 75.52(9)
N(2)–Cd(1)–O(6)#1 84.30(9)
N(3)–Cd(1)–O(5)#1 153.75(9)
N(3)–Cd(1)–N(2)
101.45(8)
N(3)–Cd(1)–O(6)#1 155.45(9)
N(4)–Cd(1)–O(5)#1 84.80(9)
N(4)–Cd(1)–O(6)#1 135.41(9)
O(5)#1–Cd(1)–O(6)#1 50.71(10)
N(1)–Cd(1)–N(4)
N(1)–Cd(1)–N(3)
N(1)–Cd(1)–O(5)#1
135.59(8)
84.63(8)
117.92(9)
N(4)–Cd(1)–N(2)
N(4)–Cd(1)–N(3)
82.97(8)
69.13(8)
Compound 6
Cd(1)–O(1)
Cd(1)–O(2)
Cd(1)–O(7)
Cd(1)–O(8)
2.322(3)
2.605(3)
2.588(3)
2.326(2)
2.270(2)
87.46(10)
94.62(10)
52.91(8)
92.97(10)
180.000(1)
120.89(8)
75.79(8)
152.25(9)
52.16(8)
Cd(1)–N(1)
Cd(1)–N(2)
Cd(2)–O(2)
Cd(2)–O(8)
2.364(3)
2.299(3)
2.284(2)
2.282(2)
2.214(2)
154.91(9)
105.16(10)
145.47(9)
83.31(10)
134.87(10)
71.62(10)
83.37(9)
96.63(9)
180.000(2)
93.96(9)
90.81(9)
180.000(1)
86.04(9)
93.96(9)
89.19(9)
90.81(9)
Compound 2
Cd(1)–O(1)
Cd(1)–O(6)#1
Cd(1)–N(1)
2.299(2)
2.272(2)
2.411(2)
81.82(8)
150.44(9)
117.66(8)
80.20(8)
91.29(9)
84.81(9)
89.04(8)
122.06(9)
Cd(1)–N(2)
Cd(1)–N(3)
Cd(1)–N(4)
2.419(2)
2.403(2)
2.440(2)
Cd(1)–O(11)#1
O(1)–Cd(1)–O(8)
O(1)–Cd(1)–O(7)
O(1)–Cd(1)–O(2)
O(1)–Cd(1)–N(1)
O(2)–Cd(2)–O(2)#3
O(7)–Cd(1)–O(2)
O(8)–Cd(1)–O(2)
O(8)–Cd(1)–N(1)
O(8)–Cd(1)–O(7)
Cd(2)–O(12)#1
N(1)–Cd(1)–O(7)
N(2)–Cd(1)–O(1)
N(2)–Cd(1)–O(2)
N(2)–Cd(1)–O(7)
N(2)–Cd(1)–O(8)
N(2)–Cd(1)–N(1)
O(8)–Cd(2)–O(2)
O(8)#3–Cd(2)–O(2)
O(8)#3–Cd(2)–O(8)
O(12)#1–Cd(2)–O(2)
O(12)#1–Cd(2)–O(8)
O(12)#1–Cd(2)–O(12)#2
O(12)#1–Cd(2)–O(2)#3
O(12)#2–Cd(2)–O(2)#3
O(12)#2–Cd(2)–O(8)
O(12)#2–Cd(2)–O(8)#3
O(1)–Cd(1)–N(1)
O(1)–Cd(1)–N(2)
O(1)–Cd(1)–N(3)
O(1)–Cd(1)–N(4)
O(6)#1–Cd(1)–O(1)
O(6)#1–Cd(1)–N(1)
O(6)#1–Cd(1)–N(2)
O(6)#1–Cd(1)–N(3)
O(6)#1–Cd(1)–N(4) 169.24(9)
N(1)–Cd(1)–N(2)
N(1)–Cd(1)–N(4)
N(2)–Cd(1)–N(4)
N(3)–Cd(1)–N(1)
N(3)–Cd(1)–N(2)
N(3)–Cd(1)–N(4)
68.77(7)
87.46(7)
95.13(7)
143.86(7)
86.59(8)
68.21(8)
O(11)#1–Cd(1)–O(1) 144.04(9)
O(11)#1–Cd(1)–O(8) 83.20(10)
O(11)#1–Cd(1)–O(7) 106.42(10)
O(11)#1–Cd(1)–O(2) 91.13(8)
O(11)#1–Cd(1)–N(1) 80.26(10)
O(11)#1–Cd(1)–N(2) 105.98(10)
Compound 3
Cu(1)–O(1)
Cu(1)–O(5)#1
Cu(1)–O(7)
O(1)–Cu(1)–N(1)
O(1)–Cu(1)–N(2)
O(1)–Cu(1)–O(7)
O(5)#1–Cu(1)–O(1)
O(5)#1–Cu(1)–N(1)
1.9420(19)
1.922(2)
2.340(2)
174.45(8)
93.80(9)
89.75(8)
94.54(9)
90.64(9)
Cu(1)–N(1)
Cu(1)–N(2)
2.042(2)
2.029(2)
O(5)#1–Cu(1)–N(2) 171.57(9)
O(5)#1–Cu(1)–O(7) 84.70(9)
N(1)–Cu(1)–O(7)
N(2)–Cu(1)–N(1)
N(2)–Cu(1)–O(7)
N(1)–Cd(1)–O(2)
82.40(9)
92.70(8)
80.98(9)
96.56(9)
Compound 7
Cd(1)–O(1)
Cd(1)–O(2)#1
Cd(1)–O(5)#2
O(1)–Cd(1)–O(6)#2
O(1)–Cd(1)–N(1)
O(1)–Cd(1)–N(2)
O(2)#1–Cd(1)–O(1)
2.2915(19)
2.2358(18)
2.2638(18)
156.16(6)
99.28(7)
Cd(1)–O(6)#2
Cd(1)–N(1)
Cd(1)–N(2)
O(5)#2–Cd(1)–O(1)
O(5)#2–Cd(1)–N(1)
O(5)#2–Cd(1)–N(2)
O(5)#2–Cd(1)–O(6)#2
N(1)–Cd(1)–O(6)#2
N(1)–Cd(1)–N(2)
N(2)–Cd(1)–O(6)#2
2.543(2)
2.316(2)
2.404(2)
105.47(7)
139.98(7)
82.41(7)
54.55(7)
92.22(7)
69.60(8)
81.10(7)
Compound 4
Zn(1)–O(1)
Zn(1)–O(5)#1
Zn(1)–O(7)
O(1)–Zn(1)–O(5)#1
O(1)–Zn(1)–O(7)
O(1)–Zn(1)–N(1)
O(1)–Zn(1)–N(2)
O(5)#1–Zn(1)–O(7)
1.9764(7)
2.0309(8)
2.0368(8)
94.10(3)
103.71(3)
150.68(3)
91.06(3)
93.23(3)
Zn(1)–N(1)
Zn(1)–N(2)
2.1119(9)
2.1456(9)
83.44(7)
O(5)#1–Zn(1)–N(1) 90.02(3)
O(5)#1–Zn(1)–N(2) 160.02(3)
O(7)–Zn(1)–N(1)
O(7)–Zn(1)–N(2)
N(1)–Zn(1)–N(2)
105.37(8)
O(2)#1–Cd(1)–O(5)#2 112.77(8)
O(2)#1–Cd(1)–O(6)#2 95.45(8)
105.03(3)
104.28(3)
76.35(3)
O(2)#1–Cd(1)–N(1)
O(2)#1–Cd(1)–N(2)
89.69(8)
158.74(8)
[a] Symmetry codes for 1: #1: x + 1, y, z; #2: x – 1, y, z; 2: #1: x,
y – 1, z; #2: x, y + 1, z; 3: #1: x – 1/2, y + 1/2, z; #2: x + 1/2, y –
1/2, z; 4: #1: –x + 1/2, y – 1/2, –z + 1/2; #2: –x + 1/2, y + 1/2, –z
+ 1/2.
[a] Symmetry codes for 5: #1: x – 3/2, –y + 1/2, z – 1/2; #2: x +
3/2, –y + 1/2, z + 1/2; 6: #1: x, y + 1, z; #2: –x + 2, –y + 1, –z +
2; #3: –x + 2, –y + 2, –z + 2; #4: x, y – 1, z; 7: #1: –x + 2, –y +
2, –z + 1; #2: –x + 1, –y + 2, –z.
Eur. J. Inorg. Chem. 2008, 239–250
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
249

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˜
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X-ray Crystallography: Intensity data were collected with a Bruker
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Data
Centre
via
www.ccdc.cam.ac.uk/
Acknowledgments
This work was supported by the National Natural Science Founda-
tion of China (grant no. 20573083) and the Natural Science Foun-
dation of Shaanxi Province (grant no. 2004B09).
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Received: June 25, 2007
Published Online: November 8, 2007
250
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Eur. J. Inorg. Chem. 2008, 239–250