Structural investigation of coordination polymers constructed from a conformational bis-triazole ligand and V-shaped bridging carboxylate anions: Hydrothermal syntheses, crystal structures, and property studies

Article abstract of DOI:10.1002/ejic.201000731

The conformational bis-triazole ligand 4,4'-bis[(1,2,4-triazol-1-yl)methyl] biphenyl (btmb, 1), was successfully synthesized, and seven new coordination polymers, namely {M(oba)(btmb)}_n [M = Cd²⁺ (2), Co ²⁺ (3), Ni^2+<

Full text of DOI:10.1002/ejic.201000731

FULL PAPER
DOI: 10.1002/ejic.201000731
Structural Investigation of Coordination Polymers Constructed from a
Conformational Bis-triazole Ligand and V-Shaped Bridging Carboxylate
Anions: Hydrothermal Syntheses, Crystal Structures, and Property Studies
Chen Ren,[a] Ping Liu,[a] Yao-Yu Wang,*[a] Wen-Huan Huang,[a] and Qi-Zhen Shi[a]
Keywords: Conformation analysis / Crystal engineering / Coordination polymers / N ligands / O ligands
The conformational bis-triazole ligand 4,4Ј-bis[(1,2,4-triazol-
1-yl)methyl]biphenyl (btmb, 1), was successfully synthesized,
and seven new coordination polymers, namely {M(oba)-
(btmb)}n [M = Cd2+ (2), Co2+ (3), Ni2+ (4), and Zn2+ (5)],
undulating networks with (4,4) sheets that are further packed
through van der Waals interactions to generate a 3D supra-
molecular structure. Complex 8 also represents a 2D network
with a 44-sql net, which is extended into a 3D supramolecular
framework by hydrogen-bonding interactions. The structural
differences of these complexes demonstrate that the confor-
mation of the btmb ligand and flexible aromatic polycarbox-
ylate anions play critical roles in the formation of the re-
sulting frameworks. Furthermore, their thermal properties
have been studied by thermogravimetric analysis (TGA) and
{M(sdba)(btmb)}n [M
=
Co2+ (6) and Cd2+ (7)], and
{[Cu(H2odpa)(btmb)(H2O)]·2H2O}n (8), (H2oba = 4,4Ј-oxydi-
benzoic acid, H2sdba = 4,4Ј-sulfonyldibenzoic acid, and
H4odpa = 4,4Ј-oxydiphthalic acid), have been synthesized by
utilizing the btmb ligand and the polymers have been char-
acterized in detail. Complexes 2–4 are isostructural exhibit-
ing 2D-layer structures and can be described as (3,4)-con- the TGA results reveal that the triazole-based frameworks
nected networks with (42.63.8)(42.6) topological notation.
Complex 5 shows 2D layers with left- and right-handed heli-
cal chains and has a (3,4)-connected net with (4.52)(4.53.72)
topology. Complexes 6 and 7 are isostructural and display 2D
have a high thermal stability, which suggests they are good
candidates for the construction of more stable complexes.
The photoluminescent properties of complexes 2, 5, and 7
have also been studied.
on conformational bis-imidazole/triazole ligands such as
1,4-bis(imidazol-1-ylmethyl)benzene, 1,4-bis(imidazolyl)-2-
butyne, 1,1Ј-(1,4-butanediyl)-bis(imidazole), 1,4-bis(tri-
azole-1-ylmethyl)benzene, and 9,10-bis(triazol-1-ylmethyl)-
anthracene,[12–15] are highly attractive because of their coor-
dinating tendency to produce entangled frameworks. There-
fore, the 4,4Ј-bis[(1,2,4-triazol-1-yl)methyl]biphenyl (btmb)
ligand is a good candidate for the construction of coordina-
tion polymers for the following reasons: (i) compared with
the bis-imidazole (bimb) ligand [bimb = 4,4Ј-bis(imidazol-
1-ylmethyl)biphenyl],[16] the 1,2,4-triazole group of btmb
exhibits a strong and typical coordination capacity and can
provide more potential coordination sites; (ii) two 1,2,4-tri-
azole groups can freely twist around two –CH2– groups
with different angles to generate different conformations
and coordination modes. In addition, two phenyl rings can
also twist around the C–C single bond with different tor-
sion angles to meet the requirements of the coordination
geometries; (iii) it is noteworthy that self-assembly of coor-
dination polymers based on trizazole ligands have high en-
Introduction
Coordination polymers are currently of interest in the
field of supramolecular chemistry and crystal engineering,
not only because of their potential applications as func-
tional solid materials for microelectronics, fluorescence,
magnetic materials, nonlinear optics, ion exchange, cataly-
sis, and sorption,[1–2] but also because of their intriguing
aesthetic structures and topologies.[3–4] The coordination
polymeric frameworks can be rationally designed by careful
control of many factors such as the solvent system, tem-
perature, pH value, the metal-to-ligand ratio, geometric
requirements of metal ions, and second building-block li-
gands.[5–6]
Up to now, a number of pyridyl-containing ligands have
been widely employed to construct coordination polymers
with a variety of novel structural motifs and desirable physi-
cal properties.[7–9] According to the reported studies, the N-
donor imidazole and triazole ligands,[10–11] especially based
[a] Key Laboratory of Synthetic and Natural Functional Molecule ergy and good thermal stability.[1d,11a,17] Especially, the high
Chemistry of the Ministry of Education, Shaanxi, Key
thermal stability is required for coordination polymers to
Laboratory of Physico-Inorganic Chemistry, College of
be practical for potential applications as functional solid
Chemistry and Materials Science, Northwest University,
Xi’an 710069, P. R. China
materials.[18]
E-mail: wyaoyu@nwu.edu.cn
On the other hand, a mixed-ligand strategy is presently
a good choice for the construction of coordination poly-
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201000731.
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mers. The V-shaped organic aromatic multicarboxylate spe-
cies have been extensively employed as building blocks to
construct coordination polymeric frameworks,[16a,19] be-
cause they show various coordination modes with metal
ions, which give rise to a great variety of multidimensional
structures and fascinating topologies. So far, to the best of
our knowledge, only a few coordination polymers with the
btmb ligand have been reported.[20]
Herein, we have successfully synthesized a series of new
coordination polymers containing the conformational btmb
ligand, namely {M(oba)(btmb)}n [M = Cd2+ (2), Co2+ (3),
Ni2+ (4), and Zn2+ (5)], {M(sdba)(btmb)}n [M = Co2+ (6)
and Cd2+ (7)], and {[Cu(H2odpa)(btmb)(H2O)]·2H2O}n (8),
(H2oba = 4,4Ј-oxydibenzoic acid, H2sdba = 4,4Ј-sulfonyldi-
benzoic acid, and H4odpa = 4,4Ј-oxydiphthalic acid). The
results indicate that the structural diversities of the com-
plexes 2–8 result from employing the different organic carb-
oxylate ligands and the conformational btmb ligand. In ad-
dition, the elemental analyses, infrared spectroscopy (IR),
X-ray diffraction (XRD) patterns, thermogravimetric analy-
ses (TGA), and the photoluminescent properties of com-
plexes 2, 5, and 7 have been investigated (Scheme 1).
Scheme 2. Structures of the organic acid ligands (H2sdba, H2oba,
and H4odpa).
Description of Crystal Structures
4,4Ј-Bis[(1,2,4-triazol-1-yl)methyl]biphenyl (btmb) (1).
The single crystal of btmb has been isolated recently by
Xu.[21] The free btmb ligand displays anti-conformational
features that extend into a 1D chain through weak C–H···N
hydrogen-bond interactions (C···N 3.381 Å) (Figure S1,
Supporting Information).
{M(oba)(btmb)}n [M = Cd2+ (2), Co2+ (3), and Ni2+ (4)].
The three complexes {M(btmb)(oba)}n [M = Cd2+ (2), Co2+
(3), and Ni2+ (4)] are isostructural with the same mono-
clinic space group, P21/c, and distorted octahedral environ-
ments of the center ions. The structure of 2 will be de-
scribed in detail herein. As shown in Figure 1 (a), the Cd
atom is coordinated by four oxygen atoms from three dif-
ferent oba2– anions [Cd(1)–O 2.231(2)–2.403(2) Å] and two
Scheme 1. The coordination modes and conformations of the btmb
ligands in complexes 2–8.
Results and Discussion
Syntheses
In this work, the 4,4Ј-bis[(1,2,4-triazol-1-yl)methyl]bi- nitrogen atoms from two independent btmb ligands [Cd(1)–
phenyl (btmb) ligand was synthesized with the aim of un- N 2.314(2)–2.319(3) Å]. Each oba2– anion adopts a bis-
derstanding the coordination of btmb. As we know, hydro- monodentate/chelating coordination mode and the cad-
thermal synthetic methods have been demonstrated to be mium centers are bridged by the oba2– anions to form a 1D
an effective and powerful technique for growing crystals of channel-like looped chain (Figure 1, b), which contains two
coordination polymers with interesting structures and spe- kinds of rings (8- and 28-membered). The flexible btmb li-
cial properties. We carried out the reaction of btmb with V- gand has a cis-conformational coordination mode and links
shaped organic acids (Scheme 2) and transition-metal salts two CdII atoms to form a 34-membered loop [Cd···Cd
in an aqueous medium in a molar ratio of 1:1:1, respec- 16.148(1) Å] (part a of Figure S2, Supporting Information).
tively. The results show that single-crystal products suitable Then, the adjacent but independent 1D looped chains are
for X-ray anyalyses were successfully obtained at 160 °C connected together by the btmb ligand to form a 2D planar
(Scheme 3). All complexes are highly stable in air at ambi- motif (Figure 1, c, left). To further understand the topologi-
ent temperature and insoluble in common organic solvents cal structure of complex 2, if the oba2– ligand is regarded
and water.
as a 3-connected node, the btmb ligand is considered as a
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Coordination Polymers Constructed from a Bis-triazole Ligand
Scheme 3. Hydrothermal syntheses of complexes 2–8.
linear linker and the metal center can be treated as a 4- ence in the coordination modes of the sdba2– anions are
connector. The resulting structure of 2 affords a (3,4)-con- due to coordinative preferences of the metal centers (Fig-
nected 2D network with a (42·63·8)(42·6) topology (Fig- ure 3, a, Figure S3, a). The structure of 6 will be described
ure 1, c, right).[13e] In addition, the 3D supramolecular in detail herein. As shown in part a of Figure 3, each CoII
structure is formed by the linking of 2D layers through van ion exhibits a distorted tetrahedron environment, composed
der Waals interactions (C30···C15 3.357 Å) (Figure 1, d).[22] of two carboxylic oxygen atoms from two sdba2– anions
{Zn(oba)(btmb)}n (5). Single-crystal X-ray structural [Co(1)–O(1) 2.002(5) Å, Co(1)–O(3) 1.963(5) Å] and two ni-
analysis reveals that 5 crystallizes in the orthorhombic trogen atoms from two triazole rings [Co(1)–N(1)
space group Pbca and exhibits a 2D planar layer structure. 2.036(7) Å; Co(1)–N(4) 2.002(8) Å]. Each sdba2– anion
Each ZnII atom shows a distorted trigonal bipyramidal bridges cobalt atoms in a monodentate/monodentate coor-
configuration, which is defined by three oxygen atoms of dination mode to form a 1D infinite zigzag chain with a
carboxyl groups of oba2– anions and two nitrogen atoms of Co···Co distance of 14.445(0) Å (Figure S3, b). Interest-
two distinct btmb ligands (Figure 2, a). The distances of ingly, the adjacent Co2+ ions are linked by anti-conforma-
Zn1–O [1.962(5)–2.227(5) Å] and Zn1–N [2.023(7)– tional btmb ligands in a Z-shaped fashion, which results
2.057(6) Å] are in the normal range. In the structure of 5, from a 1D sine wave-like chain with a Co···Co distance of
as shown in Figure 2 (b), it is of interest that the ZnII ions 16.871(7) Å (Figure S3, c). Four CoII atoms are interlinked
are linked by oba2– ligands to form an infinite 2D network by btmb and sdba2– ligands to afford a square grid with a
including left- and right-handed helical chains with a pitch large window (14.445(0)ϫ16.871(7) Å). These are further
of 11.206 Å along the a axis. The dihedral angle between connected together into a 2D undulating network with a
the two phenyl rings of the oba2– ligand is 64.76°. The btmb (4,4) sheet by considering the [CoN2O2] units as the net-
ligand exhibits a cis conformation to link two ZnII ions to work nodes (Figure 3, b). In addition, the 3D supramolec-
form the 0D loop with a distance of 15.639(1) Å, which is ular framework is stabilized by the linking of a 2D undulat-
the same as for complex 2. From a topological view, the ing network through van der Waals interactions (C16···C17
oba2– anions are considered as 3-connected nodes, and the 3.484 Å) (Figure 3, c).
ZnII ion is viewed to be a 4-connected node, then the btmb
{[Cu(H2odpa)(btmb)(H2O)]·2H2O}n (8). The single-crys-
ligand is simplified as a linker connecting the metal centers. tal X-ray structural analysis reveals that complex 8 crys-
¯
Thus, the structure of 5 can be simplified to a unique (3,4)- tallizes in the triclinic space group P1, and that there are
connected framework with a (4.52)(4.53·72) topology (Fig- two types of coordination environments around the CuII
ure 2, c).[13e]
ions in the crystal structure (Figure 4, a). The Cu1 atom
Additionally, the adjacent 2D layers are held together by has a distorted oblate octahedral geometry because of the
van der Waals forces (C17···C32 3.564 Å) to afford a 3D Jahn–Teller effect, which is defined by two carboxylic oxy-
supramolecular network along the b axis (Figure 2, d).
gen atoms of two H2odpa2– ligands [Cu1–O1 1.980(2) Å]
{M(sdba)(btmb)}n [M = Co2+ (6) and Cd2+ (7)]. The and two nitrogen atoms of two triazole rings from the anti
structures of 6 and 7 are isostructural and the only differ- conformation of the btmb ligands [Cu1–N1 1.974(2) Å] oc-
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Figure 1. (a) ORTEP diagram showing the coordination environments for CdII ions in 2. All H atoms are omitted for clarity. (b) Chain
of oba2– anions and CdII atoms forming a 1D channel. (c) View of the 2D-layer structure of complex 2 along the b axis and a schematic
representation of the (3,4)-connected 2D network with (42·63·8)(42·6) topological notation. The long rod represents the btmb ligand.
(d) Overall view of the 3D supramolecular framework, formed by the linking of 2D layers through van der Waals interactions.
cupying the equatorial plane, while two carboxylic oxygen oxygen atoms from the carboxylic groups of H2odpa2–
atoms of two H2odpa2– ligands [Cu1–O2 2.627(1) Å] are [Cu2–O3 1.963(3) Å], and two coordination water mole-
arranged in the trans-axial direction. However, the distance cules. The distance between Cu2–O12 also suggests a very
between the carboxylic oxygen (O2) atom and the Cu1 atom weak interaction [Cu2–O12 2.772(4) Å].[23] These weak in-
is in unusual and regarded as a non-negligible weak interac- teractions (Cu1–O2 and Cu2–O12) may play an important
tion.[23] Compared with the Cu1 atom, the Cu2 atom also role in fixing the metal centers in a definite conformation
occupies the center of a distorted elongated octahedral ge- in 8. Similar to complex 6, Cu1 and Cu2 [Cu···Cu
ometry that is six-coordinate. It is coordinated by two nitro- 6.152(0) Å] are linked by carboxylic groups of the H2odpa2–
gen atoms from the btmb ligands [Cu2–N4 1.977(4) Å], two ligand to form a 1D zigzag chain in a monodentate/chelat-
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Coordination Polymers Constructed from a Bis-triazole Ligand
Figure 2. (a) ORTEP diagram showing the coordination environments of the ZnII atoms in 5. All H atoms are omitted for clarity. (b) 2D
network of ZnII atoms and oba2– anions containing left- and right-handed helical chains along the a axis. (c) Schematic description of
the (3,4)-connected 2D framework built on the 3-connected oba2– anions and 4-connected ZnII centers (long linkers showing btmb
ligands). (d) Weak van der Waals interactions between the 2D nets in 5.
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Figure 3. (a) ORTEP diagram showing the coordination environments for CoII atoms in 6. All H atoms are omitted for clarity. (b) Showing
a 2D undulating network with (4,4) sheet in 6. (c) A view of the packing by weak van der Waals interactions between the 2D layers in
6 and 7.
ing coordination mode. A 1D infinite single-stranded (Figure S4, a and b).[16b] These 1D chains are interlinked
polymeric chain is also formed by anti-conformational together to generate a 2D network with 44-sql nets
btmb ligands with a Cu···Cu separation of 16.359(0) Å [6.151(8)ϫ16.591(0) Å]; the H2odpa2– ligand is simplified
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Coordination Polymers Constructed from a Bis-triazole Ligand
as a rod (Figure 4, b). Furthermore, the adjacent planar
layers are packed together with weak hydrogen-bonding
interactions [O···O 2.716(4)–2.933(1) Å] to generate a 3D
supramolecular network (Figure 4, c).
Discussion
From the structural descriptions above (Scheme 3) the
conformation of the btmb ligand has an important effect
on the constructuction of different structures in the self-
assembly process. As illustrated in Scheme 1, generally, the
long flexible btmb ligand shows two types of conformations
(cis and anti) depending on the rotation of the two trizole
rings,[16,19] which have formed distinct motifs with different
configurations. For example, metal ions were bridged by
btmb ligands with a cis conformation to form 0D loops in
2–5, whereas the 1D infinite chains based on an anti config-
uration were formed in 6–8. The different conformations of
btmb ligands may be attributed to the introduction of or-
ganic anions.[12j] In addition, although the structures of 2
and 5 display 2D networks with the same (3,4)-connected
notation, their topological structures are quite different.
The CdII ion is six-coordinate and can be described as hav-
ing a distorted octahedral geometry in 2, but the ZnII ion
is five-coordinate and has a distorted trigonal-bipyramidal
geometry. The different coordination numbers may be sub-
stantially attributed to the distinct radii of the CdII (2) and
ZnII (5) metal ions. The disparate radii of the metal ions
induce the change of the binding mode of the O/N atoms
to from different structures and topologies. It is suggested
that metal ions are responsible for the different formations
of the resulting structures.
X-ray Powder Diffraction and Thermal Properties
In order to characterize the phase purity of these com-
plexes, X-ray powder diffraction (XRD) patterns of com-
plexes 2–8 were performed at room temperature (Fig-
ure S5). Minor differences can be seen in the positions, in-
tensities, and widths of some peaks, which indicates that
these complexes were synthesized as a single phase.
To estimate the thermal stability of coordination poly-
mers 2–8, thermogravimetric analyses (TGA) were carried
out under a N2 atmosphere in the temperature range 30–
850 °C. As depicted in Figure 5, the TGA curves of these
Figure 4. (a) ORTEP diagram showing the coordination environ-
ments for CuII atoms in 8. All H atoms and lattice water molecules
and disordered atoms are omitted for clarity. (b) The 2D structure
with a 4-connected topology [6.151(8)ϫ16.591(0) Å] in 8. (c) The
3D supramolecular structure was formed through hydrogen-bond-
ing interactions (dotted lines) [O···O 2.716(4)–2.933(1) Å] in 8.
Figure 5. TGA curves of complexes 2–8 under a N2 atmosphere.
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complexes indicate that the overall frameworks of com- attributed to sdba2– ligand chelation at the CdII center and
plexes 3 and 5 began to collapse from 285 °C, while 2 and their rigidity. The emission peaks for 7 in nature are proba-
4 were more stable up to 350 °C for 2 and 395 °C for 4, bly assigned to ligand-to-metal charge-transfer (LMCT)
where the decomposition of the framework starts. For 6, no transitions.[25b,26] In comparison with 2, 5, and 7, the dif-
weight losses were observed up to 338 °C. The framework ferent emission bands may be attributed to the metal–ligand
of complex 7 is stable up to 316 °C and the rapid weight coordinative behaviors and the different architectures fea-
loss from 316 to 454 °C corresponds to the loss of the btmb turing different ligands.
ligand (calcd: 44.04%; found 43.13%), where the overall
framework begins to decompose slowly. For 8, the weight
loss (7.01%) is attributed to the release of lattice water and
coordinated water molecules in the temperature range 80–
Conclusions
170 °C, which is in good agreement with the calculated
In summary, we have successfully synthesized and char-
value (6.95%). The second step occurs over the range 170– acterized seven coordination polymers with a conforma-
464 °C, corresponding to the loss of btmb ligands (calcd: tional btmb ligand and V-shaped polycarboxylate ligands.
40.65%; found 40.02%). To some extent, the results reveal The structural diversities indicate that the conformation of
that the triazole-based frameworks have a high thermal sta- the btmb ligand and flexible aromatic polycarboxylate
bility, which is suggested as a good candidate for the con- anions play dominant roles in the assembly of the resulting
struction of more stable coordination polymers.
framework. In addition, the TGA results reveal that the tri-
azole-based frameworks have a high thermal stability,
which is suggested as a good candidate for the construction
of more stable coordination polymers. On the basis of this
work, other coordination polymers with conformational
bis-triazole ligands and aromatic organic carboxylate
anions with interesting aesthetic structures as well as physi-
cal properties will be further explored in our laboratory.
Photoluminescent Properties
The metal–organic coordination polymers, especially the
d10-metal complexes, have been investigated for luminescent
properties and for potential application as photoactive ma-
terials.[24] Therefore, in the present work, the luminescent
properties of 2, 5, and 7 as well as the free ligands were
investigated in the solid state at room temperature (Fig-
ure 6). The luminescent spectra of the free btmb ligand
shows emission at λmax = 352 nm upon excitation at
280 nm, λmax = 330 nm for H2oba and 347 nm for H2sdba
(λex = 280 nm). Complexes 2 and 5 exhibit an intense lumi-
nescence emission peak at 328 nm for 2 and λmax = 321 nm
for 5 (λex = 280 nm). In comparison with the btmb ligand,
the emission of 2 and 5 may be assigned to intraligand (π–
π*) fluorescence.[25] However, the emission peak for 7 is red-
shifted relative to that of the free ligands and exhibits an
intense luminescence emission at λmax = 372 nm upon exci-
tation at 280 nm. The enhancement of luminescence may be
Experimental Section
Reagents and Physical Measurements: All reagents and solvents em-
ployed were commercially available and used as received without
further purification. Elemental analyses were recorded with a Per-
kin–Elmer model 240C instrument. Mass spectra were determined
with an AXIMA-CFR™plus MALDI-TOF mass spectrometer. IR
spectra were recorded with a Perkin–Elmer Spectrum One spec-
trometer in the region 4000–400 cm–1 using KBr pellets. Thermal
analyses were performed with a NETZSCH STA 449C microana-
lyzer with a heating rate of 10 °Cmin–1 under a N2 atmosphere.
The X-ray powder diffraction (XRD) data were recorded with a
Rigaku RU200 diffractometer at 60 kV, 300 mA, and Cu-Kα radia-
tion (λ = 1.5406 Å), with a scan speed of 2°min–1 and a step size
of 0.02° in 2θ. Luminescence spectra for the solid samples were
investigated with a Hitachi F-4500 fluorescence spectrophotometer
at room temperature. 1H NMR spectra were recorded using
INOVA 400 MHz (Varian).
btmb (1): The 4,4Ј-bis[(1,2,4-triazol-1-yl)methyl]biphenyl (btmb) li-
gand was synthesized from literature methods.[19,14d] Yield 63%;
m.p. 168–170 °C. MS: m/z = 317.63 for [Hbtmb]+. 1H NMR
(CD3OD): δ = 5.468 (4 H), 7.393 (2 H), 7.634 (2 H), 8.008 (2 H),
8.608 (2 H) ppm.
{Cd(oba)(btmb)}n (2): A mixture containing Cd(CH3COO)2·2H2O
(0.1 mmol, 26.7 mg), btmb (0.1 mmol, 31.6 mg), H2oba (0.1 mmol,
25.8 mg), and NaOH (0.2 mmol, 8.0 mg) in H2O (10 mL) was se-
aled in a 23 mL Teflon®-lined autoclave and heated at 160 °C for
3 d. Colorless, block, single crystals suitable for X-ray diffrac-
tion were obtained in 46% yield (31.5 mg, based on Cd).
C32H24CdN6O5 (684.97): calcd. C 56.11, H 3.53, N 12.27; found C
56.32, H 3.38, N 12.62. IR (KBr): ν = 3440 (s), 3097 (m), 2926 (w),
˜
1599 (s), 1564 (m), 1532 (m), 1500 (w), 1438 (w), 1383 (s), 1300
(w), 1281 (w), 1248 (s), 1184 (m), 1157 (w), 1137 (m), 1101 (w),
Figure 6. The solid-state photoluminescent spectra of 2, 5, 7, and
the free ligands at room temperature.
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Coordination Polymers Constructed from a Bis-triazole Ligand
1009 (m), 985 (w), 878 (w), 860 (w), 827 (w), 809 (m), 786 (m), 716
(w), 676 (m), 650 (m), 620 (w), 539 (w), 504 (m) cm–1.
861 (m), 747 (s), 724 (w), 686 (w), 620 (m), 568 (m), 548 (w), 463
(w) cm–1.
{Cd(sdba)(btmb)}n (7): The synthetic method was the same as that
used for 6, except that Cd(CH3COO)2·2H2O was used instead of
Co(CH3COO)2·4H2O. Colorless block crystals of 7 were obtained
in 45% yield (33.0 mg, based on Cd). C32H24CdN6O6S (733.03):
calcd. C 52.43, H 3.30, N 11.46; found C 52.72, H 3.52, N 11.73.
{Co(oba)(btmb)}n (3): The synthetic method was the same as that
used for 2, except that Co(CH3COO)2·4H2O was used instead of
Cd(CH3COO)2·2H2O. Yield 65% (41.0 mg, based on Co).
C32H24CoN6O5 (631.50): calcd. C 60.86, H 3.83, N 13.31; found C
60.91, H 3.62, N 13.54. IR (KBr): ν = 3424 (s), 3099 (m), 2926 (w),
˜
IR (KBr): ν = 3214 (s), 3114 (s), 1815 (w), 1659 (w), 1590 (s), 1546
˜
1915 (w), 1605 (s), 1566 (w), 1531 (m), 1499 (w), 1384 (s), 1280 (w),
1247 (m), 1180 (w), 1157 (w), 1135 (m), 1098 (w), 1011 (w), 903
(w), 879 (w), 852 (w), 810 (m), 785 (m), 760 (m), 714 (w), 683 (w),
653 (w), 619 (w), 543 (m), 507 (w) cm–1.
(s), 1490 (m), 1403 (s), 1326 (w), 1297 (m), 1215 (w), 1155 (m),
1130 (m), 1101 (w), 1070 (w), 1012 (m), 968 (w), 907 (w), 865 (s),
803 (w), 777 (m), 749 (s), 695 (w), 676 (w), 619 (m), 574 (w), 494
(w), 468 (m) cm–1.
{Ni(oba)(btmb)}n (4): The procedure was the same as that used for
3, except that Co(CH3COO)2·4H2O was replaced by Ni(CH3COO)
2·4H2O. Green, suitable crystals for crystal structure determination
of 4 were obtained in 57% yield (36.0 mg, based on Ni).
C32H24N6NiO5 (631.28): calcd. C 60.88, H 3.83, N 13.31; found C
{[Cu(H2odpa)(btmb)(H2O)]·2H2O}n (8):
A mixture containing
Cu(CH3COO)2·H2O (0.1 mmol, 20.0 mg), btmb (0.1 mmol,
31.6 mg), H4odpa (0.1 mmol, 31.0 mg), and NaOH (0.2 mmol,
8.0 mg) in H2O (10 mL) was sealed in a 23 mL Teflon®-lined auto-
clave and heated at 160 °C for 3 d. Blue, block-shaped single crys-
tals suitable for X-ray diffraction were obtained in 72% yield
(56.0 mg, based on Cu). C34H30CuN6O12 (778.18): calcd. C 52.48,
60.86, H 3.61, N 13.03. IR (KBr): ν = 3430 (s), 2925 (w), 1599 (s),
˜
1530 (w), 1497 (vw), 1383 (s), 1296 (w), 1246 (m), 1156 (w), 1129
(m), 1016 (w), 878 (m), 756 (m), 682 (w), 652 (w), 618 (w), 546 (w),
504 (w) cm–1.
H 3.89, N 10.80; found C 52.67, H 3.747, N 10.77. IR (KBr): ν =
˜
3424 (s), 3123 (s), 2924 (w), 2854 (w), 1698 (s), 1612 (m), 1581 (m),
1549 (m), 1388 (s), 1281 (m), 1253 (m), 1224 (m), 1193 (m), 1128
(s), 1078 (w), 1043 (w), 1002 (w), 962 (w), 938 (w), 879 (w), 839 (w),
799 (m), 753 (m), 674 (w), 630 (w), 553 (w), 502 (w), 461 (w) cm–1.
{Zn(oba)(btmb)}n (5): The synthetic method was the same as that
used for 2, except that Zn(CH3COO)2·4H2O was used instead of
Cd(CH3COO)2·2H2O. Yield 56% (35.7 mg, based on Zn).
C32H24N6O5Zn (637.94): calcd. C 60.25, H 3.79, N 13.17; found C
X-ray Crystallography: Single-crystal X-ray diffraction analyses of
the seven complexes were carried out with a Bruker SMART
APEX II CCD diffractometer equipped with a graphite monochro-
mated Mo-Kα radiation (λ = 0.71073 Å) by using the φ/ω scan tech-
nique at room temperature. All structures were solved by direct
methods and refined by full-matrix least-squares fittings on F2 by
SHELX-97.[27] Absorption corrections were applied by using the
multi-scan program SADABS.[28] All non-hydrogen atoms were re-
fined anisotropically, the water hydrogen atoms were located from
difference Fourier maps and refined with isotropic thermal param-
eters, 1.5 times those of their carrier atoms. Hydrogen atoms of the
60.48, H 3.67, N 13.45. IR (KBr): ν = 3422 (s), 3096 (w), 1928 (w),
˜
1680 (m), 1596 (s), 1560 (w), 1501 (m), 1384 (s), 1318 (w), 1288
(w), 1250 (s), 1158 (m), 1126 (m), 1103 (w), 1003 (m), 934 (w), 877
(w), 855 (m), 828 (w), 764 (m), 693 (w), 673 (w), 650 (m), 618 (w),
544 (m) cm–1.
{Co(sdba)(btmb)}n (6): The synthetic method was the same as that
used for 3, except that H2sdba (0.1 mmol, 27.1 mg) was used in-
stead of H2oba. Yield 62% (42.1 mg, based on Co).
C32H24CoN6O6S (679.56): calcd. C 56.56, H 3.56, N 12.37; found
C 56.73, H 3.74, N 12.68. IR (KBr): ν = 3425 (s), 3098 (m), 2962
˜
(w), 2852 (w), 2665 (m), 2541 (w), 1691 (s), 1606 (m), 1562 (w), water molecules in 8 were located from the difference maps and
1493 (w), 1424 (m), 1401 (m), 1379 (w), 1330 (w), 1283 (s), 1213
(w), 1157 (s), 1121 (m), 1099 (m), 1068 (w), 1014 (m), 930 (m),
then refined by a riding model. In 5, some carbon atoms (C19,
C20, C22, C23, C25, C26, C28, C29; C19Ј, C20Ј, C22Ј, C23Ј, C25Ј,
Table 1. Crystal data and structure refinements for complexes 2–5.[a]
2
3
4
5
Empirical formula
C32H24CdN6O5
684.97
C32H24CoN6O5
631.50
C32H24NiN6O5
631.28
C32H24ZnN6O5
637.94
Mr [gmol–1]
Crystal system
Space group
monoclinic
P21/c
monoclinic
P21/c
monoclinic
P21/c
orthorhombic
Pbca
a [Å]
b [Å]
c [Å]
α [°]
15.2965(10)
16.9485(12)
11.0150(8)
90
15.056(9)
16.747(11)
10.838(7)
90
15.0103(19)
16.738(2)
10.8576(14)
90
16.6690(19)
11.1789(12)
29.645(3)
90
β [°]
102.6370(10)
90
2786.5(3)
4
1.633
0.839
102.255(8)
90
2670
102.245(2)
90
2665.8(6)
4
1.573
0.785
90
90
γ [°]
V [Å3]
5524.1(10)
8
1.534
Z
4
ρcalcd. [gcm–3]
1.571
0.700
μ [mm–1]
0.945
F [000]
θ [°]
Reflections collected
Goodness-of-fit on F2
Final R[a] indices [IϾ2σ(I)]
1384
1.82–25.10
13737
1.071
R1 = 0.0292
wR2 = 0.0761
1300
1.84–25.10
13054
1.075
R1 = 0.0891
wR2 = 0.1969
1304
1.85–25.10
13255
0.995
R1 = 0.0552
wR2 = 0.1386
2624
1.84–25.10
26061
1.115
R1 = 0.0776
wR2 = 0.1931
2
2 2
[a] R1 = Σ(|Fo| – |Fc|) / Σ|Fo|; wR2 = {Σ[w(Fo – Fc ) ] / Σ[w(Fo2)2]}1/2
.
Eur. J. Inorg. Chem. 2010, 5545–5555
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
5553

C. Ren, P. Liu, Y.-Y. Wang, W.-H. Huang, Q.-Z. Shi
FULL PAPER
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C26Ј, C28Ј, C29Ј) of two phenyl rings of the btmb ligand are disor-
dered and were refined using carbon atoms split into two sites with
a 50% occupancy. In complex 8 there is one disordered carboxylic
group, (C34, O7, O8) and (C34Ј, O7Ј, O8Ј) were refined using O
or C atoms split over two equivalent sites, with a total occupancy
of 1. The crystallographic data and selected bond lengths and
angles for 2–8 are listed in Tables 1, 2, and S1 (Supporting Infor-
mation).
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Table 2. Crystal data and structure refinements for complexes 6–
8.[a]
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6
7
8
Empirical formula
Mr [gmol–1
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C32H24CoN6O6S C32H24CdN6O6S C34H30CuN6O12
]
679.56
monoclinic
P21
6.1365(10)
16.580(3)
14.445(2)
90
99.139(2)
90
1451.0(4)
2
1.555
0.722
698
1.43–25.10
7343
733.03
monoclinic
P21
6.2057(10)
16.634(3)
14.671(3)
90
100.005(2)
90
1491.4(5)
2
1.632
0.859
740
778.18
triclinic
P1
¯
9.7697(10)
11.5172(12)
17.0312(18)
96.1170(10)
103.6930(10)
109.9310(10)
1713.2(3)
2
1.509
0.712
802
1.92–25.00
8592
γ [°]
V [Å3]
Z
[5]
ρcalcd. [gcm–3
]
μ [mm–1
]
F [000]
θ [°]
Reflections collected
1.87–25.10
7520
1.025
R1 = 0.0467
wR2 = 0.0807
Goodness-of-fit on F2 1.039
1.061
R1 = 0.0610
wR2 = 0.1820
Final R[a] indices
[IϾ2σ(I)]
R1 = 0.0554
wR2 = 0.1314
[a] R1 = Σ(|Fo| – |Fc|) / Σ|Fo|; wR2 = {[Σ[w(Fo – Fc2)2 / Σ[w(Fo ) ]}1/2
.
2
2 2
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CCDC-771063 (for 2), -771064 (for 3), -771065 (for 4), -771066
(for 5), -771067 (for 6), -771068 (for 7), -771069 (for 8) contain
the supplementary crystallographic data for this paper. These data
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Supporting Information (see also the footnote on the first page of
this article): Additional figures selected bond lengths and angles,
XRD patterns.
Acknowledgments
The authors gratefully acknowledge financial support of this work
by the National Natural Science Foundation of China (grant
number 20771090), the State Key Program of National Natural
Science of China (grant number 20931005), the Natural Science
Foundation of Shaanxi Province (grant number 2009JZ001), and
the Specialized Research Fund for the Doctoral Program of Higher
Education (grant number 20096101110005).
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Received: 5 July 2010
Published Online: November 4, 2010
Eur. J. Inorg. Chem. 2010, 5545–5555
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