Novel Supramolecular Frameworks Self-Assembled from One-Dimensional Polymeric Coordination Chains

Article abstract of DOI:10.1002/ejic.200300390

The novel supramolecular frameworks [Cd(BDC)(phen)-(H₂O)] _n (2) and [Cd₂(HBTC)₂(phen)₂] _2n·nCd(HBTC)(phen)₂ (3) have been synthesized by reaction of the metal source Cd(phen)₂(NO₃)₂ (1) with benzene-1,4-dicarboxylic acid (H₂BDC) and benzene-1,3,5-tricarboxylic acid (H₃BTC), respectively in a mixed solution of DMF/C₂H₅OH/H₂O. The three-dimensional supramolecular structure of 2 is constructed through hydrogen-bond and aromatic π-π interactions between adjacent metal-organic polymeric coordination chains. Conversely, interestingly, the supramolecular architecture 3 is formed by extending 1-D metal-organic polymeric coordination chains into a 3-D framework by hydrogen-bond interactions between polymeric coordination chains and metal-organic coordination complexes instead of by interchain hydrogen-bond interactions. Additionally, these three compounds exhibit strong fluorescence at room temperature in the solid state. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200300390

FULL PAPER
Novel Supramolecular Frameworks Self-Assembled from One-Dimensional
Polymeric Coordination Chains
Xin Shi,[a] Guangshan Zhu,*[a] Qianrong Fang,[a] Gang Wu,[a] Ge Tian,[a] Renwei Wang,[a]
Daliang Zhang,[a] Ming Xue,[a] and Shilun Qiu*[a]
Keywords: Supramolecular chemistry / Coordination modes / Fluorescence / Polymers
The novel supramolecular frameworks [Cd(BDC)(phen)-
(H2O)]n (2) and [Cd2(HBTC)2(phen)2]2n·nCd(HBTC)(phen)2
(3) have been synthesized by reaction of the metal source
Cd(phen)2(NO3)2 (1) with benzene-1,4-dicarboxylic acid
(H2BDC) and benzene-1,3,5-tricarboxylic acid (H3BTC), re-
spectively in a mixed solution of DMF/C2H5OH/H2O. The
three-dimensional supramolecular structure of 2 is con-
structed through hydrogen-bond and aromatic π−π interac-
tions between adjacent metal-organic polymeric coordina-
tion chains. Conversely, interestingly, the supramolecular
architecture 3 is formed by extending 1-D metal-organic
polymeric coordination chains into a 3-D framework by hy-
drogen-bond interactions between polymeric coordination
chains and metal-organic coordination complexes instead of
by interchain hydrogen-bond interactions. Additionally,
these three compounds exhibit strong fluorescence at room
temperature in the solid state.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
(HBTC)2(phen)2]2n·nCd(HBTC)(phen)2 (3), which are self-
assembled from metal-organic coordination compound
Cd(phen)2(NO3)2 (1) with benzene-1,4-dicarboxylic acid
(H2BDC) and benzene-1,3,5-tricarboxylic acid (H3BTC),
respectively.
Metal-organic coordination frameworks with various in-
triguing topologies have been extensively studied for their
versatile chemical and physical properties and potential ap-
plications in functional materials.[1Ϫ8] With the develop-
ment of supramolecular chemistry, self-assembly based on
molecules has become an effective approach to construct
functional coordination frameworks. Hydrogen bonds pro-
vide an ideal synthetic example for the rational design of
an organic crystalline framework.[9] Recently, attempts have
been made to combine metalϪligand coordination and hy-
drogen bond interactions to self-assemble multidimensional
metal-organic supramolecular frameworks.[10Ϫ12] Some 3-D
supramolecular frameworks have been self-assembled from
one-dimensional polymeric coordination chains, which are
generated by transition metal ions and multidentate units,
through hydrogen bonding and πϪπ interactions.[11,12]
Metal-organic coordination compounds as reactants pro-
vide not only transition metal ions but also segmental or-
ganic ligands in synthesis systems. Hence novel topologies
and, particularly, chemical and physical properties may be
obtained if metal-organic coordination compounds are
used as the metal source to prepare supramolecular frame-
works; however, we could not find any reported examples.
We report here the two novel fluorescent supramolecular
frameworks [Cd(BDC)(phen)(H2O)]n (2) and [Cd2-
Results and Discussion
Description of Crystal Structure
Cd(phen)2(NO3)2 (1)
In the asymmetric unit of coordination compound 1
(Figure 1) the seven-coordinate cadmium center is chelated
by four nitrogen atoms (N1, N2; N3, N4) of two chelating
[a]
Key Laboratory of Inorganic Synthesis
Chemistry Jilin University,
& Preparative
Changchun 130023, P. R. China
Fax: (internat.) ϩ 86-431-5671974
E-mail: sqiu@mail.jlu.edu.cn
Figure 1. Asymmetry unit of 1; thermal ellipsoids are drawn at the
50% probability level; all hydrogen atoms are omitted for clarity
Eur. J. Inorg. Chem. 2004, 185Ϫ191
DOI: 10.1002/ejic.200300390
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185

X. Shi, G. Zhu, Q. Fang, G. Wu, G. Tian, R. Wang, D. Zhang, M. Xue, S. Qiu
˚
FULL PAPER
phen ligands and three oxygen atoms (O1, O2; O4) of two C9ϪH9···O4 hydrogen bond is 3.219 A long and the
Ϫ
NO3 anions in different ways.
C9ϪH9···O4 angle is 147.20°, which are acceptable accord-
ing to recent studies.[12b,14] There are also aromatic πϪπ
stacking interactions between neighboring undulating lay-
ers. The planeϪplane distance between adjacent two phen
[Cd(BDC)(phen)(H2O)]n (2)
A single-crystal X-ray analysis revealed that 2 is self-as-
sembled from 1-D zig-zag polymeric coordination chains.
In the asymmetric unit of 2, there are one Cd atom, one
BDC ligand, one phen ligand and one coordinated H2O
molecule. [Figure 2 (a)] The cadmium atom is seven-coordi-
nate through coordination to five oxygen atoms (O1, O2;
O3, O4; O5) of two chelating carboxylate groups of two
BDC ligands, one water molecule and two nitrogen atoms
(N1, N2) of one chelating phen ligand. The bond lengths
˚
ligands of two neighboring layers is 3.517 A, which is
reasonable.[12b,15] All lateral phen ligands from neighboring
undulating layers are intercalated in a zipper-like manner,
which is similar to some previous examples.[12b,12c] Thus,
the CϪH···O hydrogen bonds along with aromatic πϪπ in-
teractions further extend the 2-D undulating layers into a
3-D supramolecular framework (Figure 3).
˚
of Cd1ϪO2 and Cd1ϪO3 are 2.567 and 2.401 A, which are
longer than those in other cadmium carboxylate coordi-
nation polymers.[13a] The distortion of the CdϪO bond may
be due to the severe steric hindrance caused by the bulky
phen group.
Figure 3. 3-D supramolecular framework along the [010] direction;
neighboring undulating 2-D layers are intercalated in a zipper-like
manner through CϪH···O hydrogen bonds and πϪπ interactions
[Cd2(HBTC)2(phen)2]2n·nCd(HBTC)(phen)2 (3)
X-ray crystallography reveals that 3 consists of 1-D poly-
meric coordination chains [Cd2(HBTC)2(phen)2]n and me-
tal-organic coordination complexes nCd(HBTC)(phen)2.
There are three six-coordinate cadmium centers in each
asymmetric unit of 3. Cd1 adopts a distorted octahedral
geometry by coordinating to four nitrogen atoms (N1, N2;
N3, N4) of two chelating phen ligands and two oxygen
Figure 2. (a) Perspective view of the coordination environment of atoms (O14; O17) of two monodentate carboxylate groups
the cadmium atom in 2; thermal ellipsoids are drawn at the 50%
from two H3BTC ligands.
Two carboxylate groups from each of two crystallograph-
ically equivalent H3BTC ligands bridge two cadmium
probability level; all hydrogen atoms are omitted for clarity; (b) 1-
D zig-zag polymeric chain
Each BDC ligand bridges two cadmium atoms in bis(bi- atoms (Cd1 and Cd1A) to form a metal-organic coordi-
dentate) fashion to form a 1-D infinite zig-zag chain [Fig- nation complex but the third carboxy group is uncoordi-
ure 2(b)]. The coordinated H2O molecules of the polymeric nated. From the difference in bond lengths between
˚
˚
chains are well positioned to form interchain hydrogen C57ϪO15 [1.209(9) A] and C57ϪO16 [1.326(9) A] in the
bonds with the carboxylate oxygen atoms. The oxygen uncoordinated carboxy group, C57ϪO15 can be assigned
atoms of coordinated H2O molecules and carboxylate oxy- to a double bond and C57ϪO16 to a single bond, and the
gen atoms of BDC ligands from adjacent chains form hydrogen atom H16 should be linked to O16 [Figure 4 (a)].
˚
strong hydrogen bonds (O2···O5 2.704 A), which combine
Cd2 also adopts a distorted octahedral geometry by co-
the 1-D zig-zag chains into 2-D undulating layers. Between ordinating to four oxygen atoms (O1, O2; O5, O8) of one
neighboring 2-D undulating layers, C atoms with hydrogen chelating carboxylate group of one H3BTC ligand, two bis-
atoms of phen ligands and carboxylate oxygen atoms of (monodentate) carboxylate groups of two different H3BTC
BDC ligands from neighboring layers form interlayer ligands and two nitrogen atoms (N5, N6) of one chelating
CϪH···O hydrogen bonds (C9ϪH9···O4). The C9···O4 in phen ligand. The coordination environment of Cd3 is same
186
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Novel Supramolecular Frameworks
FULL PAPER
Figure 5. Double chain formed by intercalating two adjacent 1-D
chains in a zipper-like manner through hydrogen bonds and πϪπ
interactions
˚
through CϪH···O hydrogen bonds (C17···O1 2.217 A,
C17ϪH17···O1 154.77°)[14] and aromatic πϪπ stacking in-
[15]
˚
teractions (planeϪplane distance 3.439 A) (Figure 5).
Each double polymeric chain is surrounded by metal-or-
ganic coordination complexes (Figure 6). Uncoordinated
Figure 4. Perspective view of (a) the coordination environment of
Cd1 in 3 and (b) the coordination environment of Cd2 and Cd3 in
3; thermal ellipsoids are drawn at the 50% probability level; all
hydrogen atoms are omitted for clarity
as that of Cd2 [Figure 4 (b)]. The bond lengths and angles
of CdϪO are similar to those of cadmium trimesate poly-
mers.[13b]
The coordinated H3BTC ligands have two unchelated
˚
carboxy groups. The CϪO bonds [C5ϪO3 1.298(9) A,
˚
C40ϪO11 1.303(10) A] are much longer than CϭO
˚
˚
[C5ϪO4 1.203(9) A, C40ϪO12 1.195(10) A] in the carboxy
groups, so C5ϪO4 and C40ϪO12 can be assigned as
double bonds and C5ϪO3 and C40ϪO11 as single bonds,
with H3 and H11 linked to O3 and O11. The IR spectrum
of 3 exhibits a broad band at ca. 3200 cmϪ1, which is typical
of the OϪH vibration of a carboxy group. This shows that
deprotonation of the H3BTC ligands is incomplete, which
is in good agreement with the uncoordinated carboxy
groups in the structure of 3.
Incompletely deprotonated H3BTC ligands using the car-
boxylate functionality link Cd2 and Cd3 to form 1-D infi-
nite polymeric chains [Cd2(HBTC)2(phen)2]n. Two adjacent
1-D chains are intercalated in a zipper-like manner[12b,12c]
Figure 6. Perspective view of hydrogen bonds between 1-D double
polymeric chains and metal-organic coordination complexes from
to form a double polymeric chain [Cd2(HBTC)2(phen)2]2n different directions
Eur. J. Inorg. Chem. 2004, 185Ϫ191
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X. Shi, G. Zhu, Q. Fang, G. Wu, G. Tian, R. Wang, D. Zhang, M. Xue, S. Qiu
FULL PAPER
carboxy oxygen atoms (O3ϪH3 and O11ϪH11) of H3BTC
ligands from the double polymeric chains point outward to
form hydrogen bonds (O3ϪH3···O18, O11ϪH11···O13)
with the carboxylate oxygen atoms (O18 and O13) from
surrounding metal-organic coordination complexes. At the
same time, uncoordinated carboxy oxygen atoms
(O16ϪH16) from the metal-organic coordination com-
plexes are well positioned to form hydrogen bonds
(O16ϪH16···O9) with carboxylate oxygen atoms (O9) from
the double polymeric chains. The O···O distances and
OϪH···O angles are listed in Table 1.
˚
Table 1. OϪO distances [A] and OϪH···O angles [°] of O···O hydro-
gen bonds in 3 (symmetry transformations used to generate equiva-
lent atoms: #1: x Ϫ 1, y, z; #2: Ϫx ϩ 1, Ϫy ϩ 1, Ϫz)
DϪH···A
d(DϪH) d(H···A) d(D···A) Ͻ(DHA)
O(3)ϪH(3)···O(18)
O(11)ϪH(11)···O(13)#1 0.82
O(16)ϪH(16)···O(9)#2 0.82
0.82
1.73
1.77
1.82
2.532(7) 166.6
2.551(8) 158.9
2.617(7) 163.4
In addition to O···O hydrogen bonds, CϪH···O hydrogen
bonds exist between double polymeric chains and metal-
organic coordination complexes. Double polymeric chains
and their surrounding metal-organic coordination com-
plexes intercalate so as to form hydrogen bonds between
them. C atoms with hydrogen atoms (C10ϪH10 and
C16ϪH16a) of a phen ligand from double polymeric chains
form CϪH···O hydrogen bonds (C10ϪH10···O18 and
C16ϪH16a···O16) with carboxylate oxygen atoms (O18 and
O16) from coordination complexes. Simultaneously, C
atoms with hydrogen atoms (C42ϪH42, C49ϪH49 and
C72ϪH72) of a phen ligands from coordination complexes
also form CϪH···O hydrogen bonds (C42ϪH42···O2,
C49ϪH49···O10 and C72ϪH72···O12) with carboxylate
oxygen atoms (O2, O10 and O12) from double polymeric
Figure 7. 3-D supramolecular architecture of 3 along [010]
direction
charge transfer) in nature, and tentatively can be assigned
to the intraligand fluorescent emission of coordinated phen
ligands due to the planar configuration of excimeric phen
molecules maintained by the cadmium ion.[16] The emission
bands for 2, at 367, 385 and 404 nm (λexc. ϭ 332 nm), can
be assigned like those of 1 [Figure 8 (c)].[16] It is reported
that free H2BDC and free H3BTC show fluorescence emis-
sion in the solid state. Their emission bands are mainly lo-
cated at about 390 nm, with a shoulder at 370 nm for free
H3BTC (H2BDC: λexc. ϭ 350 nm; H3BTC: λexc.ϭ 334 nm)
and are attributed to a π* Ǟ n transition.[17] For 2, the
H2BDC ligands show almost no contribution to the fluor-
escent emission, due to very weak fluorescent emission, re-
sulting from a π* Ǟ n transition of H2BDC, compared with
the π*Ǟπ transition of phen and/or fluorescence quenching
of carboxy groups of H2BDC (which are strong electron-
withdrawing groups). Interestingly, 3 has a single broad em-
˚
chains. The C···O distances (2.438Ϫ2.546 A) of CϪH···O
hydrogen bonds (C10ϪH10···O18, C16ϪH16a···O16,
C42ϪH42···O2, C49ϪH49···O10, C72ϪH72···O12) and the
CϪH···O angles (148.22Ϫ159.34°) are both within accept-
able ranges.[14] Thus, two kinds of complementary hydrogen
bonds form multi-linked hydrogen-bond interactions be-
tween double polymeric chains and metal-organic coordi-
nation complexes, which ultimately extend one-dimensional
double polymeric chains into a three-dimensional supra-
molecular framework along [011] and [0Ϫ11] (Figure 7).
Fluorescent Properties
Solid-state 1, 2 and 3 exhibit strong fluorescence at room ission band at 380 nm (λexc. ϭ 330 nm), which is obviously
temperature. The free phen·H2O also fluoresces in the solid different from the multi-bands of 2, and may tentatively be
state. The emission bands for free phen·H2O are at 365 and assigned to intraligand charge transfer of coordinated phen
388 nm (λexc. ϭ 310 nm), which may be attributed to the π* ligands [Figure 8 (d)]. Here H3BTC ligands also show al-
Ǟπ transition [Figure 8 (a)]. Of the emission bands for 1 at most no contribution to the fluorescent emission of 3, as
366, 389 and 410 nm (λexc. ϭ 384 nm) [Figure 8 (b)] the first with 2. The large difference between the emission bands of
two are obviously due to intraligand charge transfer of co- 2 and 3, although they are both mixed-ligand systems, may
ordinated phen ligands, similarly to the emission of free be due to the uniquely complicated structure of 3, with at-
phen·H2O. The band at 410 nm for 1 is neither LMCT (li- tachment of the dicadmium complex to the 1-D polymeric
gand-to-metal charge transfer) nor MLCT (metal-to-ligand chain through hydrogen bonds. This complicated structure
188
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Novel Supramolecular Frameworks
FULL PAPER
1-D double chains into a 3-D supramolecular framework Ϫ
in contrast to previously reported supramolecular struc-
tures constructed through interchain hydrogen bonds.
Moreover, these compounds exhibit strong fluorescence at
room temperature in the solid state.
Experimental Section
General Remarks: Elemental analyes were performed with a
PerkinϪElmer 2400 element analyzer, and inductively couple
plasma (ICP) analysis with a PerkinϪElmer Optima 3300DV ICP
spectrometer. IR spectra were obtained with a Nicolet Impact 410
FTIR spectrometer. Fluorescence spectra were obtained with a LS
55 fluorescence/phosphorescence spectrophotometer at room tem-
perature.
Preparation
Metal Source Cd(phen)2(NO3)2 (1): Synthesis under hydrothermal
conditions. The reaction of Cd(NO3)2·6H2O (0.308 g, 1.0 mmol)
with 1,10-phenanthroline monohydrate (0.257 g, 1.3 mmol) in a
solution of NaOH (10Ϫ3 mol/L, 10 mL) at 160 °C for 6 d produced
large yellow block crystals in 86% yield (0.513 g). C24H16CdN6O6
(596.83): calcd. C 48.30, H 2.680, Cd 18.83, N 14.08; found C
48.36, H 2.675, Cd 18.73, N 14.12. IR (KBr): ν˜ ϭ 3066, 1600, 1588,
Figure 8. Solid-state fluorescent emission spectra of (a) free
phen·H2O, (b) Cd(phen)2(NO3)2, (c) [Cd(BDC)(phen)(H2O)]n and
(d) [Cd2(HBTC)2(phen)2]2n·nCd(HBTC)(phen)2 at room tempera-
ture
1495, 980, 880 cmϪ1
.
Compound 2: Preparation under mild conditions by allowing
Cd(phen)2(NO3)2 (0.158 g, 0.25 mmol) and H2BDC (0.041 g,
0.25 mmol) to react in a solution of N,NЈ-dimethylformamide
(DMF) (10.0 mL), absolute ethanol (2.0 mL), and distilled water
(3.0 mL) at 55 °C for 4 d to produce large yellow block crystals in
59% yield (0.070 g). C20H14CdN2O5 (474.73): calcd. C 50.60, H
2.949, Cd 23.67, N 5.900; found C 50.52, H 2.941, Cd 23.72, N
5.884. IR (KBr): ν˜ ϭ 3325, 3079, 1625, 1606, 1541, 1418, 1012,
causes multiple charge-transfer with close transition ener-
gies, which might ultimately result in a single broad
emission band.
Conclusions
780 cmϪ1
.
Two 3-D supramolecular frameworks have been synthe-
sized by using a metal-organic coordination compound as
the metal source under mild conditions. Notably for 3, it is
the hydrogen-bonding interactions between polymeric coor-
Compound 3: Synthesis by allowing Cd(phen)2(NO3)2 (0.158 g,
0.25 mmol) and H3BTC (0.053 g, 0.25 mmol) to react in a solution
of N,NЈ-dimethylformamide (DMF) (10.0 mL), absolute ethanol
dination chains and coordination complexes that extend the (2.0 mL), and distilled water (3.0 mL) at 55 °C for 6 d. The result-
Table 2. Crystal data and structure refinement for complexes 1Ϫ3
1
2
3
Empirical formula
Formula mass
Temperature [K]
Crystal system
Space group
C24H16CdN6O6
596.83
293(2)
monoclinic
Cc
11.532(2)
15.326(3)
13.330(3)
90
104.36(3)
90
2282.4(8)
2
0.8680.7271.487
0.506
C20H14CdN2O5
474.73
293(2)
monoclinic
C2/c
25.502(9)
9.866(2)
21.239(5)
90
125.75(2)
90
4337(2)
4
C75H44Cd3N8O18
1682.38
293(2)
triclinic
¯
P1
˚
a [A]
10.192(2)
16.074(3)
23.747(5)
104.84(3)
92.26(3)
90.80(3)
3756.6(13)
2
˚
b [A]
˚
c [A]
α [°]
β [°]
γ [°]
3
˚
V [A ]
Z
ρcalcd. [gcmϪ3
]
µ [mmϪ1
]
0.518
0.914
Reflections collected
Independent reflections (Rint
R1,wR2 [I Ͼ 2σ(I)]
2617
2482 (0.019)
0.0196, 0.0524
3034
2698 (0.041)
0.0617, 0.1862
15085
11446 (0.050)
0.0607, 0.2104
)
Eur. J. Inorg. Chem. 2004, 185Ϫ191
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 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
189

X. Shi, G. Zhu, Q. Fang, G. Wu, G. Tian, R. Wang, D. Zhang, M. Xue, S. Qiu
ant colorless block crystals were filtered off, washed with absolute structures were solved by direct methods[18] and refined by full-
FULL PAPER
ethanol and dried at room temperature. The yield was about 46%
(0.064 g). C75H44Cd3N8O18 (1682.38): calcd. C 53.54, H 2.615, Cd
20.04, N 6.660; found C 53.58, H 2.620, Cd 20.07, N 6.652. IR
matrix least-squares method against F2 (SHELXL-97).[19] All non-
hydrogen atoms were refined anisotropically. Hydrogen atoms of
organic ligands were located geometrically. The crystallo-
graphic data for 1Ϫ3 are listed in Table 2, and selected bond
lengths and angles for 2 and 3 are presented in Tables 3 and 4,
respectively. CCDC-216289 for [Cd(phen)2(NO3)2], -216290 for
(KBr): ν˜ ϭ 3200, 3058, 1598, 1568, 1409, 998, 860, 676 cmϪ1
.
Single-Crystal Structure Determination: Crystallographic data for 1
and 3 were collected at 293(2) K with a Rigaku R-AXIS RAPIC
[Cd(BDC)(phen)(H2O)]
and
-216291
for
[Cd2(HBTC)2-
˚
IP diffractometer with Mo-Kα (λ ϭ 0.71073 A). Crystallographic
(phen)2·Cd(HBTC)(phen)2] contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; Fax: (internat.) ϩ 44-1223-336-033; E-mail:
deposit@ccdc.cam.ac.uk].
data for 2 were collected at 293(2) K with a Bruker-AXS Smart
˚
CCD diffractometer with Mo-Kα radiation (λ ϭ 0.71073 A). The
˚
Table 3. Selected bond lengths [A] and angles [°] for [Cd(BDC)-
(phen)(H2O)]n
Cd(1)ϪO(1)
Cd(1)ϪN(2)
Cd(1)ϪO(4)
Cd(1)ϪN(1)
O(1)ϪCd(1)ϪN(2) 93.6(3)
O(1)ϪCd(1)ϪO(4) 161.3(2)
N(2)ϪCd(1)ϪO(4) 86.26(18)
O(1)ϪCd(1)ϪN(1) 103.3(2)
N(2)ϪCd(1)ϪN(1) 70.68(18)
O(4)ϪCd(1)ϪN(1) 94.32(18)
O(1)ϪCd(1)ϪO(3) 126.1(3)
2.242(7)
2.342(5)
2.348(5)
2.363(5)
Cd(1)ϪO(3)
Cd(1)ϪO(5)
Cd(1)ϪO(2)
2.401(5)
2.408(5)
2.567(8)
Acknowledgments
We are grateful for the financial support of both the State Basic
Research Project (G2000077507) and the National Nature Science
Foundation of China (Grant no. 29873017 and 20101004).
N(2)ϪCd(1)ϪO(5) 91.02(19)
O(4)ϪCd(1)ϪO(5) 87.53(17)
N(1)ϪCd(1)ϪO(5) 161.41(17)
O(3)ϪCd(1)ϪO(5) 95.38(18)
O(1)ϪCd(1)ϪO(2) 52.5(3)
N(2)ϪCd(1)ϪO(2) 128.8(2)
O(4)ϪCd(1)ϪO(2) 138.6(2)
[1]
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N(2)ϪCd(1)ϪO(3) 140.09(17) N(1)ϪCd(1)ϪO(2) 80.8(2)
O(4)ϪCd(1)ϪO(3) 54.86(17) O(3)ϪCd(1)ϪO(2) 85.54(19)
N(1)ϪCd(1)ϪO(3) 100.81(18) O(5)ϪCd(1)ϪO(2) 109.8(2)
O(1)ϪCd(1)ϪO(5) 73.8(2)
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Cd(1)ϪO(14)
Cd(1)ϪO(17)
Cd(1)ϪN(3)
Cd(1)ϪN(4)
Cd(1)ϪN(1)
Cd(1)ϪN(2)
Cd(2)ϪO(2)
Cd(2)ϪO(8)
Cd(2)ϪN(6)
2.227(5)
2.288(5)
2.343(5)
2.359(6)
2.424(6)
2.407(6)
2.299(5)
2.294(5)
2.329(5)
Cd(2)ϪO(5)
Cd(2)ϪN(5)
Cd(2)ϪO(1)
Cd(3)ϪO(6)
Cd(3)ϪO(7)
Cd(3)ϪN(8)
Cd(3)ϪN(7)
Cd(3)ϪO(10)
Cd(3)ϪO(9)
2.328(5)
2.347(7)
2.459(5)
2.264(5)
2.318(5)
2.337(8)
2.346(8)
2.356(6)
2.433(5)
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O(14)ϪCd(1)ϪN(3) 119.1(2)
O(17)ϪCd(1)ϪN(3) 86.04(19) O(2)ϪCd(2)ϪO(1) 54.24(17)
O(14)ϪCd(1)ϪN(4) 92.0(2) O(8)ϪCd(2)ϪO(1) 138.50(18)
O(17)ϪCd(1)ϪN(4) 157.12(19) N(6)ϪCd(2)ϪO(1) 86.67(19)
N(3)ϪCd(1)ϪN(4)
O(14)ϪCd(1)ϪN(1) 151.4(2)
O(17)ϪCd(1)ϪN(1) 85.0(2)
N(6)ϪCd(2)ϪN(5) 71.2(2)
O(5)ϪCd(2)ϪN(5) 155.6(2)
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71.1(2)
O(5)ϪCd(2)ϪO(1) 92.3(2)
N(5)ϪCd(2)ϪO(1) 91.6(2)
O(6)ϪCd(3)ϪO(7) 102.9(2)
O(6)ϪCd(3)ϪN(8) 87.3(3)
O(7)ϪCd(3)ϪN(8) 157.9(3)
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N(4)ϪCd(1)ϪN(1)
O(14)ϪCd(1)ϪN(2) 83.2(2)
89.3(2)
94.8(2)
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N(3)ϪCd(1)ϪN(2)
N(4)ϪCd(1)ϪN(2)
N(1)ϪCd(1)ϪN(2)
O(2)ϪCd(2)ϪO(8)
O(2)ϪCd(2)ϪN(6)
O(8)ϪCd(2)ϪN(6)
O(2)ϪCd(2)ϪO(5)
O(8)ϪCd(2)ϪO(5)
N(6)ϪCd(2)ϪO(5)
O(2)ϪCd(2)ϪN(5)
O(8)ϪCd(2)ϪN(5)
151.3(2)
91.8(2)
68.9(2)
N(8)ϪCd(3)ϪN(7) 71.1(3)
O(6)ϪCd(3)ϪO(10) 84.57(19)
O(7)ϪCd(3)ϪO(10) 96.28(19)
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104.1(2)
85.0(2)
102.8(2)
88.5(2)
N(8)ϪCd(3)ϪO(9) 88.7(2)
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