The use of 2,1,3-benzoselenadiazole as an auxiliary ligand for the construction of new 2D silver(I)/benzene- or cyclohexane-1,3,5-tricarboxylate honeycomb networks

Article abstract of DOI:10.1002/ejic.200700930

The reaction of freshly synthesized [Ag(NH₃)₂](OH), 2,1,3-benzoselenadiazole (bsd) and benzene- or cyclohexane-1,3,5-tricarboxylic acid (H₃btc/H₃ctc) results in two new coordination polymers containing 2D Ag₃(btc) and Ag₃(ctc) hexagonal motifs, namely [Ag₃(btc)(bsd)₆]·0.5H₂O (1) and [Ag₃(ctc)(bsd)₃]·1.5bsd·3.5H ₂O (2). Complex 1 is a 3D supramolecular framework extended by deformed 2D Ag₃(btc) honeycomb nets via Se...N synthons formed between the dangling monodentate bsd groups, whereas 2 is a 3D metal-organic framework of nanoscale cages made up from ideal Ag₃(ctc) honeycomb layers and μ₂-bridging bsd ligands. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Full text of DOI:10.1002/ejic.200700930

FULL PAPER
DOI: 10.1002/ejic.200700930
The Use of 2,1,3-Benzoselenadiazole as an Auxiliary Ligand for the
Construction of New 2D Silver(I)/Benzene- or Cyclohexane-1,3,5-
tricarboxylate Honeycomb Networks
[a]
[a]
[a]
[a]
Cheng-Kang Tan, Jing Wang, Ji-Dong Leng, Ling-Ling Zheng, and
Ming-Liang Tong*[
a]
Keywords: Silver / Selenium / Carboxylate ligands / Materials science / Organic-inorganic hybrid composites
The reaction of freshly synthesized [Ag(NH
benzoselenadiazole (bsd) and benzene- or cyclohexane-
,3,5-tricarboxylic acid (H btc/H ctc) results in two new coor-
dination polymers containing 2D Ag
agonal motifs, namely [Ag (btc)(bsd)
Ag (ctc)(bsd) ]·1.5bsd·3.5H
3
)
2
](OH), 2,1,3-
honeycomb nets via Se···N synthons formed between the
dangling monodentate bsd groups, whereas 2 is a 3D metal–
organic framework of nanoscale cages made up from ideal
1
3
3
3
(btc) and Ag
]·0.5H
O (2). Complex 1 is a 3D supra-
3
3 2
(ctc) hex- Ag (ctc) honeycomb layers and µ -bridging bsd ligands.
3
6
2
O
(1) and
[
3
3
2
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
3
molecular framework extended by deformed 2D Ag (btc)
Introduction
honeycomb motif is extremely challenging, although one
2
can anticipate that the H atoms in the R (8) pattern could
2
Crystal engineering has provided a useful paradigm for be rationally replaced by metal ions. The silver(I) ion princi-
the design of organic solids, supramolecular metal com- pally exhibits linear, trigonal, and tetrahedral coordination
plexes and metal–organic frameworks (MOFs) with tunable and has a high affinity for hard donor atoms such as nitro-
[
6]
properties containing different building blocks. Much of the gen or oxygen atoms and soft donor atoms such as sulfur
[
7]
recent progress in this area is based on the idea of self- atoms, which makes it a favored and fashionable building
assembly of tailor-made building blocks that are either or- block for MOFs. Furthermore, the silver ion is apt to form
ganic molecules or metal complexes with polyfunctional or- short Ag···Ag contacts as well as ligand-unsupported inter-
[
1–3]
ganic ligands.
1,3,5-Benzenetricarboxylic acid (H btc) actions, which have been proved to be two of the most
3
and 1,3,5-cyclohexanetricarboxylic acid (H ctc), which have important factors contributing to the formation of such
3
[
8,9]
threefold symmetry, are inherently disposed to form hydro- complexes and their special properties.
gen-bonded honeycomb sheets because their carboxyl
Unfortunately, it is difficult to control the symmetry of
the resulting frameworks due to the silver(I) ion’s rich coor-
dination modes. A useful strategy in building such networks
is therefore to employ an appropriate auxiliary ligand that
can occupy one or more of the coordination sites of the
metal ions and thereby prevent the formation of compli-
cated frameworks. We decided to use 2,1,3-benzoselenadi-
azole (bsd), which may be a good candidate for the use as
an auxiliary ligand but has only been used in a similar way
groups tend to form cyclic hydrogen-bonded pairs in an
2
R (8) pattern (Scheme 1a). H btc and H ctc have been
2
3
3
widely applied as archetypical organic scaffolds for the self-
assembly of unary (containing only H btc) and binary (con-
3
taining H btc linked in an ordered fashion to other mole-
3
cules) hexagonal networks via hydrogen-bonding synthons
2
3
4
[4,5]
with R (8), R (10) or R (12) patterns.
The construc-
2
3
4
tion of a coordination polymer with a 2D M(btc/ctc)
[
10]
in a previous report from our group.
Herein we report
two novel silver coordination polymers that contain 2D
[
a] State Key Laboratory of Optoelectronic Materials and Technol-
ogies, Institute of Optoelectronic and Composite Materials & Ag (btc) and Ag (ctc) hexagonal motifs, namely
3
3
School of Chemistry and Chemical Engineering, Sun Yat-Sen
University,
[
Ag (btc)(bsd) ]·0.5H O (1) and [Ag (ctc)(bsd) ]·1.5bsd·
3 6 2 3 3
Guangzhou 510275, China
3.5H O (2), respectively, and demonstrate a new and effec-
2
Fax: +86-20-8411-2245
I
tive way to self-assemble hexagonal Ag (btc/ctc) coordina-
tion networks in the presence of 2,1,3-benzoselenadiazole
(bsd) as the auxiliary ligand (Scheme 1b).
E-mail: tongml@mail.sysu.edu.cn
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
Eur. J. Inorg. Chem. 2008, 771–778
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
771

C.-K. Tan, J. Wang, J.-D. Leng, L.-L. Zheng, M.-L. Tong
FULL PAPER
Scheme 1. Well-known 2D hexagonal net directed by the R2
and 2 (b).
(8) hydrogen-bonded pattern (a) and our strategy for the construction of 1
2
Results and Discussion
Synthesis and Characterization
It is well known that the reactions of silver(I) ions with
polycarboxylates in aqueous solution often result in the for-
mation of insoluble silver salts, presumably due to the rapid
coordination of the carboxylate ions to the silver ions to
form polymeric structures. Mak and co-workers have gener-
ated polymeric structures in silver(I) carboxylate like com-
Scheme 2. Coordination modes of the bsd ligand: monodentate
[
11]
plexes by using various zwitterionic betaine-type ligands,
with an Se···N nonbonding interaction (a) and a µ -bridging mode
2
and Smith and co-workers[ have obtained a series of Ag
polycarboxylate complexes by using ammonia to enhance
the solubility of the silver carboxylates. Similarly, Michael-
12]
(
b).
Crystal Structure
[
13]
ides and co-workers have reported a novel succinatodisil-
ver(I) complex synthesized by gel permeation. Hence, it ap-
The X-ray structural analysis reveals that 1 crystallizes
pears that the correct choice of reaction conditions may re- in the monoclinic P2 /c space group with an asymmetric
1
I
3–
sult in the formation of crystalline products that are suitable unit that contains three Ag atoms, one btc ligand, six
for X-ray structural analysis. 2,1,3-Benzoselenadiazole (bsd) monodentate bsd ligands (one of which shows twofold dis-
can coordinate to metal ions through two N atoms in a order) and half a lattice water molecule (Figure 1). Selected
monodentate or µ -bridging mode (Scheme 2). Moreover, bond lengths and angles are listed in Table 1. Ag1 is coordi-
2
the uncoordinated N atom can form a weak Se···N interac- nated in a strongly distorted tetrahedral environment to two
tion which could help in the construction of the framework O atoms from two btc3– anions and two N atoms from two
[
10]
(
Scheme 2a). In light of all this, we treated freshly synthe- bsd ligands [Ag1–O 2.240(6) and 2.244(6) Å; Ag1–N
sized [Ag(NH ) ](OH) and H btc/H ctc ligand with bsd 2.30(1) and 2.384(6) Å; N/O–Ag1–O/N 89.6(2)–146.2(2)°].
3
2
3
3
[
15]
(
4:1:4 molar ratio), which resulted in the formation of com- It also has an Ag···Ag contact
[2.872(1) Å]. Ag2 is also
plexes 1 and 2, respectively, which possess hexagonal Ag- coordinated in a strongly distorted tetrahedral coordination
I
3–
(btc/ctc) coordination networks. The auxiliary bsd ligand geometry and is surrounded by two O atoms from two btc
plays a vital role in the formation of these networks. It anions and two N atoms from two bsd ligands [Ag2–O
should be noted that complicated silver(I) complexes con- 2.532(5) and 2.566(5) Å; Ag2–N 2.203(6) and 2.211(6) Å;
3
–
2–
taining btc or Hbtc ligands have been documented pre- N/O–Ag2–O/N 77.2(2)–164.6(2)°] and also forms one weak
[
14]
viously.
Ag–O interaction (Ag2–O6 2.729 Å), while Ag3 is coordi-
772
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Eur. J. Inorg. Chem. 2008, 771–778

Silver(I)/Benzene- or Cyclohexane-1,3,5-tricarboxylate Networks
nated to one O atom from one btc3– ligand and two N
atoms from two bsd ligands in a Y-shaped coordination
geometry [Ag3–O 2.372(5) Å; Ag3–N 2.204(6) and
2.205(6) Å; N/O–Ag3–N 94.4(2)–161.6(2)°], as well as
forming one weak Ag–O interaction (Ag3–O6 2.657 Å).
3
–
Each btc ligand acts in a µ -bridging mode to connect six
6
I
3–
Ag atoms, and each Ag dimer is coordinated by two btc
2
ligands via syn,syn-O,OЈ bridges and single O-bridges to
form 2D honeycomb layers (Figure 2a) containing highly
deformed hexagonal rings (Figure 2b). Each of these rings
3
–
contains six Ag dimers and six btc ligands. There are
2
twelve bsd ligands coordinated to each hexagonal ring, ten
of which orient themselves perpendicular to the hexagonal
net. The other two are located within the hexagonal net and
Figure 1. Perspective views of the coordination geometries of the
I
3–
Ag ions and the bridging mode of the btc ligand in 1.
Table 1. Selected bond lengths [Å] and angles [°] for 1 and 2.[a]
Complex 1
Ag(1)–O(2a)
Ag(1)–O(1)
Ag(1)–N(3)
Ag(1)–N(1)
Ag(2)–N(5)
Ag(2)–N(7)
O(2a)–Ag(1)–O(1) 146.2(2)
O(2a)–Ag(1)–N(3) 106.4(3)
O(1)–Ag(1)–N(3)
2.240(6)
2.244(6)
2.295(11)
2.384(6)
2.203(6)
2.211(6)
Ag(2)–O(5b)
Ag(2)–O(3)
Ag(3)–N(11)
Ag(3)–N(9)
Ag(3)–O(3)
Ag(1)···Ag(1a)
2.532(5)
2.566(5)
2.204(6)
2.205(6)
2.372(5)
2.8722(13)
Figure 2. View of the highly deformed Ag (btc) hexagonal circle
(a), the 2D honeycomb net (bsd ligand have been omitted for clar-
ity) (b) and the 3D supramolecular architecture formed by inter-
6
6
N(7)–Ag(2)–O(5b) 104.12(19)
N(5)–Ag(2)–O(3)
N(7)–Ag(2)–O(3)
O(5b)–Ag(2)–O(3) 143.11(16)
N(11)–Ag(3)–N(9) 161.6(2)
N(11)–Ag(3)–O(3) 94.4(2)
104.54(18)
77.24(19)
layer (bsd) bridges containing self-complementary Se···N synthons
2
98.2(4)
(c) in 1. Some carbon atoms of the bsd ligands in (b) and (c) have
O(2a)–Ag(1)–N(1) 89.6(2)
been omitted for clarity. Atom types: Ag: cross-hatched circle; Se:
large open circle; O: small circle; N: circle with regular dot pattern;
C: shaded circle with highlight.
O(1)–Ag(1)–N(1)
N(3)–Ag(1)–N(1)
N(5)–Ag(2)–N(7)
103.4(2)
110.3(3)
164.6(2)
N(9)–Ag(3)–O(3)
101.9(2)
N(5)–Ag(2)–O(5b) 83.76(19)
Complex 2
are stabilized by a self-complementary Se···N interaction[10]
Ag(1)–O(2a)
Ag(1)–N(1)
Ag(1)–N(2b)
2.225(4)
2.291(5)
2.346(4)
Ag(1)–O(1)
Ag(1)···Ag(1a)
2.427(3)
2.9461(9)
[Se···N 2.855(1) Å]. The 2D hexagonal nets are further ex-
tended into a 3D supramolecular architecture (Figure 2c)
via self-complementary Se···N interactions [Se···N 2.849(1)
and 2.950(1) Å] between the interlayer dangling bsd groups.
To the best of our knowledge, only one 3D molecular
framework has been generated by self-complementary
Se···N interactions between a pair of bsd molecules.[
O(2a)–Ag(1)–N(1) 120.13(18) N(1)–Ag(1)–O(1)
O(2a)–Ag(1)–N(2b) 112.16(17) N(2b)–Ag(1)–O(1) 72.27(16)
O(2a)–Ag(1)–O(1) 149.98(16)
81.77(14)
[
3
4
a] Symmetry codes: a: –x – 1, –y + 2, –z + 1; b: –x, y + 1/2, –z +
/2 for 1; a: –x + 1, –y + 2, –z + 1; b: y – 1/3, –x + y + 1/3, –z +
/3 for 2.
10]
Eur. J. Inorg. Chem. 2008, 771–778
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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773

C.-K. Tan, J. Wang, J.-D. Leng, L.-L. Zheng, M.-L. Tong
FULL PAPER
The X-ray structural analysis of 2 reveals that it crys- Ag (ctc) (bsd) and Ag (ctc) (bsd) (Figure 4b and c and
24
2
12
12
2
6
¯
tallizes in the rhombohedral space group R3. The asymmet- Figure S1 in the Supporting Information). Each Ag (ctc) -
24
2
ric unit consists of a unique Ag atom, which lies in a gene- (bsd)12 cage has the dimensions 13.38ϫ14.23ϫ16.48 Å3
ral position, one-third of a ctc ligand, which lies across and contains a pair of Ag (ctc) motifs and six Ag (µ-bsd)
the a 3-axis, one twofold disordered bsd ligand due to rota- motifs, and each Ag (ctc) (bsd) cage contains a pair of
I
3
–
6
2
2
¯
12
2
6
tion about the N–N axis, a disordered bsd molecule with Ag (ctc) motifs and six µ-bsd motifs. The void volume
6
an occupancy of 0.5 and water guests (Figure 3a). Ag1 is (Vvoid) of 2 without guests is 21.5% per unit volume, as
[
16]
coordinated in a strongly distorted tetrahedral environment calculated by PLATON.
The twofold disordered bsd
3
–
to two O atoms from two ctc ligands and two N atoms guest molecules are located in the windows of the larger
from two bsd ligands [Ag1–O 2.226(6) and 2.426(5) Å; cages and interact with the host through Se···O nonbonding
i
Ag1–N 2.293(8) and 2.33(2)/2.38(2) Å; N/O–Ag1–O/N interactions (Se2···O2 3.054 Å; symmetry code: i = 1/3 – x,
[
17a,17b]
7
2.1(5)–149.9(2)°]. It also forms an Ag···Ag contact 5/3 – y, 2/3 – z)
as well as an edge-to-face interac-
involving bsd(host)···bsd(guest) motifs (Figure 4d).
The network topology can be simplified by considering
with each hexagonal unit consisting of six tri- the 6-connected dimeric Ag2 units and the 3-connected
3
–
[17c]
[
2.9461(9) Å]. As in 1, each ctc ligand acts as a µ -bridge tion
6
to connect three Ag dimers into ideal 2D honeycomb nets,
2
3
–
3–
gonal ctc
ligands and six Ag2 dimers (Figure 3b, ctc ligands as octahedral and trigonal nodes, respectively;
Scheme 1b). In our previous investigation on the assembly the bidentate bsd ligands can be represented simply
of coordination polymers with metal clusters as building as links between the Ag2 nodes. The resulting net is
blocks, Ag (MeCO ) was used as a secondary building unit shown in Figure 4e, which is a new (3,6)-connected
2
2 2
for the construction of 3D MOFs.[ The 2D hexagonal net
15]
[1d]
with octahedral and trigonal nodes in a 3:2 ratio.
nets of 2 are further connected by µ -bridging bsd ligands The long topological (O’Keeffe) vertex symbol is
2
[
18]
into a 3D MOF (Figure 4a) which is quite different from 4.4.4.4.4.4.6 .6 .6 .6 .6 .6 .8 .8 .*
that in 1. Interestingly, this 3D MOF can also be decon- 4.4.4 for the ctc node, which gives the short vertex symbol
structed into two types of nanoscale cage units, namely (4 ) (4 .6 .8 ) .
for the Ag node and
2
2
3
2
2
4
4
4
4
2
–
3
6
6
3
2
3
Thermogravimetric Analysis
We carried out thermal gravimetric (TG) analyses to ex-
amine the thermal stabilities of the networks and measured
the XPRD patterns to confirm the purity of the two com-
plexes (Figure 5). Samples of the complexes were heated un-
der nitrogen to 500 °C. The TGA curve of 1 (Figure 6a)
shows that this complex is stable up to 110 °C, with the
small weight loss of 0.6% at about 105 °C corresponding to
the loss of the half lattice water molecule (calculated: 0.6%).
The second weight loss of 45.2% between 110 and 172 °C
is in accordance with loss of the four bsd ligands of the
unit cell (calculated: 44.7%) that lie between the adjacent
hexagonal layers. Gradual loss of the other two bsd ligands
and btc3– ligands occurs above 172 °C, and the complex de-
composes completely to Ag O (found: 21.4%; calculated:
2
21.2%) up to 385 °C. Complex 2 is less stable than 1 due
to its porous network and many guest molecules. The TGA
curve of 2 (Figure 6b) shows loss of two of the lattice water
molecules (found: 2.4%; calculated: 2.5%) at about 55 °C,
with the others (1.9%) being lost up to 130 °C (calculated:
1
1
.8%). The second weight loss of 39.4% between 130 and
80 °C corresponds to the loss of guest bsd molecules and
one and a half of the coordinated ligands (calculated:
8.5%). The remaining half of the coordinated bsd ligand
5.9%) is lost between 180 and 240 °C (calculated: 6.4%).
3
(
The final weight loss of 12.7% up to 265 °C occurs due to
loss of the last bsd ligand, and the complex finally decom-
Figure 3. Perspective views of the coordination geometry of the AgI
posesd to Ag O residue (found: 25.1%; calculated: 24.4%)
up to 300 °C. Four endothermic peaks in the DTA curve
2
ion and the bridging mode of the ctc3– ligand (a) and the 2D
Ag
3
(ctc) honeycomb net along the c-axis (b) in 2.
also indicate the loss of various groups.
774
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Eur. J. Inorg. Chem. 2008, 771–778

Silver(I)/Benzene- or Cyclohexane-1,3,5-tricarboxylate Networks
2 2 6
Figure 4. Top-views of the 3D cage-based network (a), the nanoscale Ag24(ctc) (bsd)12 cage (b) and the Ag12(ctc) (bsd) cage (c), the
(
3,6)-connected topological net (d), and the bsd(host)···bsd(guest) interaction (e) in 2. Some carbon atoms of of the bsd ligands in (b)
and (c) have been omitted for clarity. Atom types: Ag: cross-hatched circle; Se: large open circle; O: small circle; N: circle with regular
dot pattern; C: shaded circle with highlight.
cation. The C, H, and N microanalyses were carried out with an
Conclusions
Elementar Vario-EL CHNS elemental analyzer. The IR spectra
The presence of bsd as an auxiliary ligand leads to the
formation of two novel MOFs containing 2D hexagonal
–1
were recorded from KBr pellets in the range 4000–400 cm with a
Bio-Rad FTS-7 spectrometer. X-ray powder diffraction (XPRD)
net motifs, namely [Ag (btc)(bsd) ]·0.5H O (1) and intensities for 1 and 2 were measured at 293 K with a Rigaku D/
3
6
2
[
Ag (ctc)(bsd) ]·1.5bsd·3.5H O (2), from the reaction of max-IIIA diffractometer (Cu-K , λ = 1.54056 Å). Crushed single-
3 3 2
α
freshly synthesized [Ag(NH ) ](OH) with H btc or H ctc crystalline powder samples were prepared and scanned from 5–65°
3
2
3
3
with a step of 0.1° per second. Thermal gravimetry (TG) was car-
at room temperature. Complex 1 is a 3D supramolecular
framework that is formed by interlayer Se···N interactions
between the dangling monodentate bsd groups of 2D neu-
ried out with a NETZSCH TG209F3 thermal gravimetric analyzer,
–
1
by heating the samples from 30–500 °C at a rate of 10 °Cmin .
tral deformed honeycomb-like Ag (btc) layers, whereas 2 is
a 3D metal–organic framework containing nanoscale cages
3
Synthesis of 1 and 2: Excess aqueous NH
added dropwise to a suspension of Ag O (0.116 g, 0.5 mmol) in
MeCN/H O (15 mL, 2:1 v/v) and the mixture stirred for 15 min.
3
solution was slowly
2
between ideal Ag (ctc) honeycomb layers and µ -bridging
3
2
2
bsd ligands. Complex 2 is a new (3,6)-connected topological H btc (0.053 g, 0.25 mmol) or H ctc (0.054 g, 0.25 mmol) and
3
3
net.
2,1,3-benzoselenadiazole (bsd) ligand (0.183 g, 1.0 mmol) were
then slowly added, and the mixture was stirred for 30 min. The
resultant colorless solution was allowed to stand in the dark at
room temperature for a week to give yellow block crystals of 1
Experimental Section
General Remarks: All reagents and solvents employed were com-
mercially available and were used as received without further purifi-
(yield: 0.340 g, ca. 83% based on H btc) or 2 (yield: 0.284 g, ca.
3 12 6
80% based on H ctc). 1: C45H28Ag N O6.5Se (1638.2): calcd. C
3
3
Eur. J. Inorg. Chem. 2008, 771–778
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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775

C.-K. Tan, J. Wang, J.-D. Leng, L.-L. Zheng, M.-L. Tong
FULL PAPER
Figure 5. Observed (gray) and calculated (black) X-ray powder dif-
fraction patterns for 1 (a) and 2 (b).
Figure 6. TGA (black) and DTA (gray) curves for 1 (a) and 2 (b).
Table 2. Crystal and structure refinement data for complexes 1 and 2.[a]
Compound
1
2
Empirical formula
Formula mass
Temperature [K]
Wavelength [Å]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
C
45
H
28Ag
3
N
12
O6.5Se
6
36 3 9
C H34Ag N O9.5Se4.5
1423.65
173(2)
1638.16
123(2)
0.71073
monoclinic
P2 /c
10.7459(8)
13.866(1)
32.827(2)
90
0.71073
rhombohedral
¯
1
R3
19.662(1)
19.662(1)
17.839(2)
90
β [°]
92.846(1)
90
4885.2(6)
4
2.227
5.725
90
120
5972.4(7)
6
2.375
5.646
4098
γ [°] 3
V [Å ]
Z
–3
Calculated density [gcm ]
Absorption coefficient [mm ]
F(000)
–1
3116
Crystal size [mm]
θ range for data collection [°]
Limiting indices
0.18ϫ0.11ϫ0.05
1.90–26.00
–5ՅhՅ13
0.16ϫ0.12ϫ0.08
1.65–27.75
–21ՅhՅ25
–
–
17ՅkՅ16
40ՅlՅ38
–25ՅkՅ25
–21ՅlՅ23
Reflections collected/unique
Completeness
Absorption correction
Max. and min transmission
Refinement method
23987/9569
10899/2937
99.5% (θmax = 26.00°)
multi-scan (SADABS, Bruker, 2002)
0.4222/0.7628
93.5% (θmax = 27.75°)
multi-scan (SADABS, Bruker, 2002)
0.6609/0.4653
2
2
full-matrix least squares on F
full-matrix least squares on F
Data/restrains/parameters
Goodness-of-fit on F2
R indexes [I Ͼ 2σ(I)]
R indices (all data)
9569/136/703
0.935
2937/86/196
1.095
R
R
1
= 0.0522, wR
= 0.0755, wR
2
= 0.1205
= 0.1278
R
R
1
= 0.0687, wR
= 0.0844, wR
2
= 0.2070
= 0.2184
1
2
1
2
–3
Largest diff. peak/hole [eÅ ]
a] R = Σ||F | – |F ||/Σ|F |, wR
1.636/–2.202
2.479/–2.091
[
1
o
c
o
2
= [Σw(F 2
o
– F
c
2)2/Σw(F 2)2]1/2.
o
776
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 771–778

Silver(I)/Benzene- or Cyclohexane-1,3,5-tricarboxylate Networks
3
2.99, H 1.72, N 10.26; found C 33.34, H 1.63, N 10.70. IR (KBr):
A. J. Blake, N. R. Champness, C. Wilson, M. Schröder, J. Am.
Chem. Soc. 2001, 123, 3401–3402; c) K. G. Nath, O. Ivasenko,
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F. Rosei, J. Am. Chem. Soc. 2006, 128, 4212–4213.
ν˜ = 3403 (w), 3081 (w), 3054 (w, 3010 (w), 1602 (s), 1542 (vs), 1509
(
(
m), 1481 (m), 1425 (w), 1135(w), 1090 (w), 981 (w), 950 (w), 848
–
1
w), 807 (w), 744 (vs), 711 (vs), 596 (w), 556 (w), 518 (w) cm . 2:
9.5Se4.5 (1423.7) : calcd. C 30.37, H 2.41, N 8.85;
found C 30.07, H 2.29, N 8.71. IR (KBr): ν˜ = 3379 (s), 2945 (w),
[
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655 (w), 1560 (vs), 1511 (m), 1479 (w), 1393 (s), 1351m), 1292 (w,
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[
2
655–2656; b) T. R. Shattock, P. Vishweshwar, Z. Wang, M. J.
–1
(w), 578 (w) cm .
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X-ray Crystallographic Study: Diffraction intensities for 1 and 2
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fractometer (Mo-K
applied by using the multiscan program SADABS.
α
, λ = 0.71073 Å). Absorption corrections were
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[19]
The struc-
tures were solved by direct methods and refined with a full-matrix
least-squares technique with the SHELXTL program package.[
Anisotropic thermal parameters were applied to all non-hydrogen
atoms. Hydrogen atoms were placed at calculated positions and
were included in the refinement in the riding model approximation,
with U set to 1.2- or 1.5-times those of the parent atoms. For 2,
the bsd ligand was treated as being twofold disordered around the
N–N axis of bsd, with the disordered atoms Se1, C4, C5, C6, C7,
C8, C9 and Se1Ј, C4Ј, C5Ј, C6Ј, C7Ј, C8Ј, C9Ј each having an
occupancy of 50%. The crystallographic data for 1 and 2 are listed
20]
[
2
152; b) K. A. Hirsch, S. R. Wilson, J. S. Moore, Inorg. Chem.
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in Table 2. 1: C45
space group P2 /c (no. 14), a = 10.746(1), b = 13.866(1), c =
2.827(2) Å, β = 92.846(1)°, V = 4885.2(6) Å , Z = 4, T = 123(2) K,
H28Ag
3
N
12
O6.5Se
6
, M = 1638.16, monoclinic,
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1
3
3
–3
–1
F(000) = 3116, D
.0522, wR = 0.1205 and GOF = 0.935 for 703 parameters, 6598
reflections with |F |Ն4σ(F ). 2: C36
423.65, rhombohedral, space group R3 (no. 148), a = 19.662(1), c
c α 1
= 2.227 gcm , µ(Mo-K ) = 5.725 mm ; R =
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2
1
514.
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o
o
3 9
H34Ag N O9.5Se4.5, M =
¯
[
1
=
1
3
17.839(2) Å, V = 5972.4(7) Å , Z = 6, T = 173(2) K, F(000) =
–3
–1
4098, D
c
= 2.375 gcm , µ(Mo-K
0.2070 and GOF = 1.095 for 196 parameters, 2228 reflections
|Ն4σ(F ). CCDC-628822 (1) and -628823 (2) contain the
α 1 2
) = 5.646 mm ; R = 0.0687, wR
1
=
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with |F
o
o
supplementary crystallographic data for this paper. These data can
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viewed along the c-axis in 2.
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This work was supported by the National Natural Science Founda-
tion of China (grant nos. 20525102 and 20471069), the Foundation
for the Author of National Excellent Doctoral Dissertation of
China (200122), and the Scientific and Technological Project of
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
777

C.-K. Tan, J. Wang, J.-D. Leng, L.-L. Zheng, M.-L. Tong
FULL PAPER
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Weinheim, 2006, chapter 1.3, pp. 58–85.
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Published Online: January 3, 2008
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 771–778