Copper-organic coordination polymers with porous structures

Article abstract of DOI:10.1246/bcsj.75.725

Three copper coordination polymers containing organosulfur ligands ({[Cu¹₂(bpsb)₃(ClO₄)] (ClO₄)}_n (1), {[Cu^I₂(bpsb)₃Cl] (ClO₄)},_n (2), and {[Cu^II(bpb)₂Br] (ClO₄)·3dmf·MeCN}_n (3)(bpsb = 1,2-bis[(2-pyrimidinyl)sulfanylmethyl]benzene, bpb = 1,2-bis[(4-pyridyl)sulfanylmethyl]benzene, dmf = N, N-dimethylformamide)) were synthesized and characterized by X-ray structural analysis. Complexes 1 and 2 have similar structures. In both, each bpsb molecule exhibits an exo-bidentate coordination fashion and bridges 3-coordinated copper(I) and 4-coordinated copper(I) through pyrimidinyl rings. Thus, six copper(I) centers, three 3-coordinated and three 4-coordinated located at two different planes alternatively, are linked by six bpsb molecules forming a crown-like nanocavity; such nanocavities make up a 2-D lamellar structure. In complex 3, each copper(II) center adopts a distorted square pyramidal coordination mode; each bpb molecule acts as an exo-bidentate ligand through coordinating to copper(II) atoms in two different directions to form a square unit with solvent molecule guests. Such square units share copper atoms and generate a single-stranded infinite 1-D chain structure.

Full text of DOI:10.1246/bcsj.75.725

c. Jpn.
© 2002 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 75, 725–730 (2002)
725
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Copper-Organic Coordination Polymers with Porous Structures
Copper-Organic Coordination Polymers
R.-H. Wang et al.
Rui-Hu Wang, Mao-Chun Hong,* Wei-Ping Su, Yu-Cang Liang, Rong Cao,* Ying-Jun Zhao, and
Jia-Bao Weng
02
5
0
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter,
Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P. R. China
SJA8
09-2673
290
(Received August 21, 2001)
Ⅰ
Three copper coordination polymers containing organosulfur ligands ({[Cu 2(bpsb)3(ClO4)](ClO4)}n (1),
Ⅰ
Ⅱ
{[Cu 2(bpsb)3Cl](ClO4)}n (2),and{[Cu (bpb)2Br](ClO4)•3dmf•MeCN}n (3)(bpsb=1,2-bis[(2-pyrimidinyl)sulfanylmeth-
yl]benzene, bpb = 1,2-bis[(4-pyridyl)sulfanylmethyl]benzene, dmf = N, N-dimethylformamide)) were synthesized and
characterized by X-ray structural analysis. Complexes 1 and 2 have similar structures. In both, each bpsb molecule ex-
hibits an exo-bidentate coordination fashion and bridges 3-coordinated copper(Ⅰ) and 4-coordinated copper(Ⅰ) through
pyrimidinyl rings. Thus, six copper(Ⅰ) centers, three 3-coordinated and three 4-coordinated located at two different
planes alternatively, are linked by six bpsb molecules forming a crown-like nanocavity; such nanocavities make up a 2-D
lamellar structure. In complex 3, each copper(Ⅱ) center adopts a distorted square pyramidal coordination mode; each
bpb molecule acts as an exo-bidentate ligand through coordinating to copper(Ⅱ) atoms in two different directions to form
a square unit with solvent molecule guests. Such square units share copper atoms and generate a single-stranded infinite
1-D chain structure.
01
01
.2
.3
Supramolecular syntheses by employing coordination cova-
lent chemistry and the principle of self-assembly have resulted
in numerous metal-ligand networks with fascinating structural
topologies, in which selective and spontaneous assemblies rely
principally on complexation of multidentate ligands with steric
and interactive information and two or more metal ions.1–3
Therefore, the design of ligands and the selection of metal ions
are crucial to the construction of a specific supramolecular ar-
chitecture, particularly one-, two- and three-dimensional ex-
tended network framework types owing to their potential ap-
plication to separation and catalysis. This problem has been
demonstrated by many architecturally highly sophisticated
polynuclear complexes, such as molecular grids, racks, bricks,
rings, boxes, honeycombs and helicates.4–10 For instance, rigid
ligands, such as pyrazine, 4,4-bipyridine and 1,4-benzenedi-
carboxylate, result in the formation of molecular racks and
grids.6–8 While flexible ligands, such as bipyridine groups with
a longer spacer or 2,2ꢀ:6ꢀ,2ꢁ-terpyridine and its derivates with
conformational freedom, might result in the formation of heli-
cates or networks.9–10 On the other hand, a great deal of the
structural information available from coordination chemistry
has demonstrated the importance of choosing metal ions for
supramolecular self-assembly. For example, the copper(Ⅰ) and
silver(Ⅰ) ions as extremely soft acids benefit coordination to
soft bases, such as S and unsaturated N-containing ligands, and
produce an interesting array of complexes with labile coordi-
nation modes, such as linear, trigonal, tetrahedral, pentagonal,
square-pyramidal and even octahedral fashions; however,
Fe(Ⅲ), Cu(Ⅱ), and Ln(Ⅲ) (Ln = Lanthanoid) etc. as hard acids
favor coordination to hard bases, such as O, N and P, and give
rise to a great deal of coordination polymers with high coordi-
nation numbers of over four.11
Because metal thiolato complexes are well known to adopt
various nuclearity and great structural complexity, previous in-
terests in our laboratory have concentrated on using some sim-
ple ligands with mixed phosphine or nitrogen and thiolato do-
nor atoms for supramolecular synthesis. As a result, some su-
pramolecular polymers with linear chain or 3-D network struc-
tures have been obtained.12–14 Recently, we have designed a
series of multidentate ligands containing pyrimidinyl or pyridyl
rings by using simple ligands with sulfur and nitrogen atoms
from earlier work, such as 2,4,6-tris[(4-pyridyl)methylsulfa-
nyl]-1,3,5-triazine (tpst), 1,2-bis[(2-pyrimidinyl)methylsulfa-
nyl]benzene (bpsb) and 1,2-bis[(4-pyridyl)methylsulfanyl]ben-
zene (bpb), and obtained several unique structural motifs in su-
pramolecular chemistry.15,16 Considering the basic require-
ment for supramolecular synthesis, that the coordination possi-
bility of ligands should match the steroelectronic preferences
and coordination geometry of the metal ions, we expected to
prepare some coordination polymers containing a nanometer-
sized cavity by using designed bridging ligands, bpsb, in
which a spatial effect of coordination sites prevent it from
forming high coordination-number complexes and bpb in
which a longer bis(4-pyridyl) spacer can produce bigger holes
17–18
in the ring by bridging metal ions at larger distances
(Scheme 1), and suitable metal ions.
In this paper, we describe the syntheses and the structural
characterization of two 2-D lamellar coordination polymers
Ⅰ
containing crown-like nanocavities, {[Cu 2(bpsb)3(ClO4)]-
Ⅰ
(ClO4)}n (1), {[Cu 2(bpsb)3Cl](ClO4)}n (2), and one single-
stranded 1-D chain complex containing square rings with sol-
Ⅱ
vent molecule guests, {[Cu (bpb)2Br](ClO4)•3dmf•MeCN}n
(3).

726 Bull. Chem. Soc. Jpn., 75, No. 4 (2002)
Copper-Organic Coordination Polymers
mL) solution of AgClO4 (0.22 g, 1 mmol) was added to remove
any Br−. The mixture was stirred for 30 min and then filtered. To
the filtrate was added dropwise a CH3CN (10 mL) solution of
CuCl (0.05 g, 0.5 mmol); the reaction mixture was stirred for 0.5 h
at 50 °C and then filtered. Yellow crystalline complex 2 was ob-
tained by slow diffusion of diethyl ether into the resulting solution
for two weeks. Yields: 0.11 g (0.09 mmol, 52.38%). Calcd for
C48H42Cl2Cu2N12O4S6: C, 48.40; H, 3.38; N, 13.53; S, 15.47%.
Found: C, 48.27; H, 3.26; N, 13.32; S, 15.42%. IR (KBr pellet):
3109 (vw), 3074 (vw), 3024 (w), 2960 (vw), 1566 (vs), 1549 (vs),
1491 (w), 1450 (vw), 1429 (vw), 1385 (vs), 1254 (w), 1186 (s),
1099 (s), 1088 (s), 985 (w), 951 (w), 847 (w), 812 (m), 795 (w),
773 (w), 766 (s), 748 (m), 706 (w), 648 (w), 638 (w), 623 (m), 602
(w), 565 (w), 465 (w), 449 (w) cm−1
.
Ⅱ
Preparation of {[Cu (bpb)2Br](ClO4)•3dmf•MeCN}n (3):
A solution of 1,2-bis(bromomethyl)benzene (0.13 g, 0.5 mmol)
and sodium pyridine-4-thiolate (0.12 g, 1 mmol) in dmf (15 mL)
was heated to 50 °C for 6 h with vigorous stirring. After cooling,
a pale-yellow solution was filtered. Then, a solution of
Cu(ClO4)2•6H2O (0.14 g, 0.5 mmol) in CH3CN (10 mL) was add-
ed and the reaction mixture was stirred for 1 h to give a blue solu-
tion. A dark-blue crystalline complex 3 was obtained by diffusion
of diethyl ether into the resulting solution after two days. Yields:
0.18 g (0.16 mmol, 62.07%). Calcd for C47H56BrClCuN8O7S4: C,
48.95; H 4.86; N, 9.72; S, 11.11%. Found: C, 48.17; H, 4.47; N,
9.56; S, 10.93%. IR (KBr pellet) 3070 (w), 3043 (vw), 3012 (vw),
2470 (vw), 1597 (vs), 1537 (w), 1489 (m), 1452 (w), 1427 (S),
1331 (w), 1225 (m), 1149 (m), 1120 (s), 1080 (s), 1016 (w), 827
Scheme 1.
Experimental
General Procedures and Measurements. All of the re-
agents were commercially available and used as purchased with-
out further purification. Sodium pyrimidine-2-thiolate and sodi-
um pyridine-4-thiolate were obtained through the reaction of 2-
mercaptopyrimidine and 4-mercaptopyrimidine with NaOCH3 in
MeOH, respectively. The ligands bpsb and bpb were prepared in
situ from the reaction of 1,2-bis(bromomethyl)benzene and sodi-
um pyrimidine-4-thiolate or sodium pyridine-4-thiolate, respec-
tively, in methanol. [Cu(CH3CN)4]ClO4 was prepared according
to literature methods.19 The IR spectra as a KBr disk were record-
ed on a Magna 750 FT-IR spectrophotometer. Elemental analysis
(C, H, N) was determined on an Elementar Vario ELIII elemental
(m), 723 (m), 631 (m), 503 (m) cm−1
.
Crystal Structure Determination. Single crystals of com-
plexes 1–3 with approximate dimensions (0.10×0.14×0.16 mm
for 1, 0.65×0.60×0.60 mm for 2, and 0.43×0.38×0.25 mm for
3) were used for data collections on a Siemens Smart CCD dif-
fractometer with graphite-monochromated Mo-Kα radiation (λ =
0.71073 Å) at 298 K. Empirical absorption corrections were ap-
plied by using the SADABS program for the Siemens area detec-
tor. The structures were solved by direct methods and all calcula-
tions were performed with the SHELXL PC program. The coordi-
nates of the heavy atoms were obtained from an E-map; succes-
sive difference Fourier syntheses gave all of the coordinates of the
non-hydrogen atoms. The positions of H atoms were generated
geometrically (C–H bond fixed at 0.96 Å), assigned isotropic ther-
mal parameters, and allowed to ride on their parent carbon atoms
before the final cycle of refinement. The structure was refined by
full-matrix least-squares minimization of Σ(Fo−Fc)2 with aniso-
tropic thermal parameters for all atoms, except the H atoms.
Table 1 gives the crystal data and structure determination summa-
ry for 1–3 and Table 2–4 list the selected bond lengths and angles
for 1–3. Crystallographic data (excluding structure factors) for
the three structures have been deposited in the Cambridge Crystal-
lographic Data Centre as supplementary publication No. CCDC
160678, 160679 and 160680. Copies of the data can be obtained
free of charge by applying to CCDC, 12 Union Road, Cambridge
CB21EZ, UK (Fax: (+44) 1223-336-033; Email: deposit
@ccdc.cam.ac.uk). The details of structures have been deposited
as Document No. 75017 at Office of the Editor of Bull. Chem.
Soc. Jpn.
analyzer.
Ⅰ
Preparation of {[Cu 2(bpsb)3(ClO4)](ClO4)}n (1):
A solu-
tion of 1,2-bis(bromomethyl)benzene (0.13 g, 0.5 mmol) and sodi-
um pyrimidine-2-thiolate (0.11 g, 1 mmol) in MeOH (30 mL) was
heated to 50 °C for 6 h with vigorous stirring. After cooling, a
CH3CN (10 mL) solution of AgClO4 (0.22 g, 1 mmol) was added
to remove any Br−. The mixture was stirred for 30 min and then
filtered. To the filtrate was added dropwise a CH3CN (10 mL) so-
lution of [Cu(CH3CN)4]ClO4 (0.18 g, 0.5 mmol), and the reaction
mixture was stirred for 1 h to give a yellow solution, which was
filtered. Yellow crystalline complex 1 was obtained by keeping
the resulting solution in the air for one week. Yields: 0.17 g (0.13
mmol, 78.14%). Calcd for C48H42Cl2Cu2N12O8S6: C, 44.13; H
3.22; N, 12.87; S, 14.71%. Found: C, 43.97; H, 3.16; N, 12.73; S,
14.49%. IR (KBr pellet) 3115 (vw), 3068 (vw), 2938 (vs), 1574
(s), 1551 (vs), 1491 (w), 1446 (w), 1429 (w), 1381 (vs), 1252 (w),
1217 (m), 1181 (vs), 1088 (vs), 945 (w), 847 (w), 796 (m), 762
(m), 706 (m), 687 (w), 648 (w), 623 (m), 602 (w), 563 (w), 474
(w), 463 (w), 449 (m) cm−1
.
Ⅰ
Preparation of {[Cu 2(bpsb)3Cl](ClO4)}n (2): A solution of
1,2-bis(bromomethyl)benzene (0.13 g, 0.5 mmol) and sodium py-
rimidine-2-thiolate (0.11 g, 1 mmol) in dmf (20 mL) was heated to
50 °C for 6 h with vigorous stirring. After cooling, a CH3CN (10
Results and Discussion
Syntheses: In our previous work, the self-assembly reac-
tions of bpsb and bpb ligands with the Ag(Ⅰ) species resulted in

R.-H. Wang et al.
Bull. Chem. Soc. Jpn., 75, No. 4 (2002) 727
Table 1. Crystallographic Data for the Three Crystal Structures
Ⅰ
Ⅰ
Ⅱ
Compound
{[Cu 2(bpsb)3(ClO4)](ClO4)}n {[Cu 2(bpsb)3Cl](ClO4)}n {[Cu (bpb)2Br](ClO4)•3dmf•MeCN}n
Formula
Fw
C48H42Cl2Cu2N12O8S6
1305.27
C48H42Cl2Cu2N12O4S6
1241.28
C47H56BrClCuN8O7S4
1152.14
Crystal size(mm)
Crystal system
Space group
0.10 × 0.14 × 0.16
Trigonal
P31c
0.65 × 0.60 × 0.60
Hexagonal
P63
0.43 × 0.38 × 0.25
Triclinic
P1
a/Å
b/Å
c/Å
α/°
β/°
γ/°
14.31(2)
14.31(2)
15.56(5)
14.292(2)
14.292(2)
14.769(3)
10.6173(6)
11.8589(6)
23.9307(1)
92.956(1)
100.620(1)
108.193(1)
2802.9(3)
2
1.365
1.352
293(2)
0.71073
120
2760(11)
2
1.571
1.158
293(2)
0.71073
13559
3023
120
2612.7(8)
2
1.578
1.213
293(2)
0.71073
13572
2549
V/Å3
Z
ρ
calcd/g cm−3
µ/mm−1
T/K
λ(Mo Kα)/Å
Reflections collected
Unique reflections
Observed reflections
(F > 4.0σ(F))
parameters
15381
9854
4308
1940
2299
235
1.070
223
1.041
592
1.020
S on F2
R1
0.0680
0.0335
0.0676
Rw
0.1259
0.484 and −0.784
0.0403
0.344 and −0.581
0.1192
1.037 and −1.004
∆ρmin and ∆ρ max [e/Å3]
Ⅰ
Table 2. Selected Bond Lengths [Å] and Angles [°] for {[Cu 2(bpsb)3(ClO4)](ClO4)}n
Cu(1)–N(1)
Cu(1)–N(1D)
Cu(2)–N(4)
Cu(2)–N(4E)
2.004(8)
2.004(8)
2.134(8)
2.134(8)
Cu(1)–N(1B)
Cu(2)–O(3)
Cu(2)–N(4A)
2.004(8)
1.91(2)
2.134(8)
N(1)–Cu(1)–N(1B)
N(1B)–Cu(1)–N(1D)
O(3)–Cu(2)–N(4A)
N(4A)–Cu(2)–N(4)
N(4)–Cu(2)–N(4E)
119.21(8)
119.21(8)
110.3(2)
108.6(2)
108.6(2)
N(1)–Cu(1)–N(1D)
O(3)–Cu(2)–N(4)
O(3)–Cu(2)–N(4E)
N(4A) –Cu(2)–N(4E)
119.21(8)
110.3(2)
110.3(2)
108.6(2)
Symmetry transformations used to generate equivalent atoms: A: −x+y+1,
−x+1, z; B: −y+1, x−y, z ; D: −x+y+2, −x+1, z; E: −y+1, x−y−1, z.
Ⅰ
Table 3. Selected Bond Lengths [Å] and Angles [°] for {[Cu 2(bpsb)3Cl](ClO4)}n
Cu(1)–N(1A)
Cu(1)–N(1C)
Cu(2)–N(4B)
Cu(2)–Cl(2)
1.986(3)
1.986(3)
2.149(4)
2.294(2)
Cu(1)–N(1)
Cu(2)–N(4)
Cu(2)–N(4E)
1.986(3)
2.149(4)
2.149(4)
N(1A)–Cu(1)–N(1)
N(1)–Cu(1)–N(1C)
N(4)–Cu(2)–N(4E)
N(4)–Cu(2)–Cl(2)
N(4E)–Cu(2)–Cl(2)
119.890(13)
119.890(13)
100.58(13)
117.34(11)
117.34(11)
N(1A)–Cu(1)–N(1C)
N(4)–Cu(2)–N(4B)
N(4B)–Cu(2)–N(4E)
N(4B)–Cu(2)–Cl(2)
119.890(13)
100.58(13)
100.58(13)
117.34(11)
Symmetry transformations used to generate equivalent atoms: A: −x+y+2,
−x, z; B: −x+y+2, −x+1, z; C: −y, x−y−2, z; E: −y+1, x−y−1, z.

728 Bull. Chem. Soc. Jpn., 75, No. 4 (2002)
Copper-Organic Coordination Polymers
Ⅱ
Table 4. Selected Bond Lengths [Å] and Angles [°] for {[Cu (bpb)2Br](ClO4)•
3dmf•MeCN}n
Cu(1)–N(2)
Cu(1)–N(3A)
Cu(1)–Br(1)
2.035(8)
2.043(8)
2.723(2)
Cu(1)–N(1A)
Cu(1)–N(4)
2.043(9)
2.058(8)
N(2)–Cu(1)–N(1A)
N(1A)–Cu(1)–N(3A)
N(1A)–Cu(1)–N(4)
N(2)–Cu(1)–Br(1)
N(3A)–Cu(1)–Br(1)
89.9(3)
88.2(3)
168.1(4)
94.0(3)
98.6(3)
N(2)–Cu(1)–N(3A)
N(2)–Cu(1)–N(4)
N(3A)–Cu(1)–N(4)
N(1A)–Cu(1)–Br(1)
N(4)–Cu(1)–Br(1)
167.3(4)
90.0(3)
89.3(3)
96.8(3)
95.0(3)
Symmetry transformations used to generate equivalent atoms: A: x+1, y+1, z.
several structures,16 this prompting us to extend our work to
other metal ions and hope to obtain some novel structures that
are different from those of silver(I) complexes. Unfortunately,
the reaction of bpsb with Cu(ClO4)2•6H2O in dmf/CH3CN pro-
duced an uncharacterized yellow oil, and changing the cop-
per(Ⅱ) starting materials to copper nitrate or acetate was not
helpful for the reactions. After a careful study of the coordina-
tion geometry of bpsb, we sensed that the unsatisfactory re-
sults may have been caused by a mismatching coordination ge-
ometry between bpsb and Cu(Ⅱ). As is known, Cu(Ⅱ) favors a
square-planar or square-pyramidal coordination geometry, re-
quiring four bpsb molecules to coordinate to Cu(Ⅱ) owing to
the non-chelating coordination mode of bpsb, which would
cause a large space hindrance, and thereby render the forma-
tion of stable compounds. We thus introduced Cu(Ⅰ) into the
reaction in view of the same d10 configurations and similar co-
ordination geometry between Cu(Ⅰ) and Ag(Ⅰ). As expected,
complex 1, which possesses a similar structure to its silver an-
alogue,16a was isolated from the reaction of bpsb and
[Cu(CH3CN)]ClO4 in good yields. The differences of 1 and 2
may come from the different anions present in the synthetic re-
actions, similar to the case of the Ag(Ⅰ) reaction. When bpb
was used as a ligand, it was possible for four bpb molecules to
coordinate to one Cu(Ⅱ) center, and complex 3 was isolated in
an in situ reaction of bpb with Cu(ClO4)2•6H2O, giving satis-
factory yields. However, Br− is necessary to saturate the
square-pyramidal coordination geometry of Cu(Ⅱ) in this reac-
tion, and the removal of Br− from the reaction system resulted
in a failure to isolate 3.
Fig. 1. View of the hexanuclear coppers nanocavity in 1.
Description of Complex 1: The crystal structure of com-
plex 1 is shown in Figs. 1 and 2. Copper(Ⅰ) atoms in the com-
plex have two different coordination geometry. Cu(1) is coor-
dinated by three nitrogen atoms from different, but symmetry-
equivalent, bpsb ligands related by threefold axes passing
through the Cu(1) atom. Thus, each Cu(1) atom is in an un-
20
usual, but precedent, trigonal geometry of Cu(N)3 [Cu(1)–N
= 2.004(8) Å, N–Cu(1)–N = 119.21(8)°]. However, the coor-
dination geometry around the Cu(2) atom is a distorted tetrahe-
dral arrangement with an oxygen atom of perchlorate occupy-
ing the apical position (Cu–O = 1.912(17) Å) and three nitro-
gen atoms of different bpsb ligands lying in the basal sites.
The Cu(I)–N bond distances for the four-coordinated Cu(Ⅰ) are
2.134(8) Å, which are longer than 2.004(8) Å for the three-co-
ordinated Cu(I). Each bpsb molecule acts as an exo-bidentate
ligand. Two nitrogen atoms from different pyrimidinyl rings
Fig. 2. Space-filling of the lamellar structure in complex 1,
along ab plane, coordinated perchlorates were omitted for
clarity.
coordinate to two crystallographically independent Cu(Ⅰ) at-
oms in different directions to form a 2-D lamellar structure
with crown-like nanocavities. Therefore, the six copper(Ⅰ)
centers (three 3-coordinated and the three 4-coordinated) lo-
cated at two different planes, alternatively, are linked by six

R.-H. Wang et al.
Bull. Chem. Soc. Jpn., 75, No. 4 (2002) 729
Fig. 3. View of the lamellar structure in 2, along ab plane.
flexible bpsb ligands forming a crown-like [Cu6(bpsb)6] unit
with dimensions of 20.84×14.45 Å, in which uncoordinated
Fig. 4. View of the basic box unit in the polymeric chain of 3
with perchlorates, solvent molecules omitted for clarity.
perchlorate is partially encapsulated.
The crown-like
[Cu6(bpsb)6] units generate a 2-D lamellar structure by a sym-
metry operation, which are quite different from the usual hexa-
nuclear copper(Ⅰ) units20–22 and similar to the silver(Ⅰ) coordi-
nation polymer.16a
Description of Complex 2: A crystallographic analysis
revealed that complexes 2 and 1 have similar structures.
Namely, they have an analogous coordination geometry of
Cu(Ⅰ) atoms and the same crown-like lamellar structure. The
molecular structure of complex 2 is shown in Fig. 3. Similar to
1, Cu(Ⅰ) atoms have two different coordination fashions. The
Cu(1) atom is coordinated by three nitrogen atoms from differ-
ent, but symmetrically related, bpsb molecules forming an un-
usual, but precedented, 3-coordinated trigonal geometry.20
(Cu(1)–N = 1.986(3) Å, N–Cu(1)–N = 119.889(13)°). The
Cu(2) atom exhibits a distorted tetrahedral geometry with one
Cl− occupying the apical position (Cu(2)–Cl = 2.292(2) Å)
and three nitrogen atoms from different bpsb molecules com-
prising the equatorial plane (Cu(2)–N = 2.149(4) Å, N–
Cu(2)–N = 100.58(13)°). In this complex, bpsb molecules act
as interconnecting ligands of Cu(Ⅰ) atoms with different coor-
dination geometry to form a 2-D lamellar structure with
crown-like nanocavities. The dimensions of the nanocavities
are similar to those of compound 1 and Ag(Ⅰ) polymer.16a
Description of Complex 3: A crystallographic analysis
of complex 3 indicates that it possesses an infinite 1-D poly-
meric chain which constitutes basic square units of
[Cu2(bpb)2Br2]2+. The molecular structure is shown in Figs. 4
and 5. Each Cu(Ⅱ) center acts as a joint of a square ring and is
coordinated by one Br− atom lying in the apical position and
four nitrogen atoms from different, but symmetry-equivalent,
bpb ligands occupying the basal sites. Thus, the coordination
environment around Cu(Ⅱ) can best be described as a distorted
square-pyramidal form of CuN4Br. The Cu(Ⅱ)–N(bpb) and
Cu(Ⅱ)–Br− bond distances fall in the range of 2.043(8)–
2.058(8) Å and 2.732(2) Å, respectively. The Cu(Ⅱ)–Cu(Ⅱ)
separations are of 5.613(3) Å in length. The bond angles of cis
N–Cu–N(bpb) are close to a value of 90°. Each bpb molecule
Fig. 5. Space-filling representation of complex 3 with dmf
solvent molecules in the cavities.
exhibiting an exo-bidentate coordination mode bridges two
Cu(Ⅱ) centers with two nitrogen atoms from different pyridyl
rings to form a square ring with the size of 8.5 × 8.5 Å, which
accommodates one dmf molecule; the other solvent molecules
are out of the square ring. Such square rings, constituting two
bidentate bpb ligands in which two nitrogen atoms from differ-
ent pyridyl rings coordinate to two Cu(Ⅱ) centers in different
directions and two Cu(Ⅱ) centers which are shared by two dif-
ferent square units form an infinite 1-D chain.
Conclusion
The self-assembly of two designed non-chelating bridging
ligands, bpsb and bpb, with Cu(Ⅰ) and Cu(Ⅱ), respectively, in a
1:1 metal:ligand ratio yielded two 2-D lamellar polymers con-
taining crown-like nanocavities and a single-stranded infinite
1-D chain polymer containing square rings with solvent mole-
cule guests, respectively. The ligands bpsb and bpb act as exo-
bidentate ligands through coordinating to two copper atoms in
different directions with two nitrogen atoms from different py-
rimidinyl rings or pyridyl rings, respectively. The results of
this study illustrate that a spatial effect of coordination atoms,
the geometry and rigidity of the ligand, and the coordination
form of metal ions play important roles in constructing of su-
pramolecular architecture. This contributes to own ability to

730 Bull. Chem. Soc. Jpn., 75, No. 4 (2002)
Copper-Organic Coordination Polymers
10 a) G. Baum, E. C. Constable, D. Fenske, C. E. Housecroft,
T. Kulke, M. Neuburger, and M. Zehnder, J. Chem. Soc., Dalton
Trans., 2000, 945. b) B. Hasenknopf, J.-M. Lehn, B. O. Kneisel,
G. Baum, and D. Fenske, Angew. Chem., Int. Ed. Engl., 35, 1838
(1996). c) R. Ziessel, A. Harriman, J. Suffert, M.-T. Youinou, A.
D. Cian, and J. Fischer, Angew. Chem., Int. Ed. Engl., 36, 2509
(1997).
predict and control certain structural topologies through the
self-assemble of multidentate ligands with suitable metal ions
in supramolecular chemistry and coordination chemistry. Fur-
ther research concerning self-assembly bpsb and bpb ligands
with other bridging or terminal ligating moieties and suitable
metal ions is now being explored in our laboratory.
11 a) M. Munakata, L. P. Wu, and T. Kuroda-Sowa, Bull.
Chem. Soc. Jpn., 70, 1727 (1997), and references therein. b) I.
Ino, J. C. Zhong, M. Munakata, T. Kuroda-Sowa, M. Maekawa, Y.
Suenaga, and Y. Kitamori, Inorg. Chem., 39, 4273 (2000). c) C.
M. Hartshorn and P. J. Steel, J. Chem. Soc., Dalton Trans., 1998,
3935.
This work is supported by the National Nature Science
Foundation of China and the Key Project of Chinese Academy
of Science for financial support.
References
1
a) J.-M. Lehn, “Supramolecular Chemistry — Concepts
12 Z. N. Chen, W. J. Li, B. S. Kang, M. C. Hong, Z. Y. Zhou,
T. C. W. Mak, X. M. Chen, and H. Q. Liu, Inorg. Chem., 36, 208
(1997), and references therein.
13 a) W. P. Su, M. C. Hong, J. B. Weng, R Cao, and S. F. Lu,
Angew. Chem., Int. Ed., 39, 2911 (2000). b) M. C. Hong, W. P. Su,
R. Cao, W. J. Zhang, W.-T. Wong, and J. X. Lu, Inorg. Chem., 38,
600 (1999). c) W. P. Su, R. Cao, M. C. Hong, W. J. Zhang, W.-T.
Wong, and J. X. Lu, Inorg. Chem. Commun., 2, 241 (1999)
14 Y. J. Zhao, M. C. Hong, W. P. Su, R. Cao, and W. J. Li,
Chem. Commun., 2001, 1020.
15 a) M. C. Hong, Y. J. Zhao, W. P. Su, R. Cao, M. Fujita, Z.
Y. Zhou, and A. S. C. Chan, J. Am. Chem. Soc., 122, 4819 (2000).
b) M. C. Hong, Y. J. Zhao, W. P. Su, R. Cao, M. Fujita, Z. Y. Zhou,
and A. S. C. Chan, Angew. Chem., Int. Ed., 39, 2468 (2000).
16 a) M. C. Hong, W. P. Su, R. Cao, M. Fujita, and J. X. Lu,
Chem. Eur. J., 6, 427 (2000). b) Y. J. Zhao, M. C. Hong, W. P. Su,
R. Cao, Z. Y. Zhou, and A. S. C. Chan, Chem. Lett., 6, 1 (2000).
17 L. Carlucci, G. Ciani, and D. M. Proserpio, J. Chem. Soc.,
Dalton Trans., 1999, 1799, and references therein.
18 a) M. G. Barandika, M. L. Hernández-Pino, M. K. Urtiaga,
R. Cortés, L. Lezama, M. I. Arriortua, and T. Rojo, J. Chem. Soc.,
Dalton Trans., 2000, 1469. b) K. Kasai, M. Aoyagi, and M.
Fujita, J. Am. Chem. Soc., 122, 2140 (2000). c) M. Fujita, M.
Aoyagi, and K. Orgura, Bull. Chem. Soc. Jpn., 71, 1799 (1998).
19 E. Müller, G. Bernardinelli, and J. Reedijk, Inorg. Chem.,
35, 1952 (1996).
and Perspectives,” VCH, Weinheim, (1995). b) A. D. Burrows,
C.-W. Chan, M. M. Chowdhry, J. E. McGrady, and D. M. P.
Mingos, Chem. Soc. Rev., 24, 329 (1995). c) C. Piguet, G.
Bernardinelli, and G. Hopfgartner, Chem. Rev., 97, 2005 (1997).
d) A. M. Garcia, F. J. Romero-salguero, D. M. Bassani, J.-M.
Lehn, G. Baum, and D. Fenske. Chem. Eur. J., 9, 1803 (1999).
2
a) A. Distler and S. C. Sevov, Chem. Commun., 1998, 959.
b) R. L. Paul, S. M. Couchman, J. C. Jeffery, J. A. McCleverty, Z.
R. Reeves, and M. D. Ward, J. Chem. Soc., Dalton Trans., 2000,
845.
3
G. K. H. Shimizu, G. D. Enright, C. I. Ratcliffe, J. A.
Ripmeester, and D. D. M. Wayner, Angew. Chem., Int. Ed., 37,
1407 (1998).
4
K. L. V. Mann, E. Psillakis, J. C. Jeffery, L. H. Rees, N. M.
Harden, J. A. McCleverty, M. D. Ward, D. G. Atteschi, F. Totti, F.
E. Mabbs, E. J. L. Mclnnes, P. C. Riedi, and M. Smith, J. Chem.
Soc., Dalton Trans., 1999, 339, and references therein.
5
Y. B. Dong, M. D. Smith, R. C. Layland, and H.-C. z.
Loye, Inorg. Chem., 38, 339, (1999).
J. Lu, T. Paliwala, S. C. Lim, C. Yu, T. Niu, and A. J.
Jacobson, Inorg. Chem., 116, 923 (1997).
a) P. J. Hagrman, D. Hagrman, and J. Zubieta, Angew.
6
7
Chem., Int. Ed., 38, 2639 (1999). b) K. Biradha, K. V.
Domasevitch, B. Moulton, C. Seward, and M. J. Zaworotko,
Chem. Commun., 1999, 1327. c) H. Gudbjartson, K. Biradha, K.
M. Poirier, and M. J. Zaworotko, J. Am. Chem. Soc., 121, 2599
(1999).
20 L. R. MacGillivray, S. Subramanian, and M. Zaworotko,
Chem. Commun., 1994, 1325, and references therein.
8
a) T. M. Reineke, M. Eddaoudi, M. Okeeffe, and O. M.
21 a) M. Munakata, L. P. Wu, T. Kuroda-Sowa, M. Maekawa,
K. Moriwaki, and S. Kitagawa, Inorg. Chem., 36, 5416 (1997). b)
N. Masciocchi, G. A. Ardizzoia, G. LaMonica, A. Maspero, and
A. Sironi, Angew. Chem., Int. Ed., 37, 3366 (1998).
22 a) M. Munakata, T. Kuroda-Sowa, M. Maekawa, M.
Nakamura, S. Akiyama, and S. Kitagawa, Inorg. Chem., 33, 1284
(1994). b) T. Otieno, S. J. Rettig, R. C. Thompson, and J. Trotter,
Inorg. Chem., 32, 1607 (1993). c) S. Kitagawa, M. Munakata, and
T. Tanimura, Inorg. Chem., 31, 1714 (1992).
Yaghi, Angew. Chem., Int. Ed., 38, 2590 (1999). b) H. Li, C. E.
Davis, T. L. Groy, D. G. Kelley, and O. M. Yaghi, J. Am. Chem.
Soc., 120, 2186 (1998). c) R. H. Wang, M. C. Hong, Y. C. Liang,
and R. Cao, Acta Crystallogr., Sect. E, 57, 325 (2001).
9
a) J. J. Lessmann and W. DeW. Horrocks, Jr., Inorg. Chem.,
39, 3114 (2000). b) B. L. Fei, W. Y. Sun, K. B. Yu, and W. X.
Tang, J. Chem. Soc., Dalton Trans., 2000, 805. c) P. L. Caradoc-
Davies, L. R. Hanton, and K. Lee, Chem. Commun., 2000, 783.