Syntheses and crystal structures of three one-dimensional copper(II) complexes constructed by salicylate and 4,4′-bipyridine: Ladder, zig-zag, and linear polymeric assembly

Article abstract of DOI:10.1016/S0020-1693(03)00254-8

Syntheses and crystal structures of three new compounds {trans-[Cu(Hsal)₂(4,4′-bipy)](DMF)}_n (1), {cis-[Cu(Hsal)₂(4,4′-bipy)](2H₂O)}_n (2), and [Cu₂(Hsal)₄(4,4′-bipy)]_n (3) are reported. These three compounds have trans-, cis-, and dimer geometries bearing a common motif [Cu(Hsal)₂(4,4-bipy)_n] leading to ladder, zig-zag, and linear one-dimensional (1-D) networks, respectively. The CuCu distances separated by 4,4′-bipy are different in these three compounds, which leads to an extension structure in compound 3 and a compact structure in compound 2. Conformations of 4,4′-bipy ligands in these three compounds are also different. In compound 1 there is stacking of the bidentate salicylate and the bridging salicylate from another molecule. There is also stacking of salicylate and 4,4′-bipy from another molecule in compound 2.

Full text of DOI:10.1016/S0020-1693(03)00254-8

Inorganica Chimica Acta 355 (2003) 121ꢀ126
/
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Syntheses and crystal structures of three one-dimensional copper(II)
complexes constructed by salicylate and 4,4?-bipyridine:
ladder, zig-zag, and linear polymeric assembly
Long-Guan Zhu a,*, Susumu Kitagawa b, Hitoshi Miyasaka b, Ho-Chol Chang b
a Department of Chemistry, Zhejiang University, 38 Zheda Road, Hangzhou 310027, China
b Department of Synthetic Chemistry and Biological Chemistry, Faculty of Engineering, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan
Received 7 February 2003; received in revised form 2 April 2003; accepted 5 April 2003
Abstract
Syntheses and crystal structures of three new compounds {trans-[Cu(Hsal)2(4,4?-bipy)](DMF)}n (1), {cis-[Cu(Hsal)2(4,4?-
bipy)](2H2O)}n (2), and [Cu2(Hsal)4(4,4?-bipy)]n (3) are reported. These three compounds have trans-, cis-, and dimer geometries
bearing a common motif [Cu(Hsal)2(4,4-bipy)n] leading to ladder, zig-zag, and linear one-dimensional (1-D) networks, respectively.
The Cuꢀ ꢀ ꢀCu distances separated by 4,4?-bipy are different in these three compounds, which leads to an extension structure in
compound 3 and a compact structure in compound 2. Conformations of 4,4?-bipy ligands in these three compounds are also
different. In compound 1 there is stacking of the bidentate salicylate and the bridging salicylate from another molecule. There is also
stacking of salicylate and 4,4?-bipy from another molecule in compound 2.
# 2003 Elsevier B.V. All rights reserved.
Keywords: Copper complexes; Crystal structures; One-dimension; Salicylate; Bipyridine; Assembly
1. Introduction
[4]. Although transition metal complexes with 4,4?-
bipyridine have shown many interesting networks
3d[5], few trans- and cis- coordination motifs of 4,4?-
bipy in the same formulated compounds were reported.
Examples of linear chain compounds of copper are still
limited despite a vast number of dimeric copper
carboxylates and their adducts [6]. Complexes of
salicylic acid (H2sal) are of interest from structural
and biological viewpoints [7]. The combination of 4,4?-
bipy and H2sal is expected to construct various poly-
meric compounds. Since it is useful to understand the
construction strategy of novel geometric polymers,
elucidation of the structure-directing effects of various
solvents will enable a better understanding possibilities
of crystal engineering for the synthesis of complexes
using different solvent systems. Herein, we report
examples of trans-, cis-, and dimer geometries bearing
Recently much attention has been paid in the field of
crystal engineering using bridging heterocyclic amine
bidentate ligands with transition metals to form co-
ordination polymers [1]. The 4,4?-bipyridine (4,4?-bipy)
ligand and its analogues have been used in much of this
work. The coordination polymers bearing 4,4?-bipy
ligands have been shown to form a wide range of
interesting network topologies, for example, chains,
ladders, grids, and adamantoid networks [2], and 4,4?-
bipyridine is very popular for the construction of porous
organicꢀinorganic hybrid solids with potential applica-
/
tions as catalytic, gas adsorption, or molecular sieve
materials [3]. One-dimensional (1-D) chain compounds
have been the focus of very active research because of
their special and excellent physicochemical properties
a common motif [Cu(Hsal)2(4,4?-bipy)n] (nꢁ
/
1 for 1 and
2, nꢁ0.5 for 3) in three 1-D compounds, {trans-
/
[Cu(Hsal)2(4,4?-bipy)](DMF)}n (1), {cis-[Cu(Hsal)2-
(4,4?-bipy)](2H2O)}n (2), and [Cu2(Hsal)4(4,4?-bipy)]n
(3).
* Corresponding author. Tel.: ꢂ
8795 1895.
E-mail address: chezlg@zju.edu.cn (L.-G. Zhu).
/
86-571-8796 3867; fax: ꢂ86-571-
/
0020-1693/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0020-1693(03)00254-8

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L.-G. Zhu et al. / Inorganica Chimica Acta 355 (2003) 121ꢀ126
/
2. Experimental
a maximum 2u value of 55.5 using v scan. The 18 845,
8321, and 27 198 reflections for compounds 1, 2, and 3
were collected and 5948, 4887, and 2085 were unique
reflections for 1, 2, and 3, respectively. The diameter of
the incident beam collimator was 0.5 mm and the crystal
to detector distance was 35 mm. An empirical absorp-
tion correction based on azimuthal scans of several
reflections was applied. Data were corrected for Lorentz
and polarization effects. Crystal structures for 1, 2, and
3 were solved by direct methods SIR92 [8] and expanded
using Fourier technique DIRDIF94 [9]. The non-hydrogen
atoms were refined anisotropically, while hydrogen
atoms were refined isotropically. Full-matrix least-
squares refinements based on 2911 for 1, 3687 for 2,
2.1. Preparation of the complexes
2.1.1. {trans-[Cu(Hsal)2(4,4?-bipy)](DMF)}n (1)
Crystals were grown by layer-method using two- or
three-layer solutions in a slender tube with a 0.8 cm
diameter. The upper layer solution was 1.5 ml methanol
containing 0.05 mol lꢃ1 Cu2(CH3COO)4×
/
2H2O and 0.20
mol lꢃ1 salicylic acid (H2sal), the bottom layer solution
was 1.5 ml 0.05 mol lꢃ1 4,4?-bipyridine in DMF and
water mixed solvents (ratio of DMFꢀH2O was 1:1).
/
After standing for several days, sky blue crystals grew.
They were collected by suction filtration. Anal. Calc. for
C27H25N3O7Cu: C, 57.19; H, 4.44; N, 7.41. Found: C,
57.13; H, 4.40; N, 7.28%. IR (KBr pellet, cmꢃ1):
1681(s), 1610(s), 1589(s), 1559(s), 1485(s), 1450(s),
1415(s), 1393(vs), 1253(m), 864(w), 822(m), 754(m),
703(w), 670(w), 645(w).
and 1299 for 3 observed reflections (I ꢀ3.00s(I)) and
/
the unweighted and weighted agreement factors of
Rꢁ
/
ajjFojꢃ
/
jFcjj/ajFoj and Rwꢁ
/
[a w(jFojꢃ
/
jFcj)2/
2 1/2
a wjFoj ] were used. Variable parameters for com-
pounds 1, 2, and 3 in the final cycle of full-matrix least-
squares refinements are 415, 370, and 279, respectively.
The weighting scheme was based on counting statistics.
2.1.2. {cis-[Cu(Hsal)2(4,4?-bipy)](2H2O)}n (2)
Crystals were grown using a similar layer-method as
reported for 1. The upper layer solution was 1.5 ml
Plots of a w(jFojꢃ
/
jFcj)2 versus jFoj, reflection order in
methanol containing 0.05 mol lꢃ1 Cu2(CH3COO)4×
/
data collection, sin u/l, and various classes of indices
showed no unusual trends. All calculations were per-
formed using the TEXSAN crystallographic software
package [10]. ORTEP graphs were reproduced using
ORTEP-3 for WINDOWS [11]. Crystal data and details of
2H2O and 0.20 mol lꢃ1 salicylic acid, the bottom layer
solution was 2.5 ml 0.025 mol lꢃ1 4,4?-bipyridine in
water and the middle layer was 1.0 ml waterꢀmethanol
/
(1:1) mixed solvent system. After standing for several
days, dark blue crystals grew. They were filtered by
suction filtration, washed with small amount of water,
and then dried in air. Anal. Calc. for C24H22N2O8Cu: C,
54.39; H, 4.18; N, 5.29. Found: C, 54.50; H, 4.12; N,
5.42%. IR (KBr pellet, cmꢃ1): 1612(s), 1555(m), 1482(s),
1450(s), 1415(s), 1398(vs), 1252(s), 1223(m), 869(w),
821(m), 762(m), 705(w), 671(w), 645(w).
Table 1
Crystallographic data for {trans-[Cu(Hsal)2(4,4?-bipy)](DMF)}n (1),
{cis-[Cu(Hsal)2(4,4?-bipy)](2H2O)}n (2), and [Cu2(Hsal)4(4,4?-bipy)]n
(3)
1
2
3
Formula
M
Crystal system
C
27H25CuN3O7 C24H22CuN2O8 C19H14CuNO6
2.1.3. [Cu2(Hsal)4(4,4?-bipy)]n (3)
567.06
monoclinic
P21/c (#14)
13.689(4)
11.158(3)
17.080(1)
90
529.99
triclinic
415.87
tetragonal
I41cd
Crystals were grown using a method similar to 2, but
without a middle layer. Anal. Calc. for C19H14NO6Cu:
C, 54.88; H, 3.39; N, 3.37. Found: C, 55.03; H, 3.43; N,
3.47%. IR (KBr pellet, cmꢃ1): 1632(s), 1598(vs),
1485(m), 1464(s), 1416(w), 1390(vs), 1249(m), 1217(m),
866(w), 813(w), 765(m),705(w), 674(w), 634(w).
¯
P1 (#2)
Space group
˚
/
a (A)
˚
10.377(1)
10.6890(4)
11.026(1)
86.181(3)
70.2643(9)
88.837(1)
1148.6(1)
2
13.9645(3)
13.9645(3)
38.110(1)
90
b (A)
˚
c (A)
a (8)
b (8)
g (8)
V (A )
Z
Dc (g cmꢃ3
101.038(1)
90
90
90
3
˚
2.2. Crystallography
2560(1)
4
1.471
7431.7(4)
16
1.487
)
1.532
546
Single crystals of 1, 2, and 3 were prepared by the
method described in the above procedures. All single
crystals for crystallographic analysis were mounted on
F
l (A)
1172
0.71069
9.05
3392
0.71069
12.10
˚
0.71069
10.05
m (cmꢃ1
)
glass fibers. The crystal dimensions were 0.1ꢄ
/
0.3ꢄ
/
0.5
Crystal size (mm) 0.1ꢄ
/
0.2ꢄ
/
0.3 0.05ꢄ
/
prismatic
55.5
0.3ꢄ
/
0.55 0.2ꢄ
/
0.2ꢄ0.3
/
Crystal habit
2u (8)
Plate
55.5
5948
tetragonal
55.5
2085
mm for 1, 0.05ꢄ0.3ꢄ0.55 mm for 2, and 0.2ꢄ
/
/
/
0.3ꢄ
/
0.3 mm for 3. Measurements for all compounds were
made on a Rigaku AFC 8R diffractometer with a CCD
N
4887
No. (I ꢀ
R
/
3.0s(I)) 2911
0.054
0.056
3687
0.043
0.050
1299
0.051
0.061
detector and graphite-monochromated Mo Ka radia-
˚
0.71069 A). Data were collected at room
tion (lꢁ
/
Rw
temperature (23 8C) for 1 and 2 and ꢃ100 8C for 3 to
/

L.-G. Zhu et al. / Inorganica Chimica Acta 355 (2003) 121ꢀ
/126
123
structure determinations for 1, 2, and 3 are summarized
in Table 1.
3.2. Structural descriptions of complexes 1, 2, and 3
3.2.1. Description of the crystal structures
The ORTEP drawings of 1, 2, and 3 with atom
numbering schemes are shown in Figs. 1ꢀ3. Views of
networks of these three complexes are shown in Figs. 4ꢀ
/
3. Results and discussion
/
6. The 4,4?-bipy is disordered in compound 3, but it is
not effected in comparison with the structural charac-
teristics of compounds 1, 2 and 3. Selected bond lengths
3.1. Syntheses of compounds 1, 2, and 3
Crystals of compounds 2 and 3 are stable overtime if
kept in solution, while crystals of compound 1 become
opaque, but they are stable overtime in air. Compounds
1 and 2 were obtained in different solvent systems (see
Section 2.1). The formulae of compounds 1 and 2 are
similar except for crystallized solvents (for 1, containing
DMF and for 2, H2O). Compound 1 was synthesized in
water, methanol, and N,N?-dimethylformamide mixed
solvent systems, while compounds 2 and 3 were synthe-
and angles for 1, 2, and 3 are given in Tables 2ꢀ4,
/
respectively. Geometries of the copper atoms in these
three compounds are distorted octahedral. The structure
of compound 1 is constructed from a motif of two 1-D
linear chains, which form a ladder network and the
structure of compound 2 is constructed from a motif of
a 1-D zig-zag network. The structure of compound 3 is
composed of a 1-D dimer chain from a dimer motif. The
bond length of CuÃ
/
N in compound 3 is longer than that
˚
of compound 2 or 3 (2.025 and 2.037 A in 1; 1.987 and
sized in a methanolꢀwater mixed solvent system. It is
/
˚
˚
easy to distinguish compounds 1, 2, and 3 based upon
their colors and crystal habits. Compound 1 is sky blue,
2 is dark blue, and 3 is green.
1.995 A in 2, and 2.133 A in 3), but these CuÃ
lengths are similar to these reported in reference [12]. In
general, CuÃN bond lengths of polymers with a dimer
/
N bond
/
For the synthesis of compound 3, when two layers of
solutions were put together without mixing them, a
precipitate formed immediately at the interface of the
two layers and after some days crystals of compound 3
were formed in the bottom layer.
Compounds 2 and 3 were synthesized using same
solution concentrations and the same solvents in differ-
ent layers. We did not observe changes for compounds 2
and 3 when kept in solution for 3 months.
motif are longer than that of ladder or zig-zag of 1-D
and 2-D, or 3-D networks as reported elsewhere [6,13]
and Table 8 of reference [12]. In compound 3 all
salicylates have a bridging coordination mode and in
compound 2 all salicylates are bidentately coordinated
with copper. In compound 1 there are two kinds of
coordination modes for salicylate. In compound 3 there
are short CuÃ
compared with compounds 1 and 2 because of the
Cuꢀ ꢀ ꢀCu interaction. The CuÃO bond lengths are
/
O bond distances, shown in Tables 2ꢀ4 as
/
/
Fig. 1. ORTEP view of coordination environment in complex 1 with
atom numberings.
Fig. 2. ORTEP view of coordination environment in complex 2 with
atom numberings.

124
L.-G. Zhu et al. / Inorganica Chimica Acta 355 (2003) 121ꢀ126
/
Fig. 3. ORTEP view of coordination environment in complex 3 with
atom numberings.
Fig. 5. Perspective view of 1-D zig-zag network of complex 2.
similar in compounds 2 and 3. In compound 1 the O(3)Ã
/
Hꢀ ꢀ ꢀO(2) hydrogen bond is stronger than that of O(6)Ã
/
Hꢀ ꢀ ꢀO(5) hydrogen bond in compound 2, but in
compound 2 the two hydrogen bonds are the same. In
compound 1 dihedral angles between ring planes of 4,4?-
bipy and salicylates are 77.4, 76.9, 81.4 and 84.08. In
compound 2 these dihedral angles between planes of
Fig. 4. Perspective view of 1-D ladder network of complex 1.
Fig. 6. Perspective view of 1-D linear network of complex 3.

L.-G. Zhu et al. / Inorganica Chimica Acta 355 (2003) 121ꢀ
/126
125
Table 2
Table 5
˚
˚
Selected bond lengths (A) and angles (8) for compound 1
Cuꢀ ꢀ ꢀCu distances (A) separated by 4,4?-bipy and carboxylic groups in
compounds 1, 2, and 3
Bond lengths
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
/
O(1)
O(4)
N(1)
2.001(3) Cu(1)Ã
1.957(4) Cu(1)Ã
2.037(3) Cu(1)Ã
/
O(2)
O(5*)
N(2)
2.651(4)
2.304(4)
2.025(3)
Compound CuÃ
/
N
CuÃ
/
bipyÃ
/
CuÃ
/
O
CuÃ
/
carboxyÃ
/
/
/
Cu
Cu
/
/
1
2
3
2.037,
11.16
1.957ꢀ
2.304
11.04, 11.09 1.962ꢀ
2.549
/
4.06
Bond angles
O(1)ÃCu(1)Ã
O(1)ÃCu(1)Ã
O(1)ÃCu(1)Ã
O(2)ÃCu(1)Ã
O(2)ÃCu(1)Ã
O(4)ÃCu(1)Ã
O(5*)ÃCu(1)Ã
N(1)ÃCu(1)ÃN(2)
2.025
1.987,
1.995
2.133
/
/
O(2)
O(5*)
N(2)
O(5*)
N(2)
N(1)
54.5(1) O(1)Ã
84.2(1) O(1)Ã
89.8(2) O(2)Ã
137.9(1) O(2)Ã
85.2(2) O(4)Ã
88.0(2) O(4)Ã
89.3(2) O(5*)Ã
176.7(2)
/
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
/
O(4)
N(1)
O(4)
N(1)
O(5*)
N(2)
146.9(1)
90.8(2)
92.9(1)
97.8(2)
128.9(1)
93.3(2)
87.6(2)
/
/
/
/
/
/
/
/
/
11.31
1.914ꢀ
2.041
/
2.66
/
/
/
/
/
/
/
/
/
/
/
/
the strong CuÃ
Consistently, the longer Cuꢀ ꢀ ꢀCu distances are followed
by longer CuÃN bond lengths. There are two types of
CuÃCu separations, 11.04 and 11.09 A, in compound 2.
/
Cu interaction in the dimer motif.
/
/
N(1)
/
/N(2)
/
/
/
* Symmetry operator: ꢃ
/
x, ꢃ
/
y, ꢃz.
/
˚
/
From above structural information we conclude that
there is a 1-D extension structure in compound 3 and
there is a 1-D compact structure in compound 2. It
would be very interesting to study these structural
differences for compounds 1, 2, and 3 with regard to
these different physiochemical properties.
Table 3
˚
Selected bond lengths (A) and angles (8) for compound 2
Bond lengths
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
/
O(1)
O(4)
N(1)
2.013(2)
1.962(2)
1.987(3)
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
/
O(2)
O(5)
N(2)
2.423(3)
2.549(2)
1.995(2)
/
/
/
/
Bond angles
O(1)ÃCu(1)Ã
O(1)ÃCu(1)Ã
O(1)ÃCu(1)Ã
O(2)ÃCu(1)Ã
O(2)ÃCu(1)Ã
O(4)ÃCu(1)Ã
O(5)ÃCu(1)Ã
N(1)ÃCu(1)Ã
3.2.3. Conformations of 4,4?-bipy in these three
compounds
/
/
O(2)
O(5)
N(2)
O(5)
N(2)
N(1)
N(1)
58.55(7)
95.27(8)
O(1)Ã
/
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
/
O(4)
N(1)
O(4)
N(1)
O(5)
N(2)
N(2)
91.78(10)
90.5(1)
/
/
O(1)Ã
/
/
Conformations of 4, 4?-bipy in these three molecules
are very different because of the intra- and inter-
molecular interactions. Dihedral angles between the
two pyridine rings of 4,4?-bipy are listed in Table 6. In
compound 2 the dihedral angle between two planes of
pyridine rings is zero, they are co-planar. We can
conclude that a larger dihedral angle between these
two pyridine rings is followed by a longer Cuꢀ ꢀ ꢀCu
distance due to the 4,4?-bipy ring system.
/
/
157.31(10) O(2)Ã
/
/
99.77(9)
98.55(10)
56.66(8)
92.01(10)
105.47(9)
/
/
146.11(8)
98.76(9)
159.79(9)
103.14(9)
93.6(1)
O(2)Ã
O(4)Ã
O(4)Ã
O(5)Ã
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
N(2)
Table 4
˚
Selected bond lengths (A) and angles (8) for compound 3
Bond lengths
3.2.4. Stacking effects in these compounds
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
/
O(1)
O(4)
N(1)
1.928(7)
2.041(6)
2.133(3)
Cu(1)Ã
Cu(1)Ã
/
O(3)
1.914(7)
1.995(7)
In compound 3 there is no stacking effect between
molecules because of the non-coplanar nature of two
pyridine rings of 4,4-bipy. In compound 1 there is a
stacking effect due to the bidentate salicylate and the
bridging salicylate of another molecule, the dihedral
angle and the distance of these two planes in these two
/
/O(6)
/
Bond angles
O(1)ÃCu(1)Ã
O(1)ÃCu(1)Ã
O(3)ÃCu(1)Ã
O(3)ÃCu(1)Ã
O(4)ÃCu(1)Ã
/
/
O(3)
O(6)
O(4)
N(1)
N(1)
92.8(3)
87.7(3)
87.8(3)
93.6(3)
96.5(3)
O(1)Ã
O(1)Ã
O(3)Ã
O(4)Ã
O(6)Ã
/
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
Cu(1)Ã
/
O(4)
N(1)
O(6)
O(6)
N(1)
163.8(2)
99.6(3)
170.3(2)
89.1(3)
95.8(3)
/
/
/
/
/
/
/
/
/
/
/
/
˚
salicylates are 168.248 and about 3.4 A. In the com-
/
/
/
/
pound 2 there is also a stacking effect between one
bidentate salicylate and 4,4?-bipy from another mole-
cule, the dihedral angle and the distance of these two
4,4?-bipy and salicylates are 3.9, 7.7, 89.9, and 98.68. In
compound 3, dihedral angles between planes of 4,4?-bipy
and salicylates are 10.9 and 74.88.
Table 6
The dihedral angles (8) between two pyridine rings of 4,4?-bipy in
compounds 1, 2, and 3
Compound
Dihedral angles (8)
3.2.2. Extension and compact nature of these structures
Distances between the two copper atoms connected
by 4,4?-bipy in compounds 1, 2, and 3 are listed in Table
5. In compound 3 there is a longer Cuꢀ ꢀ ꢀCu separation
1
2
3
22.681
0.000
44.888
˚
of 11.31 A than that of compounds 1 and 2 because of

126
L.-G. Zhu et al. / Inorganica Chimica Acta 355 (2003) 121ꢀ126
/
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Hubberstey, W.-S. Li, M. Schroder, Inorg. Chem. 38 (1999) 2259;
(d) M.A. Withersby, A.J. Blake, N.R. Champness, P.A. Cooke, P.
Hubberstey, M. Schroder, New J. Chem. 23 (1999) 573;
(e) S.R. Batten, R. Robson, Angew. Chem., Int. Ed. 37 (1998)
1460;
planes in salicylate and 4,4?-bipy are 7.728 and about
˚
3.45 A.
4. Conclusion
(f) A.J. Blake, N.R. Champness, P. Hubberstey, W.-S. Li, M.
Schroder, M.A. Whitersby, Coord. Chem. Rev. 183 (1999) 117.
We have demonstrated that the reactions of
[2] For example, 3-D diamond in Cu(bpy)2×
in Cu(4,4?-bipy)Cl, 2-D square grid in Cd(4,4?-bipy)2(NO3)2×
2(C6H4Br2) and 1-D ladder in Co(4,4?-bipy)1.5(NO3)2×xCH3CN.
For more examples see Ref. [3f].
/PF6, 2-D hexagonal grid
Cu2(CH3COO)4×2H2O, 4,4?-bipyridine, and salicylic
/
/
acid, using the layered-solution approach and variable
solvents, allows the isolation of three 1-D polymeric
complexes with ladder, zig-zag, linear networks bearing
a [Cu(Hsal)2(4,4-bipy)n] motif. The Cuꢀ ꢀ ꢀCu distances
separated by 4,4?-bipy are different in these three
compounds, which leads to a compact structure in
compound 2 and an extended structure in compound 3
with varying conformations of 4,4?-bipy in three com-
pounds. This effort is an example of crystal engineering
aimed at design of the variable networks with functional
properties, and is of benefit to develop chemistry of
structural diversity.
/
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5. Supplementary material
Crystallographic data for the structural analysis has
been deposited with the Cambridge Crystallographic
Data Center, CCDC Nos. 194214, 194215 and 194216
for compounds 1, 2 and 3, respectively. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge, CB2
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Acknowledgements
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The author (L.G.Z.) thanks NNSF of China (No.
50073019) for financial support.
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