Assembly and structures of five new Cu(II) complexes based on the V-shaped building block [Cu(dbsf)]

Article abstract of DOI:10.1016/j.poly.2006.10.007

Five new copper(II) complexes [Cu(dbsf)(H₂O)]_n · 0.5n(i-C₃H₇OH) (1), [Cu(dbsf)(4,4′-bpy)_0.5]_n · nH₂O (2), [Cu(dbsf)(2,2′-bpy)(H₂O)]₂ · (n-C₃H₇OH) · 0.5H₂O (3), [Cu(dbsf)(phen)(H₂O)]₂ · 1.5H₂O (4) and [Cu(dbsf)(2,2′-bpy)(H₂O)]_n · n(i-C₃H₇OH) (5) (H₂dbsf = 4,4′-dicarboxybiphenyl sulfone, 4,4′-bpy = 4,4′-bipyridine, 2,2′-bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, i-C₃H₇OH = isopropanol, n-C₃H₇OH = n-propanol) have been synthesized under hydro/solvothermal conditions. All of the complexes are assembled from V-shaped building blocks, [Cu(dbsf)]. Complex 1 is composed of 1D double-chains. In complex 2, dbsf^2- ligands and 4,4′-bpy ligands connect Cu(II) ions into catenane-like 2D layers. These catenane-like 2D layers stack in an ABAB fashion to form a 3D supramolecular network. Complexes 3 and 4 are 0D dimers, in which two [Cu(dbsf)] units encircle to form dimetal macrocyclic molecules. However, in complex 5, the V-shaped building blocks [Cu(dbsf)] are joined head-to-tail, resulting in the formation of infinite tooth-like chains. The different structures of complexes 3 and 5 may be attributed to the different solvent molecules included.

Full text of DOI:10.1016/j.poly.2006.10.007

Polyhedron 26 (2007) 1123–1132
www.elsevier.com/locate/poly
Assembly and structures of five new Cu(II) complexes based on the
V-shaped building block [Cu(dbsf)]
*
Wen-Juan Zhuang, Chang-Yan Sun, Lin-Pei Jin
School of Chemistry, Beijing Normal University, Beijing 100875, China
Received 22 July 2006; accepted 2 October 2006
Available online 17 October 2006
Abstract
Five new copper(II) complexes [Cu(dbsf)(H2O)]n Æ 0.5n(i-C3H7OH) (1), [Cu(dbsf)(4,40-bpy)0.5]n Æ nH2O (2), [Cu(dbsf)(2,20-bpy)-
(H2O)]2 Æ (n-C3H7OH) Æ 0.5H2O (3), [Cu(dbsf)(phen)(H2O)]2 Æ 1.5H2O (4) and [Cu(dbsf)(2,20-bpy)(H2O)]n Æ n(i-C3H7OH) (5) (H2dbsf =
4,40-dicarboxybiphenyl sulfone, 4,40-bpy = 4,40-bipyridine, 2,20-bpy = 2,20-bipyridine, phen = 1,10-phenanthroline, i-C3H7OH = isopro-
panol, n-C3H7OH = n-propanol) have been synthesized under hydro/solvothermal conditions. All of the complexes are assembled from
V-shaped building blocks, [Cu(dbsf)]. Complex 1 is composed of 1D double-chains. In complex 2, dbsf2ꢀ ligands and 4,40-bpy ligands
connect Cu(II) ions into catenane-like 2D layers. These catenane-like 2D layers stack in an ABAB fashion to form a 3D supramolecular
network. Complexes 3 and 4 are 0D dimers, in which two [Cu(dbsf)] units encircle to form dimetal macrocyclic molecules. However, in
complex 5, the V-shaped building blocks [Cu(dbsf)] are joined head-to-tail, resulting in the formation of infinite tooth-like chains. The
different structures of complexes 3 and 5 may be attributed to the different solvent molecules included.
ꢀ 2006 Elsevier Ltd. All rights reserved.
Keywords: 4,40-Dicarboxybiphenyl sulfone; V-shaped building block; Cu(II) complex; Hydro/solvothermal synthesis; Auxiliary ligand; Solvent molecule
1. Introduction
As far as we know, the formation of MOFs is influenced
by many factors, such as metal ions, organic ligands, coun-
terions, solvent molecules and pH of the reaction mixture,
etc. [8]. Among these factors, the selection of organic
ligands is one of the most important aspects [1a,9]. The
configuration, rigidity, substituent and coordination modes
of organic ligands have an important effect on the final
structures. Generally, polycarboxylate ligands feature
prominently in the construction of coordination com-
pounds, and the reported coordination polymers are
mostly constructed by rigid polycarboxylate ligands
[1b,4,10]. Recently, more and more attention has been paid
to the flexible polycarboxylate ligands [11], but studies
about semi-rigid V-shaped dicarboxylate ligands are rela-
tively few [6,7].
Porous metal-organic frameworks (MOFs) have
attracted much interest of chemists in the field of crystal
engineering and chemistry materials, for their intriguing
structures and molecular topologies [1], as well as their
potential applications in catalysis, gas storage, ion
exchange and molecular recognition [2]. The building block
method [1a,1b,3], because of its directive function of the
target structures as well as the expected physical properties,
has become one of the most important synthetic strategies.
Yaghi et al. have successfully constructed plenty of porous
MOFs using metal carboxylate cluster building blocks [4],
and some novel MOFs have been constructed from linear
building blocks [5]. However, there are few reports of
MOFs constructed by V-shaped building blocks [6,7].
4,40-Dicarboxybiphenyl sulfone (H2dbsf) is a typical
example of semi-rigid V-shaped dicarboxylate ligands. To
the best of our knowledge, there has been no report about
its coordination compounds. Under hydro/solvothermal
conditions, H2dbsf and the Cu(II) ion can form the
*
Corresponding author.
E-mail address: lpjin@bnu.edu.cn (L.-P. Jin).
0277-5387/$ - see front matter ꢀ 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2006.10.007

1124
W.-J. Zhuang et al. / Polyhedron 26 (2007) 1123–1132
V-shaped building block [Cu(dbsf)]. Using these V-shaped
building blocks, with the help of different auxiliary ligands,
we have successfully obtained five new copper coordination
compounds: [Cu(dbsf)(H2O)]n Æ 0.5n(i-C3H7OH) (1), [Cu-
(dbsf)(4,40-bpy)0.5]n Æ nH2O (2), [Cu(dbsf)(2,20-bpy)(H2O)]2 Æ
(n-C3H7OH) Æ 0.5H2O (3), [Cu(dbsf)(phen)(H2O)]2 Æ 1.5H2O
(4) and [Cu(dbsf)(2,20-bpy)(H2O)]n Æ n(i-C3H7OH) (5).
air. Yield: 0.002 g (4.8%). Additionally a lot of blue poly-
crystals were also obtained (ꢁ50%. Found: C, 42.09; H,
4.11%). Anal. Calc. for C15.5H14CuO7.5S (415.87): C,
44.77; H, 3.39. Found: C, 44.70; H, 3.64%. IR data (KBr
pellet, cmꢀ1): 3441s, 1633s, 1409s, 1169m, 1140w, 1100w,
742m, 727w, 523w.
2.2.2. Synthesis of [Cu(dbsf)(4,40-bpy)0.5]n Æ nH2O (2)
2. Experimental
A mixture of CuCl2 Æ 6H2O (0.017 g, 0.1 mmol),
H2dbsf (0.030 g, 0.1 mmol), 4,40-bpy Æ 2H2O (0.019 g,
0.1 mmol), NaOH aqueous solution (0.05 mL, 0.65 M),
HCl aqueous solution (0.05 mL, 1.20 M), distilled water
(5 mL) and N,N-dimethyl formamide (0.1 mL) was sealed
in a Teflon-lined stainless vessel (25 mL) and heated at
180 ꢁC for 72 h under autogenous pressure. The vessel
was then cooled slowly to room temperature. Green strip
crystals were obtained by filtration, washed with distilled
water and dried in air. Yield: 0.015 g (32.3%). Anal.
Calc. for C19H14CuNO7S (463.91): C, 49.19; H, 3.04;
N, 3.02. Found: C, 49.48; H, 3.18; N, 3.05%. IR data
(KBr pellet, cmꢀ1): 3439s, 1644s, 1608m, 1570m, 1408s,
1326w, 1302w, 1169m, 1100m, 1015w, 739s, 726w,
620w, 520m.
2.1. Materials and apparatus
All reagents were used as received without further purifi-
cation (H2dbsf from TCL). The C, H, N microanalyses were
carried out with a Vario EL elemental analyzer. The IR
spectra were recorded with a Nicolet Avatar 360 FT-IR
spectrometer using the KBr pellet technique. The thermal
analyses were performed on a ZRY-2P thermal analyzer
using a heating rate of 20 ꢁC/min from room temperature
to 900 ꢁC.
2.2. Synthesis
2.2.1. Synthesis of [Cu(dbsf)(H2O)]n Æ 0.5n(i-C3H7OH)
(1)
2.2.3. Synthesis of [Cu(dbsf)(2,20-bpy)(H2O)]2 Æ
(n-C3H7OH) Æ 0.5H2O (3)
A mixture of CuCl2 Æ 6H2O (0.017 g, 0.1 mmol), H2dbsf
(0.030 g, 0.1 mmol), NaOH aqueous solution (0.05 mL,
0.65 M), HCl aqueous solution (0.05 mL, 1.20 M), distilled
water (5 mL), isopropanol (5 mL) and N,N-dimethyl form-
amide (0.1 mL) was sealed in a Teflon-lined stainless vessel
(25 mL) and heated at 180 ꢁC for 72 h under autogenous
pressure. The vessel was then cooled slowly to room tem-
perature. Blue strip crystals were obtained by filtration,
washed with distilled water and isopropanol, and dried in
The synthesis of complex 3 was the same as that for
complex 2 but substituting 2,20-bpy (0.016 g, 0.1 mmol)
for 4,40-bpy Æ 2H2O, and n-propanol (5 mL) was also added
to the reaction mixture. Blue block crystals were obtained
by filtration, washed with distilled water and n-propanol,
and dried in air. Yield: 0.020 g (34.7%). Anal. Calc. for
C25.5H22.5CuN2O7.75S (576.55): C, 53.13; H, 3.92; N,
4.86. Found: C, 53.56; H, 4.34; N, 4.53%. IR data (KBr
Table 1
Crystal data and structure refinement parameters of complexes 1–5
Complex
1
2
3
4
5
Empirical formula
Formula weight
Crystal system
Space group
C
415.87
orthorhombic
Cmcm
15.5H14CuO7.5
S
C19H14CuNO7S
463.91
orthorhombic
Cmcm
C25.5H22.5CuN2O7.75
576.55
triclinic
S
C26H19.5CuN2O7.75
579.54
triclinic
S
C27H26CuN2O8S
602.10
monoclinic
P21/n
6.8069(9)
16.574(2)
23.762(3)
90
92.146(2)
90
ꢀ
ꢀ
P1
P1
˚
a (A)
22.073(5)
12.689(2)
11.592(2)
90
90
90
12.694(4)
13.983(4)
21.823(7)
90
90
90
6.936(4)
12.137(6)
16.324(9)
79.717(9)
88.063(10)
73.418(9)
1295.5(12)
2
6.975(5)
12.115(10)
16.749(13)
82.469(13)
85.658(12)
74.148(13)
1348.5(18)
2
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
3246.9(12)
8
3874(2)
8
2678.8(6)
4
Z
F(000)
1696
1.701
293(2)
1.85–26.30
1.514
1888
1.591
293 (2)
1.87–26.46
1.278
593
1.478
293(2)
1.78–25.01
0.974
593
1.427
293(2)
2.26–25.01
0.937
1244
1.493
293(2)
1.50–26.39
0.946
Dcalc (Mg mꢀ3
T (K)
)
h Range (ꢁ)
l (mmꢀ1
)
Goodness-of-fit
Final R indices
[I > 2r(I)]
1.054
R1 = 0.0413,
wR2 = 0.1036
1.087
R1 = 0.0617,
wR2 = 0.1221
1.073
R1 = 0.0570,
wR2 = 0.1550
1.020
R1 = 0.0562,
wR2 = 0.1475
1.046
R1 = 0.0374,
wR2 = 0.0852

W.-J. Zhuang et al. / Polyhedron 26 (2007) 1123–1132
1125
pellet, cmꢀ1): 3431s, 1600s, 1560s, 1474w, 1447w, 1398s,
1319w, 1297m, 1163s, 1133m, 1101m, 1054w, 1012w,
773w, 744s, 731m, 718w, 692w, 624m, 576w.
Table 2
a
˚
Selected bond lengths (A) and bond angles (ꢁ) for complexes 1–5
Complex 1
Cu(1)–O(1)
Cu(1)–O(4)
1.952(3) Cu(1)–O(3)#2
2.153(4)
1.981(3)
2.2.4. Synthesis of [Cu(dbsf)(phen)(H2O)]2 Æ 1.5H2O (4)
The synthesis of complex 4 followed a similar process as
for complex 2 except that 4,40-bpy Æ 2H2O was replaced by
phenÆH2O (0.020 g, 0.1 mmol), and isopropanol (5 mL) was
added to the reaction mixture. Blue strip crystals were
obtained by filtration, washed with distilled water and iso-
propanol, and dried in air. Yield: 0.031 g (53.5%). Anal.
Calc. for C26H19.5CuN2O7.75S (579.54): C, 53.89; H, 3.39;
N, 4.83. Found: C, 53.53; H, 3.76; N, 4.74%. IR data
(KBr pellet, cmꢀ1): 3423s, 1604s, 1563s, 1518w, 1426m,
1398s, 1380s, 1344m, 1298m, 1161s, 1102m, 856w, 746s,
724s, 624m, 585w.
O(1)–Cu(1)–O(4)
O(1)–Cu(1)–O(1)#1
O(1)–Cu(1)–O(3)#2
100.9(1)
89.9(2)
168.8(1)
O(1)#1–Cu(1)–O(3)#2
O(3)#2–Cu(1)–O(4)
O(3)#2–Cu(1)–O(3)#3
89.8(1)
90.1(1)
88.3(2)
Complex 2
Cu(1)–O(1)
Cu(1)–N(2)#4
1.987(5) Cu(2)–O(2)
2.10(1)
1.966(5)
2.12(1)
Cu(2)–N(1)
O(1)–Cu(1)–O(1)#1
O(1)–Cu(1)–O(1)#2
O(1)–Cu(1)–O(1)#3
O(1)–Cu(1)–N(2)#4
88.7(3)
89.9(3)
167.6(3)
96.2(1)
O(2)–Cu(2)–O(2)#1
O(2)–Cu(2)–O(2)#2
O(2)–Cu(2)–O(2)#3
O(2)–Cu(2)–N(1)
90.0(3)
88.9(3)
168.8(3)
95.6(1)
Complex 3
Cu(1)–O(1)
Cu(1)–O(7)
Cu(1)–O(5)#1
1.929(4) Cu(1)–N(1)
2.303(4) Cu(1)–N(2)
1.924(4)
1.992(5)
1.996(5)
2.2.5. Synthesis of [Cu(dbsf)(2,20-bpy)(H2O)]n Æ
n(i-C3H7OH) (5)
The synthesis of complex 5 followed the same procedure
as that for complex 2 except using 2,20-bpy (0.016 g,
0.1 mmol) instead of 4,40-bpy Æ 2H2O, and isopropanol
(5 mL) was added to the reaction mixture. Blue board crys-
tals were obtained by filtration, washed with distilled water
and isopropanol, and dried in air. Yield: 0.051 g (84.7%).
Anal. Calc. for C27H26CuN2O8S (602.10): C, 49.69; H,
3.07; N, 3.05. Found: C, 49.72; H, 3.11; N, 3.01%. IR data
(KBr pellet, cmꢀ1): 3418s, 1600s, 1560s, 1475w, 1447m,
1399s, 1298m, 1163s, 1133m, 1101m, 744m, 731w, 623w.
In the syntheses of the complexes 1–5, HCl and NaOH
solutions were added to adjust the pH of the reaction sys-
tem. Propanol and DMF were added to enhance the solu-
bility of the H2dbsf ligand. Complexes 1, 4 and 5 were
synthesized in the mixed solvent of water, isopropanol
and DMF, and 2 was formed in the mixed solvent of water
and DMF, while complex 3 was obtained in the mixed sol-
vent of water, n-propanol and DMF, showing that selectiv-
ity of the solvent plays an important role in the formation
of the complexes.
O(1)–Cu(1)–O(7)
O(1)–Cu(1)–N(1)
O(1)–Cu(1)–N(2)
O(5)#1–Cu(1)–O(1)
O(5)#1–Cu(1)–O(7)
95.5(2)
169.8(2)
93.5(2)
90.6(2)
101.0(2)
O(5)#1–Cu(1)–N(1)
93.3(2)
164.7(2)
93.0(2)
80.4(2)
93.4(2)
O(5)#1–Cu(1)–N(2)
N(1)–Cu(1)–O(7)
N(1)–Cu(1)–N(2)
N(2)–Cu(1)–O(7)
Complex 4
Cu(1)–O(1)
Cu(1)–O(7)
Cu(1)–O(5)#1
1.951(4) Cu(1)–N(1)
2.353(4) Cu(1)–N(2)
1.941(4)
2.014(4)
2.020(4)
O(1)–Cu(1)–O(7)
O(1)–Cu(1)–N(1)
O(1)–Cu(1)–N(2)
O(5)#1–Cu(1)–O(1)
O(5)#1–Cu(1)–O(7)
95.1(2)
171.8(2)
92.5(2)
91.9(2)
98.9(2)
O(5)#1–Cu(1)–N(1)
92.6(2)
167.1(2)
91.1(2)
81.8(2)
92.8(2)
O(5)#1–Cu(1)–N(2)
N(1)–Cu(1)–O(7)
N(1)–Cu(1)–N(2)
N(2)–Cu(1)–O(7)
Complex 5
Cu(1)–O(1)
Cu(1)–O(8)
Cu(1)–O(5)#1
1.943(2) Cu(1)–N(1)
2.273(2) Cu(1)–N(2)
1.955(2)
2.011(2)
2.016(2)
O(1)–Cu(1)–O(8)
O(1)–Cu(1)–O(5)#1
O(1)–Cu(1)–N(1)
O(1)–Cu(1)–N(2)
O(5)#1–Cu(1)–O(8)
a
96.82(8)
92.52(8)
168.43(8)
93.04(8)
94.18(8)
O(5)#1–Cu(1)–N(1)
91.20(9)
162.82(8)
93.83(8)
80.41(9)
101.28(8)
O(5)#1–Cu(1)–N(2)
N(1)–Cu(1)–O(8)
N(1)–Cu(1)–N(2)
N(2)–Cu(1)–O(8)
2.3. X-ray diffraction determination
Symmetry transformations used to generate equivalent atoms: For 1,
#1 ꢀx, y, z; #2 ꢀx, y ꢀ 1, z; #3 x, y ꢀ 1, z. For 2, #1 x, y, ꢀz + 1/2; #2
ꢀx + 2, y, z; #3 ꢀx + 2, y, ꢀz + 1/2; #4 x, y + 1, z. For 3, #1 ꢀx + 1, ꢀy,
ꢀz + 1. For 4, #1 ꢀx + 1, ꢀy + 1, ꢀz + 2. For 5, #1 ꢀx + 1/2, y ꢀ 1/2,
ꢀz + 1/2.
Diffraction data for complexes 1–5 were collected at
294 K on a Bruker SMART 1000 CCD diffractometer with
a graphite-monochromatized Mo Ka radiation (k =
˚
0.71073 A), using the x and u scan technique. A semi-
empirical absorption correction was applied with the SAD-
ABS program. The structures were solved by direct methods
and refined by full-matrix least-squares on F2 using the
SHELXS-97 and SHELXL-97 programs [12–14], respectively.
All non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were placed in geometrically calculated
positions. Crystallographic data for complexes 1–5 are
3. Results and discussion
3.1. Description of the structures
In complexes 1–5, the dbsf2ꢀ ligands are
completely deprotonated and are largely bent at the
sulfone-sulfur sites (C–S–C = 103.0(2)–106.5(3)ꢁ, O–S–
O = 119.1(2)–120.2(3)ꢁ). Each of them displays a V-shaped
configuration, and assembles with the Cu(II) ion to form
the V-shaped building block [Cu(dbsf)]. The coordination
˚
summarized in Table 1, and selected bond lengths (A)
and bond angles (ꢁ) are listed in Table 2 while selected
˚
hydrogen bond lengths (A) and bond angles (ꢁ) are pre-
sented in Table 3.

1126
W.-J. Zhuang et al. / Polyhedron 26 (2007) 1123–1132
Table 3
˚
Selected hydrogen bond lengths (A) and bond angles (ꢁ) for complexes 1–5
D–Hꢂ ꢂ ꢂA
Complex 1
d(D–H)
d(Hꢂ ꢂ ꢂA)
d(Dꢂ ꢂ ꢂA)
\DHA
Symmetry code
O(4)–H(4A)ꢂ ꢂ ꢂO(5wA)
O(4)–H(4A)ꢂ ꢂ ꢂO(50wB)
O(4)–H(4A)ꢂ ꢂ ꢂO(50wB)
O(4)–H(4B)ꢂ ꢂ ꢂO(3)
0.849
0.849
0.849
0.852
1.998
2.133
2.133
2.172
2.785
2.905
2.905
3.013
153.62
150.97
150.97
169.44
[x, y, zꢀ1]
[ꢀx, y, ꢀz + 1/2]
[x, y, z ꢀ 1]
[x, ꢀy + 1, ꢀz]
Complex 3
O(7)–H(7B)ꢂ ꢂ ꢂO(6)
C(13)–H(13)ꢂ ꢂ ꢂO(4)
C(22)–H(22)ꢂ ꢂ ꢂO(3)
C(21)–H(21)ꢂ ꢂ ꢂO(6)
0.850
0.930
0.930
0.930
2.337
2.547
2.376
2.403
2.803
3.232
3.253
3.318
114.87
130.80
157.30
168.00
[ꢀx, ꢀy, ꢀz + 1]
[ꢀx + 1, ꢀy ꢀ 1, ꢀz + 1]
[ꢀx + 1, ꢀy, ꢀz]
[x ꢀ 1, y + 1, zꢀ1]
Complex 4
O(7)–H(7B)ꢂ ꢂ ꢂO(6)
O(7)–H(7A)ꢂ ꢂ ꢂO(8w)
C(19)–H(19)ꢂ ꢂ ꢂO(6)
C(20)–H(20)ꢂ ꢂ ꢂO(6)
C(4)–H(4)ꢂ ꢂ ꢂO(2)
0.849
0.849
0.930
0.930
0.930
2.346
1.995
2.487
2.683
2.542
2.784
2.825
3.130
3.228
3.304
112.58
165.52
126.40
118.10
99.70
[ꢀx, ꢀy + 1, ꢀz + 2]
[ꢀx, ꢀy + 1, ꢀz + 1]
[x ꢀ 1, y + 1, zꢀ1]
[x ꢀ 1, y + 1, zꢀ1]
[x + 1, y, z]
Complex 5
O(7)–H(7A)ꢂ ꢂ ꢂO(6)
O(8)–H(8A)ꢂ ꢂ ꢂO(6)
O(8)–H(8B)ꢂ ꢂ ꢂO(2)
C(4)–H(4)ꢂ ꢂ ꢂO(2)
0.820
0.845
0.845
0.930
2.152
1.920
1.996
2.306
2.914
2.720
2.788
3.197
154.48
157.58
155.72
160.30
[ꢀx ꢀ 1/2, y ꢀ 1/2, ꢀz + 1/2]
[ꢀx + 1/2, y ꢀ 1/2, ꢀz + 1/2]
[x + 1, y, z]
[ꢀx + 1, ꢀy + 1, ꢀz]
O
S
O
S
M
M
O
O
O
O
M
M
M
O
O
O
O
C
C
C
C
M
O
O
a
b
Scheme 1. The coordination modes of the dbsf2ꢀ ligand in complexes 1–5.
2ꢀ
modes of the dbsf2ꢀ ligand in complexes 1–5 are repre-
sented in Scheme 1.
distance of 3.507 A between the phenyl rings of dbsf
ligands. Hydrogen bonds and p–p stacking interactions
result in the formation of the porous supramolecular net-
work of complex 1. Isopropanol molecules are accommo-
dated in the channels (see Fig. 1c). There are hydrogen
bonds between the oxygen atom (O(5w)) of isopropanol
molecules and coordinated water molecules of the chains
(Table 3).
˚
3.1.1. [Cu(dbsf)(H2O)]n Æ 0.5n(i-C3H7OH) (1)
In complex 1, each Cu(II) ion is coordinated to five oxy-
gen atoms, four oxygen atoms from four dbsf2ꢀ ligands
and one oxygen atom from a water molecule, as shown
in Fig. 1a. O(1), O(1C), O(3B) and O(3C) atoms form an
equatorial plane and one oxygen atom (O(4)) occupies
the axial position, giving a slightly distorted square-
pyramidal geometry. In complex 1, each dbsf2ꢀ ligand
adopts a bis(bridging-bidentate) mode (Scheme 1a) to
coordinate to four Cu(II) ions. V-Shaped building blocks
[Cu(dbsf)] are joined to form 1D double-chains, as shown
in Fig. 1b. The single 1D double-chain possesses rhombic
3.1.2. [Cu(dbsf)(4,40-bpy)0.5]n Æ nH2O (2)
In complex 2, there are two kinds of crystallographically
independent Cu(II) ions, as shown in Fig. 2a. Both Cu(1)
and Cu(2) are five-coordinated, and their coordination
environments are similar but the bond lengths and bond
angles around Cu(1) and Cu(2) are different. Each Cu(II)
ion is coordinated to four oxygen atoms of four different
dbsf2ꢀ ligands and one nitrogen atom of one 4,40-bpy mol-
ecule. In complex 2, the dbsf2ꢀ ligands adopt a bis(bridg-
ing-bidentate) mode (Scheme 1a), linking the Cu(II) ions
into a 1D double-chain structure along the a-axis, which
is similar to that in complex 1. However, because of the
introduction of 4,40-bpy molecules, these 1D [Cu(dbsf)]n
double-chains are pillared to generate 2D square-grids
(Fig. 2b). Unexpectedly, two such grids interpenetrate each
˚
voids with dimensions of about 8 · 8 A. All these double-
chains are parallel to each other. Along the c-axis, these
double-chains are arranged in an ABAB fashion and there
is a displacement between the adjacent chains, which leads
to the formation of small 1D channels (Fig. 1c). Hydrogen
bonds are observed between the coordinated water mole-
cules and the carboxylate oxygen atoms of dbsf2ꢀ ligands
among the adjacent chains along the c-axis (Table 3), and
there are p–p stacking interactions in the ab-plane, with a

W.-J. Zhuang et al. / Polyhedron 26 (2007) 1123–1132
1127
Fig. 1. (a) The coordination environment of the Cu(II) ion in complex 1 with 30% thermal ellipsoids, all hydrogen atoms are omitted for clarity. (b) The
1D double-chain structure with rhombic voids. (c) View of the supramolecular network of complex 1 along the c-direction (space-filling model represents
isopropanol molecules).
other to generate a novel catenane-like 2D layer (Fig. 2c).
Such catenane-like layers are unusual [15]. These caten-
ane-like 2D structures stack in an ABAB fashion along
the c-axis with some displacement between A and B, result-
ing in the formation of a 3D supramolecular network.
There are lattice water molecules accommodated between
the layers.
nated water molecule. The coordination geometry of the
Cu(II) ion can be described as a distorted square-pyramid.
The Cu–N bond lengths are 2.014(4) and 2.020(4) A, and
˚
the Cu–O bond lengths are in the range of 1.941(4)–2.353
˚
˚
(4) A (the Cu–N bond lengths are 1.992(5) and 1.996(5) A,
and the Cu–O bond lengths are in the range of 1.924(4)–
2ꢀ
˚
2.303 (4) A for complex 4). In complex 3, every dbsf
ligand adopts a bis(monodentate) mode (Scheme 1b), so
that two V-shaped building blocks encircle to form a macro-
cyclic dimer unit (Fig. 3a). All the dimer units are parallel,
and plenty of hydrogen bonds exist between them. Along
the a-axis, there exists O–Hꢂ ꢂ ꢂO hydrogen bonds [O(7)–
H(7B)ꢂ ꢂ ꢂO(6)] between the coordinated water molecule
and the oxygen atom of the uncoordinated carboxyl group.
In addition, three kinds of C–Hꢂ ꢂ ꢂO hydrogen bonds, such
as C(13)–H(13)ꢂ ꢂ ꢂO(4), C(22)–H(22)ꢂ ꢂ ꢂO(3) and C(21)–
H(21)ꢂ ꢂ ꢂO(6) exist in the adjacent dimers in the bc-plane.
Moreover, a p–p stacking interaction exists between 2,20-
3.1.3. [Cu(dbsf)(2,20-bpy)(H2O)]2 Æ (n-C3H7OH) Æ
0.5H2O (3) and [Cu(dbsf)(phen)(H2O)]2 Æ 1.5H2O (4)
X-ray diffraction analysis reveals that complexes 3 and 4
possess similar structures, except that the 2,20-bpy ligand in
complex 3 is replaced by a phen ligand in complex 4, and the
guest molecules are different in the two complexes
(n-C3H7OH and H2O for 3, H2O for 4). So only the struc-
ture of complex 3 will be described here. The coordination
environment of the Cu(II) ion in complex 3 is shown in
Fig. 3a. The Cu(II) ion is five-coordinated, with two oxygen
atoms from two dbsf2ꢀ ligands, two nitrogen atoms from
one 2,20-bpy ligand and one oxygen atom from a coordi-
˚
bpy ligands (the face-to-face distance is 3.639 A). These
hydrogen bonds and p–p stacking interactions lead to the

1128
W.-J. Zhuang et al. / Polyhedron 26 (2007) 1123–1132
Fig. 2. (a) The coordination environments of the Cu(II) ions in complex 2 with 30% thermal ellipsoids, all hydrogen atoms are omitted for clarity. (b) The
2D layer framework of complex 2. (c) Interpenetrated catenane-like 2D layers and its schematic view.
Fig. 3. (a) The coordination environment of the Cu(II) ion in complex 3 with 30% thermal ellipsoids, all hydrogen atoms are omitted for clarity. (b) View
of the 3D porous supramolecular structure along the a-axis, all the atoms except hydrogen atoms are shown as a space-filling model.
formation of a 3D porous supramolecular architecture [16],
as shown in Fig. 3b. Water molecules and n-propanol mol-
ecules alternately occupy the 1D channels along the a-axis.
But they are so far away from the dimers that no hydrogen
bonds are formed between the guest molecules and the
dimers.
structure. As shown in Fig. 4a, the Cu(II) ion is five-coor-
dinated and displays a distorted square-pyramidal geome-
try, which is completed by two nitrogen atoms from one
chelating 2,20-bpy ligand, two oxygen atoms from two
dbsf2ꢀ ligands, and one oxygen atom from one coordi-
nated water molecule. In complex 5, the dbsf2ꢀ ligands
adopt a bis(monodentate) mode (Scheme 1b), the same
as that in complex 3, but they connect the Cu(II) ions into
a completely different structure. V-Shaped building blocks
are joined head-to-tail to form infinite tooth-like chains
(Fig. 4b). Among these chains, there are plenty of hydro-
3.1.4. [Cu(dbsf)(2,20-bpy)(H2O)]n Æ n(i-C3H7OH) (5)
The X-ray crystallographic analysis shows that com-
plex 5 possesses 1D tooth-like chains. There is one crys-
tallographically independent Cu(II) center in the crystal

W.-J. Zhuang et al. / Polyhedron 26 (2007) 1123–1132
1129
Fig. 4. (a) The coordination environment of the Cu(II) ion in complex 5 with 30% thermal ellipsoids, all hydrogen atoms are omitted for clarity. (b) The
infinite 1D chain structure formed by V-shaped building blocks of [Cu(dbsf)]. (c) View of the 3D supramolecular structure along a-axis (space-filling model
represents solvent molecules).
gen bonds. O–Hꢂ ꢂ ꢂO hydrogen bonds are observed
between the uncoordinated oxygen atoms (O(6)) and
coordinated water molecules of the adjacent chains. Addi-
tionally, C–Hꢂ ꢂ ꢂO hydrogen bonds are observed between
Cꢂ ꢂ ꢂH (H(4)) of the 2,20-bpy molecule and the other unco-
ordinated carboxylate oxygen atoms (O(2)) of the adjacent
chain (Table 3). The 2,20-bpy molecules also participate in
face-to-face p–p stacking interactions with a separation at
channels along the a-axis, isopropanol molecules are
accommodated (Fig. 4c). They form O–Hꢂ ꢂ ꢂO hydrogen
bonds with the non-coordinated oxygen atoms (O(6)) of
the dbsf2ꢀ ligands. The formation of these hydrogen bonds
prevents the dbsf2ꢀ ligands encircling to form a dimer frag-
ment. Besides, isopropanol molecules occupy the voids of
the tooth-like chains, functioning as important supports
to the shape of the chains.
˚
the closest contact of 3.267 A, and the pyridyl planes of
the 2,20-bpy ligands are parallel to ones in the adjacent
chains. Thus a 3D supramolecular structure is formed via
hydrogen bonds and p–p stacking interactions. In the 1D
3.1.5. Comparison of the structures of complexes 1–5
By self-assembly from V-shaped building blocks [Cu(dbsf)],
we obtained five new complexes with structure described as

1130
W.-J. Zhuang et al. / Polyhedron 26 (2007) 1123–1132
Scheme 2. The simplified representation of the structures of the five complexes.
0D metallocyclic, 1D chain and 2D catenane-like layer.
From the above descriptions, it is obvious that the introduc-
ing of different auxiliary ligands has a crucial effect on the
assembly of the [Cu(dbsf)] building block and the formation
of the final structures. The simplified structures of these five
complexes are represented in Scheme 2. In complexes 1–5,
the dbsf2ꢀ ligand shows two coordination modes (Scheme
1). It adopts a bis(bridging-bidentate) mode (Scheme 1a)
in complexes 1 and 2, and the bis(monodentate) mode
(Scheme 1b) in complexes 3–5. In complex 1, V-shaped
building blocks [Cu(dbsf)] are joined to form 1D double-
chains. While in complex 2, when the bridging auxiliary
ligand 4,40-bpy is introduced, these 1D double-chains are
pillared into 2D layers. When terminal auxiliary ligands
phen/2,20-bpy were introduced into the Cu/dbsf system,
0D dimeric complexes 3 and 4 were obtained, in which every
two V-shaped building blocks [Cu(dbsf)] encircle to form
metallocyclic units in which the terminal ligands phen/
2,20-bpy prevent the structures extending to a higher
dimension.
In addition, solvent molecules impact the structure
too. It is worth noting that complexes 3 and 5 were
obtained from the same reactants in different solvents,
they possess very different structures [17]. Complex 3 is
composed of dimetal macrocyclic molecules with two
V-shaped building blocks of [Cu(dbsf)], while in complex
5, V-shaped building blocks of [Cu(dbsf)] are linked in a
head-to-tail model, and 1D tooth-like chains are orga-
nized. This may be attributed to the dissimilar solvent
molecules included. In complex 5, the free isopropanol
molecules form hydrogen bonds with the main chain so
as to prevent the dbsf2ꢀ ligands encircling to form dimer
fragments (see Fig. 4c), occupying the voids of the tooth-
like chains, and acting as important supports to the
shape of the chains.
3.2. Thermal analyses
Thermogravimetric analyses of the complexes 2–5
were carried out to examine their thermal stabilities.
The observed TG curve reveals that complex 2 looses
its lattice water molecules at the first weight loss of
3.0% (calc. 3.8%) from 64 ꢁC to 172 ꢁC. For complex
3, the TG curve shows that the uncoordinated solvent
molecules and coordinated water molecules are lost at
the first weight loss, 9.0% (calc. 9.1%) from 109 ꢁC to
201 ꢁC. While for complex 4, the uncoordinated and
coordinated water molecules are lost from 73 ꢁC to
112 ꢁC at the first weight loss of 6.2% (calc. 5.4%). In
complex 5, the first weight loss of 9.9% from 169 ꢁC to
206 ꢁC corresponds to the loss of uncoordinated isopro-
panol molecules (calc. 9.9%).
The TG curves of the complexes 3 and 5 show that fur-
ther decomposition starts when the solvent was removed,
indicating that the host framework collapses when the sol-
vent is absent.
4. Conclusions
In summary, a series of Cu/dbsf complexes were pre-
pared under hydro/solvothermal conditions. The crystal
structures of the title complexes are the first report on
metal complexes of 4,40-dicarboxybiphenyl sulfone. Differ-
ent structures of complexes 1–5 indicate that the V-shaped
dicarboxylate ligand dbsf2ꢀ has the ability of adjusting its
coordination configuration in different reaction systems

W.-J. Zhuang et al. / Polyhedron 26 (2007) 1123–1132
1131
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intelligently. Complexes 1–5 are all built up from V-shaped
building blocks [Cu(dbsf)] with diverse auxiliary ligands.
Our studies show that the configuration of the building
blocks of [Cu(dbsf)] together with the help of auxiliary
ligands has a crucial effect on the topology and configura-
tion of the final structures of the Cu(II) complexes. Addi-
tionally, the solvent molecule acting as a guest is another
notable factor for the arrangement of the 3D supramolec-
ular networks.
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