Synthesis, structure, and magnetic properties of two 1-D helical coordination polymeric Cu(II) complexes

Article abstract of DOI:10.1016/j.molstruc.2007.02.009

Two helical coordination polymeric copper(II) complexes bearing amino acid Schiff bases HL or HL′, which are condensed from 2-hydroxy-1-naphthaldehyde with 2-aminobenzoic acid or l-valine, respectively, have been prepared and characterised by X-ray crystallography. In [CuL]_n (1) the copper(II) atoms are bridged by syn-anti carboxylate groups giving infinite 1-D right-handed helical chains which are further connected by weak C-H?Cu interactions to build a 2-D network. While in [CuL′]_n (2) the carboxylate group acts as a rare monatomic bridge to connect the adjacent copper(II) atoms leading to the formation of a left-handed helical chain. Magnetic susceptibility measurements indicate that 1 exhibits weak ferromagnetic interactions whereas an antiferromagnetic coupling is established for 2. The magnetic behavior can be satisfactorily explained on the basis of the structural data.

Full text of DOI:10.1016/j.molstruc.2007.02.009

Available online at www.sciencedirect.com
Journal of Molecular Structure 872 (2008) 40–46
www.elsevier.com/locate/molstruc
Synthesis, structure, and magnetic properties of two 1-D
helical coordination polymeric Cu(II) complexes
a
a
a
a
a,
*
He-Dong Bian , Xiao-E Yang , Qing Yu , Zi-Lu Chen , Hong Liang
,
b
b
Shi-Ping Yan , Dai-Zheng Liao
a
College of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin, Guangxi 541004, PR China
b
College of Chemistry, Nankai University, Tianjin 300071, PR China
Received 15 December 2006; received in revised form 7 February 2007; accepted 7 February 2007
Available online 16 February 2007
Abstract
Two helical coordination polymeric copper(II) complexes bearing amino acid Schiff bases HL or HL0, which are condensed from 2-
hydroxy-1-naphthaldehyde with 2-aminobenzoic acid or L-valine, respectively, have been prepared and characterised by X-ray crystal-
lography. In [CuL]n (1) the copper(II) atoms are bridged by syn–anti carboxylate groups giving infinite 1-D right-handed helical chains
which are further connected by weak C–Hꢀ ꢀ ꢀCu interactions to build a 2-D network. While in [CuL0]n (2) the carboxylate group acts as a
rare monatomic bridge to connect the adjacent copper(II) atoms leading to the formation of a left-handed helical chain. Magnetic sus-
ceptibility measurements indicate that 1 exhibits weak ferromagnetic interactions whereas an antiferromagnetic coupling is established
for 2. The magnetic behavior can be satisfactorily explained on the basis of the structural data.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Schiff base; Cu(II) complex; Helical coordination polymer; Magnetic properties
1. Introduction
chain, two-, and three-dimensional systems [3]. In these
complexes, it can assume many types of bridging confor-
mations. The most important ones are triatomic syn–syn,
syn–anti, and anti–anti and monatomic (Scheme 1) [4].
The magnetic properties are closely related to the bridging
conformation adopted by the carboxylate group in these
polynuclear systems. In monoatomic and syn–anti tri-
atomic cases both weak ferromagnetic and antiferromag-
netic couplings were observed, while in the triatomic syn–
syn and anti–anti cases only antiferromagnetic interaction
was found [3a,5]. Ferromagnetic or antiferromagnetic
interactions transmitted through the syn–anti or mon-
atomic carboxylate bridges have ever been reported in clus-
tered and polymeric compounds. But seldom was
concerned about the correlation of the structure and mag-
netic properties of copper(II) complexes with helical chains
formed from the bridging of carboxylate group [5c]. In
order to obtain the magneto-structural correlation, more
detailed experiments and analyses are needed. In this
paper, we report the synthesis, structure, and magnetic
Helical structures retain a unique place in life since bio-
logical recognition is encoded within helical DNA mole-
cules [1]. Over the past decade, the design of helical metal
complexes and the study of their physical properties have
been extensively concerned not only in coordination chem-
istry but also in materials chemistry because of their simi-
larities to nucleic acids and proteins and also their
potential applications in areas such as catalysis, magne-
tism, transport processes, sensors and modelling of biolog-
ical compounds. So it is a fascinating challenge for
chemists to control the formation of helicity at the supra-
molecular level [2]. Carboxylate is a very versatile anion
that can bridge two metal ions to give a wide variety of
polynuclear complexes including one-dimensional helical
*
Corresponding author. Tel.: +86 773 5847207.
E-mail address: bianhd@mailbox.gxnu.edu.cn (H. Liang).
0022-2860/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2007.02.009

H.-D. Bian et al. / Journal of Molecular Structure 872 (2008) 40–46
41
of the filtrate. Anal. for C16H15CuNO3: Found. C, 57.69,
H, 4.51, N, 4.21, Calc. C, 57.74, H, 4.54, N, 4.21%. IR
(KBr, cmꢁ1): 3434 (w),1643 (s), 1620 (s), 1539 (m), 1506
(m), 1436 (s), 1394 (s), 1340 (m),1188 (m), 833 (m),796
(m), 755 (s), 572 (m).
Cu
Cu
Cu
Cu
O
Cu
O
O
O
O
O
O
Cu
O
Cu Cu
syn-syn
syn-anti
monoatomic
anti-anti
Scheme 1.
2.1.3. X-ray crystallography
properties of two helical coordination polymeric Cu(II)
complexes [CuL]n (1, H2L = (E)-2-((2-hydroxynaphtha-
len-1-yl)methylene-amino)benzoic acid) and [CuL]n (2,
HL0 = (S,E)-2-((2-hydroxy-naphthalen-1-yl)methyleneami-
no)-3-methyl-butanoic acid). The Cu(II) atoms are bridged
by carboxylate groups with syn–anti triatomic and mon-
atomic modes for 1 and 2, respectively. To our knowledge,
the formation of monatomic carboxylate bridges is rela-
tively rare in coordination polymeric complexes [4e]. Mag-
netic susceptibility measurements indicate that 1 exhibits a
ferromagnetic interaction, while 2 exhibits a rare antiferro-
magnetic interaction.
Diffraction intensity data for single crystals of 1 and 2
were collected at room temperature on a Bruker Smart
1000 CCD area detector equipped with graphite-mono-
˚
chromated Mo Ka radiation (k = 0.71073 A). The struc-
ture was solved by the direct method and refined by the
full-matrix least-squares method on F2 with anisotropic
thermal parameters for all nonhydrogen atoms. The hydro-
gen atoms of solvent molecules were not added, and the
other hydrogen atoms were located geometrically and
refined isotropically. All calculations were carried out using
SHELXS-97, SHELXL-97 programs [6]. Crystal data are
collected in Table 1. Selected bond lengths and angles are
listed in Table 2.
2. Experimental
2.1. Materials and syntheses
3. Results and discussion
All reagents and chemicals were purchased from com-
mercial sources and used as received.
3.1. Crystal structure
Infrared spectra were recorded as KBr pellet using a Per-
kin-Elmer Spectrum One FTIR spectrometer. Elemental
analyses (C, H, N) were performed on a Perkin-Elmer
240C analyser. Magnetic susceptibility measurements of
crystalline samples were carried out in the temperature range
of 4–300 K on a Maglab system 2000 magnetometer at a
field strength of 2000 and 5000 G for 1 and 2, respectively.
Figs. 1 and 2 give a view of complexes 1 and 2, respec-
tively. The Cu(II) atoms in both compounds are coordi-
Table 1
Crystal and structure definement data for 1 and 2
Complex
1
2
Formula
Formula weight
T (K)
C
352.82
293(2)
18H11CuNO3
C16H15CuNO3
332.83
293(2)
Crystal system
Space group
a (A)
Orthorhombic
P212121
7.253(2)
12.144(4)
16.001(5)
90
1409.2(7)
4
Orthorhombic
P212121
5.0597(16)
12.300(4)
21.824(7)
90
1358.2(8)
4
1.628
2.1.1. [CuL] (1)
One millimolar of 2-hydroxy-1-naphthaldehyde was
added to a methanol solution containing 1 mmol of 2-
aminobenzoic acid and 1 mmol of LiOH. The resulting solu-
tion was refluxed for 2 h, then 1 mmol of CuSO4Æ5H2O in
5 mL of methanol was added to afford a brown yellow solu-
tion. The mixture was transferred into a 25 mL Teflon-lined
stainless steel vessel and heated under autogenous pressure
at 85 ꢁC for 6 d. Finally it was allowed to recover to room
temperature. The dark green crystals were collected, washed
with methanol, and dried at ambient temperature. Anal. for
C18H11CuNO3: Found. C, 61.22, H: 3.11, N, 3.97%, Calc. C,
61.66, H, 3.18, N, 4.02%. IR (KBr, cmꢁ1): 3444 (w),1621
(m), 1598 (s), 1574 (m), 1537 (s), 1458 (s),1429 (m), 1409
(m), 840 (m), 768 (m), 755 (s), 571 (w), 503 (m).
˚
˚
b (A)
˚
c (A)
a, b, c (ꢁ)
3
˚
V (A )
Z
Dc (g cmꢁ3
)
1.663
1.564
716
l (mmꢁ1
F(000)
)
1.617
684
Crystal size (mm)
h (ꢁ)
0.34 · 0.20 · 0.14
2.11 to 26.18
ꢁ8 6 h 6 8,
ꢁ15 6 k 6 12,
ꢁ19 6 l 6 18
7977
1.000000 and
0.666097
2804 [0.0372]
2804
208
1.104
R1 = 0.0359
wR2 = 0.0729
R1 = 0.0524
wR2 = 0.0775
0.24 · 0.18 · 0.08
1.87 to 25.66
ꢁ26 h 6 6,
ꢁ14 6 k 6 14,
ꢁ26 6 l 6 25
7391
1.0000 and
0.786816
2560 [0.0383]
2560
193
1.134
R1 = 0.0290
wR2 = 0.0665
R1 = 0.0375
wR2 = 0.0884
Measd. reflcn.
N
Max. and min.
transmission
2.1.2. [CuL0] (2)
Nind (Rmerge
)
Nobs (I > 2r(I))
Nvar
To a methanol solution of L-valine (1 mmol) and KOH
(1 mmol) was added 5 mL of methanol solution of
2-hydroxy-1-naphthaldehyde (1 mmol). Subsequently, 1 mmol
of Cu(CH3COO)2ÆH2O was added slowly. The resulting
mixture was heated at 60 ꢁC for 2 h. The green crystals suit-
able for X-ray analysis were obtained by slow evaporation
GoF (all)
Final R indices
[I > 2r(I)]
R indices (all data)

42
H.-D. Bian et al. / Journal of Molecular Structure 872 (2008) 40–46
Table 2
ing ligand to give a distorted square-planar geometry.
˚
Select bond lengths (A) and angles (ꢁ) for 1 and 2
The metal center in 1 and 2 is displaced by 0.1022 and
˚
Complex 1
Complex 2
1.0819 A out of the least-squares plane defined by the
˚
donor atoms, respectively. Each deprotonated Schiff base
ligand acts as a tridentate ligand towards one copper(II)
center, and as a monodentate ligand towards another cop-
per(II) ion. The ligands forms two six-membered rings for
1, one six-membered ring and one five-membered chelate
ring for 2. The dihedral angle between the two related mean
ring planes is 29.3ꢁ and 16.7ꢁ for 1 and 2, respectively. The
Bond lengths (A)
Cu(1)–O(1)
Cu(1)–N(1)
Cu(1)–O(2)
Cu(1)–O(3A)
1.876(2)
1.914(3)
1.932(3)
1.940(3)
Cu(1A)–O(3)
Cu(1A)–N(1)
Cu(1A)–O(1A)
Cu(1A)–O(1)
1.875(3)
1.907(3)
1.978(2)
2.004(3)
Bond angles (ꢁ)
O(1)–Cu(1)–N(1)
O(1)–Cu(1)–O(2)
N(1)–Cu(1)–O(2)
O(1)–Cu(1)–O(3A)
N(1)–Cu(1)–O(3A)
O(2)–Cu(1)–O(3A)
93.64(10)
151.49(12)
93.18(11)
87.78(11)
164.20(12)
93.03(12)
O(3)–Cu(1A)–N(1)
O(3)–Cu(1A)–O(1A)
N(1)–Cu(1A)–O(1A)
O(3)–Cu(1A)–O(1)
N(1)–Cu(1A)–O(1)
O(1)–Cu(1A)–O(1A)
92.76(12)
89.56(11)
173.20(12)
164.01(12)
82.35(12)
97.06(6)
˚
average Cu–O bond lengths (1.916 and 1.952 A for 1 and 2,
respectively) are in agreement with the values found in
related compounds [7]. In complex 1 the carboxylate
groups bridge copper atoms along a-axis by syn–anti con-
formation, leading to an infinite 1-D right-handed helical
chain with a 21 screw axis (Fig. 3). In 2 the Cu(II) atoms
is bridged by monatomic carboxylate groups to build a
left-handed helical chain (Fig. 4), which is very rare in
metal carboxylate complexes [4e]. The dihedral angle of
the mean coordination planes around Cu and Cu0 is 65ꢁ
and 68.6ꢁ for 1 and 2, respectively. The single helix has a
Symmetry transformations used to generate the equivalent atoms: com-
plex 1, A: x ꢁ 1/2, ꢁy + 5/2, ꢁz; complex 2, A: x ꢁ 1/2, 1/2 ꢁ y, 2 ꢁ z.
˚
pitch height of 7.253 and 5.0597 A for 1 and 2, respectively,
which equal to the corresponding unit cell length a. The
pitch height of 1 is longer than that of 2, which is due to
the longer –Cu–O–C–O0–Cu0– backbone of 1 than the –
Cu–Ocarboxylate–Cu0– backbone of 2. The distance of
Cuꢀ ꢀ ꢀCu bridged by carboxylate group is 4.984 and
˚
3.577 A in 1 and 2, respectively. In the bc plane of 1, the ver-
˚
˚
tical distances of Cuꢀ ꢀ ꢀCu (3.419 A), O3ꢀ ꢀ ꢀO3 (3.398 A),
˚
and O2ꢀ ꢀ ꢀO2 (0.764 A) indicate that the shape of the helical
chain is not circularity but spindle (Fig. 3b). However, the
Fig. 1. Crystal structure of 1. Symmetry transformations used to generate
equivalent atoms: A, x ꢁ 1/2, ꢁy + 5/2, ꢁz, B, x + 1/2, ꢁy + 5/2, ꢁz.
˚
vertical distances of Cuꢀ ꢀ ꢀCu (2.529 A) and O1ꢀ ꢀ ꢀO1
˚
(1.582 A) in 2 reveal a quadrangle shape (Fig. 4b).
An interesting feature in the crystal structure of 1 is the
existence of C–Hꢀ ꢀ ꢀCu weak hydrogen bonding. As well
known, conventional ‘‘strong’’ hydrogen bonds (e.g., O–
Hꢀ ꢀ ꢀO, N–Hꢀ ꢀ ꢀO, etc.) and weak C–Hꢀ ꢀ ꢀX (where X = N,
O, p, etc.) interactions may be utilized in the deliberate
design of organic solids, possessing controlled supramolec-
ular structures with the intention that such materials may
possess specific and useful chemical, physical, or optical
properties-so-called crystal engineering [8]. However, weak
hydrogen bonding with Cu(II) is rare [9]. In our case, the
Cu(II) atom bound to the H8 from C8 of the naphthyl ring
˚
˚
with the separation of Hꢀ ꢀ ꢀCu (3.079 A), Cuꢀ ꢀ ꢀC (3.658 A)
and the angle of C–Hꢀ ꢀ ꢀCu (122.0ꢁ). These are comparable
to those for weak hydrogen bonding found in the literature
[9c]. The weak C–Hꢀ ꢀ ꢀCu interactions further connect the
single helical chains into a 2-D network (Fig. 5).
3.2. Magnetic properties
Fig. 2. Crystal structure of 2. Symmetry transformations used to generate
equivalent atoms: A, x ꢁ 1/2, ꢁy + 1/2, ꢁz + 2.
ꢀ
ꢁ
2=3
Ng2b2 1 þ Ax þ Bx2 þ Cx3 þ Dx4 þ Ex5
2J
jT
nated to the phenolic oxygen atom, imine nitrogen atom,
and one carboxylate oxygen atom from the same ligand
and another carboxylate oxygen atom from the neighbor-
v ¼
x ¼
4jT
1 þ A0x þ B0x2 þ C0x3 þ D0x4
ð1Þ

H.-D. Bian et al. / Journal of Molecular Structure 872 (2008) 40–46
43
Fig. 3. (a) Stereoview of a section of the infinite single right-handed helix of 1 (hydrogen atoms are omitted for clarity); (b) the handed helical chain
following the 21 screw axis along the a axis; (c) the Corey–Pauling–Koltun (CPK) model of the helical chain.
Fig. 4. (a) Stereoview of a section of the infinite single left-handed helix of 2 (hydrogen atoms are omitted for clarity); (b) the handed helical chain
following the 21 screw axis along the b axis; (c) the CPK model of the helical chain.
A = 5.7979916, B = 16.902653, C = 29.376885, D = 29.832959,
E = 14.036918,
center (theoretical value with g = 2, leff = 1.72lB). As the
temperature is lowed, leff increases to 3.39lB at 2 K. A
least-squares fit of the data to the Eq. (1) [10] yields the val-
ues of J = 7.08 cmꢁ1, and g = 2.09, R = 4.36 · 10ꢁ4. The
behavior is characteristic of a weak ferromagnetic interac-
tion between the copper(II) ions. This behavior can be
explained in terms of the topology of the bridge between
A0 = 2.7979916,
D0 = 4.5743114
B0 = 7.0086780,
C0 = 8.6538644,
The magnetic behaviour of 1 is shown in Fig. 6 by plot-
ting leff and vM vs. T. The value of leff at 300 K for 1 is
1.82lB, which is slight larger than one uncoupled S = 1/2

44
H.-D. Bian et al. / Journal of Molecular Structure 872 (2008) 40–46
Fig. 5. 2-D structure involving weak hydrogen bonding in 1.
Fig. 7. A plot for complex 2 of temperature dependence of vM (O) vs. T
and leff (e) vs. T. The solid lines are theoretical fits based on Eq. (2).
Fig. 6. A plot for complex 1 of temperature dependence of vM (O) vs. T
and leff (e) vs. T. The solid lines are theoretical fits based on Eq. (1).
copper(II) ions. According to Kahn’s model [11], the
exchange integral (J) can be decomposed in two terms,
one ferromagnetic (JF) and the other antiferromagnetic
contribution (JAF). In this model, the value of JAF is pro-
portional to the square of the integral overlap between
magnetic orbitals (S2). While ferromagnetic contributions
are usually small. In syn–anti Cu–O–C(R)–O0–Cu0 com-
plexes, the contributions from the 2p orbitals of the O
and O0 atoms belonging to the magnetic orbitals centered
on Cu and Cu0 are unfavorably oriented to give a strong
overlap [3a,5b,12].In our case, the value of S is very small
and is close to zero (JAF ꢂ 0), which leads to ferromagnetic
coupling. Moreover, the dihedral angle of the mean coordi-
nation planes around Cu and Cu0 is 65ꢁ. The nonplanarity
of the chain skeleton is expected to decrease the overlap
density of the magnetic orbitals in the bridging region
and to lower the antiferromagnetic contribution to such
an extent that the ferromagnetic contribution becomes pre-
dominant [3a–5b,12].
The magnetic behaviour of 2 is shown in Fig. 7. The
value of leff at 300 K is 1.65lB, which is slightly smaller
than that of one uncoupled S = 1/2 center. As the temper-
ature is lowed, leff decreases to 0.49lB at 2 K. Complex 2
exhibits a chain of copper(II) ions which are bridged by
monatomic carboxylate groups. The angle of Cu–O–Cu
in this case is 127.82ꢁ, which indicates that the magnetic
orbitals overlap in some extent. With the structure of 2 in
mind we analysed its magnetic data through the polyno-
mial expression (Eq. (2)) derived by Hall [13] which
describes well the results of Bonner and Fisher [14] on a
uniformly spaced linear chain of local spin S = 1/2:
Ng2b
kT
0:25 þ 0:144995x þ 0:30094x2
vM
¼
2 ꢃ
ð2Þ
1 þ 1:9862x þ 0:68854x2 þ 6:0626x3
where x = jJj/kT and the other parameters have their usual
meaning. The best fit of the data to Eq. (2) in the high-tem-
perature region 60–300 K yields magnetic parameters of
J = ꢁ61.6 cmꢁ1, g = 2.08, and R = 6.79 · 10ꢁ4. The result

H.-D. Bian et al. / Journal of Molecular Structure 872 (2008) 40–46
45
Table 3
Relevant magneto-structural parameters for Cu(II) complexes containing monoatomic carboxylate bridge
Compounda
/
(ꢁ)
Carboxylate pathwayb
J (cm1)
Ref.
CuꢁOꢁCu
[Cu(L1)CH3COO]2
95.34
96.1(1)
96.3(2)
96.9
98.1
98.3
101.0
101.9
102.6
95.7
104.1
105.4
109.8
127.8
E–A
E–A
E–A
E–A
E–A
E–A
E–A
E–A
E–A
ꢁ0.5
[16a]
[16b]
[16b]
[16c]
[16c]
[16d]
[16e]
[16f]
[16g]
[Cu(L2)2(CH3COO)2]
ꢁ3.02
ꢁ3.68
ꢁ1.33
ꢁ1.54
ꢁ1.5
[Cu(L3)2(CH3COO)2]
Cu2(L4)2(CH3COO)2
Cu2(L5)(CH3COO)2 2H2O
Cu2(L6)(CH3COO)22CH3OH
Cu2(L7)2(H20)2.4H202
ꢁ2.1
[Cu2 (tda)2 (bipy)2]ÆH2tda
[Cu(L8)CH3COO]2ÆH2OÆC2H5OH
+3.2
+0.63
[Cu(L9)(NH3)2]n(H2O)n
[{Cu(L10)(CH3CH2COO)}2]
[Cu2(CH2COO)2(bipy)2](ClO4)
[CuL0]n
E–A
E–A
E–A
E–E
+12
[16h]
[16i]
[16j]
ꢁ3.3
+3.6
ꢁ61.6
This work
a
HL1, 7-amino-4-methyl-5-aza-3-hepten-2-one; HL2, N-methyl-N0-(5-nitrosalicylidene)-1,3-propanediamine; HL3, N-methyl-N0-(5-bromosalicylidene)-
1,3-propanediamine; HL4, N-methyl-N0-salicylidene-1,3-propanediamine; HL5, N-methyl-N0-(5-methoxysalicylidene)-1,3-propanediamine; H2L6, N-N0-
bis(2-((o-hydroxybenzhydrylidene)amino)ethyl)-1,2-ethanediamine; HL7, N-benzoylglycine; H2L8, N-(1,1-dimethyl-2-hydroxyethyl)salicylaldimine;
H2L9, fumarate; H2L9, pyridine-2-carbaldehyde thiosemicarbazone; H2tda, thiodiacetate; bipy,2,20-bipyride.
b
E–A, equatorial–apical; E–E, equatorial–equatorial.
indicates antiferromagnetic coupling between the cop-
per(II) ions in 2.
carboxylate-bridged copper(II) complexes. The structural
characterization shows that the carboxylate group acts as
a triatomic syn–anti and a rare monoatomic bridging mode
in 1 and 2, respectively. The poor overlapping between the
metal centered magnetic orbitals through the syn–anti
bridge leads to the weak ferromagnetic coupling in 1. While
in 2, the antiferromagnetic coupling is found mainly due to
the large Cu–O–Cu angle.
The details of the magneto-structural correlation in the
cases of hydroxo, oxo, and chloro-bridged Cu(II) com-
plexes have been well studied [15]. However, there are only
a few reports on magnetic interactions between copper(II)
atoms with monatomic carboxylate bridge [16]. In these
cases, the copper(II) atoms are in square pyramidal coordi-
nation geometry and are bridged by double oxo bridges in a
out-of-plane exchange pathway, which gives a small overlap
of the magnetic orbitals. Thus only a weak magnetic
exchange was transmitted through the monatomic carbox-
ylate bridge (Table 3). The copper(II) centre of 2 in our case
is almost square planar. Hence the copper(II) ground state
is dx2ꢁy2 . For this type of geometry the antiferromagnetic
interaction would be stronger with the Cu–O–Cu angle
(u) increasing, since the copper(II) dx2ꢁy2 orbitals are then
more favourably positioned to overlap with the bridging
moiety. The angle of Cu–O–Cu (127.82(13)ꢁ) and the rather
5. Supplementary data
Supplementary data are available from The Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax:
+44 1223 336033; e-mail: deposit@ccdc.cam.ac.uk or
www: http://www.ccdc.cam.ac.uk) on request, quoting the
deposition number CCDC 275278 for 1 ad 290755 for 2.
Acknowledgements
˚
short Cu–O bond lengths (1.978(2) and 2.004(3) A) in 2
This work was supported by the Teaching and Research
Award Program for Outstanding Young Teachers in High-
er Education Institutions of MOE, P.R.C., and National
Natural Science Foundation of China (No. 20331020),
the Science Foundation of Guangxi of China (0342025).
result in effective magnetic exchange interaction through
the monatomic bridge. However, the J value obtained here
is much smaller than that of the monohydroxo-bridged cop-
per(II) complexes with similar Cu–O–Cu angle and Cu–O
bond lengths [17]. Similar to 1, the dihedral angle of the
mean coordination planes around Cu and Cu0 of 2 is
68.6ꢁ, which decreases the overlap density of the magnetic
orbitals and lower the antiferromagnetic contribution to
some extent. In addition, the monoatomic carboxylate
bridge is markedly different from OHꢁ, and thus a large
substituent effect at the bridging O atoms could make the
generalizations about the J vs. / trend less applicable [16g].
References
[1] S. Liao, C.Y. Su, H.X. Zhang, J.L. Shi, Z.Y. Zhou, H.Q. Liu, A.S.C.
Chan, B.S. Kang, Inorg. Chim. Acta 336 (2002) 151.
[2] (a) Y. Hou, E.H. Shen, S.T. Wang, E.B. Wang, D. R Xiao, Y.G. Li,
L. Xu, C.W. Hu, Inorg. Chem. Commun. 6 (2003) 1347;
(b) L. Han, M.C. Hong, Inorg. Chem. Commun. 8 (2005) 406.
[3] (a) S.K. Dey, B. Bag, K.M.A. Malik, M.S.E. Fallah, J. Ribas, S.
Mitra, Inorg. Chem. 42 (2003) 4029;
4. Conclusions
(b) S.J. Rettig, R.C. Thompson, J. Trotter, S. Xia, Inorg. Chem. 38
(1999) 1360;
We have presented here the synthesis, single-crystal
structure, and magneto-structral correlation of two 1-D
(c) J. Zhang, Z.J. Li, J.-K. Cheng, Y. Kang, Y.-Y. Qin, Y.-G. Yao,
New J. Chem. 29 (2005) 421.

46
H.-D. Bian et al. / Journal of Molecular Structure 872 (2008) 40–46
[4] (a) G.B. Deacon, R.J. Phillips, Coord. Chem. Rev. 33 (1980) 227;
(b) M. Melnik, Coord. Chem. Rev. 36 (1981) 1;
[10] G.A. Baker Jr., G.S. Rushbrooke, G.E. Gilbert, Phys. Rev. A 135
(1964) 1272.
(c) D. Schulz, T. Weyhermuller, K. Wieghardt, C. Butzlaff, A.X.
¨
[11] O. Kahn, M.F. Charlot, Nouv. J. Chim. 4 (1980) 567.
[12] (a) E. Colacio, J.-M. Dominguez-Vera, J.-P. Costes, R. Kiveka¨s,
Inorg. Chem. 31 (1992) 774;
Trautwein, Inorg. Chim. Acta 246 (1996) 387;
(d) M. Casarin, C. Corvaja, C.D. Nicola, D. Falcomer, L. Franco, M.
Monari, L. Pandolfo, C. Pettinari, F. Piccinelli, Inorg. Chem. 44
(2005) 6265;
(b) R.L. Carlin, K. Kopinga, O. Kahn, M. Verdaguer, Inorg. Chem.
25 (1986) 1786.
(e) A. Erxleben, Inorg. Chem. 40 (2001) 2928;
(f) X.Y. Yang, J.D. Ranford, J.J. Vittal, Cryst. Growth Des. 4 (2004)
781;
(g) J. Wang, F.L. Bei, X.J. Yang, L.D. Lu, X. Wang, J. Mol. Sturct.
643 (2002) 129;
[13] J.W. Hall, PhD dissertation, University of North Carolina, 1977.
[14] J.C. Bonner, M.E. Fisher, Phys. Rev. A 135 (1964) 640.
[15] (a) V. Mckee, M. Zvagulis, J.V. Dagdigian, M.G. Patch, C.A. Reed,
J. Am. Chem. Soc. 103 (1984) 384;
(b) M.S. Haddad, W.R. Wilson, D.J. Hodgson, D.N. Hendrickson, J.
Am. Chem. Soc. 103 (1981) 384;
(c) P.K. Coughlin, S.J. Lippard, J. Am. Chem. Soc. 103 (1981) 3228.
[16] (a) J.P. Costes, F. Dahan, J.P. Laurent, Inorg. Chem. 24 (1985) 1018;
(b) B. Chiari, J.H. Helms, O. Piovesana, T. Tarantelli, P.F. Zanazzi,
Inorg. Chem. 25 (1986) 2408;
(h) B.L. Chen, F.R. Fronczek, B.H. Courtney, F. Zapata, Cryst.
Growth Des. 6 (2006) 825.
[5] (a) J.P. Costes, F. Dahan, J.P. Laurent, Inorg. Chem. 24 (1985) 1018;
(b) E. Colacio, M. Ghazi, R. Kiveka¨s, J.M. Moreno, Inorg. Chem. 39
(2000) 2882;
(c) A.J. Costa-Filho, O.R. Nascimento, L. Ghivelder, R. Calvo, J.
Phys. Chem. B 105 (2001) 5039.
(c) B. Chiari, J.H. Helms, O. Piovesana, T. Tarantelli, P.F. Zanazzi,
Inorg. Chem. 25 (1986) 870;
[6] (a) G.M. Sheldrick, SADABS, Program for area detector adsorption
correction, Institute for Inorganic Chemistry, University of Go¨ttin-
gen, Germany, 1996.;
(d) B. Chiari, W.E. Hatfield, O. Piovesana, T. Tarantelli, L.W.TER
Haar, P.F. Zanazzi, Inorg. Chem. 22 (1983) 1468;
(e) E.D. Estes, W.E. Estes, R.P. Scaringe, W.E. Hatfield, D.J.
Hodgson, Inorg. Chem. 14 (1975) 2564;
(b) G.M. Sheldrick, SHELXS-97 and SHELXL-97. University of
Go¨ttingen, Germany, 1998.
(f) R. Baggio, M.T. Garland, J. Manzur, O. Pena, M. Perec, E.
˜
[7] (a) J.Y. Lu, V. Schauss, Inorg. Chem. Commun. 6 (2003) 1332;
(b) M. Mizutani, N. Maejima, K. Jitsukawa, H. Masuda, H. Einaga,
Inorg. Chim. Acta 283 (1998) 105;
Spodine, A. Vega, Inorg. Chim. Acta 286 (1999) 74;
(g) A.M. Greenway, C.J. O’Connor, J.W. Overman, E. Sinn, Inorg.
Chem. 20 (1981) 1508;
(c) S.G. Baca, S.T. Malinovskii, P. Franz, C. Ambrus, H. Stoeckli-
Evans, N. Gerbeleu, S. Decurtins, J. Solid State Chem. 177 (2004)
2841.
(h) P.S. Mukherjee, T.K. Maji, G. Mostafa, J. Ribas, M.S.E. Fallah,
N.R. Chaudhuri, Inorg. Chem. 40 (2001) 928;
´
´
(i) P. Gomez-Saiz, J. Garıa-Tojal, A. Mendia, R. Donnadieu, L.
Lezama, J.L. Pizarro, M.I. Arriortua, T. Rojo, Eur. J. Inorg. Chem.
(2003) 518;
[8] C.K. Broder, M.G. Davidson, V.T. Forsyth, J.A.K. Howard, S.
Lamb, S.A. Mason, Cryst. Growth Des. 2 (2002) 163.
[9] (a) D. Braga, F. Grepioni, G.R. Desiraju, Chem. Rev. 98 (1998) 1375;
(b) D. Braga, F. Grepioni, E. Tedesco, Organometallics 16 (1997)
1846;
(j) G. Christon, S.P. Perlepes, E. Libby, K. Folting, J.C. Huffman,
R.J. Webb, D. Hendrickson, Inorg. Chem. 29 (1990) 3657.
[17] (a) A.K. Patra, M. Ray, R. Mukherjee, Polyhedron 19 (2000) 1423;
(b) I. Castro, J. Faus, M. Julve, F. Lloret, M. Verdaguer, O. Kahn, J.
Chem. Soc. Dalton Trans. (1990) 2207;
(c) L.Y. Yang, Q.Q. Chem, Y. Li, S.X. Xiong, G.P. Li, J.S. Ma, Eur.
J. Inorg. Chem. (2004) 1478;
´
ˇ
(d) M. Castro, J. Cruz, H. Lopez-Sandoval, N. Barba-Behrens, Chem.
(c) E. Spodine, J. Manzur, M.T. Garland, M. Kiwi, O. Pena, D.
Commun. (2005) 3779.
Grandjean, L. Toupet, J. Chem. Soc., Dalton Trans. (1990) 365.