Journal of Molecular Structure 984 (2010) 416–423

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Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstruc

Novel copper(II) sulfonate–arsonates with discrete cluster, 1D chain

and layered structures
Fei-Yan Yi, Qi-Pu Lin, Tian-Hua Zhou, Jiang-Gao Mao ⇑
State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences, Fuzhou 350002, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Hydrothermal reactions of copper(II) salts with o-sulfophenylarsonic acid (o-HO3S–C6H4–AsO3H2, H3L)
Received 9 September 2010 led to a layered compound, Cu2.5(L)(OH)2 (1). Introduction of the auxiliary chelating ligands such as
Received in revised form 6 October 2010 2,20 -bipyridine (bipy) or 1,10-phenanthroline (phen) and 2,20 :60 ,20 0 -terpyridine (terpy) led to three new
Accepted 6 October 2010
copper(II) sulfonate–arsonates with lower dimensional structures, namely, mononuclear Cu(HL)(bipy)
Available online 12 October 2010
(H2O)2H2O (2), dinuclear [Cu(HL)(phen)]24H2O (3) and one-dimensional Cu(HL)(terpy)2H2O (4). Mag-
netic property measurements indicate that 1 exhibits ordinary antiferromagnetic feature, without the
Keywords:
geometric spin frustration as expected. 2 shows a typical paramagnetic behavior. There exists antiferro-
Metal sulfonate–arsonates
Inorganic–organic hybrids
magnetic interactions between the magnetic centers in dimeric 3. 4 displays an antiferromagnetic mag-
Hydrothermal reactions netic exchange interaction propagated via OASAO bridges.
Magnetic properties Ó 2010 Elsevier B.V. All rights reserved.
Crystal structures

1. Introduction a large extent by the possibility of using them as convenient model

Metal organo phosphonates are a class of inorganic–organic hy-
brid compounds with many potential applicants in the areas of
catalysis, ion exchange, proton conductivity, intercalation chemis-
try, photochemistry and materials chemistry [1–7]. Most of metal
phosphonates display a layered structure in which the metal cen-
ters are bridged by the phosphonate groups, although a variety of
0D clusters, one-dimensional (1D) chains and porous three-dimen-
sional (3D) networks have also been reported [8–14].
Metal organo arsonates are expected to display a similar struc-
tural chemistry to those of metal organo phosphonates, but the lar-
ger ionic radius of As(V) compared to P(V) could lead to some
different architectures with different physical properties. So far,
reports on metal organo arsonates are still limited [15–34]. A
variety of polyoxometalate (POM) clusters based on vanadium,
molybdenum and tungsten arsonates were reported [15–28]. Sev-
eral organo oxo tin clusters with organo arsonates were recently
synthesized solvothermally by the Ma’s group [32]. In the presence
of an auxiliary ligand such as 5-sulfoisophthalic acid monosodium
salt (NaH2SIP) or 1,3,5-benzenetricarboxylic acid (H3BTC), three
novel mixed-ligand lead(II) carcoxylate-arsonates with 1D–3D
structures have been isolated by our group [33,34]. When the sec-
ond metal linker was changed to the N-donor chelating ligands
such as phen or 2,20 -bipy, metal arsonates with lower dimensional
structures were successfully isolated [33,34]. The interest in low
dimensional copper complexes has been driven in recent years to
systems to test the physical theories and models of magnetism, as
well as of establishing useful magneto-structural correlations
[35,36]. The flexibility of the Cu(II) coordination sphere in combi-
nation with the steric and crystal packing forces leads to a tremen-
dous structural diversity of multinuclear copper(II) complexes. In
order to design low dimensional metal arsonates, one possible
route is to attach a weak coordination sulfonate group to the
arsonate ligand, such as o-HO3S–C6H4–AsO3H2, and introducing a
suitable auxiliary ligand such as 2,20 -bipyridine (bipy) or 1,10-
phenanthroline (phen) and 2,20 :60 ,200 -terpyridine (terpy). Such
methods have been proved feasibly by our previous works
[37,38]. As is shown in Scheme 1, hydrothermal reactions of cop-
per(II) salts with o-sulfophenylarsonic acid (o-HO3S–C6H4–AsO3H2,
H3L) led to a layered compound, Cu2.5(L)(OH)2 (1). Introduction of
the auxiliary chelating ligands such as 2,20 -bipyridine (bipy) or
1,10-phenanthroline (phen) and 2,20 :60 ,200 -terpyridine (terpy) led
to three new copper(II) sulfonate–arsonates with lower dimen-
sional structures, namely, mononuclear Cu(HL)(bipy)(H2O)2H2O
(2), dinuclear [Cu(HL)(phen)]24H2O (3) and one-dimensional Cu(HL)
(terpy)2H2O (4). Herein we report their syntheses, crystal struc-
tures and magnetic properties.
2. Experimental section
2.1. Materials and instrumentations

⇑ Corresponding author. o-Sulfophenylarsonic acid (o-HO3S–C6H4–AsO3H2) was synthe-

E-mail address: mjg@fjirsm.ac.cn (J.-G. Mao). sized according to procedures described previously [39,40]. All of

0022-2860/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2010.10.017
 F.-Y. Yi et al. / Journal of Molecular Structure 984 (2010) 416–423 417

2978 (w), 2875 (w), 1602 (m), 1514 (w), 1448 (w), 1422 (w), 1280
(s), 1254 (w), 1167 (m), 1144 (w), 1112 (m), 1061 (w), 1015 (m),
960 (m), 914 (w), 816 (s), 747 (m), 656 (w), 620 (w), 584 (m),
523 (w) (see Fig. S2 of the Supporting material).

2.2.2. Syntheses of 2–4

Scheme 1. The syntheses of compounds 1–4.
other chemicals were obtained from commercial sources and used
without further purification. Elemental analyses were performed
on a German Elementary Vario EL III instrument. The FT-IR spectra
were recorded on a Nicolet Magna 750 FT-IR spectrometer using
KBr pellets in the range of 4000–400 cm1. Thermogravimetric
analyses were carried out on a NETZSCH STA 449C unit at a heating
rate of 10 °C/min under an oxygen atmosphere. X-ray powder dif-
fraction (XRD) patterns (Cu Ka) were collected on a PANalytical
X’Pert PRO diffractometer. The magnetic susceptibility measure-
ments for polycrystalline samples of 1–4 were performed on a
Quantum Design MPMSXL SQUID and PPMS-9T measurement sys-
tem. The raw data were corrected for the susceptibility of the con-
tainer for TIP, and the diamagnetic contributions of the sample
using Pascal constants [41].
2.2. Synthesis
2.2.1. Synthesis of Cu2.5(L)(OH)2 1
A mixture of Cu(CH3COO)2H2O (0.05 g, 0.25 mmol) and H3L
(0.03 g, 0.10 mmol) in 10 mL of deionized water was sealed into
a Parr Teflon-lined autoclave (23 mL) and heated at 165 °C for
3 days. The initial pH values of solution is 3.0. Blue crystals of 1
were collected in about 47% (0.022 g) yield based on H3L. Its purity
was confirmed by XRD powder diffraction (see Fig. S1 of the Sup-
porting material). Anal. Calcd for C6H6AsCu2.5O8S (Mr = 471.94): C,
15.27; H, 1.28. Found: C, 15.01; H, 1.19%. IR data (KBr, cm1) for 1:
A mixture of Cu(NO3)23H2O (0.04 g, 0.15 mmol), H3L (0.04 g,
0.15 mmol) and bipy (0.02 g, 0.15 mmol) in 10 mL of deionized
water was sealed into a Parr Teflon-lined autoclave (23 mL) and
heated at 150 °C for 4 days. The initial pH value of solutions was
adjusted to 3.5 by the addition of 1 M NaOH solution. Blue crystals
for 2 were collected in about 68% (0.06 g) yield based on H3L. Com-
pounds 3 and 4 were synthesized by a similar procedure to that
used for 2 except that phen (for 3) and terpy (for 4) were used
instead of bipy. Blue crystals for 3 were collected in about 85%
(0.07 g) yield for 3 based on H3L. When the reaction solution for
4 was allowed to evaporate slowly at the room temperature, blue
crystals of 4 were collected in about 78% (0.07 g) yield based on
H3L. Their purities for 2–4 were also confirmed by XRD powder dif-
fraction (see Fig. S1 of the Supporting material). Anal. Calcd for 2
(C16H19AsCuN2O9S, Mr = 553.85): C, 34.70; H, 3.46; N, 5.06. Found:
C, 34.47; H, 3.35; N, 4.84%. For 3 (C36H34As2Cu2N4O16S2, Mr =
1119.71): C, 38.61; H, 3.06; N, 5.00. Found: C, 38.40; H, 3.01; N,
4.89%. For 4 (C21H20AsCuN3O8S, Mr = 612.92): C, 41.15; H, 3.29;
N, 6.86. Found: C, 40.91; H, 3.20; N, 6.70%. IR data (KBr, cm1)
for 2: 3422 (m), 3110 (w), 3017 (w), 2388 (w), 1628 (w), 1601
(m), 1497 (w), 1473 (w), 1448 (m), 1432 (w), 1314 (w), 1245 (s),
1180 (s), 1147 (w), 1118 (m), 1064 (m), 1020 (m), 1011 (m), 876
(vs), 836 (s), 785 (w), 764 (m), 659 (m), 637 (w), 615 (m), 568
(w), 505 (w). IR data (KBr, cm1) for 3: 3409 (m), 3060 (m), 2370
(w), 1626 (w), 1585 (w), 1520 (m), 1495 (w), 1429 (s), 1344 (w),
1271 (m), 1250 (w), 1200 (w), 1167 (s), 1143 (m), 1114 (s), 1054
(m), 1003 (s), 875 (m), 855 (s), 814 (m), 770 (w), 741 (m), 723
(m), 659 (m), 613 (s), 594 (w), 560 (w), 498 (w). IR data (KBr,
cm1) for 4: 3452 (m), 3074 (m), 2871 (w), 1639 (w), 1604 (m),
1579 (m), 1499 (w), 1477 (m), 1451 (m), 1409 (w), 1325 (m),
1256 (w), 1202 (vs), 1147 (w), 1117 (w), 1064 (m), 1022 (s), 966
(w), 914 (m), 829 (m), 778 (m), 742 (m), 709 (m), 660 (m), 616
(m), 561 (w), 514 (w), 478 (w) (see Fig. S2 of the Supporting
material).

Table 1
Crystal data and structure refinements for the four compounds.

Compound 1 2 3 4
Formula Cu2.5(L)(OH)2 Cu(HL)(bipy)(H2O)2H2O [Cu(HL)(phen)]24H2O Cu(HL)(terpy)2H2O
Formula weight 471.94 553.85 1119.71 612.92
Crystal system Triclinic Monoclinic Triclinic Triclinic
Space group P1 P21/c P1 P1
Crystal size (mm) 0.12  0.02  0.01 0.14  0.03  0.02 0.5  0.2  0.1 0.2  0.2  0.2
0
6.2757(1) 11.627(6) 8.5512(1) 7.182(9)
A)
a (Å
0
7.3745(3) 7.089(4) 10.5501(2) 10.10(1)
A)
b (Å
0
11.9163(6) 23.39(1) 12.266 16.05(2)
A)
c (Å
a (°) 86.21(1) 90 76.134(9) 102.40(3)
b (°) 81.42(1) 90.597(8) 72.01(1) 92.44(4)
c (°) 73.824(9) 90 81.52(1) 90.04(4)
0
523.55(3) 1928(2) 1018.60(2) 1136(2)
A3)
V (Å
Z 2 4 2 2
Dcalcd (g cm3) 2.994 1.908 1.825 1.792
l (mm1) 8.417 2.999 2.837 2.553
0
0.71073 0.71073 0.71073 0.71073
Wavelength (Å A)
F(0 0 0) 0.970 1.010 1.057 1.048
Reflections collected/unique 4186/2378 [Rint = 0.0306] 14,458/4345 [Rint = 0.0922] 7906/4342 [Rint = 0.0264] 8856/5109 [Rint = 0.0874]
R1, wR2 [I > 2r(I)]a 0.0285, 0.0532 0.0764, 0.1833 0.0388, 0.1003 0.0865, 0.1525
R1, wR2 (all data) 0.0443, 0.0573 0.1200, 0.2119 0.0465, 0.1068 0.1724, 0.2008
a
R1 = R||Fo|  |Fc||/R|Fo|, wR2 = {Rw[(Fo)2  (Fc)2]2/Rw[(Fo)2]2}1/2.
418 F.-Y. Yi et al. / Journal of Molecular Structure 984 (2010) 416–423

2.3. X-ray crystallography compounds were collected by the narrow frame method at
293(2) K. The data sets were corrected for Lorentz and polarization
Data collections were performed on a Saturn 70 CCD diffrac- factors as well as for absorption by a multi-scan method [42]. All
tometer (for 1, 2, 4) and a Rigaku Mercury CCD diffractometer four structures were solved by the direct methods and refined by
(for 3). All diffractometers were equipped0 with a graphite-mono- full-matrix least-squares fitting on F2 by SHELX-97 [43]. All
chromated Mo Ka radiation (k = 0.71073 Å A). Intensity data for all non-hydrogen atoms were refined with anisotropic thermal
parameters. Several atoms (S(1), O(5), O(6) and S(10 ), O(50 ), O(60 ))
Table 2 0 0 of sulfonate groups in compound 2 are severely disordered and
Selected bond lengths (Å
A) for 1–4 and hydrogen bonds (Å
A and deg) for 2–4.
each exhibits two orientations, hence the occupancy factor of each
Compound 1 site was fixed to be 50%. The lattice water molecule (O(3 W)) in
Cu(1)AO(1) 1.939(3) Cu(1)AO(4) 1.966(3)
compound 3 was disordered with O(3 W). . .O(3 W) 0
(symmetry
Cu(1)AO(2)#1 2.410(3) Cu(1)AO(7) 2.007(3)
Cu(1)AO(8) 1.897(3) Cu(2)AO(1) 1.914(2) code: x + 1, y + 1, z + 1) separation of 1.85(4) Å
A and its occu-
Cu(2)AO(1)#2 1.914(2) Cu(2)AO(7) 1.940(2) pancy is also reduced to 50%. The occupancy factor of O(2W) of 3
Cu(2)AO(7)#2 1.940(2) Cu(3)AO(2)#1 1.984(2) was reduced to 50% because of their large thermal parameters.
Cu(3)AO(2)#4 2.512(3) Cu(3)AO(3)#2 1.985(2) All hydrogen atoms were located at geometrically calculated
Cu(3)AO(7) 1.985(3) Cu(3)AO(8)#3 1.915(3)
As(1)AO(1) 1.709(3) As(1)AO(2) 1.683(2)
positions and refined with isotropic thermal parameters. Crystallo-
As(1)AO(3) 1.675(3) S(1)AO(4) 1.475(3) graphic data and structural refinements for compounds 1–4 are
S(1)AO(5) 1.442(3) S(1)AO(6) 1.429(3) summarized in Table 1. Important bond lengths and hydrogen
Compound 2 bonds are listed in Table 2.
Cu(1)AO(1) 1.902(5) Cu(1)AO(4) 2.084(5) CCDC-760472-760475 contain the supplementary crystallo-
Cu(1)AO(1 W) 2.133(6) Cu(1)AN(1) 2.002(6) graphic data for this paper. These data can be obtained free of
Cu(1)AN(2) 2.015(7)
As(1)AO(1) 1.684(6) As(1)AO(2) 1.648(5)
As(1)AO(3) 1.725(5) S(1)AO(4) 1.549(8)
S(10 )AO(4) 1.383(7) S(1)AO(5) 1.410(13)
S(10 )AO(50 )
S(10 )AO(60 )
1.437(13)
1.417(13)
S(1)AO(6) 1.421(12) (a)
Hydrogen bonds
DAHA d(DAH) d(HA) d(DA)
O(3)AH(3A)O(2 W) 0.82 1.81 2.624(9)
O(1 W)AH(1 WA)O(2)#1 0.85 2.05 2.713(9)
O(1W)AH(1WB)O(3 W)#1 0.85 1.95 2.762(17)
O(1 W)AH(1WB)O(5) 0.85 2.37 2.782(14)
O(3 W)AH(3 WA)O(5)#2 0.85 1.78 2.479(19)
O(3W)AH(3WB)O(50 )#3 0.85 2.09 2.80(2)
O(2 W)AH(2 WA)O(1)#4 0.85 2.43 2.830(9)
O(2W)AH(2WB)O(2)#5 0.85 2.31 2.774(9)
Compound 3
Cu(1)AO(3) 1.929(2) Cu(1)AO(3)#1 2.315(2)
Cu(1)AO(6) 1.989(2) Cu(1)AN(1) 2.012(3)
Cu(1)AN(2) 1.987(3)
As(1)AO(1) 1.652(2) As(1)AO(2) 1.711(2)
As(1)AO(3) 1.685(2) S(1)AO(4) 1.434(3)
S(1)AO(5) 1.432(3) S(1)AO(6) 1.484(3) (b)
Hydrogen bonds O1 Cu1 O8 Cu1
DAHA d(DAH) d(HA) d(DA) Cu3
O2 2.960 3.116
O(2)AH(2A)O(1)#2 0.82 1.73 2.551(3) O7 Cu2
O7 3.236
O(1 W)AH(1WB)O(2 W) 0.85 2.21 2.988(11) b a Cu2 O2 3.400
2.960 O7
O(1 W)AH(1WA)O(1)#3 0.85 1.99 2.749(5) Cu3 3.215
O(2 W)AH(2 WA)O(2 W)#4 0.85 2.10 2.86(3) O8 O1
c Cu1
O(2W)AH(2WB)O(3 W)#5 0.85 1.89 2.48(3)
O(3 W)AH(3WB)O(4) 0.85 1.94 2.789(12)
Compound 4
Cu(1)AO(2) 1.926(6) Cu(1)AO(5) 2.406(6) (c)
Cu(1)AO(6)#1 2.446(6) Cu(1)AN(1) 2.028(8)
Cu(1)AN(2) 1.933(7) Cu(1)AN(3) 2.028(8)
As(1)AO(1) 1.659(6) As(1)AO(2) 1.686(6)
As(1)AO(3) 1.736(6) S(1)AO(4) 1.447(7)
S(1)AO(5) 1.461(6) S(1)AO(6) 1.453(6)
Hydrogen bonds
DAHA d(DAH) d(HA) d(DA)
O(3)AH(3B)O(2 W) 0.82 1.93 2.753(10)
O(1 W)AH(1 WD)O(1) 0.85 1.93 2.777(10)
O(1W)AH(1WC)O(2)#1 0.85 2.23 2.901(10)
O(2 W)AH(2WA)O(1 W) 0.85 2.03 2.884(11) b
O(2 W)AH(2WB)O(4)#2 0.85 2.37 2.879(11)
a
Symmetry transformations used to generate equivalent atoms.
For 1: #1 x, y + 1, z; #2 x + 1, y + 1, z; #3 x, y + 2, z; #4 x, y + 1, z. Fig. 1. (a) ORTEP representation of the selected unit in compound 1. The thermal
For 2: #1 x, y + 1, z, #2 x, y  1, z; #3 x + 2, y + 1, z; #4 x + 1, y  1/2, z + 1/2; ellipsoids are drawn at 50% probability level. Symmetry code for the generated
#5 x + 1, y + 1/2, z + 1/2. atoms: (a) x, y + 1, z; (b) x + 1, y + 1, z; (c) x, y + 2, z; (d) x, y + 1, z; (e)
For 3: #1 x + 1, y + 2, z; #2 x, y + 2, z; #3 x + 1, y, z; #4 x + 2, y + 1, x, y1, z. (b) View the CuAO chain of compound 1. (c) View the 2D layered structure
z + 1; #5 x + 1, y + 1, z + 1. along c-axis. The CSO3 and CAsO3 tetrahedra are shaded in light and dark grey
For 4: #1 x  1, y, z #2 x, y  1, z. respectively.
 F.-Y. Yi et al. / Journal of Molecular Structure 984 (2010) 416–423 419

charge from The Cambridge Crystallographic Data Center via 3.1.2. Structure of Cu(HL)(bipy)(H2O)2H2O (2)
www.ccdc.cam.ac.uk/data_request/cif. Cu(HL)(bipy)(H2O)2H2O (2) is mononuclear. Its asymmetric
unit contains a copper(II) ion, one bipy ligand and one HL2 anion,
one aqua ligand as well as two lattice water molecules (Fig. 2). The
3. Results and discussion Cu(II) ion is five-coordinated by one arsonate oxygen atom and one
sulfonate oxygen atom from one HL2 anion, one aqua ligand as
3.1. Crystal structure well as a bidentate chelating bipy ligand. Its coordination geometry
can be described
0
as square pyramid. 0The CuAO (1.902(5)–
Hydrothermal reactions of copper(II) salts with o-sulfopheny- 2.133(6) ÅA) and CuAN (2.002(6)–2.015(7) Å A) distances are compa-
larsonic acid (o-HO3S–C6H4–AsO3H2, H3L) led to a layered rable to those in 1 and other Cu(II) phosphonates previously
compound Cu2.5(L)(OH)2 (1). Introducing the auxiliary chelating reported [44,45]. The HL2 anion is singly protonated, as indicated
ligands such as bipy (or phen, terpy) reduced the coordination sites by one elongated AsAO bonds (Table 2). It forms a bidentate che-
of the metal sites available for the arsonate ligands, hence, the lation with one metal ion by using one sulfonate oxygen atom
dimensionality of 2–4 are further reduced. They display various and one arsonate oxygen atom (CuAOAAsACACASAO), the other
types of structures such as mononuclear cluster in 2, dinuclear oxygen atoms are non-coordinated (Scheme 2b).
cluster in 3 and 1D chain in 4. These mononuclear cluster units are interlinked into 2D supra-
molecular layer by hydrogen bonds among aqua ligand, lattice
water molecules and non-coordination oxygen atoms of the HL2
3.1.1. Structure of Cu2.5(L)(OH)2 (1) anions (Fig. 2b). The 0
OO separations fall in the range of
There is three unique Cu2+ ions, one L3 anion and two hydroxyl 2.479(19)–2.830(9) Å A (Table 2). These 2D layers are further assem-
anions in the asymmetric unit of 1 (Fig. 1a). Cu(1) is five-coordi-
nated by one {SO3} oxygen atom, two {AsO3}2 oxygen atoms
from two L3 anions and two hydroxyl anions. Cu(2) located at
an inversion center is four-coordinate with two arsonate oxygen
atoms from two L3 anions and two hydroxyl anions (O(7)). The
coordination geometry around the Cu(2) ion can be described as
a square planar. Cu(3) is in a square pyramidal geometry composed
of three {AsO3}2 oxygen atoms from three L3 anions and two hy-
droxyl anions (O(7),0 O(8)). The CuAO distances are in the range of
1.897(3)–2.512(3) Å A, which are comparable to those reported in
copper(II) phenylphosphonates [44,45].
The L3 anion is heptadentate and bridges six metal ions. It
forms a CuAOASACACAAsAO chelating ring and also bridges with
five other copper(II) ions. The three arsonate oxygen atoms are
monodentate, bidentate and tridentate, respectively. One sulfonate
oxygen atom is unidentate and the other two remain non-coordi-
nated (Scheme 2a). There are two hydroxyl anions (O(7) and
O(8)). O(7) is tridentate and O(8) is bidentate.
The CuOx (x = 4, 5) polyhedra are interconnected via edge
sharing (O(1)AO(7), O(2)AO(2), O(2)AO(7) and O(2)AO(8)) and
corner-sharing into a 1D copper(II) oxide chain (Fig. 1b). 0
The
CuCu separations are in the range of 2.960(1)–3.400(1) Å A. Neigh-
boring 1D copper(II) oxide chains are extended into a 2D layered
structure by bridging arsonate ligand. The sulfonate groups and
organic groups of the L3 anions are orientated toward the 0
inter-
layer space (Fig. 1c). The inter layer distance is about 11.9 ÅA. These
2D layers are further assembled into the 3D supramolecular struc-
ture by very weak aromatic pp interactions between phenyl
rings of the L3 ligand (Table S1, Fig. S3). The distances from the
Fig. 2. (a) ORTEP representation of the selected unit in compound 2. The thermal
center of the phenyl ring formed by C(1), C(2), C(3), C(4), C(5)0 ellipsoids are drawn at 50% probability level. (b) View of the hydrogen bonded 2D
and C(6) to those of its symmetrically generated
0
ones are 3.750 Å A layer in compound 2. Hydrogen bonds are drawn as dashed lines. The CSO3, CAsO3
(symmetry code: x, y, 1  z) and 3.886 Å A (symmetry code: x, tetrahedra and CuO3N2 square pyramidal are shaded in light, medium and dark
1  y, 1  z). grey, respectively.

Cu Cu
Cu Cu Cu Cu Cu Cu
Cu
OO O O Cu O O O O O O OH O O
O O O OO
S As O Cu O As O
S As S S As
OH O OH

(a) (b) (c) (d)

Scheme 2. The coordinated modes of the sulfonate–arsonate ligand in compounds 1 (a), 2 (b), 3 (c) and 4 (d).
420 F.-Y. Yi et al. / Journal of Molecular Structure 984 (2010) 416–423

dinated arsonate oxygen atom (O(1) symmetry code: x, y  1, z)

(a) 0
with an O. . .O separation of 2.551(3) Å A. Such 1D chains is further
cross-linked into a 2D layer by hydrogen bonds among the
non-coordinated oxygen atoms of HL2 anions and free water
molecules (O(1W), O(2W) and 0
O(3W)) with OO separations in
the range of 2.48(3)–2.99(1) Å A (Fig. 3b). It is interesting to note that
the hydrogen bonding between water molecules led to the forma-
tion of a 1D water chain along a-axis (Fig. 3b). Finally, these 2D lay-
ers are assembled into the 3D supramolecular network by the
weak pp interactions between aromatic rings of the phen ligands
(Table S1, Fig. S5). The distances between0 centers of these aromatic
rings are in the range of 3.688–3.703 Å A, and the corresponding
dihedral angles are in the range of 0–4.9 °.

3.1.4. Structure of Cu(HL)(terpy)2H2O (4)

There is one unique Cu2+ ion, one HL2 anion, one triadentate-
chelating terpy ligand as well as two lattice water molecules in

(b)
(a)

(b)
Fig. 3. (a) ORTEP representation of the selected unit in 3. The thermal ellipsoids are a
drawn at 50% probability level. Symmetry code for the generated atoms: (a) –x+1, c
–y+2, –z. (b) View of the hydrogen bonded 2D layer in compound 3. Hydrogen b
bonds are drawn as dashed lines. The CSO3, CAsO3 tetrahedra and CuO3N2 square
pyramidal are shaded in light, medium and dark grey, respectively.
Cu1

bled into 3D supramolecular structure via weak aromatic pp

interactions between aromatic rings of the bipy ligand and HL2
ligands (Table S1, Fig. S4). The distances between0 centers of these
aromatic rings are in the range of 3.533–3.677 Å A, and the corre-
sponding dihedral angles in the 0
range of 0–5.6 °. The shortest (c)
CuCu separation is 6.689(1) ÅA.

3.1.3. Structure of [Cu(HL)(phen)]24H2O (3)

The formular of 3 contains one dinuclear [Cu2(HL)2(phen)2]
cluster and four lattice water molecules. There is one unique
Cu2+ ion in the asymmetric unit of 3 (Fig. 3a). The Cu(II) ion is
five-coordinate with two arsonate oxygen atoms and one sulfonate
oxygen atom0
from two HL2 anions. The CuAO 0 (1.929(2)–
2.315(2) ÅA) distances and CuAN (1.987(3)–2.012(3) Å A) distances
are comparable to those in 2. The HL2 ligand is tridentate and
bridges two metal ions by one arsonate oxygen and one sulfonate
oxygen atom. It forms a seven-member chelating ring
(CuAOAAsACACASAO) and bridges the second metal ion by using
the same arsonate oxygen atom (Scheme 2c).
A pair of Cu(II) ions are bridged by two HL2 ligands into a Fig. 4. (a) ORTEP representation of the selected unit in compound 4. Free water
[Cu2(HL)2(phen)2] dimeric unit with a Cu2O2 four-member ring. molecules are omitted for clarity. The thermal ellipsoids are drawn at 50%
0
probability level. Symmetry code for the generated atoms: (a) x+1, y, z; (b) x–1, y,
The CuCu instance within the dimer is 3.196(1)0 Å
A and the short-
z. (b) View the 1D chain structure of compound 4. (c) View of the supra-molecular
est inter-cluster CuCu separation is 7.704(1) Å
A. These dimeric 2D layer in compound 4. Hydrogen bonds are drawn as dashed lines. The CSO3,
units are interlinked into 1D chain by hydrogen bonds between CAsO3 tetrahedra and CuO3N3 octahedra are shaded in light, medium and dark grey,
the singly protonated arsonate oxygen atom (O(2)) and non-coor- respectively.
 F.-Y. Yi et al. / Journal of Molecular Structure 984 (2010) 416–423
the asymmetric unit of 4 (Fig. 4a). The Cu(II) ion is octahedrally
coordinate with one arsonate oxygen atom and two sulfonate oxy-
gen atoms from two HL2 anions as well as a triadentate-chelating
terpy. The CuN3O3 octahedron 0
exhibits a ‘‘4
0
+ 2” distortion, two ax-
ial CuAO bonds (2.446(6) Å A and 2.404(6)
0
Å
A) are significantly larger
than CuAN (1.933(7)–2.028(8)
0
Å
A) bonds and remaining CuAO
bond (1.926(6) Å A) The arsonate group of the HL2 ligand is singly
protonated, as indicated 0
by one much-longer AsAO bond
(As(1)AO(3) 1.736 (6) Å A). It forms a bidentate chelation with one
metal ion by using one arsonate oxygen atom and one sulfonate
oxygen atom, and also bridges with another metal ion by using an-
other sulfonate oxygen atom (Scheme 2d).
The interconnection of Cu(II) ions by sulfonate groups of the
HL2 anions results into a 1D chain along 0
the a-axis (Fig. 4b). The
shortest Cu. . .Cu separation is 7.182(9) ÅA. These chains are inter-
linked into the 2D layered structure via hydrogen bonds among lat-
tice water molecules and non-coordinated sulfonate and arsonate
oxygen 0atoms with OO separations in the range of 2.75(1)–
2.90(1) Å
A (Table 2, Fig. 4c). These 2D layers are further assembled
into the 3D supramolecular structure by weak pp interactions
occurred between aromatic rings of the terpy ligands and the phe-
nyl ring of HL2 ligands (Fig. S6). The distance between 0
centers of
these aromatic rings are in the range of 3.857–4.330 Å A (Table S1),
and the corresponding dihedral angles are in the range0 of 0–3.7 °.
The shortest interchain CuCu separation is 7.600(1) Å A.
3.2. Magnetic property studies of compounds 1–4
The temperature-dependent magnetic susceptibilities of com-
pounds 1–4 were measured at 1 kOe in the temperature range
2–300 K.
As shown in Fig. 5a, the vmT value of 1 at room temperature is
1.12 cm3 mol1 K, which is close to the spin-only value expected
for two and a half Cu2+ ions (1.13 cm3 mol1 K with S = 1/2 and
g = 2.2) per formula unit. Upon cooling, it decreases gradually to
Fig. 5. (a) Plots of the vmT and v1
m vs T for compound 1. Insert: the vm vs T plot. The
solid lines represent the best fit to Curie–Weiss law. (b) The field dependent
isothermal magnetization for 1 at 2 K and 20 K in the ±8 T range.
421
a value of 0.03 cm3 mol1 K at 2.0 K, which is striking as the ground
state of such layer should be S = 0. Fitting of the data above 25 K
with the Curie–Weiss law gave negative value (48.6(6) K) of h,
coupled with the presence of a maximum in vm at T = 20 K, indicat-
ing a dominated antiferromagnetic interactions between Cu2+ ions
in the 2D layer at low temperature.
Our previous study shows that the O–S/As–O bridges between
the magnetic ions, are not crucial for the spin-exchange interac-
tions and for deducing the spin–lattice models. Thus, the spin
topology is defined as a unique chain of alternating edge-, edge-
and corner-sharing Cu3(l3-O) triangles (Fig. 1b), which is likely
to exhibit a spin-frustrated antiferromagnetism. As depicted in
Fig. S7a, the susceptibility below 50 K is field-independent, not
indicative of the onset of a ferromagnetic phase transition. The
long-range antiferromagnetic ordering was further verified by
the broad frequency-independent peaks appearing at ca. 20 K
(only in v0m ) of ac magnetic susceptibility (Fig. S7b). The field
dependence of the magnetization, M(H) at 2 and 20 K all in-
creased almost linearly from 0 to 80 kOe and reached 0.23 and
0.24 lB, respectively, per Cu2+ ion at 80 kOe, far from the satura-
tion values of MS = 1 lB for a spin-only Cu2+ ion, further confirm-
ing the predominant antiferromagnetic coupling between the
Cu2+ ions (Fig. 5b).
1, containing irregular alternating ‘‘fused-triangles” chains, may
be easily envisaged as a geometric spin frustration. Yet, only ordin-
ary antiferromagnetic feature with a ground state S = 0 is detected.
Formally, in a tetragonal Cu2+ complex, the magnetic orbital is of
the dx2y2 type with its lobes pointing to the equatorial ligands.
As in 1, there are three inequivalent Cu sites and unequal triangle
side lengths of the Cu3(l3-O) triangle. As shown in Fig. 1b, the
magnetic orbital centered on purely square pyramidal Cu(1) over-
lap with that of the Cu(2) in a planar-square geometry, which
is responsible for the antiferromagnetic interaction. The only
clearly identifiable apical
0
position of Cu(1) is occupied by O(2)
(Cu(1)AO(2): 2.410(3) Å A), which takes, 0by contrast, an equatorial
positon of Cu(3) (Cu(3)AO(2): 1.984(2) Å A). So, the tilting of the ba-
sal planes of Cu(1) and Cu(3) ions with a dihedral angle of 66.7°, is
expected to reduce the overlap of the magnetic orbitals in the
bridging region, hence the ferromagnetic term becomes dominant.
On the basis of the above analysis, 1 can be magnetically consid-
ered as chains of Cu2+ sites with up- and down-spins as depicted
by arrows in Fig. S7c. But, due to the lack of a proper theoretical
model for such a irregular alternating chain, we did not attempt
to calculate the spin gaps.
The global feature of the vmT vs T curve of 2 is characteristic
of a typical paramagnetic behavior (Fig. 6a). The value of vmT at
room temperature is 0.44 cm3 K mol1, close to the expected
value (0.45 cm3 K mol1) for one uncoupled Cu2+ with g = 2.22
per formula unit. On cooling, the vmT value remains almost
constant and reaches 0.43 cm3 K mol1 at 2 K. The negligible
Weiss constants (h) of 0.06 is also indicative the lack of obvious
magnetic interactions between the well separated magnetic
centers in 2.
The vmT of 3 at room temperature is 0.91 cm3 K mol1, which is
very close to the theoretical value of 0.908 cm3 K mol1 for the two
isolated Cu2+ ions with S = 1/2 per formula unit. Upon cooling, the
vmT value decreases gradually, revealing that the dominant
antiferromagnetic interaction between the S = 1/2 spin centers.
Fitting of all data according to the Curie–Weiss law gave
C = 0.90 cm3 mol1 K and h = 2.84 K. Compared with the intra-
cluster magnetic interactions mediated via a pair of arsonate oxy-
gen atoms, the inter-cluster exchange coupling through weak pp
interactions is expected to be negligible. Thus, to evaluate quanti-
tatively the exchange in the dimer with four-member ring [Cu2O2],
the Bleaney–Bowers expression (Eq. (1)) based on the isotropic
Hamiltonian: H = 2J(S1S2) (S1 = S2 = 1/2) [46–50].
422 F.-Y. Yi et al. / Journal of Molecular Structure 984 (2010) 416–423

Fig. 7. TGA curves of compounds 1–4.

D ¼ 1:0 þ 2:7979916y þ 7:0086780y2 þ 8:653644y3

þ 4:5743114y4 ;

y ¼ J=2kB T

vchain
vm ¼ vchain
1  2zJ
Ng 2 b2

in which N, g, kB, and b have their usual meanings, and J is the

exchange coupling constant, and the interchain interaction (zJ)
was also considered. Fitting of magnetic data gave J/kB = 0.01 K,
zJ/kB = 0.89 K and g = 2.18 with an agreement factor R (R = R(vm
Texp  vmTcal)2/R(vmTexp)2) of 1.650  106. The magnetic
exchanges between the intra-chain Cu2+ ions interconnected via
Cu–O–S–O–Cu bridges is very weak as expected.

3.3. TGA studies

Compound 1 is stable up to 268 °C, then it exhibits three steps

Fig. 6. Plots of the vmT and v1
m vs T for compound 2 (a), 3 (b) and 4 (c). The solid
lines represent the best fit to the corresponding classical model and Curie–Weiss
law.
Ng 2 b2 2 expðJ=kB TÞ
vm ¼
kB T 1 þ 3 expðJ=kB TÞ
was used to fit the magnetic data. Inclusion of a term TIP (temper-
ature independent paramagnetism) resulted in a noticeable
improvement of the fit, with the parameters g = 2.12, J/kB = 1.15 K
and vTIP = 1.10  104. The agreement factor defined by R =
R(vmTexp  vmTcal)2/R(vmTexp)2 is equal to 2.99  106.
The plot of v1
m vs T for 4 indicates that it obeys the Curie–Weiss
law in the whole temperature range with h = 0.58 K and
C = 0.447 cm3 K mol1 (Fig. 6c). The small negative Weiss constant
indicates a weak antiferromagnetic interaction between magnetic
centers. The vmT value is 0.45 cm3 K mol1 at room temperature.
It remains almost unchanges above ca. 15 K and it decreases rap-
idly below 15 K. Since the structure of 4 is 1D, we try to fit the
experimental data by means of a S = 1/2 isotropic Heisenberg chain
model (H = JRSiSi+1, Baker equation given as follows) [45–50]:
 2=3
Ng 2 b2 N
vchain ¼
kB T D
N ¼ 1:0 þ 5:7979916y þ 16:902653y2 þ 29:376885y3
þ 29:832959y4 þ 14:036918y5 ;
of weight losses (Fig. 7). The first one (268–326 °C) is mainly due to
the combustion of two hydroxyl anions, the observed weight loss
of 7.63% is very close to the calculated value (7.62%). The other
two overlapping steps covering a temperature rang of 329–
806 °C corresponds to the combustion of sulfophenylarsonic li-
gands. The total weight loss at 806 °C is 35.79%.
ð1Þ
TGA curves of compounds 2 and 4 also exhibit three main steps
of weight losses (Fig. 7). The first step (95–121 °C for 2, 82–128 °C
for 4) corresponds to the release of two lattice water molecules.
The observed weight loss of 5.98% and 5.77% for 2 and 4 are very
close to the calculated value (6.50% and 5.88% for 2 and 4, respec-
tively). The second step (321–357 °C and 323–434 °C for 2 and 4,
respectively) corresponds to the combustion of the coordination
2,20 -bipy (or terpy) ligands. The third step (357–500 °C and 434–
536 °C for 2 and 4, respectively) overlaps with the second one, dur-
ing which the sulfonate–arsonate ligands are combusted. The total
observed weight loss is 80.95% at 500 °C for 2, 75.2% at 536 °C for 4.
Compound 3 is stable up to 332 °C, then it exhibits two continue
steps of weight losses. Such high stability is probably due to the
formation of a 1D water chain which is further interlinked to the
main framework. The first weigh loss (332–346 °C) is mainly due
to the combustion of phen ligands and the water molecules, and
the second one (346–560 °C) is mainly associated with the com-
ð2Þ bustion of sulfonate–arsonate ligands. The total observed weight
loss at 560 °C is 79%.
The final residuals for four compounds were not characterized
due to their corrosive reactions with the TGA buckets made of
Al2O3.
 F.-Y. Yi et al. / Journal of Molecular Structure 984 (2010) 416–423
4. Conclusion
In summary, the hydrothermal syntheses, crystal structures,
and characterizations of four new copper(II) sulfonate–arsonate
have been reported. The arsonate ligands are very flexible and four
types of coordination modes are found in these four compounds.
Compound 1 without an auxiliary ligand exhibits a layered struc-
ture in which the arsonate ligand bridges with six metal ions.
When the chelating auxiliary ligands such as bipy (or phen, terpy)
were applied as the second metal linker, compounds 2–4 featuring
three types of lower dimensional (two 0D and one 1D) are ob-
tained. In latter compounds, the arsonate ligands bind with much
fewer metal ions, one in 2 and two in 3 and 4). There results
may provide some insights into the rational design of the low
dimensional materials.
Acknowledgments
This work was supported by the National Natural Science Foun-
dation of China (Nos. 20973170, 20825104 and 20821061), Key
Project of Chinese Academy of Sciences (No. KJCX2-YW-H01) and
973 Program (No. 2006CB932903), the major project from FJIRSM
(SZD09001).
Appendix A. Supplementary material
Supporting Information (see also the footnote on the first page
of this article): Table of pp interactions, simulated and measured
XRD patterns, and IR spectra and 3D packing diagrams for 1–4, as
well as additional magnetic plots for 1. Supplementary data asso-
ciated with this article can be found, in the online version, at
doi:10.1016/j.molstruc.2010.10.017.
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