Article

pubs.acs.org/crystal

Syntheses, Structure, and Magnetic Properties of New 3d4f

Heterometallic Hydroxysulfates Ln2Cu(SO4)2(OH)4 (Ln = Sm, Eu, Tb, or
Dy) with a Two-Dimensional Triangle Network
Yingying Tang,, Meiyan Cui,, Wenbin Guo, Suyun Zhang, Ming Yang, and Zhangzhen He*,,

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou, Fujian 350002, P. R. China

Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese
Academy of Sciences, Fuzhou 350002, P. R. China

University of the Chinese Academy of Sciences, Beijing 100039, P. R. China

S Supporting Information
*

ABSTRACT: A series of 3d4f hydroxysulfates Ln2Cu(SO4)2(OH)4 (Ln = Sm, Eu, Tb, or Dy) have been
successfully obtained by the conventional hydrothermal
method. These compounds crystallize in the monoclinic
system in space group P21/c, showing a layered structure.
The layers are built by the LnO9 polyhedra and CuO4 planar
squares, which are separated by SO42 tetrahedra. The
topological structure of Sm3+ ions shows a distorted
honeycomb lattice, while Cu2+ ions are located at the center
of a honeycomb framework forming a triangle lattice. Magnetic
measurements reveal that the isostructural Ln2Cu(SO4)2(OH)4 exhibits dierent magnetic behaviors at low temperatures, which
may be attributed to the dierent contribution of 3d4f couplings.

INTRODUCTION
Hydroxysulfates have attracted much attention in the past
several decades, because of their various potential applications
such as cathode materials,1 porosity,2 and magnetic properties.3
Current interest in hydroxysulfates mainly focuses on
transition-metal or rare-earth-metal systems. For transitionmetal hydroxysulfates, their structures and magnetic properties
have been investigated intensively. For example, antlerite
Cu3(OH)4(SO4) features a three-legged ribbon structure built
by edge-sharing copper octahedra, behaving as a low-dimensional antiferromagnet with a small spin-canting. 4
Co5(OH)6(SO4)2(H2O)4 is composed of edge-sharing Co
OH octahedral layers and exhibits ferromagnetic behavior with
a Curie temperature of 14 K.5 Both
Na2Co3(OH)2(SO4)3(H2O)4 and Co3(OH)2(HSO4)2(SO4)(H2O)4 show a helical Co3(OH)2 ferrimagnetic chain structure,
exhibiting unusual slow magnetic relaxation behaviors.6 For
rare-earth-metal hydroxysulfates, the investigations focus on a
lanthanide contraction eect and a magnetocaloric eect
(MCE). For example, a series of compounds Ln(OH)(SO4)
(Ln = PrYb) exhibit a three-dimensional (3D) framework
composed of Ln3+ polyhedra, showing a remarkable lanthanide
contraction eect.7
Usually, the coexistence of lanthanides and 3d transitionmetal ions in a compound may lead to rich structural chemistry
and magnetic phenomena, because the diversity of coordinated
environments of lanthanide and transition-metal ions will aect
XXXX American Chemical Society

structural frameworks and magnetic exchanges. Also, the buried

4f electrons of lanthanides would have a smaller crystal-eld
eect than 3d transition-metal ions in the compounds.
Therefore, the large spinorbit coupling, single-ion anisotropy,
unquenched orbital angular momentum, and large spin values
of lanthanides ions may induce various interesting and
complicated magnetic behaviors in 3d4f metal-based compounds. These have been conrmed in many 3d4f systems
such as Na2GdMnO(AsO4)28 and Sr3HoCrO6.9,10 Although
3d4f systems have been studied intensively, hydroxysulfates
containing lanthanides and a 3d transition metal are very rare;
only YM(OH)3(SO4) (M = Cu or Ni)11,12 and Ce13Cr(HSO4)6(SO4)21(H2O)7513 have been reported.
Recently, we have successfully synthesized new transitionmetal hydroxysulfates by a hydrothermal reaction, i.e.,
M3(TeO3)(SO4)(OH)22H2O (M = Ni or Co).14 In this
work, we synthesized a series of new 3d4f hydroxysulfates
Ln2Cu(SO4)2(OH)4 (Ln = Sm, Eu, Tb, or Dy) by introducing
lanthanide ions into transition-metal hydroxysulfates. Herein,
we report on the discovery of a series of new 3d4f
hydroxysulfates Ln2Cu(SO4)2(OH)4 (Ln = Sm, Eu, Tb, or
Dy). Further, the structural features and magnetic behaviors are
also investigated.
Received: January 14, 2015
Revised: March 20, 2015

DOI: 10.1021/acs.cgd.5b00057
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Table 1. Crystal Data and Structural Renement Data for Ln2Cu(SO4)2(OH)4 (Ln = Sm, Eu, Tb, or Dy)
formula
fw
T, K
,
space group
a,
b,
c,
, deg
, deg
, deg
V, 3
Z
Dcalcd, g cm3
, cm1
maximum and minimum transmissions
GOF on F2
R1, wR2a
R1, wR2 (all data)
a

Sm2Cu(SO4)2(OH)4
624.44
room temperature
0.71073
P21/c
6.393(3)
6.792(3)
10.845(5)
90
98.616(9)
90
465.6(4)
2
4.454
152.22
1.0000, 0.6633
0.999
0.0229, 0.0582
0.0269, 0.0611

Eu2Cu(SO4)2(OH)4
627.66
room temperature
0.71073
P21/c
6.369(3)
6.760(3)
10.820(4)
90
98.600(9)
90
460.6(3)
2
4.526
162.05
1.000, 0.7136
1.077
0.0203, 0.0551
0.0225, 0.0566

Tb2Cu(SO4)2(OH)4
641.58
room temperature
0.71073
P21/c
6.321(2)
6.693(2)
10.757(4)
90
98.533(7)
90
450.1(3)
2
4.734
184.12
1.0000, 0.6558
1.019
0.0220, 0.0557
0.0243, 0.0567

Dy2Cu(SO4)2(OH)4
646.67
room temperature
0.71073
P21/c
6.304(4)
6.663(4)
10.724(6)
90
98.527(1)
90
445.5(5)
2
4.806
194.99
1.0000, 0.5156
1.134
0.0359, 0.0955
0.0397, 0.0990

R1 = ||F0| |Fc||/|F0|, and wR2 = [w(F02 Fc2)2/w(F02)2]1/2.

Figure 1. View of the oxygen coordination environments for (a) Sm, (b) Cu, and (c) S atoms.

report only its structure here. It must be noted that we cannot

synthesize single crystals of Ln2Cu(SO4)2(OH)4 (Ln = Sm, Eu, Tb, or
Dy) in the absence of K2TeO3 and H3BO3, indicating that such
additions may play important roles as mineralizers in the process of
hydrothermal reaction.
X-ray Crystallographic Studies. The small crystals of Ln2Cu(SO4)2(OH)4 (Ln = Sm, Eu, Tb, or Dy) (0.15 mm 0.15 mm
0.05 mm) were selected and mounted on glassy bers for single-crystal
X-ray diraction (XRD) measurements. Data were collected on a
Rigaku Mercury CCD diractometer equipped with graphitemonochromated Mo K radiation ( = 0.71073 ) at 293 K. The
data sets were corrected for Lorentz and polarization factors as well as
for absorption by the Multiscan method.15 The structures were
determined by direct methods and rened by full-matrix least-squares
tting on F2 by SHELX-97.16 All non-hydrogen atoms were rened
with anisotropic thermal parameters. The hydrogen atoms were
located at calculated positions and rened with isotropic thermal
parameters. The nal rened structural parameters were checked with
PLATON.17 Crystallographic data and structural renements are
summarized in Table 1. The nal rened atomic positions and
structural parameters are listed in Tables S112 of the Supporting
Information.
Magnetic Measurements. Magnetic measurements were performed using a commercial Quantum Design Physical Property
Measurement System (PPMS). Powdered samples of Sm2Cu(SO4)2(OH)4 (14.830 mg), Eu2Cu(SO4)2(OH)4 (8.760 mg), and
Dy2Cu(SO4)2(OH)4 (10.280 mg) were placed separately in a gel
capsule sample holder that was suspended in a plastic drinking straw.
The dc magnetic susceptibility was measured at 0.1 T from 300 to 2 K
(temperature scan of 5 K/min), and magnetization was measured at 2
K in an applied eld from 8 to 8 T (eld scan of 0.1 T/step). Low-

EXPERIMENTAL SECTION

Preparation of Ln2Cu(SO4)2(OH)4 (Ln = Sm, Eu, Tb, or Dy).

Single crystals of Ln2Cu(SO4)2(OH)4 (Ln = Sm, Eu, Tb, or Dy) were
synthesized by a conventional hydrothermal method. (1) For
Sm2Cu(SO4)2(OH)4, a mixture of 1.5 mmol of CuSO47H2O
(99.5%, 0.3745 g), 0.6 mmol of Sm2O3 (99.9%, 0.2087 g), 0.3 mmol
of K2TeO3 (99.5%, 0.0761 g), 0.5 mmol of H3BO3 (99.5%, 0.0309 g),
and 10 mL of deionized water was sealed in an autoclave equipped
with a Teon liner (28 mL). (2) For Eu2Cu(SO4)2(OH)4, a mixture of
1.5 mmol of CuSO47H2O (99.5%, 0.3745 g), 0.5 mmol of Eu2O3
(99.9%, 0.1770 g), 0.3 mmol of K2TeO3 (99.5%, 0.0761 g), 0.5 mmol
of H3BO3 (99.5%, 0.0309 g), and 10 mL of deionized water was sealed
in an autoclave equipped with a Teon liner (28 mL). (3) For
Tb2Cu(SO4)2(OH)4, a mixture of 1.5 mmol of CuSO47H2O (99.5%,
0.3745 g), 1 mmol of Tb4O7 (99.9%, 0.7477 g), 0.3 mmol of K2TeO3
(99.5%, 0.0761 g), 0.5 mmol of H3BO3 (99.5%, 0.0309 g), and 10 mL
of deionized water was sealed in an autoclave equipped with a Teon
liner (28 mL). (4) For Dy2Cu(SO4)2(OH)4, a mixture of 2 mmol of
CuSO47H2O (99.5%, 0.5008 g), 1 mmol of Dy2O3 (99.9%, 0.373 g),
0.3 mmol of K2TeO3 (99.5%, 0.0761 g), 1 mmol of H3BO3 (99.5%,
0.0618), and 10 mL of deionized water was sealed in autoclave
equipped with a Teon liner (28 mL). The autoclaves described above
were put into a furnace, heated at 210 C for 4 days under autogenous
pressure, and then cooled to room temperature at a rate of 2 C/h
for 4 days. The blue bulk crystals of Ln2Cu(SO4)2(OH)4 (Ln = Sm,
Eu, Tb, or Dy) were obtained and further dried at 60 C for 2 h. The
powdered samples were prepared by crushing single crystals of
Ln2Cu(SO4)2(OH)4, and their purities were conrmed by powder Xray diraction studies (Figure S1 of the Supporting Information). In
fact, the crystals of Tb2Cu(SO4)2(OH)4 were found to contain
powdered CuO impurities that were hard to clean up, and thus, we
B

DOI: 10.1021/acs.cgd.5b00057
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Figure 2. Structure of Sm2Cu(SO4)2(OH)4 for (a) 3D networks and (b) 2D layers constructed by SmO9 polyhedra and CuO4 squares.

Figure 3. Spinlattices built by (a) Sm3+ ions, (b) Cu2+ ions, and (c) a combination of Sm3+ and Cu2+ ions.
temperature magnetic susceptibilities were also measured with eldcooling (FC) and zero-eld-cooling (ZFC) regimes under 50 Oe. The
ac magnetic susceptibilities were measured at an amplitude of 3 Oe
with frequencies from 100 to 5000 Hz.

from 86.56(1) to 180. All of the CuO4 squares connect to six

Sm atoms through a pair of edge-sharing oxygen atoms
[O(1)O(2)] and four corner-sharing oxygen atoms [2O(1)
and 2O(2)]. S atoms are coordinated by four oxygen atoms,
forming SO42 tetrahedra with SO bond distances ranging
from 1.426(4) to 1.504(3) [average of 1.472(6) ] and O
SO bond angles ranging from 102.58(2) to 113.8(2) [mean
of 109.3(9)]. SO42 tetrahedra link to four Sm atoms through
corner-sharing [O(3)O(5)] or edge-sharing [O(3)O(5)]
oxygen atoms, while O(6) atoms form a dangling bond in
SO42 tetrahedra. According to the bond valence sum (BVS)
calculations, the values of Sm, Cu, and S atoms are 2.997, 1.867,
and 6.052, respectively, proving that these three atoms are
consistent with their ideal values. In addition, O(1) and O(2)
atoms in this compound are calculated to 0.944 and 0.928,
respectively, conrming both O(1) and O(2) atoms should be
OH groups for charge balancing the formula.
As shown in Figure 2a, the 3D structural framework of
Sm2Cu(SO4)2(OH)4 is composed of two-dimensional (2D)
layers and SO42 tetrahedra, in which the 2D layers in the bc
plane are composed of SmO9 polyhedra and CuO4 square
planes, while the layers are separated by SO42 tetrahedra. As
shown in Figure 2b, SmO9 polyhedra connect to each other
forming six-column tunnels in the layers, in which CuO4 square
planes are located inside the tunnels. To check the linkage of
polyhedra in the layers, it is noted that SmO9 polyhedra
connect to each other along the b-axis through face-sharing
oxygen atoms [O(1)O(2)O(3)] with the shortest
neighboring SmSm distance being 3.7(9) , while SmO9

RESULTS AND DISCUSSION

Structural Description. Single-crystal X-ray studies of
Ln2Cu(SO4)2(OH)4 (Ln = Sm, Eu, Tb, or Dy) reveal that all
the compounds are isostructural and crystallize in the
monoclinic system in space group P21/c. Thus, we take
Sm2Cu(SO4)2(OH)4 as a representative to describe their
structures in detail. For Sm2Cu(SO4)2(OH)4, one Sm atom,
one Cu atom, and one S atom are in an asymmetric unit, which
are located at Wycko positions 4e, 2b, and 4e, respectively. As
shown in Figure 1, the Sm atom is located in a 9-oxygencoordinated environment forming a SmO9 polyhedron with
SmO bond lengths in the range of 2.385(3)2.544(3) and
OSmO bond angles in the range of 55.08(1)148.28(1).
Each SmO9 polyhedron is surrounded by three Sm atoms, three
Cu atoms, and four S atoms, in which Sm connects to S atoms
by corner-sharing oxygen atoms [O(3)O(5)] or edge-sharing
oxygen atoms [O(3)O(5)], while Sm connects to Cu atoms
by two corner-sharing oxygen atoms [O(1) and O(2)] or one
pair of edge-sharing oxygen atoms [O(1)O(2)]. Sm atoms
connect to each other by one pair of edge-sharing oxygen
atoms [O(5)O(5)] or two pairs of face-sharing oxygen atoms
[O(1)O(2)O(3)]. The Cu coordination corresponds to a
CuO4 square plane with CuO bond lengths ranging from
1.958(3) to 1.964(3) and OCuO bond angles ranging
C

DOI: 10.1021/acs.cgd.5b00057
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Figure 4. Temperature dependence of magnetic susceptibility and the corresponding reciprocal for (a) Sm2Cu(SO4)2(OH)4, (b)
Eu2Cu(SO4)2(OH)4, and (c) Dy2Cu(SO4)2(OH)4.

Figure 5. TT plot for (a) Sm2Cu(SO4)2(OH)4, (b) Eu2Cu(SO4)2(OH)4, and (c) Dy2Cu(SO4)2(OH)4. The inset shows low-temperature
susceptibilities obtained with zero-eld-cooling (ZFC) and eld-cooling (FC) regimes.

Sm2Cu(TeO3)2(SO4)218 and Na3SmMn3O3(AsO4)3.19 For

Eu2Cu(SO4)2(OH)4 (Figure 4b), a peak of susceptibility is
observed at 12.8 K, showing the onset of antiferromagnetic
ordering. Typical CurieWeiss behavior is observed between
150 and 300 K, giving a Curie constant C of 4.8(7) emu mol1
K and a Weiss temperature of 186.2(1) K. The eective
magnetic moment can be calculated to be 6.2(4) B, which is
much larger than the theoretical value of 1.73 B for one Cu2+
(S = 1/2; g = 2) and two Eu3+ ions (S = 0; gJ = 1). This may also
be due to the fact that the ground state (7F0) of Eu3+ is close to
the rst excited state (7F1) and the second excited state (7F2),
leading to partial magnetic ions sitting at the excited state. It is
well-known that the magnetic moment of Eu3+ is experimentally observed to be near 3.4 B/mol of Eu in general.20
However, the ground state of Eu3+ at low temperatures is
diamagnetic (7F0), and the magnetic interactions in Eu2Cu(SO4)2(OH)4 may arise from Cu2+Cu2+ antiferromagnetic
exchange coupling. It is noted that the coupling distance
between Cu2+ ions is quite large and an antiferromagnetic
ordering at 12.8 K may indicate a strong 3d4f interaction in
the system. A similar magnetic behavior has also been observed
in Eu2Cu(TeO3)2(SO4)2.18 For Dy2Cu(SO4)2(OH)4 (Figure
4c), a sudden upturn of susceptibility appears at 13.5 K,
indicating the onset of ferromagnetic ordering. A typical
CurieWeiss behavior is observed between 60 and 300 K,
giving a Curie constant C of 28.3(1) emu mol1 K and a Weiss
temperature of 6.3(5) K. The eective magnetic moment can
be calculated to be 15.0(5) B, which is close to the theoretical
value of 15.15 B for one Cu2+ (S = 1/2; g = 2) and two Dy3+
ions (S = 15/2; gJ = 4/3).

polyhedra connect to each other along the c-axis through edgesharing oxygen atoms [O(5)O(5)] with a SmSm distance
of 4.1(9) . It must also be noted that CuO4 square planes are
located inside the tunnels built by SmO9 polyhedra, resulting in
many irregular triangles with 3-O(1)H and 3-O(2)H, in
which the SmCu distances are 3.4(3), 3.9(5), and 4.0(3) .
Removing nonmagnetic OH and SO42 groups from the
structure of Sm2Cu(SO4)2(OH)4, we note that the topological
structure of Sm3+ ions shows a distorted honeycomb lattice
(Figure 3a), while Cu2+ ions are arranged in a triangle lattice
(Figure 3b). The spinlattice built by magnetic Sm3+ and Cu2+
ions is shown in Figure 3c.
Magnetic Properties. Figure 4 shows the temperature
dependences of magnetic susceptibility () and the corresponding reciprocal (1) for Ln2Cu(SO4)2(OH)4 (Ln = Sm, Eu, or
Dy). For Sm2Cu(SO4)2(OH)4 (Figure 4a), the magnetic
susceptibility increases with a decrease in temperature, while
a sudden upturn is observed at 5.4 K, indicating the onset of
ferromagnetic ordering. Typical CurieWeiss behavior is
observed between 220 and 300 K, giving a Curie constant C
of 1.5(2) emu mol1 K and a Weiss temperature of
219.0(2) K. The eective magnetic moment can be calculated
to be 3.4(9) B based on the equation of eff2 = 8C, which has a
large derivation from the theoretical value of 2.11 B for one
Cu2+ (S = 1/2; g = 2) and two Sm3+ ions (S = 5/2; gJ = 2/7). This
may be due to the fact that the ground state (6H5/2) of Sm3+ is
quite close to the rst excited state (6H7/2), leading to partial
magnetic ions sitting at the excited state, which always makes
the experimental value inconsistent with the theoretical value
calculated from the pure ground state. Similar phenomena can
also be found in many SmO-based compounds such as
D

DOI: 10.1021/acs.cgd.5b00057
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Figure 6. Curve of magnetization (M) vs applied eld (H) at 2 K for (a) Sm2Cu(SO4)2(OH)4, (b) Eu2Cu(SO4)2(OH)4, and (c)
Dy2Cu(SO4)2(OH)4. The inset shows the hysteresis loop in the range of 8 to 8 T.

Table 2. Magnetic Data Observed for Ln2Cu(SO4)2(OH)4 (Ln = Sm, Eu, or Dy)
ion
Sm3+
Eu3+
Dy3+
a

C, emu mol1 K

eff, B

, K

TC, K

magnetic ground statea

/2
0
15
/2

1.5(2)
4.8(7)
28.3(1)

3.4(9)
6.2(4)
15.0(5)

219.0(2)
186.2(1)
6.3(5)

3.4
12.8
5

FIM
AFM
FM

gJ
2

/7
1
4
/3

Abbreviations: FIM, ferrimagnetic; AFM, antiferromagnetic; FM, ferromagnetic.

Figure 5 shows the TT plot for Ln2Cu(SO4)2(OH)4 (Ln =

Sm, Eu, or Dy). For Sm2Cu(SO4)2(OH)4 (Figure 6a), the T
T plot decreases gradually and reaches its minimum at 8 K
with a decrease in temperature, while a rapid upturn appears at
low temperatures, indicating the existence of ferromagnetic
correlation. A clear history is seen below 3.4 K between zeroeld-cooling (ZFC) and eld-cooling (FC) regimes, conrming
the characteristic irreversibility of such a ferromagnetic
component (see the inset of Figure 5a). Considering the
negative Weiss temperature and ferromagnetic component, the
magnetic ground state of Sm2Cu(SO4)2(OH)4 is suggested to
be of a ferrimagnetic type. For Eu2Cu(SO4)2(OH)4 (Figure
5b), the TT plot decreases gradually with a decrease in
temperature, and no peaks can be observed, supporting a
collinear antiferromagnetic ground state. For Dy 2 Cu(SO4)2(OH)4 (Figure 5c), the TT plot increases gradually
with a decrease in temperature, while a rapid increase with a
maximum is observed at 5 K, conrming the appearance of
ferromagnetic ordering.
Figure 6 shows the isothermal magnetization as a function of
applied eld (MH) at 2 K for Ln2Cu(SO4)2(OH)4 (Ln = Sm,
Eu, or Dy). For Sm2Cu(SO4)2(OH)4 (Figure 6a), the
magnetization increases rapidly at the low-eld range and
then increases gradually with an increasing eld up to 8 T. It is
noted that an anomaly is observed at 4 T, indicating a ledinduced magnetic transition. A clear hysteresis is observed at H
4 T with increasing and decreasing eld regimes (the inset of
Figure 6a), supporting the appearance of eld-induced
magnetic transition. For Eu2Cu(SO4)2(OH)4 (Figure 6b), the
magnetization increases linearly with an increasing eld and
does not saturate at 8 T. This nding is in good agreement with
a collinear antiferromagnetic ground state. For Dy2Cu(SO4)2(OH)4 (Figure 6c), the magnetization rapidly increases
and saturates at low eld. Furthermore, clear hysteresis and
remanent magnetization near H = 0 are observed (the inset of
Figure 6c), supporting the ferromagnetic ground state.
To further identify the nature of magnetic behaviors of
Ln2Cu(SO4)2(OH)4 (Ln = Sm, Eu, or Dy), the ac magnetic
susceptibilities were measured with dierent frequencies

(Figure S2 of the Supporting Information). We note that the

peaks of susceptibilities do not shift to high temperatures with
an increase in frequency, showing no frequency-dependent
behaviors in the systems, which give concrete evidence ruling
out the existence of single-molecule magnet (SMM) behavior
or spin-glass behavior.
It is well-known that magnetic behaviors of solid materials
are related strongly to their structures. For pure 4f lanthanidebased compounds, similar magnetic behaviors are usually
observed because of their similar structural features.2123
However, we note that Ln2Cu(SO4)2(OH)4 (Ln = Sm, Eu,
or Dy) compounds exhibit quite dierent magnetic behaviors,
although they have a similar structural feature. This may
indicate that lanthanide Ln3+ ions play a remarkable role in
magnetic behaviors of such 3d4f heterometallic hydroxysulfates. Table 2 shows the magnetic behaviors of Ln2Cu(SO4)2(OH)4 (Ln = Sm, Eu, Tb, or Dy). The change in
Weiss temperature from negative to positive is observed from
Sm3+ to Dy3+ in the systems, showing that the nearest magnetic
interactions vary from antiferromagnetic to ferromagnetic
between magnetic ions with the decreasing radii of Ln3+ ions.
This character is consistent with that observed in Ln2Cu(TeO 3 ) 2(SO 4) 2 ,18 [Ln 2Cu 4 (fsaaep)4 (NO3 ) 6]0.5(CH3 OH
H2O),24 and {Ln2[Cu(opba)]3}S,25 in which the coupling
exchanges between Ln3+ and Cu2+ ions are antiferromagnetic
for light rare earths and ferromagnetic for heavy rare earths.26
Infrared Spectroscopy. Ln2Cu(SO4)2(OH)4 (Ln = Sm,
Eu, or Dy) compounds are characterized by the FT-IR
spectrum (Figure S3 of the Supporting Information). It is
noted that all the infrared spectra are quite similar, supporting
polyhedra of these compounds with similar oxygen coordination environments. For hydroxyl groups, two sharp peaks at
3573 and 3435 cm1 are due to the stretching modes of OH
groups and another band at around 1635 and 870 cm1 can be
attributed to their bending modes. For sulfate groups, all the
fundamental modes (14) could be observed clearly in the
spectrum. The 1 (970 cm1) and 2 (454 cm1) modes
indicate the lowering of site symmetry from the Td group of
sulfate groups. In particular, the 3 mode is split into three
E

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separate peaks between 1235 and 1028 cm1, and those

between 730 and 600 cm1 can be attributed to the 4 mode of
the sulfate groups.

Johnson, K.; Sovesky, R.; Stroudt, C.; Renn, R. A. Inorg. Chem. 2011,
50, 836.
(8) West, J. P.; Queen, W. L.; Hwu, S.-J.; Michaux, K. E. Angew.
Chem., Int. Ed. 2011, 50, 3780.
(9) Hardy, V.; Martin, C.; Martinet, G.; Andre, G. Phys. Rev. B 2006,
74, 064413.
(10) Smith, M. D.; zur Loye, H.-C. Chem. Mater. 2000, 12, 2404.
(11) Wang, X. Q.; Liu, L. M.; Jacobson, A. J. J. Solid State Chem.
1999, 147, 641.
(12) Wang, X. Q.; Liu, L. M.; Ross, K.; Jacobson, A. J. Solid State Sci.
1998, 2, 109.
(13) Casari, B. M.; Langer, V. Eur. J. Inorg. Chem. 2007, 22, 3514.
(14) Tang, Y. Y.; Guo, W. B.; Zhang, S. Y.; Yang, M.; He, Z. Z. Cryst.
Growth Des. 2014, 14, 5206.
(15) CrystalClear, version 1.3.5; Rigaku Corp.: The Woodlands, TX,
1999.
(16) Sheldrick, G. M. Crystallographic Software Package, SHELXTL,
version 5.1; Bruker-AXS: Madison, WI, 1998.
(17) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7.
(18) Lin, J.; Chai, P.; Diefenbach, K.; Shatruk, M.; Albrecht-Schmitt,
T. E. Chem. Mater. 2014, 26, 2187.
(19) West, J. P.; Hwu, S.-J.; Queen, W. L. Inorg. Chem. 2009, 48,
8439.
(20) Kittel, C. Introduction of Solid State Physics, 6th ed.; Wiley: New
York, 1986.
(21) Thompson, C. M.; Tan, X. Y.; Kovnir, K.; Garlea, V. O.;
Gippius, A. A.; Yaroslavtsev, A. A.; Menushenkov, A. P.; Chernikov, R.
V.; Buttgen, N.; Kratschmer, W.; Zubavichus, Y. V.; Shatruk, M. Chem.
Mater. 2014, 26, 3825.
(22) Munoz, A.; Martinez-Lope, M. J.; Alonso, J. A.; Fernandez-Diaz,
M. T. Eur. J. Inorg. Chem. 2012, 35, 5825.
(23) Martinez-Coronado, R.; Retuerto, M.; Fernandez, M. T.;
Alonso, J. A. Dalton Trans. 2012, 41, 8575.
(24) Andruh, M.; Ramade, I.; Codjovi, E.; Guillou, O.; Kahn, O.;
Trombe, J. C. J. Am. Chem. Soc. 1993, 115, 1822.
(25) Kahn, M. L.; Mathoniere, C.; Kahn, O. Inorg. Chem. 1999, 38,
3692.
(26) Kahn, O.; Guillou, O. Research Frontiers in Magnetochemistry;
OConnor, C., Ed.; World Scientic: Singapore, 1993.

CONCLUSIONS
We have successfully obtained a series of novel 3d4f
hydroxysulfates Ln2Cu(SO4)2(OH)4 (Ln = Sm, Eu, Tb, or
Dy) by means of a conventional hydrothermal method. All of
the compounds are isostructural and crystallize in the
monoclinic system in space group P21/c. A layered structure
is composed of LnO9 polyhedra and CuO4 planar squares, and
the layers are further separated by SO42 tetrahedra. The
topological structure of Ln3+ ions corresponds to a distorted
honeycomb lattice, while Cu2+ ions are located at the hole of
the honeycomb framework forming a triangle lattice. Magnetic
measurements conrm that Ln2Cu(SO4)2(OH)4 compounds
exhibit dierent magnetic properties, in which Sm2Cu(SO4)2(OH)4 shows a ferrimagnetic ground state and Eu2Cu(SO4)2(OH)4 displays antiferromagnetic ordering at 12.8 K,
while Dy2Cu(SO4)2(OH)4 shows ferromagnetic ordering at 5
K. We believe that this study of Ln2Cu(SO4)2(OH)4 is a typical
example for investigating dierent 3d4f coupling exchanges
between magnetic ions, which strongly aect their magnetic
behaviors.

ASSOCIATED CONTENT

S Supporting Information
*

Final rened atomic positions and structural parameters, ac

magnetic susceptibilities, infrared spectra, and simulated and
experimental powder X-ray patterns for Ln2Cu(SO4)2(OH)4
(Ln = Sm, Eu, Tb, or Dy). The Supporting Information is
available free of charge on the ACS Publications website at
DOI: 10.1021/acs.cgd.5b00057.

AUTHOR INFORMATION

Corresponding Author

*E-mail: hcz1988@hotmail.com or hezz@fjirsm.ac.cn.

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
This work was nancially supported by the National Basic
Research Program of China (2012CB921701) and the National
Natural Science Foundation of China (21403234).

REFERENCES

(1) Subban, C. V.; Ati, M.; Rousse, G.; Abakumov, A. M.; Van
Tendeloo, G.; Janot, R.; Tarascon, J.-M. J. Am. Chem. Soc. 2013, 135,
3653.
(2) Rujiwatra, A.; Kepert, C. J.; Claridge, J. B.; Rosseinsky, M. J.;
Kumagai, H.; Kurmoo, M. J. Am. Chem. Soc. 2001, 123, 10584.
(3) Ben Salah, M.; Vilminot, S.; Andre, G.; Bouree-Vigneron, F.;
Richard-Plouet, M.; Mhiri, T.; Kurmoo, M. Chem. Mater. 2005, 17,
2612.
(4) Vilminot, S.; Andre, G.; Bouree-Vigneron, F.; Richard-Plouet, M.;
Kurmoo, M. Inorg. Chem. 2007, 46, 10079.
(5) Ben Salah, M.; Vilminot, S.; Andre, G.; Richard-Plouet, M.;
Takagi, S.; Kurmoo, M. J. Am. Chem. Soc. 2006, 128, 7972.
(6) Zhang, X.-M.; Li, C.-R.; Zhang, X.-H.; Zhang, W.-X.; Chen, X.-M.
Chem. Mater. 2008, 20, 2298.
(7) Zehnder, R. A.; Wilson, C. S.; Christy, H. T.; Harris, K. S.;
Chauhan, V.; Schutz, V.; Sullivan, M.; Zeller, M.; Fronczek, F. R.;
Myers, J. A.; Dammann, K.; Duck, J.; Smith, P. M.; Okuma, A.;
F

DOI: 10.1021/acs.cgd.5b00057
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