Synthesis, crystal structures, and magnetic properties of two heterobinuclear complexes with a dissymmetrical oxamidate ligand

Article abstract of DOI:10.1134/S1070328412110048

Two heterobimetallic compounds {[CuLMn(H₂O)₃ · 1.75H₂O]₂} _n (I) and {[CuLCo(H ₂O)₃ · 2H₂O]₂} _n (II) (H₄L = N-(2,5-dicarboxyl phenyl)-N′-(2-amino propyl)oxamide) have been synthesized and characterized by IR, elemental analysis, single-crystal X-ray diffraction, and magnetic properties. They crystallize in the triclinic system with space group P1. The structures of the complexes consist of neutral tetranuclear units formed through syn-anti carboxylate bridges in ladder-like chains. The magnetic properties of complexes I and II indicated antiferromagnetic interaction between the metal ions.

Full text of DOI:10.1134/S1070328412110048

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2013, Vol. 39, No. 1, pp. 119–125. © Pleiades Publishing, Ltd., 2013.
Synthesis, Crystal Structures, and Magnetic Properties of Two
Heterobinuclear Complexes with a Dissymmetrical Oxamidate Ligand1
B. L. Liu, Y. X. Wang, G. P. Li, and R. J. Tao*
Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University,
Kaifeng, Henan, 475004 P.R. China
*eꢀmail: rjtao@henu.edu.cn
Received July 14, 2011
Abstract
2H2O]2}n (II) (H4L = Nꢀ(2,5ꢀdicarboxyl phenyl)ꢀN
characterized by IR, elemental analysis, singleꢀcrystal Xꢀray diffraction, and magnetic properties. They crysꢀ
—
Two heterobimetallic compounds {[CuLMn(H2O)3
⋅ 1.75H2O]2}n (I) and {[CuLCo(H2O)3 ⋅
'ꢀ(2ꢀamino propyl)oxamide) have been synthesized and
P 1.
tallize in the triclinic system with space group
The structures of the complexes consist of neutral tetranuꢀ
clear units formed through synꢀanti carboxylate bridges in ladderꢀlike chains. The magnetic properties of
complexes and II indicated antiferromagnetic interaction between the metal ions.
I
DOI: 10.1134/S1070328412110048
INTRODUCTION
ion [5–9]. Along this line, oxamato copper(II) comꢀ
plexes used for the rational design of heteropolynuclear
compounds have received growing attention [10–12].
In the past few decades, research on molecular
magnetic materials has been of great interest [1–4].
Mixedꢀmetal materials are a major research area for
many groups around the world. In order to gain conꢀ
trol of both the nuclearity and the topology, a successꢀ
ful strategy is represented by the soꢀcalled “complexꢀ
asꢀligand” approach, utilizing a metal complex as a
Recently, we described three mononuclear copper(II)
complexes [CuL]n (L = NꢀbenzoateꢀN
–
'
ꢀ(2ꢀaminoꢀ
ethyl)oxamido (Oxbe), 2ꢀ(2ꢀ(2ꢀaminoethylamino)ꢀ2ꢀ
oxoacetamido)terephthalic acid (Aeoe) and Nꢀ(2ꢀamiꢀ
noterephthalic acid)ꢀN'ꢀ(1,3ꢀpropanediamine)oxamiꢀ
ligand to coordinate an appropriate additional metal date (Aeop):
2–
O
–
O
O
O
O
O
O
N
N
O
N
N
O
Cu
Cu
NH2
O
NH2
[Cu(Oxbe)]–
[Cu(Aeoe)]2–
2–
2–
O
O
O
O
O
O
O
O
N
N
O
N
N
O
Cu
Cu
NH2
NH2
O
O
[Cu(Aeop)]2–
[CuL]2
1
The article is published in the original.
119

120
LIU et al.
as precursors for the preparation of both homoꢀ and
heterometallic complexes [13–16]. We have now sucꢀ
cessfully synthesized a new oxamato copper(II) comꢀ
Synthesis of {[CuLMn(H2O)3
0.1 mmol (0.044 g) amount of Na2[CuL]
solved in 15 mL of water, and 15 mL of a DMF solution
containing 0.1 mmol (0.0244 g) Mn(CH3COO)2 4H2O
was added under constant stirring. The resulting blueꢀ
violet solution was filtered, and single crystals suitable
for Xꢀray crystallographic analysis were obtained by
slow evaporation of the solution. The yield was 0.036 g
⋅
1.75H2O]2}n (I).
A
⋅
H2O was disꢀ
plex CuL (L = Nꢀ(2,5ꢀdicarboxyl phenyl)ꢀN
do propyl)oxamide) and obtained two new ladderꢀlike
chain complexes – {[CuLMn(H2O)3 1.75H2O]2}n (
and {[CuLCo(H2O)3 2H2O]2}n (II). The crystal strucꢀ
'ꢀ(2ꢀamiꢀ
⋅
⋅
I)
⋅
tures and magnetic properties of complexes
have also been investigated.
I and II
(70%)
.
For C13H20.50N3O10.75MnCu
anal. calcd., %: C, 30.66;
EXPERIMENTAL
H, 4.06;
H, 4.01;
N, 8.25.
N, 8.21.
Found, %:
C, 30.72;
Materials and methods. All reagents were purꢀ
chased from commercial sources and used without
further purification. Elemental analyses for carbon,
hydrogen, and nitrogen were performed on a Perkinꢀ
Elmer 2400II elemental analyzer. The infrared spectra
were recorded on an Avatarꢀ360 spectrometer using
KBr pellets in the range of 400–4000 cm–1. Variable
temperature magnetic susceptibility data were obꢀ
Synthesis of {[CuLCo(H2O)3
plex II was prepared in a similar way as
CoCl2 6H2O being used instead of Mn(CH3COO)2
⋅
2H2O]2}n (II). Comꢀ
I
except for
⋅
⋅
4H2O. The yield was 0.032 g (62%).
For C13H21N3O11CuCo
tained on microcrystalline samples from 2 to 300 K in anal. calcd., %: C, 30.15;
H, 4.09;
H, 4.04;
N, 8.11.
N, 8.07.
a magnetic field of 10 kG, using a Quantum Design
MPMSꢀ7 SQUID magnetometer. Diamagnetic corꢀ
rections were made with Pascal parameters for all conꢀ
stituent atoms.
Found, %:
C, 30.22;
Xꢀray crystallography. The single crystals used for
data collection of compounds and II were mounted
on a Bruker Smart APEX diffractometer with a CCD
detector using graphite monochromated Mo α radiaꢀ
tion ( = 0.71073 ). Lorentz and polarization factors
I
Synthesis of the ligand H4L. A 5 mmol (0.682 g)
portion of ethyl oxalyl chloride in 10 mL of THF
(THF = tetrahydrofuran) was added dropwise to
40 mL of a THF solution of 5 mmol (0.93 g) of 2ꢀamiꢀ
noherephthalic acid. After one hour, the mixture was
added dropwise into a solution which contained
30 mL of absolute ethanol and 4.5 mL of 1,2ꢀproꢀ
K
λ
Å
were applied for the intensity data and absorption corꢀ
rections were performed using the SADABS program
[17]. The crystal structures were solved using the
SHELXL program and refined using full matrix leastꢀ
squares [18]. The positions of hydrogen atoms were
calculated theoretically and included in the final cyꢀ
cles of refinement in a riding model along with the atꢀ
tached carbons. Crystal data collection and refineꢀ
ment parameters are given in Table 1.
panediamine at 0°C. The resulting solution was stirred
for 3 h, and H4L was precipitated as a white powder,
washed with ethanol and dried under vacuum. The
yield was 1.1 g (71%).
Supplementary material for structures
been deposited with the Cambridge Crystallographic
Data Centre (no. 730894 ( ), 730895 (II); deposit@ccdc.
I and II has
For C13H15N3O6
anal. calcd., %: C, 50.49;
Found, %: C, 50.43;
H, 4.89;
H, 4.83;
N, 13.59.
N, 13.66.
I
cam.ac.uk or http://www.ccdc.cam.ac.uk).
Synthesis of the copper(II) precursor (CuL).
5 mmol (1.546 g) amount of H4L and 20 mmol (0.8 g)
of NaOH were dissolved in 100 mL of water. Then
A
RESULTS AND DISCUSSION
Xꢀray single crystal structures analyses have reꢀ
vealed that complexes I and II crystallize in the triclinꢀ
5 mmol (0.7623 g) of CuCl2
sulting violetꢀred solution was filtered and concentratꢀ
ed to 20 mL. Then ethanol was added slowly into the
filtrate, and Na2[CuL] H2O precipitated as a red
⋅ 2H2O was added. The reꢀ
P 1.
ic system, space group
They are similar in strucꢀ
ture and both consist of binuclear neutral molecule
and three coordinated water and a solvate water moleꢀ
cules, as shown in Fig. 1. The structural parameters of
⋅
polycrystalline powder and was washed with ethanol
and dried under vacuum at room temperature. The
yield was 2.2 g (89%).
the CuL fragment in I and II are almost the same. The
Cu ion is in a distorted square pyramidal CuN3O2 surꢀ
rounding. It is coordinated by one oxygen atom and
three nitrogen atoms from oxamidate bridges, and the
apical position is occupied by another carboxylic oxygen
For C13H13N3O7Na2Cu
anal. calcd., %: C, 36.08;
Found, %: C, 36.03;
H, 3.03;
H, 3.01;
N, 9.71.
N, 9.77.
atom with a bond length of 2.554
Å for I and 2.516 Å
for II. These bonds are longer than those in other
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
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2013

SYNTHESIS, CRYSTAL STRUCTURES, AND MAGNETIC PROPERTIES
121
Table 1. Crystallographic data and refinement parameters
for complexes and II
complexes reported by us [13, 14]. The Cu–N bond
lengths range between 1.901(3) and 2.017(3) in
1.894(3) and 2.015(3) in II. They are comparable
with the range found in the literature [13]. Mn(II),
and Co(II) are both coordinated by two oxygen atoms
from one oxamido ligand, three oxygen atoms from
water molecules and one oxygen atom from another
carboxylic group. The distances from copper to manꢀ
I
Å
I,
Å
Value
Parameter
I
II
Formula weight
Crystal system
Space group
509.30
517.80
Triclinic
Triclinic
ganese for
5.359 , respectively. The Mn–O bond lengths are in
the range of 2.154(3)–2.233(3) , the Co–O bond
lengths are 2.086(3)–2.143(3) , similar to values reꢀ
ported previously [13, 14].
I, copper to cobalt for II are 5.471 and
Å
P1
P1
Å
Å
a
,
Å
Å
Å
9.3093(17)
9.6018(18)
11.285(2)
81.693(3)
72.698(3)
82.159(3)
948.3(3)
2
9.2330(10)
9.4977(10)
11.2446(12)
82.633(2)
73.036(2)
82.067(2)
930.10(17)
2
b
,
In complex , as an example, the binuclear moleꢀ
I
c
,
cules are linked by coordinative bonds between carꢀ
boxylic oxygen atoms and Mn ions to give tetranuclear
neutral loops. These tetranuclear neutral loops are furꢀ
ther associated by coordinative bonds between carboxꢀ
ylic oxygen atoms and Cu ions to form a new ladderꢀ
like chain structure (Fig. 2). Selected bond lengths and
angles are listed in Table 2.
α
, deg
β
, deg
γ, deg
V
,
Å3
The ligand H4L exhibits a
the oxamidate group at
1636 cm–1 [19], a νas(COO)
(COOH)) vibration band at
1673 cm–1 [20], and
the bands of the (N–H) group (oxamidate group) at
2986 and 3110 cm–1. These bands are all missing in
ν(C=O) vibration band of
Z
∼
ρcalcd, g cm–3
(Mo
α), mm–1
, K
1.784
1.849
(ν
∼
μ
K
1.850
2.101
ν
∼
T
293(2)
293(2)
the spectrum of the three complexes because of loss of
the protons of both the COOH and N–H (oxamidate
group) groups. The new sharp strong band observed in
complexes I
(1652 cm–1) and II (1653 cm–1) is the reꢀ
sult of an overlap between νas(COO) of the ionized
λ
,
Å
0.71073
0.71073
Index ranges
–11
–11
–13
≤
≤
≤
h
k
l
≤
≤
≤
8,
11, –11
12 –13
–10
≤
≤
≤
h
k
l
≤
≤
≤ 7
10,
11,
carboxylate group and the vibration of the oxamidate
group (ν(C=O)) acting in bidendate mode. In addiꢀ
Reflections collected
4898
4630
tion, the –NH2 vibration for H4L was present for all
complexes and with a small shift from 3426 cm–1 for
Independent reflection 3320 (0.0151) 3255 (0.0165)
Rint
(
)
complex I
and 3422 cm–1 for II. Such a red shift indiꢀ
Reflections with
Parameters
I
≥
2
σ
(
I
)
2672
271
2548
271
cates that the nitrogen atom of –NH2 coordinates to
the copper ion.
The magnetic susceptibility of complex
measured in the range of 2–300 K. At room temperaꢀ
ture, the μeff value of is 5.98 μB. Upon cooling, it deꢀ
creases regularly, approaching a minimum around 2 K
with μeff = 4.81 μB
I has been
Goodnessꢀofꢀfit
1.077
1.201
R1
,
,
wR2
(
I
≥
2
σ
(
I
))*
0.0419, 0.1129 0.0410, 0.1094
0.0545, 0.1190 0.0565, 0.1153
0.552/–0.412 0.400/–0.484
I
R1
wR2 (all data)*
Å–3
.
Δρmax
/
Δρmin
,
e
There are two main kinds of magnetic interactions
for the present systems, namely: (i) Cu(1)–Mn(1) and
Cu(1)#1–Mn(1)#1 through a cisꢀoxamidate bridge;
(ii) Cu(1)–Mn(1)#3 and Mn(1)#1–Cu(1)#2 through
the cisꢀanti carboxylate oxygen bridge, as shown in Fig. 2.
1/2
2
⎡
⎤
.
wR =
F ,
o
w(F − Fc 2)2/ w(F 2)2
*
R =
1
F
o
− Fc
∑
∑
2
o
o
∑
∑
⎣
⎦
On the basis of these considerations, we take the
The interaction (i) in complex I is wellꢀknown to
system as an isolated binuclear moiety with
(i) Cu(1)–Mn(1) and Cu(1)#1–Mn(1)#1 through a
cisꢀoxamidate bridge and take (ii) into account as inꢀ
teractions between these binuclear moieties. The magꢀ
netic analysis was then carried out by using the theoꢀ
retical expression of the magnetic susceptibility deꢀ
favor an exceptionally strong antiferromagnetic interꢀ
action [21]. For (ii), it is evident that copper(II) orbitꢀ
als are mismatched for interaction to take place
through the synꢀanti carboxylate group, since the exꢀ
change pathway Cu(II)–O–C–O–Mn(II) involves
an axial position in the Cu(1) ( ) direction [22]. This
dz2
fact should cause a weak magnetic interaction.
ˆ
ˆ
ˆ
duced from the spin Hamiltonian
=
−2JSCu(1)SMn(1)
H
.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
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122
LIU et al.
(а)
(b)
O(5)
O(2)
O(6)
O(1)
O(3)
O(4)
O(4)
O(3)
O(1)
N(3)
N(1)
O(6)
O(2
Co(1)
w)
O(3w)
Cu(1)
N(2)
Cu(1)
N(3)
Mn(1)
Cu
Mn
N
O(3w)
N(1)
N(2)
O(2w)
O(2)
O(5)
O(1w)
O
O(1w)
C
Fig. 1. Molecular structures of complexes
I
(a) and II (b). The hydrogen atoms and solvent water molecules are omitted for clarity.
(a)
O(1
#1
#1
O(2w)
w)
#1
#1
#1
O(5)
N(2)
N(3)
O(2)
#1
Mn(1)
#1
Cu(1)
#1
O(4)
#1
O(1)
#1
#1
O(6)
N(1)
O(3w)
Cu
Mn
N
O(3)
O(4)
#1
O(3)
O
#1
N(1)
O(6)
O(1)
O(3
w
)
C
Cu(1)
Mn(1)
#1
O(2)
O(2w)
N(3)
N(2)
O(5)
O(1w)
(b)
Cu
Mn
N
O
C
Fig. 2. The tetranuclear unit structure of complex (a) I; 1D ladderꢀlike chain structure of complex I (b). The hydrogen atoms and
#1
solvent water molecules are omitted for clarity. Symmetry transformations used to generate equivalent atoms:
–
x
+ 2, –
y, –
z.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
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2013

SYNTHESIS, CRYSTAL STRUCTURES, AND MAGNETIC PROPERTIES
123
Table 2. Selected bond lengths (Å) and angles (deg) for complex I and II*
Bond
d,
Å
Bond
d, Å
I
Cu(1)–O(4)
Cu(1)–N(1)
Mn(1)–O(1)#1
Mn(1)–O(6)
1.892(3)
1.967(3)
2.154(3)
2.182(3)
2.195(4)
Cu(1)–N(2)
Cu(1)–N(3)
1.901(3)
2.017(3)
2.167(3)
2.190(3)
2.233(3)
Mn(1)–O(2
w
)
Mn(1)–O(5)
Mn(1)–O(3
w)
Mn(1)–O(1w
)
II
Cu(1)–O(3)
Cu(1)–N(3)
1.886(3)
1.971(3)
2.086(3)
2.092(3)
2.116(3)
Cu(1)–N(1)
Cu(1)–N(2)
Co(1)–O(2)
Co(1)–O(1)
1.894(3)
2.015(3)
2.091(3)
2.111(3)
2.143(3)
Co(1)–O(3
w)
Co(1)–O(6)#1
Co(1)–O(2
w
)
Co(1)–O(1
w)
Angle
ω
, deg
Angle
ω, deg
I
O(4)Cu(1)N(1)
O(4)Cu(1)N(3)
N(1)Cu(1)N(3)
O(1)#1Mn(1)O(6)
O(1)#1Mn(1)O(5)
O(6)Mn(1)O(5)
95.47(12)
94.99(12)
168.40(13)
102.96(10)
178.52(11)
75.70(10)
175.86(14)
94.17(15)
86.80(12)
87.09(10)
N(2)Cu(1)N(1)
N(2)Cu(1)N(3)
O(1)#1Mn(1)O(2
85.15(13)
83.84(13)
89.42(12)
90.85(12)
89.96(12)
86.44(16)
90.09(13)
94.22(11)
162.64(10)
93.50(13)
w
)
O(2
w
w
)Mn(1)O(6)
O(2
)Mn(1)O(5)
O(1)#1Mn(1)O(3
O(6)Mn(1)O(3
O(1)#1Mn(1)O(1
O(6)Mn(1)O(1
O(3 )Mn(1)O(1
w
)
O(2
O(5)Mn(1)O(3
O(2 )Mn(1)O(1
O(5)Mn(1)O(1
w)Mn(1)O(3
w
)
)
w)
w
)
w
)
w
w
)
w)
w
w
w)
II
O(3)Cu(1)N(3)
O(3)Cu(1)N(2)
N(3)Cu(1)N(2)
95.69(12)
94.85(12)
167.83(13)
90.67(11)
91.30(11)
98.94(10)
91.57(13)
88.80(13)
87.84(10)
N(1)Cu(1)N(3)
N(1)Cu(1)N(2)
85.09(13)
83.65(13)
89.76(11)
178.07(11)
79.17(10)
178.66(13)
87.99(14)
87.39(12)
94.05(11)
92.81(13)
O(3w)Co(1)O(2)
O(3w
)Co(1)O(6)#1
O(2)Co(1)O(6)#1
O(3w)Co(1)O(1)
O(2)Co(1)O(1)
O(6)#1Co(1)O(1)
O(3
O(6)#1Co(1)O(2
O(3 )Co(1)O(1
O(6)#1Co(1)O(1
O(2 )Co(1)O(1
w
)Co(1)O(2
w
)
O(2)Co(1)O(2
O(1)Co(1)O(2
O(2)Co(1)O(1
w
w
w
w
)
)
)
)
w
)
w
w)
w
)
O(1)Co(1)O(1
166.95(11)
w
w)
#1
#1
* Symmetry codes:
–
x
+ 2, –
y, –
z
for
I
;
–x + 2, –y + 1, –z + 1 for II.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
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124
LIU et al.
ative of an overall antiferromagnetic coupling, as
shown in Fig. 3b. The room temperature value for µeff
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
(a)
6.5
6.0
5.5
5.0
4.5
4.0
is 5.19 µB. Upon cooling the µeff value decreases reguꢀ
larly, approaching a minimum around 2 K with µeff
1.71 µB
=
.
The principle of the theory model about the Cu–
Co system is similar to the Cu–Mn system described
above. We also think approximately the system also as
an isolated binuclear moiety. The magnetic analysis
was then carried out by using the theoretical expresꢀ
sion of the magnetic susceptibility deduced from the
ˆ
ˆ
ˆ
spin Hamiltonian
=
the magnetic susceptibility is
The expression of
−2JSCu1SCo1.
H
0
50 100 150 200 250 300
T
(b)
, K
2
Ng2β
0.20
0.15
0.10
0.05
0
6
5
4
3
2
1
0
⎡10 + 2exp(−4J KT)⎤
χM
=
+ Nα,
⎥
⎢
KT 5 + 3exp(−4J KT)
⎣
⎦
Nα = 200 ×10−6 cm3 mol−1.
And further using molecular field approximation to
deal with magnetic exchange interactions between the
binuclear units
χM
1 − (2zj' Ng2β2)χM
'
χM
,
=
where
ferred through the cisꢀoxamidate bridge between Cu
and Co ions, zj is the magnetic interactions between
binuclear systems. α is the temperature independent
paramagnetism. The bestꢀfit parameters are
J is the magnetic exchange interaction transꢀ
0
50 100 150 200 250 300
, K
'
T
N
Fig. 3.
χ
and
μ
versus
T
plots for complexes
I
(a) and II (b).
J =
M
eff
⎯
19.7 cm–1,
g
= 2.61, zJ'
= –4.1 cm–1. Agreement
2
factor
The negative
tween Cu2+ and Co2+ ions are antiferromagnetic.
is 6.33
×
10–3.
R =
(χobsd − χcalcd
J
)
χ2obsd
value suggests that the interactions beꢀ
∑
∑
The expression of the magnetic susceptibility for a
Cu–Mn system is
Ng2β
2
⎡10exp(−6J KT) + 28⎤
χM
=
+ Nα,
⎥
⎢
⎣
KT
5exp(−6J KT) + 7
Nα = 200 ×10−6 cm3 mol−1.
⎦
ACKNOWLEDGMENTS
This work was supported by the Natural Science
Foundation of Henan Province (no. 092300410031),
the Natural Science Foundation of Henan University
(no. 2010YBZR007).
And further using molecular field approximation to
deal with magnetic exchange interactions between the
binuclear systems
χM
1 − (2zj' Ng2β2)χM
'
χM
=
,
REFERENCES
1. Niemann, A., Bossek, U., Wieghardt, K., et al., Angew.
Chem. Int. Ed., 1992, vol. 31, p. 311.
2. Chou, Y.C., Huang, S., Koner, R., et al., Inorg. Chem.
2004, vol. 43, p. 2759.
3. Stamatatos, T.C., FoguetꢀAlbiol, D., Lee, S.C., et al.,
J. Am. Chem. Soc., 2007, vol. 129, p. 9484.
4. Sakamoto, M., Manseki, K., and Okawa, H., Coord.
Chem. Rev., 2001, vol. 219–221, p. 379.
5. Winpenny, R.E.P., Chem. Soc. Rev., 1998, vol. 27, p. 447.
6. Kahn, O., Acc. Chem. Res., 2000, vol. 33, p. 647.
7. Ma, B.Q., Gao, S., Su, G., et al., Angew. Chem. Int.
Ed., 2001, vol. 40, p. 434.
where
J
is the exchange integral between Cu and Mn
is the magnetic
ions within the binuclear moiety, z j
'
,
interactions between binuclear systems. Nα is the
temperature independent paramagnetism. The best
fitting for the experimental data gives J
= –17.7 cm–1,
g
= 2.03, z j' R =
= –0.05 cm–1. The agreement factor
2
2
is 9.56
χobsd
×
10–5, which corꢀ
responds to a good match as can be seen in Fig. 3a.
(χobsd − χcalcd
)
∑
∑
The negative J value suggests that the interactions beꢀ
tween Cu and Mn ions are antiferromagnetic.
The magnetic behavior of complex II was meaꢀ
sured in the temperature range 2–300 K and is indicꢀ
8. Tang, J.K., Li, Y.Z., Wang, Q.L., et al., Inorg. Chem.
2002, vol. 41, p. 2188.
,
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
No. 1
2013

SYNTHESIS, CRYSTAL STRUCTURES, AND MAGNETIC PROPERTIES
125
9. Zhang, L., Wang, S.B., Yang, G.M., et al., Inorg. 17. Sheldrick, G.M., SADABS
,
Program for Empirical Abꢀ
sorption Correction of Area Detector Data, G ttingen
(Germany): Univ. of G ttingen, 2002.
Chem., 2003, vol. 42, p. 1462.
10. Zhu, L.N., Xu, N., Zhang, W., et al., Inorg. Chem.
2007, vol. 47, p. 1297.
11. Sun, Y.Q., Fan, L.L., Gao, D.Z., et al., Dalton Trans.,
2010, vol. 39, p. 9654.
12. Pardo, E., Train, C., Lescouezec, R., et al., Dalton
Trans., 2010, vol. 39, p. 4951.
13. Lou, W.J., Zang, S.Q., Wang, Q.L., et al., Inorg. Chim.
Acta, 2009, vol. 362, p. 3005.
14. Lou, W.J., Zang, S.Q., Zhang, W., et al., J. Coord.
Chem., 2008, vol. 61, p. 3642.
15. Lou, W.J., Zhang, Y., Cui, H., et al., Z. Naturforsch.
2010, vol. 65b, p. 607.
16. Zang, S.Q., Tao, R.J., Wang, Q.L., et al., Inorg. Chem.,
2003, vol. 42, p. 761.
ö
ö
,
18. Sheldrick, G.M., SHELXTLꢀ97, Program for Crystal
Structure Solution, G ttingen (Germany): Univ. of
ttingen, 1997.
ö
G
ö
19. Nakamoto, K., Infrared and Raman Spectra of Inorganic
and Coordination Compounds, New York: John Wily, 1997.
20. Akhiff, Y., ServerꢀCarrio, J., Sancho, A., et al., Inorg.
Chem., 1999, vol. 38, p. 1174.
21. Carlin, R.L., Kopinga, K., Kahn, O., et al., Inorg.
Chem., 1986, vol. 25, p. 1786.
,
22. Julve, M., Verdaquer, M., Gleizes, A., et al., Inorg.
Chem., 1984, vol. 23, p. 3808.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
No. 1
2013