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Journal of Molecular Structure 1046 (2013) 164170

Contents lists available at SciVerse ScienceDirect

Journal of Molecular Structure

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

Mixed ligand binuclear alkoxo-bridged copper(II) complexes derived

from aminoalcohols and nitrogen ligands
Violeta Tudor a,, Teodora Mocanu a, Floriana Tuna b, Augustin M. Madalan a, Catalin Maxim a,
Sergiu Shova c, Marius Andruh a,
a
b
c

Inorganic Chemistry Laboratory, Faculty of Chemistry, University of Bucharest, Str. Dumbrava Rosie Nr. 23, 020464 Bucharest, Romania
School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK
Petru Poni Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda, 41A, RO-700487 Iasi, Romania

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 Reactions of copper(II) with

aminoalcohols in the presence of

nitrogen ligands are investigated.
 The crystal structures of six new bisalkoxo binuclear complexes are
described.
 A strong ferromagnetic coupling was
found with one compound.

a r t i c l e

i n f o

Article history:
Received 21 February 2013
Received in revised form 15 April 2013
Accepted 15 April 2013
Available online 24 April 2013
Keywords:
Copper complexes
Monoethanolamine
Propanolamine
Binuclear complexes
Crystal structures
Magnetic properties

a b s t r a c t
Six binuclear alkoxo-bridged complexes have been obtained and cystallographically characterized. The
binuclear species are spontaneously assembled by reacting copper perchlorate with an aminoalcohol
(monoethanolamine, Hmea, or propanolamine, Hpa) in the presence of various co-ligands: 4-phenyl-pyridine (4-phpy) 4-amino-pyridine (4-apy) dipyridylamine (dpyam), 2,3-bis(2-pyridyl)pyrazine (dpp). The
six new compounds have the following formulas: [Cu(mea)(4-phpy)(ClO4)]2 1, [Cu(pa)(4-phpy)2]2(ClO4)2
2, [Cu(pa)(4-apy)(ClO4)]2 3, [Cu(mea)(dpyam)]2(ClO4)2 4, [Cu(pa)(dpyam)]2(ClO4)2 5, and [Cu(mea)
(dpp)]2(ClO4)2CH3OH 6. Except compound 1, the binuclear entities in crystals 2 6 are centrosymmetric,
with pentacoordinated copper ions. In compound 1, one copper is pentacoordinated, while the other one
is hexacoordinated. The perchlorate ions play different functions (monodentate and bridging in 1, monodentate in 3, uncoordinated in 2, 4, 5 and 6. The magnetic properties of compound 1 have been investigated and reveal a quite strong ferromagnetic coupling between the copper ions (J = + 81.9 cm1,
H = JS1S2).
2013 Elsevier B.V. All rights reserved.

1. Introduction
Aminoalcohols are polydentate ligands, which generate a very
rich coordination chemistry [1]. The hydroxo group can coordinate
as it is or can be deprotonated, the resulting alkoxo anion acting as
Corresponding author.
E-mail addresses: violetetudor@yahoo.com (V. Tudor), marius.andruh@dnt.ro
(M. Andruh).
0022-2860/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molstruc.2013.04.036

a bridge between two or three metal ions. In previous papers we

have shown that various aminoalcohols interacting with copper(II)
salts generate alkoxo-bridged binuclear species that efciently act
as nodes in constructing coordination polymers with various
dimensionalities and network topologies [2]. This is an extension
of the classical node and spacer strategy for constructing coordination polymers, formulated by Robson in 1990 [3]. As spacers we
employed either neutral (pyrazine, 4,40 -bipyridyl and bis-4-pyridyl
derivatives) or anionic ligands (e.g. polycyanido metal complexes:

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V. Tudor et al. / Journal of Molecular Structure 1046 (2013) 164170

[M(CN)]2, M = Ag+, Au+; [M(CN)4]2, M = Ni2+). Recently, Seppl

et al. described several coordination polymers obtained from binuclear alkoxo-bridged nodes and polycarboxylato spacers [4]. The
spacer molecules replace the weakly coordinated anions or solvent
molecules. The denticity of the aminoalcohol plays an important
role in dening the dimensionality of the resulting coordination
polymer. For example, bidentate aminoalcohols, such as monoethanolamine or propanolamine, are suited for the construction of 2-D
coordination polymers, while tridentate aminoalcohols (e.g. diethanolamine), which block three coordination positions at the pentacoordinated copper ions, will generate 1-D coordination polymers
[2f]. It is important to mention that, in some cases, the expected
dimensionality is reduced when the anion or the solvent molecule
are strongly coordinated to one of the two available coordination
sites of the copper ion in {Cu2(mea)2} and {Cu2(pa)2} nodes [2e].
Following our work on copper(II)-aminoalcohol systems, we
decided to isolate the alkoxo-bridged binuclear species themselves, using as co-ligands organic molecules that coordinate solely
to one metal ion (Scheme 1): 4-phenyl-pyridine (4-phpy) 4-aminopyridine (4-apy) dipyridylamine (dpyam); additionally we employed a ditopic ligand, 2,3-bis(2-pyridyl)pyrazine (dpp), but we
found that it coordinates to only one copper ion. Six new complexes have been obtained: [Cu(mea)(4-phpy)(ClO4)]2 1, [Cu(pa)
(4-phpy)2]2(ClO4)2 2, [Cu(pa)(4-apy)(ClO4)]2 3, [Cu(mea)(dpyam)]2
(ClO4)2 4, [Cu(pa)(dpyam)]2(ClO4)2 5, and [Cu(mea)(dpp)]2(ClO4)2
CH3OH 6 (mea = the anion of the monoetahnolamine; pa = the
anion of the propanolamine). Herein we report on their crystal
structures and on the magnetic properties of compound 1.
2. Experimental part
2.1. Materials and physical measurements
All reagents and solvents were reagent grade, purchased from
commercial sources and used without purication. IR spectra
(KBr pellets) were recorded on a BIO-RAD FTS 135 spectrophotometer from 4000 to 400 cm1. Absorption spectra were made with a
JASCO V-670 spectrophotometer using MgO as a standard. Magnetic measurements were performed on polycrystalline samples
restrained in eicosane, with a Quantum Design MPMS-XL SQUID
magnetometer equipped with a 7-T magnet. Data were corrected
for the diamagnetism of the samples using Pascal constants and
for the diamagnetic contributions of the sample holder by
measurement.
2.2. X-ray crystallography
Suitable single crystals of 16 were chosen for data collection.
Crystals were measured on a Xcalibur E (for compound 1) and on
a STOE IPDS II single crystal diffractometer (for crystals 26), using
graphite-monochromated Mo Ka radiation. The structures were
solved by direct methods and rened by full-matrix least-squares
techniques based on F2. All non-H atoms were rened anisotropically, and hydrogen atoms were introduced at calculated positions

165

(riding model), excepting the hydrogen atoms of the amino groups

in the crystals 3, 4 and 5.
A summary of the crystallographic data and the structure
renement for crystals 16 is given in Table 1.
2.3. Syntheses of 16
2.3.1. [Cu(mea)(4-phpy)(ClO4)]2 1
A methanolic solution (10 mL) of Cu(ClO4)26H2O (0.044 g,
0.118 mmol) was reacted with Hmea (0.022 g, 0.360 mmol) dissolved in 10 mL ethanol and the mixture was stirred at room temperature. To the resulting dark blue solution, a methanolic
solution (10 mL) of 4-phenylpyridine (0.018 g) was added under
continuous stirring. The resulted solution was stirred 2 h at room
temperature and then ltered off to remove any non-dissolved
material. Dark blue single crystals appeared after several days by
slow evaporation of the solution at room temperature in a hood.
IR (cm1, KBr): 3339(m), 3276(m), 2947(m), 2884(m), 1615(vs),
1578(m), 1485(m), 1426(m), 1120(vs), 1094(vs), 1074(vs),
1012(m), 940(w), 895(m), 880(s), 839(w), 766(w),730(w), 689(s),
626(w). UVVIS: 256, 319, 383, 589 nm.
2.3.2. [Cu(pa)(4-phpy)2]2(ClO4)2 2
An ethanolic solution (15 mL) of Cu(ClO4)2 6H2O (0.062 g,
0.167 mmol) was reacted with propanolamine (Hpa) (0.038 g,
0.505 mmol) dissolved in 15 mL ethanol and the mixture was stirred at room temperature. To the dark green solution, an ethanolic
solution (10 mL) of 4-phenylpyridine (0.026 g, 0.167 mmol) was
added under continuous stirring. The resulted dark bluegreen
solution was stirred 2 h at room temperature and then ltered off
to remove any non-dissolved material. Green single crystals suitable for X-ray diffraction studies were obtained by isopropyl ether
slow diffusion in the mother liqueur after several days. IR (cm1,
KBr): 3307(m), 3249(m), 2947(m), 2884(m), 1615(vs), 1484(s),
1421(s), 1121(vs), 940(w), 840(w), 771(m), 764(w),732(w),
699(s), 626(w). UVVIS: 264, 381, 717 nm.
2.3.3. [Cu(pa)(4-apy)(ClO4)]2 3
A solution of Cu(ClO4)26H2O (0.345 g, 0.931 mmol) in acetonitrile (5 mL) was reacted with a solution of propanolamine (Hpa)
(0.210 g, 2.79 mmol) dissolved in 10 mL acetonitrile resulting a
dark green solution. To the dark green solution, a 4-aminopyridine
(4-apy) solution (0.087 g, 0.924 mmol) in 10 mL acetonitrile was
added under continuous stirring. The resulted dark bluegreen
solution was stirred 2 h at room temperature and then ltered off
to remove any non-dissolved material. Violet single crystals suitable for X-ray diffraction studies were obtained by isopropyl ether
slow diffusion in the mother liqueur after several days. IR (cm1,
KBr): 3454(m), 3369(s), 3310(s), 3267(s), 2968(m), 2876(m),
1637(s), 1588(m), 1458(m), 1146(vs), 1113(vs), 1081(vs),
1023(vs) 940(m), 852(s), 627(s), 523(m). UVVIS: 210, 350, 580 nm.
2.3.4. [Cu(mea)(dpyam)]2(ClO4)2 4
A solution of Cu(ClO4)26H2O (0.046 g, 0.124 mmol) in 5 mL acetonitrile was reacted with Hmea (0.023 g, 0.376 mmol) dissolved in

Scheme 1. Nitrogen ligands used in this study.

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V. Tudor et al. / Journal of Molecular Structure 1046 (2013) 164170

Table 1
Crystal data and structure renement for 16.
Compound

Chemical formula
Formula weight
Crystal system
Space group
a
b
c

C26H30Cl2Cu2N4O10
756.52
Triclinic
P-1
10.4051(68)
10.4197(13)
14.7410(17)
71.4928(108)
89.4744(224)
80.2185(245)
1491.8(10), 2
200(2)
1.684
1.667
12,056
5854
R1 = 0.0295,
wR2 = 0.0790
R1 = 0.0349,
wR2 = 0.0818
1.051
0.459 and 0.552

C50H52Cl2Cu2N6O10
1094.96
Monoclinic
P21/c
10.6113(8)
9.8273(10)
25.952(2)
90.00
100.958(6)
90.00
2657.0(4), 2
293(2)
1.369
0.961
18,850
6878
R1 = 0.0602,
wR2 = 0.1309
R1 = 0.1619,
wR2 = 0.1698
0.891
0.281 and 0.271

C16H28Cl2Cu2N6O10
662.42
Monoclinic
P21/a
8.3047(10)
16.8653(17)
9.2364(12)
90.00
98.697(10)
90.00
1278.8(3),2
293(2)
1.720
1.933
14,980
4921
R1 = 0.0342,
wR2 = 0.0710
R1 = 0.0580,
wR2 = 0.0775
0.889
0.455 and 0.315

C12H15ClCuN4O5
394.27
Triclinic
P-1
7.9415(14)
9.8542(14)
10.6555(14)
77.8030(10)
81.4470(10)
76.4260(10)
787.96(20), 2
293(2)
1.662
1.585
9929
3619
R1 = 0.0555
wR2 = 0.1055
R1 = 0.1264
wR2 = 0.1247
0.877
0.577 and 0.428

C13H17ClCuN4O5
408.3
Triclinic
P-1
8.5264(17)
10.1942(19)
10.3616(17)
91.383(15)
95.760(15)
107.023(15)
855.5(3),2
293(2)
1.585
1.463
8644
3649
R1 = 0.0563
wR2 = 0.1304
R1 = 0.1021
wR2 = 0.1491
0.909
0.620 and 0.625

C34H40Cl2Cu2N10O12
978.74
Triclinic
P-1
9.6388(13)
10.2117(14)
12.7833(18)
80.460(11)
68.444(10)
63.991(10)
1051.7(3),1
293(2)
1.545
1.209
11,529
5085
R1 = 0.0573
wR2 = 0.1454
R1 = 0.0848,
wR2 = 0.1603
0.951
1.715 and 0.348

a
b

c
Volume (3), Z
Temperature (K)
Calculated density (Mg m3)
Absorption coefcient (mm1)
Reections collected
Independent reection
Final R indices [I > 2r(I)]
R indices (all data)
Goodness-of-t on F2
Dqmin and Dqmax (e 3)

Fig. 1. (a) Perspective view of the binuclear complex [Cu(mea)(4-phpy)(ClO4)]2 1; (b) detail of the packing diagram showing the formation of the supramolecular chains.

10 mL acetonitrile and the mixture was stirred at room temperature. To the resulting dark blue solution, an acetonitrile solution
(10 mL) of 2,20 -dipyridyilamine (dpyam) (0.021 g, 0.122 mmol)
was added under continuous stirring. The resulted green solution
was stirred 2 h at room temperature and then ltered off to remove any non-dissolved material. Green single crystals appeared
after several days by slow evaporation of the mother liqueur at
room temperature in a hood. IR (cm1, KBr): 3354(m), 3297(m),
3199(w), 3038(w), 2879(w), 2840(w), 1642(s), 1588(s), 1531(s),
1492(vs), 1111(vs), 1094(vs), 1089(vs), 781(s), 625(m). UVVIS:
327, 412, 889 nm.

2.3.5. [Cu(pa)(dpyam)]2(ClO4)2 5
A solution of Cu(ClO4)26H2O (0.042 g, 0.113 mmol) in 5 mL acetonitrile was reacted with Hpa (0.026 g, 0.346 mmol) dissolved in

Fig. 2. Perspective view of the cationic complex in crystal 2.

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V. Tudor et al. / Journal of Molecular Structure 1046 (2013) 164170

resulted solution was stirred 2 h at room temperature and then ltered off to remove any non-dissolved material. Green single crystals appeared after several days by slow evaporation of the solution
at room temperature in a hood. IR (cm1, KBr): 3413(vs), 2969(w),
2938(w), 2884(w), 2851(w), 1616(m), 1591(m), 1570(m),
1481(m),1403(m), 1121(vs), 1088(vs), 1035(vs), 787(m), 625(m).
UVVIS: 284, 343, 841 nm.
3. Results and discussion
The reactions between copper(II) perchlorate, the aminoalcohol
(Hmea, Hpa) in the presence of the nitrogen co-ligands lead to six
binuclear complexes in which the copper(II) ions are bridged by
two alkoxo-groups. Three types of co-ligands have been used:
monodentate (4-phenyl-pyridine, 4-amino-pyridine) and bidentate dipyridylamine; another ligand, that is ditopic, 2,3-bis(2-pyridyl)pyrazine (dpp), was found to coordinate to only one copper ion.
Fig. 3. Molecular structure of the binuclear complex [Cu(pa)(4-apy)(ClO4)]2 3.

3.1. Description of the crystal structures

10 mL acetonitrile and the mixture was stirred at room temperature. To the resulting dark green solution, an acetonitrile solution
(10 mL) of 2,20 -dipyridyilamine (dpyam) (0.019 g, 0.110 mmol)
was added under continuous stirring. The green resulted solution
was stirred 2 h at room temperature and then ltered off to remove any non-dissolved material. Green single crystals appeared
after several days by slow evaporation of the solution at room temperature in a hood. IR (cm1, KBr): 3353(m), 33316(m), 3265(m),
3219(w), 2952(w), 22,929(w), 2868(w), 2809(w), 1634(s),
1583(s), 1528(s), 1475(vs), 1121(vs), 1108(vs) 1079(vs), 1011(vs),
767(s), 623(m). UVVIS: 325, 380, 673, 970 nm.
2.3.6. [Cu(mea)(dpp)]2(ClO4)2CH3OH 6
A methanolic solution (5 mL) of Cu(ClO4)26H2O (0.042 g,
0.113 mmol) was reacted with Hmea (0.021 g, 0.343 mmol) dissolved in 10 mL methanol and the mixture was stirred at room
temperature. To the resulting dark blue solution, a methanolic
solution (15 mL) of 2,3-bis(2-pyridyl)pyrazine (dpp) (0.026 g,
0.110 mmol) was added under continuous stirring. The light green

The crystal structure of 1, [Cu(mea)(4-phpy)(ClO4)]2, consists of

neutral binuclear species (Fig. 1a). The two perchlorate ions are
coordinated to the metal ions in different ways: one bridges the
metal ions, while the other one is coordinated to only one copper
ion. The two copper(II) ions are crystallographically non-equivalent and show different coordination geometries. One copper ion
is pentacoordinated with a square pyramdidal stereochemistry;
the basal plane is formed by two alkoxo bridging oxygen atoms
(Cu1O1 = 1.9316(15); Cu1O2 = 1.9291(15) ), one nitrogen from
the mea ligand (Cu1N1AA = 1.998(2) ), and another one from the
terminal 4-phpy ligand (CuN1 = 1.9826(19) ); the apical position
is occupied by a semicoordinated oxygen atom from the bridging
perchlorate ion (Cu1O6 = 2.773 ). The trigonal distortion from
square pyramidal (SP) geometry is evaluated by the parameter s,
dened as s = [(h  /)/60] [5], where h and / are the angles between the donor atoms forming the basal plane in SP geometry
(s = 0 for an ideal SP geometry and s = 1 for the ideal trigonal bipyramidal geometry). For Cu1, the value of the s parameter is 0.07).
The second copper ion shows a distorted octahedral geometry.

Table 2
Selected bond distances () and bond angles () for 16.
1
Cu1O1
Cu1O2
Cu1N1
Cu1N1AA
Cu1Cu2
Cu2O2
Cu2O1
Cu2N2
Cu2N0AA
O1 Cu1 Cu2
O1 Cu1 N1
O1 Cu1 N1AA
O2 Cu1 Cu2
O2 Cu1 O1
O2 Cu1 N1
O2 Cu1 N1AA
O1 Cu2 Cu1
O1 Cu2 O2
O1 Cu2 N0AA
O2 Cu2 N0AA
O2 Cu2 N2
N0AA Cu2 Cu1
N2 Cu2 Cu1
Cu1 O1 Cu2
Cu1 O2 Cu2

2
1.9316(15)
1.9291(15)
1.9826(19)
1.998(2)
2.8787(6)
1.9483(16)
1.9392(16)
2.0030(19)
1.9959(19)
42.05(5)
166.94(8)
85.30(7)
42.32(5)
80.58(6)
97.46(7)
162.10(8)
41.85(4)
79.91(6)
163.18(7)
85.44(7)
175.46(7)
121.50(5)
134.61(6)
96.10(7)
95.88(7)

N1Cu1
N2Cu1
N3Cu1
O1Cu1
O1Cu1
Cu1O1a
Cu1Cu1
O1 Cu1 O1
O1 Cu1 N1
O1 Cu1 N1
O1 Cu1 N2
O1 Cu1 N2
N1 Cu1 N2
O1 Cu1 N3
O1 Cu1 N3
N1 Cu1 N3
N2 Cu1 N3
Cu1O1 Cu1
N1 Cu1 Cu1
N2 Cu1 Cu1
N3 Cu1 Cu1

3
2.000(4)
2.020(4)
2.346(4)
1.937(3)
1.937(3)
1.937(3)
3.0386(10)
76.66(14)
94.41(15)
165.41(16)
161.79(14)
94.13(14)
91.11(17)
98.69(13)
95.67(13)
97.09(16)
97.82(14)
103.345(4)
131.75(13)
130.64(12)
99.17(9)

N1Cu1
N2Cu1
O1Cu1
O1aCu1
Cu1Cu1
N2 Cu1 Cu1
N1 Cu1 Cu1
O1 Cu1 O1
O1 Cu1 N2
O1 Cu1 N2
O1 Cu1 N1
O1 Cu1 N1
N2 Cu1 N1
Cu1O1 Cu1
O1 Cu1 Cu1

4
1.9872(19)
1.9766(17)
1.9077(14)
1.9273(14)
2.9836(6)
132.67(6)
135.41(6)
77.86(6)
170.33(7)
94.23(7)
96.27(7)
173.79(7)
91.83(8)
102.14(6)
38.69(4)

Cu1O1
Cu1N1
Cu1O1
Cu1N3
Cu1N4
Cu1Cu1
O1 Cu1 N1
O1 Cu1 O
N1 Cu1 O1
O1 Cu1 N3
N1 Cu1 N3
O1 Cu1 N3
O1 Cu1 N4
N1 Cu1 N4
O1 Cu1 N4
N3 Cu1 N4
O1 Cu1 Cu1
N1 Cu1 Cu1
O1 Cu1 Cu1
N3 Cu1 Cu1
Cu1 O1 Cu1

5
1.936(3)
1.994(4)
2.066(3)
2.083(4)
2.111(6)
3.0353(13)
173.51(16)
81.38(14)
93.10(15)
95.54(14)
90.39(15)
124.36(16)
83.59(19)
95.4(2)
111.8(2)
123.0(2)
42.29(10)
132.10(13)
39.09(8)
116.47(11)
98.62(14)

Cu1O1
Cu1O1
Cu1N4
Cu1N1
Cu1N2
O1Cu1
O1 Cu1 O1
O1 Cu1 N4
O1 Cu1 N4
O1 Cu1 N1
O1 Cu1 N1
N4 Cu1 N1
O1 Cu1 N2
O1 Cu1 N2
N4 Cu1 N2
N1 Cu1 N2
Cu1O1Cu1

6
1.944(3)
1.972(3)
2.019(5)
2.046(4)
2.220(4)
1.972(3)
76.21(15)
94.53(18)
157.6(2)
168.77(16)
96.16(16)
89.6(2)
102.89(17)
101.37(16)
100.6(2)
86.56(16)
103.791(143)

N1Cu1
N2Cu1
N3Cu1
O1Cu1
O1Cu1
Cu1O1
Cu1Cu1
Cu1 O1 Cu1
O1 Cu1 O1
O1 Cu1 N2
O1 Cu1 N2
O1 Cu1 N1
O1 Cu1 N1
N2 Cu1 N1
O1 Cu1 N3
O1 Cu1 N3
N2 Cu1 N3
N1 Cu1 N3

2.026(3)
2.019(3)
2.250(3)
1.921(3)
1.965(3)
1.965(3)
2.9072(10)
96.86(11)
83.14(11)
176.00(12)
96.60(12)
84.74(14)
147.49(14)
97.47(14)
99.54(11)
103.41(11)
76.61(11)
108.30(14)

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V. Tudor et al. / Journal of Molecular Structure 1046 (2013) 164170

Fig. 4. (a) View of the cationic complex Cumeadpyam2

2 in crystal 4; (b) view of
the cationic complex Cupadpyam2
2 in crystal 5.

The equatorial plane is formed by the two bridging oxygen atoms

(Cu2O1 = 1.9392(16), Cu2O2 = 1.9483(16) ), and two nitrogen
atoms, one from the mea ligand (Cu2N0AA = 1.9959(19) ), the
other one from the 4-phpy ligand (Cu2N2 = 2.003(19) ). The apical positions are occupied by one oxygen atom from the bridging
perchlorate (Cu2O5 = 2.876 ) and one oxygen from the terminal
perchlorato ligand (Cu2O7 = 2.553 ). The intramolecular
Cu1  Cu2 distance is 2.8787(6) . The phenyl and pyridyl ring
within the 4-phpy ligand are not coplanar (dihedral angles:
9.937 for one 4-phpy molecule and 11.40 for the other one).
The analysis of the packing diagram reveals the formation of supramolecular chains, though intermolecular pp stacking interactions
(carboncarbon distances varying between 3.46 and 3.83 ) established between 4-phpy ligands (Fig. 1b).
The reaction between copper perchlorate, propanolamine and
4-phpy affords a binuclear complex, 2, with two 4-phpy molecules
coordinated to each copper ion. It is interesting to notice that
working in the same conditions but using monoethanol amine

(complex 1) only one 4-phpy ligand is attached to each copper

ion. The crystallographic investigation of 2 reveals cationic centrosymmetric complexes, Cupa4-phpy2 2
2 and perchlorate anions
(Fig. 2). Each copper(II) ion is pentacoordinated with a square pyramidal geometry (s = 0.06). Two alkoxo oxygen atoms and two
nitrogen atoms (from the pa and 4-phpy ligands) describe the basal
plane
(Cu1O1 = 1.937(3),
Cu1O1a = 1.937(3),
Cu1
N1 = 2.000(4), Cu1N2 = 2.020(4) , a = 1  x, y, 1  z), with a
nitrogen atom arising from another 4-phpy molecule into the apical position (Cu1N3 = 2.346(4) ). The distance between the copper ions within the binuclear entity is 3.039 .
The crystal structure compound 3 consists of neutral, centrosymmetric binuclear complexes, [Cu(pa)(4-apy)(ClO4)]2. The copper ions are pentacoordinated and the perchlorate ions act as
monodentate ligands (Fig. 3). The square pyramidal coordination
geometry is only slightly distorted (s = 0.03). The copper ions display a square pyramidal geometry: two bridging alkoxo oxygens
(Cu1O1 = 1.9077(14); Cu1O1a = 1.9277(14) , a = 2  x, y,
2  z) and two nitrogen atoms arising from the pa and, respectively,
4-apy
ligands
(Cu1N1 = 1.9872(19);
Cu1
N2 = 1.9766(17) ) form the basal plane, and one perchlorato oxygen is coordinated into the apical position (Cu1O2 = 2.741 ). The
intramolecular distance between the copper ions is 2.9837(5) .
Compounds 4 and 5 differ by the nature of the aminoalcohol
employed (Hmea and, respectively, Hpa), the co-ligand being the
same (dipyridylamine). Their structures are depicted in Fig. 4. In
both compounds the cooper ions are pentacoordinated (two alkoxo
bridging oxygens, one nitrogen from the corresponding aminoalcohol, and two nitrogen atoms from the chelating ligand). Both cationic complexes are centrosymmetric. The main difference
between the two structures arises from the coordination geometries of the copper ions. In compound 4 (Fig. 4a), the copper ions
show a trigonal bipyramidal stereochemistry (Cu1O1 = 1.936(3),
Cu1O1a = 2.066(3), Cu1N1 = 1.994(4), Cu1N3 = 2.083(4), Cu1
N4 = 2.111(6) , a = x, 2  y, 1  z). The apical positions are occupied by atoms N1 and O1, the value of the N1Cu1O1 being
173.51(16). The distance between the copper ions is 3.035 . In
the case of compound 5, the coordination geometry of the copper
ions is distorted square pyramidal (s = 0.19). The basal plane is described by two alkoxo oxygens (Cu1O1 = 1.944(3), Cu1
O1a = 1.972(3) , a = 1  x, y, 2  z), one nitrogen from the pa ligand (Cu1N4 = 2.019(5) ), and another one from the chelating ligand (Cu1N1 = 2.046(4) ); the apical position is occupied by one
nitrogen atom of the dpyam ligand (Cu1N2 = 2.220(4) ). The
intermetallic distance is 3.082 .
Selected bond distances and angles for compounds 16 are collected in Table 2.
The molecular structure of compound 6 is similar to those described for compounds 4 and 5. In spite of the two pockets formed
by the four nitrogen atoms, that could in principle interact with
two metal ions, the 2,3-bis(2-pyridyl)pyrazine ligand chelates only
one copper ion in 6 (Fig. 5). The binuclear cationic complex is cen-

Fig. 5. Perspective view of the cationic complex Cupadpyam2

2 in crystal 6.

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V. Tudor et al. / Journal of Molecular Structure 1046 (2013) 164170

0.6

(4)
(5)

0.5

Abs., a.u.

0.4
0.3
0.2
0.1
0.0
200

400

600

800

1000

1200

1400

, nm
Fig. 6. Diffuse reectance spectra of compounds 4 and 5.

trosymmetric, the copper ions being pentacoordinated, with a

strongly distorted square pyramidal geometry (s = 0.47), with the
following metaldonor atom distances: Cu1O1 = 1.921(3); Cu1
O1a = 1.965(3); Cu1N1 = 2.026(3), Cu1N2 = 2.019(3), Cu1
N3 = 2.250(3) , a = 2  x, y, z. The distance between the copper
ions is 2.9072(10) . The crystallization methanol molecule is
hydrogen bonded to one of the nitrogen atoms of the dpp ligand
(O6  N5 = 2.850 ).

3.2. Optical and magnetic properties

The electronic spectra of the six compounds have been recorded
by diffuse reectance technique. It is interesting to compare the
UVVIS spectra of 4 and 5, since the cooper ions in these compounds have different stereochemistries (trigonal bipyramidal
and, respectively, distorted square pyramidal), the two compounds
containing the same co-ligand. Their spectra are presented in Fig. 6.
The spectra (dd bands) show the characteristic features for the
two coordination geometries [6]: a band (889 nm) with a low
intensity shoulder at higher energy for the trigonal bipyramidal
stereochemistry, and a band (673 nm) with a low intensity shoulder at lower energy (970 nm) for the square pyramidal geometry.
The magnetic properties of hydroxo-, alkoxo-, and phenoxobridged copper(II) complexes have been intensively investigated,
from both experimental and theoretical points of view. Magnetostructural correlations have shown and justied a large dependence of the exchange coupling constant on the Cu(II)OCu(II)
bridging angle, a [7]. For the particular case of the bis-alkoxobridged binuclear copper complexes this dependence is given by
the following relationship: J = (82.1  a  7857) cm1. Particularly
interesting are complexes in which the value off the bridging angle
is lower than 95.7, since in this case the exchange interaction is
predicted to be ferromagnetic. The values of the bridging angles,
a, for the six compounds are: 1: 95.88(7) and 96.10(7); 2:
103.34(14); 3: 102.14(6); 4: 98.62(14); 5: 10,379(15); 6:
96.86(11). By analyzing these values we decided to investigate
the cryomagnetic properties of compound 1, with the smallest a
angle. The vMT vs. T as well as the magnetization vs. eld curves
are represented in Fig. 7. The room temperature value of the vMT
product (0.88 cm3 mol1 K) corresponds well to two non-interacting copper ions. By decreasing the temperature vMT increases
reaching a value of 1.08 cm3 mol1 K at T = 22 K, indicating a ferromagnetic interaction of the copper ions. Below this temperature
the vMT product decreases abruptly, as a result or the intermolec-

ular antiferromagnetic interactions. The magnetic data were tted

using the well-known BleaneyBowers equation (H = JS1S2):

vM 2Ng 2 b2 T=kT  h3 expJ=kT1

A Weiss term, h, was introduced in order to take into account
the intermolecular interactions. The best t to the data leads to
the following values: g = 2.09; J = 81.9 cm1, h = 0.36 K. The
ground state S = 1 is also conrmed by the magnetization vs. eld
curves, recorded at 2 and 4 K (inset to Fig. 7). Most of the known
bis-alkoxo-bridged binuclear cooper(II) complexes with CuOCu
angles higher than 100 are characterized by a very strong antiferromagnetic coupling between the copper ions [8]. Another important parameter that inuences, together with the a angle, the
nature and magnitude of the exchange interaction within bis-alkoxo-bridged copper complexes is the s angle, which measures
the out-of-plane shift of the carbon atom of the bridging alkoxo
group. Small values of the a angle are associated with large values
of s. A ferromagnetic coupling is favored when a diminishes and s
increases [7b,8d,9]. In our case the values of the two angles are:

Fig. 7. Temperature dependence of the vMT product for compound 1. Inset:

Magnetization vs. eld curves recorded at 2 K and 4 K.

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V. Tudor et al. / Journal of Molecular Structure 1046 (2013) 164170

a = 95.88, and s 31.9. These values are in line with other several
complexes which are characterized by a ferromagnetic interaction
[9].
4. Conclusions
Six new binuclear compounds have been synthesized and crystallographically characterized. They illustrate that the spontaneous
formation of bis-alkoxo-bridged copper(II) complexes is a general
phenomenon which leads to a rich variety of polynuclear complexes. By choosing the appropriate co-ligands, either discrete
binuclear species or coordination polymers can be assembled.
Compound 1, [Cu(mea)(4-phpy)(ClO4)]2, shows a strong ferromagnetic interaction of the metal ions, which is justied by the structural parameters at the bridge level.
[2]

Acknowledgements
Financial support from the UEFISCDI (grant PNII-ID-PCCE-20112-0050) is gratefully acknowledged. S.S. is grateful to the European
Regional Development Fund, Sectoral Operational Programme Increase of Economic Competitiveness, Priority Axis 2 (SOP IEC-A2O2.1.2-2009-2, ID 570, COD SMIS-CSNR: 12473, Contract 129/
2010-POLISILMET, for nancial support.
[3]

Appendix A. Supplementary material

CCDC 925959925964 contain the supplementary crystallographic data for compounds 16. These data can be obtained free
of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336 033; or e-mail: deposit@ccdc.cam.ac.uk. Supplementary data associated with this article
can be found, in the online version, at http://dx.doi.org/10.1016/
j.molstruc.2013.04.036.

[4]
[5]
[6]
[7]

[8]

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