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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
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
165
166
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
167
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.
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)
168
169
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.
170
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]
[4]
[5]
[6]
[7]
[8]
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