Copper N-(4'-benzo-15-crown-5)-2-(amino-N-tosyl)phenylaldiminate: Complexing and ion-selective properties

Article abstract of DOI:10.1134/S0036023608060120

Copper(II) chelate with N-(4-benzo-15-crown-5)-2-(amino-N-tosyl) phenylaldiminate CuL₂ and its coordination compounds with Li, Na, and K salts have been synthesized. Their IR spectra have been studied and assignment of the key vibration frequencies of CuL₂ and complexes based on it. On the basis of spectral, thermogravimetric, and elemental analysis datasassumptions concerning the compound structure are made. The ion-selective properties of CuL₂ are studied by potentiometry.

Full text of DOI:10.1134/S0036023608060120

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2008, Vol. 53, No. 6, pp. 884–889. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © I.S. Ivanova, A.V. Dorokhov, E.N. Pyatova, A.S. Burlov, A.D. Garnovskii, A.Yu. Tsivadze, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008,
Vol. 53, No. 6, pp. 956–961.
COORDINATION
COMPOUNDS
Copper N-(4'-Benzo-15-crown-5)-2-(amino-N-
tosyl)phenylaldiminate: Complexing
and Ion-Selective Properties
a
b
a
c
I. S. Ivanova , A. V. Dorokhov , E. N. Pyatova , A. S. Burlov ,
c
b
A. D. Garnovskii , and A. Yu. Tsivadze
a
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
b
Frumkin Institute of Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, 119991 Russia
c
Institute of Physical and Organic Chemistry, Rostov State University, pr. Stachki 194/3, Rostov-on-Don, 344104 Russia
Received May 21, 2007
Abstract—Copper(II) chelate with N-(4'-benzo-15-crown-5)-2-(amino-N-tosyl)phenylaldiminate CuL and its
2
coordination compounds with Li, Na, and K salts have been synthesized. Their IR spectra have been studied
and assignment of the key vibration frequencies of CuL and complexes based on it. On the basis of spectral,
2
thermogravimetric, and elemental analysis datasassumptions concerning the compound structure are made. The
ion-selective properties of CuL are studied by potentiometry.
2
DOI: 10.1134/S0036023608060120
In recent years, enhanced attention has been paid to alkali metals [8, 9]. To continue the studies of the
ligand systems containing simultaneously several complexing properties of ambidentate azomethine
donor centers, in particular, azomethine derivatives of
derivatives of benzo-15-crown-5, we investigated the
crown ethers and coordination compounds based on
complexing properties and potentiometric selectivity
them [1–7]. Previously, we reported the results of
studies of the ZnL chelate and its complexes with of the metal chelate CuL2.
2
Ts
X
N
H
M1/2
R
C N
C N
H
O
O
H
O
O
O
O
O
M = Zn (ZnL )
O
2
M = Cu (CuL )
O
O
2
R = H, X = NTs (HL)
R = 5-Br, X = O (HL )
Ts =
SO2
CH3
1
EXPERIMENTAL
The heteronuclear CuL complexes with lithium,
2
sodium, and potassium salts were synthesized by dis-
CuL was prepared by the following procedure.
2
solving a CuL sample in acetonitrile and adding the
2
Copper acetate (0.00001 mol) was added to a solution
of N-(4'-benzo-15-crown-5)-2-(amino-N-tosyl)phenyl-
aldimine (HL) (0.1 g, 0.00002 M) in methanol (10 mL)
and the mixture was refluxed for 2 h on a water bath.
appropriate portion of an alkali metal salt in the ratio
CuL : M = 1 : 2 (for Li and Na salts) or 1 : 1 (for K salts).
2
The solution was left in air for 5–7 days. The precipitate
The precipitate was filtered off and recrystallized from formed upon solvent evaporation was washed with
alcohol.
alcohol and dried over CaCl2.
8
84

COPPER N-(4'-BENZO-15-CROWN-5)-2-(AMINO-N-TOSYL)PHENYLALDIMINATE
885
Table 1. Results of elemental analysis of CuL and its complexes with alkali metals
2
Content (found/calculated), %
Compound
H
C
N
S
CuL C H N O S Cu
1
4.8/5.5
4.8/4.7
59.4/58.9
44.8/48.2
4.9/4.9
4.0/4.0
not analyzed
2
56 62
4
14
2
2
LiClO · CuL · 2H O
3.6/4.6
4
2
2
C H N O S Cl Li Cu
5
6
66
4
24
2
2
2
1
2
NaI · CuL · 2H O
4.0/4.5
5.6/5.1
5.1/4.8
4.9/5.0
43.7/45.4
49.6/51.9
48.7/50.7
57.6/55.2
3.7/3.8
6.6/6.3
4.2/4.2
6.8/5.6
5.2/4.3
not analyzed
5.7/4.8
2
2
C H N O S I Na Cu
5
6
66
4
24 2 2
2
1
2
NaSCN · CuL · 2H O
2 2
C H N O S I Na Cu
5
8
66
4
24 4 2
4
1
KI · CuL · H O
C H N O S I K Cu
2
2
5
6
64
4
15 2 1
1
1
KSCN · ZnL2
C H N O S K Zn
1
not analyzed
5
7
62
5
14
3
1
The elemental analysis of the obtained compounds metal salts, it was shown that the complexation in both
was carried out on a Carlo Erba analyzer. According to cases is due to coordination of the oxygen atoms of the
elemental analysis (Table 1), trinuclear complexes are macrocyclic moiety to the alkali metal. X-ray diffrac-
+
+
formed with Li and Na and binuclear complexes are tion and vibrational spectroscopy showed analysis data
+
for [5, 6, 8] that the macrocycle conformations in HL,
obtained with ä : 2 MX · ZnL · nH O (M = Li, Na; X =
2
2
1
ZnL and HL are different, being dependent not only
ClO , NCS, I; n = 0; 2) and KX · ZnL · nH O (X = I,
2
4
2
2
on the nature of the substituent in the benzene ring but
changing appreciably upon coordination of zinc cation
to the azomethine moiety. In addition, the ion-selective
NCS; n = 0; 1).
The IR absorption spectra were recorded on a Nico-
let NEXUS FT IR spectrophotometer in the range
000–400 cm (as mineral oil and hexachlorobutadi-
properties of HL and ZnL as neutral transport agents
–
1
2
4
are markedly different.
ene mulls).
The vibrational frequencies of CuL and the derived
2
Thermogravimetric measurements were carried out
complexes (Table 2) were assigned resorting to the
on a Q-1500D derivatograph in the temperature range
1
spectral data for HL, ZnL , HL , B15C5, 4'-nitrobenzo-
of 20–500°ë in platinum crucibles; the heating rate was
2
1
0 K/min.
15-crown-5, and their complexes [5, 6, 8, 9, 12–14].
Plasticized polymeric membranes containing HL,
The IR spectrum of CuL has changed with respect
2
ZnL , or CuL were prepared by a known procedure to the spectrum of HL similarly to the spectrum of
2
2
[
10] (a solution in the active component in an organic ZnL , which changes upon coordination to the azome-
2
–
1
solvent, a plasticizer, was introduced into the polyvinyl thine moiety. First, the δ(NH) band (1572 cm in HL)
chloride matrix). As the plasticizer, Ó-nitrophenyl octyl disappears upon the replacement of the proton by a cop-
ether (dielectric constant ε = 23) was used. The mem- per ion; the ν(C=N) band shifts to lower frequencies by
branes had the following composition (wt %): neutral
transport agent, 1; poly(vinyl chloride), 33; plasticizer, 66.
–1
–1
7
cm (or 4 cm for ZnL ) from its position in the
2
spectrum of HL. Second, the ν (SO ) and ν (SO )
as
2
s
2
The electroanalytical parameters of the membranes stretching vibration frequencies considerably decrease
were studied by means of the galvanic circuit
–1
–1
(
1303, 1141 cm for CuL and 1338, 1156 cm for
2
Ag|AgCl, KCl(1 M)|sample solution|membra- HL, respectively) (Table 2).
ne|internal solution|AgCl|Ag
The e.m.f. was measured by an OR-300 pH iono- gen atoms, ν (PhO) and ν (PhO), occur in the spectrum
meter (Radelkis, Hungary).
The electroanalytical parameters of ion selective
electrodes were measured according to IUPAC recom-
mendations [11] at pH 5–7. The selectivity coefficients
were determined by the biionic potential method.
The stretching vibrations involving the anisole oxy-
s
as
–1
of CuL at 1263 and 1234 cm as medium-intensity
bands (for ZnL , 1269 and 1244 cm ).
2
–1
2
–1
The region of 1140–1080 cm is known [15, 16] to
contain conformationally sensitive ν (ëOë) modes of
as
the macrocycle. In the spectrum of CuL , this region
2
–1
contains two strong bands at 1131 cm (with an inflec-
RESULTS AND DISCUSSION
–1
–1
tion at 1106 cm ) and 1082 cm (Table 2). Their posi-
In studies [9, 12] devoted to complexation of tions and intensity ratio are similar to those observed in
azomethine derivatives HL and ZnL with some alkali the spectrum of ZnL (1136 and 1082 cm ). We attrib-
–
1
2
2
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 53 No. 6 2008

8
86
IVANOVA et al.
–
1
Table 2. Assignment of key vibration frequencies (cm ) in the IR spectra of CuL and its complexes
2
2
LiClO4
2NaNCS
· CuL2
KNCS 2NaI · CuL2 KI · CuL2
Assignment
HL [6]
ZnL [9]
CuL2
–
· CuL2
2
·
CuL2
· 2H O
· H O
2
2
·
2H O
· 2H O
2
2
ν(H O)
3570
3403
3406
3448
2
3
522
ν(C≡N)
ν(C=N)
ν(CC)Ph
2056
1610
1596
2052
1607
1594
1613
1595
1609
1594
1606
1611
1609
1596
1608
1596
1591
1544
1597
1522
1
1
555
520
1
552
1552
1508
1553
1508
1553
1508
ν(CC)Ph
δ(CH2)
1502
1497
1488
1509
1511
1507
1
490
1
478
1480
1476
1478
1476
1443
1473
1457
1
1
453
423
1463
1405
1456
1444
1457
1442
1
1
447
436
1448
1396
1443
1431
1418
396
1426
1402
1
1401
1401
1400
ω(CH2),
ν(CN)
1386
1365
1362
1364
1358
1344
1360
1334
1358
1344
1359
1302
1
1
334
319
1344
1295
ν (SO )
1338
1298
1300
1303
1280
1299
1285
1300
1299
as
2
τ(CH2)
1
286
1
256
νs(PhO)
νas(PhO)
δ(CH)
1265
1249
1212
1269
1244
1208
1108
1263
1234
1200
1264
1231
1206
1261
1204
1204
1262
1204
1203
1261
1206
1203
1265br
1203
δ(CH)Ph
1
167
1172
1162
1167
1138
1
155
1158sh
1131
1160
1129
1158
1126
ν (SO )
1156
1134
1
1
1
1136
1136
1141
1131
1131
1131
s
2
νas(COC)
1131
1138
1128
128
112
100
1129
1103
1082
1126
1111sh
1083
1106sh
1082
1104
1081
δ(CH)Ph
ν(ClO4)
1092
079
1099sh
1082
1
1081
1050
1082
1053
1084
ν(CO) + ν(CC),
δ(CH)Ph
1063
1053
1063
1053
1052
1050
1055
1
029
1
013
1018
980
1020
9
9
91
78
1001
989
981
985
983
982
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 53 No. 6 2008

COPPER N-(4'-BENZO-15-CROWN-5)-2-(AMINO-N-TOSYL)PHENYLALDIMINATE
887
Table 2. (Contd.)
Assignment
2
LiClO4
2NaNCS
· CuL2
KNCS 2NaI · CuL2 KI · CuL2
HL [6]
951
ZnL [9]
CuL2
· CuL2
2
·
CuL2
· 2H O
· H O
2
2
·
2H O
· 2H O
2
2
ν(CO) + ν(CC)
947
945
938
920
945
943
945
943
938
919
906
+
ρ(CH2)
9
43
936
917
903
9
9
12
01
905
880
902
880
903
882
ρ(CH ) + ν(CO),
896
891
876
2
νpuls(M)
8
8
8
8
78
53
35
12
877
848
872
872
828
840
815
802
838
816
838
816
826
814
839
815
815
8
00
νpuls(A),
δ(CH)Ph
796
795
795
7
64
762
769
7
55
756
737
721
707
758
755
721
760
722
758
7
7
7
37
22
04
739
723
708
722
723
708
707
661
δ(ClO4)
623
Other vibrations
659
663
645
628
664
642
662
648
660
642
661
642
660
641
6
6
36
02
602
574
5
69
571
551
575
553
574
563
551
576
575
552
524
5
5
5
65
49
40
556
544
549
519
551
544
521
5
25
5
4
09
74
511
4
90
481
15
478
4
–
1
uted the band at 1136 cm in the spectrum of ZnL to both macrocycles of the molecule. Thus this range in the
2
–1
an S T S conformation unit [8]. The somewhat lower spectrum of CuL contains a split band (945 and 938 cm )
position of the high-frequency component in the spec-
trum of CuL (1131 cm ) suggests that CuL macrocy-
cles incorporate no ethylene glycol units with this con-
figuration. The band at 1082 cm is probably due to the
bending vibrations of the benzene rings.
+
–
–
2
–1
instead of a single band (947 cm ) present in the spec-
–
1
2
2
trum of ZnL . Two new bends appear: a medium-intensity
2
–1
–1
band (~920 cm ) and a strong band (~840 cm ). In the
–
1
region of out-of-plane bending vibrations of the ben-
–1
zene rings (800–700 cm ), the number, the intensity
Generally, the IR spectrum of CuL is more compli- ratio, and the positions of IR bands of CuL and ZnL
2
2
2
cated than the spectrum of ZnL over the whole spectral are also different.
2
region. Some bands are split. This is especially true for
–1
Analysis of the spectroscopic data suggests that the
macrocycle conformation in CuL differs from that in
the range 1050–400 cm (Table 2). This may be caused
by low symmetry of the molecule or specific molecular
2
packing in the crystal and by different conformations of ZnL .
2
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 53 No. 6 2008

8
88
IVANOVA et al.
The complexation of CuL with alkali metal salts positions of bands are retained. An exception is the
2
induces certain changes in the vibrational spectrum. spectrum of 2NaNCS · CuL · 2H O, which contains
2 2
–
1
However, in the IR spectra of alkali metal complexes only two bands at 758 and 707 cm in this region.
with CuL , as in the spectra of complexes with ZnL ,
the bands due to vibrations of the benzene ring and SO2
2
2
Note that the spectra of all complexes are simpler
and smoother over the whole spectral region than the
retain their positions and intensity ratios observed in
spectrum of CuL , which may attest indirectly to a
2
the spectrum of uncoordinated CuL . The ν(C=N) fre-
2
polymeric structure of complexes or to the presence of
strong hydrogen bonds in the complexes or higher con-
formational uniformity of the OCCO units in the mac-
quency of the azomethine group slightly increases as
was also observed for ZnL coordination (Table 2).
2
The most pronounced changes in the vibrational rocycles.
spectrum of CuL2 upon complex formation are
observed in conformationally sensitive regions and in
–
4
In the complex 2LiClO · CuL · 2H O, the ClO
4
2
2
anion is not bound to the lithium ion, because its spec-
the region of ν(PhO) vibrations. For example, the
trum, like the spectrum of lithium perchlorate complex
νas(PhO) frequency substantially decreases upon com-
with ZnL , exhibits only two bands typical of this ion,
2
plexation, while the ν (PhO) frequency remains almost
s
–
1
–1
ν(ClO ) at ~1099 cm and δ(ClO ) at ~623 cm .
4
4
unchanged. In the spectra of potassium and sodium
–
1
–
complexes, ν (PhO) decreases by ~30 cm and for
The NCS ion occupies an outer-sphere position in
LiClO · CuL · 2H O, by 18 cm . This is somewhat the sodium and potassium complexes, as ν(C≡N) is
greater than the decrease in ν (PhO) following the for- 2051 and 2056 cm for potassium and sodium com-
as
–
1
2
4
2
2
–
1
as
mation of similar complexes with ZnL2.
plexes, respectively. In analogous ZnL complexes, the
thiocyanate group is most likely coordinated to the
metal (2071 cm for 2NaNCS · ZnL and 2075 cm
for KNCS · ZnL2).
2
In the conformationally sensitive region of ν (ëOë)
as
–
1
–1
–1
2
(
1145–1080 cm ), the IR spectra of potassium com-
plexes somewhat differ from the spectra of the sodium
or lithium complexes. The spectrum of CuL in the
2
It was shown [17] that, for alkali metal complexes
presence of potassium exhibits in this region two strong with cyclic polyethers, the stretching frequencies of
–
1
bands, at 1130 and 1083 cm , like the spectrum of coordinated water are higher than ν(ç é) for the water
2
CuL . In the case of potassium iodide complex, the involved in hydrogen bonding to anions. The pattern of
2
high-frequency component has two peaks, 1138 and absorption in the region of stretching vibrations of
–1
1
128 cm . In the spectrum of the potassium thiocyan- water molecules in the spectra of 2NaNCS · CuL ·
2
ate complex, this region comprises an asymmetric sin- 2H O, 2NaI · CuL · 2H O, and KI · CuL · H O (broad
2
2
2
2
2
–1
–1
glet band at 1126 cm . The IR spectra of the sodium asymmetric bands at 3403, 3406, and 3448 cm ,
complexes exhibit three bands in the ν (ëOë) region: respectively) indicates that water molecules in these
as
–
1
two strong bands at 1130 and 1082 cm and one weak complexes are apparently inner-sphere ligands or are
–
1
involved in hydrogen bonds. The conclusions based on
analysis of vibrational spectra are confirmed by ther-
mogravimetric data. It was found that water is removed
at a rather high temperature with simultaneous decom-
position of complexes:
band at 1103 cm (Table 2). In the spectrum of the lith-
ium complexes, a perchlorate stretching band is present
–
1
in this region at ~1099 cm , in addition to the
–
1
ν (ëOë) bands at 1131 and 1082 cm .
as
On the basis of correlations reported in the literature
–
1
äI · CuL · H O – 360°ë, 2NaNCS · CuL · 2H O – 275°ë,
2 2 2 2
[
9] for ZnL , the bands in the range 1138–1131 cm in
2
2
NaI · CuL · 2H O – 300°ë.
the spectra of all of the described complexes can be pre-
sumably assigned to ethylene glycol units with trans-
configured C–C bonds in the macrocycles, and the
bands near 1127 cm may be due to the presence of
units with approximate TGG or SGG conformations.
2 2
Analysis of the results leads to the assumption that
coordination of lithium and sodium cations to the mac-
rocycle oxygen atoms is accompanied by incorporation
of the metal in the macrocycle cavity. This results in a
–
1
In the other conformationally sensitive region (950– change in the conformation, apparently, of only several
–
1
8
00 cm ), the IR spectra of potassium complexes also ethylene glycol units. In the case of potassium com-
differ somewhat from the spectra of sodium and lithium plexes, sandwich structures are probably formed.
complexes. The spectra of potassium complexes exhibit
Macrocyclic polyethers are efficient ion transport
–
1
in this region bands at 938 and 920 cm , like the spec-
agents, in particular, in polymer membranes [18]. This
feature of crown compounds can be used for the design
of ion-selective electrodes. Previously [9], we studied
tra of uncoordinated CuL . No such bands are present
2
in the spectra of sodium or lithium complexes (Table 2).
The regions of out-of-plane bending vibrations of HL and ZnL
as the active components of plasticized
the benzene rings (800–690 cm ) in the spectra of polymeric (poly(vinyl chloride)) membranes. In this
complexes and CuL are very similar (Table 2). Only work, we carried out similar studies for CuL . The
in com-
2
–
1
2
2
the intensity ratios of some bands do change but the potentiometric selectivity sequence for CuL
2
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 53 No. 6 2008

COPPER N-(4'-BENZO-15-CROWN-5)-2-(AMINO-N-TOSYL)PHENYLALDIMINATE
889
parison with the data for HL and ZnL is presented
ACKNOWLEDGMENTS
2
below:
This work was supported by Program no. 7 of the
Division of Chemistry and Materials Science of the
RAS.
2
+
+
+
+
2+
+
+
2+
HL: Pb > Ag > K > Rb > ëu > Na ≈ Cs ≈ Sr
+
4
2
+
>
NH > Mg [9],
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+
2+
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Neorg. Khim. 52 (11), 1813 (2007) [Russ. J. Inorg.
Chem. 52 (11), 1704 (2007)].
tive toward Ag and Pb ions, whereas CuL is selec-
tive toward Cu and is not selective toward Pb . This
2
2
+
2+
is apparently related to the difference in the geometry
1
0. E. A. Materova, A. L. Grekovich, and S. E. Didina, Ele-
of ZnL and CuL molecules and in the conformation of
2
2
ktrokhimiya 8 (12), 1829 (1972).
their macrocycles. Thus, by changing the nature of the
metal in the chelate, it is possible to change deliberately
the selectivity of neutral transport agents.
1
1
1. IUPAC Recommendation for Nomenclature of Ion-
Selective Electrodes, Pure Appl. Chem., No. 48, 127
(1976).
2. I. S. Ivanova, A. V. Dorokhov, E. N. Pyatova, et al.,
Koord. Khim. 31 (7), 512 (2005) [Russ. J. Coord. Chem.
31 (7), 483 (2005)].
The studies have shown that the complexation of
CuL with alkali metal salts form complex heteronu-
2
clear structures similar to those formed with ZnL com- 13. I. K. Kireeva, N. B. Generalova, V. A. Trofimov, and
2
A. Yu. Tsivadze, Zh. Neorg. Khim. 36 (6), 1464 (1991).
plexes where lithium and sodium ions reside in the macro-
cycle cavity of the chelate, while the potassium ions coor-
dinate the oxygen atoms of two macrocycles, apparently,
of neighboring CuL molecules to give brickwork-type
sandwich structures typical of potassium complexes of
crown-containing phtalocyanines [19].
1
4. I. S. Ivanova, I. K. Kireeva, A. V. Dorokhov, and A.Yu. Tsi-
vadze, Koord. Khim. 30 (6), 455 (2004) [Russ. J. Coord.
Chem. 30 (6), 425 (2004)].
2
1
1
1
1
5. O. A. Raevskii, V. V. Tkachev, L. O. Atovmyan, et al.,
Koord. Khim. 14 (12), 1697 (1988).
6. O. A. Raevskii, V. E. Zubarev, I. I. Bulchek, and D. G. Batyr,
Koord. Khim. 14 (9), 1193 (1988).
The change in the nature of the metal incorporated
in the chelate ring on HL coordination through the
azomethine moiety virtually does not affect the com-
plexing properties of the macrocyclic donor center but
somewhat changes the macrocycle conformation. The
selectivity of these chelates with respect to ion trans-
port in plasticized poly(vinyl chloride) membranes
markedly changes.
7. D. S. Parson, M. R. Truter, and J. N. Wingfield, Inorg.
Chim. Acta 14 (1), 45 (1975).
8. Yu. A. Ovchinnikov, V. T. Ivanov, and A. M. Shkrob,
Membrane-Active Complexones (Nauka, Moscow, 1974)
[in Russian].
1
9. Yu. Yu. Enakieva, Yu. G. Gorbunova, L. I. Demina, and
A. Yu. Tsivadze, Zh. Neorg. Khim. 48 (12), 1986 (2003)
[Russ. J. Inorg. Chem. 48 (12), 1830 (2003)].
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 53 No. 6 2008