Transition Metal Chemistry (2007) 32:374–378  Springer 2007

DOI 10.1007/s11243-006-0177-z

A new tetradentate N2O2-type Schiff base ligand. Synthesis, extractive properties

towards transition metal ions and X-ray crystal structure of its nickel complex

Mohammad Reza Yaftian*, Saeed Rayati, Reyhaneh Safarbali and Niloofar Torabi
Department of Chemistry, Faculty of Science, Zanjan University, P.O. Box 45195-313 Zanjan, Iran

Hamid Reza Khavasi

Department of Chemistry, Faculty of Sciences, University of Shahid Beheshti, Tehran, Iran

Received 09 October 2006; accepted 13 December 2006

Abstract

A new tetradentate N2O2-type Schiff base, bis(2-hydroxypropiophenone)-1,2-propanediimine (L), was synthesized

by the reaction of 1,2-propanediamine with 2-hydroxypropiophenone in EtOH. The Schiff base is able to extract
CoII, NiII, CuII and ZnII ions in aqueous NaNO3 media into a CH2Cl2 organic phase via a cation exchange mech-
anism. The observed extraction order was as follows: CuII > NiII > CoII > ZnII. Reaction of nickel acetate with the
Schiff base in EtOH afforded the neutral complex Ni Æ L. Single crystals of this complex were obtained from mixed
CHCl3-EtOH (3:1) solvent and its structure was determined by X-ray diffraction. Crystal data for Ni Æ L Æ CHCl3:
triclinic, space group P, with a = 9.005(2) Å, b = 9.625(2) Å, c = 14.212(4) Å, V = 1136.8(5) Å3, a = 106.06(2)
,
b = 106.06(2), c = 105.10(2)
, and Z = 2. A near square planar structure is observed for the studied complex.

Introduction with distilled water to remove solvent stabilizer and to

Schiff base ligands provide the opportunity to design
new systems selective to specific metal ions. These li-
gands are widely used for analytical purposes such as
their use as extracting agents in liquid-liquid [1], solid
phase [2] and cloud-point [3] extraction techniques. In
addition, the incorporation of Schiff base ligands into
PVC-membranes, as ionophores, for fabricating a vari-
ety of cation [4] and anion [5] selective potentiometric
sensors have been reported. The ability of these ligands
and their complexes to reversibly bind oxygen [6], their
catalytic activity in the hydrogenation of olefins [7], and
photochemical properties [8] have been also studied. In
this paper the binding ability of a Schiff base ligand,
namely bis(2-hydroxypropiophenone)-1,2-propanedii-
mine (L, Figure 1) has been assessed by its use as ex-
tractant in single and competitive solvent extractions of
cobalt(II), nickel(II), copper(II) and zinc(II) ions from
aqueous nitrate solutions into dichloromethane. The
nickel complex of the ligand was prepared and its struc-
ture was determined by X-ray diffraction.
Experimental
Materials
saturate with H2O. Sodium, cobalt, nickel, copper and
zinc nitrate salts were analytical reagent grade and
were used for preparation of the corresponding
solutions.
Apparatus
N.m.r. measurements were performed on a FT-Bruker
(AVC 250 MHz) spectrometer. 1H-n.m.r. data are ref-
erenced using CDCl3 (7.26 p.p.m.) and 13C{1H}-NMR
chemical shifts are reported relative to CDCl3
(77.0 p.p.m.). FT-IR spectra were recorded on a Uni-
cam (Matson 1000) spectrometer. A digital melting
point measuring device (Electrothermal 9100) was
used. A Varian (AA220) flame atomic absorption spec-
trometer (air/acetylene flame) was used for metal ion
determinations. A double beam spectrophotometer
(Shimadzu, UV-240) was used for the u.v.–vis absorp-
tion determinations. The temperature of the solution
was kept constant using a Julabo circulator thermo-
stat. A pH-meter Metrohm (model 780) was used for
pH measurements.
Synthesis of bis(2-hydroxypropiophenone)-1,2-
propanediimine (L)

All chemicals were from Merck and were used without A solution of 1,2-propanediamine (0.49 g, 0.0066 mol)
further purification. CH2Cl2 was washed three times in EtOH (30 cm3) was refluxed with 2-hydroxypropi-
ophenone (2 g, 0.013 mol) for 2 h. The yellow precipi-
* Author for correspondence: E-mail: yaftian@mail.znu.ac.in tate was filtered off and recrystallized twice from

OH HO
N N
H3C CH3
CH3
Fig. 1. Structure formula of bis(2-hydroxypropiophenone)-1,2-pro-
panediimine (L).
EtOH. The purity of the product was checked by thin
layer chromatography. Yield: 1.95 g (87%), decompo-
sition point 98–100
C. u.v.–vis. (CH2Cl2): 265, 277,
330 nm. IR (KBr): mO–H = 3439 cm)1, mC–H = 2984
cm)1, mC=N = 1618 cm)1, mC=C = 1563 cm)1, mC–O =
1163 cm)1. 1H-n.m.r. (CDCl3): d (p.p.m.) 1.18–1.29 (t,
6H, CH2CH3), 1.42,1.44 (d, 3H, NCH(CH3)CH2N),
2.74–2.99 (m, 4H, CH2CH3), 3.71, 3.86 (d, 2H,
NCH(CH3)CH2N), 4.27–4.35 (m, 1H, NCH(CH3)
CH2N), 6.75–7.78 (m, 8H, ArH), 16.16, 16.41 (s, 2H,
OH). 13C{1H}-NMR(CDCl3): d (p.p.m.) 11.78 (CH
(CH3)NCCH2CH3), 12.87 (NCCH2CH3), 20.64 (NCH
(CH3)CH2N), 20.96 (CH(CH3)NCCH2CH3), 21.18
(NCCH2CH3), 54.5 (NCH(CH3)CH2N), 55.68 (NCH
(CH3)CH2H2N), 117.30–164.33 (aromatic C), 175.81
(CH(CH3)NCCH2CH3), 177.4 (NCCH2CH3). Calcd.
for C21H26N2O2: C, 75.42; H, 7.74; N, 8.28. Found: C,
74.87; H, 7.91; N, 8.06.
Preparation of the nickel complex
Nickel acetate (1 mmol) was added to a solution of
the Schiff base (1 mmol) in absolute EtOH (15 cm3).
This solution was refluxed for 1 h. The solvent was
evaporated and the dark orange product was recrystal-
ized twice from EtOH. IR (KBr):mC–H = 2976 cm)1,
mC=N = 1584 cm)1, mC=C = 1538 cm)1, mC–O = 1146
cm)1. 1H-n.m.r. (CDCl3): d (p.p.m.) 1.15–1.27 (t, 6H,
CH2CH3), 1.57 (d, 3H, NCH(CH3)CH2N), 2.59–2.92
(m, 4H, CH2CH3), 3.09–3.72 (3H, NCH2CH
(CH3)N), 6.48–7.38 (8H, ArH). The complex was dis-
solved in CHCl3/EtOH (3:1 ratio). After slow evapora-
tion over 10 days, single crystals appropriate for
structural analysis by X-ray were obtained.
Stability of the ligand
A solution of the ligand (0.02 M) in CH2Cl2 was
stirred with an aqueous solution containing NaNO3
(0.1 M) at different pH’s (2–9) for 20 min. After
separation of the phases, the organic solvent was
evaporated. The residue was dissolved in CDCl3 and
the 1H-n.m.r. spectrum was recorded. The obtained
spectrum was compared to that of the ligand before
use in this experiment.
375
Distribution of the Schiff base
An equal volume of aqueous (0.1 M NaNO3) phase
with a given pH (2–11) and organic phase (0.001 M
solution of Schiff base in CH2Cl2) was stirred for
30 min. Adding HNO3 or NaOH solutions (0.1 M)
provided variation of the pH. The phases were sepa-
rated and the percentage of the Schiff base remaining
in the organic phase was determined, after appropriate
dilution, by absorption measurements on the organic
phase at 330 nm.
Solvent extraction experiments
Solvent extraction experiments were carried out in
stoppered glass tubes immersed in a thermostated
water bath (22.0 ± 0.1
C) using equal volumes
(5 cm3) of the organic and aqueous phases. The pH of
the aqueous phase was adjusted by addition of nitric
acid or sodium hydroxide solutions. The extraction
equilibrium was reached after 20 min under continu-
ous magnetic stirring. After separation of the phases,
the equilibrium pH was checked. The metal concentra-
tion in the organic phase was measured by AAS after
back-extraction of the phase with excess nitric acid
solution (0.1 M).
X-ray data collection and processing for the nickel
complex
A dark orange crystal of C22H25Cl3N2O2Ni Æ CHCl3
with approximate dimensions of 0.3
0.13
0.10 mm3
was mounted on a glass fiber. All measurements were
made on a STOE IPDS-II diffractometer with graphite
monochromated Mo-Ka radiation. The data were col-
lected at 293(2) K to a maximum 2h value of 26.82

and a series of x scans in 1
oscillations with 120 s
exposures. The crystal-to-detector distance was
120 mm. Crystal data and details of data collection are
given in Tables 1 and 2.
Of the 7635 collected reflections, 4442 were unique
(Rint = 0.0354), equivalents reflections that were
merged. Data were collected and integrated using the
stoe X-AREA [9] software package. The numerical
absorption coefficient, l, for Mo-Ka radiation is
1.227 mm)1. A numerical absorption correction was
applied using X-RED [10] and X-SHAPE [11] sof-
ware’s, which resulted in transmission factors in the
range 0.692–0.885. The data were corrected for Lo-
rentz and Polarizing effects. No decay correction was
applied. The structure was solved by direct/heavy-
atom Patterson methods [12]. All of the non-hydrogen
atoms were refined anisotropically. All of hydrogen
atoms were located in ideal positions except C22
hydrogen that placed in the different Fourier map. The
final cycle of full-matrix least-squares refinement by
376
Table 1. Crystallographic data for Ni Æ L Æ CHCl3 Table 2. Atom coordinates (
104) and equivalent isotropic displace-
ment parameters (Å2
103) for Ni Æ L Æ CHCl3. U(eq) is defined as
Empirical formula C22 H25 Cl3 N2 Ni O2 one third of the trace of the orthogonalized Uij tensor
Formula weight 514.48
Temperature 293 (2) (K) x y z U (eq)
Wavelength 0.71073 (Å)
Crystal system, space group Triclinic, P Ni (1) 6001 (1) 5281 (1) 6829 (1) 34 (1)
Unit cell dimensions N (1) 6726 (3) 4137 (2) 5754 (2) 38 (1)
a (Å) 9.005 (2) N (2) 5806 (3) 3723 (2) 7396 (2) 40 (1)
b (Å) 9.625 (2) C (1) 7014 (3) 7121 (3) 5596 (2) 38 (1)
c (Å) 14.212 (4) C (2) 7396 (4) 8589 (3) 5486 (2) 52 (1)
a (
) 106.06 (2) C (3) 7962 (4) 8865 (4) 4644 (2) 57 (1)
b (
) 91.32 (2) C (4) 8157 (4) 7685 (4) 3872 (2) 54 (1)
c (
) 105.10 (2) C (5) 7808 (3) 6262 (4) 3964 (2) 46 (1)
Volume 1136.8 (5) (Å)3 C (6) 7260 (3) 5926 (3) 4824 (2) 37(1)
Z, Calculated density 2, 1.503 (Mg/m3) C (7) 7044 (3) 4411 (3) 4917 (2) 37(1)
Absorption coefficient 1.227 (mm)1) C (8) 7231 (3) 3172 (3) 4040 (2) 45 (1)
F(000) 532.0 C (9) 8900 (4) 3100 (4) 3961 (3) 59 (1)
Crystal size 0.30
0.13
0.10 (mm) C (10) 6649 (4) 2634 (3) 5861 (2) 51 (1)
Theta range for data collection 1.50 to 26.82 (deg.) C (11) 6849 (4) 2808 (3) 6950 (2) 49 (1)
Limiting indices ) 11 £ h £ 11, ) 12 £ k C (12) 8509 (4) 3618 (4) 7399 (3) 61 (1)
£ 12, ) 14 £ l £ 17 C (13) 5025 (3) 3455 (3) 8114 (2) 38 (1)
Reflections collected/unique 7635/4442 [R(int) = 0.0354] C (14) 5097 (4) 2142 (3) 8494 (2) 47 (1)
Completeness to theta = 26.82 91.0% C (15) 3935 (5) 665 (4) 7901 (3) 71 (1)
Absorption correction Numerical C (16) 4030 (3) 4389 (3) 8554 (2) 37 (1)
Max. and min. transmission 0.885 and 0.692 C (17) 2956 (3) 3931 (3) 9193 (2) 48 (1)
Refinement method Full-matrix least-squares on F2 C (18) 2000 (4) 4768 (4) 9608 (2) 54 (1)
Data/restraints/parameters 4442/0/276 C (19) 2095 (3) 6135 (4) 9429 (2) 51 (1)
Goodness-of-fit on F2 1.165 C (20) 3129 (3) 6627 (3) 8814 (2) 43 (1)
Final R indices [I > 2sigma(I)] R1 = 0.0403, wR2 = 0.1205 C (21) 4122 (3) 5781 (3) 8364 (2) 36 (1)
R indices (all data) R1 = 0.0483, wR2 = 0.1295 C (22) 7986 (4) 9046 (3) 8538 (2) 54 (1)
Extinction coefficient 0.050(5) O (1) 6424 (2) 6968 (2) 6407 (1) 44 (1)
Largest diff. peak and hole 0.502 and ) 0.447 (e.A)3) O (2) 5066 (2) 6348 (2) 7789 (1) 42 (1)
Cl (1) 9110 (2) 10 658 (1) 8277 (1) 88 (1)
Cl (2) 7033 (2) 9595 (1) 9574 (1) 87 (1)
P Cl (3) 9149 (2) 7923 (1) 8717 (1) 99 (1)
minimizing w(F02 ) Fc2)2 on F2 was based on 4442
unique reflections and 276 variable parameters and
converged with unweighted and weighted agreement
Therefore in the first step of this study we assessed the
factors of (all data):
X X stability of our Schiff base under extraction conditions
R1 ¼ jjF0 j  jFc jj= jF0 j ¼ 0:0483 by comparing 1H-n.m.r. spectra of the ligand before
X X and after equilibration with the aqueous phase (0.1 M
2
wR2 ¼ ½ ðwðF0  Fc Þ2Þ= 2
wðF20 Þ2 1=2 ¼ 0:1295
NaNO3, pH = 2–9). The spectra were essentially iden-
Using the following equation, tical, revealing the stability of the ligand under these
X X conditions.
½ wðF20  F2c Þ2  = ðN0  Nv Þ1=2
The logarithm of the distribution coefficient
where N0 is number of observations and Nv is number (Kd = [L]org/[L]aq) of the Schiff base, partitioned be-
of variables, the standard deviation of an observation tween a dichloromethane organic phase and a 0.1 M
of unit weight was determined to be 1.165. The maxi- solution of NaNO3 as a function of the aqueous phase
mum and minimum peaks on the final difference map pH, is shown in Figure 2. The distribution coefficient
correspond to +0.502 and ) 0.447 e-/Å3, respectively. increases with increasing pH up to 7–8. Beyond this
Neutral atom scattering factors were taken from Cro- pH range, the distribution coefficient decreases. This
mer and Waber [13]. Anomalous description effects behavior can be explained by protonation of nitrogen
were included in Fcalc [14], the values for Df¢ and Df¢¢ atoms of the Schiff base at low pH, on one hand, and
were those of Creagh and McAuley [15]. The values ionization of hydroxyl groups at the higher pH values,
for the mass attenuation coefficients are those of on the other hand.
Creagh and Hubbell [16]. All refinements were per- Individual liquid-liquid extraction experiments for
formed using the X-STEP32 [17] crystallographic soft- cobalt(II), nickel(II), copper(II) and zinc(II) from
ware package. 0.1 M sodium nitrate solution using the Schiff base in
dichloromethane as a function of the aqueous phase
pH were carried out, and the results are shown in
Results and Discussion Figure 3. An increase in extraction percentage with
increasing aqueous phase pH suggests a cation
The possible hydrolysis of the imine moieties of Schiff exchange mechanism for the extraction process. Quan-
base ligands can prohibit their use as extractants. titative transfer of copper ions from the aqueous phase
 377

1.2 Table 3. Results of the competitive extraction of metal ionsa

Cation [M2+]0 (M) [M2+]org (M) E% logSFb

1 Cu2+ 10)4 9.81
10)5 98 –

Ni2+ 10)4 8.24
10)5 82 1.04
Co2+ 10)4 4.79
10)5 48 1.75
Zn2+ 10)4 3.62
10)5 36 1.96
0.8
a
aqueous phase: initial cation concentration, [M]0; [NaNO3], 0.1 M;
pH, 6; Organic phase: [L], 0.02 M in dichloromethane. b logSF =
logKd

log(DCu/DM); D = [M]org/[M]aq.
0.6

carried out. The results and the selectivity coefficients

0.4
0.2
0 veals a 1:1 (metal to ligand) stoichiometry. The IR
2 4 6 8 10
pH
Fig. 2. Plot of the logarithm of distribution coefficient of the Schiff
base as a function of the aqueous phase pH.
into the organic phase is achieved in the pH range
4–9. At these pH values the cobalt and zinc ions are
extracted less than 60 percent. The selectivity of the
extractant towards tested metal ions was as follows:
CuII > NiII > CoII > ZnII.
In order to further test the selectivity of the Schiff
base, competitive extraction of a mixture of CoII, NiII,
CuII and ZnII in aqueous phase (pH = 5.5) was
are given in Table 3. It seems that the extraction order
is similar to that observed in the single species extrac-
tion experiments.
In order to elucidate the stoichiometry of the nickel
complex of the Schiff base, this complex was prepared.
The analysis of the nickel content in the complex re-
12 14
spectrum of the free Schiff base shows bands at 3439,
1618 and 1163 cm)1 corresponding to O–H, C=N and
C–O groups, respectively. The peak at 3439 is absent
from the spectrum of the complex, suggests deprotona-
tion of the hydroxyl groups. A shift towards lower fre-
quencies for the C=N and C–O groups (1584 and
1146 cm)1, respectively) suggests coordination of
nitrogen and oxygen atoms to the metal in the com-
plex. The solid state structure of the Ni Æ L complex
was resolved by an X-ray diffraction study. Its crystal
structure is shown in Figure 4. Selected bond length
and angles are given in Table 4. The bond angles show
that geometry of the complex is nearly square planar.

Conclusions
100
Bis(2-hydroxypropiophenone)-1,2-propanediimine can
90 be synthesized by the reaction of 1,2-propanediamine
and 2-hydroxypropiophenone in ethanol. This
80 Schiff base binds efficiently to cobalt(II), nickel(II),

70
Extraction Percentage

60

50

40

30 Zn
Ni
20
Co
Cu
10

0
2 4 6 8 10 12
pH
Fig. 3. Extraction of metal ions (initial concentration 1
10)4 M)
from aqueous NaNO3 solutions (0.1 M) into a dichloromethane solu-
tion of L (0.02 M) as a function of pH in the single extraction exper- Fig. 4. Ortep drawing for Ni Æ L Æ CHCl3 using equivalent isotropic
iments at 22
C. temperature factors.
378
Table 4. Selected interatomic distances (Å) and angles (
) in Ni Æ - 5. J. Dai, Y. Chai, X. Zhong, Y. Liu and D. Tang, Anal. Sci., 20,
L Æ CHCl3 1661 (2004).
6. R.D. Jones, R.D. Summerville and F. Basolo, Chem. Rev., 79, 139
Distances (1979).
Ni–O(1) 1.8348 (19) C(1)–O(1) 1.310 (3) 7. G. Henrici-Olive and S. Olive, The Chemistry of the Catalyzed
Ni–O(2) 1.8313 (18) C(21)–O(2) 1.314 (3) Hydrogenation of Carbon Monoxide, Springer, Berlin, 1984.
Ni–N(1) 1.860 (2) N(1)–C(7) 1.311 (3) 8. A.H. Osman, Transition Met. Chem., 31, 35 (2006).
Ni–N(2) 1.862 (2) N(2)–C(13) 1.299 (3) 9. Stoe & Cie, X-AREA, Version 1.30: Program for the acquisition
Angles and analysis of data; Stoe & Cie GmbH: Darmatadt, Germany,
O(1)–Ni–O(2) 84.59 (8) N(1)–Ni–O(2) 172.96 (9) 2005.
O(1)–Ni–N(1) 94.48 (9) O(1)–Ni–N(2) 171.76 (10) 10. Stoe & Cie, X-RED, Version 1.28b: Program for the data reduc-
N(1)–Ni–N(2) 88.27 (10) O(2)–Ni–N(1) 172.96 (9) tion and absorption correction; Stoe & Cie GmbH: Darmatadt,
Germany, 2005.
11. Stoe & Cie, X-SHAPE, Version 2.05: Program for crystal opti-
mization for numerical absorption correction; Stoe & Cie GmbH:
copper(II) and zinc(II) ions. The X-ray diffraction Darmatadt, Germany, 2004.
analysis of the nickel complex of the Schiff base shows 12. G.M. Sheldrick, SHELX97. Program for crystal structure solution
and refinement. University of Göttingen, Germany, 1997.
that the metal ion is coordinated by nitrogen and oxy- 13. D.T. Cromer, J.T. Waber, International Tables for Crystallogra-
gen atoms in a pseudo-square planar geometry. phy, Table 2.2A, Vol. 4, The Kynoch Press, Birmingham, 1974.
14. J.A. Ibers and W.C. Hamilton, Acta Crystallogr., 17, 781 (1964).
References 15. D.C. Creagh, W.J. McAuley, International Tables for Crystal-
lography, Table 4.2.6.8, Vol. C, in A.J.C. Wilson, (ed.), pp.
219–222 l. 4, Kluwer, Boston, 1992.
1. H. Hirayama, I. Takeuchi, T. Honjo, K. Kubono and H. Koku-
16. D.C. Creagh J.H. Habbell, International Tables for Crystallog-
sen, Anal. Chem., 69, 4814 (1997).
raphy, Table 4.2.4.3, Vol. C, in A.J.C. Wilson, (ed.), pp. 200–206,
2. T. Shamspur, I. Sheikhshoaie and M.H. Mashhadizadeh, J. Anal.
Kluwer, Boston, 1992.
At. Spectrom., 20, 476 (2005).
17. Stoe & Cie, X-STEP32, Version 1.07b: Crystallographic package;
3. F. Shemirani, Sh. Dehghan Abkenar, A.A. Mirroshandel, M.
Stoe & Cie GmbH: Darmatadt, Germany, 2000.
Salavati-Niasari and R. Rahnama Kozania, Anal. Sci., 19, 1453
(2003).
4. M.R. Ganjali, P. Norouzi, A. Daftari, F. Faridbod and M.
Salavati-Niasari, Sens. Actuators B, 115, 374 (2006). TMCH 6677