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Journal of the Chinese Chemical Society, 2011, 58, 60-68

Synthesis, Structure and Solvatochromism Studies on Copper(II) Complexes Containing Ethylenediamine, Pyridine and Imidazol Ligands
Hamid Golchoubian,a* Omeleila Nazaria and Benson Kariukib
a

Department of Chemistry, University of Mazandaran, Babolsar, Postal code 47416-95447, Iran b School of Chemistry, Cardiff University, Main College, Park Place, Cardiff CF10 3AT, UK
Received June 2, 2010; Accepted December 14, 2010; Published Online January 4, 2011

Two copper(II) complexes type [Cu(en)X2](ClO4)2, where en = ethylenediamine and X = pyridine, 1 or imidazol, 2 have been synthesized and prepared on the bases of elemental analysis, spectroscopic and molar conductance measurements. The X-ray crystal analysis of these complexes demonstrated that the copper(II) ions are in square planar environments through coordination by two nitrogen atoms of the ethylenediamine and two nitrogen atoms of two pyridine or imidazol molecules and the ClO4- ions are bound weakly above and below of the molecular plane. The complexes show three ions behavior in all solvents. The complexes are soluble in various solvents and are solvatochromic. The solvatochromism of the complexes were investigated by UV-Vis spectroscopy with different solvent parameters such as DN, AN, a and b using multiple linear regression (MLR) method. The results suggested that the DN parameter of the solvent has the most contribution to the shift of the d-d absorption band of the complex 1 but in complex 2 the DN and b have almost similar importance in the observed variation in the shift of the nmax values with solvent nature. Keywords: Solvatochromism; Backward multiple linear regression; Crystal structure; Copper(II) complex; Imidazol; Pyridine.

INTRODUCTION The investigation of solvatochromic behavior of metal complexes has been of importance, because it provides a quantitative approach to recognize the solvent behavior and the role of the solvent in physico-chemical studies.1,2 The effect of the solvent on the spectral properties of molecules, generally referred as solvatochromism, has been investigated for many years, generating a copious literature.3 Solvatochromism of metal complexes can be divided into two types;4,5 the first type comprises the case where the color changes are brought about by the direct attachment of solvent molecules onto metal center, and the second type is due to the attachment of solvent molecules onto ligands. Among the former whose color changes are due to those of dd transitions, copper(II) complexes with a strong JahnTeller effect can be anticipated to show simple and regular changes in their electronic spectra according to the strength of interactions with solvent molecules at the axial sites.6-8 There are many applications for this phenomenon such as Lewis acid-base color indicator, 9 imaging, 10-13 photo* Corresponding author. E-mail: h.golchobian@umz.ac.ir

switching,14-16 and sensor materials.17 It has been known that wave numbers corresponds to absorption maxima of the compounds in solvents of used correlate well with the solvent parameters. Various solvent parameters such as Dimroth and Reichardts E T, Z Kosowar, Kamlet and Tafts a, b, p* and Gutmans donor and acceptor number, DN and AN have been introduced in literature.18-20 Each of these parameters is related to different type of interaction exist between compound and solvent. The existent dependencies between the spectral shifts and solvent parameters can be verified by computational methods. In this work, which is a continuation of our studies on the solvatochromic behavior copper(II) complexes we intend to study the electronic properties imposed by the Ndonor atoms of the monodentate ligands pyridine and imidazol on the copper(II) ion of the complexes type [Cu(en)X 2](ClO 4) 2 (Fig. 1) where en = ethylenediamine and X = pyridine or imidazol. Based on our knowledge such investigation has not been carried yet.

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RESULTS AND DISCUSSION The complexes were prepared readily in high yield with mixing of Cu(ClO4)26H2O, ethylenediamine and pyridine or imidazole with mole ratio of 1:1:2, respectively in solvent of water and methanol. The analytical data indicated the formation of the desired complexes. IR spectra The IR spectrum of complex 1 showed bands at 32703325 cm-1 attributed to the symmetric stretch of C-H aromatic of pyridine moieties which is shifted to upper frequency in compare with free pyridine molecule. Ring stretching bands appear between 1450-1608 cm-1 and out of plane bending of C-H of pyridine ring appeared at 705764 cm-1.21 CH2 rocking and Cu-N stretching vibration mode of ethylenediamine were appeared about 850-950 cm-1 and 500-610 cm-1, respectively for both complexes.21 The IR spectrum of complex 2 shows NH stretching at 3366 cm-1 and a band at 3056 cm-1 attributed to the symmetric stretch of C-H in imidazole groups. The infrared spectra of two complexes show two intense bands at around 1110 and 620 cm-1 which are attributed to presence of the ClO-4. These bands are declared to the anti-symmetric stretching and anti-symmetric bending vibration mode, respectively.22 The former is split with a poorly defined maximum showing the deformation from Td symmetry. It is well known that the degree of splitting of this band serves as a measure of the degree of the coordination of perchlorate ions to the copper(II) ion.23,24 Conductometric data The molar conductivity values of the mixed-chelate complex in solvents of nitromethane (NM), dimethyleformamide (DMF), methanol (MeOH) and acetonitrile (AN) were studied. The data are listed in Table 1. The results reveal that the complexes are 1:2 electrolytes in all solvents.25,26 Although the complexes are in molecular form in

Table 1. The molar conductance (Lm) of the complexes (W-1 cm2 mol-1, at 25 C) in some solvents Solvent Nitomethane (NM) Acetonitrile (AN) MeOH DMF
a

Compound 1 144 234 204 146 2 178 268 220 130

Standard values for 1:2 electrolytesa 150-180 220-300 160-220 130-170

the standard values taken from ref. 26.

solid state as X-ray crystal structures indicated they are electrolytes in solution. That means ClO4- ions are bound weakly above and below of the chelate planes and can be driven out by solvent molecules which leading to their solvatochromism. Single crystal X-ray analyses The view of ORTEP diagrams of the copper complexes 1 and 2 are presented in Fig. 2 and 3, respectively. The selected bond distances and bond angles for the complexes are listed in Table 2. The bond distances Cu(1)-N(1) in complex 1 and Cu(1)-N(2) in complex 2 are 2.591 and 1.991 , respectively. This difference is quiet normal be-

Fig. 1. The copper(II) complexes of [Cu(en)Py2](ClO4)2, 1 and [Cu(en)(Imzl)2](ClO4)2, 2.

Fig. 2. ORTEP diagram of complex 1 with atom labels and numbering scheme with fifty percent probability.

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Table 2. Selected bond lengths () and angles () for compound 1 and 2 Compound 1 N(1)Cu(1) N(2)Cu(1) Cu(1)O(1) N(1)Cu(1)N(1i) N(2)Cu(1)N(2i) N(2)Cu(1)N(1) N(2i)Cu(1)N(1) N(1i)-Cu(1)-N(2i) O(2)Cu(1)O(2i) N(2)-C(6)-C(6i)-N(2i) 2.019(2) 2.016(2) 2.591(2) 90.12(12) 84.34(12) 174.79(9) 92.93(9) 174.80(9) 178.97(18) 52.14(18) Compound 2 N(2)Cu(1) Cu(1)O(2) N(3)Cu(1) N(2)Cu(1)N(3) N(2)Cu(1)N(2i) N(3)Cu(1)N(3i) N(2)Cu(1)N(3i) O(2)Cu(1)O(2i) N(3)-C(4)-C(4i)-N(3i) 1.991(3) 2.632(3) 2.011(3) 176.95(13) 89.32(18) 84.05(18) 93.34(13) 177.44(13) 51.41(18)

cause pyridine and imidazole have different basicity power. The basicity of free imidazole (K b = 1.2 10 -7) is about hundred times stronger than pyridine (Kb = 2.3 10-9).27,28 The five-membered chelate ring in both complexes are puckered; the torsion angles of N(3)-C(4)-C(4i)-N(3) and N(2)-C(6)-C(6i)-N(2i) in complex 1 and 2 are 52.14 (18), 51.41 (18), respectively. The copper(II) ion resides in the plane between the coordinating atoms N(1), N(2), N(1 i) and N(2i) in both complexes. The angle between this plan and the pyridine plane is 54.21(2) in complex 1. The angle between the N4Cu plane and the imidazole plane in complex 2 is 62.28(2). The mean Cu-N(amine) distance (2.016(3) and 2.011(3) ) and the bite angles N(2)Cu(1)-N(2i) of 84.34 (12)o and N(3)-Cu(1)-N(3i) of 84.05 (18) for complexes 1 and 2, respectively are close to the corresponding average values of the copper(II) complexes with ethylenediamine reported before.29,30 The angles between two pyridine rings in complex 1 and the rings of two imidazol in complex 2 are 60.83(2), 68.87(2), respec-

tively. Two perchlorate ions lie above and below of the copper ion in both complexes; the bond lengths of Cu-OClO3 are 2.591 and 2.632 in complex 1 and 2, respectively and hence the ClO4- ions coordinated weakly to the copper(II) ions and can be driven out by the solvent molecules in solution which leads to their solvatochromism. It is found that the hydrogen bonding affects the molecular packing. In complex 1 each molecule links with two other molecules via intermolecular hydrogen bonds to form one-dimensional polymer along crystallographic c axis as illustrated in Fig 4. However, in complex 2 an additional hydrogen bond also exist between O(4) of the perchlorate ion and H(3A) of the ethylenediamine of neighboring molecules. These hydrogen bondings make a two-dimensional sheet structure along crystallographic c axis as shown in Fig. 5. Solvatochromism The UV-Vis spectra of the complexes show a broad band at visible region due to d-d transition of copper(II) ion. This transition is characteristic of copper(II) in the square planar environment associated to the 2B1g 2A 1g transition.31,32 The position of the nmax of the complexes along with their molar absorptivity and respective solvent parameter values are collected in Table 3. The Vis spectra of the complexes in selected solvents are illustrated in Fig. 6 and 7, respectively. The multiple linear regression used to deduce the solvatochromic behavior of the complexes. In this regard, hydrogen bonding ability a, electron pair donating ability b, Gutmanns DN, Mayer and Gutmanns AN were used according to Eq. (1). The frequencies of d-d absorption transition band (nmax) of each complexes in various solvents (Table 3) with their own solvent parameters were offered in

Fig. 3. ORTEP diagram of complex 2 with atom labels and numbering scheme with fifty percent probability.

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Fig. 4. Packing diagram of the complex 1 containing hydrogen bonding along crystallographic c axis.

Fig. 5. Packing diagram of the complex 2 containing hydrogen bonding along crystallographic c axis.

Eq. (1) pointed out in experimental section one by one to the statistical computer program. Specifically, in first step all variables are reviewed and evaluated to determine which one will contribute most to Eq. (1). Then the weaken variable is excluded in the model and process starts again. The quality of the obtained equations and the percentage contribution of the calculated solvatochromic parameters are presented in Table 4. The regression coefficients reported in the table suggest that the DN parameter of the solvent has the dominate contribution (52.3%) in the shift of

d-d absorption band of the complex 1. However, in complex 2 the DN and b are almost similar importance to explain the observed variation in the shift of the nmax values with solvent nature with relative contribution of 47.5 and 41.4%, respectively using normalized DNN. The negative sign of the coefficient of the DN in complexes indicates a red shift as the donor number of solvent increases. The positive sign of the b signifies opposite function of the basicity power in the solvatochromism of complex 2. The position of the band maxima in complexes shifted

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Table 3. The solvent parameter values and the maximal absorption frequencies, nmax/103cm-1 (e/M-1 cm-1) of complex 1 and 2 in various solvents Solvent Nitromethane Acetonitrile Acetone THF MeOH DMF DMSO H2O DN 2.7 14.1 17.0 20.0 23.3 26.6 29.8 18.0 AN 20.5 18.9 12.5 8.0 41.3 16.0 19.3 54.8 b 0.06 0.31 0.48 0.55 0.62 0.69 0.76 0.47 a 0.22 0.19 0.08 0.0 0.9 0.0 0.0 1.17 Complex 1 17.63 (81) 17.38 (55) 17.08 (49) 16.00 (38) 15.87 (465) 15.26 (49) 14.74 (55) 15.60 (39) Complex 2 17.75 (73) 17.53 (66) 16.38 (79) 17.33 (66) 16.85 (64) 16.67 (70) 16.25 (42) 16.65 (48)

Table 4. The correlation of the electronic spectral with the solvent parameters calculated by MLR technique Complex number 1 2 Equation nmax = 18.988 0.213 DN + 4.041 b 0.050 AN + 1.174 a DN = 52.25%, AN = 13.16%, a = 29.59%, b = 5.00% nmax = 17.359 0.550 DN + 18.689 b + 0.058 AN 2.447 a DN = 47.49%, AN = 6.10%, a = 5.10%, b = 41.39% F 5.747 9.359 S.E. 0.545 0.228 R 0.941 0.962 n 8 8

to the higher wave number as the donor number of the solvents increases. This red shift is due to the strong repulsion of the electrons in dz2 orbital by ion pair electrons of the solvent molecules that are axially coordinated to the copper center.33 The observed solvatochromism is a reverse process so that the removal of the solvent under high vacuum regenerate the original complexes. A plot of the nmax values calculated using Eq. (1) versus the nmax values observed for complexes 1 and 2 in different solvents is presented in Fig. 8 and 9.

CONCLUSION The prepared two complexes are soluble in organic solvents and show solvatochromism properties. Their solvatochromism were examined with different solvent parameters models using backward MLR computational method. The obtained results suggested that the complex 1 correlate well with DN whereas complex 2 shows good correlation with DN and b (electron pair donating scale) of the solvents. The d-d visible absorption band exhibits a red shift with the increase of the donor number (DN) (in complex 1) and DN plus electron pair donating ability of the

Fig. 6. Absorption spectra of complex 1 in selected solvents.

Fig. 7. Absorption spectra of complex 2 in selected solvents.

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Fig. 8. Plot of the n max observed against n max calculated from Eq. (1) for complex 1.

Fig. 9. Plot of the n max observed against n max calculated from Eq. (1) for complex 2.

solvents (in complex 2). This behavior was explained on the bases of the weakly coordination of the perchlorate anions in axial position of the copper(II) complexes in which are replaced by solvent molecules with different donor power or electron pair donating ability. EXPERIMENTAL SECTION All chemicals and solvents were obtained from Merck and Fluka and used without further purification. Caution: perchlorate salts are potentially explosive and should be handled with appropriate care. Conductance measurements were made at 25 oC with a Jenway 400 conductance meter on 1.00 10-3 M samples in selected solvents. Infrared spectra (potassium bromide disk) were recorded using a Bruker FT-IR instrument. The electronic absorption spectra were measured using a Braic 2100 model UV-Vis spectrophotometer. The elemental analyses were performed on a LECO 600 CHN elemental analyzer. Absolute metal percentages were determined by a Varian-spectra A-30/40 atomic absorption-flame spec-

trometer. Synthesis of complex 1 [Cu(en)Py2](ClO4)2, was prepared by adding pyridine (8 mmol) in 10 mL MeOH to an aqueous solution of Cu(ClO 4)26H2O (4 mmol in 5 mL distillated water) and stirring for about 1 h at room temperature. To the resultant blue solution, ethylenediamine (4 mmole) was then added and the reaction mixture was stirred at room temperature. Blue-violet crystals obtained were filtered, washed with cold water and dried in a dessicator. The yield was 85%. Single crystals suitable for X-ray diffraction studies were obtained by recrystallization of the complex in methanol. Selected IR data (n/cm-1 using KBr): 3325 (s), 3270 (s), 2035 (w), 1608 (m), 1592 (s), 1490 (w), 1467 (w), 1450 (s), 1112 (s), 1080 (s), 764 (m), 705 (s), 623 (s), 523 (m). Anal. calcd. for C12H 18Cl2CuN 4O 8 (Mr = 480.75) C, 29.98; H, 3.77; N, 11.65; Cu, 13.22; found: C, 30.10; H, 3.51; N, 11.51; Cu, 13.27%. Synthesis of complex 2 This compound was prepared with the same procedure as complex 1 except that imidazol was used in place of pyridine. The violet crystals were obtained with the yield of 85%. The recrystallization of the complex in MeOH provided suitable crystals for X-ray crystallography. Selected IR data (n/cm-1 using KBr): 3366 (w), 3328 (w), 3057 (w), 2935 (w), 1660 (s), 1605 (m), 1573 (w), 1542 (s), 1470 (s), 1443 (m), 1340 (m), 1286 (m), 1264 (w), 1220 (s), 1091 (s), 946 (w), 930 (w), 864 (m), 756 (m), 623 (s), 551 (w). Anal. calcd. for C8H14Cl2CuN6O8 (Mr = 456.69): C, 21.04; H, 3.09; N, 18.40; Cu, 13.91; Found: C, 21.31; H, 2.95; N, 18.26; Cu, 13.99%. X-ray crystallography A suitable single crystal of complex 1 and 2 were glued on the tip of glass fibers. The X-ray data were collected by w-scans on Nonius BV diffractometer with graphite-monochromated Mo Ka radiation (l = 0.71073 ). Data reduction, including the absorption correction, was performed with the HKL DENZO and SCALEPACK software package.34 Solution, refinement and analysis of the structure were performed by using SHELXTL programs.35,36 The structure was solved by direct methods (SIR92)37 and refined by the full-matrix least-squares method based on F2 against all reflections.38 Geometrical calculations were carried out with PLATON39 and the figures were made by the use of the ORTEP9940 and MERCURY 41 programs. The complete conditions of data collection and structure refinements are given in Table 5. The H(C) atom positions were

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Table 5. Crystal data and structure refinement parameters for compounds 1 and 2 Compound Empirical formula Formula weight color Temperature/K Wavelength/nm Crystal system Space group Unit cell dimension 1 C12H18Cl2CuN4O8 480.74 Blue 150 0.71073 Monoclinic C 2/c a = 7.6520(3) b = 17.0720(4) c = 14.0750(7) b = 99.945(3) 1811.06(12) 4 1.763 980 0.969 and 0.742 -9 h 9, -22 k 22, -18 l 18 1.55 2074/123 R = 0.0382, wR2 = 0.0829 99.6% Full-matrix least-squares on F2 1.07 2 C8H14Cl2CuN6O8 456.70 Violet 299 0.71073 Monoclinic C 2/c a = 7.5070(3) b = 15.9110(4) c = 14.5140(6) b = 98.964(2) 1712.44(11) 4 1.771 924 0.849 and 0.745 -9 h 9, -20 k 20, -18 l 18 1.63 1933/114 R = 0.0540, wR2 = 0.1467 99.1% Full-matrix least-squares on F2 1.04

Volume Z Calculated density F (000) Max. and min. transmission Limiting indices m (mm-1) Reflections collected/unique R indices (all data) Completeness to q = 27 Refinement method S
a b

R = ||Fo| - |Fc||/|Fo|. wR = [( [Fo 2 - Fc 2)2] / [w(Fo2)2]. c S = [w(Fo 2 - Fc 2)2/(Nobs - Nparam)].

calculated. All hydrogen atoms were refined in isotropic approximation in riding model with the Uiso(H) parameters equal to 1.2 Ueq(Ci), for methyl groups equal to 1.5 Ueq(Cii), where U(Ci) and U(Cii) are respectively the equivalent thermal parameters of the carbon atoms to which corresponding H atoms are bonded. Refinement of F2 was against all reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2s(F2) is used only for calculating R-factors(gt) etc., and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on all data will be even larger. Method of calculation All the absorption maxima reported were taken from experimental curves of d-d transition of the complexes. Multivariate statistical methods have been used in the classification and selection of solvents. Empirical parameters of solvent polarity were used as basic data sets. These pa-

rameters can be obtained directly from literature.43-45 The extraction of chemical information contained in such a data set can be carried out by statistical method of Multiple Linear Regression analysis (MLR). In this method, a dependent variable Y is described in terms of a series of explanatory variables X1Xn, as given in Eq. (1): Y = Y0 + a2.X2 +.+ anXn + a1.X1 (1)

It is assumed that all the explanatory variables are independent of each other and truly additive as well as relevant to the problem under study.46,47 Y is the value of a solvent dependent physicochemical property (nmax in this study) in a given solvent and Y0 is the statistical quantity corresponding to the value of this property in the gas phase or in an inert solvent. X1, X2, Xn represent independent but complementary solvent parameters, which account for the different solute/solvent interaction mechanisms. a 1, a2,an are the regression coefficients describing the sensitivity of property Y to the different solute/solvent interac-

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tion mechanisms. The postulate is that the solvent effect on a solute property Y can be represented as a linear function of some independent but complementary parameters describing the Lewis acidity and basicity of a given solvent. The AN and a, values are chosen as a measure of Lewis acidity. In addition, Gutmanns donor number DN and b were chosen as a measure of solvent basicity.45-51 In this approach, the backward procedure was used for selection of the most relevant variables. A final set of selected equations was examined for stability and validity through a variety of statistical methods. The choice of equation suitable for further consideration was made by using four criteria, namely, multiple correlation coefficients (R), standard error (S.E.), F-statistic and the number of variables (n) in the model. The best multiple linear regression model is one that has high R and F-values, low standard error, least number of variables and high prediction ability. In Parameter selection, variables with small variance t (not significant at the 5% level) were then removed. t value is the solvent-independent coefficients divided by SE. To determine the relative significance of solvent parameters, the regression coefficients are described in terms of percentage contribution value. Eq. (2) could be statistically qualified into percentage contribution factor [P(Xi)]. To attain this, the regression coefficients, which emerge from multiple regression equations are normalized to numerical range 0-1.52 Hence, percentage contribution P(X i) of a solvent parameter in multiple regression is calculated53 as in the following equation: P(Xi) = 100| a i | (2)

tary crystallographic data for compounds 1 and 2 of this paper, respectively. These data can be obtained free of charge via 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 336033). ACKNOWLEDGEMENT We are grateful for the financial support of the Mazandaran University of the Islamic Republic of Iran. REFERENCES
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|a |
i i=1

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