1 SYNTHESIS, SPECTROSCOPIC AND THERMAL ANALYSIS OF THE 2 3 4 5

HOFMANN-TYPE METAL (II) TETRACYANONICKELATE PYRIDAZINE COMPLEXES: [M(pdz)Ni(CN)4]H2O (M = Zn(II) or Cd(II))

Dursun Karaaa1, Gne Sheyla Krkolu2*

61Eskiehir Osmangazi University, The Institute of Science and Technology, Department of Physics, 726480 Eskiehir, Turkey 82Eskiehir Osmangazi University, Faculty of Arts and Sciences, Department of Physics, 26480 9Eskiehir, Turkey 10Summary: The pyridazine (pdz = C4H4N2) complexes, [M(pdz)Ni(CN)4]H2O (M = Zn(II) (1) 11and M = Cd(II) (2)), have been prepared and characterized by vibrational (FT-IR and Raman) 12spectroscopic methods, thermal and elemental analysis techniques were examined. The square 13plane [Ni(CN)4]2- anions of the complexes from the data obtained and [M(L)2]2+ (M = Zn(II) 14ve Cd(II), L = pdz) cations surrounded MNi(CN)4 polymeric layers were formed. The 15Ni(II) atoms are coordinated with a square-planar to four C atoms of the CN groups, the 16M(II) atoms are octahedrally surrounded by four N of the CN anions and with donor atoms of 17ligand. As a result examination of FT-IR and Raman spectra of the complexes were obtained 18to show Hofmann-type the structure. In addition, thermal and elemental analysis results were 19also supported by spectral data. 20 21Introduction 22 Cyano-bridged complexes, which have been of interest since the XVII th century, have

23been shown to form polymeric structures by studies over the last few decades. These 24polymeric metal complexes are especially macromolecules formed by metalmetal or metal 1 2
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25ligand metal bridge connections in one, two or three dimensions. These types of complexes 26have applications in the fields of chemistry, biology and material science and therefore they 27have been attracting increasing attention from scientists [1]. Functional polymeric cyano 28complexes can be prepared with two or more dentate ligands. These types of materials are 29packed to form crystal structures due to bridging groups and intermolecular interactions. 30Cyano-bridged polymeric complexes structurally contain chains oriented in one dimension. 31These structures may be linear, zig-zag, stepwise, lateral and pipe shaped [2]. 32 The diazine rings are building blocks of many important natural and synthetic

33compounds, e.g., nucleotides. The vibrational spectra of pyridazine were measured earlier by 34various authors [3-5]. 35 There is a group of complexes with the general formula ML2Ni(CN)4 among Hofmann

36type complexes. In this formula, L2 refers to be a bidentate or a pair of monodendate ligand 37molecules containing N-terminate donor atoms. The Hofmann-type host structure, 38[ML2Ni(CN)4], is built from the linkage of the square planar tetracyanonickelate(II) moieties 39and the [ML2]2+ groups, with the L atoms protruding above and below the [M-Ni(CN)4] layers 40[6]. The square-planar [Ni(CN)4]2- moiety may take a number of catenation modes to build up 41multidimensional structures. Based on this structure, metal(II) tetracyanonickelate(II) 42complexes have been developed using N-donor ligands such as ammonia [7], pyridine [8], O43donor ligands such as water [9], dioxane [10] and S-donor ligands as dimethylthioformamide 44[11]. 45 The aim of this study is to provide further examples of Hofmann type compounds. For

46the first time we have prepared two new Hofmann type complexes of the type: 47[Zn(C4H4N2)Ni(CN)4]H2O (1) and [Cd(C4H4N2)Ni(CN)4]H2O (2). In this study, we report the 48syntheses, spectral (FT-IR and Raman), thermal, and elemental analyses of the cyano-bridged 49polymeric complexes. 3 4
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50Experimental 51 All the chemicals used were reagent grade and used without further purification.

52Nickel(II) chloride hexahydrate (NiCl26H2O, 97%), Zinc chloride pure (ZnCl2, 99%), 53Cadmium chloride (CdCl2H2O, 98%), potassium cyanide (KCN, 96%) and pyridazine 54(C4H4N2, 98%), were purchased from commercial sources and used without further 55purification. NiCl26H2O (1.25 g, 5 mmol) was dissolved in 25 ml water and added to a 20 ml 56solution of KCN (1.30 g, 20 mmol) in water. The mixture was stirred at 50C during three 57hours. To this solution was added a solution of NiCl26H2O (0.237 g, 1 mmol), ZnCl2 (0.136 58g, 1 mmol) and CdCl2H2O (0.201 g, 1 mmol) one by one. These mixtures were refluxed with 59stirring for 3 h at 50C in a temperature-controlled bath and then the solutions were filtered 60and slowly evaporated in air. A solution of pdz (0.160 g, 2 mmol) in ethanol was added 61dropwise upon stirring to these suspensions. The solutions were refluxed with stirring for 3 h 62at 50 oC and then cooled to room temperature. The complexes were filtered and washed with 6310 ml of water and acetone and dried in air. 64Analytical Results 65 The freshly prepared samples were analyzed for C, H, and N by a LECO CHNS-932

66analyzer with the following results (calculated % / found %): [Zn(C4H4N2)Ni(CN)4]H2O (1) 67Mw=326.26 g/mol: C=29.45/29.58., H=1.85/1.98, N=25.76/25.83. [Cd(C4H4N2)Ni(CN)4]H2O 68(2) Mw=373.28 g/mol : C=25.74/25.61, H=1.62/1.94, N=22.51/22.95. 69Thermal Analyses 70 A Perkin Elmer Diamond TG/DTA thermal analyzer was used to record simultaneous

71TG, DTG and DTA curves in the static air atmosphere in the temperature range 30-700 oC 72using platinum crucibles. The thermal decomposition behaviors of the complexes 1 and 2 73were studied in the temperature range 30-700 oC in static air atmosphere. The thermal analysis 74curves of 1 and 2 complex are similar (Figs. 1 and 2). Thermal decomposition of the 5 6
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75complexes proceeds in three stages. In the first stage, complex 1 starts to lose one water 76molecule between 30 and 150 oC whereas complex 2 are related to release of one water 77molecule between 30 and 210 oC (found. % 4.77, calcd. % 4.90 for 1 and found. % 5.29, 78calcd. % 4.82 for 2). In second stage of the complexes, one pdz ligands for 1 (found. % 25.11, 79calcd. % 24.57) and one pdz ligand for 2 (found % 22.63, calcd. % 21.45) are released. The 80following stage remaining four cyano groups in complexes 1 and 2 decompose between 303 81and 397 oC for 1, 330 and 410 oC for 2 (DTAmax: 398 oC for 1 and 386 oC for 2). The final 82solid product of the thermal decomposition was identified as MO + NiO metal oxides found 83(calcd.) % = 46.96 (47.78) for 1 and found (calcd.) % = 53.30 (54.40) for 2. 84Spectra 85 The FT-IR spectra of the complexes were recorded as KBr pellets in the range of

864000400 cm-1 (2 cm-1 resolution) on a Perkin Elmer 100 FT-IR spectrometer. The Raman 87spectra were recorded in the range of 4000250 cm-1 on a Bruker Senterra Dispersive Raman 88instrument using laser excitation of 785 nm. 89Results and Discussion 90 The FT-IR and Raman spectra of the studied complexes, [Zn(C4H4N2)Ni(CN)4]H2O

91and [Cd(C4H4N2)Ni(CN)4]H2O, are shown in Figs. 3 and 4, respectively. The assignments 92[12] and the wavenumbers of the vibrational bands of pdz observed in the spectra of the 93compounds studied are listed in Table 1, together with free pdz wavenumbers for comparison 94[13]. 95 The absorption bands of complexes are observed in the region from 3700 cm-1 to 3300

96cm-1 symmetric and asymmetric (OH) stretching vibrations of the coordinated water 97molecules. Moreover, the absorption bands of complexes are observed in the region from 981650 cm-1 to 1600 cm-1 (OH) deformation vibrations. The wavenumbers of pdz in complexes 99are compared with those of free pdz. A glance at Table 1 shows that the vibrational wave

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100numbers of the pdz modes of the complexes exhibit coordination properties. Modes of the pdz 101molecule have upward and downward shifts in frequency when compared with the free 102molecule, and the shifts are metal dependent. Analogous shifts on coordination were observed 103in pyridine [8], 4,4'-bipridyl [14] and 2-methylpyrazine [15] complexes. This shifts were 104explained as the coupling of the internal modes of the aromatic molecule with the MN 105vibrations [8, 14, 16]. The CH stretching bands of pdz were observed in the 31003000 cm-1 106region. The ring (CH) modes of pdz were found downward and upward shifts in frequency 107when compared with the free molecule. The CH in-plane bending vibrational modes of the 108pdz can be observed in the 16001000 cm-1 region of the spectrum, but several other internal 109coordinates are mixed with them, e.g., the ring modes. The ring-stretching modes appear in the 110spectra of the pyridazine in the 16001000 cm-1 region. When the aromatic ring nitrogen 111involves in complex formation, certain ring modes, particularly modes 14001600 cm-1 112increase in value both due to the coupling with M (Zn(II) or Cd(II)) Npdz bond vibrations 113[17, 18] and due to alterations of the ring force field [16]. 114 The vibrational wave numbers of the [Ni(CN)4]2- group vibrations of the complexes 1

115and 2 are given in Table 2. In order to assign the bands attributable to the [Ni(CN)4]2- ion in 116the spectra, we refer to the work of McCullough et al. Who presented vibrational data for the 117salt Na2Ni(CN)4 in the solid state [19]. In this salt, [Ni(CN)4]2- anion is not coordinated to Na+ 118cation; therefore, it can be treated as an isolated unit with D 4h symmetry and thus used as a 119reference to comment on vibrational changes when MNC bonding takes place. The assigned 120wave numbers of the [Ni(CN)4]2- units of the complexes appear to be much higher than those 121for isolated [Ni(CN)4]2- ion. Such frequency shifts have been observed for Hofmann-type 122complexes [8, 18, 20, 21]. It is known that cyanide stretching modes shift to higher wave 123numbers in the case of the compounds having the [MNi(CN)4]n polymeric layers. This case 124are explained as the mechanical coupling of the internal modes of [Ni(CN)4]2- with the metal 9 10
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125M-NC vibrations. It follows that the nitrogen ends of the [Ni(CN)4]2- units are bound to M (M 126= Zn(II) or Cd(II)) atom in the compounds. Two strong and sharp bands observed in complex 1271, although there is one similar band in other complexes. Two strong and sharp absorption 128bands at 2192 cm-1 and 2165 cm-1 in the FT-IR spectrum of complex 1 can easily be attributed 129to bridging cyano and terminal cyano bands, respectively [22, 23]. 130Conclusions 131 In this study, two new Hofmann-type complexes were synthesized and investigated by

132vibrational (FT-IR and Raman) spectroscopy, thermal and elemental analyses. On the basis of 133the vibrational (FT-IR and Raman) spectroscopic results, we propose that in the case of the 134complexes the pdz molecule are coordinated to metal (Zn(II) veya (Cd(II)) ions of the 135adjacent layers of [M-Ni(CN)4]n. M (Zn(II) or (Cd(II)) atoms are bound to four N atoms of 136the CN ions and, the Ni atoms are surrounded by four C atoms of the CN groups in a square 137planar layer. Thermal analyses of complexes also support the spectroscopic conclusion. 138Acknowledgement 139This work was supported by the Research Fund of Eskiehir Osmangazi University. Project 140number: 201019024. 141References 1421. P.S. Mukherjeee, T.K. Maji, T. Mallah, E. Zangrando, L. Randaccio, N.R. Chaudhuri, 143 Inorg. Chim. Acta., 315, 249 (2001).

1442. J. Cernak, M. Orendac, I. Potocnak, J. Chomic, A. Orendacova, J. Skorsepa, A. Feher, 145 Coord. Chem. Rev., 224, 51 (2002).

1463. H.D. Stidham, J.V. Tucci, Spectrochim. Acta. 23A, 2233 (1967). 1474. Y. Ozono, Y. Nibu, Y. Shimada, R. Shimada, J. Chem. Soc. Japan., 59, 2997 (1986).

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1485. J. Vazquez, J.J. Lopez Gonzalez, F. Marquez, J.C. Otero, J.E. Boggs, 10 th International 149 150 Conference on Fourier Transform Spectroscopy, Budapest, p. B2.14 and private communication, (1995).

1516. T. Iwamoto, J. Incl. Phenom., 24, 61 (1996). 1527. H. Rayner, H.M. Powell, J. Chem. Soc., 67, 319 (1952) 1538. S. Akyz, A. B. Dempster, R. L. Morehouse, S. Suzuki, J. Mol. Struct., 17, 105 (1973). 1549. H. Yuge, C.H. Kim, T. Iwamoto, T. Kitazawa, Inorg. Chim. Acta., 257, 217 (1997). 15510. A.B. Dempster, H. Uslu, Spectrochim. Acta., 34, 71 (1978). 15611. M. enyel, G.S. Krkcolu, J. Appl. Spect., 68, 862 (2001). 15712. S. Breda, I.D. Reva, L. Lapinski, M.J. Nowak, R. Fausto, Journal of Molecular Structure, 158 786, 193 (2006).

15913. J. Vazquez, J. Jesus, L. Gozalez, F. Marquez, J. E. Boggs, Journal of Raman 160 spectroscopy, 29, 547 (1998).

16114. A. Sungur, S. Akyz, J.E.D. Davies, J. Incl. Phenom., 5, 491 (1987). 16215. G. S. Krkolu, O. Z. Yeilel, . Kavlak, O. Bykgngr, Struct. Chem., 19, 879 163 (2008).

16416. S. Suzuki, W.J. Orville-Thomas, J. Mol. Struct., 37, 321 (1977). 16517. Z. Kantarc, B. Davarcolu, C. Bayrak, J. Incl. Phenom., 39, 115 (2001). 16618. N. Ekici, Z. Kantarc, S. Akyuz, J. Incl. Phenom., 10, 9 (1991). 16719. R. L. McCullough, L. H. Jones, G. A. Crosby, Spectrochim. Acta, 16, 929 (1960). 16820. Z. Kantarc, M.M. Blbl, J. Incl. Phenom., 40, 105 (2001). 16921. Z. Kantarc, C. Bayrak, J. Incl. Phenom., 45, 59 (2003). 17022. G.S. Krkolu, O. Z. Yeilel, . Kavlak and O. Bykgngr, J. Mol. Struct., 920, 220 171 (2009).

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17223. A. Karada, . nal, A. enocak, . Uar, A. Bulut, O. Bykgngr, Polyhedron, 27, 223 173 (2008).

17424. M. Bahat, . Yurdakul, Spectrochimica Acta Part A, 58, 933 (2002). 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 194 195

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196Figure Captions 197Fig. 1. The TG, DTG and DTA curves of complex 1. 198Fig. 2. The TG, DTG and DTA curves of complex 2 199Fig. 3. The FT-IR spectra of complexes 200Fig. 4. The Raman spectra of complexes

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201Table 1. The vibrational wavenumbers (cm-1) of pdz in 1and 2.

a

Assignments (PED %)

Pyridazine

Pyridazine

Pyridazine (Liquid) 3057 m 1570 m 1563 s 1444 m 1413 vs 1281 m 1159 vw 1131 vw FT-IR 3090 vw 3076 w 3059 w 1572 m 1570 m 1449 w 1419 m 1285 w 1157 vw 1125 vw

1 Raman 1582 w 1463 vw 1431 vw 1298 w 1176 w 1141 vw FT-IR 3088 w 3077 w 3059 w 1571 s 1454 sh 1417 s 1285 m 1163 w 1121 w

2 Raman 3050 vw 1581 vw 1459 vw 1297 vw 1175 vw 1132 vw

A1 (CH)s(79.5)+ (CH)s(19.6) B2 (CH)as(97.0) A1 (CH)'s(80.0)+ (CH)s(19.7) A1 (C4C5)(46.8)+ (CH)s(18.9) B2 (CC)as(44.3)+ (CH)'as(24.4)+ (NC)as(22.7) A1 (CH)s(39.2)+ (CH)'s(24.0)+ (CC)s(19.3)+(NN) (13.7) B2 (CH)as(62.3)+ (CH)'as(23.5) B2 (CH)as(34.9)+ (NC)as(32.7)+ (CH)'as(30.5) A1 (NC)s(62.1)+(CC)s(21.0) )+ (CH)'s(10.4) A1 (CH)'s(59.2)+ (CH)s(16.4) + (NN)'s(10.4)+(NC)s(10.5) A1 (C4C5)s(41.0)+ (CH)s(22.6) + (NN)s(22.1)+

(Gas) 3086 s 3071s 3056 s 1567 m 1455 w 1413 s 1281 m 1121 sh

(CCI4 ) 3068 m 3056 m 1570 vs 1563 vs 1443 s 1412 vs 1281 m 1156 w 1129 w

1068 s (CC)'s(12.2) B2 (CC)as(42.3)+(CH)as(29.5)+ (NC)as(12.7)+ ring 1(10.4) B2 ring 1(87.1) A1(NN)(45.5)+(CC)s(34.4))+ (NC)s(15.6) B1 (CH)'s(106.4) B1 (CH)'s(97.0) A2 ring 1 (114.2) A2 ring 2 (90.0) B2 ring 3 (92.7)

1072 w

1084 m

1070 m

1082 w

1061 s 1027 w 968 m 959 m 760 s 745 s 665 w 622 vw

1062 vs 963 vs 757 s 665 s 622 w

1062 m 982 vw 962 s 758 vs 753 s 665 w 622 vw

1056 w 1011 vw 980 m 931 vw 764 m 746 m 672 w 634 vw

992 vs 949 w 767 w 756 w 686 w 649 w

1062 w 988 w 976 m 931 vw 762 s 745 m 672 w 639 vw

990 m 940 vw 756 vw 686 w 647 vw

202aTaken from Ref. [12]

203bTaken from Ref. [13]

204*Abbreviations used stretching, deformation, in-of-plane bending, w wagging, out-of-plane bending, 205Abbreviations used: m, stretching; d, deformation; w, wagging; t, twisting; r, rocking; s, strong; m, medium; w, 206weak; sh, shoulder; v, very; br, broad. *PEDs lower than 10% are not included 207 208 209 210Table 2. The vibrational wavenumbers (cm-1) of the [Ni(CN)4]2- group in 1and 2.
a

Assignments

Na2[Ni(CN)4]

K2[Ni(CN)4]H2O (2160) vs (2137) m 2122 vs 2084 m 540 w 443 w 417 s

Cd-Pyr-Ni

1 (2191) vs (2112) vw 2192 m, 2165 vs 2124 sh 575 w 448 m, 457 m 436 m

2 (2183) s (2124) vw 2154 vs 2136 sh 549 w 428 vs

A1g , (CN) B1g , (CN) Eu, (CN) (13CN) Eu , (NiC) A2u, (NiCN) Eu, (NiCN)

(2149) (2141) 2132 2128 543 448 433

(2158) vs (2135) m 2135 vs 2109 w 542 vw 424 vs

19 20

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212aTaken from Ref. [19] 213bTaken from Ref. [24]

214*Abbreviations used: s, strong; m, medium; w, weak; sh, shoulder; v, very. The symbols , and refer to 215valence, in-plane and out-of-plane vibrations, respectively. Raman spectra are given in parentheses
216 217 218 219 220 221 222 223 224 225 226 227 228 229

21 22

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230 231 232 233 234 235 236 237 238 239 240 241 242 Figure 1. The TG, DTG and DTA curves of complex 1.

23 24

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243 244
245 246 247 248 249 250 251 252 253 254 255

Figure 2. The TG, DTG and DTA curves of complex 2.

25 26

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256

257 258 259 260 261 262 263 264 265 266 267 268 269 270 27 28
14 Figure 3. The FT-IR spectra of complexes 1 and 2.

271 272

273 274 275

Figure 4. The Raman spectra of complexes 1 and 2.

29 30

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