Synthesis, Spectroscopic Studies and Crystal Structure of Ni(II) Squarate Complex with 4,4 Bipyridine

 

Louiza Zenkhri^1*, Allaoui Abdelfattah¹, Souheyla Boudjema^2,3, Ahmed boutarfaia⁴, Meriem Ben Idir¹, Marwa Djenati¹

¹Valorisation and Promotion of Saharan Resources Laboratory (VPRS), University of Kasdi Merbah Ouargla, Chemistry Department, Faculty of Mathematics and Matter Sciences, Ouargla, Algeria - 30 000

²Département De Forage et Mécanique Des Chantiers Pétroliers, Faculté Des Hydrocarbures, Des Energies Renouvelables, Des Sciences De La Terre et De l’univers, Université Kasdi  Merbah, BP 511 Route Ghardaia, Ouargla, Algeria.

³Laboratoire De Catalyse et Synthèse En Chimie Organique, Faculté Des Sciences, Université De Tlemcen,

BP 119, Imama, Tlemcen, Algeria.

⁴Laboratory of Applied Chemistry, Univ Biskra, Faculty of Exact Sciences S.N.V, Biskra 07000, Algeria

*Corresponding Author E-mail: louizazenkhri@yahoo.fr

The Squarate complex of Ni(II) with 4,4-bipyridine compound and [Ni(C₄H₂O₄)₂(C₁₀H₈N₂)₂]⁺².2Cl^- formula was synthesized by soft chemistry, using co-precipitation method. The structure was characterized using infrared spectroscopy for main functional groups confirmation and powder XRD witch show that it crystallize in the monoclinic system, with cell lattice parameters a=9.9674 Å, b=10.538, c=18.7066 Å, V=1940.83 ų. The structure is based on SBU of NiO₂N₂ lied to organic entities. The nickel (II) is tetracoordinated with the two donor atoms of 4,4 bipyridine and two oxygen atoms of the squarate, building a distorted tetraedral around the metal ion.

 

 

INTRODUCTION:

4,4'-Bipyridine is a ditopic ligand widely used in hybrid material chemistry as metal chelating ligand¹. Because of its size, it can generate materials which display high porosity and provides bridges between metal centers to give coordination polymers with potential applications as functional materials such as optic, catalysis, gas separation^2,3 and antimicrobial activities^4-6. Its aspect gives the material the susceptibility of possessing zeolitic properties through the cavities at scales of great magnitude that it can form in the crystalline structure.

 

 

Frameworks with 4,4-bipyridine  have shown interesting gas adsorption properties in recent years^7-9. Bibliographic research on 4,4-bipyridine and nickel squarates revealed the existence of numerous compounds, with structure in the form of coordination polymers of different dimensionality. In most cases, nickel is generally found in an octahedral environment^3,10-12. Nevertheless, nickel complexes exist less frequently with tetrahedral geometries known by the sp³ hybridization and rarer in the square plane known by the dsp² hybridization.

 

Recently, there has been considerable work on open-framework metal squarate in the presence of organic amines^13-15. (Chih-Chieh Wang and al 2017) have reported a metal-organic frameworks with Cd(II) ions to form a 2D layered MOF with formula [Cd(C₄O₄) (C₁₀H₈N₂)(H₂O)₂·3H₂O. This compound exhibits an interesting reversible structural transformation upon de-hydration and re-hydration for guest water molecules after dehydrated, the compound adsorbs selectively CO₂ over N₂¹⁶. R. Soules and al. determined the structure of the compound with formula (Ni(C₄O₄) (C₁₀H₈N₂) (H₂O)₂2H₂O)_n. It crystallizes in the monoclinic system, space group P2₁/c, with a = 11.724, b= 7.418, c= 19.343 Å, and β= 100.16°. The crystal structure is made of chains of squarato-Ni(II)- squarato held together by strong hydrogen bonds O…H-O¹⁷.

 

In our investigations we describe the synthesis by soft chemistry, characterization based more on infrared spectroscopy, and determination of crystallographic parameters of a dehydrated hybrid nickel material with N and O donor ligands (4,4 bipyridine and squaric acid).  Experimental data reveals a tetrahedral environment. Nickel is hybridized sp³ type, so have suggested the paramagnetic property of this compound (Figure1).

 

 

             

Figure 1. Structures of the ligands: squaric acid and 4,4 bipyridine.

 

MATERIALS AND METHODS:

Reagents and Instrumentation:

All reagents were obtained from the Aldrich Chemical and were employed without further purification. IR spectra were obtained with Agilent Technology Cary 60 series FTIR spectrometer, with ATR accessories, and a measuring range of 4000–400 cm^-1. Diffraction powder experiments were performed at room temperature on a D8 Advence X-ray spectrometer using Mo Kα radiation (λ= 0.71073 Å). The sample for measurement was prepared by depositing the dried powder on a PMMA sample holder. The crystal lattice search was carried out with the Dicvol 06 program inclu in Fullprof^{18, 19}. The program used for powder pattern simulation is HighScore Plus²⁰ and molecular graphics were obtained using ChemSketch²¹.

 

Synthesis Of [Ni(C₄H₂O₄)₂(C₁₀H₈N₂)₂]⁺².2Cl:

[Ni(C₄H₂O₄)₂(C₁₀H₈N₂)₂]⁺².2Cl^- was synthesized by Co-precipitation method, using nickel cation, squaric acid and 4,4 bipyridine as templates. To a solution of squaric acid (0,056g, 0,5.10^-3 mol) in a suitable solvent (10 mL distilled water), the amine 4,4 bipyridine (0,077g,          0,5.10^-3 mol) in 10 mL of absolute ethanol was added under constant stirring followed by (0, 237 g,.10^-3 mol) of NiCl₂,6H₂O in 10 mL distilled water. The final mixture was stirred for 15 min to obtain a homogenous solution. The yellow reaction mixture was stilled for 13 days, then a green precipitate was formed and was filtered off and this was dried in. The general reaction scheme of the complexes is mentioned as:

 

(Ni²⁺,2Cl^-)+ H₂Sq +Bipy → [M(HSq)₂ + 2 Bipy].

Where, H₂Sq =Squaric acid and Bipy

 

RESULTS AND DISCUSSION:

Identification of [Ni(C₄H₂O₄)₂(C₁₀H₈N₂)₂].2Cl^:

FTIR spectra:

The IR spectra of the complex exhibit the characteristic bands of both squarate and 4,4 bipyridine (Fig 2). The important IR absorption bands are listed in table (1). The spectrum shows a relatively weak band at (3165-            3020) cm^-1is attributed to the C-H stretching of aromatic rings, a broad and intense band at (3426-                            3402) cm^-1 correspond to the O-H stretching vibration involved in hydrogen bands. A strong bands at (1608-1592) cm^-1 due to C=N, C=C stretching respectively. The band at 636.5 cm^-1 indicated coordination of 4,4-bipyridine through the nitrogen atom to the nickel cation Ni-N. The band at 563.2 cm^-1 due to υ(Ni-O) stretching, show the complexation through the deprotnated oxygen of squaric acid. The values of the absorptions obtained are in good agreement with those reported in the literature^22-25. It is important to note the absence of the bands around 3150 cm^-1  and 1790 cm^-1  respectively characterizing O-H from water and C=O ²² resulting from the deprotonation of squaric acid. This information will facilitate the confirmation of the environment of the central atom.

 

Figure 2: FT-IR Infrared of [Ni(C₄H₂O₄)₂(C₁₀H₈N₂)₂].2Cl

 

Figure 3 : Compound X-Ray Diffractogram Obtained.

 

Table 1. IR spectral data of the complex.

Wave number (cm-1)	Band
3390 vs	O-H
3024 w	C-Harom
1608 s	C=N
1492 s	C=C
1384 ,8m	C-N
563,2 s	Ni-N
636,5 s	Ni-O

s: strong;   m: medium;     w:weak

X-Ray Diffraction Analysis:

The routine diffractogram (Figure3) has been recorded in the 2θ domain [2,70]. Identification of the phase gives no similar compound. The X-ray diffraction pattern was indexed using DIVCOL 06 program in the monoclinic crystalline system with the mesh parameters shown in Table2 and figures of merit M(20) = 47.2 and F(20)=  46(0.0064,  394).

 

 

Table 2: Crystallographic data parameters for the complex.

 

Table3: Selected bond distances (Å) and angles (Å) for the complex

 

Structure of the Complex:

From the above discussion (elemental analysis, IR spectra, RDX data) and the literature review, it can be concluded that the possible structures of the complex is given below in figure 4, as concept with Chemsketch software. This figure shows the geometry and the environment of the central cation after geometric optimization and allows this vision with the 3D viewer program in ball and stick mode. Selected bond lengths and angles are collected in Table 3.

 

 

Figure 4: Proposed molecular unit of [Ni(C₄H₂O₄)₂(C₁₀H₈N₂)₂]²⁺.2Cl^- .

 

As mentioned in the literature the compound obtained from 4,4 bipyridine with the metal cation Ni(II) and squaric acid is a charged complex, due to the bipyridine which is a neutral ligand. The excess of the two positive charges apparent on the framework of this compound is compensated by the two chloride anions.

 

A. Structure Description:

The structure consist of the [Ni(C₄H₂O₄)₂(C₁₀H₈N₂)₂]²⁺.2Cl^- units. The molecular unit (C₂₈H₂₀N₄Cl₂O₈Ni) consists of a nickel cation (Ni²⁺), two squarate (C₄H₂O₄), two molecules of 4,4-bipyridine (C₁₀H₈N₂) and chlorine anions. The first coordination sphere contains both two oxygens from the two squarate and two nitrogens from the two 4,4-bipyridine molecules (Figure 5), so that a deformed tetrahedral is formed.

 

Figure 5: Polyhedron of coordination geometry

Nickel ions are monodentate coordinated to squarate ligand thought oxygen atom of carboxylate group and nitrogen atom of 4,4-bipyrine ring, to give a distorted square plan geometry. The absence of the characteristic band of C=O (Squarate) confirms a formation of a one-dimensional structure (1D) of the compound figure 4 and not isolate entities. The cystal structure is made of stacked layers such network of formula [(Ni(C₄HO₄)₂(C₁₀H₈N₂)₂)²⁺]_n are thus formed figure 6. The presence of hydroxy ligands groups makes extensive hydrogen bonding interactions in the comlex. Cohesion of the structure is ensured by the hydrogen bonds like (Cl….H-O) and (N….H-O) and π-π interactions between both 4,4-bipyridine rings to give a building with three dimensions.

 

 

Figure 6: A stereo view of the crystal structure of layer structure.

 

The values ​​of the lengths of the bonds in the coordination polyhedron as well as the values ​​of the angles were calculated with the Shem Sketch software and are in good agreement with our hypothesis of proposition of the molecular unit Tables 3 and 4.

 

The values ​​of the bond distance Ni-O and Ni-N1 are 1.927 Å and 1.854 Å, respectively. These distances are found to be short then those of previously found in the literature and similar compounds because of the geometry optimisazion. The values ​​of the angles in the polyhedron vary only slightly: [(N1-Ni-O1) = 90.244°, (N1-Ni-O2) = 89.881°, (O1-Ni-N2) = 89.874°, (N2-Ni-O2) = 90.227° to give distorted teradedral geometry.

 

CONCLUSION:

The co-precipitation combination of divalent nickel precusor with Squarate ligand and 4,4-bipyridine as template has afforded the conception of units [Ni(C₄H₂O₄)₂(C₁₀H₈N₂)₂]²⁺.2Cl^-]. Structural analysis reveals that the Squarate ligand acte as bridge and display monodentate mode of coordination to generate a layer structure possess open framework architectures, interlinked by hydrogen bonds and π-π interaction. The title compound differs from those reported by absence of water ligands in the first coordination sphere as well as in the crystal lattice. This suggests application of this compound in adsorption field and possibility of its hydratation as perspective. This will allow us to compare the likely results with what is reported in the literature by Chih-Chieh Wang 2017 and R. Soules 1988.

 

REFERENCES:

1.      C. Kaes, A. Katz, M.W. Hosseini, Bipyridine: the most widely used ligand. A review of molecules comprising at least two 2, 2 ‘-bipyridine units, Chemical reviews, 100 (2000) 3553-3590.

2.      Y.S. Tan, E.R. Tiekink, Crystal structure of (4, 4′-bipyridyl-κN) bis [N-(2-hydroxyethyl)-N-isopropyldithiocarbamato-κ2S, S′] zinc (II)–4, 4′-bipyridyl (2/1) and its isostructural cadmium (II) analogue, Acta Crystallographica Section E: Crystallographic Communications, 73 (2017) 1642-1646.

3.      A.A. Morales-Tapia, R. Colorado-Peralta, A.M. Duarte-Hernلndez, A. Flores-Parra, J.M. Rivera, Crystal structure of catena-poly[[[tri-aqua-(4-cyano-benzoato-κO)nickel(II)]-μ-4,4'-bi-pyridine-κ(2) N:N'] 4-cyano-benzoate], Acta Crystallogr E Crystallogr Commun, 71 (2015) m197-m198.

4.      V. Pawar, S.V. Chavan, R.S. Yamgar, R. Atram, B. Thorat, S. Bisht, S.S. Sawant, Synthesis and Characterization of Novel Transition Metal Complexes of 4-Methyl-7-Hydroxy 8 Formyl Coumarin and
Their Biological Activities, Asian Journal of Research in
Chemistry, 4 (2011) 1238-1242.

5.      M.A. Bashar, M.A. Mannan, M.F. Hossen, M.S. Islam, M. Kudrat-E-Zahan, The synthesis, characterization and biological activity investigation of mixed ligand Coordinated Ni (II) Complexes, Asian J. Res. Chem, 8 (2015) 55-58.

6.      D.S. Wankhede, P. Kulkarni, N.S. Jadhav, M.D. Gurle, P.B. Wagh, O. Shankarrao, Synthesis and Characterization of Biologically Active Mixed Ligand complexes of 8-Hydroxyquinoline and Salicylaldehyde, Asian Journal of Research in Chemistry, 6 (2013) 525-530.

7.      K. Kishida, S. Horike, K. Nakagawa, S. Kitagawa, Synthesis and adsorption properties of azulene-containing porous interdigitated framework, Chemistry letters, 41 (2012) 425-426.

8.      Z. Chang, D.-S. Zhang, Q. Chen, R.-F. Li, T.-L. Hu, X.-H. Bu, Rational construction of 3D pillared metal–organic frameworks: synthesis, structures, and hydrogen adsorption properties, Inorganic chemistry, 50 (2011) 7555-7562.

9.      B. Wang, L.-H. Xie, X. Wang, X.-M. Liu, J. Li, J.-R. Li, Applications of metal–organic frameworks for green energy and environment: New advances in adsorptive gas separation, storage and removal, Green Energy & Environment, 3 (2018) 191-228.

10.   S.-Y. Yang, L.-S. Long, R.-B. Huang, L.-S. Zheng, S.W. Ng, Aqua (4, 4-bipyridine) phthalatonickel (II) trihydrate, Acta Crystallographica Section E: Structure Reports Online, 59 (2003) m507-m509.

11.   S.-C. Hsu, S.-H. Lo, C.-C. Kao, C.-H. Lin, Poly [bis (μ2-4, 4′-bipyridine) bis (3-nitrobenzoato) nickel (II)], Acta Crystallographica Section E: Structure Reports Online, 67 (2011) E67-m65.

12.   Bounab, Nawal, Synthèse de nouveaux complexes de bases de Schiff de métaux de transition asymétriques de cuivre et de nickel contenant un résidu pyrrolique électopolymérisable, Ferhat Abbas University, Setif 2011.

13.   M. Dan, K. Sivashankar, A. Cheetham, C. Rao, Amine-templated metal squarates, Journal of Solid State Chemistry, 174 (2003) 60-68.

14.   L. Zenkhri, N. Audebrand, T. Bataille, Yttrium ethylene diammonium squarate tetrahydrate, Acta Crystallographica Section E: Structure Reports Online, 67 (2011) m529-m530.

15.   C.-C. Wang, S.-Y. Ke, Y. Feng, M.-L. Ho, C.-K. Chang, Y.-C. Chuang, G.-H. Lee, Synthesis, Structural Characterization and Ligand-Enhanced Photo-Induced Color-Changing Behavior of Two Hydrogen-Bonded Ho (III)-Squarate Supramolecular Compounds, Polymers, 11 (2019) 1369.

16.   C.-C. Wang, S.-Y. Ke, K.-T. Chen, Y.-F. Hsieh, T.-H. Wang, G.-H. Lee, Y.-C. Chuang, Reversible Single-Crystal-to-Single-Crystal Structural Transformation in a Mixed-Ligand 2D Layered Metal-Organic Framework: Structural Characterization and Sorption Study, Crystals, 7 (2017) 364.

17.   R. Soules, F. Dahan, J.-P. Laurent, P. Castan, A novel co-ordination mode for the squarate ligand [dihydroxycyclobutenedionate (2–)]: synthesis, crystal structure, and magnetic properties of catena-diaqua (2, 2′-bipyridyl)-µ-(squarato-O 1, O 2)-nickel (II) dihydrate, Journal of the Chemical Society, Dalton Transactions, (1988) 587-590.

18.   A. Boultif, D. Louër, Powder pattern indexing with the dichotomy method, Journal of Applied Crystallography, 37 (2004) 724-731.

19.   D. Louer, M. Louer, Méthode d'essais et erreurs pour l'indexation automatique des diagrammes de poudre, Journal of Applied Crystallography, 5 (1972) 271-275.

20.   T. Degen, M. Sadki, E. Bron, U. Kِnig, G. Nénert, The highscore suite, Powder Diffraction, 29 (2014) S13-S18.

21.   V. ACD/Structure Elucidator, Advanced Chemistry Development, Inc., Toronto, ON, Canada, www.acdlabs.com, 2019.

22.   J. Carranza, J. Sletten, F. Lloret, M. Julve, Iron (III), chromium (III) and cobalt (II) complexes with squarate: Synthesis, crystal structure and magnetic properties, Inorganica Chimica Acta, 371 (2011) 13-19.

23.   H. Erer, O.Z. Yeşilel, O. Büyükgüngör, One-dimensional coordination polymers of Co (II) and Cd (II)-squarate with 2-methylimidazole and 4 (5)-methylimidazole ligands, Polyhedron, 29 (2010) 1163-1167.

24.   O. Zafer, H. Paşaoğlub, O.O. Yılan, O. Büyükgüngör, Syntheses, Spectral, Thermal and Structural Characterization of 2-Hydroxyanilinium and 2-Amino-3-hydroxy-pyridinium Squarates, Zeitschrift für Naturforschung B, 62 (2007) 823-828.

25.   J.S. Stevens, M. Walczak, C. Jaye, D.A. Fischer, In Situ Solid‐State Reactions Monitored by X‐ray Absorption Spectroscopy: Temperature‐Induced Proton Transfer Leads to Chemical Shifts, Chemistry–A European Journal, 22 (2016) 15600-15604.

 

 

 

 

Received on 25.11.2019                    Modified on 31.12.2019

Accepted on 21.01.2020                   ©AJRC All right reserved