SYNTHESIS, PHYSICOCHEMICAL STUDY AND CRYSTAL STRUCTURE OF BIS-(PNITROBENZOATE)-DI-(PYRAZINE) NICKEL(II)-DIHYDRATE Текст научной статьи по специальности «Химические науки»

CHEMICAL PROBLEMS 2022 no. 1 (20) ISSN 2221-8688

95

UDC: 547-285; 547-93, 41.

SYNTHESIS, PHYSICOCHEMICAL STUDY AND CRYSTAL STRUCTURE OF BIS-(P-NITROBENZOATE)-DI-(PYRAZINE) NICKEL(II)-DIHYDRATE

S.S. Hasanova

Ganja branch of the National Academy of Sciences of Azerbaijan e-mail: [email protected]

Received 14.01.2022 Accepted 18.03.2022

Abstract: The molecular structure of the new Ni(II) complex of p-nitrobenzoic acid and pyrazine was synthesized and deciphered. It found that the central atom was coordinated by the ligand of p-nitrobenzoic acid according to the monodentate type. Having the basic properties of the pyrazine molecule, it was coordinated by the nickel atom in a donor-acceptor type of bond through donor nitrogen atoms. Two water molecules through donor oxygen atoms were coordinated by nickel and complement its coordination number to six. Pyrazine molecules cross-link para-nitrobenzoate Ni(II) molecules with the help of donor nitrogen atoms and form polymeric molecules.

Keywords: polymer molecule, monodentate bond, crystal and molecular structure, pyrazine, aqua complex. DOI: 10.32737/2221-8688-2022-1-95-101

Introduction

The most promising area of coordination chemistry is the preparation of new coordination polymers with certain structural and specific functions [1]. They are of practical interest as components for a new generation of functional materials with improved characteristics. Metal-organic coordination polymers exhibit high sorption characteristics, which opens up prospects for their use, for example, in heterogeneous catalysis, in processes of separation of complex mixtures, purification and storage of industrial gases. The presence of magnetic or photoactive centers (e.g., d- and/or f-metal ions, organic radical ligands) in metal-organic polymeric molecules makes it possible to expect that molecular magnets, photomagnetics or photoactive molecules can be used to create new types of data carriers, quantum computers and various magnetic and optical-mechanical devices [2,3].

The key role in the synthesis of

coordination polymers is played by the nature of the ligands used, by the choice of suitable solvents based on transition elements and reaction conditions [4].

Organic ligands most often used to obtain coordination polymers with carboxyl groups must have more than one donor center for the coordination of different metal atoms [5].

Bearing in mind the importance of the diversity of coordination of carboxylates and in the composition of the donor nitrogen atom in the pyrazine molecule, we synthesized and deciphered the molecular and crystal structures of pyrazine adducts of Co(II) Mn(II) para-nitrobenzoates [6].

In this work, we synthesized and studied the crystal structures of a new p-nitrobenzoate Ni(II) pyrazine adduct in the (p-nitrobenzoate)2 Ni*C4H4N2 composition.

Experimental part

Single crystals for X-ray diffraction 1.25 g of sodium para - nitrobenzoate

analysis were synthesized in the following way: was dissolved in hot (50-600C) 50 ml of

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distilled water, 0.25 g of pyrazine was added to the solution.

To the resulting solution was added a solution of 2.13 grams of NiSO4H2O salt. The solution was filtered and left at room temperature in a dark place. After a few days, brown needle-shaped single crystals precipitated.

The crystalline complex was filtered and dried in a desiccator over anhydrous CaCl2.

Elemental analysis of the resulting complex was carried out on a Castech ECS 4010

CHNSO analyzer.

% calculated: C- 42.87; H-3.20; N -

11.13.

(4-NO2-C<H4-COO)2Ni-2C4H4N2

Found %: C- 43.01; H-3.26; N - 11.06.

An IR spectroscopic analysis of the obtained complex (4000-400 cm-1) was carried out on a Perkin-Elmer-spectrum 100 PI-IR

instrument. The absorption bands (sym COO ) in the region of 1650 cm-1, and (sym COO ) in the region of 1540 cm-1 were determined. The absorption bands of the C-NO2 bond appear in the region of 1365 cm-1, coordinated water molecules in the region of 827 cm-1, the N-N bond in the region of 645 cm-1, the Ni-O bond in the region of 552 cm-1.

The thermogravimetric analysis of the complex was carried out in a NETZSCH STA-409 PDPG derivatograph in air.

X-ray diffraction analysis of the single crystal was carried out in an automatic diffractometer XeaLAB AFC 11 (RINC) in the USA at the University of Virginia. The structure was solved using the Olex2 [7], Refine [8], and Shelx [9] programs. Crystallographic parameters are given in Table 1. Coordinates of atoms in Table 2 and the distance between the atoms in Table 3, bond angles in Table 4. Coordinates of hydrogen atoms in Table. 5.

CCDC 052318 Cristal size.mm3 0.152x0.050x0,038

Empirical formula C^N NiOj6 Radiation Cu Ka (A =1,54184)

Formula weight 253.52 20 range for data collection/ 8.02 to 150.08

Temperature K 294.7 (3) Index ranges -27 < h < 27, -8 < k < 8, -15 < 1 < 15

Crystal system Monoclinic Reflections collected 17980

Space group C2/c Independent reflections 1929 [Rint = 0.0182, R^ = 0.0061].

a/A 22.0922(2) Data / restraints/ parameters 929/0/175

b/ A 6.9939(1) Goodness - of - fit on F2 1.087

c/A 12.3766(1) Final R indexes [I>=2e(1)] Rj = 0.0259, wR2 = 0.0712

a/° 90 Final R indexes [all data] Rj = 0.0260, wR2 = 0.0712

P/° 94.586(1) Largest dff.peak/hole e À"3 0.28/ - 0.32

Y/° 90

Volume/ A3 1906.19(4)

Z 4

Table 1. Crystallographic data of the Ni(II) complex

Table 2. Atomic coordinates (*104 ) and their temperature factors.

Atom a/x b/x c/z U(eq)

Ni 1 5000 620.8(5) 2500 22.35912)

O13 41.59 587.3(15) 3082.4(9) 28.2(2)

O14 4630.3(6) 758.9(18) 873.9(10) 34.6(3)

O12 3620.3(5) 1788(2) 1634.7(10) 41.8(3)

N17 5000 -2385(2) 2500 25.2(3)

N18 5000 -3628(2) 2500 25.2(3)

010 1510.9(7) -542(2) 5578.9(12) 53.9(4)

N8 1495.3(6) 450(20 4766.3(12) 36.5(3)

09 1040.8(6) 1287(3) 4391.9(12) 57.7(4)

C5 3106.4(6) 1049(2) 3187.0(12) 24.7(3)

C6 3120.1(7) 178(2) 4198.6(12) 27.7(3)

C2 2057.4(7) 669(2) 4216.7(13) 28.2(3)

Table 3. Distance between atoms, d Ä

Atom Atom Length/Ä Atom Atom Length/Ä

Ni1 013 2.0449(10) 010 N8 1.220(2)

Ni1 0131 2.0449(10) N8 09 1.222(2)

Ni1 0141 2.1128(12) N8 C2 1.4706(19)

Ni1 014 2.1128(12) C5 C6 1.391(2)

Ni1 N17 2.1025(17) C5 C11 1.5102(19)

Ni1 N18 2.1030(17) C5 C4 1.393(2)

013 C11 1.2661(18) C6 C7 1.385(2)

012 C11 1.2457(19) C2 C3 1.381(2)

N17 C221 1.3375(17) C2 C7 1.380(2)

N17 C22 1.3375(17) C20 C22 1.385(2)

N18 C202 1.3360(17) C3 C4 1.383(2)

N18 C203 1.3360(17)

11-X,+Y,1/2-Z; 21-X,1+Y,1/2-Z; 3+X,1+Y,+Z

Table 4. Valence angles.

Atom Atom Atom Angle/" Atom Atom Atom Angle/"

O131 Ni1 O13 178.69(6) C203 N18 Ni1 121.64(9)

O141 Ni1 O13 87.56(5) C203 N18 C202 116.71(18)

O14 Ni1 O13 92.50(5) O9 N8 O10 123.61(14)

O14 Ni1 O131 87.56(5) C2 N8 O10 118.13(14)

O141 Ni1 O131 92.50(5) C2 N8 O9 118.25(14)

O141 Ni1 O14 174.76(7) C11 C5 C6 120.78(13)

N17 Ni1 O13 89.34(3) C4 C5 C6 119.53(13)

N17 Ni1 O131 89.34(3) C4 C5 C11 119.63(13)

N17 Ni1 O14 92.62(4) C7 C6 C5 120.46(14)

N17 Ni1 O141 92.62(4) C3 C2 N8 118.62(14)

N18 Ni1 O13 90.66(3) C7 C2 N8 118.58(14)

N18 Ni1 O131 90.66(3) C7 C2 C3 122.80(14)

N18 Ni1 O14 87.38(4) O12 C11 O13 125.66(13)

N18 Ni1 O141 87.38(4) C5 C11 O13 116.38(13)

N18 Ni1 N17 180.0 C5 C11 O12 117.95(13)

C11 O13 Ni1 125.76(10) C22 C20 N184 121.68(14)

C22 N17 Ni1 121.67(9) C20 C22 N17 121.63(14)

C221 N17 Ni1 121.67(9) C4 C3 C2 118.03(14)

C221 N17 C22 116.65(18) C2 C7 C6 118.36(14)

C202 N18 Ni1 121.64(9) C3 C4 C5 120.81(14)

11-X,+Y,1/2-Z; 21-X,1+Y,1/2-Z; 3+X,1+Y,+Z; 41-X,-1+Y,1/2-Z

Table 5. Coordinates of hydrogen atoms.

Atom X y z U(eq)

H14a 4599(11) -140(40) 560(20) 51.9(4)

H14b 4249(11) 1100(30) 1008(18) 51.9(4)

H6 3482(9) -270(30) 4518(15) 33.2(4)

H20 5437(9) -6100(30) 1224(16) 35.2(4)

H22 5462(9) -2720(30) 1230(16) 35.1(4)

H3 1649(9) 2010(30) 2905(16) 37.5(4)

H7 2613(9) -590(30) 5400(17) 35.5(4)

Crystal structures are shown in Fig. 1. Fig. 2 shows the polymer structure in the "c" axis.

Fig. 1. Crystalline and molecular structure of the Ni(II) complex

Fig. 2. Polymer structure of the Ni(II) complex along the c-axis.

Discussion

As can be seen from Fig.1, the central Ni (II) atom is coordinated by one oxygen atom of the carboxyl group, according to the monodentate type. The donor nitrogen atoms of pyrazine are coordinated by the Ni (II) atom in accord with the donor-acceptor mechanism.

Two water molecules are coordinated by the central Ni(II) atom through donor oxygen atoms, and the coordination number of the metal is raised to six.

The distance NiC with the oxygen of the

carboxyl group will be Ni(1)-0(17)=2.0443 A, Ni(1)-N(12)= 2.1025 A, Ni(l)-H2O= 2.1128 A.

Pyrazine molecules cross-link molecules through donor nitrogen atoms to form a polynuclear polymer along the "b" axis (Fig. 2).

In the polymer molecule, there are strong hydrogen bonds and between the uncoordinated oxygen atom of the carboxyl group and the OH group of the water molecule. And there are also van der Waals bonds between molecules.

References

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2. Raza H., Yildiz I., Yasmeen F., Munawar K.S., Ashfaq M., Abbas M., Ahmad M., Younus HA., Zhang S., Ahmad N. Synthesis of a 2D copper (II) -carboxylate framework having ultrafast adsorption of organic dyes. Journal of Colloid and Interface Science. 2021, vol. 602, pp. 43-54.

3. Gao E.J., Hui Y., Wang N., Jia Z.I., Zhao H.W., Wu S.Y., Zhu M.C. Synthesis, Crystal Structures, Interaction with DNA, Cytotoxicity, and Apoptosis Studies of Co(II), Cd(II) Complexes Bearing Pyrazine-2, 3-dicarboxylic Acid. Russian Journal of Coordination Chemistry. 2020 Aug; vol. 46(8), pp. 573-83.

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6. Seadat Suliddin Hasanova, Lala Nizami Mamedova, Muhammad Ashfaq, Khurram Shahzad Munawar, Elman Muhammad Movsumov, Muhammad Khalid, Muhammad Nawaz Tahir, Muhammad Imran. Synthesis, crystal structure, Hirshfeld surface analysis and theoretical investigation of polynuclear coordination polymers of cobalt and manganese complexes with nitrobenzene and pyrazine. Journal of Molecular Structure. 2022, 1250 ,

131851. https://doi.org/10.1016Zj.molstruc .20 21.131851

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BiS -(p-NiTROBENZOAT)- Di-(PiRAZiN) Ni (II) -DiHiDRAT KOMPLEKS BiRLd$MdSiNiNSiNTEZi, FiZiKi-KiMYdViANALiZi Vd MOLEKULYAR KRiSTAL

QURULUSU

S.S. Hdsdnova

Azarbaycan Milli Elmlar Akademiyasinin Ganca Bolmasi e-mail: [email protected]

Xulasa: Maqalada nikel(II) kationunun yeni kompleks birla§masi bis - (nitrobenzoato),-di (pyrazin) Ni (II) - dihidrat akva kompleksi sintez olunaraq, fiziki - kimyavi tadqiqati aparilmi§ va monokristallari alinaraq avtomatla§dirilmi§ difraktometrda molekulyar va kristal qurulu§u agilmi§dir. Malum olmu§durki, p-nitrobenzoy tur§usunda karboksil qrupunun bir oksigeni markazi atomla koordinasiyaya daxil olur. Qurulu§a daxil olan pirazin molekulu donor azot atomlari vasitasila Ni(II) ila donor - akseptor tipli rabita yaradir. Eyni zamanda koordinasiyaya daxil olan iki su molekullari Ni atomu ila rabita yaradaraq onun koordinasiya adadini altiya gatdirir. Pirazin molekullari donor azot atomlari vasitasila molekullari bir - birina tikarak polimer zancir amala gatirir.

Agar sozlari: polmer molekulu, monodentat rabita, kristal va molekulyar qurulu§, pirazin, akva kompleks, p - nitrobenzoat, Ni(II) kompleksi.

СИНТЕЗ, ФИЗИКО-ХИМИЧЕСКОЕ ИССЛЕДОВАНИЕ И КРИСТАЛЛИЧЕСКАЯ СТРУКТУРА БИС-(п-НИТРОБЕНЗОАТО)-ДИ-(ПИРАЗИН) НИКЕЛЬ(П) -ДИГИДРАТА

С.С. Гасанова

Гянджинское Отделение Азербайджанской Национальной Академии Наук

e-mail: [email protected]

Аннотация: Синтезирована и расшифрована структура нового комплекса Ni(II) с п-нитробензой кислотой и пиразином. Установлено, что центральный атом координируется лигандом п-нитробензойной кислоты по монодентатному типу. Имеющая основные свойства молекула пиразина координируется атомом никеля по донорно-акцепторному типу связи через донорные атомы азота. Две молекулы воды через донорные атомы кислорода координируются никелем и дополняет его координационное число до шести. Молекулы пиразина с помощью донорных атомов азота сшивают молекулы пара-нитробензоато Ni (II) и образуют полимерные молекулы.

Ключевые слова: полимерная молекула, кристаллическая структура, пиразин, аквакомплекс.