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66 AZERBAIJAN CHEMICAL JOURNAL № 4 2022 ISSN 2522-1841 (Online)
ISSN 0005-2531 (Print)
UDC 547-285; 547-93, 41
SYNTHEZIS AND STRUCTURAL INVESTIGATION OF 6is-(PYRAZIN 2-CARBOXYLATE)-Ni(II)-DIHIDRATE
S.S.Hasanova, E.M.Movsumov
Azerbaijan State Agrarian University
seadet_hesenova76@mail.ru movsumov1941@mail.ru
Received 26.05.2022 Accepted 14.07.2022
A new Ni (II) C pyrazine 2-carboxylic acid complex was synthesized. Single crystals were obtained for X-ray diffraction analysis and the crystal and molecular structures of the new complex were deciphered. The crystallographic parameters of complex compounds are as follows: Molecular formula is C10H10N4Ni06, Molecular weight is 340.91 k.v.; temperature during measurement is 100.0 (2) K; Absorption frequency is MoKa = 0.71073E, Syngonia - Monoclinic; space group is P2j /c, Crystal lattice parameters are: a = 5.2136A, b = 11.10073A, c = 10.15267A; / = 100.14620C, volume of the crystal lattice is V = 578.395A3, number of molecules in the crystal lattice is Z = 2, density is d = 1.956 g / cm3, absorption coefficient is 1.715 mm-1, dimensions of the single crystal are 0.20x0.18x0.15 mm3; range of teta is 3.670-30.610°C; The boundaries of the hkl planes in the crystal section are h = -7+7 k = -15 +15.l = -14+14 the total number of collected reflexes is 8546, the number of independent reflexes is 1727, the boundary of the transitions is 0.761 and 0.707. Total Rfactor = 0.0240. It has been found that the central Ni(II) atom is coordinated by one oxygen atom of the carboxyl group and a donor nitrogen atom of the pyrazine ring, forming five-membered stable bonds. Two water molecules are coordinated by the Ni(II) atom and complete the coordination number of the metal to six. The Ni-O bond distance is 2.0874 A, the Ni-N bond distance is 2.0864 A. The second oxygen atom is not coordinated by the Ni(II) atom and forms a strong hydrogen bond with coordinated water molecules.
Keywords; pyrazine-2-carboxylic acid, Ni(II) complex, five-membered stable ring, hydrogen bond, X-ray analysis, diffraction, crystal structure.
doi.org/10.32 73 7/0005-2531-2022-4-66- 70 Introduction
Pyrazin 2-carboxylic acid, which has 4 donor atoms in the molecule, forms stable coordination compounds with transition elements. Metal complexes of Cu(II), Mn(II), Ag(I), Co(II), Sr(II) have been synthesized and crystal structures have been studied [1-5]. It has been established that in all complexes the central metal atom is coordinated by one oxygen atom of the carboxyl group and a donor nitrogen atom of the pyrazine nucleus, forming a five-membered ring.
In complexes of the ligand with heavy elements such as Pb(II) [6] and Cd(II) [7], a different structure is observed. In these structures, the other donor nitrogen atom of the pyrazine ring is coordinated by the central atom and a polymer structure is formed. In the literature, Ni(II) carboxylates have been synthesized and molecular structure has been discussed. It has been established that the donor atoms of the lig-
and recoordinated with the central nickel atom in monodentate ways [7-10]
In the literature, we did not find the structure of the complex of Ni(II) with pyrazine 2-carboxylic acid. Therefore, we synthesized single crystals of the new complex and studied the molecular and crystal structures.
Experimental part
Synthesis of Ni(II) complex
2.94 g (0.01 mol) of sodium pyrazine 2-carboxylate was dissolved in 100 ml of hot (50-600C) distilled water and then 2.87 q (0.005 mol) hot (50-600C) aqueous solution of Ni-SO4.7H2O was added dropwise to blue above content. The resisting species were stirred continuously for 2 h and then filtered to remove suspension if any. The clear solution obtained was concentrated by removing excess solvent and as such for crystallization. A few days later,
a single crystal of light yellow color seemed to be at the base and along the walls of the flask. The crystals were separated by filtration and then dried in a desiccator.
Element analysis (CHN) was performed using a Costech ECS 4010 CHNSO analyzer:
Calculated % C - 26.12; H - 2.05; N -
9.56;
Found %: C - 26.34 H - 2.21; N - 9.72.
SC - XRD analysis procedure
A suitable crystal was selected and an XtaLAB AFC11 (RINC) guarantor-single dif-fractometer. The crystal was kept at 294.3(3) K during data collection. Using Olex 2 [7].
The structure was solved with the Shelx T [8]. Structure solution program using Instran-sis Phashing and refined with the Olex 2 [9] refinement package using Gauss-Newton minimization. The crystallographic parameters of complex compounds are as follows: molecular formula is Ci0Hi0N4NiO6, molecular weight is 340.91 k.v.; temperature during measurement is
100.0 (2) K; absorption frequency is MoKa = 0.71073E, syngonia - monoclinic; space group P2i /c, Crystal lattice parameters are: a = 5.2136Â, b = 11.10073Â, c = 10.15267Â; p = 100.14620C, volume of the crystal lattice is V = 578.395Â3, number of molecules in the crystal
3
lattice Z = 2, density is d = 1.956 g/ cm , absorption coefficient is 1.715 mm-1, dimensions of the single crystal are 0.20x0.18x 0 . 1 5 mm ; range of teta is 3.670-30.610°; The boundaries of the hkl planes in the crystal section are h = -7.+7, k = -15.+15.l = -14, +14, the total number of collected reflexes is 8546, the number of independent reflexes is 1727, the boundary of the transitions is 0.761 and 0.707. Total Rfactor = 0.0240.
Atomic coordinates and their temperature factors are given in Table 1.
The distances between the atoms are given in Table 2 and the valence angles are given in Table 3.
The molecular and crystal structure of Ni (II) pyrazine 2-carboxylate is shown in Figure 1.
Table 1. Atomic coordination ( x 104 ) and their temperature factors
x y z U(eq)
Ni(1) 5000 5000 5000 12(1)
O(1) 7330(2) 5722(1) 3723(1) 13(1)
O(2) 8058(2) 7411(1) 2639(1) 15(1)
O(3) 2030(2) 4744(1) 3324(1) 14(1)
N(1) 3890(2) 6806(1) 4971(1) 11(1)
N(2) 2525(2) 9214(1) 4501(1) 16(1)
C(1) 6942(2) 6834(1) 3414(1) 11(1)
C(2) 4963(2) 7469(1) 4103(1) 11(1)
C(3) 4279(2) 8673(1) 3880(1) 14(1)
C(4) 1502(2) 8549(1) 5375(1) 14(1)
C(5) 2194(2) 7245(1) 5616(1) 13(1)
Chemical bonds d, Â Chemical bonds d, Â
Ni(1)-N(1)#1 2.0864(9) N(1)-C(5) 1.3318(13)
Ni(1)-N(1) 2.0864(9) N(1)-C(2) 1.3433(13)
Ni(1)-O(1)#1 2.0874(8) N(2)-C(4) 1.3360(14)
Ni(1)-O(1) 2.0874(8) N(2)-C(3) 1.3414(14)
Ni(1)-O(3)#1 2.1092(9) C(1)-C(2) 1.5183(14)
Ni(1)-O(3) 2.1092(9) C(2)-C(3) 1.3917(14)
O(1)-C(1) 1.2810(13) C(3)-H(3) 0.9500
O(2)-C(1) 1.2373(13) C(4)-C(5) 1.3950(15)
O(3)-H(3A) 0.9089 C(4)-H(4) 0.9500
O(3)-H(3B) 0.9120 C(5)-H(5) 0.9500
Table 2. Inter-atomic bonds, dÂ
Table 3. Valent angles, œ0
Angles œ0 Angles œ0
N(1)#1-Ni(1)-N(1) 180.00(5) C(5)-N(1)-C(2) 117.80(9)
N(1)#1-Ni(1)-O(1)#1 79.18(3) C(5)-N(1)-Ni(1) 129.14(7)
N(1)-Ni(1)-O(1)#1 100.82(3) C(2)-N(1)-Ni(1) 112.91(7)
N(1)#1-Ni(1)-O(1) 100.82(3) C(4)-N(2)-C(3) 116.72(10)
N(1)-Ni(1)-O(1) 79.18(3) O(2)-C(1)-O(1) 125.64(10)
O(1)#1-Ni(1)-O(1) 180.0 O(2)-C(1)-C(2) 119.12(9)
N(1)#1-Ni(1)-O(3)#1 87.45(4) O(1)-C(1)-C(2) 115.22(9)
N(1)-Ni(1)-O(3)#1 92.55(3) N(1)-C(2)-C(3) 120.54(9)
O(1)#1-Ni(1)-O(3)#1 88.58(3) N(1)-C(2)-C(1) 116.30(9)
O(1)-Ni(1)-O(3)#1 91.42(3) C(3)-C(2)-C(1) 123.15(9)
N(1)#1-Ni(1)-O(3) 92.55(4) N(2)-C(3)-C(2) 122.05(10)
N(1)-Ni(1)-O(3) 87.45(3) N(2)-C(3)-H(3) 119.0
O(1)#1-Ni(1)-O(3) 91.42(3) C(2)-C(3)-H(3) 119.0
O(1)-Ni(1)-O(3) 88.58(3) N(2)-C(4)-C(5) 121.67(10)
O(3)#1-Ni(1)-O(3) 180.0 N(2)-C(4)-H(4) 119.2
C(1)-O(1)-Ni(1) 115.96(7) C(5)-C(4)-H(4) 119.2
Ni(1)-O(3)-H(3A) 113.8 N(1)-C(5)-C(4) 121.19(10)
Ni(1)-O(3)-H(3B) 126.1 N(1)-C(5)-H(5) 119.4
H(3A)-O(3)-H(3B) 105.6 C(4)-C(5)-H(5) 119.4
Fig. 1. Molecular and crystal structure of complexes ¿«--(pyrazine 2-carboxylate) Ni (Il)-dihydrate.
Results and discussion
As can be seen from Figure 1, the car-boxyl group expected by us and found in metal carboxylates does not form chelate or bi-dentate coordination with the central atom Ni (II). One of the carboxyl group oxygen and the donor in the pyrazine nucleus forms a che-late-type coordination with the nitrogen atom. Ni (1) -O (1) = 2.087A, Ni (1) -N (1) = 2.086A. This closeness of these bonds is observed for the first time in Ni (II) complexes. This is due to the formation of a stronger 5-membered ring. When such a ring is formed, the angles between Ni (II) and nitrogen and
between Ni (II) and oxygen are deformed to form equal angles: N (1) -Ni (1) -N (1) # = 180.000 and O (1) # - Ni (1) -O (1) = 180.000.
The C-C bond in the pyrazine molecule is the same and is in the order 1.395-1.918A. The bond between the carbon of the carboxyl group attached to the pyrazine ring and the carbon of the pyrazine ring is C (2)-C (1) = 1.518A and is much longer than the same bond found in benzoic acid derivatives (C-C =1.456A). This is due to the angular tension that occurs in the molecule as a result of coordination. However, the distance between the oxygen and carbon of the carboxyl group is
the same as in other carboxylates: C (1)-O (1) = 1.2810A; C (1)-O (2) = 1.2373A [15, 16].
Conclusions
The crystal structures of a new complex of Ni(II) with pyrazine 2-carboxylic acid have been synthesized and deciphered.
It has been established that in a complex the central atom Ni(II) is coordinated by one oxygen atom of the carboxyl group and a donor nitrogen atom of the pyrazine nucleus, forming a five-membered ring.
Two water molecules which are part of the structure and use the atom's donor oxygen to create a donor-acceptor bond, increase the coordinated number of the nickel central atom up to 6.
References
1. Kong Y.X., Di Y.Y., Gao Z.F., Dou D.M. Diaqua-b/'s(pirazine 2-carboxylato)-copper(II). J.Thermal Analysis and Colorimetry. 2016. P. 437-442.
2. Vicente R., Ribas D., Savariault J.M., Cassoux P. Diaqua-b/'s(pyrazine-2-carboxylato)-manga-nese(II). New J. Chem. 1990. P. 19-23.
3. Yu-Xian Chi, Hui-Ping D., Shu-Mai L., Jing J., Shu-Yun N., Guang N.Z. Catena-(pyrazine 2-carboxsylato)-silver(1). Spectrochim. Acta. 2013. Part A. P. 12-16
4. Shamuradov E.B., Batsanov A.S., Sharifov M., Struchkom Yu.T., Azizov T. Diaqua-b/'s(py-razine 2-carboxylato)-cobalt(II) dihydrate. 1994. Koord Chi. 20. P. 616-619.
5. Cober M.A., Mautner F.A., Viconte R. Catena-b/'s(pyrazine 2-carboxylate)-strontium(II)-tetra-hydrate, J. Mol. Struct. 2007. P. 846-851.
6. Starosta W., Leclejewichd. Catena-[aqua-b/'s-(pyrazine 2-carboxylato). Acta Crystallogr. Sect E. 2010. P. 525-531.
7. Reng Zh., Wang E.B., Chang Y.X., Kang P.L. Catena-(b/'s-pyrazine 2-carboxsilato)-aqua Cad-mium(II). Chin J. Inorg. Chem. 2009. P. 560564.
8. Rzaeva M.F., Movsumov E.M., Serchienko V.S., Ilyukin A.B. Krmstallicheskaya struktura kompleksov dvuhvalentnye So, Ni, Cd c anionami benzojnoj i 2-(acetilamino)-5-nitro-
benzojnoj kislot. Kristallografiya. 2012. № 2. C. 256-260.Andac O., Gorduk S., Yilmaz H. Synthesis, characterization and H2 Adsorbstion performances of polymeric Co(II), Ni(II) complexes of pyrazine 2,3-dicarboxylic acid 1-vinylimidazol. J. Iranian Chemical Society, 2018 Ang. V. 12. No 8. P. 1699-1708.
9. Celik F., Dilek N, Caylak D., Necefoglu H., Hakelek T. Catena - Polidiaqua-bis(4-formul-benzoato Ni(II)-pirazine, Acta Cryst Section E.,
2014. P. 65-66.
10. Dolmanov Oleg V., Bourhis Luc J., Gildea Richard J., Howard Judith A.K., Puschmann Horst. OLEX2: a complete structure solution, refinement, and analysis program. J. applied crystallography, 2009. V. 427. № 2. P. 339-341.
11. Sheldrick, George M. SHELXT- Integrated space-group and crystal-structure determination. Acta crystallographica. Section A, Foundations and advances, 2015. V. 71. No 1. P. 3-8.
12. Bourhis Luc J., Dolomanov Oleg V., Gildea Richard J., Howard Judith A.K., Puschmann Horst. The anatomy of a comprehensive constrained, restrained refinement program for the modern computing environment -Olex2 dissected. Acta crystallographica. Section A, Foundations and advances. 2015. V. 71. 1. P. 59-75.
13. Gruo F., Gao E.J., Wang N., Zhao H.W. Toning structural topologies of four Ni(II) coordination polymer of organic liquid, Cryst.Eng.Comm., 2013. P. 6191-6198.
14. Raza H.A., Yildiz i., Yasmeen F., Munawar K.S., Ashfaq M. Synthesis of a 2D Ni(II)-carboxylate. J. Colloid and Interface Science. 2021. P. 43-54.
1 5 . S eadat Suliddin Hasanova, Lala Nizami Mamedova, Muhammad Ashfaq, Khurram Shahzad Munawar, Elman Muhammad Movsumov, Muhammad Khalid, Muhammad Nawaz Tahir, Muhammad Imran, catena-((^-pyrazine)-diaqua-bis(4-nitrobenzoato)-cobalt) J. Molecular Structure, 2021. 131851, DOI: 10.1016/j.molstruc.2021.131851
16. Ashkim C.S., Hamwell M.D., Macrate C.F. Cristal structure of Catena-poly diaqua bis-(formil benzoate) Co(II). Acta Crystal., E. 79.
2015. P. 339-342.
17. Usman N.T., Hofman K.Z., Less S.M. Single crystal investigation of complexes metals of the benzoic derivatives, J. Structure. 2020. P. 15115-15119.
PiRAZiN 2-KARBON TUR§USUNUN Ni(II) METALI iLO KOMPLEKC BiRLO^MOSiNiN SiNTEZi УЭ
QURULU§ TODQiQi
S.S.Hasanova, E.M.Movsumov
Pirazin 2-karbon tur§usunun tarkibinda karboksil qrupunun donor oksigen atomlari va pirazin halqasinda iki adad donor azotatomlri oldugundan kegid elementlari ila davamli kompleksbirla§malarin amala galmasi gozlanilir. Bu sababdan da liqandin Ni(II) kompleks birla§masi sintez olunmu§ va onun monokristallari alinaraq avtomatla§dirilmi§ difraktometra molekulyar va kristal qurulu§u 6yranilmi§dir. Kompleks birla§malarin kristalloqrafik parametrlari a§agidaki kimidir: Molekul formulu CioH10N4NiO6, Molekul kutlasi 340.91 k.v.; olgma zamani temperatur 100.0(2)K; Udulma tezliyi MoK2=0,71073E.Volt, Sinqoniya Monoklinik; faza qrupu P21/c, Kristal qafasin parametrlari: a=5.2136A, b=11,10073A, c=10.15267A; в=100 14620С, Kristal qafasin hacmi V=578.395A3, Kristai qafasda yerla§an molekullarin sayi z=2, sixligi d=1.956 q/sm3, udulma amsali 1.715 mm-1, Monokristalin olgulari 0.20x0.18x0.15 mm3; tetanin haddi 3.670-30.6100C; kristal kasiyinda hkl mustavilarinin sarhadlari h=-7, +7, k=-15, +15, L=-14, +14, toplanmi§ reflekslarin umumi sayi 8546. Asili olmayan reflekslarin sayi 1727, Kegidlarin sarhaddi 0.761 va 0.707. Yekun Rfaktor=0.0240. Malum olmu§dur ki, markazi atomNi(II) liqandin karboksil qrupunun bir oksigen atomu va pirazin halqasinin donor azot atomu ila elat tipinda rabitayaradaraq be§ uzvlu davamli halqa yaradir. Karboksil qrupunun digar oksigen atomu su molekullari ila guclu hidrogen rabitasi yaradir. Ni - O rabitasi 2.0874 A, Ni-N rabitasi isa 2.0864 A olur.
Agar sozlzr: pirazin 2-karbooksil tur§usu, Ni(II) kompleksi, be§uzvlu davamli halqa, hidrogen rabitasi, rentgen qurulu§ analiz, kristal qurulu§u.
СИНТЕЗ И СТРУКТУРНОЕ ИССЛЕДОВАНИЕ КОМПЛЕКСА NI(II) С ПИРАЗИН 2-КАРБОНОВОЙ
КИСЛОТЫ
С.С.Гасанова, Э.М.Мовсумов
Синтезирован новый комплекс Ni(II) С пиразин 2-карбоновой кислоты. Получены монокристаллы для реый Кштенструктурного анализа и расшифрованы кристаллические и молекулярные структуры нового комплекса. Кристаллографические данные нового комплекса следующие: молекулярная формула C10H10N4NiO6, молекулярная масса 340.91, температура при измерение - 200.4 К, сингония моноклиник, пр.група Р21/с, параметры ячей: a=5.2136A, b=11.10073A, c=10.15267A; P=100,1462°C, объём ячейки V=578.395A3, число молекул в ячейки z=2, размер монокристталла 0.20x0.18x0.15 мм3, число собранных рефлексов 8546, число независымых рефлексов 1727, окончательный R-фактор = 0.0240. Установлено, что центральный атом Ni(II) координируется одним атомом кислорода карбоксильной группы и донорным атомом азота пиразинного ядра, образуя пяти членные устойчивыйе связи. Две молекулы воды координируются атомом Ni(II) и дополняют координационое число металла до шести. Расстояние Ni-O связи равняется 2.0874 A, расстояние Ni-N связи 2.0864 A. Второй атом кислорода не координируется атомом Ni(II) и образует силную водородную связь с координованными молекулами воды.
Ключевые слова: пиразин-2-карбоновая кислота, комплекс Ni(II), пятичленное устойчивое кольцо, водородная связь, рентгеноструктурный анализ, дифракция, кристаллическая структура.
