SYNTHESIS OF TETRAHYDRATED Na (I) SALT OF 4-CARBOXY 2-NITRO TEREPHTHALATE AND ITS STRUCTURAL STUDY Текст научной статьи по специальности «Химические науки»

150 CHEMICAL PROBLEMS 2024 no. 2 (22) ISSN 2221-8688

UDC 547.267,547.457

SYNTHESIS OF TETRAHYDRATED Na (I) SALT OF 4-CARBOXY 2-NITRO TEREPHTHALATE AND ITS STRUCTURAL STUDY

Lala N. Mamedova

Azerbaijan State Agricultural University, Ganja, Azerbaijan safarova. lala.86@mail.ru

Received 15.12.2023

Accepted 14.02.2024

Abstract: An acid sodium salt of 2-nitro-terephthalic acid was synthesized and its molecular and crystal structures were studied. The crystallographic parameters of the new compound are as follows: the chemical formula - CgHsNNaOg, Cambridge Crystallographic Database Code: 2332574, molecular weight - 269.14, the temperature during measurement of the crystal parameters - 100.0 K, monocrystalline dimension 0.18mmx0.21mmx0.15mm, Radiation CuKa A= 1.54184, the minimum value of theta 4, 0250, the maximum value of theta 749580, the number of obtained reflections 9169, the number of independent reflections 2040, syngony - triclinic, space-group P-1, the specific gravity of the monocrystal d= 1.716 g/cm3, unit cell parameters - a = 6.5034 A, b = 7 .4080 A, c= 11.1553 A, the volume of the crystal lattice V=520.79 A3, the number of molecules in the lattice Z=2, the axial angles in the triclinic system a = 92.6990 °, [= 100.1720°, Y= 99.0840°, final R factor = 0.0267. Metallic sodium ionically coordinates with the ligand. Distance between atoms - Na(1)-O(1)=2,3357 A, Na (1)-O(4)=2,3236 A, Na(1)-0(7)= 2,3855 A. Key words: tetrahydratedNa (I) salt of 4-carboxy 2-nitro terephthalate, molecular and crystal structures, triclinic syngony, ionic structure, acid salt DOI: 10.32737/2221-8688-2024-2-150-156

Introduction

2-nitroterephthalic and 2-

aminoterephthalic acids, which contain two carboxyl groups, have attracted the attention of researchers as complex-forming ligands, and their crystal and molecular structures were studied by synthesizing new complex compounds with several metals. [1-9]. Since the nitro group - NO2 and the amino group - NH2, located in the benzene ring, are in the middle position for one carboxyl group, and in the meta position for the other, this position, which affects the reactivity of the ligand, leads to the fact that the hydrogen atom is more easily replaced by alkaline metals, due to increasing its activity in the carboxyl group. This so-called

"moderating effect" is manifested in other benzoic acid derivatives, salicylic acid, and para-aminosalicylic acid, as well as in other mid-substituted derivatives [10, 11].

In this research, Na salt of nitroterephthalic acid was synthesized and used in the synthesis of the other metal coordination compounds.

The crystal structure of Na 2 -nitroterephthalate salt has not been found in the literature. Therefore, the high-quality single crystals of Na 4 - carboxy 2 - nitro terephthalate salt were obtained for X-ray structural analysis and its molecular and crystal structures were studied.

Experimental part

New Na 2 - nitroterephthalate salt was distilled water and 0.211 g (0.01 mol) of 2-synthesized as follows: 0.84 grams (0.01 mol) nitroterephthalic acid is added. The sodium salt of NaHCO3 salt is dissolved in 100 ml of will be produced by replacing the hydrogen ion

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in one of the carboxyl groups of the ligand with a sodium ion. The solution of the resulting salt was filtered through filter paper and left in the dark place at room temperature. After a few days, transparent prismatic single crystals began to fall out. The single crystals were filtered and dried in a desiccator over anhydrous CaCl2 to constant weight. The yield of the reaction was 82.4%.

Monocrystals were selected under a

Table 2 lists the coordinates of the atoms in the molecule and their corresponding temperature factors. The interatomic distances,

microscope and collected the reflexes needed to identify the crystal structure of the suitable monocrystals for X-ray structure analysis in automated diffractometer operating at XtaLAB ARC 11 (RNC) of the University of Virginia in the United States of America, and the molecular and crystal structures were determined based on special programs [12-16]. The crystallographic parameters of the crystal structure are listed in Table 1.

valence angles and coordinates of the hydrogen atoms are given in Tables 3, 4 and 5, respectively.

Table 2. Coordinates of the atoms (x104) and their temperature factors

Atom X y z Ueq

Na1 2409,8(7) 1241.6(6) 805.5(4) 13.04(15)

O2 7882,0(14) 11641.6(11) 6114.8(7) 14.2(2)

O8 8514,5(14) 13905.9(11) 8016.1(8) 14.0(2)

O4 4371,4(13) 3972.3(11) 1810.2(8) 14.6(2)

O3 7809,5(14) 3824.7(12) 1951.1(8) 16.3(2)

O1 8807,0(14) 9562.0(12) 7395.5(7) 16.0(2)

O7 1058,0(14) -1798.7(12) -84.8(8) 14.7(2)

O6 6636,3(15) 7598.1(12) 1065.6(8) 19.2(2)

O5 5423,8(15) 9861.1(12) 1837.5(8) 18.4(2)

Table 1. Crystallographic data of the Sodium Nitro-terephthalate compound

Chemical formula C8H8NNaO8 Dimension of the crystal lattice 0.18 x0.21x0.15mm3

Molecular weight 269.14 g/mol Parameters of the a=6.5034 Â

crystal lattice b=7.4080 Â

Temperature during 100.00 K c=11.1553 Â

measurement

Volume of the crystal v=520.79 Â3

lattice

Syngony triclinic

The number of the z=2

Space-group P-1 molecules in the

lattice

Density 1.716 g/cm3 Triclinic angles a= 92.6990

ß= 99.0840

Radiation CuKa = 1.54184 Y= 100.1720

Minimal value of 4.0250

Theta

Maximal value of 74.9580

Theta final R- factor R= 0.267

Measured reflexes 9169

Independent reflexes 2040

N1 6214.3(16) 8475.8(13) 1928.2(9) 12.7(2)

C7 7101.9(18) 9151.6(16) 4123.1(10) 115(2)

C6 6715.9(18) 7835.9(16) 3147.4(10) 10.9(2)

C8 6297.0(19) 4488.0(15) 2233.2(10) 12.0(2)

C2 7696.2(18) 8618.6(16) 5288.4(10) 115(2)

C5 6851.1(18) 5997.9(15) 3274.6(10) 11.0(2)

C3 7874.8(19) 6791.3(17) 5447.5(11) 13.9(3)

C4 7441.8(19) 5497.9(16) 4455.1(11) 13.7(3)

C1 8182.3(18) 9976.8(16) 6376.1(10) 12.3(2)

Table 3. Interatomic distance (d)

Chemical bond d, Â Chemical bond d, Â

Na(1) - O(4) 2.3236(9) N(1) - O(5) 1.2277(13)

Na(1) - O(1) 2.3357(9) N(1) - C(6) 1.4684(14)

Na(1) - o(7) 2.3855(10) C(7) - C(6) 1.3874(16)

Na(1)- O(71) 2.3762(9) C(7) - C(2) 1.3924(16)

Na(1) - O(6) 2.4268(9) C(6) - C(5) 1.3923(16)

Na(1) - O(5) 2.5139(10) C(8) - C(5) 1.5276(15)

O(2) - C(1) 1.3210(14) C(2) - C(3) 1.3961(16)

O(1) - C(1) 1.2182(15) C(2) - C(1) 1.4953(15)

C(8) - O (4) 1.2508(15) C(5) - C(4) 1.3984(16)

C(8) - O(3) 1.2497(15) C(3) - C(4) 1.3890(16)

N(1) - O(6) 1.2295(13)

Table 4. Valence angles (ro)

Angles

Angles

Angles

O(4)-Na O(4)-Na O(4)-Na O(4)-Na O(4)-Na O(1)-Na O(1)-Na O(1)-Na O(1)-Na O(7)-Na O(7)-Na O(7)-Na O(7)-Na

-O(1) -O(7) -O(71)

-O(6)

-O(5)

-O(7)

O(17J)

-O(6)

-O(5)

-O(71)

-O(6)

-O(5)

-O(51)

89.70(3)

106.94(3)

167.98(4)

87.56(3)

83.93(4)

86.93(3)

90.25(3)

171.95(4)

79.37(3)

85.07(3)

86.63(3)

162.55(4)

84.24(3)

O(6)-Na(1)-O(5)

C(8)-O(4)Na(1)

C(1)-O(1)-Na(1)

Na(1)-O(7)-Na(11)

N(1)-O(6)-Na(1)

N(1)-O(5)-Na(1)

Na(1)-N(1)-Na(1)

O(6)-N(1)Na(1)

O(6)-N(1)-Na(11)

O(6)-N(1)-O(6)

O(15)-N(1)-Na(1)

O(5)-N(1)-Na(11)

O(5)-N(1)-O(6)

O(5)-N(1)-C(6)

107.83(3)

133.05(7)

141.21(8)

94.93(3)

127.40(7)

145.96(8)

84.72(2)

35.47(5)

109.23(7)

117.72(9)

23.03(5)

92.32(7)

124.28(9)

118.00(9)

C(6)-N(1)-Na(1)

C(6)-N(1)-Na(11)

C(6)-C(7)-C(2)

C(7)-C(6)-N(1)

C(7)-C(6)-C(5)

C(5)-C(6)-N(1)

O(4)-C(8)-Na(1)

O(4)-C(8)-C(5)

O(3)-C(8)-Na(1)

O(3)-C(8)-O(4)

O(3)-C(8)-C(5)

C(5)-C(8)-Na(1)

C(7)-C(2)-C(3)

C(7)-C(2)-C(1)

129.64(7)

145.40(7)

118.46(10)

119.75(9)

123.39(10)

116.75(10)

30.90(5)

116.50(10)

97.74(7)

127.13(11)

116.20(10)

142.9(8)

119.67(10)

121.17(10)

Table 5. Coordinates of hydrogen atoms (x104) and their temperature factors

Atom x y z U eq

H2 8142.63 12337.64 6758.2 21

H8A 9700(20) 14630(20) 8030(15) 21

H8B 7590(20) 14590(20) 8063(15) 21

H7 6963.92 10387.5 3998.92 14

H3 8296.02 6429.46 6241.23 17

H4 7548.43 4255.83 4580.11 16

H7A 1110(30) -2520(30) -487(18) 31(5)

H7B 1620(30) -2280(30) -613(19) 38(5)

Fig. 1. The crystal structure of the Sodium 2- nitroterephthalic monomer molecule

Fig. 2. The crystal structure of the polymer molecule in the crystal lattice

Figure 1 shows the structure of the the molecule located in the lattice and connected molecule, and Figure 2 exhibits the structure of by strong hydrogen bonds.

Analysis of the obtained results. As shown in Figure 1, sodium metal replaces one of the hydrogens in dibasic 2-nitroterephthalic acid and forms an acid salt. As expected, the structure is ionic, one of the oxygens in the carboxyl group is coordinated with sodium metal Na(1) - O(1) = 2.3357A. The other oxygen of the carboxyl group forms a strong hydrogen bond with the water molecules

included in the structure. Two water molecules coordinate with sodium metal and form an aqua complex Na (1) - O(4) = 2.3236 A, Na(1) -O(7) = 2.3855 A. Two water molecules that do not coordinate with the metal molecules form a polymer molecule located in a crystal lattice by connecting monomer molecules with strong hydrogen bonds (Figure 2).

1. The coordination compound of 2-nitroterephthalic acid and acid salt of Na metal was synthesized, the molecular and crystal structures of the obtained single crystals was identified in an automated diffractometer. It was found that Na metal replaces one hydrogen atom of the carboxyl group and forms an ionic compound. The hydrogen atom in the second carboxyl group

of the ligand is not replaced by a metal atom and an acid salt of the ligand is obtained. The C-C bonds of the benzene ring in the ligand are 1.89 A in length, similar to other benzoic acid derivatives.

2. Since there is an ionic structure, the carbon-oxygen bond in the carboxyl group is identical.

References

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4-HiDRO KARBOKSi 2-NiTRO TEREFTALAT Na (1) DUZUNUN SiNTEZi V9 KRiSTAL QURULU§UNUN OYRONiLMOSi

Lala N. Mammadova

Azarbaycan Dovlat Kand Tasarrufati Universiteti, Ganca, Azdrbaycan safarova.lala.86@mail.ru

Xulasa: 4-karboksi 2-nitrotereftal tur§usunun Na tur§ duzu sintez olunaraq molekulyar va kristal qurulu§u oyranilmi§dir. Triklin sinqoniyada kristalla§an yeni birla§manin kristalloqrafik parametrlari a§agidaki kimidir: kimyavi formulu C8H8NaO8, molekul kutlasi 269.14 reflekslarin ol9ulmasi zamani temperatur 100,0K, monokristalin ol9ulari 0.18mmx0.21mmx0.15mm, radiasiya CuKa A =1.54184, Teta minimum 4.025°, Teta maksimum 74.958°, ol9ulmu§ reflekslarin sayi 9169, asili olmayan reflekslarin sayi - 2040, sinqoniya - triklin, faza qrupu - P-1, monokristalin sixligi d=1,716 q/sm3, kristal qafasin parametrlari a = 6.5034 A, b = 704080A, c = 11.1553 A, kristal qafasin hacmi V=520.79 A3, qafasda olan molekullarin sayi Z=2. Triklin bucaqlar a=92.084°, P= 99.084°, y=100.172°, son R faktoru =0.0267. Natrium metali liqantla ion tipli koordinasiya yaradir. Burada atomlararasi masafa Na(1)-O(1)=2.3357 A, Na (1)-O(4)=2.3236 A, Na(1)-0(7)=2.3855 A kimidir.

A?ar sozlar: natrium (1) 4-karboksi-2-nitrotereftalat duzunun tetrahidrati, molekulyar va kristal qurulu§, triklin sinqoniya, ion qurulu§u, tur§ duz

156

8УЭТИЕ8К ОЕ ТЕТКАИУБКАТЕБ Na (I)

СИНТЕЗ Ш (1) ТЕТРАГИДРАТНОЙ СОЛИ 4-КАРБОКСИ-2-НИТРОТЕРЕФТАЛАТА И ЕГО СТРУКТУРНОЕ ИЗУЧЕНИЕ

Лала Н. Мамедова

Азербайджанский государственный сельскохозяйственный университет,

Гянджа, Азербайджан safarova.lala.86@mail.ru

Аннотация: Синтезирована кислая натриевая соль 2-нитротерефталевой кислоты и изучена ее молекулярная и кристаллическая структура. Кристаллографические параметры нового соединения следующие: химическая формула - C8H8NNaO8, молекулярная масса - 269.14, температура при измерении параметров кристалла - 100.0 К, размер монокристалла 0.18^0.21x0.15 мм, излучение СиКа 1.54184, минимальная значение теты 4.0250, максимальное значение теты 749580, количество полученных отражений 9169, количество независимых отражений 2040, сингония - триклинная, пространственная группа Р-1, удельный вес монокристалла d= 1.716 г/см3, параметры элементарной ячейки - a = 6.5034 А, Ь = 7.4080 А, с = 11.1553 А, объем кристаллической решетки У=520.79 А3, число молекул в решетке Z=2, углы триклинной сингонии а = 92.6990°, р= 100.1720°, у= 99.0840°, окончательный R-фактор = 0.0267. Металлический натрий ионно координируется с лигандом. Расстояние между атомами Ш(1)-0(1)=2.3357 А, №(1)-0(4)=2.3236 А, №(1)-О(7)= 2.3855 А.

Ключевые слова: тетрагидратная №(1) соль 4-карбокси-2-нитротерефталата, молекулярная и кристаллическая структура, триклинная сингония, ионное строение, кислая соль