Molecular and crystal structures of 3-[(4-metoxidiphenyl)diazenil]pentane-2,4-dion Kh. J. nagiyev, A. Y. abiyeva, R. A. aliyeva, R. K. askerov, F. M. chiragov Текст научной статьи по специальности «Химические науки»

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AZ9RBAYCAN KÍMYA JURNALI № 2 2017

UDC 548.736

MOLECULAR AND CRYSTAL STRUCTURES OF 3-[(4-METOXIDIPHENYL)DIAZENIL]PENTANE-2,4-DION

Kh.J.Nagiyev, A.Y.Abiyeva, R.A.Al iyeva, R.K.Askerov, F.M.Chiragov

Baku State University [email protected] Received 13.10.2016

A new p-diketone on the base of acetilacetone - 3-[(4-metoxidiphenyl)diazenil]pentane-2,4-dion has been synthesized. Its molecular and crystal structure was solved by using of X-ray difraction methods. The crystals are monoclinic: a=8.019 (6), b=6.379(4), c=10.941(8) A, p=94.430 (13)0, V=557.9(7) A3, space group P21/m, Z=2, density (calculated) 1.394 g/cm3, absorption coefficient 0.102 mm-1, crystal size 0.20^0.30x0.27 mm3. It's been found out, that synthesized compound belongs to hydrazo-form.

Keywords: 3-[(4-metoxidiphenyl) diazenil]pentane-2,

P-diketones and their derivatives are widely used for extracting and determination of several elements [1-5]. Crystal structures of P-diketones and their complexes with different metals have been investigated and works on synthesis were published [6-8]. The aim of pre-

4-dion, X-ray analysis, crystal structure.

sent work is synthesis and determination of molecular and crystal structures of new P-di-ketone based on acetylacetone 3-[(4-methoxy-phenyl)diazenil]pentane-2,4-dion (HL) which can exist in three tautomer forms - enol-azo (I), keto-azo (II) and hydrazo (III) [9]:

CH3

CH3

C _ OH

C —N= N C = O

I

CH3

—N= N—(O)—

O C H 3

(I)

C = O

• CH—N=N—( O C=O

CH3

CH3

C=O

OCH3 C —N = NH—(o^—

O C H3

C=O

CH3

(II)

(III)

In order to find out which of these tautomer forms has the synthesized compound, molecular and crystal structure of it has been investigated by X-ray diffraction analysis.

Experimental part Synthesis. 3-[(4-methoxyphenyl)diazenil]-pentane-2,4-dion has been synthesized by azo coupling of diazotized p-methoxyaniline with acetylacetone in alkalescent environment [3]. Diazotization of p-methoxyanline is carried out by dissolving 3.075 g (0.025 mol) of it in 20 ml of water with gentle heating adding 1.0 g of crystal of KOH. Solution is cooled in the ice bath till 00C and 1.725 g (0.025 mol) of NaNO2 was added with small portions, during 30 minutes. The temperature mustn't be higher than +50C. Then mix-

ture of 2.55 ml (p=0.98 g/sm ) of acetylacetone and 15 ml of ethanol is cooled in the ice bath adding 11.952 g (0.146 mol) of C^COONa. Solution is cooled in the ice bath and p-me-thoxyaniline diazonium suspension is added with portions during 30 minutes. During the process 8.0-10 pH interval is followed. Orange colored solution was retained on the air at room temperature till precipitation of reagent. The resulting solution is filtered out and put for crystallization at room temperature. After 3 days needle crystals precipitated from mother solution, which are filtered out, washed with distilled water and dried. The composition of synthesized compound was defined by the elemental analysis method. Found, %: C - 61.18, H - 6.04, N - 11.70. Calculated, %: C - 61.47, H - 5.98, N - 11.95.

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X-ray diffraction analysis. X-ray diffraction study of HL single crystal is carried out on Bruker SMART APEX II CCD diffrac-tometer (Mo^^-radiation, ^=0.71073 Â, graphite monochromator, 9- and ro-scanning, T= 296 K). The structure is decoded by the direct method and clarified by the least square method based on F in the anisotropic approximation for non-hydrogen atoms. Hydrogen atom, which participates in forming of intermolecular hydrogen bond of N-H.. .O type, is located in different electron density syntheses. Its position is cla-

rified in the isotropic approximation. Coordination of other hydrogen atoms are calculated geometrically and clarified in the "rider" model. All calculations are performed on SHELXTL program [10]. The crystallographic characteristics of synthesized compound HL and experimental parameters are given in Table 1. CIF file containing the complete information on investigated structure of HL was deposited in CCDC under the number 1492695 where it can be freely obtained on request at the internet site: www.ccdc.cam.ac.uk/data_request/cif.

Table 1. Crystallographic data, experimental parameters and elaboration for HL molecule structure

Parameter Value

Empirical formula C12H14N2O3

Molecular weight 234.25

Temperature, K 296(2)

Wavelength, Â 0.71073

Syngony system Monoclinic

Sp. gr. P2¡/m

Unit cell dimensions:

a, Â 8.019(6)

b, Â 6.379(4)

c, Â 10.941(8)

a, degree 90

P, degree 94.430(13)

Y, degree 90

Volume, Â3 557.9(7)

Z 2

Density (calculated), g/cm3 1.394

Absorption coefficient mm-1 0.102

F(000) 248

Theta range for data collection, degree 1.867 to 27.990

Crystal size, mm3 0,20x0,30x0,27

Index ranges h, k, l -10< h <10, -8 < k <8, -14< l <14

Reflections collected 4151

Independent reflections 1339 [R(int)=0,0292]

Final R indices [I>2sigma(I)] Ri=0.0637, WR2=0.1323

R indices (all data) Ri=0.0756, wR2=0.1484

Goodness-of-fit on F2 1.983

Admax/Admrn, e • Â3 0.883/-0.948

CCDC deposited number 1492695

Results and discussions

As a results of X-ray diffraction study the synthesized compound HL is 3-[(4-methoxy-phenyl)diazenil]pentane-2,4-dion, which has empirical formula C12H14N2O3 and monoclinic syngony. At T=296 K: a=8.019(6), ¿=6.379(4), c=10.941(8) A, a=900, p=94.430(13)°, y=90°, V=557.9(7) A3, space group P2/m, Z=2, p(calc.)=1.394 g/cm3, ^=0.102 mm-1. The final

values of divergence factors: R1=0.0637, wR2=0.1323 [for 738 diffraction reflections with I >2g(I)], ^=0.0756, wR2=0.1484 on the whole array of independent diffraction reflections. The crystal size is 0.20*0.30*0.27 mm. Perspective view of the molecule with the numbering of non-hydrogen atoms is represented in the figure and its main interatomic distances and bond angles in Table 2.

32 Kh.J.NAGIYEV et al.

Table 2. The main interatomic distances and bond angles in the HL molecule

Bond d, Â Bond d, Â Bond d, Â

O(1)-C(2) 1.216(7) N(2)-C(6) 1.389(7) C(6)-C(11) 1.393(8)

O(2)-C(4) 1.226(8) C(1)-C(2) 1.450(8) C(7)-C(8) 1.358(8)

O(3)-C(9) 1.358(6) C(1)-C(4) 1.473(8) C(8)-C(9) 1.381(8)

O(3)-C(12) 1.424(7) C(2)-C(3) 1.496(8) C(9)-C(10) 1.364(9)

N(1)-N(2) 1.287(7) C(4)-C(5) 1.487(8) C(10)-C(11) 1.368(9)

N(1)-C(1) 1.308(7) C(6)-C(7) 1.360(8)

Corner œ, degree Corner œ, degree Corner œ, degree

C(9)O(3)C(12) 117.9(5) C(1)C(2)C(3) 118.0(5) C(6)C(7)C(8) 121.8(6)

N(2)N(1)C(1) 122.4(5) O(2)C(4)C(1) 120.8(6) C(7)C(8)C(9) 119.4(6)

N(1)N(2)C(6) 120.3(5) O(2)C(4)C(5) 119.1(5) C(10)C(9)O(3) 124.4(6)

N(1)C(1)C(2) 113.3(5) C(1)C(4)C(5) 120.1(5) C(10)C(9)C(8) 119.8(6)

N(1)C(1)C(4) 122.1(5) C(7)C(6)N(2) 119.2(6) O(3)C(9)C(8) 115.8(6)

C(2)C(1)C(4) 124.5(5) C(7)C(6)C(11) 118.8(6) C(9)C(10)C(11) 120.6(6)

O(1)C(2)C(1) 122.5(5) N(2)C(6)C(11) 122.0(6) C(10)C(11)C(6) 119.7(6)

O(1)C(2)C(3) 119.5(6)

02

The structure of the HL molecule with numeration of nonhydrogen atoms.

All the atoms of the molecule are in mirror symmetry plane, as a result the hydrogen atoms of the methyl groups are relatively disordered to this plane. There's sufficiently strong intermolecular hydrogen bond of N-H...O type in the molecule between N(2) and O(2) atoms (N...O distance is 2.784, N-H 0.99, H...O 1.842 Á, NHO angle is 1180). Due to this intramolecular hydrogen bond flat six-membered cycle O(2)H(1N)N(2)N(1)C(1)C(4) is formed. The geometrical parameters of this cycle (bond length, bond and torsion angles) are close to corresponding average values which indicates to its stability. N(2)-N( 1 )-C(1)-C(4) and N(1)-C(1)-C(4)-O(2) torsion angles are equal to 00 and turn of substituents on N(2) and C(1) atoms is almost impossible. It shows that molecule in the crystal has flattened planar shape that may be due to both intramolecular bonds (conjugated double bonds and intramolecular hydro-

gen bond) and influence of the crystal field (molecular packing).

Thus, the X-ray diffraction study proved that 3-[(4-methoxyphenyl)diazenil]pentane-2,4-dion in the crystal has hydrazo-form. One of ke-to-groups participates in forming of intramolecular hydrogen bond of N-H.. .O type and this complicates its participation in the reaction of complex formation.

References

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АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 2 2017

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3-[(4-METOKSlFENlL)DlAZENlL]PENTAN-2,4-DlONUN MOLEKULYAR VO

KRlSTALLlK QURULU§U

X.C.Nagiyev, A.Y.Abiyeva, R. Э.ЭНуеуа, RKOsgarov, F.M.Çiraqov

Asetilaston asasinda yeni ß-diketon - 3-[(4-metoksifenil)diazenil]pentan-2,4-dion sintez edilmiçdir. Onun molekulyar va kristallik quruluçu RQA metodu ila müayyan edilmiçdir. Monoklinik sinqoniyaya malik kristallarin qafas ôlçûlari; a=8.0i9(6), b=6.379(4), c=i0.94i(8) Â, ß=94.430(13)°, V=557.9(7) Â3, faza qr. P21/m, Z=2, p(hes.)=i.394 q/sm3, ц=0.102 mm-1, kristalin ôlçûsû 0.20*0.30*0.27 mm3. Sintez edilmiç birlaçmanin kristalda hidrazo-formada oldugu müayyan edilmiçdir.

Açar sözlar: 3-[(4-metoksifenil)diazenil]pentan-2,4-dion, rentgen qurulu§ analizi, kristallik qurulu§.

МОЛЕКУЛЯРНАЯ И КРИСТАЛЛИЧЕСКАЯ СТРУКТУРЫ 3-[(4-МЕТОКСИФЕНИЛ)ДИАЗЕНИЛ]ПЕНТАН-2,4-ДИОНА

Х.Д.Нагиев, А.Ю.Абиева, Р. А.Алиев а, Р. К.Аскеров, Ф.М.Чырагов

Синтезирован новый р-дикетон на основе ацетилацетона - 3-[(4-метоксифенил)диазенил]пентан-2,4-диона. Его молекулярная и кристаллическая структуры установлены методами РСА. Кристаллы - моноклинные: а=8.019(6), ¿=6.379(4), с=10.941(8) А, Р=94.430(13)°, V=557.9(7) А3, пр. гр. P21/m, Z=2, р(выч.)=1.394 г/см3, ц=0.102 мм-1, размер кристалла 0.20*0.30*0.27 мм3. Установлено, что синтезированное соединение в кристалле имеет гидразо-форму.

Ключевые слова: 3-[(4-метоксифенил)диазенил]пентан-2,4-дион, рентгеноструктурный анализ, кристаллическая структура.