CRYSTAL STRUCTURE OF DIAQUA-BIS(N-BENZOYLANTHRANILATO)ETHYLATO-COPPER(II) Текст научной статьи по специальности «Химические науки»

CHEMICAL SCIENCES

CRYSTAL STRUCTURE OF DIAQUA-BIS(N-BENZOYLANTHRANILATO)-

ETHYLATO-COPPER(II)

Ziyaev M.,

Junior Researcher, Laboratory of Complex Compounds, Institute of Bioorganic Chemistry,

Academy of Sciences of the Republic of Uzbekistan, Tashkent

Obidova N.,

Junior Researcher, Laboratory of Complex Compounds, Institute of Bioorganic Chemistry,

Academy of Sciences of the Republic of Uzbekistan

Nabiev U.,

Junior Researcher, Laboratory of Complex Compounds, Institute of Bioorganic Chemistry,

Academy of Sciences of the Republic of Uzbekistan

Ashurov J.,

Doctor of Science, Leading researcher, Head of Laboratory of Complex Compounds, Institute of Bioorganic Chemistry, Academy of Sciences of the Republic of Uzbekistan

Khodjaniyazov Kh.

Doctor of Science, Leading researcher, Laboratory of Complex Compounds, Institute of Bioorganic Chemistry, Academy of Sciences of the Republic of Uzbekistan

Abstract

A stable diaqua-bis(N-benzoylanthranilato)-ethylato-copper(II) complex was synthesized by the reaction of N-benzoylanthranilic acid (N-baaH) and CuSO4-5H2O in 1:1 molar ratio in ethanol. Its crystals were structurally characterized by single crystal X-ray analysis. The complex has a distorted square planar CuO5 geometry. In the crystal, molecules are linked in inversion-related mode, forming dimers, which generate alternate fl|(12) ring motifs in a linked chain that runs along (100) plane. These chains are stacking via van der Waals interactions forming a two-dimensional supramolecular network.

Keywords: X-ray analysis, N-benzoylanthranilic acid, copper(II) complex, hydrogen bonds.

1. Introduction

Anthranilic acid derivatives have been known as good inhibitors of AKR1C isoenzymes, with Ki values in low micromolar or nanomolar range. Almost 30 years ago, Penning and Talalay showed that indometh-acin and mefenamic acid, nonselective NSAIDs, strongly inhibit rat liver hydroxysteroid dehydrogenase AKR1C9, a model for human AKR1C isoenzymes [1]. Other nonselective NSAIDs and selective COX-2 inhibitors also proved to be potent inhibitors of AKR1C isoenzymes [2, 3]. For this purpose, a series of N-ben-zoyl anthranilic acid derivatives were synthesized as inhibitors of penicillin binding protein [4]. Due to their structural similarities to several known inhibitors of AKR1C enzymes, their inhibitory activity on given enzymes was tested [5, 6]. In addition, copper complexes have been much explored due to the fact that copper is

a bio-essential element responsible for numerous bio-activities in living organisms [7]. Moreover, it is well known that Cu(II) complexation plays an important role in the pharmacological profile of the antimicrobial agents [8, 9].

Here we present the synthesis and structural characterization of the new penta-coordinated copper(II) complex C30H29O9N2Cu, obtained by quantitatively yield of the title compound 1. 2. Results and Discussion The displacement ellipsoid representation and theoretical geometry structure with the atom-numbering view for diaqua-bis(N-benzoylanthranilato)-ethylato-copper(II) (1) is shown in Fig. 1. Carbon C29 and C30 atoms are disordered, and their ellipsoid probability level not shown owing to disordered shift.

Figure 1. Molecular structure of Cu(N-baa)2(H2O)2EtOHshowing the atom-numbering. Displacement ellipsoids for the non-H atoms are drawn at the 50 % probability level (except C29 and C30). The H atoms are presented

with balls with arbitrary radii.

The benzene (C1-C6 and C15-C20) rings planes are not parallel to each other and its adjacent COO-groups forming a 5.455°, 8.861° and 3.652°, respectively. The metal atom of CuO4 basis is elevated from basal position no more than 4.581°, while an angles O1-Cu-O7 and O3-Cu-O7 (83.978° and 94.427°) lead to displaced vertex of pyramid (O7). The overall geometry around the penta-coordinated copper is described as a distorted square planar geometry. The bond distances Cu—O1, Cu—O3 are 1.933(4) A, respectively, which slightly deviate from those found in literature for metal complex having N-benzoylanthranilic acid; whereas angles Cu—O1—C7 and Cu—O1—C21 (123.318° and 115.718°) deviate greatly to the reported values for

similar derivatives [10]. The Cu—O2 bond distance 3.085 A and Cu—O4 bond distance average 2.887 A, which are also in slightly great range [11].

The hydrogen bond geometry for copper(II) complex is presented in Table 2. The molecule is dimeric and is stabilized by an intramolecular N1—H1--O2 and N2—H2---O4 and intermolecular O5-H5--O2 and O5-H5-O4 hydrogen bonds; the latter generate alternate flf (12) ring motifs in a linked chain that runs along (100) plane. These chains are stacking along (41-5) via van der Waals interactions (C14—H29 and H5—H30) forming a two-dimensional supramolecular network (Table 1 and Fig. 2).

Figure 2. View of two-dimensional supramolecular network. For better viewing, the terminal intramolecular and intermolecular atoms are assigned. For clarity, H atoms have been omitted.

Table 1.

Hydrogen-bond geometry (A, °) of the complex__

D-H--A D - H d(H--A) d(D--A) <(DHA)

N1-H1---O2 0.860 1.913 2.624 139.150

N2-H2---O4 0.660 1.893 2.605 139.232

O5-H5---O21 0.701 1.980 2.673 169.720

O5-H5---O41 0.670 2.016 2.677 168.901

O61-H61---0911 0.670 2.036 2.694 167.637

O61-H61---08111 0.856 1.919 2.775 178.253

Symmetry code: (i) -x, -y + 1, -z + 1; (ii) x, - y + 3/2, z - 1/2; (iii) x, -y + 1/2, z - 1/2; (iv) x + 1, y, z; (v) -x + 1, y + 1/2, -z + 3/2; (vi) x + 1, -y + 3/2, z - 1/2; (vii) -x + 1, -y + 1, -z + 1; (viii) -x + 1, y - 1/2, -z + 3/2;

3. Material and Methods 3.1. Synthesis

The title compound 1 was obtained according to the reaction scheme 1. The crystals were grown according laboratory procedure and used low-cost standard materials for this purpose. Briefly, a mixture of N-ben-zoylanthranilic acid (0.02 g, 0.083 mmol) and

2

3.2. X-ray Analysis

A crystal of the title complex 1 having approximate dimension 0.15*0.22*0.12 mm was mounted on a glass needle using lab adhesive. All measurements were made on an Oxford Diffraction Xcalibur single crystal X-ray diffractometer using graphite monochro-mated CuKa (X =1.5418 A) radiation and CCD Ruby generation detector. Diffraction data were collected at 20 °C by the ©-scan technique. Accurate unit cell parameters and orientation matrix were obtained by a least-squares fit of several high angle reflections in the ranges 3.73° < 0 < 75.75° for the title compound. The intensity data were collected with an average four-fold redundancy per reflection and optimum resolution (0.83 A). The intensity data collection, frames integration, Lorentz-polarization correction and decay correction were done using CrysAlisPro (version 1.171.37.34)

CuSO4-5H2O (0,014 mg, 0.059 mmol) in ethanol (10 mL) was sonicated for 15 min and refluxed at 75 °C for one hour. The precipitated copper(II) compound was filtered of and recrystallized from ethanol. The crystals were isolated as a bluish solid stable in air and suitable for X-ray diffraction study at 20 °C and collected in 65 % yield.

software [12]. The structure was solved by direct methods using SHELXS-97 implemented in Olex2 program suit [13]. The refinement was carried out by full-matrix least-square method on the positional and anisotropic temperature parameters of the non-hydrogen atoms, using SHELXL-97 [14, 15]. All the H atoms were positioned geometrically and constrained to ride on their parent atom with C—H = 0.93-0.97 A, N—H = 0.86 A and O—H = 0.67-0.85 A, and with UBo(H,H) = 1.2 Ueq for ethyl H atoms and 1.5Ueq(H,H,H) for methyl H atoms. The general-purpose crystallography tool PLATON, ORTEP and MERCURY were used for structure analysis and presentation of the results [1618]. Details of the data collection, crystal parameters and refinement process of compound 1 are given in Table 2.

:ooh

+ CuS045H20

EtOH.

H2O /OEt 2 \ /

O 0H2

0

-NH

"NH

HN

Ph

""Ph P\T ^O

1

Scheme 1. Synthesis of diaqua-bis(N-benzoylanthranilato)-ethylato-copper(II).

Table 2.

Experimental details_

Crystal data

Empirical formula C30H29O9N2Cu

Mr 625.09

Crystal system, space group Monoclinic, P2j/c

Temperature (K) 293

a, b, c (Â) 13.0395(5), 16.3395(3), 14.4133(5)

ß (°) 114.689(5)

V (Â3) 2790.17(19)

Z 4

Radiation type CuKa

Crystal size (mm) 0.15x0.22x0.12

Calculated density (Mg/m3) no measured

Absorption coefficient (mm-1) 1.615

F(000) 1296

Data collection

Absorption correction no

T T 1 mim 1 max 0.689, 0.834

No. of measured, independent and observed [I > 2c(I)] reflections 12729, 5703, 4331

Rint 0.0208

Theta range for data collection (°) 3.73 to 75.75

Refinement

Index ranges -16<=h<=14, 0<=k<=20, 0<=l<=17

R[F2 > 2c(F2)], wR(F2), S 0.0442, 0.1402, 1.058

No. of reflections / restraints / parameters 5703 / 0 / 397

Goodness-of-fit on F2 1.058

Completeness, [dmm-dmax] (%) 98.04

H-atom treatment H-atom parameters constrained

4°max, 4°mm (e Â-3) 0.47, -0.55

Final R indices [I>2c(I)] R1=0.0442, wR2=0.1402

R indices (all data) R1=0.0579, wR2=0.1313

CCDC reference 2033596

Acknowledgments

The work was supported by the Program of Basic Research of the Academy of Sciences of the Uzbekistan (grant VA-FA-F7-004).

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