научная статья по теме SYNTHESES AND CRYSTAL STRUCTURES OF [NI(IIP)2] AND [CU2(PMP)2( 1,1-N3)2] · MEOH (IIP = 2-IMINOMETHYL-4,6-DIIODOPHENOLATE, PMP = 2-[(2-PHENYLAMINOETHYLIMINO)METHYL]PHENOLATE) Химия

Текст научной статьи на тему «SYNTHESES AND CRYSTAL STRUCTURES OF [NI(IIP)2] AND [CU2(PMP)2( 1,1-N3)2] · MEOH (IIP = 2-IMINOMETHYL-4,6-DIIODOPHENOLATE, PMP = 2-[(2-PHENYLAMINOETHYLIMINO)METHYL]PHENOLATE)»

КООРДИНАЦИОННАЯ ХИМИЯ, 2013, том 39, № 10, с. 594-599

УДК 541.49

SYNTHESES AND CRYSTAL STRUCTURES OF [Ni(IIP)2] AND [Cu2(PMP)2(^u-N3)2] • MeOH (IIP = 2-IMINOMETHYL-4,6-DIIODOPHENOLATE, PMP = 2-[(2-PHENYLAMINOETHYLIMINO)METHYL]PHENOLATE)

© 2013 S. S. Qian1, X. S. Cheng2, Z. L. You2, and H. L. Zhu1 *

1School of Life Sciences, Shandong University of Technology, ZiBo, 255049 P.R. China 2Department of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian, 116029 P.R. China

*E-mail: hailiang_zhu@163.com Received February 20, 2012

A new centrosymmetric mononuclear nickel(II) complex, [Ni(IIP)2] (I), and a new end-on azido-bridged dinuclear copper(II) complex, [Cu2(PMP)2(^11-N3)2] ■ MeOH (II) (IIP = 2-iminomethyl-4,6-diiodophe-nolate, PMP = 2-[(2-phenylaminoethylimino)methyl]phenolate), have been prepared from similar triden-tate Schiff bases derived from N-phenylethane-1,2-diamine with 3,5-diiodosalicylaldehyde and salicylalde-hyde, respectively. The complexes were characterized by elemental analysis, infrared spectra, and single-crystal X-ray diffraction. Complex I crystallizes in the monoclinic space group P2j/c with unit cell dimensions a = 4.936(1), b = 11.779(3), c = 15.789(4) А, в = 90.722(3)°, V = 918.0(4) A3, Z = 2, R1 = 0.0267, and wR2 = 0.0546. Complex II crystallizes in the orthorhombic space group Pna2j with unit cell dimensions a = = 23.370(2), b = 12.210(1), c = 11.438(1) A, V = 3263.8(5) A3, Z = 4, R1 = 0.0461, and wR2 = 0.0891. The Ni atom in I is in a square planar coordination, and the Cu atoms in II are in square pyramidal coordination.

DOI: 10.7868/S0132344X13090065

INTRODUCTION

Metal complexes with Schiff bases have been received considerable attention for their importance in the fields of coordination chemistry related to catalysis and enzymatic reactions, magnetism and molecular architectures [1—5]. Nickel and copper complexes with Schiff base ligands been proved to possess interesting biological, catalytic, and magnetic properties [6—10]. During the search of literature, we found that a large number of complexes with the tridentate Schiff bases derived from salicylaldehyde and its derivatives with versatile organic amines had been reported. Yet, to the best of our knowledge, no complexes have been reported for the tridentate Schiff bases 2,4-diiodo-6-[(2-phenylaminoethylimino)methyl]phenol (HIMP) and 2- [(2-phenylaminoethylimino)methyl]phenol (HPMP). As an extension of the work on the Schiff base complexes [11—13], we report in this paper the syntheses and crystal structures of two new nickel(II) and copper(II) complexes, [Ni(IIP)2] (I) and [Cu2(PMP)2(|iu-N3)2] ■ MeOH (II) (IIP = 2-imi-nomethyl-4,6-diiodophenolate, PMP = 2-[(2-phe-nylaminoethylimino)methyl]phenolate.

Y-cXh о

OH

(HIMP) (HPMP)

EXPERIMENTAL

Materials and measurements. Commercially available 3,5-diiodosalicylaldehyde, salicylaldehyde, and N-phenylethane-1,2-diamine were purchased from Aldrich and used without further purification. Other solvents and reagents were made in China and used as received. C, H, and N elemental analyses were performed with a PerkinElmer elemental analyser. The infrared spectra were recorded on a Nicolet AVATAR 360 spectrometer as KBr pellets in the 4000—400 cm-1 region. Thermal stability analysis was performed on a PerkinElmer Pyris Diamond TG-DTA thermal analyses system.

Synthesis of the Schiff base HIMP. 3,5-Diiodosal-icylaldehyde (1.0 mmol, 0.374 g) and N-phenyl-ethane-1,2-diamine (1.0 mmol, 0.136 g) were dissolved in EtOH (20 mL) with stirring. The mixture was stirred for about 30 min at room temperature to give a

yellow solution. The solvent was evaporated to give yellow gummy product of HIMP. The yield was 98%.

For C15H14N2OI2

anal. calcd., %: C, 36.6; H, 2.9; N, 5.7.

Found, %: C, 36.5; H, 2.9; N, 5.6.

Synthesis of the Schiff base HPMP. Salicylalde-hyde (1.0 mmol, 0.122 g) and N-phenylethane-1,2-diamine (1.0 mmol, 0.136 g) were dissolved in EtOH (20 mL) with stirring. The mixture was stirred for about 30 min at room temperature to give a yellow solution. The solvent was evaporated to give yellow gummy product of HPMP. The yield was 95%.

For C^H^O

anal. calcd., %: C, 75.0; H, 6.7; N, 11.7. Found, %: C, 74.8; H, 6.8; N, 11.5.

Synthesis of [Ni(IIP)2] (I). A MeOH solution (5 mL) of nickel acetate (0.1 mmol, 24.9 mg) was added to a MeOH solution (10 mL) of HIMP (0.1 mmol, 49.2 mg) with stirring. The mixture was stirred for 30 min to give a red solution. The resulting solution was allowed to stand in air for a few days. Red block-shaped crystals suitable for X-ray single crystal analysis were formed at the bottom of the vessel. The isolated product was washed three times with cold EtOH, and dried in a vacuum over anhydrous CaCl2. The yield was 21.0 mg (52% on the basis of HIMP).

For C14H8N2O2I4Ni

anal. calcd., %: C, 21.0; H, 1.0; N, 3.5.

Found, %: C, 20.8; H, 1.1; N, 3.5.

Synthesis of [Cu2(PMP)2(^u-N3)2] • MeOH (II).

A MeOH solution (5 mL) of copper acetate (0.1 mmol, 19.9 mg) was added to the mixture of a MeOH solution (10 mL) of HPMP (0.1 mmol, 24.0 mg) and sodium azide (0.1 mmol, 6.5 mg) with stirring. The mixture was stirred for 30 min to give a blue solu-

tion. The resulting solution was allowed to stand in air for a few days. Blue block-shaped crystals suitable for X-ray single crystal analysis were formed at the bottom of the vessel. The isolated product was washed three times with cold EtOH, and dried in a vacuum over anhydrous CaCl2. The yield was 16.0 mg (44% on the basis of HPMP).

For C31H34N10O3Cu2

anal. calcd., %: C, 51.6; H, 4.7; N, 19.4. Found, %: C, 51.7; H, 4.8; N, 19.2.

X-ray structure determination. Diffraction intensities for the complexes were collected at 298(2) K using a Bruker SMART 1K area-detector with MoZ„ radiation (X = 0.71073 A). The collected data were reduced using the SAINT program [14], and multi-scan absorption corrections were performed using the SADABS program [15]. The structures of the complexes were solved by direct methods and refined against F2 by full-matrix least-squares methods using the SHELXTL [16]. All of the non-hydrogen atoms were refined anisotropically. The imino H atoms in I and the amino H atoms in II were located from difference Fourier maps and refined isotropically, with N—H distances restrained to 0.90(1) A. The remaining H atoms were placed in idealized positions and constrained to ride on their parent atoms. The crystallo-graphic data for the complexes are summarized in Table 1. Selected bond lengths and angles are given in Table 2. Supplementary material has been deposited with the Cambridge Crystallographic Data Centre (nos. 825216 (I) and 867494 (II); deposit@ ccdc.cam.ac.uk or http://www.ccdc.cam. ac.uk).

RESULTS AND DISCUSSION

The complexes I and II were readily prepared by the similar synthetic procedure, as shown in Scheme. It is interesting that for the preparation of I, the starting material HIMP was changed to HIIP during the coordination.

+ Ni(MeCOO)2

T i 1

H (I)

fTN^ a ii

+ Cu(MeCOO)2 + NaN3 ■

Scheme.

o-

NNN

NNN

MeOH

\

aHN3;v (ii)

i

i

I

KOOP^HH^HOHHAtf XHMH3 TOM 39 № 10 2013 2*

Table 1. Crystallographic and experimental data for the complexes I and II

Parameter Value

I II

Fw 802.5 721.8

Crystal shape/color Block/red Block/blue

Crystal size, mm 0.20 x 0.20 x 0.18 0.23 x 0.21 x 0.21

Crystal system Monoclinic Orthorhombic

Space group P2x/c Pna21

a, A 4.936(1) 23.370(2)

b, A 11.779(3) 12.210(1)

c, A 15.789(4) 11.438(1)

ß, deg 90.722(3) 90

V, A3 918.0(4) 3263.8(5)

Z 2 4

^(MoÄ"a), mm-1 7.791 1.352

Pcalcd g cm-3 2.903 1.469

F(000) 724 1488

T T J min J max 0.3048, 0.3345 0.7462, 0.7644

Reflections measured 7095 13865

Unique reflections (Rint) 1981 6857

Observed reflections (I > 2ct(I)) 1559 4778

Parameters 109 425

Restraints 1 4

Goodness of fit on F 2 1.079 1.000

R1, wR2 (I> 2a(I))* 0.0267, 0.0546 0.0461, 0.0891

R1, wR2 (all data)* 0.0402, 0.0609 0.0800, 0.1022

Largest diff. peak and hole, e A-3 1.150 and -0.768 0.343 and -0.279

* Ri = Zii^i - i^ci№i, wR2 = [Zw ( fO - (FO )2]1/2.

The molecular structure of the complex I is shown in Fig. 1. The compound is a centrosymmetric mononuclear nickel(II) complex, with the Ni atom located at the inversion center. The Ni atom in the complex is coordinated by two phenolate O and two imine N atoms from two IIP ligands, forming a square planar geometry. The Ni—O and Ni—N bond lengths in the complex are comparable to the corresponding values observed in other Schiff base nickel(II) complexes with square planar geometies [17, 18]. In the crystal structure of the complex, molecules are linked through intermolecular N(1)-H(1)-I2i (N(1)-H(1) 0.90(1), H(1)-I(2) 3.07(5), N(1)-I(2) 3.775(4) Á, N(1)-H(1)-I(2) 137(5)°; symmetry code: '1 - x,

—1/2 + y, 1/2 — z) hydrogen bonds, forming layers parallel to the yz plane, as shown in Fig. 2.

The molecular structure of the complex II is shown in Fig. 3. The compound contains an end-on azido-bridged dinuclear copper(II) complex molecule and a methanol molecule of crystallization. The intramolecular Cu---Cu distance is 3.339(1) Â, indicating there exists strong metallophilic interaction. Each Cu atom in the complex is in a square-pyramidal coordination, with the phenolate O, imine N, and amine N atoms of the PMP ligand and one azide N atom defining the basal plane, and with the other azide N atom occupying the apical position. The deviations of the Cu(1) and Cu(2) atoms from the least-squares planes defined

KOOP,3HHAUHOHHAH XHMH3 tom 39 № 10 2013

Table 2. Selected bond lengths (Â) and angles (deg) for structures I and II

Bond d, Â Bond d, Â

Ni(1)-O(1) Cu(1)-O(1) Cu(1)-N(2) Cu(1)-N(8) Cu(2)-N(3) Cu(2)-N(4) ] 1.833(3) I 1.919(3) 2.034(4) 2.507(4) 1.930(4) 2.083(4) [ Ni(1)-N(1) I Cu(1)-N(1) Cu(1)-N(5) Cu(2)-O(2) Cu(2)-N(8) Cu(2)-N(5) 1.847(4) 1.956(4) 2.004(4) 1.916(3) 2.000(4) 2.435(4)

Angle œ, deg Angle œ, deg

O(1)Ni

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