научная статья по теме HYDROTHERMAL SYNTHESIS AND CRYSTAL STRUCTURE OF A NEW 2D METAL-ORGANIC FRAMEWORK: [ZN(BTCA)(PHEN)]N (H2BTCA = BENZOTRIAZOLE-5-CARBOXYLIC ACID, PHEN = 1,10-PHENANTHROLINE) Химия

Текст научной статьи на тему «HYDROTHERMAL SYNTHESIS AND CRYSTAL STRUCTURE OF A NEW 2D METAL-ORGANIC FRAMEWORK: [ZN(BTCA)(PHEN)]N (H2BTCA = BENZOTRIAZOLE-5-CARBOXYLIC ACID, PHEN = 1,10-PHENANTHROLINE)»

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HYDROTHERMAL SYNTHESIS AND CRYSTAL STRUCTURE OF A NEW 2D METAL-ORGANIC FRAMEWORK: [Zn(Btca)(Phen)]w (H2Btca = BENZOTRIAZOLE-5-CARBOXYLIC ACID, Phen = 1,10-PHENANTHROLINE)

© 2011 R. Y. Lu1 and Z. B. Han1, 2, *

1College of Chemistry, Liaoning University, Shenyang 110036, P.R. China 2Key Laboratory of Polyoxometalate Science of Ministry of Education, Northeast Normal University,

Changchun 130024, P.R. China *E-mail: ceshzb@lnu.edu.cn Received May 24, 2010

A new coordination polymer, [Zn(Btca)(Phen)]n (I) (H2Btca = benzotriazole-5-carboxylic acid, Phen = 1,10-phenanthroline), has hydrothermally been synthesized by the reaction of zinc nitrate, H2Btca and Phen in the presence of DMF and H2O. Single-crystal X-ray diffraction analysis reveals that in complex I the metal centers are linked by the bridging Btca ligand to form an extended two-dimensional wave-like layer decorated by Phen.

INTRODUCTION

Over the past decades, the design and synthesis of metal-organic frameworks have received rather considerable attention in the field of supramolecular chemistry and crystal engineering not only stemming from their potential applications in gas absorption [1—3], luminescence [4, 5], magnetic fields [6, 7], ion exchange [8, 9], NLO (non-linear optics) materials [10] and molecular recognition [11—14], but also from their interesting variety oftopologies [15—18]. Much ofthe work has been focused on the coordination polymers containing benzen-ecarboxylates. In recent years, heterocyclic carboxylic acids as an extension of benzenecarboxylates have been extensively employed in this field, such as pyridine-, pyrazole-, and imidazolecarboxylic acids [19]. These ligands combine the advantages of both carboxyl and aromatic heterocyclic components and are able to link various metal ions through many kinds ofcoordination fashions. Among the various heterocyclic carboxylic acids ligands, benzotriazole-5-carboxylic acid (Btca) has rarely been reported [20]. In this paper, we report the synthesis and crystal structure of[Zn(Btca)(Phen)]B (I).

EXPERIMENTAL

Materials and methods. All reagents and solvents employed were commercially available and used as received without further purification. The C, H, and N microanalyses were carried out with a PerkinElmer 240 elemental analyzer. The FT-IR spectra were recorded from KBr pellets in the 4000—400 cm-1 range on a Nicolet 5DX spectrometer.

Hydrothermal synthesis of I. A mixture of Zn(NO3)2 • • 6H2O (0.149 g, 0.5 mmol), H2Btca (0.048 g, 0.3 mmol), Phen (0.059 g, 0.3 mmol), DMF (5 ml), and H2O (5 ml) was sealed in a 23-ml teflon reactor and heated at 140°C for three days. The reaction mixture was slowly cooled to room temperature. Yellow crystals of I suitable for X-ray diffraction analysis were isolated (the yield is ~30%).

For C19H11N5O2Zn

anal. calcd., %: Found, %:

C, 56. 11; C, 56. 15;

H, 2.73; H, 2.88;

N, 17. 22. N, 17. 35.

X-ray crystal determination. The crystallographic data for I were c^hc

ollected at room temperature an a Bruker P4 diffrac-tometer with MoKa radiation (X = 0.71073 A) and a graphite monochromator using the ® scan mode. The structure was solved by direct methods and refined on F2 by full-matrix least squares using SHELXTL [21-23]. All non-hydrogen atoms were treated anisotropically. Positions of hydrogen atoms were generated geometrically. Crystallographic data and experimental details for structural analysis are summarized in Table 1. Selected bond lengths and angles are listed in Table 2. The atomic coordinates and other parameters of structure I have been deposited with the Cambridge Crystallographic Data Centre (№ 777428; deposit@ccdc.cam.ac.uk or http: //www.ccdc.cam.ac.uk).

RESULTS AND DISCUSSION Compound I exhibits a 2D wave-like layered structure in which the asymmetric unit contains one Zn2+ ion, one

Table 1. Crystallographic data and experimental details for complex I

Parameter Value

Formula weight 406.70

Crystal system Orthorhombic

Space group Pbca

Unit cell dimensions:

a, A 17.0961(19)

b, A 8.902(2)

c, A 20.622(5)

V, A3 3138.3(11)

Z 8

Pcalcd g/cm3 1.722

p, mm-1 1.593

F(000) 1648

Crystal size, nm 0.38 x 0.27 x 0.22

9 Range, deg 1.98-26.02

Reflections collected 3924

Independent reflections (R^t) 3086( 0.0382)

Max, min transmission 0.7218, 0.5843

T, K 293(2)

Goodness-of-fit on F2 1.014

Final R indices (I > 2a(T))* R1 = 0.0422, wR2 = 0.0915

R indices (all data) Rx = 0.0719, wR2 = 0.1054

Largest diff. peak and hole, e A-3 0.448 and -0.619

R = SjjiOj - |FC||/S|F0|; wR2 = ![w(fO - F2)'] /w(FO)

2 1/2

Btca2- ligand, and one Phen ligand. As shown in Fig. 1, the Zn(II) center lies in a distorted ZnN4O2 octahedral environment, which is provided by two nitrogen atoms from two different Btca2- ligands (Zn(1)—N(M) 2.085(3), Zn(1)—N(3) 2.118(3) A), two oxygen atoms from a Btca2- ligand (Zn(1)-O(LB) 2.223(3), Zn(1)-O(2$) 2.235(3) A), and two nitrogen atoms from a Phen ligand (Zn(1)-N(5) 2.189(3), Zn(1)-N(4) 2.219(3) A) (Table 2). The atoms N(3) and N(4) are axi-ally coordinated with an approximately linear NZnN angle (167°). The equatorial plane is defined by the other four atoms.

The Phen ligand in compound I does not serve as a linker or produce the dimensionality of the structure, but only decorates the 2D layer due to its coordination fashion chelating a single Zn center. The adjacent Zn(II) atoms are bridged by a nitrogen atom and a carboxyl group of the Btca2- ligand to construct a 1D chain, as shown in Fig. 2. The Btca2- ligand adopts tridentate coordination mode (Fig. 3) to link three Zn(II) centers via its two tria-zole nitrogen atoms and two oxygen atoms. The adjacent 1D chains are further connected by the nitrogen atoms of Btca2- to form an extended wave-like layer propagating approximately along the y axis (Fig. 4).

In conclusion, a new 2D coordination polymer I, has successfully been synthesized through the hydrothermal reaction. The Zn atom is surrounded by four nitrogen at-

Table 2. Selected bond lengths (A) and angles (deg) in I*

Bond d, A Bond d, A

Zn(1)-N(1)A 2.085(3) Zn(1)-N(3) 2.118(3)

Zn(1)-N(5) 2.189(3) Zn(1)-N(4) 2.219(3)

Zn(1)-O(1)A 2.223(3) Zn(1)-O(2)A 2.235(3)

Angle ro, deg Angle ro, deg

N(1)AZn(1)N(3) 96.81(11) N(1)AZn(1)N(5) 105.85(12)

N(3)Zn(1)N(5) 92.42(12) N(1)Zn(1)N(4) 90.02(11)

N(3)Zn(1)N(4) 167.01(11) N(5)Zn(1)N(4) 75.04(11)

N(1)AZn(1)O(1)B 92.27(11) N(3)Zn(1)O(1)B 100.51(11)

N(5)Zn(1)O(1)B 156.37(11) N(4)Zn(1)O(1)B 90.20(11)

N(1)AZn(1)O(2)B 151.02(11) N(3)Zn(1)O(2)B 90.77(11)

N(5)Zn(1)O(2)B 101.71(11) N(4)Zn(1)O(2)B 88.51(11)

O(1)AZn(1)O(2)B 58.81(11)

* Symmetry codes: A -x + 1/2, y + 1/2, z; B -x, y + 1/2, -z + 1/2.

HYDROTHERMAL SYNTHESIS AND CRYSTAL STRUCTURE

175

C(16)

Fig. 1. Coordination environment of the Zn(II) centers in I.

Fig. 3. Tridentate coordination mode of Btca2 ligand. КООРДИНАЦИОННАЯ ХИМИЯ том 37 № 3 2011

oms and two oxygen atoms from Btca2- and Phen ligands. The Btca2- ligand connects three Zn(II) atoms to form a two-dimensional undulated layer.

ACKNOWLEDGMENTS

This work was supported by the National Natural Science Foundation of China (grant no. 20871063).

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