научная статья по теме COORDINATION POLYMER {[CD2(NIL)2(BTCA)2] · H2O}N OF MACROCYCLIC OXAMIDE WITH BENZOTRIAZOLE-5-CARBOXYLATE: SYNTHESES, CRYSTAL STRUCTURES, AND FLUORESCENCE PROPERTIES Химия

Текст научной статьи на тему «COORDINATION POLYMER {[CD2(NIL)2(BTCA)2] · H2O}N OF MACROCYCLIC OXAMIDE WITH BENZOTRIAZOLE-5-CARBOXYLATE: SYNTHESES, CRYSTAL STRUCTURES, AND FLUORESCENCE PROPERTIES»

КООРДИНАЦИОННАЯ ХИМИЯ, 2015, том 41, № 9, с. 539-544

УДК 541.49

COORDINATION POLYMER {[Cd2(NiL)2(Btca)2] • H2O}„ OF MACROCYCLIC OXAMIDE WITH BENZOTRIAZOLE-5-CARBOXYLATE: SYNTHESES, CRYSTAL STRUCTURES, AND FLUORESCENCE PROPERTIES

© 2015 N. Xin1, 2, Y. F. Zheng1, 2, and Y. Q. Sun1, 2, *

1Tianjin Key Laboratory of Structure and Performance for Functional Molecule, College of Chemistry, Tianjin Normal University, Tianjin, 300387 P.R. China

2Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Tianjin Normal University, Tianjin, 300387P.R. China

*E-mail: hxxysyq@mail.tjnu.edu.cn

Received January 20, 2015

A novel heterometallic coordination polymer {[Cd2(NiL)2(Btca)4] • H2O}„ (I) (H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H2Btca = benzotriazole-5-carboxylic acid) was synthesized and structurally characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction (CIF file CCDC no. 1043065). Complex I exhibits a two-dimensional network structure formed by Cd2Ni2 units via the oxamide and benzotriazole-5-carboxylate bridges. It crystallizes in the monoclinic system, space group P2j/c. The lattice parameters are: a = 1.24488(8), b = 2.75370(19), c = 1.49336(10) Â, P = = 103.1070(10)° and V = 4.9859(6) Â3, Z = 4. The fluorescence properties of compound I are also discussed.

DOI: 10.7868/S0132344X15080101

INTRODUCTION

Coordination polymers are active fields of research, encompassing chemistry, physics, biology, and material science [1—4]. Especially, the heterometallic coordination polymers have recently attracted much attention because of their fascinating structures and their potential application in magnetism, luminescence, adsorption, catalysis [5—10]. However, hetero-metallic coordination polymers remain relatively scarce because of the coordinative complexity of the heterometallic ions involved in the self-assembly process [11—16]. Recently, some aromatic multicarboxy-late as co-ligands were chosen to design and construct diverse oxamido-bridged heteropolynuclear networks [17—20]. However, those containing oxamide and het-erocyclic carboxylate mix bridged polynuclear complexes have been made rarely [17—21].

Among various heterocyclic carboxylate ligands, benzotriazole-5-carboxylate (Btca2-) has been used to produce metal-organic frameworks owing to their di-

verse coordination modes and a great ability to satisfy many metal coordination preferences [22]. Furthermore, the strong n-conjugated system of large benzo-triazole ring can increase the stability of structures [17, 23]; and five coordination atoms can potentially serve as hydrogen bond acceptors and donors to assemble supramolecular structure.

With these facts in mind and in continuation of our interest in heterometallic polynuclear complexes, by using the benzotriazole-5-carboxylate and macrocy-clic oxamide complex ligand NiL, a novel 2D heterometallic coordination polymer was firstly obtained. Herein, we report the syntheses, crystal structures and fluorescence properties of the complex {[Cd2(NiL)2(Btca)2] • H2O}„ (I). The coordinated modes of the Btca2- (a—d) and the coordinated modes of the macrocylic oxamide complex ligand NiL (e) are given in Scheme:

M

.O

M

O'

,N

M

O

O

N

N

M

N

.N-M

M

N

M

(a)

(b)

M

O

M

N

M

"^N-M

V

O

N

M

N

,N

N

M

M

(c)

(d)

CX X>

—N ^ O

Parameter Value

Fw 1347.20

Crystal system Monoclinic

Space group P2i/c

a, A 12.4488(8)

b, A 27.5370(19)

c, A 14.9336(10)

P, deg 103.1070(10)

V, A3 4985.9(6)

P calcd g/cm3 1.795

Z 4

F(000) 2696

p., mm-1 1.660

Crystal size, mm 0.18 x 0.17 x 0.16

T, K 173(2)

9 Range, deg 1.58-25.01

Index ranges hkl -14 < h < 13, -32 < k < 31,

-17 < l < 15

Reflection collected 28729

Rint 0.0637

Reflections with I > 2o(I) 8792

Number of parameters 739

GOOF 1.063

R1, wR2 (I > 2a(I)) 0.0423, 0.0882

^max^mi^ e A—3 1.205/-0.536

EXPERIMENTAL

All the starting reagents were of A. R. grade and were used as purchased. The complex ligand NiL was prepared as described elsewhere [24]. Analyses of C, H and N were determined on a Perkin-Elmer 240 Elemental analyzer. IR spectrum was recorded as KBr discs on a Shimadzu IR-408 infrared spectrophotometer in the 4000—600 cm-1 range. XRPD spectra for the power were recorded with a Model D/MAX-2550V Rigaku, Japan. Test the fluorescence properties were recorded with the RF-5301PC fluorescence.

Synthesis of {[Cd2(NiL)2(Btca)2] • H2O}„ (I). A mixture of CdSO4 • 6H2O (0.01 mmol, 76.5 mg), H2Btca (0.01 mmol, 16.0 mg), NiL (0.05 mmol, 19.7 mg), H2O (10 mL) and CH3OH (4 mL) was put into an 18 mL Teflon-lined reactor, and the pH value of the solution was adjusted to about 7-8 with triethylamine. After stirring, the mixture was heated at 150°C for 72 h. Then the reaction system was cooled to room temperature during 72 h, and brown-red crystal of the compound was isolated by filtering and washing with water.

For C52H40N14O9Cd2Ni2

(e: M = Ni) Scheme.

Table 1. Crystallographic data and structure refinement of complex I

anal. calcd., %: Found, %:

C, 46.36; C, 46.35;

H, 2.99; H, 2.97;

N, 14.56. N, 14.54.

Main IR bands: 3436 s. br, 1634 s, 1584 s, 1553 s, 1475 m, 1384 s, 1311 m, 1270 m, 1160 w, 1123 w, 1082 w, 956 w, 846 w, 793 s, 750 s.

For C52H40N14O9Ni2Cd2

anal. calcd., %: C, 46.36; H, 2.99; N, 14.56. Found, %: C, 46.35; H, 2.97; N, 14.54.

X-ray crystallography. Single crystal X-ray diffraction analyses of I were carried out on a Bruker Smart Apex II CCD diffractometer equipped with a graphite monochromated MoZ„ radiation (X = 0.71073 A) by using ® scan technique at room temperature. Semi-empirical absorption corrections were applied using SADABS. All structures were solved by direct methods using the SHELXS program of the SHELXTL package and refined with SHELXL. Hydrogen atoms were added geometrically and refined with riding model position parameters and fixed iso-tropic thermal parameters. Crystal data collection and refinement parameters are given in Table 1, and selected bond lengths and angles for I is listed in Table 2.

Supplementary material has been deposited with the Cambridge Crystallographic Data Centre (no. 1043065; deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk).

RESULTS AND DISCUSSION

By using benzotriazole-5-carboxylate and macro-cylic oxamide mixed ligands as the metal linker, the

COORDINATION POLYMER {[Cd2(NiL)2(Btca)2] • H2O}„ 541

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

Bond d, Â Bond d, Â

Cd(1)-O(7)#! 2.212(3) Cd(2)-O(3) 2.468(3)

Cd(1)-N(9)#2 2.231(4) Ni(1)-N(7) 1.878(4)

Cd(1)-N(12) 2.254(4) Ni(1)-N(6) 1.880(4)

Cd(1)-O(2) 2.267(3) Ni(1)-N(8) 1.881(4)

Cd(1)-O(1) 2.426(3) Ni(1)-N(5) 1.910(4)

Cd(2)-N(14) 2.226(4) Ni(2)-N(2) 1.884(4)

Cd(2)-O(5) 2.259(3) Ni(2)-N(1) 1.886(4)

Cd(2)-O(4) 2.271(3) Ni(2)-N(3) 1.887(4)

Cd(2)-N(11)#3 2.303(4) Ni(2)-N(4) 1.905(4)

Cd(2)-O(6) 2.440(3)

Angle ю, deg Angle ю, deg

O(7)#1Cd(1)N(9)#2 103.20(13) N(11)#3Cd(2)O(6) 87.08(12)

O(7)#xCd(1)N(12) 98.76(13) N(14)Cd(2)O(3) 82.71(12)

N(9)#2Cd(1)N(12) 116.26(13) O(5)Cd(2)O(3) 94.28(12)

O(7)#xCd(1)O(2) 145.74(11) O(4)Cd(2)O(3) 69.05(11)

N(9)#2Cd(1)O(2) 100.04(13) N(11)#3Cd(2)O(3) 156.84(12)

N(12)Cd(1)O(2) 93.07(13) O(6)Cd(2)O(3) 97.35(11)

O(7)#xCd(1)O(1) 78.60(11) N(7)Ni(1)N(6) 90.85(19)

N(9)#2Cd(1)O(1) 154.93(13) N(7)Ni(1)N(8) 92.56(18)

N(12)Cd(1)O(1) 87.73(12) N(6)Ni(1)N(8) 165.46(18)

O(2)Cd(1)O(1) 69.83(11) N(7)Ni(1)N(5) 161.59(18)

N(14)Cd(2)O(5) 105.81(13) N(6)Ni(1)N(5) 94.07(18)

N(14)Cd(2)O(4) 102.01(13) N(8)Ni(1)N(5) 87.10(17)

O(5)Cd(2)O(4) 145.33(12) N(2)Ni(2)N(1) 91.25(17)

N(14)Cd(2)N(11)#3 99.97(14) N(2)Ni(2)N(3) 91.48(17)

O(5)Cd(2)N(11)#3 106.89(13) N(1)Ni(2)N(3) 166.54(17)

O(4)Cd(2)N(11)#3 87.97(13) N(2)Ni(2)N(4) 162.55(17)

N(14)Cd(2)O(6) 161.98(12) N(1)Ni(2)N(4) 86.79(17)

O(5)Cd(2)O(6) 56.18(11) N(3)Ni(2)N(4) 94.45(17)

O(4)Cd(2)O(6) 94.75(11)

* Symmetry codes: #1 -x + 1, -y, -z + 2; #2 x, y, z + 1; #3 x, -y + 1/2, z + 1/2.

new complex I has been synthesized under solvother-mal condition. The results reported here and previously reported [17, 25], clearly show that the solvothermal synthesis is a powerful and versatile tool for preparing macrocyclic oxamide and organic acid bridged heterometallic coordination polymers. Considering that the deprotonated degree of H2Btca may play a vital role in constructing the extended structure, a series of experiments were performed by varying the pH values

of the reaction system in the range of 4-9. The results show that the complex was obtained at relatively higher pH (7-8). Complex I is stable under the ambient conditions and insoluble in common solvents, such as water, alcohol, and acetonitrile.

The IR spectra of complex I clearly show the existence of benzotriazole-5-carboxylate and macrocyclic oxamido moieties in the molecules respectively. The IR spectra ofI exhibit broad absorption bands in the ran-

КООРДИНАЦИОННАЯ ХИМИЯ том 41 № 9 2015

N(9)

Fig. 1. Perspective view of asymmetric structure of Cd2Ni2 unit in I: (A) x, 0.5 — y, 0.5 + z; (B) 1 — x, —y, 2 — z; (C) x, y, 1 + z.

ge 3360—3450 cm 1, demonstrating the existence of water [26], and the spectra exhibit strong absorption bands in the region 1629—1613 cm-1 and 1588—1563 cm-1 due to the v(C=O) and the v(C=N) vibrations, respectively [26, 27]. The IR spectra of it show no bands in the region 1680—1720 cm—1, indicating complete depro-tonation of the carboxyl groups.

To confirm the phase purity of the obtained complex, the original samples were characterized by XRPD at room temperature. The experimental spectra of complex I is almost consistent with those of simulated based on the structure models derived from single-crystal X-ray diffraction data, indicating the phase purity of the products. The differences in intensity may be due to the preferred orientation of the power.

The ligands involved in this research are listed in Scheme (d) and (e). Single-crystal X-

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