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Article

Synthesis, Crystal Structure, and Luminescent Property of a Cd(II) Coordination Polymer with a N-Nicotinoylglycine Ligand

1
College of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, China
2
Department of Chemistry, Qinghai Normal University, Xining 810008, China
3
College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266061, China
*
Author to whom correspondence should be addressed.
Crystals 2017, 7(2), 33; https://doi.org/10.3390/cryst7020033
Submission received: 6 December 2016 / Revised: 19 January 2017 / Accepted: 23 January 2017 / Published: 25 January 2017

Abstract

:
A new 1D Cd(II) coordination polymer, [{CdL2(H2O)}·(H2O)3]n (HL = N-nicotinoylglycine), has been synthesized by the assembly of Cd(NO3)2·4H2O with N-nicotinoylglycine, and its composition was determined by elemental analysis, infrared, and X-ray single-crystal diffraction analysis. In this complex, the Cd(II) is seven-coordinated by two N atoms of two N-nicotinoylglycine anions, four O atoms of two N-nicotinoylglycine anions, and one O atom of a coordinated water molecule. The complex forms a 1D looped coordination polymer by the bridging of the N-nicotinoylglycine anion. The luminescent property of the N-nicotinoylglycine ligand and the Cd(II) coordination polymer has also been studied.

1. Introduction

Metal-organic coordination polymers have received great attention as an important part of coordination chemistry. Many of them that are constructed by Cd(II) ions or bridging multipodal ligands show unique structures and excellent properties in gas storage, luminescence, catalysis, and magnetism [1,2,3,4,5,6,7]. In the past decades, many multipodal ligands containing two –COO functional groups and neutral ligands, such as 4,4′-bipyridine and 1,10-phenanthroline, have been chosen to build coordination polymers [8,9,10,11,12,13]. Recently, our group has obtained some new Cd(II), Ca(II), Mg(II), and Zn(II) coordination polymer materials and have investigated their structures and properties [14,15,16,17,18]. In order to investigate the coordination behavior of ligands containing both −COO and pyridine bifunctional groups and the property of their metal complexes, herein, a new 1D Cd(II) coordination polymer, [{CdL2(H2O)}·(H2O)3]n (HL = N-nicotinoylglycine) has been synthesized and its luminescent property in the solid state has also been investigated. The chemical diagram of the Cd(II) complex is shown in Scheme 1.

2. Results and Discussion

2.1. Characterization of [{CdL2(H2O)}·(H2O)3]n

A comparison of the N-nicotinoylglycine ligand and Cd(II) complex was conducted with infrared data, and the ligand shows two characteristic absorption bands at 1725 cm−1 (ν (COO)) and 1634 cm−1 (ν (C(O)-NH)), and at 1675 cm−1 (ν (COO)) and 1636 cm−1 (ν (C(O)-NH)), respectively. The shift of COO is 50 cm−1, indicating that the oxygen atom of the COO group coordinated to Cd(II). However, The shift of C(O)-NH is 2 cm−1, indicating that the oxygen atom of the C(O)-NH group does not coordinate to Cd(II). The band at 3256 cm−1 proves that the Cd(II) complex contains water molecules [19].

2.2. Structural Description of [{CdL2(H2O)}·(H2O)3]n

The coordination environment of the Cd(II) ion in [{CdL2(H2O)}·(H2O)3]n is shown in Figure 1. Selected bond distances and bond angles are given in Table 1. Its crystal structure shows that each Cd(II) ion is seven-coordinated by four O atoms from two carboxyl group of two different N-nicotinoylglycine anion ligands, two N atoms from two different N-nicotinoylglycine anion ligands, and one O atom from a coordinated water molecule. Each Cd(II) ion adopts a distorted pengonal bipyramidal coordination environment. The carboxyl groups of N-nicotinoylglycine anion ligands adopt a didentate coordination mode in the complex molecule. The distances of Cd···Cd separated by N-nicotinoylglycine anion ligands are 10.064 Å and 9.933 Å, respectively.
In the crystal, the looped structure is formed by the bridging of N-nicotinoylglycine anion ligands (Figure 2). The 3D network is generated by π···π stacking and hydrogen bond interactions (Figure 3).

2.3. Luminescent Property

The luminescent behaviors of [{CdL2(H2O)}·(H2O)3]n and the free ligand are investigated in the solid state on a multicrystalline bulk sample. The luminescent spectrum of the Cd(II) coordination polymer is shown in Figure 4. The Cd(II) coordination polymer shows a luminescent peak at 458 nm when excited at 358 nm, however, the N-nicotinoylglycine ligand does not have a luminescent peak. Thus, the luminescent emission of the Cd(II) coordination polymer may be due to the charge transfer of ligand-to-metal [20].

3. Experimental Section

3.1. Materials and Instrumentation

N-nicotinoylglycine and Cd(NO3)2·4H2O were purchased from Xi’ya Chemical Reagent Company and used as received. C, H, and N were determined on a Elementar Vario III EL elemental analyzer (Hanau, Germany). IR spectra were recorded on a Nicolet AVATAR 360 FTIR spectrophotometer (Nicolet Instrument Inc., Madison, WI, USA) (range 4000 cm−1~400 cm−1) as KBr discs. Crystal structure of [{CdL2(H2O)}·(H2O)3]n was determined on a Bruker Smart CCD diffractometer (Bruker, Billerica, MA, USA). Luminescent spectra were recorded on a PE LS-55 spectrometer (PerkinElmer, Billerica, MA, USA).

3.2. Synthesis of [{CdL2(H2O)}·(H2O)3]n

A CH3CH2OH/H2O (v:v = 3:1) solution of N-nicotinoylglycine (0.1802 g, 1.0 mmol) and NaOH (0.040 g, 1.0 mmol) was stirred to clarify, then a water solution (3 mL) of Cd(NO3)2·4H2O (0.3085 g, 1.0 mmol) was added to the above mixture. The mixture was stirred for 5 h at 60 °C and filtered. Colorless crystals suitable were obtained after 10 days by evaporation at room temperature. Yield 52%. Anal. Calcd. for C16H22N4O10Cd: C, 35.37; H, 4.05; N, 10.32. Found: C, 35.15; H, 4.47; N, 10.11. IR νmax (cm−1): ν (H2O):3256 cm−1, ν (COO): 1675 cm−1, ν (C(O)-NH): 1636 cm−1.

3.3. Crystal Structure Determination

Crystal data of [{CdL2(H2O)}·(H2O)3]n were collected on a Bruker Smart APEX CCD diffractometer at 293(2) K using graphite-monochromated Mo radiation (λ = 0.71073 Å). The structure was solved by direct method using the SHELX program [21], and refined by full-matrix least squares on F2 using the SHELXL program [22]. Technical details of the crystal structure solutions and refinements are listed in Table 2.

4. Conclusions

In summary, [{CdL2(H2O)}·(H2O)3]n has been prepared and characterized by elemental analysis, infrared, and X-ray single-crystal diffraction analysis. The Cd(II) complex forms a 1D helix coordination polymer by the bridging of the N-nicotinoylglycine anion. The 3D network is generated by π···π stacking interactions. The luminescent property of the N-nicotinoylglycine ligand and the Cd(II) coordination polymer has also been studied.

Acknowledgments

This project was supported by the National Natural Science Foundation of China (No. 21171132), the National Natural Science Foundation of Shandong (ZR2014BL003), the Project of Shandong Province Higher Educational Science and Technology Program (J14LC01) and Science Foundation of Weifang.

Author Contributions

Tai Xi-Shi designed the method and wrote the manuscript. Wang Xin synthesized the Cd(II) coordination polymer. Li Peng-Fei analysed the crystal data of Cd(II) coordination polymer.

Conflicts of Interest

The authors confirm that this article content has no conflict of interest.

Appendix A

Crystallographic data for the structure reported in this paper has been deposited with the Cambridge Crystallographic Data Centre as supplementary publication No. CCDC 1470820. Copy of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: +44-1223-336-033; E-Mail: [email protected]).

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Scheme 1. Chemical diagram of the Cd(II) complex.
Scheme 1. Chemical diagram of the Cd(II) complex.
Crystals 07 00033 sch001
Figure 1. The coordination environment of the Cd(II) ion.
Figure 1. The coordination environment of the Cd(II) ion.
Crystals 07 00033 g001
Figure 2. One-dimensional chained structure by the bridging of ligands.
Figure 2. One-dimensional chained structure by the bridging of ligands.
Crystals 07 00033 g002
Figure 3. 3D supramolecular network structure.
Figure 3. 3D supramolecular network structure.
Crystals 07 00033 g003
Figure 4. The luminescent spectrum of the Cd(II) coordination polymer.
Figure 4. The luminescent spectrum of the Cd(II) coordination polymer.
Crystals 07 00033 g004
Table 1. Selected bond lengths d (Å) and bond angles (°) for [{CdL2(H2O)}·(H2O)3]n.
Table 1. Selected bond lengths d (Å) and bond angles (°) for [{CdL2(H2O)}·(H2O)3]n.
BonddBondd
Cd1-O42.283(3)Cd1-O62.337(3)
Cd1-N1 i2.357(3)Cd1-O1W2.361(3)
Cd1-N3 ii2.370(3)Cd1-O52.493(3)
Cd1-O22.609(3)C6-O11.222(5)
C8-O21.229(5)C8-O41.267(5)
C16-O51.251(5)O6-C161.234(5)
C1-N11.337(5)C5-N11.336(5)
C6-N21.330(5)N2-C71.441(5)
N3-C131.331(5)N3-C91.350(5)
N4-C141.327(5)N4-C151.442(5)
C16-C151.517(5)C2-C11.378(6)
C3-C21.383(6)C4-C31.385(5)
C4-C51.380(5)C4-C61.501(5)
C7-C81.528(5)C9-C101.383(6)
C10-C111.379(6)C11-C121.389(5)
AngleωAngleω
O4-Cd1-O6138.27(11)O4-Cd1-N1 i94.26(12)
O6-Cd1-N1 i94.80(11)O4-Cd1-O1W138.23(11)
O6-Cd1-O1W83.50(11)O1W-Cd1-N1 i79.14(12)
O4-Cd1-N3 ii95.42(12)O6-Cd1-N3 ii87.58(11)
N1 i-Cd1-N3 ii162.55(12)O1W-Cd1-N3 ii83.98(11)
O5-Cd1-O484.67(11)O5-Cd1-O653.62(10)
N1 i-Cd1-O5100.70(12)O5-Cd1-O1W137.09(10)
N3 ii-Cd1-O594.63(12)O4-Cd1-O252.62(10)
O6-Cd1-O2168.53(10)O2-Cd1-N1 i86.89(11)
O1W-Cd1-O285.69(10)O2-Cd1-N3 ii87.49(11)
O5-Cd1-O2137.20(10)
Symmetry transformation: ix, −y − 1, −z; iix + 1,y + 1,z + 1.
Table 2. Crystallographic data and structure refinement for [{CdL2(H2O)}·(H2O)3]n.
Table 2. Crystallographic data and structure refinement for [{CdL2(H2O)}·(H2O)3]n.
Empirical FormulaC16H22N4O10Cd
Formula weight542.77
Temperature/K293(2)
Crystal systemTriclinic
Space groupP-1
a8.3460(17)
b8.5186(17)
c16.727(3)
α100.90(3)
β94.89(3)
γ116.16(3)
Volume/Å31028.8(4)
Z2
ρcalcmg/mm31.752
μ/mm−11.124
S1.211
F(000)548
Index ranges–10 ≤ h ≤ 10,
–11 ≤ k ≤ 11,
–21 ≤ l ≤ 18
Reflections collected9521
Independent reflections4531 [R(int) = 0.0293]
Data/restraints/parameters4531/14/304
Goodness-of-fit on F21.212
Final R indexes [I >= 2σ (I)]R1 = 0.0381, wR2 = 0.1024
Final R indexes [all data]R1 = 0.0442, wR2 = 0.1055
Largest diff. peak/hole/e·Å−31.460/−0.598

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MDPI and ACS Style

Tai, X.-S.; Wang, X.; Li, P.-F. Synthesis, Crystal Structure, and Luminescent Property of a Cd(II) Coordination Polymer with a N-Nicotinoylglycine Ligand. Crystals 2017, 7, 33. https://doi.org/10.3390/cryst7020033

AMA Style

Tai X-S, Wang X, Li P-F. Synthesis, Crystal Structure, and Luminescent Property of a Cd(II) Coordination Polymer with a N-Nicotinoylglycine Ligand. Crystals. 2017; 7(2):33. https://doi.org/10.3390/cryst7020033

Chicago/Turabian Style

Tai, Xi-Shi, Xin Wang, and Peng-Fei Li. 2017. "Synthesis, Crystal Structure, and Luminescent Property of a Cd(II) Coordination Polymer with a N-Nicotinoylglycine Ligand" Crystals 7, no. 2: 33. https://doi.org/10.3390/cryst7020033

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