Synthesis and Characterization of Coordination Polymers Based on 5-Azidoisophthalic Acid†

doi:10.7503/cjcu20140957

Abstract

Abstract:

Four coordination polymers, Co(aip)(py)₃(1), Co(aip)(4,4'-bipy)(2), Mn(aip)(4,4'-bipy)(3) and Mn(aip)(dptz)(4)[Py: pyridine; 4,4'-bipy: 4,4'-dipyridyl; dptz: 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine] were synthesized by the reaction of 5-azidoisophthalic acid(H₂aip) and auxiliary ligands with transition metal. The structures of the complexes were characterized by single crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, infrared spectroscopy and thermal-gravimetric analysis. The structural analyses of compound 1 show that the complex belongs to the monoclinic system, and the space group is C2/c with a 1D chain structure. Compounds 2 and 3 belong to the monoclinic system, and the space group is C2/m with 2D network structures. For compound 4, the space group is P $1 ¯$ with a 2D network. The magnetic properties were also characterized. The results reveal that anti-ferromagnetic interaction exists in compounds 1—4.

Key words: Crystal structure, Solvothermal synthesis, Coordination polymer, Magnetic property, 5-Azidoisophthalic acid ligand

CLC Number:

O614

TrendMD:

MA Benhua, PENG Yu, HUA Jia, SHI Zhan. Synthesis and Characterization of Coordination Polymers Based on 5-Azidoisophthalic Acid^†[J]. Chem. J. Chinese Universities, 2015, 36(2): 215.

Figures/Tables 4

Table 1 Crystallographic data for complexes 1—4

Compound	1	2	3	4
Empirical formula	C₂₃H₁₈CoN₆O₄	C₁₈H₁₁CoN₅O₄	C₁₈H₁₁MnN₅O₄	C₂₀H₁₁MnN₉O₄
Formula weight	501.36	420.25	416.26	496.32
Crystal system	Monoclinic	Monoclinic	Monoclinic	Triclinic
Space group	C2/c	C2/m	C2/m	P $1 ˉ$
a/nm	2.0952(12)	1.8070(4)	1.8296(4)	0.9982(2)
b/nm	1.5897(12)	1.1587(2)	1.1613(2)	1.0215(2)
c/nm	1.4735(9)	1.0182(2)	1.0196(2)	1.4518(3)
α/(°)	90	90	90	81.58(3)
β/(°)	112.21(5)	109.42(3)	109.57(3)	76.89(3)
γ/(°)	90	90	90	71.99(3)
Volume/nm³	4.5437(5)	2.0106(7)	2.0411(7)	1.3665(5)
Z	8	4	4	2
Calculated density/(g·cm^-3)	1.466	1.388	1.355	1.206
Absorption coefficient/mm^-1	0.798	0.886	0.678	0.522
F(000)	2056	852	844	502
GOF	1.021	1.113	1.093	1.067
Final R index[I>2σ(I)]	R₁=0.0372	R₁=0.0817	R₁=0.0766	R₁=0.0819
	wR₂=0.0882	wR₂=0.2422	wR₂=0.2398	wR₂=0.2676
R index(All data)	R₁=0.0844	R₁=0.0996	R₁=0.0995	R₁=0.1252
	wR₂=0.1098	wR₂=0.2564	wR₂=0.2535	wR₂=0.2938

Table 1 Crystallographic data for complexes 1—4

Compound	1	2	3	4
Empirical formula	C₂₃H₁₈CoN₆O₄	C₁₈H₁₁CoN₅O₄	C₁₈H₁₁MnN₅O₄	C₂₀H₁₁MnN₉O₄
Formula weight	501.36	420.25	416.26	496.32
Crystal system	Monoclinic	Monoclinic	Monoclinic	Triclinic
Space group	C2/c	C2/m	C2/m	P $1 ˉ$
a/nm	2.0952(12)	1.8070(4)	1.8296(4)	0.9982(2)
b/nm	1.5897(12)	1.1587(2)	1.1613(2)	1.0215(2)
c/nm	1.4735(9)	1.0182(2)	1.0196(2)	1.4518(3)
α/(°)	90	90	90	81.58(3)
β/(°)	112.21(5)	109.42(3)	109.57(3)	76.89(3)
γ/(°)	90	90	90	71.99(3)
Volume/nm³	4.5437(5)	2.0106(7)	2.0411(7)	1.3665(5)
Z	8	4	4	2
Calculated density/(g·cm^-3)	1.466	1.388	1.355	1.206
Absorption coefficient/mm^-1	0.798	0.886	0.678	0.522
F(000)	2056	852	844	502
GOF	1.021	1.113	1.093	1.067
Final R index[I>2σ(I)]	R₁=0.0372	R₁=0.0817	R₁=0.0766	R₁=0.0819
	wR₂=0.0882	wR₂=0.2422	wR₂=0.2398	wR₂=0.2676
R index(All data)	R₁=0.0844	R₁=0.0996	R₁=0.0995	R₁=0.1252
	wR₂=0.1098	wR₂=0.2564	wR₂=0.2535	wR₂=0.2938

Fig.1 Crystal structure of complex 1(A) and the view of 1D chain of complex 1(B)

Fig.2 Crystal structure of complex 2(A), view of the 1D chain structure of [Co2(aip)2]n along a and c axes(B) and the view of the 2D layer structure along a and b axes(C)

Fig.3 Temperature dependence of χm(a) and χmT(b) for complexes 1(A), 2(B), 3(C), 4(D)

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