Synthesis and Switchable Dielectric Properties of an Inorganic-organic Hybrid Complex [H2(DABCO)CuCl4]·H2O †

doi:10.7503/cjcu20190310

Abstract

Abstract:

A novel inorganic-organic hybrid complex, [H₂(DABCO)CuCl₄]·H₂O(1), was successfully synthesized via the reaction of 1,4-diazabicyclo[2.2.2]octane, copper(Ⅱ) chloride dihydrate and hydrochloric acid. The complex was characterized by single-crystal X-ray diffraction, IR spectra, powder X-ray diffraction analysis, thermogravimetric analysis and variable-temperature dielectric measurement. Single crystal XRD analysis reveals that compound 1 belongs to monoclinic space group P2₁/c at low temperature and room temperature, and the unit cell parameters a, b, c, and V change significantly from low temperature to room temperature for the same structure phase transition. The single crystal structure shows that a two-dimensional network is formed in the bc plane through N—H…O and O—H…Cl hydrogen bonding interactions. The relative displacement of copper ions along the c-axis leads to switchable dielectric abnormal peaks and temperature dependence of its dielectric permittivity displays remarkable dielectric anisotropy along different crystal axes.

Key words: Crystal structure, Hydrogen bond, Inorganic-organic hybrid complex, Dielectric anisotropy

CLC Number:

O614.12

TrendMD:

QIN Liulei,LIU Yang,GUAN Xiaoqin,ZHENG Xiaoyuan,ZHANG Ziyu,LIU Zunqi. Synthesis and Switchable Dielectric Properties of an Inorganic-organic Hybrid Complex [H₂(DABCO)CuCl₄]·H₂O ^†[J]. Chem. J. Chinese Universities, 2020, 41(1): 70.

Figures/Tables 13

References 31

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Temperature	100 K	294 K
Chemical formula	C₆H₁₆Cl₄CuN₂O	C₆H₁₆Cl₄CuN₂O
Formula weight	336.18	336.18
Crystal size	0.13 mm×0.12 mm×0.11 mm	0.13 mm×0.12 mm×0.11 mm
Crystal system	Monoclinic	Monoclinic
Space group	P2₁/c	P2₁/c
a/nm	0.91929(2)	0.93180(11)
b/nm	0.93404(3)	0.94267(13)
c/nm	1.42687(3)	1.44795(19)
α/(°)	90.00	90.00
β/(°)	93.568(2)	93.379(11)
γ/(°)	90.00	90.00
V/nm³	1.22281(5)	1.2696(3)
Z	4	4
D_c/(g·cm^-3)	1.834	1.766
F(000)	684	684
μ/mm^-1	2.631	2.534
Reflections collected	11298	16181
Independent reflections	6549	6379
Measured 2θ range/(°)	1.000—24.992	0.885—25.242
R_int	0.0240	0.0339
R[I>2σ(I)]^a	0.0262	0.0451
wR(all data)^b	0.0592	0.0829
GOF	1.068	1.047

Temperature	100 K	294 K
Chemical formula	C₆H₁₆Cl₄CuN₂O	C₆H₁₆Cl₄CuN₂O
Formula weight	336.18	336.18
Crystal size	0.13 mm×0.12 mm×0.11 mm	0.13 mm×0.12 mm×0.11 mm
Crystal system	Monoclinic	Monoclinic
Space group	P2₁/c	P2₁/c
a/nm	0.91929(2)	0.93180(11)
b/nm	0.93404(3)	0.94267(13)
c/nm	1.42687(3)	1.44795(19)
α/(°)	90.00	90.00
β/(°)	93.568(2)	93.379(11)
γ/(°)	90.00	90.00
V/nm³	1.22281(5)	1.2696(3)
Z	4	4
D_c/(g·cm^-3)	1.834	1.766
F(000)	684	684
μ/mm^-1	2.631	2.534
Reflections collected	11298	16181
Independent reflections	6549	6379
Measured 2θ range/(°)	1.000—24.992	0.885—25.242
R_int	0.0240	0.0339
R[I>2σ(I)]^a	0.0262	0.0451
wR(all data)^b	0.0592	0.0829
GOF	1.068	1.047

Cu1—Cl1	0.22855(6)	Cu1—Cl4	0.22417(6)	Cu1—Cl2	0.22476(6)
Cu1—Cl3	0.22313(6)	N2—C2	0.14810(3)	N2—C4	0.14870(3)
N2—C6	0.14800(3)	N1—C1	0.15010(3)	N1—C3	0.15000(3)
N1—C5	0.15030(3)	C1—C2	0.15260(3)	C3—C4	0.15140(4)
C5—C6	0.15110(3)
Cl4—Cu1—Cl1	131.98(2)	Cl4—Cu1—Cl2	98.96(2)	Cl2—Cu1—Cl1	95.38(2)
Cl3—Cu1—Cl1	101.13(2)	Cl3—Cu1—Cl4	99.45(2)	Cl3—Cu1—Cl2	136.09(3)
C2—N2—C4	109.50(2)	C6—N2—C2	110.10(2)	C6—N2—C4	109.90(2)
C1—N1—C3	110.93(18)	C1—N1—C5	109.66(17)	C3—N1—C5	109.23(17)
N1—C1—C2	108.09(18)	N1—C3—C4	108.48(19)	N1—C5—C6	108.12(19)
N2—C2—C1	109.60(2)	N2—4—C3	109.50(2)	N2—C6—C5	110.13(19)

Cu1—Cl1	0.22855(6)	Cu1—Cl4	0.22417(6)	Cu1—Cl2	0.22476(6)
Cu1—Cl3	0.22313(6)	N2—C2	0.14810(3)	N2—C4	0.14870(3)
N2—C6	0.14800(3)	N1—C1	0.15010(3)	N1—C3	0.15000(3)
N1—C5	0.15030(3)	C1—C2	0.15260(3)	C3—C4	0.15140(4)
C5—C6	0.15110(3)
Cl4—Cu1—Cl1	131.98(2)	Cl4—Cu1—Cl2	98.96(2)	Cl2—Cu1—Cl1	95.38(2)
Cl3—Cu1—Cl1	101.13(2)	Cl3—Cu1—Cl4	99.45(2)	Cl3—Cu1—Cl2	136.09(3)
C2—N2—C4	109.50(2)	C6—N2—C2	110.10(2)	C6—N2—C4	109.90(2)
C1—N1—C3	110.93(18)	C1—N1—C5	109.66(17)	C3—N1—C5	109.23(17)
N1—C1—C2	108.09(18)	N1—C3—C4	108.48(19)	N1—C5—C6	108.12(19)
N2—C2—C1	109.60(2)	N2—4—C3	109.50(2)	N2—C6—C5	110.13(19)

Cu1—Cl1	0.22942(7)	Cu1—Cl4	0.22497(7)	Cu1—Cl2	0.22573(7)
Cu1—Cl3	0.22389(7)	N2—C2	0.14870(3)	N2—C4	0.14820(3)
N2—C6	0.14900(3)	N1—C1	0.15100(3)	N1—C3	0.14980(3)
N1—C5	0.14990(3)	C1—C2	0.15230(4)	C3—C4	0.15090(4)
C5—C6	0.15120(4)
Cl4—Cu1—Cl1	131.65(3)	Cl4—Cu1—Cl2	99.17(3)	Cl2—Cu1—Cl1	95.45(3)
Cl3—Cu1—Cl1	100.93(3)	Cl3—Cu1—Cl4	99.71(3)	Cl3—Cu1—Cl2	135.94(3)
C2—N2—C6	109.60(2)	C4—N2—C2	109.80(2)	C4—N2—C6	110.00(2)
C5—N1—C1	110.60(19)	C3—N1—C1	109.92(19)	C3—N1—C5	109.34(19)
N1—C1—C2	108.15(19)	N1—C5—C6	108.40(2)	N1—C3—C4	108.60(2)
N2—C2—C1	109.50(2)	N2—C4—C3	109.90(2)	N2—C6—C5	109.90(2)

Synthesis and Switchable Dielectric Properties of an Inorganic-organic Hybrid Complex [H₂(DABCO)CuCl₄]·H₂O ^†

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Figures/Tables 13

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D—H…A	d(D—H)/nm	d(H…A)/nm	d(D…A) /nm	∠D—H…A/(°)
N1—H1…Cl1^j	0.0980	0.2372	0.3188	140.21
N1—H1…Cl2ⁱ	0.0980	0.2746	0.3398	124.43
N2—H2…O1^k	0.0980	0.2146	0.2902	133.82
O1—H1D…Cl1ⁱ	0.0850	0.2313	0.3152	168.94
O1—H1C…Cl2^j	0.0850	0.2487	0.3287	158.42
O1—H1C…Cl4ⁱ	0.0850	0.2797	0.3311	120.54
O1—H1C…O1ⁱ	0.0850	0.3460	0.3020	52.59

D—H…A	d(D—H)/nm	d(H…A)/nm	d(D…A) /nm	∠D—H…A/(°)
N1—H1…Cl1^j	0.0980	0.2411	0.3229	140.72
N1—H1…Cl2ⁱ	0.0980	0.2774	0.3440	125.79
N2—H2…O1^k	0.0980	0.2194	0.2954	134.63
O1—H1D…Cl1ⁱ	0.0850	0.2347	0.3187	169.78
O1—H1C…Cl2^j	0.0850	0.2538	0.3337	156.90
O1—H1C…Cl4 ⁱ	0.0850	0.2825	0.3362	122.79
O1—H1C…O1ⁱ	0.0850	0.3481	0.3053	53.53

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