Ferro- and Antiferromagnetic Interactions in Oxalato-Centered Inverse Hexanuclear and Chain Copper(II) Complexes with Pyrazole Derivatives
Abstract
:1. Introduction
2. Experimental
2.1. Materials
2.2. Preparations of the Complexes
2.2.1. {[Cu(4-Hmpz)4][Cu(4-Hmpz)2(µ-ox-κ2O1,O2:κO2′:κO1′)(ClO4)2]}n (1)
2.2.2. {[Cu(3,4,5-Htmpz)4]2[Cu(3,4,5-Htmpz)2(µ3-ox-κ2O1,O2:κO2′:κO1′)(H2O)(ClO4)]2 [Cu2(3,4,5-Htmpz)4(µ-ox-κO1,O2:κ2O2′,O1′)]}(ClO4)4·6H2O (2)
2.3. Physical Techniques
2.4. Crystallographic Data Collection and Refinement
3. Results and Discussion
3.1. Synthesis and General Characterization
3.2. Description of the Structures
3.2.1. {[Cu(4-Hmpz)4][Cu(4-Hmpz)2(µ3-ox-κ2O1,O2:κO2′:κO1′)(ClO4)2]}n (1)
3.2.2. {[Cu(3,4,5-Htmpz)4]2[Cu(3,4,5-Htmpz)2(µ3-ox-κ2O1,O2:κO2′:κO1′)(H2O)(ClO4)]2 [Cu2(3,4,5-Htmpz)4(µ-ox-κO1,O2:κ2O2′,O1′)]}(ClO4)4·6H2O (2)
3.3. Magnetic Properties
3.4. Magneto-Structural Correlations
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
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Compound | 1 | 2 |
---|---|---|
CCDC number | 2076622 | 2076621 |
Formula | C26H36Cl2Cu2N12O12 | C102H176Cl6Cu6N32O44 |
Fw | 906.65 | 3148.68 |
Crystal system | Monoclinic | Monoclinic |
Space group | C2/c | P21/c |
a/Ǻ | 12.3020(3) | 15.3910(14) |
b/Ǻ | 23.0520(6) | 30.496(3) |
c/Ǻ | 13.6840(2) | 17.1782(17) |
α/° | 90 | 90 |
β/° | 95.1130(13) | 113.241(4) |
γ/° | 90 | 90 |
V/Ǻ3 | 3865.15(15) | 7408.6(12) |
Z | 4 | 2 |
Dc/g cm−3 | 1.558 | 1.411 |
T/K | 293(2) | 293(2) |
μ/mm−1 | 1.310 | 1.039 |
F(000) | 1856 | 3280 |
Refl. Collected | 8741 | 116,008 |
Refl. indep. [Rint] | 4430 [0.0215] | 15,028 [0.0789] |
Refl. obs. [I > 2σ(I)] | 10,171 | 10,171 |
Goodness-of-fit on F2 | 1.059 | 1.031 |
R1a [I > 2σ(I)] (all) | 0.0360 (0.0523) | 0.0489 (0.0827) |
wR2b [I > 2σ(I)] (all) | 0.0978 (0.1031) | 0.1246 (0.1432) |
Δρmax, min/e Å−3 | 0.485 and −0.433 | 0.653 and −0.566 |
Compound a | Coordination Mode | Rb/Å | R’c/Å | ∆Rd/Å | ϕe/° | ψf/° | αg/° | β/°h | ri/Å | Jj/cm−1 | Ref. |
---|---|---|---|---|---|---|---|---|---|---|---|
1 | µ3-κ2O1,O2:κO2′:κO1′ | 1.959 | 2.377 | 0.418 | 6.09 | 85.7 | 147.7 | 21.9 | 5.949 | −0.42 | This work |
2 | µ3-κ2O1,O2:κO2′:κO1 µ-κ2O1,O2:κ2O2′,O1′ | 1.948 1.994 1.994 2.016 | 2.257 2.341 | 0.309 0.347 | 13.9 5.4 | 77.5 87.8 0 | 126.5 138.1 | 19.0 17.7 | 5.418 5.703 5.224 | n.a. +0.28 −348 | This work |
4 | µ-κ2O1,O2:κO1 | 1.950 | 2.416 | 0.466 | 5.8 | 81.5 | 177.0 | 20.2 | 6.300 | −0.74 | [59] |
5a | µ-κ2O1,O2:κ2O2′,O1′ | 1.976 | 2.122 | 0.146 | 114.9 | 2.0 | −129 | [50] | |||
5b | µ-κ2O1,O2:κ2O2′,O1′ | 1.973 | 2.110 | 0.137 | 114.4 | 2.5 | −161 | [50] | |||
6 | µ4-κO1:κ2O1,O2:κO2′:κ2O2′,O1′ | 1.959 | 2.340 | 0.381 | 86.0 | 0 | 126.4 | 19.3 | 4.237 5.553 | 0 0 | [59] |
µ-κ2O1,O2:κ2O2′,O1′ | 1.984 1.985 | 2.8 | 0 | 5.176 | −312 |
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Castro, I.; Calatayud, M.L.; Orts-Arroyo, M.; Moliner, N.; Marino, N.; Lloret, F.; Ruiz-García, R.; Munno, G.D.; Julve, M. Ferro- and Antiferromagnetic Interactions in Oxalato-Centered Inverse Hexanuclear and Chain Copper(II) Complexes with Pyrazole Derivatives. Molecules 2021, 26, 2792. https://doi.org/10.3390/molecules26092792
Castro I, Calatayud ML, Orts-Arroyo M, Moliner N, Marino N, Lloret F, Ruiz-García R, Munno GD, Julve M. Ferro- and Antiferromagnetic Interactions in Oxalato-Centered Inverse Hexanuclear and Chain Copper(II) Complexes with Pyrazole Derivatives. Molecules. 2021; 26(9):2792. https://doi.org/10.3390/molecules26092792
Chicago/Turabian StyleCastro, Isabel, M. Luisa Calatayud, Marta Orts-Arroyo, Nicolás Moliner, Nadia Marino, Francesc Lloret, Rafael Ruiz-García, Giovanni De Munno, and Miguel Julve. 2021. "Ferro- and Antiferromagnetic Interactions in Oxalato-Centered Inverse Hexanuclear and Chain Copper(II) Complexes with Pyrazole Derivatives" Molecules 26, no. 9: 2792. https://doi.org/10.3390/molecules26092792