Synthesis, Crystal Structure, Spectroscopic Characterization, DFT Calculations and Cytotoxicity Assays of a New Cu(II) Complex with an Acylhydrazone Ligand Derived from Thiophene
Abstract
:1. Introduction
2. Results and Discussion
2.1. Syntheses
2.2. Crystal Structure
2.3. Vibrational Spectroscopy
2.4. EPR Spectroscopy
2.5. Electronic Spectroscopy
2.6. Cell Viability Study
2.7. Antioxidant Activity
3. Materials and Methods
3.1. Synthesis
3.2. X-ray Diffraction Data
3.3. Spectroscopy
3.4. Computational Methods
3.5. Cell Viability Study: 3-(4,5-Dimethylthiazol-2-Yl)-2,5-Diphenyltetrazolium Bromide Assay
Cell Line and Growth Conditions
3.6. Antioxidant Activity
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Empirical formula | C13 H15 Cu N3 O8 S |
Formula weight | 436.88 |
Temperature | 293(2) K |
Wavelength | 1.54184 Å |
Crystal system | Triclinic |
Space group | P-1 |
Unit cell dimensions | |
a | 9.3380(5) Å |
b | 9.6015(5) Å |
c | 11.3991(7) Å |
α | 97.334(5)° |
β | 104.595(5)° |
ɣ | 116.924(5)° |
Volume | 846.52(8) Å3 |
Z, density (calculated) | 2, 1.714 Mg/m3 |
Absorption coefficient | 3.442 mm−1 |
F(000) | 446 |
θ-range for data collection | 4.17 to 72.41° |
Index ranges | −9 ≤ h ≤ 11, −11 ≤ k ≤ 9, −14 ≤ l ≤ 13 |
Reflections collected | 7440 |
Independent reflections | 3335 [R(int) = 0.023] |
Observed reflections [I > 2σ(I)] | 2989 |
Completeness to θ = 72.41° | 99.4% |
Refinement method | Full-matrix least-squares on F2 |
Data/restraints/parameters | 3335/6/252 |
Goodness-of-fit on F2 | 1.047 |
Final R indices [I > 2σ(I)] | R1 = 0.0449, wR2 = 0.1264 |
R indices (all data) | R1 = 0.0496, wR2 = 0.1323 |
Largest diff. peak and hole | 0.641 and −0.555 e.Å−3 |
Bond Distances (Å) | Bond Angles (°) | ||||
---|---|---|---|---|---|
Exp. | Calc. | Exp. | Calc. | ||
Cu–N1 | 1.927 | 1.957 | N1–Cu–O3 | 81.6 | 79.4 |
Cu–O1 | 1.885 | 1.915 | Cu–N1–N2 | 111.7 | 112.1 |
Cu–O1W | 1.953 | 1.990 | N1–Cu–O1 | 92.8 | 91.1 |
Cu–O3 | 1.978 | 2.094 | O1–Cu–O3 | 174.4 | 161.8 |
Cu–O31 | 2.429 | 2.257 | O1W–Cu–N1 | 167.8 | 173.0 |
O1–C1 | 1.311 | 1.285 | O1W–Cu–O1 | 92.4 | 94.5 |
N1–C7 | 1.290 | 1.297 | N1–Cu–O31 | 98.0 | 92.3 |
N1–N2 | 1.376 | 1.374 | O3–Cu–O1W | 93.1 | 94.0 |
C8–N2 | 1.342 | 1.354 | O3–Cu–O31 | 96.6 | 89.2 |
C8–O3 | 1.258 | 1.247 | O1–Cu–O31 | 84.2 | 106.9 |
O31–N3 | 1.217 | 1.272 | O1W–Cu–O31 | 93.6 | 90.2 |
C2–O2 | 1.365 | 1.353 | N3–O31–Cu | 136.4 | 127.0 |
O2–C13 | 1.420 | 1.416 | |||
N3–O32 | 1.212 | 1.275 | Dihedral Angles (°) | ||
N3–O33 | 1.217 | 1.216 | Exp. | Calc. | |
C6–C7 | 1.430 | 1.417 | O3–Cu–N1–N2 | −1.5 | −9.8 |
N1–Cu–O1–C1 | 5.8 | −10.8 | |||
O3–C8–C9–S | 4.9 | −10.2 | |||
O3–C8–N2–N1 | −1.6 | 1.4 | |||
O2–C2–C1–O1 | 0.9 | 0.0 | |||
N2–C8–C9–S | −174.0 | 170.3 |
Experimental in DMSO (ε, M−1·cm−1) | Experimental, Solid Sample | Calculated (O. S.) | Transition (a) | Assignment |
---|---|---|---|---|
743 (43) | 715 ** | 843 (0.00023) | Hβ −9→ Lβ | d → d |
657 (35) | 637 ** | 670 (0.00040) | Hβ −15 → Lβ | d → d |
423 (sh) 404 (1.2 × 104) | 411 | 581 (0.00129) 573 (0.00159) 478 (0.10700) 438 (0.00123) | Hβ −16 → Lβ Hβ −17→ Lβ Hβ → Lβ Hβ −1 → Lβ | d → d d → d LMCT LMCT |
348 (sh) | 330 | 345 (0.30163) | Hα → Lα+1 | Intraligand |
335 (1.7 × 104) | 287 (0.48728) | Hβ −5 → Lβ | LMCT | |
320 (sh) | 264 (0.10541) | Hα −5 → Lα | Intraligand | |
258 * | 246 (0.02130) | Hα −1 → Lα+1 | Intraligand |
Cell Lines | IC50 CuHL | SI CuHL | IC50 CDDP | SI CDDP |
---|---|---|---|---|
MG-63 | 2.0 ± 0.5 | 1.8 | 39 ± 1.8 | 0.3 |
HT-29 | 7.4 ± 0.9 | 0.5 | 178.8 ± 4.9 | 0.06 |
A549 | 3.1 ± 0.6 | 1.2 | 114.0 ± 2.3 | 0.1 |
L929 | 3.6 ± 0.3 | 11.2 ± 1.6 |
Compound | H2L | CuHL |
---|---|---|
TEAC | 1.33 | 0.24 |
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Rodríguez, M.R.; Balsa, L.M.; Piro, O.E.; Etcheverría, G.A.; García-Tojal, J.; Pis-Diez, R.; León, I.E.; Parajón-Costa, B.P.; González-Baró, A.C. Synthesis, Crystal Structure, Spectroscopic Characterization, DFT Calculations and Cytotoxicity Assays of a New Cu(II) Complex with an Acylhydrazone Ligand Derived from Thiophene. Inorganics 2021, 9, 9. https://doi.org/10.3390/inorganics9020009
Rodríguez MR, Balsa LM, Piro OE, Etcheverría GA, García-Tojal J, Pis-Diez R, León IE, Parajón-Costa BP, González-Baró AC. Synthesis, Crystal Structure, Spectroscopic Characterization, DFT Calculations and Cytotoxicity Assays of a New Cu(II) Complex with an Acylhydrazone Ligand Derived from Thiophene. Inorganics. 2021; 9(2):9. https://doi.org/10.3390/inorganics9020009
Chicago/Turabian StyleRodríguez, María R., Lucía M. Balsa, Oscar E. Piro, Gustavo A. Etcheverría, Javier García-Tojal, Reinaldo Pis-Diez, Ignacio E. León, Beatriz P. Parajón-Costa, and Ana C. González-Baró. 2021. "Synthesis, Crystal Structure, Spectroscopic Characterization, DFT Calculations and Cytotoxicity Assays of a New Cu(II) Complex with an Acylhydrazone Ligand Derived from Thiophene" Inorganics 9, no. 2: 9. https://doi.org/10.3390/inorganics9020009