Interplay of Isomorphs and Polymorphs of Amidino-Copper(II) Complexes with Different Halides
Abstract
:1. Introduction
2. Materials and Methods
2.1. General
2.2. Synthesis of Pyrimidine-2-Carboximidamide Salt [2]+[O2C2F3]−
2.3. Synthesis of Pyrazine-2-Carboximidamide Salt [3]+[O2C2F3]−
2.4. Synthesis of Complex 4
2.5. Synthesis of Complex 5
2.6. Synthesis of Complex 6
2.7. Synthesis of Complex 7
2.8. Synthesis of Complex 8
2.9. Synthesis of 9
2.10. X-ray Structure Analysis
3. Results and Discussion
3.1. Crystal Structure of Ligand
3.2. Crystal Structure of Complexes
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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4 | 5 | 6 | 7 | 8 | 9 | |
---|---|---|---|---|---|---|
Formula | C5H6Cl2CuN4 | C5H6Br2CuN4 | C5H6Cl2CuN4 | C5H6Br2CuN4 | C12H14Cl4Cu2N6 | C10H12Cl4Cu2N8 |
Formula weight | 256.58 | 345.484 | 256.58 | 345.50 | 255.59 | 256.581 |
Temperature/K | 100 | 100 | 100 | 100 | 100 | 100 |
Crystal system | Orthorhombic | Orthorhombic | Orthorhombic | Orthorhombic | Monoclinic | Monoclinic |
Space group, Z | Pnma, 4 | Pnma, 4 | Pnma, 4 | Pnma, 4 | P21/n, 4 | P21/n, 4 |
a/Å | 8.710 (6) | 8.924 (2) | 8.6664 (2) | 8.98 (5) | 8.3731 (4) | 8.4622 (12) |
b/Å | 6.292 (5) | 6.3937 (16) | 6.2964 (2) | 6.43 (3) | 10.9315 (6) | 10.6392 (14) |
c/Å | 15.260 (11) | 15.626 (4) | 14.8940 (4) | 15.22 (14) | 9.5637 (3) | 9.6678 (13) |
α/° | 90 | 90 | 90 | 90 | 90 | 90 |
β/° | 90 | 90 | 90 | 90 | 103.022 (4) | 99.036 (5) |
γ/° | 90 | 90 | 90 | 90 | 90 | 90 |
Volume/Å3 | 836.4 (11) | 891.5 (4) | 812.72 (4) | 879 (11) | 852.86 (7) | 859.6 (2) |
ρcalcg/cm3 | 2.038 | 2.574 | 2.097 | 2.610 | 1.991 | 1.983 |
μ/mm−1 | 3.193 | 11.359 | 9.398 | 13.745 | 3.127 | 3.106 |
F(000) | 508.0 | 652.1 | 508.0 | 652.0 | 508.0 | 508.0 |
Crystal size/mm3 | 0.3 × 0.09 × 0.04 | 0.4 × 0.15 × 0.05 | 0.06 × 0.03 × 0.01 | 0.05 × 0.02 × 0.01 | 0.5 × 0.25 × 0.15 | 0.4 × 0.15 × 0.15 |
Radiation | Mo Kα (λ = 0.71073) | Mo Kα (λ = 0.71073) | Cu Kα (λ = 1.54184) | Cu Kα (λ = 1.54184) | Mo Kα (λ = 0.71073) | Mo Kα (λ = 0.71073) |
Reflections Collected | 17,318 | 11,741 | 7265 | 4587 | 7902 | 16,659 |
Independent Reflections | 1376 | 1167 | 817 | 954 | 2956 | 2610 |
Rint | 0.0488 | 0.0522 | 0.0455 | 0.0296 | 0.0463 | 0.0327 |
Data/parameters | 1376/73 | 1167/82 | 817/75 | 954/76 | 2956/121 | 2610/121 |
Goodness-of-fit on F2 | 1.344 | 1.073 | 1.103 | 1.049 | 1.050 | 1.017 |
R1 [I ≥ 2σ (I)] | 0.0697 | 0.0328 | 0.0604 | 0.0574 | 0.0420 | 0.0269 |
wR2 [I ≥ 2σ (I)] | 0.1601 | 0.0811 | 0.1548 | 0.1527 | 0.0889 | 0.0674 |
R1 [all data] | 0.0767 | 0.0440 | 0.0658 | 0.0602 | 0.0560 | 0.0343 |
Complexes | ||||||
---|---|---|---|---|---|---|
Bond, Å | 4 | 5 | 6 | 7 | 8 | 9 |
Cu1-N1 | 2.058 (7) | 2.062 (4) | 1.950 (5) | 2.071 (15) | 2.045 (2) | 2.0607 (15) |
Cu1-N2 | 1.973 (7) | 1.951 (5) | 2.050 (6) | 1.958 (12) | 1.949 (2) | 1.9504 (15) |
Cu1-Hal2 | 2.283 (3) | 2.4307 (10) | 2.2570 (2) | 2.403 (17) | 2.2745 (7) | 2.2520 (6) |
Cu1-Hal1 | 2.249 (3) | 2.3874 (9) | 2.2578 (18) | 2.396 (12) | 2.2747 (7) | 2.2540 (5) |
Cu1-Hal3 | 2.7360 (7) | 2.854 (6) | ||||
Angle, degr. | ||||||
N1-Cu1-N4 | 80.62 (3) | 80.44 (19) | 79.9 (2) | 79.2 (6) | 80.14 (9) | 79.99 (6) |
N1-Cu1-Hal1 | 92.84 (2) | 93.99 (13) | 93.28 (16) | 94.4 (6) | 94.83 (6) | 93.85 (4) |
N4-Cu1-Hal2 | 91.70 (2) | 91.47 (14) | 92.87 (17) | 93.2 (6) | 90.90 (7) | 91.10 (5) |
Hal1-Cu1-Hal2 | 94.84 (11) | 94.10 (4) | 93.94 (7) | 93.2 (6) | 92.61 (3) | 94.23 (19) |
Hal1-Cu1-Hal3 | 91.86 (2) | 92.987 (18) | ||||
Hal2-Cu1-Hal3 | 101.08 (3) | 106.225 (18) | ||||
N1-Cu1-Hal3 | 92.85 (6) | 84.73 (4) | ||||
N2-Cu1-Hal3 | 94.15 (7) | 90.09 (5) |
Contact, Å | Structure | |||
---|---|---|---|---|
In Layer | 4/Cl | 5/Br | 6/Cl | 7/Br |
Hal1…H3 (B) | 2.612 (3) | 2.629 (5) | 2.459 (13) | 2.589 (8) |
Hal1…H4A | - | - | 2.501 (16) | Disordered H |
Hal2…H2 | 2.537 (3) | 2.561 (6) | 2.517 (15) | 2.580 (5) |
Hal2…H4B(A) | 2.615 (3) | 2.615 (6) | 2.560 (15) | Disordered H |
Between Layers | ||||
Cu…Hal * | 3.174 (3) | 3.210 (8) | 3.167 (3) | 3.223 (14) |
Complex | Ligands | Temperature, °C |
---|---|---|
4 | 2, Cl | 266 |
5 | 2, Br | 263 |
6 | 3, Cl | 199.5 |
7 | 3, Br | 238 |
8 | 1, Cl | 362 |
9 | 2, Cl | 226 |
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Yamba, Z.; Peoble, A.; Novikov, E.M.; Castañeda, R.; Timofeeva, T.V. Interplay of Isomorphs and Polymorphs of Amidino-Copper(II) Complexes with Different Halides. Crystals 2024, 14, 319. https://doi.org/10.3390/cryst14040319
Yamba Z, Peoble A, Novikov EM, Castañeda R, Timofeeva TV. Interplay of Isomorphs and Polymorphs of Amidino-Copper(II) Complexes with Different Halides. Crystals. 2024; 14(4):319. https://doi.org/10.3390/cryst14040319
Chicago/Turabian StyleYamba, Zaina, Anna Peoble, Egor M. Novikov, Raúl Castañeda, and Tatiana V. Timofeeva. 2024. "Interplay of Isomorphs and Polymorphs of Amidino-Copper(II) Complexes with Different Halides" Crystals 14, no. 4: 319. https://doi.org/10.3390/cryst14040319
APA StyleYamba, Z., Peoble, A., Novikov, E. M., Castañeda, R., & Timofeeva, T. V. (2024). Interplay of Isomorphs and Polymorphs of Amidino-Copper(II) Complexes with Different Halides. Crystals, 14(4), 319. https://doi.org/10.3390/cryst14040319