CuII Complexes and Coordination Polymers with Pyridine or Pyrazine Amides and Amino Benzamides—Structures and EPR Patterns
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis of the Cu Complexes
2.2. Crystal Structures from Single Crystal XRD
2.3. X-Band EPR Spectroscopy and Magnetic Measurements
2.4. Absorption Spectroscopy in the Solid and in Solution
3. Experimental Section
3.1. Methods and Instrumentation
3.2. Single Crystal Structure Determination
3.3. Powder X-ray Diffraction (PXRD)
3.4. Syntheses
3.4.1. General
3.4.2. Synthesis of the CuII Compounds—General Method
3.4.3. Further Syntheses
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Ligand | CuII Precursor | Compound | Formula (Weight) | Space Group |
---|---|---|---|---|
Ina | Cu(BF4)2∙6H2O | [Cu(Ina)4(H2O)2](BF4)2 (1) | C24H28B2Cu1F8N8O6 (761.69) | C2/c (No. 15) d |
Ina | Cu(NO3)2∙3H2O | [Cu(Ina)2(NO3)2] (2) | C12H12Cu1N6O8 (431.81) | P212121 (No. 19) |
Ina | Cu(NO3)2∙3H2O | [Cu(Ina)2(H2O)2(NO3)2] (3) | C12H16Cu1N6O10 (467.84) | P21/c (No. 14) e |
Ina | Cu(BF4)2∙6H2O | [Cu(Ina)2(H2O)3(SiF6)]·H2O (4) | C12H20Cu1F6N4O6Si1 (521.94) | P-1 (No. 2) |
Ina | [Cu(Ina)2(NO3)2] | [Cu(Ina)2Br2] (5) | C12H12Br2Cu1N4O2 (467.61) | P21 (No. 4) f |
HIna+ a | CuCl2∙2H2O | (HIna)2[CuCl4]∙2H2O (6) | C12H18Cl4CuN4O4 (487.64) | P-1 (No. 2) |
HIna+ a | CuCl2∙2H2O | (HIna)[Cu(H2O)Cl3] (7) | C6H9Cl3Cu1N2O2 (311.05) | P-1 (No. 2) |
Pia | Cu(BF4)2∙6H2O | [Cu(Pia)2(BF4)2] (8) | C12H12B2Cu1F8N4O2 (481.41) | P-1 (No. 2) |
Pya | Cu(BF4)2∙6H2O | [Cu(Pya)2](BF4)2 (9) | C10H10B2Cu1F8N6O2 (483.38) | P21/c (No. 14) |
Pya | Cu(NO3)2∙3H2O | [Cu(Pya)2(H2O)(NO3)](NO3) (10) | C10H12Cu1N8O9 (451.80) | P-1 (No. 2) |
Pya | Cu(NO3)2∙3H2O | [Cu(Pya)(NO3)2] (11) | C5H5Cu1N5O7 (310.67) | C2/c (No. 15) |
Pyc− b | Cu(Tfa)2∙H2O | [Cu(Pyc)(Tfa)] (12) | C7H3Cu1F3N2O4 (299.65) | P212121 (No. 19) |
2-Aba | Cu(NO3)2∙3H2O | [Cu(2-Aba)2(NO3)2] (13) | C14H16Cu1N6O8 (459.86) | P21/n (No. 14) g |
4-Aba | Cu(NO3)2∙3H2O | [Cu2(4-Aba)2(H2O)3(NO3)3](NO3) (14) | C14H22Cu2N8O17 (701.46) | C2/c (No. 15) h |
4-Aba | Cu(ClO4)2∙6H2O | [Cu(4-Aba)2(EtOH)2](ClO4)2 (15) | C18H28Cl2Cu1N4O12 (626.88) | P21/c (No. 14) |
4-Aba | Cu(BF4)2∙6H2O | [Cu(4-Aba)2(EtOH)2](BF4)2 (16) | C18H28B2Cu1F8N4O4 (601.60) | P21/c (No. 14) |
4-HAba+ c | Cu(ClO4)2∙6H2O + HCl | [Cu(4-HAba)2Cl4] (17) | C14H18Cl4Cu1N4O2 (479.67) | P21/c (No. 14) |
Tba | Cu(ClO4)2∙6H2O | [Cu(Tba)2](ClO4)2 (18) | C8H16Cl2Cu1N4O12S2 (558.80) | C2/m (No. 12) |
Complex | Geometry a | T (K) | Cu–L1 b | Cu–L2 | Cu–L3 | Cu–L4 | Cu–L5 | Cu–L6 |
---|---|---|---|---|---|---|---|---|
L1–Cu–L2 | L2–Cu–L3 | L3–Cu–L4 | L1–Cu–L5 | L1–Cu–L6 | L1–Cu–L3 | L5–Cu–L6 | ||
[Cu(Ina)4(H2O)2](BF4)2 (1) | OE | 298(2) | 2.024(3) N21 | 2.045(4) N11 | =N11 | =N21 | 2.392(5) O1 | 2.645(5) O2 |
91.7(1)° | 88.9(2)° | 91.7(1)° | 86.5(1)° | 93.4(1)° | 173.0(1)° | 180° | ||
[Cu(Ina)2(NO3)2] (2) | SPy+1 | 298(2) | 1.987(5) O31 | 1.994(5) N21 | 2.002(5) N11 | 2.004(4) O41 | 2.314(4) O11 | - |
90.1(2)° | 87.7(2)° | 89.1(2)° | 78.9(2)° | - | 165.5(2)° | - | ||
[Cu(Ina)2(H2O)2(NO3)2] (3) c | OE | 296(2) | 1.984(1) O2 | 1.992(1) N1 | 2.507(1) O3 | |||
90.0(1)° | 90.0(1)° | 95.6(1)° | 84.4(1)° | 180° | 180° | |||
[Cu(Ina)2(H2O)3(SiF6)]·H2O (4) | OE | 298(2) | 1.969(2) O1 | 1.986(2) O2 | 1.999(2) N21 | 2.026(2) N11 | 2.409(2) F1 | 2.513(2) O4 |
90.1(1)° | 89.6(1)° | 88.2(1)° | 88.2(1)° | 84.9(1)° | 180° | 170.9(1)° | ||
(HIna)2[CuCl4]∙2H2O (6) | SP+2 | 298(2) | 2.263(1) Cl1 | 2.270(1) Cl2 | =Cl1 | =Cl2 | 3.360(1) = (py) | =L5 |
(HIna)[Cu(H2O)Cl3] (7) c | SPy | 298(2) | 1.980(4) O1 | 2.251(1) Cl2 | 2.268(1) Cl1 | 2.279(1) Cl3 | 2.923(1) Cl2′ | - |
87.4(1)° | 93.2(1)° | 92.6(1)° | - | - | 172.5(1)° | - | ||
[Cu(Pia)2(BF4)2] (8) | OE | 150(2) | 1.935(3) O1 | 1.958(4) N1 | =O1 | =N1 | 2.589(3) F4 | =F4 |
83.3(2)° | 96.6(1)° | 83 (2)° | 89.7(1)° | 90.3(1)° | 180° | 180° | ||
[Cu(Pya)2](BF4)2 (9) | OE | 298(2) | 1.957(2) O11 | 1.984(3) N12 | =O11 | =N12 | 2.447(3) N11 | =N11 |
82.2(1)° | 97.7(1)° | 82.2(1)° | 85.5(1)° | 94.4(1)° | 180° | 180° | ||
[Cu(Pya)2(H2O)(NO3)](NO3) (10) | Spy+1 | 298(2) | 1.935(4) O11 | 1.938(4) O21 | 1.984(4) N21 | 1.989(4) N11 | 2.234(4) O5 | 2.818(4) O43 |
82.7(1)° | 97.6(1)° | 82.7(1)° | 94.3(2)° | 89.7(1)° | 172.1(1)° | 169.8(1)° | ||
[Cu(Pya)(NO3)2] (11) | SPy | 298(2) | 1.953(2) O11 | 1.979(2) O31 | 1.998(2) N12 | 2.004(2) N11 | 2.238(2) O21 | 2.572(3) O33 |
81.6(1)° | 89.3(1)° | 92.3(1)° | 91.0(1)° | 93.6(1)° | 169.2(1)° | 136.9(1)° | ||
[Cu(Pyc)(Tfa)] (12) d | SPy | 298(2) | 1.942(5) O1 | 1.944(7) O11 | 1.997(6) O12 | 2.065(8) N11 | 2.272(8) N12 | - |
88.8(2)° | 97.6(2)° | 92.7(3)° | 96.5(3)° | - | 171.3(2)° | - | ||
[Cu(2-Aba)2(NO3)2] (13) | OE | 298(2) | 1.976(3) O1 | 2.010(4) N1 | =O1 | =N1 | 2.506(5) O3 | =O3 |
87.3(2)° | 92.7(2)° | 87.3(2)° | 92.8(1)° | 87.1(1)° | 180° | 180° | ||
[Cu2(4-Aba)2(H2O)3(NO3)3](NO3) (14) e | OD | 298(2) | 1.942(4) O11 | 1.969(4) O21 | 2.016(4) N11 | 2.034(5) O21 | 2.262(4) O32 | 2.35(1) O23 |
89.1(2)° | 88.2(2)° | 93.3(2)° | 82.9(2)° | 95.2(3)° | 176.0(2)° | 143.1(3)° | ||
[Cu(4-Aba)2(EtOH)2](ClO4)2 (15) | OE | 150(2) | 1.951(2) O11 | 2.077(4) N11 | =N11 | =O11 | 2.529(2) O21 | =O21 |
87.8(1)° | 92.1(1)° | 87.8(1)° | 94.4(1)° | 85.5(1)° | 180° | 180° | ||
[Cu(4-Aba)2(EtOH)2](BF4)2 (16) | OE | 298(2) | 1.951(2) O11 | 2.062(3) N11 | =O11 | =N11 | 2.545(2) O1 | =O1 |
87.9(1)° | 92.1(1)° | 87.9(1)° | 87.3(1)° | 92.6(1)° | 180° | 180° | ||
[Cu(4-HAba)2Cl4] (17) f | OE | 298(2) | 1.957(6) O1 | 2.313(3) Cl1 | =O1 | =Cl | 2.867(2) Cl2 | =Cl2 |
89.6(2)° | 90.4(2)° | 89.6(2)° | 98.2(2)° | 81.8(2)° | 180° | 180° | ||
[Cu(Tba)2](ClO4)2 (18) | OE | 298(2) | 1.976(2) O11 | =O11 | =O11 | =O11 | 2.625(1) S11 | =S11 |
90.9(1)° | 89.1(1)° | 90.9(1)° | 81.5(1)° | 98.4(1)° | 180° | 180° |
Compound | T (K) | gav | g‖/g1 | g2 | g⊥/g3 | Δg | Spectral Geom. | CuII Geom. |
---|---|---|---|---|---|---|---|---|
Group I | ||||||||
[Cu(Ina)2(NO3)2] (2) | 298 | 2.143 | 2.280 | 2.074 | 0.206 | axial | SPy+1 | |
[Cu(Ina)4(H2O)2](BF4)2 (1) b | 298 | 2.118 | 2.260 | 2.048 | 0.212 | axial | OE | |
(HIna)2[CuCl4].2H2O (6) | 298 | 2.132 | 2.266 | 2.082 | 2.047 | 0.219 | rhombic | SP+2 |
[Cu(Ina)2(H2O)3(SiF6)]·H2O (4) | 298 | 2.154 | 2.326 | 2.068 | 0.258 | axial | OE | |
[Cu(Ina)2(H2O)2(NO3)2] (3) | 298 | 2.156 | 2.297 | 2.085 | 0.212 | axial | OE | |
[Cu(4-HAba)2Cl4] (17) | 298 | 2.175 | 2.286 | 2.169 | 2.066 | 0.219 | rhombic | OE |
[Cu(Pya)(NO3)2] (11) | 298 | 2.179 | 2.372 | 2.083 | 0.289 | axial | SPy | |
[Cu(Pya)2(H2O)(NO3)](NO3) (10) | 298 | 2.183 | 2.400 | 2.075 | 0.325 | axial | SPy+1 | |
similar compounds | ||||||||
[Cu(CCl3COO)2(MNA)2]∙2H2O c | 298 | 2.143 | 2.280 | 2.075 | 0.205 | axial | OE | |
[Cu(Ina)2(µ-N,S-SCN)2] d | 298 | 2.20 | 2.27 | 2.07 | 0.200 | axial | OE | |
[Cu(meclof)2(2-pyca)2] e | 298 | 2.142 | 2.290 | 2.068 | 0.222 | axial | OE | |
[Cu(clof)2(4-pymeth)2(H2O)] 2H2O f | 298 | 2.128 | 2.271 | 2.054 | 0.217 | axial | SPy | |
[Cu(clof)2(Et2nia)2] f | 298 | 2.132 | 2.289 | 2.053 | 0.236 | axial | g | |
[Cu(clof)2(Ina)2] f | 298 | 2.153 | 2.285 | 2.087 | 0.198 | axial | g | |
[Cu(tolf)2(Et2nia)2)(H2O)2] h | 298 | 2.130 | 2.294 | 2.048 | 0.246 | axial | OE | |
[Cu(tolf)2(Nia)2] h | 298 | 2.157 | 2.319 | 2.076 | 0.243 | axial | g | |
Group II | ||||||||
[Cu(Pya)2](BF4)2 (9) | 298 | 2.140 | 2.204 | 2.139 | 2.078 | 0.126 | rhombic | OE |
[Cu(4-Aba)2(EtOH)2](ClO4)2 (15) | 110 | 2.137 | 2.231 | 2.123 | 2.059 | 0.172 | rhombic | OE |
[Cu(4-Aba)2(EtOH)2](ClO4)2 (15) | 298 | 2.111 | 2.200 | 2.066 | 0.133 | axial | OE | |
[Cu(4-Aba)2(EtOH)2](BF4)2 (16) | 110 | 2.139 | 2.220 | 2.140 | 2.058 | 0.162 | rhombic | OE |
[Cu(4-Aba)2(EtOH)2](BF4)2 (16) | 298 | 2.110 | 2.196 | 2.068 | 0.131 | axial | OE | |
[Cu(TBA)2](ClO4)2 (18) | 298 | 2.130 | 2.228 | 2.080 | 0.147 | axial | OE | |
similar compounds | ||||||||
[Cu2(Ina)2(µ-1,1-N3)2(µ-1,3-N3)2] d | 298 | 2.17 | 2.22 | 2.07 | 0.150 | axial | SPy+1 | |
[Cu(Ina)2(µ-1,1-N3)2(µ-O,O-SO4)]∙2H2O d | 298 | 2.17 | 2.24 | 2.18 | 2.09 | 0.150 | rhombic | SPy |
Group III | ||||||||
[Cu(Pyc)(Tfa)] (12) | 298 | 2.138 | 2.138 | 0 | isotropic | SPy | ||
[Cu(Ina)2Br2] (5) | 298 | 2.111 | 2.111 | 0 | isotropic | SPy i | ||
Group IV | ||||||||
[Cu2(Aba)2(H2O)3(NO3)3](NO3) (14) | 298 | 2.141 | 2.190 | 2.050 | 0.112 | inv. axial | OD |
Compound | μB | θCW (K) | EPR Symmetry | Symmetry Around CuII |
---|---|---|---|---|
[Cu(Ina)2(NO3)2] (2) | 1.50 | 36.9 | axial | SPy + 1 |
[Cu(Pya)(NO3)2] (11) | 1.65 | 6.55 | isotropic | SPy |
[Cu(Pyc)(Tfa)] (12) | 1.56 | 48.3 | isotropic | SPy |
[Cu(Aba)2(EtOH)2](ClO4)2 (15) | 1.52 | 42.8 | axial | OE |
Compound | λ (nm/cm−1) of d-d Bands | Colour of the Crystals | Symmetry Around CuII b |
---|---|---|---|
[Cu(Pya)2](BF4)2 (9) | 613/16,310 | blue | OE |
[Cu(Pya)2(H2O)(NO3)](NO3) (10) | 640/15,630 | blue | SPy + 1 |
[Cu(Pya)(NO3)2] (11) | 780/12,820 | blue | SPy |
[Cu(Pyc)(Tfa)] (12) | 664/15,060 | turquoise | SPy |
[Cu(Ina)2Br2] (5) | 691/14,470 | dark green | - b |
similar compounds | |||
[Cu(tolf)2(Et2nia)2)(H2O)2] c | 614/16,290 | blue | OE |
[Cu(meclof)2(2-pyca)2] d | 615/16,260 | blue | OE |
[Cu(meclof)2(Et2nia)2] d | 605/16,530 | blue | - e |
[Cu(clof)2(4-pymeth)2(H2O)] 2H2O f | 620/16,130 | blue | SPy |
[Cu(clof)2(Ina)2] f | 660/15,150 | blue | - e |
[Cu(clof)2(Et2nia)2] f | 603/16,580 | violet | - e |
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Wackerbarth, I.; Widhyadnyani, N.N.A.T.; Schmitz, S.; Stirnat, K.; Butsch, K.; Pantenburg, I.; Meyer, G.; Klein, A. CuII Complexes and Coordination Polymers with Pyridine or Pyrazine Amides and Amino Benzamides—Structures and EPR Patterns. Inorganics 2020, 8, 65. https://doi.org/10.3390/inorganics8120065
Wackerbarth I, Widhyadnyani NNAT, Schmitz S, Stirnat K, Butsch K, Pantenburg I, Meyer G, Klein A. CuII Complexes and Coordination Polymers with Pyridine or Pyrazine Amides and Amino Benzamides—Structures and EPR Patterns. Inorganics. 2020; 8(12):65. https://doi.org/10.3390/inorganics8120065
Chicago/Turabian StyleWackerbarth, Ines, Ni Nyoman Agnes Tri Widhyadnyani, Simon Schmitz, Kathrin Stirnat, Katharina Butsch, Ingo Pantenburg, Gerd Meyer, and Axel Klein. 2020. "CuII Complexes and Coordination Polymers with Pyridine or Pyrazine Amides and Amino Benzamides—Structures and EPR Patterns" Inorganics 8, no. 12: 65. https://doi.org/10.3390/inorganics8120065