A–X⋯σ Interactions—Halogen Bonds with σ-Electrons as the Lewis Base Centre
Abstract
:1. Introduction
2. Results and Discussions
2.1. Examples of Crystal Structures
2.2. Energies and Geometries of Complexes Linked by A–X⋯σ Interactions
2.3. C–X⋯σ and X–X⋯σ Interactions in Complexes of Dihydrogen and Cyclopropane
2.4. Energy Decomposition Analysis
3. Computational Approaches
4. Conclusions
Supplementary Materials
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
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Refcode | Max e.s.d. | A–X | X···σ | α | β |
---|---|---|---|---|---|
Dihydrogen as an electron donor | |||||
NOLJIH | 0.01 | B-F | 2.432 | 86.4 | 113.7 |
NOLJIH01 | 0.01 | B-F | 2.539 | 83.8 | 125.7 |
NOLJIH02 | 0.01 | B-F | 2.432 | 86.4 | 113.6 |
XAXMIT | 0.01 | B-F | 2.467 | 87.6 | 111.6 |
Cyclopropane ring as an electron donor | |||||
HEDQAL | 0.005 | C-F | 2.941 | 85.3 | 149.5 |
HEDQIT | 0.005 | C-F | 2.940 | 85.3 | 149.5 |
HIGNAO02 | 0.03 | Al-Br | 3.410 | 87.5 | 145.5 |
KIKLIA | 0.01 | C-Br | 3.332 | 89.6 | 159.7 |
OMIREI | 0.03 | C-Br | 3.430 | 89.4 | 157.1 |
PILSEK | 0.005 | C-F | 3.038 | 89.9 | 127.1 |
QUSREC | 0.01 | C-F | 3.038 | 89.9 | 148.6 |
RUNQEW | 0.005 | C–Cl | 3.262 | 88.7 | 150.1 |
SUTVOU | 0.005 | C-Br | 3.372 | 89.2 | 165.9 |
UFIYEP | 0.005 | C-F | 2.982 | 87.0 | 126.4 |
Cyclobutane ring as an electron donor | |||||
DEZDUH | 0.01 | C-F | 3.025 | 89.9 | 133.5 |
EQIXAF | 0.03 | P-F | 3.012 | 89.9 | 123.8 |
EQIXIN | 0.03 | P-F | 2.989 | 89.9 | 125.5 |
GEGDUU | 0.01 | C-F | 3.054 | 89.6 | 159.7 |
GOGXOP | 0.005 | C-F | 2.993 | 88.4 | 147.7 |
HEXYIV | 0.005 | C-F | 2.971 | 89.4 | 122.7 |
PUFSOA | 0.005 | C-F | 3.011 | 89.6 | 155.8 |
QASKAX | 0.03 | Pt-I | 3.551 | 89.1 | 189.4 |
QUBGOJ | 0.01 | B-F | 3.012 | 90.0 | 165.4 |
SITZOK | 0.005 | C-F | 3.022 | 89.8 | 153.5 |
TOHDAY | 0.005 | C–Cl | 3.265 | 89.1 | 165.1 |
TORPOX | 0.005 | C-F | 3.004 | 89.1 | 146.5 |
YAMGAU01 | 0.005 | C-F | 3.001 | 88.6 | 151.0 |
Cyclopentane ring as an electron donor | |||||
XACHOC | 0.005 | C-F | 3.020 | 89.3 | 153.2 |
HAFQEN | 0.005 | C-F | 3.024 | 89.6 | 149.4 |
NARBEQ | 0.005 | C–Cl | 3.364 | 89.9 | 170.9 |
VANNUT | 0.01 | B-F | 3.036 | 90.0 | 148.0 |
Complex | Eint1 | Eint2 | X···σ | α | β |
---|---|---|---|---|---|
H2-FCCH | −0.09 | −0.10 | 3.482 | 86.0 | 179.6 |
H2-ClCCH | −0.23 | −0.33 | 3.474 | 90.0 | 180.0 |
H2-BrCCH | −0.38 | −0.48 | 3.295 | 89.9 | 179.9 |
H2-ICCH | −0.66 | −0.62 | 3.248 | 87.2 | 177.3 |
H2-F2 | −0.13 | −0.18 | 3.240 | 89.7 | 179.6 |
H2-Cl2 | −0.31 | −0.48 | 3.134 | 90.0 | 180.0 |
H2-Br2 | −0.52 | −0.57 | 3.110 | 89.9 | 179.8 |
H2-I2 | −0.72 | −0.60 | 3.223 | 89.8 | 180.0 |
C3H6-FCCH | −0.37 | −0.48 | 3.486 | 90.0 | 180.0 |
C3H6-ClCCH | −1.16 | −1.63 | 3.394 | 90.0 | 180.0 |
C3H6-BrCCH | −1.86 | −2.14 | 3.377 | 90.0 | 180.0 |
C3H6-ICCH | −2.79 | −2.79 | 3.445 | 90.0 | 180.0 |
C3H6-F2 | −0.57 | −0.89 | 3.165 | 89.9 | 179.9 |
C3H6-Cl2 | −1.64 | −2.15 | 3.193 | 90.0 | 179.6 |
C3H6-Br2 | −2.36 | −2.63 | 3.241 | 89.8 | 179.3 |
C3H6-I2 | −2.97 | −2.97 | 3.399 | 89.4 | 179.4 |
C4H8-FCCH | −0.45 | −0.59 | 3.455 | 90.0 | 179.9 |
C4H8-ClCCH | −0.85 | −1.30 | 3.539 | 90.0 | 180.0 |
C4H8-BrCCH | −1.30 | −1.62 | 3.525 | 90.0 | 179.9 |
C4H8-ICCH | −1.92 | −1.99 | 3.610 | 89.9 | 179.8 |
C4H8-F2 | −0.45 | −0.64 | 3.390 | 87.2 | 165.5 |
C4H8-Cl2 | −0.98 | −1.53 | 3.409 | 88.3 | 170.9 |
C4H8-Br2 | −1.47 | −1.83 | 3.449 | 89.9 | 179.4 |
C4H8-I2 | −1.99 | −2.07 | 3.600 | 89.9 | 179.3 |
C5H10-ClCCH | −0.89 | −1.32 | 3.571 | 89.7 | 179.9 |
C5H10-BrCCH | −1.36 | −1.64 | 3.564 | 87.8 | 171.4 |
C5H10-ICCH | −2.01 | −2.03 | 3.643 | 86.9 | 171.0 |
C5H10-Cl2 | −1.04 | −1.54 | 3.470 | 85.5 | 164.9 |
C5H10-Br2 | −1.55 | −1.85 | 3.522 | 84.8 | 164.9 |
C5H10-I2 | −2.10 | −2.13 | 3.642 | 85.5 | 168.0 |
Complex | QLb | σHH/CC→σAX * | ρBCP |
---|---|---|---|
H2-FCCH | 0.00 | 0 | 0.001 |
H2-ClCCH | 0.00 | 0.11 | 0.002 |
H2-BrCCH | 0.00 | 0.29 | 0.004 |
H2-ICCH | 0.00 | 0.57 | 0.006 |
H2-F2 | 0.00 | 0.06 | 0.001 |
H2-Cl2 | 0.00 | 0.34 | 0.004 |
H2-Br2 | 0.01 | 0.55 | 0.006 |
H2-I2 | 0.01 | 0.1 | 0.006 |
C3H6-FCCH | 0.00 | 0 | 0.002 |
C3H6-ClCCH | 0.00 | 0.06 | 0.005 |
C3H6-BrCCH | 0.01 | 0.12 | 0.006 |
C3H6-ICCH | 0.01 | 0.26 | 0.007 |
C3H6-F2 | 0.01 | 0.07 | 0.004 |
C3H6-Cl2 | 0.02 | 0.29 | 0.007 |
C3H6-Br2 | 0.03 | 0.41 | 0.008 |
_C3H6-I2 | 0.02 | 0.37 | 0.008 |
Complex | ΔEint | ΔEPauli | ΔEelstat | ΔEorb | ΔEdisp | % ΔEelstat | % ΔEorb | % ΔEdisp |
---|---|---|---|---|---|---|---|---|
C3H6-BrCCH | −2.23 | 2.97 | −1.79 | −1.26 | −2.16 | 34 | 24 | 41 |
C3H6-ICCH | −3.47 | 4.13 | −2.53 | −2.23 | −2.83 | 33 | 29 | 37 |
C3H6-Cl2 | −2.41 | 3.48 | −2.06 | −2.01 | −1.83 | 35 | 34 | 31 |
C3H6-Br2 | −3.32 | 4.34 | −2.57 | −2.64 | −2.45 | 34 | 34 | 32 |
C3H6-I2 | −4.08 | 4.88 | −2.88 | −3.10 | −2.97 | 32 | 35 | 33 |
C4H8-ICCH | −2.60 | 2.83 | −1.17 | −1.49 | −2.76 | 22 | 27 | 51 |
C4H8-Br2 | −1.93 | 2.60 | −1.06 | −1.16 | −2.31 | 23 | 26 | 51 |
C4H8-I2 | −2.78 | 3.01 | −1.25 | −1.70 | −2.84 | 22 | 29 | 49 |
C5H10-ICCH | −2.73 | 2.95 | −1.23 | −1.58 | −2.88 | 22 | 28 | 51 |
C5H10-Br2 | −2.11 | 2.76 | −1.15 | −1.37 | −2.35 | 24 | 28 | 48 |
C5H10-I2 | −3.00 | 3.24 | −1.36 | −1.93 | −2.95 | 22 | 31 | 47 |
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Grabowski, S.J. A–X⋯σ Interactions—Halogen Bonds with σ-Electrons as the Lewis Base Centre. Molecules 2021, 26, 5175. https://doi.org/10.3390/molecules26175175
Grabowski SJ. A–X⋯σ Interactions—Halogen Bonds with σ-Electrons as the Lewis Base Centre. Molecules. 2021; 26(17):5175. https://doi.org/10.3390/molecules26175175
Chicago/Turabian StyleGrabowski, Sławomir J. 2021. "A–X⋯σ Interactions—Halogen Bonds with σ-Electrons as the Lewis Base Centre" Molecules 26, no. 17: 5175. https://doi.org/10.3390/molecules26175175