Spectroscopic and Theoretical Study of the Intramolecular π-Type Hydrogen Bonding and Conformations of 2-Cyclopenten-1-ol
Abstract
:1. Introduction
2. Results and Discussion
2.1. Calculated Molecular Conformations
2.2. Vibrational Spectra
2.3. Potential Energy Surface
3. Materials and Methods
3.1. Computations
3.1.1. Structure and Frequency Calculations
3.1.2. Potential Energy Surface
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
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| | | | | | |
2CPOL Conformers | ||||||
A | B | C | D | E | F | |
Energy | ||||||
Energy (cm−1) | 0 | 9 | 293 | 304 | 308 | 361 |
Energy (kJ/mol) | 0 | 0.11 | 3.51 | 3.64 | 3.68 | 4.32 |
Energy (kcal/mol) | 0 | 0.03 | 0.84 | 0.87 | 0.88 | 1.03 |
Relative population (%) | ||||||
At 25° | 35% | 34% | 9% | 8% | 8% | 6% |
Angles (degrees) | ||||||
Ring-puckering angle | −21.1° | 22.5° | −23.1° | 22.8° | 23.7° | −22.8° |
OH internal rotation angle, ϕ | 24.8° | 39.2° | −75.7° | −91.0° | 172.3° | 166.9° |
Distance (Å) | ||||||
O−H14 | 0.960 | 0.960 | 0.958 | 0.958 | 0.958 | 0.958 |
dH14 a | 2.682 | 3.001 | 3.019 | 3.335 | 3.680 | 3.554 |
Molecule | H﮲﮲﮲π (C=C) Distance, Å | Method | Reference |
---|---|---|---|
2-indanol (I) | 2.650 | CCSD/cc-pVTZ | This work |
2.580 | MP2/cc-pVTZ | This work | |
3-cyclopenten-1-ol (II) | 2.744 | CCSD/cc-pVTZ | This work |
2.673 | MP2/cc-pVTZ | This work | |
2-cyclohexen-1-ol (III) | 2.756 | CCSD/cc-pVTZ | This work |
2.737 | MP2/cc-pVTZ | [11] | |
2-cyclopropen-1-ol (IV) | 2.488 | CCSD/cc-pVTZ | [12] |
2.478 | MP2/cc-pVTZ | [12] | |
2-cyclopropen-1-thiol (V) | 2.774 | CCSD/cc-pVTZ | [12] |
2.740 | MP2/cc-pVTZ | [12] | |
2-cyclopropen-1-amine (VI) | 2.583 | CCSD/cc-pVTZ | [12] |
2.571 | MP2/cc-pVTZ | [12] | |
3-cyclopenten-1-amine (VII) | 2.850 | CCSD/cc-pVTZ | [13] |
2.773 | MP2/cc-pVTZ | This work | |
2-cyclopenten-1-ol (2CPOL) | 2.682 | CCSD/cc-pVTZ | This work |
2.632 | MP2/cc-pVTZ | This work |
2-Cyclopenten-1-ol | 3-Cyclopenten-1-ol | 3-Cyclopenten-1-amine | Cyclopentene | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|
Observed | Calculated | Observed | |||||||||
A | A | A | A | Puckered, Cs | |||||||
Ring-Pseudo C2v | Freq. | IR a | Freq. | (IR, R) b | Freq. c | (IR, R) d,e | Freq. f | (IR, R) d,f | Freq. e | (IR, R) b,e | |
A1 | |||||||||||
v3 | C=C stretch | 1609 | m | 1609 | (3, 80) | 1607 | (2, 46) | 1613 | (m, 88) | 1623 | (m, 91) |
v4 | CH2 deformation | 1500 | s | 1459 | (8, 67) | 1446f | (3, 19) | 1452 | (m, 17) | 1471f | (vw, 16) |
v6 | =C-H in plane wag | 1077 | m | 1095 | (10, 100) | 1108f | (4, 95) | 1109 | (w, 58) | 1101 | (w, 66) |
v8 | Ring stretch | 894 | m | 869 | (13, 60) | 832 | (5, 3) | 804 | (s, 43) | 900 | (m, 100) |
v9 | Ring angle bend | 694 | s | 692 | (6, 9) | 745 | (51, 77) | 735 | (w, 9) | 796g | (vw, 1) |
B1 | |||||||||||
v17 | CH2 deformation | 1463 | m | 1436 | (7, 77) | 1446f | (17, 19) | 1437 | (m, 4) | 1445f | (m, 23) |
B2 | |||||||||||
v25 | CH2 rock | 924 | m | 971 | (14, 36) | 948f | (29, 17) | 934 | (m, 4) | 1047 | (s, 1) |
v26 | =C-H out-of-plane wag | 726 | s | 719 | (20, 15) | 674 | (97, 12) | 671 | (s, 11) | 695 | (s, 1) |
v27 | Ring puckering | --- | --- | 119 | (2, 11) | --- | (---, ---) | --- | (---, ---) | --- | (---, ---) |
Other vibrations | |||||||||||
OH stretch | 3632 | w | 3632 | (32, 26) | 3623 | (41, 9) | N. A. | N. A. | N. A. | N. A. | |
C-H wag (up and down) | 1385 | m | 1386 | (80, 53) | 1395 | (38, 13) | 1379 | (m, 7) | N. A. | N. A. | |
COH wag | 1212 | w | 1224 | (13, 14) | 1275 | (9, 3) | N. A. | N. A. | N. A. | N. A. | |
C-O wag (up and down) | 462 | s | 487 | (5, 21) | --- | --- | N. A. | N. A. | N. A. | N. A. | |
C-O wag (sideways) | 346 (L) | w | 388 | (12, 7) | 444 | (0.5, 2) | N. A. | N. A. | N. A. | N. A. | |
vCO | C-O stretch | 1032 | m | 1045 | (75, 21) | 1048 | (54, 0.7) | N. A. | N. A. | N. A. | N. A. |
OH torsion | 217 (L) | m | 313 | (100, 21) | 397h | (---, 8) | N. A. | N. A. | N. A. | N. A. |
Conformer | Observed | Calculated | ||
---|---|---|---|---|
Frequency | Shift | Frequency | Shift | |
A | 3632 | 0 | 3632 | 0 |
B | 3632 | 0 | 3634 | 2 |
C | 3654 | 22 | 3648 | 16 |
D | 3664 | 32 | 3658 | 26 |
E | 3664 | 32 | 3656 | 24 |
F | 3644 | 12 | 3644 | 12 |
2CPOL Conformers | ||||||
---|---|---|---|---|---|---|
A | B | C | D | E | F | |
Energy, (cm−1) | ||||||
CCSD/cc-pVTZ | 0 | 9 | 293 | 304 | 308 | 361 |
MP2/cc-pVTZ | 0 | 89 | 308 | 406 | 406 | 409 |
Ring-puckering coordinate, (Å) | ||||||
CCSD/cc-pVTZ | −0.102 | 0.109 | −0.112 | 0.110 | 0.115 | −0.110 |
MP2/cc-pVTZ | −0.114 | 0.118 | −0.124 | 0.118 | 0.124 | −0.122 |
Ring-puckering angle, (degrees) | ||||||
CCSD/cc-pVTZ | −21.1° | 22.5° | −23.1° | 22.8° | 23.7° | −22.8° |
MP2/cc-pVTZ | −23.6° | 24.3° | −25.7° | 24.4° | 25.6° | −25.3° |
OH internal rotation angle, (degrees) | ||||||
CCSD/cc-pVTZ | 24.8° | 39.2° | 284.3° | 269.0° | 172.3° | 166.9° |
MP2/cc-pVTZ | 22.6° | 38.7° | 286.4° | 268.6° | 172.3° | 166.6° |
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Ocola, E.J.; Laane, J. Spectroscopic and Theoretical Study of the Intramolecular π-Type Hydrogen Bonding and Conformations of 2-Cyclopenten-1-ol. Molecules 2021, 26, 1106. https://doi.org/10.3390/molecules26041106
Ocola EJ, Laane J. Spectroscopic and Theoretical Study of the Intramolecular π-Type Hydrogen Bonding and Conformations of 2-Cyclopenten-1-ol. Molecules. 2021; 26(4):1106. https://doi.org/10.3390/molecules26041106
Chicago/Turabian StyleOcola, Esther J., and Jaan Laane. 2021. "Spectroscopic and Theoretical Study of the Intramolecular π-Type Hydrogen Bonding and Conformations of 2-Cyclopenten-1-ol" Molecules 26, no. 4: 1106. https://doi.org/10.3390/molecules26041106