Structural Refinement of Carbimazole by NMR Crystallography
Abstract
:1. Introduction
2. Results
2.1. DSC, TGA and PXRD
2.2. 1D High-Resolution 13C and 1H SSNMR Spectra
2.3. Optimization of the Crystallographic Structure
2.4. 2D SSNMR Spectra: Validation of the Optimized Structure
3. Materials and Methods
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
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JOVDIH | JOVDIH01 | |||
---|---|---|---|---|
Space Group | P n a 21 | P n m a | ||
Unit Cell | a = 7.689(2)Å b = 17.364(4)Å c = 6.637(1)Å | α = 90° β = 90° γ = 90° | a = 7.698(3)Å b = 6.650(3)Å c = 17.388(7)Å | α = 90° β = 90° γ = 90° |
Z Z′ | 4 1 | 4 1 | ||
R factor | 0.06 | - | ||
Radiation | CuKα Å | - | ||
Temperature | Room Temperature | - |
Assignment | Experimental Chemical Shift δ (ppm) | δ at the DFT Level X-ray Structure (ppm) JOVDIH01 | δ at the DFT Level X-ray Structure (ppm) JOVDIH | δ at the DFT Level Only H Optimized (ppm) JOVDIH01 | δ at the DFT Level Only H Optimized (ppm) JOVDIH | δ at the DFT Level All Atoms Optimized (ppm) JOVDIH01 | δ at the DFT Level All Atoms Optimized (ppm) JOVDIH |
---|---|---|---|---|---|---|---|
H7 | 2.31 | 2.28 (−0.03) | 1.96 (−0.35) | 2.36 (+0.05) | 2.33 (+0.02) | 2.46 (+0.15) | 2.44 (+0.13) |
H4 | 4.28 | 4.20 (−0.08) | 4.68 (+0.40) | 4.30 (+0.02) | 4.26 (−0.02) | 4.16 (−0.12) | 4.19 (−0.09) |
H6 | 5.59 | 5.77 (+0.18) | 5.85 (+0.26) | 5.45 (−0.14) | 5.56 (−0.03) | 5.44 (−0.15) | 5.42 (−0.17) |
H2 | 6.85 | 7.17 (+0.32) | 6.78 (−0.07) | 6.84 (−0.01) | 6.87 (+0.02) | 6.80 (−0.05) | 6.79 (−0.06) |
H3 | 7.85 | 7.58 (−0.27) | 7.61 (−0.24) | 7.92 (+0.07) | 7.86 (+0.01) | 8.02 (+0.17) | 8.03 (+0.18) |
RMSD | - | 0.19 | 0.29 | 0.07 | 0.02 | 0.13 | 0.13 |
C7 | 16.0 | 10.9 (−5.1) | 11.2 (−4.8) | 13.6 (−2.4) | 13.2 (−2.8) | 14.1 (−1.9) | 14.1 (−1.9) |
C4 | 35.6 | 36.5 (+0.9) | 37.3 (+1.7) | 35.7 (+0.1) | 35.8 (+0.2) | 34.9 (−0.7) | 35.1 (−0.5) |
C6 | 66.8 | 68.6 (+1.8) | 70.6 (+3.8) | 68.8 (+2.0) | 71.1 (+4.3) | 69.2 (+2.4) | 68.9 (+2.1) |
C2 | 111.0 | 116.5 (+5.5) | 110.7 (−0.3) | 111.6 (+0.6) | 108.4 (−2.6) | 110.7 (−0.3) | 110.8 (−0.2) |
C3 | 119.8 | 123.7 (+3.9) | 123.0 (+3.2) | 121.9 (+2.1) | 122.1 (+2.3) | 122.1 (+2.3) | 122.2 (+2.4) |
C5 | 148.7 | 147.8 (−0.9) | 148.3 (−0.4) | 149.1 (+0.4) | 148.6 (−0.1) | 151.1 (+2.4) | 151.1 (+2.4) |
C1 | 166.0 | 159.8 (−6.2) | 162.7 (−3.3) | 163.0 (−3.0) | 164.5 (−1.5) | 161.7 (−4.3) | 161.6 (−4.4) |
RMSD | - | 4.0 | 3.0 | 1.8 | 2.4 | 2.4 | 2.4 |
Peak No. | Coupled Nuclei | Intensity | Distance (Å) |
---|---|---|---|
1 | C7-H7 | 1.00 | 1.1 |
2 | C4-H4 | 0.99 | 1.1 |
3 | C6-H6 | 0.41 | 1.1 |
4 | C2-H2 | 0.30 | 1.1 |
5 | C3-H3 | 0.29 | 1.1 |
6 | C6-H7 | 0.20 | 2.1 |
7 | C4-H7 * | 0.19 | 3.4 |
8 | C7-H6 | 0.19 | 2.2 |
9 | C7-H4 * | 0.12 | 3.2 |
10 | C4-H3 | 0.12 | 2.8 |
11 | C3-H4 | 0.08 | 2.6 |
12 | C2-H7 * | 0.07 | 3.6 |
13 | C3-H6 * | 0.07 | 3.3 |
14 | C2-H4 * | 0.06 | 3.4 |
15 | C3-H7 * | 0.05 | 4.6 |
Peak No. | Coupled Nuclei | Intensity | Distance (Å) |
---|---|---|---|
1 | H4-H4 | 1.00 | 1.8 |
2 | H6-H6 | 0.63 | 1.8 |
3 | H7-H7 | 0.50 | 1.8 |
4 | H4-H7 * | 0.33 | 2.5 |
5 | H3-H6 * | 0.28 | 2.5 |
6 | H2-H7 * | 0.27 | 2.5 |
7 | H4-H3 | 0.23 | 2.4 |
8 | H2-H4 * | 0.22 | 2.8 |
9 | H4-H2 * | 0.21 | 2.8 |
10 | H6-H3 * | 0.20 | 2.5 |
11 | H7-H6 | 0.20 | 2.5 |
12 | H7-H2 * | 0.20 | 2.5 |
13 | H6-H7 | 0.19 | 2.5 |
14 | H7-H4 * | 0.19 | 2.5 |
15 | H3-H4 | 0.17 | 2.4 |
16 | H3-H2 | 0.17 | 2.8 |
17 | H2-H3 | 0.17 | 2.8 |
13C | R2 | 1H | R2 | |
---|---|---|---|---|
X-ray structure JOVDIH01 | δ = −1.2011 σ + 202.54 | 0.994 | δ = −1.3808 σ + 37.025 | 0.990 |
X-ray structure JOVDIH | δ = −1.0713 σ + 180.07 | 0.997 | δ = −1.0600 σ + 32.128 | 0.979 |
only H optimized JOVDIH01 | δ = −0.9883 σ + 172.46 | 0.999 | δ = −0.9975 σ + 31.289 | 0.999 |
only H optimized JOVDIH | δ = −1.0020 σ + 170.7 | 0.998 | δ = −1.0114 σ + 31.299 | 1.000 |
all atoms optimized JOVDIH01 | δ = −1.0259 σ + 172.13 | 0.998 | δ = −1.0596 σ + 31.302 | 0.995 |
all atoms optimized JOVDIH | δ = −1.0253 σ + 172.22 | 0.998 | δ = −1.0628 σ + 31.481 | 0.995 |
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Scarperi, A.; Barcaro, G.; Pajzderska, A.; Martini, F.; Carignani, E.; Geppi, M. Structural Refinement of Carbimazole by NMR Crystallography. Molecules 2021, 26, 4577. https://doi.org/10.3390/molecules26154577
Scarperi A, Barcaro G, Pajzderska A, Martini F, Carignani E, Geppi M. Structural Refinement of Carbimazole by NMR Crystallography. Molecules. 2021; 26(15):4577. https://doi.org/10.3390/molecules26154577
Chicago/Turabian StyleScarperi, Andrea, Giovanni Barcaro, Aleksandra Pajzderska, Francesca Martini, Elisa Carignani, and Marco Geppi. 2021. "Structural Refinement of Carbimazole by NMR Crystallography" Molecules 26, no. 15: 4577. https://doi.org/10.3390/molecules26154577