Spectroscopic, X-ray Diffraction and Density Functional Theory Study of Intra- and Intermolecular Hydrogen Bonds in Ortho-(4-tolylsulfonamido)benzamides
Abstract
:1. Introduction
2. Results and Discussion
2.1. Solution Phase Structural Analysis Using NMR and UV-Vis Spectroscopy
2.2. Solid-State Structural Analysis of 3a–c Using IR Spectroscopy and XRD
2.3. Computational Studies
2.3.1. Hirshfeld Interactions
2.3.2. Optimized Structures of 2a, 2b and 2c from DFT Analyses
3. Materials and Methods
3.1. Chemical Synthesis
3.1.1. Preparation of Substrates
3.1.2. Typical Procedure for the Synthesis of the 2-(p-Tolylsulfonamido)benzamides 2a–c
3.2. Instrumentation
3.3. Data Collection and Refinement
3.4. Computational Methods
3.5. Hirshfeld Surface Analyses
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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2a–c | N–H asym/sym str | C–H | C=O | N–H bend | S=O asym/sym str | S–N |
---|---|---|---|---|---|---|
2a | 3469/3362 | 2971 | 1652 | 1493 | 1313/1153 | 935 |
2b | 3473/3371 | 2921 | 1662 | 1485 | 1327/1161 | 939 |
2c | 3444/3345 | 2931 | 1668 | 1498 | 1318/1149 | 961 |
D–H…A | d(D–H) | d(H…A) | d(D…A) | <(DHA) |
---|---|---|---|---|
2a | ||||
N(1)–H(1A)…O(2)#1 | 0.886(19) | 2.180(19) | 3.0405(15) | 164(2) |
N(1)–H(1B)…O(3)#2 | 0.86(2) | 2.23(2) | 3.0542(15) | 161(2) |
N(2)–H(2)…O(1) | 0.873(18) | 1.865(18) | 2.6045(14) | 141(2) |
2b | ||||
N(1)–H(1A)…O(2)#1 | 0.87(2) | 2.17(2) | 2.9690(18) | 151(2) |
N(1)–H(1B)…O(3)#2 | 0.83(2) | 2.33(2) | 3.1462(19) | 170(2) |
N(2)–H(2)…O(1) | 0.77(2) | 1.95(2) | 2.6022(17) | 142(2) |
2c | ||||
N(1)–H(1A)…O(2)#1 | 0.82(3) | 2.14(3) | 2.947(2) | 172(2) |
N(1)–H(1B)…O(1)#2 | 0.77(2) | 2.23(3) | 2.973(2) | 164(2) |
N(2)–H(2)…O(1) | 0.80(2) | 2.09(2) | 2.7359(19) | 138(2) |
Experimental | DFT | |
---|---|---|
Bond Lengths (Å) | ||
2a: C(7)=O(1), N(2)–S(1) | 1.2410 (15), 1.6224 (10) | 1.230, 1.689 |
O(2)–S(1), O(3)–S(1) | 1.4399 (9), 1.4381 (9) | 1.458, 1.455 |
C(7)–N(1), C(8)–S(1) | 1.3331 (16), 1.7555 (12) | 1.367, 1.798 |
2b: C(7)=O(1), N(2)–S(1) | 1.2381 (18), 1.6318 (12) | 1.229, 1.692 |
O(2)–S(1), O(3)–S(1) | 1.4344 (11), 1.4363 (11) | 1.454, 1.458 |
C(7)–N(2), C(8)–S(1) | 1.333 (2), 1.7585 (15) | 1.365, 1.797 |
2c: C(7)=O(1), N(2)–S(1) | 1.242 (2), 1.6306 (14) | 1.274, 1.624 |
O(2)–S(1), O(3)–S(1) | 1.6306(14), 1.4299(12) | 1.628, 1.628 |
C(7)–N(2), S(1)–C(8) | 1.328 (2), 1.7574 (17) | 1.374, 1.784 |
Bond Angles (°) | ||
2a: N(2)–S(1)–C(8) | 107.84 (5) | 107.50 |
O(2)–S(1)–C(8) | 109.43 (5) | 108.20 |
O(3)–S(1)–C(8) | 107.47 (5) | 105.59 |
C(2)–N(2)–S(1) | 126.06 (8) | 125.58 |
2b: N(2)–S(1)–C(8) | 107.51 (7) | 107.51 |
O(2)–S(1)–C(8) | 107.71 (7) | 107.66 |
O(3)–S(1)–C(8) | 108.45 (7) | 108.35 |
C(1)–N(2)–S(1) | 123.74 (10) | 123.74 |
2c: N(2)–S(1)–C(8) | 107.08 (8) | 107.20 |
O(2)–S(1)–C(8) | 108.51 (8) | 108.47 |
O(3)–S(1)–C(8) | 107.49 (8) | 107.28 |
C(1)–N(2)–S(1) | 130.22 (12) | 129.81 |
Torsion Angles (°) | ||
2a: C(8)–S(1)–N(2)–C(2) | –53.07 (11)° | −57.10 |
C(3)–C(2)–N(2)–S(1) | −32.18 (16) | −32.38 |
C(9)–C(8)–S(1)–N(2) | −66.54 (11) | −66.05 |
O(2)–S(1)–N(2)–C(2) | −169.35 (10) | −165.75 |
2b: C(1)–N(2)–S(1)–C(8) | 64.18 (13)° | 64.54 |
C(6)–C(1)–N(2)–S(1) | 52.08 (18) | 52.26 |
C(9)–C(8–S(1)–N(2) | 66.41 (14) | 66.14 |
C(1)–N(2)–S(1)–O(3) | 179.24 (12) | 179.70 |
2c: C(1)–N(2)–S(1)–C(8) | 75.54 (17)° | 75.54 |
C(6)–C(1)–N(2)–S(1) | 11.00 (3) | 12.50 |
C(9)–C(8)–S(1)–N(2) | −110.21 (15) | 110.73 |
C(1)–N(2)–S(1)–O(3) | −40.99 (18) | −40.99 |
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Mphahlele, M.J.; Onwu, E.E.; Maluleka, M.M. Spectroscopic, X-ray Diffraction and Density Functional Theory Study of Intra- and Intermolecular Hydrogen Bonds in Ortho-(4-tolylsulfonamido)benzamides. Molecules 2021, 26, 926. https://doi.org/10.3390/molecules26040926
Mphahlele MJ, Onwu EE, Maluleka MM. Spectroscopic, X-ray Diffraction and Density Functional Theory Study of Intra- and Intermolecular Hydrogen Bonds in Ortho-(4-tolylsulfonamido)benzamides. Molecules. 2021; 26(4):926. https://doi.org/10.3390/molecules26040926
Chicago/Turabian StyleMphahlele, Malose J., Eugene E. Onwu, and Marole M. Maluleka. 2021. "Spectroscopic, X-ray Diffraction and Density Functional Theory Study of Intra- and Intermolecular Hydrogen Bonds in Ortho-(4-tolylsulfonamido)benzamides" Molecules 26, no. 4: 926. https://doi.org/10.3390/molecules26040926