Strong Hydrogen Bonds of Coordinated Ammonia Molecules
Abstract
The hydrogen bonds of noncoordinated (NH/O) and coordinated ammonia (MLNH/O) with water molecules were studied by analyzing data in the Cambridge Structural Database (CSD) and by DFT calculations. The data from the CSD on the distribution of hydrogen bond dHO distances of the coordinated ammonia show a peak in the range of 2.0–2.2 Å with a significant number of hydrogen bonds in the range of 1.8–2.0 Å. Analysis of Hirshfeld surfaces showed that coordinated NH3 molecules are involved in numerous noncovalent contacts. The DFT calculations were performed on linear complexes of silver(I), square-planar complexes of platinum(II), tetrahedral complexes of zinc(II), and octahedral complexes of cobalt(III) by varying the charge of the complexes. The calculated data show that coordinated ammonia has stronger hydrogen bonds than noncoordinated ammonia, even for neutral complexes. The hydrogen bond energy of noncoordinated ammonia is −2.3 kcal/mol, while for coordinated ammonia, attractive intera...ctions are in the range of −3.7 to −25.0 kcal/mol, depending on the metal ion and charge of the complex. The interaction energies for metal complexes from neutral to charged species are for the linear silver(I) complex from −6.0 to −10.7 kcal/mol, while for the square planar complex, interactions span from −5.9 to −19.9 kcal/mol. The tetrahedral zinc(II) complexes have interaction energy from −5.5 to −17.5 kcal/mol, while for the octahedral cobalt(III) complex, attractive interaction energies are from −3.7 to −25.0 kcal/mol. With the increasing charge of the metal complex, the hydrogen bond between coordinated ammonia and free water becomes stronger, and in accordance with that, the dHO distance becomes shorter. The bifurcated interaction is stronger than monofurcated for all complexes. The interaction energies correspond well with the electrostatic potential (Vs) values on interacting hydrogen atoms; the more positive Vs values on hydrogen atoms lead to stronger interaction. The hydrogen bond between ammonia and water molecules (−2.3 kcal/mol) is quite weak in comparison to the water/water hydrogen bond; it is 50% of the water/water hydrogen bond (−4.84 kcal/mol). Although the hydrogen bonds of coordinated ammonia are also weaker than hydrogen bonds of coordinated water molecules, the difference is smaller, indicating the importance of the coordination on the strength of hydrogen bonds.
Keywords:
Ammonia / Crystal structure / Molecules / Interaction energiesSource:
Crystal Growth and Design, 2022, 22, 1, 148-158Publisher:
- ACS
Funding / projects:
- Ministry of Science, Technological Development and Innovation of the Republic of Serbia, institutional funding - 200168 (University of Belgrade, Faculty of Chemistry) (RS-MESTD-inst-2020-200168)
- Ministry of Science, Technological Development and Innovation of the Republic of Serbia, institutional funding - 200288 (Innovation Center of the Faculty of Chemistry) (RS-MESTD-inst-2020-200288)
DOI: 10.1021/acs.cgd.1c00685
ISSN: 1528-7483
WoS: 000767204000017
Scopus: 2-s2.0-85120373814
Collections
Institution/Community
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Živković, Jelena M. AU - Veljković, Dušan Ž. AU - Zarić, Snežana D. PY - 2022 UR - http://cherry.chem.bg.ac.rs/handle/123456789/4998 AB - The hydrogen bonds of noncoordinated (NH/O) and coordinated ammonia (MLNH/O) with water molecules were studied by analyzing data in the Cambridge Structural Database (CSD) and by DFT calculations. The data from the CSD on the distribution of hydrogen bond dHO distances of the coordinated ammonia show a peak in the range of 2.0–2.2 Å with a significant number of hydrogen bonds in the range of 1.8–2.0 Å. Analysis of Hirshfeld surfaces showed that coordinated NH3 molecules are involved in numerous noncovalent contacts. The DFT calculations were performed on linear complexes of silver(I), square-planar complexes of platinum(II), tetrahedral complexes of zinc(II), and octahedral complexes of cobalt(III) by varying the charge of the complexes. The calculated data show that coordinated ammonia has stronger hydrogen bonds than noncoordinated ammonia, even for neutral complexes. The hydrogen bond energy of noncoordinated ammonia is −2.3 kcal/mol, while for coordinated ammonia, attractive interactions are in the range of −3.7 to −25.0 kcal/mol, depending on the metal ion and charge of the complex. The interaction energies for metal complexes from neutral to charged species are for the linear silver(I) complex from −6.0 to −10.7 kcal/mol, while for the square planar complex, interactions span from −5.9 to −19.9 kcal/mol. The tetrahedral zinc(II) complexes have interaction energy from −5.5 to −17.5 kcal/mol, while for the octahedral cobalt(III) complex, attractive interaction energies are from −3.7 to −25.0 kcal/mol. With the increasing charge of the metal complex, the hydrogen bond between coordinated ammonia and free water becomes stronger, and in accordance with that, the dHO distance becomes shorter. The bifurcated interaction is stronger than monofurcated for all complexes. The interaction energies correspond well with the electrostatic potential (Vs) values on interacting hydrogen atoms; the more positive Vs values on hydrogen atoms lead to stronger interaction. The hydrogen bond between ammonia and water molecules (−2.3 kcal/mol) is quite weak in comparison to the water/water hydrogen bond; it is 50% of the water/water hydrogen bond (−4.84 kcal/mol). Although the hydrogen bonds of coordinated ammonia are also weaker than hydrogen bonds of coordinated water molecules, the difference is smaller, indicating the importance of the coordination on the strength of hydrogen bonds. PB - ACS T2 - Crystal Growth and Design T1 - Strong Hydrogen Bonds of Coordinated Ammonia Molecules VL - 22 IS - 1 SP - 148 EP - 158 DO - 10.1021/acs.cgd.1c00685 ER -
@article{ author = "Živković, Jelena M. and Veljković, Dušan Ž. and Zarić, Snežana D.", year = "2022", abstract = "The hydrogen bonds of noncoordinated (NH/O) and coordinated ammonia (MLNH/O) with water molecules were studied by analyzing data in the Cambridge Structural Database (CSD) and by DFT calculations. The data from the CSD on the distribution of hydrogen bond dHO distances of the coordinated ammonia show a peak in the range of 2.0–2.2 Å with a significant number of hydrogen bonds in the range of 1.8–2.0 Å. Analysis of Hirshfeld surfaces showed that coordinated NH3 molecules are involved in numerous noncovalent contacts. The DFT calculations were performed on linear complexes of silver(I), square-planar complexes of platinum(II), tetrahedral complexes of zinc(II), and octahedral complexes of cobalt(III) by varying the charge of the complexes. The calculated data show that coordinated ammonia has stronger hydrogen bonds than noncoordinated ammonia, even for neutral complexes. The hydrogen bond energy of noncoordinated ammonia is −2.3 kcal/mol, while for coordinated ammonia, attractive interactions are in the range of −3.7 to −25.0 kcal/mol, depending on the metal ion and charge of the complex. The interaction energies for metal complexes from neutral to charged species are for the linear silver(I) complex from −6.0 to −10.7 kcal/mol, while for the square planar complex, interactions span from −5.9 to −19.9 kcal/mol. The tetrahedral zinc(II) complexes have interaction energy from −5.5 to −17.5 kcal/mol, while for the octahedral cobalt(III) complex, attractive interaction energies are from −3.7 to −25.0 kcal/mol. With the increasing charge of the metal complex, the hydrogen bond between coordinated ammonia and free water becomes stronger, and in accordance with that, the dHO distance becomes shorter. The bifurcated interaction is stronger than monofurcated for all complexes. The interaction energies correspond well with the electrostatic potential (Vs) values on interacting hydrogen atoms; the more positive Vs values on hydrogen atoms lead to stronger interaction. The hydrogen bond between ammonia and water molecules (−2.3 kcal/mol) is quite weak in comparison to the water/water hydrogen bond; it is 50% of the water/water hydrogen bond (−4.84 kcal/mol). Although the hydrogen bonds of coordinated ammonia are also weaker than hydrogen bonds of coordinated water molecules, the difference is smaller, indicating the importance of the coordination on the strength of hydrogen bonds.", publisher = "ACS", journal = "Crystal Growth and Design", title = "Strong Hydrogen Bonds of Coordinated Ammonia Molecules", volume = "22", number = "1", pages = "148-158", doi = "10.1021/acs.cgd.1c00685" }
Živković, J. M., Veljković, D. Ž.,& Zarić, S. D.. (2022). Strong Hydrogen Bonds of Coordinated Ammonia Molecules. in Crystal Growth and Design ACS., 22(1), 148-158. https://doi.org/10.1021/acs.cgd.1c00685
Živković JM, Veljković DŽ, Zarić SD. Strong Hydrogen Bonds of Coordinated Ammonia Molecules. in Crystal Growth and Design. 2022;22(1):148-158. doi:10.1021/acs.cgd.1c00685 .
Živković, Jelena M., Veljković, Dušan Ž., Zarić, Snežana D., "Strong Hydrogen Bonds of Coordinated Ammonia Molecules" in Crystal Growth and Design, 22, no. 1 (2022):148-158, https://doi.org/10.1021/acs.cgd.1c00685 . .