sigma-Hole Interactions of Covalently-Bonded Nitrogen, Phosphorus and Arsenic: A Survey of Crystal Structures
Abstract
Covalently-bonded atoms of Groups IV-VII tend to have anisotropic charge distributions, the electronic densities being less on the extensions of the bonds (sigma-holes) than in the intervening regions. These sigma-holes often give rise to positive electrostatic potentials through which the atom can interact attractively and highly directionally with negative sites (e.g., lone pairs, pi electrons and anions), forming noncovalent complexes. For Group VII this is called. halogen bonding. and has been widely studied both computationally and experimentally. For Groups IV-VI, it is only since 2007 that positive sigma-holes have been recognized as explaining many noncovalent interactions that have in some instances long been known experimentally. There is considerable experimental evidence for such interactions involving groups IV and VI, particularly in the form of surveys of crystal structures. However we have found less extensive evidence for Group V. Accordingly we have now conducted a su...rvey of the Cambridge Structural Database for crystalline close contacts of trivalent nitrogen, phosphorus and arsenic with six different types of electronegative atoms in neighboring molecules. We have found numerous close contacts that fit the criteria for sigma-hole interactions. Some of these are discussed in detail; in two instances, computed molecular electrostatic potentials are presented.
Keywords:
sigma-hole interactions / trivalent nitrogen / phosphorus and arsenic / survey of crystal structures / electrostatic potentialsSource:
Crystals, 2014, 4, 1, 12-31Publisher:
- MDPI
Funding / projects:
DOI: 10.3390/cryst4010012
ISSN: 2073-4352
WoS: 000351877100002
Scopus: 2-s2.0-84901335914
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IHTMTY - JOUR AU - Politzer, Peter AU - Murray, Jane S AU - Janjić, Goran AU - Zarić, Snežana D. PY - 2014 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/1445 AB - Covalently-bonded atoms of Groups IV-VII tend to have anisotropic charge distributions, the electronic densities being less on the extensions of the bonds (sigma-holes) than in the intervening regions. These sigma-holes often give rise to positive electrostatic potentials through which the atom can interact attractively and highly directionally with negative sites (e.g., lone pairs, pi electrons and anions), forming noncovalent complexes. For Group VII this is called. halogen bonding. and has been widely studied both computationally and experimentally. For Groups IV-VI, it is only since 2007 that positive sigma-holes have been recognized as explaining many noncovalent interactions that have in some instances long been known experimentally. There is considerable experimental evidence for such interactions involving groups IV and VI, particularly in the form of surveys of crystal structures. However we have found less extensive evidence for Group V. Accordingly we have now conducted a survey of the Cambridge Structural Database for crystalline close contacts of trivalent nitrogen, phosphorus and arsenic with six different types of electronegative atoms in neighboring molecules. We have found numerous close contacts that fit the criteria for sigma-hole interactions. Some of these are discussed in detail; in two instances, computed molecular electrostatic potentials are presented. PB - MDPI T2 - Crystals T1 - sigma-Hole Interactions of Covalently-Bonded Nitrogen, Phosphorus and Arsenic: A Survey of Crystal Structures VL - 4 IS - 1 SP - 12 EP - 31 DO - 10.3390/cryst4010012 ER -
@article{ author = "Politzer, Peter and Murray, Jane S and Janjić, Goran and Zarić, Snežana D.", year = "2014", abstract = "Covalently-bonded atoms of Groups IV-VII tend to have anisotropic charge distributions, the electronic densities being less on the extensions of the bonds (sigma-holes) than in the intervening regions. These sigma-holes often give rise to positive electrostatic potentials through which the atom can interact attractively and highly directionally with negative sites (e.g., lone pairs, pi electrons and anions), forming noncovalent complexes. For Group VII this is called. halogen bonding. and has been widely studied both computationally and experimentally. For Groups IV-VI, it is only since 2007 that positive sigma-holes have been recognized as explaining many noncovalent interactions that have in some instances long been known experimentally. There is considerable experimental evidence for such interactions involving groups IV and VI, particularly in the form of surveys of crystal structures. However we have found less extensive evidence for Group V. Accordingly we have now conducted a survey of the Cambridge Structural Database for crystalline close contacts of trivalent nitrogen, phosphorus and arsenic with six different types of electronegative atoms in neighboring molecules. We have found numerous close contacts that fit the criteria for sigma-hole interactions. Some of these are discussed in detail; in two instances, computed molecular electrostatic potentials are presented.", publisher = "MDPI", journal = "Crystals", title = "sigma-Hole Interactions of Covalently-Bonded Nitrogen, Phosphorus and Arsenic: A Survey of Crystal Structures", volume = "4", number = "1", pages = "12-31", doi = "10.3390/cryst4010012" }
Politzer, P., Murray, J. S., Janjić, G.,& Zarić, S. D.. (2014). sigma-Hole Interactions of Covalently-Bonded Nitrogen, Phosphorus and Arsenic: A Survey of Crystal Structures. in Crystals MDPI., 4(1), 12-31. https://doi.org/10.3390/cryst4010012
Politzer P, Murray JS, Janjić G, Zarić SD. sigma-Hole Interactions of Covalently-Bonded Nitrogen, Phosphorus and Arsenic: A Survey of Crystal Structures. in Crystals. 2014;4(1):12-31. doi:10.3390/cryst4010012 .
Politzer, Peter, Murray, Jane S, Janjić, Goran, Zarić, Snežana D., "sigma-Hole Interactions of Covalently-Bonded Nitrogen, Phosphorus and Arsenic: A Survey of Crystal Structures" in Crystals, 4, no. 1 (2014):12-31, https://doi.org/10.3390/cryst4010012 . .