Comparison of Intermolecular Halogen...Halogen Distances in Organic and Organometallic Crystals

• Published in: International journal of molecular sciences Vol. 24; no. 15; p. 11911
• Main Author: Grineva, Olga V
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 25.07.2023; MDPI
• Subjects: Analysis; Arrays; carbon–halogen group; Crystals; Gaussian function; halogen aggregation; Histograms; metal–halogen group; Nucleic acids; Protein binding; Proteins; Statistical analysis; van der Waals radii; Gaussian function; carbon–halogen group; van der Waals radii; halogen aggregation; metal–halogen group
• ISSN: 1422-0067; 1661-6596; 1422-0067
• DOI: 10.3390/ijms241511911

Statistical analysis of halogen...halogen intermolecular distances was performed for three sets of homomolecular crystals under normal conditions: C-Hal1...Hal2-C distances in crystals consisting of: (i) organic compounds (set Org); (ii) organometallic compounds (set Orgmet); and (iii) distances M1-Hal1...Hal2-M2 (set MHal) (in all cases Hal1 = Hal2, and in MHal M1 = M2, M is any metal). When analyzing C-Hal...Hal-C distances, a new method for estimating the values of van der Waals radii is proposed, based on the use of two subsets of distances: (i) the shortest distances from each substance less than a threshold; and (ii) all C-Hal...Hal-C distances less than the same threshold. As initial approximations for these thresholds for different Hal, the values previously introduced in investigations with the participation of the author were used ( values make it possible to perform a statistical assessment of the presence of halogen aggregates in crystals). The following values are recommended in this work to be used as universal values for crystals of organic and organometallic compounds: = 1.57, = 1.90, = 1.99, and = 2.15 Å. They are in excellent agreement with the results of some other works but significantly (by 0.10-0.17 Å) greater than the commonly used values. For the Orgmet set, slightly lower values for (2.11-2.09 Å) were obtained, but number of the C-I...I-C distances available for analysis was significantly smaller than in the other subgroups, which may be the reason for the discrepancy with value for the Org set (2.15 Å). Statistical analysis of the M-Hal...Hal-M distances was performed for the first time. A Hal-aggregation coefficient for M-Hal bonds is proposed, which allows one to estimate the propensity of M-Hal groups with certain M and Hal to participate in Hal-aggregates formed by M-Hal...Hal-M contacts. In particular, it was found that, for the Hg-Hal groups (Hal = Cl, Br, I), there is a high probability that the crystals have Hg-Hal...Hal-Hg distances with length ≤ .