Analysis of P-O-C, P-S-C and P-O-P angles: a database survey completed with four new X-ray crystal structures

SABBAGHI, Fahimeh, Mehrdad POURAYOUBI, Michal DUŠEK, Václav EIGNER, Sahar BAYAT, Krishnan DAMODARAN, Marek NEČAS and Monika KUČERÁKOVÁ. Analysis of P-O-C, P-S-C and P-O-P angles: a database survey completed with four new X-ray crystal structures. STRUCTURAL CHEMISTRY. NEW YORK: SPRINGER/PLENUM PUBLISHERS, 2016, vol. 27, No 6, p. 1831-1844. ISSN 1040-0400. Available from: https://dx.doi.org/10.1007/s11224-016-0809-7.

Basic information

• Original name: Analysis of P-O-C, P-S-C and P-O-P angles: a database survey completed with four new X-ray crystal structures
• Authors: SABBAGHI, Fahimeh (364 Islamic Republic of Iran), Mehrdad POURAYOUBI (364 Islamic Republic of Iran), Michal DUŠEK (203 Czech Republic), Václav EIGNER (203 Czech Republic), Sahar BAYAT (364 Islamic Republic of Iran), Krishnan DAMODARAN (356 India), Marek NEČAS (203 Czech Republic, guarantor, belonging to the institution) and Monika KUČERÁKOVÁ (203 Czech Republic).
• Edition: STRUCTURAL CHEMISTRY, NEW YORK, SPRINGER/PLENUM PUBLISHERS, 2016, 1040-0400.

Other information

• Original language: English
• Type of outcome: Article in a journal
• Field of Study: 10402 Inorganic and nuclear chemistry
• Country of publisher: United States of America
• Confidentiality degree: is not subject to a state or trade secret
• Impact factor: Impact factor: 1.582
• RIV identification code: RIV/00216224:14310/16:00093928
• Organization unit: Faculty of Science
• Doi: http://dx.doi.org/10.1007/s11224-016-0809-7
• UT WoS: 000386373500025
• Keywords in English: Cambridge Structural Database (CSD); Crystal structure; Analysis of bond angle; Hybridization
• Tags: AKR, rivok
• Tags: International impact, Reviewed

Abstract

Four new crystal structures, P(O)(OC6H5)(2)(NHNHC6H5) (I), P(S)(OCH3)(2)(NHCH(CH3)(2)) (II), P(S)(OCH3)(2)(NH-cyclo-C5H9) (III) and [2-Cl-C6H4CH2NH3](2)[(CH3S)P(O)(O)-O-P(O)(O)(SCH3)] (IV) were studied. The P-O-C angles were analyzed, considering phosphoryl compound (I) and thiophosphoryl compounds (II) and (III) and their analogous structures deposited in the Cambridge Structural Database (CSD), including 282 P(O)(O)(2)(N) structures (706 P-O-C angles) and 186 P(S)(O)(2)(N) structures (518 P-O-C angles) with at least one P-O-C angle. The maximum populations of P-O-C angles are within 120A degrees-122A degrees in both P(O)(O)(2)(N) and P(S)(O)(2)(N) families of structures, confirming the hybridization state close to sp (2) for the oxygen atom of P-O-C. A survey on the CSD resulted in 11 P(O)(O)(2)(S-C) structures (11 P-S-C angles), and the structure (IV) belonging to this family of compounds is the first diffraction study of a salt with a (S)P(O)(O)-O-P(O)(O)(S) skeleton in the anion component. For the P-S-C angles, the maximum population was found in the range of 100A degrees-104A degrees showing the angles within those related to unhybridized pure p orbitals (p (3)) and hybridized sp (3) for the sulfur atom of P-S-C. The analysis of 187 P(O)-O-P(O) structures (with no restriction on the other two atoms attached to phosphorus) including 538 P-O-P angles yielded the maximum population of P-O-P angles within 132A degrees-134A degrees, showing the more pronounced "s" character of the orbital (with respect to the sp (2) and toward sp) for the oxygen atom at the P-O-P moiety.