Analysis of N—H...O hydrogen bonds in new C(O)—NH—P(O)-based phosphoric triamides and analogous structures deposited in the Cambridge Structural Database

Abstract

Five new compounds belonging to the phosphoric triamide family have been synthesized: two of them with the formula XC(O)NHP(O)Y [X = CF3 (1) and CClF2 (2), Y = NHCH2C(CH3)2CH2NH] involving a 1,3-diazaphosphorinane ring part, and three 2,6-Cl2C6H3C(O)NHP(O)Z2 phosphoric triamides [Z = NHC(CH3)3 (3), N(CH3)(C6H11) (4) and N(CH3)(CH2C6H5) (5)]. The characterization was performed by (31)P{(1)H}, (1)H, (13)C NMR, IR spectroscopy besides (19)F NMR for fluorine containing compounds (1) and (2), and X-ray single-crystal structure analysis for (1), (3), (4) and (5). In each molecule the P atom has a distorted tetrahedral environment. The N atoms bonded to P atom have mainly sp(2) character with a very slight tendency to a pyramidal coordination for some amido groups. Different types of N-H···O hydrogen bonds have been analyzed for (1), (3), (4) and (5) and 118 other structures (including 194 hydrogen bonds) deposited in the Cambridge Structural Database, containing either C(O)-NH-P(O)[N(C)(C)]2 or C(O)-NH-P(O)[NH(C)]2. The participation of N(CP)-H···O=P [N(CP) = the nitrogen atom of the C(O)-NH-P(O) fragment], N-H···O=P, N-H···O=C and N(CP)-H···O=C hydrogen bonds in different hydrogen-bonded motifs are discussed. Moreover, the involvement of the O atoms of C=O or P=O in the [N(CP)-H][N-H]···O=P, [N-H]2···O=P, [N-H]2···O=C and [N-H]3···O=C groups are considered. A histogram of N···O distances, the distribution of N-H···O angles and the scatterplot of N-H···O angles versus N···O distances are studied.

Extensive analysis of N—H...O hydrogen bonding in four classes of phosphorus compounds: a combined experimental and database study

“…As there are mostly neutral N-HÁ Á ÁO hydrogen bonds in this class of compounds, the overall trends of the NÁ Á ÁO distances are nearly similar to those in the (C)P(O)(N) 2 structures and are also similar to previously studied neutral structures with C(O)NHP(O)[NHC] 2 and C(O)NHP(O)-[NC 2 ] 2 skeletons (Pourayoubi et al, 2013). A difference with regard to the (C)P(O)(N) 2 structures is that there is an absence of interaction distances of more than 3.35 Å in the (C) 2 P(O)(N) structures.…”

“…(b) Histogram after 'cone correction', considering all of the data found in the CSD and structure (I) (the angular distribution is weighted by a correction factor of 1/sin to properly reflect angular preferences). towards slightly longer NÁ Á ÁO distances compared to other previously analyzed P O-containing compounds(Pourayoubi et al, 2013), i.e. C(O)NHP(O)-based phosphoric triamides (with maximum populations in the range 2.80-2.85 Å ).…”

“…The N-HÁ Á ÁO P hydrogen bond is the most generally present interaction throughout different families of phosphoryl-based compounds that contain an NH unit, so it is regarded as the characteristic hydrogen bond in such structures. For neutral compounds with C(O)NHP(O)[NHC] 2 and C(O)NHP(O)[NC 2 ] 2 segments, the strengths of N-HÁ Á ÁO P hydrogen bonds have been evaluated (Pourayoubi et al, 2013) and here the hydrogen bonds are considered as RAHBs, with NÁ Á ÁO distances in the range 2.70-3.10 Å [moderate hydrogen bonds according to the classification of Jeffrey (1997)].…”

Two new thiophosphoramide structures:N,N′,N′′-tricyclohexylphosphorothioic triamide andO,O′-diethyl (2-phenylhydrazin-1-yl)thiophosphonate

“…For the P(S) [O] 2 [N] search, the variety of compounds deposited is larger compared with the P(S) [N] 3 skeleton and structures with [O] In a continuation of our previous reports on the structure determinations of phosphoramide (Pourayoubi, Nečas & Negari, 2012;Tarahhomi et al, 2013) and thiophosphoramide compounds (Raissi Shabari et al, 2012;Sabbaghi et al, 2012) and a CSD analysis of different aspects of phosphoramide structures (Pourayoubi et al, 2013;Pourayoubi, Jasinski et al, 2012), we report here a study of thiophosphoramide structures.…”

The synergistic co-operation of N—H...O=P hydrogen bonds and C—H...OX weak intermolecular interactions (X is =P or —C) in the (CH3O)2P(O)(NH–NHC6F5) amidophosphoester: a combined X-ray crystallographic and theoretical study

“…Phosphoramides, with a highly polarized phosphoryl O atom (P O), are interesting in the area of crystal engineering from the point of view of the formation of nearly strong N-HÁ Á ÁO P hydrogen bonds to weak C-HÁ Á ÁO P contacts (Pourayoubi et al, 2014;Saneei et al, 2018Saneei et al, , 2017, and the synergistic co-operation of hydrogen bonds noted was studied in the phosphoric triamide family (Saneei et al, 2018). In various published articles, statistical analyses of hydrogenbond strengths were carried out (Pourayoubi, Toghraee et al, 2013;Hamzehee, Pourayoubi, Nečas et al, 2017) in different classes of phosphoryl-based structures retrieved from the Cambridge Structural Database (CSD; Groom et al, 2016). Furthermore, several theoretical calculation-based studies were performed to evaluate the strengths of the N-HÁ Á ÁO P hydrogen bonds in phosphoramides (Pourayoubi, Izadyar et al, 2013;Taherzadeh et al, 2017;Vahdani Alviri et al, 2018;Sabbaghi et al, 2017) and phosphinic amides (Hamzehee, Pourayoubi, Farhadipour et al, 2017), and C-HÁ Á ÁO interactions, typically in a molecular adduct of Cl 3 C-HÁ Á ÁO P(n-Bu) 3 (Doskocz & Gancarz, 2009).…”