Phosphoric Triamides Research Articles

Energy frameworks and Hirshfeld surface analysis of supramolecular features in three new phosphoric triamides: tuning the intermolecular interactions via the substituent effect

Supramolecular features observed in the crystal structures of phosphoric triamides are mostly influenced by strong hydrogen bond interaction N—H...OP. With the aid of substituent groups a scenario can be created where the crucial role of weak interactions towards the stabilization of the overall molecular packing, in the absence of any strong interaction can be evaluated more reliably. In this context, we have studied the supramolecular features of three new phosphoric triamides 1 – 3, with [NH]P(O)[N]2, [C(O)N]2P(O)[N] and [C(O)N]2P(O)[NH] segments, respectively. The compounds crystallize in the monoclinic space groups P21/c for 1 and 2 with one phosphoric triamide molecule and in P21 for 3 with two molecules in the asymmetric unit. The intermolecular interactions and their energies are evaluated using Hirshfeld surface and energy framework analyses revealing that the presence or absence of substituent groups such as 2-oxo-3-oxazolidinyl may serve as a crucial cohesive factor in the supramolecular assembly. The substituent alters the intermolecular interaction contributions, with subsequent changes in the formation of different weak interactions and molecular assemblies. The structure of 2 bearing this substituent displays the highest energy interaction without any strong interaction. The crystal packing is stabilized by a variety of interactions involving the weak hydrogen bonds with the PO and CO acceptor sites. The effects of substituent groups on the molecular frameworks formed by various intermolecular interactions are analyzed in detail via energy framework diagrams. Finally, a biological study by the molecular docking method indicates that the studied here compounds could be appropriate candidates as SARS-CoV-2 inhibitors.

Polyanionic Imido-P(V) Ligands: From Transition Metal Complexes to Coordination Driven Self-Assemblies.

The chemistry of the imido-anions of the main group elements has been studied for more than three decades. The imido (NR)- group is isoelectronic to the oxo (=O) group and can coordinate with metal ions through its lone pairs of electrons. The polyimido-P(V) anions are well explored as they resemble the phosphorus oxo moieties such as H3 PO4 , H2 PO4 - , HPO4 2- and PO4 3- species. These imido anions are typically generated using strong main group organometallic reagents such as n BuLi, Et2 Zn, Me3 Al and n Bu2 Mg, etc. As a result, their coordination chemistry has been restricted to reactions in anhydrous aprotic solvents for a few main group metal ions. This account presents our findings on using certain soft transition metal such Ag(I) and Pd (II) for isolating these imido-P(V) anions as their corresponding self-assembled clusters and cages. Using the various salts of Ag(I) ions in reaction with 2-pyridyl (2 Py) functionalized phosphonium salts and phosphoric triamides, we obtained the mono- and dianionic form of these imido ligands {[P(N2 Py)2 (NH2 Py)2 ]- , [P(N2 Py)2 (NH2 Py)]- , [PO(N2 Py)(NH2 Py)2 ]2- } and derived interesting examples of tri, penta, hepta and octanuclear Ag(I) clusters. Interestingly, by using the salts of Pd (II) ions, the elusive imido-phosphate trianions of the type [(RN)3 PO]3- (R=t Bu, c Hex, i Pr) were generated in a facile one pot reaction as their corresponding tri- and hexanuclear clusters of the type {Pd3 [(NR)3 PO](OAc)3 }n (n=1 or 2). These trianions acts as a cis-coordinated hexadentate ligand for a trinuclear Pd (II) cluster and serve as the polyhedral building units for constructing hitherto unknown family of neutral cages in tetrahedral {Pd3 [(Ni Pr)3 PO]4 (L)6 } and cubic {Pd3 [(Ni Pr)3 PO]8 (L)12 } structures in the presence of suitable linker ligands (L2- ). These cages show interesting host-guest chemistry and post-assembly reactions. Remarkably, by employing chiral tris(imido)phosphate trianions, enantiopure chiral cages of the type [(Pd3 X*)4 (L)6 ], ([X*]3- =RRR- or SSS-[PO(N(*CH(CH3 )Ph)3 ]3- ), were synthesized and used for the chiral-recognition and enantio-separation of small racemic guest molecules. Some of these chiral cages were also shown to exhibit polyradical framework structures. In future, these and other similar types of cages are envisioned as potential molecular vessels for performing the reactions in their confined environment. The enantiomeric cages can be probed for asymmetric catalysis and the separation of a range of small chiral molecules.

Synthesis and structural study of five new phosphoric triamides: interplay between classical and non-classical intermolecular interactions

Abstract Phosphoric triamides are attractive to investigate because of their extensive applications in various fields, especially in medicine. Five new phosphoric triamides with the main parts [N]P(O)[NH]2 and [C(O)NH]P(O)[N]2 have been structurally analyzed by single crystal MoKα/synchrotron-based X-ray diffraction and characterized by spectroscopic methods (FT-IR and 1H, 13C, 31P NMR). Compounds crystallize in orthorhombic (1 with space group Pnma) and monoclinic (2 (P21/a), 3 (C2/c), 4 (P21/n) and 5 (P21/c)) crystal systems. The asymmetric unit of all structures consists of one phosphoric triamide molecule, except for 1 with one half of molecule. X-ray crystallography data reveal that the molecular architectures constructed by classical N—H … O hydrogen bonds are as 1D linear (building the R 2 1 ( 6 ) ${R}_{2}^{1}\left(6\right)$ , C(4) and R 2 2 ( 10 ) / R 2 1 ( 6 ) ${R}_{2}^{2}\left(10\right)/{R}_{2}^{1}\left(6\right)$ motifs, respectively, for 1–3) or dimeric (the R 2 2 ( 8 ) ${R}_{2}^{2}\left(8\right)$ ring motif for 4 and 5). A detailed investigation of the intermolecular interactions using Hirshfeld surface (HS) analysis illustrates that the H … H, O … H/H … O and C … H/H … C contacts for all compounds, and Cl … H/H … Cl and F … H/H … F contacts for 3–5, are the most significant contributors to the crystal packing. Moreover, based on the calculated enrichment ratios (E), the O … H/H … O contacts including the classical N—H … O hydrogen bonds for all structures are considered as favoured contacts.

Association of Non‐covalent Interactions C−H…X (X=O, F, Cl, π) and Cl…π with Hydrogen Bond Interactions N−H…O in Molecular Assembly of New Phosphoramides: A Combined X‐Ray Crystallography and Topology (AIM and Hirshfeld) Analysis

AbstractCrystal structures of six new phosphoramides with the main parts [C(O)NH]P(O)[N]2 and [NH]2P(O)[N] were determined by single crystal X‐ray diffraction and characterized by spectroscopic methods (FT‐IR and 1H, 13C, 31P NMR). X‐ray crystallography data manifest that the hydrogen bond interactions N−H…O (in all structures) accompanied by some contacts such as C−H…X (X=π, O, F and Cl) and π…π dominate the molecular architectures. Some non‐classical interactions such as Cl…π are also found in feature packing of some studied structures. A detailed investigation of these intermolecular interactions in order to illustrate the importance of non‐classical interactions in construction of molecular assemblies is presented by Hirshfeld surface (HS) analysis reflected the most important van der Waals (vdW) contributions and “Quantum Theory Atom In Molecule” (QTAIM) method especially in term of energetic feature. Hirshfeld surface analysis reveals that the prevalent interactions are of the type O…H for all structures coupled with some other short contacts such as C…C and H…F recognized by red spots on Hirshfeld surfaces and enrichment ratios (E) larger than unity (E > 1). These results are confirmed by AIM method classifying the hydrogen bond interactions N−H…O as moderate non‐covalent closed‐shell interactions and the remaining interactions above‐mentioned as vdW closed‐shell interactions in the studies phosphoric triamides. Such study to categorize the popular hydrogen bond interactions N−H…O in phosphoric triamides and the weak interactions in their molecular packing are used for the first time.

Evaluation of N–H···O hydrogen bond interactions in two new phosphoric triamides with a P(O)[NHCH(CH3)2]2segment by means of topological (AIM) calculations, Hirshfeld surface analysis and 3D energy framework approach

AbstractTwo new phosphoric triamides having a common partXP(O)[NHCH(CH3)2]2, withX =[2,3,6-F3–C6H2C(O)NH] (1)and [C6H11(CH3)N] (2), were prepared and characterized by spectroscopic techniques (FT-IR and1H-,13C-,31P-NMR) and single crystal X-ray diffraction. The asymmetric unit of1is composed of one molecule, whereas for2it consists of six symmetry independent molecules. In all molecules, the P atoms are in a distorted tetrahedral environment of one oxygen and three nitrogen atoms. The latter have mainlysp2character and a nearly planar environment. The crystal structures are stabilizedviaN–H · · · O hydrogen bond interactions, forming a linear arrangement for1and three independent parallel linear chains for2, along thebandaaxis, respectively. The intermolecular interactions in the molecular packing were analyzed using the Hirshfeld surface methodology, two-dimensional (2D) fingerprint plots and enrichment ratios (E). The prevalent interactions revealed by Hirshfeld surfaces are O · · · H type interactions for both structures1and2, additionally C · · · O for1and H · · · H interactions for2. The most favored contacts responsible for the molecular packing are C · · · F, N · · · H and O · · · H for1confirmed byEvalues greater than 1.30, whereas for2, O · · · H and N · · · H intermolecular interactions withEvalues about 1.04 representing the favored contacts. Thus, the N–H · · · O hydrogen bond interactions are the dominant interactions in both compounds. For more details, a topological AIM analysis of N–H · · · O hydrogen bond interactions was performed: NCP–H · · · O=C hydrogen bond (the NCPis referred to the nitrogen atom within the C(O)NHP(O) segment) interactions in1are stronger than N–H · · · O=P interactions in both1and2. Furthermore, a 3D topology of the molecular packingviathe energy framework approach showed that the N–H · · · O hydrogen bond interactions in C(O)NHP(O)-based phosphoric triamide are predominantly electrostatic based, while they are electrostatic-dispersion based for other phosphoric triamides with a [N]P(O)[NH]2skeleton.

Synthesis, Crystal Structure and Hirshfeld Surface (HS) Analysis of Two New Phosphoric Triamides: A Comparison of HSs for Structures with Different Molecular Assemblies

Two new phosphoric triamides, N-(2-chloro-5-fluorobenzoyl)-N′,N"-bis(morpholin-4-yl)-phosphoric triamide, (2-Cl,5-F-C6H3C(O)NH)P(O)(NC4H8O)2, 1, and N,N′-dibenzyl-N"-(2-chloro-5-fluorobenzoyl)-N,N′-diethylphosphoric triamide, (2-Cl,5-F-C6H3C(O)NH)P(O)(N(C2H5)(CH2C6H5))2, 2, were synthesized and characterized by 1H-, 13C-, 31P-, 19F-NMR and IR spectroscopies and single-crystal X-ray diffraction analysis. Different orientations of P(O) versus NH, anti in 1 and syn in 2, lead to different hydrogen bond patterns, mediated by N–H⋯O, as a linear arrangement forming a C(4) motif and a dimeric aggregate with an $$R_{2}^{2}\left( 8 \right)$$ ring motif, respectively. The crystal packing of both compounds present a three-dimensional supramolecular assembly, made by the cooperation from weak intermolecular interactions, C–H⋯O and C–H⋯π, for 1 and 2, and π⋯π for 2. Hirshfeld surface analysis demonstrates that the H⋯H contacts are decisive for both structures with contribution portions of 39.1% for 1 and 49.6% for 2. The O⋯H/H⋯O (1: 24.4% and 2: 9.6%) contacts are the characteristic intermolecular interactions, showing a pair of sharp spikes; while C⋯H/H⋯C contacts (1: 11.3% and 2: 21.7%), associated to the π⋯H/H⋯π interactions, can be illustrated as wings in the corresponding fingerprint plots. The C⋯C contacts are revealed for 2 (1.6%), associated to π⋯π interaction observed in the X-ray analysis. Two phosphoric triamides with the same [C(O)NH]P(O)[N(C)(C)]2 skeleton but with different molecular assemblies were investigated by the analysis of Hirshfeld surfaces and fingerprint plots.

A detailed theoretical and experimental study on the N[sbnd]H, P[dbnd]O and C[dbnd]O stretching frequencies in two new phosphoric triamides and a statistical comparison with analogous structures

Synthesis, X-ray structural, IR and NMR spectroscopic characterization of two new C(O)NHP(O)-based phosphoric triamides 2,3,6-F3C6H2C(O)NHP(O)[X]2 (X = NC4H8O and NHC(CH3)3) are presented. The NH…O(P/C) hydrogen bonds strengths and stretching frequencies shifts in hydrogen-bonded clusters forming graph-sets R22(8), R22(12)/R22(8) and R22(10)/R216 in the two new structures and the previously reported structure of 2-FC6H4C(O)NHP(O)[NHCH(CH3)2]2 are computationally evaluated using the Density Functional Theory (DFT) and the Atoms In Molecules (AIM) theory. It is in particular shown how the strengths of the different NH…O(P/C) HBs affect the frequencies shifts in hydrogen-bonded clusters. The study is completed by a statistical analysis using data from the Cambridge Structural Database (CSD) and the references that confirm the detailed experimental and theoretical investigations on the two new phosphoric triamides and the analogous compounds.

Synthesis and crystal structures of new phosphoric triamides: study of intermolecular interactions by semi-empirical calculations and Hirshfeld surface analysis

In the present paper, crystal structures and Hirshfeld surface analyses of two new phosphoric triamides [2,3,6-F3–C6H2C(O)NH]P(O)(X)2 (X=N(CH3)C6H11 and N(C2H5)2) and an improved model of [OH8C4N]3P(O) are investigated. Moreover, the semi-classical density sums (PIXEL) method, which enables the calculation of interaction energies for molecule–molecule pairs, and AIM calculations were used to evaluate intermolecular forces in the studied compounds. The previously reported structure [2,6-F2-C6H3C(O)NH]P(O)[NHC(CH3)3]2 with a [C(O)NH]P(O)[NH(C)]2 segment, which is different than the [C(O)NH]P(O)[N(C)(C)]2 segment in structures [2,3,6-F3–C6H2C(O)NH]P(O)(X)2, is compared to those of the newly determined structures. The Hirshfeld surface method shows that the crystal cohesions of structures [2,3,6-F3–C6H2C(O)NH]P(O)(X)2 are established via H···H, O···H/H···O, C···H/H···C, and F···H/H···F contacts, while for [OH8C4N]3P(O), H···H and O···H/H···O are the dominant contacts. From PIXEL and AIM calculations and the decomposition of the interaction energies for different molecular pairs, it is shown that the donor and acceptor capability of the atoms involved in an interaction introduces the nature and strength of that interaction. The more acidic NCP–H unit in the C(O)NHP(O) segment (compared to the NP–H unit in the P(O)[NH(C)]2 segment) and the higher H-atom acceptor group P=O (compared to C=O) in the studied structures form the strongest NCP–H···O=P intermolecular hydrogen bond.

Chiral one-dimensional hydrogen-bonded architectures constructed from single-enantiomer phosphoric triamides.

The two single-enantiomer phosphoric triamides N-(2,6-difluorobenzoyl)-N',N''-bis[(S)-(-)-α-methylbenzyl]phosphoric triamide, [2,6-F2-C6H3C(O)NH][(S)-(-)-(C6H5)CH(CH3)NH]2P(O), denoted L-1, and N-(2,6-difluorobenzoyl)-N',N''-bis[(R)-(+)-α-methylbenzyl]phosphoric triamide, [2,6-F2-C6H3C(O)NH][(R)-(+)-(C6H5)CH(CH3)NH]2P(O), denoted D-1, both C23H24F2N3O2P, have been investigated. In their structures, chiral one-dimensional hydrogen-bonded architectures are formed along [100], mediated by relatively strong N-H...O(P) and N-H...O(C) hydrogen bonds. Both assemblies include the noncentrosymmetric graph-set motifs R22(10), R21(6) and C22(8), and the compounds crystallize in the chiral space group P1. Due to the data collection of L-1 at 120 K and of D-1 at 95 K, the unit-cell dimensions and volume show a slight difference; the contraction in the volume of D-1 with respect to that in L-1 is about 0.3%. The asymmetric units of both structures consist of two independent phosphoric triamide molecules, with the main difference being seen in one of the torsion angles in the OPNHCH(CH3)(C6H5) part. The Hirshfeld surface maps of these levo and dextro isomers are very similar; however, they are near mirror images of each other. For both structures, the full fingerprint plot of each symmetry-independent molecule shows an almost asymmetric shape as a result of its different environment in the crystal packing. It is notable that NMR spectroscopy could distinguish between compounds L-1 and D-1 that have different relative stereocentres; however, the differences in chemical shifts between them were found to be about 0.02 to 0.001 ppm under calibrated temperature conditions. In each molecule, the two chiral parts are also different in NMR media, in which chemical shifts and P-H and P-C couplings have been studied.

Studying the effect of particle size on the antibacterial activity of some N-nicotinyl phosphoric triamides

ABSTRACTUsing ultrasonic top-to-down method, nanoparticles of two N-nicotinyl phosphoric triamides: C5H4NC(O)NHP(O)R, R = 4-CH3-NC5H10 (1), (CH3)3CNH2 (2) were prepared for the first time and characterized by 31P, 13C, 1H NMR, FTIR, scanning electron microscopy, energy dispersive X-ray. The average particle size of 1 and 2 were 60–70 and 40–50 nm, respectively, and the morphology was spherical for 1 and rod for 2. Solid state (powder) antibacterial effect of these compounds and two other similar reported ones, in their macro- and nanosizes, were evaluated with colony counting method on one Gram-positive (Staphylococcus aureus) and one Gram-negative (Escherichia coli) bacteria in Brain–Heart infusion culture medium. Results showed that all the macro- and nanosized compounds, except macrosized 1, were antibacterial and all nanoscaled ones had stronger antibacterial activity than their macroscaled analogues. The most effect of the particle size was observed for 1: by decreasing the particle sizes, the antibacterial activity state of 1 was changed from inactive (for macro) to potent (for nano).

Analysis, synthesis of some phosphoric triamides; database study approach

Analysis, synthesis of some phosphoric triamides; database study approach

The synergistic cooperation of NH⋯O and CH⋯O hydrogen bonds in the structures of three new phosphoric triamides

GRAPHICAL ABSTRACT

Chloro‐Bridged Hexanuclear Pd(II) Clusters Supported by cis‐Blocking Tris(imido)phosphate Trianions

AbstractTransition metal complexes derived from anionic polyimido ligands are very limited in the literature. Here we describe the deprotonation of alkyl substituted phosphoric triamides with bis(benzonitrile)palladium dichloride which results in the formation of chloro‐bridged hexanuclear palladium(II) clusters of formula {Pd3[(NR)3PO](Cl)3}2 in octahedral and prismatic geometries. These clusters consist of two trinuclear Pd3‐motifs, each cis‐protected by a tris(alkylimido)phosphate trianion, which are linked together by six μ2‐Cl bridges. A staggered arrangement of the two imido‐Pd3 units results in the formation of octahedral clusters (R=iBu, nBu, cHex, iPr and nPr), while an eclipsed conformation (R=tBu) gives rise to a prismatic cluster. A similar prismatic configuration was obtained for the mixed‐bridged clusters {Pd3[(NR)3PO](OAc)2(Cl)}2 (R=cHex and iPr), formed in the reaction involving the corresponding phosphoric triamide, Pd(OAc)2 and Pd(PhCN)2Cl2. The reaction of an octahedral cluster {Pd3[(NnPr)3PO](Cl)3}2 with 1,1’‐ferrocene dicarboxylic acid (FDC−H) gave the prismatic cluster {Pd3[(NnPr)3PO](FDC)(Cl)}2 which again consists of a mixed‐bridged environment with FDC and Cl− linkers. Further, treatment of the octahedral {Pd3[(NnPr)3PO](Cl)3}2 cluster with iPrNH2, a stronger nucleophile, leads to its symmetric cleavage and forms the trinuclear cluster {Pd3[(NR)3PO]Cl3(R'NH2)3}. We have also shown the catalytic activity of some of these Pd(II) complexes in the Suzuki reactions in both organic and aqueous phase conditions which suggest that all these imido‐Pd(II) clusters are still suitable for catalytic reactions.

Puckering behavior in six new phosphoric triamides containing aliphatic six- and seven-membered ring groups and a database survey of analogous ring-containing structures

The influence of a N heteroatom on the ring conformations of six- and seven-membered aliphatic rings in six new C(O)NHP(O)-based phosphoric triamide structures (analysed by X-ray crystallography) is investigated. Additionally the influence of steric and crystal packing effects is also studied by the analysis of Hirshfeld surfaces. The results are compared to analogous structures with three- to seven- aliphatic membered rings deposited in the Cambridge Structural Database. In the newly determined structures, the six-membered rings only show the near-chair conformation with a maximum deviation of the θ puckering parameter of 4.4° from the ideal chair value of 0°/180°, while the seven-membered rings are found in different conformations such as near-chair, twist chair and twist sofa.

Different molecular assemblies in two new phosphoric triamides with the same C(O)NHP(O)(NH)2 skeleton: crystallographic study and Hirshfeld surface analysis

Different molecular assemblies were compared in two new structures [4-CH3-C6H4C(O)NH]P(O)[NH]2(CH2)3, 1, and [4-CH3-C6H4C(O)NH]P(O)[NHC6H3(3,4-CH3)2]2, 2, belonging to the families of “cyclic phosphoric triamide” and “phosphoric triamide”, respectively. The differences in the hydrogen bond motifs were discussed (by single crystal X-ray diffraction) as a result of three factors: (1) action of two N atoms with a non-planar environment in 1 as an H-bond acceptor, (2) different orientations of three N–H bond vectors in two molecules and (3) different conformations of C=O and P=O groups. These differences lead to more complicated hydrogen bond pattern of 1, with respect to that of 2, as structure 1 may be considered as a model of four-acceptor–three-donor versus a two-acceptor–three-donor system in 2. The main discrepancies of 1 and 2, monitored by the Hirshfeld surface analysis, are related to the contribution portions of O···H/H···O contacts, in which compound 1 not only involves the greater existence of classical hydrogen bonds but also contains the further C–H···O weak interactions in its crystal packing with respect to compound 2. Instead, in 2, the shortage of O···H/H···O contacts has been partially compensated by the C···H/H···C interactions, due to the presence of more unsaturated carbon acceptors. The differences in assemblies are also reflected in the solid-state IR spectra, especially for the N–H vibration frequencies. The new compounds were further studied by 1D NMR experiments (1H, 13C, 31P), 2D NMR techniques [HMQC and HMBC (H–C correlation), HSQC (N–H correlation)], high-resolution ESI–MS, EI–MS spectrometry and IR spectroscopy.

Syntheses and structures of four new mixed-amide phosphoric triamides.

Phosphoric triamides have extensive applications in biochemistry and are also used as O-donor ligands. Four new mixed-amide phosphoric triamide structures, namely rac-N-tert-butyl-N',N''-dicyclohexyl-N''-methylphosphoric triamide, C17H36N3OP, (I), rac-N,N'-dicyclohexyl-N'-methyl-N''-(p-tolyl)phosphoric triamide, C20H34N3OP, (II), N,N',N''-tricyclohexyl-N''-methylphosphoric triamide, C19H38N3OP, (III), and 2-[cyclohexyl(methyl)amino]-5,5-dimethyl-1,3,2λ(5)-diazaphosphinan-2-one, C12H26N3OP, (IV), have been synthesized and studied by X-ray diffraction and spectroscopic methods. Structures (I) and (II) are the first diffraction studies of acyclic racemic mixed-amide phosphoric triamides. The P-N bonds resulting from the different substituent -N(CH3)(C6H11), (C6H11)NH-, 4-CH3-C6H4NH-, (tert-C4H9)NH- and -NHCH2C(CH3)2CH2NH- groups are compared, along with the different molecular volumes and electron-donor strengths. In all four structures, the molecules form extended chains through N-H...O hydrogen bonds.

Spiro- and substituted tetrahydrobenzo[b]thiophene-triazaphospholes and phosphoramidates as potent antineoplastic agents: synthesis, biological evaluation, and SAR studies

New and efficient conjugate addition reaction of trimethyl, triethyl, and triisopropyl phosphites with 2-azido-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carbonitrile was developed and furnished spiro-triazaphosphole-oxide derivatives in ≈70 % yield. Contrary to these results, linear substituted phosphoramidates were obtained from the reaction of the azide with dimethyl, diethyl, and diisopropyl phosphites. N-Alkylamino- or 2-aminotetrahydrobenzo[b]thiophene-3-carbonitrile was also isolated in ~10 % yield from the previous two reactions. In the context of this work, hexaalkylphosphorus triamides were caused to react with the same substrate afforded the corresponding phosphoric triamides only in the presence of a protonating agent (dil. alcohol). The three reactions proceeded smoothly, cleanly, and were completed within ~6 h at r.t. Pharmacological evaluation results of antibreast, anticolon, and antiprostate carcinoma cell lines properties for the products were discussed in terms of structure–activity relationship to define a chromophore for lead compounds.

Database analysis of hydrogen bond patterns in phosphoric triamides completed with seven new compounds: a crystallographic and15N NMR study

We present the synthesis and characterization of seven new phosphoric triamides followed by analysis of hydrogen bond patterns of the new compounds as well as the phosphoric triamides found in the Cambridge Structural Database (CSD). The analysis of hydrogen bond patterns updates the previous work (Toghraee, Pourayoubi and Divjakovic in Polyhedron, 2011, 30, 1680) on phosphoric triamides with a C(O)NHP(O)[N]2 skeleton, and extends the analysis to other phosphoric triamides i.e. ones without a CO attached to the N of N–PO. For the new phosphoric triamides we also investigated their spectroscopic features (31P, 1H, 13C, and 15N NMR, mass spectroscopy, IR spectroscopy), measured the 1J(15N,31P) coupling constants and discussed the effective parameters.

Three new phosphoric triamides with a [C(O)NH]P(O)[N(C)(C)]2 skeleton: a database analysis of C-N-C and P-N-C bond angles.

In N,N,N',N'-tetraethyl-N''-(4-fluorobenzoyl)phosphoric triamide, C15H25FN3O2P, (I), and N-(2,6-difluorobenzoyl)-N',N''-bis(4-methylpiperidin-1-yl)phosphoric triamide, C19H28F2N3O2P, (II), the C-N-C angle at each tertiary N atom is significantly smaller than the two P-N-C angles. For the other new structure, N,N'-dicyclohexyl-N''-(2-fluorobenzoyl)-N,N'-dimethylphosphoric triamide, C21H33FN3O2P, (III), one C-N-C angle [117.08 (12)°] has a greater value than the related P-N-C angle [115.59 (9)°] at the same N atom. Furthermore, for most of the analogous structures with a [C(=O)NH]P(=O)[N(C)(C)]2 skeleton deposited in the Cambridge Structural Database [CSD; Allen (2002). Acta Cryst. B58, 380-388], the C-N-C angle is significantly smaller than the two P-N-C angles; exceptions were found for four structures with the N-methylcyclohexylamide substituent, similar to (III), one structure with the seven-membered cyclic amide azepan-1-yl substituent and one structure with an N-methylbenzylamide substituent. The asymmetric units of (I), (II) and (III) contain one molecule, and in the crystal structures, adjacent molecules are linked via pairs of N-H···O=P hydrogen bonds to form dimers.

Discrete and Polymeric Cu(II) Complexes Derived from in Situ Generated Pyridyl-Functionalized Bis(amido)phosphate Ligands, [PO2(NHPy)2]−

New examples of Cu(II) complexes containing in situ generated bis(amido)phosphate ligands, [PO2(NHPy)2]−, have been synthesized [(L1)−, where Py = 2-pyridyl, and (L2)−, where Py = 4-pyridyl). These anionic ligands were obtained by the P–N bond hydrolysis reaction of the corresponding phosphonium salts or phosphoric triamides in the presence of Lewis acidic Cu(II) ions in polar solvents. A discrete mononuclear complex {Cu[PO2(NH2Py)2]2} (3) was obtained for the in situ ligand featuring 2-pyridyl substituents, whereas a 1D coordination polymer {[Cu(PO2(NH4Py)2)2(H2O)2]·2DMF·2H2O}∞ (4) was obtained for the ligand containing 4-pyridyl functionalities. The structural analyses show that in 3 the ligand (L1)− is bonded to the metal ion in a chelating tridentate N,N,O coordination and the coordinated P–O group is oriented in a syn fashion with respect to the pyridylamino groups. However, in 4 the ligand (L2)− is bonded in a bridging fashion to two Cu(II) ions via its pyridyl nitrogen donors. The two phosphorus-bo...