Structural diversity in phosphoramidate’s chemistry: Syntheses, spectroscopic and X-ray crystallography studies

Gholivand, Khodayar; Shariatinia‬, Zahra; Mashhadi, Seyedeh Mahdieh; Daeepour, Farzaneh; Farshidnasab, Narjes; Mahzouni, Hamid Reza; Taheri, Nasrin; Amiri, Shadi; Ansar, Sheida

doi:10.1016/j.poly.2008.10.057

Cited by 24 publications

(18 citation statements)

References 32 publications

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“…Similar results were obtained for the nitrogen atoms of structure 2b that confirm the sp 2 hybridization for the N atoms, although due to the repulsion and steric interactions, some angles are greater, and others are smaller than 120°. This observation suggests the existence of partial multiple bond character between phosphorus and nitrogen atoms that has always been confirmed by the crystallographic data of our previously reported similar compounds [29][30][31][32][33][34].…”

Section: X-ray Crystallographysupporting

confidence: 84%

Polymorphism for a novel phosphoramidate; NMR and X-ray crystallography

et al. 2010

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New phosphoramidates with formula 3-NC 5 H 4 C(O)NHP(O)XY (X=Y=Cl (1), X=Y=NH-C(CH 3 ) 3 (2a,2b), X=Y=N(C 4 H 9 ) 2 (3), X=Cl, Y=N(C 2 H 5 ) 2 (4) were synthesized and characterized by IR, 1 H-, 13 C-, 31 P-NMR spectroscopy and CHN elemental analysis. Surprisingly, the reaction of compound 2a with LaCl 3 , 7H 2 O in 3:1 M ratio leads to a polymorph of this compound (2b). NMR spectra indicate that 2 J(PNH amide ) in 2b (7.0 Hz) is very much greater than in 2a (4.1 Hz), while d( 31 P) values are identical for both of them. In IR spectra, t(P=O) is weaker but t(C=O) is stronger in 2a than in 2b. The structures of 2a, 2b were determined by X-ray crystallography. These compounds form centrosymmetric dimers via two intermolecular P=O……H-N hydrogen bonds. Strong intermolecular N-H…N, N-H…O and weak C-H…O hydrogen bonds lead to a three-dimensional polymeric cluster in the 2a while intermolecular strong N-H……N and weak C-H……O hydrogen bonds form a two-dimensional polymeric chain in 2b.

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Section: X-ray Crystallographysupporting

confidence: 84%

Polymorphism for a novel phosphoramidate; NMR and X-ray crystallography

et al. 2010

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“…The negative value for 2 may be attributed to the magnetic anisotropy of aromatic rings (of two NHC 6 H 3 -3,4-(CH 3 ) 2 groups) on the phosphorus atom existing in the cone-shaped shielding zone. Such negative values of phosphorus chemical shifts were also found in the 31 P NMR of analogous compounds, which typically include NHC 6 H 4 -4-CH 3 group bonded to P atom, for example: (Gholivand et al 2009). Table 1 lists the 1 H and 13 C NMR assignments of both compounds, with the assignments achieved by 2D experiments.…”

Section: Ir and Nmr Studymentioning

confidence: 73%

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

et al. 2017

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Different molecular assemblies were compared in two new structures [4-CH 3 -C 6 H 4 C(O)NH]P(O) [NH] 2 (-CH 2 ) 3 , 1, and [4-CH 3 -C 6 H 4 C(O)NH]P(O) [NHC 6 H 3 (3, ) 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-acceptorthree-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 ( 1 H, 13 C, 31 P), 2D NMR techniques [HMQC and HMBC (H-C correlation), HSQC (N-H correlation)], high-resolution ESI-MS, EI-MS spectrometry and IR spectroscopy.

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“…This coupling was observed neither for compounds 11-19 nor for our previously reported phosphoric triamides. 24,25,[28][29][30][31][43][44][45] Typically, 4 J (H, H) coupling constants for the phenyl ring are in the range of 1-3 Hz and particular values seem to depend as much on the pattern of substitution as the nature of the substituent. 46 The 1 H NMR spectrum of compound 3 exhibited 3 J (H, H) cis = 10⋅3 Hz and 3 J (H, H) trans = 17⋅2 Hz for the coupling of terminal CH 2 protons of -CH=CH 2 with CH proton.…”

Section: Spectroscopic Studymentioning

confidence: 99%

“…This observation suggests the existence of partial multiple bond character between phosphorus and nitrogen atoms that has always been confirmed by the crystallographic data of our previously reported similar compounds. 24,25,[28][29][30][31]42,[49][50][51] These structures contain one amidic hydrogen atom and form centrosymmetric dimers through strong intermolecular -P=O…H-N-hydrogen bonds (2) 120(2) 120(2) Wavelength (Å) 0⋅71073 0⋅71073 0⋅71073 Crystal system, space group Triclinic, P-1 Tricliniic, P-1 …”

Section: Spectroscopic Studymentioning

confidence: 99%

“…The structures of several phosphoramidates have already been determined by X-ray crystallography. [20][21][22][23][24][25][26][27][28][29][30][31] N-benzoylphosphoric triamides are one such significant category of phosphoramidates derivatives. In fact, the existence of -C(O)NHP(O)-skeleton as peptide group in these molecules cause them biologically active urease inhibitors.…”

Section: Introductionmentioning

confidence: 99%

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N-2,4-dichlorobenzoyl phosphoric triamides: Synthesis, spectroscopic and X-ray crystallography studies

2010

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New phosphoric triamides 1-9 were synthesized by the reaction of N-2,4-dichlorobenzoyl phosphoramidic dichloride with various cyclic aliphatic amines and the products were characterized by 1 H, 13 C, 31 P NMR, IR spectroscopy and elemental analysis. Surprisingly, the 1 H NMR spectrum of 2 indicated long range 6 J (P, H) coupling constant = 1⋅3, 1⋅4 Hz and those of molecules 3, 4, 6-8 display longrange 4 J (H, H) coupling constants (1⋅8-1⋅9 Hz) for the coupling of aromatic protons in 2,4-dichlorophenyl rings. 1 H NMR spectra indicated 3 J (PNCH) for enantiotopic and diastereotopic benzylic CH 2 protons in compounds 7 and 8. The spectroscopic data of newly synthesized compounds were compared with those related N-benzoyl derivatives. The structures of compounds 5, 8 and 10 (2,4-Cl 2 -2 ) have been determined by X-ray crystallography. The structures form centrosymmetric dimers through intermolecular strong -P=O…H-N-hydrogen bonds. The dimers connect to each other via rather strong and weak C-H…O plus weak C-H…Cl H-bonds to produce a 1-D network for 5 while 3-D polymeric chains for 8 and 10.

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Structural diversity in phosphoramidate’s chemistry: Syntheses, spectroscopic and X-ray crystallography studies

Cited by 24 publications

References 32 publications

Polymorphism for a novel phosphoramidate; NMR and X-ray crystallography

Polymorphism for a novel phosphoramidate; NMR and X-ray crystallography

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

N-2,4-dichlorobenzoyl phosphoric triamides: Synthesis, spectroscopic and X-ray crystallography studies

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