N-[Bis(morpholin-4-yl)phosphino­yl]-2-chloro-2,2-difluoro­acetamide

The asymmetric unit of the title compound, C10H17ClF2N3O4P, consists of two independent mol­ecules in each of which the P atom adopts a distorted tetra­hedral environment with the P=O and N—H units in a syn orientation with respect to one another. Both morpholine rings in one of the phospho­ramide mol­ecules are disordered over two sets of sites, with site occupancies of 0.766 (7) and 0.234 (7) for one ring and 0.639 (10) and 0.361 (10) for the other. In the second phospho­ramide mol­ecule, one of the NC4H8O moieties is disordered over two sets of sites with site occupancies of 0.807 (6) and 0.193 (6). In the crystal, pairs of inter­molecular N—H⋯O(P) hydrogen bonds form two independent centrosymmetric dimers

The first phospho­ramide-mercury(II) complex with a Cl₂Hg-OP[N(C)(C)]₃ segment

Mercury(II) exhibits a strong preference for linear coordination which has been attributed to relativistic effects splitting the 6p orbitals and promoting sp hybridization. If the two ligands attached to the mercury(II) ion are weak donors, the metal ion can act as a good Lewis acid and expand its coordination number. Moreover, mercury has a special affinity for softer bases, such as S and N atoms, and has much less affinity for hard bases, such as those including an O atom. The asymmetric unit of di­chlorido­[tris­(piperidin-1-yl)phos­phane oxide- ΚO]mercury(II)-di­chlorido­ mercury(II) (2/1), [HgCl₂{(C₅H₁₀N)₃PO}]₂·[HgCl₂], is composed of one HgCl₂{(C₅H₁₀N)₃PO} complex and one half of a discrete HgCl₂ entity located on an inversion centre. The coordination environment around the HgII centre in the complex component is a distorted T-shape. Bond- valence-sum calculations confirm the three-coordination mode of the HgII atom of the complex mol­ ecule. The noncovalent nature of the Hg...Cl and Hg...O inter­actions in the structure are discussed

N-(2-Chloro-2,2-difluoro­acet­yl)-N′,N′′-diisopropyl­phospho­ric triamide

In the title compound, C8H17ClF2N3O2P, the phosphoryl group and the NH unit of the C(O)NHP(O) moiety adopt a syn conformation with respect to each other. The P atom is in a tetra­hedral coordination environment and the environment of the N atom of the C(O)NHP(O) moiety is essentially planar. In the crystal, adjacent mol­ecules are linked via N—H⋯O =P and N—H⋯O =C hydrogen bonds, building R 2 2(8) and R 2 2(12) rings in a linear arrangement parallel to [110]

N,N′-Dibenzyl-N′′-(2-chloro-2,2-difluoro­acet­yl)-N,N′-dimethyl­phospho­ric triamide

In the title mol­ecule, C18H21ClF2N3O2P, the P=O and N—H groups are syn to each other. The P atom adopts a slightly distorted tetra­hedral environment and the N atoms of the tertiary amine groups are bonded in an essentially planar geometry. In the crystal, pairs of inter­molecular N—H⋯O(P) hydrogen bonds form centrosymmetric dimers

Two new organotin(IV)-phosphoryl complexes: crystal structure and Hirshfeld surface analysis

Hirshfeld surfaces and two-dimensional fingerprint plots are used to visualize and analyse intermolecular interactions in two new organotin(IV)-phosphoryl complexes: [Sn(CH₃)₂[OP(O)(OCH₃)₂]₂]n (I) and {[(4-CH₃)C₆H₄NH][C₅H₉(4-CH₃)N]₂P(O)}Sn(CH₃)₂Cl₂ (II). In (I), the asymmetric unit is composed of the Sn(CH₃)₂[OP(O)(OCH₃)₂]₂ segment bonded to the neighbouring segment through Sn–O bonds thus constructing a coordination polymer. The tin centre has an Sn[C]₂[O]₄ environment with the axial positions occupied by methyl groups and with the oxygen atoms of Sn–O bonds located at the equatorial plane, while the oxygen atoms of OCH₃ groups do not take part in the coordination interaction. In (II), the asymmetric unit contains one complete molecule and the tin centre has an Sn[C]₂[Cl]₂O trigonal bipyramid coordination environment, where the phosphoric triamide ligand and one of the chlorine atoms are placed in axial positions. Hirshfeld surface analysis on the asymmetric unit of (I) shows a contribution of 5.9 % of total interactions in crystal for Sn…O contacts related to involving of four-coordinated Sn site of asymmetric unit with two oxygen atoms of two neighbouring phosphates in the coordination polymer. The Sn centre in the asymmetric unit of (II) receives a second interaction from chlorine atom that, however, has negligible contribution portion in the total interactions (evaluated by fingerprint plot) in the crystal. On the other hand, this chlorine affects the geometry at the Sn atom and causes the open C–Sn–C bond angle (of 140.18(24)°). For both structures, the contribution of H…H contacts to the total interaction is decisive, being 59.1 % for (I) and 73.9 % for (II); so that the one distinct spike observed in each of the fingerprint plots is related to H…H contacts. The O…H (34.1 %) in (I) and the H…Cl (20.2 %) in (II) are the characteristic intermolecular contacts in the corresponding structures, monitoring as two pairs of H-bond spikes for O…H and two sharp spikes for H…Cl. Furthermore, the structure (I) does not show the C…H interaction, whereas (II) including unsaturated carbon atoms manifests such interaction (5.7 %) as two very short spikes

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

<p>The supramolecular assemblies of three new phosphoric triamides, {(C₆H₅CH₂)(CH₃)N}₂(4-CH₃-C₆H₄C(O)NH)P(O) (<b>1</b>), {(C₆H₁₁)(CH₃)N}₂(4-CH₃-C₆H₄C(O)NH)P(O) (<b>2</b>) and {(C₂H₅)₂N}₂(4-CH₃-C₆H₄C(O)NH)P(O) (<b>3</b>) were studied by single crystal X-ray diffraction as well as by Hirshfeld surface analysis. It was found that a synergistic cooperation of NH⋯O and CH⋯O hydrogen bonds occurs in all three structures, but forming unique supramolecular architectures individually. Along with the presence of centrosymmetric dimers in <b>1, 2</b> and <b>3</b>, based on a classical NH⋯O hydrogen bond, the presence of weak CH⋯O interactions play an additional and vital role in crystal architecture and construction of the final assemblies, collectively identified as a centrosymmetric dimer (0D), a 1-D array and a 3-D network, respectively. These differences in superstructures are related to the effect of aromatic, bulk and flexible groups used in the molecules designed, with a similar C(O)NHP(O) backbone. The NH⋯O contacts in <b>1, 2</b> and <b>3</b> are of the “resonance-assisted hydrogen bond” types and also the <i>anti</i>-cooperativity effect can be considered in the multi-acceptor sites P═O in <b>1</b> and <b>2</b> and C═O in <b>3</b>. All three compounds were further studied by 1D NMR experiments, 2D NMR techniques (HMQC and HMBC (H–C correlation)), high resolution ESI–MS, EI–MS spectrometry and IR spectroscopy methods.</p

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