Synthesis, crystal structure and Hirshfeld surface analysis of 2-phenyl-3-(prop-2-yn-1-yl-oxy)quin-oxaline.

In the title compound, C17H12N2O, the quinoxaline moiety shows deviations of 0.0288 (7) to -0.0370 (7) Šfrom the mean plane (r.m.s. deviation of fitted atoms = 0.0223 Å). In the crystal, corrugated layers two mol-ecules thick are formed by C-H⋯N hydrogen bonds and π-stacking inter-actions.

Diastereotopic groups in two new single-enanti-omer structures (R2)P(O)[NH-(+)CH(C2H5)(C6H5)] (R = OC6H5 and C6H5).

The crystal structures of two single-enanti-omer compounds, i.e. diphenyl [(R)-(+)-α-ethyl-benzyl-amido]-phosphate, C21H22NO3P or (C6H5O)2P(O)[NH-(R)-(+)CH(C2H5)(C6H5)] (I), and N-[(R)-(+)-α-ethyl-benz-yl]-P,P-di-phenyl-phosphinic amide, C21H22NOP or (C6H5)2P(O)[NH-R-(+)CH(C2H5)(C6H5)] (II), were studied. The different environments at the phospho-rus atoms, (O)2P(O)(N) and (C)2P(O)(N), allow the P=O/P-N bond strengths to be compared, as well as the N-H⋯O=P hydrogen-bond strengths, and P=O/N-H vibrations. The following characteristics related to diastereotopic C6H5O/C6H5 groups in I/II were considered: geometry parameters, contributions to the crystal packing, solution 13C/1H NMR chemical shifts, conformations, and NMR coupling constants. The phospho-rus-carbon coupling constants nJ PC (n = 2 and 3) in I and mJ PC (m = 1, 2, 3 and 4) in II were evaluated. For a comparative study, chiral analogous structures were retrieved from the Cambridge Structural Database (CSD) and their geometries and conformations are discussed.

Hydrogen-bond directionality and symmetry in [C(O)NH](N)2P(O)-based structures: a comparison between X-ray crystallography data and neutron-normalized values, and evaluation of reliability.

For [C(O)NH](N)2P(O)-based structures, the magnitude of the differences in the N-H...O, H...O=P and H...O=C angles has been evaluated when the N-H bond lengths, determined by X-ray diffraction, were compared to the neutron normalized values and the maximum percentage difference was obtained, i.e. about 3% for the angle even if the N-H bond lengths have a difference of about 30% (0.7 Šfor the X-ray and 1.03 Šfor the neutron-normalized value). The symmetries of the crystals are discussed with respect to the symmetry of the molecules, as well as to the symmetry of hydrogen-bonded motifs, and the role of the most directional hydrogen bond in raising the probability of obtaining centrosymmetric crystal structures is investigated. The work was performed by considering nine new X-ray crystal structures and 204 analogous structures retrieved from the Cambridge Structural Database.

Structural differences/similarities of diastereotopic groups in three new chiral phosphoramides.

The crystal structures of two single-enantiomer amidophosphoesters with an (O)2P(O)(N) skeleton and one single-enantiomer phosphoric triamide with an (N)2P(O)(N) skeleton were studied. The compounds are diphenyl [(R)-(+)-α-4-dimethylbenzylamido]phosphate, (I), and diphenyl [(S)-(-)-α-4-dimethylbenzylamido]phosphate, (II), both C21H22NO3P, and N-(2,6-difluorobenzoyl)-N',N''-bis[(R)-(+)-α-ethylbenzyl]phosphoric triamide, C25H28F2N3O2P, (III). The asymmetric units contain two amidophosphoester molecules for (I) and (II), and one phosphoric triamide molecule for (III). In the crystal structures of (I) and (II), molecules are assembled in a similar one-dimensional chiral ribbon architecture, but with almost a mirror-image relationship with respect to each other through N-H...O(P) and C-H...O(P) hydrogen bonds along [010]. In the crystal structure of (III), the chiral tape architecture along [100] is mediated by N-H...O(P) and N-H...O(C) hydrogen bonds, and the tapes are connected into slabs by C-H...O interactions (along the ab plane). The differences/similarities of the two diastereotopic phenoxy groups in (I)/(II) and the two chiral amine fragments in (III) were studied on the grounds of geometry, conformation and contribution to the crystal packing, as well as 1H and 13C signals in a solution NMR study.

Conformational analysis of two new organotin(IV) structures completed with a CSD survey.

The conformational flexibilities are studied in two new organotin(IV) complexes, namely, trans-dichloridodimethylbis[N,N',N''-tris(2-chlorobenzyl)phosphoric triamide]tin(IV), [Sn(CH3)2(C21H21Cl3N3OP)2Cl2] or Sn(CH3)2Cl2{OP[NHCH2C6H4(2-Cl)]3}2, (I), and bis(dipropylammonium) tetrachloridodimethylstannate(IV), [(CH3CH2CH2)2NH2]2[Sn(CH3)2Cl4], (II), and their analogous structures from the Cambridge Structural Database (CSD). The conformations are considered based on the N-P=O-Sn torsion angles for (I) and the C-C-C-N, C-C-N-C, C-N-C-C and N-C-C-C torsion angles for the two symmetry-independent [CH3CH2CH2NH2CH2CH2CH3]+ cations in (II), and the ±ac±sp±ac (ac = anticlinal and sp = synperiplanar) and ±ap±ap±ap±ap (ap = antiperiplanar) conformations are observed, respectively. In both structures, the four atoms in the corners of the square-planar segment of the octahedral shape around the Sn atom participate in normal hydrogen-bonding interactions as acceptors, which include two O and two Cl atoms for (I), and four Cl atoms for (II). However, the phosphoric triamide ligands block the environment around the Sn atom and limit the hydrogen-bond pattern to form a supramolecular ribbon assembly, while in the presence of small organic cations in (II), a two-dimensional hydrogen-bonded architecture is achieved. The weak interactions π-π, C-H...π and C-Cl...π in (I), and C-H...Cl in (II) do not change the dimensionality of the hydrogen-bond pattern. The 62 CSD structures analogous to (I), i.e. with an SnOPN3 segment (including 83 entries) fall into four categories of conformations based on the N-P=O-Sn torsion angles. The 132 [(CH3CH2CH2)2NH2]+ cations from 85 CSD structures are classified into seven groups based on the torsion angles noted for (II). Most of the CSD structures adopt the same associated conformations noted for (I) and (II). 15 [Sn(CH3)2Cl4]2- anions extracted from the CSD are compared with the structure of (II).

Conformational flexibility in amidophosphoesters: a CSD analysis completed with two new crystal structures of (C6H5O)2P(O)X [X = NHC7H13 and N(CH2C6H5)2].

The crystal structures of diphenyl (cycloheptylamido)phosphate, C19H24NO3P or (C6H5O)2P(O)(NHC7H13), (I), and diphenyl (dibenzylamido)phosphate, C26H24NO3P or (C6H5O)2P(O)[N(CH2C6H5)2], (II), are reported. The NHC7H13 group in (I) provides two significant hydrogen-donor sites in N-H...O and C-H...O hydrogen bonds, needed for a one-dimensional hydrogen-bond pattern along [100] in the crystal, while (II), with a (C6H5CH2)2N moiety, lacks these hydrogen bonds, but its three-dimensional supramolecular structure is mediated by C-H...π interactions. The conformational behaviour of the phenyl rings in (I), (II) and analogous structures from the Cambridge Structural Database (CSD) were studied in terms of flexibility, volume of the other group attached to phosphorus and packing forces. From this study, synclinal (±sc), anticlinal (±ac) and antiperiplanar (±ap) conformations were found to occur. In the structure of (II), there is an intramolecular Cortho-H...O interaction that imposes a +sc conformation for the phenyl ring involved. For the structures from the CSD, the +sc and ±ap conformations appear to be mainly imposed by similar Cortho-H...O intramolecular interactions. The large contribution of the C...H/H...C contacts (32.3%) in the two-dimensional fingerprint plots of (II) is a result of the C-H...π interactions. The differential scanning calorimetry (DSC) analyses exhibit peak temperatures (Tm) at 109 and 81 °C for (I) and (II), respectively, which agree with the strengths of the intermolecular contacts and the melting points.

The first coordination polymers with an [O]2[N]P(S)-Hg segment: a combined experimental, theoretical and database study.

The study of one-dimensional coordination polymers {Hg2Cl4L1}n (1), {HgBr2L1}n (2) and {Hg2Cl4L2}n (3) (L1 = (S)P(OC2H5)2NHC6H4NHP(S)(OC2H5)2 and L2 = (S)P(OC2H5)2NC4H8NP(S)(OC2H5)2) is the first such structural study of Hg(ii) coordination polymers with (O)2(N)PS-based ligands. The mercury atoms adopt a distorted trigonal pyramidal environment, Hg(Cl)3(S) for 1 and 3 and Hg(Br)2(S)2 for 2, and the difference observed in the stoichiometry of mercury halide to the thiophosphoramide ligand in 1 and 3 with respect to the one in 2 is a result of the formation of the Hg2Cl2 ring, however, the molar ratio 2 : 1 of HgX2 (X = Cl and Br) to ligand was used for the preparation of all three complexes. The strengths of mercury-sulfur and mercury-halide covalent bonds are evaluated by theoretical calculations (QTAIM and NBO) which show their principally electrostatic nature with a partial covalent contribution. The energies of interactions building supramolecular assemblies and intramolecular interactions, i.e. NHCl, NHBr, CHCl, CHBr, CHO, CHS and CHπ, are theoretically evaluated. The characteristic structural features arising from the aromatic/aliphatic linkers in the ligands and chloride/bromide attached to mercury are investigated by Hirshfeld surface analysis and fingerprint plots.

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.

The asymmetric unit of O,O'-dimethyl [(2,3,4,5,6-pentafluorophenyl)hydrazinyl]phosphonate, C8H8F5N2O3P, is composed of two symmetry-independent molecules with significant differences in the orientations of the C6F5 and OMe groups. In the crystal structure, a one-dimensional assembly is mediated from classical N-H...O hydrogen bonds, which includes R22(8), D(2) and some higher-order graph-set motifs. By also considering weak C-H...O=P and C-H...O-C intermolecular interactions, a two-dimensional network extends along the ab plane. The strengths of the hydrogen bonds were evaluated using quantum chemical calculations with the GAUSSIAN09 software package at the B3LYP/6-311G(d,p) level of theory. The LP(O) to σ*(NH) and σ*(CH) charge-transfer interactions were examined according to second-order perturbation theory in natural bond orbital (NBO) methodology. The hydrogen-bonded clusters of molecules, including N-H...O and C-H...O interactions, were constructed as input files for the calculations and the strengths of the hydrogen bonds are as follows: N-H...O [R22(8)] > N-H...O [D(2)] > C-H...O. The decomposed fingerprint plots show that the contribution portions of the F...H/H...F contacts in both molecules are the largest.

Two single-enantiomer amidophosphoesters: a database study on the chirality of (O)2P(O)(N)-based structures.

The crystal structures of two single-enantiomer amidophosphoesters with an (O)2P(O)(N) skeleton, i.e. diphenyl [(R)-(+)-α-methylbenzylamido]phosphate, (I), and diphenyl [(S)-(-)-α-methylbenzylamido]phosphate, (II), both C20H20NO3P, are reported. In both structures, chiral one-dimensional hydrogen-bonded architectures, along [010], are mediated by N-H...OP interactions. The statistically identical assemblies include the noncentrosymmetric graph-set motif C(4) and the compounds crystallize in the chiral space group P21. As a result of synergistic co-operation from C-H...O interactions, a two-dimensional superstructure is built including a noncentrosymmetric R44(22) hydrogen-bonded motif. A Cambridge Structural Database survey was performed on (O)2P(O)(N)-based structures in order to review the frequency of space groups observed in this family of compounds; the hydrogen-bond motifs in structures with chiral space groups and the types of groups inducing chirality are discussed. The 2,3JX-P (X = H or C) coupling constants from the NMR spectra of (I) and (II) have been studied. In each compound, the two diastereotopic C6H5O groups are different, which is reflected in the different chemical shifts and some coupling constants.

The (CF3C(O)NH)(C6H5CH2NH)2P(O) phosphoric triamide as a novel carrier with excellent efficiency for Cu(ii) in a liquid membrane transport system.

Transport of Ag(i), Cd(ii), Co(ii), Cu(ii), Ni(ii), Pb(ii) and Zn(ii) cations across a bulk liquid membrane (BLM) containing N,N'-dibenzyl-N''-(2,2,2-trifluoroacetyl)-phosphoric triamide (PTC) as a new carrier is studied by atomic absorption spectrometry. The results show selective and efficient transport of the copper(ii) cation from aqueous solution in the presence of the other cations. Various factors are optimized in order to obtain maximum transport efficiency. The PTC ligand is characterized by single crystal X-ray diffraction analysis, IR, NMR (19F, 31P, 1H, 13C) and mass spectroscopy. The complex formation reaction between copper(ii) and PTC is studied by a conductometric method, which shows the 1 : 1 stoichiometry for ligand and copper(ii).

Decorated single-enantiomer phosphoramide-based silica/magnetic nanocomposites for direct enantioseparation.

The nano-composites Fe3O4@SiO2@(-O3Si[(CH2)3NH])P([double bond, length as m-dash]O)(NH-R(+)CH(CH3)(C6H5))2 (Fe3O4@SiO2@PTA(+)) and Fe3O4@SiO2@(-O3Si[(CH2)3NH])P([double bond, length as m-dash]O)(NH-S(-)CH(CH3)(C6H5))2 (Fe3O4@SiO2@PTA(-)) were prepared and used for the chiral separation of five racemic mixtures (PTA = phosphoric triamide). The separation results show chiral recognition ability of these materials with respect to racemates belonging to different families of compounds (amine, acid, and amino-acid), which show their feasibility to be potential adsorbents in chiral separation. The nano-composites were characterized by FTIR, TEM, SEM, EDX, XRD, and VSM. The VSM curves of nano-composites indicate their superparamagnetic property, which is stable after their use in the separation process. Fe3O4, Fe3O4@SiO2, Fe3O4@SiO2@PTA(+) and Fe3O4@SiO2@PTA(-) are regularly spherical with uniform shape and the average sizes of 17-20, 18-23, 36-47 and 43-52 nm, respectively.

A combined X-ray crystallography and theoretical study of N-H...OX (X is =P and -C) hydrogen bonds in two new structures with a (C-O)2(N)P(=Y) (Y is O and S) skeleton.

The crystal structures of N,N'-(cyclohexane-1,4-diyl)bis(O,O'-diphenylphosphoramide), C30H32N2O6P2 or (C6H5O)2P(O)(1-NH)(C6H10)(4-NH)P(O)(OC6H5)2, (I), and N,N'-(1,4-phenylene)bis(O,O'-dimethylthiophosphoramide), C10H18N2O4P2S2 or (CH3O)2P(S)(1-NH)(C6H4)(4-NH)P(S)(OCH3)2, (II), have been investigated. In the structure of (I), with an (O)2(N)P(O) skeleton, two symmetry-independent phosphoramide molecules are linked through N-H...O=P hydrogen bonds. In the structure of (II), with an (O)2(N)P(S) skeleton, the ester O atoms take part in N-H...O-C hydrogen bonds as acceptors; the P=S groups do not participate in hydrogen-bonding interactions. The strengths of these hydrogen bonds were evaluated, using quantum chemical calculations with the GAUSSIAN09 software package at the B3LYP/6-311G(d,p) level of theory. For this, LP(O) to σ*(NH) charge transfers were studied, according to the second-order perturbation theory in natural bond orbital (NBO) methodology, for a three-component cluster of hydrogen-bonded molecules for both structures, including all of the independent N-H...O hydrogen bonds observed in the crystal packing. The details of the intermolecular interactions were studied by Hirshfeld surface maps and two-dimensional fingerprint plots.

Evaluation of N-H...S and N-H...π interactions in O,O'-diethyl N-(2,4,6-trimethylphenyl)thiophosphate: a combination of X-ray crystallographic and theoretical studies.

In the crystal structure of O,O'-diethyl N-(2,4,6-trimethylphenyl)thiophosphate, C13H22NO2PS, two symmetrically independent thiophosphoramide molecules are linked through N-H...S and N-H...π hydrogen bonds to form a noncentrosymmetric dimer, with Z' = 2. The strengths of the hydrogen bonds were evaluated using density functional theory (DFT) at the M06-2X level within the 6-311++G(d,p) basis set, and by considering the quantum theory of atoms in molecules (QTAIM). It was found that the N-H...S hydrogen bond is slightly stronger than the N-H...π hydrogen bond. This is reflected in differences between the calculated N-H stretching frequencies of the isolated molecules and the frequencies of the same N-H units involved in the different hydrogen bonds of the hydrogen-bonded dimer. For these hydrogen bonds, the corresponding charge transfers, i.e. lp (or π)→σ*, were studied, according to the second-order perturbation theory in natural bond orbital (NBO) methodology. Hirshfeld surface analysis was applied for a detailed investigation of all the contacts participating in the crystal packing.

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.

A novel tubular hydrogen-bond pattern in a new diazaphosphole oxide: a combination of X-ray crystallography and theoretical study of hydrogen bonds.

In the structure of 2-(4-chloroanilino)-1,3,2λ4-diazaphosphol-2-one, C12H11ClN3OP, each molecule is connected with four neighbouring molecules through (N-H)2...O hydrogen bonds. These hydrogen bonds form a tubular arrangement along the [001] direction built from R33(12) and R43(14) hydrogen-bond ring motifs, combined with a C(4) chain motif. The hole constructed in the tubular architecture includes a 12-atom arrangement (three P, three N, three O and three H atoms) belonging to three adjacent molecules hydrogen bonded to each other. One of the N-H groups of the diazaphosphole ring, not co-operating in classical hydrogen bonding, takes part in an N-H...π interaction. This interaction occurs within the tubular array and does not change the dimension of the hydrogen-bond pattern. The energies of the N-H...O and N-H...π hydrogen bonds were studied by NBO (natural bond orbital) analysis, using the experimental hydrogen-bonded cluster of molecules as the input file for the chemical calculations. In the 1H NMR experiment, the nitrogen-bound proton of the diazaphosphole ring has a high value of 17.2 Hz for the 2JH-P coupling constant.

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

The N-H...O hydrogen bond is the characteristic interaction in the crystal structures of N-benzyl-P-phenyl-N'-(p-tolyl)phosphonic diamide, C20H21N2OP or (C6H5)P(O)(NHCH2C6H5)(NHC6H4-p-CH3), (I), diphenylphosphinic 1-methylpropylamide, C16H20NOP or (C6H5)2P(O)[NHCH(CH3)(C2H5)], (II), (S)-1-phenylethylammonium N-[(S)-1-phenylethyl]phenylphosphonamidate, C8H12N+·C14H15NO2P- or [S-(C6H5)CH(CH3)NH3][(C6H5)P(O){S-NHCH(CH3)(C6H5)}(O)], (III), and (4-methylbenzyl)ammonium diphenylphosphinate, C8H12N+·C12H10O2P- or [4-CH3-C6H4CH2NH3][(C6H5)2P(O)(O)], (IV). This article focuses on the N-H...O hydrogen bonds by considering the structures of (I), (II), (III) and (IV), and reviewing their analogous compounds, including 43 (C)P(O)(N)2, 102 (C)2P(O)(N), 31 (C)P(O)(N)(O) and 96 (C)2P(O)(O) structures, deposited in the Cambridge Structural Database (CSD). For the structures with a (C)P(O)(N)2 segment, only neutral hydrogen bonds were found in the CSD. The other three classes of compounds included both neutral and `charge-assisted' hydrogen bonds, and the (C)2P(O)(O) structures were particularly noticeable for a high number of cation-anion compounds. The overall tendencies of N...O distances in neutral and cation-anion compounds were compared. The N-H...O hydrogen-bond angles were also analyzed for the four classes of phosphorus compounds.

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)-dichloridomercury(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 Hg(II) centre in the complex component is a distorted T-shape. Bond-valence-sum calculations confirm the three-coordination mode of the Hg(II) atom of the complex molecule. The noncovalent nature of the Hg...Cl and Hg...O interactions in the structure are discussed.

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.

Hirshfeld surface analysis of two new phosphorothioic triamide structures.

Hirshfeld surfaces and two-dimensional fingerprint plots are used to analyse the intermolecular interactions in two new phosphorothioic triamide structures, namely N,N',N''-tris(3,4-dimethylphenyl)phosphorothioic triamide acetonitrile hemisolvate, P(S)[NHC6H3-3,4-(CH3)2]3·0.5CH3CN or C24H30N3PS·0.5CH3CN, (I), and N,N',N''-tris(4-methylphenyl)phosphorothioic triamide-3-methylpiperidinium chloride (1/1), P(S)[NHC6H4(4-CH3)]3·[3-CH3-C5H9NH2](+)·Cl(-) or C21H24N3PS·C6H14N(+)·Cl(-), (II). The asymmetric unit of (I) consists of two independent phosphorothioic triamide molecules and one acetonitrile solvent molecule, whereas for (II), the asymmetric unit is composed of three components (molecule, cation and anion). In the structure of (I), the different components are organized into a six-molecule aggregate through N-H···S and N-H···N hydrogen bonds. The components of (II) are aggregated into a two-dimensional array through N-H···S and N-H···Cl hydrogen bonds. Moreover, interesting features of packing arise in this structure due to the presence of a double hydrogen-bond acceptor (the S atom of the phosphorothioic triamide molecule) and of a double hydrogen-bond donor (the N-H unit of the cation). For both (I) and (II), the full fingerprint plot of each component is asymmetric as a consequence of the presence of three fragments. These analyses reveal that H···H interactions [67.7 and 64.3% for the two symmetry-independent phosphorothioic triamide molecules of (I), 30.7% for the acetonitrile solvent of (I), 63.8% in the phosphorothioic triamide molecule of (II) and 62.9% in the 3-methylpiperidinium cation of (II)] outnumber the other contacts for all the components in both structures, except for the chloride anion of (II), which only receives the Cl···H contact. The phosphorothioic triamide molecules of both structures include unsaturated C atoms, thus presenting C···H/H···C interactions: 17.6 and 21% for the two symmetry-independent phosphorothioic triamide molecules in (I), and 22.7% for the phosphorothioic triamide molecule of (II). Furthermore, the N-H···S hydrogen bonds in both (I) and (II), and the N-H...Cl hydrogen bonds in (II), are the most prominent interactions, appearing as large red spots on the Hirshfeld surface maps. The N···H/H···N contacts in structure (I) are considerable, whereas for (II), they give a negligible contribution to the total interactions in the system.

A new phosphorothioic triamide structure: P(S)[NHCH2C6H5]3.

The structure of N,N',N''-tribenzylphosphorothioic triamide, C21H24N3PS, (I), and analysis of the bond-angle sums at the N atoms for this compound, and for 74 structures with a P(S)[N]3 skeleton and the N atom in a three-coordinate geometry found in the Cambridge Structural Database [CSD; Groom & Allen (2014). Angew. Chem. Int. Ed. 53, 662-671], are reported. For (I), the bond-angle sum at one of the N atoms [359 (1)°] shows a nearly planar configuration, while the other two show a nonplanar geometry with bond-angle sums of 342 (1) and 347 (1)°. The location of the atoms attached to the nonplanar N atoms suggests an anti orientation of the corresponding lone electron pairs (LEPs) on these N atoms with respect to the P=S group. For 74 structures with a P(S)[N]3 skeleton and with the N atom in a three-coordinate geometry, the bond-angle sums at the N atoms were found to be in the range 293-360°. Among 307 such three-coordinate N atoms, 39% (120 N atoms) have bond-angle sums in the range 359-360°, in accordance with sp(2) hybridization, and 45% (138 N atoms) have bond-angle sums in the range 352-359°, with hybridization close to sp(2). For the orientation of the LEP with respect to the P=S group, the anti orientation was found to be a general rule for N atoms, with the corresponding bond-angle sums deviating by more than 8° from the planar value of 360°. In the title structure, the S atom takes part in intermolecular (N-H···)(N-H···)S hydrogen bonds, connecting the molecules into extended chains parallel to the b axis. The co-operation of one N atom in an N-H···S hydrogen bond as an H-atom donor, and in an N-H···N hydrogen bond as an acceptor, is a novel feature of the crystal structure.