Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615014527/fa3370sup1.cif
Contains datablocks New_Global_Publ_Block, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615014527/fa3370Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615014527/fa3370IIsup3.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615014527/fa3370Isup4.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615014527/fa3370IIsup5.cml
Supplementary material

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229615014527/fa3370sup6.pdf
Divided fingetprint plots

CCDC references: 1416438; 1416437

Introduction top

Three-dimensional Hirshfeld surfaces and the corresponding two-dimensional fingerprint maps are unique for each molecule/ion constituting the asymmetric unit of a crystal structure. They provide an easy means of comparing inter­molecular contacts relative to van der Waals radii through a simple red–white–blue colour scheme (McKinnon, Jayatilaka & Spackman, 2007).

So far, this type of analysis has been applied to the study of different families of compounds, such as polymorphic systems in CS2 at low temperature (Dziubek & Katrusiak, 2004), piracetam (Fabbiani et al., 2005), R-glycylglycine (Moggach, Allan, Parsons & Sawyer, 2006), L-serine (Moggach, Marshall & Parsons, 2006), benzene (Budzianowski & Katrusiak, 2006), tetra­thia­fulvalene (McKinnon, Fabbiani & Spackman, 2007), naphthalene, phenanthrene and pyrene (Fabbiani et al., 2006) and a series of tri­aryl­carbonyl derivatives (Bacchi et al., 2006). In addition, symmetry-independent molecules within one structure (Tarahhomi et al. 2013; Gholivand et al., 2015), cation–anion compounds (Gholizadeh et al., 2014; Ling et al., 2010) and cocrystals (Clausen et al., 2010) have also been studied by Hirshfeld surface analysis.

Recently, we have used this analysis to study inter­molecular inter­actions in three different families of phospho­ramides (phospho­ric tri­amide, amido­phospho­ester and amido­pyrophosphate) (Tarahhomi et al., 2013) and also in organotin(IV)–phospho­ramide complexes (Pourayoubi, Shoghpour Bayraq et al., 2014). Such analysis has not been used to date for the study of phospho­rothioic tri­amide compounds.

In this work, we present crystal structure analyses complemented by an investigation of molecular inter­actions for two new phospho­rothioic tri­amide structures, i.e. P(S)[NHC6H3-3,4-(CH3)2]3.CH3CN, (I), and P(S)[NHC6H4(4-CH3)]3[3-CH3—C5H9NH2]+.Cl-, (II) (see Schemes 1 and 2, respectively).

Experimental top

Synthesis and crystallization top

Synthesis of P(S)[NHC~6~H~3~-3,4-(CH~3~)~2~]~3~.CH~3~CN, (I) top

A solution of 3,4-di­methyl­aniline (4.32 g, 35.76 mmol) in dry CH3CN (10 ml) was added dropwise to a solution of thio­phospho­ryl chloride (1.01 g, 5.96 mmol) in the same solvent (10 ml) under stirring at 273 K. After 3 h, the stirring was stopped and the mixture was transferred to a beaker which was kept at room temperature to evaporate the solvent. After a few days, the solid formed was washed with distilled water. White single crystals were obtained from a solution of the product in CH3CN/CHCl3 (3:1 v/v) by slow evaporation at room temperature. Yield > 70%. IR (KBr disc, ν, cm-1): 653, 810, 927, 980, 1017, 1059, 1119, 1181, 1229, 1280, 1381, 1457, 1513, 1616, 2937, 3182 (NH).

Synthesis of P(S)[NHC~6~H~4~(4-CH~3~)]~3~[3-CH~3~—C~5~H~9ÑH~2~]^+^.Cl^-^, (II) top

Compound (II) was obtained in an unsuccessful effort to prepare a mixed amido–phospho­rothioic tri­amide from a reaction of thio­phospho­ryl chloride (0.500 g, 2.95 mmol) and p-toluidine (1.264 g, 11.80 mmol) in dry CH3CN (20 ml) at 273 K in the first step of the process. The solid formed was removed and then in the second step 3-methyl piperidine (0.585 g, 5.90 mmol) was added to the filtered solution under stirring at 273 K; the reaction time was 3 h per step. After stopping the second reaction, the mixture was transferred to a beaker to evaporate the solvent at room temperature. After a few days, the solid formed was washed with distilled water and dried. Crystals of (II) were obtained from a solution of the product in CH3OH/n-C7H16 (5:1 v/v) by slow evaporation at room temperature. Yield [relative to to P(S)Cl3] > 70%. IR (KBr disc, ν, cm-1): 652, 685, 762, 803, 888, 922, 1023, 1091, 1157, 1196, 1211, 1297, 1421, 1452, 1487, 1591, 2851, 2927, 3307 (NH).

Hirshfeld surface analysis and fingerprint plots top

The three-dimensional Hirshfeld surfaces (HSs), mapped with dnorm (Spackman & McKinnon, 2002) and two-dimensional fingerprint plots of structures (I) and (II) were generated using the Crystal Explorer software (Wolff et al., 2013).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. For both structures, H atoms bonded to N atoms were found in difference Fourier maps and their coordinates were refined with a distance restraint N—H = 0.87 Å with a standatd uncertainty of 0.01 Å. All other H atoms in both structures were kept in their geometrically expected positions, with C—H = 0.96 Å. The isotropic atomic displacement parameters of the H atoms were evaluated as 1.2Ueq of the parent atom. In (II), two methyl groups bonded to aromatic rings were found to be disordered by rotation around the C—C axis. The disordered H-atom positions were clearly identified from difference Fourier maps. The occupancies for the two disordered positions were 0.51 (2) and 0.49 (2) for the methyl group at C7, and 0.40 (3) and 0.60 (3) for the methyl group at C14.

Results and discussion top

The asymmetric unit of (I) consists of two symmetry-independent phospho­rothioic tri­amide molecules [(IA) and (IB) hereafter] and one aceto­nitrile (CH3CN) solvent molecule (Fig. 1), whereas, for (II), the asymmetric unit consists of one phospho­rothioic tri­amide molecule, one 3-methyl­piperidinium cation and one chloride anion (Fig. 2). Selected geometric parameters and hydrogen-bond geometries for (I) and (II) are given in Tables 2–5. In both structures, the P atoms are within a distorted tetra­hedral P[S][N]3 environment with the bond angles ranging from 98.85 (9) (N1a—P1a—N3a) to 116.27 (7)° (S1a—P1a—N3a) for (IA), from 97.25 (10) (N1b—P1b—N2b) to 116.55 (8)° (S1b—P1b—N2b) for (IB), and from 97.91 (6) (N1—P1—N3) to 117.55 (4)° [S1—P1—N1] for (II).

The Pδb S and P—N bond lengths are within the ranges observed in analogous structures (Pourayoubi, Abrishami et al., 2014). The P—N—C angles, with values close to 120° show that the hybridization of the N atom is close to sp2. All N atoms in the structures (I) and (II) have almost planar geometry, except for atom N3a of molecule (IA). In this case, a slightly nonplanar geometry is found, reflected in the bond-angle sum at N3a [353.3 (2)°].

Moreover, the positions of atoms directly bonded to N3a suggest an anti orientation of the lone electron pair with respect to the Pδb S bond. This is similar to the recently published analysis of the Cambridge Structural Database (CSD, Version 5.35, updated in February 2014; Groom & Allen, 2014) for structures with a P(S)[N]3 fragment including nonplanar N atoms within a [P]N[X][Y] environment (X and Y are any atoms) (Raissi Shabari et al., 2015).

In the crystal structure of (I), two (IA) molecules and two (IB) molecules, together with two aceto­nitrile solvent molecules, form a six-molecule aggregate, as shown in Fig. 3. In this arrangement, the four phospho­rothioic tri­amide molecules are hydrogen bonded to each other via N—H···S hydrogen bonds, forming R22(8) and R21(6) graph-set motifs (for the symbols defined for graph-set motifs, see Etter et al., 1990). The aceto­nitrile solvent molecules are linked at the two ends of this aggregate through N—H···N hydrogen bonds (Table 3), which accompany C—H···N inter­actions, forming R21(6) and R21(8) graph-set motifs.

In the crystal structure of (II), a two-dimensional arrangement parallel to the (101) plane is built from N—H···S and N—H···Cl hydrogen bonds involving the neutral molecules, cations and anions, as shown in Fig. 4. Within this pattern, two phospho­rothioic tri­amide molecules and two cations form R22(4) graph-set motifs, through a Pδb S···[H—N]2 inter­action with one N—H unit from each adjacent CH3—C5H9NH2+ cation. In this motif, we can distinguish two kinds of three-centred hydrogen bonding, i.e. S connected with two H-donor sites (double hydrogen-bond acceptor), and an N—H unit connected to two S atoms (bifurcated hydrogen bond). The other NH unit of the cation and all three NH units of the P(S)[NHC6H4(4-CH3)]3 molecule take part in N—H···Cl hydrogen bonds.

The three-dimensional HS generated for structures (I) and (II) are presented in Figs. 5 and 6, respectively. The contacts shown in red highlight the inter­molecular inter­actions with distances closer than the sum of the van der Waals (vdW) radii, while white is used for contacts near the vdW separation, and blue represents longer contacts (McKinnon, Jayatilaka & Spackman, 2007).

For structure (I), the Hirshfeld surfaces are plotted separately for the two symmetry-independent phospho­rothioic tri­amide molecules (Figs. 5a and 5b). In these maps, two different N—H···Sδb P hydrogen bonds, connecting molecules (IA) and (IB) to each other, appear as large red areas labelled 1 and 2. The other large red spots in Fig. 5a (labels 3 and 4) correspond to pairs of N—H···Sδb P hydrogen bonds between molecules (IA). On the other hand, molecule (IB) is also linked to the aceto­nitrile solvent molecule through N—H···N (labels 6 and 7) and C—H···N (label 8). These inter­actions are seen in Fig. 5(b) as large and small red areas, respectively, in accord with the strengths of the inter­actions.

Furthermore, it should be noted that the only remarkable H···C contact in structure (I) is related to the inter­action of one methyl H atom [on the 3,4-(CH3)2C6H3NH fragment] in molecule (IB) with the aromatic ring of an adjacent molecule (IB) (C15b—H2c15b···C2b; label 9 in Fig. 5b) that is seen as a pale-red spot. The HS for the aceto­nitrile solvent molecule does not provide any further information and was not included.

Concerning the structure of (II), the Hirshfeld surfaces were generated for the P(S)[NHC6H4-4-CH3]3 molecule, for the 3-CH3—C5H9NH2+ cation and for the Cl- anion and are presented in Figs. 6(a), 6(b) and 6(c), respectively.

Three NH units of the phospho­rothioic tri­amide molecule take part in different N—H···Cl hydrogen bonds with two neighbouring Cl- anions (labels 1–3 in Fig. 6a). These hydrogen bonds and the N—H···Cl hydrogen bond between the cation and the anion (which will be discussed later) are the most important inter­actions in structure (II) and are shown as large red spots on the HS.

The S atom of the phospho­rothioic tri­amide molecule is not only involved in the two N—H···S hydrogen bonds (labels 4 and 6) with the two neighbouring cations, but it also takes part in an S···S contact with a neighbouring phospho­rothioic tri­amide molecule (label 5). A search of the CSD shows that such an inter­action was found only in one structure with a P(S)[N]3 segment, viz. [H2N][CH3NH]P(S)–N(CH3)–P(S)[NH2]2 (CSD refcode MTHPAM; Herbst-Irmer et al., 1996).

The other light-red spots in Fig. 6(a) (labels 7–15) are related to C—H···C inter­actions between the C—H units of the cation and the phospho­rothioic tri­amide molecule, with the acceptor C atom belonging to the aromatic ring of the phospho­rothioic tri­amide molecule. Furthermore, one NH unit of the cation participates in an N—H···Cl inter­action that appears as a large red spot with label 16 in Fig. 6(b).

The Cl- anion in the crystal inter­acts with the above mentioned three NH units and with another one from the cation, resulting in four deep red spots in Fig. 6(c).

Two-dimensional fingerprint plots (FPs) are derived from the Hirshfeld surface (HS) by plotting the fraction of points on the surface as a function of (de, di), where de and di represent the distances from a point on the HS to the nearest atoms outside and inside the surface, respectively. The points are coloured as a function of the fraction of surface points, ranging from blue (relatively few points) through green (moderate fraction) to red (highest fraction) (McKinnon et al., 2004).

The FPs of the chemically equivalent molecules (IA) and (IB) (Figs. 7 and 8, and Fig. S1 in the Supporting information; in the following discussion, all figure numbers with a prefix `S' refer to figures that can be found in the Supporting information) are not identical because Hirshfeld surfaces and the corresponding FPs depend on the molecular conformation, as well as on the molecular environment in the crystal (Fabbiani et al., 2007). Molecule (IA), through two different N—H···S hydrogen bonds, is linked to molecules (IA) and (IB). For its part, molecule (IB) connects to molecule (IA) through the above-mentioned inter­action and also connects to the aceto­nitrile solvent molecule via C—H···N and N—H···N inter­actions. As a result, the full FPs of molecules (IA) and (IB) are different (Figs. 7a and 8a).

Inter­actions of the types H···H, C···H/H···C, S···H/H···S and N···H/H···N exist for both molecules [Figs. 7b, 7c, S1a and S1b, respectively, for molecule (IA) , and Figs. 8b, 8c, S2a and S2b, respectively, for molecule (IB)]. Moreover, C···C inter­actions for both (IA) and (IB) and N···N and C···N inter­actions for (IB) have negligible contributions, which are not visible in FPs. The H···H contacts represent the largest relative contribution, amounting to 67.7% in (IA) and 64.3% in (IB), with one distinct spike for both molecules (Figs. 7b and 8b).

Furthermore, in the fingerprint plots of the two molecules, the C···H/H···C contacts [17.6% for (IA) (Fig. 7c) and 21% for (IB) (Fig. 8c)] appear as two short spikes, while the S···H/H···S inter­actions [10.3% in (IA) (Fig. S1a) and 7.6% for (IB) (Fig. S2a)] develop as two sharp spikes.

On the other hand, the contribution of N···H/H···N inter­actions in (IA) is very small (1.1%; Fig. S1b), whereas in (IB), it becomes more considerable (4.3%; Fig. S2b), with the differences between the spikes in the N···H diagram being very clear.

For structure (II), FPs are shown in Figs. 9(a), 9(b), 9(c), S3(a) and S3(b) for the phospho­rothioic tri­amide molecule, in Figs. 10(a), 10(b), 10(c), S4(a) and S4(b) for the 3-methyl­piperidinium cation, and in Fig. 11 for the chloride anion. The full FP for each component is not symmetric (Figs. 9a, 10a and 11), as the three components have quite different shapes and also each component has a different environment.

Figs. 9(b) and 9(c) depict the majority H···H (63.8%) and C···H/H···C (22.7%) contacts, while Fig. S3(a) shows the FP for the less important S···H/H···S (6.7%) contacts for the phospho­rothioic tri­amide molecule. As for the C···H/H···C contacts (Fig. 9c), the shortest de + di (shown as blue points on the divided fingerprint) in spikes is near 2.6 Å and for S···H/H···S (Fig. S3a), it is near 2.3 Å. In contrast to the structure of (I), the N···H/H···N inter­actions have negligible contributions to the total inter­actions in (II).

For the [3-CH3—C5H9NH2]+ cation of (II), the full fingerprint plot is shown in Fig. 10(a). The most important inter­actions are the H···H contacts (62.9%; Fig. 10b), followed by H···C (22.5%; Fig. 10c), H···S (7.4%) and H···Cl (6.1%) (Figs. S4a and S4b, respectively). All the inter­actions discussed for the cation appear as a single spike in the region de > di in divided FPs, as expected. In other words, no S···H, Cl···H and meaningful C···H inter­actions were found with the cation, hence the corresponding fingerprint plots are quite asymmetric. Additionally, an acceptor spike is revealed for the Cl···H contacts which mostly concentrates in the region of de < di, the `lower part' of the fingerprint plot (Fig. 11). As there is no other inter­action received by this anion, the inter­actions mentioned involve a 100% contribution to the Hirshfeld surface.

Computing details top

For both compounds, data collection: (CrysAlis PRO; Agilent, 2014); cell refinement: (CrysAlis PRO; Agilent, 2014); data reduction: (CrysAlis PRO; Agilent, 2014); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: JANA2006 (Petříček et al., 2014); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures top
[Figure 1] Fig. 1. Displacement ellipsoid plot (50% probability) of the components of the asymmetric unit of structure (I), showing the atom-numbering scheme. H atoms are drawn as spheres of arbitrary radii.
[Figure 2] Fig. 2. Displacement ellipsoid plot (50% probability) of the asymmetric unit of structure (II), showing the atom-numbering scheme. H atoms are drawn as spheres of arbitrary radii. Two methyl groups exhibit disorder.
[Figure 3] Fig. 3. Part of the crystal packing of structure (I), showing the hexamolecular aggregate mediated by N—H···S and N—H···N hydrogen bonds. C—H···N hydrogen bonds are also shown. The hydrogen bonds are shown as dotted lines and H atoms not involved in hydrogen bonds have been omitted for clarity. Molecules of the same colour are related by symmetry. At the two ends of the aggregate, only one motif is labelled and the black dotted lines pertain to the labelled motifs.
[Figure 4] Fig. 4. A view of the two-dimensional array of (II) built from N—H···S and N—H···Cl hydrogen bonds. The hydrogen bonds are shown as dotted lines and H atoms not involved in hydrogen bonds have been omitted for clarity. The phosphorothioic triamide molecules, cations and anions are represented as blue, red and green, respectively.
[Figure 5] Fig. 5. Front and back views of the Hirshfeld surface for (IA) and (IB). For guidance, the phosphorothioic triamide molecules are shown on the left in the corresponding orientation, and the solvent molecule is shown near the HS of molecule (IB). The hydrogen bonds according to the labels in the figures are as follows, with the labels in parentheses: (a) molecule (IA): N3b—H1n3b···S1aδb P1a (1), N2a—H1n2a···S1bδb P1b (2), N1a—H1n1a···S1aδb P1a (3), N3a—H1n3a···S1aδb P1a (4) and C16a—H2c16a···H1c5b—C5b (5); (b) molecule (IB): N3b—H1n3b···S1aδb P1a (1), N2a—H1n2a···S1bδb P1b (2), C16a—H2c16a···H1c5b—C5b (5), N2b—H1n2b···N4—C25 (6), N1b—H1n1b···N4—C25 (7), C18b—H1c18b···N4—C25 (8) and C15b—H2c15b···C2b (9).
[Figure 6] Fig. 6. Front and back views of the Hirshfeld surface for the components of structure (II). The hydrogen bonds corresponding to the labels in figures are as follows, with the labels in parentheses: (a) phosphorothioic triamide molecule: N1—H1n1···Cl1 (1), N3—H1n3···Cl1 (2), N2—H1n2···Cl1 (3), N4—H2n4···S1 (4), S1···S1 (5), N4—H2n4···S1 (6), C22—H2c22···C13 (7), C22—H2c22···C12 (8), C22—H2c22···C8 (9), C26—H1c26···C15 (10), C26—H1c26···C20 (11), C26—H1c26···C16 (12), C19—H1c19···C27 (13), C23—H2c23···C2 (14) and C7—H2c7a···C11 (15); (b) 3-methylpiperidinium cation: C22—H2c22···C13 (7), C22—H2c22···C12 (8), C22—H2c22···C8 (9), C26—H1c26···C15 (10), C26—H1c26···C20 (11), C26—H1c26···C16 (12) and N4—H1n4···Cl1 (16); (c) chloride anion: N1—H1n1···Cl1 (1), N3—H1n3···Cl1 (2), N2—H1n2···Cl1 (3) and N4—H1n4···C1l (16).
[Figure 7] Fig. 7. Two-dimensional fingerprint plots of the molecule (IA): (a) full; (b) H···H; (c) C···H/H···C.
[Figure 8] Fig. 8. Two-dimensional fingerprint plots of the molecule IB: (a) full; (b) H···H; (c) C···H/H···C.
[Figure 9] Fig. 9. Two-dimensional fingerprint plots of the phosphorothioic triamide molecule of (II): (a) full; (b) H···H; (c) C···H/H···C.
[Figure 10] Fig. 10. Two-dimensional fingerprint plots of the 3-methyl piperidinium cation of (II): (a) full; (b) H···H; (c) H···C.
[Figure 11] Fig. 11. Two-dimensional fingerprint plot for the chloride anion of structure (II): Cl···H contacts.
(I) N,N',N''-Tris(3,4-dimethylphenyl)phosphorothioic triamide acetonitrile hemisolvate top
Crystal data top
2C24H30N3PS·C2H3NZ = 2
Mr = 888.2F(000) = 948
Triclinic, P1Dx = 1.218 Mg m3
Hall symbol: -P 1Cu Kα radiation, λ = 1.54184 Å
a = 11.8547 (5) ÅCell parameters from 6051 reflections
b = 13.5312 (4) Åθ = 3.3–67.0°
c = 15.3394 (6) ŵ = 1.94 mm1
α = 91.849 (3)°T = 120 K
β = 98.378 (3)°Polygon shape, white
γ = 94.991 (3)°0.19 × 0.17 × 0.11 mm
V = 2422.56 (16) Å3
Data collection top
Agilent Xcalibur (Atlas, Gemini ultra)
diffractometer
8394 independent reflections
Radiation source: X-ray tube6369 reflections with I > 3σ(I)
Mirror monochromatorRint = 0.042
Detector resolution: 5.1873 pixels mm-1θmax = 67.1°, θmin = 3.3°
ω scansh = 1314
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
k = 1613
Tmin = 0.658, Tmax = 1l = 1813
15711 measured reflections
Refinement top
Refinement on F234 constraints
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.053Weighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2)
S = 1.45(Δ/σ)max = 0.012
8394 reflectionsΔρmax = 0.36 e Å3
568 parametersΔρmin = 0.26 e Å3
6 restraints
Crystal data top
2C24H30N3PS·C2H3Nγ = 94.991 (3)°
Mr = 888.2V = 2422.56 (16) Å3
Triclinic, P1Z = 2
a = 11.8547 (5) ÅCu Kα radiation
b = 13.5312 (4) ŵ = 1.94 mm1
c = 15.3394 (6) ÅT = 120 K
α = 91.849 (3)°0.19 × 0.17 × 0.11 mm
β = 98.378 (3)°
Data collection top
Agilent Xcalibur (Atlas, Gemini ultra)
diffractometer
8394 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
6369 reflections with I > 3σ(I)
Tmin = 0.658, Tmax = 1Rint = 0.042
15711 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0426 restraints
wR(F2) = 0.053H atoms treated by a mixture of independent and constrained refinement
S = 1.45Δρmax = 0.36 e Å3
8394 reflectionsΔρmin = 0.26 e Å3
568 parameters
Special details top

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) Multi-scan absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F2 for refinement carried out on F and F2, respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement.

The program used for refinement, Jana2006, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S are usually larger than the ones from the SHELX program.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S1a0.45406 (5)0.84796 (4)0.40382 (4)0.02819 (18)
P1a0.53714 (5)0.97192 (4)0.37541 (4)0.02405 (18)
S1b0.42803 (5)0.77086 (4)0.13783 (4)0.03331 (19)
P1b0.44642 (5)0.63722 (4)0.17822 (4)0.02589 (18)
N2a0.57137 (17)0.95709 (13)0.27667 (13)0.0275 (6)
N3b0.49367 (17)0.64552 (13)0.28479 (13)0.0287 (6)
N1b0.32971 (17)0.55794 (14)0.16015 (13)0.0306 (6)
C12a0.7301 (2)1.16239 (18)0.11946 (16)0.0331 (8)
C11a0.6892 (2)1.06682 (18)0.08830 (18)0.0395 (9)
C19a0.8508 (2)0.81035 (17)0.46913 (17)0.0332 (8)
C5b0.0520 (2)0.4793 (2)0.22765 (19)0.0426 (9)
N1a0.46811 (17)1.07283 (13)0.37898 (13)0.0282 (6)
C7b0.0875 (2)0.73721 (19)0.33593 (19)0.0447 (10)
C10b0.6953 (2)0.52333 (19)0.06945 (17)0.0356 (8)
N2b0.52934 (17)0.57056 (14)0.12711 (14)0.0326 (7)
C7a0.1551 (3)0.9734 (2)0.1337 (2)0.0524 (11)
C4b0.0283 (2)0.56120 (19)0.27607 (18)0.0389 (9)
C9a0.6256 (2)1.02799 (16)0.22549 (15)0.0274 (7)
C20b0.6401 (2)0.42819 (17)0.44595 (17)0.0335 (8)
C3b0.1072 (2)0.64451 (18)0.28598 (16)0.0333 (8)
N3a0.65448 (16)1.01093 (13)0.44398 (13)0.0261 (6)
C24b0.6973 (3)0.35174 (19)0.5011 (2)0.0453 (10)
C10a0.6383 (2)1.00005 (18)0.14031 (17)0.0379 (9)
C21b0.6625 (2)0.52997 (17)0.47083 (16)0.0297 (8)
C18b0.5133 (2)0.46978 (16)0.31617 (17)0.0339 (8)
C19b0.5650 (2)0.40171 (17)0.36961 (17)0.0367 (9)
C24a1.0261 (2)0.7873 (2)0.5773 (2)0.0465 (10)
C20a0.9300 (2)0.84639 (17)0.54029 (17)0.0337 (8)
C6b0.1508 (2)0.47772 (18)0.18969 (17)0.0364 (8)
N40.4354 (3)0.35711 (18)0.10487 (19)0.0730 (13)
C16a0.7595 (2)1.29352 (18)0.24193 (18)0.0434 (10)
C3a0.2147 (2)1.04925 (19)0.20156 (17)0.0383 (9)
C11b0.8041 (2)0.5449 (2)0.05012 (17)0.0399 (9)
C17b0.53862 (19)0.57039 (16)0.33906 (15)0.0268 (7)
C15a0.7838 (2)1.23445 (19)0.06074 (18)0.0413 (9)
C4a0.1772 (2)1.14392 (18)0.21103 (17)0.0369 (9)
C5a0.2335 (2)1.21025 (19)0.27517 (18)0.0413 (9)
C14b0.7017 (2)0.68695 (18)0.13451 (17)0.0346 (8)
C23b0.7417 (2)0.56380 (19)0.55388 (18)0.0426 (9)
C18a0.7593 (2)0.86216 (16)0.43452 (16)0.0297 (8)
C22b0.6113 (2)0.59902 (16)0.41631 (15)0.0281 (7)
C14a0.6661 (2)1.12338 (16)0.25769 (16)0.0300 (8)
C9b0.6421 (2)0.59541 (17)0.11145 (16)0.0298 (8)
C1b0.2301 (2)0.56106 (16)0.19988 (15)0.0277 (7)
C13b0.8117 (2)0.70960 (19)0.11377 (18)0.0391 (9)
C15b0.9830 (2)0.6584 (2)0.0468 (2)0.0530 (11)
C22a0.82669 (19)0.99142 (16)0.54501 (15)0.0278 (7)
C13a0.7179 (2)1.19063 (16)0.20548 (16)0.0305 (8)
C16b0.8718 (3)0.8107 (2)0.1375 (2)0.0542 (11)
C17a0.74582 (19)0.95328 (15)0.47407 (15)0.0255 (7)
C21a0.9184 (2)0.94052 (17)0.57864 (16)0.0307 (8)
C8b0.0809 (3)0.5601 (2)0.3163 (2)0.0558 (12)
C2a0.3116 (2)1.02488 (18)0.25837 (17)0.0350 (8)
C2b0.2073 (2)0.64355 (17)0.24787 (16)0.0307 (8)
C12b0.8637 (2)0.6375 (2)0.07018 (17)0.0387 (9)
C250.4266 (2)0.2741 (2)0.09140 (18)0.0421 (10)
C6a0.3295 (2)1.18666 (17)0.33053 (18)0.0365 (9)
C23a1.0045 (2)0.98559 (19)0.65409 (18)0.0401 (9)
C1a0.3692 (2)1.09322 (17)0.32166 (16)0.0306 (8)
C8a0.0732 (3)1.1710 (2)0.1498 (2)0.0602 (12)
C260.4114 (3)0.16901 (19)0.0710 (2)0.0502 (11)
H1c11a0.6964611.0464430.0289980.0474*
H1c19a0.8590670.7468320.4422780.0398*
H1c5b0.0021720.4214980.2201860.0511*
H1c7b0.1470810.7883760.3304820.0536*
H2c7b0.014680.7587930.31220.0536*
H3c7b0.0880430.7236960.3970440.0536*
H1c10b0.6558340.4587290.0540840.0427*
H1c7a0.1895280.9119840.1414710.0629*
H2c7a0.0756790.9631850.1401570.0629*
H3c7a0.1619390.9961590.075940.0629*
H1c24b0.674480.3538850.5585940.0544*
H2c24b0.6751810.2869590.4733610.0544*
H3c24b0.7789470.3655210.5065660.0544*
H1c10a0.6116880.9340190.117180.0455*
H1c18b0.4606390.4481610.2640610.0406*
H1c19b0.5480960.3324190.3529210.0441*
H1c24a1.0220430.7765140.6383990.0558*
H2c24a1.0194260.7244250.5452510.0558*
H3c24a1.0980830.8231150.5720020.0558*
H1c6b0.1646350.4197070.1566050.0436*
H1c16a0.7544681.2977760.3038170.052*
H2c16a0.8376321.308440.2333350.052*
H3c16a0.7129221.3402940.2119770.052*
H1c11b0.8399840.4943450.0218830.0479*
H1c15a0.789571.2010010.0056250.0496*
H2c15a0.7371851.2886210.0501670.0496*
H3c15a0.8589141.2595070.0891270.0496*
H1c5a0.2059781.2743060.2819730.0496*
H1c14b0.6669170.7360780.1654320.0415*
H1c23b0.8161660.5422390.5508490.0512*
H2c23b0.747490.6349520.5602320.0512*
H3c23b0.7122590.5358480.6036530.0512*
H1c18a0.7064210.8353530.3841940.0356*
H1c22b0.6269630.668430.4328550.0338*
H1c14a0.658361.1433990.3169720.0359*
H1c15b0.9944360.7265950.0319760.0636*
H2c15b1.038510.645920.096330.0636*
H3c15b0.9915370.6160220.0027380.0636*
H1c22a0.8184311.0551750.5714230.0333*
H1c16b0.8337290.8439680.179470.0651*
H2c16b0.9497250.8046840.162960.0651*
H3c16b0.8706070.8483290.0854870.0651*
H1c8b0.0625090.5754970.3785610.067*
H2c8b0.127510.6087650.2894610.067*
H3c8b0.1220960.4955190.3063870.067*
H1c2a0.3377850.9601110.2530350.042*
H1c2b0.2613790.701330.2551250.0369*
H1c6a0.3685891.2343740.3748550.0438*
H1c23a1.0128170.9395910.7004480.0481*
H2c23a1.0770141.000280.6341750.0481*
H3c23a0.9788391.0457120.6758740.0481*
H1c8a0.0220861.1123950.1327530.0722*
H2c8a0.0346291.2183060.1796010.0722*
H3c8a0.0971691.1994690.0981570.0722*
H1c260.4245920.1341410.1245480.0602*
H2c260.334650.1508770.0420290.0602*
H3c260.4647230.1517550.0328710.0602*
H1n3b0.493 (2)0.7023 (11)0.3123 (15)0.0345*
H1n1b0.328 (2)0.5095 (14)0.1221 (14)0.0367*
H1n3a0.648 (2)1.0565 (14)0.4833 (13)0.0313*
H1n2a0.544 (2)0.9012 (11)0.2494 (15)0.033*
H1n2b0.506 (2)0.5086 (9)0.1151 (18)0.0391*
H1n1a0.481 (2)1.1070 (16)0.4289 (10)0.0339*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1a0.0323 (3)0.0238 (3)0.0294 (3)0.0003 (2)0.0100 (2)0.0012 (2)
P1a0.0248 (3)0.0229 (3)0.0253 (3)0.0017 (2)0.0070 (2)0.0007 (2)
S1b0.0380 (3)0.0305 (3)0.0302 (3)0.0039 (2)0.0006 (3)0.0008 (2)
P1b0.0239 (3)0.0278 (3)0.0258 (3)0.0021 (2)0.0040 (2)0.0025 (2)
N2a0.0334 (11)0.0233 (9)0.0261 (11)0.0021 (8)0.0090 (8)0.0021 (8)
N3b0.0319 (11)0.0247 (9)0.0286 (11)0.0039 (8)0.0016 (9)0.0032 (8)
N1b0.0274 (11)0.0317 (10)0.0312 (11)0.0011 (8)0.0050 (9)0.0115 (8)
C12a0.0291 (13)0.0393 (13)0.0332 (14)0.0059 (10)0.0090 (11)0.0092 (11)
C11a0.0497 (17)0.0386 (14)0.0341 (15)0.0028 (12)0.0199 (12)0.0016 (11)
C19a0.0343 (14)0.0304 (12)0.0386 (15)0.0068 (10)0.0159 (11)0.0001 (11)
C5b0.0377 (15)0.0441 (15)0.0456 (17)0.0088 (12)0.0132 (13)0.0033 (12)
N1a0.0300 (11)0.0270 (10)0.0291 (11)0.0061 (8)0.0074 (9)0.0007 (8)
C7b0.0417 (16)0.0490 (15)0.0463 (17)0.0149 (13)0.0113 (13)0.0032 (13)
C10b0.0344 (14)0.0397 (13)0.0341 (14)0.0084 (11)0.0074 (11)0.0008 (11)
N2b0.0315 (11)0.0299 (10)0.0372 (12)0.0000 (9)0.0116 (9)0.0069 (9)
C7a0.0486 (18)0.0539 (17)0.0524 (19)0.0025 (14)0.0028 (14)0.0071 (15)
C4b0.0329 (14)0.0475 (15)0.0371 (15)0.0019 (12)0.0089 (12)0.0013 (12)
C9a0.0262 (12)0.0293 (11)0.0285 (13)0.0041 (9)0.0089 (10)0.0047 (10)
C20b0.0348 (14)0.0318 (12)0.0363 (14)0.0042 (10)0.0116 (11)0.0067 (11)
C3b0.0309 (13)0.0408 (13)0.0282 (13)0.0070 (11)0.0025 (10)0.0016 (11)
N3a0.0278 (10)0.0235 (9)0.0272 (11)0.0027 (8)0.0059 (8)0.0031 (8)
C24b0.0536 (18)0.0359 (14)0.0474 (17)0.0057 (12)0.0075 (14)0.0125 (12)
C10a0.0480 (16)0.0300 (12)0.0385 (15)0.0009 (11)0.0173 (12)0.0003 (11)
C21b0.0284 (13)0.0342 (12)0.0282 (13)0.0039 (10)0.0085 (10)0.0033 (10)
C18b0.0383 (14)0.0284 (12)0.0327 (14)0.0010 (10)0.0012 (11)0.0016 (10)
C19b0.0421 (15)0.0258 (12)0.0420 (15)0.0001 (10)0.0077 (12)0.0002 (11)
C24a0.0405 (16)0.0543 (16)0.0476 (17)0.0178 (13)0.0075 (13)0.0056 (14)
C20a0.0296 (13)0.0377 (13)0.0370 (14)0.0064 (10)0.0126 (11)0.0066 (11)
C6b0.0360 (14)0.0357 (13)0.0362 (15)0.0034 (11)0.0072 (11)0.0064 (11)
N40.131 (3)0.0330 (14)0.0522 (17)0.0003 (15)0.0126 (17)0.0056 (12)
C16a0.0485 (17)0.0375 (14)0.0435 (17)0.0047 (12)0.0101 (14)0.0023 (12)
C3a0.0382 (15)0.0439 (14)0.0330 (14)0.0038 (11)0.0109 (12)0.0008 (11)
C11b0.0351 (15)0.0523 (16)0.0356 (15)0.0160 (12)0.0088 (12)0.0055 (12)
C17b0.0267 (12)0.0270 (11)0.0272 (12)0.0016 (9)0.0059 (10)0.0016 (9)
C15a0.0399 (16)0.0451 (15)0.0407 (16)0.0001 (12)0.0121 (12)0.0106 (12)
C4a0.0368 (15)0.0378 (13)0.0383 (15)0.0044 (11)0.0106 (12)0.0090 (11)
C5a0.0418 (16)0.0370 (14)0.0463 (17)0.0071 (12)0.0075 (13)0.0049 (12)
C14b0.0289 (13)0.0382 (13)0.0364 (14)0.0046 (10)0.0041 (11)0.0003 (11)
C23b0.0495 (17)0.0418 (14)0.0348 (15)0.0065 (12)0.0017 (13)0.0039 (12)
C18a0.0294 (13)0.0287 (12)0.0316 (13)0.0010 (10)0.0091 (10)0.0036 (10)
C22b0.0301 (13)0.0261 (11)0.0283 (13)0.0024 (9)0.0053 (10)0.0011 (10)
C14a0.0295 (13)0.0319 (12)0.0288 (13)0.0004 (10)0.0076 (10)0.0018 (10)
C9b0.0273 (13)0.0371 (13)0.0264 (13)0.0063 (10)0.0066 (10)0.0042 (10)
C1b0.0253 (12)0.0333 (12)0.0239 (12)0.0030 (9)0.0015 (10)0.0001 (10)
C13b0.0299 (14)0.0463 (14)0.0401 (15)0.0014 (11)0.0009 (11)0.0107 (12)
C15b0.0322 (15)0.078 (2)0.0536 (19)0.0126 (14)0.0118 (13)0.0228 (17)
C22a0.0283 (12)0.0280 (11)0.0281 (13)0.0003 (9)0.0099 (10)0.0010 (10)
C13a0.0248 (12)0.0304 (12)0.0358 (14)0.0021 (9)0.0018 (10)0.0051 (10)
C16b0.0366 (17)0.0560 (17)0.068 (2)0.0067 (14)0.0050 (15)0.0063 (15)
C17a0.0244 (12)0.0251 (11)0.0286 (12)0.0007 (9)0.0099 (10)0.0039 (9)
C21a0.0270 (13)0.0378 (13)0.0286 (13)0.0010 (10)0.0106 (10)0.0036 (10)
C8b0.0449 (18)0.0626 (19)0.064 (2)0.0009 (14)0.0263 (16)0.0024 (16)
C2a0.0330 (14)0.0388 (13)0.0357 (14)0.0039 (11)0.0121 (11)0.0077 (11)
C2b0.0277 (13)0.0326 (12)0.0306 (13)0.0025 (10)0.0015 (10)0.0034 (10)
C12b0.0271 (13)0.0587 (16)0.0323 (14)0.0089 (12)0.0055 (11)0.0156 (12)
C250.0541 (18)0.0388 (15)0.0326 (15)0.0001 (12)0.0081 (13)0.0038 (12)
C6a0.0374 (15)0.0315 (12)0.0415 (15)0.0043 (11)0.0075 (12)0.0058 (11)
C23a0.0318 (14)0.0502 (15)0.0373 (15)0.0016 (12)0.0033 (12)0.0046 (12)
C1a0.0279 (13)0.0370 (13)0.0288 (13)0.0020 (10)0.0097 (10)0.0073 (10)
C8a0.055 (2)0.066 (2)0.059 (2)0.0148 (16)0.0014 (16)0.0086 (16)
C260.059 (2)0.0400 (15)0.0527 (19)0.0002 (13)0.0159 (15)0.0003 (13)
Geometric parameters (Å, º) top
S1a—P1a1.9643 (8)C20a—C21a1.412 (3)
P1a—N2a1.635 (2)C6b—C1b1.393 (3)
P1a—N1a1.655 (2)C6b—H1c6b0.96
P1a—N3a1.6523 (18)N4—C251.128 (4)
S1b—P1b1.9501 (8)C16a—C13a1.498 (3)
P1b—N3b1.646 (2)C16a—H1c16a0.96
P1b—N1b1.6591 (19)C16a—H2c16a0.96
P1b—N2b1.652 (2)C16a—H3c16a0.96
N2a—C9a1.427 (3)C3a—C4a1.402 (4)
N2a—H1n2a0.866 (17)C3a—C2a1.407 (4)
N3b—C17b1.425 (3)C11b—C12b1.386 (4)
N3b—H1n3b0.865 (17)C11b—H1c11b0.96
N1b—C1b1.409 (3)C17b—C22b1.383 (3)
N1b—H1n1b0.86 (2)C15a—H1c15a0.96
C12a—C11a1.385 (3)C15a—H2c15a0.96
C12a—C15a1.511 (4)C15a—H3c15a0.96
C12a—C13a1.393 (4)C4a—C5a1.366 (3)
C11a—C10a1.382 (4)C4a—C8a1.517 (4)
C11a—H1c11a0.96C5a—C6a1.385 (4)
C19a—C20a1.378 (3)C5a—H1c5a0.96
C19a—C18a1.393 (3)C14b—C9b1.380 (3)
C19a—H1c19a0.96C14b—C13b1.398 (4)
C5b—C4b1.386 (4)C14b—H1c14b0.96
C5b—C6b1.384 (4)C23b—H1c23b0.96
C5b—H1c5b0.96C23b—H2c23b0.96
N1a—C1a1.412 (3)C23b—H3c23b0.96
N1a—H1n1a0.869 (17)C18a—C17a1.388 (3)
C7b—C3b1.502 (4)C18a—H1c18a0.96
C7b—H1c7b0.96C22b—H1c22b0.96
C7b—H2c7b0.96C14a—C13a1.393 (3)
C7b—H3c7b0.96C14a—H1c14a0.96
C10b—C11b1.375 (4)C1b—C2b1.385 (3)
C10b—C9b1.396 (4)C13b—C16b1.495 (4)
C10b—H1c10b0.96C13b—C12b1.400 (4)
N2b—C9b1.406 (3)C15b—C12b1.514 (4)
N2b—H1n2b0.864 (13)C15b—H1c15b0.96
C7a—C3a1.492 (4)C15b—H2c15b0.96
C7a—H1c7a0.96C15b—H3c15b0.96
C7a—H2c7a0.96C22a—C17a1.394 (3)
C7a—H3c7a0.96C22a—C21a1.383 (3)
C4b—C3b1.390 (3)C22a—H1c22a0.96
C4b—C8b1.513 (4)C16b—H1c16b0.96
C9a—C10a1.381 (4)C16b—H2c16b0.96
C9a—C14a1.387 (3)C16b—H3c16b0.96
C20b—C24b1.503 (4)C21a—C23a1.502 (3)
C20b—C21b1.409 (3)C8b—H1c8b0.96
C20b—C19b1.380 (3)C8b—H2c8b0.96
C3b—C2b1.398 (4)C8b—H3c8b0.96
N3a—C17a1.421 (3)C2a—C1a1.380 (3)
N3a—H1n3a0.86 (2)C2a—H1c2a0.96
C24b—H1c24b0.96C2b—H1c2b0.96
C24b—H2c24b0.96C25—C261.436 (4)
C24b—H3c24b0.96C6a—C1a1.397 (3)
C10a—H1c10a0.96C6a—H1c6a0.96
C21b—C23b1.501 (3)C23a—H1c23a0.96
C21b—C22b1.393 (3)C23a—H2c23a0.96
C18b—C19b1.378 (3)C23a—H3c23a0.96
C18b—C17b1.391 (3)C8a—H1c8a0.96
C18b—H1c18b0.96C8a—H2c8a0.96
C19b—H1c19b0.96C8a—H3c8a0.96
C24a—C20a1.503 (4)C26—H1c260.96
C24a—H1c24a0.96C26—H2c260.96
C24a—H2c24a0.96C26—H3c260.96
C24a—H3c24a0.96
S1a—P1a—N2a108.21 (7)C10b—C11b—H1c11b119.02
S1a—P1a—N1a115.88 (8)C12b—C11b—H1c11b119.02
S1a—P1a—N3a116.27 (7)N3b—C17b—C18b122.24 (19)
N2a—P1a—N1a108.72 (10)N3b—C17b—C22b118.57 (19)
N2a—P1a—N3a108.38 (10)C18b—C17b—C22b119.2 (2)
N1a—P1a—N3a98.85 (9)C12a—C15a—H1c15a109.47
S1b—P1b—N3b108.31 (7)C12a—C15a—H2c15a109.47
S1b—P1b—N1b115.80 (8)C12a—C15a—H3c15a109.47
S1b—P1b—N2b116.55 (8)H1c15a—C15a—H2c15a109.47
N3b—P1b—N1b108.65 (10)H1c15a—C15a—H3c15a109.47
N3b—P1b—N2b109.73 (10)H2c15a—C15a—H3c15a109.47
N1b—P1b—N2b97.25 (10)C3a—C4a—C5a120.1 (2)
P1a—N2a—C9a128.87 (15)C3a—C4a—C8a119.1 (2)
P1a—N2a—H1n2a114.5 (16)C5a—C4a—C8a120.7 (2)
C9a—N2a—H1n2a116.0 (16)C4a—C5a—C6a121.1 (2)
P1b—N3b—C17b128.04 (15)C4a—C5a—H1c5a119.44
P1b—N3b—H1n3b117.7 (15)C6a—C5a—H1c5a119.44
C17b—N3b—H1n3b114.3 (15)C9b—C14b—C13b121.4 (2)
P1b—N1b—C1b127.14 (16)C9b—C14b—H1c14b119.32
P1b—N1b—H1n1b117.6 (17)C13b—C14b—H1c14b119.32
C1b—N1b—H1n1b115.3 (17)C21b—C23b—H1c23b109.47
C11a—C12a—C15a120.7 (2)C21b—C23b—H2c23b109.47
C11a—C12a—C13a118.2 (2)C21b—C23b—H3c23b109.47
C15a—C12a—C13a121.1 (2)H1c23b—C23b—H2c23b109.47
C12a—C11a—C10a121.7 (2)H1c23b—C23b—H3c23b109.47
C12a—C11a—H1c11a119.13H2c23b—C23b—H3c23b109.47
C10a—C11a—H1c11a119.13C19a—C18a—C17a118.8 (2)
C20a—C19a—C18a122.8 (2)C19a—C18a—H1c18a120.58
C20a—C19a—H1c19a118.61C17a—C18a—H1c18a120.58
C18a—C19a—H1c19a118.61C21b—C22b—C17b121.9 (2)
C4b—C5b—C6b122.4 (2)C21b—C22b—H1c22b119.07
C4b—C5b—H1c5b118.82C17b—C22b—H1c22b119.07
C6b—C5b—H1c5b118.82C9a—C14a—C13a121.1 (2)
P1a—N1a—C1a126.46 (15)C9a—C14a—H1c14a119.44
P1a—N1a—H1n1a115.7 (15)C13a—C14a—H1c14a119.44
C1a—N1a—H1n1a115.0 (17)C10b—C9b—N2b117.7 (2)
C3b—C7b—H1c7b109.47C10b—C9b—C14b118.8 (2)
C3b—C7b—H2c7b109.47N2b—C9b—C14b123.6 (2)
C3b—C7b—H3c7b109.47N1b—C1b—C6b118.4 (2)
H1c7b—C7b—H2c7b109.47N1b—C1b—C2b122.9 (2)
H1c7b—C7b—H3c7b109.47C6b—C1b—C2b118.7 (2)
H2c7b—C7b—H3c7b109.47C14b—C13b—C16b119.6 (2)
C11b—C10b—C9b119.9 (2)C14b—C13b—C12b119.5 (2)
C11b—C10b—H1c10b120.03C16b—C13b—C12b120.9 (2)
C9b—C10b—H1c10b120.03C12b—C15b—H1c15b109.47
P1b—N2b—C9b129.06 (16)C12b—C15b—H2c15b109.47
P1b—N2b—H1n2b117.0 (19)C12b—C15b—H3c15b109.47
C9b—N2b—H1n2b113.2 (19)H1c15b—C15b—H2c15b109.47
C3a—C7a—H1c7a109.47H1c15b—C15b—H3c15b109.47
C3a—C7a—H2c7a109.47H2c15b—C15b—H3c15b109.47
C3a—C7a—H3c7a109.47C17a—C22a—C21a122.2 (2)
H1c7a—C7a—H2c7a109.47C17a—C22a—H1c22a118.89
H1c7a—C7a—H3c7a109.47C21a—C22a—H1c22a118.89
H2c7a—C7a—H3c7a109.47C12a—C13a—C16a120.2 (2)
C5b—C4b—C3b118.2 (3)C12a—C13a—C14a120.0 (2)
C5b—C4b—C8b120.8 (2)C16a—C13a—C14a119.8 (2)
C3b—C4b—C8b121.0 (2)C13b—C16b—H1c16b109.47
N2a—C9a—C10a118.44 (19)C13b—C16b—H2c16b109.47
N2a—C9a—C14a122.8 (2)C13b—C16b—H3c16b109.47
C10a—C9a—C14a118.7 (2)H1c16b—C16b—H2c16b109.47
C24b—C20b—C21b120.5 (2)H1c16b—C16b—H3c16b109.47
C24b—C20b—C19b121.6 (2)H2c16b—C16b—H3c16b109.47
C21b—C20b—C19b117.9 (2)N3a—C17a—C18a122.83 (19)
C7b—C3b—C4b121.8 (2)N3a—C17a—C22a118.26 (19)
C7b—C3b—C2b118.4 (2)C18a—C17a—C22a118.9 (2)
C4b—C3b—C2b119.8 (2)C20a—C21a—C22a118.9 (2)
P1a—N3a—C17a126.12 (14)C20a—C21a—C23a120.9 (2)
P1a—N3a—H1n3a116.6 (16)C22a—C21a—C23a120.2 (2)
C17a—N3a—H1n3a110.6 (15)C4b—C8b—H1c8b109.47
C20b—C24b—H1c24b109.47C4b—C8b—H2c8b109.47
C20b—C24b—H2c24b109.47C4b—C8b—H3c8b109.47
C20b—C24b—H3c24b109.47H1c8b—C8b—H2c8b109.47
H1c24b—C24b—H2c24b109.47H1c8b—C8b—H3c8b109.47
H1c24b—C24b—H3c24b109.47H2c8b—C8b—H3c8b109.47
H2c24b—C24b—H3c24b109.47C3a—C2a—C1a120.6 (2)
C11a—C10a—C9a120.2 (2)C3a—C2a—H1c2a119.7
C11a—C10a—H1c10a119.89C1a—C2a—H1c2a119.7
C9a—C10a—H1c10a119.89C3b—C2b—C1b121.5 (2)
C20b—C21b—C23b120.7 (2)C3b—C2b—H1c2b119.28
C20b—C21b—C22b118.9 (2)C1b—C2b—H1c2b119.27
C23b—C21b—C22b120.4 (2)C11b—C12b—C13b118.4 (2)
C19b—C18b—C17b118.8 (2)C11b—C12b—C15b120.2 (3)
C19b—C18b—H1c18b120.59C13b—C12b—C15b121.4 (2)
C17b—C18b—H1c18b120.59N4—C25—C26177.4 (3)
C20b—C19b—C18b123.2 (2)C5a—C6a—C1a119.8 (2)
C20b—C19b—H1c19b118.38C5a—C6a—H1c6a120.12
C18b—C19b—H1c19b118.38C1a—C6a—H1c6a120.12
C20a—C24a—H1c24a109.47C21a—C23a—H1c23a109.47
C20a—C24a—H2c24a109.47C21a—C23a—H2c23a109.47
C20a—C24a—H3c24a109.47C21a—C23a—H3c23a109.47
H1c24a—C24a—H2c24a109.47H1c23a—C23a—H2c23a109.47
H1c24a—C24a—H3c24a109.47H1c23a—C23a—H3c23a109.47
H2c24a—C24a—H3c24a109.47H2c23a—C23a—H3c23a109.47
C19a—C20a—C24a121.3 (2)N1a—C1a—C2a122.6 (2)
C19a—C20a—C21a118.3 (2)N1a—C1a—C6a117.8 (2)
C24a—C20a—C21a120.3 (2)C2a—C1a—C6a119.6 (2)
C5b—C6b—C1b119.4 (2)C4a—C8a—H1c8a109.47
C5b—C6b—H1c6b120.28C4a—C8a—H2c8a109.47
C1b—C6b—H1c6b120.28C4a—C8a—H3c8a109.47
C13a—C16a—H1c16a109.47H1c8a—C8a—H2c8a109.47
C13a—C16a—H2c16a109.47H1c8a—C8a—H3c8a109.47
C13a—C16a—H3c16a109.47H2c8a—C8a—H3c8a109.47
H1c16a—C16a—H2c16a109.47C25—C26—H1c26109.47
H1c16a—C16a—H3c16a109.47C25—C26—H2c26109.47
H2c16a—C16a—H3c16a109.47C25—C26—H3c26109.47
C7a—C3a—C4a122.3 (2)H1c26—C26—H2c26109.47
C7a—C3a—C2a118.9 (2)H1c26—C26—H3c26109.47
C4a—C3a—C2a118.8 (2)H2c26—C26—H3c26109.47
C10b—C11b—C12b122.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3b—H1n3b···S1a0.866 (17)2.497 (19)3.3479 (19)168 (2)
N1b—H1n1b···N40.86 (2)2.54 (2)3.229 (3)137.5 (19)
N3a—H1n3a···S1ai0.87 (2)2.62 (2)3.430 (2)156 (2)
N2a—H1n2a···S1b0.866 (17)2.57 (2)3.410 (2)163 (2)
N2b—H1n2b···N40.865 (14)2.138 (14)2.994 (3)171 (2)
N1a—H1n1a···S1ai0.869 (17)2.606 (16)3.435 (2)160.2 (18)
C18b—H1c18b···N40.962.663.500 (4)146
Symmetry code: (i) x+1, y+2, z+1.
(II) N,N',N''-Tris(4-methylphenyl)phosphorothioic triamide–3-methylpiperidinium chloride (1/1) top
Crystal data top
C21H24N3PS·C6H14N+·ClF(000) = 1104
Mr = 517.1Dx = 1.203 Mg m3
Monoclinic, P21/nCu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yabcCell parameters from 25037 reflections
a = 14.2245 (2) Åθ = 3.7–67.1°
b = 14.2802 (3) ŵ = 2.56 mm1
c = 14.8887 (3) ÅT = 120 K
β = 109.2930 (16)°Polygon crystal, white
V = 2854.48 (10) Å30.25 × 0.21 × 0.17 mm
Z = 4
Data collection top
Agilent Xcalibur (Atlas, Gemini ultra)
diffractometer
5073 independent reflections
Radiation source: X-ray tube4567 reflections with I > 3σ(I)
Mirror monochromatorRint = 0.032
Detector resolution: 10.3745 pixels mm-1θmax = 67.1°, θmin = 3.7°
ω scansh = 1616
Absorption correction: analytical
(CrysAlis PRO; Agilent, 2014)
k = 1716
Tmin = 0.950, Tmax = 0.970l = 1717
48608 measured reflections
Refinement top
Refinement on F2171 constraints
R[F2 > 2σ(F2)] = 0.029H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.094Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0016I2)
S = 1.76(Δ/σ)max = 0.018
5073 reflectionsΔρmax = 0.22 e Å3
324 parametersΔρmin = 0.21 e Å3
11 restraints
Crystal data top
C21H24N3PS·C6H14N+·ClV = 2854.48 (10) Å3
Mr = 517.1Z = 4
Monoclinic, P21/nCu Kα radiation
a = 14.2245 (2) ŵ = 2.56 mm1
b = 14.2802 (3) ÅT = 120 K
c = 14.8887 (3) Å0.25 × 0.21 × 0.17 mm
β = 109.2930 (16)°
Data collection top
Agilent Xcalibur (Atlas, Gemini ultra)
diffractometer
5073 independent reflections
Absorption correction: analytical
(CrysAlis PRO; Agilent, 2014)
4567 reflections with I > 3σ(I)
Tmin = 0.950, Tmax = 0.970Rint = 0.032
48608 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02911 restraints
wR(F2) = 0.094H atoms treated by a mixture of independent and constrained refinement
S = 1.76Δρmax = 0.22 e Å3
5073 reflectionsΔρmin = 0.21 e Å3
324 parameters
Special details top

Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F2 for refinement carried out on F and F2, respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement.

The program used for refinement, Jana2006, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S are usually larger than the ones from the SHELX program.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cl10.65319 (3)0.28741 (2)0.11661 (2)0.02555 (12)
P10.69591 (3)0.00599 (2)0.22624 (2)0.01968 (12)
S10.60274 (3)0.00560 (2)0.09614 (2)0.02613 (13)
N10.66923 (9)0.06110 (8)0.30497 (8)0.0233 (4)
N30.80789 (9)0.03656 (8)0.23984 (8)0.0229 (4)
N20.70379 (9)0.11425 (8)0.26446 (8)0.0224 (4)
N40.44950 (9)0.82533 (9)0.07546 (8)0.0254 (4)
C100.77323 (11)0.28112 (11)0.46434 (11)0.0282 (5)
C10.58281 (10)0.05689 (10)0.33122 (9)0.0234 (4)
C160.86072 (11)0.07470 (10)0.13859 (10)0.0259 (5)
C150.87657 (11)0.00449 (9)0.19685 (10)0.0221 (5)
C60.56747 (12)0.12803 (11)0.38877 (11)0.0306 (5)
C200.96611 (11)0.05264 (11)0.21695 (10)0.0271 (5)
C130.82515 (10)0.10139 (10)0.42776 (10)0.0242 (5)
C80.75209 (10)0.15001 (10)0.35708 (9)0.0212 (4)
C110.84679 (11)0.23370 (11)0.53513 (10)0.0279 (5)
C170.93459 (12)0.10374 (11)0.10310 (10)0.0294 (5)
C50.48415 (12)0.12713 (12)0.41693 (11)0.0357 (6)
C220.51320 (11)0.75315 (11)0.13982 (10)0.0282 (5)
C40.41320 (12)0.05676 (12)0.38943 (11)0.0329 (5)
C120.87094 (11)0.14382 (11)0.51526 (10)0.0276 (5)
C181.02519 (12)0.05733 (11)0.12350 (11)0.0309 (5)
C240.29991 (11)0.77174 (12)0.11077 (11)0.0303 (5)
C90.72596 (11)0.23976 (10)0.37666 (10)0.0255 (5)
C20.51295 (11)0.01440 (11)0.30268 (11)0.0281 (5)
C230.36435 (11)0.85513 (11)0.10584 (10)0.0294 (5)
C250.36353 (12)0.69582 (12)0.17469 (11)0.0335 (6)
C191.03898 (12)0.02141 (12)0.18114 (11)0.0319 (5)
C30.42938 (12)0.01366 (12)0.33169 (11)0.0321 (6)
C270.21634 (14)0.80332 (17)0.14638 (14)0.0523 (8)
C260.45110 (12)0.66829 (11)0.14295 (11)0.0312 (5)
C140.89760 (13)0.28004 (13)0.63041 (12)0.0381 (6)
C211.10526 (13)0.09118 (14)0.08533 (13)0.0437 (7)
C70.32302 (13)0.05646 (15)0.42111 (13)0.0442 (7)
H1c100.7548980.3433980.4763440.0338*
H1c160.7992060.108710.1232670.0311*
H1c60.6150090.1779540.4089870.0367*
H1c200.9775640.1078530.2558710.0325*
H1c130.8436080.0390920.4159850.029*
H1c170.9227290.1580330.0628580.0352*
H1c50.475090.176780.4567670.0428*
H1c220.5412890.7786270.2027140.0338*
H2c220.5660090.7352760.1165410.0338*
H1c120.9209650.1097760.5635590.0331*
H1c240.2705490.7456430.0483060.0364*
H1c90.6747550.2733530.3290730.0306*
H1c40.5222120.0641250.2630260.0337*
H1c230.3248160.900220.0614810.0352*
H2c230.3891940.8843920.167230.0352*
H1c250.3878870.7179540.2391660.0401*
H2c250.3231490.6416960.1736370.0401*
H1c191.1006620.055160.1966310.0382*
H1c30.3814890.0632630.3112170.0385*
H1c270.1730880.7513580.1450860.0627*
H2c270.2441550.8261230.2103860.0627*
H3c270.179040.8523970.1061430.0627*
H1c260.4916020.6231460.1865390.0375*
H2c260.4266910.6403360.0808880.0375*
H2c14a0.9667770.2630370.6529270.0457*0.60 (3)
H3c14a0.8915930.346810.6233340.0457*0.60 (3)
H1c14a0.866630.2596320.6753590.0457*0.60 (3)
H2c211.1338710.1479920.1172370.0525*
H1c211.156160.0442720.0962340.0525*
H3c211.0766530.1028020.0182690.0525*
H3c7a0.2673040.0305980.3716230.0531*0.51 (2)
H2c7a0.3078860.119430.4343150.0531*0.51 (2)
H1c7a0.3363940.0191540.4776020.0531*0.51 (2)
H1n10.7079 (11)0.1075 (9)0.3293 (11)0.0279*
H1n30.8260 (12)0.0839 (9)0.2769 (10)0.0275*
H1n20.6780 (11)0.1536 (10)0.2199 (9)0.0268*
H1n40.4265 (12)0.8015 (11)0.0179 (8)0.0304*
H2n40.4885 (11)0.8727 (9)0.0739 (12)0.0304*
H1c7b0.3012090.0068310.4234830.0531*0.49 (2)
H2c7b0.2705440.0918510.3768780.0531*0.49 (2)
H3c7b0.3398320.0841630.4831790.0531*0.49 (2)
H1c14b0.901710.2364160.6806310.0457*0.40 (3)
H2c14b0.9634580.2992480.6341330.0457*0.40 (3)
H3c25b0.8598320.3338150.6368570.0457*0.40 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0337 (2)0.02031 (19)0.01919 (18)0.00368 (12)0.00410 (14)0.00158 (11)
P10.02053 (19)0.0173 (2)0.01818 (19)0.00150 (12)0.00233 (14)0.00186 (12)
S10.0269 (2)0.0236 (2)0.0215 (2)0.00514 (13)0.00064 (15)0.00217 (12)
N10.0221 (6)0.0211 (6)0.0241 (6)0.0011 (5)0.0042 (5)0.0062 (5)
N30.0247 (6)0.0187 (6)0.0238 (6)0.0013 (5)0.0059 (5)0.0048 (5)
N20.0254 (6)0.0183 (6)0.0190 (6)0.0010 (4)0.0015 (5)0.0033 (4)
N40.0297 (6)0.0238 (7)0.0215 (6)0.0050 (5)0.0069 (5)0.0019 (5)
C100.0336 (8)0.0252 (8)0.0284 (8)0.0024 (6)0.0137 (6)0.0044 (6)
C10.0247 (7)0.0240 (7)0.0191 (6)0.0051 (5)0.0037 (5)0.0023 (5)
C160.0262 (7)0.0240 (8)0.0249 (7)0.0009 (6)0.0051 (6)0.0000 (6)
C150.0237 (7)0.0213 (7)0.0192 (7)0.0029 (5)0.0041 (6)0.0036 (5)
C60.0348 (8)0.0257 (8)0.0306 (8)0.0020 (6)0.0099 (6)0.0048 (6)
C200.0302 (7)0.0225 (8)0.0270 (7)0.0006 (6)0.0072 (6)0.0031 (6)
C130.0240 (7)0.0230 (8)0.0239 (7)0.0008 (5)0.0059 (6)0.0013 (5)
C80.0213 (6)0.0217 (7)0.0203 (6)0.0038 (5)0.0063 (5)0.0001 (5)
C110.0268 (7)0.0348 (8)0.0235 (7)0.0053 (6)0.0103 (6)0.0052 (6)
C170.0370 (8)0.0252 (8)0.0254 (7)0.0069 (6)0.0096 (6)0.0015 (6)
C50.0415 (9)0.0345 (9)0.0335 (8)0.0081 (7)0.0156 (7)0.0038 (7)
C220.0240 (7)0.0347 (9)0.0234 (7)0.0037 (6)0.0046 (6)0.0006 (6)
C40.0335 (8)0.0381 (9)0.0294 (8)0.0081 (7)0.0134 (6)0.0058 (6)
C120.0249 (7)0.0334 (9)0.0222 (7)0.0000 (6)0.0046 (6)0.0014 (6)
C180.0351 (8)0.0300 (8)0.0306 (8)0.0083 (6)0.0150 (6)0.0117 (6)
C240.0243 (7)0.0415 (9)0.0243 (7)0.0014 (6)0.0069 (6)0.0004 (6)
C90.0271 (7)0.0245 (8)0.0240 (7)0.0012 (6)0.0073 (6)0.0023 (6)
C20.0294 (8)0.0267 (8)0.0282 (8)0.0007 (6)0.0095 (6)0.0041 (6)
C230.0347 (8)0.0259 (8)0.0255 (7)0.0063 (6)0.0074 (6)0.0017 (6)
C250.0364 (8)0.0347 (9)0.0297 (8)0.0034 (7)0.0116 (7)0.0069 (6)
C190.0287 (8)0.0315 (8)0.0361 (9)0.0012 (6)0.0116 (7)0.0091 (7)
C30.0289 (8)0.0343 (9)0.0328 (8)0.0020 (6)0.0097 (7)0.0013 (6)
C270.0367 (10)0.0848 (16)0.0382 (10)0.0120 (9)0.0162 (8)0.0008 (9)
C260.0371 (8)0.0269 (8)0.0267 (7)0.0059 (6)0.0067 (6)0.0054 (6)
C140.0379 (9)0.0453 (10)0.0288 (8)0.0019 (7)0.0079 (7)0.0119 (7)
C210.0468 (10)0.0444 (11)0.0496 (10)0.0114 (8)0.0288 (9)0.0134 (8)
C70.0404 (10)0.0545 (12)0.0450 (10)0.0077 (8)0.0238 (8)0.0040 (8)
Geometric parameters (Å, º) top
Cl1—N1i3.2365 (12)C12—H1c120.96
Cl1—N3i3.2266 (12)C18—C191.389 (2)
Cl1—N23.2296 (12)C18—C211.511 (3)
Cl1—N4ii3.1848 (12)C24—C231.519 (2)
P1—S11.9524 (4)C24—C251.527 (2)
P1—N11.6523 (14)C24—C271.521 (3)
P1—N31.6536 (13)C24—H1c240.96
P1—N21.6383 (12)C9—H1c90.96
N1—C11.409 (2)C2—C31.392 (3)
N1—H1n10.861 (13)C2—H1c40.96
N3—C151.410 (2)C23—H1c230.96
N3—H1n30.857 (13)C23—H2c230.96
N2—C81.4171 (16)C25—C261.523 (3)
N2—H1n20.854 (13)C25—H1c250.96
N4—C221.4926 (18)C25—H2c250.96
N4—C231.488 (2)C19—H1c190.96
N4—H1n40.878 (12)C3—H1c30.96
N4—H2n40.879 (15)C27—H1c270.96
C10—C111.3912 (19)C27—H2c270.96
C10—C91.387 (2)C27—H3c270.96
C10—H1c100.96C26—H1c260.96
C1—C61.392 (2)C26—H2c260.96
C1—C21.388 (2)C14—H2c14a0.96
C16—C151.398 (2)C14—H3c14a0.96
C16—C171.386 (2)C14—H1c14a0.96
C16—H1c160.96C14—H1c14b0.96
C15—C201.390 (2)C14—H2c14b0.96
C6—C51.382 (3)C14—H3c25b0.96
C6—H1c60.96C21—H2c210.96
C20—C191.387 (3)C21—H1c210.96
C20—H1c200.96C21—H3c210.96
C13—C81.3952 (17)C7—H3c7a0.96
C13—C121.3884 (19)C7—H2c7a0.96
C13—H1c130.96C7—H1c7a0.96
C8—C91.392 (2)C7—H1c7b0.96
C11—C121.386 (2)C7—H2c7b0.96
C11—C141.515 (2)C7—H3c7b0.96
C17—C181.391 (2)H2c14a—H2c14b0.5824
C17—H1c170.96H3c14a—H3c25b0.5824
C5—C41.387 (2)H1c14a—H1c14b0.5824
C5—H1c50.96H3c7a—H1c7b0.9319
C22—C261.509 (2)H3c7a—H2c7b0.8781
C22—H1c220.96H2c7a—H2c7b0.9319
C22—H2c220.96H2c7a—H3c7b0.878
C4—C31.391 (2)H1c7a—H1c7b0.878
C4—C71.506 (3)H1c7a—H3c7b0.9319
N1i—Cl1—N3i45.38 (3)N4—C23—H1c23109.47
N1i—Cl1—N2107.11 (3)N4—C23—H2c23109.47
N1i—Cl1—N4ii137.18 (4)C24—C23—H1c23109.47
N3i—Cl1—N2101.20 (3)C24—C23—H2c23109.47
N3i—Cl1—N4ii156.34 (3)H1c23—C23—H2c23108.1
N2—Cl1—N4ii99.08 (3)C24—C25—C26111.54 (14)
S1—P1—N1117.55 (4)C24—C25—H1c25109.47
S1—P1—N3115.54 (5)C24—C25—H2c25109.47
S1—P1—N2107.06 (4)C26—C25—H1c25109.47
N1—P1—N397.91 (6)C26—C25—H2c25109.47
N1—P1—N2107.83 (7)H1c25—C25—H2c25107.32
N3—P1—N2110.58 (6)C20—C19—C18121.82 (15)
Cl1iii—N1—P1107.98 (6)C20—C19—H1c19119.09
Cl1iii—N1—C1125.24 (8)C18—C19—H1c19119.09
Cl1iii—N1—H1n111.4 (11)C4—C3—C2122.00 (15)
P1—N1—C1126.73 (9)C4—C3—H1c3119
P1—N1—H1n1118.7 (12)C2—C3—H1c3119
C1—N1—H1n1114.2 (12)C24—C27—H1c27109.47
Cl1iii—N3—P1108.36 (6)C24—C27—H2c27109.47
Cl1iii—N3—C15124.12 (8)C24—C27—H3c27109.47
Cl1iii—N3—H1n37.8 (12)H1c27—C27—H2c27109.47
P1—N3—C15127.52 (9)H1c27—C27—H3c27109.47
P1—N3—H1n3116.1 (12)H2c27—C27—H3c27109.47
C15—N3—H1n3116.3 (12)C22—C26—C25110.45 (13)
Cl1—N2—P1120.76 (5)C22—C26—H1c26109.47
Cl1—N2—C8108.34 (8)C22—C26—H2c26109.47
Cl1—N2—H1n212.9 (10)C25—C26—H1c26109.47
P1—N2—C8129.31 (9)C25—C26—H2c26109.47
P1—N2—H1n2112.8 (9)H1c26—C26—H2c26108.48
C8—N2—H1n2117.7 (9)C11—C14—H2c14a109.47
Cl1ii—N4—C22103.21 (8)C11—C14—H3c14a109.47
Cl1ii—N4—C23103.86 (7)C11—C14—H1c14a109.47
Cl1ii—N4—H1n410.2 (11)C11—C14—H1c14b109.47
Cl1ii—N4—H2n4118.1 (12)C11—C14—H2c14b109.47
C22—N4—C23112.63 (12)C11—C14—H3c25b109.47
C22—N4—H1n4108.0 (10)H2c14a—C14—H3c14a109.47
C22—N4—H2n4107.1 (9)H2c14a—C14—H1c14a109.47
C23—N4—H1n4109.2 (12)H2c14a—C14—H1c14b76.84
C23—N4—H2n4111.8 (11)H2c14a—C14—H2c14b35.32
H1n4—N4—H2n4107.9 (16)H2c14a—C14—H3c25b135.26
C11—C10—C9121.00 (14)H3c14a—C14—H1c14a109.47
C11—C10—H1c10119.5H3c14a—C14—H1c14b135.26
C9—C10—H1c10119.5H3c14a—C14—H2c14b76.84
N1—C1—C6117.92 (13)H3c14a—C14—H3c25b35.32
N1—C1—C2123.27 (14)H1c14a—C14—H1c14b35.32
C6—C1—C2118.81 (15)H1c14a—C14—H2c14b135.26
C15—C16—C17119.44 (14)H1c14a—C14—H3c25b76.84
C15—C16—H1c16120.28H1c14b—C14—H2c14b109.47
C17—C16—H1c16120.28H1c14b—C14—H3c25b109.47
N3—C15—C16123.43 (13)H2c14b—C14—H3c25b109.47
N3—C15—C20117.69 (13)C18—C21—H2c21109.47
C16—C15—C20118.84 (15)C18—C21—H1c21109.47
C1—C6—C5120.31 (14)C18—C21—H3c21109.47
C1—C6—H1c6119.85H2c21—C21—H1c21109.47
C5—C6—H1c6119.85H2c21—C21—H3c21109.47
C15—C20—C19120.41 (14)H1c21—C21—H3c21109.47
C15—C20—H1c20119.79C4—C7—H3c7a109.47
C19—C20—H1c20119.79C4—C7—H2c7a109.47
C8—C13—C12119.49 (14)C4—C7—H1c7a109.47
C8—C13—H1c13120.26C4—C7—H1c7b109.47
C12—C13—H1c13120.26C4—C7—H2c7b109.47
N2—C8—C13123.75 (13)C4—C7—H3c7b109.47
N2—C8—C9117.29 (11)H3c7a—C7—H2c7a109.47
C13—C8—C9118.95 (12)H3c7a—C7—H1c7a109.47
C10—C11—C12117.81 (13)H3c7a—C7—H1c7b58.07
C10—C11—C14120.23 (14)H3c7a—C7—H2c7b54.43
C12—C11—C14121.95 (13)H3c7a—C7—H3c7b141.01
C16—C17—C18122.59 (14)H2c7a—C7—H1c7a109.47
C16—C17—H1c17118.71H2c7a—C7—H1c7b141.01
C18—C17—H1c17118.71H2c7a—C7—H2c7b58.07
C6—C5—C4122.05 (16)H2c7a—C7—H3c7b54.43
C6—C5—H1c5118.97H1c7a—C7—H1c7b54.43
C4—C5—H1c5118.97H1c7a—C7—H2c7b141.01
N4—C22—C26109.68 (11)H1c7a—C7—H3c7b58.07
N4—C22—H1c22109.47H1c7b—C7—H2c7b109.47
N4—C22—H2c22109.47H1c7b—C7—H3c7b109.47
C26—C22—H1c22109.47H2c7b—C7—H3c7b109.47
C26—C22—H2c22109.47C14—H2c14a—H2c14b72.34
H1c22—C22—H2c22109.26C14—H3c14a—H3c25b72.34
C5—C4—C3116.97 (17)C14—H1c14a—H1c14b72.34
C5—C4—C7121.45 (16)C7—H3c7a—H1c7b60.96
C3—C4—C7121.58 (15)C7—H3c7a—H2c7b62.79
C13—C12—C11122.13 (12)H1c7b—H3c7a—H2c7b120
C13—C12—H1c12118.93C7—H2c7a—H2c7b60.96
C11—C12—H1c12118.93C7—H2c7a—H3c7b62.79
C17—C18—C19116.90 (16)H2c7b—H2c7a—H3c7b120
C17—C18—C21121.66 (14)C7—H1c7a—H1c7b62.79
C19—C18—C21121.44 (15)C7—H1c7a—H3c7b60.96
C23—C24—C25110.11 (12)H1c7b—H1c7a—H3c7b120
C23—C24—C27109.76 (15)C7—H1c7b—H3c7a60.96
C23—C24—H1c24109.5C7—H1c7b—H1c7a62.79
C25—C24—C27111.33 (15)H3c7a—H1c7b—H1c7a120
C25—C24—H1c24107.86C7—H2c7b—H3c7a62.79
C27—C24—H1c24108.23C7—H2c7b—H2c7a60.97
C10—C9—C8120.61 (12)H3c7a—H2c7b—H2c7a120
C10—C9—H1c9119.7C7—H3c7b—H2c7a62.79
C8—C9—H1c9119.7C7—H3c7b—H1c7a60.96
C1—C2—C3119.86 (15)H2c7a—H3c7b—H1c7a120
C1—C2—H1c4120.07C14—H1c14b—H1c14a72.34
C3—C2—H1c4120.07C14—H2c14b—H2c14a72.34
N4—C23—C24110.81 (13)C14—H3c25b—H3c14a72.34
Symmetry codes: (i) x+3/2, y+1/2, z+1/2; (ii) x+1, y+1, z; (iii) x+3/2, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1n1···Cl1iii0.861 (14)2.399 (15)3.2365 (13)164.5 (14)
N3—H1n3···Cl1iii0.857 (13)2.381 (13)3.2267 (12)169.4 (16)
N2—H1n2···Cl10.854 (14)2.405 (14)3.2298 (12)162.6 (14)
N4—H1n4···Cl1ii0.879 (12)2.325 (13)3.1848 (12)165.9 (15)
N4—H2n4···S1iv0.880 (15)2.449 (14)3.3211 (14)171.2 (15)
Symmetry codes: (ii) x+1, y+1, z; (iii) x+3/2, y1/2, z+1/2; (iv) x, y+1, z.

Experimental details

(I)(II)
Crystal data
Chemical formula2C24H30N3PS·C2H3NC21H24N3PS·C6H14N+·Cl
Mr888.2517.1
Crystal system, space groupTriclinic, P1Monoclinic, P21/n
Temperature (K)120120
a, b, c (Å)11.8547 (5), 13.5312 (4), 15.3394 (6)14.2245 (2), 14.2802 (3), 14.8887 (3)
α, β, γ (°)91.849 (3), 98.378 (3), 94.991 (3)90, 109.2930 (16), 90
V3)2422.56 (16)2854.48 (10)
Z24
Radiation typeCu KαCu Kα
µ (mm1)1.942.56
Crystal size (mm)0.19 × 0.17 × 0.110.25 × 0.21 × 0.17
Data collection
DiffractometerAgilent Xcalibur (Atlas, Gemini ultra)
diffractometer
Agilent Xcalibur (Atlas, Gemini ultra)
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2014)
Analytical
(CrysAlis PRO; Agilent, 2014)
Tmin, Tmax0.658, 10.950, 0.970
No. of measured, independent and
observed [I > 3σ(I)] reflections
15711, 8394, 6369 48608, 5073, 4567
Rint0.0420.032
(sin θ/λ)max1)0.5980.598
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.053, 1.45 0.029, 0.094, 1.76
No. of reflections83945073
No. of parameters568324
No. of restraints611
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.36, 0.260.22, 0.21

Computer programs: (CrysAlis PRO; Agilent, 2014), SUPERFLIP (Palatinus & Chapuis, 2007), JANA2006 (Petříček et al., 2014), Mercury (Macrae et al., 2008), enCIFer (Allen et al., 2004).

Selected geometric parameters (Å, º) for (I) top
S1a—P1a1.9643 (8)N2a—C9a1.427 (3)
P1a—N2a1.635 (2)N3b—C17b1.425 (3)
P1a—N1a1.655 (2)N1b—C1b1.409 (3)
P1a—N3a1.6523 (18)N1a—C1a1.412 (3)
S1b—P1b1.9501 (8)N2b—C9b1.406 (3)
P1b—N3b1.646 (2)N3a—C17a1.421 (3)
P1b—N1b1.6591 (19)N4—C251.128 (4)
P1b—N2b1.652 (2)
S1a—P1a—N2a108.21 (7)N3b—P1b—N1b108.65 (10)
S1a—P1a—N1a115.88 (8)N3b—P1b—N2b109.73 (10)
S1a—P1a—N3a116.27 (7)N1b—P1b—N2b97.25 (10)
N2a—P1a—N1a108.72 (10)P1a—N2a—C9a128.87 (15)
N2a—P1a—N3a108.38 (10)P1b—N3b—C17b128.04 (15)
N1a—P1a—N3a98.85 (9)P1b—N1b—C1b127.14 (16)
S1b—P1b—N3b108.31 (7)P1a—N1a—C1a126.46 (15)
S1b—P1b—N1b115.80 (8)P1b—N2b—C9b129.06 (16)
S1b—P1b—N2b116.55 (8)P1a—N3a—C17a126.12 (14)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N3b—H1n3b···S1a0.866 (17)2.497 (19)3.3479 (19)168 (2)
N1b—H1n1b···N40.86 (2)2.54 (2)3.229 (3)137.5 (19)
N3a—H1n3a···S1ai0.87 (2)2.62 (2)3.430 (2)156 (2)
N2a—H1n2a···S1b0.866 (17)2.57 (2)3.410 (2)163 (2)
N2b—H1n2b···N40.865 (14)2.138 (14)2.994 (3)171 (2)
N1a—H1n1a···S1ai0.869 (17)2.606 (16)3.435 (2)160.2 (18)
Symmetry code: (i) x+1, y+2, z+1.
Selected geometric parameters (Å, º) for (II) top
P1—S11.9524 (4)N3—C151.410 (2)
P1—N11.6523 (14)N2—C81.4171 (16)
P1—N31.6536 (13)N4—C221.4926 (18)
P1—N21.6383 (12)N4—C231.488 (2)
N1—C11.409 (2)
S1—P1—N1117.55 (4)N3—P1—N2110.58 (6)
S1—P1—N3115.54 (5)P1—N1—C1126.73 (9)
S1—P1—N2107.06 (4)P1—N3—C15127.52 (9)
N1—P1—N397.91 (6)P1—N2—C8129.31 (9)
N1—P1—N2107.83 (7)C22—N4—C23112.63 (12)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1n1···Cl1i0.861 (14)2.399 (15)3.2365 (13)164.5 (14)
N3—H1n3···Cl1i0.857 (13)2.381 (13)3.2267 (12)169.4 (16)
N2—H1n2···Cl10.854 (14)2.405 (14)3.2298 (12)162.6 (14)
N4—H1n4···Cl1ii0.879 (12)2.325 (13)3.1848 (12)165.9 (15)
N4—H2n4···S1iii0.880 (15)2.449 (14)3.3211 (14)171.2 (15)
Symmetry codes: (i) x+3/2, y1/2, z+1/2; (ii) x+1, y+1, z; (iii) x, y+1, z.
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds