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The compound N,N′,N′′-tri­cyclo­hexyl­phospho­rothioic tri­amide, C18H36N3PS or P(S)[NHC6H11]3, (I), crystallizes in the space group Pnma with the mol­ecule lying across a mirror plane; one N atom lies on the mirror plane, whereas the bond-angle sum at the other N atom has a deviation of some 8° from the ideal value of 360° for a planar configuration. The orientation of the atoms attached to this nonplanar N atom corresponds to an anti orientation of the corresponding lone electron pair (LEP) with respect to the P=S group. The P=S bond length of 1.9785 (6) Å is within the expected range for compounds with a P(S)[N]3 skeleton; however, it is in the region of the longest bond lengths found for analogous structures. This may be due to the involvement of the P=S group in N—H...S=P hydrogen bonds. In O,O′-diethyl (2-phenyl­hydrazin-1-yl)thio­phospho­nate, C10H17N2O2PS or P(S)[OC2H5]2[NHNHC6H5], (II), the bond-angle sum at the N atom attached to the phenyl ring is 345.1°, whereas, for the N atom bonded to the P atom, a practically planar environment is observed, with a bond-angle sum of 359.1°. A Cambridge Structural Database [CSD; Allen (2002). Acta Cryst. B58, 380–388] analysis shows a shift of the maximum population of P=S bond lengths in compounds with a P(S)[O]2[N] skeleton to the shorter bond lengths relative to compounds with a P(S)[N]3 skeleton. The influence of this difference on the collective tendencies of N...S distances in N—H...S hydrogen bonds for structures with P(S)[N]3 and P(S)[O]2[N] segments were studied through a CSD analysis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614022608/fg3325sup1.cif
Contains datablocks New_Global_Publ_Block, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614022608/fg3325Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614022608/fg3325IIsup3.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614022608/fg3325IIsup4.cml
Supplementary material

CCDC references: 1029190; 1029191

Introduction top

Up to now, for P(S)[N]3 and P(S)[O]2[N] skeletons, 78 and 187 structures, respectively, have been deposited in the Cambridge Structural Database (CSD, Version 5.35, August 2014 update; Allen, 2002) (the metal complexes were not considered and duplicated structures deposited were excluded; however, the different X-ray measurements for one compound were considered separately in these numerations.)

Among the results of the P(S)[N]3 query, there are a few reports on the structure determinations of phospho­rothioic tri­amides with a P(S)[N(C)(C)]3 skeleton, for example ,[(CH3)2N]3P(S) (CSD refcode NAHWUO; Rudd et al., 1996). However, there is no report on a diffraction study of [RNH]3P(S) phospho­rothioic tri­amides. Of course, merely one example of a compound with a P(S)[NH]3 skeleton (and not a P(S)[NH(C)]3 skeleton) was found in the CSD for the structure of [Me3SiNH]2P(S)–NH–P(S)[NHSiMe3]–NH–P(S)[NHSiMe3]2 (CSD refcode ICEDEZ; Pinkas & Verkade, 1998).

For the P(S)[O]2[N] query, the variety in the compounds deposited is larger comapred with a P(S)[N]3 skeleton and some structures with [O]2P(S)[N—C(S)] (Babashkina et al., 2011), [O]2P(S)[N—S(O)2] (Oltean et al., 2013), [O]2P(S)[N—N] (Rybarczyk-Pirek et al., 2006) segments and so on were deposited.

In a continuation of our previous reports on the structure determinations of phospho­ramide (Pourayoubi, Nečas & Negari, 2012; Tarahhomi et al., 2013) and thio­phospho­ramide compounds (Raissi Shabari et al., 2012; Sabbaghi et al., 2012) and a CSD analysis of different aspects of phospho­ramide structures (Pourayoubi et al., 2013; Pourayoubi, Jasinski et al., 2012), we wish here to study thio­phospho­ramide structures.

Thus, two thio­phospho­ramides, with P(S)[N]3 and P(S)[O]2[N] skeletons, have been studied, viz. P(S)[NHC6H11]3, (I), and P(S)[OC2H5]2[NHNHC6H5], (II). Some differences and similarities of the structures with the mentioned skeletons are discussed considering structures (I) and (II) and the analogous structures deposited in the CSD.

Experimental top

Synthesis and crystallization top

A general procedure was previously reported for the synthesis of P(S)[NHR]3 phospho­rothioic tri­amide with reporting the 31P NMR data for some derivatives, such as P(S)[NHC6H11]3 (Hursthouse et al., 1986). Moreover, with investigating of a previously published paper, by Mel'nikov & Zen'kevich (1955), a general method was found for the synthesis of some amides and hydrazides of di­alk­oxy­thio­phospho­ric acids, such as P(S)[OC2H5]2NHNHC6H5] as well as its melting point and elemental analysis for the P atom. Then, in a newer article, by Riesel & Helbing (1992), the phospho­rous chemical shift of P(S)[OC2H5]2[NHNHC6H5] was found. The synthesis procedure reported here is similar to the literature methods but by a few modifications, for example, using the ice-bath temperature in this work instead of the reflux conditions in the article by Hursthouse et al. (1986). The details of the synthesis procedure done for this paper are as follows:

The syntheses described for the preparation of (I) and (II) begin with the reagents being combined at ice-bath temperature and the mixture then allowed to come to room temperature for the rest of the procedure. For the synthesis of (I), a solution of C6H5NH2 (60 mmol) in dry CH3CN (20 ml) was added to a solution of Cl3P(S) (10 mmol) in the same solvent (10 ml) at 273 K. After stirring for 4 h, the solid which formed was filtered off and the filtered solution was evaporated in vacuo to obtain the crude product as a solid which was washed with distilled water. Single crystals suitable for X-ray crystallography were obtained from a mixture of (I) in CH3C(O)CH3/CH3CN (1:1 v/v) by slow evaporation at room temperature. IR (cm-1): 3348, 3248, 2932, 2851, 1450, 1420, 1092, 883, 652. 31P NMR (162.0 MHz, DMSO-d6): δ 57.25 (m); 1H NMR (400.1 MHz, DMSO-d6): δ 1.05 (m, 6H), 1.15 (m, 9H), 1.51 (br m, 3H), 1.64 (br m, 6H), 1.85 (br m, 6H), 2.95 (br m, 3H), 3.63 (pseudo-t, J = 9.2/9.6 Hz, 3H, NH); 13C NMR (100.6 MHz, DMSO-d6): δ 25.75 (d, JP,C = 4.7 Hz), 35.72 (d, JP,C = 4.9 Hz), 40.44 (s), 50.48 (s) [the 31P chemical shift of P(S)[NHC6H11]3 in CDCl3 was reported at 59.1 p.p.m.; Hursthouse et al., 1986]

Compound (II) was synthesized from the reaction of C6H5NHNH2 (20 mmol) and P(S)[OC2H5]2Cl (10 mmol) in dry CH3CN [with a stirring time of 3 h and using the purification procedure mentioned for compound (I)]. Single crystals were obtained from a solution of the product in CH3C(O)CH3/CH3CN (1:1 v/v) after slow evaporation at room temperature. IR (cm-1): 3305, 2978, 2932, 2901, 1601, 1497, 1022, 957, 806, 644. 31P NMR (202.4 MHz, DMSO-d6): δ 71.08 (doublet of quintets, J = 42.7 Hz, J = 8.7/9.4/9.2/8.3 Hz); 1H NMR (500.1 MHz, DMSO-d6): δ 1.13 (t, J = 7.0 Hz, 6H), 3.55 (NH, evidence of a peak is observed near the signal 3.47 p.p.m. of water in d6-DMSO in the noted chemical shift), 3.94 (m, 4H), 6.63 (t, J = 7.2/6.6 Hz, 1H), 6.77 (d, J = 8.4 Hz, 2H), 7.08 (t, J = 7.4/7.5 Hz, 2H), 7.33 (d, J = 43.0 Hz, 1H); 13C NMR (125.8 MHz, DMSO-d6): δ 16.61 (d, JP,C = 7.9 Hz), 63.38 (d, JP,C = 5.0 Hz), 113.19 (s), 119.19 (s), 129.36 (s), 150.57 (d, JP,C = = 3.9 Hz). [In the paper published by Riesel & Helbing (1992), ethanol was reported as solvent for the 31P NMR experiment of P(S)[OC2H5]2[NHNHC6H5] (75.1 p.p.m.)]

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. Crystal data, data collection and structure refinement details are summarized in Table 1. For both (I) and (II), all H atoms were discernible in difference Fourier maps and could be refined to reasonable geometry. According to common practice, H atoms bonded to C atoms were kept in ideal positions, with C—H = 0.96 Å, while the positions of H atoms bonded to N atoms were refined freely; in both cases, Uiso(H) values were set at 1.2Ueq(C,N). All non-H atoms were refined using harmonic refinement. The disordered eth­oxy group in (II) was refined freely with the sum of the occupancies restrained to 1.

Results and discussion top

Compound (I) is the first diffraction study of an [RNH]3P(S) phospho­rothioic tri­amide. Compound (I) was synthesized from the reaction of P(S)Cl3 with cyclo­hexyl­amine (1:6 molar ratio) in dry CH3CN. This compound has crystallographically imposed mirror symmetry, with atoms N2, C7 and C10 (and related H atoms) of one C6H11NH group and the P1S1 group lying on the mirror plane (Fig. 1). Selected bond lengths and angles for (I) are given in Table 2.

The P atom is bonded in a distorted tetra­hedral P(S)[N]3 environment with the three N—P—N angles more contracted than the three N—P—S angles; the smallest and largest angles are N1—P1—N1i = 98.51 (6)° and N1—P1—S1/N1i—P1—S1 = 116.50 (4)° [symmetry code: (i) x, -y+3/2, z]. The maximum and minimum angles are related to the S1/N1/N1i part of the tetra­hedron made by the S atom and three N atoms around the P atom. Related to each cyclo­hexyl group, the rest of the NHP(S)[NHC6H11]2 segment occupies the equatorial position.

The sp2 character of the N atom should be reflected in the P—N—C angles, of course, however, these angles at N1 and N2 do not show significant differences [N1 = 123.08 (9)° and N2 = 123.54 (11)°]. Sums of the surrounding angles at these N atoms (P—N—C + C—N—H + H—N—P) show a distortion from planarity for N1 (a minor shift towards sp3-hybridization is observed), as the sum at N1 shows a deviation about 8° from the planar value of 360°, whereas the bond angles sum at atom N2 is 360°. This difference in the contribution of p orbital in hybridization reflects in the P—N bond lengths [P1—N1 = 1.6475 (11) Å and P1—N2 = 1.6284 (15) Å]. Inter­estingly, the orientation of the atoms attached to N1 (and N1i) suggests an anti orientation of the LEP in this N atom with respect to the PS group (Fig. 2). This observation is similar to what was found for RC(O)NHP(O)[NR1R2]2 phospho­ric tri­amide structures, where the orientation of atoms attached to more pyramidal N atom suggests an anti orientation with respect to the PO group (Pourayoubi, Jasinski et al., 2012).

The PS bond length [1.9785 (6) Å] is within the expected range for compounds with a P(S)[N]3 skeleton; however, it is located on the right extremity of histogram obtained from a CSD analysis of PS bond lengths (the region of the longest bond lengths; Fig. 3) for such compounds. Fig. 4 indicates the scatterplot of PS bond lengths against the related P—Nave value, (P—N1 + P—N2 + P—N3)/3, in compounds with a P(S)[N]3 skeleton. The P—Nave value may be considered as a ground of an indication of?] P—N bond strength and also the electron delocalization from the N atoms towards the P atom. As can be seen, there is a trend for elongation of PS bond length in smaller P—Nave value; however, there is considerable scatter in this correlation due to the other factors affecting these two values.

For compound (I), the P—Nave value (1.641 Å) is in the region of the smallest P—Nave values of analogous compounds deposited in the CSD (Fig. 4). So, the electronic effect can be considered for inter­pretation of the relatively long PS bond length in (I). Moreover, the effect of hydrogen bonding is important, as in the crystal structure of (I) there is (N—H···)2(N—H···)SP hydrogen bonding (Fig. 5 and Table 3) connecting the molecules into extended chains parallel to the a axis. The N···S distances in the mentioned hydrogen-bonded group are 3.4720 (12) and 3.6201 (18) Å which are within the expected range of N—H···SP hydrogen bonds, shown as histogram for related N···S distances in compounds with a P(S)[N]3 skeleton deposited in the CSD (including compounds with P(S)[NH][N]2 and P(S)[NH]2[N] segments and one example each of structures of compounds with the P(S)[N—NH]3 (CSD refcode JAQMOE; Chandrasekhar & Azhakar, 2005) and P(S)[NH]3 segments (CSD refcode ICEDEZ; Pinkas & Verkade, 1998) (Fig. 6); the total numbers of N···S distances in compounds with a P(S)[N]3 skeleton deposited in the CSD are 28 entries.

Compound (II) was synthesized from the reaction of P(S)[OC2H5]2Cl with phenyl­hydrazine (1:2 molar ratio) in dry CH3CN. Selected bond lengths and angles for (II) are given in Table 4.

The P atom is bonded in a distorted tetra­hedral P(S)[O]2[N] environment (Fig. 7) and the PS bond length [1.9302 (6) Å] is shorter than the PS bond length of (I).

A CSD analysis of PS bond lengths for compounds with a P(S)[N]3 skeleton shows the maximum population to be in the range 1.92–1.94 Å, which is populated by 70 bond lengths out of 143 (about 49% of bonds found in the CSD); a similar analysis for compounds with a P(S)[O]2[N] skeleton shows the maximum population shift to the shorter bond lengths to be in the range 1.90–1.92 Å (about 57%, 147 bonds from the total bonds of 260; Fig. 8). This is an expected result because of higher electronegativity of two O atoms in the P(S)[O]2[N] segment with respect to the atoms related to the P(S)[N]3 segment. It should be noted that the exact prediction of bond length (or the exact prediction of increasing/lowering of bond lengths with changing the groups) is impossible as electronegativity is only one of the factors affecting the bond lengths in structures and the effects of different factors and overall tendency may not be predicted exactly.

Among the two N atoms in the C6H5NHNH segment, atom N2 is significantly shifted towards sp3-hybridization relative to atom N1, which is almost perfectly planar (the bond-angle sums are 345.1 and 359.1°, respectively). Atom N2 is separated through the other N atom from the PS unit and the vector introducing the LEP orientation on this pyramidal N atom is on opposite side of the PS bond vector.

The P1—O1—C7 bond angle of 120.67 (9)° is similar to the P—O—C angles in compounds with a P(S)—O—R segment. The O2/O2' atoms of the eth­oxy group in (II) indicates disorder over two sites. In the crystal structure, molecules are linked via N—H···SP [N···S = 3.4420 (15) Å] and N—H···O [N···O = 3.1301 (16) Å] hydrogen bonds into a one-dimensional chain parallel to the c axis (Fig. 9 and Table 5). The N···S distance in (II) is shorter than in (I) and this may be because of the anti co-operativity (Steiner, 2002) of the three hydrogen bonds received by one acceptor in (I); the collective tendency of N—H···S distances in structures with a P(S)[O]2[N] segment (Fig. 10) shows more population in the longer distances for N···S inter­actions relative to the collective tendency for structures with a P(S)[N]3 skeleton (due to the differences in the electron densities on S atoms in the mentioned skeletons being reflected in differences in the corresponding PS bond lengths).

Related literature top

For related literature, see: Allen (2002); Babashkina et al. (2011); Chandrasekhar & Azhakar (2005); Hursthouse et al. (1986); Mel'nikov & Zen'kevich (1955); Oltean et al. (2013); Pinkas & Verkade (1998); Pourayoubi et al. (2013); Pourayoubi, Jasinski, Shoghpour Bayraq, Eshghi, Keeley, Bruno & Amiri Rudbari (2012); Raissi Shabari, Sabbaghi, Pourayoubi, Necas & Babiak (2012); Riesel & Helbing (1992); Rudd et al. (1996); Rybarczyk-Pirek, Dubis, Grabowski & Nawrot-Modranka (2006); Sabbaghi et al. (2012); Steiner (2002); Tarahhomi et al. (2013).

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2011) for (I); CrysAlis PRO (Agilent, 2012) for (II). Cell refinement: CrystalClear-SM Expert (Rigaku, 2011) for (I); CrysAlis PRO (Agilent, 2012) for (II). Data reduction: CrystalClear-SM Expert (Rigaku, 2011) for (I); CrysAlis PRO (Agilent, 2012) for (II). For both compounds, program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: JANA2006 (Petříček et al., 2014); molecular graphics: DIAMOND (Brandenburg & Putz, 2005) and 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 level) and atom-numbering scheme for (I). [Symmetry code: (i) x, -y+3/2, z.]
[Figure 2] Fig. 2. The anti orientation of the N1 lone electron pair (LEP) relative to PS in compound (I). For the C6H5NH groups, only the NH(C) segments are shown for clarity.
[Figure 3] Fig. 3. Histogram of the PS bond lengths in compounds with a P(S)[N]3 segment deposited in the CSD (Allen, 2002). The number of hits in each region is given above the column.
[Figure 4] Fig. 4. Scatterplot of PS bond lengths (Å) against P—Nave values in compounds with a P(S)[N]3 segment deposited in the CSD (Allen, 2002).
[Figure 5] Fig. 5. Part of the crystal packing of (I), showing the linear arrangement built from (N—H···)2(N—H···)SP groups. The hydrogen bonds are shown as dotted lines and C-bound H atoms have been omitted for clarity. [Symmetry codes: (i) x, -y+3/2, z; (ii) x-1/2, y, -z+1/2; (iii) x+1/2, y, -z+1/2.]
[Figure 6] Fig. 6. Histogram of the N···S distances of N—H···SP hydrogen bonds in compounds with a P(S)[N]3 segment deposited in the CSD (Allen, 2002). The number of hits in each region is given above the column.
[Figure 7] Fig. 7. Displacement ellipsoid plot (50% probability level) and atom-numbering scheme for (II).
[Figure 8] Fig. 8. Histogram of the PS bond lengths in compounds with a P(S)[O]2[N] segment deposited in the CSD (Allen, 2002). The number of hits in each region is given above the column.
[Figure 9] Fig. 9. Part of the crystal packing of (II), showing the linear arrangement built from N—H···SP and N—H···O hydrogen bonds. The hydrogen bonds are shown as dotted lines and C-bound H atoms have been omitted for clarity.
[Figure 10] Fig. 10. Histogram of the N···S distances of N—H···SP hydrogen bonds in compounds with a P(S)[O]2[N] segment deposited in the CSD (Allen, 2002). The number of hits in each region is given above the column.
(I) N,N',N''-Tricyclohexylphosphorothioic triamide top
Crystal data top
C18H36N3PSF(000) = 784
Mr = 357.5Dx = 1.144 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P -2xabc;-2yb;-2zacCell parameters from 7402 reflections
a = 9.0897 (7) Åθ = 3.1–33.0°
b = 18.6342 (15) ŵ = 0.24 mm1
c = 12.2598 (8) ÅT = 120 K
V = 2076.6 (3) Å3Prism, colourless
Z = 40.30 × 0.30 × 0.25 mm
Data collection top
Rigaku Saturn724+ (2x2 bin mode)
diffractometer
3731 independent reflections
Radiation source: X-ray tube2645 reflections with I > 3σ(I)
Multilayer monochromatorRint = 0.033
Detector resolution: 28.5714 pixels mm-1θmax = 33.1°, θmin = 3.7°
profile data from ω–scansh = 1113
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku, 2011)
k = 2822
Tmin = 0.852, Tmax = 1.000l = 1418
18907 measured reflections
Refinement top
Refinement on F271 constraints
R[F2 > 2σ(F2)] = 0.046H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.130Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0016I2)
S = 1.80(Δ/σ)max = 0.009
3731 reflectionsΔρmax = 0.55 e Å3
117 parametersΔρmin = 0.43 e Å3
0 restraints
Crystal data top
C18H36N3PSV = 2076.6 (3) Å3
Mr = 357.5Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 9.0897 (7) ŵ = 0.24 mm1
b = 18.6342 (15) ÅT = 120 K
c = 12.2598 (8) Å0.30 × 0.30 × 0.25 mm
Data collection top
Rigaku Saturn724+ (2x2 bin mode)
diffractometer
3731 independent reflections
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku, 2011)
2645 reflections with I > 3σ(I)
Tmin = 0.852, Tmax = 1.000Rint = 0.033
18907 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.130H atoms treated by a mixture of independent and constrained refinement
S = 1.80Δρmax = 0.55 e Å3
3731 reflectionsΔρmin = 0.43 e Å3
117 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.33232 (5)0.250.16559 (3)0.02611 (13)
P10.28701 (5)0.250.32344 (3)0.02042 (12)
N10.18573 (12)0.31698 (5)0.36876 (9)0.0237 (3)
N20.44140 (15)0.250.39081 (11)0.0241 (4)
C10.22644 (13)0.39240 (6)0.35451 (9)0.0225 (3)
C20.18747 (15)0.43367 (6)0.45813 (9)0.0274 (3)
C30.22659 (15)0.51299 (7)0.44892 (10)0.0325 (4)
C40.15119 (15)0.54697 (7)0.35078 (9)0.0292 (4)
C50.18861 (15)0.50655 (7)0.24629 (9)0.0318 (4)
C60.15165 (15)0.42683 (7)0.25592 (9)0.0284 (3)
C70.45003 (18)0.250.51050 (13)0.0225 (4)
C80.52771 (14)0.18277 (6)0.55299 (10)0.0271 (3)
C90.52988 (17)0.18259 (7)0.67752 (10)0.0333 (4)
C100.6036 (2)0.250.72171 (15)0.0384 (6)
H1c10.3304390.3943880.3411980.027*
H1c20.2385690.4130250.5190550.0329*
H2c20.0841630.4288090.4726150.0329*
H1c30.1967230.5374840.5141570.039*
H2c30.331250.5180650.4418130.039*
H1c40.0465930.5465780.3616020.0351*
H2c40.1819370.5960590.3440250.0351*
H1c50.2914550.5120460.230560.0381*
H2c50.134990.5269950.1864020.0381*
H1c60.047020.4210250.2618660.0341*
H2c60.1817930.4024370.1906680.0341*
H1c70.350820.250.5373430.027*
H1c80.6267960.1816440.5259320.0325*
H2c80.4771150.1408460.5272230.0325*
H1c90.4309180.1798530.7045620.04*
H2c90.5818830.1409940.7029870.04*
H1c100.5984150.250.7999150.046*
H2c100.7056730.250.701480.046*
H1n10.0966 (19)0.3104 (8)0.3684 (12)0.0285*
H1n20.516 (3)0.250.3542 (16)0.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0192 (2)0.0366 (2)0.0225 (2)00.00033 (14)0
P10.0164 (2)0.0230 (2)0.0219 (2)00.00019 (14)0
N10.0176 (5)0.0243 (5)0.0293 (5)0.0002 (4)0.0016 (4)0.0010 (4)
N20.0160 (7)0.0342 (7)0.0222 (6)00.0005 (5)0
C10.0196 (6)0.0234 (5)0.0246 (5)0.0001 (4)0.0014 (4)0.0008 (4)
C20.0319 (7)0.0288 (6)0.0215 (5)0.0049 (5)0.0024 (5)0.0008 (5)
C30.0369 (8)0.0289 (6)0.0318 (6)0.0044 (5)0.0071 (5)0.0053 (5)
C40.0313 (7)0.0257 (6)0.0306 (6)0.0032 (5)0.0012 (5)0.0002 (5)
C50.0400 (8)0.0284 (6)0.0268 (6)0.0056 (5)0.0066 (5)0.0054 (5)
C60.0354 (7)0.0281 (6)0.0217 (5)0.0032 (5)0.0013 (5)0.0013 (4)
C70.0191 (8)0.0273 (8)0.0212 (7)00.0000 (6)0
C80.0249 (6)0.0278 (6)0.0286 (6)0.0005 (5)0.0014 (5)0.0013 (5)
C90.0326 (7)0.0380 (7)0.0294 (6)0.0037 (6)0.0004 (5)0.0089 (5)
C100.0371 (11)0.0536 (12)0.0244 (8)00.0054 (8)0
Geometric parameters (Å, º) top
S1—P11.9785 (6)C4—H1c40.96
P1—N11.6475 (11)C4—H2c40.96
P1—N1i1.6475 (11)C5—C61.5276 (18)
P1—N21.6284 (15)C5—H1c50.96
N1—C11.4637 (15)C5—H2c50.96
N1—H1n10.819 (17)C6—H1c60.96
N2—C71.470 (2)C6—H2c60.96
N2—H1n20.81 (2)C7—C81.5295 (15)
C1—C21.5267 (16)C7—C8i1.5295 (15)
C1—C61.5280 (16)C7—H1c70.96
C1—H1c10.96C8—C91.5269 (17)
C2—C31.5244 (18)C8—H1c80.96
C2—H1c20.96C8—H2c80.96
C2—H2c20.96C9—C101.5235 (18)
C3—C41.5226 (18)C9—H1c90.96
C3—H1c30.96C9—H2c90.96
C3—H2c30.96C10—H1c100.96
C4—C51.5245 (17)C10—H2c100.96
S1—P1—N1116.50 (4)C4—C5—C6111.50 (10)
S1—P1—N1i116.50 (4)C4—C5—H1c5109.47
S1—P1—N2108.46 (5)C4—C5—H2c5109.47
N1—P1—N1i98.51 (6)C6—C5—H1c5109.47
N1—P1—N2108.09 (5)C6—C5—H2c5109.47
N1i—P1—N2108.09 (5)H1c5—C5—H2c5107.37
P1—N1—C1123.08 (9)C1—C6—C5111.82 (10)
P1—N1—H1n1116.0 (10)C1—C6—H1c6109.47
C1—N1—H1n1113.1 (10)C1—C6—H2c6109.47
P1—N2—C7123.54 (11)C5—C6—H1c6109.47
P1—N2—H1n2116.0 (15)C5—C6—H2c6109.47
C7—N2—H1n2120.5 (15)H1c6—C6—H2c6107.02
N1—C1—C2109.01 (9)N2—C7—C8111.39 (8)
N1—C1—C6112.65 (10)N2—C7—C8i111.39 (8)
N1—C1—H1c1107.84N2—C7—H1c7106.99
C2—C1—C6110.09 (10)C8—C7—C8i109.99 (12)
C2—C1—H1c1110.51C8—C7—H1c7108.48
C6—C1—H1c1106.71C8i—C7—H1c7108.48
C1—C2—C3111.88 (10)C7—C8—C9110.38 (10)
C1—C2—H1c2109.47C7—C8—H1c8109.47
C1—C2—H2c2109.47C7—C8—H2c8109.47
C3—C2—H1c2109.47C9—C8—H1c8109.47
C3—C2—H2c2109.47C9—C8—H2c8109.47
H1c2—C2—H2c2106.95H1c8—C8—H2c8108.54
C2—C3—C4110.90 (10)C8—C9—C10111.06 (11)
C2—C3—H1c3109.47C8—C9—H1c9109.47
C2—C3—H2c3109.47C8—C9—H2c9109.47
C4—C3—H1c3109.47C10—C9—H1c9109.47
C4—C3—H2c3109.47C10—C9—H2c9109.47
H1c3—C3—H2c3108H1c9—C9—H2c9107.83
C3—C4—C5110.99 (10)C9—C10—C9i111.09 (15)
C3—C4—H1c4109.47C9—C10—H1c10109.47
C3—C4—H2c4109.47C9—C10—H2c10109.47
C5—C4—H1c4109.47C9i—C10—H1c10109.47
C5—C4—H2c4109.47C9i—C10—H2c10109.47
H1c4—C4—H2c4107.91H1c10—C10—H2c10107.81
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1n1···S1ii0.819 (17)2.67 (2)3.4720 (12)161.6 (16)
N2—H1n2···S1iii0.81 (3)2.87 (3)3.6201 (18)151.3 (19)
Symmetry codes: (ii) x1/2, y+1/2, z+1/2; (iii) x+1/2, y+1/2, z+1/2.
(II) O,O'-Diethyl (2-phenylhydrazin-1-yl)thiophosphonate top
Crystal data top
C10H17N2O2PSF(000) = 552
Mr = 260.3Dx = 1.304 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ycbCell parameters from 4151 reflections
a = 9.938 (1) Åθ = 2.8–28.3°
b = 16.3798 (10) ŵ = 0.35 mm1
c = 8.4156 (6) ÅT = 120 K
β = 104.553 (11)°Block, colourless
V = 1325.96 (19) Å30.72 × 0.50 × 0.24 mm
Z = 4
Data collection top
Agilent Xcalibur Atlas Gemini ultra
diffractometer
3038 independent reflections
Radiation source: Enhance (Mo) X-ray Source2628 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.018
Detector resolution: 10.3784 pixels mm-1θmax = 28.4°, θmin = 2.8°
ω scansh = 1212
Absorption correction: analytical
(CrysAlis PRO; Agilent, 2012)
k = 2121
Tmin = 0.834, Tmax = 0.925l = 1110
9959 measured reflections
Refinement top
Refinement on F295 constraints
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.106Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0016I2)
S = 1.78(Δ/σ)max = 0.020
3038 reflectionsΔρmax = 0.28 e Å3
170 parametersΔρmin = 0.22 e Å3
0 restraints
Crystal data top
C10H17N2O2PSV = 1325.96 (19) Å3
Mr = 260.3Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.938 (1) ŵ = 0.35 mm1
b = 16.3798 (10) ÅT = 120 K
c = 8.4156 (6) Å0.72 × 0.50 × 0.24 mm
β = 104.553 (11)°
Data collection top
Agilent Xcalibur Atlas Gemini ultra
diffractometer
3038 independent reflections
Absorption correction: analytical
(CrysAlis PRO; Agilent, 2012)
2628 reflections with I > 3σ(I)
Tmin = 0.834, Tmax = 0.925Rint = 0.018
9959 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.78Δρmax = 0.28 e Å3
3038 reflectionsΔρmin = 0.22 e Å3
170 parameters
Special details top

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.36.21 Analytical numeric absorption correction based on crystal shape

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
P10.37825 (4)0.65703 (2)0.16541 (4)0.02538 (13)
S10.29032 (4)0.60178 (3)0.03656 (5)0.03637 (15)
N10.41906 (14)0.75074 (8)0.13022 (14)0.0335 (4)
N20.49967 (14)0.79743 (8)0.25809 (15)0.0291 (4)
C10.63310 (15)0.82052 (9)0.24912 (16)0.0262 (4)
C20.70142 (18)0.88202 (10)0.3522 (2)0.0377 (5)
C30.83635 (19)0.90318 (10)0.3536 (2)0.0441 (6)
C40.90453 (18)0.86428 (11)0.2507 (2)0.0459 (6)
C50.83576 (17)0.80426 (11)0.1470 (2)0.0402 (6)
C60.70137 (16)0.78226 (9)0.14481 (18)0.0301 (5)
O10.29147 (11)0.65959 (6)0.29807 (12)0.0297 (3)
C70.14686 (16)0.68387 (10)0.25369 (19)0.0354 (5)
C80.0704 (2)0.63514 (14)0.3511 (3)0.0645 (9)
O20.5236 (2)0.62451 (14)0.2532 (3)0.0251 (7)0.594 (5)
C90.5358 (3)0.53861 (16)0.2956 (4)0.0456 (11)0.594 (5)
C100.68324 (19)0.51985 (10)0.3903 (2)0.0422 (6)
O2'0.4957 (4)0.6096 (2)0.3090 (4)0.0279 (11)0.406 (5)
C9'0.6220 (4)0.5809 (2)0.2679 (4)0.0318 (13)0.406 (5)
H1c20.6545460.9099950.4230410.0452*
H1c30.8829920.9451830.4264590.0529*
H1c40.9982690.8788540.2515310.055*
H1c50.8823110.7771690.0748040.0482*
H1c60.6550860.7404760.0710840.0361*
H1c70.1081920.6738610.1388730.0425*
H2c70.1397830.7408120.2773920.0425*
H1c80.025250.6519010.3247850.0774*
H2c80.0757620.5782950.325680.0774*
H3c80.1110920.6436950.4660350.0774*
H1n10.4039 (19)0.7681 (11)0.033 (2)0.0402*
H1n20.4557 (18)0.8324 (11)0.286 (2)0.0349*
H1c90.4729870.5255670.3619390.0547*0.594 (5)
H2c90.5126280.5064290.1971290.0547*0.594 (5)
H1c100.6908120.4629880.4188180.0506*0.594 (5)
H2c100.745940.5324720.3236390.0506*0.594 (5)
H3c100.7064980.5521890.4885590.0506*0.594 (5)
H1c10'0.7621840.4955920.362350.0506*0.406 (5)
H2c10'0.7123080.5453140.496160.0506*0.406 (5)
H3c10'0.6156570.4783650.393210.0506*0.406 (5)
H1c9'0.5981160.5561040.16110.0381*0.406 (5)
H2c9'0.6854890.6256110.2740980.0381*0.406 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0212 (2)0.0296 (2)0.0243 (2)0.00049 (13)0.00370 (15)0.00535 (13)
S10.0354 (3)0.0426 (3)0.0295 (2)0.00730 (16)0.00498 (17)0.01288 (16)
N10.0415 (8)0.0430 (7)0.0168 (6)0.0157 (6)0.0085 (5)0.0011 (5)
N20.0359 (7)0.0312 (6)0.0224 (6)0.0075 (5)0.0116 (5)0.0053 (5)
C10.0326 (8)0.0240 (6)0.0207 (6)0.0019 (6)0.0041 (6)0.0064 (5)
C20.0469 (10)0.0301 (8)0.0358 (9)0.0101 (7)0.0099 (7)0.0037 (6)
C30.0457 (10)0.0328 (9)0.0466 (10)0.0131 (7)0.0019 (8)0.0045 (7)
C40.0281 (9)0.0453 (10)0.0590 (11)0.0000 (7)0.0014 (8)0.0170 (9)
C50.0293 (9)0.0459 (10)0.0446 (9)0.0091 (7)0.0080 (7)0.0059 (7)
C60.0309 (8)0.0297 (7)0.0272 (7)0.0037 (6)0.0026 (6)0.0029 (6)
O10.0281 (6)0.0365 (6)0.0250 (5)0.0037 (4)0.0075 (4)0.0037 (4)
C70.0302 (8)0.0389 (8)0.0395 (9)0.0023 (7)0.0131 (7)0.0039 (7)
C80.0459 (12)0.0671 (13)0.0930 (17)0.0046 (10)0.0405 (12)0.0307 (13)
O20.0209 (11)0.0241 (10)0.0288 (13)0.0021 (8)0.0035 (8)0.0012 (9)
C90.0395 (18)0.0312 (15)0.064 (2)0.0048 (12)0.0101 (14)0.0131 (13)
C100.0501 (11)0.0331 (8)0.0355 (8)0.0109 (7)0.0040 (7)0.0040 (7)
O2'0.0272 (17)0.0368 (18)0.0202 (17)0.0020 (13)0.0067 (12)0.0018 (13)
C9'0.031 (2)0.037 (2)0.0279 (19)0.0108 (17)0.0077 (15)0.0054 (15)
Geometric parameters (Å, º) top
P1—S11.9302 (6)C7—C81.484 (3)
P1—N11.6335 (14)C7—H1c70.96
P1—O11.5734 (12)C7—H2c70.96
P1—O21.543 (2)C8—H1c80.96
N1—N21.3970 (17)C8—H2c80.96
N1—H1n10.839 (18)C8—H3c80.96
N2—C11.399 (2)O2—C91.449 (4)
N2—H1n20.791 (19)C9—C101.513 (3)
C1—C21.390 (2)C9—H1c90.96
C1—C61.387 (2)C9—H2c90.96
C2—C31.382 (3)C10—C9'1.455 (4)
C2—H1c20.96C10—H1c100.96
C3—C41.382 (3)C10—H2c100.96
C3—H1c30.96C10—H3c100.96
C4—C51.377 (2)C10—H1c10'0.96
C4—H1c40.96C10—H2c10'0.96
C5—C61.379 (2)C10—H3c10'0.96
C5—H1c50.96O2'—C9'1.461 (6)
C6—H1c60.96C9'—H1c9'0.96
O1—C71.4468 (19)C9'—H2c9'0.96
S1—P1—N1111.04 (5)C8—C7—H1c7109.47
S1—P1—O1115.45 (4)C8—C7—H2c7109.47
S1—P1—O2114.96 (10)H1c7—C7—H2c7110.08
N1—P1—O1107.99 (7)C7—C8—H1c8109.47
N1—P1—O299.55 (10)C7—C8—H2c8109.47
O1—P1—O2106.49 (12)C7—C8—H3c8109.47
P1—N1—N2119.69 (9)H1c8—C8—H2c8109.47
P1—N1—H1n1120.1 (12)H1c8—C8—H3c8109.47
N2—N1—H1n1119.3 (12)H2c8—C8—H3c8109.47
N1—N2—C1118.31 (13)P1—O2—C9117.59 (19)
N1—N2—H1n2111.8 (12)O2'—O2—C9'100.8 (4)
C1—N2—H1n2115.0 (13)O2—C9—C10109.7 (2)
N2—C1—C2118.89 (14)O2—C9—H1c9109.47
N2—C1—C6122.21 (12)O2—C9—H2c9109.47
C2—C1—C6118.86 (15)C10—C9—H1c9109.47
C1—C2—C3120.49 (17)C10—C9—H2c9109.47
C1—C2—H1c2119.75H1c9—C9—H2c9109.28
C3—C2—H1c2119.75C9—C10—H1c10109.47
C2—C3—C4120.44 (15)C9—C10—H2c10109.47
C2—C3—H1c3119.78C9—C10—H3c10109.47
C4—C3—H1c3119.78C9'—C10—H1c10'109.47
C3—C4—C5118.87 (17)C9'—C10—H2c10'109.47
C3—C4—H1c4120.56C9'—C10—H3c10'109.47
C5—C4—H1c4120.56H1c10—C10—H2c10109.47
C4—C5—C6121.34 (17)H1c10—C10—H3c10109.47
C4—C5—H1c5119.33H2c10—C10—H3c10109.47
C6—C5—H1c5119.33H1c10'—C10—H2c10'109.47
C1—C6—C5119.98 (14)H1c10'—C10—H3c10'109.47
C1—C6—H1c6120.01H2c10'—C10—H3c10'109.47
C5—C6—H1c6120.01C10—C9'—O2'106.6 (3)
P1—O1—C7120.67 (9)C10—C9'—H1c9'109.47
O1—C7—C8108.85 (13)C10—C9'—H2c9'109.47
O1—C7—H1c7109.47O2'—C9'—H1c9'109.47
O1—C7—H2c7109.47O2'—C9'—H2c9'109.47
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1n1···O1i0.839 (18)2.338 (17)3.1301 (16)157.6 (18)
N2—H1n2···S1ii0.790 (18)2.708 (18)3.4420 (15)155.5 (16)
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x, y+3/2, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC18H36N3PSC10H17N2O2PS
Mr357.5260.3
Crystal system, space groupOrthorhombic, PnmaMonoclinic, P21/c
Temperature (K)120120
a, b, c (Å)9.0897 (7), 18.6342 (15), 12.2598 (8)9.938 (1), 16.3798 (10), 8.4156 (6)
α, β, γ (°)90, 90, 9090, 104.553 (11), 90
V3)2076.6 (3)1325.96 (19)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.240.35
Crystal size (mm)0.30 × 0.30 × 0.250.72 × 0.50 × 0.24
Data collection
DiffractometerRigaku Saturn724+ (2x2 bin mode)
diffractometer
Agilent Xcalibur Atlas Gemini ultra
diffractometer
Absorption correctionMulti-scan
(CrystalClear-SM Expert; Rigaku, 2011)
Analytical
(CrysAlis PRO; Agilent, 2012)
Tmin, Tmax0.852, 1.0000.834, 0.925
No. of measured, independent and
observed [I > 3σ(I)] reflections
18907, 3731, 2645 9959, 3038, 2628
Rint0.0330.018
(sin θ/λ)max1)0.7670.669
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.130, 1.80 0.034, 0.106, 1.78
No. of reflections37313038
No. of parameters117170
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)0.55, 0.430.28, 0.22

Computer programs: CrystalClear-SM Expert (Rigaku, 2011), CrysAlis PRO (Agilent, 2012), SUPERFLIP (Palatinus & Chapuis, 2007), JANA2006 (Petříček et al., 2014), DIAMOND (Brandenburg & Putz, 2005) and Mercury (Macrae et al., 2008), enCIFer (Allen et al., 2004).

Selected geometric parameters (Å, º) for (I) top
S1—P11.9785 (6)P1—N21.6284 (15)
P1—N11.6475 (11)N1—C11.4637 (15)
P1—N1i1.6475 (11)N2—C71.470 (2)
S1—P1—N1116.50 (4)N1—P1—N2108.09 (5)
S1—P1—N1i116.50 (4)N1i—P1—N2108.09 (5)
S1—P1—N2108.46 (5)P1—N1—C1123.08 (9)
N1—P1—N1i98.51 (6)P1—N2—C7123.54 (11)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1n1···S1ii0.819 (17)2.67 (2)3.4720 (12)161.6 (16)
N2—H1n2···S1iii0.81 (3)2.87 (3)3.6201 (18)151.3 (19)
Symmetry codes: (ii) x1/2, y+1/2, z+1/2; (iii) x+1/2, y+1/2, z+1/2.
Selected geometric parameters (Å, º) for (II) top
P1—S11.9302 (6)N1—N21.3970 (17)
P1—N11.6335 (14)N2—C11.399 (2)
P1—O11.5734 (12)O2—C91.449 (4)
P1—O21.543 (2)O2'—C9'1.461 (6)
S1—P1—N1111.04 (5)O1—P1—O2106.49 (12)
S1—P1—O1115.45 (4)P1—N1—N2119.69 (9)
S1—P1—O2114.96 (10)N1—N2—C1118.31 (13)
N1—P1—O1107.99 (7)P1—O1—C7120.67 (9)
N1—P1—O299.55 (10)P1—O2—C9117.59 (19)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1n1···O1i0.839 (18)2.338 (17)3.1301 (16)157.6 (18)
N2—H1n2···S1ii0.790 (18)2.708 (18)3.4420 (15)155.5 (16)
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x, y+3/2, z+1/2.
 

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