Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614022608/fg3325sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614022608/fg3325Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614022608/fg3325IIsup3.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614022608/fg3325IIsup4.cml |
CCDC references: 1029190; 1029191
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.
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.)]
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.
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 P1═S1 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 P═S 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 P═O group (Pourayoubi, Jasinski et al., 2012).
The P═S 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 P═S bond lengths (the region of the longest bond lengths; Fig. 3) for such compounds. Fig. 4 indicates the scatterplot of P═S 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 P═S 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 P═S 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···)S═P 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···S═P 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 P═S bond length [1.9302 (6) Å] is shorter than the P═S bond length of (I).
A CSD analysis of P═S 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 P═S unit and the vector introducing the LEP orientation on this pyramidal N atom is on opposite side of the P═S 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···S═P [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 P═S bond lengths).
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).
C18H36N3PS | F(000) = 784 |
Mr = 357.5 | Dx = 1.144 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P -2xabc;-2yb;-2zac | Cell parameters from 7402 reflections |
a = 9.0897 (7) Å | θ = 3.1–33.0° |
b = 18.6342 (15) Å | µ = 0.24 mm−1 |
c = 12.2598 (8) Å | T = 120 K |
V = 2076.6 (3) Å3 | Prism, colourless |
Z = 4 | 0.30 × 0.30 × 0.25 mm |
Rigaku Saturn724+ (2x2 bin mode) diffractometer | 3731 independent reflections |
Radiation source: X-ray tube | 2645 reflections with I > 3σ(I) |
Multilayer monochromator | Rint = 0.033 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 33.1°, θmin = 3.7° |
profile data from ω–scans | h = −11→13 |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | k = −28→22 |
Tmin = 0.852, Tmax = 1.000 | l = −14→18 |
18907 measured reflections |
Refinement on F2 | 71 constraints |
R[F2 > 2σ(F2)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.130 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0016I2) |
S = 1.80 | (Δ/σ)max = 0.009 |
3731 reflections | Δρmax = 0.55 e Å−3 |
117 parameters | Δρmin = −0.43 e Å−3 |
0 restraints |
C18H36N3PS | V = 2076.6 (3) Å3 |
Mr = 357.5 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 9.0897 (7) Å | µ = 0.24 mm−1 |
b = 18.6342 (15) Å | T = 120 K |
c = 12.2598 (8) Å | 0.30 × 0.30 × 0.25 mm |
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 = 1.000 | Rint = 0.033 |
18907 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.80 | Δρmax = 0.55 e Å−3 |
3731 reflections | Δρmin = −0.43 e Å−3 |
117 parameters |
x | y | z | Uiso*/Ueq | ||
S1 | 0.33232 (5) | 0.25 | 0.16559 (3) | 0.02611 (13) | |
P1 | 0.28701 (5) | 0.25 | 0.32344 (3) | 0.02042 (12) | |
N1 | 0.18573 (12) | 0.31698 (5) | 0.36876 (9) | 0.0237 (3) | |
N2 | 0.44140 (15) | 0.25 | 0.39081 (11) | 0.0241 (4) | |
C1 | 0.22644 (13) | 0.39240 (6) | 0.35451 (9) | 0.0225 (3) | |
C2 | 0.18747 (15) | 0.43367 (6) | 0.45813 (9) | 0.0274 (3) | |
C3 | 0.22659 (15) | 0.51299 (7) | 0.44892 (10) | 0.0325 (4) | |
C4 | 0.15119 (15) | 0.54697 (7) | 0.35078 (9) | 0.0292 (4) | |
C5 | 0.18861 (15) | 0.50655 (7) | 0.24629 (9) | 0.0318 (4) | |
C6 | 0.15165 (15) | 0.42683 (7) | 0.25592 (9) | 0.0284 (3) | |
C7 | 0.45003 (18) | 0.25 | 0.51050 (13) | 0.0225 (4) | |
C8 | 0.52771 (14) | 0.18277 (6) | 0.55299 (10) | 0.0271 (3) | |
C9 | 0.52988 (17) | 0.18259 (7) | 0.67752 (10) | 0.0333 (4) | |
C10 | 0.6036 (2) | 0.25 | 0.72171 (15) | 0.0384 (6) | |
H1c1 | 0.330439 | 0.394388 | 0.341198 | 0.027* | |
H1c2 | 0.238569 | 0.413025 | 0.519055 | 0.0329* | |
H2c2 | 0.084163 | 0.428809 | 0.472615 | 0.0329* | |
H1c3 | 0.196723 | 0.537484 | 0.514157 | 0.039* | |
H2c3 | 0.33125 | 0.518065 | 0.441813 | 0.039* | |
H1c4 | 0.046593 | 0.546578 | 0.361602 | 0.0351* | |
H2c4 | 0.181937 | 0.596059 | 0.344025 | 0.0351* | |
H1c5 | 0.291455 | 0.512046 | 0.23056 | 0.0381* | |
H2c5 | 0.13499 | 0.526995 | 0.186402 | 0.0381* | |
H1c6 | 0.04702 | 0.421025 | 0.261866 | 0.0341* | |
H2c6 | 0.181793 | 0.402437 | 0.190668 | 0.0341* | |
H1c7 | 0.35082 | 0.25 | 0.537343 | 0.027* | |
H1c8 | 0.626796 | 0.181644 | 0.525932 | 0.0325* | |
H2c8 | 0.477115 | 0.140846 | 0.527223 | 0.0325* | |
H1c9 | 0.430918 | 0.179853 | 0.704562 | 0.04* | |
H2c9 | 0.581883 | 0.140994 | 0.702987 | 0.04* | |
H1c10 | 0.598415 | 0.25 | 0.799915 | 0.046* | |
H2c10 | 0.705673 | 0.25 | 0.70148 | 0.046* | |
H1n1 | 0.0966 (19) | 0.3104 (8) | 0.3684 (12) | 0.0285* | |
H1n2 | 0.516 (3) | 0.25 | 0.3542 (16) | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0192 (2) | 0.0366 (2) | 0.0225 (2) | 0 | −0.00033 (14) | 0 |
P1 | 0.0164 (2) | 0.0230 (2) | 0.0219 (2) | 0 | −0.00019 (14) | 0 |
N1 | 0.0176 (5) | 0.0243 (5) | 0.0293 (5) | −0.0002 (4) | 0.0016 (4) | 0.0010 (4) |
N2 | 0.0160 (7) | 0.0342 (7) | 0.0222 (6) | 0 | 0.0005 (5) | 0 |
C1 | 0.0196 (6) | 0.0234 (5) | 0.0246 (5) | −0.0001 (4) | 0.0014 (4) | 0.0008 (4) |
C2 | 0.0319 (7) | 0.0288 (6) | 0.0215 (5) | 0.0049 (5) | −0.0024 (5) | 0.0008 (5) |
C3 | 0.0369 (8) | 0.0289 (6) | 0.0318 (6) | 0.0044 (5) | −0.0071 (5) | −0.0053 (5) |
C4 | 0.0313 (7) | 0.0257 (6) | 0.0306 (6) | 0.0032 (5) | 0.0012 (5) | −0.0002 (5) |
C5 | 0.0400 (8) | 0.0284 (6) | 0.0268 (6) | 0.0056 (5) | 0.0066 (5) | 0.0054 (5) |
C6 | 0.0354 (7) | 0.0281 (6) | 0.0217 (5) | 0.0032 (5) | −0.0013 (5) | −0.0013 (4) |
C7 | 0.0191 (8) | 0.0273 (8) | 0.0212 (7) | 0 | 0.0000 (6) | 0 |
C8 | 0.0249 (6) | 0.0278 (6) | 0.0286 (6) | 0.0005 (5) | −0.0014 (5) | 0.0013 (5) |
C9 | 0.0326 (7) | 0.0380 (7) | 0.0294 (6) | 0.0037 (6) | 0.0004 (5) | 0.0089 (5) |
C10 | 0.0371 (11) | 0.0536 (12) | 0.0244 (8) | 0 | −0.0054 (8) | 0 |
S1—P1 | 1.9785 (6) | C4—H1c4 | 0.96 |
P1—N1 | 1.6475 (11) | C4—H2c4 | 0.96 |
P1—N1i | 1.6475 (11) | C5—C6 | 1.5276 (18) |
P1—N2 | 1.6284 (15) | C5—H1c5 | 0.96 |
N1—C1 | 1.4637 (15) | C5—H2c5 | 0.96 |
N1—H1n1 | 0.819 (17) | C6—H1c6 | 0.96 |
N2—C7 | 1.470 (2) | C6—H2c6 | 0.96 |
N2—H1n2 | 0.81 (2) | C7—C8 | 1.5295 (15) |
C1—C2 | 1.5267 (16) | C7—C8i | 1.5295 (15) |
C1—C6 | 1.5280 (16) | C7—H1c7 | 0.96 |
C1—H1c1 | 0.96 | C8—C9 | 1.5269 (17) |
C2—C3 | 1.5244 (18) | C8—H1c8 | 0.96 |
C2—H1c2 | 0.96 | C8—H2c8 | 0.96 |
C2—H2c2 | 0.96 | C9—C10 | 1.5235 (18) |
C3—C4 | 1.5226 (18) | C9—H1c9 | 0.96 |
C3—H1c3 | 0.96 | C9—H2c9 | 0.96 |
C3—H2c3 | 0.96 | C10—H1c10 | 0.96 |
C4—C5 | 1.5245 (17) | C10—H2c10 | 0.96 |
S1—P1—N1 | 116.50 (4) | C4—C5—C6 | 111.50 (10) |
S1—P1—N1i | 116.50 (4) | C4—C5—H1c5 | 109.47 |
S1—P1—N2 | 108.46 (5) | C4—C5—H2c5 | 109.47 |
N1—P1—N1i | 98.51 (6) | C6—C5—H1c5 | 109.47 |
N1—P1—N2 | 108.09 (5) | C6—C5—H2c5 | 109.47 |
N1i—P1—N2 | 108.09 (5) | H1c5—C5—H2c5 | 107.37 |
P1—N1—C1 | 123.08 (9) | C1—C6—C5 | 111.82 (10) |
P1—N1—H1n1 | 116.0 (10) | C1—C6—H1c6 | 109.47 |
C1—N1—H1n1 | 113.1 (10) | C1—C6—H2c6 | 109.47 |
P1—N2—C7 | 123.54 (11) | C5—C6—H1c6 | 109.47 |
P1—N2—H1n2 | 116.0 (15) | C5—C6—H2c6 | 109.47 |
C7—N2—H1n2 | 120.5 (15) | H1c6—C6—H2c6 | 107.02 |
N1—C1—C2 | 109.01 (9) | N2—C7—C8 | 111.39 (8) |
N1—C1—C6 | 112.65 (10) | N2—C7—C8i | 111.39 (8) |
N1—C1—H1c1 | 107.84 | N2—C7—H1c7 | 106.99 |
C2—C1—C6 | 110.09 (10) | C8—C7—C8i | 109.99 (12) |
C2—C1—H1c1 | 110.51 | C8—C7—H1c7 | 108.48 |
C6—C1—H1c1 | 106.71 | C8i—C7—H1c7 | 108.48 |
C1—C2—C3 | 111.88 (10) | C7—C8—C9 | 110.38 (10) |
C1—C2—H1c2 | 109.47 | C7—C8—H1c8 | 109.47 |
C1—C2—H2c2 | 109.47 | C7—C8—H2c8 | 109.47 |
C3—C2—H1c2 | 109.47 | C9—C8—H1c8 | 109.47 |
C3—C2—H2c2 | 109.47 | C9—C8—H2c8 | 109.47 |
H1c2—C2—H2c2 | 106.95 | H1c8—C8—H2c8 | 108.54 |
C2—C3—C4 | 110.90 (10) | C8—C9—C10 | 111.06 (11) |
C2—C3—H1c3 | 109.47 | C8—C9—H1c9 | 109.47 |
C2—C3—H2c3 | 109.47 | C8—C9—H2c9 | 109.47 |
C4—C3—H1c3 | 109.47 | C10—C9—H1c9 | 109.47 |
C4—C3—H2c3 | 109.47 | C10—C9—H2c9 | 109.47 |
H1c3—C3—H2c3 | 108 | H1c9—C9—H2c9 | 107.83 |
C3—C4—C5 | 110.99 (10) | C9—C10—C9i | 111.09 (15) |
C3—C4—H1c4 | 109.47 | C9—C10—H1c10 | 109.47 |
C3—C4—H2c4 | 109.47 | C9—C10—H2c10 | 109.47 |
C5—C4—H1c4 | 109.47 | C9i—C10—H1c10 | 109.47 |
C5—C4—H2c4 | 109.47 | C9i—C10—H2c10 | 109.47 |
H1c4—C4—H2c4 | 107.91 | H1c10—C10—H2c10 | 107.81 |
Symmetry code: (i) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1n1···S1ii | 0.819 (17) | 2.67 (2) | 3.4720 (12) | 161.6 (16) |
N2—H1n2···S1iii | 0.81 (3) | 2.87 (3) | 3.6201 (18) | 151.3 (19) |
Symmetry codes: (ii) x−1/2, −y+1/2, −z+1/2; (iii) x+1/2, −y+1/2, −z+1/2. |
C10H17N2O2PS | F(000) = 552 |
Mr = 260.3 | Dx = 1.304 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2ycb | Cell parameters from 4151 reflections |
a = 9.938 (1) Å | θ = 2.8–28.3° |
b = 16.3798 (10) Å | µ = 0.35 mm−1 |
c = 8.4156 (6) Å | T = 120 K |
β = 104.553 (11)° | Block, colourless |
V = 1325.96 (19) Å3 | 0.72 × 0.50 × 0.24 mm |
Z = 4 |
Agilent Xcalibur Atlas Gemini ultra diffractometer | 3038 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2628 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.018 |
Detector resolution: 10.3784 pixels mm-1 | θmax = 28.4°, θmin = 2.8° |
ω scans | h = −12→12 |
Absorption correction: analytical (CrysAlis PRO; Agilent, 2012) | k = −21→21 |
Tmin = 0.834, Tmax = 0.925 | l = −11→10 |
9959 measured reflections |
Refinement on F2 | 95 constraints |
R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.106 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0016I2) |
S = 1.78 | (Δ/σ)max = 0.020 |
3038 reflections | Δρmax = 0.28 e Å−3 |
170 parameters | Δρmin = −0.22 e Å−3 |
0 restraints |
C10H17N2O2PS | V = 1325.96 (19) Å3 |
Mr = 260.3 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.938 (1) Å | µ = 0.35 mm−1 |
b = 16.3798 (10) Å | T = 120 K |
c = 8.4156 (6) Å | 0.72 × 0.50 × 0.24 mm |
β = 104.553 (11)° |
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 = 0.925 | Rint = 0.018 |
9959 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.78 | Δρmax = 0.28 e Å−3 |
3038 reflections | Δρmin = −0.22 e Å−3 |
170 parameters |
Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.36.21 Analytical numeric absorption correction based on crystal shape |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
P1 | 0.37825 (4) | 0.65703 (2) | 0.16541 (4) | 0.02538 (13) | |
S1 | 0.29032 (4) | 0.60178 (3) | −0.03656 (5) | 0.03637 (15) | |
N1 | 0.41906 (14) | 0.75074 (8) | 0.13022 (14) | 0.0335 (4) | |
N2 | 0.49967 (14) | 0.79743 (8) | 0.25809 (15) | 0.0291 (4) | |
C1 | 0.63310 (15) | 0.82052 (9) | 0.24912 (16) | 0.0262 (4) | |
C2 | 0.70142 (18) | 0.88202 (10) | 0.3522 (2) | 0.0377 (5) | |
C3 | 0.83635 (19) | 0.90318 (10) | 0.3536 (2) | 0.0441 (6) | |
C4 | 0.90453 (18) | 0.86428 (11) | 0.2507 (2) | 0.0459 (6) | |
C5 | 0.83576 (17) | 0.80426 (11) | 0.1470 (2) | 0.0402 (6) | |
C6 | 0.70137 (16) | 0.78226 (9) | 0.14481 (18) | 0.0301 (5) | |
O1 | 0.29147 (11) | 0.65959 (6) | 0.29807 (12) | 0.0297 (3) | |
C7 | 0.14686 (16) | 0.68387 (10) | 0.25369 (19) | 0.0354 (5) | |
C8 | 0.0704 (2) | 0.63514 (14) | 0.3511 (3) | 0.0645 (9) | |
O2 | 0.5236 (2) | 0.62451 (14) | 0.2532 (3) | 0.0251 (7) | 0.594 (5) |
C9 | 0.5358 (3) | 0.53861 (16) | 0.2956 (4) | 0.0456 (11) | 0.594 (5) |
C10 | 0.68324 (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) |
H1c2 | 0.654546 | 0.909995 | 0.423041 | 0.0452* | |
H1c3 | 0.882992 | 0.945183 | 0.426459 | 0.0529* | |
H1c4 | 0.998269 | 0.878854 | 0.251531 | 0.055* | |
H1c5 | 0.882311 | 0.777169 | 0.074804 | 0.0482* | |
H1c6 | 0.655086 | 0.740476 | 0.071084 | 0.0361* | |
H1c7 | 0.108192 | 0.673861 | 0.138873 | 0.0425* | |
H2c7 | 0.139783 | 0.740812 | 0.277392 | 0.0425* | |
H1c8 | −0.02525 | 0.651901 | 0.324785 | 0.0774* | |
H2c8 | 0.075762 | 0.578295 | 0.32568 | 0.0774* | |
H3c8 | 0.111092 | 0.643695 | 0.466035 | 0.0774* | |
H1n1 | 0.4039 (19) | 0.7681 (11) | 0.033 (2) | 0.0402* | |
H1n2 | 0.4557 (18) | 0.8324 (11) | 0.286 (2) | 0.0349* | |
H1c9 | 0.472987 | 0.525567 | 0.361939 | 0.0547* | 0.594 (5) |
H2c9 | 0.512628 | 0.506429 | 0.197129 | 0.0547* | 0.594 (5) |
H1c10 | 0.690812 | 0.462988 | 0.418818 | 0.0506* | 0.594 (5) |
H2c10 | 0.74594 | 0.532472 | 0.323639 | 0.0506* | 0.594 (5) |
H3c10 | 0.706498 | 0.552189 | 0.488559 | 0.0506* | 0.594 (5) |
H1c10' | 0.762184 | 0.495592 | 0.36235 | 0.0506* | 0.406 (5) |
H2c10' | 0.712308 | 0.545314 | 0.49616 | 0.0506* | 0.406 (5) |
H3c10' | 0.615657 | 0.478365 | 0.39321 | 0.0506* | 0.406 (5) |
H1c9' | 0.598116 | 0.556104 | 0.1611 | 0.0381* | 0.406 (5) |
H2c9' | 0.685489 | 0.625611 | 0.274098 | 0.0381* | 0.406 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0212 (2) | 0.0296 (2) | 0.0243 (2) | 0.00049 (13) | 0.00370 (15) | −0.00535 (13) |
S1 | 0.0354 (3) | 0.0426 (3) | 0.0295 (2) | −0.00730 (16) | 0.00498 (17) | −0.01288 (16) |
N1 | 0.0415 (8) | 0.0430 (7) | 0.0168 (6) | −0.0157 (6) | 0.0085 (5) | −0.0011 (5) |
N2 | 0.0359 (7) | 0.0312 (6) | 0.0224 (6) | −0.0075 (5) | 0.0116 (5) | −0.0053 (5) |
C1 | 0.0326 (8) | 0.0240 (6) | 0.0207 (6) | −0.0019 (6) | 0.0041 (6) | 0.0064 (5) |
C2 | 0.0469 (10) | 0.0301 (8) | 0.0358 (9) | −0.0101 (7) | 0.0099 (7) | −0.0037 (6) |
C3 | 0.0457 (10) | 0.0328 (9) | 0.0466 (10) | −0.0131 (7) | −0.0019 (8) | 0.0045 (7) |
C4 | 0.0281 (9) | 0.0453 (10) | 0.0590 (11) | 0.0000 (7) | 0.0014 (8) | 0.0170 (9) |
C5 | 0.0293 (9) | 0.0459 (10) | 0.0446 (9) | 0.0091 (7) | 0.0080 (7) | 0.0059 (7) |
C6 | 0.0309 (8) | 0.0297 (7) | 0.0272 (7) | 0.0037 (6) | 0.0026 (6) | 0.0029 (6) |
O1 | 0.0281 (6) | 0.0365 (6) | 0.0250 (5) | −0.0037 (4) | 0.0075 (4) | 0.0037 (4) |
C7 | 0.0302 (8) | 0.0389 (8) | 0.0395 (9) | 0.0023 (7) | 0.0131 (7) | 0.0039 (7) |
C8 | 0.0459 (12) | 0.0671 (13) | 0.0930 (17) | 0.0046 (10) | 0.0405 (12) | 0.0307 (13) |
O2 | 0.0209 (11) | 0.0241 (10) | 0.0288 (13) | 0.0021 (8) | 0.0035 (8) | 0.0012 (9) |
C9 | 0.0395 (18) | 0.0312 (15) | 0.064 (2) | 0.0048 (12) | 0.0101 (14) | 0.0131 (13) |
C10 | 0.0501 (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) |
P1—S1 | 1.9302 (6) | C7—C8 | 1.484 (3) |
P1—N1 | 1.6335 (14) | C7—H1c7 | 0.96 |
P1—O1 | 1.5734 (12) | C7—H2c7 | 0.96 |
P1—O2 | 1.543 (2) | C8—H1c8 | 0.96 |
N1—N2 | 1.3970 (17) | C8—H2c8 | 0.96 |
N1—H1n1 | 0.839 (18) | C8—H3c8 | 0.96 |
N2—C1 | 1.399 (2) | O2—C9 | 1.449 (4) |
N2—H1n2 | 0.791 (19) | C9—C10 | 1.513 (3) |
C1—C2 | 1.390 (2) | C9—H1c9 | 0.96 |
C1—C6 | 1.387 (2) | C9—H2c9 | 0.96 |
C2—C3 | 1.382 (3) | C10—C9' | 1.455 (4) |
C2—H1c2 | 0.96 | C10—H1c10 | 0.96 |
C3—C4 | 1.382 (3) | C10—H2c10 | 0.96 |
C3—H1c3 | 0.96 | C10—H3c10 | 0.96 |
C4—C5 | 1.377 (2) | C10—H1c10' | 0.96 |
C4—H1c4 | 0.96 | C10—H2c10' | 0.96 |
C5—C6 | 1.379 (2) | C10—H3c10' | 0.96 |
C5—H1c5 | 0.96 | O2'—C9' | 1.461 (6) |
C6—H1c6 | 0.96 | C9'—H1c9' | 0.96 |
O1—C7 | 1.4468 (19) | C9'—H2c9' | 0.96 |
S1—P1—N1 | 111.04 (5) | C8—C7—H1c7 | 109.47 |
S1—P1—O1 | 115.45 (4) | C8—C7—H2c7 | 109.47 |
S1—P1—O2 | 114.96 (10) | H1c7—C7—H2c7 | 110.08 |
N1—P1—O1 | 107.99 (7) | C7—C8—H1c8 | 109.47 |
N1—P1—O2 | 99.55 (10) | C7—C8—H2c8 | 109.47 |
O1—P1—O2 | 106.49 (12) | C7—C8—H3c8 | 109.47 |
P1—N1—N2 | 119.69 (9) | H1c8—C8—H2c8 | 109.47 |
P1—N1—H1n1 | 120.1 (12) | H1c8—C8—H3c8 | 109.47 |
N2—N1—H1n1 | 119.3 (12) | H2c8—C8—H3c8 | 109.47 |
N1—N2—C1 | 118.31 (13) | P1—O2—C9 | 117.59 (19) |
N1—N2—H1n2 | 111.8 (12) | O2'—O2—C9' | 100.8 (4) |
C1—N2—H1n2 | 115.0 (13) | O2—C9—C10 | 109.7 (2) |
N2—C1—C2 | 118.89 (14) | O2—C9—H1c9 | 109.47 |
N2—C1—C6 | 122.21 (12) | O2—C9—H2c9 | 109.47 |
C2—C1—C6 | 118.86 (15) | C10—C9—H1c9 | 109.47 |
C1—C2—C3 | 120.49 (17) | C10—C9—H2c9 | 109.47 |
C1—C2—H1c2 | 119.75 | H1c9—C9—H2c9 | 109.28 |
C3—C2—H1c2 | 119.75 | C9—C10—H1c10 | 109.47 |
C2—C3—C4 | 120.44 (15) | C9—C10—H2c10 | 109.47 |
C2—C3—H1c3 | 119.78 | C9—C10—H3c10 | 109.47 |
C4—C3—H1c3 | 119.78 | C9'—C10—H1c10' | 109.47 |
C3—C4—C5 | 118.87 (17) | C9'—C10—H2c10' | 109.47 |
C3—C4—H1c4 | 120.56 | C9'—C10—H3c10' | 109.47 |
C5—C4—H1c4 | 120.56 | H1c10—C10—H2c10 | 109.47 |
C4—C5—C6 | 121.34 (17) | H1c10—C10—H3c10 | 109.47 |
C4—C5—H1c5 | 119.33 | H2c10—C10—H3c10 | 109.47 |
C6—C5—H1c5 | 119.33 | H1c10'—C10—H2c10' | 109.47 |
C1—C6—C5 | 119.98 (14) | H1c10'—C10—H3c10' | 109.47 |
C1—C6—H1c6 | 120.01 | H2c10'—C10—H3c10' | 109.47 |
C5—C6—H1c6 | 120.01 | C10—C9'—O2' | 106.6 (3) |
P1—O1—C7 | 120.67 (9) | C10—C9'—H1c9' | 109.47 |
O1—C7—C8 | 108.85 (13) | C10—C9'—H2c9' | 109.47 |
O1—C7—H1c7 | 109.47 | O2'—C9'—H1c9' | 109.47 |
O1—C7—H2c7 | 109.47 | O2'—C9'—H2c9' | 109.47 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1n1···O1i | 0.839 (18) | 2.338 (17) | 3.1301 (16) | 157.6 (18) |
N2—H1n2···S1ii | 0.790 (18) | 2.708 (18) | 3.4420 (15) | 155.5 (16) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C18H36N3PS | C10H17N2O2PS |
Mr | 357.5 | 260.3 |
Crystal system, space group | Orthorhombic, Pnma | Monoclinic, P21/c |
Temperature (K) | 120 | 120 |
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, 90 | 90, 104.553 (11), 90 |
V (Å3) | 2076.6 (3) | 1325.96 (19) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.24 | 0.35 |
Crystal size (mm) | 0.30 × 0.30 × 0.25 | 0.72 × 0.50 × 0.24 |
Data collection | ||
Diffractometer | Rigaku Saturn724+ (2x2 bin mode) diffractometer | Agilent Xcalibur Atlas Gemini ultra diffractometer |
Absorption correction | Multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | Analytical (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.852, 1.000 | 0.834, 0.925 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 18907, 3731, 2645 | 9959, 3038, 2628 |
Rint | 0.033 | 0.018 |
(sin θ/λ)max (Å−1) | 0.767 | 0.669 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.130, 1.80 | 0.034, 0.106, 1.78 |
No. of reflections | 3731 | 3038 |
No. of parameters | 117 | 170 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.55, −0.43 | 0.28, −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).
S1—P1 | 1.9785 (6) | P1—N2 | 1.6284 (15) |
P1—N1 | 1.6475 (11) | N1—C1 | 1.4637 (15) |
P1—N1i | 1.6475 (11) | N2—C7 | 1.470 (2) |
S1—P1—N1 | 116.50 (4) | N1—P1—N2 | 108.09 (5) |
S1—P1—N1i | 116.50 (4) | N1i—P1—N2 | 108.09 (5) |
S1—P1—N2 | 108.46 (5) | P1—N1—C1 | 123.08 (9) |
N1—P1—N1i | 98.51 (6) | P1—N2—C7 | 123.54 (11) |
Symmetry code: (i) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1n1···S1ii | 0.819 (17) | 2.67 (2) | 3.4720 (12) | 161.6 (16) |
N2—H1n2···S1iii | 0.81 (3) | 2.87 (3) | 3.6201 (18) | 151.3 (19) |
Symmetry codes: (ii) x−1/2, −y+1/2, −z+1/2; (iii) x+1/2, −y+1/2, −z+1/2. |
P1—S1 | 1.9302 (6) | N1—N2 | 1.3970 (17) |
P1—N1 | 1.6335 (14) | N2—C1 | 1.399 (2) |
P1—O1 | 1.5734 (12) | O2—C9 | 1.449 (4) |
P1—O2 | 1.543 (2) | O2'—C9' | 1.461 (6) |
S1—P1—N1 | 111.04 (5) | O1—P1—O2 | 106.49 (12) |
S1—P1—O1 | 115.45 (4) | P1—N1—N2 | 119.69 (9) |
S1—P1—O2 | 114.96 (10) | N1—N2—C1 | 118.31 (13) |
N1—P1—O1 | 107.99 (7) | P1—O1—C7 | 120.67 (9) |
N1—P1—O2 | 99.55 (10) | P1—O2—C9 | 117.59 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1n1···O1i | 0.839 (18) | 2.338 (17) | 3.1301 (16) | 157.6 (18) |
N2—H1n2···S1ii | 0.790 (18) | 2.708 (18) | 3.4420 (15) | 155.5 (16) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2. |