Two derivatives of (N-phenylthioureidoalkyl)phosphonates

The structures of di­phenyl [3-methyl-1-(3-phenyl­thio­ureido)­butyl]­phosphonate and di­phenyl [2-methyl-1-(3-phenyl­thio­ureido)­butyl]­phosphonate, both C₂₄H₂₇N₂O₃PS, are reported. In both compounds, the thio­urea moiety adopts a syn–syn conformation (i.e. the S—C—N—C torsion angles are synperi­planar), which enables N—H...O hydrogen bonds to be formed between centrosymmetrically related mol­ecules. The geometries around the P atoms can be described as distorted tetrahedral. Some of the functional groups in each structure are disordered. The bulk of the different alkyl substituents between the amide and phosphonate groups influences the molecular conformation and crystal packing. Although the structures of these compounds and two related derivatives appear to be similar, they are not isostructural.

S1. Comment

This paper is a part of our systematic investigations of organophosphorus derivatives of thiourea (Chęcińska et al., 2001a,b). Diphenyl (N-phenylthioureidoalkyl)phosphonates have applications in the synthesis of phosphonic analogues of natural amino acids (Kudzin & Stec, 1978). Moreover, this class of phosphonates presents a structural analogy to phenylthiocarbamoylamino acids and is therefore considered to represent compounds with the potential of biological activity. Here, the crystal structures of two compounds in this class, diphenyl [3-methyl-1-(3-phenylthioureido)butyl]phosphonate, (I), and diphenyl [2-methyl-1-(3-phenylthioureido)butyl]phosphonate, (II), are reported. \sch

The title compounds differ only in the nature of the substituent attached to the methine atom C2, namely an iso-butyl group for (I) and a sec-butyl for (II). Both structures exhibit positional disorder (see Experimental). In (I), two methyl groups are disordered, with site occupancy factors of 0.673 (9) and 0.327 (9). In (II), one phenyl ring, C21—C26, of the phosphonate group is positionally disordered over two orientations with equal site occupancies. The dihedral angle between the best planes of the disordered orientations of this phenyl ring is 4.4 (2)°.

As expected, the thioureide groups are planar in both structures. The maximum deviation of atoms H1 and H2 from the mean planes defined by atoms S1, C1, N1 and N2 is 0.03 (2) Å For which compound? The S1═C1 bond lengths in (I) and (II) are slightly shorter than the unweighted mean value of 1.681 Å for thioureas (Allen et al., 1987). Nevertheless, the geometries of the thioureide groups in (I) and (II) are similar; neither the N-Csp² (N1—C1 or N2—C1) distances nor the S1—C1—N1 or S1—C1—N2 angles differ significantly.

In both compounds, the two substituents of the thioureide group (the phenyl ring and the butylphosphonate group) adopt a syn-syn conformation with respect to the thiourea moiety (see torsion angles in Tables 1 and 3). The syn-syn conformation, found here, is rarely observed. A search of the Cambridge Structural Database (Version 5.23, April 2002 release; Allen, 2002) for structures containing the SC(NHC)₂ fragment of (I) and (II) (restraints: atom S is terminal and the N—C bonds are acyclic; see Scheme 2) revealed 70 fragments (62 refcodes). Among these structures, only 11 examples have the substituents in a syn-syn conformation, with the S—C—N—C torsion angles within the range 0 ± 11°. In the other thiourea compounds, the syn-anti conformation is preferred.

In both title compounds, the syn-syn conformation of the thiourea fragment enables the formation of N—H···O hydrogen bonds between pairs of molecules related by a centre of inversion. As a result, characteristic dimers are formed (Figs. 3 and 4). The combination of the two intermolecular N1—H1···O1ⁱ and N2—H2···O1ⁱ hydrogen bonds [symmetry code: (i) −x, −y, −z for (I) and 1 − x, 1 − y, 1 − z for (II)] creates a loop pattern, with a binary graph-set descriptor (Bernstein et al., 1995) of R₂¹(6). The hydrogen bonds within this motif have very similar geometries and are almost symmetric.

For the structures of the analogous C2-methyl, (III), and C2-iso-propyl, (IV), derivatives of (N-phenylthioureidoalkyl)phosphonates, reported earlier by Chęcińska et al. (2001a,b), an identical hydrogen-bonding pattern was found. Considering the related structures of (I)-(IV) together, it is interesting to compare the distances between the hydrogen-bond donors and accceptors. The mean intermolecular N···O distance increases in the order (III) [2.897 (3) Å], (I) [2.916 (3) Å], (II) [2.953 (2) Å] and (IV) [2.954 (3) Å], in accordance with the steric bulk of the substituent attached to the methine atom C2. Although the C2 substituent has the same number of atoms in (I) and (II), the mean N···O distances are different. The substitution at atom C3 [in (II) and (IV)] generates distinctly greater steric hindrance between the molecules of the hydrogen-bonded dimer than does subsitution at atom C4 [in (I)].

The coordination of the P atom in each structure is slightly distorted tetrahedral. The deformations of the tetrahedra can be explained by the steric effects of the different substituents and bond types, viz. the double P1═O1 and single P1—C2 bonds. The spatial requirements of the different substituents at C2 in the structures of (I)-(IV) also have an influence on the angular deformation of the PO₃C tetrahedra. In the structures (III), (I), (IV) and (II) (with substituents Me, i-Bu, ⁱPr, sec-Bu, respectively), the C2—P1—O1 angle is 113.74 (12), 115.25 (12), 116.26 (10) and 116.82 (10)°, respectively, while the C2—P1—O3 angle is 107.37 (11), 105.40 (11), 105.32 (11) and 104.85 (10)°, respectively. In other words, the size of the C2 substituents and the mode of their embranchment influence both the molecular structure and the relative positions of the molecules in the hydrogen-bonded dimers.

The molecular structures of compounds (I) and (II) are similar to those of (III) and (IV) (Chęcińska et al., 2001a,b), which suggests that their crystals may be isostructural. The pairs of compounds (I)/(III) and (II)/(IV) crystallize in the same space group [a transformation from space group P2₁/n to P2₁/c is needed for (IV)]. A basic prerequisite of isostructurality is similarity of the unit cells, which can be estimated by means of the Π index [(a+b+c/a'+b'+c')-1, where a, b, c, a', b' and c' are the orthogonalized lattice parameters; Fábián & Kálmán, 1999]. For the crystal pairs (I)/(III) and (II)/(IV), the Π values are 0.031 and 0.045, respectively. In the latter case, however, the Π index is misleading, since the differences between the b and c axes compensate each other (Table 5). Despite some degree of similarity between the unit cells, the structures are not isostructural, which is shown by the low values of the volumetric isostructurality index, I_v, [percentage ratio of the overlapping volume of molecules in analysed structures to the average of the corresponding molecular volumes; Fábián & Kálmán, 1999]. This parameter is 19.1% for (I)/(III) and 30% for (II)/(IV); for isostructural pairs, I_v is close to 100%. The compared structures are not isostructural because of the different arrangements of the molecules in their crystal lattices. This observation prompted further investigation into why these molecules exhibit different packing motifs. In order to answer this question, a detailed analysis of the conformations of the presented structures was performed.

The iso-butyl and methyl derivatives, (I) and (III), have significantly different molecular conformations (Fig. 5). The main difference is that the bulky phenyl groups have different orientations in (I) and (III), and the dihedral angles between the best planes of the corresponding phenyl rings in (I) and (III) differ by 0.2–45.7 (1)°. It is likely that the different steric requirements of the C2 substituents result in different packing arrangements for (I) and (III), which then influences the conformation of the molecules.

In contrast, the conformations of the molecules of (II) and (IV) are similar (Fig. 6). There are no significant differences between the bond lengths and angles of (II) and (IV), and the dihedral angles between the best planes of the phenyl rings differ by not more than 4.2 (1)°. However, despite their conformational similarity, the packing arrangements of the molecules of (II) and (IV) in their crystals differ (Figs. 7 and 8). Nevertheless, both structures comprise similar columns of hydrogen-bonded dimers (see the central columns of molecules in Figs. 7 and 8). The presence of a common pattern that is infinite in one dimension can be termed one-dimensional isostructurality.

In both compounds (I) and (II), weak intramolecular C—H···S and C—H···O hydrogen bonds probably exist, with H···S and H···O contacts slightly less than the sum of the van der Waals radii (Taylor & Kennard, 1982). As shown in Tables 2 and 4, the geometries of these interactions are strongly bent.

Table 5. Comparison of unit-cell parameters (Å, °) for (I)-(IV).

S2. Experimental

Compounds (I) and (II) were prepared according to the method of Kudzin & Stec (1978). (N-Phenylthioureidoalkyl)phosphonates were obtained by condensation of the appropriate aldehydes, N-phenylthiourea and triphenyl phosphite. For (I), m.p. 396–398 K; ³¹P NMR: δ 16.8 p.p.m. (AcOH/AcOD); MS/CI: [M+1]⁺ 455 (22%), [M+1–94]⁺ 361 (100%). For (II), m.p. 428–433 K; ³¹P NMR: δ 16.2 p.p.m. (AcOH/AcOD); MS/CI: [M+1]⁺ 455 (100%), [M+1–94]⁺ 361 (50%). All melting points are uncorrected. The ³¹P NMR spectra were recorded with a Bruker 200 AC spectrometer at 81.01 MHz. The mass spectra (MS/CI) were obtained with a Finnigan MAT 75 s pectrometer using the chemical ionization (isobutane) technique. The title compounds were crystallized by slow evaporation of a chloroform/ethanol solvent system (Ratio?).

S3. Refinement

During the refinement of (I), two methyl atoms, C5 and C6, revealed very anisotropic atomic displacement parameters, so two sets of split sites were introduced for these atoms. In the subsequent refinement, the site occupation factors refined to 0.673 (9) and 0.327 (9) for C5A/C6A and C5B/C6B, respectively. Bond-length restraints were applied to all C—C bonds involving the disordered atoms. The atoms of the C21—C26 phenyl ring of (II) were disordered. Two components of the disorder were modelled, using rigid planar hexagons for the phenyl rings. Refinement of the site occupation factors of the disordered atoms indicated that the two conformations were approximately equally occupied. Subsequently, the occupancies of the disordered atoms were fixed at 0.5 and similarity restraints were applied to the atomic displacement parameters of those disordered atoms that were within 1.7 Å of each other. The distances between atom pairs O2—C21A and O2—C21B were restrained to be equal, with an effective standard uncertainty of 0.003 Å. In both compounds, the amide H atoms were clearly revealed in the difference maps. Their atomic coordinates were refined with the N–H distances restrained to a common value, while their U_iso values were refined freely. All other H atoms were placed in geometrically idealized positions, with C—H distances in the range 0.93–0.98 Å, and constrained to ride on their parent atoms, with U_iso(H) = 1.2 U_eq(C) [or 1.5 U_eq(C) for the methyl groups]. Collected reflections with 2θ above 50° were omitted because of their poor quality.

Computing details

For both compounds, data collection: CrysAlis CCD in KM-4 CCD Software (Kuma, 2001); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED in KM-4 CCD Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1998); software used to prepare material for publication: PARST97 (Nardelli, 1996).

Figures

	Fig. 1. The molecular structure of (I) with the atom-numbering scheme. The minor disorder components (atoms C5B and C6B) have been omitted for clarity. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular structure of (II) with the atom-numbering scheme. The second component of the disordered phenyl ring (C21B—C26B) has been omitted for clarity. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The hydrogen-bonded dimers in (I) [symmetry code: (i) −x,-y,-z]. H atoms bonded to C atoms have been omitted.
	Fig. 4. The hydrogen-bonded dimers in (II) [symmetry code: (ii) 1 − x, 1 − y, 1 − z]. H atoms bonded to C atoms have been omitted.
	Fig. 5. A superposition of the skeletons of (I) (continuous line) and (III) (dashed line), viewed down the S1—C1 bond.
	Fig. 6. A superposition of the skeletons of (II) (continuous line) and (IV) (dashed line), viewed down the S1—C1 bond.
	Fig. 7. The crystal packing of (II).
	Fig. 8. The crystal packing of (IV).

(I) diphenyl [3-methyl-1-(3-phenylthioureido)butyl]phosphonate

Crystal data

C24H27N2O3PS	Z = 2
Mr = 454.51	F(000) = 480
Triclinic, P1	Dx = 1.235 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.1931 (7) Å	Cell parameters from 6268 reflections
b = 10.5503 (5) Å	θ = 1.8–25.8°
c = 11.9560 (7) Å	µ = 0.23 mm^−1
α = 90.932 (4)°	T = 293 K
β = 103.252 (5)°	Prism, colourless
γ = 101.923 (5)°	0.45 × 0.20 × 0.17 mm
V = 1221.78 (12) Å^3

Data collection

Kuma KM-4 CCD area-detector diffractometer	2883 reflections with I > 2σ(I)
Radiation source: CX-Mo12x0.4-S Seifert Mo tube	Rint = 0.034
Graphite monochromator	θmax = 25.0°, θmin = 3.5°
ω scans	h = −12→10
12829 measured reflections	k = −12→12
4288 independent reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: mixed
wR(F^2) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0833P)^2] where P = (Fo^2 + 2Fc^2)/3
4288 reflections	(Δ/σ)max < 0.001
307 parameters	Δρmax = 0.38 e Å^−3
18 restraints	Δρmin = −0.23 e Å^−3

Special details

Experimental. In order to monitor crystal decay, 2 standard frames were recorded after every 50 frames.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.40957 (7)	0.34031 (7)	0.15910 (6)	0.0691 (3)
N1	0.1853 (2)	0.2333 (2)	0.23068 (18)	0.0670 (6)
H1	0.104 (2)	0.188 (3)	0.216 (2)	0.075 (9)*
N2	0.1648 (2)	0.2042 (2)	0.04012 (18)	0.0583 (6)
H2	0.0881 (19)	0.162 (2)	0.041 (2)	0.055 (8)*
C1	0.2469 (3)	0.2564 (2)	0.1424 (2)	0.0532 (6)
C2	0.2049 (3)	0.2064 (2)	−0.0692 (2)	0.0569 (6)
H201	0.3006	0.2551	−0.0561	0.068*
C3	0.1140 (4)	0.2728 (3)	−0.1606 (2)	0.0823 (9)
H301	0.1323	0.2559	−0.2349	0.099*
H302	0.0179	0.2337	−0.1652	0.099*
C4	0.1357 (4)	0.4173 (3)	−0.1378 (3)	0.0893 (10)
H4A	0.1340	0.4363	−0.0577	0.107*	0.673 (9)
H4B	0.2323	0.4396	−0.0944	0.107*	0.327 (9)
C5A	0.2714 (6)	0.4818 (6)	−0.1570 (7)	0.124 (3)	0.673 (9)
H51A	0.3435	0.4539	−0.1030	0.186*	0.673 (9)
H52A	0.2832	0.5742	−0.1465	0.186*	0.673 (9)
H53A	0.2757	0.4591	−0.2340	0.186*	0.673 (9)
C6A	0.0229 (9)	0.4681 (7)	−0.2171 (10)	0.162 (5)	0.673 (9)
H61A	0.0356	0.4656	−0.2942	0.243*	0.673 (9)
H62A	0.0267	0.5560	−0.1921	0.243*	0.673 (9)
H63A	−0.0652	0.4151	−0.2156	0.243*	0.673 (9)
C5B	0.0634 (15)	0.4564 (13)	−0.0517 (10)	0.128 (6)	0.327 (9)
H51B	0.0769	0.5492	−0.0456	0.192*	0.327 (9)
H52B	0.1004	0.4266	0.0219	0.192*	0.327 (9)
H53B	−0.0335	0.4184	−0.0761	0.192*	0.327 (9)
C6B	0.138 (3)	0.5051 (17)	−0.2351 (14)	0.160 (9)	0.327 (9)
H61B	0.2233	0.5111	−0.2585	0.240*	0.327 (9)
H62B	0.1314	0.5899	−0.2101	0.240*	0.327 (9)
H63B	0.0620	0.4705	−0.2988	0.240*	0.327 (9)
P1	0.19924 (7)	0.04026 (6)	−0.11142 (6)	0.0588 (2)
O1	0.06818 (18)	−0.05100 (17)	−0.11522 (14)	0.0649 (5)
O2	0.2416 (2)	0.05432 (18)	−0.23047 (16)	0.0754 (6)
O3	0.32753 (18)	0.00418 (18)	−0.02859 (17)	0.0726 (5)
C11	0.2499 (3)	0.2707 (2)	0.3481 (2)	0.0607 (7)
C12	0.2947 (4)	0.1816 (3)	0.4226 (2)	0.0909 (10)
H12	0.2841	0.0964	0.3947	0.109*
C13	0.3550 (4)	0.2162 (4)	0.5380 (2)	0.1065 (12)
H13	0.3869	0.1554	0.5865	0.128*
C14	0.3675 (4)	0.3414 (4)	0.5805 (3)	0.1124 (14)
H14	0.4038	0.3646	0.6586	0.135*
C15	0.3258 (5)	0.4320 (4)	0.5063 (3)	0.1404 (19)
H15	0.3378	0.5175	0.5341	0.168*
C16	0.2661 (4)	0.3967 (3)	0.3909 (3)	0.1114 (13)
H16	0.2369	0.4582	0.3420	0.134*
C21	0.2224 (3)	−0.0536 (3)	−0.3081 (2)	0.0664 (7)
C22	0.0978 (3)	−0.0934 (3)	−0.3854 (3)	0.0823 (9)
H22	0.0254	−0.0525	−0.3845	0.099*
C23	0.0814 (4)	−0.1946 (4)	−0.4642 (3)	0.1017 (12)
H23	−0.0026	−0.2226	−0.5174	0.122*
C24	0.1882 (5)	−0.2548 (4)	−0.4652 (3)	0.1123 (13)
H24	0.1767	−0.3230	−0.5193	0.135*
C25	0.3110 (5)	−0.2147 (4)	−0.3870 (3)	0.1094 (13)
H25	0.3831	−0.2558	−0.3881	0.131*
C26	0.3296 (4)	−0.1137 (4)	−0.3063 (3)	0.0891 (10)
H26	0.4129	−0.0871	−0.2520	0.107*
C31	0.3264 (3)	−0.0937 (3)	0.0504 (3)	0.0639 (7)
C32	0.3693 (3)	−0.2013 (3)	0.0254 (3)	0.0908 (10)
H32	0.3936	−0.2123	−0.0439	0.109*
C33	0.3764 (4)	−0.2951 (4)	0.1053 (5)	0.1152 (14)
H33	0.4049	−0.3703	0.0894	0.138*
C34	0.3418 (4)	−0.2772 (5)	0.2067 (5)	0.1202 (16)
H34	0.3469	−0.3398	0.2604	0.144*
C35	0.2997 (5)	−0.1674 (5)	0.2294 (4)	0.1234 (14)
H35	0.2761	−0.1556	0.2989	0.148*
C36	0.2913 (4)	−0.0738 (3)	0.1514 (3)	0.0977 (11)
H36	0.2625	0.0012	0.1671	0.117*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0571 (5)	0.0725 (5)	0.0688 (5)	−0.0001 (3)	0.0102 (3)	−0.0038 (4)
N1	0.0579 (15)	0.0792 (16)	0.0529 (13)	−0.0058 (12)	0.0103 (11)	−0.0062 (11)
N2	0.0517 (14)	0.0622 (13)	0.0551 (13)	0.0007 (11)	0.0114 (11)	−0.0021 (10)
C1	0.0568 (15)	0.0497 (13)	0.0500 (14)	0.0095 (11)	0.0086 (12)	0.0004 (11)
C2	0.0601 (16)	0.0578 (14)	0.0490 (14)	0.0043 (12)	0.0129 (12)	0.0004 (11)
C3	0.109 (3)	0.076 (2)	0.0605 (18)	0.0273 (18)	0.0108 (17)	0.0082 (15)
C4	0.113 (3)	0.076 (2)	0.088 (2)	0.031 (2)	0.030 (2)	0.0174 (17)
C5A	0.121 (6)	0.089 (4)	0.157 (6)	0.006 (4)	0.041 (5)	0.012 (4)
C6A	0.134 (7)	0.094 (5)	0.229 (11)	0.035 (5)	−0.029 (7)	0.055 (5)
C5B	0.176 (14)	0.105 (9)	0.126 (11)	0.046 (9)	0.069 (10)	−0.004 (8)
C6B	0.20 (3)	0.139 (14)	0.175 (17)	0.053 (15)	0.091 (17)	0.075 (12)
P1	0.0605 (5)	0.0578 (4)	0.0557 (4)	0.0018 (3)	0.0188 (3)	0.0000 (3)
O1	0.0623 (11)	0.0679 (11)	0.0578 (11)	−0.0037 (9)	0.0173 (8)	−0.0045 (8)
O2	0.0968 (15)	0.0654 (11)	0.0671 (12)	0.0027 (10)	0.0395 (11)	−0.0026 (9)
O3	0.0570 (11)	0.0684 (12)	0.0908 (14)	0.0075 (9)	0.0185 (10)	0.0182 (10)
C11	0.0593 (16)	0.0668 (16)	0.0517 (15)	0.0075 (13)	0.0101 (12)	0.0011 (13)
C12	0.107 (3)	0.076 (2)	0.083 (2)	0.0188 (18)	0.0098 (19)	0.0111 (17)
C13	0.117 (3)	0.128 (3)	0.067 (2)	0.026 (2)	0.006 (2)	0.031 (2)
C14	0.097 (3)	0.179 (4)	0.058 (2)	0.044 (3)	0.0011 (18)	−0.014 (3)
C15	0.181 (5)	0.133 (4)	0.092 (3)	0.070 (3)	−0.027 (3)	−0.049 (3)
C16	0.155 (4)	0.089 (2)	0.079 (2)	0.050 (2)	−0.014 (2)	−0.0118 (19)
C21	0.074 (2)	0.0712 (17)	0.0564 (16)	0.0130 (15)	0.0241 (14)	0.0015 (13)
C22	0.079 (2)	0.105 (2)	0.0640 (18)	0.0304 (18)	0.0104 (16)	0.0013 (17)
C23	0.097 (3)	0.126 (3)	0.069 (2)	0.021 (2)	−0.0018 (19)	−0.015 (2)
C24	0.142 (4)	0.111 (3)	0.081 (3)	0.038 (3)	0.015 (3)	−0.026 (2)
C25	0.119 (3)	0.118 (3)	0.099 (3)	0.052 (3)	0.020 (2)	−0.023 (2)
C26	0.076 (2)	0.110 (3)	0.080 (2)	0.024 (2)	0.0114 (17)	−0.0103 (19)
C31	0.0473 (15)	0.0585 (16)	0.080 (2)	0.0058 (12)	0.0081 (13)	0.0077 (14)
C32	0.090 (2)	0.068 (2)	0.116 (3)	0.0187 (18)	0.025 (2)	0.003 (2)
C33	0.094 (3)	0.073 (2)	0.172 (5)	0.024 (2)	0.012 (3)	0.027 (3)
C34	0.089 (3)	0.104 (3)	0.147 (4)	0.012 (2)	−0.008 (3)	0.062 (3)
C35	0.149 (4)	0.130 (4)	0.100 (3)	0.040 (3)	0.035 (3)	0.041 (3)
C36	0.130 (3)	0.081 (2)	0.096 (3)	0.039 (2)	0.039 (2)	0.024 (2)

Geometric parameters (Å, º)

S1—C1	1.676 (3)	O3—C31	1.411 (3)
N1—C1	1.348 (3)	C11—C12	1.380 (4)
N1—C11	1.418 (3)	C11—C16	1.381 (4)
N1—H1	0.843 (17)	C12—C13	1.3844 (19)
N2—C1	1.348 (3)	C12—H12	0.9300
N2—C2	1.455 (3)	C13—C14	1.378 (6)
N2—H2	0.817 (16)	C13—H13	0.9300
C2—C3	1.541 (4)	C14—C15	1.381 (6)
C2—P1	1.802 (3)	C14—H14	0.9300
C2—H201	0.9800	C15—C16	1.384 (5)
C3—C4	1.505 (3)	C15—H15	0.9300
C3—H301	0.9700	C16—H16	0.9300
C3—H302	0.9700	C21—C26	1.368 (4)
C4—C5A	1.480 (4)	C21—C22	1.369 (4)
C4—C5B	1.495 (5)	C22—C23	1.370 (5)
C4—C6B	1.499 (5)	C22—H22	0.9300
C4—C6A	1.510 (4)	C23—C24	1.371 (5)
C4—H4A	0.9800	C23—H23	0.9300
C4—H4B	0.9800	C24—C25	1.360 (5)
C5A—H51A	0.9600	C24—H24	0.9300
C5A—H52A	0.9600	C25—C26	1.379 (5)
C5A—H53A	0.9600	C25—H25	0.9300
C6A—H61A	0.9600	C26—H26	0.9300
C6A—H62A	0.9600	C31—C32	1.350 (4)
C6A—H63A	0.9600	C31—C36	1.360 (4)
C5B—H51B	0.9600	C32—C33	1.387 (6)
C5B—H52B	0.9600	C32—H32	0.9300
C5B—H53B	0.9600	C33—C34	1.359 (6)
C6B—H61B	0.9600	C33—H33	0.9300
C6B—H62B	0.9600	C34—C35	1.359 (6)
C6B—H63B	0.9600	C34—H34	0.9300
P1—O1	1.4673 (18)	C35—C36	1.371 (5)
P1—O3	1.568 (2)	C35—H35	0.9300
P1—O2	1.5800 (19)	C36—H36	0.9300
O2—C21	1.409 (3)
C1—N1—C11	125.1 (2)	O1—P1—C2	115.25 (12)
C1—N1—H1	117.9 (19)	O3—P1—C2	105.40 (11)
C11—N1—H1	116.8 (19)	O2—P1—C2	101.83 (11)
C1—N2—C2	125.7 (2)	C21—O2—P1	121.96 (16)
C1—N2—H2	116.9 (17)	C31—O3—P1	127.05 (16)
C2—N2—H2	117.2 (17)	C12—C11—C16	118.5 (2)
N2—C1—N1	113.1 (2)	C12—C11—N1	120.9 (2)
N2—C1—S1	123.8 (2)	C16—C11—N1	120.5 (2)
N1—C1—S1	123.11 (18)	C11—C12—C13	121.5 (3)
N2—C2—C3	112.3 (2)	C11—C12—H12	119.3
N2—C2—P1	106.35 (16)	C13—C12—H12	119.3
C3—C2—P1	113.29 (17)	C14—C13—C12	119.5 (3)
N2—C2—H201	108.2	C14—C13—H13	120.2
C3—C2—H201	108.2	C12—C13—H13	120.2
P1—C2—H201	108.2	C13—C14—C15	119.5 (3)
C4—C3—C2	114.5 (2)	C13—C14—H14	120.3
C4—C3—H301	108.6	C15—C14—H14	120.3
C2—C3—H301	108.6	C14—C15—C16	120.5 (3)
C4—C3—H302	108.6	C14—C15—H15	119.7
C2—C3—H302	108.6	C16—C15—H15	119.7
H301—C3—H302	107.6	C11—C16—C15	120.4 (3)
C5B—C4—C6B	113.9 (9)	C11—C16—H16	119.8
C5A—C4—C3	109.5 (3)	C15—C16—H16	119.8
C5B—C4—C3	114.3 (6)	C26—C21—C22	121.7 (3)
C6B—C4—C3	120.1 (8)	C26—C21—O2	119.3 (3)
C5A—C4—C6A	109.5 (6)	C22—C21—O2	118.9 (3)
C3—C4—C6A	110.1 (4)	C21—C22—C23	118.8 (3)
C5A—C4—H4A	109.2	C21—C22—H22	120.6
C3—C4—H4A	109.2	C23—C22—H22	120.6
C6A—C4—H4A	109.2	C22—C23—C24	120.4 (3)
C5B—C4—H4B	101.6	C22—C23—H23	119.8
C6B—C4—H4B	101.6	C24—C23—H23	119.8
C3—C4—H4B	101.6	C25—C24—C23	120.0 (3)
C4—C5A—H51A	109.5	C25—C24—H24	120.0
C4—C5A—H52A	109.5	C23—C24—H24	120.0
H51A—C5A—H52A	109.5	C24—C25—C26	120.7 (4)
C4—C5A—H53A	109.5	C24—C25—H25	119.6
H51A—C5A—H53A	109.5	C26—C25—H25	119.6
H52A—C5A—H53A	109.5	C21—C26—C25	118.4 (3)
C4—C6A—H61A	109.5	C21—C26—H26	120.8
C4—C6A—H62A	109.5	C25—C26—H26	120.8
H61A—C6A—H62A	109.5	C32—C31—C36	122.2 (3)
C4—C6A—H63A	109.5	C32—C31—O3	117.9 (3)
H61A—C6A—H63A	109.5	C36—C31—O3	119.7 (3)
H62A—C6A—H63A	109.5	C31—C32—C33	118.7 (4)
C4—C5B—H51B	109.5	C31—C32—H32	120.7
C4—C5B—H52B	109.5	C33—C32—H32	120.7
H51B—C5B—H52B	109.5	C34—C33—C32	120.0 (4)
C4—C5B—H53B	109.5	C34—C33—H33	120.0
H51B—C5B—H53B	109.5	C32—C33—H33	120.0
H52B—C5B—H53B	109.5	C33—C34—C35	119.8 (4)
C4—C6B—H61B	109.5	C33—C34—H34	120.1
C4—C6B—H62B	109.5	C35—C34—H34	120.1
H61B—C6B—H62B	109.5	C34—C35—C36	121.1 (4)
C4—C6B—H63B	109.5	C34—C35—H35	119.5
H61B—C6B—H63B	109.5	C36—C35—H35	119.5
H62B—C6B—H63B	109.5	C31—C36—C35	118.2 (4)
O1—P1—O3	114.06 (11)	C31—C36—H36	120.9
O1—P1—O2	115.05 (10)	C35—C36—H36	120.9
O3—P1—O2	103.78 (11)
C2—N2—C1—N1	−176.2 (2)	N1—C11—C12—C13	−178.5 (3)
C2—N2—C1—S1	3.2 (4)	C11—C12—C13—C14	1.8 (6)
C11—N1—C1—N2	176.4 (2)	C12—C13—C14—C15	−3.1 (6)
C11—N1—C1—S1	−3.0 (4)	C13—C14—C15—C16	2.8 (7)
C1—N2—C2—C3	−121.6 (3)	C12—C11—C16—C15	−0.2 (6)
C1—N2—C2—P1	114.0 (2)	N1—C11—C16—C15	178.2 (4)
N2—C2—C3—C4	69.9 (3)	C14—C15—C16—C11	−1.2 (7)
P1—C2—C3—C4	−169.5 (2)	P1—O2—C21—C26	−95.4 (3)
C2—C3—C4—C5A	71.3 (5)	P1—O2—C21—C22	86.3 (3)
C2—C3—C4—C5B	−80.0 (7)	C26—C21—C22—C23	−1.2 (5)
C2—C3—C4—C6B	139.2 (12)	O2—C21—C22—C23	177.0 (3)
C2—C3—C4—C6A	−168.2 (6)	C21—C22—C23—C24	0.1 (5)
N2—C2—P1—O1	53.8 (2)	C22—C23—C24—C25	0.4 (6)
C3—C2—P1—O1	−70.0 (2)	C23—C24—C25—C26	0.0 (7)
N2—C2—P1—O3	−72.87 (18)	C22—C21—C26—C25	1.7 (5)
C3—C2—P1—O3	163.3 (2)	O2—C21—C26—C25	−176.6 (3)
N2—C2—P1—O2	179.06 (16)	C24—C25—C26—C21	−1.1 (6)
C3—C2—P1—O2	55.2 (2)	P1—O3—C31—C32	107.9 (3)
O1—P1—O2—C21	−40.5 (3)	P1—O3—C31—C36	−76.3 (3)
O3—P1—O2—C21	84.8 (2)	C36—C31—C32—C33	0.6 (5)
C2—P1—O2—C21	−165.9 (2)	O3—C31—C32—C33	176.3 (3)
O1—P1—O3—C31	−8.7 (3)	C31—C32—C33—C34	−0.6 (6)
O2—P1—O3—C31	−134.6 (2)	C32—C33—C34—C35	0.3 (7)
C2—P1—O3—C31	118.7 (2)	C33—C34—C35—C36	0.0 (7)
C1—N1—C11—C12	−102.0 (3)	C32—C31—C36—C35	−0.3 (5)
C1—N1—C11—C16	79.7 (4)	O3—C31—C36—C35	−176.0 (3)
C16—C11—C12—C13	−0.1 (5)	C34—C35—C36—C31	0.0 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.84 (2)	2.13 (2)	2.917 (3)	154 (2)
N2—H2···O1^i	0.82 (2)	2.15 (2)	2.915 (3)	156 (2)
C2—H201···S1	0.98	2.62	3.138 (2)	113
C3—H301···O2	0.97	2.59	3.062 (4)	110

Symmetry code: (i) −x, −y, −z.

(II) diphenyl [2-methyl-1-(3-phenylthioureido)butyl]phosphonate

Crystal data

C24H27N2O3PS	F(000) = 960
Mr = 454.51	Dx = 1.278 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 11020 reflections
a = 9.9402 (4) Å	θ = 1.9–26.9°
b = 16.7505 (6) Å	µ = 0.23 mm^−1
c = 14.1979 (5) Å	T = 293 K
β = 91.973 (3)°	Prism, colourless
V = 2362.60 (15) Å^3	0.45 × 0.32 × 0.25 mm
Z = 4

Data collection

Kuma KM-4 CCD area-detector diffractometer	4148 independent reflections
Radiation source: CX-Mo12x0.4-S Seifert Mo tube	3184 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ω scans	θmax = 25.0°, θmin = 3.5°
Absorption correction: numerical (X-RED; Stoe & Cie, 1999)	h = −11→11
Tmin = 0.901, Tmax = 0.950	k = −19→19
14062 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: mixed
wR(F^2) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0682P)^2 + 0.0422P] where P = (Fo^2 + 2Fc^2)/3
4148 reflections	(Δ/σ)max < 0.001
320 parameters	Δρmax = 0.32 e Å^−3
231 restraints	Δρmin = −0.28 e Å^−3

Special details

Experimental. In order to monitor crystal decay, 2 standard frames were recorded after every 50 frames.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.41733 (9)	0.33503 (4)	0.22394 (5)	0.0764 (3)
C1	0.4009 (2)	0.41162 (13)	0.29735 (15)	0.0475 (5)
N1	0.3649 (2)	0.48546 (12)	0.26852 (14)	0.0552 (5)
H1	0.361 (2)	0.5208 (13)	0.3087 (16)	0.055 (7)*
N2	0.42313 (19)	0.40706 (11)	0.39175 (13)	0.0495 (5)
H2	0.410 (2)	0.4484 (12)	0.4229 (15)	0.046 (6)*
C2	0.4646 (2)	0.33567 (13)	0.44276 (15)	0.0475 (5)
H201	0.4751	0.2932	0.3962	0.057*
C3	0.3601 (2)	0.30688 (15)	0.51237 (18)	0.0618 (7)
H301	0.4006	0.2621	0.5475	0.074*
C4	0.3240 (3)	0.37063 (19)	0.5847 (2)	0.0861 (9)
H401	0.2638	0.3482	0.6291	0.129*
H402	0.2810	0.4149	0.5529	0.129*
H403	0.4044	0.3887	0.6175	0.129*
C5	0.2356 (3)	0.27521 (19)	0.4608 (3)	0.0914 (10)
H501	0.1630	0.2727	0.5046	0.110*
H502	0.2092	0.3128	0.4115	0.110*
C6	0.2515 (4)	0.1946 (2)	0.4173 (4)	0.1354 (17)
H601	0.2826	0.1574	0.4647	0.203*
H602	0.3158	0.1976	0.3685	0.203*
H603	0.1664	0.1771	0.3909	0.203*
P1	0.62958 (6)	0.35621 (3)	0.49463 (4)	0.04534 (19)
O1	0.64574 (15)	0.43137 (8)	0.54679 (10)	0.0505 (4)
O2	0.65682 (16)	0.27821 (9)	0.55433 (12)	0.0605 (5)
O3	0.72806 (18)	0.34712 (10)	0.41148 (13)	0.0674 (5)
C11	0.3427 (3)	0.50966 (14)	0.17258 (16)	0.0538 (6)
C12	0.4325 (3)	0.56019 (19)	0.1326 (2)	0.0804 (8)
H12	0.5086	0.5766	0.1673	0.096*
C13	0.4115 (4)	0.5871 (2)	0.0411 (2)	0.1054 (12)
H13	0.4733	0.6214	0.0146	0.126*
C14	0.3012 (5)	0.5637 (2)	−0.0093 (2)	0.0975 (11)
H14	0.2871	0.5816	−0.0709	0.117*
C15	0.2104 (4)	0.5139 (2)	0.0299 (2)	0.0940 (10)
H15	0.1342	0.4981	−0.0051	0.113*
C16	0.2307 (3)	0.48615 (19)	0.12255 (19)	0.0772 (8)
H16	0.1685	0.4522	0.1492	0.093*
C31	0.8092 (2)	0.40726 (14)	0.37285 (18)	0.0558 (6)
C32	0.9315 (3)	0.42194 (18)	0.4143 (2)	0.0761 (8)
H32	0.9592	0.3951	0.4689	0.091*
C33	1.0139 (3)	0.4775 (2)	0.3738 (3)	0.0988 (11)
H33	1.0981	0.4884	0.4013	0.119*
C34	0.9730 (5)	0.5167 (2)	0.2939 (3)	0.1024 (12)
H34	1.0286	0.5545	0.2672	0.123*
C35	0.8493 (4)	0.4999 (2)	0.2530 (2)	0.0994 (11)
H35	0.8213	0.5263	0.1981	0.119*
C36	0.7656 (3)	0.4438 (2)	0.2928 (2)	0.0778 (8)
H36	0.6819	0.4317	0.2651	0.093*
C21A	0.7620 (5)	0.2735 (5)	0.6187 (3)	0.0614 (11)	0.50
C22A	0.7274 (4)	0.2986 (4)	0.7079 (4)	0.0685 (11)	0.50
H22A	0.6423	0.3196	0.7173	0.082*	0.50
C23A	0.8199 (4)	0.2923 (3)	0.7832 (3)	0.0798 (13)	0.50
H23A	0.7967	0.3091	0.8429	0.096*	0.50
C24A	0.9471 (4)	0.2609 (3)	0.7692 (3)	0.0812 (14)	0.50
H24A	1.0090	0.2567	0.8196	0.097*	0.50
C25A	0.9818 (4)	0.2358 (3)	0.6800 (3)	0.0803 (13)	0.50
H25A	1.0669	0.2148	0.6706	0.096*	0.50
C26A	0.8892 (5)	0.2421 (4)	0.6047 (3)	0.0737 (12)	0.50
H26A	0.9124	0.2253	0.5450	0.088*	0.50
C21B	0.7645 (4)	0.2668 (5)	0.6162 (4)	0.0612 (11)	0.50
C22B	0.7693 (4)	0.2888 (4)	0.7107 (4)	0.0711 (11)	0.50
H22B	0.6964	0.3147	0.7363	0.085*	0.50
C23B	0.8831 (4)	0.2719 (3)	0.7669 (3)	0.0770 (13)	0.50
H23B	0.8863	0.2866	0.8301	0.092*	0.50
C24B	0.9920 (3)	0.2331 (3)	0.7286 (3)	0.0776 (13)	0.50
H24B	1.0681	0.2218	0.7661	0.093*	0.50
C25B	0.9872 (4)	0.2111 (3)	0.6341 (3)	0.0773 (13)	0.50
H25B	1.0601	0.1852	0.6085	0.093*	0.50
C26B	0.8735 (5)	0.2280 (4)	0.5779 (3)	0.0684 (12)	0.50
H26B	0.8703	0.2133	0.5147	0.082*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.1148 (6)	0.0614 (4)	0.0518 (4)	0.0187 (4)	−0.0161 (4)	−0.0198 (3)
C1	0.0529 (13)	0.0469 (13)	0.0421 (12)	0.0004 (10)	−0.0052 (10)	−0.0042 (10)
N1	0.0812 (14)	0.0473 (12)	0.0368 (11)	0.0036 (10)	−0.0037 (10)	−0.0034 (9)
N2	0.0683 (13)	0.0410 (11)	0.0384 (10)	0.0050 (9)	−0.0078 (9)	−0.0078 (9)
C2	0.0582 (13)	0.0393 (11)	0.0445 (12)	0.0011 (10)	−0.0039 (10)	−0.0025 (10)
C3	0.0578 (15)	0.0575 (15)	0.0698 (17)	−0.0032 (12)	−0.0007 (13)	0.0124 (13)
C4	0.089 (2)	0.094 (2)	0.077 (2)	0.0047 (17)	0.0307 (16)	0.0088 (18)
C5	0.0635 (18)	0.082 (2)	0.128 (3)	−0.0081 (15)	−0.0093 (18)	0.016 (2)
C6	0.125 (3)	0.078 (2)	0.199 (5)	−0.020 (2)	−0.060 (3)	−0.003 (3)
P1	0.0528 (3)	0.0391 (3)	0.0439 (3)	0.0005 (2)	−0.0016 (3)	−0.0037 (2)
O1	0.0643 (10)	0.0414 (8)	0.0455 (8)	−0.0007 (7)	−0.0030 (7)	−0.0060 (7)
O2	0.0635 (10)	0.0434 (9)	0.0729 (11)	−0.0014 (7)	−0.0200 (9)	0.0059 (8)
O3	0.0781 (12)	0.0537 (10)	0.0719 (12)	−0.0082 (8)	0.0259 (9)	−0.0175 (9)
C11	0.0688 (15)	0.0527 (14)	0.0398 (13)	0.0089 (12)	−0.0022 (11)	−0.0012 (11)
C12	0.093 (2)	0.083 (2)	0.0641 (18)	−0.0123 (17)	−0.0077 (15)	0.0172 (16)
C13	0.142 (3)	0.099 (3)	0.076 (2)	−0.017 (2)	0.006 (2)	0.031 (2)
C14	0.145 (3)	0.092 (2)	0.0546 (19)	0.023 (2)	−0.013 (2)	0.0104 (18)
C15	0.096 (2)	0.121 (3)	0.063 (2)	0.016 (2)	−0.0290 (18)	−0.012 (2)
C16	0.0814 (19)	0.092 (2)	0.0577 (17)	−0.0027 (16)	−0.0077 (15)	−0.0055 (15)
C31	0.0584 (15)	0.0534 (14)	0.0566 (15)	−0.0032 (11)	0.0149 (12)	−0.0122 (12)
C32	0.0632 (17)	0.083 (2)	0.0824 (19)	−0.0003 (14)	0.0015 (15)	−0.0018 (16)
C33	0.068 (2)	0.110 (3)	0.119 (3)	−0.0288 (19)	0.017 (2)	−0.023 (2)
C34	0.119 (3)	0.086 (2)	0.105 (3)	−0.035 (2)	0.052 (3)	−0.012 (2)
C35	0.138 (3)	0.095 (2)	0.066 (2)	−0.001 (2)	0.022 (2)	0.0113 (18)
C36	0.0784 (19)	0.093 (2)	0.0624 (18)	−0.0052 (17)	0.0039 (15)	−0.0023 (17)
C21A	0.0656 (19)	0.052 (2)	0.066 (2)	−0.0098 (18)	−0.0155 (19)	0.0160 (19)
C22A	0.075 (2)	0.059 (2)	0.070 (2)	−0.012 (2)	−0.018 (2)	0.020 (2)
C23A	0.082 (3)	0.077 (2)	0.079 (2)	−0.006 (2)	−0.023 (2)	0.025 (2)
C24A	0.077 (3)	0.083 (3)	0.082 (2)	−0.003 (2)	−0.024 (2)	0.025 (2)
C25A	0.074 (2)	0.084 (3)	0.081 (3)	−0.003 (2)	−0.026 (2)	0.022 (2)
C26A	0.072 (2)	0.072 (2)	0.076 (2)	−0.003 (2)	−0.016 (2)	0.018 (2)
C21B	0.0644 (19)	0.052 (2)	0.066 (2)	−0.0084 (18)	−0.0152 (19)	0.0189 (18)
C22B	0.074 (2)	0.066 (2)	0.072 (2)	−0.009 (2)	−0.017 (2)	0.0199 (19)
C23B	0.073 (3)	0.083 (3)	0.073 (2)	−0.008 (2)	−0.023 (2)	0.026 (2)
C24B	0.076 (2)	0.085 (3)	0.070 (3)	−0.008 (2)	−0.020 (2)	0.026 (2)
C25B	0.074 (2)	0.080 (3)	0.077 (3)	0.000 (2)	−0.017 (2)	0.020 (2)
C26B	0.065 (2)	0.067 (2)	0.071 (2)	0.000 (2)	−0.017 (2)	0.018 (2)

Geometric parameters (Å, º)

S1—C1	1.664 (2)	C15—C16	1.403 (4)
C1—N1	1.347 (3)	C15—H15	0.9300
C1—N2	1.353 (3)	C16—H16	0.9300
N1—C11	1.431 (3)	C31—C36	1.349 (4)
N1—H1	0.825 (19)	C31—C32	1.354 (4)
N2—C2	1.450 (3)	C32—C33	1.379 (4)
N2—H2	0.833 (19)	C32—H32	0.9300
C2—C3	1.535 (3)	C33—C34	1.360 (5)
C2—P1	1.808 (2)	C33—H33	0.9300
C2—H201	0.9800	C34—C35	1.371 (5)
C3—C5	1.513 (4)	C34—H34	0.9300
C3—C4	1.533 (4)	C35—C36	1.389 (4)
C3—H301	0.9800	C35—H35	0.9300
C4—H401	0.9600	C36—H36	0.9300
C4—H402	0.9600	C21A—C22A	1.3900
C4—H403	0.9600	C21A—C26A	1.3900
C5—C6	1.494 (5)	C22A—C23A	1.3900
C5—H501	0.9700	C22A—H22A	0.9300
C5—H502	0.9700	C23A—C24A	1.3900
C6—H601	0.9600	C23A—H23A	0.9300
C6—H602	0.9600	C24A—C25A	1.3900
C6—H603	0.9600	C24A—H24A	0.9300
P1—O1	1.4667 (14)	C25A—C26A	1.3900
P1—O3	1.5668 (17)	C25A—H25A	0.9300
P1—O2	1.5758 (16)	C26A—H26A	0.9300
O2—C21A	1.367 (3)	C21B—C22B	1.3900
O2—C21B	1.375 (2)	C21B—C26B	1.3900
O3—C31	1.413 (3)	C22B—C23B	1.3900
C11—C16	1.358 (4)	C22B—H22B	0.9300
C11—C12	1.368 (4)	C23B—C24B	1.3900
C12—C13	1.384 (4)	C23B—H23B	0.9300
C12—H12	0.9300	C24B—C25B	1.3900
C13—C14	1.347 (5)	C24B—H24B	0.9300
C13—H13	0.9300	C25B—C26B	1.3900
C14—C15	1.362 (5)	C25B—H25B	0.9300
C14—H14	0.9300	C26B—H26B	0.9300
N1—C1—N2	112.66 (19)	C14—C15—C16	120.7 (3)
N1—C1—S1	123.24 (17)	C14—C15—H15	119.6
N2—C1—S1	124.10 (17)	C16—C15—H15	119.6
C1—N1—C11	125.4 (2)	C11—C16—C15	118.9 (3)
C1—N1—H1	117.9 (16)	C11—C16—H16	120.6
C11—N1—H1	116.4 (16)	C15—C16—H16	120.6
C1—N2—C2	125.10 (19)	C36—C31—C32	122.8 (3)
C1—N2—H2	117.1 (15)	C36—C31—O3	118.6 (2)
C2—N2—H2	117.8 (15)	C32—C31—O3	118.4 (2)
N2—C2—C3	113.19 (19)	C31—C32—C33	118.6 (3)
N2—C2—P1	106.53 (14)	C31—C32—H32	120.7
C3—C2—P1	114.94 (16)	C33—C32—H32	120.7
N2—C2—H201	107.3	C34—C33—C32	120.6 (3)
C3—C2—H201	107.3	C34—C33—H33	119.7
P1—C2—H201	107.3	C32—C33—H33	119.7
C5—C3—C4	111.2 (2)	C33—C34—C35	119.5 (3)
C5—C3—C2	111.0 (2)	C33—C34—H34	120.3
C4—C3—C2	113.1 (2)	C35—C34—H34	120.3
C5—C3—H301	107.1	C34—C35—C36	120.5 (3)
C4—C3—H301	107.1	C34—C35—H35	119.7
C2—C3—H301	107.1	C36—C35—H35	119.7
C3—C4—H401	109.5	C31—C36—C35	118.0 (3)
C3—C4—H402	109.5	C31—C36—H36	121.0
H401—C4—H402	109.5	C35—C36—H36	121.0
C3—C4—H403	109.5	O2—C21A—C22A	112.6 (4)
H401—C4—H403	109.5	O2—C21A—C26A	127.2 (4)
H402—C4—H403	109.5	C22A—C21A—C26A	120.0
C6—C5—C3	114.8 (3)	C23A—C22A—C21A	120.0
C6—C5—H501	108.6	C23A—C22A—H22A	120.0
C3—C5—H501	108.6	C21A—C22A—H22A	120.0
C6—C5—H502	108.6	C22A—C23A—C24A	120.0
C3—C5—H502	108.6	C22A—C23A—H23A	120.0
H501—C5—H502	107.5	C24A—C23A—H23A	120.0
C5—C6—H601	109.5	C23A—C24A—C25A	120.0
C5—C6—H602	109.5	C23A—C24A—H24A	120.0
H601—C6—H602	109.5	C25A—C24A—H24A	120.0
C5—C6—H603	109.5	C26A—C25A—C24A	120.0
H601—C6—H603	109.5	C26A—C25A—H25A	120.0
H602—C6—H603	109.5	C24A—C25A—H25A	120.0
O1—P1—O3	113.79 (9)	C25A—C26A—C21A	120.0
O1—P1—O2	115.23 (9)	C25A—C26A—H26A	120.0
O3—P1—O2	102.97 (10)	C21A—C26A—H26A	120.0
O1—P1—C2	116.82 (10)	O2—C21B—C22B	125.5 (4)
O3—P1—C2	104.85 (10)	O2—C21B—C26B	114.5 (4)
O2—P1—C2	101.42 (9)	C22B—C21B—C26B	120.0
C21A—O2—P1	121.4 (4)	C23B—C22B—C21B	120.0
C21B—O2—P1	125.1 (4)	C23B—C22B—H22B	120.0
C31—O3—P1	127.09 (14)	C21B—C22B—H22B	120.0
C16—C11—C12	119.8 (2)	C22B—C23B—C24B	120.0
C16—C11—N1	120.8 (2)	C22B—C23B—H23B	120.0
C12—C11—N1	119.3 (2)	C24B—C23B—H23B	120.0
C11—C12—C13	120.8 (3)	C25B—C24B—C23B	120.0
C11—C12—H12	119.6	C25B—C24B—H24B	120.0
C13—C12—H12	119.6	C23B—C24B—H24B	120.0
C14—C13—C12	119.9 (3)	C26B—C25B—C24B	120.0
C14—C13—H13	120.1	C26B—C25B—H25B	120.0
C12—C13—H13	120.1	C24B—C25B—H25B	120.0
C13—C14—C15	120.0 (3)	C25B—C26B—C21B	120.0
C13—C14—H14	120.0	C25B—C26B—H26B	120.0
C15—C14—H14	120.0	C21B—C26B—H26B	120.0
N2—C1—N1—C11	176.1 (2)	C12—C11—C16—C15	0.6 (4)
S1—C1—N1—C11	−3.4 (3)	N1—C11—C16—C15	177.5 (3)
N1—C1—N2—C2	−179.2 (2)	C14—C15—C16—C11	−0.1 (5)
S1—C1—N2—C2	0.2 (3)	P1—O3—C31—C36	−99.1 (3)
C1—N2—C2—C3	−116.7 (2)	P1—O3—C31—C32	85.3 (3)
C1—N2—C2—P1	116.0 (2)	C36—C31—C32—C33	1.1 (4)
N2—C2—C3—C5	69.0 (3)	O3—C31—C32—C33	176.5 (2)
P1—C2—C3—C5	−168.28 (18)	C31—C32—C33—C34	0.0 (5)
N2—C2—C3—C4	−56.8 (3)	C32—C33—C34—C35	−0.7 (5)
P1—C2—C3—C4	65.9 (3)	C33—C34—C35—C36	0.4 (6)
C4—C3—C5—C6	−157.9 (3)	C32—C31—C36—C35	−1.4 (4)
C2—C3—C5—C6	75.2 (4)	O3—C31—C36—C35	−176.8 (2)
N2—C2—P1—O1	49.14 (18)	C34—C35—C36—C31	0.6 (5)
C3—C2—P1—O1	−77.09 (18)	P1—O2—C21A—C22A	89.7 (4)
N2—C2—P1—O3	−77.85 (16)	P1—O2—C21A—C26A	−95.2 (5)
C3—C2—P1—O3	155.92 (17)	O2—C21A—C22A—C23A	175.5 (6)
N2—C2—P1—O2	175.26 (14)	C26A—C21A—C22A—C23A	0.0
C3—C2—P1—O2	49.03 (18)	C21A—C22A—C23A—C24A	0.0
O1—P1—O2—C21A	−41.6 (3)	C22A—C23A—C24A—C25A	0.0
O3—P1—O2—C21A	82.9 (3)	C23A—C24A—C25A—C26A	0.0
C2—P1—O2—C21A	−168.7 (3)	C24A—C25A—C26A—C21A	0.0
O1—P1—O2—C21B	−45.6 (4)	O2—C21A—C26A—C25A	−174.7 (7)
O3—P1—O2—C21B	78.9 (3)	C22A—C21A—C26A—C25A	0.0
C2—P1—O2—C21B	−172.8 (3)	P1—O2—C21B—C22B	87.1 (5)
O1—P1—O3—C31	−12.2 (2)	P1—O2—C21B—C26B	−94.7 (4)
O2—P1—O3—C31	−137.7 (2)	O2—C21B—C22B—C23B	178.2 (7)
C2—P1—O3—C31	116.6 (2)	C26B—C21B—C22B—C23B	0.0
C1—N1—C11—C16	73.4 (3)	C21B—C22B—C23B—C24B	0.0
C1—N1—C11—C12	−109.8 (3)	C22B—C23B—C24B—C25B	0.0
C16—C11—C12—C13	−0.7 (5)	C23B—C24B—C25B—C26B	0.0
N1—C11—C12—C13	−177.6 (3)	C24B—C25B—C26B—C21B	0.0
C11—C12—C13—C14	0.2 (6)	O2—C21B—C26B—C25B	−178.4 (6)
C12—C13—C14—C15	0.3 (6)	C22B—C21B—C26B—C25B	0.0
C13—C14—C15—C16	−0.3 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.82 (2)	2.20 (2)	2.974 (2)	155 (2)
N2—H2···O1^i	0.83 (2)	2.14 (2)	2.932 (2)	159 (2)
C2—H201···S1	0.98	2.59	3.126 (2)	115
C3—H301···O2	0.98	2.56	3.027 (3)	109

Symmetry code: (i) −x+1, −y+1, −z+1.