3-[(Di­phenyl­phosphino­thio­yl)­oxy]-N-methyl­propan-1-aminium di­phenyl­phosphanyl­thio­ate

The title salt, C₁₆H₂₁NOPS⁺·C₁₂H₁₀OPS, was synthesized from the reaction between 3-(methyl­amino)­propan-1-ol and PPh₂(S)Cl in the presence of Et₃N. Its structure has been identified using spectroscopic methods and X-ray analysis. Single crystals were obtained from ethanol by slow evaporation. In the asymmetric unit, a cation–anion pair is formed through an inter­molecular N—H...O [N...O = 2.6974 (18) Å] hydrogen bond. The mol­ecules are packed through N—H...O and N—H...S hydrogen bonds in the crystal and these hydrogen bonds are responsible for the high melting point. The P atoms of the anion and cation both have distorted tetra­hedral environments.

S1. Intruduction

Neutral thio­phospho­ryl compounds can react both as nucleophiles and as electrophiles and are resistant to hydrolysis. Group B metals are extracted particularly well by these compounds (Teichmann et al., 1967). Di­phenyl­phosphanyl­thioic chloride reacts with H₂NOSiMe₃ and Et₃N in CH₂Cl₂, and desilylation of the product yields a phospho­namidate (Harger, 1997). Likewise, di­phenyl­phosphanyl­thioic chloride reacts with sulfur and Et₃N to yield the ammonia salt Ph₂P(S)S^-.HNEt₃⁺, and upon further reaction with HCl, the acid Ph₂P(S)SH is generated (Wagner et al., 2012). A similar reaction does not occur with H₂S. The corresponding anion of di­thio­phospho­rus ligands, [R₂PSO]^-, are ambident nucleophiles, and easily react with hard or soft metals because of the terminal S and O atoms. This type of group can play an important role as a monodentate, bidentate or bridging ligand in coordination (Silvestru et al., 1997). Di­phenyl­phosphanyldi­thioic acid and its derivatives can be used in different applications, e.g. as flame retardants for polystyrene foams, as UV-stabilizers, as corrosion inhibitors or as photochemically crosslinkable coatings in polyolefins (Wagner et al., 2012). A reaction similar to a Michael addition can occur with tri­ethyl­ammonium di­phenyl­phosphanyldi­thio­ate and different acrylates. Thus, we attempted the synthesis of an inter­esting product, a novel diphosphine phosphinite di­sulfide ligand, namely O-{3-[(di­phenyl­phosphino­thioyl)(methyl)­amino]­propyl di­phenyl­(sulfanyl­idene)phosphinite, (II), in order to study its structure and properties. Our approach was to react PPh₂(S)Cl and MeNH(CH₂)₃OH in toluene in the presence of Et₃N. We expected that the two acidic H atoms of the amine and hy­droxy groups would leave by adding the NEt₃ and PPh₂SCl. Before obtaning a crystal of (I) and determining its structure, we believed that we had synthesized (II). The expected product should be oily, but the product obtained had a high melting point (427–430 K) and was quite soluble in water. This product was determined to be the ammonium salt, 3-[(di­phenyl­phosphino­thioyl)­oxy]-N-methyl­propan-1-aminium di­phenyl­phosphanyl­thio­ate, (I), which was surprising since PPh₂(S)Cl should be hydrolyzed with water in the presence of NEt₃ (Cupertino et al., 1988), and the halogenophosphine compounds should be easily exchangeble with the –OH group under basic hydrolysis conditions. Thus, PPh₂(S)OH should be attached to the amine group. Unhydrolyzed PPh₂SCl could react with the –OH group,and the –OH group is attached to the PPh₂(S)– group as expected, but it is surprising that the amine group is protonated (Wen et al., 2013). We have also obtained similar results in the reaction of 3-mercaptopropan-1-ol with PPh₂(S)Cl in the presence of Et₃N and PPh₂(S)Cl, and generated the products PPh₂(S)–OPPh₂(S) and PPh₂(S)SH (İrişli et al., 2014).

S2. Experimental

S2.1. Synthesis and crystallization

Tri­ethyl­amine (0.056 ml, 0.0004 mol) was added slowly to a suspension of 3-(methyl­amino)­propan-1-ol (0.019 ml, 0.0002 mol) in toluene. A solution of PPh₂SCl (0.08 ml, 0.0004 mol) in toluene was added slowly dropwise at 195 K. After addition, the mixture was stirred at room temprature for 24 h. Tri­ethyl­amine hydro­chloride were separated with a canula. The toluene was evaporated off under a vacuum. The product was recrystallized from dicholoro­methane/hexane (1:3 v/v) (m.p. 427–430) and the single crystal used for analysis was obtained from ethanol by slow evaporation. FT–IR (KBr, cm^-1): (P═S) 632.13, 613.35. ³¹P{¹H} NMR (H₃PO₄, CDCl₃): δ 84.73 and 59.67. ¹H NMR (TMS, CDCl₃): δ 7.78, 7.45 and 7.29 (m, 20H), 3.93 (m, 2H), 2.88 (t, 2H), 2.13 (m, 2H), 2.43 (s, 3H). Analysis was calculated for C₂₈H₃₁NO₂P₂S₂: C 62.32, H 5.79, N 2.60, S 11.88%; found: C 61.93, H 6.00, N 2.52, S 10.87%.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were evident from a difference map and were included in the refinement by restraints on the attached atom. All H atoms were positioned geometrically and treated using a riding model, fixing the bond lengths at 0.90, 0.93, 0.97 and 0.96 Å for NH₂, CH, CH₂ and CH₃ atoms, respectively. The displacement parameters of the H atoms were fixed at U_iso(H) = 1.5U_eq(C) for methyl H atoms and at 1.5U_eq(C) otherwise.

S3. Results and discussion

The structure of (I) (Fig. 1) has been studied by spectroscopic methods and also X-ray diffraction. The ³¹P{¹H} NMR spectrum of the compound has two singlets at 84.73 and 59.67 p.p.m. These are consistent with similar compounds in the literature (Silvestru et al., 1997; Karaman et al., 2014; Balakrishna et al., 2005). The results of the elemental analysis is in agreement with the proposed molecular structure. A single crystal of (I) was obtained from ethanol by slow evaporation. In the cation of (I), the three methyl­ene groups, the ammonium group and the (di­phenyl­phosphino­thioyl)­oxy group are aligned in a zigzag conformation. The two P—S bond lengths are equivalent and suggest a P═O double bond. The O—P bond lengths are slightly different [1.5102 (13) and 1.5916 (12) Å], suggesting a P—O single bond (Du et al., 2013; Güzelsoylu et al., 2011; Balakrishna et al., 2005). Both P atoms in the salt have distorted tetra­hedral environments (Table 2). The protonated N atom forms a hydrogen bond with one of the O atoms (Table 3). As shown in the packing diagram (Fig. 2), anions and cations are linked by inter­molecular N1—H1A···S1ⁱ, N1—H1A···O1ⁱ and N1—H1B···O1 hydrogen bonds (see Table 3 for geometric details and symmetry codes). The N1—H1A···O1ⁱ and N1—H1B···O1 hydrogen bonds generate R₄²(8) rings, while N1—H1A···O1ⁱ and N1—H1A···S1ⁱ generate R₁²(4) rings. In addition, an intra­molecular C8—H8···O1 hydrogen bond [add details to Table 3] generates an S(5) rings (Bernstein et al., 1995).

The final crystallographic information was deposited with the Cambridge Crystallographic Data Centre (CCDC 931171).

Related literature

For general background to 3-[(diphenylphosphanyl)oxy]-N-methylpropan-1-aminium diphenylphosphanylthioate, see: Balakrishna et al. (2005); Silvestru, et al. (1997); Wagner et al. (2012); Cupertino et al. (1988).

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A packing diagram of the crystal structure of (I), showing the formation of R4^2(8) and R1^2(4) versus S(5) rings.

3-[(Diphenylphosphinothioyl)oxy]-N-methylpropan-1-aminium diphenylphosphanylthioate

Crystal data

C16H21NOPS^+·C12H10OPS^−	Z = 2
Mr = 539.60	F(000) = 568
Triclinic, P1	Dx = 1.248 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6999 (4) Å	Cell parameters from 26612 reflections
b = 13.1458 (6) Å	θ = 2.5–28.0°
c = 13.6405 (5) Å	µ = 0.32 mm^−1
α = 86.201 (3)°	T = 296 K
β = 72.482 (3)°	Prism, light yellow
γ = 74.886 (3)°	0.62 × 0.52 × 0.43 mm
V = 1436.09 (11) Å^3

Data collection

STOE IPDS 2 diffractometer	5944 independent reflections
Radiation source: fine-focus sealed tube	5051 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
rotation method scans	θmax = 26.5°, θmin = 2.5°
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	h = −10→10
Tmin = 0.812, Tmax = 0.890	k = −16→16
26612 measured reflections	l = −17→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.107	w = 1/[σ^2(Fo^2) + (0.0553P)^2 + 0.2299P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
5944 reflections	Δρmax = 0.26 e Å^−3
316 parameters	Δρmin = −0.20 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.6055 (2)	0.19208 (14)	0.90041 (13)	0.0543 (4)
C2	0.6165 (3)	0.10835 (19)	0.96607 (19)	0.0799 (6)
H2	0.5235	0.1028	1.0199	0.096*
C3	0.7660 (4)	0.0319 (2)	0.9524 (3)	0.1087 (9)
H3	0.7721	−0.0247	0.9970	0.130*
C4	0.9012 (4)	0.0389 (3)	0.8756 (3)	0.1117 (11)
H4	1.0013	−0.0117	0.8683	0.134*
C5	0.8928 (3)	0.1199 (3)	0.8082 (3)	0.1080 (9)
H5	0.9866	0.1235	0.7542	0.130*
C6	0.7455 (3)	0.1970 (2)	0.81964 (18)	0.0810 (6)
H6	0.7405	0.2521	0.7733	0.097*
C7	0.3644 (2)	0.30809 (16)	0.80174 (13)	0.0596 (4)
C8	0.3683 (3)	0.3962 (2)	0.74201 (18)	0.0883 (7)
H8	0.4025	0.4510	0.7616	0.106*
C9	0.3214 (4)	0.4039 (4)	0.6523 (2)	0.1312 (15)
H9	0.3243	0.4640	0.6124	0.157*
C10	0.2723 (4)	0.3255 (5)	0.6232 (2)	0.151 (2)
H10	0.2396	0.3315	0.5637	0.181*
C11	0.2700 (4)	0.2369 (4)	0.6805 (3)	0.1328 (15)
H11	0.2386	0.1818	0.6589	0.159*
C12	0.3142 (3)	0.2278 (2)	0.77086 (19)	0.0915 (7)
H12	0.3098	0.1676	0.8105	0.110*
C13	0.9202 (2)	0.83033 (14)	0.58955 (13)	0.0555 (4)
C14	0.9102 (3)	0.87892 (17)	0.49778 (17)	0.0726 (5)
H14	0.9813	0.8474	0.4359	0.087*
C15	0.7958 (4)	0.9736 (2)	0.4973 (2)	0.0942 (7)
H15	0.7889	1.0056	0.4354	0.113*
C16	0.6919 (3)	1.0207 (2)	0.5888 (2)	0.0946 (7)
H16	0.6149	1.0848	0.5885	0.114*
C17	0.7008 (3)	0.9741 (2)	0.6804 (2)	0.0866 (7)
H17	0.6307	1.0068	0.7420	0.104*
C18	0.8131 (2)	0.87914 (18)	0.68161 (16)	0.0699 (5)
H18	0.8178	0.8472	0.7439	0.084*
C19	1.2090 (2)	0.73882 (13)	0.65667 (13)	0.0526 (4)
C20	1.1615 (2)	0.75061 (17)	0.76300 (14)	0.0668 (5)
H20	1.0623	0.7363	0.8029	0.080*
C21	1.2614 (3)	0.78362 (18)	0.80945 (17)	0.0738 (5)
H21	1.2291	0.7915	0.8806	0.089*
C22	1.4074 (3)	0.8047 (2)	0.75140 (19)	0.0790 (6)
H22	1.4742	0.8268	0.7831	0.095*
C23	1.4560 (3)	0.7934 (2)	0.6462 (2)	0.0837 (6)
H23	1.5548	0.8086	0.6068	0.100*
C24	1.3581 (2)	0.75960 (17)	0.59883 (16)	0.0671 (5)
H24	1.3924	0.7507	0.5278	0.081*
C25	0.8658 (3)	0.58874 (18)	0.65139 (14)	0.0702 (5)
H25A	0.9283	0.5267	0.6087	0.084*
H25B	0.7985	0.6366	0.6141	0.084*
C26	0.7562 (2)	0.55808 (16)	0.75089 (14)	0.0613 (4)
H26A	0.6767	0.5260	0.7364	0.074*
H26B	0.6941	0.6209	0.7925	0.074*
C27	0.8554 (2)	0.48216 (15)	0.81037 (14)	0.0607 (4)
H27A	0.9069	0.4160	0.7724	0.073*
H27B	0.9434	0.5107	0.8181	0.073*
C28	0.8414 (3)	0.3920 (2)	0.9757 (2)	0.0889 (7)
H28A	0.7658	0.3823	1.0412	0.133*
H28B	0.9247	0.4224	0.9857	0.133*
H28C	0.8942	0.3250	0.9411	0.133*
N1	0.74885 (16)	0.46270 (11)	0.91284 (10)	0.0518 (3)
H1A	0.6938	0.5295	0.9491	0.062*
H1B	0.6633	0.4322	0.9045	0.062*
O1	0.47105 (16)	0.39949 (10)	0.92942 (11)	0.0684 (3)
O2	0.97829 (16)	0.63961 (10)	0.67623 (9)	0.0606 (3)
P1	0.41972 (5)	0.30015 (3)	0.92019 (3)	0.05055 (12)
P2	1.07451 (5)	0.70846 (4)	0.59135 (3)	0.05304 (12)
S1	0.23717 (6)	0.27242 (5)	1.03546 (4)	0.07647 (17)
S2	1.18746 (8)	0.64414 (5)	0.45718 (4)	0.07759 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0572 (9)	0.0562 (9)	0.0545 (9)	−0.0183 (7)	−0.0183 (7)	−0.0083 (7)
C2	0.0853 (14)	0.0787 (14)	0.0820 (14)	−0.0202 (11)	−0.0363 (12)	0.0092 (11)
C3	0.127 (2)	0.0795 (17)	0.129 (2)	−0.0037 (16)	−0.072 (2)	0.0113 (16)
C4	0.0848 (18)	0.109 (2)	0.136 (3)	0.0171 (16)	−0.0527 (19)	−0.038 (2)
C5	0.0664 (14)	0.126 (2)	0.107 (2)	0.0030 (15)	−0.0069 (14)	−0.0305 (19)
C6	0.0657 (12)	0.0861 (15)	0.0764 (13)	−0.0109 (11)	−0.0046 (10)	−0.0078 (11)
C7	0.0446 (8)	0.0802 (12)	0.0500 (9)	−0.0122 (8)	−0.0098 (7)	−0.0062 (8)
C8	0.0715 (13)	0.1087 (18)	0.0695 (13)	−0.0081 (12)	−0.0150 (10)	0.0191 (12)
C9	0.0824 (18)	0.199 (4)	0.0717 (17)	0.017 (2)	−0.0162 (14)	0.037 (2)
C10	0.0704 (17)	0.298 (7)	0.0568 (16)	0.014 (3)	−0.0230 (13)	−0.025 (3)
C11	0.093 (2)	0.230 (5)	0.089 (2)	−0.040 (2)	−0.0363 (17)	−0.057 (3)
C12	0.0890 (15)	0.126 (2)	0.0736 (13)	−0.0400 (15)	−0.0293 (12)	−0.0206 (13)
C13	0.0561 (9)	0.0614 (10)	0.0588 (9)	−0.0278 (8)	−0.0201 (7)	−0.0001 (7)
C14	0.0800 (13)	0.0750 (13)	0.0686 (12)	−0.0249 (11)	−0.0272 (10)	0.0065 (10)
C15	0.1062 (19)	0.0842 (16)	0.1014 (18)	−0.0238 (14)	−0.0483 (16)	0.0213 (14)
C16	0.0856 (16)	0.0720 (14)	0.128 (2)	−0.0091 (12)	−0.0426 (16)	−0.0026 (15)
C17	0.0714 (13)	0.0846 (16)	0.0994 (17)	−0.0107 (11)	−0.0222 (12)	−0.0196 (13)
C18	0.0642 (11)	0.0793 (13)	0.0676 (11)	−0.0190 (10)	−0.0190 (9)	−0.0065 (10)
C19	0.0481 (8)	0.0528 (9)	0.0568 (9)	−0.0169 (7)	−0.0125 (7)	0.0040 (7)
C20	0.0647 (11)	0.0859 (13)	0.0568 (10)	−0.0364 (10)	−0.0144 (8)	0.0071 (9)
C21	0.0788 (13)	0.0876 (14)	0.0669 (12)	−0.0326 (11)	−0.0299 (10)	0.0060 (10)
C22	0.0670 (12)	0.0933 (16)	0.0918 (15)	−0.0328 (11)	−0.0353 (11)	0.0044 (12)
C23	0.0537 (11)	0.1080 (18)	0.0953 (16)	−0.0370 (11)	−0.0169 (10)	0.0038 (13)
C24	0.0519 (9)	0.0810 (13)	0.0655 (11)	−0.0224 (9)	−0.0085 (8)	0.0023 (9)
C25	0.0835 (13)	0.0878 (14)	0.0575 (10)	−0.0531 (11)	−0.0211 (9)	0.0043 (9)
C26	0.0571 (10)	0.0736 (11)	0.0604 (10)	−0.0325 (9)	−0.0151 (8)	0.0050 (8)
C27	0.0456 (8)	0.0617 (10)	0.0670 (10)	−0.0173 (7)	−0.0021 (7)	0.0021 (8)
C28	0.0918 (16)	0.0878 (16)	0.0896 (16)	−0.0134 (13)	−0.0424 (13)	0.0208 (12)
N1	0.0475 (7)	0.0514 (7)	0.0554 (7)	−0.0143 (6)	−0.0116 (6)	−0.0009 (6)
O1	0.0617 (7)	0.0594 (7)	0.0878 (9)	−0.0213 (6)	−0.0185 (6)	−0.0168 (6)
O2	0.0712 (8)	0.0685 (7)	0.0521 (6)	−0.0398 (6)	−0.0149 (5)	0.0059 (5)
P1	0.0492 (2)	0.0557 (2)	0.0486 (2)	−0.01871 (18)	−0.01083 (16)	−0.00791 (17)
P2	0.0567 (2)	0.0580 (2)	0.0467 (2)	−0.02530 (19)	−0.00928 (17)	0.00079 (17)
S1	0.0625 (3)	0.1044 (4)	0.0553 (3)	−0.0284 (3)	0.0000 (2)	−0.0022 (3)
S2	0.0904 (4)	0.0810 (4)	0.0556 (3)	−0.0280 (3)	−0.0051 (2)	−0.0113 (2)

Geometric parameters (Å, º)

C1—C2	1.374 (3)	C17—H17	0.9300
C1—C6	1.388 (3)	C18—H18	0.9300
C1—P1	1.8149 (18)	C19—C24	1.385 (2)
C2—C3	1.391 (4)	C19—C20	1.391 (2)
C2—H2	0.9300	C19—P2	1.8003 (17)
C3—C4	1.338 (5)	C20—C21	1.382 (3)
C3—H3	0.9300	C20—H20	0.9300
C4—C5	1.362 (5)	C21—C22	1.366 (3)
C4—H4	0.9300	C21—H21	0.9300
C5—C6	1.385 (4)	C22—C23	1.375 (3)
C5—H5	0.9300	C22—H22	0.9300
C6—H6	0.9300	C23—C24	1.381 (3)
C7—C8	1.373 (3)	C23—H23	0.9300
C7—C12	1.376 (3)	C24—H24	0.9300
C7—P1	1.8092 (18)	C25—O2	1.446 (2)
C8—C9	1.391 (4)	C25—C26	1.504 (2)
C8—H8	0.9300	C25—H25A	0.9700
C9—C10	1.339 (6)	C25—H25B	0.9700
C9—H9	0.9300	C26—C27	1.505 (3)
C10—C11	1.360 (6)	C26—H26A	0.9700
C10—H10	0.9300	C26—H26B	0.9700
C11—C12	1.386 (4)	C27—N1	1.475 (2)
C11—H11	0.9300	C27—H27A	0.9700
C12—H12	0.9300	C27—H27B	0.9700
C13—C14	1.383 (3)	C28—N1	1.472 (3)
C13—C18	1.396 (3)	C28—H28A	0.9600
C13—P2	1.8064 (19)	C28—H28B	0.9600
C14—C15	1.377 (3)	C28—H28C	0.9600
C14—H14	0.9300	N1—H1A	0.9700
C15—C16	1.374 (4)	N1—H1B	0.9700
C15—H15	0.9300	O1—P1	1.5102 (13)
C16—C17	1.370 (4)	O2—P2	1.5916 (12)
C16—H16	0.9300	P1—S1	1.9621 (6)
C17—C18	1.372 (3)	P2—S2	1.9285 (6)
C2—C1—C6	118.5 (2)	C21—C20—H20	119.9
C2—C1—P1	122.52 (16)	C19—C20—H20	119.9
C6—C1—P1	118.91 (16)	C22—C21—C20	120.3 (2)
C1—C2—C3	120.3 (3)	C22—C21—H21	119.8
C1—C2—H2	119.8	C20—C21—H21	119.8
C3—C2—H2	119.8	C21—C22—C23	120.2 (2)
C4—C3—C2	120.6 (3)	C21—C22—H22	119.9
C4—C3—H3	119.7	C23—C22—H22	119.9
C2—C3—H3	119.7	C22—C23—C24	120.08 (19)
C3—C4—C5	120.3 (3)	C22—C23—H23	120.0
C3—C4—H4	119.9	C24—C23—H23	120.0
C5—C4—H4	119.9	C23—C24—C19	120.32 (19)
C4—C5—C6	120.4 (3)	C23—C24—H24	119.8
C4—C5—H5	119.8	C19—C24—H24	119.8
C6—C5—H5	119.8	O2—C25—C26	107.61 (14)
C5—C6—C1	119.9 (3)	O2—C25—H25A	110.2
C5—C6—H6	120.1	C26—C25—H25A	110.2
C1—C6—H6	120.1	O2—C25—H25B	110.2
C8—C7—C12	118.7 (2)	C26—C25—H25B	110.2
C8—C7—P1	120.17 (18)	H25A—C25—H25B	108.5
C12—C7—P1	121.07 (18)	C25—C26—C27	111.96 (16)
C7—C8—C9	120.4 (3)	C25—C26—H26A	109.2
C7—C8—H8	119.8	C27—C26—H26A	109.2
C9—C8—H8	119.8	C25—C26—H26B	109.2
C10—C9—C8	120.3 (4)	C27—C26—H26B	109.2
C10—C9—H9	119.8	H26A—C26—H26B	107.9
C8—C9—H9	119.8	N1—C27—C26	111.22 (14)
C9—C10—C11	120.1 (3)	N1—C27—H27A	109.4
C9—C10—H10	119.9	C26—C27—H27A	109.4
C11—C10—H10	119.9	N1—C27—H27B	109.4
C10—C11—C12	120.6 (4)	C26—C27—H27B	109.4
C10—C11—H11	119.7	H27A—C27—H27B	108.0
C12—C11—H11	119.7	N1—C28—H28A	109.5
C7—C12—C11	119.7 (3)	N1—C28—H28B	109.5
C7—C12—H12	120.1	H28A—C28—H28B	109.5
C11—C12—H12	120.1	N1—C28—H28C	109.5
C14—C13—C18	118.90 (19)	H28A—C28—H28C	109.5
C14—C13—P2	120.91 (15)	H28B—C28—H28C	109.5
C18—C13—P2	120.15 (15)	C28—N1—C27	113.31 (16)
C15—C14—C13	120.5 (2)	C28—N1—H1A	108.9
C15—C14—H14	119.7	C27—N1—H1A	108.9
C13—C14—H14	119.7	C28—N1—H1B	108.9
C16—C15—C14	119.8 (2)	C27—N1—H1B	108.9
C16—C15—H15	120.1	H1A—N1—H1B	107.7
C14—C15—H15	120.1	C25—O2—P2	119.19 (11)
C17—C16—C15	120.5 (2)	O1—P1—C1	106.82 (7)
C17—C16—H16	119.7	O1—P1—C7	107.21 (9)
C15—C16—H16	119.7	O1—P1—S1	115.73 (6)
C16—C17—C18	120.1 (2)	C1—P1—C7	105.28 (8)
C16—C17—H17	119.9	C1—P1—S1	111.17 (6)
C18—C17—H17	119.9	C7—P1—S1	110.05 (6)
C17—C18—C13	120.2 (2)	O2—P2—C13	104.60 (8)
C17—C18—H18	119.9	O2—P2—C19	100.29 (7)
C13—C18—H18	119.9	O2—P2—S2	116.62 (5)
C24—C19—C20	118.95 (17)	C13—P2—C19	105.68 (8)
C24—C19—P2	118.95 (14)	C13—P2—S2	113.39 (6)
C20—C19—P2	121.88 (13)	C19—P2—S2	114.75 (6)
C21—C20—C19	120.10 (17)
C6—C1—C2—C3	1.2 (3)	O2—C25—C26—C27	−60.9 (2)
P1—C1—C2—C3	−174.68 (19)	C25—C26—C27—N1	173.30 (15)
C1—C2—C3—C4	0.3 (4)	C26—C27—N1—C28	−177.79 (18)
C2—C3—C4—C5	−1.7 (5)	C26—C25—O2—P2	−163.24 (13)
C3—C4—C5—C6	1.4 (5)	C8—C7—P1—O1	−2.42 (18)
C4—C5—C6—C1	0.1 (4)	C12—C7—P1—O1	179.06 (16)
C2—C1—C6—C5	−1.5 (3)	C8—C7—P1—C1	−115.91 (16)
P1—C1—C6—C5	174.6 (2)	C12—C7—P1—C1	65.57 (18)
C12—C7—C8—C9	0.3 (3)	C8—C7—P1—S1	124.21 (15)
P1—C7—C8—C9	−178.22 (18)	C12—C7—P1—S1	−54.31 (18)
C7—C8—C9—C10	−0.1 (4)	C2—C1—P1—O1	120.98 (17)
C8—C9—C10—C11	−0.9 (5)	C6—C1—P1—O1	−54.92 (17)
C9—C10—C11—C12	1.7 (5)	C2—C1—P1—C7	−125.26 (17)
C8—C7—C12—C11	0.5 (3)	C6—C1—P1—C7	58.84 (17)
P1—C7—C12—C11	179.0 (2)	C2—C1—P1—S1	−6.13 (18)
C10—C11—C12—C7	−1.5 (4)	C6—C1—P1—S1	177.97 (14)
C18—C13—C14—C15	−0.3 (3)	C25—O2—P2—C19	−173.93 (15)
P2—C13—C14—C15	−177.83 (18)	C25—O2—P2—C13	76.72 (16)
C13—C14—C15—C16	0.6 (4)	C25—O2—P2—S2	−49.40 (16)
C14—C15—C16—C17	−0.2 (4)	C24—C19—P2—O2	153.72 (15)
C15—C16—C17—C18	−0.5 (4)	C20—C19—P2—O2	−31.72 (17)
C16—C17—C18—C13	0.8 (3)	C24—C19—P2—C13	−97.79 (16)
C14—C13—C18—C17	−0.4 (3)	C20—C19—P2—C13	76.77 (17)
P2—C13—C18—C17	177.10 (16)	C24—C19—P2—S2	27.91 (17)
C24—C19—C20—C21	0.7 (3)	C20—C19—P2—S2	−157.53 (14)
P2—C19—C20—C21	−173.90 (16)	C14—C13—P2—O2	−138.99 (15)
C19—C20—C21—C22	−0.1 (3)	C18—C13—P2—O2	43.56 (16)
C20—C21—C22—C23	0.1 (4)	C14—C13—P2—C19	115.64 (15)
C21—C22—C23—C24	−0.7 (4)	C18—C13—P2—C19	−61.81 (16)
C22—C23—C24—C19	1.3 (4)	C14—C13—P2—S2	−10.88 (17)
C20—C19—C24—C23	−1.3 (3)	C18—C13—P2—S2	171.66 (13)
P2—C19—C24—C23	173.47 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1^i	0.97	1.94	2.7933 (19)	146
N1—H1A···S1^i	0.97	2.85	3.6379 (15)	138
N1—H1B···O1	0.97	1.76	2.6974 (18)	161

Symmetry code: (i) −x+1, −y+1, −z+2.