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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614002757/qs3034sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614002757/qs3034Isup2.hkl
Contains datablock I

CCDC reference: 931171

Intruduction top

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).

Experimental top

Synthesis and crystallization top

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): (PS) 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%.

Refinement top

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 Uiso(H) = 1.5Ueq(C) for methyl H atoms and at 1.5Ueq(C) otherwise.

Results and discussion top

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 PO 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 top

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 top

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 top
[Figure 1] 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.
[Figure 2] Fig. 2. A packing diagram of the crystal structure of (I), showing the formation of R42(8) and R12(4) versus S(5) rings.
3-[(Diphenylphosphinothioyl)oxy]-N-methylpropan-1-aminium diphenylphosphanylthioate top
Crystal data top
C16H21NOPS+·C12H10OPSZ = 2
Mr = 539.60F(000) = 568
Triclinic, P1Dx = 1.248 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.6999 (4) ÅCell parameters from 26612 reflections
b = 13.1458 (6) Åθ = 2.5–28.0°
c = 13.6405 (5) ŵ = 0.32 mm1
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) Å3
Data collection top
STOE IPDS 2
diffractometer
5944 independent reflections
Radiation source: fine-focus sealed tube5051 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.048
rotation method scansθmax = 26.5°, θmin = 2.5°
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)
h = 1010
Tmin = 0.812, Tmax = 0.890k = 1616
26612 measured reflectionsl = 1717
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.107 w = 1/[σ2(Fo2) + (0.0553P)2 + 0.2299P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
5944 reflectionsΔρmax = 0.26 e Å3
316 parametersΔρmin = 0.20 e Å3
Crystal data top
C16H21NOPS+·C12H10OPSγ = 74.886 (3)°
Mr = 539.60V = 1436.09 (11) Å3
Triclinic, P1Z = 2
a = 8.6999 (4) ÅMo Kα radiation
b = 13.1458 (6) ŵ = 0.32 mm1
c = 13.6405 (5) ÅT = 296 K
α = 86.201 (3)°0.62 × 0.52 × 0.43 mm
β = 72.482 (3)°
Data collection top
STOE IPDS 2
diffractometer
5944 independent reflections
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)
5051 reflections with I > 2σ(I)
Tmin = 0.812, Tmax = 0.890Rint = 0.048
26612 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.107H-atom parameters constrained
S = 1.04Δρmax = 0.26 e Å3
5944 reflectionsΔρmin = 0.20 e Å3
316 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
C10.6055 (2)0.19208 (14)0.90041 (13)0.0543 (4)
C20.6165 (3)0.10835 (19)0.96607 (19)0.0799 (6)
H20.52350.10281.01990.096*
C30.7660 (4)0.0319 (2)0.9524 (3)0.1087 (9)
H30.77210.02470.99700.130*
C40.9012 (4)0.0389 (3)0.8756 (3)0.1117 (11)
H41.00130.01170.86830.134*
C50.8928 (3)0.1199 (3)0.8082 (3)0.1080 (9)
H50.98660.12350.75420.130*
C60.7455 (3)0.1970 (2)0.81964 (18)0.0810 (6)
H60.74050.25210.77330.097*
C70.3644 (2)0.30809 (16)0.80174 (13)0.0596 (4)
C80.3683 (3)0.3962 (2)0.74201 (18)0.0883 (7)
H80.40250.45100.76160.106*
C90.3214 (4)0.4039 (4)0.6523 (2)0.1312 (15)
H90.32430.46400.61240.157*
C100.2723 (4)0.3255 (5)0.6232 (2)0.151 (2)
H100.23960.33150.56370.181*
C110.2700 (4)0.2369 (4)0.6805 (3)0.1328 (15)
H110.23860.18180.65890.159*
C120.3142 (3)0.2278 (2)0.77086 (19)0.0915 (7)
H120.30980.16760.81050.110*
C130.9202 (2)0.83033 (14)0.58955 (13)0.0555 (4)
C140.9102 (3)0.87892 (17)0.49778 (17)0.0726 (5)
H140.98130.84740.43590.087*
C150.7958 (4)0.9736 (2)0.4973 (2)0.0942 (7)
H150.78891.00560.43540.113*
C160.6919 (3)1.0207 (2)0.5888 (2)0.0946 (7)
H160.61491.08480.58850.114*
C170.7008 (3)0.9741 (2)0.6804 (2)0.0866 (7)
H170.63071.00680.74200.104*
C180.8131 (2)0.87914 (18)0.68161 (16)0.0699 (5)
H180.81780.84720.74390.084*
C191.2090 (2)0.73882 (13)0.65667 (13)0.0526 (4)
C201.1615 (2)0.75061 (17)0.76300 (14)0.0668 (5)
H201.06230.73630.80290.080*
C211.2614 (3)0.78362 (18)0.80945 (17)0.0738 (5)
H211.22910.79150.88060.089*
C221.4074 (3)0.8047 (2)0.75140 (19)0.0790 (6)
H221.47420.82680.78310.095*
C231.4560 (3)0.7934 (2)0.6462 (2)0.0837 (6)
H231.55480.80860.60680.100*
C241.3581 (2)0.75960 (17)0.59883 (16)0.0671 (5)
H241.39240.75070.52780.081*
C250.8658 (3)0.58874 (18)0.65139 (14)0.0702 (5)
H25A0.92830.52670.60870.084*
H25B0.79850.63660.61410.084*
C260.7562 (2)0.55808 (16)0.75089 (14)0.0613 (4)
H26A0.67670.52600.73640.074*
H26B0.69410.62090.79250.074*
C270.8554 (2)0.48216 (15)0.81037 (14)0.0607 (4)
H27A0.90690.41600.77240.073*
H27B0.94340.51070.81810.073*
C280.8414 (3)0.3920 (2)0.9757 (2)0.0889 (7)
H28A0.76580.38231.04120.133*
H28B0.92470.42240.98570.133*
H28C0.89420.32500.94110.133*
N10.74885 (16)0.46270 (11)0.91284 (10)0.0518 (3)
H1A0.69380.52950.94910.062*
H1B0.66330.43220.90450.062*
O10.47105 (16)0.39949 (10)0.92942 (11)0.0684 (3)
O20.97829 (16)0.63961 (10)0.67623 (9)0.0606 (3)
P10.41972 (5)0.30015 (3)0.92019 (3)0.05055 (12)
P21.07451 (5)0.70846 (4)0.59135 (3)0.05304 (12)
S10.23717 (6)0.27242 (5)1.03546 (4)0.07647 (17)
S21.18746 (8)0.64414 (5)0.45718 (4)0.07759 (17)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0572 (9)0.0562 (9)0.0545 (9)0.0183 (7)0.0183 (7)0.0083 (7)
C20.0853 (14)0.0787 (14)0.0820 (14)0.0202 (11)0.0363 (12)0.0092 (11)
C30.127 (2)0.0795 (17)0.129 (2)0.0037 (16)0.072 (2)0.0113 (16)
C40.0848 (18)0.109 (2)0.136 (3)0.0171 (16)0.0527 (19)0.038 (2)
C50.0664 (14)0.126 (2)0.107 (2)0.0030 (15)0.0069 (14)0.0305 (19)
C60.0657 (12)0.0861 (15)0.0764 (13)0.0109 (11)0.0046 (10)0.0078 (11)
C70.0446 (8)0.0802 (12)0.0500 (9)0.0122 (8)0.0098 (7)0.0062 (8)
C80.0715 (13)0.1087 (18)0.0695 (13)0.0081 (12)0.0150 (10)0.0191 (12)
C90.0824 (18)0.199 (4)0.0717 (17)0.017 (2)0.0162 (14)0.037 (2)
C100.0704 (17)0.298 (7)0.0568 (16)0.014 (3)0.0230 (13)0.025 (3)
C110.093 (2)0.230 (5)0.089 (2)0.040 (2)0.0363 (17)0.057 (3)
C120.0890 (15)0.126 (2)0.0736 (13)0.0400 (15)0.0293 (12)0.0206 (13)
C130.0561 (9)0.0614 (10)0.0588 (9)0.0278 (8)0.0201 (7)0.0001 (7)
C140.0800 (13)0.0750 (13)0.0686 (12)0.0249 (11)0.0272 (10)0.0065 (10)
C150.1062 (19)0.0842 (16)0.1014 (18)0.0238 (14)0.0483 (16)0.0213 (14)
C160.0856 (16)0.0720 (14)0.128 (2)0.0091 (12)0.0426 (16)0.0026 (15)
C170.0714 (13)0.0846 (16)0.0994 (17)0.0107 (11)0.0222 (12)0.0196 (13)
C180.0642 (11)0.0793 (13)0.0676 (11)0.0190 (10)0.0190 (9)0.0065 (10)
C190.0481 (8)0.0528 (9)0.0568 (9)0.0169 (7)0.0125 (7)0.0040 (7)
C200.0647 (11)0.0859 (13)0.0568 (10)0.0364 (10)0.0144 (8)0.0071 (9)
C210.0788 (13)0.0876 (14)0.0669 (12)0.0326 (11)0.0299 (10)0.0060 (10)
C220.0670 (12)0.0933 (16)0.0918 (15)0.0328 (11)0.0353 (11)0.0044 (12)
C230.0537 (11)0.1080 (18)0.0953 (16)0.0370 (11)0.0169 (10)0.0038 (13)
C240.0519 (9)0.0810 (13)0.0655 (11)0.0224 (9)0.0085 (8)0.0023 (9)
C250.0835 (13)0.0878 (14)0.0575 (10)0.0531 (11)0.0211 (9)0.0043 (9)
C260.0571 (10)0.0736 (11)0.0604 (10)0.0325 (9)0.0151 (8)0.0050 (8)
C270.0456 (8)0.0617 (10)0.0670 (10)0.0173 (7)0.0021 (7)0.0021 (8)
C280.0918 (16)0.0878 (16)0.0896 (16)0.0134 (13)0.0424 (13)0.0208 (12)
N10.0475 (7)0.0514 (7)0.0554 (7)0.0143 (6)0.0116 (6)0.0009 (6)
O10.0617 (7)0.0594 (7)0.0878 (9)0.0213 (6)0.0185 (6)0.0168 (6)
O20.0712 (8)0.0685 (7)0.0521 (6)0.0398 (6)0.0149 (5)0.0059 (5)
P10.0492 (2)0.0557 (2)0.0486 (2)0.01871 (18)0.01083 (16)0.00791 (17)
P20.0567 (2)0.0580 (2)0.0467 (2)0.02530 (19)0.00928 (17)0.00079 (17)
S10.0625 (3)0.1044 (4)0.0553 (3)0.0284 (3)0.0000 (2)0.0022 (3)
S20.0904 (4)0.0810 (4)0.0556 (3)0.0280 (3)0.0051 (2)0.0113 (2)
Geometric parameters (Å, º) top
C1—C21.374 (3)C17—H170.9300
C1—C61.388 (3)C18—H180.9300
C1—P11.8149 (18)C19—C241.385 (2)
C2—C31.391 (4)C19—C201.391 (2)
C2—H20.9300C19—P21.8003 (17)
C3—C41.338 (5)C20—C211.382 (3)
C3—H30.9300C20—H200.9300
C4—C51.362 (5)C21—C221.366 (3)
C4—H40.9300C21—H210.9300
C5—C61.385 (4)C22—C231.375 (3)
C5—H50.9300C22—H220.9300
C6—H60.9300C23—C241.381 (3)
C7—C81.373 (3)C23—H230.9300
C7—C121.376 (3)C24—H240.9300
C7—P11.8092 (18)C25—O21.446 (2)
C8—C91.391 (4)C25—C261.504 (2)
C8—H80.9300C25—H25A0.9700
C9—C101.339 (6)C25—H25B0.9700
C9—H90.9300C26—C271.505 (3)
C10—C111.360 (6)C26—H26A0.9700
C10—H100.9300C26—H26B0.9700
C11—C121.386 (4)C27—N11.475 (2)
C11—H110.9300C27—H27A0.9700
C12—H120.9300C27—H27B0.9700
C13—C141.383 (3)C28—N11.472 (3)
C13—C181.396 (3)C28—H28A0.9600
C13—P21.8064 (19)C28—H28B0.9600
C14—C151.377 (3)C28—H28C0.9600
C14—H140.9300N1—H1A0.9700
C15—C161.374 (4)N1—H1B0.9700
C15—H150.9300O1—P11.5102 (13)
C16—C171.370 (4)O2—P21.5916 (12)
C16—H160.9300P1—S11.9621 (6)
C17—C181.372 (3)P2—S21.9285 (6)
C2—C1—C6118.5 (2)C21—C20—H20119.9
C2—C1—P1122.52 (16)C19—C20—H20119.9
C6—C1—P1118.91 (16)C22—C21—C20120.3 (2)
C1—C2—C3120.3 (3)C22—C21—H21119.8
C1—C2—H2119.8C20—C21—H21119.8
C3—C2—H2119.8C21—C22—C23120.2 (2)
C4—C3—C2120.6 (3)C21—C22—H22119.9
C4—C3—H3119.7C23—C22—H22119.9
C2—C3—H3119.7C22—C23—C24120.08 (19)
C3—C4—C5120.3 (3)C22—C23—H23120.0
C3—C4—H4119.9C24—C23—H23120.0
C5—C4—H4119.9C23—C24—C19120.32 (19)
C4—C5—C6120.4 (3)C23—C24—H24119.8
C4—C5—H5119.8C19—C24—H24119.8
C6—C5—H5119.8O2—C25—C26107.61 (14)
C5—C6—C1119.9 (3)O2—C25—H25A110.2
C5—C6—H6120.1C26—C25—H25A110.2
C1—C6—H6120.1O2—C25—H25B110.2
C8—C7—C12118.7 (2)C26—C25—H25B110.2
C8—C7—P1120.17 (18)H25A—C25—H25B108.5
C12—C7—P1121.07 (18)C25—C26—C27111.96 (16)
C7—C8—C9120.4 (3)C25—C26—H26A109.2
C7—C8—H8119.8C27—C26—H26A109.2
C9—C8—H8119.8C25—C26—H26B109.2
C10—C9—C8120.3 (4)C27—C26—H26B109.2
C10—C9—H9119.8H26A—C26—H26B107.9
C8—C9—H9119.8N1—C27—C26111.22 (14)
C9—C10—C11120.1 (3)N1—C27—H27A109.4
C9—C10—H10119.9C26—C27—H27A109.4
C11—C10—H10119.9N1—C27—H27B109.4
C10—C11—C12120.6 (4)C26—C27—H27B109.4
C10—C11—H11119.7H27A—C27—H27B108.0
C12—C11—H11119.7N1—C28—H28A109.5
C7—C12—C11119.7 (3)N1—C28—H28B109.5
C7—C12—H12120.1H28A—C28—H28B109.5
C11—C12—H12120.1N1—C28—H28C109.5
C14—C13—C18118.90 (19)H28A—C28—H28C109.5
C14—C13—P2120.91 (15)H28B—C28—H28C109.5
C18—C13—P2120.15 (15)C28—N1—C27113.31 (16)
C15—C14—C13120.5 (2)C28—N1—H1A108.9
C15—C14—H14119.7C27—N1—H1A108.9
C13—C14—H14119.7C28—N1—H1B108.9
C16—C15—C14119.8 (2)C27—N1—H1B108.9
C16—C15—H15120.1H1A—N1—H1B107.7
C14—C15—H15120.1C25—O2—P2119.19 (11)
C17—C16—C15120.5 (2)O1—P1—C1106.82 (7)
C17—C16—H16119.7O1—P1—C7107.21 (9)
C15—C16—H16119.7O1—P1—S1115.73 (6)
C16—C17—C18120.1 (2)C1—P1—C7105.28 (8)
C16—C17—H17119.9C1—P1—S1111.17 (6)
C18—C17—H17119.9C7—P1—S1110.05 (6)
C17—C18—C13120.2 (2)O2—P2—C13104.60 (8)
C17—C18—H18119.9O2—P2—C19100.29 (7)
C13—C18—H18119.9O2—P2—S2116.62 (5)
C24—C19—C20118.95 (17)C13—P2—C19105.68 (8)
C24—C19—P2118.95 (14)C13—P2—S2113.39 (6)
C20—C19—P2121.88 (13)C19—P2—S2114.75 (6)
C21—C20—C19120.10 (17)
C6—C1—C2—C31.2 (3)O2—C25—C26—C2760.9 (2)
P1—C1—C2—C3174.68 (19)C25—C26—C27—N1173.30 (15)
C1—C2—C3—C40.3 (4)C26—C27—N1—C28177.79 (18)
C2—C3—C4—C51.7 (5)C26—C25—O2—P2163.24 (13)
C3—C4—C5—C61.4 (5)C8—C7—P1—O12.42 (18)
C4—C5—C6—C10.1 (4)C12—C7—P1—O1179.06 (16)
C2—C1—C6—C51.5 (3)C8—C7—P1—C1115.91 (16)
P1—C1—C6—C5174.6 (2)C12—C7—P1—C165.57 (18)
C12—C7—C8—C90.3 (3)C8—C7—P1—S1124.21 (15)
P1—C7—C8—C9178.22 (18)C12—C7—P1—S154.31 (18)
C7—C8—C9—C100.1 (4)C2—C1—P1—O1120.98 (17)
C8—C9—C10—C110.9 (5)C6—C1—P1—O154.92 (17)
C9—C10—C11—C121.7 (5)C2—C1—P1—C7125.26 (17)
C8—C7—C12—C110.5 (3)C6—C1—P1—C758.84 (17)
P1—C7—C12—C11179.0 (2)C2—C1—P1—S16.13 (18)
C10—C11—C12—C71.5 (4)C6—C1—P1—S1177.97 (14)
C18—C13—C14—C150.3 (3)C25—O2—P2—C19173.93 (15)
P2—C13—C14—C15177.83 (18)C25—O2—P2—C1376.72 (16)
C13—C14—C15—C160.6 (4)C25—O2—P2—S249.40 (16)
C14—C15—C16—C170.2 (4)C24—C19—P2—O2153.72 (15)
C15—C16—C17—C180.5 (4)C20—C19—P2—O231.72 (17)
C16—C17—C18—C130.8 (3)C24—C19—P2—C1397.79 (16)
C14—C13—C18—C170.4 (3)C20—C19—P2—C1376.77 (17)
P2—C13—C18—C17177.10 (16)C24—C19—P2—S227.91 (17)
C24—C19—C20—C210.7 (3)C20—C19—P2—S2157.53 (14)
P2—C19—C20—C21173.90 (16)C14—C13—P2—O2138.99 (15)
C19—C20—C21—C220.1 (3)C18—C13—P2—O243.56 (16)
C20—C21—C22—C230.1 (4)C14—C13—P2—C19115.64 (15)
C21—C22—C23—C240.7 (4)C18—C13—P2—C1961.81 (16)
C22—C23—C24—C191.3 (4)C14—C13—P2—S210.88 (17)
C20—C19—C24—C231.3 (3)C18—C13—P2—S2171.66 (13)
P2—C19—C24—C23173.47 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.971.942.7933 (19)146
N1—H1A···S1i0.972.853.6379 (15)138
N1—H1B···O10.971.762.6974 (18)161
Symmetry code: (i) x+1, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC16H21NOPS+·C12H10OPS
Mr539.60
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)8.6999 (4), 13.1458 (6), 13.6405 (5)
α, β, γ (°)86.201 (3), 72.482 (3), 74.886 (3)
V3)1436.09 (11)
Z2
Radiation typeMo Kα
µ (mm1)0.32
Crystal size (mm)0.62 × 0.52 × 0.43
Data collection
DiffractometerSTOE IPDS 2
diffractometer
Absorption correctionIntegration
(X-RED32; Stoe & Cie, 2002)
Tmin, Tmax0.812, 0.890
No. of measured, independent and
observed [I > 2σ(I)] reflections
26612, 5944, 5051
Rint0.048
(sin θ/λ)max1)0.628
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.107, 1.04
No. of reflections5944
No. of parameters316
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.26, 0.20

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top
C1—P11.8149 (18)O1—P11.5102 (13)
C7—P11.8092 (18)O2—P21.5916 (12)
C13—P21.8064 (19)P1—S11.9621 (6)
C19—P21.8003 (17)P2—S21.9285 (6)
O1—P1—C1106.82 (7)O2—P2—C13104.60 (8)
O1—P1—C7107.21 (9)O2—P2—C19100.29 (7)
O1—P1—S1115.73 (6)O2—P2—S2116.62 (5)
C1—P1—C7105.28 (8)C13—P2—C19105.68 (8)
C1—P1—S1111.17 (6)C13—P2—S2113.39 (6)
C7—P1—S1110.05 (6)C19—P2—S2114.75 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.971.942.7933 (19)145.9
N1—H1A···S1i0.972.853.6379 (15)138.4
N1—H1B···O10.971.762.6974 (18)160.5
Symmetry code: (i) x+1, y+1, z+2.
 

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