Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614002757/qs3034sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614002757/qs3034Isup2.hkl |
CCDC reference: 931171
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).
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%.
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.
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).
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).
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) Å3 |
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 on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H-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 reflections | Δρmax = 0.26 e Å−3 |
316 parameters | Δρmin = −0.20 e Å−3 |
C16H21NOPS+·C12H10OPS− | γ = 74.886 (3)° |
Mr = 539.60 | V = 1436.09 (11) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.6999 (4) Å | Mo Kα radiation |
b = 13.1458 (6) Å | µ = 0.32 mm−1 |
c = 13.6405 (5) Å | T = 296 K |
α = 86.201 (3)° | 0.62 × 0.52 × 0.43 mm |
β = 72.482 (3)° |
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 = 0.890 | Rint = 0.048 |
26612 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.26 e Å−3 |
5944 reflections | Δρmin = −0.20 e Å−3 |
316 parameters |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.97 | 1.94 | 2.7933 (19) | 146 |
N1—H1A···S1i | 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. |
Experimental details
Crystal data | |
Chemical formula | C16H21NOPS+·C12H10OPS− |
Mr | 539.60 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 1436.09 (11) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.32 |
Crystal size (mm) | 0.62 × 0.52 × 0.43 |
Data collection | |
Diffractometer | STOE IPDS 2 diffractometer |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.812, 0.890 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26612, 5944, 5051 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.107, 1.04 |
No. of reflections | 5944 |
No. of parameters | 316 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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).
C1—P1 | 1.8149 (18) | O1—P1 | 1.5102 (13) |
C7—P1 | 1.8092 (18) | O2—P2 | 1.5916 (12) |
C13—P2 | 1.8064 (19) | P1—S1 | 1.9621 (6) |
C19—P2 | 1.8003 (17) | P2—S2 | 1.9285 (6) |
O1—P1—C1 | 106.82 (7) | O2—P2—C13 | 104.60 (8) |
O1—P1—C7 | 107.21 (9) | O2—P2—C19 | 100.29 (7) |
O1—P1—S1 | 115.73 (6) | O2—P2—S2 | 116.62 (5) |
C1—P1—C7 | 105.28 (8) | C13—P2—C19 | 105.68 (8) |
C1—P1—S1 | 111.17 (6) | C13—P2—S2 | 113.39 (6) |
C7—P1—S1 | 110.05 (6) | C19—P2—S2 | 114.75 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.97 | 1.94 | 2.7933 (19) | 145.9 |
N1—H1A···S1i | 0.97 | 2.85 | 3.6379 (15) | 138.4 |
N1—H1B···O1 | 0.97 | 1.76 | 2.6974 (18) | 160.5 |
Symmetry code: (i) −x+1, −y+1, −z+2. |