Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101018200/na1537sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101018200/na1537IIIasup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101018200/na1537IIIbsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101018200/na1537IVsup4.hkl |
CCDC references: 182037; 182038; 182039
The bis(amide), (I), was prepared according to the literature method of Denmark et al. (1994) from commercially available (1R,2R)-1,2-cyclohexanediamine and triflic anhydride. In the presence of KH in tetrahydrofuran (THF), the bis(amide) yields the dipotassium salt, (II), which, on treatment with diethyl phosphoramidous dichloride (Whitaker et al., 1995), provides the phosphine, (IIIa) (92% yield; m.p. 336–338 K). The phosphine (IIIb) was obtained by an analogous procedure (86% yield; m.p. 339–341 K). The bis(phosphine) ligand, (IV), was prepared from (II) by reaction with methyl imidodiphosphorus tetrachloride (King & Gimeno, 1978) (82% yield; m.p. 473–475 K). The phosphines (IIIa), (IIIb) and (IV) are rather stable to hydrolysis and oxidation and can be stored for several months at room temperature without decomposition.
Spectroscopic data for (IIIa): [α]25D = -35 (c 0.8, THF); 1H NMR (CDCl3, 200 MHz, δ, p.p.m.): 1.15 (t, J = 7.2 Hz, 6H), 1.20–1.65 (m, 4H), 1.80–1.95 (m, 2H), 2.55–2.70 (m, 2H), 2.90–3.40 (m, 5H), 3,59 (td, J = 3.1 and 10.6 Hz, 1H); 13C NMR (CDCl3, 50 MHz, δ, p.p.m.): 13.8, 13.9, 23.9, 24.4, 29.6, 30.6, 41.4, 41.7, 65.7 (d, J = 5.5 Hz), 67.3 (d, J= 5.5 Hz); 19F NMR (CDCl3, 188.3 MHz, δ, p.p.m.): -76.1 (br s, 3 F), -77.6 (d, J = 11.4 Hz, 3 F); 31P NMR (CDCl3, 81 MHz,δ, p.p.m.): 99.3 (s large, 2P); IR (cm-1): 1458, 1448, 1392, 1219, 1196; MS (CI) m/z: 480 [100%, (M+H)+], 407 (3.7%), 396 (10.8%), 346 (2.5%). Analysis calculated for C12H20F6N3O4PS2: C 30.06, N 8,77, H 4.20%; found: C 29.87, N 9.01, H 3.92%.
Spectroscopic data for (IIIb): [α]25D = -42 (c 0.9, THF); 1H NMR (CDCl3, 200 MHz, δ, p.p.m.): 1.15–1.65 (m, 4H), 1.75–1.95 (m, 2H), 2.50–2.70 (m, 2H), 2.73 (s, 3H), 2.78 (s, 3H), 3.57 (td, J = 3.5 and 10.6 Hz, 1H), 3,66 (td, J = 3.0 and 10.6 Hz, 1H); 13C NMR (CDCl3, 50 MHz, d, p.p.m.): 23.4, 23.9, 29.3, 29.9, 37.4, 37.9, 65.4 (d, J = 4.5 Hz), 66.9 (d, J = 4,5 Hz); 19F NMR (CDCl3, 188.3 MHz, d, p.p.m.): -76.5 (d, J =11.5 Hz, 3 F), -77.60 (d, J = 9.8 Hz, 3 F); 31P NMR (CDCl3, 81 MHz, d, p.p.m.): 102.90 (s, 2P); IR (film, n, cm-1): 3293, 2952, 1462, 1451, 1392; MS (CI) m/z: 452 [100%, (M+H)+], 318 (6.9%). Analysis calculated for C10H16F6N3O4PS2: C 26.61, N 9.31, H 3.57%; found: C 26.42, N 9.47, H 3.84%.
Spectroscopic data for (IV): [α]25D = -34 (c 1.0, THF); 1H NMR (CDCl3, 200 MHz,δ, p.p.m.): 1.22 (t, J = 10.4 Hz, 4H), 1.4–1.7 (m, 4H), 1.84 (br s, 4H), 2.5–2.7 (m, 4H), 3.01 (t, J = 9.1 Hz, 3H), 3.34 (t, J = 10.4 Hz, 2H), 3.98 (s, 2H); 13C NMR (CDCl3, 50 MHz,δ, p.p.m.): 23.8, 24.4, 28.9, 30.0, 34.3, 67.5, 68.8; 19F NMR (CDCl3, 188.3 MHz,δ, p.p.m.): -73.58 (br s, 6 F), -76.82 (s, 6 F); 31P NMR (CDCl3, 81 MHz, δ, p.p.m.): 103.5 (s, 2P); IR (cm-1): 3054, 1265; MS (CI) m/z: 861 [100%, (M+NH4+)], 844 (24.4%), 774 (9.3%), 436 (14.2%), 397 (93.6%). Analysis calculated for C17H23F12N5O8P2S4: C 24.35, N 8.10, H 2.46%; found: C 24,19, N 8,30, H 2.72%.
Compounds (IIIa) and (IIIb) were analyzed in racemic form and compound (IV) as the (R,R)-enantiomer. H atoms were placed in calculated positions and not refined. In compound (IV), the loss of symmetry from P21/m to P21 and the high disorder of the co-crystallized CHCl3 molecule were responsible for the relatively rough R factors observed for this structure. The treatment for this disorder was as follows. The occupancy factor of the site of the solvent molecule was first refined and then fixed at 0.982756. The three Cl atoms were statistically spread over five different sites. The sum of the five occupancy factors was then set to three times the occupancy factor of the site of the solvent molecule, i.e. 3*0.983 = 2.949. The loss of symmetry arises from the fact that the pseudo mirror plane exists neither for the highly disordered solvent molecule nor for the cyclohexyl group, which would become a phenyl group in contradiction with the chemical nature of the compound. Space group P21 has a twofold screw axis. The heaviest atom might be choosen as an origin and its coordinate along this twofold screw axis might then be fixed and not refined. Here, the heaviest atom is Cl, but since it is part of a severe disordered solvent molecule we prefered to choose as origin an S atom on the main molecule, which is far less disordered, and an S atom is not much lighter than a Cl atom. Doing this, we could reach a better refinement of the molecular structure.
For all compounds, data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: TEXSAN (Molecular Structure Corporation, 1992-1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
C12H20F6N3O4PS2 | Z = 2 |
Mr = 479.39 | F(000) = 492.00 |
Triclinic, P1 | Dx = 1.553 Mg m−3 |
Hall symbol: -P1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.657 (2) Å | Cell parameters from 25 reflections |
b = 10.352 (2) Å | θ = 10.0–11.1° |
c = 12.859 (3) Å | µ = 0.41 mm−1 |
α = 104.81 (1)° | T = 293 K |
β = 93.08 (2)° | Prism, colourless |
γ = 111.21 (2)° | 0.20 × 0.20 × 0.15 mm |
V = 1024.9 (5) Å3 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.025 |
Radiation source: X-ray tube | θmax = 30.0°, θmin = 2.2° |
Graphite monochromator | h = −12→12 |
ω/2θ scans | k = −14→14 |
6193 measured reflections | l = 0→18 |
5947 independent reflections | 2 standard reflections every 120 reflections |
3678 reflections with I > 3σ(I) | intensity decay: 2.0% |
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters not refined |
wR(F2) = 0.063 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.00063|Fo|2] |
S = 1.95 | (Δ/σ)max = 0.005 |
3678 reflections | Δρmax = 0.43 e Å−3 |
253 parameters | Δρmin = −0.34 e Å−3 |
C12H20F6N3O4PS2 | γ = 111.21 (2)° |
Mr = 479.39 | V = 1024.9 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.657 (2) Å | Mo Kα radiation |
b = 10.352 (2) Å | µ = 0.41 mm−1 |
c = 12.859 (3) Å | T = 293 K |
α = 104.81 (1)° | 0.20 × 0.20 × 0.15 mm |
β = 93.08 (2)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.025 |
6193 measured reflections | 2 standard reflections every 120 reflections |
5947 independent reflections | intensity decay: 2.0% |
3678 reflections with I > 3σ(I) |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.063 | H-atom parameters not refined |
S = 1.95 | Δρmax = 0.43 e Å−3 |
3678 reflections | Δρmin = −0.34 e Å−3 |
253 parameters |
Refinement. For compound (IIIb), in order to have angle values closer to those of compound (IIIa), we chose the following cell parameters: a = 8.972 (2), b = 9.116 (6) and c = 12.990 (7) Å, and α = 97.40 (4), β = 104.03 (4) and γ = 60.58 (4)°. This was in preference to the three-acute cell, with a' = 8.972 (2), b' = 9.116 (6) and c' = 12.990 (7) Å, and α' = 82.60 (4), β' = 75.97 (4) and γ' = 60.58 (4)°. There was also a possibility for a monoclinic C cell, with a'' = 8.972, b'' = 15.881 and c'' = 12.990 Å, and α'' = 89.38, β'' = 104.03 and γ'' = 89.94°, but the α'' value is too far from 90° and the symmetry relations were not respected. |
x | y | z | Uiso*/Ueq | ||
S13 | 1.02144 (7) | 1.06656 (5) | 0.86241 (4) | 0.0538 (1) | |
S14 | 0.72711 (6) | 0.47601 (6) | 0.73474 (4) | 0.0544 (1) | |
P2 | 0.78330 (6) | 0.77520 (5) | 0.75681 (4) | 0.0426 (1) | |
F19 | 1.2412 (2) | 1.1270 (2) | 0.7305 (1) | 0.1060 (5) | |
F20 | 1.1711 (3) | 1.2993 (2) | 0.8086 (2) | 0.1290 (7) | |
F21 | 1.0036 (3) | 1.1208 (2) | 0.6764 (1) | 0.1135 (6) | |
F22 | 0.8234 (2) | 0.4536 (3) | 0.9221 (2) | 0.1616 (7) | |
F23 | 0.6296 (3) | 0.5291 (3) | 0.9226 (1) | 0.1379 (8) | |
F24 | 0.5796 (3) | 0.3098 (2) | 0.8486 (2) | 0.1576 (8) | |
O15 | 1.1439 (2) | 1.1296 (2) | 0.9574 (1) | 0.0695 (4) | |
O16 | 0.8643 (2) | 1.0794 (2) | 0.8634 (1) | 0.0736 (4) | |
O17 | 0.7955 (2) | 0.3775 (2) | 0.6799 (2) | 0.0844 (5) | |
O18 | 0.5710 (2) | 0.4722 (2) | 0.6912 (1) | 0.0720 (5) | |
N1 | 0.9950 (2) | 0.9007 (1) | 0.8061 (1) | 0.0412 (3) | |
N3 | 0.8608 (2) | 0.6395 (2) | 0.7673 (1) | 0.0427 (3) | |
N10 | 0.7636 (2) | 0.7717 (2) | 0.6287 (1) | 0.0522 (4) | |
C4 | 1.0443 (2) | 0.6837 (2) | 0.7771 (1) | 0.0445 (4) | |
C5 | 1.1137 (2) | 0.8403 (2) | 0.8437 (1) | 0.0443 (4) | |
C6 | 1.2977 (2) | 0.9119 (2) | 0.8390 (2) | 0.0626 (6) | |
C7 | 1.3904 (3) | 0.8326 (3) | 0.8832 (2) | 0.0759 (7) | |
C8 | 1.3157 (3) | 0.6715 (3) | 0.8295 (2) | 0.0724 (6) | |
C9 | 1.1277 (3) | 0.6027 (2) | 0.8264 (2) | 0.0594 (5) | |
C11 | 1.1162 (4) | 1.1589 (3) | 0.7636 (2) | 0.0785 (7) | |
C12 | 0.6911 (3) | 0.4392 (3) | 0.8656 (2) | 0.0830 (7) | |
C25 | 0.8855 (3) | 0.7697 (3) | 0.5546 (2) | 0.0633 (6) | |
C26 | 0.8523 (4) | 0.6232 (3) | 0.4787 (2) | 0.0871 (8) | |
C27 | 0.5944 (3) | 0.7499 (3) | 0.5791 (2) | 0.0765 (7) | |
C28 | 0.5895 (4) | 0.8825 (4) | 0.5532 (3) | 0.131 (1) | |
H1 | 1.0728 | 0.6794 | 0.7063 | 0.053* | |
H2 | 1.1040 | 0.8429 | 0.9173 | 0.053* | |
H3 | 1.3130 | 0.9068 | 0.7656 | 0.075* | |
H4 | 1.3398 | 1.0105 | 0.8820 | 0.075* | |
H5 | 1.5037 | 0.8697 | 0.8719 | 0.091* | |
H6 | 1.3872 | 0.8503 | 0.9592 | 0.091* | |
H7 | 1.3682 | 0.6278 | 0.8685 | 0.087* | |
H8 | 1.3378 | 0.6532 | 0.7568 | 0.087* | |
H9 | 1.1043 | 0.6078 | 0.8984 | 0.071* | |
H10 | 1.0859 | 0.5040 | 0.7833 | 0.071* | |
H11 | 0.8845 | 0.8324 | 0.5122 | 0.076* | |
H12 | 0.9935 | 0.8049 | 0.5971 | 0.076* | |
H13 | 0.9328 | 0.6314 | 0.4308 | 0.105* | |
H14 | 0.8601 | 0.5606 | 0.5195 | 0.105* | |
H15 | 0.7428 | 0.5845 | 0.4374 | 0.105* | |
H16 | 0.5598 | 0.6719 | 0.5135 | 0.092* | |
H17 | 0.5188 | 0.7260 | 0.6286 | 0.092* | |
H18 | 0.6180 | 0.9599 | 0.6187 | 0.157* | |
H19 | 0.6676 | 0.9096 | 0.5058 | 0.157* | |
H20 | 0.4797 | 0.8615 | 0.5187 | 0.157* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S13 | 0.0782 (3) | 0.0469 (2) | 0.0446 (2) | 0.0345 (2) | 0.0133 (2) | 0.0115 (2) |
S14 | 0.0510 (3) | 0.0480 (2) | 0.0549 (3) | 0.0107 (2) | −0.0008 (2) | 0.0139 (2) |
P2 | 0.0439 (2) | 0.0575 (2) | 0.0365 (2) | 0.0281 (2) | 0.0094 (2) | 0.0178 (2) |
F19 | 0.122 (1) | 0.095 (1) | 0.130 (1) | 0.0456 (8) | 0.0656 (9) | 0.0666 (8) |
F20 | 0.202 (2) | 0.0496 (7) | 0.135 (2) | 0.0399 (9) | 0.036 (1) | 0.0369 (8) |
F21 | 0.144 (1) | 0.124 (1) | 0.0819 (9) | 0.039 (1) | 0.0170 (9) | 0.0656 (7) |
F22 | 0.089 (1) | 0.271 (2) | 0.151 (1) | 0.032 (1) | 0.0050 (9) | 0.1656 (9) |
F23 | 0.160 (2) | 0.185 (2) | 0.092 (1) | 0.068 (1) | 0.061 (1) | 0.070 (1) |
F24 | 0.130 (2) | 0.126 (1) | 0.194 (2) | −0.018 (1) | 0.022 (1) | 0.109 (1) |
O15 | 0.094 (1) | 0.0529 (7) | 0.0509 (8) | 0.0299 (7) | −0.0007 (7) | −0.0012 (6) |
O16 | 0.0982 (9) | 0.0778 (7) | 0.0757 (9) | 0.0647 (6) | 0.0254 (7) | 0.0264 (7) |
O17 | 0.080 (1) | 0.0516 (8) | 0.104 (1) | 0.0209 (7) | 0.009 (1) | 0.0013 (9) |
O18 | 0.0510 (8) | 0.074 (1) | 0.074 (1) | 0.0080 (7) | −0.0124 (7) | 0.0211 (8) |
N1 | 0.0488 (7) | 0.0423 (6) | 0.0368 (6) | 0.0233 (5) | 0.0079 (5) | 0.0104 (5) |
N3 | 0.0391 (6) | 0.0464 (7) | 0.0461 (7) | 0.0180 (5) | 0.0047 (5) | 0.0174 (6) |
N10 | 0.0565 (8) | 0.0709 (9) | 0.0374 (7) | 0.0318 (6) | 0.0041 (6) | 0.0197 (6) |
C4 | 0.0404 (8) | 0.0466 (8) | 0.0494 (9) | 0.0198 (6) | 0.0098 (7) | 0.0144 (7) |
C5 | 0.0442 (8) | 0.0485 (8) | 0.0417 (8) | 0.0243 (6) | 0.0046 (7) | 0.0070 (7) |
C6 | 0.0434 (9) | 0.054 (1) | 0.080 (1) | 0.0137 (8) | 0.0081 (9) | 0.012 (1) |
C7 | 0.0413 (9) | 0.078 (1) | 0.095 (2) | 0.0272 (9) | −0.003 (1) | −0.001 (1) |
C8 | 0.054 (1) | 0.078 (1) | 0.097 (2) | 0.0421 (8) | 0.012 (1) | 0.021 (1) |
C9 | 0.0553 (9) | 0.0549 (9) | 0.074 (1) | 0.0307 (7) | 0.0011 (9) | 0.0165 (9) |
C11 | 0.114 (2) | 0.055 (1) | 0.077 (1) | 0.034 (1) | 0.024 (1) | 0.0324 (9) |
C12 | 0.065 (1) | 0.093 (2) | 0.091 (1) | 0.010 (1) | 0.009 (1) | 0.058 (1) |
C25 | 0.076 (1) | 0.086 (1) | 0.0378 (8) | 0.037 (1) | 0.0162 (8) | 0.0272 (8) |
C26 | 0.107 (2) | 0.104 (2) | 0.052 (1) | 0.050 (1) | 0.017 (1) | 0.011 (1) |
C27 | 0.074 (1) | 0.107 (2) | 0.059 (1) | 0.045 (1) | −0.007 (1) | 0.030 (1) |
C28 | 0.128 (2) | 0.155 (2) | 0.156 (3) | 0.089 (1) | −0.003 (2) | 0.077 (2) |
P2—N1 | 1.783 (2) | C5—H2 | 0.95 |
P2—N3 | 1.792 (2) | C6—C7 | 1.519 (4) |
P2—N10 | 1.637 (2) | C6—H3 | 0.95 |
S13—O15 | 1.412 (2) | C6—H4 | 0.95 |
S13—O16 | 1.414 (2) | C7—C8 | 1.503 (3) |
S13—N1 | 1.608 (1) | C7—H5 | 0.95 |
S13—C11 | 1.834 (3) | C7—H6 | 0.95 |
S14—O17 | 1.415 (2) | C8—C9 | 1.516 (3) |
S14—O18 | 1.418 (2) | C8—H7 | 0.95 |
S14—N3 | 1.596 (1) | C8—H8 | 0.95 |
S14—C12 | 1.837 (3) | C9—H9 | 0.95 |
F19—C11 | 1.303 (3) | C9—H10 | 0.95 |
F20—C11 | 1.309 (3) | C25—C26 | 1.494 (4) |
F21—C11 | 1.320 (3) | C25—H11 | 0.95 |
F22—C12 | 1.262 (3) | C25—H12 | 0.95 |
F23—C12 | 1.318 (4) | C26—H13 | 0.95 |
F24—C12 | 1.291 (3) | C26—H14 | 0.95 |
N1—C5 | 1.499 (2) | C26—H15 | 0.95 |
N3—C4 | 1.474 (2) | C27—C28 | 1.507 (4) |
N10—C25 | 1.461 (3) | C27—H16 | 0.95 |
N10—C27 | 1.480 (3) | C27—H17 | 0.95 |
C4—C5 | 1.501 (2) | C28—H18 | 0.95 |
C4—C9 | 1.513 (3) | C28—H19 | 0.95 |
C4—H1 | 0.95 | C28—H20 | 0.95 |
C5—C6 | 1.506 (3) | ||
F19···F24i | 2.917 (3) | ||
N1—P2—N3 | 85.47 (7) | C7—C8—C9 | 113.7 (2) |
N1—P2—N10 | 101.42 (8) | C7—C8—H7 | 108.4 |
N3—P2—N10 | 107.71 (8) | C7—C8—H8 | 108.4 |
O15—S13—O16 | 120.8 (1) | C9—C8—H7 | 108.4 |
O15—S13—N1 | 111.24 (9) | C9—C8—H8 | 108.4 |
O15—S13—C11 | 105.4 (1) | H7—C8—H8 | 109.5 |
O16—S13—N1 | 110.12 (8) | C4—C9—C8 | 109.0 (2) |
O16—S13—C11 | 104.0 (1) | C4—C9—H9 | 109.6 |
N1—S13—C11 | 103.4 (1) | C4—C9—H10 | 109.6 |
O17—S14—O18 | 121.3 (1) | C8—C9—H9 | 109.6 |
O17—S14—N3 | 111.5 (1) | C8—C9—H10 | 109.6 |
O17—S14—C12 | 105.9 (1) | H9—C9—H10 | 109.5 |
O18—S14—N3 | 108.26 (9) | S13—C11—F19 | 112.8 (2) |
O18—S14—C12 | 103.8 (1) | S13—C11—F20 | 109.1 (2) |
N3—S14—C12 | 104.5 (1) | S13—C11—F21 | 110.1 (2) |
S13—N1—P2 | 116.20 (9) | F19—C11—F20 | 108.4 (2) |
S13—N1—C5 | 120.3 (1) | F19—C11—F21 | 107.0 (2) |
P2—N1—C5 | 115.9 (1) | F20—C11—F21 | 109.3 (2) |
S14—N3—P2 | 117.01 (9) | S14—C12—F22 | 112.8 (2) |
S14—N3—C4 | 125.2 (1) | S14—C12—F23 | 109.5 (2) |
P2—N3—C4 | 115.8 (1) | S14—C12—F24 | 109.6 (2) |
P2—N10—C25 | 127.9 (1) | F22—C12—F23 | 108.2 (3) |
P2—N10—C27 | 115.4 (1) | F22—C12—F24 | 109.7 (3) |
C25—N10—C27 | 116.2 (2) | F23—C12—F24 | 106.8 (3) |
N3—C4—C5 | 104.2 (1) | N10—C25—C26 | 114.4 (2) |
N3—C4—C9 | 119.5 (2) | N10—C25—H11 | 108.2 |
N3—C4—H1 | 107.7 | N10—C25—H12 | 108.2 |
C5—C4—C9 | 109.5 (1) | C26—C25—H11 | 108.2 |
C5—C4—H1 | 107.7 | C26—C25—H12 | 108.2 |
C9—C4—H1 | 107.7 | H11—C25—H12 | 109.5 |
N1—C5—C4 | 104.8 (1) | C25—C26—H13 | 109.5 |
N1—C5—C6 | 118.9 (2) | C25—C26—H14 | 109.5 |
N1—C5—H2 | 107.3 | C25—C26—H15 | 109.5 |
C4—C5—C6 | 110.8 (2) | H13—C26—H14 | 109.5 |
C4—C5—H2 | 107.3 | H13—C26—H15 | 109.5 |
C6—C5—H2 | 107.3 | H14—C26—H15 | 109.5 |
C5—C6—C7 | 108.5 (2) | N10—C27—C28 | 112.8 (2) |
C5—C6—H3 | 109.7 | N10—C27—H16 | 108.6 |
C5—C6—H4 | 109.7 | N10—C27—H17 | 108.6 |
C7—C6—H3 | 109.7 | C28—C27—H16 | 108.6 |
C7—C6—H4 | 109.7 | C28—C27—H17 | 108.6 |
H3—C6—H4 | 109.5 | H16—C27—H17 | 109.5 |
C6—C7—C8 | 113.1 (2) | C27—C28—H18 | 109.5 |
C6—C7—H5 | 108.6 | C27—C28—H19 | 109.5 |
C6—C7—H6 | 108.6 | C27—C28—H20 | 109.5 |
C8—C7—H5 | 108.6 | H18—C28—H19 | 109.5 |
C8—C7—H6 | 108.6 | H18—C28—H20 | 109.5 |
H5—C7—H6 | 109.5 | H19—C28—H20 | 109.5 |
Symmetry code: (i) x+1, y+1, z. |
C10H16F6N3O4PS2 | Z = 2 |
Mr = 451.34 | F(000) = 460.00 |
Triclinic, P1 | Dx = 1.670 Mg m−3 |
Hall symbol: -P1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.972 (2) Å | Cell parameters from 25 reflections |
b = 9.116 (6) Å | θ = 10.0–12.3° |
c = 12.990 (7) Å | µ = 0.47 mm−1 |
α = 97.40 (4)° | T = 293 K |
β = 104.03 (4)° | Prism, colourless |
γ = 60.58 (4)° | 0.25 × 0.18 × 0.18 mm |
V = 897.8 (9) Å3 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.022 |
Radiation source: X-ray tube | θmax = 30.0°, θmin = 2.6° |
Graphite monochromator | h = −12→12 |
ω scans | k = −12→12 |
5444 measured reflections | l = 0→18 |
5227 independent reflections | 2 standard reflections every 120 reflections |
3076 reflections with I > 3σ(I) | intensity decay: 10.8% |
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters not refined |
wR(F2) = 0.070 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.00090|Fo|2] |
S = 1.91 | (Δ/σ)max = 0.008 |
3076 reflections | Δρmax = 0.53 e Å−3 |
235 parameters | Δρmin = −0.39 e Å−3 |
C10H16F6N3O4PS2 | γ = 60.58 (4)° |
Mr = 451.34 | V = 897.8 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.972 (2) Å | Mo Kα radiation |
b = 9.116 (6) Å | µ = 0.47 mm−1 |
c = 12.990 (7) Å | T = 293 K |
α = 97.40 (4)° | 0.25 × 0.18 × 0.18 mm |
β = 104.03 (4)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.022 |
5444 measured reflections | 2 standard reflections every 120 reflections |
5227 independent reflections | intensity decay: 10.8% |
3076 reflections with I > 3σ(I) |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.070 | H-atom parameters not refined |
S = 1.91 | Δρmax = 0.53 e Å−3 |
3076 reflections | Δρmin = −0.39 e Å−3 |
235 parameters |
Refinement. For compound (IIIb), in order to have angle values closer to those of compound (IIIa), we chose the following cell parameters: a = 8.972 (2), b = 9.116 (6) and c = 12.990 (7) Å, and α = 97.40 (4), β = 104.03 (4) and γ = 60.58 (4)°. This was in preference to the three-acute cell, with a' = 8.972 (2), b' = 9.116 (6) and c' = 12.990 (7) Å, and α' = 82.60 (4), β' = 75.97 (4) and γ' = 60.58 (4)°. There was also a possibility for a monoclinic C cell, with a'' = 8.972, b'' = 15.881 and c'' = 12.990 Å, and α'' = 89.38, β'' = 104.03 and γ'' = 89.94°, but the α'' value is too far from 90° and the symmetry relations were not respected. |
x | y | z | Uiso*/Ueq | ||
S13 | 0.74601 (8) | −0.16281 (9) | 0.39594 (5) | 0.0601 (2) | |
S14 | 0.42988 (7) | 0.24040 (7) | 0.05433 (4) | 0.0455 (1) | |
P2 | 0.64602 (6) | 0.10912 (7) | 0.25814 (4) | 0.0432 (1) | |
F19 | 0.9284 (3) | −0.3171 (3) | 0.2516 (2) | 0.1114 (6) | |
F20 | 0.9839 (3) | −0.4718 (3) | 0.3810 (2) | 0.1248 (7) | |
F21 | 0.7511 (3) | −0.4036 (3) | 0.2609 (2) | 0.1072 (7) | |
F22 | 0.3710 (3) | 0.5333 (2) | 0.1387 (2) | 0.1034 (6) | |
F23 | 0.1438 (2) | 0.5052 (2) | 0.0915 (2) | 0.0979 (6) | |
F24 | 0.2557 (3) | 0.5384 (2) | −0.0252 (2) | 0.1002 (6) | |
O15 | 0.8729 (3) | −0.1095 (3) | 0.4379 (2) | 0.0968 (7) | |
O16 | 0.6789 (3) | −0.2161 (3) | 0.4634 (2) | 0.0848 (6) | |
O17 | 0.5926 (2) | 0.2232 (2) | 0.0475 (1) | 0.0630 (4) | |
O18 | 0.3334 (2) | 0.1879 (2) | −0.0298 (1) | 0.0604 (4) | |
N1 | 0.5956 (2) | −0.0295 (2) | 0.3110 (1) | 0.0469 (4) | |
N3 | 0.4450 (2) | 0.1696 (2) | 0.1659 (1) | 0.0392 (4) | |
N10 | 0.5951 (2) | 0.2767 (3) | 0.3356 (2) | 0.0548 (5) | |
C4 | 0.3478 (3) | 0.0784 (3) | 0.1738 (2) | 0.0522 (5) | |
C5 | 0.4108 (3) | 0.0112 (3) | 0.2830 (2) | 0.0587 (6) | |
C6 | 0.3521 (3) | −0.1130 (4) | 0.2951 (2) | 0.0701 (7) | |
C7 | 0.1599 (4) | −0.0387 (4) | 0.2577 (3) | 0.0901 (9) | |
C8 | 0.0835 (4) | 0.0506 (5) | 0.1541 (3) | 0.0904 (9) | |
C9 | 0.1549 (3) | 0.1622 (4) | 0.1371 (3) | 0.0736 (8) | |
C11 | 0.8579 (4) | −0.3486 (4) | 0.3174 (3) | 0.0799 (8) | |
C12 | 0.2909 (4) | 0.4689 (3) | 0.0667 (2) | 0.0683 (7) | |
C25 | 0.7401 (4) | 0.2975 (4) | 0.4020 (3) | 0.0914 (9) | |
C26 | 0.4288 (4) | 0.3851 (4) | 0.3688 (2) | 0.0682 (7) | |
H1 | 0.3908 | −0.0179 | 0.1290 | 0.063* | |
H2 | 0.3534 | 0.1047 | 0.3268 | 0.070* | |
H3 | 0.3825 | −0.1418 | 0.3678 | 0.084* | |
H4 | 0.4085 | −0.2114 | 0.2544 | 0.084* | |
H5 | 0.1313 | −0.1274 | 0.2513 | 0.108* | |
H6 | 0.1066 | 0.0397 | 0.3102 | 0.108* | |
H7 | 0.1042 | −0.0320 | 0.0990 | 0.109* | |
H8 | −0.0390 | 0.1185 | 0.1494 | 0.109* | |
H9 | 0.1261 | 0.1860 | 0.0637 | 0.088* | |
H10 | 0.1042 | 0.2645 | 0.1758 | 0.088* | |
H11 | 0.7588 | 0.2646 | 0.4724 | 0.110* | |
H12 | 0.8430 | 0.2292 | 0.3747 | 0.110* | |
H13 | 0.7130 | 0.4122 | 0.4020 | 0.110* | |
H14 | 0.4282 | 0.3409 | 0.4309 | 0.082* | |
H15 | 0.3354 | 0.3892 | 0.3136 | 0.082* | |
H16 | 0.4150 | 0.4954 | 0.3832 | 0.082* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S13 | 0.0560 (3) | 0.0686 (3) | 0.0410 (3) | −0.0195 (3) | −0.0007 (2) | 0.0165 (2) |
S14 | 0.0511 (2) | 0.0442 (2) | 0.0376 (2) | −0.0182 (2) | 0.0107 (2) | 0.0035 (2) |
P2 | 0.0343 (2) | 0.0513 (3) | 0.0429 (3) | −0.0196 (2) | 0.0057 (2) | 0.0027 (2) |
F19 | 0.097 (1) | 0.110 (1) | 0.107 (1) | −0.013 (1) | 0.0565 (9) | 0.020 (1) |
F20 | 0.096 (1) | 0.088 (1) | 0.121 (2) | 0.017 (1) | 0.015 (1) | 0.049 (1) |
F21 | 0.104 (1) | 0.073 (1) | 0.118 (2) | −0.025 (1) | 0.023 (1) | −0.017 (1) |
F22 | 0.133 (1) | 0.0543 (8) | 0.105 (1) | −0.0425 (8) | 0.002 (1) | −0.0085 (9) |
F23 | 0.079 (1) | 0.061 (1) | 0.126 (1) | 0.0008 (8) | 0.0442 (9) | 0.011 (1) |
F24 | 0.120 (1) | 0.0702 (9) | 0.092 (1) | −0.0258 (9) | 0.011 (1) | 0.0413 (8) |
O15 | 0.078 (1) | 0.114 (2) | 0.079 (1) | −0.046 (1) | −0.035 (1) | 0.029 (1) |
O16 | 0.085 (1) | 0.101 (1) | 0.058 (1) | −0.0288 (9) | 0.0160 (8) | 0.0325 (9) |
O17 | 0.0647 (8) | 0.0729 (9) | 0.0634 (9) | −0.0350 (6) | 0.0235 (7) | 0.0084 (7) |
O18 | 0.0711 (9) | 0.0685 (9) | 0.0375 (8) | −0.0327 (7) | 0.0044 (7) | 0.0014 (7) |
N1 | 0.0419 (8) | 0.0531 (9) | 0.0417 (9) | −0.0202 (6) | 0.0014 (7) | 0.0101 (7) |
N3 | 0.0358 (7) | 0.0458 (8) | 0.0348 (8) | −0.0178 (6) | 0.0068 (6) | 0.0033 (6) |
N10 | 0.0562 (9) | 0.065 (1) | 0.049 (1) | −0.0367 (7) | 0.0076 (8) | −0.0077 (8) |
C4 | 0.0467 (9) | 0.078 (1) | 0.041 (1) | −0.0378 (8) | 0.0013 (8) | 0.0080 (9) |
C5 | 0.0415 (9) | 0.067 (1) | 0.068 (1) | −0.0230 (8) | 0.0075 (9) | 0.019 (1) |
C6 | 0.079 (1) | 0.091 (1) | 0.065 (1) | −0.0585 (9) | 0.009 (1) | 0.011 (1) |
C7 | 0.063 (1) | 0.106 (2) | 0.121 (2) | −0.047 (1) | 0.026 (1) | 0.019 (2) |
C8 | 0.064 (1) | 0.151 (2) | 0.082 (2) | −0.073 (1) | 0.005 (1) | 0.009 (2) |
C9 | 0.037 (1) | 0.081 (2) | 0.093 (2) | −0.020 (1) | −0.001 (1) | 0.025 (2) |
C11 | 0.061 (2) | 0.068 (2) | 0.077 (2) | 0.002 (1) | 0.018 (1) | 0.024 (1) |
C12 | 0.081 (2) | 0.047 (1) | 0.062 (1) | −0.019 (1) | 0.010 (1) | 0.007 (1) |
C25 | 0.083 (2) | 0.108 (2) | 0.089 (2) | −0.062 (1) | 0.003 (2) | −0.025 (2) |
C26 | 0.080 (1) | 0.074 (1) | 0.062 (1) | −0.044 (1) | 0.030 (1) | −0.024 (1) |
P2—N1 | 1.791 (2) | C4—C9 | 1.483 (3) |
P2—N3 | 1.771 (2) | C4—H1 | 0.95 |
P2—N10 | 1.642 (2) | C5—C6 | 1.502 (4) |
S13—O15 | 1.416 (2) | C5—H2 | 0.95 |
S13—O16 | 1.421 (2) | C6—C7 | 1.483 (4) |
S13—N1 | 1.590 (2) | C6—H3 | 0.95 |
S13—C11 | 1.816 (3) | C6—H4 | 0.95 |
S14—O17 | 1.414 (2) | C7—C8 | 1.494 (5) |
S14—O18 | 1.409 (2) | C7—H5 | 0.95 |
S14—N3 | 1.611 (2) | C7—H6 | 0.95 |
S14—C12 | 1.838 (3) | C8—C9 | 1.504 (5) |
F19—C11 | 1.310 (4) | C8—H7 | 0.95 |
F20—C11 | 1.327 (3) | C8—H8 | 0.95 |
F21—C11 | 1.321 (4) | C9—H9 | 0.95 |
F22—C12 | 1.298 (4) | C9—H10 | 0.95 |
F23—C12 | 1.307 (4) | C25—H11 | 0.95 |
F24—C12 | 1.319 (3) | C25—H12 | 0.95 |
N1—C5 | 1.469 (3) | C25—H13 | 0.95 |
N3—C4 | 1.496 (3) | C26—H14 | 0.95 |
N10—C25 | 1.459 (4) | C26—H15 | 0.95 |
N10—C26 | 1.463 (3) | C26—H16 | 0.95 |
C4—C5 | 1.484 (3) | ||
F19···F23i | 2.947 (3) | ||
N1—P2—N3 | 86.05 (8) | C6—C7—C8 | 116.7 (3) |
N1—P2—N10 | 107.3 (1) | C6—C7—H5 | 107.6 |
N3—P2—N10 | 100.80 (8) | C6—C7—H6 | 107.6 |
O15—S13—O16 | 121.2 (1) | C8—C7—H5 | 107.6 |
O15—S13—N1 | 108.7 (1) | C8—C7—H6 | 107.6 |
O15—S13—C11 | 103.8 (2) | H5—C7—H6 | 109.5 |
O16—S13—N1 | 112.5 (1) | C7—C8—C9 | 115.6 (3) |
O16—S13—C11 | 104.6 (2) | C7—C8—H7 | 107.9 |
N1—S13—C11 | 104.3 (1) | C7—C8—H8 | 107.9 |
O17—S14—O18 | 121.1 (1) | C9—C8—H7 | 107.9 |
O17—S14—N3 | 110.3 (1) | C9—C8—H8 | 107.9 |
O17—S14—C12 | 104.0 (1) | H7—C8—H8 | 109.5 |
O18—S14—N3 | 110.9 (1) | C4—C9—C8 | 110.6 (2) |
O18—S14—C12 | 105.2 (1) | C4—C9—H9 | 109.2 |
N3—S14—C12 | 103.5 (1) | C4—C9—H10 | 109.2 |
S13—N1—P2 | 117.1 (1) | C8—C9—H9 | 109.2 |
S13—N1—C5 | 126.9 (2) | C8—C9—H10 | 109.2 |
P2—N1—C5 | 115.2 (1) | H9—C9—H10 | 109.5 |
S14—N3—P2 | 116.2 (1) | S13—C11—F19 | 111.0 (3) |
S14—N3—C4 | 121.3 (1) | S13—C11—F20 | 109.7 (2) |
P2—N3—C4 | 115.7 (1) | S13—C11—F21 | 112.1 (2) |
P2—N10—C25 | 116.8 (2) | F19—C11—F20 | 108.4 (3) |
P2—N10—C26 | 128.0 (2) | F19—C11—F21 | 107.8 (3) |
C25—N10—C26 | 113.0 (2) | F20—C11—F21 | 107.8 (3) |
N3—C4—C5 | 106.7 (2) | S14—C12—F22 | 110.7 (2) |
N3—C4—C9 | 119.3 (2) | S14—C12—F23 | 111.7 (2) |
N3—C4—H1 | 105.1 | S14—C12—F24 | 108.5 (2) |
C5—C4—C9 | 114.3 (2) | F22—C12—F23 | 108.5 (3) |
C5—C4—H1 | 105.1 | F22—C12—F24 | 108.6 (3) |
C9—C4—H1 | 105.1 | F23—C12—F24 | 108.7 (2) |
N1—C5—C4 | 104.8 (2) | N10—C25—H11 | 109.5 |
N1—C5—C6 | 122.3 (2) | N10—C25—H12 | 109.5 |
N1—C5—H2 | 105.4 | N10—C25—H13 | 109.5 |
C4—C5—C6 | 112.2 (2) | H11—C25—H12 | 109.5 |
C4—C5—H2 | 105.4 | H11—C25—H13 | 109.5 |
C6—C5—H2 | 105.4 | H12—C25—H13 | 109.5 |
C5—C6—C7 | 110.2 (2) | N10—C26—H14 | 109.5 |
C5—C6—H3 | 109.3 | N10—C26—H15 | 109.5 |
C5—C6—H4 | 109.3 | N10—C26—H16 | 109.5 |
C7—C6—H3 | 109.3 | H14—C26—H15 | 109.5 |
C7—C6—H4 | 109.3 | H14—C26—H16 | 109.5 |
H3—C6—H4 | 109.5 | H15—C26—H16 | 109.5 |
Symmetry code: (i) x+1, y−1, z. |
C17H23F12N5O8P2S4·0.98(CHCl3) | F(000) = 954.06 |
Mr = 960.65 | Dx = 1.767 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 25 reflections |
a = 8.812 (4) Å | θ = 10.0–11.6° |
b = 13.897 (3) Å | µ = 0.68 mm−1 |
c = 14.728 (6) Å | T = 293 K |
β = 90.21 (3)° | Monoclinic prism, colourless |
V = 1803 (1) Å3 | 0.22 × 0.20 × 0.15 mm |
Z = 2 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.031 |
Radiation source: X-ray tube | θmax = 30.9°, θmin = 2.0° |
Graphite monochromator | h = −12→12 |
ω/2θ scans | k = 0→20 |
5666 measured reflections | l = 0→20 |
5519 independent reflections | 2 standard reflections every 120 reflections |
4855 reflections with I > 0 | intensity decay: 7.0% |
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.086 | H-atom parameters not refined |
wR(F2) = 0.051 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.00013|Fo|2] |
S = 1.88 | (Δ/σ)max = 0.007 |
4855 reflections | Δρmax = 0.46 e Å−3 |
486 parameters | Δρmin = −0.61 e Å−3 |
C17H23F12N5O8P2S4·0.98(CHCl3) | V = 1803 (1) Å3 |
Mr = 960.65 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.812 (4) Å | µ = 0.68 mm−1 |
b = 13.897 (3) Å | T = 293 K |
c = 14.728 (6) Å | 0.22 × 0.20 × 0.15 mm |
β = 90.21 (3)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.031 |
5666 measured reflections | 2 standard reflections every 120 reflections |
5519 independent reflections | intensity decay: 7.0% |
4855 reflections with I > 0 |
R[F2 > 2σ(F2)] = 0.086 | 0 restraints |
wR(F2) = 0.051 | H-atom parameters not refined |
S = 1.88 | Δρmax = 0.46 e Å−3 |
4855 reflections | Δρmin = −0.61 e Å−3 |
486 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl50 | 0.2039 (3) | 0.2634 (3) | 0.1674 (1) | 0.1483 (8) | 0.908 |
Cl51 | 0.3289 (8) | 0.3505 (5) | 0.3153 (4) | 0.161 (2) | 0.387 |
Cl52 | 0.0720 (3) | 0.2825 (3) | 0.3473 (2) | 0.188 (1) | 0.844 |
Cl53 | 0.3574 (7) | 0.2083 (7) | 0.3307 (4) | 0.191 (3) | 0.378 |
Cl54 | 0.3230 (9) | 0.1652 (4) | 0.3031 (5) | 0.156 (2) | 0.431 |
S13 | 0.6893 (1) | 0.4471 | 0.89379 (8) | 0.0458 (3) | |
S14 | 0.6784 (1) | 0.06162 (7) | 0.90237 (8) | 0.0472 (3) | |
S37 | 0.3134 (1) | 0.45383 (8) | 0.68345 (8) | 0.0470 (3) | |
S38 | 0.3120 (1) | 0.07042 (8) | 0.68187 (8) | 0.0447 (3) | |
P2 | 0.59560 (9) | 0.2537 (1) | 0.85283 (5) | 0.0365 (2) | |
P27 | 0.30204 (8) | 0.2614 (1) | 0.75138 (5) | 0.0351 (2) | |
F19 | 0.9742 (4) | 0.4147 (3) | 0.9363 (3) | 0.116 (1) | |
F20 | 0.9415 (4) | 0.5221 (3) | 0.8400 (3) | 0.126 (2) | |
F21 | 0.9170 (4) | 0.3732 (3) | 0.8046 (3) | 0.095 (1) | |
F22 | 0.9652 (4) | 0.0878 (4) | 0.9360 (3) | 0.129 (2) | |
F23 | 0.8970 (4) | 0.1358 (3) | 0.8106 (3) | 0.147 (2) | |
F24 | 0.9197 (4) | −0.0113 (3) | 0.8322 (3) | 0.116 (1) | |
F43 | 0.0802 (4) | 0.5269 (3) | 0.6043 (3) | 0.115 (1) | |
F44 | 0.0758 (4) | 0.3751 (3) | 0.6114 (3) | 0.105 (1) | |
F45 | 0.2175 (5) | 0.4408 (3) | 0.5178 (2) | 0.113 (1) | |
F46 | 0.0683 (4) | 0.1542 (3) | 0.6164 (3) | 0.104 (1) | |
F47 | 0.2051 (4) | 0.0826 (3) | 0.5168 (2) | 0.101 (1) | |
F48 | 0.0675 (4) | 0.0029 (3) | 0.6055 (3) | 0.106 (1) | |
O15 | 0.6774 (4) | 0.5183 (2) | 0.9628 (2) | 0.062 (1) | |
O16 | 0.6180 (4) | 0.4567 (2) | 0.8080 (2) | 0.066 (1) | |
O17 | 0.6796 (4) | −0.0057 (2) | 0.9730 (2) | 0.066 (1) | |
O18 | 0.5975 (4) | 0.0460 (2) | 0.8218 (2) | 0.071 (1) | |
O39 | 0.2368 (4) | 0.4646 (2) | 0.7668 (2) | 0.0580 (9) | |
O40 | 0.4152 (4) | 0.5242 (2) | 0.6494 (2) | 0.0586 (9) | |
O41 | 0.2405 (4) | 0.0602 (2) | 0.7674 (2) | 0.0560 (9) | |
O42 | 0.4068 (4) | −0.0002 (2) | 0.6451 (2) | 0.062 (1) | |
N1 | 0.6486 (4) | 0.3429 (2) | 0.9305 (2) | 0.047 (1) | |
N3 | 0.6352 (4) | 0.1692 (2) | 0.9385 (2) | 0.0355 (8) | |
N10 | 0.4050 (3) | 0.2558 (3) | 0.8490 (1) | 0.0348 (6) | |
N26 | 0.3882 (4) | 0.3479 (2) | 0.6824 (2) | 0.0393 (9) | |
N28 | 0.3887 (4) | 0.1749 (2) | 0.6810 (2) | 0.0399 (9) | |
C4 | 0.7007 (5) | 0.2083 (3) | 1.0235 (3) | 0.044 (1) | |
C5 | 0.6446 (5) | 0.3113 (3) | 1.0299 (3) | 0.039 (1) | |
C6 | 0.7332 (6) | 0.3646 (3) | 1.0995 (3) | 0.063 (1) | |
C7 | 0.7094 (9) | 0.3166 (4) | 1.1909 (4) | 0.084 (2) | |
C8 | 0.7287 (8) | 0.2097 (4) | 1.1904 (4) | 0.081 (2) | |
C9 | 0.6571 (7) | 0.1555 (3) | 1.1118 (3) | 0.068 (1) | |
C11 | 0.8937 (6) | 0.4378 (4) | 0.8648 (4) | 0.074 (2) | |
C12 | 0.8778 (6) | 0.0704 (3) | 0.8673 (4) | 0.059 (1) | |
C25 | 0.3078 (4) | 0.2537 (5) | 0.9312 (2) | 0.0491 (9) | |
C29 | 0.4747 (5) | 0.2130 (3) | 0.6014 (3) | 0.044 (1) | |
C30 | 0.5200 (4) | 0.3134 (3) | 0.6302 (3) | 0.040 (1) | |
C31 | 0.5769 (6) | 0.3702 (3) | 0.5492 (3) | 0.057 (1) | |
C32 | 0.7148 (6) | 0.3170 (4) | 0.5147 (3) | 0.069 (2) | |
C33 | 0.6876 (7) | 0.2118 (4) | 0.4906 (4) | 0.079 (2) | |
C34 | 0.6146 (6) | 0.1584 (4) | 0.5716 (3) | 0.068 (1) | |
C35 | 0.1624 (6) | 0.4472 (4) | 0.6015 (4) | 0.067 (2) | |
C36 | 0.1522 (6) | 0.0782 (4) | 0.5997 (4) | 0.075 (2) | |
C49 | 0.222 (1) | 0.256 (1) | 0.2864 (6) | 0.272 (5) | 0.983 |
H1 | 0.8081 | 0.2089 | 1.0183 | 0.053* | |
H2 | 0.5416 | 0.3098 | 1.0487 | 0.046* | |
H3 | 0.6995 | 0.4294 | 1.1021 | 0.075* | |
H4 | 0.8379 | 0.3632 | 1.0843 | 0.075* | |
H5 | 0.7805 | 0.3430 | 1.2327 | 0.101* | |
H6 | 0.6094 | 0.3307 | 1.2106 | 0.101* | |
H7 | 0.8345 | 0.1965 | 1.1898 | 0.098* | |
H8 | 0.6858 | 0.1854 | 1.2449 | 0.098* | |
H9 | 0.6941 | 0.0913 | 1.1103 | 0.082* | |
H10 | 0.5498 | 0.1547 | 1.1182 | 0.082* | |
H11 | 0.3352 | 0.2002 | 0.9679 | 0.059* | |
H12 | 0.2044 | 0.2480 | 0.9135 | 0.059* | |
H13 | 0.3216 | 0.3114 | 0.9647 | 0.059* | |
H14 | 0.4072 | 0.2178 | 0.5512 | 0.053* | |
H15 | 0.6025 | 0.3072 | 0.6716 | 0.047* | |
H16 | 0.6038 | 0.4336 | 0.5671 | 0.068* | |
H17 | 0.5009 | 0.3731 | 0.5033 | 0.068* | |
H18 | 0.7910 | 0.3195 | 0.5604 | 0.083* | |
H19 | 0.7499 | 0.3491 | 0.4618 | 0.083* | |
H20 | 0.6216 | 0.2083 | 0.4396 | 0.095* | |
H21 | 0.7817 | 0.1823 | 0.4762 | 0.095* | |
H22 | 0.6850 | 0.1550 | 0.6205 | 0.081* | |
H23 | 0.5868 | 0.0952 | 0.5536 | 0.081* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl50 | 0.183 (2) | 0.175 (2) | 0.087 (1) | 0.022 (3) | 0.005 (1) | 0.020 (2) |
Cl51 | 0.194 (5) | 0.190 (5) | 0.098 (3) | −0.116 (4) | 0.013 (4) | −0.041 (3) |
Cl52 | 0.138 (2) | 0.276 (4) | 0.149 (2) | 0.095 (2) | −0.003 (2) | −0.076 (2) |
Cl53 | 0.111 (4) | 0.35 (1) | 0.112 (4) | 0.080 (5) | −0.009 (3) | 0.057 (5) |
Cl54 | 0.187 (5) | 0.116 (3) | 0.163 (5) | 0.070 (3) | −0.007 (4) | −0.037 (3) |
S13 | 0.0437 (6) | 0.0333 (5) | 0.0602 (7) | −0.0036 (4) | −0.0035 (5) | 0.0059 (5) |
S14 | 0.0489 (6) | 0.0333 (5) | 0.0593 (7) | 0.0048 (5) | −0.0072 (5) | −0.0067 (5) |
S37 | 0.0510 (6) | 0.0328 (5) | 0.0571 (6) | 0.0033 (5) | −0.0080 (5) | 0.0019 (5) |
S38 | 0.0555 (6) | 0.0330 (5) | 0.0456 (6) | −0.0087 (5) | −0.0047 (5) | −0.0014 (5) |
P2 | 0.0358 (4) | 0.0361 (4) | 0.0375 (4) | −0.0021 (6) | −0.0028 (3) | 0.0008 (6) |
P27 | 0.0347 (4) | 0.0340 (4) | 0.0367 (4) | −0.0024 (6) | −0.0028 (3) | −0.0004 (7) |
F19 | 0.050 (2) | 0.163 (4) | 0.135 (3) | 0.018 (2) | −0.013 (2) | −0.001 (3) |
F20 | 0.079 (2) | 0.074 (2) | 0.224 (5) | −0.032 (2) | 0.048 (3) | 0.009 (3) |
F21 | 0.077 (2) | 0.088 (2) | 0.121 (2) | −0.013 (2) | 0.040 (2) | −0.038 (2) |
F22 | 0.048 (2) | 0.175 (4) | 0.164 (4) | 0.011 (2) | −0.019 (2) | −0.026 (3) |
F23 | 0.094 (2) | 0.153 (3) | 0.196 (4) | 0.045 (2) | 0.080 (2) | 0.089 (3) |
F24 | 0.086 (2) | 0.089 (2) | 0.174 (4) | 0.023 (2) | 0.026 (2) | −0.043 (2) |
F43 | 0.098 (3) | 0.093 (2) | 0.155 (3) | 0.036 (2) | −0.042 (2) | 0.024 (2) |
F44 | 0.091 (2) | 0.098 (2) | 0.126 (3) | −0.029 (2) | −0.053 (2) | 0.025 (2) |
F45 | 0.118 (3) | 0.140 (3) | 0.083 (2) | −0.011 (3) | −0.044 (2) | 0.017 (2) |
F46 | 0.086 (2) | 0.091 (2) | 0.135 (3) | 0.023 (2) | −0.060 (2) | −0.023 (2) |
F47 | 0.105 (2) | 0.148 (3) | 0.050 (2) | −0.034 (2) | −0.023 (2) | 0.001 (2) |
F48 | 0.095 (2) | 0.095 (2) | 0.129 (3) | −0.052 (2) | −0.041 (2) | −0.001 (2) |
O15 | 0.065 (2) | 0.034 (2) | 0.088 (2) | 0.003 (1) | −0.002 (2) | −0.005 (2) |
O16 | 0.077 (2) | 0.058 (2) | 0.061 (2) | −0.007 (2) | −0.015 (2) | 0.021 (2) |
O17 | 0.086 (2) | 0.040 (2) | 0.071 (2) | 0.011 (2) | 0.011 (2) | 0.006 (2) |
O18 | 0.075 (2) | 0.053 (2) | 0.084 (2) | 0.013 (2) | −0.028 (2) | −0.028 (2) |
O39 | 0.068 (2) | 0.045 (2) | 0.062 (2) | 0.009 (2) | 0.000 (2) | −0.011 (2) |
O40 | 0.062 (2) | 0.036 (1) | 0.078 (2) | −0.003 (1) | −0.008 (2) | 0.012 (2) |
O41 | 0.061 (2) | 0.050 (2) | 0.058 (2) | −0.012 (2) | 0.008 (2) | 0.007 (2) |
O42 | 0.079 (2) | 0.038 (2) | 0.068 (2) | 0.003 (2) | 0.002 (2) | −0.008 (2) |
N1 | 0.065 (2) | 0.034 (2) | 0.041 (2) | −0.009 (2) | −0.017 (2) | 0.007 (2) |
N3 | 0.036 (2) | 0.032 (2) | 0.039 (2) | 0.008 (1) | −0.003 (1) | 0.001 (1) |
N10 | 0.037 (1) | 0.033 (1) | 0.034 (1) | 0.000 (2) | 0.000 (1) | 0.002 (2) |
N26 | 0.045 (2) | 0.037 (2) | 0.036 (2) | 0.002 (1) | 0.002 (2) | 0.007 (1) |
N28 | 0.048 (2) | 0.028 (1) | 0.043 (2) | −0.004 (1) | 0.004 (2) | −0.004 (1) |
C4 | 0.045 (2) | 0.040 (2) | 0.048 (2) | −0.008 (2) | −0.008 (2) | 0.000 (2) |
C5 | 0.048 (2) | 0.032 (2) | 0.037 (2) | 0.000 (2) | −0.002 (2) | −0.001 (2) |
C6 | 0.093 (3) | 0.039 (2) | 0.056 (3) | −0.003 (2) | −0.028 (2) | −0.008 (2) |
C7 | 0.158 (6) | 0.051 (3) | 0.043 (3) | −0.015 (3) | −0.025 (3) | −0.009 (2) |
C8 | 0.135 (5) | 0.060 (3) | 0.049 (3) | −0.019 (3) | −0.028 (3) | 0.002 (3) |
C9 | 0.112 (4) | 0.049 (2) | 0.043 (2) | −0.017 (3) | −0.018 (2) | 0.010 (2) |
C11 | 0.044 (3) | 0.074 (3) | 0.103 (4) | −0.020 (3) | 0.009 (3) | −0.011 (3) |
C12 | 0.061 (3) | 0.045 (2) | 0.072 (3) | 0.006 (2) | 0.005 (3) | −0.002 (2) |
C25 | 0.043 (2) | 0.066 (2) | 0.039 (2) | 0.000 (3) | 0.002 (1) | −0.009 (3) |
C29 | 0.051 (2) | 0.043 (2) | 0.037 (2) | −0.009 (2) | 0.001 (2) | −0.003 (2) |
C30 | 0.039 (2) | 0.038 (2) | 0.042 (2) | −0.002 (2) | 0.001 (2) | 0.003 (2) |
C31 | 0.072 (3) | 0.045 (2) | 0.053 (2) | 0.003 (2) | 0.016 (2) | 0.012 (2) |
C32 | 0.074 (3) | 0.069 (3) | 0.066 (3) | −0.010 (3) | 0.035 (2) | 0.003 (3) |
C33 | 0.102 (4) | 0.068 (3) | 0.068 (3) | −0.007 (3) | 0.048 (3) | 0.003 (3) |
C34 | 0.081 (3) | 0.052 (3) | 0.070 (3) | −0.007 (2) | 0.031 (3) | −0.022 (2) |
C35 | 0.062 (3) | 0.066 (3) | 0.073 (3) | −0.005 (3) | −0.005 (3) | 0.022 (3) |
C36 | 0.082 (3) | 0.058 (3) | 0.085 (3) | −0.025 (3) | −0.049 (3) | 0.008 (3) |
C49 | 0.208 (8) | 0.46 (2) | 0.149 (6) | 0.20 (1) | −0.058 (6) | −0.156 (9) |
P2—N1 | 1.749 (4) | N3—C4 | 1.480 (5) |
P2—N3 | 1.758 (3) | N10—C25 | 1.485 (4) |
P2—N10 | 1.681 (2) | N26—C30 | 1.475 (5) |
P27—N10 | 1.699 (2) | N28—C29 | 1.495 (5) |
P27—N26 | 1.749 (3) | C4—C5 | 1.517 (5) |
P27—N28 | 1.763 (3) | C4—C9 | 1.544 (6) |
S13—O15 | 1.423 (3) | C4—H1 | 0.95 |
S13—O16 | 1.416 (3) | C5—C6 | 1.484 (6) |
S13—N1 | 1.588 (3) | C5—H2 | 0.95 |
S13—C11 | 1.857 (5) | C6—C7 | 1.518 (7) |
Cl50—C49 | 1.762 (9) | C6—H3 | 0.95 |
Cl51—C49 | 1.67 (2) | C6—H4 | 0.95 |
Cl52—C49 | 1.64 (1) | C7—C8 | 1.495 (6) |
Cl53—C49 | 1.51 (1) | C7—H5 | 0.95 |
Cl54—C49 | 1.57 (2) | C7—H6 | 0.95 |
S14—O17 | 1.399 (4) | C8—C9 | 1.518 (7) |
S14—O18 | 1.399 (4) | C8—H7 | 0.95 |
S14—N3 | 1.632 (3) | C8—H8 | 0.95 |
S14—C12 | 1.837 (5) | C9—H9 | 0.95 |
S37—O39 | 1.411 (3) | C9—H10 | 0.95 |
S37—O40 | 1.420 (3) | C25—H11 | 0.95 |
S37—N26 | 1.613 (4) | C25—H12 | 0.95 |
S37—C35 | 1.796 (6) | C25—H13 | 0.95 |
S38—O41 | 1.418 (3) | C29—C30 | 1.511 (5) |
S38—O42 | 1.399 (3) | C29—C34 | 1.514 (7) |
S38—N28 | 1.601 (3) | C29—H14 | 0.95 |
S38—C36 | 1.856 (5) | C30—C31 | 1.518 (6) |
F19—C11 | 1.309 (7) | C30—H15 | 0.95 |
F20—C11 | 1.298 (6) | C31—C32 | 1.512 (7) |
F21—C11 | 1.278 (6) | C31—H16 | 0.95 |
F22—C12 | 1.293 (6) | C31—H17 | 0.95 |
F23—C12 | 1.247 (6) | C32—C33 | 1.523 (7) |
F24—C12 | 1.301 (6) | C32—H18 | 0.95 |
F43—C35 | 1.324 (6) | C32—H19 | 0.95 |
F44—C35 | 1.267 (6) | C33—C34 | 1.548 (7) |
F45—C35 | 1.329 (6) | C33—H20 | 0.95 |
F46—C36 | 1.313 (6) | C33—H21 | 0.95 |
F47—C36 | 1.310 (7) | C34—H22 | 0.95 |
F48—C36 | 1.288 (6) | C34—H23 | 0.95 |
N1—C5 | 1.528 (5) | ||
F20···O39i | 2.931 (5) | ||
N1—P2—N3 | 87.3 (1) | C4—C9—H9 | 109.9 |
N1—P2—N10 | 105.9 (2) | C4—C9—H10 | 109.9 |
N3—P2—N10 | 103.3 (2) | C8—C9—H9 | 109.9 |
N10—P27—N26 | 106.9 (2) | C8—C9—H10 | 109.9 |
N10—P27—N28 | 103.6 (2) | H9—C9—H10 | 109.5 |
N26—P27—N28 | 86.4 (1) | S13—C11—F19 | 110.8 (4) |
P2—N10—P27 | 124.0 (1) | S13—C11—F20 | 108.5 (4) |
O15—S13—O16 | 122.6 (2) | S13—C11—F21 | 111.6 (4) |
O15—S13—N1 | 111.9 (2) | F19—C11—F20 | 105.8 (5) |
O15—S13—C11 | 106.7 (2) | F19—C11—F21 | 107.4 (5) |
O16—S13—N1 | 106.8 (2) | F20—C11—F21 | 112.7 (5) |
O16—S13—C11 | 103.2 (3) | S14—C12—F22 | 111.1 (4) |
N1—S13—C11 | 103.6 (2) | S14—C12—F23 | 111.7 (4) |
O17—S14—O18 | 122.0 (2) | S14—C12—F24 | 109.1 (4) |
O17—S14—N3 | 111.8 (2) | F22—C12—F23 | 107.8 (5) |
O17—S14—C12 | 104.4 (2) | F22—C12—F24 | 107.8 (5) |
O18—S14—N3 | 107.5 (2) | F23—C12—F24 | 109.3 (5) |
O18—S14—C12 | 104.9 (2) | N10—C25—H11 | 109.5 |
N3—S14—C12 | 104.8 (2) | N10—C25—H12 | 109.5 |
O39—S37—O40 | 122.6 (2) | N10—C25—H13 | 109.5 |
O39—S37—N26 | 107.6 (2) | H11—C25—H12 | 109.5 |
O39—S37—C35 | 103.5 (2) | H11—C25—H13 | 109.5 |
O40—S37—N26 | 111.5 (2) | H12—C25—H13 | 109.5 |
O40—S37—C35 | 105.4 (2) | N28—C29—C30 | 104.0 (3) |
N26—S37—C35 | 104.4 (2) | N28—C29—C34 | 117.7 (4) |
O41—S38—O42 | 122.8 (2) | N28—C29—H14 | 108.5 |
O41—S38—N28 | 106.7 (2) | C30—C29—C34 | 109.2 (4) |
O41—S38—C36 | 104.3 (2) | C30—C29—H14 | 108.5 |
O42—S38—N28 | 112.3 (2) | C34—C29—H14 | 108.5 |
O42—S38—C36 | 103.9 (2) | N26—C30—C29 | 103.8 (3) |
N28—S38—C36 | 105.2 (2) | N26—C30—C31 | 120.3 (3) |
S13—N1—P2 | 118.9 (2) | N26—C30—H15 | 107.3 |
S13—N1—C5 | 126.5 (3) | C29—C30—C31 | 110.3 (3) |
P2—N1—C5 | 114.6 (2) | C29—C30—H15 | 107.3 |
S14—N3—P2 | 115.1 (2) | C31—C30—H15 | 107.3 |
S14—N3—C4 | 121.4 (3) | C30—C31—C32 | 106.2 (4) |
P2—N3—C4 | 115.9 (2) | C30—C31—H16 | 110.3 |
P2—N3—H1 | 112.7 | C30—C31—H17 | 110.3 |
P2—N10—C25 | 123.5 (2) | C32—C31—H16 | 110.3 |
P27—N10—C25 | 112.5 (2) | C32—C31—H17 | 110.3 |
S37—N26—P27 | 116.3 (2) | H16—C31—H17 | 109.5 |
S37—N26—C30 | 128.6 (3) | C31—C32—C33 | 114.9 (5) |
S37—N26—H15 | 130.7 | C31—C32—H18 | 108.1 |
P27—N26—C30 | 115.1 (2) | C31—C32—H19 | 108.1 |
S38—N28—P27 | 115.4 (2) | C33—C32—H18 | 108.1 |
S38—N28—C29 | 122.9 (3) | C33—C32—H19 | 108.1 |
P27—N28—C29 | 116.2 (2) | H18—C32—H19 | 109.5 |
N3—C4—C5 | 105.9 (3) | C32—C33—C34 | 110.3 (4) |
N3—C4—C9 | 116.1 (3) | C32—C33—H20 | 109.3 |
N3—C4—H1 | 108.8 | C32—C33—H21 | 109.3 |
C5—C4—C9 | 108.3 (4) | C34—C33—H20 | 109.3 |
C5—C4—H1 | 108.8 | C34—C33—H21 | 109.3 |
C9—C4—H1 | 108.8 | H20—C33—H21 | 109.5 |
N1—C5—C4 | 101.7 (3) | C29—C34—C33 | 108.9 (4) |
N1—C5—C6 | 120.3 (3) | C29—C34—H22 | 109.6 |
N1—C5—H2 | 108.1 | C29—C34—H23 | 109.6 |
C4—C5—C6 | 110.1 (4) | C33—C34—H22 | 109.6 |
C4—C5—H2 | 108.1 | C33—C34—H23 | 109.6 |
C6—C5—H2 | 108.1 | H22—C34—H23 | 109.5 |
C5—C6—C7 | 108.6 (4) | S37—C35—F43 | 109.9 (4) |
C5—C6—H3 | 109.7 | S37—C35—F44 | 114.1 (4) |
C5—C6—H4 | 109.7 | S37—C35—F45 | 110.7 (4) |
C7—C6—H3 | 109.7 | F43—C35—F44 | 109.2 (5) |
C7—C6—H4 | 109.7 | F43—C35—F45 | 106.6 (5) |
H2—C6—H3 | 96.4 | F44—C35—F45 | 106.1 (5) |
H2—C6—H4 | 136.5 | S38—C36—F46 | 110.5 (4) |
H3—C6—H4 | 109.5 | S38—C36—F47 | 109.8 (4) |
C6—C7—C8 | 114.6 (5) | S38—C36—F48 | 110.4 (4) |
C6—C7—H5 | 108.2 | F46—C36—F47 | 109.8 (5) |
C6—C7—H6 | 108.2 | F46—C36—F48 | 108.3 (5) |
C6—C7—H8 | 140.2 | F47—C36—F48 | 107.9 (5) |
C8—C7—H5 | 108.2 | Cl50—C49—Cl51 | 105 (1) |
C8—C7—H6 | 108.2 | Cl50—C49—Cl52 | 117.5 (6) |
H5—C7—H6 | 109.5 | Cl50—C49—Cl53 | 121.5 (6) |
C7—C8—C9 | 116.7 (5) | Cl50—C49—Cl54 | 104.6 (6) |
C7—C8—H7 | 107.6 | Cl51—C49—Cl52 | 98.1 (8) |
C7—C8—H8 | 107.6 | Cl51—C49—Cl53 | 78.0 (7) |
C9—C8—H7 | 107.6 | Cl51—C49—Cl54 | 105.9 (6) |
C9—C8—H8 | 107.6 | Cl52—C49—Cl53 | 119.8 (7) |
H7—C8—H8 | 109.5 | Cl52—C49—Cl54 | 124 (1) |
C4—C9—C8 | 107.6 (4) | Cl53—C49—Cl54 | 29.4 (5) |
Symmetry code: (i) x+1, y, z. |
Experimental details
(IIIa) | (IIIb) | (IV) | |
Crystal data | |||
Chemical formula | C12H20F6N3O4PS2 | C10H16F6N3O4PS2 | C17H23F12N5O8P2S4·0.98(CHCl3) |
Mr | 479.39 | 451.34 | 960.65 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 | Monoclinic, P21 |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 8.657 (2), 10.352 (2), 12.859 (3) | 8.972 (2), 9.116 (6), 12.990 (7) | 8.812 (4), 13.897 (3), 14.728 (6) |
α, β, γ (°) | 104.81 (1), 93.08 (2), 111.21 (2) | 97.40 (4), 104.03 (4), 60.58 (4) | 90, 90.21 (3), 90 |
V (Å3) | 1024.9 (5) | 897.8 (9) | 1803 (1) |
Z | 2 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.41 | 0.47 | 0.68 |
Crystal size (mm) | 0.20 × 0.20 × 0.15 | 0.25 × 0.18 × 0.18 | 0.22 × 0.20 × 0.15 |
Data collection | |||
Diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed reflections | 6193, 5947, 3678 [I > 3σ(I)] | 5444, 5227, 3076 [I > 3σ(I)] | 5666, 5519, 4855 (I > 0) |
Rint | 0.025 | 0.022 | 0.031 |
(sin θ/λ)max (Å−1) | 0.703 | 0.703 | 0.722 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.063, 1.95 | 0.049, 0.070, 1.91 | 0.086, 0.051, 1.88 |
No. of reflections | 3678 | 3076 | 4855 |
No. of parameters | 253 | 235 | 486 |
H-atom treatment | H-atom parameters not refined | H-atom parameters not refined | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.43, −0.34 | 0.53, −0.39 | 0.46, −0.61 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, TEXSAN (Molecular Structure Corporation, 1992-1997), SIR92 (Altomare et al., 1993), TEXSAN, ORTEPII (Johnson, 1976).
P2—N1 | 1.783 (2) | P2—N10 | 1.637 (2) |
P2—N3 | 1.792 (2) | ||
N1—P2—N3 | 85.47 (7) | N3—P2—N10 | 107.71 (8) |
N1—P2—N10 | 101.42 (8) |
P2—N1 | 1.791 (2) | P2—N10 | 1.642 (2) |
P2—N3 | 1.771 (2) | ||
N1—P2—N3 | 86.05 (8) | N3—P2—N10 | 100.80 (8) |
N1—P2—N10 | 107.3 (1) |
P2—N1 | 1.749 (4) | P27—N10 | 1.699 (2) |
P2—N3 | 1.758 (3) | P27—N26 | 1.749 (3) |
P2—N10 | 1.681 (2) | P27—N28 | 1.763 (3) |
N1—P2—N3 | 87.3 (1) | N10—P27—N28 | 103.6 (2) |
N1—P2—N10 | 105.9 (2) | N26—P27—N28 | 86.4 (1) |
N3—P2—N10 | 103.3 (2) | P2—N10—P27 | 124.0 (1) |
N10—P27—N26 | 106.9 (2) |
(IIIa) | (IIIb) | (IV) | |
S distances from ring planes | |||
S13 | -0.298 (1) | 0.387 (1) | 0.667 (1) |
S14 | -0.321 (1) | 0.553 (1) | 0.460 (1) |
S37 | 0.774 (1) | ||
S38 | 0.373 (1) | ||
Bonded torsion angles | |||
N10-P2-N1-S13 | 94.9 (1) | -89.8 (1) | -94.6 (2) |
N10-P2-N3-S14 | -80.5 (1) | 99.0 (1) | 99.2 (2) |
N10-P27-N26-S37 | -98.1 (2) | ||
N10-P27-N28-S38 | 94.9 (2) | ||
Non-bonded torsion angles | |||
S13-N1···N3-S14 | 51.5 (5) | 30.9 (5) | 5.4 (9) |
S13-N1···N26-S37 | -43.5 (2) | ||
S37-N26···N28-S38 | -1.9 (9) | ||
S14-N3···N28-S38 | 43.8 (2) | ||
N distances from surrounding planes | |||
N1···(P2/C5/S13) | 0.260 (1) | 0.080 (2) | 0.019 (4) |
N3···(P2/C4/S14) | 0.132 (1) | 0.246 (2) | 0.258 (4) |
N26···(P27/C30/S37) | 0.004 (3) | ||
N28···(P27/C29/S38) | 0.220 (3) | ||
N-P distances | |||
P2-N1 | 1.783 (2) | 1.791 (2) | 1.749 (4) |
P2-N3 | 1.792 (2) | 1.771 (2) | 1.758 (3) |
P2-N10 | 1.637 (2) | 1.642 (2) | 1.681 (2) |
P27-N26 | 1.749 (3) | ||
P27-N28 | 1.763 (3) | ||
P27-N10 | 1.699 (2) |
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Phosphorus(III) ligands of the type PR3, where R is, for example, an alkyl, alkoxy or aryl group, are ubiquitous in homogeneous catalysis (Collman et al., 1987; Levason, 1990; McCauliffe, 1987; Pignolet, 1983). While certain R groups can impart significant π-acceptor character to these ligands, the number of ligands that approach the π-acceptor ability of CO is rather small (Brookhart et al., 1992; Moloy & Petersen 1995; Phillips et al., 1988; Schnabel & Roddick, 1993). This may change rapidly, however, because recent publications (Gimbert et al., 1999; Jolly et al., 1990; Kundig et al., 1994; van Leeuwen & Roobeck, 1983, 1981) have shown that certain transition-metal-catalyzed transformations are considerably more successful when less electron-rich phosphorus ligands are used. In contrast with the large number of phosphines, the phosphinites (Jacobsen et al., 1999), phosphites (Hilgraf & Pfalz, 1999), diazaphospholes (Brunel et al., 1998) and, to a lesser degree, phosphoramidites (Feringa, 2000), that have frequently been employed as ligands in asymmetric catalysis, and electron-deficient mono- and bidentate tris(amino)phosphine derivatives, have rarely been used, although phosphoramides have acted as ligands (Hersh et al., 1996) and have served as Lewis bases (Denmark et al., 1994) in various asymmetric procedures.
The trifluoromethanesulfonylamino group is strongly electron-withdrawing and, therefore, should substantially affect phosphorus σ-donation and π-acidity. With this in mind, two new types of chiral phosphorus ligands that could be expected to approach the π-acceptor ability of CO have been prepared from (1R,2R)-N,N'-bis(trifluoromethanesulfonyl)-1,2-cyclohexanediamine, (I) (Denmark et al., 1998; Takahashi et al., 1992), namely [(4R,5R)-1,3-bis(trifluoromethanesulfonyl)perhydro-1,3,2-benzodiazaphosphol-2- yl)diethylamine, (IIIa) and bis[(4R,5R)-1,3-bis(trifluoromethanesulfonyl)perhydro-1,3,2-benzodiazaphosphol- 2-yl]methylamine chloroform solvate, (IV). \sch
X-ray diffraction analysis of these new compounds (Figs. 1 and 2) indicates some interesting differences. The dimethylamine analogue (IIIb) of (IIIa) has also been prepared, and displays bond distances and angles very close to those of (IIIa) (Tables 1 and 2). A minor difference between the two is the conformation of the six- and five-membered rings, which are inverted. In the potentially monodentate (IIIa), the trifluoromethyl groups are trans and perpendicular to the mean plane defined by the five-membered ring, whereas in the potentially bidentate (IV), the trifluoromethyl groups are cis. This is especially clear when considering the distances of the S atoms from the least-squares weighted plane through each ring (Table 4), where each pair being the same sign means that both atoms are on the same side with respect to the plane. In addition, the first set of torsion angles in Table 4 indicates the orientation of the trifluoromethyl groups with respect to the P—Namine bond (not the plane through the ring). Finally, the reciprocal orientation of the trifluoromethyl groups might be defined by the second set of torsion angles in Table 4, between directions involving non-bonded atoms.
Despite the strong sp2 character of the N atoms of the five-membered ring, the bonds about these atoms are not all coplanar, as indicated by the values of the distances of the N atoms from the planes defined by the atoms surrounding them (Table 4).
In both (IIIa) and (IV), the internal N—P—N angle is approximately 86°. The N—P bond distances for all three compiunds are compared in Table 4, showing that significant differences are observed between the distances involving Nring and those involving Namine. The averages for P—Nring are 1.784 (5) Å for (IIIa) and (IIIb), and 1.755 (3) Å for (IV), while the averages for P—Namine are 1.639 (3) Å for (IIIa) and (IIIb), and 1.690 (9) Å for (IV). [For a discussion of the nature of the P—N bond, see Kremer et al. (1996)]. The observed difference for the P—N10 distance suggests that there is a reduced electron density at P in the bis(phosphine), and thus greater π-accepting ability. This apparent electronic difference may contribute to the ability of the chelating phosphine to give rise to metal complexes. For example, (IV), but not (IIIa) or (IIIb), has been shown to react with the hexacarbonylphenylacetylene dicobalt complex to give, by thermal substitution of two additional carbonyl groups, the resulting bis(phosphine) dicobalt tetracarbonylphenylacetylene complex (D. Konya, unpublished results).