Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112036396/fa3282sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112036396/fa3282Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112036396/fa3282IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112036396/fa3282IIIsup4.hkl |
CCDC references: 906577; 906578; 906579
For related literature, see: Allen (2002); Döring et al. (2012); Dehghanpour et al. (2008, 2010); Gholivand et al. (2005, 2007); Gholivand, Alizadehgan, Arshadi & Firooz (2006); Gholivand, Mojahed, Salehi & Alizadehgan (2006); Gholivand, Shariatinia & Pourayoubi (2006); Gubina et al. (2000); Marsh (2009); Pourayoubi et al. (2011); Rebrova et al. (1992); Toghraee et al. (2011).
Three starting materials with the general formula XC(O)NHP(O)Cl2 (X = CClF2, 3-F-C6H4 and 3,5-F2-C6H3) were synthesized from the reaction between phosphorus pentachloride (16.7 mmol) and the corresponding XC(O)NH2 amide (16.7 mmol) in dry CCl4 at 358 K (about 3 h) followed by treatment with formic acid (16.7 mmol) at ice-bath temperature.
For the preparation of (I), a solution of dibenzylamine (4 mmol) in dry CHCl3 (5 ml) was added to a solution of CClF2C(O)NHP(O)Cl2 (1 mmol) in the same solvent (10 ml) at 273 K. After stirring for 5 h, the solvent was removed and the product was washed with distilled water. Single crystals were obtained from a solution of (I) in CH3OH–CHCl3 [ratio? volume?] by slow evaporation at 273 K.
For the preparation of (II), a solution of dibenzylamine (4 mmol) in dry CHCl3 (5 ml) was added to a solution of 3-F-C6H4C(O)NHP(O)Cl2 (1 mmol) in the same solvent (20 ml) and the resulting solution stirred at 273 K for 4 h. The solvent was the evaporated in vacuo and the product washed with distilled water. Colorless single crystals were obtained from a CH3CN solution by slow evaporation at room temperature.
For the preparation of (III), a solution of dibenzylamine (4 mmol) in dry CHCl3 was added to a solution of 3,5-F2-C6H3C(O)NHP(O)Cl2 (1 mmol) in the same solvent (20 ml). After stirring at 273 K for 4 h, the solvent was evaporated in vacuo and the product was washed with distilled water. Colorless single crystals were obtained from a CH3CN solution by slow evaporation at room temperature.
For compounds (I), (II) and (III), atom H1N was located in a difference map and refined isotropically. All of the remaining H atoms were placed at calculated positions and refined using a riding model, with C—H bond lengths of 0.93 (CH) or 0.97 Å (CH2). The isotropic displacement parameters for these H atoms were set at 1.2 times Ueq of their respective parent atoms. The largest difference peak and hole for (II) were 1.117 (3.01 Å from H15A) and -0.322 e Å-3 , with the positive peak in a small void of 57 Å3. This and a second difference peak in the void appeared to represent occupation by a diffuse source of electron density. Platon SQUEEZE estimated a total of 4 electrons per cell in the void, and no further action was taken. The results reported for this structure have not had SQUEEZE applied.
Data collection: APEX2 (Bruker, 2007) for (I); CrysAlis PRO (Oxford Diffraction, 2010) for (II), (III). Cell refinement: SAINT (Bruker, 2007) for (I); CrysAlis PRO (Oxford Diffraction, 2010) for (II), (III). Data reduction: SAINT (Bruker, 2007) for (I); CrysAlis RED (Oxford Diffraction, 2010) for (II), (III). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: XPW (Siemens, 1996) and Mercury (Macrae et al., 2008) for (I); SHELXTL (Sheldrick, 2008) for (II), (III). Software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and enCIFer (Allen et al., 2004) for (I); SHELXTL (Sheldrick, 2008) for (II), (III).
C30H29ClF2N3O2P | F(000) = 1184 |
Mr = 567.98 | Dx = 1.317 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 9995 reflections |
a = 10.8298 (3) Å | θ = 2.6–29.0° |
b = 9.9164 (3) Å | µ = 0.23 mm−1 |
c = 26.6740 (8) Å | T = 296 K |
β = 91.539 (1)° | Irregular, colorless |
V = 2863.56 (15) Å3 | 0.56 × 0.51 × 0.48 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 6905 independent reflections |
Radiation source: fine-focus sealed tube | 5873 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ϕ and ω scans | θmax = 28.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −14→14 |
Tmin = 0.694, Tmax = 0.746 | k = −13→13 |
31854 measured reflections | l = −35→22 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0663P)2 + 1.1866P] where P = (Fo2 + 2Fc2)/3 |
6905 reflections | (Δ/σ)max = 0.001 |
356 parameters | Δρmax = 0.78 e Å−3 |
0 restraints | Δρmin = −0.68 e Å−3 |
C30H29ClF2N3O2P | V = 2863.56 (15) Å3 |
Mr = 567.98 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.8298 (3) Å | µ = 0.23 mm−1 |
b = 9.9164 (3) Å | T = 296 K |
c = 26.6740 (8) Å | 0.56 × 0.51 × 0.48 mm |
β = 91.539 (1)° |
Bruker APEXII CCD diffractometer | 6905 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 5873 reflections with I > 2σ(I) |
Tmin = 0.694, Tmax = 0.746 | Rint = 0.019 |
31854 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.134 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.78 e Å−3 |
6905 reflections | Δρmin = −0.68 e Å−3 |
356 parameters |
Experimental. IR (KBr, ν, cm-1): 3064, 3036, 2901, 2868, 2758, 1736, 1602, 1586, 1494, 1454, 1372, 1360, 1347, 1301, 1285, 1213, 1185, 1173, 1137, 1124, 1103, 1068, 1026, 977, 954, 944, 921, 905, 858, 833, 820, 808, 747, 725, 699, 671, 622, 609, 599, 581, 543, 520, 486, 465, 437, 416. |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(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 | ||
Cl1 | 0.34696 (6) | 0.83086 (7) | 1.01897 (2) | 0.0761 (2) | |
P1 | −0.01521 (3) | 0.88010 (4) | 0.925175 (13) | 0.03216 (11) | |
O1 | 0.25772 (12) | 0.85020 (15) | 0.89093 (5) | 0.0507 (3) | |
F2 | 0.33710 (12) | 1.06452 (13) | 0.98342 (5) | 0.0678 (3) | |
O2 | −0.10455 (10) | 0.92420 (13) | 0.96253 (4) | 0.0423 (3) | |
F3 | 0.45045 (11) | 0.9261 (2) | 0.94339 (6) | 0.0911 (5) | |
C3 | 0.21381 (19) | 0.5602 (2) | 0.94220 (7) | 0.0526 (4) | |
H3 | 0.1984 | 0.6344 | 0.9624 | 0.063* | |
N2 | −0.01394 (12) | 0.71619 (14) | 0.91926 (5) | 0.0366 (3) | |
N3 | −0.02763 (13) | 0.94120 (13) | 0.86824 (5) | 0.0359 (3) | |
C5 | 0.3281 (2) | 0.3594 (3) | 0.92671 (13) | 0.0817 (8) | |
H5 | 0.3909 | 0.2994 | 0.9357 | 0.098* | |
C4 | 0.3070 (2) | 0.4708 (3) | 0.95599 (10) | 0.0676 (6) | |
H4 | 0.3550 | 0.4861 | 0.9849 | 0.081* | |
C2 | 0.14316 (17) | 0.54042 (17) | 0.89859 (7) | 0.0435 (4) | |
C1 | 0.04933 (16) | 0.64269 (17) | 0.87983 (6) | 0.0406 (3) | |
H1A | 0.0907 | 0.7074 | 0.8588 | 0.049* | |
H1B | −0.0122 | 0.5966 | 0.8590 | 0.049* | |
C15 | −0.11343 (17) | 0.87955 (18) | 0.83075 (6) | 0.0431 (4) | |
H15A | −0.1387 | 0.7921 | 0.8432 | 0.052* | |
H15B | −0.0690 | 0.8644 | 0.8002 | 0.052* | |
C16 | −0.22776 (18) | 0.96065 (18) | 0.81805 (6) | 0.0464 (4) | |
C17 | −0.3107 (2) | 0.9971 (2) | 0.85393 (9) | 0.0591 (5) | |
H17 | −0.2945 | 0.9747 | 0.8873 | 0.071* | |
C18 | −0.4180 (2) | 1.0668 (3) | 0.84101 (13) | 0.0811 (8) | |
H18 | −0.4734 | 1.0899 | 0.8656 | 0.097* | |
C19 | −0.4422 (3) | 1.1013 (3) | 0.79216 (17) | 0.0992 (11) | |
H19 | −0.5138 | 1.1486 | 0.7835 | 0.119* | |
C12 | −0.4023 (3) | 0.4794 (4) | 0.86672 (11) | 0.0975 (11) | |
H12 | −0.4691 | 0.4473 | 0.8476 | 0.117* | |
C11 | −0.2996 (3) | 0.4016 (3) | 0.87355 (12) | 0.0941 (10) | |
H11 | −0.2968 | 0.3163 | 0.8591 | 0.113* | |
C10 | −0.1990 (2) | 0.4484 (2) | 0.90186 (10) | 0.0679 (6) | |
H10 | −0.1299 | 0.3939 | 0.9068 | 0.081* | |
C9 | −0.20186 (17) | 0.57579 (19) | 0.92262 (7) | 0.0464 (4) | |
C14 | −0.3073 (2) | 0.6534 (3) | 0.91567 (9) | 0.0618 (5) | |
H14 | −0.3108 | 0.7391 | 0.9298 | 0.074* | |
C13 | −0.4071 (2) | 0.6045 (4) | 0.88796 (11) | 0.0859 (9) | |
H13 | −0.4778 | 0.6570 | 0.8837 | 0.103* | |
C8 | −0.09195 (17) | 0.63158 (19) | 0.95136 (6) | 0.0450 (4) | |
H8A | −0.1202 | 0.6851 | 0.9792 | 0.054* | |
H8B | −0.0429 | 0.5576 | 0.9650 | 0.054* | |
C22 | 0.00184 (18) | 1.08433 (17) | 0.85889 (6) | 0.0428 (4) | |
H22A | 0.0603 | 1.1155 | 0.8845 | 0.051* | |
H22B | −0.0728 | 1.1376 | 0.8615 | 0.051* | |
C23 | 0.05588 (17) | 1.10691 (18) | 0.80788 (6) | 0.0450 (4) | |
C24 | 0.0088 (2) | 1.2072 (2) | 0.77678 (8) | 0.0567 (5) | |
H24 | −0.0581 | 1.2583 | 0.7869 | 0.068* | |
C25 | 0.0605 (3) | 1.2321 (3) | 0.73065 (9) | 0.0738 (7) | |
H25 | 0.0287 | 1.3004 | 0.7102 | 0.089* | |
C26 | 0.1577 (3) | 1.1569 (3) | 0.71521 (9) | 0.0805 (8) | |
H26 | 0.1921 | 1.1736 | 0.6842 | 0.097* | |
C27 | 0.2046 (3) | 1.0564 (3) | 0.74549 (9) | 0.0818 (8) | |
H27 | 0.2705 | 1.0045 | 0.7349 | 0.098* | |
C28 | 0.1544 (2) | 1.0320 (3) | 0.79184 (8) | 0.0635 (6) | |
H28 | 0.1875 | 0.9644 | 0.8123 | 0.076* | |
C20 | −0.3615 (4) | 1.0664 (3) | 0.75625 (13) | 0.1020 (12) | |
H20 | −0.3786 | 1.0897 | 0.7230 | 0.122* | |
C21 | −0.2532 (3) | 0.9960 (3) | 0.76855 (8) | 0.0723 (7) | |
H21 | −0.1985 | 0.9729 | 0.7437 | 0.087* | |
N1 | 0.12407 (12) | 0.93551 (15) | 0.94785 (5) | 0.0365 (3) | |
C29 | 0.23604 (15) | 0.90400 (17) | 0.93035 (6) | 0.0388 (3) | |
C30 | 0.34493 (16) | 0.9375 (2) | 0.96680 (7) | 0.0486 (4) | |
C6 | 0.2570 (3) | 0.3369 (2) | 0.88443 (13) | 0.0815 (8) | |
H6 | 0.2709 | 0.2607 | 0.8650 | 0.098* | |
C7 | 0.1647 (2) | 0.4263 (2) | 0.87036 (9) | 0.0608 (5) | |
H7 | 0.1165 | 0.4096 | 0.8416 | 0.073* | |
H1N | 0.1250 (19) | 0.973 (2) | 0.9743 (8) | 0.045 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0827 (4) | 0.0806 (4) | 0.0631 (3) | −0.0111 (3) | −0.0368 (3) | 0.0119 (3) |
P1 | 0.03187 (19) | 0.0408 (2) | 0.02364 (17) | −0.00448 (15) | −0.00330 (13) | −0.00506 (14) |
O1 | 0.0456 (7) | 0.0691 (9) | 0.0377 (6) | 0.0010 (6) | 0.0033 (5) | −0.0091 (6) |
F2 | 0.0607 (7) | 0.0626 (8) | 0.0790 (8) | −0.0172 (6) | −0.0199 (6) | −0.0090 (6) |
O2 | 0.0358 (6) | 0.0590 (7) | 0.0321 (5) | −0.0039 (5) | 0.0005 (4) | −0.0121 (5) |
F3 | 0.0335 (6) | 0.1605 (16) | 0.0793 (9) | −0.0125 (8) | 0.0032 (6) | −0.0236 (10) |
C3 | 0.0542 (11) | 0.0543 (11) | 0.0492 (10) | −0.0010 (8) | −0.0022 (8) | 0.0084 (8) |
N2 | 0.0418 (7) | 0.0402 (7) | 0.0278 (6) | −0.0057 (5) | 0.0005 (5) | −0.0005 (5) |
N3 | 0.0429 (7) | 0.0371 (7) | 0.0271 (6) | −0.0051 (5) | −0.0071 (5) | −0.0019 (5) |
C5 | 0.0554 (13) | 0.0619 (14) | 0.129 (2) | 0.0098 (11) | 0.0169 (15) | 0.0348 (16) |
C4 | 0.0511 (12) | 0.0753 (15) | 0.0761 (15) | −0.0016 (10) | −0.0018 (10) | 0.0312 (12) |
C2 | 0.0454 (9) | 0.0393 (8) | 0.0459 (9) | −0.0060 (7) | 0.0042 (7) | 0.0017 (7) |
C1 | 0.0495 (9) | 0.0419 (8) | 0.0302 (7) | −0.0039 (7) | −0.0020 (6) | −0.0049 (6) |
C15 | 0.0546 (10) | 0.0459 (9) | 0.0282 (7) | −0.0052 (7) | −0.0117 (6) | −0.0049 (6) |
C16 | 0.0542 (10) | 0.0432 (9) | 0.0406 (8) | −0.0112 (8) | −0.0184 (7) | 0.0063 (7) |
C17 | 0.0599 (12) | 0.0556 (11) | 0.0613 (12) | −0.0002 (9) | −0.0104 (9) | 0.0066 (9) |
C18 | 0.0569 (13) | 0.0632 (14) | 0.122 (2) | 0.0019 (11) | −0.0191 (14) | 0.0033 (15) |
C19 | 0.0776 (19) | 0.0694 (17) | 0.147 (3) | −0.0003 (14) | −0.059 (2) | 0.0147 (19) |
C12 | 0.0754 (19) | 0.140 (3) | 0.0764 (17) | −0.058 (2) | −0.0095 (14) | −0.0003 (18) |
C11 | 0.102 (2) | 0.087 (2) | 0.094 (2) | −0.0529 (18) | 0.0100 (17) | −0.0222 (16) |
C10 | 0.0686 (14) | 0.0563 (12) | 0.0788 (15) | −0.0201 (10) | 0.0070 (11) | −0.0052 (11) |
C9 | 0.0500 (10) | 0.0484 (9) | 0.0408 (8) | −0.0145 (8) | 0.0015 (7) | 0.0089 (7) |
C14 | 0.0556 (12) | 0.0673 (13) | 0.0624 (12) | −0.0083 (10) | −0.0022 (9) | 0.0120 (10) |
C13 | 0.0547 (13) | 0.121 (3) | 0.0815 (18) | −0.0183 (15) | −0.0113 (12) | 0.0195 (17) |
C8 | 0.0509 (9) | 0.0496 (10) | 0.0345 (8) | −0.0097 (8) | −0.0010 (7) | 0.0089 (7) |
C22 | 0.0543 (10) | 0.0360 (8) | 0.0380 (8) | −0.0042 (7) | −0.0024 (7) | −0.0016 (6) |
C23 | 0.0512 (10) | 0.0451 (9) | 0.0384 (8) | −0.0095 (7) | −0.0054 (7) | 0.0040 (7) |
C24 | 0.0730 (13) | 0.0460 (10) | 0.0506 (10) | −0.0031 (9) | −0.0087 (9) | 0.0065 (8) |
C25 | 0.103 (2) | 0.0638 (14) | 0.0536 (12) | −0.0141 (13) | −0.0128 (12) | 0.0232 (11) |
C26 | 0.0878 (18) | 0.104 (2) | 0.0501 (12) | −0.0216 (16) | 0.0092 (12) | 0.0218 (13) |
C27 | 0.0684 (15) | 0.120 (2) | 0.0577 (13) | 0.0108 (15) | 0.0155 (11) | 0.0137 (14) |
C28 | 0.0617 (12) | 0.0823 (15) | 0.0467 (10) | 0.0117 (11) | 0.0044 (9) | 0.0156 (10) |
C20 | 0.120 (3) | 0.094 (2) | 0.089 (2) | −0.0125 (19) | −0.066 (2) | 0.0334 (17) |
C21 | 0.0889 (16) | 0.0790 (15) | 0.0471 (11) | −0.0152 (13) | −0.0307 (11) | 0.0169 (10) |
N1 | 0.0337 (6) | 0.0485 (8) | 0.0271 (6) | −0.0058 (5) | −0.0035 (5) | −0.0085 (5) |
C29 | 0.0350 (8) | 0.0483 (9) | 0.0330 (7) | −0.0056 (6) | −0.0024 (6) | 0.0012 (6) |
C30 | 0.0346 (8) | 0.0640 (12) | 0.0470 (9) | −0.0062 (8) | −0.0048 (7) | −0.0033 (8) |
C6 | 0.0720 (16) | 0.0443 (11) | 0.129 (2) | 0.0051 (11) | 0.0243 (17) | −0.0049 (14) |
C7 | 0.0618 (12) | 0.0457 (10) | 0.0753 (14) | −0.0061 (9) | 0.0092 (10) | −0.0103 (10) |
P1—N1 | 1.7011 (13) | C12—H12 | 0.9300 |
P1—N2 | 1.6331 (14) | C11—C10 | 1.388 (4) |
P1—N3 | 1.6373 (13) | C11—H11 | 0.9300 |
P1—O2 | 1.4739 (11) | C10—C9 | 1.380 (3) |
Cl1—C30 | 1.748 (2) | C10—H10 | 0.9300 |
O1—C29 | 1.208 (2) | C9—C14 | 1.385 (3) |
F2—C30 | 1.338 (2) | C9—C8 | 1.504 (2) |
F3—C30 | 1.322 (2) | C14—C13 | 1.381 (3) |
C3—C4 | 1.385 (3) | C14—H14 | 0.9300 |
C3—C2 | 1.389 (3) | C13—H13 | 0.9300 |
C3—H3 | 0.9300 | C8—H8A | 0.9700 |
N2—C1 | 1.465 (2) | C8—H8B | 0.9700 |
N2—C8 | 1.480 (2) | C22—C23 | 1.512 (2) |
N3—C22 | 1.477 (2) | C22—H22A | 0.9700 |
N3—C15 | 1.4788 (19) | C22—H22B | 0.9700 |
C5—C6 | 1.367 (4) | C23—C28 | 1.378 (3) |
C5—C4 | 1.375 (4) | C23—C24 | 1.383 (3) |
C5—H5 | 0.9300 | C24—C25 | 1.388 (3) |
C4—H4 | 0.9300 | C24—H24 | 0.9300 |
C2—C7 | 1.383 (3) | C25—C26 | 1.363 (4) |
C2—C1 | 1.511 (2) | C25—H25 | 0.9300 |
C1—H1A | 0.9700 | C26—C27 | 1.372 (4) |
C1—H1B | 0.9700 | C26—H26 | 0.9300 |
C15—C16 | 1.507 (3) | C27—C28 | 1.385 (3) |
C15—H15A | 0.9700 | C27—H27 | 0.9300 |
C15—H15B | 0.9700 | C28—H28 | 0.9300 |
C16—C17 | 1.378 (3) | C20—C21 | 1.396 (4) |
C16—C21 | 1.387 (2) | C20—H20 | 0.9300 |
C17—C18 | 1.387 (3) | C21—H21 | 0.9300 |
C17—H17 | 0.9300 | N1—C29 | 1.348 (2) |
C18—C19 | 1.366 (5) | N1—H1N | 0.80 (2) |
C18—H18 | 0.9300 | C29—C30 | 1.544 (2) |
C19—C20 | 1.359 (5) | C6—C7 | 1.381 (4) |
C19—H19 | 0.9300 | C6—H6 | 0.9300 |
C12—C11 | 1.362 (5) | C7—H7 | 0.9300 |
C12—C13 | 1.366 (5) | ||
O2—P1—N1 | 104.82 (7) | C13—C14—C9 | 120.5 (3) |
O2—P1—N2 | 111.59 (7) | C13—C14—H14 | 119.8 |
O2—P1—N3 | 118.57 (7) | C9—C14—H14 | 119.8 |
N1—P1—N2 | 110.25 (7) | C12—C13—C14 | 120.2 (3) |
N1—P1—N3 | 105.08 (7) | C12—C13—H13 | 119.9 |
N2—P1—N3 | 106.23 (7) | C14—C13—H13 | 119.9 |
C4—C3—C2 | 120.9 (2) | N2—C8—C9 | 111.72 (13) |
C4—C3—H3 | 119.6 | N2—C8—H8A | 109.3 |
C2—C3—H3 | 119.6 | C9—C8—H8A | 109.3 |
C1—N2—C8 | 114.75 (14) | N2—C8—H8B | 109.3 |
C1—N2—P1 | 124.74 (11) | C9—C8—H8B | 109.3 |
C8—N2—P1 | 120.13 (11) | H8A—C8—H8B | 107.9 |
C22—N3—C15 | 114.69 (13) | N3—C22—C23 | 112.63 (14) |
C15—N3—P1 | 120.57 (11) | N3—C22—H22A | 109.1 |
C22—N3—P1 | 119.96 (10) | C23—C22—H22A | 109.1 |
C6—C5—C4 | 120.1 (2) | N3—C22—H22B | 109.1 |
C6—C5—H5 | 120.0 | C23—C22—H22B | 109.1 |
C4—C5—H5 | 120.0 | H22A—C22—H22B | 107.8 |
C5—C4—C3 | 119.6 (2) | C28—C23—C24 | 118.53 (18) |
C5—C4—H4 | 120.2 | C28—C23—C22 | 121.41 (17) |
C3—C4—H4 | 120.2 | C24—C23—C22 | 120.04 (18) |
C7—C2—C3 | 118.32 (19) | C23—C24—C25 | 120.6 (2) |
C7—C2—C1 | 119.39 (17) | C23—C24—H24 | 119.7 |
C3—C2—C1 | 122.20 (16) | C25—C24—H24 | 119.7 |
N2—C1—C2 | 114.80 (13) | C26—C25—C24 | 120.3 (2) |
N2—C1—H1A | 108.6 | C26—C25—H25 | 119.9 |
C2—C1—H1A | 108.6 | C24—C25—H25 | 119.9 |
N2—C1—H1B | 108.6 | C25—C26—C27 | 119.8 (2) |
C2—C1—H1B | 108.6 | C25—C26—H26 | 120.1 |
H1A—C1—H1B | 107.5 | C27—C26—H26 | 120.1 |
N3—C15—C16 | 115.39 (14) | C26—C27—C28 | 120.3 (3) |
N3—C15—H15A | 108.4 | C26—C27—H27 | 119.9 |
C16—C15—H15A | 108.4 | C28—C27—H27 | 119.9 |
N3—C15—H15B | 108.4 | C23—C28—C27 | 120.6 (2) |
C16—C15—H15B | 108.4 | C23—C28—H28 | 119.7 |
H15A—C15—H15B | 107.5 | C27—C28—H28 | 119.7 |
C17—C16—C21 | 118.6 (2) | C19—C20—C21 | 120.9 (3) |
C17—C16—C15 | 122.06 (16) | C19—C20—H20 | 119.5 |
C21—C16—C15 | 119.3 (2) | C21—C20—H20 | 119.5 |
C16—C17—C18 | 121.0 (2) | C16—C21—C20 | 119.6 (3) |
C16—C17—H17 | 119.5 | C16—C21—H21 | 120.2 |
C18—C17—H17 | 119.5 | C20—C21—H21 | 120.2 |
C19—C18—C17 | 120.0 (3) | C29—N1—P1 | 126.83 (11) |
C19—C18—H18 | 120.0 | C29—N1—H1N | 115.1 (15) |
C17—C18—H18 | 120.0 | P1—N1—H1N | 117.1 (15) |
C20—C19—C18 | 119.8 (3) | O1—C29—N1 | 126.99 (15) |
C20—C19—H19 | 120.1 | O1—C29—C30 | 118.70 (15) |
C18—C19—H19 | 120.1 | N1—C29—C30 | 114.27 (14) |
C11—C12—C13 | 120.0 (3) | F3—C30—F2 | 107.49 (17) |
C11—C12—H12 | 120.0 | F3—C30—C29 | 109.84 (15) |
C13—C12—H12 | 120.0 | F2—C30—C29 | 110.93 (16) |
C12—C11—C10 | 120.6 (3) | F3—C30—Cl1 | 109.36 (15) |
C12—C11—H11 | 119.7 | F2—C30—Cl1 | 107.76 (13) |
C10—C11—H11 | 119.7 | C29—C30—Cl1 | 111.35 (13) |
C9—C10—C11 | 119.9 (3) | C5—C6—C7 | 120.5 (2) |
C9—C10—H10 | 120.0 | C5—C6—H6 | 119.8 |
C11—C10—H10 | 120.0 | C7—C6—H6 | 119.8 |
C10—C9—C14 | 118.8 (2) | C6—C7—C2 | 120.6 (2) |
C10—C9—C8 | 121.0 (2) | C6—C7—H7 | 119.7 |
C14—C9—C8 | 120.13 (19) | C2—C7—H7 | 119.7 |
O2—P1—N2—C1 | 169.65 (12) | C1—N2—C8—C9 | −67.4 (2) |
N3—P1—N2—C1 | 39.05 (15) | P1—N2—C8—C9 | 105.97 (16) |
N1—P1—N2—C1 | −74.29 (14) | C10—C9—C8—N2 | 95.6 (2) |
O2—P1—N2—C8 | −2.96 (14) | C14—C9—C8—N2 | −83.1 (2) |
N3—P1—N2—C8 | −133.56 (12) | C15—N3—C22—C23 | −57.0 (2) |
N1—P1—N2—C8 | 113.09 (12) | P1—N3—C22—C23 | 147.32 (13) |
O2—P1—N3—C22 | 69.94 (15) | N3—C22—C23—C28 | −51.2 (2) |
N2—P1—N3—C22 | −163.55 (13) | N3—C22—C23—C24 | 130.71 (18) |
N1—P1—N3—C22 | −46.70 (14) | C28—C23—C24—C25 | −0.5 (3) |
O2—P1—N3—C15 | −84.28 (14) | C22—C23—C24—C25 | 177.64 (19) |
N2—P1—N3—C15 | 42.23 (14) | C23—C24—C25—C26 | 0.7 (4) |
N1—P1—N3—C15 | 159.09 (13) | C24—C25—C26—C27 | −0.2 (4) |
C6—C5—C4—C3 | −0.4 (4) | C25—C26—C27—C28 | −0.6 (5) |
C2—C3—C4—C5 | −1.4 (3) | C24—C23—C28—C27 | −0.3 (4) |
C4—C3—C2—C7 | 2.7 (3) | C22—C23—C28—C27 | −178.4 (2) |
C4—C3—C2—C1 | −173.96 (18) | C26—C27—C28—C23 | 0.8 (4) |
C8—N2—C1—C2 | −64.23 (18) | C18—C19—C20—C21 | −0.4 (5) |
P1—N2—C1—C2 | 122.80 (14) | C17—C16—C21—C20 | −0.3 (3) |
C7—C2—C1—N2 | 149.48 (17) | C15—C16—C21—C20 | 177.4 (2) |
C3—C2—C1—N2 | −33.9 (2) | C19—C20—C21—C16 | 0.3 (4) |
C22—N3—C15—C16 | −48.0 (2) | O2—P1—N1—C29 | 170.32 (14) |
P1—N3—C15—C16 | 107.54 (15) | N2—P1—N1—C29 | 50.10 (16) |
N3—C15—C16—C17 | −58.8 (2) | N3—P1—N1—C29 | −63.97 (16) |
N3—C15—C16—C21 | 123.49 (19) | P1—N1—C29—O1 | 13.5 (3) |
C21—C16—C17—C18 | 0.5 (3) | P1—N1—C29—C30 | −164.11 (13) |
C15—C16—C17—C18 | −177.19 (19) | O1—C29—C30—F3 | 13.3 (3) |
C16—C17—C18—C19 | −0.6 (4) | N1—C29—C30—F3 | −168.88 (17) |
C17—C18—C19—C20 | 0.5 (4) | O1—C29—C30—F2 | 131.99 (18) |
C13—C12—C11—C10 | −0.2 (5) | N1—C29—C30—F2 | −50.2 (2) |
C12—C11—C10—C9 | −1.2 (4) | O1—C29—C30—Cl1 | −108.00 (17) |
C11—C10—C9—C14 | 1.6 (3) | N1—C29—C30—Cl1 | 69.82 (19) |
C11—C10—C9—C8 | −177.0 (2) | C4—C5—C6—C7 | 0.9 (4) |
C10—C9—C14—C13 | −0.7 (3) | C5—C6—C7—C2 | 0.4 (4) |
C8—C9—C14—C13 | 177.9 (2) | C3—C2—C7—C6 | −2.2 (3) |
C11—C12—C13—C14 | 1.1 (4) | C1—C2—C7—C6 | 174.6 (2) |
C9—C14—C13—C12 | −0.6 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.80 (2) | 1.98 (2) | 2.7788 (17) | 172 (2) |
Symmetry code: (i) −x, −y+2, −z+2. |
C35H33FN3O2P | Z = 2 |
Mr = 577.61 | F(000) = 608 |
Triclinic, P1 | Dx = 1.263 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.0173 (10) Å | Cell parameters from 6536 reflections |
b = 11.2362 (8) Å | θ = 3.3–32.3° |
c = 14.5992 (12) Å | µ = 0.13 mm−1 |
α = 99.351 (6)° | T = 173 K |
β = 109.960 (8)° | Chunk, colorless |
γ = 91.135 (7)° | 0.48 × 0.40 × 0.36 mm |
V = 1519.0 (2) Å3 |
Xcalibur, Eos, Gemini diffractometer | 9840 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 8118 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 16.1500 pixels mm-1 | θmax = 32.3°, θmin = 3.3° |
ω scans | h = −14→14 |
Absorption correction: multi-scan CrysAlis PRO, Oxford Diffraction, 2010. | k = −15→16 |
Tmin = 0.943, Tmax = 1.000 | l = −21→21 |
17423 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.143 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0785P)2 + 0.4137P] where P = (Fo2 + 2Fc2)/3 |
9840 reflections | (Δ/σ)max = 0.001 |
383 parameters | Δρmax = 1.12 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C35H33FN3O2P | γ = 91.135 (7)° |
Mr = 577.61 | V = 1519.0 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.0173 (10) Å | Mo Kα radiation |
b = 11.2362 (8) Å | µ = 0.13 mm−1 |
c = 14.5992 (12) Å | T = 173 K |
α = 99.351 (6)° | 0.48 × 0.40 × 0.36 mm |
β = 109.960 (8)° |
Xcalibur, Eos, Gemini diffractometer | 9840 independent reflections |
Absorption correction: multi-scan CrysAlis PRO, Oxford Diffraction, 2010. | 8118 reflections with I > 2σ(I) |
Tmin = 0.943, Tmax = 1.000 | Rint = 0.021 |
17423 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.143 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 1.12 e Å−3 |
9840 reflections | Δρmin = −0.32 e Å−3 |
383 parameters |
Experimental. IR (KBr, ν, cm-1): 3080, 3064, 3031, 2888, 2864, 1681, 1588, 1495, 1455, 1365, 1356, 1316, 1285, 1279, 1209, 1190, 1099, 1064, 1029, 1004, 951, 936, 916, 902, 887, 884, 802, 748, 700, 675, 604, 596, 585, 557, 527, 485, 462, 432. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
P1 | 0.61224 (3) | 0.52499 (3) | 0.17147 (2) | 0.01907 (8) | |
F1 | 0.09542 (14) | 0.11276 (10) | −0.14885 (8) | 0.0595 (3) | |
O1 | 0.43362 (11) | 0.37517 (10) | 0.25151 (7) | 0.0341 (2) | |
O2 | 0.64579 (9) | 0.56565 (8) | 0.08984 (6) | 0.02406 (18) | |
N1 | 0.46767 (11) | 0.42457 (9) | 0.11608 (7) | 0.02139 (19) | |
H1N | 0.4313 (18) | 0.4221 (15) | 0.0549 (13) | 0.029 (4)* | |
N2 | 0.56350 (11) | 0.62438 (9) | 0.24783 (7) | 0.02175 (19) | |
N3 | 0.75016 (11) | 0.46451 (10) | 0.24019 (7) | 0.02328 (19) | |
C1 | 0.26260 (13) | 0.28721 (11) | 0.09631 (9) | 0.0248 (2) | |
C2 | 0.24014 (15) | 0.23735 (12) | −0.00175 (10) | 0.0301 (3) | |
H2 | 0.3069 | 0.2517 | −0.0308 | 0.036* | |
C3 | 0.11489 (18) | 0.16555 (13) | −0.05481 (11) | 0.0378 (3) | |
C4 | 0.01102 (18) | 0.14373 (15) | −0.01578 (15) | 0.0471 (4) | |
H4 | −0.0735 | 0.0977 | −0.0545 | 0.057* | |
C5 | 0.03640 (18) | 0.19228 (17) | 0.08265 (16) | 0.0509 (4) | |
H5 | −0.0311 | 0.1777 | 0.1111 | 0.061* | |
C6 | 0.16203 (16) | 0.26254 (14) | 0.13908 (13) | 0.0380 (3) | |
H6 | 0.1794 | 0.2933 | 0.2056 | 0.046* | |
C7 | 0.39457 (13) | 0.36511 (11) | 0.16160 (9) | 0.0233 (2) | |
C8 | 0.76361 (13) | 0.43097 (12) | 0.33578 (8) | 0.0248 (2) | |
H8A | 0.6737 | 0.4397 | 0.3466 | 0.030* | |
H8B | 0.8355 | 0.4861 | 0.3883 | 0.030* | |
C9 | 0.80392 (14) | 0.30247 (12) | 0.34142 (9) | 0.0265 (2) | |
C10 | 0.71824 (16) | 0.20475 (13) | 0.27461 (11) | 0.0347 (3) | |
H10 | 0.6336 | 0.2185 | 0.2269 | 0.042* | |
C11 | 0.75667 (19) | 0.08760 (15) | 0.27790 (14) | 0.0442 (4) | |
H11 | 0.6990 | 0.0235 | 0.2319 | 0.053* | |
C12 | 0.8805 (2) | 0.06598 (16) | 0.34936 (16) | 0.0492 (4) | |
H12 | 0.9072 | −0.0126 | 0.3513 | 0.059* | |
C13 | 0.96441 (19) | 0.16098 (18) | 0.41774 (15) | 0.0514 (4) | |
H13 | 1.0469 | 0.1462 | 0.4670 | 0.062* | |
C14 | 0.92681 (16) | 0.27899 (15) | 0.41383 (12) | 0.0392 (3) | |
H14 | 0.9847 | 0.3427 | 0.4602 | 0.047* | |
C15 | 0.87940 (14) | 0.45173 (13) | 0.21260 (9) | 0.0277 (2) | |
H15A | 0.8555 | 0.4606 | 0.1440 | 0.033* | |
H15B | 0.9101 | 0.3711 | 0.2182 | 0.033* | |
C16 | 1.00150 (13) | 0.54409 (12) | 0.27702 (10) | 0.0272 (2) | |
C17 | 1.11964 (15) | 0.51077 (14) | 0.34877 (11) | 0.0326 (3) | |
H17 | 1.1249 | 0.4305 | 0.3572 | 0.039* | |
C18 | 1.23005 (16) | 0.59669 (16) | 0.40806 (12) | 0.0391 (3) | |
H18 | 1.3085 | 0.5734 | 0.4557 | 0.047* | |
C19 | 1.22389 (17) | 0.71609 (16) | 0.39659 (13) | 0.0402 (3) | |
H19 | 1.2972 | 0.7735 | 0.4369 | 0.048* | |
C20 | 1.10789 (17) | 0.74988 (15) | 0.32468 (14) | 0.0415 (3) | |
H20 | 1.1036 | 0.8301 | 0.3161 | 0.050* | |
C21 | 0.99754 (16) | 0.66420 (14) | 0.26510 (12) | 0.0365 (3) | |
H21 | 0.9201 | 0.6877 | 0.2167 | 0.044* | |
C22 | 0.67207 (13) | 0.71875 (11) | 0.31683 (8) | 0.0241 (2) | |
H22A | 0.6710 | 0.7887 | 0.2855 | 0.029* | |
H22B | 0.7655 | 0.6883 | 0.3304 | 0.029* | |
C23 | 0.64753 (13) | 0.75728 (11) | 0.41343 (8) | 0.0241 (2) | |
C24 | 0.61737 (16) | 0.67221 (13) | 0.46430 (10) | 0.0312 (3) | |
H24 | 0.6060 | 0.5905 | 0.4365 | 0.037* | |
C25 | 0.60394 (18) | 0.70759 (16) | 0.55601 (10) | 0.0375 (3) | |
H25 | 0.5848 | 0.6497 | 0.5897 | 0.045* | |
C26 | 0.61904 (19) | 0.82884 (18) | 0.59725 (11) | 0.0450 (4) | |
H26 | 0.6110 | 0.8527 | 0.6591 | 0.054* | |
C27 | 0.6460 (2) | 0.91451 (16) | 0.54692 (13) | 0.0471 (4) | |
H27 | 0.6547 | 0.9963 | 0.5743 | 0.057* | |
C28 | 0.66030 (16) | 0.87901 (13) | 0.45523 (11) | 0.0342 (3) | |
H28 | 0.6786 | 0.9373 | 0.4216 | 0.041* | |
C29 | 0.41673 (13) | 0.66476 (12) | 0.21893 (9) | 0.0250 (2) | |
H29A | 0.3962 | 0.6948 | 0.2785 | 0.030* | |
H29B | 0.3496 | 0.5956 | 0.1823 | 0.030* | |
C30 | 0.39415 (13) | 0.76240 (12) | 0.15641 (9) | 0.0253 (2) | |
C31 | 0.39678 (17) | 0.88282 (13) | 0.19750 (11) | 0.0367 (3) | |
H31 | 0.4097 | 0.9041 | 0.2644 | 0.044* | |
C32 | 0.38032 (19) | 0.97234 (15) | 0.13996 (15) | 0.0476 (4) | |
H32 | 0.3821 | 1.0530 | 0.1683 | 0.057* | |
C33 | 0.36147 (18) | 0.94131 (17) | 0.04103 (16) | 0.0482 (4) | |
H33 | 0.3524 | 1.0011 | 0.0026 | 0.058* | |
C34 | 0.3560 (2) | 0.82113 (18) | −0.00112 (13) | 0.0480 (4) | |
H34 | 0.3417 | 0.8001 | −0.0683 | 0.058* | |
C35 | 0.37159 (18) | 0.73209 (15) | 0.05590 (10) | 0.0369 (3) | |
H35 | 0.3670 | 0.6514 | 0.0268 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.02207 (14) | 0.02263 (14) | 0.01297 (12) | 0.00043 (10) | 0.00599 (10) | 0.00493 (10) |
F1 | 0.0821 (8) | 0.0427 (6) | 0.0359 (5) | −0.0171 (5) | 0.0037 (5) | −0.0028 (4) |
O1 | 0.0346 (5) | 0.0483 (6) | 0.0208 (4) | −0.0061 (4) | 0.0085 (4) | 0.0136 (4) |
O2 | 0.0274 (4) | 0.0299 (4) | 0.0163 (3) | −0.0020 (3) | 0.0084 (3) | 0.0070 (3) |
N1 | 0.0246 (5) | 0.0254 (5) | 0.0139 (4) | −0.0018 (3) | 0.0059 (3) | 0.0054 (3) |
N2 | 0.0239 (5) | 0.0245 (5) | 0.0159 (4) | 0.0023 (3) | 0.0056 (3) | 0.0038 (3) |
N3 | 0.0242 (5) | 0.0304 (5) | 0.0169 (4) | 0.0048 (4) | 0.0079 (4) | 0.0072 (4) |
C1 | 0.0259 (5) | 0.0213 (5) | 0.0276 (6) | 0.0018 (4) | 0.0084 (4) | 0.0076 (4) |
C2 | 0.0378 (7) | 0.0233 (6) | 0.0279 (6) | −0.0022 (5) | 0.0086 (5) | 0.0075 (5) |
C3 | 0.0462 (8) | 0.0236 (6) | 0.0334 (7) | −0.0032 (5) | 0.0017 (6) | 0.0045 (5) |
C4 | 0.0340 (8) | 0.0339 (8) | 0.0615 (11) | −0.0078 (6) | 0.0049 (7) | 0.0027 (7) |
C5 | 0.0346 (8) | 0.0483 (10) | 0.0705 (12) | −0.0095 (7) | 0.0257 (8) | −0.0017 (9) |
C6 | 0.0339 (7) | 0.0377 (7) | 0.0447 (8) | −0.0047 (6) | 0.0204 (6) | −0.0002 (6) |
C7 | 0.0242 (5) | 0.0261 (5) | 0.0215 (5) | 0.0016 (4) | 0.0083 (4) | 0.0084 (4) |
C8 | 0.0289 (6) | 0.0293 (6) | 0.0155 (5) | 0.0047 (4) | 0.0056 (4) | 0.0064 (4) |
C9 | 0.0274 (6) | 0.0309 (6) | 0.0227 (5) | 0.0060 (4) | 0.0080 (4) | 0.0101 (5) |
C10 | 0.0352 (7) | 0.0324 (7) | 0.0322 (7) | 0.0044 (5) | 0.0052 (5) | 0.0084 (5) |
C11 | 0.0485 (9) | 0.0311 (7) | 0.0523 (9) | 0.0040 (6) | 0.0159 (7) | 0.0089 (7) |
C12 | 0.0491 (9) | 0.0391 (8) | 0.0676 (12) | 0.0176 (7) | 0.0238 (9) | 0.0229 (8) |
C13 | 0.0391 (9) | 0.0531 (10) | 0.0589 (11) | 0.0186 (7) | 0.0051 (8) | 0.0264 (9) |
C14 | 0.0321 (7) | 0.0436 (8) | 0.0351 (7) | 0.0076 (6) | 0.0003 (6) | 0.0127 (6) |
C15 | 0.0275 (6) | 0.0338 (6) | 0.0238 (5) | 0.0064 (5) | 0.0114 (5) | 0.0053 (5) |
C16 | 0.0243 (5) | 0.0338 (6) | 0.0269 (6) | 0.0053 (4) | 0.0121 (5) | 0.0080 (5) |
C17 | 0.0283 (6) | 0.0377 (7) | 0.0337 (7) | 0.0060 (5) | 0.0103 (5) | 0.0121 (6) |
C18 | 0.0280 (7) | 0.0510 (9) | 0.0367 (7) | 0.0013 (6) | 0.0064 (6) | 0.0144 (7) |
C19 | 0.0329 (7) | 0.0449 (8) | 0.0420 (8) | −0.0046 (6) | 0.0134 (6) | 0.0062 (7) |
C20 | 0.0355 (7) | 0.0357 (7) | 0.0568 (10) | 0.0021 (6) | 0.0177 (7) | 0.0145 (7) |
C21 | 0.0288 (6) | 0.0397 (8) | 0.0433 (8) | 0.0055 (5) | 0.0109 (6) | 0.0176 (6) |
C22 | 0.0294 (6) | 0.0246 (5) | 0.0181 (5) | −0.0011 (4) | 0.0083 (4) | 0.0034 (4) |
C23 | 0.0261 (5) | 0.0273 (6) | 0.0164 (5) | 0.0039 (4) | 0.0050 (4) | 0.0025 (4) |
C24 | 0.0441 (7) | 0.0310 (6) | 0.0218 (5) | 0.0070 (5) | 0.0143 (5) | 0.0069 (5) |
C25 | 0.0466 (8) | 0.0493 (9) | 0.0214 (6) | 0.0119 (6) | 0.0151 (6) | 0.0117 (6) |
C26 | 0.0524 (9) | 0.0598 (10) | 0.0223 (6) | 0.0142 (8) | 0.0154 (6) | −0.0007 (6) |
C27 | 0.0596 (10) | 0.0396 (8) | 0.0371 (8) | 0.0067 (7) | 0.0179 (7) | −0.0096 (6) |
C28 | 0.0404 (7) | 0.0289 (6) | 0.0313 (6) | 0.0033 (5) | 0.0123 (6) | 0.0004 (5) |
C29 | 0.0266 (5) | 0.0289 (6) | 0.0212 (5) | 0.0053 (4) | 0.0091 (4) | 0.0072 (4) |
C30 | 0.0268 (5) | 0.0276 (6) | 0.0228 (5) | 0.0075 (4) | 0.0089 (4) | 0.0071 (4) |
C31 | 0.0397 (7) | 0.0306 (7) | 0.0321 (7) | 0.0088 (5) | 0.0038 (6) | 0.0025 (5) |
C32 | 0.0430 (9) | 0.0289 (7) | 0.0616 (11) | 0.0060 (6) | 0.0039 (8) | 0.0132 (7) |
C33 | 0.0367 (8) | 0.0540 (10) | 0.0666 (11) | 0.0153 (7) | 0.0202 (8) | 0.0404 (9) |
C34 | 0.0572 (10) | 0.0644 (11) | 0.0406 (8) | 0.0331 (9) | 0.0283 (8) | 0.0321 (8) |
C35 | 0.0504 (8) | 0.0398 (8) | 0.0252 (6) | 0.0202 (6) | 0.0156 (6) | 0.0120 (5) |
P1—N1 | 1.6922 (10) | C16—C21 | 1.388 (2) |
P1—N2 | 1.6484 (11) | C16—C17 | 1.3916 (18) |
P1—N3 | 1.6400 (11) | C17—C18 | 1.392 (2) |
P1—O2 | 1.4786 (9) | C17—H17 | 0.9300 |
F1—C3 | 1.3500 (19) | C18—C19 | 1.379 (2) |
O1—C7 | 1.2200 (15) | C18—H18 | 0.9300 |
N1—C7 | 1.3716 (15) | C19—C20 | 1.382 (2) |
N1—H1N | 0.837 (18) | C19—H19 | 0.9300 |
N2—C22 | 1.4768 (15) | C20—C21 | 1.391 (2) |
N2—C29 | 1.4868 (16) | C20—H20 | 0.9300 |
N3—C8 | 1.4672 (15) | C21—H21 | 0.9300 |
N3—C15 | 1.4844 (16) | C22—C23 | 1.5096 (17) |
C1—C2 | 1.3886 (18) | C22—H22A | 0.9700 |
C1—C6 | 1.3987 (19) | C22—H22B | 0.9700 |
C1—C7 | 1.4984 (17) | C23—C28 | 1.3886 (19) |
C2—C3 | 1.3851 (19) | C23—C24 | 1.3888 (18) |
C2—H2 | 0.9300 | C24—C25 | 1.3860 (19) |
C3—C4 | 1.381 (3) | C24—H24 | 0.9300 |
C4—C5 | 1.385 (3) | C25—C26 | 1.380 (2) |
C4—H4 | 0.9300 | C25—H25 | 0.9300 |
C5—C6 | 1.388 (2) | C26—C27 | 1.376 (3) |
C5—H5 | 0.9300 | C26—H26 | 0.9300 |
C6—H6 | 0.9300 | C27—C28 | 1.390 (2) |
C8—C9 | 1.5144 (18) | C27—H27 | 0.9300 |
C8—H8A | 0.9700 | C28—H28 | 0.9300 |
C8—H8B | 0.9700 | C29—C30 | 1.5107 (17) |
C9—C14 | 1.3847 (18) | C29—H29A | 0.9700 |
C9—C10 | 1.3917 (19) | C29—H29B | 0.9700 |
C10—C11 | 1.382 (2) | C30—C31 | 1.3839 (19) |
C10—H10 | 0.9300 | C30—C35 | 1.3887 (18) |
C11—C12 | 1.377 (3) | C31—C32 | 1.390 (2) |
C11—H11 | 0.9300 | C31—H31 | 0.9300 |
C12—C13 | 1.374 (3) | C32—C33 | 1.375 (3) |
C12—H12 | 0.9300 | C32—H32 | 0.9300 |
C13—C14 | 1.390 (2) | C33—C34 | 1.382 (3) |
C13—H13 | 0.9300 | C33—H33 | 0.9300 |
C14—H14 | 0.9300 | C34—C35 | 1.381 (2) |
C15—C16 | 1.5181 (19) | C34—H34 | 0.9300 |
C15—H15A | 0.9700 | C35—H35 | 0.9300 |
C15—H15B | 0.9700 | ||
N1—P1—N2 | 103.81 (5) | C21—C16—C17 | 118.52 (13) |
N1—P1—N3 | 112.50 (5) | C21—C16—C15 | 120.36 (12) |
N2—P1—N3 | 106.54 (5) | C17—C16—C15 | 121.13 (12) |
O2—P1—N1 | 105.60 (5) | C16—C17—C18 | 120.50 (14) |
O2—P1—N2 | 118.92 (5) | C16—C17—H17 | 119.8 |
O2—P1—N3 | 109.48 (5) | C18—C17—H17 | 119.8 |
C7—N1—P1 | 127.16 (8) | C19—C18—C17 | 120.46 (14) |
C7—N1—H1N | 118.5 (12) | C19—C18—H18 | 119.8 |
P1—N1—H1N | 113.4 (12) | C17—C18—H18 | 119.8 |
C22—N2—C29 | 113.09 (10) | C18—C19—C20 | 119.51 (15) |
C22—N2—P1 | 117.96 (8) | C18—C19—H19 | 120.2 |
C29—N2—P1 | 121.34 (8) | C20—C19—H19 | 120.2 |
C8—N3—C15 | 114.81 (10) | C19—C20—C21 | 120.18 (15) |
C8—N3—P1 | 124.58 (8) | C19—C20—H20 | 119.9 |
C15—N3—P1 | 120.32 (8) | C21—C20—H20 | 119.9 |
C2—C1—C6 | 120.18 (13) | C16—C21—C20 | 120.82 (14) |
C2—C1—C7 | 122.70 (12) | C16—C21—H21 | 119.6 |
C6—C1—C7 | 117.09 (12) | C20—C21—H21 | 119.6 |
C3—C2—C1 | 117.73 (14) | N2—C22—C23 | 112.56 (10) |
C3—C2—H2 | 121.1 | N2—C22—H22A | 109.1 |
C1—C2—H2 | 121.1 | C23—C22—H22A | 109.1 |
F1—C3—C4 | 118.74 (14) | N2—C22—H22B | 109.1 |
F1—C3—C2 | 117.89 (15) | C23—C22—H22B | 109.1 |
C4—C3—C2 | 123.36 (15) | H22A—C22—H22B | 107.8 |
C3—C4—C5 | 118.09 (14) | C28—C23—C24 | 118.56 (12) |
C3—C4—H4 | 121.0 | C28—C23—C22 | 120.38 (12) |
C5—C4—H4 | 121.0 | C24—C23—C22 | 121.01 (11) |
C4—C5—C6 | 120.33 (16) | C25—C24—C23 | 120.85 (14) |
C4—C5—H5 | 119.8 | C25—C24—H24 | 119.6 |
C6—C5—H5 | 119.8 | C23—C24—H24 | 119.6 |
C5—C6—C1 | 120.23 (15) | C26—C25—C24 | 119.88 (15) |
C5—C6—H6 | 119.9 | C26—C25—H25 | 120.1 |
C1—C6—H6 | 119.9 | C24—C25—H25 | 120.1 |
O1—C7—N1 | 122.00 (11) | C27—C26—C25 | 120.03 (14) |
O1—C7—C1 | 120.72 (11) | C27—C26—H26 | 120.0 |
N1—C7—C1 | 117.28 (10) | C25—C26—H26 | 120.0 |
N3—C8—C9 | 112.68 (10) | C26—C27—C28 | 120.08 (15) |
N3—C8—H8A | 109.1 | C26—C27—H27 | 120.0 |
C9—C8—H8A | 109.1 | C28—C27—H27 | 120.0 |
N3—C8—H8B | 109.1 | C23—C28—C27 | 120.58 (15) |
C9—C8—H8B | 109.1 | C23—C28—H28 | 119.7 |
H8A—C8—H8B | 107.8 | C27—C28—H28 | 119.7 |
C14—C9—C10 | 118.16 (13) | N2—C29—C30 | 113.65 (10) |
C14—C9—C8 | 120.79 (12) | N2—C29—H29A | 108.8 |
C10—C9—C8 | 121.05 (11) | C30—C29—H29A | 108.8 |
C11—C10—C9 | 121.19 (14) | N2—C29—H29B | 108.8 |
C11—C10—H10 | 119.4 | C30—C29—H29B | 108.8 |
C9—C10—H10 | 119.4 | H29A—C29—H29B | 107.7 |
C12—C11—C10 | 119.90 (16) | C31—C30—C35 | 118.79 (13) |
C12—C11—H11 | 120.1 | C31—C30—C29 | 121.26 (12) |
C10—C11—H11 | 120.1 | C35—C30—C29 | 119.95 (12) |
C13—C12—C11 | 119.76 (16) | C30—C31—C32 | 120.80 (15) |
C13—C12—H12 | 120.1 | C30—C31—H31 | 119.6 |
C11—C12—H12 | 120.1 | C32—C31—H31 | 119.6 |
C12—C13—C14 | 120.42 (15) | C33—C32—C31 | 119.79 (16) |
C12—C13—H13 | 119.8 | C33—C32—H32 | 120.1 |
C14—C13—H13 | 119.8 | C31—C32—H32 | 120.1 |
C9—C14—C13 | 120.55 (16) | C32—C33—C34 | 119.86 (15) |
C9—C14—H14 | 119.7 | C32—C33—H33 | 120.1 |
C13—C14—H14 | 119.7 | C34—C33—H33 | 120.1 |
N3—C15—C16 | 112.84 (10) | C35—C34—C33 | 120.36 (16) |
N3—C15—H15A | 109.0 | C35—C34—H34 | 119.8 |
C16—C15—H15A | 109.0 | C33—C34—H34 | 119.8 |
N3—C15—H15B | 109.0 | C34—C35—C30 | 120.37 (15) |
C16—C15—H15B | 109.0 | C34—C35—H35 | 119.8 |
H15A—C15—H15B | 107.8 | C30—C35—H35 | 119.8 |
O2—P1—N1—C7 | −177.83 (10) | C10—C9—C14—C13 | 1.4 (2) |
N3—P1—N1—C7 | 62.80 (12) | C8—C9—C14—C13 | −179.03 (15) |
N2—P1—N1—C7 | −51.98 (12) | C12—C13—C14—C9 | 0.4 (3) |
O2—P1—N2—C22 | −69.72 (10) | C8—N3—C15—C16 | −69.52 (14) |
N3—P1—N2—C22 | 54.45 (9) | P1—N3—C15—C16 | 104.64 (11) |
N1—P1—N2—C22 | 173.40 (8) | N3—C15—C16—C21 | −73.76 (16) |
O2—P1—N2—C29 | 77.75 (10) | N3—C15—C16—C17 | 106.47 (14) |
N3—P1—N2—C29 | −158.08 (9) | C21—C16—C17—C18 | 1.0 (2) |
N1—P1—N2—C29 | −39.13 (10) | C15—C16—C17—C18 | −179.27 (13) |
O2—P1—N3—C8 | 170.38 (10) | C16—C17—C18—C19 | 0.1 (2) |
N2—P1—N3—C8 | 40.57 (11) | C17—C18—C19—C20 | −0.9 (2) |
N1—P1—N3—C8 | −72.54 (11) | C18—C19—C20—C21 | 0.7 (3) |
O2—P1—N3—C15 | −3.18 (11) | C17—C16—C21—C20 | −1.1 (2) |
N2—P1—N3—C15 | −132.99 (10) | C15—C16—C21—C20 | 179.08 (14) |
N1—P1—N3—C15 | 113.90 (10) | C19—C20—C21—C16 | 0.3 (2) |
C6—C1—C2—C3 | 1.3 (2) | C29—N2—C22—C23 | 61.38 (13) |
C7—C1—C2—C3 | 179.24 (12) | P1—N2—C22—C23 | −148.57 (9) |
C1—C2—C3—F1 | −177.25 (13) | N2—C22—C23—C28 | −135.97 (12) |
C1—C2—C3—C4 | 1.5 (2) | N2—C22—C23—C24 | 46.59 (16) |
F1—C3—C4—C5 | 176.03 (16) | C28—C23—C24—C25 | −1.7 (2) |
C2—C3—C4—C5 | −2.7 (3) | C22—C23—C24—C25 | 175.83 (13) |
C3—C4—C5—C6 | 1.2 (3) | C23—C24—C25—C26 | 0.7 (2) |
C4—C5—C6—C1 | 1.5 (3) | C24—C25—C26—C27 | 0.6 (3) |
C2—C1—C6—C5 | −2.7 (2) | C25—C26—C27—C28 | −1.0 (3) |
C7—C1—C6—C5 | 179.17 (15) | C24—C23—C28—C27 | 1.3 (2) |
P1—N1—C7—O1 | −3.97 (19) | C22—C23—C28—C27 | −176.22 (14) |
P1—N1—C7—C1 | 175.47 (9) | C26—C27—C28—C23 | 0.0 (3) |
C2—C1—C7—O1 | −156.09 (13) | C22—N2—C29—C30 | 67.33 (13) |
C6—C1—C7—O1 | 21.96 (19) | P1—N2—C29—C30 | −81.59 (12) |
C2—C1—C7—N1 | 24.46 (18) | N2—C29—C30—C31 | −100.23 (15) |
C6—C1—C7—N1 | −157.50 (13) | N2—C29—C30—C35 | 79.14 (15) |
C15—N3—C8—C9 | −57.00 (14) | C35—C30—C31—C32 | −1.4 (2) |
P1—N3—C8—C9 | 129.12 (10) | C29—C30—C31—C32 | 177.98 (14) |
N3—C8—C9—C14 | 121.40 (14) | C30—C31—C32—C33 | −0.1 (3) |
N3—C8—C9—C10 | −59.07 (17) | C31—C32—C33—C34 | 1.4 (3) |
C14—C9—C10—C11 | −2.2 (2) | C32—C33—C34—C35 | −1.0 (3) |
C8—C9—C10—C11 | 178.24 (15) | C33—C34—C35—C30 | −0.5 (3) |
C9—C10—C11—C12 | 1.2 (3) | C31—C30—C35—C34 | 1.7 (2) |
C10—C11—C12—C13 | 0.7 (3) | C29—C30—C35—C34 | −177.66 (14) |
C11—C12—C13—C14 | −1.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O2i | 0.93 | 2.45 | 3.1124 (16) | 128 |
C25—H25···O1ii | 0.93 | 2.45 | 3.2342 (17) | 142 |
N1—H1N···O2i | 0.837 (18) | 2.017 (18) | 2.8497 (13) | 173.7 (17) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1. |
C35H32F2N3O2P | Z = 2 |
Mr = 595.61 | F(000) = 624 |
Triclinic, P1 | Dx = 1.341 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.9526 (11) Å | Cell parameters from 6783 reflections |
b = 12.2897 (10) Å | θ = 3.2–32.3° |
c = 12.7463 (12) Å | µ = 0.14 mm−1 |
α = 102.074 (7)° | T = 173 K |
β = 104.462 (8)° | Chunk, colorless |
γ = 118.262 (9)° | 0.32 × 0.28 × 0.16 mm |
V = 1474.5 (2) Å3 |
Oxford Diffraction Xcalibur (Eos, Gemini) diffractometer | 9523 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 7763 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
Detector resolution: 16.1500 pixels mm-1 | θmax = 32.4°, θmin = 3.2° |
ω scans | h = −17→17 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | k = −17→18 |
Tmin = 0.992, Tmax = 1.000 | l = −18→18 |
17265 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0513P)2 + 0.4759P] where P = (Fo2 + 2Fc2)/3 |
9523 reflections | (Δ/σ)max < 0.001 |
392 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C35H32F2N3O2P | γ = 118.262 (9)° |
Mr = 595.61 | V = 1474.5 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.9526 (11) Å | Mo Kα radiation |
b = 12.2897 (10) Å | µ = 0.14 mm−1 |
c = 12.7463 (12) Å | T = 173 K |
α = 102.074 (7)° | 0.32 × 0.28 × 0.16 mm |
β = 104.462 (8)° |
Oxford Diffraction Xcalibur (Eos, Gemini) diffractometer | 9523 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 7763 reflections with I > 2σ(I) |
Tmin = 0.992, Tmax = 1.000 | Rint = 0.019 |
17265 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.41 e Å−3 |
9523 reflections | Δρmin = −0.37 e Å−3 |
392 parameters |
Experimental. IR (KBr, ν, cm-1): 3089, 3076, 3032, 2921, 2860, 1675, 1623, 1599, 1494, 1447, 1355, 1321, 1224, 1190, 1124, 1101, 1068, 1057, 1030, 987, 949, 913, 902, 871, 807, 796, 773, 749, 743, 697, 665, 614, 600, 571, 542, 523, 516, 476, 465, 410. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
P1 | 0.43740 (3) | −0.02169 (3) | 0.30322 (2) | 0.01984 (7) | |
F1 | 0.49638 (11) | 0.40250 (9) | 0.77758 (7) | 0.0432 (2) | |
F2 | 0.26919 (12) | 0.48796 (10) | 0.48246 (9) | 0.0500 (3) | |
O1 | 0.32602 (10) | 0.14761 (9) | 0.26412 (8) | 0.02789 (19) | |
O2 | 0.48794 (10) | −0.08185 (9) | 0.37548 (7) | 0.02689 (18) | |
N1 | 0.42791 (11) | 0.09006 (10) | 0.39671 (9) | 0.02233 (19) | |
H1N | 0.4533 (18) | 0.0941 (18) | 0.4664 (17) | 0.039 (5)* | |
N2 | 0.28600 (11) | −0.14105 (10) | 0.19524 (9) | 0.02231 (19) | |
N3 | 0.53297 (10) | 0.06323 (10) | 0.24067 (8) | 0.02067 (18) | |
C1 | 0.38081 (11) | 0.26075 (11) | 0.46306 (10) | 0.01907 (19) | |
C2 | 0.32275 (12) | 0.32957 (12) | 0.42896 (11) | 0.0239 (2) | |
H2 | 0.2837 | 0.3146 | 0.3503 | 0.029* | |
C3 | 0.32482 (14) | 0.42044 (13) | 0.51513 (13) | 0.0295 (3) | |
C4 | 0.38077 (15) | 0.44723 (13) | 0.63302 (12) | 0.0311 (3) | |
H4 | 0.3794 | 0.5080 | 0.6892 | 0.037* | |
C5 | 0.43884 (14) | 0.37847 (12) | 0.66256 (11) | 0.0272 (2) | |
C6 | 0.44136 (13) | 0.28633 (11) | 0.58150 (10) | 0.0233 (2) | |
H6 | 0.4823 | 0.2426 | 0.6053 | 0.028* | |
C7 | 0.37487 (12) | 0.16138 (11) | 0.36620 (10) | 0.0203 (2) | |
C8 | 0.63319 (12) | 0.20891 (12) | 0.29033 (10) | 0.0242 (2) | |
H8A | 0.7257 | 0.2287 | 0.3274 | 0.029* | |
H8B | 0.6129 | 0.2489 | 0.3508 | 0.029* | |
C9 | 0.63249 (12) | 0.27303 (11) | 0.20105 (11) | 0.0240 (2) | |
C10 | 0.51002 (13) | 0.24232 (12) | 0.11758 (11) | 0.0259 (2) | |
H10 | 0.4247 | 0.1758 | 0.1121 | 0.031* | |
C11 | 0.51447 (15) | 0.31028 (14) | 0.04249 (12) | 0.0319 (3) | |
H11 | 0.4323 | 0.2884 | −0.0133 | 0.038* | |
C12 | 0.64137 (18) | 0.41068 (15) | 0.05066 (15) | 0.0413 (3) | |
H12 | 0.6444 | 0.4569 | 0.0012 | 0.050* | |
C13 | 0.76264 (17) | 0.44130 (16) | 0.13250 (17) | 0.0451 (4) | |
H13 | 0.8478 | 0.5085 | 0.1382 | 0.054* | |
C14 | 0.75871 (14) | 0.37255 (14) | 0.20666 (14) | 0.0355 (3) | |
H14 | 0.8414 | 0.3932 | 0.2607 | 0.043* | |
C15 | 0.56485 (12) | −0.01043 (12) | 0.15817 (10) | 0.0237 (2) | |
H15A | 0.5631 | 0.0188 | 0.0931 | 0.028* | |
H15B | 0.4923 | −0.1050 | 0.1267 | 0.028* | |
C16 | 0.70388 (13) | 0.00782 (12) | 0.21205 (10) | 0.0244 (2) | |
C17 | 0.81851 (14) | 0.09705 (15) | 0.19713 (12) | 0.0314 (3) | |
H17 | 0.8106 | 0.1478 | 0.1545 | 0.038* | |
C18 | 0.94557 (15) | 0.11212 (17) | 0.24496 (14) | 0.0387 (3) | |
H18 | 1.0219 | 0.1727 | 0.2344 | 0.046* | |
C19 | 0.95815 (16) | 0.03721 (18) | 0.30793 (15) | 0.0415 (3) | |
H19 | 1.0428 | 0.0469 | 0.3401 | 0.050* | |
C20 | 0.84434 (19) | −0.0522 (2) | 0.32287 (19) | 0.0516 (5) | |
H20 | 0.8524 | −0.1028 | 0.3656 | 0.062* | |
C21 | 0.71770 (16) | −0.06731 (17) | 0.27473 (16) | 0.0418 (4) | |
H21 | 0.6414 | −0.1287 | 0.2848 | 0.050* | |
C22 | 0.23433 (12) | −0.13973 (12) | 0.07795 (10) | 0.0230 (2) | |
H22A | 0.2531 | −0.1913 | 0.0250 | 0.028* | |
H22B | 0.2858 | −0.0483 | 0.0830 | 0.028* | |
C23 | 0.08095 (12) | −0.19524 (12) | 0.02627 (10) | 0.0226 (2) | |
C24 | 0.03004 (14) | −0.12016 (13) | 0.06257 (12) | 0.0300 (3) | |
H24 | 0.0907 | −0.0354 | 0.1220 | 0.036* | |
C25 | −0.11001 (15) | −0.16988 (14) | 0.01136 (13) | 0.0354 (3) | |
H25 | −0.1426 | −0.1186 | 0.0369 | 0.042* | |
C26 | −0.20173 (14) | −0.29556 (14) | −0.07766 (13) | 0.0340 (3) | |
H26 | −0.2955 | −0.3283 | −0.1125 | 0.041* | |
C27 | −0.15325 (14) | −0.37201 (14) | −0.11446 (13) | 0.0350 (3) | |
H27 | −0.2146 | −0.4570 | −0.1735 | 0.042* | |
C28 | −0.01251 (13) | −0.32199 (13) | −0.06331 (12) | 0.0298 (3) | |
H28 | 0.0196 | −0.3736 | −0.0891 | 0.036* | |
C29 | 0.21642 (14) | −0.27347 (12) | 0.20305 (11) | 0.0271 (2) | |
H29A | 0.2825 | −0.2988 | 0.2194 | 0.033* | |
H29B | 0.1413 | −0.3387 | 0.1274 | 0.033* | |
C30 | 0.15810 (13) | −0.27986 (12) | 0.29566 (11) | 0.0240 (2) | |
C31 | 0.10079 (17) | −0.20779 (16) | 0.32146 (14) | 0.0372 (3) | |
H31 | 0.1002 | −0.1515 | 0.2829 | 0.045* | |
C32 | 0.04429 (18) | −0.21939 (18) | 0.40456 (16) | 0.0436 (4) | |
H32 | 0.0078 | −0.1694 | 0.4224 | 0.052* | |
C33 | 0.04182 (15) | −0.30452 (16) | 0.46101 (13) | 0.0364 (3) | |
H33 | 0.0020 | −0.3134 | 0.5153 | 0.044* | |
C34 | 0.09897 (13) | −0.37615 (13) | 0.43611 (12) | 0.0294 (3) | |
H34 | 0.0982 | −0.4332 | 0.4741 | 0.035* | |
C35 | 0.15751 (13) | −0.36316 (12) | 0.35458 (11) | 0.0254 (2) | |
H35 | 0.1969 | −0.4109 | 0.3391 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.02944 (15) | 0.02422 (14) | 0.01462 (12) | 0.02134 (12) | 0.00770 (10) | 0.00797 (10) |
F1 | 0.0675 (6) | 0.0436 (5) | 0.0207 (4) | 0.0381 (5) | 0.0116 (4) | 0.0057 (3) |
F2 | 0.0756 (7) | 0.0585 (6) | 0.0564 (6) | 0.0610 (6) | 0.0298 (5) | 0.0292 (5) |
O1 | 0.0383 (5) | 0.0348 (5) | 0.0193 (4) | 0.0276 (4) | 0.0084 (4) | 0.0110 (3) |
O2 | 0.0434 (5) | 0.0341 (4) | 0.0190 (4) | 0.0323 (4) | 0.0113 (4) | 0.0124 (3) |
N1 | 0.0343 (5) | 0.0279 (5) | 0.0164 (4) | 0.0251 (4) | 0.0100 (4) | 0.0092 (4) |
N2 | 0.0303 (5) | 0.0216 (4) | 0.0181 (4) | 0.0161 (4) | 0.0084 (4) | 0.0101 (3) |
N3 | 0.0250 (4) | 0.0229 (4) | 0.0165 (4) | 0.0169 (4) | 0.0066 (3) | 0.0048 (3) |
C1 | 0.0211 (5) | 0.0196 (5) | 0.0214 (5) | 0.0141 (4) | 0.0091 (4) | 0.0087 (4) |
C2 | 0.0274 (5) | 0.0265 (5) | 0.0274 (6) | 0.0204 (5) | 0.0114 (5) | 0.0130 (4) |
C3 | 0.0355 (6) | 0.0294 (6) | 0.0397 (7) | 0.0266 (5) | 0.0178 (6) | 0.0165 (5) |
C4 | 0.0425 (7) | 0.0266 (6) | 0.0353 (7) | 0.0253 (6) | 0.0202 (6) | 0.0103 (5) |
C5 | 0.0357 (6) | 0.0243 (5) | 0.0222 (5) | 0.0190 (5) | 0.0102 (5) | 0.0062 (4) |
C6 | 0.0300 (6) | 0.0227 (5) | 0.0224 (5) | 0.0193 (5) | 0.0089 (4) | 0.0081 (4) |
C7 | 0.0249 (5) | 0.0230 (5) | 0.0192 (5) | 0.0176 (4) | 0.0086 (4) | 0.0089 (4) |
C8 | 0.0231 (5) | 0.0237 (5) | 0.0194 (5) | 0.0137 (4) | 0.0032 (4) | 0.0021 (4) |
C9 | 0.0251 (5) | 0.0203 (5) | 0.0233 (5) | 0.0130 (4) | 0.0084 (4) | 0.0033 (4) |
C10 | 0.0269 (6) | 0.0234 (5) | 0.0258 (6) | 0.0136 (5) | 0.0097 (5) | 0.0088 (4) |
C11 | 0.0409 (7) | 0.0317 (6) | 0.0287 (6) | 0.0231 (6) | 0.0146 (5) | 0.0132 (5) |
C12 | 0.0548 (9) | 0.0356 (7) | 0.0455 (9) | 0.0259 (7) | 0.0296 (8) | 0.0232 (7) |
C13 | 0.0396 (8) | 0.0341 (7) | 0.0617 (11) | 0.0148 (6) | 0.0293 (8) | 0.0223 (7) |
C14 | 0.0263 (6) | 0.0294 (6) | 0.0427 (8) | 0.0126 (5) | 0.0123 (6) | 0.0090 (6) |
C15 | 0.0269 (5) | 0.0276 (5) | 0.0187 (5) | 0.0190 (5) | 0.0078 (4) | 0.0046 (4) |
C16 | 0.0282 (6) | 0.0287 (6) | 0.0224 (5) | 0.0208 (5) | 0.0103 (4) | 0.0077 (4) |
C17 | 0.0334 (6) | 0.0418 (7) | 0.0294 (6) | 0.0249 (6) | 0.0162 (5) | 0.0173 (5) |
C18 | 0.0300 (7) | 0.0484 (8) | 0.0422 (8) | 0.0234 (6) | 0.0175 (6) | 0.0177 (7) |
C19 | 0.0343 (7) | 0.0560 (9) | 0.0454 (9) | 0.0341 (7) | 0.0150 (6) | 0.0176 (7) |
C20 | 0.0513 (9) | 0.0695 (12) | 0.0746 (13) | 0.0495 (9) | 0.0330 (9) | 0.0491 (10) |
C21 | 0.0387 (8) | 0.0498 (9) | 0.0652 (11) | 0.0341 (7) | 0.0283 (7) | 0.0384 (8) |
C22 | 0.0251 (5) | 0.0266 (5) | 0.0181 (5) | 0.0148 (5) | 0.0078 (4) | 0.0101 (4) |
C23 | 0.0249 (5) | 0.0235 (5) | 0.0207 (5) | 0.0137 (4) | 0.0090 (4) | 0.0105 (4) |
C24 | 0.0311 (6) | 0.0267 (6) | 0.0283 (6) | 0.0183 (5) | 0.0056 (5) | 0.0056 (5) |
C25 | 0.0342 (7) | 0.0346 (7) | 0.0386 (7) | 0.0249 (6) | 0.0098 (6) | 0.0072 (6) |
C26 | 0.0252 (6) | 0.0332 (7) | 0.0394 (7) | 0.0164 (5) | 0.0100 (5) | 0.0098 (6) |
C27 | 0.0259 (6) | 0.0259 (6) | 0.0393 (7) | 0.0109 (5) | 0.0088 (5) | 0.0023 (5) |
C28 | 0.0272 (6) | 0.0257 (6) | 0.0336 (7) | 0.0151 (5) | 0.0120 (5) | 0.0057 (5) |
C29 | 0.0402 (7) | 0.0232 (5) | 0.0245 (6) | 0.0203 (5) | 0.0147 (5) | 0.0118 (4) |
C30 | 0.0276 (5) | 0.0239 (5) | 0.0228 (5) | 0.0158 (5) | 0.0088 (4) | 0.0107 (4) |
C31 | 0.0520 (9) | 0.0453 (8) | 0.0418 (8) | 0.0385 (7) | 0.0261 (7) | 0.0272 (7) |
C32 | 0.0541 (9) | 0.0610 (10) | 0.0491 (9) | 0.0468 (9) | 0.0313 (8) | 0.0296 (8) |
C33 | 0.0352 (7) | 0.0484 (8) | 0.0352 (7) | 0.0253 (6) | 0.0199 (6) | 0.0205 (6) |
C34 | 0.0290 (6) | 0.0312 (6) | 0.0270 (6) | 0.0146 (5) | 0.0104 (5) | 0.0154 (5) |
C35 | 0.0296 (6) | 0.0253 (5) | 0.0250 (6) | 0.0172 (5) | 0.0102 (5) | 0.0122 (4) |
P1—N1 | 1.6880 (10) | C16—C21 | 1.3804 (18) |
P1—N2 | 1.6488 (11) | C16—C17 | 1.3822 (18) |
P1—N3 | 1.6443 (11) | C17—C18 | 1.3915 (19) |
P1—O2 | 1.4798 (9) | C17—H17 | 0.9300 |
F1—C5 | 1.3537 (15) | C18—C19 | 1.376 (2) |
F2—C3 | 1.3538 (14) | C18—H18 | 0.9300 |
O1—C7 | 1.2236 (14) | C19—C20 | 1.377 (2) |
N1—C7 | 1.3664 (14) | C19—H19 | 0.9300 |
N1—H1N | 0.847 (19) | C20—C21 | 1.387 (2) |
N2—C22 | 1.4748 (14) | C20—H20 | 0.9300 |
N2—C29 | 1.4756 (15) | C21—H21 | 0.9300 |
N3—C8 | 1.4687 (15) | C22—C23 | 1.5115 (16) |
N3—C15 | 1.4829 (14) | C22—H22A | 0.9700 |
C1—C6 | 1.3936 (16) | C22—H22B | 0.9700 |
C1—C2 | 1.3945 (15) | C23—C24 | 1.3891 (17) |
C1—C7 | 1.5047 (15) | C23—C28 | 1.3961 (17) |
C2—C3 | 1.3789 (17) | C24—C25 | 1.3858 (19) |
C2—H2 | 0.9300 | C24—H24 | 0.9300 |
C3—C4 | 1.377 (2) | C25—C26 | 1.385 (2) |
C4—C5 | 1.3768 (18) | C25—H25 | 0.9300 |
C4—H4 | 0.9300 | C26—C27 | 1.3805 (19) |
C5—C6 | 1.3816 (16) | C26—H26 | 0.9300 |
C6—H6 | 0.9300 | C27—C28 | 1.3921 (19) |
C8—C9 | 1.5141 (18) | C27—H27 | 0.9300 |
C8—H8A | 0.9700 | C28—H28 | 0.9300 |
C8—H8B | 0.9700 | C29—C30 | 1.5111 (17) |
C9—C14 | 1.3925 (18) | C29—H29A | 0.9700 |
C9—C10 | 1.3959 (17) | C29—H29B | 0.9700 |
C10—C11 | 1.3908 (18) | C30—C31 | 1.3882 (18) |
C10—H10 | 0.9300 | C30—C35 | 1.3890 (16) |
C11—C12 | 1.389 (2) | C31—C32 | 1.388 (2) |
C11—H11 | 0.9300 | C31—H31 | 0.9300 |
C12—C13 | 1.377 (3) | C32—C33 | 1.382 (2) |
C12—H12 | 0.9300 | C32—H32 | 0.9300 |
C13—C14 | 1.389 (2) | C33—C34 | 1.380 (2) |
C13—H13 | 0.9300 | C33—H33 | 0.9300 |
C14—H14 | 0.9300 | C34—C35 | 1.3863 (18) |
C15—C16 | 1.5151 (16) | C34—H34 | 0.9300 |
C15—H15A | 0.9700 | C35—H35 | 0.9300 |
C15—H15B | 0.9700 | ||
N1—P1—N2 | 113.07 (5) | C21—C16—C17 | 118.49 (12) |
N1—P1—N3 | 105.18 (5) | C21—C16—C15 | 120.46 (12) |
N2—P1—N3 | 105.51 (5) | C17—C16—C15 | 121.02 (11) |
O2—P1—N1 | 105.15 (5) | C16—C17—C18 | 121.00 (13) |
O2—P1—N2 | 109.06 (5) | C16—C17—H17 | 119.5 |
O2—P1—N3 | 119.05 (5) | C18—C17—H17 | 119.5 |
C7—N1—P1 | 125.60 (8) | C19—C18—C17 | 119.91 (14) |
C7—N1—H1N | 120.9 (12) | C19—C18—H18 | 120.0 |
P1—N1—H1N | 113.3 (12) | C17—C18—H18 | 120.0 |
C22—N2—C29 | 115.46 (10) | C18—C19—C20 | 119.44 (13) |
C22—N2—P1 | 125.00 (8) | C18—C19—H19 | 120.3 |
C29—N2—P1 | 116.99 (8) | C20—C19—H19 | 120.3 |
C8—N3—C15 | 113.59 (9) | C19—C20—C21 | 120.50 (15) |
C8—N3—P1 | 125.14 (8) | C19—C20—H20 | 119.7 |
C15—N3—P1 | 116.41 (8) | C21—C20—H20 | 119.7 |
C6—C1—C2 | 120.19 (10) | C16—C21—C20 | 120.65 (14) |
C6—C1—C7 | 123.37 (10) | C16—C21—H21 | 119.7 |
C2—C1—C7 | 116.44 (10) | C20—C21—H21 | 119.7 |
C3—C2—C1 | 118.15 (11) | N2—C22—C23 | 114.47 (9) |
C3—C2—H2 | 120.9 | N2—C22—H22A | 108.6 |
C1—C2—H2 | 120.9 | C23—C22—H22A | 108.6 |
F2—C3—C4 | 117.80 (12) | N2—C22—H22B | 108.6 |
F2—C3—C2 | 118.35 (12) | C23—C22—H22B | 108.6 |
C4—C3—C2 | 123.85 (11) | H22A—C22—H22B | 107.6 |
C5—C4—C3 | 115.88 (11) | C24—C23—C28 | 118.32 (11) |
C5—C4—H4 | 122.1 | C24—C23—C22 | 121.29 (11) |
C3—C4—H4 | 122.1 | C28—C23—C22 | 120.33 (11) |
F1—C5—C4 | 118.00 (11) | C25—C24—C23 | 120.87 (12) |
F1—C5—C6 | 118.29 (11) | C25—C24—H24 | 119.6 |
C4—C5—C6 | 123.71 (12) | C23—C24—H24 | 119.6 |
C5—C6—C1 | 118.19 (11) | C26—C25—C24 | 120.34 (13) |
C5—C6—H6 | 120.9 | C26—C25—H25 | 119.8 |
C1—C6—H6 | 120.9 | C24—C25—H25 | 119.8 |
O1—C7—N1 | 121.81 (10) | C27—C26—C25 | 119.65 (13) |
O1—C7—C1 | 120.41 (10) | C27—C26—H26 | 120.2 |
N1—C7—C1 | 117.77 (10) | C25—C26—H26 | 120.2 |
N3—C8—C9 | 113.99 (9) | C26—C27—C28 | 120.05 (13) |
N3—C8—H8A | 108.8 | C26—C27—H27 | 120.0 |
C9—C8—H8A | 108.8 | C28—C27—H27 | 120.0 |
N3—C8—H8B | 108.8 | C27—C28—C23 | 120.78 (12) |
C9—C8—H8B | 108.8 | C27—C28—H28 | 119.6 |
H8A—C8—H8B | 107.6 | C23—C28—H28 | 119.6 |
C14—C9—C10 | 118.38 (12) | N2—C29—C30 | 114.45 (10) |
C14—C9—C8 | 118.93 (12) | N2—C29—H29A | 108.6 |
C10—C9—C8 | 122.56 (11) | C30—C29—H29A | 108.6 |
C11—C10—C9 | 120.60 (12) | N2—C29—H29B | 108.6 |
C11—C10—H10 | 119.7 | C30—C29—H29B | 108.6 |
C9—C10—H10 | 119.7 | H29A—C29—H29B | 107.6 |
C12—C11—C10 | 120.16 (14) | C31—C30—C35 | 118.62 (12) |
C12—C11—H11 | 119.9 | C31—C30—C29 | 121.91 (11) |
C10—C11—H11 | 119.9 | C35—C30—C29 | 119.44 (11) |
C13—C12—C11 | 119.60 (14) | C30—C31—C32 | 120.28 (13) |
C13—C12—H12 | 120.2 | C30—C31—H31 | 119.9 |
C11—C12—H12 | 120.2 | C32—C31—H31 | 119.9 |
C12—C13—C14 | 120.43 (14) | C33—C32—C31 | 120.62 (14) |
C12—C13—H13 | 119.8 | C33—C32—H32 | 119.7 |
C14—C13—H13 | 119.8 | C31—C32—H32 | 119.7 |
C13—C14—C9 | 120.81 (14) | C34—C33—C32 | 119.42 (13) |
C13—C14—H14 | 119.6 | C34—C33—H33 | 120.3 |
C9—C14—H14 | 119.6 | C32—C33—H33 | 120.3 |
N3—C15—C16 | 114.46 (9) | C33—C34—C35 | 120.11 (12) |
N3—C15—H15A | 108.6 | C33—C34—H34 | 119.9 |
C16—C15—H15A | 108.6 | C35—C34—H34 | 119.9 |
N3—C15—H15B | 108.6 | C34—C35—C30 | 120.93 (12) |
C16—C15—H15B | 108.6 | C34—C35—H35 | 119.5 |
H15A—C15—H15B | 107.6 | C30—C35—H35 | 119.5 |
O2—P1—N1—C7 | −174.13 (10) | C11—C12—C13—C14 | 0.0 (2) |
N3—P1—N1—C7 | 59.38 (11) | C12—C13—C14—C9 | −1.0 (2) |
N2—P1—N1—C7 | −55.24 (12) | C10—C9—C14—C13 | 1.2 (2) |
O2—P1—N2—C22 | −148.50 (9) | C8—C9—C14—C13 | −174.90 (13) |
N3—P1—N2—C22 | −19.53 (11) | C8—N3—C15—C16 | 60.84 (13) |
N1—P1—N2—C22 | 94.90 (10) | P1—N3—C15—C16 | −95.82 (11) |
O2—P1—N2—C29 | 12.48 (10) | N3—C15—C16—C21 | 82.20 (16) |
N3—P1—N2—C29 | 141.45 (9) | N3—C15—C16—C17 | −99.52 (14) |
N1—P1—N2—C29 | −104.12 (9) | C21—C16—C17—C18 | −0.6 (2) |
O2—P1—N3—C8 | −94.45 (10) | C15—C16—C17—C18 | −178.90 (13) |
N2—P1—N3—C8 | 142.75 (9) | C16—C17—C18—C19 | 0.2 (2) |
N1—P1—N3—C8 | 22.97 (10) | C17—C18—C19—C20 | 0.0 (3) |
O2—P1—N3—C15 | 59.19 (10) | C18—C19—C20—C21 | 0.2 (3) |
N2—P1—N3—C15 | −63.61 (9) | C17—C16—C21—C20 | 0.8 (2) |
N1—P1—N3—C15 | 176.61 (8) | C15—C16—C21—C20 | 179.14 (16) |
C6—C1—C2—C3 | −1.29 (18) | C19—C20—C21—C16 | −0.6 (3) |
C7—C1—C2—C3 | 179.30 (11) | C29—N2—C22—C23 | 57.53 (14) |
C1—C2—C3—F2 | 179.68 (11) | P1—N2—C22—C23 | −141.23 (9) |
C1—C2—C3—C4 | −0.1 (2) | N2—C22—C23—C24 | 77.82 (14) |
F2—C3—C4—C5 | −178.67 (12) | N2—C22—C23—C28 | −104.96 (13) |
C2—C3—C4—C5 | 1.1 (2) | C28—C23—C24—C25 | 0.1 (2) |
C3—C4—C5—F1 | 179.37 (12) | C22—C23—C24—C25 | 177.40 (12) |
C3—C4—C5—C6 | −0.8 (2) | C23—C24—C25—C26 | −0.3 (2) |
F1—C5—C6—C1 | 179.36 (11) | C24—C25—C26—C27 | 0.7 (2) |
C4—C5—C6—C1 | −0.5 (2) | C25—C26—C27—C28 | −0.9 (2) |
C2—C1—C6—C5 | 1.55 (18) | C26—C27—C28—C23 | 0.7 (2) |
C7—C1—C6—C5 | −179.08 (11) | C24—C23—C28—C27 | −0.3 (2) |
P1—N1—C7—O1 | 1.24 (18) | C22—C23—C28—C27 | −177.62 (13) |
P1—N1—C7—C1 | −177.54 (8) | C22—N2—C29—C30 | −125.48 (11) |
C6—C1—C7—O1 | −176.63 (11) | P1—N2—C29—C30 | 71.71 (13) |
C2—C1—C7—O1 | 2.76 (16) | N2—C29—C30—C31 | 35.58 (18) |
C6—C1—C7—N1 | 2.16 (17) | N2—C29—C30—C35 | −146.45 (12) |
C2—C1—C7—N1 | −178.45 (10) | C35—C30—C31—C32 | 0.0 (2) |
C15—N3—C8—C9 | 66.04 (12) | C29—C30—C31—C32 | 177.99 (14) |
P1—N3—C8—C9 | −139.68 (9) | C30—C31—C32—C33 | −1.3 (3) |
N3—C8—C9—C14 | −138.17 (12) | C31—C32—C33—C34 | 1.4 (3) |
N3—C8—C9—C10 | 45.92 (15) | C32—C33—C34—C35 | −0.4 (2) |
C14—C9—C10—C11 | −0.36 (18) | C33—C34—C35—C30 | −0.9 (2) |
C8—C9—C10—C11 | 175.57 (11) | C31—C30—C35—C34 | 1.06 (19) |
C9—C10—C11—C12 | −0.6 (2) | C29—C30—C35—C34 | −176.98 (12) |
C10—C11—C12—C13 | 0.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O2i | 0.93 | 2.22 | 3.1123 (14) | 162 |
N1—H1N···O2i | 0.847 (19) | 2.024 (19) | 2.8659 (13) | 172.8 (17) |
Symmetry code: (i) −x+1, −y, −z+1. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C30H29ClF2N3O2P | C35H33FN3O2P | C35H32F2N3O2P |
Mr | 567.98 | 577.61 | 595.61 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 296 | 173 | 173 |
a, b, c (Å) | 10.8298 (3), 9.9164 (3), 26.6740 (8) | 10.0173 (10), 11.2362 (8), 14.5992 (12) | 11.9526 (11), 12.2897 (10), 12.7463 (12) |
α, β, γ (°) | 90, 91.539 (1), 90 | 99.351 (6), 109.960 (8), 91.135 (7) | 102.074 (7), 104.462 (8), 118.262 (9) |
V (Å3) | 2863.56 (15) | 1519.0 (2) | 1474.5 (2) |
Z | 4 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.23 | 0.13 | 0.14 |
Crystal size (mm) | 0.56 × 0.51 × 0.48 | 0.48 × 0.40 × 0.36 | 0.32 × 0.28 × 0.16 |
Data collection | |||
Diffractometer | Bruker APEXII CCD diffractometer | Xcalibur, Eos, Gemini diffractometer | Oxford Diffraction Xcalibur (Eos, Gemini) diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) | Multi-scan CrysAlis PRO, Oxford Diffraction, 2010. | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) |
Tmin, Tmax | 0.694, 0.746 | 0.943, 1.000 | 0.992, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 31854, 6905, 5873 | 17423, 9840, 8118 | 17265, 9523, 7763 |
Rint | 0.019 | 0.021 | 0.019 |
(sin θ/λ)max (Å−1) | 0.660 | 0.753 | 0.753 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.134, 1.05 | 0.048, 0.143, 1.04 | 0.042, 0.116, 1.05 |
No. of reflections | 6905 | 9840 | 9523 |
No. of parameters | 356 | 383 | 392 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.78, −0.68 | 1.12, −0.32 | 0.41, −0.37 |
Computer programs: APEX2 (Bruker, 2007), CrysAlis PRO (Oxford Diffraction, 2010), SAINT (Bruker, 2007), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XPW (Siemens, 1996) and Mercury (Macrae et al., 2008), SHELXTL (Sheldrick, 2008) and enCIFer (Allen et al., 2004).
P1—N1 | 1.7011 (13) | F3—C30 | 1.322 (2) |
P1—N2 | 1.6331 (14) | N2—C1 | 1.465 (2) |
P1—N3 | 1.6373 (13) | N2—C8 | 1.480 (2) |
P1—O2 | 1.4739 (11) | N3—C22 | 1.477 (2) |
Cl1—C30 | 1.748 (2) | N3—C15 | 1.4788 (19) |
O1—C29 | 1.208 (2) | N1—C29 | 1.348 (2) |
F2—C30 | 1.338 (2) | ||
O2—P1—N1 | 104.82 (7) | C8—N2—P1 | 120.13 (11) |
O2—P1—N2 | 111.59 (7) | C22—N3—C15 | 114.69 (13) |
O2—P1—N3 | 118.57 (7) | C15—N3—P1 | 120.57 (11) |
N1—P1—N2 | 110.25 (7) | C22—N3—P1 | 119.96 (10) |
N1—P1—N3 | 105.08 (7) | C29—N1—P1 | 126.83 (11) |
N2—P1—N3 | 106.23 (7) | O1—C29—N1 | 126.99 (15) |
C1—N2—C8 | 114.75 (14) | F3—C30—F2 | 107.49 (17) |
C1—N2—P1 | 124.74 (11) | F3—C30—Cl1 | 109.36 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.80 (2) | 1.98 (2) | 2.7788 (17) | 172 (2) |
Symmetry code: (i) −x, −y+2, −z+2. |
P1—N1 | 1.6922 (10) | N1—C7 | 1.3716 (15) |
P1—N2 | 1.6484 (11) | N2—C22 | 1.4768 (15) |
P1—N3 | 1.6400 (11) | N2—C29 | 1.4868 (16) |
P1—O2 | 1.4786 (9) | N3—C8 | 1.4672 (15) |
F1—C3 | 1.3500 (19) | N3—C15 | 1.4844 (16) |
O1—C7 | 1.2200 (15) | ||
N1—P1—N2 | 103.81 (5) | C22—N2—C29 | 113.09 (10) |
N1—P1—N3 | 112.50 (5) | C22—N2—P1 | 117.96 (8) |
N2—P1—N3 | 106.54 (5) | C29—N2—P1 | 121.34 (8) |
O2—P1—N1 | 105.60 (5) | C8—N3—C15 | 114.81 (10) |
O2—P1—N2 | 118.92 (5) | C8—N3—P1 | 124.58 (8) |
O2—P1—N3 | 109.48 (5) | C15—N3—P1 | 120.32 (8) |
C7—N1—P1 | 127.16 (8) | O1—C7—N1 | 122.00 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O2i | 0.93 | 2.45 | 3.1124 (16) | 128.4 |
C25—H25···O1ii | 0.93 | 2.45 | 3.2342 (17) | 142.4 |
N1—H1N···O2i | 0.837 (18) | 2.017 (18) | 2.8497 (13) | 173.7 (17) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1. |
P1—N1 | 1.6880 (10) | O1—C7 | 1.2236 (14) |
P1—N2 | 1.6488 (11) | N1—C7 | 1.3664 (14) |
P1—N3 | 1.6443 (11) | N2—C22 | 1.4748 (14) |
P1—O2 | 1.4798 (9) | N2—C29 | 1.4756 (15) |
F1—C5 | 1.3537 (15) | N3—C8 | 1.4687 (15) |
F2—C3 | 1.3538 (14) | N3—C15 | 1.4829 (14) |
N1—P1—N2 | 113.07 (5) | C22—N2—C29 | 115.46 (10) |
N1—P1—N3 | 105.18 (5) | C22—N2—P1 | 125.00 (8) |
N2—P1—N3 | 105.51 (5) | C29—N2—P1 | 116.99 (8) |
O2—P1—N1 | 105.15 (5) | C8—N3—C15 | 113.59 (9) |
O2—P1—N2 | 109.06 (5) | C8—N3—P1 | 125.14 (8) |
O2—P1—N3 | 119.05 (5) | C15—N3—P1 | 116.41 (8) |
C7—N1—P1 | 125.60 (8) | O1—C7—N1 | 121.81 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O2i | 0.93 | 2.22 | 3.1123 (14) | 161.6 |
N1—H1N···O2i | 0.847 (19) | 2.024 (19) | 2.8659 (13) | 172.8 (17) |
Symmetry code: (i) −x+1, −y, −z+1. |
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The N—P═O group is the basic skeleton of a large family of compounds called phosphoramides. The environment of the N atom bonded to the P atom in these compounds tends toward planarity (Pourayoubi et al., 2011), similar to N atoms bonded to C atoms in organic amides (Döring et al., 2012), unless the N atom is in an environment with an inherent distortion (Rebrova et al., 1992).
We present here three new phosphoric triamides with a C(O)NHP(O)[N]2 skeleton, where `[N]2' denotes two tertiary N atoms belonging to an amido group; these compounds are N,N,N',N'-tetrabenzyl-N''-(2-chloro-2,2-difluoroacetyl)phosphoric triamide, (I), N,N,N',N'-tetrabenzyl-N''-(3-fluorobenzoyl)phosphoric triamide, (II), and N,N,N',N'-tetrabenzyl-N''-(3,5-difluorobenzoyl)phosphoric triamide, (III). The geometries of the tertiary N atoms in these compounds are analyzed and compared with those of analogous structures deposited in the Cambridge Structural Database (CSD, Version 5.32, May 2011 update; Allen, 2002; for each example, the CSD refcode is given in capitals followed by the primary reference). All three N atoms in the C(O)NHP(O)[N]2 core are amido N atoms. For clarity, the N atom in the C(O)NHP(O) fragment is designated as NC(O)NHP(O), whereas the other two N atoms are designated as Namido atoms.
In (I), (II) and (III), the asymmetric unit contains one molecule, with the C(O)NHP(O)[N]2 skeleton (Figa. 1, 2 and 3). The P atom exhibits a distorted tetrahedral environment, which is reflected in the bond lengths and angles in the [N]P(O)[N]2 fragment (Tables 1, 3 and 5), similar to that observed for related phosphoramide derivatives (Pourayoubi et al., 2011). The P═ O and P—N bond lengths, as well as the bond angles at the P atom, are comparable to those in similar compounds (Pourayoubi et al., 2011). In (I)–(III), the widest angle about the P atom is observed in one of the two O—P—Namido angles, whereas the narrowest angle for (I) and (III) is O—P—NC(O)NHP(O) and for (II) is an Namido—P—NC(O)NHP(O) angle.
In the C(O)NHP(O) fragment of (I), (II) and (III), the P—N bond is longer and the O—P—N angle is contracted compared with the other two P—N bonds and the other two O—P—N angles in each molecule. The bond distance trend is seen in a histogram of P—Namide and P—NC(O)NHP(O) distances (Fig. 4). This histogram covers the P—N bond lengths in all phosphoric triamides with C(O)NHP(O)[N]2 and C(O)NHP(O)[NH]2 fragments found in the CSD. In the range 1.60–1.66 Å, only P—Namide bonds are found; and in the range 1.68–1.74 Å only P—NC(O)NHP(O) bonds are found, while in the range 1.66–1.68 Å, both types of P—N bonds are observed. The number of P—Namide bond entries is twice the number of P—NC(O)NHP(O) bonds found in the CSD for phosphoramides with C(O)NHP(O) fragments. Compounds with [C(O)NH]P(O)[N]X (X ≠ N), such as compounds with a [C(O)NH]P(O)[N][O] skeleton, have not been reported. Also, compounds with a [C(O)NH]2P(O)[N] fragment have not been reported to date.
The two tertiary N atoms in each of (I), (II) and (III) show sp2 character with a slight deviation from planarity, wherein one of the two benzylamido N atoms shows a slightly higher deviation than the other. The sum of the surrounding bond angles (2 × P—N—C + C—N—C) at N2 and N3 in (I) are 359.6 (2) and 355.2 (2)°, respectively. In (II) and (III), the higher values are 359.71 (15) and 357.45 (15)°, respectively, while the lower values are 352.39 (15) and 355.14 (14)°, respectively. Thus, the differences in these bond-angle sums are small. The more pyramidal of the tertiary N atoms in these molecules [i.e. N3 in (I) and (III), and N2 in (II)] are oriented so that the lone electron pair (LEP) is anti with respect to the P═ O group.
Fig. 5 shows the slight pyramidality of one of the N atoms in compound (I) with the LEP anti relative to P═O.
The bond-angle sums for phosphoric triamides with C(O)NHP(O)[N]2 skeletons found in the CSD were also examined (`[N]' denotes a tertiary N atom). Compounds with three-membered cyclic amido substituents were excluded from consideration, as ring strain affects the sum of the surrounding bond angles at the tertiary N atoms, which can deviate significantly from 360° (in the range 292.3–311.8°). Compounds with disorder in the N or surrounding atoms were also excluded.
Fig. 6 shows the sum of surrounding bond angles around the two tertiary N atoms (as different colors) in 60 compounds with C(O)NHP(O)[N]2 fragments; the bond-angle sum varies in the range 339.1–360°. The entries are arranged from smallest difference (leftmost) to largest (rightmost). The greatest difference is found for C6H5C(O)NHP(O)[NC3H6]2 (LAYMII; Gholivand et al., 2005), with values of 357.96 and 340.49°, respectively. In this example, similar to compounds (I), (II) and (III), the LEP of the N atom adopts an anti orientation relative to the P═O group (entry 60; Fig. 6). This situation is also observed for entries 59 (LARTII01; Marsh, 2009), 58 (WIYTUT; Gubina et al., 2000), 57 (VEHTAE; Gholivand, Alizadehgan et al., 2006), 56 (VEFLUO; Gholivand, Mojahed et al., 2006), 55 (LIVWAP; Dehghanpour et al., 2008), 54 (KEBPUD; Gholivand, Shariatinia & Pourayoubi, 2006), 53 (BUVJOS; Dehghanpour et al., 2010), 52 and 51 (SIRXIB and SIRXEX; Gholivand et al., 2007), 50 (BUVJIM; Dehghanpour et al., 2010) and 49 (VEHTAE; Gholivand, Alizadehgan et al., 2006), with ΔSUM (= SUM1 - SUM2) ranging from 14.3 to 5.9°, where the LEP of the more pyramidal N atom is anti relative to P═O.
Of the three angles at the tertiary N atoms, the C—N—C angles in all the studied structures have a significantly lower value than those of the two P—N—C angles.
For each of (I), (II) and (III), the phosphoryl and carbonyl groups, which are separated by an N atom, have a relative anti disposition. The O/P/N/C torsion angles in (I), (II) and (III) are 169.65 (12), -177.83 (10) and -174.13 (10)°, respectively. Similar relative orientations have been observed for a majority of the compounds with C(O)NHP(O)[N]2 skeletons (Toghraee et al., 2011).
In (I), (II) and (III), adjacent molecules are linked via pairs of P═ O···H—N hydrogen bonds forming dimers with Ci symmetry (Tables 2, 4 and 6). For structures (II) and (III), phosphoryl atom O2 receives a second hydrogen bond (C—H···O) from the inversion-related molecule. A view of the packing in the crystal structure of compound (III) is shown in Fig. 7. Another C—H···O interaction is also observed in structure (II) (Table 5) involving carbonyl atom O1 as acceptor.
In summary, three new [XC(O)NH]P(O)[N(CH2C6H5)2]2 phosphoric triamides (X = CClF2, 3-F-C6H4 and 3,5-F2-C6H3) were studied by X-ray crystallography and compared with analogous compounds deposited in the CSD. In the C(O)NHP(O) fragment of these compounds, the P—N bond is longer and the O—P—N angle is contracted compared with the two remaining P—N bonds and O—P—N angles. For compounds having a C(O)NHP(O)[N]2 fragment, the geometry of the tertiary N atoms was also examined. Among the three angles around these atoms, the C—N—C angles in all reported structures have significantly lower values than do the two P—N—C angles. The sums of the bond angles at the tertiary N atoms have been used to evaluate their pyramidality. An anti orientation of the lone electron pair of the more pyramidal N atom relative to P═O is observed for compounds with ΔSUM (= SUM1 - SUM2) ranging from 14.3 to 5.9°.