Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111042454/eg3076sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111042454/eg3076IIasup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111042454/eg3076IIbsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111042454/eg3076IIcsup4.hkl |
CCDC references: 855972; 855973; 855974
For related literature, see: Grossmann et al. (2003); Jones et al. (1999); Kishikawa et al. (1997); Schwarzer & Weber (2008); Schwarzer et al. (2010); Srivastava et al. (1991); Sun et al. (1999); Verma & Singh (1976, 1978); Weber et al. (1991).
The starting N-phenylmaleimides (Ia)–(Ic) (see Scheme) were prepared as described by Schwarzer & Weber (2008). The title compounds (IIa)–(IIc) were synthesized in a similiar manner to the fulvene adducts described by Schwarzer et al. (2010). To a stirred solution of the respective N-phenylmaleimide (Ia)–(Ic) (10 mmol) in benzene (25 ml), a solution of anthracene (10 mmol) in benzene (25 ml) was added. The mixture was heated to reflux for 5 h and allowed to cool to room temperature. The solid precipitate that formed was collected and dried in vacuum. Recrystallization of the crude products from acetone yielded the pure compounds as colourless solids. Single crystals of compounds (IIa)–(IIc) were obtained from benzene solutions.
Data for (IIa): yield 2.46 g (63%). Analysis calculated for C24H15F2NO2: C 74.41, H 3.90, N 3.62%; found: C 74.52, H 4.17, N 3.67%. IR (KBr): νmax (cm-1) 3076 (CHAr), 1781, 1709 (C═O), 1621, 1610 (C═CAr), 1372, 1181 (C—N—C), 1285 (CArF). 1H NMR (CDCl3): δ 7.44–7.21 (m, 8H, Ar—H), 6.74 (m, 1H, H-1), 6.14 (m, 2H, Ar—H), 4.88 (s, 2H, H-6), 3.38 (s, 2H, H-5); 13C NMR (CDCl3): δ 175.27 (C═O), 163.93, 161.45 (d, 1JC–F = -249.5 Hz, C-2), 141.04, 138.60 (C-7a, C-7b), 133.25 (C-4), 127.33, 126.98 (C-9a, C-9b), 125.12, 124.38 (C-8a, C-8b), 110.12 (d, 2JC–F = 27.8 Hz, C-3), 104.42 (t, 2JC–F = 25.4 Hz, C-1), 47.04 (C-6), 45.91 (C-5). MS: m/e 387 [M]+, 209, 178 (100), 101.
Data for (IIb): yield 2.93 g (72%). Analysis calculated for C24H14F3NO2: C 71.11, H 3.48, N 3.46%; found: C 71.40, H 3.72, N 3.37%. IR (KBr): νmax (cm-1) 3068 (CHAr), 1786, 1722 (C═O), 1608, 1522 (C═CAr), 1357, 1186 (C—N—C), 1205 (CArF). 1H NMR (CDCl3): δ 7.47–7.16 (m, 8H, Ar—H), 6.68, 6.56 (s, 2H, H-2, H-2'), 6.14 (m, 2H, Ar—H), 4.87 (s, 2H, H-6), 3.43 (s, 2H, H-5); 13C NMR (CDCl3): δ 174.25 (C═O), 164.13, 161.61 (d, 1JC–F = -253.5 Hz, C-1), 159.67, 157.10 (d, 1JC–F = -258.5 Hz, C-3), 141.45, 138.29 (C-7a, C-7b), 127.29, 126.83 (C-9a, C-9b), 125.12, 124.25 (C-8a, C-8b), 105.44 (t, 2JC–F = 17.5, C-4), 100.98 (m, C-2), 47.38 (C-6), 45.34 (C-5). MS: m/e 405 [M]+, 202, 178 (100), 101.
Data for (IIc): yield 2.81 g (64%). Analysis calculated for C24H12F5NO2: C 65.31, H 2.74, N 3.17%; found: C 65.49, H 2.96, N 3.03%. IR (KBr): νmax (cm-1) 3079 (CHAr), 1797, 1729 (C═O), 1626, 1528 (C═CAr), 1372, 1186 (C—N—C), 1259 (CArF). 1H NMR (CDCl3): δ 7.41–7.18 (m, 8H, Ar—H), 4.87 (s, 2H, H-6, s), 3.45 (s, 2H, H-5); 13C NMR (CDCl3): δ 173.95 (C═O), 144.56, 141.99 (d, 1JC–F = - 258.5 Hz, C-3), 143.42, 140.86 (d, 1JC–F = -257.5 Hz, C-1), 141.30, 138.21 (C-7a, C-7b), 139.02, 136.51 (t, 1JC—F = -252.5 Hz, C-2), 127.56, 127.03 (C-9a, C-9b), 125.21, 124.37 (C-8a, C-8b), 106.66 (t, 2JC–F = 16.1 Hz, C-4), 47.63 (C-6), 45.62 (C-5). MS: m/e 441 [M]+, 202, 178 (100), 101.
For compounds (IIa)–(IIc), H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95–1.00 Å and Uiso(H) = 1.2–1.5 Ueq(parent atom). The inferior crystal quality for compound (IIc) is also reflected in a high Rint value.
For all compounds, data collection: SMART (Bruker, 2007); cell refinement: SMART (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
C24H15F2NO2 | F(000) = 800 |
Mr = 387.37 | Dx = 1.475 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 18.229 (2) Å | Cell parameters from 5782 reflections |
b = 11.7659 (13) Å | θ = 2.2–31.4° |
c = 8.1599 (10) Å | µ = 0.11 mm−1 |
β = 94.852 (4)° | T = 93 K |
V = 1743.9 (4) Å3 | Splitter, colourless |
Z = 4 | 0.40 × 0.23 × 0.23 mm |
Bruker SMART CCD area-detector diffractometer | 2714 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Graphite monochromator | θmax = 25.0°, θmin = 2.1° |
ϕ and ω scans | h = −21→21 |
16554 measured reflections | k = −13→13 |
3043 independent reflections | l = −9→9 |
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) = 0.112 | H-atom parameters constrained |
S = 1.18 | w = 1/[σ2(Fo2) + (0.0212P)2 + 2.9969P] where P = (Fo2 + 2Fc2)/3 |
3043 reflections | (Δ/σ)max < 0.001 |
262 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C24H15F2NO2 | V = 1743.9 (4) Å3 |
Mr = 387.37 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 18.229 (2) Å | µ = 0.11 mm−1 |
b = 11.7659 (13) Å | T = 93 K |
c = 8.1599 (10) Å | 0.40 × 0.23 × 0.23 mm |
β = 94.852 (4)° |
Bruker SMART CCD area-detector diffractometer | 2714 reflections with I > 2σ(I) |
16554 measured reflections | Rint = 0.032 |
3043 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.18 | Δρmax = 0.27 e Å−3 |
3043 reflections | Δρmin = −0.21 e Å−3 |
262 parameters |
Experimental. Data for (IIa): yield 2.46 g (63%). Analysis calculated for C24H15F2NO2: C 74.41, H 3.90, N 3.62%; found: C 74.52, H 4.17, N 3.67%. IR (KBr): νmax (cm-1) 3076 (CHAr), 1781, 1709 (C═O), 1621, 1610 (C═CAr), 1372, 1181 (C—N—C), 1285 (CArF). 1H NMR (CDCl3): δ 7.44–7.21 (m, 8H, Ar—H), 6.74 (m, 1H, H-1), 6.14 (m, 2H, Ar—H), 4.88 (s, 2H, H-6), 3.38 (s, 2H, H-5); 13C NMR (CDCl3): δ 175.27 (C═O), 163.93, 161.45 (d, 1JC–F = -249.5 Hz, C-2), 141.04, 138.60 (C-7a, C-7b), 133.25 (C-4), 127.33, 126.98 (C-9a, C-9b), 125.12, 124.38 (C-8a, C-8b), 110.12 (d, 2JC–F = 27.8 Hz, C-3), 104.42 (t, 2JC–F = 25.4 Hz, C-1), 47.04 (C-6), 45.91 (C-5). MS: m/e 387 [M]+, 209, 178 (100), 101. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 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. H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95–0.98 Å and Uiso(H) = 1.2–1.5 Ueq(parent atom). |
x | y | z | Uiso*/Ueq | ||
O1 | 0.22080 (9) | 0.23466 (14) | 0.4012 (2) | 0.0188 (4) | |
O2 | 0.34559 (9) | 0.48851 (14) | 0.1009 (2) | 0.0187 (4) | |
N1 | 0.29850 (10) | 0.34778 (17) | 0.2611 (2) | 0.0142 (4) | |
F1 | 0.44912 (8) | 0.01525 (12) | 0.3063 (2) | 0.0284 (4) | |
F2 | 0.54170 (8) | 0.35828 (13) | 0.53401 (19) | 0.0275 (4) | |
C1 | 0.37474 (13) | 0.1780 (2) | 0.2833 (3) | 0.0177 (5) | |
H1 | 0.3363 | 0.1359 | 0.2257 | 0.021* | |
C2 | 0.44046 (13) | 0.1271 (2) | 0.3382 (3) | 0.0193 (5) | |
C3 | 0.49801 (13) | 0.1849 (2) | 0.4217 (3) | 0.0209 (5) | |
H3 | 0.5428 | 0.1481 | 0.4581 | 0.025* | |
C4 | 0.48682 (13) | 0.2988 (2) | 0.4492 (3) | 0.0196 (5) | |
C5 | 0.42280 (13) | 0.3561 (2) | 0.3980 (3) | 0.0184 (5) | |
H5 | 0.4173 | 0.4350 | 0.4186 | 0.022* | |
C6 | 0.36683 (12) | 0.2932 (2) | 0.3150 (3) | 0.0142 (5) | |
C7 | 0.23006 (12) | 0.3128 (2) | 0.3080 (3) | 0.0144 (5) | |
C8 | 0.17085 (12) | 0.3902 (2) | 0.2262 (3) | 0.0145 (5) | |
H8 | 0.1356 | 0.3450 | 0.1515 | 0.017* | |
C9 | 0.21323 (12) | 0.47515 (19) | 0.1256 (3) | 0.0138 (5) | |
H9 | 0.1963 | 0.4692 | 0.0061 | 0.017* | |
C10 | 0.29345 (12) | 0.4418 (2) | 0.1540 (3) | 0.0136 (5) | |
C11 | 0.12817 (12) | 0.4557 (2) | 0.3567 (3) | 0.0146 (5) | |
H11 | 0.0994 | 0.4033 | 0.4233 | 0.018* | |
C12 | 0.07913 (13) | 0.5402 (2) | 0.2585 (3) | 0.0151 (5) | |
C13 | 0.00274 (13) | 0.5441 (2) | 0.2488 (3) | 0.0170 (5) | |
H13 | −0.0242 | 0.4917 | 0.3089 | 0.020* | |
C14 | −0.03395 (13) | 0.6267 (2) | 0.1491 (3) | 0.0191 (5) | |
H14 | −0.0862 | 0.6307 | 0.1423 | 0.023* | |
C15 | 0.00538 (13) | 0.7027 (2) | 0.0600 (3) | 0.0193 (5) | |
H15 | −0.0202 | 0.7580 | −0.0076 | 0.023* | |
C16 | 0.08209 (13) | 0.6985 (2) | 0.0689 (3) | 0.0170 (5) | |
H16 | 0.1089 | 0.7502 | 0.0074 | 0.020* | |
C17 | 0.11857 (13) | 0.6176 (2) | 0.1689 (3) | 0.0144 (5) | |
C18 | 0.20136 (12) | 0.5988 (2) | 0.1886 (3) | 0.0142 (5) | |
H18 | 0.2286 | 0.6566 | 0.1274 | 0.017* | |
C19 | 0.22644 (13) | 0.59681 (19) | 0.3713 (3) | 0.0145 (5) | |
C20 | 0.28687 (12) | 0.6542 (2) | 0.4460 (3) | 0.0152 (5) | |
H20 | 0.3150 | 0.7035 | 0.3837 | 0.018* | |
C21 | 0.30578 (13) | 0.6385 (2) | 0.6141 (3) | 0.0181 (5) | |
H21 | 0.3472 | 0.6772 | 0.6661 | 0.022* | |
C22 | 0.26451 (13) | 0.5669 (2) | 0.7059 (3) | 0.0182 (5) | |
H22 | 0.2767 | 0.5588 | 0.8208 | 0.022* | |
C23 | 0.20508 (13) | 0.5067 (2) | 0.6292 (3) | 0.0168 (5) | |
H23 | 0.1776 | 0.4562 | 0.6912 | 0.020* | |
C24 | 0.18627 (12) | 0.5211 (2) | 0.4619 (3) | 0.0142 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0173 (9) | 0.0177 (9) | 0.0218 (9) | −0.0009 (7) | 0.0028 (7) | 0.0058 (7) |
O2 | 0.0164 (9) | 0.0201 (9) | 0.0204 (9) | 0.0004 (7) | 0.0055 (7) | 0.0027 (7) |
N1 | 0.0123 (10) | 0.0143 (10) | 0.0157 (10) | −0.0008 (8) | 0.0009 (8) | 0.0000 (8) |
F1 | 0.0268 (8) | 0.0179 (8) | 0.0407 (9) | 0.0073 (6) | 0.0035 (7) | 0.0005 (7) |
F2 | 0.0153 (7) | 0.0337 (9) | 0.0324 (9) | −0.0035 (6) | −0.0053 (6) | −0.0024 (7) |
C1 | 0.0163 (12) | 0.0195 (13) | 0.0176 (12) | −0.0014 (10) | 0.0031 (9) | −0.0010 (10) |
C2 | 0.0204 (13) | 0.0151 (13) | 0.0231 (13) | 0.0031 (10) | 0.0061 (10) | 0.0041 (10) |
C3 | 0.0144 (12) | 0.0266 (14) | 0.0218 (13) | 0.0044 (10) | 0.0028 (10) | 0.0050 (11) |
C4 | 0.0129 (12) | 0.0278 (14) | 0.0179 (12) | −0.0042 (10) | 0.0003 (9) | −0.0003 (10) |
C5 | 0.0186 (12) | 0.0179 (13) | 0.0192 (12) | −0.0001 (10) | 0.0038 (9) | −0.0001 (10) |
C6 | 0.0125 (11) | 0.0161 (12) | 0.0146 (12) | 0.0010 (9) | 0.0039 (9) | 0.0031 (9) |
C7 | 0.0123 (11) | 0.0145 (12) | 0.0162 (12) | −0.0005 (9) | 0.0015 (9) | −0.0021 (10) |
C8 | 0.0132 (11) | 0.0154 (12) | 0.0149 (11) | −0.0017 (9) | 0.0017 (9) | −0.0003 (9) |
C9 | 0.0137 (11) | 0.0154 (12) | 0.0123 (11) | −0.0014 (9) | 0.0008 (9) | −0.0004 (9) |
C10 | 0.0154 (12) | 0.0153 (12) | 0.0099 (11) | −0.0009 (9) | 0.0004 (9) | −0.0035 (9) |
C11 | 0.0127 (11) | 0.0166 (12) | 0.0149 (11) | 0.0014 (9) | 0.0034 (9) | 0.0027 (9) |
C12 | 0.0153 (12) | 0.0168 (12) | 0.0133 (11) | −0.0003 (9) | 0.0015 (9) | −0.0024 (9) |
C13 | 0.0141 (12) | 0.0206 (13) | 0.0168 (12) | −0.0008 (10) | 0.0039 (9) | −0.0021 (10) |
C14 | 0.0134 (12) | 0.0253 (14) | 0.0184 (12) | 0.0031 (10) | 0.0004 (9) | −0.0015 (10) |
C15 | 0.0199 (13) | 0.0199 (13) | 0.0174 (12) | 0.0050 (10) | −0.0018 (10) | −0.0006 (10) |
C16 | 0.0192 (12) | 0.0167 (12) | 0.0151 (12) | 0.0000 (10) | 0.0011 (9) | 0.0001 (9) |
C17 | 0.0146 (11) | 0.0153 (12) | 0.0132 (11) | 0.0017 (9) | −0.0001 (9) | −0.0013 (9) |
C18 | 0.0142 (12) | 0.0144 (12) | 0.0140 (11) | −0.0003 (9) | 0.0017 (9) | 0.0032 (9) |
C19 | 0.0153 (12) | 0.0126 (12) | 0.0157 (12) | 0.0042 (9) | 0.0026 (9) | −0.0007 (9) |
C20 | 0.0137 (11) | 0.0150 (12) | 0.0172 (12) | 0.0017 (9) | 0.0026 (9) | 0.0006 (9) |
C21 | 0.0162 (12) | 0.0177 (13) | 0.0202 (12) | 0.0023 (10) | −0.0006 (9) | −0.0042 (10) |
C22 | 0.0208 (12) | 0.0216 (13) | 0.0123 (11) | 0.0042 (10) | 0.0013 (9) | −0.0006 (10) |
C23 | 0.0165 (12) | 0.0178 (12) | 0.0166 (12) | 0.0041 (10) | 0.0049 (9) | 0.0029 (10) |
C24 | 0.0120 (11) | 0.0150 (12) | 0.0158 (12) | 0.0027 (9) | 0.0028 (9) | −0.0013 (9) |
O1—C7 | 1.214 (3) | C11—H11 | 1.0000 |
O2—C10 | 1.210 (3) | C12—C13 | 1.389 (3) |
N1—C7 | 1.398 (3) | C12—C17 | 1.404 (3) |
N1—C10 | 1.408 (3) | C13—C14 | 1.400 (3) |
N1—C6 | 1.437 (3) | C13—H13 | 0.9500 |
F1—C2 | 1.353 (3) | C14—C15 | 1.389 (4) |
F2—C4 | 1.361 (3) | C14—H14 | 0.9500 |
C1—C2 | 1.380 (3) | C15—C16 | 1.395 (3) |
C1—C6 | 1.389 (3) | C15—H15 | 0.9500 |
C1—H1 | 0.9500 | C16—C17 | 1.386 (3) |
C2—C3 | 1.380 (4) | C16—H16 | 0.9500 |
C3—C4 | 1.377 (4) | C17—C18 | 1.520 (3) |
C3—H3 | 0.9500 | C18—C19 | 1.522 (3) |
C4—C5 | 1.382 (3) | C18—H18 | 1.0000 |
C5—C6 | 1.390 (3) | C19—C20 | 1.388 (3) |
C5—H5 | 0.9500 | C19—C24 | 1.403 (3) |
C7—C8 | 1.522 (3) | C20—C21 | 1.398 (3) |
C8—C9 | 1.542 (3) | C20—H20 | 0.9500 |
C8—C11 | 1.573 (3) | C21—C22 | 1.390 (3) |
C8—H8 | 1.0000 | C21—H21 | 0.9500 |
C9—C10 | 1.513 (3) | C22—C23 | 1.397 (3) |
C9—C18 | 1.564 (3) | C22—H22 | 0.9500 |
C9—H9 | 1.0000 | C23—C24 | 1.389 (3) |
C11—C24 | 1.516 (3) | C23—H23 | 0.9500 |
C11—C12 | 1.519 (3) | ||
C7—N1—C10 | 112.86 (19) | C8—C11—H11 | 112.2 |
C7—N1—C6 | 123.72 (19) | C13—C12—C17 | 120.3 (2) |
C10—N1—C6 | 123.41 (19) | C13—C12—C11 | 126.5 (2) |
C2—C1—C6 | 117.6 (2) | C17—C12—C11 | 113.3 (2) |
C2—C1—H1 | 121.2 | C12—C13—C14 | 118.9 (2) |
C6—C1—H1 | 121.2 | C12—C13—H13 | 120.5 |
F1—C2—C1 | 118.2 (2) | C14—C13—H13 | 120.5 |
F1—C2—C3 | 118.5 (2) | C15—C14—C13 | 120.5 (2) |
C1—C2—C3 | 123.3 (2) | C15—C14—H14 | 119.7 |
C4—C3—C2 | 116.3 (2) | C13—C14—H14 | 119.7 |
C4—C3—H3 | 121.9 | C14—C15—C16 | 120.6 (2) |
C2—C3—H3 | 121.9 | C14—C15—H15 | 119.7 |
F2—C4—C3 | 118.1 (2) | C16—C15—H15 | 119.7 |
F2—C4—C5 | 117.9 (2) | C17—C16—C15 | 118.9 (2) |
C3—C4—C5 | 124.0 (2) | C17—C16—H16 | 120.5 |
C4—C5—C6 | 117.0 (2) | C15—C16—H16 | 120.5 |
C4—C5—H5 | 121.5 | C16—C17—C12 | 120.7 (2) |
C6—C5—H5 | 121.5 | C16—C17—C18 | 125.8 (2) |
C1—C6—C5 | 121.8 (2) | C12—C17—C18 | 113.4 (2) |
C1—C6—N1 | 118.7 (2) | C17—C18—C19 | 108.62 (18) |
C5—C6—N1 | 119.5 (2) | C17—C18—C9 | 105.31 (18) |
O1—C7—N1 | 124.7 (2) | C19—C18—C9 | 105.61 (18) |
O1—C7—C8 | 126.6 (2) | C17—C18—H18 | 112.3 |
N1—C7—C8 | 108.66 (19) | C19—C18—H18 | 112.3 |
C7—C8—C9 | 104.64 (18) | C9—C18—H18 | 112.3 |
C7—C8—C11 | 111.70 (18) | C20—C19—C24 | 120.5 (2) |
C9—C8—C11 | 109.95 (18) | C20—C19—C18 | 125.7 (2) |
C7—C8—H8 | 110.1 | C24—C19—C18 | 113.5 (2) |
C9—C8—H8 | 110.1 | C19—C20—C21 | 119.2 (2) |
C11—C8—H8 | 110.1 | C19—C20—H20 | 120.4 |
C10—C9—C8 | 105.75 (18) | C21—C20—H20 | 120.4 |
C10—C9—C18 | 110.48 (18) | C22—C21—C20 | 120.6 (2) |
C8—C9—C18 | 109.80 (18) | C22—C21—H21 | 119.7 |
C10—C9—H9 | 110.2 | C20—C21—H21 | 119.7 |
C8—C9—H9 | 110.2 | C21—C22—C23 | 120.0 (2) |
C18—C9—H9 | 110.2 | C21—C22—H22 | 120.0 |
O2—C10—N1 | 124.6 (2) | C23—C22—H22 | 120.0 |
O2—C10—C9 | 127.3 (2) | C24—C23—C22 | 119.7 (2) |
N1—C10—C9 | 108.09 (19) | C24—C23—H23 | 120.1 |
C24—C11—C12 | 108.57 (19) | C22—C23—H23 | 120.1 |
C24—C11—C8 | 105.69 (18) | C23—C24—C19 | 119.9 (2) |
C12—C11—C8 | 105.46 (18) | C23—C24—C11 | 126.7 (2) |
C24—C11—H11 | 112.2 | C19—C24—C11 | 113.2 (2) |
C12—C11—H11 | 112.2 | ||
C6—C1—C2—F1 | −179.2 (2) | C8—C11—C12—C13 | 118.6 (2) |
C6—C1—C2—C3 | −0.3 (4) | C24—C11—C12—C17 | 53.0 (2) |
F1—C2—C3—C4 | 179.2 (2) | C8—C11—C12—C17 | −59.9 (2) |
C1—C2—C3—C4 | 0.2 (4) | C17—C12—C13—C14 | −0.2 (3) |
C2—C3—C4—F2 | 178.7 (2) | C11—C12—C13—C14 | −178.6 (2) |
C2—C3—C4—C5 | −0.3 (4) | C12—C13—C14—C15 | 0.6 (4) |
F2—C4—C5—C6 | −178.5 (2) | C13—C14—C15—C16 | −0.3 (4) |
C3—C4—C5—C6 | 0.5 (4) | C14—C15—C16—C17 | −0.4 (4) |
C2—C1—C6—C5 | 0.5 (4) | C15—C16—C17—C12 | 0.7 (3) |
C2—C1—C6—N1 | −179.1 (2) | C15—C16—C17—C18 | 177.9 (2) |
C4—C5—C6—C1 | −0.5 (3) | C13—C12—C17—C16 | −0.4 (3) |
C4—C5—C6—N1 | 179.0 (2) | C11—C12—C17—C16 | 178.2 (2) |
C7—N1—C6—C1 | 57.4 (3) | C13—C12—C17—C18 | −177.9 (2) |
C10—N1—C6—C1 | −122.0 (2) | C11—C12—C17—C18 | 0.6 (3) |
C7—N1—C6—C5 | −122.2 (2) | C16—C17—C18—C19 | 129.6 (2) |
C10—N1—C6—C5 | 58.4 (3) | C12—C17—C18—C19 | −53.0 (3) |
C10—N1—C7—O1 | −178.9 (2) | C16—C17—C18—C9 | −117.7 (2) |
C6—N1—C7—O1 | 1.6 (4) | C12—C17—C18—C9 | 59.7 (2) |
C10—N1—C7—C8 | −0.3 (3) | C10—C9—C18—C17 | −174.61 (18) |
C6—N1—C7—C8 | −179.70 (19) | C8—C9—C18—C17 | −58.4 (2) |
O1—C7—C8—C9 | 178.6 (2) | C10—C9—C18—C19 | −59.8 (2) |
N1—C7—C8—C9 | −0.1 (2) | C8—C9—C18—C19 | 56.5 (2) |
O1—C7—C8—C11 | 59.6 (3) | C17—C18—C19—C20 | −133.8 (2) |
N1—C7—C8—C11 | −119.0 (2) | C9—C18—C19—C20 | 113.6 (2) |
C7—C8—C9—C10 | 0.3 (2) | C17—C18—C19—C24 | 51.8 (3) |
C11—C8—C9—C10 | 120.43 (19) | C9—C18—C19—C24 | −60.7 (2) |
C7—C8—C9—C18 | −118.87 (19) | C24—C19—C20—C21 | −2.1 (3) |
C11—C8—C9—C18 | 1.2 (2) | C18—C19—C20—C21 | −176.1 (2) |
C7—N1—C10—O2 | 178.0 (2) | C19—C20—C21—C22 | −0.3 (3) |
C6—N1—C10—O2 | −2.6 (3) | C20—C21—C22—C23 | 2.2 (4) |
C7—N1—C10—C9 | 0.5 (2) | C21—C22—C23—C24 | −1.7 (4) |
C6—N1—C10—C9 | 179.93 (19) | C22—C23—C24—C19 | −0.7 (3) |
C8—C9—C10—O2 | −177.9 (2) | C22—C23—C24—C11 | 174.3 (2) |
C18—C9—C10—O2 | −59.1 (3) | C20—C19—C24—C23 | 2.6 (3) |
C8—C9—C10—N1 | −0.5 (2) | C18—C19—C24—C23 | 177.3 (2) |
C18—C9—C10—N1 | 118.3 (2) | C20—C19—C24—C11 | −173.0 (2) |
C7—C8—C11—C24 | 57.5 (2) | C18—C19—C24—C11 | 1.6 (3) |
C9—C8—C11—C24 | −58.2 (2) | C12—C11—C24—C23 | 130.4 (2) |
C7—C8—C11—C12 | 172.43 (19) | C8—C11—C24—C23 | −116.8 (2) |
C9—C8—C11—C12 | 56.7 (2) | C12—C11—C24—C19 | −54.2 (2) |
C24—C11—C12—C13 | −128.5 (2) | C8—C11—C24—C19 | 58.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22···O2i | 0.95 | 2.65 | 3.552 (3) | 160 |
C5—H5···F2ii | 0.95 | 2.56 | 3.458 (3) | 157 |
C9—H9···O1iii | 1.00 | 2.60 | 3.084 (3) | 110 |
Symmetry codes: (i) x, y, z+1; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z−1/2. |
C24H14F3NO2 | F(000) = 832 |
Mr = 405.36 | Dx = 1.530 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 17.687 (2) Å | Cell parameters from 7452 reflections |
b = 12.3369 (14) Å | θ = 2.3–33.3° |
c = 8.1066 (9) Å | µ = 0.12 mm−1 |
β = 95.716 (7)° | T = 90 K |
V = 1760.1 (3) Å3 | Splitter, colourless |
Z = 4 | 0.46 × 0.45 × 0.23 mm |
Bruker SMART CCD area-detector diffractometer | 4058 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.036 |
Graphite monochromator | θmax = 30.0°, θmin = 2.3° |
ϕ and ω scans | h = −24→24 |
26961 measured reflections | k = −17→17 |
5138 independent reflections | l = −11→11 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0549P)2 + 0.7101P] where P = (Fo2 + 2Fc2)/3 |
5138 reflections | (Δ/σ)max = 0.002 |
271 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C24H14F3NO2 | V = 1760.1 (3) Å3 |
Mr = 405.36 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 17.687 (2) Å | µ = 0.12 mm−1 |
b = 12.3369 (14) Å | T = 90 K |
c = 8.1066 (9) Å | 0.46 × 0.45 × 0.23 mm |
β = 95.716 (7)° |
Bruker SMART CCD area-detector diffractometer | 4058 reflections with I > 2σ(I) |
26961 measured reflections | Rint = 0.036 |
5138 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.46 e Å−3 |
5138 reflections | Δρmin = −0.24 e Å−3 |
271 parameters |
Experimental. Data for (IIb): yield 2.93 g (72%). Analysis calculated for C24H14F3NO2: C 71.11, H 3.48, N 3.46%; found: C 71.40, H 3.72, N 3.37%. IR (KBr): νmax (cm-1) 3068 (CHAr), 1786, 1722 (C═O), 1608, 1522 (C═CAr), 1357, 1186 (C—N—C), 1205 (CArF). 1H NMR (CDCl3): δ 7.47–7.16 (m, 8H, Ar—H), 6.68, 6.56 (s, 2H, H-2, H-2'), 6.14 (m, 2H, Ar—H), 4.87 (s, 2H, H-6), 3.43 (s, 2H, H-5); 13C NMR (CDCl3): δ 174.25 (C═O), 164.13, 161.61 (d, 1JC–F = -253.5 Hz, C-1), 159.67, 157.10 (d, 1JC–F = -258.5 Hz, C-3), 141.45, 138.29 (C-7a, C-7b), 127.29, 126.83 (C-9a, C-9b), 125.12, 124.25 (C-8a, C-8b), 105.44 (t, 2JC–F = 17.5, C-4), 100.98 (m, C-2), 47.38 (C-6), 45.34 (C-5). MS: m/e 405 [M]+, 202, 178 (100), 101. |
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. H atoms were positioned geometrically and allowed to ride on their parent atoms, with C–H = 0.95–1.00 Å and Uiso(H) = 1.2–1.5 Ueq(parent atom). |
x | y | z | Uiso*/Ueq | ||
O1 | 0.21787 (5) | 0.25185 (7) | 0.44608 (11) | 0.01599 (18) | |
O2 | 0.35278 (5) | 0.47545 (8) | 0.13620 (11) | 0.01868 (19) | |
N1 | 0.30028 (5) | 0.35162 (8) | 0.30437 (12) | 0.01185 (19) | |
F1 | 0.32643 (4) | 0.13564 (6) | 0.25230 (10) | 0.02037 (17) | |
F2 | 0.56774 (4) | 0.15184 (7) | 0.54609 (11) | 0.02304 (18) | |
F3 | 0.41634 (4) | 0.46318 (6) | 0.48709 (11) | 0.02094 (17) | |
C1 | 0.38132 (7) | 0.19152 (10) | 0.34073 (15) | 0.0138 (2) | |
C2 | 0.44715 (7) | 0.13852 (10) | 0.39948 (15) | 0.0156 (2) | |
H2 | 0.4540 | 0.0632 | 0.3815 | 0.019* | |
C3 | 0.50249 (7) | 0.20079 (10) | 0.48582 (16) | 0.0157 (2) | |
C4 | 0.49521 (7) | 0.31036 (10) | 0.51512 (16) | 0.0165 (2) | |
H4 | 0.5350 | 0.3510 | 0.5733 | 0.020* | |
C5 | 0.42724 (7) | 0.35790 (10) | 0.45562 (15) | 0.0145 (2) | |
C6 | 0.36889 (7) | 0.30081 (9) | 0.36730 (14) | 0.0124 (2) | |
C7 | 0.22883 (6) | 0.32215 (9) | 0.34774 (14) | 0.0116 (2) | |
C8 | 0.17021 (6) | 0.39429 (9) | 0.25201 (14) | 0.0112 (2) | |
H8 | 0.1338 | 0.3493 | 0.1787 | 0.013* | |
C9 | 0.21589 (7) | 0.46906 (9) | 0.14649 (14) | 0.0116 (2) | |
H9 | 0.2001 | 0.4575 | 0.0258 | 0.014* | |
C10 | 0.29776 (7) | 0.43654 (10) | 0.18793 (14) | 0.0127 (2) | |
C11 | 0.12623 (6) | 0.46439 (9) | 0.37128 (14) | 0.0112 (2) | |
H11 | 0.0952 | 0.4191 | 0.4416 | 0.013* | |
C12 | 0.07775 (7) | 0.54213 (10) | 0.26103 (14) | 0.0124 (2) | |
C13 | −0.00074 (7) | 0.54978 (10) | 0.24810 (15) | 0.0152 (2) | |
H13 | −0.0297 | 0.5024 | 0.3096 | 0.018* | |
C14 | −0.03688 (7) | 0.62825 (11) | 0.14323 (16) | 0.0179 (2) | |
H14 | −0.0906 | 0.6350 | 0.1350 | 0.021* | |
C15 | 0.00515 (7) | 0.69606 (11) | 0.05135 (16) | 0.0186 (3) | |
H15 | −0.0200 | 0.7491 | −0.0192 | 0.022* | |
C16 | 0.08394 (7) | 0.68718 (10) | 0.06147 (15) | 0.0157 (2) | |
H16 | 0.1127 | 0.7330 | −0.0028 | 0.019* | |
C17 | 0.11979 (7) | 0.61020 (10) | 0.16702 (14) | 0.0124 (2) | |
C18 | 0.20417 (6) | 0.59010 (9) | 0.19432 (14) | 0.0110 (2) | |
H18 | 0.2335 | 0.6409 | 0.1287 | 0.013* | |
C19 | 0.22812 (6) | 0.59733 (9) | 0.37837 (14) | 0.0107 (2) | |
C20 | 0.28882 (7) | 0.65648 (9) | 0.45248 (14) | 0.0128 (2) | |
H20 | 0.3180 | 0.7009 | 0.3871 | 0.015* | |
C21 | 0.30678 (7) | 0.65045 (10) | 0.62331 (15) | 0.0143 (2) | |
H21 | 0.3486 | 0.6905 | 0.6744 | 0.017* | |
C22 | 0.26395 (7) | 0.58621 (10) | 0.71941 (15) | 0.0153 (2) | |
H22 | 0.2759 | 0.5836 | 0.8362 | 0.018* | |
C23 | 0.20338 (7) | 0.52543 (10) | 0.64443 (14) | 0.0134 (2) | |
H23 | 0.1744 | 0.4807 | 0.7097 | 0.016* | |
C24 | 0.18585 (6) | 0.53078 (9) | 0.47418 (14) | 0.0112 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0151 (4) | 0.0140 (4) | 0.0187 (4) | −0.0011 (3) | 0.0010 (3) | 0.0048 (3) |
O2 | 0.0162 (4) | 0.0192 (5) | 0.0221 (5) | 0.0011 (3) | 0.0092 (3) | 0.0043 (3) |
N1 | 0.0108 (4) | 0.0109 (4) | 0.0139 (5) | 0.0009 (3) | 0.0016 (3) | 0.0012 (3) |
F1 | 0.0194 (4) | 0.0140 (4) | 0.0260 (4) | −0.0012 (3) | −0.0061 (3) | −0.0054 (3) |
F2 | 0.0156 (4) | 0.0216 (4) | 0.0304 (4) | 0.0067 (3) | −0.0050 (3) | 0.0007 (3) |
F3 | 0.0171 (4) | 0.0117 (4) | 0.0334 (4) | 0.0001 (3) | −0.0005 (3) | −0.0060 (3) |
C1 | 0.0147 (5) | 0.0124 (5) | 0.0143 (5) | −0.0017 (4) | 0.0006 (4) | −0.0013 (4) |
C2 | 0.0175 (6) | 0.0114 (5) | 0.0177 (6) | 0.0019 (4) | 0.0016 (4) | 0.0009 (4) |
C3 | 0.0125 (5) | 0.0173 (6) | 0.0174 (6) | 0.0036 (4) | 0.0016 (4) | 0.0021 (4) |
C4 | 0.0125 (5) | 0.0167 (6) | 0.0200 (6) | −0.0010 (4) | 0.0003 (4) | −0.0015 (4) |
C5 | 0.0133 (5) | 0.0108 (5) | 0.0196 (6) | −0.0003 (4) | 0.0032 (4) | −0.0012 (4) |
C6 | 0.0117 (5) | 0.0120 (5) | 0.0137 (5) | 0.0007 (4) | 0.0024 (4) | 0.0011 (4) |
C7 | 0.0123 (5) | 0.0098 (5) | 0.0127 (5) | −0.0004 (4) | 0.0006 (4) | −0.0015 (4) |
C8 | 0.0112 (5) | 0.0107 (5) | 0.0115 (5) | −0.0006 (4) | 0.0002 (4) | 0.0008 (4) |
C9 | 0.0140 (5) | 0.0111 (5) | 0.0096 (5) | 0.0004 (4) | 0.0013 (4) | 0.0006 (4) |
C10 | 0.0159 (5) | 0.0117 (5) | 0.0109 (5) | 0.0013 (4) | 0.0032 (4) | −0.0005 (4) |
C11 | 0.0102 (5) | 0.0119 (5) | 0.0117 (5) | −0.0005 (4) | 0.0016 (4) | 0.0017 (4) |
C12 | 0.0130 (5) | 0.0124 (5) | 0.0115 (5) | 0.0010 (4) | −0.0003 (4) | −0.0003 (4) |
C13 | 0.0135 (5) | 0.0172 (6) | 0.0149 (5) | 0.0005 (4) | 0.0008 (4) | −0.0006 (4) |
C14 | 0.0134 (5) | 0.0203 (6) | 0.0193 (6) | 0.0038 (5) | −0.0021 (4) | −0.0019 (5) |
C15 | 0.0196 (6) | 0.0171 (6) | 0.0179 (6) | 0.0047 (5) | −0.0041 (5) | 0.0017 (4) |
C16 | 0.0191 (6) | 0.0133 (5) | 0.0141 (5) | 0.0004 (4) | −0.0009 (4) | 0.0021 (4) |
C17 | 0.0130 (5) | 0.0124 (5) | 0.0114 (5) | 0.0014 (4) | −0.0006 (4) | −0.0008 (4) |
C18 | 0.0118 (5) | 0.0103 (5) | 0.0107 (5) | 0.0002 (4) | 0.0005 (4) | 0.0012 (4) |
C19 | 0.0117 (5) | 0.0101 (5) | 0.0103 (5) | 0.0021 (4) | 0.0011 (4) | −0.0002 (4) |
C20 | 0.0132 (5) | 0.0107 (5) | 0.0144 (5) | 0.0006 (4) | 0.0019 (4) | −0.0001 (4) |
C21 | 0.0143 (5) | 0.0132 (5) | 0.0150 (6) | 0.0008 (4) | −0.0004 (4) | −0.0037 (4) |
C22 | 0.0182 (6) | 0.0171 (6) | 0.0103 (5) | 0.0018 (5) | 0.0004 (4) | −0.0025 (4) |
C23 | 0.0146 (5) | 0.0148 (5) | 0.0112 (5) | 0.0021 (4) | 0.0027 (4) | 0.0010 (4) |
C24 | 0.0102 (5) | 0.0110 (5) | 0.0123 (5) | 0.0023 (4) | 0.0010 (4) | −0.0006 (4) |
O1—C7 | 1.2067 (15) | C11—H11 | 1.0000 |
O2—C10 | 1.1977 (15) | C12—C13 | 1.3849 (16) |
N1—C7 | 1.3933 (15) | C12—C17 | 1.3971 (17) |
N1—C10 | 1.4079 (15) | C13—C14 | 1.4002 (17) |
N1—C6 | 1.4150 (14) | C13—H13 | 0.9500 |
F1—C1 | 1.3390 (13) | C14—C15 | 1.3847 (19) |
F2—C3 | 1.3502 (14) | C14—H14 | 0.9500 |
F3—C5 | 1.3413 (14) | C15—C16 | 1.3921 (18) |
C1—C2 | 1.3782 (16) | C15—H15 | 0.9500 |
C1—C6 | 1.3864 (17) | C16—C17 | 1.3885 (16) |
C2—C3 | 1.3790 (17) | C16—H16 | 0.9500 |
C2—H2 | 0.9500 | C17—C18 | 1.5073 (16) |
C3—C4 | 1.3807 (18) | C18—C19 | 1.5125 (15) |
C4—C5 | 1.3806 (16) | C18—H18 | 1.0000 |
C4—H4 | 0.9500 | C19—C20 | 1.3847 (15) |
C5—C6 | 1.3881 (16) | C19—C24 | 1.3971 (16) |
C7—C8 | 1.5196 (15) | C20—C21 | 1.3916 (16) |
C8—C9 | 1.5404 (16) | C20—H20 | 0.9500 |
C8—C11 | 1.5613 (16) | C21—C22 | 1.3879 (18) |
C8—H8 | 1.0000 | C21—H21 | 0.9500 |
C9—C10 | 1.5079 (16) | C22—C23 | 1.3963 (16) |
C9—C18 | 1.5618 (16) | C22—H22 | 0.9500 |
C9—H9 | 1.0000 | C23—C24 | 1.3856 (16) |
C11—C12 | 1.5170 (15) | C23—H23 | 0.9500 |
C11—C24 | 1.5178 (15) | ||
C7—N1—C10 | 113.22 (10) | C8—C11—H11 | 112.3 |
C7—N1—C6 | 124.07 (10) | C13—C12—C17 | 120.11 (11) |
C10—N1—C6 | 122.69 (10) | C13—C12—C11 | 126.24 (11) |
F1—C1—C2 | 118.89 (11) | C17—C12—C11 | 113.65 (10) |
F1—C1—C6 | 117.79 (10) | C12—C13—C14 | 119.12 (12) |
C2—C1—C6 | 123.32 (11) | C12—C13—H13 | 120.4 |
C1—C2—C3 | 116.33 (11) | C14—C13—H13 | 120.4 |
C1—C2—H2 | 121.8 | C15—C14—C13 | 120.47 (11) |
C3—C2—H2 | 121.8 | C15—C14—H14 | 119.8 |
F2—C3—C4 | 117.81 (11) | C13—C14—H14 | 119.8 |
F2—C3—C2 | 118.19 (11) | C14—C15—C16 | 120.58 (11) |
C4—C3—C2 | 123.99 (11) | C14—C15—H15 | 119.7 |
C3—C4—C5 | 116.66 (11) | C16—C15—H15 | 119.7 |
C3—C4—H4 | 121.7 | C17—C16—C15 | 118.89 (12) |
C5—C4—H4 | 121.7 | C17—C16—H16 | 120.6 |
F3—C5—C4 | 118.79 (11) | C15—C16—H16 | 120.6 |
F3—C5—C6 | 118.41 (10) | C16—C17—C12 | 120.80 (11) |
C4—C5—C6 | 122.79 (11) | C16—C17—C18 | 125.99 (11) |
C1—C6—C5 | 116.89 (10) | C12—C17—C18 | 113.20 (10) |
C1—C6—N1 | 121.22 (10) | C17—C18—C19 | 108.12 (9) |
C5—C6—N1 | 121.88 (10) | C17—C18—C9 | 105.95 (9) |
O1—C7—N1 | 124.31 (11) | C19—C18—C9 | 105.68 (9) |
O1—C7—C8 | 127.73 (11) | C17—C18—H18 | 112.2 |
N1—C7—C8 | 107.95 (9) | C19—C18—H18 | 112.2 |
C7—C8—C9 | 105.39 (9) | C9—C18—H18 | 112.2 |
C7—C8—C11 | 111.40 (9) | C20—C19—C24 | 120.21 (10) |
C9—C8—C11 | 109.48 (9) | C20—C19—C18 | 126.01 (10) |
C7—C8—H8 | 110.2 | C24—C19—C18 | 113.64 (10) |
C9—C8—H8 | 110.2 | C19—C20—C21 | 119.60 (11) |
C11—C8—H8 | 110.2 | C19—C20—H20 | 120.2 |
C10—C9—C8 | 105.19 (9) | C21—C20—H20 | 120.2 |
C10—C9—C18 | 110.32 (9) | C22—C21—C20 | 120.39 (11) |
C8—C9—C18 | 110.17 (9) | C22—C21—H21 | 119.8 |
C10—C9—H9 | 110.4 | C20—C21—H21 | 119.8 |
C8—C9—H9 | 110.4 | C21—C22—C23 | 120.01 (11) |
C18—C9—H9 | 110.4 | C21—C22—H22 | 120.0 |
O2—C10—N1 | 124.08 (11) | C23—C22—H22 | 120.0 |
O2—C10—C9 | 127.66 (11) | C24—C23—C22 | 119.60 (11) |
N1—C10—C9 | 108.24 (10) | C24—C23—H23 | 120.2 |
C12—C11—C24 | 107.68 (9) | C22—C23—H23 | 120.2 |
C12—C11—C8 | 105.82 (9) | C23—C24—C19 | 120.18 (11) |
C24—C11—C8 | 106.11 (9) | C23—C24—C11 | 126.58 (11) |
C12—C11—H11 | 112.3 | C19—C24—C11 | 113.11 (10) |
C24—C11—H11 | 112.3 | ||
F1—C1—C2—C3 | 178.28 (11) | C9—C8—C11—C24 | −57.66 (11) |
C6—C1—C2—C3 | −1.19 (19) | C24—C11—C12—C13 | −126.93 (12) |
C1—C2—C3—F2 | 179.73 (11) | C8—C11—C12—C13 | 119.93 (12) |
C1—C2—C3—C4 | −0.03 (19) | C24—C11—C12—C17 | 53.04 (13) |
F2—C3—C4—C5 | −178.50 (12) | C8—C11—C12—C17 | −60.10 (12) |
C2—C3—C4—C5 | 1.3 (2) | C17—C12—C13—C14 | −1.66 (18) |
C3—C4—C5—F3 | 177.25 (11) | C11—C12—C13—C14 | 178.31 (11) |
C3—C4—C5—C6 | −1.37 (19) | C12—C13—C14—C15 | 1.15 (19) |
F1—C1—C6—C5 | −178.40 (11) | C13—C14—C15—C16 | 0.1 (2) |
C2—C1—C6—C5 | 1.08 (18) | C14—C15—C16—C17 | −0.90 (19) |
F1—C1—C6—N1 | 0.51 (17) | C15—C16—C17—C12 | 0.38 (18) |
C2—C1—C6—N1 | 180.00 (11) | C15—C16—C17—C18 | −179.49 (11) |
F3—C5—C6—C1 | −178.36 (11) | C13—C12—C17—C16 | 0.90 (18) |
C4—C5—C6—C1 | 0.27 (18) | C11—C12—C17—C16 | −179.07 (10) |
F3—C5—C6—N1 | 2.73 (18) | C13—C12—C17—C18 | −179.21 (10) |
C4—C5—C6—N1 | −178.64 (12) | C11—C12—C17—C18 | 0.83 (14) |
C7—N1—C6—C1 | 61.03 (16) | C16—C17—C18—C19 | 125.87 (12) |
C10—N1—C6—C1 | −117.69 (13) | C12—C17—C18—C19 | −54.01 (13) |
C7—N1—C6—C5 | −120.11 (13) | C16—C17—C18—C9 | −121.22 (12) |
C10—N1—C6—C5 | 61.17 (16) | C12—C17—C18—C9 | 58.90 (12) |
C10—N1—C7—O1 | −179.52 (11) | C10—C9—C18—C17 | −173.50 (9) |
C6—N1—C7—O1 | 1.65 (18) | C8—C9—C18—C17 | −57.79 (11) |
C10—N1—C7—C8 | −0.21 (13) | C10—C9—C18—C19 | −58.90 (12) |
C6—N1—C7—C8 | −179.04 (10) | C8—C9—C18—C19 | 56.80 (11) |
O1—C7—C8—C9 | 179.64 (12) | C17—C18—C19—C20 | −131.32 (12) |
N1—C7—C8—C9 | 0.36 (12) | C9—C18—C19—C20 | 115.59 (12) |
O1—C7—C8—C11 | 61.00 (15) | C17—C18—C19—C24 | 53.06 (13) |
N1—C7—C8—C11 | −118.28 (10) | C9—C18—C19—C24 | −60.03 (12) |
C7—C8—C9—C10 | −0.37 (11) | C24—C19—C20—C21 | −0.92 (17) |
C11—C8—C9—C10 | 119.55 (10) | C18—C19—C20—C21 | −176.28 (11) |
C7—C8—C9—C18 | −119.26 (10) | C19—C20—C21—C22 | −0.43 (18) |
C11—C8—C9—C18 | 0.66 (12) | C20—C21—C22—C23 | 1.29 (18) |
C7—N1—C10—O2 | 178.64 (11) | C21—C22—C23—C24 | −0.78 (18) |
C6—N1—C10—O2 | −2.52 (18) | C22—C23—C24—C19 | −0.57 (17) |
C7—N1—C10—C9 | −0.04 (13) | C22—C23—C24—C11 | 175.10 (11) |
C6—N1—C10—C9 | 178.81 (10) | C20—C19—C24—C23 | 1.43 (17) |
C8—C9—C10—O2 | −178.35 (12) | C18—C19—C24—C23 | 177.33 (10) |
C18—C9—C10—O2 | −59.57 (16) | C20—C19—C24—C11 | −174.79 (10) |
C8—C9—C10—N1 | 0.26 (12) | C18—C19—C24—C11 | 1.11 (14) |
C18—C9—C10—N1 | 119.05 (10) | C12—C11—C24—C23 | 130.14 (12) |
C7—C8—C11—C12 | 172.74 (9) | C8—C11—C24—C23 | −116.91 (12) |
C9—C8—C11—C12 | 56.57 (11) | C12—C11—C24—C19 | −53.94 (12) |
C7—C8—C11—C24 | 58.51 (11) | C8—C11—C24—C19 | 59.01 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···F3i | 0.95 | 2.51 | 3.2030 (15) | 130 |
C21—H21···F2ii | 0.95 | 2.62 | 3.3051 (14) | 129 |
C14—H14···O1iii | 0.95 | 2.70 | 3.5544 (15) | 150 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+3/2; (iii) −x, y+1/2, −z+1/2. |
C24H12F5NO2 | Dx = 1.580 Mg m−3 |
Mr = 441.35 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pccn | Cell parameters from 808 reflections |
a = 18.259 (4) Å | θ = 2.2–19.9° |
b = 24.104 (6) Å | µ = 0.14 mm−1 |
c = 8.4301 (18) Å | T = 93 K |
V = 3710.1 (14) Å3 | Needle, colourless |
Z = 8 | 0.49 × 0.07 × 0.05 mm |
F(000) = 1792 |
Bruker SMART CCD area-detector diffractometer | 1997 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.152 |
Graphite monochromator | θmax = 26.0°, θmin = 1.4° |
ϕ and ω scans | h = −22→22 |
20727 measured reflections | k = −29→24 |
3652 independent reflections | l = −9→10 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.064 | H-atom parameters constrained |
wR(F2) = 0.174 | w = 1/[σ2(Fo2) + (0.0803P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
3652 reflections | Δρmax = 0.45 e Å−3 |
290 parameters | Δρmin = −0.45 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0130 (11) |
C24H12F5NO2 | V = 3710.1 (14) Å3 |
Mr = 441.35 | Z = 8 |
Orthorhombic, Pccn | Mo Kα radiation |
a = 18.259 (4) Å | µ = 0.14 mm−1 |
b = 24.104 (6) Å | T = 93 K |
c = 8.4301 (18) Å | 0.49 × 0.07 × 0.05 mm |
Bruker SMART CCD area-detector diffractometer | 1997 reflections with I > 2σ(I) |
20727 measured reflections | Rint = 0.152 |
3652 independent reflections |
R[F2 > 2σ(F2)] = 0.064 | 0 restraints |
wR(F2) = 0.174 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.45 e Å−3 |
3652 reflections | Δρmin = −0.45 e Å−3 |
290 parameters |
Experimental. Data for (IIc): yield 2.81 g (64%). Analysis calculated for C24H12F5NO2: C 65.31, H 2.74, N 3.17%; found: C 65.49, H 2.96, N 3.03%. IR (KBr): νmax (cm-1) 3079 (CHAr), 1797, 1729 (C═O), 1626, 1528 (C═CAr), 1372, 1186 (C—N—C), 1259 (CArF). 1H NMR (CDCl3): δ 7.41–7.18 (m, 8H, Ar—H), 4.87 (s, 2H, H-6, s), 3.45 (s, 2H, H-5); 13C NMR (CDCl3): δ 173.95 (C═O), 144.56, 141.99 (d, 1JC–F = - 258.5 Hz, C-3), 143.42, 140.86 (d, 1JC–F = -257.5 Hz, C-1), 141.30, 138.21 (C-7a, C-7b), 139.02, 136.51 (t, 1JC—F = -252.5 Hz, C-2), 127.56, 127.03 (C-9a, C-9b), 125.21, 124.37 (C-8a, C-8b), 106.66 (t, 2JC–F = 16.1 Hz, C-4), 47.63 (C-6), 45.62 (C-5). MS: m/e 441 [M]+, 202, 178 (100), 101. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 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. H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95–0.98 and Uiso(H) = 1.2–1.5 Ueq(parent atom). |
x | y | z | Uiso*/Ueq | ||
O1 | 0.51398 (14) | 0.44263 (12) | 0.5471 (3) | 0.0250 (7) | |
O2 | 0.42128 (14) | 0.33349 (12) | 0.1505 (3) | 0.0237 (7) | |
N1 | 0.45758 (16) | 0.38258 (14) | 0.3737 (4) | 0.0187 (8) | |
F1 | 0.30567 (11) | 0.37739 (9) | 0.4140 (3) | 0.0260 (6) | |
F2 | 0.24363 (11) | 0.31724 (10) | 0.6489 (3) | 0.0299 (6) | |
F3 | 0.32951 (12) | 0.26414 (10) | 0.8658 (3) | 0.0294 (6) | |
F4 | 0.47869 (12) | 0.26691 (10) | 0.8363 (3) | 0.0278 (6) | |
F5 | 0.54000 (11) | 0.32218 (10) | 0.5905 (3) | 0.0263 (6) | |
C1 | 0.3490 (2) | 0.34867 (18) | 0.5142 (5) | 0.0201 (9) | |
C2 | 0.3174 (2) | 0.31911 (17) | 0.6367 (5) | 0.0215 (10) | |
C3 | 0.3605 (2) | 0.29201 (17) | 0.7452 (4) | 0.0221 (10) | |
C4 | 0.4358 (2) | 0.29375 (17) | 0.7297 (5) | 0.0217 (9) | |
C5 | 0.4666 (2) | 0.32155 (17) | 0.6050 (5) | 0.0214 (10) | |
C6 | 0.4242 (2) | 0.35059 (17) | 0.4956 (5) | 0.0208 (9) | |
C7 | 0.5015 (2) | 0.42842 (18) | 0.4111 (5) | 0.0200 (9) | |
C8 | 0.5291 (2) | 0.45356 (17) | 0.2590 (4) | 0.0196 (9) | |
H8 | 0.5082 | 0.4916 | 0.2450 | 0.023* | |
C9 | 0.50129 (19) | 0.41494 (17) | 0.1264 (4) | 0.0173 (9) | |
H9 | 0.4707 | 0.4363 | 0.0494 | 0.021* | |
C10 | 0.4547 (2) | 0.37121 (17) | 0.2100 (5) | 0.0186 (9) | |
C11 | 0.6150 (2) | 0.45643 (17) | 0.2581 (4) | 0.0202 (9) | |
H11 | 0.6345 | 0.4822 | 0.3408 | 0.024* | |
C12 | 0.63542 (19) | 0.47465 (17) | 0.0906 (5) | 0.0201 (10) | |
C13 | 0.6725 (2) | 0.52231 (18) | 0.0488 (5) | 0.0242 (10) | |
H13 | 0.6878 | 0.5479 | 0.1279 | 0.029* | |
C14 | 0.6874 (2) | 0.53252 (19) | −0.1114 (5) | 0.0261 (10) | |
H14 | 0.7128 | 0.5653 | −0.1414 | 0.031* | |
C15 | 0.6651 (2) | 0.49475 (19) | −0.2276 (5) | 0.0260 (10) | |
H15 | 0.6756 | 0.5019 | −0.3361 | 0.031* | |
C16 | 0.62765 (19) | 0.44687 (18) | −0.1848 (5) | 0.0232 (10) | |
H16 | 0.6126 | 0.4211 | −0.2638 | 0.028* | |
C17 | 0.61225 (19) | 0.43680 (17) | −0.0259 (5) | 0.0197 (9) | |
C18 | 0.56851 (19) | 0.38839 (16) | 0.0393 (5) | 0.0204 (9) | |
H18 | 0.5533 | 0.3618 | −0.0457 | 0.025* | |
C19 | 0.61386 (19) | 0.36044 (17) | 0.1681 (5) | 0.0191 (9) | |
C20 | 0.6265 (2) | 0.30408 (19) | 0.1811 (5) | 0.0263 (10) | |
H20 | 0.6075 | 0.2792 | 0.1042 | 0.032* | |
C21 | 0.6679 (2) | 0.28419 (19) | 0.3092 (5) | 0.0285 (11) | |
H21 | 0.6763 | 0.2455 | 0.3206 | 0.034* | |
C22 | 0.6965 (2) | 0.3209 (2) | 0.4191 (5) | 0.0296 (11) | |
H22 | 0.7258 | 0.3071 | 0.5036 | 0.035* | |
C23 | 0.6831 (2) | 0.37753 (19) | 0.4080 (5) | 0.0248 (10) | |
H23 | 0.7025 | 0.4024 | 0.4847 | 0.030* | |
C24 | 0.6409 (2) | 0.39716 (17) | 0.2824 (4) | 0.0196 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0317 (15) | 0.0235 (17) | 0.0197 (18) | 0.0050 (13) | −0.0021 (12) | −0.0011 (13) |
O2 | 0.0215 (14) | 0.0264 (18) | 0.0232 (17) | −0.0027 (13) | −0.0010 (12) | −0.0015 (13) |
N1 | 0.0233 (17) | 0.018 (2) | 0.0145 (19) | 0.0006 (15) | 0.0011 (13) | −0.0009 (14) |
F1 | 0.0241 (12) | 0.0303 (15) | 0.0235 (14) | 0.0048 (11) | −0.0008 (9) | 0.0035 (11) |
F2 | 0.0211 (13) | 0.0378 (17) | 0.0309 (15) | −0.0019 (11) | 0.0042 (10) | 0.0011 (12) |
F3 | 0.0325 (13) | 0.0352 (16) | 0.0204 (14) | −0.0063 (11) | 0.0052 (10) | 0.0076 (11) |
F4 | 0.0313 (13) | 0.0277 (15) | 0.0245 (14) | 0.0030 (11) | −0.0051 (10) | 0.0062 (11) |
F5 | 0.0209 (12) | 0.0303 (15) | 0.0277 (14) | 0.0021 (11) | 0.0014 (9) | 0.0045 (11) |
C1 | 0.020 (2) | 0.026 (3) | 0.014 (2) | 0.0036 (18) | −0.0030 (15) | −0.0013 (18) |
C2 | 0.020 (2) | 0.024 (3) | 0.020 (2) | 0.0010 (18) | 0.0045 (17) | −0.0034 (19) |
C3 | 0.029 (2) | 0.023 (3) | 0.014 (2) | −0.0008 (19) | 0.0037 (17) | −0.0011 (18) |
C4 | 0.028 (2) | 0.019 (2) | 0.018 (2) | 0.0000 (18) | −0.0036 (17) | −0.0039 (18) |
C5 | 0.018 (2) | 0.020 (3) | 0.026 (3) | 0.0001 (18) | 0.0047 (17) | −0.0010 (18) |
C6 | 0.026 (2) | 0.018 (2) | 0.018 (2) | −0.0006 (19) | 0.0003 (16) | −0.0018 (18) |
C7 | 0.023 (2) | 0.021 (2) | 0.016 (2) | 0.0054 (18) | −0.0008 (16) | −0.0047 (18) |
C8 | 0.025 (2) | 0.017 (2) | 0.017 (2) | 0.0023 (17) | 0.0011 (16) | 0.0001 (17) |
C9 | 0.0185 (19) | 0.019 (2) | 0.014 (2) | 0.0025 (17) | 0.0024 (15) | 0.0020 (16) |
C10 | 0.0170 (19) | 0.023 (3) | 0.016 (2) | 0.0086 (18) | 0.0002 (15) | 0.0006 (18) |
C11 | 0.022 (2) | 0.021 (2) | 0.017 (2) | −0.0012 (18) | −0.0018 (16) | −0.0025 (18) |
C12 | 0.0134 (19) | 0.027 (3) | 0.020 (2) | 0.0019 (17) | −0.0026 (16) | 0.0045 (19) |
C13 | 0.018 (2) | 0.030 (3) | 0.025 (3) | 0.0008 (19) | −0.0033 (17) | 0.001 (2) |
C14 | 0.020 (2) | 0.027 (3) | 0.031 (3) | −0.0020 (19) | −0.0008 (18) | 0.012 (2) |
C15 | 0.023 (2) | 0.040 (3) | 0.015 (2) | −0.001 (2) | −0.0002 (17) | 0.006 (2) |
C16 | 0.017 (2) | 0.032 (3) | 0.020 (2) | −0.0014 (19) | −0.0015 (16) | −0.001 (2) |
C17 | 0.0153 (18) | 0.025 (2) | 0.019 (2) | 0.0023 (17) | 0.0003 (15) | 0.0003 (18) |
C18 | 0.019 (2) | 0.023 (3) | 0.019 (2) | 0.0004 (18) | −0.0021 (16) | −0.0040 (17) |
C19 | 0.0149 (19) | 0.025 (3) | 0.017 (2) | −0.0001 (17) | 0.0040 (15) | 0.0007 (18) |
C20 | 0.020 (2) | 0.029 (3) | 0.030 (3) | 0.0028 (19) | 0.0060 (17) | 0.001 (2) |
C21 | 0.025 (2) | 0.024 (3) | 0.037 (3) | 0.003 (2) | 0.0083 (19) | 0.009 (2) |
C22 | 0.020 (2) | 0.044 (3) | 0.025 (3) | 0.008 (2) | 0.0013 (17) | 0.012 (2) |
C23 | 0.019 (2) | 0.034 (3) | 0.022 (2) | 0.0008 (19) | −0.0003 (16) | 0.001 (2) |
C24 | 0.0188 (19) | 0.022 (2) | 0.018 (2) | 0.0000 (17) | 0.0032 (16) | 0.0007 (18) |
O1—C7 | 1.218 (4) | C11—H11 | 1.0000 |
O2—C10 | 1.204 (5) | C12—C13 | 1.379 (6) |
N1—C7 | 1.402 (5) | C12—C17 | 1.406 (6) |
N1—C10 | 1.408 (5) | C13—C14 | 1.400 (6) |
N1—C6 | 1.422 (5) | C13—H13 | 0.9500 |
F1—C1 | 1.348 (4) | C14—C15 | 1.398 (6) |
F2—C2 | 1.352 (4) | C14—H14 | 0.9500 |
F3—C3 | 1.343 (4) | C15—C16 | 1.389 (6) |
F4—C4 | 1.356 (4) | C15—H15 | 0.9500 |
F5—C5 | 1.345 (4) | C16—C17 | 1.390 (5) |
C1—C2 | 1.380 (6) | C16—H16 | 0.9500 |
C1—C6 | 1.383 (5) | C17—C18 | 1.517 (5) |
C2—C3 | 1.372 (6) | C18—C19 | 1.523 (5) |
C3—C4 | 1.382 (5) | C18—H18 | 1.0000 |
C4—C5 | 1.368 (5) | C19—C20 | 1.382 (6) |
C5—C6 | 1.393 (6) | C19—C24 | 1.398 (5) |
C7—C8 | 1.505 (6) | C20—C21 | 1.403 (6) |
C8—C9 | 1.541 (5) | C20—H20 | 0.9500 |
C8—C11 | 1.568 (5) | C21—C22 | 1.383 (6) |
C8—H8 | 1.0000 | C21—H21 | 0.9500 |
C9—C10 | 1.527 (5) | C22—C23 | 1.390 (6) |
C9—C18 | 1.567 (5) | C22—H22 | 0.9500 |
C9—H9 | 1.0000 | C23—C24 | 1.393 (5) |
C11—C24 | 1.519 (6) | C23—H23 | 0.9500 |
C11—C12 | 1.525 (5) | ||
C7—N1—C10 | 113.3 (3) | C8—C11—H11 | 112.3 |
C7—N1—C6 | 120.7 (3) | C13—C12—C17 | 120.7 (4) |
C10—N1—C6 | 125.9 (3) | C13—C12—C11 | 126.6 (4) |
F1—C1—C2 | 119.3 (3) | C17—C12—C11 | 112.7 (3) |
F1—C1—C6 | 119.6 (4) | C12—C13—C14 | 119.2 (4) |
C2—C1—C6 | 121.1 (4) | C12—C13—H13 | 120.4 |
F2—C2—C3 | 120.3 (4) | C14—C13—H13 | 120.4 |
F2—C2—C1 | 119.3 (3) | C15—C14—C13 | 120.4 (4) |
C3—C2—C1 | 120.4 (4) | C15—C14—H14 | 119.8 |
F3—C3—C2 | 120.1 (3) | C13—C14—H14 | 119.8 |
F3—C3—C4 | 120.4 (4) | C16—C15—C14 | 120.1 (4) |
C2—C3—C4 | 119.5 (4) | C16—C15—H15 | 119.9 |
F4—C4—C5 | 120.3 (3) | C14—C15—H15 | 119.9 |
F4—C4—C3 | 119.8 (4) | C15—C16—C17 | 119.7 (4) |
C5—C4—C3 | 119.8 (4) | C15—C16—H16 | 120.2 |
F5—C5—C4 | 119.0 (3) | C17—C16—H16 | 120.2 |
F5—C5—C6 | 119.2 (3) | C16—C17—C12 | 119.9 (4) |
C4—C5—C6 | 121.7 (4) | C16—C17—C18 | 126.2 (4) |
C1—C6—C5 | 117.4 (4) | C12—C17—C18 | 113.9 (3) |
C1—C6—N1 | 121.7 (4) | C17—C18—C19 | 108.2 (3) |
C5—C6—N1 | 120.8 (3) | C17—C18—C9 | 105.6 (3) |
O1—C7—N1 | 122.7 (4) | C19—C18—C9 | 105.8 (3) |
O1—C7—C8 | 128.8 (4) | C17—C18—H18 | 112.3 |
N1—C7—C8 | 108.5 (3) | C19—C18—H18 | 112.3 |
C7—C8—C9 | 105.3 (3) | C9—C18—H18 | 112.3 |
C7—C8—C11 | 110.9 (3) | C20—C19—C24 | 120.6 (4) |
C9—C8—C11 | 110.6 (3) | C20—C19—C18 | 125.6 (4) |
C7—C8—H8 | 110.0 | C24—C19—C18 | 113.8 (4) |
C9—C8—H8 | 110.0 | C19—C20—C21 | 119.1 (4) |
C11—C8—H8 | 110.0 | C19—C20—H20 | 120.4 |
C10—C9—C8 | 105.4 (3) | C21—C20—H20 | 120.4 |
C10—C9—C18 | 111.8 (3) | C22—C21—C20 | 120.0 (4) |
C8—C9—C18 | 109.2 (3) | C22—C21—H21 | 120.0 |
C10—C9—H9 | 110.1 | C20—C21—H21 | 120.0 |
C8—C9—H9 | 110.1 | C21—C22—C23 | 121.1 (4) |
C18—C9—H9 | 110.1 | C21—C22—H22 | 119.5 |
O2—C10—N1 | 125.1 (4) | C23—C22—H22 | 119.5 |
O2—C10—C9 | 127.7 (4) | C22—C23—C24 | 118.8 (4) |
N1—C10—C9 | 107.3 (3) | C22—C23—H23 | 120.6 |
C24—C11—C12 | 108.7 (3) | C24—C23—H23 | 120.6 |
C24—C11—C8 | 105.6 (3) | C23—C24—C19 | 120.3 (4) |
C12—C11—C8 | 105.2 (3) | C23—C24—C11 | 126.5 (4) |
C24—C11—H11 | 112.3 | C19—C24—C11 | 113.1 (3) |
C12—C11—H11 | 112.3 | ||
F1—C1—C2—F2 | 3.3 (6) | C18—C9—C10—N1 | 116.7 (3) |
C6—C1—C2—F2 | −178.6 (4) | C7—C8—C11—C24 | 57.3 (4) |
F1—C1—C2—C3 | −176.5 (4) | C9—C8—C11—C24 | −59.2 (4) |
C6—C1—C2—C3 | 1.6 (6) | C7—C8—C11—C12 | 172.2 (3) |
F2—C2—C3—F3 | −1.0 (6) | C9—C8—C11—C12 | 55.7 (4) |
C1—C2—C3—F3 | 178.8 (4) | C24—C11—C12—C13 | −128.6 (4) |
F2—C2—C3—C4 | 179.2 (4) | C8—C11—C12—C13 | 118.7 (4) |
C1—C2—C3—C4 | −1.0 (6) | C24—C11—C12—C17 | 51.4 (4) |
F3—C3—C4—F4 | 0.4 (6) | C8—C11—C12—C17 | −61.3 (4) |
C2—C3—C4—F4 | −179.8 (4) | C17—C12—C13—C14 | −0.4 (6) |
F3—C3—C4—C5 | 179.0 (4) | C11—C12—C13—C14 | 179.5 (4) |
C2—C3—C4—C5 | −1.2 (6) | C12—C13—C14—C15 | −0.2 (6) |
F4—C4—C5—F5 | −0.5 (6) | C13—C14—C15—C16 | 0.3 (6) |
C3—C4—C5—F5 | −179.1 (3) | C14—C15—C16—C17 | 0.2 (6) |
F4—C4—C5—C6 | −178.5 (4) | C15—C16—C17—C12 | −0.8 (5) |
C3—C4—C5—C6 | 2.9 (6) | C15—C16—C17—C18 | 176.4 (4) |
F1—C1—C6—C5 | 178.1 (3) | C13—C12—C17—C16 | 0.9 (6) |
C2—C1—C6—C5 | 0.1 (6) | C11—C12—C17—C16 | −179.0 (3) |
F1—C1—C6—N1 | 0.5 (6) | C13—C12—C17—C18 | −176.7 (3) |
C2—C1—C6—N1 | −177.6 (4) | C11—C12—C17—C18 | 3.4 (4) |
F5—C5—C6—C1 | 179.7 (4) | C16—C17—C18—C19 | 127.8 (4) |
C4—C5—C6—C1 | −2.3 (6) | C12—C17—C18—C19 | −54.8 (4) |
F5—C5—C6—N1 | −2.7 (6) | C16—C17—C18—C9 | −119.3 (4) |
C4—C5—C6—N1 | 175.3 (4) | C12—C17—C18—C9 | 58.1 (4) |
C7—N1—C6—C1 | 114.3 (4) | C10—C9—C18—C17 | −175.6 (3) |
C10—N1—C6—C1 | −69.5 (5) | C8—C9—C18—C17 | −59.4 (4) |
C7—N1—C6—C5 | −63.2 (5) | C10—C9—C18—C19 | −61.1 (4) |
C10—N1—C6—C5 | 113.0 (4) | C8—C9—C18—C19 | 55.2 (4) |
C10—N1—C7—O1 | −175.7 (3) | C17—C18—C19—C20 | −131.7 (4) |
C6—N1—C7—O1 | 0.9 (6) | C9—C18—C19—C20 | 115.5 (4) |
C10—N1—C7—C8 | 3.1 (4) | C17—C18—C19—C24 | 50.9 (4) |
C6—N1—C7—C8 | 179.8 (3) | C9—C18—C19—C24 | −61.9 (4) |
O1—C7—C8—C9 | 174.8 (4) | C24—C19—C20—C21 | −1.0 (6) |
N1—C7—C8—C9 | −4.0 (4) | C18—C19—C20—C21 | −178.2 (3) |
O1—C7—C8—C11 | 55.0 (5) | C19—C20—C21—C22 | −1.1 (6) |
N1—C7—C8—C11 | −123.8 (3) | C20—C21—C22—C23 | 2.0 (6) |
C7—C8—C9—C10 | 3.4 (4) | C21—C22—C23—C24 | −0.7 (6) |
C11—C8—C9—C10 | 123.4 (3) | C22—C23—C24—C19 | −1.4 (6) |
C7—C8—C9—C18 | −116.8 (3) | C22—C23—C24—C11 | 174.3 (4) |
C11—C8—C9—C18 | 3.1 (4) | C20—C19—C24—C23 | 2.3 (6) |
C7—N1—C10—O2 | 178.9 (4) | C18—C19—C24—C23 | 179.8 (3) |
C6—N1—C10—O2 | 2.5 (6) | C20—C19—C24—C11 | −174.0 (3) |
C7—N1—C10—C9 | −0.8 (4) | C18—C19—C24—C11 | 3.5 (5) |
C6—N1—C10—C9 | −177.3 (3) | C12—C11—C24—C23 | 128.6 (4) |
C8—C9—C10—O2 | 178.5 (4) | C8—C11—C24—C23 | −118.9 (4) |
C18—C9—C10—O2 | −63.0 (5) | C12—C11—C24—C19 | −55.4 (4) |
C8—C9—C10—N1 | −1.7 (4) | C8—C11—C24—C19 | 57.0 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···O1i | 0.95 | 2.46 | 3.070 (5) | 122 |
C8—H8···O1ii | 1.00 | 2.40 | 3.091 (5) | 126 |
Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y+1, −z+1. |
Experimental details
(IIa) | (IIb) | (IIc) | |
Crystal data | |||
Chemical formula | C24H15F2NO2 | C24H14F3NO2 | C24H12F5NO2 |
Mr | 387.37 | 405.36 | 441.35 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c | Orthorhombic, Pccn |
Temperature (K) | 93 | 90 | 93 |
a, b, c (Å) | 18.229 (2), 11.7659 (13), 8.1599 (10) | 17.687 (2), 12.3369 (14), 8.1066 (9) | 18.259 (4), 24.104 (6), 8.4301 (18) |
α, β, γ (°) | 90, 94.852 (4), 90 | 90, 95.716 (7), 90 | 90, 90, 90 |
V (Å3) | 1743.9 (4) | 1760.1 (3) | 3710.1 (14) |
Z | 4 | 4 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.12 | 0.14 |
Crystal size (mm) | 0.40 × 0.23 × 0.23 | 0.46 × 0.45 × 0.23 | 0.49 × 0.07 × 0.05 |
Data collection | |||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16554, 3043, 2714 | 26961, 5138, 4058 | 20727, 3652, 1997 |
Rint | 0.032 | 0.036 | 0.152 |
(sin θ/λ)max (Å−1) | 0.595 | 0.703 | 0.617 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.112, 1.18 | 0.039, 0.106, 1.02 | 0.064, 0.174, 1.00 |
No. of reflections | 3043 | 5138 | 3652 |
No. of parameters | 262 | 271 | 290 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.21 | 0.46, −0.24 | 0.45, −0.45 |
Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22···O2i | 0.95 | 2.65 | 3.552 (3) | 159.8 |
C5—H5···F2ii | 0.95 | 2.56 | 3.458 (3) | 156.8 |
C9—H9···O1iii | 1.00 | 2.60 | 3.084 (3) | 109.8 |
Symmetry codes: (i) x, y, z+1; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···F3i | 0.95 | 2.51 | 3.2030 (15) | 129.5 |
C21—H21···F2ii | 0.95 | 2.62 | 3.3051 (14) | 129.0 |
C14—H14···O1iii | 0.95 | 2.70 | 3.5544 (15) | 150.3 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+3/2; (iii) −x, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···O1i | 0.95 | 2.46 | 3.070 (5) | 121.8 |
C8—H8···O1ii | 1.00 | 2.40 | 3.091 (5) | 125.7 |
Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y+1, −z+1. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
N-Phenyl-substituted ethanoanthracenedicarboximides with different substituents at the phenyl unit are known to form crystalline inclusion compounds with a variety of solvents (Weber et al., 1991). On the other hand, the efficiency of the photoreaction of anthracene and differently substituted maleimides as a function of the dienophile concentration has been reported (Sun et al., 1999). Moreover, anthracene-2,6-dicarboxylate derivatives modified with maleimides have been used in poly(ethylene terephthalate) copolymers (Jones et al. 1999). Investigations of the conformational environment of the selected derivatives were described by Csöregh et al. (2003), while Grossmann et al. (2003) reported NMR spectroscopic analysis of the geometric features of the ortho-substituted molecules. Verma and co-workers reported on several detailed studies on the analysis of the rotation around the Caryl—N bond in, for example, o-OMe-, o-Me-, o-Cl- and o-Br-substituted N-arylimides with dynamic and temperature-dependent NMR spectroscopy (Verma & Singh, 1976, 1978; Srivastava et al., 1991). A detailed analysis of the conformational influence of the imide ring in fluorinated N-phenylmaleimides has recently been reported by Schwarzer & Weber (2008).
We describe here the preparation of three new ethanoanthracenedicarboximides, (IIa)–(IIc), having N-phenyl substitutents with different modes of fluorine substitution (see Scheme) and report on their single-crystal X-ray structures. These pentacyclic dicarboximides were synthesized analogously to the bridged fulvene adducts described by Schwarzer et al. (2010). Attempts to achieve inclusion compounds from crystallization using different solvents were unsuccessful. Single crystals suitable for X-ray crystallography in the present study were grown from benzene solution.
Remarkably, (IIa) and (IIb) are isomorphous. Only minor differences between their packing arise due to the differences in fluorine substitution in the C1–C6 ring. Even the C—H···F contacts are comparable [C5—H5···F2 = 2.56 Å in (IIa) and C4—H4···F3 = 2.51 Å in (IIb), both along (-x+1, -y+1, -z+1)]. Similar structures with related cell parameters were also reported by Kishikawa et al. (1997), Grossmann et al. (2003) and Goh & White (2009).
The semi-rigid ethanoanthracenedicarboximido moiety of the title compounds (Fig. 1) shows the typical geometry observed in earlier studies (Weber et al., 1991; Csöregh et al., 2003) confirming the expected bond lengths and angles. The `V' shape of the dihydroanthracene moiety is a structural property best described by the angle between the phenylene rings [49.43 (8)° in (IIa), 53.24 (4)° in (IIb) and 51.47 (10)° in (IIc)]. Another feature is the angle between the imide unit and the benzene ring, describing the intramolecular attractive and repulsive forces between the carbonyl O atoms and the ortho-phenyl H or F atoms. While N-phenylmaleimides (Ia) and (Ib), as the starting compounds of the synthesis (see Scheme), show torsion angles of 52.3 (Ia) and 66.5° (Ib) according to Schwarzer & Weber (2008), the dihydroanthracene derivatives (IIa)–(IIc) exhibit torsion angles of 57.83 (7), 60.88 (4) and 66.25 (13)°, respectively.
The closest centre-to-centre distance between adjacent aryl units is 4.0871 (15) Å for (IIa) and 4.0533 (8) Å for (IIb). Hence, in (IIa) and (IIb), weak stacking interactions form zigzag chains (Fig. 2) extending along the crystallographic c axis. The angles between the stacks are 25.14° (IIa) and 24.53° (IIb). On the other hand, a centre-to-centre distance greater than 5.4 Å in the crystal packing of (IIc) indicates no relevant stacking interactions.
Several C—H···O and C—H···F contacts are found in the packings. In (IIa), two C—H···O contacts complete the chain generated by the π-stacking interactions, while one C—H···F contact forms dimers. As in the case of (IIa), the trifluorinated derivative (IIb) also does not show F···F contacts, but a bifurcated C—H···O and two C—H···F interactions generate a network structure instead of a single or zigzag chain. In contrast, in (IIc), with the maximum number of F atoms on the phenyl ring, F···F contacts [2.811 (3) Å, Θ1 = 114.9 (2)° and Θ2 = 111.2 (2)°] occur, giving rise to zigzag chains. These chains are parallel to the zigzag chain along the crystallographic c axis formed by the bifurcated C—H···O contact. In conclusion, (IIa) and (IIb) show a similar crystal packing, while differences are seen in the crystal packing of (IIc), owing to the perfluorinated N-phenyl ring.