Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807036847/nc2047sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807036847/nc2047Isup2.hkl |
CCDC reference: 663690
The starting materials were purchased from Acros and used without purification. The title compound (I) was synthesized according to the method described previously (Shou et al., 2006). IR (KBr,cm-1): 1705, 1598, 1515, 1489, 1256. 1H NMR (500 MHz, δ in p.p.m., CDCl3): 7.43–7.40 (m, 2H), 7.25–7.22 (m, 2H), 6.78–6.74 (m, 2H), 6.44–6.41 (m, 2H), 4.75 (s, br, 1H), 4.49 (d, J = 6.6 Hz, 1H), 2.72–2.70 (m, 1H), 2.42–2.39 (m, 1H), 2.34–2.31 (m, 1H), 1.98–1.89 (m, 2H), 1.88–1.85 (m, 1H), 1.75–1.63 (m, 3H). 13C NMR (125 MHz, δ in p.p.m., CDCl3): 212.7, 157.1 (d, JC—F = 234.4 Hz), 143.5, 140.8, 131.8, 129.3, 121.2, 115.7 (d, JC—F = 22.5 Hz), 114.9 (d, JC—F = 7.5 Hz), 58.7, 57.4, 42.4, 31.8, 28.1, 24.3. Melting point: 386–387 K. MS (ESI): m/z 399 ([M+Na]+). Calculated for C19H19BrFNO: C 60.65, H 5.09, N 3.72%; found: C 60.70, H 5.12, N 3.70%. The crystal used for the data collection was obtained by slow evaporation of the solvent from a saturated hexane-dichloromethane solution of I at room temperature.
The N—H H atom was located in the difference map, fixed at this position and refined as riding with Uiso(H) = 1.2Ueq(N). The C—H H atoms were placed in calculated positions, with C—H = 0.93 Å (aromatic), 0.97 Å (methylene) and 0.98 Å (methine) and were refined as riding with Uiso(H) = 1.2Ueq(C).
β-Amino carbonyl moieties are found as structural units of a number of biologically active natural products. As a part of a project on the synthesis of such compounds the crystal structure analysis was performed. In the crystal structure of the title compound (I) the dihedral angle between the phenyl rings C8—C13 and C14—C19 is 74.84 (1)°. The six-membered ring (C1—C6) is in a chair conformation. A pair of weak intermolecular N—H···O hydrogen bonds link the molecules into dimers (Fig.1 and Table 1).
For related literature, see: Shou et al. (2006).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
C19H19BrFNO | F(000) = 768 |
Mr = 376.26 | Dx = 1.448 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1759 reflections |
a = 12.6501 (14) Å | θ = 4.5–41.2° |
b = 8.2310 (9) Å | µ = 2.40 mm−1 |
c = 17.0111 (18) Å | T = 295 K |
β = 103.031 (2)° | Prismatic, colorless |
V = 1725.6 (3) Å3 | 0.37 × 0.31 × 0.17 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 3060 independent reflections |
Radiation source: fine-focus sealed tube | 1669 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.120 |
φ and ω scans | θmax = 25.1°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→15 |
Tmin = 0.450, Tmax = 0.660 | k = −9→9 |
8450 measured reflections | l = −20→20 |
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) = 0.113 | H-atom parameters constrained |
S = 0.82 | w = 1/[σ2(Fo2) + (0.0443P)2] where P = (Fo2 + 2Fc2)/3 |
3060 reflections | (Δ/σ)max < 0.001 |
208 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
C19H19BrFNO | V = 1725.6 (3) Å3 |
Mr = 376.26 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.6501 (14) Å | µ = 2.40 mm−1 |
b = 8.2310 (9) Å | T = 295 K |
c = 17.0111 (18) Å | 0.37 × 0.31 × 0.17 mm |
β = 103.031 (2)° |
Bruker SMART CCD area-detector diffractometer | 3060 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1669 reflections with I > 2σ(I) |
Tmin = 0.450, Tmax = 0.660 | Rint = 0.120 |
8450 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 0.82 | Δρmax = 0.51 e Å−3 |
3060 reflections | Δρmin = −0.38 e Å−3 |
208 parameters |
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 | ||
Br1 | 0.04416 (4) | −0.08221 (6) | 0.22974 (3) | 0.0824 (2) | |
F1 | 0.4047 (2) | −0.0544 (3) | 0.82439 (15) | 0.1046 (10) | |
N1 | 0.3694 (2) | 0.3266 (4) | 0.55354 (17) | 0.0530 (8) | |
H1 | 0.4227 | 0.3337 | 0.5347 | 0.064* | |
O1 | 0.4507 (2) | 0.7010 (3) | 0.53240 (16) | 0.0698 (8) | |
C1 | 0.3566 (3) | 0.6596 (5) | 0.5257 (2) | 0.0497 (9) | |
C2 | 0.2870 (3) | 0.7350 (5) | 0.5766 (2) | 0.0626 (11) | |
H2A | 0.3290 | 0.8137 | 0.6132 | 0.075* | |
H2B | 0.2620 | 0.6518 | 0.6085 | 0.075* | |
C3 | 0.1896 (3) | 0.8187 (6) | 0.5221 (3) | 0.0732 (12) | |
H3A | 0.1414 | 0.8591 | 0.5547 | 0.088* | |
H3B | 0.2145 | 0.9108 | 0.4956 | 0.088* | |
C4 | 0.1277 (3) | 0.7028 (5) | 0.4588 (3) | 0.0693 (12) | |
H4A | 0.0967 | 0.6162 | 0.4851 | 0.083* | |
H4B | 0.0687 | 0.7605 | 0.4236 | 0.083* | |
C5 | 0.2005 (3) | 0.6311 (5) | 0.4095 (2) | 0.0630 (11) | |
H5A | 0.2255 | 0.7171 | 0.3791 | 0.076* | |
H5B | 0.1592 | 0.5547 | 0.3711 | 0.076* | |
C6 | 0.3002 (3) | 0.5429 (4) | 0.4614 (2) | 0.0480 (9) | |
H6 | 0.3501 | 0.5158 | 0.4269 | 0.058* | |
C7 | 0.2709 (3) | 0.3845 (4) | 0.5007 (2) | 0.0470 (9) | |
H7 | 0.2194 | 0.4120 | 0.5339 | 0.056* | |
C8 | 0.2161 (3) | 0.2645 (4) | 0.4365 (2) | 0.0477 (9) | |
C9 | 0.2742 (3) | 0.1833 (5) | 0.3891 (2) | 0.0598 (11) | |
H9 | 0.3489 | 0.1980 | 0.3986 | 0.072* | |
C10 | 0.2239 (3) | 0.0810 (5) | 0.3282 (2) | 0.0630 (11) | |
H10 | 0.2642 | 0.0292 | 0.2961 | 0.076* | |
C11 | 0.1146 (3) | 0.0558 (5) | 0.3149 (2) | 0.0566 (10) | |
C12 | 0.0553 (3) | 0.1319 (5) | 0.3614 (2) | 0.0636 (11) | |
H12 | −0.0192 | 0.1156 | 0.3519 | 0.076* | |
C13 | 0.1063 (3) | 0.2331 (5) | 0.4227 (2) | 0.0598 (11) | |
H13 | 0.0658 | 0.2816 | 0.4557 | 0.072* | |
C14 | 0.3719 (3) | 0.2214 (4) | 0.6170 (2) | 0.0466 (9) | |
C15 | 0.2835 (3) | 0.1887 (5) | 0.6498 (2) | 0.0568 (10) | |
H15 | 0.2157 | 0.2295 | 0.6247 | 0.068* | |
C16 | 0.2939 (3) | 0.0961 (5) | 0.7196 (2) | 0.0657 (11) | |
H16 | 0.2345 | 0.0783 | 0.7422 | 0.079* | |
C17 | 0.3928 (4) | 0.0321 (5) | 0.7540 (2) | 0.0668 (12) | |
C18 | 0.4799 (3) | 0.0540 (5) | 0.7218 (3) | 0.0689 (12) | |
H18 | 0.5463 | 0.0074 | 0.7458 | 0.083* | |
C19 | 0.4693 (3) | 0.1465 (5) | 0.6528 (2) | 0.0621 (11) | |
H19 | 0.5288 | 0.1591 | 0.6297 | 0.074* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0878 (4) | 0.0778 (4) | 0.0732 (4) | −0.0049 (3) | 0.0003 (3) | −0.0205 (2) |
F1 | 0.1045 (19) | 0.124 (2) | 0.0783 (18) | −0.0166 (17) | 0.0050 (15) | 0.0468 (17) |
N1 | 0.0448 (17) | 0.063 (2) | 0.0512 (18) | 0.0024 (16) | 0.0108 (15) | 0.0142 (17) |
O1 | 0.0537 (17) | 0.077 (2) | 0.0808 (19) | −0.0162 (15) | 0.0184 (15) | −0.0109 (16) |
C1 | 0.053 (2) | 0.053 (2) | 0.042 (2) | 0.000 (2) | 0.0104 (19) | 0.0009 (18) |
C2 | 0.070 (3) | 0.062 (3) | 0.058 (2) | −0.009 (2) | 0.020 (2) | −0.015 (2) |
C3 | 0.061 (3) | 0.062 (3) | 0.102 (3) | 0.005 (2) | 0.028 (3) | −0.008 (3) |
C4 | 0.054 (2) | 0.062 (3) | 0.085 (3) | 0.006 (2) | 0.003 (2) | 0.006 (2) |
C5 | 0.073 (3) | 0.056 (3) | 0.051 (2) | −0.007 (2) | −0.003 (2) | 0.002 (2) |
C6 | 0.052 (2) | 0.046 (2) | 0.048 (2) | −0.0002 (18) | 0.0161 (18) | 0.0005 (18) |
C7 | 0.045 (2) | 0.050 (2) | 0.046 (2) | 0.0038 (18) | 0.0112 (18) | 0.0047 (18) |
C8 | 0.043 (2) | 0.042 (2) | 0.058 (2) | 0.0014 (18) | 0.0113 (19) | 0.0044 (18) |
C9 | 0.044 (2) | 0.068 (3) | 0.071 (3) | −0.006 (2) | 0.020 (2) | −0.010 (2) |
C10 | 0.062 (3) | 0.062 (3) | 0.070 (3) | −0.001 (2) | 0.025 (2) | −0.011 (2) |
C11 | 0.059 (3) | 0.054 (3) | 0.054 (2) | 0.000 (2) | 0.008 (2) | 0.0022 (19) |
C12 | 0.040 (2) | 0.069 (3) | 0.079 (3) | 0.002 (2) | 0.008 (2) | −0.008 (2) |
C13 | 0.047 (2) | 0.064 (3) | 0.071 (3) | 0.004 (2) | 0.018 (2) | −0.011 (2) |
C14 | 0.046 (2) | 0.045 (2) | 0.049 (2) | −0.0001 (18) | 0.0097 (19) | −0.0003 (18) |
C15 | 0.053 (2) | 0.066 (3) | 0.052 (2) | 0.006 (2) | 0.013 (2) | 0.002 (2) |
C16 | 0.069 (3) | 0.077 (3) | 0.055 (2) | −0.005 (2) | 0.023 (2) | 0.005 (2) |
C17 | 0.086 (3) | 0.062 (3) | 0.046 (2) | −0.010 (3) | 0.001 (2) | 0.011 (2) |
C18 | 0.056 (3) | 0.074 (3) | 0.072 (3) | 0.001 (2) | 0.006 (2) | 0.024 (2) |
C19 | 0.050 (2) | 0.072 (3) | 0.065 (3) | 0.002 (2) | 0.016 (2) | 0.012 (2) |
Br1—C11 | 1.898 (4) | C7—C8 | 1.519 (5) |
F1—C17 | 1.371 (4) | C7—H7 | 0.9800 |
N1—C14 | 1.378 (4) | C8—C13 | 1.379 (5) |
N1—C7 | 1.444 (4) | C8—C9 | 1.380 (5) |
N1—H1 | 0.8111 | C9—C10 | 1.375 (5) |
O1—C1 | 1.218 (4) | C9—H9 | 0.9300 |
C1—C2 | 1.501 (5) | C10—C11 | 1.366 (5) |
C1—C6 | 1.509 (5) | C10—H10 | 0.9300 |
C2—C3 | 1.529 (5) | C11—C12 | 1.359 (5) |
C2—H2A | 0.9700 | C12—C13 | 1.377 (5) |
C2—H2B | 0.9700 | C12—H12 | 0.9300 |
C3—C4 | 1.517 (5) | C13—H13 | 0.9300 |
C3—H3A | 0.9700 | C14—C15 | 1.385 (5) |
C3—H3B | 0.9700 | C14—C19 | 1.389 (5) |
C4—C5 | 1.499 (5) | C15—C16 | 1.391 (5) |
C4—H4A | 0.9700 | C15—H15 | 0.9300 |
C4—H4B | 0.9700 | C16—C17 | 1.363 (6) |
C5—C6 | 1.548 (5) | C16—H16 | 0.9300 |
C5—H5A | 0.9700 | C17—C18 | 1.349 (6) |
C5—H5B | 0.9700 | C18—C19 | 1.380 (5) |
C6—C7 | 1.547 (5) | C18—H18 | 0.9300 |
C6—H6 | 0.9800 | C19—H19 | 0.9300 |
C14—N1—C7 | 124.0 (3) | N1—C7—H7 | 108.0 |
C14—N1—H1 | 118.7 | C8—C7—H7 | 108.0 |
C7—N1—H1 | 114.1 | C6—C7—H7 | 108.0 |
O1—C1—C2 | 121.2 (3) | C13—C8—C9 | 117.3 (3) |
O1—C1—C6 | 122.5 (3) | C13—C8—C7 | 121.5 (3) |
C2—C1—C6 | 116.0 (3) | C9—C8—C7 | 121.2 (3) |
C1—C2—C3 | 109.5 (3) | C10—C9—C8 | 121.3 (3) |
C1—C2—H2A | 109.8 | C10—C9—H9 | 119.3 |
C3—C2—H2A | 109.8 | C8—C9—H9 | 119.3 |
C1—C2—H2B | 109.8 | C11—C10—C9 | 119.8 (4) |
C3—C2—H2B | 109.8 | C11—C10—H10 | 120.1 |
H2A—C2—H2B | 108.2 | C9—C10—H10 | 120.1 |
C4—C3—C2 | 111.3 (3) | C12—C11—C10 | 120.3 (4) |
C4—C3—H3A | 109.4 | C12—C11—Br1 | 119.6 (3) |
C2—C3—H3A | 109.4 | C10—C11—Br1 | 120.0 (3) |
C4—C3—H3B | 109.4 | C11—C12—C13 | 119.6 (4) |
C2—C3—H3B | 109.4 | C11—C12—H12 | 120.2 |
H3A—C3—H3B | 108.0 | C13—C12—H12 | 120.2 |
C5—C4—C3 | 111.2 (3) | C12—C13—C8 | 121.6 (4) |
C5—C4—H4A | 109.4 | C12—C13—H13 | 119.2 |
C3—C4—H4A | 109.4 | C8—C13—H13 | 119.2 |
C5—C4—H4B | 109.4 | N1—C14—C15 | 124.0 (3) |
C3—C4—H4B | 109.4 | N1—C14—C19 | 118.9 (3) |
H4A—C4—H4B | 108.0 | C15—C14—C19 | 117.0 (3) |
C4—C5—C6 | 112.9 (3) | C14—C15—C16 | 121.4 (4) |
C4—C5—H5A | 109.0 | C14—C15—H15 | 119.3 |
C6—C5—H5A | 109.0 | C16—C15—H15 | 119.3 |
C4—C5—H5B | 109.0 | C17—C16—C15 | 118.7 (4) |
C6—C5—H5B | 109.0 | C17—C16—H16 | 120.7 |
H5A—C5—H5B | 107.8 | C15—C16—H16 | 120.7 |
C1—C6—C7 | 110.1 (3) | C18—C17—C16 | 121.9 (4) |
C1—C6—C5 | 107.8 (3) | C18—C17—F1 | 119.1 (4) |
C7—C6—C5 | 113.5 (3) | C16—C17—F1 | 119.0 (4) |
C1—C6—H6 | 108.4 | C17—C18—C19 | 119.2 (4) |
C7—C6—H6 | 108.4 | C17—C18—H18 | 120.4 |
C5—C6—H6 | 108.4 | C19—C18—H18 | 120.4 |
N1—C7—C8 | 115.0 (3) | C18—C19—C14 | 121.6 (4) |
N1—C7—C6 | 106.9 (3) | C18—C19—H19 | 119.2 |
C8—C7—C6 | 110.7 (3) | C14—C19—H19 | 119.2 |
O1—C1—C2—C3 | 119.2 (4) | C7—C8—C9—C10 | −176.5 (3) |
C6—C1—C2—C3 | −55.2 (4) | C8—C9—C10—C11 | −1.5 (6) |
C1—C2—C3—C4 | 54.1 (4) | C9—C10—C11—C12 | 0.3 (6) |
C2—C3—C4—C5 | −56.3 (4) | C9—C10—C11—Br1 | 178.9 (3) |
C3—C4—C5—C6 | 56.5 (4) | C10—C11—C12—C13 | −0.8 (6) |
O1—C1—C6—C7 | 115.0 (4) | Br1—C11—C12—C13 | −179.4 (3) |
C2—C1—C6—C7 | −70.6 (4) | C11—C12—C13—C8 | 2.4 (6) |
O1—C1—C6—C5 | −120.7 (4) | C9—C8—C13—C12 | −3.5 (6) |
C2—C1—C6—C5 | 53.7 (4) | C7—C8—C13—C12 | 176.1 (3) |
C4—C5—C6—C1 | −53.2 (4) | C7—N1—C14—C15 | −16.0 (5) |
C4—C5—C6—C7 | 69.1 (4) | C7—N1—C14—C19 | 166.3 (3) |
C14—N1—C7—C8 | −78.0 (4) | N1—C14—C15—C16 | −172.5 (3) |
C14—N1—C7—C6 | 158.8 (3) | C19—C14—C15—C16 | 5.3 (6) |
C1—C6—C7—N1 | −52.9 (4) | C14—C15—C16—C17 | −2.4 (6) |
C5—C6—C7—N1 | −173.9 (3) | C15—C16—C17—C18 | −1.0 (6) |
C1—C6—C7—C8 | −178.8 (3) | C15—C16—C17—F1 | 177.7 (3) |
C5—C6—C7—C8 | 60.2 (4) | C16—C17—C18—C19 | 1.2 (7) |
N1—C7—C8—C13 | 132.0 (4) | F1—C17—C18—C19 | −177.4 (4) |
C6—C7—C8—C13 | −106.8 (4) | C17—C18—C19—C14 | 1.9 (7) |
N1—C7—C8—C9 | −48.4 (5) | N1—C14—C19—C18 | 172.9 (4) |
C6—C7—C8—C9 | 72.8 (4) | C15—C14—C19—C18 | −5.0 (6) |
C13—C8—C9—C10 | 3.0 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.81 | 2.19 | 2.978 (4) | 166 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C19H19BrFNO |
Mr | 376.26 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 295 |
a, b, c (Å) | 12.6501 (14), 8.2310 (9), 17.0111 (18) |
β (°) | 103.031 (2) |
V (Å3) | 1725.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.40 |
Crystal size (mm) | 0.37 × 0.31 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.450, 0.660 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8450, 3060, 1669 |
Rint | 0.120 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.113, 0.82 |
No. of reflections | 3060 |
No. of parameters | 208 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.38 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.81 | 2.19 | 2.978 (4) | 165.7 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
β-Amino carbonyl moieties are found as structural units of a number of biologically active natural products. As a part of a project on the synthesis of such compounds the crystal structure analysis was performed. In the crystal structure of the title compound (I) the dihedral angle between the phenyl rings C8—C13 and C14—C19 is 74.84 (1)°. The six-membered ring (C1—C6) is in a chair conformation. A pair of weak intermolecular N—H···O hydrogen bonds link the molecules into dimers (Fig.1 and Table 1).