Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025767/om2117sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025767/om2117Isup2.hkl |
CCDC reference: 645292
The title compound was synthesized according to procedure of Yuan et al., 2004. Crystals appropriate for data collection were obtained by slow evaporation of a CH3COCH3/C6H6 (100:1, v/v) solution at 283 K.
All H atoms were initially located in a difference Fourier map. The methyl H atoms were then constrained to an ideal geometry with C—H distances of 0.98 Å and Uiso(H) = 1.5Ueq(C), but each group was allowed to rotate freely about its C—C bond. All other H atoms bonded to carbon were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances in the range 0.95–1.00 Å and Uiso(H) = 1.2Ueq(C). The O—H and N—H H atom coordinates were allowed to refine but the thermal parameters were fixed.
Derivatives of indole have received much attention because of their widespread applications in materials science, agrichemicals, and pharmaceuticals (Ramirez & Garcia-Rubio, 2003). Their preparation and functionalization continues to be a fascinating subject in organic synthesis due to the frequent appearance of indoles in biologically interesting compounds (Bandini et al., 2005). The title compound, an example of a derivatized indole core, is shown in Figure 1. In the crystal, C—H···O hydrogen bonds, (Table 1) link the molecules in rows along the c axis (Fig. 2)
For related literature, see: Bandini et al. (2005); Ramirez & Garcia-Rubio (2003); Yuan et al. (2004).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2001b) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL.
C18H17BrN2O2 | F(000) = 380 |
Mr = 373.25 | Dx = 1.558 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2442 reflections |
a = 4.5759 (6) Å | θ = 0.0–0.0° |
b = 9.4134 (11) Å | µ = 2.60 mm−1 |
c = 18.540 (2) Å | T = 296 K |
β = 95.049 (2)° | Block, colorless |
V = 795.51 (17) Å3 | 0.20 × 0.20 × 0.10 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 3482 independent reflections |
Radiation source: fine-focus sealed tube | 2936 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
φ and ω scans | θmax = 28.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001a) | h = −6→5 |
Tmin = 0.625, Tmax = 0.781 | k = −11→12 |
5321 measured reflections | l = −22→24 |
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)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.063 | w = 1/[σ2(Fo2)] where P = (Fo2 + 2Fc2)/3 |
S = 0.95 | (Δ/σ)max = 0.002 |
3482 reflections | Δρmax = 0.40 e Å−3 |
215 parameters | Δρmin = −0.32 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 1456 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.015 (7) |
C18H17BrN2O2 | V = 795.51 (17) Å3 |
Mr = 373.25 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 4.5759 (6) Å | µ = 2.60 mm−1 |
b = 9.4134 (11) Å | T = 296 K |
c = 18.540 (2) Å | 0.20 × 0.20 × 0.10 mm |
β = 95.049 (2)° |
Bruker SMART CCD area-detector diffractometer | 3482 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001a) | 2936 reflections with I > 2σ(I) |
Tmin = 0.625, Tmax = 0.781 | Rint = 0.021 |
5321 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.063 | Δρmax = 0.40 e Å−3 |
S = 0.95 | Δρmin = −0.32 e Å−3 |
3482 reflections | Absolute structure: Flack (1983), 1456 Friedel pairs |
215 parameters | Absolute structure parameter: 0.015 (7) |
1 restraint |
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 | 1.14694 (7) | −0.31988 (3) | 0.737099 (16) | 0.06370 (11) | |
C1 | 0.6534 (6) | 0.0039 (3) | 0.81575 (12) | 0.0391 (6) | |
H1A | 0.5425 | 0.0180 | 0.8548 | 0.047* | |
C2 | 0.8019 (6) | −0.1216 (3) | 0.80734 (13) | 0.0433 (6) | |
H2 | 0.7932 | −0.1936 | 0.8414 | 0.052* | |
C3 | 0.9654 (6) | −0.1411 (3) | 0.74796 (13) | 0.0391 (5) | |
C4 | 0.9924 (5) | −0.0383 (2) | 0.69649 (12) | 0.0341 (5) | |
H4 | 1.1062 | −0.0534 | 0.6580 | 0.041* | |
C5 | 0.8429 (5) | 0.0900 (2) | 0.70371 (11) | 0.0298 (5) | |
C6 | 0.6757 (5) | 0.1082 (3) | 0.76376 (12) | 0.0318 (5) | |
C7 | 0.8163 (5) | 0.2179 (2) | 0.66256 (11) | 0.0317 (5) | |
C8 | 0.6355 (5) | 0.3059 (3) | 0.69713 (12) | 0.0357 (5) | |
H8 | 0.5795 | 0.3967 | 0.6817 | 0.043* | |
C9 | 0.3612 (5) | 0.3018 (3) | 0.81004 (12) | 0.0403 (5) | |
H9A | 0.2210 | 0.2306 | 0.8225 | 0.048* | |
H9B | 0.2518 | 0.3806 | 0.7874 | 0.048* | |
C10 | 0.5304 (5) | 0.3531 (3) | 0.87805 (12) | 0.0362 (5) | |
C11 | 0.7243 (6) | 0.4648 (3) | 0.87613 (14) | 0.0482 (6) | |
H11 | 0.7512 | 0.5078 | 0.8320 | 0.058* | |
C12 | 0.8776 (7) | 0.5135 (4) | 0.93757 (19) | 0.0689 (9) | |
H12 | 1.0081 | 0.5887 | 0.9350 | 0.083* | |
C13 | 0.8399 (8) | 0.4520 (5) | 1.00341 (18) | 0.0757 (11) | |
H13 | 0.9437 | 0.4858 | 1.0453 | 0.091* | |
C14 | 0.6496 (9) | 0.3411 (4) | 1.00709 (15) | 0.0733 (11) | |
H14 | 0.6246 | 0.2985 | 1.0514 | 0.088* | |
C15 | 0.4936 (7) | 0.2922 (3) | 0.94434 (13) | 0.0545 (7) | |
H15 | 0.3624 | 0.2173 | 0.9470 | 0.065* | |
C16 | 0.9457 (5) | 0.2509 (2) | 0.59302 (12) | 0.0352 (5) | |
H16 | 1.1449 | 0.2120 | 0.5951 | 0.042* | |
C17 | 0.7595 (5) | 0.1810 (3) | 0.53065 (10) | 0.0338 (4) | |
C18 | 0.3941 (7) | 0.2177 (3) | 0.42835 (13) | 0.0538 (8) | |
H18A | 0.5083 | 0.1786 | 0.3921 | 0.081* | |
H18B | 0.2787 | 0.2955 | 0.4081 | 0.081* | |
H18C | 0.2667 | 0.1457 | 0.4446 | 0.081* | |
H1 | 1.088 (8) | 0.418 (4) | 0.5528 (18) | 0.081* | |
H2A | 0.572 (7) | 0.358 (3) | 0.4998 (16) | 0.065* | |
N1 | 0.5491 (5) | 0.2407 (2) | 0.75786 (10) | 0.0357 (5) | |
N2 | 0.5881 (5) | 0.2677 (2) | 0.48896 (11) | 0.0400 (5) | |
O1 | 0.9600 (4) | 0.40069 (17) | 0.58655 (9) | 0.0473 (4) | |
O2 | 0.7673 (4) | 0.05083 (18) | 0.52216 (9) | 0.0470 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0778 (2) | 0.03513 (14) | 0.0805 (2) | 0.01527 (16) | 0.02007 (15) | 0.01439 (16) |
C1 | 0.0485 (15) | 0.0387 (14) | 0.0309 (11) | −0.0056 (11) | 0.0081 (11) | 0.0018 (10) |
C2 | 0.0576 (16) | 0.0373 (14) | 0.0348 (12) | −0.0030 (12) | 0.0021 (11) | 0.0105 (10) |
C3 | 0.0440 (14) | 0.0296 (12) | 0.0428 (13) | 0.0029 (10) | −0.0012 (11) | 0.0021 (10) |
C4 | 0.0362 (12) | 0.0327 (12) | 0.0333 (11) | −0.0003 (9) | 0.0023 (10) | −0.0031 (9) |
C5 | 0.0320 (12) | 0.0310 (12) | 0.0260 (11) | −0.0047 (9) | 0.0010 (9) | −0.0029 (9) |
C6 | 0.0364 (14) | 0.0324 (13) | 0.0262 (11) | −0.0044 (10) | 0.0001 (10) | −0.0015 (10) |
C7 | 0.0372 (12) | 0.0282 (13) | 0.0295 (11) | −0.0015 (8) | 0.0017 (9) | −0.0013 (8) |
C8 | 0.0437 (14) | 0.0301 (12) | 0.0329 (12) | 0.0022 (10) | 0.0010 (10) | −0.0012 (10) |
C9 | 0.0381 (13) | 0.0436 (14) | 0.0400 (13) | 0.0040 (11) | 0.0082 (10) | −0.0024 (11) |
C10 | 0.0405 (13) | 0.0346 (13) | 0.0347 (12) | 0.0062 (10) | 0.0096 (10) | −0.0053 (10) |
C11 | 0.0534 (17) | 0.0466 (16) | 0.0447 (14) | −0.0031 (13) | 0.0046 (13) | −0.0055 (12) |
C12 | 0.0581 (19) | 0.065 (2) | 0.081 (2) | −0.0043 (16) | −0.0046 (17) | −0.0260 (18) |
C13 | 0.078 (2) | 0.086 (3) | 0.058 (2) | 0.036 (2) | −0.0207 (18) | −0.0336 (19) |
C14 | 0.113 (3) | 0.077 (3) | 0.0312 (15) | 0.044 (2) | 0.0104 (17) | 0.0035 (15) |
C15 | 0.075 (2) | 0.0504 (17) | 0.0411 (15) | 0.0064 (16) | 0.0212 (14) | 0.0033 (13) |
C16 | 0.0404 (13) | 0.0287 (12) | 0.0371 (12) | −0.0001 (10) | 0.0070 (10) | 0.0034 (9) |
C17 | 0.0456 (11) | 0.0293 (10) | 0.0283 (9) | 0.0020 (13) | 0.0135 (9) | 0.0016 (12) |
C18 | 0.0660 (17) | 0.058 (2) | 0.0360 (12) | −0.0011 (13) | −0.0042 (12) | 0.0037 (11) |
N1 | 0.0426 (12) | 0.0356 (11) | 0.0297 (10) | 0.0011 (10) | 0.0072 (9) | −0.0021 (8) |
N2 | 0.0551 (13) | 0.0321 (11) | 0.0327 (10) | 0.0015 (10) | 0.0028 (9) | 0.0017 (9) |
O1 | 0.0682 (12) | 0.0299 (10) | 0.0453 (9) | −0.0101 (9) | 0.0148 (9) | 0.0029 (7) |
O2 | 0.0721 (13) | 0.0283 (9) | 0.0405 (9) | 0.0045 (9) | 0.0045 (9) | −0.0032 (7) |
Br1—C3 | 1.895 (2) | C10—C15 | 1.380 (3) |
C1—C2 | 1.378 (4) | C11—C12 | 1.363 (4) |
C1—C6 | 1.386 (3) | C11—H11 | 0.9300 |
C1—H1A | 0.9300 | C12—C13 | 1.376 (5) |
C2—C3 | 1.397 (4) | C12—H12 | 0.9300 |
C2—H2 | 0.9300 | C13—C14 | 1.365 (5) |
C3—C4 | 1.372 (3) | C13—H13 | 0.9300 |
C4—C5 | 1.400 (3) | C14—C15 | 1.389 (5) |
C4—H4 | 0.9300 | C14—H14 | 0.9300 |
C5—C6 | 1.416 (3) | C15—H15 | 0.9300 |
C5—C7 | 1.425 (3) | C16—O1 | 1.418 (3) |
C6—N1 | 1.375 (3) | C16—C17 | 1.524 (3) |
C7—C8 | 1.369 (3) | C16—H16 | 0.9800 |
C7—C16 | 1.498 (3) | C17—O2 | 1.236 (4) |
C8—N1 | 1.371 (3) | C17—N2 | 1.331 (3) |
C8—H8 | 0.9300 | C18—N2 | 1.448 (3) |
C9—N1 | 1.467 (3) | C18—H18A | 0.9600 |
C9—C10 | 1.500 (3) | C18—H18B | 0.9600 |
C9—H9A | 0.9700 | C18—H18C | 0.9600 |
C9—H9B | 0.9700 | N2—H2A | 0.87 (3) |
C10—C11 | 1.378 (4) | O1—H1 | 0.91 (4) |
C2—C1—C6 | 117.5 (2) | C10—C11—H11 | 119.3 |
C2—C1—H1A | 121.3 | C11—C12—C13 | 120.3 (3) |
C6—C1—H1A | 121.3 | C11—C12—H12 | 119.9 |
C1—C2—C3 | 120.4 (2) | C13—C12—H12 | 119.9 |
C1—C2—H2 | 119.8 | C14—C13—C12 | 119.8 (3) |
C3—C2—H2 | 119.8 | C14—C13—H13 | 120.1 |
C4—C3—C2 | 122.9 (2) | C12—C13—H13 | 120.1 |
C4—C3—Br1 | 119.02 (18) | C13—C14—C15 | 119.6 (3) |
C2—C3—Br1 | 118.10 (18) | C13—C14—H14 | 120.2 |
C3—C4—C5 | 117.9 (2) | C15—C14—H14 | 120.2 |
C3—C4—H4 | 121.1 | C10—C15—C14 | 121.0 (3) |
C5—C4—H4 | 121.1 | C10—C15—H15 | 119.5 |
C4—C5—C6 | 118.8 (2) | C14—C15—H15 | 119.5 |
C4—C5—C7 | 134.2 (2) | O1—C16—C7 | 107.67 (18) |
C6—C5—C7 | 107.0 (2) | O1—C16—C17 | 113.1 (2) |
N1—C6—C1 | 129.9 (2) | C7—C16—C17 | 109.08 (18) |
N1—C6—C5 | 107.5 (2) | O1—C16—H16 | 109.0 |
C1—C6—C5 | 122.6 (2) | C7—C16—H16 | 109.0 |
C8—C7—C5 | 106.69 (19) | C17—C16—H16 | 109.0 |
C8—C7—C16 | 125.3 (2) | O2—C17—N2 | 123.8 (2) |
C5—C7—C16 | 127.91 (19) | O2—C17—C16 | 120.3 (2) |
C7—C8—N1 | 110.1 (2) | N2—C17—C16 | 116.0 (2) |
C7—C8—H8 | 125.0 | N2—C18—H18A | 109.5 |
N1—C8—H8 | 125.0 | N2—C18—H18B | 109.5 |
N1—C9—C10 | 113.0 (2) | H18A—C18—H18B | 109.5 |
N1—C9—H9A | 109.0 | N2—C18—H18C | 109.5 |
C10—C9—H9A | 109.0 | H18A—C18—H18C | 109.5 |
N1—C9—H9B | 109.0 | H18B—C18—H18C | 109.5 |
C10—C9—H9B | 109.0 | C8—N1—C6 | 108.7 (2) |
H9A—C9—H9B | 107.8 | C8—N1—C9 | 126.5 (2) |
C11—C10—C15 | 118.0 (2) | C6—N1—C9 | 124.8 (2) |
C11—C10—C9 | 120.7 (2) | C17—N2—C18 | 122.7 (2) |
C15—C10—C9 | 121.3 (2) | C17—N2—H2A | 121 (2) |
C12—C11—C10 | 121.3 (3) | C18—N2—H2A | 116 (2) |
C12—C11—H11 | 119.3 | C16—O1—H1 | 106 (2) |
C6—C1—C2—C3 | −0.5 (4) | C11—C12—C13—C14 | 0.4 (5) |
C1—C2—C3—C4 | 1.3 (4) | C12—C13—C14—C15 | −0.6 (5) |
C1—C2—C3—Br1 | −176.7 (2) | C11—C10—C15—C14 | −0.7 (4) |
C2—C3—C4—C5 | −1.4 (4) | C9—C10—C15—C14 | −179.5 (2) |
Br1—C3—C4—C5 | 176.59 (17) | C13—C14—C15—C10 | 0.7 (4) |
C3—C4—C5—C6 | 0.8 (3) | C8—C7—C16—O1 | 25.1 (3) |
C3—C4—C5—C7 | −179.7 (2) | C5—C7—C16—O1 | −158.0 (2) |
C2—C1—C6—N1 | 178.8 (2) | C8—C7—C16—C17 | −97.9 (3) |
C2—C1—C6—C5 | 0.0 (4) | C5—C7—C16—C17 | 78.9 (3) |
C4—C5—C6—N1 | −179.2 (2) | O1—C16—C17—O2 | 167.5 (2) |
C7—C5—C6—N1 | 1.2 (2) | C7—C16—C17—O2 | −72.7 (3) |
C4—C5—C6—C1 | −0.1 (3) | O1—C16—C17—N2 | −14.3 (3) |
C7—C5—C6—C1 | −179.7 (2) | C7—C16—C17—N2 | 105.5 (2) |
C4—C5—C7—C8 | 179.5 (2) | C7—C8—N1—C6 | 0.4 (3) |
C6—C5—C7—C8 | −1.0 (3) | C7—C8—N1—C9 | 178.4 (2) |
C4—C5—C7—C16 | 2.1 (4) | C1—C6—N1—C8 | −180.0 (2) |
C6—C5—C7—C16 | −178.3 (2) | C5—C6—N1—C8 | −1.0 (2) |
C5—C7—C8—N1 | 0.4 (3) | C1—C6—N1—C9 | 1.9 (4) |
C16—C7—C8—N1 | 177.8 (2) | C5—C6—N1—C9 | −179.1 (2) |
N1—C9—C10—C11 | 65.1 (3) | C10—C9—N1—C8 | −101.6 (3) |
N1—C9—C10—C15 | −116.1 (3) | C10—C9—N1—C6 | 76.2 (3) |
C15—C10—C11—C12 | 0.5 (4) | O2—C17—N2—C18 | −0.7 (3) |
C9—C10—C11—C12 | 179.4 (3) | C16—C17—N2—C18 | −178.8 (2) |
C10—C11—C12—C13 | −0.3 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1 | 0.87 (3) | 2.32 (3) | 2.682 (3) | 105 (2) |
C18—H18C···O1i | 0.96 | 2.57 | 3.395 (3) | 144 |
N2—H2A···O2ii | 0.87 (3) | 2.40 (3) | 3.119 (3) | 139 (3) |
O1—H1···O2iii | 0.91 (4) | 2.02 (4) | 2.839 (2) | 149 (3) |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+1, y+1/2, −z+1; (iii) −x+2, y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C18H17BrN2O2 |
Mr | 373.25 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 296 |
a, b, c (Å) | 4.5759 (6), 9.4134 (11), 18.540 (2) |
β (°) | 95.049 (2) |
V (Å3) | 795.51 (17) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.60 |
Crystal size (mm) | 0.20 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001a) |
Tmin, Tmax | 0.625, 0.781 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5321, 3482, 2936 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.660 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.063, 0.95 |
No. of reflections | 3482 |
No. of parameters | 215 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.32 |
Absolute structure | Flack (1983), 1456 Friedel pairs |
Absolute structure parameter | 0.015 (7) |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2001b) and PLATON (Spek, 2003), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1 | 0.87 (3) | 2.32 (3) | 2.682 (3) | 105 (2) |
C18—H18C···O1i | 0.96 | 2.57 | 3.395 (3) | 143.7 |
N2—H2A···O2ii | 0.87 (3) | 2.40 (3) | 3.119 (3) | 139 (3) |
O1—H1···O2iii | 0.91 (4) | 2.02 (4) | 2.839 (2) | 149 (3) |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+1, y+1/2, −z+1; (iii) −x+2, y+1/2, −z+1. |
Derivatives of indole have received much attention because of their widespread applications in materials science, agrichemicals, and pharmaceuticals (Ramirez & Garcia-Rubio, 2003). Their preparation and functionalization continues to be a fascinating subject in organic synthesis due to the frequent appearance of indoles in biologically interesting compounds (Bandini et al., 2005). The title compound, an example of a derivatized indole core, is shown in Figure 1. In the crystal, C—H···O hydrogen bonds, (Table 1) link the molecules in rows along the c axis (Fig. 2)