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The crystal and molecular structures of the three 4-ketotetrahydroindoles 2-(4-chlorophenyl)-1-(4-fluorophenyl)-6,6-dimethyl-4,5,6,7-tetrahydro-1
H-indol-4-one (C
22H
19ClFNO), (I), 1-(4-fluorophenyl)-2-(4-methoxyphenyl)-6,6-dimethyl-4,5,6,7-tetrahydro-1
H-indol-4-one (C
23H
22FNO
2), (II), and 6,6-dimethyl-1,2-diphenyl-4,5,6,7-tetrahydro-1
H-indol-4-one (C
22H
21NO), (III), have been determined
via single-crystal X-ray diffraction in order to study the intermolecular interactions therein. All three structures are stabilized
via intermolecular C—H
O and C—H
π interactions, generating different molecular motifs.
Supporting information
CCDC references: 235354; 235355; 235356
Compounds (I)-(III) were synthesized using the procedure of Nagarajan et al. (1985). Single crystals suitable for X-ray diffraction studies were grown from solutions in acetone (analytical reagent) by slow evaporation at 283 K.
The ranges of the C—H bond lengths in (I), (II) and (III) are 0.91 (3)–1.08 (3), 0.93 (2)–1.01 (3) and 0.93 (2)–1.05 (2) Å, respectively.
For all compounds, data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997), CAMERON (Watkin et al., 1993) and PLATON (Spek 2003); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON.
(I) 2-(4-chlorophenyl)-1-(4-fluorophenyl)-6,6-dimethyl-4,5,6,7-tetrahydro- 1
H-indol-4-one
top
Crystal data top
C22H19ClFNO | Z = 2 |
Mr = 367.83 | F(000) = 384 |
Triclinic, P1 | Dx = 1.292 Mg m−3 |
Hall symbol: -P 1 | Melting point: 507 K |
a = 9.246 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.228 (4) Å | Cell parameters from 2435 reflections |
c = 11.177 (4) Å | θ = 2.3–21.2° |
α = 80.529 (6)° | µ = 0.22 mm−1 |
β = 86.335 (7)° | T = 293 K |
γ = 65.120 (6)° | Plate, colourless |
V = 945.7 (6) Å3 | 0.50 × 0.30 × 0.20 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3788 independent reflections |
Radiation source: fine-focus sealed tube | 2811 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ϕ and ω scans | θmax = 26.4°, θmin = 1.9° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.844, Tmax = 0.957 | k = −12→12 |
9987 measured reflections | l = −13→13 |
Refinement top
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.118 | All H-atom parameters refined |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0455P)2 + 0.2584P] where P = (Fo2 + 2Fc2)/3 |
3788 reflections | (Δ/σ)max < 0.001 |
311 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Crystal data top
C22H19ClFNO | γ = 65.120 (6)° |
Mr = 367.83 | V = 945.7 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.246 (3) Å | Mo Kα radiation |
b = 10.228 (4) Å | µ = 0.22 mm−1 |
c = 11.177 (4) Å | T = 293 K |
α = 80.529 (6)° | 0.50 × 0.30 × 0.20 mm |
β = 86.335 (7)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3788 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2811 reflections with I > 2σ(I) |
Tmin = 0.844, Tmax = 0.957 | Rint = 0.024 |
9987 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.118 | All H-atom parameters refined |
S = 1.04 | Δρmax = 0.20 e Å−3 |
3788 reflections | Δρmin = −0.22 e Å−3 |
311 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.66030 (9) | 0.27487 (8) | 0.99603 (6) | 0.0893 (3) | |
N1 | 0.74427 (17) | 0.54652 (15) | 0.39864 (14) | 0.0445 (4) | |
O1 | 0.5159 (3) | 1.04382 (16) | 0.30251 (16) | 0.0989 (7) | |
F1 | 1.1009 (2) | −0.02663 (15) | 0.34244 (18) | 0.1180 (6) | |
C1 | 0.6736 (2) | 0.60481 (19) | 0.50405 (17) | 0.0449 (4) | |
C2 | 0.6048 (2) | 0.7529 (2) | 0.47288 (19) | 0.0505 (5) | |
C3 | 0.5853 (3) | 0.9258 (2) | 0.2686 (2) | 0.0588 (5) | |
C4 | 0.6250 (3) | 0.9138 (2) | 0.1373 (2) | 0.0600 (6) | |
C5 | 0.7828 (3) | 0.7863 (2) | 0.1146 (2) | 0.0594 (5) | |
C6 | 0.7775 (3) | 0.6433 (2) | 0.1792 (2) | 0.0572 (5) | |
C7 | 0.7189 (2) | 0.65797 (19) | 0.30515 (17) | 0.0466 (4) | |
C8 | 0.6317 (2) | 0.78683 (19) | 0.34852 (18) | 0.0487 (5) | |
C9 | 0.8369 (2) | 0.39556 (18) | 0.38695 (17) | 0.0451 (4) | |
C10 | 0.9871 (3) | 0.3220 (2) | 0.4367 (2) | 0.0607 (6) | |
C11 | 1.0767 (3) | 0.1786 (2) | 0.4214 (3) | 0.0760 (7) | |
C12 | 1.0124 (3) | 0.1143 (2) | 0.3575 (2) | 0.0734 (7) | |
C13 | 0.8633 (3) | 0.1833 (3) | 0.3088 (2) | 0.0772 (7) | |
C14 | 0.7741 (3) | 0.3273 (2) | 0.3234 (2) | 0.0637 (6) | |
C15 | 0.6749 (2) | 0.51810 (19) | 0.62245 (17) | 0.0457 (4) | |
C16 | 0.6757 (3) | 0.5763 (2) | 0.72673 (19) | 0.0551 (5) | |
C17 | 0.6686 (3) | 0.5037 (2) | 0.8405 (2) | 0.0620 (6) | |
C18 | 0.6626 (2) | 0.3697 (2) | 0.85213 (19) | 0.0570 (5) | |
C19 | 0.6614 (2) | 0.3093 (2) | 0.7518 (2) | 0.0562 (5) | |
C20 | 0.6669 (2) | 0.3830 (2) | 0.6379 (2) | 0.0508 (5) | |
C21 | 0.8021 (5) | 0.7823 (4) | −0.0217 (3) | 0.0885 (9) | |
C22 | 0.9196 (4) | 0.8080 (4) | 0.1648 (4) | 0.0913 (9) | |
H2 | 0.547 (2) | 0.817 (2) | 0.5230 (17) | 0.049 (5)* | |
H4A | 0.625 (2) | 1.005 (2) | 0.0972 (19) | 0.063 (6)* | |
H4B | 0.539 (3) | 0.900 (2) | 0.1011 (19) | 0.068 (6)* | |
H6A | 0.880 (3) | 0.563 (2) | 0.1784 (18) | 0.061 (6)* | |
H6B | 0.705 (2) | 0.619 (2) | 0.1332 (18) | 0.057 (6)* | |
H10 | 1.029 (3) | 0.369 (2) | 0.483 (2) | 0.072 (7)* | |
H11 | 1.181 (3) | 0.129 (3) | 0.458 (2) | 0.093 (8)* | |
H13 | 0.823 (3) | 0.136 (3) | 0.265 (2) | 0.087 (8)* | |
H14 | 0.672 (3) | 0.380 (3) | 0.289 (2) | 0.083 (8)* | |
H16 | 0.683 (2) | 0.666 (2) | 0.7170 (18) | 0.058 (6)* | |
H17 | 0.669 (3) | 0.548 (2) | 0.909 (2) | 0.070 (7)* | |
H19 | 0.659 (2) | 0.217 (2) | 0.7612 (18) | 0.060 (6)* | |
H20 | 0.663 (2) | 0.341 (2) | 0.5701 (19) | 0.056 (6)* | |
H21A | 0.813 (3) | 0.870 (3) | −0.066 (3) | 0.105 (9)* | |
H21B | 0.711 (4) | 0.768 (3) | −0.060 (3) | 0.122 (12)* | |
H21C | 0.897 (3) | 0.703 (3) | −0.033 (2) | 0.082 (8)* | |
H22A | 1.010 (4) | 0.731 (4) | 0.149 (3) | 0.115 (11)* | |
H22B | 0.910 (4) | 0.811 (3) | 0.261 (3) | 0.121 (11)* | |
H22C | 0.926 (3) | 0.894 (3) | 0.123 (3) | 0.110 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.1093 (6) | 0.0859 (5) | 0.0681 (4) | −0.0433 (4) | 0.0167 (4) | 0.0020 (3) |
N1 | 0.0443 (9) | 0.0342 (8) | 0.0510 (9) | −0.0102 (6) | −0.0023 (7) | −0.0121 (7) |
O1 | 0.1506 (18) | 0.0356 (9) | 0.0811 (12) | −0.0081 (10) | −0.0041 (11) | −0.0136 (8) |
F1 | 0.1249 (14) | 0.0436 (8) | 0.1618 (17) | −0.0023 (8) | 0.0004 (12) | −0.0426 (9) |
C1 | 0.0418 (10) | 0.0387 (10) | 0.0535 (11) | −0.0126 (8) | −0.0030 (8) | −0.0151 (8) |
C2 | 0.0500 (11) | 0.0385 (10) | 0.0581 (13) | −0.0091 (9) | −0.0026 (9) | −0.0189 (9) |
C3 | 0.0648 (13) | 0.0404 (11) | 0.0633 (14) | −0.0118 (10) | −0.0105 (10) | −0.0106 (10) |
C4 | 0.0698 (15) | 0.0411 (11) | 0.0642 (14) | −0.0197 (10) | −0.0120 (11) | 0.0001 (10) |
C5 | 0.0628 (13) | 0.0518 (12) | 0.0597 (13) | −0.0213 (10) | 0.0017 (10) | −0.0061 (10) |
C6 | 0.0633 (14) | 0.0435 (11) | 0.0578 (13) | −0.0140 (10) | 0.0020 (11) | −0.0125 (10) |
C7 | 0.0457 (10) | 0.0376 (10) | 0.0533 (11) | −0.0126 (8) | −0.0071 (9) | −0.0088 (8) |
C8 | 0.0497 (11) | 0.0372 (10) | 0.0544 (12) | −0.0112 (8) | −0.0080 (9) | −0.0106 (8) |
C9 | 0.0470 (11) | 0.0340 (9) | 0.0521 (11) | −0.0131 (8) | 0.0021 (8) | −0.0117 (8) |
C10 | 0.0505 (12) | 0.0414 (11) | 0.0883 (16) | −0.0140 (9) | −0.0091 (11) | −0.0161 (11) |
C11 | 0.0538 (14) | 0.0440 (12) | 0.116 (2) | −0.0049 (11) | −0.0105 (14) | −0.0133 (13) |
C12 | 0.0820 (17) | 0.0346 (11) | 0.0926 (18) | −0.0094 (11) | 0.0063 (14) | −0.0240 (11) |
C13 | 0.097 (2) | 0.0520 (13) | 0.0861 (18) | −0.0246 (14) | −0.0119 (15) | −0.0310 (13) |
C14 | 0.0649 (14) | 0.0492 (12) | 0.0741 (15) | −0.0148 (11) | −0.0128 (12) | −0.0218 (11) |
C15 | 0.0384 (10) | 0.0385 (10) | 0.0564 (12) | −0.0101 (8) | −0.0006 (8) | −0.0127 (9) |
C16 | 0.0665 (13) | 0.0401 (11) | 0.0595 (13) | −0.0209 (10) | 0.0032 (10) | −0.0142 (10) |
C17 | 0.0736 (15) | 0.0586 (13) | 0.0546 (13) | −0.0254 (11) | 0.0065 (11) | −0.0187 (11) |
C18 | 0.0514 (12) | 0.0539 (12) | 0.0599 (13) | −0.0180 (9) | 0.0083 (10) | −0.0069 (10) |
C19 | 0.0509 (12) | 0.0448 (11) | 0.0736 (15) | −0.0213 (9) | 0.0075 (10) | −0.0099 (11) |
C20 | 0.0483 (11) | 0.0454 (11) | 0.0609 (13) | −0.0188 (9) | 0.0031 (9) | −0.0164 (10) |
C21 | 0.113 (3) | 0.0669 (18) | 0.0729 (18) | −0.0294 (19) | 0.0206 (18) | −0.0073 (14) |
C22 | 0.0693 (19) | 0.086 (2) | 0.123 (3) | −0.0384 (17) | 0.0025 (18) | −0.010 (2) |
Geometric parameters (Å, º) top
Cl1—C18 | 1.740 (2) | C10—C11 | 1.381 (3) |
N1—C7 | 1.364 (2) | C10—H10 | 0.96 (2) |
N1—C1 | 1.405 (2) | C11—C12 | 1.355 (4) |
N1—C9 | 1.440 (2) | C11—H11 | 0.96 (3) |
O1—C3 | 1.217 (2) | C12—C13 | 1.358 (4) |
F1—C12 | 1.358 (2) | C13—C14 | 1.384 (3) |
C1—C2 | 1.365 (3) | C13—H13 | 0.93 (3) |
C1—C15 | 1.464 (3) | C14—H14 | 0.94 (2) |
C2—C8 | 1.409 (3) | C15—C16 | 1.395 (3) |
C2—H2 | 0.91 (2) | C15—C20 | 1.397 (3) |
C3—C8 | 1.456 (3) | C16—C17 | 1.375 (3) |
C3—C4 | 1.502 (3) | C16—H16 | 0.94 (2) |
C4—C5 | 1.534 (3) | C17—C18 | 1.379 (3) |
C4—H4A | 0.96 (2) | C17—H17 | 0.95 (2) |
C4—H4B | 0.98 (2) | C18—C19 | 1.370 (3) |
C5—C22 | 1.527 (4) | C19—C20 | 1.378 (3) |
C5—C21 | 1.528 (4) | C19—H19 | 0.94 (2) |
C5—C6 | 1.540 (3) | C20—H20 | 0.94 (2) |
C6—C7 | 1.483 (3) | C21—H21A | 0.99 (3) |
C6—H6A | 0.96 (2) | C21—H21B | 1.04 (3) |
C6—H6B | 1.00 (2) | C21—H21C | 0.93 (3) |
C7—C8 | 1.374 (2) | C22—H22A | 0.91 (3) |
C9—C10 | 1.373 (3) | C22—H22B | 1.08 (3) |
C9—C14 | 1.373 (3) | C22—H22C | 0.95 (3) |
| | | |
C7—N1—C1 | 109.06 (14) | C12—C11—C10 | 118.4 (2) |
C7—N1—C9 | 123.19 (15) | C12—C11—H11 | 123.1 (15) |
C1—N1—C9 | 127.67 (15) | C10—C11—H11 | 118.4 (16) |
C2—C1—N1 | 106.91 (17) | C11—C12—F1 | 118.3 (2) |
C2—C1—C15 | 128.35 (17) | C11—C12—C13 | 123.2 (2) |
N1—C1—C15 | 124.73 (15) | F1—C12—C13 | 118.5 (2) |
C1—C2—C8 | 108.24 (17) | C12—C13—C14 | 118.3 (2) |
C1—C2—H2 | 125.5 (12) | C12—C13—H13 | 120.8 (16) |
C8—C2—H2 | 126.2 (12) | C14—C13—H13 | 120.9 (16) |
O1—C3—C8 | 123.9 (2) | C9—C14—C13 | 119.7 (2) |
O1—C3—C4 | 121.3 (2) | C9—C14—H14 | 119.4 (15) |
C8—C3—C4 | 114.77 (17) | C13—C14—H14 | 120.9 (15) |
C3—C4—C5 | 114.82 (18) | C16—C15—C20 | 117.46 (19) |
C3—C4—H4A | 108.7 (12) | C16—C15—C1 | 118.54 (17) |
C5—C4—H4A | 110.3 (12) | C20—C15—C1 | 123.91 (17) |
C3—C4—H4B | 107.5 (13) | C17—C16—C15 | 121.4 (2) |
C5—C4—H4B | 107.6 (12) | C17—C16—H16 | 120.7 (12) |
H4A—C4—H4B | 107.7 (17) | C15—C16—H16 | 117.9 (12) |
C22—C5—C21 | 110.6 (3) | C16—C17—C18 | 119.5 (2) |
C22—C5—C4 | 108.9 (2) | C16—C17—H17 | 118.5 (14) |
C21—C5—C4 | 108.9 (2) | C18—C17—H17 | 122.0 (14) |
C22—C5—C6 | 110.3 (2) | C19—C18—C17 | 120.8 (2) |
C21—C5—C6 | 109.5 (2) | C19—C18—Cl1 | 119.62 (17) |
C4—C5—C6 | 108.68 (18) | C17—C18—Cl1 | 119.60 (18) |
C7—C6—C5 | 110.59 (17) | C18—C19—C20 | 119.6 (2) |
C7—C6—H6A | 110.9 (13) | C18—C19—H19 | 119.8 (13) |
C5—C6—H6A | 111.2 (13) | C20—C19—H19 | 120.6 (13) |
C7—C6—H6B | 109.6 (12) | C19—C20—C15 | 121.3 (2) |
C5—C6—H6B | 109.4 (11) | C19—C20—H20 | 118.5 (12) |
H6A—C6—H6B | 105.0 (17) | C15—C20—H20 | 120.2 (12) |
N1—C7—C8 | 108.00 (17) | C5—C21—H21A | 111.8 (17) |
N1—C7—C6 | 126.16 (16) | C5—C21—H21B | 113.2 (18) |
C8—C7—C6 | 125.83 (18) | H21A—C21—H21B | 110 (2) |
C7—C8—C2 | 107.78 (17) | C5—C21—H21C | 107.5 (16) |
C7—C8—C3 | 120.59 (19) | H21A—C21—H21C | 107 (2) |
C2—C8—C3 | 131.62 (17) | H21B—C21—H21C | 107 (2) |
C10—C9—C14 | 120.58 (18) | C5—C22—H22A | 105 (2) |
C10—C9—N1 | 120.35 (17) | C5—C22—H22B | 112.7 (17) |
C14—C9—N1 | 119.06 (17) | H22A—C22—H22B | 110 (3) |
C9—C10—C11 | 119.8 (2) | C5—C22—H22C | 110.8 (19) |
C9—C10—H10 | 120.1 (13) | H22A—C22—H22C | 108 (3) |
C11—C10—H10 | 120.1 (14) | H22B—C22—H22C | 110 (3) |
| | | |
C7—N1—C1—C2 | 0.2 (2) | C4—C3—C8—C2 | −174.4 (2) |
C9—N1—C1—C2 | 177.12 (17) | C7—N1—C9—C10 | 106.0 (2) |
C7—N1—C1—C15 | 179.41 (16) | C1—N1—C9—C10 | −70.5 (3) |
C9—N1—C1—C15 | −3.7 (3) | C7—N1—C9—C14 | −72.7 (3) |
N1—C1—C2—C8 | 0.3 (2) | C1—N1—C9—C14 | 110.7 (2) |
C15—C1—C2—C8 | −178.91 (18) | C14—C9—C10—C11 | 0.9 (4) |
O1—C3—C4—C5 | 145.5 (2) | N1—C9—C10—C11 | −177.9 (2) |
C8—C3—C4—C5 | −36.3 (3) | C9—C10—C11—C12 | −0.3 (4) |
C3—C4—C5—C22 | −62.9 (3) | C10—C11—C12—F1 | 179.9 (2) |
C3—C4—C5—C21 | 176.5 (2) | C10—C11—C12—C13 | −0.8 (4) |
C3—C4—C5—C6 | 57.3 (3) | C11—C12—C13—C14 | 1.2 (4) |
C22—C5—C6—C7 | 72.3 (3) | F1—C12—C13—C14 | −179.5 (2) |
C21—C5—C6—C7 | −165.8 (2) | C10—C9—C14—C13 | −0.4 (4) |
C4—C5—C6—C7 | −47.0 (2) | N1—C9—C14—C13 | 178.3 (2) |
C1—N1—C7—C8 | −0.6 (2) | C12—C13—C14—C9 | −0.6 (4) |
C9—N1—C7—C8 | −177.68 (16) | C2—C1—C15—C16 | −32.3 (3) |
C1—N1—C7—C6 | 178.39 (19) | N1—C1—C15—C16 | 148.67 (18) |
C9—N1—C7—C6 | 1.3 (3) | C2—C1—C15—C20 | 144.2 (2) |
C5—C6—C7—N1 | −158.22 (18) | N1—C1—C15—C20 | −34.9 (3) |
C5—C6—C7—C8 | 20.6 (3) | C20—C15—C16—C17 | −0.1 (3) |
N1—C7—C8—C2 | 0.7 (2) | C1—C15—C16—C17 | 176.55 (19) |
C6—C7—C8—C2 | −178.24 (19) | C15—C16—C17—C18 | 0.9 (3) |
N1—C7—C8—C3 | −179.65 (17) | C16—C17—C18—C19 | −0.9 (3) |
C6—C7—C8—C3 | 1.4 (3) | C16—C17—C18—Cl1 | 177.85 (17) |
C1—C2—C8—C7 | −0.6 (2) | C17—C18—C19—C20 | 0.2 (3) |
C1—C2—C8—C3 | 179.8 (2) | Cl1—C18—C19—C20 | −178.56 (15) |
O1—C3—C8—C7 | −175.8 (2) | C18—C19—C20—C15 | 0.6 (3) |
C4—C3—C8—C7 | 6.1 (3) | C16—C15—C20—C19 | −0.6 (3) |
O1—C3—C8—C2 | 3.7 (4) | C1—C15—C20—C19 | −177.08 (18) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1i | 0.90 (2) | 2.50 (2) | 3.358 (3) | 158 (2) |
C10—H10···Cg1ii | 0.96 (2) | 2.93 | 3.723 (3) | 142 |
C14—H14···Cg2iii | 0.94 (2) | 2.90 | 3.804 (3) | 162 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z+1. |
(II) 1-(4-fluorophenyl)-2-(4-methoxyphenyl)-6,6-dimethyl-4,5,6,7-tetrahydro- 1
H-indol-4-one
top
Crystal data top
C23H22FNO2 | F(000) = 768 |
Mr = 363.42 | Dx = 1.237 Mg m−3 |
Monoclinic, P21/n | Melting point: 494 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 10.112 (2) Å | Cell parameters from 974 reflections |
b = 19.073 (4) Å | θ = 2.7–24.3° |
c = 11.287 (3) Å | µ = 0.09 mm−1 |
β = 116.348 (3)° | T = 293 K |
V = 1950.8 (8) Å3 | Prism, colourless |
Z = 4 | 0.40 × 0.30 × 0.20 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3562 independent reflections |
Radiation source: sealed tube | 2818 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ϕ and ω scans | θmax = 25.4°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.887, Tmax = 0.983 | k = −22→21 |
14313 measured reflections | l = −13→13 |
Refinement top
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | All H-atom parameters refined |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0502P)2 + 0.3423P] where P = (Fo2 + 2Fc2)/3 |
3562 reflections | (Δ/σ)max < 0.001 |
332 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
Crystal data top
C23H22FNO2 | V = 1950.8 (8) Å3 |
Mr = 363.42 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.112 (2) Å | µ = 0.09 mm−1 |
b = 19.073 (4) Å | T = 293 K |
c = 11.287 (3) Å | 0.40 × 0.30 × 0.20 mm |
β = 116.348 (3)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3562 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2818 reflections with I > 2σ(I) |
Tmin = 0.887, Tmax = 0.983 | Rint = 0.024 |
14313 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.106 | All H-atom parameters refined |
S = 1.04 | Δρmax = 0.15 e Å−3 |
3562 reflections | Δρmin = −0.19 e Å−3 |
332 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
F1 | 0.25458 (15) | 0.35840 (6) | 0.68136 (15) | 0.1001 (5) | |
O1 | 0.81733 (13) | −0.04919 (6) | 0.59350 (12) | 0.0591 (3) | |
O2 | 0.74360 (13) | 0.41255 (7) | 0.27699 (13) | 0.0692 (4) | |
N1 | 0.58615 (13) | 0.15763 (6) | 0.58559 (12) | 0.0422 (3) | |
C1 | 0.66762 (15) | 0.16589 (8) | 0.51285 (15) | 0.0421 (3) | |
C2 | 0.73415 (17) | 0.10389 (8) | 0.51610 (15) | 0.0439 (4) | |
C3 | 0.73646 (16) | −0.01635 (8) | 0.62834 (15) | 0.0438 (4) | |
C4 | 0.6681 (2) | −0.05015 (9) | 0.70871 (18) | 0.0511 (4) | |
C5 | 0.63399 (19) | −0.00126 (9) | 0.79896 (16) | 0.0539 (4) | |
C6 | 0.5407 (2) | 0.06088 (9) | 0.71829 (18) | 0.0519 (4) | |
C7 | 0.60495 (16) | 0.09075 (7) | 0.63381 (14) | 0.0417 (3) | |
C8 | 0.69592 (15) | 0.05605 (8) | 0.59254 (14) | 0.0419 (3) | |
C9 | 0.50004 (16) | 0.21030 (7) | 0.61026 (15) | 0.0419 (3) | |
C10 | 0.56745 (19) | 0.26830 (9) | 0.68513 (18) | 0.0548 (4) | |
C11 | 0.4849 (2) | 0.31890 (9) | 0.7094 (2) | 0.0643 (5) | |
C12 | 0.3365 (2) | 0.30926 (9) | 0.6576 (2) | 0.0625 (5) | |
C13 | 0.2667 (2) | 0.25201 (10) | 0.5838 (2) | 0.0642 (5) | |
C14 | 0.34993 (18) | 0.20199 (9) | 0.55971 (18) | 0.0522 (4) | |
C15 | 0.67816 (16) | 0.23226 (8) | 0.45051 (14) | 0.0427 (4) | |
C16 | 0.81536 (18) | 0.25265 (9) | 0.46274 (18) | 0.0529 (4) | |
C17 | 0.83263 (19) | 0.31212 (9) | 0.40332 (18) | 0.0573 (4) | |
C18 | 0.71305 (17) | 0.35407 (8) | 0.32950 (15) | 0.0473 (4) | |
C19 | 0.57575 (19) | 0.33536 (9) | 0.31572 (17) | 0.0543 (4) | |
C20 | 0.55954 (18) | 0.27460 (9) | 0.37593 (18) | 0.0555 (4) | |
C21 | 0.5437 (4) | −0.04221 (14) | 0.8545 (3) | 0.0829 (7) | |
C22 | 0.7775 (3) | 0.02470 (16) | 0.9109 (2) | 0.0837 (7) | |
C23 | 0.6276 (3) | 0.45901 (14) | 0.2033 (3) | 0.0835 (7) | |
H2 | 0.7935 (17) | 0.0944 (8) | 0.4719 (14) | 0.045 (4)* | |
H4A | 0.7330 (19) | −0.0871 (9) | 0.7600 (16) | 0.059 (5)* | |
H4B | 0.575 (2) | −0.0728 (9) | 0.6444 (17) | 0.060 (5)* | |
H6A | 0.532 (2) | 0.0967 (10) | 0.7770 (18) | 0.067 (5)* | |
H6B | 0.437 (2) | 0.0456 (9) | 0.6609 (17) | 0.061 (5)* | |
H10 | 0.674 (2) | 0.2724 (9) | 0.7212 (17) | 0.068 (5)* | |
H11 | 0.529 (2) | 0.3602 (11) | 0.762 (2) | 0.078 (6)* | |
H13 | 0.161 (2) | 0.2480 (10) | 0.5496 (18) | 0.077 (6)* | |
H14 | 0.3025 (17) | 0.1611 (9) | 0.5099 (16) | 0.052 (4)* | |
H16 | 0.901 (2) | 0.2242 (10) | 0.5145 (17) | 0.066 (5)* | |
H17 | 0.930 (2) | 0.3261 (10) | 0.4126 (18) | 0.071 (5)* | |
H19 | 0.489 (2) | 0.3630 (9) | 0.2640 (17) | 0.065 (5)* | |
H20 | 0.462 (2) | 0.2606 (9) | 0.3635 (17) | 0.066 (5)* | |
H21A | 0.838 (2) | 0.0544 (12) | 0.882 (2) | 0.094 (7)* | |
H21B | 0.840 (3) | −0.0166 (14) | 0.959 (3) | 0.113 (9)* | |
H21C | 0.758 (3) | 0.0566 (13) | 0.970 (3) | 0.116 (9)* | |
H22A | 0.604 (2) | −0.0790 (13) | 0.910 (2) | 0.096 (7)* | |
H23B | 0.575 (3) | 0.4718 (13) | 0.252 (3) | 0.114 (9)* | |
H22C | 0.522 (3) | −0.0119 (14) | 0.911 (3) | 0.116 (9)* | |
H23A | 0.555 (3) | 0.4363 (13) | 0.124 (3) | 0.112 (9)* | |
H22B | 0.447 (3) | −0.0596 (15) | 0.783 (3) | 0.130 (11)* | |
H23C | 0.671 (2) | 0.4962 (12) | 0.181 (2) | 0.092 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F1 | 0.1069 (10) | 0.0639 (7) | 0.1599 (13) | 0.0262 (7) | 0.0866 (10) | −0.0064 (8) |
O1 | 0.0650 (7) | 0.0424 (6) | 0.0790 (8) | 0.0106 (5) | 0.0402 (7) | 0.0023 (6) |
O2 | 0.0616 (7) | 0.0595 (8) | 0.0907 (9) | 0.0040 (6) | 0.0375 (7) | 0.0307 (7) |
N1 | 0.0440 (7) | 0.0343 (7) | 0.0515 (7) | 0.0028 (5) | 0.0240 (6) | 0.0015 (6) |
C1 | 0.0405 (8) | 0.0382 (8) | 0.0486 (9) | −0.0014 (6) | 0.0205 (7) | 0.0011 (7) |
C2 | 0.0441 (8) | 0.0419 (9) | 0.0513 (9) | 0.0017 (7) | 0.0261 (7) | 0.0001 (7) |
C3 | 0.0404 (8) | 0.0380 (8) | 0.0477 (9) | 0.0008 (6) | 0.0146 (7) | −0.0026 (7) |
C4 | 0.0518 (10) | 0.0401 (9) | 0.0580 (10) | 0.0037 (8) | 0.0213 (8) | 0.0095 (8) |
C5 | 0.0616 (10) | 0.0524 (10) | 0.0488 (9) | 0.0055 (8) | 0.0256 (8) | 0.0092 (8) |
C6 | 0.0602 (11) | 0.0470 (10) | 0.0577 (10) | 0.0059 (8) | 0.0344 (9) | 0.0067 (8) |
C7 | 0.0431 (8) | 0.0359 (8) | 0.0456 (8) | 0.0010 (6) | 0.0193 (7) | 0.0014 (6) |
C8 | 0.0419 (8) | 0.0365 (8) | 0.0473 (8) | 0.0017 (6) | 0.0196 (7) | −0.0003 (7) |
C9 | 0.0442 (8) | 0.0354 (8) | 0.0483 (8) | 0.0030 (6) | 0.0225 (7) | 0.0023 (7) |
C10 | 0.0478 (9) | 0.0457 (10) | 0.0683 (11) | −0.0037 (8) | 0.0234 (9) | −0.0082 (8) |
C11 | 0.0736 (13) | 0.0419 (10) | 0.0824 (13) | −0.0031 (9) | 0.0393 (11) | −0.0156 (9) |
C12 | 0.0724 (12) | 0.0415 (10) | 0.0892 (13) | 0.0145 (9) | 0.0500 (11) | 0.0037 (9) |
C13 | 0.0465 (10) | 0.0550 (11) | 0.0947 (14) | 0.0075 (9) | 0.0346 (10) | 0.0043 (10) |
C14 | 0.0457 (9) | 0.0419 (9) | 0.0669 (11) | −0.0016 (7) | 0.0231 (8) | −0.0031 (8) |
C15 | 0.0437 (8) | 0.0379 (8) | 0.0473 (8) | −0.0003 (6) | 0.0210 (7) | 0.0009 (7) |
C16 | 0.0439 (9) | 0.0492 (10) | 0.0678 (11) | 0.0064 (8) | 0.0269 (8) | 0.0127 (8) |
C17 | 0.0451 (9) | 0.0554 (11) | 0.0770 (12) | 0.0007 (8) | 0.0323 (9) | 0.0142 (9) |
C18 | 0.0518 (9) | 0.0430 (9) | 0.0513 (9) | −0.0018 (7) | 0.0267 (8) | 0.0056 (7) |
C19 | 0.0456 (9) | 0.0536 (10) | 0.0603 (10) | 0.0060 (8) | 0.0205 (8) | 0.0151 (8) |
C20 | 0.0396 (8) | 0.0557 (10) | 0.0684 (11) | −0.0023 (8) | 0.0212 (8) | 0.0124 (9) |
C21 | 0.111 (2) | 0.0746 (15) | 0.0873 (17) | 0.0171 (15) | 0.0656 (17) | 0.0314 (14) |
C22 | 0.0902 (16) | 0.0896 (18) | 0.0526 (12) | 0.0009 (15) | 0.0149 (12) | −0.0037 (12) |
C23 | 0.0764 (15) | 0.0693 (15) | 0.1024 (19) | 0.0072 (13) | 0.0374 (15) | 0.0427 (14) |
Geometric parameters (Å, º) top
F1—C12 | 1.3545 (18) | C10—H10 | 0.972 (18) |
O1—C3 | 1.2252 (17) | C11—C12 | 1.359 (3) |
O2—C18 | 1.3613 (18) | C11—H11 | 0.97 (2) |
O2—C23 | 1.409 (2) | C12—C13 | 1.365 (3) |
N1—C7 | 1.3667 (18) | C13—C14 | 1.377 (2) |
N1—C1 | 1.4065 (18) | C13—H13 | 0.96 (2) |
N1—C9 | 1.4352 (18) | C14—H14 | 0.956 (17) |
C1—C2 | 1.353 (2) | C15—C20 | 1.380 (2) |
C1—C15 | 1.475 (2) | C15—C16 | 1.388 (2) |
C2—C8 | 1.422 (2) | C16—C17 | 1.368 (2) |
C2—H2 | 0.953 (15) | C16—H16 | 0.968 (19) |
C3—C8 | 1.446 (2) | C17—C18 | 1.379 (2) |
C3—C4 | 1.508 (2) | C17—H17 | 0.976 (19) |
C4—C5 | 1.529 (2) | C18—C19 | 1.374 (2) |
C4—H4A | 0.962 (18) | C19—C20 | 1.389 (2) |
C4—H4B | 0.996 (18) | C19—H19 | 0.967 (19) |
C5—C22 | 1.523 (3) | C20—H20 | 0.974 (18) |
C5—C21 | 1.531 (3) | C21—H22A | 0.96 (2) |
C5—C6 | 1.537 (2) | C21—H22C | 0.96 (3) |
C6—C7 | 1.485 (2) | C21—H22B | 1.01 (3) |
C6—H6A | 0.981 (19) | C22—H21A | 0.99 (2) |
C6—H6B | 1.001 (18) | C22—H21B | 1.01 (3) |
C7—C8 | 1.3717 (19) | C22—H21C | 0.99 (3) |
C9—C14 | 1.373 (2) | C23—H23B | 0.95 (3) |
C9—C10 | 1.375 (2) | C23—H23A | 0.97 (3) |
C10—C11 | 1.381 (2) | C23—H23C | 0.93 (2) |
| | | |
C18—O2—C23 | 118.80 (15) | F1—C12—C11 | 118.46 (17) |
C7—N1—C1 | 108.84 (11) | F1—C12—C13 | 118.56 (17) |
C7—N1—C9 | 124.41 (12) | C11—C12—C13 | 122.98 (16) |
C1—N1—C9 | 126.72 (12) | C12—C13—C14 | 118.60 (17) |
C2—C1—N1 | 107.42 (12) | C12—C13—H13 | 119.2 (12) |
C2—C1—C15 | 128.52 (13) | C14—C13—H13 | 122.1 (12) |
N1—C1—C15 | 124.03 (12) | C9—C14—C13 | 119.86 (17) |
C1—C2—C8 | 108.15 (13) | C9—C14—H14 | 120.8 (9) |
C1—C2—H2 | 124.9 (9) | C13—C14—H14 | 119.4 (9) |
C8—C2—H2 | 126.9 (9) | C20—C15—C16 | 117.19 (14) |
O1—C3—C8 | 123.05 (14) | C20—C15—C1 | 124.48 (13) |
O1—C3—C4 | 121.62 (14) | C16—C15—C1 | 118.28 (13) |
C8—C3—C4 | 115.30 (13) | C17—C16—C15 | 121.55 (15) |
C3—C4—C5 | 116.06 (14) | C17—C16—H16 | 119.1 (10) |
C3—C4—H4A | 107.6 (10) | C15—C16—H16 | 119.4 (10) |
C5—C4—H4A | 110.0 (10) | C16—C17—C18 | 120.58 (15) |
C3—C4—H4B | 106.5 (9) | C16—C17—H17 | 121.0 (11) |
C5—C4—H4B | 109.3 (10) | C18—C17—H17 | 118.4 (11) |
H4A—C4—H4B | 107.0 (14) | O2—C18—C19 | 125.22 (15) |
C22—C5—C4 | 109.72 (17) | O2—C18—C17 | 115.52 (14) |
C22—C5—C21 | 110.4 (2) | C19—C18—C17 | 119.25 (15) |
C4—C5—C21 | 108.26 (17) | C18—C19—C20 | 119.60 (16) |
C22—C5—C6 | 110.44 (17) | C18—C19—H19 | 121.9 (10) |
C4—C5—C6 | 109.65 (13) | C20—C19—H19 | 118.5 (10) |
C21—C5—C6 | 108.35 (16) | C15—C20—C19 | 121.82 (15) |
C7—C6—C5 | 110.33 (13) | C15—C20—H20 | 118.7 (10) |
C7—C6—H6A | 111.2 (10) | C19—C20—H20 | 119.5 (10) |
C5—C6—H6A | 110.5 (10) | C5—C21—H22A | 108.5 (13) |
C7—C6—H6B | 109.2 (10) | C5—C21—H22C | 108.7 (16) |
C5—C6—H6B | 110.5 (10) | H22A—C21—H22C | 106 (2) |
H6A—C6—H6B | 105.0 (14) | C5—C21—H22B | 112.7 (15) |
N1—C7—C8 | 108.11 (12) | H22A—C21—H22B | 113 (2) |
N1—C7—C6 | 126.19 (13) | H22C—C21—H22B | 108 (2) |
C8—C7—C6 | 125.70 (14) | C5—C22—H21A | 114.4 (13) |
C7—C8—C2 | 107.48 (13) | C5—C22—H21B | 109.5 (15) |
C7—C8—C3 | 121.03 (13) | H21A—C22—H21B | 107.3 (19) |
C2—C8—C3 | 131.49 (13) | C5—C22—H21C | 111.0 (15) |
C14—C9—C10 | 120.20 (14) | H21A—C22—H21C | 102 (2) |
C14—C9—N1 | 119.51 (14) | H21B—C22—H21C | 112 (2) |
C10—C9—N1 | 120.28 (13) | O2—C23—H23B | 110.7 (16) |
C9—C10—C11 | 120.37 (16) | O2—C23—H23A | 110.7 (16) |
C9—C10—H10 | 118.5 (10) | H23B—C23—H23A | 105 (2) |
C11—C10—H10 | 121.2 (10) | O2—C23—H23C | 105.8 (14) |
C12—C11—C10 | 117.98 (17) | H23B—C23—H23C | 115 (2) |
C12—C11—H11 | 119.7 (12) | H23A—C23—H23C | 110 (2) |
C10—C11—H11 | 122.4 (12) | | |
| | | |
C7—N1—C1—C2 | 0.61 (16) | C7—N1—C9—C14 | −66.4 (2) |
C9—N1—C1—C2 | 178.88 (14) | C1—N1—C9—C14 | 115.63 (17) |
C7—N1—C1—C15 | −177.52 (13) | C7—N1—C9—C10 | 112.95 (17) |
C9—N1—C1—C15 | 0.7 (2) | C1—N1—C9—C10 | −65.1 (2) |
N1—C1—C2—C8 | −0.56 (17) | C14—C9—C10—C11 | −0.4 (3) |
C15—C1—C2—C8 | 177.46 (14) | N1—C9—C10—C11 | −179.74 (15) |
O1—C3—C4—C5 | 151.96 (15) | C9—C10—C11—C12 | 0.2 (3) |
C8—C3—C4—C5 | −29.9 (2) | C10—C11—C12—F1 | 179.66 (17) |
C3—C4—C5—C22 | −68.4 (2) | C10—C11—C12—C13 | 0.4 (3) |
C3—C4—C5—C21 | 171.05 (18) | F1—C12—C13—C14 | −179.90 (16) |
C3—C4—C5—C6 | 53.03 (19) | C11—C12—C13—C14 | −0.6 (3) |
C22—C5—C6—C7 | 74.1 (2) | C10—C9—C14—C13 | 0.2 (3) |
C4—C5—C6—C7 | −46.9 (2) | N1—C9—C14—C13 | 179.50 (15) |
C21—C5—C6—C7 | −164.91 (18) | C12—C13—C14—C9 | 0.3 (3) |
C1—N1—C7—C8 | −0.41 (16) | C2—C1—C15—C20 | 135.86 (18) |
C9—N1—C7—C8 | −178.73 (13) | N1—C1—C15—C20 | −46.4 (2) |
C1—N1—C7—C6 | 178.56 (15) | C2—C1—C15—C16 | −41.5 (2) |
C9—N1—C7—C6 | 0.2 (2) | N1—C1—C15—C16 | 136.24 (16) |
C5—C6—C7—N1 | −155.93 (15) | C20—C15—C16—C17 | −0.1 (3) |
C5—C6—C7—C8 | 22.9 (2) | C1—C15—C16—C17 | 177.44 (16) |
N1—C7—C8—C2 | 0.06 (17) | C15—C16—C17—C18 | 0.4 (3) |
C6—C7—C8—C2 | −178.92 (15) | C23—O2—C18—C19 | 0.7 (3) |
N1—C7—C8—C3 | 179.97 (13) | C23—O2—C18—C17 | −178.3 (2) |
C6—C7—C8—C3 | 1.0 (2) | C16—C17—C18—O2 | 178.84 (16) |
C1—C2—C8—C7 | 0.32 (17) | C16—C17—C18—C19 | −0.2 (3) |
C1—C2—C8—C3 | −179.58 (16) | O2—C18—C19—C20 | −179.13 (16) |
O1—C3—C8—C7 | 179.99 (15) | C17—C18—C19—C20 | −0.1 (3) |
C4—C3—C8—C7 | 1.9 (2) | C16—C15—C20—C19 | −0.3 (3) |
O1—C3—C8—C2 | −0.1 (3) | C1—C15—C20—C19 | −177.66 (15) |
C4—C3—C8—C2 | −178.19 (16) | C18—C19—C20—C15 | 0.4 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O1i | 0.97 (2) | 2.41 (2) | 3.366 (2) | 169 (1) |
C14—H14···O1ii | 0.96 (2) | 2.48 (2) | 3.428 (2) | 173 (1) |
C4—H4B···Cg1ii | 1.00 (2) | 2.69 | 3.606 (2) | 166 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+1, −y, −z+1. |
(III) 6,6-dimethyl-1,2-diphenyl-4,5,6,7-tetrahydro-1
H-indol-4-one
top
Crystal data top
C22H21NO | Z = 2 |
Mr = 315.40 | F(000) = 336 |
Triclinic, P1 | Dx = 1.169 Mg m−3 |
Hall symbol: -P 1 | Melting point: 482 K |
a = 9.315 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.793 (5) Å | Cell parameters from 985 reflections |
c = 11.048 (6) Å | θ = 2.4–24.2° |
α = 81.362 (9)° | µ = 0.07 mm−1 |
β = 65.691 (7)° | T = 293 K |
γ = 77.999 (8)° | Block, colourless |
V = 896.0 (8) Å3 | 0.35 × 0.30 × 0.20 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3259 independent reflections |
Radiation source: sealed tube | 2604 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
ϕ and ω scans | θmax = 25.4°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.946, Tmax = 0.986 | k = −11→11 |
7395 measured reflections | l = −12→13 |
Refinement top
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | All H-atom parameters refined |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0528P)2 + 0.121P] where P = (Fo2 + 2Fc2)/3 |
3259 reflections | (Δ/σ)max < 0.001 |
301 parameters | Δρmax = 0.13 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
Crystal data top
C22H21NO | γ = 77.999 (8)° |
Mr = 315.40 | V = 896.0 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.315 (5) Å | Mo Kα radiation |
b = 9.793 (5) Å | µ = 0.07 mm−1 |
c = 11.048 (6) Å | T = 293 K |
α = 81.362 (9)° | 0.35 × 0.30 × 0.20 mm |
β = 65.691 (7)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3259 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2604 reflections with I > 2σ(I) |
Tmin = 0.946, Tmax = 0.986 | Rint = 0.014 |
7395 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.104 | All H-atom parameters refined |
S = 1.04 | Δρmax = 0.13 e Å−3 |
3259 reflections | Δρmin = −0.17 e Å−3 |
301 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.28072 (13) | 0.23798 (11) | 0.69871 (10) | 0.0393 (3) | |
O1 | 0.49380 (13) | 0.19296 (13) | 0.25063 (10) | 0.0642 (3) | |
C1 | 0.15640 (15) | 0.26748 (14) | 0.65309 (13) | 0.0394 (3) | |
C2 | 0.22397 (16) | 0.25684 (15) | 0.51884 (13) | 0.0420 (3) | |
C3 | 0.51835 (16) | 0.19015 (15) | 0.35162 (13) | 0.0431 (3) | |
C4 | 0.68424 (17) | 0.14790 (18) | 0.35118 (15) | 0.0487 (4) | |
C5 | 0.71311 (16) | 0.21092 (15) | 0.45697 (14) | 0.0457 (3) | |
C6 | 0.58507 (17) | 0.17938 (17) | 0.59576 (15) | 0.0455 (3) | |
C7 | 0.42332 (15) | 0.21093 (14) | 0.59246 (13) | 0.0384 (3) | |
C8 | 0.39170 (15) | 0.22049 (14) | 0.48016 (13) | 0.0394 (3) | |
C9 | 0.26477 (16) | 0.24451 (14) | 0.83309 (12) | 0.0403 (3) | |
C10 | 0.20043 (18) | 0.36894 (16) | 0.89371 (15) | 0.0489 (4) | |
C11 | 0.1867 (2) | 0.37528 (19) | 1.02188 (16) | 0.0562 (4) | |
C12 | 0.2375 (2) | 0.2583 (2) | 1.08890 (16) | 0.0605 (5) | |
C13 | 0.3022 (2) | 0.1343 (2) | 1.02774 (16) | 0.0649 (5) | |
C14 | 0.3162 (2) | 0.12617 (17) | 0.89933 (15) | 0.0547 (4) | |
C15 | −0.01448 (16) | 0.29904 (15) | 0.73970 (13) | 0.0424 (3) | |
C16 | −0.11164 (17) | 0.40663 (17) | 0.69814 (15) | 0.0508 (4) | |
C17 | −0.27475 (19) | 0.4344 (2) | 0.77108 (19) | 0.0637 (5) | |
C18 | −0.3431 (2) | 0.3564 (2) | 0.8878 (2) | 0.0696 (5) | |
C19 | −0.2492 (2) | 0.2513 (2) | 0.93185 (19) | 0.0705 (5) | |
C20 | −0.0853 (2) | 0.22134 (18) | 0.85879 (16) | 0.0584 (4) | |
C21 | 0.8764 (2) | 0.1419 (2) | 0.4570 (2) | 0.0680 (5) | |
C22 | 0.7097 (3) | 0.36887 (19) | 0.4255 (2) | 0.0652 (5) | |
H2 | 0.1666 (17) | 0.2680 (14) | 0.4612 (14) | 0.045 (4)* | |
H4A | 0.761 (2) | 0.1727 (17) | 0.2616 (18) | 0.066 (5)* | |
H4B | 0.701 (2) | 0.0449 (19) | 0.3678 (16) | 0.067 (5)* | |
H6A | 0.6068 (17) | 0.0805 (17) | 0.6255 (14) | 0.050 (4)* | |
H6B | 0.5899 (18) | 0.2307 (16) | 0.6634 (16) | 0.054 (4)* | |
H10 | 0.165 (2) | 0.4500 (18) | 0.8462 (16) | 0.065 (5)* | |
H11 | 0.143 (2) | 0.463 (2) | 1.0643 (17) | 0.072 (5)* | |
H12 | 0.230 (2) | 0.2643 (18) | 1.1758 (18) | 0.072 (5)* | |
H13 | 0.337 (2) | 0.050 (2) | 1.0744 (19) | 0.086 (6)* | |
H14 | 0.361 (2) | 0.039 (2) | 0.8553 (18) | 0.071 (5)* | |
H16 | −0.061 (2) | 0.4652 (18) | 0.6129 (17) | 0.067 (5)* | |
H17 | −0.342 (2) | 0.513 (2) | 0.7411 (19) | 0.085 (6)* | |
H18 | −0.457 (3) | 0.377 (2) | 0.938 (2) | 0.093 (6)* | |
H19 | −0.288 (2) | 0.198 (2) | 1.012 (2) | 0.090 (6)* | |
H20 | −0.018 (2) | 0.1455 (18) | 0.8871 (16) | 0.060 (5)* | |
H21A | 0.723 (2) | 0.416 (2) | 0.494 (2) | 0.091 (7)* | |
H21B | 0.609 (2) | 0.417 (2) | 0.4139 (17) | 0.075 (5)* | |
H21C | 0.800 (3) | 0.386 (2) | 0.337 (2) | 0.095 (7)* | |
H22A | 0.960 (3) | 0.158 (2) | 0.369 (2) | 0.099 (7)* | |
H22B | 0.880 (2) | 0.034 (2) | 0.478 (2) | 0.092 (6)* | |
H22C | 0.896 (2) | 0.178 (2) | 0.528 (2) | 0.089 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0375 (6) | 0.0475 (7) | 0.0306 (6) | −0.0048 (5) | −0.0117 (5) | −0.0048 (5) |
O1 | 0.0511 (6) | 0.1027 (9) | 0.0342 (6) | −0.0018 (6) | −0.0143 (5) | −0.0137 (5) |
C1 | 0.0350 (7) | 0.0462 (8) | 0.0361 (7) | −0.0062 (6) | −0.0129 (6) | −0.0038 (6) |
C2 | 0.0366 (7) | 0.0553 (9) | 0.0346 (7) | −0.0062 (6) | −0.0149 (6) | −0.0040 (6) |
C3 | 0.0418 (8) | 0.0486 (8) | 0.0354 (8) | −0.0058 (6) | −0.0119 (6) | −0.0049 (6) |
C4 | 0.0379 (8) | 0.0564 (10) | 0.0429 (9) | −0.0015 (7) | −0.0083 (7) | −0.0086 (7) |
C5 | 0.0350 (7) | 0.0514 (8) | 0.0482 (8) | −0.0049 (6) | −0.0145 (6) | −0.0048 (6) |
C6 | 0.0424 (8) | 0.0537 (9) | 0.0432 (8) | −0.0059 (6) | −0.0208 (7) | −0.0029 (7) |
C7 | 0.0365 (7) | 0.0424 (7) | 0.0347 (7) | −0.0059 (5) | −0.0125 (6) | −0.0032 (5) |
C8 | 0.0362 (7) | 0.0471 (8) | 0.0325 (7) | −0.0059 (6) | −0.0112 (6) | −0.0040 (5) |
C9 | 0.0398 (7) | 0.0484 (8) | 0.0317 (7) | −0.0076 (6) | −0.0124 (6) | −0.0041 (6) |
C10 | 0.0519 (9) | 0.0498 (9) | 0.0447 (8) | −0.0034 (7) | −0.0198 (7) | −0.0065 (7) |
C11 | 0.0569 (10) | 0.0655 (11) | 0.0468 (9) | −0.0026 (8) | −0.0187 (8) | −0.0215 (8) |
C12 | 0.0609 (10) | 0.0862 (13) | 0.0355 (8) | −0.0107 (9) | −0.0186 (8) | −0.0107 (8) |
C13 | 0.0783 (12) | 0.0709 (12) | 0.0437 (9) | −0.0018 (9) | −0.0295 (9) | 0.0032 (8) |
C14 | 0.0690 (10) | 0.0510 (9) | 0.0409 (8) | −0.0006 (8) | −0.0222 (8) | −0.0052 (7) |
C15 | 0.0378 (7) | 0.0510 (8) | 0.0368 (7) | −0.0095 (6) | −0.0099 (6) | −0.0100 (6) |
C16 | 0.0421 (8) | 0.0638 (10) | 0.0440 (9) | −0.0036 (7) | −0.0145 (7) | −0.0104 (7) |
C17 | 0.0430 (9) | 0.0809 (12) | 0.0659 (11) | 0.0009 (8) | −0.0189 (8) | −0.0243 (9) |
C18 | 0.0384 (9) | 0.0863 (13) | 0.0745 (13) | −0.0114 (9) | −0.0033 (9) | −0.0321 (10) |
C19 | 0.0604 (11) | 0.0804 (13) | 0.0532 (11) | −0.0303 (10) | 0.0051 (9) | −0.0086 (9) |
C20 | 0.0526 (9) | 0.0614 (10) | 0.0500 (9) | −0.0139 (8) | −0.0083 (8) | 0.0005 (8) |
C21 | 0.0403 (9) | 0.0882 (15) | 0.0744 (13) | −0.0021 (9) | −0.0237 (9) | −0.0108 (11) |
C22 | 0.0676 (12) | 0.0571 (10) | 0.0710 (13) | −0.0197 (9) | −0.0248 (10) | 0.0015 (9) |
Geometric parameters (Å, º) top
N1—C7 | 1.3696 (17) | C11—C12 | 1.376 (2) |
N1—C1 | 1.4057 (18) | C11—H11 | 0.974 (19) |
N1—C9 | 1.4399 (18) | C12—C13 | 1.379 (3) |
O1—C3 | 1.2231 (17) | C12—H12 | 0.945 (18) |
C1—C2 | 1.363 (2) | C13—C14 | 1.383 (2) |
C1—C15 | 1.4747 (19) | C13—H13 | 0.97 (2) |
C2—C8 | 1.419 (2) | C14—H14 | 0.976 (19) |
C2—H2 | 0.968 (15) | C15—C20 | 1.392 (2) |
C3—C8 | 1.4486 (19) | C15—C16 | 1.393 (2) |
C3—C4 | 1.512 (2) | C16—C17 | 1.385 (2) |
C4—C5 | 1.537 (2) | C16—H16 | 1.011 (18) |
C4—H4A | 0.984 (17) | C17—C18 | 1.372 (3) |
C4—H4B | 0.989 (18) | C17—H17 | 1.00 (2) |
C5—C22 | 1.530 (2) | C18—C19 | 1.374 (3) |
C5—C21 | 1.530 (2) | C18—H18 | 0.97 (2) |
C5—C6 | 1.541 (2) | C19—C20 | 1.392 (3) |
C6—C7 | 1.488 (2) | C19—H19 | 0.93 (2) |
C6—H6A | 0.982 (16) | C20—H20 | 0.970 (17) |
C6—H6B | 0.982 (17) | C21—H22A | 0.98 (2) |
C7—C8 | 1.3745 (19) | C21—H22B | 1.05 (2) |
C9—C10 | 1.380 (2) | C21—H22C | 1.00 (2) |
C9—C14 | 1.383 (2) | C22—H21A | 1.01 (2) |
C10—C11 | 1.378 (2) | C22—H21B | 1.01 (2) |
C10—H10 | 0.963 (16) | C22—H21C | 1.01 (2) |
| | | |
C7—N1—C1 | 108.99 (11) | C12—C11—C10 | 120.19 (16) |
C7—N1—C9 | 124.53 (11) | C12—C11—H11 | 120.0 (10) |
C1—N1—C9 | 126.34 (11) | C10—C11—H11 | 119.8 (10) |
C2—C1—N1 | 107.35 (12) | C11—C12—C13 | 119.92 (16) |
C2—C1—C15 | 128.18 (12) | C11—C12—H12 | 119.6 (11) |
N1—C1—C15 | 124.44 (12) | C13—C12—H12 | 120.4 (11) |
C1—C2—C8 | 107.92 (12) | C12—C13—C14 | 120.55 (16) |
C1—C2—H2 | 125.7 (9) | C12—C13—H13 | 120.9 (12) |
C8—C2—H2 | 126.4 (9) | C14—C13—H13 | 118.6 (12) |
O1—C3—C8 | 122.93 (13) | C9—C14—C13 | 118.94 (16) |
O1—C3—C4 | 121.66 (13) | C9—C14—H14 | 119.7 (10) |
C8—C3—C4 | 115.36 (12) | C13—C14—H14 | 121.3 (10) |
C3—C4—C5 | 115.46 (12) | C20—C15—C16 | 118.15 (14) |
C3—C4—H4A | 107.9 (10) | C20—C15—C1 | 122.82 (14) |
C5—C4—H4A | 110.2 (10) | C16—C15—C1 | 118.95 (13) |
C3—C4—H4B | 106.3 (10) | C17—C16—C15 | 121.34 (16) |
C5—C4—H4B | 108.0 (10) | C17—C16—H16 | 119.7 (10) |
H4A—C4—H4B | 108.7 (14) | C15—C16—H16 | 119.0 (10) |
C22—C5—C21 | 109.51 (15) | C18—C17—C16 | 119.88 (18) |
C22—C5—C4 | 110.08 (14) | C18—C17—H17 | 119.7 (11) |
C21—C5—C4 | 108.92 (14) | C16—C17—H17 | 120.3 (12) |
C22—C5—C6 | 110.67 (14) | C17—C18—C19 | 119.79 (17) |
C21—C5—C6 | 108.03 (14) | C17—C18—H18 | 119.1 (12) |
C4—C5—C6 | 109.59 (13) | C19—C18—H18 | 121.1 (12) |
C7—C6—C5 | 110.56 (12) | C18—C19—C20 | 120.91 (18) |
C7—C6—H6A | 109.4 (9) | C18—C19—H19 | 123.8 (13) |
C5—C6—H6A | 110.0 (9) | C20—C19—H19 | 115.2 (13) |
C7—C6—H6B | 111.1 (9) | C15—C20—C19 | 119.92 (17) |
C5—C6—H6B | 111.4 (9) | C15—C20—H20 | 118.2 (10) |
H6A—C6—H6B | 104.2 (12) | C19—C20—H20 | 121.8 (10) |
N1—C7—C8 | 107.92 (12) | C5—C21—H22A | 110.1 (13) |
N1—C7—C6 | 126.65 (12) | C5—C21—H22B | 109.9 (11) |
C8—C7—C6 | 125.42 (12) | H22A—C21—H22B | 108.1 (17) |
C7—C8—C2 | 107.81 (12) | C5—C21—H22C | 110.6 (12) |
C7—C8—C3 | 121.25 (13) | H22A—C21—H22C | 110.7 (18) |
C2—C8—C3 | 130.89 (13) | H22B—C21—H22C | 107.4 (16) |
C10—C9—C14 | 120.72 (14) | C5—C22—H21A | 113.3 (12) |
C10—C9—N1 | 119.78 (12) | C5—C22—H21B | 112.2 (11) |
C14—C9—N1 | 119.49 (13) | H21A—C22—H21B | 108.6 (16) |
C11—C10—C9 | 119.68 (15) | C5—C22—H21C | 108.6 (12) |
C11—C10—H10 | 120.9 (10) | H21A—C22—H21C | 108.1 (17) |
C9—C10—H10 | 119.5 (10) | H21B—C22—H21C | 105.7 (15) |
| | | |
C7—N1—C1—C2 | 0.61 (15) | C4—C3—C8—C7 | 0.08 (19) |
C9—N1—C1—C2 | 176.41 (12) | O1—C3—C8—C2 | 0.3 (2) |
C7—N1—C1—C15 | 178.82 (12) | C4—C3—C8—C2 | −177.02 (14) |
C9—N1—C1—C15 | −5.4 (2) | C7—N1—C9—C10 | 115.85 (15) |
N1—C1—C2—C8 | −0.02 (15) | C1—N1—C9—C10 | −59.32 (18) |
C15—C1—C2—C8 | −178.14 (13) | C7—N1—C9—C14 | −63.29 (18) |
O1—C3—C4—C5 | 152.69 (14) | C1—N1—C9—C14 | 121.54 (16) |
C8—C3—C4—C5 | −29.93 (19) | C14—C9—C10—C11 | −0.3 (2) |
C3—C4—C5—C22 | −68.18 (17) | N1—C9—C10—C11 | −179.40 (13) |
C3—C4—C5—C21 | 171.73 (14) | C9—C10—C11—C12 | 0.3 (2) |
C3—C4—C5—C6 | 53.75 (17) | C10—C11—C12—C13 | −0.1 (3) |
C22—C5—C6—C7 | 74.74 (17) | C11—C12—C13—C14 | −0.2 (3) |
C21—C5—C6—C7 | −165.38 (14) | C10—C9—C14—C13 | 0.0 (2) |
C4—C5—C6—C7 | −46.84 (17) | N1—C9—C14—C13 | 179.14 (14) |
C1—N1—C7—C8 | −0.96 (15) | C12—C13—C14—C9 | 0.2 (3) |
C9—N1—C7—C8 | −176.85 (11) | C2—C1—C15—C20 | 132.34 (17) |
C1—N1—C7—C6 | 177.94 (13) | N1—C1—C15—C20 | −45.5 (2) |
C9—N1—C7—C6 | 2.0 (2) | C2—C1—C15—C16 | −44.4 (2) |
C5—C6—C7—N1 | −158.14 (13) | N1—C1—C15—C16 | 137.79 (15) |
C5—C6—C7—C8 | 20.6 (2) | C20—C15—C16—C17 | −1.4 (2) |
N1—C7—C8—C2 | 0.94 (15) | C1—C15—C16—C17 | 175.52 (14) |
C6—C7—C8—C2 | −177.98 (13) | C15—C16—C17—C18 | 0.9 (3) |
N1—C7—C8—C3 | −176.76 (12) | C16—C17—C18—C19 | 0.2 (3) |
C6—C7—C8—C3 | 4.3 (2) | C17—C18—C19—C20 | −0.8 (3) |
C1—C2—C8—C7 | −0.56 (16) | C16—C15—C20—C19 | 0.7 (2) |
C1—C2—C8—C3 | 176.83 (14) | C1—C15—C20—C19 | −176.04 (15) |
O1—C3—C8—C7 | 177.42 (14) | C18—C19—C20—C15 | 0.4 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O1i | 0.97 (2) | 2.57 (2) | 3.533 (3) | 173 (1) |
C19—H19···O1ii | 0.93 (2) | 2.58 (2) | 3.389 (3) | 145 (2) |
C4—H4B···Cg1i | 0.99 (2) | 2.74 | 3.723 (3) | 172 |
C11—H11···Cg2iii | 0.97 (2) | 2.75 | 3.620 (3) | 149 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z+1; (iii) −x, −y+1, −z+2. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C22H19ClFNO | C23H22FNO2 | C22H21NO |
Mr | 367.83 | 363.42 | 315.40 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 9.246 (3), 10.228 (4), 11.177 (4) | 10.112 (2), 19.073 (4), 11.287 (3) | 9.315 (5), 9.793 (5), 11.048 (6) |
α, β, γ (°) | 80.529 (6), 86.335 (7), 65.120 (6) | 90, 116.348 (3), 90 | 81.362 (9), 65.691 (7), 77.999 (8) |
V (Å3) | 945.7 (6) | 1950.8 (8) | 896.0 (8) |
Z | 2 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.22 | 0.09 | 0.07 |
Crystal size (mm) | 0.50 × 0.30 × 0.20 | 0.40 × 0.30 × 0.20 | 0.35 × 0.30 × 0.20 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.844, 0.957 | 0.887, 0.983 | 0.946, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9987, 3788, 2811 | 14313, 3562, 2818 | 7395, 3259, 2604 |
Rint | 0.024 | 0.024 | 0.014 |
(sin θ/λ)max (Å−1) | 0.625 | 0.602 | 0.602 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.118, 1.04 | 0.041, 0.106, 1.04 | 0.040, 0.104, 1.04 |
No. of reflections | 3788 | 3562 | 3259 |
No. of parameters | 311 | 332 | 301 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.20, −0.22 | 0.15, −0.19 | 0.13, −0.17 |
Selected torsion angles (º) for (I) topC9—N1—C1—C15 | −3.7 (3) | C5—C6—C7—C8 | 20.6 (3) |
O1—C3—C4—C5 | 145.5 (2) | C6—C7—C8—C3 | 1.4 (3) |
C8—C3—C4—C5 | −36.3 (3) | C4—C3—C8—C7 | 6.1 (3) |
C3—C4—C5—C6 | 57.3 (3) | C7—N1—C9—C10 | 106.0 (2) |
C4—C5—C6—C7 | −47.0 (2) | N1—C1—C15—C16 | 148.67 (18) |
C9—N1—C7—C8 | −177.68 (16) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1i | 0.90 (2) | 2.50 (2) | 3.358 (3) | 158 (2) |
C10—H10···Cg1ii | 0.96 (2) | 2.93 | 3.723 (3) | 142 |
C14—H14···Cg2iii | 0.94 (2) | 2.90 | 3.804 (3) | 162 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z+1. |
Selected torsion angles (º) for (II) topC9—N1—C1—C15 | 0.7 (2) | C5—C6—C7—C8 | 22.9 (2) |
O1—C3—C4—C5 | 151.96 (15) | C6—C7—C8—C3 | 1.0 (2) |
C8—C3—C4—C5 | −29.9 (2) | C4—C3—C8—C7 | 1.9 (2) |
C3—C4—C5—C6 | 53.03 (19) | C7—N1—C9—C10 | 112.95 (17) |
C4—C5—C6—C7 | −46.9 (2) | N1—C1—C15—C16 | 136.24 (16) |
C9—N1—C7—C8 | −178.73 (13) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O1i | 0.97 (2) | 2.41 (2) | 3.366 (2) | 169 (1) |
C14—H14···O1ii | 0.96 (2) | 2.48 (2) | 3.428 (2) | 173 (1) |
C4—H4B···Cg1ii | 1.00 (2) | 2.69 | 3.606 (2) | 166 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+1, −y, −z+1. |
Selected torsion angles (º) for (III) topC9—N1—C1—C15 | −5.4 (2) | C5—C6—C7—C8 | 20.6 (2) |
O1—C3—C4—C5 | 152.69 (14) | C6—C7—C8—C3 | 4.3 (2) |
C8—C3—C4—C5 | −29.93 (19) | C4—C3—C8—C7 | 0.08 (19) |
C3—C4—C5—C6 | 53.75 (17) | C7—N1—C9—C10 | 115.85 (15) |
C4—C5—C6—C7 | −46.84 (17) | N1—C1—C15—C16 | 137.79 (15) |
C9—N1—C7—C8 | −176.85 (11) | | |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O1i | 0.97 (2) | 2.57 (2) | 3.533 (3) | 173 (1) |
C19—H19···O1ii | 0.93 (2) | 2.58 (2) | 3.389 (3) | 145 (2) |
C4—H4B···Cg1i | 0.99 (2) | 2.74 | 3.723 (3) | 172 |
C11—H11···Cg2iii | 0.97 (2) | 2.75 | 3.620 (3) | 149 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z+1; (iii) −x, −y+1, −z+2. |
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The generation of different types of packing motifs in crystalline lattices has been illustrated in detail in the literature. Different types of intermolecular interactions, such as hydrogen bonding (Desiraju, 1989, 2000, 2002; Aakeroy, 1997; Guru Row, 1999; Hunter et al., 2001), C—H···π interactions (Nishio et al., 1995; Umezawa et al., 1999; Takahashi et al., 2000), π–π stacking (Hunter, 1993, 1994) and C—H···O hydrogen bonding (Desiraju & Steiner, 1999; Steiner, 2002) have been reviewed extensively. Recently, it has been shown that `organic fluorine' provides similar interactions, to generate packing motifs in the presence or absence of other intermolecular forces (Prasanna & Guru Row, 2000a,b,c, 2001). We have been interested in the study of the role of organic fluorine in the packing of organic molecules which show biological activity (Choudhury Urs Guru Row & Nagarajan, 2002; Choudhury Urs Smith et al., 2002). Against this background, we report here the crystal and molecular structures of 2-(4-chlorophenyl)-1-(4-fluorophenyl)-6,6-dimethyl-4,5,6,7-tetrahydro- −1H-indol-4-one, (I), and 1-(4-fluorophenyl)-2-(4-methoxyphenyl)-6,6- dimethyl-4,5,6,7-tetrahydro-1H-indol-4-one, (II), and compare these with the corresponding unsubstituted compound 6,6-dimethyl-1,2-diphenyl-4,5,6,7-tetrahydro-1H-indol-4-one, (III) (Varghese et al., 1986), the structure of which we have redetermined. \sch
Most unsubstituted 4-ketotetrahydroindoles have been found to be biologically inactive (Remers et al., 1971) and the inactivity was attributed to the extended conjugation of the C═O group with the indole N atom (Weiss et al., 1968). In order to delocalize the lone pair of electrons on N and to facilitate the activity of the keto function, a series of 1,2-diaryl derivatives were synthesized (Nagarajan et al., 1985). It was found that differently substituted phenyl groups on the 1- or 2-positions facilitate biological activity. Compound (I) of the present study was inactive, whereas (II) showed considerable activity, as reported by Nagarajan et al. (1985). We have redetermined the structure of the unsubstituted compound, (III), since the intermolecular interactions were not discussed in detail in the earlier report by Varghese et al. (1986).
In compound (I), the six-membered ring of the tetrahydroindole (Fig. 1) has an envelope conformation, with atom C5 − 0.641 (3) Å from the C3/C4/C6/C7/C8 plane. Selected torsion angles are given in Table 1. The dihedral angle between the 1-(4-fluorophenyl) and 2-(4-chlorophenyl) rings is 69.84 (7)°. The packing of the molecules in the crystal lattice (Fig. 2) is stabilized via C—H···O and C—H···π interactions (Table 2). There are two independent C—H···π interactions, which link the molecules in the b direction. Thus, molecules packed around the inversion centres at (1/2,1/2,1/2) and (1,1/2,1/2) are linked by pairs of independent C—H···π interactions. C—H···O interactions about the inversion centre at (1/2,1,1/2) then serve to link these chains to form sheets of molecules in the bc plane In Fig. 2 and Table 2, Cg1 is the centroid of the five-membered N1/C1/C2/C8/C7 ring and Cg2 is the centroid of the C9—C14 phenyl ring. It is of interest to note that there are no interactions involving the halogen atoms, though the structure contains a Cl as well as an F.
In compound (II), the six-membered ring of the tetrahydroindole (Fig. 3) has an envelope conformation, with atom C5 − 0.618 (2) Å from the C3/C4/C6/C7/C8 plane, similar to what was observed for (I). Selected torsion angles are given in Table 3. The dihedral angle between the 1-(4-fluorophenyl) and 2-(4-methoxyphenyl) rings is 60.94 (4)°. The molecules pack in the unit cell (Fig. 4) via two different C—H···O interactions (Table 4) in the (101) plane, generating a sheet structure. This is further stabilized by an additional C—H···π interaction which reinforces the two-dimensional sheet (Fig. 4). In Table 4, Cg1 is the centroid of the five-membered N1/C1/C2/C8/C7 ring. Once again, it is to be noted that the F atom does not generate any significant interaction.
In compound (III), the six-membered ring of the tetrahydroindole (Fig. 5) has an envelope conformation, with atom C5 − 0.632 (2) Å from the C3/C4/C6/C7/C8 plane. Selected torsion angles are given in Table 5. The dihedral angle between the 1-phenyl and 2-phenyl rings is 62.99 (6)°. The variation in dihedral angles in (I), (II) and (III) clearly shows that the conformations of the molecules are significantly different among the three compounds. The molecules of (III) pack in the unit cell via two different C—H···O interactions (Fig. 6 and Table 6) generating a `ladder' motif, which is further reinforced by a C—H···π interaction involving C4—H4B (Table 6). In Table 6, Cg1 is the centroid of the five-membered N1/C1/C2/C8/C7 ring and Cg2 is the centroid of the C9–C14 phenyl ring. These ladders are then linked to form a two-dimensional sheet in the (101) plane via a further C—H···π interaction involving C11—H11 and the centroid Cg2 at (-x, 1 − y, 2 − z).
These three structures illustrate the coexistance of C—H···O and C—H···π interactions to generate different packing motifs with altered molecular conformations. Such subtle variations might have a significant impact on the biological activities of such compounds. Indeed, only compound (II) is found to be biologically active.