organic compounds
(E)-1-([1,1′-Biphenyl]-4-yl)-2-(1,3,3-trimethylindolin-2-ylidene)ethanone
aFacultad de Ciencias Químicas, Universidad de Colima, km 9 Carr. Colima-Coquimatlán s/n, Coquimatlán, Colima 28400, Mexico, bInstituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, México D.F. 04510, Mexico, and cInstituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, México D.F. 04510, Mexico
*Correspondence e-mail: oscar_vazquez@ucol.mx
The title compound, C25H23NO, consists of a biphenyl-4-carbonyl unit attached to an exocyclic double bond group at position 2 of an indole unit, which presents methyl groups as substituents at positions 1 and 3. The molecular conformation is s-cis with an E configuration, supported by weak intramolecular C—H⋯O contacts involving the methyl groups and the carbonyl function. The rings of the biphenyl group are twisted by 37.13 (5)°. In the crystal, C—H⋯O and C—H⋯π interactions link the molecules.
Related literature
For background to the Fisher base (2,3-dihydro-1H-1,3,3-trimethyl-2-methyleneindole), see: Minkin (2004); Przhiyalgovskaya et al. (1987). For applications of derivatives of the Fisher base in materials and organic synthesis, see: Corns et al. (2009); Shimkin et al. (2006); Song et al. (2005); Tarshits et al. (2005); Cui & Kim (2004).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: SMART (Bruker, 1999); cell SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2002); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536811045168/bh2373sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811045168/bh2373Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536811045168/bh2373Isup3.cml
A mixture of 4-biphenylcarboxylic acid (9.59 g, 48.38 mmol) and thionyl chloride (1.5 eq., 8.63 g, 72.57 mmol) in 24 ml of dry benzene was refluxed for 1.5 h, afterward the solvent and the excess of thionyl chloride was evaporated under vacuum. For complete removal of the thionyl chloride, 24 ml of petroleum ether was added to the residue and then eliminated under vacuum. The 4-biphenyl-carbonyl chloride thus obtained was dissolved in 60 ml of dry benzene, then added to a mixture of the Fischer base 1,3,3-trimethyl-2-methyleneindoline (1 eq., 8.38 g, 48.38 mmol) and triethylamine (1.2 eq., 5.81 g, 58.04 mmol) in 60 ml of dry benzene. The reaction mixture was maintained at 40 °C for 2 h, after that it was allowed to stand overnight at room temperature. The final reaction mixture was first washed with water and the organic phase was separated and removed under vacuum. The resulting solid was washed successively with isopropyl alcohol. The crude product was purified using a
with chloroform as a mobile phase. Suitable crystals for X-ray diffraction were obtained from toluene by slow evaporation.The positional parameters of H atoms were calculated geometrically (C—H = 0.93 Å for aromatic CH and 0.96 Å for methyl CH3). The displacement parameters for H atoms were fixed as Uiso(H) = 1.2Ueq(carrier atom) or Uiso(H) = 1.5Ueq(carrier atom).
The compound 2,3-dihydro-1H-1,3,3-trimethyl-2-methyleneindole, well known as the Fischer base, has been widely used in organic synthesis as precursor of different types of chemical switches (Minkin, 2004; Przhiyalgovskaya et al., 1987). Products with different skills to work as switches have been used in optoelectronics (Shimkin et al., 2006), as organic electroluminescent materials (Cui & Kim, 2004) and dyes (Song et al., 2005). Moreover, the enaminoketone derivatives of the Fischer base, like the title compound, are important intermediates for the synthesis of spiropyrans and spirooxazines (Corns et al., 2009), as well as for the preparation of acetylenic products via enaminoketone fragmentation (Tarshits et al., 2005).
The structure of the title compound [alternative name: (E)-2,3-dihydro-2-(biphenylacylidene)-1,3,3-trimethyl-1H-indol], C25H23NO, has monoclinic (P21/c) symmetry. The
exhibits C—H···O intramolecular contacts in a bifurcated fashion with C19 and C20 as the donor atoms and the O atom of carbonyl group O1 as the acceptor (Table 1, Fig. 1). Moreover, despite the molecule presents high conjugation degree, the molecule is not planar; the benzene group (C12···C17) is rotated with respect to indole group (N1···C9) with the dihedral angle of 33.19 (5)°, while the biphenyl rings presents rotation showed by the dihedral angle of 37.13 (5)°.The intermolecular assembly presents an antiparallel arrangement in a head-to-tail stacking mode especially favored by edge-to-face weak C—H···π interaction between 2.739 to 2.891 Å (see Table 2). Moreover, the weak C—H···O interaction formed by C24–H24C···O1 propagates in the ac plane (Fig. 2).
For backgroung to the Fisher base (2,3-dihydro-1H-1,3,3-trimethyl-2-methyleneindole), see: Minkin (2004); Przhiyalgovskaya et al. (1987). For applications of derivatives of the Fisher base in materials and organic synthesis, see: Corns et al. (2009); Shimkin et al. (2006); Song et al. (2005); Tarshits et al. (2005); Cui & Kim (2004).
Data collection: SMART (Bruker, 1999); cell
SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2002); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound. Displacement ellipsoids for non-H atom are drawn at the 30% of probability level. | |
Fig. 2. The crystal packing of the title compound viewed down the a axis, showing the molecules intermolecularly connected by weak O—H···O interactions (dashed lines). H atoms not involved in hydrogen bonding have been omitted. |
C25H23NO | F(000) = 752 |
Mr = 353.44 | Dx = 1.203 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7167 reflections |
a = 12.3274 (13) Å | θ = 2.1–25.3° |
b = 15.7586 (16) Å | µ = 0.07 mm−1 |
c = 10.3848 (11) Å | T = 298 K |
β = 104.719 (2)° | Prism, yellow |
V = 1951.2 (4) Å3 | 0.36 × 0.28 × 0.26 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 2585 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.033 |
Graphite monochromator | θmax = 25.4°, θmin = 1.7° |
Detector resolution: 0.83 pixels mm-1 | h = −14→14 |
ω scans | k = −18→19 |
15883 measured reflections | l = −12→12 |
3584 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.065P)2] where P = (Fo2 + 2Fc2)/3 |
3584 reflections | (Δ/σ)max < 0.001 |
247 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
0 constraints |
C25H23NO | V = 1951.2 (4) Å3 |
Mr = 353.44 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.3274 (13) Å | µ = 0.07 mm−1 |
b = 15.7586 (16) Å | T = 298 K |
c = 10.3848 (11) Å | 0.36 × 0.28 × 0.26 mm |
β = 104.719 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 2585 reflections with I > 2σ(I) |
15883 measured reflections | Rint = 0.033 |
3584 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.18 e Å−3 |
3584 reflections | Δρmin = −0.18 e Å−3 |
247 parameters |
x | y | z | Uiso*/Ueq | ||
O1 | 0.11145 (9) | 0.15214 (6) | 0.45956 (10) | 0.0720 (3) | |
N1 | −0.10316 (9) | 0.01690 (6) | 0.12145 (10) | 0.0495 (3) | |
C2 | −0.04032 (10) | 0.06729 (8) | 0.22033 (12) | 0.0443 (3) | |
C3 | −0.09068 (10) | 0.15640 (7) | 0.20258 (12) | 0.0429 (3) | |
C4 | −0.26386 (11) | 0.20310 (9) | 0.01194 (13) | 0.0520 (3) | |
H4 | −0.2620 | 0.2591 | 0.0405 | 0.062* | |
C5 | −0.34517 (11) | 0.17673 (10) | −0.09918 (14) | 0.0577 (4) | |
H5 | −0.3978 | 0.2153 | −0.1458 | 0.069* | |
C6 | −0.34813 (11) | 0.09381 (10) | −0.14058 (14) | 0.0579 (4) | |
H6 | −0.4032 | 0.0770 | −0.2153 | 0.069* | |
C7 | −0.27119 (12) | 0.03476 (9) | −0.07375 (13) | 0.0555 (4) | |
H7 | −0.2736 | −0.0214 | −0.1017 | 0.067* | |
C8 | −0.19038 (10) | 0.06262 (8) | 0.03644 (12) | 0.0447 (3) | |
C9 | −0.18599 (10) | 0.14580 (8) | 0.07967 (12) | 0.0424 (3) | |
C10 | 0.04982 (11) | 0.03623 (8) | 0.31302 (13) | 0.0527 (4) | |
H10 | 0.0659 | −0.0207 | 0.3034 | 0.063* | |
C11 | 0.12365 (11) | 0.07890 (9) | 0.42363 (13) | 0.0523 (4) | |
C12 | 0.22233 (11) | 0.02928 (8) | 0.50225 (13) | 0.0472 (3) | |
C13 | 0.26762 (11) | 0.04889 (9) | 0.63521 (13) | 0.0530 (4) | |
H13 | 0.2360 | 0.0924 | 0.6741 | 0.064* | |
C14 | 0.35843 (11) | 0.00524 (9) | 0.71096 (13) | 0.0528 (4) | |
H14 | 0.3854 | 0.0185 | 0.8007 | 0.063* | |
C15 | 0.41041 (10) | −0.05831 (8) | 0.65561 (12) | 0.0447 (3) | |
C16 | 0.36776 (10) | −0.07546 (8) | 0.52088 (13) | 0.0490 (3) | |
H16 | 0.4028 | −0.1160 | 0.4802 | 0.059* | |
C17 | 0.27469 (11) | −0.03366 (8) | 0.44639 (13) | 0.0504 (3) | |
H17 | 0.2465 | −0.0478 | 0.3572 | 0.060* | |
C18 | −0.08214 (14) | −0.07245 (9) | 0.10425 (17) | 0.0717 (5) | |
H18A | −0.0069 | −0.0797 | 0.0960 | 0.107* | |
H18B | −0.1341 | −0.0931 | 0.0253 | 0.107* | |
H18C | −0.0916 | −0.1036 | 0.1801 | 0.107* | |
C19 | −0.00644 (11) | 0.22263 (9) | 0.17900 (15) | 0.0586 (4) | |
H19A | 0.0231 | 0.2048 | 0.1063 | 0.088* | |
H19B | 0.0537 | 0.2282 | 0.2580 | 0.088* | |
H19C | −0.0435 | 0.2763 | 0.1579 | 0.088* | |
C20 | −0.13763 (13) | 0.18132 (10) | 0.32054 (13) | 0.0621 (4) | |
H20A | −0.1736 | 0.2357 | 0.3036 | 0.093* | |
H20B | −0.0775 | 0.1843 | 0.4000 | 0.093* | |
H20C | −0.1912 | 0.1396 | 0.3319 | 0.093* | |
C21 | 0.50510 (10) | −0.10866 (8) | 0.73665 (13) | 0.0483 (3) | |
C22 | 0.59153 (11) | −0.13759 (9) | 0.68482 (15) | 0.0555 (4) | |
H22 | 0.5925 | −0.1234 | 0.5982 | 0.067* | |
C23 | 0.67627 (12) | −0.18739 (9) | 0.76088 (17) | 0.0687 (5) | |
H23 | 0.7339 | −0.2061 | 0.7251 | 0.082* | |
C24 | 0.67611 (15) | −0.20941 (10) | 0.88879 (19) | 0.0773 (5) | |
H24 | 0.7326 | −0.2437 | 0.9391 | 0.093* | |
C25 | 0.59186 (15) | −0.18033 (11) | 0.94158 (17) | 0.0782 (5) | |
H25 | 0.5919 | −0.1944 | 1.0286 | 0.094* | |
C26 | 0.50713 (12) | −0.13039 (10) | 0.86699 (15) | 0.0640 (4) | |
H26 | 0.4507 | −0.1110 | 0.9043 | 0.077* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0676 (7) | 0.0569 (7) | 0.0752 (7) | 0.0108 (5) | −0.0118 (6) | −0.0149 (5) |
N1 | 0.0500 (6) | 0.0393 (6) | 0.0520 (6) | 0.0035 (5) | −0.0001 (5) | −0.0079 (5) |
C2 | 0.0436 (7) | 0.0426 (7) | 0.0450 (7) | −0.0015 (6) | 0.0081 (6) | −0.0031 (6) |
C3 | 0.0419 (7) | 0.0388 (7) | 0.0466 (7) | 0.0005 (5) | 0.0089 (6) | −0.0039 (6) |
C4 | 0.0483 (8) | 0.0471 (8) | 0.0605 (9) | 0.0028 (6) | 0.0138 (7) | 0.0052 (6) |
C5 | 0.0444 (8) | 0.0685 (10) | 0.0574 (9) | 0.0055 (7) | 0.0075 (7) | 0.0158 (8) |
C6 | 0.0464 (8) | 0.0744 (11) | 0.0476 (8) | −0.0038 (7) | 0.0024 (6) | 0.0030 (7) |
C7 | 0.0546 (8) | 0.0565 (8) | 0.0512 (8) | −0.0033 (7) | 0.0058 (7) | −0.0082 (7) |
C8 | 0.0421 (7) | 0.0478 (8) | 0.0433 (7) | 0.0000 (6) | 0.0092 (6) | −0.0010 (6) |
C9 | 0.0403 (7) | 0.0438 (7) | 0.0436 (7) | −0.0009 (5) | 0.0116 (6) | 0.0013 (6) |
C10 | 0.0513 (8) | 0.0421 (7) | 0.0575 (9) | 0.0042 (6) | 0.0004 (7) | −0.0033 (6) |
C11 | 0.0502 (8) | 0.0483 (8) | 0.0536 (8) | 0.0014 (6) | 0.0044 (7) | −0.0017 (7) |
C12 | 0.0445 (7) | 0.0486 (8) | 0.0454 (7) | −0.0028 (6) | 0.0058 (6) | 0.0012 (6) |
C13 | 0.0490 (8) | 0.0539 (8) | 0.0535 (8) | 0.0030 (6) | 0.0080 (7) | −0.0059 (6) |
C14 | 0.0498 (8) | 0.0616 (9) | 0.0428 (7) | −0.0012 (7) | 0.0040 (6) | −0.0036 (7) |
C15 | 0.0385 (7) | 0.0461 (7) | 0.0476 (7) | −0.0050 (6) | 0.0074 (6) | 0.0036 (6) |
C16 | 0.0455 (7) | 0.0496 (8) | 0.0512 (8) | 0.0011 (6) | 0.0111 (6) | −0.0014 (6) |
C17 | 0.0503 (8) | 0.0555 (8) | 0.0419 (7) | −0.0009 (6) | 0.0052 (6) | −0.0018 (6) |
C18 | 0.0715 (10) | 0.0470 (9) | 0.0850 (11) | 0.0077 (7) | −0.0012 (9) | −0.0164 (8) |
C19 | 0.0524 (8) | 0.0474 (8) | 0.0721 (10) | −0.0047 (6) | 0.0088 (7) | 0.0017 (7) |
C20 | 0.0611 (9) | 0.0707 (10) | 0.0547 (9) | 0.0088 (8) | 0.0151 (7) | −0.0113 (7) |
C21 | 0.0423 (7) | 0.0448 (7) | 0.0542 (8) | −0.0062 (6) | 0.0059 (6) | 0.0023 (6) |
C22 | 0.0464 (8) | 0.0543 (8) | 0.0618 (9) | −0.0025 (6) | 0.0061 (7) | −0.0063 (7) |
C23 | 0.0493 (9) | 0.0616 (10) | 0.0860 (12) | 0.0067 (7) | 0.0001 (8) | −0.0153 (9) |
C24 | 0.0683 (11) | 0.0556 (10) | 0.0896 (13) | 0.0104 (8) | −0.0137 (10) | 0.0073 (9) |
C25 | 0.0781 (12) | 0.0776 (11) | 0.0711 (11) | 0.0085 (10) | 0.0042 (9) | 0.0251 (9) |
C26 | 0.0575 (9) | 0.0707 (10) | 0.0617 (10) | 0.0040 (7) | 0.0114 (8) | 0.0175 (8) |
O1—C11 | 1.2340 (16) | C14—H14 | 0.9300 |
N1—C2 | 1.3714 (15) | C15—C16 | 1.3904 (18) |
N1—C8 | 1.4043 (15) | C15—C21 | 1.4836 (17) |
N1—C18 | 1.4509 (17) | C16—C17 | 1.3775 (17) |
C2—C10 | 1.3628 (17) | C16—H16 | 0.9300 |
C2—C3 | 1.5276 (17) | C17—H17 | 0.9300 |
C3—C9 | 1.5085 (17) | C18—H18A | 0.9600 |
C3—C20 | 1.5329 (18) | C18—H18B | 0.9600 |
C3—C19 | 1.5352 (18) | C18—H18C | 0.9600 |
C4—C9 | 1.3742 (17) | C19—H19A | 0.9600 |
C4—C5 | 1.3861 (19) | C19—H19B | 0.9600 |
C4—H4 | 0.9300 | C19—H19C | 0.9600 |
C5—C6 | 1.373 (2) | C20—H20A | 0.9600 |
C5—H5 | 0.9300 | C20—H20B | 0.9600 |
C6—C7 | 1.3830 (19) | C20—H20C | 0.9600 |
C6—H6 | 0.9300 | C21—C22 | 1.3871 (19) |
C7—C8 | 1.3840 (17) | C21—C26 | 1.3902 (19) |
C7—H7 | 0.9300 | C22—C23 | 1.3826 (19) |
C8—C9 | 1.3821 (18) | C22—H22 | 0.9300 |
C10—C11 | 1.4383 (17) | C23—C24 | 1.373 (2) |
C10—H10 | 0.9300 | C23—H23 | 0.9300 |
C11—C12 | 1.5010 (18) | C24—C25 | 1.371 (2) |
C12—C13 | 1.3864 (17) | C24—H24 | 0.9300 |
C12—C17 | 1.3883 (18) | C25—C26 | 1.378 (2) |
C13—C14 | 1.3775 (18) | C25—H25 | 0.9300 |
C13—H13 | 0.9300 | C26—H26 | 0.9300 |
C14—C15 | 1.3897 (19) | ||
C2—N1—C8 | 111.73 (10) | C14—C15—C16 | 117.39 (12) |
C2—N1—C18 | 124.71 (11) | C14—C15—C21 | 121.99 (12) |
C8—N1—C18 | 123.55 (11) | C16—C15—C21 | 120.58 (12) |
C10—C2—N1 | 121.67 (12) | C17—C16—C15 | 121.35 (13) |
C10—C2—C3 | 130.46 (11) | C17—C16—H16 | 119.3 |
N1—C2—C3 | 107.87 (10) | C15—C16—H16 | 119.3 |
C9—C3—C2 | 101.86 (9) | C16—C17—C12 | 121.08 (12) |
C9—C3—C20 | 109.48 (10) | C16—C17—H17 | 119.5 |
C2—C3—C20 | 111.31 (11) | C12—C17—H17 | 119.5 |
C9—C3—C19 | 110.69 (11) | N1—C18—H18A | 109.5 |
C2—C3—C19 | 111.94 (11) | N1—C18—H18B | 109.5 |
C20—C3—C19 | 111.18 (11) | H18A—C18—H18B | 109.5 |
C9—C4—C5 | 119.50 (13) | N1—C18—H18C | 109.5 |
C9—C4—H4 | 120.2 | H18A—C18—H18C | 109.5 |
C5—C4—H4 | 120.2 | H18B—C18—H18C | 109.5 |
C6—C5—C4 | 120.13 (13) | C3—C19—H19A | 109.5 |
C6—C5—H5 | 119.9 | C3—C19—H19B | 109.5 |
C4—C5—H5 | 119.9 | H19A—C19—H19B | 109.5 |
C5—C6—C7 | 121.52 (13) | C3—C19—H19C | 109.5 |
C5—C6—H6 | 119.2 | H19A—C19—H19C | 109.5 |
C7—C6—H6 | 119.2 | H19B—C19—H19C | 109.5 |
C6—C7—C8 | 117.34 (13) | C3—C20—H20A | 109.5 |
C6—C7—H7 | 121.3 | C3—C20—H20B | 109.5 |
C8—C7—H7 | 121.3 | H20A—C20—H20B | 109.5 |
C9—C8—C7 | 122.01 (12) | C3—C20—H20C | 109.5 |
C9—C8—N1 | 108.77 (10) | H20A—C20—H20C | 109.5 |
C7—C8—N1 | 129.22 (12) | H20B—C20—H20C | 109.5 |
C4—C9—C8 | 119.49 (12) | C22—C21—C26 | 118.11 (13) |
C4—C9—C3 | 130.76 (12) | C22—C21—C15 | 121.79 (12) |
C8—C9—C3 | 109.74 (10) | C26—C21—C15 | 120.07 (13) |
C2—C10—C11 | 129.28 (13) | C23—C22—C21 | 120.55 (14) |
C2—C10—H10 | 115.4 | C23—C22—H22 | 119.7 |
C11—C10—H10 | 115.4 | C21—C22—H22 | 119.7 |
O1—C11—C10 | 125.30 (12) | C24—C23—C22 | 120.63 (16) |
O1—C11—C12 | 117.83 (12) | C24—C23—H23 | 119.7 |
C10—C11—C12 | 116.86 (12) | C22—C23—H23 | 119.7 |
C13—C12—C17 | 117.59 (12) | C25—C24—C23 | 119.32 (15) |
C13—C12—C11 | 119.42 (12) | C25—C24—H24 | 120.3 |
C17—C12—C11 | 122.92 (12) | C23—C24—H24 | 120.3 |
C14—C13—C12 | 121.37 (13) | C24—C25—C26 | 120.61 (16) |
C14—C13—H13 | 119.3 | C24—C25—H25 | 119.7 |
C12—C13—H13 | 119.3 | C26—C25—H25 | 119.7 |
C13—C14—C15 | 121.13 (12) | C25—C26—C21 | 120.77 (15) |
C13—C14—H14 | 119.4 | C25—C26—H26 | 119.6 |
C15—C14—H14 | 119.4 | C21—C26—H26 | 119.6 |
C8—N1—C2—C10 | −179.03 (12) | N1—C2—C10—C11 | −179.06 (13) |
C18—N1—C2—C10 | 0.1 (2) | C3—C2—C10—C11 | 1.0 (2) |
C8—N1—C2—C3 | 0.94 (14) | C2—C10—C11—O1 | 6.0 (2) |
C18—N1—C2—C3 | −179.94 (13) | C2—C10—C11—C12 | −174.96 (14) |
C10—C2—C3—C9 | 178.67 (14) | O1—C11—C12—C13 | 26.4 (2) |
N1—C2—C3—C9 | −1.30 (13) | C10—C11—C12—C13 | −152.73 (13) |
C10—C2—C3—C20 | −64.73 (18) | O1—C11—C12—C17 | −150.53 (14) |
N1—C2—C3—C20 | 115.30 (12) | C10—C11—C12—C17 | 30.35 (19) |
C10—C2—C3—C19 | 60.39 (18) | C17—C12—C13—C14 | −2.6 (2) |
N1—C2—C3—C19 | −119.58 (12) | C11—C12—C13—C14 | −179.74 (12) |
C9—C4—C5—C6 | 0.4 (2) | C12—C13—C14—C15 | 2.2 (2) |
C4—C5—C6—C7 | 0.0 (2) | C13—C14—C15—C16 | 0.5 (2) |
C5—C6—C7—C8 | −0.3 (2) | C13—C14—C15—C21 | −177.26 (12) |
C6—C7—C8—C9 | 0.35 (19) | C14—C15—C16—C17 | −2.71 (19) |
C6—C7—C8—N1 | −179.92 (13) | C21—C15—C16—C17 | 175.13 (12) |
C2—N1—C8—C9 | −0.12 (15) | C15—C16—C17—C12 | 2.2 (2) |
C18—N1—C8—C9 | −179.25 (13) | C13—C12—C17—C16 | 0.5 (2) |
C2—N1—C8—C7 | −179.88 (12) | C11—C12—C17—C16 | 177.46 (12) |
C18—N1—C8—C7 | 1.0 (2) | C14—C15—C21—C22 | −146.14 (14) |
C5—C4—C9—C8 | −0.41 (19) | C16—C15—C21—C22 | 36.12 (18) |
C5—C4—C9—C3 | −179.14 (12) | C14—C15—C21—C26 | 35.92 (18) |
C7—C8—C9—C4 | 0.03 (19) | C16—C15—C21—C26 | −141.81 (14) |
N1—C8—C9—C4 | −179.75 (11) | C26—C21—C22—C23 | 0.7 (2) |
C7—C8—C9—C3 | 179.01 (12) | C15—C21—C22—C23 | −177.27 (12) |
N1—C8—C9—C3 | −0.77 (14) | C21—C22—C23—C24 | 0.3 (2) |
C2—C3—C9—C4 | −179.92 (13) | C22—C23—C24—C25 | −1.1 (2) |
C20—C3—C9—C4 | 62.16 (18) | C23—C24—C25—C26 | 0.9 (3) |
C19—C3—C9—C4 | −60.75 (18) | C24—C25—C26—C21 | 0.2 (2) |
C2—C3—C9—C8 | 1.25 (13) | C22—C21—C26—C25 | −0.9 (2) |
C20—C3—C9—C8 | −116.67 (12) | C15—C21—C26—C25 | 177.07 (14) |
C19—C3—C9—C8 | 120.42 (12) |
Cg1, Cg2 and Cg3 are the centroids of the C21–C26, C12–C17 and C4–C9 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19B···O1 | 0.96 | 2.36 | 3.112 (2) | 135 |
C20—H20B···O1 | 0.96 | 2.31 | 3.078 (2) | 137 |
C24—H24···O1i | 0.93 | 2.54 | 3.465 (2) | 171 |
C7—H7···Cg1ii | 0.93 | 2.74 | 3.5436 (16) | 145 |
C20—H20C···Cg2iii | 0.96 | 2.81 | 3.7562 (17) | 167 |
C26—H26···Cg3iii | 0.93 | 2.89 | 3.7700 (17) | 158 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x−1, y, z−1; (iii) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C25H23NO |
Mr | 353.44 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 12.3274 (13), 15.7586 (16), 10.3848 (11) |
β (°) | 104.719 (2) |
V (Å3) | 1951.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.36 × 0.28 × 0.26 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15883, 3584, 2585 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.603 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.106, 0.97 |
No. of reflections | 3584 |
No. of parameters | 247 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.18 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2002), SHELXTL (Sheldrick, 2008).
Cg1, Cg2 and Cg3 are the centroids of the C21–C26, C12–C17 and C4–C9 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19B···O1 | 0.96 | 2.360 | 3.112 (2) | 134.84 |
C20—H20B···O1 | 0.96 | 2.309 | 3.078 (2) | 136.50 |
C24—H24···O1i | 0.93 | 2.544 | 3.465 (2) | 170.6 |
C7—H7···Cg1ii | 0.93 | 2.74 | 3.5436 (16) | 145 |
C20—H20C···Cg2iii | 0.96 | 2.81 | 3.7562 (17) | 167 |
C26—H26···Cg3iii | 0.93 | 2.89 | 3.7700 (17) | 158 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x−1, y, z−1; (iii) −x, −y, −z+1. |
Footnotes
‡Additional author for correspondence, e-mail: armandop@ucol.mx.
Acknowledgements
We are grateful for funding from CONACyT (project No. 52115-Y).
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The compound 2,3-dihydro-1H-1,3,3-trimethyl-2-methyleneindole, well known as the Fischer base, has been widely used in organic synthesis as precursor of different types of chemical switches (Minkin, 2004; Przhiyalgovskaya et al., 1987). Products with different skills to work as switches have been used in optoelectronics (Shimkin et al., 2006), as organic electroluminescent materials (Cui & Kim, 2004) and dyes (Song et al., 2005). Moreover, the enaminoketone derivatives of the Fischer base, like the title compound, are important intermediates for the synthesis of spiropyrans and spirooxazines (Corns et al., 2009), as well as for the preparation of acetylenic products via enaminoketone fragmentation (Tarshits et al., 2005).
The structure of the title compound [alternative name: (E)-2,3-dihydro-2-(biphenylacylidene)-1,3,3-trimethyl-1H-indol], C25H23NO, has monoclinic (P21/c) symmetry. The crystal structure exhibits C—H···O intramolecular contacts in a bifurcated fashion with C19 and C20 as the donor atoms and the O atom of carbonyl group O1 as the acceptor (Table 1, Fig. 1). Moreover, despite the molecule presents high conjugation degree, the molecule is not planar; the benzene group (C12···C17) is rotated with respect to indole group (N1···C9) with the dihedral angle of 33.19 (5)°, while the biphenyl rings presents rotation showed by the dihedral angle of 37.13 (5)°.
The intermolecular assembly presents an antiparallel arrangement in a head-to-tail stacking mode especially favored by edge-to-face weak C—H···π interaction between 2.739 to 2.891 Å (see Table 2). Moreover, the weak C—H···O interaction formed by C24–H24C···O1 propagates in the ac plane (Fig. 2).