research communications
H-indole-2-carboxylate)
of dimethyl 3,3′-[(4-fluorophenyl)methylene]bis(1aChemical Engineering Department, Nanjing Polytechnic Institute, Nanjing 210048, People's Republic of China
*Correspondence e-mail: njutshs@126.com
In the title compound, C27H21FN2O4, the mean planes of the indole ring systems (r.m.s. deviations = 0.0263 and 0.0160 Å) are approximately perpendicular to one another, making a dihedral angle of 84.0 (5)°; the fluorobenzene ring is twisted with respect to the mean planes of the two indole ring systems at 89.5 (5) and 84.6 (3)°. In the crystal, pairs of N—H⋯O hydrogen bonds link the molecules into inversion dimers, which are further linked by N—H⋯O hydrogen bonds into supramolecular chains propagated along the b-axis direction. Weak C—H⋯π interactions are observed between neighbouring chains.
Keywords: crystal structure; MRI contrast agent; indole; bis-indolymethane; N—H⋯O hydrogen bonds; C—H⋯π interactions.
CCDC reference: 1421585
1. Chemical context
Bis(indolyl)methane derivatives have been found widely in various terrestrial and marine natural resources (Porter et al., 1977; Sundberg, 1996), and have many applications in pharmaceuticals with diverse activities, such as anticancer, antileishmanial and antihyperlipidemic (Chang et al., 1999; Ge et al., 1999). Other, bis(indoly)methane derivatives can also be used as a precursor for MRI contrast agents (Ni, 2008). In recent years, we have reported the synthesis and crystal structures of some similar compounds (Sun et al., 2012, 2013, 2014; Li et al., 2014; Lu et al., 2014). Now we report herein another bis(indoly)methane compound.
2. Structural commentary
The molecular structure of the title compound is shown in Fig. 1. The two indole ring systems are approximately planar, the maximum deviations being 0.049 (3) and 0.030 (2) Å; the mean planes of the two indole ring systems nearly perpendicular to each other [dihedral angle = 84.0 (5)°] while the benzene ring (C22–C27) is twisted to the N1/C2–C9 and N2/C12–C19 indole ring systems by dihedral angles of 89.5 (5) and 84.6 (3)°, respectively. The carboxyl groups are approximately co-planar with the attached indole ring systems, the dihedral angles between the carboxyl groups and the mean planes of attached indole ring systems are 10.8 (3) and 12.3 (4)°.
3. Supramolecular features
In the crystal, pairs of N1—H1A⋯O4i [symmetry code: (i) x, y + 1, z] hydrogen bonds link the molecules into inversion dimmers, which are further linked by N2—H2A⋯O2ii [symmetry code: (ii) 1 − x, 1 − y, 1 − z] hydrogen bonds into supramolecular chains propagated along the b axis (Table 1 and Fig. 2). Weak C—H⋯π interactions are also observed between neighbouring chains.
4. Database survey
Several similar structures have been reported previously, i.e. diethyl 3,3′-(phenylmethylene)bis(1H-indole-2-carboxylate) (Sun et al., 2012), dimethyl 3,3′-(phenylmethylene)bis(1H-indole-2-carboxylate) (Sun et al., 2013), dimethyl 3,3′-[(4-chlorophenyl) methylene]bis(1H-indole-2-carboxylate) (Li et al., 2014), dimethyl 3,3′-[(3-nitrophenyl) methylene]bis(1H-indole-2-carboxylate) ethanol monosolvate (Sun et al., 2014) and dimethyl 3,3′-[(3-fluorophenyl)methylene]bis(1H-indole-2-carboxylate) (Lu et al., 2014). In those structures, the two indole ring systems are also nearly perpendicular to each other, the dihedral angles being 82.0 (5), 84.5 (5), 79.5 (4), 89.3 (5) and 87.8 (5)°, respectively.
5. Synthesis and crystallization
Methyl indole-2-carboxylate (17.5 g, 100 mmol) was dissolved in 200 ml methanol; commercially available 4-fluorobenzaldehyde (6.2 g, 50 mmol) was added and the mixture was heated to reflux temperature. Concentrated HCl (3.7 ml) was added and the reaction was left for 1 h. After cooling the white product was filtered off and washed thoroughly with methanol. The reaction was monitored by TLC (CHCl3:hexane = 1:1). Yield was 90%. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of a methanol solution. 1H NMR (300 MHz, DMSO) δ 11.81 (s, 2H), 7.59–7.36 (m, 3H), 7.13 (dd, J = 15.1, 7.2 Hz, 6H), 6.71 (t, J = 7.5 Hz, 2H), 6.60 (d, J = 8.3 Hz, 2H), 3.77 (s, 6H).
6. Refinement
Crystal data, data collection and structure . H atoms were positioned geometrically with N—H = 0.86 Å and C—H = 0.93–0.98 Å, and constrained to ride on their parent atoms. Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H atoms and 1.2 for the others.
details are summarized in Table 2
|
Supporting information
CCDC reference: 1421585
10.1107/S205698901501628X/xu5870sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S205698901501628X/xu5870Isup2.hkl
Supporting information file. DOI: 10.1107/S205698901501628X/xu5870Isup3.cml
Bis(indolyl)methane derivatives have been found widely in various terrestrial and marine natural resources (Porter et al., 1977; Sundberg, 1996), and have many applications in pharmaceuticals with diverse activities, such as anticancer, antileishmanial and antihyperlipidemic (Chang et al., 1999; Ge et al., 1999). Other, bis(indoly)methane derivatives can also be used as a precursor for MRI contrast agents (Ni, 2008). In recent years, we have reported the synthesis and crystal structures of some similar compounds (Sun et al., 2012, 2013, 2014; Li et al., 2014; Lu et al., 2014). Now we report herein another bis(indoly)methane compound.
The molecular structure of the title compound is shown in Fig. 1. The two indole ring systems are approximately planar, the maximum deviations being 0.49 (3) and 0.30 (2) Å; the mean planes of the two indole ring systems nearly perpendicular to each other [dihedral angle = 84.0 (5)°] while the benzene ring (C22–C27) is twisted to the N1/C2–C9 and N2/C12–C19 indole ring systems by dihedral angles of 89.5 (5) and 84.6 (3)°, respectively. The carboxyl groups are approximately co-planar with the attached indole ring systems, the dihedral angles between the carboxyl groups and the mean planes of attached indole ring systems are 10.8 (3) and 12.3 (4)°.
In the crystal, pairs of N1—H1A···O4i [symmetry code: (i) x, y + 1, z] hydrogen bonds link the molecules into inversion dimmers, which are further linked by N2—H2A···O2ii [symmetry code: (ii) 1 - x, 1 - y, 1 - z] hydrogen bonds into supramolecular chains propagated along the b axis (Table 1 and Fig. 2). Weak C—H···π interactions are also observed between neighbouring chains.
Several similar structures have been reported previously, i.e. diethyl 3,3'-(phenylmethylene)bis(1H-indole-2-carboxylate) (Sun et al., 2012), dimethyl 3,3'-(phenylmethylene)bis(1H-indole-2-carboxylate) (Sun et al., 2013), dimethyl 3,3'-[(4-chlorophenyl) methylene]bis(1H-indole-2-carboxylate) (Li et al., 2014), dimethyl 3,3'-[(3-nitrophenyl) methylene]bis(1H-indole-2-carboxylate) ethanol monosolvate (Sun et al., 2014) and dimethyl 3,3'-[(3-fluorophenyl)methylene]bis(1H-indole-2-carboxylate) (Lu et al., 2014). In those structures, the two indole ring systems are also nearly perpendicular to each other, the dihedral angles are 82.0 (5), 84.5 (5), 79.5 (4) , 89.3 (5) and 87.8 (5)°, respectively.
Methyl indole-2-carboxylate (17.5 g, 100 mmol) was dissolved in 200 ml methanol; commercially available 4-fluorobenzaldehyde (6.2 g, 50 mmol) was added and the mixture was heated to reflux temperature. Concentrated HCl (3.7 ml) was added and the reaction was left for 1 h. After cooling the white product was filtered off and washed thoroughly with methanol. The reaction was monitored by TLC (CHCl3:hexane = 1:1). Yield was 90%. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of a methanol solution. 1H NMR (300 MHz, DMSO) δ 11.81 (s, 2H), 7.59–7.36 (m, 3H), 7.13 (dd, J = 15.1, 7.2 Hz, 6H), 6.71 (t, J = 7.5 Hz, 2H), 6.60 (d, J = 8.3 Hz, 2H), 3.77 (s, 6H).
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell
CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of the title molecule, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines. |
C27H21FN2O4 | Z = 2 |
Mr = 456.46 | F(000) = 476 |
Triclinic, P1 | Dx = 1.294 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.7270 (19) Å | Cell parameters from 25 reflections |
b = 10.122 (2) Å | θ = 9–13° |
c = 13.441 (3) Å | µ = 0.09 mm−1 |
α = 68.15 (3)° | T = 293 K |
β = 73.69 (3)° | Block, colorless |
γ = 89.73 (3)° | 0.30 × 0.20 × 0.10 mm |
V = 1171.4 (4) Å3 |
Nonius CAD-4 diffractometer | 2756 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.040 |
Graphite monochromator | θmax = 25.4°, θmin = 1.7° |
ω/2θ scans | h = 0→11 |
Absorption correction: ψ scan (North et al., 1968) | k = −12→12 |
Tmin = 0.973, Tmax = 0.991 | l = −15→16 |
4587 measured reflections | 3 standard reflections every 200 reflections |
4311 independent reflections | intensity decay: 1% |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.075P)2] where P = (Fo2 + 2Fc2)/3 |
4311 reflections | (Δ/σ)max < 0.001 |
307 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C27H21FN2O4 | γ = 89.73 (3)° |
Mr = 456.46 | V = 1171.4 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.7270 (19) Å | Mo Kα radiation |
b = 10.122 (2) Å | µ = 0.09 mm−1 |
c = 13.441 (3) Å | T = 293 K |
α = 68.15 (3)° | 0.30 × 0.20 × 0.10 mm |
β = 73.69 (3)° |
Nonius CAD-4 diffractometer | 2756 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.040 |
Tmin = 0.973, Tmax = 0.991 | 3 standard reflections every 200 reflections |
4587 measured reflections | intensity decay: 1% |
4311 independent reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.16 e Å−3 |
4311 reflections | Δρmin = −0.18 e Å−3 |
307 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 | ||
N1 | 0.6800 (2) | 1.1318 (2) | 0.27546 (18) | 0.0513 (6) | |
H1A | 0.6727 | 1.1742 | 0.3213 | 0.062* | |
C1 | 0.7071 (2) | 0.8060 (2) | 0.20833 (19) | 0.0382 (5) | |
H1B | 0.7844 | 0.7680 | 0.2409 | 0.046* | |
O1 | 0.6875 (3) | 0.9631 (2) | 0.47878 (17) | 0.0872 (7) | |
N2 | 0.4265 (2) | 0.49916 (19) | 0.39447 (16) | 0.0465 (5) | |
H2A | 0.3987 | 0.4100 | 0.4353 | 0.056* | |
O2 | 0.7270 (2) | 0.77039 (17) | 0.43616 (14) | 0.0554 (5) | |
C2 | 0.6977 (2) | 0.9558 (2) | 0.2084 (2) | 0.0386 (5) | |
O3 | 0.8103 (2) | 0.52264 (18) | 0.29747 (17) | 0.0636 (5) | |
C3 | 0.6956 (2) | 1.0904 (2) | 0.1197 (2) | 0.0395 (6) | |
O4 | 0.6464 (2) | 0.32942 (17) | 0.38907 (16) | 0.0633 (5) | |
C4 | 0.7094 (3) | 1.1362 (2) | 0.0044 (2) | 0.0479 (6) | |
H4A | 0.7174 | 1.0699 | −0.0292 | 0.058* | |
F | 0.8690 (2) | 0.7816 (2) | −0.22102 (14) | 0.0854 (6) | |
C5 | 0.7110 (3) | 1.2785 (3) | −0.0579 (2) | 0.0559 (7) | |
H5B | 0.7218 | 1.3084 | −0.1342 | 0.067* | |
C6 | 0.6967 (3) | 1.3798 (3) | −0.0089 (3) | 0.0627 (8) | |
H6A | 0.6972 | 1.4757 | −0.0534 | 0.075* | |
C7 | 0.6819 (3) | 1.3414 (3) | 0.1023 (3) | 0.0587 (7) | |
H7A | 0.6717 | 1.4090 | 0.1348 | 0.070* | |
C8 | 0.6827 (3) | 1.1961 (2) | 0.1658 (2) | 0.0464 (6) | |
C9 | 0.6911 (3) | 0.9871 (2) | 0.3010 (2) | 0.0443 (6) | |
C10 | 0.7028 (3) | 0.8940 (3) | 0.4101 (2) | 0.0485 (6) | |
C11 | 0.7075 (5) | 0.8835 (4) | 0.5877 (3) | 0.1118 (15) | |
H11A | 0.6940 | 0.9428 | 0.6304 | 0.168* | |
H11B | 0.8033 | 0.8555 | 0.5773 | 0.168* | |
H11C | 0.6386 | 0.7997 | 0.6272 | 0.168* | |
C12 | 0.5725 (3) | 0.7045 (2) | 0.28357 (19) | 0.0384 (5) | |
C13 | 0.4254 (3) | 0.7349 (2) | 0.30284 (19) | 0.0408 (6) | |
C14 | 0.3562 (3) | 0.8584 (3) | 0.2647 (2) | 0.0502 (7) | |
H14A | 0.4102 | 0.9463 | 0.2179 | 0.060* | |
C15 | 0.2095 (3) | 0.8478 (3) | 0.2971 (2) | 0.0616 (8) | |
H15A | 0.1641 | 0.9295 | 0.2720 | 0.074* | |
C16 | 0.1249 (3) | 0.7167 (3) | 0.3675 (3) | 0.0649 (8) | |
H16A | 0.0250 | 0.7130 | 0.3880 | 0.078* | |
C17 | 0.1881 (3) | 0.5942 (3) | 0.4064 (2) | 0.0587 (7) | |
H17A | 0.1327 | 0.5073 | 0.4538 | 0.070* | |
C18 | 0.3376 (3) | 0.6042 (2) | 0.37256 (19) | 0.0441 (6) | |
C19 | 0.5672 (3) | 0.5583 (2) | 0.34119 (19) | 0.0399 (6) | |
C20 | 0.6760 (3) | 0.4588 (3) | 0.3467 (2) | 0.0460 (6) | |
C21 | 0.9232 (3) | 0.4299 (3) | 0.2909 (3) | 0.0868 (11) | |
H21A | 1.0152 | 0.4869 | 0.2540 | 0.130* | |
H21B | 0.9091 | 0.3751 | 0.2490 | 0.130* | |
H21C | 0.9203 | 0.3662 | 0.3653 | 0.130* | |
C22 | 0.7510 (2) | 0.8014 (2) | 0.09177 (19) | 0.0386 (6) | |
C23 | 0.6484 (3) | 0.7791 (3) | 0.0436 (2) | 0.0495 (6) | |
H23A | 0.5512 | 0.7679 | 0.0834 | 0.059* | |
C24 | 0.6868 (3) | 0.7731 (3) | −0.0611 (2) | 0.0527 (7) | |
H24A | 0.6170 | 0.7588 | −0.0924 | 0.063* | |
C25 | 0.8294 (3) | 0.7885 (3) | −0.1176 (2) | 0.0543 (7) | |
C26 | 0.9337 (3) | 0.8114 (3) | −0.0755 (3) | 0.0698 (9) | |
H26A | 1.0304 | 0.8225 | −0.1164 | 0.084* | |
C27 | 0.8938 (3) | 0.8180 (3) | 0.0304 (2) | 0.0581 (7) | |
H27A | 0.9648 | 0.8339 | 0.0600 | 0.070* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0702 (15) | 0.0321 (11) | 0.0561 (14) | 0.0069 (10) | −0.0203 (11) | −0.0209 (10) |
C1 | 0.0363 (13) | 0.0298 (12) | 0.0485 (14) | 0.0036 (10) | −0.0142 (11) | −0.0142 (10) |
O1 | 0.158 (2) | 0.0616 (13) | 0.0675 (14) | 0.0279 (14) | −0.0540 (15) | −0.0379 (12) |
N2 | 0.0553 (13) | 0.0267 (10) | 0.0480 (12) | −0.0034 (9) | −0.0092 (10) | −0.0086 (9) |
O2 | 0.0728 (13) | 0.0346 (10) | 0.0542 (11) | 0.0024 (8) | −0.0202 (9) | −0.0113 (8) |
C2 | 0.0337 (12) | 0.0299 (12) | 0.0494 (14) | 0.0010 (9) | −0.0114 (11) | −0.0131 (11) |
O3 | 0.0548 (12) | 0.0421 (10) | 0.0936 (15) | 0.0147 (9) | −0.0217 (11) | −0.0262 (10) |
C3 | 0.0353 (13) | 0.0292 (12) | 0.0511 (15) | 0.0006 (10) | −0.0136 (11) | −0.0119 (11) |
O4 | 0.0838 (14) | 0.0297 (10) | 0.0768 (13) | 0.0119 (9) | −0.0245 (11) | −0.0209 (9) |
C4 | 0.0477 (15) | 0.0340 (13) | 0.0594 (17) | −0.0002 (11) | −0.0175 (13) | −0.0139 (12) |
F | 0.0945 (14) | 0.1087 (15) | 0.0628 (11) | 0.0344 (11) | −0.0181 (10) | −0.0482 (11) |
C5 | 0.0586 (17) | 0.0418 (15) | 0.0601 (17) | −0.0014 (12) | −0.0234 (14) | −0.0074 (13) |
C6 | 0.071 (2) | 0.0319 (14) | 0.078 (2) | 0.0014 (13) | −0.0318 (17) | −0.0065 (14) |
C7 | 0.076 (2) | 0.0311 (13) | 0.074 (2) | 0.0059 (13) | −0.0321 (16) | −0.0184 (13) |
C8 | 0.0462 (15) | 0.0326 (13) | 0.0599 (17) | 0.0033 (11) | −0.0173 (12) | −0.0165 (12) |
C9 | 0.0514 (15) | 0.0285 (12) | 0.0521 (15) | 0.0017 (10) | −0.0146 (12) | −0.0152 (11) |
C10 | 0.0569 (17) | 0.0396 (14) | 0.0511 (16) | −0.0015 (12) | −0.0172 (13) | −0.0190 (12) |
C11 | 0.192 (5) | 0.096 (3) | 0.071 (2) | 0.030 (3) | −0.064 (3) | −0.041 (2) |
C12 | 0.0473 (14) | 0.0292 (12) | 0.0387 (13) | 0.0027 (10) | −0.0115 (11) | −0.0142 (10) |
C13 | 0.0462 (14) | 0.0312 (12) | 0.0402 (13) | −0.0007 (10) | −0.0068 (11) | −0.0128 (10) |
C14 | 0.0493 (16) | 0.0332 (13) | 0.0606 (17) | 0.0054 (11) | −0.0125 (13) | −0.0128 (12) |
C15 | 0.0484 (17) | 0.0472 (16) | 0.080 (2) | 0.0104 (13) | −0.0138 (15) | −0.0185 (15) |
C16 | 0.0446 (16) | 0.0591 (18) | 0.075 (2) | 0.0039 (13) | −0.0047 (14) | −0.0182 (16) |
C17 | 0.0469 (17) | 0.0479 (16) | 0.0610 (18) | −0.0098 (13) | −0.0009 (13) | −0.0098 (13) |
C18 | 0.0522 (16) | 0.0342 (13) | 0.0399 (14) | −0.0009 (11) | −0.0080 (12) | −0.0122 (11) |
C19 | 0.0498 (15) | 0.0288 (12) | 0.0415 (13) | 0.0022 (10) | −0.0135 (11) | −0.0141 (10) |
C20 | 0.0596 (17) | 0.0342 (13) | 0.0483 (15) | 0.0067 (12) | −0.0182 (13) | −0.0190 (11) |
C21 | 0.066 (2) | 0.073 (2) | 0.130 (3) | 0.0350 (18) | −0.033 (2) | −0.047 (2) |
C22 | 0.0382 (13) | 0.0279 (11) | 0.0464 (14) | 0.0021 (9) | −0.0085 (11) | −0.0137 (10) |
C23 | 0.0410 (15) | 0.0523 (15) | 0.0546 (16) | 0.0014 (12) | −0.0085 (12) | −0.0240 (13) |
C24 | 0.0574 (18) | 0.0510 (16) | 0.0564 (17) | 0.0068 (13) | −0.0199 (14) | −0.0259 (13) |
C25 | 0.0631 (19) | 0.0544 (16) | 0.0486 (16) | 0.0144 (13) | −0.0121 (14) | −0.0270 (13) |
C26 | 0.0444 (17) | 0.094 (2) | 0.072 (2) | 0.0155 (16) | −0.0050 (15) | −0.0420 (19) |
C27 | 0.0397 (15) | 0.0742 (19) | 0.0661 (19) | 0.0057 (13) | −0.0142 (14) | −0.0345 (16) |
N1—C8 | 1.364 (3) | C11—H11A | 0.9600 |
N1—C9 | 1.386 (3) | C11—H11B | 0.9600 |
N1—H1A | 0.8600 | C11—H11C | 0.9600 |
C1—C12 | 1.513 (3) | C12—C19 | 1.385 (3) |
C1—C2 | 1.519 (3) | C12—C13 | 1.434 (3) |
C1—C22 | 1.522 (3) | C13—C14 | 1.410 (3) |
C1—H1B | 0.9800 | C13—C18 | 1.413 (3) |
O1—C10 | 1.328 (3) | C14—C15 | 1.362 (4) |
O1—C11 | 1.453 (4) | C14—H14A | 0.9300 |
N2—C18 | 1.366 (3) | C15—C16 | 1.403 (4) |
N2—C19 | 1.372 (3) | C15—H15A | 0.9300 |
N2—H2A | 0.8600 | C16—C17 | 1.371 (4) |
O2—C10 | 1.209 (3) | C16—H16A | 0.9300 |
C2—C9 | 1.379 (3) | C17—C18 | 1.389 (4) |
C2—C3 | 1.443 (3) | C17—H17A | 0.9300 |
O3—C20 | 1.329 (3) | C19—C20 | 1.456 (3) |
O3—C21 | 1.446 (3) | C21—H21A | 0.9600 |
C3—C4 | 1.409 (3) | C21—H21B | 0.9600 |
C3—C8 | 1.411 (3) | C21—H21C | 0.9600 |
O4—C20 | 1.216 (3) | C22—C27 | 1.376 (3) |
C4—C5 | 1.368 (3) | C22—C23 | 1.393 (3) |
C4—H4A | 0.9300 | C23—C24 | 1.375 (3) |
F—C25 | 1.363 (3) | C23—H23A | 0.9300 |
C5—C6 | 1.398 (4) | C24—C25 | 1.359 (4) |
C5—H5B | 0.9300 | C24—H24A | 0.9300 |
C6—C7 | 1.362 (4) | C25—C26 | 1.351 (4) |
C6—H6A | 0.9300 | C26—C27 | 1.393 (4) |
C7—C8 | 1.400 (3) | C26—H26A | 0.9300 |
C7—H7A | 0.9300 | C27—H27A | 0.9300 |
C9—C10 | 1.454 (3) | ||
C8—N1—C9 | 108.9 (2) | C13—C12—C1 | 128.2 (2) |
C8—N1—H1A | 125.6 | C14—C13—C18 | 117.7 (2) |
C9—N1—H1A | 125.6 | C14—C13—C12 | 134.8 (2) |
C12—C1—C2 | 113.09 (19) | C18—C13—C12 | 107.4 (2) |
C12—C1—C22 | 110.81 (18) | C15—C14—C13 | 119.3 (2) |
C2—C1—C22 | 114.33 (18) | C15—C14—H14A | 120.3 |
C12—C1—H1B | 106.0 | C13—C14—H14A | 120.3 |
C2—C1—H1B | 106.0 | C14—C15—C16 | 121.7 (3) |
C22—C1—H1B | 106.0 | C14—C15—H15A | 119.1 |
C10—O1—C11 | 116.2 (2) | C16—C15—H15A | 119.1 |
C18—N2—C19 | 109.29 (19) | C17—C16—C15 | 120.7 (3) |
C18—N2—H2A | 125.4 | C17—C16—H16A | 119.6 |
C19—N2—H2A | 125.4 | C15—C16—H16A | 119.6 |
C9—C2—C3 | 105.93 (19) | C16—C17—C18 | 117.8 (2) |
C9—C2—C1 | 123.5 (2) | C16—C17—H17A | 121.1 |
C3—C2—C1 | 130.5 (2) | C18—C17—H17A | 121.1 |
C20—O3—C21 | 116.5 (2) | N2—C18—C17 | 129.7 (2) |
C4—C3—C8 | 117.4 (2) | N2—C18—C13 | 107.6 (2) |
C4—C3—C2 | 135.5 (2) | C17—C18—C13 | 122.7 (2) |
C8—C3—C2 | 107.1 (2) | N2—C19—C12 | 109.9 (2) |
C5—C4—C3 | 119.7 (2) | N2—C19—C20 | 116.4 (2) |
C5—C4—H4A | 120.2 | C12—C19—C20 | 133.4 (2) |
C3—C4—H4A | 120.2 | O4—C20—O3 | 123.3 (2) |
C4—C5—C6 | 121.3 (3) | O4—C20—C19 | 123.0 (2) |
C4—C5—H5B | 119.4 | O3—C20—C19 | 113.7 (2) |
C6—C5—H5B | 119.4 | O3—C21—H21A | 109.5 |
C7—C6—C5 | 121.5 (2) | O3—C21—H21B | 109.5 |
C7—C6—H6A | 119.2 | H21A—C21—H21B | 109.5 |
C5—C6—H6A | 119.2 | O3—C21—H21C | 109.5 |
C6—C7—C8 | 117.3 (3) | H21A—C21—H21C | 109.5 |
C6—C7—H7A | 121.4 | H21B—C21—H21C | 109.5 |
C8—C7—H7A | 121.4 | C27—C22—C23 | 117.5 (2) |
N1—C8—C7 | 128.8 (2) | C27—C22—C1 | 121.2 (2) |
N1—C8—C3 | 108.2 (2) | C23—C22—C1 | 121.4 (2) |
C7—C8—C3 | 122.9 (2) | C24—C23—C22 | 121.9 (2) |
C2—C9—N1 | 109.8 (2) | C24—C23—H23A | 119.0 |
C2—C9—C10 | 129.3 (2) | C22—C23—H23A | 119.0 |
N1—C9—C10 | 120.8 (2) | C25—C24—C23 | 118.2 (3) |
O2—C10—O1 | 123.1 (2) | C25—C24—H24A | 120.9 |
O2—C10—C9 | 125.4 (2) | C23—C24—H24A | 120.9 |
O1—C10—C9 | 111.4 (2) | C26—C25—C24 | 122.6 (3) |
O1—C11—H11A | 109.5 | C26—C25—F | 118.6 (3) |
O1—C11—H11B | 109.5 | C24—C25—F | 118.8 (3) |
H11A—C11—H11B | 109.5 | C25—C26—C27 | 118.8 (3) |
O1—C11—H11C | 109.5 | C25—C26—H26A | 120.6 |
H11A—C11—H11C | 109.5 | C27—C26—H26A | 120.6 |
H11B—C11—H11C | 109.5 | C22—C27—C26 | 121.1 (3) |
C19—C12—C13 | 105.8 (2) | C22—C27—H27A | 119.5 |
C19—C12—C1 | 125.9 (2) | C26—C27—H27A | 119.5 |
C12—C1—C2—C9 | 66.6 (3) | C1—C12—C13—C18 | 175.5 (2) |
C22—C1—C2—C9 | −165.3 (2) | C18—C13—C14—C15 | 0.8 (4) |
C12—C1—C2—C3 | −114.3 (3) | C12—C13—C14—C15 | 177.2 (3) |
C22—C1—C2—C3 | 13.8 (3) | C13—C14—C15—C16 | −0.1 (4) |
C9—C2—C3—C4 | 174.6 (3) | C14—C15—C16—C17 | 0.1 (5) |
C1—C2—C3—C4 | −4.6 (4) | C15—C16—C17—C18 | −0.8 (4) |
C9—C2—C3—C8 | −2.0 (3) | C19—N2—C18—C17 | 178.4 (3) |
C1—C2—C3—C8 | 178.8 (2) | C19—N2—C18—C13 | −0.1 (3) |
C8—C3—C4—C5 | 0.5 (3) | C16—C17—C18—N2 | −176.8 (3) |
C2—C3—C4—C5 | −175.8 (3) | C16—C17—C18—C13 | 1.6 (4) |
C3—C4—C5—C6 | −1.1 (4) | C14—C13—C18—N2 | 177.1 (2) |
C4—C5—C6—C7 | 0.6 (4) | C12—C13—C18—N2 | −0.2 (3) |
C5—C6—C7—C8 | 0.5 (4) | C14—C13—C18—C17 | −1.6 (4) |
C9—N1—C8—C7 | −176.3 (3) | C12—C13—C18—C17 | −178.8 (2) |
C9—N1—C8—C3 | 0.1 (3) | C18—N2—C19—C12 | 0.3 (3) |
C6—C7—C8—N1 | 174.9 (3) | C18—N2—C19—C20 | −174.2 (2) |
C6—C7—C8—C3 | −1.0 (4) | C13—C12—C19—N2 | −0.4 (3) |
C4—C3—C8—N1 | −176.1 (2) | C1—C12—C19—N2 | −175.7 (2) |
C2—C3—C8—N1 | 1.2 (3) | C13—C12—C19—C20 | 172.8 (2) |
C4—C3—C8—C7 | 0.6 (4) | C1—C12—C19—C20 | −2.5 (4) |
C2—C3—C8—C7 | 177.9 (2) | C21—O3—C20—O4 | 3.2 (4) |
C3—C2—C9—N1 | 2.1 (3) | C21—O3—C20—C19 | −174.6 (2) |
C1—C2—C9—N1 | −178.7 (2) | N2—C19—C20—O4 | 4.8 (4) |
C3—C2—C9—C10 | −173.9 (2) | C12—C19—C20—O4 | −168.0 (3) |
C1—C2—C9—C10 | 5.3 (4) | N2—C19—C20—O3 | −177.5 (2) |
C8—N1—C9—C2 | −1.4 (3) | C12—C19—C20—O3 | 9.7 (4) |
C8—N1—C9—C10 | 175.0 (2) | C12—C1—C22—C27 | −145.7 (2) |
C11—O1—C10—O2 | 2.5 (4) | C2—C1—C22—C27 | 85.1 (3) |
C11—O1—C10—C9 | −175.7 (3) | C12—C1—C22—C23 | 33.8 (3) |
C2—C9—C10—O2 | 3.3 (4) | C2—C1—C22—C23 | −95.4 (3) |
N1—C9—C10—O2 | −172.3 (2) | C27—C22—C23—C24 | 0.2 (4) |
C2—C9—C10—O1 | −178.5 (2) | C1—C22—C23—C24 | −179.3 (2) |
N1—C9—C10—O1 | 5.9 (3) | C22—C23—C24—C25 | 0.5 (4) |
C2—C1—C12—C19 | −148.6 (2) | C23—C24—C25—C26 | −1.0 (4) |
C22—C1—C12—C19 | 81.6 (3) | C23—C24—C25—F | 179.4 (2) |
C2—C1—C12—C13 | 37.2 (3) | C24—C25—C26—C27 | 0.6 (5) |
C22—C1—C12—C13 | −92.7 (3) | F—C25—C26—C27 | −179.8 (2) |
C19—C12—C13—C14 | −176.2 (3) | C23—C22—C27—C26 | −0.6 (4) |
C1—C12—C13—C14 | −1.1 (4) | C1—C22—C27—C26 | 178.9 (2) |
C19—C12—C13—C18 | 0.4 (2) | C25—C26—C27—C22 | 0.1 (5) |
Cg1, Cg4 and Cg5 are the centroids of the N1-ring, C14-ring and C22-ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4i | 0.86 | 2.07 | 2.903 (3) | 162 |
N2—H2A···O2ii | 0.86 | 2.07 | 2.892 (3) | 159 |
C4—H4A···Cg5 | 0.93 | 2.82 | 3.622 (3) | 146 |
C5—H5B···Cg4iii | 0.93 | 2.84 | 3.705 (3) | 156 |
C26—H26A···Cg1iv | 0.93 | 2.69 | 3.587 (4) | 161 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+2, −z; (iv) −x+2, −y+2, −z. |
Cg1, Cg4 and Cg5 are the centroids of the N1-ring, C14-ring and C22-ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4i | 0.86 | 2.07 | 2.903 (3) | 162 |
N2—H2A···O2ii | 0.86 | 2.07 | 2.892 (3) | 159 |
C4—H4A···Cg5 | 0.93 | 2.82 | 3.622 (3) | 146 |
C5—H5B···Cg4iii | 0.93 | 2.84 | 3.705 (3) | 156 |
C26—H26A···Cg1iv | 0.93 | 2.69 | 3.587 (4) | 161 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+2, −z; (iv) −x+2, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | C27H21FN2O4 |
Mr | 456.46 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.7270 (19), 10.122 (2), 13.441 (3) |
α, β, γ (°) | 68.15 (3), 73.69 (3), 89.73 (3) |
V (Å3) | 1171.4 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.973, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4587, 4311, 2756 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.603 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.147, 1.00 |
No. of reflections | 4311 |
No. of parameters | 307 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.18 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors thank the Center of Testing and Analysis, Nanjing University, for support. Funding for this research was provided by Nanjing Polytechnic Institute, China (NHKY-2015-01).
References
Chang, Y.-C., Riby, J., Chang, G. H.-F., Peng, B., Firestone, G. & Bjeldanes, L. F. (1999). Biochem. Pharmacol. 58, 825–834. CrossRef PubMed CAS Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Ge, X., Fares, F. A. & Yannai, S. (1999). Anticancer Res. 19, 3199–3203. Web of Science PubMed CAS Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Li, Y., Sun, H., Jiang, H., Xu, N. & Xu, H. (2014). Acta Cryst. E70, 259–261. CSD CrossRef IUCr Journals Google Scholar
Lu, X.-H., Sun, H.-S. & Hu, J. (2014). Acta Cryst. E70, 593–595. CSD CrossRef IUCr Journals Google Scholar
Ni, Y.-C. (2008). Curr. Med. Imaging Rev. 4, 96–112. Web of Science CrossRef CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Porter, J. K., Bacon, C. W., Robbins, J. D., Himmelsbach, D. S. & Higman, H. C. (1977). J. Agric. Food Chem. 25, 88–93. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, H.-S., Li, Y.-L., Jiang, H., Xu, N. & Xu, H. (2014). Acta Cryst. E70, 370–372. CSD CrossRef IUCr Journals Google Scholar
Sun, H.-S., Li, Y.-L., Xu, N., Xu, H. & Zhang, J.-D. (2012). Acta Cryst. E68, o2764. CSD CrossRef IUCr Journals Google Scholar
Sun, H.-S., Li, Y.-L., Xu, N., Xu, H. & Zhang, J.-D. (2013). Acta Cryst. E69, o1516. CSD CrossRef IUCr Journals Google Scholar
Sundberg, R. J. (1996). The Chemistry of Indoles, p. 113. New York: Academic Press. Google Scholar
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.