Diethyl 3,3′-[(3-fluoro­phen­yl)methyl­ene]bis­(1H-indole-2-carboxyl­ate)

Jiang, H.; Li, Y.-L.; Zhou, J.; Sun, H.-S.; Zhang, Q.-Y.; Shi, X.-H.; Zhang, Z.-Y.; Ling, T.

doi:10.1107/S2414314620009128

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 7| July 2020| x200912

https://doi.org/10.1107/S2414314620009128

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Diethyl 3,3′-[(3-fluorophenyl)methylene]bis(1H-indole-2-carboxylate)

Hong Jiang,^a Yu-Long Li,^a Jin Zhou,^a,^b Hong-Shun Sun,^a ^* Qing-Yu Zhang,^a Xing-Hao Shi,^a Zhi-Yuan Zhang ^a and Tian Ling ^a

^aTargeted MRI Contrast Agents Laboratory of Jiangsu Province, Nanjing Polytechnic Institute, Nanjing 210048, People's Republic of China, and ^bCollege of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, People's Republic of China
^*Correspondence e-mail: njutshs@126.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 8 June 2020; accepted 3 July 2020; online 10 July 2020)

In the title compound, C₂₉H₂₅FN₂O₄, the mean planes of the indole ring systems are approximately perpendicular to one another [dihedral angle = 88.3 (4)°]. The benzene ring is twisted with respect to the indole ring systems by 49.8 (5) and 77.6 (3)°. In the crystal, pairs of N—H⋯O hydrogen bonds link the molecules into the inversion dimers which are further linked into supramolecular chains propagating along the [110] direction.

Keywords: crystal structure; bisindole; MRI; contrast agents.

CCDC reference: 2014000

Structure description

There are abundant bis(indolyl)methane derivatives in various terrestrial and marine natural resources (Sundberg, 1996 ). As part of our ongoing studies of bis(indoyl)methane compounds, we now report the synthesis and crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. The indole ring systems are nearly perpendicular to one another [dihedral angle = 88.3 (4)°] while the benzene ring (C2–C7) is twisted with respect to the N1/C8–C15 and N2/C19–C26 indole ring systems with dihedral angles of 49.8 (5) and 77.6 (3)°, respectively. The carboxyl groups are approximately co-planar with their attached indole ring systems, the dihedral angles between the carboxyl groups and the mean planes of the N1/C8–C15 and N2/C19–C26 indole ring systems being 6.2 (5) and 6.4 (4)°, respectively.

Figure 1
The molecular structure of the title molecule with displacement ellipsoids drawn at the 30% probability level.

In the crystal, pairwise N1—H1A⋯O1ⁱ and N2—H2A⋯O4ⁱⁱ hydrogen bonds both generate R₂²(8) loops; together these lead to [110] chains of molecules. A weak C11—H11A⋯O4ⁱⁱⁱ interaction also occurs, which links the chains into (001) sheets (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.86	2.16	2.918 (11)	147
N2—H2A⋯O4ⁱⁱ	0.86	2.08	2.904 (9)	159
C11—H11A⋯O4ⁱⁱⁱ	0.93	2.58	3.498 (13)	171
Symmetry codes: (i) -x, -y, -z+1; (ii) -x+1, -y+1, -z+1; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Several similar structures have been reported previously, viz. diethyl 3,3′-(phenylmethylene)bis(1H-indole-2-carboxylate) (Sun et al., 2012 ), dimethyl 3,3′-[(3-fluorophenyl)methylene]bis(1H-indole-2-carboxylate) (Lu et al., 2014 ), dimethyl 3,3′-[(4-fluorophenyl)methylene]bis(1H-indole-2-carboxylate) (Sun et al., 2015 ) and dimethyl 3,3′-[(2-fluorophenyl)methylene]bis(1H-indole-2-carboxylate) (Lu et al., 2017 ). In these structures, the indole ring systems are also nearly perpendicular to one another, making dihedral angles of 82.0 (5), 87.8 (5), 84.0 (5) and 86.0 (5)°, respectively.

Synthesis and crystallization

Ethyl indole-2-carboxylate (1.88 g, 10 mmol) was dissolved in 20 ml of ethanol and 3-fluorobenzaldehyde (0.62 g, 5 mmol) and concentrated HCl (0.5 ml) was added. The mixture was heated to reflux temperature for 2 h. After cooling, the white product was filtered off and washed thoroughly with ethanol (yield = 92%). Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₉H₂₅FN₂O₄
M_r	484.51
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.9960 (18), 15.921 (3), 18.297 (4)
β (°)	102.59 (3)
V (Å³)	2557.6 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968 )
T_min, T_max	0.982, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	5000, 4685, 1424
R_int	0.131
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.143, 0.306, 1.30
No. of reflections	4685
No. of parameters	319
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.72
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994 ), XCAD4 (Harms & Wocadlo, 1995 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 2014000

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314620009128/hb4349sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620009128/hb4349Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314620009128/hb4349Isup3.cml

checkCIF report

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: 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).

Diethyl 3,3'-[(3-fluorophenyl)methylene]bis(1H-indole-2-carboxylate) top

Crystal data top

C₂₉H₂₅FN₂O₄	F(000) = 1016
M_r = 484.51	D_x = 1.258 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.9960 (18) Å	Cell parameters from 25 reflections
b = 15.921 (3) Å	θ = 9–12°
c = 18.297 (4) Å	µ = 0.09 mm⁻¹
β = 102.59 (3)°	T = 293 K
V = 2557.6 (9) Å³	Block, colorless
Z = 4	0.20 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1424 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.131
Graphite monochromator	θ_max = 25.4°, θ_min = 1.7°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = 0→19
T_min = 0.982, T_max = 0.991	l = −22→21
5000 measured reflections	3 standard reflections every 200 reflections
4685 independent reflections	intensity decay: 1%

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)] = 0.143	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.306	H atoms treated by a mixture of independent and constrained refinement
S = 1.30	w = 1/[σ²(F_o²) + (0.060P)²] where P = (F_o² + 2F_c²)/3
4685 reflections	(Δ/σ)_max = 0.009
319 parameters	Δρ_max = 0.56 e Å⁻³
0 restraints	Δρ_min = −0.71 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

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. The constraint U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(methyl C) was applied in all cases.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
F	0.5574 (10)	0.2828 (5)	0.1783 (4)	0.154 (4)
O1	0.1733 (8)	0.0523 (4)	0.5601 (4)	0.080 (2)
N1	0.0972 (9)	0.0284 (4)	0.4084 (5)	0.063 (2)
H1A	0.0468	−0.0028	0.4327	0.076*
C1	0.3860 (9)	0.1906 (5)	0.3962 (5)	0.045 (2)
H1B	0.4561	0.1763	0.4434	0.054*
N2	0.3321 (8)	0.4124 (4)	0.4463 (4)	0.054 (2)
H2A	0.3634	0.4597	0.4668	0.064*
O2	0.3615 (8)	0.1390 (4)	0.5478 (4)	0.078 (2)
C2	0.4782 (11)	0.1845 (6)	0.3395 (6)	0.049 (3)
O3	0.6571 (7)	0.2781 (3)	0.4797 (3)	0.0609 (19)
C3	0.5727 (12)	0.1140 (8)	0.3428 (7)	0.094 (5)
H3A	0.5770	0.0753	0.3812	0.112*
O4	0.6412 (7)	0.4138 (4)	0.5044 (4)	0.071 (2)
C4	0.659 (2)	0.1009 (11)	0.2907 (12)	0.143 (7)
H4A	0.7197	0.0531	0.2945	0.172*
C5	0.6584 (19)	0.1558 (11)	0.2334 (11)	0.129 (7)
H5A	0.7151	0.1471	0.1972	0.155*
C6	0.5694 (16)	0.2231 (10)	0.2335 (7)	0.092 (4)
C7	0.4733 (12)	0.2417 (7)	0.2840 (6)	0.071 (3)
H7A	0.4121	0.2893	0.2792	0.086*
C8	0.2671 (10)	0.1236 (5)	0.3855 (6)	0.050 (3)
C9	0.1838 (10)	0.0882 (5)	0.3150 (6)	0.051 (3)
C10	0.1875 (12)	0.1021 (6)	0.2409 (7)	0.080 (4)
H10A	0.2524	0.1420	0.2276	0.096*
C11	0.0911 (12)	0.0547 (7)	0.1867 (6)	0.082 (4)
H11A	0.0929	0.0626	0.1366	0.099*
C12	−0.0061 (14)	−0.0033 (7)	0.2053 (7)	0.088 (4)
H12A	−0.0678	−0.0341	0.1673	0.105*
C13	−0.0162 (12)	−0.0175 (6)	0.2762 (7)	0.077 (3)
H13A	−0.0844	−0.0565	0.2878	0.092*
C14	0.0816 (11)	0.0295 (6)	0.3329 (7)	0.058 (3)
C15	0.2065 (11)	0.0855 (6)	0.4391 (6)	0.057 (3)
C16	0.2487 (12)	0.0887 (6)	0.5223 (7)	0.061 (3)
C17	0.4070 (12)	0.1489 (9)	0.6278 (6)	0.108 (5)
H17A	0.3662	0.2010	0.6427	0.129*
H17B	0.3673	0.1029	0.6525	0.129*
C18	0.5630 (13)	0.1500 (7)	0.6483 (7)	0.112
H18A	0.5940	0.1565	0.7016	0.168*
H18B	0.6015	0.1960	0.6241	0.168*
H18C	0.6027	0.0982	0.6337	0.168*
C19	0.3282 (9)	0.2778 (5)	0.4087 (5)	0.039 (2)
C20	0.1817 (11)	0.3129 (5)	0.3856 (5)	0.049 (3)
C21	0.0406 (12)	0.2819 (6)	0.3459 (6)	0.069 (3)
H21A	0.0315	0.2268	0.3286	0.082*
C22	−0.0847 (13)	0.3351 (7)	0.3330 (6)	0.077 (4)
H22A	−0.1789	0.3152	0.3073	0.092*
C23	−0.0710 (13)	0.4196 (7)	0.3585 (6)	0.089 (4)
H23A	−0.1560	0.4544	0.3490	0.106*
C24	0.0652 (12)	0.4502 (6)	0.3968 (6)	0.071 (3)
H24A	0.0749	0.5056	0.4131	0.085*
C25	0.1893 (11)	0.3958 (5)	0.4105 (5)	0.054 (3)
C26	0.4231 (11)	0.3414 (5)	0.4456 (5)	0.044 (2)
C27	0.5740 (11)	0.3489 (5)	0.4795 (5)	0.045 (2)
C28	0.8156 (10)	0.2802 (6)	0.5124 (6)	0.075 (3)
H28A	0.8324	0.2942	0.5651	0.089*
H28B	0.8662	0.3218	0.4877	0.089*
C29	0.8750 (12)	0.1962 (7)	0.5028 (6)	0.101 (4)
H29A	0.9824	0.1948	0.5241	0.152*
H29B	0.8573	0.1830	0.4504	0.152*
H29C	0.8242	0.1557	0.5276	0.152*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F	0.256 (10)	0.129 (7)	0.088 (6)	−0.081 (7)	0.063 (6)	−0.033 (5)
O1	0.085 (6)	0.085 (5)	0.073 (6)	−0.020 (4)	0.022 (4)	0.013 (4)
N1	0.076 (6)	0.026 (4)	0.088 (7)	−0.012 (4)	0.016 (6)	−0.001 (5)
C1	0.050 (6)	0.033 (5)	0.053 (7)	−0.012 (5)	0.011 (5)	0.000 (5)
N2	0.058 (5)	0.031 (4)	0.065 (6)	−0.009 (4)	0.001 (5)	−0.015 (4)
O2	0.081 (5)	0.091 (6)	0.060 (5)	−0.032 (5)	0.014 (4)	−0.005 (4)
C2	0.057 (7)	0.035 (6)	0.065 (8)	−0.025 (5)	0.033 (6)	−0.021 (5)
O3	0.068 (5)	0.036 (4)	0.072 (5)	0.002 (4)	0.001 (4)	−0.004 (3)
C3	0.068 (8)	0.109 (11)	0.117 (12)	−0.005 (8)	0.049 (8)	−0.068 (9)
O4	0.079 (5)	0.030 (4)	0.093 (5)	−0.004 (4)	−0.008 (4)	−0.016 (4)
C4	0.132 (15)	0.105 (14)	0.18 (2)	−0.017 (12)	0.016 (15)	−0.038 (13)
C5	0.132 (14)	0.101 (13)	0.169 (19)	−0.033 (12)	0.065 (14)	−0.106 (13)
C6	0.113 (11)	0.097 (11)	0.066 (10)	−0.081 (9)	0.022 (9)	−0.013 (9)
C7	0.079 (8)	0.067 (8)	0.077 (9)	−0.039 (7)	0.036 (7)	−0.046 (7)
C8	0.062 (7)	0.025 (5)	0.061 (7)	−0.011 (5)	0.013 (6)	−0.002 (5)
C9	0.063 (7)	0.025 (5)	0.069 (8)	−0.017 (5)	0.023 (6)	−0.012 (6)
C10	0.104 (9)	0.053 (7)	0.077 (9)	−0.029 (6)	0.009 (8)	−0.024 (7)
C11	0.097 (9)	0.081 (8)	0.070 (9)	−0.023 (7)	0.021 (7)	−0.029 (7)
C12	0.105 (10)	0.074 (9)	0.084 (10)	−0.019 (8)	0.023 (9)	−0.040 (8)
C13	0.084 (8)	0.034 (6)	0.112 (10)	−0.010 (6)	0.019 (8)	−0.028 (7)
C14	0.063 (7)	0.032 (6)	0.076 (9)	0.006 (5)	0.006 (7)	−0.015 (6)
C15	0.069 (7)	0.031 (6)	0.067 (8)	0.007 (5)	0.010 (7)	−0.003 (6)
C16	0.053 (7)	0.039 (6)	0.094 (10)	−0.010 (6)	0.022 (7)	0.006 (6)
C17	0.062 (8)	0.200 (14)	0.058 (9)	−0.006 (8)	0.008 (7)	−0.030 (9)
C18	0.112	0.112	0.112	0.000	0.024	0.000
C19	0.041 (6)	0.026 (5)	0.049 (6)	−0.005 (4)	0.010 (5)	−0.006 (4)
C20	0.065 (7)	0.032 (5)	0.047 (6)	−0.009 (5)	0.008 (6)	−0.004 (5)
C21	0.072 (8)	0.042 (6)	0.085 (9)	−0.001 (6)	0.003 (7)	−0.010 (6)
C22	0.089 (9)	0.061 (8)	0.070 (8)	−0.002 (7)	−0.008 (7)	−0.015 (6)
C23	0.086 (9)	0.072 (8)	0.098 (10)	0.028 (7)	−0.002 (8)	−0.001 (8)
C24	0.068 (8)	0.039 (6)	0.097 (9)	−0.002 (6)	−0.003 (7)	−0.013 (6)
C25	0.054 (7)	0.036 (6)	0.063 (7)	−0.001 (5)	−0.007 (6)	0.004 (5)
C26	0.053 (6)	0.036 (5)	0.044 (6)	0.003 (5)	0.009 (5)	−0.001 (5)
C27	0.060 (7)	0.030 (5)	0.042 (6)	0.006 (5)	0.001 (5)	−0.008 (5)
C28	0.053 (7)	0.056 (7)	0.100 (9)	0.015 (6)	−0.016 (7)	0.001 (6)
C29	0.097 (9)	0.099 (9)	0.104 (10)	0.053 (8)	0.012 (8)	−0.007 (8)

Geometric parameters (Å, º) top

F—C6	1.374 (13)	C11—C12	1.365 (13)
O1—C16	1.216 (10)	C11—H11A	0.9300
N1—C14	1.356 (11)	C12—C13	1.339 (13)
N1—C15	1.367 (10)	C12—H12A	0.9300
N1—H1A	0.8600	C13—C14	1.418 (12)
C1—C2	1.464 (11)	C13—H13A	0.9300
C1—C8	1.492 (10)	C15—C16	1.488 (13)
C1—C19	1.517 (10)	C17—C18	1.371 (12)
C1—H1B	0.9800	C17—H17A	0.9700
N2—C25	1.335 (10)	C17—H17B	0.9700
N2—C26	1.398 (9)	C18—H18A	0.9600
N2—H2A	0.8600	C18—H18B	0.9600
O2—C16	1.297 (10)	C18—H18C	0.9600
O2—C17	1.440 (11)	C19—C26	1.399 (10)
C2—C7	1.359 (13)	C19—C20	1.409 (11)
C2—C3	1.401 (13)	C20—C25	1.394 (11)
O3—C27	1.351 (9)	C20—C21	1.407 (11)
O3—C28	1.421 (9)	C21—C22	1.389 (12)
C3—C4	1.370 (18)	C21—H21A	0.9300
C3—H3A	0.9300	C22—C23	1.420 (12)
O4—C27	1.234 (9)	C22—H22A	0.9300
C4—C5	1.363 (19)	C23—C24	1.361 (12)
C4—H4A	0.9300	C23—H23A	0.9300
C5—C6	1.339 (18)	C24—C25	1.392 (11)
C5—H5A	0.9300	C24—H24A	0.9300
C6—C7	1.426 (15)	C26—C27	1.370 (11)
C7—H7A	0.9300	C28—C29	1.465 (11)
C8—C15	1.364 (11)	C28—H28A	0.9700
C8—C9	1.457 (12)	C28—H28B	0.9700
C9—C10	1.382 (12)	C29—H29A	0.9600
C9—C14	1.400 (11)	C29—H29B	0.9600
C10—C11	1.389 (12)	C29—H29C	0.9600
C10—H10A	0.9300

C14—N1—C15	108.4 (9)	C8—C15—C16	131.9 (10)
C14—N1—H1A	125.8	O1—C16—O2	125.4 (11)
C15—N1—H1A	125.8	O1—C16—C15	121.1 (10)
C2—C1—C8	111.1 (7)	O2—C16—C15	113.2 (10)
C2—C1—C19	115.7 (7)	C18—C17—O2	109.1 (10)
C8—C1—C19	114.4 (7)	C18—C17—H17A	109.9
C2—C1—H1B	104.7	O2—C17—H17A	109.9
C8—C1—H1B	104.7	C18—C17—H17B	109.9
C19—C1—H1B	104.7	O2—C17—H17B	109.9
C25—N2—C26	109.7 (7)	H17A—C17—H17B	108.3
C25—N2—H2A	125.1	C17—C18—H18A	109.5
C26—N2—H2A	125.1	C17—C18—H18B	109.5
C16—O2—C17	117.4 (9)	H18A—C18—H18B	109.5
C7—C2—C3	119.2 (11)	C17—C18—H18C	109.5
C7—C2—C1	123.7 (10)	H18A—C18—H18C	109.5
C3—C2—C1	117.1 (10)	H18B—C18—H18C	109.5
C27—O3—C28	119.0 (7)	C26—C19—C20	106.9 (7)
C4—C3—C2	121.6 (15)	C26—C19—C1	122.8 (8)
C4—C3—H3A	119.2	C20—C19—C1	130.2 (7)
C2—C3—H3A	119.2	C25—C20—C21	118.4 (9)
C3—C4—C5	122.0 (19)	C25—C20—C19	107.5 (8)
C3—C4—H4A	119.0	C21—C20—C19	134.1 (8)
C5—C4—H4A	119.0	C22—C21—C20	118.8 (9)
C6—C5—C4	114.4 (18)	C22—C21—H21A	120.6
C6—C5—H5A	122.8	C20—C21—H21A	120.6
C4—C5—H5A	122.8	C21—C22—C23	120.8 (10)
C5—C6—F	120.2 (17)	C21—C22—H22A	119.6
C5—C6—C7	127.9 (14)	C23—C22—H22A	119.6
F—C6—C7	111.8 (15)	C24—C23—C22	120.8 (10)
C2—C7—C6	114.8 (11)	C24—C23—H23A	119.6
C2—C7—H7A	122.6	C22—C23—H23A	119.6
C6—C7—H7A	122.6	C23—C24—C25	117.8 (9)
C15—C8—C9	104.8 (8)	C23—C24—H24A	121.1
C15—C8—C1	127.7 (9)	C25—C24—H24A	121.1
C9—C8—C1	127.4 (9)	N2—C25—C24	127.8 (9)
C10—C9—C14	119.6 (10)	N2—C25—C20	108.8 (8)
C10—C9—C8	133.6 (9)	C24—C25—C20	123.4 (9)
C14—C9—C8	106.8 (9)	C27—C26—N2	116.7 (8)
C11—C10—C9	117.9 (10)	C27—C26—C19	136.2 (8)
C11—C10—H10A	121.0	N2—C26—C19	107.1 (7)
C9—C10—H10A	121.0	O4—C27—O3	118.1 (8)
C12—C11—C10	121.6 (11)	O4—C27—C26	126.7 (8)
C12—C11—H11A	119.2	O3—C27—C26	114.9 (8)
C10—C11—H11A	119.2	O3—C28—C29	106.7 (8)
C13—C12—C11	122.5 (12)	O3—C28—H28A	110.4
C13—C12—H12A	118.7	C29—C28—H28A	110.4
C11—C12—H12A	118.7	O3—C28—H28B	110.4
C12—C13—C14	117.2 (11)	C29—C28—H28B	110.4
C12—C13—H13A	121.4	H28A—C28—H28B	108.6
C14—C13—H13A	121.4	C28—C29—H29A	109.5
N1—C14—C9	108.6 (9)	C28—C29—H29B	109.5
N1—C14—C13	130.4 (11)	H29A—C29—H29B	109.5
C9—C14—C13	121.0 (11)	C28—C29—H29C	109.5
N1—C15—C8	111.4 (9)	H29A—C29—H29C	109.5
N1—C15—C16	116.3 (10)	H29B—C29—H29C	109.5

C8—C1—C2—C7	110.8 (9)	C17—O2—C16—O1	3.8 (15)
C19—C1—C2—C7	−21.8 (13)	C17—O2—C16—C15	177.6 (9)
C8—C1—C2—C3	−67.4 (11)	N1—C15—C16—O1	−11.3 (14)
C19—C1—C2—C3	159.9 (8)	C8—C15—C16—O1	176.3 (10)
C7—C2—C3—C4	−0.8 (16)	N1—C15—C16—O2	174.6 (8)
C1—C2—C3—C4	177.5 (11)	C8—C15—C16—O2	2.1 (15)
C2—C3—C4—C5	1 (2)	C16—O2—C17—C18	138.6 (11)
C3—C4—C5—C6	1 (2)	C2—C1—C19—C26	−72.7 (11)
C4—C5—C6—F	−179.3 (12)	C8—C1—C19—C26	156.2 (8)
C4—C5—C6—C7	−3 (2)	C2—C1—C19—C20	104.3 (11)
C3—C2—C7—C6	−0.4 (13)	C8—C1—C19—C20	−26.8 (14)
C1—C2—C7—C6	−178.6 (8)	C26—C19—C20—C25	−1.7 (10)
C5—C6—C7—C2	2.2 (17)	C1—C19—C20—C25	−179.0 (9)
F—C6—C7—C2	179.2 (8)	C26—C19—C20—C21	179.0 (10)
C2—C1—C8—C15	149.4 (10)	C1—C19—C20—C21	1.6 (18)
C19—C1—C8—C15	−77.3 (12)	C25—C20—C21—C22	0.2 (15)
C2—C1—C8—C9	−34.5 (13)	C19—C20—C21—C22	179.5 (10)
C19—C1—C8—C9	98.8 (11)	C20—C21—C22—C23	0.8 (16)
C15—C8—C9—C10	177.8 (11)	C21—C22—C23—C24	−0.5 (18)
C1—C8—C9—C10	1.0 (17)	C22—C23—C24—C25	−0.6 (17)
C15—C8—C9—C14	−1.5 (10)	C26—N2—C25—C24	−177.8 (10)
C1—C8—C9—C14	−178.2 (8)	C26—N2—C25—C20	0.5 (11)
C14—C9—C10—C11	−1.9 (15)	C23—C24—C25—N2	179.7 (10)
C8—C9—C10—C11	178.9 (10)	C23—C24—C25—C20	1.7 (16)
C9—C10—C11—C12	0.9 (16)	C21—C20—C25—N2	−179.8 (8)
C10—C11—C12—C13	0.7 (19)	C19—C20—C25—N2	0.7 (11)
C11—C12—C13—C14	−1.2 (18)	C21—C20—C25—C24	−1.4 (15)
C15—N1—C14—C9	0.3 (10)	C19—C20—C25—C24	179.1 (9)
C15—N1—C14—C13	−179.8 (9)	C25—N2—C26—C27	179.2 (8)
C10—C9—C14—N1	−178.7 (9)	C25—N2—C26—C19	−1.5 (10)
C8—C9—C14—N1	0.7 (10)	C20—C19—C26—C27	−179.0 (11)
C10—C9—C14—C13	1.4 (14)	C1—C19—C26—C27	−1.4 (16)
C8—C9—C14—C13	−179.2 (8)	C20—C19—C26—N2	1.9 (10)
C12—C13—C14—N1	−179.8 (10)	C1—C19—C26—N2	179.5 (8)
C12—C13—C14—C9	0.1 (15)	C28—O3—C27—O4	3.8 (13)
C14—N1—C15—C8	−1.3 (11)	C28—O3—C27—C26	178.8 (8)
C14—N1—C15—C16	−175.3 (8)	N2—C26—C27—O4	−7.4 (14)
C9—C8—C15—N1	1.7 (10)	C19—C26—C27—O4	173.6 (10)
C1—C8—C15—N1	178.5 (8)	N2—C26—C27—O3	178.1 (7)
C9—C8—C15—C16	174.4 (9)	C19—C26—C27—O3	−1.0 (16)
C1—C8—C15—C16	−8.8 (16)	C27—O3—C28—C29	−178.8 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.16	2.918 (11)	147
N2—H2A···O4ⁱⁱ	0.86	2.08	2.904 (9)	159
C11—H11A···O4ⁱⁱⁱ	0.93	2.58	3.498 (13)	171

Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x−1/2, −y+1/2, z−1/2.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

Funding information

Funding for this research was provided by: Natural Science Foundation of Jiangsu Province (grant No. BK20181486); Natural Science Foundation of the Jiangsu Higher Education Institutions (grant No. 17KJB320001); Training program of Students Innovation and Entrepreneurship in Jiangsu Province (grant No. 201812920002Y); Overseas Training Program for Excellent Young Teachers and Principals of Jiangsu Province; Qing Lan Project of Jiangsu Province; Natural Science Foundation of Nanjing Polytechnic Institute (grant No. NHKY-2019-07).

References

Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Lu, X.-H., Sun, H.-S., Cai, Y., Chen, L.-L. & Chen, Y.-F. (2017). Acta Cryst. E73, 1790–1792. Web of Science 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
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals 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., Jiang, H., Xu, N. & Xu, H. (2015). Acta Cryst. E71, 1140–1142. Web of Science 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
Sundberg, R. J. (1996). The Chemistry of Indoles, p. 113. New York: Academic Press. Google Scholar