Two new isatin derivatives: 1-benzyl-4,5,6-trimeth­oxyindoline-2,3-dione and 1-benzyl-5-fluoro­indoline-2,3-dione

Isatin (1H-indole-2,3-dione) derivatives represent synthetically useful substrates which can be used to prepare a broad range of heterocyclic compounds. In the title compounds, C₁₈H₁₇NO₅, (I), and C₁₅H₁₀FNO₂, (II), the isatin ring systems are planar and form a dihedral angle of 73.04 (7)° in (I) and 76.82 (11)° in (II) with the benzyl groups. The bicyclic scaffolds in both compounds are almost superimposable, with an r.m.s. deviation of 0.061 Å. The crystal structures of both derivatives are stabilized by C—H...O inter­actions. These contacts generate an R¹₂(7) ring motif in (I) and a C(7) chain motif in (II).

S1. Introduction

Isatin (1H-indole-2,3-dione) derivatives represent synthetically useful substrates which can be used to prepare a broad range of heterocyclic compounds including examples of pharmacological significance (Bekircan & Bektas, 2008). Such isatin compounds are of inter­est due to their biological activity (Feng et al., 2010) and widespread use as synthetic precursors (da Silva et al., 2001). They show potent anti­convulsant activity at low concentrations (Mathur & Nain, 2014). The high affinity of isatin Schiff bases for chelation towards transition metal ions leads to a wide range of biological activities (Premanathan et al., 2012). We report here an iodine-mediated process for C—H functionalization of sp, sp² and sp³ C atoms in isatin synthesis. Copper-mediated cross-de­hydrogenative C—N annulations and de­alkyl­ative C—N annulations of 2'-N-aryl/alkyl­amino­aceto­phenones and 2'-N,N-di­alkyl­amino­aceto­phenones, respectively, give isatins in good yields, and the NMR spectra [Does not follow from previous clause?] of the title compounds are in agreement with values reported in the literature (Ilangovan & Satish, 2013; Satish et al., 2015). As part of our inter­est in the identification of bioactive compounds and in our attempt to understand the above reaction mechanisms, we report here the synthesis and structure of two isatin derivatives, the title compounds, (I) and (II).

S2. Experimental

S2.1. Synthesis and crystallization

Preparation of 1-benzyl-4,5,6-tri­meth­oxy­indoline-2,3-dione, (I)

To a solution of 1-(2-(benzyl­amino)-2,3,4-tri­meth­oxy­phenyl)­ethanone (100 mg, 0.317 mmol) [In what solvent?], Cu(OAc)₂·H₂O (31.6 mg, 0.158 mmol), NaOAc (39 mg, 0.475 mmol) and di­methyl­siloxane (DMSO; 2 ml) were added at ambient temperature and the mixture heated to 353 K for 15 h in air. Progress of the reaction was monitored by thin-layer chromotography (TLC). Upon completion, the reaction mixture was allowed to cool to ambient temperature and then diluted with ethyl acetate and water. The organic phase was separated, dried over Na₂SO₄, filtered and concentrated. The crude product was purified by silica-gel column chromatography using hexane–ethyl acetate (9:1 v/v) as eluent. It was recrystallized from a solution in a hexane–ethyl acetate mixture (9:1 v/v) by slow evaporation. The solution was allowed to cool to room temperature (298 K) [When had it been re-heated?]. Good quality single crystals of (I) were obtained after 2 d and a crystal suitable for X-ray diffraction study was selected under an optical microscope. Compound (I) was obtained as a red solid, yield 89% (92.3 mg), m.p. 424–425 K. Spectroscopic analysis: ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.): 7.27–7.38 (m, 5H), 5.99 (s, 1H), 4.89 (s, 2H), 4.20 (s, 3H), 3.81 (s, 3H), 3.73 (s, 3H); ¹³C NMR (100 MHz, CDCl₃, δ, p.p.m.): 177.56, 162.24, 159.37, 154.20, 148.68, 136.39, 134.95, 129.08, 128.16, 127.29, 102.62, 90.54, 62.25, 61.48, 56.60, 43.95.

Preparation of 1-benzyl-5-fluoro­indoline-2,3-dione, (II)

To a solution of benzyl­(2-ethynyl-4-fluoro­phenyl)­amine (100 mg, 0.444 mmol) [In what solvent?], I₂ (22.5 mg, 0.088 mmol) and DMSO (3 ml) were added and the mixture heated to 373 K for 3 h in air. Progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was allowed to cool to ambient temperature and then quenched with aqueous sodium thio­sulfate and ethyl acetate. The organic phase was separated, dried over Na₂SO₄, filtered and concentrated. The crude product was purified by silica-gel column chromatography using hexane–ethyl acetate (9:1 v/v). It was recrystallized from a solution in a hexane–ethyl acetate mixture (9:1 v/v) by slow evaporation. The solution was allowed to cool to room temperature (298 K) [When had it been re-heated?]. Good quality single crystals of (II) were obtained after 3 d and a crystal suitable for X-ray diffraction study was selected under an optical microscope. Compound (II) was obtained as a red solid, yield 72% (81.5 mg), m.p. 408–410 K. Spectroscopic analysis: ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.): 7.28–7.18 (m, 6H), 7.11 (td, J = 2.4, 2.8 and 2.8 Hz, 1H), 6.66 (dd, J = 3.6 and 3.6 Hz, 1H), 4.83 (s, 2H); ¹³C NMR (100 MHz, CDCl₃, δ, p.p.m.): 182.7, 160.6, 158.1, 158.1, 146.8, 134.2, 129.1, 128.3, 127.4, 124.8, 124.6, 118.3, 118.2, 112.5, 112.3, 112.3, 44.2. [In the CIF tables, both crystals are described as 'solid', which is self-evident. The item #_exptl_crystal_description should be a description of the shape of the crystal, e.g. block. Please supply these details and we will add them to the CIF]

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. In (I), C-bound H atoms were included in calculated positions and treated as riding, with C—H = 0.93–0.97 Å, and with U_iso(H) = 1.5U_eq(C) for methyl H atoms or 1.2U_eq(C) for other H atoms. A similar procedure was carried out for (II). The initial structure model for both compounds showed values greater than 0.7 for the Flack parameter (Flack, 1983), so the structure models were inverted. In both cases, rather high standard uncertainties for the Flack parameter preclude reliable assignment of the absolute structure.

S3. Results and discussion

Perspective views of (I) and (II) are provided in Figs. 1 and 2, respectively. Corresponding bond distances and angles of the isatin ring systems in (I) and (II) are essentially equivalent and comparable with those in related structures (Helliwell et al., 2012; Lötter et al., 2007). A superposition of the isatin ring systems in (I) and (II) (Fig. 3) gives an r.m.s. deviation of 0.061 Å and underlines the conformational similarity between these molecules (Gans & Shalloway, 2001).

The isatin ring systems are almost planar, with r.m.s. deviations of the fitted atom [Specify?] amounting to 0.046 Å in (I) and 0.009 Å in (II); the bicyclic scaffolds subtend dihedral angles of 73.04 (7) and 76.82 (11)° with the benzyl groups in (I) and (II), respectively. The relative conformation about the bond joining the isatin and benzyl residues in (I) and (II) is defined by C9—N1—C1—C2 torsion angles of −2.7 (3)° in (I) and −4.8 (7)° in (II); thus, these conformations are syn-periplanar. The sums of the bond angles around atom N1 are almost 360.0° (Table 2) in both (I) and (II), indicating little evidence for the presence of sp³ lone pairs.

The crystal structures of (I) and (II) are stabilized by non-classical C—H···O hydrogen bonds (Tables 3 and 4). In (I), the shortest contacts give rise to an intra­molecular R(6) (Bernstein et al., 1995) and an inter­molecular R¹₂(7) motif (Fig. 4). The structure of (II) extends along the [110] direction with the contact between C3 and O2 via H3, generating a C(7) motif (Fig. 5).

Computing details

Data collection: SMART (Bruker, 2008) for (I); SMART (Bruker, 2004) for (II). Cell refinement: SAINT (Bruker, 2008) for (I); SAINT (Bruker, 2004) for (II). Data reduction: SAINT (Bruker, 2008) for (I); SAINT (Bruker, 2004) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: QMOL (Gans & Shalloway, 2001), Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecular structure of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. A superimposed fit of the isatin derivatives (I) (black) and (II) (green).
	Fig. 4. The most relevant C–H···O interactions in (I), shown as dashed lines. H atoms not involved in short contacts have been omitted for clarity. [Symmetry code: (i) 2 − x, 1/2 + y, −1/2 − z.] [For the sake of clarity, we would prefer atom labels to be on the background and not on or overlapping atoms. Can a revised plot be supplied?]
	Fig. 5. The packing in (II), showing the C–H···O interactions along the [110] direction as dashed lines; a C(7) motif is generated. H atoms not involved in short contacts have been omitted for clarity.

(I) 1-Benzyl-4,5,6-trimethoxyindoline-2,3-dione

Crystal data

C18H17NO5	F(000) = 688
Mr = 327.32	Dx = 1.394 Mg m^−3
Orthorhombic, P212121	Melting point: 425 K
a = 7.548 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.066 (5) Å	µ = 0.10 mm^−1
c = 15.815 (5) Å	T = 293 K
V = 1559.7 (13) Å^3	Block, red
Z = 4	0.20 × 0.15 × 0.10 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer	3720 independent reflections
Radiation source: fine-focus sealed tube	3183 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ω and φ scans	θmax = 28.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −10→9
Tmin = 0.980, Tmax = 0.990	k = −16→17
8685 measured reflections	l = −19→16

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.038	w = 1/[σ^2(Fo^2) + (0.0562P)^2 + 0.1642P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.102	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.17 e Å^−3
3720 reflections	Δρmin = −0.31 e Å^−3
220 parameters	Absolute structure: Flack x parameter determined using 1221 quotients [(I^+) - (I^-)]/[(I^+) + (I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: −0.2 (3)
Primary atom site location: structure-invariant direct methods

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.9380 (2)	0.80276 (13)	−0.21083 (11)	0.0359 (4)
O1	1.0084 (3)	0.95829 (13)	−0.27160 (11)	0.0575 (5)
O2	0.9315 (3)	1.03455 (12)	−0.10170 (12)	0.0566 (5)
O3	0.8453 (3)	0.92388 (13)	0.06095 (10)	0.0565 (5)
O4	0.7933 (2)	0.71734 (12)	0.12615 (9)	0.0427 (4)
O5	0.8121 (2)	0.56330 (11)	0.01949 (10)	0.0464 (4)
C1	0.8981 (2)	0.76966 (16)	−0.12762 (13)	0.0334 (4)
C2	0.8753 (3)	0.67042 (15)	−0.10177 (13)	0.0362 (4)
H2	0.8814	0.6158	−0.1394	0.043*
C3	0.8421 (3)	0.65593 (15)	−0.01495 (13)	0.0359 (4)
C4	0.8361 (3)	0.73723 (16)	0.04315 (13)	0.0350 (4)
C5	0.8571 (3)	0.83774 (16)	0.01407 (13)	0.0371 (5)
C6	0.8882 (3)	0.85266 (16)	−0.07256 (13)	0.0358 (4)
C7	0.9269 (3)	0.94496 (17)	−0.12030 (14)	0.0406 (5)
C8	0.9645 (3)	0.90645 (16)	−0.21160 (14)	0.0406 (5)
C9	0.9552 (3)	0.73712 (17)	−0.28543 (13)	0.0398 (5)
H9A	0.9979	0.6703	−0.2683	0.048*
H9B	1.0416	0.7665	−0.3238	0.048*
C10	0.7804 (3)	0.72530 (16)	−0.33074 (12)	0.0362 (4)
C11	0.7229 (3)	0.80044 (18)	−0.38612 (15)	0.0472 (5)
H11	0.7956	0.8562	−0.3974	0.057*
C12	0.5587 (4)	0.7939 (2)	−0.42497 (17)	0.0575 (7)
H12	0.5225	0.8444	−0.4626	0.069*
C13	0.4492 (4)	0.7119 (2)	−0.40751 (17)	0.0600 (7)
H13	0.3373	0.7081	−0.4320	0.072*
C14	0.5064 (4)	0.6353 (2)	−0.35341 (17)	0.0552 (6)
H14	0.4338	0.5794	−0.3422	0.066*
C15	0.6721 (3)	0.64206 (18)	−0.31603 (14)	0.0444 (5)
H15	0.7107	0.5899	−0.2806	0.053*
C16	0.8733 (5)	0.9228 (2)	0.14907 (16)	0.0615 (7)
H16A	0.9757	0.8821	0.1618	0.092*
H16B	0.7715	0.8941	0.1767	0.092*
H16C	0.8917	0.9915	0.1688	0.092*
C17	0.9261 (4)	0.6656 (2)	0.17463 (16)	0.0537 (6)
H17A	1.0367	0.7013	0.1694	0.080*
H17B	0.9394	0.5969	0.1541	0.080*
H17C	0.8912	0.6640	0.2330	0.080*
C18	0.8117 (4)	0.47563 (17)	−0.03439 (16)	0.0559 (7)
H18A	0.9263	0.4679	−0.0599	0.084*
H18B	0.7240	0.4843	−0.0778	0.084*
H18C	0.7844	0.4157	−0.0017	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0411 (9)	0.0385 (9)	0.0281 (8)	−0.0028 (7)	−0.0030 (7)	0.0020 (7)
O1	0.0827 (13)	0.0496 (9)	0.0402 (9)	−0.0133 (9)	0.0000 (9)	0.0113 (8)
O2	0.0830 (13)	0.0352 (8)	0.0516 (10)	−0.0059 (8)	−0.0035 (10)	0.0002 (7)
O3	0.0898 (13)	0.0418 (9)	0.0379 (9)	0.0031 (9)	−0.0002 (9)	−0.0062 (7)
O4	0.0428 (8)	0.0532 (9)	0.0320 (7)	−0.0017 (7)	0.0059 (6)	0.0027 (6)
O5	0.0630 (10)	0.0375 (8)	0.0385 (8)	−0.0092 (8)	0.0022 (7)	0.0036 (6)
C1	0.0292 (9)	0.0395 (10)	0.0314 (10)	−0.0015 (8)	−0.0027 (8)	0.0029 (8)
C2	0.0404 (10)	0.0351 (10)	0.0331 (10)	−0.0018 (8)	−0.0014 (9)	−0.0015 (8)
C3	0.0353 (10)	0.0342 (10)	0.0381 (11)	−0.0035 (8)	−0.0016 (8)	0.0031 (8)
C4	0.0314 (10)	0.0431 (11)	0.0306 (10)	−0.0012 (9)	0.0021 (8)	0.0015 (8)
C5	0.0367 (11)	0.0385 (11)	0.0362 (11)	−0.0011 (9)	−0.0001 (8)	−0.0045 (8)
C6	0.0375 (10)	0.0347 (10)	0.0351 (11)	−0.0023 (8)	−0.0016 (8)	0.0001 (8)
C7	0.0446 (11)	0.0387 (11)	0.0384 (11)	−0.0035 (9)	−0.0048 (9)	0.0035 (9)
C8	0.0440 (11)	0.0395 (11)	0.0382 (11)	−0.0043 (9)	−0.0064 (9)	0.0037 (9)
C9	0.0424 (11)	0.0458 (11)	0.0311 (10)	0.0035 (10)	0.0019 (9)	−0.0024 (9)
C10	0.0435 (10)	0.0401 (10)	0.0249 (9)	0.0055 (9)	0.0033 (8)	−0.0060 (8)
C11	0.0559 (13)	0.0469 (12)	0.0388 (12)	0.0054 (10)	−0.0007 (11)	0.0049 (10)
C12	0.0641 (15)	0.0656 (16)	0.0430 (13)	0.0192 (14)	−0.0109 (12)	0.0019 (11)
C13	0.0472 (13)	0.090 (2)	0.0429 (13)	0.0109 (14)	−0.0085 (11)	−0.0148 (14)
C14	0.0533 (14)	0.0636 (15)	0.0488 (14)	−0.0098 (13)	0.0014 (11)	−0.0146 (12)
C15	0.0558 (14)	0.0440 (11)	0.0333 (11)	−0.0005 (11)	−0.0014 (10)	−0.0030 (9)
C16	0.093 (2)	0.0507 (14)	0.0403 (13)	−0.0020 (14)	0.0006 (14)	−0.0106 (11)
C17	0.0646 (16)	0.0560 (14)	0.0404 (13)	−0.0027 (12)	−0.0063 (12)	0.0087 (11)
C18	0.086 (2)	0.0361 (11)	0.0456 (13)	−0.0067 (12)	−0.0069 (14)	0.0021 (10)

Geometric parameters (Å, º)

N1—C8	1.370 (3)	C9—H9B	0.9700
N1—C1	1.418 (3)	C10—C15	1.381 (3)
N1—C9	1.464 (3)	C10—C11	1.386 (3)
O1—C8	1.212 (3)	C11—C12	1.386 (4)
O2—C7	1.207 (3)	C11—H11	0.9300
O3—C5	1.351 (3)	C12—C13	1.381 (4)
O3—C16	1.410 (3)	C12—H12	0.9300
O4—C4	1.377 (2)	C13—C14	1.386 (4)
O4—C17	1.432 (3)	C13—H13	0.9300
O5—C3	1.346 (2)	C14—C15	1.386 (4)
O5—C18	1.428 (3)	C14—H14	0.9300
C1—C2	1.370 (3)	C15—H15	0.9300
C1—C6	1.393 (3)	C16—H16A	0.9600
C2—C3	1.409 (3)	C16—H16B	0.9600
C2—H2	0.9300	C16—H16C	0.9600
C3—C4	1.405 (3)	C17—H17A	0.9600
C4—C5	1.400 (3)	C17—H17B	0.9600
C5—C6	1.404 (3)	C17—H17C	0.9600
C6—C7	1.453 (3)	C18—H18A	0.9600
C7—C8	1.555 (3)	C18—H18B	0.9600
C9—C10	1.510 (3)	C18—H18C	0.9600
C9—H9A	0.9700
C8—N1—C1	109.94 (17)	C15—C10—C11	118.6 (2)
C8—N1—C9	124.00 (18)	C15—C10—C9	121.2 (2)
C1—N1—C9	126.02 (18)	C11—C10—C9	120.1 (2)
C5—O3—C16	121.64 (19)	C10—C11—C12	121.1 (2)
C4—O4—C17	115.81 (18)	C10—C11—H11	119.4
C3—O5—C18	118.70 (17)	C12—C11—H11	119.4
C2—C1—C6	122.93 (19)	C13—C12—C11	119.7 (2)
C2—C1—N1	126.31 (19)	C13—C12—H12	120.2
C6—C1—N1	110.74 (17)	C11—C12—H12	120.2
C1—C2—C3	116.12 (18)	C12—C13—C14	119.8 (2)
C1—C2—H2	121.9	C12—C13—H13	120.1
C3—C2—H2	121.9	C14—C13—H13	120.1
O5—C3—C4	114.18 (18)	C15—C14—C13	119.9 (3)
O5—C3—C2	123.03 (18)	C15—C14—H14	120.1
C4—C3—C2	122.79 (18)	C13—C14—H14	120.1
O4—C4—C5	121.11 (18)	C10—C15—C14	120.9 (2)
O4—C4—C3	119.23 (18)	C10—C15—H15	119.6
C5—C4—C3	119.37 (18)	C14—C15—H15	119.6
O3—C5—C4	126.42 (19)	O3—C16—H16A	109.5
O3—C5—C6	115.54 (19)	O3—C16—H16B	109.5
C4—C5—C6	118.01 (18)	H16A—C16—H16B	109.5
C1—C6—C5	120.73 (19)	O3—C16—H16C	109.5
C1—C6—C7	108.11 (18)	H16A—C16—H16C	109.5
C5—C6—C7	131.0 (2)	H16B—C16—H16C	109.5
O2—C7—C6	133.2 (2)	O4—C17—H17A	109.5
O2—C7—C8	122.3 (2)	O4—C17—H17B	109.5
C6—C7—C8	104.52 (17)	H17A—C17—H17B	109.5
O1—C8—N1	126.9 (2)	O4—C17—H17C	109.5
O1—C8—C7	126.6 (2)	H17A—C17—H17C	109.5
N1—C8—C7	106.56 (17)	H17B—C17—H17C	109.5
N1—C9—C10	111.39 (17)	O5—C18—H18A	109.5
N1—C9—H9A	109.4	O5—C18—H18B	109.5
C10—C9—H9A	109.4	H18A—C18—H18B	109.5
N1—C9—H9B	109.4	O5—C18—H18C	109.5
C10—C9—H9B	109.4	H18A—C18—H18C	109.5
H9A—C9—H9B	108.0	H18B—C18—H18C	109.5
C8—N1—C1—C2	−175.4 (2)	C4—C5—C6—C1	−0.1 (3)
C9—N1—C1—C2	2.7 (3)	O3—C5—C6—C7	6.7 (3)
C8—N1—C1—C6	3.2 (2)	C4—C5—C6—C7	−175.2 (2)
C9—N1—C1—C6	−178.73 (19)	C1—C6—C7—O2	178.4 (3)
C6—C1—C2—C3	−0.5 (3)	C5—C6—C7—O2	−6.0 (4)
N1—C1—C2—C3	177.94 (18)	C1—C6—C7—C8	−0.8 (2)
C18—O5—C3—C4	178.7 (2)	C5—C6—C7—C8	174.7 (2)
C18—O5—C3—C2	−0.8 (3)	C1—N1—C8—O1	176.5 (2)
C1—C2—C3—O5	178.1 (2)	C9—N1—C8—O1	−1.5 (4)
C1—C2—C3—C4	−1.4 (3)	C1—N1—C8—C7	−3.6 (2)
C17—O4—C4—C5	−114.1 (2)	C9—N1—C8—C7	178.32 (18)
C17—O4—C4—C3	72.1 (3)	O2—C7—C8—O1	3.3 (4)
O5—C3—C4—O4	−3.1 (3)	C6—C7—C8—O1	−177.4 (2)
C2—C3—C4—O4	176.46 (19)	O2—C7—C8—N1	−176.6 (2)
O5—C3—C4—C5	−177.05 (19)	C6—C7—C8—N1	2.7 (2)
C2—C3—C4—C5	2.5 (3)	C8—N1—C9—C10	−91.5 (3)
C16—O3—C5—C4	23.5 (4)	C1—N1—C9—C10	90.7 (2)
C16—O3—C5—C6	−158.6 (2)	N1—C9—C10—C15	−96.1 (2)
O4—C4—C5—O3	2.4 (3)	N1—C9—C10—C11	81.7 (2)
C3—C4—C5—O3	176.2 (2)	C15—C10—C11—C12	1.3 (3)
O4—C4—C5—C6	−175.51 (18)	C9—C10—C11—C12	−176.6 (2)
C3—C4—C5—C6	−1.6 (3)	C10—C11—C12—C13	0.9 (4)
C2—C1—C6—C5	1.2 (3)	C11—C12—C13—C14	−2.0 (4)
N1—C1—C6—C5	−177.40 (19)	C12—C13—C14—C15	1.0 (4)
C2—C1—C6—C7	177.35 (19)	C11—C10—C15—C14	−2.3 (3)
N1—C1—C6—C7	−1.3 (2)	C9—C10—C15—C14	175.5 (2)
O3—C5—C6—C1	−178.2 (2)	C13—C14—C15—C10	1.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17B···O5	0.96	2.38	2.924 (3)	116

(II) 1-Benzyl-5-fluoroindoline-2,3-dione

Crystal data

C15H10FNO2	Dx = 1.392 Mg m^−3
Mr = 255.24	Melting point: 410 K
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
a = 6.6616 (12) Å	Cell parameters from 2807 reflections
b = 4.8577 (10) Å	θ = 2.1–30.6°
c = 19.099 (4) Å	µ = 0.10 mm^−1
β = 99.821 (6)°	T = 296 K
V = 609.0 (2) Å^3	Block, red
Z = 2	0.35 × 0.30 × 0.25 mm
F(000) = 264

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer	1859 independent reflections
Radiation source: fine-focus sealed tube	1318 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
ω and φ scans	θmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −7→7
Tmin = 0.963, Tmax = 0.979	k = −5→5
7057 measured reflections	l = −20→22

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.055	w = 1/[σ^2(Fo^2) + 0.2695P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.080	(Δ/σ)max < 0.001
S = 1.16	Δρmax = 0.21 e Å^−3
1859 reflections	Δρmin = −0.17 e Å^−3
172 parameters	Absolute structure: Flack x parameter determined using 484 quotients [(I^+) - (I^-)]/[(I^+) + (I^-)] (Parsons et al., 2013)
2 restraints	Absolute structure parameter: 0.2 (7)
Primary atom site location: structure-invariant direct methods

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
F1	0.5155 (5)	0.9209 (8)	0.93948 (19)	0.0784 (12)
N1	0.6635 (6)	0.2072 (9)	1.1660 (2)	0.0408 (12)
O1	0.4421 (7)	−0.1119 (9)	1.2022 (3)	0.0751 (14)
O2	0.1608 (6)	0.1218 (9)	1.0805 (2)	0.0722 (13)
C1	0.6498 (7)	0.4013 (11)	1.1103 (3)	0.0353 (14)
C2	0.7988 (8)	0.5760 (11)	1.0944 (3)	0.0419 (15)
H2	0.9282	0.5779	1.1219	0.050*
C3	0.7496 (9)	0.7494 (12)	1.0360 (3)	0.0496 (17)
H3	0.8478	0.8678	1.0238	0.060*
C4	0.5574 (9)	0.7473 (13)	0.9962 (3)	0.0494 (16)
C5	0.4064 (8)	0.5751 (12)	1.0110 (3)	0.0480 (16)
H5	0.2772	0.5755	0.9834	0.058*
C6	0.4546 (8)	0.4019 (11)	1.0686 (3)	0.0385 (14)
C7	0.3358 (9)	0.1944 (12)	1.0989 (3)	0.0486 (16)
C8	0.4836 (9)	0.0692 (12)	1.1633 (3)	0.0515 (17)
C9	0.8499 (8)	0.1397 (11)	1.2160 (3)	0.0467 (15)
H9A	0.9603	0.1122	1.1895	0.056*
H9B	0.8293	−0.0322	1.2396	0.056*
C10	0.9120 (9)	0.3594 (10)	1.2717 (3)	0.0418 (14)
C11	0.7832 (9)	0.4374 (12)	1.3171 (3)	0.0541 (17)
H11	0.6549	0.3573	1.3128	0.065*
C12	0.8420 (11)	0.6342 (14)	1.3693 (3)	0.065 (2)
H12	0.7532	0.6861	1.3996	0.078*
C13	1.0316 (12)	0.7520 (14)	1.3761 (3)	0.069 (2)
H13	1.0714	0.8829	1.4112	0.082*
C14	1.1626 (10)	0.6773 (13)	1.3312 (4)	0.0644 (19)
H14	1.2907	0.7582	1.3356	0.077*
C15	1.1029 (9)	0.4804 (12)	1.2793 (3)	0.0521 (17)
H15	1.1921	0.4288	1.2492	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.090 (3)	0.075 (3)	0.065 (2)	0.003 (2)	0.000 (2)	0.023 (2)
N1	0.037 (3)	0.034 (3)	0.051 (3)	−0.003 (2)	0.007 (3)	0.002 (3)
O1	0.077 (3)	0.069 (3)	0.085 (4)	−0.012 (3)	0.031 (3)	0.018 (3)
O2	0.042 (3)	0.079 (3)	0.098 (4)	−0.014 (2)	0.018 (2)	−0.012 (3)
C1	0.036 (4)	0.029 (3)	0.042 (4)	−0.004 (3)	0.010 (3)	−0.005 (3)
C2	0.036 (4)	0.044 (4)	0.045 (4)	0.002 (3)	0.001 (3)	−0.006 (3)
C3	0.049 (4)	0.045 (4)	0.056 (5)	−0.009 (3)	0.013 (4)	−0.001 (3)
C4	0.059 (5)	0.041 (4)	0.046 (4)	0.004 (3)	0.003 (3)	0.003 (3)
C5	0.042 (4)	0.053 (5)	0.046 (4)	0.005 (3)	−0.002 (3)	−0.008 (4)
C6	0.034 (4)	0.038 (4)	0.044 (4)	−0.003 (3)	0.007 (3)	−0.010 (3)
C7	0.034 (4)	0.056 (4)	0.060 (4)	−0.001 (3)	0.019 (3)	−0.014 (3)
C8	0.057 (4)	0.046 (4)	0.055 (5)	−0.003 (3)	0.020 (3)	−0.001 (4)
C9	0.049 (4)	0.039 (4)	0.052 (4)	0.006 (3)	0.008 (3)	0.004 (3)
C10	0.051 (4)	0.033 (3)	0.041 (4)	0.008 (3)	0.005 (3)	0.008 (3)
C11	0.057 (4)	0.050 (4)	0.057 (4)	0.003 (3)	0.014 (3)	0.003 (4)
C12	0.087 (6)	0.060 (5)	0.051 (5)	0.017 (4)	0.018 (4)	−0.003 (4)
C13	0.095 (6)	0.055 (4)	0.048 (5)	0.009 (4)	−0.011 (4)	−0.004 (4)
C14	0.059 (5)	0.065 (5)	0.063 (5)	−0.012 (4)	−0.007 (4)	−0.001 (4)
C15	0.045 (4)	0.059 (4)	0.051 (4)	0.008 (3)	0.004 (3)	−0.003 (4)

Geometric parameters (Å, º)

F1—C4	1.364 (6)	C7—C8	1.563 (8)
N1—C8	1.367 (7)	C9—C10	1.514 (7)
N1—C1	1.413 (6)	C9—H9A	0.9700
N1—C9	1.469 (6)	C9—H9B	0.9700
O1—C8	1.213 (6)	C10—C11	1.373 (7)
O2—C7	1.211 (6)	C10—C15	1.386 (8)
C1—C2	1.378 (6)	C11—C12	1.389 (8)
C1—C6	1.404 (7)	C11—H11	0.9300
C2—C3	1.392 (8)	C12—C13	1.372 (9)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.373 (7)	C13—C14	1.373 (9)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.374 (7)	C14—C15	1.386 (8)
C5—C6	1.378 (7)	C14—H14	0.9300
C5—H5	0.9300	C15—H15	0.9300
C6—C7	1.461 (8)
C8—N1—C1	110.8 (4)	N1—C8—C7	105.6 (5)
C8—N1—C9	123.6 (5)	N1—C9—C10	113.5 (4)
C1—N1—C9	125.3 (4)	N1—C9—H9A	108.9
C2—C1—C6	120.4 (5)	C10—C9—H9A	108.9
C2—C1—N1	128.3 (5)	N1—C9—H9B	108.9
C6—C1—N1	111.3 (4)	C10—C9—H9B	108.9
C1—C2—C3	118.0 (5)	H9A—C9—H9B	107.7
C1—C2—H2	121.0	C11—C10—C15	118.5 (6)
C3—C2—H2	121.0	C11—C10—C9	120.9 (5)
C4—C3—C2	120.6 (5)	C15—C10—C9	120.6 (5)
C4—C3—H3	119.7	C10—C11—C12	120.9 (6)
C2—C3—H3	119.7	C10—C11—H11	119.6
F1—C4—C3	118.7 (6)	C12—C11—H11	119.6
F1—C4—C5	118.8 (6)	C13—C12—C11	119.8 (6)
C3—C4—C5	122.5 (6)	C13—C12—H12	120.1
C4—C5—C6	117.1 (5)	C11—C12—H12	120.1
C4—C5—H5	121.4	C12—C13—C14	120.3 (6)
C6—C5—H5	121.4	C12—C13—H13	119.9
C5—C6—C1	121.4 (5)	C14—C13—H13	119.9
C5—C6—C7	132.0 (5)	C13—C14—C15	119.6 (6)
C1—C6—C7	106.6 (5)	C13—C14—H14	120.2
O2—C7—C6	130.2 (6)	C15—C14—H14	120.2
O2—C7—C8	124.1 (6)	C14—C15—C10	120.9 (6)
C6—C7—C8	105.6 (5)	C14—C15—H15	119.5
O1—C8—N1	128.5 (6)	C10—C15—H15	119.5
O1—C8—C7	125.9 (6)
C8—N1—C1—C2	−178.9 (5)	C1—N1—C8—O1	179.2 (6)
C9—N1—C1—C2	−4.8 (8)	C9—N1—C8—O1	4.9 (9)
C8—N1—C1—C6	1.1 (6)	C1—N1—C8—C7	−1.2 (5)
C9—N1—C1—C6	175.2 (5)	C9—N1—C8—C7	−175.4 (4)
C6—C1—C2—C3	−0.4 (7)	O2—C7—C8—O1	−0.1 (9)
N1—C1—C2—C3	179.6 (5)	C6—C7—C8—O1	−179.5 (6)
C1—C2—C3—C4	0.7 (8)	O2—C7—C8—N1	−179.8 (5)
C2—C3—C4—F1	179.9 (5)	C6—C7—C8—N1	0.9 (5)
C2—C3—C4—C5	−0.7 (9)	C8—N1—C9—C10	−111.8 (6)
F1—C4—C5—C6	179.7 (5)	C1—N1—C9—C10	74.8 (6)
C3—C4—C5—C6	0.4 (8)	N1—C9—C10—C11	59.0 (7)
C4—C5—C6—C1	−0.1 (8)	N1—C9—C10—C15	−123.0 (5)
C4—C5—C6—C7	−179.3 (6)	C15—C10—C11—C12	0.4 (8)
C2—C1—C6—C5	0.1 (7)	C9—C10—C11—C12	178.4 (5)
N1—C1—C6—C5	−179.9 (5)	C10—C11—C12—C13	−0.3 (9)
C2—C1—C6—C7	179.5 (5)	C11—C12—C13—C14	0.4 (10)
N1—C1—C6—C7	−0.5 (6)	C12—C13—C14—C15	−0.5 (9)
C5—C6—C7—O2	−0.2 (10)	C13—C14—C15—C10	0.5 (9)
C1—C6—C7—O2	−179.5 (6)	C11—C10—C15—C14	−0.4 (8)
C5—C6—C7—C8	179.1 (6)	C9—C10—C15—C14	−178.5 (5)
C1—C6—C7—C8	−0.2 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2^i	0.93	2.50	3.272 (7)	140
C9—H9A···O2^ii	0.97	2.66	3.580 (7)	159

Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y, z.