An analysis of C—H...O and C—H...π interactions in three substituted 4-ketotetra­hydro­indoles

The crystal and molecular structures of the three 4-ketotetrahydro­indoles 2-(4-chloro­phenyl)-1-(4-fluoro­phenyl)-6,6-dimethyl-4,5,6,7-tetra­hydro-1H-indol-4-one (C₂₂H₁₉ClFNO), (I), 1-(4-fluoro­phenyl)-2-(4-methoxy­phenyl)-6,6-di­methyl-4,5,6,7-tetra­hydro-1H-indol-4-one (C₂₃H₂₂FNO₂), (II), and 6,6-dimethyl-1,2-di­phenyl-4,5,6,7-tetra­hydro-1H-indol-4-one (C₂₂H₂₁NO), (III), have been determined via single-crystal X-ray diffraction in order to study the intermolecular interactions therein. All three structures are stabilized via intermolecular C—H...O and C—H...π interactions, generating different molecular motifs.

S1. Comment

The generation of different types of packing motifs in crystalline lattices has been illustrated in detail in the literature. Different types of intermolecular interactions, such as hydrogen bonding (Desiraju, 1989, 2000, 2002; Aakeroy, 1997; Guru Row, 1999; Hunter et al., 2001), C—H···π interactions (Nishio et al., 1995; Umezawa et al., 1999; Takahashi et al., 2000), π–π stacking (Hunter, 1993, 1994) and C—H···O hydrogen bonding (Desiraju & Steiner, 1999; Steiner, 2002) have been reviewed extensively. Recently, it has been shown that `organic fluorine' provides similar interactions, to generate packing motifs in the presence or absence of other intermolecular forces (Prasanna & Guru Row, 2000a,b,c, 2001). We have been interested in the study of the role of organic fluorine in the packing of organic molecules which show biological activity (Choudhury Urs Guru Row & Nagarajan, 2002; Choudhury Urs Smith et al., 2002). Against this background, we report here the crystal and molecular structures of 2-(4-chlorophenyl)-1-(4-fluorophenyl)-6,6-dimethyl-4,5,6,7-tetrahydro- −1H-indol-4-one, (I), and 1-(4-fluorophenyl)-2-(4-methoxyphenyl)-6,6- dimethyl-4,5,6,7-tetrahydro-1H-indol-4-one, (II), and compare these with the corresponding unsubstituted compound 6,6-dimethyl-1,2-diphenyl-4,5,6,7-tetrahydro-1H-indol-4-one, (III) (Varghese et al., 1986), the structure of which we have redetermined. \sch

Most unsubstituted 4-ketotetrahydroindoles have been found to be biologically inactive (Remers et al., 1971) and the inactivity was attributed to the extended conjugation of the C═O group with the indole N atom (Weiss et al., 1968). In order to delocalize the lone pair of electrons on N and to facilitate the activity of the keto function, a series of 1,2-diaryl derivatives were synthesized (Nagarajan et al., 1985). It was found that differently substituted phenyl groups on the 1- or 2-positions facilitate biological activity. Compound (I) of the present study was inactive, whereas (II) showed considerable activity, as reported by Nagarajan et al. (1985). We have redetermined the structure of the unsubstituted compound, (III), since the intermolecular interactions were not discussed in detail in the earlier report by Varghese et al. (1986).

In compound (I), the six-membered ring of the tetrahydroindole (Fig. 1) has an envelope conformation, with atom C5 − 0.641 (3) Å from the C3/C4/C6/C7/C8 plane. Selected torsion angles are given in Table 1. The dihedral angle between the 1-(4-fluorophenyl) and 2-(4-chlorophenyl) rings is 69.84 (7)°. The packing of the molecules in the crystal lattice (Fig. 2) is stabilized via C—H···O and C—H···π interactions (Table 2). There are two independent C—H···π interactions, which link the molecules in the b direction. Thus, molecules packed around the inversion centres at (1/2,1/2,1/2) and (1,1/2,1/2) are linked by pairs of independent C—H···π interactions. C—H···O interactions about the inversion centre at (1/2,1,1/2) then serve to link these chains to form sheets of molecules in the bc plane In Fig. 2 and Table 2, Cg1 is the centroid of the five-membered N1/C1/C2/C8/C7 ring and Cg2 is the centroid of the C9—C14 phenyl ring. It is of interest to note that there are no interactions involving the halogen atoms, though the structure contains a Cl as well as an F.

In compound (II), the six-membered ring of the tetrahydroindole (Fig. 3) has an envelope conformation, with atom C5 − 0.618 (2) Å from the C3/C4/C6/C7/C8 plane, similar to what was observed for (I). Selected torsion angles are given in Table 3. The dihedral angle between the 1-(4-fluorophenyl) and 2-(4-methoxyphenyl) rings is 60.94 (4)°. The molecules pack in the unit cell (Fig. 4) via two different C—H···O interactions (Table 4) in the (101) plane, generating a sheet structure. This is further stabilized by an additional C—H···π interaction which reinforces the two-dimensional sheet (Fig. 4). In Table 4, Cg1 is the centroid of the five-membered N1/C1/C2/C8/C7 ring. Once again, it is to be noted that the F atom does not generate any significant interaction.

In compound (III), the six-membered ring of the tetrahydroindole (Fig. 5) has an envelope conformation, with atom C5 − 0.632 (2) Å from the C3/C4/C6/C7/C8 plane. Selected torsion angles are given in Table 5. The dihedral angle between the 1-phenyl and 2-phenyl rings is 62.99 (6)°. The variation in dihedral angles in (I), (II) and (III) clearly shows that the conformations of the molecules are significantly different among the three compounds. The molecules of (III) pack in the unit cell via two different C—H···O interactions (Fig. 6 and Table 6) generating a `ladder' motif, which is further reinforced by a C—H···π interaction involving C4—H4B (Table 6). In Table 6, Cg1 is the centroid of the five-membered N1/C1/C2/C8/C7 ring and Cg2 is the centroid of the C9–C14 phenyl ring. These ladders are then linked to form a two-dimensional sheet in the (101) plane via a further C—H···π interaction involving C11—H11 and the centroid Cg2 at (-x, 1 − y, 2 − z).

These three structures illustrate the coexistance of C—H···O and C—H···π interactions to generate different packing motifs with altered molecular conformations. Such subtle variations might have a significant impact on the biological activities of such compounds. Indeed, only compound (II) is found to be biologically active.

S2. Experimental

Compounds (I)-(III) were synthesized using the procedure of Nagarajan et al. (1985). Single crystals suitable for X-ray diffraction studies were grown from solutions in acetone (analytical reagent) by slow evaporation at 283 K.

S3. Refinement

The ranges of the C—H bond lengths in (I), (II) and (III) are 0.91 (3)–1.08 (3), 0.93 (2)–1.01 (3) and 0.93 (2)–1.05 (2) Å, respectively.

Computing details

For all compounds, data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997), CAMERON (Watkin et al., 1993) and PLATON (Spek 2003); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON.

Figures

	Fig. 1. A view of the molecule of (I), showing the atom-numbering scheme and with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity.
	Fig. 2. A packing diagram for (I), showing the C—H···O hydrogen-bonded dimer and the intermolecular C—H···π interaction. Cg1 is the centroid of the five-membered N1/C1/C2/C8/C7 ring and Cg2 is the centroid of the C9—C14 phenyl ring. Atoms labelled with a dollar sign (), hash (#) or asterisk (*) are at symmetry positions (1 − x, 2 − y, 1 − z), (2 − x, 1 − y, 1 − z) and (1 − x, 1 − y, 1 − z), respectively.
	Fig. 3. A view of the molecule of (II), showing the atom-numbering scheme and with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity.
	Fig. 4. A stereo view of the packing of (II), showing the C—H···O hydrogen-bonded sheet motif and C—H···π interactions.
	Fig. 5. A view of the molecule of (III), showing the atom-numbering scheme and with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity.
	Fig. 6. A stereo view of the packing of (III), showing the C—H···O hydrogen-bonded ladder motif and C—H···π interactions

(I) 2-(4-chlorophenyl)-1-(4-fluorophenyl)-6,6-dimethyl-4,5,6,7-tetrahydro- 1H-indol-4-one

Crystal data

C22H19ClFNO	Z = 2
Mr = 367.83	F(000) = 384
Triclinic, P1	Dx = 1.292 Mg m^−3
Hall symbol: -P 1	Melting point: 507 K
a = 9.246 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.228 (4) Å	Cell parameters from 2435 reflections
c = 11.177 (4) Å	θ = 2.3–21.2°
α = 80.529 (6)°	µ = 0.22 mm^−1
β = 86.335 (7)°	T = 293 K
γ = 65.120 (6)°	Plate, colourless
V = 945.7 (6) Å^3	0.50 × 0.30 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3788 independent reflections
Radiation source: fine-focus sealed tube	2811 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ϕ and ω scans	θmax = 26.4°, θmin = 1.9°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.844, Tmax = 0.957	k = −12→12
9987 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	All H-atom parameters refined
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0455P)^2 + 0.2584P] where P = (Fo^2 + 2Fc^2)/3
3788 reflections	(Δ/σ)max < 0.001
311 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cl1	0.66030 (9)	0.27487 (8)	0.99603 (6)	0.0893 (3)
N1	0.74427 (17)	0.54652 (15)	0.39864 (14)	0.0445 (4)
O1	0.5159 (3)	1.04382 (16)	0.30251 (16)	0.0989 (7)
F1	1.1009 (2)	−0.02663 (15)	0.34244 (18)	0.1180 (6)
C1	0.6736 (2)	0.60481 (19)	0.50405 (17)	0.0449 (4)
C2	0.6048 (2)	0.7529 (2)	0.47288 (19)	0.0505 (5)
C3	0.5853 (3)	0.9258 (2)	0.2686 (2)	0.0588 (5)
C4	0.6250 (3)	0.9138 (2)	0.1373 (2)	0.0600 (6)
C5	0.7828 (3)	0.7863 (2)	0.1146 (2)	0.0594 (5)
C6	0.7775 (3)	0.6433 (2)	0.1792 (2)	0.0572 (5)
C7	0.7189 (2)	0.65797 (19)	0.30515 (17)	0.0466 (4)
C8	0.6317 (2)	0.78683 (19)	0.34852 (18)	0.0487 (5)
C9	0.8369 (2)	0.39556 (18)	0.38695 (17)	0.0451 (4)
C10	0.9871 (3)	0.3220 (2)	0.4367 (2)	0.0607 (6)
C11	1.0767 (3)	0.1786 (2)	0.4214 (3)	0.0760 (7)
C12	1.0124 (3)	0.1143 (2)	0.3575 (2)	0.0734 (7)
C13	0.8633 (3)	0.1833 (3)	0.3088 (2)	0.0772 (7)
C14	0.7741 (3)	0.3273 (2)	0.3234 (2)	0.0637 (6)
C15	0.6749 (2)	0.51810 (19)	0.62245 (17)	0.0457 (4)
C16	0.6757 (3)	0.5763 (2)	0.72673 (19)	0.0551 (5)
C17	0.6686 (3)	0.5037 (2)	0.8405 (2)	0.0620 (6)
C18	0.6626 (2)	0.3697 (2)	0.85213 (19)	0.0570 (5)
C19	0.6614 (2)	0.3093 (2)	0.7518 (2)	0.0562 (5)
C20	0.6669 (2)	0.3830 (2)	0.6379 (2)	0.0508 (5)
C21	0.8021 (5)	0.7823 (4)	−0.0217 (3)	0.0885 (9)
C22	0.9196 (4)	0.8080 (4)	0.1648 (4)	0.0913 (9)
H2	0.547 (2)	0.817 (2)	0.5230 (17)	0.049 (5)*
H4A	0.625 (2)	1.005 (2)	0.0972 (19)	0.063 (6)*
H4B	0.539 (3)	0.900 (2)	0.1011 (19)	0.068 (6)*
H6A	0.880 (3)	0.563 (2)	0.1784 (18)	0.061 (6)*
H6B	0.705 (2)	0.619 (2)	0.1332 (18)	0.057 (6)*
H10	1.029 (3)	0.369 (2)	0.483 (2)	0.072 (7)*
H11	1.181 (3)	0.129 (3)	0.458 (2)	0.093 (8)*
H13	0.823 (3)	0.136 (3)	0.265 (2)	0.087 (8)*
H14	0.672 (3)	0.380 (3)	0.289 (2)	0.083 (8)*
H16	0.683 (2)	0.666 (2)	0.7170 (18)	0.058 (6)*
H17	0.669 (3)	0.548 (2)	0.909 (2)	0.070 (7)*
H19	0.659 (2)	0.217 (2)	0.7612 (18)	0.060 (6)*
H20	0.663 (2)	0.341 (2)	0.5701 (19)	0.056 (6)*
H21A	0.813 (3)	0.870 (3)	−0.066 (3)	0.105 (9)*
H21B	0.711 (4)	0.768 (3)	−0.060 (3)	0.122 (12)*
H21C	0.897 (3)	0.703 (3)	−0.033 (2)	0.082 (8)*
H22A	1.010 (4)	0.731 (4)	0.149 (3)	0.115 (11)*
H22B	0.910 (4)	0.811 (3)	0.261 (3)	0.121 (11)*
H22C	0.926 (3)	0.894 (3)	0.123 (3)	0.110 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1093 (6)	0.0859 (5)	0.0681 (4)	−0.0433 (4)	0.0167 (4)	0.0020 (3)
N1	0.0443 (9)	0.0342 (8)	0.0510 (9)	−0.0102 (6)	−0.0023 (7)	−0.0121 (7)
O1	0.1506 (18)	0.0356 (9)	0.0811 (12)	−0.0081 (10)	−0.0041 (11)	−0.0136 (8)
F1	0.1249 (14)	0.0436 (8)	0.1618 (17)	−0.0023 (8)	0.0004 (12)	−0.0426 (9)
C1	0.0418 (10)	0.0387 (10)	0.0535 (11)	−0.0126 (8)	−0.0030 (8)	−0.0151 (8)
C2	0.0500 (11)	0.0385 (10)	0.0581 (13)	−0.0091 (9)	−0.0026 (9)	−0.0189 (9)
C3	0.0648 (13)	0.0404 (11)	0.0633 (14)	−0.0118 (10)	−0.0105 (10)	−0.0106 (10)
C4	0.0698 (15)	0.0411 (11)	0.0642 (14)	−0.0197 (10)	−0.0120 (11)	0.0001 (10)
C5	0.0628 (13)	0.0518 (12)	0.0597 (13)	−0.0213 (10)	0.0017 (10)	−0.0061 (10)
C6	0.0633 (14)	0.0435 (11)	0.0578 (13)	−0.0140 (10)	0.0020 (11)	−0.0125 (10)
C7	0.0457 (10)	0.0376 (10)	0.0533 (11)	−0.0126 (8)	−0.0071 (9)	−0.0088 (8)
C8	0.0497 (11)	0.0372 (10)	0.0544 (12)	−0.0112 (8)	−0.0080 (9)	−0.0106 (8)
C9	0.0470 (11)	0.0340 (9)	0.0521 (11)	−0.0131 (8)	0.0021 (8)	−0.0117 (8)
C10	0.0505 (12)	0.0414 (11)	0.0883 (16)	−0.0140 (9)	−0.0091 (11)	−0.0161 (11)
C11	0.0538 (14)	0.0440 (12)	0.116 (2)	−0.0049 (11)	−0.0105 (14)	−0.0133 (13)
C12	0.0820 (17)	0.0346 (11)	0.0926 (18)	−0.0094 (11)	0.0063 (14)	−0.0240 (11)
C13	0.097 (2)	0.0520 (13)	0.0861 (18)	−0.0246 (14)	−0.0119 (15)	−0.0310 (13)
C14	0.0649 (14)	0.0492 (12)	0.0741 (15)	−0.0148 (11)	−0.0128 (12)	−0.0218 (11)
C15	0.0384 (10)	0.0385 (10)	0.0564 (12)	−0.0101 (8)	−0.0006 (8)	−0.0127 (9)
C16	0.0665 (13)	0.0401 (11)	0.0595 (13)	−0.0209 (10)	0.0032 (10)	−0.0142 (10)
C17	0.0736 (15)	0.0586 (13)	0.0546 (13)	−0.0254 (11)	0.0065 (11)	−0.0187 (11)
C18	0.0514 (12)	0.0539 (12)	0.0599 (13)	−0.0180 (9)	0.0083 (10)	−0.0069 (10)
C19	0.0509 (12)	0.0448 (11)	0.0736 (15)	−0.0213 (9)	0.0075 (10)	−0.0099 (11)
C20	0.0483 (11)	0.0454 (11)	0.0609 (13)	−0.0188 (9)	0.0031 (9)	−0.0164 (10)
C21	0.113 (3)	0.0669 (18)	0.0729 (18)	−0.0294 (19)	0.0206 (18)	−0.0073 (14)
C22	0.0693 (19)	0.086 (2)	0.123 (3)	−0.0384 (17)	0.0025 (18)	−0.010 (2)

Geometric parameters (Å, º)

Cl1—C18	1.740 (2)	C10—C11	1.381 (3)
N1—C7	1.364 (2)	C10—H10	0.96 (2)
N1—C1	1.405 (2)	C11—C12	1.355 (4)
N1—C9	1.440 (2)	C11—H11	0.96 (3)
O1—C3	1.217 (2)	C12—C13	1.358 (4)
F1—C12	1.358 (2)	C13—C14	1.384 (3)
C1—C2	1.365 (3)	C13—H13	0.93 (3)
C1—C15	1.464 (3)	C14—H14	0.94 (2)
C2—C8	1.409 (3)	C15—C16	1.395 (3)
C2—H2	0.91 (2)	C15—C20	1.397 (3)
C3—C8	1.456 (3)	C16—C17	1.375 (3)
C3—C4	1.502 (3)	C16—H16	0.94 (2)
C4—C5	1.534 (3)	C17—C18	1.379 (3)
C4—H4A	0.96 (2)	C17—H17	0.95 (2)
C4—H4B	0.98 (2)	C18—C19	1.370 (3)
C5—C22	1.527 (4)	C19—C20	1.378 (3)
C5—C21	1.528 (4)	C19—H19	0.94 (2)
C5—C6	1.540 (3)	C20—H20	0.94 (2)
C6—C7	1.483 (3)	C21—H21A	0.99 (3)
C6—H6A	0.96 (2)	C21—H21B	1.04 (3)
C6—H6B	1.00 (2)	C21—H21C	0.93 (3)
C7—C8	1.374 (2)	C22—H22A	0.91 (3)
C9—C10	1.373 (3)	C22—H22B	1.08 (3)
C9—C14	1.373 (3)	C22—H22C	0.95 (3)
C7—N1—C1	109.06 (14)	C12—C11—C10	118.4 (2)
C7—N1—C9	123.19 (15)	C12—C11—H11	123.1 (15)
C1—N1—C9	127.67 (15)	C10—C11—H11	118.4 (16)
C2—C1—N1	106.91 (17)	C11—C12—F1	118.3 (2)
C2—C1—C15	128.35 (17)	C11—C12—C13	123.2 (2)
N1—C1—C15	124.73 (15)	F1—C12—C13	118.5 (2)
C1—C2—C8	108.24 (17)	C12—C13—C14	118.3 (2)
C1—C2—H2	125.5 (12)	C12—C13—H13	120.8 (16)
C8—C2—H2	126.2 (12)	C14—C13—H13	120.9 (16)
O1—C3—C8	123.9 (2)	C9—C14—C13	119.7 (2)
O1—C3—C4	121.3 (2)	C9—C14—H14	119.4 (15)
C8—C3—C4	114.77 (17)	C13—C14—H14	120.9 (15)
C3—C4—C5	114.82 (18)	C16—C15—C20	117.46 (19)
C3—C4—H4A	108.7 (12)	C16—C15—C1	118.54 (17)
C5—C4—H4A	110.3 (12)	C20—C15—C1	123.91 (17)
C3—C4—H4B	107.5 (13)	C17—C16—C15	121.4 (2)
C5—C4—H4B	107.6 (12)	C17—C16—H16	120.7 (12)
H4A—C4—H4B	107.7 (17)	C15—C16—H16	117.9 (12)
C22—C5—C21	110.6 (3)	C16—C17—C18	119.5 (2)
C22—C5—C4	108.9 (2)	C16—C17—H17	118.5 (14)
C21—C5—C4	108.9 (2)	C18—C17—H17	122.0 (14)
C22—C5—C6	110.3 (2)	C19—C18—C17	120.8 (2)
C21—C5—C6	109.5 (2)	C19—C18—Cl1	119.62 (17)
C4—C5—C6	108.68 (18)	C17—C18—Cl1	119.60 (18)
C7—C6—C5	110.59 (17)	C18—C19—C20	119.6 (2)
C7—C6—H6A	110.9 (13)	C18—C19—H19	119.8 (13)
C5—C6—H6A	111.2 (13)	C20—C19—H19	120.6 (13)
C7—C6—H6B	109.6 (12)	C19—C20—C15	121.3 (2)
C5—C6—H6B	109.4 (11)	C19—C20—H20	118.5 (12)
H6A—C6—H6B	105.0 (17)	C15—C20—H20	120.2 (12)
N1—C7—C8	108.00 (17)	C5—C21—H21A	111.8 (17)
N1—C7—C6	126.16 (16)	C5—C21—H21B	113.2 (18)
C8—C7—C6	125.83 (18)	H21A—C21—H21B	110 (2)
C7—C8—C2	107.78 (17)	C5—C21—H21C	107.5 (16)
C7—C8—C3	120.59 (19)	H21A—C21—H21C	107 (2)
C2—C8—C3	131.62 (17)	H21B—C21—H21C	107 (2)
C10—C9—C14	120.58 (18)	C5—C22—H22A	105 (2)
C10—C9—N1	120.35 (17)	C5—C22—H22B	112.7 (17)
C14—C9—N1	119.06 (17)	H22A—C22—H22B	110 (3)
C9—C10—C11	119.8 (2)	C5—C22—H22C	110.8 (19)
C9—C10—H10	120.1 (13)	H22A—C22—H22C	108 (3)
C11—C10—H10	120.1 (14)	H22B—C22—H22C	110 (3)
C7—N1—C1—C2	0.2 (2)	C4—C3—C8—C2	−174.4 (2)
C9—N1—C1—C2	177.12 (17)	C7—N1—C9—C10	106.0 (2)
C7—N1—C1—C15	179.41 (16)	C1—N1—C9—C10	−70.5 (3)
C9—N1—C1—C15	−3.7 (3)	C7—N1—C9—C14	−72.7 (3)
N1—C1—C2—C8	0.3 (2)	C1—N1—C9—C14	110.7 (2)
C15—C1—C2—C8	−178.91 (18)	C14—C9—C10—C11	0.9 (4)
O1—C3—C4—C5	145.5 (2)	N1—C9—C10—C11	−177.9 (2)
C8—C3—C4—C5	−36.3 (3)	C9—C10—C11—C12	−0.3 (4)
C3—C4—C5—C22	−62.9 (3)	C10—C11—C12—F1	179.9 (2)
C3—C4—C5—C21	176.5 (2)	C10—C11—C12—C13	−0.8 (4)
C3—C4—C5—C6	57.3 (3)	C11—C12—C13—C14	1.2 (4)
C22—C5—C6—C7	72.3 (3)	F1—C12—C13—C14	−179.5 (2)
C21—C5—C6—C7	−165.8 (2)	C10—C9—C14—C13	−0.4 (4)
C4—C5—C6—C7	−47.0 (2)	N1—C9—C14—C13	178.3 (2)
C1—N1—C7—C8	−0.6 (2)	C12—C13—C14—C9	−0.6 (4)
C9—N1—C7—C8	−177.68 (16)	C2—C1—C15—C16	−32.3 (3)
C1—N1—C7—C6	178.39 (19)	N1—C1—C15—C16	148.67 (18)
C9—N1—C7—C6	1.3 (3)	C2—C1—C15—C20	144.2 (2)
C5—C6—C7—N1	−158.22 (18)	N1—C1—C15—C20	−34.9 (3)
C5—C6—C7—C8	20.6 (3)	C20—C15—C16—C17	−0.1 (3)
N1—C7—C8—C2	0.7 (2)	C1—C15—C16—C17	176.55 (19)
C6—C7—C8—C2	−178.24 (19)	C15—C16—C17—C18	0.9 (3)
N1—C7—C8—C3	−179.65 (17)	C16—C17—C18—C19	−0.9 (3)
C6—C7—C8—C3	1.4 (3)	C16—C17—C18—Cl1	177.85 (17)
C1—C2—C8—C7	−0.6 (2)	C17—C18—C19—C20	0.2 (3)
C1—C2—C8—C3	179.8 (2)	Cl1—C18—C19—C20	−178.56 (15)
O1—C3—C8—C7	−175.8 (2)	C18—C19—C20—C15	0.6 (3)
C4—C3—C8—C7	6.1 (3)	C16—C15—C20—C19	−0.6 (3)
O1—C3—C8—C2	3.7 (4)	C1—C15—C20—C19	−177.08 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1^i	0.90 (2)	2.50 (2)	3.358 (3)	158 (2)
C10—H10···Cg1^ii	0.96 (2)	2.93	3.723 (3)	142
C14—H14···Cg2^iii	0.94 (2)	2.90	3.804 (3)	162

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

(II) 1-(4-fluorophenyl)-2-(4-methoxyphenyl)-6,6-dimethyl-4,5,6,7-tetrahydro- 1H-indol-4-one

Crystal data

C23H22FNO2	F(000) = 768
Mr = 363.42	Dx = 1.237 Mg m^−3
Monoclinic, P21/n	Melting point: 494 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 10.112 (2) Å	Cell parameters from 974 reflections
b = 19.073 (4) Å	θ = 2.7–24.3°
c = 11.287 (3) Å	µ = 0.09 mm^−1
β = 116.348 (3)°	T = 293 K
V = 1950.8 (8) Å^3	Prism, colourless
Z = 4	0.40 × 0.30 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3562 independent reflections
Radiation source: sealed tube	2818 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ϕ and ω scans	θmax = 25.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.887, Tmax = 0.983	k = −22→21
14313 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	All H-atom parameters refined
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0502P)^2 + 0.3423P] where P = (Fo^2 + 2Fc^2)/3
3562 reflections	(Δ/σ)max < 0.001
332 parameters	Δρmax = 0.15 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
F1	0.25458 (15)	0.35840 (6)	0.68136 (15)	0.1001 (5)
O1	0.81733 (13)	−0.04919 (6)	0.59350 (12)	0.0591 (3)
O2	0.74360 (13)	0.41255 (7)	0.27699 (13)	0.0692 (4)
N1	0.58615 (13)	0.15763 (6)	0.58559 (12)	0.0422 (3)
C1	0.66762 (15)	0.16589 (8)	0.51285 (15)	0.0421 (3)
C2	0.73415 (17)	0.10389 (8)	0.51610 (15)	0.0439 (4)
C3	0.73646 (16)	−0.01635 (8)	0.62834 (15)	0.0438 (4)
C4	0.6681 (2)	−0.05015 (9)	0.70871 (18)	0.0511 (4)
C5	0.63399 (19)	−0.00126 (9)	0.79896 (16)	0.0539 (4)
C6	0.5407 (2)	0.06088 (9)	0.71829 (18)	0.0519 (4)
C7	0.60495 (16)	0.09075 (7)	0.63381 (14)	0.0417 (3)
C8	0.69592 (15)	0.05605 (8)	0.59254 (14)	0.0419 (3)
C9	0.50004 (16)	0.21030 (7)	0.61026 (15)	0.0419 (3)
C10	0.56745 (19)	0.26830 (9)	0.68513 (18)	0.0548 (4)
C11	0.4849 (2)	0.31890 (9)	0.7094 (2)	0.0643 (5)
C12	0.3365 (2)	0.30926 (9)	0.6576 (2)	0.0625 (5)
C13	0.2667 (2)	0.25201 (10)	0.5838 (2)	0.0642 (5)
C14	0.34993 (18)	0.20199 (9)	0.55971 (18)	0.0522 (4)
C15	0.67816 (16)	0.23226 (8)	0.45051 (14)	0.0427 (4)
C16	0.81536 (18)	0.25265 (9)	0.46274 (18)	0.0529 (4)
C17	0.83263 (19)	0.31212 (9)	0.40332 (18)	0.0573 (4)
C18	0.71305 (17)	0.35407 (8)	0.32950 (15)	0.0473 (4)
C19	0.57575 (19)	0.33536 (9)	0.31572 (17)	0.0543 (4)
C20	0.55954 (18)	0.27460 (9)	0.37593 (18)	0.0555 (4)
C21	0.5437 (4)	−0.04221 (14)	0.8545 (3)	0.0829 (7)
C22	0.7775 (3)	0.02470 (16)	0.9109 (2)	0.0837 (7)
C23	0.6276 (3)	0.45901 (14)	0.2033 (3)	0.0835 (7)
H2	0.7935 (17)	0.0944 (8)	0.4719 (14)	0.045 (4)*
H4A	0.7330 (19)	−0.0871 (9)	0.7600 (16)	0.059 (5)*
H4B	0.575 (2)	−0.0728 (9)	0.6444 (17)	0.060 (5)*
H6A	0.532 (2)	0.0967 (10)	0.7770 (18)	0.067 (5)*
H6B	0.437 (2)	0.0456 (9)	0.6609 (17)	0.061 (5)*
H10	0.674 (2)	0.2724 (9)	0.7212 (17)	0.068 (5)*
H11	0.529 (2)	0.3602 (11)	0.762 (2)	0.078 (6)*
H13	0.161 (2)	0.2480 (10)	0.5496 (18)	0.077 (6)*
H14	0.3025 (17)	0.1611 (9)	0.5099 (16)	0.052 (4)*
H16	0.901 (2)	0.2242 (10)	0.5145 (17)	0.066 (5)*
H17	0.930 (2)	0.3261 (10)	0.4126 (18)	0.071 (5)*
H19	0.489 (2)	0.3630 (9)	0.2640 (17)	0.065 (5)*
H20	0.462 (2)	0.2606 (9)	0.3635 (17)	0.066 (5)*
H21A	0.838 (2)	0.0544 (12)	0.882 (2)	0.094 (7)*
H21B	0.840 (3)	−0.0166 (14)	0.959 (3)	0.113 (9)*
H21C	0.758 (3)	0.0566 (13)	0.970 (3)	0.116 (9)*
H22A	0.604 (2)	−0.0790 (13)	0.910 (2)	0.096 (7)*
H23B	0.575 (3)	0.4718 (13)	0.252 (3)	0.114 (9)*
H22C	0.522 (3)	−0.0119 (14)	0.911 (3)	0.116 (9)*
H23A	0.555 (3)	0.4363 (13)	0.124 (3)	0.112 (9)*
H22B	0.447 (3)	−0.0596 (15)	0.783 (3)	0.130 (11)*
H23C	0.671 (2)	0.4962 (12)	0.181 (2)	0.092 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.1069 (10)	0.0639 (7)	0.1599 (13)	0.0262 (7)	0.0866 (10)	−0.0064 (8)
O1	0.0650 (7)	0.0424 (6)	0.0790 (8)	0.0106 (5)	0.0402 (7)	0.0023 (6)
O2	0.0616 (7)	0.0595 (8)	0.0907 (9)	0.0040 (6)	0.0375 (7)	0.0307 (7)
N1	0.0440 (7)	0.0343 (7)	0.0515 (7)	0.0028 (5)	0.0240 (6)	0.0015 (6)
C1	0.0405 (8)	0.0382 (8)	0.0486 (9)	−0.0014 (6)	0.0205 (7)	0.0011 (7)
C2	0.0441 (8)	0.0419 (9)	0.0513 (9)	0.0017 (7)	0.0261 (7)	0.0001 (7)
C3	0.0404 (8)	0.0380 (8)	0.0477 (9)	0.0008 (6)	0.0146 (7)	−0.0026 (7)
C4	0.0518 (10)	0.0401 (9)	0.0580 (10)	0.0037 (8)	0.0213 (8)	0.0095 (8)
C5	0.0616 (10)	0.0524 (10)	0.0488 (9)	0.0055 (8)	0.0256 (8)	0.0092 (8)
C6	0.0602 (11)	0.0470 (10)	0.0577 (10)	0.0059 (8)	0.0344 (9)	0.0067 (8)
C7	0.0431 (8)	0.0359 (8)	0.0456 (8)	0.0010 (6)	0.0193 (7)	0.0014 (6)
C8	0.0419 (8)	0.0365 (8)	0.0473 (8)	0.0017 (6)	0.0196 (7)	−0.0003 (7)
C9	0.0442 (8)	0.0354 (8)	0.0483 (8)	0.0030 (6)	0.0225 (7)	0.0023 (7)
C10	0.0478 (9)	0.0457 (10)	0.0683 (11)	−0.0037 (8)	0.0234 (9)	−0.0082 (8)
C11	0.0736 (13)	0.0419 (10)	0.0824 (13)	−0.0031 (9)	0.0393 (11)	−0.0156 (9)
C12	0.0724 (12)	0.0415 (10)	0.0892 (13)	0.0145 (9)	0.0500 (11)	0.0037 (9)
C13	0.0465 (10)	0.0550 (11)	0.0947 (14)	0.0075 (9)	0.0346 (10)	0.0043 (10)
C14	0.0457 (9)	0.0419 (9)	0.0669 (11)	−0.0016 (7)	0.0231 (8)	−0.0031 (8)
C15	0.0437 (8)	0.0379 (8)	0.0473 (8)	−0.0003 (6)	0.0210 (7)	0.0009 (7)
C16	0.0439 (9)	0.0492 (10)	0.0678 (11)	0.0064 (8)	0.0269 (8)	0.0127 (8)
C17	0.0451 (9)	0.0554 (11)	0.0770 (12)	0.0007 (8)	0.0323 (9)	0.0142 (9)
C18	0.0518 (9)	0.0430 (9)	0.0513 (9)	−0.0018 (7)	0.0267 (8)	0.0056 (7)
C19	0.0456 (9)	0.0536 (10)	0.0603 (10)	0.0060 (8)	0.0205 (8)	0.0151 (8)
C20	0.0396 (8)	0.0557 (10)	0.0684 (11)	−0.0023 (8)	0.0212 (8)	0.0124 (9)
C21	0.111 (2)	0.0746 (15)	0.0873 (17)	0.0171 (15)	0.0656 (17)	0.0314 (14)
C22	0.0902 (16)	0.0896 (18)	0.0526 (12)	0.0009 (15)	0.0149 (12)	−0.0037 (12)
C23	0.0764 (15)	0.0693 (15)	0.1024 (19)	0.0072 (13)	0.0374 (15)	0.0427 (14)

Geometric parameters (Å, º)

F1—C12	1.3545 (18)	C10—H10	0.972 (18)
O1—C3	1.2252 (17)	C11—C12	1.359 (3)
O2—C18	1.3613 (18)	C11—H11	0.97 (2)
O2—C23	1.409 (2)	C12—C13	1.365 (3)
N1—C7	1.3667 (18)	C13—C14	1.377 (2)
N1—C1	1.4065 (18)	C13—H13	0.96 (2)
N1—C9	1.4352 (18)	C14—H14	0.956 (17)
C1—C2	1.353 (2)	C15—C20	1.380 (2)
C1—C15	1.475 (2)	C15—C16	1.388 (2)
C2—C8	1.422 (2)	C16—C17	1.368 (2)
C2—H2	0.953 (15)	C16—H16	0.968 (19)
C3—C8	1.446 (2)	C17—C18	1.379 (2)
C3—C4	1.508 (2)	C17—H17	0.976 (19)
C4—C5	1.529 (2)	C18—C19	1.374 (2)
C4—H4A	0.962 (18)	C19—C20	1.389 (2)
C4—H4B	0.996 (18)	C19—H19	0.967 (19)
C5—C22	1.523 (3)	C20—H20	0.974 (18)
C5—C21	1.531 (3)	C21—H22A	0.96 (2)
C5—C6	1.537 (2)	C21—H22C	0.96 (3)
C6—C7	1.485 (2)	C21—H22B	1.01 (3)
C6—H6A	0.981 (19)	C22—H21A	0.99 (2)
C6—H6B	1.001 (18)	C22—H21B	1.01 (3)
C7—C8	1.3717 (19)	C22—H21C	0.99 (3)
C9—C14	1.373 (2)	C23—H23B	0.95 (3)
C9—C10	1.375 (2)	C23—H23A	0.97 (3)
C10—C11	1.381 (2)	C23—H23C	0.93 (2)
C18—O2—C23	118.80 (15)	F1—C12—C11	118.46 (17)
C7—N1—C1	108.84 (11)	F1—C12—C13	118.56 (17)
C7—N1—C9	124.41 (12)	C11—C12—C13	122.98 (16)
C1—N1—C9	126.72 (12)	C12—C13—C14	118.60 (17)
C2—C1—N1	107.42 (12)	C12—C13—H13	119.2 (12)
C2—C1—C15	128.52 (13)	C14—C13—H13	122.1 (12)
N1—C1—C15	124.03 (12)	C9—C14—C13	119.86 (17)
C1—C2—C8	108.15 (13)	C9—C14—H14	120.8 (9)
C1—C2—H2	124.9 (9)	C13—C14—H14	119.4 (9)
C8—C2—H2	126.9 (9)	C20—C15—C16	117.19 (14)
O1—C3—C8	123.05 (14)	C20—C15—C1	124.48 (13)
O1—C3—C4	121.62 (14)	C16—C15—C1	118.28 (13)
C8—C3—C4	115.30 (13)	C17—C16—C15	121.55 (15)
C3—C4—C5	116.06 (14)	C17—C16—H16	119.1 (10)
C3—C4—H4A	107.6 (10)	C15—C16—H16	119.4 (10)
C5—C4—H4A	110.0 (10)	C16—C17—C18	120.58 (15)
C3—C4—H4B	106.5 (9)	C16—C17—H17	121.0 (11)
C5—C4—H4B	109.3 (10)	C18—C17—H17	118.4 (11)
H4A—C4—H4B	107.0 (14)	O2—C18—C19	125.22 (15)
C22—C5—C4	109.72 (17)	O2—C18—C17	115.52 (14)
C22—C5—C21	110.4 (2)	C19—C18—C17	119.25 (15)
C4—C5—C21	108.26 (17)	C18—C19—C20	119.60 (16)
C22—C5—C6	110.44 (17)	C18—C19—H19	121.9 (10)
C4—C5—C6	109.65 (13)	C20—C19—H19	118.5 (10)
C21—C5—C6	108.35 (16)	C15—C20—C19	121.82 (15)
C7—C6—C5	110.33 (13)	C15—C20—H20	118.7 (10)
C7—C6—H6A	111.2 (10)	C19—C20—H20	119.5 (10)
C5—C6—H6A	110.5 (10)	C5—C21—H22A	108.5 (13)
C7—C6—H6B	109.2 (10)	C5—C21—H22C	108.7 (16)
C5—C6—H6B	110.5 (10)	H22A—C21—H22C	106 (2)
H6A—C6—H6B	105.0 (14)	C5—C21—H22B	112.7 (15)
N1—C7—C8	108.11 (12)	H22A—C21—H22B	113 (2)
N1—C7—C6	126.19 (13)	H22C—C21—H22B	108 (2)
C8—C7—C6	125.70 (14)	C5—C22—H21A	114.4 (13)
C7—C8—C2	107.48 (13)	C5—C22—H21B	109.5 (15)
C7—C8—C3	121.03 (13)	H21A—C22—H21B	107.3 (19)
C2—C8—C3	131.49 (13)	C5—C22—H21C	111.0 (15)
C14—C9—C10	120.20 (14)	H21A—C22—H21C	102 (2)
C14—C9—N1	119.51 (14)	H21B—C22—H21C	112 (2)
C10—C9—N1	120.28 (13)	O2—C23—H23B	110.7 (16)
C9—C10—C11	120.37 (16)	O2—C23—H23A	110.7 (16)
C9—C10—H10	118.5 (10)	H23B—C23—H23A	105 (2)
C11—C10—H10	121.2 (10)	O2—C23—H23C	105.8 (14)
C12—C11—C10	117.98 (17)	H23B—C23—H23C	115 (2)
C12—C11—H11	119.7 (12)	H23A—C23—H23C	110 (2)
C10—C11—H11	122.4 (12)
C7—N1—C1—C2	0.61 (16)	C7—N1—C9—C14	−66.4 (2)
C9—N1—C1—C2	178.88 (14)	C1—N1—C9—C14	115.63 (17)
C7—N1—C1—C15	−177.52 (13)	C7—N1—C9—C10	112.95 (17)
C9—N1—C1—C15	0.7 (2)	C1—N1—C9—C10	−65.1 (2)
N1—C1—C2—C8	−0.56 (17)	C14—C9—C10—C11	−0.4 (3)
C15—C1—C2—C8	177.46 (14)	N1—C9—C10—C11	−179.74 (15)
O1—C3—C4—C5	151.96 (15)	C9—C10—C11—C12	0.2 (3)
C8—C3—C4—C5	−29.9 (2)	C10—C11—C12—F1	179.66 (17)
C3—C4—C5—C22	−68.4 (2)	C10—C11—C12—C13	0.4 (3)
C3—C4—C5—C21	171.05 (18)	F1—C12—C13—C14	−179.90 (16)
C3—C4—C5—C6	53.03 (19)	C11—C12—C13—C14	−0.6 (3)
C22—C5—C6—C7	74.1 (2)	C10—C9—C14—C13	0.2 (3)
C4—C5—C6—C7	−46.9 (2)	N1—C9—C14—C13	179.50 (15)
C21—C5—C6—C7	−164.91 (18)	C12—C13—C14—C9	0.3 (3)
C1—N1—C7—C8	−0.41 (16)	C2—C1—C15—C20	135.86 (18)
C9—N1—C7—C8	−178.73 (13)	N1—C1—C15—C20	−46.4 (2)
C1—N1—C7—C6	178.56 (15)	C2—C1—C15—C16	−41.5 (2)
C9—N1—C7—C6	0.2 (2)	N1—C1—C15—C16	136.24 (16)
C5—C6—C7—N1	−155.93 (15)	C20—C15—C16—C17	−0.1 (3)
C5—C6—C7—C8	22.9 (2)	C1—C15—C16—C17	177.44 (16)
N1—C7—C8—C2	0.06 (17)	C15—C16—C17—C18	0.4 (3)
C6—C7—C8—C2	−178.92 (15)	C23—O2—C18—C19	0.7 (3)
N1—C7—C8—C3	179.97 (13)	C23—O2—C18—C17	−178.3 (2)
C6—C7—C8—C3	1.0 (2)	C16—C17—C18—O2	178.84 (16)
C1—C2—C8—C7	0.32 (17)	C16—C17—C18—C19	−0.2 (3)
C1—C2—C8—C3	−179.58 (16)	O2—C18—C19—C20	−179.13 (16)
O1—C3—C8—C7	179.99 (15)	C17—C18—C19—C20	−0.1 (3)
C4—C3—C8—C7	1.9 (2)	C16—C15—C20—C19	−0.3 (3)
O1—C3—C8—C2	−0.1 (3)	C1—C15—C20—C19	−177.66 (15)
C4—C3—C8—C2	−178.19 (16)	C18—C19—C20—C15	0.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1^i	0.97 (2)	2.41 (2)	3.366 (2)	169 (1)
C14—H14···O1^ii	0.96 (2)	2.48 (2)	3.428 (2)	173 (1)
C4—H4B···Cg1^ii	1.00 (2)	2.69	3.606 (2)	166

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+1, −y, −z+1.

(III) 6,6-dimethyl-1,2-diphenyl-4,5,6,7-tetrahydro-1H-indol-4-one

Crystal data

C22H21NO	Z = 2
Mr = 315.40	F(000) = 336
Triclinic, P1	Dx = 1.169 Mg m^−3
Hall symbol: -P 1	Melting point: 482 K
a = 9.315 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.793 (5) Å	Cell parameters from 985 reflections
c = 11.048 (6) Å	θ = 2.4–24.2°
α = 81.362 (9)°	µ = 0.07 mm^−1
β = 65.691 (7)°	T = 293 K
γ = 77.999 (8)°	Block, colourless
V = 896.0 (8) Å^3	0.35 × 0.30 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3259 independent reflections
Radiation source: sealed tube	2604 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
ϕ and ω scans	θmax = 25.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.946, Tmax = 0.986	k = −11→11
7395 measured reflections	l = −12→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.104	All H-atom parameters refined
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0528P)^2 + 0.121P] where P = (Fo^2 + 2Fc^2)/3
3259 reflections	(Δ/σ)max < 0.001
301 parameters	Δρmax = 0.13 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
N1	0.28072 (13)	0.23798 (11)	0.69871 (10)	0.0393 (3)
O1	0.49380 (13)	0.19296 (13)	0.25063 (10)	0.0642 (3)
C1	0.15640 (15)	0.26748 (14)	0.65309 (13)	0.0394 (3)
C2	0.22397 (16)	0.25684 (15)	0.51884 (13)	0.0420 (3)
C3	0.51835 (16)	0.19015 (15)	0.35162 (13)	0.0431 (3)
C4	0.68424 (17)	0.14790 (18)	0.35118 (15)	0.0487 (4)
C5	0.71311 (16)	0.21092 (15)	0.45697 (14)	0.0457 (3)
C6	0.58507 (17)	0.17938 (17)	0.59576 (15)	0.0455 (3)
C7	0.42332 (15)	0.21093 (14)	0.59246 (13)	0.0384 (3)
C8	0.39170 (15)	0.22049 (14)	0.48016 (13)	0.0394 (3)
C9	0.26477 (16)	0.24451 (14)	0.83309 (12)	0.0403 (3)
C10	0.20043 (18)	0.36894 (16)	0.89371 (15)	0.0489 (4)
C11	0.1867 (2)	0.37528 (19)	1.02188 (16)	0.0562 (4)
C12	0.2375 (2)	0.2583 (2)	1.08890 (16)	0.0605 (5)
C13	0.3022 (2)	0.1343 (2)	1.02774 (16)	0.0649 (5)
C14	0.3162 (2)	0.12617 (17)	0.89933 (15)	0.0547 (4)
C15	−0.01448 (16)	0.29904 (15)	0.73970 (13)	0.0424 (3)
C16	−0.11164 (17)	0.40663 (17)	0.69814 (15)	0.0508 (4)
C17	−0.27475 (19)	0.4344 (2)	0.77108 (19)	0.0637 (5)
C18	−0.3431 (2)	0.3564 (2)	0.8878 (2)	0.0696 (5)
C19	−0.2492 (2)	0.2513 (2)	0.93185 (19)	0.0705 (5)
C20	−0.0853 (2)	0.22134 (18)	0.85879 (16)	0.0584 (4)
C21	0.8764 (2)	0.1419 (2)	0.4570 (2)	0.0680 (5)
C22	0.7097 (3)	0.36887 (19)	0.4255 (2)	0.0652 (5)
H2	0.1666 (17)	0.2680 (14)	0.4612 (14)	0.045 (4)*
H4A	0.761 (2)	0.1727 (17)	0.2616 (18)	0.066 (5)*
H4B	0.701 (2)	0.0449 (19)	0.3678 (16)	0.067 (5)*
H6A	0.6068 (17)	0.0805 (17)	0.6255 (14)	0.050 (4)*
H6B	0.5899 (18)	0.2307 (16)	0.6634 (16)	0.054 (4)*
H10	0.165 (2)	0.4500 (18)	0.8462 (16)	0.065 (5)*
H11	0.143 (2)	0.463 (2)	1.0643 (17)	0.072 (5)*
H12	0.230 (2)	0.2643 (18)	1.1758 (18)	0.072 (5)*
H13	0.337 (2)	0.050 (2)	1.0744 (19)	0.086 (6)*
H14	0.361 (2)	0.039 (2)	0.8553 (18)	0.071 (5)*
H16	−0.061 (2)	0.4652 (18)	0.6129 (17)	0.067 (5)*
H17	−0.342 (2)	0.513 (2)	0.7411 (19)	0.085 (6)*
H18	−0.457 (3)	0.377 (2)	0.938 (2)	0.093 (6)*
H19	−0.288 (2)	0.198 (2)	1.012 (2)	0.090 (6)*
H20	−0.018 (2)	0.1455 (18)	0.8871 (16)	0.060 (5)*
H21A	0.723 (2)	0.416 (2)	0.494 (2)	0.091 (7)*
H21B	0.609 (2)	0.417 (2)	0.4139 (17)	0.075 (5)*
H21C	0.800 (3)	0.386 (2)	0.337 (2)	0.095 (7)*
H22A	0.960 (3)	0.158 (2)	0.369 (2)	0.099 (7)*
H22B	0.880 (2)	0.034 (2)	0.478 (2)	0.092 (6)*
H22C	0.896 (2)	0.178 (2)	0.528 (2)	0.089 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0375 (6)	0.0475 (7)	0.0306 (6)	−0.0048 (5)	−0.0117 (5)	−0.0048 (5)
O1	0.0511 (6)	0.1027 (9)	0.0342 (6)	−0.0018 (6)	−0.0143 (5)	−0.0137 (5)
C1	0.0350 (7)	0.0462 (8)	0.0361 (7)	−0.0062 (6)	−0.0129 (6)	−0.0038 (6)
C2	0.0366 (7)	0.0553 (9)	0.0346 (7)	−0.0062 (6)	−0.0149 (6)	−0.0040 (6)
C3	0.0418 (8)	0.0486 (8)	0.0354 (8)	−0.0058 (6)	−0.0119 (6)	−0.0049 (6)
C4	0.0379 (8)	0.0564 (10)	0.0429 (9)	−0.0015 (7)	−0.0083 (7)	−0.0086 (7)
C5	0.0350 (7)	0.0514 (8)	0.0482 (8)	−0.0049 (6)	−0.0145 (6)	−0.0048 (6)
C6	0.0424 (8)	0.0537 (9)	0.0432 (8)	−0.0059 (6)	−0.0208 (7)	−0.0029 (7)
C7	0.0365 (7)	0.0424 (7)	0.0347 (7)	−0.0059 (5)	−0.0125 (6)	−0.0032 (5)
C8	0.0362 (7)	0.0471 (8)	0.0325 (7)	−0.0059 (6)	−0.0112 (6)	−0.0040 (5)
C9	0.0398 (7)	0.0484 (8)	0.0317 (7)	−0.0076 (6)	−0.0124 (6)	−0.0041 (6)
C10	0.0519 (9)	0.0498 (9)	0.0447 (8)	−0.0034 (7)	−0.0198 (7)	−0.0065 (7)
C11	0.0569 (10)	0.0655 (11)	0.0468 (9)	−0.0026 (8)	−0.0187 (8)	−0.0215 (8)
C12	0.0609 (10)	0.0862 (13)	0.0355 (8)	−0.0107 (9)	−0.0186 (8)	−0.0107 (8)
C13	0.0783 (12)	0.0709 (12)	0.0437 (9)	−0.0018 (9)	−0.0295 (9)	0.0032 (8)
C14	0.0690 (10)	0.0510 (9)	0.0409 (8)	−0.0006 (8)	−0.0222 (8)	−0.0052 (7)
C15	0.0378 (7)	0.0510 (8)	0.0368 (7)	−0.0095 (6)	−0.0099 (6)	−0.0100 (6)
C16	0.0421 (8)	0.0638 (10)	0.0440 (9)	−0.0036 (7)	−0.0145 (7)	−0.0104 (7)
C17	0.0430 (9)	0.0809 (12)	0.0659 (11)	0.0009 (8)	−0.0189 (8)	−0.0243 (9)
C18	0.0384 (9)	0.0863 (13)	0.0745 (13)	−0.0114 (9)	−0.0033 (9)	−0.0321 (10)
C19	0.0604 (11)	0.0804 (13)	0.0532 (11)	−0.0303 (10)	0.0051 (9)	−0.0086 (9)
C20	0.0526 (9)	0.0614 (10)	0.0500 (9)	−0.0139 (8)	−0.0083 (8)	0.0005 (8)
C21	0.0403 (9)	0.0882 (15)	0.0744 (13)	−0.0021 (9)	−0.0237 (9)	−0.0108 (11)
C22	0.0676 (12)	0.0571 (10)	0.0710 (13)	−0.0197 (9)	−0.0248 (10)	0.0015 (9)

Geometric parameters (Å, º)

N1—C7	1.3696 (17)	C11—C12	1.376 (2)
N1—C1	1.4057 (18)	C11—H11	0.974 (19)
N1—C9	1.4399 (18)	C12—C13	1.379 (3)
O1—C3	1.2231 (17)	C12—H12	0.945 (18)
C1—C2	1.363 (2)	C13—C14	1.383 (2)
C1—C15	1.4747 (19)	C13—H13	0.97 (2)
C2—C8	1.419 (2)	C14—H14	0.976 (19)
C2—H2	0.968 (15)	C15—C20	1.392 (2)
C3—C8	1.4486 (19)	C15—C16	1.393 (2)
C3—C4	1.512 (2)	C16—C17	1.385 (2)
C4—C5	1.537 (2)	C16—H16	1.011 (18)
C4—H4A	0.984 (17)	C17—C18	1.372 (3)
C4—H4B	0.989 (18)	C17—H17	1.00 (2)
C5—C22	1.530 (2)	C18—C19	1.374 (3)
C5—C21	1.530 (2)	C18—H18	0.97 (2)
C5—C6	1.541 (2)	C19—C20	1.392 (3)
C6—C7	1.488 (2)	C19—H19	0.93 (2)
C6—H6A	0.982 (16)	C20—H20	0.970 (17)
C6—H6B	0.982 (17)	C21—H22A	0.98 (2)
C7—C8	1.3745 (19)	C21—H22B	1.05 (2)
C9—C10	1.380 (2)	C21—H22C	1.00 (2)
C9—C14	1.383 (2)	C22—H21A	1.01 (2)
C10—C11	1.378 (2)	C22—H21B	1.01 (2)
C10—H10	0.963 (16)	C22—H21C	1.01 (2)
C7—N1—C1	108.99 (11)	C12—C11—C10	120.19 (16)
C7—N1—C9	124.53 (11)	C12—C11—H11	120.0 (10)
C1—N1—C9	126.34 (11)	C10—C11—H11	119.8 (10)
C2—C1—N1	107.35 (12)	C11—C12—C13	119.92 (16)
C2—C1—C15	128.18 (12)	C11—C12—H12	119.6 (11)
N1—C1—C15	124.44 (12)	C13—C12—H12	120.4 (11)
C1—C2—C8	107.92 (12)	C12—C13—C14	120.55 (16)
C1—C2—H2	125.7 (9)	C12—C13—H13	120.9 (12)
C8—C2—H2	126.4 (9)	C14—C13—H13	118.6 (12)
O1—C3—C8	122.93 (13)	C9—C14—C13	118.94 (16)
O1—C3—C4	121.66 (13)	C9—C14—H14	119.7 (10)
C8—C3—C4	115.36 (12)	C13—C14—H14	121.3 (10)
C3—C4—C5	115.46 (12)	C20—C15—C16	118.15 (14)
C3—C4—H4A	107.9 (10)	C20—C15—C1	122.82 (14)
C5—C4—H4A	110.2 (10)	C16—C15—C1	118.95 (13)
C3—C4—H4B	106.3 (10)	C17—C16—C15	121.34 (16)
C5—C4—H4B	108.0 (10)	C17—C16—H16	119.7 (10)
H4A—C4—H4B	108.7 (14)	C15—C16—H16	119.0 (10)
C22—C5—C21	109.51 (15)	C18—C17—C16	119.88 (18)
C22—C5—C4	110.08 (14)	C18—C17—H17	119.7 (11)
C21—C5—C4	108.92 (14)	C16—C17—H17	120.3 (12)
C22—C5—C6	110.67 (14)	C17—C18—C19	119.79 (17)
C21—C5—C6	108.03 (14)	C17—C18—H18	119.1 (12)
C4—C5—C6	109.59 (13)	C19—C18—H18	121.1 (12)
C7—C6—C5	110.56 (12)	C18—C19—C20	120.91 (18)
C7—C6—H6A	109.4 (9)	C18—C19—H19	123.8 (13)
C5—C6—H6A	110.0 (9)	C20—C19—H19	115.2 (13)
C7—C6—H6B	111.1 (9)	C15—C20—C19	119.92 (17)
C5—C6—H6B	111.4 (9)	C15—C20—H20	118.2 (10)
H6A—C6—H6B	104.2 (12)	C19—C20—H20	121.8 (10)
N1—C7—C8	107.92 (12)	C5—C21—H22A	110.1 (13)
N1—C7—C6	126.65 (12)	C5—C21—H22B	109.9 (11)
C8—C7—C6	125.42 (12)	H22A—C21—H22B	108.1 (17)
C7—C8—C2	107.81 (12)	C5—C21—H22C	110.6 (12)
C7—C8—C3	121.25 (13)	H22A—C21—H22C	110.7 (18)
C2—C8—C3	130.89 (13)	H22B—C21—H22C	107.4 (16)
C10—C9—C14	120.72 (14)	C5—C22—H21A	113.3 (12)
C10—C9—N1	119.78 (12)	C5—C22—H21B	112.2 (11)
C14—C9—N1	119.49 (13)	H21A—C22—H21B	108.6 (16)
C11—C10—C9	119.68 (15)	C5—C22—H21C	108.6 (12)
C11—C10—H10	120.9 (10)	H21A—C22—H21C	108.1 (17)
C9—C10—H10	119.5 (10)	H21B—C22—H21C	105.7 (15)
C7—N1—C1—C2	0.61 (15)	C4—C3—C8—C7	0.08 (19)
C9—N1—C1—C2	176.41 (12)	O1—C3—C8—C2	0.3 (2)
C7—N1—C1—C15	178.82 (12)	C4—C3—C8—C2	−177.02 (14)
C9—N1—C1—C15	−5.4 (2)	C7—N1—C9—C10	115.85 (15)
N1—C1—C2—C8	−0.02 (15)	C1—N1—C9—C10	−59.32 (18)
C15—C1—C2—C8	−178.14 (13)	C7—N1—C9—C14	−63.29 (18)
O1—C3—C4—C5	152.69 (14)	C1—N1—C9—C14	121.54 (16)
C8—C3—C4—C5	−29.93 (19)	C14—C9—C10—C11	−0.3 (2)
C3—C4—C5—C22	−68.18 (17)	N1—C9—C10—C11	−179.40 (13)
C3—C4—C5—C21	171.73 (14)	C9—C10—C11—C12	0.3 (2)
C3—C4—C5—C6	53.75 (17)	C10—C11—C12—C13	−0.1 (3)
C22—C5—C6—C7	74.74 (17)	C11—C12—C13—C14	−0.2 (3)
C21—C5—C6—C7	−165.38 (14)	C10—C9—C14—C13	0.0 (2)
C4—C5—C6—C7	−46.84 (17)	N1—C9—C14—C13	179.14 (14)
C1—N1—C7—C8	−0.96 (15)	C12—C13—C14—C9	0.2 (3)
C9—N1—C7—C8	−176.85 (11)	C2—C1—C15—C20	132.34 (17)
C1—N1—C7—C6	177.94 (13)	N1—C1—C15—C20	−45.5 (2)
C9—N1—C7—C6	2.0 (2)	C2—C1—C15—C16	−44.4 (2)
C5—C6—C7—N1	−158.14 (13)	N1—C1—C15—C16	137.79 (15)
C5—C6—C7—C8	20.6 (2)	C20—C15—C16—C17	−1.4 (2)
N1—C7—C8—C2	0.94 (15)	C1—C15—C16—C17	175.52 (14)
C6—C7—C8—C2	−177.98 (13)	C15—C16—C17—C18	0.9 (3)
N1—C7—C8—C3	−176.76 (12)	C16—C17—C18—C19	0.2 (3)
C6—C7—C8—C3	4.3 (2)	C17—C18—C19—C20	−0.8 (3)
C1—C2—C8—C7	−0.56 (16)	C16—C15—C20—C19	0.7 (2)
C1—C2—C8—C3	176.83 (14)	C1—C15—C20—C19	−176.04 (15)
O1—C3—C8—C7	177.42 (14)	C18—C19—C20—C15	0.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O1^i	0.97 (2)	2.57 (2)	3.533 (3)	173 (1)
C19—H19···O1^ii	0.93 (2)	2.58 (2)	3.389 (3)	145 (2)
C4—H4B···Cg1^i	0.99 (2)	2.74	3.723 (3)	172
C11—H11···Cg2^iii	0.97 (2)	2.75	3.620 (3)	149

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