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ISSN: 2056-9890
Volume 72| Part 5| May 2016| Pages 699-703
doi:10.1107/S2056989016006162

Different N—H⋯π inter­actions in two indole derivatives

CROSSMARK_Color_square_no_text.svg
Jamie R. Kerr,a Laurent Trembleau,a John M. D. Storey,a James L. Wardella,b and William T. A. Harrisona*

aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, and bFundação Oswaldo Cruz, Instituto de Tecnologia em Fármacos-Far Manguinhos, 21041-250 Rio de Janeiro, RJ, Brazil
*Correspondence e-mail: w.harrison@abdn.ac.uk

Edited by S. Parkin, University of Kentucky, USA (Received 7 April 2016; accepted 12 April 2016; online 15 April 2016)

We describe the syntheses and crystal structures of two indole derivatives, namely 6-isopropyl-3-(2-nitro-1-phenyl­eth­yl)-1H-indole, C19H20N2O2, (I), and 2-(4-meth­oxy­phen­yl)-3-(2-nitro-1-phenyl­eth­yl)-1H-indole, C23H20N2O3, (II); the latter crystallizes with two mol­ecules (A and B) with similar conformations (r.m.s. overlay fit = 0.139 Å) in the asymmetric unit. Despite the presence of O atoms as potential acceptors for classical hydrogen bonds, the dominant inter­molecular inter­action in each crystal is an N—H⋯π bond, which generates chains in (I) and A+A and B+B inversion dimers in (II). A different aromatic ring acts as the acceptor in each case. The packing is consolidated by C—H⋯π inter­actions in each case but aromatic π–π stacking inter­actions are absent.

CCDC references: 1473664; 1473663

1. Chemical context

N—H⋯π inter­actions are now a well-recognised type of `non-classical' weak bond (Desiraju & Steiner, 1999[Desiraju, G. R. & Steiner, T. (1999). In The Weak Hydrogen Bond in Structural Chemistry and Biology. Oxford University Press.]). They are of special significance in biological systems (Burley & Petsko, 1986[Burley, S. K. & Petsko, G. A. (1986). FEBS Lett. 203, 139-143.]; Levitt & Perutz, 1998[Levitt, M. & Perutz, M. F. (1998). J. Mol. Biol. 201, 751-754.]) and are thought to play an important role in establishing protein secondary structures (Lavanya et al., 2014[Lavanya, P., Ramaiah, S. & Anbarasu, A. (2014). Comput. Biol. Med. 46, 22-28.]). They may even influence the charge-transport properties of organic semiconductors (Zhao et al., 2009[Zhao, H., Jiang, L., Dong, H., Li, H., Hu, W. & Ong, B. (2009). ChemPhysChem, 10, 2345-2348.]). The presence of N—H⋯π inter­actions in indole complexes with aromatic species has been investigated by IR spectroscopy (Muñoz et al., 2004[Muñoz, M. A., Ferrero, R., Carmona, C. & Balón, M. (2004). Spectrochim. Acta Part A, 60, 193-200.]), and such bonds have also been observed in many crystal structures of indole derivatives (e.g. Krishna et al., 1999[Krishna, R., Velmurugan, D., Babu, G. & Perumal, P. T. (1999). Acta Cryst. C55, 75-78.]; Cordes et al., 2011[Cordes, D. B., Hua, G., Slawin, A. M. Z. & Woollins, J. D. (2011). Acta Cryst. E67, o1606.]).

[Scheme 1]

As part of our ongoing synthetic, biological (Kerr, 2013[Kerr, J. R. (2013). PhD thesis, University of Aberdeen, Scotland.]) and structural studies (Kerr et al., 2015[Kerr, J. R., Trembleau, L., Storey, J. M. D., Wardell, J. L. & Harrison, W. T. A. (2015). Acta Cryst. E71, 654-659.], 2016[Kerr, J. R., Trembleau, L., Storey, J. M. D., Wardell, J. L. & Harrison, W. T. A. (2016). Acta Cryst. E72, 363-369.]) of variously substituted indole derivatives, we now report the syntheses and crystal structures of 6-isopropyl-3-(2-nitro-1-phenyl­eth­yl)-1H-indole, C19H20N2O2, (I)[link], and 2-(4-meth­oxy­phen­yl)-3-(2-nitro-1-phenyl­eth­yl)-1H-indole, C23H20N2O3, (II)[link], in which N—H⋯π bonds are the most important inter­molecular inter­actions, but result in quite different structures.

2. Structural commentary

Compound (I)[link] crystallizes in a Sohncke space group with one mol­ecule in the asymmetric unit (Fig. 1[link]). The absolute structure was indeterminate in the present study and C9 was assigned an arbitrary S configuration (given the synthesis, we presume that the bulk sample consists of a statistical mixture of enanti­omers). The dihedral angle between the mean plane of the N1/C1–C8 indole ring system (r.m.s. deviation = 0.018 Å) and the C11–C16 phenyl ring is 83.59 (11)°. Atom C17 of the 6-isopropyl substituent deviates slightly from the indole plane, by −0.092 (6) Å. In terms of the terminal carbon atoms of this group, C18 and C19 deviate from the indole plane by −1.461 (6) and 1.030 (6) Å, respectively. Atom C9 shows a relatively large deviation from the indole plane of −0.084 (6) Å, perhaps because of steric crowding. In terms of the orientation of the substituents attached to C9, the C6—C7—C9—C10 torsion angle of 174.6 (5)° (anti about C7—C9) indicates that the C10 atom of the CH2NO2 group lies roughly in the plane of the indole ring, whereas the C6—C7—C9—C11 angle of −61.6 (7)° (gauche about C7—C9) indicates that the pendant ring lies to one side of the indole plane. Finally, the C7—C9—C10—N2 torsion angle of −176.5 (4)° indicates a near anti conformation about the C9—C10 bond.

[Figure 1]
Figure 1
The mol­ecular structure of (I)[link], showing 50% probability displacement ellipsoids.

There are two mol­ecules, A (Fig. 2[link]) and B, in the asymmetric unit of (II)[link]. The space group for (II)[link] is centrosymmetric and the stereogenic centres (C9 in mol­ecule A and C32 in mol­ecule B) were arbitrarily assigned an S configuration for ease of comparison with compound (I)[link].

[Figure 2]
Figure 2
The mol­ecular structure of the N1 mol­ecule in (II)[link], showing 50% probability displacement ellipsoids. The mol­ecular structure of the N3 mol­ecule is very similar.

In mol­ecule A, the dihedral angles between the indole (N1/C1–C8) mean plane (r.m.s. deviation = 0.012 Å) and the C11–C16 and C17–C22 rings are 65.49 (4) and 66.26 (4)°, respectively. The deviations of C9 and C17 from the indole plane are 0.017 (2) and 0.0168 (19) Å, respectively; C23 deviates from the C17–C22 plane by 0.322 (3) Å. The equivalent data for mol­ecule B are 0.005 Å (N3/C24–C31 r.m.s. deviation), 64.92 (4)° (C34 ring), 58.31 (5)° (C40 ring), −0.071 (2) Å (C32), −0.014 (2) Å (C40), −0.214 (3) Å (C46). These data indicate that mol­ecules A and B have similar but not quite identical conformations: the unweighted r.m.s. overlay fit for the 28 non-hydrogen atoms is 0.139 Å (Fig. 3[link]).

[Figure 3]
Figure 3
Overlay plot of the conformations of the N1 mol­ecules (black) and N3 mol­ecules (red) in the crystal of (II)[link].

As just noted, mol­ecules A and B in (II)[link] have similar conformations, but the local geometry about the stereogenic atoms C9 and C32 are completely different from the corresponding local geometry about C9 in (I)[link]. This can be seen in the following data for the N1 mol­ecule in (II)[link]: the C6—C7—C9—C10 torsion angle is −42.9 (2)° (compressed gauche about C7—C9) and the C6—C7—C9—C11 angle is 83.76 (19)° (expanded gauche about C7—C9); the C7—C9—C10—N2 torsion angle of −58.42 (17)° (gauche about C9—C10) is also completely different from the corresponding angle in (I)[link]. The corresponding torsion angles for the N3 mol­ecule in (II)[link] are −38.4 (2), 87.50 (19) and −56.24 (19)°, respectively. In essence, the 2-nitro 1-phenyl ethyl substituent has rotated around the C7—C9 bond, so that the H atom attached to C9 and C32 in (II)[link] lies approximately above C8 whereas in (I)[link] the CH2NO2 group takes on this role.

3. Supra­molecular features

In the crystal of (I)[link], the mol­ecules are linked by N—H⋯π inter­actions (Table 1[link], Fig. 4[link]) to generate [010] chains, in which adjacent mol­ecules are related by the 21 screw axis. The acceptor ring is the C1–C6 benzene ring of the indole system; the dihedral angle between any adjacent pair of indole ring systems in the chain is 68.89 (8)°. The chain appears to be reinforced by a C—H⋯π bond from the C2—H2 group of the benzene ring syn to the N—H group to the five-membered ring of the same adjacent mol­ecule; the H⋯π separation is actually marginally shorter for this bond than for the N—H⋯π bond. Two further C—H⋯π inter­actions (Fig. 5[link]) also occur in the crystal of (I)[link]: based on their lengths, these are presumably significantly weaker than the C2—H2 bond. They arise from adjacent C—H groups on the pendant C11–C16 benzene ring with the acceptor rings being another C11–C16 ring and the C1–C6 indole ring of the same adjacent mol­ecule. Taken together, the inter­molecular inter­actions lead to (100) sheets in the crystal of (I)[link].

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

Cg1, Cg2 and Cg3 are the centroids of the N1/C1/C6–C8, C1–C6 and C11–C16 rings, respectively.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1⋯Cg2i 0.84 (6) 2.64 (6) 3.386 (5) 148 (6)
C2—H2⋯Cg1i 0.95 2.63 3.468 (6) 147
C14—H14⋯Cg2ii 0.95 2.79 3.638 (6) 148
C15—H15⋯Cg3ii 0.95 2.87 3.551 (7) 129
Symmetry codes: (i) [-x+1, y-{\script{1\over 2}}, -z+1]; (ii) [-x+1, y+{\script{1\over 2}}, -z].
[Figure 4]
Figure 4
Partial packing diagram for (I)[link], showing the formation of [010] chains linked by N—H⋯π and C—H⋯π inter­actions (double-dashed lines). [Symmetry codes: (i) 1 − x, y − [{1\over 2}], 1 − z; (ii) 1 − x, y + [{1\over 2}], 1 − z.] All H atoms, except H1 and H2, have been omitted for clarity. The orange circles indicate ring centroids.
[Figure 5]
Figure 5
Fragment of the packing for (I)[link], showing C—H⋯π bonds arising from adjacent C—H groups of the pendant benzene ring. All H atoms, except H14 and H15, have been omitted for clarity. [Symmetry code: (i) 1 − x, y + [{1\over 2}], −z.] The orange circles indicate ring centroids.

In the crystal of (II)[link], inversion dimers linked by pairs of N—H⋯π inter­actions (Table 2[link], Fig. 6[link]) occur for both independent mol­ecules. In this case, the acceptor ring is the pendant C11–C16 or C34–C39 benzene ring for mol­ecules A and B, respectively. This bonding mode possibly correlates with the different orientation of the substituents attached to C9 and C32, as described above. Again, the N—H⋯π bonds appear to be reinforced, but this time by two pairs of C—H⋯π inter­actions. As for (I)[link], they arise from adjacent C—H groups in a benzene ring but this time they are part of the pendant 4-meth­oxy­benzene ring at the indole 2-position. Further C—H⋯π bonds link the A+A and B+B dimers into a three-dimensional network in the crystal of (II)[link].

Table 2
Hydrogen-bond geometry (Å, °) for (II)[link]

Cg1, Cg2, Cg3, Cg6, Cg7 and Cg8 are the centroids of the N1/C1/C6–C8, C1–C6, C11–C16, N3/C24/C29–C34--C31, C24–C29 and C34–C39 rings, respectively.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1⋯Cg3i 0.886 (19) 2.640 (19) 3.3631 (15) 139.6 (15)
N3—H3⋯Cg8ii 0.875 (18) 2.582 (19) 3.3364 (15) 144.9 (16)
C14—H14⋯Cg2iii 0.95 2.58 3.4228 (18) 149
C21—H21⋯Cg2i 0.95 2.69 3.4133 (17) 134
C22—H22⋯Cg1i 0.95 2.68 3.4543 (17) 138
C23—H23B⋯Cg3iv 0.98 2.79 3.6739 (18) 150
C37—H37⋯Cg6v 0.95 2.86 3.7660 (18) 160
C41—H41⋯Cg6ii 0.95 2.70 3.3793 (17) 129
C42—H42⋯Cg7ii 0.95 2.67 3.3627 (17) 130
Symmetry codes: (i) -x+1, -y, -z; (ii) -x+2, -y+1, -z+1; (iii) x, y-1, z; (iv) -x+2, -y, -z; (v) x, y+1, z.
[Figure 6]
Figure 6
An inversion dimer of N1 mol­ecules in the crystal of (II)[link] linked by pairs of N—H⋯π and C—H⋯π inter­actions (double-dashed lines). [Symmetry code: (i) 1 − x, −y, −z.] The N3 mol­ecules associate into similar dimers. The orange circles indicate ring centroids.

4. Database survey

There are over 7000 crystal structures of indole derivatives in the Cambridge Structural Database (CSD; Groom et al., 2016[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]), but none of them have an iso-propyl group at the 6-position. Six structures contain a p-meth­oxy­benzene grouping at the 2-position and four contain a 2-nitro-1-phenyl­ethyl grouping at the 3-position; these latter structures are the ones recently described by us (Kerr et al., 2015[Kerr, J. R., Trembleau, L., Storey, J. M. D., Wardell, J. L. & Harrison, W. T. A. (2015). Acta Cryst. E71, 654-659.]).

5. Synthesis and crystallization

To prepare (I)[link], 6-iso­propyl­indole (452 mg, 2.84 mmol), trans-β-nitro­styrene (28, 429 mg, 2.88 mmol) and sulfamic acid (57 mg, 0.59 mmol) were stirred in EtOH (10 ml) at 323 K for 48 h. Evaporation of the solvent and flash chromatography (1:6 EtOAc, hexa­nes) gave 6-isopropyl-3-(2-nitro-1-phenyl­eth­yl)-1H-indole as an orange solid (550 mg, 63%). Red blades of (I)[link] were recrystallized from methanol solution. δC (101 MHz; CDCl3) 144.0 (Cq), 139.3 (Cq), 136.9 (Cq), 127.9 (Cq), 127.8 (CH), 127.5 (CH), 124.3 (CH), 121.1 (CH), 119.4 (CH), 118.6 (CH), 114.3 (Cq), 108.5 (CH), 79.5 (CH2), 41.6 (CH), 34.3 (CH) and 24.4 (CH3); δH (400 MHz; CDCl3) 7.89 (1 H, br s), 7.30–7.21 (5 H, m), 7.18–7.15 (1 H, m), 7.12 (1 H, t, J 0.6), 6.90 (2 H, td, J, 1.5, 8.8), 5.08 (1 H, t, J 8.0), 4.97 (1 H, dd, J 7.4, 12.2), 4.85 (1 H, dd, J 8.4, 12.4), 2.91 (1 H, sp, J 6.9) and 1.20 (6 H, d, J 6.8); Rf 0.16 (1:6 ethyl acetate, hexa­nes); m.p. 374–376 K; IR (KBr, cm−1) 3433, 3007, 2924,1550, 1429, 1377, 1089 and 750; HRMS (ESI) for C19H21N2O2 [M + H]+ calculated 309.1604, found 309.1619.

To prepare (II)[link], 2-bromo-3-(2-nitro-1-phenyl­eth­yl)-1H-indole (Kerr et al., 2015[Kerr, J. R., Trembleau, L., Storey, J. M. D., Wardell, J. L. & Harrison, W. T. A. (2015). Acta Cryst. E71, 654-659.]) (90 mg, 0.26 mmol), 4-meth­oxy­phenyl­boronic acid (53 mg, 0.35 mmol), Na2CO3 (29 mg, 0.27 mmol), LiCl (22 mg, 0.52 mmol) and tetra­kis­(tri­phenyl­phosphine)palladium(0) (12 mg, 0.01 mmol) were placed in a microwave reactor vessel under argon. Degassed water (4 ml), toluene (6 ml) and ethanol (6 ml) were added and the reaction was heated to 373 K (high absorbance mode, 30 W, 8 bar) for 2 h. The mixture was acidified to pH 2 with 10% HCl(aq) then extracted into EtOAc (10 ml × 3). The combined organic phases were washed with water (10 ml) and saturated NaCl(aq) (10 ml) then dried (magnesium sulfate), filtered and evaporated under reduced pressure. Flash chromatography of the isolated solid (1:5 ethyl acetate, hexa­nes) afforded 2-(4-meth­oxy­phen­yl)-3-(2-nitro-1-phenyl­eth­yl)-1H-indole as a colourless solid (48 mg, 50%). Colourless chunks of (II)[link] were recrystallized from methanol solution. δC (63 MHz; CDCl3) 159.9 (Cq), 140.0 (Cq), 136.9 (Cq), 135.9 (CH), 130.1 (CH), 128.9 (Cq), 127.1 (CH), 125.0 (CH), 124.5 (Cq), 122.2 (Cq), 120.2 (CH), 119.8 (CH), 114.4 (CH), 111.3 (CH), 110.0 (CH), 109.1 (Cq), 79.1 (CH2), 55.4 (CH3) and 40.9 (CH); δH (250 MHz; CDCl3) 8.08 (1 H, br s), 7.45–7.25 (9 H, m), 7.19–6.90 (4 H, m), 5.19 (1 H, t, J 6.9) 5.10–5.01 (2 H, m) and 3.76 (3 H, s); Rf 0.09 (1:5 EtOAc, hexa­nes); m.p. 472 K (EtOH); IR (Nujol, cm−1) 3401, 3013, 2854, 1616, 1548, 1324, 1250, 1203, 1099, 870 and 746; HRMS (ESI) for C23H21N2O3 [M + H]+ calculated 373.1553, found 373.1546.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. The N-bound H atoms were located in difference maps and their positions were freely refined. The C-bound H atoms were geometrically placed (C—H = 0.93–0.98 Å) and refined as riding atoms. The constraint Uiso(H) = 1.2Ueq(C, N carrier) or 1.5Ueq(methyl carrier) was applied in all cases. The –CH3 groups were allowed to rotate, but not to tip, to best fit the electron density. Due to the similarity in the a and c unit-cell parameters for (I)[link], twinning models were applied, but no improvement in fit resulted.

Table 3
Experimental details

  (I) (II)
Crystal data
Chemical formula C19H20N2O2 C23H20N2O3
Mr 308.37 372.41
Crystal system, space group Monoclinic, P21 Triclinic, P[\overline{1}]
Temperature (K) 100 100
a, b, c (Å) 12.4525 (9), 5.7360 (4), 12.5896 (9) 9.2014 (5), 9.4543 (7), 21.6201 (14)
α, β, γ (°) 90, 116.081 (6), 90 98.563 (4), 93.416 (4), 98.354 (4)
V (Å3) 807.68 (11) 1833.7 (2)
Z 2 4
Radiation type Mo Kα Mo Kα
μ (mm−1) 0.08 0.09
Crystal size (mm) 0.28 × 0.05 × 0.01 0.10 × 0.06 × 0.06
 
Data collection
Diffractometer Rigaku Mercury CCD Rigaku Mercury CCD
No. of measured, independent and observed [I > 2σ(I)] reflections 7830, 3498, 2259 24774, 8621, 6769
Rint 0.107 0.038
(sin θ/λ)max (Å−1) 0.649 0.668
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.081, 0.164, 1.12 0.046, 0.124, 1.03
No. of reflections 3498 8621
No. of parameters 213 513
No. of restraints 1 0
H-atom treatment H atoms treated by a mixture of independent and constrained refinement H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.28, −0.24 0.62, −0.31
Computer programs: CrystalClear (Rigaku, 2012[Rigaku (2012). CrystalClear. Rigaku Corporation, Tokyo, Japan.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information

CCDC references: 1473664; 1473663

Crystal structure: contains datablocks I, II, global. DOI: 10.1107/S2056989016006162/pk2578sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989016006162/pk2578Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S2056989016006162/pk2578IIsup3.hkl

Supporting information file. DOI: 10.1107/S2056989016006162/pk2578Isup4.cml

Supporting information file. DOI: 10.1107/S2056989016006162/pk2578IIsup5.cml

checkCIF report


Chemical context top

N—H···π inter­actions are now a well-recognised type of 'non-classical' weak bond (Desiraju & Steiner, 1999). They are of special significance in biological systems (Burley & Petsko, 1986; Levitt & Perutz, 1998) and are thought to play an important role in establishing protein secondary structures (Lavanya et al., 2014). They may even influence the charge-transport properties of organic semiconductors (Zhao et al., 2009). The presence of N—H···π inter­actions in indole complexes with aromatic species has been investigated by IR spectroscopy (Muñoz et al., 2004), and such bonds have also been observed in many crystal structures of indole derivatives (e.g. Krishna et al., 1999; Cordes et al., 2011).

As part of our ongoing synthetic, biological (Kerr, 2013) and structural studies (Kerr et al., 2015, 2016) of variously substituted indole derivatives, we now report the syntheses and crystal structures of 6-iso­propyl-3-(2-nitro-1-phenyl­ethyl)-1H-indole, C19H20N2O2, (I), and 2-(4-meth­oxy­phenyl)-3-(2-nitro-1-phenyl­ethyl)-1H-indole, C23H20N2O3, (II), in which N—H···π bonds are the most important inter­molecular inter­actions, but result in quite different structures.

Structural commentary top

Compound (I) crystallizes in a Sohncke space group with one molecule in the asymmetric unit (Fig. 1). The absolute structure was indeterminate in the present study and C9 was assigned an arbitrary S configuration (given the synthesis, we presume that the bulk sample consists of a statistical mixture of enanti­omers). The dihedral angle between the mean plane of the N1/C1–C8 indole ring system (r.m.s. deviation = 0.018 Å) and the C11–C16 benzene ring is 83.59 (11)°. Atom C17 of the 6-iso­propyl substituent deviates slightly from the indole plane, by –0.092 (6) Å. In terms of the terminal carbon atoms of this group, C18 and C19 deviate from the indole plane by –1.461 (6) and 1.030 (6) Å, respectively. Atom C9 shows a relatively large deviation from the indole plane of –0.084 (6) Å, perhaps because of steric crowding. In terms of the orientation of the substituents attached to C9, the C6—C7—C9—C10 torsion angle of 174.6 (5)° (anti about C7—C9) indicates that the C10 atom of the CH2NO2 group lies roughly in the plane of the indole ring, whereas the C6—C7—C9—C11 angle of –61.6 (7)° (gauche about C7—C9) indicates that the pendant ring lies to one side of the indole plane. Finally, the C7—C9—C10—N2 torsion angle of –176.5 (4)° indicates a near anti conformation about the C9—C10 bond.

There are two molecules, A (Fig. 2) and B, in the asymmetric unit of (II). The space group for (II) is centrosymmetric and the stereogenic centres (C9 in molecule A and C32 in molecule B) were arbitrarily assigned an S configuration for ease of comparison with compound (I).

In molecule A, the dihedral angles between the indole (N1/C1–C8) mean plane (r.m.s. deviation = 0.012 Å) and the C11–C16 and C17–C22 rings are 65.49 (4) and 66.26 (4)°, respectively. The deviations of C9 and C17 from the indole plane are 0.017 (2) and 0.0168 (19) Å, respectively; C23 deviates from the C17–C22 plane by 0.322 (3) Å. The equivalent data for molecule B are 0.005 Å (N3/C24–C31 r.m.s. deviation), 64.92 (4)° (C34 ring), 58.31 (5)° (C40 ring), –0.071 (2) Å (C32), –0.014 (2) Å (C40), –0.214 (3) Å (C46). These data indicate that molecules A and B have similar but not quite identical conformations: the unweighted r.m.s. overlay fit for the 28 non-hydrogen atoms is 0.139 Å (Fig. 3).

As just noted, molecules A and B in (II) have similar conformations, but the local geometry about the stereogenic atoms C9 and C32 are completely different from the corresponding local geometry about C9 in (I). This can be seen in the following data for the N1 molecule in (II): the C6—C7—C9—C10 torsion angle is –42.9 (2)° (compressed gauche about C7—C9) and the C6—C7—C9—C11 angle is 83.76 (19)° (expanded gauche about C7—C9); the C7—C9—C10—N2 torsion angle of –58.42 (17)° (gauche about C9—C10) is also completely different from the corresponding angle in (I). The corresponding torsion angles for the N3 molecule in (II) are -38.4 (2), 87.50 (19) and –56.24 (19)°, respectively. In essence, the 2-nitro 1-phenyl ethyl substituent has rotated around the C7—C9 bond, so that the H atom attached to C9 and C32 in (II) lies approximately above C8 whereas in (I) the CH2NO2 group takes on this role.

Supra­molecular features top

In the crystal of (I), the molecules are linked by N—H···π inter­actions (Table 2, Fig. 4) to generate [010] chains, in which adjacent molecules are related by the 21 screw axis. The acceptor ring is the C1–C6 benzene ring of the indole system; the dihedral angle between any adjacent pair of indole ring systems in the chain is 68.89 (8)°. The chain appears to be reinforced by a C—H···π bond from the C2—H2 group of the benzene ring syn to the N—H group to the five-membered ring of the same adjacent molecule; the H···π separation is actually marginally shorter for this bond than for the N—H···π bond. Two further C—H···π inter­actions (Fig. 5) also occur in the crystal of (I): based on their lengths, these are presumably significantly weaker than the C2—H2 bond. They arise from adjacent C—H groups on the pendant C11–C16 benzene ring with the acceptor rings being another C11–C16 ring and the C1–C6 indole ring of the same adjacent molecule. Taken together, the inter­molecular inter­actions lead to (100) sheets in the crystal of (I).

In the crystal of (II), inversion dimers linked by pairs of N—H···π inter­actions (Table 3, Fig. 6) occur for both independent molecules. In this case, the acceptor ring is the pendant C11–C16 or C34–C39 benzene ring for molecules A and B, respectively. This bonding mode possibly correlates with the different orientation of the substituents attached to C9 and C32, as described above. Again, the N—H···π bonds appear to be reinforced, but this time by two pairs of C—H···π inter­actions. As for (I), they arise from adjacent C—H groups in a benzene ring but this time they are part of the pendant 4-meth­oxy­benzene ring at the indole 2-position. Further C—H···π bonds link the A+A and B+B dimers into a three-dimensional network in the crystal of (II).

Database survey top

There are over 7000 crystal structures of indole derivatives in the Cambridge Structural Database (CSD; Groom et al., 2016), but none of them have an iso-propyl group at the 6-position. Six structures contain a p-meth­oxy­benzene grouping at the 2-position and four contain a 2-nitro-1-phenyl­ethyl grouping at the 3-position; these latter structures are the ones recently described by us (Kerr et al., 2015).

Synthesis and crystallization top

To prepare (I), 6-iso­propyl­indole (452 mg, 2.84 mmol), trans-β-nitro­styrene (28, 429 mg, 2.88 mmol) and sulfamic acid (57 mg,0.59 mmol) were stirred in EtOH (10 ml) at 323 K for 48 h. Evaporation of the solvent and flash chromatography (1:6 EtOAc, hexanes) gave 6-iso­propyl-3-(2-nitro-1-phenyl­ethyl)-1H-indole as an orange solid (550 mg, 63%). Red blades of (I) were recrystallized from methanol solution. δC (101 MHz; CDCl3) 144.0 (Cq), 139.3 (Cq), 136.9 (Cq), 127.9 (Cq), 127.8 (CH), 127.5 (CH), 124.3 (CH), 121.1 (CH), 119.4 (CH), 118.6 (CH), 114.3 (Cq), 108.5 (CH), 79.5 (CH2), 41.6 (CH), 34.3 (CH) and 24.4 (CH3); δH (400 MHz; CDCl3) 7.89 (1 H, br s), 7.30–7.21 (5 H, m), 7.18–7.15 (1 H, m), 7.12 (1 H, t, J 0.6), 6.90 (2 H, td, J, 1.5, 8.8), 5.08 (1 H, t, J 8.0), 4.97 (1 H, dd, J 7.4, 12.2), 4.85 (1 H, dd, J 8.4, 12.4), 2.91 (1 H, sp, J 6.9) and 1.20 (6 H, d, J 6.8); Rf 0.16 (1:6 ethyl acetate, hexanes); m.p. 374–376 K; IR (KBr, cm-1) 3433, 3007, 2924,1550, 1429, 1377, 1089 and 750; HRMS (ESI) for C19H21N2O2 [M + H]+ calculated 309.1604, found 309.1619.

To prepare (II), 2-bromo-3-(2-nitro-1-phenyl­ethyl)-1H-indole (Kerr et al., 2015) (90 mg, 0.26 mmol), 4-meth­oxy­phenyl­boronic acid (78, 53 mg, 0.35 mmol), Na2CO3 (29 mg, 0.27 mmol), LiCl (22 mg, 0.52 mmol) and tetra­kis(tri­phenyl­phosphine)palladium(0) (12 mg, 0.01 mmol) were placed in a microwave reactor vessel under argon. Degassed water (4 ml), toluene (6 ml) and ethanol (6 ml) were added and the reaction was heated to 373 K (high absorbance mode, 30 W, 8 bar) for 2 h. The mixture was acidified to pH 2 with 10% HCl(aq) then extracted into EtOAc (10 ml × 3). The combined organic phases were washed with water (10 ml) and saturated NaCl(aq) (10 ml) then dried (magnesium sulfate), filtered and evaporated under reduced pressure. Flash chromatography of the isolated solid (1:5 ethyl acetate, hexanes) afforded 2-(4-meth­oxy­phenyl)-3-(2-nitro-1-phenyl­ethyl)-1H-indole as a colourless solid (48 mg, 50%). Colourless chunks of (II) were recrystallized from methanol solution. δC (63 MHz; CDCl3) 159.9 (Cq), 140.0 (Cq), 136.9 (Cq), 135.9 (CH), 130.1 (CH), 128.9 (Cq), 127.1 (CH), 125.0 (CH), 124.5 (Cq), 122.2 (Cq), 120.2 (CH), 119.8 (CH), 114.4 (CH), 111.3 (CH), 110.0 (CH), 109.1 (Cq), 79.1 (CH2), 55.4 (CH3) and 40.9 (CH); δH (250 MHz; CDCl3) 8.08 (1 H, br s), 7.45–7.25 (9 H, m), 7.19–6.90 (4 H, m), 5.19 (1 H, t, J 6.9) 5.10–5.01 (2 H, m) and 3.76 (3 H, s); Rf 0.09 (1:5 EtOAc, hexanes); m.p. 472 K (EtOH); IR (Nujol, cm-1) 3401, 3013, 2854, 1616, 1548, 1324, 1250, 1203, 1099, 870 and 746; HRMS (ESI) for C23H21N2O3 [M + H]+ calculated 373.1553, found 373.1546.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 3. The N-bound H atoms were located in difference maps and their positions were freely refined. The C-bound H atoms were geometrically placed (C—H = 0.93–0.98 Å) and refined as riding atoms. The constraint Uiso(H) = 1.2Ueq(C, N carrier) or 1.5Ueq(methyl carrier) was applied in all cases. The –CH3 groups were allowed to rotate, but not to tip, to best fit the electron density. Due to the similarity in the a and c unit-cell parameters for (I), twinning models were applied, but no improvement in fit resulted.

Structure description top

N—H···π inter­actions are now a well-recognised type of 'non-classical' weak bond (Desiraju & Steiner, 1999). They are of special significance in biological systems (Burley & Petsko, 1986; Levitt & Perutz, 1998) and are thought to play an important role in establishing protein secondary structures (Lavanya et al., 2014). They may even influence the charge-transport properties of organic semiconductors (Zhao et al., 2009). The presence of N—H···π inter­actions in indole complexes with aromatic species has been investigated by IR spectroscopy (Muñoz et al., 2004), and such bonds have also been observed in many crystal structures of indole derivatives (e.g. Krishna et al., 1999; Cordes et al., 2011).

As part of our ongoing synthetic, biological (Kerr, 2013) and structural studies (Kerr et al., 2015, 2016) of variously substituted indole derivatives, we now report the syntheses and crystal structures of 6-iso­propyl-3-(2-nitro-1-phenyl­ethyl)-1H-indole, C19H20N2O2, (I), and 2-(4-meth­oxy­phenyl)-3-(2-nitro-1-phenyl­ethyl)-1H-indole, C23H20N2O3, (II), in which N—H···π bonds are the most important inter­molecular inter­actions, but result in quite different structures.

Compound (I) crystallizes in a Sohncke space group with one molecule in the asymmetric unit (Fig. 1). The absolute structure was indeterminate in the present study and C9 was assigned an arbitrary S configuration (given the synthesis, we presume that the bulk sample consists of a statistical mixture of enanti­omers). The dihedral angle between the mean plane of the N1/C1–C8 indole ring system (r.m.s. deviation = 0.018 Å) and the C11–C16 benzene ring is 83.59 (11)°. Atom C17 of the 6-iso­propyl substituent deviates slightly from the indole plane, by –0.092 (6) Å. In terms of the terminal carbon atoms of this group, C18 and C19 deviate from the indole plane by –1.461 (6) and 1.030 (6) Å, respectively. Atom C9 shows a relatively large deviation from the indole plane of –0.084 (6) Å, perhaps because of steric crowding. In terms of the orientation of the substituents attached to C9, the C6—C7—C9—C10 torsion angle of 174.6 (5)° (anti about C7—C9) indicates that the C10 atom of the CH2NO2 group lies roughly in the plane of the indole ring, whereas the C6—C7—C9—C11 angle of –61.6 (7)° (gauche about C7—C9) indicates that the pendant ring lies to one side of the indole plane. Finally, the C7—C9—C10—N2 torsion angle of –176.5 (4)° indicates a near anti conformation about the C9—C10 bond.

There are two molecules, A (Fig. 2) and B, in the asymmetric unit of (II). The space group for (II) is centrosymmetric and the stereogenic centres (C9 in molecule A and C32 in molecule B) were arbitrarily assigned an S configuration for ease of comparison with compound (I).

In molecule A, the dihedral angles between the indole (N1/C1–C8) mean plane (r.m.s. deviation = 0.012 Å) and the C11–C16 and C17–C22 rings are 65.49 (4) and 66.26 (4)°, respectively. The deviations of C9 and C17 from the indole plane are 0.017 (2) and 0.0168 (19) Å, respectively; C23 deviates from the C17–C22 plane by 0.322 (3) Å. The equivalent data for molecule B are 0.005 Å (N3/C24–C31 r.m.s. deviation), 64.92 (4)° (C34 ring), 58.31 (5)° (C40 ring), –0.071 (2) Å (C32), –0.014 (2) Å (C40), –0.214 (3) Å (C46). These data indicate that molecules A and B have similar but not quite identical conformations: the unweighted r.m.s. overlay fit for the 28 non-hydrogen atoms is 0.139 Å (Fig. 3).

As just noted, molecules A and B in (II) have similar conformations, but the local geometry about the stereogenic atoms C9 and C32 are completely different from the corresponding local geometry about C9 in (I). This can be seen in the following data for the N1 molecule in (II): the C6—C7—C9—C10 torsion angle is –42.9 (2)° (compressed gauche about C7—C9) and the C6—C7—C9—C11 angle is 83.76 (19)° (expanded gauche about C7—C9); the C7—C9—C10—N2 torsion angle of –58.42 (17)° (gauche about C9—C10) is also completely different from the corresponding angle in (I). The corresponding torsion angles for the N3 molecule in (II) are -38.4 (2), 87.50 (19) and –56.24 (19)°, respectively. In essence, the 2-nitro 1-phenyl ethyl substituent has rotated around the C7—C9 bond, so that the H atom attached to C9 and C32 in (II) lies approximately above C8 whereas in (I) the CH2NO2 group takes on this role.

In the crystal of (I), the molecules are linked by N—H···π inter­actions (Table 2, Fig. 4) to generate [010] chains, in which adjacent molecules are related by the 21 screw axis. The acceptor ring is the C1–C6 benzene ring of the indole system; the dihedral angle between any adjacent pair of indole ring systems in the chain is 68.89 (8)°. The chain appears to be reinforced by a C—H···π bond from the C2—H2 group of the benzene ring syn to the N—H group to the five-membered ring of the same adjacent molecule; the H···π separation is actually marginally shorter for this bond than for the N—H···π bond. Two further C—H···π inter­actions (Fig. 5) also occur in the crystal of (I): based on their lengths, these are presumably significantly weaker than the C2—H2 bond. They arise from adjacent C—H groups on the pendant C11–C16 benzene ring with the acceptor rings being another C11–C16 ring and the C1–C6 indole ring of the same adjacent molecule. Taken together, the inter­molecular inter­actions lead to (100) sheets in the crystal of (I).

In the crystal of (II), inversion dimers linked by pairs of N—H···π inter­actions (Table 3, Fig. 6) occur for both independent molecules. In this case, the acceptor ring is the pendant C11–C16 or C34–C39 benzene ring for molecules A and B, respectively. This bonding mode possibly correlates with the different orientation of the substituents attached to C9 and C32, as described above. Again, the N—H···π bonds appear to be reinforced, but this time by two pairs of C—H···π inter­actions. As for (I), they arise from adjacent C—H groups in a benzene ring but this time they are part of the pendant 4-meth­oxy­benzene ring at the indole 2-position. Further C—H···π bonds link the A+A and B+B dimers into a three-dimensional network in the crystal of (II).

There are over 7000 crystal structures of indole derivatives in the Cambridge Structural Database (CSD; Groom et al., 2016), but none of them have an iso-propyl group at the 6-position. Six structures contain a p-meth­oxy­benzene grouping at the 2-position and four contain a 2-nitro-1-phenyl­ethyl grouping at the 3-position; these latter structures are the ones recently described by us (Kerr et al., 2015).

Synthesis and crystallization top

To prepare (I), 6-iso­propyl­indole (452 mg, 2.84 mmol), trans-β-nitro­styrene (28, 429 mg, 2.88 mmol) and sulfamic acid (57 mg,0.59 mmol) were stirred in EtOH (10 ml) at 323 K for 48 h. Evaporation of the solvent and flash chromatography (1:6 EtOAc, hexanes) gave 6-iso­propyl-3-(2-nitro-1-phenyl­ethyl)-1H-indole as an orange solid (550 mg, 63%). Red blades of (I) were recrystallized from methanol solution. δC (101 MHz; CDCl3) 144.0 (Cq), 139.3 (Cq), 136.9 (Cq), 127.9 (Cq), 127.8 (CH), 127.5 (CH), 124.3 (CH), 121.1 (CH), 119.4 (CH), 118.6 (CH), 114.3 (Cq), 108.5 (CH), 79.5 (CH2), 41.6 (CH), 34.3 (CH) and 24.4 (CH3); δH (400 MHz; CDCl3) 7.89 (1 H, br s), 7.30–7.21 (5 H, m), 7.18–7.15 (1 H, m), 7.12 (1 H, t, J 0.6), 6.90 (2 H, td, J, 1.5, 8.8), 5.08 (1 H, t, J 8.0), 4.97 (1 H, dd, J 7.4, 12.2), 4.85 (1 H, dd, J 8.4, 12.4), 2.91 (1 H, sp, J 6.9) and 1.20 (6 H, d, J 6.8); Rf 0.16 (1:6 ethyl acetate, hexanes); m.p. 374–376 K; IR (KBr, cm-1) 3433, 3007, 2924,1550, 1429, 1377, 1089 and 750; HRMS (ESI) for C19H21N2O2 [M + H]+ calculated 309.1604, found 309.1619.

To prepare (II), 2-bromo-3-(2-nitro-1-phenyl­ethyl)-1H-indole (Kerr et al., 2015) (90 mg, 0.26 mmol), 4-meth­oxy­phenyl­boronic acid (78, 53 mg, 0.35 mmol), Na2CO3 (29 mg, 0.27 mmol), LiCl (22 mg, 0.52 mmol) and tetra­kis(tri­phenyl­phosphine)palladium(0) (12 mg, 0.01 mmol) were placed in a microwave reactor vessel under argon. Degassed water (4 ml), toluene (6 ml) and ethanol (6 ml) were added and the reaction was heated to 373 K (high absorbance mode, 30 W, 8 bar) for 2 h. The mixture was acidified to pH 2 with 10% HCl(aq) then extracted into EtOAc (10 ml × 3). The combined organic phases were washed with water (10 ml) and saturated NaCl(aq) (10 ml) then dried (magnesium sulfate), filtered and evaporated under reduced pressure. Flash chromatography of the isolated solid (1:5 ethyl acetate, hexanes) afforded 2-(4-meth­oxy­phenyl)-3-(2-nitro-1-phenyl­ethyl)-1H-indole as a colourless solid (48 mg, 50%). Colourless chunks of (II) were recrystallized from methanol solution. δC (63 MHz; CDCl3) 159.9 (Cq), 140.0 (Cq), 136.9 (Cq), 135.9 (CH), 130.1 (CH), 128.9 (Cq), 127.1 (CH), 125.0 (CH), 124.5 (Cq), 122.2 (Cq), 120.2 (CH), 119.8 (CH), 114.4 (CH), 111.3 (CH), 110.0 (CH), 109.1 (Cq), 79.1 (CH2), 55.4 (CH3) and 40.9 (CH); δH (250 MHz; CDCl3) 8.08 (1 H, br s), 7.45–7.25 (9 H, m), 7.19–6.90 (4 H, m), 5.19 (1 H, t, J 6.9) 5.10–5.01 (2 H, m) and 3.76 (3 H, s); Rf 0.09 (1:5 EtOAc, hexanes); m.p. 472 K (EtOH); IR (Nujol, cm-1) 3401, 3013, 2854, 1616, 1548, 1324, 1250, 1203, 1099, 870 and 746; HRMS (ESI) for C23H21N2O3 [M + H]+ calculated 373.1553, found 373.1546.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 3. The N-bound H atoms were located in difference maps and their positions were freely refined. The C-bound H atoms were geometrically placed (C—H = 0.93–0.98 Å) and refined as riding atoms. The constraint Uiso(H) = 1.2Ueq(C, N carrier) or 1.5Ueq(methyl carrier) was applied in all cases. The –CH3 groups were allowed to rotate, but not to tip, to best fit the electron density. Due to the similarity in the a and c unit-cell parameters for (I), twinning models were applied, but no improvement in fit resulted.

Computing details top

For both compounds, data collection: CrystalClear (Rigaku, 2012); cell refinement: CrystalClear (Rigaku, 2012); data reduction: CrystalClear (Rigaku, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. The molecular structure of the N1 molecule in (II), showing 50% probability displacement ellipsoids. The molecular structure of the N3 molecule is very similar.
[Figure 3] Fig. 3. Overlay plot of the conformations of the N1 molecules (black) and N3 molecules (red) in the crystal of (II).
[Figure 4] Fig. 4. Partial packing diagram for (I), showing the formation of [010] chains linked by N—H···π and C—H···π interactions (double-dashed lines). [Symmetry codes: (i) 1 - x, y - 1/2, 1 - z; (ii) 1 - x, y + 1/2, 1 - z.] All H atoms, except H1 and H2, have been omitted for clarity. The orange circles indicate ring centroids.
[Figure 5] Fig. 5. Fragment of the packing for (I), showing C—H···π bonds arising from adjacent C—H groups of the pendant benzene ring. All H atoms, except H14 and H15, have been omitted for clarity. [Symmetry code: (i) 1 - x, y + 1/2, -z.] The orange circles indicate ring centroids.
[Figure 6] Fig. 6. An inversion dimer of N1 molecules in the crystal of (II) linked by pairs of N—H···π and C—H···π interactions (double-dashed lines). [Symmetry code: (i) 1 - x, -y, -z.] The N3 molecules associate into similar dimers. The orange circles indicate ring centroids.
(I) 6-Isopropyl-3-(2-nitro-1-phenylethyl)-1H-indole top
Crystal data top
C19H20N2O2F(000) = 328
Mr = 308.37Dx = 1.268 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 12.4525 (9) ÅCell parameters from 6780 reflections
b = 5.7360 (4) Åθ = 3.1–27.5°
c = 12.5896 (9) ŵ = 0.08 mm−1
β = 116.081 (6)°T = 100 K
V = 807.68 (11) Å3Blade, light red
Z = 20.28 × 0.05 × 0.01 mm
Data collection top
Rigaku Mercury CCD
diffractometer		Rint = 0.107
ω scansθmax = 27.5°, θmin = 3.1°
7830 measured reflectionsh = −13→16
3498 independent reflectionsk = −7→7
2259 reflections with I > 2σ(I)l = −16→13
Refinement top
Refinement on F21 restraint
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.081H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.164 w = 1/[σ2(Fo2) + (0.0357P)2 + 0.4188P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max < 0.001
3498 reflectionsΔρmax = 0.28 e Å−3
213 parametersΔρmin = −0.24 e Å−3
Crystal data top
C19H20N2O2V = 807.68 (11) Å3
Mr = 308.37Z = 2
Monoclinic, P21Mo Kα radiation
a = 12.4525 (9) ŵ = 0.08 mm−1
b = 5.7360 (4) ÅT = 100 K
c = 12.5896 (9) Å0.28 × 0.05 × 0.01 mm
β = 116.081 (6)°
Data collection top
Rigaku Mercury CCD
diffractometer		2259 reflections with I > 2σ(I)
7830 measured reflectionsRint = 0.107
3498 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0811 restraint
wR(F2) = 0.164H atoms treated by a mixture of independent and constrained refinement
S = 1.12Δρmax = 0.28 e Å−3
3498 reflectionsΔρmin = −0.24 e Å−3
213 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.5003 (5)0.1427 (9)0.3881 (4)0.0226 (13)
C20.3850 (5)0.0617 (12)0.3609 (4)0.0254 (13)
H20.3737−0.07520.39720.031*
C30.2883 (5)0.1850 (11)0.2804 (5)0.0264 (13)
C40.3092 (5)0.3871 (10)0.2291 (4)0.0257 (14)
H40.24220.47260.17470.031*
C50.4222 (5)0.4675 (10)0.2538 (4)0.0241 (13)
H50.43290.60610.21830.029*
C60.5208 (5)0.3389 (10)0.3329 (4)0.0239 (12)
C70.6491 (5)0.3646 (10)0.3796 (4)0.0245 (13)
C80.6977 (5)0.1894 (10)0.4586 (5)0.0256 (13)
H80.78110.16420.50380.031*
C90.7126 (5)0.5512 (11)0.3434 (4)0.0232 (12)
H90.68480.70630.35770.028*
C100.8468 (5)0.5371 (11)0.4194 (4)0.0263 (13)
H10A0.86430.54840.50400.032*
H10B0.87710.38510.40670.032*
C110.6842 (4)0.5377 (10)0.2123 (4)0.0222 (12)
C120.7189 (5)0.3446 (10)0.1683 (4)0.0264 (13)
H120.75580.21600.21870.032*
C130.6998 (5)0.3383 (11)0.0510 (5)0.0293 (14)
H130.72450.20660.02160.035*
C140.6451 (5)0.5229 (11)−0.0224 (5)0.0288 (14)
H140.63230.5190−0.10250.035*
C150.6086 (5)0.7141 (11)0.0200 (5)0.0280 (13)
H150.56920.8400−0.03150.034*
C160.6298 (5)0.7225 (11)0.1384 (5)0.0258 (13)
H160.60650.85580.16800.031*
C170.1618 (5)0.0955 (10)0.2462 (5)0.0294 (14)
H170.1681−0.03830.29950.035*
C180.1043 (5)0.0033 (12)0.1182 (5)0.0405 (17)
H18A0.1532−0.12370.11060.061*
H18B0.09940.12980.06390.061*
H18C0.0238−0.05470.09860.061*
C190.0831 (6)0.2786 (12)0.2629 (6)0.0420 (18)
H19A0.00470.21090.24490.063*
H19B0.07320.41000.20960.063*
H19C0.12050.33340.34500.063*
N10.6094 (4)0.0531 (9)0.4643 (4)0.0260 (11)
N20.9084 (4)0.7309 (9)0.3883 (4)0.0267 (11)
H10.625 (5)−0.056 (11)0.514 (5)0.032*
O10.9829 (4)0.6817 (8)0.3538 (4)0.0414 (11)
O20.8825 (4)0.9308 (7)0.4015 (4)0.0376 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.035 (3)0.016 (3)0.020 (3)0.006 (2)0.015 (2)0.000 (2)
C20.035 (3)0.022 (3)0.026 (3)−0.003 (3)0.020 (3)−0.002 (3)
C30.033 (3)0.026 (4)0.023 (3)−0.003 (3)0.015 (2)−0.005 (3)
C40.033 (3)0.023 (4)0.022 (3)0.002 (3)0.013 (2)−0.002 (2)
C50.037 (3)0.017 (3)0.022 (3)0.001 (3)0.017 (3)0.000 (2)
C60.033 (3)0.019 (3)0.023 (3)0.002 (3)0.016 (2)0.000 (3)
C70.034 (3)0.022 (3)0.020 (3)0.002 (3)0.015 (2)−0.002 (2)
C80.025 (3)0.027 (3)0.028 (3)0.004 (3)0.015 (2)−0.002 (3)
C90.031 (3)0.016 (3)0.025 (3)0.000 (3)0.015 (2)0.003 (3)
C100.032 (3)0.023 (3)0.028 (3)0.000 (3)0.016 (2)0.003 (3)
C110.027 (3)0.017 (3)0.023 (3)−0.003 (3)0.013 (2)−0.001 (3)
C120.035 (3)0.019 (3)0.024 (3)−0.004 (3)0.012 (2)0.003 (3)
C130.040 (3)0.023 (3)0.029 (3)−0.003 (3)0.019 (3)−0.004 (3)
C140.042 (4)0.024 (3)0.025 (3)−0.007 (3)0.019 (3)−0.005 (3)
C150.033 (3)0.024 (3)0.027 (3)−0.001 (3)0.013 (2)0.005 (3)
C160.032 (3)0.021 (3)0.028 (3)0.000 (3)0.016 (2)−0.001 (3)
C170.034 (3)0.026 (4)0.029 (3)−0.003 (3)0.015 (3)0.003 (3)
C180.039 (4)0.038 (5)0.044 (4)−0.005 (3)0.018 (3)−0.005 (3)
C190.036 (4)0.041 (5)0.057 (4)−0.001 (3)0.027 (3)−0.009 (3)
N10.033 (3)0.024 (3)0.026 (2)0.007 (2)0.017 (2)0.006 (2)
N20.028 (3)0.024 (3)0.029 (3)0.000 (2)0.013 (2)−0.004 (2)
O10.048 (3)0.033 (3)0.057 (3)−0.002 (2)0.036 (2)−0.010 (2)
O20.042 (3)0.018 (2)0.057 (3)0.002 (2)0.025 (2)−0.006 (2)
Geometric parameters (Å, º) top
C1—N11.372 (7)C11—C121.389 (8)
C1—C21.400 (7)C12—C131.389 (7)
C1—C61.404 (7)C12—H120.9500
C2—C31.380 (8)C13—C141.373 (8)
C2—H20.9500C13—H130.9500
C3—C41.406 (8)C14—C151.381 (8)
C3—C171.527 (8)C14—H140.9500
C4—C51.380 (7)C15—C161.397 (7)
C4—H40.9500C15—H150.9500
C5—C61.403 (7)C16—H160.9500
C5—H50.9500C17—C191.513 (8)
C6—C71.447 (7)C17—C181.541 (8)
C7—C81.355 (8)C17—H171.0000
C7—C91.516 (8)C18—H18A0.9800
C8—N11.377 (7)C18—H18B0.9800
C8—H80.9500C18—H18C0.9800
C9—C101.519 (7)C19—H19A0.9800
C9—C111.530 (7)C19—H19B0.9800
C9—H91.0000C19—H19C0.9800
C10—N21.497 (7)N1—H10.84 (6)
C10—H10A0.9900N2—O11.217 (6)
C10—H10B0.9900N2—O21.222 (6)
C11—C161.376 (8)
N1—C1—C2129.8 (5)C13—C12—C11120.4 (5)
N1—C1—C6107.9 (5)C13—C12—H12119.8
C2—C1—C6122.3 (5)C11—C12—H12119.8
C3—C2—C1118.7 (5)C14—C13—C12119.9 (6)
C3—C2—H2120.7C14—C13—H13120.1
C1—C2—H2120.7C12—C13—H13120.1
C2—C3—C4118.8 (5)C13—C14—C15120.2 (5)
C2—C3—C17119.6 (5)C13—C14—H14119.9
C4—C3—C17121.6 (5)C15—C14—H14119.9
C5—C4—C3123.2 (5)C14—C15—C16120.0 (5)
C5—C4—H4118.4C14—C15—H15120.0
C3—C4—H4118.4C16—C15—H15120.0
C4—C5—C6118.2 (5)C11—C16—C15120.0 (5)
C4—C5—H5120.9C11—C16—H16120.0
C6—C5—H5120.9C15—C16—H16120.0
C5—C6—C1118.7 (5)C19—C17—C3112.2 (5)
C5—C6—C7134.5 (5)C19—C17—C18110.6 (5)
C1—C6—C7106.8 (5)C3—C17—C18111.0 (4)
C8—C7—C6106.3 (5)C19—C17—H17107.6
C8—C7—C9128.4 (5)C3—C17—H17107.6
C6—C7—C9125.4 (5)C18—C17—H17107.6
C7—C8—N1110.5 (5)C17—C18—H18A109.5
C7—C8—H8124.8C17—C18—H18B109.5
N1—C8—H8124.8H18A—C18—H18B109.5
C7—C9—C10110.3 (5)C17—C18—H18C109.5
C7—C9—C11112.7 (5)H18A—C18—H18C109.5
C10—C9—C11110.3 (4)H18B—C18—H18C109.5
C7—C9—H9107.8C17—C19—H19A109.5
C10—C9—H9107.8C17—C19—H19B109.5
C11—C9—H9107.8H19A—C19—H19B109.5
N2—C10—C9110.1 (4)C17—C19—H19C109.5
N2—C10—H10A109.6H19A—C19—H19C109.5
C9—C10—H10A109.6H19B—C19—H19C109.5
N2—C10—H10B109.6C1—N1—C8108.6 (5)
C9—C10—H10B109.6C1—N1—H1129 (4)
H10A—C10—H10B108.2C8—N1—H1122 (4)
C16—C11—C12119.5 (5)O1—N2—O2123.6 (5)
C16—C11—C9120.1 (5)O1—N2—C10118.7 (5)
C12—C11—C9120.3 (5)O2—N2—C10117.7 (5)
N1—C1—C2—C3179.9 (5)C7—C9—C10—N2−176.5 (4)
C6—C1—C2—C3−2.6 (8)C11—C9—C10—N258.4 (6)
C1—C2—C3—C4−0.2 (7)C7—C9—C11—C16118.9 (6)
C1—C2—C3—C17177.9 (5)C10—C9—C11—C16−117.3 (6)
C2—C3—C4—C51.0 (8)C7—C9—C11—C12−64.5 (6)
C17—C3—C4—C5−177.0 (5)C10—C9—C11—C1259.3 (7)
C3—C4—C5—C60.9 (7)C16—C11—C12—C130.6 (8)
C4—C5—C6—C1−3.5 (7)C9—C11—C12—C13−176.0 (5)
C4—C5—C6—C7179.8 (5)C11—C12—C13—C14−0.8 (8)
N1—C1—C6—C5−177.5 (5)C12—C13—C14—C15−0.2 (8)
C2—C1—C6—C54.5 (8)C13—C14—C15—C161.4 (8)
N1—C1—C6—C70.0 (5)C12—C11—C16—C150.6 (8)
C2—C1—C6—C7−178.0 (5)C9—C11—C16—C15177.2 (5)
C5—C6—C7—C8176.5 (6)C14—C15—C16—C11−1.6 (8)
C1—C6—C7—C8−0.4 (6)C2—C3—C17—C19126.2 (6)
C5—C6—C7—C9−4.3 (9)C4—C3—C17—C19−55.7 (7)
C1—C6—C7—C9178.7 (5)C2—C3—C17—C18−109.4 (6)
C6—C7—C8—N10.7 (6)C4—C3—C17—C1868.6 (7)
C9—C7—C8—N1−178.4 (5)C2—C1—N1—C8178.2 (5)
C8—C7—C9—C10−6.4 (8)C6—C1—N1—C80.4 (5)
C6—C7—C9—C10174.6 (5)C7—C8—N1—C1−0.7 (6)
C8—C7—C9—C11117.3 (6)C9—C10—N2—O1−120.8 (5)
C6—C7—C9—C11−61.6 (7)C9—C10—N2—O260.7 (6)
Hydrogen-bond geometry (Å, º) top
Cg1, Cg2 and Cg3 are the centroids of the N1/C1/C6–C8, C1–C6 and C11–C16 rings, respectively.
D—H···AD—HH···AD···AD—H···A
N1—H1···Cg2i0.84 (6)2.64 (6)3.386 (5)148 (6)
C2—H2···Cg1i0.952.633.468 (6)147
C14—H14···Cg2ii0.952.793.638 (6)148
C15—H15···Cg3ii0.952.873.551 (7)129
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+1, y+1/2, −z.
(II) 2-(4-Methoxyphenyl)-3-(2-nitro-1-phenylethyl)-1H-indole top
Crystal data top
C23H20N2O3Z = 4
Mr = 372.41F(000) = 784
Triclinic, P1Dx = 1.349 Mg m−3
a = 9.2014 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.4543 (7) ÅCell parameters from 22268 reflections
c = 21.6201 (14) Åθ = 2.2–27.5°
α = 98.563 (4)°µ = 0.09 mm−1
β = 93.416 (4)°T = 100 K
γ = 98.354 (4)°Plate, colourless
V = 1833.7 (2) Å30.10 × 0.06 × 0.06 mm
Data collection top
Rigaku Mercury CCD
diffractometer		Rint = 0.038
ω scansθmax = 28.4°, θmin = 2.2°
24774 measured reflectionsh = −11→11
8621 independent reflectionsk = −12→12
6769 reflections with I > 2σ(I)l = −28→28
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: mixed
wR(F2) = 0.124H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0548P)2 + 0.8021P]
where P = (Fo2 + 2Fc2)/3
8621 reflections(Δ/σ)max < 0.001
513 parametersΔρmax = 0.62 e Å−3
0 restraintsΔρmin = −0.31 e Å−3
Crystal data top
C23H20N2O3γ = 98.354 (4)°
Mr = 372.41V = 1833.7 (2) Å3
Triclinic, P1Z = 4
a = 9.2014 (5) ÅMo Kα radiation
b = 9.4543 (7) ŵ = 0.09 mm−1
c = 21.6201 (14) ÅT = 100 K
α = 98.563 (4)°0.10 × 0.06 × 0.06 mm
β = 93.416 (4)°
Data collection top
Rigaku Mercury CCD
diffractometer		6769 reflections with I > 2σ(I)
24774 measured reflectionsRint = 0.038
8621 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.124H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.62 e Å−3
8621 reflectionsΔρmin = −0.31 e Å−3
513 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.49618 (16)0.34164 (15)0.06414 (6)0.0170 (3)
C20.38705 (17)0.42054 (15)0.08413 (7)0.0189 (3)
H2A0.32010.44950.05510.023*
C30.38042 (17)0.45411 (16)0.14638 (7)0.0213 (3)
H3A0.30870.50940.16240.026*
C40.47956 (18)0.40736 (16)0.18735 (7)0.0222 (3)
H40.47370.43290.23120.027*
C50.58536 (17)0.32607 (16)0.16733 (7)0.0199 (3)
H50.64970.29500.19680.024*
C60.59606 (16)0.29082 (15)0.10432 (7)0.0171 (3)
C70.68766 (16)0.21018 (15)0.06651 (7)0.0177 (3)
C80.64249 (16)0.21756 (15)0.00713 (7)0.0173 (3)
C90.81582 (17)0.13561 (16)0.08290 (7)0.0217 (3)
H90.87200.12490.04470.026*
C100.92103 (18)0.22377 (17)0.13441 (8)0.0245 (3)
H10A1.00270.16980.14280.029*
H10B0.86950.23890.17320.029*
C110.77242 (16)−0.01722 (16)0.09801 (7)0.0188 (3)
C120.84562 (17)−0.12686 (16)0.07252 (7)0.0217 (3)
H120.9215−0.10600.04580.026*
C130.81037 (18)−0.26753 (17)0.08526 (8)0.0254 (3)
H130.8620−0.34140.06720.030*
C140.70126 (18)−0.29942 (17)0.12382 (7)0.0244 (3)
H140.6775−0.39490.13290.029*
C150.62638 (18)−0.19130 (17)0.14925 (7)0.0243 (3)
H150.5502−0.21270.17580.029*
C160.66181 (17)−0.05090 (16)0.13627 (7)0.0214 (3)
H160.60920.02250.15400.026*
C170.70037 (16)0.15610 (15)−0.04944 (7)0.0180 (3)
C180.77075 (17)0.24493 (16)−0.08755 (7)0.0212 (3)
H180.78000.3471−0.07640.025*
C190.82656 (17)0.18773 (16)−0.14060 (7)0.0214 (3)
H190.87350.2487−0.16710.026*
C200.81369 (16)0.03855 (16)−0.15535 (7)0.0190 (3)
C210.74181 (17)−0.05225 (16)−0.11828 (7)0.0207 (3)
H210.7316−0.1544−0.12970.025*
C220.68649 (17)0.00643 (16)−0.06567 (7)0.0204 (3)
H220.6379−0.0547−0.03960.025*
C230.9661 (2)0.06002 (19)−0.23777 (7)0.0297 (4)
H23A1.0146−0.0009−0.26820.045*
H23B1.04090.1233−0.20790.045*
H23C0.90830.1192−0.25990.045*
N10.52777 (14)0.29681 (13)0.00553 (6)0.0173 (2)
H10.471 (2)0.3091 (19)−0.0271 (9)0.021*
N20.98391 (15)0.36924 (15)0.11821 (7)0.0272 (3)
O11.01892 (15)0.37644 (15)0.06681 (6)0.0391 (3)
O21.00019 (16)0.47097 (14)0.15869 (7)0.0418 (3)
O30.87109 (12)−0.02940 (12)−0.20477 (5)0.0229 (2)
C241.07078 (17)0.27498 (15)0.60018 (7)0.0186 (3)
C251.19481 (18)0.23268 (16)0.62786 (7)0.0222 (3)
H251.25100.17000.60460.027*
C261.23137 (18)0.28475 (17)0.68904 (7)0.0245 (3)
H261.31420.25800.71020.029*
C271.14771 (19)0.37763 (17)0.72123 (7)0.0252 (3)
H271.17560.41360.76430.030*
C281.02574 (18)0.42001 (17)0.69332 (7)0.0224 (3)
H280.97150.48420.71690.027*
C290.98380 (16)0.36824 (15)0.63114 (7)0.0182 (3)
C300.86833 (17)0.38853 (16)0.58743 (7)0.0184 (3)
C310.88891 (16)0.30774 (15)0.53304 (6)0.0178 (3)
C320.73865 (18)0.46891 (17)0.59473 (7)0.0222 (3)
H320.66270.42160.56000.027*
C330.6680 (2)0.45620 (18)0.65431 (8)0.0279 (4)
H33A0.58170.50770.65510.033*
H33B0.73890.50430.69010.033*
C340.76883 (17)0.62946 (16)0.58830 (7)0.0203 (3)
C350.89706 (19)0.72001 (17)0.61460 (7)0.0241 (3)
H350.97190.68180.63600.029*
C360.9164 (2)0.86699 (18)0.60972 (7)0.0272 (4)
H361.00450.92800.62780.033*
C370.8086 (2)0.92481 (18)0.57886 (8)0.0296 (4)
H370.82141.02540.57670.035*
C380.6826 (2)0.83509 (19)0.55131 (8)0.0297 (4)
H380.60910.87330.52910.036*
C390.66297 (18)0.68832 (18)0.55610 (7)0.0252 (3)
H390.57570.62730.53700.030*
C400.80143 (17)0.28679 (16)0.47391 (7)0.0186 (3)
C410.78144 (17)0.40508 (16)0.44448 (7)0.0204 (3)
H410.82570.49980.46370.024*
C420.69952 (17)0.38631 (17)0.38876 (7)0.0216 (3)
H420.68800.46690.36840.026*
C430.63290 (17)0.24818 (17)0.36192 (7)0.0213 (3)
C440.65272 (18)0.12873 (17)0.39006 (7)0.0231 (3)
H440.60820.03410.37090.028*
C450.73698 (18)0.14931 (16)0.44560 (7)0.0219 (3)
H450.75160.06830.46510.026*
C460.4670 (2)0.1044 (2)0.28258 (8)0.0346 (4)
H46A0.40590.11350.24510.052*
H46B0.40350.06960.31380.052*
H46C0.53450.03550.27120.052*
N31.01008 (14)0.23898 (13)0.54058 (6)0.0186 (3)
H31.050 (2)0.193 (2)0.5094 (9)0.022*
N40.61859 (17)0.30122 (17)0.66247 (8)0.0351 (4)
O40.55989 (17)0.21888 (16)0.61780 (8)0.0474 (4)
O50.6370 (2)0.26938 (18)0.71306 (8)0.0575 (4)
O60.54974 (13)0.24217 (13)0.30834 (5)0.0278 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0182 (7)0.0134 (6)0.0185 (6)−0.0002 (5)−0.0014 (5)0.0033 (5)
C20.0184 (7)0.0157 (7)0.0230 (7)0.0027 (6)−0.0002 (6)0.0054 (5)
C30.0219 (8)0.0159 (7)0.0263 (7)0.0025 (6)0.0044 (6)0.0034 (6)
C40.0270 (8)0.0195 (7)0.0189 (7)0.0001 (6)0.0012 (6)0.0029 (5)
C50.0226 (8)0.0170 (7)0.0197 (7)0.0002 (6)−0.0027 (6)0.0056 (5)
C60.0180 (7)0.0117 (6)0.0209 (7)−0.0004 (5)−0.0022 (5)0.0045 (5)
C70.0164 (7)0.0136 (6)0.0231 (7)0.0004 (5)−0.0009 (5)0.0053 (5)
C80.0157 (7)0.0131 (6)0.0229 (7)0.0013 (5)0.0004 (5)0.0041 (5)
C90.0194 (8)0.0192 (7)0.0276 (8)0.0037 (6)−0.0007 (6)0.0078 (6)
C100.0229 (8)0.0216 (8)0.0295 (8)0.0031 (6)−0.0026 (6)0.0082 (6)
C110.0180 (7)0.0173 (7)0.0208 (7)0.0020 (6)−0.0053 (5)0.0059 (5)
C120.0199 (8)0.0226 (7)0.0228 (7)0.0048 (6)−0.0024 (6)0.0043 (6)
C130.0255 (9)0.0196 (7)0.0296 (8)0.0062 (6)−0.0080 (6)0.0006 (6)
C140.0272 (9)0.0171 (7)0.0270 (8)−0.0014 (6)−0.0116 (6)0.0074 (6)
C150.0236 (8)0.0250 (8)0.0233 (7)−0.0018 (6)−0.0039 (6)0.0084 (6)
C160.0205 (8)0.0202 (7)0.0234 (7)0.0048 (6)−0.0029 (6)0.0036 (6)
C170.0159 (7)0.0179 (7)0.0200 (7)0.0030 (6)−0.0021 (5)0.0037 (5)
C180.0227 (8)0.0162 (7)0.0260 (7)0.0057 (6)0.0007 (6)0.0053 (6)
C190.0217 (8)0.0198 (7)0.0244 (7)0.0038 (6)0.0022 (6)0.0083 (6)
C200.0156 (7)0.0234 (7)0.0179 (7)0.0043 (6)−0.0022 (5)0.0028 (5)
C210.0205 (8)0.0157 (7)0.0244 (7)0.0007 (6)−0.0011 (6)0.0012 (5)
C220.0198 (8)0.0185 (7)0.0223 (7)0.0000 (6)0.0003 (6)0.0045 (5)
C230.0347 (10)0.0337 (9)0.0195 (7)−0.0004 (7)0.0050 (7)0.0048 (6)
N10.0175 (6)0.0176 (6)0.0174 (6)0.0048 (5)−0.0016 (5)0.0041 (4)
N20.0180 (7)0.0245 (7)0.0394 (8)0.0016 (5)−0.0014 (6)0.0094 (6)
O10.0357 (8)0.0405 (8)0.0374 (7)−0.0061 (6)0.0004 (6)0.0074 (6)
O20.0470 (9)0.0270 (7)0.0482 (8)0.0013 (6)0.0062 (7)−0.0006 (6)
O30.0264 (6)0.0230 (5)0.0185 (5)0.0029 (5)0.0020 (4)0.0021 (4)
C240.0212 (8)0.0158 (7)0.0178 (6)−0.0010 (6)−0.0010 (5)0.0048 (5)
C250.0234 (8)0.0185 (7)0.0247 (7)0.0028 (6)−0.0012 (6)0.0055 (6)
C260.0231 (8)0.0250 (8)0.0252 (8)0.0001 (6)−0.0065 (6)0.0105 (6)
C270.0299 (9)0.0271 (8)0.0168 (7)−0.0023 (7)−0.0030 (6)0.0062 (6)
C280.0258 (8)0.0230 (7)0.0173 (7)0.0004 (6)0.0010 (6)0.0038 (5)
C290.0195 (7)0.0179 (7)0.0172 (6)0.0004 (6)0.0002 (5)0.0056 (5)
C300.0189 (7)0.0183 (7)0.0179 (6)0.0007 (6)0.0005 (5)0.0048 (5)
C310.0191 (7)0.0163 (7)0.0180 (7)0.0001 (6)−0.0011 (5)0.0057 (5)
C320.0220 (8)0.0213 (7)0.0237 (7)0.0026 (6)0.0020 (6)0.0055 (6)
C330.0297 (9)0.0270 (8)0.0284 (8)0.0050 (7)0.0059 (7)0.0073 (6)
C340.0227 (8)0.0210 (7)0.0184 (7)0.0051 (6)0.0055 (6)0.0042 (5)
C350.0278 (9)0.0262 (8)0.0183 (7)0.0036 (7)0.0014 (6)0.0040 (6)
C360.0349 (10)0.0245 (8)0.0197 (7)−0.0024 (7)0.0072 (6)0.0002 (6)
C370.0421 (11)0.0208 (8)0.0288 (8)0.0062 (7)0.0147 (7)0.0077 (6)
C380.0317 (9)0.0304 (9)0.0329 (9)0.0118 (7)0.0099 (7)0.0149 (7)
C390.0235 (8)0.0276 (8)0.0262 (8)0.0049 (7)0.0043 (6)0.0079 (6)
C400.0181 (7)0.0210 (7)0.0164 (6)0.0013 (6)−0.0002 (5)0.0049 (5)
C410.0214 (8)0.0192 (7)0.0195 (7)−0.0007 (6)−0.0001 (6)0.0044 (5)
C420.0225 (8)0.0228 (7)0.0204 (7)0.0017 (6)−0.0011 (6)0.0092 (6)
C430.0199 (8)0.0271 (8)0.0162 (6)0.0008 (6)−0.0024 (5)0.0056 (6)
C440.0261 (8)0.0209 (7)0.0204 (7)0.0001 (6)−0.0026 (6)0.0027 (6)
C450.0258 (8)0.0200 (7)0.0197 (7)0.0024 (6)−0.0023 (6)0.0059 (6)
C460.0381 (11)0.0361 (10)0.0236 (8)−0.0102 (8)−0.0110 (7)0.0062 (7)
N30.0206 (7)0.0196 (6)0.0152 (6)0.0030 (5)−0.0014 (5)0.0028 (5)
N40.0287 (8)0.0320 (8)0.0469 (9)0.0046 (7)0.0123 (7)0.0104 (7)
O40.0411 (8)0.0394 (8)0.0608 (10)−0.0023 (7)0.0144 (7)0.0094 (7)
O50.0674 (11)0.0575 (10)0.0579 (10)0.0112 (8)0.0167 (8)0.0370 (8)
O60.0310 (7)0.0303 (6)0.0194 (5)−0.0034 (5)−0.0103 (5)0.0078 (4)
Geometric parameters (Å, º) top
C1—N11.3377 (18)C24—N31.3478 (18)
C1—C21.387 (2)C24—C251.394 (2)
C1—C61.410 (2)C24—C291.400 (2)
C2—C31.343 (2)C25—C261.345 (2)
C2—H2A0.9500C25—H250.9500
C3—C41.396 (2)C26—C271.388 (2)
C3—H3A0.9500C26—H260.9500
C4—C51.376 (2)C27—C281.381 (2)
C4—H40.9500C27—H270.9500
C5—C61.366 (2)C28—C291.372 (2)
C5—H50.9500C28—H280.9500
C6—C71.429 (2)C29—C301.432 (2)
C7—C81.341 (2)C30—C311.343 (2)
C7—C91.510 (2)C30—C321.509 (2)
C8—N11.3820 (19)C31—N31.3830 (19)
C8—C171.440 (2)C31—C401.441 (2)
C9—C101.494 (2)C32—C331.490 (2)
C9—C111.530 (2)C32—C341.531 (2)
C9—H91.0000C32—H321.0000
C10—N21.512 (2)C33—N41.509 (2)
C10—H10A0.9900C33—H33A0.9900
C10—H10B0.9900C33—H33B0.9900
C11—C161.381 (2)C34—C351.389 (2)
C11—C121.382 (2)C34—C391.391 (2)
C12—C131.394 (2)C35—C361.396 (2)
C12—H120.9500C35—H350.9500
C13—C141.371 (2)C36—C371.383 (3)
C13—H130.9500C36—H360.9500
C14—C151.380 (2)C37—C381.379 (3)
C14—H140.9500C37—H370.9500
C15—C161.394 (2)C38—C391.393 (2)
C15—H150.9500C38—H380.9500
C16—H160.9500C39—H390.9500
C17—C181.384 (2)C40—C451.383 (2)
C17—C221.391 (2)C40—C411.395 (2)
C18—C191.356 (2)C41—C421.357 (2)
C18—H180.9500C41—H410.9500
C19—C201.385 (2)C42—C431.385 (2)
C19—H190.9500C42—H420.9500
C20—O31.3398 (17)C43—O61.3389 (17)
C20—C211.386 (2)C43—C441.389 (2)
C21—C221.351 (2)C44—C451.363 (2)
C21—H210.9500C44—H440.9500
C22—H220.9500C45—H450.9500
C23—O31.4240 (19)C46—O61.425 (2)
C23—H23A0.9800C46—H46A0.9800
C23—H23B0.9800C46—H46B0.9800
C23—H23C0.9800C46—H46C0.9800
N1—H10.886 (19)N3—H30.875 (18)
N2—O11.1841 (19)N4—O51.186 (2)
N2—O21.1856 (19)N4—O41.193 (2)
N1—C1—C2128.86 (14)N3—C24—C25129.20 (14)
N1—C1—C6106.46 (13)N3—C24—C29105.99 (13)
C2—C1—C6124.68 (13)C25—C24—C29124.81 (14)
C3—C2—C1116.96 (14)C26—C25—C24116.94 (15)
C3—C2—H2A121.5C26—C25—H25121.5
C1—C2—H2A121.5C24—C25—H25121.5
C2—C3—C4119.63 (14)C25—C26—C27119.82 (15)
C2—C3—H3A120.2C25—C26—H26120.1
C4—C3—H3A120.2C27—C26—H26120.1
C5—C4—C3123.24 (14)C28—C27—C26122.88 (14)
C5—C4—H4118.4C28—C27—H27118.6
C3—C4—H4118.4C26—C27—H27118.6
C6—C5—C4118.74 (14)C29—C28—C27119.17 (15)
C6—C5—H5120.6C29—C28—H28120.4
C4—C5—H5120.6C27—C28—H28120.4
C5—C6—C1116.72 (14)C28—C29—C24116.38 (14)
C5—C6—C7134.97 (14)C28—C29—C30134.77 (14)
C1—C6—C7108.31 (12)C24—C29—C30108.84 (12)
C8—C7—C6105.06 (13)C31—C30—C29105.15 (13)
C8—C7—C9122.53 (13)C31—C30—C32122.19 (14)
C6—C7—C9132.32 (13)C29—C30—C32132.51 (13)
C7—C8—N1110.65 (13)C30—C31—N3110.11 (13)
C7—C8—C17127.68 (14)C30—C31—C40128.18 (14)
N1—C8—C17121.66 (13)N3—C31—C40121.70 (13)
C10—C9—C7112.94 (13)C33—C32—C30113.41 (13)
C10—C9—C11109.64 (12)C33—C32—C34108.23 (12)
C7—C9—C11114.72 (12)C30—C32—C34115.66 (13)
C10—C9—H9106.3C33—C32—H32106.3
C7—C9—H9106.3C30—C32—H32106.3
C11—C9—H9106.3C34—C32—H32106.3
C9—C10—N2112.11 (13)C32—C33—N4113.00 (14)
C9—C10—H10A109.2C32—C33—H33A109.0
N2—C10—H10A109.2N4—C33—H33A109.0
C9—C10—H10B109.2C32—C33—H33B109.0
N2—C10—H10B109.2N4—C33—H33B109.0
H10A—C10—H10B107.9H33A—C33—H33B107.8
C16—C11—C12118.10 (14)C35—C34—C39118.41 (14)
C16—C11—C9122.57 (13)C35—C34—C32122.49 (14)
C12—C11—C9119.33 (14)C39—C34—C32119.08 (14)
C11—C12—C13121.32 (15)C34—C35—C36120.23 (16)
C11—C12—H12119.3C34—C35—H35119.9
C13—C12—H12119.3C36—C35—H35119.9
C14—C13—C12120.07 (15)C37—C36—C35120.76 (16)
C14—C13—H13120.0C37—C36—H36119.6
C12—C13—H13120.0C35—C36—H36119.6
C13—C14—C15119.29 (14)C38—C37—C36119.40 (15)
C13—C14—H14120.4C38—C37—H37120.3
C15—C14—H14120.4C36—C37—H37120.3
C14—C15—C16120.43 (15)C37—C38—C39119.95 (16)
C14—C15—H15119.8C37—C38—H38120.0
C16—C15—H15119.8C39—C38—H38120.0
C11—C16—C15120.79 (14)C34—C39—C38121.22 (16)
C11—C16—H16119.6C34—C39—H39119.4
C15—C16—H16119.6C38—C39—H39119.4
C18—C17—C22119.76 (13)C45—C40—C41119.30 (14)
C18—C17—C8120.44 (13)C45—C40—C31120.40 (13)
C22—C17—C8119.80 (13)C41—C40—C31120.31 (13)
C19—C18—C17120.71 (14)C42—C41—C40120.70 (14)
C19—C18—H18119.6C42—C41—H41119.7
C17—C18—H18119.6C40—C41—H41119.7
C18—C19—C20118.60 (14)C41—C42—C43119.13 (14)
C18—C19—H19120.7C41—C42—H42120.4
C20—C19—H19120.7C43—C42—H42120.4
O3—C20—C19123.68 (14)O6—C43—C42114.42 (13)
O3—C20—C21114.75 (13)O6—C43—C44124.49 (14)
C19—C20—C21121.55 (13)C42—C43—C44121.09 (14)
C22—C21—C20119.10 (14)C45—C44—C43118.99 (14)
C22—C21—H21120.4C45—C44—H44120.5
C20—C21—H21120.4C43—C44—H44120.5
C21—C22—C17120.25 (14)C44—C45—C40120.77 (14)
C21—C22—H22119.9C44—C45—H45119.6
C17—C22—H22119.9C40—C45—H45119.6
O3—C23—H23A109.5O6—C46—H46A109.5
O3—C23—H23B109.5O6—C46—H46B109.5
H23A—C23—H23B109.5H46A—C46—H46B109.5
O3—C23—H23C109.5O6—C46—H46C109.5
H23A—C23—H23C109.5H46A—C46—H46C109.5
H23B—C23—H23C109.5H46B—C46—H46C109.5
C1—N1—C8109.50 (12)C24—N3—C31109.90 (12)
C1—N1—H1120.6 (11)C24—N3—H3125.5 (12)
C8—N1—H1129.3 (11)C31—N3—H3123.7 (12)
O1—N2—O2122.88 (15)O5—N4—O4123.94 (18)
O1—N2—C10119.27 (14)O5—N4—C33118.26 (17)
O2—N2—C10117.80 (15)O4—N4—C33117.78 (16)
C20—O3—C23116.20 (12)C43—O6—C46116.24 (13)
N1—C1—C2—C3−178.82 (14)N3—C24—C25—C26−179.75 (15)
C6—C1—C2—C32.2 (2)C29—C24—C25—C260.8 (2)
C1—C2—C3—C4−1.0 (2)C24—C25—C26—C27−0.8 (2)
C2—C3—C4—C5−0.5 (2)C25—C26—C27—C280.3 (2)
C3—C4—C5—C61.0 (2)C26—C27—C28—C290.3 (2)
C4—C5—C6—C10.1 (2)C27—C28—C29—C24−0.4 (2)
C4—C5—C6—C7−179.51 (15)C27—C28—C29—C30−179.21 (16)
N1—C1—C6—C5179.10 (13)N3—C24—C29—C28−179.75 (13)
C2—C1—C6—C5−1.8 (2)C25—C24—C29—C28−0.2 (2)
N1—C1—C6—C7−1.20 (16)N3—C24—C29—C30−0.62 (16)
C2—C1—C6—C7177.94 (14)C25—C24—C29—C30178.93 (14)
C5—C6—C7—C8−179.37 (16)C28—C29—C30—C31179.30 (17)
C1—C6—C7—C81.01 (16)C24—C29—C30—C310.40 (16)
C5—C6—C7—C9−2.8 (3)C28—C29—C30—C32−5.2 (3)
C1—C6—C7—C9177.56 (14)C24—C29—C30—C32175.88 (15)
C6—C7—C8—N1−0.45 (16)C29—C30—C31—N3−0.02 (16)
C9—C7—C8—N1−177.42 (12)C32—C30—C31—N3−176.09 (13)
C6—C7—C8—C17178.90 (14)C29—C30—C31—C40178.55 (14)
C9—C7—C8—C171.9 (2)C32—C30—C31—C402.5 (2)
C8—C7—C9—C10133.17 (15)C31—C30—C32—C33136.46 (16)
C6—C7—C9—C10−42.9 (2)C29—C30—C32—C33−38.4 (2)
C8—C7—C9—C11−100.19 (17)C31—C30—C32—C34−97.65 (17)
C6—C7—C9—C1183.76 (19)C29—C30—C32—C3487.50 (19)
C7—C9—C10—N2−58.42 (17)C30—C32—C33—N4−56.24 (19)
C11—C9—C10—N2172.28 (13)C34—C32—C33—N4174.02 (14)
C10—C9—C11—C1683.64 (18)C33—C32—C34—C3586.90 (18)
C7—C9—C11—C16−44.7 (2)C30—C32—C34—C35−41.6 (2)
C10—C9—C11—C12−96.58 (17)C33—C32—C34—C39−91.71 (17)
C7—C9—C11—C12135.11 (15)C30—C32—C34—C39139.81 (14)
C16—C11—C12—C13−0.6 (2)C39—C34—C35—C361.4 (2)
C9—C11—C12—C13179.65 (14)C32—C34—C35—C36−177.20 (13)
C11—C12—C13—C14−0.1 (2)C34—C35—C36—C370.1 (2)
C12—C13—C14—C150.6 (2)C35—C36—C37—C38−1.7 (2)
C13—C14—C15—C16−0.4 (2)C36—C37—C38—C391.6 (2)
C12—C11—C16—C150.7 (2)C35—C34—C39—C38−1.4 (2)
C9—C11—C16—C15−179.52 (14)C32—C34—C39—C38177.22 (14)
C14—C15—C16—C11−0.2 (2)C37—C38—C39—C34−0.1 (2)
C7—C8—C17—C18−114.00 (18)C30—C31—C40—C45−121.49 (18)
N1—C8—C17—C1865.3 (2)N3—C31—C40—C4556.9 (2)
C7—C8—C17—C2265.5 (2)C30—C31—C40—C4158.8 (2)
N1—C8—C17—C22−115.22 (16)N3—C31—C40—C41−122.77 (16)
C22—C17—C18—C19−0.1 (2)C45—C40—C41—C420.2 (2)
C8—C17—C18—C19179.44 (14)C31—C40—C41—C42179.86 (14)
C17—C18—C19—C20−1.0 (2)C40—C41—C42—C431.4 (2)
C18—C19—C20—O3−176.55 (14)C41—C42—C43—O6177.38 (14)
C18—C19—C20—C211.9 (2)C41—C42—C43—C44−2.2 (2)
O3—C20—C21—C22176.83 (14)O6—C43—C44—C45−178.21 (15)
C19—C20—C21—C22−1.8 (2)C42—C43—C44—C451.3 (2)
C20—C21—C22—C170.7 (2)C43—C44—C45—C400.3 (2)
C18—C17—C22—C210.2 (2)C41—C40—C45—C44−1.0 (2)
C8—C17—C22—C21−179.29 (14)C31—C40—C45—C44179.25 (15)
C2—C1—N1—C8−178.16 (14)C25—C24—N3—C31−178.91 (14)
C6—C1—N1—C80.93 (16)C29—C24—N3—C310.60 (16)
C7—C8—N1—C1−0.30 (17)C30—C31—N3—C24−0.37 (17)
C17—C8—N1—C1−179.70 (13)C40—C31—N3—C24−179.06 (13)
C9—C10—N2—O1−41.3 (2)C32—C33—N4—O5139.49 (17)
C9—C10—N2—O2141.02 (15)C32—C33—N4—O4−42.3 (2)
C19—C20—O3—C238.6 (2)C42—C43—O6—C46−173.68 (15)
C21—C20—O3—C23−169.94 (13)C44—C43—O6—C465.8 (2)
Hydrogen-bond geometry (Å, º) top
Cg1, Cg2, Cg3, Cg6, Cg7 and Cg8 are the centroids of the N1/C1/C6–C8, C1–C6, C11–C16, N3/C24/C29–C31, C24–C29 and C34–C39 rings, respectively.
D—H···AD—HH···AD···AD—H···A
N1—H1···Cg3i0.886 (19)2.640 (19)3.3631 (15)139.6 (15)
N3—H3···Cg8ii0.875 (18)2.582 (19)3.3364 (15)144.9 (16)
C14—H14···Cg2iii0.952.583.4228 (18)149
C21—H21···Cg2i0.952.693.4133 (17)134
C22—H22···Cg1i0.952.683.4543 (17)138
C23—H23B···Cg3iv0.982.793.6739 (18)150
C37—H37···Cg6v0.952.863.7660 (18)160
C41—H41···Cg6ii0.952.703.3793 (17)129
C42—H42···Cg7ii0.952.673.3627 (17)130
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y+1, −z+1; (iii) x, y−1, z; (iv) −x+2, −y, −z; (v) x, y+1, z.
Hydrogen-bond geometry (Å, º) for (I) top
Cg1, Cg2 and Cg3 are the centroids of the N1/C1/C6–C8, C1–C6 and C11–C16 rings, respectively.
D—H···AD—HH···AD···AD—H···A
N1—H1···Cg2i0.84 (6)2.64 (6)3.386 (5)148 (6)
C2—H2···Cg1i0.952.633.468 (6)147
C14—H14···Cg2ii0.952.793.638 (6)148
C15—H15···Cg3ii0.952.873.551 (7)129
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+1, y+1/2, −z.
Hydrogen-bond geometry (Å, º) for (II) top
Cg1, Cg2, Cg3, Cg6, Cg7 and Cg8 are the centroids of the N1/C1/C6–C8, C1–C6, C11–C16, N3/C24/C29–C31, C24–C29 and C34–C39 rings, respectively.
D—H···AD—HH···AD···AD—H···A
N1—H1···Cg3i0.886 (19)2.640 (19)3.3631 (15)139.6 (15)
N3—H3···Cg8ii0.875 (18)2.582 (19)3.3364 (15)144.9 (16)
C14—H14···Cg2iii0.952.583.4228 (18)149
C21—H21···Cg2i0.952.693.4133 (17)134
C22—H22···Cg1i0.952.683.4543 (17)138
C23—H23B···Cg3iv0.982.793.6739 (18)150
C37—H37···Cg6v0.952.863.7660 (18)160
C41—H41···Cg6ii0.952.703.3793 (17)129
C42—H42···Cg7ii0.952.673.3627 (17)130
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y+1, −z+1; (iii) x, y−1, z; (iv) −x+2, −y, −z; (v) x, y+1, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC19H20N2O2C23H20N2O3
Mr308.37372.41
Crystal system, space groupMonoclinic, P21Triclinic, P1
Temperature (K)100100
a, b, c (Å)12.4525 (9), 5.7360 (4), 12.5896 (9)9.2014 (5), 9.4543 (7), 21.6201 (14)
α, β, γ (°)90, 116.081 (6), 9098.563 (4), 93.416 (4), 98.354 (4)
V (Å3)807.68 (11)1833.7 (2)
Z24
Radiation typeMo KαMo Kα
µ (mm−1)0.080.09
Crystal size (mm)0.28 × 0.05 × 0.010.10 × 0.06 × 0.06
Data collection
DiffractometerRigaku Mercury CCDRigaku Mercury CCD
Absorption correction––
No. of measured, independent and
observed [I > 2σ(I)] reflections		7830, 3498, 2259 24774, 8621, 6769
Rint0.1070.038
(sin θ/λ)max (Å−1)0.6490.668
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.081, 0.164, 1.12 0.046, 0.124, 1.03
No. of reflections34988621
No. of parameters213513
No. of restraints10
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.28, −0.240.62, −0.31

Computer programs: CrystalClear (Rigaku, 2012), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012), publCIF (Westrip, 2010).

 

Acknowledgements

We thank the EPSRC National Crystallography Service (University of Southampton) for the data collections and the EPSRC National Mass Spectrometry Service (University of Swansea) for the HRMS data.

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ISSN: 2056-9890
Volume 72| Part 5| May 2016| Pages 699-703
doi:10.1107/S2056989016006162
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