4-[2-(Benzyl­amino)­phen­yl]-2,6-dimethyl­quinoline N-oxide

Geffe, M.; Schollmeyer, D.; Detert, H.

doi:10.1107/S1600536812011002

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1106

doi:10.1107/S1600536812011002

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4-[2-(Benzylamino)phenyl]-2,6-dimethylquinoline N-oxide

Mario Geffe,^a Dieter Schollmeyer ^a and Heiner Detert ^a ^*

^aUniversity Mainz, Duesbergweg 10-14, 55099 Mainz, Germany
^*Correspondence e-mail: detert@uni-mainz.de

(Received 12 March 2012; accepted 13 March 2012; online 17 March 2012)

The title compound, C₂₄H₂₂N₂O, was obtained in a two-step procedure from the corresponding 4-(2-iodophenyl)quinoline. The quinoline system is approximately planar [maximum deviation from the least-squares plane = 0.021 (2) Å]. The planes of the quinoline system and the phenyl ring subtend a dihedral angle of 78.08 (8)°. In the crystal, pairs of molecules are connected via a center of symmetry and linked by a pair of angular N—H⋯O hydrogen bond. These dimers form columns oriented along the c axis.

Related literature

For aminations of iodolium salts, see: Letessier et al. (2011a ,b ), Letessier & Detert (2012 ). For quinoline N-oxides, see: Moreno-Fuquen et al. (2007 ); Ivashevskaja et al. (2002 ); Fahlquist et al. (2006 ). For heteroanalogous carbazoles, see: Dassonneville et al. (2010 , 2011 ); Nissen & Detert (2011 ). For Buchwald-Hartwig amination, see: Hartwig (1999 ); Muci & Buchwald (2002 ). For twist of o-substituted biaryls, see: Miao et al. (2009 ); Moschel et al. (2011 ).

Experimental

Crystal data

C₂₄H₂₂N₂O
M_r = 354.44
Monoclinic, P 2₁ /n
a = 10.1656 (3) Å
b = 14.1135 (5) Å
c = 12.9372 (4) Å
β = 91.547 (3)°
V = 1855.46 (11) Å³
Z = 4
Cu Kα radiation
μ = 0.61 mm⁻¹
T = 193 K
0.26 × 0.18 × 0.18 mm

Data collection

Stoe IPDS 2T diffractometer
18005 measured reflections
3120 independent reflections
2803 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.154
S = 1.10
3120 reflections
246 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N7—H7⋯O24ⁱ	0.96	2.03	2.7852 (17)	134
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: X-AREA (Stoe & Cie, 2011); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2011); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812011002/bt5844sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812011002/bt5844Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812011002/bt5844Isup3.cml

checkCIF report

Comment top

As part of a larger project on the synthesis of heteroanalogous carbazoles (Dassonneville et al. (2011), Dassonneville et al. (2010); Nissen & Detert (2011) iodolium salts became interesting as intermediates. Their twofold Buchwald-Hartwig amination with primary amines results in the formation of the pyrrole ring leading to carbazoles (Letessier et al. (2011a)) or carbolines (Letessier et al. (2011b), Letessier & Detert (2012)). The attempted formation of a benzo-quinolino-annulated iodolium salt via oxidation of the 4-(2-iodophenyl)quinoline and electrophilic ring closure failed. A mixture of two compounds, probably the iodosophenyl-quinoline and the iodophenyl-quinoline-N-oxide was obtained instead. Upon standing in chloroform solution, the former slowly isomerizes to the latter compound. Buchwald-Hartwig amination of the inseparable mixture with benzyl amine and Pd₂(dba)₃/Xantphos as catalytic system results in the formation of the title compound (ca 35%).

The title compound crystallizes as a centrosymmetric dimer stabilized by hydrogen bonding from the amino group to the N-oxide. The dimers are arranged in independent columns along the c axis. The bonds N7—H7 (0.9629 Å) and H7—O24 (2.03 Å) open an angle of 134°.

The quinoline framework is essentially planar with a maximal deviation of 0.021 (2) Å at C17 from the mean square plane. The dihedral angle between the mean planes of the quinoline and the adjacent phenyl ring is 64.61 (6)° and the mean planes of the phenyl rings open an angle of 78.08 (8)°. The amino group is coplanar with the mean plane of the phenyl ring: C8—N7-phenyl: 0.128 (2)°.

Related literature top

For aminations of iodolium salts, see: Letessier et al. (2011a,b), Letessier & Detert (2012). For quinoline N-oxides, see: Moreno-Fuquen et al. (2007); Ivashevskaja et al. (2002); Fahlquist et al. (2006). For heteroanalogous carbazoles, see: Dassonneville et al. (2010, 2011); Nissen & Detert (2011). For Buchwald-Hartwig amination, see: Hartwig (1999); Muci & Buchwald (2002). For torsion of o-substituted biaryls, see: Miao et al. (2009); Moschel et al. (2011).

Experimental top

2,6-Dimethyl-4-(2-iodophenyl)quinoline (53.9 mg, 0.15 mmol) was dissolved in 1.5 ml of dichloromethane in a flame-dried Schlenk tube and at 273 K. 11.6 µL(17.1 mg, 0.15 mmol) of trifluoromethane sulfonic acid were added. While stirring and cooling, mCPBA (38.8 mg, 0.23 mmol) was added. After 10 min trifluoromethansulfonic acid (23.3 µL, 34.2 mg, 0.3 mmol) was added and stirring continued for 30 min. The solvent was removed in vacuo, diethyl ether (5 ml) was added. An oily layer separated which crystallized upon standing for 8 h. The crystalline solid was isolated by suction filtration and washed with cold ether. Yield: 27.8 mg of a mixture of two compounds (ca 1: 0.6). In a Schlenk tube, this product (380 mg) was suspended in toluene (10 ml) and benzyl amine (96.4 mg, 0.9 mmol), Pd₂(dba)₃ (27.6 mg, 0.03 mmol), Xanthphos (52.2 mg, 0.09 mmol) and Cs₂CO₃ (684.3 mg, 2.1 mmol) were added. The mixture was stirred over night at 373 K, cooled, filtered through celite and the filter cake was washed with ethyl acetate (50 ml). The pooled organic solutions were washed with water, brine, and dried over MgSO₄. After removal of the solvents in vacuo, the residue was purified by chromatography on Al₂O₃ with gradient elution starting with petroleum ether, followed by ethyl acetate and finally methanol. yield: 124.2 mg (0.35 mmol) of the title compound (R_f = 0.68 SiO₂, ethyl acetate/methanol = 1/1) as yellow crystals with m. p. = 497 - 499 K. 4-(2-(Benzylamino)phenyl-2,6-dimethylquinoline (60 mg, 0.18 mmol, colorless solid, m. p. = 448 - 450 K) was isolated as a first fraction (R_f = 0.56 (SiO₂, petroleum ether/ethyl acetate = 1/1)

Structure description top

For aminations of iodolium salts, see: Letessier et al. (2011a,b), Letessier & Detert (2012). For quinoline N-oxides, see: Moreno-Fuquen et al. (2007); Ivashevskaja et al. (2002); Fahlquist et al. (2006). For heteroanalogous carbazoles, see: Dassonneville et al. (2010, 2011); Nissen & Detert (2011). For Buchwald-Hartwig amination, see: Hartwig (1999); Muci & Buchwald (2002). For torsion of o-substituted biaryls, see: Miao et al. (2009); Moschel et al. (2011).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2011); cell refinement: X-AREA (Stoe & Cie, 2011); data reduction: X-RED (Stoe & Cie, 2011); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

Fig. 1. View of compound I. Displacement ellipsoids are drawn at the 50% probability level.

4-[2-(Benzylamino)phenyl]-2,6-dimethylquinoline N-oxide top

Crystal data top

C₂₄H₂₂N₂O	F(000) = 752
M_r = 354.44	D_x = 1.269 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 449 K
Hall symbol: -P 2yn	Cu Kα radiation, λ = 1.54178 Å
a = 10.1656 (3) Å	Cell parameters from 27155 reflections
b = 14.1135 (5) Å	θ = 3.1–68.2°
c = 12.9372 (4) Å	µ = 0.61 mm⁻¹
β = 91.547 (3)°	T = 193 K
V = 1855.46 (11) Å³	Needle, yellow
Z = 4	0.26 × 0.18 × 0.18 mm

Data collection top

Stoe IPDS 2T diffractometer	2803 reflections with I > 2σ(I)
Radiation source: Incoatec microSource Cu	R_int = 0.034
X-ray mirror monochromator	θ_max = 66.5°, θ_min = 4.6°
Detector resolution: 6.67 pixels mm^-1	h = −12→12
rotation method scans	k = −16→16
18005 measured reflections	l = −13→13
3120 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.099P)² + 0.2406P] where P = (F_o² + 2F_c²)/3
3120 reflections	(Δ/σ)_max < 0.001
246 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₄H₂₂N₂O	V = 1855.46 (11) Å³
M_r = 354.44	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 10.1656 (3) Å	µ = 0.61 mm⁻¹
b = 14.1135 (5) Å	T = 193 K
c = 12.9372 (4) Å	0.26 × 0.18 × 0.18 mm
β = 91.547 (3)°

Data collection top

Stoe IPDS 2T diffractometer	2803 reflections with I > 2σ(I)
18005 measured reflections	R_int = 0.034
3120 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.154	H-atom parameters constrained
S = 1.10	Δρ_max = 0.17 e Å⁻³
3120 reflections	Δρ_min = −0.18 e Å⁻³
246 parameters

Special details top

Experimental. ¹H-NMR (400 MHz, CDCl₃): δ = 8.71 (d, ³J = 8.9 Hz, 1 H), 7.59 (dd, ³J = 8.9 Hz, 4 J = 1.7 Hz, 1 H), 7.43 (s, 1 H), 7.36 - 7.16 (m, 7 H), 7.11 (dd, 3 J = 7.4 Hz, ⁴J = 1.5 Hz, 1 H), 6.84 (t, ³J = 7.4 Hz, 1 H), 6.75 (d, ³J = 8.2 Hz, 1 H), 4.30 (s, 2 H, CH₂), 2.71 (s, 3 H, CH₃), 2.47 (s, 3 H, CH₃).

¹³C-NMR (75 MHz, CDCl₃): δ = 145.6, 144.0, 140.4, 139.7, 137.0, 133.4, 131.8, 130.3, 129.4, 128.3 (2 C), 128.0, 126.7 (2 C), 126.5, 125.5, 125.1, 121.8, 119.4, 115.7, 110.4, 45.9, 21.0, 18.2.

IR (ATR) ν = 3324, 3016, 2910, 2857, 1597, 1573, 1520, 1410, 1385, 1319, 1300, 1237, 1201, 1162, 1105, 982, 925, 872, 823, 795, 738, 699 cm^-1.

ESI-MS: 355.2 (M+H)⁺

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.71651 (14)	0.61537 (10)	0.20685 (11)	0.0467 (4)
C2	0.77995 (15)	0.65594 (11)	0.12222 (12)	0.0519 (4)
H2	0.7410	0.7089	0.0880	0.062*
C3	0.89744 (16)	0.62050 (12)	0.08793 (13)	0.0561 (4)
H3	0.9384	0.6496	0.0309	0.067*
C4	0.95605 (15)	0.54320 (12)	0.13561 (13)	0.0570 (4)
H4	1.0372	0.5190	0.1122	0.068*
C5	0.89426 (14)	0.50159 (11)	0.21827 (13)	0.0520 (4)
H5	0.9344	0.4485	0.2513	0.062*
C6	0.77536 (14)	0.53505 (10)	0.25443 (11)	0.0461 (4)
N7	0.60350 (13)	0.65335 (9)	0.24471 (10)	0.0533 (4)
H7	0.5685	0.6237	0.3051	0.064*
C8	0.53902 (15)	0.73596 (11)	0.20054 (12)	0.0533 (4)
H8A	0.6068	0.7844	0.1866	0.064*
H8B	0.4795	0.7627	0.2524	0.064*
C9	0.46014 (14)	0.71777 (10)	0.10157 (12)	0.0507 (4)
C10	0.46398 (16)	0.78089 (11)	0.01988 (13)	0.0572 (4)
H10	0.5201	0.8346	0.0249	0.069*
C11	0.38731 (18)	0.76708 (12)	−0.06926 (14)	0.0637 (5)
H11	0.3914	0.8110	−0.1247	0.076*
C12	0.30522 (17)	0.68959 (13)	−0.07725 (15)	0.0640 (5)
H12	0.2516	0.6805	−0.1377	0.077*
C13	0.30119 (17)	0.62530 (13)	0.00294 (16)	0.0660 (5)
H13	0.2456	0.5713	−0.0028	0.079*
C14	0.37786 (16)	0.63914 (12)	0.09166 (14)	0.0608 (4)
H14	0.3744	0.5945	0.1465	0.073*
C15	0.71631 (14)	0.48715 (10)	0.34537 (12)	0.0474 (4)
C15A	0.59375 (14)	0.43752 (10)	0.33858 (12)	0.0491 (4)
C16	0.51672 (14)	0.43056 (10)	0.24628 (13)	0.0520 (4)
H16	0.5461	0.4613	0.1858	0.062*
C17	0.40017 (15)	0.38053 (11)	0.24148 (15)	0.0596 (4)
C18	0.35773 (17)	0.33600 (13)	0.33235 (18)	0.0695 (5)
H18	0.2770	0.3020	0.3302	0.083*
C19	0.42868 (17)	0.34010 (12)	0.42324 (17)	0.0670 (5)
H19	0.3978	0.3092	0.4832	0.080*
C19A	0.54775 (15)	0.39039 (11)	0.42727 (13)	0.0549 (4)
N20	0.62225 (14)	0.39157 (10)	0.51958 (11)	0.0584 (4)
C21	0.73692 (17)	0.43875 (11)	0.52665 (13)	0.0567 (4)
C22	0.78247 (16)	0.48609 (11)	0.43914 (12)	0.0529 (4)
H22	0.8636	0.5192	0.4452	0.063*
C23	0.31976 (18)	0.37395 (14)	0.14289 (18)	0.0732 (5)
H23A	0.2438	0.4165	0.1465	0.110*
H23B	0.2890	0.3087	0.1330	0.110*
H23C	0.3739	0.3924	0.0846	0.110*
O24	0.57999 (13)	0.34483 (10)	0.59927 (10)	0.0755 (4)
C25	0.8079 (2)	0.43775 (15)	0.62843 (14)	0.0725 (5)
H25A	0.8872	0.4770	0.6248	0.109*
H25B	0.8328	0.3726	0.6462	0.109*
H25C	0.7505	0.4631	0.6815	0.109*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0483 (8)	0.0467 (8)	0.0453 (8)	−0.0049 (6)	0.0027 (6)	−0.0022 (6)
C2	0.0552 (8)	0.0504 (8)	0.0504 (9)	−0.0038 (6)	0.0054 (6)	0.0039 (6)
C3	0.0553 (9)	0.0606 (9)	0.0529 (9)	−0.0096 (7)	0.0093 (7)	0.0038 (7)
C4	0.0469 (8)	0.0643 (10)	0.0603 (10)	−0.0025 (7)	0.0106 (7)	0.0007 (7)
C5	0.0482 (8)	0.0514 (8)	0.0565 (9)	−0.0014 (6)	0.0029 (7)	0.0016 (6)
C6	0.0469 (7)	0.0450 (7)	0.0464 (8)	−0.0060 (6)	0.0025 (6)	−0.0020 (6)
N7	0.0584 (8)	0.0509 (7)	0.0513 (8)	0.0061 (5)	0.0123 (6)	0.0076 (5)
C8	0.0588 (9)	0.0458 (8)	0.0557 (9)	0.0033 (6)	0.0101 (7)	0.0010 (6)
C9	0.0492 (8)	0.0465 (8)	0.0569 (9)	0.0076 (6)	0.0108 (6)	0.0007 (6)
C10	0.0603 (9)	0.0472 (8)	0.0641 (10)	0.0020 (7)	0.0032 (7)	0.0051 (7)
C11	0.0701 (10)	0.0568 (9)	0.0638 (11)	0.0095 (8)	−0.0024 (8)	0.0065 (8)
C12	0.0578 (9)	0.0650 (10)	0.0688 (11)	0.0128 (8)	−0.0036 (8)	−0.0081 (8)
C13	0.0590 (10)	0.0599 (10)	0.0792 (12)	−0.0035 (7)	0.0018 (8)	−0.0045 (8)
C14	0.0603 (9)	0.0541 (9)	0.0683 (11)	−0.0014 (7)	0.0103 (8)	0.0060 (8)
C15	0.0491 (8)	0.0420 (7)	0.0513 (9)	0.0026 (6)	0.0068 (6)	0.0002 (6)
C15A	0.0494 (8)	0.0400 (7)	0.0584 (9)	0.0041 (6)	0.0122 (6)	0.0014 (6)
C16	0.0507 (8)	0.0435 (8)	0.0621 (10)	0.0006 (6)	0.0084 (7)	−0.0015 (6)
C17	0.0486 (8)	0.0467 (8)	0.0838 (12)	0.0007 (6)	0.0078 (8)	−0.0028 (7)
C18	0.0492 (9)	0.0546 (9)	0.1052 (16)	−0.0036 (7)	0.0162 (9)	0.0077 (9)
C19	0.0559 (9)	0.0568 (10)	0.0895 (13)	0.0044 (7)	0.0254 (9)	0.0170 (8)
C19A	0.0535 (8)	0.0469 (8)	0.0651 (11)	0.0093 (6)	0.0174 (7)	0.0074 (7)
N20	0.0649 (8)	0.0536 (8)	0.0578 (9)	0.0140 (6)	0.0227 (6)	0.0111 (6)
C21	0.0651 (9)	0.0525 (8)	0.0530 (10)	0.0118 (7)	0.0120 (7)	0.0027 (7)
C22	0.0574 (8)	0.0491 (8)	0.0523 (9)	0.0026 (6)	0.0052 (7)	0.0007 (6)
C23	0.0560 (10)	0.0622 (10)	0.1011 (15)	−0.0063 (8)	−0.0062 (9)	−0.0083 (9)
O24	0.0814 (8)	0.0774 (9)	0.0694 (9)	0.0177 (6)	0.0337 (7)	0.0280 (6)
C25	0.0907 (13)	0.0757 (12)	0.0512 (10)	0.0172 (10)	0.0075 (9)	0.0057 (8)

Geometric parameters (Å, º) top

C1—N7	1.370 (2)	C13—H13	0.9500
C1—C2	1.407 (2)	C14—H14	0.9500
C1—C6	1.415 (2)	C15—C22	1.371 (2)
C2—C3	1.379 (2)	C15—C15A	1.430 (2)
C2—H2	0.9500	C15A—C16	1.414 (2)
C3—C4	1.381 (2)	C15A—C19A	1.417 (2)
C3—H3	0.9500	C16—C17	1.379 (2)
C4—C5	1.385 (2)	C16—H16	0.9500
C4—H4	0.9500	C17—C18	1.411 (3)
C5—C6	1.390 (2)	C17—C23	1.499 (3)
C5—H5	0.9500	C18—C19	1.364 (3)
C6—C15	1.497 (2)	C18—H18	0.9500
N7—C8	1.448 (2)	C19—C19A	1.403 (2)
N7—H7	0.9629	C19—H19	0.9500
C8—C9	1.514 (2)	C19A—N20	1.397 (2)
C8—H8A	0.9900	N20—O24	1.3064 (17)
C8—H8B	0.9900	N20—C21	1.343 (2)
C9—C10	1.384 (2)	C21—C22	1.404 (2)
C9—C14	1.393 (2)	C21—C25	1.484 (3)
C10—C11	1.388 (2)	C22—H22	0.9500
C10—H10	0.9500	C23—H23A	0.9800
C11—C12	1.378 (3)	C23—H23B	0.9800
C11—H11	0.9500	C23—H23C	0.9800
C12—C13	1.380 (3)	C25—H25A	0.9800
C12—H12	0.9500	C25—H25B	0.9800
C13—C14	1.384 (3)	C25—H25C	0.9800

N7—C1—C2	121.68 (14)	C9—C14—H14	119.6
N7—C1—C6	120.44 (13)	C22—C15—C15A	117.05 (14)
C2—C1—C6	117.85 (13)	C22—C15—C6	120.19 (13)
C3—C2—C1	121.45 (15)	C15A—C15—C6	122.70 (14)
C3—C2—H2	119.3	C16—C15A—C19A	117.66 (14)
C1—C2—H2	119.3	C16—C15A—C15	123.22 (14)
C2—C3—C4	120.66 (15)	C19A—C15A—C15	119.10 (15)
C2—C3—H3	119.7	C17—C16—C15A	121.95 (15)
C4—C3—H3	119.7	C17—C16—H16	119.0
C3—C4—C5	118.73 (15)	C15A—C16—H16	119.0
C3—C4—H4	120.6	C16—C17—C18	118.18 (17)
C5—C4—H4	120.6	C16—C17—C23	121.20 (16)
C4—C5—C6	122.15 (15)	C18—C17—C23	120.62 (15)
C4—C5—H5	118.9	C19—C18—C17	122.21 (16)
C6—C5—H5	118.9	C19—C18—H18	118.9
C5—C6—C1	119.14 (13)	C17—C18—H18	118.9
C5—C6—C15	118.80 (13)	C18—C19—C19A	119.28 (17)
C1—C6—C15	122.01 (13)	C18—C19—H19	120.4
C1—N7—C8	123.31 (13)	C19A—C19—H19	120.4
C1—N7—H7	116.8	N20—C19A—C19	119.02 (15)
C8—N7—H7	119.8	N20—C19A—C15A	120.24 (14)
N7—C8—C9	114.90 (13)	C19—C19A—C15A	120.72 (17)
N7—C8—H8A	108.5	O24—N20—C21	119.97 (15)
C9—C8—H8A	108.5	O24—N20—C19A	119.11 (14)
N7—C8—H8B	108.5	C21—N20—C19A	120.91 (13)
C9—C8—H8B	108.5	N20—C21—C22	119.03 (15)
H8A—C8—H8B	107.5	N20—C21—C25	117.11 (15)
C10—C9—C14	118.15 (15)	C22—C21—C25	123.85 (16)
C10—C9—C8	120.76 (14)	C15—C22—C21	123.65 (15)
C14—C9—C8	121.04 (14)	C15—C22—H22	118.2
C9—C10—C11	121.16 (16)	C21—C22—H22	118.2
C9—C10—H10	119.4	C17—C23—H23A	109.5
C11—C10—H10	119.4	C17—C23—H23B	109.5
C12—C11—C10	119.94 (16)	H23A—C23—H23B	109.5
C12—C11—H11	120.0	C17—C23—H23C	109.5
C10—C11—H11	120.0	H23A—C23—H23C	109.5
C11—C12—C13	119.73 (16)	H23B—C23—H23C	109.5
C11—C12—H12	120.1	C21—C25—H25A	109.5
C13—C12—H12	120.1	C21—C25—H25B	109.5
C12—C13—C14	120.23 (16)	H25A—C25—H25B	109.5
C12—C13—H13	119.9	C21—C25—H25C	109.5
C14—C13—H13	119.9	H25A—C25—H25C	109.5
C13—C14—C9	120.79 (16)	H25B—C25—H25C	109.5
C13—C14—H14	119.6

N7—C1—C2—C3	176.45 (14)	C6—C15—C15A—C16	−1.0 (2)
C6—C1—C2—C3	−1.6 (2)	C22—C15—C15A—C19A	−0.2 (2)
C1—C2—C3—C4	0.5 (2)	C6—C15—C15A—C19A	177.09 (13)
C2—C3—C4—C5	0.3 (2)	C19A—C15A—C16—C17	0.5 (2)
C3—C4—C5—C6	0.1 (2)	C15—C15A—C16—C17	178.62 (14)
C4—C5—C6—C1	−1.3 (2)	C15A—C16—C17—C18	0.4 (2)
C4—C5—C6—C15	−178.91 (14)	C15A—C16—C17—C23	179.98 (14)
N7—C1—C6—C5	−176.09 (14)	C16—C17—C18—C19	−0.8 (3)
C2—C1—C6—C5	2.0 (2)	C23—C17—C18—C19	179.66 (16)
N7—C1—C6—C15	1.4 (2)	C17—C18—C19—C19A	0.2 (3)
C2—C1—C6—C15	179.53 (13)	C18—C19—C19A—N20	−177.79 (14)
C2—C1—N7—C8	1.3 (2)	C18—C19—C19A—C15A	0.7 (2)
C6—C1—N7—C8	179.29 (13)	C16—C15A—C19A—N20	177.44 (12)
C1—N7—C8—C9	77.05 (18)	C15—C15A—C19A—N20	−0.8 (2)
N7—C8—C9—C10	−138.41 (15)	C16—C15A—C19A—C19	−1.1 (2)
N7—C8—C9—C14	44.11 (19)	C15—C15A—C19A—C19	−179.29 (14)
C14—C9—C10—C11	0.6 (2)	C19—C19A—N20—O24	0.9 (2)
C8—C9—C10—C11	−176.96 (14)	C15A—C19A—N20—O24	−177.63 (13)
C9—C10—C11—C12	0.2 (2)	C19—C19A—N20—C21	179.90 (15)
C10—C11—C12—C13	−1.0 (3)	C15A—C19A—N20—C21	1.4 (2)
C11—C12—C13—C14	0.9 (3)	O24—N20—C21—C22	178.06 (13)
C12—C13—C14—C9	−0.0 (3)	C19A—N20—C21—C22	−0.9 (2)
C10—C9—C14—C13	−0.7 (2)	O24—N20—C21—C25	−2.3 (2)
C8—C9—C14—C13	176.86 (15)	C19A—N20—C21—C25	178.73 (13)
C5—C6—C15—C22	61.76 (19)	C15A—C15—C22—C21	0.6 (2)
C1—C6—C15—C22	−115.76 (16)	C6—C15—C22—C21	−176.72 (14)
C5—C6—C15—C15A	−115.43 (16)	N20—C21—C22—C15	−0.1 (2)
C1—C6—C15—C15A	67.05 (19)	C25—C21—C22—C15	−179.72 (15)
C22—C15—C15A—C16	−178.31 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7···O24ⁱ	0.96	2.03	2.7852 (17)	134

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₄H₂₂N₂O
M_r	354.44
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	193
a, b, c (Å)	10.1656 (3), 14.1135 (5), 12.9372 (4)
β (°)	91.547 (3)
V (Å³)	1855.46 (11)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.61
Crystal size (mm)	0.26 × 0.18 × 0.18

Data collection
Diffractometer	Stoe IPDS 2T
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	18005, 3120, 2803
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.154, 1.10
No. of reflections	3120
No. of parameters	246
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.18

Computer programs: X-AREA (Stoe & Cie, 2011), X-RED (Stoe & Cie, 2011), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7···O24ⁱ	0.96	2.03	2.7852 (17)	134

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The authors are grateful to Heinz Kolshorn for the NMR spectra and invaluable discussions.

References

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