2-(4-Meth­oxy­benz­yl)-4,6-diphenyl-2,5-diaza­bicyclo­[2.2.2]oct-5-en-3-one

Alen, J.; Dobrzańska, L.; Van Meervelt, L.; De Borggraeve, W.M.

doi:10.1107/S1600536811012165

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Pages o1070-o1071

doi:10.1107/S1600536811012165

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2-(4-Methoxybenzyl)-4,6-diphenyl-2,5-diazabicyclo[2.2.2]oct-5-en-3-one

Jo Alen,^a Liliana Dobrzańska,^a ^* Luc Van Meervelt ^b and Wim M. De Borggraeve ^a

^aMolecular Design & Synthesis, Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F – box 2404, B-3001 Leuven, Belgium, and ^bBiomolecular Architecture, Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F – box 2404, B-3001 Leuven, Belgium
^*Correspondence e-mail: lianger@chem.kuleuven.be

(Received 29 March 2011; accepted 31 March 2011; online 7 April 2011)

In the crystal structure of the title compound, C₂₆H₂₄N₂O₂, weak intermolecular C—H⋯π interactions involving the benzene of the p-methoxy benzyl group and one of the phenyl rings result in the formation of chains consisting of alternating enantiomers. Weak C—H ⋯O interactions with the methoxy O atom lead to the formation of layers, which are interlinked by further C—H⋯O interactions into a three-dimensional assembly.

Related literature

For our studies on pyrazinone chemistry, see: De Borggraeve et al. (2004 ); Azzam et al. (2004 ); Alen et al. (2007a ); Rombouts et al. (2003 ). For a crystal structure with a 2,5-diazabicyclo[2.2.2]oct-5-en-3-one core, see: Rusinov et al. (2009 ). For crystal structures with a similar 2,5-diazabicyclo[2.2.2]octane-3,6-dione core, see: Alen et al. (2007b ); Holl et al. (2008 ).

Experimental

Crystal data

C₂₆H₂₄N₂O₂
M_r = 396.47
Triclinic, $[P \overline 1]$
a = 6.2770 (1) Å
b = 11.5684 (2) Å
c = 14.1443 (2) Å
α = 85.497 (1)°
β = 89.900 (1)°
γ = 76.144 (1)°
V = 993.97 (3) Å³
Z = 2
Cu Kα radiation
μ = 0.67 mm⁻¹
T = 100 K
0.34 × 0.18 × 0.15 mm

Data collection

Bruker SMART 6000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.805, T_max = 0.907
10093 measured reflections
3473 independent reflections
2894 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.105
S = 1.05
3473 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C22–C27 and C9–C14 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯Cg2ⁱ	0.99	2.96	3.906 (2)	159
C21—H21A⋯Cg1ⁱⁱ	0.99	2.56	3.411 (2)	144
C19—H19⋯O28ⁱⁱⁱ	0.95	2.51	3.457 (2)	172
C13—H13⋯O30^iv	0.95	2.56	3.368 (2)	143
C29—H29A⋯O30^v	0.98	2.50	3.383 (2)	150
Symmetry codes: (i) -x, -y+1, -z+2; (ii) -x+1, -y+1, -z+1; (iii) -x+1, -y, -z+1; (iv) x-1, y, z; (v) -x, -y+1, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2002 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012165/hg5019sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811012165/hg5019Isup2.hkl

checkCIF report

Comment top

During the course of our studies on 3,5-dichloropyrazinones (Azzam et al., 2004; Alen et al., 2007a) and their conversion to aminopiperidinone carboxylate systems (Rombouts et al., 2003; De Borggraeve et al., 2004), we have isolated the title compound. Although quite a few studies deal with bicyclo[2.2.2]octane systems, only one structure with the 2,5-diazabicyclo[2.2.2]oct-5-en-3-one core (Rusinov et al., 2009) has been reported till now. Quite a few structures contain the similar 2,5-diazabicyclo[2.2.2]octane-3,6-dione core. Of those, two have very close resemblance to the title molecule due to a benzyl substituent on N4. One of those was obtained by us (Alen et al., 2007b) and the other one was published by Wünsch and co-workers (Holl et al., 2008).

The presented structure crystallizes in the triclinic space group P1 with one molecule in the asymmetric unit (Fig. 1). All three aromatic rings participate in weak C—H···π interactions, acting as a donor (C15–C20) or acceptors (C9–C14 and C22–C27). Intramolecular interactions C20—H20···Cg1, (where Cg1 is the centroid of the C22–C27 ring; the C20···Cg1 distance is 3.790 (2) Å, and the C20—H20···Cg1 angle is 149°) influence the orientation of these two rings towards each other. The dihedral angle between their planes is 52.75 (4)°. Rings C9–C14 and C22–C27, with dihedral angles 12.77 (9)° between their corresponding planes and -117.75 (1)° between C9–C4–C21–C22, are involved in weak intermolecular C—H···π interactions. These interactions, namely C8—H8A···Cg2ⁱ (where Cg2 is the centroid of C9–C14, the C8···Cg2 distance is 3.906 (2) Å; symmetry operation (i): -x,1 - y,2 - z) and C21—H21A···Cg1ⁱⁱ (the C21···Cg1 distance is 3.411 (2) Å; symmetry code (ii): 1 - x,1 - y,1 - z), lead to the formation of chains of alternating enantiomers along [-1 0 1] (Fig. 2).These chains are interlinked by C19—H19···O28 interactions to form layers, which are expanded in the third dimension through a number of C—H···O interactions involving O30 (Fig. 3, Table 1).

Related literature top

For our studies on pyrazinone chemistry, see: De Borggraeve et al. (2004); Azzam et al. (2004); Alen et al. (2007a); Rombouts et al. (2003). For a crystal structure with a 2,5-diazabicyclo[2.2.2]oct-5-en-3-one core, see: Rusinov et al. (2009). For crystal structures with a similar 2,5-diazabicyclo[2.2.2]octane-3,6-dione core, see: Alen et al. (2007b); Holl et al. (2008).

Experimental top

1-(4-methoxybenzyl)-3,5-diphenylpyrazin-2(1H)-one (5 mmol) was dissolved in toluene and heated at 145 °C in a stainless steel bomb under ethene pressure (35 atm) for 4 h. The progress of the Diels-Alder cycloaddition was monitored on TLC, by the disappearance of the starting pyrazinone. After evaporation of the solvent, the crude residue was purified by column chromatography to yield the title compound. Single crystals suitable for X-ray diffraction were obtained by slow evaporation from a chloroform solution.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule; displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Fragment of the chain formed by C—H···π interactions; red centroids derive from C22–C27 ring (Cg1), blue from C9–C14 (Cg2).
	Fig. 3. Representation of the packing viewed down the a axis; weak C19—H19···O28 interactions facilitating the formation of layers are indicated by blue dashed lines; C13—H13···O30 and C29—H29A···O30 interactions stabilizing the three-dimensional assembly are presented in orange. Symmetry codes are listed in Table 1.

2-(4-Methoxybenzyl)-4,6-diphenyl-2,5-diazabicyclo[2.2.2]oct-5-en-3-one top

Crystal data top

C₂₆H₂₄N₂O₂	Z = 2
M_r = 396.47	F(000) = 420
Triclinic, P1	D_x = 1.325 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 6.2770 (1) Å	Cell parameters from 3657 reflections
b = 11.5684 (2) Å	θ = 4.0–68.4°
c = 14.1443 (2) Å	µ = 0.67 mm⁻¹
α = 85.497 (1)°	T = 100 K
β = 89.900 (1)°	Block, colorless
γ = 76.144 (1)°	0.34 × 0.18 × 0.15 mm
V = 993.97 (3) Å³

Data collection top

Bruker SMART 6000 diffractometer	3473 independent reflections
Radiation source: fine-focus sealed tube	2894 reflections with I > 2σ(I)
Crossed Göbel mirrors monochromator	R_int = 0.028
ω and ϕ scans	θ_max = 68.5°, θ_min = 4.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −7→7
T_min = 0.805, T_max = 0.907	k = −13→13
10093 measured reflections	l = −16→16

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0591P)² + 0.2042P] where P = (F_o² + 2F_c²)/3
3473 reflections	(Δ/σ)_max < 0.001
272 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₂₆H₂₄N₂O₂	γ = 76.144 (1)°
M_r = 396.47	V = 993.97 (3) Å³
Triclinic, P1	Z = 2
a = 6.2770 (1) Å	Cu Kα radiation
b = 11.5684 (2) Å	µ = 0.67 mm⁻¹
c = 14.1443 (2) Å	T = 100 K
α = 85.497 (1)°	0.34 × 0.18 × 0.15 mm
β = 89.900 (1)°

Data collection top

Bruker SMART 6000 diffractometer	3473 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	2894 reflections with I > 2σ(I)
T_min = 0.805, T_max = 0.907	R_int = 0.028
10093 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.05	Δρ_max = 0.25 e Å⁻³
3473 reflections	Δρ_min = −0.27 e Å⁻³
272 parameters

Special details top

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	0.3365 (2)	0.39618 (12)	0.79614 (10)	0.0184 (3)
H1	0.4452	0.3253	0.7747	0.022*
N2	0.30988 (19)	0.50050 (10)	0.72762 (8)	0.0182 (3)
C3	0.1528 (2)	0.59721 (12)	0.74710 (9)	0.0169 (3)
C4	0.0393 (2)	0.57044 (12)	0.84081 (9)	0.0162 (3)
N5	−0.04137 (19)	0.46034 (10)	0.83215 (8)	0.0167 (3)
C6	0.1113 (2)	0.37223 (12)	0.80940 (9)	0.0167 (3)
C7	0.2259 (2)	0.54041 (12)	0.91838 (9)	0.0181 (3)
H7B	0.2907	0.6099	0.9226	0.022*
H7A	0.1645	0.5227	0.9809	0.022*
C8	0.4036 (2)	0.43205 (13)	0.89272 (10)	0.0195 (3)
H8A	0.4150	0.3651	0.9420	0.023*
H8B	0.5477	0.4527	0.8881	0.023*
C9	−0.1499 (2)	0.67346 (12)	0.86188 (10)	0.0170 (3)
C10	−0.1369 (3)	0.74953 (13)	0.93157 (10)	0.0242 (3)
H10	−0.0042	0.7384	0.9670	0.029*
C11	−0.3152 (3)	0.84182 (13)	0.95039 (11)	0.0278 (4)
H11	−0.3041	0.8920	0.9992	0.033*
C12	−0.5084 (3)	0.86085 (13)	0.89838 (11)	0.0252 (3)
H12	−0.6301	0.9239	0.9113	0.030*
C13	−0.5227 (2)	0.78717 (13)	0.82731 (11)	0.0252 (3)
H13	−0.6542	0.8000	0.7907	0.030*
C14	−0.3449 (2)	0.69462 (12)	0.80964 (11)	0.0219 (3)
H14	−0.3566	0.6445	0.7608	0.026*
C15	0.0681 (2)	0.25323 (12)	0.79874 (10)	0.0184 (3)
C16	−0.1056 (2)	0.22043 (12)	0.84705 (10)	0.0200 (3)
H16	−0.1934	0.2741	0.8872	0.024*
C17	−0.1512 (2)	0.11049 (13)	0.83698 (11)	0.0256 (3)
H17	−0.2689	0.0889	0.8705	0.031*
C18	−0.0242 (3)	0.03196 (13)	0.77777 (12)	0.0282 (4)
H18	−0.0539	−0.0439	0.7714	0.034*
C19	0.1452 (3)	0.06430 (13)	0.72808 (11)	0.0273 (4)
H19	0.2291	0.0116	0.6862	0.033*
C20	0.1933 (2)	0.17386 (13)	0.73923 (10)	0.0230 (3)
H20	0.3122	0.1947	0.7061	0.028*
C21	0.4620 (2)	0.49909 (13)	0.64896 (10)	0.0200 (3)
H21B	0.6110	0.4935	0.6746	0.024*
H21A	0.4168	0.5750	0.6086	0.024*
C22	0.4685 (2)	0.39600 (12)	0.58928 (9)	0.0185 (3)
C23	0.2800 (2)	0.38246 (12)	0.54412 (10)	0.0200 (3)
H23	0.1450	0.4391	0.5516	0.024*
C24	0.2841 (2)	0.28809 (12)	0.48822 (10)	0.0206 (3)
H24	0.1534	0.2800	0.4584	0.025*
C25	0.4826 (2)	0.20556 (12)	0.47653 (10)	0.0204 (3)
C26	0.6727 (2)	0.21824 (13)	0.52098 (10)	0.0215 (3)
H26	0.8082	0.1624	0.5128	0.026*
C27	0.6647 (2)	0.31205 (13)	0.57704 (10)	0.0204 (3)
H27	0.7950	0.3193	0.6076	0.024*
O28	0.50771 (17)	0.10994 (9)	0.42322 (7)	0.0259 (3)
C29	0.3127 (3)	0.08362 (14)	0.38884 (12)	0.0289 (4)
H29B	0.2193	0.0710	0.4424	0.043*
H29C	0.3514	0.0112	0.3547	0.043*
H29A	0.2334	0.1506	0.3458	0.043*
O30	0.10832 (16)	0.69324 (8)	0.69944 (7)	0.0208 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0169 (7)	0.0183 (7)	0.0186 (7)	−0.0017 (5)	0.0005 (5)	−0.0013 (5)
N2	0.0193 (6)	0.0193 (6)	0.0159 (6)	−0.0043 (5)	0.0026 (5)	−0.0015 (5)
C3	0.0166 (7)	0.0202 (7)	0.0155 (7)	−0.0064 (5)	−0.0013 (5)	−0.0041 (5)
C4	0.0177 (7)	0.0169 (7)	0.0151 (7)	−0.0060 (5)	−0.0002 (5)	−0.0025 (5)
N5	0.0178 (6)	0.0171 (6)	0.0156 (6)	−0.0047 (5)	−0.0003 (4)	−0.0018 (4)
C6	0.0178 (7)	0.0186 (7)	0.0126 (6)	−0.0026 (5)	−0.0012 (5)	0.0002 (5)
C7	0.0174 (7)	0.0235 (7)	0.0142 (7)	−0.0069 (6)	−0.0005 (5)	−0.0010 (5)
C8	0.0170 (8)	0.0245 (7)	0.0169 (7)	−0.0054 (6)	−0.0006 (5)	0.0002 (6)
C9	0.0189 (8)	0.0159 (7)	0.0171 (7)	−0.0065 (5)	0.0026 (5)	0.0001 (5)
C10	0.0262 (8)	0.0232 (8)	0.0229 (8)	−0.0042 (6)	−0.0026 (6)	−0.0045 (6)
C11	0.0383 (10)	0.0211 (8)	0.0228 (8)	−0.0030 (6)	−0.0013 (7)	−0.0077 (6)
C12	0.0263 (8)	0.0164 (7)	0.0304 (8)	−0.0001 (6)	0.0059 (6)	−0.0030 (6)
C13	0.0192 (8)	0.0201 (7)	0.0363 (9)	−0.0044 (6)	−0.0024 (6)	−0.0030 (6)
C14	0.0225 (8)	0.0173 (7)	0.0268 (8)	−0.0049 (6)	−0.0013 (6)	−0.0070 (6)
C15	0.0187 (8)	0.0172 (7)	0.0177 (7)	−0.0015 (5)	−0.0055 (5)	−0.0004 (5)
C16	0.0176 (8)	0.0190 (7)	0.0225 (7)	−0.0023 (5)	−0.0050 (5)	−0.0021 (6)
C17	0.0198 (8)	0.0238 (8)	0.0333 (8)	−0.0064 (6)	−0.0054 (6)	0.0003 (6)
C18	0.0304 (9)	0.0172 (7)	0.0365 (9)	−0.0043 (6)	−0.0121 (7)	−0.0033 (6)
C19	0.0312 (9)	0.0199 (7)	0.0274 (8)	0.0024 (6)	−0.0051 (6)	−0.0074 (6)
C20	0.0232 (8)	0.0208 (7)	0.0225 (7)	−0.0004 (6)	−0.0017 (6)	−0.0013 (6)
C21	0.0198 (8)	0.0227 (7)	0.0189 (7)	−0.0074 (6)	0.0040 (5)	−0.0034 (6)
C22	0.0214 (8)	0.0212 (7)	0.0140 (7)	−0.0074 (6)	0.0023 (5)	0.0002 (5)
C23	0.0190 (8)	0.0207 (7)	0.0196 (7)	−0.0034 (6)	0.0018 (5)	−0.0006 (6)
C24	0.0209 (8)	0.0230 (7)	0.0193 (7)	−0.0082 (6)	−0.0012 (6)	−0.0005 (6)
C25	0.0268 (8)	0.0184 (7)	0.0171 (7)	−0.0075 (6)	0.0019 (6)	−0.0020 (5)
C26	0.0192 (8)	0.0205 (7)	0.0235 (7)	−0.0021 (6)	0.0019 (6)	−0.0026 (6)
C27	0.0187 (8)	0.0239 (7)	0.0192 (7)	−0.0069 (6)	−0.0007 (5)	−0.0008 (6)
O28	0.0269 (6)	0.0229 (5)	0.0293 (6)	−0.0059 (4)	−0.0015 (4)	−0.0096 (4)
C29	0.0319 (9)	0.0225 (8)	0.0340 (9)	−0.0083 (7)	−0.0084 (7)	−0.0067 (7)
O30	0.0241 (6)	0.0189 (5)	0.0191 (5)	−0.0053 (4)	0.0002 (4)	0.0013 (4)

Geometric parameters (Å, º) top

C1—N2	1.4641 (18)	C15—C20	1.394 (2)
C1—C6	1.5129 (19)	C15—C16	1.398 (2)
C1—C8	1.5460 (18)	C16—C17	1.386 (2)
C1—H1	1.0000	C16—H16	0.9500
N2—C3	1.3485 (18)	C17—C18	1.390 (2)
N2—C21	1.4633 (17)	C17—H17	0.9500
C3—O30	1.2252 (17)	C18—C19	1.383 (2)
C3—C4	1.5489 (19)	C18—H18	0.9500
C4—N5	1.4922 (17)	C19—C20	1.392 (2)
C4—C9	1.5149 (19)	C19—H19	0.9500
C4—C7	1.5641 (18)	C20—H20	0.9500
N5—C6	1.2820 (18)	C21—C22	1.5070 (19)
C6—C15	1.4843 (19)	C21—H21B	0.9900
C7—C8	1.5322 (19)	C21—H21A	0.9900
C7—H7B	0.9900	C22—C23	1.393 (2)
C7—H7A	0.9900	C22—C27	1.394 (2)
C8—H8A	0.9900	C23—C24	1.393 (2)
C8—H8B	0.9900	C23—H23	0.9500
C9—C10	1.387 (2)	C24—C25	1.395 (2)
C9—C14	1.391 (2)	C24—H24	0.9500
C10—C11	1.391 (2)	C25—O28	1.3653 (17)
C10—H10	0.9500	C25—C26	1.393 (2)
C11—C12	1.382 (2)	C26—C27	1.385 (2)
C11—H11	0.9500	C26—H26	0.9500
C12—C13	1.384 (2)	C27—H27	0.9500
C12—H12	0.9500	O28—C29	1.4250 (18)
C13—C14	1.387 (2)	C29—H29B	0.9800
C13—H13	0.9500	C29—H29C	0.9800
C14—H14	0.9500	C29—H29A	0.9800

N2—C1—C6	106.68 (11)	C9—C14—H14	119.3
N2—C1—C8	107.79 (11)	C20—C15—C16	118.74 (13)
C6—C1—C8	106.12 (11)	C20—C15—C6	121.48 (13)
N2—C1—H1	112.0	C16—C15—C6	119.75 (12)
C6—C1—H1	112.0	C17—C16—C15	120.75 (14)
C8—C1—H1	112.0	C17—C16—H16	119.6
C3—N2—C21	123.95 (12)	C15—C16—H16	119.6
C3—N2—C1	115.85 (11)	C16—C17—C18	119.89 (15)
C21—N2—C1	119.96 (11)	C16—C17—H17	120.1
O30—C3—N2	125.58 (12)	C18—C17—H17	120.1
O30—C3—C4	124.51 (12)	C19—C18—C17	119.93 (14)
N2—C3—C4	109.89 (11)	C19—C18—H18	120.0
N5—C4—C9	110.11 (11)	C17—C18—H18	120.0
N5—C4—C3	108.07 (10)	C18—C19—C20	120.23 (14)
C9—C4—C3	111.77 (11)	C18—C19—H19	119.9
N5—C4—C7	107.65 (10)	C20—C19—H19	119.9
C9—C4—C7	113.68 (11)	C19—C20—C15	120.42 (15)
C3—C4—C7	105.25 (11)	C19—C20—H20	119.8
C6—N5—C4	112.30 (11)	C15—C20—H20	119.8
N5—C6—C15	121.31 (12)	N2—C21—C22	112.07 (11)
N5—C6—C1	116.26 (12)	N2—C21—H21B	109.2
C15—C6—C1	122.43 (12)	C22—C21—H21B	109.2
C8—C7—C4	109.57 (11)	N2—C21—H21A	109.2
C8—C7—H7B	109.8	C22—C21—H21A	109.2
C4—C7—H7B	109.8	H21B—C21—H21A	107.9
C8—C7—H7A	109.8	C23—C22—C27	118.15 (13)
C4—C7—H7A	109.8	C23—C22—C21	121.17 (12)
H7B—C7—H7A	108.2	C27—C22—C21	120.68 (12)
C7—C8—C1	107.33 (11)	C24—C23—C22	121.73 (13)
C7—C8—H8A	110.2	C24—C23—H23	119.1
C1—C8—H8A	110.2	C22—C23—H23	119.1
C7—C8—H8B	110.2	C23—C24—C25	119.11 (13)
C1—C8—H8B	110.2	C23—C24—H24	120.4
H8A—C8—H8B	108.5	C25—C24—H24	120.4
C10—C9—C14	117.80 (13)	O28—C25—C26	115.66 (13)
C10—C9—C4	122.53 (13)	O28—C25—C24	124.54 (13)
C14—C9—C4	119.66 (12)	C26—C25—C24	119.80 (13)
C9—C10—C11	121.05 (14)	C27—C26—C25	120.19 (13)
C9—C10—H10	119.5	C27—C26—H26	119.9
C11—C10—H10	119.5	C25—C26—H26	119.9
C12—C11—C10	120.35 (14)	C26—C27—C22	121.01 (13)
C12—C11—H11	119.8	C26—C27—H27	119.5
C10—C11—H11	119.8	C22—C27—H27	119.5
C11—C12—C13	119.34 (14)	C25—O28—C29	117.06 (11)
C11—C12—H12	120.3	O28—C29—H29B	109.5
C13—C12—H12	120.3	O28—C29—H29C	109.5
C12—C13—C14	119.95 (14)	H29B—C29—H29C	109.5
C12—C13—H13	120.0	O28—C29—H29A	109.5
C14—C13—H13	120.0	H29B—C29—H29A	109.5
C13—C14—C9	121.49 (13)	H29C—C29—H29A	109.5
C13—C14—H14	119.3

C6—C1—N2—C3	51.84 (15)	C4—C9—C10—C11	−178.69 (13)
C8—C1—N2—C3	−61.78 (15)	C9—C10—C11—C12	−1.2 (2)
C6—C1—N2—C21	−133.60 (12)	C10—C11—C12—C13	0.0 (2)
C8—C1—N2—C21	112.78 (13)	C11—C12—C13—C14	0.7 (2)
C21—N2—C3—O30	4.4 (2)	C12—C13—C14—C9	−0.1 (2)
C1—N2—C3—O30	178.72 (12)	C10—C9—C14—C13	−1.1 (2)
C21—N2—C3—C4	−174.13 (11)	C4—C9—C14—C13	179.33 (13)
C1—N2—C3—C4	0.19 (16)	N5—C6—C15—C20	153.12 (13)
O30—C3—C4—N5	126.98 (13)	C1—C6—C15—C20	−28.10 (19)
N2—C3—C4—N5	−54.46 (14)	N5—C6—C15—C16	−25.04 (19)
O30—C3—C4—C9	5.66 (18)	C1—C6—C15—C16	153.74 (13)
N2—C3—C4—C9	−175.79 (11)	C20—C15—C16—C17	0.8 (2)
O30—C3—C4—C7	−118.21 (14)	C6—C15—C16—C17	178.97 (13)
N2—C3—C4—C7	60.35 (13)	C15—C16—C17—C18	−0.4 (2)
C9—C4—N5—C6	176.59 (11)	C16—C17—C18—C19	−0.9 (2)
C3—C4—N5—C6	54.24 (14)	C17—C18—C19—C20	1.9 (2)
C7—C4—N5—C6	−58.98 (14)	C18—C19—C20—C15	−1.5 (2)
C4—N5—C6—C15	178.84 (11)	C16—C15—C20—C19	0.2 (2)
C4—N5—C6—C1	−0.01 (16)	C6—C15—C20—C19	−177.95 (13)
N2—C1—C6—N5	−53.75 (15)	C3—N2—C21—C22	−129.16 (13)
C8—C1—C6—N5	61.00 (15)	C1—N2—C21—C22	56.75 (16)
N2—C1—C6—C15	127.41 (13)	N2—C21—C22—C23	59.17 (17)
C8—C1—C6—C15	−117.83 (13)	N2—C21—C22—C27	−121.48 (14)
N5—C4—C7—C8	55.29 (14)	C27—C22—C23—C24	0.2 (2)
C9—C4—C7—C8	177.54 (11)	C21—C22—C23—C24	179.53 (12)
C3—C4—C7—C8	−59.81 (13)	C22—C23—C24—C25	−0.5 (2)
C4—C7—C8—C1	2.67 (14)	C23—C24—C25—O28	−179.64 (13)
N2—C1—C8—C7	56.69 (14)	C23—C24—C25—C26	0.3 (2)
C6—C1—C8—C7	−57.31 (13)	O28—C25—C26—C27	−179.72 (12)
N5—C4—C9—C10	134.06 (13)	C24—C25—C26—C27	0.3 (2)
C3—C4—C9—C10	−105.81 (15)	C25—C26—C27—C22	−0.7 (2)
C7—C4—C9—C10	13.18 (18)	C23—C22—C27—C26	0.5 (2)
N5—C4—C9—C14	−46.41 (16)	C21—C22—C27—C26	−178.88 (13)
C3—C4—C9—C14	73.72 (15)	C26—C25—O28—C29	170.61 (13)
C7—C4—C9—C14	−167.29 (12)	C24—C25—O28—C29	−9.5 (2)
C14—C9—C10—C11	1.8 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C22–C27 and C9–C14 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···O28ⁱ	0.95	2.51	3.457 (2)	172
C13—H13···O30ⁱⁱ	0.95	2.56	3.368 (2)	143
C29—H29A···O30ⁱⁱⁱ	0.98	2.50	3.383 (2)	150
C8—H8A···Cg2^iv	0.99	2.96	3.906 (2)	159
C21—H21A···Cg1^v	0.99	2.56	3.411 (2)	144

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

Experimental details

Crystal data
Chemical formula	C₂₆H₂₄N₂O₂
M_r	396.47
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.2770 (1), 11.5684 (2), 14.1443 (2)
α, β, γ (°)	85.497 (1), 89.900 (1), 76.144 (1)
V (Å³)	993.97 (3)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.67
Crystal size (mm)	0.34 × 0.18 × 0.15

Data collection
Diffractometer	Bruker SMART 6000 diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.805, 0.907
No. of measured, independent and observed [I > 2σ(I)] reflections	10093, 3473, 2894
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.105, 1.05
No. of reflections	3473
No. of parameters	272
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.27

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C22–C27 and C9–C14 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···O28ⁱ	0.95	2.51	3.457 (2)	172
C13—H13···O30ⁱⁱ	0.95	2.56	3.368 (2)	143
C29—H29A···O30ⁱⁱⁱ	0.98	2.50	3.383 (2)	150
C8—H8A···Cg2^iv	0.99	2.96	3.906 (2)	159
C21—H21A···Cg1^v	0.99	2.56	3.411 (2)	144

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

Acknowledgements

The authors thank the Fonds Wetenschappelijk Onderzoek – Vlaanderen (FWO) for financial support.

References

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Volume 67| Part 5| May 2011| Pages o1070-o1071

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