3-Nitroso-2,4,6,8-tetra­phenyl-3,7-diaza­bicyclo­[3.3.1]nonan-9-one

Natarajan, S.; Mathews, R.

doi:10.1107/S1600536811022203

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1686

doi:10.1107/S1600536811022203

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3-Nitroso-2,4,6,8-tetraphenyl-3,7-diazabicyclo[3.3.1]nonan-9-one

Sampath Natarajan ^a ^* and Rita Mathews ^a

^aDepartment of Advanced Technology Fusion, Konkuk University, 1 Hwayang-dong, Gwangjin-gu, Seoul 143 701, Republic of Korea
^*Correspondence e-mail: sampath@konkuk.ac.kr

(Received 11 April 2011; accepted 8 June 2011; online 18 June 2011)

In the title compound, C₃₁H₂₇N₃O₂, the two piperidine rings fused to each other each adopt a slightly distorted chair conformation. The phenyl rings on the N-unsubstituted piperidine ring occupy an equatorial position, while those on the N-nitroso-substituted piperidine ring are in axial positions. The NO group is approximately coplanar with the piperidine ring with a maximum deviation of 0.048 (4) Å. The dihedral angles between the mean planes of the axially and equatorially oriented phenyl rings are 27.7 (1) and 31.9 (1)°, respectively. Molecular packing is stabilized by weak intermolecular C—H⋯O and C—H⋯π interactions.

Related literature

For piperidine ring conformations, see: Hofer (1976 ); Ramalingam et al. (1979 ); Mulekar & Berlin (1989 ); Pandiarajan et al. (1991 ); Rogers & Woodbrey (1962 ). For related structures, see: Hemalatha & Nagarajan (2010 ); Sampath et al. (2005 ). For puckering parameters, see: Cremer & Pople (1975 ). For the synthesis of the title compound, see: Noller & Baliah (1948 ).

Experimental

Crystal data

C₃₁H₂₇N₃O₂
M_r = 473.56
Monoclinic, P 2₁ /c
a = 18.723 (4) Å
b = 8.8319 (17) Å
c = 15.806 (3) Å
β = 104.728 (3)°
V = 2527.8 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.26 × 0.23 × 0.21 mm

Data collection

Bruker SMART APEX CCD diffractometer
19483 measured reflections
5385 independent reflections
3235 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.081
wR(F²) = 0.187
S = 1.06
5385 reflections
334 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C31–C36 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18—H18⋯O3	0.93	2.94	3.607 (1)	130
C20—H20⋯O1	0.93	2.79	3.622 (4)	150
C24—H24⋯O2	0.93	2.64	3.276 (5)	126
C36—H36⋯O3	0.93	2.80	3.415 (9)	125
C17—H17⋯O1ⁱ	0.93	2.66	3.311 (4)	128
C22—H22⋯O1ⁱⁱ	0.93	2.74	3.579 (5)	150
C32—H32⋯O2ⁱⁱⁱ	0.93	2.43	3.127 (6)	132
C34—H34⋯O3^iv	0.93	2.24	2.878 (1)	125
C29—H29⋯Cg1^v	0.93	2.87	3.677	146
Symmetry codes: (i) x, y-1, z; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -z+1; (v) $[x, -y+{\script{1\over 2}}, z-{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811022203/jj2089sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811022203/jj2089Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811022203/jj2089Isup3.cml

checkCIF report

Comment top

The piperidine ring system offers a wide variety of conformational flexibility such as chair, boat and twisted boat conformations (Hofer, 1976). However, both the chair and slightly distorted chair conformations are found to be the most favored (Ramalingam et al., 1979; Mulekar & Berlin, 1989). N-nitroso piperidine compounds have been shown to occupy both axial and equatorial positions with the mean plane of the N—NO₂ group being coplanar to the mean plane of the piperidine ring (Hemalatha & Nagarajan, 2010; Sampath et al., 2005). The phenyl rings tend to occupy equatorial positions when the N—NO₂ group orients itself perpendicular to the piperidine ring to avoid steric hindrance. π-electron delocalization on the N—N—O group, which restricts the free rotation of N—N bond, results in orientations that are planar (syn; Pandiarajan et al., 1991) or perpendicular (anti; Rogers & Woodbrey, 1962) with respect to the piperidine ring. In 2,6-diphenyl-3-methyl-N-nitrosopiperidin- 4-one (Hemalatha & Nagarajan, 2010) the nitroso group shows both syn and anti conformations while the piperidine ring displays a boat conformation which may influence the phenyl rings to occupy axial and equitorial positions with respect to the piperidine ring.

In the title compound both piperidine rings adopt a slightly distorted chair conformation (Cremer & Pople, 1975) with puckering parameters parameters Q, θ and ϕ of 0.538 (3) Å, 18.0 (3)°, 142.8 (1)° [N-substituted piperidine ring (N1/C2/C8/C9/C7/C6)] and 0.657 (2) Å, 173.2 (3)° and 51.0 (2)° [N-free piperidine ring (N4/C5/C7/C9/C8/C3)], respectively (Fig. 1). For an ideal chair θ has a value of 0 or 180°. In the N-substituted piperidine ring (N1/C2/C8/C9/C7/C6) the N atom displays sp² hybridization, as evidenced by sum of angles around the N1 atom being nearly equal to 360° [C2/N1/C6 = 122.0 (2)°, C2/N1/N2 = 123.2 (3)° and C6/N1/N2 = 114.8 (3)°]}.

Phenyl rings C13–C18 and C19–C24 are substituted axially in the N—NO₂ piperidine ring. Torsion angles for phenyl ring C13–C18 {C6/N1/C2/C13 = 79.7 (3)°; C9/C8/C2/C13 = -69.2 (3)°} and for phenyl ring C19–C24 [C2/N1/C6/C19 = -88.8 (3)°; C9/C7/C6/C19 = 84.1 (3)°}] support this observation. The dihedral angle between these phenyl rings is 27.7 (1)°. Phenyl rings C25–C30 and C31–C36 are oriented equatorially to the piperidine ring. Torsion angles for phenyl ring C25–C30 [C3/N4/C5/C25 = 172.9 (2)°, C9/C7/C5/C25 = -171.7 (2)°] and C31–C36 [C9/C8/C3/C31 = 178.8 (2)°, C5/N4/C3/C31 = -176.2 (2)°] support this observation. The dihedral angle between these phenyl rings is 31.9 (1)°. Molecular packing is stabilized by weak C—H···O intra and intermolecular interactions and weak C—H···π intermolecular interactions (Table 1, Fig. 2).

Related literature top

For piperidine ring conformations, see: Hofer (1976); Ramalingam et al. (1979); Mulekar & Berlin (1989); Pandiarajan et al. (1991); Rogers & Woodbrey (1962). For related structures, see: Hemalatha & Nagarajan (2010); Sampath et al. (2005). For puckering parameters, see: Cremer & Pople (1975). For the synthesis of the title compound, see: Noller & Baliah (1948). Three references have been added to this section - please check they are in the correct places for their subjects.

Experimental top

Noller & Baliah (1948) developed a novel method to synthesize piperidin-4-one derivatives by the Mannich condensation reaction using respective aldehydes and ketones with ammonium acetate in the ratio of [2:1:1], respectively. The title compound was synthesized using benzaldehyde (0.2 M), acetone (0.1) and ammonium acetate (0.1M) added to pure ethanol and heated on a hot plate up to the boiling range. The resulting product of diazabicyclic[3.3.1]nonan-9-one was separated out and treated with an equimolar (1:1) quantity of NaNO₂/HCl/80% ethanol and kept at 80° C for 4 h with vigorous stirring. The resuling title compound was separated out and crystals were grown using acetonitrile as the solvent.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SMART (Bruker, 2004); data reduction: SMART (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. ORTEP diagram of the title molecule with the atom numbering scheme. Displacement ellipsoid are drawn at 30% probability level. H atoms were removed for clarity.
	Fig. 2. Packing diagram of the title compound viewed down the b axis. Dashed lines indicate weak C—H···O intra and intermolecular interactions.

3-Nitroso-2,4,6,8-tetraphenyl-3,7-diazabicyclo[3.3.1]nonan-9-one top

Crystal data top

C₃₁H₂₇N₃O₂	F(000) = 1000
M_r = 473.56	D_x = 1.244 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 19483 reflections
a = 18.723 (4) Å	θ = 2.3–27.7°
b = 8.8319 (17) Å	µ = 0.08 mm⁻¹
c = 15.806 (3) Å	T = 293 K
β = 104.728 (3)°	Block, yellow
V = 2527.8 (8) Å³	0.26 × 0.23 × 0.21 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	3235 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.056
Graphite monochromator	θ_max = 27.7°, θ_min = 2.3°
ω scans	h = −23→21
19483 measured reflections	k = −11→10
5385 independent reflections	l = −20→20

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)] = 0.081	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.187	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0715P)² + 0.6524P] where P = (F_o² + 2F_c²)/3
5385 reflections	(Δ/σ)_max < 0.001
334 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₃₁H₂₇N₃O₂	V = 2527.8 (8) Å³
M_r = 473.56	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.723 (4) Å	µ = 0.08 mm⁻¹
b = 8.8319 (17) Å	T = 293 K
c = 15.806 (3) Å	0.26 × 0.23 × 0.21 mm
β = 104.728 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	3235 reflections with I > 2σ(I)
19483 measured reflections	R_int = 0.056
5385 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.081	0 restraints
wR(F²) = 0.187	H-atom parameters constrained
S = 1.06	Δρ_max = 0.32 e Å⁻³
5385 reflections	Δρ_min = −0.29 e Å⁻³
334 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	Occ. (<1)
O1	0.16505 (12)	0.9901 (2)	0.43401 (14)	0.0741 (6)
O2	0.33486 (19)	0.5848 (4)	0.2575 (2)	0.0838 (10)	0.70
O3	0.3644 (5)	0.5232 (10)	0.3459 (6)	0.093 (3)	0.30
N1	0.27775 (12)	0.6798 (2)	0.34371 (15)	0.0527 (6)
N2	0.32788 (19)	0.5919 (4)	0.3247 (3)	0.0898 (11)
N4	0.35556 (12)	0.9558 (2)	0.38245 (13)	0.0536 (6)
H4	0.3933	0.9259	0.3653	0.064*
C2	0.27407 (15)	0.6783 (3)	0.43486 (18)	0.0516 (7)
H2	0.3192	0.6290	0.4687	0.062*
C3	0.34747 (15)	0.9322 (3)	0.47096 (17)	0.0543 (7)
H3	0.3419	1.0322	0.4953	0.065*
C5	0.29317 (15)	1.0350 (3)	0.32634 (18)	0.0545 (7)
H5	0.2862	1.1294	0.3558	0.065*
C6	0.22947 (14)	0.7796 (3)	0.27724 (17)	0.0503 (7)
H6	0.2550	0.7961	0.2311	0.060*
C7	0.22234 (15)	0.9354 (3)	0.31808 (18)	0.0540 (7)
H7	0.1799	0.9887	0.2809	0.065*
C8	0.27560 (15)	0.8422 (3)	0.46805 (18)	0.0515 (7)
H8	0.2679	0.8404	0.5271	0.062*
C9	0.21246 (16)	0.9267 (3)	0.40905 (19)	0.0549 (7)
C13	0.20946 (16)	0.5843 (3)	0.44686 (19)	0.0580 (7)
C14	0.16836 (19)	0.6217 (4)	0.5048 (2)	0.0810 (10)
H14	0.1786	0.7108	0.5370	0.097*
C15	0.1124 (2)	0.5289 (5)	0.5158 (3)	0.1094 (14)
H15	0.0856	0.5562	0.5555	0.131*
C16	0.0954 (2)	0.3983 (5)	0.4698 (4)	0.1124 (15)
H16	0.0572	0.3367	0.4774	0.135*
C17	0.1357 (2)	0.3594 (4)	0.4123 (3)	0.0961 (13)
H17	0.1248	0.2701	0.3805	0.115*
C18	0.19191 (18)	0.4497 (3)	0.4006 (2)	0.0742 (9)
H18	0.2187	0.4207	0.3611	0.089*
C19	0.15692 (15)	0.7006 (3)	0.23480 (17)	0.0542 (7)
C20	0.09218 (17)	0.7261 (4)	0.2579 (2)	0.0790 (10)
H20	0.0910	0.7970	0.3010	0.095*
C21	0.0286 (2)	0.6478 (6)	0.2178 (3)	0.1031 (13)
H21	−0.0146	0.6645	0.2352	0.124*
C22	0.0291 (2)	0.5462 (5)	0.1529 (3)	0.1059 (14)
H22	−0.0141	0.4959	0.1250	0.127*
C23	0.0928 (2)	0.5184 (4)	0.1291 (2)	0.0902 (11)
H23	0.0934	0.4483	0.0853	0.108*
C24	0.15639 (18)	0.5950 (4)	0.1703 (2)	0.0703 (9)
H24	0.1999	0.5748	0.1543	0.084*
C25	0.30623 (15)	1.0759 (3)	0.23874 (17)	0.0511 (7)
C26	0.26664 (17)	1.1952 (3)	0.1924 (2)	0.0643 (8)
H26	0.2324	1.2468	0.2151	0.077*
C27	0.27791 (18)	1.2380 (3)	0.1124 (2)	0.0707 (9)
H27	0.2507	1.3171	0.0810	0.085*
C28	0.32896 (18)	1.1636 (3)	0.0797 (2)	0.0661 (8)
H28	0.3372	1.1932	0.0265	0.079*
C29	0.36835 (16)	1.0447 (3)	0.12552 (18)	0.0597 (8)
H29	0.4033	0.9944	0.1033	0.072*
C30	0.35600 (15)	1.0001 (3)	0.20431 (18)	0.0562 (7)
H30	0.3817	0.9180	0.2342	0.067*
C31	0.41479 (15)	0.8592 (3)	0.53034 (17)	0.0544 (7)
C32	0.42814 (19)	0.8818 (4)	0.6201 (2)	0.0715 (9)
H32	0.3973	0.9457	0.6414	0.086*
C33	0.4857 (2)	0.8118 (5)	0.6777 (2)	0.0869 (11)
H33	0.4932	0.8268	0.7376	0.104*
C34	0.53198 (19)	0.7201 (4)	0.6469 (3)	0.0856 (11)
H34	0.5714	0.6729	0.6858	0.103*
C35	0.52064 (18)	0.6971 (4)	0.5588 (2)	0.0773 (9)
H35	0.5525	0.6347	0.5381	0.093*
C36	0.46200 (17)	0.7664 (3)	0.5005 (2)	0.0653 (8)
H36	0.4545	0.7501	0.4408	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0797 (15)	0.0625 (13)	0.0918 (15)	0.0167 (12)	0.0435 (12)	−0.0036 (11)
O2	0.084 (2)	0.102 (3)	0.073 (2)	0.0220 (19)	0.035 (2)	−0.008 (2)
O3	0.071 (6)	0.098 (7)	0.104 (7)	0.057 (5)	0.010 (5)	−0.026 (5)
N1	0.0479 (13)	0.0444 (13)	0.0656 (15)	0.0035 (11)	0.0142 (11)	−0.0147 (11)
N2	0.061 (2)	0.080 (2)	0.138 (3)	0.0025 (17)	0.043 (2)	−0.046 (2)
N4	0.0585 (14)	0.0537 (13)	0.0498 (13)	0.0027 (11)	0.0160 (11)	0.0018 (10)
C2	0.0512 (16)	0.0430 (15)	0.0568 (16)	0.0047 (12)	0.0065 (12)	−0.0032 (12)
C3	0.0674 (19)	0.0408 (15)	0.0549 (17)	−0.0088 (13)	0.0158 (14)	−0.0089 (12)
C5	0.0640 (18)	0.0404 (14)	0.0599 (17)	0.0002 (13)	0.0170 (14)	−0.0034 (13)
C6	0.0507 (16)	0.0524 (16)	0.0493 (15)	−0.0006 (13)	0.0153 (12)	−0.0047 (12)
C7	0.0532 (17)	0.0478 (16)	0.0607 (17)	0.0107 (13)	0.0141 (13)	0.0007 (13)
C8	0.0606 (17)	0.0444 (15)	0.0523 (16)	0.0012 (13)	0.0191 (13)	−0.0053 (12)
C9	0.0620 (18)	0.0377 (14)	0.0709 (19)	−0.0018 (13)	0.0276 (15)	−0.0084 (13)
C13	0.0533 (18)	0.0453 (16)	0.0697 (19)	0.0009 (13)	0.0050 (15)	0.0067 (14)
C14	0.075 (2)	0.068 (2)	0.108 (3)	−0.0119 (18)	0.038 (2)	0.0035 (19)
C15	0.087 (3)	0.107 (3)	0.147 (4)	−0.019 (3)	0.053 (3)	0.012 (3)
C16	0.074 (3)	0.093 (3)	0.162 (5)	−0.028 (2)	0.017 (3)	0.031 (3)
C17	0.079 (3)	0.056 (2)	0.132 (4)	−0.022 (2)	−0.012 (2)	0.009 (2)
C18	0.073 (2)	0.0497 (18)	0.089 (2)	−0.0035 (16)	0.0001 (17)	0.0031 (16)
C19	0.0469 (16)	0.0601 (17)	0.0524 (16)	−0.0047 (13)	0.0067 (13)	0.0097 (14)
C20	0.0501 (19)	0.103 (3)	0.079 (2)	0.0021 (18)	0.0086 (16)	0.004 (2)
C21	0.053 (2)	0.148 (4)	0.101 (3)	−0.005 (2)	0.006 (2)	0.023 (3)
C22	0.074 (3)	0.123 (4)	0.102 (3)	−0.043 (3)	−0.013 (2)	0.024 (3)
C23	0.086 (3)	0.089 (3)	0.083 (2)	−0.032 (2)	0.000 (2)	−0.005 (2)
C24	0.076 (2)	0.069 (2)	0.0625 (19)	−0.0207 (17)	0.0114 (16)	−0.0060 (16)
C25	0.0558 (17)	0.0409 (14)	0.0543 (16)	−0.0061 (13)	0.0098 (13)	0.0000 (12)
C26	0.071 (2)	0.0507 (17)	0.073 (2)	0.0058 (15)	0.0221 (16)	0.0036 (15)
C27	0.086 (2)	0.0535 (18)	0.072 (2)	0.0068 (17)	0.0191 (18)	0.0160 (16)
C28	0.081 (2)	0.0608 (19)	0.0581 (18)	−0.0090 (17)	0.0204 (16)	0.0047 (15)
C29	0.0651 (19)	0.0565 (18)	0.0562 (18)	−0.0012 (15)	0.0130 (14)	−0.0037 (14)
C30	0.0600 (18)	0.0480 (16)	0.0574 (17)	0.0004 (14)	0.0087 (14)	−0.0002 (13)
C31	0.0575 (18)	0.0530 (16)	0.0503 (16)	−0.0200 (14)	0.0089 (13)	−0.0020 (13)
C32	0.075 (2)	0.079 (2)	0.0576 (19)	−0.0224 (18)	0.0117 (17)	−0.0106 (16)
C33	0.080 (3)	0.113 (3)	0.056 (2)	−0.040 (2)	−0.0030 (19)	0.004 (2)
C34	0.064 (2)	0.096 (3)	0.082 (3)	−0.028 (2)	−0.0077 (19)	0.020 (2)
C35	0.061 (2)	0.078 (2)	0.088 (3)	−0.0081 (17)	0.0083 (18)	0.0080 (19)
C36	0.0650 (19)	0.068 (2)	0.0611 (18)	−0.0108 (17)	0.0129 (16)	−0.0003 (16)

Geometric parameters (Å, º) top

O1—C9	1.198 (3)	C17—H17	0.9300
O2—N2	1.106 (4)	C18—H18	0.9300
O2—O3	1.471 (10)	C19—C20	1.370 (4)
O3—N2	0.912 (7)	C19—C24	1.380 (4)
N1—N2	1.310 (4)	C20—C21	1.383 (5)
N1—C2	1.460 (3)	C20—H20	0.9300
N1—C6	1.488 (3)	C21—C22	1.365 (6)
N4—C5	1.454 (3)	C21—H21	0.9300
N4—C3	1.460 (3)	C22—C23	1.360 (5)
N4—H4	0.8600	C22—H22	0.9300
C2—C13	1.518 (4)	C23—C24	1.381 (4)
C2—C8	1.537 (3)	C23—H23	0.9300
C2—H2	0.9800	C24—H24	0.9300
C3—C31	1.511 (4)	C25—C30	1.368 (4)
C3—C8	1.553 (4)	C25—C26	1.385 (4)
C3—H3	0.9800	C26—C27	1.387 (4)
C5—C25	1.510 (4)	C26—H26	0.9300
C5—C7	1.569 (4)	C27—C28	1.364 (4)
C5—H5	0.9800	C27—H27	0.9300
C6—C19	1.522 (4)	C28—C29	1.378 (4)
C6—C7	1.541 (4)	C28—H28	0.9300
C6—H6	0.9800	C29—C30	1.381 (4)
C7—C9	1.498 (4)	C29—H29	0.9300
C7—H7	0.9800	C30—H30	0.9300
C8—C9	1.505 (4)	C31—C36	1.374 (4)
C8—H8	0.9800	C31—C32	1.391 (4)
C13—C14	1.378 (4)	C32—C33	1.369 (5)
C13—C18	1.390 (4)	C32—H32	0.9300
C14—C15	1.376 (5)	C33—C34	1.364 (5)
C14—H14	0.9300	C33—H33	0.9300
C15—C16	1.357 (6)	C34—C35	1.369 (5)
C15—H15	0.9300	C34—H34	0.9300
C16—C17	1.365 (6)	C35—C36	1.384 (4)
C16—H16	0.9300	C35—H35	0.9300
C17—C18	1.370 (5)	C36—H36	0.9300

N2—O3—O2	48.6 (5)	C16—C17—C18	121.2 (4)
N2—N1—C2	115.9 (3)	C16—C17—H17	119.4
N2—N1—C6	122.1 (3)	C18—C17—H17	119.4
C2—N1—C6	122.0 (2)	C17—C18—C13	120.9 (4)
O3—N2—O2	93.1 (7)	C17—C18—H18	119.6
O3—N2—N1	145.5 (9)	C13—C18—H18	119.6
O2—N2—N1	121.4 (5)	C20—C19—C24	117.8 (3)
C5—N4—C3	113.0 (2)	C20—C19—C6	123.9 (3)
C5—N4—H4	123.5	C24—C19—C6	118.2 (3)
C3—N4—H4	123.5	C19—C20—C21	120.9 (4)
N1—C2—C13	111.5 (2)	C19—C20—H20	119.6
N1—C2—C8	109.1 (2)	C21—C20—H20	119.6
C13—C2—C8	114.7 (2)	C22—C21—C20	120.2 (4)
N1—C2—H2	107.0	C22—C21—H21	119.9
C13—C2—H2	107.0	C20—C21—H21	119.9
C8—C2—H2	107.0	C23—C22—C21	120.1 (4)
N4—C3—C31	112.5 (2)	C23—C22—H22	120.0
N4—C3—C8	110.2 (2)	C21—C22—H22	120.0
C31—C3—C8	112.3 (2)	C22—C23—C24	119.5 (4)
N4—C3—H3	107.2	C22—C23—H23	120.3
C31—C3—H3	107.2	C24—C23—H23	120.3
C8—C3—H3	107.2	C23—C24—C19	121.6 (3)
N4—C5—C25	112.5 (2)	C23—C24—H24	119.2
N4—C5—C7	108.2 (2)	C19—C24—H24	119.2
C25—C5—C7	112.9 (2)	C30—C25—C26	119.3 (3)
N4—C5—H5	107.7	C30—C25—C5	122.2 (2)
C25—C5—H5	107.7	C26—C25—C5	118.5 (3)
C7—C5—H5	107.7	C25—C26—C27	120.3 (3)
N1—C6—C19	110.7 (2)	C25—C26—H26	119.9
N1—C6—C7	109.6 (2)	C27—C26—H26	119.9
C19—C6—C7	115.5 (2)	C28—C27—C26	119.8 (3)
N1—C6—H6	106.8	C28—C27—H27	120.1
C19—C6—H6	106.8	C26—C27—H27	120.1
C7—C6—H6	106.8	C27—C28—C29	120.1 (3)
C9—C7—C6	113.7 (2)	C27—C28—H28	120.0
C9—C7—C5	104.9 (2)	C29—C28—H28	120.0
C6—C7—C5	112.0 (2)	C28—C29—C30	120.1 (3)
C9—C7—H7	108.7	C28—C29—H29	120.0
C6—C7—H7	108.7	C30—C29—H29	120.0
C5—C7—H7	108.7	C25—C30—C29	120.4 (3)
C9—C8—C2	108.2 (2)	C25—C30—H30	119.8
C9—C8—C3	107.6 (2)	C29—C30—H30	119.8
C2—C8—C3	115.7 (2)	C36—C31—C32	118.1 (3)
C9—C8—H8	108.4	C36—C31—C3	123.3 (3)
C2—C8—H8	108.4	C32—C31—C3	118.5 (3)
C3—C8—H8	108.4	C33—C32—C31	121.4 (3)
O1—C9—C7	125.1 (3)	C33—C32—H32	119.3
O1—C9—C8	124.0 (3)	C31—C32—H32	119.3
C7—C9—C8	110.6 (2)	C34—C33—C32	119.6 (3)
C14—C13—C18	117.2 (3)	C34—C33—H33	120.2
C14—C13—C2	123.3 (3)	C32—C33—H33	120.2
C18—C13—C2	119.4 (3)	C33—C34—C35	120.2 (3)
C13—C14—C15	120.9 (4)	C33—C34—H34	119.9
C13—C14—H14	119.6	C35—C34—H34	119.9
C15—C14—H14	119.6	C34—C35—C36	120.2 (3)
C16—C15—C14	121.4 (4)	C34—C35—H35	119.9
C16—C15—H15	119.3	C36—C35—H35	119.9
C14—C15—H15	119.3	C31—C36—C35	120.4 (3)
C15—C16—C17	118.4 (4)	C31—C36—H36	119.8
C15—C16—H16	120.8	C35—C36—H36	119.8
C17—C16—H16	120.8

O2—O3—N2—N1	178.8 (13)	C8—C2—C13—C18	163.9 (2)
O3—O2—N2—N1	−179.2 (9)	C18—C13—C14—C15	−0.1 (5)
C2—N1—N2—O3	1.2 (14)	C2—C13—C14—C15	−177.2 (3)
C6—N1—N2—O3	178.9 (13)	C13—C14—C15—C16	−0.4 (6)
C2—N1—N2—O2	179.8 (3)	C14—C15—C16—C17	0.5 (7)
C6—N1—N2—O2	−2.5 (5)	C15—C16—C17—C18	−0.2 (6)
N2—N1—C2—C13	−102.7 (3)	C16—C17—C18—C13	−0.2 (5)
C6—N1—C2—C13	79.6 (3)	C14—C13—C18—C17	0.4 (5)
N2—N1—C2—C8	129.5 (3)	C2—C13—C18—C17	177.6 (3)
C6—N1—C2—C8	−48.2 (3)	N1—C6—C19—C20	99.8 (3)
C5—N4—C3—C31	−176.2 (2)	C7—C6—C19—C20	−25.5 (4)
C5—N4—C3—C8	57.7 (3)	N1—C6—C19—C24	−79.0 (3)
C3—N4—C5—C25	172.9 (2)	C7—C6—C19—C24	155.7 (3)
C3—N4—C5—C7	−61.8 (3)	C24—C19—C20—C21	0.2 (5)
N2—N1—C6—C19	93.7 (3)	C6—C19—C20—C21	−178.6 (3)
C2—N1—C6—C19	−88.8 (3)	C19—C20—C21—C22	−1.6 (6)
N2—N1—C6—C7	−137.7 (3)	C20—C21—C22—C23	1.9 (6)
C2—N1—C6—C7	39.8 (3)	C21—C22—C23—C24	−0.7 (6)
N1—C6—C7—C9	−42.0 (3)	C22—C23—C24—C19	−0.7 (5)
C19—C6—C7—C9	83.9 (3)	C20—C19—C24—C23	0.9 (5)
N1—C6—C7—C5	76.7 (3)	C6—C19—C24—C23	179.8 (3)
C19—C6—C7—C5	−157.4 (2)	N4—C5—C25—C30	23.0 (3)
N4—C5—C7—C9	63.2 (3)	C7—C5—C25—C30	−99.8 (3)
C25—C5—C7—C9	−171.7 (2)	N4—C5—C25—C26	−156.5 (2)
N4—C5—C7—C6	−60.6 (3)	C7—C5—C25—C26	80.7 (3)
C25—C5—C7—C6	64.6 (3)	C30—C25—C26—C27	−0.6 (4)
N1—C2—C8—C9	56.8 (3)	C5—C25—C26—C27	178.9 (3)
C13—C2—C8—C9	−69.1 (3)	C25—C26—C27—C28	−0.9 (5)
N1—C2—C8—C3	−63.9 (3)	C26—C27—C28—C29	1.1 (5)
C13—C2—C8—C3	170.1 (2)	C27—C28—C29—C30	0.3 (4)
N4—C3—C8—C9	−55.1 (3)	C26—C25—C30—C29	2.0 (4)
C31—C3—C8—C9	178.7 (2)	C5—C25—C30—C29	−177.5 (2)
N4—C3—C8—C2	66.0 (3)	C28—C29—C30—C25	−1.8 (4)
C31—C3—C8—C2	−60.3 (3)	N4—C3—C31—C36	−27.2 (4)
C6—C7—C9—O1	−129.3 (3)	C8—C3—C31—C36	97.7 (3)
C5—C7—C9—O1	108.0 (3)	N4—C3—C31—C32	155.5 (2)
C6—C7—C9—C8	57.3 (3)	C8—C3—C31—C32	−79.5 (3)
C5—C7—C9—C8	−65.3 (3)	C36—C31—C32—C33	−1.2 (4)
C2—C8—C9—O1	122.8 (3)	C3—C31—C32—C33	176.2 (3)
C3—C8—C9—O1	−111.6 (3)	C31—C32—C33—C34	1.2 (5)
C2—C8—C9—C7	−63.8 (3)	C32—C33—C34—C35	−0.5 (5)
C3—C8—C9—C7	61.8 (3)	C33—C34—C35—C36	−0.2 (5)
N1—C2—C13—C14	−143.8 (3)	C32—C31—C36—C35	0.5 (4)
C8—C2—C13—C14	−19.1 (4)	C3—C31—C36—C35	−176.8 (3)
N1—C2—C13—C18	39.2 (3)	C34—C35—C36—C31	0.2 (5)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C31–C36 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···O3	0.93	2.94	3.607 (1)	130
C20—H20···O1	0.93	2.79	3.622 (4)	150
C24—H24···O2	0.93	2.64	3.276 (5)	126
C36—H36···O3	0.93	2.80	3.415 (9)	125
C17—H17···O1ⁱ	0.93	2.66	3.311 (4)	128
C22—H22···O1ⁱⁱ	0.93	2.74	3.579 (5)	150
C32—H32···O2ⁱⁱⁱ	0.93	2.43	3.127 (6)	132
C34—H34···O3^iv	0.93	2.24	2.878 (1)	125
C29—H29···Cg1^v	0.93	2.87	3.677	146

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

Experimental details

Crystal data
Chemical formula	C₃₁H₂₇N₃O₂
M_r	473.56
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	18.723 (4), 8.8319 (17), 15.806 (3)
β (°)	104.728 (3)
V (Å³)	2527.8 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.26 × 0.23 × 0.21

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	19483, 5385, 3235
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.654

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.081, 0.187, 1.06
No. of reflections	5385
No. of parameters	334
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.29

Computer programs: SMART (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C31–C36 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···O3	0.93	2.94	3.607 (1)	130
C20—H20···O1	0.93	2.79	3.622 (4)	150
C24—H24···O2	0.93	2.64	3.276 (5)	126
C36—H36···O3	0.93	2.80	3.415 (9)	125
C17—H17···O1ⁱ	0.93	2.66	3.311 (4)	128
C22—H22···O1ⁱⁱ	0.93	2.74	3.579 (5)	150
C32—H32···O2ⁱⁱⁱ	0.93	2.43	3.127 (6)	132
C34—H34···O3^iv	0.93	2.24	2.878 (1)	125
C29—H29···Cg1^v	0.93	2.87	3.677	146

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

References

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