2,7-Bis(2-nitro­phen­yl)-9-octyl-9H-carbazole

Wrobel, N.; Schollmeyer, D.; Detert, H.

doi:10.1107/S1600536812012780

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1249

doi:10.1107/S1600536812012780

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2,7-Bis(2-nitrophenyl)-9-octyl-9H-carbazole

Norma Wrobel,^a Dieter Schollmeyer ^a and Heiner Detert ^a ^*

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

(Received 19 March 2012; accepted 23 March 2012; online 31 March 2012)

The title compound, C₃₂H₃₁N₃O₄, was obtained in a Suzuki coupling of carbazole diboronic acid and bromonitrobenzene. In the crystal, the molecule adopts a non-symmetric conformation. The carbazole ring system is approximately planar [maximum deviation from the least-squares plane = 0.039 (2) Å]. The planes of the carbazole unit and the benzene rings subtend dihedral angles of 48.42 (7) and 41.81 (6)°. The dihedral angles between the planes of the nitrophenyl rings and the nitro groups are 44.34 (19) and 61.64 (15)°. The crystal is built from two strands of parallel molecules with interdigitated octyl chains. These strands are symmetry related by a twofold screw axis.

Related literature

For Suzuki cross-couplings, see: Miyaura & Suzuki (1995 ). For the Cadogan reaction, see: Cadogan (1962 ). For indolocarbazoles, see: Nemkovich et al. (2009 ). For heteroanalogous carbazoles, see: Dassonneville et al. (2011 ); Letessier & Detert (2012 ). For the structures of aryl-substituted carbazoles and substituted p-terphenyls, see: Letessier et al. (2011 ); Jones et al. (2005 ); Moschel et al. (2011 ); Wrobel et al. (2012 ).

Experimental

Crystal data

C₃₂H₃₁N₃O₄
M_r = 521.60
Monoclinic, P 2₁ /c
a = 8.722 (2) Å
b = 7.987 (2) Å
c = 39.508 (11) Å
β = 95.044 (6)°
V = 2741.5 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 173 K
0.50 × 0.04 × 0.04 mm

Data collection

Bruker SMART APEXII diffractometer
15053 measured reflections
6525 independent reflections
2814 reflections with I > 2σ(I)
R_int = 0.099

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.137
S = 0.93
6525 reflections
353 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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/S1600536812012780/rz2725sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812012780/rz2725Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812012780/rz2725Isup3.cml

checkCIF report

Comment top

The title compound was prepared as an intermediate in a larger project on carbazoles and heteroanalogous carbazoles, see Dassonneville et al. (2011), Letessier et al. (2011), Letessier & Detert (2012). Indolocarbazoles (Nemkovich et al. 2009) are prepared by Cadogan reaction (Cadogan, 1962).

The molecule adopts a non-symmetric conformation with a nearly planar carbazole unit (maximum deviation from the least-squares plane = 0.039 (2) Å at C7). Attached to N9 is the octyl chain in an an all-trans conformation. The planes of the carbazole unit and the benzene rings subtend dihedral angles of 48.42 (7)° (ring C1–C9a and ring C18–C23) and 41.81 (6)° (ring C4b–C8a and ring C27–C32). Dihedral angles between the planes of the benzene rings and the nitro groups are 44.34 (19)° and 61.64 (35)°. Whereas the dihedral angles between the aromatic rings are comparable to those found in a o-nitrobiaryl with an additional o-substituent (Wrobel et al.., 2012), the dihedral angles between the planes of the niro groups and the adjacent benzene ring are even larger. Both nitro goups are oriented toward the N9 nitrogen atom of the carbazole. Two strands of parallel molecules with interdigitated octyl chains, symmetry-related by a twofold screw axis, build the crystal.

Related literature top

For Suzuki cross-couplings, see: Miyaura & Suzuki (1995). For the Cadogan reaction, see: Cadogan (1962). For indolocarbazoles, see: Nemkovich et al. (2009). For heteroanalogous carbazoles, see: Dassonneville et al. (2011); Letessier & Detert (2012). For the structures of aryl-substituted carbazoles and substituted p-terphenyls, see: Letessier et al. (2011); Jones et al. (2005); Moschel et al. (2011); Wrobel et al. (2012).

Experimental top

N-Octylcarbazol-2,7-diboronic acid (1 g, 1.88 mmol) and 2-bromonitrobenzene (0.75 g, 3.71 mmol) were dissolved in toluene (4.5 ml). A solution of K₂CO₃ (2M, 3 ml) was added and the mixture was stirred for 30 min. Palladium acetate (34 mg, 0.15 mmol) and triphenylphosphine (159 mg, 0.606 mmol) were added to the stirred solution. After refluxing for 48 h, the mixture was cooled, diluted with water (15 ml) and extracted with dichloromethane (3 × 25 ml). The pooled extracts were washed with water, brine, and dried (MgSO₄). The residue was recrystallized from methanol to give the analytically pure compound. Greenish needles-like crystals suitable for X-rax analysis were grown by slow evaporation of a chloroform / methanol (1:1 v/v) solution. M. p. = 411-412 K.

Structure description top

For Suzuki cross-couplings, see: Miyaura & Suzuki (1995). For the Cadogan reaction, see: Cadogan (1962). For indolocarbazoles, see: Nemkovich et al. (2009). For heteroanalogous carbazoles, see: Dassonneville et al. (2011); Letessier & Detert (2012). For the structures of aryl-substituted carbazoles and substituted p-terphenyls, see: Letessier et al. (2011); Jones et al. (2005); Moschel et al. (2011); Wrobel et al. (2012).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing section of the monoclinic crystal down the a axis. Molecules shown in equal colors are shifted by y/b = 1 along the b axis. Red/blue (green/black) molecules are related by the twofold screw axis.

2,7-Bis(2-nitrophenyl)-9-octyl-9H-carbazole top

Crystal data top

C₃₂H₃₁N₃O₄	F(000) = 1104
M_r = 521.60	D_x = 1.264 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 411 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.722 (2) Å	Cell parameters from 951 reflections
b = 7.987 (2) Å	θ = 2.3–20.4°
c = 39.508 (11) Å	µ = 0.08 mm⁻¹
β = 95.044 (6)°	T = 173 K
V = 2741.5 (13) Å³	Needle, green
Z = 4	0.50 × 0.04 × 0.04 mm

Data collection top

Bruker SMART APEXII diffractometer	2814 reflections with I > 2σ(I)
Radiation source: sealed Tube	R_int = 0.099
Graphite monochromator	θ_max = 28.0°, θ_min = 2.1°
CCD scan	h = −11→11
15053 measured reflections	k = −9→10
6525 independent reflections	l = −51→52

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.0415P)²] where P = (F_o² + 2F_c²)/3
6525 reflections	(Δ/σ)_max < 0.001
353 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₃₂H₃₁N₃O₄	V = 2741.5 (13) Å³
M_r = 521.60	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.722 (2) Å	µ = 0.08 mm⁻¹
b = 7.987 (2) Å	T = 173 K
c = 39.508 (11) Å	0.50 × 0.04 × 0.04 mm
β = 95.044 (6)°

Data collection top

Bruker SMART APEXII diffractometer	2814 reflections with I > 2σ(I)
15053 measured reflections	R_int = 0.099
6525 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.137	H-atom parameters constrained
S = 0.93	Δρ_max = 0.22 e Å⁻³
6525 reflections	Δρ_min = −0.22 e Å⁻³
353 parameters

Special details top

Experimental. ¹H-NMR (400 MHz, CDCl₃): δ = 0.81 (m, 3 H, CH₃), 1.20 - 1.40 (m, 10 H, CH₂), 1.91 (qui, 2 H, β-CH₂), 4.28 (t, 2 H, N—CH₂), 7.18 (dd, J = 8.1 Hz, J= 1.2 Hz, 2 H), 7.34 (s, 2 H, 1-H, 8-H, carbazol), 7.49 (ddd, 2 H, 4-H phenyl), 7.56 - 7.68 (m, 4 H), 7.86 (d, 2 H, J = 7.5 Hz), 8.13 (d, 2 H, J = 8 Hz)

¹³C-NMR (75 MHz, CDCl₃): δ = 14.1, 22.6, 27.3, 28.9, 29.1, 29.3, 31.8, 43.3, 108.3, 119.2, 120.8, 122.4, 124.0, 128.0, 132.1, 132.3, 135.1, 137.0, 141.0, 149.8.

ESI-MS: (M+H⁺): m/z = 522

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	0.1501 (3)	0.0908 (3)	0.07930 (6)	0.0281 (6)
H1	0.2497	0.0686	0.0901	0.034*
C2	0.0823 (3)	−0.0170 (3)	0.05459 (6)	0.0281 (6)
C3	−0.0668 (3)	0.0158 (3)	0.03934 (6)	0.0294 (7)
H3	−0.1128	−0.0593	0.0228	0.035*
C4	−0.1471 (3)	0.1566 (3)	0.04823 (6)	0.0295 (6)
H4	−0.2474	0.1779	0.0377	0.035*
C4A	−0.0806 (3)	0.2665 (3)	0.07251 (6)	0.0268 (6)
C4B	−0.1301 (3)	0.4184 (3)	0.08774 (6)	0.0271 (6)
C5	−0.2635 (3)	0.5156 (4)	0.08451 (7)	0.0340 (7)
H5	−0.3474	0.4841	0.0689	0.041*
C6	−0.2731 (3)	0.6580 (3)	0.10414 (7)	0.0350 (7)
H6	−0.3635	0.7248	0.1015	0.042*
C7	−0.1520 (3)	0.7057 (3)	0.12791 (6)	0.0302 (7)
C8	−0.0166 (3)	0.6129 (3)	0.13098 (6)	0.0303 (7)
H8	0.0681	0.6467	0.1462	0.036*
C8A	−0.0080 (3)	0.4701 (3)	0.11135 (6)	0.0272 (6)
N9	0.1124 (2)	0.3575 (3)	0.11075 (5)	0.0296 (6)
C9A	0.0684 (3)	0.2310 (3)	0.08774 (6)	0.0265 (6)
C10	0.2587 (3)	0.3693 (3)	0.13157 (6)	0.0323 (7)
H10A	0.2981	0.4852	0.1305	0.039*
H10B	0.3344	0.2941	0.1221	0.039*
C11	0.2451 (3)	0.3226 (4)	0.16865 (6)	0.0353 (7)
H11A	0.1706	0.3987	0.1783	0.042*
H11B	0.2049	0.2071	0.1698	0.042*
C12	0.3993 (3)	0.3338 (4)	0.18988 (7)	0.0351 (7)
H12A	0.4665	0.2415	0.1834	0.042*
H12B	0.4498	0.4408	0.1849	0.042*
C13	0.3825 (3)	0.3236 (4)	0.22768 (7)	0.0361 (7)
H13A	0.3269	0.2191	0.2323	0.043*
H13B	0.3183	0.4187	0.2341	0.043*
C14	0.5335 (3)	0.3266 (4)	0.25009 (6)	0.0346 (7)
H14A	0.5926	0.2240	0.2458	0.042*
H14B	0.5950	0.4240	0.2437	0.042*
C15	0.5117 (3)	0.3369 (4)	0.28762 (6)	0.0358 (7)
H15A	0.4468	0.2416	0.2936	0.043*
H15B	0.4549	0.4411	0.2918	0.043*
C16	0.6591 (3)	0.3349 (4)	0.31096 (7)	0.0393 (8)
H16A	0.7267	0.4268	0.3044	0.047*
H16B	0.7135	0.2279	0.3079	0.047*
C17	0.6310 (4)	0.3547 (4)	0.34818 (7)	0.0545 (9)
H17A	0.5803	0.4622	0.3515	0.082*
H17B	0.7296	0.3512	0.3621	0.082*
H17C	0.5650	0.2634	0.3549	0.082*
C18	0.1673 (3)	−0.1675 (3)	0.04443 (6)	0.0258 (6)
C19	0.3244 (3)	−0.1658 (3)	0.03964 (6)	0.0278 (6)
C20	0.4070 (3)	−0.3068 (3)	0.03240 (7)	0.0331 (7)
H20	0.5144	−0.2999	0.0301	0.040*
C21	0.3302 (4)	−0.4589 (4)	0.02854 (7)	0.0403 (8)
H21	0.3847	−0.5576	0.0235	0.048*
C22	0.1740 (4)	−0.4661 (4)	0.03203 (7)	0.0397 (8)
H22	0.1205	−0.5693	0.0289	0.048*
C23	0.0956 (3)	−0.3233 (3)	0.04001 (6)	0.0347 (7)
H23	−0.0114	−0.3314	0.0426	0.042*
N24	0.4094 (3)	−0.0065 (3)	0.04073 (6)	0.0338 (6)
O25	0.5191 (2)	0.0084 (3)	0.06205 (6)	0.0545 (6)
O26	0.3683 (2)	0.1017 (2)	0.01991 (5)	0.0440 (6)
C27	−0.1633 (3)	0.8555 (3)	0.14989 (7)	0.0304 (7)
C28	−0.1202 (3)	0.8539 (3)	0.18486 (6)	0.0296 (7)
C29	−0.1115 (3)	0.9962 (4)	0.20483 (7)	0.0383 (7)
H29	−0.0766	0.9900	0.2283	0.046*
C30	−0.1546 (3)	1.1479 (4)	0.19000 (8)	0.0428 (8)
H30	−0.1502	1.2473	0.2033	0.051*
C31	−0.2040 (4)	1.1544 (4)	0.15588 (8)	0.0440 (8)
H31	−0.2362	1.2581	0.1459	0.053*
C32	−0.2070 (3)	1.0114 (3)	0.13615 (7)	0.0389 (7)
H32	−0.2398	1.0193	0.1126	0.047*
N33	−0.0912 (3)	0.6934 (3)	0.20279 (6)	0.0417 (7)
O34	−0.1798 (3)	0.5768 (2)	0.19591 (5)	0.0500 (6)
O35	0.0185 (3)	0.6880 (3)	0.22437 (6)	0.0664 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0242 (16)	0.0352 (16)	0.0244 (14)	0.0019 (13)	−0.0007 (12)	0.0019 (13)
C2	0.0278 (17)	0.0343 (16)	0.0222 (13)	−0.0012 (13)	0.0027 (12)	0.0011 (13)
C3	0.0278 (17)	0.0376 (17)	0.0226 (13)	−0.0033 (14)	0.0020 (11)	−0.0034 (13)
C4	0.0222 (16)	0.0418 (17)	0.0242 (13)	0.0014 (14)	0.0004 (11)	0.0039 (14)
C4A	0.0253 (17)	0.0349 (16)	0.0208 (13)	0.0013 (13)	0.0044 (11)	0.0024 (13)
C4B	0.0257 (17)	0.0352 (16)	0.0198 (13)	0.0039 (13)	−0.0004 (11)	0.0024 (13)
C5	0.0271 (17)	0.0465 (18)	0.0268 (14)	0.0034 (14)	−0.0074 (12)	0.0002 (14)
C6	0.0317 (18)	0.0416 (18)	0.0312 (15)	0.0136 (14)	−0.0009 (13)	0.0010 (15)
C7	0.0340 (18)	0.0303 (16)	0.0264 (14)	0.0052 (13)	0.0030 (13)	0.0034 (13)
C8	0.0303 (18)	0.0339 (17)	0.0263 (14)	0.0030 (13)	−0.0008 (12)	0.0007 (13)
C8A	0.0250 (17)	0.0322 (16)	0.0241 (13)	0.0036 (13)	0.0004 (12)	0.0016 (13)
N9	0.0249 (14)	0.0373 (14)	0.0250 (11)	0.0035 (11)	−0.0076 (10)	−0.0025 (11)
C9A	0.0284 (17)	0.0319 (16)	0.0192 (12)	−0.0024 (13)	0.0017 (11)	−0.0025 (12)
C10	0.0274 (17)	0.0378 (17)	0.0303 (15)	0.0021 (13)	−0.0051 (12)	−0.0058 (14)
C11	0.0356 (18)	0.0381 (17)	0.0310 (15)	0.0054 (14)	−0.0045 (13)	−0.0007 (14)
C12	0.0349 (18)	0.0360 (17)	0.0326 (15)	0.0034 (14)	−0.0074 (13)	−0.0042 (14)
C13	0.0346 (18)	0.0395 (17)	0.0327 (15)	0.0013 (14)	−0.0052 (13)	−0.0023 (14)
C14	0.0384 (19)	0.0341 (17)	0.0294 (15)	−0.0002 (14)	−0.0072 (13)	−0.0036 (13)
C15	0.0397 (19)	0.0371 (17)	0.0294 (15)	0.0009 (14)	−0.0045 (13)	−0.0031 (14)
C16	0.0403 (19)	0.0414 (18)	0.0345 (16)	0.0066 (15)	−0.0067 (14)	−0.0060 (15)
C17	0.070 (3)	0.054 (2)	0.0366 (17)	0.0176 (18)	−0.0127 (16)	−0.0055 (17)
C18	0.0278 (17)	0.0325 (16)	0.0169 (12)	−0.0024 (13)	0.0003 (11)	−0.0004 (12)
C19	0.0345 (18)	0.0248 (15)	0.0234 (13)	−0.0033 (13)	−0.0012 (12)	0.0013 (12)
C20	0.0331 (18)	0.0313 (17)	0.0349 (16)	0.0053 (14)	0.0023 (13)	−0.0002 (14)
C21	0.053 (2)	0.0267 (17)	0.0412 (17)	0.0063 (15)	0.0052 (15)	0.0017 (14)
C22	0.053 (2)	0.0297 (17)	0.0364 (17)	−0.0093 (15)	0.0018 (15)	0.0011 (14)
C23	0.0385 (19)	0.0352 (18)	0.0301 (15)	−0.0070 (15)	0.0007 (13)	−0.0002 (14)
N24	0.0304 (16)	0.0332 (15)	0.0382 (14)	0.0016 (12)	0.0054 (12)	−0.0020 (13)
O25	0.0323 (14)	0.0598 (15)	0.0676 (15)	−0.0086 (11)	−0.0162 (12)	−0.0030 (13)
O26	0.0521 (15)	0.0321 (12)	0.0479 (13)	−0.0019 (10)	0.0062 (11)	0.0087 (11)
C27	0.0277 (17)	0.0316 (16)	0.0323 (15)	0.0016 (13)	0.0053 (12)	0.0025 (14)
C28	0.0337 (18)	0.0275 (15)	0.0283 (14)	0.0040 (13)	0.0064 (12)	0.0049 (13)
C29	0.0390 (19)	0.0394 (18)	0.0366 (16)	−0.0024 (15)	0.0046 (13)	−0.0079 (16)
C30	0.048 (2)	0.0298 (17)	0.053 (2)	−0.0068 (15)	0.0198 (16)	−0.0048 (16)
C31	0.051 (2)	0.0314 (18)	0.051 (2)	0.0019 (15)	0.0148 (16)	0.0074 (17)
C32	0.044 (2)	0.0357 (17)	0.0376 (16)	0.0007 (15)	0.0061 (14)	0.0064 (15)
N33	0.0542 (19)	0.0428 (17)	0.0287 (13)	0.0105 (14)	0.0078 (13)	0.0047 (13)
O34	0.0712 (17)	0.0279 (12)	0.0522 (14)	0.0002 (11)	0.0137 (12)	0.0040 (11)
O35	0.0716 (18)	0.0771 (18)	0.0473 (14)	0.0137 (14)	−0.0129 (13)	0.0204 (13)

Geometric parameters (Å, º) top

C1—C9A	1.384 (3)	C14—H14A	0.9900
C1—C2	1.393 (3)	C14—H14B	0.9900
C1—H1	0.9500	C15—C16	1.515 (4)
C2—C3	1.409 (3)	C15—H15A	0.9900
C2—C18	1.486 (4)	C15—H15B	0.9900
C3—C4	1.386 (4)	C16—C17	1.520 (4)
C3—H3	0.9500	C16—H16A	0.9900
C4—C4A	1.388 (3)	C16—H16B	0.9900
C4—H4	0.9500	C17—H17A	0.9800
C4A—C9A	1.413 (3)	C17—H17B	0.9800
C4A—C4B	1.438 (3)	C17—H17C	0.9800
C4B—C5	1.395 (4)	C18—C23	1.397 (3)
C4B—C8A	1.414 (3)	C18—C19	1.399 (4)
C5—C6	1.383 (4)	C19—C20	1.381 (3)
C5—H5	0.9500	C19—N24	1.471 (3)
C6—C7	1.403 (4)	C20—C21	1.390 (4)
C6—H6	0.9500	C20—H20	0.9500
C7—C8	1.390 (4)	C21—C22	1.382 (4)
C7—C27	1.487 (4)	C21—H21	0.9500
C8—C8A	1.385 (3)	C22—C23	1.380 (4)
C8—H8	0.9500	C22—H22	0.9500
C8A—N9	1.385 (3)	C23—H23	0.9500
N9—C9A	1.390 (3)	N24—O25	1.224 (3)
N9—C10	1.459 (3)	N24—O26	1.225 (3)
C10—C11	1.526 (4)	C27—C32	1.398 (3)
C10—H10A	0.9900	C27—C28	1.400 (4)
C10—H10B	0.9900	C28—C29	1.382 (4)
C11—C12	1.524 (4)	C28—N33	1.475 (3)
C11—H11A	0.9900	C29—C30	1.383 (4)
C11—H11B	0.9900	C29—H29	0.9500
C12—C13	1.515 (4)	C30—C31	1.379 (4)
C12—H12A	0.9900	C30—H30	0.9500
C12—H12B	0.9900	C31—C32	1.381 (4)
C13—C14	1.522 (4)	C31—H31	0.9500
C13—H13A	0.9900	C32—H32	0.9500
C13—H13B	0.9900	N33—O35	1.225 (3)
C14—C15	1.514 (4)	N33—O34	1.225 (3)

C9A—C1—C2	118.2 (2)	C13—C14—H14A	108.9
C9A—C1—H1	120.9	C15—C14—H14B	108.9
C2—C1—H1	120.9	C13—C14—H14B	108.9
C1—C2—C3	120.3 (2)	H14A—C14—H14B	107.8
C1—C2—C18	119.8 (2)	C14—C15—C16	115.0 (2)
C3—C2—C18	119.9 (2)	C14—C15—H15A	108.5
C4—C3—C2	120.7 (2)	C16—C15—H15A	108.5
C4—C3—H3	119.7	C14—C15—H15B	108.5
C2—C3—H3	119.7	C16—C15—H15B	108.5
C3—C4—C4A	119.9 (2)	H15A—C15—H15B	107.5
C3—C4—H4	120.1	C15—C16—C17	112.8 (3)
C4A—C4—H4	120.1	C15—C16—H16A	109.0
C4—C4A—C9A	118.7 (2)	C17—C16—H16A	109.0
C4—C4A—C4B	134.4 (3)	C15—C16—H16B	109.0
C9A—C4A—C4B	106.8 (2)	C17—C16—H16B	109.0
C5—C4B—C8A	118.1 (2)	H16A—C16—H16B	107.8
C5—C4B—C4A	135.2 (2)	C16—C17—H17A	109.5
C8A—C4B—C4A	106.6 (2)	C16—C17—H17B	109.5
C6—C5—C4B	119.8 (2)	H17A—C17—H17B	109.5
C6—C5—H5	120.1	C16—C17—H17C	109.5
C4B—C5—H5	120.1	H17A—C17—H17C	109.5
C5—C6—C7	121.3 (2)	H17B—C17—H17C	109.5
C5—C6—H6	119.4	C23—C18—C19	115.1 (2)
C7—C6—H6	119.4	C23—C18—C2	121.7 (2)
C8—C7—C6	119.8 (2)	C19—C18—C2	123.1 (2)
C8—C7—C27	118.5 (2)	C20—C19—C18	123.7 (2)
C6—C7—C27	121.7 (2)	C20—C19—N24	116.2 (2)
C8A—C8—C7	118.5 (2)	C18—C19—N24	120.1 (2)
C8A—C8—H8	120.7	C19—C20—C21	118.7 (3)
C7—C8—H8	120.7	C19—C20—H20	120.6
N9—C8A—C8	128.5 (2)	C21—C20—H20	120.6
N9—C8A—C4B	109.1 (2)	C22—C21—C20	119.7 (3)
C8—C8A—C4B	122.3 (2)	C22—C21—H21	120.2
C8A—N9—C9A	108.5 (2)	C20—C21—H21	120.2
C8A—N9—C10	125.1 (2)	C23—C22—C21	120.1 (3)
C9A—N9—C10	126.4 (2)	C23—C22—H22	120.0
C1—C9A—N9	128.9 (2)	C21—C22—H22	120.0
C1—C9A—C4A	122.3 (2)	C22—C23—C18	122.6 (3)
N9—C9A—C4A	108.9 (2)	C22—C23—H23	118.7
N9—C10—C11	112.8 (2)	C18—C23—H23	118.7
N9—C10—H10A	109.0	O25—N24—O26	123.9 (2)
C11—C10—H10A	109.0	O25—N24—C19	117.7 (2)
N9—C10—H10B	109.0	O26—N24—C19	118.3 (2)
C11—C10—H10B	109.0	C32—C27—C28	115.6 (3)
H10A—C10—H10B	107.8	C32—C27—C7	121.3 (2)
C12—C11—C10	112.0 (2)	C28—C27—C7	122.9 (2)
C12—C11—H11A	109.2	C29—C28—C27	123.5 (3)
C10—C11—H11A	109.2	C29—C28—N33	116.2 (2)
C12—C11—H11B	109.2	C27—C28—N33	120.1 (2)
C10—C11—H11B	109.2	C28—C29—C30	118.6 (3)
H11A—C11—H11B	107.9	C28—C29—H29	120.7
C13—C12—C11	112.5 (2)	C30—C29—H29	120.7
C13—C12—H12A	109.1	C31—C30—C29	119.8 (3)
C11—C12—H12A	109.1	C31—C30—H30	120.1
C13—C12—H12B	109.1	C29—C30—H30	120.1
C11—C12—H12B	109.1	C30—C31—C32	120.6 (3)
H12A—C12—H12B	107.8	C30—C31—H31	119.7
C12—C13—C14	114.7 (2)	C32—C31—H31	119.7
C12—C13—H13A	108.6	C31—C32—C27	121.7 (3)
C14—C13—H13A	108.6	C31—C32—H32	119.1
C12—C13—H13B	108.6	C27—C32—H32	119.1
C14—C13—H13B	108.6	O35—N33—O34	124.5 (3)
H13A—C13—H13B	107.6	O35—N33—C28	117.1 (3)
C15—C14—C13	113.2 (2)	O34—N33—C28	118.4 (2)
C15—C14—H14A	108.9

C9A—C1—C2—C3	−1.3 (4)	C11—C12—C13—C14	177.5 (2)
C9A—C1—C2—C18	179.1 (2)	C12—C13—C14—C15	173.2 (2)
C1—C2—C3—C4	1.0 (4)	C13—C14—C15—C16	178.2 (2)
C18—C2—C3—C4	−179.3 (2)	C14—C15—C16—C17	177.0 (2)
C2—C3—C4—C4A	−0.3 (4)	C1—C2—C18—C23	136.3 (3)
C3—C4—C4A—C9A	−0.2 (4)	C3—C2—C18—C23	−43.3 (3)
C3—C4—C4A—C4B	−178.9 (3)	C1—C2—C18—C19	−41.6 (3)
C4—C4A—C4B—C5	0.3 (5)	C3—C2—C18—C19	138.7 (3)
C9A—C4A—C4B—C5	−178.4 (3)	C23—C18—C19—C20	−2.5 (4)
C4—C4A—C4B—C8A	179.5 (3)	C2—C18—C19—C20	175.6 (2)
C9A—C4A—C4B—C8A	0.7 (3)	C23—C18—C19—N24	174.8 (2)
C8A—C4B—C5—C6	−0.0 (4)	C2—C18—C19—N24	−7.2 (4)
C4A—C4B—C5—C6	179.1 (3)	C18—C19—C20—C21	2.1 (4)
C4B—C5—C6—C7	−1.2 (4)	N24—C19—C20—C21	−175.3 (2)
C5—C6—C7—C8	2.8 (4)	C19—C20—C21—C22	−0.1 (4)
C5—C6—C7—C27	−178.1 (2)	C20—C21—C22—C23	−1.4 (4)
C6—C7—C8—C8A	−3.0 (4)	C21—C22—C23—C18	0.9 (4)
C27—C7—C8—C8A	177.8 (2)	C19—C18—C23—C22	1.0 (4)
C7—C8—C8A—N9	−178.4 (3)	C2—C18—C23—C22	−177.1 (2)
C7—C8—C8A—C4B	1.8 (4)	C20—C19—N24—O25	−61.9 (3)
C5—C4B—C8A—N9	179.9 (2)	C18—C19—N24—O25	120.6 (3)
C4A—C4B—C8A—N9	0.5 (3)	C20—C19—N24—O26	116.7 (3)
C5—C4B—C8A—C8	−0.3 (4)	C18—C19—N24—O26	−60.8 (3)
C4A—C4B—C8A—C8	−179.6 (2)	C8—C7—C27—C32	127.9 (3)
C8—C8A—N9—C9A	178.5 (3)	C6—C7—C27—C32	−51.2 (4)
C4B—C8A—N9—C9A	−1.6 (3)	C8—C7—C27—C28	−47.1 (4)
C8—C8A—N9—C10	−0.1 (4)	C6—C7—C27—C28	133.7 (3)
C4B—C8A—N9—C10	179.8 (2)	C32—C27—C28—C29	−3.7 (4)
C2—C1—C9A—N9	−178.4 (2)	C7—C27—C28—C29	171.5 (3)
C2—C1—C9A—C4A	0.8 (4)	C32—C27—C28—N33	172.1 (2)
C8A—N9—C9A—C1	−178.7 (3)	C7—C27—C28—N33	−12.6 (4)
C10—N9—C9A—C1	−0.2 (4)	C27—C28—C29—C30	3.3 (4)
C8A—N9—C9A—C4A	2.1 (3)	N33—C28—C29—C30	−172.8 (3)
C10—N9—C9A—C4A	−179.4 (2)	C28—C29—C30—C31	−0.4 (4)
C4—C4A—C9A—C1	−0.0 (4)	C29—C30—C31—C32	−1.7 (4)
C4B—C4A—C9A—C1	179.0 (2)	C30—C31—C32—C27	1.1 (4)
C4—C4A—C9A—N9	179.3 (2)	C28—C27—C32—C31	1.5 (4)
C4B—C4A—C9A—N9	−1.7 (3)	C7—C27—C32—C31	−173.9 (3)
C8A—N9—C10—C11	74.3 (3)	C29—C28—N33—O35	−44.5 (4)
C9A—N9—C10—C11	−104.0 (3)	C27—C28—N33—O35	139.3 (3)
N9—C10—C11—C12	179.4 (2)	C29—C28—N33—O34	133.6 (3)
C10—C11—C12—C13	168.0 (2)	C27—C28—N33—O34	−42.6 (4)

Experimental details

Crystal data
Chemical formula	C₃₂H₃₁N₃O₄
M_r	521.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	8.722 (2), 7.987 (2), 39.508 (11)
β (°)	95.044 (6)
V (Å³)	2741.5 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.50 × 0.04 × 0.04

Data collection
Diffractometer	Bruker SMART APEXII
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	15053, 6525, 2814
R_int	0.099
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.137, 0.93
No. of reflections	6525
No. of parameters	353
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.22

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Acknowledgements

The authors are grateful to A. Oehlhof and S. Mallon for preparative assistance.

References

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