N-Cyclo­hexyl-5H,7H-13,15-dimethyl-9-nitro-5-oxophenanthrido[4,4a,5-bc][1,4]benzoxazepine-7-carboxamide

Luo, J.-L.; Wu, J.-L.

doi:10.1107/S1600536809028712

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1996

doi:10.1107/S1600536809028712

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N-Cyclohexyl-5H,7H-13,15-dimethyl-9-nitro-5-oxophenanthrido[4,4a,5-bc][1,4]benzoxazepine-7-carboxamide

Jia-Lu Luo ^a and Jin-Long Wu ^a ^*

^aLaboratory of Asymmetric Catalysis and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang 310027, People's Republic of China
^*Correspondence e-mail: wyz@zju.edu.cn

(Received 16 July 2009; accepted 20 July 2009; online 25 July 2009)

In the title compound, C₂₉H₂₇N₃O₅, a dibenz[b,f][1,4]oxazepine derivative, the cyclohexane ring adopts a chair conformation, the oxazepine seven-membered ring has a twist-boat conformation, and the piperidin-2-one ring assumes a flattened boat conformation. Intermolecular N—H⋯O hydrogen bonding between imino and nitro groups links two molecules into a centrosymmetric dimer.

Related literature

For the biological activity of dibenz[b,f][1,4]oxazepines, see: Klunder et al. (1992 ); Merluzzi et al. (1990 ); Nagarajan et al. (1986 ); Hallinan et al. (1993 , 1996 ). For our recent microwave-assisted synthesis of dibenz[b,f][1,4]oxazepines, see: Dai & Shi (2007 ); Xing et al. (2006 ). For microwave-assisted palladium-catalysed intramolecular direct arylation, see: Wu et al. (2007 ).

Experimental

Crystal data

C₂₉H₂₇N₃O₅
M_r = 497.54
Monoclinic, P 2₁ /c
a = 10.7451 (4) Å
b = 27.8791 (7) Å
c = 8.4917 (3) Å
β = 105.428 (13)°
V = 2452.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.28 × 0.26 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: none
23870 measured reflections
5594 independent reflections
3756 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.127
S = 1.00
5594 reflections
336 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O3ⁱ	0.86	2.29	3.046 (2)	147
Symmetry code: (i) -x+1, -y, -z+2.

Data collection: PROCESS-AUTO (Rigaku, 2006 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028712/xu2558sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809028712/xu2558Isup2.hkl

checkCIF report

Comment top

The title compound, C₂₉H₂₇N₃O₅, is viewed as the derivative of dibenz[b,f][1,4]oxazepines, which have been reported to deliver various biological activities such as non-nucleoside inhibitor of HIV-1 reverse transcriptase (Klunder et al., 1992; Merluzzi et al., 1990), antidepressant (Nagarajan et al., 1986), and PGE₂ antagonist and analgesic (Hallinan et al., 1993, 1996). The title compound has recently been obtained during microwave-assisted synthesis of a derivative of dibenz[b,f][1,4]oxazepines (Dai & Shi, 2007; Xing et al., 2006) with a microwave-assisted palladium-catalyzed intramolecular direct arylation reaction (Wu et al., 2007). We report here its crystal structure.

In the molecular structure (Fig. 1) there are one cyclohexane, one oxazepine and one piperidin-2-one rings. The cyclohexane ring adopts a chair conformation with atoms C16 and C19 deviated from the mean plane formed by the other four atoms by 0.677 (3) and -0.673 (4) Å, respectively. The 7-membered oxazepine ring has a twist-boat conformation, and the piperidin-2-one assumes a flatboat conformation. Intermolecular N—H···O hydrogen-bond bonding between imino and nitro groups (Table 1) links two molecules into the centro-symmetric dimer.

Related literature top

For the biological activity of dibenz[b,f][1,4]oxazepines, see: Klunder et al. (1992); Merluzzi et al. (1990); Nagarajan et al. (1986); Hallinan et al. (1993, 1996). For our recent microwave-assisted synthesis of dibenz[b,f][1,4]oxazepines, see: Dai & Shi (2007); Xing et al. (2006). For microwave-assisted palladium-catalysed intramolecular direct arylation, see: Wu et al. (2007).

Experimental top

A 10-ml pressurized process vial was charged with the bromide (59.5 mg, 0.10 mmol), Pd(OAc)₂ (0.6 mg, 0.0026 mmol), 1,1'-bis(diphenylphosphino)ferrocene (1.6 mg, 0.0028 mmol), and K₂CO₃ (27.7 mg, 0.20 mmol) and it was sealed with a cap containing a silicon septum. The vial was then evacuated and backfilled with N₂ (repeated for several times) through the cap using a needle. To the degassed vial was added degassed anhydrous PhMe (2 ml) through the cap using a syringe. The loaded vial was then placed into the microwave reactor cavity and was heated at 423 K for 1 h. After cooled to room temperature the resultant mixture was filtered off through a plug of Celite with washing by EtOAc. The combined filtrate was evaporated under reduced pressure. The residue was purified by column chromatography (silica gel, 20% EtOAc in petroleum ether) to furnish the title compound in 95% yield (48.5 mg) as a pale yellow solid. m.p. > 555 K (EtOAc-hexane). Single crystals suitable for X-ray diffraction of the title compound were grown in the mixed solvent of ethyl acetate and hexane.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: CrystalStructure (Rigaku, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku, 2007).

Figures top

Fig. 1. A view of (1). Displacement ellipsoids are drawn at 40% probability level and H atoms are shown as small circles of arbitary radii.

N-Cyclohexyl-5H,7H-13,15-dimethyl-9-nitro-5- oxophenanthrido[4,4a,5-bc][1,4]benzoxazepine-7-carboxamide top

Crystal data top

C₂₉H₂₇N₃O₅	F(000) = 1048
M_r = 497.54	D_x = 1.348 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 15928 reflections
a = 10.7451 (4) Å	θ = 3.1–27.5°
b = 27.8791 (7) Å	µ = 0.09 mm⁻¹
c = 8.4917 (3) Å	T = 296 K
β = 105.428 (13)°	Chunk, yellow
V = 2452.1 (2) Å³	0.28 × 0.26 × 0.11 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	3756 reflections with I > 2σ(I)
Radiation source: rolling anode	R_int = 0.054
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
Detector resolution: 10.00 pixels mm^-1	h = −13→13
ω scans	k = −36→35
23870 measured reflections	l = −10→10
5594 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.127	w = 1/[σ²(F_o²) + (0.0432P)² + 1P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
5594 reflections	Δρ_max = 0.29 e Å⁻³
336 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0051 (10)

Crystal data top

C₂₉H₂₇N₃O₅	V = 2452.1 (2) Å³
M_r = 497.54	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.7451 (4) Å	µ = 0.09 mm⁻¹
b = 27.8791 (7) Å	T = 296 K
c = 8.4917 (3) Å	0.28 × 0.26 × 0.11 mm
β = 105.428 (13)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3756 reflections with I > 2σ(I)
23870 measured reflections	R_int = 0.054
5594 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.00	Δρ_max = 0.29 e Å⁻³
5594 reflections	Δρ_min = −0.23 e Å⁻³
336 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)
O2	0.52077 (12)	0.14876 (4)	0.75758 (15)	0.0441 (3)
N1	0.30895 (13)	0.12575 (5)	0.46737 (17)	0.0363 (3)
O5	0.53052 (13)	0.12552 (5)	0.37217 (15)	0.0509 (4)
C13	0.43278 (17)	0.18313 (6)	0.6721 (2)	0.0371 (4)
C14	0.32745 (16)	0.17213 (6)	0.5375 (2)	0.0355 (4)
N3	0.63285 (14)	0.07287 (6)	0.56536 (19)	0.0429 (4)
H3	0.6229	0.0498	0.6281	0.052*
C10	0.27335 (18)	0.25731 (7)	0.5195 (2)	0.0423 (4)
C9	0.23969 (17)	0.20945 (6)	0.4689 (2)	0.0383 (4)
C22	0.40912 (16)	0.07561 (6)	0.7002 (2)	0.0381 (4)
O1	0.20934 (15)	0.07613 (5)	0.25999 (19)	0.0654 (4)
C12	0.46090 (18)	0.22939 (7)	0.7269 (2)	0.0419 (4)
C1	0.40183 (16)	0.08658 (6)	0.5246 (2)	0.0364 (4)
H1	0.3657	0.0581	0.4615	0.044*
C16	0.76257 (17)	0.08427 (6)	0.5510 (2)	0.0406 (4)
H16	0.7586	0.0869	0.4347	0.049*
C3	0.10767 (18)	0.15002 (7)	0.2797 (2)	0.0437 (4)
C11	0.38132 (19)	0.26588 (7)	0.6456 (2)	0.0453 (4)
H11	0.4019	0.2974	0.6779	0.054*
C27	0.46631 (17)	0.10965 (7)	0.8143 (2)	0.0411 (4)
C15	0.52969 (17)	0.09773 (6)	0.4828 (2)	0.0378 (4)
C2	0.21089 (18)	0.11460 (7)	0.3296 (2)	0.0440 (4)
N2	0.3006 (2)	−0.01158 (8)	0.9665 (3)	0.0698 (6)
C8	0.11937 (18)	0.19597 (7)	0.3490 (2)	0.0430 (4)
C23	0.35448 (18)	0.03542 (7)	0.7497 (2)	0.0455 (5)
H23	0.3150	0.0120	0.6749	0.055*
C24	0.3602 (2)	0.03099 (8)	0.9136 (3)	0.0521 (5)
C26	0.4739 (2)	0.10462 (8)	0.9787 (2)	0.0531 (5)
H26	0.5151	0.1276	1.0540	0.064*
O3	0.3241 (2)	−0.01856 (7)	1.1134 (2)	0.0931 (7)
C25	0.4187 (2)	0.06458 (8)	1.0275 (3)	0.0581 (6)
H25	0.4211	0.0604	1.1369	0.070*
C4	−0.0059 (2)	0.13491 (9)	0.1673 (3)	0.0583 (6)
H4	−0.0109	0.1043	0.1223	0.070*
C28	0.2043 (2)	0.30111 (7)	0.4341 (3)	0.0576 (5)
H28A	0.1288	0.3071	0.4712	0.086*
H28B	0.1793	0.2957	0.3183	0.086*
H28C	0.2609	0.3283	0.4585	0.086*
C29	0.5782 (2)	0.24052 (8)	0.8644 (3)	0.0555 (5)
H29A	0.5820	0.2744	0.8856	0.067*	0.50
H29B	0.6544	0.2307	0.8345	0.067*	0.50
H29C	0.5729	0.2236	0.9608	0.067*	0.50
H29D	0.6243	0.2114	0.9017	0.067*	0.50
H29E	0.5518	0.2551	0.9528	0.067*	0.50
H29F	0.6333	0.2622	0.8265	0.067*	0.50
C21	0.8092 (2)	0.13172 (8)	0.6321 (3)	0.0585 (6)
H21A	0.8113	0.1302	0.7469	0.070*
H21B	0.7498	0.1570	0.5819	0.070*
C7	0.0090 (2)	0.22515 (8)	0.3054 (3)	0.0586 (6)
H7	0.0109	0.2553	0.3529	0.070*
C19	1.0384 (2)	0.10368 (9)	0.6890 (3)	0.0697 (7)
H19A	1.1223	0.1111	0.6728	0.084*
H19B	1.0475	0.1017	0.8055	0.084*
C18	0.9917 (2)	0.05620 (8)	0.6100 (3)	0.0624 (6)
H18A	1.0508	0.0311	0.6621	0.075*
H18B	0.9910	0.0573	0.4956	0.075*
O4	0.2348 (2)	−0.03785 (8)	0.8627 (3)	0.1074 (8)
C17	0.85656 (19)	0.04450 (8)	0.6240 (3)	0.0560 (5)
H17A	0.8275	0.0146	0.5676	0.067*
H17B	0.8588	0.0403	0.7382	0.067*
C5	−0.1100 (2)	0.16528 (10)	0.1235 (3)	0.0711 (7)
H5	−0.1851	0.1557	0.0470	0.085*
C6	−0.1020 (2)	0.21008 (10)	0.1942 (3)	0.0717 (7)
H6	−0.1729	0.2305	0.1661	0.086*
C20	0.9432 (2)	0.14320 (9)	0.6151 (4)	0.0747 (7)
H20A	0.9397	0.1468	0.5004	0.090*
H20B	0.9725	0.1733	0.6696	0.090*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0353 (7)	0.0476 (7)	0.0436 (7)	0.0026 (6)	0.0003 (6)	0.0016 (6)
N1	0.0318 (7)	0.0418 (8)	0.0331 (7)	0.0010 (6)	0.0050 (6)	−0.0007 (6)
O5	0.0476 (8)	0.0657 (9)	0.0409 (7)	0.0051 (7)	0.0144 (6)	0.0145 (7)
C13	0.0336 (9)	0.0430 (9)	0.0344 (9)	0.0014 (7)	0.0084 (7)	0.0016 (7)
C14	0.0333 (9)	0.0417 (9)	0.0324 (8)	−0.0011 (7)	0.0104 (7)	0.0008 (7)
N3	0.0347 (8)	0.0480 (9)	0.0470 (9)	0.0021 (7)	0.0125 (7)	0.0101 (7)
C10	0.0417 (10)	0.0443 (10)	0.0441 (10)	0.0042 (8)	0.0169 (9)	0.0052 (8)
C9	0.0356 (9)	0.0453 (10)	0.0349 (9)	0.0020 (8)	0.0111 (7)	0.0045 (7)
C22	0.0305 (9)	0.0470 (10)	0.0362 (9)	0.0065 (8)	0.0075 (7)	0.0064 (8)
O1	0.0584 (9)	0.0635 (9)	0.0603 (9)	0.0070 (8)	−0.0088 (7)	−0.0223 (8)
C12	0.0398 (10)	0.0487 (10)	0.0381 (9)	−0.0044 (8)	0.0122 (8)	−0.0032 (8)
C1	0.0348 (9)	0.0392 (9)	0.0334 (8)	0.0006 (7)	0.0059 (7)	0.0002 (7)
C16	0.0346 (9)	0.0459 (10)	0.0425 (10)	−0.0002 (8)	0.0126 (8)	0.0001 (8)
C3	0.0342 (10)	0.0584 (11)	0.0356 (9)	0.0001 (8)	0.0044 (8)	0.0035 (8)
C11	0.0486 (11)	0.0430 (10)	0.0462 (10)	−0.0027 (9)	0.0157 (9)	−0.0042 (8)
C27	0.0354 (9)	0.0495 (10)	0.0372 (9)	0.0088 (8)	0.0077 (8)	0.0050 (8)
C15	0.0377 (10)	0.0432 (10)	0.0323 (9)	−0.0003 (8)	0.0088 (7)	−0.0010 (7)
C2	0.0380 (10)	0.0523 (11)	0.0384 (9)	−0.0018 (8)	0.0047 (8)	−0.0022 (8)
N2	0.0618 (13)	0.0776 (14)	0.0797 (15)	0.0213 (11)	0.0359 (12)	0.0415 (12)
C8	0.0364 (10)	0.0525 (11)	0.0400 (10)	0.0029 (8)	0.0103 (8)	0.0088 (8)
C23	0.0352 (10)	0.0522 (11)	0.0487 (11)	0.0043 (8)	0.0106 (8)	0.0113 (9)
C24	0.0451 (11)	0.0619 (13)	0.0548 (12)	0.0168 (10)	0.0229 (10)	0.0215 (10)
C26	0.0589 (13)	0.0615 (13)	0.0362 (10)	0.0213 (11)	0.0078 (9)	0.0017 (9)
O3	0.1025 (15)	0.1061 (15)	0.0891 (13)	0.0394 (12)	0.0579 (12)	0.0579 (11)
C25	0.0669 (14)	0.0724 (14)	0.0402 (11)	0.0292 (12)	0.0234 (10)	0.0174 (10)
C4	0.0450 (12)	0.0729 (14)	0.0485 (11)	−0.0028 (11)	−0.0022 (9)	−0.0050 (10)
C28	0.0593 (13)	0.0470 (11)	0.0654 (13)	0.0083 (10)	0.0145 (11)	0.0086 (10)
C29	0.0500 (12)	0.0595 (12)	0.0526 (12)	−0.0089 (10)	0.0061 (10)	−0.0104 (10)
C21	0.0457 (12)	0.0549 (12)	0.0732 (14)	0.0015 (10)	0.0132 (11)	−0.0130 (11)
C7	0.0457 (12)	0.0596 (13)	0.0654 (14)	0.0090 (10)	0.0059 (11)	0.0089 (11)
C19	0.0393 (12)	0.0793 (16)	0.0898 (17)	−0.0087 (11)	0.0158 (12)	−0.0193 (14)
C18	0.0400 (11)	0.0662 (14)	0.0813 (16)	0.0054 (10)	0.0168 (11)	−0.0123 (12)
O4	0.1032 (17)	0.1027 (16)	0.1141 (18)	−0.0339 (14)	0.0253 (14)	0.0357 (14)
C17	0.0417 (11)	0.0503 (12)	0.0751 (15)	0.0034 (9)	0.0140 (10)	0.0007 (10)
C5	0.0402 (12)	0.0983 (19)	0.0620 (14)	0.0048 (12)	−0.0087 (11)	0.0015 (14)
C6	0.0434 (13)	0.0856 (18)	0.0755 (16)	0.0171 (12)	−0.0030 (12)	0.0097 (14)
C20	0.0544 (14)	0.0601 (14)	0.108 (2)	−0.0151 (11)	0.0187 (14)	−0.0168 (14)

Geometric parameters (Å, º) top

O2—C27	1.383 (2)	C23—C24	1.382 (3)
O2—C13	1.405 (2)	C23—H23	0.9300
N1—C2	1.386 (2)	C24—C25	1.373 (3)
N1—C14	1.415 (2)	C26—C25	1.379 (3)
N1—C1	1.472 (2)	C26—H26	0.9300
O5—C15	1.219 (2)	C25—H25	0.9300
C13—C12	1.377 (2)	C4—C5	1.373 (3)
C13—C14	1.412 (2)	C4—H4	0.9300
C14—C9	1.421 (2)	C28—H28A	0.9600
N3—C15	1.337 (2)	C28—H28B	0.9600
N3—C16	1.466 (2)	C28—H28C	0.9600
N3—H3	0.8600	C29—H29A	0.9600
C10—C11	1.374 (3)	C29—H29B	0.9600
C10—C9	1.419 (3)	C29—H29C	0.9600
C10—C28	1.510 (3)	C29—H29D	0.9600
C9—C8	1.466 (3)	C29—H29E	0.9600
C22—C27	1.378 (3)	C29—H29F	0.9600
C22—C23	1.381 (3)	C21—C20	1.519 (3)
C22—C1	1.503 (2)	C21—H21A	0.9700
O1—C2	1.223 (2)	C21—H21B	0.9700
C12—C11	1.389 (3)	C7—C6	1.375 (3)
C12—C29	1.505 (3)	C7—H7	0.9300
C1—C15	1.540 (2)	C19—C18	1.508 (3)
C1—H1	0.9800	C19—C20	1.521 (4)
C16—C21	1.514 (3)	C19—H19A	0.9700
C16—C17	1.517 (3)	C19—H19B	0.9700
C16—H16	0.9800	C18—C17	1.524 (3)
C3—C4	1.400 (3)	C18—H18A	0.9700
C3—C8	1.401 (3)	C18—H18B	0.9700
C3—C2	1.461 (3)	C17—H17A	0.9700
C11—H11	0.9300	C17—H17B	0.9700
C27—C26	1.384 (3)	C5—C6	1.378 (4)
N2—O4	1.217 (3)	C5—H5	0.9300
N2—O3	1.221 (3)	C6—H6	0.9300
N2—C24	1.474 (3)	C20—H20A	0.9700
C8—C7	1.404 (3)	C20—H20B	0.9700

C27—O2—C13	115.38 (13)	C5—C4—C3	119.9 (2)
C2—N1—C14	123.40 (15)	C5—C4—H4	120.0
C2—N1—C1	114.14 (14)	C3—C4—H4	120.0
C14—N1—C1	122.12 (13)	C10—C28—H28A	109.5
C12—C13—O2	114.03 (15)	C10—C28—H28B	109.5
C12—C13—C14	122.24 (16)	H28A—C28—H28B	109.5
O2—C13—C14	123.68 (15)	C10—C28—H28C	109.5
C13—C14—N1	122.13 (15)	H28A—C28—H28C	109.5
C13—C14—C9	118.32 (16)	H28B—C28—H28C	109.5
N1—C14—C9	119.54 (15)	C12—C29—H29A	109.5
C15—N3—C16	121.20 (15)	C12—C29—H29B	109.5
C15—N3—H3	119.4	H29A—C29—H29B	109.5
C16—N3—H3	119.4	C12—C29—H29C	109.5
C11—C10—C9	119.59 (17)	H29A—C29—H29C	109.5
C11—C10—C28	116.01 (18)	H29B—C29—H29C	109.5
C9—C10—C28	124.19 (18)	C12—C29—H29D	109.5
C14—C9—C10	118.47 (16)	H29A—C29—H29D	141.1
C14—C9—C8	117.61 (16)	H29B—C29—H29D	56.3
C10—C9—C8	123.91 (16)	H29C—C29—H29D	56.3
C27—C22—C23	119.37 (17)	C12—C29—H29E	109.5
C27—C22—C1	116.93 (16)	H29A—C29—H29E	56.3
C23—C22—C1	123.55 (17)	H29B—C29—H29E	141.1
C13—C12—C11	117.88 (17)	H29C—C29—H29E	56.3
C13—C12—C29	121.21 (17)	H29D—C29—H29E	109.5
C11—C12—C29	120.83 (17)	C12—C29—H29F	109.5
N1—C1—C22	109.29 (14)	H29A—C29—H29F	56.3
N1—C1—C15	110.02 (14)	H29B—C29—H29F	56.3
C22—C1—C15	117.11 (14)	H29C—C29—H29F	141.1
N1—C1—H1	106.6	H29D—C29—H29F	109.5
C22—C1—H1	106.6	H29E—C29—H29F	109.5
C15—C1—H1	106.6	C16—C21—C20	110.38 (18)
N3—C16—C21	110.99 (15)	C16—C21—H21A	109.6
N3—C16—C17	110.60 (15)	C20—C21—H21A	109.6
C21—C16—C17	110.42 (17)	C16—C21—H21B	109.6
N3—C16—H16	108.2	C20—C21—H21B	109.6
C21—C16—H16	108.2	H21A—C21—H21B	108.1
C17—C16—H16	108.2	C6—C7—C8	121.4 (2)
C4—C3—C8	121.73 (18)	C6—C7—H7	119.3
C4—C3—C2	116.84 (18)	C8—C7—H7	119.3
C8—C3—C2	121.33 (16)	C18—C19—C20	110.2 (2)
C10—C11—C12	122.71 (18)	C18—C19—H19A	109.6
C10—C11—H11	118.6	C20—C19—H19A	109.6
C12—C11—H11	118.6	C18—C19—H19B	109.6
C22—C27—O2	116.68 (15)	C20—C19—H19B	109.6
C22—C27—C26	122.35 (19)	H19A—C19—H19B	108.1
O2—C27—C26	120.94 (18)	C19—C18—C17	111.34 (18)
O5—C15—N3	123.95 (17)	C19—C18—H18A	109.4
O5—C15—C1	119.73 (16)	C17—C18—H18A	109.4
N3—C15—C1	116.14 (15)	C19—C18—H18B	109.4
O1—C2—N1	120.96 (17)	C17—C18—H18B	109.4
O1—C2—C3	122.76 (17)	H18A—C18—H18B	108.0
N1—C2—C3	116.18 (16)	C16—C17—C18	110.87 (18)
O4—N2—O3	124.5 (2)	C16—C17—H17A	109.5
O4—N2—C24	118.7 (2)	C18—C17—H17A	109.5
O3—N2—C24	116.8 (3)	C16—C17—H17B	109.5
C3—C8—C7	116.36 (18)	C18—C17—H17B	109.5
C3—C8—C9	119.33 (16)	H17A—C17—H17B	108.1
C7—C8—C9	124.15 (18)	C4—C5—C6	119.3 (2)
C24—C23—C22	118.1 (2)	C4—C5—H5	120.4
C24—C23—H23	121.0	C6—C5—H5	120.4
C22—C23—H23	121.0	C7—C6—C5	121.2 (2)
C25—C24—C23	122.5 (2)	C7—C6—H6	119.4
C25—C24—N2	119.3 (2)	C5—C6—H6	119.4
C23—C24—N2	118.2 (2)	C19—C20—C21	111.0 (2)
C25—C26—C27	118.1 (2)	C19—C20—H20A	109.4
C25—C26—H26	120.9	C21—C20—H20A	109.4
C27—C26—H26	120.9	C19—C20—H20B	109.4
C24—C25—C26	119.56 (18)	C21—C20—H20B	109.4
C24—C25—H25	120.2	H20A—C20—H20B	108.0
C26—C25—H25	120.2

C27—O2—C13—C12	129.21 (16)	N1—C1—C15—N3	161.90 (15)
C27—O2—C13—C14	−53.3 (2)	C22—C1—C15—N3	36.3 (2)
C12—C13—C14—N1	171.12 (16)	C14—N1—C2—O1	169.55 (18)
O2—C13—C14—N1	−6.2 (3)	C1—N1—C2—O1	−3.9 (3)
C12—C13—C14—C9	−7.3 (3)	C14—N1—C2—C3	−13.8 (2)
O2—C13—C14—C9	175.38 (15)	C1—N1—C2—C3	172.76 (15)
C2—N1—C14—C13	−176.13 (16)	C4—C3—C2—O1	11.5 (3)
C1—N1—C14—C13	−3.2 (2)	C8—C3—C2—O1	−172.22 (19)
C2—N1—C14—C9	2.3 (2)	C4—C3—C2—N1	−165.04 (17)
C1—N1—C14—C9	175.19 (15)	C8—C3—C2—N1	11.2 (3)
C13—C14—C9—C10	10.7 (2)	C4—C3—C8—C7	3.0 (3)
N1—C14—C9—C10	−167.78 (15)	C2—C3—C8—C7	−173.10 (18)
C13—C14—C9—C8	−169.55 (15)	C4—C3—C8—C9	178.60 (18)
N1—C14—C9—C8	12.0 (2)	C2—C3—C8—C9	2.5 (3)
C11—C10—C9—C14	−7.5 (3)	C14—C9—C8—C3	−14.1 (2)
C28—C10—C9—C14	167.06 (17)	C10—C9—C8—C3	165.58 (17)
C11—C10—C9—C8	172.82 (17)	C14—C9—C8—C7	161.12 (18)
C28—C10—C9—C8	−12.7 (3)	C10—C9—C8—C7	−19.1 (3)
O2—C13—C12—C11	177.86 (15)	C27—C22—C23—C24	−0.3 (3)
C14—C13—C12—C11	0.3 (3)	C1—C22—C23—C24	−175.65 (17)
O2—C13—C12—C29	1.1 (2)	C22—C23—C24—C25	−0.6 (3)
C14—C13—C12—C29	−176.40 (17)	C22—C23—C24—N2	179.31 (17)
C2—N1—C1—C22	−124.19 (16)	O4—N2—C24—C25	170.6 (2)
C14—N1—C1—C22	62.3 (2)	O3—N2—C24—C25	−11.2 (3)
C2—N1—C1—C15	105.92 (17)	O4—N2—C24—C23	−9.4 (3)
C14—N1—C1—C15	−67.58 (19)	O3—N2—C24—C23	168.84 (19)
C27—C22—C1—N1	−69.71 (19)	C22—C27—C26—C25	−1.8 (3)
C23—C22—C1—N1	105.78 (19)	O2—C27—C26—C25	−179.40 (17)
C27—C22—C1—C15	56.2 (2)	C23—C24—C25—C26	0.3 (3)
C23—C22—C1—C15	−128.31 (18)	N2—C24—C25—C26	−179.63 (18)
C15—N3—C16—C21	70.1 (2)	C27—C26—C25—C24	0.9 (3)
C15—N3—C16—C17	−167.00 (17)	C8—C3—C4—C5	−0.6 (3)
C9—C10—C11—C12	0.4 (3)	C2—C3—C4—C5	175.6 (2)
C28—C10—C11—C12	−174.57 (18)	N3—C16—C21—C20	−179.58 (19)
C13—C12—C11—C10	3.3 (3)	C17—C16—C21—C20	57.4 (2)
C29—C12—C11—C10	180.00 (18)	C3—C8—C7—C6	−3.3 (3)
C23—C22—C27—O2	179.20 (15)	C9—C8—C7—C6	−178.7 (2)
C1—C22—C27—O2	−5.1 (2)	C20—C19—C18—C17	−56.0 (3)
C23—C22—C27—C26	1.5 (3)	N3—C16—C17—C18	−179.81 (18)
C1—C22—C27—C26	177.21 (17)	C21—C16—C17—C18	−56.6 (2)
C13—O2—C27—C22	75.73 (19)	C19—C18—C17—C16	56.3 (3)
C13—O2—C27—C26	−106.56 (19)	C3—C4—C5—C6	−1.5 (4)
C16—N3—C15—O5	12.4 (3)	C8—C7—C6—C5	1.4 (4)
C16—N3—C15—C1	−172.54 (15)	C4—C5—C6—C7	1.1 (4)
N1—C1—C15—O5	−22.8 (2)	C18—C19—C20—C21	57.0 (3)
C22—C1—C15—O5	−148.36 (17)	C16—C21—C20—C19	−57.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O3ⁱ	0.86	2.29	3.046 (2)	147

Symmetry code: (i) −x+1, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₉H₂₇N₃O₅
M_r	497.54
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	10.7451 (4), 27.8791 (7), 8.4917 (3)
β (°)	105.428 (13)
V (Å³)	2452.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.28 × 0.26 × 0.11

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	23870, 5594, 3756
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.127, 1.00
No. of reflections	5594
No. of parameters	336
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.23

Computer programs: PROCESS-AUTO (Rigaku, 2006), CrystalStructure (Rigaku, 2007), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O3ⁱ	0.86	2.29	3.046 (2)	147.0

Symmetry code: (i) −x+1, −y, −z+2.

Acknowledgements

This work was supported by a research grant from the National Natural Science Foundation of China (grant No. 20672092). Professor Wei-Min Dai is thanked for his valuable suggestions. Mr Jianming Gu and Ms Xiurong Hu of the X-ray crystallography facility of Zhejiang University are acknowledged for their assistance with the crystal structural analysis.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Dai, W. M. & Shi, J. (2007). Comb. Chem. High Throughput Screening, 10, 837–856. Web of Science CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hallinan, E. A., Hagen, T. J., Husa, R. K., Tsymbalvo, S., Rao, S. N., vanHoeck, J. P., Rafferty, M. F., Stapelfeld, A., Savage, M. A. & Reichman, M. (1993). J. Med. Chem. 36, 3293–3299. CrossRef CAS PubMed Web of Science Google Scholar
Hallinan, E. A., Hagen, T. J., Tsymbalov, S., Husa, R. K., Lee, A. C., Stapelfeld, A. & Savage, M. A. (1996). J. Med. Chem. 39, 609–613. CrossRef CAS PubMed Web of Science Google Scholar
Klunder, J. M., Hargrave, K. D., West, M. A., Cullen, E., Pal, K., Behnke, M. L., Kapadia, S. R., McNeil, D. W., Wu, J. C., Chow, G. C. & Adams, J. (1992). J. Med. Chem. 35, 1887–1897. CrossRef PubMed CAS Web of Science Google Scholar
Merluzzi, V. J., Hargrave, K. D., Labadia, M., Grozinger, K., Skoog, M., Wu, J. C., Shih, C.-K., Eckner, K., Hattox, S., Adams, J., Rosenthal, A. S., Faanes, R., Eckner, R. J., Koup, R. A. & Sullivan, J. L. (1990). Science, 250, 1411–1413. CrossRef PubMed CAS Web of Science Google Scholar
Nagarajan, K., David, J., Kulkarni, Y. S., Hendi, S. B., Shenoy, S. J. & Upadhyaya, P. (1986). Eur. J. Med. Chem. 21, 21–26. CAS Google Scholar
Rigaku (2006). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2007). CrystalStructure. Rigaku Americas Corporation, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wu, J., Nie, L., Luo, J. & Dai, W.-M. (2007). Synlett, pp. 2728–2732. Google Scholar
Xing, X., Wu, J., Luo, J. & Dai, W.-M. (2006). Synlett, pp. 2099–2103. Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

N-Cyclo­hexyl-5H,7H-13,15-di­methyl-9-nitro-5-oxophenanthrido[4,4a,5-bc][1,4]benzoxazepine-7-carboxamide

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

N-Cyclohexyl-5H,7H-13,15-dimethyl-9-nitro-5-oxophenanthrido[4,4a,5-bc][1,4]benzoxazepine-7-carboxamide