rac-7-[(2E)-But-2-eno­yl]-13-chloro-N-cyclo­hexyl-7,8-dihydro-5H-isochromeno[4,3-c]phenanthridine-8-carboxamide

Ye, N.; Wu, J.-L.

doi:10.1107/S1600536812005946

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o748

doi:10.1107/S1600536812005946

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rac-7-[(2E)-But-2-enoyl]-13-chloro-N-cyclohexyl-7,8-dihydro-5H-isochromeno[4,3-c]phenanthridine-8-carboxamide

Ning Ye ^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 6 January 2012; accepted 10 February 2012; online 17 February 2012)

In the title compound, C₃₁H₂₉ClN₂O₃, the two heterocyclic rings, belonging to a system of five condensed rings, adopt conformations intermediate between twist-boat and sofa. The secondary amide group is involved in a weak intramolecular N—H⋯N hydrogen bond. In the crystal, molecules are linked by pairs of C—H⋯Cl hydrogen bonds to form inversion dimers. These dimers are linked via a C—H⋯O interaction to form chains propagating along the b-axis direction.

Related literature

For the Ugi four-component reaction of 2-aminophenols, see: Xing et al. (2006 ); Dai et al. (2008 ). For microwave-assisted intramolecular direct arylation, see: Wu et al. (2007 ).

Experimental

Crystal data

C₃₁H₂₉ClN₂O₃
M_r = 513.01
Monoclinic, P 2₁ /n
a = 13.2616 (8) Å
b = 13.4515 (7) Å
c = 14.8338 (9) Å
β = 95.067 (2)°
V = 2635.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 296 K
0.35 × 0.32 × 0.20 mm

Data collection

Rigaku RAXIS-RAPID/ZJUG diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.930, T_max = 0.965
21259 measured reflections
4884 independent reflections
2797 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.197
S = 1.00
4884 reflections
336 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1	0.86	2.41	2.758 (3)	105
C23—H23B⋯Cl1ⁱ	0.97	2.74	3.473 (4)	133
C14—H14⋯O3ⁱⁱ	0.93	2.58	3.391 (5)	146
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku, 2006 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku Americas and Rigaku, 2007 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812005946/gk2448sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812005946/gk2448Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812005946/gk2448Isup3.cml

checkCIF report

Comment top

The title compound, C₃₁H₂₉ClN₂O₃, is a derivative of 7,8- dihydro-5H-6-oxa-7-azapicene, which was obtained from U-4CR of 2-amino-4-chlorophenol, 2-bromobenzaldehyde, (E)- crotonic acid and cyclohexyl isocyanide (Xing et al., 2006; Dai et al., 2008) followed by O-benzylation and palladium catalyzed intramolecular arylation (Wu et al., 2007). The structure of the title compound has been characterized by spectroscopic methods with further confirmation by X-ray analysis. We report here its crystal structure.

In the molecule of the title compound (Fig. 1), there are three benzene rings and the middle one was fused with two other benzene rings by CH₂O and CH₂N bridges closing six-membered heterocyclic rings. The middle benzene ring is twisted relative to two other benzene rings by 30.7 (3)° and 15.7( 3)°. In the crystal structure, the molecules are linked by two C—H···Cl weak hydrogen bonds into centrosymmetric dimers (Fig. 2).

Related literature top

For the Ugi four-component reaction of 2-aminophenols, see: Xing et al. (2006); Dai et al. (2008). For microwave- assisted intramolecular direct arylation, see: Wu et al. (2007).

Experimental top

A solution of 2-amino-4-chlorophenol (3.0 mmol) and 2-bromobenzaldehyde (3.0 mmol) in MeOH (5 ml) was stirred at room temperature for 15 min. To the resultant mixture was added (E)-crotonic acid (3.0 mmol) followed by stirring for 5 min at the same temperature. Cyclohexyl isocyanide (3.0 mmol) was then added to the above mixture followed by stirring at 323 K for 48 h. The white precipitate of the U-4CR product was collected by filtration and the solid was washed with methanol (3 ml). The combined filtrate was concentrated under reduced pressure and the residue was purified by flash column chromatography over silica gel [eluting with 25% EtOAc in PE (b.p. 333–363 K)] to give additional portion of the U-4CR product. The yield of the U-4CR is 70%. A solution of the above U-4CR product (2.0 mmol), 2-bromobenzyl bromide (2.4 mmol), and K₂CO₃ (3.0 mmol) in acetone (reagent grade, 10 ml) was heated at 323 K for 2 h. The reaction was allowed to cool to room temperature. After adding water, the mixture was extracted using EtOAc (3 x 10 ml). The combined organic layer was dried over anhydrous Na₂SO₄, filtered off, and then evaporated under reduced pressure. The residue was purified by flash column chromatography over silica gel [eluting with 20% EtOAc in PE (b.p. 333–363 K)] to give the O-benzylation product (96%).

A 10-ml pressurized process vial was charged with the above O-benzylation product (0.15 mmol), Pd(OAc)₂ (7.5 x 10^-3 mmol; 5 mol %), K₂CO₃ (0.3 mmol), and PCy₃HBF₄ (1.5 x 10^-2 mmol, 10 mol %). The vial was sealed with a cap containing a silicon septum. The vial was evacuated and backfilled with N₂ (repeated for three times) through the cap using a needle. To the degassed vial was added degassed anhydrous MeCN (3 ml) through the cap using a syringe. The loaded vial was then placed into the microwave reactor cavity and was heated at 433 K for 80 min. After cooling to room temperature the reaction mixture was concentrated under reduced pressure and the residue was purified by flash column chromatography over silica gel [eluting with 25% EtOAc in PE (b.p. 333–363 K)] to give the title compound as a yellow solid (49 mg, 63%; m.p. 459–461 K (EtOAc-hexane). Single crystals suitable for X-ray diffraction were grown from a EtOAc/hexane mixture.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: CrystalStructure (Rigaku Americas and Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 40% probability level. H atoms are shown as a small spheres of arbitrary radius.
	Fig. 2. Centrosymmetric dimers by C—H···Cl hydrogen bonds. Symmetry code:(i) 1 - x, 1 - y, 1 - z.

rac-7-[(2E)-But-2-enoyl]-13-chloro-N-cyclohexyl- 7,8-dihydro-5H-isochromeno[4,3-c]phenanthridine-8-carboxamide top

Crystal data top

C₃₁H₂₉ClN₂O₃	F(000) = 1080
M_r = 513.01	D_x = 1.293 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 12604 reflections
a = 13.2616 (8) Å	θ = 3.0–27.4°
b = 13.4515 (7) Å	µ = 0.18 mm⁻¹
c = 14.8338 (9) Å	T = 296 K
β = 95.067 (2)°	Block, colorless
V = 2635.8 (3) Å³	0.35 × 0.32 × 0.20 mm
Z = 4

Data collection top

Rigaku RAXIS-RAPID/ZJUG diffractometer	4884 independent reflections
Radiation source: rolling anode	2797 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 10.00 pixels mm^-1	θ_max = 25.5°, θ_min = 3.0°
ω scans	h = −16→14
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −16→16
T_min = 0.930, T_max = 0.965	l = −17→17
21259 measured 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)] = 0.056	H-atom parameters constrained
wR(F²) = 0.197	w = 1/[σ²(F_o²) + (0.095P)² + 1.2622P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
4884 reflections	Δρ_max = 0.22 e Å⁻³
336 parameters	Δρ_min = −0.44 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0130 (19)

Crystal data top

C₃₁H₂₉ClN₂O₃	V = 2635.8 (3) Å³
M_r = 513.01	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.2616 (8) Å	µ = 0.18 mm⁻¹
b = 13.4515 (7) Å	T = 296 K
c = 14.8338 (9) Å	0.35 × 0.32 × 0.20 mm
β = 95.067 (2)°

Data collection top

Rigaku RAXIS-RAPID/ZJUG diffractometer	4884 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2797 reflections with I > 2σ(I)
T_min = 0.930, T_max = 0.965	R_int = 0.048
21259 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.197	H-atom parameters constrained
S = 1.00	Δρ_max = 0.22 e Å⁻³
4884 reflections	Δρ_min = −0.44 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
Cl1	0.57920 (9)	0.38756 (8)	0.47028 (9)	0.1040 (5)
O1	0.79308 (16)	0.71162 (15)	0.66645 (13)	0.0592 (6)
O2	0.51089 (18)	0.79850 (19)	0.41811 (15)	0.0731 (7)
O3	0.88187 (18)	0.83063 (16)	0.43610 (16)	0.0692 (7)
N1	0.76583 (18)	0.72488 (17)	0.48317 (15)	0.0485 (6)
N2	0.60639 (19)	0.82566 (19)	0.54842 (16)	0.0576 (7)
H2	0.6676	0.8320	0.5721	0.069*
C1	0.6860 (2)	0.7620 (2)	0.41769 (19)	0.0525 (7)
H1	0.7130	0.8192	0.3867	0.063*
C2	0.6609 (2)	0.6817 (2)	0.3479 (2)	0.0589 (8)
C3	0.6369 (3)	0.7041 (3)	0.2577 (2)	0.0764 (10)
H3	0.6320	0.7701	0.2393	0.092*
C4	0.6202 (3)	0.6291 (4)	0.1945 (3)	0.0940 (13)
H4	0.6018	0.6446	0.1342	0.113*
C5	0.6307 (3)	0.5322 (4)	0.2208 (3)	0.0940 (13)
H5	0.6224	0.4820	0.1776	0.113*
C6	0.6535 (3)	0.5080 (3)	0.3105 (3)	0.0770 (10)
H6	0.6603	0.4415	0.3273	0.092*
C7	0.6663 (2)	0.5820 (2)	0.3765 (2)	0.0593 (8)
C8	0.6843 (2)	0.5634 (2)	0.4748 (2)	0.0543 (8)
C9	0.6473 (3)	0.4825 (2)	0.5230 (3)	0.0641 (9)
C10	0.6594 (3)	0.4779 (2)	0.6151 (3)	0.0675 (9)
H10	0.6339	0.4231	0.6439	0.081*
C11	0.7086 (2)	0.5524 (2)	0.6681 (2)	0.0591 (8)
C12	0.7110 (3)	0.5590 (3)	0.7674 (2)	0.0653 (9)
C13	0.6507 (3)	0.4996 (3)	0.8181 (3)	0.0873 (12)
H13	0.6072	0.4525	0.7899	0.105*
C14	0.6565 (4)	0.5118 (4)	0.9117 (3)	0.1064 (17)
H14	0.6177	0.4715	0.9460	0.128*
C15	0.7185 (4)	0.5825 (5)	0.9541 (3)	0.1045 (16)
H15	0.7215	0.5896	1.0166	0.125*
C16	0.7759 (3)	0.6425 (4)	0.9043 (2)	0.0876 (12)
H16	0.8166	0.6915	0.9328	0.105*
C17	0.7733 (3)	0.6302 (3)	0.8105 (2)	0.0670 (9)
C18	0.8411 (3)	0.6891 (3)	0.7556 (2)	0.0725 (10)
H18A	0.8593	0.7507	0.7869	0.087*
H18B	0.9028	0.6519	0.7496	0.087*
C19	0.7487 (2)	0.6314 (2)	0.6215 (2)	0.0504 (7)
C20	0.7366 (2)	0.6362 (2)	0.52781 (19)	0.0488 (7)
C21	0.5920 (2)	0.7966 (2)	0.46243 (19)	0.0505 (7)
C22	0.5240 (2)	0.8474 (2)	0.60503 (19)	0.0533 (7)
H22	0.4599	0.8336	0.5692	0.064*
C23	0.5303 (3)	0.7807 (3)	0.6868 (2)	0.0775 (11)
H23A	0.5934	0.7928	0.7234	0.093*
H23B	0.5295	0.7118	0.6676	0.093*
C24	0.4415 (4)	0.7998 (3)	0.7433 (3)	0.1050 (15)
H24A	0.3787	0.7830	0.7081	0.126*
H24B	0.4478	0.7575	0.7964	0.126*
C25	0.4383 (4)	0.9064 (3)	0.7721 (3)	0.0954 (14)
H25A	0.4975	0.9211	0.8131	0.114*
H25B	0.3788	0.9174	0.8044	0.114*
C26	0.4355 (3)	0.9754 (3)	0.6917 (3)	0.0875 (12)
H26A	0.4392	1.0437	0.7127	0.105*
H26B	0.3719	0.9669	0.6549	0.105*
C27	0.5232 (3)	0.9550 (3)	0.6338 (3)	0.0753 (10)
H27A	0.5167	0.9973	0.5806	0.090*
H27B	0.5868	0.9710	0.6682	0.090*
C28	0.8642 (2)	0.7546 (2)	0.4774 (2)	0.0519 (7)
C29	0.9452 (2)	0.6895 (2)	0.5181 (2)	0.0622 (8)
H29	0.9285	0.6381	0.5560	0.075*
C30	1.0403 (3)	0.7021 (3)	0.5023 (3)	0.0793 (11)
H30	1.0556	0.7577	0.4688	0.095*
C31	1.1257 (3)	0.6351 (4)	0.5333 (3)	0.1114 (16)
H31A	1.1018	0.5839	0.5711	0.167*
H31B	1.1778	0.6728	0.5670	0.167*
H31C	1.1527	0.6054	0.4817	0.167*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0962 (8)	0.0717 (6)	0.1430 (11)	−0.0234 (5)	0.0050 (7)	−0.0170 (6)
O1	0.0654 (14)	0.0622 (13)	0.0484 (12)	−0.0042 (10)	−0.0033 (10)	0.0042 (10)
O2	0.0611 (15)	0.1040 (18)	0.0528 (13)	0.0172 (13)	−0.0030 (12)	−0.0067 (12)
O3	0.0746 (16)	0.0604 (13)	0.0752 (15)	−0.0084 (11)	0.0224 (12)	0.0076 (12)
N1	0.0487 (14)	0.0486 (13)	0.0488 (13)	−0.0027 (11)	0.0070 (11)	0.0074 (11)
N2	0.0509 (15)	0.0712 (16)	0.0511 (15)	0.0036 (12)	0.0063 (12)	−0.0106 (12)
C1	0.0565 (18)	0.0570 (17)	0.0444 (16)	0.0068 (14)	0.0072 (14)	0.0064 (13)
C2	0.0571 (19)	0.074 (2)	0.0464 (17)	0.0115 (16)	0.0094 (15)	−0.0041 (15)
C3	0.088 (3)	0.092 (3)	0.0493 (19)	0.023 (2)	0.0087 (18)	−0.0014 (19)
C4	0.102 (3)	0.125 (4)	0.054 (2)	0.020 (3)	0.002 (2)	−0.019 (2)
C5	0.089 (3)	0.119 (4)	0.072 (3)	0.011 (3)	0.001 (2)	−0.041 (3)
C6	0.074 (2)	0.081 (2)	0.075 (3)	0.0063 (19)	0.003 (2)	−0.023 (2)
C7	0.0512 (18)	0.072 (2)	0.0546 (18)	0.0052 (15)	0.0040 (15)	−0.0145 (16)
C8	0.0501 (18)	0.0527 (16)	0.0602 (19)	0.0050 (14)	0.0056 (15)	−0.0017 (14)
C9	0.058 (2)	0.0506 (17)	0.084 (3)	−0.0041 (14)	0.0056 (18)	−0.0002 (17)
C10	0.063 (2)	0.0535 (18)	0.087 (3)	−0.0015 (15)	0.0115 (19)	0.0172 (18)
C11	0.0567 (19)	0.0575 (18)	0.064 (2)	0.0049 (15)	0.0082 (16)	0.0153 (16)
C12	0.061 (2)	0.075 (2)	0.061 (2)	0.0131 (17)	0.0134 (17)	0.0249 (17)
C13	0.084 (3)	0.097 (3)	0.085 (3)	0.009 (2)	0.028 (2)	0.034 (2)
C14	0.096 (4)	0.138 (4)	0.092 (3)	0.022 (3)	0.044 (3)	0.053 (3)
C15	0.088 (3)	0.160 (5)	0.069 (3)	0.031 (3)	0.028 (3)	0.035 (3)
C16	0.073 (3)	0.130 (3)	0.060 (2)	0.021 (2)	0.0050 (19)	0.014 (2)
C17	0.059 (2)	0.088 (2)	0.0541 (19)	0.0130 (19)	0.0061 (16)	0.0145 (18)
C18	0.068 (2)	0.099 (3)	0.0489 (19)	−0.0030 (19)	−0.0044 (16)	0.0071 (18)
C19	0.0463 (17)	0.0498 (16)	0.0552 (18)	0.0016 (13)	0.0042 (14)	0.0070 (14)
C20	0.0494 (17)	0.0472 (15)	0.0502 (17)	0.0017 (13)	0.0074 (13)	0.0045 (13)
C21	0.058 (2)	0.0492 (16)	0.0444 (16)	0.0078 (14)	0.0065 (15)	0.0014 (13)
C22	0.0527 (18)	0.0602 (17)	0.0476 (16)	0.0029 (14)	0.0087 (14)	−0.0040 (14)
C23	0.098 (3)	0.070 (2)	0.067 (2)	0.006 (2)	0.024 (2)	0.0056 (18)
C24	0.132 (4)	0.099 (3)	0.093 (3)	0.006 (3)	0.059 (3)	0.014 (2)
C25	0.104 (3)	0.117 (3)	0.070 (2)	0.009 (3)	0.039 (2)	−0.012 (2)
C26	0.094 (3)	0.080 (2)	0.092 (3)	0.016 (2)	0.030 (2)	−0.017 (2)
C27	0.091 (3)	0.060 (2)	0.079 (2)	0.0059 (18)	0.031 (2)	−0.0018 (17)
C28	0.0542 (18)	0.0525 (16)	0.0506 (17)	−0.0058 (14)	0.0136 (14)	−0.0058 (14)
C29	0.0525 (19)	0.069 (2)	0.066 (2)	−0.0002 (15)	0.0118 (16)	0.0002 (16)
C30	0.056 (2)	0.099 (3)	0.084 (3)	−0.0011 (19)	0.0132 (19)	−0.001 (2)
C31	0.059 (3)	0.141 (4)	0.134 (4)	0.021 (3)	0.007 (3)	0.000 (3)

Geometric parameters (Å, º) top

Cl1—C9	1.713 (3)	C14—C15	1.373 (7)
O1—C19	1.373 (3)	C14—H14	0.9300
O1—C18	1.448 (4)	C15—C16	1.370 (6)
O2—C21	1.211 (4)	C15—H15	0.9300
O3—C28	1.225 (3)	C16—C17	1.397 (5)
N1—C28	1.374 (4)	C16—H16	0.9300
N1—C20	1.434 (3)	C17—C18	1.492 (5)
N1—C1	1.460 (4)	C18—H18A	0.9700
N2—C21	1.332 (4)	C18—H18B	0.9700
N2—C22	1.465 (3)	C19—C20	1.387 (4)
N2—H2	0.8600	C22—C23	1.506 (4)
C1—C2	1.513 (4)	C22—C27	1.510 (4)
C1—C21	1.535 (4)	C22—H22	0.9800
C1—H1	0.9800	C23—C24	1.525 (5)
C2—C3	1.382 (4)	C23—H23A	0.9700
C2—C7	1.407 (4)	C23—H23B	0.9700
C3—C4	1.381 (5)	C24—C25	1.498 (6)
C3—H3	0.9300	C24—H24A	0.9700
C4—C5	1.363 (6)	C24—H24B	0.9700
C4—H4	0.9300	C25—C26	1.510 (5)
C5—C6	1.378 (6)	C25—H25A	0.9700
C5—H5	0.9300	C25—H25B	0.9700
C6—C7	1.396 (4)	C26—C27	1.530 (5)
C6—H6	0.9300	C26—H26A	0.9700
C7—C8	1.478 (4)	C26—H26B	0.9700
C8—C20	1.401 (4)	C27—H27A	0.9700
C8—C9	1.413 (4)	C27—H27B	0.9700
C9—C10	1.364 (5)	C28—C29	1.473 (4)
C10—C11	1.399 (5)	C29—C30	1.315 (4)
C10—H10	0.9300	C29—H29	0.9300
C11—C19	1.397 (4)	C30—C31	1.488 (6)
C11—C12	1.474 (5)	C30—H30	0.9300
C12—C17	1.384 (5)	C31—H31A	0.9600
C12—C13	1.398 (5)	C31—H31B	0.9600
C13—C14	1.392 (6)	C31—H31C	0.9600
C13—H13	0.9300

C19—O1—C18	114.5 (2)	O1—C18—H18B	109.2
C28—N1—C20	124.6 (2)	C17—C18—H18B	109.2
C28—N1—C1	119.7 (2)	H18A—C18—H18B	107.9
C20—N1—C1	112.5 (2)	O1—C19—C20	117.1 (2)
C21—N2—C22	123.9 (3)	O1—C19—C11	121.6 (3)
C21—N2—H2	118.1	C20—C19—C11	121.0 (3)
C22—N2—H2	118.1	C19—C20—C8	122.5 (3)
N1—C1—C2	108.3 (2)	C19—C20—N1	119.3 (3)
N1—C1—C21	112.6 (2)	C8—C20—N1	117.6 (3)
C2—C1—C21	112.0 (3)	O2—C21—N2	124.0 (3)
N1—C1—H1	107.9	O2—C21—C1	119.2 (3)
C2—C1—H1	107.9	N2—C21—C1	116.8 (3)
C21—C1—H1	107.9	N2—C22—C23	110.6 (3)
C3—C2—C7	120.1 (3)	N2—C22—C27	112.2 (3)
C3—C2—C1	121.7 (3)	C23—C22—C27	110.2 (3)
C7—C2—C1	118.2 (3)	N2—C22—H22	107.9
C4—C3—C2	120.5 (4)	C23—C22—H22	107.9
C4—C3—H3	119.8	C27—C22—H22	107.9
C2—C3—H3	119.8	C22—C23—C24	110.6 (3)
C5—C4—C3	119.9 (4)	C22—C23—H23A	109.5
C5—C4—H4	120.1	C24—C23—H23A	109.5
C3—C4—H4	120.1	C22—C23—H23B	109.5
C4—C5—C6	120.7 (4)	C24—C23—H23B	109.5
C4—C5—H5	119.7	H23A—C23—H23B	108.1
C6—C5—H5	119.7	C25—C24—C23	111.2 (4)
C5—C6—C7	120.8 (4)	C25—C24—H24A	109.4
C5—C6—H6	119.6	C23—C24—H24A	109.4
C7—C6—H6	119.6	C25—C24—H24B	109.4
C6—C7—C2	117.9 (3)	C23—C24—H24B	109.4
C6—C7—C8	124.8 (3)	H24A—C24—H24B	108.0
C2—C7—C8	117.3 (3)	C24—C25—C26	111.2 (3)
C20—C8—C9	115.6 (3)	C24—C25—H25A	109.4
C20—C8—C7	117.7 (3)	C26—C25—H25A	109.4
C9—C8—C7	126.5 (3)	C24—C25—H25B	109.4
C10—C9—C8	121.8 (3)	C26—C25—H25B	109.4
C10—C9—Cl1	115.7 (3)	H25A—C25—H25B	108.0
C8—C9—Cl1	122.4 (3)	C25—C26—C27	111.5 (3)
C9—C10—C11	122.5 (3)	C25—C26—H26A	109.3
C9—C10—H10	118.8	C27—C26—H26A	109.3
C11—C10—H10	118.8	C25—C26—H26B	109.3
C19—C11—C10	116.5 (3)	C27—C26—H26B	109.3
C19—C11—C12	118.2 (3)	H26A—C26—H26B	108.0
C10—C11—C12	124.9 (3)	C22—C27—C26	110.8 (3)
C17—C12—C13	119.6 (3)	C22—C27—H27A	109.5
C17—C12—C11	117.6 (3)	C26—C27—H27A	109.5
C13—C12—C11	122.8 (4)	C22—C27—H27B	109.5
C14—C13—C12	119.0 (5)	C26—C27—H27B	109.5
C14—C13—H13	120.5	H27A—C27—H27B	108.1
C12—C13—H13	120.5	O3—C28—N1	119.9 (3)
C15—C14—C13	121.1 (4)	O3—C28—C29	122.4 (3)
C15—C14—H14	119.4	N1—C28—C29	117.6 (3)
C13—C14—H14	119.4	C30—C29—C28	121.8 (3)
C16—C15—C14	120.0 (4)	C30—C29—H29	119.1
C16—C15—H15	120.0	C28—C29—H29	119.1
C14—C15—H15	120.0	C29—C30—C31	125.7 (4)
C15—C16—C17	120.1 (5)	C29—C30—H30	117.1
C15—C16—H16	120.0	C31—C30—H30	117.1
C17—C16—H16	120.0	C30—C31—H31A	109.5
C12—C17—C16	120.2 (3)	C30—C31—H31B	109.5
C12—C17—C18	118.6 (3)	H31A—C31—H31B	109.5
C16—C17—C18	121.1 (4)	C30—C31—H31C	109.5
O1—C18—C17	111.9 (3)	H31A—C31—H31C	109.5
O1—C18—H18A	109.2	H31B—C31—H31C	109.5
C17—C18—H18A	109.2

C28—N1—C1—C2	101.4 (3)	C15—C16—C17—C18	−175.2 (4)
C20—N1—C1—C2	−59.1 (3)	C19—O1—C18—C17	−48.5 (4)
C28—N1—C1—C21	−134.2 (3)	C12—C17—C18—O1	36.9 (4)
C20—N1—C1—C21	65.2 (3)	C16—C17—C18—O1	−146.4 (3)
N1—C1—C2—C3	−143.1 (3)	C18—O1—C19—C20	−155.8 (3)
C21—C1—C2—C3	92.2 (4)	C18—O1—C19—C11	30.0 (4)
N1—C1—C2—C7	34.5 (4)	C10—C11—C19—O1	176.0 (3)
C21—C1—C2—C7	−90.3 (3)	C12—C11—C19—O1	2.7 (4)
C7—C2—C3—C4	−1.4 (5)	C10—C11—C19—C20	2.1 (4)
C1—C2—C3—C4	176.1 (3)	C12—C11—C19—C20	−171.2 (3)
C2—C3—C4—C5	−2.2 (6)	O1—C19—C20—C8	−174.1 (3)
C3—C4—C5—C6	2.9 (7)	C11—C19—C20—C8	0.1 (4)
C4—C5—C6—C7	0.0 (6)	O1—C19—C20—N1	−3.0 (4)
C5—C6—C7—C2	−3.5 (5)	C11—C19—C20—N1	171.1 (3)
C5—C6—C7—C8	176.0 (3)	C9—C8—C20—C19	−2.0 (4)
C3—C2—C7—C6	4.2 (5)	C7—C8—C20—C19	173.2 (3)
C1—C2—C7—C6	−173.4 (3)	C9—C8—C20—N1	−173.3 (3)
C3—C2—C7—C8	−175.3 (3)	C7—C8—C20—N1	2.0 (4)
C1—C2—C7—C8	7.1 (4)	C28—N1—C20—C19	71.5 (4)
C6—C7—C8—C20	153.5 (3)	C1—N1—C20—C19	−129.1 (3)
C2—C7—C8—C20	−27.0 (4)	C28—N1—C20—C8	−117.0 (3)
C6—C7—C8—C9	−31.8 (5)	C1—N1—C20—C8	42.4 (3)
C2—C7—C8—C9	147.6 (3)	C22—N2—C21—O2	10.9 (5)
C20—C8—C9—C10	1.9 (5)	C22—N2—C21—C1	−171.1 (3)
C7—C8—C9—C10	−172.9 (3)	N1—C1—C21—O2	−156.4 (3)
C20—C8—C9—Cl1	178.5 (2)	C2—C1—C21—O2	−34.0 (4)
C7—C8—C9—Cl1	3.8 (5)	N1—C1—C21—N2	25.5 (4)
C8—C9—C10—C11	0.2 (5)	C2—C1—C21—N2	147.8 (3)
Cl1—C9—C10—C11	−176.7 (3)	C21—N2—C22—C23	120.5 (3)
C9—C10—C11—C19	−2.2 (5)	C21—N2—C22—C27	−116.1 (3)
C9—C10—C11—C12	170.6 (3)	N2—C22—C23—C24	−177.2 (3)
C19—C11—C12—C17	−15.1 (4)	C27—C22—C23—C24	58.2 (4)
C10—C11—C12—C17	172.2 (3)	C22—C23—C24—C25	−57.6 (5)
C19—C11—C12—C13	162.3 (3)	C23—C24—C25—C26	55.3 (6)
C10—C11—C12—C13	−10.3 (5)	C24—C25—C26—C27	−54.3 (5)
C17—C12—C13—C14	−1.6 (6)	N2—C22—C27—C26	179.2 (3)
C11—C12—C13—C14	−178.9 (3)	C23—C22—C27—C26	−57.0 (4)
C12—C13—C14—C15	1.5 (7)	C25—C26—C27—C22	55.2 (5)
C13—C14—C15—C16	0.1 (7)	C20—N1—C28—O3	178.4 (3)
C14—C15—C16—C17	−1.6 (7)	C1—N1—C28—O3	20.4 (4)
C13—C12—C17—C16	0.1 (5)	C20—N1—C28—C29	1.5 (4)
C11—C12—C17—C16	177.6 (3)	C1—N1—C28—C29	−156.5 (3)
C13—C12—C17—C18	176.9 (3)	O3—C28—C29—C30	−9.2 (5)
C11—C12—C17—C18	−5.6 (5)	N1—C28—C29—C30	167.6 (3)
C15—C16—C17—C12	1.5 (6)	C28—C29—C30—C31	−174.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1	0.86	2.41	2.758 (3)	105
C23—H23B···Cl1ⁱ	0.97	2.74	3.473 (4)	133
C14—H14···O3ⁱⁱ	0.93	2.58	3.391 (5)	146

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

Experimental details

Crystal data
Chemical formula	C₃₁H₂₉ClN₂O₃
M_r	513.01
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	13.2616 (8), 13.4515 (7), 14.8338 (9)
β (°)	95.067 (2)
V (Å³)	2635.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.35 × 0.32 × 0.20

Data collection
Diffractometer	Rigaku RAXIS-RAPID/ZJUG diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.930, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	21259, 4884, 2797
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.197, 1.00
No. of reflections	4884
No. of parameters	336
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.44

Computer programs: PROCESS-AUTO (Rigaku, 2006), CrystalStructure (Rigaku Americas and Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1	0.86	2.41	2.758 (3)	105
C23—H23B···Cl1ⁱ	0.97	2.74	3.473 (4)	133
C14—H14···O3ⁱⁱ	0.93	2.58	3.391 (5)	146

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

Acknowledgements

This work was supported by a research grant from the Natural Science Foundation of China (grant No. 20672092). The authors thank Professor Wei-Min Dai for his valuable suggestion. Mr Jianming Gu of the X-ray crystallography facility of Zhejiang University is acknowledged for his assistance with the crystal structural analysis.

References

Dai, W.-M., Shi, J. & Wu, J. (2008). Synlett, pp. 2716–2720. Web of Science CrossRef Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2006). PROCESS-AUTO. Rigaku Americas Corporation, The Woodlands, Texas, USA. Google Scholar
Rigaku Americas and Rigaku (2007). CrystalStructure. Rigaku Americas, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. 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., Feng, G. & Dai, W.-M. (2006). Tetrahedron, 62, 6774–6781. Web of Science CrossRef CAS Google Scholar

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Volume 68| Part 3| March 2012| Page o748

doi:10.1107/S1600536812005946

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

rac-7-[(2E)-But-2-eno­yl]-13-chloro-N-cyclo­hexyl-7,8-di­hydro-5H-isochromeno[4,3-c]phenanthridine-8-carboxamide

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

rac-7-[(2E)-But-2-enoyl]-13-chloro-N-cyclohexyl-7,8-dihydro-5H-isochromeno[4,3-c]phenanthridine-8-carboxamide