Spiro­[indene-1,1′-benzo[e]indolin]-2′-one

Jin-Xiang Chen; Yu-Qin Wang; Shu-Wen Liu; Wei-Er Lin; Zhi-Peng Chen

doi:10.1107/S1600536810049809

. 2010 Dec 4;67(Pt 1):o9. doi: 10.1107/S1600536810049809

Spiro[indene-1,1′-benzo[e]indolin]-2′-one

Jin-Xiang Chen ^a,^*, Yu-Qin Wang ^a, Shu-Wen Liu ^a, Wei-Er Lin ^a, Zhi-Peng Chen ^a

PMCID: PMC3050306 PMID: 21522798

Abstract

In the title compound, C₂₀H₁₃NO, the indene ring is disordered over two sites with an occupancy ratio of 0.557 (2):0.443 (2). Both disordered components of indene are nearly perpendicular to the naphthalene ring system, making dihedral angles of 90.9 (2) and 85.0 (5)°. The five-membered ring of the 1H-pyrrol-2(3H)-one adopts an envelope conformation with the spiro C atom at the flap position. Intermolecular classical N—H⋯O and weak C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For the biological activity of spiro lactams, see: Tsuda et al. (2004 ▶); Chen et al. (2005 ▶). For the synthesis of the title compound, see: Ready et al. (2004 ▶); Schoemaker & Speckamp (1978 ▶).

Experimental

Crystal data

C₂₀H₁₃NO
M _r = 283.31
Monoclinic,
a = 13.0150 (18) Å
b = 7.9180 (11) Å
c = 15.537 (2) Å
β = 112.030 (2)°
V = 1484.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.50 × 0.41 × 0.33 mm

Data collection

Rigaku Mercury diffractometer
6913 measured reflections
2526 independent reflections
1984 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.074
wR(F ²) = 0.199
S = 1.06
2526 reflections
203 parameters
30 restraints
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2001 ▶); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810049809/xu5073sup1.cif

e-67-000o9-sup1.cif^{(25.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049809/xu5073Isup2.hkl

e-67-000o9-Isup2.hkl^{(124.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.86	1.99	2.815 (3)	162
C18—H18A⋯O1ⁱⁱ	0.93	2.35	3.064 (5)	133

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work was supported by the Medical Scientific Research Foundation of Guangdong Province (No. B107) and the Guangzhou Municipal Scientific and Technological Project, China (No. 2007 J1-C0251).

supplementary crystallographic information

Comment

In the past decades, spiro lactams have been attracted considerable interest because they are commonly found as subunits of many natural products. Some of them have significant biological activities, including multiple drug resistance reversing, antifungal and antitumor activities (Tsuda et al.,2004). Synthetic methods directed to these classes of spiro lactam compounds have been developed (Ready et al., 2004). Among them, spiro cyclizations of N-acyliminium ions with an internalalkene nucleophile were first described by Speckamp (Schoemaker et al., 1978). Reductive coupling of acrylates with isocyanates to furnish spiro lactam skeleton was used by Wood [Ready et al., 2004]. The title compound I was synthesized in one step through a new ring-rearrangement reaction. It was undertaken as a continuation of our efforts towards synthesis of dibenzoxanthenes which exhibit a wide variety of biological activities [Chen et al., 2005].

The asymmetric unit of I contains one independent spiro-[indene-1,3'-(2',3'-dihydro-2'-oxa-benzo[e]indole)] molecule. In the complex I, the naphthyl ring and indene ring are almost perpendicular to each other, making a diheral angle of 90.9 (2)°. All bond lengths and bond angles are in the normal ranges and comparable to those observed in the similar substituted spiro-[indene-1,3'-(2',3'-dihydro-2'-oxa-benzo[e]indole)], except the disordered part of indene ring. The C(11)=O(1) bond length of 1.215 (4) Å of oxa-indole moiety conforms to the value for a double bond.

In the crystal of I, there are two types hydrogen bonding interactions: one type is classical hydrogen bonding between O(1) atom and N(1) atom from oxa-benzo[e]indole moiety, the other one is unclassical hydrogen bonding between O(1) atom and C(18) atom from the phenyl group. The molecule I was linked together by a double strong classical intermolecular hydrogen bonds of N(1)—H1A···O(1), thereby forming a dimer structure, while the dimers were futher linked by the unclassical hydrogen bonds of C(18)—HA···O(1), thereby forming a two dimessional network structure.

Experimental

Into a stirred solution of CuCl₂.2H₂O (17 mg, 0.1 mmol) in methanol (5 ml) was added a solution of ethanolamine (6 mg, 0.1 mmol) in methanol (2 ml). After 10 min. a solution of 2-amino-2'-hydroxy-1,1'-binaphthyl (0.1 mmol) in methanol (2 ml) was added and the reaction mixture was stirred at 323 K. When the reaction was completed, the solvent was removed under reduced pressure. The residue was extracted with AcOEt (10 ml), washed with 5% ammonia (10 ml) and water (10 ml), then dried with Na₂SO₄, and the solvent was removed under reduced pressure. Thick layer chromatography of the residue (hexane:ethyl acetate, 10:1) followed by recrystallization from acetone gave the title complex as red crystals. Yield: ca 82%.