3,3-Dimethyl-1,2,3,4-tetra­hydro­cyclo­penta­[b]indole-1,2-dione (bruceolline E)

Jordon, J.A.; Badenock, J.C.; Gribble, G.W.; Jasinski, J.P.; Golen, J.A.

doi:10.1107/S1600536812000517

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages o364-o365

doi:10.1107/S1600536812000517

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3,3-Dimethyl-1,2,3,4-tetrahydrocyclopenta[b]indole-1,2-dione (bruceolline E)

Jason A. Jordon,^a Jeanese C. Badenock,^a Gordon W. Gribble,^b Jerry P. Jasinski ^c ^* and James A. Golen ^c

^aDepartment of Biological and Chemical Sciences, University of the West Indies, Cave Hill, Barbados, ^bDepartment Chemistry, Dartmouth College, Hanover, NH 03755-3564, USA, and ^cDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA
^*Correspondence e-mail: jjasinski@keene.edu

(Received 28 December 2011; accepted 5 January 2012; online 11 January 2012)

The title compound, C₁₃H₁₁NO₂, crystallizes with two molecules in the asymmetric unit. The crystal packing is stabilized by N—H⋯O hydrogen bonds, which link the molecules into chains along [10 $[\overline1]$ ], and weak C—H⋯O interactions.

Related literature

For the first isolation of bruceolline E as yellow needles, see: Ouyang et al. (1994 ). For the first total synthesis of bruceolline E in three steps from the known ethyl indole-1-carboxylate, see: Jordan et al. (2011 ). For examples of similar tandem acylation/Nazarov cyclization with pyrroles, see: Song et al. (2006 ). For examples of Nazarov cyclizations with indoles, see: Bergman & Venemalm (1992 ); Cheng & Cheung (1996 ); Ishikura et al. (2000 ); Miki et al. (2001 ); Churruca et al. (2010 ). For examples of α-diketone oxidations using selenium dioxide, see: Gribble et al. (1988 ); Xu et al. (2002 ); Belsey et al. (2006 ). For related cyclopenta[b]indolone alkaloids and their analogues, see: Cheng et al. (1991 ); Garcia-Pichel & Castenholz (1991 ); Garcia-Pichel et al. (1992 ); Proteau et al. (1993 ); Ekebergh et al. (2011 ); Kobayashi et al. (1994 ); Jacquemard et al. (2004 ); Ploutno & Carmeli (2001 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₃H₁₁NO₂
M_r = 213.23
Triclinic, $[P \overline 1]$
a = 9.1091 (7) Å
b = 11.5337 (8) Å
c = 11.8745 (9) Å
α = 63.230 (7)°
β = 80.596 (6)°
γ = 79.970 (6)°
V = 1091.69 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 170 K
0.28 × 0.25 × 0.24 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.976, T_max = 0.979
10062 measured reflections
5644 independent reflections
4698 reflections with I > 2σ(I)
R_int = 0.012

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.157
S = 1.05
5644 reflections
299 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1NA⋯O2A	0.89 (1)	1.95 (1)	2.8025 (16)	161 (2)
N1A—H1NB⋯O2ⁱ	0.92 (1)	1.87 (1)	2.7686 (16)	164 (2)
C9A—H9AA⋯O1ⁱ	0.95	2.51	3.376 (2)	152
C12A—H12B⋯O2ⁱ	0.98	2.57	3.430 (2)	146
Symmetry code: (i) x-1, y, z+1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812000517/qm2048sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812000517/qm2048Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812000517/qm2048Isup3.cml

checkCIF report

Comment top

The fused indole alkaloid bruceolline E was first isolated as yellow needles from the root wood Brucea mollis Wall. Var. tonkinensis Lecomte and reported by Ohmoto (Ouyang et al., 1994). Our synthesis of this cyclopenta[b]indolone natural product included a tandem acylation/Nazarov cyclization sequence (Song et al., 2006) and insertion of the α-diketone functionality using selenium dioxide (Gribble et al., 1988) in 60% yield. Similar Nazarov cyclizations with indoles (Bergman & Venemalm, 1992; Cheng & Cheung, 1996; Ishikura et al., 2000; Miki et al., 2001; Churruca et al., 2010) have been reported. Related α-diketone oxidations using selenium dioxide (Xu et al., 2002; Belsey et al., 2006) and cyclopenta[b]indolone natural product alkaloid analogues such as scytonemin (Garcia-Pichel & Castenholz 1991; Garcia-Pichel et al. 1992; Proteau et al. 1993; Ekebergh et al. 2011), nostodione (Kobayashi et al., 1994) and prenostodione (Ploutno & Carmeli, 2001) have also been reported. Our efforts have yielded the first total synthesis of bruceolline E (Jordan et al., 2011), in three steps from the known ethyl indole-1-carboxylate.

We now report herein the first crystal structure of the title compound, C₁₃H₁₁NO₂, bruceolline E, which confirms the cyclopenta[b] indole moiety and the α-diketone functionalities earlier assigned by NMR methods.

In the crystal structure of the title compound, C₁₃H₁₁NO₂, two molecules crystallize in the asymmetric unit (Fig. 1). Bond lengths are in normal ranges (Allen et al., 1987). Crystal packing is stabilized by N—H···O hydrogen bonds (Table 1) and weak C—H···O intermolecular interactions linking these 1-D chains along [011] (Fig. 2).

Related literature top

For the first isolation of bruceolline E as yellow needles, see: Ouyang et al. (1994). For the first total synthesis of bruceolline E in three steps from the known ethyl indole-1-carboxylate, see: Jordan et al. (2011). For examples of similar tandem acylation/Nazarov cyclization with pyrroles, see: Song et al. (2006). For examples of Nazarov cyclizations with indoles, see: Bergman & Venemalm (1992); Cheng & Cheung (1996); Ishikura et al. (2000); Miki et al. (2001); Churruca et al. (2010). For examples of α-diketone oxidations using selenium dioxide, see: Gribble et al. (1988); Xu et al. (2002); Belsey et al. (2006). For related cyclopenta[b]indolone alkaloids and their analogues, see: Cheng et al. (1991); Garcia-Pichel & Castenholz (1991); Garcia-Pichel et al. (1992); Proteau et al. (1993); Ekebergh et al. (2011); Kobayashi et al. (1994); Jacquemard et al. (2004); Ploutno & Carmeli (2001). For standard bond lengths, see: Allen et al. (1987).

Experimental top

A solution of 3,3-dimethyl-1,2-dioxo-2,3-dihydro-1H-cyclopenta[b] indole-4-carboxylic acid ethyl ester (0.58 g, 2.03 mmol, 1 eq.), anhydrous THF (30 mL) and TBAF (10.2 mL, 1.0 M in THF, 10.2 mmol, 5.02 eq.) was stirred under argon at reflux for 2 h (Jacquemard et al., 2004). The mixture was allowed to cool before quenching with saturated NH₄Cl. After extraction with CH₂Cl₂ (3 x 40 mL), the organic layers were combined, dried over MgSO₄ and concentrated in vacuo to give a yellow solid. Flash column chromatography (100% EtOAc) gave the product as a yellow solid (0.42 g, 97%). Crystals suitable for X-ray diffraction were grown from methanol [m.p. 562- 563 K (dec); literature value 562- 564 K (dec)].

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound with two molecules in the asymmetric unit showing the atom labeling scheme and 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound viewed along the a axis. Dashed lines indicate N—H···O hydrogen bonds forming infinite 1-D chains along [011]. The remaining H atoms have been removed for clarity.

3,3-Dimethyl-1,2,3,4-tetrahydrocyclopenta[b]indole-1,2-dione top

Crystal data top

C₁₃H₁₁NO₂	Z = 4
M_r = 213.23	F(000) = 448
Triclinic, P1	D_x = 1.297 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1091 (7) Å	Cell parameters from 5810 reflections
b = 11.5337 (8) Å	θ = 3.3–32.3°
c = 11.8745 (9) Å	µ = 0.09 mm⁻¹
α = 63.230 (7)°	T = 170 K
β = 80.596 (6)°	Block, yellow
γ = 79.970 (6)°	0.28 × 0.25 × 0.24 mm
V = 1091.69 (14) Å³

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	5644 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4698 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.012
Detector resolution: 16.1500 pixels mm^-1	θ_max = 28.7°, θ_min = 3.3°
ω scans	h = −12→11
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −15→15
T_min = 0.976, T_max = 0.979	l = −15→16
10062 measured reflections

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0864P)² + 0.2278P] where P = (F_o² + 2F_c²)/3
5644 reflections	(Δ/σ)_max < 0.001
299 parameters	Δρ_max = 0.36 e Å⁻³
2 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₃H₁₁NO₂	γ = 79.970 (6)°
M_r = 213.23	V = 1091.69 (14) Å³
Triclinic, P1	Z = 4
a = 9.1091 (7) Å	Mo Kα radiation
b = 11.5337 (8) Å	µ = 0.09 mm⁻¹
c = 11.8745 (9) Å	T = 170 K
α = 63.230 (7)°	0.28 × 0.25 × 0.24 mm
β = 80.596 (6)°

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	5644 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	4698 reflections with I > 2σ(I)
T_min = 0.976, T_max = 0.979	R_int = 0.012
10062 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	2 restraints
wR(F²) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.36 e Å⁻³
5644 reflections	Δρ_min = −0.20 e Å⁻³
299 parameters

Special details top

Experimental. ¹H NMR (600 MHz, DMSO-d6) δ 12.9 (bs, 1H), 7.85 7.84 (d, J = 8.0 Hz, 1H), 7.62 7.61 (d, J = 8.1 Hz, 1H), 7.42 7.39 (t, J = 7.4 Hz, 1H), 7.34–7.31 (t, J = 7.7 Hz, 1H), 1.44 (s, 6H). ¹³C NMR (150 MHz, DMSO-d₆) δ 206.6, 175.2, 171.0, 140.0, 125.4, 123.4, 121.5, 121.1, 121.0, 113.6, 41.6, 22.9; IR ν(KBr) 3418, 1750, 1665, 1469, 1453, 1210, 1152, 1094, 1013; UV λ_max (95% MeOH) 256, 264, 272, 342 nm. Anal. Calcd for C₁₃H₁₁NO₂: C, 73.22; H, 5.20; N 6.57. Found: C, 72.48; H, 5.30; N 6.40.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O1	0.75420 (16)	0.86467 (16)	0.18664 (11)	0.0673 (4)
O2	1.05510 (14)	0.75658 (14)	0.25613 (11)	0.0591 (3)
N1	0.76832 (12)	0.67293 (11)	0.63752 (10)	0.0329 (2)
H1NA	0.6811 (16)	0.6811 (16)	0.6806 (15)	0.039*
C1	0.67431 (15)	0.78837 (13)	0.41344 (12)	0.0330 (3)
C2	0.78552 (17)	0.80931 (15)	0.29437 (13)	0.0413 (3)
C3	0.94630 (16)	0.75106 (15)	0.33304 (13)	0.0398 (3)
C4	0.93046 (14)	0.69760 (13)	0.46734 (12)	0.0330 (3)
C5	1.01358 (15)	0.62976 (14)	0.57632 (13)	0.0358 (3)
C6	1.16300 (17)	0.58148 (19)	0.59556 (18)	0.0522 (4)
H6A	1.2361	0.5907	0.5260	0.063*
C7	1.2022 (2)	0.5200 (2)	0.7181 (2)	0.0653 (5)
H7A	1.3038	0.4862	0.7326	0.078*
C8	1.0970 (2)	0.5060 (2)	0.82122 (19)	0.0618 (5)
H8A	1.1280	0.4626	0.9044	0.074*
C9	0.94890 (19)	0.55398 (18)	0.80488 (15)	0.0496 (4)
H9A	0.8771	0.5453	0.8751	0.060*
C10	0.90872 (15)	0.61552 (14)	0.68187 (13)	0.0351 (3)
C11	0.78265 (14)	0.71996 (12)	0.51124 (11)	0.0289 (3)
C12	0.6013 (2)	0.92013 (15)	0.40795 (16)	0.0497 (4)
H12D	0.5338	0.9061	0.4851	0.074*
H12E	0.5442	0.9664	0.3338	0.074*
H12F	0.6791	0.9724	0.4014	0.074*
C13	0.55503 (18)	0.70394 (18)	0.42566 (17)	0.0495 (4)
H13D	0.4878	0.6899	0.5029	0.074*
H13E	0.6036	0.6194	0.4300	0.074*
H13F	0.4972	0.7484	0.3519	0.074*
N1A	0.10484 (12)	0.81468 (12)	1.00094 (10)	0.0343 (3)
H1NB	0.0732 (19)	0.8074 (16)	1.0812 (13)	0.041*
O1A	0.61629 (13)	0.64860 (15)	0.94255 (14)	0.0651 (4)
O2A	0.46978 (13)	0.73188 (12)	0.71755 (11)	0.0529 (3)
C1A	0.38431 (14)	0.72921 (13)	1.03441 (13)	0.0336 (3)
C2A	0.48880 (15)	0.69922 (14)	0.93239 (15)	0.0390 (3)
C3A	0.40683 (16)	0.74091 (13)	0.81363 (13)	0.0370 (3)
C4A	0.25841 (14)	0.78537 (13)	0.84578 (12)	0.0320 (3)
C5A	0.11410 (15)	0.83713 (13)	0.79856 (12)	0.0333 (3)
C6A	0.05507 (19)	0.87076 (16)	0.68526 (14)	0.0452 (3)
H6AA	0.1159	0.8600	0.6169	0.054*
C7A	−0.0938 (2)	0.92010 (18)	0.67500 (16)	0.0538 (4)
H7AA	−0.1353	0.9443	0.5980	0.065*
C8A	−0.18450 (19)	0.93526 (19)	0.77470 (18)	0.0568 (4)
H8AA	−0.2867	0.9692	0.7644	0.068*
C9A	−0.12946 (17)	0.90208 (18)	0.88854 (16)	0.0490 (4)
H9AA	−0.1916	0.9120	0.9568	0.059*
C10A	0.02018 (15)	0.85378 (13)	0.89824 (12)	0.0345 (3)
C11A	0.24447 (14)	0.77534 (12)	0.96840 (12)	0.0292 (3)
C12A	0.37519 (19)	0.60627 (17)	1.15941 (16)	0.0512 (4)
H12A	0.3434	0.5371	1.1456	0.077*
H12B	0.3025	0.6255	1.2211	0.077*
H12C	0.4738	0.5772	1.1919	0.077*
C13A	0.43957 (19)	0.83897 (17)	1.04967 (18)	0.0518 (4)
H13A	0.3713	0.8599	1.1125	0.078*
H13B	0.4424	0.9168	0.9681	0.078*
H13C	0.5403	0.8104	1.0781	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0641 (8)	0.0963 (10)	0.0291 (6)	0.0029 (7)	−0.0074 (5)	−0.0196 (6)
O2	0.0437 (6)	0.0938 (9)	0.0361 (6)	−0.0042 (6)	0.0117 (5)	−0.0315 (6)
N1	0.0271 (5)	0.0433 (6)	0.0241 (5)	−0.0003 (4)	0.0009 (4)	−0.0134 (4)
C1	0.0307 (6)	0.0383 (6)	0.0268 (6)	0.0014 (5)	−0.0042 (5)	−0.0127 (5)
C2	0.0429 (8)	0.0511 (8)	0.0273 (6)	−0.0021 (6)	−0.0012 (5)	−0.0165 (6)
C3	0.0350 (7)	0.0536 (8)	0.0310 (7)	−0.0033 (6)	0.0050 (5)	−0.0217 (6)
C4	0.0268 (6)	0.0428 (7)	0.0290 (6)	−0.0010 (5)	0.0014 (5)	−0.0175 (5)
C5	0.0284 (6)	0.0448 (7)	0.0356 (7)	0.0001 (5)	−0.0040 (5)	−0.0200 (6)
C6	0.0291 (7)	0.0757 (11)	0.0557 (10)	0.0045 (7)	−0.0059 (6)	−0.0351 (9)
C7	0.0378 (8)	0.0923 (14)	0.0728 (13)	0.0151 (9)	−0.0260 (9)	−0.0432 (11)
C8	0.0568 (11)	0.0806 (13)	0.0488 (10)	0.0086 (9)	−0.0269 (8)	−0.0273 (9)
C9	0.0471 (8)	0.0654 (10)	0.0334 (7)	0.0002 (7)	−0.0100 (6)	−0.0190 (7)
C10	0.0308 (6)	0.0429 (7)	0.0306 (6)	−0.0012 (5)	−0.0042 (5)	−0.0157 (5)
C11	0.0272 (6)	0.0335 (6)	0.0242 (6)	−0.0014 (4)	−0.0002 (4)	−0.0124 (5)
C12	0.0527 (9)	0.0409 (8)	0.0455 (8)	0.0076 (7)	−0.0038 (7)	−0.0149 (7)
C13	0.0394 (8)	0.0611 (9)	0.0523 (9)	−0.0075 (7)	−0.0085 (7)	−0.0263 (8)
N1A	0.0278 (5)	0.0469 (6)	0.0250 (5)	0.0028 (4)	−0.0006 (4)	−0.0159 (5)
O1A	0.0302 (6)	0.0908 (10)	0.0778 (9)	0.0113 (6)	−0.0046 (6)	−0.0463 (8)
O2A	0.0440 (6)	0.0689 (7)	0.0422 (6)	0.0004 (5)	0.0130 (5)	−0.0290 (6)
C1A	0.0280 (6)	0.0371 (6)	0.0338 (6)	0.0001 (5)	−0.0046 (5)	−0.0145 (5)
C2A	0.0272 (6)	0.0417 (7)	0.0461 (8)	−0.0024 (5)	0.0023 (5)	−0.0199 (6)
C3A	0.0342 (7)	0.0394 (7)	0.0345 (7)	−0.0039 (5)	0.0063 (5)	−0.0169 (5)
C4A	0.0311 (6)	0.0372 (6)	0.0257 (6)	−0.0032 (5)	0.0011 (5)	−0.0135 (5)
C5A	0.0327 (6)	0.0379 (6)	0.0271 (6)	−0.0041 (5)	−0.0013 (5)	−0.0126 (5)
C6A	0.0510 (9)	0.0542 (8)	0.0301 (7)	−0.0077 (7)	−0.0054 (6)	−0.0170 (6)
C7A	0.0543 (10)	0.0644 (10)	0.0390 (8)	−0.0065 (8)	−0.0201 (7)	−0.0142 (7)
C8A	0.0380 (8)	0.0717 (11)	0.0517 (10)	0.0019 (7)	−0.0157 (7)	−0.0179 (8)
C9A	0.0313 (7)	0.0662 (10)	0.0415 (8)	0.0043 (7)	−0.0037 (6)	−0.0199 (7)
C10A	0.0309 (6)	0.0406 (7)	0.0273 (6)	−0.0015 (5)	−0.0031 (5)	−0.0115 (5)
C11A	0.0266 (6)	0.0316 (6)	0.0261 (6)	−0.0010 (4)	0.0000 (4)	−0.0112 (5)
C12A	0.0402 (8)	0.0522 (9)	0.0417 (8)	0.0038 (6)	−0.0067 (6)	−0.0054 (7)
C13A	0.0453 (9)	0.0570 (9)	0.0638 (11)	−0.0044 (7)	−0.0134 (8)	−0.0336 (8)

Geometric parameters (Å, º) top

O1—C2	1.2023 (18)	N1A—C11A	1.3301 (16)
O2—C3	1.2224 (17)	N1A—C10A	1.4057 (17)
N1—C11	1.3371 (16)	N1A—H1NB	0.919 (14)
N1—C10	1.4009 (17)	O1A—C2A	1.2042 (17)
N1—H1NA	0.887 (14)	O2A—C3A	1.2304 (17)
C1—C11	1.4910 (17)	C1A—C11A	1.4949 (17)
C1—C12	1.5260 (19)	C1A—C12A	1.525 (2)
C1—C13	1.530 (2)	C1A—C13A	1.532 (2)
C1—C2	1.5470 (19)	C1A—C2A	1.5424 (19)
C2—C3	1.551 (2)	C2A—C3A	1.545 (2)
C3—C4	1.4192 (19)	C3A—C4A	1.4151 (18)
C4—C11	1.3863 (17)	C4A—C11A	1.3937 (17)
C4—C5	1.4359 (19)	C4A—C5A	1.4370 (18)
C5—C6	1.3920 (19)	C5A—C6A	1.3939 (19)
C5—C10	1.4100 (19)	C5A—C10A	1.4095 (18)
C6—C7	1.379 (3)	C6A—C7A	1.378 (2)
C6—H6A	0.9500	C6A—H6AA	0.9500
C7—C8	1.392 (3)	C7A—C8A	1.390 (3)
C7—H7A	0.9500	C7A—H7AA	0.9500
C8—C9	1.376 (2)	C8A—C9A	1.383 (2)
C8—H8A	0.9500	C8A—H8AA	0.9500
C9—C10	1.386 (2)	C9A—C10A	1.3822 (19)
C9—H9A	0.9500	C9A—H9AA	0.9500
C12—H12D	0.9800	C12A—H12A	0.9800
C12—H12E	0.9800	C12A—H12B	0.9800
C12—H12F	0.9800	C12A—H12C	0.9800
C13—H13D	0.9800	C13A—H13A	0.9800
C13—H13E	0.9800	C13A—H13B	0.9800
C13—H13F	0.9800	C13A—H13C	0.9800

C11—N1—C10	108.76 (11)	C11A—N1A—C10A	108.31 (11)
C11—N1—H1NA	121.8 (11)	C11A—N1A—H1NB	122.5 (11)
C10—N1—H1NA	129.4 (11)	C10A—N1A—H1NB	129.0 (11)
C11—C1—C12	113.21 (12)	C11A—C1A—C12A	114.55 (12)
C11—C1—C13	113.17 (12)	C11A—C1A—C13A	111.77 (11)
C12—C1—C13	110.52 (13)	C12A—C1A—C13A	111.60 (14)
C11—C1—C2	98.41 (10)	C11A—C1A—C2A	97.98 (10)
C12—C1—C2	109.97 (12)	C12A—C1A—C2A	110.59 (12)
C13—C1—C2	110.99 (12)	C13A—C1A—C2A	109.51 (12)
O1—C2—C1	125.61 (14)	O1A—C2A—C1A	125.67 (14)
O1—C2—C3	124.13 (14)	O1A—C2A—C3A	123.63 (14)
C1—C2—C3	110.25 (11)	C1A—C2A—C3A	110.69 (11)
O2—C3—C4	132.30 (14)	O2A—C3A—C4A	132.76 (14)
O2—C3—C2	123.08 (13)	O2A—C3A—C2A	122.40 (13)
C4—C3—C2	104.62 (11)	C4A—C3A—C2A	104.84 (11)
C11—C4—C3	110.28 (12)	C11A—C4A—C3A	109.89 (12)
C11—C4—C5	107.02 (11)	C11A—C4A—C5A	107.00 (11)
C3—C4—C5	142.68 (12)	C3A—C4A—C5A	143.11 (13)
C6—C5—C10	119.17 (14)	C6A—C5A—C10A	119.22 (13)
C6—C5—C4	135.02 (13)	C6A—C5A—C4A	135.42 (13)
C10—C5—C4	105.80 (11)	C10A—C5A—C4A	105.36 (11)
C7—C6—C5	118.31 (16)	C7A—C6A—C5A	118.32 (15)
C7—C6—H6A	120.8	C7A—C6A—H6AA	120.8
C5—C6—H6A	120.8	C5A—C6A—H6AA	120.8
C6—C7—C8	121.72 (16)	C6A—C7A—C8A	121.50 (14)
C6—C7—H7A	119.1	C6A—C7A—H7AA	119.3
C8—C7—H7A	119.1	C8A—C7A—H7AA	119.3
C9—C8—C7	121.20 (16)	C9A—C8A—C7A	121.55 (15)
C9—C8—H8A	119.4	C9A—C8A—H8AA	119.2
C7—C8—H8A	119.4	C7A—C8A—H8AA	119.2
C8—C9—C10	117.32 (16)	C10A—C9A—C8A	116.88 (15)
C8—C9—H9A	121.3	C10A—C9A—H9AA	121.6
C10—C9—H9A	121.3	C8A—C9A—H9AA	121.6
C9—C10—N1	129.67 (13)	C9A—C10A—N1A	128.81 (13)
C9—C10—C5	122.27 (13)	C9A—C10A—C5A	122.53 (13)
N1—C10—C5	108.06 (11)	N1A—C10A—C5A	108.66 (11)
N1—C11—C4	110.35 (11)	N1A—C11A—C4A	110.66 (11)
N1—C11—C1	133.24 (11)	N1A—C11A—C1A	132.96 (12)
C4—C11—C1	116.41 (11)	C4A—C11A—C1A	116.33 (11)
C1—C12—H12D	109.5	C1A—C12A—H12A	109.5
C1—C12—H12E	109.5	C1A—C12A—H12B	109.5
H12D—C12—H12E	109.5	H12A—C12A—H12B	109.5
C1—C12—H12F	109.5	C1A—C12A—H12C	109.5
H12D—C12—H12F	109.5	H12A—C12A—H12C	109.5
H12E—C12—H12F	109.5	H12B—C12A—H12C	109.5
C1—C13—H13D	109.5	C1A—C13A—H13A	109.5
C1—C13—H13E	109.5	C1A—C13A—H13B	109.5
H13D—C13—H13E	109.5	H13A—C13A—H13B	109.5
C1—C13—H13F	109.5	C1A—C13A—H13C	109.5
H13D—C13—H13F	109.5	H13A—C13A—H13C	109.5
H13E—C13—H13F	109.5	H13B—C13A—H13C	109.5

C11—C1—C2—O1	−178.28 (17)	C11A—C1A—C2A—O1A	−174.04 (15)
C12—C1—C2—O1	−59.7 (2)	C12A—C1A—C2A—O1A	−54.0 (2)
C13—C1—C2—O1	62.9 (2)	C13A—C1A—C2A—O1A	69.41 (19)
C11—C1—C2—C3	0.43 (15)	C11A—C1A—C2A—C3A	4.93 (13)
C12—C1—C2—C3	118.96 (14)	C12A—C1A—C2A—C3A	124.99 (13)
C13—C1—C2—C3	−118.44 (13)	C13A—C1A—C2A—C3A	−111.62 (13)
O1—C2—C3—O2	−0.2 (3)	O1A—C2A—C3A—O2A	−4.3 (2)
C1—C2—C3—O2	−178.95 (15)	C1A—C2A—C3A—O2A	176.71 (13)
O1—C2—C3—C4	179.30 (17)	O1A—C2A—C3A—C4A	175.40 (15)
C1—C2—C3—C4	0.57 (16)	C1A—C2A—C3A—C4A	−3.60 (15)
O2—C3—C4—C11	178.02 (17)	O2A—C3A—C4A—C11A	−179.98 (16)
C2—C3—C4—C11	−1.44 (16)	C2A—C3A—C4A—C11A	0.37 (15)
O2—C3—C4—C5	−0.2 (3)	O2A—C3A—C4A—C5A	0.6 (3)
C2—C3—C4—C5	−179.69 (18)	C2A—C3A—C4A—C5A	−179.08 (17)
C11—C4—C5—C6	−179.60 (17)	C11A—C4A—C5A—C6A	179.17 (16)
C3—C4—C5—C6	−1.3 (3)	C3A—C4A—C5A—C6A	−1.4 (3)
C11—C4—C5—C10	−0.31 (15)	C11A—C4A—C5A—C10A	−0.72 (15)
C3—C4—C5—C10	177.97 (19)	C3A—C4A—C5A—C10A	178.74 (17)
C10—C5—C6—C7	0.7 (3)	C10A—C5A—C6A—C7A	0.4 (2)
C4—C5—C6—C7	179.91 (18)	C4A—C5A—C6A—C7A	−179.47 (16)
C5—C6—C7—C8	−0.3 (3)	C5A—C6A—C7A—C8A	−0.6 (3)
C6—C7—C8—C9	−0.4 (3)	C6A—C7A—C8A—C9A	0.3 (3)
C7—C8—C9—C10	0.6 (3)	C7A—C8A—C9A—C10A	0.3 (3)
C8—C9—C10—N1	−179.92 (16)	C8A—C9A—C10A—N1A	178.99 (15)
C8—C9—C10—C5	−0.2 (3)	C8A—C9A—C10A—C5A	−0.6 (3)
C11—N1—C10—C9	−179.70 (16)	C11A—N1A—C10A—C9A	−179.67 (15)
C11—N1—C10—C5	0.51 (16)	C11A—N1A—C10A—C5A	−0.06 (16)
C6—C5—C10—C9	−0.5 (2)	C6A—C5A—C10A—C9A	0.2 (2)
C4—C5—C10—C9	−179.92 (15)	C4A—C5A—C10A—C9A	−179.88 (14)
C6—C5—C10—N1	179.31 (14)	C6A—C5A—C10A—N1A	−179.42 (13)
C4—C5—C10—N1	−0.11 (15)	C4A—C5A—C10A—N1A	0.48 (15)
C10—N1—C11—C4	−0.73 (15)	C10A—N1A—C11A—C4A	−0.41 (15)
C10—N1—C11—C1	179.04 (14)	C10A—N1A—C11A—C1A	176.95 (13)
C3—C4—C11—N1	−178.24 (12)	C3A—C4A—C11A—N1A	−178.94 (11)
C5—C4—C11—N1	0.65 (16)	C5A—C4A—C11A—N1A	0.72 (15)
C3—C4—C11—C1	1.95 (17)	C3A—C4A—C11A—C1A	3.22 (16)
C5—C4—C11—C1	−179.16 (11)	C5A—C4A—C11A—C1A	−177.13 (11)
C12—C1—C11—N1	62.8 (2)	C12A—C1A—C11A—N1A	60.7 (2)
C13—C1—C11—N1	−63.97 (19)	C13A—C1A—C11A—N1A	−67.49 (19)
C2—C1—C11—N1	178.83 (15)	C2A—C1A—C11A—N1A	177.73 (14)
C12—C1—C11—C4	−117.46 (14)	C12A—C1A—C11A—C4A	−122.05 (14)
C13—C1—C11—C4	115.79 (14)	C13A—C1A—C11A—C4A	109.76 (14)
C2—C1—C11—C4	−1.41 (15)	C2A—C1A—C11A—C4A	−5.02 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NA···O2A	0.89 (1)	1.95 (1)	2.8025 (16)	161 (2)
N1A—H1NB···O2ⁱ	0.92 (1)	1.87 (1)	2.7686 (16)	164 (2)
C9A—H9AA···O1ⁱ	0.95	2.51	3.376 (2)	152
C12A—H12B···O2ⁱ	0.98	2.57	3.430 (2)	146

Symmetry code: (i) x−1, y, z+1.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁NO₂
M_r	213.23
Crystal system, space group	Triclinic, P1
Temperature (K)	170
a, b, c (Å)	9.1091 (7), 11.5337 (8), 11.8745 (9)
α, β, γ (°)	63.230 (7), 80.596 (6), 79.970 (6)
V (Å³)	1091.69 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.28 × 0.25 × 0.24

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2010)
T_min, T_max	0.976, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	10062, 5644, 4698
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.157, 1.05
No. of reflections	5644
No. of parameters	299
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.20

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NA···O2A	0.887 (14)	1.950 (14)	2.8025 (16)	160.7 (16)
N1A—H1NB···O2ⁱ	0.919 (14)	1.874 (14)	2.7686 (16)	163.9 (16)
C9A—H9AA···O1ⁱ	0.95	2.51	3.376 (2)	151.6
C12A—H12B···O2ⁱ	0.98	2.57	3.430 (2)	146.3

Symmetry code: (i) x−1, y, z+1.

Acknowledgements

JCB wishes to thank the School of Graduate Studies and Research, UWI, and the Government of Barbados for the funding of this research. JPJ acknowledges the NSF–MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

References

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Volume 68| Part 2| February 2012| Pages o364-o365

doi:10.1107/S1600536812000517

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

3,3-Di­methyl-1,2,3,4-tetra­hydro­cyclo­penta­[b]indole-1,2-dione (bruceolline E)

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

3,3-Dimethyl-1,2,3,4-tetrahydrocyclopenta[b]indole-1,2-dione (bruceolline E)