Bruceolline J: 2-hy-droxy-3,3-dimethyl-2,3-di-hydro-cyclo-penta-[b]indol-1(4H)-one.

The 12-membered cyclo-penta-[b]indole ring system in the title compound, C13H13NO2, deviates only slightly from planarity (r.m.s. deviation = 0.051 Å). In the crystal, N-H⋯O and O-H⋯O hydrogen bonds link the mol-ecules into sheets parallel to (100). The five-membered cyclopentanone ring is in slightly distorted envelope conformation with the C atom bearing the hydroxy substituent as the flap.

Related literature

For a review of compounds isolated from Brucea sp. plants, see: Liu et al. (2009 ▶). For the first isolation of bruceolline J, see: Chen et al. (2011 ▶). For the DDQ-mediated selective oxidation of indole side chains, see: Oikawa & Yonemitsu (1977 ▶). For examples of the reduction of α-keto esters with sodium borohydride, see Dalla et al. (1999 ▶). For the enanti­oselective reduction of related sterically hindered ketones with β-chloro­diisopinocampheylborane, see: Brown et al. (1986 ▶). For the isolation of related bruceollines, see: Ouyang et al. (1994a ▶,b ▶, 1995 ▶). For the crystal structure of bruceolline D, see: Lopchuk et al. (2013 ▶). For the total synthesis and crystal structure of bruceolline E, see: Jordan et al. (2011 ▶, 2012) ▶. For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C13H13NO2

M = 215.24

Monoclinic,

a = 8.2951 (3) Å

b = 12.3070 (4) Å

c = 10.7340 (4) Å

β = 97.207 (3)°

V = 1087.15 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 173 K

0.44 × 0.38 × 0.34 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer

Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T min = 0.782, T max = 1.000

13545 measured reflections

3753 independent reflections

2888 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.134

S = 1.04

3753 reflections

148 parameters

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.25 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: XP in SHELXTL.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813020527/bt6922sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813020527/bt6922Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813020527/bt6922Isup3.cml

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

C13H13NO2	F(000) = 456
Mr = 215.24	Dx = 1.315 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.7107 Å
a = 8.2951 (3) Å	Cell parameters from 3528 reflections
b = 12.3070 (4) Å	θ = 3.3–32.9°
c = 10.7340 (4) Å	µ = 0.09 mm−1
β = 97.207 (3)°	T = 173 K
V = 1087.15 (7) Å3	Irregular, colourless
Z = 4	0.44 × 0.38 × 0.34 mm

Agilent Xcalibur (Eos, Gemini) diffractometer	3753 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2888 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Detector resolution: 16.0416 pixels mm-1	θmax = 33.0°, θmin = 3.4°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	k = −17→18
Tmin = 0.782, Tmax = 1.000	l = −16→15
13545 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048	H-atom parameters constrained
wR(F2) = 0.134	w = 1/[σ2(Fo2) + (0.0662P)2 + 0.2062P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
3753 reflections	Δρmax = 0.40 e Å−3
148 parameters	Δρmin = −0.25 e Å−3
0 restraints

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.

	x	y	z	Uiso*/Ueq
O1	0.83909 (11)	0.55666 (6)	0.93513 (8)	0.03008 (19)
O2	1.13253 (11)	0.51818 (7)	0.82424 (8)	0.0297 (2)
H2	1.1552	0.4933	0.8972	0.045*
N1	0.76891 (11)	0.21451 (7)	0.76238 (9)	0.0246 (2)
H1	0.7945	0.1602	0.7152	0.030*
C1	0.83979 (13)	0.31258 (8)	0.77083 (10)	0.0221 (2)
C2	0.98429 (13)	0.35821 (9)	0.71904 (10)	0.0233 (2)
C3	0.98044 (14)	0.47719 (8)	0.77069 (10)	0.0242 (2)
H3	0.9398	0.5254	0.6986	0.029*
C4	0.85291 (13)	0.47926 (8)	0.86414 (9)	0.0230 (2)
C5	0.76844 (13)	0.37877 (9)	0.85201 (10)	0.0233 (2)
C6	0.64335 (13)	0.31588 (9)	0.90039 (10)	0.0239 (2)
C7	0.53565 (14)	0.33227 (11)	0.98851 (11)	0.0301 (2)
H7	0.5298	0.4006	1.0290	0.036*
C8	0.43771 (15)	0.24690 (12)	1.01561 (13)	0.0365 (3)
H8	0.3650	0.2567	1.0764	0.044*
C9	0.44313 (15)	0.14681 (12)	0.95594 (14)	0.0383 (3)
H9	0.3739	0.0899	0.9768	0.046*
C10	0.54722 (15)	0.12837 (10)	0.86689 (13)	0.0333 (3)
H10	0.5498	0.0604	0.8252	0.040*
C11	0.64742 (13)	0.21344 (9)	0.84131 (10)	0.0249 (2)
C12	1.13707 (14)	0.29740 (10)	0.77445 (12)	0.0309 (2)
H12A	1.2332	0.3343	0.7503	0.046*
H12B	1.1332	0.2228	0.7424	0.046*
H12C	1.1429	0.2961	0.8662	0.046*
C13	0.96704 (18)	0.35481 (12)	0.57537 (11)	0.0364 (3)
H13A	0.8664	0.3917	0.5411	0.055*
H13B	0.9636	0.2790	0.5471	0.055*
H13C	1.0601	0.3916	0.5460	0.055*

	U11	U22	U33	U12	U13	U23
O1	0.0424 (5)	0.0199 (4)	0.0285 (4)	0.0036 (3)	0.0066 (3)	−0.0047 (3)
O2	0.0386 (5)	0.0241 (4)	0.0273 (4)	−0.0099 (3)	0.0075 (3)	0.0006 (3)
N1	0.0267 (4)	0.0190 (4)	0.0284 (4)	0.0002 (3)	0.0046 (3)	−0.0042 (3)
C1	0.0248 (5)	0.0199 (4)	0.0216 (4)	0.0009 (4)	0.0033 (3)	−0.0015 (4)
C2	0.0279 (5)	0.0229 (5)	0.0197 (4)	−0.0015 (4)	0.0056 (4)	−0.0019 (4)
C3	0.0332 (6)	0.0189 (4)	0.0210 (5)	−0.0019 (4)	0.0051 (4)	0.0009 (4)
C4	0.0303 (5)	0.0184 (4)	0.0201 (4)	0.0036 (4)	0.0023 (4)	0.0001 (3)
C5	0.0266 (5)	0.0210 (5)	0.0228 (5)	0.0021 (4)	0.0056 (4)	−0.0008 (4)
C6	0.0233 (5)	0.0238 (5)	0.0245 (5)	0.0022 (4)	0.0027 (4)	0.0020 (4)
C7	0.0265 (5)	0.0358 (6)	0.0289 (5)	0.0046 (4)	0.0064 (4)	0.0019 (5)
C8	0.0271 (6)	0.0474 (7)	0.0364 (6)	0.0022 (5)	0.0090 (5)	0.0099 (6)
C9	0.0282 (6)	0.0386 (7)	0.0485 (8)	−0.0043 (5)	0.0068 (5)	0.0136 (6)
C10	0.0293 (6)	0.0262 (6)	0.0436 (7)	−0.0029 (4)	0.0022 (5)	0.0052 (5)
C11	0.0232 (5)	0.0227 (5)	0.0283 (5)	0.0013 (4)	0.0017 (4)	0.0023 (4)
C12	0.0276 (6)	0.0250 (5)	0.0405 (6)	0.0014 (4)	0.0062 (4)	−0.0033 (5)
C13	0.0477 (7)	0.0408 (7)	0.0217 (5)	−0.0070 (6)	0.0080 (5)	−0.0050 (5)

O1—C4	1.2341 (13)	C6—C11	1.4136 (15)
O2—H2	0.8400	C7—H7	0.9500
O2—C3	1.4122 (14)	C7—C8	1.3812 (19)
N1—H1	0.8800	C8—H8	0.9500
N1—C1	1.3406 (13)	C8—C9	1.392 (2)
N1—C11	1.3956 (14)	C9—H9	0.9500
C1—C2	1.4928 (15)	C9—C10	1.3849 (19)
C1—C5	1.3793 (14)	C10—H10	0.9500
C2—C3	1.5675 (15)	C10—C11	1.3854 (16)
C2—C12	1.5267 (16)	C12—H12A	0.9800
C2—C13	1.5313 (15)	C12—H12B	0.9800
C3—H3	1.0000	C12—H12C	0.9800
C3—C4	1.5467 (15)	C13—H13A	0.9800
C4—C5	1.4194 (15)	C13—H13B	0.9800
C5—C6	1.4425 (15)	C13—H13C	0.9800
C6—C7	1.3948 (15)
C3—O2—H2	109.5	C6—C7—H7	120.8
C1—N1—H1	125.9	C8—C7—C6	118.46 (12)
C1—N1—C11	108.15 (9)	C8—C7—H7	120.8
C11—N1—H1	125.9	C7—C8—H8	119.2
N1—C1—C2	132.79 (9)	C7—C8—C9	121.50 (12)
N1—C1—C5	110.80 (10)	C9—C8—H8	119.2
C5—C1—C2	116.19 (9)	C8—C9—H9	119.3
C1—C2—C3	99.60 (8)	C10—C9—C8	121.45 (11)
C1—C2—C12	109.66 (9)	C10—C9—H9	119.3
C1—C2—C13	112.76 (9)	C9—C10—H10	121.5
C12—C2—C3	111.89 (9)	C9—C10—C11	117.03 (12)
C12—C2—C13	110.31 (10)	C11—C10—H10	121.5
C13—C2—C3	112.23 (9)	N1—C11—C6	108.88 (9)
O2—C3—C2	114.89 (9)	C10—C11—N1	128.63 (11)
O2—C3—H3	107.5	C10—C11—C6	122.44 (11)
O2—C3—C4	112.27 (8)	C2—C12—H12A	109.5
C2—C3—H3	107.5	C2—C12—H12B	109.5
C4—C3—C2	106.90 (8)	C2—C12—H12C	109.5
C4—C3—H3	107.5	H12A—C12—H12B	109.5
O1—C4—C3	122.49 (10)	H12A—C12—H12C	109.5
O1—C4—C5	130.25 (10)	H12B—C12—H12C	109.5
C5—C4—C3	107.22 (8)	C2—C13—H13A	109.5
C1—C5—C4	109.06 (9)	C2—C13—H13B	109.5
C1—C5—C6	107.19 (10)	C2—C13—H13C	109.5
C4—C5—C6	143.48 (10)	H13A—C13—H13B	109.5
C7—C6—C5	135.84 (11)	H13A—C13—H13C	109.5
C7—C6—C11	119.12 (10)	H13B—C13—H13C	109.5
C11—C6—C5	104.97 (9)
O1—C4—C5—C1	−172.60 (11)	C4—C5—C6—C11	−173.69 (15)
O1—C4—C5—C6	0.2 (2)	C5—C1—C2—C3	−7.02 (12)
O2—C3—C4—O1	41.66 (14)	C5—C1—C2—C12	110.49 (11)
O2—C3—C4—C5	−136.56 (9)	C5—C1—C2—C13	−126.17 (11)
N1—C1—C2—C3	178.95 (11)	C5—C6—C7—C8	−175.79 (12)
N1—C1—C2—C12	−63.53 (15)	C5—C6—C11—N1	0.33 (12)
N1—C1—C2—C13	59.81 (16)	C5—C6—C11—C10	177.91 (11)
N1—C1—C5—C4	176.56 (9)	C6—C7—C8—C9	−0.91 (19)
N1—C1—C5—C6	1.03 (13)	C7—C6—C11—N1	−177.07 (10)
C1—N1—C11—C6	0.28 (12)	C7—C6—C11—C10	0.51 (17)
C1—N1—C11—C10	−177.10 (12)	C7—C8—C9—C10	0.1 (2)
C1—C2—C3—O2	134.83 (9)	C8—C9—C10—C11	0.97 (19)
C1—C2—C3—C4	9.56 (10)	C9—C10—C11—N1	175.78 (11)
C1—C5—C6—C7	175.93 (13)	C9—C10—C11—C6	−1.28 (18)
C1—C5—C6—C11	−0.81 (12)	C11—N1—C1—C2	173.45 (11)
C2—C1—C5—C4	1.24 (13)	C11—N1—C1—C5	−0.82 (12)
C2—C1—C5—C6	−174.29 (9)	C11—C6—C7—C8	0.61 (17)
C2—C3—C4—O1	168.51 (10)	C12—C2—C3—O2	19.00 (12)
C2—C3—C4—C5	−9.72 (11)	C12—C2—C3—C4	−106.28 (10)
C3—C4—C5—C1	5.44 (12)	C13—C2—C3—O2	−105.63 (11)
C3—C4—C5—C6	178.25 (14)	C13—C2—C3—C4	129.09 (10)
C4—C5—C6—C7	3.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1i	0.84	1.90	2.7245 (12)	168
N1—H1···O2ii	0.88	1.91	2.7500 (12)	158

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1i	0.84	1.90	2.7245 (12)	168
N1—H1⋯O2ii	0.88	1.91	2.7500 (12)	158

Symmetry codes: (i) ; (ii) .