supplementary materials


sj5328 scheme

Acta Cryst. (2013). E69, o1043    [ doi:10.1107/S1600536813014955 ]

Bruceolline D: 3,3-dimethyl-1H,4H-cyclopenta[b]indol-2(3H)-one

J. M. Lopchuk, G. W. Gribble and J. P. Jasinski

Abstract top

The title compound, C13H13NO, crystallizes with four independent molecules in the asymmetric unit. The 12-membered penta[b]indole rings are essentially planar, with maximum deviations ranging from 0.034 (4) to 0.036 (4) Å in the four unique molecules. In the crystal, weak C-H...O interactions are observed, which link the molecules into chains along [010].

Comment top

Bruceolline D is a cyclopent[b]indole alkaloid which was first isolated from the root wood of Brucea mollis var. tonkinensis (Ouyang et al., 1994). Our total synthesis of bruceolline D was achieved by methylation of 2-methylcyclopentane-1,3-dione (Agosta et al., 1970) followed by a palladium-catalyzed cyclization with 2-chloroaniline in 88% yield (Nazare et al., 2004). The reaction of phenylhydrazine with 2-methylcyclopentane-1,3-dione (Fischer indole synthesis) under thermal and acidic conditions has been investigated (Dashkevich, 1978). Other structurally similar bruceollines have been isolated more recently (Chen et al., 2011). Bruceolline E has been synthesized by a sequential Nazarov cyclization/selenium dioxide oxidation (Jordan et al., 2011) and the crystal structure determined (Jordan et al., 2012). In view of the importance of cyclopent[b]indole alkaloids, we report here the crystal structure of the title compound, C13H13NO, (I).

The title compound, (I), crystallizes with four molecules in the asymmetric unit (Fig. 1). In the planar 12-member cyclopenta[b]indol-2(1H,3H,4H) rings, the maximum deviations from planarity are at C4A, 0.034 (4) Å, C3B, 0.034 (4) Å, C4C, -0.036 (4) Å and C4D, -0.035 (4) Å) atoms, respectively. Bond lengths are in normal ranges (Allen et al., 1987). In the crystal weak intermolecular C—H···O interactions are observed (Table 1) which link the molecules into chains along [010] and contribute to crystal packing stability (Fig. 2).

Related literature top

For the first isolation of bruceolline D, see: Ouyang et al. (1994). For a Fischer indole synthesis approach to bruceolline D, see: Dashkevich (1978). For the methylation of 2-methylcyclopentane-1,3-dione, see: Agosta et al. (1970). For the palladium-catalysed synthesis of related fused indole structures, see: Nazare et al. (2004). For the isolation of related bruceollines, see: Chen et al. (2011). For the total synthesis and crystal structure of bruceolline E, see: Jordan et al. (2011, 2012). For standard bond lengths, see: Allen et al. (1987).

Experimental top

2-Chloroaniline (255 mg, 2.0 mmol, 1 equiv.), 2,2-dimethylcyclopentane-1, 3-dione (757 mg, 6.0 mmol, 3 equiv.), acetic acid (180 mg, 3.0 mmol, 3 equiv.), magnesium sulfate (120 mg, 1.0 mmol, 0.5 equiv.), and dimethylacetamide (6 mL) were added to a 25 mL round bottom flask. After bubbling argon through the mixture for 10 minutes, potassium phosphate tribasic (552 mg, 2.6 mmol, 1.3 equiv.) and Pd(t-Bu3P)2 (101 mg, 0.2 mmol, 0.1 equiv.) were added and the flask sealed with a septum. After bubbling argon through the reaction mixture for an additional 5 minutes, the flask was heated for 16 hours at 125°C. After the reaction was complete (monitored by TLC), the mixture was cooled to room temperature and filtered to remove insoluble material (Fig. 3). The filtered solids were washed with dimethylacetamide (3 x 2 mL). Water (40 mL) was added to the filtrate and the aqueous mixture was extracted with ethyl acetate (3 x 50 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by flash chromatography (20% ethyl acetate in pentane) to yield the desired product (I) as a pale yellow solid (350 mg, 88%). Single crystals suitable for diffraction were grown from dichloromethane layered with pentane (liquid/liquid diffusion) at ambient temperature [m.p. 434–436 K (dec); literature value 433–435 K (dec) (Ouyang et al., (1994)].

Refinement top

All of the H atoms were placed in their calculated positions and refined using a riding model with Atom—H lengths of 0.95Å (CH), 0.99Å (CH2), 0.98Å (CH3) or 0.88Å (NH). Isotropic displacement parameters for these atoms were set to 1.2 (CH, CH2 NH) or 1.5 (CH3) times Ueq of the parent atom. All methyl substituents were refined as rotating groups. The maximum and minimum residual electron density peaks of 0.69 and -0.33 eÅ-3 were located 1.38 Å, and 1.31 Å from the H12D, and C11D atoms, respectively.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound showing the atom labeling scheme and 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. Packing diagram of the title compound viewed along the c axis. Dashed lines indicate weak C—H···O intermolecular interactions forming 1-D chains along (010). H atoms not involved in these intermolecular interactions have been omitted for clarity.
[Figure 3] Fig. 3. Synthesis of (I).
3,3-dimethyl-1H,4H-cyclopenta[b]indol-2(3H)-one top
Crystal data top
C13H13NODx = 1.230 Mg m3
Mr = 199.24Cu Kα radiation, λ = 1.5418 Å
Orthorhombic, Pbc21Cell parameters from 11183 reflections
a = 10.13410 (14) Åθ = 3.0–72.4°
b = 21.9219 (3) ŵ = 0.62 mm1
c = 19.3747 (3) ÅT = 173 K
V = 4304.27 (11) Å3Prism, colourless
Z = 160.32 × 0.18 × 0.06 mm
F(000) = 1696
Data collection top
Agilent Xcalibur (Eos, Gemini)
diffractometer
7612 independent reflections
Radiation source: Enhance (Cu) X-ray Source7097 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
Detector resolution: 16.0416 pixels mm-1θmax = 72.6°, θmin = 4.0°
ω scansh = 1212
Absorption correction: multi-scan
(CrysAlis PRO and CrysAlis RED; Agilent, 2012)
k = 2619
Tmin = 0.876, Tmax = 1.000l = 2023
28235 measured reflections
Refinement top
Refinement on F21 restraint
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.068H-atom parameters constrained
wR(F2) = 0.174 w = 1/[σ2(Fo2) + (0.1346P)2 + 0.5786P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
7612 reflectionsΔρmax = 0.69 e Å3
549 parametersΔρmin = 0.33 e Å3
Crystal data top
C13H13NOV = 4304.27 (11) Å3
Mr = 199.24Z = 16
Orthorhombic, Pbc21Cu Kα radiation
a = 10.13410 (14) ŵ = 0.62 mm1
b = 21.9219 (3) ÅT = 173 K
c = 19.3747 (3) Å0.32 × 0.18 × 0.06 mm
Data collection top
Agilent Xcalibur (Eos, Gemini)
diffractometer
7612 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO and CrysAlis RED; Agilent, 2012)
7097 reflections with I > 2σ(I)
Tmin = 0.876, Tmax = 1.000Rint = 0.038
28235 measured reflectionsθmax = 72.6°
Refinement top
R[F2 > 2σ(F2)] = 0.068H-atom parameters constrained
wR(F2) = 0.174Δρmax = 0.69 e Å3
S = 1.04Δρmin = 0.33 e Å3
7612 reflectionsAbsolute structure: ?
549 parametersAbsolute structure parameter: ?
1 restraintRogers parameter: ?
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1A0.9027 (4)0.55207 (13)0.52430 (17)0.0587 (9)
N1A0.9928 (3)0.72326 (13)0.67458 (17)0.0311 (7)
H1A1.00140.71620.71910.037*
C1A0.9695 (3)0.68058 (15)0.62468 (19)0.0301 (7)
C2A0.9463 (4)0.61292 (16)0.6263 (2)0.0353 (8)
C3A0.9229 (4)0.60183 (16)0.5480 (2)0.0384 (8)
C4A0.9289 (4)0.66154 (16)0.50654 (19)0.0353 (8)
H4AA0.99830.66000.47070.042*
H4AB0.84300.67090.48460.042*
C5A0.9618 (3)0.70689 (15)0.56179 (18)0.0279 (6)
C6A0.9823 (3)0.77087 (15)0.57072 (19)0.0268 (7)
C7A0.9849 (3)0.82163 (16)0.5269 (2)0.0301 (7)
H7A0.97460.81690.47850.036*
C8A1.0027 (3)0.87872 (16)0.5556 (2)0.0347 (8)
H8A1.00370.91350.52640.042*
C9A1.0194 (4)0.88624 (17)0.6267 (2)0.0382 (9)
H9A1.03100.92620.64470.046*
C10A1.0195 (4)0.83725 (16)0.6713 (2)0.0339 (8)
H10A1.03210.84270.71950.041*
C11A1.0003 (3)0.77912 (15)0.64301 (19)0.0271 (7)
C12A1.0664 (4)0.57622 (19)0.6513 (3)0.0545 (11)
H12A1.14500.58900.62550.082*
H12B1.05070.53260.64360.082*
H12C1.08020.58370.70060.082*
C13A0.8226 (4)0.59501 (19)0.6668 (2)0.0455 (9)
H13A0.83690.60270.71600.068*
H13B0.80410.55160.65960.068*
H13C0.74740.61930.65060.068*
O1B0.4157 (3)0.15987 (11)0.55334 (18)0.0456 (7)
N1B0.6744 (3)0.34522 (12)0.56110 (16)0.0312 (6)
H1B0.76090.34190.56350.037*
C1B0.5864 (3)0.29805 (14)0.55585 (18)0.0273 (6)
C2B0.6016 (3)0.23033 (14)0.5527 (2)0.0312 (7)
C3B0.4528 (3)0.21198 (15)0.5510 (2)0.0323 (7)
C4B0.3632 (3)0.26770 (14)0.5476 (2)0.0339 (7)
H4BA0.31480.26950.50320.041*
H4BB0.29930.26820.58620.041*
C5B0.4611 (3)0.31874 (15)0.55362 (19)0.0289 (7)
C6B0.4668 (3)0.38412 (14)0.55765 (18)0.0282 (7)
C7B0.3743 (3)0.43185 (16)0.55652 (18)0.0339 (7)
H7B0.28250.42350.55410.041*
C8B0.4203 (4)0.49188 (15)0.55907 (19)0.0366 (8)
H8B0.35900.52460.55830.044*
C9B0.5547 (4)0.50435 (16)0.5627 (2)0.0368 (8)
H9B0.58280.54570.56410.044*
C10B0.6479 (4)0.45913 (15)0.56428 (19)0.0345 (7)
H10B0.73940.46840.56690.041*
C11B0.6032 (3)0.39884 (14)0.56189 (18)0.0295 (7)
C12B0.6717 (4)0.20825 (18)0.4870 (2)0.0469 (10)
H12D0.62600.22450.44640.070*
H12E0.67050.16360.48550.070*
H12F0.76320.22260.48720.070*
C13B0.6669 (4)0.20277 (16)0.6170 (2)0.0446 (9)
H13D0.75980.21510.61870.067*
H13E0.66130.15820.61480.067*
H13F0.62140.21740.65840.067*
O1C0.6041 (4)0.69989 (13)0.37896 (17)0.0555 (8)
N1C0.5290 (3)0.52512 (13)0.23148 (17)0.0328 (7)
H1C0.52290.53130.18670.039*
C1C0.5509 (3)0.56889 (15)0.28084 (18)0.0294 (7)
C2C0.5704 (4)0.63639 (16)0.27780 (19)0.0347 (7)
C3C0.5900 (3)0.64918 (16)0.3560 (2)0.0365 (8)
C4C0.5840 (4)0.59052 (16)0.39915 (19)0.0349 (7)
H4CA0.66900.58250.42260.042*
H4CB0.51260.59230.43390.042*
C5C0.5558 (3)0.54359 (15)0.34498 (18)0.0288 (6)
C6C0.5340 (3)0.47964 (14)0.33686 (18)0.0267 (7)
C7C0.5275 (3)0.42955 (16)0.3818 (2)0.0318 (7)
H7C0.53780.43520.43010.038*
C8C0.5058 (3)0.37180 (16)0.3550 (2)0.0348 (8)
H8C0.50020.33770.38500.042*
C9C0.4921 (4)0.36376 (16)0.2839 (2)0.0372 (9)
H9C0.47760.32380.26660.045*
C10C0.4987 (3)0.41164 (16)0.2377 (2)0.0334 (8)
H10C0.49040.40530.18940.040*
C11C0.5181 (3)0.46927 (15)0.2650 (2)0.0280 (7)
C12C0.4486 (4)0.67119 (17)0.2516 (3)0.0506 (11)
H12G0.43390.66150.20280.076*
H12H0.46320.71510.25680.076*
H12I0.37110.65910.27860.076*
C13C0.6936 (4)0.6559 (2)0.2375 (2)0.0460 (9)
H13G0.77070.63410.25550.069*
H13H0.70680.69990.24280.069*
H13I0.68190.64600.18860.069*
O1D0.0630 (3)0.59408 (11)0.35172 (17)0.0451 (7)
N1D0.1833 (3)0.40513 (11)0.35371 (16)0.0299 (6)
H1D0.27000.40700.35510.036*
C1D0.0984 (3)0.45404 (15)0.35461 (18)0.0282 (6)
C2D0.1177 (3)0.52123 (14)0.35591 (19)0.0307 (7)
C3D0.0296 (3)0.54136 (15)0.3543 (2)0.0333 (8)
C4D0.1232 (3)0.48702 (16)0.3542 (2)0.0375 (8)
H4DA0.17790.48600.39650.045*
H4DB0.18150.48740.31320.045*
C5D0.0288 (3)0.43463 (15)0.3519 (2)0.0307 (7)
C6D0.0265 (3)0.36943 (15)0.3490 (2)0.0315 (7)
C7D0.1231 (4)0.32326 (17)0.3459 (2)0.0399 (8)
H7D0.21430.33310.34440.048*
C8D0.0809 (4)0.26286 (17)0.3451 (2)0.0430 (9)
H8D0.14470.23110.34340.052*
C9D0.0526 (4)0.24775 (16)0.3467 (2)0.0394 (8)
H9D0.07790.20600.34630.047*
C10D0.1482 (4)0.29203 (15)0.34891 (19)0.0372 (8)
H10D0.23910.28150.34950.045*
C11D0.1085 (3)0.35272 (14)0.35022 (18)0.0304 (7)
C12D0.1847 (4)0.5439 (2)0.4218 (2)0.0487 (10)
H12J0.13540.52940.46210.073*
H12K0.18640.58860.42180.073*
H12L0.27520.52830.42370.073*
C13D0.1868 (4)0.54571 (17)0.2920 (2)0.0469 (10)
H13J0.28030.53440.29340.070*
H13K0.17890.59020.29070.070*
H13L0.14590.52830.25060.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.093 (3)0.0354 (15)0.0473 (17)0.0261 (15)0.0177 (17)0.0125 (12)
N1A0.0434 (16)0.0309 (15)0.0191 (15)0.0056 (11)0.0003 (11)0.0026 (11)
C1A0.0331 (16)0.0282 (16)0.0289 (18)0.0043 (12)0.0039 (13)0.0030 (13)
C2A0.0396 (18)0.0309 (17)0.036 (2)0.0089 (14)0.0013 (15)0.0004 (14)
C3A0.0433 (19)0.0360 (18)0.0359 (19)0.0109 (14)0.0103 (15)0.0050 (15)
C4A0.0418 (18)0.0346 (18)0.0296 (18)0.0074 (14)0.0006 (15)0.0044 (14)
C5A0.0297 (14)0.0294 (15)0.0246 (17)0.0031 (12)0.0031 (12)0.0038 (13)
C6A0.0249 (13)0.0302 (17)0.0253 (17)0.0019 (11)0.0011 (12)0.0030 (13)
C7A0.0284 (15)0.0322 (17)0.0298 (19)0.0015 (12)0.0036 (13)0.0016 (14)
C8A0.0301 (15)0.0266 (16)0.047 (3)0.0029 (12)0.0020 (15)0.0054 (17)
C9A0.0363 (18)0.0285 (17)0.050 (3)0.0012 (13)0.0013 (16)0.0117 (17)
C10A0.0384 (18)0.0317 (18)0.032 (2)0.0030 (13)0.0054 (15)0.0081 (15)
C11A0.0286 (15)0.0296 (17)0.0231 (19)0.0011 (12)0.0020 (12)0.0041 (13)
C12A0.048 (2)0.037 (2)0.079 (3)0.0004 (17)0.006 (2)0.005 (2)
C13A0.051 (2)0.049 (2)0.036 (2)0.0195 (17)0.0049 (17)0.0028 (16)
O1B0.0417 (14)0.0260 (12)0.069 (2)0.0092 (10)0.0051 (14)0.0036 (12)
N1B0.0253 (12)0.0252 (12)0.0432 (17)0.0049 (9)0.0014 (12)0.0024 (11)
C1B0.0288 (14)0.0213 (14)0.0319 (17)0.0054 (11)0.0013 (13)0.0010 (12)
C2B0.0284 (15)0.0244 (15)0.041 (2)0.0005 (11)0.0026 (14)0.0028 (13)
C3B0.0289 (15)0.0291 (16)0.039 (2)0.0075 (12)0.0052 (14)0.0022 (14)
C4B0.0246 (14)0.0309 (16)0.046 (2)0.0035 (12)0.0009 (14)0.0026 (14)
C5B0.0296 (15)0.0256 (15)0.0316 (19)0.0002 (12)0.0010 (13)0.0010 (13)
C6B0.0378 (17)0.0210 (15)0.0259 (18)0.0045 (11)0.0021 (13)0.0002 (12)
C7B0.0355 (16)0.0349 (17)0.0312 (17)0.0017 (13)0.0011 (14)0.0003 (14)
C8B0.054 (2)0.0264 (16)0.0290 (18)0.0120 (14)0.0023 (16)0.0009 (14)
C9B0.059 (2)0.0238 (16)0.0274 (18)0.0080 (14)0.0063 (16)0.0031 (13)
C10B0.0397 (17)0.0307 (16)0.0331 (18)0.0095 (13)0.0014 (14)0.0028 (14)
C11B0.0331 (15)0.0270 (15)0.0285 (17)0.0001 (12)0.0003 (13)0.0003 (13)
C12B0.039 (2)0.042 (2)0.060 (3)0.0008 (15)0.0147 (18)0.0147 (18)
C13B0.041 (2)0.0298 (18)0.063 (3)0.0036 (14)0.0026 (18)0.0105 (17)
O1C0.080 (2)0.0346 (14)0.0520 (18)0.0222 (14)0.0161 (16)0.0098 (12)
N1C0.0434 (16)0.0320 (16)0.0229 (16)0.0052 (11)0.0011 (12)0.0013 (12)
C1C0.0256 (15)0.0336 (16)0.0290 (18)0.0027 (12)0.0017 (13)0.0030 (13)
C2C0.0385 (17)0.0318 (17)0.0339 (19)0.0077 (13)0.0003 (14)0.0007 (14)
C3C0.0373 (17)0.0343 (18)0.038 (2)0.0114 (13)0.0063 (15)0.0059 (15)
C4C0.0399 (18)0.0328 (17)0.0320 (18)0.0050 (13)0.0017 (15)0.0045 (14)
C5C0.0238 (13)0.0320 (15)0.0305 (17)0.0016 (11)0.0006 (13)0.0021 (13)
C6C0.0230 (13)0.0305 (16)0.0264 (18)0.0009 (11)0.0003 (12)0.0022 (13)
C7C0.0309 (15)0.0314 (17)0.033 (2)0.0024 (13)0.0005 (13)0.0034 (14)
C8C0.0300 (15)0.0283 (17)0.046 (2)0.0033 (12)0.0000 (15)0.0055 (17)
C9C0.0391 (18)0.0226 (16)0.050 (3)0.0024 (12)0.0020 (15)0.0048 (16)
C10C0.0304 (16)0.0330 (19)0.037 (2)0.0017 (12)0.0007 (14)0.0119 (16)
C11C0.0239 (14)0.0292 (17)0.031 (2)0.0025 (11)0.0002 (12)0.0015 (14)
C12C0.052 (2)0.0301 (19)0.070 (3)0.0010 (16)0.009 (2)0.0078 (18)
C13C0.047 (2)0.052 (2)0.039 (2)0.0212 (17)0.0042 (17)0.0021 (17)
O1D0.0455 (14)0.0275 (12)0.0624 (19)0.0103 (10)0.0065 (14)0.0039 (12)
N1D0.0255 (12)0.0268 (13)0.0375 (16)0.0054 (10)0.0005 (11)0.0014 (11)
C1D0.0270 (14)0.0257 (15)0.0318 (17)0.0062 (12)0.0000 (13)0.0008 (13)
C2D0.0287 (14)0.0236 (14)0.0397 (19)0.0005 (11)0.0046 (14)0.0010 (13)
C3D0.0384 (18)0.0251 (15)0.037 (2)0.0061 (13)0.0032 (15)0.0051 (14)
C4D0.0242 (14)0.0321 (16)0.056 (2)0.0039 (13)0.0032 (15)0.0058 (16)
C5D0.0315 (16)0.0238 (15)0.037 (2)0.0031 (12)0.0013 (14)0.0021 (14)
C6D0.0381 (17)0.0264 (16)0.0302 (19)0.0005 (12)0.0028 (14)0.0018 (14)
C7D0.0367 (17)0.0410 (19)0.042 (2)0.0044 (15)0.0063 (16)0.0023 (16)
C8D0.061 (2)0.0346 (18)0.034 (2)0.0183 (16)0.0113 (18)0.0035 (15)
C9D0.069 (2)0.0227 (16)0.0268 (19)0.0078 (15)0.0089 (17)0.0018 (14)
C10D0.0519 (19)0.0309 (16)0.0287 (17)0.0095 (14)0.0089 (16)0.0024 (14)
C11D0.0378 (17)0.0271 (15)0.0263 (16)0.0022 (12)0.0028 (14)0.0045 (13)
C12D0.0408 (19)0.046 (2)0.059 (3)0.0044 (16)0.0154 (18)0.0166 (18)
C13D0.041 (2)0.0347 (18)0.064 (3)0.0014 (15)0.0044 (18)0.0107 (18)
Geometric parameters (Å, º) top
O1A—C3A1.201 (4)O1C—C3C1.206 (4)
N1A—H1A0.8800N1C—H1C0.8800
N1A—C1A1.366 (4)N1C—C1C1.373 (4)
N1A—C11A1.371 (4)N1C—C11C1.390 (5)
C1A—C2A1.502 (5)C1C—C2C1.494 (5)
C1A—C5A1.350 (5)C1C—C5C1.362 (5)
C2A—C3A1.554 (5)C2C—C3C1.554 (5)
C2A—C12A1.537 (6)C2C—C12C1.537 (6)
C2A—C13A1.531 (5)C2C—C13C1.533 (5)
C3A—C4A1.537 (5)C3C—C4C1.534 (5)
C4A—H4AA0.9900C4C—H4CA0.9900
C4A—H4AB0.9900C4C—H4CB0.9900
C4A—C5A1.498 (4)C4C—C5C1.497 (5)
C5A—C6A1.429 (4)C5C—C6C1.428 (4)
C6A—C7A1.400 (5)C6C—C7C1.403 (5)
C6A—C11A1.424 (5)C6C—C11C1.420 (5)
C7A—H7A0.9500C7C—H7C0.9500
C7A—C8A1.381 (5)C7C—C8C1.386 (5)
C8A—H8A0.9500C8C—H8C0.9500
C8A—C9A1.398 (7)C8C—C9C1.395 (6)
C9A—H9A0.9500C9C—H9C0.9500
C9A—C10A1.378 (6)C9C—C10C1.381 (6)
C10A—H10A0.9500C10C—H10C0.9500
C10A—C11A1.401 (5)C10C—C11C1.383 (5)
C12A—H12A0.9800C12C—H12G0.9800
C12A—H12B0.9800C12C—H12H0.9800
C12A—H12C0.9800C12C—H12I0.9800
C13A—H13A0.9800C13C—H13G0.9800
C13A—H13B0.9800C13C—H13H0.9800
C13A—H13C0.9800C13C—H13I0.9800
O1B—C3B1.204 (4)O1D—C3D1.205 (4)
N1B—H1B0.8800N1D—H1D0.8800
N1B—C1B1.370 (4)N1D—C1D1.375 (4)
N1B—C11B1.379 (4)N1D—C11D1.378 (4)
C1B—C2B1.494 (4)C1D—C2D1.486 (4)
C1B—C5B1.349 (4)C1D—C5D1.359 (5)
C2B—C3B1.561 (4)C2D—C3D1.558 (4)
C2B—C12B1.536 (5)C2D—C12D1.529 (5)
C2B—C13B1.534 (5)C2D—C13D1.521 (6)
C3B—C4B1.523 (4)C3D—C4D1.522 (5)
C4B—H4BA0.9900C4D—H4DA0.9900
C4B—H4BB0.9900C4D—H4DB0.9900
C4B—C5B1.500 (4)C4D—C5D1.495 (4)
C5B—C6B1.437 (4)C5D—C6D1.431 (5)
C6B—C7B1.405 (5)C6D—C7D1.409 (5)
C6B—C11B1.422 (5)C6D—C11D1.417 (5)
C7B—H7B0.9500C7D—H7D0.9500
C7B—C8B1.397 (5)C7D—C8D1.391 (5)
C8B—H8B0.9500C8D—H8D0.9500
C8B—C9B1.391 (5)C8D—C9D1.393 (6)
C9B—H9B0.9500C9D—H9D0.9500
C9B—C10B1.370 (5)C9D—C10D1.372 (5)
C10B—H10B0.9500C10D—H10D0.9500
C10B—C11B1.398 (4)C10D—C11D1.390 (5)
C12B—H12D0.9800C12D—H12J0.9800
C12B—H12E0.9800C12D—H12K0.9800
C12B—H12F0.9800C12D—H12L0.9800
C13B—H13D0.9800C13D—H13J0.9800
C13B—H13E0.9800C13D—H13K0.9800
C13B—H13F0.9800C13D—H13L0.9800
C1A—N1A—H1A126.1C1C—N1C—H1C126.2
C1A—N1A—C11A107.8 (3)C1C—N1C—C11C107.7 (3)
C11A—N1A—H1A126.1C11C—N1C—H1C126.2
N1A—C1A—C2A133.5 (3)N1C—C1C—C2C133.3 (3)
C5A—C1A—N1A110.9 (3)C5C—C1C—N1C110.9 (3)
C5A—C1A—C2A115.5 (3)C5C—C1C—C2C115.8 (3)
C1A—C2A—C3A99.1 (3)C1C—C2C—C3C99.0 (3)
C1A—C2A—C12A113.6 (3)C1C—C2C—C12C113.5 (3)
C1A—C2A—C13A113.1 (3)C1C—C2C—C13C113.8 (3)
C12A—C2A—C3A110.3 (4)C12C—C2C—C3C109.6 (3)
C13A—C2A—C3A109.6 (3)C13C—C2C—C3C110.0 (3)
C13A—C2A—C12A110.7 (3)C13C—C2C—C12C110.4 (3)
O1A—C3A—C2A122.7 (4)O1C—C3C—C2C122.7 (4)
O1A—C3A—C4A125.5 (4)O1C—C3C—C4C125.2 (4)
C4A—C3A—C2A111.7 (3)C4C—C3C—C2C112.0 (3)
C3A—C4A—H4AA111.5C3C—C4C—H4CA111.4
C3A—C4A—H4AB111.5C3C—C4C—H4CB111.4
H4AA—C4A—H4AB109.3H4CA—C4C—H4CB109.3
C5A—C4A—C3A101.6 (3)C5C—C4C—C3C101.6 (3)
C5A—C4A—H4AA111.5C5C—C4C—H4CA111.4
C5A—C4A—H4AB111.5C5C—C4C—H4CB111.4
C1A—C5A—C4A112.0 (3)C1C—C5C—C4C111.5 (3)
C1A—C5A—C6A107.6 (3)C1C—C5C—C6C107.1 (3)
C6A—C5A—C4A140.4 (3)C6C—C5C—C4C141.4 (3)
C7A—C6A—C5A135.2 (3)C7C—C6C—C5C135.0 (3)
C7A—C6A—C11A119.6 (3)C7C—C6C—C11C118.5 (3)
C11A—C6A—C5A105.2 (3)C11C—C6C—C5C106.4 (3)
C6A—C7A—H7A120.7C6C—C7C—H7C120.3
C8A—C7A—C6A118.6 (4)C8C—C7C—C6C119.3 (4)
C8A—C7A—H7A120.7C8C—C7C—H7C120.3
C7A—C8A—H8A119.4C7C—C8C—H8C120.0
C7A—C8A—C9A121.3 (4)C7C—C8C—C9C120.1 (4)
C9A—C8A—H8A119.4C9C—C8C—H8C120.0
C8A—C9A—H9A119.1C8C—C9C—H9C118.7
C10A—C9A—C8A121.7 (3)C10C—C9C—C8C122.6 (3)
C10A—C9A—H9A119.1C10C—C9C—H9C118.7
C9A—C10A—H10A121.2C9C—C10C—H10C121.5
C9A—C10A—C11A117.6 (4)C9C—C10C—C11C117.0 (4)
C11A—C10A—H10A121.2C11C—C10C—H10C121.5
N1A—C11A—C6A108.6 (3)N1C—C11C—C6C107.9 (3)
N1A—C11A—C10A130.2 (3)C10C—C11C—N1C129.6 (4)
C10A—C11A—C6A121.2 (3)C10C—C11C—C6C122.5 (3)
C2A—C12A—H12A109.5C2C—C12C—H12G109.5
C2A—C12A—H12B109.5C2C—C12C—H12H109.5
C2A—C12A—H12C109.5C2C—C12C—H12I109.5
H12A—C12A—H12B109.5H12G—C12C—H12H109.5
H12A—C12A—H12C109.5H12G—C12C—H12I109.5
H12B—C12A—H12C109.5H12H—C12C—H12I109.5
C2A—C13A—H13A109.5C2C—C13C—H13G109.5
C2A—C13A—H13B109.5C2C—C13C—H13H109.5
C2A—C13A—H13C109.5C2C—C13C—H13I109.5
H13A—C13A—H13B109.5H13G—C13C—H13H109.5
H13A—C13A—H13C109.5H13G—C13C—H13I109.5
H13B—C13A—H13C109.5H13H—C13C—H13I109.5
C1B—N1B—H1B126.2C1D—N1D—H1D126.1
C1B—N1B—C11B107.7 (3)C1D—N1D—C11D107.9 (3)
C11B—N1B—H1B126.2C11D—N1D—H1D126.1
N1B—C1B—C2B133.3 (3)N1D—C1D—C2D133.7 (3)
C5B—C1B—N1B111.2 (3)C5D—C1D—N1D110.4 (3)
C5B—C1B—C2B115.5 (3)C5D—C1D—C2D115.8 (3)
C1B—C2B—C3B99.0 (2)C1D—C2D—C3D98.9 (2)
C1B—C2B—C12B113.2 (3)C1D—C2D—C12D113.3 (3)
C1B—C2B—C13B113.8 (3)C1D—C2D—C13D113.4 (3)
C12B—C2B—C3B110.4 (3)C12D—C2D—C3D110.5 (3)
C13B—C2B—C3B109.4 (3)C13D—C2D—C3D109.0 (3)
C13B—C2B—C12B110.4 (3)C13D—C2D—C12D111.2 (3)
O1B—C3B—C2B123.1 (3)O1D—C3D—C2D122.8 (3)
O1B—C3B—C4B125.2 (3)O1D—C3D—C4D125.2 (3)
C4B—C3B—C2B111.7 (3)C4D—C3D—C2D112.0 (3)
C3B—C4B—H4BA111.5C3D—C4D—H4DA111.4
C3B—C4B—H4BB111.5C3D—C4D—H4DB111.4
H4BA—C4B—H4BB109.3H4DA—C4D—H4DB109.3
C5B—C4B—C3B101.6 (3)C5D—C4D—C3D101.7 (3)
C5B—C4B—H4BA111.5C5D—C4D—H4DA111.4
C5B—C4B—H4BB111.5C5D—C4D—H4DB111.4
C1B—C5B—C4B112.0 (3)C1D—C5D—C4D111.4 (3)
C1B—C5B—C6B107.2 (3)C1D—C5D—C6D107.4 (3)
C6B—C5B—C4B140.8 (3)C6D—C5D—C4D141.2 (3)
C7B—C6B—C5B135.7 (3)C7D—C6D—C5D135.1 (3)
C7B—C6B—C11B118.7 (3)C7D—C6D—C11D119.1 (3)
C11B—C6B—C5B105.6 (3)C11D—C6D—C5D105.9 (3)
C6B—C7B—H7B120.7C6D—C7D—H7D121.0
C8B—C7B—C6B118.6 (3)C8D—C7D—C6D118.1 (3)
C8B—C7B—H7B120.7C8D—C7D—H7D121.0
C7B—C8B—H8B119.5C7D—C8D—H8D119.2
C9B—C8B—C7B120.9 (3)C7D—C8D—C9D121.6 (3)
C9B—C8B—H8B119.5C9D—C8D—H8D119.2
C8B—C9B—H9B118.9C8D—C9D—H9D119.4
C10B—C9B—C8B122.3 (3)C10D—C9D—C8D121.2 (3)
C10B—C9B—H9B118.9C10D—C9D—H9D119.4
C9B—C10B—H10B121.3C9D—C10D—H10D120.9
C9B—C10B—C11B117.4 (3)C9D—C10D—C11D118.2 (3)
C11B—C10B—H10B121.3C11D—C10D—H10D120.9
N1B—C11B—C6B108.3 (3)N1D—C11D—C6D108.4 (3)
N1B—C11B—C10B129.5 (3)N1D—C11D—C10D129.8 (3)
C10B—C11B—C6B122.1 (3)C10D—C11D—C6D121.8 (3)
C2B—C12B—H12D109.5C2D—C12D—H12J109.5
C2B—C12B—H12E109.5C2D—C12D—H12K109.5
C2B—C12B—H12F109.5C2D—C12D—H12L109.5
H12D—C12B—H12E109.5H12J—C12D—H12K109.5
H12D—C12B—H12F109.5H12J—C12D—H12L109.5
H12E—C12B—H12F109.5H12K—C12D—H12L109.5
C2B—C13B—H13D109.5C2D—C13D—H13J109.5
C2B—C13B—H13E109.5C2D—C13D—H13K109.5
C2B—C13B—H13F109.5C2D—C13D—H13L109.5
H13D—C13B—H13E109.5H13J—C13D—H13K109.5
H13D—C13B—H13F109.5H13J—C13D—H13L109.5
H13E—C13B—H13F109.5H13K—C13D—H13L109.5
O1A—C3A—C4A—C5A177.7 (4)O1C—C3C—C4C—C5C176.0 (4)
N1A—C1A—C2A—C3A177.7 (4)N1C—C1C—C2C—C3C179.4 (4)
N1A—C1A—C2A—C12A65.4 (5)N1C—C1C—C2C—C12C64.6 (5)
N1A—C1A—C2A—C13A61.8 (5)N1C—C1C—C2C—C13C62.7 (5)
N1A—C1A—C5A—C4A176.8 (3)N1C—C1C—C5C—C4C178.2 (3)
N1A—C1A—C5A—C6A0.4 (4)N1C—C1C—C5C—C6C0.8 (4)
C1A—N1A—C11A—C6A0.6 (4)C1C—N1C—C11C—C6C0.0 (4)
C1A—N1A—C11A—C10A178.3 (3)C1C—N1C—C11C—C10C178.5 (3)
C1A—C2A—C3A—O1A178.3 (4)C1C—C2C—C3C—O1C176.9 (4)
C1A—C2A—C3A—C4A1.8 (4)C1C—C2C—C3C—C4C1.1 (4)
C1A—C5A—C6A—C7A179.2 (4)C1C—C5C—C6C—C7C179.9 (4)
C1A—C5A—C6A—C11A0.8 (3)C1C—C5C—C6C—C11C0.7 (3)
C2A—C1A—C5A—C4A1.0 (4)C2C—C1C—C5C—C4C1.5 (4)
C2A—C1A—C5A—C6A178.3 (3)C2C—C1C—C5C—C6C179.5 (3)
C2A—C3A—C4A—C5A2.3 (4)C2C—C3C—C4C—C5C1.9 (4)
C3A—C4A—C5A—C1A2.0 (4)C3C—C4C—C5C—C1C2.1 (4)
C3A—C4A—C5A—C6A177.9 (4)C3C—C4C—C5C—C6C179.5 (4)
C4A—C5A—C6A—C7A3.1 (7)C4C—C5C—C6C—C7C1.4 (7)
C4A—C5A—C6A—C11A175.2 (4)C4C—C5C—C6C—C11C177.7 (4)
C5A—C1A—C2A—C3A0.5 (4)C5C—C1C—C2C—C3C0.2 (4)
C5A—C1A—C2A—C12A117.4 (4)C5C—C1C—C2C—C12C115.8 (4)
C5A—C1A—C2A—C13A115.4 (4)C5C—C1C—C2C—C13C116.9 (4)
C5A—C6A—C7A—C8A177.2 (3)C5C—C6C—C7C—C8C179.1 (3)
C5A—C6A—C11A—N1A0.8 (3)C5C—C6C—C11C—N1C0.4 (3)
C5A—C6A—C11A—C10A178.2 (3)C5C—C6C—C11C—C10C178.1 (3)
C6A—C7A—C8A—C9A0.7 (5)C6C—C7C—C8C—C9C0.7 (5)
C7A—C6A—C11A—N1A179.5 (3)C7C—C6C—C11C—N1C179.8 (3)
C7A—C6A—C11A—C10A0.5 (5)C7C—C6C—C11C—C10C1.2 (5)
C7A—C8A—C9A—C10A0.3 (5)C7C—C8C—C9C—C10C0.2 (6)
C8A—C9A—C10A—C11A0.9 (5)C8C—C9C—C10C—C11C0.9 (5)
C9A—C10A—C11A—N1A178.3 (3)C9C—C10C—C11C—N1C179.8 (3)
C9A—C10A—C11A—C6A0.5 (5)C9C—C10C—C11C—C6C1.6 (5)
C11A—N1A—C1A—C2A177.2 (4)C11C—N1C—C1C—C2C179.8 (3)
C11A—N1A—C1A—C5A0.1 (4)C11C—N1C—C1C—C5C0.5 (4)
C11A—C6A—C7A—C8A1.1 (5)C11C—C6C—C7C—C8C0.0 (5)
C12A—C2A—C3A—O1A58.9 (5)C12C—C2C—C3C—O1C57.9 (5)
C12A—C2A—C3A—C4A121.2 (3)C12C—C2C—C3C—C4C120.1 (3)
C13A—C2A—C3A—O1A63.2 (5)C13C—C2C—C3C—O1C63.6 (5)
C13A—C2A—C3A—C4A116.8 (4)C13C—C2C—C3C—C4C118.4 (3)
O1B—C3B—C4B—C5B174.0 (4)O1D—C3D—C4D—C5D175.3 (4)
N1B—C1B—C2B—C3B177.2 (4)N1D—C1D—C2D—C3D178.6 (4)
N1B—C1B—C2B—C12B66.0 (5)N1D—C1D—C2D—C12D64.4 (5)
N1B—C1B—C2B—C13B61.2 (5)N1D—C1D—C2D—C13D63.4 (5)
N1B—C1B—C5B—C4B179.8 (3)N1D—C1D—C5D—C4D178.9 (3)
N1B—C1B—C5B—C6B0.0 (4)N1D—C1D—C5D—C6D0.0 (4)
C1B—N1B—C11B—C6B0.6 (4)C1D—N1D—C11D—C6D0.1 (4)
C1B—N1B—C11B—C10B177.7 (4)C1D—N1D—C11D—C10D179.2 (4)
C1B—C2B—C3B—O1B174.5 (4)C1D—C2D—C3D—O1D176.7 (4)
C1B—C2B—C3B—C4B4.4 (4)C1D—C2D—C3D—C4D1.5 (4)
C1B—C5B—C6B—C7B178.4 (4)C1D—C5D—C6D—C7D179.6 (4)
C1B—C5B—C6B—C11B0.3 (4)C1D—C5D—C6D—C11D0.0 (4)
C2B—C1B—C5B—C4B0.6 (5)C2D—C1D—C5D—C4D2.7 (5)
C2B—C1B—C5B—C6B179.6 (3)C2D—C1D—C5D—C6D178.4 (3)
C2B—C3B—C4B—C5B4.8 (4)C2D—C3D—C4D—C5D2.9 (4)
C3B—C4B—C5B—C1B3.3 (4)C3D—C4D—C5D—C1D3.3 (4)
C3B—C4B—C5B—C6B177.1 (5)C3D—C4D—C5D—C6D178.3 (5)
C4B—C5B—C6B—C7B1.2 (8)C4D—C5D—C6D—C7D1.2 (9)
C4B—C5B—C6B—C11B179.3 (5)C4D—C5D—C6D—C11D178.5 (5)
C5B—C1B—C2B—C3B2.3 (4)C5D—C1D—C2D—C3D0.7 (4)
C5B—C1B—C2B—C12B114.6 (4)C5D—C1D—C2D—C12D117.6 (4)
C5B—C1B—C2B—C13B118.3 (4)C5D—C1D—C2D—C13D114.5 (4)
C5B—C6B—C7B—C8B177.4 (4)C5D—C6D—C7D—C8D178.8 (4)
C5B—C6B—C11B—N1B0.5 (4)C5D—C6D—C11D—N1D0.1 (4)
C5B—C6B—C11B—C10B177.8 (3)C5D—C6D—C11D—C10D179.2 (3)
C6B—C7B—C8B—C9B0.0 (5)C6D—C7D—C8D—C9D0.5 (6)
C7B—C6B—C11B—N1B179.0 (3)C7D—C6D—C11D—N1D179.6 (3)
C7B—C6B—C11B—C10B0.6 (5)C7D—C6D—C11D—C10D0.5 (6)
C7B—C8B—C9B—C10B0.3 (6)C7D—C8D—C9D—C10D0.3 (6)
C8B—C9B—C10B—C11B0.2 (6)C8D—C9D—C10D—C11D0.7 (6)
C9B—C10B—C11B—N1B178.3 (4)C9D—C10D—C11D—N1D178.7 (4)
C9B—C10B—C11B—C6B0.3 (5)C9D—C10D—C11D—C6D0.3 (5)
C11B—N1B—C1B—C2B179.9 (4)C11D—N1D—C1D—C2D177.9 (4)
C11B—N1B—C1B—C5B0.4 (4)C11D—N1D—C1D—C5D0.1 (4)
C11B—C6B—C7B—C8B0.5 (5)C11D—C6D—C7D—C8D0.9 (6)
C12B—C2B—C3B—O1B66.5 (5)C12D—C2D—C3D—O1D64.2 (5)
C12B—C2B—C3B—C4B114.6 (3)C12D—C2D—C3D—C4D117.5 (4)
C13B—C2B—C3B—O1B55.2 (5)C13D—C2D—C3D—O1D58.2 (5)
C13B—C2B—C3B—C4B123.7 (3)C13D—C2D—C3D—C4D120.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9B—H9B···O1Bi0.952.513.427 (4)162
C10B—H10B···O1A0.952.613.379 (5)139
C12B—H12D···O1Cii0.982.733.497 (6)136
C9D—H9D···O1Diii0.952.463.372 (4)161
C10D—H10D···O1Cii0.952.463.274 (5)144
C12D—H12J···O1Aiv0.982.693.485 (6)138
Symmetry codes: (i) x+1, y+1/2, z; (ii) x+1, y1/2, z; (iii) x, y1/2, z; (iv) x1, y, z.

Experimental details

Crystal data
Chemical formulaC13H13NO
Mr199.24
Crystal system, space groupOrthorhombic, Pbc21
Temperature (K)173
a, b, c (Å)10.13410 (14), 21.9219 (3), 19.3747 (3)
V3)4304.27 (11)
Z16
Radiation typeCu Kα
µ (mm1)0.62
Crystal size (mm)0.32 × 0.18 × 0.06
Data collection
DiffractometerAgilent Xcalibur (Eos, Gemini)
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO and CrysAlis RED; Agilent, 2012)
Tmin, Tmax0.876, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
28235, 7612, 7097
Rint0.038
(sin θ/λ)max1)0.619
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.068, 0.174, 1.04
No. of reflections7612
No. of parameters549
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.69, 0.33

Computer programs: CrysAlis PRO (Agilent, 2012), CrysAlis PRO (Agilent, 2012), SUPERFLIP (Palatinus & Chapuis, 2007), SHELXL2012 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9B—H9B···O1Bi0.952.513.427 (4)161.7
C10B—H10B···O1A0.952.613.379 (5)138.9
C12B—H12D···O1Cii0.982.733.497 (6)135.8
C9D—H9D···O1Diii0.952.463.372 (4)160.6
C10D—H10D···O1Cii0.952.463.274 (5)143.7
C12D—H12J···O1Aiv0.982.693.485 (6)137.9
Symmetry codes: (i) x+1, y+1/2, z; (ii) x+1, y1/2, z; (iii) x, y1/2, z; (iv) x1, y, z.
Acknowledgements top

JML acknowledges support from a Graduate Assistance in Areas of National Need (GAANN) fellowship. GWG acknowledges support by the Donors of the Petroleum Research Fund (PRF), administered by the American Chemical Society, and by Wyeth. JPJ acknowledges the NSF MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

references
References top

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