(1R,3R,3aS,8aR)-4-Oxo-3-phenyl-1-[(1R)-1-phenyl-eth-yl]deca-hydro-cyclo-hepta-[b]pyrrol-1-ium bromide.

The title chiral compound, C(23)H(28)NO(+)·Br(-), was obtained from an optically active amino-ethanol precursor. The pyrrolidine heterocycle has an envelope conformation, with the C atom α-positioned with respect to the keto group deviating by 0.570 (6) Å from the mean plane of other atoms. The trans-fused seven-membered ring adopts a pseudo-chair conformation. The two phenyl rings form a dihedral angle of 85.1 (2)°. The cationic center and the bromide anion are connected through an N-H⋯Br hydrogen bond.

Related literature

For general background to the aza-Cope–Mannich sequence, see: Overman (1992 ▶, 2009 ▶). For natural products with cyclo­hepta­[b]pyrrolidine, see: Earley et al. (2005 ▶); Martin et al. (2008 ▶). For biologically active compounds, see: Tamiz et al. (2000 ▶). For the preparation of cis-cyclo­hepta­[b]pyrrolidines, see: Belov et al. (2011 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C23H28NO+·Br−

M = 414.36

Monoclinic,

a = 6.7996 (4) Å

b = 13.3136 (8) Å

c = 11.3167 (8) Å

β = 94.449 (5)°

V = 1021.38 (11) Å3

Z = 2

Mo Kα radiation

μ = 2.02 mm−1

T = 295 K

0.25 × 0.25 × 0.13 mm

Data collection

Stoe STADI-VARI Pilatus-100K diffractometer

Absorption correction: integration (X-RED32; Stoe & Cie, 2012 ▶) T min = 0.229, T max = 0.482

8956 measured reflections

2995 independent reflections

2116 reflections with I > 2σ(I)

R int = 0.071

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.104

S = 0.97

2995 reflections

230 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.41 e Å−3

Δρmin = −0.29 e Å−3

Absolute structure: Flack (1983 ▶), 897 Friedel pairs

Flack parameter: −0.018 (14)

Data collection: X-AREA (Stoe & Cie, 2012 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2012 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global. DOI: 10.1107/S1600536812028073/ld2065sup1.cif

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

C23H28NO+·Br−	F(000) = 432
Mr = 414.36	Dx = 1.347 Mg m−3
Monoclinic, P21	Melting point = 498.1–498.5 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 6.7996 (4) Å	Cell parameters from 6482 reflections
b = 13.3136 (8) Å	θ = 1.8–29.2°
c = 11.3167 (8) Å	µ = 2.02 mm−1
β = 94.449 (5)°	T = 295 K
V = 1021.38 (11) Å3	Prism, colourless
Z = 2	0.25 × 0.25 × 0.13 mm

Stoe STADI-VARI Pilatus-100K diffractometer	2995 independent reflections
Radiation source: LFF Sealed Tube	2116 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.071
Detector resolution: 5.81 pixels mm-1	θmax = 26.0°, θmin = 1.8°
Rotation method scans	h = −8→8
Absorption correction: integration (X-AREA; Stoe & Cie, 2012)	k = −16→11
Tmin = 0.229, Tmax = 0.482	l = −13→9
8956 measured reflections

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)] = 0.043	H-atom parameters constrained
wR(F2) = 0.104	w = 1/[σ2(Fo2) + (0.0568P)2] where P = (Fo2 + 2Fc2)/3
S = 0.97	(Δ/σ)max < 0.001
2995 reflections	Δρmax = 0.41 e Å−3
230 parameters	Δρmin = −0.29 e Å−3
1 restraint	Absolute structure: Flack (1983), 897 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.018 (14)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S/i> 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 > 2σ(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.

	x	y	z	Uiso*/Ueq
Br1	−0.23660 (6)	0.27140 (5)	−0.02750 (6)	0.0688 (2)
N1	0.1339 (5)	0.1146 (3)	−0.0108 (3)	0.0368 (8)
H1	0.0142	0.1407	−0.0358	0.044*
C2	0.2616 (6)	0.2019 (4)	0.0343 (4)	0.0395 (10)
H2A	0.1855	0.2636	0.0320	0.047*
H2B	0.3723	0.2105	−0.0139	0.047*
C3	0.3348 (4)	0.1755 (3)	0.1631 (2)	0.0388 (10)
H3	0.4556	0.1353	0.1630	0.047*
C31	0.3719 (4)	0.2642 (3)	0.2411 (2)	0.0458 (9)
C32	0.5629 (4)	0.2789 (3)	0.2920 (2)	0.0660 (14)
H32	0.6633	0.2354	0.2738	0.079*
C33	0.6034 (13)	0.3576 (6)	0.3693 (6)	0.086 (2)
H33	0.7321	0.3668	0.4016	0.104*
C34	0.4647 (15)	0.4206 (7)	0.3991 (6)	0.091 (3)
H34	0.4953	0.4724	0.4525	0.110*
C35	0.2722 (14)	0.4082 (5)	0.3494 (6)	0.083 (2)
H35	0.1731	0.4518	0.3692	0.100*
C36	0.2295 (9)	0.3297 (4)	0.2695 (5)	0.0582 (14)
H36	0.1016	0.3221	0.2353	0.070*
C4	0.1632 (7)	0.1082 (4)	0.2013 (4)	0.0406 (10)
H4	0.0528	0.1510	0.2208	0.049*
C5	0.2251 (8)	0.0412 (4)	0.3074 (5)	0.0548 (13)
O5	0.3950 (7)	0.0369 (5)	0.3429 (4)	0.0983 (18)
C6	0.0720 (9)	−0.0179 (6)	0.3648 (5)	0.0705 (16)
H6A	0.0666	0.0073	0.4450	0.085*
H6B	0.1173	−0.0869	0.3711	0.085*
C7	−0.1365 (8)	−0.0190 (5)	0.3073 (5)	0.0598 (14)
H7A	−0.1853	0.0494	0.3033	0.072*
H7B	−0.2188	−0.0566	0.3579	0.072*
C8	−0.1601 (10)	−0.0640 (5)	0.1835 (6)	0.0589 (16)
H8A	−0.2954	−0.0866	0.1682	0.071*
H8B	−0.0757	−0.1226	0.1815	0.071*
C9	−0.1110 (7)	0.0073 (4)	0.0835 (5)	0.0496 (12)
H9A	−0.1374	−0.0270	0.0083	0.059*
H9B	−0.1983	0.0649	0.0836	0.059*
C10	0.1002 (6)	0.0443 (4)	0.0921 (4)	0.0402 (11)
H10	0.1891	−0.0135	0.0893	0.048*
C11	0.2090 (7)	0.0586 (4)	−0.1164 (4)	0.0424 (11)
H11	0.1282	−0.0021	−0.1274	0.051*
C12	0.4193 (7)	0.0238 (5)	−0.0901 (5)	0.0547 (13)
H12A	0.5038	0.0811	−0.0764	0.082*
H12B	0.4603	−0.0136	−0.1565	0.082*
H12C	0.4276	−0.0181	−0.0210	0.082*
C13	0.1697 (9)	0.1210 (4)	−0.2284 (5)	0.0470 (13)
C14	0.3192 (9)	0.1652 (5)	−0.2867 (6)	0.0695 (17)
H14	0.4491	0.1614	−0.2547	0.083*
C15	0.2742 (13)	0.2154 (6)	−0.3935 (7)	0.089 (2)
H15	0.3748	0.2438	−0.4336	0.107*
C16	0.0841 (14)	0.2229 (6)	−0.4391 (6)	0.085 (2)
H16	0.0558	0.2555	−0.5111	0.102*
C17	−0.0640 (12)	0.1837 (6)	−0.3811 (6)	0.083 (2)
H17	−0.1939	0.1909	−0.4123	0.100*
C18	−0.0238 (9)	0.1330 (5)	−0.2762 (5)	0.0640 (15)
H18	−0.1269	0.1063	−0.2368	0.077*

	U11	U22	U33	U12	U13	U23
Br1	0.0468 (2)	0.0492 (3)	0.1123 (5)	0.0021 (4)	0.0192 (2)	0.0044 (5)
N1	0.0392 (18)	0.039 (2)	0.032 (2)	−0.0024 (16)	0.0008 (15)	0.0033 (17)
C2	0.044 (2)	0.037 (2)	0.038 (3)	−0.0071 (19)	0.0080 (18)	−0.002 (2)
C3	0.040 (2)	0.043 (3)	0.033 (3)	−0.0001 (19)	0.0018 (18)	−0.002 (2)
C31	0.058 (2)	0.046 (2)	0.033 (2)	0.001 (4)	0.0015 (17)	0.008 (3)
C32	0.073 (3)	0.069 (4)	0.053 (3)	−0.016 (4)	−0.014 (2)	−0.006 (4)
C33	0.112 (6)	0.082 (5)	0.060 (4)	−0.023 (5)	−0.027 (4)	0.003 (4)
C34	0.157 (9)	0.076 (5)	0.040 (4)	−0.049 (6)	0.001 (4)	−0.010 (4)
C35	0.142 (7)	0.052 (4)	0.059 (4)	−0.005 (4)	0.037 (4)	−0.009 (3)
C36	0.074 (3)	0.055 (3)	0.048 (3)	−0.006 (3)	0.014 (3)	−0.001 (3)
C4	0.046 (2)	0.042 (3)	0.034 (3)	0.005 (2)	0.0054 (19)	0.005 (2)
C5	0.063 (3)	0.057 (3)	0.044 (3)	0.006 (3)	0.007 (2)	0.007 (3)
O5	0.067 (3)	0.144 (5)	0.081 (3)	0.003 (3)	−0.015 (2)	0.061 (3)
C6	0.083 (4)	0.074 (4)	0.054 (3)	−0.007 (4)	0.005 (3)	0.025 (4)
C7	0.062 (3)	0.058 (3)	0.063 (3)	0.001 (3)	0.025 (3)	0.014 (3)
C8	0.057 (3)	0.057 (4)	0.064 (4)	−0.013 (3)	0.015 (3)	0.013 (3)
C9	0.050 (2)	0.052 (3)	0.047 (3)	−0.015 (2)	0.001 (2)	0.008 (2)
C10	0.041 (2)	0.043 (3)	0.036 (3)	0.000 (2)	0.0045 (19)	0.006 (2)
C11	0.051 (3)	0.041 (3)	0.037 (3)	−0.006 (2)	0.010 (2)	−0.008 (2)
C12	0.056 (3)	0.053 (3)	0.056 (3)	0.010 (2)	0.012 (2)	0.001 (3)
C13	0.062 (3)	0.042 (3)	0.038 (3)	−0.004 (2)	0.008 (2)	0.000 (3)
C14	0.069 (4)	0.074 (4)	0.067 (4)	0.010 (3)	0.021 (3)	0.017 (4)
C15	0.120 (6)	0.084 (5)	0.069 (5)	0.011 (4)	0.046 (4)	0.029 (4)
C16	0.135 (7)	0.080 (5)	0.040 (4)	0.023 (5)	0.008 (4)	0.006 (3)
C17	0.109 (5)	0.095 (5)	0.044 (4)	0.004 (5)	−0.011 (4)	0.006 (4)
C18	0.071 (4)	0.076 (4)	0.044 (3)	−0.009 (3)	−0.004 (3)	0.003 (3)

N1—C2	1.515 (6)	C6—H6B	0.9700
N1—C10	1.525 (6)	C7—C8	1.521 (9)
N1—C11	1.530 (6)	C7—H7A	0.9700
N1—H1	0.9100	C7—H7B	0.9700
C2—C3	1.543 (5)	C8—C9	1.534 (8)
C2—H2A	0.9700	C8—H8A	0.9700
C2—H2B	0.9700	C8—H8B	0.9700
C3—C31	1.484 (5)	C9—C10	1.514 (6)
C3—C4	1.559 (5)	C9—H9A	0.9700
C3—H3	0.9800	C9—H9B	0.9700
C31—C36	1.360 (6)	C10—H10	0.9800
C31—C32	1.393 (4)	C11—C12	1.511 (7)
C32—C33	1.380 (9)	C11—C13	1.522 (8)
C32—H32	0.9300	C11—H11	0.9800
C33—C34	1.325 (12)	C12—H12A	0.9600
C33—H33	0.9300	C12—H12B	0.9600
C34—C35	1.394 (11)	C12—H12C	0.9600
C34—H34	0.9300	C13—C14	1.385 (8)
C35—C36	1.397 (9)	C13—C18	1.392 (8)
C35—H35	0.9300	C14—C15	1.393 (9)
C36—H36	0.9300	C14—H14	0.9300
C4—C5	1.528 (7)	C15—C16	1.358 (11)
C4—C10	1.535 (7)	C15—H15	0.9300
C4—H4	0.9800	C16—C17	1.350 (11)
C5—O5	1.195 (7)	C16—H16	0.9300
C5—C6	1.493 (8)	C17—C18	1.375 (9)
C6—C7	1.514 (8)	C17—H17	0.9300
C6—H6A	0.9700	C18—H18	0.9300
C2—N1—C10	109.3 (3)	C8—C7—H7A	108.4
C2—N1—C11	114.8 (3)	C6—C7—H7B	108.4
C10—N1—C11	112.1 (4)	C8—C7—H7B	108.4
C2—N1—H1	106.7	H7A—C7—H7B	107.5
C10—N1—H1	106.7	C7—C8—C9	115.0 (5)
C11—N1—H1	106.7	C7—C8—H8A	108.5
N1—C2—C3	106.2 (3)	C9—C8—H8A	108.5
N1—C2—H2A	110.5	C7—C8—H8B	108.5
C3—C2—H2A	110.5	C9—C8—H8B	108.5
N1—C2—H2B	110.5	H8A—C8—H8B	107.5
C3—C2—H2B	110.5	C10—C9—C8	114.4 (5)
H2A—C2—H2B	108.7	C10—C9—H9A	108.7
C31—C3—C2	114.1 (2)	C8—C9—H9A	108.7
C31—C3—C4	112.8 (2)	C10—C9—H9B	108.7
C2—C3—C4	101.5 (3)	C8—C9—H9B	108.7
C31—C3—H3	109.4	H9A—C9—H9B	107.6
C2—C3—H3	109.4	C9—C10—N1	110.4 (4)
C4—C3—H3	109.4	C9—C10—C4	115.9 (4)
C36—C31—C32	118.0 (3)	N1—C10—C4	103.0 (4)
C36—C31—C3	124.1 (3)	C9—C10—H10	109.1
C32—C31—C3	117.9 (3)	N1—C10—H10	109.1
C33—C32—C31	120.2 (4)	C4—C10—H10	109.1
C33—C32—H32	119.9	C12—C11—C13	115.7 (4)
C31—C32—H32	119.9	C12—C11—N1	111.3 (4)
C34—C33—C32	122.1 (7)	C13—C11—N1	109.7 (4)
C34—C33—H33	119.0	C12—C11—H11	106.5
C32—C33—H33	119.0	C13—C11—H11	106.5
C33—C34—C35	119.1 (7)	N1—C11—H11	106.5
C33—C34—H34	120.4	C11—C12—H12A	109.5
C35—C34—H34	120.4	C11—C12—H12B	109.5
C34—C35—C36	119.4 (7)	H12A—C12—H12B	109.5
C34—C35—H35	120.3	C11—C12—H12C	109.5
C36—C35—H35	120.3	H12A—C12—H12C	109.5
C31—C36—C35	121.1 (6)	H12B—C12—H12C	109.5
C31—C36—H36	119.4	C14—C13—C18	118.2 (5)
C35—C36—H36	119.4	C14—C13—C11	122.7 (5)
C5—C4—C10	110.6 (4)	C18—C13—C11	119.0 (5)
C5—C4—C3	112.8 (4)	C13—C14—C15	119.8 (6)
C10—C4—C3	105.3 (3)	C13—C14—H14	120.1
C5—C4—H4	109.4	C15—C14—H14	120.1
C10—C4—H4	109.4	C16—C15—C14	120.2 (6)
C3—C4—H4	109.4	C16—C15—H15	119.9
O5—C5—C6	121.2 (5)	C14—C15—H15	119.9
O5—C5—C4	119.5 (5)	C17—C16—C15	120.7 (7)
C6—C5—C4	119.4 (5)	C17—C16—H16	119.6
C5—C6—C7	118.7 (5)	C15—C16—H16	119.6
C5—C6—H6A	107.7	C16—C17—C18	120.3 (7)
C7—C6—H6A	107.7	C16—C17—H17	119.9
C5—C6—H6B	107.7	C18—C17—H17	119.9
C7—C6—H6B	107.7	C17—C18—C13	120.7 (6)
H6A—C6—H6B	107.1	C17—C18—H18	119.7
C6—C7—C8	115.4 (5)	C13—C18—H18	119.7
C6—C7—H7A	108.4
C10—N1—C2—C3	9.1 (4)	C7—C8—C9—C10	61.4 (7)
C11—N1—C2—C3	−117.9 (4)	C8—C9—C10—N1	−179.8 (5)
N1—C2—C3—C31	−150.5 (2)	C8—C9—C10—C4	−63.3 (6)
N1—C2—C3—C4	−28.9 (4)	C2—N1—C10—C9	139.4 (4)
C2—C3—C31—C36	63.8 (4)	C11—N1—C10—C9	−92.1 (5)
C4—C3—C31—C36	−51.3 (4)	C2—N1—C10—C4	15.1 (4)
C2—C3—C31—C32	−118.9 (2)	C11—N1—C10—C4	143.5 (4)
C4—C3—C31—C32	125.9 (2)	C5—C4—C10—C9	83.8 (5)
C36—C31—C32—C33	0.3 (4)	C3—C4—C10—C9	−154.1 (4)
C3—C31—C32—C33	−177.1 (4)	C5—C4—C10—N1	−155.5 (4)
C31—C32—C33—C34	0.9 (9)	C3—C4—C10—N1	−33.5 (4)
C32—C33—C34—C35	−1.1 (11)	C2—N1—C11—C12	54.3 (5)
C33—C34—C35—C36	0.1 (10)	C10—N1—C11—C12	−71.1 (5)
C32—C31—C36—C35	−1.3 (6)	C2—N1—C11—C13	−75.0 (5)
C3—C31—C36—C35	176.0 (4)	C10—N1—C11—C13	159.5 (4)
C34—C35—C36—C31	1.1 (9)	C12—C11—C13—C14	−15.9 (8)
C31—C3—C4—C5	−78.0 (4)	N1—C11—C13—C14	111.1 (6)
C2—C3—C4—C5	159.5 (4)	C12—C11—C13—C18	162.8 (5)
C31—C3—C4—C10	161.3 (2)	N1—C11—C13—C18	−70.3 (6)
C2—C3—C4—C10	38.8 (4)	C18—C13—C14—C15	−3.3 (10)
C10—C4—C5—O5	109.6 (6)	C11—C13—C14—C15	175.4 (6)
C3—C4—C5—O5	−8.0 (8)	C13—C14—C15—C16	1.4 (11)
C10—C4—C5—C6	−70.3 (6)	C14—C15—C16—C17	1.2 (12)
C3—C4—C5—C6	172.1 (5)	C15—C16—C17—C18	−1.8 (12)
O5—C5—C6—C7	−172.8 (7)	C16—C17—C18—C13	−0.2 (11)
C4—C5—C6—C7	7.1 (9)	C14—C13—C18—C17	2.7 (10)
C5—C6—C7—C8	62.0 (8)	C11—C13—C18—C17	−176.0 (6)
C6—C7—C8—C9	−81.5 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	0.91	2.44	3.266 (4)	151

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br1	0.91	2.44	3.266 (4)	151