Crystal structure of (±)-(5SR,6SR)-6-ethenyl-1-[(RS)-1-phenyl­eth­oxy]-1-aza­spiro­[4.5]decan-2-one

Oishi, T.; Yamamoto, S.; Yokoyama, T.; Kobayashi, A.; Sato, T.; Chida, N.

doi:10.1107/S2056989015021209

Crystal structure of (±)-(5SR,6SR)-6-ethenyl-1-[(RS)-1-phenylethoxy]-1-azaspiro[4.5]decan-2-one

T. Oishi, S. Yamamoto, T. Yokoyama, A. Kobayashi, T. Sato and N. Chida

In the title compound, the pyrrolidine and cyclohexane rings exhibit envelope and chair conformations, respectively. In the crystal, C—H

O interactions connect the molecules into tape structures.

Keywords: crystal structure; pyrrolidine; cyclohexane; N-alkoxy-N-alkylamide; hydrogen bonding.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015021209/is5431sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989015021209/is5431Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989015021209/is5431Isup3.cml Supplementary material

CCDC reference: 1435676

checkCIF report

Key indicators

Single-crystal X-ray study
T = 90 K
Mean (C-C) = 0.002 Å
R factor = 0.034
wR factor = 0.083
Data-to-parameter ratio = 14.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H20    ..  O13     ..       2.61 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595         19 Report

Alert level G
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00200 Degree
PLAT793_ALERT_4_G The Model has Chirality at C5      (Centro SPGR)          S Verify
PLAT793_ALERT_4_G The Model has Chirality at C10     (Centro SPGR)          S Verify
PLAT793_ALERT_4_G The Model has Chirality at C15     (Centro SPGR)          R Verify
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          66 %
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          1 Report

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010) and PLATON (Spek, 2009).

(±)-(5SR,6SR)-6-Ethenyl-1-[(RS)-1-phenylethoxy]-1-azaspiro[4.5]decan-2-one top

Crystal data top

C₁₉H₂₅NO₂	F(000) = 324
M_r = 299.41	D_x = 1.222 Mg m⁻³
Triclinic, P1	Melting point: 357.8 K
a = 8.9032 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.6307 (5) Å	Cell parameters from 5086 reflections
c = 11.3401 (6) Å	θ = 2.7–25.1°
α = 93.306 (2)°	µ = 0.08 mm⁻¹
β = 108.710 (2)°	T = 90 K
γ = 114.929 (2)°	Plate, colorless
V = 813.83 (8) Å³	0.29 × 0.24 × 0.20 mm
Z = 2

Data collection top

Bruker D8 Venture diffractometer	2861 independent reflections
Radiation source: fine-focus sealed tube	2304 reflections with I > 2σ(I)
Multilayered confocal mirror monochromator	R_int = 0.028
Detector resolution: 10.4167 pixels mm^-1	θ_max = 25.0°, θ_min = 2.4°
φ and ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −11→11
T_min = 0.98, T_max = 0.98	l = −13→13
14217 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0345P)² + 0.2546P] where P = (F_o² + 2F_c²)/3
2861 reflections	(Δ/σ)_max = 0.003
200 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Special details top

Experimental. IR (film): 2933, 2859, 1708, 1451, 1047, 916, 700 cm^-1; ¹H NMR (500 MHz, CDCl₃): δ (p.p.m.) 7.41–7.38 (m, 2H; H18 & H22), 7.37–7.28 (m, 3H; H19–21), 5.66 (ddd, J = 17.5, 10.6, 6.9 Hz, 1H; H11), 5.27 (q, J = 6.6 Hz, 1H; H15), 5.15 (ddd, J = 17.5, 1.7, 1.4 Hz, 1H; H12A), 5.09 (ddd, J = 10.6, 1.7, 1.2 Hz, 1H; H12B), 2.46 (ddddd, J = 11.5, 6.9, 4.0, 1.4, 1.2 Hz, 1H; H10), 2.24 (ddd, J = 17.5, 10.9, 3.7 Hz, 1H; H3B), 2.17 (ddd, J = 17.5, 10.3, 7.8 Hz, 1H; H3A), 1.98 (ddd, J = 14.0, 10.3, 3.7 Hz, 1H; H4A), 1.72–1.68 (m, 1H; H9B), 1.66 (d, J = 6.6 Hz, 3H; H16ABC), 1.63–1.57 (m, 1H; H7B), 1.49–1.41 (m, 2H; H4B & H8B), 1.31–1.20 (m, 2H; H6A & H9A), 1.17–1.01 (m, 2H; H7A & H8A), 0.90–0.82 (m, 1H; H6B). ¹³C NMR (125 MHz, CDCl₃): δ (p.p.m.) 172.8 (C; C2), 141.5 (C; C17), 137.6 (CH; C11), 128.4 (CH; C20), 128.3 (CH; C19 & C21), 127.7 (CH; C18 & C22), 117.8 (CH₂; C12), 83.2 (CH; C15), 66.7 (C; C5), 44.6 (CH; C10), 37.6 (CH₂; C6), 27.7 (CH₂; C9), 27.3 (CH₂; C3), 25.0 (CH₂; C7), 22.8 (CH₂; C8), 22.6 (CH₂; C4), 21.2 (CH₃; C16).

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

Problematic one reflection with |I(obs)-I(calc)|/σW(I) greater than 10 (5 4 0) has been omitted in the final refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.38594 (14)	0.18774 (12)	0.71854 (10)	0.0150 (3)
C2	0.27948 (18)	0.23274 (15)	0.63314 (13)	0.0181 (3)
C3	0.35545 (19)	0.27324 (18)	0.53172 (13)	0.0239 (3)
H3A	0.3831	0.3823	0.5236	0.029*
H3B	0.2694	0.2009	0.448	0.029*
C4	0.52667 (18)	0.25541 (17)	0.57599 (12)	0.0204 (3)
H4A	0.6283	0.3505	0.5734	0.024*
H4B	0.5107	0.1636	0.5197	0.024*
C5	0.56353 (17)	0.23207 (15)	0.71449 (12)	0.0161 (3)
C6	0.61336 (18)	0.09955 (16)	0.73662 (13)	0.0187 (3)
H6A	0.6112	0.0754	0.8199	0.022*
H6B	0.5232	0.0039	0.6691	0.022*
C7	0.79862 (18)	0.14278 (17)	0.73554 (14)	0.0224 (3)
H7A	0.7978	0.157	0.6496	0.027*
H7B	0.8281	0.056	0.7539	0.027*
C8	0.94114 (18)	0.29350 (17)	0.83460 (14)	0.0239 (3)
H8A	0.9525	0.2752	0.9213	0.029*
H8B	1.0582	0.3232	0.8274	0.029*
C9	0.89331 (18)	0.42710 (16)	0.81564 (13)	0.0207 (3)
H9A	0.8956	0.4533	0.7329	0.025*
H9B	0.9842	0.5214	0.8842	0.025*
C10	0.70790 (17)	0.38388 (15)	0.81750 (13)	0.0169 (3)
H10	0.7115	0.358	0.9022	0.02*
C11	0.65709 (18)	0.51421 (16)	0.80790 (12)	0.0197 (3)
H11	0.5532	0.4978	0.824	0.024*
C12	0.7417 (2)	0.64903 (16)	0.77944 (13)	0.0250 (3)
H12A	0.8464	0.6713	0.7625	0.03*
H12B	0.6981	0.7239	0.7759	0.03*
O13	0.14599 (13)	0.23609 (11)	0.63826 (9)	0.0236 (2)
O14	0.36946 (11)	0.17339 (10)	0.83675 (8)	0.0157 (2)
C15	0.20748 (17)	0.02915 (15)	0.82165 (12)	0.0162 (3)
H15	0.1019	0.0301	0.7556	0.019*
C16	0.19176 (19)	0.04574 (16)	0.94965 (13)	0.0205 (3)
H16A	0.3004	0.0563	1.0167	0.031*
H16B	0.0876	−0.0475	0.949	0.031*
H16C	0.1771	0.1393	0.9664	0.031*
C17	0.22033 (17)	−0.11480 (15)	0.77798 (12)	0.0161 (3)
C18	0.14415 (17)	−0.18306 (16)	0.64821 (13)	0.0193 (3)
H18	0.0813	−0.1409	0.5897	0.023*
C19	0.15846 (19)	−0.31154 (16)	0.60300 (14)	0.0236 (3)
H19	0.1063	−0.3567	0.514	0.028*
C20	0.24866 (19)	−0.37425 (16)	0.68731 (14)	0.0257 (3)
H20	0.2588	−0.4624	0.6564	0.031*
C21	0.32436 (19)	−0.30816 (16)	0.81723 (14)	0.0228 (3)
H21	0.3859	−0.3515	0.8755	0.027*
C22	0.31044 (17)	−0.17913 (15)	0.86219 (13)	0.0178 (3)
H22	0.3628	−0.1342	0.9513	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0159 (6)	0.0195 (6)	0.0124 (6)	0.0089 (5)	0.0073 (4)	0.0061 (5)
C2	0.0188 (7)	0.0155 (7)	0.0185 (7)	0.0079 (6)	0.0056 (6)	0.0034 (6)
C3	0.0249 (8)	0.0299 (8)	0.0180 (7)	0.0131 (7)	0.0086 (6)	0.0095 (6)
C4	0.0212 (7)	0.0236 (8)	0.0171 (7)	0.0096 (6)	0.0093 (6)	0.0045 (6)
C5	0.0139 (7)	0.0186 (7)	0.0176 (7)	0.0070 (6)	0.0087 (6)	0.0044 (6)
C6	0.0176 (7)	0.0172 (7)	0.0221 (7)	0.0081 (6)	0.0089 (6)	0.0033 (6)
C7	0.0213 (8)	0.0246 (8)	0.0281 (8)	0.0137 (7)	0.0133 (6)	0.0073 (6)
C8	0.0169 (7)	0.0295 (8)	0.0286 (8)	0.0117 (7)	0.0111 (6)	0.0086 (7)
C9	0.0169 (7)	0.0222 (8)	0.0204 (7)	0.0065 (6)	0.0075 (6)	0.0043 (6)
C10	0.0176 (7)	0.0178 (7)	0.0160 (7)	0.0077 (6)	0.0078 (6)	0.0050 (6)
C11	0.0187 (7)	0.0203 (8)	0.0187 (7)	0.0082 (6)	0.0071 (6)	0.0019 (6)
C12	0.0284 (8)	0.0212 (8)	0.0251 (8)	0.0113 (7)	0.0103 (6)	0.0050 (6)
O13	0.0204 (5)	0.0311 (6)	0.0255 (5)	0.0165 (5)	0.0092 (4)	0.0106 (5)
O14	0.0160 (5)	0.0175 (5)	0.0138 (5)	0.0060 (4)	0.0080 (4)	0.0046 (4)
C15	0.0112 (7)	0.0171 (7)	0.0199 (7)	0.0053 (6)	0.0070 (5)	0.0055 (6)
C16	0.0215 (7)	0.0217 (7)	0.0244 (8)	0.0116 (6)	0.0136 (6)	0.0074 (6)
C17	0.0107 (6)	0.0164 (7)	0.0199 (7)	0.0034 (6)	0.0082 (6)	0.0058 (6)
C18	0.0133 (7)	0.0198 (7)	0.0199 (7)	0.0034 (6)	0.0062 (6)	0.0050 (6)
C19	0.0217 (8)	0.0185 (7)	0.0229 (8)	0.0018 (6)	0.0105 (6)	−0.0006 (6)
C20	0.0262 (8)	0.0161 (7)	0.0362 (9)	0.0073 (7)	0.0177 (7)	0.0024 (7)
C21	0.0203 (7)	0.0195 (8)	0.0322 (9)	0.0100 (6)	0.0125 (6)	0.0098 (6)
C22	0.0145 (7)	0.0180 (7)	0.0192 (7)	0.0051 (6)	0.0076 (6)	0.0050 (6)

Geometric parameters (Å, º) top

N1—C2	1.3528 (17)	C10—C11	1.5015 (18)
N1—O14	1.4028 (13)	C10—H10	1.0
N1—C5	1.4712 (16)	C11—C12	1.3182 (19)
C2—O13	1.2220 (16)	C11—H11	0.95
C2—C3	1.5035 (19)	C12—H12A	0.95
C3—C4	1.5313 (19)	C12—H12B	0.95
C3—H3A	0.99	O14—C15	1.4711 (15)
C3—H3B	0.99	C15—C17	1.5070 (18)
C4—C5	1.5483 (18)	C15—C16	1.5082 (18)
C4—H4A	0.99	C15—H15	1.0
C4—H4B	0.99	C16—H16A	0.98
C5—C6	1.5269 (18)	C16—H16B	0.98
C5—C10	1.5524 (18)	C16—H16C	0.98
C6—C7	1.5260 (18)	C17—C18	1.3893 (19)
C6—H6A	0.99	C17—C22	1.3911 (18)
C6—H6B	0.99	C18—C19	1.383 (2)
C7—C8	1.524 (2)	C18—H18	0.95
C7—H7A	0.99	C19—C20	1.381 (2)
C7—H7B	0.99	C19—H19	0.95
C8—C9	1.5225 (19)	C20—C21	1.387 (2)
C8—H8A	0.99	C20—H20	0.95
C8—H8B	0.99	C21—C22	1.3845 (19)
C9—C10	1.5305 (18)	C21—H21	0.95
C9—H9A	0.99	C22—H22	0.95
C9—H9B	0.99

C2—N1—O14	119.24 (10)	C10—C9—H9B	109.3
C2—N1—C5	116.41 (10)	H9A—C9—H9B	107.9
O14—N1—C5	117.39 (9)	C11—C10—C9	114.62 (11)
O13—C2—N1	125.63 (12)	C11—C10—C5	111.76 (11)
O13—C2—C3	127.65 (12)	C9—C10—C5	110.36 (10)
N1—C2—C3	106.72 (11)	C11—C10—H10	106.5
C2—C3—C4	105.52 (11)	C9—C10—H10	106.5
C2—C3—H3A	110.6	C5—C10—H10	106.5
C4—C3—H3A	110.6	C12—C11—C10	126.73 (13)
C2—C3—H3B	110.6	C12—C11—H11	116.6
C4—C3—H3B	110.6	C10—C11—H11	116.6
H3A—C3—H3B	108.8	C11—C12—H12A	120.0
C3—C4—C5	107.09 (10)	C11—C12—H12B	120.0
C3—C4—H4A	110.3	H12A—C12—H12B	120.0
C5—C4—H4A	110.3	N1—O14—C15	110.49 (9)
C3—C4—H4B	110.3	O14—C15—C17	110.98 (10)
C5—C4—H4B	110.3	O14—C15—C16	103.77 (10)
H4A—C4—H4B	108.6	C17—C15—C16	116.12 (11)
N1—C5—C6	110.47 (10)	O14—C15—H15	108.6
N1—C5—C4	99.85 (10)	C17—C15—H15	108.6
C6—C5—C4	112.75 (11)	C16—C15—H15	108.6
N1—C5—C10	110.47 (10)	C15—C16—H16A	109.5
C6—C5—C10	109.45 (10)	C15—C16—H16B	109.5
C4—C5—C10	113.53 (11)	H16A—C16—H16B	109.5
C7—C6—C5	111.89 (11)	C15—C16—H16C	109.5
C7—C6—H6A	109.2	H16A—C16—H16C	109.5
C5—C6—H6A	109.2	H16B—C16—H16C	109.5
C7—C6—H6B	109.2	C18—C17—C22	118.66 (12)
C5—C6—H6B	109.2	C18—C17—C15	118.77 (12)
H6A—C6—H6B	107.9	C22—C17—C15	122.54 (12)
C8—C7—C6	111.07 (11)	C19—C18—C17	120.93 (13)
C8—C7—H7A	109.4	C19—C18—H18	119.5
C6—C7—H7A	109.4	C17—C18—H18	119.5
C8—C7—H7B	109.4	C20—C19—C18	119.98 (13)
C6—C7—H7B	109.4	C20—C19—H19	120.0
H7A—C7—H7B	108.0	C18—C19—H19	120.0
C9—C8—C7	111.06 (11)	C19—C20—C21	119.80 (13)
C9—C8—H8A	109.4	C19—C20—H20	120.1
C7—C8—H8A	109.4	C21—C20—H20	120.1
C9—C8—H8B	109.4	C22—C21—C20	120.10 (13)
C7—C8—H8B	109.4	C22—C21—H21	119.9
H8A—C8—H8B	108.0	C20—C21—H21	119.9
C8—C9—C10	111.81 (11)	C21—C22—C17	120.53 (13)
C8—C9—H9A	109.3	C21—C22—H22	119.7
C10—C9—H9A	109.3	C17—C22—H22	119.7
C8—C9—H9B	109.3

O14—N1—C2—O13	−14.0 (2)	N1—C5—C10—C11	−52.82 (13)
C5—N1—C2—O13	−164.04 (13)	C6—C5—C10—C11	−174.67 (10)
O14—N1—C2—C3	167.24 (10)	C4—C5—C10—C11	58.38 (14)
C5—N1—C2—C3	17.17 (15)	N1—C5—C10—C9	178.38 (10)
O13—C2—C3—C4	177.61 (13)	C6—C5—C10—C9	56.53 (13)
N1—C2—C3—C4	−3.62 (15)	C4—C5—C10—C9	−70.42 (13)
C2—C3—C4—C5	−9.48 (15)	C9—C10—C11—C12	10.9 (2)
C2—N1—C5—C6	−141.15 (11)	C5—C10—C11—C12	−115.63 (15)
O14—N1—C5—C6	68.22 (13)	C2—N1—O14—C15	75.55 (13)
C2—N1—C5—C4	−22.22 (14)	C5—N1—O14—C15	−134.67 (10)
O14—N1—C5—C4	−172.85 (10)	N1—O14—C15—C17	64.29 (12)
C2—N1—C5—C10	97.60 (13)	N1—O14—C15—C16	−170.29 (9)
O14—N1—C5—C10	−53.03 (13)	O14—C15—C17—C18	−95.21 (13)
C3—C4—C5—N1	17.59 (13)	C16—C15—C17—C18	146.62 (12)
C3—C4—C5—C6	134.83 (12)	O14—C15—C17—C22	82.70 (14)
C3—C4—C5—C10	−99.97 (13)	C16—C15—C17—C22	−35.46 (17)
N1—C5—C6—C7	−178.92 (11)	C22—C17—C18—C19	−0.54 (19)
C4—C5—C6—C7	70.32 (14)	C15—C17—C18—C19	177.46 (12)
C10—C5—C6—C7	−57.07 (14)	C17—C18—C19—C20	0.3 (2)
C5—C6—C7—C8	56.61 (15)	C18—C19—C20—C21	0.1 (2)
C6—C7—C8—C9	−54.81 (15)	C19—C20—C21—C22	−0.4 (2)
C7—C8—C9—C10	55.59 (15)	C20—C21—C22—C17	0.2 (2)
C8—C9—C10—C11	176.19 (11)	C18—C17—C22—C21	0.28 (19)
C8—C9—C10—C5	−56.57 (14)	C15—C17—C22—C21	−177.64 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···O13	1.00	2.42	3.0437 (16)	120
C18—H18···O13ⁱ	0.95	2.53	3.2864 (17)	136
C20—H20···O13ⁱⁱ	0.95	2.61	3.4307 (17)	145

Symmetry codes: (i) −x, −y, −z+1; (ii) x, y−1, z.

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Crystal structure of (±)-(5SR,6SR)-6-ethenyl-1-[(RS)-1-phenyl­eth­oxy]-1-aza­spiro­[4.5]decan-2-one

Supporting information

Key indicators

checkCIF/PLATON results

Crystal structure of (±)-(5SR,6SR)-6-ethenyl-1-[(RS)-1-phenylethoxy]-1-azaspiro[4.5]decan-2-one