tert-Butyl 6-oxo-2,7-diaza­spiro[4.4]nonane-2-carboxyl­ate

Yang, J.

doi:10.1107/S160053681105046X

organic compounds

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Volume 67| Part 12| December 2011| Page o3492

https://doi.org/10.1107/S160053681105046X

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tert-Butyl 6-oxo-2,7-diazaspiro[4.4]nonane-2-carboxylate

Jie Yang ^a ^*

^aMicroscale Science Institute , Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: yangjiewf72@126.com

(Received 26 October 2011; accepted 24 November 2011; online 30 November 2011)

In the title molecule, C₁₂H₂₀N₂O₃, both five-membered rings are in envelope conformations. In the crystal, N—H⋯O hydrogen bonds link the molecules into chains along [010].

Related literature

For applications of substituted pyrrolidines, see: Domagala et al. (1993 ); Pedder et al. (1976 ); Blanco & Sardina (1994 ); Husinec & Savic (2005 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₂H₂₀N₂O₃
M_r = 240.30
Monoclinic, C 2
a = 10.495 (5) Å
b = 6.283 (3) Å
c = 19.247 (10) Å
β = 97.029 (8)°
V = 1259.7 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 173 K
0.21 × 0.15 × 0.06 mm

Data collection

Rigaku Saturn 724+ diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ) T_min = 0.981, T_max = 0.995
3265 measured reflections
1557 independent reflections
1452 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.105
S = 1.09
1557 reflections
157 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.88	1.97	2.848 (3)	175
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+1]$ .

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear; data reduction: CrystalClear; 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: https://doi.org/10.1107/S160053681105046X/lh5363sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681105046X/lh5363Isup2.hkl

checkCIF report

Comment top

Depending on the substitution pattern and functionalization, different substituted pyrrolidines have been shown to be effective antibacterials or fungicides agents and glycosidase inhibitors (Domagala et al., 1993; Pedder et al., 1976; Blanco et al., 1994); Husinec et al., 2005). The crystal structure of the title compound is reportede herein.

In the molecule (Fig. 1), all bond lengths and angles are within normal ranges (Allen et al., 1987). Both five-membered rings are in envelope conformations with C3 and C5 forming the flap. Atoms C6-C8/O2/O3/N2 are essentially planar, with a maximum deviation of 0.0082 (24) Å. In the crystal, N—H···O hydrogen bonds link molecules to form one dimensional chains along [010] (see Table 1).

Related literature top

For applications of substituted pyrrolidines, see: Domagala et al. (1993); Pedder et al. (1976); Blanco & Sardina (1994); Husinec & Savic (2005). For standard bond lengths, see: Allen et al. (1987).

Experimental top

Tert-butyl 6-oxo-2,7-diazasiro[4.4]nonane-2-carboxylate was synthesized with methyl 1-tert-butyl 3-ethyl 3-(cyanomethyl)pyrrolidine-1,3-dicarboxylate (13.4g) and Raney Ni (3.4g) in methanol under H2(50 Psi) atmosphere at room temperature.

Single crystals of the compound suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature. In the absence of anomalous dispersion effects the Friedel pairs were merged.

Structure description top

For applications of substituted pyrrolidines, see: Domagala et al. (1993); Pedder et al. (1976); Blanco & Sardina (1994); Husinec & Savic (2005). For standard bond lengths, see: Allen et al. (1987).

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); 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. The molecular structure of the title compound with displacement ellipsoids are drawn at the 30% probability level.

tert-Butyl 6-oxo-2,7-diazaspiro[4.4]nonane-2-carboxylate top

Crystal data top

C₁₂H₂₀N₂O₃	F(000) = 520
M_r = 240.30	D_x = 1.267 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 2422 reflections
a = 10.495 (5) Å	θ = 1.1–27.5°
b = 6.283 (3) Å	µ = 0.09 mm⁻¹
c = 19.247 (10) Å	T = 173 K
β = 97.029 (8)°	Platelet, colorless
V = 1259.7 (11) Å³	0.21 × 0.15 × 0.06 mm
Z = 4

Data collection top

Rigaku Saturn 724+ diffractometer	1557 independent reflections
Radiation source: rotating anode	1452 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.039
ω scans at fixed χ = 45°	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	h = −13→7
T_min = 0.981, T_max = 0.995	k = −8→8
3265 measured reflections	l = −23→25

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.032P)² + 0.9713P] where P = (F_o² + 2F_c²)/3
1557 reflections	(Δ/σ)_max < 0.001
157 parameters	Δρ_max = 0.23 e Å⁻³
1 restraint	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₂H₂₀N₂O₃	V = 1259.7 (11) Å³
M_r = 240.30	Z = 4
Monoclinic, C2	Mo Kα radiation
a = 10.495 (5) Å	µ = 0.09 mm⁻¹
b = 6.283 (3) Å	T = 173 K
c = 19.247 (10) Å	0.21 × 0.15 × 0.06 mm
β = 97.029 (8)°

Data collection top

Rigaku Saturn 724+ diffractometer	1557 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	1452 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.995	R_int = 0.039
3265 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	1 restraint
wR(F²) = 0.105	H-atom parameters constrained
S = 1.09	Δρ_max = 0.23 e Å⁻³
1557 reflections	Δρ_min = −0.18 e Å⁻³
157 parameters

Special details top

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 > 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.

Absolute configuration is unknown, there being no firm chemical evidence for its assignment to hand and it having not been established by anomalous dispersion effects in diffraction measurements on the crystal. An arbitrary choice of enantiomer has been made.

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

	x	y	z	U_iso*/U_eq
O1	0.2715 (2)	0.4600 (3)	0.43850 (10)	0.0313 (5)
O2	0.33362 (17)	0.2042 (3)	0.18571 (9)	0.0289 (5)
O3	0.55006 (19)	0.1382 (4)	0.19625 (10)	0.0332 (5)
N1	0.3406 (2)	0.8081 (4)	0.44345 (11)	0.0255 (5)
H1	0.3028	0.8474	0.4798	0.031*
N2	0.4618 (2)	0.3546 (4)	0.27139 (12)	0.0275 (5)
C1	0.3315 (3)	0.6117 (5)	0.41741 (13)	0.0219 (6)
C2	0.4181 (3)	0.9527 (5)	0.40704 (14)	0.0279 (6)
H2B	0.5037	0.9751	0.4339	0.033*
H2A	0.3750	1.0920	0.3984	0.033*
C3	0.4286 (3)	0.8347 (5)	0.33812 (13)	0.0234 (6)
H3B	0.5134	0.8596	0.3220	0.028*
H3A	0.3605	0.8813	0.3011	0.028*
C4	0.4118 (3)	0.5993 (5)	0.35651 (13)	0.0209 (5)
C5	0.5419 (3)	0.4915 (5)	0.38093 (13)	0.0241 (6)
H5B	0.6051	0.5963	0.4027	0.029*
H5A	0.5317	0.3766	0.4150	0.029*
C6	0.5835 (3)	0.4018 (5)	0.31360 (15)	0.0303 (7)
H6B	0.6336	0.5078	0.2902	0.036*
H6A	0.6357	0.2714	0.3230	0.036*
C7	0.3515 (2)	0.4573 (5)	0.29695 (13)	0.0233 (6)
H7B	0.2936	0.3505	0.3143	0.028*
H7A	0.3024	0.5428	0.2596	0.028*
C8	0.4568 (2)	0.2247 (5)	0.21527 (13)	0.0244 (6)
C9	0.3028 (3)	0.0912 (5)	0.11865 (14)	0.0290 (7)
C10	0.3776 (3)	0.1875 (7)	0.06389 (15)	0.0461 (9)
H10A	0.3444	0.1321	0.0176	0.069*
H10C	0.4686	0.1501	0.0745	0.069*
H10B	0.3683	0.3427	0.0641	0.069*
C11	0.3283 (3)	−0.1464 (6)	0.12960 (17)	0.0381 (8)
H11B	0.2717	−0.2031	0.1620	0.057*
H11C	0.4180	−0.1680	0.1492	0.057*
H11A	0.3117	−0.2205	0.0846	0.057*
C12	0.1607 (3)	0.1350 (7)	0.10196 (17)	0.0419 (8)
H12A	0.1281	0.0648	0.0579	0.063*
H12C	0.1466	0.2888	0.0974	0.063*
H12B	0.1154	0.0799	0.1398	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0348 (12)	0.0317 (11)	0.0293 (10)	−0.0073 (10)	0.0115 (8)	0.0027 (10)
O2	0.0228 (10)	0.0378 (11)	0.0253 (9)	0.0021 (10)	0.0002 (7)	−0.0106 (10)
O3	0.0261 (11)	0.0410 (13)	0.0335 (10)	0.0050 (10)	0.0074 (8)	−0.0098 (10)
N1	0.0263 (12)	0.0276 (13)	0.0234 (11)	0.0030 (11)	0.0066 (9)	−0.0023 (11)
N2	0.0190 (11)	0.0345 (13)	0.0284 (11)	0.0033 (11)	0.0004 (9)	−0.0091 (11)
C1	0.0200 (13)	0.0256 (13)	0.0200 (11)	−0.0001 (12)	0.0015 (10)	0.0016 (11)
C2	0.0280 (15)	0.0235 (13)	0.0322 (14)	0.0000 (13)	0.0033 (11)	0.0014 (13)
C3	0.0197 (13)	0.0265 (14)	0.0247 (12)	0.0022 (12)	0.0059 (10)	0.0037 (12)
C4	0.0193 (12)	0.0224 (13)	0.0211 (11)	0.0013 (12)	0.0025 (10)	0.0009 (11)
C5	0.0206 (13)	0.0249 (14)	0.0262 (13)	−0.0010 (12)	0.0001 (10)	−0.0014 (12)
C6	0.0183 (13)	0.0383 (18)	0.0336 (14)	0.0040 (13)	0.0001 (11)	−0.0076 (13)
C7	0.0181 (13)	0.0271 (13)	0.0252 (12)	0.0021 (12)	0.0053 (10)	−0.0021 (12)
C8	0.0219 (13)	0.0270 (14)	0.0248 (13)	0.0016 (12)	0.0048 (10)	−0.0003 (12)
C9	0.0309 (15)	0.0351 (16)	0.0212 (13)	−0.0022 (14)	0.0033 (11)	−0.0045 (13)
C10	0.048 (2)	0.062 (3)	0.0283 (15)	−0.009 (2)	0.0058 (14)	0.0031 (17)
C11	0.0388 (18)	0.0359 (17)	0.0394 (17)	−0.0022 (16)	0.0030 (14)	−0.0081 (15)
C12	0.0337 (18)	0.050 (2)	0.0395 (17)	0.0044 (17)	−0.0073 (14)	−0.0070 (17)

Geometric parameters (Å, º) top

O1—C1	1.238 (3)	C5—C6	1.525 (4)
O2—C8	1.353 (3)	C5—H5B	0.9900
O2—C9	1.474 (3)	C5—H5A	0.9900
O3—C8	1.214 (3)	C6—H6B	0.9900
N1—C1	1.331 (4)	C6—H6A	0.9900
N1—C2	1.454 (4)	C7—H7B	0.9900
N1—H1	0.8800	C7—H7A	0.9900
N2—C8	1.350 (3)	C9—C12	1.511 (4)
N2—C6	1.458 (4)	C9—C10	1.516 (4)
N2—C7	1.462 (3)	C9—C11	1.526 (5)
C1—C4	1.527 (4)	C10—H10A	0.9800
C2—C3	1.535 (4)	C10—H10C	0.9800
C2—H2B	0.9900	C10—H10B	0.9800
C2—H2A	0.9900	C11—H11B	0.9800
C3—C4	1.536 (4)	C11—H11C	0.9800
C3—H3B	0.9900	C11—H11A	0.9800
C3—H3A	0.9900	C12—H12A	0.9800
C4—C7	1.527 (4)	C12—H12C	0.9800
C4—C5	1.545 (4)	C12—H12B	0.9800

C8—O2—C9	120.7 (2)	N2—C6—H6A	111.1
C1—N1—C2	114.6 (2)	C5—C6—H6A	111.1
C1—N1—H1	122.7	H6B—C6—H6A	109.1
C2—N1—H1	122.7	N2—C7—C4	103.8 (2)
C8—N2—C6	121.0 (2)	N2—C7—H7B	111.0
C8—N2—C7	125.5 (2)	C4—C7—H7B	111.0
C6—N2—C7	113.5 (2)	N2—C7—H7A	111.0
O1—C1—N1	127.3 (3)	C4—C7—H7A	111.0
O1—C1—C4	124.3 (3)	H7B—C7—H7A	109.0
N1—C1—C4	108.4 (2)	O3—C8—N2	123.9 (3)
N1—C2—C3	102.6 (2)	O3—C8—O2	126.5 (3)
N1—C2—H2B	111.2	N2—C8—O2	109.6 (2)
C3—C2—H2B	111.2	O2—C9—C12	101.8 (2)
N1—C2—H2A	111.2	O2—C9—C10	109.8 (3)
C3—C2—H2A	111.2	C12—C9—C10	111.2 (3)
H2B—C2—H2A	109.2	O2—C9—C11	109.5 (2)
C2—C3—C4	104.1 (2)	C12—C9—C11	111.1 (3)
C2—C3—H3B	110.9	C10—C9—C11	112.9 (3)
C4—C3—H3B	110.9	C9—C10—H10A	109.5
C2—C3—H3A	110.9	C9—C10—H10C	109.5
C4—C3—H3A	110.9	H10A—C10—H10C	109.5
H3B—C3—H3A	109.0	C9—C10—H10B	109.5
C1—C4—C7	112.9 (2)	H10A—C10—H10B	109.5
C1—C4—C3	102.6 (2)	H10C—C10—H10B	109.5
C7—C4—C3	116.0 (2)	C9—C11—H11B	109.5
C1—C4—C5	109.8 (2)	C9—C11—H11C	109.5
C7—C4—C5	104.0 (2)	H11B—C11—H11C	109.5
C3—C4—C5	111.7 (2)	C9—C11—H11A	109.5
C6—C5—C4	103.8 (2)	H11B—C11—H11A	109.5
C6—C5—H5B	111.0	H11C—C11—H11A	109.5
C4—C5—H5B	111.0	C9—C12—H12A	109.5
C6—C5—H5A	111.0	C9—C12—H12C	109.5
C4—C5—H5A	111.0	H12A—C12—H12C	109.5
H5B—C5—H5A	109.0	C9—C12—H12B	109.5
N2—C6—C5	103.1 (2)	H12A—C12—H12B	109.5
N2—C6—H6B	111.1	H12C—C12—H12B	109.5
C5—C6—H6B	111.1

C2—N1—C1—O1	−179.7 (3)	C7—N2—C6—C5	15.7 (3)
C2—N1—C1—C4	1.7 (3)	C4—C5—C6—N2	−30.5 (3)
C1—N1—C2—C3	15.7 (3)	C8—N2—C7—C4	−175.1 (3)
N1—C2—C3—C4	−25.8 (3)	C6—N2—C7—C4	5.9 (3)
O1—C1—C4—C7	37.5 (4)	C1—C4—C7—N2	−143.8 (2)
N1—C1—C4—C7	−143.8 (2)	C3—C4—C7—N2	98.2 (3)
O1—C1—C4—C3	163.1 (3)	C5—C4—C7—N2	−24.9 (3)
N1—C1—C4—C3	−18.2 (3)	C6—N2—C8—O3	0.5 (4)
O1—C1—C4—C5	−78.0 (3)	C7—N2—C8—O3	−178.4 (3)
N1—C1—C4—C5	100.7 (3)	C6—N2—C8—O2	179.2 (3)
C2—C3—C4—C1	26.7 (3)	C7—N2—C8—O2	0.3 (4)
C2—C3—C4—C7	150.2 (2)	C9—O2—C8—O3	−8.6 (4)
C2—C3—C4—C5	−90.8 (2)	C9—O2—C8—N2	172.7 (2)
C1—C4—C5—C6	155.7 (2)	C8—O2—C9—C12	−172.4 (3)
C7—C4—C5—C6	34.6 (3)	C8—O2—C9—C10	−54.6 (4)
C3—C4—C5—C6	−91.2 (3)	C8—O2—C9—C11	69.9 (3)
C8—N2—C6—C5	−163.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.88	1.97	2.848 (3)	175

Symmetry code: (i) −x+1/2, y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₂₀N₂O₃
M_r	240.30
Crystal system, space group	Monoclinic, C2
Temperature (K)	173
a, b, c (Å)	10.495 (5), 6.283 (3), 19.247 (10)
β (°)	97.029 (8)
V (Å³)	1259.7 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.21 × 0.15 × 0.06

Data collection
Diffractometer	Rigaku Saturn 724+
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2007)
T_min, T_max	0.981, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	3265, 1557, 1452
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.105, 1.09
No. of reflections	1557
No. of parameters	157
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.18

Computer programs: CrystalClear (Rigaku, 2007), 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—H1···O1ⁱ	0.88	1.97	2.848 (3)	174.5

Symmetry code: (i) −x+1/2, y+1/2, −z+1.

Acknowledgements

The author would like to thank the Shandong Provincial Natural Science Foundation, China (Y2008B29) and the Weifang Technology Development Project (2010).

References

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