organic compounds
tert-Butyl 6-oxo-2,7-diazaspiro[4.4]nonane-2-carboxylate
aMicroscale Science Institute , Weifang University, Weifang 261061, People's Republic of China
*Correspondence e-mail: yangjiewf72@126.com
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
|
Refinement
|
Data collection: CrystalClear (Rigaku, 2007); cell 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
https://doi.org/10.1107/S160053681105046X/lh5363sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681105046X/lh5363Isup2.hkl
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
effects the Friedel pairs were merged.All H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H distances in the range 0.98–0.99 Å, and with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(Cmethyl). The N—H distance is 0.88 Å, with Uiso(H) = 1.2Ueq(N).
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
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).
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).
Data collection: CrystalClear (Rigaku, 2007); cell
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).Fig. 1. The molecular structure of the title compound with displacement ellipsoids are drawn at the 30% probability level. |
C12H20N2O3 | F(000) = 520 |
Mr = 240.30 | Dx = 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 |
Rigaku Saturn 724+ diffractometer | 1557 independent reflections |
Radiation source: rotating anode | 1452 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.039 |
ω scans at fixed χ = 45° | θmax = 27.5°, θmin = 2.1° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007) | h = −13→7 |
Tmin = 0.981, Tmax = 0.995 | k = −8→8 |
3265 measured reflections | l = −23→25 |
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(Fo2) + (0.032P)2 + 0.9713P] where P = (Fo2 + 2Fc2)/3 |
1557 reflections | (Δ/σ)max < 0.001 |
157 parameters | Δρmax = 0.23 e Å−3 |
1 restraint | Δρmin = −0.18 e Å−3 |
C12H20N2O3 | V = 1259.7 (11) Å3 |
Mr = 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)° |
Rigaku Saturn 724+ diffractometer | 1557 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007) | 1452 reflections with I > 2σ(I) |
Tmin = 0.981, Tmax = 0.995 | Rint = 0.039 |
3265 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 1 restraint |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.23 e Å−3 |
1557 reflections | Δρmin = −0.18 e Å−3 |
157 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.981, 0.995 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3265, 1557, 1452 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.23, −0.18 |
Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
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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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).