Crystal structure of (1R,4R)-tert-butyl 3-oxo-2-oxa-5-aza-bicyclo-[2.2.2]octane-5-carboxyl-ate.

In the title compound, C11H17NO4, commonly known as N-tert-but-oxy-carbonyl-5-hy-droxy-d-pipecolic acid lactone, the absolute configuration is (1R,4R) due to the enantiomeric purity of the starting material which remains unchanged during the course of the reaction. In the crystal there no inter-molecular hydrogen bonds.

Related literature

For background information on 5-hy­droxy­pipecolic acid and related compounds, see: Witkop & Foltz (1957 ▸); Hoarau et al. (1996 ▸); Sun et al. (2008 ▸). For the synthesis of a related compound, see: Krishnamurthy et al. (2014 ▸). For crystal structures of related lactones, see: (1S,4S) conformer, racemic mixture, Moriguchi, Krishnamurthy, Arai & Tsuge (2014 ▸); Moriguchi, Krishnamurthy, Arai, Matsumoto et al. (2014 ▸).

Experimental

Crystal data

C11H17NO4

M = 227.26

Orthorhombic,

a = 9.6472 (4) Å

b = 9.7084 (4) Å

c = 12.2323 (5) Å

V = 1145.66 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 90 K

0.45 × 0.40 × 0.40 mm

Data collection

Bruker APEX2 KY CCD diffractometer

Absorption correction: multi-scan SADABS (Bruker, 2009 ▸) T min = 0.870, T max = 0.961

13518 measured reflections

2791 independent reflections

2728 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.081

S = 1.03

2791 reflections

148 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.27 e Å−3

Absolute structure: Flack (1983 ▸), 2933 Friedel pairs

Absolute structure parameter: 0.1 (7)

Data collection: APEX2 (Bruker,2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; 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: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015010476/zs2333sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010476/zs2333Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015010476/zs2333Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015010476/zs2333fig1.tif

Mol­ecular configuration and atom numbering scheme for the title compound with displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are omitted for clarity.

Click here for additional data file.

. DOI: 10.1107/S2056989015010476/zs2333fig2.tif

Crystal packing diagram of the title compound.

Click here for additional data file.

. DOI: 10.1107/S2056989015010476/zs2333fig3.tif

Synthetic scheme for the title compound (I).

CCDC reference: 1062075

Additional supporting information: crystallographic information; 3D view; checkCIF report

C11H17NO4	Dx = 1.318 Mg m−3
Mr = 227.26	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 9630 reflections
a = 9.6472 (4) Å	θ = 2.7–28.7°
b = 9.7084 (4) Å	µ = 0.10 mm−1
c = 12.2323 (5) Å	T = 90 K
V = 1145.66 (8) Å3	Prism, colorless
Z = 4	0.45 × 0.40 × 0.40 mm
F(000) = 488

Bruker APEX2 KY CCD diffractometer	2791 independent reflections
Radiation source: fine-focus sealed tube	2728 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 16.6666 pixels mm-1	θmax = 28.7°, θmin = 2.7°
φ and ω–scans	h = −12→12
Absorption correction: multi-scan SADABS (Bruker, 2009)	k = −12→12
Tmin = 0.870, Tmax = 0.961	l = −16→16
13518 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.030	w = 1/[σ2(Fo2) + (0.0583P)2 + 0.1302P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.081	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.24 e Å−3
2791 reflections	Δρmin = −0.27 e Å−3
148 parameters	Extinction correction: SHELXL97
0 restraints	Extinction coefficient: 0.0015
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 2933 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.1 (7)

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.

	x	y	z	Uiso*/Ueq
C1	0.65404 (10)	0.31574 (9)	0.06026 (7)	0.01427 (18)
H1	0.71	0.2937	−0.0063	0.017*
C2	0.49996 (10)	0.33409 (10)	0.03171 (8)	0.0176 (2)
H2A	0.4628	0.2485	−0.0011	0.021*
H2B	0.4883	0.41	−0.0215	0.021*
C3	0.42204 (10)	0.36786 (11)	0.13907 (9)	0.0206 (2)
H3B	0.378	0.4597	0.1335	0.025*
H3A	0.3485	0.2987	0.1521	0.025*
C4	0.52501 (11)	0.36654 (10)	0.23335 (8)	0.01785 (19)
H4	0.475	0.3836	0.3037	0.021*
C5	0.63878 (10)	0.47291 (11)	0.21909 (8)	0.0178 (2)
H5B	0.5993	0.567	0.2175	0.021*
H5A	0.7064	0.4671	0.2798	0.021*
C6	0.66134 (10)	0.19956 (10)	0.14366 (8)	0.01762 (19)
C7	0.81399 (10)	0.51222 (9)	0.07261 (8)	0.01444 (19)
C8	0.96933 (10)	0.70326 (10)	0.12123 (8)	0.01618 (19)
C9	1.10001 (11)	0.61760 (12)	0.11084 (11)	0.0276 (2)
H9A	1.0964	0.5638	0.0431	0.041*
H9B	1.1072	0.5551	0.1735	0.041*
H9C	1.181	0.6785	0.1092	0.041*
C10	0.94288 (14)	0.79172 (11)	0.02135 (10)	0.0272 (3)
H10A	0.8622	0.8507	0.0345	0.041*
H10B	0.925	0.7324	−0.0419	0.041*
H10C	1.0243	0.8492	0.0069	0.041*
C11	0.97332 (14)	0.79157 (13)	0.22359 (10)	0.0311 (3)
H11A	0.9866	0.7325	0.2877	0.047*
H11B	0.8858	0.842	0.2307	0.047*
H11C	1.0502	0.8572	0.2184	0.047*
N1	0.70560 (9)	0.44009 (8)	0.11448 (7)	0.01612 (17)
O1	0.71703 (8)	0.08995 (8)	0.13238 (7)	0.02526 (18)
O2	0.59161 (8)	0.23044 (8)	0.23684 (6)	0.01975 (16)
O3	0.86922 (8)	0.48744 (7)	−0.01469 (6)	0.01893 (16)
O4	0.84801 (7)	0.61426 (7)	0.14236 (6)	0.01846 (16)

	U11	U22	U33	U12	U13	U23
C1	0.0141 (4)	0.0119 (4)	0.0168 (4)	−0.0019 (3)	0.0008 (3)	−0.0028 (3)
C2	0.0155 (5)	0.0172 (4)	0.0201 (4)	−0.0010 (4)	−0.0030 (3)	−0.0007 (3)
C3	0.0129 (4)	0.0230 (5)	0.0259 (5)	0.0005 (4)	0.0000 (4)	−0.0014 (4)
C4	0.0160 (4)	0.0179 (4)	0.0196 (4)	−0.0001 (4)	0.0032 (4)	−0.0012 (4)
C5	0.0166 (4)	0.0198 (4)	0.0172 (4)	−0.0019 (4)	0.0050 (3)	−0.0052 (3)
C6	0.0143 (4)	0.0171 (4)	0.0215 (5)	−0.0016 (3)	−0.0017 (4)	−0.0002 (4)
C7	0.0145 (4)	0.0126 (4)	0.0162 (4)	0.0002 (3)	−0.0017 (3)	0.0000 (3)
C8	0.0151 (4)	0.0155 (4)	0.0179 (4)	−0.0058 (4)	−0.0001 (3)	−0.0001 (3)
C9	0.0166 (5)	0.0241 (5)	0.0421 (6)	−0.0010 (4)	−0.0024 (4)	0.0012 (5)
C10	0.0361 (6)	0.0179 (5)	0.0275 (5)	−0.0039 (4)	−0.0051 (4)	0.0051 (4)
C11	0.0330 (6)	0.0349 (6)	0.0255 (6)	−0.0171 (5)	0.0039 (5)	−0.0126 (5)
N1	0.0161 (4)	0.0161 (4)	0.0162 (4)	−0.0040 (3)	0.0032 (3)	−0.0056 (3)
O1	0.0252 (4)	0.0171 (3)	0.0334 (4)	0.0050 (3)	−0.0025 (4)	0.0002 (3)
O2	0.0211 (4)	0.0186 (3)	0.0195 (3)	0.0009 (3)	0.0015 (3)	0.0029 (3)
O3	0.0219 (4)	0.0184 (3)	0.0165 (3)	−0.0038 (3)	0.0041 (3)	−0.0022 (3)
O4	0.0175 (3)	0.0185 (3)	0.0194 (3)	−0.0073 (3)	0.0040 (3)	−0.0059 (3)

C1—N1	1.4645 (11)	C6—O2	1.3570 (12)
C1—C6	1.5225 (13)	C7—O3	1.2175 (12)
C1—C2	1.5373 (14)	C7—O4	1.3481 (11)
C1—H1	1.0	C7—N1	1.3587 (12)
C2—C3	1.5482 (14)	C8—O4	1.4776 (11)
C2—H2A	0.99	C8—C9	1.5156 (15)
C2—H2B	0.99	C8—C10	1.5150 (14)
C3—C4	1.5222 (15)	C8—C11	1.5180 (14)
C3—H3B	0.99	C9—H9A	0.98
C3—H3A	0.99	C9—H9B	0.98
C4—O2	1.4699 (13)	C9—H9C	0.98
C4—C5	1.5171 (13)	C10—H10A	0.98
C4—H4	1.0	C10—H10B	0.98
C5—N1	1.4677 (12)	C10—H10C	0.98
C5—H5B	0.99	C11—H11A	0.98
C5—H5A	0.99	C11—H11B	0.98
C6—O1	1.2000 (12)	C11—H11C	0.98
N1—C1—C6	106.95 (7)	O3—C7—O4	126.43 (9)
N1—C1—C2	109.62 (8)	O3—C7—N1	124.45 (9)
C6—C1—C2	106.43 (8)	O4—C7—N1	109.12 (8)
N1—C1—H1	111.2	O4—C8—C9	110.65 (8)
C6—C1—H1	111.2	O4—C8—C10	109.82 (8)
C2—C1—H1	111.2	C9—C8—C10	112.55 (9)
C1—C2—C3	107.54 (8)	O4—C8—C11	101.89 (8)
C1—C2—H2A	110.2	C9—C8—C11	110.98 (10)
C3—C2—H2A	110.2	C10—C8—C11	110.44 (9)
C1—C2—H2B	110.2	C8—C9—H9A	109.5
C3—C2—H2B	110.2	C8—C9—H9B	109.5
H2A—C2—H2B	108.5	H9A—C9—H9B	109.5
C4—C3—C2	108.91 (8)	C8—C9—H9C	109.5
C4—C3—H3B	109.9	H9A—C9—H9C	109.5
C2—C3—H3B	109.9	H9B—C9—H9C	109.5
C4—C3—H3A	109.9	C8—C10—H10A	109.5
C2—C3—H3A	109.9	C8—C10—H10B	109.5
H3B—C3—H3A	108.3	H10A—C10—H10B	109.5
O2—C4—C5	107.40 (8)	C8—C10—H10C	109.5
O2—C4—C3	108.35 (8)	H10A—C10—H10C	109.5
C5—C4—C3	112.29 (9)	H10B—C10—H10C	109.5
O2—C4—H4	109.6	C8—C11—H11A	109.5
C5—C4—H4	109.6	C8—C11—H11B	109.5
C3—C4—H4	109.6	H11A—C11—H11B	109.5
N1—C5—C4	105.68 (8)	C8—C11—H11C	109.5
N1—C5—H5B	110.6	H11A—C11—H11C	109.5
C4—C5—H5B	110.6	H11B—C11—H11C	109.5
N1—C5—H5A	110.6	C7—N1—C1	121.03 (8)
C4—C5—H5A	110.6	C7—N1—C5	123.69 (8)
H5B—C5—H5A	108.7	C1—N1—C5	115.13 (8)
O1—C6—O2	120.96 (9)	C6—O2—C4	113.01 (7)
O1—C6—C1	126.91 (9)	C7—O4—C8	120.79 (7)
O2—C6—C1	112.10 (8)
N1—C1—C2—C3	−56.55 (10)	C6—C1—N1—C7	123.18 (10)
C6—C1—C2—C3	58.77 (10)	C2—C1—N1—C7	−121.84 (9)
C1—C2—C3—C4	−1.58 (11)	C6—C1—N1—C5	−52.53 (11)
C2—C3—C4—O2	−57.69 (10)	C2—C1—N1—C5	62.46 (10)
C2—C3—C4—C5	60.76 (11)	C4—C5—N1—C7	−179.64 (9)
O2—C4—C5—N1	61.20 (10)	C4—C5—N1—C1	−4.06 (11)
C3—C4—C5—N1	−57.81 (10)	O1—C6—O2—C4	−177.27 (9)
N1—C1—C6—O1	−126.60 (11)	C1—C6—O2—C4	0.91 (11)
C2—C1—C6—O1	116.29 (11)	C5—C4—O2—C6	−61.30 (10)
N1—C1—C6—O2	55.36 (10)	C3—C4—O2—C6	60.21 (10)
C2—C1—C6—O2	−61.75 (10)	O3—C7—O4—C8	−4.98 (15)
O3—C7—N1—C1	5.74 (15)	N1—C7—O4—C8	175.60 (8)
O4—C7—N1—C1	−174.83 (8)	C10—C8—O4—C7	67.57 (11)
O3—C7—N1—C5	−178.93 (9)	C9—C8—O4—C7	−57.30 (12)
O4—C7—N1—C5	0.50 (13)	C11—C8—O4—C7	−175.35 (9)