Crystal structure of benzyl 3-oxo-2-oxa-5-aza-bicyclo-[2.2.1]heptane-5-carboxyl-ate.

The title compound, C13H13NO4 (also known as N-benzyl-oxycarbonyl-4-hy-droxy-l-proline lactone), crystallizes with two mol-ecules in the asymmetric unit. They have slightly different conformations: the fused ring systems almost overlap, but different C-O-C-C torsion angles for the central chains of -155.5 (2) and -178.6 (2)° lead to different twists for the terminal benzene ring. In the crystal, the mol-ecules are linked by C-H⋯O inter-actions, generating a three-dimensional network. The absolute structure was established based on an unchanging chiral centre in the synthesis.

Related literature

For biological background, see: Dickens et al. (2008 ▸); Erdmann & Wennemers (2011 ▸); Krishnamurthy et al. (2014 ▸); Gómez-Vidal & Silverman (2001 ▸). For the synthesis, see: Lombardo et al. (2012 ▸).

Experimental

Crystal data

C13H13NO4

M = 247.24

Monoclinic,

a = 11.212 (2) Å

b = 8.8943 (16) Å

c = 12.258 (2) Å

β = 105.345 (2)°

V = 1178.8 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 90 K

0.40 × 0.35 × 0.30 mm

Data collection

Bruker APEX II KY CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T min = 0.709, T max = 0.969

11252 measured reflections

4157 independent reflections

4079 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.073

S = 1.06

4157 reflections

325 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.17 e Å−3

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: Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015010464/hb7435sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010464/hb7435Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015010464/hb7435fig1.tif

Mol­ecular configuration 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/S2056989015010464/hb7435fig2.tif

Crystal packing diagram of the title compound.

Click here for additional data file.

. DOI: 10.1107/S2056989015010464/hb7435fig3.tif

Synthetic scheme for the title compound (I)

CCDC reference: 1402251

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

C13H13NO4	Z = 4
Mr = 247.24	F(000) = 520
Monoclinic, P21	Dx = 1.393 Mg m−3
a = 11.212 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.8943 (16) Å	µ = 0.10 mm−1
c = 12.258 (2) Å	T = 90 K
β = 105.345 (2)°	Prism, colorless
V = 1178.8 (4) Å3	0.40 × 0.35 × 0.30 mm

Bruker APEX II KY CCD diffractometer	4157 independent reflections
Radiation source: fine-focus sealed tube	4079 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Detector resolution: 8.333 pixels mm-1	θmax = 25.0°, θmin = 1.7°
φandω–scans	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −10→10
Tmin = 0.709, Tmax = 0.969	l = −14→14
11252 measured reflections

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0404P)2 + 0.1656P] where P = (Fo2 + 2Fc2)/3
4157 reflections	(Δ/σ)max < 0.001
325 parameters	Δρmax = 0.19 e Å−3
1 restraint	Δρmin = −0.16 e Å−3

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	0.03159 (12)	0.45789 (16)	0.37070 (12)	0.0215 (3)
H1	−0.0256	0.4019	0.31	0.026*
C2	−0.02168 (13)	0.52285 (17)	0.46339 (12)	0.0235 (3)
H2A	−0.0862	0.5968	0.4356	0.028*
H2B	−0.0493	0.4465	0.5077	0.028*
C3	0.10287 (13)	0.59254 (17)	0.52422 (12)	0.0229 (3)
H3	0.1023	0.6507	0.592	0.027*
C4	0.19041 (13)	0.45866 (17)	0.54550 (11)	0.0229 (3)
H4A	0.2754	0.4888	0.5535	0.027*
H4B	0.1852	0.4018	0.6116	0.027*
C5	0.09010 (12)	0.59924 (16)	0.33634 (11)	0.0210 (3)
C6	0.19212 (13)	0.25806 (16)	0.39927 (12)	0.0218 (3)
C7	0.35825 (16)	0.0823 (2)	0.44690 (14)	0.0356 (4)
H7A	0.4176	0.1195	0.4083	0.043*
H7B	0.3012	0.0154	0.3961	0.043*
C8	0.42360 (14)	0.00050 (16)	0.55255 (13)	0.0265 (3)
C9	0.35980 (13)	−0.10101 (17)	0.60196 (15)	0.0319 (4)
H9	0.2765	−0.1189	0.5683	0.038*
C10	0.41768 (15)	−0.17599 (18)	0.70017 (15)	0.0341 (4)
H10	0.3731	−0.2425	0.7328	0.041*
C11	0.54297 (15)	−0.15203 (18)	0.75052 (14)	0.0310 (3)
H11	0.5828	−0.2035	0.8161	0.037*
C12	0.60744 (13)	−0.05120 (18)	0.70219 (13)	0.0290 (3)
H12	0.6911	−0.0349	0.7354	0.035*
C13	0.54857 (13)	0.02589 (18)	0.60467 (13)	0.0281 (3)
H13	0.5926	0.095	0.5737	0.034*
C14	0.96660 (12)	0.95675 (15)	0.18254 (11)	0.0199 (3)
H14	0.9969	0.9291	0.2625	0.024*
C15	1.06237 (13)	0.96354 (17)	0.11437 (12)	0.0228 (3)
H15A	1.1262	1.0383	0.1421	0.027*
H15B	1.0989	0.8666	0.1065	0.027*
C16	0.96511 (13)	1.01286 (16)	0.00832 (12)	0.0230 (3)
H16	0.9969	1.0321	−0.0575	0.028*
C17	0.86734 (13)	0.88969 (16)	−0.00859 (11)	0.0227 (3)
H17A	0.7863	0.926	−0.0497	0.027*
H17B	0.8892	0.8029	−0.0472	0.027*
C18	0.90739 (12)	1.11153 (16)	0.15699 (11)	0.0200 (3)
C19	0.81590 (12)	0.74552 (15)	0.15094 (12)	0.0190 (3)
C20	0.66990 (14)	0.54756 (16)	0.09787 (12)	0.0257 (3)
H20A	0.6144	0.5876	0.1394	0.031*
H20B	0.7242	0.4745	0.145	0.031*
C21	0.59844 (12)	0.47712 (16)	−0.01037 (12)	0.0224 (3)
C22	0.47838 (13)	0.52208 (17)	−0.06415 (13)	0.0259 (3)
H22	0.4391	0.5936	−0.0305	0.031*
C23	0.41709 (13)	0.46052 (18)	−0.16784 (13)	0.0280 (3)
H23	0.3365	0.49	−0.2028	0.034*
C24	0.47492 (14)	0.35578 (17)	−0.21940 (13)	0.0293 (3)
H24	0.4339	0.3158	−0.2894	0.035*
C25	0.59509 (15)	0.31033 (18)	−0.16600 (14)	0.0310 (3)
H25	0.6349	0.2404	−0.2006	0.037*
C26	0.65512 (13)	0.36930 (17)	−0.06153 (13)	0.0262 (3)
H26	0.7344	0.3364	−0.0251	0.031*
N1	0.13918 (11)	0.37446 (13)	0.43984 (10)	0.0227 (3)
N2	0.87336 (11)	0.85642 (14)	0.11057 (9)	0.0213 (2)
O1	0.10735 (9)	0.63621 (12)	0.24784 (8)	0.0278 (2)
O2	0.13217 (9)	0.68041 (11)	0.43299 (8)	0.0233 (2)
O3	0.15344 (9)	0.20350 (13)	0.30604 (9)	0.0302 (2)
O4	0.29114 (9)	0.20752 (12)	0.47981 (8)	0.0267 (2)
O5	0.85762 (8)	1.19197 (12)	0.21078 (8)	0.0252 (2)
O6	0.91040 (9)	1.14515 (11)	0.04972 (8)	0.0232 (2)
O7	0.82890 (8)	0.71808 (11)	0.25057 (8)	0.0224 (2)
O8	0.74174 (9)	0.66846 (11)	0.06459 (8)	0.0244 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0192 (6)	0.0193 (7)	0.0234 (7)	0.0006 (6)	0.0013 (5)	−0.0015 (6)
C2	0.0206 (7)	0.0251 (7)	0.0246 (7)	0.0012 (6)	0.0055 (6)	0.0036 (6)
C3	0.0257 (7)	0.0239 (7)	0.0195 (7)	0.0011 (6)	0.0068 (6)	0.0003 (6)
C4	0.0246 (7)	0.0232 (7)	0.0200 (7)	0.0005 (6)	0.0043 (5)	0.0000 (6)
C5	0.0185 (6)	0.0229 (7)	0.0204 (7)	0.0071 (5)	0.0031 (5)	0.0010 (5)
C6	0.0188 (6)	0.0196 (7)	0.0268 (7)	−0.0004 (5)	0.0056 (5)	0.0016 (6)
C7	0.0374 (9)	0.0358 (8)	0.0343 (8)	0.0174 (7)	0.0109 (7)	−0.0006 (7)
C8	0.0245 (7)	0.0228 (8)	0.0325 (8)	0.0074 (6)	0.0081 (6)	−0.0035 (6)
C9	0.0171 (7)	0.0253 (8)	0.0502 (10)	−0.0003 (6)	0.0031 (6)	−0.0034 (7)
C10	0.0282 (8)	0.0255 (8)	0.0497 (10)	0.0006 (6)	0.0123 (7)	0.0060 (7)
C11	0.0278 (8)	0.0301 (8)	0.0329 (8)	0.0075 (6)	0.0042 (6)	0.0019 (6)
C12	0.0172 (7)	0.0322 (8)	0.0360 (8)	0.0036 (6)	0.0041 (6)	−0.0069 (7)
C13	0.0242 (7)	0.0253 (7)	0.0383 (9)	0.0007 (6)	0.0144 (7)	−0.0027 (7)
C14	0.0181 (6)	0.0208 (7)	0.0198 (6)	−0.0006 (5)	0.0032 (5)	−0.0009 (5)
C15	0.0201 (7)	0.0227 (7)	0.0262 (7)	0.0004 (6)	0.0073 (5)	−0.0026 (6)
C16	0.0262 (7)	0.0216 (7)	0.0239 (7)	0.0022 (6)	0.0111 (6)	−0.0007 (6)
C17	0.0253 (7)	0.0238 (7)	0.0183 (7)	−0.0008 (6)	0.0047 (5)	−0.0011 (6)
C18	0.0147 (6)	0.0220 (7)	0.0225 (7)	−0.0046 (5)	0.0034 (5)	−0.0025 (5)
C19	0.0149 (6)	0.0178 (7)	0.0238 (7)	0.0030 (5)	0.0043 (5)	−0.0001 (5)
C20	0.0267 (7)	0.0222 (8)	0.0284 (8)	−0.0069 (6)	0.0075 (6)	0.0006 (6)
C21	0.0213 (7)	0.0200 (7)	0.0266 (7)	−0.0057 (6)	0.0077 (5)	0.0017 (6)
C22	0.0224 (7)	0.0222 (7)	0.0345 (8)	0.0009 (6)	0.0103 (6)	0.0006 (6)
C23	0.0174 (7)	0.0278 (7)	0.0362 (8)	−0.0019 (6)	0.0028 (6)	0.0057 (7)
C24	0.0284 (8)	0.0271 (8)	0.0295 (8)	−0.0064 (6)	0.0026 (6)	−0.0028 (6)
C25	0.0298 (8)	0.0269 (8)	0.0376 (8)	0.0013 (6)	0.0112 (6)	−0.0057 (7)
C26	0.0178 (7)	0.0252 (7)	0.0350 (8)	0.0008 (6)	0.0061 (6)	0.0018 (6)
N1	0.0230 (6)	0.0191 (6)	0.0225 (6)	0.0033 (5)	0.0001 (5)	−0.0003 (5)
N2	0.0221 (6)	0.0216 (6)	0.0182 (6)	−0.0028 (5)	0.0016 (5)	−0.0011 (5)
O1	0.0283 (5)	0.0338 (6)	0.0224 (5)	0.0082 (5)	0.0086 (4)	0.0067 (4)
O2	0.0272 (5)	0.0203 (5)	0.0220 (5)	−0.0007 (4)	0.0058 (4)	0.0011 (4)
O3	0.0254 (5)	0.0293 (6)	0.0332 (6)	0.0024 (5)	0.0028 (4)	−0.0082 (5)
O4	0.0253 (5)	0.0249 (5)	0.0288 (5)	0.0079 (4)	0.0052 (4)	0.0010 (4)
O5	0.0210 (5)	0.0265 (5)	0.0280 (5)	−0.0002 (4)	0.0060 (4)	−0.0053 (4)
O6	0.0266 (5)	0.0192 (5)	0.0239 (5)	0.0018 (4)	0.0068 (4)	0.0018 (4)
O7	0.0207 (5)	0.0234 (5)	0.0226 (5)	0.0002 (4)	0.0049 (4)	0.0023 (4)
O8	0.0253 (5)	0.0230 (5)	0.0239 (5)	−0.0070 (4)	0.0048 (4)	−0.0011 (4)

C1—N1	1.4776 (17)	C14—N2	1.4763 (17)
C1—C5	1.528 (2)	C14—C18	1.525 (2)
C1—C2	1.530 (2)	C14—C15	1.5263 (19)
C1—H1	0.98	C14—H14	0.98
C2—C3	1.530 (2)	C15—C16	1.524 (2)
C2—H2A	0.97	C15—H15A	0.97
C2—H2B	0.97	C15—H15B	0.97
C3—O2	1.4710 (17)	C16—O6	1.4775 (16)
C3—C4	1.521 (2)	C16—C17	1.525 (2)
C3—H3	0.98	C16—H16	0.98
C4—N1	1.4746 (18)	C17—N2	1.4742 (18)
C4—H4A	0.97	C17—H17A	0.97
C4—H4B	0.97	C17—H17B	0.97
C5—O1	1.1973 (18)	C18—O5	1.2053 (17)
C5—O2	1.3606 (17)	C18—O6	1.3576 (17)
C6—O3	1.2113 (18)	C19—O7	1.2158 (17)
C6—N1	1.3519 (19)	C19—N2	1.3423 (18)
C6—O4	1.3526 (17)	C19—O8	1.3475 (16)
C7—O4	1.4592 (18)	C20—O8	1.4648 (16)
C7—C8	1.497 (2)	C20—C21	1.494 (2)
C7—H7A	0.97	C20—H20A	0.97
C7—H7B	0.97	C20—H20B	0.97
C8—C9	1.387 (2)	C21—C26	1.388 (2)
C8—C13	1.396 (2)	C21—C22	1.392 (2)
C9—C10	1.379 (2)	C22—C23	1.388 (2)
C9—H9	0.93	C22—H22	0.93
C10—C11	1.393 (2)	C23—C24	1.380 (2)
C10—H10	0.93	C23—H23	0.93
C11—C12	1.380 (2)	C24—C25	1.393 (2)
C11—H11	0.93	C24—H24	0.93
C12—C13	1.385 (2)	C25—C26	1.383 (2)
C12—H12	0.93	C25—H25	0.93
C13—H13	0.93	C26—H26	0.93
N1—C1—C5	103.08 (11)	C15—C14—H14	116.7
N1—C1—C2	100.58 (11)	C16—C15—C14	91.73 (10)
C5—C1—C2	100.05 (11)	C16—C15—H15A	113.3
N1—C1—H1	116.8	C14—C15—H15A	113.3
C5—C1—H1	116.8	C16—C15—H15B	113.3
C2—C1—H1	116.8	C14—C15—H15B	113.3
C3—C2—C1	91.69 (11)	H15A—C15—H15B	110.7
C3—C2—H2A	113.3	O6—C16—C15	101.81 (10)
C1—C2—H2A	113.3	O6—C16—C17	105.66 (10)
C3—C2—H2B	113.3	C15—C16—C17	103.63 (11)
C1—C2—H2B	113.3	O6—C16—H16	114.8
H2A—C2—H2B	110.7	C15—C16—H16	114.8
O2—C3—C4	106.41 (11)	C17—C16—H16	114.8
O2—C3—C2	101.74 (11)	N2—C17—C16	99.60 (11)
C4—C3—C2	103.34 (12)	N2—C17—H17A	111.9
O2—C3—H3	114.6	C16—C17—H17A	111.9
C4—C3—H3	114.6	N2—C17—H17B	111.9
C2—C3—H3	114.6	C16—C17—H17B	111.9
N1—C4—C3	99.40 (11)	H17A—C17—H17B	109.6
N1—C4—H4A	111.9	O5—C18—O6	122.20 (13)
C3—C4—H4A	111.9	O5—C18—C14	131.54 (13)
N1—C4—H4B	111.9	O6—C18—C14	106.07 (11)
C3—C4—H4B	111.9	O7—C19—N2	125.19 (13)
H4A—C4—H4B	109.6	O7—C19—O8	124.89 (12)
O1—C5—O2	122.78 (14)	N2—C19—O8	109.92 (12)
O1—C5—C1	131.28 (13)	O8—C20—C21	105.41 (11)
O2—C5—C1	105.77 (11)	O8—C20—H20A	110.7
O3—C6—N1	124.85 (13)	C21—C20—H20A	110.7
O3—C6—O4	125.12 (13)	O8—C20—H20B	110.7
N1—C6—O4	109.97 (12)	C21—C20—H20B	110.7
O4—C7—C8	107.58 (12)	H20A—C20—H20B	108.8
O4—C7—H7A	110.2	C26—C21—C22	119.05 (13)
C8—C7—H7A	110.2	C26—C21—C20	119.26 (13)
O4—C7—H7B	110.2	C22—C21—C20	121.62 (13)
C8—C7—H7B	110.2	C23—C22—C21	120.20 (14)
H7A—C7—H7B	108.5	C23—C22—H22	119.9
C9—C8—C13	118.47 (14)	C21—C22—H22	119.9
C9—C8—C7	120.22 (14)	C24—C23—C22	120.46 (14)
C13—C8—C7	121.29 (14)	C24—C23—H23	119.8
C10—C9—C8	121.21 (14)	C22—C23—H23	119.8
C10—C9—H9	119.4	C23—C24—C25	119.60 (14)
C8—C9—H9	119.4	C23—C24—H24	120.2
C9—C10—C11	119.95 (15)	C25—C24—H24	120.2
C9—C10—H10	120.0	C26—C25—C24	119.89 (15)
C11—C10—H10	120.0	C26—C25—H25	120.1
C12—C11—C10	119.38 (15)	C24—C25—H25	120.1
C12—C11—H11	120.3	C25—C26—C21	120.76 (13)
C10—C11—H11	120.3	C25—C26—H26	119.6
C11—C12—C13	120.54 (14)	C21—C26—H26	119.6
C11—C12—H12	119.7	C6—N1—C4	127.24 (12)
C13—C12—H12	119.7	C6—N1—C1	123.02 (11)
C12—C13—C8	120.43 (14)	C4—N1—C1	108.53 (11)
C12—C13—H13	119.8	C19—N2—C17	127.75 (12)
C8—C13—H13	119.8	C19—N2—C14	123.84 (11)
N2—C14—C18	102.83 (10)	C17—N2—C14	108.07 (11)
N2—C14—C15	100.74 (11)	C5—O2—C3	106.52 (11)
C18—C14—C15	100.54 (11)	C6—O4—C7	115.82 (11)
N2—C14—H14	116.7	C18—O6—C16	106.04 (10)
C18—C14—H14	116.7	C19—O8—C20	115.16 (10)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O5i	0.98	2.42	3.3493 (18)	159
C2—H2A···O7ii	0.97	2.46	3.2116 (18)	134
C3—H3···O5iii	0.98	2.37	3.2816 (18)	155
C4—H4B···O7iii	0.97	2.39	3.3408 (18)	168
C15—H15A···O3iv	0.97	2.44	3.1382 (19)	128
C16—H16···O1v	0.98	2.49	3.2207 (18)	131
C26—H26···O6vi	0.93	2.58	3.4584 (19)	157

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C1H1O5i	0.98	2.42	3.3493(18)	159
C2H2AO7ii	0.97	2.46	3.2116(18)	134
C3H3O5iii	0.98	2.37	3.2816(18)	155
C4H4BO7iii	0.97	2.39	3.3408(18)	168
C15H15AO3iv	0.97	2.44	3.1382(19)	128
C16H16O1v	0.98	2.49	3.2207(18)	131
C26H26O6vi	0.93	2.58	3.4584(19)	157

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .