Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107006646/gz3069sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107006646/gz3069Isup2.hkl |
CCDC reference: 641823
For related literature, see: Allen et al. (1998); Bernstein et al. (1995); Cremer & Pople (1975); Jones (2003); Miao et al. (1995); Stefanowicz et al. (2005, 2006).
The synthesis of benzyl (3S)-1-hydroxy-2,5-dioxopyrrolidin-3-ylcarbamate was carried out according to the following procedure. Cbz-L-aspartic acid anhydride (1 g, 4 mmol) was added to a solution of hydroxylamine hydrochloride NH3(OH)Cl (0.30 g, 4 mmol) and NaOH (0.16 g, 4 mmol) dissolved in a water–dioxane mixture (1:1 v/v; 4 ml). The solution was stirred for 15 min at room temperature and then for 1 h at 323 K. The water and dioxane were then evaporated under reduced pressure and the residue was heated at 398 K for 20 min in vacuo. The product was extracted with anhydrous ethyl acetate (30 ml). Single crystals of (I) were obtained by slow evaporation from an ethyl acetate solution (yield 77%; m.p. 413–414.5 K). The crystals of (I) are hygroscopic and not stable in air; on removal from the ethyl acetate solution they become matt and break. Analysis: [α]D24 = -39.7° (c = 1.40, MeOH); ESI–MS m/z 287 [MNa]+.
The absolute configuration of the chiral C atom was established in agreement with the absolute configuration of the L-enantiomer of aspartic acid, which was used for the synthesis of the compound (I). Friedel opposites were merged for the refinement. Other investigations showed the lack of racemization in the synthetic route of the present compound (Stefanowicz et al., 2006). Only the aliphatic and aromatic H atoms were positioned geometrically and refined as riding on their parent atoms, with C—H = 0.95–1.00 Å and Uiso(H) = 1.2Ueq(C). Other H atoms were located in a difference Fourier map and their positions refined, with N—H = 0.84 (3) Å and O—H = 0.80 (3)–0.87 (3) Å; their Uiso(H) values were constrained to 1.2Ueq(parent atom). [Please check rephrasing]
Data collection: KM-4 CCD Software (Oxford Diffraction, 2004); cell refinement: KM-4 CCD Software; data reduction: KM-4 CCD Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXL97.
C12H12N2O5 | F(000) = 552 |
Mr = 264.24 | Dx = 1.477 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 5987 reflections |
a = 12.910 (3) Å | θ = 3.2–30.0° |
b = 7.077 (4) Å | µ = 0.12 mm−1 |
c = 14.001 (3) Å | T = 100 K |
β = 111.67 (3)° | Plate, colourless |
V = 1188.8 (8) Å3 | 0.28 × 0.25 × 0.20 mm |
Z = 4 |
Oxford KM4 CCD area-detector diffractometer | 3070 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.043 |
Graphite monochromator | θmax = 30.0°, θmin = 3.2° |
Detector resolution: 0 pixels mm-1 | h = −18→14 |
ω scans | k = −9→9 |
17662 measured reflections | l = −19→19 |
3640 independent 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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0473P)2] where P = (Fo2 + 2Fc2)/3 |
3640 reflections | (Δ/σ)max < 0.001 |
355 parameters | Δρmax = 0.22 e Å−3 |
1 restraint | Δρmin = −0.22 e Å−3 |
C12H12N2O5 | V = 1188.8 (8) Å3 |
Mr = 264.24 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 12.910 (3) Å | µ = 0.12 mm−1 |
b = 7.077 (4) Å | T = 100 K |
c = 14.001 (3) Å | 0.28 × 0.25 × 0.20 mm |
β = 111.67 (3)° |
Oxford KM4 CCD area-detector diffractometer | 3070 reflections with I > 2σ(I) |
17662 measured reflections | Rint = 0.043 |
3640 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 1 restraint |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.22 e Å−3 |
3640 reflections | Δρmin = −0.22 e Å−3 |
355 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 > 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. |
x | y | z | Uiso*/Ueq | ||
O1A | 0.70860 (12) | 0.2164 (2) | 0.48559 (12) | 0.0289 (4) | |
O2A | 0.79722 (13) | 0.1400 (2) | 0.33584 (11) | 0.0243 (3) | |
H1A | 0.766 (2) | 0.032 (4) | 0.3117 (19) | 0.029* | |
O3A | 1.00027 (13) | −0.0542 (2) | 0.42948 (13) | 0.0320 (4) | |
O4A | 0.79080 (12) | 0.2630 (2) | 0.74929 (11) | 0.0214 (3) | |
O5A | 0.74498 (12) | −0.0335 (2) | 0.78135 (11) | 0.0205 (3) | |
N1A | 0.84965 (14) | 0.1030 (2) | 0.43960 (13) | 0.0193 (4) | |
N2A | 0.83702 (15) | 0.0016 (3) | 0.67733 (14) | 0.0210 (4) | |
H2NA | 0.823 (2) | −0.114 (4) | 0.6695 (18) | 0.025* | |
C1A | 0.80102 (16) | 0.1503 (3) | 0.50842 (15) | 0.0192 (4) | |
C2A | 0.88554 (16) | 0.1060 (3) | 0.61501 (15) | 0.0196 (4) | |
H2A | 0.9159 | 0.2278 | 0.6505 | 0.024* | |
C3A | 0.98004 (16) | 0.0006 (3) | 0.59489 (16) | 0.0223 (4) | |
H31A | 1.0526 | 0.0631 | 0.6313 | 0.027* | |
H32A | 0.9847 | −0.1320 | 0.6186 | 0.027* | |
C4A | 0.95052 (16) | 0.0083 (3) | 0.48021 (16) | 0.0219 (4) | |
C5A | 0.79084 (16) | 0.0917 (3) | 0.73619 (15) | 0.0179 (4) | |
C6A | 0.71173 (16) | 0.0379 (3) | 0.86245 (15) | 0.0201 (4) | |
H61A | 0.6525 | −0.0440 | 0.8690 | 0.024* | |
H62A | 0.6807 | 0.1667 | 0.8444 | 0.024* | |
C7A | 0.80870 (16) | 0.0439 (3) | 0.96372 (15) | 0.0180 (4) | |
C8A | 0.79748 (17) | 0.1455 (3) | 1.04528 (16) | 0.0218 (4) | |
H8A | 0.7303 | 0.2120 | 1.0351 | 0.026* | |
C9A | 0.88372 (18) | 0.1498 (3) | 1.14095 (16) | 0.0248 (4) | |
H9A | 0.8757 | 0.2199 | 1.1957 | 0.030* | |
C10A | 0.98165 (18) | 0.0513 (3) | 1.15624 (17) | 0.0266 (5) | |
H10A | 1.0408 | 0.0536 | 1.2215 | 0.032* | |
C11A | 0.99277 (17) | −0.0503 (3) | 1.07613 (16) | 0.0263 (5) | |
H11A | 1.0596 | −0.1181 | 1.0867 | 0.032* | |
C12A | 0.90701 (16) | −0.0540 (3) | 0.98037 (16) | 0.0226 (4) | |
H12A | 0.9157 | −0.1240 | 0.9259 | 0.027* | |
O3B | 0.51201 (12) | 0.4240 (2) | 0.56098 (12) | 0.0296 (4) | |
O2B | 0.72170 (13) | 0.5982 (2) | 0.65733 (11) | 0.0238 (3) | |
H1B | 0.741 (2) | 0.494 (4) | 0.6791 (19) | 0.029* | |
O1B | 0.79804 (12) | 0.7224 (2) | 0.50629 (12) | 0.0271 (3) | |
O4B | 0.69593 (12) | 0.8229 (2) | 0.24594 (11) | 0.0238 (3) | |
O5B | 0.74485 (11) | 0.5468 (2) | 0.19123 (11) | 0.0199 (3) | |
N1B | 0.66311 (13) | 0.5835 (2) | 0.55306 (12) | 0.0187 (4) | |
N2B | 0.66563 (14) | 0.5380 (3) | 0.30778 (13) | 0.0197 (4) | |
H2NB | 0.6846 (19) | 0.424 (4) | 0.3122 (17) | 0.024* | |
C4B | 0.56044 (16) | 0.4951 (3) | 0.51081 (16) | 0.0206 (4) | |
C3B | 0.52739 (16) | 0.5038 (3) | 0.39590 (16) | 0.0221 (4) | |
H31B | 0.4535 | 0.5645 | 0.3635 | 0.027* | |
H32B | 0.5240 | 0.3753 | 0.3669 | 0.027* | |
C2B | 0.61842 (16) | 0.6223 (3) | 0.37743 (15) | 0.0198 (4) | |
H2B | 0.5862 | 0.7482 | 0.3494 | 0.024* | |
C1B | 0.70671 (16) | 0.6509 (3) | 0.48407 (15) | 0.0183 (4) | |
C5B | 0.70265 (16) | 0.6496 (3) | 0.24930 (14) | 0.0181 (4) | |
C6B | 0.77324 (16) | 0.6497 (3) | 0.11328 (15) | 0.0209 (4) | |
H61B | 0.8393 | 0.5908 | 0.1056 | 0.025* | |
H62B | 0.7923 | 0.7820 | 0.1358 | 0.025* | |
C7B | 0.67727 (16) | 0.6474 (3) | 0.01147 (15) | 0.0190 (4) | |
C8B | 0.68887 (17) | 0.5607 (3) | −0.07384 (17) | 0.0217 (4) | |
H8B | 0.7580 | 0.5042 | −0.0670 | 0.026* | |
C9B | 0.60116 (17) | 0.5559 (3) | −0.16815 (16) | 0.0241 (4) | |
H9B | 0.6103 | 0.4966 | −0.2254 | 0.029* | |
C10B | 0.50023 (17) | 0.6379 (3) | −0.17846 (17) | 0.0240 (4) | |
H10B | 0.4395 | 0.6327 | −0.2426 | 0.029* | |
C11B | 0.48770 (17) | 0.7279 (3) | −0.09499 (16) | 0.0255 (5) | |
H11B | 0.4188 | 0.7864 | −0.1028 | 0.031* | |
C12B | 0.57518 (16) | 0.7325 (3) | −0.00050 (16) | 0.0233 (4) | |
H12B | 0.5659 | 0.7934 | 0.0563 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0275 (8) | 0.0308 (9) | 0.0296 (8) | 0.0091 (7) | 0.0119 (7) | 0.0030 (7) |
O2A | 0.0360 (8) | 0.0195 (8) | 0.0161 (7) | −0.0004 (7) | 0.0082 (6) | 0.0005 (6) |
O3A | 0.0361 (8) | 0.0307 (9) | 0.0381 (9) | 0.0067 (8) | 0.0240 (8) | 0.0012 (8) |
O4A | 0.0280 (7) | 0.0175 (8) | 0.0192 (7) | −0.0015 (6) | 0.0093 (6) | −0.0004 (6) |
O5A | 0.0280 (7) | 0.0173 (8) | 0.0202 (7) | −0.0030 (6) | 0.0138 (6) | −0.0005 (6) |
N1A | 0.0248 (9) | 0.0188 (9) | 0.0149 (8) | 0.0006 (7) | 0.0081 (7) | 0.0014 (6) |
N2A | 0.0295 (9) | 0.0153 (9) | 0.0211 (9) | −0.0032 (8) | 0.0130 (7) | −0.0005 (7) |
C1A | 0.0228 (10) | 0.0160 (9) | 0.0207 (10) | 0.0003 (9) | 0.0101 (8) | −0.0005 (8) |
C2A | 0.0234 (10) | 0.0190 (10) | 0.0175 (10) | −0.0014 (8) | 0.0089 (8) | 0.0003 (7) |
C3A | 0.0180 (9) | 0.0233 (11) | 0.0254 (11) | 0.0002 (8) | 0.0077 (8) | 0.0007 (8) |
C4A | 0.0237 (10) | 0.0177 (10) | 0.0277 (11) | −0.0013 (8) | 0.0136 (9) | 0.0001 (8) |
C5A | 0.0189 (9) | 0.0188 (10) | 0.0143 (9) | −0.0007 (8) | 0.0039 (8) | 0.0010 (7) |
C6A | 0.0224 (9) | 0.0215 (10) | 0.0203 (10) | 0.0011 (8) | 0.0125 (8) | 0.0022 (8) |
C7A | 0.0201 (9) | 0.0169 (10) | 0.0191 (10) | −0.0014 (8) | 0.0097 (8) | 0.0017 (8) |
C8A | 0.0271 (10) | 0.0178 (10) | 0.0241 (11) | 0.0023 (9) | 0.0138 (9) | 0.0013 (8) |
C9A | 0.0367 (11) | 0.0201 (10) | 0.0185 (10) | −0.0024 (10) | 0.0112 (9) | −0.0022 (8) |
C10A | 0.0285 (11) | 0.0251 (12) | 0.0229 (11) | −0.0051 (9) | 0.0055 (9) | 0.0037 (9) |
C11A | 0.0228 (10) | 0.0285 (12) | 0.0285 (12) | 0.0026 (9) | 0.0105 (9) | 0.0058 (10) |
C12A | 0.0252 (10) | 0.0228 (11) | 0.0231 (11) | 0.0035 (9) | 0.0130 (9) | 0.0020 (9) |
O3B | 0.0316 (8) | 0.0315 (9) | 0.0322 (8) | −0.0070 (7) | 0.0194 (7) | −0.0013 (7) |
O2B | 0.0335 (8) | 0.0198 (8) | 0.0151 (7) | −0.0015 (7) | 0.0053 (6) | 0.0004 (6) |
O1B | 0.0249 (8) | 0.0284 (8) | 0.0287 (8) | −0.0088 (7) | 0.0106 (7) | −0.0040 (7) |
O4B | 0.0313 (8) | 0.0175 (8) | 0.0228 (8) | 0.0008 (6) | 0.0103 (7) | 0.0000 (6) |
O5B | 0.0254 (7) | 0.0183 (7) | 0.0192 (7) | 0.0015 (6) | 0.0121 (6) | 0.0022 (6) |
N1B | 0.0223 (8) | 0.0181 (9) | 0.0153 (8) | −0.0005 (7) | 0.0066 (7) | −0.0003 (7) |
N2B | 0.0262 (9) | 0.0156 (9) | 0.0195 (9) | 0.0019 (7) | 0.0112 (7) | −0.0003 (7) |
C4B | 0.0216 (10) | 0.0173 (10) | 0.0237 (10) | 0.0008 (8) | 0.0092 (9) | −0.0023 (8) |
C3B | 0.0192 (9) | 0.0232 (11) | 0.0232 (10) | −0.0006 (8) | 0.0068 (8) | −0.0029 (8) |
C2B | 0.0234 (10) | 0.0219 (11) | 0.0165 (10) | 0.0021 (8) | 0.0101 (8) | −0.0009 (8) |
C1B | 0.0218 (10) | 0.0145 (9) | 0.0197 (10) | 0.0007 (8) | 0.0090 (8) | −0.0010 (8) |
C5B | 0.0192 (9) | 0.0189 (10) | 0.0135 (9) | 0.0001 (8) | 0.0030 (7) | −0.0014 (8) |
C6B | 0.0234 (10) | 0.0209 (10) | 0.0208 (10) | −0.0014 (9) | 0.0108 (8) | 0.0026 (8) |
C7B | 0.0227 (10) | 0.0149 (10) | 0.0208 (10) | −0.0011 (8) | 0.0097 (8) | 0.0025 (8) |
C8B | 0.0241 (10) | 0.0189 (10) | 0.0254 (11) | 0.0028 (8) | 0.0131 (9) | 0.0034 (8) |
C9B | 0.0332 (11) | 0.0202 (11) | 0.0205 (11) | −0.0012 (9) | 0.0117 (9) | 0.0011 (8) |
C10B | 0.0247 (10) | 0.0229 (11) | 0.0218 (10) | −0.0054 (9) | 0.0056 (8) | 0.0037 (9) |
C11B | 0.0225 (10) | 0.0279 (11) | 0.0283 (11) | 0.0035 (10) | 0.0120 (9) | 0.0081 (9) |
C12B | 0.0270 (10) | 0.0249 (11) | 0.0220 (10) | 0.0036 (9) | 0.0140 (9) | 0.0038 (9) |
O1A—C1A | 1.210 (2) | O3B—C4B | 1.209 (2) |
O2A—N1A | 1.382 (2) | O2B—N1B | 1.378 (2) |
O2A—H1A | 0.87 (3) | O2B—H1B | 0.80 (3) |
O3A—C4A | 1.204 (2) | O1B—C1B | 1.213 (2) |
O4A—C5A | 1.226 (3) | O4B—C5B | 1.229 (3) |
O5A—C5A | 1.346 (2) | O5B—C5B | 1.347 (2) |
O5A—C6A | 1.445 (2) | O5B—C6B | 1.467 (2) |
N1A—C1A | 1.372 (3) | N1B—C1B | 1.371 (3) |
N1A—C4A | 1.386 (3) | N1B—C4B | 1.385 (3) |
N2A—C5A | 1.343 (3) | N2B—C5B | 1.346 (3) |
N2A—C2A | 1.450 (3) | N2B—C2B | 1.455 (3) |
N2A—H2NA | 0.84 (3) | N2B—H2NB | 0.84 (3) |
C1A—C2A | 1.521 (3) | C4B—C3B | 1.506 (3) |
C2A—C3A | 1.542 (3) | C3B—C2B | 1.541 (3) |
C2A—H2A | 1.0000 | C3B—H31B | 0.9900 |
C3A—C4A | 1.508 (3) | C3B—H32B | 0.9900 |
C3A—H31A | 0.9900 | C2B—C1B | 1.521 (3) |
C3A—H32A | 0.9900 | C2B—H2B | 1.0000 |
C6A—C7A | 1.506 (3) | C6B—C7B | 1.504 (3) |
C6A—H61A | 0.9900 | C6B—H61B | 0.9900 |
C6A—H62A | 0.9900 | C6B—H62B | 0.9900 |
C7A—C12A | 1.388 (3) | C7B—C8B | 1.399 (3) |
C7A—C8A | 1.401 (3) | C7B—C12B | 1.402 (3) |
C8A—C9A | 1.390 (3) | C8B—C9B | 1.387 (3) |
C8A—H8A | 0.9500 | C8B—H8B | 0.9500 |
C9A—C10A | 1.390 (3) | C9B—C10B | 1.384 (3) |
C9A—H9A | 0.9500 | C9B—H9B | 0.9500 |
C10A—C11A | 1.384 (3) | C10B—C11B | 1.392 (3) |
C10A—H10A | 0.9500 | C10B—H10B | 0.9500 |
C11A—C12A | 1.388 (3) | C11B—C12B | 1.387 (3) |
C11A—H11A | 0.9500 | C11B—H11B | 0.9500 |
C12A—H12A | 0.9500 | C12B—H12B | 0.9500 |
N1A—O2A—H1A | 102.6 (17) | N1B—O2B—H1B | 107.9 (19) |
C5A—O5A—C6A | 116.66 (16) | C5B—O5B—C6B | 116.67 (16) |
C1A—N1A—O2A | 121.23 (16) | C1B—N1B—O2B | 120.84 (16) |
C1A—N1A—C4A | 115.74 (17) | C1B—N1B—C4B | 115.69 (17) |
O2A—N1A—C4A | 122.95 (16) | O2B—N1B—C4B | 123.42 (16) |
C5A—N2A—C2A | 121.06 (18) | C5B—N2B—C2B | 119.85 (18) |
C5A—N2A—H2NA | 115.1 (17) | C5B—N2B—H2NB | 116.7 (16) |
C2A—N2A—H2NA | 122.5 (17) | C2B—N2B—H2NB | 121.9 (16) |
O1A—C1A—N1A | 124.86 (19) | O3B—C4B—N1B | 123.95 (19) |
O1A—C1A—C2A | 128.27 (19) | O3B—C4B—C3B | 129.37 (19) |
N1A—C1A—C2A | 106.86 (16) | N1B—C4B—C3B | 106.66 (17) |
N2A—C2A—C1A | 112.50 (16) | C4B—C3B—C2B | 105.59 (16) |
N2A—C2A—C3A | 114.23 (17) | C4B—C3B—H31B | 110.6 |
C1A—C2A—C3A | 104.48 (16) | C2B—C3B—H31B | 110.6 |
N2A—C2A—H2A | 108.5 | C4B—C3B—H32B | 110.6 |
C1A—C2A—H2A | 108.5 | C2B—C3B—H32B | 110.6 |
C3A—C2A—H2A | 108.5 | H31B—C3B—H32B | 108.8 |
C4A—C3A—C2A | 105.74 (16) | N2B—C2B—C1B | 111.41 (16) |
C4A—C3A—H31A | 110.6 | N2B—C2B—C3B | 115.06 (17) |
C2A—C3A—H31A | 110.6 | C1B—C2B—C3B | 104.44 (16) |
C4A—C3A—H32A | 110.6 | N2B—C2B—H2B | 108.6 |
C2A—C3A—H32A | 110.6 | C1B—C2B—H2B | 108.6 |
H31A—C3A—H32A | 108.7 | C3B—C2B—H2B | 108.6 |
O3A—C4A—N1A | 124.09 (19) | O1B—C1B—N1B | 125.28 (19) |
O3A—C4A—C3A | 129.41 (19) | O1B—C1B—C2B | 127.77 (19) |
N1A—C4A—C3A | 106.49 (17) | N1B—C1B—C2B | 106.94 (16) |
O4A—C5A—N2A | 125.86 (19) | O4B—C5B—N2B | 124.96 (19) |
O4A—C5A—O5A | 123.79 (19) | O4B—C5B—O5B | 123.67 (19) |
N2A—C5A—O5A | 110.35 (18) | N2B—C5B—O5B | 111.33 (18) |
O5A—C6A—C7A | 111.40 (16) | O5B—C6B—C7B | 110.78 (15) |
O5A—C6A—H61A | 109.3 | O5B—C6B—H61B | 109.5 |
C7A—C6A—H61A | 109.3 | C7B—C6B—H61B | 109.5 |
O5A—C6A—H62A | 109.3 | O5B—C6B—H62B | 109.5 |
C7A—C6A—H62A | 109.3 | C7B—C6B—H62B | 109.5 |
H61A—C6A—H62A | 108.0 | H61B—C6B—H62B | 108.1 |
C12A—C7A—C8A | 118.85 (19) | C8B—C7B—C12B | 118.59 (18) |
C12A—C7A—C6A | 122.31 (18) | C8B—C7B—C6B | 120.21 (17) |
C8A—C7A—C6A | 118.79 (18) | C12B—C7B—C6B | 121.19 (18) |
C9A—C8A—C7A | 120.62 (19) | C9B—C8B—C7B | 121.10 (19) |
C9A—C8A—H8A | 119.7 | C9B—C8B—H8B | 119.4 |
C7A—C8A—H8A | 119.7 | C7B—C8B—H8B | 119.4 |
C10A—C9A—C8A | 119.8 (2) | C10B—C9B—C8B | 119.7 (2) |
C10A—C9A—H9A | 120.1 | C10B—C9B—H9B | 120.2 |
C8A—C9A—H9A | 120.1 | C8B—C9B—H9B | 120.2 |
C11A—C10A—C9A | 119.8 (2) | C9B—C10B—C11B | 120.1 (2) |
C11A—C10A—H10A | 120.1 | C9B—C10B—H10B | 120.0 |
C9A—C10A—H10A | 120.1 | C11B—C10B—H10B | 120.0 |
C10A—C11A—C12A | 120.5 (2) | C12B—C11B—C10B | 120.4 (2) |
C10A—C11A—H11A | 119.7 | C12B—C11B—H11B | 119.8 |
C12A—C11A—H11A | 119.7 | C10B—C11B—H11B | 119.8 |
C7A—C12A—C11A | 120.4 (2) | C11B—C12B—C7B | 120.2 (2) |
C7A—C12A—H12A | 119.8 | C11B—C12B—H12B | 119.9 |
C11A—C12A—H12A | 119.8 | C7B—C12B—H12B | 119.9 |
O2A—N1A—C1A—O1A | 4.3 (3) | C1B—N1B—C4B—O3B | 178.1 (2) |
C4A—N1A—C1A—O1A | −172.5 (2) | O2B—N1B—C4B—O3B | 0.6 (3) |
O2A—N1A—C1A—C2A | −174.98 (16) | C1B—N1B—C4B—C3B | −0.6 (2) |
C4A—N1A—C1A—C2A | 8.2 (2) | O2B—N1B—C4B—C3B | −178.04 (17) |
C5A—N2A—C2A—C1A | −89.0 (2) | O3B—C4B—C3B—C2B | 176.7 (2) |
C5A—N2A—C2A—C3A | 152.09 (18) | N1B—C4B—C3B—C2B | −4.7 (2) |
O1A—C1A—C2A—N2A | 48.1 (3) | C5B—N2B—C2B—C1B | −92.2 (2) |
N1A—C1A—C2A—N2A | −132.62 (18) | C5B—N2B—C2B—C3B | 149.15 (18) |
O1A—C1A—C2A—C3A | 172.6 (2) | C4B—C3B—C2B—N2B | 130.09 (18) |
N1A—C1A—C2A—C3A | −8.2 (2) | C4B—C3B—C2B—C1B | 7.6 (2) |
N2A—C2A—C3A—C4A | 128.98 (18) | O2B—N1B—C1B—O1B | 2.0 (3) |
C1A—C2A—C3A—C4A | 5.6 (2) | C4B—N1B—C1B—O1B | −175.6 (2) |
C1A—N1A—C4A—O3A | 174.9 (2) | O2B—N1B—C1B—C2B | −176.80 (16) |
O2A—N1A—C4A—O3A | −1.9 (3) | C4B—N1B—C1B—C2B | 5.7 (2) |
C1A—N1A—C4A—C3A | −4.4 (2) | N2B—C2B—C1B—O1B | 48.4 (3) |
O2A—N1A—C4A—C3A | 178.82 (17) | C3B—C2B—C1B—O1B | 173.2 (2) |
C2A—C3A—C4A—O3A | 179.5 (2) | N2B—C2B—C1B—N1B | −132.85 (18) |
C2A—C3A—C4A—N1A | −1.3 (2) | C3B—C2B—C1B—N1B | −8.0 (2) |
C2A—N2A—C5A—O4A | −5.1 (3) | C2B—N2B—C5B—O4B | −3.3 (3) |
C2A—N2A—C5A—O5A | 175.89 (17) | C2B—N2B—C5B—O5B | 179.04 (16) |
C6A—O5A—C5A—O4A | −10.9 (3) | C6B—O5B—C5B—O4B | −6.3 (3) |
C6A—O5A—C5A—N2A | 168.10 (16) | C6B—O5B—C5B—N2B | 171.47 (16) |
C5A—O5A—C6A—C7A | −83.3 (2) | C5B—O5B—C6B—C7B | −93.0 (2) |
O5A—C6A—C7A—C12A | −16.1 (3) | O5B—C6B—C7B—C8B | −117.6 (2) |
O5A—C6A—C7A—C8A | 166.63 (17) | O5B—C6B—C7B—C12B | 62.9 (3) |
C12A—C7A—C8A—C9A | 0.7 (3) | C12B—C7B—C8B—C9B | −0.9 (3) |
C6A—C7A—C8A—C9A | 178.00 (18) | C6B—C7B—C8B—C9B | 179.54 (19) |
C7A—C8A—C9A—C10A | −0.6 (3) | C7B—C8B—C9B—C10B | −0.1 (3) |
C8A—C9A—C10A—C11A | 0.1 (3) | C8B—C9B—C10B—C11B | 1.3 (3) |
C9A—C10A—C11A—C12A | 0.3 (3) | C9B—C10B—C11B—C12B | −1.4 (3) |
C8A—C7A—C12A—C11A | −0.3 (3) | C10B—C11B—C12B—C7B | 0.4 (3) |
C6A—C7A—C12A—C11A | −177.5 (2) | C8B—C7B—C12B—C11B | 0.8 (3) |
C10A—C11A—C12A—C7A | −0.2 (3) | C6B—C7B—C12B—C11B | −179.72 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2A—H1A···O4Bi | 0.87 (3) | 1.80 (3) | 2.667 (2) | 173 (3) |
N2A—H2NA···O2Bi | 0.84 (3) | 2.39 (3) | 3.184 (3) | 158 (2) |
N2A—H2NA···O1Bi | 0.84 (3) | 2.47 (2) | 3.000 (3) | 122 (2) |
O2B—H1B···O4A | 0.80 (3) | 1.90 (3) | 2.689 (2) | 172 (3) |
N2B—H2NB···O2A | 0.84 (3) | 2.43 (3) | 3.237 (3) | 162 (2) |
C2A—H2A···O3Aii | 1.00 | 2.39 | 3.004 (3) | 119 |
C2B—H2B···O3Biii | 1.00 | 2.43 | 3.035 (3) | 118 |
Symmetry codes: (i) x, y−1, z; (ii) −x+2, y+1/2, −z+1; (iii) −x+1, y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H12N2O5 |
Mr | 264.24 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 100 |
a, b, c (Å) | 12.910 (3), 7.077 (4), 14.001 (3) |
β (°) | 111.67 (3) |
V (Å3) | 1188.8 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.28 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Oxford KM4 CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17662, 3640, 3070 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.083, 1.00 |
No. of reflections | 3640 |
No. of parameters | 355 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.22 |
Computer programs: KM-4 CCD Software (Oxford Diffraction, 2004), KM-4 CCD Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Bruker, 1998), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O2A—H1A···O4Bi | 0.87 (3) | 1.80 (3) | 2.667 (2) | 173 (3) |
N2A—H2NA···O2Bi | 0.84 (3) | 2.39 (3) | 3.184 (3) | 158 (2) |
N2A—H2NA···O1Bi | 0.84 (3) | 2.47 (2) | 3.000 (3) | 122 (2) |
O2B—H1B···O4A | 0.80 (3) | 1.90 (3) | 2.689 (2) | 172 (3) |
N2B—H2NB···O2A | 0.84 (3) | 2.43 (3) | 3.237 (3) | 162 (2) |
C2A—H2A···O3Aii | 1.00 | 2.39 | 3.004 (3) | 119.1 |
C2B—H2B···O3Biii | 1.00 | 2.43 | 3.035 (3) | 118.3 |
Symmetry codes: (i) x, y−1, z; (ii) −x+2, y+1/2, −z+1; (iii) −x+1, y+1/2, −z+1. |
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The title compound, (I), is a cyclic derivative of L-aspartic acid and belongs to the group of chiral N-hydroxysuccinimides. With the aim of synthesizing a new class of L-aspartic acid-based sulfonic esters of N-hydroxysuccinimides, we obtained (I) by reacting hydroxylamine with Cbz-L-aspartic acid anhydride (Cbz is carbobenzoxy) in a water–dioxane system. As part of our studies of N-oxysuccinimide ring geometry (Stefanowicz et al. 2005, 2006), we report here the molecular and supramolecular structure of (I), which offers a wide range of intermolecular interactions, such as classical N—H···O and O—H···O hydrogen bonds, short carbonyl–carbonyl O···C interactions, and C—H···O and C—H···π(arene) contacts.
Compound (I) crystallizes in the space group P21 with two independent molecules in the asymmetric unit, A and B (Fig. 1). Superposition of these two molecules is shown in Fig. 2. They differ mainly in the orientation of the benzyl moiety, with the O5—C6—C7—C8 torsion angles being 166.6 (2) and -117.6 (2)° for molecules A and B, respectively. Atoms N1 of molecules A and B are characterized by planar geometry, with deviations from the plane defined by atoms C1/C4/O2 of 0.023 (2) and 0.019 (2) Å, respectively. Comparison of these values with the data available for analogous compounds such as N-hydroxysuccinimide [0.061 (2) Å; Jones, 2003] and N-hydroxyphtalimide [0.108 (6) Å; Miao et al., 1995] indicates increased sp2 character of the succinimide N atom for (I). The succinimide ring geometry of (I) is also slightly puckered compared with the virtually planar geometries of the N-hydroxyphtalimide and N-hydroxysuccinimide five-membered rings, which both have r.m.s. deviations of less than 0.02 Å. This difference can be explained by the substitution of atoms C2A/B by an aminobenzocarboxy moiety in (I), while in the other two compounds, both aromatic or methylene C atoms are geometrically equal. The puckering parameters (Cremer & Pople, 1975) for (I) are q2 = 0.079 (2) Å and ψ2 = 227 (1)° for molecule A, and q2 = 0.081 (2) Å and ψ2 = 251 (1)° for molecule B, indicating a twisted conformation on C1A—C2A and an approximate envelope conformation at C2B for the five-membered rings of molecules A and B, respectively.
The hydrogen-bond network is built up from the combination of three N—H···O and two O—H···O hydrogen bonds that link molecules A with neighbouring molecules B to form one-dimensional substructural ribbon motifs, augmented by short C═O···C═O carbonyl–carbonyl interactions between adjacent succinimide rings (Fig. 3). The strength of the C═ O···C═O interactions can be compared with medium-strength hydrogen bonds (Allen et al., 1998). Adjacent ribbons are linked via chains of C—H···O contacts between molecules of the same type to form two-dimensional sheets (Fig. 4). Only short C—H···π(arene) interactions link neighbouring sheets, generating a three-dimensional complex network (Fig. 5).
Atoms N2B and O2B from molecule B act as hydrogen-bond donors to atoms O2A and O4A from molecule A, respectively. The combination of these two hydrogen bonds gives an R22(14) ring (Bernstein et al., 1995). Atom O2A also acts as a hydrogen-bond donor to atom O4B of a neighbouring molecule at (x, y - 1, z), and atom N2A is a hydrogen-bond donor to atoms O1B and O2B, both at (x, y - 1, z), so R22(13), R22(14) and R21(5) ring motifs are generated (Fig. 3). Propagation of these motifs by simple translation along the b axis gives a one-dimensional substructural ribbon motif, which is additionally supported by C═O···C═O interactions between adjacent A and B molecules, e.g. O1A···C1B [2.848 (2) Å] and O1A···C4B [3.074 (2) Å], and O1Bi···C1A [3.028 (2) Å] and O1Bi···C4A [2.938 (2) Å] (Fig. 3). These contacts do not occur in the crystal structures of N-hydroxyphtalimide (Miao et al., 1995) and N-hydroxysuccinimide (Jones, 2003). Atoms C2A and C2B act as hydrogen-bond donors to atoms O3Aii and O3Biii, respectively, both linking molecules of the same type from adjacent ribbons (Fig. 4). Propagation of these short C—H···O contacts by a 21 screw axis (1/2, y, 1/2) and translation along the a axis generate a two-dimensional sheet of C—H···O chains linked into ribbons in the ab plane. Adjacent sheets are linked via C—H···π (arene) interactions (Fig. 5), with C6A···π(arene)iv and C6B···π(arene)v distances of 3.401 (2) and 3.428 (2) Å, respectively, providing a complex three-dimensional framework.
It is worth mentioning that the characteristic C(5) motif of the O—H···O hydrogen-bonding combination in simple N-hydroxyimides (Miao et al., 1995; Jones, 2003) is absent from the structure of (I). The hydrogen-bonding geometry is listed in Table 1.