Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105035134/gd1417sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105035134/gd1417Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105035134/gd1417IIsup3.hkl |
CCDC references: 294333; 294334
Under a nitrogen atmosphere, small portions of iodosylbenzene diacetate (3.865 g, 12 mmol) were added at room temperature to a solution of 2-isopropyl-4,7-dihydro-1,3-dioxepine (2.560 g, 18 mmol) and N-aminosuccinimide (1.141 g, 10 mmol) in dry acetonitrile (30 ml) over a period of 2.5 h. After stirring for a further 15 h, the reaction mixture was evaporated under reduced pressure. The oily residue was purified by column chromatography (silica gel, cyclohexane 100 → ethylacetate–cyclohexane: 80:20) to give the separated isomers, (I) and (II), as colourless solids (total yield 1.602 g, 6.3 mmol, 63%). Single crystals of isomer (I) (exo) for X-ray diffraction studies were obtained by slow evaporation from acetone (m.p. 413–415 K). Spectroscopic analysis: 1H NMR (500 MHz, CDCl3, δ, p.p.m.): 0.90 [d, 6H, J = 6.84 Hz, CH(CH3)2], 1.84 [m, 1H, CH(CH3)2], 2.63 [s, 4H, CO—(CH2)2—CO], 2.82 (m, 2H, CH—N), 3.84 (m, 2H, O—CH2), 4.12 (d, 1H, J = 6.84 Hz, O—CHR—O), 4.56 (m, 2H, O—CH2); 13C NMR (125 MHz, CDCl3, δ, p.p.m.): 172.45 (2 C, CO), 112.42 (1 C, O—CHR—O), 66.64 (2 C, O—CH2), 47.46 (2 C, CH—N), 31.56 [1 C, CH(CH3)2], 26.46 [2 C, CO-(CH2)2-CO], 17.74 [2 C, CH(CH3)2]. Single crystals of isomer (II) (endo) for X-ray diffraction studies were obtained by recrystallization from diethyl ether–acetone (Ratio?) at 253 K (m.p. 415–417 K). Spectroscopic analysis: 1H NMR (500 MHz, CDCl3, δ, p.p.m.): 0.88 [d, 6H, J = 6.88 Hz, CH(CH3)2], 1.83 [m, 1H, CH(CH3)2], 2.62 [s, 4H, CO—(CH2)2—CO], 2.71 (m, 2H, CH—N), 3.94 (d, 1H, J = 6.83 Hz, O—CHR—O), 3.98 (m, 2H, O—CH2), 4.62 (m, 2H, O—CH2); 13C NMR (125 MHz, CDCl3, δ, p.p.m.): 172.70 (2 C, CO), 111.28 (1 C, O—CHR—O), 65.36 (2 C, O—CH2), 48.15 (2 C, CH—N), 32.23 [1 C, CH(CH3)2], 26.60 [2 C, CO—(CH2)2—CO], 17.72 [2 C, CH(CH3)2]. APCI-MS, mixture of isomers: m/z (%) = 255 (100) [M+H]+; 287 (21) [M+H+MeOH]+.
H atoms were treated as riding, with C—H distances in the range 0.98–1.00 Å and Uiso(H) = 1.2Ueq(C). [Please check added text] The Friedel-equivalent reflections were merged.
For both compounds, data collection: Please provide missing details; cell refinement: Please provide missing details; data reduction: Please provide missing details; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Please provide missing details; software used to prepare material for publication: Please provide missing details.
C12H18N2O4 | F(000) = 272 |
Mr = 254.28 | Dx = 1.363 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 7302 reflections |
a = 6.1449 (11) Å | θ = 1.6–26.0° |
b = 7.8343 (10) Å | µ = 0.10 mm−1 |
c = 13.080 (3) Å | T = 153 K |
β = 100.250 (15)° | Plate, colourless |
V = 619.6 (2) Å3 | 0.47 × 0.41 × 0.05 mm |
Z = 2 |
Stoe IPDS 2 diffractometer | 1244 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 998 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.057 |
Detector resolution: 6.67 pixels mm-1 | θmax = 25.5°, θmin = 1.6° |
rotation scans | h = −7→7 |
Absorption correction: integration X-RED32 (Stoe & Cie, 2004) | k = −9→9 |
Tmin = 0.954, Tmax = 0.995 | l = −15→15 |
8393 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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.044P)2] where P = (Fo2 + 2Fc2)/3 |
1244 reflections | (Δ/σ)max = 0.004 |
165 parameters | Δρmax = 0.14 e Å−3 |
1 restraint | Δρmin = −0.21 e Å−3 |
C12H18N2O4 | V = 619.6 (2) Å3 |
Mr = 254.28 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.1449 (11) Å | µ = 0.10 mm−1 |
b = 7.8343 (10) Å | T = 153 K |
c = 13.080 (3) Å | 0.47 × 0.41 × 0.05 mm |
β = 100.250 (15)° |
Stoe IPDS 2 diffractometer | 1244 independent reflections |
Absorption correction: integration X-RED32 (Stoe & Cie, 2004) | 998 reflections with I > 2σ(I) |
Tmin = 0.954, Tmax = 0.995 | Rint = 0.057 |
8393 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 1 restraint |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.14 e Å−3 |
1244 reflections | Δρmin = −0.21 e Å−3 |
165 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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.1562 (5) | 0.8397 (4) | 0.6551 (2) | 0.0359 (7) | |
H1A | 0.2998 | 0.8933 | 0.6500 | 0.043* | |
H1B | 0.1719 | 0.7149 | 0.6472 | 0.043* | |
C2 | 0.1003 (5) | 0.8771 (4) | 0.7606 (2) | 0.0310 (6) | |
H2A | 0.1520 | 0.9890 | 0.7930 | 0.037* | |
C3 | −0.1000 (4) | 0.8033 (4) | 0.7901 (2) | 0.0314 (6) | |
H3A | −0.1692 | 0.8701 | 0.8411 | 0.038* | |
C4 | −0.2544 (5) | 0.6976 (4) | 0.7130 (2) | 0.0345 (7) | |
H4B | −0.1758 | 0.5945 | 0.6951 | 0.041* | |
H4A | −0.3809 | 0.6599 | 0.7448 | 0.041* | |
C5 | −0.1931 (4) | 0.7912 (4) | 0.5452 (2) | 0.0314 (6) | |
H5A | −0.1396 | 0.6725 | 0.5364 | 0.038* | |
C6 | −0.3220 (5) | 0.8561 (4) | 0.4427 (2) | 0.0341 (6) | |
H6A | −0.3517 | 0.9805 | 0.4504 | 0.041* | |
C7 | −0.1823 (5) | 0.8357 (4) | 0.3577 (2) | 0.0403 (7) | |
H7A | −0.1594 | 0.7141 | 0.3457 | 0.048* | |
H7B | −0.0389 | 0.8916 | 0.3796 | 0.048* | |
H7C | −0.2592 | 0.8885 | 0.2933 | 0.048* | |
C8 | −0.5429 (5) | 0.7652 (4) | 0.4124 (2) | 0.0421 (8) | |
H8C | −0.6164 | 0.8051 | 0.3439 | 0.051* | |
H8B | −0.6364 | 0.7902 | 0.4639 | 0.051* | |
H8A | −0.5180 | 0.6418 | 0.4100 | 0.051* | |
C9 | 0.3970 (5) | 0.8568 (4) | 0.9687 (2) | 0.0357 (7) | |
C10 | 0.4386 (5) | 0.8615 (4) | 1.0854 (2) | 0.0403 (7) | |
H10A | 0.4573 | 0.9805 | 1.1109 | 0.048* | |
H10B | 0.5731 | 0.7958 | 1.1143 | 0.048* | |
C11 | 0.2335 (5) | 0.7804 (4) | 1.1162 (2) | 0.0398 (7) | |
H11B | 0.2757 | 0.6853 | 1.1656 | 0.048* | |
H11A | 0.1492 | 0.8658 | 1.1490 | 0.048* | |
C12 | 0.0983 (5) | 0.7156 (4) | 1.0165 (2) | 0.0354 (7) | |
N1 | 0.1217 (4) | 0.7252 (3) | 0.83085 (17) | 0.0313 (5) | |
N2 | 0.2005 (4) | 0.7706 (3) | 0.93619 (15) | 0.0299 (5) | |
O1 | 0.5120 (3) | 0.9170 (3) | 0.91070 (15) | 0.0453 (6) | |
O2 | −0.0704 (4) | 0.6317 (3) | 1.00440 (16) | 0.0455 (6) | |
O3 | −0.0102 (3) | 0.9024 (3) | 0.57294 (13) | 0.0347 (5) | |
O4 | −0.3350 (3) | 0.7922 (3) | 0.62015 (13) | 0.0341 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0300 (14) | 0.0462 (19) | 0.0319 (14) | 0.0004 (14) | 0.0061 (12) | −0.0008 (14) |
C2 | 0.0335 (15) | 0.0281 (15) | 0.0319 (14) | −0.0004 (13) | 0.0070 (11) | −0.0002 (13) |
C3 | 0.0298 (14) | 0.0342 (15) | 0.0304 (14) | 0.0046 (13) | 0.0061 (12) | 0.0005 (12) |
C4 | 0.0354 (17) | 0.0419 (18) | 0.0264 (15) | −0.0042 (13) | 0.0060 (12) | 0.0062 (12) |
C5 | 0.0313 (14) | 0.0350 (15) | 0.0297 (14) | −0.0041 (14) | 0.0100 (11) | −0.0007 (12) |
C6 | 0.0385 (15) | 0.0330 (15) | 0.0312 (14) | −0.0001 (14) | 0.0071 (12) | −0.0014 (13) |
C7 | 0.0489 (18) | 0.0394 (18) | 0.0337 (15) | 0.0013 (15) | 0.0105 (13) | 0.0011 (14) |
C8 | 0.0404 (18) | 0.048 (2) | 0.0363 (16) | −0.0014 (16) | 0.0033 (13) | 0.0020 (15) |
C9 | 0.0326 (15) | 0.0352 (16) | 0.0390 (15) | 0.0023 (14) | 0.0056 (13) | −0.0040 (14) |
C10 | 0.0422 (17) | 0.0441 (18) | 0.0325 (16) | −0.0001 (15) | 0.0008 (12) | −0.0032 (15) |
C11 | 0.0488 (18) | 0.0388 (17) | 0.0308 (14) | −0.0048 (16) | 0.0042 (13) | −0.0029 (14) |
C12 | 0.0452 (19) | 0.0292 (15) | 0.0311 (15) | 0.0009 (15) | 0.0048 (13) | 0.0017 (13) |
N1 | 0.0355 (13) | 0.0292 (12) | 0.0289 (12) | 0.0022 (10) | 0.0045 (10) | −0.0009 (10) |
N2 | 0.0345 (13) | 0.0311 (13) | 0.0235 (11) | −0.0004 (11) | 0.0031 (10) | −0.0034 (11) |
O1 | 0.0347 (11) | 0.0612 (14) | 0.0418 (12) | −0.0036 (11) | 0.0113 (10) | −0.0026 (11) |
O2 | 0.0491 (14) | 0.0462 (13) | 0.0404 (11) | −0.0146 (12) | 0.0059 (10) | 0.0044 (11) |
O3 | 0.0346 (11) | 0.0390 (12) | 0.0304 (10) | −0.0033 (10) | 0.0057 (8) | 0.0040 (9) |
O4 | 0.0307 (10) | 0.0428 (11) | 0.0295 (10) | 0.0019 (9) | 0.0072 (8) | 0.0045 (9) |
C1—O3 | 1.432 (3) | C6—H6A | 1.0000 |
C1—C2 | 1.509 (4) | C7—H7A | 0.9800 |
C1—H1A | 0.9900 | C7—H7B | 0.9800 |
C1—H1B | 0.9900 | C7—H7C | 0.9800 |
C2—C3 | 1.472 (4) | C8—H8C | 0.9800 |
C2—N1 | 1.495 (3) | C8—H8B | 0.9800 |
C2—H2A | 1.0000 | C8—H8A | 0.9800 |
C3—N1 | 1.502 (4) | C9—O1 | 1.219 (3) |
C3—C4 | 1.504 (4) | C9—N2 | 1.382 (4) |
C3—H3A | 1.0000 | C9—C10 | 1.503 (4) |
C4—O4 | 1.434 (3) | C10—C11 | 1.528 (4) |
C4—H4B | 0.9900 | C10—H10A | 0.9900 |
C4—H4A | 0.9900 | C10—H10B | 0.9900 |
C5—O3 | 1.417 (3) | C11—C12 | 1.504 (4) |
C5—O4 | 1.423 (3) | C11—H11B | 0.9900 |
C5—C6 | 1.519 (4) | C11—H11A | 0.9900 |
C5—H5A | 1.0000 | C12—O2 | 1.213 (3) |
C6—C8 | 1.521 (4) | C12—N2 | 1.385 (4) |
C6—C7 | 1.529 (4) | N1—N2 | 1.422 (3) |
O3—C1—C2 | 111.8 (2) | C6—C7—H7B | 109.5 |
O3—C1—H1A | 109.3 | H7A—C7—H7B | 109.5 |
C2—C1—H1A | 109.3 | C6—C7—H7C | 109.5 |
O3—C1—H1B | 109.3 | H7A—C7—H7C | 109.5 |
C2—C1—H1B | 109.3 | H7B—C7—H7C | 109.5 |
H1A—C1—H1B | 107.9 | C6—C8—H8C | 109.5 |
C3—C2—N1 | 60.83 (18) | C6—C8—H8B | 109.5 |
C3—C2—C1 | 120.0 (2) | H8C—C8—H8B | 109.5 |
N1—C2—C1 | 113.4 (2) | C6—C8—H8A | 109.5 |
C3—C2—H2A | 116.8 | H8C—C8—H8A | 109.5 |
N1—C2—H2A | 116.8 | H8B—C8—H8A | 109.5 |
C1—C2—H2A | 116.8 | O1—C9—N2 | 124.7 (3) |
C2—C3—N1 | 60.33 (17) | O1—C9—C10 | 127.5 (3) |
C2—C3—C4 | 119.8 (2) | N2—C9—C10 | 107.8 (2) |
N1—C3—C4 | 116.0 (2) | C9—C10—C11 | 104.9 (2) |
C2—C3—H3A | 116.3 | C9—C10—H10A | 110.8 |
N1—C3—H3A | 116.3 | C11—C10—H10A | 110.8 |
C4—C3—H3A | 116.3 | C9—C10—H10B | 110.8 |
O4—C4—C3 | 111.4 (2) | C11—C10—H10B | 110.8 |
O4—C4—H4B | 109.3 | H10A—C10—H10B | 108.8 |
C3—C4—H4B | 109.3 | C12—C11—C10 | 105.5 (2) |
O4—C4—H4A | 109.3 | C12—C11—H11B | 110.7 |
C3—C4—H4A | 109.3 | C10—C11—H11B | 110.7 |
H4B—C4—H4A | 108.0 | C12—C11—H11A | 110.7 |
O3—C5—O4 | 112.1 (2) | C10—C11—H11A | 110.7 |
O3—C5—C6 | 106.6 (2) | H11B—C11—H11A | 108.8 |
O4—C5—C6 | 108.6 (2) | O2—C12—N2 | 124.2 (3) |
O3—C5—H5A | 109.8 | O2—C12—C11 | 128.6 (3) |
O4—C5—H5A | 109.8 | N2—C12—C11 | 107.3 (3) |
C6—C5—H5A | 109.8 | N2—N1—C2 | 112.0 (2) |
C5—C6—C8 | 112.0 (2) | N2—N1—C3 | 111.9 (2) |
C5—C6—C7 | 109.6 (2) | C2—N1—C3 | 58.84 (17) |
C8—C6—C7 | 110.7 (2) | C9—N2—C12 | 114.1 (2) |
C5—C6—H6A | 108.2 | C9—N2—N1 | 123.2 (2) |
C8—C6—H6A | 108.2 | C12—N2—N1 | 122.3 (2) |
C7—C6—H6A | 108.2 | C5—O3—C1 | 114.2 (2) |
C6—C7—H7A | 109.5 | C5—O4—C4 | 114.8 (2) |
C12H18N2O4 | F(000) = 1088 |
Mr = 254.28 | Dx = 1.330 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 10318 reflections |
a = 24.470 (3) Å | θ = 1.7–25.6° |
b = 8.8444 (8) Å | µ = 0.10 mm−1 |
c = 11.8252 (14) Å | T = 153 K |
β = 97.119 (9)° | Plate, colourless |
V = 2539.6 (5) Å3 | 0.66 × 0.65 × 0.25 mm |
Z = 8 |
Stoe IPDS 2 diffractometer | 4465 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 2623 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.033 |
Detector resolution: 6.67 pixels mm-1 | θmax = 25.0°, θmin = 1.7° |
rotation scans | h = −29→29 |
Absorption correction: integration X-RED32 (Stoe & Cie, 2004) | k = −10→10 |
Tmin = 0.914, Tmax = 0.972 | l = −13→14 |
18062 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.084 | w = 1/[σ2(Fo2) + (0.0484P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.90 | (Δ/σ)max < 0.001 |
4465 reflections | Δρmax = 0.21 e Å−3 |
330 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0028 (4) |
C12H18N2O4 | V = 2539.6 (5) Å3 |
Mr = 254.28 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 24.470 (3) Å | µ = 0.10 mm−1 |
b = 8.8444 (8) Å | T = 153 K |
c = 11.8252 (14) Å | 0.66 × 0.65 × 0.25 mm |
β = 97.119 (9)° |
Stoe IPDS 2 diffractometer | 4465 independent reflections |
Absorption correction: integration X-RED32 (Stoe & Cie, 2004) | 2623 reflections with I > 2σ(I) |
Tmin = 0.914, Tmax = 0.972 | Rint = 0.033 |
18062 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 0.90 | Δρmax = 0.21 e Å−3 |
4465 reflections | Δρmin = −0.15 e Å−3 |
330 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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.13853 (6) | 0.1498 (2) | 0.37970 (13) | 0.0339 (4) | |
H1A | 0.1338 | 0.0495 | 0.3427 | 0.041* | |
H1B | 0.1604 | 0.2128 | 0.3327 | 0.041* | |
C2 | 0.08288 (6) | 0.22056 (18) | 0.37812 (14) | 0.0284 (4) | |
H2A | 0.0625 | 0.2297 | 0.2997 | 0.034* | |
C3 | 0.06445 (6) | 0.33025 (18) | 0.45939 (13) | 0.0269 (4) | |
H3A | 0.0343 | 0.3984 | 0.4248 | 0.032* | |
C4 | 0.09820 (6) | 0.39655 (18) | 0.56193 (13) | 0.0302 (4) | |
H4B | 0.1149 | 0.4918 | 0.5387 | 0.036* | |
H4A | 0.0732 | 0.4228 | 0.6186 | 0.036* | |
C5 | 0.18282 (6) | 0.26653 (17) | 0.54868 (13) | 0.0274 (4) | |
H5A | 0.1868 | 0.3502 | 0.4934 | 0.033* | |
C6 | 0.23653 (7) | 0.24463 (19) | 0.62595 (15) | 0.0335 (4) | |
H6A | 0.2313 | 0.1617 | 0.6811 | 0.040* | |
C7 | 0.28230 (7) | 0.1981 (2) | 0.55652 (17) | 0.0496 (5) | |
H7A | 0.2880 | 0.2782 | 0.5020 | 0.060* | |
H7B | 0.2719 | 0.1043 | 0.5152 | 0.060* | |
H7C | 0.3164 | 0.1818 | 0.6078 | 0.060* | |
C8 | 0.25272 (7) | 0.3879 (2) | 0.69348 (14) | 0.0403 (4) | |
H8A | 0.2229 | 0.4171 | 0.7372 | 0.048* | |
H8B | 0.2594 | 0.4696 | 0.6409 | 0.048* | |
H8C | 0.2863 | 0.3692 | 0.7458 | 0.048* | |
C9 | −0.02191 (7) | 0.04486 (18) | 0.32502 (13) | 0.0291 (4) | |
C10 | −0.08362 (6) | 0.04812 (19) | 0.29875 (14) | 0.0332 (4) | |
H10A | −0.0992 | −0.0543 | 0.3057 | 0.040* | |
H10B | −0.0948 | 0.0859 | 0.2205 | 0.040* | |
C11 | −0.10334 (7) | 0.15492 (19) | 0.38645 (14) | 0.0352 (4) | |
H11B | −0.1242 | 0.2404 | 0.3482 | 0.042* | |
H11A | −0.1274 | 0.1009 | 0.4344 | 0.042* | |
C12 | −0.05208 (7) | 0.21086 (18) | 0.45773 (14) | 0.0290 (4) | |
C13 | 0.40029 (6) | 0.88727 (18) | 0.43325 (13) | 0.0295 (4) | |
H13A | 0.3829 | 0.9826 | 0.4541 | 0.035* | |
H13B | 0.4260 | 0.9128 | 0.3776 | 0.035* | |
C14 | 0.43315 (6) | 0.82396 (18) | 0.53816 (13) | 0.0269 (4) | |
H14A | 0.4622 | 0.8944 | 0.5743 | 0.032* | |
C15 | 0.41454 (6) | 0.71207 (18) | 0.61837 (13) | 0.0277 (4) | |
H15A | 0.4339 | 0.7225 | 0.6975 | 0.033* | |
C16 | 0.35980 (6) | 0.6350 (2) | 0.61452 (12) | 0.0316 (4) | |
H16B | 0.3660 | 0.5331 | 0.6484 | 0.038* | |
H16A | 0.3372 | 0.6924 | 0.6636 | 0.038* | |
C17 | 0.31634 (7) | 0.75532 (17) | 0.44628 (13) | 0.0270 (4) | |
H17A | 0.3132 | 0.8384 | 0.5025 | 0.032* | |
C18 | 0.26201 (7) | 0.73858 (18) | 0.36962 (15) | 0.0322 (4) | |
H18A | 0.2577 | 0.8290 | 0.3185 | 0.039* | |
C19 | 0.26088 (7) | 0.5990 (2) | 0.29422 (14) | 0.0411 (4) | |
H19A | 0.2618 | 0.5080 | 0.3417 | 0.049* | |
H19B | 0.2930 | 0.5999 | 0.2522 | 0.049* | |
H19C | 0.2271 | 0.5993 | 0.2402 | 0.049* | |
C20 | 0.21412 (7) | 0.7386 (2) | 0.44041 (17) | 0.0441 (5) | |
H20C | 0.1794 | 0.7304 | 0.3898 | 0.053* | |
H20B | 0.2144 | 0.8329 | 0.4840 | 0.053* | |
H20A | 0.2178 | 0.6525 | 0.4930 | 0.053* | |
C21 | 0.55121 (7) | 0.71403 (18) | 0.54804 (14) | 0.0288 (4) | |
C22 | 0.60214 (7) | 0.6605 (2) | 0.62166 (15) | 0.0358 (4) | |
H22A | 0.6218 | 0.7467 | 0.6616 | 0.043* | |
H22B | 0.6274 | 0.6090 | 0.5749 | 0.043* | |
C23 | 0.58212 (6) | 0.55098 (19) | 0.70676 (14) | 0.0337 (4) | |
H23A | 0.5988 | 0.4499 | 0.7000 | 0.040* | |
H23B | 0.5919 | 0.5881 | 0.7857 | 0.040* | |
C24 | 0.52063 (6) | 0.54374 (18) | 0.67696 (13) | 0.0284 (4) | |
N1 | 0.04750 (5) | 0.16772 (14) | 0.46420 (10) | 0.0262 (3) | |
N2 | −0.00770 (5) | 0.14746 (14) | 0.41301 (10) | 0.0265 (3) | |
N3 | 0.45186 (5) | 0.66313 (14) | 0.53454 (10) | 0.0257 (3) | |
N4 | 0.50663 (5) | 0.64627 (14) | 0.58886 (10) | 0.0256 (3) | |
O1 | 0.01112 (5) | −0.02834 (13) | 0.27952 (9) | 0.0359 (3) | |
O2 | −0.04824 (5) | 0.29651 (13) | 0.53843 (10) | 0.0366 (3) | |
O3 | 0.16959 (4) | 0.13044 (12) | 0.48916 (8) | 0.0310 (3) | |
O4 | 0.14114 (4) | 0.30286 (12) | 0.61645 (8) | 0.0291 (3) | |
O5 | 0.54759 (5) | 0.80150 (13) | 0.46811 (10) | 0.0367 (3) | |
O6 | 0.48765 (4) | 0.46768 (13) | 0.72011 (9) | 0.0360 (3) | |
O7 | 0.35839 (4) | 0.79079 (12) | 0.37859 (8) | 0.0290 (3) | |
O8 | 0.32862 (4) | 0.61822 (12) | 0.50495 (8) | 0.0285 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0327 (9) | 0.0431 (11) | 0.0256 (8) | −0.0001 (8) | 0.0026 (7) | −0.0043 (7) |
C2 | 0.0280 (9) | 0.0323 (9) | 0.0245 (8) | −0.0021 (7) | 0.0025 (7) | 0.0017 (7) |
C3 | 0.0273 (9) | 0.0253 (8) | 0.0277 (8) | −0.0012 (7) | 0.0021 (7) | 0.0023 (7) |
C4 | 0.0285 (8) | 0.0296 (9) | 0.0322 (9) | 0.0027 (8) | 0.0025 (7) | −0.0020 (7) |
C5 | 0.0272 (8) | 0.0275 (9) | 0.0275 (9) | −0.0015 (7) | 0.0031 (7) | 0.0017 (7) |
C6 | 0.0315 (9) | 0.0331 (10) | 0.0348 (10) | −0.0024 (7) | 0.0006 (7) | 0.0060 (7) |
C7 | 0.0306 (10) | 0.0551 (13) | 0.0618 (13) | 0.0070 (9) | 0.0002 (9) | −0.0058 (10) |
C8 | 0.0321 (8) | 0.0484 (11) | 0.0396 (9) | −0.0089 (8) | 0.0021 (7) | 0.0000 (8) |
C9 | 0.0330 (9) | 0.0267 (9) | 0.0272 (9) | −0.0019 (8) | 0.0021 (7) | 0.0010 (7) |
C10 | 0.0285 (9) | 0.0352 (10) | 0.0346 (9) | −0.0015 (8) | −0.0013 (7) | −0.0014 (7) |
C11 | 0.0287 (9) | 0.0338 (10) | 0.0426 (10) | 0.0033 (8) | 0.0022 (7) | −0.0018 (7) |
C12 | 0.0302 (9) | 0.0267 (9) | 0.0305 (9) | 0.0012 (7) | 0.0053 (7) | 0.0029 (7) |
C13 | 0.0308 (9) | 0.0284 (9) | 0.0290 (8) | −0.0033 (8) | 0.0028 (7) | 0.0015 (7) |
C14 | 0.0269 (9) | 0.0257 (9) | 0.0282 (9) | −0.0014 (7) | 0.0043 (7) | −0.0035 (7) |
C15 | 0.0297 (9) | 0.0327 (9) | 0.0208 (8) | 0.0023 (7) | 0.0026 (7) | −0.0007 (7) |
C16 | 0.0276 (8) | 0.0439 (11) | 0.0231 (8) | −0.0020 (7) | 0.0024 (6) | 0.0034 (7) |
C17 | 0.0283 (9) | 0.0256 (9) | 0.0275 (9) | 0.0012 (7) | 0.0045 (7) | −0.0016 (6) |
C18 | 0.0297 (9) | 0.0302 (10) | 0.0350 (10) | 0.0007 (7) | −0.0031 (7) | 0.0006 (7) |
C19 | 0.0391 (9) | 0.0425 (10) | 0.0389 (9) | −0.0016 (8) | −0.0059 (7) | −0.0065 (8) |
C20 | 0.0293 (9) | 0.0461 (12) | 0.0561 (12) | 0.0022 (8) | 0.0018 (8) | −0.0037 (8) |
C21 | 0.0294 (9) | 0.0269 (9) | 0.0305 (9) | −0.0022 (7) | 0.0052 (7) | −0.0041 (7) |
C22 | 0.0268 (9) | 0.0369 (10) | 0.0433 (10) | −0.0032 (8) | 0.0023 (7) | 0.0009 (8) |
C23 | 0.0300 (9) | 0.0357 (10) | 0.0343 (9) | 0.0012 (8) | −0.0006 (7) | 0.0019 (7) |
C24 | 0.0286 (9) | 0.0281 (9) | 0.0286 (9) | −0.0001 (7) | 0.0032 (7) | −0.0016 (7) |
N1 | 0.0246 (7) | 0.0275 (7) | 0.0261 (7) | −0.0008 (6) | 0.0015 (5) | 0.0013 (5) |
N2 | 0.0253 (7) | 0.0268 (8) | 0.0267 (7) | 0.0001 (6) | 0.0004 (5) | 0.0001 (5) |
N3 | 0.0244 (7) | 0.0273 (7) | 0.0251 (7) | 0.0003 (6) | 0.0016 (5) | −0.0019 (5) |
N4 | 0.0229 (7) | 0.0263 (8) | 0.0272 (7) | −0.0017 (6) | 0.0017 (5) | −0.0007 (5) |
O1 | 0.0332 (7) | 0.0366 (7) | 0.0377 (7) | 0.0031 (6) | 0.0030 (5) | −0.0079 (5) |
O2 | 0.0392 (7) | 0.0354 (7) | 0.0355 (7) | 0.0037 (6) | 0.0062 (5) | −0.0055 (5) |
O3 | 0.0302 (6) | 0.0304 (6) | 0.0314 (6) | 0.0013 (5) | 0.0004 (5) | −0.0010 (5) |
O4 | 0.0281 (6) | 0.0346 (6) | 0.0246 (6) | 0.0008 (5) | 0.0035 (5) | 0.0006 (5) |
O5 | 0.0377 (7) | 0.0366 (7) | 0.0364 (7) | −0.0050 (6) | 0.0074 (5) | 0.0052 (6) |
O6 | 0.0329 (7) | 0.0368 (7) | 0.0380 (7) | −0.0040 (6) | 0.0034 (5) | 0.0075 (5) |
O7 | 0.0289 (6) | 0.0333 (6) | 0.0247 (6) | −0.0041 (5) | 0.0022 (5) | −0.0009 (5) |
O8 | 0.0288 (6) | 0.0296 (6) | 0.0263 (6) | −0.0012 (5) | −0.0001 (4) | 0.0025 (5) |
C1—O3 | 1.4279 (18) | C13—C14 | 1.501 (2) |
C1—C2 | 1.497 (2) | C13—H13A | 0.9900 |
C1—H1A | 0.9900 | C13—H13B | 0.9900 |
C1—H1B | 0.9900 | C14—C15 | 1.481 (2) |
C2—C3 | 1.475 (2) | C14—N3 | 1.497 (2) |
C2—N1 | 1.4908 (19) | C14—H14A | 1.0000 |
C2—H2A | 1.0000 | C15—N3 | 1.4928 (19) |
C3—N1 | 1.499 (2) | C15—C16 | 1.499 (2) |
C3—C4 | 1.499 (2) | C15—H15A | 1.0000 |
C3—H3A | 1.0000 | C16—O8 | 1.4276 (17) |
C4—O4 | 1.4277 (18) | C16—H16B | 0.9900 |
C4—H4B | 0.9900 | C16—H16A | 0.9900 |
C4—H4A | 0.9900 | C17—O8 | 1.4108 (18) |
C5—O4 | 1.4101 (18) | C17—O7 | 1.4149 (18) |
C5—O3 | 1.4115 (18) | C17—C18 | 1.521 (2) |
C5—C6 | 1.517 (2) | C17—H17A | 1.0000 |
C5—H5A | 1.0000 | C18—C19 | 1.521 (2) |
C6—C8 | 1.524 (2) | C18—C20 | 1.522 (2) |
C6—C7 | 1.525 (2) | C18—H18A | 1.0000 |
C6—H6A | 1.0000 | C19—H19A | 0.9800 |
C7—H7A | 0.9800 | C19—H19B | 0.9800 |
C7—H7B | 0.9800 | C19—H19C | 0.9800 |
C7—H7C | 0.9800 | C20—H20C | 0.9800 |
C8—H8A | 0.9800 | C20—H20B | 0.9800 |
C8—H8B | 0.9800 | C20—H20A | 0.9800 |
C8—H8C | 0.9800 | C21—O5 | 1.2161 (19) |
C9—O1 | 1.2125 (18) | C21—N4 | 1.383 (2) |
C9—N2 | 1.392 (2) | C21—C22 | 1.506 (2) |
C9—C10 | 1.504 (2) | C22—C23 | 1.521 (2) |
C10—C11 | 1.525 (2) | C22—H22A | 0.9900 |
C10—H10A | 0.9900 | C22—H22B | 0.9900 |
C10—H10B | 0.9900 | C23—C24 | 1.504 (2) |
C11—C12 | 1.506 (2) | C23—H23A | 0.9900 |
C11—H11B | 0.9900 | C23—H23B | 0.9900 |
C11—H11A | 0.9900 | C24—O6 | 1.2109 (18) |
C12—O2 | 1.2129 (19) | C24—N4 | 1.3915 (19) |
C12—N2 | 1.384 (2) | N1—N2 | 1.4215 (17) |
C13—O7 | 1.4259 (18) | N3—N4 | 1.4205 (17) |
O3—C1—C2 | 116.29 (13) | N3—C14—C13 | 117.74 (12) |
O3—C1—H1A | 108.2 | C15—C14—H14A | 113.6 |
C2—C1—H1A | 108.2 | N3—C14—H14A | 113.6 |
O3—C1—H1B | 108.2 | C13—C14—H14A | 113.6 |
C2—C1—H1B | 108.2 | C14—C15—N3 | 60.43 (10) |
H1A—C1—H1B | 107.4 | C14—C15—C16 | 128.99 (13) |
C3—C2—N1 | 60.72 (10) | N3—C15—C16 | 117.77 (13) |
C3—C2—C1 | 128.17 (14) | C14—C15—H15A | 112.9 |
N1—C2—C1 | 117.71 (13) | N3—C15—H15A | 112.9 |
C3—C2—H2A | 113.2 | C16—C15—H15A | 112.9 |
N1—C2—H2A | 113.2 | O8—C16—C15 | 116.74 (12) |
C1—C2—H2A | 113.2 | O8—C16—H16B | 108.1 |
C2—C3—N1 | 60.16 (10) | C15—C16—H16B | 108.1 |
C2—C3—C4 | 127.00 (13) | O8—C16—H16A | 108.1 |
N1—C3—C4 | 118.14 (12) | C15—C16—H16A | 108.1 |
C2—C3—H3A | 113.6 | H16B—C16—H16A | 107.3 |
N1—C3—H3A | 113.6 | O8—C17—O7 | 110.08 (12) |
C4—C3—H3A | 113.6 | O8—C17—C18 | 109.06 (13) |
O4—C4—C3 | 116.04 (13) | O7—C17—C18 | 109.13 (13) |
O4—C4—H4B | 108.3 | O8—C17—H17A | 109.5 |
C3—C4—H4B | 108.3 | O7—C17—H17A | 109.5 |
O4—C4—H4A | 108.3 | C18—C17—H17A | 109.5 |
C3—C4—H4A | 108.3 | C17—C18—C19 | 112.30 (13) |
H4B—C4—H4A | 107.4 | C17—C18—C20 | 110.36 (14) |
O4—C5—O3 | 109.90 (12) | C19—C18—C20 | 111.29 (14) |
O4—C5—C6 | 108.69 (13) | C17—C18—H18A | 107.6 |
O3—C5—C6 | 108.63 (13) | C19—C18—H18A | 107.6 |
O4—C5—H5A | 109.9 | C20—C18—H18A | 107.6 |
O3—C5—H5A | 109.9 | C18—C19—H19A | 109.5 |
C6—C5—H5A | 109.9 | C18—C19—H19B | 109.5 |
C5—C6—C8 | 111.03 (14) | H19A—C19—H19B | 109.5 |
C5—C6—C7 | 110.45 (14) | C18—C19—H19C | 109.5 |
C8—C6—C7 | 110.25 (15) | H19A—C19—H19C | 109.5 |
C5—C6—H6A | 108.3 | H19B—C19—H19C | 109.5 |
C8—C6—H6A | 108.3 | C18—C20—H20C | 109.5 |
C7—C6—H6A | 108.3 | C18—C20—H20B | 109.5 |
C6—C7—H7A | 109.5 | H20C—C20—H20B | 109.5 |
C6—C7—H7B | 109.5 | C18—C20—H20A | 109.5 |
H7A—C7—H7B | 109.5 | H20C—C20—H20A | 109.5 |
C6—C7—H7C | 109.5 | H20B—C20—H20A | 109.5 |
H7A—C7—H7C | 109.5 | O5—C21—N4 | 124.22 (15) |
H7B—C7—H7C | 109.5 | O5—C21—C22 | 128.67 (16) |
C6—C8—H8A | 109.5 | N4—C21—C22 | 107.11 (13) |
C6—C8—H8B | 109.5 | C21—C22—C23 | 105.75 (13) |
H8A—C8—H8B | 109.5 | C21—C22—H22A | 110.6 |
C6—C8—H8C | 109.5 | C23—C22—H22A | 110.6 |
H8A—C8—H8C | 109.5 | C21—C22—H22B | 110.6 |
H8B—C8—H8C | 109.5 | C23—C22—H22B | 110.6 |
O1—C9—N2 | 124.16 (15) | H22A—C22—H22B | 108.7 |
O1—C9—C10 | 128.77 (15) | C24—C23—C22 | 105.49 (13) |
N2—C9—C10 | 107.06 (14) | C24—C23—H23A | 110.6 |
C9—C10—C11 | 105.41 (13) | C22—C23—H23A | 110.6 |
C9—C10—H10A | 110.7 | C24—C23—H23B | 110.6 |
C11—C10—H10A | 110.7 | C22—C23—H23B | 110.6 |
C9—C10—H10B | 110.7 | H23A—C23—H23B | 108.8 |
C11—C10—H10B | 110.7 | O6—C24—N4 | 124.22 (14) |
H10A—C10—H10B | 108.8 | O6—C24—C23 | 128.66 (15) |
C12—C11—C10 | 105.81 (13) | N4—C24—C23 | 107.10 (13) |
C12—C11—H11B | 110.6 | N2—N1—C2 | 110.51 (12) |
C10—C11—H11B | 110.6 | N2—N1—C3 | 110.94 (11) |
C12—C11—H11A | 110.6 | C2—N1—C3 | 59.12 (10) |
C10—C11—H11A | 110.6 | C12—N2—C9 | 114.50 (13) |
H11B—C11—H11A | 108.7 | C12—N2—N1 | 122.38 (12) |
O2—C12—N2 | 124.45 (15) | C9—N2—N1 | 122.46 (13) |
O2—C12—C11 | 128.59 (15) | N4—N3—C15 | 110.54 (11) |
N2—C12—C11 | 106.96 (13) | N4—N3—C14 | 111.20 (11) |
O7—C13—C14 | 115.66 (13) | C15—N3—C14 | 59.40 (9) |
O7—C13—H13A | 108.4 | C21—N4—C24 | 114.33 (13) |
C14—C13—H13A | 108.4 | C21—N4—N3 | 122.52 (12) |
O7—C13—H13B | 108.4 | C24—N4—N3 | 122.54 (12) |
C14—C13—H13B | 108.4 | C5—O3—C1 | 114.39 (12) |
H13A—C13—H13B | 107.4 | C5—O4—C4 | 114.79 (11) |
C15—C14—N3 | 60.17 (10) | C17—O7—C13 | 114.12 (12) |
C15—C14—C13 | 127.08 (13) | C17—O8—C16 | 114.48 (12) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C12H18N2O4 | C12H18N2O4 |
Mr | 254.28 | 254.28 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21/c |
Temperature (K) | 153 | 153 |
a, b, c (Å) | 6.1449 (11), 7.8343 (10), 13.080 (3) | 24.470 (3), 8.8444 (8), 11.8252 (14) |
β (°) | 100.250 (15) | 97.119 (9) |
V (Å3) | 619.6 (2) | 2539.6 (5) |
Z | 2 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.10 |
Crystal size (mm) | 0.47 × 0.41 × 0.05 | 0.66 × 0.65 × 0.25 |
Data collection | ||
Diffractometer | Stoe IPDS 2 diffractometer | Stoe IPDS 2 diffractometer |
Absorption correction | Integration X-RED32 (Stoe & Cie, 2004) | Integration X-RED32 (Stoe & Cie, 2004) |
Tmin, Tmax | 0.954, 0.995 | 0.914, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8393, 1244, 998 | 18062, 4465, 2623 |
Rint | 0.057 | 0.033 |
(sin θ/λ)max (Å−1) | 0.605 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.076, 1.02 | 0.031, 0.084, 0.90 |
No. of reflections | 1244 | 4465 |
No. of parameters | 165 | 330 |
No. of restraints | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.14, −0.21 | 0.21, −0.15 |
Computer programs: Please provide missing details, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997).
Fused aziridines, e.g. N-arenesulfonyl-protected 1,3-dioxepanoaziridines, are of interest as potent antihypoglycaemic agents (Dumić et al., 1993, 1995; Oresić et al., 2001; Filić et al., 1996). Such compounds have been prepared from trans-acetylaminochlorodioxepanes by ring-closure dehydrohalogenation and subsequent N-protection with arenesulfonylchlorides. Direct aziridination of 4,7-dihydro-1,3-dioxepins using sulfonylazides as the nitrogen source failed (Dumić et al., 1993). The crystal structures of these compounds have been thoroughly studied in order to develop quantitative structure–property and structure–activity relationship models.
Recently, we have developed a new aziridination procedure using N-aminosuccinimide as the nitrogen source and iodosylbenzene diacetate as the oxidizing agent, which directly leads to N-amino-protected fused dioxepanoaziridines (Flock et al., 2005). Thus, a diastereomeric mixture of the title compounds, (I) and (II) (Figs 1 and 2), was obtained from 2-isopropyl-4,7-dihydro-1,3-dioxepin, N-aminosuccinimide and iodosylbenzene diacetate. The relative configurations of these compounds are of interest with respect to their reactivity and stability.
Separation of the diastereomeric mixture by column chromatography afforded (I) and (II) as colourless solids. However, determination of the relative configurations using nuclear Overhauser experiments failed because of the flexibility of the dioxepin moiety in solution. After recrystallization from diethyl ether–acetone and evaporation from acetone, respectively, (I) and (II) crystallized as well formed plate-like colourless crystals.
The exo isomer, (I), crystallizes in the non-centrosymmetric space group P21 with Z' = 1, but the absolute configuration could not be determined. The endo isomer, (II), crystallizes in space group P21/c with Z' = 2. The difference between the two independent molecules in (II) lies in the conformation of the isopropyl substituent around the C5—C6 and C17—C18 bonds (Fig. 2). Neither isomer shows any strong intermolecular interactions.
In both isomers, the isopropyl substituent at the acetalic unit was found in a quasi-equatorial position. Analysis of the endo isomer, (II), reveals that the dioxepanoaziridine moiety adopts a boat–chair (BC) conformation, while for the exo isomer, (I), the preferred conformation in the solid state is the chair–chair (CC) conformation. The substituent on the aziridine N atom occupies, in both cases, the anti position with respect to the dioxepane ring, which supports previous results found for 8-sulfonyl-protected bicyclooctane derivatives (Dumić et al., 1995).