Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028139/dn2179sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028139/dn2179Isup2.hkl |
CCDC reference: 654962
To a precooled solution of anhydrous HMDS (0.387 g, 2.4 mmol) in anhydrous THF (3.5 ml) at 0°C, was added dropwise a 2.5 M solution of n-BuLi (0.96 ml, 2.4 mmol) in hexane. After stired 0.5 h, the fresh prepared LiHMDS-THF solution was dropwised at 0°C under argon to a solution of (2R,3R)-N-Benzhydryl-N-(2-cyclopropyl-2-oxoethyl)-2,3-epoxybutyramide (0.699 g, 2 mmol) in dry THF (20 ml). The cooling bath was removed and the mixture warmed to 20°C for 3 h. The reaction was quenched with a 1 M solution of HCl (2 ml). After dilution with ethyl acetate (10 ml), the solution was washed with NaHCO3 solution (5%, 3×10 ml), brine (2×10 ml), dried over anhydrous MgSO4, concentrated under vacuum and the crude product was purified by column chromatography (petroleum ether/ethyl acetate, 10:1 v/v) to give the titled compound as a white solid with 80% yield (Laurent et al., 2004). Single crystals of (I) were developed in ethyl acetate solution by slow evaporation.
All H atoms attached to C atoms and O atom were fixed geometrically and treated as riding with C—H = 0.93 Å (Caromatic), 0.97 Å (Cmethylene), 0.96 Å (Cmethyl), 0.98 Å (Cmethine) and O—H =0.82 Å with Uiso(H) = 1.2Ueq(Caromatic, Cmethylene, Cmethine and O) and with Uiso(H) = 1.5Ueq(Cmethyl).
In the absence of significant anomalous scattering, the absolute configuration could not be reliably determined by X-ray analyses and then the Friedel pairs were merged and any references to the Flack parameter were removed.
In the course of the synthesis of acetoxyazetidinone, which is used as a key structure for the preparation of carbapenems, which are a growing class of β-lactam antibiotics (Walsh, 2000), the title compound, (I), was prepared and obtained as single crystals suitable for X-ray structural analysis.
The molecular structure of (I) is shown in Fig. 1. The correct enantiomer has been assigned by reference to an unchanging chiral center (C8) in the synthetic procedure (Tinant et al., 2003). Bond lengths and angles in (I) are in agreement with values reported for a similar compound (Wang et al., 2006). The dihedral angle between the C11-phenyl and C17-phenyl planes is 74.8 (2)°. Molecules are linked into helicoidal chains running along the b axis, through O—H···O hydrogen bonds. The chains are further connected through weak C—H···O intermolecular hydrogen bonds to build up a three dimensionnal network (table 1).
For general background see: Walsh (2000). For related structures see: Tinant et al. (2003); Wang et al. (2006). For related literature, see: Laurent et al. (2004).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure of (I) showing the atom-numbering scheme. Ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. |
C22H23NO3 | Z = 4 |
Mr = 349.41 | F(000) = 744 |
Monoclinic, C2 | Dx = 1.240 Mg m−3 |
Hall symbol: C 2y | Mo Kα radiation, λ = 0.71073 Å |
a = 18.8279 (13) Å | µ = 0.08 mm−1 |
b = 6.1645 (4) Å | T = 153 K |
c = 16.3539 (10) Å | Chunk, colourless |
β = 99.529 (6)° | 0.42 × 0.40 × 0.35 mm |
V = 1871.9 (2) Å3 |
Bruker APEX area-detector diffractometer | 2007 independent reflections |
Radiation source: fine-focus sealed tube | 1312 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
φ and ω scans | θmax = 26.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −23→19 |
Tmin = 0.966, Tmax = 0.972 | k = −7→7 |
6131 measured reflections | l = −20→20 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.157 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0938P)2] where P = (Fo2 + 2Fc2)/3 |
2007 reflections | (Δ/σ)max = 0.001 |
237 parameters | Δρmax = 0.17 e Å−3 |
1 restraint | Δρmin = −0.19 e Å−3 |
C22H23NO3 | V = 1871.9 (2) Å3 |
Mr = 349.41 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 18.8279 (13) Å | µ = 0.08 mm−1 |
b = 6.1645 (4) Å | T = 153 K |
c = 16.3539 (10) Å | 0.42 × 0.40 × 0.35 mm |
β = 99.529 (6)° |
Bruker APEX area-detector diffractometer | 2007 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 1312 reflections with I > 2σ(I) |
Tmin = 0.966, Tmax = 0.972 | Rint = 0.034 |
6131 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 1 restraint |
wR(F2) = 0.157 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.17 e Å−3 |
2007 reflections | Δρmin = −0.19 e Å−3 |
237 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 | 0.7696 (2) | 0.1736 (7) | 0.1309 (2) | 0.0406 (10) | |
C2 | 0.6968 (2) | 0.1326 (7) | 0.0804 (2) | 0.0410 (10) | |
H2 | 0.6929 | −0.0194 | 0.0626 | 0.049* | |
C3 | 0.6685 (2) | 0.1585 (7) | 0.1658 (2) | 0.0395 (10) | |
H3 | 0.6373 | 0.2849 | 0.1676 | 0.047* | |
C4 | 0.6360 (2) | −0.0499 (8) | 0.1902 (3) | 0.0467 (11) | |
C5 | 0.5585 (2) | −0.0728 (8) | 0.1700 (3) | 0.0520 (12) | |
H5 | 0.5304 | 0.0612 | 0.1600 | 0.062* | |
C6 | 0.5307 (2) | −0.2690 (9) | 0.1179 (3) | 0.0591 (13) | |
H6A | 0.4877 | −0.2505 | 0.0767 | 0.071* | |
H6B | 0.5659 | −0.3690 | 0.1024 | 0.071* | |
C7 | 0.5227 (3) | −0.2602 (10) | 0.2050 (4) | 0.0776 (17) | |
H7A | 0.5527 | −0.3558 | 0.2432 | 0.093* | |
H7B | 0.4746 | −0.2374 | 0.2175 | 0.093* | |
C8 | 0.6701 (2) | 0.2772 (7) | 0.0089 (3) | 0.0434 (10) | |
H8 | 0.7022 | 0.2608 | −0.0322 | 0.052* | |
C9 | 0.5949 (2) | 0.2184 (11) | −0.0319 (3) | 0.0699 (15) | |
H9A | 0.5633 | 0.2224 | 0.0085 | 0.105* | |
H9B | 0.5949 | 0.0750 | −0.0549 | 0.105* | |
H9C | 0.5786 | 0.3202 | −0.0754 | 0.105* | |
C10 | 0.7803 (2) | 0.1968 (8) | 0.2885 (2) | 0.0463 (10) | |
H10 | 0.8022 | 0.0532 | 0.2991 | 0.056* | |
C11 | 0.8416 (2) | 0.3641 (8) | 0.3034 (2) | 0.0436 (11) | |
C12 | 0.9019 (2) | 0.3201 (12) | 0.3639 (3) | 0.0648 (15) | |
H12 | 0.9053 | 0.1918 | 0.3943 | 0.078* | |
C13 | 0.9561 (3) | 0.4749 (16) | 0.3768 (3) | 0.084 (2) | |
H13 | 0.9957 | 0.4504 | 0.4180 | 0.101* | |
C14 | 0.9539 (3) | 0.6563 (14) | 0.3328 (4) | 0.082 (2) | |
H14 | 0.9922 | 0.7533 | 0.3423 | 0.099* | |
C15 | 0.8956 (3) | 0.7012 (10) | 0.2738 (4) | 0.0690 (15) | |
H15 | 0.8941 | 0.8296 | 0.2437 | 0.083* | |
C16 | 0.8382 (3) | 0.5553 (8) | 0.2583 (3) | 0.0571 (13) | |
H16 | 0.7983 | 0.5859 | 0.2184 | 0.069* | |
C17 | 0.7270 (2) | 0.2264 (8) | 0.3487 (2) | 0.0449 (11) | |
C18 | 0.6888 (3) | 0.4147 (8) | 0.3508 (3) | 0.0513 (12) | |
H18 | 0.6943 | 0.5261 | 0.3140 | 0.062* | |
C19 | 0.6418 (3) | 0.4411 (11) | 0.4073 (3) | 0.0654 (15) | |
H19 | 0.6155 | 0.5685 | 0.4080 | 0.079* | |
C20 | 0.6348 (3) | 0.2774 (13) | 0.4620 (3) | 0.078 (2) | |
H20 | 0.6033 | 0.2938 | 0.4998 | 0.094* | |
C21 | 0.6738 (3) | 0.0894 (11) | 0.4616 (3) | 0.0720 (16) | |
H21 | 0.6694 | −0.0199 | 0.4996 | 0.086* | |
C22 | 0.7194 (3) | 0.0628 (9) | 0.4050 (3) | 0.0631 (14) | |
H22 | 0.7453 | −0.0654 | 0.4044 | 0.076* | |
N1 | 0.74373 (17) | 0.1984 (6) | 0.20291 (19) | 0.0427 (8) | |
O1 | 0.83222 (16) | 0.1818 (6) | 0.11784 (18) | 0.0582 (9) | |
O2 | 0.67671 (18) | −0.1934 (6) | 0.2210 (2) | 0.0668 (10) | |
O3 | 0.67549 (19) | 0.4940 (5) | 0.03812 (18) | 0.0557 (9) | |
H3A | 0.6622 | 0.5771 | −0.0006 | 0.084* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.036 (2) | 0.050 (3) | 0.0348 (18) | 0.0004 (19) | 0.0028 (16) | −0.004 (2) |
C2 | 0.039 (2) | 0.048 (3) | 0.036 (2) | −0.0072 (19) | 0.0073 (17) | −0.0043 (19) |
C3 | 0.035 (2) | 0.045 (3) | 0.040 (2) | 0.0032 (18) | 0.0087 (16) | 0.0036 (19) |
C4 | 0.047 (2) | 0.052 (3) | 0.044 (2) | 0.003 (2) | 0.0146 (19) | 0.006 (2) |
C5 | 0.041 (2) | 0.049 (3) | 0.069 (3) | 0.004 (2) | 0.016 (2) | −0.004 (2) |
C6 | 0.040 (2) | 0.073 (4) | 0.059 (3) | 0.000 (2) | −0.006 (2) | −0.012 (3) |
C7 | 0.072 (4) | 0.085 (4) | 0.087 (4) | −0.020 (3) | 0.043 (3) | 0.000 (4) |
C8 | 0.040 (2) | 0.048 (3) | 0.044 (2) | −0.0073 (19) | 0.0147 (18) | −0.010 (2) |
C9 | 0.050 (3) | 0.088 (4) | 0.067 (3) | −0.010 (3) | −0.006 (2) | 0.010 (3) |
C10 | 0.049 (2) | 0.049 (3) | 0.041 (2) | 0.011 (2) | 0.0063 (17) | 0.000 (2) |
C11 | 0.035 (2) | 0.060 (3) | 0.034 (2) | 0.003 (2) | 0.0004 (16) | −0.013 (2) |
C12 | 0.044 (3) | 0.109 (4) | 0.039 (2) | 0.004 (3) | 0.0000 (19) | −0.011 (3) |
C13 | 0.045 (3) | 0.153 (7) | 0.051 (3) | −0.007 (4) | −0.003 (2) | −0.033 (4) |
C14 | 0.060 (4) | 0.107 (5) | 0.083 (4) | −0.023 (4) | 0.023 (3) | −0.042 (4) |
C15 | 0.060 (3) | 0.063 (3) | 0.088 (3) | −0.010 (3) | 0.020 (3) | −0.027 (3) |
C16 | 0.042 (3) | 0.057 (3) | 0.074 (3) | −0.006 (2) | 0.014 (2) | −0.017 (3) |
C17 | 0.045 (2) | 0.051 (3) | 0.038 (2) | −0.001 (2) | 0.0043 (16) | 0.004 (2) |
C18 | 0.054 (3) | 0.058 (3) | 0.043 (2) | 0.008 (2) | 0.011 (2) | 0.008 (2) |
C19 | 0.053 (3) | 0.090 (4) | 0.057 (3) | 0.002 (3) | 0.018 (2) | −0.004 (3) |
C20 | 0.074 (4) | 0.117 (6) | 0.049 (3) | −0.033 (4) | 0.024 (3) | −0.006 (3) |
C21 | 0.090 (4) | 0.079 (4) | 0.047 (3) | −0.027 (4) | 0.010 (3) | 0.018 (3) |
C22 | 0.074 (3) | 0.059 (3) | 0.055 (3) | −0.004 (3) | 0.005 (3) | 0.021 (3) |
N1 | 0.0403 (19) | 0.050 (2) | 0.0386 (16) | −0.0009 (17) | 0.0100 (14) | −0.0008 (18) |
O1 | 0.0389 (17) | 0.078 (2) | 0.0610 (17) | −0.0016 (16) | 0.0181 (13) | −0.0173 (19) |
O2 | 0.052 (2) | 0.060 (2) | 0.080 (2) | 0.0008 (18) | −0.0124 (16) | 0.024 (2) |
O3 | 0.073 (2) | 0.049 (2) | 0.0468 (17) | −0.0001 (17) | 0.0157 (16) | 0.0040 (16) |
C1—O1 | 1.234 (5) | C10—C17 | 1.530 (6) |
C1—N1 | 1.355 (5) | C10—C11 | 1.536 (6) |
C1—C2 | 1.500 (6) | C10—H10 | 0.9800 |
C2—C8 | 1.490 (6) | C11—C16 | 1.386 (7) |
C2—C3 | 1.582 (5) | C11—C12 | 1.403 (6) |
C2—H2 | 0.9800 | C12—C13 | 1.388 (9) |
C3—N1 | 1.466 (5) | C12—H12 | 0.9300 |
C3—C4 | 1.506 (6) | C13—C14 | 1.327 (11) |
C3—H3 | 0.9800 | C13—H13 | 0.9300 |
C4—O2 | 1.223 (6) | C14—C15 | 1.365 (9) |
C4—C5 | 1.449 (6) | C14—H14 | 0.9300 |
C5—C7 | 1.497 (7) | C15—C16 | 1.397 (7) |
C5—C6 | 1.521 (7) | C15—H15 | 0.9300 |
C5—H5 | 0.9800 | C16—H16 | 0.9300 |
C6—C7 | 1.457 (7) | C17—C18 | 1.369 (7) |
C6—H6A | 0.9700 | C17—C22 | 1.389 (6) |
C6—H6B | 0.9700 | C18—C19 | 1.391 (6) |
C7—H7A | 0.9700 | C18—H18 | 0.9300 |
C7—H7B | 0.9700 | C19—C20 | 1.369 (9) |
C8—O3 | 1.417 (6) | C19—H19 | 0.9300 |
C8—C9 | 1.507 (6) | C20—C21 | 1.373 (10) |
C8—H8 | 0.9800 | C20—H20 | 0.9300 |
C9—H9A | 0.9600 | C21—C22 | 1.371 (8) |
C9—H9B | 0.9600 | C21—H21 | 0.9300 |
C9—H9C | 0.9600 | C22—H22 | 0.9300 |
C10—N1 | 1.454 (5) | O3—H3A | 0.8200 |
O1—C1—N1 | 129.6 (4) | H9B—C9—H9C | 109.5 |
O1—C1—C2 | 136.4 (3) | N1—C10—C17 | 111.2 (3) |
N1—C1—C2 | 94.0 (3) | N1—C10—C11 | 111.8 (3) |
C8—C2—C1 | 119.3 (3) | C17—C10—C11 | 111.9 (3) |
C8—C2—C3 | 120.9 (3) | N1—C10—H10 | 107.2 |
C1—C2—C3 | 84.7 (3) | C17—C10—H10 | 107.2 |
C8—C2—H2 | 109.9 | C11—C10—H10 | 107.2 |
C1—C2—H2 | 109.9 | C16—C11—C12 | 120.0 (5) |
C3—C2—H2 | 109.9 | C16—C11—C10 | 121.3 (4) |
N1—C3—C4 | 116.2 (3) | C12—C11—C10 | 118.7 (5) |
N1—C3—C2 | 86.5 (3) | C13—C12—C11 | 117.6 (6) |
C4—C3—C2 | 111.0 (3) | C13—C12—H12 | 121.2 |
N1—C3—H3 | 113.4 | C11—C12—H12 | 121.2 |
C4—C3—H3 | 113.4 | C14—C13—C12 | 122.7 (6) |
C2—C3—H3 | 113.4 | C14—C13—H13 | 118.6 |
O2—C4—C5 | 124.2 (4) | C12—C13—H13 | 118.6 |
O2—C4—C3 | 118.1 (4) | C13—C14—C15 | 120.3 (6) |
C5—C4—C3 | 117.5 (4) | C13—C14—H14 | 119.9 |
C4—C5—C7 | 119.2 (5) | C15—C14—H14 | 119.9 |
C4—C5—C6 | 116.4 (4) | C14—C15—C16 | 120.3 (6) |
C7—C5—C6 | 57.7 (4) | C14—C15—H15 | 119.8 |
C4—C5—H5 | 116.8 | C16—C15—H15 | 119.8 |
C7—C5—H5 | 116.8 | C11—C16—C15 | 119.0 (5) |
C6—C5—H5 | 116.8 | C11—C16—H16 | 120.5 |
C7—C6—C5 | 60.3 (3) | C15—C16—H16 | 120.5 |
C7—C6—H6A | 117.7 | C18—C17—C22 | 119.2 (4) |
C5—C6—H6A | 117.7 | C18—C17—C10 | 121.4 (4) |
C7—C6—H6B | 117.7 | C22—C17—C10 | 119.4 (4) |
C5—C6—H6B | 117.7 | C17—C18—C19 | 120.6 (5) |
H6A—C6—H6B | 114.9 | C17—C18—H18 | 119.7 |
C6—C7—C5 | 62.0 (3) | C19—C18—H18 | 119.7 |
C6—C7—H7A | 117.6 | C20—C19—C18 | 119.3 (6) |
C5—C7—H7A | 117.6 | C20—C19—H19 | 120.3 |
C6—C7—H7B | 117.6 | C18—C19—H19 | 120.3 |
C5—C7—H7B | 117.6 | C19—C20—C21 | 120.6 (5) |
H7A—C7—H7B | 114.7 | C19—C20—H20 | 119.7 |
O3—C8—C2 | 107.7 (3) | C21—C20—H20 | 119.7 |
O3—C8—C9 | 112.7 (4) | C22—C21—C20 | 120.0 (5) |
C2—C8—C9 | 111.9 (4) | C22—C21—H21 | 120.0 |
O3—C8—H8 | 108.1 | C20—C21—H21 | 120.0 |
C2—C8—H8 | 108.1 | C21—C22—C17 | 120.3 (5) |
C9—C8—H8 | 108.1 | C21—C22—H22 | 119.8 |
C8—C9—H9A | 109.5 | C17—C22—H22 | 119.8 |
C8—C9—H9B | 109.5 | C1—N1—C10 | 130.9 (3) |
H9A—C9—H9B | 109.5 | C1—N1—C3 | 94.7 (3) |
C8—C9—H9C | 109.5 | C10—N1—C3 | 132.0 (3) |
H9A—C9—H9C | 109.5 | C8—O3—H3A | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O1i | 0.82 | 2.04 | 2.783 (4) | 150 |
C18—H18···O2ii | 0.93 | 2.29 | 3.199 (6) | 165 |
Symmetry codes: (i) −x+3/2, y+1/2, −z; (ii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C22H23NO3 |
Mr | 349.41 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 153 |
a, b, c (Å) | 18.8279 (13), 6.1645 (4), 16.3539 (10) |
β (°) | 99.529 (6) |
V (Å3) | 1871.9 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.42 × 0.40 × 0.35 |
Data collection | |
Diffractometer | Bruker APEX area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2002) |
Tmin, Tmax | 0.966, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6131, 2007, 1312 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.157, 1.07 |
No. of reflections | 2007 |
No. of parameters | 237 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.19 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O1i | 0.82 | 2.04 | 2.783 (4) | 149.9 |
C18—H18···O2ii | 0.93 | 2.29 | 3.199 (6) | 165.4 |
Symmetry codes: (i) −x+3/2, y+1/2, −z; (ii) x, y+1, z. |
In the course of the synthesis of acetoxyazetidinone, which is used as a key structure for the preparation of carbapenems, which are a growing class of β-lactam antibiotics (Walsh, 2000), the title compound, (I), was prepared and obtained as single crystals suitable for X-ray structural analysis.
The molecular structure of (I) is shown in Fig. 1. The correct enantiomer has been assigned by reference to an unchanging chiral center (C8) in the synthetic procedure (Tinant et al., 2003). Bond lengths and angles in (I) are in agreement with values reported for a similar compound (Wang et al., 2006). The dihedral angle between the C11-phenyl and C17-phenyl planes is 74.8 (2)°. Molecules are linked into helicoidal chains running along the b axis, through O—H···O hydrogen bonds. The chains are further connected through weak C—H···O intermolecular hydrogen bonds to build up a three dimensionnal network (table 1).