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The title compound, C22H23NO3, was obtained by the reaction of (2R,3R)-N-benzhydryl-N-(2-cyclo­propyl-2-oxoeth­yl)-2,3-epoxy­butyramide with Lithium bis(trimethylsilyl)amide in tetra­hydro­furan solution. The absolute configuration has been assigned by reference to an unchanging chiral centre in the synthetic procedure. The mol­ecular packing is stabilized by inter­molecular O—H...O and C—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028139/dn2179sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028139/dn2179Isup2.hkl
Contains datablock I

CCDC reference: 654962

Key indicators

  • Single-crystal X-ray study
  • T = 153 K
  • Mean [sigma](C-C) = 0.007 Å
  • R factor = 0.046
  • wR factor = 0.157
  • Data-to-parameter ratio = 8.5

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C7 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 26.00 From the CIF: _reflns_number_total 2007 Count of symmetry unique reflns 2026 Completeness (_total/calc) 99.06% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C8 = . R PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

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).

Related literature top

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).

Experimental top

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.

Refinement top

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.

Structure description top

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).

Computing details top

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.

Figures top
[Figure 1] 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.
(3S,4S)-1-Benzhydryl-4-(cyclopropylcarbonyl)- 3-[(1R)-1-hydroxyethyl]azetidin-2-one top
Crystal data top
C22H23NO3Z = 4
Mr = 349.41F(000) = 744
Monoclinic, C2Dx = 1.240 Mg m3
Hall symbol: C 2yMo Kα radiation, λ = 0.71073 Å
a = 18.8279 (13) ŵ = 0.08 mm1
b = 6.1645 (4) ÅT = 153 K
c = 16.3539 (10) ÅChunk, colourless
β = 99.529 (6)°0.42 × 0.40 × 0.35 mm
V = 1871.9 (2) Å3
Data collection top
Bruker APEX area-detector
diffractometer
2007 independent reflections
Radiation source: fine-focus sealed tube1312 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
φ and ω scansθmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
h = 2319
Tmin = 0.966, Tmax = 0.972k = 77
6131 measured reflectionsl = 2020
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.157H-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 parametersΔρmax = 0.17 e Å3
1 restraintΔρmin = 0.19 e Å3
Crystal data top
C22H23NO3V = 1871.9 (2) Å3
Mr = 349.41Z = 4
Monoclinic, C2Mo Kα radiation
a = 18.8279 (13) ŵ = 0.08 mm1
b = 6.1645 (4) ÅT = 153 K
c = 16.3539 (10) Å0.42 × 0.40 × 0.35 mm
β = 99.529 (6)°
Data collection top
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 = 0.972Rint = 0.034
6131 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0461 restraint
wR(F2) = 0.157H-atom parameters constrained
S = 1.07Δρmax = 0.17 e Å3
2007 reflectionsΔρmin = 0.19 e Å3
237 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.7696 (2)0.1736 (7)0.1309 (2)0.0406 (10)
C20.6968 (2)0.1326 (7)0.0804 (2)0.0410 (10)
H20.69290.01940.06260.049*
C30.6685 (2)0.1585 (7)0.1658 (2)0.0395 (10)
H30.63730.28490.16760.047*
C40.6360 (2)0.0499 (8)0.1902 (3)0.0467 (11)
C50.5585 (2)0.0728 (8)0.1700 (3)0.0520 (12)
H50.53040.06120.16000.062*
C60.5307 (2)0.2690 (9)0.1179 (3)0.0591 (13)
H6A0.48770.25050.07670.071*
H6B0.56590.36900.10240.071*
C70.5227 (3)0.2602 (10)0.2050 (4)0.0776 (17)
H7A0.55270.35580.24320.093*
H7B0.47460.23740.21750.093*
C80.6701 (2)0.2772 (7)0.0089 (3)0.0434 (10)
H80.70220.26080.03220.052*
C90.5949 (2)0.2184 (11)0.0319 (3)0.0699 (15)
H9A0.56330.22240.00850.105*
H9B0.59490.07500.05490.105*
H9C0.57860.32020.07540.105*
C100.7803 (2)0.1968 (8)0.2885 (2)0.0463 (10)
H100.80220.05320.29910.056*
C110.8416 (2)0.3641 (8)0.3034 (2)0.0436 (11)
C120.9019 (2)0.3201 (12)0.3639 (3)0.0648 (15)
H120.90530.19180.39430.078*
C130.9561 (3)0.4749 (16)0.3768 (3)0.084 (2)
H130.99570.45040.41800.101*
C140.9539 (3)0.6563 (14)0.3328 (4)0.082 (2)
H140.99220.75330.34230.099*
C150.8956 (3)0.7012 (10)0.2738 (4)0.0690 (15)
H150.89410.82960.24370.083*
C160.8382 (3)0.5553 (8)0.2583 (3)0.0571 (13)
H160.79830.58590.21840.069*
C170.7270 (2)0.2264 (8)0.3487 (2)0.0449 (11)
C180.6888 (3)0.4147 (8)0.3508 (3)0.0513 (12)
H180.69430.52610.31400.062*
C190.6418 (3)0.4411 (11)0.4073 (3)0.0654 (15)
H190.61550.56850.40800.079*
C200.6348 (3)0.2774 (13)0.4620 (3)0.078 (2)
H200.60330.29380.49980.094*
C210.6738 (3)0.0894 (11)0.4616 (3)0.0720 (16)
H210.66940.01990.49960.086*
C220.7194 (3)0.0628 (9)0.4050 (3)0.0631 (14)
H220.74530.06540.40440.076*
N10.74373 (17)0.1984 (6)0.20291 (19)0.0427 (8)
O10.83222 (16)0.1818 (6)0.11784 (18)0.0582 (9)
O20.67671 (18)0.1934 (6)0.2210 (2)0.0668 (10)
O30.67549 (19)0.4940 (5)0.03812 (18)0.0557 (9)
H3A0.66220.57710.00060.084*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.036 (2)0.050 (3)0.0348 (18)0.0004 (19)0.0028 (16)0.004 (2)
C20.039 (2)0.048 (3)0.036 (2)0.0072 (19)0.0073 (17)0.0043 (19)
C30.035 (2)0.045 (3)0.040 (2)0.0032 (18)0.0087 (16)0.0036 (19)
C40.047 (2)0.052 (3)0.044 (2)0.003 (2)0.0146 (19)0.006 (2)
C50.041 (2)0.049 (3)0.069 (3)0.004 (2)0.016 (2)0.004 (2)
C60.040 (2)0.073 (4)0.059 (3)0.000 (2)0.006 (2)0.012 (3)
C70.072 (4)0.085 (4)0.087 (4)0.020 (3)0.043 (3)0.000 (4)
C80.040 (2)0.048 (3)0.044 (2)0.0073 (19)0.0147 (18)0.010 (2)
C90.050 (3)0.088 (4)0.067 (3)0.010 (3)0.006 (2)0.010 (3)
C100.049 (2)0.049 (3)0.041 (2)0.011 (2)0.0063 (17)0.000 (2)
C110.035 (2)0.060 (3)0.034 (2)0.003 (2)0.0004 (16)0.013 (2)
C120.044 (3)0.109 (4)0.039 (2)0.004 (3)0.0000 (19)0.011 (3)
C130.045 (3)0.153 (7)0.051 (3)0.007 (4)0.003 (2)0.033 (4)
C140.060 (4)0.107 (5)0.083 (4)0.023 (4)0.023 (3)0.042 (4)
C150.060 (3)0.063 (3)0.088 (3)0.010 (3)0.020 (3)0.027 (3)
C160.042 (3)0.057 (3)0.074 (3)0.006 (2)0.014 (2)0.017 (3)
C170.045 (2)0.051 (3)0.038 (2)0.001 (2)0.0043 (16)0.004 (2)
C180.054 (3)0.058 (3)0.043 (2)0.008 (2)0.011 (2)0.008 (2)
C190.053 (3)0.090 (4)0.057 (3)0.002 (3)0.018 (2)0.004 (3)
C200.074 (4)0.117 (6)0.049 (3)0.033 (4)0.024 (3)0.006 (3)
C210.090 (4)0.079 (4)0.047 (3)0.027 (4)0.010 (3)0.018 (3)
C220.074 (3)0.059 (3)0.055 (3)0.004 (3)0.005 (3)0.021 (3)
N10.0403 (19)0.050 (2)0.0386 (16)0.0009 (17)0.0100 (14)0.0008 (18)
O10.0389 (17)0.078 (2)0.0610 (17)0.0016 (16)0.0181 (13)0.0173 (19)
O20.052 (2)0.060 (2)0.080 (2)0.0008 (18)0.0124 (16)0.024 (2)
O30.073 (2)0.049 (2)0.0468 (17)0.0001 (17)0.0157 (16)0.0040 (16)
Geometric parameters (Å, º) top
C1—O11.234 (5)C10—C171.530 (6)
C1—N11.355 (5)C10—C111.536 (6)
C1—C21.500 (6)C10—H100.9800
C2—C81.490 (6)C11—C161.386 (7)
C2—C31.582 (5)C11—C121.403 (6)
C2—H20.9800C12—C131.388 (9)
C3—N11.466 (5)C12—H120.9300
C3—C41.506 (6)C13—C141.327 (11)
C3—H30.9800C13—H130.9300
C4—O21.223 (6)C14—C151.365 (9)
C4—C51.449 (6)C14—H140.9300
C5—C71.497 (7)C15—C161.397 (7)
C5—C61.521 (7)C15—H150.9300
C5—H50.9800C16—H160.9300
C6—C71.457 (7)C17—C181.369 (7)
C6—H6A0.9700C17—C221.389 (6)
C6—H6B0.9700C18—C191.391 (6)
C7—H7A0.9700C18—H180.9300
C7—H7B0.9700C19—C201.369 (9)
C8—O31.417 (6)C19—H190.9300
C8—C91.507 (6)C20—C211.373 (10)
C8—H80.9800C20—H200.9300
C9—H9A0.9600C21—C221.371 (8)
C9—H9B0.9600C21—H210.9300
C9—H9C0.9600C22—H220.9300
C10—N11.454 (5)O3—H3A0.8200
O1—C1—N1129.6 (4)H9B—C9—H9C109.5
O1—C1—C2136.4 (3)N1—C10—C17111.2 (3)
N1—C1—C294.0 (3)N1—C10—C11111.8 (3)
C8—C2—C1119.3 (3)C17—C10—C11111.9 (3)
C8—C2—C3120.9 (3)N1—C10—H10107.2
C1—C2—C384.7 (3)C17—C10—H10107.2
C8—C2—H2109.9C11—C10—H10107.2
C1—C2—H2109.9C16—C11—C12120.0 (5)
C3—C2—H2109.9C16—C11—C10121.3 (4)
N1—C3—C4116.2 (3)C12—C11—C10118.7 (5)
N1—C3—C286.5 (3)C13—C12—C11117.6 (6)
C4—C3—C2111.0 (3)C13—C12—H12121.2
N1—C3—H3113.4C11—C12—H12121.2
C4—C3—H3113.4C14—C13—C12122.7 (6)
C2—C3—H3113.4C14—C13—H13118.6
O2—C4—C5124.2 (4)C12—C13—H13118.6
O2—C4—C3118.1 (4)C13—C14—C15120.3 (6)
C5—C4—C3117.5 (4)C13—C14—H14119.9
C4—C5—C7119.2 (5)C15—C14—H14119.9
C4—C5—C6116.4 (4)C14—C15—C16120.3 (6)
C7—C5—C657.7 (4)C14—C15—H15119.8
C4—C5—H5116.8C16—C15—H15119.8
C7—C5—H5116.8C11—C16—C15119.0 (5)
C6—C5—H5116.8C11—C16—H16120.5
C7—C6—C560.3 (3)C15—C16—H16120.5
C7—C6—H6A117.7C18—C17—C22119.2 (4)
C5—C6—H6A117.7C18—C17—C10121.4 (4)
C7—C6—H6B117.7C22—C17—C10119.4 (4)
C5—C6—H6B117.7C17—C18—C19120.6 (5)
H6A—C6—H6B114.9C17—C18—H18119.7
C6—C7—C562.0 (3)C19—C18—H18119.7
C6—C7—H7A117.6C20—C19—C18119.3 (6)
C5—C7—H7A117.6C20—C19—H19120.3
C6—C7—H7B117.6C18—C19—H19120.3
C5—C7—H7B117.6C19—C20—C21120.6 (5)
H7A—C7—H7B114.7C19—C20—H20119.7
O3—C8—C2107.7 (3)C21—C20—H20119.7
O3—C8—C9112.7 (4)C22—C21—C20120.0 (5)
C2—C8—C9111.9 (4)C22—C21—H21120.0
O3—C8—H8108.1C20—C21—H21120.0
C2—C8—H8108.1C21—C22—C17120.3 (5)
C9—C8—H8108.1C21—C22—H22119.8
C8—C9—H9A109.5C17—C22—H22119.8
C8—C9—H9B109.5C1—N1—C10130.9 (3)
H9A—C9—H9B109.5C1—N1—C394.7 (3)
C8—C9—H9C109.5C10—N1—C3132.0 (3)
H9A—C9—H9C109.5C8—O3—H3A109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O1i0.822.042.783 (4)150
C18—H18···O2ii0.932.293.199 (6)165
Symmetry codes: (i) x+3/2, y+1/2, z; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC22H23NO3
Mr349.41
Crystal system, space groupMonoclinic, C2
Temperature (K)153
a, b, c (Å)18.8279 (13), 6.1645 (4), 16.3539 (10)
β (°) 99.529 (6)
V3)1871.9 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.42 × 0.40 × 0.35
Data collection
DiffractometerBruker APEX area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2002)
Tmin, Tmax0.966, 0.972
No. of measured, independent and
observed [I > 2σ(I)] reflections
6131, 2007, 1312
Rint0.034
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.157, 1.07
No. of reflections2007
No. of parameters237
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O1i0.822.042.783 (4)149.9
C18—H18···O2ii0.932.293.199 (6)165.4
Symmetry codes: (i) x+3/2, y+1/2, z; (ii) x, y+1, z.
 

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