(3S,5R,6S)-Di­phenyl­methyl 1-oxo-6-bromo­penicillanate

In the title compound, C₂₁H₂₀BrNO₄S, a key inter­mediate in the synthesis of the widely used β-lactamase inhibitor tazobactam, the five-membered thia­zolidine ring adopts an envelope conformation and the four-membered azetidine ring is in a distorted planar conformation. The crystal structure features C—H...O hydrogen bonds and a weak C—H...π inter­action.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.033
• wR factor = 0.083
• Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1       --O1       .        5.5 s.u.
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00605 Ang.
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -0.869 Report
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT012_ALERT_1_G N.O.K.   _shelx_res_checksum Found in CIF ......     Please Check
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT791_ALERT_4_G Model has Chirality at C3          (Chiral SPGR)          S Verify
PLAT791_ALERT_4_G Model has Chirality at C5          (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G Model has Chirality at C6          (Chiral SPGR)          S Verify
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2018 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          2 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   9 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

(3S,5R,6S)-Diphenylmethyl 1-oxo-6-bromopenicillanate

Crystal data

C21H20BrNO4S	Dx = 1.519 Mg m^−3
Mr = 462.35	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P41	Cell parameters from 5313 reflections
Hall symbol: P 4w	θ = 2.2–20.7°
a = 11.076 (2) Å	µ = 2.16 mm^−1
c = 16.478 (3) Å	T = 293 K
V = 2021.4 (7) Å^3	Block, yellow
Z = 4	0.30 × 0.25 × 0.20 mm
F(000) = 944

Data collection

Bruker Kappa APEXII CCD diffractometer	4005 independent reflections
Radiation source: fine-focus sealed tube	2553 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.072
ω and φ scan	θmax = 26.1°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −13→13
Tmin = 0.563, Tmax = 0.672	k = −13→13
20917 measured reflections	l = −20→20

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.0349P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.89	(Δ/σ)max < 0.001
4005 reflections	Δρmax = 0.20 e Å^−3
255 parameters	Δρmin = −0.27 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.016 (8)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.00718 (4)	−0.08038 (4)	0.19956 (3)	0.07083 (18)
S1	0.35274 (8)	0.13083 (9)	0.18370 (7)	0.0532 (3)
O1	0.3126 (3)	0.1885 (3)	0.10598 (17)	0.0729 (9)
O2	−0.0067 (3)	0.2442 (3)	0.16015 (19)	0.0668 (9)
O3	0.1395 (2)	0.3262 (2)	0.39477 (18)	0.0509 (7)
O4	0.2319 (2)	0.4801 (2)	0.33087 (14)	0.0433 (7)
N1	0.1482 (2)	0.1911 (2)	0.24983 (18)	0.0340 (7)
C2	0.3557 (3)	0.2540 (3)	0.2593 (3)	0.0478 (11)
C3	0.2217 (3)	0.2991 (3)	0.2603 (2)	0.0355 (9)
H3	0.2088	0.3525	0.2137	0.043*
C5	0.2117 (3)	0.0786 (3)	0.2304 (2)	0.0393 (10)
H5	0.2207	0.0213	0.2753	0.047*
C6	0.1117 (3)	0.0491 (3)	0.1688 (2)	0.0433 (10)
H6	0.1423	0.0410	0.1132	0.052*
C7	0.0661 (3)	0.1762 (3)	0.1875 (3)	0.0429 (9)
C8	0.3934 (4)	0.1997 (4)	0.3415 (3)	0.0725 (15)
H8A	0.4010	0.2630	0.3809	0.109*
H8B	0.4695	0.1591	0.3357	0.109*
H8C	0.3333	0.1431	0.3591	0.109*
C9	0.4420 (4)	0.3490 (4)	0.2290 (4)	0.090 (2)
H9A	0.4384	0.4183	0.2640	0.135*
H9B	0.4200	0.3722	0.1749	0.135*
H9C	0.5226	0.3172	0.2290	0.135*
C10	0.1903 (3)	0.3669 (3)	0.3367 (2)	0.0385 (9)
C11	0.2093 (3)	0.5603 (3)	0.4013 (2)	0.0392 (9)
H11	0.2150	0.5123	0.4511	0.047*
C12	0.0850 (3)	0.6124 (3)	0.3960 (3)	0.0385 (9)
C13	0.0227 (4)	0.6223 (4)	0.3241 (3)	0.0489 (11)
H13	0.0566	0.5940	0.2761	0.059*
C14	−0.0922 (4)	0.6754 (4)	0.3235 (3)	0.0641 (13)
H14	−0.1342	0.6831	0.2749	0.077*
C15	−0.1417 (4)	0.7151 (4)	0.3933 (4)	0.0660 (13)
H15	−0.2187	0.7483	0.3925	0.079*
C16	−0.0808 (4)	0.7075 (4)	0.4651 (3)	0.0628 (13)
H16	−0.1156	0.7363	0.5127	0.075*
C17	0.0334 (4)	0.6563 (3)	0.4664 (3)	0.0508 (11)
H17	0.0756	0.6515	0.5150	0.061*
C18	0.3106 (3)	0.6508 (3)	0.4006 (2)	0.0370 (9)
C19	0.3129 (4)	0.7455 (4)	0.3469 (3)	0.0479 (11)
H19	0.2509	0.7545	0.3094	0.057*
C20	0.4071 (4)	0.8277 (4)	0.3484 (3)	0.0542 (12)
H20	0.4083	0.8914	0.3116	0.065*
C21	0.4986 (4)	0.8154 (4)	0.4038 (3)	0.0568 (12)
H21	0.5617	0.8708	0.4047	0.068*
C22	0.4969 (3)	0.7212 (4)	0.4581 (3)	0.0597 (12)
H22	0.5587	0.7129	0.4959	0.072*
C23	0.4040 (3)	0.6394 (3)	0.4562 (3)	0.0486 (10)
H23	0.4036	0.5755	0.4928	0.058*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0570 (3)	0.0518 (3)	0.1037 (4)	−0.0182 (2)	0.0112 (3)	−0.0148 (3)
S1	0.0352 (5)	0.0467 (6)	0.0777 (9)	−0.0011 (4)	0.0143 (6)	−0.0181 (6)
O1	0.075 (2)	0.090 (2)	0.054 (2)	−0.0136 (18)	0.0229 (18)	−0.0001 (18)
O2	0.0562 (19)	0.0591 (19)	0.085 (2)	0.0144 (16)	−0.0230 (16)	0.0023 (17)
O3	0.0619 (18)	0.0393 (16)	0.0516 (17)	−0.0119 (13)	0.0178 (16)	−0.0062 (14)
O4	0.0485 (15)	0.0305 (14)	0.0509 (17)	−0.0064 (12)	0.0093 (13)	−0.0076 (12)
N1	0.0290 (16)	0.0246 (16)	0.0486 (19)	0.0025 (12)	0.0027 (15)	−0.0078 (14)
C2	0.030 (2)	0.043 (2)	0.070 (3)	−0.0048 (19)	0.012 (2)	−0.015 (2)
C3	0.035 (2)	0.0265 (19)	0.046 (2)	−0.0021 (16)	0.0077 (18)	−0.0008 (17)
C5	0.039 (2)	0.032 (2)	0.047 (3)	0.0025 (17)	0.0037 (18)	−0.0097 (17)
C6	0.043 (2)	0.038 (2)	0.049 (3)	−0.0055 (17)	0.0026 (19)	−0.0081 (19)
C7	0.042 (2)	0.034 (2)	0.053 (3)	−0.0004 (17)	−0.001 (2)	−0.002 (2)
C8	0.052 (3)	0.083 (4)	0.082 (4)	0.016 (2)	−0.023 (3)	−0.030 (3)
C9	0.058 (3)	0.061 (3)	0.151 (6)	−0.027 (3)	0.045 (3)	−0.033 (3)
C10	0.033 (2)	0.030 (2)	0.053 (3)	−0.0017 (17)	0.002 (2)	−0.009 (2)
C11	0.048 (2)	0.032 (2)	0.038 (2)	−0.0027 (17)	0.0054 (19)	−0.0052 (18)
C12	0.039 (2)	0.030 (2)	0.046 (2)	−0.0059 (16)	0.000 (2)	−0.0033 (18)
C13	0.044 (2)	0.047 (2)	0.056 (3)	−0.0034 (19)	0.000 (2)	−0.011 (2)
C14	0.046 (3)	0.063 (3)	0.083 (4)	−0.006 (2)	−0.015 (3)	−0.010 (3)
C15	0.047 (3)	0.044 (3)	0.107 (4)	0.001 (2)	−0.001 (3)	−0.007 (3)
C16	0.061 (3)	0.049 (3)	0.079 (4)	0.010 (2)	0.020 (3)	−0.010 (3)
C17	0.061 (3)	0.042 (2)	0.049 (3)	0.007 (2)	0.005 (2)	−0.007 (2)
C18	0.033 (2)	0.032 (2)	0.046 (2)	0.0010 (16)	−0.0013 (18)	−0.0067 (19)
C19	0.040 (2)	0.048 (3)	0.057 (3)	−0.0060 (19)	−0.006 (2)	0.002 (2)
C20	0.051 (3)	0.045 (2)	0.066 (3)	−0.008 (2)	0.008 (2)	−0.002 (2)
C21	0.039 (2)	0.056 (3)	0.075 (3)	−0.003 (2)	0.003 (2)	−0.021 (3)
C22	0.042 (2)	0.053 (3)	0.085 (3)	0.004 (2)	−0.019 (2)	−0.009 (3)
C23	0.043 (2)	0.037 (2)	0.065 (3)	0.0060 (17)	−0.011 (2)	0.001 (2)

Geometric parameters (Å, º)

Br1—C6	1.912 (4)	C11—C12	1.495 (5)
S1—O1	1.499 (3)	C11—C18	1.505 (5)
S1—C5	1.835 (4)	C11—H11	0.9800
S1—C2	1.847 (4)	C12—C13	1.375 (6)
O2—C7	1.191 (4)	C12—C17	1.382 (5)
O3—C10	1.199 (4)	C13—C14	1.401 (6)
O4—C10	1.338 (4)	C13—H13	0.9300
O4—C11	1.484 (4)	C14—C15	1.348 (7)
N1—C7	1.382 (5)	C14—H14	0.9300
N1—C3	1.458 (4)	C15—C16	1.364 (6)
N1—C5	1.466 (4)	C15—H15	0.9300
C2—C9	1.506 (6)	C16—C17	1.386 (6)
C2—C8	1.540 (6)	C16—H16	0.9300
C2—C3	1.567 (5)	C17—H17	0.9300
C3—C10	1.505 (5)	C18—C19	1.372 (5)
C3—H3	0.9800	C18—C23	1.388 (5)
C5—C6	1.537 (5)	C19—C20	1.385 (6)
C5—H5	0.9800	C19—H19	0.9300
C6—C7	1.528 (5)	C20—C21	1.371 (6)
C6—H6	0.9800	C20—H20	0.9300
C8—H8A	0.9600	C21—C22	1.374 (6)
C8—H8B	0.9600	C21—H21	0.9300
C8—H8C	0.9600	C22—C23	1.371 (5)
C9—H9A	0.9600	C22—H22	0.9300
C9—H9B	0.9600	C23—H23	0.9300
C9—H9C	0.9600
O1—S1—C5	103.90 (17)	O3—C10—O4	124.8 (3)
O1—S1—C2	105.5 (2)	O3—C10—C3	126.0 (3)
C5—S1—C2	88.00 (16)	O4—C10—C3	109.1 (3)
C10—O4—C11	116.5 (3)	O4—C11—C12	109.9 (3)
C7—N1—C3	123.6 (3)	O4—C11—C18	105.5 (3)
C7—N1—C5	93.0 (3)	C12—C11—C18	115.4 (3)
C3—N1—C5	117.1 (3)	O4—C11—H11	108.6
C9—C2—C8	113.1 (4)	C12—C11—H11	108.6
C9—C2—C3	112.4 (3)	C18—C11—H11	108.6
C8—C2—C3	111.8 (3)	C13—C12—C17	119.2 (4)
C9—C2—S1	107.7 (3)	C13—C12—C11	122.9 (4)
C8—C2—S1	108.0 (3)	C17—C12—C11	117.9 (4)
C3—C2—S1	103.1 (3)	C12—C13—C14	119.7 (4)
N1—C3—C10	112.3 (3)	C12—C13—H13	120.1
N1—C3—C2	105.4 (3)	C14—C13—H13	120.1
C10—C3—C2	112.8 (3)	C15—C14—C13	120.0 (4)
N1—C3—H3	108.7	C15—C14—H14	120.0
C10—C3—H3	108.7	C13—C14—H14	120.0
C2—C3—H3	108.7	C14—C15—C16	121.3 (4)
N1—C5—C6	88.8 (3)	C14—C15—H15	119.4
N1—C5—S1	103.4 (2)	C16—C15—H15	119.4
C6—C5—S1	113.8 (3)	C15—C16—C17	119.3 (4)
N1—C5—H5	115.7	C15—C16—H16	120.4
C6—C5—H5	115.7	C17—C16—H16	120.4
S1—C5—H5	115.7	C12—C17—C16	120.6 (4)
C7—C6—C5	84.8 (3)	C12—C17—H17	119.7
C7—C6—Br1	115.9 (3)	C16—C17—H17	119.7
C5—C6—Br1	114.8 (3)	C19—C18—C23	118.8 (4)
C7—C6—H6	112.8	C19—C18—C11	121.8 (3)
C5—C6—H6	112.8	C23—C18—C11	119.4 (3)
Br1—C6—H6	112.8	C18—C19—C20	120.4 (4)
O2—C7—N1	130.6 (3)	C18—C19—H19	119.8
O2—C7—C6	136.9 (4)	C20—C19—H19	119.8
N1—C7—C6	92.4 (3)	C21—C20—C19	120.2 (4)
C2—C8—H8A	109.5	C21—C20—H20	119.9
C2—C8—H8B	109.5	C19—C20—H20	119.9
H8A—C8—H8B	109.5	C20—C21—C22	119.9 (4)
C2—C8—H8C	109.5	C20—C21—H21	120.0
H8A—C8—H8C	109.5	C22—C21—H21	120.0
H8B—C8—H8C	109.5	C23—C22—C21	119.8 (4)
C2—C9—H9A	109.5	C23—C22—H22	120.1
C2—C9—H9B	109.5	C21—C22—H22	120.1
H9A—C9—H9B	109.5	C22—C23—C18	120.9 (4)
C2—C9—H9C	109.5	C22—C23—H23	119.5
H9A—C9—H9C	109.5	C18—C23—H23	119.5
H9B—C9—H9C	109.5
O1—S1—C2—C9	−58.9 (3)	C5—C6—C7—N1	−7.5 (3)
C5—S1—C2—C9	−162.8 (3)	Br1—C6—C7—N1	107.6 (3)
O1—S1—C2—C8	178.6 (3)	C11—O4—C10—O3	−1.9 (5)
C5—S1—C2—C8	74.7 (3)	C11—O4—C10—C3	−179.8 (3)
O1—S1—C2—C3	60.1 (3)	N1—C3—C10—O3	20.8 (5)
C5—S1—C2—C3	−43.8 (3)	C2—C3—C10—O3	−98.2 (4)
C7—N1—C3—C10	114.4 (4)	N1—C3—C10—O4	−161.3 (3)
C5—N1—C3—C10	−131.4 (3)	C2—C3—C10—O4	79.7 (4)
C7—N1—C3—C2	−122.4 (4)	C10—O4—C11—C12	−82.9 (4)
C5—N1—C3—C2	−8.2 (4)	C10—O4—C11—C18	152.0 (3)
C9—C2—C3—N1	152.1 (4)	O4—C11—C12—C13	−23.0 (5)
C8—C2—C3—N1	−79.5 (4)	C18—C11—C12—C13	96.2 (4)
S1—C2—C3—N1	36.3 (3)	O4—C11—C12—C17	159.5 (3)
C9—C2—C3—C10	−85.0 (4)	C18—C11—C12—C17	−81.4 (4)
C8—C2—C3—C10	43.4 (4)	C17—C12—C13—C14	−0.7 (6)
S1—C2—C3—C10	159.2 (3)	C11—C12—C13—C14	−178.2 (4)
C7—N1—C5—C6	−7.8 (3)	C12—C13—C14—C15	−0.8 (6)
C3—N1—C5—C6	−138.3 (3)	C13—C14—C15—C16	1.6 (7)
C7—N1—C5—S1	106.4 (2)	C14—C15—C16—C17	−0.9 (7)
C3—N1—C5—S1	−24.1 (4)	C13—C12—C17—C16	1.3 (6)
O1—S1—C5—N1	−66.7 (3)	C11—C12—C17—C16	179.0 (4)
C2—S1—C5—N1	38.7 (3)	C15—C16—C17—C12	−0.6 (6)
O1—S1—C5—C6	28.0 (3)	O4—C11—C18—C19	76.6 (4)
C2—S1—C5—C6	133.5 (3)	C12—C11—C18—C19	−45.0 (5)
N1—C5—C6—C7	7.1 (3)	O4—C11—C18—C23	−104.1 (4)
S1—C5—C6—C7	−97.1 (3)	C12—C11—C18—C23	134.3 (4)
N1—C5—C6—Br1	−109.1 (3)	C23—C18—C19—C20	0.2 (6)
S1—C5—C6—Br1	146.69 (19)	C11—C18—C19—C20	179.5 (4)
C3—N1—C7—O2	−43.8 (6)	C18—C19—C20—C21	−0.4 (6)
C5—N1—C7—O2	−169.4 (5)	C19—C20—C21—C22	0.1 (6)
C3—N1—C7—C6	133.5 (3)	C20—C21—C22—C23	0.3 (6)
C5—N1—C7—C6	7.9 (3)	C21—C22—C23—C18	−0.5 (6)
C5—C6—C7—O2	169.5 (5)	C19—C18—C23—C22	0.2 (6)
Br1—C6—C7—O2	−75.4 (6)	C11—C18—C23—C22	−179.1 (4)

Hydrogen-bond geometry (Å, º)

Cg is the centroid of the C18–C23 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21···O2^i	0.93	2.54	3.465 (5)	171
C22—H22···O1^ii	0.93	2.55	3.375 (5)	148
C14—H14···Cg^iii	0.93	2.68	3.533 (5)	153

Symmetry codes: (i) −y+1, x+1, z+1/4; (ii) −x+1, −y+1, z+1/2; (iii) y−1, −x+1, z−1/4.