5-tert-Butyl­peroxy-5-(oxiran-2-yl)-1-(prop-2-ynyl)­pyrrolidin-2-one

The title compound, C₁₃H₁₉NO₄, contains the 5-tert-butyl­peroxy-, 5-oxiranyl- and 1-prop-2-ynyl-substituted pyrrolidin-2-one ring system in an envelope conformation, with one CH₂ C atom out of the plane by 0.272 (3) Å.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.040
• wR factor = 0.096
• Data-to-parameter ratio = 12.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           24.90
         From the CIF: _reflns_number_total               2041
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         2338
         Completeness (_total/calc)             87.30%
          Alert B: < 90% complete (theta max?)


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 0 Alert Level C = Please check

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S1. Comment

The action of tert-butyl hydroperoxide and tin(IV) chloride upon allylic alcohols containing a lactam ring leads mainly to epoxy alkyl peroxides with high diastereoselection. The structure of the title compound, (I), is the anti-diastereoisomer of one such peroxide. The core of the structure is a pyrrolidinone ring in an envelope conformation (Cremer & Pople, 1975), with C6 out of the ring plane by 0.272 (3) Å. The substituents consist of a prop-2-ynyl chain attached to the ring N atom and both t-butylperoxy and oxiranyl moieties attached to C7 in the 5-position, making it an S configuration. All bond lengths and angles were found to be within expected ranges. No classic hydrogen bonds were found; however, a number of C—H···O interactions with separations less than the sum of the van der Waals radii (Bondi, 1964) were found to form a three-dimensional network. These interactions are detailed in Table 2.

S2. Experimental

The reaction of a diperoxide and an epoxy peroxide in the presence of SnCl₄ produced a mixture of diastereoisomers. Crystals of (I) were obtained from an ethyl acetate/petroleum ether (313–333 K) mixture (Hursthouse et al., 1995; Marson et al., 2001).

S3. Refinement

Details of the data collection method are described by Darr et al. (1993). H atoms were treated as riding atoms (C—H = 0.93 and 0.97 Å).

Computing details

Data collection: MADNES (Pflugrath & Messerschmidt, 1989); cell refinement: MADNES; data reduction: ABSMAD (Karaulov, 1992); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: CAMERON (Watkin et al., 1993).

Figures

Fig. 1. View of (I) shown with 50% probability displacement ellipsoids.

(I)

Crystal data

C13H19NO4	F(000) = 544
Mr = 253.29	Dx = 1.257 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71069 Å
a = 10.2870 (14) Å	Cell parameters from 5318 reflections
b = 10.729 (2) Å	θ = 2.5–24.9°
c = 13.1233 (13) Å	µ = 0.09 mm^−1
β = 112.423 (13)°	T = 150 K
V = 1338.9 (4) Å^3	Block, colourless
Z = 4	0.2 × 0.2 × 0.15 mm

Data collection

FAST TV area-detector diffractometer	1516 reflections with I > 2σ(I)
ϕ and ω scans	Rint = 0.073
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983)	θmax = 24.9°, θmin = 2.5°
Tmin = 0.985, Tmax = 0.989	h = −11→12
5318 measured reflections	k = −9→12
2041 independent reflections	l = −14→14

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.040	w = 1/[σ^2(Fo^2) + (0.0482P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.096	(Δ/σ)max = 0.003
S = 0.91	Δρmax = 0.23 e Å^−3
2041 reflections	Δρmin = −0.19 e Å^−3
166 parameters

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.33428 (13)	0.50201 (12)	0.30627 (12)	0.0190 (4)
O1	0.57416 (12)	0.51488 (11)	0.38099 (10)	0.0290 (4)
O2	0.14074 (12)	0.62273 (11)	0.19129 (10)	0.0255 (3)
O3	0.23830 (12)	0.71414 (11)	0.17439 (10)	0.0278 (3)
O4	0.01181 (12)	0.53935 (11)	0.36334 (11)	0.0318 (4)
C1	0.3271 (2)	0.3980 (2)	0.2334 (2)	0.0273 (5)
H1A	0.4181	0.3880	0.2282	0.033*
H1B	0.2593	0.4175	0.1602	0.033*
C2	0.2873 (2)	0.2796 (2)	0.2693 (2)	0.0264 (5)
C3	0.2535 (2)	0.1852 (2)	0.2981 (2)	0.0364 (5)
H3	0.2268	0.1107	0.3208	0.044*
C4	0.4584 (2)	0.5569 (2)	0.36907 (14)	0.0212 (4)
C5	0.4280 (2)	0.6738 (2)	0.41816 (15)	0.0235 (4)
H5A	0.4534	0.7467	0.38615	0.028*
H5B	0.4797	0.6752	0.49731	0.028*
C6	0.2695 (2)	0.6708 (2)	0.39061 (15)	0.0229 (4)
H6A	0.2504	0.6479	0.45502	0.028*
H6B	0.2280	0.7518	0.36488	0.028*
C7	0.2102 (2)	0.5729 (2)	0.29977 (14)	0.0208 (4)
C8	0.0963 (2)	0.48882 (15)	0.3084 (2)	0.0223 (4)
H8	0.0459	0.43817	0.2431	0.027*
C9	0.1048 (2)	0.4362 (2)	0.4126 (2)	0.0317 (5)
H9A	0.0629	0.3549	0.4114	0.038*
H9B	0.1888	0.4529	0.4774	0.038*
C10	0.1530 (2)	0.8031 (2)	0.09353 (15)	0.0224 (4)
C11	0.0782 (2)	0.7378 (2)	−0.0160 (2)	0.0354 (5)
H11A	0.0201	0.7966	−0.0690	0.053*
H11B	0.0206	0.6719	−0.0066	0.053*
H11C	0.1464	0.7036	−0.0416	0.053*
C12	0.0529 (2)	0.8694 (2)	0.1350 (2)	0.0313 (5)
H12A	0.0007	0.9309	0.0821	0.047*
H12B	0.1054	0.9092	0.2040	0.047*
H12C	−0.0109	0.8099	0.1451	0.047*
C13	0.2633 (2)	0.8938 (2)	0.0877 (2)	0.0323 (5)
H13A	0.2183	0.9591	0.0363	0.048*
H13B	0.3283	0.8506	0.0638	0.048*
H13C	0.3131	0.9292	0.1593	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0203 (8)	0.0166 (8)	0.0198 (8)	−0.0004 (6)	0.0074 (6)	−0.0026 (6)
O1	0.0222 (7)	0.0344 (8)	0.0295 (8)	0.0050 (6)	0.0087 (6)	0.0017 (6)
O2	0.0234 (7)	0.0265 (7)	0.0232 (7)	−0.0051 (6)	0.0053 (5)	0.0096 (6)
O3	0.0198 (7)	0.0318 (7)	0.0306 (8)	0.0001 (6)	0.0084 (5)	0.0136 (6)
O4	0.0306 (7)	0.0284 (7)	0.0427 (9)	0.0031 (6)	0.0209 (6)	0.0029 (6)
C1	0.0319 (11)	0.0256 (11)	0.0258 (11)	0.0008 (9)	0.0125 (8)	−0.0032 (9)
C2	0.0268 (11)	0.0218 (10)	0.0271 (11)	0.0012 (9)	0.0064 (8)	−0.0068 (9)
C3	0.0399 (12)	0.0247 (11)	0.0383 (13)	−0.0042 (10)	0.0079 (10)	−0.0044 (10)
C4	0.0225 (10)	0.0229 (10)	0.0170 (10)	0.0014 (9)	0.0064 (7)	0.0063 (8)
C5	0.0252 (10)	0.0187 (10)	0.0237 (11)	−0.0028 (8)	0.0062 (8)	0.0007 (8)
C6	0.0272 (10)	0.0191 (9)	0.0227 (11)	0.0004 (8)	0.0097 (8)	0.0002 (8)
C7	0.0217 (9)	0.0185 (9)	0.0212 (10)	0.0021 (8)	0.0069 (8)	0.0042 (8)
C8	0.0218 (9)	0.0190 (9)	0.0259 (11)	0.0018 (8)	0.0090 (8)	0.0003 (8)
C9	0.0292 (11)	0.0308 (11)	0.0328 (12)	−0.0021 (9)	0.0094 (9)	0.0107 (9)
C10	0.0220 (10)	0.0230 (10)	0.0215 (10)	0.0040 (8)	0.0075 (8)	0.0088 (8)
C11	0.0420 (12)	0.0391 (12)	0.0247 (12)	−0.0020 (10)	0.0124 (9)	0.0037 (9)
C12	0.0336 (11)	0.0272 (11)	0.0363 (13)	0.0031 (9)	0.0170 (9)	0.0065 (9)
C13	0.0264 (11)	0.0365 (11)	0.0338 (12)	0.0019 (9)	0.0114 (9)	0.0136 (10)

Geometric parameters (Å, º)

N1—C4	1.361 (2)	C2—C3	1.179 (3)
N1—C1	1.453 (2)	C4—C5	1.496 (2)
N1—C7	1.460 (2)	C5—C6	1.529 (2)
O1—C4	1.227 (2)	C6—C7	1.530 (2)
O2—C7	1.431 (2)	C7—C8	1.517 (2)
O2—O3	1.479 (2)	C8—C9	1.451 (3)
O3—C10	1.448 (2)	C10—C12	1.513 (2)
O4—C8	1.431 (2)	C10—C13	1.519 (2)
O4—C9	1.445 (2)	C10—C11	1.518 (3)
C1—C2	1.467 (3)
C4—N1—C1	122.10 (14)	N1—C7—C8	111.62 (13)
C4—N1—C7	114.00 (13)	O2—C7—C6	114.72 (14)
C1—N1—C7	122.54 (13)	N1—C7—C6	103.43 (13)
C7—O2—O3	106.66 (11)	C8—C7—C6	116.09 (15)
C10—O3—O2	106.92 (11)	O4—C8—C9	60.15 (11)
C8—O4—C9	60.63 (11)	O4—C8—C7	116.58 (14)
N1—C1—C2	113.8 (2)	C9—C8—C7	122.1 (2)
C3—C2—C1	179.0 (2)	O4—C9—C8	59.22 (11)
O1—C4—N1	124.0 (2)	O3—C10—C12	110.57 (14)
O1—C4—C5	127.3 (2)	O3—C10—C13	101.79 (13)
N1—C4—C5	108.76 (14)	C12—C10—C13	109.94 (15)
C4—C5—C6	105.05 (13)	O3—C10—C11	109.63 (14)
C7—C6—C5	105.71 (14)	C12—C10—C11	112.8 (2)
O2—C7—N1	110.28 (13)	C13—C10—C11	111.5 (2)
O2—C7—C8	100.92 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···O1^i	0.96	2.59	3.387 (2)	140
C3—H3···O1^ii	0.93	2.42	3.275 (3)	153
C9—H9B···O1^iii	0.97	2.46	3.420 (2)	169
C5—H5A···O4^iv	0.97	2.42	3.348 (2)	160

Symmetry codes: (i) x−1/2, −y+3/2, z; (ii) x−1/2, −y+1/2, z; (iii) −x+1, −y+1, −z+1; (iv) x+1/2, −y+3/2, z.