1-Ethyl 2-methyl 3,4-bis­(acet­yloxy)pyrrolidine-1,2-di­carboxyl­ate: crystal structure, Hirshfeld surface analysis and computational chemistry

The tetra-substituted pyrrolidine ring in the title compound has a twisted conformation about the central C—C bond with the N-bound ethyl­carboxyl­ate group in an equatorial position and the remaining substituents in axial positions. In the crystal, methyl- and methyl­ene-C—H...O(carbon­yl) inter­actions involving all four carbonyl-O atoms lead to supra­molecular double-layers.

Key indicators

• Single-crystal X-ray study
• T = 290 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.042
• wR factor = 0.128
• Data-to-parameter ratio = 22.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3       ..O1       .       2.62 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3       ..O3       .       2.61 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H11A     ..O7       .       2.66 Ang.
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...    -18.288 Report
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -1.230 Report
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          5 Report

Alert level G
PLAT793_ALERT_4_G Model has Chirality at C1          (Centro SPGR)          R Verify
PLAT793_ALERT_4_G Model has Chirality at C2          (Centro SPGR)          S Verify
PLAT793_ALERT_4_G Model has Chirality at C3          (Centro SPGR)          S Verify
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         18 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          3 Info

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

   0 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
   4 ALERT type 3 Indicator that the structure quality may be low
   7 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

Computing details

Data collection: CAD-4 EXPRESS (Enraf Nonius, 1989); cell refinement: CAD-4 EXPRESS (Enraf Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR2014 (Burla et al., 2015); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), MarvinSketch (ChemAxon, 2010) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

1-Ethyl 2-methyl 3,4-bis(acetyloxy)pyrrolidine-1,2-dicarboxylate

Crystal data

C13H19NO8	Z = 2
Mr = 317.29	F(000) = 336
Triclinic, P1	Dx = 1.338 Mg m^−3
a = 6.8291 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.8670 (11) Å	Cell parameters from 25 reflections
c = 15.814 (3) Å	θ = 10.8–18.2°
α = 100.607 (11)°	µ = 0.11 mm^−1
β = 99.011 (10)°	T = 290 K
γ = 105.054 (7)°	Irregular, colourless
V = 787.5 (2) Å^3	0.40 × 0.35 × 0.10 mm

Data collection

Enraf Nonius TurboCAD-4 diffractometer	θmax = 30.0°, θmin = 2.7°
Radiation source: Enraf Nonius FR590	h = −9→9
non–profiled ω/2θ scans	k = 0→11
4880 measured reflections	l = −22→21
4573 independent reflections	3 standard reflections every 120 min
2571 reflections with I > 2σ(I)	intensity decay: 2%
Rint = 0.020

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0579P)^2 + 0.0763P] where P = (Fo^2 + 2Fc^2)/3
4573 reflections	(Δ/σ)max = 0.001
203 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
O1	0.28490 (19)	0.08131 (19)	0.64555 (9)	0.0568 (3)
O2	0.12213 (18)	0.24723 (18)	0.57354 (8)	0.0513 (3)
O3	0.35221 (19)	0.33818 (18)	0.83767 (9)	0.0586 (3)
O4	0.20434 (18)	0.14935 (17)	0.91551 (8)	0.0504 (3)
O5	−0.5275 (2)	−0.0729 (2)	0.83254 (9)	0.0662 (4)
O6	−0.32790 (16)	−0.06328 (15)	0.73314 (7)	0.0424 (3)
O7	−0.2014 (3)	0.6135 (2)	0.78612 (11)	0.0753 (4)
O8	−0.08692 (17)	0.40628 (15)	0.84074 (7)	0.0426 (3)
N1	0.0250 (2)	0.1764 (2)	0.69258 (9)	0.0433 (3)
C1	0.0322 (2)	0.0990 (2)	0.76913 (10)	0.0372 (3)
H1	0.041065	−0.024702	0.752792	0.045*
C2	−0.1782 (2)	0.0948 (2)	0.79177 (10)	0.0357 (3)
H2	−0.177363	0.096071	0.853908	0.043*
C3	−0.2178 (2)	0.2626 (2)	0.76694 (10)	0.0388 (3)
H3	−0.364464	0.257939	0.758613	0.047*
C4	−0.1353 (2)	0.2683 (2)	0.68313 (11)	0.0430 (4)
H4A	−0.244190	0.204920	0.631224	0.052*
H4B	−0.076679	0.392201	0.679209	0.052*
C5	0.1565 (2)	0.1615 (2)	0.63798 (10)	0.0424 (4)
C6	0.2518 (3)	0.2410 (3)	0.50973 (13)	0.0631 (5)
H6A	0.234590	0.116529	0.480776	0.076*
H6B	0.396809	0.298206	0.538377	0.076*
C7	0.1853 (4)	0.3399 (4)	0.44469 (15)	0.0818 (7)
H7A	0.041201	0.282919	0.417435	0.123*
H7B	0.266749	0.337723	0.400460	0.123*
H7C	0.204764	0.463198	0.474089	0.123*
C8	0.2155 (2)	0.2132 (2)	0.84352 (11)	0.0404 (3)
C9	0.3834 (3)	0.2283 (4)	0.98760 (14)	0.0766 (7)
H9A	0.506912	0.224946	0.966399	0.115*
H9B	0.370682	0.160845	1.032257	0.115*
H9C	0.391528	0.351722	1.012025	0.115*
C10	−0.4972 (2)	−0.1374 (2)	0.76304 (12)	0.0461 (4)
C11	−0.6347 (3)	−0.3050 (3)	0.69971 (16)	0.0697 (6)
H11A	−0.581462	−0.404559	0.706145	0.104*
H11B	−0.639848	−0.289168	0.640732	0.104*
H11C	−0.771979	−0.329842	0.711270	0.104*
C12	−0.0926 (3)	0.5768 (2)	0.84243 (13)	0.0500 (4)
C13	0.0585 (4)	0.7066 (3)	0.92107 (15)	0.0696 (6)
H13A	0.194942	0.735689	0.908739	0.104*
H13B	0.058933	0.652183	0.970653	0.104*
H13C	0.018502	0.815216	0.934292	0.104*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0482 (7)	0.0740 (9)	0.0610 (8)	0.0303 (7)	0.0206 (6)	0.0223 (7)
O2	0.0509 (7)	0.0668 (8)	0.0457 (6)	0.0205 (6)	0.0212 (5)	0.0231 (6)
O3	0.0431 (6)	0.0550 (8)	0.0714 (8)	0.0012 (6)	0.0106 (6)	0.0205 (7)
O4	0.0476 (6)	0.0545 (7)	0.0462 (6)	0.0117 (6)	0.0003 (5)	0.0186 (6)
O5	0.0573 (8)	0.0702 (10)	0.0703 (9)	0.0073 (7)	0.0301 (7)	0.0171 (8)
O6	0.0357 (5)	0.0405 (6)	0.0475 (6)	0.0065 (5)	0.0088 (5)	0.0092 (5)
O7	0.0854 (11)	0.0571 (9)	0.0929 (11)	0.0370 (8)	0.0070 (9)	0.0284 (8)
O8	0.0440 (6)	0.0367 (6)	0.0497 (6)	0.0151 (5)	0.0096 (5)	0.0122 (5)
N1	0.0395 (7)	0.0576 (9)	0.0448 (7)	0.0230 (6)	0.0144 (6)	0.0243 (6)
C1	0.0345 (7)	0.0403 (8)	0.0423 (8)	0.0148 (6)	0.0098 (6)	0.0168 (7)
C2	0.0327 (7)	0.0348 (8)	0.0397 (8)	0.0087 (6)	0.0082 (6)	0.0105 (6)
C3	0.0322 (7)	0.0404 (8)	0.0458 (8)	0.0125 (6)	0.0082 (6)	0.0127 (7)
C4	0.0411 (8)	0.0497 (10)	0.0446 (8)	0.0186 (7)	0.0094 (7)	0.0196 (7)
C5	0.0359 (7)	0.0520 (10)	0.0389 (8)	0.0111 (7)	0.0086 (6)	0.0118 (7)
C6	0.0635 (12)	0.0808 (15)	0.0527 (11)	0.0219 (11)	0.0292 (9)	0.0195 (10)
C7	0.0946 (17)	0.112 (2)	0.0566 (12)	0.0356 (15)	0.0357 (12)	0.0387 (13)
C8	0.0357 (7)	0.0424 (9)	0.0477 (9)	0.0155 (7)	0.0101 (6)	0.0154 (7)
C9	0.0645 (13)	0.0948 (18)	0.0570 (12)	0.0172 (12)	−0.0142 (10)	0.0169 (12)
C10	0.0358 (8)	0.0443 (9)	0.0596 (10)	0.0088 (7)	0.0106 (7)	0.0200 (8)
C11	0.0448 (10)	0.0558 (12)	0.0917 (16)	−0.0003 (9)	0.0043 (10)	0.0075 (11)
C12	0.0516 (9)	0.0402 (9)	0.0677 (12)	0.0181 (8)	0.0229 (9)	0.0213 (9)
C13	0.0803 (14)	0.0425 (11)	0.0764 (14)	0.0050 (10)	0.0192 (12)	0.0075 (10)

Geometric parameters (Å, º)

O1—C5	1.2098 (19)	C3—H3	0.9800
O2—C5	1.345 (2)	C4—H4A	0.9700
O2—C6	1.446 (2)	C4—H4B	0.9700
O3—C8	1.1961 (19)	C6—C7	1.484 (3)
O4—C8	1.3312 (19)	C6—H6A	0.9700
O4—C9	1.445 (2)	C6—H6B	0.9700
O5—C10	1.195 (2)	C7—H7A	0.9600
O6—C10	1.3499 (19)	C7—H7B	0.9600
O6—C2	1.4385 (18)	C7—H7C	0.9600
O7—C12	1.195 (2)	C9—H9A	0.9600
O8—C12	1.348 (2)	C9—H9B	0.9600
O8—C3	1.4496 (19)	C9—H9C	0.9600
N1—C5	1.351 (2)	C10—C11	1.483 (3)
N1—C1	1.4518 (19)	C11—H11A	0.9600
N1—C4	1.464 (2)	C11—H11B	0.9600
C1—C8	1.524 (2)	C11—H11C	0.9600
C1—C2	1.528 (2)	C12—C13	1.496 (3)
C1—H1	0.9800	C13—H13A	0.9600
C2—C3	1.521 (2)	C13—H13B	0.9600
C2—H2	0.9800	C13—H13C	0.9600
C3—C4	1.523 (2)
C5—O2—C6	115.92 (14)	O2—C6—H6B	110.4
C8—O4—C9	115.73 (15)	C7—C6—H6B	110.4
C10—O6—C2	116.20 (12)	H6A—C6—H6B	108.6
C12—O8—C3	118.19 (13)	C6—C7—H7A	109.5
C5—N1—C1	121.34 (13)	C6—C7—H7B	109.5
C5—N1—C4	125.77 (13)	H7A—C7—H7B	109.5
C1—N1—C4	112.89 (12)	C6—C7—H7C	109.5
N1—C1—C8	111.47 (13)	H7A—C7—H7C	109.5
N1—C1—C2	102.32 (12)	H7B—C7—H7C	109.5
C8—C1—C2	113.23 (13)	O3—C8—O4	124.90 (16)
N1—C1—H1	109.9	O3—C8—C1	125.34 (15)
C8—C1—H1	109.9	O4—C8—C1	109.73 (13)
C2—C1—H1	109.9	O4—C9—H9A	109.5
O6—C2—C3	108.78 (12)	O4—C9—H9B	109.5
O6—C2—C1	106.68 (12)	H9A—C9—H9B	109.5
C3—C2—C1	103.23 (12)	O4—C9—H9C	109.5
O6—C2—H2	112.5	H9A—C9—H9C	109.5
C3—C2—H2	112.5	H9B—C9—H9C	109.5
C1—C2—H2	112.5	O5—C10—O6	122.72 (16)
O8—C3—C2	102.26 (11)	O5—C10—C11	125.62 (16)
O8—C3—C4	111.80 (12)	O6—C10—C11	111.66 (16)
C2—C3—C4	103.54 (13)	C10—C11—H11A	109.5
O8—C3—H3	112.8	C10—C11—H11B	109.5
C2—C3—H3	112.8	H11A—C11—H11B	109.5
C4—C3—H3	112.8	C10—C11—H11C	109.5
N1—C4—C3	103.35 (12)	H11A—C11—H11C	109.5
N1—C4—H4A	111.1	H11B—C11—H11C	109.5
C3—C4—H4A	111.1	O7—C12—O8	122.72 (18)
N1—C4—H4B	111.1	O7—C12—C13	126.78 (18)
C3—C4—H4B	111.1	O8—C12—C13	110.46 (16)
H4A—C4—H4B	109.1	C12—C13—H13A	109.5
O1—C5—O2	125.04 (15)	C12—C13—H13B	109.5
O1—C5—N1	124.93 (15)	H13A—C13—H13B	109.5
O2—C5—N1	110.02 (14)	C12—C13—H13C	109.5
O2—C6—C7	106.76 (17)	H13A—C13—H13C	109.5
O2—C6—H6A	110.4	H13B—C13—H13C	109.5
C7—C6—H6A	110.4
C5—N1—C1—C8	76.02 (19)	C2—C3—C4—N1	−27.36 (15)
C4—N1—C1—C8	−103.88 (15)	C6—O2—C5—O1	−0.3 (3)
C5—N1—C1—C2	−162.67 (14)	C6—O2—C5—N1	−179.62 (15)
C4—N1—C1—C2	17.43 (18)	C1—N1—C5—O1	2.0 (3)
C10—O6—C2—C3	−96.72 (15)	C4—N1—C5—O1	−178.13 (17)
C10—O6—C2—C1	152.54 (13)	C1—N1—C5—O2	−178.67 (14)
N1—C1—C2—O6	80.73 (14)	C4—N1—C5—O2	1.2 (2)
C8—C1—C2—O6	−159.17 (12)	C5—O2—C6—C7	178.98 (17)
N1—C1—C2—C3	−33.83 (15)	C9—O4—C8—O3	−6.4 (3)
C8—C1—C2—C3	86.27 (14)	C9—O4—C8—C1	171.57 (15)
C12—O8—C3—C2	−176.59 (13)	N1—C1—C8—O3	−8.7 (2)
C12—O8—C3—C4	73.23 (17)	C2—C1—C8—O3	−123.40 (18)
O6—C2—C3—O8	168.91 (11)	N1—C1—C8—O4	173.33 (13)
C1—C2—C3—O8	−78.04 (13)	C2—C1—C8—O4	58.60 (17)
O6—C2—C3—C4	−74.78 (14)	C2—O6—C10—O5	3.0 (2)
C1—C2—C3—C4	38.26 (15)	C2—O6—C10—C11	−176.72 (15)
C5—N1—C4—C3	−173.74 (15)	C3—O8—C12—O7	0.4 (2)
C1—N1—C4—C3	6.15 (18)	C3—O8—C12—C13	−177.58 (14)
O8—C3—C4—N1	82.01 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O5^i	0.96	2.53	3.403 (3)	151
C3—H3···O1^ii	0.98	2.62	3.419 (2)	139
C3—H3···O3^ii	0.98	2.61	3.453 (2)	144
C11—H11A···O7^iii	0.96	2.66	3.329 (3)	127

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