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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2610.
Published online 2009 October 3. doi:  10.1107/S1600536809039452
PMCID: PMC2971100

Bis{[1-(tert-butoxy­carbonyl)­pyrrolidin-2-yl]meth­yl} carbonate

Abstract

The asymmetric unit of the title compound, C21H36N2O7, consists of two independent half-mol­ecules, the other halves being generated by twofold rotational axes. The two independent half-mol­ecules are related by a pseudo-inversion center. In one, the pyrrolidine ring adopts a twist conformation whereas in the other it is in an envelope conformation. The crystal packing is stabilized by C—H(...)O hydrogen bonds.

Related literature

For the use of proline derivatives in organocatalysis, see: Dalko & Moisan (2004 [triangle]). For the synthesis, see: Wiegrebe et al. (1974 [triangle]).

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Object name is e-65-o2610-scheme1.jpg

Experimental

Crystal data

  • C21H36N2O7
  • M r = 428.52
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2610-efi1.jpg
  • a = 21.995 (5) Å
  • b = 9.9534 (18) Å
  • c = 10.531 (2) Å
  • β = 100.631 (3)°
  • V = 2265.9 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 93 K
  • 0.43 × 0.40 × 0.33 mm

Data collection

  • Rigaku AFC10/Saturn724+ diffractometer
  • Absorption correction: none
  • 9271 measured reflections
  • 2735 independent reflections
  • 2473 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.073
  • S = 1.00
  • 2735 reflections
  • 280 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.19 e Å−3

Data collection: RAPID-AUTO (Rigaku, 2004 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP in SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809039452/ci2927sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809039452/ci2927Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Centre for Testing and Analysis, Cheng Du Branch, Chinese Academy of Sciences, for analytical support.

supplementary crystallographic information

Comment

Proline derivatives are one of the most important catalysts in organocatalysis (Dalko et al., 2004). Here, we report the crystal structure of the title compound.

The asymmetric unit of the title compound consists of one-half each of two crystallographically independent molecules (Fig. 1). The other halves are generated by crystallographic twofold rotational axes. Bond lengths and angles of these two molecules agree with each other and are normal. In one of the independent unit the pyrrolidine ring (N1/C1-C4) adopts a twist conformation whereas in the other the pyrrolidine ring (N2/C12-C15) adopts an envelope conformation.

The crystal packing is stabilized by C—H···O hydrogen bonds (Table 1).

Experimental

The title compound was synthesized according to the method reported in the literature (Wiegrebe et al., 1974). Colourless single crystals suitable for X-ray diffraction were obtained by slow evaporation of a methanol solution.

Refinement

All H atoms were placed in calculated positions, with C-H = 0.98-1.00 Å, and refined using a riding model, with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
Views of the two independent molecules of the title compound, showing 30% probability displacement ellipsoids and the atomic numbering. Atoms labelled with the suffix A are generated by the symmetry operation (1-x, y, 1-z) in one of the molecules (with ...

Crystal data

C21H36N2O7F(000) = 928
Mr = 428.52Dx = 1.256 Mg m3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2yCell parameters from 3700 reflections
a = 21.995 (5) Åθ = 3.1–27.5°
b = 9.9534 (18) ŵ = 0.09 mm1
c = 10.531 (2) ÅT = 93 K
β = 100.631 (3)°Block, colourless
V = 2265.9 (8) Å30.43 × 0.40 × 0.33 mm
Z = 4

Data collection

Rigaku AFC10/Saturn724+ diffractometer2473 reflections with I > 2σ(I)
Radiation source: Rotating AnodeRint = 0.026
graphiteθmax = 27.5°, θmin = 3.1°
Detector resolution: 28.5714 pixels mm-1h = −28→28
multi–scank = −12→10
9271 measured reflectionsl = −12→13
2735 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.073w = 1/[σ2(Fo2) + (0.041P)2 + 0.316P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
2735 reflectionsΔρmax = 0.20 e Å3
280 parametersΔρmin = −0.19 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0009 (3)

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.
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)

xyzUiso*/Ueq
O10.61523 (6)0.82679 (13)0.77609 (13)0.0210 (3)
O20.70399 (6)0.83717 (14)0.92900 (13)0.0251 (3)
O30.54724 (6)1.15192 (13)0.54879 (13)0.0262 (3)
O40.50000.9521 (2)0.50000.0226 (4)
N10.65682 (7)1.02483 (17)0.83522 (14)0.0178 (4)
C10.70038 (9)1.1193 (2)0.91204 (18)0.0210 (4)
H1A0.74351.10000.90310.025*
H1B0.69731.11581.00460.025*
C20.67903 (8)1.2547 (2)0.85289 (18)0.0219 (4)
H2A0.69781.27410.77630.026*
H2B0.68941.32820.91650.026*
C30.60872 (8)1.23572 (19)0.81495 (18)0.0230 (4)
H3A0.58851.24520.89100.028*
H3B0.59051.30180.74840.028*
C40.60199 (8)1.09260 (18)0.76148 (17)0.0169 (4)
H40.56341.05040.78040.020*
C50.60269 (8)1.0861 (2)0.61761 (17)0.0209 (4)
H5A0.64001.13190.59870.025*
H5B0.60360.99130.58960.025*
C60.50001.0718 (3)0.50000.0188 (6)
C70.66228 (8)0.8903 (2)0.85346 (17)0.0184 (4)
C80.61266 (9)0.6788 (2)0.77050 (18)0.0195 (4)
C90.66997 (10)0.6233 (2)0.7267 (2)0.0275 (5)
H9A0.70630.63760.79470.033*
H9B0.67590.66970.64780.033*
H9C0.66460.52690.70930.033*
C100.60458 (10)0.6224 (2)0.90045 (19)0.0248 (4)
H10A0.57030.66850.92960.030*
H10B0.64270.63610.96380.030*
H10C0.59560.52600.89180.030*
C110.55506 (10)0.6543 (2)0.6687 (2)0.0274 (5)
H11A0.55960.69880.58800.033*
H11B0.51880.69080.69880.033*
H11C0.54960.55760.65360.033*
O50.87815 (6)0.72148 (13)0.73864 (12)0.0195 (3)
O60.79858 (6)0.70687 (14)0.56549 (12)0.0224 (3)
O70.97677 (6)0.38716 (13)0.90069 (11)0.0193 (3)
O81.00000.5876 (2)1.00000.0284 (5)
N20.84043 (7)0.52083 (17)0.67249 (14)0.0172 (4)
C120.79789 (8)0.4284 (2)0.59120 (17)0.0198 (4)
H12A0.79870.44190.49840.024*
H12B0.75500.43930.60570.024*
C130.82406 (10)0.2922 (2)0.63755 (19)0.0240 (5)
H13A0.85830.26590.59350.029*
H13B0.79170.22190.62270.029*
C140.84733 (9)0.31487 (19)0.78185 (18)0.0235 (4)
H14A0.87890.24710.81730.028*
H14B0.81280.31040.83030.028*
C150.87548 (7)0.45583 (18)0.78907 (16)0.0156 (3)
H15A0.86800.50330.86840.019*
C160.94416 (7)0.45378 (19)0.78534 (16)0.0183 (4)
H16A0.95140.40520.70740.022*
H16B0.95970.54680.78150.022*
C171.00000.4671 (3)1.00000.0172 (5)
C180.83557 (8)0.6552 (2)0.65213 (17)0.0171 (4)
C190.88191 (9)0.8700 (2)0.73624 (18)0.0199 (4)
C200.93749 (10)0.8980 (2)0.84211 (19)0.0258 (4)
H20A0.97420.85490.82010.031*
H20B0.92980.86190.92430.031*
H20C0.94430.99510.85020.031*
C210.89438 (10)0.9192 (2)0.60638 (18)0.0270 (5)
H21A0.85770.90350.53950.032*
H21B0.92970.87020.58440.032*
H21C0.90371.01560.61170.032*
C220.82306 (9)0.9276 (2)0.7694 (2)0.0265 (4)
H22A0.81560.88760.85020.032*
H22B0.78820.90730.69970.032*
H22C0.82731.02520.77980.032*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0213 (7)0.0133 (8)0.0254 (7)−0.0019 (5)−0.0034 (5)0.0023 (5)
O20.0217 (7)0.0242 (9)0.0260 (7)0.0008 (6)−0.0046 (6)0.0067 (6)
O30.0272 (7)0.0192 (7)0.0259 (7)−0.0017 (6)−0.0118 (6)0.0039 (6)
O40.0231 (9)0.0178 (12)0.0262 (10)0.0000.0024 (8)0.000
N10.0147 (7)0.0170 (9)0.0193 (8)−0.0025 (6)−0.0027 (6)0.0010 (6)
C10.0165 (9)0.0244 (12)0.0198 (9)−0.0046 (8)−0.0027 (7)0.0003 (8)
C20.0190 (9)0.0201 (11)0.0242 (10)−0.0026 (8)−0.0021 (8)−0.0018 (8)
C30.0189 (8)0.0226 (10)0.0259 (9)0.0026 (8)0.0000 (7)−0.0038 (8)
C40.0120 (7)0.0179 (10)0.0201 (9)−0.0004 (7)0.0011 (6)0.0010 (7)
C50.0169 (8)0.0244 (10)0.0197 (9)0.0006 (7)−0.0011 (7)0.0013 (7)
C60.0212 (12)0.0211 (16)0.0131 (12)0.0000.0003 (10)0.000
C70.0150 (8)0.0222 (11)0.0174 (8)−0.0016 (8)0.0011 (7)0.0006 (8)
C80.0225 (9)0.0136 (10)0.0208 (10)−0.0004 (8)0.0002 (8)0.0001 (7)
C90.0298 (10)0.0281 (12)0.0254 (10)0.0028 (9)0.0070 (8)0.0013 (9)
C100.0323 (11)0.0189 (11)0.0241 (10)−0.0016 (8)0.0077 (8)0.0016 (8)
C110.0307 (11)0.0189 (11)0.0286 (11)−0.0009 (9)−0.0053 (9)−0.0011 (9)
O50.0218 (6)0.0140 (8)0.0201 (6)−0.0001 (5)−0.0032 (5)−0.0006 (5)
O60.0211 (7)0.0220 (8)0.0215 (7)0.0048 (6)−0.0028 (6)0.0028 (6)
O70.0184 (6)0.0175 (7)0.0187 (6)0.0002 (5)−0.0049 (5)0.0004 (5)
O80.0403 (12)0.0182 (12)0.0235 (10)0.000−0.0028 (9)0.000
N20.0160 (8)0.0170 (9)0.0160 (7)0.0004 (6)−0.0041 (6)0.0005 (6)
C120.0184 (9)0.0193 (11)0.0192 (9)−0.0021 (8)−0.0031 (7)−0.0018 (8)
C130.0250 (10)0.0184 (12)0.0244 (10)−0.0052 (8)−0.0062 (8)−0.0005 (8)
C140.0230 (9)0.0212 (10)0.0236 (9)−0.0057 (8)−0.0029 (7)0.0043 (8)
C150.0150 (7)0.0159 (9)0.0147 (8)0.0012 (7)−0.0003 (6)0.0006 (7)
C160.0155 (8)0.0223 (10)0.0157 (8)0.0007 (7)−0.0008 (6)0.0010 (7)
C170.0122 (11)0.0201 (16)0.0189 (12)0.0000.0017 (10)0.000
C180.0165 (8)0.0178 (11)0.0169 (9)0.0013 (7)0.0030 (7)0.0001 (7)
C190.0248 (10)0.0127 (11)0.0215 (9)0.0014 (8)0.0030 (8)0.0015 (8)
C200.0296 (10)0.0191 (11)0.0268 (10)−0.0037 (8)−0.0003 (8)−0.0023 (8)
C210.0345 (11)0.0222 (12)0.0246 (10)−0.0019 (9)0.0065 (9)0.0017 (8)
C220.0286 (10)0.0189 (11)0.0331 (10)0.0022 (8)0.0086 (9)−0.0040 (9)

Geometric parameters (Å, °)

O1—C71.350 (2)O5—C181.352 (2)
O1—C81.475 (2)O5—C191.482 (2)
O2—C71.219 (2)O6—C181.219 (2)
O3—C61.335 (2)O7—C171.338 (2)
O3—C51.455 (2)O7—C161.4519 (19)
O4—C61.191 (4)O8—C171.200 (4)
N1—C71.355 (3)N2—C181.355 (3)
N1—C41.472 (2)N2—C121.469 (2)
N1—C11.473 (2)N2—C151.473 (2)
C1—C21.522 (3)C12—C131.518 (3)
C1—H1A0.99C12—H12A0.99
C1—H1B0.99C12—H12B0.99
C2—C31.536 (2)C13—C141.528 (3)
C2—H2A0.99C13—H13A0.99
C2—H2B0.99C13—H13B0.99
C3—C41.529 (3)C14—C151.530 (3)
C3—H3A0.99C14—H14A0.99
C3—H3B0.99C14—H14B0.99
C4—C51.519 (2)C15—C161.518 (2)
C4—H41.00C15—H15A1.00
C5—H5A0.99C16—H16A0.99
C5—H5B0.99C16—H16B0.99
C6—O3i1.335 (2)C17—O7ii1.338 (2)
C8—C101.520 (3)C19—C221.514 (3)
C8—C111.521 (3)C19—C201.520 (3)
C8—C91.524 (3)C19—C211.524 (3)
C9—H9A0.98C20—H20A0.98
C9—H9B0.98C20—H20B0.98
C9—H9C0.98C20—H20C0.98
C10—H10A0.98C21—H21A0.98
C10—H10B0.98C21—H21B0.98
C10—H10C0.98C21—H21C0.98
C11—H11A0.98C22—H22A0.98
C11—H11B0.98C22—H22B0.98
C11—H11C0.98C22—H22C0.98
C7—O1—C8120.75 (16)C18—O5—C19120.63 (15)
C6—O3—C5116.37 (15)C17—O7—C16116.16 (15)
C7—N1—C4124.77 (16)C18—N2—C12120.16 (16)
C7—N1—C1121.41 (17)C18—N2—C15125.37 (15)
C4—N1—C1112.57 (16)C12—N2—C15112.93 (15)
N1—C1—C2102.72 (15)N2—C12—C13102.06 (14)
N1—C1—H1A111.2N2—C12—H12A111.4
C2—C1—H1A111.2C13—C12—H12A111.4
N1—C1—H1B111.2N2—C12—H12B111.4
C2—C1—H1B111.2C13—C12—H12B111.4
H1A—C1—H1B109.1H12A—C12—H12B109.2
C1—C2—C3102.54 (16)C12—C13—C14103.02 (16)
C1—C2—H2A111.3C12—C13—H13A111.2
C3—C2—H2A111.3C14—C13—H13A111.2
C1—C2—H2B111.3C12—C13—H13B111.2
C3—C2—H2B111.3C14—C13—H13B111.2
H2A—C2—H2B109.2H13A—C13—H13B109.1
C4—C3—C2103.59 (15)C13—C14—C15104.08 (15)
C4—C3—H3A111.0C13—C14—H14A110.9
C2—C3—H3A111.0C15—C14—H14A110.9
C4—C3—H3B111.0C13—C14—H14B110.9
C2—C3—H3B111.0C15—C14—H14B110.9
H3A—C3—H3B109.0H14A—C14—H14B109.0
N1—C4—C5110.40 (14)N2—C15—C16110.76 (13)
N1—C4—C3102.62 (14)N2—C15—C14102.50 (14)
C5—C4—C3112.86 (15)C16—C15—C14112.45 (15)
N1—C4—H4110.2N2—C15—H15A110.3
C5—C4—H4110.2C16—C15—H15A110.3
C3—C4—H4110.2C14—C15—H15A110.3
O3—C5—C4108.41 (14)O7—C16—C15108.95 (13)
O3—C5—H5A110.0O7—C16—H16A109.9
C4—C5—H5A110.0C15—C16—H16A109.9
O3—C5—H5B110.0O7—C16—H16B109.9
C4—C5—H5B110.0C15—C16—H16B109.9
H5A—C5—H5B108.4H16A—C16—H16B108.3
O4—C6—O3i126.69 (12)O8—C17—O7126.48 (11)
O4—C6—O3126.69 (12)O8—C17—O7ii126.48 (11)
O3i—C6—O3106.6 (2)O7—C17—O7ii107.0 (2)
O2—C7—O1126.3 (2)O6—C18—O5125.61 (19)
O2—C7—N1123.91 (19)O6—C18—N2123.86 (19)
O1—C7—N1109.83 (16)O5—C18—N2110.51 (16)
O1—C8—C10110.09 (16)O5—C19—C22108.72 (16)
O1—C8—C11102.07 (16)O5—C19—C20102.10 (15)
C10—C8—C11110.79 (17)C22—C19—C20111.57 (16)
O1—C8—C9110.27 (16)O5—C19—C21110.84 (16)
C10—C8—C9112.29 (17)C22—C19—C21112.85 (17)
C11—C8—C9110.88 (16)C20—C19—C21110.23 (17)
C8—C9—H9A109.5C19—C20—H20A109.5
C8—C9—H9B109.5C19—C20—H20B109.5
H9A—C9—H9B109.5H20A—C20—H20B109.5
C8—C9—H9C109.5C19—C20—H20C109.5
H9A—C9—H9C109.5H20A—C20—H20C109.5
H9B—C9—H9C109.5H20B—C20—H20C109.5
C8—C10—H10A109.5C19—C21—H21A109.5
C8—C10—H10B109.5C19—C21—H21B109.5
H10A—C10—H10B109.5H21A—C21—H21B109.5
C8—C10—H10C109.5C19—C21—H21C109.5
H10A—C10—H10C109.5H21A—C21—H21C109.5
H10B—C10—H10C109.5H21B—C21—H21C109.5
C8—C11—H11A109.5C19—C22—H22A109.5
C8—C11—H11B109.5C19—C22—H22B109.5
H11A—C11—H11B109.5H22A—C22—H22B109.5
C8—C11—H11C109.5C19—C22—H22C109.5
H11A—C11—H11C109.5H22A—C22—H22C109.5
H11B—C11—H11C109.5H22B—C22—H22C109.5
C7—N1—C1—C2176.45 (17)C18—N2—C12—C13174.22 (16)
C4—N1—C1—C2−15.76 (19)C15—N2—C12—C13−19.19 (18)
N1—C1—C2—C333.84 (18)N2—C12—C13—C1435.11 (18)
C1—C2—C3—C4−40.29 (18)C12—C13—C14—C15−39.24 (19)
C7—N1—C4—C5−81.3 (2)C18—N2—C15—C16−78.9 (2)
C1—N1—C4—C5111.38 (17)C12—N2—C15—C16115.30 (16)
C7—N1—C4—C3158.15 (17)C18—N2—C15—C14160.90 (17)
C1—N1—C4—C3−9.15 (19)C12—N2—C15—C14−4.86 (18)
C2—C3—C4—N130.20 (18)C13—C14—C15—N226.95 (18)
C2—C3—C4—C5−88.61 (17)C13—C14—C15—C16−92.03 (17)
C6—O3—C5—C4−98.00 (16)C17—O7—C16—C15−94.52 (15)
N1—C4—C5—O3178.94 (14)N2—C15—C16—O7−179.11 (14)
C3—C4—C5—O3−66.87 (18)C14—C15—C16—O7−65.08 (18)
C5—O3—C6—O4−5.10 (16)C16—O7—C17—O8−5.21 (14)
C5—O3—C6—O3i174.90 (16)C16—O7—C17—O7ii174.79 (14)
C8—O1—C7—O2−4.2 (3)C19—O5—C18—O61.8 (3)
C8—O1—C7—N1175.71 (15)C19—O5—C18—N2−179.82 (14)
C4—N1—C7—O2−169.34 (17)C12—N2—C18—O6−2.7 (3)
C1—N1—C7—O2−3.1 (3)C15—N2—C18—O6−167.50 (16)
C4—N1—C7—O110.8 (3)C12—N2—C18—O5178.84 (14)
C1—N1—C7—O1176.99 (15)C15—N2—C18—O514.0 (2)
C7—O1—C8—C1064.9 (2)C18—O5—C19—C2265.4 (2)
C7—O1—C8—C11−177.36 (15)C18—O5—C19—C20−176.56 (15)
C7—O1—C8—C9−59.5 (2)C18—O5—C19—C21−59.2 (2)

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2B···O2iii0.992.603.223 (2)121
C5—H5A···O6iv0.992.503.380 (2)148
C13—H13B···O6v0.992.543.231 (2)127

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2927).

References

  • Dalko, P. I. & Moisan, L. (2004). Angew. Chem. Int. Ed.43, 5138–5175. [PubMed]
  • Rigaku (2004). RAPID-AUTO Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wiegrebe, W., Herrmann, E. G., Schlunegger, U. P. & Budzikiewicz, H. (1974). Helv. Chim. Acta, 57, 301–314. [PubMed]

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