Related literature {#sec1}
==================

For the tandem 'domino' Diels--Alder reaction, see: Wasserman & Kitzing (1969[@bb8]); Winkler (1996[@bb9]); Padwa & Bur (2007[@bb5]). For related compounds, see: Lautens & Fillion (1996[@bb3], 1997[@bb4]); Domingo *et al.*, (2000[@bb2]).

Experimental {#sec2}
============

 {#sec2.1}

### Crystal data {#sec2.1.1}

C~27~H~29~NO~11~*M* *~r~* = 543.51Monoclinic,*a* = 16.1430 (7) Å*b* = 9.1365 (4) Å*c* = 16.9658 (7) Åβ = 95.019 (1)°*V* = 2492.70 (18) Å^3^*Z* = 4Mo *K*α radiationμ = 0.11 mm^−1^*T* = 120 K0.30 × 0.25 × 0.20 mm

### Data collection {#sec2.1.2}

Bruker SMART 1K CCD diffractometerAbsorption correction: multi-scan (*SADABS*; Sheldrick, 1998[@bb6]) *T* ~min~ = 0.966, *T* ~max~ = 0.97527638 measured reflections7186 independent reflections5342 reflections with *I* \> 2σ(*I*)*R* ~int~ = 0.041

### Refinement {#sec2.1.3}

*R*\[*F* ^2^ \> 2σ(*F* ^2^)\] = 0.054*wR*(*F* ^2^) = 0.151*S* = 1.007186 reflections358 parametersH-atom parameters constrainedΔρ~max~ = 0.48 e Å^−3^Δρ~min~ = −0.27 e Å^−3^

 {#d5e430}

Data collection: *SMART* (Bruker, 1998[@bb1]); cell refinement: *SAINT-Plus* (Bruker, 1998[@bb1]); data reduction: *SAINT-Plus*; program(s) used to solve structure: *SHELXTL* (Sheldrick, 2008[@bb7]); program(s) used to refine structure: *SHELXTL*; molecular graphics: *SHELXTL*; software used to prepare material for publication: *SHELXTL*.

Supplementary Material
======================

Crystal structure: contains datablocks global, I. DOI: [10.1107/S1600536809050600/rk2182sup1.cif](http://dx.doi.org/10.1107/S1600536809050600/rk2182sup1.cif)

Structure factors: contains datablocks I. DOI: [10.1107/S1600536809050600/rk2182Isup2.hkl](http://dx.doi.org/10.1107/S1600536809050600/rk2182Isup2.hkl)

Additional supplementary materials: [crystallographic information](http://scripts.iucr.org/cgi-bin/sendsupfiles?rk2182&file=rk2182sup0.html&mime=text/html); [3D view](http://scripts.iucr.org/cgi-bin/sendcif?rk2182sup1&Qmime=cif); [checkCIF report](http://scripts.iucr.org/cgi-bin/paper?rk2182&checkcif=yes)

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: [RK2182](http://scripts.iucr.org/cgi-bin/sendsup?rk2182)).

We thank Professor Abel M. Maharramov for fruitful discussions and help in this work.

Comment
=======

The tandem \"domino\" Diels--Alder reaction consists of two consecutive Diels--Alder cycloadditions between two dienes and an acetylenic dienophile acting as a bisdienophile. To the best of our knowledge, only a few papers on tandem \"domino\" Diels--Alder reaction for furan species (when furan derivatives are used as the diene components) have been published (Lautens & Fillion, 1996, 1997; Domingo *et al.*, 2000). Meanwhile, the tandem \"domino\" Diels--Alder reaction gives rise to the rapid construction of bridged polyoxacyclic systems (Wasserman & Kitzing, 1969; Winkler, 1996; Padwa & Bur, 2007). This work demonstrates the stereoselectivity (*exo*--*exo*--adduct) of the reaction of 2,6--difurylpiperidinone with dimethyl acetylene dicarboxylate (*DMAD*). The reaction passes through initial Michael addition of *DMAD* molecule to the nitrogen atom of piperidone with subsequent (4 + 2) cycloaddition of another *DMAD* molecule by the furan ring. The intramolecular \"domino\" Diels--Alder reaction within the generated adduct completes the process on the last stage (Fig. 1).

The molecule of title compound, I, comprises a fused hexacyclic system containing four five--membered rings (two dihydrofuran and two tetrahydrofuran) and two six--membered rings (tetrahydropyridinone and piperidine) (Fig. 2). All four five--membered rings of the tetracyclic fragment have usual *envelope* conformations, and the six--membered rings adopt the slightly flattened *boat* and *chair* conformations, respectively. The nitrogen N1 atom has a trigonal--planar geometry (sum of the bond angles is 359.68 (12)°). The dihedral angle between the planes of the tetrahydropyridinone and piperidine rings is 66.48 (8)°. The carboxylate ligand at the C3 carbon atom lies practically in the plane of the O1C1C2C3C4 dihydrofuran ring (the C2---C3---C18---O7 torsion angle is -8.1 (2)°), while that at the C2 carbon atom is turned out of this plane (the C3---C2---C16═O4 torsion angle is -52.2 (3)°). Such disposion of the carboxylate substituents is determined by both steric reasons and intermolecular C19---H19C···O8^i^ hydrogen bond \[C19···O8^i^ = 3.011 (2)Å, H19C···O8^i^ = 2.70Å, C19---H19C···O8^i^ = 99°\] and attractive antiparallel C16═O4···C16^ii^═O4^ii^ interactions \[C16···O4^ii^ = 2.995 (2)Å\]. The methyl substituents at the C11 and C13 carbon atoms occupy the sterically unfavourable axial positions, which can be explained by the direction of the intramolecular \"domino\" Diels--Alder reaction. Symmetry codes: (i) -1/2+*x*, 2.5-*y*, 1/2+*z*; (ii) 1-*x*, 2-*y*, -*z*.

The molecules I are diastereomers and possess ten asymmetric centers at the C1, C4, C5, C6, C9, C10, C11, C13, C14 and C15 carbon atoms. The crystal of I is racemate and consists of enantiomeric pairs with the relative configuration of the centers *rac*--1*R\**,4*S\**,5*R\**,\\ 6*S\**,9*R\**,10*R\**,11*S\**,\\ 13*R\**,14*S\**,15*S\**.

Experimental {#experimental}
============

The solution of (2*R\**,3*S\**,5*R\**,6*S\**)-2,6-di(2-furyl)-3,5-dimethylpiperidin-4-one (1.0 g, 3.86 mmol) and *DMAD* (1.0 ml, 7.92 mmol) in 10 ml toluene was refluxed for 12 h. Then toluene solvent was evaporated to volume \~ 3 ml, and 6 ml of diethyl ether was added to the solution. The next day 0.8 g of the precipitate formed was filtered off and washed with diethyl ether (2×10 ml). The target compound I (0.45 g, 0.83 mmol) was obtained by re--crystallization from ethyl acetate--*DMF* mixture as white solid. Yield 21%. M.p. = 498--500 K. IR, ν/cm^-1^: 1573 (C═C), 1624 (C═O), 1713 (brd.) and 1735 (brd.) (CO~2~*Me*). Mass spectrum, *m*/*z* (I~r~(%)): 544 (21), 543 \[*M*^+^\] (77), 528 (24), 515 (15), 514 (28), 512 (46), 500 (20), 485 (28), 484 (100), 482 (23), 206 (16), 192 (14), 191 (23), 135 (36), 108 (47), 107 (25), 79 (24), 77 (16), 69 (22), 59 (15). ^1^H NMR (CDCl~3~, 296 K): δ = 6.36 (dd, 1H, H7, ^3^*J* = 5.5, 1.7), 6.28 (d, 1H, H8, ^3^*J* = 5.5), 4.98 (s, 1H, H2\'), 4.95 (s, 1H, H4), 4.82 (d, 1H, H6, ^3^*J* = 1.7), 4.65 (brs, 1H, H14), 4.13 (brs, 1H, H10), 3.88 (s, 3H, CO~2~*Me*), 3.74 (s, 3H, CO~2~*Me*), 3.66 (s, 3H, CO~2~*Me*), 3.55 (s, 3H, CO~2~*Me*), 2.83 (m, 2H, H11, H13), 2.13 (d, 1H, H5, ^3^*J* = 6.1), 2.06(d, 1H, H15, ^3^*J* = 6.1), 1.24 (d, 3H, *Me*11, ^3^*J* = 7.8), 1.20 (d, 3H, *Me*13, ^3^*J* = 7.8). ^13^C NMR (CDCl~3~, 296 K): δ = 210.7 (s, C12), 167.7 (s, CO~2~*Me*), 165.4 (s, CO~2~*Me*), 163.0 (s, CO~2~*Me*), 162.2 (s, CO~2~*Me*), 154.9 (s, C1\'), 148.3 (brs, C2)^a)^, 144.5 (brs, C3)^a)^, 140.6 (d, C8, *J* = 177.5), 138.6 (d, C7, *J* = 177.5), 90.2 (s, C1)^b)^, 87.4 (s, C9)^b)^, 86.7 (d, C4, *J* = 161.5), 81.0 (d, C2\', *J* = 169.5), 80.2 (d, C6, *J* = 165.5), 59.8 (brd, C4, *J* \>\> 140)^c)^, 55.6 (brd, C10, *J* \>\> 140)^c)^, 52.8 (q, CO~2~*Me*, *J* = 148.7), 52.5 (q, CO~2~*Me*, *J* = 148.7), 52.0 (q, CO~2~*Me*, *J* = 147.7), 50.8 (q, CO~2~*Me*, *J* = 146.5), 49.5 (d, C5, *J* = 146.0)^d)^, 49.0 (d, C15, *J* = 150.0)^d)^, 43.9 (d, C11, *J* = 137.5)^e)^, 43.5 (d, C13, *J* = 137.5)^e)^, 19.3 (q, *Me*11, *J* = 129.5)^f)^, 19.9 (q, *Me*13, *J* = 129.5)^f)^. The alternative correlation of signals marked by the identical letters is possible.

Refinement {#refinement}
==========

The hydrogen atoms were placed in calculated positions with C---H = 0.95--1.00Å and refined in the riding model with fixed isotropic displacement parameters: *U*~iso~(H) = 1.5*U*~eq~(C) for CH~3~--groups and *U*~iso~(H) = 1.2*U*~eq~(C) for the other groups.

23 reflections, with experimentally observed *F*^2^deviating significantly from the theoretically calculated *F*^2^, were omitted from the refinement. Moreover, 80 reflections were not measured because the angle limits.

Figures
=======

![Construction of bridged polyheterocyclic system using the tandem \"domino\" Diels--Alder reaction.](e-65-o3243-fig1){#Fap1}

![Molecular structure of I with the atom numbering scheme. Displacement ellipsoids are shown at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius.](e-65-o3243-fig2){#Fap2}

Crystal data {#tablewrapcrystaldatalong}
============

  ------------------------- ---------------------------------------
  C~27~H~29~NO~11~          *F*(000) = 1144
  *M~r~* = 543.51           *D*~x~ = 1.448 Mg m^−3^
  Monoclinic, *P*2~1~/*n*   Mo *K*α radiation, λ = 0.71073 Å
  Hall symbol: -P 2yn       Cell parameters from 5735 reflections
  *a* = 16.1430 (7) Å       θ = 2.4--29.2°
  *b* = 9.1365 (4) Å        µ = 0.11 mm^−1^
  *c* = 16.9658 (7) Å       *T* = 120 K
  β = 95.019 (1)°           Prism, colourless
  *V* = 2492.70 (18) Å^3^   0.30 × 0.25 × 0.20 mm
  *Z* = 4                   
  ------------------------- ---------------------------------------

Data collection {#tablewrapdatacollectionlong}
===============

  --------------------------------------------------------------- --------------------------------------
  Bruker SMART 1K CCD diffractometer                              7186 independent reflections
  Radiation source: fine--focus sealed tube                       5342 reflections with *I* \> 2σ(*I*)
  graphite                                                        *R*~int~ = 0.041
  φ and ω--scans                                                  θ~max~ = 30.0°, θ~min~ = 1.7°
  Absorption correction: multi-scan (*SADABS*; Sheldrick, 1998)   *h* = −22→22
  *T*~min~ = 0.966, *T*~max~ = 0.975                              *k* = −12→12
  27638 measured reflections                                      *l* = −23→23
  --------------------------------------------------------------- --------------------------------------

Refinement {#tablewraprefinementdatalong}
==========

  ------------------------------------- ---------------------------------------------------------------------------------------------
  Refinement on *F*^2^                  Primary atom site location: structure-invariant direct methods
  Least-squares matrix: full            Secondary atom site location: difference Fourier map
  *R*\[*F*^2^ \> 2σ(*F*^2^)\] = 0.054   Hydrogen site location: inferred from neighbouring sites
  *wR*(*F*^2^) = 0.151                  H-atom parameters constrained
  *S* = 1.00                            *w* = 1/\[σ^2^(*F*~o~^2^) + (0.080*P*)^2^ + 1.3*P*\] where *P* = (*F*~o~^2^ + 2*F*~c~^2^)/3
  7186 reflections                      (Δ/σ)~max~ \< 0.001
  358 parameters                        Δρ~max~ = 0.48 e Å^−3^
  0 restraints                          Δρ~min~ = −0.27 e Å^−3^
  ------------------------------------- ---------------------------------------------------------------------------------------------

Special details {#specialdetails}
===============

  ---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
  Geometry. All s.u.\'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.\'s are taken into account individually in the estimation of s.u.\'s in distances, angles and torsion angles; correlations between s.u.\'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.\'s is used for estimating s.u.\'s involving l.s. planes.
  Refinement. Refinement of *F*^2^ against ALL reflections. The weighted *R*--factor *wR* and goodness of fit *S* are based on *F*^2^, conventional *R*--factors *R* are based on *F*, with *F* set to zero for negative *F*^2^. The threshold expression of *F*^2^ \> σ(*F*^2^) is used only for calculating *R*--factors(gt) *etc*. and is not relevant to the choice of reflections for refinement. *R*--factors based on *F*^2^ 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 (Å^2^) {#tablewrapcoords}
==================================================================================================

  ------ -------------- -------------- --------------- -------------------- --
         *x*            *y*            *z*             *U*~iso~\*/*U*~eq~   
  O1     0.66037 (7)    0.73825 (11)   0.16225 (6)     0.0195 (2)           
  O2     0.82627 (7)    0.72867 (12)   0.19163 (6)     0.0202 (2)           
  O3     0.74127 (8)    0.44442 (13)   0.07291 (7)     0.0293 (3)           
  O4     0.48781 (7)    1.10219 (14)   0.06739 (7)     0.0268 (3)           
  O5     0.62045 (7)    1.14017 (12)   0.04217 (7)     0.0240 (2)           
  O6     0.52775 (8)    0.94821 (14)   0.32897 (7)     0.0287 (3)           
  O7     0.49113 (7)    1.11141 (13)   0.23301 (7)     0.0241 (2)           
  O8     0.77295 (8)    1.22882 (15)   −0.15191 (8)    0.0336 (3)           
  O9     0.64719 (8)    1.16118 (14)   −0.20844 (7)    0.0307 (3)           
  O10    0.90731 (7)    1.01714 (13)   −0.09026 (7)    0.0266 (3)           
  O11    0.85640 (7)    1.14089 (12)   0.01008 (7)     0.0243 (2)           
  N1     0.76190 (8)    0.86475 (14)   0.00228 (7)     0.0180 (2)           
  C1     0.67163 (9)    0.86143 (16)   0.11122 (8)     0.0175 (3)           
  C2     0.59850 (9)    0.95863 (16)   0.13139 (9)     0.0188 (3)           
  C3     0.58971 (9)    0.93231 (17)   0.20836 (9)     0.0198 (3)           
  C4     0.65717 (9)    0.82082 (17)   0.23434 (9)     0.0199 (3)           
  H4A    0.6466         0.7617         0.2820          0.024\*              
  C5     0.74072 (9)    0.90776 (17)   0.24083 (9)     0.0191 (3)           
  H5A    0.7386         0.9993         0.2729          0.023\*              
  C6     0.82038 (10)   0.81583 (17)   0.26217 (9)     0.0214 (3)           
  H6A    0.8208         0.7589         0.3125          0.026\*              
  C7     0.89349 (10)   0.91955 (18)   0.25724 (10)    0.0243 (3)           
  H7A    0.9270         0.9616         0.3002          0.029\*              
  C8     0.90099 (9)    0.93947 (17)   0.18049 (9)     0.0220 (3)           
  H8A    0.9416         0.9965         0.1571          0.026\*              
  C9     0.83021 (9)    0.85078 (16)   0.13799 (9)     0.0181 (3)           
  C10    0.83343 (9)    0.80270 (17)   0.05110 (8)     0.0186 (3)           
  H10A   0.8856         0.8423         0.0315          0.022\*              
  C11    0.83281 (10)   0.63446 (17)   0.03981 (9)     0.0222 (3)           
  H11A   0.8722         0.5907         0.0821          0.027\*              
  C12    0.74763 (10)   0.56647 (17)   0.04577 (9)     0.0228 (3)           
  C13    0.67115 (10)   0.65018 (16)   0.01109 (9)     0.0204 (3)           
  H13A   0.6218         0.6154         0.0376          0.024\*              
  C14    0.68070 (9)    0.81581 (16)   0.02491 (8)     0.0175 (3)           
  H14A   0.6365         0.8668         −0.0098         0.021\*              
  C15    0.75006 (9)    0.93764 (16)   0.15166 (8)     0.0172 (3)           
  H15A   0.7536         1.0440         0.1386          0.021\*              
  C16    0.56052 (9)    1.07353 (17)   0.07847 (9)     0.0196 (3)           
  C17    0.59264 (12)   1.25239 (19)   −0.01392 (11)   0.0313 (4)           
  H17A   0.6409         1.2969         −0.0358         0.047\*              
  H17B   0.5621         1.3276         0.0128          0.047\*              
  H17C   0.5561         1.2088         −0.0568         0.047\*              
  C18    0.53357 (9)    0.99724 (17)   0.26329 (9)     0.0211 (3)           
  C19    0.43121 (11)   1.1740 (2)     0.28212 (10)    0.0302 (4)           
  H19A   0.4012         1.2536         0.2534          0.045\*              
  H19B   0.4603         1.2125         0.3309          0.045\*              
  H19C   0.3917         1.0983         0.2953          0.045\*              
  C20    0.86328 (11)   0.5938 (2)     −0.04121 (10)   0.0277 (3)           
  H20A   0.8500         0.4911         −0.0532         0.042\*              
  H20B   0.9236         0.6081         −0.0394         0.042\*              
  H20C   0.8356         0.6564         −0.0824         0.042\*              
  C21    0.65541 (11)   0.62021 (18)   −0.07856 (9)    0.0259 (3)           
  H21A   0.6602         0.5150         −0.0884         0.039\*              
  H21B   0.6966         0.6731         −0.1068         0.039\*              
  H21C   0.5994         0.6535         −0.0974         0.039\*              
  C22    0.76839 (9)    0.96972 (16)   −0.05400 (8)    0.0184 (3)           
  C23    0.70725 (10)   1.01164 (18)   −0.10936 (9)    0.0225 (3)           
  H23A   0.6581         0.9544         −0.1172         0.027\*              
  C24    0.71528 (10)   1.14222 (18)   −0.15703 (9)    0.0233 (3)           
  C25    0.64617 (13)   1.2919 (2)     −0.25582 (11)   0.0353 (4)           
  H25A   0.5969         1.2913         −0.2940         0.053\*              
  H25B   0.6964         1.2954         −0.2843         0.053\*              
  H25C   0.6445         1.3779         −0.2215         0.053\*              
  C26    0.85240 (9)    1.04562 (17)   −0.04942 (9)    0.0202 (3)           
  C27    0.93291 (11)   1.22305 (19)   0.02193 (11)    0.0289 (4)           
  H27A   0.9278         1.2971         0.0630          0.043\*              
  H27B   0.9441         1.2712         −0.0276         0.043\*              
  H27C   0.9788         1.1565         0.0385          0.043\*              
  ------ -------------- -------------- --------------- -------------------- --

Atomic displacement parameters (Å^2^) {#tablewrapadps}
=====================================

  ----- ------------- ------------ ------------ ------------- ------------- -------------
        *U*^11^       *U*^22^      *U*^33^      *U*^12^       *U*^13^       *U*^23^
  O1    0.0250 (5)    0.0177 (5)   0.0160 (5)   −0.0013 (4)   0.0033 (4)    0.0015 (4)
  O2    0.0250 (5)    0.0192 (5)   0.0161 (5)   0.0026 (4)    0.0007 (4)    0.0018 (4)
  O3    0.0440 (7)    0.0190 (5)   0.0246 (6)   −0.0015 (5)   0.0014 (5)    0.0023 (4)
  O4    0.0211 (5)    0.0352 (6)   0.0237 (6)   0.0041 (5)    −0.0015 (4)   −0.0004 (5)
  O5    0.0240 (5)    0.0224 (5)   0.0254 (6)   −0.0025 (4)   −0.0001 (4)   0.0054 (4)
  O6    0.0299 (6)    0.0364 (7)   0.0205 (5)   0.0039 (5)    0.0063 (4)    0.0049 (5)
  O7    0.0258 (6)    0.0265 (6)   0.0209 (5)   0.0056 (4)    0.0066 (4)    0.0001 (4)
  O8    0.0315 (7)    0.0329 (7)   0.0358 (7)   −0.0082 (5)   −0.0001 (5)   0.0111 (5)
  O9    0.0343 (7)    0.0316 (6)   0.0248 (6)   −0.0023 (5)   −0.0053 (5)   0.0111 (5)
  O10   0.0233 (5)    0.0306 (6)   0.0267 (6)   −0.0011 (5)   0.0066 (4)    −0.0008 (5)
  O11   0.0248 (6)    0.0238 (6)   0.0243 (6)   −0.0033 (4)   0.0025 (4)    −0.0043 (4)
  N1    0.0177 (6)    0.0195 (6)   0.0167 (6)   0.0010 (4)    0.0016 (4)    0.0028 (5)
  C1    0.0195 (7)    0.0171 (6)   0.0159 (6)   0.0003 (5)    0.0013 (5)    0.0024 (5)
  C2    0.0171 (6)    0.0195 (7)   0.0199 (7)   −0.0014 (5)   0.0019 (5)    0.0002 (5)
  C3    0.0193 (7)    0.0207 (7)   0.0192 (7)   −0.0021 (5)   0.0014 (5)    −0.0005 (5)
  C4    0.0240 (7)    0.0201 (7)   0.0158 (6)   0.0004 (5)    0.0032 (5)    0.0012 (5)
  C5    0.0210 (7)    0.0200 (7)   0.0160 (6)   0.0025 (5)    0.0001 (5)    −0.0002 (5)
  C6    0.0243 (7)    0.0222 (7)   0.0172 (7)   0.0037 (6)    −0.0011 (5)   0.0002 (6)
  C7    0.0228 (7)    0.0266 (8)   0.0226 (7)   0.0035 (6)    −0.0039 (6)   −0.0035 (6)
  C8    0.0186 (7)    0.0219 (7)   0.0249 (7)   0.0001 (5)    −0.0016 (5)   −0.0019 (6)
  C9    0.0191 (6)    0.0177 (6)   0.0173 (6)   0.0016 (5)    −0.0001 (5)   0.0004 (5)
  C10   0.0184 (6)    0.0200 (7)   0.0174 (7)   0.0021 (5)    0.0012 (5)    0.0000 (5)
  C11   0.0281 (8)    0.0190 (7)   0.0191 (7)   0.0040 (6)    0.0008 (6)    −0.0010 (5)
  C12   0.0330 (8)    0.0207 (7)   0.0147 (6)   0.0011 (6)    0.0026 (6)    −0.0031 (5)
  C13   0.0247 (7)    0.0191 (7)   0.0173 (7)   −0.0035 (5)   0.0021 (5)    −0.0007 (5)
  C14   0.0181 (6)    0.0183 (6)   0.0161 (6)   −0.0005 (5)   0.0019 (5)    0.0010 (5)
  C15   0.0187 (6)    0.0166 (6)   0.0165 (6)   0.0009 (5)    0.0019 (5)    0.0008 (5)
  C16   0.0225 (7)    0.0195 (7)   0.0168 (6)   −0.0002 (5)   0.0009 (5)    −0.0023 (5)
  C17   0.0414 (10)   0.0237 (8)   0.0278 (8)   −0.0015 (7)   −0.0029 (7)   0.0080 (7)
  C18   0.0184 (7)    0.0243 (7)   0.0206 (7)   −0.0021 (5)   0.0020 (5)    −0.0013 (6)
  C19   0.0304 (8)    0.0358 (9)   0.0256 (8)   0.0077 (7)    0.0098 (7)    −0.0033 (7)
  C20   0.0303 (8)    0.0291 (8)   0.0240 (8)   0.0062 (7)    0.0042 (6)    −0.0037 (6)
  C21   0.0344 (9)    0.0232 (8)   0.0196 (7)   −0.0029 (6)   −0.0011 (6)   −0.0027 (6)
  C22   0.0208 (7)    0.0180 (7)   0.0166 (6)   0.0000 (5)    0.0035 (5)    0.0001 (5)
  C23   0.0248 (7)    0.0232 (7)   0.0191 (7)   −0.0036 (6)   0.0002 (6)    0.0037 (6)
  C24   0.0268 (8)    0.0244 (8)   0.0186 (7)   0.0007 (6)    0.0023 (6)    0.0033 (6)
  C25   0.0502 (11)   0.0295 (9)   0.0253 (8)   0.0029 (8)    −0.0018 (8)   0.0103 (7)
  C26   0.0214 (7)    0.0194 (7)   0.0196 (7)   −0.0004 (5)   0.0012 (5)    0.0030 (5)
  C27   0.0289 (8)    0.0254 (8)   0.0312 (9)   −0.0075 (6)   −0.0030 (7)   −0.0015 (7)
  ----- ------------- ------------ ------------ ------------- ------------- -------------

Geometric parameters (Å, °) {#tablewrapgeomlong}
===========================

  ----------------------- -------------- ----------------------- --------------
  O1---C1                 1.4410 (17)    C8---H8A                0.9500
  O1---C4                 1.4418 (18)    C9---C10                1.543 (2)
  O2---C9                 1.4447 (18)    C9---C15                1.552 (2)
  O2---C6                 1.4475 (18)    C10---C11               1.549 (2)
  O3---C12                1.214 (2)      C10---H10A              1.0000
  O4---C16                1.2013 (19)    C11---C12               1.520 (2)
  O5---C16                1.3379 (19)    C11---C20               1.545 (2)
  O5---C17                1.4435 (19)    C11---H11A              1.0000
  O6---C18                1.2123 (19)    C12---C13               1.526 (2)
  O7---C18                1.3265 (19)    C13---C14               1.537 (2)
  O7---C19                1.4485 (19)    C13---C21               1.544 (2)
  O8---C24                1.219 (2)      C13---H13A              1.0000
  O9---C24                1.353 (2)      C14---H14A              1.0000
  O9---C25                1.439 (2)      C15---H15A              1.0000
  O10---C26               1.2005 (19)    C17---H17A              0.9800
  O11---C26               1.3302 (19)    C17---H17B              0.9800
  O11---C27               1.4442 (19)    C17---H17C              0.9800
  N1---C22                1.3638 (19)    C19---H19A              0.9800
  N1---C14                1.4676 (18)    C19---H19B              0.9800
  N1---C10                1.4743 (18)    C19---H19C              0.9800
  C1---C2                 1.540 (2)      C20---H20A              0.9800
  C1---C14                1.542 (2)      C20---H20B              0.9800
  C1---C15                1.551 (2)      C20---H20C              0.9800
  C2---C3                 1.347 (2)      C21---H21A              0.9800
  C2---C16                1.479 (2)      C21---H21B              0.9800
  C3---C18                1.480 (2)      C21---H21C              0.9800
  C3---C4                 1.528 (2)      C22---C23               1.357 (2)
  C4---C5                 1.561 (2)      C22---C26               1.519 (2)
  C4---H4A                1.0000         C23---C24               1.454 (2)
  C5---C6                 1.552 (2)      C23---H23A              0.9500
  C5---C15                1.558 (2)      C25---H25A              0.9800
  C5---H5A                1.0000         C25---H25B              0.9800
  C6---C7                 1.522 (2)      C25---H25C              0.9800
  C6---H6A                1.0000         C27---H27A              0.9800
  C7---C8                 1.331 (2)      C27---H27B              0.9800
  C7---H7A                0.9500         C27---H27C              0.9800
  C8---C9                 1.529 (2)                              
                                                                 
  C1---O1---C4            96.70 (10)     C12---C13---H13A        108.5
  C9---O2---C6            96.06 (11)     C14---C13---H13A        108.5
  C16---O5---C17          115.52 (13)    C21---C13---H13A        108.5
  C18---O7---C19          115.85 (13)    N1---C14---C13          109.88 (12)
  C24---O9---C25          115.81 (14)    N1---C14---C1           109.11 (11)
  C26---O11---C27         115.46 (13)    C13---C14---C1          113.24 (12)
  C22---N1---C14          121.50 (12)    N1---C14---H14A         108.2
  C22---N1---C10          124.01 (12)    C13---C14---H14A        108.2
  C14---N1---C10          114.17 (11)    C1---C14---H14A         108.2
  O1---C1---C2            100.22 (11)    C1---C15---C9           111.29 (12)
  O1---C1---C14           112.76 (12)    C1---C15---C5           101.90 (11)
  C2---C1---C14           120.36 (12)    C9---C15---C5           102.02 (11)
  O1---C1---C15           103.05 (11)    C1---C15---H15A         113.5
  C2---C1---C15           104.77 (11)    C9---C15---H15A         113.5
  C14---C1---C15          113.57 (12)    C5---C15---H15A         113.5
  C3---C2---C16           129.93 (14)    O4---C16---O5           124.39 (15)
  C3---C2---C1            105.09 (13)    O4---C16---C2           126.66 (14)
  C16---C2---C1           124.03 (12)    O5---C16---C2           108.93 (12)
  C2---C3---C18           131.38 (14)    O5---C17---H17A         109.5
  C2---C3---C4            105.41 (13)    O5---C17---H17B         109.5
  C18---C3---C4           123.09 (13)    H17A---C17---H17B       109.5
  O1---C4---C3            100.46 (11)    O5---C17---H17C         109.5
  O1---C4---C5            103.37 (11)    H17A---C17---H17C       109.5
  C3---C4---C5            105.71 (12)    H17B---C17---H17C       109.5
  O1---C4---H4A           115.2          O6---C18---O7           124.59 (15)
  C3---C4---H4A           115.2          O6---C18---C3           122.12 (15)
  C5---C4---H4A           115.2          O7---C18---C3           113.29 (13)
  C6---C5---C15           99.94 (11)     O7---C19---H19A         109.5
  C6---C5---C4            115.74 (13)    O7---C19---H19B         109.5
  C15---C5---C4           100.20 (11)    H19A---C19---H19B       109.5
  C6---C5---H5A           113.1          O7---C19---H19C         109.5
  C15---C5---H5A          113.1          H19A---C19---H19C       109.5
  C4---C5---H5A           113.1          H19B---C19---H19C       109.5
  O2---C6---C7            100.94 (12)    C11---C20---H20A        109.5
  O2---C6---C5            102.59 (11)    C11---C20---H20B        109.5
  C7---C6---C5            106.32 (13)    H20A---C20---H20B       109.5
  O2---C6---H6A           115.1          C11---C20---H20C        109.5
  C7---C6---H6A           115.1          H20A---C20---H20C       109.5
  C5---C6---H6A           115.1          H20B---C20---H20C       109.5
  C8---C7---C6            106.04 (14)    C13---C21---H21A        109.5
  C8---C7---H7A           127.0          C13---C21---H21B        109.5
  C6---C7---H7A           127.0          H21A---C21---H21B       109.5
  C7---C8---C9            105.12 (14)    C13---C21---H21C        109.5
  C7---C8---H8A           127.4          H21A---C21---H21C       109.5
  C9---C8---H8A           127.4          H21B---C21---H21C       109.5
  O2---C9---C8            100.63 (11)    C23---C22---N1          125.97 (14)
  O2---C9---C10           112.88 (12)    C23---C22---C26         119.91 (13)
  C8---C9---C10           121.00 (13)    N1---C22---C26          114.09 (12)
  O2---C9---C15           102.57 (11)    C22---C23---C24         121.47 (14)
  C8---C9---C15           104.88 (12)    C22---C23---H23A        119.3
  C10---C9---C15          112.73 (11)    C24---C23---H23A        119.3
  N1---C10---C9           109.69 (12)    O8---C24---O9           122.35 (15)
  N1---C10---C11          108.41 (12)    O8---C24---C23          126.71 (15)
  C9---C10---C11          113.59 (12)    O9---C24---C23          110.90 (14)
  N1---C10---H10A         108.3          O9---C25---H25A         109.5
  C9---C10---H10A         108.3          O9---C25---H25B         109.5
  C11---C10---H10A        108.3          H25A---C25---H25B       109.5
  C12---C11---C20         108.73 (13)    O9---C25---H25C         109.5
  C12---C11---C10         113.16 (13)    H25A---C25---H25C       109.5
  C20---C11---C10         110.46 (13)    H25B---C25---H25C       109.5
  C12---C11---H11A        108.1          O10---C26---O11         126.20 (14)
  C20---C11---H11A        108.1          O10---C26---C22         124.93 (14)
  C10---C11---H11A        108.1          O11---C26---C22         108.74 (12)
  O3---C12---C11          120.50 (15)    O11---C27---H27A        109.5
  O3---C12---C13          120.94 (15)    O11---C27---H27B        109.5
  C11---C12---C13         118.40 (13)    H27A---C27---H27B       109.5
  C12---C13---C14         111.57 (12)    O11---C27---H27C        109.5
  C12---C13---C21         110.41 (13)    H27A---C27---H27C       109.5
  C14---C13---C21         109.30 (12)    H27B---C27---H27C       109.5
                                                                 
  C4---O1---C1---C2       −52.41 (12)    C11---C12---C13---C21   83.94 (16)
  C4---O1---C1---C14      178.34 (12)    C22---N1---C14---C13    121.65 (14)
  C4---O1---C1---C15      55.50 (12)     C10---N1---C14---C13    −64.54 (15)
  O1---C1---C2---C3       32.96 (14)     C22---N1---C14---C1     −113.65 (14)
  C14---C1---C2---C3      157.09 (13)    C10---N1---C14---C1     60.16 (15)
  C15---C1---C2---C3      −73.59 (14)    C12---C13---C14---N1    48.24 (16)
  O1---C1---C2---C16      −157.27 (13)   C21---C13---C14---N1    −74.16 (15)
  C14---C1---C2---C16     −33.1 (2)      C12---C13---C14---C1    −74.04 (16)
  C15---C1---C2---C16     96.17 (15)     C21---C13---C14---C1    163.56 (13)
  C16---C2---C3---C18     7.4 (3)        O1---C1---C14---N1      −119.65 (13)
  C1---C2---C3---C18      176.34 (15)    C2---C1---C14---N1      122.40 (13)
  C16---C2---C3---C4      −168.69 (15)   C15---C1---C14---N1     −2.90 (16)
  C1---C2---C3---C4       0.24 (15)      O1---C1---C14---C13     3.06 (17)
  C1---O1---C4---C3       52.76 (12)     C2---C1---C14---C13     −114.90 (14)
  C1---O1---C4---C5       −56.33 (12)    C15---C1---C14---C13    119.81 (13)
  C2---C3---C4---O1       −33.38 (15)    O1---C1---C15---C9      74.61 (13)
  C18---C3---C4---O1      150.11 (13)    C2---C1---C15---C9      179.06 (11)
  C2---C3---C4---C5       73.85 (15)     C14---C1---C15---C9     −47.69 (16)
  C18---C3---C4---C5      −102.66 (15)   O1---C1---C15---C5      −33.49 (13)
  O1---C4---C5---C6       −71.63 (15)    C2---C1---C15---C5      70.96 (13)
  C3---C4---C5---C6       −176.75 (12)   C14---C1---C15---C5     −155.79 (12)
  O1---C4---C5---C15      34.72 (13)     O2---C9---C15---C1      −75.60 (13)
  C3---C4---C5---C15      −70.39 (13)    C8---C9---C15---C1      179.64 (12)
  C9---O2---C6---C7       −51.13 (12)    C10---C9---C15---C1     46.09 (16)
  C9---O2---C6---C5       58.53 (12)     O2---C9---C15---C5      32.42 (13)
  C15---C5---C6---O2      −37.45 (14)    C8---C9---C15---C5      −72.34 (14)
  C4---C5---C6---O2       69.06 (15)     C10---C9---C15---C5     154.11 (12)
  C15---C5---C6---C7      68.10 (14)     C6---C5---C15---C1      117.98 (12)
  C4---C5---C6---C7       174.61 (12)    C4---C5---C15---C1      −0.67 (13)
  O2---C6---C7---C8       31.52 (16)     C6---C5---C15---C9      2.87 (14)
  C5---C6---C7---C8       −75.21 (16)    C4---C5---C15---C9      −115.78 (12)
  C6---C7---C8---C9       1.65 (16)      C17---O5---C16---O4     −0.5 (2)
  C6---O2---C9---C8       52.09 (12)     C17---O5---C16---C2     177.92 (13)
  C6---O2---C9---C10      −177.52 (12)   C3---C2---C16---O4      −52.2 (3)
  C6---O2---C9---C15      −55.94 (12)    C1---C2---C16---O4      140.73 (16)
  C7---C8---C9---O2       −34.40 (15)    C3---C2---C16---O5      129.43 (17)
  C7---C8---C9---C10      −159.45 (14)   C1---C2---C16---O5      −37.64 (19)
  C7---C8---C9---C15      71.79 (15)     C19---O7---C18---O6     −3.3 (2)
  C22---N1---C10---C9     111.90 (15)    C19---O7---C18---C3     176.24 (13)
  C14---N1---C10---C9     −61.74 (16)    C2---C3---C18---O6      171.50 (16)
  C22---N1---C10---C11    −123.55 (15)   C4---C3---C18---O6      −13.0 (2)
  C14---N1---C10---C11    62.81 (15)     C2---C3---C18---O7      −8.1 (2)
  O2---C9---C10---N1      120.82 (13)    C4---C3---C18---O7      167.45 (13)
  C8---C9---C10---N1      −120.03 (14)   C14---N1---C22---C23    −19.1 (2)
  C15---C9---C10---N1     5.17 (17)      C10---N1---C22---C23    167.72 (15)
  O2---C9---C10---C11     −0.66 (17)     C14---N1---C22---C26    158.92 (13)
  C8---C9---C10---C11     118.48 (15)    C10---N1---C22---C26    −14.3 (2)
  C15---C9---C10---C11    −116.31 (14)   N1---C22---C23---C24    168.41 (14)
  N1---C10---C11---C12    −46.70 (16)    C26---C22---C23---C24   −9.5 (2)
  C9---C10---C11---C12    75.50 (16)     C25---O9---C24---O8     −1.2 (2)
  N1---C10---C11---C20    75.47 (15)     C25---O9---C24---C23    176.67 (15)
  C9---C10---C11---C20    −162.33 (13)   C22---C23---C24---O8    −2.7 (3)
  C20---C11---C12---O3    89.83 (17)     C22---C23---C24---O9    179.48 (15)
  C10---C11---C12---O3    −147.04 (14)   C27---O11---C26---O10   4.3 (2)
  C20---C11---C12---C13   −85.50 (16)    C27---O11---C26---C22   −179.67 (13)
  C10---C11---C12---C13   37.63 (18)     C23---C22---C26---O10   −82.3 (2)
  O3---C12---C13---C14    146.87 (14)    N1---C22---C26---O10    99.52 (18)
  C11---C12---C13---C14   −37.82 (18)    C23---C22---C26---O11   101.56 (16)
  O3---C12---C13---C21    −91.37 (17)    N1---C22---C26---O11    −76.58 (16)
  ----------------------- -------------- ----------------------- --------------

Hydrogen-bond geometry (Å, °) {#tablewraphbondslong}
=============================

  -------------------- --------- --------- ----------- ---------------
  *D*---H···*A*        *D*---H   H···*A*   *D*···*A*   *D*---H···*A*
  C19---H19C···O8^i^   0.98      2.70      3.011 (2)   99
  -------------------- --------- --------- ----------- ---------------

Symmetry codes: (i) *x*−1/2, −*y*+5/2, *z*+1/2.

###### Hydrogen-bond geometry (Å, °)

  *D*---H⋯*A*          *D*---H   H⋯*A*   *D*⋯*A*     *D*---H⋯*A*
  -------------------- --------- ------- ----------- -------------
  C19---H19*C*⋯O8^i^   0.98      2.70    3.011 (2)   99

Symmetry code: (i) .
