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

For a detailed account of the design of organic polar crystals, see: Pecaut & Bagieu-Beucher (1993[@bb12]).  For hydrogen bonding in nitro­phenol complexes, see: In *et al.* ( 1997[@bb9]); Zadrenko *et al.* ( 1997[@bb17]); Mizutani *et al.* ( 1998[@bb11]).  For the supra­molecular architecture of mol­ecular complexes of trinitro­phenols, see: Botoshansky *et al.* ( 1994[@bb2]); Vembu *et al.* ( 2003[@bb16]).  For puckering paramaters, see: Cremer & Pople (1975[@bb4]).  For hydrogen-bonding criteria, see: Desiraju & Steiner (1999[@bb6]); Desiraju (1989[@bb5]); Jeffrey (1997[@bb10]).  For graph-set notation, see: Bernstein *et al.* ( 1995[@bb1]); Etter (1990[@bb7]). 

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

 {#sec2.1}

### Crystal data {#sec2.1.1}

C~4~H~10~NO^+^·C~6~H~2~N~3~O~7~ ^−^*M* *~r~* = 316.24Triclinic,*a* = 8.3179 (5) Å*b* = 9.5733 (5) Å*c* = 16.8451 (10) Åα = 91.292 (4)°β = 98.604 (4)°γ = 107.589 (4)°*V* = 1261.00 (13) Å^3^*Z* = 4Cu *K*α radiationμ = 1.28 mm^−1^*T* = 90.0 (5) K0.25 × 0.22 × 0.13 mm

### Data collection {#sec2.1.2}

Bruker Kappa APEXII CCD area-detector diffractometerAbsorption correction: multi-scan (*SADABS*; Sheldrick, 2006[@bb13]) *T* ~min~ = 0.745, *T* ~max~ = 0.85114930 measured reflections4520 independent reflections4172 reflections with *I* \> 2σ(*I*)*R* ~int~ = 0.025

### Refinement {#sec2.1.3}

*R*\[*F* ^2^ \> 2σ(*F* ^2^)\] = 0.029*wR*(*F* ^2^) = 0.075*S* = 1.044520 reflections494 parametersAll H-atom parameters refinedΔρ~max~ = 0.25 e Å^−3^Δρ~min~ = −0.21 e Å^−3^

 {#d5e953}

Data collection: *APEX2* (Bruker, 2006[@bb3]); cell refinement: *APEX2* and *SAINT* (Bruker, 2006[@bb3]); data reduction: *SAINT*; program(s) used to solve structure: *SHELXS97* (Sheldrick, 2008[@bb14]); program(s) used to refine structure: *SHELXL97* (Sheldrick, 2008[@bb14]); molecular graphics: *PLATON* (Spek, 2003[@bb15]); software used to prepare material for publication: *SHELXL97*. 

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

Crystal structure: contains datablocks I, global.  DOI: [10.1107/S1600536808042657/sj2568sup1.cif](http://dx.doi.org/10.1107/S1600536808042657/sj2568sup1.cif)

Structure factors: contains datablocks I. DOI: [10.1107/S1600536808042657/sj2568Isup2.hkl](http://dx.doi.org/10.1107/S1600536808042657/sj2568Isup2.hkl)

Additional supplementary materials: [crystallographic information](http://scripts.iucr.org/cgi-bin/sendsupfiles?sj2568&file=sj2568sup0.html&mime=text/html); [3D view](http://scripts.iucr.org/cgi-bin/sendcif?sj2568sup1&Qmime=cif); [checkCIF report](http://scripts.iucr.org/cgi-bin/paper?sj2568&checkcif=yes)

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: [SJ2568](http://scripts.iucr.org/cgi-bin/sendsup?sj2568)). 

NV thanks the University Grants Commission (UGC), Government of India, for a minor research project grant \[MRP-2219/06(UGC-SERO)\]. 

Comment
=======

The design of organic polar crystals for quadratic non-linear optical applications is supported by the observation that the organic molecules containing π-electron systems asymmetrized by electron donor and acceptor groups are highly polarizable entities in which problems of transparency and crystal growth may arise from their molecular crystal packing (Pecaut & Bagieu-Beucher, 1993).  It is known that nitrophenols act not only as π-acceptor to form various π-stacking complexes with other aromatic molecules, but also as an acidic ligand to form salts through specific electrostatic or H-bonding interactions (In *et al.*,  1997).  The bonding of electron-donor acceptor complexes strongly depends on the nature of the partners.  The linkage could involve not only electrostatic interactions, but also the formation of molecular complexes (Zadrenko *et al.*,  1997).  It has been reported that proton transferred thermochromic complexes were formed between phenols and amines in apolar solvents at low temperature if an appropriate H-bonding network between phenols and amines were present to stabilize it (Mizutani *et al.*,  1998).  Pyridinium picrate has been reported in two crystalline phases and it appears in both phases as an internally linked H-bonded ion pair.  These two phases are termed as molecular crystals rather than salts based on their structural arrangements (Botoshansky *et al.*,  1994).  A similar structural arrangement has also been reported for 4-dimethylaminopyridinium picrate (Vembu *et al.*,  2003).  In continuation of our investigations on the supramolecular architecture of picrates, the X-ray diffraction study on the title compound is carried out. 

The asymmetric unit of (I) contains two morpholinium cations and and two 2,4,6-trinitrophenolate anions. ( Fig.1).  The morpholinium cation is puckered in both the molecules with the Cremer and Pople puckering parameters Q, θ and φ (Cremer & Pople, 1975) in the two molecules being, 0.590 (1)Å & 0.588 (1) Å, 179.7 (2)° & 0.7 (1)°, 285 (13)° & 63 (11)°, respectively.  The morpolinium cation in both the molecules adopt a chair conformation as discerned from the respective torsion angles. 

The crystal structure of (I) is stabilized by N---H···O and C---H···O interactions.  The range of H···O distances (Table 1) found in (I) agrees with those found for N---H···O (Jeffrey, 1997) and C---H···O hydrogen bonds (Desiraju & Steiner, 1999).  The N20A---H20B···O7B^i^ and N20A---H20B···O15B^i^ interactions form a pair of bifurcated donor bonds that form a motif of graph set (Bernstein *et al.*,  1995; Etter, 1990) *R*~1~^2^(6).  Another pair of bifurcated donor bonds consists of the N20B---H20C···O7A^ii^ and N20B---H20C···O9A^ii^ interactions that also generate a *R*~1~^2^(6) motif.  The N20B---H20D···O12A^iii^ and C21B---H21C···O12A^iii^ interactions constitute a pair of bifurcated acceptor bonds that generate a ring motif of graph set *R*~2~^1^(5).  The N20A---H20A···O17B, N20A---H20B···O7B^i^ and N20A---H20B···O15B^i^ interactions generate a cooperative H-bonded network.  Another cooperative H-bonded network is formed by the interactions, N20B---H20C···O7A^ii^, N20B---H20C···O9A^ii^, N20B---H20D···O12A^iii^ and N20B---H20D···O17A^iv^. These two networks generate an infinite one dimensional chain along the base vector \[100\].  The C18A---H18A···*Cg*4^viii^ interaction (Table 2) is classified as an offset face to face interaction with γ = 4.45° and perpendicular distance 2.897Å whereas the C22B---H22C···*Cg*3^ix^ is termed as edge to face interaction with γ = 20.34° with a perpendicular distance 2.956Å where *Cg*4 is the centroid of the ring formed by the atoms C1B---C6B and *Cg*3 is the centroid of the ring formed by the atoms C1A---C6A. There are two face to face π···π interactions in the title compound with coordinates *Cg*3···*Cg*3 (2 - *x*, 1 - *y*, -*z*) with α = 0.00°, β & γ = 19.38°, with perpendicular distance 3.449Å and *Cg*4···*Cg*4 (2 - *x*, 1 - *y*, 1 - *z*) with α = 0.02°, β & γ = 18.71°, and perpendicular distance 3.461 Å.

The interplay of strong N---H···O and weak C---H···O, C---H···π and π···π interactions with different strengths, directional preferences and distances presents a complex mosaic of interactions.  The three dimensional arrangement of 2,4,6-trinitrophenolate and morpholinium moieties in the unit cell, shows that the title compound is an internally linked hydrogen bonded ion pair and hence can be regarded as a molecular crystal rather than a salt. 

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

2,4,6-Trinitrophenol (5.2 mmol) dissolved in aqueous ethanol (25 ml) was added dropwise to morpholine (5.7 mmol) in aqueous ethanol (25 ml).  The above solution was constantly stirred at room temperature for 2 hrs.  The precipitated product was filtered and recrystallized from aqueous ethanol.  Yield 75% (3.9 mmol). 

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

All H-atoms were located in difference maps and their positions and isotropic displacement parameters were freely refined. 

Figures
=======

![ The asymmetric unit of (I) with the atoms labelled and displacement ellipsoids depicted at the 50% probability level for all non-H atoms.  H-atoms are drawn as spheres of arbitrary radius.](e-65-0o156-fig1){#Fap1}

![ The molecular packing viewed down the a-axis.  Dashed lines represent the N---H···O and C---H···O interactions within the lattice.](e-65-0o156-fig2){#Fap2}

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

  ------------------------------------ ---------------------------------------
  C~4~H~10~NO^+^·C~6~H~2~N~3~O~7~^−^   *Z* = 4
  *M~r~* = 316.24                      *F*(000) = 656
  Triclinic, *P*1                      *D*~x~ = 1.666 Mg m^−3^
  Hall symbol: -P 1                    Melting point: 418 K
  *a* = 8.3179 (5) Å                   Cu *K*α radiation, λ = 1.54178 Å
  *b* = 9.5733 (5) Å                   Cell parameters from 9038 reflections
  *c* = 16.8451 (10) Å                 θ = 2.6--70.3°
  α = 91.292 (4)°                      µ = 1.28 mm^−1^
  β = 98.604 (4)°                      *T* = 90 K
  γ = 107.589 (4)°                     Needle, yellow
  *V* = 1261.00 (13) Å^3^              0.25 × 0.22 × 0.13 mm
  ------------------------------------ ---------------------------------------

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

  --------------------------------------------------------------- --------------------------------------
  Bruker Kappa APEXII CCD area-detector diffractometer            4520 independent reflections
  Radiation source: fine-focus sealed tube                        4172 reflections with *I* \> 2σ(*I*)
  graphite                                                        *R*~int~ = 0.025
  φ and ω scans                                                   θ~max~ = 70.4°, θ~min~ = 2.7°
  Absorption correction: multi-scan (*SADABS*; Sheldrick, 2006)   *h* = −9→8
  *T*~min~ = 0.745, *T*~max~ = 0.851                              *k* = −11→11
  14930 measured reflections                                      *l* = −20→20
  --------------------------------------------------------------- --------------------------------------

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

  ---------------------------------------------------------------- ----------------------------------------------------------------------------------------------------
  Refinement on *F*^2^                                             Secondary atom site location: difference Fourier map
  Least-squares matrix: full                                       Hydrogen site location: inferred from neighbouring sites
  *R*\[*F*^2^ \> 2σ(*F*^2^)\] = 0.029                              All H-atom parameters refined
  *wR*(*F*^2^) = 0.075                                             *w* = 1/\[σ^2^(*F*~o~^2^) + (0.0404*P*)^2^ + 0.5962*P*\] where *P* = (*F*~o~^2^ + 2*F*~c~^2^)/3
  *S* = 1.04                                                       (Δ/σ)~max~ \< 0.001
  4520 reflections                                                 Δρ~max~ = 0.25 e Å^−3^
  494 parameters                                                   Δρ~min~ = −0.21 e Å^−3^
  0 restraints                                                     Extinction correction: *SHELXL97* (Sheldrick, 2008), Fc^\*^=kFc\[1+0.001xFc^2^λ^3^/sin(2θ)\]^-1/4^
  Primary atom site location: structure-invariant direct methods   Extinction coefficient: 0.0031 (2)
  ---------------------------------------------------------------- ----------------------------------------------------------------------------------------------------

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

  -----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
  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 *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~   
  C1A    1.09611 (17)   0.49974 (13)    −0.12320 (7)   0.0127 (3)           
  C2A    1.25008 (16)   0.60126 (14)    −0.07769 (7)   0.0132 (3)           
  C3A    1.25234 (17)   0.72107 (14)    −0.03028 (7)   0.0136 (3)           
  C4A    1.10041 (17)   0.74600 (14)    −0.02152 (7)   0.0133 (3)           
  C5A    0.94390 (17)   0.65574 (14)    −0.06295 (7)   0.0132 (3)           
  C6A    0.94588 (16)   0.53913 (14)    −0.11109 (7)   0.0130 (3)           
  O7A    1.09018 (12)   0.39624 (10)    −0.17139 (5)   0.0155 (2)           
  N8A    1.41454 (14)   0.58076 (12)    −0.08198 (6)   0.0147 (2)           
  O9A    1.42204 (12)   0.45459 (10)    −0.09063 (6)   0.0192 (2)           
  O10A   1.54125 (12)   0.69100 (10)    −0.07467 (6)   0.0212 (2)           
  N11A   1.10530 (14)   0.86621 (12)    0.03319 (6)    0.0143 (2)           
  O12A   0.96928 (12)   0.87274 (10)    0.05109 (5)    0.0179 (2)           
  O13A   1.24520 (12)   0.95709 (10)    0.05934 (6)    0.0194 (2)           
  N14A   0.78244 (14)   0.44885 (12)    −0.15723 (6)   0.0134 (2)           
  O15A   0.74323 (12)   0.31494 (10)    −0.15316 (6)   0.0189 (2)           
  O16A   0.69331 (12)   0.51112 (11)    −0.19769 (6)   0.0199 (2)           
  O17A   0.10539 (11)   0.00176 (10)    0.25016 (6)    0.0168 (2)           
  C18A   0.20658 (18)   −0.08501 (15)   0.28608 (9)    0.0184 (3)           
  C19A   0.32219 (18)   −0.00503 (15)   0.36195 (8)    0.0171 (3)           
  N20A   0.43482 (14)   0.13842 (12)    0.34067 (7)    0.0133 (2)           
  C21A   0.32929 (17)   0.22701 (14)    0.30180 (8)    0.0145 (3)           
  C22A   0.21200 (17)   0.13892 (15)    0.22823 (8)    0.0162 (3)           
  C1B    1.20643 (17)   0.72087 (13)    0.48672 (7)    0.0131 (3)           
  C2B    1.02460 (17)   0.69732 (14)    0.46441 (7)    0.0136 (3)           
  C3B    0.91624 (17)   0.59563 (14)    0.40640 (7)    0.0133 (3)           
  C4B    0.98544 (17)   0.50853 (14)    0.36284 (7)    0.0133 (3)           
  C5B    1.15875 (17)   0.52696 (14)    0.37604 (7)    0.0134 (3)           
  C6B    1.26371 (16)   0.62652 (14)    0.43659 (8)    0.0134 (3)           
  O7B    1.30043 (12)   0.81736 (10)    0.53895 (5)    0.0166 (2)           
  N8B    0.95032 (14)   0.79251 (12)    0.50610 (6)    0.0141 (2)           
  O9B    0.97719 (12)   0.80272 (10)    0.57994 (5)    0.0181 (2)           
  O10B   0.86456 (13)   0.85646 (11)    0.46437 (6)    0.0208 (2)           
  N11B   0.87435 (14)   0.39640 (12)    0.30331 (6)    0.0143 (2)           
  O12B   0.93987 (12)   0.32440 (10)    0.26417 (5)    0.0172 (2)           
  O13B   0.71918 (12)   0.37736 (11)    0.29419 (6)    0.0204 (2)           
  N14B   1.44400 (14)   0.63651 (12)    0.44848 (6)    0.0152 (2)           
  O15B   1.52754 (12)   0.66652 (11)    0.51713 (6)    0.0196 (2)           
  O16B   1.50511 (12)   0.61178 (11)    0.38943 (6)    0.0214 (2)           
  O17B   0.59893 (12)   0.00091 (10)    0.24493 (5)    0.0160 (2)           
  C18B   0.71842 (18)   −0.05139 (15)   0.29696 (8)    0.0170 (3)           
  C19B   0.72407 (18)   −0.19629 (15)   0.26204 (8)    0.0160 (3)           
  N20B   0.77466 (14)   −0.17515 (12)   0.18046 (6)    0.0132 (2)           
  C21B   0.65320 (17)   −0.11684 (14)   0.12743 (8)    0.0144 (3)           
  C22B   0.64834 (18)   0.02484 (15)    0.16719 (8)    0.0157 (3)           
  H3A    1.360 (2)      0.7844 (18)     −0.0031 (10)   0.017 (4)\*          
  H5A    0.838 (2)      0.6748 (17)     −0.0584 (9)    0.016 (4)\*          
  H18A   0.271 (2)      −0.1092 (17)    0.2483 (10)    0.018 (4)\*          
  H18B   0.126 (2)      −0.1764 (19)    0.2992 (10)    0.023 (4)\*          
  H19A   0.396 (2)      −0.0592 (18)    0.3852 (10)    0.018 (4)\*          
  H19B   0.261 (2)      0.0171 (17)     0.4011 (10)    0.017 (4)\*          
  H20A   0.500 (2)      0.1174 (18)     0.3066 (10)    0.019 (4)\*          
  H20B   0.508 (2)      0.1873 (19)     0.3868 (11)    0.025 (4)\*          
  H21A   0.263 (2)      0.2475 (16)     0.3409 (9)     0.012 (4)\*          
  H21B   0.405 (2)      0.3182 (18)     0.2864 (9)     0.018 (4)\*          
  H22A   0.135 (2)      0.1928 (17)     0.2053 (9)     0.015 (4)\*          
  H22B   0.276 (2)      0.1212 (17)     0.1890 (10)    0.017 (4)\*          
  H3B    0.797 (2)      0.5873 (17)     0.3967 (10)    0.017 (4)\*          
  H5B    1.207 (2)      0.4711 (17)     0.3456 (10)    0.014 (4)\*          
  H18C   0.827 (2)      0.0221 (17)     0.3037 (9)     0.014 (4)\*          
  H18D   0.680 (2)      −0.0648 (18)    0.3484 (10)    0.020 (4)\*          
  H19C   0.809 (2)      −0.2287 (17)    0.2940 (10)    0.017 (4)\*          
  H19D   0.616 (2)      −0.2714 (18)    0.2553 (10)    0.019 (4)\*          
  H20C   0.780 (2)      −0.260 (2)      0.1599 (10)    0.022 (4)\*          
  H20D   0.885 (2)      −0.109 (2)      0.1881 (10)    0.024 (4)\*          
  H21C   0.689 (2)      −0.1002 (17)    0.0762 (10)    0.015 (4)\*          
  H21D   0.543 (2)      −0.1912 (17)    0.1218 (9)     0.014 (4)\*          
  H22C   0.760 (2)      0.1022 (18)     0.1722 (9)     0.018 (4)\*          
  H22D   0.560 (2)      0.0609 (17)     0.1341 (10)    0.016 (4)\*          
  ------ -------------- --------------- -------------- -------------------- --

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

  ------ ------------ ------------ ------------ ------------ ------------- -------------
         *U*^11^      *U*^22^      *U*^33^      *U*^12^      *U*^13^       *U*^23^
  C1A    0.0151 (7)   0.0122 (6)   0.0111 (6)   0.0043 (5)   0.0024 (5)    0.0033 (5)
  C2A    0.0119 (7)   0.0151 (6)   0.0135 (6)   0.0050 (5)   0.0031 (5)    0.0029 (5)
  C3A    0.0138 (7)   0.0142 (6)   0.0116 (6)   0.0027 (5)   0.0018 (5)    0.0023 (5)
  C4A    0.0165 (7)   0.0122 (6)   0.0114 (6)   0.0045 (5)   0.0029 (5)    0.0006 (5)
  C5A    0.0133 (7)   0.0150 (6)   0.0123 (6)   0.0050 (5)   0.0040 (5)    0.0036 (5)
  C6A    0.0118 (7)   0.0143 (6)   0.0117 (6)   0.0022 (5)   0.0017 (5)    0.0024 (5)
  O7A    0.0157 (5)   0.0145 (4)   0.0162 (4)   0.0054 (4)   0.0012 (4)    −0.0020 (3)
  N8A    0.0128 (6)   0.0155 (5)   0.0153 (5)   0.0042 (4)   0.0013 (4)    −0.0010 (4)
  O9A    0.0166 (5)   0.0165 (5)   0.0254 (5)   0.0081 (4)   0.0005 (4)    −0.0028 (4)
  O10A   0.0123 (5)   0.0175 (5)   0.0313 (5)   0.0006 (4)   0.0049 (4)    −0.0021 (4)
  N11A   0.0162 (6)   0.0144 (5)   0.0129 (5)   0.0053 (4)   0.0027 (4)    0.0010 (4)
  O12A   0.0177 (5)   0.0205 (5)   0.0184 (5)   0.0081 (4)   0.0075 (4)    0.0000 (4)
  O13A   0.0166 (5)   0.0169 (5)   0.0210 (5)   0.0016 (4)   0.0003 (4)    −0.0051 (4)
  N14A   0.0122 (6)   0.0152 (5)   0.0127 (5)   0.0035 (4)   0.0031 (4)    −0.0003 (4)
  O15A   0.0174 (5)   0.0138 (5)   0.0227 (5)   0.0013 (4)   0.0027 (4)    −0.0010 (4)
  O16A   0.0151 (5)   0.0239 (5)   0.0201 (5)   0.0073 (4)   −0.0019 (4)   0.0037 (4)
  O17A   0.0115 (5)   0.0159 (5)   0.0202 (5)   0.0018 (4)   −0.0005 (4)   0.0002 (4)
  C18A   0.0145 (7)   0.0140 (6)   0.0254 (7)   0.0033 (5)   0.0014 (6)    −0.0002 (5)
  C19A   0.0150 (7)   0.0168 (6)   0.0193 (7)   0.0043 (5)   0.0027 (6)    0.0043 (5)
  N20A   0.0124 (6)   0.0141 (5)   0.0130 (5)   0.0041 (4)   0.0014 (5)    −0.0013 (4)
  C21A   0.0126 (7)   0.0139 (6)   0.0173 (6)   0.0051 (5)   0.0020 (5)    −0.0001 (5)
  C22A   0.0138 (7)   0.0186 (7)   0.0156 (6)   0.0044 (5)   0.0015 (5)    0.0019 (5)
  C1B    0.0146 (7)   0.0130 (6)   0.0117 (6)   0.0041 (5)   0.0021 (5)    0.0031 (5)
  C2B    0.0150 (7)   0.0142 (6)   0.0127 (6)   0.0056 (5)   0.0039 (5)    0.0024 (5)
  C3B    0.0132 (7)   0.0151 (6)   0.0120 (6)   0.0046 (5)   0.0027 (5)    0.0042 (5)
  C4B    0.0129 (7)   0.0130 (6)   0.0120 (6)   0.0016 (5)   0.0013 (5)    0.0009 (5)
  C5B    0.0162 (7)   0.0133 (6)   0.0122 (6)   0.0054 (5)   0.0044 (5)    0.0021 (5)
  C6B    0.0117 (7)   0.0145 (6)   0.0142 (6)   0.0037 (5)   0.0030 (5)    0.0032 (5)
  O7B    0.0156 (5)   0.0167 (5)   0.0160 (4)   0.0048 (4)   −0.0013 (4)   −0.0037 (4)
  N8B    0.0123 (6)   0.0140 (5)   0.0154 (5)   0.0034 (4)   0.0022 (4)    0.0004 (4)
  O9B    0.0205 (5)   0.0218 (5)   0.0126 (4)   0.0068 (4)   0.0041 (4)    −0.0011 (4)
  O10B   0.0216 (5)   0.0218 (5)   0.0216 (5)   0.0128 (4)   −0.0010 (4)   0.0004 (4)
  N11B   0.0143 (6)   0.0143 (5)   0.0131 (5)   0.0021 (4)   0.0031 (4)    0.0020 (4)
  O12B   0.0206 (5)   0.0164 (5)   0.0148 (4)   0.0062 (4)   0.0032 (4)    −0.0021 (3)
  O13B   0.0117 (5)   0.0231 (5)   0.0226 (5)   0.0006 (4)   0.0018 (4)    −0.0030 (4)
  N14B   0.0140 (6)   0.0161 (5)   0.0154 (5)   0.0046 (4)   0.0020 (4)    −0.0006 (4)
  O15B   0.0161 (5)   0.0258 (5)   0.0164 (5)   0.0091 (4)   −0.0037 (4)   −0.0045 (4)
  O16B   0.0155 (5)   0.0316 (6)   0.0183 (5)   0.0077 (4)   0.0060 (4)    −0.0025 (4)
  O17B   0.0165 (5)   0.0209 (5)   0.0137 (4)   0.0101 (4)   0.0030 (4)    0.0005 (3)
  C18B   0.0163 (7)   0.0227 (7)   0.0136 (6)   0.0092 (6)   0.0008 (5)    −0.0006 (5)
  C19B   0.0155 (7)   0.0190 (7)   0.0152 (6)   0.0074 (6)   0.0035 (5)    0.0030 (5)
  N20B   0.0120 (6)   0.0127 (5)   0.0147 (5)   0.0037 (5)   0.0025 (4)    −0.0015 (4)
  C21B   0.0115 (7)   0.0180 (6)   0.0129 (6)   0.0040 (5)   0.0010 (5)    0.0004 (5)
  C22B   0.0160 (7)   0.0176 (6)   0.0149 (6)   0.0068 (6)   0.0034 (5)    0.0025 (5)
  ------ ------------ ------------ ------------ ------------ ------------- -------------

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

  --------------------------- -------------- --------------------------- --------------
  C1A---O7A                   1.2511 (16)    C1B---O7B                   1.2489 (16)
  C1A---C2A                   1.4466 (19)    C1B---C2B                   1.4490 (19)
  C1A---C6A                   1.4502 (18)    C1B---C6B                   1.4498 (18)
  C2A---C3A                   1.3765 (18)    C2B---C3B                   1.3705 (19)
  C2A---N8A                   1.4513 (17)    C2B---N8B                   1.4652 (16)
  C3A---C4A                   1.3829 (19)    C3B---C4B                   1.3978 (18)
  C3A---H3A                   0.957 (17)     C3B---H3B                   0.958 (17)
  C4A---C5A                   1.3963 (19)    C4B---C5B                   1.3811 (19)
  C4A---N11A                  1.4449 (16)    C4B---N11B                  1.4445 (17)
  C5A---C6A                   1.3705 (18)    C5B---C6B                   1.3777 (18)
  C5A---H5A                   0.968 (17)     C5B---H5B                   0.943 (16)
  C6A---N14A                  1.4638 (17)    C6B---N14B                  1.4563 (17)
  N8A---O10A                  1.2340 (15)    N8B---O9B                   1.2266 (14)
  N8A---O9A                   1.2347 (14)    N8B---O10B                  1.2292 (15)
  N11A---O12A                 1.2324 (15)    N11B---O13B                 1.2328 (15)
  N11A---O13A                 1.2339 (15)    N11B---O12B                 1.2333 (14)
  N14A---O16A                 1.2262 (15)    N14B---O16B                 1.2318 (15)
  N14A---O15A                 1.2298 (14)    N14B---O15B                 1.2356 (15)
  O17A---C18A                 1.4343 (16)    O17B---C22B                 1.4332 (15)
  O17A---C22A                 1.4363 (16)    O17B---C18B                 1.4376 (16)
  C18A---C19A                 1.5126 (19)    C18B---C19B                 1.5110 (18)
  C18A---H18A                 0.956 (17)     C18B---H18C                 0.954 (17)
  C18A---H18B                 0.982 (18)     C18B---H18D                 0.967 (17)
  C19A---N20A                 1.4957 (17)    C19B---N20B                 1.4968 (16)
  C19A---H19A                 0.964 (17)     C19B---H19C                 0.952 (17)
  C19A---H19B                 0.949 (17)     C19B---H19D                 0.957 (17)
  N20A---C21A                 1.4905 (16)    N20B---C21B                 1.4912 (17)
  N20A---H20A                 0.905 (18)     N20B---H20C                 0.888 (18)
  N20A---H20B                 0.930 (19)     N20B---H20D                 0.930 (19)
  C21A---C22A                 1.5141 (18)    C21B---C22B                 1.5134 (18)
  C21A---H21A                 0.972 (16)     C21B---H21C                 0.956 (16)
  C21A---H21B                 0.976 (17)     C21B---H21D                 0.965 (17)
  C22A---H22A                 0.977 (16)     C22B---H22C                 0.985 (17)
  C22A---H22B                 0.952 (17)     C22B---H22D                 1.003 (17)
                                                                         
  O7A---C1A---C2A             125.64 (12)    O7B---C1B---C2B             123.19 (12)
  O7A---C1A---C6A             122.87 (12)    O7B---C1B---C6B             125.55 (12)
  C2A---C1A---C6A             111.33 (11)    C2B---C1B---C6B             111.10 (11)
  C3A---C2A---C1A             123.85 (12)    C3B---C2B---C1B             125.69 (12)
  C3A---C2A---N8A             116.39 (11)    C3B---C2B---N8B             116.95 (12)
  C1A---C2A---N8A             119.75 (11)    C1B---C2B---N8B             117.34 (11)
  C2A---C3A---C4A             119.83 (12)    C2B---C3B---C4B             118.12 (12)
  C2A---C3A---H3A             118.7 (10)     C2B---C3B---H3B             119.4 (9)
  C4A---C3A---H3A             121.5 (10)     C4B---C3B---H3B             122.5 (10)
  C3A---C4A---C5A             121.30 (12)    C5B---C4B---C3B             121.14 (12)
  C3A---C4A---N11A            118.73 (12)    C5B---C4B---N11B            119.13 (11)
  C5A---C4A---N11A            119.96 (11)    C3B---C4B---N11B            119.72 (12)
  C6A---C5A---C4A             117.54 (12)    C6B---C5B---C4B             119.39 (12)
  C6A---C5A---H5A             120.9 (9)      C6B---C5B---H5B             118.8 (10)
  C4A---C5A---H5A             121.6 (9)      C4B---C5B---H5B             121.8 (10)
  C5A---C6A---C1A             126.08 (12)    C5B---C6B---C1B             124.41 (12)
  C5A---C6A---N14A            117.30 (11)    C5B---C6B---N14B            116.21 (11)
  C1A---C6A---N14A            116.57 (11)    C1B---C6B---N14B            119.37 (11)
  O10A---N8A---O9A            123.17 (11)    O9B---N8B---O10B            124.48 (11)
  O10A---N8A---C2A            117.99 (10)    O9B---N8B---C2B             118.06 (10)
  O9A---N8A---C2A             118.82 (10)    O10B---N8B---C2B            117.46 (10)
  O12A---N11A---O13A          123.45 (11)    O13B---N11B---O12B          123.32 (11)
  O12A---N11A---C4A           118.20 (11)    O13B---N11B---C4B           118.51 (11)
  O13A---N11A---C4A           118.35 (11)    O12B---N11B---C4B           118.17 (11)
  O16A---N14A---O15A          124.03 (11)    O16B---N14B---O15B          123.11 (11)
  O16A---N14A---C6A           118.12 (10)    O16B---N14B---C6B           118.08 (11)
  O15A---N14A---C6A           117.85 (10)    O15B---N14B---C6B           118.80 (10)
  C18A---O17A---C22A          110.98 (10)    C22B---O17B---C18B          111.02 (10)
  O17A---C18A---C19A          110.48 (11)    O17B---C18B---C19B          110.24 (11)
  O17A---C18A---H18A          110.1 (10)     O17B---C18B---H18C          108.1 (9)
  C19A---C18A---H18A          111.4 (10)     C19B---C18B---H18C          111.9 (9)
  O17A---C18A---H18B          106.4 (10)     O17B---C18B---H18D          107.6 (10)
  C19A---C18A---H18B          109.9 (10)     C19B---C18B---H18D          109.5 (10)
  H18A---C18A---H18B          108.4 (14)     H18C---C18B---H18D          109.4 (13)
  N20A---C19A---C18A          108.48 (11)    N20B---C19B---C18B          108.76 (11)
  N20A---C19A---H19A          107.1 (10)     N20B---C19B---H19C          106.8 (9)
  C18A---C19A---H19A          111.6 (10)     C18B---C19B---H19C          111.0 (9)
  N20A---C19A---H19B          106.8 (10)     N20B---C19B---H19D          107.1 (10)
  C18A---C19A---H19B          112.8 (10)     C18B---C19B---H19D          112.9 (10)
  H19A---C19A---H19B          109.8 (14)     H19C---C19B---H19D          110.0 (14)
  C21A---N20A---C19A          110.29 (10)    C21B---N20B---C19B          110.35 (10)
  C21A---N20A---H20A          110.8 (10)     C21B---N20B---H20C          112.0 (11)
  C19A---N20A---H20A          107.0 (10)     C19B---N20B---H20C          109.3 (11)
  C21A---N20A---H20B          112.2 (11)     C21B---N20B---H20D          111.0 (11)
  C19A---N20A---H20B          109.0 (11)     C19B---N20B---H20D          106.7 (11)
  H20A---N20A---H20B          107.4 (15)     H20C---N20B---H20D          107.3 (15)
  N20A---C21A---C22A          108.92 (10)    N20B---C21B---C22B          109.01 (10)
  N20A---C21A---H21A          107.5 (9)      N20B---C21B---H21C          109.5 (10)
  C22A---C21A---H21A          110.5 (9)      C22B---C21B---H21C          110.5 (9)
  N20A---C21A---H21B          109.1 (10)     N20B---C21B---H21D          106.1 (9)
  C22A---C21A---H21B          110.3 (9)      C22B---C21B---H21D          110.9 (9)
  H21A---C21A---H21B          110.6 (13)     H21C---C21B---H21D          110.7 (13)
  O17A---C22A---C21A          110.50 (11)    O17B---C22B---C21B          110.54 (10)
  O17A---C22A---H22A          106.6 (9)      O17B---C22B---H22C          109.9 (9)
  C21A---C22A---H22A          109.2 (9)      C21B---C22B---H22C          111.5 (9)
  O17A---C22A---H22B          109.8 (10)     O17B---C22B---H22D          107.0 (9)
  C21A---C22A---H22B          110.8 (10)     C21B---C22B---H22D          109.7 (9)
  H22A---C22A---H22B          109.8 (13)     H22C---C22B---H22D          108.1 (13)
                                                                         
  O7A---C1A---C2A---C3A       174.43 (12)    O7B---C1B---C2B---C3B       178.42 (12)
  C6A---C1A---C2A---C3A       −1.07 (17)     C6B---C1B---C2B---C3B       2.76 (18)
  O7A---C1A---C2A---N8A       −4.32 (19)     O7B---C1B---C2B---N8B       −0.12 (18)
  C6A---C1A---C2A---N8A       −179.83 (10)   C6B---C1B---C2B---N8B       −175.78 (10)
  C1A---C2A---C3A---C4A       2.82 (19)      C1B---C2B---C3B---C4B       −1.76 (19)
  N8A---C2A---C3A---C4A       −178.39 (11)   N8B---C2B---C3B---C4B       176.79 (11)
  C2A---C3A---C4A---C5A       −3.08 (19)     C2B---C3B---C4B---C5B       −1.87 (18)
  C2A---C3A---C4A---N11A      175.50 (11)    C2B---C3B---C4B---N11B      177.69 (11)
  C3A---C4A---C5A---C6A       1.64 (18)      C3B---C4B---C5B---C6B       4.11 (19)
  N11A---C4A---C5A---C6A      −176.93 (11)   N11B---C4B---C5B---C6B      −175.46 (11)
  C4A---C5A---C6A---C1A       0.14 (19)      C4B---C5B---C6B---C1B       −2.93 (19)
  C4A---C5A---C6A---N14A      −177.27 (11)   C4B---C5B---C6B---N14B      178.15 (11)
  O7A---C1A---C6A---C5A       −176.08 (12)   O7B---C1B---C6B---C5B       −175.89 (12)
  C2A---C1A---C6A---C5A       −0.42 (18)     C2B---C1B---C6B---C5B       −0.36 (17)
  O7A---C1A---C6A---N14A      1.35 (18)      O7B---C1B---C6B---N14B      3.00 (19)
  C2A---C1A---C6A---N14A      177.01 (10)    C2B---C1B---C6B---N14B      178.53 (10)
  C3A---C2A---N8A---O10A      −30.04 (16)    C3B---C2B---N8B---O9B       128.96 (12)
  C1A---C2A---N8A---O10A      148.81 (12)    C1B---C2B---N8B---O9B       −52.38 (15)
  C3A---C2A---N8A---O9A       148.13 (12)    C3B---C2B---N8B---O10B      −50.82 (16)
  C1A---C2A---N8A---O9A       −33.03 (17)    C1B---C2B---N8B---O10B      127.85 (12)
  C3A---C4A---N11A---O12A     −167.89 (11)   C5B---C4B---N11B---O13B     177.35 (11)
  C5A---C4A---N11A---O12A     10.72 (17)     C3B---C4B---N11B---O13B     −2.22 (17)
  C3A---C4A---N11A---O13A     12.32 (17)     C5B---C4B---N11B---O12B     −2.60 (17)
  C5A---C4A---N11A---O13A     −169.08 (11)   C3B---C4B---N11B---O12B     177.83 (11)
  C5A---C6A---N14A---O16A     50.61 (16)     C5B---C6B---N14B---O16B     30.79 (16)
  C1A---C6A---N14A---O16A     −127.06 (12)   C1B---C6B---N14B---O16B     −148.19 (12)
  C5A---C6A---N14A---O15A     −129.58 (12)   C5B---C6B---N14B---O15B     −147.88 (12)
  C1A---C6A---N14A---O15A     52.76 (15)     C1B---C6B---N14B---O15B     33.14 (17)
  C22A---O17A---C18A---C19A   60.91 (14)     C22B---O17B---C18B---C19B   −61.09 (14)
  O17A---C18A---C19A---N20A   −58.84 (14)    O17B---C18B---C19B---N20B   58.66 (14)
  C18A---C19A---N20A---C21A   57.62 (14)     C18B---C19B---N20B---C21B   −57.23 (14)
  C19A---N20A---C21A---C22A   −57.29 (13)    C19B---N20B---C21B---C22B   56.75 (13)
  C18A---O17A---C22A---C21A   −60.32 (14)    C18B---O17B---C22B---C21B   60.61 (14)
  N20A---C21A---C22A---O17A   57.97 (14)     N20B---C21B---C22B---O17B   −57.89 (14)
  --------------------------- -------------- --------------------------- --------------

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

  -------------------------- ------------ ------------ ------------- ---------------
  *D*---H···*A*              *D*---H      H···*A*      *D*···*A*     *D*---H···*A*
  N20A---H20A···O17B         0.905 (18)   1.938 (18)   2.8011 (14)   158.9 (15)
  C21A---H21B···O13B         0.976 (17)   2.485 (16)   3.1491 (16)   125.1 (12)
  C22B---H22C···O12B         0.985 (17)   2.531 (17)   3.3427 (16)   139.6 (12)
  N20A---H20B···O7B^i^       0.930 (19)   1.885 (19)   2.6838 (14)   142.6 (15)
  N20A---H20B···O15B^i^      0.930 (19)   2.225 (18)   2.9229 (15)   131.2 (14)
  C18B---H18C···O9B^i^       0.954 (17)   2.559 (16)   3.3078 (17)   135.5 (12)
  N20B---H20C···O7A^ii^      0.888 (18)   1.930 (18)   2.6911 (14)   142.8 (15)
  N20B---H20C···O9A^ii^      0.888 (18)   2.255 (18)   2.9248 (15)   132.1 (14)
  N20B---H20D···O12A^iii^    0.930 (19)   2.528 (17)   2.8693 (14)   102.0 (12)
  C18B---H18D···O10B^iii^    0.967 (17)   2.571 (17)   3.1533 (16)   118.8 (12)
  C21B---H21C···O12A^iii^    0.956 (16)   2.514 (16)   3.1210 (16)   121.4 (12)
  N20B---H20D···O17A^iv^     0.930 (19)   1.946 (19)   2.8182 (14)   155.4 (15)
  C3B---H3B···O16B^v^        0.958 (17)   2.495 (18)   3.4394 (17)   168.5 (13)
  C5A---H5A···O10A^v^        0.968 (17)   2.492 (17)   3.4436 (16)   167.7 (13)
  C18A---H18A···O15A^vi^     0.956 (17)   2.474 (17)   3.2628 (17)   139.7 (13)
  C21B---H21D···O15A^vi^     0.965 (17)   2.461 (17)   3.3679 (16)   156.6 (12)
  C21A---H21A···O9B^vii^     0.972 (16)   2.499 (16)   3.4139 (16)   156.8 (12)
  C21A---H21B···O16A^viii^   0.976 (17)   2.473 (16)   3.1274 (16)   124.2 (12)
  C22A---H22B···O13A^ix^     0.952 (17)   2.595 (17)   3.3916 (16)   141.3 (13)
  C18A---H18A···Cg4^ix^      0.958 (18)   2.906        3.718         140.37
  C22B---H22C···Cg3^x^       0.991 (18)   3.152        3.896         133.06
  -------------------------- ------------ ------------ ------------- ---------------

Symmetry codes: (i) −*x*+2, −*y*+1, −*z*+1; (ii) −*x*+2, −*y*, −*z*; (iii) *x*, *y*−1, *z*; (iv) *x*+1, *y*, *z*; (v) *x*−1, *y*, *z*; (vi) −*x*+1, −*y*, −*z*; (vii) −*x*+1, −*y*+1, −*z*+1; (viii) −*x*+1, −*y*+1, −*z*; (ix) *x*−1, *y*−1, *z*; (x) −*x*+2, −*y*+1, −*z*. 

###### Hydrogen-bond geometry (Å, °)

  *D*---H⋯*A*                    *D*---H      H⋯*A*        *D*⋯*A*       *D*---H⋯*A*
  ------------------------------ ------------ ------------ ------------- -------------
  N20*A*---H20*A*⋯O17*B*         0.905 (18)   1.938 (18)   2.8011 (14)   158.9 (15)
  C21*A*---H21*B*⋯O13*B*         0.976 (17)   2.485 (16)   3.1491 (16)   125.1 (12)
  C22*B*---H22*C*⋯O12*B*         0.985 (17)   2.531 (17)   3.3427 (16)   139.6 (12)
  N20*A*---H20*B*⋯O7*B*^i^       0.930 (19)   1.885 (19)   2.6838 (14)   142.6 (15)
  N20*A*---H20*B*⋯O15*B*^i^      0.930 (19)   2.225 (18)   2.9229 (15)   131.2 (14)
  C18*B*---H18*C*⋯O9*B*^i^       0.954 (17)   2.559 (16)   3.3078 (17)   135.5 (12)
  N20*B*---H20*C*⋯O7*A*^ii^      0.888 (18)   1.930 (18)   2.6911 (14)   142.8 (15)
  N20*B*---H20*C*⋯O9*A*^ii^      0.888 (18)   2.255 (18)   2.9248 (15)   132.1 (14)
  N20*B*---H20*D*⋯O12*A*^iii^    0.930 (19)   2.528 (17)   2.8693 (14)   102.0 (12)
  C18*B*---H18*D*⋯O10*B*^iii^    0.967 (17)   2.571 (17)   3.1533 (16)   118.8 (12)
  C21*B*---H21*C*⋯O12*A*^iii^    0.956 (16)   2.514 (16)   3.1210 (16)   121.4 (12)
  N20*B*---H20*D*⋯O17*A*^iv^     0.930 (19)   1.946 (19)   2.8182 (14)   155.4 (15)
  C3*B*---H3*B*⋯O16*B*^v^        0.958 (17)   2.495 (18)   3.4394 (17)   168.5 (13)
  C5*A*---H5*A*⋯O10*A*^v^        0.968 (17)   2.492 (17)   3.4436 (16)   167.7 (13)
  C18*A*---H18*A*⋯O15*A*^vi^     0.956 (17)   2.474 (17)   3.2628 (17)   139.7 (13)
  C21*B*---H21*D*⋯O15*A*^vi^     0.965 (17)   2.461 (17)   3.3679 (16)   156.6 (12)
  C21*A*---H21*A*⋯O9*B*^vii^     0.972 (16)   2.499 (16)   3.4139 (16)   156.8 (12)
  C21*A*---H21*B*⋯O16*A*^viii^   0.976 (17)   2.473 (16)   3.1274 (16)   124.2 (12)
  C22*A*---H22*B*⋯O13*A*^ix^     0.952 (17)   2.595 (17)   3.3916 (16)   141.3 (13)
  C18*A*---H18*A*⋯*Cg*4^ix^      0.958 (18)   2.906        3.718         140.37
  C22*B*---H22*C*⋯*Cg*3^x^       0.991 (18)   3.152        3.896         133.06

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) . * Cg*3 and *Cg*4 are the centroids of the C1*A*--C6*A* and C1*B--*C6*B* rings, respectively.