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

For background information on mefloquine and derivatives, see: Kunin & Ellis (2007[@bb7]); Maguire *et al.* ( 2006[@bb8]); Dow *et al.* ( 2004[@bb2]).  For selected crystal structures of mefloquine and its salts, see: Obaleye *et al.* ( 2009[@bb9]); Skórska *et al.* ( 2005[@bb13]); Karle & Karle (1991[@bb5], 2002[@bb6]); Wardell *et al.* ( 2010[@bb15], 2011[@bb14]). 

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

 {#sec2.1}

### Crystal data {#sec2.1.1}

C~17~H~17~F~6~N~2~O^+^·C~7~H~5~N~2~O~4~ ^−^·1.5H~2~O*M* *~r~* = 587.48Triclinic,*a* = 9.1705 (5) Å*b* = 12.5446 (9) Å*c* = 12.7788 (8) Åα = 66.278 (4)°β = 77.261 (4)°γ = 71.537 (4)°*V* = 1269.23 (14) Å^3^*Z* = 2Mo *K*α radiationμ = 0.14 mm^−1^*T* = 120 K0.28 × 0.16 × 0.10 mm

### Data collection {#sec2.1.2}

Bruker--Nonius APEXII CCD camera on κ-goniostat diffractometerAbsorption correction: multi-scan (*SADABS*; Sheldrick, 2007[@bb11]) *T* ~min~ = 0.640, *T* ~max~ = 0.74625681 measured reflections5832 independent reflections3477 reflections with *I* \> 2σ(*I*)*R* ~int~ = 0.078

### Refinement {#sec2.1.3}

*R*\[*F* ^2^ \> 2σ(*F* ^2^)\] = 0.064*wR*(*F* ^2^) = 0.174*S* = 1.035832 reflections416 parameters15 restraintsH atoms treated by a mixture of independent and constrained refinementΔρ~max~ = 0.39 e Å^−3^Δρ~min~ = −0.38 e Å^−3^

 {#d5e745}

Data collection: *COLLECT* (Hooft, 1998[@bb4]); cell refinement: *DENZO* (Otwinowski & Minor, 1997[@bb10]) and *COLLECT*; data reduction: *DENZO* and *COLLECT*; program(s) used to solve structure: *SHELXS97* (Sheldrick, 2008[@bb12]); program(s) used to refine structure: *SHELXL97* (Sheldrick, 2008[@bb12]); molecular graphics: *ORTEP-3* (Farrugia, 1997[@bb3]) and *DIAMOND* (Brandenburg, 2006[@bb1]); software used to prepare material for publication: *publCIF* (Westrip, 2010[@bb16]). 

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

Crystal structure: contains datablock(s) global, I. DOI: [10.1107/S160053681104270X/lh5355sup1.cif](http://dx.doi.org/10.1107/S160053681104270X/lh5355sup1.cif)

Structure factors: contains datablock(s) I. DOI: [10.1107/S160053681104270X/lh5355Isup2.hkl](http://dx.doi.org/10.1107/S160053681104270X/lh5355Isup2.hkl)

Additional supplementary materials: [crystallographic information](http://scripts.iucr.org/cgi-bin/sendsupfiles?lh5355&file=lh5355sup0.html&mime=text/html); [3D view](http://scripts.iucr.org/cgi-bin/sendcif?lh5355sup1&Qmime=cif); [checkCIF report](http://scripts.iucr.org/cgi-bin/paper?lh5355&checkcif=yes)

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: [LH5355](http://scripts.iucr.org/cgi-bin/sendsup?lh5355)). 

The use of the EPSRC X-ray crystallographic service at the University of Southampton, England, and the valuable assistance of the staff there is gratefully acknowledged.  JLW acknowledges support from CAPES and FAPEMIG (Brazil). 

Comment
=======

A synthetic analogue of quinine, mefloquine, is manufactured as the racemic *erythro* hydrochloride salt, and is used in the prevention and treatment of malaria in combination with other drugs (Maguire *et al.*,  2006).  While it is known that both enantiomers of *erythro* mefloquinium hydrochloride are active, the (+) form is the more potent against the D6 and W2 strains of *Plasmodium falciparum* (Karle & Karle, 2002).  After its introduction in 1971, mefloquine has proved to be an effective anti-malarial agent, in part due to its long half-life and the fact that it is a good prophylactic.  A widespread resistance of *Plasmodium sp*.  developed by the end of the 20th century.  This, together with undesirable side-effects \[*e.g*.  anxiety, aggression, seizures, nightmares, neuropathy, insomnia, acute depression and urinary disorders\] have resulted in a decline in its use (Dow *et al.*,  2004).  Derivatives of mefloquine are also been investigated against for efficacy against other diseases, *e.g*.  as anti-viral and anti-tuberculosis agents (Kunin & Ellis, 2007).  A few crystal structures of mefloquine (Skórska *et al.*,  2005) and mefloquinium salts, including the hydrated chloride (Karle & Karle, 2002; Skórska *et al.*,  2005), methylsulfonate (Karle & Karle, 1991), tetrachlorocobaltate (Skórska *et al.*,  2005), and tetrachlorocuprate and tetrabromocadmate salts (Obaleye *et al.*,  2009) have been reported.  We now report the structure of the title salt, (I), in continuation of structural studies in this area (Wardell *et al.*,  2010; Wardell *et al.*,  2011). 

The asymmetric unit of (I) comprises a piperidin-1-ium cation, a 3-amino-5-nitrobenzoate anion, and three fractionally occupied \[*i.e*.  0.414 (3), 0.627 (6) and 0.459 (5)\] disordered water molecules of solvation; the ions are illustrated in Fig.  1.  The confirmation of protonation at the amine-N2 atom is found in the nature of the intermolecular interactions, see below, as well as in the equivalence of the C---O bond distances \[O2---C18 = 1.251 (4) Å and O3---C18 = 1.246 (4) Å\] in the anion.  Overall, the cation has an *L*-shaped conformation as the quinolinyl residue is approximately orthogonal to the rest of the cation; the C2--C3--C12--C13 torsion angle is -102.9 (3) °.  The six-membered piperidin-1-ium ring adopts a chair conformation.  The anion is effectively planar with both of the carboxylate \[O2---C18---C19---C20 torsion angle = 179.7 (2)°\] and nitro \[O4---N3---C21---C20 torsion angle = -3.9 (3)°\] groups being co-planar with the benzene ring to which it is connected

The crystal packing is stabilized by hydrogen bonding, Table 1, that leads to layers in the *ab* plane.  The carboxylate-O2 atom accepts two hydrogen bonds, one from the cation-OH and the other from the anion-amino-H. The carboxylate-O3 atom accepts a single interaction, *i.e*.  from an ammonium-H. The second amino-H atom connects to nitro-O while the second ammonium-H hydrogen bonds water-O atoms.  Water molecules form hydrogen bonds with each other and also donor hydrogen bonds to the cation-O atom, anion-O atoms and a weak contact to the F6 atom, Table 1.  A view of the unit-cell contents is shown in Fig.  2 indicating layers stack along the *c* axis. 

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

A solution of mefloquine (0.383 g, 1 mmol) and 3-amino-5-nitrobenzoic acid (0.18 g. 1 mmol) in EtOH (15 ml) was refluxed for 20 min.  On maintaining the reaction mixture at room temperature, crystals of the title salt slowly formed. * M*.pt.:  503--504 K (dec.).  IR ν: 3600--2200(br), 1632, 1612, 1555, 1518, 1472, 1435, 1389, 1344, 1310, 1265, 1217, 1184, 1150, 1109, 1078, 1013, 970, 934, 918, 899, 887, 866, 839, 795, 783, 743, 725, 665, 542, 444 cm^-1^.

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

The C-bound H atoms were geometrically placed (C---H = 0.95--1.00 Å) and refined as riding with *U~iso~*(H) = 1.2*U~eq~*(C).  The O---H and N---H H atoms were located from a difference map and refined with O---H = 0.84±0.01 Å and N---H = 0.88--0.92±0.01 Å, respectively, and with *U~iso~*(H) = *yU~eq~*(O or N) with *y* = 1.5 for O and *y* = 1.2 for N. There are a total of 1.5 water molecules in the asymmetric unit and these are disordered over three positions with site occupancies factors of 0.414 (3), 0.627 (6) and 0.459 (5); hydrogen atoms were located for each of these and refined as described above. 

Figures
=======

![ The molecular structures of the components comprising the asymmetric unit in (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.  The disordered water molecules of solvation have been omitted for reasons of clarity.](e-67-o3019-fig1){#Fap1}

![ A view in projection along the a axis of the unit-cell contents in (I) showing the alternation of cations and anions along the c axis.  The O---H···O, N---H···O and O---H···F interactions are shown as orange, blue and green dashed lines, respectively.](e-67-o3019-fig2){#Fap2}

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

  ----------------------------------------------------- ----------------------------------------
  C~17~H~17~F~6~N~2~O^+^·C~7~H~5~N~2~O~4~^−^·1.5H~2~O   *Z* = 2
  *M~r~* = 587.48                                       *F*(000) = 606
  Triclinic, *P*1                                       *D*~x~ = 1.537 Mg m^−3^
  Hall symbol: -P 1                                     Mo *K*α radiation, λ = 0.71073 Å
  *a* = 9.1705 (5) Å                                    Cell parameters from 30639 reflections
  *b* = 12.5446 (9) Å                                   θ = 2.9--27.5°
  *c* = 12.7788 (8) Å                                   µ = 0.14 mm^−1^
  α = 66.278 (4)°                                       *T* = 120 K
  β = 77.261 (4)°                                       Block, orange
  γ = 71.537 (4)°                                       0.28 × 0.16 × 0.10 mm
  *V* = 1269.23 (14) Å^3^                               
  ----------------------------------------------------- ----------------------------------------

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

  ---------------------------------------------------------------- --------------------------------------
  Bruker--Nonius APEXII CCD camera on κ-goniostat diffractometer   5832 independent reflections
  Radiation source: Bruker-Nonius FR591 rotating anode             3477 reflections with *I* \> 2σ(*I*)
  10cm confocal mirrors                                            *R*~int~ = 0.078
  Detector resolution: 9.091 pixels mm^-1^                         θ~max~ = 27.6°, θ~min~ = 3.0°
  φ & ω scans                                                      *h* = −11→11
  Absorption correction: multi-scan (*SADABS*; Sheldrick, 2007)    *k* = −16→16
  *T*~min~ = 0.640, *T*~max~ = 0.746                               *l* = −16→16
  25681 measured reflections                                       
  ---------------------------------------------------------------- --------------------------------------

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*\[*F*^2^ \> 2σ(*F*^2^)\] = 0.064                              H atoms treated by a mixture of independent and constrained refinement
  *wR*(*F*^2^) = 0.174                                             *w* = 1/\[σ^2^(*F*~o~^2^) + (0.0836*P*)^2^ + 0.2367*P*\] where *P* = (*F*~o~^2^ + 2*F*~c~^2^)/3
  *S* = 1.03                                                       (Δ/σ)~max~ \< 0.001
  5832 reflections                                                 Δρ~max~ = 0.39 e Å^−3^
  416 parameters                                                   Δρ~min~ = −0.38 e Å^−3^
  15 restraints                                                    Extinction correction: *SHELXL97*, Fc^\*^=kFc\[1+0.001xFc^2^λ^3^/sin(2θ)\]^-1/4^
  Primary atom site location: structure-invariant direct methods   Extinction coefficient: 0.032 (4)
  ---------------------------------------------------------------- -------------------------------------------------------------------------------------------------

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^ \> 2σ(*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~   Occ. ( \<1)
  F1     0.87381 (17)   0.49471 (18)   0.83650 (15)   0.0532 (5)           
  F2     0.74544 (19)   0.50218 (18)   0.99348 (14)   0.0515 (5)           
  F3     0.7703 (2)     0.66464 (17)   0.8535 (2)     0.0766 (7)           
  F4     0.55227 (19)   0.21925 (14)   0.99220 (14)   0.0443 (4)           
  F5     0.69944 (17)   0.22502 (14)   0.83406 (15)   0.0457 (5)           
  F6     0.51655 (18)   0.13558 (14)   0.88618 (15)   0.0443 (4)           
  O1     0.3030 (2)     0.89697 (16)   0.68621 (16)   0.0321 (4)           
  H1     0.287 (4)      0.940 (2)      0.6179 (12)    0.048\*              
  O2     0.2506 (2)     1.03009 (17)   0.46810 (18)   0.0442 (5)           
  O3     0.0666 (2)     1.19038 (17)   0.39087 (19)   0.0437 (5)           
  O4     0.0825 (2)     1.58565 (17)   0.37663 (17)   0.0409 (5)           
  O5     0.2815 (3)     1.60038 (18)   0.42819 (19)   0.0509 (6)           
  O1W    0.3447 (6)     1.0482 (5)     0.7901 (4)     0.0431 (14)          0.414 (3)
  H1W1   0.358 (8)      0.991 (5)      0.768 (7)      0.065\*              0.414 (3)
  H1W2   0.413 (7)      1.086 (6)      0.754 (6)      0.065\*              0.414 (3)
  O2W    0.0428 (4)     1.1348 (3)     0.7158 (3)     0.0449 (11)          0.627 (6)
  H2W1   0.128 (3)      1.133 (4)      0.733 (5)      0.067\*              0.627 (6)
  H2W2   −0.006 (5)     1.2078 (17)    0.689 (5)      0.067\*              0.627 (6)
  O3W    −0.0625 (6)    1.1518 (4)     0.6409 (4)     0.0467 (16)          0.459 (5)
  H3W1   −0.022 (9)     1.158 (6)      0.573 (3)      0.070\*              0.459 (5)
  H3W2   −0.096 (9)     1.221 (3)      0.644 (6)      0.070\*              0.459 (5)
  N1     0.5885 (2)     0.46024 (19)   0.84811 (18)   0.0284 (5)           
  N2     −0.0203 (2)    0.9090 (2)     0.7489 (2)     0.0297 (5)           
  H21    −0.039 (3)     0.895 (3)      0.6913 (17)    0.036\*              
  H22    0.008 (3)      0.9766 (16)    0.727 (2)      0.036\*              
  N3     0.2069 (3)     1.5407 (2)     0.41647 (19)   0.0338 (5)           
  N4     0.6061 (3)     1.1835 (2)     0.5903 (2)     0.0467 (7)           
  H41    0.657 (3)      1.1130 (16)    0.585 (3)      0.056\*              
  H42    0.660 (3)      1.230 (3)      0.590 (3)      0.056\*              
  C1     0.6030 (3)     0.5648 (2)     0.8371 (2)     0.0273 (6)           
  C2     0.4964 (3)     0.6767 (2)     0.7926 (2)     0.0269 (6)           
  H2A    0.5132         0.7488         0.7899         0.032\*              
  C3     0.3666 (3)     0.6788 (2)     0.7529 (2)     0.0261 (6)           
  C4     0.3486 (3)     0.5686 (2)     0.7576 (2)     0.0262 (6)           
  C5     0.2229 (3)     0.5601 (2)     0.7155 (2)     0.0295 (6)           
  H5     0.1475         0.6313         0.6800         0.035\*              
  C6     0.2094 (3)     0.4515 (2)     0.7256 (2)     0.0320 (6)           
  H6A    0.1254         0.4478         0.6962         0.038\*              
  C7     0.3189 (3)     0.3440 (2)     0.7793 (2)     0.0325 (6)           
  H7     0.3071         0.2686         0.7868         0.039\*              
  C8     0.4418 (3)     0.3481 (2)     0.8204 (2)     0.0295 (6)           
  C9     0.4616 (3)     0.4604 (2)     0.8081 (2)     0.0273 (6)           
  C10    0.7471 (3)     0.5578 (2)     0.8802 (2)     0.0322 (6)           
  C11    0.5530 (3)     0.2330 (2)     0.8820 (3)     0.0350 (6)           
  C12    0.2441 (3)     0.7967 (2)     0.7111 (2)     0.0278 (6)           
  H12A   0.2092         0.8029         0.6396         0.033\*              
  C13    0.1041 (3)     0.7996 (2)     0.8030 (2)     0.0281 (6)           
  H13    0.0664         0.7264         0.8232         0.034\*              
  C14    −0.1666 (3)    0.9248 (3)     0.8275 (3)     0.0371 (7)           
  H14A   −0.2144        0.8581         0.8453         0.045\*              
  H14B   −0.2404        1.0013         0.7885         0.045\*              
  C15    −0.1351 (3)    0.9265 (3)     0.9384 (2)     0.0374 (7)           
  H15A   −0.2316        0.9299         0.9914         0.045\*              
  H15B   −0.1005        0.9994         0.9217         0.045\*              
  C16    −0.0107 (3)    0.8142 (3)     0.9959 (2)     0.0385 (7)           
  H16A   0.0126         0.8192         1.0656         0.046\*              
  H16B   −0.0491        0.7416         1.0196         0.046\*              
  C17    0.1353 (3)     0.8042 (3)     0.9131 (2)     0.0328 (6)           
  H17A   0.2141         0.7304         0.9506         0.039\*              
  H17B   0.1773         0.8742         0.8939         0.039\*              
  C18    0.1878 (3)     1.1404 (2)     0.4389 (2)     0.0297 (6)           
  C19    0.2628 (3)     1.2185 (2)     0.4629 (2)     0.0273 (6)           
  C20    0.1963 (3)     1.3416 (2)     0.4311 (2)     0.0275 (6)           
  H20    0.1021         1.3781         0.3969         0.033\*              
  C21    0.2735 (3)     1.4088 (2)     0.4515 (2)     0.0294 (6)           
  C22    0.4084 (3)     1.3611 (2)     0.5017 (2)     0.0322 (6)           
  H22A   0.4565         1.4115         0.5137         0.039\*              
  C23    0.4745 (3)     1.2369 (2)     0.5350 (2)     0.0325 (6)           
  C24    0.3990 (3)     1.1676 (2)     0.5141 (2)     0.0297 (6)           
  H24    0.4425         1.0832         0.5356         0.036\*              
  ------ -------------- -------------- -------------- -------------------- ------------

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

  ----- ------------- ------------- ------------- -------------- -------------- --------------
        *U*^11^       *U*^22^       *U*^33^       *U*^12^        *U*^13^        *U*^23^
  F1    0.0231 (8)    0.0818 (14)   0.0522 (11)   −0.0005 (8)    −0.0032 (7)    −0.0318 (10)
  F2    0.0431 (10)   0.0790 (14)   0.0330 (9)    −0.0209 (9)    −0.0030 (7)    −0.0173 (9)
  F3    0.0609 (12)   0.0301 (11)   0.140 (2)     −0.0128 (9)    −0.0556 (13)   −0.0075 (12)
  F4    0.0490 (10)   0.0316 (10)   0.0437 (10)   −0.0045 (7)    −0.0151 (8)    −0.0043 (8)
  F5    0.0274 (8)    0.0313 (9)    0.0670 (12)   0.0030 (7)     −0.0015 (8)    −0.0161 (9)
  F6    0.0432 (9)    0.0209 (9)    0.0658 (11)   −0.0029 (7)    −0.0133 (8)    −0.0129 (8)
  O1    0.0339 (10)   0.0219 (10)   0.0374 (10)   −0.0080 (8)    −0.0063 (8)    −0.0055 (8)
  O2    0.0627 (13)   0.0206 (11)   0.0550 (13)   −0.0047 (9)    −0.0330 (11)   −0.0102 (9)
  O3    0.0380 (11)   0.0283 (11)   0.0703 (14)   −0.0028 (9)    −0.0203 (10)   −0.0201 (11)
  O4    0.0492 (12)   0.0263 (11)   0.0478 (12)   −0.0050 (9)    −0.0130 (10)   −0.0133 (10)
  O5    0.0781 (15)   0.0252 (11)   0.0601 (14)   −0.0162 (10)   −0.0286 (12)   −0.0129 (10)
  O1W   0.050 (3)     0.044 (3)     0.040 (3)     −0.017 (2)     −0.003 (2)     −0.019 (3)
  O2W   0.043 (2)     0.032 (2)     0.056 (2)     −0.0070 (15)   −0.0043 (17)   −0.0147 (18)
  O3W   0.049 (3)     0.030 (3)     0.055 (3)     −0.005 (2)     −0.003 (2)     −0.014 (2)
  N1    0.0231 (11)   0.0252 (12)   0.0322 (12)   −0.0050 (9)    0.0003 (9)     −0.0081 (10)
  N2    0.0301 (11)   0.0209 (12)   0.0385 (13)   −0.0007 (9)    −0.0104 (10)   −0.0120 (10)
  N3    0.0525 (15)   0.0229 (12)   0.0296 (12)   −0.0110 (11)   −0.0067 (11)   −0.0107 (10)
  N4    0.0625 (17)   0.0285 (14)   0.0600 (17)   −0.0056 (12)   −0.0316 (14)   −0.0185 (13)
  C1    0.0240 (12)   0.0243 (14)   0.0288 (13)   −0.0051 (10)   −0.0005 (10)   −0.0066 (11)
  C2    0.0273 (13)   0.0208 (13)   0.0288 (13)   −0.0066 (10)   0.0010 (10)    −0.0069 (11)
  C3    0.0259 (13)   0.0218 (13)   0.0250 (12)   −0.0032 (10)   −0.0005 (10)   −0.0060 (11)
  C4    0.0239 (12)   0.0234 (14)   0.0273 (13)   −0.0038 (10)   −0.0009 (10)   −0.0077 (11)
  C5    0.0267 (13)   0.0240 (14)   0.0338 (14)   0.0004 (10)    −0.0028 (11)   −0.0119 (12)
  C6    0.0265 (13)   0.0310 (15)   0.0389 (15)   −0.0043 (11)   −0.0037 (11)   −0.0152 (13)
  C7    0.0300 (14)   0.0257 (15)   0.0416 (15)   −0.0041 (11)   −0.0019 (12)   −0.0153 (13)
  C8    0.0256 (13)   0.0246 (14)   0.0354 (14)   −0.0014 (10)   −0.0016 (11)   −0.0125 (12)
  C9    0.0207 (12)   0.0269 (14)   0.0299 (13)   −0.0044 (10)   0.0010 (10)    −0.0089 (11)
  C10   0.0311 (14)   0.0240 (14)   0.0366 (15)   −0.0069 (11)   −0.0026 (12)   −0.0065 (12)
  C11   0.0308 (14)   0.0220 (14)   0.0465 (17)   −0.0028 (11)   −0.0034 (12)   −0.0099 (13)
  C12   0.0268 (13)   0.0188 (13)   0.0336 (14)   −0.0023 (10)   −0.0065 (11)   −0.0061 (11)
  C13   0.0261 (13)   0.0150 (13)   0.0379 (14)   −0.0004 (10)   −0.0057 (11)   −0.0067 (11)
  C14   0.0246 (13)   0.0301 (16)   0.0555 (18)   −0.0004 (11)   −0.0057 (12)   −0.0186 (14)
  C15   0.0319 (14)   0.0318 (16)   0.0440 (16)   −0.0014 (12)   0.0000 (12)    −0.0162 (14)
  C16   0.0350 (15)   0.0324 (16)   0.0402 (16)   −0.0012 (12)   0.0003 (12)    −0.0131 (14)
  C17   0.0294 (13)   0.0281 (15)   0.0371 (15)   −0.0019 (11)   −0.0072 (11)   −0.0102 (12)
  C18   0.0413 (15)   0.0230 (14)   0.0255 (13)   −0.0078 (12)   −0.0068 (11)   −0.0081 (11)
  C19   0.0386 (14)   0.0244 (14)   0.0201 (12)   −0.0106 (11)   −0.0022 (11)   −0.0077 (11)
  C20   0.0354 (14)   0.0232 (14)   0.0258 (13)   −0.0089 (11)   −0.0023 (11)   −0.0102 (11)
  C21   0.0457 (16)   0.0197 (13)   0.0235 (13)   −0.0080 (11)   −0.0043 (11)   −0.0083 (11)
  C22   0.0469 (16)   0.0258 (15)   0.0300 (14)   −0.0127 (12)   −0.0069 (12)   −0.0121 (12)
  C23   0.0470 (16)   0.0283 (15)   0.0272 (13)   −0.0104 (12)   −0.0108 (12)   −0.0106 (12)
  C24   0.0422 (15)   0.0213 (14)   0.0254 (13)   −0.0069 (11)   −0.0070 (11)   −0.0073 (11)
  ----- ------------- ------------- ------------- -------------- -------------- --------------

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

  -------------------- ------------ ----------------------- -------------
  F1---C10             1.333 (3)    C4---C5                 1.423 (4)
  F2---C10             1.329 (3)    C4---C9                 1.425 (4)
  F3---C10             1.318 (3)    C5---C6                 1.359 (4)
  F4---C11             1.346 (3)    C5---H5                 0.9500
  F5---C11             1.338 (3)    C6---C7                 1.414 (4)
  F6---C11             1.345 (3)    C6---H6A                0.9500
  O1---C12             1.417 (3)    C7---C8                 1.367 (4)
  O1---H1              0.839 (10)   C7---H7                 0.9500
  O2---C18             1.249 (3)    C8---C9                 1.419 (4)
  O3---C18             1.248 (3)    C8---C11                1.501 (4)
  O4---N3              1.223 (3)    C12---C13               1.540 (3)
  O5---N3              1.230 (3)    C12---H12A              1.0000
  O1W---H1W1           0.843 (10)   C13---C17               1.523 (4)
  O1W---H1W2           0.843 (10)   C13---H13               1.0000
  O2W---H2W1           0.849 (10)   C14---C15               1.516 (4)
  O2W---H2W2           0.845 (10)   C14---H14A              0.9900
  O3W---H2W2           1.36 (5)     C14---H14B              0.9900
  O3W---H3W1           0.843 (10)   C15---C16               1.532 (4)
  O3W---H3W2           0.843 (10)   C15---H15A              0.9900
  N1---C1              1.307 (3)    C15---H15B              0.9900
  N1---C9              1.370 (3)    C16---C17               1.518 (4)
  N2---C14             1.499 (3)    C16---H16A              0.9900
  N2---C13             1.502 (3)    C16---H16B              0.9900
  N2---H21             0.885 (10)   C17---H17A              0.9900
  N2---H22             0.886 (10)   C17---H17B              0.9900
  N3---C21             1.481 (3)    C18---C19               1.513 (4)
  N4---C23             1.374 (4)    C19---C24               1.384 (4)
  N4---H41             0.881 (10)   C19---C20               1.389 (4)
  N4---H42             0.877 (10)   C20---C21               1.384 (3)
  C1---C2              1.409 (4)    C20---H20               0.9500
  C1---C10             1.506 (4)    C21---C22               1.368 (4)
  C2---C3              1.382 (4)    C22---C23               1.399 (4)
  C2---H2A             0.9500       C22---H22A              0.9500
  C3---C4              1.420 (4)    C23---C24               1.399 (4)
  C3---C12             1.520 (3)    C24---H24               0.9500
                                                            
  C12---O1---H1        105 (2)      O1---C12---C3           111.4 (2)
  H1W1---O1W---H1W2    108.9 (18)   O1---C12---C13          108.89 (19)
  H2W1---O2W---H2W2    107.6 (17)   C3---C12---C13          110.1 (2)
  H2W2---O3W---H3W1    114 (6)      O1---C12---H12A         108.8
  H2W2---O3W---H3W2    49 (6)       C3---C12---H12A         108.8
  H3W1---O3W---H3W2    108.9 (18)   C13---C12---H12A        108.8
  C1---N1---C9         116.9 (2)    N2---C13---C17          109.3 (2)
  C14---N2---C13       113.7 (2)    N2---C13---C12          106.8 (2)
  C14---N2---H21       108.8 (18)   C17---C13---C12         115.0 (2)
  C13---N2---H21       103.5 (19)   N2---C13---H13          108.5
  C14---N2---H22       105.2 (18)   C17---C13---H13         108.5
  C13---N2---H22       112.4 (19)   C12---C13---H13         108.5
  H21---N2---H22       113 (3)      N2---C14---C15          111.1 (2)
  O4---N3---O5         122.9 (2)    N2---C14---H14A         109.4
  O4---N3---C21        119.5 (2)    C15---C14---H14A        109.4
  O5---N3---C21        117.6 (2)    N2---C14---H14B         109.4
  C23---N4---H41       114 (2)      C15---C14---H14B        109.4
  C23---N4---H42       118 (2)      H14A---C14---H14B       108.0
  H41---N4---H42       117 (3)      C14---C15---C16         110.9 (2)
  N1---C1---C2         125.9 (2)    C14---C15---H15A        109.5
  N1---C1---C10        114.0 (2)    C16---C15---H15A        109.5
  C2---C1---C10        120.1 (2)    C14---C15---H15B        109.5
  C3---C2---C1         118.1 (2)    C16---C15---H15B        109.5
  C3---C2---H2A        121.0        H15A---C15---H15B       108.1
  C1---C2---H2A        121.0        C17---C16---C15         110.0 (2)
  C2---C3---C4         118.5 (2)    C17---C16---H16A        109.7
  C2---C3---C12        119.6 (2)    C15---C16---H16A        109.7
  C4---C3---C12        121.8 (2)    C17---C16---H16B        109.7
  C3---C4---C5         123.5 (2)    C15---C16---H16B        109.7
  C3---C4---C9         118.3 (2)    H16A---C16---H16B       108.2
  C5---C4---C9         118.2 (2)    C16---C17---C13         111.5 (2)
  C6---C5---C4         120.8 (2)    C16---C17---H17A        109.3
  C6---C5---H5         119.6        C13---C17---H17A        109.3
  C4---C5---H5         119.6        C16---C17---H17B        109.3
  C5---C6---C7         120.8 (2)    C13---C17---H17B        109.3
  C5---C6---H6A        119.6        H17A---C17---H17B       108.0
  C7---C6---H6A        119.6        O3---C18---O2           123.9 (2)
  C8---C7---C6         120.3 (2)    O3---C18---C19          117.8 (2)
  C8---C7---H7         119.9        O2---C18---C19          118.3 (2)
  C6---C7---H7         119.9        C24---C19---C20         120.2 (2)
  C7---C8---C9         120.2 (2)    C24---C19---C18         119.9 (2)
  C7---C8---C11        119.6 (2)    C20---C19---C18         119.8 (2)
  C9---C8---C11        120.1 (2)    C21---C20---C19         117.0 (2)
  N1---C9---C8         118.1 (2)    C21---C20---H20         121.5
  N1---C9---C4         122.2 (2)    C19---C20---H20         121.5
  C8---C9---C4         119.6 (2)    C22---C21---C20         124.0 (2)
  F3---C10---F2        108.0 (2)    C22---C21---N3          117.7 (2)
  F3---C10---F1        106.2 (2)    C20---C21---N3          118.2 (2)
  F2---C10---F1        105.0 (2)    C21---C22---C23         119.0 (2)
  F3---C10---C1        112.7 (2)    C21---C22---H22A        120.5
  F2---C10---C1        112.3 (2)    C23---C22---H22A        120.5
  F1---C10---C1        112.1 (2)    N4---C23---C24          120.7 (2)
  F5---C11---F6        106.4 (2)    N4---C23---C22          121.4 (2)
  F5---C11---F4        106.9 (2)    C24---C23---C22         117.8 (2)
  F6---C11---F4        105.7 (2)    C19---C24---C23         121.9 (2)
  F5---C11---C8        113.6 (2)    C19---C24---H24         119.1
  F6---C11---C8        112.1 (2)    C23---C24---H24         119.1
  F4---C11---C8        111.6 (2)                            
                                                            
  C9---N1---C1---C2    3.1 (4)      C9---C8---C11---F4      61.3 (3)
  C9---N1---C1---C10   −178.5 (2)   C2---C3---C12---O1      18.0 (3)
  N1---C1---C2---C3    −2.3 (4)     C4---C3---C12---O1      −164.9 (2)
  C10---C1---C2---C3   179.3 (2)    C2---C3---C12---C13     −102.9 (3)
  C1---C2---C3---C4    −0.9 (3)     C4---C3---C12---C13     74.2 (3)
  C1---C2---C3---C12   176.3 (2)    C14---N2---C13---C17    −55.4 (3)
  C2---C3---C4---C5    −177.6 (2)   C14---N2---C13---C12    179.6 (2)
  C12---C3---C4---C5   5.3 (4)      O1---C12---C13---N2     66.0 (2)
  C2---C3---C4---C9    3.0 (3)      C3---C12---C13---N2     −171.6 (2)
  C12---C3---C4---C9   −174.1 (2)   O1---C12---C13---C17    −55.4 (3)
  C3---C4---C5---C6    −177.9 (2)   C3---C12---C13---C17    67.0 (3)
  C9---C4---C5---C6    1.4 (4)      C13---N2---C14---C15    55.0 (3)
  C4---C5---C6---C7    0.7 (4)      N2---C14---C15---C16    −54.2 (3)
  C5---C6---C7---C8    −1.0 (4)     C14---C15---C16---C17   56.0 (3)
  C6---C7---C8---C9    −0.9 (4)     C15---C16---C17---C13   −57.8 (3)
  C6---C7---C8---C11   177.1 (2)    N2---C13---C17---C16    56.6 (3)
  C1---N1---C9---C8    −179.1 (2)   C12---C13---C17---C16   176.7 (2)
  C1---N1---C9---C4    −0.6 (3)     O3---C18---C19---C24    −178.8 (2)
  C7---C8---C9---N1    −178.4 (2)   O2---C18---C19---C24    1.1 (3)
  C11---C8---C9---N1   3.6 (3)      O3---C18---C19---C20    −0.2 (3)
  C7---C8---C9---C4    3.0 (4)      O2---C18---C19---C20    179.7 (2)
  C11---C8---C9---C4   −175.0 (2)   C24---C19---C20---C21   0.9 (3)
  C3---C4---C9---N1    −2.3 (3)     C18---C19---C20---C21   −177.7 (2)
  C5---C4---C9---N1    178.3 (2)    C19---C20---C21---C22   −0.8 (4)
  C3---C4---C9---C8    176.1 (2)    C19---C20---C21---N3    178.9 (2)
  C5---C4---C9---C8    −3.2 (3)     O4---N3---C21---C22     −176.4 (2)
  N1---C1---C10---F3   170.9 (2)    O5---N3---C21---C22     4.3 (3)
  C2---C1---C10---F3   −10.5 (3)    O4---N3---C21---C20     3.9 (3)
  N1---C1---C10---F2   −66.8 (3)    O5---N3---C21---C20     −175.4 (2)
  C2---C1---C10---F2   111.7 (3)    C20---C21---C22---C23   0.0 (4)
  N1---C1---C10---F1   51.2 (3)     N3---C21---C22---C23    −179.6 (2)
  C2---C1---C10---F1   −130.3 (2)   C21---C22---C23---N4    −177.1 (3)
  C7---C8---C11---F5   122.3 (3)    C21---C22---C23---C24   0.6 (4)
  C9---C8---C11---F5   −59.7 (3)    C20---C19---C24---C23   −0.3 (4)
  C7---C8---C11---F6   1.7 (3)      C18---C19---C24---C23   178.3 (2)
  C9---C8---C11---F6   179.7 (2)    N4---C23---C24---C19    177.3 (3)
  C7---C8---C11---F4   −116.7 (3)   C22---C23---C24---C19   −0.4 (4)
  -------------------- ------------ ----------------------- -------------

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

  --------------------- ---------- ---------- ----------- ---------------
  *D*---H···*A*         *D*---H    H···*A*    *D*···*A*   *D*---H···*A*
  O1---H1···O2          0.84 (1)   1.83 (1)   2.669 (3)   178 (3)
  N4---H41···O2^i^      0.88 (1)   2.04 (1)   2.900 (3)   164 (3)
  N2---H21···O3^ii^     0.89 (1)   1.87 (1)   2.717 (3)   159 (3)
  N4---H42···O5^iii^    0.88 (1)   2.27 (2)   3.101 (3)   159 (3)
  N2---H22···O2W        0.89 (1)   2.05 (1)   2.916 (4)   165 (3)
  N2---H22···O3W        0.89 (1)   1.98 (2)   2.727 (5)   141 (3)
  OWw---H1W1···O1       0.84 (1)   2.08 (4)   2.867 (5)   156 (8)
  O1W---H1W2···F6^iv^   0.84 (1)   2.47 (7)   2.867 (5)   110 (6)
  O2W---H2W1···O1W      0.85 (1)   2.07 (2)   2.859 (6)   154 (4)
  O2W---H2W2···O4^v^    0.85 (1)   2.30 (2)   3.119 (4)   165 (4)
  O3W---H3W1···O3       0.84 (1)   2.21 (1)   3.049 (5)   174 (7)
  O3W---H3W2···O4^v^    0.84 (1)   2.37 (3)   3.158 (5)   156 (7)
  O3W---H3W2···O5^v^    0.84 (1)   2.32 (6)   3.016 (5)   140 (7)
  --------------------- ---------- ---------- ----------- ---------------

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

###### Hydrogen-bond geometry (Å, °)

  *D*---H⋯*A*             *D*---H    H⋯*A*      *D*⋯*A*     *D*---H⋯*A*
  ----------------------- ---------- ---------- ----------- -------------
  O1---H1⋯O2              0.84 (1)   1.83 (1)   2.669 (3)   178 (3)
  N4---H41⋯O2^i^          0.88 (1)   2.04 (1)   2.900 (3)   164 (3)
  N2---H21⋯O3^ii^         0.89 (1)   1.87 (1)   2.717 (3)   159 (3)
  N4---H42⋯O5^iii^        0.88 (1)   2.27 (2)   3.101 (3)   159 (3)
  N2---H22⋯O2*W*          0.89 (1)   2.05 (1)   2.916 (4)   165 (3)
  N2---H22⋯O3*W*          0.89 (1)   1.98 (2)   2.727 (5)   141 (3)
  OWw---H1*W*1⋯O1         0.84 (1)   2.08 (4)   2.867 (5)   156 (8)
  O1*W*---H1*W*2⋯F6^iv^   0.84 (1)   2.47 (7)   2.867 (5)   110 (6)
  O2*W*---H2*W*1⋯O1*W*    0.85 (1)   2.07 (2)   2.859 (6)   154 (4)
  O2*W*---H2*W*2⋯O4^v^    0.85 (1)   2.30 (2)   3.119 (4)   165 (4)
  O3*W*---H3*W*1⋯O3       0.84 (1)   2.21 (1)   3.049 (5)   174 (7)
  O3*W*---H3*W*2⋯O4^v^    0.84 (1)   2.37 (3)   3.158 (5)   156 (7)
  O3*W*---H3*W*2⋯O5^v^    0.84 (1)   2.32 (6)   3.016 (5)   140 (7)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) . 

[^1]: Additional correspondence author, e-mail: j.wardell\@abdn.ac.uk.