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

For the synthesis of 2-(diisopropyl­thio­phospho­ryl­amino)­pyridine, see: Smith & Sisler (1961[@bb8]); Bichler *et al.* (2011[@bb2]). For Cu, Pd, and Fe complexes of 2-(diisopropyl­thio­phospho­ryl­amino)­pyridine, see: Öztopcu *et al.* (2011[@bb6]); Bichler *et al.* (2011[@bb2]); Holzhacker *et al.* (2011[@bb4]). For an review on S-bearing transition-metal catalysts, see: Bayón *et al.* (1999[@bb1]).

Experimental   {#sec2}
==============

 {#sec2.1}

### Crystal data   {#sec2.1.1}

C~11~H~20~N~2~PS^+^·BF~4~ ^−^*M* *~r~* = 330.13Triclinic,*a* = 9.5816 (1) Å*b* = 11.3855 (2) Å*c* = 14.3650 (2) Åα = 88.221 (1)°β = 86.067 (1)°γ = 82.299 (1)°*V* = 1548.93 (4) Å^3^*Z* = 4Mo *K*α radiationμ = 0.34 mm^−1^*T* = 100 K0.54 × 0.40 × 0.38 mm

### Data collection   {#sec2.1.2}

Bruker Kappa APEXII CCD diffractometerAbsorption correction: multi-scan (*SADABS*; Bruker, 2008[@bb3]) *T* ~min~ = 0.79, *T* ~max~ = 0.8640158 measured reflections8997 independent reflections8332 reflections with *I* \> 2σ(*I*)*R* ~int~ = 0.026

### Refinement   {#sec2.1.3}

*R*\[*F* ^2^ \> 2σ(*F* ^2^)\] = 0.027*wR*(*F* ^2^) = 0.076*S* = 1.028997 reflections385 parametersH atoms treated by a mixture of independent and constrained refinementΔρ~max~ = 0.72 e Å^−3^Δρ~min~ = −0.55 e Å^−3^

 {#d5e614}

Data collection: *APEX2* (Bruker, 2008[@bb3]); cell refinement: *SAINT* (Bruker, 2008[@bb3]); data reduction: *SAINT* and *XPREP* (Bruker, 2008[@bb3]); program(s) used to solve structure: *SHELXS97* (Sheldrick, 2008[@bb7]); program(s) used to refine structure: *SHELXL97* (Sheldrick, 2008[@bb7]); molecular graphics: *Mercury* (Macrae *et al.*, 2006[@bb5]); software used to prepare material for publication: *PLATON* (Spek, 2009[@bb9]) and *publCIF* (Westrip, 2010[@bb10]).

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

Crystal structure: contains datablock(s) I, global. DOI: [10.1107/S1600536812022295/ez2293sup1.cif](http://dx.doi.org/10.1107/S1600536812022295/ez2293sup1.cif)

Structure factors: contains datablock(s) I. DOI: [10.1107/S1600536812022295/ez2293Isup2.hkl](http://dx.doi.org/10.1107/S1600536812022295/ez2293Isup2.hkl)

Supplementary material file. DOI: [10.1107/S1600536812022295/ez2293Isup3.cml](http://dx.doi.org/10.1107/S1600536812022295/ez2293Isup3.cml)

Additional supplementary materials: [crystallographic information](http://scripts.iucr.org/cgi-bin/sendsupfiles?ez2293&file=ez2293sup0.html&mime=text/html); [3D view](http://scripts.iucr.org/cgi-bin/sendcif?ez2293sup1&Qmime=cif); [checkCIF report](http://scripts.iucr.org/cgi-bin/paper?ez2293&checkcif=yes)

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: [EZ2293](http://scripts.iucr.org/cgi-bin/sendsup?ez2293)).

Financial support by the Fonds zur Förderung der wissenschaftlichen Forschung (FWF) is gratefully acknowledged (project No. P24202).

Comment
=======

Dialkyl- and diaryl-thiophosphoryl derivatives of 2-aminopyridine are chelating bidentate ligands, which furnish a pyridine nitrogen as a hard and a sulfur as a soft donor site for transition metal coordination. This dual property is desirable for reactive transition metal complexes (Bayón *et al.*, 1999) and, accordingly, a variety of such complexes have been studied in recent years (Öztopcu *et al.*, 2011; Bichler *et al.*, 2011). During recent work in this field (Holzhacker *et al.*, 2011), the title compound was obtained in suitable crystals and was studied by X-ray diffraction. It crystallizes in the triclinic space group *P*1 and contains two formula units \[C~11~H~20~N~2~PS\]^+^(BF~4~)^-^ in the asymmetric unit (Fig. 1). In (I), both organocations \[*SN-^i^Pr*\]H^+^ possess very similar bond lengths and bond angles, but differ significantly in their conformation, as can be seen from the torsion angles S1---P1---N2---C1 = -18.72 (10)° and P1---N2---C1---N1 = -16.91 (14)° in the first cation and corresponding values of -35.14 (10)° and +6.74 (14)° in the second cation. The conformation of the \[*SN-^i^Pr*\]H^+^ moiety in (I) is related to that of its metal chelate complexes (Öztopcu *et al.*, 2011; Bichler *et al.*, 2011; Holzhacker *et al.*, 2011), which have the S atoms like in (I) *syn*-oriented to the pyridine N, but different from the solid state structure of the unprotonated neutral parent molecule \[*SN-^i^Pr*\], in which the S atom points away from the pyridine nitrogen corresponding to a S1---P1---N2---C1 torsion angle near 180° (Öztopcu *et al.*, 2011). Compared with the neutral parent molecule \[*SN-^i^Pr*\], the bond lengths and bond angles in (I) are modestly altered by the pyridine N-protonation with subtle changes of about 0.01 - 0.02 Å in the P1---N2---C1---N1---C5 / P2---N4---C12---N3---C16 system and a significant increase of the ring bond angles C1---N1---C5 / C12---N3---C16 from *ca* 117° in \[*SN-^i^Pr*\] (Öztopcu *et al.*, 2011) to *ca* 123° in \[*SN-^i^Pr*\]H^+^ of (I). Both pyridinium moieties in (I) donate strongly bent intramolecular hydrogen bonds to the sulfur atoms as acceptors with N···S distances of 3.136 (1) Å and 3.130 (1) Å for cation 1and 2, respectively (Table 1). For cation 1, the N1---H1n group has in addition to S1 also a fluorine F2(1 + *x*,*y*,*z*) nearby and the entire interaction has to be classified as an asymmetrically branched bifurcated hydrogen bond (N1---H1n···S1,F2; the sum of the three bond angles about H1n is 358°). The phosphorylamine NH groups, which are distinctly acidic irrespective whether the pyridine fragment is protonated or not, form comparatively straight N---H···F hydrogen bonds to the BF~4~ anions with N···F distances of 2.807 (1) and 2.871 (1) Å (Table 1). In the parent compound \[*SN-^i^Pr*\] the phosphorylamine NH groups donate intermolecular N---H···S hydrogen bonds of N···S = 3.38 and 3.47 Å to neighbouring molecules (Öztopcu *et al.*, 2011). A partial packing diagram showing the N---H donated hydrogen bonds in (I) is presented in Fig. 2. Three-dimensional coherence of the structure is provided by five different C---H···F and three C---H···S interactions listed in Table 1.

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

2-(Diisopropylthiophosphorylamino)-pyridine (Öztopcu *et al.*, 2011; Smith & Sisler, 1961; 1.03 mmol, 250 mg) was dissolved in dry CH~2~Cl~2~ and 1.05 equivalent of HBF~4~ in Et~2~O was added. The solvent was removed under reduced pressure and the solid residue was washed twice with 15 ml dry Et~2~O. Yield: 326 mg, 95.7%, white solid. Colourless crystals of the title compound for X-ray diffraction were obtained from a CH~2~Cl~2~ solution by vapour diffusion of Et~2~O. ^1^H NMR (δ, CD~2~Cl~2~, 20°C): 15.15 (bs, 1H, \[pyH\]^+^), 8.12 (t, J = 7.8 Hz, 1H, py^6^),7.98 -- 7.90 (m, 2H, py^4^, NH), 7.84 (d, J = 9.0 Hz, 1H, py^3^),7.25 (t, 6.8 Hz, 1H, py^5^), 2.65 -- 2.51 (m, 2H, C*H*(CH~3~)~2~), 1.38 -- 1.23 (m, 12H, CH(C*H*~3~)~2~). ^13^C{^1^H}NMR (δ, CH~2~Cl~2~, 20°C): 154.6 (s, py^2^), 146.0(s, py^6^), 135.0 (s, py^4^), 118.2 (s, py^5^), 117.2 (s, py^3^), 31.1 (d, J = 57.2 Hz, *C*H(CH~3~)~2~), 15.4 (s, CH(*C*H~3~)~2~), 15.1 (s, CH(*C*H~3~)~2~). ^31^P{^1^H}NMR (δ, CD~2~Cl~2~, 20°C): 107.2.

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

C-bonded H atoms were placed in calculated positions and thereafter treated as riding, C---H = 0.95--1.00 Å, *U*~iso~(H) = 1.2*U*~eq~(C). N-bonded H atoms were fully refined.

Figures
=======

![The asymmetric unit of (I) with displacement ellipsoids at the 50% probability level and dashed red lines for hydrogen bonds.](e-68-o1835-fig1){#Fap1}

![Partial packing diagram of the structure viewed along \[001\] showing only the N---H···S and N---H···F hydrogen bonds as dashed lines. C-bonded H-atoms omitted for clarity.](e-68-o1835-fig2){#Fap2}

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

  ------------------------------ ---------------------------------------
  C~11~H~20~N~2~PS^+^·BF~4~^−^   *Z* = 4
  *M~r~* = 330.13                *F*(000) = 688
  Triclinic, *P*1                *D*~x~ = 1.416 Mg m^−3^
  *a* = 9.5816 (1) Å             Mo *K*α radiation, λ = 0.71073 Å
  *b* = 11.3855 (2) Å            Cell parameters from 9086 reflections
  *c* = 14.3650 (2) Å            θ = 2.3--30.5°
  α = 88.221 (1)°                µ = 0.34 mm^−1^
  β = 86.067 (1)°                *T* = 100 K
  γ = 82.299 (1)°                Prism, colourless
  *V* = 1548.93 (4) Å^3^         0.54 × 0.40 × 0.38 mm
  ------------------------------ ---------------------------------------

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

  ------------------------------------------------------------ --------------------------------------
  Bruker Kappa APEXII CCD diffractometer                       8997 independent reflections
  Radiation source: fine-focus sealed tube                     8332 reflections with *I* \> 2σ(*I*)
  Graphite monochromator                                       *R*~int~ = 0.026
  φ and ω scans                                                θ~max~ = 30.0°, θ~min~ = 2.3°
  Absorption correction: multi-scan (*SADABS*; Bruker, 2008)   *h* = −13→13
  *T*~min~ = 0.79, *T*~max~ = 0.86                             *k* = −16→16
  40158 measured reflections                                   *l* = −20→20
  ------------------------------------------------------------ --------------------------------------

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*\[*F*^2^ \> 2σ(*F*^2^)\] = 0.027   Hydrogen site location: inferred from neighbouring sites
  *wR*(*F*^2^) = 0.076                  H atoms treated by a mixture of independent and constrained refinement
  *S* = 1.02                            *w* = 1/\[σ^2^(*F*~o~^2^) + (0.0381*P*)^2^ + 0.7013*P*\] where *P* = (*F*~o~^2^ + 2*F*~c~^2^)/3
  8997 reflections                      (Δ/σ)~max~ = 0.001
  385 parameters                        Δρ~max~ = 0.72 e Å^−3^
  0 restraints                          Δρ~min~ = −0.55 e Å^−3^
  ------------------------------------- -------------------------------------------------------------------------------------------------

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~   
  P1     0.78596 (2)     0.65777 (2)     0.445334 (16)    0.01166 (5)          
  S1     0.96769 (2)     0.63976 (2)     0.374765 (18)    0.01685 (5)          
  N1     0.87680 (9)     0.91293 (7)     0.39707 (6)      0.01373 (15)         
  H1N    0.9345 (17)     0.8543 (14)     0.4094 (11)      0.026 (4)\*          
  N2     0.69381 (9)     0.79586 (7)     0.43140 (6)      0.01417 (15)         
  H2N    0.6070 (17)     0.7983 (13)     0.4336 (11)      0.023 (4)\*          
  C1     0.73899 (10)    0.89975 (8)     0.40033 (6)      0.01231 (16)         
  C2     0.64302 (10)    0.99596 (8)     0.37087 (7)      0.01522 (17)         
  H2     0.5447          0.9905          0.3742           0.018\*              
  C3     0.69272 (11)    1.09772 (9)     0.33728 (7)      0.01724 (18)         
  H3     0.6283          1.1623          0.3163           0.021\*              
  C4     0.83746 (11)    1.10760 (9)     0.33348 (7)      0.01743 (18)         
  H4     0.8720          1.1779          0.3099           0.021\*              
  C5     0.92708 (10)    1.01375 (9)     0.36444 (7)      0.01606 (17)         
  H5     1.0254          1.0187          0.3633           0.019\*              
  C6     0.80053 (10)    0.63744 (8)     0.57047 (7)      0.01523 (17)         
  H6     0.8573          0.5584          0.5809           0.018\*              
  C7     0.88217 (12)    0.73112 (10)    0.60746 (7)      0.02037 (19)         
  H7A    0.8247          0.8090          0.6048           0.031\*              
  H7B    0.9704          0.7333          0.5690           0.031\*              
  H7C    0.9036          0.7110          0.6722           0.031\*              
  C8     0.65750 (12)    0.63545 (11)    0.62449 (7)      0.0227 (2)           
  H8A    0.6714          0.6250          0.6913           0.034\*              
  H8B    0.6124          0.5696          0.6033           0.034\*              
  H8C    0.5971          0.7104          0.6134           0.034\*              
  C9     0.66301 (10)    0.56210 (8)     0.40889 (7)      0.01525 (17)         
  H9     0.5714          0.5805          0.4465           0.018\*              
  C10    0.72355 (12)    0.43267 (9)     0.42862 (8)      0.0225 (2)           
  H10A   0.6565          0.3803          0.4117           0.034\*              
  H10B   0.7397          0.4216          0.4951           0.034\*              
  H10C   0.8131          0.4134          0.3917           0.034\*              
  C11    0.63660 (12)    0.58331 (11)    0.30551 (8)      0.0232 (2)           
  H11A   0.7265          0.5699          0.2681           0.035\*              
  H11B   0.5927          0.6651          0.2956           0.035\*              
  H11C   0.5737          0.5285          0.2866           0.035\*              
  P2     0.28135 (2)     0.17525 (2)     0.010066 (16)    0.01218 (5)          
  S2     0.45868 (3)     0.20511 (2)     −0.055680 (18)   0.01840 (6)          
  N3     0.36925 (9)     0.40856 (7)     0.08654 (6)      0.01469 (15)         
  H3N    0.4264 (17)     0.3527 (14)     0.0599 (11)      0.026 (4)\*          
  N4     0.18559 (9)     0.30094 (7)     0.05392 (6)      0.01499 (15)         
  H4N    0.0991 (18)     0.3036 (14)     0.0574 (11)      0.026 (4)\*          
  C12    0.23059 (10)    0.39780 (8)     0.09024 (6)      0.01343 (16)         
  C13    0.13552 (10)    0.48762 (9)     0.13349 (7)      0.01662 (18)         
  H13    0.0371          0.4825          0.1382           0.020\*              
  C14    0.18682 (11)    0.58298 (9)     0.16883 (7)      0.01770 (18)         
  H14    0.1229          0.6438          0.1983           0.021\*              
  C15    0.33146 (11)    0.59206 (9)     0.16226 (7)      0.01705 (18)         
  H15    0.3662          0.6585          0.1864           0.020\*              
  C16    0.42105 (10)    0.50322 (9)     0.12037 (7)      0.01625 (17)         
  H16    0.5197          0.5073          0.1148           0.020\*              
  C17    0.30506 (11)    0.07372 (9)     0.10941 (7)      0.01614 (17)         
  H17    0.3626          −0.0008         0.0863           0.019\*              
  C18    0.38861 (12)    0.12465 (11)    0.18215 (8)      0.0233 (2)           
  H18A   0.3314          0.1939          0.2104           0.035\*              
  H18B   0.4757          0.1483          0.1519           0.035\*              
  H18C   0.4122          0.0643          0.2307           0.035\*              
  C19    0.16526 (12)    0.04013 (11)    0.15352 (8)      0.0239 (2)           
  H19A   0.1840          −0.0155         0.2060           0.036\*              
  H19B   0.1168          0.0028          0.1068           0.036\*              
  H19C   0.1055          0.1116          0.1760           0.036\*              
  C20    0.15834 (11)    0.12086 (9)     −0.06363 (7)     0.01632 (17)         
  H20    0.0659          0.1196          −0.0270          0.020\*              
  C21    0.21606 (12)    −0.00593 (10)   −0.09231 (8)     0.0229 (2)           
  H21A   0.1512          −0.0352         −0.1333          0.034\*              
  H21B   0.2249          −0.0573         −0.0364          0.034\*              
  H21C   0.3089          −0.0063         −0.1255          0.034\*              
  C22    0.13528 (14)    0.20246 (11)    −0.14931 (8)     0.0268 (2)           
  H22A   0.2242          0.2008          −0.1876          0.040\*              
  H22B   0.1031          0.2836          −0.1292          0.040\*              
  H22C   0.0638          0.1752          −0.1861          0.040\*              
  B1     0.28660 (12)    0.85386 (10)    0.39883 (8)      0.0185 (2)           
  F1     0.40011 (7)     0.79614 (7)     0.44747 (6)      0.02936 (16)         
  F2     0.16085 (7)     0.84002 (7)     0.44969 (5)      0.02751 (15)         
  F3     0.28753 (12)    0.80759 (9)     0.31181 (6)      0.0517 (3)           
  F4     0.29860 (8)     0.97445 (6)     0.39163 (6)      0.03064 (16)         
  B2     −0.19867 (12)   0.34423 (10)    0.11792 (9)      0.0193 (2)           
  F5     −0.10985 (7)    0.28359 (7)     0.04786 (6)      0.03054 (16)         
  F6     −0.22706 (8)    0.46261 (6)     0.09101 (5)      0.02529 (14)         
  F7     −0.12520 (9)    0.33533 (7)     0.19898 (6)      0.03483 (18)         
  F8     −0.32269 (8)    0.29481 (7)     0.13303 (7)      0.03629 (19)         
  ------ --------------- --------------- ---------------- -------------------- --

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

  ----- -------------- -------------- -------------- -------------- -------------- --------------
        *U*^11^        *U*^22^        *U*^33^        *U*^12^        *U*^13^        *U*^23^
  P1    0.00889 (10)   0.01168 (10)   0.01423 (10)   −0.00092 (7)   −0.00103 (8)   0.00099 (8)
  S1    0.01067 (10)   0.01698 (11)   0.02161 (11)   0.00076 (8)    0.00251 (8)    0.00108 (8)
  N1    0.0098 (4)     0.0138 (4)     0.0175 (4)     −0.0012 (3)    −0.0016 (3)    0.0018 (3)
  N2    0.0077 (3)     0.0133 (3)     0.0212 (4)     −0.0011 (3)    −0.0006 (3)    0.0034 (3)
  C1    0.0104 (4)     0.0136 (4)     0.0130 (4)     −0.0015 (3)    −0.0009 (3)    0.0000 (3)
  C2    0.0113 (4)     0.0149 (4)     0.0192 (4)     −0.0002 (3)    −0.0028 (3)    0.0011 (3)
  C3    0.0167 (4)     0.0144 (4)     0.0203 (4)     0.0002 (3)     −0.0036 (3)    0.0013 (3)
  C4    0.0187 (5)     0.0146 (4)     0.0197 (4)     −0.0048 (3)    −0.0020 (3)    0.0010 (3)
  C5    0.0137 (4)     0.0165 (4)     0.0189 (4)     −0.0054 (3)    −0.0008 (3)    0.0002 (3)
  C6    0.0152 (4)     0.0150 (4)     0.0156 (4)     −0.0018 (3)    −0.0033 (3)    0.0020 (3)
  C7    0.0188 (5)     0.0234 (5)     0.0204 (5)     −0.0058 (4)    −0.0050 (4)    −0.0022 (4)
  C8    0.0224 (5)     0.0301 (5)     0.0168 (4)     −0.0102 (4)    0.0016 (4)     0.0003 (4)
  C9    0.0134 (4)     0.0155 (4)     0.0175 (4)     −0.0037 (3)    −0.0022 (3)    −0.0005 (3)
  C10   0.0230 (5)     0.0148 (4)     0.0306 (5)     −0.0038 (4)    −0.0053 (4)    −0.0009 (4)
  C11   0.0247 (5)     0.0281 (5)     0.0188 (5)     −0.0081 (4)    −0.0068 (4)    −0.0007 (4)
  P2    0.01002 (11)   0.01213 (10)   0.01402 (10)   −0.00055 (8)   0.00027 (8)    −0.00110 (8)
  S2    0.01374 (11)   0.01706 (11)   0.02344 (12)   −0.00190 (8)   0.00638 (9)    −0.00245 (9)
  N3    0.0101 (4)     0.0149 (4)     0.0187 (4)     −0.0008 (3)    0.0009 (3)     −0.0029 (3)
  N4    0.0087 (4)     0.0140 (4)     0.0221 (4)     −0.0010 (3)    0.0005 (3)     −0.0040 (3)
  C12   0.0112 (4)     0.0140 (4)     0.0149 (4)     −0.0013 (3)    −0.0002 (3)    −0.0001 (3)
  C13   0.0111 (4)     0.0163 (4)     0.0219 (4)     −0.0009 (3)    0.0021 (3)     −0.0029 (3)
  C14   0.0155 (4)     0.0164 (4)     0.0206 (4)     −0.0008 (3)    0.0023 (3)     −0.0037 (3)
  C15   0.0168 (4)     0.0169 (4)     0.0180 (4)     −0.0043 (3)    −0.0003 (3)    −0.0027 (3)
  C16   0.0125 (4)     0.0180 (4)     0.0188 (4)     −0.0038 (3)    −0.0011 (3)    −0.0010 (3)
  C17   0.0152 (4)     0.0162 (4)     0.0167 (4)     −0.0010 (3)    −0.0018 (3)    0.0014 (3)
  C18   0.0216 (5)     0.0291 (5)     0.0200 (5)     −0.0042 (4)    −0.0075 (4)    0.0022 (4)
  C19   0.0221 (5)     0.0290 (5)     0.0214 (5)     −0.0091 (4)    −0.0004 (4)    0.0065 (4)
  C20   0.0152 (4)     0.0172 (4)     0.0166 (4)     −0.0009 (3)    −0.0025 (3)    −0.0030 (3)
  C21   0.0235 (5)     0.0197 (5)     0.0256 (5)     −0.0005 (4)    −0.0041 (4)    −0.0084 (4)
  C22   0.0315 (6)     0.0278 (5)     0.0212 (5)     −0.0007 (4)    −0.0100 (4)    0.0021 (4)
  B1    0.0149 (5)     0.0196 (5)     0.0203 (5)     0.0000 (4)     −0.0001 (4)    0.0008 (4)
  F1    0.0104 (3)     0.0298 (4)     0.0461 (4)     0.0001 (2)     −0.0016 (3)    0.0148 (3)
  F2    0.0114 (3)     0.0351 (4)     0.0361 (4)     −0.0048 (3)    −0.0026 (3)    0.0074 (3)
  F3    0.0758 (7)     0.0500 (5)     0.0258 (4)     0.0059 (5)     0.0004 (4)     −0.0137 (4)
  F4    0.0229 (3)     0.0203 (3)     0.0485 (4)     −0.0036 (3)    −0.0036 (3)    0.0086 (3)
  B2    0.0127 (5)     0.0187 (5)     0.0265 (5)     −0.0025 (4)    0.0001 (4)     −0.0003 (4)
  F5    0.0173 (3)     0.0304 (4)     0.0427 (4)     0.0002 (3)     0.0051 (3)     −0.0121 (3)
  F6    0.0251 (3)     0.0212 (3)     0.0275 (3)     0.0022 (2)     0.0010 (3)     0.0046 (3)
  F7    0.0384 (4)     0.0365 (4)     0.0310 (4)     −0.0084 (3)    −0.0118 (3)    0.0121 (3)
  F8    0.0160 (3)     0.0299 (4)     0.0636 (5)     −0.0087 (3)    0.0073 (3)     −0.0091 (4)
  ----- -------------- -------------- -------------- -------------- -------------- --------------

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

  -------------------- ------------- ----------------------- -------------
  P1---N2              1.7100 (8)    N3---C12                1.3478 (12)
  P1---C6              1.8177 (10)   N3---C16                1.3612 (12)
  P1---C9              1.8199 (10)   N3---H3N                0.862 (16)
  P1---S1              1.9434 (3)    N4---C12                1.3669 (12)
  N1---C1              1.3463 (12)   N4---H4N                0.824 (17)
  N1---C5              1.3614 (12)   C12---C13               1.4049 (13)
  N1---H1N             0.831 (17)    C13---C14               1.3746 (14)
  N2---C1              1.3651 (12)   C13---H13               0.9500
  N2---H2N             0.827 (16)    C14---C15               1.4001 (14)
  C1---C2              1.4069 (12)   C14---H14               0.9500
  C2---C3              1.3725 (13)   C15---C16               1.3625 (14)
  C2---H2              0.9500        C15---H15               0.9500
  C3---C4              1.4035 (14)   C16---H16               0.9500
  C3---H3              0.9500        C17---C18               1.5315 (14)
  C4---C5              1.3617 (14)   C17---C19               1.5323 (15)
  C4---H4              0.9500        C17---H17               1.0000
  C5---H5              0.9500        C18---H18A              0.9800
  C6---C8              1.5303 (15)   C18---H18B              0.9800
  C6---C7              1.5323 (14)   C18---H18C              0.9800
  C6---H6              1.0000        C19---H19A              0.9800
  C7---H7A             0.9800        C19---H19B              0.9800
  C7---H7B             0.9800        C19---H19C              0.9800
  C7---H7C             0.9800        C20---C22               1.5290 (15)
  C8---H8A             0.9800        C20---C21               1.5334 (14)
  C8---H8B             0.9800        C20---H20               1.0000
  C8---H8C             0.9800        C21---H21A              0.9800
  C9---C11             1.5300 (14)   C21---H21B              0.9800
  C9---C10             1.5349 (14)   C21---H21C              0.9800
  C9---H9              1.0000        C22---H22A              0.9800
  C10---H10A           0.9800        C22---H22B              0.9800
  C10---H10B           0.9800        C22---H22C              0.9800
  C10---H10C           0.9800        B1---F3                 1.3704 (14)
  C11---H11A           0.9800        B1---F2                 1.3904 (13)
  C11---H11B           0.9800        B1---F4                 1.3932 (13)
  C11---H11C           0.9800        B1---F1                 1.4097 (13)
  P2---N4              1.7063 (8)    B2---F8                 1.3828 (13)
  P2---C17             1.8155 (10)   B2---F6                 1.3870 (13)
  P2---C20             1.8168 (10)   B2---F7                 1.3956 (14)
  P2---S2              1.9517 (3)    B2---F5                 1.4078 (14)
                                                             
  N2---P1---C6         105.14 (4)    C12---N3---C16          123.33 (8)
  N2---P1---C9         102.21 (4)    C12---N3---H3N          117.0 (10)
  C6---P1---C9         108.40 (5)    C16---N3---H3N          119.6 (10)
  N2---P1---S1         112.59 (3)    C12---N4---P2           129.67 (7)
  C6---P1---S1         113.15 (3)    C12---N4---H4N          113.3 (11)
  C9---P1---S1         114.42 (3)    P2---N4---H4N           116.9 (11)
  C1---N1---C5         122.89 (8)    N3---C12---N4           120.31 (8)
  C1---N1---H1N        118.4 (11)    N3---C12---C13          118.05 (9)
  C5---N1---H1N        118.3 (11)    N4---C12---C13          121.63 (9)
  C1---N2---P1         130.31 (7)    C14---C13---C12         119.09 (9)
  C1---N2---H2N        113.2 (11)    C14---C13---H13         120.5
  P1---N2---H2N        115.3 (11)    C12---C13---H13         120.5
  N1---C1---N2         120.84 (8)    C13---C14---C15         121.22 (9)
  N1---C1---C2         118.15 (8)    C13---C14---H14         119.4
  N2---C1---C2         121.00 (8)    C15---C14---H14         119.4
  C3---C2---C1         119.39 (9)    C16---C15---C14         118.29 (9)
  C3---C2---H2         120.3         C16---C15---H15         120.9
  C1---C2---H2         120.3         C14---C15---H15         120.9
  C2---C3---C4         120.87 (9)    N3---C16---C15          120.00 (9)
  C2---C3---H3         119.6         N3---C16---H16          120.0
  C4---C3---H3         119.6         C15---C16---H16         120.0
  C5---C4---C3         118.20 (9)    C18---C17---C19         110.96 (9)
  C5---C4---H4         120.9         C18---C17---P2          110.62 (7)
  C3---C4---H4         120.9         C19---C17---P2          112.78 (7)
  N1---C5---C4         120.46 (9)    C18---C17---H17         107.4
  N1---C5---H5         119.8         C19---C17---H17         107.4
  C4---C5---H5         119.8         P2---C17---H17          107.4
  C8---C6---C7         111.65 (8)    C17---C18---H18A        109.5
  C8---C6---P1         112.90 (7)    C17---C18---H18B        109.5
  C7---C6---P1         110.39 (7)    H18A---C18---H18B       109.5
  C8---C6---H6         107.2         C17---C18---H18C        109.5
  C7---C6---H6         107.2         H18A---C18---H18C       109.5
  P1---C6---H6         107.2         H18B---C18---H18C       109.5
  C6---C7---H7A        109.5         C17---C19---H19A        109.5
  C6---C7---H7B        109.5         C17---C19---H19B        109.5
  H7A---C7---H7B       109.5         H19A---C19---H19B       109.5
  C6---C7---H7C        109.5         C17---C19---H19C        109.5
  H7A---C7---H7C       109.5         H19A---C19---H19C       109.5
  H7B---C7---H7C       109.5         H19B---C19---H19C       109.5
  C6---C8---H8A        109.5         C22---C20---C21         111.04 (9)
  C6---C8---H8B        109.5         C22---C20---P2          110.40 (7)
  H8A---C8---H8B       109.5         C21---C20---P2          109.04 (7)
  C6---C8---H8C        109.5         C22---C20---H20         108.8
  H8A---C8---H8C       109.5         C21---C20---H20         108.8
  H8B---C8---H8C       109.5         P2---C20---H20          108.8
  C11---C9---C10       111.19 (9)    C20---C21---H21A        109.5
  C11---C9---P1        110.76 (7)    C20---C21---H21B        109.5
  C10---C9---P1        108.62 (7)    H21A---C21---H21B       109.5
  C11---C9---H9        108.7         C20---C21---H21C        109.5
  C10---C9---H9        108.7         H21A---C21---H21C       109.5
  P1---C9---H9         108.7         H21B---C21---H21C       109.5
  C9---C10---H10A      109.5         C20---C22---H22A        109.5
  C9---C10---H10B      109.5         C20---C22---H22B        109.5
  H10A---C10---H10B    109.5         H22A---C22---H22B       109.5
  C9---C10---H10C      109.5         C20---C22---H22C        109.5
  H10A---C10---H10C    109.5         H22A---C22---H22C       109.5
  H10B---C10---H10C    109.5         H22B---C22---H22C       109.5
  C9---C11---H11A      109.5         F3---B1---F2            110.21 (10)
  C9---C11---H11B      109.5         F3---B1---F4            110.25 (10)
  H11A---C11---H11B    109.5         F2---B1---F4            108.31 (9)
  C9---C11---H11C      109.5         F3---B1---F1            110.41 (10)
  H11A---C11---H11C    109.5         F2---B1---F1            108.90 (9)
  H11B---C11---H11C    109.5         F4---B1---F1            108.70 (9)
  N4---P2---C17        105.30 (4)    F8---B2---F6            110.45 (9)
  N4---P2---C20        102.38 (4)    F8---B2---F7            110.28 (10)
  C17---P2---C20       108.02 (5)    F6---B2---F7            109.24 (9)
  N4---P2---S2         112.71 (3)    F8---B2---F5            110.69 (9)
  C17---P2---S2        113.40 (3)    F6---B2---F5            108.88 (9)
  C20---P2---S2        114.10 (4)    F7---B2---F5            107.23 (9)
                                                             
  C6---P1---N2---C1    104.90 (9)    C17---P2---N4---C12     88.97 (10)
  C9---P1---N2---C1    −141.95 (9)   C20---P2---N4---C12     −158.17 (9)
  S1---P1---N2---C1    −18.72 (10)   S2---P2---N4---C12      −35.14 (10)
  C5---N1---C1---N2    178.31 (9)    C16---N3---C12---N4     179.23 (9)
  C5---N1---C1---C2    −1.71 (14)    C16---N3---C12---C13    −1.73 (14)
  P1---N2---C1---N1    −16.91 (14)   P2---N4---C12---N3      6.74 (14)
  P1---N2---C1---C2    163.11 (8)    P2---N4---C12---C13     −172.27 (8)
  N1---C1---C2---C3    2.07 (14)     N3---C12---C13---C14    0.93 (14)
  N2---C1---C2---C3    −177.95 (9)   N4---C12---C13---C14    179.96 (9)
  C1---C2---C3---C4    −1.09 (15)    C12---C13---C14---C15   0.13 (15)
  C2---C3---C4---C5    −0.32 (15)    C13---C14---C15---C16   −0.48 (15)
  C1---N1---C5---C4    0.30 (15)     C12---N3---C16---C15    1.40 (15)
  C3---C4---C5---N1    0.75 (15)     C14---C15---C16---N3    −0.25 (15)
  N2---P1---C6---C8    64.31 (8)     N4---P2---C17---C18     −62.07 (8)
  C9---P1---C6---C8    −44.41 (8)    C20---P2---C17---C18    −170.90 (7)
  S1---P1---C6---C8    −172.43 (6)   S2---P2---C17---C18     61.61 (8)
  N2---P1---C6---C7    −61.44 (8)    N4---P2---C17---C19     62.85 (8)
  C9---P1---C6---C7    −170.16 (7)   C20---P2---C17---C19    −45.98 (9)
  S1---P1---C6---C7    61.82 (7)     S2---P2---C17---C19     −173.47 (7)
  N2---P1---C9---C11   64.39 (8)     N4---P2---C20---C22     69.74 (8)
  C6---P1---C9---C11   175.09 (7)    C17---P2---C20---C22    −179.43 (7)
  S1---P1---C9---C11   −57.61 (8)    S2---P2---C20---C22     −52.35 (8)
  N2---P1---C9---C10   −173.23 (7)   N4---P2---C20---C21     −168.00 (7)
  C6---P1---C9---C10   −62.53 (8)    C17---P2---C20---C21    −57.18 (8)
  S1---P1---C9---C10   64.77 (8)     S2---P2---C20---C21     69.91 (8)
  -------------------- ------------- ----------------------- -------------

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

  -------------------- ------------ ------------ ------------- ---------------
  *D*---H···*A*        *D*---H      H···*A*      *D*···*A*     *D*---H···*A*
  N1---H1*N*···S1      0.831 (17)   2.482 (16)   3.1356 (9)    136.3 (14)
  N1---H1*N*···F2^i^   0.831 (17)   2.266 (16)   2.8820 (10)   131.2 (14)
  N2---H2*N*···F1      0.827 (16)   1.982 (17)   2.8073 (10)   175.6 (15)
  N3---H3*N*···S2      0.862 (16)   2.375 (16)   3.1297 (9)    146.4 (14)
  N4---H4*N*···F5      0.824 (17)   2.059 (17)   2.8714 (11)   168.7 (15)
  C2---H2···F4         0.95         2.39         3.3341 (12)   177
  C4---H4···F7^ii^     0.95         2.36         3.2290 (12)   151
  C6---H6···S1^iii^    1.00         2.71         3.7038 (10)   172
  C13---H13···F7       0.95         2.53         3.2968 (13)   138
  C14---H14···S1^iv^   0.95         2.85         3.5328 (10)   129
  C15---H15···F3       0.95         2.52         3.2773 (13)   137
  C16---H16···F6^i^    0.95         2.41         3.3406 (12)   165
  C17---H17···S2^v^    1.00         2.73         3.7128 (10)   169
  -------------------- ------------ ------------ ------------- ---------------

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

###### Hydrogen-bond geometry (Å, °)

  *D*---H⋯*A*        *D*---H      H⋯*A*        *D*⋯*A*       *D*---H⋯*A*
  ------------------ ------------ ------------ ------------- -------------
  N1---H1*N*⋯S1      0.831 (17)   2.482 (16)   3.1356 (9)    136.3 (14)
  N1---H1*N*⋯F2^i^   0.831 (17)   2.266 (16)   2.8820 (10)   131.2 (14)
  N2---H2*N*⋯F1      0.827 (16)   1.982 (17)   2.8073 (10)   175.6 (15)
  N3---H3*N*⋯S2      0.862 (16)   2.375 (16)   3.1297 (9)    146.4 (14)
  N4---H4*N*⋯F5      0.824 (17)   2.059 (17)   2.8714 (11)   168.7 (15)
  C2---H2⋯F4         0.95         2.39         3.3341 (12)   177
  C4---H4⋯F7^ii^     0.95         2.36         3.2290 (12)   151
  C6---H6⋯S1^iii^    1.00         2.71         3.7038 (10)   172
  C13---H13⋯F7       0.95         2.53         3.2968 (13)   138
  C14---H14⋯S1^iv^   0.95         2.85         3.5328 (10)   129
  C15---H15⋯F3       0.95         2.52         3.2773 (13)   137
  C16---H16⋯F6^i^    0.95         2.41         3.3406 (12)   165
  C17---H17⋯S2^v^    1.00         2.73         3.7128 (10)   169

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