supplementary materials


br2211 scheme

Acta Cryst. (2013). E69, o87    [ doi:10.1107/S1600536812049914 ]

Triphenyl[(triphenylphosphoranylidene)amino]phosphonium tetrakis(pentafluorophenyl)borate

P. Vanýsek and C. Zheng

Abstract top

In the title molecular salt, C36H30NP2+·C24BF20-, the P-N bond lengths in the cation are equal [1.573 (2) and 1.572 (2) Å], indicating a resonance structure and the P-N-P bond angle is 144.79 (12)°. In the crystal, weak C-H...F interactions link the cations and the anions.

Comment top

Salts of very hydrophobic cations and anions are very desirable for electrochemical studies of interfaces between polar organic solvent and water, commonly known as ITIES (Interface between Two Immiscible Electrolyte Solutions). These systems require an aqueous phase with very hydrophilic salt and a nonaqueous one with very hydrophobic salt, to be used as supporting electrolytes for their respective phases without leaching into the opposite phases. Thus, compound such as the current bis(triphenylphosphoranylidene)-ammonium tetrakis(pentafluorophenyl)borate are natural choice of materials for this purpose (Luo et al. 2006, Fermín et al. 1999, Su et al. 2008a,b, Stephenson et al. 2005). Its CAS registry number is 227603–93-2.

In the work of Luo and coworkers (Luo et al. 2006) this compound was used to study the fine structure of interface between two liquids using X-ray reflectivity of the interface. Vanýsek & Novák (2009) calculated the Gibbs energies of the transport for the individual ions between water and dichloroethane, the common organic phase for ITIES work. The structural information is important for understanding these Gibbs free energies.

Related literature top

For details of the preparation, see: Fermín et al. (1999); Gobry (2001). For electrochemical studies of interfaces between polar organic solvents and water, see: Luo et al. (2006); Fermín et al. (1999); Su et al. (2008a,b); Stephenson et al. (2005). For an X-ray reflectivity study of the interface, see: Luo et al. (2006). For a Gibbs free-energy study of the compound, see: Vanýsek & Novák (2009).

Experimental top

The preparation method is based on the metathesis of the starting materials with the elimination of water-soluble LiCl. The framework of the procedure is described in (Fermín et al. 1999). The starting materials used were bis(triphenylphosphoranylidene)-ammonium chloride (Aldrich) and either lithium or potassium tetrakis(pentafluorophenyl)borate (Boulder Scientific Company). In later preparations potassium tetrakis(pentafluorophenyl)borate (also from Boulder Scientific Company) was used, with identical electrochemical results. Both starting materials were dissolved in a methanol:water 2:1 mixture, with a minimum of 10 ml per gram of starting materials used. The solutions were combined and the precipitate formed was rinsed in copious amounts of a methanol:water 2:1 mixture, followed by large amount of distilled water. The product was vacuum-filtered and dried. The recrystallization was done from hot acetone (Gobry 2001). The yield was 82%. It is possible to obtain higher yields, however, the intended use of the product is very sensitive to any impurity, and the product would deteriorate with higher recovery. Also, it was noted that the vacuum filtration needs to be done rapidly, as prolonged drying on the filter apparently contaminates the product with contaminants from the air, which are visible in the electrochemical work. The melting point of the carefully prepared product was 234–235°C.

Refinement top

The hydrogen atoms on carbon atoms were refined using the riding model in SHELXL with the Uiso equal to 1.5 times of that of the preceding carbon atoms for the methyl groups and 1.3 times for the rings. The C—H distances are equal to 0.97 and 0.96 Å for the CH2 and CH3 groups, respectively.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SMART and SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid drawing of the title compound shown at the 50% probability level.
Triphenyl[(triphenylphosphoranylidene)amino]phosphonium tetrakis(pentafluorophenyl)borate top
Crystal data top
C36H30NP2+·C24BF20F(000) = 2448
Mr = 1217.60Dx = 1.528 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 264 reflections
a = 13.3081 (15) Åθ = 3–14°
b = 25.196 (3) ŵ = 0.20 mm1
c = 16.0355 (18) ÅT = 298 K
β = 100.094 (2)°Fragment, colorless
V = 5293.7 (10) Å30.60 × 0.50 × 0.30 mm
Z = 4
Data collection top
Bruker SMART CCD PLATFORM
diffractometer
9311 independent reflections
Radiation source: fine-focus sealed tube7829 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
Detector resolution: 0 pixels mm-1θmax = 25.0°, θmin = 1.5°
ω scansh = 1515
Absorption correction: multi-scan
(SADABS; Sheldrick, 2006)
k = 2929
Tmin = 0.212, Tmax = 0.264l = 1919
39430 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.104 w = 1/[σ2(Fo2) + (0.0481P)2 + 1.7949P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
9311 reflectionsΔρmax = 0.28 e Å3
758 parametersΔρmin = 0.26 e Å3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0087 (4)
Crystal data top
C36H30NP2+·C24BF20V = 5293.7 (10) Å3
Mr = 1217.60Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.3081 (15) ŵ = 0.20 mm1
b = 25.196 (3) ÅT = 298 K
c = 16.0355 (18) Å0.60 × 0.50 × 0.30 mm
β = 100.094 (2)°
Data collection top
Bruker SMART CCD PLATFORM
diffractometer
9311 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2006)
7829 reflections with I > 2σ(I)
Tmin = 0.212, Tmax = 0.264Rint = 0.030
39430 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.104Δρmax = 0.28 e Å3
S = 1.07Δρmin = 0.26 e Å3
9311 reflectionsAbsolute structure: ?
758 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.22856 (4)0.088527 (18)0.29937 (3)0.04277 (13)
P20.08106 (4)0.000796 (19)0.25127 (3)0.04512 (13)
N10.16074 (13)0.04472 (7)0.24696 (11)0.0542 (4)
B10.91160 (15)0.33507 (8)0.35287 (13)0.0420 (4)
C1010.22876 (14)0.14614 (7)0.23395 (12)0.0470 (4)
C1020.20818 (17)0.14035 (9)0.14671 (14)0.0588 (5)
H1020.19330.10700.12300.071*
C1030.2096 (2)0.18354 (11)0.09540 (16)0.0738 (7)
H1030.19610.17950.03690.089*
C1040.2308 (2)0.23262 (10)0.12998 (18)0.0800 (7)
H1040.23050.26200.09480.096*
C1050.2527 (2)0.23908 (9)0.21653 (19)0.0783 (7)
H1050.26820.27260.23950.094*
C1060.25171 (18)0.19583 (8)0.26909 (15)0.0627 (6)
H1060.26630.20000.32760.075*
C1070.35801 (14)0.06606 (8)0.33088 (13)0.0492 (4)
C1080.43941 (17)0.10045 (10)0.33679 (18)0.0742 (7)
H1080.42860.13570.32040.089*
C1090.53677 (19)0.08255 (13)0.3670 (2)0.0962 (10)
H1090.59150.10590.37090.115*
C1100.5536 (2)0.03128 (14)0.3912 (2)0.0895 (9)
H1100.61970.01970.41180.107*
C1110.4741 (2)0.00317 (11)0.38521 (19)0.0833 (8)
H1110.48570.03840.40160.100*
C1120.37625 (18)0.01402 (9)0.35500 (16)0.0671 (6)
H1120.32210.00970.35090.081*
C1130.18575 (14)0.10953 (7)0.39451 (12)0.0455 (4)
C1140.23645 (16)0.09499 (9)0.47400 (13)0.0578 (5)
H1140.29700.07580.47960.069*
C1150.1971 (2)0.10899 (11)0.54487 (15)0.0724 (6)
H1150.23090.09890.59820.087*
C1160.1086 (2)0.13773 (10)0.53727 (16)0.0740 (7)
H1160.08260.14710.58540.089*
C1170.05825 (19)0.15274 (10)0.45875 (16)0.0704 (6)
H1170.00170.17230.45380.084*
C1180.09619 (16)0.13889 (8)0.38735 (14)0.0576 (5)
H1180.06190.14920.33420.069*
C2010.08078 (16)0.04373 (8)0.16191 (13)0.0536 (5)
C2020.0057 (2)0.06931 (14)0.12396 (19)0.0982 (10)
H2020.06750.06250.14130.118*
C2030.0013 (3)0.10510 (17)0.0602 (2)0.1279 (15)
H2030.06010.12310.03560.154*
C2040.0878 (3)0.11453 (14)0.0326 (2)0.1086 (11)
H2040.08960.13820.01150.130*
C2050.1749 (3)0.08897 (13)0.0701 (2)0.0983 (10)
H2050.23630.09560.05190.118*
C2060.1715 (2)0.05368 (11)0.13461 (18)0.0802 (8)
H2060.23070.03640.16010.096*
C2070.04614 (15)0.02379 (8)0.24891 (12)0.0494 (4)
C2080.12093 (16)0.00698 (9)0.27598 (14)0.0591 (5)
H2080.10530.04100.29670.071*
C2090.21786 (18)0.01270 (12)0.27225 (15)0.0723 (7)
H2090.26800.00820.28950.087*
C2100.2409 (2)0.06321 (13)0.24306 (18)0.0826 (8)
H2100.30610.07680.24210.099*
C2110.1687 (2)0.09353 (11)0.2155 (2)0.0900 (8)
H2110.18510.12760.19510.108*
C2120.07110 (18)0.07410 (9)0.21757 (17)0.0709 (6)
H2120.02240.09480.19790.085*
C2130.11038 (15)0.04065 (8)0.34557 (13)0.0500 (4)
C2140.09871 (16)0.01864 (9)0.42253 (13)0.0577 (5)
H2140.06960.01480.42410.069*
C2150.13004 (19)0.04620 (11)0.49680 (15)0.0719 (6)
H2150.12220.03100.54820.086*
C2160.1718 (2)0.09477 (12)0.49585 (19)0.0883 (8)
H2160.19350.11290.54630.106*
C2170.1820 (3)0.11706 (12)0.4210 (2)0.1101 (11)
H2170.21030.15080.42050.132*
C2180.1510 (2)0.09061 (10)0.34541 (18)0.0825 (8)
H2180.15770.10670.29450.099*
C3010.93347 (13)0.31757 (7)0.25836 (11)0.0429 (4)
C3020.94568 (14)0.26411 (7)0.24073 (12)0.0463 (4)
C3030.96279 (15)0.24450 (8)0.16489 (13)0.0526 (5)
C3040.96834 (16)0.27838 (9)0.09941 (13)0.0554 (5)
C3050.95460 (15)0.33148 (9)0.11172 (13)0.0545 (5)
C3060.93588 (14)0.34953 (7)0.18875 (12)0.0479 (4)
C3070.91300 (14)0.39991 (7)0.36903 (11)0.0464 (4)
C3080.99731 (16)0.42967 (8)0.35719 (13)0.0530 (5)
C3091.00838 (18)0.48316 (9)0.37307 (14)0.0629 (6)
C3100.9343 (2)0.50981 (8)0.40492 (15)0.0685 (6)
C3110.85109 (19)0.48278 (9)0.42072 (14)0.0654 (6)
C3120.84172 (16)0.42897 (8)0.40271 (13)0.0530 (5)
C3131.00187 (14)0.31447 (7)0.43143 (12)0.0461 (4)
C3141.09755 (15)0.29544 (8)0.42482 (14)0.0536 (5)
C3151.17082 (16)0.28180 (9)0.49416 (17)0.0669 (6)
C3161.15124 (18)0.28808 (10)0.57383 (16)0.0713 (7)
C3171.05887 (19)0.30817 (10)0.58441 (14)0.0669 (6)
C3180.98807 (15)0.32090 (8)0.51411 (13)0.0529 (5)
C3190.79839 (13)0.30774 (7)0.35379 (11)0.0430 (4)
C3200.77678 (14)0.26317 (7)0.39764 (12)0.0467 (4)
C3210.68163 (16)0.24029 (8)0.38989 (13)0.0532 (5)
C3220.60085 (16)0.26158 (9)0.33584 (14)0.0587 (5)
C3230.61746 (15)0.30516 (9)0.28948 (13)0.0576 (5)
C3240.71371 (14)0.32658 (8)0.29868 (12)0.0479 (4)
F3020.94100 (10)0.22779 (4)0.30197 (7)0.0595 (3)
F3030.97370 (11)0.19200 (5)0.15422 (9)0.0742 (4)
F3040.98522 (11)0.26021 (6)0.02472 (8)0.0785 (4)
F3050.95914 (12)0.36579 (5)0.04829 (8)0.0769 (4)
F3060.91801 (10)0.40232 (4)0.19218 (7)0.0616 (3)
F3081.07512 (9)0.40554 (5)0.32848 (9)0.0659 (3)
F3091.09217 (12)0.50916 (6)0.35857 (11)0.0893 (5)
F3100.94318 (14)0.56211 (5)0.42144 (11)0.1008 (5)
F3110.77742 (13)0.50779 (6)0.45293 (10)0.0935 (5)
F3120.75641 (9)0.40614 (5)0.42110 (8)0.0664 (3)
F3141.12606 (9)0.28882 (6)0.34921 (8)0.0721 (4)
F3151.26140 (10)0.26230 (7)0.48210 (11)0.0992 (5)
F3161.22159 (13)0.27484 (8)0.64166 (11)0.1081 (6)
F3171.03870 (13)0.31549 (8)0.66281 (9)0.1008 (5)
F3180.89929 (9)0.34100 (6)0.52933 (8)0.0679 (3)
F3200.85042 (9)0.23824 (4)0.45267 (8)0.0590 (3)
F3210.66743 (10)0.19687 (5)0.43540 (9)0.0748 (4)
F3220.50761 (10)0.23982 (7)0.32793 (10)0.0859 (4)
F3230.53981 (9)0.32680 (7)0.23466 (9)0.0838 (4)
F3240.72415 (9)0.36956 (5)0.25024 (7)0.0612 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0420 (3)0.0386 (2)0.0477 (3)0.00422 (19)0.0077 (2)0.00334 (19)
P20.0464 (3)0.0417 (3)0.0464 (3)0.0080 (2)0.0059 (2)0.0044 (2)
N10.0582 (10)0.0510 (9)0.0530 (10)0.0141 (8)0.0086 (8)0.0045 (7)
B10.0403 (11)0.0400 (10)0.0454 (11)0.0034 (8)0.0066 (9)0.0007 (9)
C1010.0431 (10)0.0453 (10)0.0545 (11)0.0031 (8)0.0138 (8)0.0000 (8)
C1020.0622 (13)0.0597 (13)0.0559 (12)0.0098 (10)0.0139 (10)0.0008 (10)
C1030.0812 (17)0.0812 (17)0.0610 (14)0.0122 (13)0.0184 (12)0.0128 (12)
C1040.0964 (19)0.0672 (16)0.0828 (18)0.0039 (14)0.0331 (15)0.0241 (14)
C1050.103 (2)0.0440 (12)0.095 (2)0.0081 (12)0.0368 (16)0.0011 (12)
C1060.0812 (15)0.0469 (11)0.0631 (13)0.0071 (10)0.0213 (11)0.0029 (10)
C1070.0462 (10)0.0480 (11)0.0541 (11)0.0013 (8)0.0106 (8)0.0097 (9)
C1080.0492 (12)0.0613 (14)0.111 (2)0.0041 (10)0.0112 (12)0.0058 (13)
C1090.0464 (14)0.097 (2)0.143 (3)0.0048 (14)0.0106 (15)0.0153 (19)
C1100.0524 (15)0.112 (2)0.104 (2)0.0246 (15)0.0116 (14)0.0087 (18)
C1110.0806 (18)0.0742 (17)0.095 (2)0.0304 (15)0.0159 (15)0.0037 (14)
C1120.0615 (13)0.0541 (13)0.0853 (16)0.0069 (10)0.0119 (12)0.0011 (11)
C1130.0474 (10)0.0404 (9)0.0490 (10)0.0040 (8)0.0096 (8)0.0015 (8)
C1140.0520 (11)0.0656 (13)0.0533 (12)0.0031 (10)0.0023 (9)0.0056 (10)
C1150.0772 (16)0.0892 (17)0.0493 (12)0.0032 (13)0.0070 (11)0.0033 (12)
C1160.0854 (17)0.0832 (17)0.0589 (14)0.0027 (14)0.0280 (13)0.0085 (12)
C1170.0711 (15)0.0704 (15)0.0755 (16)0.0178 (12)0.0290 (12)0.0033 (12)
C1180.0581 (12)0.0584 (12)0.0577 (12)0.0119 (10)0.0136 (10)0.0076 (10)
C2010.0562 (12)0.0546 (12)0.0504 (11)0.0132 (9)0.0103 (9)0.0098 (9)
C2020.0683 (16)0.135 (3)0.092 (2)0.0332 (17)0.0164 (14)0.0606 (19)
C2030.102 (2)0.165 (4)0.116 (3)0.048 (2)0.017 (2)0.085 (3)
C2040.131 (3)0.116 (3)0.083 (2)0.031 (2)0.0339 (19)0.0561 (19)
C2050.099 (2)0.104 (2)0.101 (2)0.0166 (18)0.0425 (18)0.0427 (18)
C2060.0694 (15)0.0855 (17)0.0899 (18)0.0198 (13)0.0258 (13)0.0352 (15)
C2070.0503 (11)0.0502 (11)0.0463 (10)0.0041 (9)0.0042 (8)0.0026 (8)
C2080.0541 (12)0.0654 (13)0.0574 (12)0.0054 (10)0.0089 (10)0.0011 (10)
C2090.0535 (13)0.100 (2)0.0646 (14)0.0073 (13)0.0125 (11)0.0033 (13)
C2100.0543 (14)0.103 (2)0.0866 (18)0.0136 (14)0.0031 (13)0.0163 (16)
C2110.0741 (18)0.0708 (17)0.117 (2)0.0143 (14)0.0046 (16)0.0090 (16)
C2120.0595 (14)0.0594 (14)0.0907 (17)0.0003 (11)0.0042 (12)0.0106 (12)
C2130.0479 (10)0.0448 (10)0.0557 (12)0.0067 (8)0.0050 (9)0.0008 (9)
C2140.0595 (12)0.0587 (12)0.0546 (12)0.0034 (10)0.0089 (10)0.0011 (10)
C2150.0724 (15)0.0866 (18)0.0551 (13)0.0064 (13)0.0069 (11)0.0059 (12)
C2160.098 (2)0.087 (2)0.0738 (18)0.0075 (16)0.0001 (15)0.0252 (15)
C2170.159 (3)0.0665 (17)0.101 (2)0.0421 (19)0.013 (2)0.0207 (17)
C2180.116 (2)0.0552 (14)0.0746 (17)0.0185 (14)0.0122 (15)0.0001 (12)
C3010.0374 (9)0.0428 (10)0.0478 (10)0.0004 (7)0.0055 (8)0.0002 (8)
C3020.0449 (10)0.0439 (10)0.0498 (11)0.0006 (8)0.0073 (8)0.0016 (8)
C3030.0513 (11)0.0456 (11)0.0611 (12)0.0009 (8)0.0103 (9)0.0108 (9)
C3040.0545 (12)0.0646 (13)0.0482 (11)0.0031 (10)0.0121 (9)0.0122 (10)
C3050.0552 (12)0.0616 (13)0.0473 (11)0.0041 (10)0.0113 (9)0.0062 (9)
C3060.0487 (10)0.0419 (10)0.0531 (11)0.0010 (8)0.0085 (8)0.0009 (8)
C3070.0486 (10)0.0446 (10)0.0435 (10)0.0048 (8)0.0012 (8)0.0018 (8)
C3080.0547 (12)0.0484 (11)0.0528 (11)0.0012 (9)0.0008 (9)0.0032 (9)
C3090.0701 (14)0.0510 (12)0.0612 (13)0.0111 (11)0.0061 (11)0.0009 (10)
C3100.0911 (18)0.0402 (11)0.0653 (14)0.0018 (11)0.0111 (12)0.0093 (10)
C3110.0793 (16)0.0544 (13)0.0573 (13)0.0225 (12)0.0022 (11)0.0126 (10)
C3120.0551 (12)0.0521 (11)0.0494 (11)0.0085 (9)0.0025 (9)0.0031 (9)
C3130.0424 (10)0.0415 (10)0.0522 (11)0.0000 (8)0.0025 (8)0.0016 (8)
C3140.0456 (11)0.0520 (11)0.0609 (12)0.0030 (9)0.0033 (9)0.0023 (9)
C3150.0439 (12)0.0655 (14)0.0854 (17)0.0069 (10)0.0053 (11)0.0032 (12)
C3160.0595 (14)0.0737 (15)0.0698 (16)0.0021 (11)0.0189 (12)0.0110 (12)
C3170.0733 (15)0.0719 (15)0.0501 (13)0.0051 (12)0.0042 (11)0.0057 (11)
C3180.0486 (11)0.0543 (12)0.0541 (12)0.0004 (9)0.0040 (9)0.0018 (9)
C3190.0417 (10)0.0455 (10)0.0417 (10)0.0038 (8)0.0073 (8)0.0026 (8)
C3200.0472 (10)0.0464 (10)0.0458 (10)0.0043 (8)0.0063 (8)0.0003 (8)
C3210.0573 (12)0.0499 (11)0.0534 (11)0.0073 (9)0.0126 (9)0.0006 (9)
C3220.0455 (11)0.0729 (14)0.0571 (12)0.0124 (10)0.0075 (9)0.0053 (11)
C3230.0427 (11)0.0766 (14)0.0501 (11)0.0060 (10)0.0016 (9)0.0001 (10)
C3240.0473 (11)0.0510 (11)0.0450 (10)0.0036 (8)0.0072 (8)0.0034 (8)
F3020.0773 (8)0.0417 (6)0.0612 (7)0.0070 (5)0.0170 (6)0.0067 (5)
F3030.0954 (10)0.0495 (7)0.0810 (9)0.0035 (6)0.0244 (7)0.0173 (6)
F3040.0904 (10)0.0924 (10)0.0574 (8)0.0034 (8)0.0261 (7)0.0191 (7)
F3050.1014 (10)0.0772 (9)0.0558 (7)0.0018 (7)0.0238 (7)0.0140 (6)
F3060.0833 (8)0.0429 (6)0.0588 (7)0.0033 (5)0.0135 (6)0.0070 (5)
F3080.0517 (7)0.0638 (7)0.0835 (9)0.0074 (6)0.0159 (6)0.0063 (6)
F3090.0929 (11)0.0649 (8)0.1046 (11)0.0309 (8)0.0017 (8)0.0006 (8)
F3100.1391 (15)0.0436 (7)0.1065 (12)0.0027 (8)0.0149 (10)0.0187 (7)
F3110.1077 (12)0.0761 (9)0.0955 (11)0.0365 (8)0.0145 (9)0.0252 (8)
F3120.0588 (7)0.0692 (8)0.0741 (8)0.0123 (6)0.0193 (6)0.0087 (6)
F3140.0485 (7)0.0950 (10)0.0732 (8)0.0164 (6)0.0115 (6)0.0094 (7)
F3150.0496 (8)0.1182 (13)0.1218 (13)0.0288 (8)0.0072 (8)0.0010 (10)
F3160.0850 (11)0.1322 (14)0.0890 (11)0.0130 (10)0.0353 (9)0.0211 (10)
F3170.1074 (12)0.1400 (15)0.0498 (8)0.0071 (11)0.0006 (8)0.0090 (8)
F3180.0613 (7)0.0901 (9)0.0535 (7)0.0097 (6)0.0135 (6)0.0017 (6)
F3200.0547 (7)0.0544 (7)0.0653 (7)0.0043 (5)0.0033 (5)0.0157 (5)
F3210.0767 (9)0.0646 (8)0.0830 (9)0.0181 (6)0.0140 (7)0.0145 (7)
F3220.0519 (7)0.1139 (12)0.0890 (10)0.0278 (7)0.0045 (7)0.0040 (9)
F3230.0474 (7)0.1192 (12)0.0777 (9)0.0048 (7)0.0092 (6)0.0232 (8)
F3240.0561 (7)0.0659 (7)0.0585 (7)0.0054 (6)0.0018 (5)0.0185 (6)
Geometric parameters (Å, º) top
P1—N11.5727 (16)C209—H2090.9300
P1—C1011.7913 (19)C210—C2111.361 (4)
P1—C1131.7992 (19)C210—H2100.9300
P1—C1071.800 (2)C211—C2121.383 (4)
P2—N11.5717 (16)C211—H2110.9300
P2—C2011.795 (2)C212—H2120.9300
P2—C2071.797 (2)C213—C2181.370 (3)
P2—C2131.800 (2)C213—C2141.386 (3)
B1—C3011.653 (3)C214—C2151.378 (3)
B1—C3071.654 (3)C214—H2140.9300
B1—C3191.659 (3)C215—C2161.346 (4)
B1—C3131.664 (3)C215—H2150.9300
C101—C1061.385 (3)C216—C2171.352 (4)
C101—C1021.385 (3)C216—H2160.9300
C102—C1031.367 (3)C217—C2181.382 (4)
C102—H1020.9300C217—H2170.9300
C103—C1041.364 (4)C218—H2180.9300
C103—H1030.9300C301—C3061.381 (3)
C104—C1051.377 (4)C301—C3021.392 (3)
C104—H1040.9300C302—F3021.352 (2)
C105—C1061.379 (3)C302—C3031.368 (3)
C105—H1050.9300C303—F3031.345 (2)
C106—H1060.9300C303—C3041.365 (3)
C107—C1121.376 (3)C304—F3041.338 (2)
C107—C1081.377 (3)C304—C3051.369 (3)
C108—C1091.377 (4)C305—F3051.344 (2)
C108—H1080.9300C305—C3061.379 (3)
C109—C1101.356 (4)C306—F3061.354 (2)
C109—H1090.9300C307—C3121.381 (3)
C110—C1111.360 (4)C307—C3081.390 (3)
C110—H1100.9300C308—F3081.349 (2)
C111—C1121.377 (3)C308—C3091.375 (3)
C111—H1110.9300C309—F3091.348 (3)
C112—H1120.9300C309—C3101.363 (3)
C113—C1141.383 (3)C310—F3101.345 (2)
C113—C1181.390 (3)C310—C3111.362 (4)
C114—C1151.378 (3)C311—F3111.343 (3)
C114—H1140.9300C311—C3121.387 (3)
C115—C1161.369 (4)C312—F3121.351 (2)
C115—H1150.9300C313—C3181.380 (3)
C116—C1171.372 (4)C313—C3141.382 (3)
C116—H1160.9300C314—F3141.343 (2)
C117—C1181.375 (3)C314—C3151.387 (3)
C117—H1170.9300C315—F3151.347 (3)
C118—H1180.9300C315—C3161.357 (4)
C201—C2021.365 (3)C316—F3161.347 (3)
C201—C2061.378 (3)C316—C3171.367 (3)
C202—C2031.372 (4)C317—F3171.343 (3)
C202—H2020.9300C317—C3181.374 (3)
C203—C2041.357 (5)C318—F3181.346 (2)
C203—H2030.9300C319—C3201.382 (3)
C204—C2051.370 (4)C319—C3241.388 (3)
C204—H2040.9300C320—F3201.353 (2)
C205—C2061.371 (4)C320—C3211.377 (3)
C205—H2050.9300C321—F3211.347 (2)
C206—H2060.9300C321—C3221.367 (3)
C207—C2121.383 (3)C322—F3221.342 (2)
C207—C2081.390 (3)C322—C3231.366 (3)
C208—C2091.374 (3)C323—F3231.349 (2)
C208—H2080.9300C323—C3241.374 (3)
C209—C2101.372 (4)C324—F3241.354 (2)
N1—P1—C101108.38 (9)C211—C210—C209120.2 (2)
N1—P1—C113114.97 (9)C211—C210—H210119.9
C101—P1—C113106.94 (9)C209—C210—H210119.9
N1—P1—C107111.15 (9)C210—C211—C212120.5 (3)
C101—P1—C107108.65 (9)C210—C211—H211119.8
C113—P1—C107106.52 (9)C212—C211—H211119.8
N1—P2—C201108.16 (9)C207—C212—C211119.9 (2)
N1—P2—C207112.82 (9)C207—C212—H212120.1
C201—P2—C207108.72 (9)C211—C212—H212120.1
N1—P2—C213113.29 (9)C218—C213—C214118.4 (2)
C201—P2—C213107.71 (10)C218—C213—P2122.58 (18)
C207—P2—C213105.94 (9)C214—C213—P2118.88 (16)
P2—N1—P1144.79 (12)C215—C214—C213120.2 (2)
C301—B1—C307114.10 (15)C215—C214—H214119.9
C301—B1—C319101.75 (14)C213—C214—H214119.9
C307—B1—C319113.19 (15)C216—C215—C214120.8 (2)
C301—B1—C313113.04 (15)C216—C215—H215119.6
C307—B1—C313101.69 (14)C214—C215—H215119.6
C319—B1—C313113.59 (15)C215—C216—C217119.6 (3)
C106—C101—C102119.78 (19)C215—C216—H216120.2
C106—C101—P1121.14 (16)C217—C216—H216120.2
C102—C101—P1119.06 (15)C216—C217—C218121.2 (3)
C103—C102—C101120.2 (2)C216—C217—H217119.4
C103—C102—H102119.9C218—C217—H217119.4
C101—C102—H102119.9C213—C218—C217119.9 (3)
C104—C103—C102120.1 (2)C213—C218—H218120.1
C104—C103—H103120.0C217—C218—H218120.1
C102—C103—H103120.0C306—C301—C302112.34 (17)
C103—C104—C105120.6 (2)C306—C301—B1128.20 (16)
C103—C104—H104119.7C302—C301—B1119.35 (16)
C105—C104—H104119.7F302—C302—C303115.92 (16)
C104—C105—C106120.0 (2)F302—C302—C301119.07 (16)
C104—C105—H105120.0C303—C302—C301125.00 (18)
C106—C105—H105120.0F303—C303—C304119.71 (18)
C105—C106—C101119.4 (2)F303—C303—C302120.45 (19)
C105—C106—H106120.3C304—C303—C302119.84 (18)
C101—C106—H106120.3F304—C304—C303120.99 (19)
C112—C107—C108118.8 (2)F304—C304—C305120.7 (2)
C112—C107—P1119.44 (16)C303—C304—C305118.27 (18)
C108—C107—P1121.60 (17)F305—C305—C304119.63 (19)
C109—C108—C107119.9 (2)F305—C305—C306120.30 (19)
C109—C108—H108120.1C304—C305—C306120.06 (18)
C107—C108—H108120.1F306—C306—C305114.89 (17)
C110—C109—C108120.7 (3)F306—C306—C301120.71 (17)
C110—C109—H109119.6C305—C306—C301124.39 (18)
C108—C109—H109119.6C312—C307—C308113.18 (18)
C109—C110—C111120.0 (2)C312—C307—B1126.54 (18)
C109—C110—H110120.0C308—C307—B1119.91 (16)
C111—C110—H110120.0F308—C308—C309116.18 (19)
C110—C111—C112120.0 (3)F308—C308—C307119.32 (17)
C110—C111—H111120.0C309—C308—C307124.5 (2)
C112—C111—H111120.0F309—C309—C310120.0 (2)
C107—C112—C111120.5 (2)F309—C309—C308120.6 (2)
C107—C112—H112119.7C310—C309—C308119.4 (2)
C111—C112—H112119.7F310—C310—C311119.9 (2)
C114—C113—C118119.32 (18)F310—C310—C309120.8 (2)
C114—C113—P1121.85 (15)C311—C310—C309119.2 (2)
C118—C113—P1118.74 (15)F311—C311—C310120.6 (2)
C115—C114—C113119.9 (2)F311—C311—C312119.6 (2)
C115—C114—H114120.1C310—C311—C312119.8 (2)
C113—C114—H114120.1F312—C312—C307121.39 (18)
C116—C115—C114120.5 (2)F312—C312—C311114.77 (19)
C116—C115—H115119.8C307—C312—C311123.8 (2)
C114—C115—H115119.8C318—C313—C314113.21 (17)
C115—C116—C117120.1 (2)C318—C313—B1119.40 (16)
C115—C116—H116119.9C314—C313—B1127.07 (17)
C117—C116—H116119.9F314—C314—C313121.49 (18)
C116—C117—C118120.2 (2)F314—C314—C315115.01 (19)
C116—C117—H117119.9C313—C314—C315123.5 (2)
C118—C117—H117119.9F315—C315—C316120.1 (2)
C117—C118—C113120.1 (2)F315—C315—C314119.7 (2)
C117—C118—H118120.0C316—C315—C314120.1 (2)
C113—C118—H118120.0F316—C316—C315120.7 (2)
C202—C201—C206119.3 (2)F316—C316—C317120.3 (2)
C202—C201—P2121.60 (18)C315—C316—C317119.0 (2)
C206—C201—P2118.94 (16)F317—C317—C316119.9 (2)
C201—C202—C203120.0 (3)F317—C317—C318121.0 (2)
C201—C202—H202120.0C316—C317—C318119.1 (2)
C203—C202—H202120.0F318—C318—C317115.86 (19)
C204—C203—C202120.8 (3)F318—C318—C313119.16 (17)
C204—C203—H203119.6C317—C318—C313125.0 (2)
C202—C203—H203119.6C320—C319—C324112.57 (17)
C203—C204—C205119.7 (3)C320—C319—B1127.74 (16)
C203—C204—H204120.1C324—C319—B1119.32 (16)
C205—C204—H204120.1F320—C320—C321114.46 (17)
C206—C205—C204119.9 (3)F320—C320—C319121.18 (16)
C206—C205—H205120.1C321—C320—C319124.36 (18)
C204—C205—H205120.1F321—C321—C322119.54 (18)
C205—C206—C201120.3 (2)F321—C321—C320120.35 (18)
C205—C206—H206119.8C322—C321—C320120.11 (19)
C201—C206—H206119.8F322—C322—C323120.8 (2)
C212—C207—C208119.0 (2)F322—C322—C321120.7 (2)
C212—C207—P2119.29 (16)C323—C322—C321118.45 (19)
C208—C207—P2121.65 (16)F323—C323—C322120.07 (19)
C209—C208—C207120.2 (2)F323—C323—C324120.3 (2)
C209—C208—H208119.9C322—C323—C324119.63 (18)
C207—C208—H208119.9F324—C324—C323116.12 (17)
C210—C209—C208120.1 (2)F324—C324—C319119.03 (16)
C210—C209—H209119.9C323—C324—C319124.86 (18)
C208—C209—H209119.9
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C118—H118···F302i0.932.553.188 (2)126
C212—H212···F303i0.932.553.229 (3)131
Symmetry code: (i) x1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C118—H118···F302i0.932.553.188 (2)126
C212—H212···F303i0.932.553.229 (3)131
Symmetry code: (i) x1, y, z.
Acknowledgements top

The authors acknowledge support from the NSF-CHE0615129.

references
References top

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119.

Bruker (1999). SMART and SAINT. Bruker Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Fermín, D. J., Duong, H. D., Ding, Z., Brevet, P. F. & Girault, H. H. (1999). Phys. Chem. Chem. Phys. 1, 1461–1467.

Gobry, V. (2001). Thesis, École Polytechnique Fédérale de Lausanne, Switzerland.

Luo, G., Málková, S., Yoon, J., Schultz, D. G., Lin, B., Meron, M., Benjamin, I., Vanýsek, P. & Schlossman, M. L. (2006). J. Electroanal. Chem. 593, 142–158.

Sheldrick, G. M. (2006). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Stephenson, M. J., Holmes, S. M. & Dryfe, R. A. W. (2005). Angew. Chem. Int. Ed. 44, 3075–3078.

Su, B., Li, F., Partovi-Nia, R., Gros, C., Barbe, J.-M., Samec, Z. & Girault, H. H. (2008a). Chem. Commun. 40, 5037–5038.

Su, B., Partovi-Nia, R., Li, F., Hojeij, M., Prudent, M., Corminboeuf, C., Samec, Z. & Girault, H. H. (2008b). Angew. Chem. Int. Ed. 47, 4675–4678.

Vanýsek, P. & Novák, V. (2009). ECS Trans. 19, 55–63.