2-[(Diisopropyl­thio­phosphor­yl)amino]­pyridinium tetra­fluoro­borate

Holzhacker, C.; Kirchner, K.; Mereiter, K.

doi:10.1107/S1600536812022295

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Pages o1835-o1836

doi:10.1107/S1600536812022295

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2-[(Diisopropylthiophosphoryl)amino]pyridinium tetrafluoroborate

Christian Holzhacker,^a Karl Kirchner ^a and Kurt Mereiter ^b ^*

^aInstitute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/163, A-1060 Vienna, Austria, and ^bInstitute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/164SC, A-1060 Vienna, Austria
^*Correspondence e-mail: kurt.mereiter@tuwien.ac.at

(Received 5 April 2012; accepted 16 May 2012; online 23 May 2012)

The title compound, C₁₁H₂₀N₂PS⁺·BF₄⁻, is a salt of 2-(diisopropylthiophosphorylamino)pyridine, a chelating bidentate ligand that furnishes an S atom as a soft donor and a pyridine N atom as a hard atom for transition-metal complexation. The title salt crystallizes with two formula units in the asymmetric unit. The two independent cations are protonated at the pyridine N atoms and have the S atoms syn-oriented to them so as to form bent intramolecular N—H⋯S hydrogen bonds, one of which one is bifurcated by involving also an N—H⋯F interaction. The phosphorylamino NH groups form near linear hydrogen bonds to proximal tetrafluoroborate anions. Five weak C—H⋯F and three weak C—H⋯S interactions link the constituents into a three-dimensional framework. As a result of the crystal packing, the two cations differ notably in conformation, as can be seen from the S—P—N—C torsion angles of −18.7 (1)° in the first and −35.1 (1)° in the second cation.

Related literature

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

Experimental

Crystal data

C₁₁H₂₀N₂PS⁺·BF₄⁻
M_r = 330.13
Triclinic, $[P \overline 1]$
a = 9.5816 (1) Å
b = 11.3855 (2) Å
c = 14.3650 (2) Å
α = 88.221 (1)°
β = 86.067 (1)°
γ = 82.299 (1)°
V = 1548.93 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 100 K
0.54 × 0.40 × 0.38 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.79, T_max = 0.86
40158 measured reflections
8997 independent reflections
8332 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.076
S = 1.02
8997 reflections
385 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S1	0.831 (17)	2.482 (16)	3.1356 (9)	136.3 (14)
N1—H1N⋯F2ⁱ	0.831 (17)	2.266 (16)	2.8820 (10)	131.2 (14)
N2—H2N⋯F1	0.827 (16)	1.982 (17)	2.8073 (10)	175.6 (15)
N3—H3N⋯S2	0.862 (16)	2.375 (16)	3.1297 (9)	146.4 (14)
N4—H4N⋯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⋯F7ⁱⁱ	0.95	2.36	3.2290 (12)	151
C6—H6⋯S1ⁱⁱⁱ	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⋯F6ⁱ	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.

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812022295/ez2293sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812022295/ez2293Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812022295/ez2293Isup3.cml

checkCIF report

Comment top

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 P1 and contains two formula units [C₁₁H₂₀N₂PS]⁺(BF₄)^- in the asymmetric unit (Fig. 1). In (I), both organocations [SN-ⁱPr]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-ⁱPr]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-ⁱPr], 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-ⁱPr], 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-ⁱPr] (Öztopcu et al., 2011) to ca 123° in [SN-ⁱPr]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 BF₄ anions with N···F distances of 2.807 (1) and 2.871 (1) Å (Table 1). In the parent compound [SN-ⁱPr] 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.

Related literature top

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

Experimental top

2-(Diisopropylthiophosphorylamino)-pyridine (Öztopcu et al., 2011; Smith & Sisler, 1961; 1.03 mmol, 250 mg) was dissolved in dry CH₂Cl₂ and 1.05 equivalent of HBF₄ in Et₂O was added. The solvent was removed under reduced pressure and the solid residue was washed twice with 15 ml dry Et₂O. Yield: 326 mg, 95.7%, white solid. Colourless crystals of the title compound for X-ray diffraction were obtained from a CH₂Cl₂ solution by vapour diffusion of Et₂O. ¹H NMR (δ, CD₂Cl₂, 20°C): 15.15 (bs, 1H, [pyH]⁺), 8.12 (t, J = 7.8 Hz, 1H, py⁶),7.98 – 7.90 (m, 2H, py⁴, NH), 7.84 (d, J = 9.0 Hz, 1H, py³),7.25 (t, 6.8 Hz, 1H, py⁵), 2.65 – 2.51 (m, 2H, CH(CH₃)₂), 1.38 – 1.23 (m, 12H, CH(CH₃)₂). ¹³C{¹H}NMR (δ, CH₂Cl₂, 20°C): 154.6 (s, py²), 146.0(s, py⁶), 135.0 (s, py⁴), 118.2 (s, py⁵), 117.2 (s, py³), 31.1 (d, J = 57.2 Hz, CH(CH₃)₂), 15.4 (s, CH(CH₃)₂), 15.1 (s, CH(CH₃)₂). ³¹P{¹H}NMR (δ, CD₂Cl₂, 20°C): 107.2.

Computing details top

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

Figures top

	Fig. 1. The asymmetric unit of (I) with displacement ellipsoids at the 50% probability level and dashed red lines for hydrogen bonds.
	Fig. 2. 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.

2-[(Diisopropylthiophosphoryl)amino]pyridinium tetrafluoroborate top

Crystal data top

C₁₁H₂₀N₂PS⁺·BF₄⁻	Z = 4
M_r = 330.13	F(000) = 688
Triclinic, P1	D_x = 1.416 Mg m⁻³
a = 9.5816 (1) Å	Mo Kα 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) Å³	0.54 × 0.40 × 0.38 mm

Data collection top

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 top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0381P)² + 0.7013P] where P = (F_o² + 2F_c²)/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

Crystal data top

C₁₁H₂₀N₂PS⁺·BF₄⁻	γ = 82.299 (1)°
M_r = 330.13	V = 1548.93 (4) Å³
Triclinic, P1	Z = 4
a = 9.5816 (1) Å	Mo Kα radiation
b = 11.3855 (2) Å	µ = 0.34 mm⁻¹
c = 14.3650 (2) Å	T = 100 K
α = 88.221 (1)°	0.54 × 0.40 × 0.38 mm
β = 86.067 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	8997 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	8332 reflections with I > 2σ(I)
T_min = 0.79, T_max = 0.86	R_int = 0.026
40158 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.72 e Å⁻³
8997 reflections	Δρ_min = −0.55 e Å⁻³
385 parameters

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

	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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

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) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1	0.831 (17)	2.482 (16)	3.1356 (9)	136.3 (14)
N1—H1N···F2ⁱ	0.831 (17)	2.266 (16)	2.8820 (10)	131.2 (14)
N2—H2N···F1	0.827 (16)	1.982 (17)	2.8073 (10)	175.6 (15)
N3—H3N···S2	0.862 (16)	2.375 (16)	3.1297 (9)	146.4 (14)
N4—H4N···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···F7ⁱⁱ	0.95	2.36	3.2290 (12)	151
C6—H6···S1ⁱⁱⁱ	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···F6ⁱ	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.

Experimental details

Crystal data
Chemical formula	C₁₁H₂₀N₂PS⁺·BF₄⁻
M_r	330.13
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	9.5816 (1), 11.3855 (2), 14.3650 (2)
α, β, γ (°)	88.221 (1), 86.067 (1), 82.299 (1)
V (Å³)	1548.93 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.54 × 0.40 × 0.38

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.79, 0.86
No. of measured, independent and observed [I > 2σ(I)] reflections	40158, 8997, 8332
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.076, 1.02
No. of reflections	8997
No. of parameters	385
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.55

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SAINT and XPREP (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1	0.831 (17)	2.482 (16)	3.1356 (9)	136.3 (14)
N1—H1N···F2ⁱ	0.831 (17)	2.266 (16)	2.8820 (10)	131.2 (14)
N2—H2N···F1	0.827 (16)	1.982 (17)	2.8073 (10)	175.6 (15)
N3—H3N···S2	0.862 (16)	2.375 (16)	3.1297 (9)	146.4 (14)
N4—H4N···F5	0.824 (17)	2.059 (17)	2.8714 (11)	168.7 (15)
C2—H2···F4	0.95	2.39	3.3341 (12)	176.8
C4—H4···F7ⁱⁱ	0.95	2.36	3.2290 (12)	151.3
C6—H6···S1ⁱⁱⁱ	1.00	2.71	3.7038 (10)	171.9
C13—H13···F7	0.95	2.53	3.2968 (13)	137.7
C14—H14···S1^iv	0.95	2.85	3.5328 (10)	129.4
C15—H15···F3	0.95	2.52	3.2773 (13)	136.6
C16—H16···F6ⁱ	0.95	2.41	3.3406 (12)	164.7
C17—H17···S2^v	1.00	2.73	3.7128 (10)	169.0

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.

Acknowledgements

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

References

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