Trimethyl­sulfonium 1-amino-6-fluoro-2,3,4,5,7,8,9,10,11,12-decaiodo-1-carba-closo-dodeca­borate

Finze, M.; Reiss, G.J.

doi:10.1107/S1600536812004424

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o640

doi:10.1107/S1600536812004424

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Trimethylsulfonium 1-amino-6-fluoro-2,3,4,5,7,8,9,10,11,12-decaiodo-1-carba-closo-dodecaborate

Maik Finze ^a ^* and Guido J. Reiss ^b

^aInstitut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, D-97074 Würzburg, Germany, and ^bInstitut für Anorganische Chemie und Strukturchemie, Lehrstuhl II: Material- und Strukturforschung, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany
^*Correspondence e-mail: maik.finze@uni-wuerzburg.de

(Received 26 January 2012; accepted 2 February 2012; online 10 February 2012)

In the asymmetric unit of the title salt, C₃H₉S⁺·CH₂B₁₁FI₁₀N⁻ or (CH₃)₃S[1-H₂N-6-F-closo-1-CB₁₁I₁₀], both ions lie in general positions. The anion is perfectly ordered and so the positions of the C—NH₂ vertex and the fluorine substituent are clearly assigned. The relatively short C—N bond length may be interpreted in terms of a very electron deficient {closo-1-CB₁₁} cluster.

Related literature

For a general overview on monocarba-closo-dodecaborates, see: Körbe et al. (2006 ). For the synthesis and properties of 1-aminomonocarba-closo-dodecaboron clusters, see: Jelínek et al. (1986 ); Srivastava et al. (1996 ); Finze (2007 , 2009 ); Finze et al. (2007 ); Finze & Sprenger (2010 ). For studies on the proton affinity of halogenated {closo-1-CB₁₁} clusters, see: Himmelspach et al. (2011 , 2012 ). For the formation of (CH₃)₃S⁺ from dimethyl sulfoxide, see: Nifontova & Lavrentiev (1993 ); Forrester et al. (1995 ); Park et al. (2005 ). For the structure of (CH₃)₃SBr, see: Svensson & Kloo (1996 ).

Experimental

Crystal data

C₃H₉S⁺·CH₂B₁₁FI₁₀N⁻
M_r = 1512.11
Monoclinic, P 2₁ /n
a = 10.0672 (1) Å
b = 16.7057 (2) Å
c = 17.5574 (2) Å
β = 93.175 (1)°
V = 2948.26 (6) Å³
Z = 4
Mo Kα radiation
μ = 10.59 mm⁻¹
T = 100 K
0.79 × 0.28 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ), based on expressions derived by Clark & Reid (1995 )] T_min = 0.040, T_max = 0.204
30584 measured reflections
5482 independent reflections
5282 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.052
S = 1.31
5482 reflections
264 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.06 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2011 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812004424/ru2027sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812004424/ru2027Isup2.hkl

checkCIF report

Comment top

Monocarba-closo-dodecaborates with amino groups that are bonded to the cluster carbon or boron atoms are potential building blocks for a broad range of applications (Körbe et al., 2006). The properties of the amino group are strongly influenced by (i) the other substituents of the {closo-1-CB₁₁} cluster (Jelínek et al. 1986; Srivastava et al. 1996; Finze et al., 2007; Finze, 2007) and (ii) the type of cluster atom that it is bonded to (Finze, 2009).

Halogenation of all boron vertices of the {closo-1-CB₁₁} cluster (Körbe et al., 2006) results in a decrease of the electron density in the cluster. For example, this effect is evident from the calculated proton affinity of [closo-1-CB₁₁X₁₁]^2– that strongly decreases from X = H to X = halogen (Himmelspach et al., 2012). A further example is the coordination of CH₃CN or H₂O to Hg^II of the dianionic mercury(II) complex [Hg(closo-1-CB₁₁F₁₁)₂]^2–, which is related to the Lewis-acidity of mercury (Himmelspach et al., 2011). In contrast, for the complex [Hg(closo-1-CB₁₁H₁₁)₂]^2– that possess a lower Lewis-acidity at the mercury atom no coordination of a third ligand was observed (Himmelspach et al., 2012). Similarly, a much lower electron density at the amino group is found for halogenated {1-H₂N-closo-1-CB₁₁} clusters in comparison to [1-H₂N-closo-1-CB₁₁H₁₁]^-: The non-halogenated anion is easily protonated to yield 1-H₃N-closo-1-CB₁₁H₁₁ (pK_a = 6.0) (Jelínek et al. 1986; Finze, 2009) while the attempted protonation of [1-H₂N-6-F-closo-1-CB₁₁I₁₀]^- with conc. hydrochloric acid failed (Finze & Sprenger, 2010).

Treatment of a solution of H(solv)[1-H₂N-6-F-closo-1-CB₁₁I₁₀] in dimethyl sulfoxide (DMSO) with methanol and conc. hydrochloric acid results in the slow formation of crystals of the trimethylsulfonium salt Me₃S[1-H₂N-6-F-closo-1-CB₁₁I₁₀]. Similar reactions of DMSO to result in trimethylsulfonium salts were reported earlier (e.g. Nifontova & Lavrentiev, 1993; Forrester et al., 1995; Park et al., 2005).

The title compound trimethylsulfonium-1-amino-6-fluoro-1-carba-closo-dodecaborate (Figure 1) crystallizes in the monoclinic space group P2₁/n with one formula unit in the asymmetric unit. The position of the C–NH₂ and the B–F vertex of the [1-H₂N-6-F-closo-1-CB₁₁I₁₀]^- anion are clearly assigned (i) from comparative refinements and (ii) the C–N and B–F as well as the inner-cluster C–B bond lengths are similar to values reported for [1-H₂N-closo-1-CB₁₁F₁₁]^- and [1-H₂N-6-HO-closo-1-CB₁₁F₁₀]^- (Finze et al., 2007). The bond lengths and angles of the trimethylsulfonium cation are similar to those reported for other (CH₃)₃S⁺ salts, for example (CH₃)₃SBr (Svensson & Kloo, 1996).

Related literature top

For a general overview on monocarba-closo-dodecaborates, see: Körbe et al. (2006). For the synthesis and properties of 1-aminomonocarba-closo-dodecaboron clusters, see: Jelínek et al. (1986); Srivastava et al. (1996); Finze (2007, 2009); Finze et al. (2007); Finze & Sprenger (2010). For studies on the proton affinity of halogenated {closo-1-CB₁₁} clusters, see: Himmelspach et al. (2011, 2012). For the formation of (CH₃)₃S⁺ from dimethyl sulfoxide, see: Nifontova & Lavrentiev (1993); Forrester et al. (1995); Park et al. (2005). For the structure of (CH₃)₃SBr, see: Svensson & Kloo (1996).

Experimental top

[Et₄N][1-H₂N-6-F-closo-1-CB₁₁I₁₀] (50 mg, 0.03 mmol), which was synthesized according to a published procedure (Finze & Sprenger, 2010), was suspended in a mixture of aqueous HCl (50 ml, 10% v/v) and diethyl ether (50 ml). After 30 minutes of stirring the solid dissolved. The ethereal layer was separated and the aqueous solution was extracted with Et₂O (2 x 20 ml). The combined ether phases were dried with MgSO₄, filtered, and most of the diethyl ether was removed under reduced pressure. DMSO was added (2 ml) and the residual Et₂O was removed under reduced pressure. Methanol (2 ml) and conc. hydrochloric acid (4 ml) was added. According to ¹¹B{¹H}-NMR spectroscopy the [1-H₂N-6-F-closo-1-CB₁₁I₁₀]^- anion was not protonated. After 3 month crystals of the title compound were obtained from the reaction mixture. ¹H NMR (500.13 MHz, CD₂Cl₂): d = 2.90 p.p.m. (s, (CH₃)₃S⁺) (the signal of the protons of the amino group was not observed as a result of signal broadening). ¹¹B NMR (160.46 MHz, CD₂Cl₂): d = -1.6 (s, 1 B, BF, B-2), -14.3 (s, 1 B, B-12), -17.1 (s, 2 B, B-4 and B-5), -18.9 (s, 2 B, B-8 and B-10), -18.9 (s, 2 B, B-3 and B-6), -19.2 (s, 2 B, B-7 and B-11), -21.0 (s, 1 B, B-9). IR (ATR): n_as(NH₂) 3362 versus, n_s(NH₂) 3297 cm^-1 versus.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2011); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. The structure of the asymmetric unit, showing 50% probability displacement ellipsoids. Hydrogen atoms are shown as spheres of arbitrary radius.

Trimethylsulfonium 1-amino-6-fluoro-2,3,4,5,7,8,9,10,11,12-decaiodo- 1-carba-closo-dodecaborate top

Crystal data top

C₃H₉S⁺·CH₂B₁₁FI₁₀N⁻	F(000) = 2608
M_r = 1512.11	D_x = 3.407 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 35017 reflections
a = 10.0672 (1) Å	θ = 3.0–34.0°
b = 16.7057 (2) Å	µ = 10.59 mm⁻¹
c = 17.5574 (2) Å	T = 100 K
β = 93.175 (1)°	Block, colourless
V = 2948.26 (6) Å³	0.79 × 0.28 × 0.20 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	5482 independent reflections
Radiation source: fine-focus sealed tube	5282 reflections with I > 2σ(I)
Equatorial mounted graphite monochromator	R_int = 0.029
Detector resolution: 16.2711 pixels mm^-1	θ_max = 25.5°, θ_min = 3.2°
ω scans	h = −12→12
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)]	k = −20→20
T_min = 0.040, T_max = 0.204	l = −21→21
30584 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.052	w = 1/[σ²(F_o²) + (0.014P)² + 16.P] where P = (F_o² + 2F_c²)/3
S = 1.31	(Δ/σ)_max = 0.001
5482 reflections	Δρ_max = 1.06 e Å⁻³
264 parameters	Δρ_min = −0.61 e Å⁻³
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.000548 (19)

Crystal data top

C₃H₉S⁺·CH₂B₁₁FI₁₀N⁻	V = 2948.26 (6) Å³
M_r = 1512.11	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.0672 (1) Å	µ = 10.59 mm⁻¹
b = 16.7057 (2) Å	T = 100 K
c = 17.5574 (2) Å	0.79 × 0.28 × 0.20 mm
β = 93.175 (1)°

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	5482 independent reflections
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)]	5282 reflections with I > 2σ(I)
T_min = 0.040, T_max = 0.204	R_int = 0.029
30584 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	2 restraints
wR(F²) = 0.052	H atoms treated by a mixture of independent and constrained refinement
S = 1.31	w = 1/[σ²(F_o²) + (0.014P)² + 16.P] where P = (F_o² + 2F_c²)/3
5482 reflections	Δρ_max = 1.06 e Å⁻³
264 parameters	Δρ_min = −0.61 e Å⁻³

Special details top

Experimental. CrysAlisPro, Oxford Diffraction (2009). Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (1995).

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
C1	0.2112 (5)	0.3730 (3)	0.5075 (3)	0.0111 (10)
N1	0.2183 (4)	0.4462 (3)	0.4682 (2)	0.0107 (9)
H12	0.292 (4)	0.475 (4)	0.480 (4)	0.034 (14)*
H11	0.148 (5)	0.478 (4)	0.475 (4)	0.034 (14)*
B2	0.2708 (6)	0.3639 (4)	0.6030 (3)	0.0105 (11)
I2	0.34637 (3)	0.46793 (2)	0.661845 (19)	0.01491 (9)
B3	0.3549 (6)	0.3180 (4)	0.5266 (3)	0.0087 (11)
I3	0.54383 (3)	0.36148 (2)	0.494809 (19)	0.01425 (9)
B4	0.2327 (6)	0.2837 (4)	0.4561 (3)	0.0090 (11)
I4	0.27883 (3)	0.28803 (2)	0.338027 (18)	0.01482 (9)
B5	0.0752 (6)	0.3128 (3)	0.4868 (3)	0.0088 (11)
I5	−0.08352 (3)	0.35589 (2)	0.411424 (19)	0.01391 (8)
B6	0.0985 (6)	0.3608 (4)	0.5781 (3)	0.0094 (11)
F6	0.0191 (3)	0.42395 (19)	0.59388 (17)	0.0160 (7)
B7	0.3288 (6)	0.2642 (4)	0.6136 (3)	0.0112 (12)
I7	0.49137 (3)	0.23918 (2)	0.694333 (18)	0.01296 (8)
B8	0.3054 (6)	0.2145 (4)	0.5231 (3)	0.0092 (11)
I8	0.44339 (4)	0.12326 (2)	0.49050 (2)	0.01707 (9)
B9	0.1296 (6)	0.2120 (4)	0.4979 (3)	0.0105 (11)
I9	0.03159 (4)	0.11836 (2)	0.43173 (2)	0.02016 (9)
B10	0.0465 (6)	0.2599 (4)	0.5729 (3)	0.0105 (11)
I10	−0.15349 (3)	0.23210 (2)	0.60119 (2)	0.01709 (9)
B11	0.1677 (6)	0.2908 (4)	0.6452 (3)	0.0104 (11)
I11	0.12763 (4)	0.29664 (2)	0.763929 (19)	0.01921 (9)
B12	0.1890 (6)	0.1985 (3)	0.5955 (3)	0.0089 (11)
I12	0.17344 (4)	0.08517 (2)	0.65238 (2)	0.01909 (9)
S1	0.16683 (16)	0.54368 (9)	0.20914 (9)	0.0228 (3)
C11	0.2577 (8)	0.5579 (5)	0.2974 (5)	0.044 (2)
H111	0.2125	0.5962	0.3275	0.066*
H112	0.3452	0.5773	0.2883	0.066*
H113	0.2647	0.5079	0.3243	0.066*
C12	0.2548 (8)	0.4642 (4)	0.1672 (4)	0.0377 (18)
H121	0.3398	0.4833	0.1528	0.057*
H122	0.2047	0.4450	0.1228	0.057*
H123	0.2675	0.4214	0.2034	0.057*
C13	0.0275 (7)	0.4896 (4)	0.2388 (5)	0.0403 (19)
H131	0.0574	0.4445	0.2689	0.060*
H132	−0.0246	0.4712	0.1948	0.060*
H133	−0.0258	0.5238	0.2687	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.011 (3)	0.011 (3)	0.011 (2)	0.001 (2)	0.001 (2)	0.000 (2)
N1	0.009 (2)	0.010 (2)	0.013 (2)	0.0001 (17)	0.0016 (17)	0.0037 (18)
B2	0.012 (3)	0.009 (3)	0.011 (3)	−0.001 (2)	−0.001 (2)	0.000 (2)
I2	0.01739 (18)	0.01209 (18)	0.01497 (17)	−0.00177 (13)	−0.00148 (13)	−0.00448 (13)
B3	0.007 (3)	0.011 (3)	0.008 (3)	0.001 (2)	0.001 (2)	−0.001 (2)
I3	0.00892 (16)	0.01894 (19)	0.01509 (17)	−0.00289 (13)	0.00248 (13)	0.00286 (14)
B4	0.010 (3)	0.012 (3)	0.005 (2)	0.003 (2)	−0.002 (2)	0.000 (2)
I4	0.01385 (17)	0.0234 (2)	0.00719 (16)	0.00384 (14)	0.00041 (12)	−0.00055 (13)
B5	0.008 (3)	0.008 (3)	0.011 (3)	0.001 (2)	−0.001 (2)	0.000 (2)
I5	0.01020 (17)	0.01890 (19)	0.01234 (16)	0.00449 (13)	−0.00204 (13)	0.00323 (13)
B6	0.006 (3)	0.012 (3)	0.011 (3)	0.001 (2)	0.001 (2)	0.001 (2)
F6	0.0159 (16)	0.0151 (16)	0.0170 (16)	0.0052 (13)	0.0020 (12)	−0.0007 (13)
B7	0.012 (3)	0.010 (3)	0.012 (3)	0.000 (2)	−0.003 (2)	−0.001 (2)
I7	0.01068 (17)	0.01716 (19)	0.01059 (16)	0.00013 (13)	−0.00340 (12)	0.00326 (13)
B8	0.007 (3)	0.010 (3)	0.011 (3)	0.004 (2)	0.000 (2)	0.001 (2)
I8	0.01617 (18)	0.01587 (19)	0.01883 (18)	0.00825 (14)	−0.00215 (14)	−0.00469 (14)
B9	0.008 (3)	0.010 (3)	0.013 (3)	0.003 (2)	−0.003 (2)	−0.001 (2)
I9	0.01760 (19)	0.01479 (19)	0.0273 (2)	−0.00160 (14)	−0.00620 (15)	−0.00826 (15)
B10	0.007 (3)	0.015 (3)	0.010 (3)	0.000 (2)	0.000 (2)	0.000 (2)
I10	0.00822 (17)	0.0216 (2)	0.02161 (18)	−0.00206 (14)	0.00219 (13)	0.00644 (15)
B11	0.013 (3)	0.013 (3)	0.006 (3)	−0.001 (2)	0.002 (2)	0.002 (2)
I11	0.01868 (19)	0.0299 (2)	0.00953 (16)	0.00059 (15)	0.00519 (13)	0.00235 (15)
B12	0.008 (3)	0.006 (3)	0.012 (3)	0.002 (2)	−0.001 (2)	0.004 (2)
I12	0.01749 (18)	0.01344 (19)	0.0260 (2)	−0.00212 (14)	−0.00231 (15)	0.01093 (15)
S1	0.0301 (8)	0.0173 (7)	0.0215 (7)	0.0052 (6)	0.0055 (6)	0.0044 (6)
C11	0.034 (4)	0.044 (5)	0.052 (5)	−0.004 (3)	−0.017 (4)	−0.013 (4)
C12	0.051 (5)	0.022 (4)	0.044 (4)	0.011 (3)	0.032 (4)	0.003 (3)
C13	0.024 (4)	0.030 (4)	0.067 (5)	−0.007 (3)	0.011 (3)	−0.020 (4)

Geometric parameters (Å, º) top

C1—N1	1.409 (7)	B7—B8	1.796 (8)
C1—B5	1.721 (8)	B7—B12	1.799 (8)
C1—B3	1.730 (7)	B7—B11	1.798 (8)
C1—B6	1.738 (7)	B7—I7	2.146 (6)
C1—B2	1.756 (8)	B8—B12	1.796 (8)
C1—B4	1.764 (8)	B8—B9	1.800 (8)
N1—H12	0.898 (10)	B8—I8	2.161 (6)
N1—H11	0.896 (10)	B9—B10	1.788 (8)
B2—B6	1.767 (8)	B9—B12	1.797 (8)
B2—B7	1.772 (8)	B9—I9	2.155 (6)
B2—B11	1.788 (8)	B10—B11	1.787 (8)
B2—B3	1.797 (8)	B10—B12	1.791 (8)
B2—I2	2.140 (6)	B10—I10	2.151 (6)
B3—B4	1.791 (8)	B11—B12	1.791 (8)
B3—B8	1.799 (8)	B11—I11	2.148 (6)
B3—B7	1.804 (8)	B12—I12	2.150 (6)
B3—I3	2.139 (6)	S1—C13	1.770 (7)
B4—B9	1.771 (8)	S1—C11	1.771 (7)
B4—B5	1.771 (8)	S1—C12	1.778 (6)
B4—B8	1.778 (8)	C11—H111	0.9600
B4—I4	2.150 (5)	C11—H112	0.9600
B5—B9	1.778 (8)	C11—H113	0.9600
B5—B10	1.787 (8)	C12—H121	0.9600
B5—B6	1.795 (8)	C12—H122	0.9600
B5—I5	2.143 (6)	C12—H123	0.9600
B6—F6	1.361 (7)	C13—H131	0.9600
B6—B10	1.765 (8)	C13—H132	0.9600
B6—B11	1.774 (8)	C13—H133	0.9600

N1—C1—B5	117.7 (4)	B11—B7—B3	108.3 (4)
N1—C1—B3	119.5 (4)	B2—B7—I7	119.1 (4)
B5—C1—B3	112.1 (4)	B8—B7—I7	123.5 (4)
N1—C1—B6	120.2 (4)	B12—B7—I7	124.0 (4)
B5—C1—B6	62.5 (3)	B11—B7—I7	120.8 (3)
B3—C1—B6	111.8 (4)	B3—B7—I7	121.0 (4)
N1—C1—B2	121.3 (4)	B4—B8—B12	107.7 (4)
B5—C1—B2	112.1 (4)	B4—B8—B7	108.3 (4)
B3—C1—B2	62.1 (3)	B12—B8—B7	60.1 (3)
B6—C1—B2	60.7 (3)	B4—B8—B3	60.1 (3)
N1—C1—B4	118.3 (4)	B12—B8—B3	108.0 (4)
B5—C1—B4	61.1 (3)	B7—B8—B3	60.2 (3)
B3—C1—B4	61.6 (3)	B4—B8—B9	59.3 (3)
B6—C1—B4	111.7 (4)	B12—B8—B9	59.9 (3)
B2—C1—B4	111.8 (4)	B7—B8—B9	107.9 (4)
C1—N1—H12	114 (5)	B3—B8—B9	107.3 (4)
C1—N1—H11	113 (5)	B4—B8—I8	122.0 (3)
H12—N1—H11	108 (7)	B12—B8—I8	122.5 (3)
C1—B2—B6	59.1 (3)	B7—B8—I8	120.3 (3)
C1—B2—B7	105.9 (4)	B3—B8—I8	120.4 (3)
B6—B2—B7	108.2 (4)	B9—B8—I8	123.8 (4)
C1—B2—B11	106.2 (4)	B4—B9—B5	59.9 (3)
B6—B2—B11	59.9 (3)	B4—B9—B10	108.2 (4)
B7—B2—B11	60.7 (3)	B5—B9—B10	60.2 (3)
C1—B2—B3	58.3 (3)	B4—B9—B12	108.0 (4)
B6—B2—B3	107.4 (4)	B5—B9—B12	107.9 (4)
B7—B2—B3	60.7 (3)	B10—B9—B12	59.9 (3)
B11—B2—B3	109.0 (4)	B4—B9—B8	59.7 (3)
C1—B2—I2	119.0 (3)	B5—B9—B8	107.3 (4)
B6—B2—I2	117.5 (4)	B10—B9—B8	107.6 (4)
B7—B2—I2	127.4 (4)	B12—B9—B8	59.9 (3)
B11—B2—I2	123.6 (4)	B4—B9—I9	121.9 (4)
B3—B2—I2	122.5 (4)	B5—B9—I9	119.9 (3)
C1—B3—B4	60.1 (3)	B10—B9—I9	120.2 (4)
C1—B3—B2	59.7 (3)	B12—B9—I9	122.8 (4)
B4—B3—B2	108.6 (4)	B8—B9—I9	124.3 (4)
C1—B3—B8	106.1 (4)	B6—B10—B11	59.9 (3)
B4—B3—B8	59.4 (3)	B6—B10—B5	60.7 (3)
B2—B3—B8	107.1 (4)	B11—B10—B5	108.7 (4)
C1—B3—B7	105.6 (4)	B6—B10—B9	108.4 (4)
B4—B3—B7	107.4 (4)	B11—B10—B9	108.8 (4)
B2—B3—B7	58.9 (3)	B5—B10—B9	59.6 (3)
B8—B3—B7	59.8 (3)	B6—B10—B12	107.7 (4)
C1—B3—I3	121.0 (4)	B11—B10—B12	60.1 (3)
B4—B3—I3	121.0 (3)	B5—B10—B12	107.8 (4)
B2—B3—I3	120.8 (3)	B9—B10—B12	60.3 (3)
B8—B3—I3	124.5 (3)	B6—B10—I10	118.2 (3)
B7—B3—I3	124.3 (3)	B11—B10—I10	120.6 (3)
C1—B4—B9	105.6 (4)	B5—B10—I10	120.0 (3)
C1—B4—B5	58.3 (3)	B9—B10—I10	123.8 (4)
B9—B4—B5	60.3 (3)	B12—B10—I10	125.0 (4)
C1—B4—B8	105.6 (4)	B6—B11—B10	59.4 (3)
B9—B4—B8	61.0 (3)	B6—B11—B12	107.3 (4)
B5—B4—B8	108.6 (4)	B10—B11—B12	60.1 (3)
C1—B4—B3	58.3 (3)	B6—B11—B2	59.5 (3)
B9—B4—B3	109.0 (4)	B10—B11—B2	107.0 (4)
B5—B4—B3	107.1 (4)	B12—B11—B2	107.4 (4)
B8—B4—B3	60.6 (3)	B6—B11—B7	106.7 (4)
C1—B4—I4	120.3 (3)	B10—B11—B7	107.6 (4)
B9—B4—I4	125.9 (4)	B12—B11—B7	60.2 (3)
B5—B4—I4	122.0 (3)	B2—B11—B7	59.2 (3)
B8—B4—I4	123.9 (3)	B6—B11—I11	121.8 (4)
B3—B4—I4	118.6 (3)	B10—B11—I11	123.0 (3)
C1—B5—B4	60.6 (3)	B12—B11—I11	123.1 (4)
C1—B5—B9	107.1 (4)	B2—B11—I11	121.0 (4)
B4—B5—B9	59.9 (3)	B7—B11—I11	122.1 (3)
C1—B5—B10	105.9 (4)	B11—B12—B10	59.9 (3)
B4—B5—B10	108.2 (4)	B11—B12—B8	108.5 (4)
B9—B5—B10	60.2 (3)	B10—B12—B8	107.7 (4)
C1—B5—B6	59.2 (3)	B11—B12—B9	108.3 (4)
B4—B5—B6	108.7 (4)	B10—B12—B9	59.8 (3)
B9—B5—B6	107.5 (4)	B8—B12—B9	60.2 (3)
B10—B5—B6	59.0 (3)	B11—B12—B7	60.1 (3)
C1—B5—I5	119.4 (3)	B10—B12—B7	107.4 (4)
B4—B5—I5	123.6 (3)	B8—B12—B7	60.0 (3)
B9—B5—I5	126.9 (4)	B9—B12—B7	107.9 (4)
B10—B5—I5	122.6 (3)	B11—B12—I12	121.2 (3)
B6—B5—I5	117.2 (3)	B10—B12—I12	122.0 (3)
F6—B6—C1	117.9 (4)	B8—B12—I12	121.8 (3)
F6—B6—B10	125.1 (4)	B9—B12—I12	121.6 (4)
C1—B6—B10	106.2 (4)	B7—B12—I12	122.1 (3)
F6—B6—B2	120.4 (5)	C13—S1—C11	101.0 (4)
C1—B6—B2	60.1 (3)	C13—S1—C12	99.3 (3)
B10—B6—B2	109.0 (4)	C11—S1—C12	102.5 (4)
F6—B6—B11	126.1 (4)	S1—C11—H111	109.5
C1—B6—B11	107.6 (4)	S1—C11—H112	109.5
B10—B6—B11	60.7 (3)	H111—C11—H112	109.5
B2—B6—B11	60.7 (3)	S1—C11—H113	109.5
F6—B6—B5	118.6 (4)	H111—C11—H113	109.5
C1—B6—B5	58.3 (3)	H112—C11—H113	109.5
B10—B6—B5	60.3 (3)	S1—C12—H121	109.5
B2—B6—B5	108.2 (4)	S1—C12—H122	109.5
B11—B6—B5	109.0 (4)	H121—C12—H122	109.5
B2—B7—B8	108.4 (4)	S1—C12—H123	109.5
B2—B7—B12	107.7 (4)	H121—C12—H123	109.5
B8—B7—B12	59.9 (3)	H122—C12—H123	109.5
B2—B7—B11	60.1 (3)	S1—C13—H131	109.5
B8—B7—B11	108.1 (4)	S1—C13—H132	109.5
B12—B7—B11	59.7 (3)	H131—C13—H132	109.5
B2—B7—B3	60.4 (3)	S1—C13—H133	109.5
B8—B7—B3	60.0 (3)	H131—C13—H133	109.5
B12—B7—B3	107.7 (4)	H132—C13—H133	109.5

Experimental details

Crystal data
Chemical formula	C₃H₉S⁺·CH₂B₁₁FI₁₀N⁻
M_r	1512.11
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	10.0672 (1), 16.7057 (2), 17.5574 (2)
β (°)	93.175 (1)
V (Å³)	2948.26 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	10.59
Crystal size (mm)	0.79 × 0.28 × 0.20

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction	Analytical [CrysAlis PRO (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)]
T_min, T_max	0.040, 0.204
No. of measured, independent and observed [I > 2σ(I)] reflections	30584, 5482, 5282
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.052, 1.31
No. of reflections	5482
No. of parameters	264
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.014P)² + 16.P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.06, −0.61

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2011), publCIF (Westrip, 2010).

Acknowledgements

The financial support of the Deutsche Forschungsgemeinschaft (FI 1628/2-1) is gratefully acknowledged.

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