Literature DB >> 22412544

Trimethyl-sulfonium 1-amino-6-fluoro-2,3,4,5,7,8,9,10,11,12-decaiodo-1-carba-closo-dodeca-borate.

Maik Finze, Guido J Reiss.   

Abstract

In the asymmetric unit of the title salt, C(3)H(9)S(+)·CH(2)B(11)FI(10)N(-) or (CH(3))(3)S[1-H(2)N-6-F-closo-1-CB(11)I(10)], both ions lie in general positions. The anion is perfectly ordered and so the positions of the C-NH(2) vertex and the fluorine substituent are clearly assigned. The relatively short C-N bond length may be inter-preted in terms of a very electron deficient {closo-1-CB(11)} cluster.

Entities:  

Year:  2012        PMID： 22412544      PMCID： PMC3295433          DOI： 10.1107/S1600536812004424

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


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 = 1512.11 Monoclinic, 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 ▶), 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[F 2 > 2σ(F 2)] = 0.024 wR(F 2) = 0.052 S = 1.31 5482 reflections 264 parameters 2 restraints H atoms treated by a mixture of independent and constrained refinement Δρmax = 1.06 e Å−3 Δρmin = −0.61 e Å−3 Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); 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 ▶). Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812004424/ru2027sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812004424/ru2027Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C3H9S+·CH2B11FI10N−F(000) = 2608
Mr = 1512.11Dx = 3.407 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 35017 reflections
a = 10.0672 (1) Åθ = 3.0–34.0°
b = 16.7057 (2) ŵ = 10.59 mm−1
c = 17.5574 (2) ÅT = 100 K
β = 93.175 (1)°Block, colourless
V = 2948.26 (6) Å30.79 × 0.28 × 0.20 mm
Z = 4
Oxford Diffraction Xcalibur Eos diffractometer5482 independent reflections
Radiation source: fine-focus sealed tube5282 reflections with I > 2σ(I)
Equatorial mounted graphite monochromatorRint = 0.029
Detector resolution: 16.2711 pixels mm-1θmax = 25.5°, θmin = 3.2°
ω scansh = −12→12
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)]k = −20→20
Tmin = 0.040, Tmax = 0.204l = −21→21
30584 measured reflections
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.052w = 1/[σ2(Fo2) + (0.014P)2 + 16.P] where P = (Fo2 + 2Fc2)/3
S = 1.31(Δ/σ)max = 0.001
5482 reflectionsΔρmax = 1.06 e Å−3
264 parametersΔρmin = −0.61 e Å−3
2 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.000548 (19)
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.
xyzUiso*/Ueq
C10.2112 (5)0.3730 (3)0.5075 (3)0.0111 (10)
N10.2183 (4)0.4462 (3)0.4682 (2)0.0107 (9)
H120.292 (4)0.475 (4)0.480 (4)0.034 (14)*
H110.148 (5)0.478 (4)0.475 (4)0.034 (14)*
B20.2708 (6)0.3639 (4)0.6030 (3)0.0105 (11)
I20.34637 (3)0.46793 (2)0.661845 (19)0.01491 (9)
B30.3549 (6)0.3180 (4)0.5266 (3)0.0087 (11)
I30.54383 (3)0.36148 (2)0.494809 (19)0.01425 (9)
B40.2327 (6)0.2837 (4)0.4561 (3)0.0090 (11)
I40.27883 (3)0.28803 (2)0.338027 (18)0.01482 (9)
B50.0752 (6)0.3128 (3)0.4868 (3)0.0088 (11)
I5−0.08352 (3)0.35589 (2)0.411424 (19)0.01391 (8)
B60.0985 (6)0.3608 (4)0.5781 (3)0.0094 (11)
F60.0191 (3)0.42395 (19)0.59388 (17)0.0160 (7)
B70.3288 (6)0.2642 (4)0.6136 (3)0.0112 (12)
I70.49137 (3)0.23918 (2)0.694333 (18)0.01296 (8)
B80.3054 (6)0.2145 (4)0.5231 (3)0.0092 (11)
I80.44339 (4)0.12326 (2)0.49050 (2)0.01707 (9)
B90.1296 (6)0.2120 (4)0.4979 (3)0.0105 (11)
I90.03159 (4)0.11836 (2)0.43173 (2)0.02016 (9)
B100.0465 (6)0.2599 (4)0.5729 (3)0.0105 (11)
I10−0.15349 (3)0.23210 (2)0.60119 (2)0.01709 (9)
B110.1677 (6)0.2908 (4)0.6452 (3)0.0104 (11)
I110.12763 (4)0.29664 (2)0.763929 (19)0.01921 (9)
B120.1890 (6)0.1985 (3)0.5955 (3)0.0089 (11)
I120.17344 (4)0.08517 (2)0.65238 (2)0.01909 (9)
S10.16683 (16)0.54368 (9)0.20914 (9)0.0228 (3)
C110.2577 (8)0.5579 (5)0.2974 (5)0.044 (2)
H1110.21250.59620.32750.066*
H1120.34520.57730.28830.066*
H1130.26470.50790.32430.066*
C120.2548 (8)0.4642 (4)0.1672 (4)0.0377 (18)
H1210.33980.48330.15280.057*
H1220.20470.44500.12280.057*
H1230.26750.42140.20340.057*
C130.0275 (7)0.4896 (4)0.2388 (5)0.0403 (19)
H1310.05740.44450.26890.060*
H132−0.02460.47120.19480.060*
H133−0.02580.52380.26870.060*
U11U22U33U12U13U23
C10.011 (3)0.011 (3)0.011 (2)0.001 (2)0.001 (2)0.000 (2)
N10.009 (2)0.010 (2)0.013 (2)0.0001 (17)0.0016 (17)0.0037 (18)
B20.012 (3)0.009 (3)0.011 (3)−0.001 (2)−0.001 (2)0.000 (2)
I20.01739 (18)0.01209 (18)0.01497 (17)−0.00177 (13)−0.00148 (13)−0.00448 (13)
B30.007 (3)0.011 (3)0.008 (3)0.001 (2)0.001 (2)−0.001 (2)
I30.00892 (16)0.01894 (19)0.01509 (17)−0.00289 (13)0.00248 (13)0.00286 (14)
B40.010 (3)0.012 (3)0.005 (2)0.003 (2)−0.002 (2)0.000 (2)
I40.01385 (17)0.0234 (2)0.00719 (16)0.00384 (14)0.00041 (12)−0.00055 (13)
B50.008 (3)0.008 (3)0.011 (3)0.001 (2)−0.001 (2)0.000 (2)
I50.01020 (17)0.01890 (19)0.01234 (16)0.00449 (13)−0.00204 (13)0.00323 (13)
B60.006 (3)0.012 (3)0.011 (3)0.001 (2)0.001 (2)0.001 (2)
F60.0159 (16)0.0151 (16)0.0170 (16)0.0052 (13)0.0020 (12)−0.0007 (13)
B70.012 (3)0.010 (3)0.012 (3)0.000 (2)−0.003 (2)−0.001 (2)
I70.01068 (17)0.01716 (19)0.01059 (16)0.00013 (13)−0.00340 (12)0.00326 (13)
B80.007 (3)0.010 (3)0.011 (3)0.004 (2)0.000 (2)0.001 (2)
I80.01617 (18)0.01587 (19)0.01883 (18)0.00825 (14)−0.00215 (14)−0.00469 (14)
B90.008 (3)0.010 (3)0.013 (3)0.003 (2)−0.003 (2)−0.001 (2)
I90.01760 (19)0.01479 (19)0.0273 (2)−0.00160 (14)−0.00620 (15)−0.00826 (15)
B100.007 (3)0.015 (3)0.010 (3)0.000 (2)0.000 (2)0.000 (2)
I100.00822 (17)0.0216 (2)0.02161 (18)−0.00206 (14)0.00219 (13)0.00644 (15)
B110.013 (3)0.013 (3)0.006 (3)−0.001 (2)0.002 (2)0.002 (2)
I110.01868 (19)0.0299 (2)0.00953 (16)0.00059 (15)0.00519 (13)0.00235 (15)
B120.008 (3)0.006 (3)0.012 (3)0.002 (2)−0.001 (2)0.004 (2)
I120.01749 (18)0.01344 (19)0.0260 (2)−0.00212 (14)−0.00231 (15)0.01093 (15)
S10.0301 (8)0.0173 (7)0.0215 (7)0.0052 (6)0.0055 (6)0.0044 (6)
C110.034 (4)0.044 (5)0.052 (5)−0.004 (3)−0.017 (4)−0.013 (4)
C120.051 (5)0.022 (4)0.044 (4)0.011 (3)0.032 (4)0.003 (3)
C130.024 (4)0.030 (4)0.067 (5)−0.007 (3)0.011 (3)−0.020 (4)
C1—N11.409 (7)B7—B81.796 (8)
C1—B51.721 (8)B7—B121.799 (8)
C1—B31.730 (7)B7—B111.798 (8)
C1—B61.738 (7)B7—I72.146 (6)
C1—B21.756 (8)B8—B121.796 (8)
C1—B41.764 (8)B8—B91.800 (8)
N1—H120.898 (10)B8—I82.161 (6)
N1—H110.896 (10)B9—B101.788 (8)
B2—B61.767 (8)B9—B121.797 (8)
B2—B71.772 (8)B9—I92.155 (6)
B2—B111.788 (8)B10—B111.787 (8)
B2—B31.797 (8)B10—B121.791 (8)
B2—I22.140 (6)B10—I102.151 (6)
B3—B41.791 (8)B11—B121.791 (8)
B3—B81.799 (8)B11—I112.148 (6)
B3—B71.804 (8)B12—I122.150 (6)
B3—I32.139 (6)S1—C131.770 (7)
B4—B91.771 (8)S1—C111.771 (7)
B4—B51.771 (8)S1—C121.778 (6)
B4—B81.778 (8)C11—H1110.9600
B4—I42.150 (5)C11—H1120.9600
B5—B91.778 (8)C11—H1130.9600
B5—B101.787 (8)C12—H1210.9600
B5—B61.795 (8)C12—H1220.9600
B5—I52.143 (6)C12—H1230.9600
B6—F61.361 (7)C13—H1310.9600
B6—B101.765 (8)C13—H1320.9600
B6—B111.774 (8)C13—H1330.9600
N1—C1—B5117.7 (4)B11—B7—B3108.3 (4)
N1—C1—B3119.5 (4)B2—B7—I7119.1 (4)
B5—C1—B3112.1 (4)B8—B7—I7123.5 (4)
N1—C1—B6120.2 (4)B12—B7—I7124.0 (4)
B5—C1—B662.5 (3)B11—B7—I7120.8 (3)
B3—C1—B6111.8 (4)B3—B7—I7121.0 (4)
N1—C1—B2121.3 (4)B4—B8—B12107.7 (4)
B5—C1—B2112.1 (4)B4—B8—B7108.3 (4)
B3—C1—B262.1 (3)B12—B8—B760.1 (3)
B6—C1—B260.7 (3)B4—B8—B360.1 (3)
N1—C1—B4118.3 (4)B12—B8—B3108.0 (4)
B5—C1—B461.1 (3)B7—B8—B360.2 (3)
B3—C1—B461.6 (3)B4—B8—B959.3 (3)
B6—C1—B4111.7 (4)B12—B8—B959.9 (3)
B2—C1—B4111.8 (4)B7—B8—B9107.9 (4)
C1—N1—H12114 (5)B3—B8—B9107.3 (4)
C1—N1—H11113 (5)B4—B8—I8122.0 (3)
H12—N1—H11108 (7)B12—B8—I8122.5 (3)
C1—B2—B659.1 (3)B7—B8—I8120.3 (3)
C1—B2—B7105.9 (4)B3—B8—I8120.4 (3)
B6—B2—B7108.2 (4)B9—B8—I8123.8 (4)
C1—B2—B11106.2 (4)B4—B9—B559.9 (3)
B6—B2—B1159.9 (3)B4—B9—B10108.2 (4)
B7—B2—B1160.7 (3)B5—B9—B1060.2 (3)
C1—B2—B358.3 (3)B4—B9—B12108.0 (4)
B6—B2—B3107.4 (4)B5—B9—B12107.9 (4)
B7—B2—B360.7 (3)B10—B9—B1259.9 (3)
B11—B2—B3109.0 (4)B4—B9—B859.7 (3)
C1—B2—I2119.0 (3)B5—B9—B8107.3 (4)
B6—B2—I2117.5 (4)B10—B9—B8107.6 (4)
B7—B2—I2127.4 (4)B12—B9—B859.9 (3)
B11—B2—I2123.6 (4)B4—B9—I9121.9 (4)
B3—B2—I2122.5 (4)B5—B9—I9119.9 (3)
C1—B3—B460.1 (3)B10—B9—I9120.2 (4)
C1—B3—B259.7 (3)B12—B9—I9122.8 (4)
B4—B3—B2108.6 (4)B8—B9—I9124.3 (4)
C1—B3—B8106.1 (4)B6—B10—B1159.9 (3)
B4—B3—B859.4 (3)B6—B10—B560.7 (3)
B2—B3—B8107.1 (4)B11—B10—B5108.7 (4)
C1—B3—B7105.6 (4)B6—B10—B9108.4 (4)
B4—B3—B7107.4 (4)B11—B10—B9108.8 (4)
B2—B3—B758.9 (3)B5—B10—B959.6 (3)
B8—B3—B759.8 (3)B6—B10—B12107.7 (4)
C1—B3—I3121.0 (4)B11—B10—B1260.1 (3)
B4—B3—I3121.0 (3)B5—B10—B12107.8 (4)
B2—B3—I3120.8 (3)B9—B10—B1260.3 (3)
B8—B3—I3124.5 (3)B6—B10—I10118.2 (3)
B7—B3—I3124.3 (3)B11—B10—I10120.6 (3)
C1—B4—B9105.6 (4)B5—B10—I10120.0 (3)
C1—B4—B558.3 (3)B9—B10—I10123.8 (4)
B9—B4—B560.3 (3)B12—B10—I10125.0 (4)
C1—B4—B8105.6 (4)B6—B11—B1059.4 (3)
B9—B4—B861.0 (3)B6—B11—B12107.3 (4)
B5—B4—B8108.6 (4)B10—B11—B1260.1 (3)
C1—B4—B358.3 (3)B6—B11—B259.5 (3)
B9—B4—B3109.0 (4)B10—B11—B2107.0 (4)
B5—B4—B3107.1 (4)B12—B11—B2107.4 (4)
B8—B4—B360.6 (3)B6—B11—B7106.7 (4)
C1—B4—I4120.3 (3)B10—B11—B7107.6 (4)
B9—B4—I4125.9 (4)B12—B11—B760.2 (3)
B5—B4—I4122.0 (3)B2—B11—B759.2 (3)
B8—B4—I4123.9 (3)B6—B11—I11121.8 (4)
B3—B4—I4118.6 (3)B10—B11—I11123.0 (3)
C1—B5—B460.6 (3)B12—B11—I11123.1 (4)
C1—B5—B9107.1 (4)B2—B11—I11121.0 (4)
B4—B5—B959.9 (3)B7—B11—I11122.1 (3)
C1—B5—B10105.9 (4)B11—B12—B1059.9 (3)
B4—B5—B10108.2 (4)B11—B12—B8108.5 (4)
B9—B5—B1060.2 (3)B10—B12—B8107.7 (4)
C1—B5—B659.2 (3)B11—B12—B9108.3 (4)
B4—B5—B6108.7 (4)B10—B12—B959.8 (3)
B9—B5—B6107.5 (4)B8—B12—B960.2 (3)
B10—B5—B659.0 (3)B11—B12—B760.1 (3)
C1—B5—I5119.4 (3)B10—B12—B7107.4 (4)
B4—B5—I5123.6 (3)B8—B12—B760.0 (3)
B9—B5—I5126.9 (4)B9—B12—B7107.9 (4)
B10—B5—I5122.6 (3)B11—B12—I12121.2 (3)
B6—B5—I5117.2 (3)B10—B12—I12122.0 (3)
F6—B6—C1117.9 (4)B8—B12—I12121.8 (3)
F6—B6—B10125.1 (4)B9—B12—I12121.6 (4)
C1—B6—B10106.2 (4)B7—B12—I12122.1 (3)
F6—B6—B2120.4 (5)C13—S1—C11101.0 (4)
C1—B6—B260.1 (3)C13—S1—C1299.3 (3)
B10—B6—B2109.0 (4)C11—S1—C12102.5 (4)
F6—B6—B11126.1 (4)S1—C11—H111109.5
C1—B6—B11107.6 (4)S1—C11—H112109.5
B10—B6—B1160.7 (3)H111—C11—H112109.5
B2—B6—B1160.7 (3)S1—C11—H113109.5
F6—B6—B5118.6 (4)H111—C11—H113109.5
C1—B6—B558.3 (3)H112—C11—H113109.5
B10—B6—B560.3 (3)S1—C12—H121109.5
B2—B6—B5108.2 (4)S1—C12—H122109.5
B11—B6—B5109.0 (4)H121—C12—H122109.5
B2—B7—B8108.4 (4)S1—C12—H123109.5
B2—B7—B12107.7 (4)H121—C12—H123109.5
B8—B7—B1259.9 (3)H122—C12—H123109.5
B2—B7—B1160.1 (3)S1—C13—H131109.5
B8—B7—B11108.1 (4)S1—C13—H132109.5
B12—B7—B1159.7 (3)H131—C13—H132109.5
B2—B7—B360.4 (3)S1—C13—H133109.5
B8—B7—B360.0 (3)H131—C13—H133109.5
B12—B7—B3107.7 (4)H132—C13—H133109.5
  7 in total

1.  Synthesis of Highly Iodinated Icosahedral Mono- and Dicarbon Carboranes.

Authors:  Rajiv R. Srivastava; Donald K. Hamlin; D. Scott Wilbur
Journal:  J Org Chem       Date:  1996-12-13       Impact factor: 4.354

2.  Carbon extrusion/cluster contraction: synthesis of the fluorinated cyano-closo-undecaborate K2[3-NC-closo-B11F10].

Authors:  Maik Finze
Journal:  Angew Chem Int Ed Engl       Date:  2007       Impact factor: 15.336

3.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

4.  Salts of the Lewis-acidic dianion [Hg(closo-1-CB11F11)2]2-: coordination of acetonitrile and water.

Authors:  Alexander Himmelspach; Manfred Zähres; Maik Finze
Journal:  Inorg Chem       Date:  2011-03-11       Impact factor: 5.165

5.  Chemistry of the carba-closo-dodecaborate(-) anion, CB(11)H(12)(-).

Authors:  Stefanie Körbe; Peter J Schreiber; Josef Michl
Journal:  Chem Rev       Date:  2006-12       Impact factor: 60.622

6.  Synthesis and characterization of 2-mono- and 1,2-diaminocarba-closo-dodecaborates M[1-R-2-H2N-closo-CB11H10] (R=H, Ph, H2N, CyHN).

Authors:  Maik Finze
Journal:  Chemistry       Date:  2009       Impact factor: 5.236

7.  [1-H2N-CB11F11]---synthesis and reactions of a functionalized fluorinated carbadodecaborate anion.

Authors:  Maik Finze; Guido J Reiss; Manfred Zähres
Journal:  Inorg Chem       Date:  2007-10-19       Impact factor: 5.165
  7 in total

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