Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812042584/ng5300sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536812042584/ng5300Isup2.hkl |
CCDC reference: 909910
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.010 Å
- R factor = 0.058
- wR factor = 0.138
- Data-to-parameter ratio = 6.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) ..... 6.51 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds ............... 0.0097 Ang PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 2
Alert level G FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C6 H3 B1 F5 Na1 Atom count from _chemical_formula_moiety:C6 H3 B1 F5 REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.61 From the CIF: _reflns_number_total 775 Count of symmetry unique reflns 784 Completeness (_total/calc) 98.85% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension . 2 PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF .... ? PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ ? PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 6
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 3 ALERT level C = Check. Ensure it is not caused by an omission or oversight 6 ALERT level G = General information/check it is not something unexpected 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
In a round bottom flask (C6F5)B(OMe)2 (0.16 g, 0.65 mmol) was dissolved in 10 ml diethyl ether. Under stirring a 1 m solution of Li[AlH4] in diethyl ether (1.2 mmol, 1.1 ml) was added via canula. A brown slurry was obtained which was treated with 3 ml aqueous NaOH (3 mmol) and 15 ml benzene. Insoluble material was removed by filtration from the organic layer. Single crystals of the title compound were obtained of the concentrated benzene solution (5 ml). Yield 20%.
Due to the absence of anomalous scatterers, the absolute structure could not be determined and 414 Friedel pairs were merged. H atoms were located in a difference map, but geometrically positioned and refined using a riding model with fixed individual displacement parameters [U(H) = 1.5 Ueq(B)] and with B—H = 0.98 Å. The BH3 group was allowed to rotate but not to tip.
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
Na+·C6H3BF5− | F(000) = 200 |
Mr = 203.88 | Dx = 1.798 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 1888 reflections |
a = 4.6813 (10) Å | θ = 3.7–25.5° |
b = 6.1986 (16) Å | µ = 0.24 mm−1 |
c = 12.993 (3) Å | T = 173 K |
β = 92.995 (17)° | Plate, colourless |
V = 376.51 (15) Å3 | 0.21 × 0.18 × 0.03 mm |
Z = 2 |
STOE IPDS II two-circle- diffractometer | 775 independent reflections |
Radiation source: fine-focus sealed tube | 601 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.116 |
ω scans | θmax = 25.6°, θmin = 3.6° |
Absorption correction: multi-scan (MULABS; Spek, 2009 and Blessing, 1995) | h = −5→5 |
Tmin = 0.951, Tmax = 0.993 | k = −6→7 |
2267 measured reflections | l = −15→15 |
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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0711P)2] where P = (Fo2 + 2Fc2)/3 |
775 reflections | (Δ/σ)max < 0.001 |
119 parameters | Δρmax = 0.37 e Å−3 |
1 restraint | Δρmin = −0.45 e Å−3 |
Na+·C6H3BF5− | V = 376.51 (15) Å3 |
Mr = 203.88 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 4.6813 (10) Å | µ = 0.24 mm−1 |
b = 6.1986 (16) Å | T = 173 K |
c = 12.993 (3) Å | 0.21 × 0.18 × 0.03 mm |
β = 92.995 (17)° |
STOE IPDS II two-circle- diffractometer | 775 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2009 and Blessing, 1995) | 601 reflections with I > 2σ(I) |
Tmin = 0.951, Tmax = 0.993 | Rint = 0.116 |
2267 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 1 restraint |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.37 e Å−3 |
775 reflections | Δρmin = −0.45 e Å−3 |
119 parameters |
Experimental. ; |
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. |
x | y | z | Uiso*/Ueq | ||
Na1 | 0.8015 (5) | 0.5576 (5) | 0.5911 (2) | 0.0289 (6) | |
B1 | 0.7013 (14) | 0.7940 (13) | 0.4048 (5) | 0.0245 (15) | |
H1A | 0.6928 | 0.9477 | 0.3873 | 0.037* | |
H1B | 0.8948 | 0.7573 | 0.4316 | 0.037* | |
H1C | 0.5643 | 0.7628 | 0.4573 | 0.037* | |
C1 | 0.6218 (11) | 0.6519 (12) | 0.3025 (5) | 0.0228 (13) | |
C2 | 0.7487 (11) | 0.4581 (11) | 0.2778 (5) | 0.0258 (14) | |
C3 | 0.6739 (13) | 0.3361 (12) | 0.1908 (5) | 0.0297 (15) | |
C4 | 0.4582 (12) | 0.4078 (14) | 0.1233 (5) | 0.0325 (16) | |
C5 | 0.3237 (12) | 0.6030 (13) | 0.1438 (5) | 0.0316 (18) | |
C6 | 0.4083 (12) | 0.7149 (12) | 0.2310 (5) | 0.0275 (15) | |
F2 | 0.9668 (7) | 0.3764 (7) | 0.3429 (3) | 0.0351 (10) | |
F3 | 0.8099 (8) | 0.1482 (7) | 0.1730 (3) | 0.0420 (11) | |
F4 | 0.3794 (9) | 0.2917 (10) | 0.0395 (3) | 0.0495 (13) | |
F5 | 0.1147 (7) | 0.6743 (8) | 0.0784 (3) | 0.0426 (12) | |
F6 | 0.2667 (7) | 0.9043 (7) | 0.2468 (3) | 0.0351 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Na1 | 0.0223 (10) | 0.0281 (14) | 0.0361 (14) | −0.0006 (11) | −0.0003 (9) | 0.0047 (13) |
B1 | 0.020 (3) | 0.028 (4) | 0.026 (3) | −0.002 (3) | 0.000 (3) | 0.002 (4) |
C1 | 0.015 (2) | 0.025 (3) | 0.028 (3) | −0.005 (2) | 0.001 (2) | 0.004 (3) |
C2 | 0.017 (2) | 0.028 (3) | 0.032 (4) | 0.003 (3) | −0.005 (2) | 0.007 (3) |
C3 | 0.028 (3) | 0.025 (4) | 0.037 (4) | 0.001 (3) | 0.008 (3) | −0.006 (3) |
C4 | 0.023 (3) | 0.044 (4) | 0.029 (3) | −0.002 (3) | −0.002 (3) | −0.006 (3) |
C5 | 0.018 (2) | 0.047 (5) | 0.028 (4) | 0.001 (3) | −0.002 (2) | 0.003 (3) |
C6 | 0.018 (3) | 0.039 (4) | 0.027 (3) | 0.007 (3) | 0.007 (2) | 0.007 (3) |
F2 | 0.0276 (18) | 0.031 (2) | 0.045 (2) | 0.0079 (18) | −0.0124 (16) | 0.003 (2) |
F3 | 0.040 (2) | 0.033 (2) | 0.052 (3) | 0.012 (2) | 0.0000 (18) | −0.009 (2) |
F4 | 0.039 (2) | 0.066 (3) | 0.043 (3) | 0.006 (2) | −0.0056 (18) | −0.022 (3) |
F5 | 0.0262 (17) | 0.068 (3) | 0.033 (2) | 0.015 (2) | −0.0083 (15) | 0.005 (2) |
F6 | 0.0262 (17) | 0.044 (3) | 0.035 (2) | 0.0156 (18) | −0.0050 (15) | −0.002 (2) |
Na1—F6i | 2.348 (5) | C2—C3 | 1.389 (10) |
Na1—F2ii | 2.392 (5) | C3—F3 | 1.353 (9) |
Na1—B1iii | 2.842 (7) | C3—C4 | 1.376 (10) |
Na1—B1i | 2.868 (8) | C4—F4 | 1.342 (9) |
B1—C1 | 1.621 (10) | C4—C5 | 1.396 (11) |
B1—H1A | 0.9800 | C5—F5 | 1.337 (7) |
B1—H1B | 0.9800 | C5—C6 | 1.370 (10) |
B1—H1C | 0.9800 | C6—F6 | 1.369 (8) |
C1—C6 | 1.385 (9) | F2—Na1iii | 2.392 (5) |
C1—C2 | 1.385 (10) | F6—Na1iv | 2.348 (5) |
C2—F2 | 1.387 (7) | ||
F6i—Na1—F2ii | 95.35 (17) | F2—C2—C1 | 119.1 (6) |
F6i—Na1—B1iii | 84.3 (2) | C3—C2—C1 | 124.6 (6) |
F2ii—Na1—B1iii | 96.5 (2) | F3—C3—C4 | 120.3 (7) |
F6i—Na1—B1i | 66.57 (18) | F3—C3—C2 | 120.5 (6) |
F2ii—Na1—B1i | 145.2 (2) | C4—C3—C2 | 119.2 (6) |
B1iii—Na1—B1i | 110.1 (3) | F4—C4—C3 | 120.4 (7) |
C1—B1—H1A | 109.5 | F4—C4—C5 | 120.8 (6) |
C1—B1—H1B | 109.5 | C3—C4—C5 | 118.8 (6) |
H1A—B1—H1B | 109.5 | F5—C5—C6 | 121.9 (7) |
C1—B1—H1C | 109.5 | F5—C5—C4 | 119.2 (6) |
H1A—B1—H1C | 109.5 | C6—C5—C4 | 118.9 (6) |
H1B—B1—H1C | 109.5 | F6—C6—C5 | 115.9 (6) |
C6—C1—C2 | 113.1 (6) | F6—C6—C1 | 118.6 (6) |
C6—C1—B1 | 121.6 (6) | C5—C6—C1 | 125.4 (6) |
C2—C1—B1 | 125.3 (6) | C2—F2—Na1iii | 145.7 (4) |
F2—C2—C3 | 116.3 (6) | C6—F6—Na1iv | 124.9 (4) |
C6—C1—C2—F2 | 179.8 (5) | F4—C4—C5—C6 | 179.2 (6) |
B1—C1—C2—F2 | −1.5 (8) | C3—C4—C5—C6 | −0.9 (9) |
C6—C1—C2—C3 | −0.1 (8) | F5—C5—C6—F6 | −0.3 (9) |
B1—C1—C2—C3 | 178.6 (6) | C4—C5—C6—F6 | −179.6 (6) |
F2—C2—C3—F3 | 0.2 (9) | F5—C5—C6—C1 | 179.8 (6) |
C1—C2—C3—F3 | −179.9 (6) | C4—C5—C6—C1 | 0.5 (9) |
F2—C2—C3—C4 | 179.7 (6) | C2—C1—C6—F6 | −179.9 (5) |
C1—C2—C3—C4 | −0.4 (9) | B1—C1—C6—F6 | 1.4 (8) |
F3—C3—C4—F4 | 0.4 (10) | C2—C1—C6—C5 | 0.0 (9) |
C2—C3—C4—F4 | −179.2 (6) | B1—C1—C6—C5 | −178.7 (6) |
F3—C3—C4—C5 | −179.6 (6) | C3—C2—F2—Na1iii | −30.8 (9) |
C2—C3—C4—C5 | 0.9 (9) | C1—C2—F2—Na1iii | 149.3 (5) |
F4—C4—C5—F5 | −0.2 (9) | C5—C6—F6—Na1iv | 151.8 (4) |
C3—C4—C5—F5 | 179.7 (6) | C1—C6—F6—Na1iv | −28.2 (7) |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+2, y+1/2, −z+1; (iii) −x+2, y−1/2, −z+1; (iv) −x+1, y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | Na+·C6H3BF5− |
Mr | 203.88 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 173 |
a, b, c (Å) | 4.6813 (10), 6.1986 (16), 12.993 (3) |
β (°) | 92.995 (17) |
V (Å3) | 376.51 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.21 × 0.18 × 0.03 |
Data collection | |
Diffractometer | STOE IPDS II two-circle- diffractometer |
Absorption correction | Multi-scan (MULABS; Spek, 2009 and Blessing, 1995) |
Tmin, Tmax | 0.951, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2267, 775, 601 |
Rint | 0.116 |
(sin θ/λ)max (Å−1) | 0.608 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.138, 1.01 |
No. of reflections | 775 |
No. of parameters | 119 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.45 |
Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).
The hydridoborates [(C6F5)BH3]- and [(C6F5)2BH2]- are convenient starting materials for the in situ generation of the boranes (C6F5)BH2 and (C6F5)2BH (Schnurr et al., 2011). In this paper we report the crystal structure of Na[(C6F5)BH3] which was obtained from the reaction mixture of (C6F5)B(OMe)2 and Li[AlH4] by a cation exchange with NaOH (Fig. 1).
The title compound (Fig. 2) is composed of discrete anions and cations. The sodium cations are surrounded by four anions with three short Na···B [Na1···B1 2.848 (8) Å, Na1···B1i 2.842 (7) Å, Na1···B1ii 2.868 (8) Å; symmetry operators: (i) -x + 2, y - 1/2, -z + 1, (ii) -x + 1, y - 1/2, -z + 1] and two short Na···F [Na1···F6ii 2.348 (5) Å, Na1···F2ii 2.392 (5) Å] contacts (Fig. 3).
It is remarkable that this is the first structure with an pentafluorophenyl ring carrying a BH3 group. A search in the Cambridge Crystallographic Database (CSD, Version 5.33 of November 2011, plus three updates (Allen, (2002). Acta Cryst. B58, 380–388) yielded no hit at all for this fragment.