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The crystal structure of the title compound, Na[(C6F5)BH3], is composed of discrete anions and cations. The sodium cations are surrounded by four anions with three short Na...B [2.848 (8), 2.842 (7) and 2.868 (8) Å] and two short Na...F contacts [2.348 (5) and 2.392 (5) Å], forming a three-dimensional network. The anion is the first structural example of a pentafluorophenyl ring carrying a BH3 group.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812042584/ng5300sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536812042584/ng5300Isup2.hkl
Contains datablock I

CCDC reference: 909910

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](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

Comment top

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.

Related literature top

For synthetic background, see: Schnurr et al. (2011). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

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%.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. Reaction scheme for obtaining the title compound.
[Figure 2] Fig. 2. Perspective view of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. Environment of a sodium cation.
Sodium pentafluorophenylborate top
Crystal data top
Na+·C6H3BF5F(000) = 200
Mr = 203.88Dx = 1.798 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 1888 reflections
a = 4.6813 (10) Åθ = 3.7–25.5°
b = 6.1986 (16) ŵ = 0.24 mm1
c = 12.993 (3) ÅT = 173 K
β = 92.995 (17)°Plate, colourless
V = 376.51 (15) Å30.21 × 0.18 × 0.03 mm
Z = 2
Data collection top
STOE IPDS II two-circle-
diffractometer
775 independent reflections
Radiation source: fine-focus sealed tube601 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.116
ω scansθmax = 25.6°, θmin = 3.6°
Absorption correction: multi-scan
(MULABS; Spek, 2009 and Blessing, 1995)
h = 55
Tmin = 0.951, Tmax = 0.993k = 67
2267 measured reflectionsl = 1515
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138H-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 parametersΔρmax = 0.37 e Å3
1 restraintΔρmin = 0.45 e Å3
Crystal data top
Na+·C6H3BF5V = 376.51 (15) Å3
Mr = 203.88Z = 2
Monoclinic, P21Mo Kα radiation
a = 4.6813 (10) ŵ = 0.24 mm1
b = 6.1986 (16) ÅT = 173 K
c = 12.993 (3) Å0.21 × 0.18 × 0.03 mm
β = 92.995 (17)°
Data collection top
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 = 0.993Rint = 0.116
2267 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0581 restraint
wR(F2) = 0.138H-atom parameters constrained
S = 1.01Δρmax = 0.37 e Å3
775 reflectionsΔρmin = 0.45 e Å3
119 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Na10.8015 (5)0.5576 (5)0.5911 (2)0.0289 (6)
B10.7013 (14)0.7940 (13)0.4048 (5)0.0245 (15)
H1A0.69280.94770.38730.037*
H1B0.89480.75730.43160.037*
H1C0.56430.76280.45730.037*
C10.6218 (11)0.6519 (12)0.3025 (5)0.0228 (13)
C20.7487 (11)0.4581 (11)0.2778 (5)0.0258 (14)
C30.6739 (13)0.3361 (12)0.1908 (5)0.0297 (15)
C40.4582 (12)0.4078 (14)0.1233 (5)0.0325 (16)
C50.3237 (12)0.6030 (13)0.1438 (5)0.0316 (18)
C60.4083 (12)0.7149 (12)0.2310 (5)0.0275 (15)
F20.9668 (7)0.3764 (7)0.3429 (3)0.0351 (10)
F30.8099 (8)0.1482 (7)0.1730 (3)0.0420 (11)
F40.3794 (9)0.2917 (10)0.0395 (3)0.0495 (13)
F50.1147 (7)0.6743 (8)0.0784 (3)0.0426 (12)
F60.2667 (7)0.9043 (7)0.2468 (3)0.0351 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Na10.0223 (10)0.0281 (14)0.0361 (14)0.0006 (11)0.0003 (9)0.0047 (13)
B10.020 (3)0.028 (4)0.026 (3)0.002 (3)0.000 (3)0.002 (4)
C10.015 (2)0.025 (3)0.028 (3)0.005 (2)0.001 (2)0.004 (3)
C20.017 (2)0.028 (3)0.032 (4)0.003 (3)0.005 (2)0.007 (3)
C30.028 (3)0.025 (4)0.037 (4)0.001 (3)0.008 (3)0.006 (3)
C40.023 (3)0.044 (4)0.029 (3)0.002 (3)0.002 (3)0.006 (3)
C50.018 (2)0.047 (5)0.028 (4)0.001 (3)0.002 (2)0.003 (3)
C60.018 (3)0.039 (4)0.027 (3)0.007 (3)0.007 (2)0.007 (3)
F20.0276 (18)0.031 (2)0.045 (2)0.0079 (18)0.0124 (16)0.003 (2)
F30.040 (2)0.033 (2)0.052 (3)0.012 (2)0.0000 (18)0.009 (2)
F40.039 (2)0.066 (3)0.043 (3)0.006 (2)0.0056 (18)0.022 (3)
F50.0262 (17)0.068 (3)0.033 (2)0.015 (2)0.0083 (15)0.005 (2)
F60.0262 (17)0.044 (3)0.035 (2)0.0156 (18)0.0050 (15)0.002 (2)
Geometric parameters (Å, º) top
Na1—F6i2.348 (5)C2—C31.389 (10)
Na1—F2ii2.392 (5)C3—F31.353 (9)
Na1—B1iii2.842 (7)C3—C41.376 (10)
Na1—B1i2.868 (8)C4—F41.342 (9)
B1—C11.621 (10)C4—C51.396 (11)
B1—H1A0.9800C5—F51.337 (7)
B1—H1B0.9800C5—C61.370 (10)
B1—H1C0.9800C6—F61.369 (8)
C1—C61.385 (9)F2—Na1iii2.392 (5)
C1—C21.385 (10)F6—Na1iv2.348 (5)
C2—F21.387 (7)
F6i—Na1—F2ii95.35 (17)F2—C2—C1119.1 (6)
F6i—Na1—B1iii84.3 (2)C3—C2—C1124.6 (6)
F2ii—Na1—B1iii96.5 (2)F3—C3—C4120.3 (7)
F6i—Na1—B1i66.57 (18)F3—C3—C2120.5 (6)
F2ii—Na1—B1i145.2 (2)C4—C3—C2119.2 (6)
B1iii—Na1—B1i110.1 (3)F4—C4—C3120.4 (7)
C1—B1—H1A109.5F4—C4—C5120.8 (6)
C1—B1—H1B109.5C3—C4—C5118.8 (6)
H1A—B1—H1B109.5F5—C5—C6121.9 (7)
C1—B1—H1C109.5F5—C5—C4119.2 (6)
H1A—B1—H1C109.5C6—C5—C4118.9 (6)
H1B—B1—H1C109.5F6—C6—C5115.9 (6)
C6—C1—C2113.1 (6)F6—C6—C1118.6 (6)
C6—C1—B1121.6 (6)C5—C6—C1125.4 (6)
C2—C1—B1125.3 (6)C2—F2—Na1iii145.7 (4)
F2—C2—C3116.3 (6)C6—F6—Na1iv124.9 (4)
C6—C1—C2—F2179.8 (5)F4—C4—C5—C6179.2 (6)
B1—C1—C2—F21.5 (8)C3—C4—C5—C60.9 (9)
C6—C1—C2—C30.1 (8)F5—C5—C6—F60.3 (9)
B1—C1—C2—C3178.6 (6)C4—C5—C6—F6179.6 (6)
F2—C2—C3—F30.2 (9)F5—C5—C6—C1179.8 (6)
C1—C2—C3—F3179.9 (6)C4—C5—C6—C10.5 (9)
F2—C2—C3—C4179.7 (6)C2—C1—C6—F6179.9 (5)
C1—C2—C3—C40.4 (9)B1—C1—C6—F61.4 (8)
F3—C3—C4—F40.4 (10)C2—C1—C6—C50.0 (9)
C2—C3—C4—F4179.2 (6)B1—C1—C6—C5178.7 (6)
F3—C3—C4—C5179.6 (6)C3—C2—F2—Na1iii30.8 (9)
C2—C3—C4—C50.9 (9)C1—C2—F2—Na1iii149.3 (5)
F4—C4—C5—F50.2 (9)C5—C6—F6—Na1iv151.8 (4)
C3—C4—C5—F5179.7 (6)C1—C6—F6—Na1iv28.2 (7)
Symmetry codes: (i) x+1, y1/2, z+1; (ii) x+2, y+1/2, z+1; (iii) x+2, y1/2, z+1; (iv) x+1, y+1/2, z+1.

Experimental details

Crystal data
Chemical formulaNa+·C6H3BF5
Mr203.88
Crystal system, space groupMonoclinic, P21
Temperature (K)173
a, b, c (Å)4.6813 (10), 6.1986 (16), 12.993 (3)
β (°) 92.995 (17)
V3)376.51 (15)
Z2
Radiation typeMo Kα
µ (mm1)0.24
Crystal size (mm)0.21 × 0.18 × 0.03
Data collection
DiffractometerSTOE IPDS II two-circle-
diffractometer
Absorption correctionMulti-scan
(MULABS; Spek, 2009 and Blessing, 1995)
Tmin, Tmax0.951, 0.993
No. of measured, independent and
observed [I > 2σ(I)] reflections
2267, 775, 601
Rint0.116
(sin θ/λ)max1)0.608
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.138, 1.01
No. of reflections775
No. of parameters119
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.37, 0.45

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

 

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