Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048453/sf3049sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048453/sf3049Isup2.hkl |
CCDC reference: 667134
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (K-F) = 0.001 Å
- R factor = 0.014
- wR factor = 0.035
- Data-to-parameter ratio = 21.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Ga1 PLAT732_ALERT_1_C Angle Calc 35.41(3), Rep 35.41(1) ...... 2.73 su-Ra F1 -GA1 -K1 1.555 1.555 1.555 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 2.86 Ratio
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: C12 H36 F4 Ga4 K4 Atom count from _chemical_formula_moiety:C12 H36 F4 K4 ABSTM02_ALERT_3_G The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.225 0.292 Tmin and Tmax expected: 0.133 0.195 RR = 1.128 Please check that your absorption correction is appropriate. REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values From the CIF: _diffrn_reflns_theta_max 25.85 From the CIF: _reflns_number_total 453 From the CIF: _diffrn_reflns_limit_ max hkl 21. 19. 20. From the CIF: _diffrn_reflns_limit_ min hkl -21. -5. -21. TEST1: Expected hkl limits for theta max Calculated maximum hkl 21. 21. 21. Calculated minimum hkl -21. -21. -21. 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 25.85 From the CIF: _reflns_number_total 453 Count of symmetry unique reflns 258 Completeness (_total/calc) 175.58% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 195 Fraction of Friedel pairs measured 0.756 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Ga(CH3)3 has been synthesized by reaction of GaCl3 with methyl lithium in diethylether. (KF)4·4Ga(CH3)3 was prepared by complexation with potassium fluoride in toluene similar to the procedure described by Starowieyski et al. (Starowieyski et al., 2000).
The potassium fluoride adduct (KF)4·4GaMe3, (1), is a suitable intermediate in the purification of GaMe3, since this reactive compound can be liberated by simply heating (1) in vacuum (Starowieyski et al., 2000). (1) crystallizes in space group F43c, z = 8. The K and F atoms in (1) form a heterocubane structure with the fluorine atoms coordinating to the gallium atoms of the Ga(CH3)3 groups. This extends the number of valence electrons of the gallium atoms from six to a complete octet and increases the stability significantly (Elschenbroich, 2003). The first report on the synthesis of the KF–Ga(CH3)3 complex appeared in 1974 (Wilson & Dehnicke, 1974). Originally the structure of (1) was reported in space group P43m, z = 1 (Starowieyski et al., 2000). However, then the carbon atom of the refined methyl group occupies a general position resulting in disorder with half occupancy. Isostructural with (1) is the potassium silanolate [KOSi(CH3)3]4, which also has originally been characterized by powder diffraction and described in space group P43m (Weiss et al., 1970); the structure analysis has been corrected after refinement in space group F43c (Pauer & Sheldrick, 1993).
We observed reflections with non-integer Miller indices in (1), if indexing is based on the cubic primitive cell, and succeeded in refinement in space group F43c with twice the lattice parameter a and without disorder of the methyl group. Similar to the isostructural potassium silanolate, these reflections were obviously not recognized in the original structure analysis. This is understandable, since only few reflections hkl with odd indices are allowed at low diffraction angles because of the zonal extinctions in F43c, that allow Miller indices hhl only for h,l = 2n. Therefore only two reflections with odd indices at 2Θ angles below 20° can be observed. A data set collected at 180 K gives the same results with lattice parameter a = 17.608 (2) Å and smaller thermal ellipsoids.
The unit cell of (1) contains eight formula units (KF)4·4Ga(CH3)3 with the K, F and Ga atoms on the threefold axes. The K4F4 heterocubane shows K–F–K angles of 98.07 (5) °. The main difference to the description in P43m is the well ordered arrangement of the methyl groups. Important geometric parameters of (1) are summerized in table 2.
For related literature, see: Elschenbroich (2003); Pauer & Sheldrick (1993); Sheldrick (1997); Starowieyski et al. (2000); Weiss et al. (1970); Wilson & Dehnicke (1974).
Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005) and X-RED (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND2 (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Fig. 1. Structure of (KF)4·4Ga(CH3)3 showing 50% probability ellipsoids (hydrogen atoms omitted). |
[K4Ga4(CH3)12F4] | Dx = 1.640 Mg m−3 |
Mr = 691.69 | Mo Kα radiation, λ = 0.71073 Å |
Cubic, F43c | Cell parameters from 4321 reflections |
Hall symbol: F -4c 2 3 | θ = 2.0–29.6° |
a = 17.760 (2) Å | µ = 4.42 mm−1 |
V = 5601.8 (11) Å3 | T = 295 K |
Z = 8 | Block, colorless |
F(000) = 2752 | 0.48 × 0.40 × 0.37 mm |
Stoe IPDS 2T diffractometer | 453 independent reflections |
Radiation source: fine-focus sealed tube | 376 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.045 |
Detector resolution: 6.67 pixels mm-1 | θmax = 25.9°, θmin = 2.3° |
rotation method, ω scans | h = −21→21 |
Absorption correction: numerical (X-RED; Stoe & Cie, 2001) | k = −5→19 |
Tmin = 0.225, Tmax = 0.292 | l = −21→20 |
2577 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.014 | w = 1/[σ2(Fo2) + (0.013P)2 + 2.0232P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.035 | (Δ/σ)max = 0.002 |
S = 1.10 | Δρmax = 0.13 e Å−3 |
453 reflections | Δρmin = −0.18 e Å−3 |
21 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00081 (6) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 195 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.02 (2) |
[K4Ga4(CH3)12F4] | Z = 8 |
Mr = 691.69 | Mo Kα radiation |
Cubic, F43c | µ = 4.42 mm−1 |
a = 17.760 (2) Å | T = 295 K |
V = 5601.8 (11) Å3 | 0.48 × 0.40 × 0.37 mm |
Stoe IPDS 2T diffractometer | 453 independent reflections |
Absorption correction: numerical (X-RED; Stoe & Cie, 2001) | 376 reflections with I > 2σ(I) |
Tmin = 0.225, Tmax = 0.292 | Rint = 0.045 |
2577 measured reflections |
R[F2 > 2σ(F2)] = 0.014 | H-atom parameters constrained |
wR(F2) = 0.035 | Δρmax = 0.13 e Å−3 |
S = 1.10 | Δρmin = −0.18 e Å−3 |
453 reflections | Absolute structure: Flack (1983), 195 Friedel pairs |
21 parameters | Absolute structure parameter: 0.02 (2) |
0 restraints |
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 | ||
K1 | 0.57967 (2) | 0.57967 (2) | 0.42033 (2) | 0.0535 (2) | |
F1 | 0.56874 (6) | 0.56874 (6) | 0.56874 (6) | 0.0508 (5) | |
Ga1 | 0.632228 (10) | 0.632228 (10) | 0.632228 (10) | 0.03593 (14) | |
C1 | 0.62937 (17) | 0.58083 (14) | 0.73121 (12) | 0.0619 (6) | |
H1A | 0.5784 | 0.5672 | 0.7430 | 0.093* | |
H1B | 0.6484 | 0.6141 | 0.7693 | 0.093* | |
H1C | 0.6599 | 0.5363 | 0.7293 | 0.093* |
U11 | U22 | U33 | U12 | U13 | U23 | |
K1 | 0.0535 (2) | 0.0535 (2) | 0.0535 (2) | −0.00930 (18) | 0.00930 (18) | 0.00930 (18) |
F1 | 0.0508 (5) | 0.0508 (5) | 0.0508 (5) | −0.0086 (5) | −0.0086 (5) | −0.0086 (5) |
Ga1 | 0.03593 (14) | 0.03593 (14) | 0.03593 (14) | −0.00040 (7) | −0.00040 (7) | −0.00040 (7) |
C1 | 0.0710 (17) | 0.0682 (15) | 0.0465 (13) | 0.0086 (14) | 0.0009 (13) | 0.0141 (11) |
K1—F1 | 2.6501 (10) | F1—Ga1 | 1.9528 (18) |
K1—F1i | 2.6502 (10) | F1—K1i | 2.6502 (10) |
K1—F1ii | 2.6502 (10) | F1—K1ii | 2.6502 (10) |
K1—C1iii | 3.473 (2) | Ga1—C1vii | 1.982 (2) |
K1—C1iv | 3.473 (2) | Ga1—C1viii | 1.982 (2) |
K1—C1v | 3.473 (2) | Ga1—C1 | 1.982 (2) |
K1—Ga1i | 3.9881 (6) | Ga1—K1ii | 3.9882 (6) |
K1—Ga1ii | 3.9881 (5) | Ga1—K1i | 3.9882 (5) |
K1—Ga1 | 3.9881 (5) | C1—H1A | 0.96 |
K1—K1i | 4.0023 (13) | C1—H1B | 0.96 |
K1—K1ii | 4.0023 (13) | C1—H1C | 0.96 |
K1—K1vi | 4.0023 (13) | ||
F1—K1—F1i | 81.31 (6) | C1iii—K1—K1ii | 100.60 (5) |
F1—K1—F1ii | 81.31 (6) | C1iv—K1—K1ii | 149.72 (5) |
F1i—K1—F1ii | 81.31 (6) | C1v—K1—K1ii | 133.47 (4) |
F1—K1—C1iii | 95.47 (5) | Ga1i—K1—K1ii | 109.327 (10) |
F1i—K1—C1iii | 168.81 (5) | Ga1ii—K1—K1ii | 59.882 (9) |
F1ii—K1—C1iii | 108.91 (6) | Ga1—K1—K1ii | 59.884 (9) |
F1—K1—C1iv | 108.91 (6) | K1i—K1—K1ii | 60.0 |
F1i—K1—C1iv | 95.47 (5) | F1—K1—K1vi | 84.06 (4) |
F1ii—K1—C1iv | 168.81 (5) | F1i—K1—K1vi | 40.97 (2) |
C1iii—K1—C1iv | 75.35 (7) | F1ii—K1—K1vi | 40.97 (2) |
F1—K1—C1v | 168.81 (5) | C1iii—K1—K1vi | 149.72 (5) |
F1i—K1—C1v | 108.91 (6) | C1iv—K1—K1vi | 133.47 (4) |
F1ii—K1—C1v | 95.47 (5) | C1v—K1—K1vi | 100.60 (5) |
C1iii—K1—C1v | 75.35 (7) | Ga1i—K1—K1vi | 59.882 (9) |
C1iv—K1—C1v | 75.34 (7) | Ga1ii—K1—K1vi | 59.882 (9) |
F1—K1—Ga1i | 100.42 (2) | Ga1—K1—K1vi | 109.329 (11) |
F1i—K1—Ga1i | 25.27 (3) | K1i—K1—K1vi | 60.0 |
F1ii—K1—Ga1i | 100.42 (2) | K1ii—K1—K1vi | 60.0 |
C1iii—K1—Ga1i | 148.41 (5) | Ga1—F1—K1 | 119.32 (4) |
C1iv—K1—Ga1i | 73.72 (4) | Ga1—F1—K1i | 119.32 (4) |
C1v—K1—Ga1i | 90.69 (5) | K1—F1—K1i | 98.07 (5) |
F1—K1—Ga1ii | 100.42 (2) | Ga1—F1—K1ii | 119.32 (4) |
F1i—K1—Ga1ii | 100.42 (2) | K1—F1—K1ii | 98.07 (5) |
F1ii—K1—Ga1ii | 25.27 (3) | K1i—F1—K1ii | 98.06 (5) |
C1iii—K1—Ga1ii | 90.69 (5) | F1—Ga1—C1vii | 103.38 (8) |
C1iv—K1—Ga1ii | 148.41 (5) | F1—Ga1—C1viii | 103.38 (8) |
C1v—K1—Ga1ii | 73.72 (4) | C1vii—Ga1—C1viii | 114.82 (6) |
Ga1i—K1—Ga1ii | 112.761 (9) | F1—Ga1—C1 | 103.38 (8) |
F1—K1—Ga1 | 25.27 (3) | C1vii—Ga1—C1 | 114.81 (6) |
F1i—K1—Ga1 | 100.42 (2) | C1viii—Ga1—C1 | 114.81 (6) |
F1ii—K1—Ga1 | 100.42 (2) | F1—Ga1—K1 | 35.407 (11) |
C1iii—K1—Ga1 | 73.72 (4) | C1vii—Ga1—K1 | 76.52 (8) |
C1iv—K1—Ga1 | 90.69 (5) | C1viii—Ga1—K1 | 94.34 (9) |
C1v—K1—Ga1 | 148.40 (5) | C1—Ga1—K1 | 136.33 (8) |
Ga1i—K1—Ga1 | 112.763 (9) | F1—Ga1—K1ii | 35.408 (11) |
Ga1ii—K1—Ga1 | 112.763 (9) | C1vii—Ga1—K1ii | 136.33 (8) |
F1—K1—K1i | 40.97 (2) | C1viii—Ga1—K1ii | 76.52 (8) |
F1i—K1—K1i | 40.97 (2) | C1—Ga1—K1ii | 94.34 (9) |
F1ii—K1—K1i | 84.06 (4) | K1—Ga1—K1ii | 60.234 (17) |
C1iii—K1—K1i | 133.48 (4) | F1—Ga1—K1i | 35.408 (11) |
C1iv—K1—K1i | 100.60 (5) | C1vii—Ga1—K1i | 94.34 (9) |
C1v—K1—K1i | 149.72 (5) | C1viii—Ga1—K1i | 136.33 (8) |
Ga1i—K1—K1i | 59.882 (9) | C1—Ga1—K1i | 76.52 (8) |
Ga1ii—K1—K1i | 109.327 (10) | K1—Ga1—K1i | 60.234 (17) |
Ga1—K1—K1i | 59.884 (9) | K1ii—Ga1—K1i | 60.233 (17) |
F1—K1—K1ii | 40.97 (2) | Ga1—C1—H1A | 109.5 |
F1i—K1—K1ii | 84.06 (4) | Ga1—C1—H1B | 109.5 |
F1ii—K1—K1ii | 40.97 (2) | Ga1—C1—H1B | 109.5 |
Symmetry codes: (i) x, −y+1, −z+1; (ii) −x+1, y, −z+1; (iii) x, −z+3/2, −y+1; (iv) −z+3/2, y, −x+1; (v) y, x, z−1/2; (vi) −x+1, −y+1, z; (vii) z, x, y; (viii) y, z, x. |
Experimental details
Crystal data | |
Chemical formula | [K4Ga4(CH3)12F4] |
Mr | 691.69 |
Crystal system, space group | Cubic, F43c |
Temperature (K) | 295 |
a (Å) | 17.760 (2) |
V (Å3) | 5601.8 (11) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 4.42 |
Crystal size (mm) | 0.48 × 0.40 × 0.37 |
Data collection | |
Diffractometer | Stoe IPDS 2T |
Absorption correction | Numerical (X-RED; Stoe & Cie, 2001) |
Tmin, Tmax | 0.225, 0.292 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2577, 453, 376 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.613 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.014, 0.035, 1.10 |
No. of reflections | 453 |
No. of parameters | 21 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.13, −0.18 |
Absolute structure | Flack (1983), 195 Friedel pairs |
Absolute structure parameter | 0.02 (2) |
Computer programs: X-AREA (Stoe & Cie, 2005) and X-RED (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND2 (Brandenburg, 1998).
K1—F1 | 2.6501 (10) | Ga1—C1 | 1.982 (2) |
F1—Ga1 | 1.9528 (18) | ||
F1—K1—F1i | 81.31 (6) | F1—Ga1—C1 | 103.38 (8) |
K1—F1—K1i | 98.07 (5) | C1ii—Ga1—C1 | 114.81 (6) |
Symmetry codes: (i) x, −y+1, −z+1; (ii) z, x, y. |
The potassium fluoride adduct (KF)4·4GaMe3, (1), is a suitable intermediate in the purification of GaMe3, since this reactive compound can be liberated by simply heating (1) in vacuum (Starowieyski et al., 2000). (1) crystallizes in space group F43c, z = 8. The K and F atoms in (1) form a heterocubane structure with the fluorine atoms coordinating to the gallium atoms of the Ga(CH3)3 groups. This extends the number of valence electrons of the gallium atoms from six to a complete octet and increases the stability significantly (Elschenbroich, 2003). The first report on the synthesis of the KF–Ga(CH3)3 complex appeared in 1974 (Wilson & Dehnicke, 1974). Originally the structure of (1) was reported in space group P43m, z = 1 (Starowieyski et al., 2000). However, then the carbon atom of the refined methyl group occupies a general position resulting in disorder with half occupancy. Isostructural with (1) is the potassium silanolate [KOSi(CH3)3]4, which also has originally been characterized by powder diffraction and described in space group P43m (Weiss et al., 1970); the structure analysis has been corrected after refinement in space group F43c (Pauer & Sheldrick, 1993).
We observed reflections with non-integer Miller indices in (1), if indexing is based on the cubic primitive cell, and succeeded in refinement in space group F43c with twice the lattice parameter a and without disorder of the methyl group. Similar to the isostructural potassium silanolate, these reflections were obviously not recognized in the original structure analysis. This is understandable, since only few reflections hkl with odd indices are allowed at low diffraction angles because of the zonal extinctions in F43c, that allow Miller indices hhl only for h,l = 2n. Therefore only two reflections with odd indices at 2Θ angles below 20° can be observed. A data set collected at 180 K gives the same results with lattice parameter a = 17.608 (2) Å and smaller thermal ellipsoids.
The unit cell of (1) contains eight formula units (KF)4·4Ga(CH3)3 with the K, F and Ga atoms on the threefold axes. The K4F4 heterocubane shows K–F–K angles of 98.07 (5) °. The main difference to the description in P43m is the well ordered arrangement of the methyl groups. Important geometric parameters of (1) are summerized in table 2.