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metal-organic compounds
Tetrakis(diethyl ether)tetra-μ4-oxido-octakis(pentafluorophenyl)octazinc
aInstitut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany
*Correspondence e-mail: bolte@chemie.uni-frankfurt.de
Molecules of the title compound, [Zn8(C6F5)8O4(C4H10O)4], are located on a special position of . As a result, there is just one quarter-molecule in the The title compound features a Zn4O4 cube. Each Zn atom in the cube carries a pentafluorophenyl substituent. Each O atom is bonded to a further Zn atom, which is connected to a pentafluorophenyl substituent and the O atom of a diethyl ether molecule. All ether C atoms are disordered over two sets of sites with a site occupation factor of 0.51 (2) for the major occupied site.
Related literature
For background to metal organyls bearing pentafluorophenyl groups, see: Noltes & van den Hurk (1964); Hayashi et al. (2011
); Sun et al. (1998
); Weidenbruch et al. (1989
). For the values of the signals observed in the 1H NMR spectrum of free Et2O in [D8]THF, see: Fulmer et al. (2010
).
Experimental
Crystal data
|
Data collection: X-AREA (Stoe & Cie, 2001); cell X-AREA; data reduction: X-AREA; 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.
Supporting information
https://doi.org/10.1107/S160053681103697X/kj2188sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681103697X/kj2188Isup2.hkl
All transformations were carried out under an atmosphere of dry nitrogen using Schlenk techniques. Solvents (diethyl ether, toluene) were freshly distilled from sodium/benzophenone and hexane from sodium prior to use. NMR spectra were recorded on a Bruker Avance 300 (1H, 19F{1H} and a DPX 250 (13C{1H}).
values (1H, 13C{1H}) are reported in p.p.m. relative to SiMe4 and were referenced to residual solvent signals. The 19F{1H} NMR values were referenced to external CFCl3. The MALDI spectrum was recorded on a FISONS Instruments VG TofSpec using ATT as a matrix. Abbreviations: d = doublet, t = triplet, q = quartet, m = multiplet, br = broad, n.o. = signal not observed.In a round bottom flask anhydrous ZnCl2 (5.40 g, 39.6 mmol) was suspended in diethyl ether (50 ml) and cooled to -30°C. Under stirring, a solution of Mg[C6F5]Br in diethyl ether (79.4 mmol, 100 ml) was added via canula and the mixture was allowed to warm to room temperature over night. Insoluble material was removed by filtration and the solvent was evaporated under reduced pressure. A viscous brown slurry was obtained which was heated to 140°C for a period of approximately 3 h. The residue obtained was dissolved in a 2 : 1 mixture of toluene and hexane and stored at -30°C for 24 h. After the first crystal crop of (Et2O)2Zn[C6F5]2 had been separated the mother liquor was stored at -30°C for a period of approximately two months yielding crystals of the title compound. This can be attributed to the intrusion of moisture over the period of storage. 1H (300.0 MHz, [D8]THF, 25°C): δ = 3.39 (q, 3JH—H = 7.0 Hz, O(CH2CH3)2) (the values for the signals observed in the 1H NMR spectrum equal the values published for free Et2O in [D8]THF; Fulmer et al., 2010), 1.11 p.p.m. (t, 3JH—H = 7.0 Hz, O(CH2CH3)2); 13C{1H} NMR (62.9 MHz, [D8]THF, 25°C): δ = 149.5 (br d, 1JC—F = 226 Hz, (o-C6F5)-a or b), 149.2 (br d, 1JC—F = 223 Hz, (o-C6F5)-a or b), 140.5 (br d, 1JC—F = 258 Hz, (p-C6F5)-a,b), 137.1 p.p.m. (br d, 1JC—F = 249 Hz, (m-C6F5)-a,b), Et2O Signals, n.o. (ZnC); 19F{1H} NMR (282.3 MHz, [D8]THF, 25°C): δ = -111.42 (m, (o-C6F5)-a or b), -114.53 (m, (o-C6F5)-a or b), -156.20 (t, 3JF—F = 19 Hz, (p-C6F5)-a or b), -156.58 (t, 3JF—F = 19 Hz, (p-C6F5)-a or b), -161.32 (m, (m-C6F5)-a or b), -161.65 p.p.m. (m, (m-C6F5)-a or b). MALDI+ m/z (%): 554.89 (100) [C6F5(Et2O)ZnOZnC6F5+1]+, calcd for [C6F5(Et2O)ZnOZnC6F5+1]+: 554.91 (100).
H atoms were geometrically positioned and refined using a riding model with fixed individual displacement parameters [U(H) = 1.2 Ueq(C) or U(H) = 1.5 Ueq(Cmethyl)] using a riding model with C—H(methylene) = 0.99Å or C—H(methyl) = 0.98 Å, respectively.
Since the first synthesis of Zn[C6F5]2 in 1964 many applications of synthesized pentafluorophenyl organyls have been documented (Noltes & van den Hurk, 1964). Despite the long existence and common usage of Zn[C6F5]2, its reactivity towards water has not yet been investigated well. Very recently we have studied the chemical behavior of a series of mesityl derivatives of group 12 elements (Hayashi et al., 2011). It has been shown that the Zn derivative Zn[Mes]2 is more reactive towards acids than M[Mes]2 (M = Cd, Hg). In this paper we report the
of the product which was obtained from the 1 : 1 reaction of (Et2O)2Zn[C6F5]2 with water. Bis(pentafluorophenyl)zinc was synthesized by slight modification of the method reported in the literature via conversion of Mg[C6F5]Br with ZnCl2 in diethyl ether (Noltes & van den Hurk, 1964; Sun et al., 1998). It is interesting to note that the partial hydrolysis of (Et2O)2Zn[C6F5]2 yields the oxide [C6F5(Et2O)ZnOZnC6F5]4 whereas the 1 : 1 reaction of the corresponding Cd[C6F5]2 with water produces the hydroxy derivative [C6F5CdOH]4 (Weidenbruch et al., 1989). In the solid state the Cd hydroxide [C6F5CdOH]4 also displays a heterocubane structure.Molecules of the title compound, C64H40F40O8Zn8, are located on a special position of 4. As a result of that, there is just a quarter of a molecule in the The title compound features an Zn4O4 cube. Each Zn atom in the cube carries a pentafluorophenyl substituent. Each O atom is bonded to a further Zn atom which is connected to a pentafluorophenyl substituent and the O atom of a diethyl ether molecule.
For background to pentafluorophenyl organyls, see: Noltes & van den Hurk (1964); Hayashi et al. (2011); Sun et al. (1998); Weidenbruch et al. (1989). For the
values for the signals observed in the 1H NMR spectrum of free Et2O in [D8]THF, see: Fulmer et al. (2010).Data collection: X-AREA (Stoe & Cie, 2001); cell
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).[Zn8(C6F5)8O4(C4H10O)4] | Dx = 1.705 Mg m−3 |
Mr = 2219.92 | Mo Kα radiation, λ = 0.71073 Å |
Cubic, P43n | Cell parameters from 44493 reflections |
Hall symbol: P -4n 2 3 | θ = 2.5–25.8° |
a = 23.4948 (6) Å | µ = 2.31 mm−1 |
V = 12969.3 (6) Å3 | T = 173 K |
Z = 6 | Block, colourless |
F(000) = 6528 | 0.35 × 0.33 × 0.32 mm |
Stoe IPDS II two-circle diffractometer | 4000 independent reflections |
Radiation source: fine-focus sealed tube | 3655 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.096 |
ω scans | θmax = 25.5°, θmin = 2.5° |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | h = −27→28 |
Tmin = 0.498, Tmax = 0.525 | k = −18→28 |
75864 measured reflections | l = −28→28 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.038 | w = 1/[σ2(Fo2) + (0.0574P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.093 | (Δ/σ)max = 0.001 |
S = 1.08 | Δρmax = 0.57 e Å−3 |
4000 reflections | Δρmin = −0.40 e Å−3 |
271 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00131 (12) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 1839 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.002 (19) |
[Zn8(C6F5)8O4(C4H10O)4] | Z = 6 |
Mr = 2219.92 | Mo Kα radiation |
Cubic, P43n | µ = 2.31 mm−1 |
a = 23.4948 (6) Å | T = 173 K |
V = 12969.3 (6) Å3 | 0.35 × 0.33 × 0.32 mm |
Stoe IPDS II two-circle diffractometer | 4000 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | 3655 reflections with I > 2σ(I) |
Tmin = 0.498, Tmax = 0.525 | Rint = 0.096 |
75864 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.093 | Δρmax = 0.57 e Å−3 |
S = 1.08 | Δρmin = −0.40 e Å−3 |
4000 reflections | Absolute structure: Flack (1983), 1839 Friedel pairs |
271 parameters | Absolute structure parameter: −0.002 (19) |
0 restraints |
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 | Occ. (<1) | |
Zn1 | 0.50037 (3) | 0.061641 (18) | 0.20605 (2) | 0.03607 (14) | |
Zn2 | 0.48836 (2) | 0.12803 (2) | 0.33083 (3) | 0.04580 (17) | |
O1 | 0.50255 (15) | 0.06020 (12) | 0.29312 (12) | 0.0371 (6) | |
C1 | 0.4214 (3) | 0.1702 (3) | 0.3561 (3) | 0.0620 (16) | |
C2 | 0.4150 (3) | 0.1966 (3) | 0.4078 (3) | 0.077 (2) | |
C3 | 0.3657 (5) | 0.2226 (4) | 0.4255 (4) | 0.110 (3) | |
C4 | 0.3189 (5) | 0.2225 (5) | 0.3911 (6) | 0.135 (5) | |
C5 | 0.3221 (3) | 0.1967 (4) | 0.3404 (5) | 0.114 (4) | |
C6 | 0.3732 (3) | 0.1700 (3) | 0.3230 (4) | 0.078 (2) | |
C11 | 0.51854 (19) | 0.1320 (2) | 0.1628 (2) | 0.0425 (10) | |
C12 | 0.5218 (2) | 0.18472 (19) | 0.1880 (2) | 0.0441 (11) | |
C13 | 0.5437 (3) | 0.2323 (2) | 0.1619 (3) | 0.0557 (14) | |
C14 | 0.5638 (3) | 0.2287 (2) | 0.1076 (3) | 0.0542 (13) | |
C15 | 0.5611 (3) | 0.1768 (3) | 0.0799 (2) | 0.0552 (13) | |
C16 | 0.5389 (2) | 0.1301 (2) | 0.1077 (2) | 0.0483 (12) | |
F2 | 0.4605 (3) | 0.1988 (2) | 0.44346 (18) | 0.1052 (16) | |
F3 | 0.3626 (4) | 0.2482 (3) | 0.4764 (3) | 0.179 (4) | |
F4 | 0.2699 (4) | 0.2452 (4) | 0.4065 (4) | 0.230 (6) | |
F5 | 0.2763 (2) | 0.1940 (3) | 0.3044 (4) | 0.169 (3) | |
F6 | 0.37461 (18) | 0.1443 (2) | 0.2707 (2) | 0.0906 (13) | |
F12 | 0.5028 (2) | 0.19094 (11) | 0.24282 (12) | 0.0634 (8) | |
F13 | 0.5465 (2) | 0.28246 (13) | 0.18992 (18) | 0.0851 (12) | |
F14 | 0.58640 (19) | 0.27394 (15) | 0.08172 (19) | 0.0782 (11) | |
F15 | 0.5811 (2) | 0.17297 (16) | 0.02661 (16) | 0.0878 (13) | |
F16 | 0.53988 (18) | 0.08019 (14) | 0.07952 (15) | 0.0698 (10) | |
O2 | 0.5635 (2) | 0.1608 (3) | 0.3571 (3) | 0.100 (2) | |
C21 | 0.6146 (17) | 0.1819 (17) | 0.3404 (17) | 0.146 (15)* | 0.38 (2) |
H21A | 0.6265 | 0.1634 | 0.3044 | 0.175* | 0.38 (2) |
H21B | 0.6437 | 0.1733 | 0.3697 | 0.175* | 0.38 (2) |
C21' | 0.5649 (6) | 0.2278 (6) | 0.3605 (6) | 0.082 (4)* | 0.62 (2) |
H21C | 0.5293 | 0.2433 | 0.3442 | 0.099* | 0.62 (2) |
H21D | 0.5671 | 0.2397 | 0.4008 | 0.099* | 0.62 (2) |
C22 | 0.6107 (12) | 0.2494 (8) | 0.3312 (10) | 0.265 (12) | |
H22A | 0.5833 | 0.2656 | 0.3583 | 0.397* | 0.38 (2) |
H22B | 0.5981 | 0.2575 | 0.2923 | 0.397* | 0.38 (2) |
H22C | 0.6482 | 0.2665 | 0.3375 | 0.397* | 0.38 (2) |
H22D | 0.6171 | 0.2890 | 0.3428 | 0.397* | 0.62 (2) |
H22E | 0.6030 | 0.2480 | 0.2903 | 0.397* | 0.62 (2) |
H22F | 0.6447 | 0.2268 | 0.3398 | 0.397* | 0.62 (2) |
C23 | 0.5877 (7) | 0.1302 (8) | 0.4201 (8) | 0.079 (5)* | 0.49 (2) |
H23A | 0.6238 | 0.1099 | 0.4125 | 0.095* | 0.49 (2) |
H23B | 0.5959 | 0.1609 | 0.4479 | 0.095* | 0.49 (2) |
C24 | 0.5464 (9) | 0.0897 (8) | 0.4457 (8) | 0.089 (6)* | 0.49 (2) |
H24A | 0.5658 | 0.0663 | 0.4743 | 0.133* | 0.49 (2) |
H24B | 0.5307 | 0.0652 | 0.4159 | 0.133* | 0.49 (2) |
H24C | 0.5155 | 0.1110 | 0.4639 | 0.133* | 0.49 (2) |
C23' | 0.6024 (6) | 0.1326 (6) | 0.3793 (6) | 0.069 (5)* | 0.51 (2) |
H23C | 0.6346 | 0.1576 | 0.3901 | 0.083* | 0.51 (2) |
H23D | 0.6165 | 0.1031 | 0.3527 | 0.083* | 0.51 (2) |
C24' | 0.5754 (9) | 0.1044 (9) | 0.4335 (8) | 0.086 (5)* | 0.51 (2) |
H24D | 0.6040 | 0.0808 | 0.4526 | 0.129* | 0.51 (2) |
H24E | 0.5431 | 0.0806 | 0.4221 | 0.129* | 0.51 (2) |
H24F | 0.5622 | 0.1341 | 0.4596 | 0.129* | 0.51 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0371 (3) | 0.0301 (2) | 0.0410 (3) | −0.0003 (2) | 0.0001 (3) | 0.00158 (19) |
Zn2 | 0.0421 (3) | 0.0406 (3) | 0.0547 (3) | 0.0011 (2) | 0.0038 (2) | −0.0109 (2) |
O1 | 0.0337 (14) | 0.0367 (14) | 0.0410 (14) | 0.0009 (14) | 0.0006 (15) | −0.0018 (12) |
C1 | 0.066 (4) | 0.047 (3) | 0.073 (4) | 0.006 (3) | 0.025 (3) | 0.010 (3) |
C2 | 0.085 (5) | 0.067 (4) | 0.078 (5) | 0.028 (4) | 0.026 (4) | 0.010 (3) |
C3 | 0.137 (9) | 0.108 (7) | 0.084 (6) | 0.046 (6) | 0.057 (6) | 0.008 (5) |
C4 | 0.109 (8) | 0.163 (10) | 0.133 (9) | 0.086 (8) | 0.072 (8) | 0.056 (8) |
C5 | 0.059 (5) | 0.123 (7) | 0.160 (9) | 0.030 (5) | 0.027 (5) | 0.080 (7) |
C6 | 0.062 (4) | 0.068 (4) | 0.103 (6) | 0.012 (3) | 0.022 (4) | 0.035 (4) |
C11 | 0.042 (2) | 0.039 (2) | 0.047 (3) | 0.0014 (19) | −0.0014 (19) | 0.004 (2) |
C12 | 0.052 (3) | 0.032 (2) | 0.049 (3) | −0.0018 (19) | 0.008 (2) | 0.0038 (19) |
C13 | 0.066 (3) | 0.033 (3) | 0.068 (4) | 0.000 (2) | 0.011 (3) | 0.000 (2) |
C14 | 0.059 (3) | 0.039 (3) | 0.065 (3) | −0.003 (2) | 0.013 (3) | 0.014 (2) |
C15 | 0.065 (3) | 0.055 (3) | 0.045 (3) | 0.001 (3) | 0.014 (2) | 0.014 (2) |
C16 | 0.057 (3) | 0.037 (3) | 0.051 (3) | 0.000 (2) | −0.001 (2) | 0.005 (2) |
F2 | 0.143 (4) | 0.107 (3) | 0.066 (3) | 0.031 (3) | 0.020 (3) | −0.018 (2) |
F3 | 0.243 (9) | 0.166 (6) | 0.128 (5) | 0.095 (6) | 0.100 (5) | −0.006 (4) |
F4 | 0.170 (7) | 0.269 (10) | 0.251 (9) | 0.169 (7) | 0.136 (7) | 0.128 (8) |
F5 | 0.064 (3) | 0.209 (7) | 0.234 (8) | 0.047 (4) | 0.016 (4) | 0.103 (6) |
F6 | 0.066 (2) | 0.094 (3) | 0.111 (4) | −0.005 (2) | −0.013 (2) | 0.017 (3) |
F12 | 0.093 (2) | 0.0402 (14) | 0.0566 (16) | −0.0037 (18) | 0.024 (2) | 0.0002 (12) |
F13 | 0.131 (3) | 0.0357 (17) | 0.089 (3) | −0.0218 (19) | 0.031 (3) | −0.0054 (17) |
F14 | 0.092 (3) | 0.0508 (19) | 0.092 (3) | −0.0078 (18) | 0.029 (2) | 0.0174 (18) |
F15 | 0.135 (4) | 0.067 (2) | 0.061 (2) | 0.004 (2) | 0.044 (2) | 0.0093 (18) |
F16 | 0.110 (3) | 0.0468 (17) | 0.0532 (18) | −0.0039 (18) | 0.0130 (19) | −0.0072 (14) |
O2 | 0.064 (3) | 0.113 (4) | 0.124 (5) | −0.027 (3) | 0.006 (3) | −0.065 (4) |
C22 | 0.39 (3) | 0.168 (18) | 0.24 (2) | −0.10 (2) | 0.00 (2) | −0.021 (16) |
Zn1—C11 | 1.987 (5) | C15—F15 | 1.339 (6) |
Zn1—O1i | 1.988 (3) | C15—C16 | 1.379 (7) |
Zn1—O1 | 2.047 (3) | C16—F16 | 1.347 (6) |
Zn1—O1ii | 2.062 (3) | O2—C23' | 1.244 (14) |
Zn1—Zn1iii | 2.8965 (8) | O2—C21 | 1.36 (4) |
Zn1—Zn1ii | 2.9087 (8) | O2—C21' | 1.576 (14) |
Zn1—Zn1i | 2.9087 (8) | O2—C23 | 1.74 (2) |
Zn2—O1 | 1.854 (3) | C21—C22 | 1.61 (4) |
Zn2—C1 | 1.951 (6) | C21—H21A | 0.9900 |
Zn2—O2 | 2.022 (5) | C21—H21B | 0.9900 |
O1—Zn1ii | 1.988 (3) | C21'—C22 | 1.37 (2) |
O1—Zn1i | 2.062 (3) | C21'—H21C | 0.9900 |
C1—C2 | 1.373 (10) | C21'—H21D | 0.9900 |
C1—C6 | 1.373 (11) | C22—H22A | 0.9800 |
C2—F2 | 1.359 (9) | C22—H22B | 0.9800 |
C2—C3 | 1.373 (11) | C22—H22C | 0.9800 |
C3—F3 | 1.340 (11) | C22—H22D | 0.9800 |
C3—C4 | 1.365 (17) | C22—H22E | 0.9800 |
C4—F4 | 1.319 (9) | C22—H22F | 0.9800 |
C4—C5 | 1.339 (17) | C23—C24 | 1.49 (3) |
C5—F5 | 1.371 (12) | C23—H23A | 0.9900 |
C5—C6 | 1.415 (11) | C23—H23B | 0.9900 |
C6—F6 | 1.370 (10) | C24—H24A | 0.9800 |
C11—C12 | 1.375 (7) | C24—H24B | 0.9800 |
C11—C16 | 1.381 (7) | C24—H24C | 0.9800 |
C12—F12 | 1.373 (6) | C23'—C24' | 1.57 (2) |
C12—C13 | 1.374 (7) | C23'—H23C | 0.9900 |
C13—F13 | 1.352 (7) | C23'—H23D | 0.9900 |
C13—C14 | 1.363 (8) | C24'—H24D | 0.9800 |
C14—F14 | 1.335 (6) | C24'—H24E | 0.9800 |
C14—C15 | 1.385 (8) | C24'—H24F | 0.9800 |
C11—Zn1—O1i | 137.71 (16) | F16—C16—C11 | 119.6 (4) |
C11—Zn1—O1 | 121.31 (16) | C15—C16—C11 | 123.3 (5) |
O1i—Zn1—O1 | 89.80 (12) | C23'—O2—C21 | 70.4 (17) |
C11—Zn1—O1ii | 117.83 (16) | C23'—O2—C21' | 119.7 (9) |
O1i—Zn1—O1ii | 88.69 (11) | C21—O2—C23 | 96.1 (18) |
O1—Zn1—O1ii | 87.78 (12) | C21'—O2—C23 | 111.2 (9) |
C11—Zn1—Zn1iii | 146.43 (14) | C23'—O2—Zn2 | 124.5 (8) |
O1i—Zn1—Zn1iii | 45.37 (9) | C21—O2—Zn2 | 145.4 (18) |
O1—Zn1—Zn1iii | 89.06 (8) | C21'—O2—Zn2 | 114.4 (6) |
O1ii—Zn1—Zn1iii | 43.33 (9) | C23—O2—Zn2 | 112.8 (7) |
C11—Zn1—Zn1ii | 132.34 (14) | O2—C21—C22 | 110 (3) |
O1i—Zn1—Zn1ii | 89.85 (8) | O2—C21—H21A | 109.6 |
O1—Zn1—Zn1ii | 43.08 (9) | C22—C21—H21A | 109.6 |
O1ii—Zn1—Zn1ii | 44.72 (8) | O2—C21—H21B | 109.6 |
Zn1iii—Zn1—Zn1ii | 60.137 (9) | C22—C21—H21B | 109.6 |
C11—Zn1—Zn1i | 151.96 (14) | H21A—C21—H21B | 108.1 |
O1i—Zn1—Zn1i | 44.68 (8) | C22—C21'—O2 | 111.2 (13) |
O1—Zn1—Zn1i | 45.14 (9) | C22—C21'—H21C | 109.4 |
O1ii—Zn1—Zn1i | 88.44 (8) | O2—C21'—H21C | 109.4 |
Zn1iii—Zn1—Zn1i | 60.137 (9) | C22—C21'—H21D | 109.4 |
Zn1ii—Zn1—Zn1i | 59.724 (18) | O2—C21'—H21D | 109.4 |
O1—Zn2—C1 | 136.6 (2) | H21C—C21'—H21D | 108.0 |
O1—Zn2—O2 | 108.4 (2) | C21'—C22—C21 | 67.1 (16) |
C1—Zn2—O2 | 114.7 (2) | C21'—C22—H22A | 46.1 |
Zn2—O1—Zn1ii | 137.41 (17) | C21—C22—H22A | 109.5 |
Zn2—O1—Zn1 | 117.33 (14) | C21'—C22—H22B | 107.6 |
Zn1ii—O1—Zn1 | 92.24 (12) | C21—C22—H22B | 109.5 |
Zn2—O1—Zn1i | 116.75 (17) | H22A—C22—H22B | 109.5 |
Zn1ii—O1—Zn1i | 91.30 (11) | C21'—C22—H22C | 141.3 |
Zn1—O1—Zn1i | 90.14 (12) | C21—C22—H22C | 109.5 |
C2—C1—C6 | 114.3 (6) | H22A—C22—H22C | 109.5 |
C2—C1—Zn2 | 125.9 (6) | H22B—C22—H22C | 109.5 |
C6—C1—Zn2 | 119.4 (5) | C21'—C22—H22D | 109.5 |
F2—C2—C3 | 117.4 (8) | C21—C22—H22D | 153.1 |
F2—C2—C1 | 118.4 (6) | C21'—C22—H22E | 109.5 |
C3—C2—C1 | 124.1 (9) | H22C—C22—H22E | 109.2 |
F3—C3—C4 | 119.0 (9) | H22D—C22—H22E | 109.5 |
F3—C3—C2 | 121.0 (11) | C21'—C22—H22F | 109.5 |
C4—C3—C2 | 120.0 (9) | H22D—C22—H22F | 109.5 |
F4—C4—C5 | 118.4 (14) | H22E—C22—H22F | 109.5 |
F4—C4—C3 | 122.8 (13) | C24—C23—O2 | 113.2 (12) |
C5—C4—C3 | 118.8 (8) | C24—C23—H23A | 108.9 |
C4—C5—F5 | 121.7 (9) | O2—C23—H23A | 108.9 |
C4—C5—C6 | 120.4 (10) | C24—C23—H23B | 108.9 |
F5—C5—C6 | 117.9 (11) | O2—C23—H23B | 108.9 |
F6—C6—C1 | 119.3 (6) | H23A—C23—H23B | 107.7 |
F6—C6—C5 | 118.4 (8) | C23—C24—H24A | 109.5 |
C1—C6—C5 | 122.3 (9) | C23—C24—H24B | 109.5 |
C12—C11—C16 | 114.4 (4) | H24A—C24—H24B | 109.5 |
C12—C11—Zn1 | 122.8 (4) | C23—C24—H24C | 109.5 |
C16—C11—Zn1 | 121.8 (4) | H24A—C24—H24C | 109.5 |
C11—C12—F12 | 118.8 (4) | H24B—C24—H24C | 109.5 |
C11—C12—C13 | 124.2 (5) | O2—C23'—C24' | 105.6 (12) |
F12—C12—C13 | 117.0 (4) | O2—C23'—H23C | 110.6 |
F13—C13—C14 | 119.5 (5) | C24'—C23'—H23C | 110.6 |
F13—C13—C12 | 120.7 (5) | O2—C23'—H23D | 110.6 |
C14—C13—C12 | 119.7 (5) | C24'—C23'—H23D | 110.6 |
F14—C14—C13 | 121.0 (5) | H23C—C23'—H23D | 108.8 |
F14—C14—C15 | 120.3 (5) | C23'—C24'—H24D | 109.5 |
C13—C14—C15 | 118.7 (5) | C23'—C24'—H24E | 109.5 |
F15—C15—C16 | 121.5 (5) | H24D—C24'—H24E | 109.5 |
F15—C15—C14 | 118.9 (5) | C23'—C24'—H24F | 109.5 |
C16—C15—C14 | 119.6 (5) | H24D—C24'—H24F | 109.5 |
F16—C16—C15 | 117.0 (5) | H24E—C24'—H24F | 109.5 |
C1—Zn2—O1—Zn1ii | −146.6 (3) | O1—Zn1—C11—C16 | 154.2 (4) |
O2—Zn2—O1—Zn1ii | 26.8 (4) | O1ii—Zn1—C11—C16 | 48.6 (5) |
C1—Zn2—O1—Zn1 | 84.5 (3) | Zn1iii—Zn1—C11—C16 | 2.3 (6) |
O2—Zn2—O1—Zn1 | −102.0 (3) | Zn1ii—Zn1—C11—C16 | 101.3 (4) |
C1—Zn2—O1—Zn1i | −20.8 (4) | Zn1i—Zn1—C11—C16 | −153.7 (3) |
O2—Zn2—O1—Zn1i | 152.7 (3) | C16—C11—C12—F12 | −179.8 (5) |
C11—Zn1—O1—Zn2 | 27.9 (3) | Zn1—C11—C12—F12 | −11.1 (7) |
O1i—Zn1—O1—Zn2 | −121.8 (2) | C16—C11—C12—C13 | −0.5 (8) |
O1ii—Zn1—O1—Zn2 | 149.5 (2) | Zn1—C11—C12—C13 | 168.2 (4) |
Zn1iii—Zn1—O1—Zn2 | −167.19 (17) | C11—C12—C13—F13 | −178.7 (5) |
Zn1ii—Zn1—O1—Zn2 | 148.2 (3) | F12—C12—C13—F13 | 0.6 (8) |
Zn1i—Zn1—O1—Zn2 | −120.5 (2) | C11—C12—C13—C14 | 0.0 (9) |
C11—Zn1—O1—Zn1ii | −120.25 (17) | F12—C12—C13—C14 | 179.4 (5) |
O1ii—Zn1—O1—Zn1ii | 1.30 (11) | F13—C13—C14—F14 | 0.2 (10) |
Zn1iii—Zn1—O1—Zn1ii | 44.64 (9) | C12—C13—C14—F14 | −178.6 (6) |
Zn1i—Zn1—O1—Zn1ii | 91.31 (11) | F13—C13—C14—C15 | 179.4 (6) |
C11—Zn1—O1—Zn1i | 148.44 (17) | C12—C13—C14—C15 | 0.6 (9) |
O1i—Zn1—O1—Zn1i | −1.31 (11) | F14—C14—C15—F15 | −0.5 (9) |
Zn1iii—Zn1—O1—Zn1i | −46.67 (9) | C13—C14—C15—F15 | −179.7 (6) |
Zn1ii—Zn1—O1—Zn1i | −91.31 (11) | F14—C14—C15—C16 | 178.5 (6) |
O1—Zn2—C1—C2 | 136.8 (5) | C13—C14—C15—C16 | −0.7 (9) |
O2—Zn2—C1—C2 | −36.4 (7) | F15—C15—C16—F16 | 2.1 (9) |
O1—Zn2—C1—C6 | −36.3 (6) | C14—C15—C16—F16 | −176.9 (5) |
O2—Zn2—C1—C6 | 150.5 (5) | F15—C15—C16—C11 | 179.3 (6) |
C6—C1—C2—F2 | 179.8 (6) | C14—C15—C16—C11 | 0.3 (9) |
Zn2—C1—C2—F2 | 6.4 (10) | C12—C11—C16—F16 | 177.5 (5) |
C6—C1—C2—C3 | −1.9 (11) | Zn1—C11—C16—F16 | 8.7 (7) |
Zn2—C1—C2—C3 | −175.4 (6) | C12—C11—C16—C15 | 0.3 (8) |
F2—C2—C3—F3 | −1.0 (13) | Zn1—C11—C16—C15 | −168.5 (5) |
C1—C2—C3—F3 | −179.2 (8) | O1—Zn2—O2—C23' | −43.3 (10) |
F2—C2—C3—C4 | 179.2 (9) | C1—Zn2—O2—C23' | 131.7 (10) |
C1—C2—C3—C4 | 0.9 (15) | O1—Zn2—O2—C21 | 63 (3) |
F3—C3—C4—F4 | −1.9 (17) | C1—Zn2—O2—C21 | −122 (3) |
C2—C3—C4—F4 | 178.0 (9) | O1—Zn2—O2—C21' | 150.0 (6) |
F3—C3—C4—C5 | −179.8 (10) | C1—Zn2—O2—C21' | −35.0 (7) |
C2—C3—C4—C5 | 0.1 (17) | O1—Zn2—O2—C23 | −81.5 (7) |
F4—C4—C5—F5 | 0.7 (16) | C1—Zn2—O2—C23 | 93.6 (7) |
C3—C4—C5—F5 | 178.7 (9) | C23'—O2—C21—C22 | −147 (3) |
F4—C4—C5—C6 | −177.8 (8) | C21'—O2—C21—C22 | −12.3 (19) |
C3—C4—C5—C6 | 0.2 (16) | C23—O2—C21—C22 | −123 (2) |
C2—C1—C6—F6 | −179.5 (6) | Zn2—O2—C21—C22 | 90 (4) |
Zn2—C1—C6—F6 | −5.7 (8) | C23'—O2—C21'—C22 | 64.6 (18) |
C2—C1—C6—C5 | 2.2 (10) | C21—O2—C21'—C22 | 14 (2) |
Zn2—C1—C6—C5 | 176.0 (6) | C23—O2—C21'—C22 | 102.7 (16) |
C4—C5—C6—F6 | −179.7 (8) | Zn2—O2—C21'—C22 | −128.0 (14) |
F5—C5—C6—F6 | 1.7 (10) | O2—C21'—C22—C21 | −12 (2) |
C4—C5—C6—C1 | −1.4 (13) | O2—C21—C22—C21' | 14 (2) |
F5—C5—C6—C1 | −179.9 (7) | C23'—O2—C23—C24 | −123 (2) |
O1i—Zn1—C11—C12 | 117.9 (4) | C21—O2—C23—C24 | −166 (2) |
O1—Zn1—C11—C12 | −13.6 (5) | C21'—O2—C23—C24 | 124.9 (13) |
O1ii—Zn1—C11—C12 | −119.3 (4) | Zn2—O2—C23—C24 | −5.3 (15) |
Zn1iii—Zn1—C11—C12 | −165.5 (3) | C21—O2—C23'—C24' | 157 (2) |
Zn1ii—Zn1—C11—C12 | −66.6 (5) | C21'—O2—C23'—C24' | 107.9 (13) |
Zn1i—Zn1—C11—C12 | 38.5 (6) | C23—O2—C23'—C24' | 22.7 (14) |
O1i—Zn1—C11—C16 | −74.3 (5) | Zn2—O2—C23'—C24' | −58.2 (15) |
Symmetry codes: (i) −y+1/2, x−1/2, −z+1/2; (ii) y+1/2, −x+1/2, −z+1/2; (iii) −x+1, −y, z. |
Experimental details
Crystal data | |
Chemical formula | [Zn8(C6F5)8O4(C4H10O)4] |
Mr | 2219.92 |
Crystal system, space group | Cubic, P43n |
Temperature (K) | 173 |
a (Å) | 23.4948 (6) |
V (Å3) | 12969.3 (6) |
Z | 6 |
Radiation type | Mo Kα |
µ (mm−1) | 2.31 |
Crystal size (mm) | 0.35 × 0.33 × 0.32 |
Data collection | |
Diffractometer | Stoe IPDS II two-circle |
Absorption correction | Multi-scan (MULABS; Spek, 2009; Blessing, 1995) |
Tmin, Tmax | 0.498, 0.525 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 75864, 4000, 3655 |
Rint | 0.096 |
(sin θ/λ)max (Å−1) | 0.605 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.093, 1.08 |
No. of reflections | 4000 |
No. of parameters | 271 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.57, −0.40 |
Absolute structure | Flack (1983), 1839 Friedel pairs |
Absolute structure parameter | −0.002 (19) |
Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).
References
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Fulmer, G. R., Miller, A. J. M., Sherden, N. H., Gottlieb, H. E., Nudelman, A., Stoltz, B. M., Bercaw, J. E. & Goldberg, K. I. (2010). Organometallics, 29, 2176–2179. Web of Science CrossRef CAS Google Scholar
Hayashi, M., Bolte, M., Wagner, M. & Lerner, H.-W. (2011). Z. Anorg. Allg. Chem. 637, 646–649. Web of Science CSD CrossRef CAS Google Scholar
Noltes, J. G. & van den Hurk, J. W. G. (1964). J. Organomet. Chem. 1, 377–383. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany. Google Scholar
Sun, Y., Piers, W. E. & Parvez, M. (1998). Can. J. Chem. 76, 513–517. Web of Science CrossRef CAS Google Scholar
Weidenbruch, M., Herrndorf, M., Schäfer, A., Pohl, S. & Saak, W. (1989). J. Organomet. Chem. 361, 139–145. CSD CrossRef CAS Web of Science Google Scholar
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Since the first synthesis of Zn[C6F5]2 in 1964 many applications of synthesized pentafluorophenyl organyls have been documented (Noltes & van den Hurk, 1964). Despite the long existence and common usage of Zn[C6F5]2, its reactivity towards water has not yet been investigated well. Very recently we have studied the chemical behavior of a series of mesityl derivatives of group 12 elements (Hayashi et al., 2011). It has been shown that the Zn derivative Zn[Mes]2 is more reactive towards acids than M[Mes]2 (M = Cd, Hg). In this paper we report the crystal structure of the product which was obtained from the 1 : 1 reaction of (Et2O)2Zn[C6F5]2 with water. Bis(pentafluorophenyl)zinc was synthesized by slight modification of the method reported in the literature via conversion of Mg[C6F5]Br with ZnCl2 in diethyl ether (Noltes & van den Hurk, 1964; Sun et al., 1998). It is interesting to note that the partial hydrolysis of (Et2O)2Zn[C6F5]2 yields the oxide [C6F5(Et2O)ZnOZnC6F5]4 whereas the 1 : 1 reaction of the corresponding Cd[C6F5]2 with water produces the hydroxy derivative [C6F5CdOH]4 (Weidenbruch et al., 1989). In the solid state the Cd hydroxide [C6F5CdOH]4 also displays a heterocubane structure.
Molecules of the title compound, C64H40F40O8Zn8, are located on a special position of site symmetry 4. As a result of that, there is just a quarter of a molecule in the asymmetric unit. The title compound features an Zn4O4 cube. Each Zn atom in the cube carries a pentafluorophenyl substituent. Each O atom is bonded to a further Zn atom which is connected to a pentafluorophenyl substituent and the O atom of a diethyl ether molecule.