Tetra­kis(diethyl ether)tetra-μ4-oxido-octa­kis­(penta­fluoro­phen­yl)octa­zinc

Franz, D.; Lerner, H.-W.; Bolte, M.

doi:10.1107/S160053681103697X

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page m1395

https://doi.org/10.1107/S160053681103697X

Open

access

Tetrakis(diethyl ether)tetra-μ₄-oxido-octakis(pentafluorophenyl)octazinc

Daniel Franz,^a Hans-Wolfram Lerner ^a and Michael Bolte ^a ^*

^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

(Received 25 August 2011; accepted 12 September 2011; online 17 September 2011)

Molecules of the title compound, [Zn₈(C₆F₅)₈O₄(C₄H₁₀O)₄], are located on a special position of site symmetry $[\overline{4}]$ . As a result, there is just one quarter-molecule in the asymmetric unit. 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 chemical shift values of the signals observed in the ¹H NMR spectrum of free Et₂O in [D₈]THF, see: Fulmer et al. (2010 ).

Experimental

Crystal data

[Zn₈(C₆F₅)₈O₄(C₄H₁₀O)₄]
M_r = 2219.92
Cubic, $[P \overline 43n ]$
a = 23.4948 (6) Å
V = 12969.3 (6) Å³
Z = 6
Mo Kα radiation
μ = 2.31 mm⁻¹
T = 173 K
0.35 × 0.33 × 0.32 mm

Data collection

Stoe IPDS II two-circle diffractometer
Absorption correction: multi-scan (MULABS; Spek, 2009 ; Blessing, 1995 ) T_min = 0.498, T_max = 0.525
75864 measured reflections
4000 independent reflections
3655 reflections with I > 2σ(I)
R_int = 0.096

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.093
S = 1.08
4000 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.40 e Å⁻³
Absolute structure: Flack (1983 ), 1839 Friedel pairs
Flack parameter: −0.002 (19)

Data collection: X-AREA (Stoe & Cie, 2001 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681103697X/kj2188sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681103697X/kj2188Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 chemical shift values for the signals observed in the ¹H NMR spectrum of free Et₂O in [D₈]THF, see: Fulmer et al. (2010).

Experimental top

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}). Chemical shift values (¹H, ¹³C{¹H}) are reported in p.p.m. relative to SiMe₄ and were referenced to residual solvent signals. The ¹⁹F{¹H} NMR chemical shift 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, ³J_H—H = 7.0 Hz, O(CH₂CH₃)₂) (the chemical shift 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, 3J_H—H = 7.0 Hz, O(CH₂CH₃)₂); ¹³C{¹H} NMR (62.9 MHz, [D₈]THF, 25°C): δ = 149.5 (br d, ¹J_C—F = 226 Hz, (o-C₆F₅)-a or b), 149.2 (br d, ¹J_C—F = 223 Hz, (o-C₆F₅)-a or b), 140.5 (br d, ¹J_C—F = 258 Hz, (p-C₆F₅)-a,b), 137.1 p.p.m. (br d, ¹J_C—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, ³J_F—F = 19 Hz, (p-C₆F₅)-a or b), -156.58 (t, ³J_F—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).

Structure description top

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

	Fig. 1. Perspective view of the title compound with displacement ellipsoids at the 30% probability level; H atoms and the minor occupied disordered atoms have been omitted for clarity. Colour codes: C: grey, F: light green, O: red, Zn: blue.
	Fig. 2. Perspective view of central core of the title compound with displacement ellipsoids at the 30% probability level; Ether C atoms, F and H atoms have been omitted for clarity. Colour codes: C: grey, F: light green, O: red, Zn: blue.
	Fig. 3. Preparation of the title compound.

Tetrakis(diethyl ether)tetra-µ₄-oxido-octakis(pentafluorophenyl)octazinc top

Crystal data top

[Zn₈(C₆F₅)₈O₄(C₄H₁₀O)₄]	D_x = 1.705 Mg m⁻³
M_r = 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

Data collection top

Stoe IPDS II two-circle diffractometer	4000 independent reflections
Radiation source: fine-focus sealed tube	3655 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.096
ω scans	θ_max = 25.5°, θ_min = 2.5°
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	h = −27→28
T_min = 0.498, T_max = 0.525	k = −18→28
75864 measured reflections	l = −28→28

Refinement top

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(F_o²) + (0.0574P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.093	(Δ/σ)_max = 0.001
S = 1.08	Δρ_max = 0.57 e Å⁻³
4000 reflections	Δρ_min = −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)

Crystal data top

[Zn₈(C₆F₅)₈O₄(C₄H₁₀O)₄]	Z = 6
M_r = 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

Data collection top

Stoe IPDS II two-circle diffractometer	4000 independent reflections
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	3655 reflections with I > 2σ(I)
T_min = 0.498, T_max = 0.525	R_int = 0.096
75864 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.093	Δρ_max = 0.57 e Å⁻³
S = 1.08	Δρ_min = −0.40 e Å⁻³
4000 reflections	Absolute structure: Flack (1983), 1839 Friedel pairs
271 parameters	Absolute structure parameter: −0.002 (19)
0 restraints

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

	x	y	z	U_iso*/U_eq	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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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]
M_r	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)
T_min, T_max	0.498, 0.525
No. of measured, independent and observed [I > 2σ(I)] reflections	75864, 4000, 3655
R_int	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
Δρ_max, Δρ_min (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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.