Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113025559/fa3322sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113025559/fa3322Isup2.hkl |
CCDC reference: 960993
The development of mixed-valence CuII/CuI complexes is important for a variety of chemical, biochemical and engineering processes due to their interesting magnetic (Chen et al., 2006; Goher et al., 2007), optical (Xu et al., 2006), catalytic (King, 1994; Simonovic et al., 2009) and conduction (Kim et al., 2011) properties. Mixed-valence copper systems are intrinsically diverse, as copper(II) and copper(I) centers are known to exhibit a range of different coordination environments (Liu et al., 2012). Despite the great demand for such systems, simple direct synthetic routes towards mixed-valence copper complexes are often unavailable and the target products are generally obtained by partial reduction/oxidation of starting materials. Reduction of CuII salts is commonly used for the preparation of metal–organic frameworks where CuII cations are reduced by amines or nitrogen-containing heterocycles during a solvothermal synthesis (Wen et al., 2004; Wang & Wang, 2008; Zhu et al., 2011). It should be noted that CuII cations have a tendency to proceed beyond the CuI state to reach the undesired metallic Cu0 state under reducing conditions. In turn, CuI compounds are often unstable towards oxidation in solution and special care is needed to carry out these reactions. The accidental formation of a giant CuI,II cluster based on the oxidation of a CuSCN starting material has been reported recently (He et al., 2008).
It is clear that such oxidation/reduction methods are generally not very predictable or reliable, and frequently lead to a mixture of products. As an alternative, we offer an original small-scale `solvent-free' approach that relies on co-deposition of complementary volatile donor and acceptor building units from the gas phase. This method allows the synthesis of novel and unique organometallic and supramolecular products in a solvent-free environment (Petrukhina, 2007; Filatov & Petrukhina, 2010). This synthetic method excludes hazardous and toxic organic solvents from the chemical transformations and thus concomitantly addresses environmental concerns by saving resources and limiting waste. If needed, solvent molecules can be introduced in a controlled manner through the use of solvates or adducts (Dikarev et al., 2004). The products are deposited in the form of single crystals, and this ease of crystallization has allowed us to utilize X-ray diffraction methods for their structural characterization. As a result, we have proved this synthetic method to be effective for the preparation of new main group (Zabula et al., 2010) and transition metal complexes (Petrukhina et al., 2004; Sevryugina et al., 2007; Sevryugina & Petrukhina, 2008), for the investigation of the ligating properties of various weak donors (Petrukhina et al., 2005; Dikarev et al., 2008), for the entrapment of reactive intermediates formed in the gas phase (Petrukhina et al., 2003; Dikarev et al., 2003), and for utilizing weak intermolecular metal–π and π–π aromatic interactions in supramolecular assembly (Petrukhina et al., 2006; Filatov et al., 2006, 2010). Herein, we describe the use of this method for the straightforward preparation of the title mixed-valence supramolecular product, {[CuI4(O2CCF3)4]2–{µ2-OC(CH3)2}2–[CuII2(O2CCF3)4]}, (I), comprised of copper(I) and copper(II) trifluoroacetate units.
All manipulations were performed under an inert atmosphere employing standard Schlenk techniques. Sublimation–deposition procedures were carried out in small Pyrex glass ampoules (outside diameter 1.1 cm) of varied length (5–8 cm). The ampoules were evacuated to ca 10 -2 Torr (1 Torr = 133.322 Pa), sealed and placed in an electric furnace having a small (ca 5 K) temperature gradient along the length of the tube. [CuI4(O2CCF3)4] was synthesized following the previously reported procedure (Cotton et al., 2000). [CuII2(O2CCF3)4].2OC(CH3)2 was obtained from copper(II) trifluoroacetate hydrate by recrystallization from acetone. IR spectra were recorded on a Perkin–Elmer FT–IR spectrometer (Spectrum 100) in the 4000–600 cm-1 range, using a universal ATR accessory.
For the synthesis of (I), a mixture of [CuI4(O2CCF3)4] (0.036 g, 0.051 mmol) and [CuII2(O2CCF3)4].2OC(CH3)2 (0.002 g, 0.003 mmol) was sealed in an evacuated Pyrex tube. The ampoule was placed in an electric furnace at 377 K. Blue–green [CIF states just green?] plates of (I) appeared in the cold zone of the ampoule in ca 6 d (yield 46%). IR (νmax, cm-1): 1710 (w), 1638 (s), 1630 (s), 1469 (m), 1447 (m), 1191 (s), 1140 (s), 857 (m), 794 (m), 783 (w), 729 (s).
H atoms, all belonging to methyl groups, were included at calculated positions, with C—H = 0.98 Å, and refined using a riding model with free rotation about the local C—C bond. For all H atoms, Uiso(H) = 1.5Ueq(C).
For the specific preparation of (I), we used a bis-acetone adduct of [CuII2(O2CCF3)4] and a very electrophilic tetranuclear [CuI4(O2CCF3)4] complex (Cotton et al., 2000) as pre-designed building blocks. Co-deposition was carried out as described in the Experimental section. The IR spectrum of (I) is dominated by strong absorptions of the trifluoroacetate groups of the copper(I) and copper(II) units. Stretches at 1638 and 1447 cm-1 are attributed to the asymmetric and symmetric CO vibrations of the carboxylic acid groups of copper(II) trifluoroacetate. Vibration peaks at 1630 and 1469 cm-1 can be assigned to the asymmetric and symmetric CO stretches of the carboxylic acid groups of copper(I) trifluoroacetate. The C═O vibration of the bridging acetone is observed at 1710 cm-1. In the previously characterized acetone adduct of a fully fluorinated carboxylate, CuII perfluorooctylate, the C═O stretch was observed at 1714 cm-1 (Motreff et al., 2009). Thus, IR vibrational spectroscopy of (I) shows the co-crystallization of CuI and CuII trifluoroacetates and acetone molecules. The particular coordination mode of the acetone was revealed by a single-crystal X-ray diffraction analysis.
Complex (I) (Fig. 1) crystallizes in the triclinic space group P1. The asymmetric unit contains one dinuclear CuII trifluoroacetate paddlewheel complex, two tetramers of CuI trifluoroacetate, and two acetone molecules connecting the metal units together (Fig. 1). The total number of independent Cu atoms in (I) is ten. It can be noted that CF3 groups generally have a strong tendency to be rotationally disordered but are found to be well-behaved in the title product.
For the copper(I) trifluoroacetate fragment of (I), the arrangement of the four independent Cu atoms can be described as a rhombus, with the CuCu distances ranging from 2.7443 (8) to 2.8258 (9) Å (Table 2). The short CuCu diagonals in the two independent tetracopper units are 2.9257 (9) and 2.9333 (9) Å. It is interesting to note that the CuCu contacts are elongated compared with unligated [CuI4(O2CCF3)4], where distances as short as 2.719 (1) Å were observed (Cotton et al., 2000). The trifluoroacetate ligands bridge the four pairs of adjacent Cu atoms around the tetramer in an alternating fashion above and below the Cu4 plane. The internal Cu—O distances range from 1.876 (3) to 1.922 (3) Å (Table 2).
The central [CuII2(O2CCF3)4] complex represents a standard tetrabridged paddlewheel structure, with the intramolecular Cu—O distances spanning the range 1.964 (3) to 1.994 (3) Å. Again, an elongation of these bonds is observed compared with the unligated complex. The Cu···Cu contact inside the dimer is 2.7171 (8) Å. While the structure of the bis-acetone adduct of [CuII2(O2CCF3)4] is not available and thus a direct structural comparison with (I) cannot be made, a similar shortening of the Cu···Cu distances (2.73-2.77 Å) has been observed in other O- (Zhang et al., 2005) or N-donor (Karpova et al., 1998) adducts. This is substantially shorter than that in the unligated [CuII2(O2CCF3)4] complex [3.086 (2) Å], thus showing the effect of the coordinated acetone on the paddlewheel structure.
The C10═O9 and C13═O10 bond distances in the µ2-bridged acetone molecules are 1.225 (6) and 1.235 (6) Å, respectively. The planar configuration of both acetone molecules is preserved in (I). Overall, the coordinated acetone molecules are not significantly affected by complexation and their geometric parameters are similar to those in the mixed-metal {[CuI4(O2CCF3)4]–{µ2-OC(CH3)2}2–[RhII2(O2CCF3)4]} complex, in which CuII trifluoroacetate is replaced by RhII trifluoroacetate (Dikarev et al., 2004). The acetone molecules bridge the copper units in an asymmetric fashion: the CuII1···O9 distance is 2.167 (3) Å, while CuI7···O9 = 2.627 (3) Å. Similarly, CuII2···O10 = 2.153 (3) Å, while the CuI8···O10 distance of 2.736 (3) Å is much longer. Additional contacts, CuI7···O17 and CuI8···O16, are observed between the dicopper(II) and tetracopper(I) units [2.539 (3) and 2.509 (3) Å, respectively].
The {[CuI4(O2CCF3)4]2–{µ2-OC(CH3)2}2–[CuII2(O2CCF3)4]} molecules are involved in a number of intermolecular CuI···O interactions with contacts shorter than 3.32 Å, which is the sum of the van der Waals radii of Cu and O [1.40 Å for an O atom (Bondi, 1964) and 1.92 Å for a Cu atom (Batsanov, 2011)]. All three open ends of the electrophilic copper(I) tetramer bind to O atoms of the trifluoroacetate groups of neighboring copper(I) units (Fig. 2).
Two Cu atoms, Cu5 and Cu6, exhibit one contact each with atoms O22B and O23A of 2.761 (3) and 2.670 (3) Å, respectively [symmetry codes: (A) -x + 1, -y + 1, -z + 1; (B) -x + 2, -y + 1, -z + 1]. Atom Cu3 makes two intermolecular contacts with atoms O20A and O25B of 2.550 (3) and 2.734 (3) Å, respectively. Both tetracopper(I) units are involved in such Cu···O intermolecular interactions, resulting in a two-dimensional layered network in the structure of (I) (Fig. 3).
In summary, a new product, {[CuI4(O2CCF3)4]2–{µ2-OC(CH3)2}2–[CuII2(O2CCF3)4]}, has been prepared by co-deposition of two complementary volatile building blocks. This complex is of interest from the viewpoint of gas-phase supramolecular synthesis and also because of its rare acetone bridging mode. These results illustrate that the deposition method allows for additional possibilities in supramolecular design, by utilizing intermolecular interactions and coordination bonds in ways that conventional solution chemistry cannot provide.
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Cu10(C2F3O2)12(C3H6O)2] | Z = 2 |
Mr = 2107.80 | F(000) = 2028 |
Triclinic, P1 | Dx = 2.414 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.4999 (12) Å | Cell parameters from 9710 reflections |
b = 11.1689 (15) Å | θ = 2.2–28.3° |
c = 32.202 (4) Å | µ = 3.78 mm−1 |
α = 94.586 (2)° | T = 100 K |
β = 90.880 (2)° | Plate, blue–green |
γ = 107.708 (2)° | 0.28 × 0.12 × 0.08 mm |
V = 2900.4 (7) Å3 |
Bruker SMART APEX CCD area-detector diffractometer | 12733 independent reflections |
Radiation source: fine-focus sealed tube | 9129 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
0.30° ω scans | θmax = 28.3°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −11→11 |
Tmin = 0.417, Tmax = 0.752 | k = −14→14 |
24771 measured reflections | l = −42→40 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0582P)2 + 1.4275P] where P = (Fo2 + 2Fc2)/3 |
12733 reflections | (Δ/σ)max = 0.001 |
923 parameters | Δρmax = 1.11 e Å−3 |
0 restraints | Δρmin = −0.69 e Å−3 |
[Cu10(C2F3O2)12(C3H6O)2] | γ = 107.708 (2)° |
Mr = 2107.80 | V = 2900.4 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.4999 (12) Å | Mo Kα radiation |
b = 11.1689 (15) Å | µ = 3.78 mm−1 |
c = 32.202 (4) Å | T = 100 K |
α = 94.586 (2)° | 0.28 × 0.12 × 0.08 mm |
β = 90.880 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 12733 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 9129 reflections with I > 2σ(I) |
Tmin = 0.417, Tmax = 0.752 | Rint = 0.028 |
24771 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.02 | Δρmax = 1.11 e Å−3 |
12733 reflections | Δρmin = −0.69 e Å−3 |
923 parameters |
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 | ||
Cu1 | 0.84624 (7) | 0.85609 (5) | 0.229302 (17) | 0.01998 (13) | |
Cu2 | 0.70886 (7) | 0.64445 (5) | 0.268447 (17) | 0.02041 (13) | |
Cu3 | 0.76510 (7) | 0.49615 (5) | 0.513826 (17) | 0.02304 (13) | |
Cu4 | 0.71979 (7) | 0.99617 (5) | −0.014572 (17) | 0.02316 (14) | |
Cu5 | 0.93249 (7) | 0.63998 (5) | 0.453168 (17) | 0.02274 (14) | |
Cu6 | 0.58627 (7) | 0.48554 (5) | 0.440841 (18) | 0.02338 (14) | |
Cu7 | 0.76356 (7) | 0.89698 (6) | 0.123212 (18) | 0.02648 (14) | |
Cu8 | 0.75390 (7) | 0.61214 (6) | 0.377191 (18) | 0.02812 (15) | |
Cu9 | 0.57146 (7) | 0.85419 (5) | 0.047960 (17) | 0.02267 (14) | |
Cu10 | 0.91852 (7) | 1.01153 (5) | 0.055059 (18) | 0.02308 (14) | |
O1 | 0.6598 (4) | 1.1336 (3) | 0.01274 (9) | 0.0214 (7) | |
O2 | 0.8471 (4) | 1.1544 (3) | 0.06578 (10) | 0.0261 (7) | |
O3 | 1.0224 (4) | 0.8816 (3) | 0.05148 (10) | 0.0226 (7) | |
O4 | 0.9040 (4) | 0.7999 (3) | 0.10962 (10) | 0.0289 (8) | |
O5 | 0.6108 (4) | 0.9826 (3) | 0.13949 (10) | 0.0288 (8) | |
O6 | 0.4586 (4) | 0.9541 (3) | 0.07910 (9) | 0.0235 (7) | |
O7 | 0.6480 (4) | 0.7318 (3) | 0.01734 (10) | 0.0236 (7) | |
O8 | 0.7809 (4) | 0.8516 (3) | −0.03294 (9) | 0.0226 (7) | |
O9 | 0.9316 (4) | 1.0139 (3) | 0.19159 (10) | 0.0236 (7) | |
O10 | 0.6021 (4) | 0.4861 (3) | 0.30392 (10) | 0.0234 (7) | |
O11 | 0.6620 (4) | 0.9111 (3) | 0.25095 (10) | 0.0272 (7) | |
O12 | 0.5391 (4) | 0.7290 (3) | 0.28038 (10) | 0.0251 (7) | |
O13 | 1.0119 (4) | 0.7724 (3) | 0.21357 (10) | 0.0244 (7) | |
O14 | 0.9059 (4) | 0.6001 (3) | 0.24933 (10) | 0.0260 (7) | |
O15 | 0.9640 (4) | 0.9178 (3) | 0.28379 (10) | 0.0282 (8) | |
O16 | 0.8431 (4) | 0.7461 (3) | 0.31773 (9) | 0.0238 (7) | |
O17 | 0.6956 (4) | 0.7554 (3) | 0.18256 (9) | 0.0236 (7) | |
O18 | 0.5983 (4) | 0.5741 (3) | 0.21397 (10) | 0.0277 (7) | |
O19 | 0.6141 (4) | 0.7110 (3) | 0.38992 (10) | 0.0302 (8) | |
O20 | 0.4801 (4) | 0.6143 (3) | 0.44399 (10) | 0.0239 (7) | |
O21 | 0.6617 (4) | 0.3439 (3) | 0.43056 (10) | 0.0263 (7) | |
O22 | 0.8289 (4) | 0.3600 (3) | 0.48767 (10) | 0.0242 (7) | |
O23 | 0.7054 (4) | 0.6421 (3) | 0.53096 (10) | 0.0237 (7) | |
O24 | 0.8543 (4) | 0.7620 (3) | 0.48308 (10) | 0.0233 (7) | |
O25 | 1.0448 (4) | 0.5393 (3) | 0.42186 (9) | 0.0238 (7) | |
O26 | 0.8976 (4) | 0.5187 (3) | 0.36097 (10) | 0.0300 (8) | |
C1 | 0.7404 (5) | 1.1859 (4) | 0.04596 (14) | 0.0196 (9) | |
C2 | 0.6977 (5) | 1.3024 (4) | 0.06557 (14) | 0.0220 (10) | |
C3 | 0.9968 (5) | 0.8051 (4) | 0.07949 (14) | 0.0205 (9) | |
C4 | 1.0942 (5) | 0.7092 (4) | 0.07952 (14) | 0.0210 (9) | |
C5 | 0.4933 (5) | 0.9907 (4) | 0.11698 (15) | 0.0221 (10) | |
C6 | 0.3786 (6) | 1.0541 (5) | 0.14109 (15) | 0.0287 (11) | |
C7 | 0.7283 (5) | 0.7503 (4) | −0.01496 (14) | 0.0203 (9) | |
C8 | 0.7728 (6) | 0.6345 (4) | −0.03497 (14) | 0.0239 (10) | |
C9 | 1.0117 (7) | 1.2173 (5) | 0.16634 (17) | 0.0389 (13) | |
H9A | 0.9619 | 1.1708 | 0.1399 | 0.058* | |
H9B | 1.1267 | 1.2661 | 0.1624 | 0.058* | |
H9C | 0.9497 | 1.2747 | 0.1758 | 0.058* | |
C10 | 1.0066 (6) | 1.1266 (5) | 0.19818 (15) | 0.0283 (11) | |
C11 | 1.1045 (11) | 1.1817 (6) | 0.2387 (2) | 0.082 (3) | |
H11A | 1.0342 | 1.2110 | 0.2583 | 0.123* | |
H11B | 1.2004 | 1.2529 | 0.2332 | 0.123* | |
H11C | 1.1422 | 1.1169 | 0.2508 | 0.123* | |
C12 | 0.6474 (9) | 0.3163 (6) | 0.26017 (19) | 0.0567 (18) | |
H12A | 0.6612 | 0.3735 | 0.2380 | 0.085* | |
H12B | 0.5671 | 0.2348 | 0.2506 | 0.085* | |
H12C | 0.7538 | 0.3041 | 0.2671 | 0.085* | |
C13 | 0.5860 (6) | 0.3723 (5) | 0.29823 (15) | 0.0261 (10) | |
C14 | 0.5072 (7) | 0.2838 (5) | 0.33002 (16) | 0.0360 (12) | |
H14A | 0.4777 | 0.3315 | 0.3539 | 0.054* | |
H14B | 0.5852 | 0.2415 | 0.3394 | 0.054* | |
H14C | 0.4074 | 0.2206 | 0.3175 | 0.054* | |
C15 | 0.5508 (5) | 0.8379 (5) | 0.27070 (14) | 0.0229 (10) | |
C16 | 0.4176 (6) | 0.8951 (5) | 0.28763 (14) | 0.0232 (10) | |
C17 | 1.0075 (5) | 0.6683 (4) | 0.22605 (13) | 0.0209 (9) | |
C18 | 1.1415 (6) | 0.6105 (5) | 0.20936 (15) | 0.0256 (10) | |
C19 | 0.9352 (5) | 0.8573 (4) | 0.31549 (14) | 0.0203 (9) | |
C20 | 1.0185 (6) | 0.9308 (5) | 0.35669 (15) | 0.0269 (11) | |
C21 | 0.6132 (5) | 0.6409 (4) | 0.18387 (14) | 0.0213 (10) | |
C22 | 0.5235 (6) | 0.5723 (5) | 0.14248 (14) | 0.0253 (10) | |
C23 | 0.5106 (5) | 0.6956 (4) | 0.41775 (14) | 0.0197 (9) | |
C24 | 0.4074 (6) | 0.7881 (4) | 0.41728 (15) | 0.0241 (10) | |
C25 | 0.7595 (5) | 0.3092 (4) | 0.45290 (14) | 0.0222 (10) | |
C26 | 0.8073 (6) | 0.1932 (4) | 0.43481 (15) | 0.0237 (10) | |
C27 | 0.7648 (5) | 0.7430 (4) | 0.51428 (14) | 0.0213 (9) | |
C28 | 0.7204 (6) | 0.8590 (5) | 0.53341 (14) | 0.0245 (10) | |
C29 | 1.0101 (5) | 0.5047 (5) | 0.38344 (14) | 0.0231 (10) | |
C30 | 1.1205 (6) | 0.4372 (5) | 0.35985 (15) | 0.0288 (11) | |
F1 | 0.7134 (4) | 1.3896 (3) | 0.03851 (9) | 0.0368 (7) | |
F2 | 0.5393 (3) | 1.2669 (3) | 0.07708 (10) | 0.0357 (7) | |
F3 | 0.7930 (3) | 1.3561 (3) | 0.09948 (9) | 0.0306 (6) | |
F4 | 1.1843 (3) | 0.7082 (3) | 0.04576 (8) | 0.0280 (6) | |
F5 | 1.1991 (3) | 0.7381 (3) | 0.11314 (9) | 0.0326 (7) | |
F6 | 0.9934 (3) | 0.5929 (3) | 0.08168 (10) | 0.0366 (7) | |
F7 | 0.2597 (3) | 1.0702 (3) | 0.11597 (9) | 0.0361 (7) | |
F8 | 0.4628 (4) | 1.1667 (3) | 0.15956 (10) | 0.0442 (8) | |
F9 | 0.3027 (4) | 0.9824 (3) | 0.17063 (9) | 0.0429 (8) | |
F10 | 0.8125 (4) | 0.6467 (3) | −0.07487 (8) | 0.0333 (7) | |
F11 | 0.6483 (4) | 0.5285 (3) | −0.03379 (10) | 0.0377 (7) | |
F12 | 0.9043 (4) | 0.6222 (3) | −0.01409 (9) | 0.0379 (7) | |
F13 | 0.3829 (3) | 0.9722 (3) | 0.26179 (9) | 0.0361 (7) | |
F14 | 0.2756 (3) | 0.8052 (3) | 0.29408 (9) | 0.0310 (7) | |
F15 | 0.4735 (4) | 0.9621 (3) | 0.32429 (9) | 0.0353 (7) | |
F16 | 1.2824 (3) | 0.7002 (3) | 0.20204 (8) | 0.0296 (6) | |
F17 | 1.0826 (3) | 0.5406 (3) | 0.17324 (9) | 0.0327 (7) | |
F18 | 1.1784 (4) | 0.5356 (3) | 0.23572 (9) | 0.0374 (7) | |
F19 | 1.1681 (4) | 1.0072 (4) | 0.35118 (10) | 0.0571 (10) | |
F20 | 0.9260 (5) | 0.9973 (4) | 0.37208 (11) | 0.0615 (11) | |
F21 | 1.0329 (4) | 0.8542 (3) | 0.38529 (10) | 0.0458 (8) | |
F22 | 0.4695 (4) | 0.6491 (3) | 0.12032 (9) | 0.0399 (8) | |
F23 | 0.6283 (4) | 0.5324 (3) | 0.11910 (9) | 0.0446 (9) | |
F24 | 0.3938 (4) | 0.4746 (3) | 0.14878 (10) | 0.0489 (9) | |
F25 | 0.3043 (3) | 0.7555 (3) | 0.38337 (9) | 0.0334 (7) | |
F26 | 0.5038 (4) | 0.9062 (3) | 0.41525 (10) | 0.0363 (7) | |
F27 | 0.3155 (3) | 0.7864 (3) | 0.45076 (8) | 0.0282 (6) | |
F28 | 0.7210 (3) | 0.1405 (3) | 0.39969 (9) | 0.0295 (6) | |
F29 | 0.9688 (3) | 0.2293 (3) | 0.42642 (9) | 0.0323 (7) | |
F30 | 0.7830 (4) | 0.1065 (3) | 0.46225 (9) | 0.0368 (7) | |
F31 | 0.5879 (4) | 0.8697 (3) | 0.51253 (9) | 0.0380 (7) | |
F32 | 0.8440 (4) | 0.9666 (3) | 0.53168 (9) | 0.0364 (7) | |
F33 | 0.6812 (4) | 0.8486 (3) | 0.57340 (9) | 0.0344 (7) | |
F34 | 1.1994 (4) | 0.5057 (3) | 0.33025 (10) | 0.0462 (9) | |
F35 | 1.0281 (4) | 0.3251 (3) | 0.34163 (10) | 0.0451 (8) | |
F36 | 1.2341 (4) | 0.4150 (3) | 0.38484 (9) | 0.0396 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0212 (3) | 0.0220 (3) | 0.0169 (3) | 0.0065 (2) | 0.0022 (2) | 0.0031 (2) |
Cu2 | 0.0215 (3) | 0.0226 (3) | 0.0178 (3) | 0.0070 (2) | 0.0026 (2) | 0.0041 (2) |
Cu3 | 0.0275 (3) | 0.0253 (3) | 0.0195 (3) | 0.0121 (2) | 0.0056 (2) | 0.0039 (2) |
Cu4 | 0.0270 (3) | 0.0255 (3) | 0.0209 (3) | 0.0130 (2) | 0.0046 (2) | 0.0040 (2) |
Cu5 | 0.0233 (3) | 0.0258 (3) | 0.0202 (3) | 0.0085 (2) | 0.0065 (2) | 0.0028 (2) |
Cu6 | 0.0236 (3) | 0.0253 (3) | 0.0242 (3) | 0.0112 (2) | 0.0031 (2) | 0.0046 (2) |
Cu7 | 0.0279 (3) | 0.0373 (4) | 0.0205 (3) | 0.0181 (3) | 0.0060 (2) | 0.0065 (3) |
Cu8 | 0.0298 (3) | 0.0413 (4) | 0.0205 (3) | 0.0198 (3) | 0.0079 (2) | 0.0087 (3) |
Cu9 | 0.0235 (3) | 0.0266 (3) | 0.0193 (3) | 0.0093 (2) | 0.0059 (2) | 0.0025 (2) |
Cu10 | 0.0234 (3) | 0.0251 (3) | 0.0242 (3) | 0.0118 (2) | 0.0015 (2) | 0.0049 (2) |
O1 | 0.0243 (16) | 0.0239 (17) | 0.0192 (16) | 0.0112 (13) | 0.0019 (13) | 0.0056 (13) |
O2 | 0.0254 (17) | 0.0232 (18) | 0.033 (2) | 0.0122 (14) | 0.0001 (14) | 0.0008 (15) |
O3 | 0.0240 (16) | 0.0234 (17) | 0.0228 (17) | 0.0098 (13) | 0.0048 (13) | 0.0050 (14) |
O4 | 0.0327 (19) | 0.042 (2) | 0.0214 (17) | 0.0225 (16) | 0.0099 (14) | 0.0110 (15) |
O5 | 0.0272 (18) | 0.040 (2) | 0.0250 (18) | 0.0190 (16) | 0.0020 (14) | 0.0001 (15) |
O6 | 0.0259 (17) | 0.0284 (18) | 0.0172 (16) | 0.0104 (14) | 0.0033 (13) | −0.0004 (14) |
O7 | 0.0266 (17) | 0.0234 (18) | 0.0216 (17) | 0.0087 (14) | 0.0060 (13) | 0.0010 (14) |
O8 | 0.0277 (17) | 0.0256 (18) | 0.0173 (16) | 0.0116 (14) | 0.0040 (13) | 0.0031 (13) |
O9 | 0.0230 (16) | 0.0254 (18) | 0.0238 (17) | 0.0090 (14) | 0.0012 (13) | 0.0050 (14) |
O10 | 0.0222 (16) | 0.0227 (18) | 0.0261 (18) | 0.0071 (13) | 0.0016 (13) | 0.0058 (14) |
O11 | 0.0297 (18) | 0.0292 (19) | 0.0247 (18) | 0.0109 (15) | 0.0067 (14) | 0.0049 (15) |
O12 | 0.0213 (16) | 0.0286 (19) | 0.0269 (18) | 0.0098 (14) | 0.0022 (13) | 0.0030 (15) |
O13 | 0.0232 (16) | 0.0294 (19) | 0.0247 (18) | 0.0130 (14) | 0.0044 (13) | 0.0061 (14) |
O14 | 0.0279 (17) | 0.0284 (19) | 0.0239 (18) | 0.0100 (14) | 0.0075 (14) | 0.0080 (14) |
O15 | 0.0291 (18) | 0.032 (2) | 0.0219 (18) | 0.0066 (15) | −0.0009 (14) | 0.0020 (15) |
O16 | 0.0266 (17) | 0.0291 (19) | 0.0158 (16) | 0.0083 (14) | 0.0015 (13) | 0.0025 (14) |
O17 | 0.0260 (17) | 0.0273 (18) | 0.0176 (16) | 0.0081 (14) | 0.0018 (13) | 0.0022 (14) |
O18 | 0.0320 (19) | 0.0251 (18) | 0.0246 (18) | 0.0064 (15) | −0.0012 (14) | 0.0044 (15) |
O19 | 0.0329 (19) | 0.040 (2) | 0.0259 (18) | 0.0198 (16) | 0.0127 (15) | 0.0136 (16) |
O20 | 0.0218 (16) | 0.0253 (18) | 0.0257 (18) | 0.0070 (13) | 0.0056 (13) | 0.0092 (14) |
O21 | 0.0265 (17) | 0.0260 (18) | 0.0287 (19) | 0.0105 (14) | 0.0039 (14) | 0.0061 (15) |
O22 | 0.0288 (17) | 0.0269 (18) | 0.0193 (17) | 0.0114 (14) | 0.0051 (13) | 0.0038 (14) |
O23 | 0.0282 (17) | 0.0265 (18) | 0.0193 (17) | 0.0124 (14) | 0.0062 (13) | 0.0024 (14) |
O24 | 0.0231 (16) | 0.0239 (18) | 0.0236 (17) | 0.0080 (13) | 0.0055 (13) | 0.0022 (14) |
O25 | 0.0236 (17) | 0.0291 (18) | 0.0182 (17) | 0.0076 (14) | 0.0024 (13) | 0.0015 (14) |
O26 | 0.0314 (19) | 0.045 (2) | 0.0189 (17) | 0.0193 (17) | 0.0062 (14) | 0.0041 (15) |
C1 | 0.020 (2) | 0.018 (2) | 0.020 (2) | 0.0047 (17) | 0.0044 (17) | 0.0052 (18) |
C2 | 0.023 (2) | 0.019 (2) | 0.026 (2) | 0.0076 (18) | 0.0012 (18) | 0.0058 (19) |
C3 | 0.018 (2) | 0.022 (2) | 0.021 (2) | 0.0049 (18) | −0.0008 (17) | 0.0017 (19) |
C4 | 0.023 (2) | 0.023 (2) | 0.019 (2) | 0.0100 (19) | 0.0065 (18) | 0.0051 (19) |
C5 | 0.021 (2) | 0.019 (2) | 0.025 (3) | 0.0030 (18) | 0.0075 (18) | 0.0030 (19) |
C6 | 0.032 (3) | 0.040 (3) | 0.018 (2) | 0.018 (2) | 0.003 (2) | −0.002 (2) |
C7 | 0.018 (2) | 0.026 (3) | 0.018 (2) | 0.0094 (18) | −0.0019 (17) | −0.0013 (19) |
C8 | 0.025 (2) | 0.025 (3) | 0.021 (2) | 0.0066 (19) | 0.0022 (19) | 0.002 (2) |
C9 | 0.052 (3) | 0.024 (3) | 0.039 (3) | 0.007 (2) | −0.005 (3) | 0.008 (2) |
C10 | 0.031 (3) | 0.030 (3) | 0.024 (3) | 0.008 (2) | 0.002 (2) | 0.000 (2) |
C11 | 0.135 (7) | 0.043 (4) | 0.041 (4) | −0.012 (4) | −0.030 (4) | 0.009 (3) |
C12 | 0.088 (5) | 0.034 (3) | 0.047 (4) | 0.014 (3) | 0.027 (4) | 0.005 (3) |
C13 | 0.028 (3) | 0.026 (3) | 0.022 (2) | 0.005 (2) | 0.0013 (19) | 0.003 (2) |
C14 | 0.046 (3) | 0.029 (3) | 0.030 (3) | 0.007 (2) | 0.001 (2) | 0.004 (2) |
C15 | 0.024 (2) | 0.029 (3) | 0.016 (2) | 0.009 (2) | −0.0019 (18) | 0.0015 (19) |
C16 | 0.024 (2) | 0.027 (3) | 0.020 (2) | 0.010 (2) | 0.0020 (18) | 0.004 (2) |
C17 | 0.021 (2) | 0.025 (3) | 0.016 (2) | 0.0068 (19) | −0.0010 (17) | 0.0004 (19) |
C18 | 0.024 (2) | 0.031 (3) | 0.026 (3) | 0.012 (2) | 0.0043 (19) | 0.005 (2) |
C19 | 0.021 (2) | 0.025 (2) | 0.017 (2) | 0.0100 (19) | 0.0006 (17) | 0.0017 (19) |
C20 | 0.027 (3) | 0.031 (3) | 0.025 (3) | 0.013 (2) | −0.001 (2) | −0.003 (2) |
C21 | 0.015 (2) | 0.029 (3) | 0.022 (2) | 0.0115 (19) | 0.0006 (17) | −0.001 (2) |
C22 | 0.025 (2) | 0.034 (3) | 0.018 (2) | 0.012 (2) | 0.0023 (18) | −0.002 (2) |
C23 | 0.021 (2) | 0.018 (2) | 0.021 (2) | 0.0061 (18) | 0.0001 (17) | 0.0021 (18) |
C24 | 0.024 (2) | 0.025 (3) | 0.024 (2) | 0.0064 (19) | 0.0066 (19) | 0.007 (2) |
C25 | 0.021 (2) | 0.021 (2) | 0.024 (2) | 0.0060 (18) | 0.0081 (18) | 0.0032 (19) |
C26 | 0.023 (2) | 0.025 (3) | 0.025 (3) | 0.0102 (19) | −0.0027 (19) | 0.002 (2) |
C27 | 0.019 (2) | 0.028 (3) | 0.020 (2) | 0.0104 (19) | 0.0002 (17) | 0.0050 (19) |
C28 | 0.029 (3) | 0.027 (3) | 0.018 (2) | 0.009 (2) | 0.0000 (19) | 0.0006 (19) |
C29 | 0.023 (2) | 0.031 (3) | 0.018 (2) | 0.010 (2) | 0.0082 (18) | 0.010 (2) |
C30 | 0.031 (3) | 0.040 (3) | 0.019 (2) | 0.015 (2) | 0.006 (2) | 0.004 (2) |
F1 | 0.057 (2) | 0.0279 (17) | 0.0312 (17) | 0.0205 (15) | 0.0036 (14) | 0.0073 (13) |
F2 | 0.0227 (14) | 0.0320 (17) | 0.0495 (19) | 0.0068 (12) | 0.0091 (13) | −0.0080 (14) |
F3 | 0.0330 (16) | 0.0303 (16) | 0.0298 (16) | 0.0138 (13) | −0.0076 (12) | −0.0048 (13) |
F4 | 0.0292 (15) | 0.0316 (16) | 0.0279 (15) | 0.0147 (12) | 0.0093 (12) | 0.0077 (12) |
F5 | 0.0301 (15) | 0.0433 (18) | 0.0294 (16) | 0.0166 (13) | 0.0018 (12) | 0.0115 (13) |
F6 | 0.0338 (16) | 0.0201 (15) | 0.055 (2) | 0.0055 (12) | 0.0134 (14) | 0.0063 (14) |
F7 | 0.0343 (16) | 0.056 (2) | 0.0271 (16) | 0.0290 (15) | −0.0009 (12) | −0.0027 (14) |
F8 | 0.0444 (19) | 0.043 (2) | 0.045 (2) | 0.0185 (16) | −0.0042 (15) | −0.0170 (16) |
F9 | 0.0435 (18) | 0.063 (2) | 0.0331 (17) | 0.0281 (17) | 0.0245 (14) | 0.0195 (16) |
F10 | 0.0467 (18) | 0.0350 (17) | 0.0205 (15) | 0.0159 (14) | 0.0102 (13) | 0.0006 (12) |
F11 | 0.0388 (17) | 0.0254 (16) | 0.0442 (19) | 0.0038 (13) | 0.0123 (14) | −0.0019 (14) |
F12 | 0.0413 (17) | 0.0420 (19) | 0.0391 (18) | 0.0291 (15) | −0.0088 (14) | −0.0077 (14) |
F13 | 0.0374 (17) | 0.0441 (19) | 0.0367 (18) | 0.0239 (14) | 0.0098 (13) | 0.0162 (14) |
F14 | 0.0249 (14) | 0.0367 (17) | 0.0326 (16) | 0.0102 (12) | 0.0067 (12) | 0.0061 (13) |
F15 | 0.0359 (16) | 0.0412 (18) | 0.0293 (16) | 0.0149 (14) | 0.0044 (13) | −0.0072 (14) |
F16 | 0.0216 (14) | 0.0378 (17) | 0.0305 (16) | 0.0100 (12) | 0.0065 (11) | 0.0045 (13) |
F17 | 0.0394 (17) | 0.0326 (17) | 0.0255 (16) | 0.0123 (13) | 0.0034 (12) | −0.0063 (13) |
F18 | 0.0398 (17) | 0.0478 (19) | 0.0378 (18) | 0.0288 (15) | 0.0120 (14) | 0.0192 (15) |
F19 | 0.0399 (19) | 0.070 (3) | 0.036 (2) | −0.0170 (17) | 0.0002 (15) | −0.0126 (17) |
F20 | 0.070 (2) | 0.084 (3) | 0.048 (2) | 0.060 (2) | −0.0198 (18) | −0.036 (2) |
F21 | 0.059 (2) | 0.047 (2) | 0.0281 (17) | 0.0115 (17) | −0.0147 (15) | 0.0018 (15) |
F22 | 0.0509 (19) | 0.045 (2) | 0.0291 (17) | 0.0263 (16) | −0.0169 (14) | −0.0063 (14) |
F23 | 0.0379 (18) | 0.064 (2) | 0.0361 (18) | 0.0283 (17) | −0.0039 (14) | −0.0242 (16) |
F24 | 0.0439 (19) | 0.050 (2) | 0.0345 (19) | −0.0109 (16) | −0.0059 (15) | −0.0010 (15) |
F25 | 0.0333 (16) | 0.0443 (19) | 0.0280 (16) | 0.0186 (14) | 0.0003 (12) | 0.0086 (14) |
F26 | 0.0381 (17) | 0.0210 (15) | 0.050 (2) | 0.0073 (13) | 0.0139 (14) | 0.0103 (14) |
F27 | 0.0302 (15) | 0.0288 (16) | 0.0293 (16) | 0.0128 (12) | 0.0089 (12) | 0.0079 (12) |
F28 | 0.0305 (15) | 0.0269 (15) | 0.0318 (16) | 0.0112 (12) | −0.0051 (12) | −0.0022 (12) |
F29 | 0.0230 (14) | 0.0360 (17) | 0.0387 (17) | 0.0123 (12) | 0.0056 (12) | −0.0054 (13) |
F30 | 0.0508 (19) | 0.0277 (16) | 0.0366 (18) | 0.0167 (14) | 0.0047 (14) | 0.0120 (14) |
F31 | 0.0399 (17) | 0.0417 (19) | 0.0391 (18) | 0.0254 (15) | −0.0096 (14) | −0.0064 (14) |
F32 | 0.0393 (17) | 0.0238 (16) | 0.0425 (19) | 0.0050 (13) | 0.0090 (14) | −0.0015 (13) |
F33 | 0.0472 (18) | 0.0335 (17) | 0.0239 (15) | 0.0149 (14) | 0.0111 (13) | −0.0003 (13) |
F34 | 0.050 (2) | 0.064 (2) | 0.0343 (18) | 0.0277 (18) | 0.0264 (15) | 0.0149 (16) |
F35 | 0.050 (2) | 0.045 (2) | 0.0406 (19) | 0.0199 (16) | −0.0041 (15) | −0.0169 (16) |
F36 | 0.0356 (17) | 0.068 (2) | 0.0272 (16) | 0.0353 (16) | −0.0009 (13) | −0.0045 (15) |
Cu1—O13 | 1.965 (3) | O26—C29 | 1.245 (5) |
Cu1—O11 | 1.966 (3) | C1—C2 | 1.545 (6) |
Cu1—O15 | 1.972 (3) | C2—F3 | 1.335 (5) |
Cu1—O17 | 1.991 (3) | C2—F1 | 1.336 (5) |
Cu1—O9 | 2.167 (3) | C2—F2 | 1.350 (5) |
Cu1—Cu2 | 2.7171 (8) | C3—C4 | 1.540 (6) |
Cu2—O18 | 1.964 (3) | C4—F6 | 1.329 (5) |
Cu2—O12 | 1.977 (3) | C4—F4 | 1.340 (5) |
Cu2—O14 | 1.979 (3) | C4—F5 | 1.345 (5) |
Cu2—O16 | 1.994 (3) | C5—C6 | 1.553 (6) |
Cu2—O10 | 2.153 (3) | C6—F8 | 1.329 (6) |
Cu3—O23 | 1.895 (3) | C6—F9 | 1.338 (6) |
Cu3—O22 | 1.904 (3) | C6—F7 | 1.348 (5) |
Cu3—Cu6 | 2.7540 (9) | C7—C8 | 1.550 (6) |
Cu3—Cu5 | 2.7599 (8) | C8—F11 | 1.331 (5) |
Cu4—O8 | 1.896 (3) | C8—F10 | 1.340 (5) |
Cu4—O1 | 1.914 (3) | C8—F12 | 1.344 (5) |
Cu4—Cu9 | 2.7443 (8) | C9—C10 | 1.490 (7) |
Cu4—Cu10 | 2.7489 (8) | C9—H9A | 0.9800 |
Cu5—O24 | 1.895 (3) | C9—H9B | 0.9800 |
Cu5—O25 | 1.922 (3) | C9—H9C | 0.9800 |
Cu5—Cu8 | 2.8043 (9) | C10—C11 | 1.517 (8) |
Cu5—Cu6 | 2.9257 (9) | C11—H11A | 0.9800 |
Cu6—O21 | 1.888 (3) | C11—H11B | 0.9800 |
Cu6—O20 | 1.914 (3) | C11—H11C | 0.9800 |
Cu6—Cu8 | 2.7492 (8) | C12—C13 | 1.503 (7) |
Cu7—O4 | 1.876 (3) | C12—H12A | 0.9800 |
Cu7—O5 | 1.889 (3) | C12—H12B | 0.9800 |
Cu7—O9 | 2.627 (3) | C12—H12C | 0.9800 |
Cu7—O17 | 2.539 (3) | C13—C14 | 1.501 (6) |
Cu7—Cu10 | 2.7750 (8) | C14—H14A | 0.9800 |
Cu7—Cu9 | 2.8258 (9) | C14—H14B | 0.9800 |
Cu8—O19 | 1.882 (3) | C14—H14C | 0.9800 |
Cu8—O10 | 2.736 (3) | C15—C16 | 1.547 (6) |
Cu8—O16 | 2.508 (3) | C16—F13 | 1.336 (5) |
Cu8—O26 | 1.887 (3) | C16—F15 | 1.344 (5) |
Cu9—O7 | 1.899 (3) | C16—F14 | 1.346 (5) |
Cu9—O6 | 1.917 (3) | C17—C18 | 1.553 (6) |
Cu9—Cu10 | 2.9333 (9) | C18—F18 | 1.336 (5) |
Cu10—O2 | 1.882 (3) | C18—F16 | 1.345 (5) |
Cu10—O3 | 1.912 (3) | C18—F17 | 1.347 (5) |
O1—C1 | 1.261 (5) | C19—C20 | 1.542 (6) |
O2—C1 | 1.252 (5) | C20—F20 | 1.313 (5) |
O3—C3 | 1.268 (5) | C20—F19 | 1.322 (6) |
O4—C3 | 1.254 (5) | C20—F21 | 1.334 (6) |
O5—C5 | 1.255 (5) | C21—C22 | 1.548 (6) |
O6—C5 | 1.256 (5) | C22—F24 | 1.326 (5) |
O7—C7 | 1.249 (5) | C22—F23 | 1.330 (5) |
O8—C7 | 1.273 (5) | C22—F22 | 1.336 (5) |
O9—C10 | 1.225 (6) | C23—C24 | 1.547 (6) |
O10—C13 | 1.235 (6) | C24—F26 | 1.332 (5) |
O11—C15 | 1.264 (5) | C24—F27 | 1.339 (5) |
O12—C15 | 1.254 (5) | C24—F25 | 1.344 (5) |
O13—C17 | 1.250 (5) | C25—C26 | 1.546 (6) |
O14—C17 | 1.265 (5) | C26—F28 | 1.330 (5) |
O15—C19 | 1.256 (5) | C26—F30 | 1.335 (5) |
O16—C19 | 1.259 (5) | C26—F29 | 1.347 (5) |
O17—C21 | 1.262 (5) | C27—C28 | 1.541 (6) |
O18—C21 | 1.255 (5) | C28—F32 | 1.340 (5) |
O19—C23 | 1.250 (5) | C28—F33 | 1.340 (5) |
O20—C23 | 1.261 (5) | C28—F31 | 1.344 (5) |
O21—C25 | 1.258 (5) | C29—C30 | 1.546 (6) |
O22—C25 | 1.264 (5) | C30—F34 | 1.329 (5) |
O23—C27 | 1.254 (5) | C30—F36 | 1.339 (5) |
O24—C27 | 1.262 (5) | C30—F35 | 1.341 (6) |
O25—C29 | 1.269 (5) | ||
O13—Cu1—O11 | 168.91 (13) | O4—C3—O3 | 127.7 (4) |
O13—Cu1—O15 | 90.07 (14) | O4—C3—C4 | 113.2 (4) |
O11—Cu1—O15 | 88.13 (14) | O3—C3—C4 | 119.0 (4) |
O13—Cu1—O17 | 90.10 (13) | F6—C4—F4 | 107.9 (4) |
O11—Cu1—O17 | 88.79 (13) | F6—C4—F5 | 107.8 (4) |
O15—Cu1—O17 | 164.81 (14) | F4—C4—F5 | 107.4 (3) |
O13—Cu1—O9 | 97.37 (12) | F6—C4—C3 | 111.0 (4) |
O11—Cu1—O9 | 93.67 (13) | F4—C4—C3 | 113.3 (4) |
O15—Cu1—O9 | 104.34 (13) | F5—C4—C3 | 109.2 (4) |
O17—Cu1—O9 | 90.70 (12) | O5—C5—O6 | 128.9 (4) |
O13—Cu1—Cu2 | 83.87 (9) | O5—C5—C6 | 112.8 (4) |
O11—Cu1—Cu2 | 85.05 (10) | O6—C5—C6 | 118.3 (4) |
O15—Cu1—Cu2 | 83.01 (10) | F8—C6—F9 | 107.8 (4) |
O17—Cu1—Cu2 | 81.90 (9) | F8—C6—F7 | 107.5 (4) |
O9—Cu1—Cu2 | 172.50 (9) | F9—C6—F7 | 107.1 (4) |
O18—Cu2—O12 | 90.19 (14) | F8—C6—C5 | 111.7 (4) |
O18—Cu2—O14 | 88.78 (14) | F9—C6—C5 | 110.3 (4) |
O12—Cu2—O14 | 165.11 (13) | F7—C6—C5 | 112.2 (4) |
O18—Cu2—O16 | 168.51 (14) | O7—C7—O8 | 128.8 (4) |
O12—Cu2—O16 | 88.84 (13) | O7—C7—C8 | 115.1 (4) |
O14—Cu2—O16 | 89.22 (13) | O8—C7—C8 | 116.1 (4) |
O18—Cu2—O10 | 99.09 (13) | F11—C8—F10 | 107.8 (4) |
O12—Cu2—O10 | 95.91 (13) | F11—C8—F12 | 108.3 (4) |
O14—Cu2—O10 | 98.93 (12) | F10—C8—F12 | 107.4 (4) |
O16—Cu2—O10 | 92.40 (13) | F11—C8—C7 | 111.6 (4) |
O18—Cu2—Cu1 | 84.88 (10) | F10—C8—C7 | 112.1 (4) |
O12—Cu2—Cu1 | 81.96 (10) | F12—C8—C7 | 109.4 (4) |
O14—Cu2—Cu1 | 83.15 (9) | C10—C9—H9A | 109.5 |
O16—Cu2—Cu1 | 83.65 (9) | C10—C9—H9B | 109.5 |
O10—Cu2—Cu1 | 175.53 (9) | H9A—C9—H9B | 109.5 |
O23—Cu3—O22 | 170.41 (13) | C10—C9—H9C | 109.5 |
O23—Cu3—Cu6 | 86.44 (10) | H9A—C9—H9C | 109.5 |
O22—Cu3—Cu6 | 86.08 (10) | H9B—C9—H9C | 109.5 |
O23—Cu3—Cu5 | 84.31 (10) | O9—C10—C9 | 122.0 (5) |
O22—Cu3—Cu5 | 87.02 (10) | O9—C10—C11 | 122.1 (5) |
Cu6—Cu3—Cu5 | 64.09 (2) | C9—C10—C11 | 115.8 (5) |
O8—Cu4—O1 | 170.82 (13) | C10—C11—H11A | 109.5 |
O8—Cu4—Cu9 | 84.46 (9) | C10—C11—H11B | 109.5 |
O1—Cu4—Cu9 | 87.60 (9) | H11A—C11—H11B | 109.5 |
O8—Cu4—Cu10 | 85.91 (9) | C10—C11—H11C | 109.5 |
O1—Cu4—Cu10 | 86.53 (9) | H11A—C11—H11C | 109.5 |
Cu9—Cu4—Cu10 | 64.55 (2) | H11B—C11—H11C | 109.5 |
O24—Cu5—O25 | 170.39 (14) | C13—C12—H12A | 109.5 |
O24—Cu5—Cu3 | 80.59 (10) | C13—C12—H12B | 109.5 |
O25—Cu5—Cu3 | 106.94 (10) | H12A—C12—H12B | 109.5 |
O24—Cu5—Cu8 | 99.93 (10) | C13—C12—H12C | 109.5 |
O25—Cu5—Cu8 | 82.48 (10) | H12A—C12—H12C | 109.5 |
Cu3—Cu5—Cu8 | 114.99 (3) | H12B—C12—H12C | 109.5 |
O24—Cu5—Cu6 | 86.79 (10) | O10—C13—C14 | 120.9 (4) |
O25—Cu5—Cu6 | 102.21 (10) | O10—C13—C12 | 122.2 (4) |
Cu3—Cu5—Cu6 | 57.85 (2) | C14—C13—C12 | 116.9 (5) |
Cu8—Cu5—Cu6 | 57.30 (2) | C13—C14—H14A | 109.5 |
O21—Cu6—O20 | 169.94 (14) | C13—C14—H14B | 109.5 |
O21—Cu6—Cu8 | 94.74 (10) | H14A—C14—H14B | 109.5 |
O20—Cu6—Cu8 | 84.56 (9) | C13—C14—H14C | 109.5 |
O21—Cu6—Cu3 | 78.88 (10) | H14A—C14—H14C | 109.5 |
O20—Cu6—Cu3 | 110.40 (10) | H14B—C14—H14C | 109.5 |
Cu8—Cu6—Cu3 | 117.01 (3) | O12—C15—O11 | 129.2 (4) |
O21—Cu6—Cu5 | 87.78 (10) | O12—C15—C16 | 116.0 (4) |
O20—Cu6—Cu5 | 100.36 (10) | O11—C15—C16 | 114.7 (4) |
Cu8—Cu6—Cu5 | 59.13 (2) | F13—C16—F15 | 108.0 (4) |
Cu3—Cu6—Cu5 | 58.05 (2) | F13—C16—F14 | 107.9 (4) |
O4—Cu7—O5 | 174.83 (15) | F15—C16—F14 | 108.0 (4) |
O4—Cu7—Cu10 | 78.72 (10) | F13—C16—C15 | 112.1 (4) |
O5—Cu7—Cu10 | 106.12 (11) | F15—C16—C15 | 108.9 (4) |
O4—Cu7—Cu9 | 100.09 (11) | F14—C16—C15 | 111.8 (4) |
O5—Cu7—Cu9 | 80.85 (10) | O13—C17—O14 | 129.5 (4) |
Cu10—Cu7—Cu9 | 63.16 (2) | O13—C17—C18 | 116.0 (4) |
O19—Cu8—O26 | 175.98 (14) | O14—C17—C18 | 114.5 (4) |
O19—Cu8—Cu6 | 80.54 (10) | F18—C18—F16 | 107.9 (4) |
O26—Cu8—Cu6 | 103.38 (11) | F18—C18—F17 | 108.0 (4) |
O19—Cu8—Cu5 | 101.44 (11) | F16—C18—F17 | 108.4 (4) |
O26—Cu8—Cu5 | 81.29 (10) | F18—C18—C17 | 112.3 (4) |
Cu6—Cu8—Cu5 | 63.57 (2) | F16—C18—C17 | 111.9 (4) |
O7—Cu9—O6 | 169.93 (14) | F17—C18—C17 | 108.2 (4) |
O7—Cu9—Cu4 | 81.25 (10) | O15—C19—O16 | 127.8 (4) |
O6—Cu9—Cu4 | 105.67 (10) | O15—C19—C20 | 115.4 (4) |
O7—Cu9—Cu7 | 101.76 (10) | O16—C19—C20 | 116.7 (4) |
O6—Cu9—Cu7 | 82.18 (10) | F20—C20—F19 | 109.2 (4) |
Cu4—Cu9—Cu7 | 114.86 (3) | F20—C20—F21 | 107.2 (4) |
O7—Cu9—Cu10 | 86.13 (10) | F19—C20—F21 | 107.5 (4) |
O6—Cu9—Cu10 | 103.71 (10) | F20—C20—C19 | 108.6 (4) |
Cu4—Cu9—Cu10 | 57.80 (2) | F19—C20—C19 | 111.9 (4) |
Cu7—Cu9—Cu10 | 57.58 (2) | F21—C20—C19 | 112.2 (4) |
O2—Cu10—O3 | 169.64 (14) | O18—C21—O17 | 128.6 (4) |
O2—Cu10—Cu4 | 78.35 (10) | O18—C21—C22 | 115.6 (4) |
O3—Cu10—Cu4 | 111.40 (10) | O17—C21—C22 | 115.8 (4) |
O2—Cu10—Cu7 | 93.28 (10) | F24—C22—F23 | 109.1 (4) |
O3—Cu10—Cu7 | 85.53 (9) | F24—C22—F22 | 107.3 (4) |
Cu4—Cu10—Cu7 | 116.39 (3) | F23—C22—F22 | 107.0 (4) |
O2—Cu10—Cu9 | 88.90 (10) | F24—C22—C21 | 112.1 (4) |
O3—Cu10—Cu9 | 99.27 (10) | F23—C22—C21 | 109.5 (4) |
Cu4—Cu10—Cu9 | 57.65 (2) | F22—C22—C21 | 111.8 (4) |
Cu7—Cu10—Cu9 | 59.27 (2) | O19—C23—O20 | 128.3 (4) |
C1—O1—Cu4 | 116.7 (3) | O19—C23—C24 | 112.7 (4) |
C1—O2—Cu10 | 128.6 (3) | O20—C23—C24 | 118.9 (4) |
C3—O3—Cu10 | 118.6 (3) | F26—C24—F27 | 107.8 (4) |
C3—O4—Cu7 | 129.1 (3) | F26—C24—F25 | 108.2 (4) |
C5—O5—Cu7 | 125.4 (3) | F27—C24—F25 | 107.7 (4) |
C5—O6—Cu9 | 122.3 (3) | F26—C24—C23 | 111.2 (4) |
C7—O7—Cu9 | 124.8 (3) | F27—C24—C23 | 113.2 (4) |
C7—O8—Cu4 | 120.5 (3) | F25—C24—C23 | 108.5 (4) |
C10—O9—Cu1 | 135.9 (3) | O21—C25—O22 | 128.2 (4) |
C13—O10—Cu2 | 133.5 (3) | O21—C25—C26 | 116.1 (4) |
C15—O11—Cu1 | 120.1 (3) | O22—C25—C26 | 115.7 (4) |
C15—O12—Cu2 | 123.4 (3) | F28—C26—F30 | 108.8 (4) |
C17—O13—Cu1 | 121.7 (3) | F28—C26—F29 | 108.2 (4) |
C17—O14—Cu2 | 121.5 (3) | F30—C26—F29 | 107.9 (4) |
C19—O15—Cu1 | 123.5 (3) | F28—C26—C25 | 111.8 (4) |
C19—O16—Cu2 | 121.7 (3) | F30—C26—C25 | 110.8 (4) |
C21—O17—Cu1 | 123.0 (3) | F29—C26—C25 | 109.3 (4) |
C21—O18—Cu2 | 121.1 (3) | O23—C27—O24 | 128.4 (4) |
C23—O19—Cu8 | 126.6 (3) | O23—C27—C28 | 116.5 (4) |
C23—O20—Cu6 | 119.8 (3) | O24—C27—C28 | 115.1 (4) |
C25—O21—Cu6 | 128.0 (3) | F32—C28—F33 | 107.8 (4) |
C25—O22—Cu3 | 118.1 (3) | F32—C28—F31 | 107.9 (4) |
C27—O23—Cu3 | 120.9 (3) | F33—C28—F31 | 107.2 (4) |
C27—O24—Cu5 | 125.4 (3) | F32—C28—C27 | 112.4 (4) |
C29—O25—Cu5 | 121.7 (3) | F33—C28—C27 | 111.9 (4) |
C29—O26—Cu8 | 125.4 (3) | F31—C28—C27 | 109.5 (4) |
O2—C1—O1 | 128.8 (4) | O26—C29—O25 | 128.8 (4) |
O2—C1—C2 | 115.6 (4) | O26—C29—C30 | 113.4 (4) |
O1—C1—C2 | 115.5 (4) | O25—C29—C30 | 117.7 (4) |
F3—C2—F1 | 108.2 (4) | F34—C30—F36 | 107.9 (4) |
F3—C2—F2 | 107.7 (4) | F34—C30—F35 | 108.0 (4) |
F1—C2—F2 | 107.7 (4) | F36—C30—F35 | 107.0 (4) |
F3—C2—C1 | 112.1 (4) | F34—C30—C29 | 110.5 (4) |
F1—C2—C1 | 111.5 (4) | F36—C30—C29 | 112.9 (4) |
F2—C2—C1 | 109.4 (4) | F35—C30—C29 | 110.3 (4) |
Experimental details
Crystal data | |
Chemical formula | [Cu10(C2F3O2)12(C3H6O)2] |
Mr | 2107.80 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 8.4999 (12), 11.1689 (15), 32.202 (4) |
α, β, γ (°) | 94.586 (2), 90.880 (2), 107.708 (2) |
V (Å3) | 2900.4 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.78 |
Crystal size (mm) | 0.28 × 0.12 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.417, 0.752 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24771, 12733, 9129 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.126, 1.02 |
No. of reflections | 12733 |
No. of parameters | 923 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.11, −0.69 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXTL (Sheldrick, 2008).
Cu1—O13 | 1.965 (3) | Cu5—Cu6 | 2.9257 (9) |
Cu1—O11 | 1.966 (3) | Cu6—O21 | 1.888 (3) |
Cu1—O15 | 1.972 (3) | Cu6—O20 | 1.914 (3) |
Cu1—O17 | 1.991 (3) | Cu6—Cu8 | 2.7492 (8) |
Cu1—O9 | 2.167 (3) | Cu7—O4 | 1.876 (3) |
Cu1—Cu2 | 2.7171 (8) | Cu7—O5 | 1.889 (3) |
Cu2—O18 | 1.964 (3) | Cu7—O9 | 2.627 (3) |
Cu2—O12 | 1.977 (3) | Cu7—O17 | 2.539 (3) |
Cu2—O14 | 1.979 (3) | Cu7—Cu10 | 2.7750 (8) |
Cu2—O16 | 1.994 (3) | Cu7—Cu9 | 2.8258 (9) |
Cu2—O10 | 2.153 (3) | Cu8—O19 | 1.882 (3) |
Cu3—O23 | 1.895 (3) | Cu8—O10 | 2.736 (3) |
Cu3—O22 | 1.904 (3) | Cu8—O16 | 2.508 (3) |
Cu3—Cu6 | 2.7540 (9) | Cu8—O26 | 1.887 (3) |
Cu3—Cu5 | 2.7599 (8) | Cu9—O7 | 1.899 (3) |
Cu4—O8 | 1.896 (3) | Cu9—O6 | 1.917 (3) |
Cu4—O1 | 1.914 (3) | Cu9—Cu10 | 2.9333 (9) |
Cu4—Cu9 | 2.7443 (8) | Cu10—O2 | 1.882 (3) |
Cu4—Cu10 | 2.7489 (8) | Cu10—O3 | 1.912 (3) |
Cu5—O24 | 1.895 (3) | O9—C10 | 1.225 (6) |
Cu5—O25 | 1.922 (3) | O10—C13 | 1.235 (6) |
Cu5—Cu8 | 2.8043 (9) |