Bis(1,1,1,5,5,5-hexa­fluoro­pentane-2,4-dionato)tetra­kis­(μ₄-1,1,1,5,5,5-hexa­fluoro­pentane-2,2,4,4-tetra­olato)copper(II)octa­tin(II): a prospective precursor for Cu-doped SnO₂ films

The crystal structure of a tin-rich heterometallic supra­molecular product, [CuSn₈(C₅HF₆O₂)₂(C₅H₂F₆O₄)₄] or [Sn₄(hfpt)₂–Cu(hfac)₂–Sn₄(hfpt)₂], (I), is reported (hfpt is the tetra­anion of 1,1,1,5,5,5-hexa­fluoro­pentane-2,2,4,4-tetraol and hfac is the anion of 1,1,1,5,5,5-hexa­fluoro­pentane-2,4-dione). Reaction between tin(II) tetra­olate, [Sn₄(hfpt)₂], and copper(II) β-diketonate, [Cu(hfac)₂], was utilized for the preparation of (I). The asymmetric unit consists of the whole [Sn₄(hfpt)₂] unit and half of a [Cu(hfac)₂] unit, with the Cu atom lying on an inversion center. Inter­molecular Cu...O inter­actions from the axial positions of copper in [Cu(hfac)₂] and O atoms of the hfpt ligand in [Sn₄(hfpt)₂] mediate the formation of a sandwich-type structure for (I). Additional inter­molecular Sn...O inter­actions between neighbouring [Sn₄(hfpt)₂] units complete a two-dimensional network.

S1. Introduction

The growing demand for accurate and cost-effective air-quality analytical methods for environmental monitoring, automotive and medical/healthcare applications, as well as for domestic and industrial security, has led to the search for new materials and techniques to enhance the performance of viable gas sensors. Tin(IV) oxide is a wide-bandgap semiconductor employed in a variety of industrial applications, including solid state gas sensors, transparent conductors, and oxidation catalysts (Batzill et al., 2005). Semiconductor oxide gas sensors like SnO₂ have been widely studied due to their range of condu­cta­nce variability and response towards both oxidizing and reducing gases (Niranjan et al., 2003). Additives to SnO₂ have been used for sensitizing and increasing the detection response to particular gases. The doping of SnO₂ ceramics with copper has been studied extensively, resulting in considerably higher sensitivity and selectivity for hydrogen sulfide detection due to the copper cations, which help to promote the dissociation of H₂S (Manorama et al., 1994; Galdikas et al., 1995; Devi et al., 1995; Rumyantseva et al., 1996, 1997). This type of sensor has been under constant development because of the toxic and corrosive nature of hydrogen sulfide. During the past several years, thin/thick films of CuO–SnO₂ (Devi et al., 1995; Mangamma et al., 1998; Vasiliev et al., 1999) or Cu-doped SnO₂ (Niranjan et al., 2003) have been prepared using different techniques, i.e. aerosol deposition (Akimov et al., 1994), liquid-phase co-precipitation (Zhou, 2003), thermal evaporation (Katti et al., 2003), and sol-gel methods (Baker et al., 2007).

The inter­est in materials that incorporate more than one type of metal atom has generated a need for single-source precursors (SSP) – molecules containing all of the necessary elements in the proper ratios and decomposable in a controlled manner under mild conditions to yield phase-pure compounds (Jones, 2002; Hubert-Pfalzgraf, 2004; Bloor et al., 2011). It has been established that heterometallic (main group transition metal) β-diketonates can be effectively used as single-source precursors for mixed-metal oxide materials (Zhang et al., 2009; Navulla et al., 2011). Recently, we have reported (Wei et al., 2011) the preparation of a unique homoleptic tetra­nuclear complex [Sn₄(hfpt)₂] (hfpt^4- is the tetra­anion of 1,1,1,5,5,5-hexa­fluoro­pentane-2,2,4,4-tetraol). This work revealed the great potential of tetra­olate ligands, which are capable of bridging multiple metal atoms in the formation of polynuclear and heterometallic complexes. Moreover, a tetra­olate compound was shown to exhibit clean low-temperature decomposition yielding phase-pure SnO₂ oxide (Wei et al., 2011). Herein we report the synthesis and solid-state structure of a new tin-rich heteroleptic complex [Sn₄(hfpt)₂–Cu(hfac)₂–Sn₄(hfpt)₂], (I), a prospective single-source precursor for copper-doped SnO₂ films or nanoparticles (hfac^- is the anion of 1,1,1,5,5,5-hexa­fluoro­pentane-2,4-dione).

S2. Experimental

S2.1. Synthesis and crystallization

All manipulations were carried out in a dry oxygen-free di­nitro­gen atmosphere by employing standard Schlenk-line and glove-box techniques. [Sn₄(hfpt)₂] (Wei et al., 2011) and [Cu(hfac)₂] (Maverick et al., 2002) were prepared according to literature procedures.

For the synthesis of (I), a mixture of tin tetra­olate [Sn₄(hfpt)₂] (0.120 g, 0.124 mmol) and copper β-diketonate [Cu(hfac)₂] (0.030 g, 0.062 mmol) was refluxed for 30 min in hexanes (10 ml) to afford a blue solution. The reaction mixture was concentrated by the removal of hexanes (ca 8 ml) under vacuum, and the remaining solution was placed in the freezer (273 K, 3 d) to yield light-blue crystals of the title compound.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The CF₃ groups of [Cu(hfac)₂] were found to be rotationally disordered. This disorder was individually modelled in both cases with two orientations and relative occupancies of 1:1 for the two parts. The C—F bond lengths were restrained to 1.34 (1) Å. The geometries of the two disordered parts were restrained to be similar. The anisotropic displacement parameters of the disordered –CF₃ groups in the direction of the bonds were restrained to be equal with a standard uncertainty of 0.01 Ų. They were also restrained to have the same U^ij components with a standard uncertainty of 0.04 Ų. H atoms were included at calculated positions (methyl­ene C—H = 0.97 Å and C3—H3 = 0.93 Å) and refined as riders, with U_iso(H) = 1.2U_eq(C).

S3. Results and discussion

The asymmetric unit of (I) consists of the whole [Sn₄(hfpt)₂] fragment and half of the [Cu(hfac)₂] moiety with the Cu atom lying on an inversion center. The molecular structure is comprised of a planar β-diketonate unit sandwiched between two tetra­nuclear [Sn₄(hfpt)₂] units (Fig. 1). Each [Sn₄(hfpt)₂] unit consists of four metal atoms which make up a butterfly tetra­hedron with two longer and two shorter Sn···Sn distances of 3.668 (9)/3.742 (1) and 4.953 (9)/4.966 (1) Å. Each of the Sn atoms is coordinated by two O atoms from each tetra­dentate tetra­olate ligand maintaining a pyramidal coordination, as expected for Sn²⁺, which has a lone electron pair. For each tin centre three of the Sn—O bonds are shorter with the distances ranging from 2.083 (3) to 2.222 (3) Å, while one is longer [2.659 (3)—2.887 (3) Å] (Table 2). The same is observed in [Sn₄(hfpt)₂] itself (Wei et al., 2011) with three shorter bonds [2.126 (2)–2.200 (2) Å] and one longer with a distance of 2.750 (2) Å. There are several changes in the corresponding Sn—O distances in the [Sn₄(hfpt)₂] units of (I), most notably in the elongation by 0.14 Å in the Sn1—O3 bond [2.887 (3) Å] as opposed to 2.750 (2) Å for [Sn₄(hfpt)₂] itself. This can be attributed to the O3 atoms in (I) being involved in additional noncovalent inter­actions with Cu1.

The [Cu(hfac)₂] unit of (I), which sits on an inversion centre, consists of two fluorinated chelating β-diketonate ligands with equatorial Cu—O distances of 1.924 (2) and 1.927 (3) Å, and cis-O—Cu—O angles of 92.28 (10) and 87.72 (10)°. There is a negligible change in (I) from the O—Cu—O angles of 93.24 and 86.76° in unsolvated [Cu(hfac)₂]; however, a comparison of Cu—O distances reveals that one of the bonds is more than 0.01 Å shorter [1.914 (3) Å] in the unsolvated species. Elongation of Cu—O bonds is generally observed in Cu^II β-diketonates upon coordination of O-donor ligands (Xu et al., 2000; Maverick et al., 2002; Visintin et al., 2005; Pampaloni et al., 2005; Filyakova et al., 2009; Pointillart et al., 2010) in comparison with unsolvated species. In most cases, the effect is more pronounced than is observed in (I).

The two additional Cu···O inter­actions [Cu1···O3 = Cu1···O3A = 2.985 (3) Å; Fig. 1] at the axial positions of the planar β-diketonate unit in (I) provide an elongated o­cta­hedral coordination environment around the Cu atom. These axial contacts are significantly longer than those in the previously reported [Cu(hfac)₂] complexes with O-donor ligands, which commonly span the range from 1.98 to 2.60 Å. The previously reported trinuclear complex [Bi(hfac)₃–Cu(hfac)₂–Bi(hfac)₃] (Dikarev et al., 2005) also has a planar [Cu(hfac)₂] unit, sandwiched between two Bi(hfac)₃ units. This sandwich complex exhibits essentially the same equatorial Cu—O bond lengths of 1.926 (2) and 1.928 (2) Å as in (I) and a shorter inter­molecular axial contact of an O atom of [Bi(hfac)₃] and the Cu atom of [Cu(hfac)₂] [2.588 (2) Å]. While the axial Cu1···O3 and Cu1···O3A contacts in (I) are longer in comparison to previously reported structures, they are still less than the sum of the van der Waals radii of Cu and O (3.42 Å; Bondi, 1964; Batsanov, 2011).

In addition to Cu···O inter­actions, inter­molecular noncovalent Sn···O inter­actions between neighbouring [Sn₄(hfpt)₂] units are also observed in (I) [Sn4···O6(-x+2, -y+1, -z+1) = 3.467 (3) Å], leading to the formation of a one-dimensional zigzag chain shown in Fig. 2(a). These chains are further linked into a three-dimensional supra­molecular structure through the additional rather long Sn···O inter­actions between neighbouring units [Sn2···O9(x, -y+3/2, z+1/2) = 3.624 (2) Å; Fig. 2b]. Similar inter­molecular inter­actions are also found in the crystal packing of homoleptic [Sn₄(hfpt)₂], with inter­molecular Sn···O contacts of 3.646 (2) Å. These noncovalent Sn···O inter­actions are all within the sum of the van der Waals radii of Sn and O atoms (3.81 Å; Bondi, 1964; Batsanov, 2011).

In summary, a new product, [Sn₄(hfpt)₂–Cu(hfac)₂–Sn₄(hfpt)₂] (I), has been prepared by the direct reaction of the homometallic complexes [Sn₄(hfpt)₂] and [Cu(hfac)₂]. The product represents an unusual tin-rich heteroleptic complex with Sn to Cu ratio of 8:1. This new single-source precursor should provide an attractive low-temperature preparative route to Cu-doped SnO₂ thin films.

Related literature

For related literature, see: Akimov et al. (1994); Baker et al. (2007); Batsanov (2011); Batzill & Diebold (2005); Bloor et al. (2011); Bondi (1964); Devi et al. (1995); Dikarev et al. (2005); Filyakova et al. (2009); Galdikas et al. (1995); Hubert-Pfalzgraf (2004); Jones (2002); Katti et al. (2003); Mangamma et al. (1998); Manorama et al. (1994); Maverick et al. (2002); Navulla et al. (2011); Niranjan et al. (2003); Pampaloni et al. (2005); Pointillart et al. (2010); Rumyantseva et al. (1996, 1997); Vasiliev et al. (1999); Visintin et al. (2005); Wei et al. (2011); Xu et al. (2000); Zhang et al. (2009); Zhou (2003).

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL (Bruker, 2003); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: SHELXTL (Bruker, 2003).

Figures

	Fig. 1. The molecular structure of (I), showing symmetry-equivalent atoms. Displacement ellipsoids are drawn at the 30% probability level. Cu···O interactions are represented as dashed lines. The –CF3 groups of the [Cu(hfac)2] unit were found to be rotationally disordered, and only one of the orientations is shown. [Symmetry code: (A) -x+1, -y+1, -z+1.]
	Fig. 2. (a) A view of the one-dimensional polymeric chain in (I). (b) A perspective view of the three-dimensional structure of (I). Intermolecular Cu···O and Sn···O interactions are represented as dashed lines. F and H atoms have been omitted for clarity.

Bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)tetrakis(µ₄-1,1,1,5,5,5-hexafluoropentane-2,2,4,4-tetraolato)copper(II)octatin(II)

Crystal data

[CuSn8(C5HF6O2)2(C5H2F6O4)4]	F(000) = 2206
Mr = 2387.61	Dx = 2.706 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8340 reflections
a = 16.716 (4) Å	θ = 2.2–28.5°
b = 12.535 (3) Å	µ = 3.88 mm^−1
c = 15.232 (4) Å	T = 293 K
β = 113.331 (3)°	Block, green
V = 2930.6 (12) Å^3	0.41 × 0.32 × 0.08 mm
Z = 2

Data collection

Bruker SMART APEX CCD area-detector diffractometer	7021 independent reflections
Radiation source: fine-focus sealed tube	6002 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
0.30° ω scans	θmax = 28.7°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −22→22
Tmin = 0.299, Tmax = 0.746	k = −16→16
22479 measured reflections	l = −19→19

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H-atom parameters constrained
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.034P)^2 + 1.9804P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
7021 reflections	Δρmax = 0.69 e Å^−3
485 parameters	Δρmin = −0.94 e Å^−3
72 restraints	Extinction correction: SHELXTL (Bruker, 2003), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00174 (9)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Sn1	0.684173 (15)	0.752594 (19)	0.357845 (16)	0.04280 (8)
Sn2	0.722793 (15)	0.662221 (19)	0.605542 (16)	0.04115 (7)
Sn3	0.954002 (15)	0.67365 (2)	0.641146 (16)	0.04504 (8)
Sn4	0.876168 (16)	0.57890 (2)	0.393423 (16)	0.04587 (8)
Cu1	0.5000	0.5000	0.5000	0.0600 (2)
O1	0.4189 (2)	0.51489 (19)	0.36893 (18)	0.0595 (7)
O2	0.50640 (18)	0.65192 (18)	0.51989 (17)	0.0508 (6)
O3	0.65463 (16)	0.5836 (2)	0.47029 (17)	0.0508 (6)
O4	0.74531 (15)	0.59573 (18)	0.39061 (16)	0.0415 (5)
O5	0.83692 (15)	0.57699 (19)	0.60977 (17)	0.0463 (5)
O6	0.90733 (17)	0.4984 (2)	0.52585 (18)	0.0519 (6)
O7	0.73745 (15)	0.78600 (19)	0.50852 (15)	0.0425 (5)
O8	0.86137 (16)	0.7866 (2)	0.64342 (15)	0.0448 (5)
O9	0.80713 (16)	0.7857 (2)	0.36022 (16)	0.0480 (6)
O10	0.91559 (16)	0.71384 (19)	0.49138 (15)	0.0433 (5)
C2	0.3957 (3)	0.6016 (3)	0.3251 (3)	0.0532 (9)
C3	0.4155 (3)	0.7026 (3)	0.3617 (3)	0.0613 (11)
H3	0.3929	0.7608	0.3217	0.074*
C4	0.4681 (2)	0.7197 (3)	0.4563 (3)	0.0473 (8)
C6	0.6297 (3)	0.4715 (3)	0.3372 (3)	0.0556 (9)
C7	0.6988 (2)	0.5251 (3)	0.4263 (2)	0.0437 (7)
C8	0.7584 (3)	0.4395 (3)	0.4904 (3)	0.0525 (9)
H8A	0.7700	0.3868	0.4504	0.063*
H8B	0.7279	0.4038	0.5246	0.063*
C9	0.8454 (2)	0.4811 (3)	0.5633 (2)	0.0464 (8)
C10	0.8811 (3)	0.3966 (3)	0.6434 (3)	0.0609 (10)
C11	0.7772 (2)	0.9429 (3)	0.6031 (2)	0.0485 (8)
C12	0.8116 (2)	0.8473 (3)	0.5646 (2)	0.0404 (7)
C13	0.8619 (2)	0.8907 (3)	0.5078 (2)	0.0440 (7)
H13A	0.9175	0.9179	0.5524	0.053*
H13B	0.8297	0.9503	0.4694	0.053*
C14	0.8789 (2)	0.8101 (3)	0.4421 (2)	0.0421 (7)
C15	0.9473 (3)	0.8577 (3)	0.4085 (3)	0.0527 (9)
C5	0.4868 (3)	0.8347 (3)	0.4919 (3)	0.0619 (10)
F1	0.5674 (4)	0.8541 (7)	0.5307 (15)	0.144 (6)	0.50
F2	0.4566 (12)	0.8491 (7)	0.5598 (10)	0.130 (3)	0.50
F3	0.4440 (9)	0.9050 (5)	0.4284 (6)	0.107 (4)	0.50
F1X	0.5362 (9)	0.8432 (6)	0.5809 (5)	0.109 (4)	0.50
F2X	0.4195 (5)	0.8884 (8)	0.4777 (12)	0.125 (4)	0.50
F3X	0.5277 (11)	0.8858 (7)	0.4437 (10)	0.126 (3)	0.50
C1	0.3392 (3)	0.5887 (3)	0.2185 (3)	0.0715 (13)
F4	0.3318 (11)	0.6725 (7)	0.1638 (7)	0.139 (6)	0.50
F5	0.2645 (7)	0.5429 (11)	0.2013 (12)	0.115 (5)	0.50
F6	0.3768 (7)	0.5174 (7)	0.1811 (6)	0.087 (3)	0.50
F4X	0.2867 (7)	0.6736 (6)	0.1878 (6)	0.115 (4)	0.50
F5X	0.2821 (6)	0.5123 (8)	0.2061 (11)	0.092 (4)	0.50
F6X	0.3824 (8)	0.5681 (13)	0.1669 (8)	0.172 (8)	0.50
F7	0.73584 (15)	0.91254 (19)	0.65804 (16)	0.0609 (6)
F8	0.72132 (18)	1.0016 (2)	0.53164 (17)	0.0718 (7)
F9	0.84192 (17)	1.00768 (18)	0.65598 (17)	0.0658 (6)
F10	0.9220 (2)	0.9522 (2)	0.3658 (2)	0.0784 (7)
F11	1.02471 (16)	0.8712 (2)	0.48021 (17)	0.0709 (7)
F12	0.95949 (17)	0.7935 (2)	0.34485 (17)	0.0706 (7)
F13	0.57335 (16)	0.5415 (2)	0.27939 (17)	0.0723 (7)
F14	0.58367 (18)	0.3982 (2)	0.3600 (2)	0.0819 (8)
F15	0.66715 (18)	0.4213 (2)	0.28552 (18)	0.0726 (7)
F16	0.83044 (19)	0.3855 (2)	0.6919 (2)	0.0823 (8)
F17	0.8861 (2)	0.3013 (2)	0.6074 (2)	0.0930 (9)
F18	0.96074 (17)	0.4219 (2)	0.70774 (18)	0.0748 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.03952 (13)	0.04925 (14)	0.03276 (12)	0.00568 (10)	0.00701 (9)	−0.00056 (9)
Sn2	0.04109 (13)	0.04987 (14)	0.03410 (12)	0.00357 (10)	0.01661 (10)	−0.00235 (9)
Sn3	0.03698 (13)	0.06191 (16)	0.03252 (12)	0.01043 (10)	0.00982 (9)	0.00194 (9)
Sn4	0.05030 (14)	0.05373 (15)	0.03582 (12)	0.00782 (11)	0.01946 (10)	−0.00474 (10)
Cu1	0.0848 (5)	0.0310 (3)	0.0409 (3)	0.0047 (3)	0.0001 (3)	0.0025 (2)
O1	0.0807 (19)	0.0349 (12)	0.0444 (13)	−0.0015 (12)	0.0051 (13)	0.0065 (10)
O2	0.0631 (16)	0.0351 (12)	0.0443 (13)	0.0048 (11)	0.0109 (12)	0.0019 (10)
O3	0.0436 (13)	0.0633 (16)	0.0426 (13)	0.0050 (12)	0.0140 (11)	−0.0115 (11)
O4	0.0410 (12)	0.0401 (12)	0.0408 (12)	0.0000 (10)	0.0133 (10)	−0.0039 (9)
O5	0.0454 (13)	0.0481 (14)	0.0417 (12)	0.0102 (11)	0.0132 (10)	−0.0012 (10)
O6	0.0545 (15)	0.0555 (15)	0.0481 (14)	0.0121 (12)	0.0231 (12)	0.0064 (11)
O7	0.0438 (13)	0.0474 (13)	0.0359 (11)	−0.0003 (10)	0.0152 (10)	−0.0051 (10)
O8	0.0498 (14)	0.0524 (14)	0.0311 (11)	0.0100 (11)	0.0147 (10)	0.0020 (10)
O9	0.0501 (14)	0.0617 (15)	0.0314 (11)	−0.0015 (12)	0.0153 (10)	−0.0010 (10)
O10	0.0491 (13)	0.0482 (13)	0.0333 (11)	0.0045 (11)	0.0170 (10)	0.0003 (9)
C2	0.057 (2)	0.0413 (19)	0.049 (2)	−0.0028 (17)	0.0085 (17)	0.0079 (15)
C3	0.071 (3)	0.0374 (18)	0.054 (2)	−0.0014 (18)	0.0025 (19)	0.0111 (16)
C4	0.050 (2)	0.0306 (16)	0.057 (2)	0.0018 (14)	0.0162 (17)	0.0021 (14)
C6	0.058 (2)	0.055 (2)	0.052 (2)	−0.0130 (19)	0.0208 (19)	−0.0135 (17)
C7	0.0463 (19)	0.0465 (18)	0.0388 (17)	−0.0019 (15)	0.0176 (14)	−0.0062 (14)
C8	0.061 (2)	0.0450 (19)	0.055 (2)	0.0008 (17)	0.0269 (18)	−0.0022 (16)
C9	0.053 (2)	0.0447 (18)	0.0436 (18)	0.0124 (16)	0.0221 (16)	0.0039 (14)
C10	0.070 (3)	0.057 (2)	0.061 (2)	0.019 (2)	0.033 (2)	0.0127 (19)
C11	0.053 (2)	0.050 (2)	0.0398 (18)	0.0081 (17)	0.0158 (16)	−0.0057 (15)
C12	0.0425 (17)	0.0437 (17)	0.0315 (15)	0.0045 (14)	0.0109 (13)	−0.0039 (12)
C13	0.0476 (19)	0.0432 (18)	0.0398 (17)	−0.0017 (15)	0.0158 (15)	−0.0004 (14)
C14	0.0447 (18)	0.0479 (18)	0.0350 (16)	0.0016 (15)	0.0170 (14)	0.0029 (13)
C15	0.054 (2)	0.064 (2)	0.0455 (19)	−0.0078 (18)	0.0249 (17)	−0.0020 (17)
C5	0.063 (3)	0.041 (2)	0.073 (3)	0.0061 (18)	0.017 (2)	−0.0038 (18)
F1	0.046 (3)	0.049 (4)	0.287 (17)	−0.010 (3)	0.014 (6)	−0.037 (9)
F2	0.215 (12)	0.076 (5)	0.140 (8)	0.022 (7)	0.112 (9)	−0.016 (5)
F3	0.161 (10)	0.034 (3)	0.083 (5)	0.016 (5)	0.003 (5)	0.004 (3)
F1X	0.134 (8)	0.054 (4)	0.081 (5)	0.007 (6)	−0.020 (5)	−0.027 (3)
F2X	0.067 (4)	0.079 (7)	0.203 (13)	0.037 (4)	0.024 (7)	−0.046 (7)
F3X	0.185 (10)	0.055 (5)	0.185 (10)	−0.044 (6)	0.122 (9)	−0.028 (5)
C1	0.082 (3)	0.056 (2)	0.052 (2)	−0.008 (2)	0.000 (2)	0.0107 (19)
F4	0.265 (16)	0.064 (4)	0.047 (4)	−0.015 (6)	0.019 (7)	0.019 (3)
F5	0.055 (4)	0.205 (14)	0.066 (6)	−0.015 (6)	0.004 (4)	−0.001 (9)
F6	0.110 (6)	0.107 (5)	0.038 (4)	0.005 (4)	0.023 (3)	−0.008 (3)
F4X	0.145 (8)	0.071 (5)	0.055 (5)	0.010 (5)	−0.039 (5)	0.019 (3)
F5X	0.102 (8)	0.058 (3)	0.068 (5)	−0.031 (4)	−0.018 (5)	0.007 (3)
F6X	0.095 (6)	0.37 (2)	0.044 (4)	−0.058 (11)	0.020 (4)	0.041 (10)
F7	0.0660 (14)	0.0692 (15)	0.0554 (13)	0.0069 (11)	0.0323 (11)	−0.0126 (11)
F8	0.0825 (17)	0.0670 (15)	0.0581 (13)	0.0329 (13)	0.0194 (13)	0.0014 (11)
F9	0.0778 (16)	0.0560 (13)	0.0607 (14)	−0.0093 (12)	0.0242 (12)	−0.0219 (11)
F10	0.096 (2)	0.0731 (16)	0.0775 (17)	−0.0051 (15)	0.0470 (16)	0.0213 (14)
F11	0.0543 (13)	0.0975 (19)	0.0621 (14)	−0.0185 (13)	0.0244 (12)	−0.0088 (13)
F12	0.0749 (16)	0.0939 (18)	0.0599 (14)	−0.0091 (14)	0.0447 (13)	−0.0115 (13)
F13	0.0609 (15)	0.0817 (17)	0.0531 (13)	−0.0076 (13)	0.0001 (11)	−0.0111 (12)
F14	0.0785 (18)	0.0809 (18)	0.0857 (19)	−0.0359 (15)	0.0317 (15)	−0.0108 (15)
F15	0.0857 (18)	0.0706 (16)	0.0629 (15)	−0.0133 (13)	0.0307 (14)	−0.0317 (12)
F16	0.0885 (19)	0.093 (2)	0.0782 (17)	0.0175 (16)	0.0468 (16)	0.0356 (15)
F17	0.120 (2)	0.0517 (15)	0.105 (2)	0.0318 (16)	0.042 (2)	0.0131 (14)
F18	0.0674 (16)	0.0909 (19)	0.0611 (15)	0.0252 (14)	0.0202 (13)	0.0260 (13)

Geometric parameters (Å, º)

Sn1—Sn4	3.7359 (8)	C2—C3	1.369 (5)
Sn1—Sn2	3.7424 (9)	C2—C1	1.530 (6)
Sn1—Sn3	4.9526 (9)	C3—C4	1.376 (5)
Sn2—Sn3	3.6868 (10)	C3—H3	0.9300
Sn2—Sn4	4.9664 (9)	C4—C5	1.528 (5)
Sn3—Sn4	3.6677 (9)	C6—F14	1.330 (5)
Sn1—O9	2.083 (3)	C6—F13	1.332 (5)
Sn1—O7	2.149 (2)	C6—F15	1.341 (5)
Sn1—O4	2.181 (2)	C6—C7	1.545 (5)
Sn1—O3	2.887 (3)	C7—C8	1.525 (5)
Sn2—O3	2.158 (2)	C8—C9	1.530 (5)
Sn2—O5	2.165 (2)	C8—H8A	0.9700
Sn2—O7	2.222 (2)	C8—H8B	0.9700
Sn2—O8	2.659 (3)	C9—C10	1.546 (5)
Sn3—O8	2.109 (2)	C10—F17	1.331 (5)
Sn3—O10	2.170 (2)	C10—F16	1.333 (5)
Sn3—O5	2.188 (3)	C10—F18	1.342 (5)
Sn3—O6	2.727 (3)	C11—F7	1.334 (4)
Sn4—O6	2.128 (2)	C11—F9	1.337 (4)
Sn4—O10	2.178 (2)	C11—F8	1.340 (4)
Sn4—O4	2.181 (2)	C11—C12	1.542 (5)
Sn4—O9	2.800 (3)	C12—C13	1.525 (5)
Cu1—O2^i	1.924 (2)	C13—C14	1.525 (5)
Cu1—O2	1.924 (2)	C13—H13A	0.9700
Cu1—O1^i	1.927 (3)	C13—H13B	0.9700
Cu1—O1	1.927 (3)	C14—C15	1.546 (5)
O1—C2	1.254 (4)	C15—F11	1.332 (4)
O2—C4	1.257 (4)	C15—F12	1.336 (4)
O3—C7	1.387 (4)	C15—F10	1.336 (5)
O4—C7	1.421 (4)	C5—F1	1.262 (6)
O5—C9	1.430 (4)	C5—F3	1.294 (6)
O6—C9	1.383 (4)	C5—F2	1.330 (7)
O7—C12	1.421 (4)	C1—F5	1.302 (8)
O8—C12	1.387 (4)	C1—F4	1.316 (6)
O9—C14	1.380 (4)	C1—F6	1.342 (7)
O10—C14	1.425 (4)
O9—Sn1—O7	87.36 (9)	C9—C8—H8A	108.6
O9—Sn1—O4	78.79 (10)	C7—C8—H8B	108.6
O7—Sn1—O4	88.44 (9)	C9—C8—H8B	108.6
O3—Sn2—O5	85.92 (9)	H8A—C8—H8B	107.6
O3—Sn2—O7	80.77 (9)	O6—C9—O5	108.0 (3)
O5—Sn2—O7	92.08 (9)	O6—C9—C8	113.9 (3)
O8—Sn3—O10	87.01 (8)	O5—C9—C8	113.2 (3)
O8—Sn3—O5	77.08 (10)	O6—C9—C10	108.4 (3)
O10—Sn3—O5	91.85 (9)	O5—C9—C10	105.6 (3)
O6—Sn4—O10	79.92 (9)	C8—C9—C10	107.3 (3)
O6—Sn4—O4	86.08 (9)	F17—C10—F16	107.0 (4)
O10—Sn4—O4	88.13 (9)	F17—C10—F18	107.9 (3)
O2^i—Cu1—O2	180.0	F16—C10—F18	106.5 (3)
O2^i—Cu1—O1^i	92.28 (10)	F17—C10—C9	111.0 (3)
O2—Cu1—O1^i	87.72 (10)	F16—C10—C9	112.2 (3)
O2^i—Cu1—O1	87.72 (10)	F18—C10—C9	112.1 (4)
O2—Cu1—O1	92.28 (10)	F7—C11—F9	107.0 (3)
O1^i—Cu1—O1	180.00 (19)	F7—C11—F8	107.4 (3)
C2—O1—Cu1	125.3 (2)	F9—C11—F8	107.1 (3)
C4—O2—Cu1	124.6 (2)	F7—C11—C12	112.4 (3)
C7—O3—Sn2	121.4 (2)	F9—C11—C12	111.5 (3)
C7—O4—Sn1	111.82 (19)	F8—C11—C12	111.2 (3)
C7—O4—Sn4	128.9 (2)	O8—C12—O7	107.8 (3)
Sn1—O4—Sn4	117.85 (10)	O8—C12—C13	114.2 (3)
C9—O5—Sn2	131.2 (2)	O7—C12—C13	113.4 (3)
C9—O5—Sn3	108.5 (2)	O8—C12—C11	106.4 (3)
Sn2—O5—Sn3	115.77 (11)	O7—C12—C11	106.3 (3)
C9—O6—Sn4	121.6 (2)	C13—C12—C11	108.2 (3)
C12—O7—Sn1	129.88 (19)	C12—C13—C14	115.1 (3)
C12—O7—Sn2	106.15 (18)	C12—C13—H13A	108.5
Sn1—O7—Sn2	117.78 (11)	C14—C13—H13A	108.5
C12—O8—Sn3	123.15 (19)	C12—C13—H13B	108.5
C14—O9—Sn1	123.98 (19)	C14—C13—H13B	108.5
C14—O10—Sn3	129.54 (19)	H13A—C13—H13B	107.5
C14—O10—Sn4	110.28 (18)	O9—C14—O10	109.1 (3)
Sn3—O10—Sn4	115.03 (11)	O9—C14—C13	114.7 (3)
O1—C2—C3	127.6 (4)	O10—C14—C13	111.6 (3)
O1—C2—C1	113.8 (3)	O9—C14—C15	106.2 (3)
C3—C2—C1	118.6 (3)	O10—C14—C15	106.3 (3)
C2—C3—C4	121.5 (3)	C13—C14—C15	108.4 (3)
C2—C3—H3	119.3	F11—C15—F12	107.1 (3)
C4—C3—H3	119.3	F11—C15—F10	107.7 (3)
O2—C4—C3	128.4 (3)	F12—C15—F10	106.9 (3)
O2—C4—C5	113.2 (3)	F11—C15—C14	112.5 (3)
C3—C4—C5	118.4 (3)	F12—C15—C14	110.7 (3)
F14—C6—F13	107.3 (3)	F10—C15—C14	111.7 (3)
F14—C6—F15	106.4 (3)	F1—C5—F3	112.9 (9)
F13—C6—F15	107.1 (3)	F1—C5—F2	105.9 (10)
F14—C6—C7	112.3 (3)	F3—C5—F2	102.8 (7)
F13—C6—C7	112.4 (3)	F1—C5—C4	112.2 (5)
F15—C6—C7	111.0 (3)	F3—C5—C4	113.7 (5)
O3—C7—O4	109.4 (3)	F2—C5—C4	108.4 (5)
O3—C7—C8	113.6 (3)	F5—C1—F4	112.4 (10)
O4—C7—C8	111.5 (3)	F5—C1—F6	101.1 (9)
O3—C7—C6	107.3 (3)	F4—C1—F6	101.8 (8)
O4—C7—C6	105.4 (3)	F5—C1—C2	113.6 (8)
C8—C7—C6	109.2 (3)	F4—C1—C2	116.8 (6)
C7—C8—C9	114.7 (3)	F6—C1—C2	109.0 (5)
C7—C8—H8A	108.6

Symmetry code: (i) −x+1, −y+1, −z+1.