Crystal structure of the coordination polymer catena-poly[[[(acetonitrile-κN)copper(I)]-μ3-1,3-dithiolane-κ3S:S:S′] hexafluoridophosphate]

Knauer, L.; Knorr, M.; Viau, L.; Strohmann, C.

doi:10.1107/S205698901901627X

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Volume 76| Part 1| January 2020| Pages 38-41

https://doi.org/10.1107/S205698901901627X

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Crystal structure of the coordination polymer catena-poly[[[(acetonitrile-κN)copper(I)]-μ₃-1,3-dithiolane-κ³S:S:S′] hexafluoridophosphate]

Lena Knauer,^a Michael Knorr,^b ^* Lydie Viau ^b and Carsten Strohmann ^a ^*

^aAnorganische Chemie, Technische Universität Dortmund, Otto-Hahn-Strasse 6, D-44227 Dortmund, Germany, and ^bInstitut UTINAM UMR 6213 CNRS, Université Bourgogne Franche-Comté, 16 Route de Gray, 25030 Besançon Cedex, France
^*Correspondence e-mail: michael.knorr@univ-fcomte.fr, carsten-strohmann@tu-dortmund.de

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 19 November 2019; accepted 3 December 2019; online 1 January 2020)

The polymeric title compound, [Cu₂(C₂H₃N)₂(C₃H₆S₂)₂](PF₆)₂, represents an example of a one-dimensional coordination polymer resulting from the reaction of [Cu(MeCN)₄][PF₆] with 1,3-dithiolane. The cationic one-dimensional ribbon consists of two copper(I) centers each ligated by one acetonitrile molecule and interconnected through two bridging 1,3-dithiolane ligands. One S-donor site of each ligand is κ¹-bound to Cu, whereas the second S atom acts as a four-electron donor, bridging two Cu atoms in a κ⁴-bonding mode. The positive charge of each copper cation is compensated for by a hexafluoridophosphate counter-ion. In the crystal, the polymer chains are linked by a series of C—H⋯F hydrogen bonds, forming a supramolecular framework.

Keywords: crystal structure; copper complex; coordination polymer; thioether; C—H⋯F hydrogen bonding.

CCDC reference: 1969688

1. Chemical context

The five-membered heterocyclic ligand tetrahydrothiophene (THT) is known to form a great variety of molecular complexes and coordination polymers (CPs) with various transition metals. Notably, for the soft coinage metal ions copper(I), silver(I) and gold(I), numerous structurally characterized examples coordinated by terminal or bridging THT ligands have been documented (Ahrland et al., 1993 ; Dembo et al., 2010 ; Norén & Oskarsson, 1985 ; Mälger et al., 1992 ; Usón et al., 1984 ). Even mixed-valence (Cu^I–Cu^II) compounds such as polymeric penta-μ-chloro-tris-μ-tetrahydrothiophenetetracopper(I,II) have been prepared (Ainscough et al., 1985 ). In the case of the five-membered heterocycle 1,2-dithiolane, in which one CH₂ unit is replaced by a second sulfur atom, there is one report on its coordination to Hg₂(NO₃)₂ yielding the Hg^I adduct 1,2-dithiolane·Hg₂(NO₃)₂ (Brodersen & Rölz, 1977 ). Furthermore, the dinuclear organometallic species [η⁵-CpMn(CO)₂(μ₂-1,2-dithiolane)]₂ has been characterized crystallographically (Braunwarth et al., 1991 ). The fluxional complexes [M(CO)₅(1,3-dithiolane)] (M = Cr, Mo, W) ligated by the isomeric heterocycle 1,3-dithiolane (1,3-dithiacyclopentane) have been investigated by NMR spectroscopy (Abel et al., 1990 ).

In a comparative study with respect to our previous work on the coordination chemistry of the open-chain dithioether analogues RS-CH₂-SR (Chaabéne et al., 2016 ; Knorr et al., 2014 ; Peindy et al., 2007 ) and in part to fill the gap between the versatile coordination chemistry of THT (see above) and the almost unexplored coordination chemistry of 1,3-dithiolane, we recently described in detail the construction and structural features of molecular clusters and coordination networks, with dimensionalities varying from 0D–2D by reacting 1,3-dithiolane and its ferrocenyl derivative substituted at the 2-position with CuX salts (X = Cl, Br, I) (Raghuvanshi et al., 2017 ). However, surprisingly, a survey of the Cambridge Structural Database (Groom et al., 2016 ), reveals that apart from our CuX–1,3-dithiolane compounds, no other unsubstituted 1,3-dithiolane complexes have been structurally characterized. We have now extended our project on the coordination chemistry of this cyclic dithioether using [Cu(MeCN)₄][PF₆] as reactant to obtain the title polymeric ionic salt-like material, which could be interesting for electrochemical investigations.

2. Structural commentary

We have previously described (Raghuvanshi et al., 2017), the structural features of the ribbon-like structures of compounds [{Cu(μ₂-Br)}(μ₂-L1)]_n and [{Cu(μ₂-Cl)}(μ₂-L1)]_n, formed upon treatment of CuBr and CuCl with 1,3-dithiolane (L1). The title complex salt, a ribbon of composition [Cu(1,3-dithiane)(MeCN)]_n⁺ (CP1) also results from the reaction of [Cu(MeCN)₄][PF₆] with L1, but its architecture is quite different.

The molecular structure of the asymmetric unit of the title complex is illustrated in Fig. 1, and selected bond lengths and bond angles are given in Table 1. The ribbon-like structure is built upon individual Cu^I atoms, each ligated by a datively bound MeCN ligand and interconnected to the neighbouring metal centers by two bridging dithiolane ligands (Fig. 2). Overall, the architecture of CP1 is quite reminiscent of that of the 1D polymeric tetrafluoridoborate salt [Cu(1,3-dithiane)(MeCN)]_n⁺ (Knaust & Keller, 2003 ). Nevertheless, there is one difference. Whereas the asymmetric unit of the latter salt (crystallizing in the orthorhombic Sohncke space group P2₁2₁2₁) contains three unique copper(I) centers, that of CP1 (crystallizing in the orthorhombic non-centrosymmetric space group Pna2₁) contains only two unique Cu^I atoms. Each displays a CuNS₃ four-coordinate environment; see Table 1 [L—Cu—L angles: 99.97 (7) to 119.47 (11)° for Cu1, and 99.29 (11) to 118.69 (4)° for Cu2]. The τ₄ descriptor for fourfold coordination is = 0.89 for both atoms Cu1 and Cu2, indicating that each have a trigonal-pyramidal geometry (τ₄ = 1 for a perfect tetrahedral geometry, = 0 for a perfect square planar geometry and = 0.85 for a perfect trigonal-pyramidal geometry; Yang et al., 2007 ).

Table 1
Selected geometric parameters (Å, °)

Cu1—N1	1.973 (3)	Cu2—N2	1.980 (3)
Cu1—S1	2.2630 (10)	Cu2—S3	2.2886 (11)
Cu1—S2ⁱ	2.3305 (9)	Cu2—S4ⁱ	2.3281 (9)
Cu1—S4ⁱ	2.3367 (11)	Cu2—S2	2.3357 (11)

N1—Cu1—S1	119.47 (11)	N2—Cu2—S4ⁱ	99.29 (11)
N1—Cu1—S2ⁱ	99.97 (9)	S3—Cu2—S4ⁱ	118.69 (4)
S1—Cu1—S2ⁱ	115.68 (4)	N2—Cu2—S2	106.03 (13)
N1—Cu1—S4ⁱ	105.68 (12)	S3—Cu2—S2	115.99 (4)
S1—Cu1—S4ⁱ	110.65 (4)	S4ⁱ—Cu2—S2	102.03 (4)
S2ⁱ—Cu1—S4ⁱ	103.69 (4)	Cu1ⁱⁱ—S2—Cu2	111.28 (4)
N2—Cu2—S3	112.75 (12)	Cu2ⁱⁱ—S4—Cu1ⁱⁱ	104.54 (4)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ .

Figure 1
A view of the asymmetric unit of the title compound, with atom labelling [symmetry codes: (i) x − $[{1\over 2}]$ , −y + $[{3\over 2}]$ , z; (ii) x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , z]. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
A partial view along the b axis of the crystal packing of the title compound. For clarity, the H atoms and the PF₆⁻ anions have been omitted.

The coordination environment for each of the Cu^I centers includes three bridging dithiolane ligands and one terminal acetonitrile ligand. All Cu—S bond lengths are in the range 2.2630 (10)–2.3367 (11) Å, the mean Cu—S bond length of 2.314 (12) Å is quite similar to that in [Cu(1,3-dithiane)(MeCN)]_n⁺. In addition, the mean Cu—N bond distance matches well with that of [Cu(1,3-dithiane)(MeCN)]_n [1.979 (4) versus 1.984 (7) Å]. The three dithiolane ligands each have one S atom that is a two-electron donor and one S atom that is a μ₂-four-electron donor. The Cu⋯Cu separations of ca 3.689–3.852 Å are far above the sum of the van der Waals radii of two Cu atoms (2.8 Å), excluding any bonding interaction. These two bonding modes lead to the formation of a ribbon-like coordination polymer, which runs parallel to the a axis, where each copper(I) center is bonded to two μ₂-S atoms and one μ₁-S atom (Fig. 2 and Table 1).

3. Supramolecular features

The crystal packing of the title compound is illustrated in Fig. 3, and shows the ribbon-like structures, propagating along the a-axis direction, that are linked by a number of C—H⋯F hydrogen bonds, forming a supramolecular framework (Fig. 3 and Table 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯F9ⁱⁱⁱ	0.99	2.55	3.264 (4)	129
C1—H1A⋯F12ⁱⁱⁱ	0.99	2.40	3.277 (5)	147
C2—H2A⋯F9ⁱⁱⁱ	0.99	2.50	3.287 (5)	136
C3—H3B⋯F4ⁱⁱ	0.99	2.42	3.376 (5)	161
C5—H5C⋯F6^iv	0.98	2.54	3.426 (6)	151
C8—H8A⋯F11	0.99	2.34	3.186 (5)	143
C8—H8B⋯F2^v	0.99	2.46	3.323 (5)	145
C10—H10A⋯F7ⁱⁱ	0.99	2.31	3.221 (5)	152
C10—H10B⋯F1ⁱⁱ	0.99	2.48	3.264 (5)	136
Symmetry codes: (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (iii) $[-x+1, -y+1, z+{\script{1\over 2}}]$ ; (iv) x, y+1, z; (v) $[-x+1, -y+1, z-{\script{1\over 2}}]$ .

Figure 3
A view along the a axis of the crystal packing of the title compound. The C—H⋯F hydrogen bonds (Table 2

) are shown as dashed lines. For clarity, only the H atoms involved in these interactions have been included.

4. Database survey

Other examples of crystallographically characterized 1,3-dithiolane complexes substituted at the 2-position found in the Cambridge Structural Database (CSD, version 5.40, update August 2019; Groom et al., 2016) include catena-[(μ₅-1,3-dithiolane-2-carboxylato)(μ₄-1,3-dithiolane-2-carboxylato)(μ₂-trifluoromethanesulfonato-O,O′)trisilver(I)] (CSD refcode FAQIPY; Gondi et al., 2011 ), catena-[(μ₃-1,3-dithiolane-2-methanol-S,S,S′)(nitrato-O)silver(I)] (HESLUN; Zhang et al., 2006 ), chlorotriphenylphosphine[2,5-bis(1,3-dithiolan-2-yl)phenyl-S]palladium(II) (IVUFEK; Vicente et al., 2004 ), rac-trans-dichlorobis{[2-(1,3-dithiolan-2-yl)phenyl](diphenyl)phosphine}ruthenium(II) chloroform solvate (TUMKOC; Bayly et al., 2009 ). Other examples of related 1,3-dithiane copper(I) coordination polymers have also been reported (Raghuvanshi et al., 2019 ).

5. Synthesis and crystallization

The reaction scheme for the synthesis of the title compound is illustrated in Fig. 4. To a solution of [Cu(MeCN)₄][PF₆] (372 mg, 0.1 mmol) in CH₂Cl₂ (10 ml) was added an equimolar amount of 1,3-dithiolane (L1) via a syringe. The solution was stirred at 293 K for 2 h, then layered with Et₂O (10 ml) and stored in a refrigerator for 2 days. Colourless block-like crystals formed progressively (245 mg, 68% yield).

Figure 4
Reaction scheme for the synthesis of the title compound, CP1.

Elemental analysis calculated for C₁₀H₁₈Cu₂F₁₂N₂P₂S₄: C, 16.88; H, 2.54; N, 3.94; S, 18.03%. Found: C, 16.44; H, 2.28; N, 3.44; S, 17.81%. IR (ATR; cm⁻¹): 2280 w (weak) (CN), 835 vs (very strong) (PF₆).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The C-bound H atoms were included in calculated positions and treated as riding: C—H = 0.98–0.99 Å with U_iso(H) = 1.5U_eq(C-methyl) and 1.2U_eq(C) for other H atoms. The structure was refined as a two-component inversion twin; BASF = 0.121 (12). In the final cycles of refinement three reflections were omitted; one was affected by the backstop and two were most disagreeable reflections.

Table 3
Experimental details

Crystal data
Chemical formula	[Cu₂(C₂H₃N)₂(C₃H₆S₂)₂] (PF₆)₂
M_r	711.52
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	105
a, b, c (Å)	11.8409 (9), 12.9273 (9), 15.2921 (11)
V (Å³)	2340.8 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.41
Crystal size (mm)	0.33 × 0.32 × 0.27

Data collection
Diffractometer	Bruker D8 VENTURE area detector
Absorption correction	Multi-scan (TWINABS; Bruker, 2016 )
T_min, T_max	0.608, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	40393, 8122, 7092
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.769

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.080, 1.03
No. of reflections	8122
No. of parameters	293
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.93, −0.73
Computer programs: APEX2 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ), Mercury (Macrae et al., 2008 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1969688

Crystal structure: contains datablocks Global, I. DOI: https://doi.org/10.1107/S205698901901627X/su5530sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901901627X/su5530Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698901901627X/su5530Isup3.cdx

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: ShelXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2(Dolomanov et al., 2009), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

catena-Poly[[[(acetonitrile-κN)copper(I)]-µ₃-1,3-dithiolane-κ³S:S:S'] hexafluoridophosphate] top

Crystal data top

[Cu₂(C₂H₃N)₂(C₃H₆S₂)₂](PF₆)₂	D_x = 2.019 Mg m⁻³
M_r = 711.52	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 9565 reflections
a = 11.8409 (9) Å	θ = 2.7–31.8°
b = 12.9273 (9) Å	µ = 2.41 mm⁻¹
c = 15.2921 (11) Å	T = 105 K
V = 2340.8 (3) Å³	Block, colourless
Z = 4	0.33 × 0.32 × 0.27 mm
F(000) = 1408

Data collection top

Bruker D8 VENTURE area detector diffractometer	8122 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	7092 reflections with I > 2σ(I)
HELIOS mirror optics monochromator	R_int = 0.040
Detector resolution: 10.4167 pixels mm^-1	θ_max = 33.1°, θ_min = 2.3°
ω and φ scans	h = −17→17
Absorption correction: multi-scan (TWINABS; Bruker, 2016)	k = −19→18
T_min = 0.608, T_max = 0.746	l = −21→23
40393 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.034	w = 1/[σ²(F_o²) + (0.0388P)² + 1.7169P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.080	(Δ/σ)_max = 0.001
S = 1.03	Δρ_max = 0.93 e Å⁻³
8122 reflections	Δρ_min = −0.73 e Å⁻³
293 parameters	Extinction correction: (SHELXL-2018/3; Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0012 (3)
Primary atom site location: dual	Absolute structure: Refined as an inversion twin.
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.115 (11)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a two-component inversion twin

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.84315 (3)	0.78973 (3)	0.57850 (3)	0.01740 (10)
Cu2	0.59217 (4)	0.80128 (3)	0.43586 (3)	0.01907 (10)
S1	0.73437 (7)	0.71169 (7)	0.68074 (6)	0.01758 (17)
S2	0.53256 (7)	0.75921 (6)	0.57705 (6)	0.01552 (15)
S3	0.47858 (7)	0.74560 (8)	0.32430 (7)	0.02113 (18)
S4	0.28017 (7)	0.75139 (6)	0.43792 (6)	0.01688 (16)
N1	0.8599 (3)	0.9416 (2)	0.5802 (3)	0.0218 (6)
N2	0.6146 (3)	0.9531 (3)	0.4352 (3)	0.0271 (7)
C1	0.6181 (3)	0.6541 (3)	0.6216 (3)	0.0176 (6)
H1A	0.572111	0.610665	0.661277	0.021*
H1B	0.646981	0.609859	0.573648	0.021*
C2	0.6454 (3)	0.8120 (3)	0.7273 (3)	0.0216 (7)
H2A	0.595280	0.781936	0.772430	0.026*
H2B	0.692894	0.865649	0.755319	0.026*
C3	0.5748 (3)	0.8604 (3)	0.6548 (3)	0.0229 (8)
H3A	0.619383	0.914115	0.624196	0.027*
H3B	0.506878	0.893506	0.680033	0.027*
C4	0.8973 (3)	1.0220 (3)	0.5899 (3)	0.0233 (7)
C5	0.9471 (4)	1.1236 (3)	0.6047 (3)	0.0337 (10)
H5A	1.026569	1.122572	0.586966	0.051*
H5B	0.941772	1.141126	0.666932	0.051*
H5C	0.906273	1.175400	0.570202	0.051*
C6	0.6404 (4)	1.0373 (4)	0.4332 (4)	0.0384 (10)
C7	0.6757 (8)	1.1462 (5)	0.4299 (6)	0.081 (3)
H7A	0.631809	1.182650	0.385163	0.122*
H7B	0.756221	1.150048	0.415362	0.122*
H7C	0.662709	1.178524	0.486982	0.122*
C8	0.3636 (3)	0.6684 (3)	0.3662 (3)	0.0212 (7)
H8A	0.393246	0.608356	0.399149	0.025*
H8B	0.316389	0.642406	0.317440	0.025*
C9	0.3864 (3)	0.8562 (3)	0.3071 (3)	0.0250 (8)
H9A	0.431480	0.917698	0.290743	0.030*
H9B	0.332220	0.841488	0.259437	0.030*
C10	0.3233 (3)	0.8761 (3)	0.3924 (3)	0.0241 (8)
H10A	0.256090	0.919716	0.381185	0.029*
H10B	0.372927	0.912903	0.434195	0.029*
P1	0.83561 (9)	0.41114 (8)	0.64167 (8)	0.0243 (2)
F1	0.8514 (2)	0.5141 (2)	0.5834 (2)	0.0352 (6)
F2	0.8195 (2)	0.3098 (2)	0.7025 (2)	0.0381 (7)
F3	0.9652 (2)	0.3807 (2)	0.6263 (2)	0.0400 (6)
F4	0.8733 (3)	0.4757 (2)	0.72667 (18)	0.0373 (6)
F5	0.7068 (2)	0.4413 (2)	0.6591 (3)	0.0478 (8)
F6	0.8011 (3)	0.3459 (3)	0.5585 (2)	0.0564 (10)
P2	0.56386 (9)	0.42170 (8)	0.34899 (7)	0.0242 (2)
F7	0.6297 (4)	0.5004 (3)	0.2875 (2)	0.0639 (11)
F8	0.4947 (4)	0.3435 (3)	0.4073 (2)	0.0765 (14)
F9	0.5737 (2)	0.3338 (2)	0.27453 (18)	0.0295 (5)
F10	0.6798 (2)	0.3850 (2)	0.3895 (2)	0.0402 (7)
F11	0.5557 (2)	0.5097 (2)	0.4233 (2)	0.0394 (7)
F12	0.4494 (3)	0.4601 (3)	0.3056 (3)	0.0836 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01103 (17)	0.02016 (19)	0.0210 (2)	−0.00064 (14)	0.00107 (16)	−0.00060 (19)
Cu2	0.01171 (18)	0.0229 (2)	0.0226 (2)	−0.00045 (15)	0.00019 (17)	0.00155 (19)
S1	0.0107 (3)	0.0221 (4)	0.0200 (4)	0.0000 (3)	−0.0009 (3)	0.0023 (3)
S2	0.0092 (3)	0.0186 (3)	0.0188 (4)	0.0002 (3)	0.0004 (3)	0.0008 (4)
S3	0.0130 (4)	0.0303 (4)	0.0201 (4)	0.0001 (3)	0.0025 (3)	−0.0025 (4)
S4	0.0098 (3)	0.0221 (4)	0.0187 (4)	0.0007 (3)	0.0008 (3)	0.0005 (4)
N1	0.0211 (14)	0.0210 (13)	0.0232 (15)	0.0036 (11)	0.0000 (14)	−0.0005 (14)
N2	0.0294 (17)	0.0244 (14)	0.0275 (16)	−0.0013 (13)	−0.0028 (17)	0.0032 (16)
C1	0.0109 (13)	0.0188 (15)	0.0232 (17)	0.0004 (12)	−0.0012 (13)	0.0041 (13)
C2	0.0162 (16)	0.0276 (17)	0.0210 (18)	−0.0007 (13)	0.0018 (13)	−0.0030 (15)
C3	0.0167 (16)	0.0221 (16)	0.030 (2)	0.0020 (13)	−0.0030 (14)	−0.0058 (15)
C4	0.0253 (18)	0.0239 (17)	0.0208 (18)	0.0042 (14)	−0.0024 (15)	−0.0012 (15)
C5	0.044 (3)	0.0210 (18)	0.036 (2)	−0.0023 (17)	−0.010 (2)	−0.0038 (17)
C6	0.050 (3)	0.030 (2)	0.036 (2)	−0.0020 (19)	−0.009 (2)	0.006 (2)
C7	0.115 (7)	0.031 (3)	0.097 (6)	−0.017 (3)	−0.028 (6)	0.022 (4)
C8	0.0131 (15)	0.0248 (17)	0.026 (2)	−0.0002 (13)	0.0027 (13)	−0.0048 (15)
C9	0.0189 (17)	0.032 (2)	0.0241 (19)	−0.0009 (14)	−0.0017 (14)	0.0094 (16)
C10	0.0189 (17)	0.0233 (17)	0.030 (2)	0.0052 (14)	0.0044 (15)	0.0058 (15)
P1	0.0237 (5)	0.0215 (4)	0.0276 (5)	0.0015 (4)	−0.0041 (4)	0.0034 (4)
F1	0.0441 (15)	0.0313 (12)	0.0302 (13)	0.0015 (11)	−0.0016 (13)	0.0093 (12)
F2	0.0352 (14)	0.0288 (13)	0.0505 (18)	0.0056 (11)	0.0069 (13)	0.0147 (12)
F3	0.0305 (13)	0.0460 (15)	0.0434 (16)	0.0103 (12)	0.0071 (12)	0.0068 (14)
F4	0.0461 (16)	0.0389 (14)	0.0269 (13)	−0.0004 (13)	−0.0021 (13)	−0.0024 (11)
F5	0.0238 (13)	0.0352 (14)	0.084 (3)	0.0063 (11)	−0.0003 (14)	0.0167 (16)
F6	0.080 (3)	0.0400 (16)	0.049 (2)	0.0039 (16)	−0.0306 (18)	−0.0073 (14)
P2	0.0207 (4)	0.0254 (5)	0.0267 (5)	0.0014 (4)	−0.0027 (4)	−0.0060 (4)
F7	0.125 (3)	0.0390 (17)	0.0273 (15)	−0.034 (2)	−0.010 (2)	0.0043 (13)
F8	0.089 (3)	0.086 (3)	0.054 (2)	−0.059 (2)	0.040 (2)	−0.024 (2)
F9	0.0261 (12)	0.0282 (11)	0.0341 (14)	0.0008 (10)	−0.0020 (10)	−0.0097 (11)
F10	0.0383 (15)	0.0422 (15)	0.0400 (16)	0.0129 (13)	−0.0168 (13)	−0.0089 (13)
F11	0.0354 (14)	0.0431 (14)	0.0397 (17)	0.0112 (12)	−0.0089 (12)	−0.0241 (13)
F12	0.061 (2)	0.093 (3)	0.097 (3)	0.052 (2)	−0.053 (2)	−0.069 (3)

Geometric parameters (Å, º) top

Cu1—N1	1.973 (3)	C5—H5A	0.9800
Cu1—S1	2.2630 (10)	C5—H5B	0.9800
Cu1—S2ⁱ	2.3305 (9)	C5—H5C	0.9800
Cu1—S4ⁱ	2.3367 (11)	C6—C7	1.469 (7)
Cu2—N2	1.980 (3)	C7—H7A	0.9800
Cu2—S3	2.2886 (11)	C7—H7B	0.9800
Cu2—S4ⁱ	2.3281 (9)	C7—H7C	0.9800
Cu2—S2	2.3357 (11)	C8—H8A	0.9900
S1—C1	1.808 (4)	C8—H8B	0.9900
S1—C2	1.817 (4)	C9—C10	1.524 (6)
S2—C1	1.827 (4)	C9—H9A	0.9900
S2—C3	1.836 (4)	C9—H9B	0.9900
S3—C8	1.806 (4)	C10—H10A	0.9900
S3—C9	1.817 (4)	C10—H10B	0.9900
S4—C8	1.825 (4)	P1—F6	1.579 (3)
S4—C10	1.830 (4)	P1—F5	1.597 (3)
N1—C4	1.140 (5)	P1—F3	1.602 (3)
N2—C6	1.132 (6)	P1—F4	1.608 (3)
C1—H1A	0.9900	P1—F1	1.613 (3)
C1—H1B	0.9900	P1—F2	1.617 (3)
C2—C3	1.523 (6)	P2—F8	1.577 (4)
C2—H2A	0.9900	P2—F10	1.579 (3)
C2—H2B	0.9900	P2—F12	1.588 (3)
C3—H3A	0.9900	P2—F7	1.590 (4)
C3—H3B	0.9900	P2—F11	1.611 (3)
C4—C5	1.456 (6)	P2—F9	1.613 (3)

N1—Cu1—S1	119.47 (11)	H5B—C5—H5C	109.5
N1—Cu1—S2ⁱ	99.97 (9)	N2—C6—C7	179.0 (7)
S1—Cu1—S2ⁱ	115.68 (4)	C6—C7—H7A	109.5
N1—Cu1—S4ⁱ	105.68 (12)	C6—C7—H7B	109.5
S1—Cu1—S4ⁱ	110.65 (4)	H7A—C7—H7B	109.5
S2ⁱ—Cu1—S4ⁱ	103.69 (4)	C6—C7—H7C	109.5
N2—Cu2—S3	112.75 (12)	H7A—C7—H7C	109.5
N2—Cu2—S4ⁱ	99.29 (11)	H7B—C7—H7C	109.5
S3—Cu2—S4ⁱ	118.69 (4)	S3—C8—S4	107.2 (2)
N2—Cu2—S2	106.03 (13)	S3—C8—H8A	110.3
S3—Cu2—S2	115.99 (4)	S4—C8—H8A	110.3
S4ⁱ—Cu2—S2	102.03 (4)	S3—C8—H8B	110.3
C1—S1—C2	92.80 (17)	S4—C8—H8B	110.3
C1—S1—Cu1	105.74 (13)	H8A—C8—H8B	108.5
C2—S1—Cu1	106.41 (13)	C10—C9—S3	107.7 (3)
C1—S2—C3	97.91 (17)	C10—C9—H9A	110.2
C1—S2—Cu1ⁱⁱ	109.15 (11)	S3—C9—H9A	110.2
C3—S2—Cu1ⁱⁱ	116.70 (13)	C10—C9—H9B	110.2
C1—S2—Cu2	110.50 (13)	S3—C9—H9B	110.2
C3—S2—Cu2	110.50 (14)	H9A—C9—H9B	108.5
Cu1ⁱⁱ—S2—Cu2	111.28 (4)	C9—C10—S4	108.2 (3)
C8—S3—C9	91.90 (18)	C9—C10—H10A	110.0
C8—S3—Cu2	110.66 (14)	S4—C10—H10A	110.0
C9—S3—Cu2	102.31 (14)	C9—C10—H10B	110.0
C8—S4—C10	97.95 (18)	S4—C10—H10B	110.0
C8—S4—Cu2ⁱⁱ	109.72 (13)	H10A—C10—H10B	108.4
C10—S4—Cu2ⁱⁱ	121.31 (13)	F6—P1—F5	91.0 (2)
C8—S4—Cu1ⁱⁱ	104.29 (13)	F6—P1—F3	89.9 (2)
C10—S4—Cu1ⁱⁱ	117.50 (15)	F5—P1—F3	178.8 (2)
Cu2ⁱⁱ—S4—Cu1ⁱⁱ	104.54 (4)	F6—P1—F4	178.58 (19)
C4—N1—Cu1	161.5 (3)	F5—P1—F4	90.19 (18)
C6—N2—Cu2	172.0 (4)	F3—P1—F4	88.87 (17)
S1—C1—S2	107.58 (19)	F6—P1—F1	91.48 (18)
S1—C1—H1A	110.2	F5—P1—F1	90.12 (16)
S2—C1—H1A	110.2	F3—P1—F1	90.55 (16)
S1—C1—H1B	110.2	F4—P1—F1	89.24 (16)
S2—C1—H1B	110.2	F6—P1—F2	89.98 (19)
H1A—C1—H1B	108.5	F5—P1—F2	89.37 (16)
C3—C2—S1	109.0 (3)	F3—P1—F2	89.94 (15)
C3—C2—H2A	109.9	F4—P1—F2	89.31 (17)
S1—C2—H2A	109.9	F1—P1—F2	178.46 (18)
C3—C2—H2B	109.9	F8—P2—F10	92.1 (2)
S1—C2—H2B	109.9	F8—P2—F12	89.6 (3)
H2A—C2—H2B	108.3	F10—P2—F12	178.1 (3)
C2—C3—S2	109.2 (3)	F8—P2—F7	177.8 (2)
C2—C3—H3A	109.8	F10—P2—F7	89.9 (2)
S2—C3—H3A	109.8	F12—P2—F7	88.4 (3)
C2—C3—H3B	109.8	F8—P2—F11	91.27 (19)
S2—C3—H3B	109.8	F10—P2—F11	89.26 (15)
H3A—C3—H3B	108.3	F12—P2—F11	91.32 (16)
N1—C4—C5	178.2 (5)	F7—P2—F11	89.70 (18)
C4—C5—H5A	109.5	F8—P2—F9	89.15 (17)
C4—C5—H5B	109.5	F10—P2—F9	90.17 (15)
H5A—C5—H5B	109.5	F12—P2—F9	89.25 (16)
C4—C5—H5C	109.5	F7—P2—F9	89.90 (17)
H5A—C5—H5C	109.5	F11—P2—F9	179.30 (16)

C2—S1—C1—S2	40.7 (2)	C9—S3—C8—S4	−41.9 (2)
Cu1—S1—C1—S2	−67.21 (18)	Cu2—S3—C8—S4	62.0 (2)
C3—S2—C1—S1	−23.4 (2)	C10—S4—C8—S3	22.5 (2)
Cu1ⁱⁱ—S2—C1—S1	−145.34 (13)	Cu2ⁱⁱ—S4—C8—S3	149.92 (14)
Cu2—S2—C1—S1	91.98 (18)	Cu1ⁱⁱ—S4—C8—S3	−98.58 (18)
C1—S1—C2—C3	−48.2 (3)	C8—S3—C9—C10	51.8 (3)
Cu1—S1—C2—C3	59.1 (3)	Cu2—S3—C9—C10	−59.9 (3)
S1—C2—C3—S2	37.2 (3)	S3—C9—C10—S4	−41.7 (3)
C1—S2—C3—C2	−8.0 (3)	C8—S4—C10—C9	11.4 (3)
Cu1ⁱⁱ—S2—C3—C2	108.1 (2)	Cu2ⁱⁱ—S4—C10—C9	−107.6 (2)
Cu2—S2—C3—C2	−123.5 (2)	Cu1ⁱⁱ—S4—C10—C9	122.1 (3)

Symmetry codes: (i) x+1/2, −y+3/2, z; (ii) x−1/2, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···F9ⁱⁱⁱ	0.99	2.55	3.264 (4)	129
C1—H1A···F12ⁱⁱⁱ	0.99	2.40	3.277 (5)	147
C2—H2A···F9ⁱⁱⁱ	0.99	2.50	3.287 (5)	136
C3—H3B···F4ⁱⁱ	0.99	2.42	3.376 (5)	161
C5—H5C···F6^iv	0.98	2.54	3.426 (6)	151
C8—H8A···F11	0.99	2.34	3.186 (5)	143
C8—H8B···F2^v	0.99	2.46	3.323 (5)	145
C10—H10A···F7ⁱⁱ	0.99	2.31	3.221 (5)	152
C10—H10B···F1ⁱⁱ	0.99	2.48	3.264 (5)	136

Symmetry codes: (ii) x−1/2, −y+3/2, z; (iii) −x+1, −y+1, z+1/2; (iv) x, y+1, z; (v) −x+1, −y+1, z−1/2.

Acknowledgements

Lena Knauer would like to thank the `Fonds der Chemischen Industrie' for a doctoral fellowship.

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