Crystal structure of the two-dimensional coordination polymer poly[di-μ-bromido-bis­(μ-tetra­hydro­thiophene)­dicopper(I)]

Knorr, M.; Viau, L.; Rousselin, Y.; Kubicki, M.M.

doi:10.1107/S2056989021006460

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 77| Part 7| July 2021| Pages 744-748

https://doi.org/10.1107/S2056989021006460

Open

access

Crystal structure of the two-dimensional coordination polymer poly[di-μ-bromido-bis(μ-tetrahydrothiophene)dicopper(I)]

Michael Knorr,^a ^* Lydie Viau,^a ^* Yoann Rousselin ^b and Marek M. Kubicki ^b ^*

^aInstitut UTINAM UMR CNRS 6213, Université Bourgogne Franche-Comté, 16 route de Gray, 25030 Besançon, France, and ^bICMUB UMR CNRS 6302, Université Bourgogne Franche-Comté, 9 avenue Alain Savary, 21078 Dijon, France
^*Correspondence e-mail: michael.knorr@univ-fcomte.fr, lydie.viau@univ-fcomte.fr, marek.kubicki@u-bourgogne.fr

Edited by C. Schulzke, Universität Greifswald, Germany (Received 21 May 2021; accepted 21 June 2021; online 25 June 2021)

The polymeric title compound, [Cu₂Br₂(C₄H₈S)₂]_n, CP1, represents an example of a two-dimensional coordination polymer resulting from reaction of CuBr with tetrahydrothiophene (THT) in MeCN solution. The two-dimensional layers consist of two different types of rhomboid-shaped dinuclear Cu(μ₂-Br)₂Cu secondary building units (SBUs); one with a quite loose Cu⋯Cu separation of 3.3348 (10) Å and a second one with a much closer intermetallic contact of 2.9044 (9) Å. These SBUs are interconnected through bridging THT ligands, in which the S atom acts as a four-electron donor bridging each Cu(μ₂-Br)₂Cu unit in a μ₂-bonding mode. In the crystal, the layers are linked by very weak C—H⋯·Br hydrogen bonds with H⋯Br distances of 2.95 Å, thus giving rise to a three-dimensional supramolecular network.

Keywords: crystal structure; two-dimensional coordination polymer; Cu₂Br₂ rhomboids; tetrahydrothiophene; C—H⋯Br hydrogen bonding..

CCDC reference: 2091214

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. In addition, numerous structurally characterized examples coordinated by terminal or bridging THT ligands have been documented for the soft coinage metal ions Cu^I, Ag^I and Au^I (Usón et al., 1984 ; Noren & Oskarsson, 1985 ; Mälger et al., 1992 ; Ahrland et al., 1993 ; López-De-Luzuriaga et al., 1997 ; Ahrens & Jones, 2000 ). The research group of Pike has shown that depending on the reaction conditions, the treatment of CuI with THT affords dinuclear [(THT)₂Cu(μ₂-I)₂Cu(THT)₂], or the tetranuclear closed cubane-type cluster [(Cu₄(μ₃-I)₄(THT)₄] or [(CuI)₁₀(THT)₇(MeCN)]_n (Henline et al., 2014 ). The latter contains the mixed motif [(Cu₄I₄(THT)](μ₂-THT)₂(Cu₂I₂)(μ₂-THT)₂[Cu₄I₄(THT)] held together side-by-side by two μ₂-THT assembling ligands to form a 1D ladder structure. Furthermore, the two-dimensional CP [(CuI)₃(THT)₃·MeCN]_n featuring a sheet structure in which Cu₃(THT) rings are linked in trigonal directions by rhomboid Cu₂I₂ dimers is literature-known (Henline et al., 2014). The luminescent product [(CuI)₄(THT)₂]_n consisting of Cu₄I₄ cubane units knit into a 3D network by μ₂-THT ligands was also described previously (Noren & Oskarsson, 1987 ; Henline et al., 2014). A series of solvent-dependent 2D polymers results from treatment of [Cu(CO)Cl]_n with THT in THF, CH₂Cl₂ and DMF, exhibiting the composition [(CuCl)(THT)]_n (THF), [(CuCl)(THT)]_n (CH₂Cl₂), and [(CuCl)₃(THT)₂]_n (DMF), respectively. The materials obtained in THF and CH₂Cl₂ are polymorphs (Solari et al., 1996 ). A mono-dimensional ribbon [(CuCl)₂(THT)₃]_n is generated by reaction of CuCl in neat THT (Mälger et al., 1992). Even mixed-valence Cu^I/Cu^II compounds such as polymeric penta-μ-chloro-tris-μ-tetrahydrothiophene-tetracopper(I,II) have been observed (Ainscough et al., 1985 ). Mälger and co-workers also showed that the treatment of CuBr in neat THT leads to the formation of a very labile rhomboid-based 1D polymer of the type [(CuBr)₂(THT)₃]_n isostructural with its [(CuCl)₂(THT)₃]_n analogue (Mälger et al., 1992) (CSD JUDKOI).

In the context of our research interest in the assembly of molecular cluster compounds and coordination polymers by complexation of dialkyl sulfides R–S–R or dithiolane- and dithiane-based thiaheterocycles with CuX salts (Knorr et al., 2010 , 2015 ; Lapprand et al., 2013 ; Raghuvanshi et al., 2017 , 2019 ; Schlachter et al., 2018 ; Knauer et al., 2020 ), we have also investigated the complexation of CuBr by THT in acetonitrile as solvent (see Fig. 5) and present here the respective crystal structure, which differs both in composition and dimensionality (two-dimensional vs mono-dimensional) from the CP [(CuBr)₂(THT)₃]_n reported by Mälger. Note that this colourless material crystallizes easily in the form of large well-shaped crystals that are stable in a THT-saturated environment, but decomposes rapidly by dissociation of volatile THT upon exposure to air.

Figure 5
Reaction scheme for the synthesis of CP1.

2. Structural commentary

The crystal structure of CP1 of composition [(CuBr)₂(THT)₂]_n is built of Cu(μ₂-Br)₂Cu rhomboids as SBUs and tetrahydrothiophene ligands. The asymmetric unit contains two independent planar Cu₂Br₂ units placed over the symmetry centres at ½, 0, 0 (Cu1Br1)₂ and 1, 0, ½ (Cu2Br2)₂. They are connected through the sulfur atoms of thiophene ligands acting, like in all bridging monothioethers, as four-electron donors (Fig. 1). The bridging S1 atoms develop the chains of alternating (Cu1Br1)₂ and (Cu2Br2)₂ SBUs parallel to one diagonal [ $[\overline{1}]$ 01] direction of the a0c face of the unit cell (labelled on Fig. 2 from Cu2h to Cu2i), whereas the S2 atoms develop the analogous chains labelled from Cu2e to Cu2f parallel to the second diagonal [101] direction of this face. The thus formed 2D layers lie over the (010) planes (Fig. 2). This is the essential difference from the 1D polymer [(CuBr)₂(THT)₃]_n described by Mälger (Mälger et al., 1992) in which only one THT molecule acts as a bridging ligand, developing a chain in one direction, whereas the two other THT molecules are terminal. The outstanding feature of the structure of CP1 consists of largely different (0.43 Å) Cu⋯Cu distances in (Cu1Br1)₂ and (Cu2Br2)₂ units [3.3348 (10) Å vs 2.9044 (9) Å], albeit in similar chemical surroundings. Contrary to these metal-to-metal separations, the Cu—Br and Cu—S bond lengths are similar in both rhomboids. In the 1D polymer of Mälger, the Cu⋯Cu distance of 2.7784 (7) Å is significantly shorter than in CP1. Note that the presence of two independent Cu₂Br₂ SBUs has been also reported for the structure of Cu₂Br₂(1,4-oxathiane)₂ but the difference between the Cu⋯Cu distances therein is equal only to 0.12 Å [2.740 (3) Å vs 2.865 (4) Å; Barnes & Paton, 1982 ; CSD BOGTIA]. This difference is still smaller in two other CPs with different Cu₂Br₂ SBUs: [{Cu(μ₂-Br)₂Cu}{μ-PhS(CH₂)₃SPh}₂]_n [dCu⋯Cu = 2.794 (1) and 2.776 (1) Å; Knorr et al., 2012 ; CSD ZEHREL] and in [{Cu(μ₂-Br)₂Cu}{μ-p-MeC₆H₄SCH₂C≡CCH₂SC₆H₄Me-p]_n [dCu⋯Cu = 2.9306 (14) and 2.9662 (14) Å; Bonnot et al., 2015 ; CSD QUPXOQ]. These observations indicate a high flexibility of the Cu₂Br₂ units. It is worth noting that the Cu⋯Cu distances in coordination polymers containing dibromodicopper units and bridging monothioethers have been observed in the range from 2.740 (3) Å in Cu₂Br₂(1,4-oxathiane)₂ (Barnes & Paton, 1982) to 3.074 (1) Å at 115 K in [(Cu₂Br₂)(Cu₄Br₄)(SMeEt)₆]_n (Knorr et al., 2010). Thus, the Cu1⋯ Cu1 distance of 3.3348 (10) Å in CP1 is the longest one observed in Cu₂Br₂ CPs with bridging monothioethers. The coordination polyhedra of the Cu1 and Cu2 atoms are best described as distorted tetrahedral. Even though the values of four-coordinate geometry τ₄ indexes of Yang (Yang et al., 2007 ) of 0.88 support a trigonal–pyramidal geometry (theoretical values are equal to 0.85 for C_3v and 1.0 for T_d symmetries), the tetrahedral character THC_DA parameters of Höpfl (0.66 for Cu1 and 0.60 for Cu2) are closer to the tetrahedral (THC = 1.0) than pyramidal (THC = 0) geometries (Höpfl, 1999 ). Moreover, the sums of all six bond angles around Cu1 (656.7°) and Cu2 (656.1°) are very close to the value expected for T_d symmetry (657°) and far from that of 630° in an ideal trigonal–pyramidal geometry.

Figure 1
A view of CP1 depicting the independent Cu₂Br₂ SBUs and THT ligands. Ellipsoids are shown at the 50% probability level. Only the major component of disordered atom C7 is shown. Symmetry codes: (i) −x + 2, −y, −z + 1; (ii) x + 1, y, z;) iii) −x + 1, −y, −z; (iv) −x + 1, −y, −z + 1.

Figure 2
Projection of one layer on the a0c plane in the structure of CP1. Hydrogen atoms are omitted for clarity. Only the major component of disordered C7 atom is shown. Symmetry codes: (a) − x + 1, −y, −z; (b) −x + 1, −y, −z + 1; (c) −x, −y, −z + 1; (d) x − 1, y, z; (e) x, y, z + 1; (f) −x, −y, −z; (g) x − 1, y, z + 1; (h) −x, −y, −z + 2; (i) x, y, z + 1; (j) x, y, z − 1.

3. Supramolecular features

The layers are built through dative Cu—S coordination bonds. There are also weak non-covalent CH⋯HC [d(H1A⋯H8AA) = 2.36 Å] van der Waals contacts and C—H⋯Br [d(Br2⋯H4B) = 2.90 Å; d(Br2⋯H5B) = 2.89 Å] hydrogen bonds within the layers (Fig. 3 and Table 1). More interestingly, the interlayer connectivity for formation of a supramolecular 3D structure is apparently limited only to very weak C—H⋯Br hydrogen bonds (Fig. 4). The Br2⋯H7AA distance of 2.95 Å is shorter by only 0.10 Å than the sum of the van der Waals radii (Bondi, 1964 ). It is noteworthy that only bromine Br2 participates in hydrogen-bonding contacts and not the bromine atom Br1. In the Cu1Br1 rhomboids, the Br⋯ Br distance is short, the Cu⋯Cu distance is long and there are no Br⋯H bonds, while in the Cu2Br2 rhomboids the opposite is observed with long Br⋯Br and short Cu⋯Cu distances and the presence of Br2⋯H interactions. However, we don't believe that the presence or absence of weak hydrogen bonding alone may explain the large difference in the Cu⋯Cu distances.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4B⋯Br2^iv	0.99	2.90	3.566 (4)	125
C5—H5B⋯Br2ⁱⁱ	0.99	2.89	3.556 (4)	126
C7A—H7AA⋯Br2^v	0.99	2.95	3.885 (6)	157
Symmetry codes: (ii) ; (iv) ; (v) .

Figure 3
Intralayer CH⋯Br and CH⋯HC non-covalent interactions. Symmetry codes: (a) x − 1, y, z; (b) −x + 1, −y, −z + 1; (c) −x, −y, −z + 1; (d) x − 2, y, z; (e) −x + 2, −y, −z + 1.

Figure 4
Interlayer CH⋯Br hydrogen bonds. Symmetry codes: (a) x, y + 1, z; (b) −x + 1, −y + 1, −z + 1; (c) −x + 1, −y, −z + 1; (d) x − 1, y, z; (e) x − 1, y + 1, z.

4. Database survey

The rich structural diversity of THT-ligated molecular and polymeric copper(I) halide compounds was already laid out extensively in the Chemical context section above. Further examples found in a database survey using CONQUEST (Bruno et al., 2002 ) comprise, for example, the three-dimensional MOF [tris(μ₂-cyano)-tris(μ₂-THT)tricopper(I)]_n (CSD ITEZOX), which was isolated upon treatment of CuCN with THT (Dembo et al., 2010 ). An example of a cationic dinuclear bipyridine-bridged complex is (μ-4,4′-bipyridine)bis(THT)tetrakis(triphenylphosphine)di-copperbis(tetrafluoroborate) (CSD MOJWOZ; Royzman et al., 2014 ). A structurally characterized molecular organometallic aryl complex [2,6-bis(2,4,6-triisopropylphenyl)phenyl](THT)copper(I) (CSD DOPMUR) is another relevant contribution in this context (Groysman & Holm, 2009 ). There is also the interesting case of the tetranuclear compound cyclo[tetrakis(μ₂-mesitylidene)bis(THT-copper)dicopper(I)] featuring bridging aryl groups and terminal bound THT ligands (Meyer et al., 1989 ). For selected examples of molecular thioether-ligated complexes incorporating dinuclear Cu(μ₂-Br)₂Cu SBUs, see: [{Cu(μ₂-Br)₂Cu}{1-oxa-4,7-dithiacyclononane}₂] [Lucas et al., 1997 ; CSD NONWOC, dCu⋯Cu = 2.852 (2) Å]; [{Cu(μ₂-Br)₂Cu}{phenyl propargyl sulfide}₄] [Kokoli et al., 2013 ; CSD VEQXUM, dCu⋯Cu = 3.0062 (7) Å]. For selected examples of mono-dimensional thioether-assembled CPs incorporating dinuclear Cu(μ₂-Br)₂Cu SBUs, see: [{Cu(μ₂-Br)₂Cu}{μ-PhSCH₂SPh}₂]_n [Knorr et al., 2014 ; CSD FOWZIC, dCu⋯Cu = 2.9192 (8) Å]; [{Cu(μ₂-Br)₂Cu}{μ-PhS(CH₂)₃SPh}₂]_n [Knorr et al., 2012; CSD ZEHREL, dCu⋯Cu = 2.794 (1) and 2.776 (1) Å]; [Cu(μ₂-Br)₂Cu{μ-p-EtSCH₂C₆H₄C₆H₄CH₂SEt-p}₂]_n [Toyota et al., 1996 ; CSD ZARYUM01, dCu⋯Cu = 2.918 (11) Å]; [Cu(μ₂-Br)₂Cu{μ-O₂S₂-macrocycle)₂]_n [Park et al., 2012 ; CSD GAXHIY, dCu⋯Cu = 2.927 (1) Å].

For selected examples of two-dimensional thioether-assembled CPs incorporating dinuclear Cu(μ₂-Br)₂Cu SBUs, see: [{Cu₂(μ₂-Br)₂}(tetrathiaphthalazinophane)₂]_n [Chen et al., 1993 ; CSD HANGUY, dCu⋯Cu = 3.06 (8) Å]; [{Cu(μ₂-Br)₂Cu}(μ₂-2-isobutyl-1,3-dithiane)₂]_n [Raghuvanshi et al., 2019; CSD JIZQOB, dCu⋯Cu = 2.9057 (8) Å]; [{Cu(μ₂-Br)₂Cu}{μ-PhCH₂S(CH₂)₆SCH₂Ph}₂]_n [Schlachter et al., 2020 ; CSD IHIBUZ, dCu⋯Cu = 2.953 (3) Å]; [{Cu(μ₂-Br)₂Cu}{μ-PhCH₂S(CH₂)₇SCH₂Ph}₂]_n [Schlachter et al., 2020; CSD IHICOU, dCu⋯Cu = 2.7081 (4) Å]; [{Cu(μ₂-Br)₂Cu}(μ-1,2,4,5-tetramethylmercaptobenzene)]_n [Suenaga et al., 1997 ; CSD WIQMIS, dCu⋯Cu = 3.1073 (12) Å]. An evaluation of these examples emphasizes that the Cu⋯Cu separations within the dinuclear Cu(μ₂-Br)₂Cu SBUs are quite variable.

5. Synthesis and crystallization

To a solution of CuBr (1.43 g, 10.0 mmol) in MeCN (12 mL) was added neat THT (1.058 g, 12.0 mmol) via syringe. The solution turned brownish-red and a colourless microcrystalline material commenced to precipitate. The suspension was stirred at 293 K for 2 h, then heated 2 min to reflux until all product dissolved. While slowly warming to ambient temperature, colourless crystals formed progressively (Fig. 5). Filtering off the product after 1 d and storing the mother liquor in a refrigerator afforded a second crop of CP1. Overall yield (1.80 g, 78% yield). Calculated for C₈H₁₆Br₂Cu₂S₂: C, 20.74 H, 3.48; S, 13.84. Found: C, 20.35; H, 3.28, S, 13.41%.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were placed in calculated positions and treated with a riding model. C—H distances were set to 0.99 Å with U_iso(H) = 1.2U_eq(C). C7 in one of the THT ligands as well as the riding methylene hydrogen atoms on C6, C7 and C8 are disordered over two locations. Their occupancy factors refined to 0.77 (1) and 0.23 (1). The disorder was modelled using a SADI constraint for the affected C—C distances.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu₂Br₂(C₄H₈S)₂]
M_r	463.23
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	115
a, b, c (Å)	6.8076 (3), 9.7078 (4), 10.1579 (4)
α, β, γ (°)	75.804 (2), 89.845 (2), 89.594 (2)
V (Å³)	650.79 (5)
Z	2
Radiation type	Mo Kα₁
μ (mm⁻¹)	9.69
Crystal size (mm)	0.25 × 0.15 × 0.1

Data collection
Diffractometer	Nonius Kappa APEXII
Absorption correction	Multi-scan (Blessing, 1995 )
T_min, T_max	0.024, 0.072
No. of measured, independent and observed [I > 2σ(I)] reflections	5297, 2954, 2743
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.075, 1.09
No. of reflections	2954
No. of parameters	132
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.82, −0.91
Computer programs: COLLECT (Nonius, 1997 ), HKL, DENZO and SCALEPACK (Otwinowski & Minor 1997 ), SIR97 (Burla et al., 2007 ), SHELXL2018/3 (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2091214

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021006460/yz2008sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021006460/yz2008Isup2.hkl

checkCIF report

Computing details top

Data collection: COLLECT (Nonius, 1997); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SIR97 (Burla et al., 2007); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[di-µ-bromido-bis(µ-tetrahydrothiophene)dicopper(I)] top

Crystal data top

[Cu₂Br₂(C₄H₈S)₂]	Z = 2
M_r = 463.23	F(000) = 448
Triclinic, P1	D_x = 2.364 Mg m⁻³
a = 6.8076 (3) Å	Mo Kα₁ radiation, λ = 0.71073 Å
b = 9.7078 (4) Å	Cell parameters from 2662 reflections
c = 10.1579 (4) Å	θ = 1.0–27.5°
α = 75.804 (2)°	µ = 9.69 mm⁻¹
β = 89.845 (2)°	T = 115 K
γ = 89.594 (2)°	Prism, clear light colourless
V = 650.79 (5) Å³	0.25 × 0.15 × 0.1 mm

Data collection top

Nonius Kappa APEXII diffractometer	2954 independent reflections
Radiation source: X-ray tube, Siemens KFF Mo 2K-180	2743 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 9 pixels mm^-1	θ_max = 27.6°, θ_min = 3.0°
φ and ω scans'	h = −8→8
Absorption correction: multi-scan (Blessing, 1995)	k = −12→12
T_min = 0.024, T_max = 0.072	l = −12→13
5297 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.0333P)² + 2.0511P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
2954 reflections	Δρ_max = 0.82 e Å⁻³
132 parameters	Δρ_min = −0.91 e Å⁻³
6 restraints

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br1	0.66540 (5)	0.15468 (4)	−0.03837 (3)	0.01461 (10)
Br2	0.83088 (5)	0.17939 (4)	0.45014 (4)	0.01506 (10)
Cu1	0.51313 (7)	−0.00292 (5)	0.16455 (5)	0.01505 (11)
Cu2	0.82082 (6)	−0.08288 (5)	0.51958 (4)	0.01385 (11)
S1	0.31065 (12)	0.13645 (9)	0.26538 (8)	0.01195 (17)
S2	0.70032 (12)	−0.14665 (9)	0.33197 (9)	0.01222 (17)
C1	0.4015 (6)	0.3198 (4)	0.2177 (4)	0.0192 (8)
H1A	0.375096	0.368406	0.290963	0.023*
H1B	0.544740	0.320766	0.200413	0.023*
C2	0.2910 (6)	0.3928 (4)	0.0890 (4)	0.0206 (8)
H2A	0.354608	0.371724	0.008315	0.025*
H2B	0.289017	0.496987	0.077765	0.025*
C3	0.0821 (6)	0.3339 (4)	0.1059 (4)	0.0226 (8)
H3A	0.010384	0.370283	0.175423	0.027*
H3B	0.009678	0.363357	0.018959	0.027*
C4	0.0989 (6)	0.1729 (4)	0.1496 (4)	0.0163 (7)
H4A	0.121252	0.132901	0.069998	0.020*
H4B	−0.022152	0.131202	0.196654	0.020*
C5	0.9163 (6)	−0.2030 (4)	0.2504 (4)	0.0179 (7)
H5A	0.902627	−0.175035	0.150356	0.022*
H5B	1.036738	−0.159227	0.275978	0.022*
C6	0.9258 (7)	−0.3639 (5)	0.3012 (5)	0.0325 (10)
H6AA	1.003988	−0.405261	0.237893	0.039*	0.771 (13)
H6AB	0.988725	−0.390717	0.391775	0.039*	0.771 (13)
H6BC	0.911154	−0.407662	0.223452	0.039*	0.229 (13)
H6BD	1.055839	−0.392163	0.342976	0.039*	0.229 (13)
C7A	0.7197 (8)	−0.4183 (6)	0.3098 (6)	0.0265 (16)	0.771 (13)
H7AA	0.716201	−0.518002	0.364131	0.032*	0.771 (13)
H7AB	0.669637	−0.415264	0.217672	0.032*	0.771 (13)
C7B	0.7690 (16)	−0.4178 (16)	0.4028 (15)	0.016 (5)*	0.229 (13)
H7BA	0.732673	−0.515246	0.398840	0.019*	0.229 (13)
H7BB	0.819357	−0.422099	0.495122	0.019*	0.229 (13)
C8	0.5925 (6)	−0.3246 (4)	0.3767 (4)	0.0188 (8)
H8AA	0.591371	−0.362462	0.476472	0.023*	0.771 (13)
H8AB	0.455767	−0.321214	0.343042	0.023*	0.771 (13)
H8BC	0.508814	−0.337978	0.458646	0.023*	0.229 (13)
H8BD	0.513653	−0.342444	0.300886	0.023*	0.229 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01355 (17)	0.01735 (19)	0.01357 (17)	−0.00288 (13)	0.00077 (13)	−0.00496 (14)
Br2	0.01333 (17)	0.01052 (18)	0.02045 (19)	0.00292 (13)	−0.00208 (13)	−0.00219 (14)
Cu1	0.0167 (2)	0.0148 (2)	0.0137 (2)	0.00320 (17)	−0.00176 (16)	−0.00354 (17)
Cu2	0.0162 (2)	0.0132 (2)	0.0120 (2)	0.00180 (17)	−0.00123 (16)	−0.00298 (17)
S1	0.0142 (4)	0.0100 (4)	0.0108 (4)	0.0027 (3)	−0.0016 (3)	−0.0010 (3)
S2	0.0140 (4)	0.0111 (4)	0.0119 (4)	0.0016 (3)	−0.0012 (3)	−0.0037 (3)
C1	0.0254 (19)	0.0107 (18)	0.0198 (18)	−0.0041 (15)	−0.0019 (15)	−0.0003 (14)
C2	0.0212 (19)	0.0146 (19)	0.0218 (19)	0.0013 (15)	−0.0009 (15)	0.0036 (15)
C3	0.0189 (18)	0.018 (2)	0.027 (2)	0.0055 (15)	−0.0040 (16)	0.0000 (16)
C4	0.0198 (17)	0.0151 (18)	0.0138 (16)	0.0055 (14)	−0.0060 (14)	−0.0030 (14)
C5	0.0190 (18)	0.0183 (19)	0.0159 (17)	0.0070 (14)	0.0055 (14)	−0.0033 (14)
C6	0.038 (3)	0.021 (2)	0.041 (3)	0.0089 (19)	0.007 (2)	−0.012 (2)
C7A	0.036 (3)	0.018 (3)	0.028 (3)	−0.002 (2)	−0.010 (2)	−0.009 (2)
C8	0.0243 (19)	0.0141 (19)	0.0171 (17)	−0.0067 (15)	−0.0020 (15)	−0.0018 (14)

Geometric parameters (Å, º) top

Br1—Cu1	2.4755 (6)	C3—C4	1.520 (5)
Br1—Cu1ⁱ	2.5000 (6)	C4—H4A	0.9900
Br2—Cu2ⁱⁱ	2.5349 (6)	C4—H4B	0.9900
Br2—Cu2	2.4711 (6)	C5—H5A	0.9900
Cu1—Cu1ⁱ	3.3348 (10)	C5—H5B	0.9900
Cu1—S1	2.3292 (9)	C5—C6	1.522 (6)
Cu1—S2	2.2991 (10)	C6—H6AA	0.9900
Cu2—Cu2ⁱⁱ	2.9044 (9)	C6—H6AB	0.9900
Cu2—S1ⁱⁱⁱ	2.2982 (9)	C6—H6BC	0.9900
Cu2—S2	2.2983 (9)	C6—H6BD	0.9900
S1—C1	1.837 (4)	C6—C7A	1.497 (7)
S1—C4	1.840 (4)	C6—C7B	1.488 (12)
S2—C5	1.831 (4)	C7A—H7AA	0.9900
S2—C8	1.833 (4)	C7A—H7AB	0.9900
C1—H1A	0.9900	C7A—C8	1.526 (6)
C1—H1B	0.9900	C7B—H7BA	0.9900
C1—C2	1.523 (5)	C7B—H7BB	0.9900
C2—H2A	0.9900	C7B—C8	1.484 (12)
C2—H2B	0.9900	C8—H8AA	0.9900
C2—C3	1.530 (5)	C8—H8AB	0.9900
C3—H3A	0.9900	C8—H8BC	0.9900
C3—H3B	0.9900	C8—H8BD	0.9900

Cu1—Br1—Cu1ⁱ	84.167 (19)	S1—C4—H4A	110.7
Cu2—Br2—Cu2ⁱⁱ	70.916 (19)	S1—C4—H4B	110.7
Br1—Cu1—Br1ⁱ	95.832 (19)	C3—C4—S1	105.3 (3)
S1—Cu1—Br1	107.82 (3)	C3—C4—H4A	110.7
S1—Cu1—Br1ⁱ	114.58 (3)	C3—C4—H4B	110.7
S2—Cu1—Br1	121.51 (3)	H4A—C4—H4B	108.8
S2—Cu1—Br1ⁱ	108.88 (3)	S2—C5—H5A	110.6
S2—Cu1—S1	108.12 (3)	S2—C5—H5B	110.6
Br2—Cu2—Br2ⁱⁱ	109.084 (19)	H5A—C5—H5B	108.7
Br2ⁱⁱ—Cu2—Cu2ⁱⁱ	53.516 (16)	C6—C5—S2	105.7 (3)
Br2—Cu2—Cu2ⁱⁱ	55.568 (17)	C6—C5—H5A	110.6
S1ⁱⁱⁱ—Cu2—Br2	105.18 (3)	C6—C5—H5B	110.6
S1ⁱⁱⁱ—Cu2—Br2ⁱⁱ	104.86 (3)	C5—C6—H6AA	110.2
S1ⁱⁱⁱ—Cu2—Cu2ⁱⁱ	116.52 (3)	C5—C6—H6AB	110.2
S2—Cu2—Br2	104.11 (3)	C5—C6—H6BC	109.3
S2—Cu2—Br2ⁱⁱ	105.71 (3)	C5—C6—H6BD	109.3
S2—Cu2—Cu2ⁱⁱ	116.35 (3)	H6AA—C6—H6AB	108.5
S2—Cu2—S1ⁱⁱⁱ	127.13 (4)	H6BC—C6—H6BD	108.0
Cu2ⁱⁱⁱ—S1—Cu1	128.70 (4)	C7A—C6—C5	107.7 (4)
C1—S1—Cu1	108.21 (14)	C7A—C6—H6AA	110.2
C1—S1—Cu2ⁱⁱⁱ	111.26 (13)	C7A—C6—H6AB	110.2
C1—S1—C4	94.46 (18)	C7B—C6—C5	111.5 (6)
C4—S1—Cu1	102.71 (12)	C7B—C6—H6BC	109.3
C4—S1—Cu2ⁱⁱⁱ	105.46 (13)	C7B—C6—H6BD	109.3
Cu2—S2—Cu1	125.08 (4)	C6—C7A—H7AA	110.0
C5—S2—Cu1	107.52 (13)	C6—C7A—H7AB	110.0
C5—S2—Cu2	104.92 (13)	C6—C7A—C8	108.3 (4)
C5—S2—C8	93.98 (19)	H7AA—C7A—H7AB	108.4
C8—S2—Cu1	108.84 (13)	C8—C7A—H7AA	110.0
C8—S2—Cu2	111.74 (13)	C8—C7A—H7AB	110.0
S1—C1—H1A	110.6	C6—C7B—H7BA	109.4
S1—C1—H1B	110.6	C6—C7B—H7BB	109.4
H1A—C1—H1B	108.7	H7BA—C7B—H7BB	108.0
C2—C1—S1	105.9 (3)	C8—C7B—C6	111.0 (9)
C2—C1—H1A	110.6	C8—C7B—H7BA	109.4
C2—C1—H1B	110.6	C8—C7B—H7BB	109.4
C1—C2—H2A	110.5	S2—C8—H8AA	110.4
C1—C2—H2B	110.5	S2—C8—H8AB	110.4
C1—C2—C3	106.3 (3)	S2—C8—H8BC	111.3
H2A—C2—H2B	108.7	S2—C8—H8BD	111.3
C3—C2—H2A	110.5	C7A—C8—S2	106.8 (3)
C3—C2—H2B	110.5	C7A—C8—H8AA	110.4
C2—C3—H3A	110.3	C7A—C8—H8AB	110.4
C2—C3—H3B	110.3	C7B—C8—S2	102.3 (6)
H3A—C3—H3B	108.5	C7B—C8—H8BC	111.3
C4—C3—C2	107.3 (3)	C7B—C8—H8BD	111.3
C4—C3—H3A	110.3	H8AA—C8—H8AB	108.6
C4—C3—H3B	110.3	H8BC—C8—H8BD	109.2

Cu1—S1—C1—C2	91.5 (3)	S2—C5—C6—C7B	−3.4 (8)
Cu1—S1—C4—C3	−123.6 (2)	C1—S1—C4—C3	−13.8 (3)
Cu1—S2—C5—C6	−128.8 (3)	C1—C2—C3—C4	−49.3 (4)
Cu1—S2—C8—C7A	103.2 (3)	C2—C3—C4—S1	37.6 (4)
Cu1—S2—C8—C7B	143.3 (6)	C4—S1—C1—C2	−13.4 (3)
Cu2ⁱⁱⁱ—S1—C1—C2	−121.9 (2)	C5—S2—C8—C7A	−6.8 (3)
Cu2ⁱⁱⁱ—S1—C4—C3	99.7 (3)	C5—S2—C8—C7B	33.3 (6)
Cu2—S2—C5—C6	96.1 (3)	C5—C6—C7A—C8	−45.0 (5)
Cu2—S2—C8—C7A	−114.6 (3)	C5—C6—C7B—C8	30.0 (12)
Cu2—S2—C8—C7B	−74.5 (6)	C6—C7A—C8—S2	30.3 (5)
S1—C1—C2—C3	37.0 (4)	C6—C7B—C8—S2	−40.9 (11)
S2—C5—C6—C7A	38.3 (4)	C8—S2—C5—C6	−17.7 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···Br2^iv	0.99	2.90	3.566 (4)	125
C5—H5B···Br2ⁱⁱ	0.99	2.89	3.556 (4)	126
C7A—H7AA···Br2^v	0.99	2.95	3.885 (6)	157

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

Funding information

The authors thank the CNRS for financial support.

References

Ahrens, B. & Jones, P. G. (2000). Z. Naturforsch. Teil B, 55, 803–813. CrossRef CAS Google Scholar
Ahrland, S., Dreisch, K., Norén, B. & Oskarsson, A. (1993). Mater. Chem. Phys. 35, 281–289. CSD CrossRef CAS Web of Science Google Scholar
Ainscough, E. W., Brodie, A. M., Husbands, J. M., Gainsford, G. J., Gabe, E. J. & Curtis, N. F. (1985). J. Chem. Soc. Dalton Trans. pp. 151–158. CSD CrossRef Web of Science Google Scholar
Barnes, J. C. & Paton, J. D. (1982). Acta Cryst. B38, 3091–3093. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bondi, A. (1964). J. Phys. Chem. 68, 441–451. CrossRef CAS Web of Science Google Scholar
Bonnot, A., Knorr, M., Strohmann, C., Golz, C., Fortin, D. & Harvey, P. D. (2015). J. Inorg. Organomet. Polym. 25, 480–494. Web of Science CSD CrossRef CAS Google Scholar
Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389–397. Web of Science CrossRef CAS IUCr Journals Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G., Siliqi, D. & Spagna, R. (2007). J. Appl. Cryst. 40, 609–613. Web of Science CrossRef CAS IUCr Journals Google Scholar
Chen, L., Thompson, L. K., Tandon, S. & Bridson, J. N. (1993). Inorg. Chem. 32, 4063–4068. CSD CrossRef CAS Google Scholar
Dembo, M. D., Dunaway, L. E., Jones, J. S., Lepekhina, E. A., McCullough, S. M., Ming, J. L., Li, X., Baril-Robert, F., Patterson, H. H., Bayse, C. A. & Pike, R. D. (2010). Inorg. Chim. Acta, 364, 102–114. Web of Science CSD CrossRef CAS Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groysman, S. & Holm, R. H. (2009). Inorg. Chem. 48, 621–627. CSD CrossRef PubMed CAS Google Scholar
Henline, K. M., Wang, C., Pike, R. D., Ahern, J. C., Sousa, B., Patterson, H. H., Kerr, A. T. & Cahill, C. L. (2014). Cryst. Growth Des. 14, 1449–1458. Web of Science CSD CrossRef CAS Google Scholar
Höpfl, H. (1999). J. Organomet. Chem. 581, 129–149. Google Scholar
Knauer, L., Knorr, M., Viau, L. & Strohmann, C. (2020). Acta Cryst. E76, 38–41. Web of Science CSD CrossRef IUCr Journals Google Scholar
Knorr, M., Bonnot, A., Lapprand, A., Khatyr, A., Strohmann, C., Kubicki, M. M., Rousselin, Y. & Harvey, P. D. (2015). Inorg. Chem. 54, 4076–4093. Web of Science CSD CrossRef CAS PubMed Google Scholar
Knorr, M., Guyon, F., Khatyr, A., Strohmann, C., Allain, M., Aly, S. M., Lapprand, A., Fortin, D. & Harvey, P. D. (2012). Inorg. Chem. 51, 9917–9934. CSD CrossRef CAS PubMed Google Scholar
Knorr, M., Khatyr, A., Dini Aleo, A., El Yaagoubi, A., Strohmann, C., Kubicki, M. M., Rousselin, Y., Aly, S. M., Fortin, D., Lapprand, A. & Harvey, P. D. (2014). Cryst. Growth Des. 14, 5373–5387. Web of Science CSD CrossRef CAS Google Scholar
Knorr, M., Pam, A., Khatyr, A., Strohmann, C., Kubicki, M. M., Rousselin, Y., Aly, S. M., Fortin, D. & Harvey, P. D. (2010). Inorg. Chem. 49, 5834–5844. Web of Science CSD CrossRef CAS PubMed Google Scholar
Kokoli, T., Olsson, S., Björemark, P. M., Persson, S. & Håkansson, M. (2013). J. Organomet. Chem. 724, 17–22. Web of Science CSD CrossRef CAS Google Scholar
Lapprand, A., Bonnot, A., Knorr, M., Rousselin, Y., Kubicki, M. M., Fortin, D. & Harvey, P. D. (2013). Chem. Commun. 49, 8848–8850. CSD CrossRef CAS Google Scholar
López-De-Luzuriaga, J.-M., Schier, A. & Schmidbaur, H. (1997). Chem. Ber. Recl, 130, 647–650. Google Scholar
Lucas, C. R., Liang, W., Miller, D. O. & Bridson, J. N. (1997). Inorg. Chem. 36, 4508–4513. CSD CrossRef PubMed CAS Web of Science Google Scholar
Mälger, H., Olbrich, F., Kopf, J., Abeln, D. & Weiss, E. (1992). Z. Naturforsch. Teil B, 47, 1276–1280. Google Scholar
Meyer, E. M., Gambarotta, S., Floriani, C., Chiesi-Villa, A. & Guastini, C. (1989). Organometallics, 8, 1067–1079. CSD CrossRef CAS Web of Science Google Scholar
Nonius (1997). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Norén, B. & Oskarsson, A. (1985). Acta Chem. Scand. 39a, 701–709. Google Scholar
Norén, B. & Oskarsson, A. (1987). Acta Chem. Scand. 41a, 12–17. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Park, I.-H., Kim, H. J. & Lee, S. S. (2012). CrystEngComm, 14, 4589–4995. CSD CrossRef CAS Google Scholar
Raghuvanshi, A., Dargallay, N. J., Knorr, M., Viau, L., Knauer, L. & Strohmann, C. (2017). J. Inorg. Organomet. Polym. 27, 1501–1513. Web of Science CSD CrossRef CAS Google Scholar
Raghuvanshi, A., Knorr, M., Knauer, L., Strohmann, C., Boullanger, S., Moutarlier, V. & Viau, L. (2019). Inorg. Chem. 58, 5753–5775. Web of Science CSD CrossRef CAS PubMed Google Scholar
Royzman, D. E., Noviello, A. M., Henline, K. M., Pike, R. D., Killarney, J. P., Patterson, H. H., Crawford, C. & Assefa, Z. (2014). J. Inorg. Organomet. Polym. 24, 66–77. CSD CrossRef CAS Google Scholar
Schlachter, A., Lapprand, A., Fortin, D., Strohmann, C., Harvey, P. D. & Knorr, M. (2020). Inorg. Chem. 59, 3686–3708. CSD CrossRef CAS PubMed Google Scholar
Schlachter, A., Viau, L., Fortin, D., Knauer, L., Strohmann, C., Knorr, M. & Harvey, P. D. (2018). Inorg. Chem. 57, 13564–13576. Web of Science CSD CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Solari, E., De Angelis, S., Latronico, M., Floriani, C., Chiesi-Villa, A. & Rizzoli, C. (1996). J. Clust Sci. 7, 553–566. CSD CrossRef CAS Google Scholar
Suenaga, Y., Maekawa, M., Kuroda-Sowa, T., Munakata, M., Morimoto, H., Hiyama, N. & Kitagawa, S. (1997). Anal. Sci. 13, 1047–1049. CrossRef CAS Google Scholar
Toyota, S., Matsuda, Y., Nagaoka, S., Oki, M. & Akashi, H. (1996). Bull. Chem. Soc. Jpn, 69, 3115–3121. CSD CrossRef CAS Google Scholar
Usón, R., Laguna, A., Laguna, M., Manzano, B. R., Jones, P. G. & Sheldrick, G. M. (1984). J. Chem. Soc. Dalton Trans. pp. 285–292. Google Scholar
Yang, L., Powell, D. R. & Houser, R. P. (2007). Dalton Trans. pp. 955–964. Web of Science CSD CrossRef PubMed CAS 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.