Crystal structure and Hirshfeld analysis of di-μ-bromido-bis­[(1-{[dimeth­yl(phenyl­thio­meth­yl)sil­yl]meth­yl}piperidine-κ2N,S)copper(I)] and di-μ-iodido-bis­[(1-{[dimeth­yl(phenyl­thio­meth­yl)sil­yl]meth­yl}piperidine-κ2N,S)copper(I)]

Schäper, K.; Knorr, M.; Strohmann, C.

doi:10.1107/S2056989026009862

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ISSN: 2056-9890

Volume 82| Part 11| November 2026|

https://doi.org/10.1107/S2056989026009862

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Crystal structure and Hirshfeld analysis of di-μ-bromido-bis[(1-{[dimethyl(phenylthiomethyl)silyl]methyl}piperidine-κ²N,S)copper(I)] and di-μ-iodido-bis[(1-{[dimethyl(phenylthiomethyl)silyl]methyl}piperidine-κ²N,S)copper(I)]

Kai Schäper,^a Michael Knorr ^b ^* and Carsten Strohmann ^a ^*

^aTU Dortmund University, Institute for Inorganic Chemistry, Otto-Hahn-Strasse 6, 44227 Dortmund, Germany, and ^bUniversité Marie et Louis Pasteur, Institute UTINAM UMR 6213 CNRS, 16 Route de Gray, 25030 Besançon, France
^*Correspondence e-mail: [email protected], [email protected]

Edited by A. Briceno, Venezuelan Institute of Scientific Research, Venezuela (Received 17 June 2026; accepted 22 September 2026; online 2 October 2026)

The use of 1-{[dimethyl(phenylthiomethyl)silyl]methyl}piperidine piperidine as chelating ligand has been probed by complexation on CuI and CuBr in MeCN solution to afford the dinuclear S,N-chelate title complexes, [Cu₂I₂(C₁₅H₂₅NSSi)₂] and [Cu₂Br₂(C₁₅H₂₅NSSi)₂], which feature a halide-bridged rhomboid-shaped Cu(μ₂-X)Cu (X = I, Br) core with Cu⋯Cu contacts of 2.8249 (5) and 2.7631 (6) Å, respectively. The two isostructural complexes crystalize in the triclinic space group P1 with half molecule in the asymmetric unit. An analysis of the Hirshfeld surfaces shows that H⋯H (van der Waals) interactions dominate with a contact percentage of over 80% in both complexes.

Keywords: crystal structure; dinuclear Cu^I complexes; iodine bridges; bromine bridges; organosilyl S,N donor.

CCDC references: 2590083; 2590084

1. Chemical context

In previous work, we have investigated the potential of the [(piperidinomethyl)silylmethyl] fragment for organic transformations and the preparation of cyclometallated Pd^II complexes (Schildbach et al., 2004 ), (Colquhoun, et al., 2012 ), (Koller et al., 2017 ). In this context we have also synthesized 1-{[dimethyl(phenylthiomethyl)silyl]methyl}piperidine, 1, by treatment of the organosulfur compound (chloromethyl)dimethyl[(phenylthio)methyl]silane with piperidine (Koller et al., 2017). Based on our experience on the coordination of dytopic ligands possessing both a hard N-donor site and a soft S-donor site according to the hard and soft acids and bases (HSAB) concept (Pearson, 1963 ), such as thioether functionalized 2-azabutadienes (Jacquot-Rousseau et al., 2005 ; Kinghat et al., 2024 ; Kubicki et al., 2025 ), we have chosen the soft copper(I) salts CuI and CuBr for the complexation studies. Cu^I is known to form mononuclear complexes with bidentate ligands (Kinghat et al., 2016 ), but in most cases the dinuclear μ₂-halide-bridged rhomboid dimer L₂Cu(μ₂-X)CuL₂ or higher nuclear clusters such as the Cu₄X₄ cubane cluster are formed (Kim et al., 2007 ; Bovin et al., 2023 ). For example, we reported recently on the structure of the rhomboid-shaped dimer [L₂Cu(μ₂-I)CuL₂] [L₂ = (ⁱPrS)₂C=C(H)—N=CPh₂] (CSD refcode IYEVAN; Kinghat et al., 2024), in which the two copper centers are additionally coordinated by the sulfur and nitrogen donor atoms in a chelating manner. This motif is also present in redox-active, tetradentate S,N-donor ligands that simultaneously coordinate both copper(I) centers (CSD refcode SAYJIO; Curcio et al., 2017 ). The applications are not limited to redox chemistry; luminescence properties have also been observed for rhomboid Cu⋯Cu dimers upon excitation by visible light (Zhang et al., 2009 ; Kobayashi et al., 2013 ; Shou et al., 2017 ). This luminescence is also observed for species embedded in supramolecular assemblies, such as metallocages (Xu et al., 2021 ).

A characteristic feature associated with the formation of Cu⋯Cu polynuclear clusters is the observation of Cu⋯Cu distance below the sum of the van der Waals radii (2.8 Å; Bondi, 1964 ). This interaction is referred to as ‘cuprophilicity' and is indicative of an attractive interaction between the copper(I) centers (Che et al., 2000 ). The shortened intermetallic distance can be enforced by bridging ligands such as μ₂-halides, but can also occur in a ligand-unsupported fashion (Siemeling et al., 1997 ; Cotton et al., 1988 ). While most S,N-chelating ligands are based on thioether and pyridine or imine functionalities (Curcio et al., 2017; Cheon et al., 2013 ; Zhang et al., 2009; Kinghat et al., 2024), we report here two examples of rhomboid copper(I) halide dimers coordinated by organosilicon-bridged S,N-donor ligands, utilizing amine moieties as N-donors. In the herein reported examples of silicon-bridged ligands, the silicon center enhances the coordination ability of the donor sites by increasing the electron density of their neighboring carbon centers (Schneider et al., 2023 ; Chen et al., 2013 ; Khatyr et al. 2026 ).

2. Structural commentary

The title compounds Cu₂I₂[PhSCH₂Si(Me₂)CH₂Pip]₂ (2a) and Cu₂Br₂[PhSCH₂Si(Me₂)CH₂Pip]₂ (2b) crystallize at room temperature from acetonitrile in the centrosymmetric space group P $[\overline{1}]$ with half a molecule in the asymmetric unit. The asymmetric units of the complexes are shown in Fig. 1, and characteristic bond parameters are listed in Tables 1 and 2. Both structures feature the same ligand, 1-{[dimethyl(phenylthiomethyl)silyl]methyl}piperidine, which comprises an amine and a thioether Lewis donor moiety bridged via an SiMe₂ group as spacer. The S1—C7 bond length of 1.792 (2) Å and 1.798 (2) Å and the N1—C10 bond lengths of 1.483 (3) Å and 1.489 (3) Å for 2a and 2b, respectively, are consistent with typical values reported for such bond environments (Allen et al., 1987 ). Slight deviations from the ideal tetrahedral angle (109.5°) are observed around the nitrogen atom. In compound 2a, the bond angles around N1 range from 107.69 (16) to 113.40 (13)° while in compound 2b they vary between 107.77 (16) and 112.46 (13)°. The N1—Cu1—S1 bite angles of 97.68 (5)° (2a) and 98.95 (5)° (2b) contribute to a slightly distorted tetrahedral geometry around the Cu^I centers. The t₄ parameters (Yang et al., 2007 ) of 0.87 (2a) and 0.88 (2b) indicate a low degree of distortion in the tetrahedral coordination environment, in contrast to other reported examples of this structural motif. The maximum t₄ of 1.00 describes an ideal tetrahedral coordination environment, whereas a t₄ of 0 indicates an ideal square-planar coordination environment. A common coordination pattern in Cu^I halides is the formation of rhomboid dimers, which can exhibit a dissymmetric bridging by the halides (Kinghat et al., 2014 ). However, in both reported compounds a torsion angle of 0°, enforced by inversion symmetry at the center of the dimer, prevents this dissymmetry. A notable difference between the two structures lies in the Cu⋯Cu distances, which amounts to 2.8249 (5) Å for compound 2a, while in compound 2b it is slightly shorter at 2.7631 (6) Å. The latter value falls below the sum of the van der Waals radii of the two copper(I) centers (2.8 Å; Bondi, 1964), suggesting the presence of a weak Cu⋯Cu interaction.

Table 1
Selected geometric parameters (Å, °) for 2a

I1—Cu1	2.5940 (3)	Cu1—S1	2.3533 (6)
I1—Cu1ⁱ	2.6445 (3)	S1—C7	1.792 (2)
Cu1⋯Cu1ⁱ	2.8249 (5)

N1—Cu1—S1	97.68 (5)	C10—N1—Cu1	107.94 (12)
N1—Cu1—I1	122.78 (5)	C10—N1—C15	109.23 (15)
N1—Cu1—I1ⁱ	103.18 (5)	C11—N1—Cu1	110.19 (12)
S1—Cu1—I1	108.475 (16)	C11—N1—C10	107.69 (16)
S1—Cu1—I1ⁱ	108.077 (16)	C11—N1—C15	108.24 (16)
I1—Cu1—I1ⁱ	114.743 (10)	C15—N1—Cu1	113.40 (13)

Cu1ⁱ—I1—Cu1—I1ⁱ	0	Cu1ⁱ—I1ⁱ—Cu1—I1	0
Symmetry code: (i) .

Table 2
Selected geometric parameters (Å, °) for 2b

Br1—Cu1	2.5197 (4)	Cu1—S1	2.3208 (6)
Br1—Cu1ⁱ	2.4416 (4)	S1—C7	1.798 (2)
Cu1⋯Cu1ⁱ	2.7631 (6)

N1—Cu1—S1	98.95 (5)	C10—N1—Cu1	108.05 (13)
N1—Cu1—Br1	100.62 (5)	C11—N1—Cu1	110.20 (13)
N1—Cu1—Br1ⁱ	123.97 (5)	C11—N1—C10	107.77 (16)
S1—Cu1—Br1	109.379 (19)	C15—N1—Cu1	112.46 (13)
S1—Cu1—Br1ⁱ	110.223 (18)	C15—N1—C10	109.70 (17)
Br1ⁱ—Cu1—Br1	112.332 (14)	C15—N1—C11	108.56 (17)

Cu1ⁱⁱ—Br1—Cu1—I1ⁱⁱ	0	Cu1ⁱⁱ—Br1ⁱⁱ—Cu1—I1	0
Symmetry codes: (i) ; (ii) .

Figure 1
Asymmetric units of 2a and 2b with displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

For a detailed insight into the crystal packing, a Hirshfeld surface analysis was performed (Spackman & Jayatilaka, 2009 ). The Hirshfeld surface and the corresponding two-dimensional fingerprint plots were generated and analysed using CrystalExplorer21 (Spackman et al. 2021 ). The Hirshfeld surface was mapped over d_norm in the range of −0.0729 to 1.4226 arbitrary units for compound 2a and −0.0255 to 1.5298 arbitrary units for compound 2b. While the Hirshfeld surfaces are shown in Fig. 2 (2a) and Fig. 4 (2b), the contribution of the different intermolecular interactions are depicted in the two-dimensional fingerprint plots Fig. 3 (2a) and Fig. 5 (2b). Intermolecular interactions are represented by the color coding on the surface: red spots indicate close contacts, whereas blue and white regions correspond to areas of no significant interaction. Both title compounds exhibit a close contact between the halide center and the hydrogen center H3 of a neighboring molecule H3⋯I1/I1⋯H3 within compound 2a and H3⋯Br1/Br1⋯H3 within compound 2b as can be seen from the Hirshfeld surfaces. Although these contacts are marked as close contacts on the surface, their contribution to the overall surface interactions is relatively small 5.1% for H⋯Br/Br⋯H and 5.9% for H⋯I/I⋯H making them comparable in magnitude. The largest contribution to the interactions in both compounds arises from weak van der Waals H⋯H contacts: 82.8% in compound 2a and 83.2% in compound 2b. This is followed by C⋯H/H⋯C interactions, contributing to 8.3% and 8.5%, respectively. The smallest contribution comes from S⋯H/H⋯S interactions at 3.1% in 2a and 3.0% in 2b. The crystal packing of both title compounds is illustrated in Fig. 6 and is characterized by propagation along the b-axis, which is promoted by the aforementioned close H⋯I/I⋯H interactions.

Figure 2
Hirshfeld surface analysis of 2a showing close contacts in the crystal. The H3⋯I1ⁱⁱⁱ and I1ⁱ⋯H3ⁱⁱ contacts are indicated by the red spots [symmetry codes: (i) −x, 1 − y, 1 − z; (ii) −x, 2 − y, 1 − z; (iii) x, 1 + y, z].

Figure 3
Two-dimensional fingerprint plots for compound 2a showing (a) all contributions, and those delineated into (b) H⋯H, (c) C⋯H/H⋯C and (d) I⋯H/H⋯I-interactions.

Figure 4
Hirshfeld surface analysis of 2b showing close contacts in the crystal. The H3ⁱ⋯Br1 and Br1ⁱ⋯H3 contacts are indicated by the red spots [symmetry code: (i) 1 − x, 1 − y, 2 − z].

Figure 5
Two-dimensional fingerprint plots for compound 2b showing (a) all contributions, and those delineated into (b) H⋯H, (c) C⋯H/H⋯C and (d) Br⋯H/H⋯Br-interactions.

Figure 6
The packing of the solid state structures of 2a (left) and 2b (right) along the b axis.

4. Database survey

A search of the Cambridge Crystallographic Database (Groom et al., 2016 ; WebCSD September 2025) revealed several structures of rhomboid-shaped dimeric CuI complexes, in which the metal centers are internally bridged by halide anions and additionally coordinated by S,N-donor ligands. The most common nitrogen donors in these complexes are imine moieties, as observed in structures such as (CSD AXEWIL, AXEWOR; Flörke et al., 2016 ) and (CSD BURYOE; Flörke, 2015 ). Note that for dimer AXEWOR (bis{N-[2-(benzylsulfanyl)phenyl]-1,3-dimethylimidazolidin-2-imine}bis(μ-iodo)-dicopper) featuring a particular short Cu⋯Cu bond of only 2.5492 (4) Å, a deformation of the planar Cu(μ₂-I)Cu core to a butterfly-shaped cluster is noticed, the μ₂-I atoms forming the wing tips (Flörke et al., 2016). Aromatic pyridine-type and nitrile-based nitrogen donors have also been employed in similar coordination environments (CSD BARGARF; Lee et al., 2017 , CSD JIZZDE; Raghuvanshi et al., 2019 ). Depending on the reaction conditions, CuI is reported to form with t-butylsulfanyl)ethyl)pyridine the dinuclear species bis(μ₂-iodo)bis{2-[2-(t-butylsulfanyl)ethyl]pyridine}dicopper or a heptanuclear pinwheel-shaped Cu₇I₇ cluster (CSD XENZIB; Cheon et al., 2013). The entries are dominated by discrete dinuclear [(S,N)Cu(μ₂-I)Cu(S,N)] species, but also some macrocyclic scaffolds such as tetrakis(μ₂-iodo)-bis{μ₂-4,6-bis[(pyrid-2-ylmethyl)sulfanylmethyl]dibenzo(b,d)furan}tetracopper are known (CSD EHOFEM; Caradoc-Davies & Hanton, 2003 ). Using polydentate ligands such as 2,3-bis(t-butylthiomethyl)quinoxaline also allows the assembly of supramolecular networks incorporating the Cu(μ₂-I)Cu motif (CSD NUHQOX; Zhang et al., 2009). According to the database survey, only one example exists in which a secondary amine-based S,N-donor ligand is coordinated to an iodine-bridged copper(I) dimer (CSD TOTQAU; Cran et al., 1996 ). The Cu⋯Cu distances reported for the two independent molecules of bis(μ₂-iodo)-bis[N-methyl-2-(t-butylthio)-1-phenyl-ethylamine-N,S]dicopper [2.587 (1) and 2.650 (2) Å] are considerably shorter than those of 2a. Likewise, no reports were identified involving organosilicon-bridged mixed S,N-donor ligands coordinating the mentioned copper(I) dimers. A variation of this structural motif, replacing a N-donor moiety with a second thioether, leads to the formation of another organosilicon-bridged ligand capable of chelating the targeted copper(I) dimer, as demonstrated by Yim et al. (CSD TAKWIM; Yim et al., 2003 ). The coordination pattern of dithioethers is also present in copper halide coordination polymers. These types of organometallic polymers are of significant interest due to their intense luminescent properties (Harvey & Knorr, 2010 ). In particular, copper(I) halides coordinated to bis(arylthio)methane ligands (Knorr et al., 2015 ). For bromide-bridged copper(I) complexes featuring a S,N-donor set, apart from two Cu^II species (Al-Noaimi et al., 2024 ), just a single match was found, namely bis(μ-bromo)bis{1,3-dimethyl-N-[2-(phenylsulfanyl)phenyl]imidazolidin-2-imine}dicopper with d(Cu⋯Cu) = 2.7545 (5) Å (CSD HUWWIH0; Flörke et al., 2016). For examples of rhomboid-shaped discrete Cu(μ₂-I)Cu complexes featuring mixed N,O or P,O donors sets, see CSD refcodes POHKED (Rofouei & Hashempur, 2008 ), BEMBAZ (Shou et al., 2017) and XOVROR (Kinghat et al. 2014).

5. Synthesis and crystallization

Di-μ-iodido-bis[(1-{[dimethyl(phenylthiomethyl)silyl]methyl}iperidine-k²N¹,S¹)copper(I)] (2a) was synthesized by adding ligand 1 (614 mg, 2.2 mmol, 1.10 eq.) to CuI (380 mg, 2 mmol, 1.00 eq.) dissolved in acetonitrile (8 mL) at room temperature. For complete crystallization the sample was stored for one day at 278 K. Compound 2a was isolated in the form of colorless blocks. Accordingly, di-μ-bromido-bis[(1-{[dimethyl(phenylthiomethyl)silyl]methyl}piperidine-k²N¹,S¹)copper(I)] (2b) was prepared by adding 1 (614 mg, 2.2 mmol, 1.10 eq.) to CuBr (286 mg, 2.0 mmol, 1.00 eq.) dissolved in 8 mL acetonitrile at room temperature. The sample was also stored at 278 K for one day, allowing the isolation of 2b as colorless blocks.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms were positioned geometrically (C—H = 0.95–1.00 Å) and refined using a riding model, with U_iso(H) = 1.2U_eq(C) for CH₂ and CH hydrogen atoms and U_iso(H) = 1.5U_eq(C) for CH₃ hydrogen atoms. Idealized methyl groups were refined as rotating groups.

Table 3
Experimental details

	2a	2b
Crystal data
Chemical formula	[Cu₂I₂(C₁₅H₂₅NSSi)₂]	[Cu₂Br₂(C₁₅H₂₅NSSi)₂]
M_r	939.90	845.92
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$
Temperature (K)	173	173
a, b, c (Å)	9.9789 (4), 10.0149 (4), 10.1038 (5)	9.8697 (9), 9.9427 (6), 10.0331 (6)
α, β, γ (°)	74.788 (4), 74.367 (4), 73.590 (4)	73.450 (5), 73.529 (6), 73.946 (6)
V (Å³)	913.64 (7)	884.28 (12)
Z	1	1
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	3.06	3.67
Crystal size (mm)	0.2 × 0.1 × 0.1	0.2 × 0.1 × 0.1

Data collection
Diffractometer	Xcalibur, Sapphire3	Xcalibur, Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO, Agilent, 2014 )	Multi-scan (CrysAlis PRO, Agilent, 2014)
T_min, T_max	0.866, 1.000	0.815, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13850, 4322, 4000	11578, 3479, 3121
R_int	0.024	0.034
(sin θ/λ)_max (Å⁻¹)	0.686	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.046, 1.07	0.024, 0.056, 1.05
No. of reflections	4322	3479
No. of parameters	183	183
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.37	0.39, −0.32
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), OLEX2 (Dolomanov et al., 2009 ), CrystalExplorer21 (Spackman et al. 2021) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2590083; 2590084

Crystal structure: contains datablocks 2a, 2b, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989026009862/zn2050sup1.cif

Structure factors: contains datablock 2a. DOI: https://doi.org/10.1107/S2056989026009862/zn20502asup2.hkl

Structure factors: contains datablock 2b. DOI: https://doi.org/10.1107/S2056989026009862/zn20502bsup3.hkl

checkCIF report

Computing details top

Di-µ-bromido-bis[(1-{[dimethyl(phenylthiomethyl)silyl]methyl}piperidine-κ²N,S)copper(I)] (2a) top

Crystal data top

[Cu₂I₂(C₁₅H₂₅NSSi)₂]	Z = 1
M_r = 939.90	F(000) = 468
Triclinic, P1	D_x = 1.708 Mg m⁻³
a = 9.9789 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0149 (4) Å	Cell parameters from 4665 reflections
c = 10.1038 (5) Å	θ = 2.7–29.0°
α = 74.788 (4)°	µ = 3.06 mm⁻¹
β = 74.367 (4)°	T = 173 K
γ = 73.590 (4)°	Block, colourless
V = 913.64 (7) Å³	0.2 × 0.1 × 0.1 mm

Data collection top

Xcalibur, Sapphire3 diffractometer	4322 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4000 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
Detector resolution: 16.0560 pixels mm^-1	θ_max = 29.2°, θ_min = 2.2°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlisPro, Agilent, 2014)	k = −12→12
T_min = 0.866, T_max = 1.000	l = −13→13
13850 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.021	H-atom parameters constrained
wR(F²) = 0.046	w = 1/[σ²(F_o²) + (0.0167P)² + 0.3459P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
4322 reflections	Δρ_max = 0.52 e Å⁻³
183 parameters	Δρ_min = −0.37 e Å⁻³
0 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
I1	0.06780 (2)	0.31973 (2)	0.66613 (2)	0.01743 (5)
Cu1	0.14416 (3)	0.50933 (3)	0.44902 (3)	0.01735 (6)
S1	0.25677 (5)	0.64989 (5)	0.51718 (5)	0.01584 (11)
Si1	0.37208 (6)	0.74081 (6)	0.20604 (6)	0.01785 (13)
N1	0.30834 (17)	0.45600 (18)	0.27033 (18)	0.0158 (4)
C1	0.1595 (2)	0.7237 (2)	0.6666 (2)	0.0159 (4)
C2	0.1194 (2)	0.8681 (2)	0.6652 (2)	0.0215 (5)
H2	0.138647	0.934342	0.579854	0.026*
C3	0.0510 (2)	0.9157 (2)	0.7887 (2)	0.0259 (5)
H3	0.024847	1.014691	0.787903	0.031*
C4	0.0207 (2)	0.8207 (2)	0.9126 (2)	0.0243 (5)
H4	−0.026991	0.854107	0.996773	0.029*
C5	0.0600 (2)	0.6769 (2)	0.9138 (2)	0.0220 (5)
H5	0.039332	0.611119	0.999112	0.026*
C6	0.1292 (2)	0.6278 (2)	0.7914 (2)	0.0191 (4)
H6	0.155968	0.528652	0.792739	0.023*
C7	0.2573 (2)	0.7982 (2)	0.3721 (2)	0.0178 (4)
H7A	0.294285	0.870873	0.392614	0.021*
H7B	0.158342	0.841553	0.358996	0.021*
C8	0.3348 (3)	0.8914 (3)	0.0575 (2)	0.0280 (5)
H8A	0.349905	0.977373	0.074527	0.042*
H8B	0.235479	0.907385	0.049422	0.042*
H8C	0.399209	0.868585	−0.029822	0.042*
C9	0.5620 (2)	0.7058 (3)	0.2169 (3)	0.0288 (5)
H9A	0.623247	0.661353	0.139147	0.043*
H9B	0.576520	0.641839	0.306276	0.043*
H9C	0.586400	0.795547	0.211184	0.043*
C10	0.3219 (2)	0.5896 (2)	0.1665 (2)	0.0179 (4)
H10A	0.229140	0.629380	0.137285	0.022*
H10B	0.393116	0.562221	0.082991	0.022*
C11	0.2662 (2)	0.3637 (2)	0.2033 (2)	0.0222 (5)
H11A	0.336944	0.349938	0.115239	0.027*
H11B	0.172338	0.411965	0.178583	0.027*
C12	0.2562 (2)	0.2195 (2)	0.2968 (3)	0.0256 (5)
H12A	0.232010	0.160950	0.245354	0.031*
H12B	0.178821	0.232026	0.380775	0.031*
C13	0.3966 (2)	0.1432 (2)	0.3423 (3)	0.0278 (5)
H13A	0.383521	0.056052	0.413550	0.033*
H13B	0.470069	0.114689	0.260604	0.033*
C14	0.4464 (2)	0.2396 (2)	0.4035 (2)	0.0221 (5)
H14A	0.381405	0.253883	0.494406	0.026*
H14B	0.543355	0.193165	0.421308	0.026*
C15	0.4494 (2)	0.3824 (2)	0.3059 (2)	0.0199 (5)
H15A	0.479042	0.442933	0.350873	0.024*
H15B	0.521309	0.368636	0.218482	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01694 (7)	0.01668 (8)	0.01766 (8)	−0.00597 (5)	−0.00423 (5)	0.00114 (5)
Cu1	0.01938 (13)	0.01682 (13)	0.01575 (13)	−0.00612 (10)	−0.00242 (10)	−0.00227 (10)
S1	0.0175 (2)	0.0163 (3)	0.0149 (3)	−0.0056 (2)	−0.00332 (19)	−0.0033 (2)
Si1	0.0171 (3)	0.0197 (3)	0.0156 (3)	−0.0066 (2)	−0.0014 (2)	−0.0012 (2)
N1	0.0154 (8)	0.0190 (9)	0.0150 (9)	−0.0044 (7)	−0.0045 (7)	−0.0051 (7)
C1	0.0158 (10)	0.0211 (11)	0.0136 (10)	−0.0055 (8)	−0.0053 (8)	−0.0047 (8)
C2	0.0293 (12)	0.0163 (11)	0.0182 (11)	−0.0075 (9)	−0.0055 (9)	0.0007 (9)
C3	0.0352 (13)	0.0166 (11)	0.0256 (12)	−0.0024 (10)	−0.0065 (10)	−0.0073 (10)
C4	0.0305 (12)	0.0256 (12)	0.0179 (11)	−0.0049 (10)	−0.0052 (9)	−0.0079 (10)
C5	0.0293 (12)	0.0219 (12)	0.0168 (11)	−0.0097 (9)	−0.0062 (9)	−0.0013 (9)
C6	0.0242 (11)	0.0156 (10)	0.0191 (11)	−0.0057 (9)	−0.0079 (9)	−0.0012 (9)
C7	0.0217 (11)	0.0172 (10)	0.0154 (10)	−0.0091 (9)	−0.0034 (8)	−0.0003 (8)
C8	0.0324 (13)	0.0267 (13)	0.0203 (12)	−0.0077 (10)	−0.0002 (10)	−0.0013 (10)
C9	0.0217 (12)	0.0346 (14)	0.0306 (14)	−0.0100 (10)	−0.0038 (10)	−0.0050 (11)
C10	0.0160 (10)	0.0236 (11)	0.0136 (10)	−0.0041 (9)	−0.0026 (8)	−0.0036 (9)
C11	0.0246 (11)	0.0275 (12)	0.0187 (11)	−0.0076 (9)	−0.0044 (9)	−0.0100 (10)
C12	0.0310 (12)	0.0249 (12)	0.0273 (13)	−0.0110 (10)	−0.0061 (10)	−0.0111 (10)
C13	0.0323 (13)	0.0197 (12)	0.0328 (14)	−0.0062 (10)	−0.0064 (10)	−0.0078 (10)
C14	0.0191 (11)	0.0195 (11)	0.0267 (12)	−0.0018 (9)	−0.0075 (9)	−0.0033 (10)
C15	0.0151 (10)	0.0208 (11)	0.0249 (12)	−0.0038 (9)	−0.0055 (8)	−0.0052 (9)

Geometric parameters (Å, º) top

I1—Cu1	2.5940 (3)	C7—H7A	0.9900
I1—Cu1ⁱ	2.6445 (3)	C7—H7B	0.9900
Cu1—Cu1ⁱ	2.8249 (5)	C8—H8A	0.9800
Cu1—S1	2.3533 (6)	C8—H8B	0.9800
Cu1—N1	2.1556 (17)	C8—H8C	0.9800
S1—C1	1.777 (2)	C9—H9A	0.9800
S1—C7	1.792 (2)	C9—H9B	0.9800
Si1—C7	1.886 (2)	C9—H9C	0.9800
Si1—C8	1.861 (2)	C10—H10A	0.9900
Si1—C9	1.855 (2)	C10—H10B	0.9900
Si1—C10	1.886 (2)	C11—H11A	0.9900
N1—C10	1.483 (3)	C11—H11B	0.9900
N1—C11	1.480 (3)	C11—C12	1.517 (3)
N1—C15	1.484 (3)	C12—H12A	0.9900
C1—C2	1.385 (3)	C12—H12B	0.9900
C1—C6	1.388 (3)	C12—C13	1.522 (3)
C2—H2	0.9500	C13—H13A	0.9900
C2—C3	1.385 (3)	C13—H13B	0.9900
C3—H3	0.9500	C13—C14	1.521 (3)
C3—C4	1.377 (3)	C14—H14A	0.9900
C4—H4	0.9500	C14—H14B	0.9900
C4—C5	1.380 (3)	C14—C15	1.512 (3)
C5—H5	0.9500	C15—H15A	0.9900
C5—C6	1.384 (3)	C15—H15B	0.9900
C6—H6	0.9500

N1—Cu1—S1	97.68 (5)	H7A—C7—H7B	108.1
N1—Cu1—I1	122.78 (5)	Si1—C8—H8A	109.5
N1—Cu1—I1ⁱ	103.18 (5)	Si1—C8—H8B	109.5
S1—Cu1—I1	108.475 (16)	Si1—C8—H8C	109.5
S1—Cu1—I1ⁱ	108.077 (16)	H8A—C8—H8B	109.5
Cu1—I1—Cu1ⁱ	65.257 (10)	H8A—C8—H8C	109.5
I1—Cu1—I1ⁱ	114.743 (10)	H8B—C8—H8C	109.5
I1ⁱ—Cu1—Cu1ⁱ	56.508 (10)	Si1—C9—H9A	109.5
I1—Cu1—Cu1ⁱ	58.234 (10)	Si1—C9—H9B	109.5
S1—Cu1—Cu1ⁱ	125.555 (19)	Si1—C9—H9C	109.5
N1—Cu1—Cu1ⁱ	135.29 (5)	H9A—C9—H9B	109.5
C1—S1—Cu1	115.60 (7)	H9A—C9—H9C	109.5
C1—S1—C7	105.22 (10)	H9B—C9—H9C	109.5
C7—S1—Cu1	101.58 (7)	Si1—C10—H10A	106.6
C8—Si1—C7	107.28 (10)	Si1—C10—H10B	106.6
C8—Si1—C10	104.34 (10)	N1—C10—Si1	122.89 (14)
C9—Si1—C7	107.99 (10)	N1—C10—H10A	106.6
C9—Si1—C8	109.50 (11)	N1—C10—H10B	106.6
C9—Si1—C10	114.44 (11)	H10A—C10—H10B	106.6
C10—Si1—C7	113.00 (9)	N1—C11—H11A	109.0
C10—N1—Cu1	107.94 (12)	N1—C11—H11B	109.0
C10—N1—C15	109.23 (15)	N1—C11—C12	112.88 (18)
C11—N1—Cu1	110.19 (12)	H11A—C11—H11B	107.8
C11—N1—C10	107.69 (16)	C12—C11—H11A	109.0
C11—N1—C15	108.24 (16)	C12—C11—H11B	109.0
C15—N1—Cu1	113.40 (13)	C11—C12—H12A	109.4
C2—C1—S1	123.74 (17)	C11—C12—H12B	109.4
C2—C1—C6	119.77 (19)	C11—C12—C13	111.07 (18)
C6—C1—S1	116.43 (16)	H12A—C12—H12B	108.0
C1—C2—H2	120.1	C13—C12—H12A	109.4
C1—C2—C3	119.7 (2)	C13—C12—H12B	109.4
C3—C2—H2	120.1	C12—C13—H13A	109.6
C2—C3—H3	119.7	C12—C13—H13B	109.6
C4—C3—C2	120.6 (2)	H13A—C13—H13B	108.1
C4—C3—H3	119.7	C14—C13—C12	110.35 (19)
C3—C4—H4	120.2	C14—C13—H13A	109.6
C3—C4—C5	119.6 (2)	C14—C13—H13B	109.6
C5—C4—H4	120.2	C13—C14—H14A	109.3
C4—C5—H5	119.8	C13—C14—H14B	109.3
C4—C5—C6	120.4 (2)	H14A—C14—H14B	107.9
C6—C5—H5	119.8	C15—C14—C13	111.69 (19)
C1—C6—H6	120.1	C15—C14—H14A	109.3
C5—C6—C1	119.9 (2)	C15—C14—H14B	109.3
C5—C6—H6	120.1	N1—C15—C14	112.25 (17)
S1—C7—Si1	110.86 (11)	N1—C15—H15A	109.2
S1—C7—H7A	109.5	N1—C15—H15B	109.2
S1—C7—H7B	109.5	C14—C15—H15A	109.2
Si1—C7—H7A	109.5	C14—C15—H15B	109.2
Si1—C7—H7B	109.5	H15A—C15—H15B	107.9

Cu1—S1—C1—C2	−121.35 (17)	C7—Si1—C10—N1	−51.87 (19)
Cu1—S1—C1—C6	61.48 (17)	C8—Si1—C7—S1	168.04 (11)
Cu1—S1—C7—Si1	−64.61 (10)	C8—Si1—C10—N1	−168.07 (16)
Cu1—N1—C10—Si1	60.38 (17)	C9—Si1—C7—S1	−74.02 (14)
Cu1—N1—C11—C12	−65.5 (2)	C9—Si1—C10—N1	72.28 (19)
Cu1—N1—C15—C14	63.7 (2)	C10—Si1—C7—S1	53.60 (14)
S1—C1—C2—C3	−176.20 (17)	C10—N1—C11—C12	176.99 (17)
S1—C1—C6—C5	176.87 (16)	C10—N1—C15—C14	−175.84 (17)
N1—C11—C12—C13	−56.6 (2)	C11—N1—C10—Si1	179.33 (14)
C1—S1—C7—Si1	174.54 (10)	C11—N1—C15—C14	−58.8 (2)
C1—C2—C3—C4	−1.0 (3)	C11—C12—C13—C14	51.3 (3)
C2—C1—C6—C5	−0.4 (3)	C12—C13—C14—C15	−51.8 (2)
C2—C3—C4—C5	0.6 (4)	C13—C14—C15—N1	56.9 (2)
C3—C4—C5—C6	−0.1 (3)	C15—N1—C10—Si1	−63.3 (2)
C4—C5—C6—C1	0.0 (3)	C15—N1—C11—C12	59.0 (2)
C6—C1—C2—C3	0.9 (3)	Cu1ⁱ—I1—Cu1—I1ⁱ	0
C7—S1—C1—C2	−10.2 (2)	Cu1ⁱ—I1ⁱ—Cu1—I1	0
C7—S1—C1—C6	172.64 (16)

Symmetry code: (i) −x, −y+1, −z+1.

Di-µ-iodido-bis[(1-{[dimethyl(phenylthiomethyl)silyl]methyl}piperidine-κ²N,S)copper(I)] (2b) top

Crystal data top

[Cu₂Br₂(C₁₅H₂₅NSSi)₂]	Z = 1
M_r = 845.92	F(000) = 432
Triclinic, P1	D_x = 1.588 Mg m⁻³
a = 9.8697 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9427 (6) Å	Cell parameters from 5514 reflections
c = 10.0331 (6) Å	θ = 2.7–29.0°
α = 73.450 (5)°	µ = 3.67 mm⁻¹
β = 73.529 (6)°	T = 173 K
γ = 73.946 (6)°	Block, colourless
V = 884.28 (12) Å³	0.2 × 0.1 × 0.1 mm

Data collection top

Xcalibur, Sapphire3 diffractometer	3479 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3121 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 16.0560 pixels mm^-1	θ_max = 26.0°, θ_min = 2.2°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlisPro, Agilent, 2014)	k = −12→12
T_min = 0.815, T_max = 1.000	l = −12→12
11578 measured reflections

Refinement top

Refinement on F²	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	H-atom parameters constrained
wR(F²) = 0.056	w = 1/[σ²(F_o²) + (0.0217P)² + 0.1872P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3479 reflections	Δρ_max = 0.39 e Å⁻³
183 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
Br1	0.44330 (2)	0.16667 (2)	0.83511 (2)	0.01766 (7)
Cu1	0.64346 (3)	0.01004 (3)	0.95483 (3)	0.01744 (8)
S1	0.75500 (6)	0.15336 (6)	1.01668 (6)	0.01535 (13)
Si1	0.87510 (7)	0.24369 (7)	0.69886 (6)	0.01714 (15)
N1	0.80590 (19)	−0.04401 (19)	0.77416 (18)	0.0144 (4)
C1	0.6580 (2)	0.2289 (2)	1.1663 (2)	0.0149 (5)
C2	0.6241 (3)	0.3746 (2)	1.1623 (2)	0.0203 (5)
H2	0.646215	0.441359	1.074519	0.024*
C3	0.5580 (3)	0.4226 (3)	1.2866 (2)	0.0237 (6)
H3	0.536757	0.522468	1.283898	0.028*
C4	0.5225 (3)	0.3271 (3)	1.4146 (2)	0.0234 (6)
H4	0.476526	0.360868	1.499371	0.028*
C5	0.5546 (3)	0.1816 (3)	1.4181 (2)	0.0200 (5)
H5	0.530215	0.115342	1.505759	0.024*
C6	0.6222 (2)	0.1319 (2)	1.2946 (2)	0.0181 (5)
H6	0.643874	0.032017	1.297541	0.022*
C7	0.7568 (3)	0.3027 (2)	0.8650 (2)	0.0186 (5)
H7A	0.793498	0.377756	0.882548	0.022*
H7B	0.657043	0.344529	0.851143	0.022*
C8	1.0676 (3)	0.2078 (3)	0.7091 (3)	0.0259 (6)
H8A	1.129729	0.165515	0.629573	0.039*
H8B	1.081440	0.140825	0.799549	0.039*
H8C	1.093103	0.298004	0.703684	0.039*
C9	0.8400 (3)	0.3960 (3)	0.5453 (2)	0.0266 (6)
H9A	0.852695	0.483819	0.561937	0.040*
H9B	0.740823	0.409670	0.535477	0.040*
H9C	0.908085	0.374756	0.457758	0.040*
C10	0.8212 (2)	0.0911 (2)	0.6644 (2)	0.0167 (5)
H10A	0.727342	0.131098	0.635901	0.020*
H10B	0.892652	0.063205	0.579862	0.020*
C11	0.7603 (3)	−0.1381 (2)	0.7116 (2)	0.0199 (5)
H11A	0.832123	−0.154694	0.623141	0.024*
H11B	0.666236	−0.088987	0.685868	0.024*
C12	0.7457 (3)	−0.2822 (2)	0.8139 (3)	0.0225 (5)
H12A	0.667195	−0.266790	0.898499	0.027*
H12B	0.719428	−0.342937	0.766290	0.027*
C13	0.8855 (3)	−0.3588 (3)	0.8609 (3)	0.0246 (6)
H13A	0.959846	−0.389626	0.779328	0.030*
H13B	0.869890	−0.445559	0.936751	0.030*
C14	0.9384 (3)	−0.2601 (2)	0.9167 (2)	0.0207 (5)
H14A	0.871620	−0.242401	1.007412	0.025*
H14B	1.035159	−0.307698	0.936562	0.025*
C15	0.9471 (2)	−0.1180 (2)	0.8106 (2)	0.0179 (5)
H15A	0.979252	−0.055672	0.851440	0.021*
H15B	1.019779	−0.135032	0.722678	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01788 (13)	0.01598 (12)	0.01710 (13)	−0.00516 (10)	−0.00396 (10)	0.00099 (9)
Cu1	0.01935 (16)	0.01641 (15)	0.01617 (15)	−0.00650 (12)	−0.00149 (13)	−0.00287 (12)
S1	0.0178 (3)	0.0148 (3)	0.0142 (3)	−0.0049 (2)	−0.0034 (2)	−0.0031 (2)
Si1	0.0182 (3)	0.0174 (3)	0.0147 (3)	−0.0063 (3)	−0.0020 (3)	−0.0010 (3)
N1	0.0137 (10)	0.0153 (9)	0.0152 (9)	−0.0038 (8)	−0.0042 (8)	−0.0037 (8)
C1	0.0134 (11)	0.0194 (12)	0.0146 (11)	−0.0040 (10)	−0.0058 (10)	−0.0051 (9)
C2	0.0246 (13)	0.0180 (12)	0.0178 (12)	−0.0046 (10)	−0.0059 (11)	−0.0021 (10)
C3	0.0300 (14)	0.0147 (12)	0.0276 (13)	−0.0026 (11)	−0.0077 (12)	−0.0072 (10)
C4	0.0259 (14)	0.0270 (14)	0.0189 (12)	−0.0011 (11)	−0.0061 (11)	−0.0106 (11)
C5	0.0240 (13)	0.0222 (13)	0.0143 (11)	−0.0062 (11)	−0.0062 (10)	−0.0014 (10)
C6	0.0222 (13)	0.0154 (12)	0.0192 (12)	−0.0068 (10)	−0.0071 (10)	−0.0026 (9)
C7	0.0225 (13)	0.0171 (12)	0.0170 (12)	−0.0083 (10)	−0.0040 (10)	−0.0014 (9)
C8	0.0226 (13)	0.0297 (14)	0.0256 (13)	−0.0115 (11)	−0.0026 (11)	−0.0037 (11)
C9	0.0310 (15)	0.0231 (13)	0.0209 (13)	−0.0092 (12)	−0.0022 (12)	0.0023 (11)
C10	0.0175 (12)	0.0197 (12)	0.0122 (11)	−0.0047 (10)	−0.0019 (10)	−0.0030 (9)
C11	0.0228 (13)	0.0232 (13)	0.0190 (12)	−0.0059 (11)	−0.0073 (11)	−0.0092 (10)
C12	0.0279 (14)	0.0202 (13)	0.0255 (13)	−0.0084 (11)	−0.0070 (11)	−0.0101 (10)
C13	0.0285 (14)	0.0174 (12)	0.0291 (14)	−0.0067 (11)	−0.0058 (12)	−0.0057 (11)
C14	0.0172 (12)	0.0194 (12)	0.0253 (13)	−0.0031 (10)	−0.0080 (11)	−0.0019 (10)
C15	0.0138 (12)	0.0178 (12)	0.0228 (12)	−0.0028 (10)	−0.0051 (10)	−0.0052 (10)

Geometric parameters (Å, º) top

Br1—Cu1	2.5197 (4)	C7—H7A	0.9900
Br1—Cu1ⁱ	2.4416 (4)	C7—H7B	0.9900
Cu1—Cu1ⁱ	2.7631 (6)	C8—H8A	0.9800
Cu1—S1	2.3208 (6)	C8—H8B	0.9800
Cu1—N1	2.1391 (18)	C8—H8C	0.9800
S1—C1	1.778 (2)	C9—H9A	0.9800
S1—C7	1.798 (2)	C9—H9B	0.9800
Si1—C7	1.887 (2)	C9—H9C	0.9800
Si1—C8	1.861 (2)	C10—H10A	0.9900
Si1—C9	1.863 (2)	C10—H10B	0.9900
Si1—C10	1.885 (2)	C11—H11A	0.9900
N1—C10	1.489 (3)	C11—H11B	0.9900
N1—C11	1.483 (3)	C11—C12	1.523 (3)
N1—C15	1.478 (3)	C12—H12A	0.9900
C1—C2	1.385 (3)	C12—H12B	0.9900
C1—C6	1.391 (3)	C12—C13	1.514 (3)
C2—H2	0.9500	C13—H13A	0.9900
C2—C3	1.384 (3)	C13—H13B	0.9900
C3—H3	0.9500	C13—C14	1.520 (3)
C3—C4	1.381 (3)	C14—H14A	0.9900
C4—H4	0.9500	C14—H14B	0.9900
C4—C5	1.385 (3)	C14—C15	1.515 (3)
C5—H5	0.9500	C15—H15A	0.9900
C5—C6	1.386 (3)	C15—H15B	0.9900
C6—H6	0.9500

N1—Cu1—S1	98.95 (5)	H7A—C7—H7B	108.1
N1—Cu1—Br1	100.62 (5)	Si1—C8—H8A	109.5
N1—Cu1—Br1ⁱ	123.97 (5)	Si1—C8—H8B	109.5
S1—Cu1—Br1	109.379 (19)	Si1—C8—H8C	109.5
S1—Cu1—Br1ⁱ	110.223 (18)	H8A—C8—H8B	109.5
Br1ⁱ—Cu1—Br1	112.332 (14)	H8A—C8—H8C	109.5
Cu1ⁱ—Br1—Cu1	67.668 (13)	H8B—C8—H8C	109.5
Br1ⁱ—Cu1—Cu1ⁱ	57.513 (12)	Si1—C9—H9A	109.5
Br1—Cu1—Cu1ⁱ	54.819 (12)	Si1—C9—H9B	109.5
S1—Cu1—Cu1ⁱ	127.45 (2)	Si1—C9—H9C	109.5
N1—Cu1—Cu1ⁱ	131.44 (5)	H9A—C9—H9B	109.5
C1—S1—Cu1	116.49 (7)	H9A—C9—H9C	109.5
C1—S1—C7	105.35 (10)	H9B—C9—H9C	109.5
C7—S1—Cu1	101.37 (8)	Si1—C10—H10A	106.7
C8—Si1—C7	108.62 (11)	Si1—C10—H10B	106.7
C8—Si1—C9	109.66 (12)	N1—C10—Si1	122.41 (15)
C8—Si1—C10	114.59 (11)	N1—C10—H10A	106.7
C9—Si1—C7	106.74 (11)	N1—C10—H10B	106.7
C9—Si1—C10	104.44 (11)	H10A—C10—H10B	106.6
C10—Si1—C7	112.43 (10)	N1—C11—H11A	109.2
C10—N1—Cu1	108.05 (13)	N1—C11—H11B	109.2
C11—N1—Cu1	110.20 (13)	N1—C11—C12	112.25 (18)
C11—N1—C10	107.77 (16)	H11A—C11—H11B	107.9
C15—N1—Cu1	112.46 (13)	C12—C11—H11A	109.2
C15—N1—C10	109.70 (17)	C12—C11—H11B	109.2
C15—N1—C11	108.56 (17)	C11—C12—H12A	109.4
C2—C1—S1	123.93 (17)	C11—C12—H12B	109.4
C2—C1—C6	119.8 (2)	H12A—C12—H12B	108.0
C6—C1—S1	116.20 (17)	C13—C12—C11	111.02 (19)
C1—C2—H2	120.1	C13—C12—H12A	109.4
C3—C2—C1	119.8 (2)	C13—C12—H12B	109.4
C3—C2—H2	120.1	C12—C13—H13A	109.6
C2—C3—H3	119.6	C12—C13—H13B	109.6
C4—C3—C2	120.7 (2)	C12—C13—C14	110.39 (19)
C4—C3—H3	119.6	H13A—C13—H13B	108.1
C3—C4—H4	120.3	C14—C13—H13A	109.6
C3—C4—C5	119.4 (2)	C14—C13—H13B	109.6
C5—C4—H4	120.3	C13—C14—H14A	109.3
C4—C5—H5	119.8	C13—C14—H14B	109.3
C4—C5—C6	120.4 (2)	H14A—C14—H14B	108.0
C6—C5—H5	119.8	C15—C14—C13	111.55 (19)
C1—C6—H6	120.1	C15—C14—H14A	109.3
C5—C6—C1	119.8 (2)	C15—C14—H14B	109.3
C5—C6—H6	120.1	N1—C15—C14	111.56 (18)
S1—C7—Si1	110.73 (12)	N1—C15—H15A	109.3
S1—C7—H7A	109.5	N1—C15—H15B	109.3
S1—C7—H7B	109.5	C14—C15—H15A	109.3
Si1—C7—H7A	109.5	C14—C15—H15B	109.3
Si1—C7—H7B	109.5	H15A—C15—H15B	108.0

Cu1—S1—C1—C2	−124.41 (19)	C7—Si1—C10—N1	−53.0 (2)
Cu1—S1—C1—C6	58.85 (19)	C8—Si1—C7—S1	−72.86 (14)
Cu1—S1—C7—Si1	−64.89 (12)	C8—Si1—C10—N1	71.6 (2)
Cu1—N1—C10—Si1	60.00 (19)	C9—Si1—C7—S1	168.97 (12)
Cu1—N1—C11—C12	−64.1 (2)	C9—Si1—C10—N1	−168.38 (18)
Cu1—N1—C15—C14	62.6 (2)	C10—Si1—C7—S1	55.03 (15)
S1—C1—C2—C3	−175.05 (18)	C10—N1—C11—C12	178.24 (19)
S1—C1—C6—C5	175.94 (17)	C10—N1—C15—C14	−177.15 (17)
N1—C11—C12—C13	−56.6 (3)	C11—N1—C10—Si1	179.07 (16)
C1—S1—C7—Si1	173.31 (11)	C11—N1—C15—C14	−59.6 (2)
C1—C2—C3—C4	−1.3 (4)	C11—C12—C13—C14	51.7 (3)
C2—C1—C6—C5	−0.9 (3)	C12—C13—C14—C15	−52.5 (3)
C2—C3—C4—C5	0.4 (4)	C13—C14—C15—N1	57.5 (3)
C3—C4—C5—C6	0.2 (4)	C15—N1—C10—Si1	−62.9 (2)
C4—C5—C6—C1	0.1 (4)	C15—N1—C11—C12	59.5 (2)
C6—C1—C2—C3	1.6 (4)	Cu1ⁱⁱ—Br1—Cu1—I1ⁱⁱ	0
C7—S1—C1—C2	−13.0 (2)	Cu1ⁱⁱ—Br1ⁱⁱ—Cu1—I1	0
C7—S1—C1—C6	170.27 (17)

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

Selected geometric parameters (Å, °) for 2a top

I1—Cu1	2.5940 (3)
I1—Cu1i	2.6445 (3)
Cu1···Cu1i	2.8249 (5)
Cu1—S1	2.3533 (6)
S1—C7	1.792 (2)
N1—Cu1—S1	97.68 (5)
N1—Cu1—I1	122.78 (5)
N1—Cu1—I1i	103.18 (5)
S1—Cu1—I1	108.475 (16)
S1—Cu1—I1i	108.077 (16)
I1—Cu1—I1i	114.743 (10)
C10—N1—Cu1	107.94 (12)
C10—N1—C15	109.23 (15)
C11—N1—Cu1	110.19 (12)
C11—N1—C10	107.69 (16)
C11—N1—C15	108.24 (16)
C15—N1—Cu1	113.40 (13)
Cu1i—I1—Cu1—I1i	0.000
Cu1i—I1i—Cu1—I1	0.000

Symmetry code: (i) -x, 1 - y, 1 - z.

Selected geometric parameters (Å, °) for 2b. top

Br1—Cu1	2.5197 (4)
Br1—Cu1i	2.4416 (4)
Cu1···Cu1i	2.7631 (6)
Cu1—S1	2.3208 (6)
S1—C7	1.798 (2)
N1–Cu1—S1	98.95 (5)
N1—Cu1—Br1	100.62 (5)
N1—Cu1—Br1i	123.97 (5)
S1—Cu1—Br1	109.379 (19)
S1—Cu1—Br1i	110.223 (18)
Br1—Cu1—Br1i	112.332 (14)
C10—N1—Cu1	108.05 (13)
C11—N1—Cu1	110.20 (13)
C11—N1—C10	107.77 (16)
C15—N1—Cu1	112.46 (13)
C15—N1—C10	109.70 (17)
C15—N1—C11	108.56 (17)
Cu1i—Br1—Cu1—Br1i	0.000
Cu1i—Br1i—Cu1—Br1	0.000

Symmetry code: (i) 1–x, –y, 2–z

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