Isomorphous dinuclear copper(I) complexes bridged by 4-methyl-1H-1,2,4-triazole-5-thiol­ate ligands: chloride and bromide analogues

Ahmad, A.; Saowanit, S.; Leesakul, N.; Amornpitoksuk, P.; Temram, T.; Rujiralai, T.; Saithong, S.

doi:10.1107/S2056989026007516

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ISSN: 2056-9890

Volume 82| Part 8| August 2026| Pages 992-997

https://doi.org/10.1107/S2056989026007516

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Isomorphous dinuclear copper(I) complexes bridged by 4-methyl-1H-1,2,4-triazole-5-thiolate ligands: chloride and bromide analogues

Alfandi Ahmad,^a Sudthana Saowanit,^a Nararak Leesakul,^a Pongsaton Amornpitoksuk,^a Thitirat Temram,^a Thitima Rujiralai ^a and Saowanit Saithong ^a,^b ^*

^aDivision of Physical Science and Center of Excellence for Innovation in Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90110, Thailand, and ^bMedical Science Research and Innovation Institute, Research and Development Office, Prince of Songkla University, Hat-Yai 901120, Thailand
^*Correspondence e-mail: [email protected]

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 30 June 2026; accepted 22 July 2026; online 31 July 2026)

The title isomorphous copper(I) coordination complexes, bis(μ-4-methyl-1H-1,2,4-triazole-5-thiolato)bis[chlorido(triphenylphosphane)copper(II)], [Cu₂(C₃H₅N₃S)₂Cl₂(C₁₈H₁₅P)₂], and bis(μ-4-methyl-1H-1,2,4-triazole-5-thiolato)bis[bromido(triphenylphosphane)copper(II)], [Cu₂(C₃H₅N₃S)₂Br₂(C₁₈H₁₅P)₂], were synthesized from copper(I) halide salts and a mixed-ligand system containing Hmptrz and PPh₃ in acetonitrile (Hmptrz = 4-methyl-1H-1,2,4-triazole-5-thione and PPh₃ = triphenylphosphine). The asymmetric unit comprises one-half of the dinuclear complex, with each copper(I) center exhibiting a distorted tetrahedral coordination geometry defined by one halide ion, one phosphorus atom from PPh₃, and two μ-S bridging from Hmptrz bridging molecules. The two μ-S bridges [Cu—S—Cu ≃ 70.2°] connect pairs of copper(I) atoms to generate a lozenge-shaped, centrosymmetric Cu₂S₂ core. In the extended structure C—H⋯X (X = Cl or Br) hydrogen bonds link the dimers into a three-dimensional supramolecular architecture. Hirshfeld surface and two-dimensional fingerprint plot analyses were also carried out to investigate and quantify the intermolecular contacts governing the crystal packing.

Keywords: dinuclear complex; 4-methyl-1H-1,2,4-triazole-5-thione; triphenyl phosphane; isomorphous structure; crystal structure.

CCDC references: 2575198; 2575197

1. Chemical context

In recent years, the development of highly efficient luminescent transition-metal complexes has attracted substantial interest due to their widespread applications in organic light-emitting diodes (OLEDs), photocatalysis, and chemical sensing. While noble-metal complexes based on Ir^III (Kerzig et al., 2019 ; Pfund et al., 2020 ; Schreier et al., 2022 ) and Pt^II (Lai & Che, 2004 ; Guerchais et al., 2011 ; Ma et al., 2013 ; Zhong et al., 2013 ; Li et al., 2016 ) have historically dominated the field, their low crustal abundance and high cost limit their large-scale industrial viability. Therefore, research has shifted significantly toward earth-abundant, cost-effective first-row transition metals. Among these, Cu^I complexes have attracted interest because their closed-shell 3d¹⁰ electronic configuration suppresses metal-centered non-radiative decay pathways and supports metal–ligand charge-transfer (MLCT) transitions. However, photoexcitation may induce pseudo-Jahn–Teller distortion, resulting in a flattening of the coordination geometry and enhanced non-radiative deactivation in solution. To circumvent these geometric liabilities, research has increasingly focused on dinuclear copper(I) architectures. Utilizing bridging ligands – such as rigid multi-nitrogen heterocycles or phosphines — secures two copper(I) centers in close spatial proximity. This structural dimerization confers several vital photophysical advantages: (i) enhanced rigidity, which effectively suppresses non-radiative Jahn–Teller distortions (Cao et al., 2026 ), (ii) metal–metal interactions, driven by the close Cu⋯Cu spatial proximity that modulates the frontier molecular orbitals (Chatterjee et al., 2024 ) and (iii) promoted thermally activated delayed fluorescence (TADF) via minimized singlet-triplet energy splitting (Li et al., 2020 ; Housecroft & Constable, 2022 ). Motivated by these advantages, we decided to investigate the synthesis and photophysical properties of a series of copper(I) complexes featuring a mixed-ligand system composed of 4-methyl-1H-1,2,4-triazole-5-thione (C₃H₅N₃S; Hmptrz) and triphenylphosphine (C₁₈H₁₅P; PPh₃). In this design, the triazole-thione derivative, Hmptrz, is expected to act as a bridging ligand to link the copper(I) centers into close spatial proximity, while the bulky PPh₃ co-ligands offer steric interference that stabilizes the coordination sphere. This distinct mixed-ligand environment is hypothesized to enhance structural rigidity, which fundamentally optimizes the luminescent performance for multifaceted technological applications. We now report the syntheses and structures of the title compounds, [Cu₂(C₃H₅N₃S)₂(C₁₈H₁₅P)₂Cl₂] (I) and [Cu₂(C₃H₅N₃S)₂(C₁₈H₁₅P)₂Br₂] (II).

2. Structural commentary

Complexes (I) and (II) are isostructural and crystallize in the triclinic space group Pī. The asymmetric unit comprises one Cu^I cation, a terminal halide ligand (Cl⁻ or Br^–), one PPh₃ ligand, and one S-bridging Hmptrz molecule. Crystal symmetry results in the Hmptrz molecules bridging two Cu^I cations to form a dinuclear structure. Thus, a centrosymmetric Cu₂S₂ core resides about an inversion center, with each Cu^I center adopting a pseudotetrahedral geometry. The coordination sphere of the entire molecule contains a central Cu₂S₂ core, a pair of terminally bonded halide ions, two S-bridging Hmptrz ligands, and two terminal PPh₃ ligands. Both complexes exhibit similar coordination geometries around the metal centers, best described as distorted tetrahedral (Fig. 1, Tables 1 and 2). For example, the bond angles around the copper center range from 95.874 (17)° to 115.482 (18)° for the chloro complex (I) and from 96.366 (17)° to 116.06 (2)° for the bromo complex (II). The observed Cu–halide distances are 2.3002 (5) Å for Cu1—Cl1 in (I) and 2.4284 (4) Å for Cu1—Br1 in (II). The Cu1—S1 bond lengths are 2.3245 (5) Å and 2.5781 (5) Å for (I) and 2.3268 (6) Å and 2.5501 (7) Å for (II). The Hmptrz ligand acts as a bridging motif via its S atom, linking two copper centers. The Cu₂S₂ core is a common structural feature in this family of complexes (Taylor et al., 1974 ) and adopts a distinctive lozenge geometry characterized by alternating short and long Cu⋯S bridging distances. This variation can be attributed to the orbital characteristics and electron-density distribution of the bridging sulfur atom. The S—Cu—S and Cu—S—Cu bond angles are 109.682 (15) and 70.318 (15)° for (I), and 109.762 (19) and 70.238 (19)° for (II), respectively. These angles are consistent with those commonly observed in related structures (Grifasi et al., 2015 ). Given that the sum of the van der Waals radii for two copper atoms is approximately 2.8 Å (Huheey et al., 1993 ), the observed Cu1⋯Cu1ⁱ [symmetry code: (i) 1 − x, 1 − y, 1 − z) separations of 2.8308 (5) Å for (I) and 2.8115 (6) Å for (II) indicate a minor Cu⋯Cu interaction. This is typical for dinuclear Cu^I complexes with rhomboidal Cu₂S₂ cores, whereas the lozenge geometry generally permits only weak Cu^I⋯Cu^I (cuprophilic) interactions (Lobana et al., 2008 , 2009 ). Both complexes exhibit a weak intramolecular N—H⋯X (X = Cl, Br) hydrogen bond (Fig. 2, Tables 3 and 4).

Table 1
Selected geometric parameters (Å, °) for (I)

Cu1—P1	2.2324 (5)	Cu1—S1	2.3245 (5)
Cu1—Cl1	2.3002 (5)	Cu1—S1ⁱ	2.5781 (5)

P1—Cu1—Cl1	113.502 (19)	Cl1—Cu1—S1ⁱ	95.874 (17)
P1—Cu1—S1	115.482 (18)	S1—Cu1—S1ⁱ	109.682 (15)
Cl1—Cu1—S1	112.318 (18)	Cu1—S1—Cu1ⁱ	70.318 (15)
P1—Cu1—S1ⁱ	108.064 (18)
Symmetry code: (i) .

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

Cu1—P1	2.2376 (6)	Cu1—Br1	2.4284 (4)
Cu1—S1	2.3268 (6)	Cu1—S1ⁱ	2.5501 (7)

P1—Cu1—S1	116.06 (2)	S1—Cu1—S1ⁱ	109.762 (19)
P1—Cu1—Br1	110.271 (19)	Br1—Cu1—S1ⁱ	96.366 (17)
S1—Cu1—Br1	113.182 (18)	Cu1—S1—Cu1ⁱ	70.238 (19)
P1—Cu1—S1ⁱ	109.40 (2)
Symmetry code: (i) .

Table 3
Hydrogen-bond geometry (Å, °) for (I)

Cg4 is the centroid of the C10–C15 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1	0.83 (2)	2.33 (2)	3.1080 (18)	155.8 (19)
C2—H2⋯Cl1ⁱⁱ	0.93	2.79	3.439 (2)	128
C7—H7⋯Cg4ⁱⁱⁱ	0.93	2.81	3.626 (4)	147
Symmetry codes: (ii) ; (iii) .

Table 4
Hydrogen-bond geometry (Å, °) for (II)

Cg4 is the centroid of the C10–C15 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br1	0.87 (2)	2.42 (2)	3.235 (2)	156 (2)
C2—H2⋯Br1ⁱⁱ	0.93	2.90	3.563 (2)	130
C7—H7⋯Cg4ⁱⁱⁱ	0.93	2.81	3.638 (4)	149
Symmetry codes: (ii) ; (iii) .

Figure 1
The molecular structures of the title dinuclear complexes (X: Cl or Br) with 30% displacement ellipsoids.

Figure 2
The intramolecular interaction, N—H⋯Cl or N—H⋯Br in (I) and (II), respectively.

3. Supramolecular features

In the extended structures, weak C—H⋯X (X = Cl, Br) hydrogen-bonding interactions are observed (Tables 3 and 4) between adjacent molecules (Figs. 3a and 3b). These interactions generate supramolecular chains extending along the diagonal direction of the (110) plane (Fig. 3). In addition, both complexes exhibit similar C—H⋯π interactions. For crystal-packing analysis, a commonly accepted geometrical criterion for a significant C—H⋯π interaction is an H⋯Cg distance shorter than 3.5 Å together with a C—H⋯Cg angle greater than 110°. In both structures, the C7—H7 group interacts with the centroid of the phenyl ring (Cg4 is the centroid of the C10–C15 ring), with H⋯Cg distances of 2.81 Å in both (I) and (II). These interactions link neighbouring molecules through their aromatic rings, forming supramolecular chains propagating parallel to the a-axis direction (Fig. 4). To gain further insight into the crystal packing, a Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ; Turner et al., 2017 ) was performed. The corresponding two-dimensional fingerprint plots were used to quantify the relative contributions of the various intermolecular contacts to the crystal packing (Rohl et al., 2008 ). The percentage contributions of the individual intermolecular contacts are presented in Fig. 5.

Figure 3
The intermolecular interactions, (a) C—H⋯Cl for (I) and (b) C—H⋯Br for (II).

Figure 4
The C—H⋯π intermolecular interactions of (a) (I) and (b) (II).

Figure 5
The two-dimensional fingerprint plots for (a) (I) and (b) (II) showing all interactions and those delineated into H⋯H, H⋯C/C⋯H, H⋯X/X⋯H and N ⋯H/H⋯N interactions (X: Cl or Br).

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.47; Groom et al., 2016 ) for copper(I) halide complexes containing μ-S-bridging thione ligands and phosphine co-ligands revealed numerous dinuclear Cu^I complexes featuring a Cu₂S₂ core. Representative examples incorporating a single μ-S-bridging thione ligand include CSD refcodes FOCBII01 and FONBEP (Stergioudis et al., 1987 ), JADRUB (Mentzafos et al., 1989 ), IVEREG (Aslanidis et al., 2004 ), ETUCUN02, HOMYOY, MEPVIN01, HOMZAL, HOMYAK, HOMYEO and HOMYUE (Bowmaker et al., 2009b ), together with WUDFUX and WUDGEI (Bowmaker et al., 2009a ).

A number of closely related dinuclear Cu^I complexes containing μ-S-bridging thione ligands in combination with phosphine ligands have also been reported. These include JADHAX and VIPBIF (Karagiannidis et al., 1989 , 1990 ), JITFOH (Hadjikakou et al., 1991 ), YEZDOW (Aslanidis et al., 1994 ), GADHID (Aslanidis et al., 2002 ), WALROR (Hadjikakou et al., 2005 ), CITFAN (Mamais et al., 2008 ), TOMFIM (Papazoglou et al., 2014 ), ADIGUS (Varna et al., 2016 ) and TEQQAK (Karasmani et al., 2018 ). Despite differences in the nature of the thione, phosphine and terminal halide ligands, these complexes share a common Cu₂S₂ core and a distorted tetrahedral coordination geometry around the Cu^I centres. The title compounds therefore belong to this family of dinuclear Cu^I complexes and expand the structural diversity of μ-S-bridged copper(I) phosphine compounds.

5. Synthesis and crystallization

Synthesis of (I)

4-Methyl-4H-1,2,4-triazole-3-thiol (0.175 g, 1.52 mmol) was dissolved in 20 ml of acetonitrile and heated to 343 K. Copper(I) chloride (0.150 g, 1.52 mmol) was then added, and the reaction mixture was stirred continuously at 343 K for 3 h. Subsequently, a solution of triphenylphosphine in acetonitrile (10 ml) was added dropwise, and the mixture was stirred for a further 2 h at the same temperature. The reaction mixture was filtered to remove the insoluble solid. The clear filtrate was left to evaporate slowly at room temperature. After several days, colorless crystals of (I) suitable for X-ray diffraction were obtained. The crystals were separated and dried. The crystals obtained consisted of a mixture of crystalline products. Therefore, neither the isolated yield nor the elemental analysis could be determined for the target complex. Nevertheless, a suitable single crystal was selected for single-crystal X-ray diffraction analysis.

Synthesis of (II)

A mixture of copper(I) bromide (0.150 g, 1.05 mmol) and 4-methyl-4H-1,2,4-triazole-3-thiol (0.120 g, 1.04 mmol) was dissolved in 20 ml of acetonitrile and heated to 343 K and stirred continuously for 3 h. In a separate vessel, triphenylphosphine (0.550 g, 2.10 mmol, 2 equiv.) was dissolved in 10 ml of acetonitrile and added dropwise to the reaction mixture. The resulting solution was stirred at 343 K for an additional 2 h and subsequently filtered to remove any insoluble material. The clear filtrate was allowed to evaporate slowly at room temperature, affording colorless crystals of (II) after several days. The crystals were collected by filtration and dried. Yield: 0.4315 g (79.5%). m.p. 217.7–218.7 °C. Analysis calculated for C₄₂H₄₀Br₂Cu₂N₆P₂S₂ (%): C, 48.42; H, 3.87; N, 8.07; S, 6.16. Found (%): C, 48.62; H, 3.91; N, 7.75; S, 6.55.

6. Refinement

Crystal data collection and structure refinement details are summarized in Table 5. The hydrogen atoms attached to nitrogen atoms were located from the electron-density map and refined isotropically with distance restraints for complex (II). All hydrogen atoms bonded to carbon atoms were placed in calculated idealized positions and refined using a riding model with U_iso(H) = 1.2U_eq(C).

Table 5
Experimental details

	(I)	(II)
Crystal data
Chemical formula	[Cu₂(C₃H₅N₃S)₂Cl₂(C₁₈H₁₅P)₂]	[Cu₂(C₃H₅N₃S)₂Br₂(C₁₈H₁₅P)₂]
M_r	952.84	1041.76
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$
Temperature (K)	296	296
a, b, c (Å)	9.2083 (5), 9.5646 (5), 14.3564 (8)	9.2762 (5), 9.7772 (5), 14.3655 (8)
α, β, γ (°)	103.561 (1), 92.318 (1), 118.208 (1)	103.420 (1), 92.476 (1), 118.188 (1)
V (Å³)	1066.17 (10)	1099.12 (10)
Z	1	1
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	1.33	2.99
Crystal size (mm)	0.32 × 0.13 × 0.10	0.18 × 0.13 × 0.10

Data collection
Diffractometer	Bruker APEX CCD area-detector	Bruker APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )	Multi-scan (SADABS; Krause et al., 2015)
T_min, T_max	0.860, 1.000	0.726, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15046, 5278, 4507	30282, 5290, 4690
R_int	0.021	0.026
(sin θ/λ)_max (Å⁻¹)	0.667	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.083, 1.03	0.031, 0.076, 1.05
No. of reflections	5278	5290
No. of parameters	258	258
No. of restraints	0	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.50	0.74, −0.53
Computer programs: SMART and SAINT (Bruker, 2003 ), SHELXT2018/3 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ), WinGX (Farrugia, 2012 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2575198; 2575197

Crystal structure: contains datablocks I, II, global. DOI: https://doi.org/10.1107/S2056989026007516/hb8238sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989026007516/hb8238Isup6.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989026007516/hb8238IIsup7.hkl

checkCIF report

Computing details top

Bis(µ-4-methyl-1H-1,2,4-triazole-5-thiolato)bis[chlorido(triphenylphosphane)copper(II)] (I) top

Crystal data top

[Cu₂(C₃H₅N₃S)₂Cl₂(C₁₈H₁₅P)₂]	Z = 1
M_r = 952.84	F(000) = 488
Triclinic, P1	D_x = 1.484 Mg m⁻³
a = 9.2083 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.5646 (5) Å	Cell parameters from 5142 reflections
c = 14.3564 (8) Å	θ = 2.5–28.1°
α = 103.561 (1)°	µ = 1.33 mm⁻¹
β = 92.318 (1)°	T = 296 K
γ = 118.208 (1)°	Block, colourless
V = 1066.17 (10) Å³	0.32 × 0.13 × 0.10 mm

Data collection top

Bruker APEX CCD area-detector diffractometer	4507 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Frames, each covering 0.3 ° in ω scans	θ_max = 28.3°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −12→12
T_min = 0.860, T_max = 1.000	k = −12→12
15046 measured reflections	l = −19→19
5278 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0419P)² + 0.3004P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
5278 reflections	Δρ_max = 0.66 e Å⁻³
258 parameters	Δρ_min = −0.50 e Å⁻³

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
Cu1	0.45470 (3)	0.36495 (3)	0.41651 (2)	0.03899 (8)
Cl1	0.45147 (6)	0.14000 (5)	0.45015 (4)	0.03800 (11)
S1	0.25331 (5)	0.41894 (6)	0.48179 (3)	0.03421 (11)
P1	0.46539 (6)	0.36199 (6)	0.26103 (3)	0.03079 (11)
N1	0.2033 (2)	0.1872 (2)	0.57685 (13)	0.0382 (4)
N2	0.0905 (2)	0.0875 (2)	0.62506 (13)	0.0457 (4)
N3	0.00374 (18)	0.23889 (19)	0.57215 (11)	0.0356 (3)
C1	0.1536 (2)	0.2784 (2)	0.54386 (12)	0.0302 (3)
C2	−0.0271 (2)	0.1241 (3)	0.62062 (15)	0.0434 (5)
H2	−0.122763	0.076982	0.647673	0.052*
C3	−0.1077 (3)	0.2990 (3)	0.54849 (19)	0.0525 (5)
H3A	−0.116480	0.293619	0.480730	0.079*
H3B	−0.063635	0.411647	0.587164	0.079*
H3C	−0.216549	0.231376	0.561966	0.079*
C4	0.6647 (2)	0.3853 (2)	0.23112 (13)	0.0361 (4)
C5	0.7146 (3)	0.2824 (3)	0.25912 (16)	0.0495 (5)
H5	0.645492	0.204952	0.289060	0.059*
C6	0.8672 (3)	0.2953 (4)	0.24249 (19)	0.0618 (7)
H6	0.899317	0.225109	0.260256	0.074*
C7	0.9712 (3)	0.4120 (4)	0.19961 (19)	0.0636 (7)
H7	1.073705	0.420877	0.188839	0.076*
C8	0.9241 (3)	0.5143 (4)	0.17303 (19)	0.0639 (7)
H8	0.994978	0.592659	0.144147	0.077*
C9	0.7712 (3)	0.5029 (3)	0.18860 (16)	0.0480 (5)
H9	0.740429	0.573759	0.170576	0.058*
C10	0.4354 (2)	0.5133 (2)	0.21824 (13)	0.0323 (4)
C11	0.4370 (2)	0.6428 (2)	0.28772 (14)	0.0384 (4)
H11	0.449372	0.647418	0.353168	0.046*
C12	0.4203 (3)	0.7650 (3)	0.26076 (18)	0.0529 (5)
H12	0.425226	0.853073	0.308020	0.063*
C13	0.3965 (3)	0.7558 (3)	0.1645 (2)	0.0617 (6)
H13	0.385835	0.838188	0.146377	0.074*
C14	0.3881 (3)	0.6251 (3)	0.09386 (18)	0.0602 (6)
H14	0.368879	0.618120	0.028394	0.072*
C15	0.4082 (3)	0.5046 (3)	0.12038 (15)	0.0452 (5)
H15	0.403477	0.417266	0.072648	0.054*
C16	0.3106 (2)	0.1657 (2)	0.17376 (14)	0.0365 (4)
C17	0.3434 (3)	0.0950 (3)	0.08679 (16)	0.0493 (5)
H17	0.450010	0.145782	0.071450	0.059*
C18	0.2170 (4)	−0.0512 (3)	0.02293 (19)	0.0654 (7)
H18	0.238580	−0.097701	−0.035577	0.078*
C19	0.0606 (4)	−0.1272 (3)	0.0458 (2)	0.0728 (8)
H19	−0.023333	−0.225805	0.003076	0.087*
C20	0.0267 (3)	−0.0590 (3)	0.1313 (2)	0.0700 (8)
H20	−0.080403	−0.110475	0.145972	0.084*
C21	0.1520 (3)	0.0867 (3)	0.19603 (17)	0.0498 (5)
H21	0.129383	0.131575	0.254638	0.060*
H1	0.281 (3)	0.173 (3)	0.5592 (15)	0.036 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.05047 (15)	0.04642 (15)	0.03399 (13)	0.03140 (12)	0.01482 (10)	0.01793 (10)
Cl1	0.0379 (2)	0.0318 (2)	0.0493 (3)	0.02040 (18)	0.00945 (19)	0.01311 (19)
S1	0.0319 (2)	0.0366 (2)	0.0415 (2)	0.01964 (19)	0.01161 (18)	0.01718 (19)
P1	0.0334 (2)	0.0362 (2)	0.0282 (2)	0.02067 (19)	0.00782 (17)	0.01070 (18)
N1	0.0323 (8)	0.0397 (9)	0.0464 (9)	0.0176 (7)	0.0107 (7)	0.0190 (7)
N2	0.0398 (9)	0.0447 (9)	0.0520 (10)	0.0156 (8)	0.0108 (7)	0.0245 (8)
N3	0.0272 (7)	0.0374 (8)	0.0379 (8)	0.0128 (6)	0.0075 (6)	0.0102 (7)
C1	0.0260 (8)	0.0296 (8)	0.0308 (8)	0.0121 (7)	0.0041 (6)	0.0054 (7)
C2	0.0335 (9)	0.0443 (11)	0.0455 (11)	0.0117 (8)	0.0102 (8)	0.0173 (9)
C3	0.0368 (10)	0.0645 (14)	0.0697 (15)	0.0315 (10)	0.0179 (10)	0.0270 (12)
C4	0.0348 (9)	0.0443 (10)	0.0301 (9)	0.0224 (8)	0.0064 (7)	0.0060 (8)
C5	0.0496 (12)	0.0617 (13)	0.0524 (13)	0.0370 (11)	0.0152 (10)	0.0205 (11)
C6	0.0568 (14)	0.0818 (18)	0.0621 (15)	0.0508 (14)	0.0072 (12)	0.0111 (13)
C7	0.0372 (11)	0.0853 (19)	0.0593 (15)	0.0328 (12)	0.0087 (10)	−0.0001 (13)
C8	0.0414 (12)	0.0753 (17)	0.0663 (16)	0.0216 (12)	0.0220 (11)	0.0197 (13)
C9	0.0395 (10)	0.0522 (12)	0.0508 (12)	0.0212 (9)	0.0112 (9)	0.0152 (10)
C10	0.0310 (8)	0.0353 (9)	0.0325 (9)	0.0170 (7)	0.0063 (7)	0.0115 (7)
C11	0.0382 (9)	0.0381 (10)	0.0373 (10)	0.0195 (8)	0.0051 (8)	0.0071 (8)
C12	0.0592 (13)	0.0385 (11)	0.0649 (15)	0.0282 (10)	0.0130 (11)	0.0126 (10)
C13	0.0758 (16)	0.0567 (14)	0.0763 (17)	0.0430 (13)	0.0196 (13)	0.0364 (13)
C14	0.0803 (17)	0.0720 (16)	0.0493 (13)	0.0468 (14)	0.0155 (12)	0.0331 (12)
C15	0.0609 (13)	0.0520 (12)	0.0347 (10)	0.0355 (11)	0.0128 (9)	0.0156 (9)
C16	0.0417 (10)	0.0325 (9)	0.0378 (10)	0.0198 (8)	0.0023 (8)	0.0120 (8)
C17	0.0579 (13)	0.0468 (12)	0.0435 (11)	0.0282 (10)	0.0053 (10)	0.0090 (9)
C18	0.0844 (19)	0.0522 (14)	0.0479 (13)	0.0341 (14)	−0.0100 (13)	−0.0024 (11)
C19	0.0754 (18)	0.0426 (13)	0.0695 (18)	0.0128 (13)	−0.0243 (15)	0.0055 (12)
C20	0.0493 (14)	0.0553 (15)	0.085 (2)	0.0073 (12)	−0.0041 (13)	0.0297 (15)
C21	0.0443 (11)	0.0475 (12)	0.0548 (13)	0.0187 (10)	0.0059 (9)	0.0194 (10)

Geometric parameters (Å, º) top

Cu1—P1	2.2324 (5)	C7—H7	0.9300
Cu1—Cl1	2.3002 (5)	C8—C9	1.392 (3)
Cu1—S1	2.3245 (5)	C8—H8	0.9300
Cu1—S1ⁱ	2.5781 (5)	C9—H9	0.9300
Cu1—Cu1ⁱ	2.8308 (5)	C10—C11	1.390 (3)
S1—C1	1.7042 (18)	C10—C15	1.393 (3)
P1—C4	1.8236 (18)	C11—C12	1.385 (3)
P1—C10	1.8249 (18)	C11—H11	0.9300
P1—C16	1.8299 (19)	C12—C13	1.366 (4)
N1—C1	1.323 (2)	C12—H12	0.9300
N1—N2	1.378 (2)	C13—C14	1.380 (4)
N1—H1	0.83 (2)	C13—H13	0.9300
N2—C2	1.289 (3)	C14—C15	1.381 (3)
N3—C1	1.355 (2)	C14—H14	0.9300
N3—C2	1.360 (3)	C15—H15	0.9300
N3—C3	1.456 (3)	C16—C21	1.383 (3)
C2—H2	0.9300	C16—C17	1.391 (3)
C3—H3A	0.9600	C17—C18	1.388 (3)
C3—H3B	0.9600	C17—H17	0.9300
C3—H3C	0.9600	C18—C19	1.368 (4)
C4—C9	1.388 (3)	C18—H18	0.9300
C4—C5	1.392 (3)	C19—C20	1.370 (4)
C5—C6	1.387 (3)	C19—H19	0.9300
C5—H5	0.9300	C20—C21	1.387 (3)
C6—C7	1.379 (4)	C20—H20	0.9300
C6—H6	0.9300	C21—H21	0.9300
C7—C8	1.361 (4)

P1—Cu1—Cl1	113.502 (19)	C5—C6—H6	120.0
P1—Cu1—S1	115.482 (18)	C8—C7—C6	120.2 (2)
Cl1—Cu1—S1	112.318 (18)	C8—C7—H7	119.9
P1—Cu1—S1ⁱ	108.064 (18)	C6—C7—H7	119.9
Cl1—Cu1—S1ⁱ	95.874 (17)	C7—C8—C9	120.7 (2)
S1—Cu1—S1ⁱ	109.682 (15)	C7—C8—H8	119.6
P1—Cu1—Cu1ⁱ	129.471 (18)	C9—C8—H8	119.6
Cl1—Cu1—Cu1ⁱ	113.892 (17)	C4—C9—C8	119.8 (2)
S1—Cu1—Cu1ⁱ	59.042 (14)	C4—C9—H9	120.1
S1ⁱ—Cu1—Cu1ⁱ	50.639 (13)	C8—C9—H9	120.1
C1—S1—Cu1	107.31 (6)	C11—C10—C15	118.44 (17)
C1—S1—Cu1ⁱ	107.96 (6)	C11—C10—P1	117.70 (14)
Cu1—S1—Cu1ⁱ	70.318 (15)	C15—C10—P1	123.84 (15)
C4—P1—C10	106.20 (8)	C12—C11—C10	120.85 (19)
C4—P1—C16	103.39 (9)	C12—C11—H11	119.6
C10—P1—C16	102.43 (8)	C10—C11—H11	119.6
C4—P1—Cu1	110.54 (6)	C13—C12—C11	119.8 (2)
C10—P1—Cu1	118.81 (6)	C13—C12—H12	120.1
C16—P1—Cu1	114.02 (6)	C11—C12—H12	120.1
C1—N1—N2	113.14 (16)	C12—C13—C14	120.5 (2)
C1—N1—H1	123.6 (15)	C12—C13—H13	119.8
N2—N1—H1	121.7 (15)	C14—C13—H13	119.8
C2—N2—N1	102.62 (16)	C13—C14—C15	120.0 (2)
C1—N3—C2	106.78 (16)	C13—C14—H14	120.0
C1—N3—C3	126.20 (17)	C15—C14—H14	120.0
C2—N3—C3	126.87 (17)	C14—C15—C10	120.4 (2)
N1—C1—N3	104.63 (15)	C14—C15—H15	119.8
N1—C1—S1	129.03 (13)	C10—C15—H15	119.8
N3—C1—S1	126.33 (14)	C21—C16—C17	119.12 (19)
N2—C2—N3	112.83 (17)	C21—C16—P1	117.20 (16)
N2—C2—H2	123.6	C17—C16—P1	123.66 (16)
N3—C2—H2	123.6	C18—C17—C16	120.0 (2)
N3—C3—H3A	109.5	C18—C17—H17	120.0
N3—C3—H3B	109.5	C16—C17—H17	120.0
H3A—C3—H3B	109.5	C19—C18—C17	120.1 (3)
N3—C3—H3C	109.5	C19—C18—H18	119.9
H3A—C3—H3C	109.5	C17—C18—H18	119.9
H3B—C3—H3C	109.5	C18—C19—C20	120.5 (2)
C9—C4—C5	119.14 (18)	C18—C19—H19	119.8
C9—C4—P1	124.71 (16)	C20—C19—H19	119.8
C5—C4—P1	116.03 (15)	C19—C20—C21	120.0 (3)
C6—C5—C4	120.2 (2)	C19—C20—H20	120.0
C6—C5—H5	119.9	C21—C20—H20	120.0
C4—C5—H5	119.9	C16—C21—C20	120.3 (2)
C7—C6—C5	120.0 (2)	C16—C21—H21	119.9
C7—C6—H6	120.0	C20—C21—H21	119.9

C1—N1—N2—C2	−0.7 (2)	C4—P1—C10—C11	−113.94 (15)
N2—N1—C1—N3	0.6 (2)	C16—P1—C10—C11	137.94 (15)
N2—N1—C1—S1	179.34 (14)	Cu1—P1—C10—C11	11.29 (16)
C2—N3—C1—N1	−0.3 (2)	C4—P1—C10—C15	67.28 (18)
C3—N3—C1—N1	−176.07 (18)	C16—P1—C10—C15	−40.84 (18)
C2—N3—C1—S1	−179.03 (14)	Cu1—P1—C10—C15	−167.50 (14)
C3—N3—C1—S1	5.2 (3)	C15—C10—C11—C12	−3.2 (3)
Cu1—S1—C1—N1	18.99 (18)	P1—C10—C11—C12	177.95 (16)
Cu1ⁱ—S1—C1—N1	−55.36 (18)	C10—C11—C12—C13	2.2 (3)
Cu1—S1—C1—N3	−162.55 (14)	C11—C12—C13—C14	0.3 (4)
Cu1ⁱ—S1—C1—N3	123.10 (15)	C12—C13—C14—C15	−1.7 (4)
N1—N2—C2—N3	0.5 (2)	C13—C14—C15—C10	0.6 (4)
C1—N3—C2—N2	−0.2 (2)	C11—C10—C15—C14	1.8 (3)
C3—N3—C2—N2	175.6 (2)	P1—C10—C15—C14	−179.41 (18)
C10—P1—C4—C9	2.9 (2)	C4—P1—C16—C21	160.08 (15)
C16—P1—C4—C9	110.31 (18)	C10—P1—C16—C21	−89.67 (16)
Cu1—P1—C4—C9	−127.27 (16)	Cu1—P1—C16—C21	40.01 (17)
C10—P1—C4—C5	178.92 (15)	C4—P1—C16—C17	−21.18 (19)
C16—P1—C4—C5	−73.65 (16)	C10—P1—C16—C17	89.07 (18)
Cu1—P1—C4—C5	48.78 (17)	Cu1—P1—C16—C17	−141.25 (15)
C9—C4—C5—C6	−1.5 (3)	C21—C16—C17—C18	1.1 (3)
P1—C4—C5—C6	−177.77 (18)	P1—C16—C17—C18	−177.57 (17)
C4—C5—C6—C7	1.1 (4)	C16—C17—C18—C19	−0.8 (4)
C5—C6—C7—C8	−0.4 (4)	C17—C18—C19—C20	0.7 (4)
C6—C7—C8—C9	0.0 (4)	C18—C19—C20—C21	−1.0 (4)
C5—C4—C9—C8	1.1 (3)	C17—C16—C21—C20	−1.4 (3)
P1—C4—C9—C8	177.08 (18)	P1—C16—C21—C20	177.38 (18)
C7—C8—C9—C4	−0.4 (4)	C19—C20—C21—C16	1.3 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg4 is the centroid of the C10–C15 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.83 (2)	2.33 (2)	3.1080 (18)	155.8 (19)
C2—H2···Cl1ⁱⁱ	0.93	2.79	3.439 (2)	128
C7—H7···Cg4ⁱⁱⁱ	0.93	2.81	3.626 (4)	147

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

Bis(µ-4-methyl-1H-1,2,4-triazole-5-thiolato)bis[bromido(triphenylphosphane)copper(II)] (II) top

Crystal data top

[Cu₂(C₃H₅N₃S)₂Br₂(C₁₈H₁₅P)₂]	Z = 1
M_r = 1041.76	F(000) = 524
Triclinic, P1	D_x = 1.574 Mg m⁻³
a = 9.2762 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7772 (5) Å	Cell parameters from 4760 reflections
c = 14.3655 (8) Å	θ = 2.5–27.0°
α = 103.420 (1)°	µ = 2.99 mm⁻¹
β = 92.476 (1)°	T = 296 K
γ = 118.188 (1)°	Block, colourless
V = 1099.12 (10) Å³	0.18 × 0.13 × 0.10 mm

Data collection top

Bruker APEX CCD area-detector diffractometer	4690 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
Frames, each covering 0.3 ° in ω scans	θ_max = 28.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −12→12
T_min = 0.726, T_max = 1.000	k = −12→12
30282 measured reflections	l = −18→18
5290 independent reflections

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.076	w = 1/[σ²(F_o²) + (0.0332P)² + 0.7926P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
5290 reflections	Δρ_max = 0.74 e Å⁻³
258 parameters	Δρ_min = −0.53 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Cu1	0.45873 (4)	0.37211 (4)	0.41591 (2)	0.04068 (8)
Br1	0.45899 (3)	0.13662 (3)	0.44388 (2)	0.04157 (7)
S1	0.25583 (7)	0.41875 (7)	0.48190 (4)	0.03694 (12)
P1	0.46591 (7)	0.36575 (7)	0.25953 (4)	0.03364 (12)
N1	0.2049 (3)	0.1890 (3)	0.57543 (16)	0.0434 (4)
N2	0.0933 (3)	0.0923 (3)	0.62374 (17)	0.0522 (5)
N3	0.0100 (2)	0.2438 (2)	0.57337 (14)	0.0402 (4)
C1	0.1576 (3)	0.2809 (3)	0.54395 (15)	0.0341 (4)
C2	−0.0215 (3)	0.1307 (3)	0.62101 (19)	0.0493 (6)
H2	−0.115806	0.085686	0.648695	0.059*
C3	−0.0971 (3)	0.3089 (4)	0.5529 (3)	0.0620 (8)
H3A	−0.121376	0.290030	0.484005	0.093*
H3B	−0.041336	0.423162	0.584681	0.093*
H3C	−0.198766	0.256126	0.576615	0.093*
C4	0.6634 (3)	0.3905 (3)	0.22766 (16)	0.0400 (5)
C5	0.7133 (4)	0.2863 (4)	0.2506 (2)	0.0561 (7)
H5	0.644763	0.206714	0.278193	0.067*
C6	0.8648 (4)	0.3010 (5)	0.2323 (2)	0.0672 (8)
H6	0.896827	0.230381	0.246886	0.081*
C7	0.9675 (4)	0.4193 (4)	0.1929 (2)	0.0677 (9)
H7	1.068841	0.428532	0.180602	0.081*
C8	0.9216 (4)	0.5236 (4)	0.1716 (2)	0.0673 (8)
H8	0.992237	0.604263	0.145300	0.081*
C9	0.7694 (3)	0.5098 (4)	0.1890 (2)	0.0521 (6)
H9	0.739135	0.581630	0.174412	0.063*
C10	0.4330 (3)	0.5114 (3)	0.21502 (16)	0.0354 (4)
C11	0.4350 (3)	0.6386 (3)	0.28340 (18)	0.0433 (5)
H11	0.449233	0.644998	0.349061	0.052*
C12	0.4162 (4)	0.7560 (3)	0.2553 (2)	0.0582 (7)
H12	0.420455	0.842247	0.301857	0.070*
C13	0.3910 (4)	0.7446 (4)	0.1582 (3)	0.0671 (8)
H13	0.380165	0.824414	0.139116	0.081*
C14	0.3819 (4)	0.6159 (4)	0.0892 (2)	0.0627 (8)
H14	0.361021	0.607044	0.023583	0.075*
C15	0.4034 (3)	0.4995 (3)	0.11675 (18)	0.0483 (6)
H15	0.398143	0.413249	0.069674	0.058*
C16	0.3119 (3)	0.1715 (3)	0.17498 (17)	0.0413 (5)
C17	0.3427 (4)	0.1003 (3)	0.0884 (2)	0.0558 (7)
H17	0.447284	0.150032	0.071603	0.067*
C18	0.2163 (5)	−0.0456 (4)	0.0269 (2)	0.0741 (10)
H18	0.236950	−0.093564	−0.031009	0.089*
C19	0.0623 (5)	−0.1189 (4)	0.0509 (3)	0.0820 (12)
H19	−0.021660	−0.216111	0.009202	0.098*
C20	0.0310 (4)	−0.0497 (4)	0.1361 (3)	0.0764 (10)
H20	−0.074323	−0.099934	0.151897	0.092*
C21	0.1551 (3)	0.0944 (3)	0.1989 (2)	0.0554 (7)
H21	0.133495	0.139842	0.257166	0.066*
H1	0.286 (3)	0.175 (3)	0.5569 (18)	0.037 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.05287 (17)	0.04652 (17)	0.03529 (15)	0.03174 (14)	0.01301 (12)	0.01691 (12)
Br1	0.04191 (13)	0.03418 (12)	0.05408 (15)	0.02244 (10)	0.00859 (10)	0.01417 (10)
S1	0.0346 (3)	0.0394 (3)	0.0437 (3)	0.0212 (2)	0.0104 (2)	0.0169 (2)
P1	0.0375 (3)	0.0385 (3)	0.0303 (3)	0.0227 (2)	0.0072 (2)	0.0104 (2)
N1	0.0371 (10)	0.0468 (11)	0.0527 (12)	0.0216 (9)	0.0123 (9)	0.0227 (9)
N2	0.0451 (12)	0.0494 (12)	0.0591 (14)	0.0152 (10)	0.0111 (10)	0.0286 (11)
N3	0.0293 (9)	0.0435 (11)	0.0423 (11)	0.0145 (8)	0.0060 (8)	0.0111 (9)
C1	0.0285 (10)	0.0330 (10)	0.0334 (10)	0.0122 (8)	0.0018 (8)	0.0044 (8)
C2	0.0385 (12)	0.0504 (14)	0.0489 (14)	0.0121 (11)	0.0105 (10)	0.0189 (11)
C3	0.0409 (14)	0.079 (2)	0.080 (2)	0.0362 (14)	0.0187 (13)	0.0302 (17)
C4	0.0390 (11)	0.0494 (13)	0.0331 (11)	0.0253 (10)	0.0056 (9)	0.0071 (9)
C5	0.0578 (16)	0.0678 (18)	0.0611 (17)	0.0426 (15)	0.0184 (13)	0.0233 (14)
C6	0.0623 (18)	0.087 (2)	0.0688 (19)	0.0545 (18)	0.0097 (15)	0.0131 (17)
C7	0.0437 (15)	0.090 (2)	0.0646 (19)	0.0369 (16)	0.0111 (13)	0.0050 (17)
C8	0.0423 (15)	0.078 (2)	0.073 (2)	0.0240 (15)	0.0171 (14)	0.0202 (17)
C9	0.0436 (13)	0.0591 (16)	0.0534 (15)	0.0249 (12)	0.0120 (11)	0.0163 (13)
C10	0.0365 (11)	0.0407 (11)	0.0340 (11)	0.0222 (9)	0.0074 (8)	0.0122 (9)
C11	0.0459 (13)	0.0401 (12)	0.0417 (12)	0.0220 (11)	0.0035 (10)	0.0072 (10)
C12	0.0668 (18)	0.0435 (14)	0.0700 (19)	0.0337 (14)	0.0132 (14)	0.0118 (13)
C13	0.081 (2)	0.0636 (18)	0.082 (2)	0.0475 (17)	0.0206 (17)	0.0384 (17)
C14	0.084 (2)	0.080 (2)	0.0483 (15)	0.0519 (18)	0.0178 (14)	0.0357 (15)
C15	0.0628 (16)	0.0581 (15)	0.0363 (12)	0.0380 (13)	0.0126 (11)	0.0161 (11)
C16	0.0472 (13)	0.0385 (12)	0.0398 (12)	0.0226 (10)	0.0000 (10)	0.0124 (9)
C17	0.0675 (18)	0.0514 (15)	0.0472 (14)	0.0327 (14)	0.0029 (13)	0.0057 (12)
C18	0.098 (3)	0.0552 (18)	0.0558 (18)	0.0387 (19)	−0.0143 (17)	−0.0039 (14)
C19	0.088 (3)	0.0470 (17)	0.080 (2)	0.0178 (18)	−0.031 (2)	0.0075 (17)
C20	0.0567 (18)	0.0612 (19)	0.088 (3)	0.0086 (15)	−0.0081 (17)	0.0306 (19)
C21	0.0486 (14)	0.0540 (16)	0.0600 (17)	0.0205 (13)	0.0048 (12)	0.0223 (13)

Geometric parameters (Å, º) top

Cu1—P1	2.2376 (6)	C7—H7	0.9300
Cu1—S1	2.3268 (6)	C8—C9	1.393 (4)
Cu1—Br1	2.4284 (4)	C8—H8	0.9300
Cu1—S1ⁱ	2.5501 (7)	C9—H9	0.9300
Cu1—Cu1ⁱ	2.8115 (6)	C10—C11	1.386 (3)
S1—C1	1.706 (2)	C10—C15	1.394 (3)
P1—C4	1.824 (2)	C11—C12	1.382 (4)
P1—C16	1.827 (2)	C11—H11	0.9300
P1—C10	1.829 (2)	C12—C13	1.374 (5)
N1—C1	1.323 (3)	C12—H12	0.9300
N1—N2	1.374 (3)	C13—C14	1.373 (5)
N1—H1	0.873 (16)	C13—H13	0.9300
N2—C2	1.287 (4)	C14—C15	1.381 (4)
N3—C1	1.355 (3)	C14—H14	0.9300
N3—C2	1.356 (3)	C15—H15	0.9300
N3—C3	1.461 (3)	C16—C21	1.389 (4)
C2—H2	0.9300	C16—C17	1.389 (4)
C3—H3A	0.9600	C17—C18	1.391 (4)
C3—H3B	0.9600	C17—H17	0.9300
C3—H3C	0.9600	C18—C19	1.366 (6)
C4—C9	1.379 (4)	C18—H18	0.9300
C4—C5	1.396 (4)	C19—C20	1.368 (6)
C5—C6	1.386 (4)	C19—H19	0.9300
C5—H5	0.9300	C20—C21	1.383 (4)
C6—C7	1.369 (5)	C20—H20	0.9300
C6—H6	0.9300	C21—H21	0.9300
C7—C8	1.363 (5)

P1—Cu1—S1	116.06 (2)	C5—C6—H6	119.9
P1—Cu1—Br1	110.271 (19)	C8—C7—C6	120.2 (3)
S1—Cu1—Br1	113.182 (18)	C8—C7—H7	119.9
P1—Cu1—S1ⁱ	109.40 (2)	C6—C7—H7	119.9
S1—Cu1—S1ⁱ	109.762 (19)	C7—C8—C9	120.3 (3)
Br1—Cu1—S1ⁱ	96.366 (17)	C7—C8—H8	119.9
P1—Cu1—Cu1ⁱ	131.67 (2)	C9—C8—H8	119.9
S1—Cu1—Cu1ⁱ	58.606 (18)	C4—C9—C8	120.5 (3)
Br1—Cu1—Cu1ⁱ	115.238 (16)	C4—C9—H9	119.8
S1ⁱ—Cu1—Cu1ⁱ	51.156 (16)	C8—C9—H9	119.8
C1—S1—Cu1	108.45 (8)	C11—C10—C15	118.7 (2)
C1—S1—Cu1ⁱ	107.43 (7)	C11—C10—P1	117.67 (17)
Cu1—S1—Cu1ⁱ	70.238 (19)	C15—C10—P1	123.67 (18)
C4—P1—C16	103.53 (11)	C12—C11—C10	120.9 (2)
C4—P1—C10	105.42 (11)	C12—C11—H11	119.6
C16—P1—C10	102.79 (10)	C10—C11—H11	119.6
C4—P1—Cu1	111.26 (8)	C13—C12—C11	119.7 (3)
C16—P1—Cu1	113.44 (8)	C13—C12—H12	120.1
C10—P1—Cu1	118.92 (7)	C11—C12—H12	120.1
C1—N1—N2	113.2 (2)	C14—C13—C12	120.2 (3)
C1—N1—H1	123.6 (17)	C14—C13—H13	119.9
N2—N1—H1	121.9 (17)	C12—C13—H13	119.9
C2—N2—N1	102.7 (2)	C13—C14—C15	120.4 (3)
C1—N3—C2	107.0 (2)	C13—C14—H14	119.8
C1—N3—C3	125.8 (2)	C15—C14—H14	119.8
C2—N3—C3	127.1 (2)	C14—C15—C10	120.0 (2)
N1—C1—N3	104.35 (19)	C14—C15—H15	120.0
N1—C1—S1	129.51 (17)	C10—C15—H15	120.0
N3—C1—S1	126.13 (17)	C21—C16—C17	119.1 (3)
N2—C2—N3	112.7 (2)	C21—C16—P1	117.3 (2)
N2—C2—H2	123.6	C17—C16—P1	123.6 (2)
N3—C2—H2	123.6	C16—C17—C18	119.7 (3)
N3—C3—H3A	109.5	C16—C17—H17	120.1
N3—C3—H3B	109.5	C18—C17—H17	120.1
H3A—C3—H3B	109.5	C19—C18—C17	120.4 (3)
N3—C3—H3C	109.5	C19—C18—H18	119.8
H3A—C3—H3C	109.5	C17—C18—H18	119.8
H3B—C3—H3C	109.5	C18—C19—C20	120.2 (3)
C9—C4—C5	118.6 (2)	C18—C19—H19	119.9
C9—C4—P1	124.8 (2)	C20—C19—H19	119.9
C5—C4—P1	116.5 (2)	C19—C20—C21	120.4 (3)
C6—C5—C4	120.2 (3)	C19—C20—H20	119.8
C6—C5—H5	119.9	C21—C20—H20	119.8
C4—C5—H5	119.9	C20—C21—C16	120.1 (3)
C7—C6—C5	120.2 (3)	C20—C21—H21	119.9
C7—C6—H6	119.9	C16—C21—H21	119.9

C1—N1—N2—C2	−0.6 (3)	C4—P1—C10—C11	−114.09 (19)
N2—N1—C1—N3	0.4 (3)	C16—P1—C10—C11	137.76 (19)
N2—N1—C1—S1	179.53 (18)	Cu1—P1—C10—C11	11.5 (2)
C2—N3—C1—N1	0.0 (2)	C4—P1—C10—C15	67.1 (2)
C3—N3—C1—N1	−177.4 (2)	C16—P1—C10—C15	−41.1 (2)
C2—N3—C1—S1	−179.18 (18)	Cu1—P1—C10—C15	−167.33 (18)
C3—N3—C1—S1	3.5 (3)	C15—C10—C11—C12	−3.1 (4)
Cu1—S1—C1—N1	17.2 (2)	P1—C10—C11—C12	178.0 (2)
Cu1ⁱ—S1—C1—N1	−57.3 (2)	C10—C11—C12—C13	1.6 (4)
Cu1—S1—C1—N3	−163.92 (17)	C11—C12—C13—C14	1.1 (5)
Cu1ⁱ—S1—C1—N3	121.68 (18)	C12—C13—C14—C15	−2.2 (5)
N1—N2—C2—N3	0.6 (3)	C13—C14—C15—C10	0.6 (5)
C1—N3—C2—N2	−0.4 (3)	C11—C10—C15—C14	2.0 (4)
C3—N3—C2—N2	176.9 (3)	P1—C10—C15—C14	−179.2 (2)
C16—P1—C4—C9	114.6 (2)	C4—P1—C16—C21	160.9 (2)
C10—P1—C4—C9	7.0 (2)	C10—P1—C16—C21	−89.5 (2)
Cu1—P1—C4—C9	−123.2 (2)	Cu1—P1—C16—C21	40.2 (2)
C16—P1—C4—C5	−69.7 (2)	C4—P1—C16—C17	−20.6 (2)
C10—P1—C4—C5	−177.3 (2)	C10—P1—C16—C17	89.0 (2)
Cu1—P1—C4—C5	52.5 (2)	Cu1—P1—C16—C17	−141.3 (2)
C9—C4—C5—C6	−1.6 (4)	C21—C16—C17—C18	0.5 (4)
P1—C4—C5—C6	−177.5 (2)	P1—C16—C17—C18	−178.0 (2)
C4—C5—C6—C7	0.9 (5)	C16—C17—C18—C19	0.2 (5)
C5—C6—C7—C8	0.2 (5)	C17—C18—C19—C20	−0.4 (5)
C6—C7—C8—C9	−0.5 (5)	C18—C19—C20—C21	−0.3 (5)
C5—C4—C9—C8	1.2 (4)	C19—C20—C21—C16	1.1 (5)
P1—C4—C9—C8	176.8 (2)	C17—C16—C21—C20	−1.2 (4)
C7—C8—C9—C4	−0.2 (5)	P1—C16—C21—C20	177.5 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg4 is the centroid of the C10–C15 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	0.87 (2)	2.42 (2)	3.235 (2)	156 (2)
C2—H2···Br1ⁱⁱ	0.93	2.90	3.563 (2)	130
C7—H7···Cg4ⁱⁱⁱ	0.93	2.81	3.638 (4)	149

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

Acknowledgements

Financial support by FF 68 (grant No. SCI6801309S) is gratefully acknowledged and this work was partially supported by the Faculty of Science, Prince of Songkla University (No. 364002). The authors would like to acknowledge MSc Scholarship No. PSU_GSS 2567–025) and the Medical Science Research and Innovation Institute for supporting SC-XRD data.

Funding information

Funding for this research was provided by: FF 68 (grant No. SCI6801309S); MSc (scholarship No. PSU_GSS 2567–025). This work was partially supported by the Faculty of Science, Prince of Songkla University (grant No. 364002).

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Isomorphous dinuclear copper(I) complexes bridged by 4-methyl-1H-1,2,4-triazole-5-thiol­ate ligands: chloride and bromide analogues

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

Funding information

References

research communications

Isomorphous dinuclear copper(I) complexes bridged by 4-methyl-1H-1,2,4-triazole-5-thiolate ligands: chloride and bromide analogues

3. Supramolecular features