Ligand-forced dimerization of copper(I)–olefin complexes bearing a 1,3,4-thia­diazole core

As an important class of heterocyclic compounds, 1,3,4-thia­diazo­les have a broad range of potential applications in medicine, agriculture and materials chemistry, and were found to be excellent precursors for the crystal engineering of organometallic materials. The coordinating behaviour of allyl derivatives of 1,3,4-thia­diazo­les with respect to transition metal ions has been little studied. Five new crystalline copper(I) π-complexes have been obtained by means of an alternating current electrochemical technique and have been characterized by single-crystal X-ray diffraction and IR spectroscopy. The compounds are bis­[μ-5-methyl-N-(prop-2-en-1-yl)-1,3,4-thia­diazol-2-amine]­bis­[nitratocopper(I)], [Cu₂(NO₃)₂(C₆H₉N₃S)₂], (1), bis­[μ-5-methyl-N-(prop-2-en-1-yl)-1,3,4-thia­diazol-2-amine]­bis­[(tetra­fluoro­borato)copper(I)], [Cu₂(BF₄)₂(C₆H₉N₃S)₂], (2), μ-aqua-bis­{μ-5-[(prop-2-en-1-yl)sulfan­yl]-1,3,4-thia­diazol-2-amine}­bis­[nitrato­copper(I)], [Cu₂(NO₃)₂(C₅H₇N₃S₂)₂(H₂O)], (3), μ-aqua-(hexa­fluoro­silicato)bis­{μ-5-[(prop-2-en-1-yl)sulfan­yl]-1,3,4-thia­diazol-2-amine}­di­copper(I)–aceto­nitrile–water (2/1/4), [Cu₂(SiF₆)(C₅H₇N₃S₂)₂(H₂O)]·0.5CH₃CN·2H₂O, (4), and μ-benzene­sulfonato-bis­{μ-5-[(prop-2-en-1-yl)sulfan­yl]-1,3,4-thia­diazol-2-amine}­dicopper(I) benzene­sulfonate–methanol–water (1/1/1), [Cu₂(C₆H₅O₃S)(C₅H₇N₃S₂)₂](C₆H₅O₃S)·CH₃OH·H₂O, (5). The structure of the ligand 5-methyl-N-(prop-2-en-1-yl)-1,3,4-thia­diazol-2-amine (Mepeta), C₆H₉N₃S, was also structurally characterized. Both Mepeta and 5-[(prop-2-en-1-yl)sulfan­yl]-1,3,4-thia­diazol-2-amine (Pesta) (denoted L) reveal a strong tendency to form dimeric {Cu₂L₂}²⁺ fragments, being attached to the metal atom in a chelating–bridging mode via two thia­diazole N atoms and an allylic C=C bond. Flexibility of the {Cu₂(Pesta)₂}²⁺ unit allows the Cu^I atom site to be split into two positions with different metal-coordination environments, thus enabling the competitive participation of different molecules in bonding to the metal centre. The Pesta ligand in (4) allows the Cu^I atom to vary between water O-atom and hexa­fluorosilicate F-atom coordination, resulting in the rare case of a direct Cu^I⋯FSiF₅²⁻ inter­action. Extensive three-dimensional hydrogen-bonding patterns are formed in the reported crystal structures. Complex (5) should be considered as the first known example of a Cu^I(C₆H₅SO₃) coordination com­pound. To determine the hydrogen-bond inter­actions in the structures of (1) and (2), a Hirshfeld surface analysis has been performed.

1. Introduction

As an important class of heterocyclic compounds, 1,3,4-thia­diazo­les have a broad range of potential applications in medicine as anti­bacterial, anti­oxidant, anti­depressant, anti­diabetic, anti­fungal, anti-inflammatory and anti­tumor agents (Khan et al., 2010; Cressier et al., 2009; Li et al., 2014; Moshafi et al., 2011; Pattn et al., 2011; Lee et al., 2010; Xu et al., 2013; Zhang et al., 2014). In agriculture, these compounds can be used as pesticides, insecticides and plant-growth-regulating agents (Gilden et al., 2010; Alves et al., 2012). They have applications in materials chemistry because of their inter­esting optical and electronic properties (Tao et al., 2010; Granadino-Roldán et al., 2011; He et al., 2010). Due to their electron-deficient nature and good electron-accepting ability, 1,3,4-thia­diazo­les were found to be excellent precursors for the crystal engineering of organometallic materials, possessing potential catalytic, luminescent, magnetic, nonlinear optic and other properties (Hu et al., 2014; Trukhina et al., 2010; Higashihara et al., 2012). Among these, heterometallic coordination polymers based on 1,3,4-thia­diazole-2,5-di­thiol­ates show optical transitions with gaps varying from 1.90 to 2.24 eV, indicating their semiconductor properties (Li et al., 2008). A three-dimensional supra­molecular network compound (via inter­layer π–π stacking inter­actions and strong hydrogen bonding), based on the cadmium complex with 2-amino-5-mercapto-1,3,4-thia­diazole, shows a blue photoluminescence in the solid state at room temperature (Zhang et al., 2007). The aromatic 1,3,4-thia­diazole ring allows good π-electron conjugation and the accompanying (in the case of amino or hy­droxy substituents) proton-transfer and charge-transfer processes provide an excellent ability to promote the synthesis of heavy-metal clusters. For example, the first known tetra­nuclear Cu^I complex (Cu⋯·Cu = 2.74 Å) of the aza­nide-type forms as a result of metal-induced deprotonation of 2-allyl­amino-5-phenyl-1,3,4-thia­diazole in aceto­nitrile under alternating current (ac) electrochemical conditions (Slyvka et al., 2015). Similarly, cobalt-induced reductive nucleo­philic addition of 2-amino-1,3,4-thia­diazole to aceto­nitrile also shows deprotonation of the same amine N atom, resulting in the N-(1,3,4-thia­diazol-2-yl)acetimidamide com­plex (Deng et al., 2008).

In recent years, specific attention have been paid to the investigation of copper(I) π-complexes with allyl derivatives of heterocyclic compounds, since the simultaneous presence of a heterocyclic core and an allylic radical bonded to them plays an important role in the formation of unusual inorganic fragments (Slyvka et al., 2013). The contribution from the π-dative (Cu→C=C) π-component of a Cu^I–olefin bond to the tetra­hedral ligand field leads to a splitting of the copper-ion d orbitals and brings about a considerable deformation of the initial tetra­hedral copper(I) environment to trigonal pyramidal. Such a distortion of the copper(I) polyhedron is accompanied by an elongation of the Cu—L_ap bond (ap is apical) compared to the Cu—(C=C) and Cu—L_bas bonds (where L_bas are heterocyclic donor N, O or S atoms). Therefore, the apical position of the Cu^I polyhedron becomes a selector of the coordinated inorganic anion, depending on the L_bas atom nature (i.e. the type of heterocyclic core), solvent type and other basal co-ligands. For instance, in the structure of the copper(I) hexa­fluoro­silicate π-complex with 1-allyl­benzotriazole, the first known example representing a direct Cu^I⋯FSiF₅²⁻ inter­action was observed {the apical position of the copper(I) polyhedron is occupied by an F atom of the bridging SiF₆²⁻ anion [Cu—F = 2.439 (2) Å], while the basal positions are occupied by an allylic C=C bond, a triazole N atom and a solvent water mol­ecule} (Goreshnik et al., 2011).

Taking into account the mutual presence of two neighbouring nucleophilic N atoms in the 1,3,4-thia­diazole ring and the electron-deficient nature of the core, the appearance of an allyl substituent on this ring should significantly influence its unusual coordination abilities. This assertion is confirmed by the recently studied structure of [Cu₂(Mepeta)₂]SiF₆·C₆H₆ [Mepeta is 5-methyl-N-(prop-2-en-1-yl)-1,3,4-thia­diazol-2-amine], in which a Cu^I⋯FSiF₅²⁻ inter­action was also observed. Despite the fact that allyl derivatives of 1,3,4-thia­diazo­les were first obtained more than a century ago (Pulvermacher, 1894), their coordinating behaviour with respect to transition metal ions has been little studied. Overall, only a few copper(I) (CuCl, CuCF₃SO₃ and Cu₂SiF₆) π-complexes with Mepeta and Phepeta [5-phenyl-N-(prop-2-en-1-yl)-1,3,4-thia­diazol-2-amine] have been synthesized and structurally characterized by X-ray diffraction and Raman spectroscopy (Ardan et al., 2013; Slyvka, 2015; Goreshnik et al., 2016), and these only recently.

To fill the knowledge gap mentioned above and to explore the coordination behaviour of other allyl derivatives of thia­diazo­les, such as Pesta, with respect to diverse copper(I) salts, we report the synthesis and structures of five new π-complexes, namely [Cu(NO₃)(Mepeta)]₂, (1), [Cu(BF₄)(Mepeta)]₂, (2), [Cu₂(NO₃)₂(Pesta)₂(H₂O)], (3), [Cu₂(SiF₆)(Pesta)₂(H₂O)]·0.5CH₃CN·2H₂O, (4), and [Cu₂(C₆H₅SO₃)(Pesta)₂](C₆H₅SO₃)·CH₃OH·H₂O, (5), highlighting the influence of the ligand coordination mode in the rare case of Cu^I⋯FSiF₅²⁻ coordination.

2. Experimental

2.1. General considerations

Unless mentioned otherwise, all chemicals were obtained from commercial sources and used without further purification. The ¹H NMR spectrum for Mepeta was measured on a Bruker Avance 400 MHz NMR spectrometer and the ¹H NMR spectrum of Pesta was measured on a Bruker Avance 500 MHz NMR instrument. The chemical shifts are reported in ppm relative to the residual peak of deuterated CDCl₃ or CD₃CN for the ¹H data. The IR spectra were recorded on Bruker Vertex 70 FT–IR and Bruker IFS-88 spectrometers as KBr pellets. Diffraction data for Mepeta were collected on a Kuma KM-4-CCD diffractometer with Mo Kα radiation (λ = 0.71073 Å).

2.2. Preparation of the ligands Mepeta and Pesta

5-Methyl-N-(prop-2-en-1-yl)-1,3,4-thia­diazol-2-amine (Mepeta) was prepared according to the literature procedure of Ardan et al. (2013) (see Scheme 1). Recrystallization of Mepeta from water leads to lamellar crystals suitable for single-crystal X-ray study. The total yield was 63%. ¹H NMR (400 MHz, CDCl₃): δ 6.36 (s, 1H), 5.97–5.87 (m, 1H), 5.32 (d, J = 17.2 Hz, 1H), 5.22 (d, J = 10.4 Hz, 1H), 3.94 (d, J = 5.6 Hz, 2H), 2.57 (s, 3H). IR (KBr, cm⁻¹): 3179 (vs), 3076 (m), 2978 (vs), 2915 (s), 2855 (m), 2768 (m), 2357 (m), 2334 (w), 1643 (m), 1566 (vs), 1491 (vs), 1456 (s), 1435 (m), 1417 (s), 1336 (m), 1267 (m), 1214 (s), 1187 (m), 1145 (w), 1084 (m), 1008 (w), 992 (m), 960 (m), 925 (s), 814 (w), 756 (m), 650 (m), 617 (w), 522 (w).

5-Amino-1,3,4-thia­diazole-2-thiol (Att) was prepared according to the literature procedure of Guha (1922) (see Scheme 2). 5-[(Prop-2-en-1-yl)sulfan­yl]-1,3,4-thia­diazol-2-am­ine (Pesta) was synthesized in one step by stirring Att (20 mmol, 3.46 g) with 3-chloro­prop-1-ene (23 mmol, 1.76 g) at 343 K in the presence of KOH (20 mmol, 1.12 g) in an ethanol solution for 8 h. The total yield was 92%. ¹H NMR (500 MHz, CD₃CN): δ 5.93 (ddt, J = 17.1, 10.0, 7.0 Hz, 1H), 5.80 (s, 2H), 5.21 (dq, J = 17.0, 1.4 Hz, 1H), 5.12 (ddt, J = 10.0, 1.6, 0.9 Hz, 1H), 3.72–3.65 (m, 2H). IR (KBr, cm⁻¹): 3279 (vs), 3093 (vs), 2959 (vs), 2923 (vs), 2785 (m), 2686 (m), 2337 (w), 1845 (w), 1643 (s), 1518 (vs), 1464 (s), 1424 (s), 1398 (m), 1376 (m), 1329 (m), 1233 (m), 1198 (w), 1141 (m), 1098 (m), 1062 (s), 1050 (s), 987 (s), 922 (vs), 867 (m), 779 (w), 729 (m), 686 (m), 617 (m), 580 (m), 545 (w).

2.3. Syntheses of complexes (1)–(5)

Crystals of complexes (1)–(5) were obtained under alternating current electrochemical synthesis conditions (Mykhalichko & Mys'kiv, 1998), starting with a water–aceto­nitrile or methanol–toluene solution of Mepeta or Pesta and the corresponding copper(II) salt.

2.3.1. Preparation of [Cu(NO₃)(Mepeta)]₂, (1)

To an ethanol solution (2 ml) of Mepeta (1.1 mmol, 0.17 g), an ethanol solution (2.5 ml) of Cu(NO₃)₂·3H₂O (1.0 mmol, 0.24 g) was added. The resulting dark-green solution was placed in a small 5 ml test tube and a cork was added fitted with copper-wire electrodes. An alternating current (fre­quency 50 Hz) of 0.45 V was applied for 7 d, during which time good-quality colourless crystals of (1) appeared on the electrodes. IR (nujol, cm⁻¹): 3450 (m), 3215 (m), 2996 (m), 2392 (w), 1576 (m), 1509 (w), 1384 (vs), 1220 (m), 1043 (w), 976 (w), 942 (w), 898 (w), 826 (w), 785 (w), 717 (w), 676 (w), 620 (w), 544 (w), 514 (w).

2.3.2. Preparation of [Cu(BF₄)(Mepeta)]₂, (2)

To an ethanol solution (2 ml) of Mepeta (1.1 mmol, 0.17 g), an ethanol solution (2.5 ml) of Cu(BF₄)₂·6H₂O (1.0 mmol, 0.26 g) was added. The resulting dark-green solution was subjected to an alternating current (frequency 50 Hz) at 0.42 V and, after 1 d, good-quality colourless crystals of (2) appeared on the copper-wire electrodes. IR (KBr, cm⁻¹): 3338 (s), 3094 (w), 3036 (m), 2926 (w), 2367 (m), 2337 (m), 1565 (vs), 1522 (s), 1503 (s), 1445 (s), 1420 (m), 1387 (m), 1333 (s), 1284 (s), 1262 (m), 1246 (w), 1224 (s), 1068 (vs), 1012 (vs), 978 (vs), 946 (s), 903 (m), 786 (m), 703 (w), 683 (w), 599 (w), 546 (m), 519 (m).

2.3.3. Preparation of [Cu₂(NO₃)₂(Pesta)₂(H₂O)], (3)

Pesta (1.0 mmol, 0.17 g) was dissolved in an aceto­nitrile solution (4.5 ml) of Cu(NO₃)₂·3H₂O (1.0 mmol, 0.24 g). An alternating current (frequency 50 Hz) of 0.50 V was applied for 5 d, during which time good-quality colourless crystals of (3) appeared on the copper-wire electrodes. IR (KBr, cm⁻¹): 2955 (vs), 2922 (vs), 2852 (vs), 1463 (s), 1377 (s), 1342 (m), 1153 (w), 1044 (w), 723 (m), 511 (w).

2.3.4. Preparation of [Cu₂(SiF₆)(Pesta)₂(H₂O)]·0.5CH₃CN·2H₂O, (4)

A solution of Pesta (1.0 mmol, 0.17 g) in aceto­nitrile (3.8 ml) was added to a saturated water solution (0.9 ml) of CuSiF₆·4H₂O (in a 5 ml test tube). The mixture was stirred carefully. The resulting mixture consisted of an upper dark layer (aceto­nitrile) and a lower light-green layer (water). It was subjected to alternating current reduction (frequency 50 Hz, 0.5 V) (the aceto­nitrile layer became fully colourless and, after 4–5 d, only a few good-quality colourless crystals of (4) had appeared on the copper-wire electrodes.

2.3.5. Preparation of [Cu₂(C₆H₅SO₃)(Pesta)₂](C₆H₅SO₃)·CH₃OH·H₂O, (5)

A solution of Pesta (1.0 mmol, 0.17 g) and Cu(C₆H₅SO₃)₂·6H₂O was prepared in a mixture of methanol (2.3 ml) and toluene (2.2 ml). The resulting green-coloured solution was subjected to alternating current (frequency 50 Hz, 0.45 V). After 1 d the solution became colourless and good-quality colourless crystals of (5) appeared on the copper electrodes. IR (KBr, cm⁻¹): 3498 (m), 3279 (s), 3122 (s), 2956 (vs), 2922 (vs), 2854 (vs), 1626 (s), 1540 (s), 1456 (vs), 1374 (s), 1346 (w), 1247 (w), 1220 (s), 1172 (vs), 1122 (vs), 1065 (m), 1035 (s), 1015 (s), 993 (m), 932 (w), 882 (vw), 753 (m), 727 (s), 692 (m), 609 (s), 563 (m).

2.4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The Mepeta structure was refined as a racemic twin with a ratio of the components of 0.73 (11):0.27 (11). The amine H atom in Mepeta itself and the ligand amine H atoms in complexes (1)–(5) were derived from difference Fourier maps and refined with U_iso(H) = 1.2U_eq(N). The water H atoms in (3)–(5) were derived from difference Fourier maps and refined with U_iso(H) = 1.5U_eq(O). The other H atoms were refined in ideal positions (riding model), with C—H = 0.99 (methyl and methyl­ene) or 0.95 Å (otherwise) and U_iso(H) = 1.5U_eq(C) for methyl H atoms or 1.2U_eq(C) otherwise. Some of the reflections, for which a considerable difference between the observed and calculated intensities were observed, were omitted from the final refinement cycles [4, 5, 1 and 3 reflections for (1)–(3) and (5), respectively]. In the Mepeta structure, the allyl group (atoms C7, C8 and C9) is disordered over two sites, with an occupancy ratio of 0.660 (6):0.340 (6). In (3), the allyl­sulfanyl group (atoms S12, C17, C18 and C19), together with Cu1, as well as the allyl group (atoms C27, C28 and C29), together with Cu2, are disordered over two sites, with occupancy ratios of 0.765 (6):0.235 (6) and 0.794 (7):0.206 (7), respectively. In (4), the allyl group (atoms C17, C18 and C19) is disordered over two sites, with an occupancy ratio of 0.616 (8):0.384 (8); the allyl group (atoms C27, C28 and C29), together with Cu2, is disordered over two sites, with a fixed occupancy ratio of 0.88:0.12 and the hexa­fluoro­silicate F atoms (F3, F4, F5 and F6) are disordered over four sites, with an occupancy ratio of 0.426 (3):0.287 (3):0.172 (3):0.115 (3). In (4), the chemically equivalent bond lengths and angles involving the disordered C27, C28 and C29 atoms (as well as the disordered F3, F4, F5 and F6 atoms) were restrained to obtain similar geometries. In (5), two allyl groups (atoms C17/C18/C19 and C27/C28/C29) are disordered over two sites, with occupancy ratios of 0.80 (1):0.20 (1) and 0.66 (1):0.34 (1), respectively; one benzene­sulfonate anion (atoms S3, O31, O32 and O33) is disordered over two sites, with an occupancy ratio of 0.644 (6):0.356 (6). The measured crystal of (1) appeared to be twinned by reticular merohedry, with two components rotated with respect to each other by ∼180° around the direct-space a axis. 974 reflections were overlapped, whereas 3705 and 3735 reflections were isolated for components (1) and (2), respectively. Data reduction was conducted taking into account both twin domains and an HKLF 5 file was produced. The final refined twin ratio for (1) was 0.4489 (8):0.5511 (8).

Table 1
Experimental details

For all compounds, H atoms were treated by a mixture of independent and constrained refinement. Mepeta was refined as an inversion twin [absolute structure parameter = 0.27 (11)].

	Mepeta	(1)	(2)
Crystal data
Chemical formula	C6H9N3S	[Cu2(NO3)2(C6H9N3S)2]	[Cu2(BF4)2(C6H9N3S)2]
Mr	155.22	561.54	611.14
Crystal system, space group	Orthorhombic, Pna21	Triclinic, P	Triclinic, P
Temperature (K)	120	100	100
a, b, c (Å)	8.843 (3), 17.485 (5), 5.041 (3)	7.235 (3), 7.548 (3), 10.297 (4)	7.754 (3), 7.965 (3), 10.372 (4)
α, β, γ (°)	90, 90, 90	105.42 (3), 98.15 (3), 112.43 (3)	67.57 (3), 89.99 (3), 61.07 (3)
V (Å^3)	779.4 (6)	482.0 (4)	504.6 (4)
Z	4	1	1
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm^−1)	0.34	2.47	2.40
Crystal size (mm)	0.98 × 0.42 × 0.11	0.43 × 0.21 × 0.14	0.44 × 0.23 × 0.18
Data collection
Diffractometer	Kuma KM-4-CCD	Rigaku Xcalibur Onyx	Rigaku Xcalibur Onyx
Absorption correction	Analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	Analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	Analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]
Tmin, Tmax	0.801, 0.964	0.542, 0.768	0.498, 0.711
No. of measured, independent and observed [I > 2σ(I)] reflections	11519, 3214, 2812	8459, 8459, 6900	8712, 4784, 4163
Rint	0.051	0.020	0.014
(sin θ/λ)max (Å^−1)	0.843	0.876	0.876
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.042, 0.105, 1.06	0.034, 0.096, 1.06	0.022, 0.061, 1.07
No. of reflections	3214	8459	4784
No. of parameters	124	141	149
No. of restraints	1	0	0
Δρmax, Δρmin (e Å^−3)	0.31, −0.31	0.88, −1.03	0.56, −0.51

	(3)	(4)	(5)
Crystal data
Chemical formula	[Cu2(NO3)2(C5H7N3S2)2(H2O)]	[Cu2(SiF6)(C5H7N3S2)2(H2O)]·0.5C2H3N·2H2O	[Cu2(C6H5O3S)(C5H7N3S2)2](C6H5O3S)·CH4O·H2O
Mr	615.63	688.24	837.97
Crystal system, space group	Monoclinic, P21/c	Monoclinic, P21/n	Monoclinic, P21/c
Temperature (K)	100	260	110
a, b, c (Å)	7.379 (3), 18.780 (5), 14.702 (4)	11.899 (4), 11.442 (4), 17.678 (5)	14.944 (4), 16.587 (5), 14.658 (4)
α, β, γ (°)	90, 94.82 (3), 90	90, 102.04 (3), 90	90, 117.91 (3), 90
V (Å^3)	2030.2 (11)	2353.9 (13)	3210.7 (17)
Z	4	4	4
Radiation type	Mo Kα	Mo Kα	Cu Kα
μ (mm^−1)	2.56	2.29	5.77
Crystal size (mm)	0.3 × 0.18 × 0.13	0.52 × 0.17 × 0.09	0.45 × 0.32 × 0.17
Data collection
Diffractometer	Rigaku Xcalibur Ruby	Rigaku Xcalibur Sapphire2 (large Be window)	Rigaku Xcalibur Onyx
Absorption correction	Analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	Analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	Analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]
Tmin, Tmax	0.577, 0.776	0.452, 0.825	0.248, 0.540
No. of measured, independent and observed [I > 2σ(I)] reflections	11883, 6647, 4618	24572, 5649, 3717	16595, 6741, 6073
Rint	0.037	0.053	0.056
(sin θ/λ)max (Å^−1)	0.752	0.661	0.634
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.045, 0.115, 1.01	0.037, 0.087, 1.02	0.057, 0.166, 1.05
No. of reflections	6647	5649	6741
No. of parameters	346	412	487
No. of restraints	0	245	3
Δρmax, Δρmin (e Å^−3)	0.68, −0.70	0.47, −0.38	1.03, −1.49
Computer programs: CrysAlis PRO (Rigaku OD, 2015), CrysAlis CCD (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b) and OLEX2 (Dolomanov et al., 2009).

2.5. Hirshfeld surface analysis and fingerprint plots

The three-dimensional Hirshfeld surfaces (HSs) and two-dimensional fingerprint plots for (1) and (2) were generated using Crystal Explorer (Wolff et al., 2012; Spackman & Jayatilaka, 2009).

3. Results and discussion

Mepeta crystallizes in the noncentrosymmetric space group Pna2₁, with one mol­ecule in the asymmetric unit (Fig. 1). The C2—N3 and C2—N1 bond lengths are consistent with delocalization of the electrons between the thia­diazole ring and the N atom of the amino group. The C2—N1 bond length of 1.338 (3) Å is slightly shorter than a nominal C_ar—N(sp²)H bond length of 1.353 Å, while the C2—N3 bond length of 1.319 (2) Å is slightly longer than the neighbouring C5—N4 bond [1.293 (3) Å] of the same thia­diazole ring. The H atom of the amino group participates in N—H⋯N hydrogen bonding (Table 2) with the thia­diazole N3 atom of the nearest mol­ecule, forming an infinite hydrogen-bonded chain in the [100] direction (Fig. 2). Neighbouring Mepeta mol­ecules within the chain are twisted relative to each other by 89.33 (3)°, thus enabling a larger allyl-group mobility in the space (d ∼ 6 × 9 Å) between the thia­diazole rings of the nearest chains. Therefore, the C atoms of the allyl groups are disordered over two sites [the site-occupation factors are 0.660 (6) for A and 0.340 (6) for B], so that the methene H atom (with a site-occupation factor of 0.340) from one {Mepeta}_∞ chain is connected to the thia­diazole N4 atom of the nearest chain by a weak hydrogen bond (C8B—H8B⋯N4^iv = 2.38 Å; Table 2). The dihedral angles between the plane of the thia­diazole ring and the N1—C7A and N1—C7B bonds of the allyl­amino group are 4.2 (4) and −10.2 (4)°, respectively. The double-bond distances C8A=C9A and C8B=C9B are 1.325 (10) and 1.412 (19) Å, respectively.

Table 2
Hydrogen-bond geometry (Å, °) for Mepeta

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N3^i	0.88 (3)	2.02 (3)	2.860 (2)	159 (3)
C7A—H7AA⋯S1^ii	0.99	2.97	3.462 (4)	112
C7B—H7BA⋯S1^iii	0.99	2.96	3.880 (8)	156
C8B—H8B⋯N4^iv	0.95	2.38	3.295 (5)	163
Symmetry codes: (i) ; (ii) x, y, z-1; (iii) ; (iv) .

Figure 1 The independent part in the Mepeta crystal structure. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2 The hydrogen-bonded chains (dashed lines) in the Mepeta structure.

Crystals of (1) and (2) (see Scheme 3) are similar to the previously studied [Cu(CF₃SO₃)(Mepeta)]₂ π-complex (Goreshnik et al., 2016). The asymmetric unit contains one Cu^I centre, one Mepeta ligand and one nitrate ligand in (1) or one tetra­fluoro­borate ligand in (2) (donoted An). The Mepeta mol­ecule is coordinated to the metal centre via the two N atoms of the thia­diazole ring and the allylic C=C bond in a chelating–bridging mode. The trigonal–pyramidal Cu^I environment in the basal plane includes the N3 atom and the C=C bond of one thia­diazole ligand and the N4 atom of another heterocyclic ring. The apical position of the metal coordination polyhedron is occupied by either weakly coordinating O or F atoms of NO₃⁻ or BF₄⁻ in (1) and (2), respectively. Therefore, two Cu^I atoms are bridged by two neighbouring Mepeta mol­ecules, connecting them into centrosymmetrical [Cu(NO₃)(Mepeta)]₂, (1), and [Cu(BF₄)(Mepeta)]₂, (2), dimers (Fig. 3). The Cu⋯Cu distance of 3.472 (2) Å in (1) and of 3.488 (2) Å in (2) are too long for a cuprophilic inter­action (Lake & Willans, 2013). Two thia­diazole rings from the same dimer are entirely coplanar. It is inter­esting to note that S-allyl derivatives of 1-aryl-­substituted 1H-tetra­zole-5-thiol have the same tridentate–chelate coordination mode, connecting two Cu^I atoms by means of an allylic C=C bond and two tetra­zole N atoms into centrosymmetric {[Cu(L)(H₂O)]⁺}₂ dimers (Slyvka et al., 2009, 2010).

Figure 3 Centrosymmetric [Cu(An)(Mepeta)]2 dimers in the structures of (a) (1) and (b) (2). Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) −x + 1, −y + 1, −z + 1.]

The strength of the Cu^I—(C=C) inter­action is confirmed by the fact that the allylic C=C bonds are slightly elongated to 1.360 (3) Å in (1) and 1.3706 (16) Å (2) [compared with a nominal value of 1.33 Å and a value of 1.340 (7) Å in Mepeta]. The Cu^I atom deviates from the base of the trigonal pyramid by Δ = 0.132 (3) Å in (1) and 0.062 (2) Å in (2), while the angle τ between the C=C bond and the basal plane is 11.3 (1)° in (1) and 12.5 (1)° in (2). This conclusion is also confirmed by the rather short Cu—m distances (m is the mid-point of C=C bond) and the rather large C—Cu—C angles (Table 3).

Table 3
Selected geometric parameters (Å, °) of (1) and (2)

m is the mid-point of the C=C bond.

Complex (1)
Cu1—N3	1.9938 (17)	Cu1—m	1.940 (1)
Cu1—N4^i	1.9693 (19)	Cu1—O1	2.473 (3)
Cu1—C8	2.038 (2)	C8—C9	1.360 (3)
Cu1—C9	2.073 (2)
N4^i—Cu1—N3	114.48 (7)	O1—Cu—m	97.76 (5)
C8—Cu1—C9	38.62 (8)	C9—C8—C7	122.8 (2)
Complex (2)
Cu1—N3	2.0036 (15)	Cu1—m	1.9454 (9)
Cu1—N4^i	1.9646 (11)	Cu1 – F1	2.6670 (15)
Cu1—C8	2.0451 (12)	C8—C9	1.3706 (16)
Cu1—C9	2.0799 (15)
N4^i—Cu1—N3	114.54 (5)	F1—Cu—m	95.51 (3)
C8—Cu1—C9	38.80 (5)	C9—C8—C7	123.77 (10)
Symmetry code: (i) −x + 1, −y + 1, −z + 1.

Through N—H⋯X [X = O in (1) or F in (2)] (Table 4) hydrogen bonds between the H atom of the ligand amino group and the X atoms of the NO₃⁻ ligand in (1) or the BF₄⁻ ligand in (2), neighbouring [Cu(Mepeta)(An)]₂ fragments are linked into hydrogen-bonded stair-like chains extending in the [010] direction (Fig. 4). These chains are inter­penetrated by a variety of C—H⋯X contacts to produce a three-dimensional framework.

Table 4
Hydrogen-bond geometry (Å, °) for (1) and (2)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
Complex (1)
N2—H2⋯O1^ii	0.80 (3)	2.32 (3)	3.034 (3)	150 (2)
N2—H2⋯O2^ii	0.80 (3)	2.24 (3)	2.970 (3)	153 (2)
Complex (2)
N2—H2⋯F2^ii	0.87 (2)	1.95 (2)	2.7874 (14)	160 (1)
N2—H2⋯F3^ii	0.87 (2)	2.53 (2)	3.242 (2)	140 (1)
C7—H7B⋯F4^iii	0.99	2.53	3.4900 (17)	163
Symmetry codes: (ii) x, y-1, z; (iii) -x+1, -y+1, -z.

Figure 4 The hydrogen-bonded array in the structure of the [Cu(BF4)(Mepeta)]2 π-complex, (2).

The organic–inorganic hybrid π-complex (3) (see Scheme 4) crystallizes in the centrosymmetric space group P2₁/c. The asymmetric unit contains two Cu^I centres, two Pesta ligands, one bridging aqua ligand and two nitrate ligands. Similar to Mepeta, Pesta is coordinated to copper(I) via the thia­diazole N3 and N4 atoms and the allylic C=C bond in a chelating–bridging mode. In contrast to the {Cu₂(Mepeta)₂}²⁺ units in (1) and (2), two Cu^I atoms in (3) are connected by two Pesta ligands into a noncentrosymmetric {Cu₂(Pesta)₂}²⁺ unit (Fig. 5a). The planes of the thia­diazole rings from the same dimer form a dihedral angle of 31.2 (1)°. The conformational flexibility of the dimer allows the Cu^I atom site to be split over two positions with different coordination environments. The trigonal–pyramidal environments of atoms Cu1A and Cu2A [site-occupation factors = 0.765 (6) and 0.794 (7), respectively] in the basal plane include the C=C bond and two N atoms of neighbouring Pesta ligands, while the apical positions are occupied by weakly coordinated O atoms of NO₃⁻ ligands (Table 5). The common apical position of the two trigonal pyramids of the other Cu1B and Cu2B pair [site-occupation factors = 0.235 (7) and 0.206 (7)] is occupied by a bridging aqua mol­ecule. The distances from Cu1A and Cu2A to the water O atom of 2.835 (7) and 2.767 (7) Å, respectively, are significantly longer than the formally limiting distance (2.63 Å; Slyvka et al., 2013) of a Cu—O_ap inter­action [in the case of copper(I) π-complexes with allyl derivatives of heterocycles], but at the same time it is slightly shorter than the sum of the van der Waals radii of 2.92 Å (Bondi, 1964).

Table 5
Selected geometric parameters (Å, °) of (3)

m and m′ are the mid-points of the allylic C18A=C19A and C28A=C29A bonds, respectively.

Cu1A—N13	2.045 (3)	Cu2A—C28A	2.062 (4)
Cu1A—N24	1.962 (2)	Cu2A—C29A	2.052 (8)
Cu1A—C18A	2.054 (4)	Cu2B—O1	2.341 (7)
Cu1A—C19A	2.039 (6)	Cu1A—O11	2.4416 (29)
Cu1B—O1	2.363 (7)	Cu2A—O21	2.5391 (31)
Cu2A—N14	1.974 (3)	C18A—C19A	1.374 (9)
Cu2A—N23	1.998 (3)	C28A—C29A	1.369 (11)
Cu1A—m	1.928 (2)	Cu2A—m′	1.940 (2)
N24—Cu1A—N13	110.12 (11)	C19A—C18A—C17A	125.4 (5)
C19A—Cu1A—C18A	39.2 (2)	C29A—C28A—C27A	125.9 (5)
N14—Cu2A—N23	111.13 (12)	O11—Cu1A—m	98.77 (8)
C29A—Cu2A—C28A	38.9 (3)	O21—Cu2A—m′	101.25 (8)

Figure 5 (a) The independent part of the structure of (3) and (b) the cationic [Cu2(Mepeta)2(H2O)2]^2+ dimer in the [Cu2(Mepeta)2(H2O)2]SiF6·2.5H2O complex (Ardan et al., 2013). One of the two disordered positions of the allyl­sulfanyl group and the metal atom in (3), i.e. with the lower site-occupancy factor, are shown in semi-transparent mode. Displacement ellipsoids are drawn at the 20% probability level.

The H atoms of the ligand amino group and the coordinated water mol­ecule participate in X—H⋯Y (X and Y = N or O) hydrogen bonding with NO₃⁻ ligands, forming a three-dimensional hydrogen-bonded network (Table 6).

Table 6
Hydrogen-bond geometry (Å, °) for (3)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O13^i	0.93 (5)	2.01 (5)	2.846 (4)	149 (4)
O1—H1B⋯O22^ii	0.99 (5)	2.29 (5)	3.142 (4)	143 (4)
O1—H1B⋯O23^ii	0.99 (5)	2.25 (5)	2.946 (3)	126 (3)
N12—H12A⋯O13^iii	0.93 (4)	2.16 (4)	3.053 (4)	161 (3)
N12—H12B⋯O22	0.84 (4)	2.09 (4)	2.918 (4)	166 (3)
N22—H22A⋯O12	0.85 (4)	2.07 (4)	2.895 (4)	163 (3)
N22—H22B⋯O23^iv	0.82 (3)	2.07 (3)	2.856 (3)	162 (3)
Symmetry codes: (i) x-1, y, z; (ii) ; (iii) ; (iv) -x+1, -y+1, -z.

A similar {Cu₂(Pesta)₂}²⁺ unit was found in the structure of (4) (see Scheme 5). The asymmetric unit contains two Cu^I centres, two Pesta ligands, one bridging aqua ligand and one anionic SiF₆²⁻ ligand (Fig. 6a). The planes of the thia­diazole rings from the same dimer form a dihedral angle of 28.3 (1)°. The π-complex [Cu₂(SiF₆)(Pesta)₂(H₂O)]·0.5CH₃CN·2H₂O, (4), may be considered as a rare example of the direct Cu^I—F(SiF₆²⁻) inter­action. This inter­action has been found previously in only two Cu₂SiF₆ π-complexes with 1-allyl­benzotriazole, Abtr (Goreshnik et al., 2011) and Mepeta (Goreshnik et al., 2016). Despite the fact that the SiF₆²⁻ anions are not directly coordinated to the Cu^I atom, but form hydrogen bonds with the coordinated water mol­ecules, the Pesta ligand allows the Cu^I ion to be divided between two positions with water O-atom or hexafluorosilicate F-atom coordination (Fig. 6a), resulting in the splitting of one Cu^I position of the {Cu₂(Pesta)₂}²⁺ unit into two sites, i.e. Cu2A and Cu2B (0.88:0.12). The Cu2B⋯F1 distance of 2.833 (16) Å in (4) is longer than the Cu^I⋯F distance of 2.44 Å in [Cu₂(SiF₆)(Abtr)₂(H₂O)₂]·2H₂O (Goreshnik et al., 2011), but is still shorter than the sum of the van der Waals radii (2.87 Å). The above inter­action results in a lower U_eq(F1) value of 0.0531 (5) Ų compared with the U_eq(F2) value of 0.0641 (6) Ų, while the other F atoms of the SiF₆²⁻ anion are disordered in a carousel-like mode. Thus, the two Cu^I atoms have different coordination environments: Cu1 and Cu2A have a trigonal–pyramidal surrounding, with a common apical water mol­ecule, while the apical position of the Cu2B polyhedron is occupied by a weakly coordinated F atom of the SiF₆²⁻ anion (Fig. 6). For comparison, in a previously studied π-complex of Cu₂SiF₆ with Mepeta, viz. [Cu₂(Mepeta)₂(H₂O)₂]SiF₆·2.5H₂O, the noncentrosymmetric {Cu₂(Mepeta)₂}²⁺ unit was also found (Fig. 5b), but each Cu^I atom is linked with a different apical water mol­ecule (Ardan et al., 2013). Moreover, two coordinated water mol­ecules in the last case are located on the same side of the dimer unit [as was found for the NO₃⁻ ligands in (3); Fig. 5a].

Figure 6 The structural arrangement in π-complexes (a) (4) and (b) (5). One of the two disordered positions of the Cu, C and F atoms in (4), and of the C, O and S atoms in (5), i.e. with the lower site-occupancy factor, is shown in semi-transparent mode. Displacement ellipsoids are drawn at the 30% probability level.

The H atoms of the ligand amino group in (4) are involved in N—H⋯F hydrogen bonding with the F1 and F2 atoms of two neighbouring SiF₆²⁻ anions, connecting {Cu₂(SiF₆)(Pesta)₂(H₂O)} units into hydrogen-bonded layers. The latter, by means of O—H⋯O- and O—H⋯F-type hydrogen bonds involving atoms of the coordinated and constitutional water mol­ecules, are inter­penetrated into a supra­molecular structure (Table 7).

Table 7
Hydrogen-bond geometry (Å, °) for (4)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N12—H12A⋯F1	0.86 (3)	2.14 (4)	2.973 (4)	163 (3)
N12—H12B⋯F2^i	0.86 (4)	2.04 (4)	2.827 (3)	152 (3)
N22—H22A⋯F2^ii	0.93 (4)	2.05 (4)	2.903 (4)	153 (3)
N22—H22B⋯F5A^iii	0.83 (4)	1.83 (4)	2.638 (5)	165 (4)
N22—H22B⋯F5B^iii	0.83 (4)	1.98 (4)	2.758 (9)	157 (4)
N22—H22B⋯F5C^iii	0.83 (4)	2.50 (4)	3.27 (2)	154 (4)
N22—H22B⋯F4D^iii	0.83 (4)	2.00 (4)	2.766 (15)	153 (4)
O1—H1A⋯N1	0.91	1.89	2.789 (10)	175
O1—H1B⋯O2	0.90	1.85	2.698 (4)	156
O2—H2A⋯F5B^iv	0.87	1.98	2.819 (11)	163
O2—H2A⋯F5C^iv	0.87	1.52	2.385 (12)	169
O2—H2A⋯F5D^iv	0.87	1.64	2.427 (15)	150
O2—H2B⋯F3C^v	0.87	1.59	2.383 (11)	149
O2—H2B⋯F3D^v	0.87	1.59	2.465 (18)	177
O2—H2B⋯F4A^v	0.87	2.09	2.952 (9)	169
Symmetry codes: (i) ; (ii) ; (iii) -x-1, -y-1, -z; (iv) ; (v) x+1, y, z.

The structure most similar to [Cu₂(Mepeta)₂(H₂O)₂]SiF₆·2.5H₂O is the π-complex (5) (see Scheme 6) (Fig. 6b). Two O atoms of the benzene­sulfonate ligand in (5) are bound to the two Cu^I atoms of the same {Cu₂(Pesta)₂}²⁺ unit, while the other benzene­sulfonate anion is involved in N—H⋯O hydrogen bonding with the ligand amine group. The tendency for the O atom to be bound simultaneously to the two metal atoms of the dimer appears to be common for dimeric {Cu₂(Pesta)₂}²⁺ cations. Therefore, the sulfonate group of the anion in (5) is disordered over two sites (O31A/O32A/O33A and O31B/O32B/O33B), with an occupancy ratio of 0.644 (6):0.356 (6), and one O atom of the lower-occupancy unit plays the same role as the water mol­ecule in (3), binding two metal centres. The planes of the thia­diazole rings from the same dimer in (5) form a dihedral angle of 34.4 (1)°. By means of a variety of N—H⋯O and O—H⋯O hydrogen bonds (Table 8), the above dimers are connected into a hydrogen-bonded framework (Fig. 7). To the best of our knowledge, complex (5) is the first known example of a Cu^I(C₆H₅SO₃) coordination compound [for comparison, there are eight entries in the Cambridge Structural Database (Groom et al., 2016) for Cu^II(C₆H₅SO₃) coordination complexes].

Table 8
Hydrogen-bond geometry (Å, °) for (5)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N12—H12A⋯O51^i	0.91 (5)	1.94 (5)	2.765 (4)	150 (4)
N12—H12B⋯O41	0.87 (5)	2.00 (5)	2.867 (4)	174 (4)
N22—H22A⋯O42^ii	0.90 (5)	2.04 (5)	2.896 (4)	158 (4)
N22—H22B⋯O61^iii	0.86 (5)	1.96 (5)	2.758 (4)	154 (4)
O61—H61⋯O43^iv	0.75 (6)	1.98 (6)	2.726 (4)	174 (6)
O51—H51A⋯O43^v	0.82 (6)	2.00 (7)	2.790 (4)	164 (6)
O51—H51B⋯O32B	0.81 (7)	2.20 (7)	3.010 (11)	170 (6)
O51—H51B⋯O33A	0.81 (7)	1.84 (7)	2.641 (7)	168 (6)
Symmetry codes: (i) ; (ii) -x+2, -y+1, -z+1; (iii) ; (iv) -x+2, -y+1, -z+2; (v) -x+1, -y+1, -z+1.

Figure 7 The hydrogen-bonded array in [Cu2(SiF6)(Pesta)2(H2O)]·CH3OH·2H2O, (4). Displacement ellipsoids are drawn at the 30% probability level.

3.1. Hirshfeld surface analysis

The Hirshfeld surfaces were built for [Cu(NO₃)(Mepeta)]₂, (1), and [Cu(BF₄)(Mepeta)]₂, (2), to analyze the inter­actions between the units. The most prominent inter­actions, between Mepeta H atoms and nitrate O atoms in (1), as well as between Mepeta H atoms and tetrafluoroborate F atoms, can be seen in the Hirshfeld surface plots as the bright and pale-pink areas (Fig. 8a). Fingerprint plots were produced to show the inter­molecular surface bond lengths, with the regions highlighted for H⋯O, H⋯F and H⋯S inter­actions. The contribution to the surface area for H⋯H contacts is 27.7% in (1) and 24.4% in (2).

Figure 8 Hirshfeld surface analysis of the [Cu(NO3)(Mepeta)]2, (1), and [Cu(BF4)(Mepeta)]2, (2), dimers. (a) The Hirshfeld surfaces mapped with dnorm, which highlights both the donor and acceptor ability. (b) Fingerprint plots for the dimeric units resolved into (L)H⋯O(NO3^−) or (L)H⋯F(BF4^−) contacts. (c) Fingerprint plots for the dimeric units resolved into (L)H⋯S contacts. (d) Fingerprint plots for the dimeric units resolved into H⋯H contacts. The full fingerprint appears beneath each decomposed plot in grey.

4. Summary

The syntheses and crystal structures of 5-methyl-N-(prop-2-en-1-yl)-1,3,4-thia­diazol-2-amine (Mepeta) and five copper(I) π-complexes with Mepeta and 5-(prop-2-en-1-ylsulfan­yl)-1,3,4-thia­diazol-2-amine (Pesta) have been described. Mepeta itself crystallizes in the noncentrosymmetric space group Pna2₁, with one mol­ecule in the asymmetric unit. Both Mepeta and Pesta reveal a strong tendency towards the formation of dimeric {Cu₂L₂}²⁺ fragments, being attached to the metal atom in a chelating–bridging mode via two thia­diazole N atoms and an allylic C=C bond. The symmetry of the {Cu₂(Mepeta)₂}²⁺ unit depends on the charge of the anion; centrosymetric units were found in the presence of singly charged anions and a noncentrosymmetric dimer was found in the case of the doubly charged SiF₆²⁻ ion. The flexibility of the {Cu₂(Pesta)₂}²⁺ unit allows the Cu^I atom site to be split over two positions with different coordination environments, thus enabling the competitive participation of different molecules in bonding to the metal centre. Pesta allows the Cu^I ion to be divided between two positions with water O-atom or hexafluorosilicate F-atom coordination, resulting in the rare case of a direct Cu^I⋯FSiF₅²⁻ inter­action. The tendency of oxygen to be bound simultaneously to two metal atoms in the dimeric {Cu₂(Pesta)₂}²⁺ cation is confirmed by the presence of disorder in the benzene­sulfonate anion. By a variety of sufficiently strong hydrogen bonds, the dimeric {Cu₂(L)₂(An)₂} (An = NO₃⁻, BF₄⁻ and SiF₆²⁻) units participate in supra­molecular structure formation. Structure (5) should be considered as the first known example of a Cu^I(C₆H₅SO₃) coordination compound.

Supporting information

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2015) for mepeta, (1), (3), (5); CrysAlis CCD (Oxford Diffraction, 2010) for (2), (4). Cell refinement: CrysAlis PRO (Rigaku OD, 2015) for mepeta, (1), (3), (5); CrysAlis RED (Oxford Diffraction, 2010) for (2), (4). Data reduction: CrysAlis PRO (Rigaku OD, 2015) for mepeta, (1), (3), (5); CrysAlis RED (Oxford Diffraction, 2010) for (2), (4). For all compounds, program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(mepeta) 5-Methyl-N-(prop-2-en-1-yl)-1,3,4-thiadiazol-2-amine

Crystal data

C6H9N3S	Dx = 1.323 Mg m^−3
Mr = 155.22	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 5973 reflections
a = 8.843 (3) Å	θ = 3.3–36.3°
b = 17.485 (5) Å	µ = 0.34 mm^−1
c = 5.041 (3) Å	T = 120 K
V = 779.4 (6) Å^3	Plate, clear light colourless
Z = 4	0.98 × 0.42 × 0.11 mm
F(000) = 328

Data collection

Kuma KM-4-CCD diffractometer	3214 independent reflections
Radiation source: Kuma KM-4-CCD, Kuma KM-4-CCD	2812 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 8.3359 pixels mm^-1	θmax = 36.8°, θmin = 3.3°
ω scans	h = −14→11
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	k = −27→26
Tmin = 0.801, Tmax = 0.964	l = −7→8
11519 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.042	w = 1/[σ^2(Fo^2) + (0.061P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.105	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.31 e Å^−3
3214 reflections	Δρmin = −0.31 e Å^−3
124 parameters	Absolute structure: Refined as an inversion twin
1 restraint	Absolute structure parameter: 0.27 (11)
Primary atom site location: structure-invariant direct methods

Special details

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

Refinement. Refined as a 2-component inversion twin

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.77479 (4)	0.83578 (2)	0.66791 (14)	0.03107 (13)
N1	0.71891 (16)	0.73279 (10)	0.2801 (4)	0.0345 (3)
H1	0.814 (3)	0.7180 (15)	0.295 (6)	0.041*
N3	0.51665 (15)	0.80284 (9)	0.4639 (4)	0.0335 (3)
N4	0.48989 (16)	0.85941 (10)	0.6522 (5)	0.0387 (3)
C2	0.66088 (16)	0.78417 (9)	0.4483 (4)	0.0279 (3)
C5	0.6107 (2)	0.88210 (11)	0.7732 (4)	0.0346 (4)
C6	0.6120 (3)	0.94181 (13)	0.9846 (5)	0.0469 (5)
H6A	0.6634	0.9218	1.1422	0.070*
H6B	0.5078	0.9556	1.0302	0.070*
H6C	0.6656	0.9872	0.9200	0.070*
C7A	0.6390 (4)	0.69117 (19)	0.0720 (8)	0.0276 (6)	0.660 (6)
H7AA	0.7062	0.6857	−0.0841	0.033*	0.660 (6)
H7AB	0.5492	0.7209	0.0164	0.033*	0.660 (6)
C7B	0.5939 (6)	0.6893 (4)	0.1468 (17)	0.0275 (12)	0.340 (6)
H7BA	0.5253	0.6662	0.2798	0.033*	0.340 (6)
H7BB	0.5343	0.7234	0.0298	0.033*	0.340 (6)
C8A	0.5898 (3)	0.61366 (15)	0.1627 (7)	0.0326 (6)	0.660 (6)
H8A	0.5342	0.6083	0.3229	0.039*	0.660 (6)
C8B	0.6714 (5)	0.6288 (3)	−0.0111 (11)	0.0296 (13)	0.340 (6)
H8B	0.7532	0.6415	−0.1250	0.035*	0.340 (6)
C9A	0.6238 (13)	0.5524 (6)	0.020 (3)	0.061 (4)	0.660 (6)
H9AA	0.6794	0.5578	−0.1404	0.073*	0.660 (6)
H9AB	0.5926	0.5032	0.0774	0.073*	0.660 (6)
C9B	0.621 (2)	0.5524 (9)	0.012 (3)	0.042 (6)	0.340 (6)
H9BA	0.5394	0.5403	0.1260	0.051*	0.340 (6)
H9BB	0.6694	0.5132	−0.0877	0.051*	0.340 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.02516 (16)	0.0356 (2)	0.0324 (2)	−0.00651 (12)	−0.00796 (18)	0.0006 (2)
N1	0.0290 (6)	0.0327 (8)	0.0417 (8)	0.0004 (5)	−0.0151 (6)	−0.0023 (7)
N3	0.0227 (5)	0.0346 (8)	0.0430 (9)	−0.0016 (5)	−0.0083 (6)	0.0042 (7)
N4	0.0308 (6)	0.0407 (8)	0.0446 (9)	0.0035 (5)	−0.0044 (8)	0.0040 (9)
C2	0.0228 (5)	0.0278 (7)	0.0330 (9)	−0.0057 (5)	−0.0094 (6)	0.0072 (6)
C5	0.0360 (7)	0.0346 (9)	0.0332 (9)	0.0007 (6)	−0.0027 (7)	0.0042 (7)
C6	0.0613 (12)	0.0426 (11)	0.0368 (11)	0.0010 (10)	−0.0021 (10)	−0.0012 (9)
C7A	0.0245 (13)	0.0283 (13)	0.0302 (16)	−0.0014 (11)	−0.0038 (11)	0.0017 (12)
C7B	0.0136 (17)	0.037 (3)	0.032 (3)	−0.0037 (17)	−0.001 (2)	−0.012 (3)
C8A	0.0305 (10)	0.0327 (12)	0.0344 (13)	−0.0051 (8)	−0.0006 (13)	0.0042 (14)
C8B	0.0218 (17)	0.039 (3)	0.027 (3)	−0.0006 (16)	0.0011 (16)	−0.0031 (19)
C9A	0.056 (6)	0.035 (5)	0.092 (8)	0.005 (4)	−0.003 (5)	0.007 (4)
C9B	0.054 (10)	0.031 (8)	0.042 (8)	0.004 (6)	−0.012 (6)	−0.026 (6)

Geometric parameters (Å, º)

S1—C2	1.7478 (18)	C7A—H7AB	0.9900
S1—C5	1.744 (2)	C7A—C8A	1.495 (4)
N1—H1	0.88 (3)	C7B—H7BA	0.9900
N1—C2	1.338 (3)	C7B—H7BB	0.9900
N1—C7A	1.459 (4)	C7B—C8B	1.490 (9)
N1—C7B	1.501 (5)	C8A—H8A	0.9500
N3—N4	1.391 (3)	C8A—C9A	1.325 (10)
N3—C2	1.319 (2)	C8B—H8B	0.9500
N4—C5	1.293 (3)	C8B—C9B	1.412 (19)
C5—C6	1.492 (3)	C9A—H9AA	0.9500
C6—H6A	0.9800	C9A—H9AB	0.9500
C6—H6B	0.9800	C9B—H9BA	0.9500
C6—H6C	0.9800	C9B—H9BB	0.9500
C7A—H7AA	0.9900
C5—S1—C2	87.31 (9)	N1—C7A—C8A	111.9 (3)
C2—N1—H1	120.7 (19)	H7AA—C7A—H7AB	107.9
C2—N1—C7A	127.2 (2)	C8A—C7A—H7AA	109.2
C2—N1—C7B	110.0 (3)	C8A—C7A—H7AB	109.2
C7A—N1—H1	112.0 (19)	N1—C7B—H7BA	110.7
C7B—N1—H1	126.2 (18)	N1—C7B—H7BB	110.7
C2—N3—N4	112.41 (14)	H7BA—C7B—H7BB	108.8
C5—N4—N3	113.55 (15)	C8B—C7B—N1	105.1 (4)
N1—C2—S1	121.81 (11)	C8B—C7B—H7BA	110.7
N3—C2—S1	113.06 (15)	C8B—C7B—H7BB	110.7
N3—C2—N1	125.11 (16)	C7A—C8A—H8A	120.0
N4—C5—S1	113.66 (16)	C9A—C8A—C7A	120.0 (6)
N4—C5—C6	123.92 (19)	C9A—C8A—H8A	120.0
C6—C5—S1	122.42 (15)	C7B—C8B—H8B	120.5
C5—C6—H6A	109.5	C9B—C8B—C7B	118.9 (8)
C5—C6—H6B	109.5	C9B—C8B—H8B	120.5
C5—C6—H6C	109.5	C8A—C9A—H9AA	120.0
H6A—C6—H6B	109.5	C8A—C9A—H9AB	120.0
H6A—C6—H6C	109.5	H9AA—C9A—H9AB	120.0
H6B—C6—H6C	109.5	C8B—C9B—H9BA	120.0
N1—C7A—H7AA	109.2	C8B—C9B—H9BB	120.0
N1—C7A—H7AB	109.2	H9BA—C9B—H9BB	120.0
N1—C7A—C8A—C9A	−128.3 (6)	C2—N1—C7B—C8B	−174.0 (4)
N1—C7B—C8B—C9B	130.5 (9)	C2—N3—N4—C5	−0.1 (2)
N3—N4—C5—S1	0.0 (2)	C5—S1—C2—N1	178.47 (17)
N3—N4—C5—C6	−179.6 (2)	C5—S1—C2—N3	−0.01 (15)
N4—N3—C2—S1	0.0 (2)	C7A—N1—C2—S1	−174.1 (2)
N4—N3—C2—N1	−178.39 (18)	C7A—N1—C2—N3	4.2 (4)
C2—S1—C5—N4	−0.02 (16)	C7B—N1—C2—S1	171.5 (4)
C2—S1—C5—C6	179.64 (18)	C7B—N1—C2—N3	−10.2 (4)
C2—N1—C7A—C8A	−96.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3^i	0.88 (3)	2.02 (3)	2.860 (2)	159 (3)
C7A—H7AA···S1^ii	0.99	2.97	3.462 (4)	112
C7B—H7BA···S1^iii	0.99	2.96	3.880 (8)	156
C8B—H8B···N4^iv	0.95	2.38	3.295 (5)	163

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

(1) Bis[µ-5-methyl-N-(prop-2-en-1-yl)-1,3,4-thiadiazol-2-amine]bis[nitratocopper(I)]

Crystal data

[Cu2(NO3)2(C6H9N3S)2]	Z = 1
Mr = 561.54	F(000) = 284
Triclinic, P1	Dx = 1.934 Mg m^−3
a = 7.235 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.548 (3) Å	Cell parameters from 3143 reflections
c = 10.297 (4) Å	θ = 3.1–38.5°
α = 105.42 (3)°	µ = 2.47 mm^−1
β = 98.15 (3)°	T = 100 K
γ = 112.43 (3)°	Block, clear colourless
V = 482.0 (4) Å^3	0.43 × 0.21 × 0.14 mm

Data collection

Rigaku Xcalibur Onyx diffractometer	8459 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	6900 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 8.1956 pixels mm^-1	θmax = 38.5°, θmin = 3.1°
ω and φ scans	h = −7→12
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	k = −13→12
Tmin = 0.542, Tmax = 0.768	l = −14→14
8459 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.061P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
8459 reflections	Δρmax = 0.88 e Å^−3
141 parameters	Δρmin = −1.03 e Å^−3

Special details

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

Refinement. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.57775 (3)	0.57834 (3)	0.68133 (2)	0.01261 (7)
S1	0.18975 (7)	−0.09982 (7)	0.47322 (5)	0.01402 (10)
O1	0.2950 (3)	0.6861 (3)	0.6800 (2)	0.0308 (4)
O2	0.2567 (3)	0.8531 (3)	0.8713 (2)	0.0348 (4)
O3	0.1088 (3)	0.5240 (3)	0.7949 (2)	0.0312 (4)
N1	0.2182 (3)	0.6865 (3)	0.7824 (2)	0.0193 (4)
N2	0.4533 (3)	0.1392 (3)	0.72781 (19)	0.0161 (3)
H2	0.411 (4)	0.037 (4)	0.746 (3)	0.019*
N3	0.4220 (2)	0.2864 (2)	0.55566 (17)	0.0122 (3)
N4	0.3167 (2)	0.2273 (2)	0.41582 (17)	0.0123 (3)
C2	0.3733 (3)	0.1302 (3)	0.6002 (2)	0.0127 (3)
C5	0.1895 (3)	0.0338 (3)	0.3607 (2)	0.0134 (3)
C6	0.0538 (3)	−0.0697 (3)	0.2141 (2)	0.0177 (4)
H6A	0.1375	−0.0900	0.1497	0.027*
H6B	−0.0103	0.0155	0.1914	0.027*
H6C	−0.0551	−0.2026	0.2048	0.027*
C7	0.6182 (3)	0.3254 (3)	0.8338 (2)	0.0161 (4)
H7A	0.7481	0.3591	0.8043	0.019*
H7B	0.6431	0.3010	0.9231	0.019*
C8	0.5662 (3)	0.5039 (3)	0.8573 (2)	0.0150 (4)
H8	0.4246	0.4786	0.8447	0.018*
C9	0.7131 (3)	0.7002 (3)	0.8957 (2)	0.0177 (4)
H9A	0.8556	0.7289	0.9089	0.021*
H9B	0.6733	0.8086	0.9095	0.021*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01666 (12)	0.00964 (10)	0.00970 (11)	0.00374 (9)	0.00286 (9)	0.00403 (8)
S1	0.0159 (2)	0.00918 (18)	0.0168 (2)	0.00455 (16)	0.00471 (18)	0.00559 (17)
O1	0.0361 (10)	0.0419 (10)	0.0367 (10)	0.0264 (9)	0.0210 (8)	0.0279 (9)
O2	0.0434 (11)	0.0194 (8)	0.0398 (11)	0.0152 (7)	0.0100 (9)	0.0064 (8)
O3	0.0275 (9)	0.0200 (7)	0.0523 (12)	0.0074 (7)	0.0187 (8)	0.0224 (8)
N1	0.0164 (8)	0.0178 (8)	0.0296 (10)	0.0088 (7)	0.0069 (7)	0.0148 (8)
N2	0.0208 (8)	0.0123 (7)	0.0162 (8)	0.0057 (6)	0.0053 (6)	0.0087 (7)
N3	0.0162 (7)	0.0104 (6)	0.0098 (7)	0.0051 (6)	0.0036 (6)	0.0045 (6)
N4	0.0151 (7)	0.0098 (6)	0.0109 (7)	0.0042 (5)	0.0039 (6)	0.0036 (6)
C2	0.0136 (8)	0.0102 (7)	0.0153 (9)	0.0050 (6)	0.0054 (7)	0.0055 (7)
C5	0.0152 (8)	0.0103 (7)	0.0153 (9)	0.0057 (7)	0.0049 (7)	0.0050 (7)
C6	0.0184 (9)	0.0112 (7)	0.0168 (9)	0.0028 (7)	−0.0007 (7)	0.0029 (7)
C7	0.0198 (9)	0.0165 (8)	0.0134 (9)	0.0082 (7)	0.0034 (7)	0.0074 (7)
C8	0.0195 (9)	0.0174 (8)	0.0099 (8)	0.0083 (7)	0.0042 (7)	0.0070 (7)
C9	0.0238 (10)	0.0164 (8)	0.0098 (8)	0.0070 (7)	0.0009 (7)	0.0048 (7)

Geometric parameters (Å, º)

Cu1—N3	1.9940 (19)	N4—Cu1^i	1.9690 (18)
Cu1—N4^i	1.9690 (18)	N4—C5	1.299 (2)
Cu1—C8	2.038 (2)	C5—C6	1.491 (3)
Cu1—C9	2.073 (2)	C6—H6A	0.9800
S1—C2	1.741 (2)	C6—H6B	0.9800
S1—C5	1.727 (2)	C6—H6C	0.9800
O1—N1	1.259 (3)	C7—H7A	0.9900
O2—N1	1.243 (2)	C7—H7B	0.9900
O3—N1	1.233 (2)	C7—C8	1.502 (3)
N2—H2	0.80 (3)	C8—H8	0.9500
N2—C2	1.331 (3)	C8—C9	1.360 (3)
N2—C7	1.458 (3)	C9—H9A	0.9500
N3—N4	1.393 (2)	C9—H9B	0.9500
N3—C2	1.319 (3)
N3—Cu1—C8	92.55 (8)	C5—C6—H6A	109.5
N3—Cu1—C9	129.43 (8)	C5—C6—H6B	109.5
N4^i—Cu1—N3	114.48 (7)	C5—C6—H6C	109.5
N4^i—Cu1—C8	152.33 (8)	H6A—C6—H6B	109.5
N4^i—Cu1—C9	113.75 (9)	H6A—C6—H6C	109.5
C8—Cu1—C9	38.62 (8)	H6B—C6—H6C	109.5
C5—S1—C2	87.58 (10)	N2—C7—H7A	109.1
O2—N1—O1	118.97 (19)	N2—C7—H7B	109.1
O3—N1—O1	120.4 (2)	N2—C7—C8	112.34 (17)
O3—N1—O2	120.6 (2)	H7A—C7—H7B	107.9
C2—N2—H2	118.5 (18)	C8—C7—H7A	109.1
C2—N2—C7	122.94 (18)	C8—C7—H7B	109.1
C7—N2—H2	118.6 (18)	Cu1—C8—H8	92.0
N4—N3—Cu1	122.79 (13)	C7—C8—Cu1	105.91 (14)
C2—N3—Cu1	123.96 (14)	C7—C8—H8	118.6
C2—N3—N4	112.03 (15)	C9—C8—Cu1	72.10 (13)
N3—N4—Cu1^i	117.17 (12)	C9—C8—C7	122.76 (19)
C5—N4—Cu1^i	127.96 (15)	C9—C8—H8	118.6
C5—N4—N3	113.16 (17)	Cu1—C9—H9A	106.6
N2—C2—S1	121.22 (15)	Cu1—C9—H9B	93.9
N3—C2—S1	113.25 (15)	C8—C9—Cu1	69.28 (13)
N3—C2—N2	125.52 (18)	C8—C9—H9A	120.0
N4—C5—S1	113.95 (16)	C8—C9—H9B	120.0
N4—C5—C6	124.60 (19)	H9A—C9—H9B	120.0
C6—C5—S1	121.45 (14)
Cu1—N3—N4—Cu1^i	27.76 (18)	N4—N3—C2—N2	178.15 (18)
Cu1—N3—N4—C5	−165.92 (13)	C2—S1—C5—N4	0.82 (15)
Cu1—N3—C2—S1	166.41 (9)	C2—S1—C5—C6	−179.44 (17)
Cu1—N3—C2—N2	−14.2 (3)	C2—N2—C7—C8	52.9 (3)
Cu1^i—N4—C5—S1	162.81 (10)	C2—N3—N4—Cu1^i	−164.39 (13)
Cu1^i—N4—C5—C6	−16.9 (3)	C2—N3—N4—C5	1.9 (2)
N2—C7—C8—Cu1	−70.33 (19)	C5—S1—C2—N2	−179.15 (17)
N2—C7—C8—C9	−149.0 (2)	C5—S1—C2—N3	0.30 (15)
N3—N4—C5—S1	−1.7 (2)	C7—N2—C2—S1	175.35 (14)
N3—N4—C5—C6	178.57 (17)	C7—N2—C2—N3	−4.0 (3)
N4—N3—C2—S1	−1.3 (2)	C7—C8—C9—Cu1	97.74 (19)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^ii	0.80 (3)	2.32 (3)	3.034 (3)	150 (2)
N2—H2···O2^ii	0.80 (3)	2.24 (3)	2.970 (3)	153 (2)
N2—H2···N1^ii	0.80 (3)	2.63 (3)	3.426 (3)	172 (2)
C6—H6B···O2^iii	0.98	2.44	3.391 (3)	164
C6—H6C···O3^iv	0.98	2.31	3.142 (3)	143
C7—H7A···O3^v	0.99	2.45	3.415 (3)	164
C8—H8···O3	0.95	2.44	3.350 (3)	160
C8—H8···N1	0.95	2.68	3.391 (3)	133

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

(2) Bis[µ-5-methyl-N-(prop-2-en-1-yl)-1,3,4-thiadiazol-2-amine]bis[(tetrafluoroborato)copper(I)]

Crystal data

[Cu2(BF4)2(C6H9N3S)2]	Z = 1
Mr = 611.14	F(000) = 304
Triclinic, P1	Dx = 2.011 Mg m^−3
a = 7.754 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.965 (3) Å	Cell parameters from 6709 reflections
c = 10.372 (4) Å	θ = 3.0–38.4°
α = 67.57 (3)°	µ = 2.40 mm^−1
β = 89.99 (3)°	T = 100 K
γ = 61.07 (3)°	Block, clear colourless
V = 504.6 (4) Å^3	0.44 × 0.23 × 0.18 mm

Data collection

Rigaku Xcalibur Onyx diffractometer	4784 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4163 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
Detector resolution: 8.1956 pixels mm^-1	θmax = 38.5°, θmin = 3.0°
ω and π scans	h = −12→10
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	k = −13→13
Tmin = 0.498, Tmax = 0.711	l = −16→18
8712 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.022	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.061	w = 1/[σ^2(Fo^2) + (0.037P)^2 + 0.007P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
4784 reflections	Δρmax = 0.56 e Å^−3
149 parameters	Δρmin = −0.51 e Å^−3
0 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.40020 (2)	0.60430 (2)	0.31778 (2)	0.01224 (4)
S1	0.81824 (4)	−0.10490 (3)	0.52116 (2)	0.01379 (5)
N2	0.52780 (14)	0.17402 (13)	0.27870 (9)	0.01616 (15)
H2	0.574 (2)	0.071 (2)	0.2533 (17)	0.019*
N3	0.56082 (13)	0.29189 (12)	0.44914 (8)	0.01262 (13)
N4	0.67773 (12)	0.20945 (12)	0.58491 (8)	0.01243 (13)
C2	0.61534 (15)	0.14328 (14)	0.40314 (10)	0.01299 (15)
C5	0.81566 (15)	0.00725 (14)	0.63542 (10)	0.01316 (15)
C6	0.96188 (16)	−0.12310 (15)	0.77723 (10)	0.01759 (18)
H6A	1.0653	−0.2615	0.7825	0.026*
H6B	0.8898	−0.1449	0.8537	0.026*
H6C	1.0266	−0.0486	0.7887	0.026*
C7	0.35674 (15)	0.37956 (15)	0.17735 (10)	0.01552 (16)
H7A	0.2370	0.4161	0.2201	0.019*
H7B	0.3234	0.3696	0.0894	0.019*
C8	0.40423 (15)	0.55286 (15)	0.13881 (10)	0.01463 (16)
H8	0.5411	0.5147	0.1408	0.018*
C9	0.26128 (16)	0.76235 (15)	0.10109 (10)	0.01708 (17)
H9A	0.1232	0.8052	0.0982	0.020*
H9B	0.3003	0.8647	0.0779	0.020*
F1	0.77274 (12)	0.53404 (11)	0.31378 (8)	0.02589 (15)
F2	0.58069 (11)	0.88916 (10)	0.16685 (8)	0.02546 (15)
F3	0.90363 (12)	0.74658 (12)	0.27778 (8)	0.02710 (15)
F4	0.84274 (12)	0.66901 (12)	0.09893 (8)	0.02720 (15)
B1	0.77701 (18)	0.70789 (18)	0.21457 (12)	0.01625 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01465 (6)	0.01181 (5)	0.00981 (5)	−0.00615 (4)	0.00179 (4)	−0.00534 (4)
S1	0.01564 (11)	0.01145 (9)	0.01421 (9)	−0.00626 (8)	0.00329 (8)	−0.00664 (7)
N2	0.0183 (4)	0.0156 (3)	0.0151 (3)	−0.0070 (3)	0.0018 (3)	−0.0096 (3)
N3	0.0145 (3)	0.0130 (3)	0.0110 (3)	−0.0068 (3)	0.0030 (3)	−0.0064 (2)
N4	0.0141 (3)	0.0123 (3)	0.0109 (3)	−0.0068 (3)	0.0027 (3)	−0.0052 (2)
C2	0.0140 (4)	0.0136 (3)	0.0136 (3)	−0.0077 (3)	0.0043 (3)	−0.0072 (3)
C5	0.0147 (4)	0.0131 (3)	0.0124 (3)	−0.0074 (3)	0.0037 (3)	−0.0060 (3)
C6	0.0192 (5)	0.0134 (4)	0.0152 (4)	−0.0057 (3)	−0.0005 (3)	−0.0053 (3)
C7	0.0170 (4)	0.0175 (4)	0.0135 (3)	−0.0095 (3)	0.0012 (3)	−0.0075 (3)
C8	0.0166 (4)	0.0180 (4)	0.0111 (3)	−0.0095 (3)	0.0035 (3)	−0.0075 (3)
C9	0.0207 (5)	0.0170 (4)	0.0116 (3)	−0.0092 (3)	0.0004 (3)	−0.0053 (3)
F1	0.0294 (4)	0.0217 (3)	0.0270 (3)	−0.0169 (3)	0.0054 (3)	−0.0063 (3)
F2	0.0218 (3)	0.0197 (3)	0.0337 (4)	−0.0066 (3)	0.0039 (3)	−0.0163 (3)
F3	0.0303 (4)	0.0363 (4)	0.0294 (4)	−0.0246 (3)	0.0069 (3)	−0.0183 (3)
F4	0.0300 (4)	0.0323 (4)	0.0234 (3)	−0.0140 (3)	0.0106 (3)	−0.0191 (3)
B1	0.0183 (5)	0.0171 (4)	0.0183 (4)	−0.0105 (4)	0.0054 (4)	−0.0106 (4)

Geometric parameters (Å, º)

Cu1—N3	2.0036 (15)	C6—H6A	0.9800
Cu1—N4^i	1.9646 (11)	C6—H6B	0.9800
Cu1—C8	2.0451 (12)	C6—H6C	0.9800
Cu1—C9	2.0799 (15)	C7—H7A	0.9900
S1—C2	1.7397 (16)	C7—H7B	0.9900
S1—C5	1.7301 (11)	C7—C8	1.5072 (15)
N2—H2	0.869 (15)	C8—H8	0.9500
N2—C2	1.3361 (13)	C8—C9	1.3706 (16)
N2—C7	1.4597 (16)	C9—H9A	0.9500
N3—N4	1.3983 (13)	C9—H9B	0.9500
N3—C2	1.3244 (13)	F1—B1	1.3908 (15)
N4—Cu1^i	1.9645 (11)	F2—B1	1.4055 (16)
N4—C5	1.3046 (14)	F3—B1	1.3914 (14)
C5—C6	1.4910 (16)	F4—B1	1.3873 (14)
N3—Cu1—C8	92.88 (5)	H6A—C6—H6C	109.5
N3—Cu1—C9	130.27 (5)	H6B—C6—H6C	109.5
N4^i—Cu1—N3	114.54 (5)	N2—C7—H7A	109.4
N4^i—Cu1—C8	152.58 (4)	N2—C7—H7B	109.4
N4^i—Cu1—C9	114.25 (5)	N2—C7—C8	111.16 (9)
C8—Cu1—C9	38.80 (5)	H7A—C7—H7B	108.0
C5—S1—C2	87.64 (6)	C8—C7—H7A	109.4
C2—N2—H2	120.4 (10)	C8—C7—H7B	109.4
C2—N2—C7	122.90 (9)	Cu1—C8—H8	93.4
C7—N2—H2	116.6 (10)	C7—C8—Cu1	104.65 (7)
N4—N3—Cu1	122.78 (7)	C7—C8—H8	118.1
C2—N3—Cu1	122.80 (7)	C9—C8—Cu1	71.97 (7)
C2—N3—N4	111.58 (9)	C9—C8—C7	123.77 (10)
N3—N4—Cu1^i	117.92 (7)	C9—C8—H8	118.1
C5—N4—Cu1^i	128.40 (7)	Cu1—C9—H9A	105.1
C5—N4—N3	113.33 (9)	Cu1—C9—H9B	95.4
N2—C2—S1	121.34 (8)	C8—C9—Cu1	69.23 (7)
N3—C2—S1	113.61 (8)	C8—C9—H9A	120.0
N3—C2—N2	125.05 (9)	C8—C9—H9B	120.0
N4—C5—S1	113.80 (8)	H9A—C9—H9B	120.0
N4—C5—C6	125.29 (9)	F1—B1—F2	108.91 (10)
C6—C5—S1	120.91 (8)	F1—B1—F3	110.33 (10)
C5—C6—H6A	109.5	F3—B1—F2	108.25 (9)
C5—C6—H6B	109.5	F4—B1—F1	109.58 (9)
C5—C6—H6C	109.5	F4—B1—F2	109.39 (10)
H6A—C6—H6B	109.5	F4—B1—F3	110.34 (10)
Cu1—N3—N4—Cu1^i	25.80 (10)	N4—N3—C2—N2	178.42 (9)
Cu1—N3—N4—C5	−160.39 (7)	C2—S1—C5—N4	−1.04 (8)
Cu1—N3—C2—S1	159.58 (5)	C2—S1—C5—C6	179.13 (9)
Cu1—N3—C2—N2	−20.20 (14)	C2—N2—C7—C8	54.40 (13)
Cu1^i—N4—C5—S1	173.28 (5)	C2—N3—N4—Cu1^i	−172.82 (7)
Cu1^i—N4—C5—C6	−6.89 (15)	C2—N3—N4—C5	1.00 (11)
N2—C7—C8—Cu1	−72.62 (9)	C5—S1—C2—N2	−178.59 (9)
N2—C7—C8—C9	−150.50 (9)	C5—S1—C2—N3	1.63 (8)
N3—N4—C5—S1	0.26 (11)	C7—N2—C2—S1	179.68 (8)
N3—N4—C5—C6	−179.91 (9)	C7—N2—C2—N3	−0.55 (16)
N4—N3—C2—S1	−1.80 (10)	C7—C8—C9—Cu1	95.87 (9)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···F2^ii	0.87 (2)	1.95 (2)	2.7874 (14)	160 (1)
N2—H2···F3^ii	0.87 (2)	2.53 (2)	3.242 (2)	140 (1)
C6—H6A···F1^iii	0.98	2.51	3.4175 (19)	154
C6—H6B···F4^iv	0.98	2.54	3.4628 (19)	157
C6—H6C···F3^v	0.98	2.56	3.4824 (18)	157
C7—H7B···F4^vi	0.99	2.53	3.4900 (17)	163
C8—H8···F1	0.95	2.64	3.2956 (18)	127

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

(3) µ-Aqua-bis{µ-5-[(prop-2-en-1-yl)sulfanyl]-1,3,4-thiadiazol-2-amine}bis[nitratocopper(I)]

Crystal data

[Cu2(NO3)2(C5H7N3S2)2(H2O)]	F(000) = 1240
Mr = 615.63	Dx = 2.014 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.379 (3) Å	Cell parameters from 3740 reflections
b = 18.780 (5) Å	θ = 2.8–32.2°
c = 14.702 (4) Å	µ = 2.56 mm^−1
β = 94.82 (3)°	T = 100 K
V = 2030.2 (11) Å^3	Block, clear colourless
Z = 4	0.3 × 0.18 × 0.13 mm

Data collection

Rigaku Xcalibur Ruby diffractometer	6647 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4618 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 10.3456 pixels mm^-1	θmax = 32.3°, θmin = 2.8°
ω scans	h = −7→11
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	k = −28→16
Tmin = 0.577, Tmax = 0.776	l = −21→17
11883 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.115	w = 1/[σ^2(Fo^2) + (0.046P)^2 + 0.307P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
6647 reflections	Δρmax = 0.68 e Å^−3
346 parameters	Δρmin = −0.70 e Å^−3
0 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1A	0.6758 (2)	0.54841 (9)	0.28897 (8)	0.0254 (2)	0.765 (6)
Cu1B	0.6292 (7)	0.5656 (2)	0.2979 (3)	0.0226 (6)	0.235 (6)
Cu2A	0.4280 (2)	0.67847 (8)	0.15853 (14)	0.0280 (2)	0.794 (7)
Cu2B	0.4045 (8)	0.6712 (3)	0.1832 (4)	0.0222 (7)	0.206 (7)
S11	0.88194 (11)	0.77496 (4)	0.33415 (5)	0.03405 (17)
S12A	0.9467 (2)	0.64460 (14)	0.45789 (9)	0.0351 (4)	0.765 (6)
S12B	0.9288 (9)	0.6667 (3)	0.4581 (4)	0.0348 (14)*	0.235 (6)
S21	0.32163 (10)	0.45394 (3)	0.06167 (5)	0.02596 (15)
S22	0.09397 (10)	0.58465 (4)	0.02178 (5)	0.02980 (16)
O1	0.3426 (4)	0.61593 (15)	0.31989 (18)	0.0561 (8)
H1A	0.262 (7)	0.578 (3)	0.323 (3)	0.084*
H1B	0.326 (6)	0.647 (2)	0.373 (3)	0.084*
O21	0.5703 (3)	0.69954 (12)	0.00949 (15)	0.0405 (5)
O22	0.4733 (3)	0.80878 (11)	0.00474 (15)	0.0381 (5)
O23	0.4103 (4)	0.73874 (12)	−0.10980 (15)	0.0468 (6)
N2	0.4863 (4)	0.74886 (13)	−0.03207 (16)	0.0321 (6)
N12	0.6913 (4)	0.81795 (15)	0.17938 (18)	0.0358 (6)
H12A	0.750 (5)	0.8612 (18)	0.189 (2)	0.043*
H12B	0.624 (5)	0.8080 (19)	0.132 (2)	0.043*
N13	0.7304 (3)	0.65507 (13)	0.29752 (15)	0.0280 (5)
N14	0.6605 (3)	0.70080 (12)	0.22911 (15)	0.0264 (5)
N22	0.6172 (4)	0.40718 (13)	0.16391 (18)	0.0301 (5)
H22A	0.717 (5)	0.4157 (17)	0.196 (2)	0.036*
H22B	0.585 (5)	0.3677 (17)	0.146 (2)	0.036*
N23	0.4050 (3)	0.57409 (11)	0.13393 (15)	0.0231 (4)
N24	0.5332 (3)	0.52684 (12)	0.17360 (14)	0.0238 (4)
C12	0.8423 (4)	0.68604 (17)	0.35797 (19)	0.0318 (6)
C15	0.7307 (4)	0.76500 (15)	0.23714 (19)	0.0287 (6)
C17A	0.7803 (6)	0.5763 (2)	0.4787 (3)	0.0313 (10)	0.765 (6)
H17A	0.8043	0.5588	0.5421	0.038*	0.765 (6)
H17B	0.6575	0.5979	0.4732	0.038*	0.765 (6)
C17B	0.8942 (19)	0.5707 (7)	0.4540 (9)	0.033 (3)*	0.235 (6)
H17C	0.9706	0.5504	0.4082	0.040*	0.235 (6)
H17D	0.9375	0.5505	0.5141	0.040*	0.235 (6)
C18A	0.7815 (6)	0.5150 (2)	0.4155 (2)	0.0320 (10)	0.765 (6)
H18A	0.8945	0.5027	0.3932	0.038*	0.765 (6)
C18B	0.7029 (16)	0.5471 (6)	0.4311 (7)	0.019 (2)*	0.235 (6)
H18B	0.6054	0.5772	0.4447	0.023*	0.235 (6)
C19A	0.6328 (11)	0.4744 (4)	0.3864 (4)	0.0318 (13)	0.765 (6)
H19A	0.5172	0.4850	0.4071	0.038*	0.765 (6)
H19B	0.6456	0.4359	0.3456	0.038*	0.765 (6)
C19B	0.669 (4)	0.4866 (14)	0.3933 (19)	0.038 (7)*	0.235 (6)
H19C	0.7658	0.4562	0.3796	0.045*	0.235 (6)
H19D	0.5463	0.4720	0.3791	0.045*	0.235 (6)
C22	0.2827 (4)	0.54435 (13)	0.07774 (17)	0.0227 (5)
C25	0.5102 (4)	0.46214 (14)	0.14025 (18)	0.0247 (5)
C27A	0.0483 (5)	0.65593 (18)	0.1045 (3)	0.0288 (9)	0.794 (7)
H27A	−0.0763	0.6745	0.0898	0.035*	0.794 (7)
H27B	0.0539	0.6353	0.1667	0.035*	0.794 (7)
C27B	0.0940 (17)	0.6732 (6)	0.0521 (8)	0.020 (3)*	0.206 (7)
H27C	0.1816	0.6983	0.0159	0.024*	0.206 (7)
H27D	−0.0281	0.6927	0.0336	0.024*	0.206 (7)
C28A	0.1794 (5)	0.71578 (19)	0.1038 (3)	0.0298 (9)	0.794 (7)
H28A	0.2256	0.7269	0.0471	0.036*	0.794 (7)
C28B	0.1379 (17)	0.6907 (7)	0.1468 (9)	0.021 (3)*	0.206 (7)
H28B	0.1072	0.6591	0.1936	0.025*	0.206 (7)
C29A	0.2400 (13)	0.7564 (4)	0.1775 (7)	0.0273 (14)	0.794 (7)
H29A	0.1975	0.7472	0.2356	0.033*	0.794 (7)
H29B	0.3244	0.7938	0.1705	0.033*	0.794 (7)
C29B	0.220 (6)	0.750 (2)	0.167 (3)	0.047 (13)*	0.206 (7)
H29C	0.2503	0.7817	0.1197	0.057*	0.206 (7)
H29D	0.2501	0.7629	0.2291	0.057*	0.206 (7)
O11	0.9655 (3)	0.52030 (11)	0.22839 (16)	0.0409 (5)
O12	0.9797 (3)	0.40739 (11)	0.25601 (18)	0.0424 (6)
O13	1.2039 (3)	0.47483 (12)	0.30109 (17)	0.0440 (6)
N1	1.0495 (3)	0.46788 (13)	0.26096 (17)	0.0291 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1A	0.0284 (5)	0.0246 (5)	0.0226 (3)	−0.0032 (3)	−0.0014 (3)	0.0019 (3)
Cu1B	0.0236 (14)	0.0197 (12)	0.0243 (10)	0.0019 (9)	0.0010 (9)	0.0013 (8)
Cu2A	0.0269 (4)	0.0242 (4)	0.0322 (6)	−0.0001 (3)	−0.0019 (4)	−0.0069 (4)
Cu2B	0.0211 (14)	0.0241 (13)	0.0210 (17)	0.0010 (10)	0.0004 (11)	−0.0033 (12)
S11	0.0330 (4)	0.0402 (4)	0.0290 (3)	−0.0121 (3)	0.0033 (3)	−0.0092 (3)
S12A	0.0342 (7)	0.0434 (10)	0.0260 (5)	−0.0039 (7)	−0.0083 (4)	0.0001 (6)
S21	0.0265 (3)	0.0213 (3)	0.0293 (3)	0.0002 (3)	−0.0021 (3)	−0.0018 (2)
S22	0.0271 (4)	0.0277 (3)	0.0331 (4)	0.0004 (3)	−0.0067 (3)	−0.0001 (3)
O1	0.0697 (19)	0.0507 (15)	0.0515 (15)	−0.0236 (14)	0.0268 (14)	−0.0185 (12)
O21	0.0516 (15)	0.0365 (12)	0.0335 (11)	0.0071 (11)	0.0034 (10)	0.0053 (9)
O22	0.0520 (14)	0.0264 (10)	0.0363 (11)	−0.0083 (10)	0.0056 (10)	−0.0030 (9)
O23	0.0761 (19)	0.0342 (12)	0.0280 (11)	−0.0094 (12)	−0.0078 (11)	0.0015 (9)
N2	0.0456 (16)	0.0268 (12)	0.0243 (11)	−0.0089 (11)	0.0054 (10)	0.0010 (9)
N12	0.0432 (16)	0.0323 (13)	0.0317 (13)	−0.0092 (12)	0.0027 (11)	−0.0041 (11)
N13	0.0279 (12)	0.0348 (12)	0.0213 (10)	−0.0054 (10)	0.0026 (9)	−0.0019 (9)
N14	0.0284 (12)	0.0280 (11)	0.0230 (10)	−0.0042 (10)	0.0036 (9)	−0.0031 (9)
N22	0.0272 (13)	0.0253 (12)	0.0369 (13)	0.0026 (10)	−0.0036 (10)	−0.0005 (10)
N23	0.0221 (11)	0.0249 (11)	0.0222 (10)	0.0015 (9)	0.0009 (8)	−0.0007 (8)
N24	0.0241 (11)	0.0251 (11)	0.0217 (10)	0.0017 (9)	−0.0002 (8)	−0.0004 (8)
C12	0.0288 (14)	0.0427 (17)	0.0242 (13)	−0.0068 (13)	0.0035 (11)	−0.0044 (12)
C15	0.0289 (14)	0.0322 (14)	0.0261 (13)	−0.0061 (12)	0.0075 (11)	−0.0064 (11)
C17A	0.035 (2)	0.034 (2)	0.0250 (18)	0.0057 (17)	0.0033 (15)	0.0022 (15)
C18A	0.037 (2)	0.036 (2)	0.0227 (17)	0.0091 (19)	0.0003 (15)	0.0018 (15)
C19A	0.048 (4)	0.024 (2)	0.022 (2)	−0.003 (3)	−0.001 (2)	0.0059 (17)
C22	0.0237 (13)	0.0209 (11)	0.0233 (12)	−0.0004 (10)	0.0005 (9)	−0.0007 (9)
C25	0.0242 (13)	0.0254 (12)	0.0249 (12)	0.0006 (11)	0.0037 (10)	0.0017 (10)
C27A	0.0245 (17)	0.0233 (16)	0.039 (2)	0.0042 (14)	0.0035 (15)	0.0003 (14)
C28A	0.0298 (19)	0.0235 (17)	0.037 (2)	0.0039 (15)	0.0055 (15)	0.0001 (15)
C29A	0.027 (3)	0.019 (2)	0.036 (3)	0.0021 (18)	0.003 (2)	−0.008 (2)
O11	0.0340 (12)	0.0339 (11)	0.0556 (14)	0.0059 (10)	0.0085 (10)	0.0185 (10)
O12	0.0344 (12)	0.0255 (10)	0.0654 (16)	0.0004 (9)	−0.0067 (11)	0.0016 (10)
O13	0.0293 (12)	0.0375 (12)	0.0633 (16)	−0.0031 (10)	−0.0071 (11)	0.0079 (11)
N1	0.0244 (12)	0.0280 (12)	0.0355 (13)	0.0025 (10)	0.0068 (10)	0.0038 (10)

Geometric parameters (Å, º)

Cu1A—N13	2.045 (3)	N13—C12	1.299 (4)
Cu1A—N24	1.962 (2)	N14—C15	1.314 (4)
Cu1A—C18A	2.054 (4)	N22—H22A	0.85 (4)
Cu1A—C19A	2.039 (6)	N22—H22B	0.82 (3)
Cu1B—Cu2B	3.009 (7)	N22—C25	1.328 (4)
Cu1B—O1	2.363 (7)	N23—N24	1.389 (3)
Cu1B—N13	1.838 (4)	N23—C22	1.297 (3)
Cu1B—N24	2.038 (4)	N24—C25	1.316 (3)
Cu1B—C18B	2.019 (11)	C17A—H17A	0.9900
Cu1B—C19B	2.05 (3)	C17A—H17B	0.9900
Cu2A—N14	1.974 (3)	C17A—C18A	1.480 (6)
Cu2A—N23	1.998 (3)	C17B—H17C	0.9900
Cu2A—C28A	2.062 (4)	C17B—H17D	0.9900
Cu2A—C29A	2.052 (8)	C17B—C18B	1.490 (17)
Cu2B—O1	2.341 (7)	C18A—H18A	0.9500
Cu2B—N14	2.029 (6)	C18A—C19A	1.374 (9)
Cu2B—N23	1.962 (6)	C18B—H18B	0.9500
Cu2B—C28B	2.028 (13)	C18B—C19B	1.28 (3)
Cu2B—C29B	2.02 (5)	C19A—H19A	0.9500
S11—C12	1.736 (3)	C19A—H19B	0.9500
S11—C15	1.746 (3)	C19B—H19C	0.9500
S12A—C12	1.779 (3)	C19B—H19D	0.9500
S12A—C17A	1.819 (4)	C27A—H27A	0.9900
S12B—C12	1.596 (7)	C27A—H27B	0.9900
S12B—C17B	1.823 (14)	C27A—C28A	1.484 (5)
S21—C22	1.741 (3)	C27B—H27C	0.9900
S21—C25	1.739 (3)	C27B—H27D	0.9900
S22—C22	1.731 (3)	C27B—C28B	1.441 (17)
S22—C27A	1.859 (4)	C28A—H28A	0.9500
S22—C27B	1.721 (12)	C28A—C29A	1.369 (11)
O1—H1A	0.93 (5)	C28B—H28B	0.9500
O1—H1B	0.99 (5)	C28B—C29B	1.30 (4)
O21—N2	1.246 (3)	C29A—H29A	0.9500
O22—N2	1.256 (3)	C29A—H29B	0.9500
O23—N2	1.244 (3)	C29B—H29C	0.9500
N12—H12A	0.93 (4)	C29B—H29D	0.9500
N12—H12B	0.84 (4)	O11—N1	1.238 (3)
N12—C15	1.324 (4)	O12—N1	1.247 (3)
N13—N14	1.389 (3)	O13—N1	1.245 (3)
N13—Cu1A—C18A	100.70 (14)	N13—C12—S12A	125.1 (2)
N24—Cu1A—N13	110.12 (11)	N13—C12—S12B	135.4 (3)
N24—Cu1A—C18A	148.79 (15)	N12—C15—S11	122.3 (2)
N24—Cu1A—C19A	111.3 (2)	N14—C15—S11	113.1 (2)
C19A—Cu1A—N13	131.7 (2)	N14—C15—N12	124.6 (3)
C19A—Cu1A—C18A	39.2 (2)	S12A—C17A—H17A	108.8
O1—Cu1B—Cu2B	49.91 (17)	S12A—C17A—H17B	108.8
N13—Cu1B—Cu2B	66.50 (19)	H17A—C17A—H17B	107.7
N13—Cu1B—O1	90.2 (2)	C18A—C17A—S12A	113.8 (3)
N13—Cu1B—N24	115.78 (19)	C18A—C17A—H17A	108.8
N13—Cu1B—C18B	94.8 (3)	C18A—C17A—H17B	108.8
N13—Cu1B—C19B	129.1 (7)	S12B—C17B—H17C	108.4
N24—Cu1B—Cu2B	66.39 (16)	S12B—C17B—H17D	108.4
N24—Cu1B—O1	91.02 (19)	H17C—C17B—H17D	107.5
N24—Cu1B—C19B	112.0 (7)	C18B—C17B—S12B	115.4 (10)
C18B—Cu1B—Cu2B	138.4 (4)	C18B—C17B—H17C	108.4
C18B—Cu1B—O1	96.1 (4)	C18B—C17B—H17D	108.4
C18B—Cu1B—N24	148.6 (4)	Cu1A—C18A—H18A	92.3
C18B—Cu1B—C19B	36.7 (7)	C17A—C18A—Cu1A	108.0 (3)
C19B—Cu1B—Cu2B	154.4 (8)	C17A—C18A—H18A	117.3
C19B—Cu1B—O1	105.9 (8)	C19A—C18A—Cu1A	69.8 (3)
N14—Cu2A—N23	111.13 (12)	C19A—C18A—C17A	125.4 (5)
N14—Cu2A—C28A	146.92 (15)	C19A—C18A—H18A	117.3
N14—Cu2A—C29A	110.2 (3)	Cu1B—C18B—H18B	87.4
N23—Cu2A—C28A	101.74 (14)	C17B—C18B—Cu1B	109.9 (8)
N23—Cu2A—C29A	132.6 (3)	C17B—C18B—H18B	119.7
C29A—Cu2A—C28A	38.9 (3)	C19B—C18B—Cu1B	72.8 (14)
O1—Cu2B—Cu1B	50.57 (17)	C19B—C18B—C17B	120.6 (17)
N14—Cu2B—Cu1B	62.64 (17)	C19B—C18B—H18B	119.7
N14—Cu2B—O1	94.6 (2)	Cu1A—C19A—H19A	106.2
N23—Cu2B—Cu1B	64.95 (19)	Cu1A—C19A—H19B	92.7
N23—Cu2B—O1	84.9 (3)	C18A—C19A—Cu1A	71.0 (3)
N23—Cu2B—N14	110.3 (3)	C18A—C19A—H19A	120.0
N23—Cu2B—C28B	95.9 (4)	C18A—C19A—H19B	120.0
N23—Cu2B—C29B	131.6 (13)	H19A—C19A—H19B	120.0
C28B—Cu2B—Cu1B	138.0 (5)	Cu1B—C19B—H19C	110.8
C28B—Cu2B—O1	93.0 (4)	Cu1B—C19B—H19D	88.8
C28B—Cu2B—N14	153.3 (5)	C18B—C19B—Cu1B	70.4 (13)
C29B—Cu2B—Cu1B	152.5 (15)	C18B—C19B—H19C	120.0
C29B—Cu2B—O1	104.5 (15)	C18B—C19B—H19D	120.0
C29B—Cu2B—N14	115.9 (13)	H19C—C19B—H19D	120.0
C29B—Cu2B—C28B	37.4 (13)	S22—C22—S21	119.80 (15)
C12—S11—C15	87.41 (14)	N23—C22—S21	113.1 (2)
C12—S12A—C17A	101.29 (17)	N23—C22—S22	127.1 (2)
C12—S12B—C17B	98.6 (5)	N22—C25—S21	122.0 (2)
C25—S21—C22	87.44 (13)	N24—C25—S21	113.6 (2)
C22—S22—C27A	100.77 (15)	N24—C25—N22	124.4 (3)
C27B—S22—C22	108.4 (4)	S22—C27A—H27A	109.0
Cu1B—O1—H1A	107 (3)	S22—C27A—H27B	109.0
Cu1B—O1—H1B	121 (3)	H27A—C27A—H27B	107.8
Cu2B—O1—Cu1B	79.52 (18)	C28A—C27A—S22	112.7 (3)
Cu2B—O1—H1A	124 (3)	C28A—C27A—H27A	109.0
Cu2B—O1—H1B	118 (3)	C28A—C27A—H27B	109.0
H1A—O1—H1B	106 (4)	S22—C27B—H27C	107.9
O21—N2—O22	120.5 (2)	S22—C27B—H27D	107.9
O23—N2—O21	120.3 (2)	H27C—C27B—H27D	107.2
O23—N2—O22	119.2 (3)	C28B—C27B—S22	117.8 (10)
H12A—N12—H12B	124 (3)	C28B—C27B—H27C	107.9
C15—N12—H12A	119 (2)	C28B—C27B—H27D	107.9
C15—N12—H12B	116 (2)	Cu2A—C28A—H28A	92.5
N14—N13—Cu1A	120.13 (17)	C27A—C28A—Cu2A	107.4 (2)
N14—N13—Cu1B	116.2 (2)	C27A—C28A—H28A	117.0
C12—N13—Cu1A	126.3 (2)	C29A—C28A—Cu2A	70.2 (4)
C12—N13—Cu1B	130.0 (2)	C29A—C28A—C27A	125.9 (5)
C12—N13—N14	113.3 (2)	C29A—C28A—H28A	117.0
N13—N14—Cu2A	120.19 (18)	Cu2B—C28B—H28B	88.9
N13—N14—Cu2B	110.5 (2)	C27B—C28B—Cu2B	110.3 (9)
C15—N14—Cu2A	124.1 (2)	C27B—C28B—H28B	120.6
C15—N14—Cu2B	129.1 (3)	C29B—C28B—Cu2B	71 (2)
C15—N14—N13	112.5 (2)	C29B—C28B—C27B	119 (3)
H22A—N22—H22B	124 (3)	C29B—C28B—H28B	120.6
C25—N22—H22A	118 (2)	Cu2A—C29A—H29A	105.7
C25—N22—H22B	118 (2)	Cu2A—C29A—H29B	93.2
N24—N23—Cu2A	120.41 (17)	C28A—C29A—Cu2A	71.0 (4)
N24—N23—Cu2B	117.4 (2)	C28A—C29A—H29A	120.0
C22—N23—Cu2A	125.57 (19)	C28A—C29A—H29B	120.0
C22—N23—Cu2B	127.8 (2)	H29A—C29A—H29B	120.0
C22—N23—N24	113.9 (2)	Cu2B—C29B—H29C	110.2
N23—N24—Cu1A	121.87 (17)	Cu2B—C29B—H29D	88.2
N23—N24—Cu1B	108.7 (2)	C28B—C29B—Cu2B	72 (2)
C25—N24—Cu1A	123.76 (19)	C28B—C29B—H29C	120.0
C25—N24—Cu1B	133.5 (2)	C28B—C29B—H29D	120.0
C25—N24—N23	111.8 (2)	H29C—C29B—H29D	120.0
S11—C12—S12A	121.24 (18)	O11—N1—O12	120.7 (3)
S12B—C12—S11	110.1 (3)	O11—N1—O13	120.6 (3)
N13—C12—S11	113.6 (2)	O13—N1—O12	118.7 (2)
Cu1A—N13—N14—Cu2A	29.4 (3)	N23—N24—C25—S21	−3.1 (3)
Cu1A—N13—N14—C15	−169.9 (2)	N23—N24—C25—N22	177.7 (3)
Cu1A—N13—C12—S11	170.37 (15)	N24—Cu1B—N13—N14	30.0 (4)
Cu1A—N13—C12—S12A	−10.5 (4)	N24—Cu1B—N13—C12	−159.7 (3)
Cu1A—N24—C25—S21	159.03 (15)	N24—N23—C22—S21	−4.0 (3)
Cu1A—N24—C25—N22	−20.2 (4)	N24—N23—C22—S22	175.27 (19)
Cu1B—N13—N14—Cu2B	23.5 (3)	C12—S11—C15—N12	−179.7 (3)
Cu1B—N13—N14—C15	175.6 (3)	C12—S11—C15—N14	1.2 (2)
Cu1B—N13—C12—S11	−173.2 (3)	C12—S12A—C17A—C18A	75.0 (3)
Cu1B—N13—C12—S12B	−5.7 (6)	C12—S12B—C17B—C18B	−55.7 (10)
Cu1B—N24—C25—S21	145.9 (3)	C12—N13—N14—Cu2A	−157.0 (2)
Cu1B—N24—C25—N22	−33.3 (5)	C12—N13—N14—Cu2B	−148.3 (3)
Cu2A—N14—C15—S11	156.82 (16)	C12—N13—N14—C15	3.7 (3)
Cu2A—N14—C15—N12	−22.3 (4)	C15—S11—C12—S12A	−178.2 (2)
Cu2A—N23—N24—Cu1A	26.1 (3)	C15—S11—C12—S12B	−169.8 (3)
Cu2A—N23—N24—C25	−171.39 (19)	C15—S11—C12—N13	0.9 (2)
Cu2A—N23—C22—S21	171.75 (15)	C17A—S12A—C12—S11	151.7 (2)
Cu2A—N23—C22—S22	−9.0 (4)	C17A—S12A—C12—N13	−27.3 (3)
Cu2B—Cu1B—N13—N14	−16.0 (2)	C17A—C18A—C19A—Cu1A	98.2 (4)
Cu2B—Cu1B—N13—C12	154.3 (3)	C17B—S12B—C12—S11	−172.0 (5)
Cu2B—N14—C15—S11	142.6 (3)	C17B—S12B—C12—N13	20.1 (8)
Cu2B—N14—C15—N12	−36.5 (5)	C17B—C18B—C19B—Cu1B	−103.3 (13)
Cu2B—N23—N24—Cu1B	17.8 (3)	C18B—Cu1B—N13—N14	−157.4 (4)
Cu2B—N23—N24—C25	174.6 (3)	C18B—Cu1B—N13—C12	12.8 (5)
Cu2B—N23—C22—S21	−172.7 (3)	C19B—Cu1B—N13—N14	−172.0 (11)
Cu2B—N23—C22—S22	6.5 (4)	C19B—Cu1B—N13—C12	−1.8 (12)
S12A—C17A—C18A—Cu1A	−71.1 (3)	C22—S21—C25—N22	−180.0 (3)
S12A—C17A—C18A—C19A	−148.7 (4)	C22—S21—C25—N24	0.8 (2)
S12B—C17B—C18B—Cu1B	72.2 (11)	C22—S22—C27A—C28A	74.8 (3)
S12B—C17B—C18B—C19B	153.6 (17)	C22—S22—C27B—C28B	−43.0 (11)
S22—C27A—C28A—Cu2A	−69.4 (3)	C22—N23—N24—Cu1A	−157.90 (19)
S22—C27A—C28A—C29A	−147.2 (5)	C22—N23—N24—Cu1B	−152.1 (2)
S22—C27B—C28B—Cu2B	69.6 (12)	C22—N23—N24—C25	4.6 (3)
S22—C27B—C28B—C29B	148 (3)	C25—S21—C22—S22	−177.47 (18)
O1—Cu1B—N13—N14	−61.2 (2)	C25—S21—C22—N23	1.9 (2)
O1—Cu1B—N13—C12	109.0 (3)	C27A—S22—C22—S21	150.13 (18)
N13—N14—C15—S11	−3.0 (3)	C27A—S22—C22—N23	−29.1 (3)
N13—N14—C15—N12	177.9 (3)	C27A—C28A—C29A—Cu2A	97.5 (4)
N14—N13—C12—S11	−2.8 (3)	C27B—S22—C22—S21	179.8 (5)
N14—N13—C12—S12A	176.3 (2)	C27B—S22—C22—N23	0.5 (5)
N14—N13—C12—S12B	164.8 (4)	C27B—C28B—C29B—Cu2B	−103.2 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O13^i	0.93 (5)	2.01 (5)	2.846 (4)	149 (4)
O1—H1B···O22^ii	0.99 (5)	2.29 (5)	3.142 (4)	143 (4)
O1—H1B···O23^ii	0.99 (5)	2.25 (5)	2.946 (3)	126 (3)
O1—H1B···N2^ii	0.99 (5)	2.63 (5)	3.453 (4)	140 (4)
N12—H12A···O12^iii	0.93 (4)	2.26 (4)	3.038 (4)	141 (3)
N12—H12A···O13^iii	0.93 (4)	2.16 (4)	3.053 (4)	161 (3)
N12—H12A···N1^iii	0.93 (4)	2.56 (4)	3.475 (4)	169 (3)
N12—H12B···O22	0.84 (4)	2.09 (4)	2.918 (4)	166 (3)
N22—H22A···O12	0.85 (4)	2.07 (4)	2.895 (4)	163 (3)
N22—H22B···O23^iv	0.82 (3)	2.07 (3)	2.856 (3)	162 (3)
C17A—H17A···O13^v	0.99	2.40	3.369 (5)	167
C17A—H17B···O22^ii	0.99	2.29	3.175 (5)	149
C18A—H18A···O11	0.95	2.54	3.170 (5)	124
C18A—H18A···N1	0.95	2.43	3.258 (5)	146
C18B—H18B···O1	0.95	2.66	3.268 (12)	123
C18B—H18B···O22^ii	0.95	2.54	3.417 (12)	154
C27A—H27B···O11^i	0.99	2.45	3.219 (4)	134
C27B—H27C···N2	0.99	2.59	3.540 (13)	160
C27B—H27D···S11^vi	0.99	3.01	3.581 (12)	118
C27B—H27D···S12B^vi	0.99	2.87	3.487 (14)	121
C28A—H28A···O22	0.95	2.51	3.226 (5)	133
C28A—H28A···N2	0.95	2.37	3.204 (5)	147
C28B—H28B···O1	0.95	2.57	3.175 (13)	122

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

(4) µ-Aqua-(hexafluorosilicato)bis{µ-5-[(prop-2-en-1-yl)sulfanyl]-1,3,4-thiadiazol-2-amine}dicopper(I) acetonitrile hemisolvate dihydrate

Crystal data

[Cu2(SiF6)(C5H7N3S2)2(H2O)]·0.5C2H3N·2H2O	F(000) = 1380
Mr = 688.24	Dx = 1.942 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.899 (4) Å	Cell parameters from 9071 reflections
b = 11.442 (4) Å	θ = 2.9–36.8°
c = 17.678 (5) Å	µ = 2.29 mm^−1
β = 102.04 (3)°	T = 260 K
V = 2353.9 (13) Å^3	Prism, clear colourless
Z = 4	0.52 × 0.17 × 0.09 mm

Data collection

Rigaku Xcalibur Sapphire2 (large Be window) diffractometer	5649 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3717 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
Detector resolution: 8.3359 pixels mm^-1	θmax = 28.0°, θmin = 2.9°
ω scans	h = −15→15
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	k = −15→12
Tmin = 0.452, Tmax = 0.825	l = −23→23
24572 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.087	w = 1/[σ^2(Fo^2) + (0.042P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
5649 reflections	Δρmax = 0.47 e Å^−3
412 parameters	Δρmin = −0.38 e Å^−3
245 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C12	−0.3873 (2)	−1.0688 (2)	0.07294 (15)	0.0321 (6)
C15	−0.4799 (2)	−0.9721 (2)	0.16465 (16)	0.0305 (6)
C22	−0.3561 (3)	−0.5332 (2)	0.05978 (17)	0.0357 (7)
C25	−0.3182 (3)	−0.6313 (2)	−0.05172 (16)	0.0353 (7)
Cu1	−0.26289 (3)	−0.86456 (3)	0.02532 (2)	0.03965 (12)
N12	−0.5426 (2)	−0.9414 (3)	0.21542 (17)	0.0434 (7)
H12A	−0.562 (3)	−0.869 (3)	0.211 (2)	0.052*
H12B	−0.590 (3)	−0.987 (3)	0.230 (2)	0.052*
N13	−0.36247 (19)	−0.9572 (2)	0.08057 (13)	0.0312 (5)
N14	−0.4136 (2)	−0.9013 (2)	0.13454 (13)	0.0320 (5)
N22	−0.2988 (3)	−0.6624 (3)	−0.12019 (16)	0.0537 (8)
H22A	−0.288 (3)	−0.737 (3)	−0.139 (2)	0.064*
H22B	−0.288 (3)	−0.609 (3)	−0.150 (2)	0.064*
N23	−0.3555 (2)	−0.6453 (2)	0.06740 (13)	0.0327 (5)
N24	−0.3312 (2)	−0.7043 (2)	0.00340 (12)	0.0338 (5)
O1	−0.1575 (2)	−0.7886 (2)	0.14329 (14)	0.0535 (6)
H1A	−0.1317	−0.7155	0.1371	0.080*
H1B	−0.0955	−0.8336	0.1620	0.080*
O2	0.0394 (2)	−0.9116 (3)	0.15841 (17)	0.0727 (8)
H2A	0.0713	−0.9607	0.1940	0.109*
H2B	0.0844	−0.8516	0.1583	0.109*
S11	−0.47951 (7)	−1.11532 (6)	0.13071 (4)	0.03665 (18)
S12	−0.33947 (8)	−1.16900 (7)	0.01339 (5)	0.0477 (2)
S21	−0.33098 (8)	−0.48476 (7)	−0.02800 (5)	0.0456 (2)
C17A	−0.2451 (6)	−1.0907 (5)	−0.0365 (4)	0.0449 (17)	0.617 (10)
H17A	−0.1995	−1.1480	−0.0572	0.054*	0.617 (10)
H17B	−0.2926	−1.0510	−0.0802	0.054*	0.617 (10)
C18A	−0.1651 (5)	−1.0035 (4)	0.0071 (4)	0.0404 (17)	0.617 (10)
H18A	−0.1392	−1.0130	0.0601	0.048*	0.617 (10)
C19A	−0.1303 (15)	−0.9146 (16)	−0.0265 (11)	0.054 (5)	0.617 (10)
H19A	−0.1555	−0.9041	−0.0795	0.065*	0.617 (10)
H19B	−0.0800	−0.8611	0.0022	0.065*	0.617 (10)
C27A	−0.4091 (3)	−0.5095 (3)	0.2051 (2)	0.0449 (9)	0.88
H27A	−0.4137	−0.4558	0.2468	0.054*	0.88
H27B	−0.4841	−0.5453	0.1888	0.054*	0.88
C28A	−0.3229 (4)	−0.6045 (3)	0.2367 (2)	0.0415 (9)	0.88
H28A	−0.2485	−0.5999	0.2282	0.050*	0.88
C29A	−0.3530 (8)	−0.6966 (5)	0.2773 (4)	0.0501 (19)	0.88
H29A	−0.4272	−0.7019	0.2860	0.060*	0.88
H29B	−0.2993	−0.7542	0.2962	0.060*	0.88
Cu2A	−0.36197 (18)	−0.7398 (3)	0.1618 (2)	0.0345 (4)	0.88
S22A	−0.37812 (15)	−0.42713 (12)	0.12585 (9)	0.0447 (3)	0.88
C17B	−0.2026 (9)	−1.1074 (8)	0.0012 (7)	0.042 (3)*	0.383 (10)
H17C	−0.1555	−1.0932	0.0521	0.051*	0.383 (10)
H17D	−0.1635	−1.1657	−0.0237	0.051*	0.383 (10)
C18B	−0.2086 (7)	−0.9980 (7)	−0.0438 (6)	0.034 (2)*	0.383 (10)
H18B	−0.2687	−0.9927	−0.0867	0.041*	0.383 (10)
C19B	−0.135 (2)	−0.902 (3)	−0.0297 (15)	0.034 (5)*	0.383 (10)
H19C	−0.0738	−0.9021	0.0124	0.041*	0.383 (10)
H19D	−0.1482	−0.8375	−0.0625	0.041*	0.383 (10)
C27B	−0.298 (3)	−0.510 (3)	0.2236 (19)	0.065 (9)*	0.12
H27C	−0.2242	−0.5457	0.2237	0.078*	0.12
H27D	−0.2866	−0.4536	0.2655	0.078*	0.12
C28B	−0.376 (2)	−0.603 (2)	0.2419 (15)	0.027 (6)*	0.12
H28B	−0.4533	−0.5838	0.2353	0.032*	0.12
C29B	−0.345 (4)	−0.712 (2)	0.267 (3)	0.018 (8)*	0.12
H29C	−0.2684	−0.7356	0.2748	0.022*	0.12
H29D	−0.4001	−0.7645	0.2772	0.022*	0.12
Cu2B	−0.3927 (13)	−0.736 (2)	0.1605 (14)	0.033 (3)	0.12
S22B	−0.3398 (9)	−0.4323 (12)	0.1362 (7)	0.035 (3)*	0.12
F1	−0.62718 (17)	−0.70348 (17)	0.16507 (10)	0.0531 (5)
F2	−0.81507 (19)	−0.63711 (17)	0.27744 (12)	0.0641 (6)
Si1	−0.72257 (8)	−0.67000 (7)	0.21978 (5)	0.0384 (2)
F3A	−0.7269 (6)	−0.8125 (4)	0.2448 (4)	0.0351 (13)*	0.428 (3)
F5A	−0.7214 (8)	−0.5319 (4)	0.1966 (4)	0.0492 (14)*	0.428 (3)
F6A	−0.6161 (5)	−0.6498 (7)	0.2977 (3)	0.0509 (17)*	0.428 (3)
F3B	−0.7584 (8)	−0.8120 (5)	0.2227 (6)	0.0309 (19)*	0.288 (3)
F4B	−0.8174 (7)	−0.6539 (12)	0.1374 (4)	0.055 (3)*	0.288 (3)
F5B	−0.6735 (9)	−0.5315 (5)	0.2150 (6)	0.0382 (18)*	0.288 (3)
F6B	−0.6144 (7)	−0.6912 (11)	0.2998 (4)	0.047 (2)*	0.288 (3)
F3C	−0.7978 (15)	−0.7868 (13)	0.1936 (11)	0.069 (4)*	0.168 (3)
F4C	−0.8099 (11)	−0.5889 (17)	0.1521 (8)	0.052 (3)*	0.168 (3)
F5C	−0.6468 (12)	−0.5443 (11)	0.2502 (12)	0.060 (4)*	0.168 (3)
F6C	−0.6360 (12)	−0.7418 (14)	0.2924 (6)	0.038 (3)*	0.168 (3)
F3D	−0.8290 (15)	−0.7443 (19)	0.1626 (12)	0.065 (6)*	0.116 (3)
F4D	−0.7765 (17)	−0.5445 (12)	0.1737 (9)	0.023 (3)*	0.116 (3)
F5D	−0.6264 (15)	−0.590 (2)	0.2817 (12)	0.063 (6)*	0.116 (3)
F6D	−0.6817 (17)	−0.7901 (13)	0.2728 (10)	0.026 (3)*	0.116 (3)
C2	−0.0535 (7)	−0.4794 (9)	0.0952 (6)	0.075 (3)	0.5
C3	−0.001 (3)	−0.379 (2)	0.0769 (18)	0.100 (11)	0.5
H3A	0.0722	−0.3702	0.1111	0.150*	0.5
H3B	−0.0487	−0.3127	0.0821	0.150*	0.5
H3C	0.0088	−0.3837	0.0245	0.150*	0.5
N1	−0.0887 (8)	−0.5623 (9)	0.1155 (6)	0.089 (3)	0.5
F4A	−0.8329 (5)	−0.6949 (7)	0.1425 (4)	0.0542 (16)*	0.428 (3)
O4	−0.011 (2)	−0.3481 (18)	0.0721 (15)	0.097 (5)	0.5
O3	−0.0385 (6)	−0.6046 (6)	0.0816 (4)	0.0777 (18)	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C12	0.0349 (16)	0.0308 (15)	0.0307 (14)	0.0005 (13)	0.0069 (13)	0.0024 (12)
C15	0.0343 (15)	0.0247 (14)	0.0316 (14)	−0.0003 (12)	0.0047 (12)	0.0031 (11)
C22	0.0451 (17)	0.0271 (15)	0.0377 (15)	−0.0006 (13)	0.0149 (14)	0.0005 (12)
C25	0.0465 (18)	0.0282 (15)	0.0332 (15)	0.0027 (13)	0.0129 (13)	0.0012 (12)
Cu1	0.0469 (2)	0.0295 (2)	0.0491 (2)	0.00365 (17)	0.02508 (18)	0.00394 (16)
N12	0.0483 (17)	0.0327 (15)	0.0571 (17)	−0.0018 (13)	0.0290 (14)	−0.0010 (13)
N13	0.0350 (13)	0.0281 (12)	0.0327 (12)	0.0019 (10)	0.0120 (10)	0.0006 (10)
N14	0.0357 (13)	0.0273 (12)	0.0361 (13)	0.0011 (10)	0.0148 (11)	−0.0008 (10)
N22	0.089 (2)	0.0409 (17)	0.0393 (15)	0.0028 (17)	0.0326 (16)	0.0034 (13)
N23	0.0425 (14)	0.0260 (12)	0.0313 (12)	−0.0015 (11)	0.0114 (11)	−0.0010 (10)
N24	0.0448 (15)	0.0319 (13)	0.0266 (11)	0.0006 (11)	0.0118 (11)	0.0003 (10)
O1	0.0438 (13)	0.0496 (14)	0.0677 (15)	0.0009 (11)	0.0130 (12)	0.0152 (12)
O2	0.0505 (16)	0.098 (2)	0.0692 (18)	0.0040 (15)	0.0127 (14)	0.0034 (17)
S11	0.0417 (4)	0.0286 (4)	0.0427 (4)	−0.0049 (3)	0.0160 (3)	−0.0023 (3)
S12	0.0672 (6)	0.0310 (4)	0.0514 (5)	−0.0026 (4)	0.0274 (4)	−0.0090 (3)
S21	0.0727 (6)	0.0275 (4)	0.0417 (4)	0.0013 (4)	0.0237 (4)	0.0058 (3)
C17A	0.047 (4)	0.053 (4)	0.040 (3)	0.004 (3)	0.020 (3)	−0.010 (3)
C18A	0.040 (3)	0.042 (3)	0.045 (4)	0.011 (2)	0.019 (3)	0.004 (2)
C19A	0.056 (6)	0.055 (8)	0.063 (7)	0.024 (4)	0.041 (4)	0.008 (4)
C27A	0.066 (3)	0.0340 (19)	0.0399 (19)	−0.0042 (18)	0.0238 (19)	−0.0056 (15)
C28A	0.044 (3)	0.048 (2)	0.0343 (19)	−0.010 (2)	0.0116 (19)	−0.0099 (16)
C29A	0.070 (4)	0.052 (3)	0.031 (3)	−0.004 (3)	0.018 (2)	−0.009 (2)
Cu2A	0.0476 (11)	0.0274 (4)	0.0305 (4)	−0.0023 (8)	0.0126 (8)	0.0006 (3)
S22A	0.0631 (11)	0.0244 (6)	0.0524 (8)	−0.0018 (7)	0.0253 (8)	−0.0050 (5)
Cu2B	0.041 (7)	0.032 (3)	0.027 (2)	−0.002 (5)	0.007 (5)	−0.0004 (19)
F1	0.0664 (13)	0.0538 (12)	0.0482 (10)	−0.0033 (10)	0.0328 (10)	0.0035 (9)
F2	0.0802 (15)	0.0500 (12)	0.0762 (14)	0.0223 (11)	0.0487 (12)	0.0078 (10)
Si1	0.0500 (5)	0.0294 (4)	0.0402 (4)	0.0016 (4)	0.0193 (4)	0.0037 (3)
C2	0.048 (5)	0.087 (7)	0.087 (6)	−0.002 (5)	0.007 (4)	−0.034 (6)
C3	0.15 (2)	0.070 (16)	0.084 (12)	−0.057 (16)	0.034 (12)	−0.023 (11)
N1	0.074 (6)	0.075 (6)	0.119 (8)	−0.029 (5)	0.021 (5)	−0.012 (6)
O4	0.115 (10)	0.059 (8)	0.127 (9)	0.003 (7)	0.051 (7)	0.013 (6)
O3	0.070 (4)	0.067 (4)	0.093 (5)	−0.008 (3)	0.011 (4)	0.013 (4)

Geometric parameters (Å, º)

C12—N13	1.311 (4)	C28A—H28A	0.9300
C12—S11	1.731 (3)	C28A—C29A	1.364 (6)
C12—S12	1.731 (3)	C28A—Cu2A	2.027 (5)
C15—N12	1.328 (4)	C29A—H29A	0.9300
C15—N14	1.319 (3)	C29A—H29B	0.9300
C15—S11	1.745 (3)	C29A—Cu2A	2.082 (7)
C22—N23	1.289 (4)	C17B—H17C	0.9700
C22—S21	1.732 (3)	C17B—H17D	0.9700
C22—S22A	1.742 (3)	C17B—C18B	1.476 (15)
C22—S22B	1.757 (13)	C18B—H18B	0.9300
C25—N22	1.328 (4)	C18B—C19B	1.39 (3)
C25—N24	1.317 (3)	C19B—H19C	0.9300
C25—S21	1.742 (3)	C19B—H19D	0.9300
Cu1—N13	1.991 (2)	C27B—H27C	0.9700
Cu1—N24	2.010 (2)	C27B—H27D	0.9700
Cu1—O1	2.364 (3)	C27B—C28B	1.487 (18)
Cu1—C18A	2.035 (5)	C27B—S22B	1.76 (3)
Cu1—C19A	2.064 (18)	C28B—H28B	0.9300
Cu1—C18B	2.138 (8)	C28B—C29B	1.358 (18)
Cu1—C19B	2.01 (3)	C28B—Cu2B	2.08 (4)
N12—H12A	0.86 (3)	C29B—H29C	0.9300
N12—H12B	0.86 (4)	C29B—H29D	0.9300
N13—N14	1.389 (3)	C29B—Cu2B	1.87 (5)
N14—Cu2A	1.975 (4)	F1—Si1	1.682 (2)
N14—Cu2B	1.95 (3)	F2—Si1	1.691 (2)
N22—H22A	0.93 (4)	Si1—F3A	1.693 (4)
N22—H22B	0.83 (4)	Si1—F5A	1.633 (4)
N23—N24	1.399 (3)	Si1—F6A	1.682 (5)
N23—Cu2A	2.003 (4)	Si1—F3B	1.683 (6)
N23—Cu2B	2.07 (3)	Si1—F4B	1.656 (7)
O1—H1A	0.9054	Si1—F5B	1.697 (6)
O1—H1B	0.9041	Si1—F6B	1.719 (7)
O2—H2A	0.8695	Si1—F3C	1.621 (9)
O2—H2B	0.8712	Si1—F4C	1.689 (9)
S12—C17A	1.804 (6)	Si1—F5C	1.723 (9)
S12—C17B	1.828 (10)	Si1—F6C	1.682 (8)
C17A—H17A	0.9700	Si1—F3D	1.678 (11)
C17A—H17B	0.9700	Si1—F4D	1.709 (9)
C17A—C18A	1.480 (9)	Si1—F5D	1.681 (10)
C18A—H18A	0.9300	Si1—F6D	1.677 (9)
C18A—C19A	1.29 (2)	Si1—F4A	1.710 (5)
C19A—H19A	0.9300	C2—C3	1.38 (3)
C19A—H19B	0.9300	C2—N1	1.126 (12)
C27A—H27A	0.9700	C3—H3A	0.9600
C27A—H27B	0.9700	C3—H3B	0.9600
C27A—C28A	1.519 (5)	C3—H3C	0.9600
C27A—S22A	1.790 (4)
N13—C12—S11	113.3 (2)	H17C—C17B—H17D	107.3
N13—C12—S12	127.7 (2)	C18B—C17B—S12	116.5 (8)
S12—C12—S11	118.98 (17)	C18B—C17B—H17C	108.2
N12—C15—S11	121.6 (2)	C18B—C17B—H17D	108.2
N14—C15—N12	125.3 (3)	Cu1—C18B—H18B	98.5
N14—C15—S11	113.1 (2)	C17B—C18B—Cu1	106.5 (6)
N23—C22—S21	114.4 (2)	C17B—C18B—H18B	116.0
N23—C22—S22A	128.4 (2)	C19B—C18B—Cu1	65.6 (12)
N23—C22—S22B	125.2 (5)	C19B—C18B—C17B	128.0 (14)
S21—C22—S22A	117.13 (17)	C19B—C18B—H18B	116.0
S21—C22—S22B	117.8 (5)	Cu1—C19B—H19C	99.3
N22—C25—S21	121.2 (2)	Cu1—C19B—H19D	95.2
N24—C25—N22	125.0 (3)	C18B—C19B—Cu1	75.4 (13)
N24—C25—S21	113.8 (2)	C18B—C19B—H19C	120.0
N13—Cu1—N24	108.81 (10)	C18B—C19B—H19D	120.0
N13—Cu1—O1	91.35 (9)	H19C—C19B—H19D	120.0
N13—Cu1—C18A	94.59 (16)	H27C—C27B—H27D	107.1
N13—Cu1—C19A	131.2 (5)	C28B—C27B—H27C	107.7
N13—Cu1—C18B	100.4 (2)	C28B—C27B—H27D	107.7
N13—Cu1—C19B	135.2 (9)	C28B—C27B—S22B	118 (2)
N24—Cu1—O1	87.32 (9)	S22B—C27B—H27C	107.7
N24—Cu1—C18A	154.62 (17)	S22B—C27B—H27D	107.7
N24—Cu1—C19A	118.9 (5)	C27B—C28B—H28B	116.8
N24—Cu1—C18B	134.4 (3)	C27B—C28B—Cu2B	110 (2)
N24—Cu1—C19B	114.6 (9)	C29B—C28B—C27B	126 (3)
C18A—Cu1—O1	102.20 (19)	C29B—C28B—H28B	116.8
C18A—Cu1—C19A	36.6 (6)	C29B—C28B—Cu2B	62 (2)
C19A—Cu1—O1	100.4 (5)	Cu2B—C28B—H28B	97.7
C18B—Cu1—O1	126.8 (3)	C28B—C29B—H29C	120.0
C19B—Cu1—O1	101.0 (6)	C28B—C29B—H29D	120.0
C19B—Cu1—C18B	39.1 (8)	C28B—C29B—Cu2B	78 (2)
C15—N12—H12A	112 (2)	H29C—C29B—H29D	120.0
C15—N12—H12B	123 (2)	Cu2B—C29B—H29C	100.7
H12A—N12—H12B	116 (3)	Cu2B—C29B—H29D	91.1
C12—N13—Cu1	127.76 (19)	N14—Cu2B—N23	109.7 (12)
C12—N13—N14	113.4 (2)	N14—Cu2B—C28B	149.8 (15)
N14—N13—Cu1	118.83 (17)	N23—Cu2B—C28B	100.2 (13)
C15—N14—N13	112.3 (2)	C29B—Cu2B—N14	111.9 (15)
C15—N14—Cu2A	131.2 (2)	C29B—Cu2B—N23	131.2 (17)
C15—N14—Cu2B	124.0 (6)	C29B—Cu2B—C28B	39.8 (9)
N13—N14—Cu2A	116.08 (19)	C22—S22B—C27B	108.0 (13)
N13—N14—Cu2B	123.8 (6)	F1—Si1—F2	178.11 (12)
C25—N22—H22A	129 (2)	F1—Si1—F3A	89.52 (17)
C25—N22—H22B	117 (3)	F1—Si1—F6A	91.1 (2)
H22A—N22—H22B	114 (3)	F1—Si1—F3B	90.2 (2)
C22—N23—N24	113.2 (2)	F1—Si1—F5B	84.4 (2)
C22—N23—Cu2A	128.6 (2)	F1—Si1—F6B	87.8 (3)
C22—N23—Cu2B	125.7 (7)	F1—Si1—F4C	96.1 (5)
N24—N23—Cu2A	117.60 (19)	F1—Si1—F5C	89.9 (5)
N24—N23—Cu2B	121.1 (7)	F1—Si1—F6C	87.0 (4)
C25—N24—Cu1	128.1 (2)	F1—Si1—F4D	98.5 (4)
C25—N24—N23	111.6 (2)	F1—Si1—F4A	90.0 (2)
N23—N24—Cu1	115.34 (16)	F2—Si1—F3A	89.89 (17)
Cu1—O1—H1A	111.4	F2—Si1—F5B	95.5 (2)
Cu1—O1—H1B	110.8	F2—Si1—F6B	90.3 (3)
H1A—O1—H1B	107.4	F2—Si1—F5C	89.4 (5)
H2A—O2—H2B	109.5	F2—Si1—F4D	82.7 (4)
C12—S11—C15	87.83 (14)	F2—Si1—F4A	91.8 (2)
C12—S12—C17A	106.6 (2)	F3A—Si1—F4A	89.3 (3)
C12—S12—C17B	103.3 (3)	F5A—Si1—F1	92.0 (2)
C22—S21—C25	87.00 (14)	F5A—Si1—F2	88.7 (2)
S12—C17A—H17A	107.7	F5A—Si1—F3A	178.5 (3)
S12—C17A—H17B	107.7	F5A—Si1—F6A	91.6 (3)
H17A—C17A—H17B	107.1	F5A—Si1—F4A	90.3 (3)
C18A—C17A—S12	118.6 (5)	F6A—Si1—F2	87.1 (2)
C18A—C17A—H17A	107.7	F6A—Si1—F3A	88.7 (3)
C18A—C17A—H17B	107.7	F6A—Si1—F4A	177.7 (3)
Cu1—C18A—H18A	90.7	F3B—Si1—F2	89.7 (2)
C17A—C18A—Cu1	106.4 (4)	F3B—Si1—F5B	174.2 (4)
C17A—C18A—H18A	119.1	F3B—Si1—F6B	89.4 (4)
C19A—C18A—Cu1	72.9 (7)	F4B—Si1—F1	86.4 (3)
C19A—C18A—C17A	121.7 (10)	F4B—Si1—F2	95.5 (3)
C19A—C18A—H18A	119.1	F4B—Si1—F3B	90.2 (4)
Cu1—C19A—H19A	107.2	F4B—Si1—F5B	91.8 (4)
Cu1—C19A—H19B	92.2	F4B—Si1—F6B	174.2 (5)
C18A—C19A—Cu1	70.5 (9)	F5B—Si1—F6B	88.1 (4)
C18A—C19A—H19A	120.0	F3C—Si1—F1	92.7 (6)
C18A—C19A—H19B	120.0	F3C—Si1—F2	88.0 (6)
H19A—C19A—H19B	120.0	F3C—Si1—F4C	91.7 (5)
H27A—C27A—H27B	107.5	F3C—Si1—F5C	177.4 (8)
C28A—C27A—H27A	108.4	F3C—Si1—F6C	91.7 (5)
C28A—C27A—H27B	108.4	F4C—Si1—F2	85.6 (5)
C28A—C27A—S22A	115.5 (3)	F4C—Si1—F5C	88.1 (5)
S22A—C27A—H27A	108.4	F6C—Si1—F2	91.2 (4)
S22A—C27A—H27B	108.4	F6C—Si1—F4C	175.3 (6)
C27A—C28A—H28A	119.5	F6C—Si1—F5C	88.4 (5)
C27A—C28A—Cu2A	105.2 (3)	F3D—Si1—F1	93.0 (8)
C29A—C28A—C27A	121.0 (5)	F3D—Si1—F2	88.4 (8)
C29A—C28A—H28A	119.5	F3D—Si1—F4D	88.7 (6)
C29A—C28A—Cu2A	72.8 (3)	F3D—Si1—F5D	174.0 (11)
Cu2A—C28A—H28A	92.0	F5D—Si1—F1	92.8 (7)
C28A—C29A—H29A	120.0	F5D—Si1—F2	85.8 (7)
C28A—C29A—H29B	120.0	F5D—Si1—F4D	89.3 (6)
C28A—C29A—Cu2A	68.4 (3)	F6D—Si1—F1	89.0 (5)
H29A—C29A—H29B	120.0	F6D—Si1—F2	89.7 (5)
Cu2A—C29A—H29A	106.9	F6D—Si1—F3D	90.9 (6)
Cu2A—C29A—H29B	94.4	F6D—Si1—F4D	172.4 (6)
N14—Cu2A—N23	111.49 (19)	F6D—Si1—F5D	90.3 (6)
N14—Cu2A—C28A	153.0 (2)	N1—C2—C3	174.2 (17)
N14—Cu2A—C29A	114.2 (2)	C2—C3—H3A	109.5
N23—Cu2A—C28A	95.1 (2)	C2—C3—H3B	109.5
N23—Cu2A—C29A	133.3 (2)	C2—C3—H3C	109.5
C28A—Cu2A—C29A	38.75 (19)	H3A—C3—H3B	109.5
C22—S22A—C27A	104.05 (16)	H3A—C3—H3C	109.5
S12—C17B—H17C	108.2	H3B—C3—H3C	109.5
S12—C17B—H17D	108.2
C12—N13—N14—C15	−2.4 (3)	S12—C12—S11—C15	−179.84 (18)
C12—N13—N14—Cu2A	170.8 (2)	S12—C17A—C18A—Cu1	−72.0 (6)
C12—N13—N14—Cu2B	179.3 (7)	S12—C17A—C18A—C19A	−151.8 (9)
C12—S12—C17A—C18A	40.2 (6)	S12—C17B—C18B—Cu1	69.4 (9)
C12—S12—C17B—C18B	−68.3 (8)	S12—C17B—C18B—C19B	141.0 (17)
C22—N23—N24—C25	−2.2 (3)	S21—C22—N23—N24	1.7 (3)
C22—N23—N24—Cu1	154.9 (2)	S21—C22—N23—Cu2A	172.19 (16)
Cu1—N13—N14—C15	177.89 (18)	S21—C22—N23—Cu2B	−175.7 (6)
Cu1—N13—N14—Cu2A	−9.0 (3)	S21—C22—S22A—C27A	176.71 (19)
Cu1—N13—N14—Cu2B	−0.5 (8)	S21—C22—S22B—C27B	−150.7 (11)
N12—C15—N14—N13	−177.4 (3)	S21—C25—N24—Cu1	−151.74 (16)
N12—C15—N14—Cu2A	10.8 (4)	S21—C25—N24—N23	1.7 (3)
N12—C15—N14—Cu2B	1.0 (8)	C17A—C18A—C19A—Cu1	99.0 (7)
N12—C15—S11—C12	178.4 (3)	C27A—C28A—C29A—Cu2A	97.7 (4)
N13—C12—S11—C15	0.0 (2)	C28A—C27A—S22A—C22	51.8 (3)
N13—C12—S12—C17A	0.9 (4)	Cu2A—N23—N24—C25	−173.8 (2)
N13—C12—S12—C17B	26.1 (5)	Cu2A—N23—N24—Cu1	−16.7 (3)
N14—C15—S11—C12	−1.3 (2)	S22A—C22—N23—N24	−178.0 (2)
N22—C25—N24—Cu1	29.1 (5)	S22A—C22—N23—Cu2A	−7.5 (4)
N22—C25—N24—N23	−177.4 (3)	S22A—C22—S21—C25	179.1 (2)
N22—C25—S21—C22	178.5 (3)	S22A—C27A—C28A—C29A	−157.8 (4)
N23—C22—S21—C25	−0.6 (2)	S22A—C27A—C28A—Cu2A	−79.0 (3)
N23—C22—S22A—C27A	−3.6 (4)	C17B—C18B—C19B—Cu1	−92.4 (13)
N23—C22—S22B—C27B	10.0 (13)	C27B—C28B—C29B—Cu2B	−96 (3)
N24—C25—S21—C22	−0.7 (2)	C28B—C27B—S22B—C22	−60 (3)
S11—C12—N13—Cu1	−178.94 (13)	C28B—C29B—Cu2B—N14	−166.5 (17)
S11—C12—N13—N14	1.3 (3)	C28B—C29B—Cu2B—N23	47 (3)
S11—C12—S12—C17A	−179.3 (3)	Cu2B—N23—N24—C25	175.3 (6)
S11—C12—S12—C17B	−154.2 (4)	Cu2B—N23—N24—Cu1	−27.6 (6)
S11—C15—N14—N13	2.3 (3)	S22B—C22—N23—N24	−159.6 (5)
S11—C15—N14—Cu2A	−169.48 (18)	S22B—C22—N23—Cu2B	23.0 (8)
S11—C15—N14—Cu2B	−179.3 (7)	S22B—C22—S21—C25	162.2 (4)
S12—C12—N13—Cu1	0.8 (4)	S22B—C27B—C28B—C29B	133 (3)
S12—C12—N13—N14	−178.9 (2)	S22B—C27B—C28B—Cu2B	63 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12A···F1	0.86 (3)	2.14 (4)	2.973 (4)	163 (3)
N12—H12A···F3A	0.86 (3)	2.26 (4)	2.780 (6)	119 (3)
N12—H12A···F3B	0.86 (3)	2.48 (4)	2.990 (9)	119 (3)
N12—H12A···F6C	0.86 (3)	2.35 (4)	2.989 (14)	132 (3)
N12—H12A···F6D	0.86 (3)	2.17 (4)	2.733 (13)	123 (3)
N12—H12B···F2^i	0.86 (4)	2.04 (4)	2.827 (3)	152 (3)
N22—H22A···F2^ii	0.93 (4)	2.05 (4)	2.903 (4)	153 (3)
N22—H22A···F6C^ii	0.93 (4)	2.40 (4)	2.931 (15)	117 (3)
N22—H22B···F5A^iii	0.83 (4)	1.83 (4)	2.638 (5)	165 (4)
N22—H22B···F3B^ii	0.83 (4)	2.52 (4)	2.931 (9)	112 (3)
N22—H22B···F5B^iii	0.83 (4)	1.98 (4)	2.758 (9)	157 (4)
N22—H22B···F4C^iii	0.83 (4)	2.55 (4)	3.250 (19)	142 (3)
N22—H22B···F5C^iii	0.83 (4)	2.50 (4)	3.27 (2)	154 (4)
N22—H22B···F4D^iii	0.83 (4)	2.00 (4)	2.766 (15)	153 (4)
O1—H1A···N1	0.91	1.89	2.789 (10)	175
O1—H1A···O3	0.91	2.06	2.875 (7)	149
O1—H1B···O2	0.90	1.85	2.698 (4)	156
O2—H2A···F5A^iv	0.87	2.48	3.293 (9)	156
O2—H2A···F6A^iv	0.87	2.23	2.926 (8)	138
O2—H2A···F5B^iv	0.87	1.98	2.819 (11)	163
O2—H2A···F6B^iv	0.87	2.68	3.361 (13)	136
O2—H2A···F5C^iv	0.87	1.52	2.385 (12)	169
O2—H2A···F5D^iv	0.87	1.64	2.427 (15)	150
O2—H2B···F3A^v	0.87	2.48	3.095 (9)	128
O2—H2B···F3B^v	0.87	2.03	2.691 (9)	132
O2—H2B···F4B^v	0.87	2.61	3.464 (13)	168
O2—H2B···F3C^v	0.87	1.59	2.383 (11)	149
O2—H2B···F3D^v	0.87	1.59	2.465 (18)	177
O2—H2B···F4A^v	0.87	2.09	2.952 (9)	169
C17A—H17A···F4A^vi	0.97	2.43	3.333 (8)	155
C27A—H27A···O2^vii	0.97	2.52	3.322 (5)	140
C27A—H27B···F1	0.97	2.46	3.376 (4)	157
C27B—H27D···O1^vii	0.97	2.66	3.57 (4)	157
C28B—H28B···F1	0.93	2.57	3.23 (3)	128

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

(5) µ-Benzenesulfonato-bis{µ-5-[(prop-2-en-1-yl)sulfanyl]-1,3,4-thiadiazol-2-amine}dicopper(I) benzenesulfonate methanol monosolvate monohydrate

Crystal data

[Cu2(C6H5O3S)(C5H7N3S2)2](C6H5O3S)·CH4O·H2O	F(000) = 1712
Mr = 837.97	Dx = 1.734 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 14.944 (4) Å	Cell parameters from 10457 reflections
b = 16.587 (5) Å	θ = 3.4–77.6°
c = 14.658 (4) Å	µ = 5.77 mm^−1
β = 117.91 (3)°	T = 110 K
V = 3210.7 (17) Å^3	Block, clear colourless
Z = 4	0.45 × 0.32 × 0.17 mm

Data collection

Rigaku Xcalibur Onyx diffractometer	6741 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source	6073 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
Detector resolution: 8.1956 pixels mm^-1	θmax = 78.0°, θmin = 3.4°
ω scans	h = −16→18
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	k = −20→17
Tmin = 0.248, Tmax = 0.540	l = −18→16
16595 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.057	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.166	w = 1/[σ^2(Fo^2) + (0.108P)^2 + 2.144P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
6741 reflections	Δρmax = 1.03 e Å^−3
487 parameters	Δρmin = −1.49 e Å^−3
3 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.71463 (4)	0.46102 (3)	0.25333 (4)	0.03132 (15)
Cu2	0.70615 (4)	0.53623 (3)	0.46302 (4)	0.03199 (15)
S11	0.74240 (6)	0.73187 (5)	0.27560 (6)	0.03241 (18)
S12	0.68469 (9)	0.63190 (6)	0.08869 (7)	0.0451 (2)
S21	0.80874 (6)	0.27825 (5)	0.50610 (6)	0.03168 (18)
S22	0.73084 (6)	0.36872 (5)	0.62865 (5)	0.03159 (18)
S31A	0.4810 (3)	0.4424 (3)	0.2480 (3)	0.0304 (6)	0.644 (6)
S31B	0.4816 (6)	0.4310 (5)	0.2230 (5)	0.0296 (11)	0.356 (6)
O31A	0.5331 (3)	0.4589 (3)	0.1884 (4)	0.0449 (11)	0.644 (6)
O31B	0.5736 (4)	0.4754 (4)	0.2891 (5)	0.0310 (16)	0.356 (6)
O32A	0.5256 (3)	0.4869 (3)	0.3451 (3)	0.0448 (11)	0.644 (6)
O32B	0.3953 (7)	0.4564 (6)	0.2366 (9)	0.037 (2)	0.356 (6)
O33A	0.3728 (4)	0.4551 (4)	0.1911 (4)	0.0383 (12)	0.644 (6)
O33B	0.4610 (5)	0.4282 (5)	0.1179 (5)	0.0378 (18)	0.356 (6)
N12	0.7894 (2)	0.72597 (17)	0.4762 (2)	0.0345 (6)
H12A	0.797 (3)	0.781 (3)	0.478 (4)	0.041*
H12B	0.814 (4)	0.700 (3)	0.535 (4)	0.041*
N13	0.7226 (2)	0.57953 (16)	0.2809 (2)	0.0289 (5)
N14	0.74612 (19)	0.60649 (16)	0.37976 (18)	0.0262 (5)
N22	0.8476 (2)	0.28718 (18)	0.3451 (2)	0.0360 (6)
H22A	0.871 (4)	0.315 (3)	0.308 (4)	0.043*
H22B	0.871 (4)	0.239 (3)	0.362 (4)	0.043*
N23	0.75070 (18)	0.42421 (16)	0.46223 (18)	0.0257 (5)
N24	0.7777 (2)	0.40025 (16)	0.38683 (19)	0.0276 (5)
C12	0.7161 (3)	0.63734 (19)	0.2188 (3)	0.0320 (6)
C15	0.7616 (2)	0.68478 (19)	0.3896 (2)	0.0295 (6)
C17A	0.7197 (3)	0.5307 (3)	0.0744 (3)	0.0357 (11)	0.801 (10)
H17A	0.7098	0.5241	0.0032	0.043*	0.801 (10)
H17B	0.7927	0.5233	0.1221	0.043*	0.801 (10)
C17B	0.6409 (11)	0.5277 (9)	0.0557 (11)	0.027 (4)*	0.199 (10)
H17C	0.5832	0.5191	0.0701	0.033*	0.199 (10)
H17D	0.6157	0.5200	−0.0193	0.033*	0.199 (10)
C18A	0.6618 (3)	0.4659 (3)	0.0951 (3)	0.0333 (10)	0.801 (10)
H18A	0.5946	0.4772	0.0821	0.040*	0.801 (10)
C18B	0.7173 (13)	0.4671 (8)	0.1108 (11)	0.022 (4)*	0.199 (10)
H18B	0.7859	0.4825	0.1345	0.026*	0.199 (10)
C19	0.7008 (3)	0.3910 (2)	0.1317 (2)	0.0388 (7)
H19A	0.7679	0.3781	0.1453	0.047*	0.801 (10)
H19B	0.6608	0.3520	0.1435	0.047*	0.801 (10)
H19C	0.6336	0.3727	0.1097	0.047*	0.199 (10)
H19D	0.7564	0.3558	0.1685	0.047*	0.199 (10)
C22	0.7610 (2)	0.36726 (18)	0.5270 (2)	0.0274 (6)
C25	0.8116 (2)	0.32546 (19)	0.4009 (2)	0.0289 (6)
C27A	0.7145 (4)	0.4774 (3)	0.6479 (4)	0.0346 (13)	0.664 (10)
H27A	0.6940	0.4827	0.7028	0.042*	0.664 (10)
H27B	0.7806	0.5049	0.6722	0.042*	0.664 (10)
C28A	0.6385 (4)	0.5191 (4)	0.5539 (4)	0.0368 (14)	0.664 (10)
H28A	0.5841	0.4891	0.5025	0.044*	0.664 (10)
C29A	0.6456 (12)	0.6009 (6)	0.5396 (12)	0.035 (4)	0.664 (10)
H29A	0.6999	0.6313	0.5905	0.042*	0.664 (10)
H29B	0.5963	0.6266	0.4789	0.042*	0.664 (10)
C27B	0.6490 (6)	0.4546 (5)	0.6003 (6)	0.023 (2)*	0.336 (10)
H27C	0.5910	0.4487	0.5304	0.027*	0.336 (10)
H27D	0.6221	0.4573	0.6504	0.027*	0.336 (10)
C28B	0.7036 (6)	0.5298 (5)	0.6054 (6)	0.022 (2)*	0.336 (10)
H28B	0.7748	0.5334	0.6477	0.026*	0.336 (10)
C29B	0.648 (3)	0.5963 (14)	0.546 (3)	0.049 (11)*	0.336 (10)
H29C	0.5769	0.5921	0.5042	0.058*	0.336 (10)
H29D	0.6819	0.6454	0.5484	0.058*	0.336 (10)
C31	0.5023 (2)	0.3352 (2)	0.2756 (3)	0.0331 (6)
C32	0.5006 (3)	0.2774 (3)	0.2070 (3)	0.0487 (9)
H32	0.4892	0.2926	0.1399	0.058*
C33	0.5157 (3)	0.1973 (3)	0.2365 (4)	0.0594 (12)
H33	0.5148	0.1577	0.1893	0.071*
C34	0.5320 (3)	0.1741 (3)	0.3333 (4)	0.0549 (11)
H34	0.5425	0.1190	0.3531	0.066*
C35	0.5329 (3)	0.2328 (3)	0.4021 (3)	0.0480 (9)
H35	0.5434	0.2178	0.4690	0.058*
C36	0.5186 (2)	0.3121 (2)	0.3729 (3)	0.0403 (7)
H36	0.5200	0.3519	0.4201	0.048*
S41	0.97251 (6)	0.62170 (5)	0.76431 (6)	0.03256 (19)
O41	0.8831 (2)	0.6489 (2)	0.6743 (2)	0.0575 (8)
O42	1.0634 (2)	0.66597 (18)	0.7849 (2)	0.0463 (6)
O43	0.95553 (18)	0.61808 (18)	0.85462 (19)	0.0414 (6)
C41	0.9942 (2)	0.5208 (2)	0.7391 (3)	0.0338 (6)
C42	1.0076 (3)	0.5059 (3)	0.6531 (3)	0.0448 (8)
H42	1.0049	0.5489	0.6090	0.054*
C43	1.0252 (3)	0.4279 (3)	0.6323 (4)	0.0608 (12)
H43	1.0348	0.4171	0.5739	0.073*
C44	1.0287 (3)	0.3646 (3)	0.6973 (5)	0.0641 (14)
H44	1.0403	0.3110	0.6827	0.077*
C45	1.0155 (3)	0.3804 (3)	0.7818 (4)	0.0577 (12)
H45	1.0188	0.3375	0.8262	0.069*
C46	0.9975 (3)	0.4584 (2)	0.8035 (3)	0.0429 (8)
H46	0.9874	0.4688	0.8618	0.052*
O61	0.9016 (2)	0.35933 (15)	0.9454 (2)	0.0377 (5)
H61	0.944 (4)	0.366 (3)	0.999 (4)	0.057*
C61	0.8226 (4)	0.4136 (3)	0.9263 (4)	0.0536 (10)
H61A	0.7620	0.3975	0.8633	0.080*
H61B	0.8430	0.4680	0.9176	0.080*
H61C	0.8078	0.4131	0.9847	0.080*
O51	0.1975 (3)	0.38050 (17)	0.0872 (3)	0.0481 (7)
H51A	0.162 (5)	0.379 (4)	0.116 (5)	0.072*
H51B	0.248 (5)	0.407 (4)	0.124 (5)	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0483 (3)	0.0242 (3)	0.0271 (2)	0.00226 (17)	0.0224 (2)	0.00268 (16)
Cu2	0.0501 (3)	0.0251 (3)	0.0337 (3)	0.00360 (18)	0.0305 (2)	0.00246 (17)
S11	0.0443 (4)	0.0243 (4)	0.0373 (4)	0.0033 (3)	0.0263 (3)	0.0055 (3)
S12	0.0792 (6)	0.0346 (4)	0.0339 (4)	0.0096 (4)	0.0367 (4)	0.0095 (3)
S21	0.0415 (4)	0.0272 (4)	0.0332 (4)	0.0057 (3)	0.0232 (3)	0.0079 (3)
S22	0.0376 (4)	0.0373 (4)	0.0247 (3)	0.0021 (3)	0.0186 (3)	0.0059 (3)
S31A	0.0278 (7)	0.0293 (11)	0.0368 (17)	−0.0016 (6)	0.0175 (11)	−0.0018 (10)
S31B	0.0242 (12)	0.037 (3)	0.026 (2)	0.0010 (14)	0.0107 (16)	0.0011 (17)
O31A	0.047 (2)	0.045 (2)	0.058 (3)	−0.0005 (17)	0.037 (2)	0.0055 (19)
O31B	0.027 (3)	0.031 (3)	0.027 (3)	−0.006 (2)	0.006 (2)	0.003 (2)
O32A	0.0359 (18)	0.040 (2)	0.048 (2)	0.0005 (15)	0.0107 (16)	−0.0140 (18)
O32B	0.027 (4)	0.044 (4)	0.044 (5)	0.006 (3)	0.021 (4)	0.001 (5)
O33A	0.029 (2)	0.046 (2)	0.033 (3)	0.0025 (18)	0.010 (2)	0.005 (3)
O33B	0.037 (3)	0.050 (4)	0.026 (3)	0.008 (3)	0.014 (3)	0.007 (3)
N12	0.0449 (14)	0.0252 (13)	0.0334 (13)	−0.0004 (11)	0.0183 (12)	−0.0012 (11)
N13	0.0416 (13)	0.0260 (12)	0.0270 (12)	0.0024 (10)	0.0226 (10)	0.0005 (10)
N14	0.0341 (11)	0.0251 (12)	0.0238 (11)	0.0009 (9)	0.0172 (9)	0.0004 (9)
N22	0.0517 (16)	0.0263 (13)	0.0432 (15)	0.0076 (11)	0.0333 (13)	0.0047 (11)
N23	0.0310 (11)	0.0282 (12)	0.0217 (10)	0.0011 (9)	0.0155 (9)	0.0005 (9)
N24	0.0382 (12)	0.0256 (12)	0.0279 (11)	0.0031 (9)	0.0229 (10)	0.0011 (9)
C12	0.0454 (16)	0.0265 (15)	0.0326 (15)	0.0027 (12)	0.0253 (13)	0.0030 (12)
C15	0.0285 (12)	0.0292 (15)	0.0335 (14)	0.0039 (11)	0.0170 (11)	0.0030 (12)
C17A	0.046 (2)	0.036 (2)	0.036 (2)	0.0079 (16)	0.0287 (18)	0.0045 (16)
C18A	0.031 (2)	0.041 (2)	0.0251 (18)	0.0033 (15)	0.0113 (15)	0.0050 (15)
C19	0.0546 (19)	0.0335 (17)	0.0251 (14)	0.0007 (14)	0.0160 (13)	−0.0073 (12)
C22	0.0316 (13)	0.0283 (14)	0.0259 (13)	0.0035 (11)	0.0164 (11)	0.0049 (11)
C25	0.0323 (13)	0.0265 (14)	0.0306 (13)	−0.0002 (11)	0.0171 (11)	0.0025 (11)
C27A	0.044 (3)	0.038 (3)	0.026 (2)	0.000 (2)	0.020 (2)	0.0006 (19)
C28A	0.034 (3)	0.050 (3)	0.039 (3)	0.005 (2)	0.027 (2)	0.004 (2)
C29A	0.058 (7)	0.029 (4)	0.043 (6)	0.012 (2)	0.044 (5)	0.002 (2)
C31	0.0235 (12)	0.0339 (16)	0.0368 (15)	−0.0038 (11)	0.0099 (11)	0.0002 (13)
C32	0.0465 (19)	0.060 (3)	0.046 (2)	−0.0038 (17)	0.0271 (16)	−0.0105 (18)
C33	0.050 (2)	0.054 (3)	0.075 (3)	−0.0051 (18)	0.030 (2)	−0.026 (2)
C34	0.0360 (16)	0.036 (2)	0.077 (3)	−0.0033 (14)	0.0136 (18)	0.0017 (19)
C35	0.0403 (17)	0.050 (2)	0.0416 (18)	0.0047 (16)	0.0091 (14)	0.0146 (16)
C36	0.0332 (14)	0.045 (2)	0.0309 (15)	0.0037 (13)	0.0054 (12)	0.0004 (14)
S41	0.0324 (3)	0.0379 (4)	0.0270 (3)	0.0006 (3)	0.0136 (3)	0.0044 (3)
O41	0.0610 (17)	0.0601 (19)	0.0351 (13)	0.0229 (15)	0.0089 (12)	0.0111 (13)
O42	0.0559 (15)	0.0435 (15)	0.0536 (15)	−0.0159 (12)	0.0374 (13)	−0.0107 (12)
O43	0.0360 (11)	0.0578 (16)	0.0362 (12)	0.0015 (10)	0.0216 (10)	0.0022 (11)
C41	0.0238 (12)	0.0399 (17)	0.0347 (15)	−0.0034 (12)	0.0113 (11)	0.0019 (13)
C42	0.0428 (17)	0.050 (2)	0.0473 (19)	−0.0056 (15)	0.0257 (15)	−0.0039 (17)
C43	0.050 (2)	0.064 (3)	0.076 (3)	−0.009 (2)	0.036 (2)	−0.024 (2)
C44	0.0369 (18)	0.043 (2)	0.112 (4)	−0.0040 (15)	0.034 (2)	−0.013 (2)
C45	0.0361 (17)	0.041 (2)	0.088 (3)	−0.0022 (15)	0.023 (2)	0.012 (2)
C46	0.0321 (15)	0.044 (2)	0.051 (2)	−0.0039 (13)	0.0174 (14)	0.0094 (16)
O61	0.0455 (12)	0.0322 (12)	0.0347 (12)	−0.0001 (10)	0.0183 (10)	−0.0046 (10)
C61	0.067 (3)	0.037 (2)	0.058 (2)	0.0139 (18)	0.031 (2)	0.0029 (18)
O51	0.0623 (17)	0.0329 (13)	0.0722 (19)	0.0012 (12)	0.0506 (16)	−0.0025 (13)

Geometric parameters (Å, º)

Cu1—O31A	2.418 (4)	C18B—C19	1.348 (14)
Cu1—O31B	2.409 (7)	C19—H19A	0.9500
Cu1—N13	1.999 (3)	C19—H19B	0.9500
Cu1—N24	2.002 (3)	C19—H19C	0.9500
Cu1—C18A	2.072 (4)	C19—H19D	0.9500
Cu1—C18B	2.111 (14)	C27A—H27A	0.9900
Cu1—C19	2.055 (3)	C27A—H27B	0.9900
Cu2—N14	1.972 (2)	C27A—C28A	1.484 (7)
Cu2—N23	1.976 (3)	C28A—H28A	0.9500
Cu2—C28A	2.033 (4)	C28A—C29A	1.384 (11)
Cu2—C29A	2.044 (11)	C29A—H29A	0.9500
Cu2—C28B	2.107 (8)	C29A—H29B	0.9500
Cu2—C29B	2.06 (4)	C27B—H27C	0.9900
S11—C12	1.732 (3)	C27B—H27D	0.9900
S11—C15	1.743 (3)	C27B—C28B	1.473 (10)
S12—C12	1.740 (3)	C28B—H28B	0.9500
S12—C17A	1.799 (4)	C28B—C29B	1.408 (17)
S12—C17B	1.830 (15)	C29B—H29C	0.9500
S21—C22	1.728 (3)	C29B—H29D	0.9500
S21—C25	1.748 (3)	C31—C32	1.380 (5)
S22—C22	1.747 (3)	C31—C36	1.384 (5)
S22—C27A	1.858 (6)	C32—H32	0.9500
S22—C27B	1.795 (8)	C32—C33	1.383 (7)
S31A—O31A	1.444 (5)	C33—H33	0.9500
S31A—O32A	1.458 (5)	C33—C34	1.378 (7)
S31A—O33A	1.447 (7)	C34—H34	0.9500
S31A—C31	1.819 (6)	C34—C35	1.398 (7)
S31B—O31B	1.458 (9)	C35—H35	0.9500
S31B—O32B	1.457 (11)	C35—C36	1.369 (6)
S31B—O33B	1.424 (8)	C36—H36	0.9500
S31B—C31	1.729 (9)	S41—O41	1.442 (3)
N12—H12A	0.91 (5)	S41—O42	1.446 (3)
N12—H12B	0.87 (5)	S41—O43	1.461 (2)
N12—C15	1.326 (4)	S41—C41	1.775 (4)
N13—N14	1.395 (3)	C41—C42	1.389 (5)
N13—C12	1.294 (4)	C41—C46	1.386 (5)
N14—C15	1.315 (4)	C42—H42	0.9500
N22—H22A	0.90 (5)	C42—C43	1.383 (7)
N22—H22B	0.86 (5)	C43—H43	0.9500
N22—C25	1.331 (4)	C43—C44	1.402 (8)
N23—N24	1.400 (3)	C44—H44	0.9500
N23—C22	1.296 (4)	C44—C45	1.367 (8)
N24—C25	1.319 (4)	C45—H45	0.9500
C17A—H17A	0.9900	C45—C46	1.388 (6)
C17A—H17B	0.9900	C46—H46	0.9500
C17A—C18A	1.498 (6)	O61—H61	0.75 (6)
C17B—H17C	0.9900	O61—C61	1.404 (5)
C17B—H17D	0.9900	C61—H61A	0.9800
C17B—C18B	1.45 (2)	C61—H61B	0.9800
C18A—H18A	0.9500	C61—H61C	0.9800
C18A—C19	1.369 (6)	O51—H51A	0.82 (6)
C18B—H18B	0.9500	O51—H51B	0.81 (7)
N13—Cu1—O31A	92.50 (13)	C18A—C19—H19A	120.0
N13—Cu1—O31B	80.46 (17)	C18A—C19—H19B	120.0
N13—Cu1—N24	109.96 (11)	C18B—C19—Cu1	73.4 (6)
N13—Cu1—C18A	98.26 (15)	C18B—C19—H19C	120.0
N13—Cu1—C18B	97.3 (4)	C18B—C19—H19D	120.0
N13—Cu1—C19	134.67 (13)	H19A—C19—H19B	120.0
N24—Cu1—O31A	107.80 (13)	H19C—C19—H19D	120.0
N24—Cu1—O31B	84.07 (16)	S21—C22—S22	117.10 (17)
N24—Cu1—C18A	150.68 (15)	N23—C22—S21	114.2 (2)
N24—Cu1—C18B	140.6 (4)	N23—C22—S22	128.7 (2)
N24—Cu1—C19	111.94 (13)	N22—C25—S21	120.8 (2)
C18A—Cu1—O31A	77.89 (17)	N24—C25—S21	113.1 (2)
C18B—Cu1—O31B	129.4 (5)	N24—C25—N22	126.1 (3)
C19—Cu1—O31A	90.65 (16)	S22—C27A—H27A	108.7
C19—Cu1—O31B	120.10 (19)	S22—C27A—H27B	108.7
C19—Cu1—C18A	38.75 (16)	H27A—C27A—H27B	107.6
C19—Cu1—C18B	37.7 (4)	C28A—C27A—S22	114.1 (4)
N14—Cu2—N23	110.59 (10)	C28A—C27A—H27A	108.7
N14—Cu2—C28A	151.09 (18)	C28A—C27A—H27B	108.7
N14—Cu2—C29A	111.7 (3)	Cu2—C28A—H28A	93.4
N14—Cu2—C28B	142.6 (2)	C27A—C28A—Cu2	105.9 (3)
N14—Cu2—C29B	114.5 (6)	C27A—C28A—H28A	119.4
N23—Cu2—C28A	98.32 (18)	C29A—C28A—Cu2	70.6 (5)
N23—Cu2—C29A	137.2 (3)	C29A—C28A—C27A	121.2 (8)
N23—Cu2—C28B	96.9 (2)	C29A—C28A—H28A	119.4
N23—Cu2—C29B	134.1 (5)	Cu2—C29A—H29A	106.0
C28A—Cu2—C29A	39.7 (3)	Cu2—C29A—H29B	94.0
C29B—Cu2—C28B	39.5 (6)	C28A—C29A—Cu2	69.7 (4)
C12—S11—C15	87.34 (15)	C28A—C29A—H29A	120.0
C12—S12—C17A	103.40 (18)	C28A—C29A—H29B	120.0
C12—S12—C17B	102.6 (5)	H29A—C29A—H29B	120.0
C22—S21—C25	87.48 (14)	S22—C27B—H27C	109.4
C22—S22—C27A	104.32 (18)	S22—C27B—H27D	109.4
C22—S22—C27B	103.5 (3)	H27C—C27B—H27D	108.0
O31A—S31A—O32A	111.4 (4)	C28B—C27B—S22	111.1 (6)
O31A—S31A—O33A	113.5 (4)	C28B—C27B—H27C	109.4
O31A—S31A—C31	103.4 (3)	C28B—C27B—H27D	109.4
O32A—S31A—C31	109.0 (3)	Cu2—C28B—H28B	96.3
O33A—S31A—O32A	111.4 (4)	C27B—C28B—Cu2	105.0 (5)
O33A—S31A—C31	107.7 (4)	C27B—C28B—H28B	120.7
O31B—S31B—C31	104.6 (5)	C29B—C28B—Cu2	68.2 (15)
O32B—S31B—O31B	112.5 (7)	C29B—C28B—C27B	118.7 (17)
O32B—S31B—C31	101.0 (6)	C29B—C28B—H28B	120.7
O33B—S31B—O31B	113.2 (6)	Cu2—C29B—H29C	103.6
O33B—S31B—O32B	113.6 (7)	Cu2—C29B—H29D	94.0
O33B—S31B—C31	110.8 (5)	C28B—C29B—Cu2	72.3 (13)
S31A—O31A—Cu1	126.0 (3)	C28B—C29B—H29C	120.0
S31B—O31B—Cu1	117.0 (4)	C28B—C29B—H29D	120.0
H12A—N12—H12B	118 (4)	H29C—C29B—H29D	120.0
C15—N12—H12A	122 (3)	C32—C31—S31A	125.1 (3)
C15—N12—H12B	119 (3)	C32—C31—S31B	112.0 (3)
N14—N13—Cu1	119.16 (19)	C32—C31—C36	119.6 (4)
C12—N13—Cu1	127.5 (2)	C36—C31—S31A	115.3 (3)
C12—N13—N14	113.1 (3)	C36—C31—S31B	128.4 (3)
N13—N14—Cu2	116.85 (19)	C31—C32—H32	120.2
C15—N14—Cu2	127.2 (2)	C31—C32—C33	119.6 (4)
C15—N14—N13	112.1 (2)	C33—C32—H32	120.2
H22A—N22—H22B	116 (4)	C32—C33—H33	119.5
C25—N22—H22A	121 (3)	C34—C33—C32	121.0 (4)
C25—N22—H22B	119 (3)	C34—C33—H33	119.5
N24—N23—Cu2	119.61 (18)	C33—C34—H34	120.5
C22—N23—Cu2	127.3 (2)	C33—C34—C35	119.1 (4)
C22—N23—N24	113.1 (3)	C35—C34—H34	120.5
N23—N24—Cu1	116.81 (18)	C34—C35—H35	120.1
C25—N24—Cu1	126.6 (2)	C36—C35—C34	119.8 (4)
C25—N24—N23	112.0 (2)	C36—C35—H35	120.1
S11—C12—S12	117.25 (18)	C31—C36—H36	119.5
N13—C12—S11	114.0 (2)	C35—C36—C31	120.9 (4)
N13—C12—S12	128.7 (3)	C35—C36—H36	119.5
N12—C15—S11	121.6 (3)	O41—S41—O42	114.2 (2)
N14—C15—S11	113.3 (2)	O41—S41—O43	111.24 (18)
N14—C15—N12	125.1 (3)	O41—S41—C41	106.60 (18)
S12—C17A—H17A	108.6	O42—S41—O43	112.07 (16)
S12—C17A—H17B	108.6	O42—S41—C41	106.11 (16)
H17A—C17A—H17B	107.5	O43—S41—C41	105.98 (17)
C18A—C17A—S12	114.8 (3)	C42—C41—S41	118.3 (3)
C18A—C17A—H17A	108.6	C46—C41—S41	121.0 (3)
C18A—C17A—H17B	108.6	C46—C41—C42	120.7 (4)
S12—C17B—H17C	108.6	C41—C42—H42	120.3
S12—C17B—H17D	108.6	C43—C42—C41	119.3 (4)
H17C—C17B—H17D	107.6	C43—C42—H42	120.3
C18B—C17B—S12	114.6 (11)	C42—C43—H43	119.9
C18B—C17B—H17C	108.6	C42—C43—C44	120.1 (4)
C18B—C17B—H17D	108.6	C44—C43—H43	119.9
Cu1—C18A—H18A	92.6	C43—C44—H44	120.1
C17A—C18A—Cu1	107.5 (3)	C45—C44—C43	119.8 (4)
C17A—C18A—H18A	118.3	C45—C44—H44	120.1
C19—C18A—Cu1	69.9 (2)	C44—C45—H45	119.6
C19—C18A—C17A	123.4 (4)	C44—C45—C46	120.8 (4)
C19—C18A—H18A	118.3	C46—C45—H45	119.6
Cu1—C18B—H18B	99.7	C41—C46—C45	119.3 (4)
C17B—C18B—Cu1	102.1 (10)	C41—C46—H46	120.3
C17B—C18B—H18B	116.7	C45—C46—H46	120.3
C19—C18B—Cu1	68.9 (6)	C61—O61—H61	109 (4)
C19—C18B—C17B	126.6 (14)	O61—C61—H61A	109.5
C19—C18B—H18B	116.7	O61—C61—H61B	109.5
Cu1—C19—H19A	106.1	O61—C61—H61C	109.5
Cu1—C19—H19B	92.5	H61A—C61—H61B	109.5
Cu1—C19—H19C	97.9	H61A—C61—H61C	109.5
Cu1—C19—H19D	98.6	H61B—C61—H61C	109.5
C18A—C19—Cu1	71.3 (2)	H51A—O51—H51B	107 (6)
Cu1—N13—N14—Cu2	−28.8 (3)	C12—S11—C15—N14	−1.4 (2)
Cu1—N13—N14—C15	171.7 (2)	C12—S12—C17A—C18A	63.3 (4)
Cu1—N13—C12—S11	−172.29 (16)	C12—S12—C17B—C18B	−63.0 (11)
Cu1—N13—C12—S12	7.9 (5)	C12—N13—N14—Cu2	156.3 (2)
Cu1—N24—C25—S21	−153.25 (16)	C12—N13—N14—C15	−3.2 (4)
Cu1—N24—C25—N22	28.4 (5)	C15—S11—C12—S12	179.4 (2)
Cu2—N14—C15—S11	−154.08 (16)	C15—S11—C12—N13	−0.5 (3)
Cu2—N14—C15—N12	26.2 (4)	C17A—S12—C12—S11	154.6 (2)
Cu2—N23—N24—Cu1	−26.2 (3)	C17A—S12—C12—N13	−25.5 (4)
Cu2—N23—N24—C25	176.0 (2)	C17A—C18A—C19—Cu1	98.2 (4)
Cu2—N23—C22—S21	−176.45 (14)	C17B—S12—C12—S11	−169.9 (5)
Cu2—N23—C22—S22	5.0 (4)	C17B—S12—C12—N13	9.9 (6)
S12—C17A—C18A—Cu1	−73.8 (3)	C17B—C18B—C19—Cu1	−89.6 (14)
S12—C17A—C18A—C19	−151.0 (3)	C22—S21—C25—N22	177.7 (3)
S12—C17B—C18B—Cu1	81.3 (11)	C22—S21—C25—N24	−0.8 (2)
S12—C17B—C18B—C19	153.9 (10)	C22—S22—C27A—C28A	55.9 (4)
S22—C27A—C28A—Cu2	−75.7 (4)	C22—S22—C27B—C28B	−64.8 (6)
S22—C27A—C28A—C29A	−152.3 (6)	C22—N23—N24—Cu1	155.4 (2)
S22—C27B—C28B—Cu2	80.4 (6)	C22—N23—N24—C25	−2.4 (4)
S22—C27B—C28B—C29B	153.5 (18)	C25—S21—C22—S22	178.01 (19)
S31A—C31—C32—C33	−178.5 (3)	C25—S21—C22—N23	−0.7 (2)
S31A—C31—C36—C35	178.2 (3)	C27A—S22—C22—S21	166.1 (2)
S31B—C31—C32—C33	−179.9 (4)	C27A—S22—C22—N23	−15.4 (3)
S31B—C31—C36—C35	179.4 (4)	C27A—C28A—C29A—Cu2	97.3 (5)
O31A—S31A—C31—C32	−39.7 (5)	C27B—S22—C22—S21	−162.1 (3)
O31A—S31A—C31—C36	142.0 (3)	C27B—S22—C22—N23	16.4 (4)
O31B—S31B—C31—C32	−118.6 (4)	C27B—C28B—C29B—Cu2	−95.7 (12)
O31B—S31B—C31—C36	61.8 (6)	C31—S31A—O31A—Cu1	−70.9 (4)
O32A—S31A—O31A—Cu1	46.0 (5)	C31—S31B—O31B—Cu1	83.3 (5)
O32A—S31A—C31—C32	−158.4 (3)	C31—C32—C33—C34	0.3 (6)
O32A—S31A—C31—C36	23.3 (4)	C32—C31—C36—C35	−0.2 (5)
O32B—S31B—O31B—Cu1	−168.0 (6)	C32—C33—C34—C35	0.2 (6)
O32B—S31B—C31—C32	124.4 (6)	C33—C34—C35—C36	−0.6 (6)
O32B—S31B—C31—C36	−55.2 (7)	C34—C35—C36—C31	0.6 (6)
O33A—S31A—O31A—Cu1	172.8 (4)	C36—C31—C32—C33	−0.3 (5)
O33A—S31A—C31—C32	80.6 (5)	S41—C41—C42—C43	179.6 (3)
O33A—S31A—C31—C36	−97.7 (4)	S41—C41—C46—C45	−179.4 (3)
O33B—S31B—O31B—Cu1	−37.5 (8)	O41—S41—C41—C42	58.2 (3)
O33B—S31B—C31—C32	3.7 (7)	O41—S41—C41—C46	−121.7 (3)
O33B—S31B—C31—C36	−175.9 (4)	O42—S41—C41—C42	−63.9 (3)
N13—N14—C15—S11	2.8 (3)	O42—S41—C41—C46	116.2 (3)
N13—N14—C15—N12	−176.9 (3)	O43—S41—C41—C42	176.8 (3)
N14—N13—C12—S11	2.1 (3)	O43—S41—C41—C46	−3.1 (3)
N14—N13—C12—S12	−177.7 (2)	C41—C42—C43—C44	0.3 (6)
N23—N24—C25—S21	1.9 (3)	C42—C41—C46—C45	0.7 (5)
N23—N24—C25—N22	−176.5 (3)	C42—C43—C44—C45	−0.5 (6)
N24—N23—C22—S21	1.9 (3)	C43—C44—C45—C46	0.7 (6)
N24—N23—C22—S22	−176.6 (2)	C44—C45—C46—C41	−0.9 (6)
C12—S11—C15—N12	178.3 (3)	C46—C41—C42—C43	−0.4 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12A···O51^i	0.91 (5)	1.94 (5)	2.765 (4)	150 (4)
N12—H12B···O41	0.87 (5)	2.00 (5)	2.867 (4)	174 (4)
N22—H22A···O42^ii	0.90 (5)	2.04 (5)	2.896 (4)	158 (4)
N22—H22B···O61^iii	0.86 (5)	1.96 (5)	2.758 (4)	154 (4)
C17A—H17A···O33A^iv	0.99	2.54	3.476 (7)	157
C17B—H17D···S31B^iv	0.99	2.76	3.676 (16)	154
C17B—H17D···O33B^iv	0.99	1.61	2.387 (16)	132
C18A—H18A···O31A	0.95	2.17	2.835 (6)	126
C27A—H27A···O33A^v	0.99	2.44	3.377 (8)	159
C28A—H28A···O32A	0.95	2.05	2.769 (7)	131
C27B—H27D···O32B^v	0.99	2.29	3.133 (13)	142
C28B—H28B···S41	0.95	3.01	3.891 (8)	155
C28B—H28B···O41	0.95	2.42	3.096 (9)	128
O61—H61···O43^vi	0.75 (6)	1.98 (6)	2.726 (4)	174 (6)
C61—H61B···O51^v	0.98	2.58	3.426 (5)	145
O51—H51A···O43^v	0.82 (6)	2.00 (7)	2.790 (4)	164 (6)
O51—H51B···O32B	0.81 (7)	2.20 (7)	3.010 (11)	170 (6)
O51—H51B···O33A	0.81 (7)	1.84 (7)	2.641 (7)	168 (6)

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