Structural diversity in copper(I) iodide complexes with 6-thioxopiperidin-2-one, piperidine-2,6-di­thione and isoindoline-1,3-di­thione ligands

Copper(I) iodide complexes are well known for displaying a diverse array of structural features even when only small changes in ligand design are made. This structural diversity is well displayed by five copper(I) iodide compounds reported here with closely related piperidine-2,6-di­thione (SNS), isoindoline-1,3-di­thione (SNS6), and 6-thioxopiperidin-2-one (SNO) ligands: di-μ-iodido-bis­[(aceto­nitrile-κN)(6-sulfanylidenepiperidin-2-one-κS)copper(I)], [Cu₂I₂(CH₃CN)₂(C₅H₇NOS)₂] (I), bis­(aceto­nitrile-κN)tetra-μ₃-iodido-bis­(6-sulfanylidenepiperidin-2-one-κS)-tetra­hedro-tetra­copper(I), [Cu₄I₄(CH₃CN)₄(C₅H₇NOS)₄] (II), catena-poly[[(μ-6-sulfanylidenepiperidin-2-one-κ²O:S)copper(I)]-μ₃-iodido], [CuI(C₅H₇NOS)]_n (III), poly[[(piperidine-2,6-di­thione-κS)copper(I)]-μ₃-iodido], [CuI(C₅H₇NS₂)]_n (IV), and poly[[(μ-isoindoline-1,3-di­thione-κ²S:S)copper(I)]-μ₃-iodido], [CuI(C₈H₅NS₂)]_n (V). Compounds I and II crystallize as discrete dimeric and tetra­meric complexes, whereas III, IV, and V crystallize as polymeric two-dimensional sheets. To the best of our knowledge, compound III is the first instance of an extended hexa­gonal [Cu₃I₃] structure that is not supported by bridging ligands. Structures I, II, and IV display weak to moderately strong Cu⋯Cu cuprophilic inter­actions [Cu⋯Cu inter­nuclear distances range between 2.5803 (10) and 2.8485 (14) Å]. All structures except III display weak hydrogen-bonding inter­actions between the N—H of the ligand and the μ₂ and μ₃-I⁻ atoms. Structure III contains classical N–H⋯O inter­actions between the SNO ligands that connect the mol­ecules in a three-dimensional framework. Complex V features π–π stacking inter­actions between the aryl rings of the SNS6 ligands within the same polymeric sheet. In structure IV, there were three partially occupied solvent mol­ecules of di­chloro­methane and one partially occupied mol­ecule of aceto­nitrile present in the asymmetric unit. The SQUEEZE routine [Spek (2015). Acta Cryst. C71, 9–18] was used to correct the diffraction data for diffuse scattering effects and to identify the solvent mol­ecules. The given chemical formula and other crystal data do not take into account the solvent mol­ecules.

1. Chemical context

Copper (I) iodide compounds have been of inter­est for the past 50 years because of their diverse structural (Peng et al., 2010) and spectroscopic properties (Ford et al., 1999; Hardt & Pierre, 1973). In particular, Cu^I complexes range from simple Cu₂I₂L₂ dimers (L = Lewis basic ligands) to complex three-dimensional coordination polymers (Peng et al., 2010). Traditionally, soft Lewis basic donors such as thiols or phosphines have been used as ligands to the Cu^I centers. We were inter­ested in exploring the structures of Cu^I coordination complexes with three ligands, piperidine-2,6-di­thione (SNS), isoindoline-1,3-di­thione (SNS6), and 6-thioxopiperidin-2-one (SNO) (Fig. 1). These ligands have been previously utilized in our work due to their polydentate binding modes, which provide individual binding sites that display a range of `hard' to `soft' Lewis basic behavior (Dolinar & Berry, 2013, 2014). Herein we report the synthesis and structural characterization of a series of five copper(I) iodide complexes with piperidine-2,6-di­thione (SNS), isoindoline-1,3-di­thione (SNS6), and 6-thioxopiperidin-2-one (SNO) ligands.

Figure 1 Diagrams of the three ligands used in the preparation of structures I–V.

2. Structural commentary

Compound I crystallizes as a discrete dimer with a rhombic Cu₂(μ₂-I)₂ core that resides on a crystallographic inversion center; thus, only one half of the dimer is symmetry-independent (Fig. 2). The rhombic core is close to having an ideal geometry with almost equal Cu—I distances (Table 1). Each Cu center is coordinated by two μ₂-I⁻ atoms, one mol­ecule of aceto­nitrile, and the thione moiety of the SNO ligand and has a slightly distorted tetra­hedral geometry (I—Cu—I and I—Cu—L angles of 100.19 (3)–118.719 (16)°; L = SNO or aceto­nitrile). The Cu⋯Cu inter­nuclear distance of 2.7274 (6) Å is slightly shorter than the sum of the covalent radii (ca 2.87 Å) and is consistent with a weak cuprophilic inter­action. The Cu—N and Cu—S distances (Table 1) in I are similar to the Cu—N and Cu—S distances in other discrete Cu₂(μ₂-I)₂ dimers reported to the Cambridge Structural Database (CSD) and selected with moderate search criteria (Groom et al. 2016; no errors, no polymers, single-crystal structures only). The SNO ligand adopts an envelope conformation, with a 49.07 (9)° dihedral angle between the planes defined by atoms C2–C3–C4 and C2–C1–N1–C5–C4.

Table 1
Selected bond lengths for structures I–V

	I^a		II^b		III^c		IV^d		V^e
Cu—I	I1—Cu1	2.6261 (6)	I1—Cu1	2.6451 (6)	I1—Cu1	2.6264 (11)	I1—Cu1	2.6365 (8)	I1—Cu1	2.6152 (13)
	I1—Cu1^i	2.6321 (7)	I1—Cu2^i	2.7017 (7)	I1—Cu1^i	2.6709 (12)	I1—Cu1^i	2.6687 (8)	I1—Cu1^i	2.6798 (13)
			I1—Cu2	2.7250 (6)	I1—Cu1^ii	2.6342 (10)	I2—Cu2	2.6719 (8)
			I2—Cu1	2.7796 (6)			I2—Cu2^ii	2.6724 (8)
			I2—Cu1^i	2.6542 (6)
			I2—Cu2	2.6456 (6)
Cu⋯Cu	Cu1—Cu1^i	2.7274 (6)	Cu1—Cu1^i	2.8150 (11)
			Cu1—Cu2	2.7864 (8)
			Cu1—Cu2^i	2.7106 (8)
			Cu2—Cu2^i	2.5803 (10)
Cu—S	Cu1—S1	2.3205 (6)	Cu1–S1	2.2869 (10)	Cu1—S1	2.2827 (15)	Cu1—S1	2.3086 (14)	Cu1—S1	2.269 (2)
							Cu1—S4^iii	2.3075 (13)	Cu1—S2^ii	2.273 (2)
							Cu2—S2	2.2802 (15)
							Cu2—S3	2.2933 (15)
Cu—N	Cu1—N2	2.0225 (10)	Cu2—N2	1.974 (3)
Symmetry codes: (a) (i) −x + 1, −y + 1, −z for I; (b) (i) −x + 1, y, −z +  for II; (c) (i) -x + 1/2, −y + , z −  and (ii) x, −y + 1, z −  for III; (d) (i) −x, −y, −z + 1; (ii) −x + 1, −y + 1, −z + 1 and (iii) −x + 1, −y, −z + 1 for IV; (e) (i) x, y − 1, z and (ii) x, −y + 1, z +  for V.

Figure 2 A mol­ecular drawing of I with 50% probability ellipsoids. Dotted lines are used to indicate hydrogen-bonding inter­actions. All H atoms bound to C atoms are omitted. [Symmetry code: (i) −x + 1, −y + 1, −z.]

Complex II crystallizes with a Cu₄(μ₃-I)₄ core; the four Cu atoms form a distorted tetra­hedron with μ₃-I⁻ atoms capping each of the tetra­hedron faces (Fig. 3). The center of the tetra­hedron resides on a crystallographic twofold axis and therefore only two of the Cu centers are symmetry-independent. These two Cu atoms have different first coordination spheres: Cu1 is coordinated by three μ₃-I⁻ atoms and one thione-bound SNO ligand; Cu2 is coordinated by three μ₃-I⁻ atoms and one aceto­nitrile ligand. Both Cu atoms have a distorted tetra­hedral geometry [I—Cu—I and I—Cu—L angles between 97.98 (3) and 118.71 (2)°; L = SNO or aceto­nitrile]. The inter­nuclear Cu⋯Cu distances vary between 2.5803 (10) and 2.8150 (11) Å (Table 1), which (similarly to I) are indicative of weak to moderately strong cuprophilic inter­actions between Cu atoms in the tetra­hedron. The Cu1—S and Cu2—N distances in II (Table 1) are slightly shorter than the Cu—S and Cu—N distances in I as a result of the increase from two μ₂-I⁻ to three μ₃-I⁻ atoms coordinating to each Cu center. The SNO ligand adopts an envelope conformation with a 47.5 (2)° dihedral angle between the planes defined by atoms C2–C3–C4 and C2–C1–N1–C5–C4.

Figure 3 A mol­ecular drawing of II shown with 50% probability ellipsoids. Dotted lines are used to indicate hydrogen-bonding inter­actions. All H atoms bound to C atoms are omitted. [Symmetry code: (i) −x + 1, y, −z + .]

Compound III crystallizes with layered two-dimensional polymeric sheets with a repeat (and symmetry-independent) unit formula of [Cu(μ₃-I)(SNO)]. The Cu atoms are coordinated by three μ₃-I⁻ atoms and one SNO ligand and have distorted tetra­hedral geometries [I—Cu—I and I—Cu—S angles of 97.12 (4)–120.62 (4)°] (Fig. 4). The I⁻ ions have distorted trigonal pyramidal geometries [Cu—I—Cu angles of 99.58 (3)–116.92 (2)°] with two short and one long Cu—I bonds (Table 1). The polymeric sheet is based on fused Cu₃I₃ six-membered rings with a screw-boat conformation (³S₂ with puckering amplitude Q = 1.3385 Å; Cremer & Pople, 1975) that propagate parallel to and stack perpendicularly to the (100) crystallographic plane (Fig. 5). These fused six-membered rings are reminiscent of the zinc-blend structure present in crystalline γ-CuI (Gruzintsev & Zagorodnev, 2012) except that the anions are μ₃ rather than μ₄. Each polymeric sheet is insulated by a sheath of SNO ligands, whose Cu—S bonds are perpendicular to the plane of propagation of the Cu₃I₃ rings (Fig. 6). The Cu⋯Cu distances between neighboring Cu atoms in the Cu₃I₃ rings measure between 4.2226 (15) and 4.5148 (15) Å, which are outside the range of inter­nuclear distances for cuprophilic inter­actions.

Figure 4 A mol­ecular drawing of the symmetry-independent portion of III with the full coordination sphere of the Cu center shown. All atoms are shown with 50% probability ellipsoids; all H atoms bound to C atoms are omitted. [Symmetry codes: (i) x, −y + 1, z − ; (ii) −x + , −y + , z − .]

Figure 5 A mol­ecular drawing of III's Cu3I3 fused rings viewed along the crystallographic a axis with 50% probability ellipsoids. All H atoms bound to C atoms are omitted.

Figure 6 A mol­ecular drawing of III viewed along the crystallographic b axis with 50% probability ellipsoids. Dotted lines are used to indicate hydrogen-bonding inter­actions. All H atoms bound to C atoms are omitted.

Similarly to III, IV crystallizes with layered two-dimensional polymeric sheets with the symmetry-independent unit formula [Cu(μ₂-I)(μ₂-SNS)]₂ (Fig. 7); the Cu and μ₂-I⁻ atoms form Cu₂(μ₂-I)₂ rhombi where the center of each rhombus resides on a crystallographic inversion center. Thus, the symmetry-independent unit is best described as containing two structurally distinct [Cu₂(μ₂-I)₂(μ₂-SNS)₂] half-dimers. The structures of the symmetry-independent Cu₂(μ₂-I)₂ rhombi differ in two notable ways: first, while the Cu₂(μ₂-I)₂ rhombus formed by Cu1, I1, and their symmetry-equivalents is slightly distorted, the rhombus formed by Cu2, I2, and their symmetry-equivalents is near ideal (Table 1). Secondly, the Cu⋯Cu distances in the rhombi differ by ca 0.07 Å [2.8485 (14) Å for the Cu1 rhombus; 2.7746 (15) Å for the Cu2 rhombus]. These values are consistent with little to no Cu⋯Cu cuprophilic inter­action in the Cu1 dimer while also indicating that there is a weak Cu⋯Cu cuprophilic inter­action in the Cu2 dimer. For both half dimers, the Cu atom's distorted tetra­hedral [I—Cu—I angles between 115.06 (3) and 117.46 (3)° and S—Cu—I angles of 96.95 (4)–119.35 (6)°] coordination sphere is filled by two thione moieties from the μ₂-SNS ligand; however, only one of these μ₂-SNS ligands per Cu atom is symmetry-independent (Fig. 8).

Figure 7 A mol­ecular drawing of the repeat unit of IV shown with 50% probability ellipsoids.

Figure 8 A mol­ecular drawing of IV with the full coordination spheres of the Cu centers shown with selected atom labels. All atoms are shown with 50% probability ellipsoids; dotted lines are used to indicate hydrogen-bonding inter­actions. All H atoms bound to C atoms are omitted. [Symmetry codes: (i) −x, −y, 1 − z; (ii) 1 − x, 1 − y, 1 − z; (iii) 1 − x, 1 − y, 1 − z; (iv) −1 + x, y, z]

In contrast to the monodentate SNO ligands in III, which only permit polymer propagation in III through the μ₃-I⁻ atoms, the bidentate SNS ligand facilitates polymer propagation in IV. This results in the formation of rings formed by four [Cu(μ₂-I)₂(μ₂-SNS)] units. The propagation of these rings in the (001) crystallographic plane results in a mesh-like sheet structure, and the layering of these sheets perpendicularly to the (001) plane results in the presence of sizable solvent-accessible voids (ca 200 ų) in the structure (Fig. 9). These voids are filled with a combination of aceto­nitrile and di­chloro­methane in an approximately 2:1 ratio; however, these solvent species were positionally disordered and the PLATON SQUEEZE routine (Spek, 2015) was required to model the diffuse electron density from the solvent species in these voids (see Refinement section).

Figure 9 A mol­ecular drawing of IV viewed along the [101] crystallographic direction with 50% probability ellipsoids. All H atoms bound to C atoms are omitted.

Complex V also crystallizes as two-dimensional polymeric sheets with the symmetry-independent unit formula [Cu(μ₂-I)(μ₂-SNS6)] (Fig. 10). The Cu center is coordinated by two μ₂-I⁻ atoms and two thione moieties of the μ₂-SNS6 ligands and has a distorted tetra­hedral geometry [I—Cu—I and I—Cu—S angles between 100.30 (6) and 120.16 (7)°]. Whereas the two S—Cu distances are almost identical, the two Cu—I distances are quite different (Table 1).

Figure 10 A mol­ecular drawing of the symmetry-independent portion of V with the full coordination sphere of the Cu center shown. All atoms are shown with 50% probability ellipsoids; dotted lines are used to indicate hydrogen-bonding inter­actions. All H atoms bound to C atoms are omitted. [Symmetry codes: (i) x, 1 + y, z; (ii) x, 1 − y,  + z.]

The polymeric sheet propagates parallel to the (100) crystallographic plane. The μ₂-I⁻ atoms bridge two Cu centers and form Cu–I zigzag chains that propagate parallel to the [010] crystallographic direction. Similarly to IV, the μ₂-SNS6 ligands participate in the polymer propagation in V by bridging two Cu atoms and connecting the Cu–I chains and are generated by the c glide plane (Fig. 11). Among the five structures discussed, V is the only non-centrosymmetric structure. This results in a packing motif with a polar arrangement of SNS6 ligands on one side of the inorganic sheets, which results in a smaller spacing between the inorganic layers [7.598 (3) Å, see Fig. 12] in V than in III [14.134 (5) Å, see Fig. 13].

Figure 11 A mol­ecular drawing of V viewed along the crystallographic b axis with 50% probability ellipsoids with emphasis on the weak N—H⋯I inter­actions (dotted lines). All H atoms bound to C atoms are omitted.

Figure 12 A mol­ecular drawing of V viewed along the crystallographic c axis with 50% probability ellipsoids. Dotted lines are used to indicate hydrogen-bonding inter­actions. All H atoms bound to C atoms are omitted.

Figure 13 A mol­ecular drawing of III viewed along the crystallographic c axis with 50% probability ellipsoids. Dotted lines are used to indicate hydrogen-bonding inter­actions. All H atoms bound to C atoms are omitted.

3. Supra­molecular features

Among the five structures reported in this work, III, IV, and V crystallize as polymeric sheets; their extended structural characteristics are described above. In addition to the polymeric structural features in III, IV, and V, there are also several types of inter­molecular inter­actions present in each of the five structures that are relevant to a description of their supra­molecular architectures.

All structures except III display non-classical (e.g., H-atom acceptors that are not N, O or Cl) hydrogen-bonding inter­actions between the N—H of the SNO/SNS/SNS6 ligands and the μ₂–I⁻/μ₃–I⁻ atoms. According to our statistical analysis of 3396 N—H⋯I inter­actions observed in 2030 structures reported to the CSD, their D⋯A distances range from 3.15 to 4.12 Å with a mean D⋯A distance of 3.69 (13) Å. The D⋯A distances in structures I, II, IV, and V are typical for these types of inter­actions (Table 2). For structures I and II, the N—H⋯I inter­action is intra­molecular. For IV, there are two symmetry-independent hydrogen–bonding inter­actions, which is expected given that the structure contains two symmetry-independent SNS ligands. The first, between atoms N1—H1⋯I1ⁱⁱ [symmetry code: (ii) −x + 1, −y + 1, −z + 1], is a stronger inter­action; the second is between atoms N2^iv—H2^iv⋯I1 [symmetry code: (iv) x + 1, y, z] and is a weaker inter­action (Table 2). Both inter­actions form S(6) hydrogen-bonding motifs (Etter et al. 1990), which provide some rigidity to the mesh-like sheet of the polymer.

Table 2
Hydrogen bonding geometries for I–V

	D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
I^a	N1—H1⋯I1^i	0.857 (12)	2.845 (13)	3.6980 (12)	173.8 (13)
II	N1—H1⋯I2	0.870 (19)	2.81 (2)	3.672 (3)	170 (4)
III^b	N1—H1⋯O1^iii	0.86 (2)	2.03 (2)	2.881 (5)	171 (5)
IV^c	N1—H1⋯I2^ii	0.88	2.79	3.628 (4)	160.9
	N2—H2⋯I1^iv	0.88	2.90	3.679 (4)	149.2
V^d	N1—H1⋯I1^iii	0.88	2.84	3.692 (7)	163.2
Symmetry codes: (a) (i) −x + 1, −y + 1, −z for I; (b) (iii) −x + 1, −y + 1, −z + 2 for III; (c) (ii) −x + 1, −y + 1, −z + 1 and (iv) x + 1, y, z for IV; (d) (iii) x, −y + 1, z −  for IV.

Structure III is unique among all the structures discussed in this work as it is the only structure to exhibit classical hydrogen-bonding inter­actions. There are two identical hydrogen bonds per SNO ligand, with the N—H serving as an H-bond donor and the O atom serving as an H-bond acceptor [N1—H1⋯O1ⁱⁱⁱ and N1ⁱⁱⁱ—Hⁱⁱⁱ⋯O1; symmetry code: (iii) −x + 1, −y + 1, −z + 2]. These hydrogen bonds are relatively strong (Table 2) and form R₂²(8) motifs between the stacked [Cu₃I₃]_n polymeric layers. Their presence leads to an extended three-dimensional framework structure, where the propagation of the [Cu₃I₃]_n polymeric sheets accounts for two dimensions and the connection of those sheets through the hydrogen-bonding inter­actions provides the third (Fig. 13).

Structure V has two distinct types of inter­molecular inter­actions. First, there is the non-classical hydrogen-bonding inter­action between the N—H of the SNS6 ligand and the symmetry-equivalent μ₂-I⁻ atoms [N1—H1⋯I1^ii; symmetry code: (ii) x, 1 − y, − + z] within the same polymeric sheet. This inter­action forms R₂²(6) motifs that are of typical strength (see Figs. 10 and 11; Table 2). In addition to the non-classical hydrogen-bonding inter­actions, there are also π–π stacking inter­actions between SNS6 ligands within the same polymeric sheet due to the presence of the extended π system in the SNS6 ligand backbone. These inter­actions, formed by the overlap between the five-membered rings with atoms C1–C2–C7–C8–N1 (R₅) and the phenyl rings with atoms C2ⁱ–C3ⁱ–C4ⁱ–C5ⁱ–C6ⁱ–C7ⁱ (R₆) [symmetry code: (i) x, 1 + y, z], is of moderate strength [plane R₅ to R₆ centroid distance: 3.369 (5) Å; R₅ to R₆ centroid offset distance: 1.165 (14) Å]. These π–π stacking inter­actions, in tandem with the increased size of the SNS6 ligand relative to the SNS/SNO ligands, results in a tightly packed two-dimensional sheet (packing coefficient: 71.8%), which prevents the formation of the more mesh-like structure seen in IV (packing coefficient: 54.1%) (Kitaigorodskii, 1973).

4. Database survey

All searches in the Cambridge Structural Database (Version 5.41, latest update May 2020; Groom et al. 2016) were performed with moderate search criteria (for structures I and II: no errors or ions, not polymeric, only single crystal structures; for structures III, IV, and V: no errors or ions, only single crystal structures. The surveys of the database for each individual structure are described below.

I: A search for Cu₂(μ₂-I)₂ dimers with two neutral ligands binding with one nitro­gen and one sulfur atom resulted in 17 matches. Only one had a homometallic [Cu(μ₂-I)₂(S)(N)]₂ type structure where the S and N donors were part of monodentate ligands, which indicates that the coordination environment in I is a relatively unusual one. This structure, bis­[(μ₂-iodo)(aceto­nitrile)(tri­phenyl­thio­phospho­rane)copper(I)] (refcode: OCALOT; Lobana et al., 2001), has similar Cu—S and Cu—N distances and a slightly longer Cu—I distance. However, OCALOT has a dramatically longer Cu⋯Cu distance [3.4141 (16) Å] than that in I (Table 1). This elongation is likely due to the larger steric requirements of the SPPh₃ sulfur donor ligand in OCALOT.

II: a survey of the Cambridge Structural Database for Cu₄(μ₃-I)₄ tetra­hedrons with a mix of two Cu I₃N coordination spheres and two I₃S coordination spheres provided only one match, octa­kis­(μ₃-iodo)­bis­{μ₂-bis­[(2,4-di­methyl­phen­yl)thio]­methane-S,S′}tetra­kis­(aceto­nitrile)­octa­copper(I) aceto­nitrile tetra­hydro­furan solvate (refcode: ENAXAT; Martínez-Alanis et al., 2011), which features two Cu₄(μ₃-I)₄ tetra­hedrons. Two of the Cu centers in each tetra­hedron have a (μ₃-I)₃(NCCH₃) coordination sphere. The other two Cu centers have (μ₃-I)₃S coordination spheres with bridging bis­[(3,5-di­methyl­phen­yl)thio]­methane ligands that tether the two tetra­hedra together. The geometric parameters of this structure [Cu⋯Cu, Cu—I, Cu—S, and Cu—N distances: 2.69 (3), 2.68 (4), 2.315 (11), and Cu—N 1.979 (6) Å] are very similar to those in II.

An additional, broader search for all non-polymeric Cu₄(μ₃-I) tetra­hedra yielded 130 results for Cu₄(μ₃-I)₄(L)₄ (L = N, S, P, I, O, As) tetra­hedra with L as a neutral ligand. All of the resulting structures had identical first coordination spheres for each of the Cu centers [e.g., Cu₄(μ₃-I)₄(L)₄, rather than the Cu₄(μ₃-I)₄(L)₂(L′)₂ in II]. To the best of our knowledge, II is the first reported instance of a non-polymeric Cu₄(μ₃-I)₄ tetra­hedron with N and (non-bridging) S ligands.

III: A search for structures containing Cu₃(μ₃-X)₃ ring motifs that did not contain Cu₄(μ₃-X)₄ (X = any halogen) tetra­hedral motifs yielded 60 structures. Four of them contained Cu₃(μ₃-X)₃ motifs and one of them (DENQEV; Liu et al., 2018) contained a Cu₃(μ₃-X)₃ ring motif. This structure, catena-[bis­[μ-5-(1-amino­eth­yl)tetra­zolato]tetra­kis­(μ-iodo)­copper(II)tetra­copper(I)], contains four monovalent and one divalent symmetry-independent Cu centers that form a one-dimensional ribbon. This ribbon, in combination with the bridging (1S)-1-(5-tetra­zol­yl) ethyl­amine ligands, forms a three-dimensional network. There are a few other examples of copper halide extended structures based on Cu₃(μ₃-X)₃ ring motifs that are both one-dimensional (Näther & Jess, 2003; Oliver et al., 1977) and two-dimensional (Blake et al., 1999; Haakansson et al., 1991; Haakansson & Jagner, 1990). Among these, the [Cu₂I₂(μ₃-1,3,5-triazine)]_∞ structure reported by Blake et al. is the only two-dimensional sheet with hexa­gonal Cu₃I₃ rings and μ₃-triazine linkers. To the best of our knowledge, III is the first instance of this extended hexa­gonal Cu₃I₃ structure that is not supported by bridging ligands.

IV: A search for polymeric structures containing Cu₂(μ₂-X)₂(μ₂-S) (X = F⁻, Cl⁻, Br⁻, I⁻) rhombi afforded 91 matches that included 35 polymeric homometallic structures. Among the 35 structures, 23 were two-dimensional polymers. Whereas there were no closely related matches for IV, a similar structure (JIZPEQ; Raghuvanshi et al., 2019) was found. This structure has the same chemical composition as IV except with μ₂-1,3-di­thiane ligands rather than μ₂-SNS ligands. In contrast to the two-dimensional mesh-like structure of IV, JIZPEQ crystallizes with one-dimensional chains with links comprised of two Cu₂(μ₂-I)₂ rhombi and two μ₂-1,3-di­thiane ligands. The geometric parameters of the Cu₂(μ₂-I)₂ rhombi are in good agreement with those in IV [Cu⋯Cu, Cu—I (average), and Cu—S (average) distances: 2.8904 (6), 2.63 (2), and 2.329 (3) Å].

V: A search for structures with Cu—X zigzag chains that did not contain the Cu₂(μ₂-X)₂ rhombus afforded 112 matches. Among these, 56 were for polymeric homometallic structures and three of these [refcodes: AFUDUA (Caradoc-Davies et al., 2002), CIQQOL (Musina et al., 2017), and FIWWAK (Cingolani et al., 2005)] contained one-dimensional Cu—I⁻ zigzag chains. All three structures contain tetra­hedral Cu^I centers coordinated by the two μ₂-I atoms and two neutral donor ligands (binding with sulfur and nitro­gen for AFUNDA, arsenic for CIQQOL, and FIWWAK). These structures have similar geometries to that of V except for the Cu–ligand distances.

5. Synthesis and crystallization

The ligands piperidine-2,6-di­thione (SNS) and 6-thioxopiperidin-2-one (SNO) were purchased from Sigma–Aldrich and used as received. Isoindoline-1,3-di­thione (SNS6) was prepared in a similar manner to that previously described in the literature (Yde et al., 1984).

Unless otherwise specified, all reactions were performed at room temperature under a dry N₂ atmosphere using standard glovebox methods.

I was prepared by combining 10 ml of a clear yellow solution of 6-thioxopiperidin-2-one (0.500 mmol) in di­chloro­methane with 10 mL of a colorless solution of CuI (0.502 mmol) in aceto­nitrile. Upon combination, the solution turned a bright-orange color. Vapor diffusion of the orange solution with diethyl ether afforded large, yellow, block-shaped crystals of I after three days.

Two by-products were also obtained from the reaction of 6-thioxopiperidin-2-one and CuI. The first (II) were small, yellow, plate-shaped crystals that co-crystallized with the larger yellow block-shaped crystals of I. The second by-product formed after exposing the initial orange solution from the reaction of 6-thioxopiperidin-2-one and CuI to air, and allowing that solution to slowly evaporate in air for approximately one week. After this time, small, red–orange crystals of III were obtained.

IV was prepared by layering 10 mL of a clear yellow solution of piperidine-2,6-di­thione (1.01 mmol) in di­chloro­methane over 10 mL of a colorless solution of CuI (1.00 mmol) in aceto­nitrile. Dark-red crystals of IV were obtained after one week.

Black, needle-shaped crystals of V were obtained in a similar manner to IV, with the exception that 1.00 mmol of isoindoline-1,3-di­thione was used instead of piperidine-2,6-di­thione.

6. Refinement

For structure I, the diffraction data were consistent with the space groups P1 and P; the E-statistics were consistent for the centrosymmetric space group P and were used to make the final space-group determination. For structures II–V, a combination of the systematic absences in the diffraction data and the E-statistics were used to assign the centrosymmetric space groups C2/c (II), Pbcn (III), P2₁/c (IV) and the non-centrosymmetric space group Cc (V).

The structures were solved via intrinsic phasing and refined by least-squares refinement on F² followed by difference-Fourier synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. Unless otherwise specified, all hydrogen atoms were included in the final structure-factor calculation at idealized positions and were allowed to ride on the neighboring atoms with relative isotropic displacement coefficients.

The coordinates of the H atoms bound to N atoms in structures I, II, and III were refined freely with a distance restraint for each N—H distance.

In structure IV, there were three partially occupied solvent mol­ecules of di­chloro­methane and one partially occupied mol­ecule of aceto­nitrile present in the asymmetric unit. A significant amount of time was invested in identifying and refining the disordered mol­ecules. Bond-length restraints were applied to model the mol­ecules, but the resulting isotropic displacement coefficients suggested the mol­ecules were mobile. In addition, the refinement was computationally unstable. The SQUEEZE option (Spek, 2015) of the PLATON software suite (Spek, 2020) was used to correct the diffraction data for diffuse scattering effects and to identify the solvent mol­ecule. PLATON calculated the upper limit of volume that can be occupied by the solvent in the unit cell to be 615 ų. This solvent-accessible volume is comprised of two smaller (ca 115 ų) and two larger (ca 196 ų) solvent-accessible voids and is 27% of the unit-cell volume. The program calculated 155 electrons in the unit cell for the diffuse species. This corresponds to approximately one mol­ecule of di­chloro­methane (42 electrons) that is 50% occupied and one mol­ecule of aceto­nitrile (22 electrons) in the asymmetric unit. It is very likely that the solvent mol­ecules are disordered over several positions. All derived results in Tables 1 and 2 are based on the known contents. No data are given for the diffusely scattering species.

Crystal data, data collection and structure refinement details are summarized in Table 3.

Table 3
Experimental details

	I	II	III	IV	V
Crystal data
Chemical formula	[Cu2I2(C2H3N)2(C5H7NOS)2]	[Cu4I4(C2H3N)2(C5H7NOS)2]	[CuI(C5H7NOS)]	[Cu2I2(C5H7NS2)2]	[CuI(C8H5NS2)]
Mr	721.34	1102.22	319.62	671.35	369.69
Crystal system, space group	Triclinic, P	Monoclinic, C2/c	Orthorhombic, Pbcn	Monoclinic, P21/c	Monoclinic, Cc
Temperature (K)	100	105	100	100	100
a, b, c (Å)	8.121 (2), 8.433 (2), 9.154 (2)	14.4669 (8), 12.2157 (7), 16.9969 (11)	26.982 (11), 8.195 (4), 7.351 (3)	13.2866 (9), 11.6974 (13), 14.8089 (9)	15.174 (5), 4.1188 (16), 15.785 (6)
α, β, γ (°)	68.918 (12), 80.523 (12), 71.270 (9)	90, 112.562 (5), 90	90, 90, 90	90, 96.998 (6), 90	90, 92.98 (2), 90
V (Å^3)	553.2 (2)	2773.9 (3)	1625.4 (13)	2284.4 (3)	985.2 (6)
Z	1	4	8	4	4
Radiation type	Mo Kα	Cu Kα	Cu Kα	Cu Kα	Mo Kα
μ (mm^−1)	4.92	39.97	35.47	26.87	5.72
Crystal size (mm)	0.15 × 0.13 × 0.13	0.1 × 0.08 × 0.04	0.08 × 0.07 × 0.03	0.22 × 0.13 × 0.09	0.30 × 0.02 × 0.01
Data collection
Diffractometer	Bruker APEXII Quazar	Bruker SMART APEXII area detector	Bruker SMART APEXII area detector	Bruker SMART APEXII area detector	Bruker APEXII Quazar
Absorption correction	Multi-scan (SADABS; Bruker, 2016)	Multi-scan (SADABS; Bruker, 2016)	Multi-scan SADABS; Bruker, 2016)	Multi-scan (SADABS; Bruker, 2016)	Multi-scan (SADABS; Bruker, 2016)
Tmin, Tmax	0.079, 0.120	0.042, 0.188	0.030, 0.144	0.009, 0.094	0.322, 0.404
No. of measured, independent and observed [I > 2σ(I)] reflections	17922, 4099, 3988	23553, 2753, 2669	25274, 1631, 1467	78133, 4597, 4236	11871, 3603, 3226
Rint	0.021	0.060	0.051	0.063	0.041
(sin θ/λ)max (Å^−1)	0.779	0.622	0.622	0.622	0.770
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.012, 0.030, 1.07	0.026, 0.063, 1.10	0.032, 0.082, 1.07	0.048, 0.126, 1.06	0.036, 0.089, 1.06
No. of reflections	4099	2753	1631	4597	3603
No. of parameters	122	140	94	181	118
No. of restraints	1	1	1	0	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H-atom parameters constrained	H-atom parameters constrained
Δρmax, Δρmin (e Å^−3)	0.43, −0.34	0.84, −1.25	1.31, −1.03	1.58, −0.49	3.17, −1.13
Absolute structure	–	–	–	–	Flack x determined using 1438 quotients [(I^+)−(I^−)]/[(I^+)+(I^−)] (Parsons et al., 2013)
Absolute structure parameter	–	–	–	–	0.034 (12)
Computer programs: APEX3 (Bruker, 2017), APEX2 and SAINT (Bruker, 2013), SHELXT (Sheldrick, 2015a), SHELXL (Sheldrick, 2015b), and OLEX2 (Dolomanov et al., 2009).

Supporting information

Computing details

Data collection: APEX3 (Bruker, 2017) for (I), (V); APEX2 (Bruker, 2013) for (II), (III), (IV). Cell refinement: APEX3 (Bruker, 2017) for (I), (V); SAINT (Bruker, 2013) for (II), (III), (IV). Data reduction: APEX3 (Bruker, 2017) for (I), (V); SAINT (Bruker, 2013) for (II), (III), (IV). For all structures, program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Di-µ-iodido-bis[(acetonitrile-κN)(6-sulfanylidenepiperidin-2-one-κS)copper(I)] (I)

Crystal data

[Cu2I2(C2H3N)2(C5H7NOS)2]	Z = 1
Mr = 721.34	F(000) = 344
Triclinic, P1	Dx = 2.165 Mg m^−3
a = 8.121 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.433 (2) Å	Cell parameters from 9905 reflections
c = 9.154 (2) Å	θ = 2.4–33.6°
α = 68.918 (12)°	µ = 4.92 mm^−1
β = 80.523 (12)°	T = 100 K
γ = 71.270 (9)°	Block, yellow
V = 553.2 (2) Å^3	0.15 × 0.13 × 0.13 mm

Data collection

Bruker APEXII Quazar diffractometer	4099 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	3988 reflections with I > 2σ(I)
Mirror optics monochromator	Rint = 0.021
Detector resolution: 7.9 pixels mm^-1	θmax = 33.6°, θmin = 2.4°
0.5° ω and 0.5° φ scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −12→13
Tmin = 0.079, Tmax = 0.120	l = −14→13
17922 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.012	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.030	w = 1/[σ^2(Fo^2) + (0.010P)^2 + 0.2P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
4099 reflections	Δρmax = 0.43 e Å^−3
122 parameters	Δρmin = −0.34 e Å^−3
1 restraint

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
I1	0.71563 (2)	0.27834 (2)	−0.05209 (2)	0.01894 (2)
Cu1	0.45123 (2)	0.38128 (2)	0.13294 (2)	0.01894 (3)
S1	0.56399 (3)	0.24010 (4)	0.37914 (3)	0.01986 (5)
O1	0.05297 (11)	0.66482 (10)	0.51701 (10)	0.02183 (14)
N1	0.28752 (11)	0.45357 (12)	0.47278 (10)	0.01722 (15)
H1	0.278 (2)	0.5149 (19)	0.3753 (15)	0.021*
N2	0.26648 (13)	0.25871 (13)	0.15713 (11)	0.02214 (17)
C1	0.41889 (13)	0.30218 (13)	0.51318 (11)	0.01629 (16)
C2	0.42947 (14)	0.19443 (14)	0.68381 (12)	0.02105 (18)
H2A	0.508966	0.227581	0.731337	0.025*
H2B	0.479000	0.067327	0.694709	0.025*
C3	0.25216 (15)	0.22197 (14)	0.77191 (12)	0.02196 (19)
H3A	0.265859	0.157362	0.885379	0.026*
H3B	0.176642	0.174405	0.734521	0.026*
C4	0.16790 (15)	0.41932 (14)	0.74515 (12)	0.02137 (19)
H4A	0.048628	0.437280	0.795116	0.026*
H4B	0.235816	0.462532	0.795254	0.026*
C5	0.15956 (13)	0.52448 (13)	0.57383 (12)	0.01738 (17)
C6	0.17193 (13)	0.17425 (13)	0.20890 (12)	0.01823 (17)
C7	0.05487 (15)	0.06411 (15)	0.27580 (14)	0.02279 (19)
H7A	0.012545	0.043830	0.191652	0.034*
H7B	−0.044124	0.123970	0.332437	0.034*
H7C	0.117167	−0.049821	0.348452	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.02097 (3)	0.01735 (3)	0.01597 (3)	−0.00396 (2)	0.00281 (2)	−0.00554 (2)
Cu1	0.02026 (6)	0.01995 (6)	0.01757 (6)	−0.00817 (5)	0.00300 (4)	−0.00688 (5)
S1	0.01667 (10)	0.02251 (11)	0.01925 (11)	−0.00292 (9)	0.00063 (8)	−0.00856 (9)
O1	0.0229 (4)	0.0176 (3)	0.0234 (4)	−0.0036 (3)	0.0001 (3)	−0.0073 (3)
N1	0.0191 (4)	0.0168 (4)	0.0141 (3)	−0.0045 (3)	0.0007 (3)	−0.0044 (3)
N2	0.0219 (4)	0.0223 (4)	0.0229 (4)	−0.0073 (3)	0.0004 (3)	−0.0079 (3)
C1	0.0164 (4)	0.0175 (4)	0.0165 (4)	−0.0059 (3)	−0.0013 (3)	−0.0062 (3)
C2	0.0237 (5)	0.0204 (4)	0.0161 (4)	−0.0028 (4)	−0.0038 (3)	−0.0044 (3)
C3	0.0292 (5)	0.0181 (4)	0.0165 (4)	−0.0082 (4)	0.0017 (4)	−0.0033 (3)
C4	0.0270 (5)	0.0200 (4)	0.0159 (4)	−0.0075 (4)	0.0037 (4)	−0.0059 (3)
C5	0.0192 (4)	0.0169 (4)	0.0176 (4)	−0.0071 (3)	0.0020 (3)	−0.0071 (3)
C6	0.0180 (4)	0.0177 (4)	0.0183 (4)	−0.0029 (3)	−0.0013 (3)	−0.0069 (3)
C7	0.0233 (5)	0.0219 (5)	0.0254 (5)	−0.0108 (4)	0.0042 (4)	−0.0088 (4)

Geometric parameters (Å, º)

I1—Cu1	2.6261 (6)	C2—H2B	0.9900
I1—Cu1^i	2.6321 (7)	C2—C3	1.5216 (16)
Cu1—Cu1^i	2.7274 (6)	C3—H3A	0.9900
Cu1—S1	2.3205 (6)	C3—H3B	0.9900
Cu1—N2	2.0225 (10)	C3—C4	1.5260 (16)
S1—C1	1.6607 (11)	C4—H4A	0.9900
O1—C5	1.2117 (13)	C4—H4B	0.9900
N1—H1	0.857 (12)	C4—C5	1.4988 (15)
N1—C1	1.3493 (13)	C6—C7	1.4518 (15)
N1—C5	1.4055 (13)	C7—H7A	0.9800
N2—C6	1.1446 (14)	C7—H7B	0.9800
C1—C2	1.4987 (15)	C7—H7C	0.9800
C2—H2A	0.9900
Cu1—I1—Cu1^i	62.489 (13)	C3—C2—H2B	109.2
I1—Cu1—I1^i	117.511 (13)	C2—C3—H3A	109.7
I1^i—Cu1—Cu1^i	58.647 (16)	C2—C3—H3B	109.7
I1—Cu1—Cu1^i	58.864 (17)	C2—C3—C4	109.71 (9)
S1—Cu1—I1	102.61 (2)	H3A—C3—H3B	108.2
S1—Cu1—I1^i	118.719 (16)	C4—C3—H3A	109.7
S1—Cu1—Cu1^i	132.375 (17)	C4—C3—H3B	109.7
N2—Cu1—I1^i	105.18 (3)	C3—C4—H4A	109.3
N2—Cu1—I1	111.38 (3)	C3—C4—H4B	109.3
N2—Cu1—Cu1^i	127.14 (3)	H4A—C4—H4B	108.0
N2—Cu1—S1	100.19 (3)	C5—C4—C3	111.49 (9)
C1—S1—Cu1	109.94 (4)	C5—C4—H4A	109.3
C1—N1—H1	118.1 (10)	C5—C4—H4B	109.3
C1—N1—C5	127.15 (9)	O1—C5—N1	118.17 (9)
C5—N1—H1	114.7 (10)	O1—C5—C4	125.23 (10)
C6—N2—Cu1	162.96 (9)	N1—C5—C4	116.60 (9)
N1—C1—S1	121.16 (8)	N2—C6—C7	178.87 (12)
N1—C1—C2	117.20 (9)	C6—C7—H7A	109.5
C2—C1—S1	121.63 (8)	C6—C7—H7B	109.5
C1—C2—H2A	109.2	C6—C7—H7C	109.5
C1—C2—H2B	109.2	H7A—C7—H7B	109.5
C1—C2—C3	112.14 (9)	H7A—C7—H7C	109.5
H2A—C2—H2B	107.9	H7B—C7—H7C	109.5
C3—C2—H2A	109.2
Cu1—S1—C1—N1	−20.58 (9)	C1—C2—C3—C4	−54.31 (12)
Cu1—S1—C1—C2	160.32 (7)	C2—C3—C4—C5	54.18 (12)
S1—C1—C2—C3	−153.63 (8)	C3—C4—C5—O1	153.16 (10)
N1—C1—C2—C3	27.24 (13)	C3—C4—C5—N1	−27.45 (13)
C1—N1—C5—O1	178.41 (10)	C5—N1—C1—S1	−177.90 (8)
C1—N1—C5—C4	−1.02 (15)	C5—N1—C1—C2	1.24 (15)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···I1^i	0.86 (1)	2.85 (1)	3.6980 (12)	174 (1)

Symmetry code: (i) −x+1, −y+1, −z.

Bis(acetonitrile-κN)tetra-µ₃-iodido-bis(6-sulfanylidenepiperidin-2-one-κS)-tetrahedro-tetracopper(I) (II)

Crystal data

[Cu4I4(C2H3N)2(C5H7NOS)2]	F(000) = 2032
Mr = 1102.22	Dx = 2.639 Mg m^−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
a = 14.4669 (8) Å	Cell parameters from 9916 reflections
b = 12.2157 (7) Å	θ = 4.9–73.4°
c = 16.9969 (11) Å	µ = 39.97 mm^−1
β = 112.562 (5)°	T = 105 K
V = 2773.9 (3) Å^3	Block, yellow
Z = 4	0.1 × 0.08 × 0.04 mm

Data collection

Bruker SMART APEXII area detector diffractometer	2753 independent reflections
Radiation source: sealed X-ray tube, Siemens, K FFCU 2K 90	2669 reflections with I > 2σ(I)
Equatorially mounted graphite monochromator	Rint = 0.060
Detector resolution: 7.9 pixels mm^-1	θmax = 73.4°, θmin = 4.9°
0.60° ω and 0.6° φ scans	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −15→15
Tmin = 0.042, Tmax = 0.188	l = −19→20
23553 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.063	w = 1/[σ^2(Fo^2) + (0.0336P)^2 + 8.1228P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.001
2753 reflections	Δρmax = 0.84 e Å^−3
140 parameters	Δρmin = −1.25 e Å^−3
1 restraint

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
I1	0.60668 (2)	0.86418 (2)	0.17606 (2)	0.01452 (8)
I2	0.64470 (2)	0.62302 (2)	0.36802 (2)	0.01064 (8)
Cu1	0.56033 (4)	0.66150 (4)	0.20182 (3)	0.01367 (13)
Cu2	0.57587 (4)	0.82337 (4)	0.32174 (3)	0.01552 (13)
S1	0.60446 (7)	0.54868 (7)	0.11461 (5)	0.01569 (19)
O1	0.6145 (2)	0.2772 (2)	0.32682 (16)	0.0174 (6)
N1	0.6055 (2)	0.3917 (3)	0.22074 (19)	0.0126 (6)
H1	0.606 (4)	0.445 (3)	0.255 (2)	0.015*
N2	0.6525 (3)	0.9386 (3)	0.4015 (2)	0.0169 (7)
C1	0.6091 (3)	0.4194 (3)	0.1448 (2)	0.0123 (7)
C2	0.6188 (3)	0.3267 (3)	0.0903 (2)	0.0159 (8)
H2A	0.690589	0.314522	0.102177	0.019*
H2B	0.585384	0.347436	0.029590	0.019*
C3	0.5734 (3)	0.2208 (3)	0.1056 (2)	0.0202 (8)
H3A	0.587416	0.160825	0.072514	0.024*
H3B	0.499919	0.228893	0.086154	0.024*
C4	0.6177 (3)	0.1928 (3)	0.2001 (3)	0.0191 (8)
H4A	0.581117	0.129536	0.210478	0.023*
H4B	0.688502	0.170761	0.216276	0.023*
C5	0.6128 (3)	0.2859 (3)	0.2552 (2)	0.0132 (7)
C6	0.6848 (3)	1.0148 (3)	0.4409 (2)	0.0148 (7)
C7	0.7242 (3)	1.1137 (3)	0.4894 (2)	0.0180 (8)
H7A	0.709649	1.176523	0.450663	0.027*
H7B	0.796763	1.106656	0.519796	0.027*
H7C	0.692732	1.124854	0.530632	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01753 (14)	0.01161 (13)	0.01566 (13)	−0.00092 (8)	0.00776 (10)	0.00418 (7)
I2	0.01430 (13)	0.01007 (13)	0.00576 (12)	0.00111 (7)	0.00185 (9)	0.00183 (7)
Cu1	0.0197 (3)	0.0114 (3)	0.0103 (2)	0.0035 (2)	0.0062 (2)	0.00158 (19)
Cu2	0.0167 (3)	0.0119 (3)	0.0134 (2)	−0.0027 (2)	0.0007 (2)	−0.00354 (19)
S1	0.0246 (5)	0.0150 (4)	0.0113 (4)	0.0070 (3)	0.0112 (4)	0.0050 (3)
O1	0.0214 (14)	0.0183 (13)	0.0118 (11)	−0.0011 (11)	0.0056 (11)	0.0035 (10)
N1	0.0198 (17)	0.0107 (14)	0.0071 (13)	0.0003 (12)	0.0049 (12)	−0.0007 (11)
N2	0.0173 (16)	0.0157 (16)	0.0139 (14)	−0.0037 (13)	0.0019 (12)	−0.0027 (13)
C1	0.0123 (17)	0.0152 (18)	0.0078 (14)	0.0021 (13)	0.0021 (13)	0.0000 (13)
C2	0.0216 (19)	0.0150 (18)	0.0118 (15)	0.0062 (15)	0.0071 (15)	−0.0020 (13)
C3	0.023 (2)	0.019 (2)	0.0190 (18)	−0.0007 (16)	0.0083 (16)	−0.0087 (15)
C4	0.027 (2)	0.0127 (18)	0.0225 (18)	−0.0004 (15)	0.0145 (17)	−0.0027 (15)
C5	0.0111 (17)	0.0135 (17)	0.0132 (16)	−0.0019 (13)	0.0029 (14)	−0.0001 (13)
C6	0.0169 (18)	0.0143 (18)	0.0091 (14)	0.0025 (14)	0.0003 (14)	0.0011 (14)
C7	0.029 (2)	0.0071 (17)	0.0103 (16)	−0.0010 (15)	−0.0003 (15)	−0.0020 (13)

Geometric parameters (Å, º)

I1—Cu1	2.6451 (6)	N1—C5	1.405 (5)
I1—Cu2^i	2.7017 (7)	N2—C6	1.137 (5)
I1—Cu2	2.7250 (6)	C1—C2	1.504 (5)
I2—Cu1	2.6542 (6)	C2—H2A	0.9900
I2—Cu1^i	2.7796 (6)	C2—H2B	0.9900
I2—Cu2	2.6456 (6)	C2—C3	1.518 (6)
Cu1—Cu1^i	2.8150 (11)	C3—H3A	0.9900
Cu1—Cu2	2.7864 (8)	C3—H3B	0.9900
Cu1—Cu2^i	2.7106 (8)	C3—C4	1.523 (5)
Cu2—Cu2^i	2.5803 (10)	C4—H4A	0.9900
Cu1—S1	2.2869 (10)	C4—H4B	0.9900
Cu2—N2	1.974 (3)	C4—C5	1.492 (5)
S1—C1	1.654 (4)	C6—C7	1.451 (5)
O1—C5	1.213 (5)	C7—H7A	0.9800
N1—H1	0.870 (19)	C7—H7B	0.9800
N1—C1	1.354 (5)	C7—H7C	0.9800
Cu1—I1—Cu2^i	60.911 (18)	N2—Cu2—I1^i	98.80 (11)
Cu1—I1—Cu2	62.493 (17)	N2—Cu2—I1	104.44 (10)
Cu2^i—I1—Cu2	56.78 (2)	N2—Cu2—I2	114.05 (10)
Cu1—I2—Cu1^i	62.35 (2)	N2—Cu2—Cu1	151.07 (11)
Cu2—I2—Cu1	63.439 (17)	N2—Cu2—Cu1^i	143.75 (11)
Cu2—I2—Cu1^i	59.892 (17)	N2—Cu2—Cu2^i	134.36 (10)
I1—Cu1—I2	107.43 (2)	C1—S1—Cu1	111.24 (13)
I1—Cu1—I2^i	112.60 (2)	C1—N1—H1	117 (3)
I1—Cu1—Cu1^i	110.454 (13)	C1—N1—C5	127.1 (3)
I1—Cu1—Cu2^i	60.576 (18)	C5—N1—H1	115 (3)
I1—Cu1—Cu2	60.157 (18)	C6—N2—Cu2	169.7 (3)
I2—Cu1—I2^i	113.84 (2)	N1—C1—S1	121.6 (3)
I2—Cu1—Cu1^i	61.007 (19)	N1—C1—C2	116.4 (3)
I2^i—Cu1—Cu1^i	56.64 (2)	C2—C1—S1	122.0 (3)
I2^i—Cu1—Cu2	101.87 (2)	C1—C2—H2A	109.0
I2—Cu1—Cu2^i	107.32 (2)	C1—C2—H2B	109.0
I2—Cu1—Cu2	58.129 (16)	C1—C2—C3	112.8 (3)
Cu2^i—Cu1—I2^i	57.602 (18)	H2A—C2—H2B	107.8
Cu2^i—Cu1—Cu1^i	60.53 (2)	C3—C2—H2A	109.0
Cu2—Cu1—Cu1^i	57.881 (18)	C3—C2—H2B	109.0
Cu2^i—Cu1—Cu2	55.97 (2)	C2—C3—H3A	109.7
S1—Cu1—I1	107.77 (3)	C2—C3—H3B	109.7
S1—Cu1—I2^i	97.98 (3)	C2—C3—C4	109.7 (3)
S1—Cu1—I2	117.03 (3)	H3A—C3—H3B	108.2
S1—Cu1—Cu1^i	140.07 (3)	C4—C3—H3A	109.7
S1—Cu1—Cu2	159.65 (4)	C4—C3—H3B	109.7
S1—Cu1—Cu2^i	135.38 (3)	C3—C4—H4A	109.0
I1^i—Cu2—I1	118.71 (2)	C3—C4—H4B	109.0
I1^i—Cu2—Cu1^i	58.512 (18)	H4A—C4—H4B	107.8
I1^i—Cu2—Cu1	109.64 (2)	C5—C4—C3	112.9 (3)
I1—Cu2—Cu1	57.350 (16)	C5—C4—H4A	109.0
I2—Cu2—I1^i	115.15 (2)	C5—C4—H4B	109.0
I2—Cu2—I1	105.38 (2)	O1—C5—N1	117.9 (3)
I2—Cu2—Cu1^i	62.509 (18)	O1—C5—C4	125.1 (3)
I2—Cu2—Cu1	58.432 (17)	N1—C5—C4	117.0 (3)
Cu1^i—Cu2—I1	111.24 (2)	N2—C6—C7	178.5 (4)
Cu1^i—Cu2—Cu1	61.59 (3)	C6—C7—H7A	109.5
Cu2^i—Cu2—I1	61.16 (2)	C6—C7—H7B	109.5
Cu2^i—Cu2—I1^i	62.06 (2)	C6—C7—H7C	109.5
Cu2^i—Cu2—I2	111.572 (12)	H7A—C7—H7B	109.5
Cu2^i—Cu2—Cu1	60.528 (19)	H7A—C7—H7C	109.5
Cu2^i—Cu2—Cu1^i	63.50 (2)	H7B—C7—H7C	109.5
Cu1—S1—C1—N1	−11.4 (4)	C1—C2—C3—C4	−53.9 (4)
Cu1—S1—C1—C2	169.3 (3)	C2—C3—C4—C5	51.0 (5)
S1—C1—C2—C3	−152.4 (3)	C3—C4—C5—O1	156.9 (4)
N1—C1—C2—C3	28.3 (5)	C3—C4—C5—N1	−22.9 (5)
C1—N1—C5—O1	175.3 (4)	C5—N1—C1—S1	−177.2 (3)
C1—N1—C5—C4	−4.9 (6)	C5—N1—C1—C2	2.1 (6)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···I2	0.87 (2)	2.81 (2)	3.672 (3)	170 (4)

catena-Poly[[(µ-6-sulfanylidenepiperidin-2-one-κ²O:S)copper(I)]-µ₃-iodido] (III)

Crystal data

[CuI(C5H7NOS)]	Dx = 2.612 Mg m^−3
Mr = 319.62	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pbcn	Cell parameters from 6676 reflections
a = 26.982 (11) Å	θ = 3.3–73.1°
b = 8.195 (4) Å	µ = 35.47 mm^−1
c = 7.351 (3) Å	T = 100 K
V = 1625.4 (13) Å^3	Plate, orange
Z = 8	0.08 × 0.07 × 0.03 mm
F(000) = 1200

Data collection

Bruker SMART APEXII area detector diffractometer	1631 independent reflections
Radiation source: sealed X-ray tube, Siemens, K FFCU 2K 90	1467 reflections with I > 2σ(I)
Equatorially mounted graphite monochromator	Rint = 0.051
Detector resolution: 7.9 pixels mm^-1	θmax = 73.6°, θmin = 3.3°
0.60° ω and 0.6° φ scans	h = −32→33
Absorption correction: multi-scan SADABS; Bruker, 2016)	k = −10→9
Tmin = 0.030, Tmax = 0.144	l = −9→9
25274 measured reflections

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.055P)^2 + 1.1889P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
1631 reflections	Δρmax = 1.31 e Å^−3
94 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.

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

	x	y	z	Uiso*/Ueq
I1	0.23415 (2)	0.59898 (3)	0.50901 (3)	0.02390 (13)
Cu1	0.28100 (2)	0.62683 (8)	0.82066 (9)	0.02635 (18)
S1	0.36555 (4)	0.63113 (12)	0.83026 (14)	0.0266 (2)
O1	0.50567 (13)	0.2890 (4)	0.9865 (4)	0.0346 (8)
N1	0.43783 (13)	0.4297 (5)	0.9030 (5)	0.0274 (8)
H1	0.4550 (18)	0.516 (4)	0.923 (7)	0.033*
C1	0.38916 (15)	0.4443 (5)	0.8540 (6)	0.0253 (8)
C2	0.35970 (15)	0.2932 (5)	0.8285 (6)	0.0269 (8)
H2A	0.334849	0.311483	0.731519	0.032*
H2B	0.341637	0.268491	0.942412	0.032*
C3	0.39185 (16)	0.1470 (5)	0.7775 (7)	0.0303 (9)
H3A	0.405740	0.162739	0.654072	0.036*
H3B	0.371432	0.046611	0.776524	0.036*
C4	0.43403 (17)	0.1289 (6)	0.9153 (7)	0.0333 (10)
H4A	0.420142	0.095872	1.034455	0.040*
H4B	0.456863	0.041794	0.874268	0.040*
C5	0.46238 (17)	0.2851 (6)	0.9374 (6)	0.0299 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.02516 (19)	0.0217 (2)	0.02479 (19)	0.00135 (8)	0.00003 (9)	−0.00010 (9)
Cu1	0.0258 (3)	0.0243 (3)	0.0290 (4)	0.0002 (2)	−0.0002 (2)	0.0001 (3)
S1	0.0245 (5)	0.0238 (5)	0.0315 (5)	0.0009 (4)	−0.0001 (4)	−0.0002 (4)
O1	0.0273 (16)	0.0285 (16)	0.048 (2)	0.0009 (14)	−0.0039 (13)	−0.0007 (14)
N1	0.0253 (18)	0.0211 (17)	0.036 (2)	−0.0028 (13)	0.0010 (15)	−0.0012 (15)
C1	0.0257 (19)	0.025 (2)	0.0252 (19)	0.0017 (16)	0.0007 (16)	−0.0006 (17)
C2	0.0245 (19)	0.025 (2)	0.031 (2)	−0.0007 (16)	0.0000 (17)	−0.0015 (17)
C3	0.029 (2)	0.023 (2)	0.039 (2)	−0.0018 (16)	0.0003 (18)	−0.0042 (19)
C4	0.029 (2)	0.025 (2)	0.046 (3)	−0.0004 (18)	−0.001 (2)	0.001 (2)
C5	0.028 (2)	0.028 (2)	0.034 (2)	0.0032 (17)	0.0023 (17)	0.0001 (19)

Geometric parameters (Å, º)

I1—Cu1	2.6264 (11)	C2—H2A	0.9900
I1—Cu1^i	2.6709 (12)	C2—H2B	0.9900
I1—Cu1^ii	2.6342 (10)	C2—C3	1.526 (6)
Cu1—S1	2.2827 (15)	C3—H3A	0.9900
S1—C1	1.668 (4)	C3—H3B	0.9900
O1—C5	1.223 (6)	C3—C4	1.531 (6)
N1—H1	0.86 (2)	C4—H4A	0.9900
N1—C1	1.367 (6)	C4—H4B	0.9900
N1—C5	1.381 (6)	C4—C5	1.500 (6)
C1—C2	1.483 (6)
Cu1—I1—Cu1^ii	106.77 (3)	H2A—C2—H2B	107.8
Cu1—I1—Cu1^i	116.92 (2)	C3—C2—H2A	109.1
Cu1^ii—I1—Cu1^i	113.08 (4)	C3—C2—H2B	109.1
I1^iii—Cu1—I1^iv	104.19 (4)	C2—C3—H3A	109.7
I1—Cu1—I1^iv	116.85 (3)	C2—C3—H3B	109.7
I1—Cu1—I1^iii	99.58 (3)	C2—C3—C4	109.6 (4)
S1—Cu1—I1^iv	97.12 (4)	H3A—C3—H3B	108.2
S1—Cu1—I1	120.62 (4)	C4—C3—H3A	109.7
S1—Cu1—I1^iii	118.31 (4)	C4—C3—H3B	109.7
C1—S1—Cu1	111.76 (15)	C3—C4—H4A	109.3
C1—N1—H1	120 (4)	C3—C4—H4B	109.3
C1—N1—C5	125.7 (4)	H4A—C4—H4B	108.0
C5—N1—H1	115 (4)	C5—C4—C3	111.6 (4)
N1—C1—S1	118.4 (3)	C5—C4—H4A	109.3
N1—C1—C2	118.3 (4)	C5—C4—H4B	109.3
C2—C1—S1	123.3 (3)	O1—C5—N1	119.3 (4)
C1—C2—H2A	109.1	O1—C5—C4	122.8 (4)
C1—C2—H2B	109.1	N1—C5—C4	117.9 (4)
C1—C2—C3	112.5 (3)
Cu1—S1—C1—N1	−165.4 (3)	C1—C2—C3—C4	52.5 (5)
Cu1—S1—C1—C2	13.3 (4)	C2—C3—C4—C5	−52.7 (5)
S1—C1—C2—C3	155.5 (3)	C3—C4—C5—O1	−154.2 (5)
N1—C1—C2—C3	−25.9 (5)	C3—C4—C5—N1	26.9 (6)
C1—N1—C5—O1	−177.4 (4)	C5—N1—C1—S1	176.5 (4)
C1—N1—C5—C4	1.5 (7)	C5—N1—C1—C2	−2.2 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^v	0.86 (2)	2.03 (2)	2.881 (5)	171 (5)

Symmetry code: (v) −x+1, −y+1, −z+2.

Poly[[(piperidine-2,6-dithione-κS)copper(I)]-µ₃-iodido] (IV)

Crystal data

[Cu2I2(C5H7NS2)2]	F(000) = 1264
Mr = 671.35	Dx = 1.952 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 13.2866 (9) Å	Cell parameters from 9761 reflections
b = 11.6974 (13) Å	θ = 3.4–73.6°
c = 14.8089 (9) Å	µ = 26.87 mm^−1
β = 96.998 (6)°	T = 100 K
V = 2284.4 (3) Å^3	Block, red
Z = 4	0.22 × 0.13 × 0.09 mm

Data collection

Bruker SMART APEXII area detector diffractometer	4597 independent reflections
Radiation source: sealed X-ray tube, Siemens, K FFCU 2K 90	4236 reflections with I > 2σ(I)
Equatorially mounted graphite monochromator	Rint = 0.063
Detector resolution: 7.9 pixels mm^-1	θmax = 73.6°, θmin = 3.4°
0.60° ω and 0.6° φ scans	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −14→14
Tmin = 0.009, Tmax = 0.094	l = −18→18
78133 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.126	w = 1/[σ^2(Fo^2) + (0.0963P)^2 + 0.866P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
4597 reflections	Δρmax = 1.58 e Å^−3
181 parameters	Δρmin = −0.48 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
I2	0.55860 (2)	0.62760 (3)	0.40198 (2)	0.04041 (13)
I1	−0.04785 (2)	0.16932 (3)	0.55075 (2)	0.04179 (13)
Cu1	0.09352 (5)	0.01033 (6)	0.55762 (5)	0.03868 (18)
Cu2	0.50067 (5)	0.41451 (7)	0.43516 (5)	0.04040 (19)
S4	0.88076 (9)	0.04448 (10)	0.29165 (8)	0.0381 (3)
S2	0.38476 (10)	0.38690 (11)	0.31034 (9)	0.0419 (3)
S3	0.64474 (10)	0.30477 (12)	0.45389 (8)	0.0444 (3)
S1	0.24194 (9)	0.09681 (11)	0.52729 (8)	0.0410 (3)
N1	0.2946 (3)	0.2359 (4)	0.4050 (3)	0.0400 (9)
H1	0.341595	0.255812	0.449306	0.048*
N2	0.7560 (3)	0.1895 (4)	0.3534 (3)	0.0393 (9)
H2	0.784079	0.164625	0.406656	0.047*
C6	0.6808 (4)	0.2704 (4)	0.3544 (3)	0.0392 (10)
C1	0.2258 (4)	0.1562 (5)	0.4253 (3)	0.0399 (10)
C10	0.7913 (4)	0.1441 (4)	0.2793 (4)	0.0373 (10)
C5	0.2980 (4)	0.2881 (4)	0.3228 (4)	0.0400 (10)
C2	0.1396 (4)	0.1307 (5)	0.3541 (4)	0.0451 (12)
H2A	0.077033	0.121868	0.383553	0.054*
H2B	0.152702	0.056988	0.324839	0.054*
C9	0.7453 (4)	0.1855 (5)	0.1882 (3)	0.0414 (11)
H9A	0.687396	0.135704	0.165575	0.050*
H9B	0.796127	0.180538	0.144760	0.050*
C7	0.6364 (5)	0.3190 (5)	0.2646 (4)	0.0473 (12)
H7A	0.620041	0.400624	0.272580	0.057*
H7B	0.572524	0.278409	0.243395	0.057*
C4	0.2216 (4)	0.2518 (5)	0.2464 (4)	0.0449 (11)
H4A	0.247023	0.184112	0.216075	0.054*
H4B	0.211015	0.314198	0.200990	0.054*
C8	0.7087 (5)	0.3083 (5)	0.1928 (4)	0.0480 (12)
H8A	0.673595	0.331533	0.132807	0.058*
H8B	0.767460	0.359753	0.208203	0.058*
C3	0.1218 (4)	0.2229 (5)	0.2805 (4)	0.0474 (12)
H3A	0.072927	0.194853	0.229493	0.057*
H3B	0.092969	0.292195	0.305907	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I2	0.0431 (2)	0.0411 (2)	0.0377 (2)	−0.00315 (12)	0.00764 (14)	0.00019 (12)
I1	0.0442 (2)	0.0404 (2)	0.0395 (2)	0.00544 (12)	0.00003 (14)	−0.00445 (12)
Cu1	0.0398 (4)	0.0393 (4)	0.0368 (4)	0.0010 (3)	0.0043 (3)	0.0020 (3)
Cu2	0.0397 (4)	0.0416 (4)	0.0404 (4)	0.0001 (3)	0.0066 (3)	−0.0006 (3)
S4	0.0389 (6)	0.0400 (6)	0.0356 (5)	0.0026 (4)	0.0055 (4)	0.0004 (5)
S2	0.0425 (6)	0.0427 (6)	0.0406 (6)	−0.0043 (5)	0.0054 (5)	0.0042 (5)
S3	0.0462 (7)	0.0530 (7)	0.0346 (6)	0.0106 (5)	0.0069 (5)	0.0011 (5)
S1	0.0416 (6)	0.0460 (7)	0.0352 (6)	−0.0036 (5)	0.0034 (5)	0.0044 (5)
N1	0.039 (2)	0.044 (2)	0.0367 (19)	−0.0026 (17)	0.0041 (16)	0.0006 (18)
N2	0.039 (2)	0.044 (2)	0.0346 (19)	0.0019 (17)	0.0018 (16)	0.0039 (17)
C6	0.041 (2)	0.038 (2)	0.038 (2)	0.0000 (19)	0.0046 (19)	0.003 (2)
C1	0.041 (3)	0.044 (3)	0.035 (2)	0.000 (2)	0.004 (2)	0.001 (2)
C10	0.036 (2)	0.037 (2)	0.039 (2)	−0.0020 (18)	0.0048 (19)	0.001 (2)
C5	0.038 (2)	0.042 (3)	0.040 (2)	0.001 (2)	0.0050 (19)	−0.001 (2)
C2	0.047 (3)	0.051 (3)	0.037 (3)	−0.008 (2)	0.003 (2)	0.003 (2)
C9	0.046 (3)	0.044 (3)	0.034 (2)	0.005 (2)	0.006 (2)	−0.001 (2)
C7	0.055 (3)	0.049 (3)	0.037 (3)	0.013 (2)	0.004 (2)	0.002 (2)
C4	0.049 (3)	0.045 (3)	0.040 (3)	−0.005 (2)	0.004 (2)	0.006 (2)
C8	0.062 (3)	0.047 (3)	0.035 (2)	0.012 (3)	0.010 (2)	0.006 (2)
C3	0.042 (3)	0.057 (3)	0.042 (3)	−0.004 (2)	0.001 (2)	0.002 (2)

Geometric parameters (Å, º)

I1—Cu1	2.6365 (8)	C1—C2	1.490 (7)
I1—Cu1^i	2.6687 (8)	C10—C9	1.491 (7)
I2—Cu2	2.6719 (8)	C5—C4	1.487 (7)
I2—Cu2^ii	2.6724 (8)	C2—H2A	0.9900
Cu1—S4^iii	2.3075 (13)	C2—H2B	0.9900
Cu1—S1	2.3086 (14)	C2—C3	1.531 (8)
Cu2—S2	2.2802 (15)	C9—H9A	0.9900
Cu2—S3	2.2933 (15)	C9—H9B	0.9900
S4—C10	1.659 (5)	C9—C8	1.521 (7)
S2—C5	1.659 (5)	C7—H7A	0.9900
S3—C6	1.654 (5)	C7—H7B	0.9900
S1—C1	1.652 (5)	C7—C8	1.522 (8)
N1—H1	0.8800	C4—H4A	0.9900
N1—C1	1.365 (7)	C4—H4B	0.9900
N1—C5	1.367 (7)	C4—C3	1.514 (8)
N2—H2	0.8800	C8—H8A	0.9900
N2—C6	1.378 (7)	C8—H8B	0.9900
N2—C10	1.354 (7)	C3—H3A	0.9900
C6—C7	1.498 (7)	C3—H3B	0.9900
Cu2—I2—Cu2^ii	62.54 (3)	C1—C2—H2A	108.8
Cu1—I1—Cu1^i	64.94 (3)	C1—C2—H2B	108.8
I1—Cu1—I1^i	115.06 (3)	C1—C2—C3	113.7 (5)
S4^iii—Cu1—I1	104.72 (4)	H2A—C2—H2B	107.7
S4^iii—Cu1—I1^i	111.04 (4)	C3—C2—H2A	108.8
S4^iii—Cu1—S1	106.30 (5)	C3—C2—H2B	108.8
S1—Cu1—I1^i	111.41 (4)	C10—C9—H9A	109.4
S1—Cu1—I1	107.75 (4)	C10—C9—H9B	109.4
I2—Cu2—I2^ii	117.46 (3)	C10—C9—C8	111.3 (4)
S2—Cu2—I2^ii	117.47 (4)	H9A—C9—H9B	108.0
S2—Cu2—I2	99.46 (4)	C8—C9—H9A	109.4
S2—Cu2—S3	119.35 (6)	C8—C9—H9B	109.4
S3—Cu2—I2^ii	96.95 (4)	C6—C7—H7A	109.2
S3—Cu2—I2	106.83 (5)	C6—C7—H7B	109.2
C10—S4—Cu1^iii	108.78 (18)	C6—C7—C8	112.1 (5)
C5—S2—Cu2	114.75 (19)	H7A—C7—H7B	107.9
C6—S3—Cu2	110.88 (19)	C8—C7—H7A	109.2
C1—S1—Cu1	110.1 (2)	C8—C7—H7B	109.2
C1—N1—H1	116.7	C5—C4—H4A	109.5
C1—N1—C5	126.6 (5)	C5—C4—H4B	109.5
C5—N1—H1	116.7	C5—C4—C3	110.7 (5)
C6—N2—H2	116.5	H4A—C4—H4B	108.1
C10—N2—H2	116.5	C3—C4—H4A	109.5
C10—N2—C6	127.0 (4)	C3—C4—H4B	109.5
N2—C6—S3	117.7 (4)	C9—C8—C7	109.9 (5)
N2—C6—C7	117.3 (4)	C9—C8—H8A	109.7
C7—C6—S3	125.0 (4)	C9—C8—H8B	109.7
N1—C1—S1	118.2 (4)	C7—C8—H8A	109.7
N1—C1—C2	117.3 (5)	C7—C8—H8B	109.7
C2—C1—S1	124.5 (4)	H8A—C8—H8B	108.2
N2—C10—S4	120.0 (4)	C2—C3—H3A	109.8
N2—C10—C9	117.5 (4)	C2—C3—H3B	109.8
C9—C10—S4	122.5 (4)	C4—C3—C2	109.2 (5)
N1—C5—S2	120.6 (4)	C4—C3—H3A	109.8
N1—C5—C4	117.2 (4)	C4—C3—H3B	109.8
C4—C5—S2	122.2 (4)	H3A—C3—H3B	108.3
Cu1^iii—S4—C10—N2	8.2 (5)	N2—C6—C7—C8	−23.4 (7)
Cu1^iii—S4—C10—C9	−170.5 (4)	N2—C10—C9—C8	29.6 (7)
Cu1—S1—C1—N1	162.9 (4)	C6—N2—C10—S4	−178.4 (4)
Cu1—S1—C1—C2	−15.7 (5)	C6—N2—C10—C9	0.4 (8)
Cu2—S2—C5—N1	4.8 (5)	C6—C7—C8—C9	51.7 (7)
Cu2—S2—C5—C4	−174.9 (4)	C1—N1—C5—S2	177.9 (4)
Cu2—S3—C6—N2	−169.5 (3)	C1—N1—C5—C4	−2.4 (8)
Cu2—S3—C6—C7	9.3 (5)	C1—C2—C3—C4	48.8 (7)
S4—C10—C9—C8	−151.7 (4)	C10—N2—C6—S3	175.3 (4)
S2—C5—C4—C3	−145.6 (4)	C10—N2—C6—C7	−3.7 (8)
S3—C6—C7—C8	157.7 (4)	C10—C9—C8—C7	−54.8 (6)
S1—C1—C2—C3	160.4 (4)	C5—N1—C1—S1	175.1 (4)
N1—C1—C2—C3	−18.2 (7)	C5—N1—C1—C2	−6.3 (8)
N1—C5—C4—C3	34.7 (7)	C5—C4—C3—C2	−56.3 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···I2^ii	0.88	2.79	3.628 (4)	161
N2—H2···I1^iv	0.88	2.90	3.679 (4)	149

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

Poly[[(µ-isoindoline-1,3-dithione-κ²S:S)copper(I)]-µ₃-iodido] (V)

Crystal data

[CuI(C8H5NS2)]	F(000) = 696
Mr = 369.69	Dx = 2.492 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 15.174 (5) Å	Cell parameters from 4507 reflections
b = 4.1188 (16) Å	θ = 2.6–31.9°
c = 15.785 (6) Å	µ = 5.72 mm^−1
β = 92.98 (2)°	T = 100 K
V = 985.2 (6) Å^3	Block, black
Z = 4	0.30 × 0.02 × 0.01 mm

Data collection

Bruker APEXII Quazar diffractometer	3603 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	3226 reflections with I > 2σ(I)
Mirror optics monochromator	Rint = 0.041
Detector resolution: 7.9 pixels mm^-1	θmax = 33.2°, θmin = 2.6°
0.5° ω and 0.5° φ scans	h = −22→22
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −6→6
Tmin = 0.322, Tmax = 0.404	l = −23→23
11871 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.036	w = 1/[σ^2(Fo^2) + (0.0417P)^2 + 7.0163P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.089	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 3.17 e Å^−3
3603 reflections	Δρmin = −1.13 e Å^−3
118 parameters	Absolute structure: Flack x determined using 1438 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
2 restraints	Absolute structure parameter: 0.034 (12)
Primary atom site location: dual

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
I1	0.68957 (2)	0.10931 (10)	0.74974 (2)	0.01374 (11)
Cu1	0.59491 (6)	0.5992 (2)	0.69164 (6)	0.0146 (2)
S1	0.60747 (14)	0.6607 (5)	0.54996 (12)	0.0139 (3)
S2	0.46550 (14)	0.2757 (5)	0.25028 (12)	0.0146 (3)
N1	0.5450 (5)	0.4774 (16)	0.3969 (4)	0.0133 (12)
H1	0.587624	0.579000	0.371951	0.016*
C1	0.5382 (5)	0.4700 (18)	0.4850 (5)	0.0122 (13)
C2	0.4596 (5)	0.2691 (18)	0.4975 (5)	0.0124 (14)
C3	0.4197 (5)	0.1812 (19)	0.5712 (5)	0.0147 (14)
H3	0.442699	0.252848	0.625113	0.018*
C4	0.3448 (5)	−0.015 (2)	0.5639 (5)	0.0148 (14)
H4	0.316667	−0.082004	0.613403	0.018*
C5	0.3106 (5)	−0.115 (2)	0.4828 (5)	0.0165 (15)
H5	0.259718	−0.249734	0.478913	0.020*
C6	0.3493 (5)	−0.0227 (18)	0.4093 (5)	0.0128 (13)
H6	0.325668	−0.090075	0.355269	0.015*
C7	0.4244 (5)	0.1733 (18)	0.4172 (5)	0.0125 (13)
C8	0.4795 (5)	0.3123 (19)	0.3538 (5)	0.0118 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0131 (2)	0.01109 (17)	0.0169 (2)	−0.0009 (2)	−0.00081 (15)	−0.0008 (2)
Cu1	0.0155 (5)	0.0162 (5)	0.0122 (5)	−0.0008 (4)	0.0004 (4)	−0.0010 (4)
S1	0.0141 (9)	0.0150 (8)	0.0124 (8)	0.0001 (6)	0.0003 (7)	−0.0011 (6)
S2	0.0132 (8)	0.0185 (9)	0.0120 (8)	−0.0011 (7)	−0.0002 (7)	−0.0017 (7)
N1	0.014 (3)	0.014 (3)	0.012 (3)	0.001 (2)	0.001 (2)	0.001 (2)
C1	0.012 (3)	0.012 (3)	0.013 (3)	0.003 (2)	0.000 (3)	0.002 (3)
C2	0.012 (4)	0.009 (3)	0.017 (3)	0.006 (3)	0.002 (3)	0.000 (2)
C3	0.014 (3)	0.013 (3)	0.017 (3)	0.002 (3)	0.002 (3)	0.001 (3)
C4	0.010 (3)	0.018 (3)	0.017 (4)	0.001 (3)	0.003 (3)	0.002 (3)
C5	0.012 (3)	0.018 (4)	0.019 (4)	−0.002 (3)	−0.003 (3)	0.001 (3)
C6	0.011 (3)	0.011 (3)	0.017 (3)	0.000 (2)	−0.001 (3)	0.001 (3)
C7	0.015 (3)	0.009 (3)	0.014 (3)	0.002 (2)	0.002 (3)	0.001 (2)
C8	0.011 (3)	0.013 (3)	0.012 (3)	0.003 (2)	0.002 (3)	0.000 (2)

Geometric parameters (Å, º)

I1—Cu1	2.6152 (13)	C2—C7	1.405 (11)
I1—Cu1^i	2.6798 (13)	C3—H3	0.9500
Cu1—S1	2.269 (2)	C3—C4	1.394 (12)
Cu1—S2^ii	2.273 (2)	C4—H4	0.9500
S1—C1	1.632 (8)	C4—C5	1.417 (12)
S2—C8	1.645 (7)	C5—H5	0.9500
N1—H1	0.8800	C5—C6	1.380 (11)
N1—C1	1.400 (10)	C6—H6	0.9500
N1—C8	1.357 (10)	C6—C7	1.396 (11)
C1—C2	1.473 (11)	C7—C8	1.455 (11)
C2—C3	1.388 (11)
Cu1—I1—Cu1^i	102.12 (4)	C2—C3—H3	120.9
I1—Cu1—I1^iii	102.12 (4)	C2—C3—C4	118.1 (8)
S1—Cu1—I1^iii	100.30 (6)	C4—C3—H3	120.9
S1—Cu1—I1	111.05 (6)	C3—C4—H4	120.0
S1—Cu1—S2^ii	119.65 (8)	C3—C4—C5	120.1 (8)
S2^ii—Cu1—I1^iii	98.16 (7)	C5—C4—H4	120.0
S2^ii—Cu1—I1	120.16 (7)	C4—C5—H5	119.1
C1—S1—Cu1	118.8 (3)	C6—C5—C4	121.8 (8)
C8—S2—Cu1^iv	108.3 (3)	C6—C5—H5	119.1
C1—N1—H1	123.3	C5—C6—H6	121.1
C8—N1—H1	123.3	C5—C6—C7	117.7 (7)
C8—N1—C1	113.3 (7)	C7—C6—H6	121.1
N1—C1—S1	122.3 (6)	C2—C7—C8	107.7 (7)
N1—C1—C2	104.3 (7)	C6—C7—C2	120.9 (7)
C2—C1—S1	133.3 (6)	C6—C7—C8	131.4 (7)
C3—C2—C1	130.6 (7)	N1—C8—S2	126.7 (6)
C3—C2—C7	121.4 (7)	N1—C8—C7	106.6 (6)
C7—C2—C1	108.0 (7)	C7—C8—S2	126.7 (6)
Cu1—S1—C1—N1	−175.6 (5)	C2—C7—C8—S2	−179.1 (6)
Cu1—S1—C1—C2	5.3 (9)	C2—C7—C8—N1	1.0 (8)
Cu1^iv—S2—C8—N1	18.3 (8)	C3—C2—C7—C6	−2.0 (11)
Cu1^iv—S2—C8—C7	−161.5 (6)	C3—C2—C7—C8	178.2 (7)
S1—C1—C2—C3	0.4 (13)	C3—C4—C5—C6	−0.2 (12)
S1—C1—C2—C7	178.6 (6)	C4—C5—C6—C7	0.4 (12)
N1—C1—C2—C3	−178.9 (8)	C5—C6—C7—C2	0.7 (11)
N1—C1—C2—C7	−0.6 (8)	C5—C6—C7—C8	−179.6 (8)
C1—N1—C8—S2	178.7 (6)	C6—C7—C8—S2	1.1 (12)
C1—N1—C8—C7	−1.5 (9)	C6—C7—C8—N1	−178.7 (8)
C1—C2—C3—C4	−179.8 (8)	C7—C2—C3—C4	2.1 (11)
C1—C2—C7—C6	179.5 (7)	C8—N1—C1—S1	−178.0 (6)
C1—C2—C7—C8	−0.2 (8)	C8—N1—C1—C2	1.3 (8)
C2—C3—C4—C5	−1.0 (12)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···I1^iv	0.88	2.84	3.692 (7)	163

Symmetry code: (iv) x, −y+1, z−1/2.