Snapshot and crystallographic observations of kinetic and thermodynamic products for NO2S2 macrocyclic complexes

Park, I.-H.; Kang, Y.; Lee, E.; Ju, H.; Kim, S.; Seo, S.; Jung, J.H.; Lee, S.S.

doi:10.1107/S2052252517015081

research papers

IUCrJ

Volume 5| Part 1| January 2018| Pages 45-53

ISSN: 2052-2525

https://doi.org/10.1107/S2052252517015081

CHEMISTRY | CRYSTENG

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Snapshot and crystallographic observations of kinetic and thermodynamic products for NO₂S₂ macrocyclic complexes

In-Hyeok Park,^a Yunji Kang,^a Eunji Lee,^a Huiyeong Ju,^a Seulgi Kim,^a Sujin Seo,^a Jong Hwa Jung ^a and Shim Sung Lee ^a ^*

^aDepartment of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju 52828, Republic of Korea
^*Correspondence e-mail: sslee@gnu.ac.kr

Edited by C.-Y. Su, Sun Yat-Sen University, China (Received 18 August 2017; accepted 17 October 2017)

Direct observation and structural characterization of a kinetic product and a thermodynamic product for complexes with an NO₂S₂ macrocycle (L) are reported. L reacts with copper(I) iodide to give a mononuclear complex [Cu(L)]₂(Cu₂I₄)·2CH₂Cl₂ (1), featuring three separate units. When cadmium(II) iodide was reacted with L, an anion-coordinated complex [Cd(L)I]₂(Cd₂I₆)·4CH₃CN (2) with a needle-type crystal shape was formed as the kinetic product. Interestingly, when the needle-type kinetic product was left undisturbed in the mother solution it gradually transformed to the pseudo-dimer complex [Cd₂(L)₂I₂](Cd₂I₆) (3) with a brick-type crystal shape as the thermodynamic product. The dissolution–recrystallization process resulted in the elimination of the lattice solvent molecules (acetonitrile) in 2 and the contraction of two neighboring macrocyclic complex units [Cd(L)I]⁺, forming the pseudo-dimer 3 via an intermolecular Cd⋯I interaction between two monomers. For the entire process from kinetic to thermodynamic products, it was possible to obtain sequential photographic snapshots, single-crystal X-ray structures and powder X-ray diffraction patterns. For the copper(I) and cadmium(II) complexes, competitive NMR results agree with the solid-state data that show copper(I) has a higher affinity for L than does cadmium(II).

Keywords: snapshots; kinetic products; thermodynamic products; single-crystal-to-single-crystal transformations; crystal engineering; molecular crystals.

CCDC references: 1566938; 1566939; 1566940; 1566941; 1566942

1. Introduction

Similar to organic reactions, self-assembly of synthetic coordination processes affords not only thermodynamic products but also kinetic products when the energy for the latter is trapped in local minima (Percec et al., 2011 ; Gammon et al., 2010 ; Hwang et al., 2004 ; Hasenknopf et al., 1998 ). In principle, the reason for the two products is the difference in their activation energy: kinetic products form rapidly and they usually occur at lower temperature, while thermodynamic products form slowly or at higher temperatures (Fig. 1) (Martí-Rujas & Kawano, 2013 ; Martí-Rujas et al., 2011 ). The kinetic states in the self-assembly of coordination products play a crucial role in understanding the mechanism and final products as well as the fundamental aspects of functionalization (Percec et al., 2011; Gammon et al., 2010; Hwang et al., 2004; Hasenknopf et al., 1998; Martí-Rujas & Kawano, 2013; Martí-Rujas et al., 2011). However, it is hard to recognize or separate these two products completely and structurally characterize them in the single-crystal state as pure forms due to the difficulty of growing single crystals, because fast precipitation so often leads to the kinetic product. Kawano and co-workers proposed an ab initio powder X-ray diffraction (PXRD) approach as an alternative methodology to overcome these difficulties (Martí-Rujas & Kawano, 2013; Martí-Rujas et al., 2011). Recently, Ohtsu & Kawano (2017 ) highlighted the kinetic effect in self-assembly of coordination networks.

Figure 1
Reaction routes for a kinetic product via fast crystallization and a thermodynamic product via slow crystallization in the assembly reaction.

In our previous work, removal of the coordinated or noncoordinated solvent molecules of supramolecular complexes has played a key role in the reaction process between the kinetic and thermodynamic products (Lee et al., 2010 , 2013 ; Ju et al., 2015 , 2017 ). We recently isolated a 19-membered NO₂S₂ macrocycle L (see scheme) and a 38-membered macrocycle from the mixed products of the [1:1] and [2:2] cyclization reactions, respectively (Kang et al., 2016 ). In complexes with copper(I) iodide, the smaller macrocycle L forms a typical mononuclear complex in which all donors in the ring cavity cooperatively bind to the central copper(I) ion (Kang et al., 2016), while the larger macrocycle affords a tetranuclear bis(macrocycle) complex adopting a double-decker structure as a first example of this type (Kang et al., 2016). Sulfur donors in crown-type macrocycles have a tendency to lead metal coordination outside the cavity (exo-coordination) to form discrete or infinite complexes with some thiaphilic metal ions (Lee, Kim et al., 2008 ; Lee, Lee et al., 2008 ; Park et al., 2012 , 2014 ). However, the presence of a pyridine subunit in L is expected to locate the metal ion inside the cavity (Lee et al., 2016 , 2015 ; Drahoš et al., 2017 ; Fedorov et al., 2017 ). Considering the binding affinity of L to metal ions with respect to their donor basicity, we have employed copper(I) and cadmium(II) ions (iodide form).

In the present work, the ligand L yields two products of CdI₂ with different crystal habits depending on the reaction time. Sometimes a mixture of crystalline products can be separated manually in pure form under a microscope because of their different crystal habits (Moreno-Calvo et al., 2010 ; Ryu et al., 2014 ; Park et al., 2014). In view of these intriguing results we decided to follow the reaction process more closely, in order to obtain insight into the structural and mechanical factors that may act. Fortunately, we were able to obtain a series of snapshot images for the two products with different crystal habits exhibiting growth–dissolution–recrystallization depending on the time between the kinetic and thermodynamic control processes. Here, we report several complexes of L which offer an opportunity to identify the kinetic and thermodynamic products via visual methods because of the slow reaction process and different crystal habits. The details are discussed below.

2. Results and discussion

2.1. Copper(I) iodide complex 1

L was prepared as described by us previously (Kang et al., 2016). The reaction of L in dichloromethane with CuI in acetonitrile afforded a colorless crystalline product, 1. The X-ray analysis revealed that 1 features three separate metal-containing units with the formula [Cu(L)]₂(Cu₂I₄)·2CH₂Cl₂: two macrocyclic copper(I) complex cations [Cu(L)]⁺ and one anionic copper(I) iodide cluster (Cu₂I₄)²⁻ (Fig. 2 and Table 1). Since the inversion center is located in the middle of the anionic cluster, the asymmetric unit contains one macrocyclic cation and one half of the cluster. In the macrocyclic complex cation, the copper(I) center binds to all donors of L in a twisted conformation, adopting a distorted square-pyramidal coordination geometry (τ = 0.25; Addison et al., 1984 ) with atoms N1, O1, O2 and S1 defining a square plane, and atom S2 the apex. The Cu₂I₄ cluster is planar, similar to other examples reported (Haase et al., 2011 ; Basu et al., 1987 ; Kia et al., 2007 ; Bhaduri et al., 1991 ). The Cu1—N1 bond distance [2.032 (8) Å] is consistent with the strong coordination of copper(I) toward the pyridine N atom. The Cu—S bond distances [Cu1—S1 = 2.274 (3) Å and Cu1—S2 = 2.255 (3) Å] are typical and the Cu—O bond distances [Cu1—O1 = 2.712 (7) Å and Cu1—O2 = 2.657 (8) Å] are also normal.

Table 1
Crystallographic data and refinement parameters

	1	2	3	4	5
CCDC refcode	1566938	1566939	1566940	1566941	1566942
Formula	C₃₀H₂₉Cl₂Cu₂I₂NO₂ S₂	C₂₉H₂₇Cd₂I₄NO₂S₂	C₅₈H₅₄Cd₄I₈N₂O₄S	C₁₁₆H₁₀₆Cd₈I₁₆N₄O₈S₈	C₂₉H₂₇CdCuI₃NO₂S₂
Formula weight	951.44	1218.03	2436.07	4870.12	1042.28
Crystal system	Triclinic	Monoclinic	Triclinic	Triclinic	Triclinic
Space group	$[P{\overline 1}]$	C2/c	$[P{\overline 1}]$	$[P{\overline 1}]$	$[P{\overline 1}]$
a (Å)	11.7925 (4)	23.3017 (6)	11.660 (3)	11.3166 (11)	8.9645 (2)
b (Å)	11.9665 (4)	13.4569 (4)	12.147 (3)	13.4404 (15)	14.4098 (3)
c (Å)	13.4375 (4)	26.9935 (7)	12.585 (4)	24.586 (2)	14.8826 (3)
α (°)	93.290 (2)	90	75.142 (11)	86.655 (7)	65.8530 (10)
β (°)	95.681 (2)	102.9630 (10)	87.056 (13)	89.396 (6)	73.3860 (10)
γ (°)	118.683 (2)	90	86.996 (13)	78.371 (7)	81.5460 (10)
V (Å³)	1643.38 (10)	8248.6 (4)	1719.2	3656.6 (6)	1680.04 (6)
Z	2	8	1	1	2
D_calc (Mg m⁻³)	1.923	2.092	2.353	2.212	2.060
μ (mm⁻¹)	3.491	4.158	4.977	4.680	4.172
2θ_max (°)	52.00	52.00	52.00	48.00	52.00
Reflections collected	22525	36289	28690	23781	28556
Independent reflections	6174 (R_int = 0.0384)	8103 (R_int = 0.0499)	6745 (R_int = 0.0283)	8432 (R_int = 0.0842)	6602 (R_int = 0.0254)
Goodness-of-fit on F²	1.113	1.112	1.062	1.129	1.042
R₁, wR₂ [I > 2σ(I)]	0.0738, 0.2191	0.0432, 0.0992	0.0205, 0.0440	0.1848, 0.4191	0.0168, 0.0376
R₁, wR₂ (all data)	0.0935, 0.2336	0.0535, 0.1025	0.0247, 0.0457	0.2147, 0.4304	0.0194, 0.0388

Figure 2
The molecular structure of 1, [Cu(L)]₂(Cu₂I₄)·2CH₂Cl₂, showing the three separate metal-containing units. The noncoordinated solvent molecule has been omitted.

Recently, we have reported a copper(I) iodide complex of L with the formula [Cu(L)]I₃·ether isolated from dichloromethane/acetonitrile/ether (Kang et al., 2016). In this case, the cationic complex part [Cu(L)]⁺ is also five-coordinate, adopting a distorted square-pyramidal geometry (τ = 0.31), but one triiodide ion (I₃⁻) exists as a counteranion due to the partial oxidation of copper(I) to copper(II) (Kang et al., 2016; Lee et al., 2017 ).

2.2. Cadmium(II) iodide complexes: kinetic product 2 and thermodynamic product 3

It is notable that the complexation of L with CdI₂ yields two products whose crystal shapes are different, 2 forming needles and 3 forming bricks, and their compositions change depending on the reaction time (Fig. 3). In these observations, we provide decisive evidence for the stepwise formation of a kinetic product and a thermodynamic product, not only to the naked eye but also via a crystallographic approach. The details are discussed in the next section.

Figure 3
Cartoon presentation of time-dependent crystal growth, dissolution and recrystallization in the mother solution: 2 forms needles and 3 forms bricks.

When L was reacted with CdI₂ in dichloromethane/acetonitrile, as mentioned above, two products, 2 and 3, identified by eye due to their different crystal habits, were isolated. Thus, time-series snapshots for the single-crystal growth process were recorded by optical microscope photography (Fig. 4, see also Fig. S1 and Movie S1 in the supporting information). Indeed, slow evaporation of this reaction mixture for 10 h gave a colorless needle-shaped crystalline product 2 (Fig. 4a). When the needle-shaped product 2 was left undisturbed in the mother solution, a small brick-shaped crystalline product 3 appeared after 34 h (Fig. 4b). Thereafter, the size and number of crystals of the brick-shaped product 3 increased and the needle-shaped crystals of 2 gradually disappeared (Figs. 4c–4e). After 96 h, 2 disappeared completely and only 3 was present (Fig. 4f).

Figure 4
Time-series snapshot optical microscope images for 2 and 3 in the mother solution. (a) Needle-shaped crystals of 2 obtained after 10 h. (b) Brick-shaped crystals of 3 appear (orange circles). (c)–(f) The needles of 2 disappear gradually and the number and size of the bricks of 3 increase. (g) Only the brick-shaped crystals of 3 exist after 96 h.

Single-crystal X-ray analysis revealed that the two observed types of crystals, 2 and 3, have different cell parameters, compositions and structures (Moreno-Calvo et al., 2010; Ryu et al., 2014; Park et al., 2014). For instance, the needle-shaped product, 2, crystallizes in the monoclinic space group C2/c with the formula [Cd(L)I]₂(Cd₂I₆)·4CH₃CN (Fig. 5a, and Table S2 in the supporting information), while the brick-shaped product, 3, crystallizes in the triclinic space group $[P{\overline 1}]$ with the formula [Cd₂(L)₂I₂](Cd₂I₆) (Fig. 5b, and Table S3 in the supporting information]. Comparison of the PXRD patterns for each separate product and the simulated patterns for the corresponding single crystals indicates that the two species are effectively separate, showing bulk purity (Fig. 6). Even though both complexes share some common features, it is of great interest to compare these two structures to reveal what happens during the reaction process in solution.

Figure 5
Molecular structures of (a) 2, [Cd(L)I]₂(Cd₂I₆)·4CH₃CN, and (b) 3, [Cd₂(L)₂I₂](Cd₂I₆), isolated from the dissolution–recrystallization process involving the loss of lattice solvent molecules from 2 (acetonitrile, not shown) in solution. The anionic (Cd₂I₆)²⁻ clusters in both products have been omitted. The distances between Cd1 and I1A are 3.5768(8) Å (red arrow) in 2 and 3.3827(8) Å (dashed lines) in 3.

Figure 6
The PXRD patterns of 2, 3 and 4.

Again, complex 2 contains three separate metal-containing units: two macrocyclic complex cation units [Cd(L)I]⁺ and one anionic cadmium(II) iodide cluster unit (Cd₂I₆)²⁻ (not shown in Fig. 5a). In 2, the two macrocyclic complex units face each other with a Cd1⋯I1A distance of 3.5768 (8) Å, which is similar to the sum of the van der Waals radii r_VDW (3.56 Å; Bondi, 1964 ) (Fig. 5a). The Cd^II center in the macrocyclic complex unit is six-coordinate, being bound to all five donors from L which adopts a bent and twisted conformation. The coordination sphere is completed by one iodide anion, with the Cd1—I1 bond distance being 2.7422 (7) Å.

The key structural feature of 3 is its pseudo-dimeric form via the associated change in the Cd1A⋯I1 distance from 3.5768 (8) to 3.3827 (8) Å; the latter value is shorter than its r_VDW (3.56 Å) (Fig. 5b). Large conformation changes in the macrocycle are also observed due to the removal of the lattice solvent molecules and the dimeric interaction. The metal centers in both 2 and 3 are six-coordinate, adopting a monocapped square-pyramidal geometry (Fig. 7). However, the rearrangement from 2 to 3 involves geometric changes to the coordination sphere as well as conformational changes of L. Considering the interatomic distances between Cd1A and I1, it might be concluded that the removal of the lattice acetonitrile molecules in 2 induces the contraction of the molecule, resulting in the pseudo-dimer formation of 3.

Figure 7
The coordination geometry of the cadmium(II) center in (a) 2 and (b) 3, showing a distorted monocapped square-pyramidal arrangement.

Some modified crystallization approaches were also carried out, affording isolation of brick-shaped 3 directly from the reaction mixture (Lee et al., 2010, 2013; Ju et al., 2015, 2017). For example, under identical reaction conditions but with stirring at 50°C for 20 min (Fig. 5), a solid precipitate was obtained. The PXRD pattern confirmed that this solid is pure complex 3 (Fig. 6), suggesting direct preparation at the higher temperature as depicted in Fig. 1. Alternatively, when several single crystals of 3 were added as seeds to the corresponding freshly prepared reaction mixture solution, a large quantity of brick-shaped 3 was obtained via extra crystal nucleation and crystal growth without the appearance of the metastable species 2. Furthermore, solvent diffusion of a dichloromethane solution of L into an acetonitrile solution of cadmium(II) iodide gave only product 3.

When we consider the snapshot images together with the high temperature and the seeding approaches showing direct preparation of 3, the observed crystal habit changing from 2 to 3 in the mother solution can be understood in terms of the reaction process, from kinetic product 2 to thermodynamic product 3. Earlier, our time-dependent crystallization experiments showed that a one-dimensional silver(I) perchlorate coordination polymer of an O₂S₂ macrocycle is a kinetic product and transforms into a thermodynamically more stable two-dimensional network (Lee et al., 2010). More recently, our group introduced a disilver(I) solvato-complex of a 40-membered N₄O₄S₄ macrocycle as a kinetic product which shows rearrangement to the desolvated thermodynamic product (Lee et al., 2013).

2.3. A single-crystal-to-single-crystal transformation of 2 in air

In air, unlike in the mother solution, kinetic product 2, [Cd(L)I]₂(Cd₂I₆)·4CH₃CN, showed a different transformation behavior (Fig. 8). In 2, as mentioned, four lattice acetonitrile molecules are trapped in each formula unit. When colorless crystals of 2 were filtered off and isolated from the mother solution and kept in air, we confirmed that three lattice acetonitrile molecules were removed by sublimation within several hours to give compound 4, [Cd(L)I]₂[(Cd₂I₆)·CH₃CN] (Fig. 8). During this partial sublimation process, the crystals lost transparency but it was possible to obtain the single-crystal structure. Notably, the removal of the lattice solvent molecules by partial sublimation also induced some structural changes in the complex.

Figure 8
The SCSC transformation of 2 (top) to 4 (bottom) via the partial removal of the lattice solvent molecules. The anionic clusters (Cd₂I₆)²⁻ have been omitted.

Unlike the parent complex 2, for example, complex 4 has two crystallographically different Cd^II atoms (Cd1 and Cd2). In addition, some changes in the pairwise interaction between two macrocyclic complex units were observed: the distance between Cd1A and I1 in 2 is 3.5768 (8) Å, while it is 3.415 (7) Å (Cd1A⋯I1) and 3.690 (7) Å (Cd2⋯I2B) in 4. Due to the sublimation of the solvent molecules followed by the structural change, 4 shows a high R₁ value (0.1848; Table 1). Recently, we reported some examples of the sliding rearrangement of a double-decker type complex (Kang et al., 2016) of the [2:2] cyclization analogue of L and a one-dimensional coordination polymer of the bis-dithiamacrocycle (Kim et al., 2016 ) via a single-crystal-to-single-crystal (SCSC) transformation upon desolvation in air. The homogeneity of 4 was confirmed by PXRD patterns (Fig. 6). Exposure of 4 to acetonitrile liquid and vapor results in no structural change, suggesting that the above structural transformation is not reversible.

2.4. Complexation with a mixture of CuI and CdI₂

As an extension of the above homonuclear copper(I) iodide complex 1 and cadmium(II) iodide complexes 2–4, we investigated the relative reactivity of copper(I) and cadmium(II) as soft acids towards L in both the solid and solution states. When a mixture of copper(I) iodide and cadmium(II) iodide was reacted with L in acetonitrile/dichloromethane, a yellow block-shaped crystalline product 5 was isolated. X-ray analysis revealed that 5 contains three separate metal-containing parts in the formula [Cu(L)]₂(Cd₂I₆) (Fig. 9a): two macrocyclic monocopper(I) complex cations and one (Cd₂I₆)²⁻ cluster anion, indicating a preferential coordination affinity of copper(I) over cadmium(II) towards L. Since the inversion center exists in the middle of the (Cd₂I₆)²⁻ cluster, the asymmetric unit contains one macrocyclic copper(I) complex unit and half a cluster. The copper(I) center inside the cavity is five-coordinate, being bound by all the donors from L in a twisted conformation. The Cu^I coordination geometry is a distorted square-pyramidal geometry (τ = 0.29) with donors S1, O1, O2 and N1 of L defining a distorted square plane and the S2 donor in an axial position (Fig. 9b).

Figure 9
The molecular structure of 5, [Cu(L)]₂(Cd₂I₆), showing the three separate parts. (a) A general view and (b) the distorted square-pyramidal coordination geometry of the copper(I) center. [Symmetry code: (A) 1 - x, 1 - y, 1 - z.]

2.5. Comparative NMR study of Cu^I and Cd^II complexation

Comparative NMR experiments for the competition reactions of copper(I) and cadmium(II) toward L were also performed. In Fig. 10, the signals of the aliphatic protons (H₁–H₃) in L are well resolved and identified. As shown in Fig. 10(a) line (B), the addition of 1–4 equivalents of copper(I) causes downfield shifts for H₁–H₃ of 0.15–0.3 p.p.m. and indicates that complexation with fast ligand exchange is occurring on the NMR time scale. In this case, the chemical shift changes are H₃ > H₂ > H₁, indicating that copper(I) favors binding to the S donors rather than to the O donors. Further addition of cadmium(II) (1–4 equivalents) led to no significant chemical shift changes [Fig. 10a lines (F) and (I)], suggesting that the copper(I) complex formed earlier is maintained and no further reaction occurs (as proposed in Fig. 10c).

Figure 10
¹H NMR spectra of the aliphatic region for L in CD₃CN via stepwise addition of (a) Cd²⁺ and Cu⁺, and (b) Cu⁺ and Cd²⁺. [L] = 5 mM. (c) The proposed complexation equilibria between the corresponding species in solution.

Comparative NMR experiments for the above competition reaction were also performed in the reverse order of salt addition [that is, cadmium(II) followed by copper(I)]. As shown in Fig. 10(b) lines (A) and (E), the cadmium(II) complexation proceeds by two steps. First, the addition of one equivalent of cadmium(II) causes downfield shifts for H₁–H₃. On addition of another one equivalent of cadmium(II), further downfield shifts of each peak were observed, in keeping with the formation of a dicadmium(II) species [Cd₂L]⁴⁺ (Fig. 10b). On addition of one equivalent of copper(I), larger upfield shifts occur and the spectral pattern in Fig. 10(a) line (I) becomes the same as that shown in Fig. 10(b) line (I), suggesting that the respective reactions finally reach the formation of the monocopper(I) species [CuL]⁺ (Fig. 10c, anticlockwise direction starting from L). Again, this result agrees with the solid-state data in showing that copper(I) has a higher affinity for L than does cadmium(II). Considering the size effect of the metal ions [Cd^II (4d¹⁰) is slightly larger than Cu^I (3d¹⁰)] on their affinity towards the 19-membered ring cavity of L, Cd^II is expected to have a higher affinity, unlike the results obtained from the X-ray and NMR data in this work. Consequently, the greater thiaphilic nature of Cu^I than of Cd^II could be the main reason associated with the shorter bond distances of Cu^I—S (2.25–2.27 Å) in 1 than those of Cd^II—S (2.67–2.74 Å) in 2.

3. Conclusions

In summary, sequential photographic snapshots, single-crystal X-ray structures and PXRD patterns of cadmium(II) iodide complexes of an NO₂S₃ macrocycle enable us to identify kinetic and thermodynamic products. From the visual data, it was found that the reaction process from the kinetic product to the thermodynamic product resulted in the elimination of the lattice solvents and the contraction of two facing macrocyclic complex units, resulting in the formation of a pseudo-dimer via a Cd⋯I interaction. In the competition reactions, L shows preferential complexation behavior towards copper(I) over cadmium(II) in both solid and solution states.

4. Experimental

4.1. General

All chemicals were purchased from commercial sources and used as received. All solvents used were of reagent grade. Elemental analyses were carried out on a LECO CHNS-932 elemental analyzer. Thermogravimetric analyses were recorded on a TA Instruments TGA-Q50 thermogravimetric analyzer. The FT–IR spectra were recorded using a Thermo Fisher Scientific Nicolet iS 10 FT–IR spectrometer with KBr pellets.

4.2. Preparation of [Cu(L)]₂(Cu₂I₄)·2CH₂Cl₂, 1

CuI (12 mg, 0.062 mmol) was dissolved in methanol (l.0 ml) and added to a solution of L (10 mg, 0.021 mmol) in dichloromethane (l.0 ml). A white precipitate formed immediately and this was filtered off. Colorless crystalline 1 suitable for X-ray analysis was obtained by vapor diffusion of diethyl ether into a dimethylformamide (0.5 ml) solution of the precipitate (yield 35%). Analysis, calculated for C₆₀H₅₈Cl₄Cu₄I₄N₂O₄S₄: C 38.98, H 3.10, N 1.54, S 7.05%; found: C 39.23, H 3.27, N 1.44, S 6.83%. IR (KBr pellet, ν, cm⁻¹): 2925, 2855, 1719, 1655, 1560, 1459, 1377, 1341, 1296, 1245, 1219, 1186, 1159, 1106, 1048, 1027, 807, 753.

4.3. Preparation of [Cd(L)I]₂(Cd₂I₆)·4CH₃CN, 2, and [Cd₂(L)₂I₂](Cd₂I₆), 3

A solution of CdI₂ (24 mg, 0.066 mmol) in acetonitrile (0.5 ml) was added to a solution of L (10 mg, 0.021 mmol) in dichloromethane (0.5 ml). Slow evaporation of the solution afforded two kinds of crystals: at the beginning (within 2 d) colorless needle-shaped crystals of 2 formed in the vial, which converted to the pale-yellow block-shaped crystals of 3 after 4 d. Separately, white precipitates of 2 and 3 were obtained from a reaction mixture of L and CdI₂ in acetonitrile/dichloromethane at room temperature and 50°C for 10 min, respectively. For 3, yield 70%. Analysis, calculated for C₅₈H₅₄Cd₄I₈N₂O₄S₄: C 28.59, H 2.23, N 1.15, S 5.26%; found: C 28.47, H 2.14, N 1.35, S 5.45%. IR (KBr pellet, ν, cm⁻¹): 2958, 2920, 2863, 1925, 1719, 1686, 1604, 1579, 1560, 1543, 1508, 1490, 1455, 1440, 1400, 1385, 1372, 1290, 1277, 1246, 1220, 1181, 1161, 1111, 1099, 1047, 1032, 943, 902, 869, 842.

4.4. Preparation of [Cd(L)I]₂(Cd₂I₆)₂·CH₃CN, 4

Single crystals of 4 were obtained from single crystals of 2 which had been kept at room temperature for 10 min in air. Analysis, calculated for C₁₂₀H₁₁₄Cd₈I₁₆N₆O₈S₈: C 29.09, H 2.32, N 1.70, S 5.18%; found: C 28.75, H 2.18, N 1.24, S 5.44%. IR (KBr pellet, ν, cm⁻¹): 3051, 2957, 2919, 2344, 1719, 1638, 1604, 1579, 1560, 1543, 1490, 1454, 1440, 1412, 1400, 1385, 1371, 1292, 1276, 1246, 1220, 1193, 1180, 1160, 1111, 1098, 1047, 1032, 1012, 902, 867, 841, 807.

4.5. Preparation of [Cu(L)]₂(Cd₂I₆), 5

CuI (12 mg, 0.062 mmol) and CdI₂ (24 mg, 0.066 mmol) were dissolved in acetonitrile (l.0 ml) and the solution was layered on a solution of L (10 mg, 0.08 mmol) in dichloromethane (l.0 ml). The (layered) mixture afforded a yellow crystalline product, 5, suitable for X-ray analysis (yield 45%). Analysis, calculated for C₅₈H₅₄Cd₂Cu₂I₆N₂O₄S₄: C 33.42, H 2.61, N 1.34, S 6.15%; found: C 33.77, H 2.53, N 1.28, S 6.41%. IR (KBr pellet, ν, cm⁻¹): 2966, 2926, 2855, 1871, 1735, 1655, 1560, 1491, 1459, 1490, 1459, 1253, 1244, 1218, 1188, 1161, 1106, 1075, 1048, 1023, 958, 939, 908, 758, 742.

4.6. X-ray crystallographic analysis

Crystal data for 1–5 were collected at 173 K on a Bruker SMART APEXII ULTRA diffractometer equipped with graphite monochromated Mo Kα radiation (λ = 0.71073 Å) generated by a rotating anode. The cell parameters for the compounds were obtained from a least-squares refinement of the spot (from 36 collected frames). Data collection, data reduction and absorption correction were carried out using the software package APEX2 (Bruker, 2008 ). All calculations for the structure determination were carried out using the SHELXTL package (Bruker, 2001 ). In all cases, all non-hydrogen atoms were refined anisotropically, and all hydrogen atoms were placed in idealized positions and refined isotropically in a riding manner along with their respective parent atoms. Due to the sublimation of the solvent molecules (acetonitrile) of 2 followed by a structural change, 4 shows relatively high R values. Since the remaining lattice solvent molecules (four acetonitrile molecules in 2 and one acetonitrile molecule in 4) are highly disordered, the contribution of solvent electron density was removed using the SQUEEZE routine in PLATON (Spek, 2009 ). Several SHELXTL restraints were used in the refinements of 1 and 4. In 1, SADI was used to keep within a reasonable geometry for the non-disordered part of the dichloromethane molecule. In 4, SADI, DFIX, SIMU and soft constraints were used to keep within a reasonable geometry for the non-disordered part of the macrocyclic ligand. Relevant crystal data collection and refinement data for the crystal structures of 1–5 are summarized in Table 1, and in Tables S1–S5 in the supporting information.

Supporting information

CCDC references: 1566938; 1566939; 1566940; 1566941; 1566942

Crystal structure: contains datablocks 1, 2, 3, 4, 5. DOI: https://doi.org/10.1107/S2052252517015081/yc5012sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2052252517015081/yc50121sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2052252517015081/yc50122sup3.hkl

Structure factors: contains datablock 3. DOI: https://doi.org/10.1107/S2052252517015081/yc50123sup4.hkl

Structure factors: contains datablock 4. DOI: https://doi.org/10.1107/S2052252517015081/yc50124sup5.hkl

Structure factors: contains datablock 5. DOI: https://doi.org/10.1107/S2052252517015081/yc50125sup6.hkl

Time-series snapshots for the single-crystal growth process, Fig. S1. DOI: https://doi.org/10.1107/S2052252517015081/yc5012sup7.gif

Time-series snapshots for the single-crystal growth process, Movie S1. DOI: https://doi.org/10.1107/S2052252517015081/yc5012sup8.mov

Additional tables. DOI: https://doi.org/10.1107/S2052252517015081/yc5012sup9.pdf

Computing details top

For all structures, data collection: Bruker APEX2; cell refinement: Bruker SAINT; data reduction: Bruker SAINT. Program(s) used to solve structure: Bruker SHELXTL for (1), (2), (3), (4); SHELXS97 (Sheldrick, 2008) for (5). Program(s) used to refine structure: Bruker SHELXTL for (1); SHELXL2014/7 (Sheldrick, 2014) for (2), (3), (4); SHELXL97 (Sheldrick, 2008) for (5). For all structures, molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

(1) top

Crystal data top

C₃₀H₂₉Cl₂Cu₂I₂NO₂S₂	Z = 2
M_r = 951.44	F(000) = 924
Triclinic, P1	D_x = 1.923 Mg m⁻³
a = 11.7925 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.9665 (4) Å	Cell parameters from 6962 reflections
c = 13.4375 (4) Å	θ = 2.3–27.0°
α = 93.290 (2)°	µ = 3.49 mm⁻¹
β = 95.681 (2)°	T = 173 K
γ = 118.683 (2)°	Plate, pink
V = 1643.38 (9) Å³	0.10 × 0.06 × 0.04 mm

Data collection top

Bruker APEX-II CCD diffractometer	6174 independent reflections
Radiation source: fine-focus sealed tube	4789 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
φ and ω scans	θ_max = 26.0°, θ_min = 1.5°
Absorption correction: multi-scan SADABS	h = −14→14
T_min = 0.722, T_max = 0.873	k = −14→14
22525 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.234	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.1254P)² + 21.3275P] where P = (F_o² + 2F_c²)/3
6174 reflections	(Δ/σ)_max = 0.001
370 parameters	Δρ_max = 3.30 e Å⁻³
1 restraint	Δρ_min = −2.78 e Å⁻³

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Cu1	0.70988 (12)	0.20707 (12)	0.86183 (9)	0.0224 (3)
Cu2	0.93539 (15)	0.88287 (15)	0.46019 (11)	0.0389 (4)
I1	0.91757 (7)	1.05828 (7)	0.36858 (5)	0.0316 (2)
I2	0.81705 (8)	0.65719 (8)	0.37430 (6)	0.0446 (3)
S1	0.4984 (2)	0.1255 (2)	0.79061 (18)	0.0230 (5)
S2	0.8488 (2)	0.2193 (3)	0.75367 (18)	0.0230 (5)
O1	0.7952 (6)	0.0632 (7)	0.9593 (5)	0.0235 (15)
O2	0.7012 (7)	0.4240 (8)	0.8932 (5)	0.0299 (16)
N1	0.7811 (7)	0.2833 (8)	1.0081 (6)	0.0201 (17)
C1	0.7805 (10)	0.2112 (10)	1.0804 (8)	0.025 (2)
C2	0.8167 (11)	0.2578 (13)	1.1816 (8)	0.036 (3)
H2A	0.8166	0.2040	1.2309	0.043*
C3	0.8536 (12)	0.3866 (13)	1.2093 (8)	0.040 (3)
H3A	0.8766	0.4217	1.2782	0.048*
C4	0.8557 (11)	0.4606 (11)	1.1351 (8)	0.032 (2)
H4A	0.8811	0.5484	1.1520	0.038*
C5	0.8216 (9)	0.4085 (10)	1.0371 (8)	0.024 (2)
C6	0.8290 (10)	0.4888 (11)	0.9526 (8)	0.028 (2)
H6A	0.8511	0.5766	0.9798	0.033*
H6B	0.8963	0.4946	0.9113	0.033*
C7	0.6853 (10)	0.4511 (10)	0.7984 (8)	0.025 (2)
C8	0.7804 (11)	0.5512 (11)	0.7562 (8)	0.031 (2)
H8A	0.8640	0.6052	0.7942	0.037*
C9	0.7533 (14)	0.5724 (12)	0.6582 (9)	0.040 (3)
H9A	0.8181	0.6409	0.6292	0.048*
C10	0.6316 (12)	0.4932 (12)	0.6035 (8)	0.035 (3)
H10A	0.6126	0.5070	0.5364	0.042*
C11	0.5380 (12)	0.3947 (11)	0.6457 (8)	0.032 (2)
H11A	0.4542	0.3418	0.6075	0.038*
C12	0.5629 (10)	0.3706 (11)	0.7431 (8)	0.027 (2)
C13	0.4656 (10)	0.2597 (11)	0.7898 (8)	0.028 (2)
H13A	0.3773	0.2293	0.7524	0.034*
H13B	0.4655	0.2897	0.8600	0.034*
C14	0.4865 (10)	0.0887 (11)	0.6555 (8)	0.027 (2)
H14A	0.3964	0.0605	0.6230	0.033*
H14B	0.5466	0.1669	0.6273	0.033*
C15	0.5209 (10)	−0.0159 (11)	0.6331 (7)	0.026 (2)
C16	0.4209 (11)	−0.1414 (11)	0.6226 (8)	0.032 (2)
H16A	0.3340	−0.1599	0.6281	0.039*
C17	0.4494 (14)	−0.2415 (12)	0.6038 (9)	0.042 (3)
H17A	0.3810	−0.3279	0.5976	0.050*
C18	0.5712 (14)	−0.2175 (13)	0.5944 (9)	0.042 (3)
H18A	0.5887	−0.2863	0.5823	0.050*
C19	0.6697 (12)	−0.0934 (12)	0.6024 (8)	0.033 (3)
H19A	0.7551	−0.0770	0.5939	0.040*
C20	0.6479 (10)	0.0107 (11)	0.6230 (7)	0.027 (2)
C21	0.7589 (10)	0.1449 (11)	0.6275 (8)	0.029 (2)
H21A	0.7240	0.1990	0.5999	0.035*
H21B	0.8209	0.1438	0.5834	0.035*
C22	0.9016 (10)	0.1037 (11)	0.7823 (8)	0.026 (2)
H22A	0.8239	0.0184	0.7816	0.031*
H22B	0.9514	0.0966	0.7294	0.031*
C23	0.9865 (9)	0.1410 (9)	0.8843 (7)	0.021 (2)
C24	1.1195 (10)	0.1886 (11)	0.8918 (9)	0.030 (2)
H24A	1.1592	0.2063	0.8322	0.037*
C25	1.1963 (10)	0.2110 (11)	0.9815 (8)	0.027 (2)
H25A	1.2875	0.2425	0.9840	0.033*
C26	1.1398 (10)	0.1875 (10)	1.0690 (9)	0.030 (2)
H26A	1.1926	0.2035	1.1319	0.036*
C27	1.0058 (10)	0.1405 (10)	1.0650 (8)	0.027 (2)
H27A	0.9667	0.1242	1.1248	0.032*
C28	0.9301 (9)	0.1176 (9)	0.9719 (8)	0.022 (2)
C29	0.7380 (10)	0.0730 (11)	1.0450 (8)	0.028 (2)
H29A	0.7638	0.0345	1.1000	0.034*
H29B	0.6417	0.0244	1.0280	0.034*
Cl1S	0.5146 (9)	0.7735 (11)	0.8731 (8)	0.171 (4)
Cl2S	0.4434 (9)	0.5256 (9)	0.9127 (7)	0.148 (3)
C1S	0.4817 (16)	0.6243 (11)	0.8211 (12)	0.070 (5)
H1SA	0.4078	0.5902	0.7654	0.084*
H1SB	0.5591	0.6303	0.7937	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0251 (6)	0.0189 (7)	0.0253 (6)	0.0125 (5)	0.0038 (5)	0.0013 (5)
Cu2	0.0394 (8)	0.0372 (9)	0.0422 (8)	0.0202 (7)	0.0078 (6)	0.0035 (7)
I1	0.0362 (4)	0.0318 (5)	0.0317 (4)	0.0212 (4)	0.0007 (3)	0.0052 (3)
I2	0.0460 (5)	0.0356 (5)	0.0461 (5)	0.0146 (4)	0.0105 (4)	0.0028 (4)
S1	0.0216 (11)	0.0189 (13)	0.0289 (12)	0.0093 (10)	0.0079 (9)	0.0052 (10)
S2	0.0184 (11)	0.0223 (14)	0.0283 (12)	0.0096 (10)	0.0054 (9)	0.0040 (10)
O1	0.020 (3)	0.016 (4)	0.035 (4)	0.008 (3)	0.007 (3)	0.004 (3)
O2	0.027 (4)	0.030 (5)	0.032 (4)	0.014 (3)	0.003 (3)	0.011 (3)
N1	0.017 (4)	0.016 (5)	0.028 (4)	0.010 (3)	0.002 (3)	−0.003 (3)
C1	0.021 (5)	0.024 (6)	0.031 (5)	0.012 (4)	0.008 (4)	0.006 (4)
C2	0.038 (6)	0.045 (8)	0.031 (6)	0.026 (6)	0.002 (5)	0.006 (5)
C3	0.045 (7)	0.051 (8)	0.027 (5)	0.030 (6)	−0.004 (5)	−0.009 (5)
C4	0.033 (6)	0.026 (6)	0.041 (6)	0.019 (5)	0.005 (5)	−0.005 (5)
C5	0.018 (5)	0.022 (6)	0.034 (5)	0.012 (4)	0.001 (4)	0.001 (4)
C6	0.026 (5)	0.026 (6)	0.033 (5)	0.014 (5)	0.002 (4)	0.001 (4)
C7	0.027 (5)	0.022 (6)	0.032 (5)	0.017 (5)	0.004 (4)	0.002 (4)
C8	0.033 (6)	0.024 (6)	0.035 (6)	0.013 (5)	0.006 (4)	0.006 (5)
C9	0.058 (8)	0.025 (7)	0.039 (6)	0.020 (6)	0.016 (6)	0.010 (5)
C10	0.051 (7)	0.029 (7)	0.029 (5)	0.022 (6)	0.004 (5)	0.005 (5)
C11	0.042 (6)	0.029 (7)	0.035 (6)	0.027 (6)	0.000 (5)	0.000 (5)
C12	0.023 (5)	0.026 (6)	0.039 (6)	0.016 (5)	0.007 (4)	0.002 (4)
C13	0.028 (5)	0.029 (6)	0.036 (6)	0.022 (5)	0.005 (4)	0.002 (5)
C14	0.023 (5)	0.031 (6)	0.027 (5)	0.013 (5)	0.004 (4)	0.002 (4)
C15	0.030 (5)	0.027 (6)	0.022 (5)	0.014 (5)	0.005 (4)	0.004 (4)
C16	0.032 (6)	0.025 (6)	0.037 (6)	0.013 (5)	0.003 (5)	0.000 (5)
C17	0.060 (8)	0.017 (6)	0.044 (7)	0.017 (6)	−0.003 (6)	−0.002 (5)
C18	0.067 (9)	0.040 (8)	0.033 (6)	0.041 (7)	−0.001 (6)	−0.006 (5)
C19	0.038 (6)	0.036 (7)	0.032 (6)	0.024 (6)	0.003 (5)	−0.007 (5)
C20	0.027 (5)	0.037 (7)	0.017 (4)	0.016 (5)	0.006 (4)	0.001 (4)
C21	0.024 (5)	0.036 (7)	0.024 (5)	0.013 (5)	0.002 (4)	0.002 (4)
C22	0.026 (5)	0.024 (6)	0.030 (5)	0.014 (5)	0.006 (4)	0.002 (4)
C23	0.024 (5)	0.012 (5)	0.033 (5)	0.014 (4)	0.002 (4)	0.001 (4)
C24	0.026 (5)	0.021 (6)	0.045 (6)	0.011 (5)	0.007 (5)	0.004 (5)
C25	0.018 (5)	0.028 (6)	0.039 (6)	0.014 (5)	0.002 (4)	0.002 (5)
C26	0.029 (5)	0.016 (6)	0.044 (6)	0.014 (5)	−0.005 (5)	0.002 (4)
C27	0.033 (5)	0.019 (6)	0.037 (6)	0.019 (5)	0.011 (4)	0.008 (4)
C28	0.023 (5)	0.008 (5)	0.038 (5)	0.010 (4)	0.008 (4)	0.003 (4)
C29	0.029 (5)	0.027 (6)	0.035 (5)	0.016 (5)	0.014 (4)	0.011 (5)
Cl1S	0.123 (6)	0.196 (10)	0.185 (8)	0.088 (7)	−0.059 (6)	−0.011 (7)
Cl2S	0.133 (6)	0.140 (7)	0.177 (8)	0.077 (6)	0.013 (6)	−0.018 (6)
C1S	0.052 (9)	0.071 (12)	0.068 (10)	0.018 (9)	0.010 (8)	−0.017 (9)

Geometric parameters (Å, º) top

Cu1—N1	2.032 (8)	C7—C8	1.389 (16)
Cu1—S2	2.255 (3)	C7—C12	1.392 (15)
Cu1—S1	2.274 (3)	C8—C9	1.390 (16)
Cu2—I2	2.5057 (17)	C9—C10	1.380 (18)
Cu2—Cu2ⁱ	2.561 (3)	C10—C11	1.372 (18)
Cu2—I1	2.5757 (17)	C11—C12	1.390 (15)
Cu2—I1ⁱ	2.5784 (16)	C12—C13	1.499 (16)
I1—Cu2ⁱ	2.5785 (16)	C14—C15	1.514 (15)
S1—C14	1.818 (10)	C15—C16	1.382 (16)
S1—C13	1.825 (10)	C15—C20	1.396 (14)
S2—C22	1.815 (10)	C16—C17	1.407 (16)
S2—C21	1.832 (10)	C17—C18	1.344 (19)
O1—C28	1.387 (12)	C18—C19	1.366 (19)
O1—C29	1.417 (12)	C19—C20	1.405 (15)
O2—C7	1.349 (12)	C20—C21	1.501 (16)
O2—C6	1.442 (12)	C22—C23	1.518 (14)
N1—C1	1.334 (13)	C23—C24	1.379 (14)
N1—C5	1.355 (13)	C23—C28	1.386 (14)
C1—C2	1.382 (15)	C24—C25	1.363 (15)
C1—C29	1.510 (16)	C25—C26	1.385 (16)
C2—C3	1.401 (18)	C26—C27	1.394 (15)
C3—C4	1.365 (18)	C27—C28	1.393 (15)
C4—C5	1.358 (15)	Cl1S—C1S	1.722 (13)
C5—C6	1.511 (15)	Cl2S—C1S	1.697 (13)

N1—Cu1—S2	119.6 (2)	C7—C8—C9	120.1 (11)
N1—Cu1—S1	125.1 (2)	C10—C9—C8	119.5 (12)
S2—Cu1—S1	115.05 (10)	C11—C10—C9	120.2 (11)
I2—Cu2—Cu2ⁱ	176.68 (10)	C10—C11—C12	121.5 (11)
I2—Cu2—I1	118.37 (6)	C11—C12—C7	118.2 (11)
Cu2ⁱ—Cu2—I1	60.26 (6)	C11—C12—C13	123.1 (10)
I2—Cu2—I1ⁱ	121.12 (7)	C7—C12—C13	118.7 (10)
Cu2ⁱ—Cu2—I1ⁱ	60.15 (6)	C12—C13—S1	113.5 (7)
I1—Cu2—I1ⁱ	120.42 (6)	C15—C14—S1	110.7 (7)
Cu2—I1—Cu2ⁱ	59.58 (6)	C16—C15—C20	120.2 (10)
C14—S1—C13	98.8 (5)	C16—C15—C14	117.4 (9)
C14—S1—Cu1	108.9 (3)	C20—C15—C14	122.5 (10)
C13—S1—Cu1	106.8 (4)	C15—C16—C17	119.1 (11)
C22—S2—C21	98.4 (5)	C18—C17—C16	121.4 (12)
C22—S2—Cu1	107.2 (4)	C17—C18—C19	119.6 (11)
C21—S2—Cu1	110.3 (3)	C18—C19—C20	121.7 (11)
C28—O1—C29	117.0 (8)	C15—C20—C19	118.0 (10)
C7—O2—C6	119.7 (8)	C15—C20—C21	122.6 (10)
C1—N1—C5	117.1 (8)	C19—C20—C21	119.3 (9)
C1—N1—Cu1	122.0 (7)	C20—C21—S2	114.9 (7)
C5—N1—Cu1	120.7 (7)	C23—C22—S2	112.2 (7)
N1—C1—C2	123.3 (10)	C24—C23—C28	118.2 (9)
N1—C1—C29	115.6 (9)	C24—C23—C22	121.1 (9)
C2—C1—C29	121.1 (10)	C28—C23—C22	120.4 (9)
C1—C2—C3	118.1 (11)	C25—C24—C23	122.4 (10)
C4—C3—C2	118.5 (10)	C24—C25—C26	119.3 (10)
C5—C4—C3	119.9 (11)	C25—C26—C27	120.2 (10)
N1—C5—C4	123.0 (10)	C28—C27—C26	119.0 (10)
N1—C5—C6	115.5 (9)	C23—C28—O1	115.7 (9)
C4—C5—C6	121.5 (10)	C23—C28—C27	120.8 (9)
O2—C6—C5	105.6 (8)	O1—C28—C27	123.4 (9)
O2—C7—C8	124.6 (10)	O1—C29—C1	111.2 (8)
O2—C7—C12	114.9 (10)	Cl2S—C1S—Cl1S	108.2 (10)
C8—C7—C12	120.5 (10)

Symmetry code: (i) −x+2, −y+2, −z+1.

(2) top

Crystal data top

C₂₉H₂₇Cd₂I₄NO₂S₂	F(000) = 4512
M_r = 1218.03	D_x = 1.962 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 23.3017 (6) Å	Cell parameters from 9484 reflections
b = 13.4569 (4) Å	θ = 2.2–26.9°
c = 26.9935 (7) Å	µ = 4.15 mm⁻¹
β = 102.963 (1)°	T = 173 K
V = 8248.6 (4) Å³	Needle, colourless
Z = 8	0.24 × 0.07 × 0.04 mm

Data collection top

Bruker APEX-II CCD diffractometer	6760 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.050
Absorption correction: multi-scan SADABS	θ_max = 26.0°, θ_min = 1.6°
T_min = 0.435, T_max = 0.851	h = −28→28
36289 measured reflections	k = −15→16
8103 independent reflections	l = −33→33

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.103	w = 1/[σ²(F_o²) + (0.0281P)² + 115.2429P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
8103 reflections	Δρ_max = 1.49 e Å⁻³
362 parameters	Δρ_min = −0.91 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
I1	0.43100 (2)	0.91855 (4)	0.52336 (2)	0.03691 (13)
I2	0.45809 (2)	0.41593 (4)	0.81128 (2)	0.03181 (12)
I3	0.64996 (2)	0.51409 (4)	0.84762 (2)	0.03908 (14)
I4	0.60782 (3)	0.18524 (4)	0.80892 (2)	0.04304 (15)
Cd1	0.54881 (2)	0.87965 (4)	0.55728 (2)	0.02864 (13)
Cd2	0.57467 (3)	0.37768 (4)	0.79557 (2)	0.03299 (14)
S1	0.55129 (7)	0.80366 (13)	0.46359 (6)	0.0258 (4)
S2	0.57244 (8)	0.71247 (14)	0.61020 (6)	0.0282 (4)
O1	0.5143 (2)	0.9178 (4)	0.65211 (18)	0.0336 (12)
O2	0.6539 (2)	0.8744 (4)	0.55757 (19)	0.0333 (12)
N1	0.6020 (3)	0.9983 (4)	0.6112 (2)	0.0276 (13)
C1	0.6562 (3)	1.0253 (5)	0.6055 (3)	0.0304 (17)
C2	0.6835 (4)	1.1129 (6)	0.6253 (3)	0.046 (2)
H2A	0.7213	1.1306	0.6204	0.055*
C3	0.6533 (5)	1.1736 (6)	0.6524 (3)	0.055 (3)
H3A	0.6698	1.2355	0.6654	0.066*
C4	0.5992 (4)	1.1440 (6)	0.6607 (3)	0.042 (2)
H4A	0.5793	1.1836	0.6807	0.051*
C5	0.5751 (4)	1.0570 (6)	0.6396 (2)	0.0329 (18)
C6	0.5161 (4)	1.0219 (6)	0.6472 (3)	0.0381 (19)
H6A	0.5081	1.0533	0.6781	0.046*
H6B	0.4848	1.0431	0.6179	0.046*
C7	0.5460 (4)	0.8749 (6)	0.6973 (3)	0.0343 (17)
C8	0.5717 (4)	0.9305 (6)	0.7399 (3)	0.040 (2)
H8A	0.5704	1.0010	0.7389	0.048*
C9	0.5989 (5)	0.8817 (7)	0.7836 (3)	0.053 (2)
H9A	0.6150	0.9185	0.8135	0.064*
C10	0.6030 (4)	0.7798 (7)	0.7842 (3)	0.049 (2)
H10A	0.6242	0.7465	0.8137	0.059*
C11	0.5772 (4)	0.7281 (7)	0.7433 (3)	0.042 (2)
H11A	0.5787	0.6576	0.7449	0.050*
C12	0.5480 (4)	0.7730 (5)	0.6980 (3)	0.0338 (18)
C13	0.5209 (3)	0.7137 (6)	0.6513 (3)	0.0327 (17)
H13A	0.4833	0.7444	0.6335	0.039*
H13B	0.5128	0.6450	0.6609	0.039*
C14	0.5483 (3)	0.6063 (5)	0.5682 (3)	0.0332 (17)
H14A	0.5782	0.5939	0.5481	0.040*
H14B	0.5471	0.5469	0.5896	0.040*
C15	0.4901 (3)	0.6166 (5)	0.5326 (3)	0.0284 (16)
C16	0.4385 (4)	0.5916 (6)	0.5488 (3)	0.0355 (18)
H16A	0.4417	0.5680	0.5825	0.043*
C17	0.3843 (4)	0.6002 (6)	0.5175 (3)	0.043 (2)
H17A	0.3502	0.5849	0.5299	0.052*
C18	0.3783 (3)	0.6319 (6)	0.4665 (3)	0.0376 (18)
H18A	0.3406	0.6373	0.4443	0.045*
C19	0.4266 (3)	0.6536 (6)	0.4508 (3)	0.0342 (17)
H19A	0.4222	0.6753	0.4167	0.041*
C20	0.4831 (3)	0.6468 (5)	0.4807 (2)	0.0248 (15)
C21	0.5348 (3)	0.6705 (5)	0.4589 (2)	0.0267 (15)
H21A	0.5265	0.6500	0.4227	0.032*
H21B	0.5695	0.6327	0.4773	0.032*
C22	0.6281 (3)	0.8026 (6)	0.4580 (3)	0.0331 (17)
H22A	0.6304	0.7713	0.4253	0.040*
H22B	0.6422	0.8719	0.4576	0.040*
C23	0.6681 (3)	0.7467 (5)	0.5012 (2)	0.0261 (15)
C24	0.6893 (3)	0.6525 (6)	0.4932 (3)	0.0333 (17)
H24A	0.6783	0.6222	0.4607	0.040*
C25	0.7268 (3)	0.6027 (6)	0.5334 (3)	0.0386 (19)
H25A	0.7427	0.5398	0.5278	0.046*
C26	0.7405 (3)	0.6454 (6)	0.5811 (3)	0.040 (2)
H26A	0.7659	0.6116	0.6084	0.048*
C27	0.7180 (3)	0.7358 (6)	0.5893 (3)	0.0365 (18)
H27A	0.7275	0.7649	0.6222	0.044*
C28	0.6815 (3)	0.7846 (5)	0.5499 (3)	0.0282 (16)
C29	0.6902 (4)	0.9561 (6)	0.5778 (4)	0.046 (2)
H29A	0.7023	0.9925	0.5499	0.055*
H29B	0.7261	0.9319	0.6016	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0285 (3)	0.0360 (3)	0.0431 (3)	0.0057 (2)	0.0014 (2)	0.0031 (2)
I2	0.0440 (3)	0.0323 (3)	0.0193 (2)	−0.0026 (2)	0.00772 (19)	−0.00396 (19)
I3	0.0382 (3)	0.0368 (3)	0.0368 (3)	−0.0059 (2)	−0.0031 (2)	−0.0037 (2)
I4	0.0671 (4)	0.0298 (3)	0.0289 (3)	0.0023 (3)	0.0038 (2)	0.0004 (2)
Cd1	0.0275 (3)	0.0299 (3)	0.0268 (3)	0.0046 (2)	0.0025 (2)	−0.0031 (2)
Cd2	0.0418 (3)	0.0300 (3)	0.0249 (3)	−0.0020 (3)	0.0026 (2)	0.0003 (2)
S1	0.0262 (9)	0.0277 (9)	0.0217 (8)	0.0004 (7)	0.0013 (7)	0.0042 (7)
S2	0.0328 (9)	0.0299 (10)	0.0209 (8)	0.0020 (8)	0.0039 (7)	−0.0005 (7)
O1	0.046 (3)	0.033 (3)	0.023 (2)	0.007 (2)	0.009 (2)	0.004 (2)
O2	0.030 (3)	0.029 (3)	0.036 (3)	0.003 (2)	0.000 (2)	−0.013 (2)
N1	0.037 (3)	0.020 (3)	0.024 (3)	0.002 (3)	0.002 (2)	−0.002 (2)
C1	0.045 (5)	0.019 (4)	0.024 (3)	0.009 (3)	0.001 (3)	−0.002 (3)
C2	0.054 (5)	0.027 (4)	0.051 (5)	−0.002 (4)	−0.002 (4)	−0.003 (4)
C3	0.096 (8)	0.019 (4)	0.040 (5)	−0.011 (5)	−0.004 (5)	−0.011 (4)
C4	0.065 (6)	0.031 (4)	0.034 (4)	0.013 (4)	0.016 (4)	−0.001 (3)
C5	0.053 (5)	0.029 (4)	0.015 (3)	0.018 (4)	0.004 (3)	0.005 (3)
C6	0.050 (5)	0.037 (5)	0.027 (4)	0.011 (4)	0.008 (3)	−0.002 (3)
C7	0.047 (5)	0.032 (4)	0.026 (4)	0.011 (4)	0.013 (3)	0.010 (3)
C8	0.065 (6)	0.028 (4)	0.024 (4)	0.011 (4)	0.004 (4)	0.001 (3)
C9	0.086 (7)	0.048 (6)	0.022 (4)	−0.007 (5)	0.005 (4)	−0.004 (4)
C10	0.074 (6)	0.045 (5)	0.027 (4)	0.006 (5)	0.006 (4)	0.010 (4)
C11	0.062 (5)	0.043 (5)	0.019 (4)	0.006 (4)	0.006 (4)	0.012 (3)
C12	0.058 (5)	0.024 (4)	0.020 (3)	−0.001 (4)	0.012 (3)	0.000 (3)
C13	0.042 (4)	0.026 (4)	0.032 (4)	−0.005 (3)	0.012 (3)	0.002 (3)
C14	0.046 (5)	0.024 (4)	0.027 (4)	0.006 (3)	0.004 (3)	0.003 (3)
C15	0.040 (4)	0.019 (3)	0.026 (4)	0.000 (3)	0.009 (3)	−0.004 (3)
C16	0.050 (5)	0.027 (4)	0.034 (4)	−0.004 (4)	0.018 (4)	−0.003 (3)
C17	0.046 (5)	0.044 (5)	0.044 (5)	−0.018 (4)	0.019 (4)	−0.011 (4)
C18	0.025 (4)	0.042 (5)	0.042 (4)	0.003 (3)	0.001 (3)	−0.003 (4)
C19	0.038 (4)	0.035 (4)	0.028 (4)	−0.003 (3)	0.003 (3)	−0.007 (3)
C20	0.033 (4)	0.014 (3)	0.025 (3)	−0.003 (3)	0.003 (3)	−0.004 (3)
C21	0.032 (4)	0.027 (4)	0.020 (3)	0.001 (3)	0.003 (3)	−0.003 (3)
C22	0.031 (4)	0.042 (5)	0.024 (4)	−0.001 (3)	0.003 (3)	0.004 (3)
C23	0.026 (4)	0.030 (4)	0.023 (3)	−0.001 (3)	0.006 (3)	−0.002 (3)
C24	0.030 (4)	0.035 (4)	0.036 (4)	0.002 (3)	0.009 (3)	−0.005 (3)
C25	0.026 (4)	0.030 (4)	0.062 (5)	0.006 (3)	0.014 (4)	0.009 (4)
C26	0.027 (4)	0.046 (5)	0.045 (5)	0.012 (4)	0.005 (3)	0.017 (4)
C27	0.033 (4)	0.048 (5)	0.028 (4)	0.007 (4)	0.006 (3)	0.002 (3)
C28	0.024 (4)	0.032 (4)	0.028 (4)	0.009 (3)	0.006 (3)	−0.003 (3)
C29	0.045 (5)	0.038 (5)	0.056 (5)	−0.005 (4)	0.011 (4)	−0.022 (4)

Geometric parameters (Å, º) top

I1—Cd1	2.7422 (7)	C4—C5	1.368 (11)
I2—Cd2ⁱ	2.8598 (7)	C5—C6	1.510 (12)
I2—Cd2	2.8882 (8)	C7—C12	1.372 (10)
I3—Cd2	2.7046 (7)	C7—C8	1.390 (11)
I4—Cd2	2.7033 (8)	C8—C9	1.374 (11)
Cd1—N1	2.321 (6)	C9—C10	1.374 (13)
Cd1—O2	2.447 (5)	C10—C11	1.330 (12)
Cd1—S2	2.6557 (19)	C11—C12	1.396 (10)
Cd1—S1	2.7404 (18)	C12—C13	1.506 (10)
Cd2—I2ⁱ	2.8599 (7)	C14—C15	1.482 (10)
S1—C22	1.828 (7)	C15—C16	1.411 (10)
S1—C21	1.832 (7)	C15—C20	1.431 (9)
S2—C13	1.809 (7)	C16—C17	1.357 (12)
S2—C14	1.832 (7)	C17—C18	1.418 (11)
O1—C7	1.401 (8)	C18—C19	1.320 (11)
O1—C6	1.409 (9)	C19—C20	1.385 (10)
O2—C28	1.407 (8)	C20—C21	1.490 (10)
O2—C29	1.420 (9)	C22—C23	1.520 (10)
N1—C5	1.351 (9)	C23—C28	1.379 (9)
N1—C1	1.355 (10)	C23—C24	1.394 (10)
C1—C2	1.388 (11)	C24—C25	1.401 (11)
C1—C29	1.524 (10)	C25—C26	1.381 (12)
C2—C3	1.389 (13)	C26—C27	1.363 (11)
C3—C4	1.386 (13)	C27—C28	1.370 (10)

Cd2ⁱ—I2—Cd2	82.36 (2)	C4—C5—C6	120.9 (7)
N1—Cd1—O2	67.96 (19)	O1—C6—C5	111.7 (6)
N1—Cd1—S2	103.20 (15)	C12—C7—C8	121.3 (7)
O2—Cd1—S2	83.53 (13)	C12—C7—O1	115.7 (7)
N1—Cd1—S1	135.71 (15)	C8—C7—O1	122.9 (7)
O2—Cd1—S1	76.35 (12)	C9—C8—C7	118.9 (8)
S2—Cd1—S1	97.79 (5)	C10—C9—C8	120.4 (8)
N1—Cd1—I1	115.57 (15)	C11—C10—C9	119.6 (8)
O2—Cd1—I1	158.79 (13)	C10—C11—C12	122.9 (8)
S2—Cd1—I1	114.37 (5)	C7—C12—C11	116.9 (7)
S1—Cd1—I1	89.43 (4)	C7—C12—C13	120.8 (7)
I4—Cd2—I3	116.64 (3)	C11—C12—C13	122.3 (7)
I4—Cd2—I2ⁱ	108.09 (2)	C12—C13—S2	107.9 (5)
I3—Cd2—I2ⁱ	113.39 (2)	C15—C14—S2	116.0 (5)
I4—Cd2—I2	113.66 (3)	C16—C15—C20	116.9 (7)
I3—Cd2—I2	108.94 (2)	C16—C15—C14	119.7 (7)
I2ⁱ—Cd2—I2	93.95 (2)	C20—C15—C14	123.3 (7)
C22—S1—C21	100.4 (4)	C17—C16—C15	121.8 (7)
C22—S1—Cd1	107.6 (2)	C16—C17—C18	120.3 (7)
C21—S1—Cd1	112.5 (2)	C19—C18—C17	118.2 (7)
C13—S2—C14	103.4 (4)	C18—C19—C20	124.5 (7)
C13—S2—Cd1	103.6 (3)	C19—C20—C15	118.2 (7)
C14—S2—Cd1	109.3 (2)	C19—C20—C21	120.3 (6)
C7—O1—C6	118.1 (6)	C15—C20—C21	121.5 (6)
C28—O2—C29	117.9 (6)	C20—C21—S1	110.9 (5)
C28—O2—Cd1	121.0 (4)	C23—C22—S1	112.6 (5)
C29—O2—Cd1	119.3 (4)	C28—C23—C24	118.2 (7)
C5—N1—C1	118.1 (6)	C28—C23—C22	121.1 (6)
C5—N1—Cd1	120.5 (5)	C24—C23—C22	120.5 (6)
C1—N1—Cd1	119.6 (4)	C23—C24—C25	119.7 (7)
N1—C1—C2	122.9 (7)	C26—C25—C24	119.8 (7)
N1—C1—C29	119.5 (6)	C27—C26—C25	120.4 (7)
C2—C1—C29	117.6 (7)	C26—C27—C28	119.7 (7)
C1—C2—C3	117.3 (9)	C27—C28—C23	122.1 (7)
C4—C3—C2	120.2 (8)	C27—C28—O2	121.5 (6)
C5—C4—C3	118.9 (8)	C23—C28—O2	116.4 (6)
N1—C5—C4	122.5 (8)	O2—C29—C1	109.3 (7)
N1—C5—C6	116.6 (7)

Symmetry code: (i) −x+1, y, −z+3/2.

(3) top

Crystal data top

C₅₈H₅₄Cd₄I₈N₂O₄S₄	Z = 1
M_r = 2436.07	F(000) = 1128
Triclinic, P1	D_x = 2.353 Mg m⁻³
a = 11.660 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.147 (3) Å	Cell parameters from 9132 reflections
c = 12.585 (4) Å	θ = 2.4–28.4°
α = 75.142 (11)°	µ = 4.98 mm⁻¹
β = 87.056 (13)°	T = 173 K
γ = 86.996 (13)°	Block, colourless
V = 1719.2 (8) Å³	0.14 × 0.09 × 0.08 mm

Data collection top

Bruker APEX-II CCD diffractometer	6018 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.028
Absorption correction: multi-scan	θ_max = 26.0°, θ_min = 1.7°
	h = −14→14
28690 measured reflections	k = −14→14
6745 independent reflections	l = −15→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.021	H-atom parameters constrained
wR(F²) = 0.046	w = 1/[σ²(F_o²) + (0.0149P)² + 1.4801P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.002
6745 reflections	Δρ_max = 1.42 e Å⁻³
361 parameters	Δρ_min = −1.16 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
I1	0.62247 (2)	0.43008 (2)	0.89896 (2)	0.03269 (5)
I2	1.01894 (2)	−0.16721 (2)	0.48612 (2)	0.03822 (6)
I3	0.95448 (2)	0.09314 (2)	0.15983 (2)	0.05247 (7)
I4	0.66156 (2)	0.03206 (2)	0.42216 (2)	0.04602 (7)
Cd1	0.39016 (2)	0.39221 (2)	0.93283 (2)	0.03191 (6)
Cd2	0.89292 (2)	0.03513 (2)	0.37694 (2)	0.03771 (6)
S1	0.34902 (6)	0.59802 (6)	0.79258 (6)	0.03052 (16)
S2	0.33845 (6)	0.29372 (7)	0.77553 (6)	0.03280 (17)
O1	0.46792 (17)	0.16895 (17)	1.00624 (16)	0.0331 (5)
O2	0.17769 (17)	0.44975 (19)	0.95656 (16)	0.0362 (5)
N1	0.3124 (2)	0.2909 (2)	1.09663 (19)	0.0280 (5)
C1	0.2120 (2)	0.3234 (2)	1.1382 (2)	0.0294 (6)
C2	0.1789 (3)	0.2828 (3)	1.2474 (3)	0.0373 (7)
H2A	0.1065	0.3059	1.2745	0.045*
C3	0.2517 (3)	0.2087 (3)	1.3166 (3)	0.0410 (8)
H3A	0.2316	0.1820	1.3926	0.049*
C4	0.3545 (3)	0.1737 (3)	1.2740 (2)	0.0376 (8)
H4A	0.4057	0.1218	1.3203	0.045*
C5	0.3819 (2)	0.2145 (2)	1.1640 (2)	0.0299 (7)
C6	0.4919 (3)	0.1773 (3)	1.1144 (2)	0.0319 (7)
H6A	0.5515	0.2335	1.1104	0.038*
H6B	0.5201	0.1025	1.1597	0.038*
C7	0.5557 (3)	0.1366 (2)	0.9411 (2)	0.0316 (7)
C8	0.6678 (3)	0.1143 (3)	0.9716 (3)	0.0386 (8)
H8A	0.6894	0.1181	1.0423	0.046*
C9	0.7494 (3)	0.0860 (3)	0.8967 (3)	0.0481 (9)
H9A	0.8270	0.0694	0.9170	0.058*
C10	0.7186 (3)	0.0820 (3)	0.7938 (3)	0.0515 (9)
H10A	0.7750	0.0643	0.7429	0.062*
C11	0.6053 (3)	0.1039 (3)	0.7643 (3)	0.0437 (8)
H11A	0.5845	0.1003	0.6933	0.052*
C12	0.5212 (3)	0.1310 (2)	0.8375 (3)	0.0340 (7)
C13	0.3980 (3)	0.1473 (3)	0.8103 (3)	0.0365 (7)
H13A	0.3524	0.1028	0.8739	0.044*
H13B	0.3872	0.1142	0.7475	0.044*
C14	0.4343 (3)	0.3603 (3)	0.6598 (2)	0.0373 (7)
H14A	0.4978	0.3953	0.6871	0.045*
H14B	0.4683	0.3014	0.6246	0.045*
C15	0.3703 (2)	0.4498 (3)	0.5767 (2)	0.0318 (7)
C16	0.3141 (3)	0.4151 (3)	0.4963 (3)	0.0423 (8)
H16A	0.3142	0.3363	0.4988	0.051*
C17	0.2581 (3)	0.4928 (3)	0.4129 (3)	0.0456 (9)
H17A	0.2214	0.4676	0.3582	0.055*
C18	0.2561 (3)	0.6069 (3)	0.4101 (3)	0.0429 (8)
H18A	0.2185	0.6610	0.3528	0.051*
C19	0.3087 (3)	0.6426 (3)	0.4907 (2)	0.0367 (7)
H19A	0.3061	0.7214	0.4885	0.044*
C20	0.3657 (2)	0.5653 (3)	0.5750 (2)	0.0313 (7)
C21	0.4226 (3)	0.6123 (3)	0.6578 (2)	0.0355 (7)
H21A	0.4339	0.6944	0.6247	0.043*
H21B	0.4999	0.5744	0.6700	0.043*
C22	0.1967 (3)	0.6207 (3)	0.7659 (3)	0.0356 (7)
H22A	0.1596	0.6588	0.8202	0.043*
H22B	0.1882	0.6733	0.6921	0.043*
C23	0.1331 (2)	0.5147 (2)	0.7706 (2)	0.0299 (7)
C24	0.0857 (3)	0.4970 (3)	0.6778 (3)	0.0412 (8)
H24A	0.0941	0.5524	0.6095	0.049*
C25	0.0268 (3)	0.4008 (4)	0.6829 (3)	0.0563 (10)
H25A	−0.0049	0.3899	0.6185	0.068*
C26	0.0136 (3)	0.3208 (4)	0.7804 (4)	0.0585 (11)
H26A	−0.0282	0.2548	0.7839	0.070*
C27	0.0610 (3)	0.3353 (3)	0.8747 (3)	0.0428 (8)
H27A	0.0526	0.2792	0.9426	0.051*
C28	0.1200 (2)	0.4313 (3)	0.8687 (2)	0.0309 (7)
C29	0.1322 (3)	0.4086 (3)	1.0667 (2)	0.0388 (8)
H29A	0.0583	0.3727	1.0646	0.047*
H29B	0.1165	0.4738	1.0996	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.02912 (11)	0.03471 (12)	0.03501 (11)	−0.00425 (8)	0.00121 (8)	−0.01018 (9)
I2	0.04028 (12)	0.03363 (12)	0.04013 (12)	0.00684 (9)	−0.00472 (9)	−0.00930 (9)
I3	0.05806 (15)	0.06057 (17)	0.03465 (13)	0.00353 (12)	0.00391 (11)	−0.00691 (11)
I4	0.02996 (12)	0.05859 (16)	0.04756 (14)	0.00171 (10)	−0.00366 (9)	−0.01023 (11)
Cd1	0.02803 (12)	0.03427 (13)	0.02920 (12)	−0.00075 (9)	0.00331 (9)	−0.00134 (10)
Cd2	0.03274 (13)	0.04300 (15)	0.03409 (13)	0.00324 (10)	−0.00193 (10)	−0.00463 (11)
S1	0.0359 (4)	0.0288 (4)	0.0273 (4)	−0.0039 (3)	−0.0011 (3)	−0.0074 (3)
S2	0.0295 (4)	0.0343 (4)	0.0336 (4)	0.0015 (3)	0.0002 (3)	−0.0075 (3)
O1	0.0306 (11)	0.0370 (12)	0.0330 (11)	0.0006 (9)	0.0012 (9)	−0.0122 (10)
O2	0.0310 (11)	0.0461 (14)	0.0275 (11)	−0.0060 (10)	0.0005 (9)	−0.0014 (10)
N1	0.0288 (13)	0.0276 (13)	0.0268 (13)	−0.0031 (10)	0.0027 (10)	−0.0055 (11)
C1	0.0303 (16)	0.0299 (16)	0.0278 (16)	−0.0052 (12)	0.0033 (12)	−0.0074 (13)
C2	0.0348 (17)	0.0403 (19)	0.0342 (18)	−0.0027 (14)	0.0062 (14)	−0.0057 (15)
C3	0.050 (2)	0.044 (2)	0.0262 (17)	−0.0028 (16)	0.0048 (15)	−0.0045 (15)
C4	0.046 (2)	0.0336 (18)	0.0302 (17)	0.0005 (15)	−0.0023 (14)	−0.0030 (14)
C5	0.0340 (16)	0.0225 (15)	0.0331 (17)	−0.0029 (12)	−0.0026 (13)	−0.0062 (13)
C6	0.0360 (17)	0.0285 (17)	0.0300 (16)	0.0023 (13)	−0.0035 (13)	−0.0053 (13)
C7	0.0333 (17)	0.0231 (16)	0.0375 (17)	0.0010 (12)	0.0054 (13)	−0.0080 (13)
C8	0.0383 (18)	0.0271 (17)	0.048 (2)	0.0022 (13)	0.0002 (15)	−0.0071 (15)
C9	0.0386 (19)	0.040 (2)	0.064 (2)	0.0045 (15)	0.0077 (17)	−0.0123 (18)
C10	0.050 (2)	0.042 (2)	0.060 (2)	0.0057 (17)	0.0181 (18)	−0.0147 (18)
C11	0.058 (2)	0.0300 (18)	0.043 (2)	0.0044 (15)	0.0075 (17)	−0.0119 (15)
C12	0.0412 (18)	0.0203 (16)	0.0397 (18)	0.0003 (13)	0.0038 (14)	−0.0077 (13)
C13	0.0442 (19)	0.0278 (17)	0.0402 (18)	−0.0018 (14)	−0.0022 (14)	−0.0135 (14)
C14	0.0359 (17)	0.042 (2)	0.0307 (17)	0.0052 (14)	0.0029 (13)	−0.0063 (15)
C15	0.0278 (15)	0.0381 (18)	0.0276 (16)	0.0007 (13)	0.0032 (12)	−0.0063 (14)
C16	0.047 (2)	0.043 (2)	0.0388 (19)	0.0008 (16)	0.0027 (15)	−0.0156 (16)
C17	0.046 (2)	0.063 (3)	0.0316 (18)	−0.0005 (17)	−0.0076 (15)	−0.0180 (17)
C18	0.0352 (18)	0.058 (2)	0.0306 (18)	0.0065 (16)	−0.0053 (14)	−0.0036 (16)
C19	0.0346 (17)	0.0384 (19)	0.0321 (17)	0.0047 (14)	0.0045 (13)	−0.0025 (14)
C20	0.0268 (15)	0.0399 (19)	0.0264 (16)	−0.0015 (13)	0.0072 (12)	−0.0085 (14)
C21	0.0363 (17)	0.0386 (19)	0.0296 (16)	−0.0081 (14)	0.0022 (13)	−0.0041 (14)
C22	0.0363 (17)	0.0292 (17)	0.0369 (18)	0.0087 (13)	0.0033 (14)	−0.0033 (14)
C23	0.0225 (15)	0.0291 (17)	0.0354 (17)	0.0079 (12)	−0.0017 (12)	−0.0053 (13)
C24	0.0298 (17)	0.055 (2)	0.0361 (18)	0.0029 (15)	−0.0064 (14)	−0.0064 (16)
C25	0.043 (2)	0.079 (3)	0.053 (2)	−0.012 (2)	−0.0079 (17)	−0.024 (2)
C26	0.043 (2)	0.062 (3)	0.078 (3)	−0.0200 (19)	−0.003 (2)	−0.027 (2)
C27	0.0333 (18)	0.039 (2)	0.051 (2)	−0.0049 (14)	0.0048 (15)	−0.0026 (16)
C28	0.0197 (14)	0.0343 (18)	0.0361 (17)	0.0043 (12)	−0.0005 (12)	−0.0057 (14)
C29	0.0306 (17)	0.053 (2)	0.0287 (17)	0.0026 (15)	0.0064 (13)	−0.0048 (15)

Geometric parameters (Å, º) top

I1—Cd1	2.7643 (8)	C4—C5	1.372 (4)
I2—Cd2	2.8609 (7)	C5—C6	1.498 (4)
I2—Cd2ⁱ	2.8937 (7)	C7—C8	1.375 (4)
I3—Cd2	2.7096 (8)	C7—C12	1.402 (4)
I4—Cd2	2.7284 (8)	C8—C9	1.397 (5)
Cd1—N1	2.283 (2)	C9—C10	1.375 (5)
Cd1—O2	2.562 (2)	C10—C11	1.384 (5)
Cd1—S2	2.6697 (10)	C11—C12	1.395 (4)
Cd1—S1	2.7007 (10)	C12—C13	1.486 (4)
Cd2—I2ⁱ	2.8937 (7)	C14—C15	1.499 (4)
S1—C22	1.819 (3)	C15—C16	1.395 (4)
S1—C21	1.832 (3)	C15—C20	1.396 (4)
S2—C13	1.828 (3)	C16—C17	1.383 (5)
S2—C14	1.830 (3)	C17—C18	1.376 (5)
O1—C7	1.383 (3)	C18—C19	1.382 (5)
O1—C6	1.434 (3)	C19—C20	1.394 (4)
O2—C28	1.394 (4)	C20—C21	1.507 (4)
O2—C29	1.432 (3)	C22—C23	1.505 (4)
N1—C1	1.340 (4)	C23—C24	1.387 (4)
N1—C5	1.351 (4)	C23—C28	1.390 (4)
C1—C2	1.378 (4)	C24—C25	1.372 (5)
C1—C29	1.501 (4)	C25—C26	1.363 (5)
C2—C3	1.372 (4)	C26—C27	1.389 (5)
C3—C4	1.379 (5)	C27—C28	1.368 (4)

Cd2—I2—Cd2ⁱ	87.28 (2)	C4—C5—C6	120.9 (3)
N1—Cd1—O2	68.67 (8)	O1—C6—C5	107.1 (2)
N1—Cd1—S2	108.61 (7)	C8—C7—O1	124.3 (3)
O2—Cd1—S2	90.03 (5)	C8—C7—C12	121.9 (3)
N1—Cd1—S1	136.33 (6)	O1—C7—C12	113.8 (3)
O2—Cd1—S1	71.82 (5)	C7—C8—C9	118.8 (3)
S2—Cd1—S1	89.05 (3)	C10—C9—C8	120.6 (3)
N1—Cd1—I1	122.75 (6)	C9—C10—C11	120.0 (3)
O2—Cd1—I1	155.06 (5)	C10—C11—C12	120.9 (3)
S2—Cd1—I1	104.83 (2)	C11—C12—C7	117.8 (3)
S1—Cd1—I1	88.24 (2)	C11—C12—C13	121.7 (3)
I3—Cd2—I4	114.705 (16)	C7—C12—C13	120.4 (3)
I3—Cd2—I2	110.028 (18)	C12—C13—S2	116.8 (2)
I4—Cd2—I2	114.726 (19)	C15—C14—S2	110.8 (2)
I3—Cd2—I2ⁱ	117.63 (2)	C16—C15—C20	118.9 (3)
I4—Cd2—I2ⁱ	105.210 (18)	C16—C15—C14	117.8 (3)
I2—Cd2—I2ⁱ	92.72 (2)	C20—C15—C14	123.4 (3)
C22—S1—C21	105.78 (15)	C17—C16—C15	121.6 (3)
C22—S1—Cd1	110.53 (10)	C18—C17—C16	119.3 (3)
C21—S1—Cd1	112.84 (11)	C17—C18—C19	119.9 (3)
C13—S2—C14	101.13 (15)	C18—C19—C20	121.4 (3)
C13—S2—Cd1	108.41 (11)	C19—C20—C15	118.9 (3)
C14—S2—Cd1	103.18 (11)	C19—C20—C21	117.7 (3)
C7—O1—C6	119.3 (2)	C15—C20—C21	123.4 (3)
C28—O2—C29	119.9 (2)	C20—C21—S1	117.7 (2)
C28—O2—Cd1	107.90 (16)	C23—C22—S1	115.4 (2)
C29—O2—Cd1	113.29 (16)	C24—C23—C28	117.8 (3)
C1—N1—C5	118.6 (2)	C24—C23—C22	121.4 (3)
C1—N1—Cd1	121.66 (19)	C28—C23—C22	120.7 (3)
C5—N1—Cd1	117.77 (19)	C25—C24—C23	121.1 (3)
N1—C1—C2	122.0 (3)	C26—C25—C24	120.1 (3)
N1—C1—C29	120.5 (2)	C25—C26—C27	120.3 (3)
C2—C1—C29	117.4 (3)	C28—C27—C26	119.2 (3)
C3—C2—C1	119.2 (3)	C27—C28—C23	121.5 (3)
C2—C3—C4	119.0 (3)	C27—C28—O2	123.5 (3)
C5—C4—C3	119.3 (3)	C23—C28—O2	114.9 (3)
N1—C5—C4	121.8 (3)	O2—C29—C1	112.8 (2)
N1—C5—C6	117.3 (3)

Symmetry code: (i) −x+2, −y, −z+1.

(4) top

Crystal data top

C₁₁₆H₁₀₆Cd₈I₁₆N₄O₈S₈	Z = 1
M_r = 4870.12	F(000) = 2254
Triclinic, P1	D_x = 2.212 Mg m⁻³
a = 11.3166 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.4404 (15) Å	Cell parameters from 7371 reflections
c = 24.586 (2) Å	θ = 2.2–23.3°
α = 86.655 (7)°	µ = 4.68 mm⁻¹
β = 89.396 (6)°	T = 171 K
γ = 78.371 (7)°	Needle, colourless
V = 3656.6 (6) Å³	0.28 × 0.07 × 0.04 mm

Data collection top

Bruker APEX-II CCD diffractometer	6056 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.084
Absorption correction: multi-scan SADABS	θ_max = 23.3°, θ_min = 2.6°
T_min = 0.354, T_max = 0.835	h = −12→11
23781 measured reflections	k = −14→14
8432 independent reflections	l = −27→27

Refinement top

Refinement on F²	1058 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.185	H-atom parameters constrained
wR(F²) = 0.430	w = 1/[σ²(F_o²) + (0.0399P)² + 1891.6968P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max < 0.001
8432 reflections	Δρ_max = 3.80 e Å⁻³
625 parameters	Δρ_min = −1.97 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
I1	0.8278 (5)	0.4588 (4)	0.01012 (19)	0.0463 (13)
I2	0.6656 (4)	0.3836 (3)	0.47947 (17)	0.0361 (11)
I3	0.1337 (5)	−0.0839 (4)	0.20741 (17)	0.0424 (13)
I4	−0.0914 (5)	0.0091 (4)	0.35744 (18)	0.0533 (15)
I5	−0.1638 (4)	−0.2639 (3)	0.29398 (17)	0.0387 (12)
I6	−0.2511 (4)	−0.0287 (3)	0.17434 (16)	0.0385 (12)
I7	−0.4491 (5)	−0.2967 (4)	0.16511 (18)	0.0465 (13)
I8	−0.5310 (5)	−0.0557 (4)	0.29864 (17)	0.0445 (13)
Cd1	1.0374 (5)	0.3747 (4)	0.06605 (18)	0.0347 (12)
Cd2	0.4349 (5)	0.3914 (4)	0.44006 (17)	0.0311 (12)
Cd3	−0.0758 (5)	−0.0802 (4)	0.26107 (19)	0.0390 (13)
Cd4	−0.3730 (5)	−0.1681 (4)	0.23137 (19)	0.0386 (13)
S1	1.0101 (14)	0.2126 (12)	0.1296 (6)	0.035 (4)
S2	1.1323 (12)	0.2687 (10)	−0.0232 (6)	0.040 (4)
S3	0.4220 (13)	0.2289 (11)	0.3863 (5)	0.029 (3)
S4	0.3772 (12)	0.3336 (9)	0.5417 (6)	0.029 (3)
O1	1.254 (4)	0.308 (3)	0.0877 (17)	0.041 (5)
O2	0.869 (4)	0.443 (3)	0.1553 (17)	0.044 (8)
O3	0.204 (4)	0.420 (3)	0.4350 (16)	0.035 (5)
O4	0.573 (4)	0.408 (3)	0.3429 (15)	0.034 (7)
N1	1.104 (4)	0.470 (3)	0.1298 (15)	0.039 (7)
C1	1.025 (3)	0.553 (3)	0.1500 (17)	0.041 (7)
C2	1.071 (4)	0.629 (3)	0.1731 (17)	0.042 (7)
H2A	1.0175	0.6861	0.1869	0.050*
C3	1.195 (4)	0.623 (3)	0.1759 (17)	0.042 (7)
H3A	1.2262	0.6751	0.1917	0.051*
C4	1.273 (3)	0.540 (3)	0.1557 (18)	0.043 (7)
H4A	1.3579	0.5355	0.1576	0.051*
C5	1.228 (3)	0.464 (3)	0.1326 (17)	0.043 (7)
C6	1.311 (7)	0.379 (6)	0.117 (3)	0.054 (14)
H6A	1.3519	0.3424	0.1501	0.064*
H6B	1.3728	0.4017	0.0936	0.064*
C7	1.306 (4)	0.213 (2)	0.0890 (16)	0.043 (6)
C8	1.337 (4)	0.152 (3)	0.1363 (12)	0.044 (7)
H8A	1.3258	0.1803	0.1708	0.053*
C9	1.385 (4)	0.048 (3)	0.1330 (13)	0.044 (7)
H9A	1.4058	0.0066	0.1653	0.053*
C10	1.401 (4)	0.006 (2)	0.0825 (16)	0.043 (7)
H10A	1.4336	−0.0641	0.0802	0.052*
C11	1.370 (4)	0.068 (3)	0.0352 (12)	0.042 (7)
H11A	1.3814	0.0390	0.0007	0.050*
C12	1.323 (4)	0.171 (3)	0.0385 (13)	0.042 (6)
C13	1.2930 (13)	0.235 (5)	−0.013 (2)	0.044 (7)
H13A	1.3309	0.1968	−0.0443	0.053*
H13B	1.3262	0.2974	−0.0117	0.053*
C14	1.100 (4)	0.1431 (14)	−0.024 (3)	0.047 (8)
H14A	1.1213	0.1140	−0.0602	0.056*
H14B	1.1449	0.0971	0.0045	0.056*
C15	0.956 (3)	0.160 (4)	−0.0141 (18)	0.047 (7)
C16	0.884 (4)	0.188 (4)	−0.0600 (14)	0.049 (7)
H16A	0.9191	0.2022	−0.0941	0.058*
C17	0.760 (4)	0.194 (4)	−0.0561 (15)	0.050 (7)
H17A	0.7105	0.2128	−0.0875	0.060*
C18	0.709 (3)	0.173 (4)	−0.0063 (18)	0.050 (7)
H18A	0.6239	0.1773	−0.0036	0.059*
C19	0.781 (4)	0.146 (4)	0.0397 (14)	0.047 (7)
H19A	0.7458	0.1311	0.0737	0.056*
C20	0.905 (4)	0.139 (4)	0.0358 (15)	0.046 (7)
C21	0.995 (6)	0.111 (2)	0.0871 (15)	0.041 (7)
H21A	1.0756	0.0813	0.0733	0.049*
H21B	0.9671	0.0578	0.1104	0.049*
C22	0.8588 (19)	0.246 (5)	0.1555 (19)	0.035 (7)
H22A	0.8045	0.2898	0.1287	0.041*
H22B	0.8258	0.1841	0.1654	0.041*
C23	0.877 (4)	0.305 (3)	0.2080 (11)	0.033 (6)
C24	0.876 (4)	0.254 (2)	0.2588 (14)	0.034 (6)
H24A	0.8820	0.1821	0.2613	0.040*
C25	0.867 (4)	0.307 (3)	0.3058 (11)	0.033 (6)
H25A	0.8666	0.2723	0.3405	0.040*
C26	0.858 (4)	0.412 (3)	0.3021 (11)	0.033 (6)
H26A	0.8521	0.4488	0.3343	0.039*
C27	0.859 (4)	0.463 (2)	0.2514 (14)	0.033 (6)
H27A	0.8529	0.5350	0.2489	0.040*
C28	0.868 (4)	0.410 (3)	0.2043 (11)	0.032 (6)
C29	0.891 (6)	0.561 (5)	0.143 (2)	0.039 (8)
H29A	0.8657	0.5860	0.1052	0.046*
H29B	0.8448	0.6074	0.1687	0.046*
N2	0.347 (3)	0.521 (2)	0.3790 (13)	0.028 (6)
C30	0.429 (3)	0.565 (3)	0.3479 (15)	0.034 (7)
C31	0.389 (3)	0.658 (3)	0.3191 (15)	0.036 (7)
H31A	0.4447	0.6882	0.2979	0.043*
C32	0.269 (3)	0.707 (2)	0.3215 (15)	0.037 (6)
H32A	0.2419	0.7700	0.3018	0.044*
C33	0.188 (3)	0.662 (3)	0.3526 (16)	0.035 (7)
H33A	0.1053	0.6956	0.3542	0.042*
C34	0.227 (3)	0.570 (3)	0.3814 (14)	0.033 (7)
C35	0.150 (6)	0.509 (6)	0.409 (3)	0.06 (2)
H35A	0.1003	0.5509	0.4357	0.077*
H35B	0.0937	0.4928	0.3815	0.077*
C36	0.140 (3)	0.354 (2)	0.4582 (12)	0.037 (6)
C37	0.076 (3)	0.311 (3)	0.4217 (10)	0.037 (6)
H37A	0.0726	0.3331	0.3842	0.045*
C38	0.015 (4)	0.235 (3)	0.4400 (13)	0.037 (6)
H38A	−0.0292	0.2054	0.4150	0.044*
C39	0.019 (4)	0.203 (3)	0.4948 (14)	0.037 (6)
H39A	−0.0220	0.1507	0.5072	0.044*
C40	0.084 (4)	0.246 (3)	0.5313 (10)	0.037 (6)
H40A	0.0872	0.2237	0.5687	0.045*
C41	0.145 (3)	0.322 (3)	0.5130 (11)	0.037 (6)
C42	0.2159 (12)	0.368 (3)	0.5489 (14)	0.034 (6)
H42A	0.1950	0.3508	0.5870	0.040*
H42B	0.1917	0.4432	0.5429	0.040*
C43	0.402 (5)	0.1969 (9)	0.5463 (18)	0.031 (7)
H43A	0.3902	0.1721	0.5843	0.038*
H43B	0.3430	0.1737	0.5229	0.038*
C44	0.525 (3)	0.157 (3)	0.5284 (12)	0.031 (6)
C45	0.619 (3)	0.145 (3)	0.5654 (11)	0.034 (6)
H45A	0.6064	0.1752	0.5996	0.040*
C46	0.733 (3)	0.091 (3)	0.5523 (12)	0.034 (6)
H46A	0.7975	0.0832	0.5776	0.041*
C47	0.752 (3)	0.047 (3)	0.5022 (14)	0.033 (6)
H47A	0.8297	0.0099	0.4933	0.039*
C48	0.658 (3)	0.058 (3)	0.4652 (11)	0.029 (6)
C49	0.544 (3)	0.113 (3)	0.4783 (11)	0.029 (6)
C50	0.438 (5)	0.125 (2)	0.4368 (13)	0.026 (6)
H50A	0.3617	0.1316	0.4577	0.032*
H50B	0.4477	0.0607	0.4176	0.032*
C51	0.564 (2)	0.207 (5)	0.3507 (15)	0.027 (6)
H51A	0.6260	0.2253	0.3739	0.033*
H51B	0.5881	0.1331	0.3448	0.033*
C52	0.561 (4)	0.266 (3)	0.2963 (10)	0.031 (6)
C53	0.557 (4)	0.212 (2)	0.2498 (13)	0.032 (6)
H53A	0.5529	0.1424	0.2529	0.038*
C54	0.558 (4)	0.262 (3)	0.1986 (11)	0.032 (6)
H54A	0.5549	0.2258	0.1667	0.039*
C55	0.563 (4)	0.365 (3)	0.1940 (10)	0.031 (6)
H55A	0.5642	0.3984	0.1590	0.038*
C56	0.568 (4)	0.418 (2)	0.2405 (13)	0.031 (6)
H56A	0.5714	0.4876	0.2374	0.037*
C57	0.567 (4)	0.368 (3)	0.2917 (11)	0.031 (6)
C58	0.547 (6)	0.524 (5)	0.343 (2)	0.033 (7)
H58A	0.5907	0.5436	0.3743	0.039*
H58B	0.5783	0.5516	0.3094	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.051 (3)	0.034 (3)	0.053 (3)	−0.006 (3)	−0.007 (2)	−0.002 (2)
I2	0.035 (3)	0.027 (3)	0.046 (2)	−0.008 (2)	−0.0022 (19)	0.0013 (19)
I3	0.050 (3)	0.037 (3)	0.039 (2)	−0.007 (3)	0.012 (2)	−0.003 (2)
I4	0.092 (4)	0.040 (3)	0.036 (2)	−0.028 (3)	0.018 (2)	−0.015 (2)
I5	0.052 (3)	0.024 (3)	0.040 (2)	−0.007 (2)	0.002 (2)	−0.0040 (18)
I6	0.050 (3)	0.032 (3)	0.035 (2)	−0.013 (2)	0.0119 (19)	0.0013 (18)
I7	0.065 (4)	0.033 (3)	0.046 (3)	−0.016 (3)	0.007 (2)	−0.010 (2)
I8	0.066 (4)	0.032 (3)	0.035 (2)	−0.010 (3)	0.019 (2)	−0.0079 (19)
Cd1	0.044 (3)	0.025 (3)	0.037 (2)	−0.010 (2)	0.002 (2)	−0.0050 (19)
Cd2	0.034 (3)	0.026 (3)	0.033 (2)	−0.009 (2)	0.0056 (19)	0.0031 (19)
Cd3	0.051 (4)	0.031 (3)	0.036 (2)	−0.010 (3)	0.010 (2)	−0.008 (2)
Cd4	0.050 (4)	0.031 (3)	0.039 (3)	−0.015 (3)	0.011 (2)	−0.005 (2)
S1	0.037 (9)	0.029 (7)	0.038 (6)	−0.005 (6)	0.007 (5)	−0.001 (5)
S2	0.052 (8)	0.035 (8)	0.038 (7)	−0.017 (6)	0.013 (5)	−0.002 (5)
S3	0.030 (6)	0.025 (6)	0.033 (5)	−0.008 (5)	0.004 (4)	0.001 (4)
S4	0.035 (6)	0.028 (6)	0.027 (5)	−0.011 (5)	0.007 (4)	−0.002 (4)
O1	0.046 (9)	0.033 (9)	0.046 (11)	−0.010 (6)	0.006 (7)	−0.010 (7)
O2	0.06 (2)	0.038 (12)	0.037 (9)	−0.014 (11)	0.002 (9)	−0.004 (8)
O3	0.035 (8)	0.027 (9)	0.043 (10)	−0.008 (6)	0.004 (6)	0.002 (7)
O4	0.044 (18)	0.032 (10)	0.029 (9)	−0.011 (9)	−0.004 (9)	−0.001 (7)
N1	0.049 (10)	0.030 (10)	0.041 (14)	−0.010 (7)	0.004 (8)	−0.007 (10)
C1	0.050 (11)	0.031 (10)	0.044 (15)	−0.009 (8)	0.005 (8)	−0.008 (10)
C2	0.050 (12)	0.032 (10)	0.045 (14)	−0.009 (8)	0.006 (9)	−0.010 (10)
C3	0.050 (12)	0.032 (11)	0.046 (14)	−0.009 (9)	0.005 (10)	−0.010 (10)
C4	0.049 (11)	0.032 (11)	0.047 (15)	−0.010 (8)	0.004 (9)	−0.011 (10)
C5	0.049 (10)	0.033 (11)	0.050 (16)	−0.009 (8)	0.002 (8)	−0.012 (11)
C6	0.048 (11)	0.040 (13)	0.08 (3)	−0.008 (8)	0.000 (10)	−0.025 (17)
C7	0.049 (12)	0.033 (9)	0.045 (11)	−0.007 (7)	0.010 (8)	−0.009 (7)
C8	0.051 (14)	0.034 (10)	0.046 (11)	−0.005 (9)	0.011 (9)	−0.007 (8)
C9	0.052 (15)	0.033 (10)	0.046 (12)	−0.005 (9)	0.013 (10)	−0.006 (8)
C10	0.051 (15)	0.033 (10)	0.046 (12)	−0.007 (9)	0.014 (10)	−0.006 (8)
C11	0.050 (14)	0.032 (10)	0.045 (11)	−0.008 (8)	0.014 (9)	−0.007 (8)
C12	0.050 (13)	0.032 (9)	0.045 (10)	−0.009 (8)	0.011 (8)	−0.008 (7)
C13	0.054 (10)	0.034 (13)	0.047 (12)	−0.013 (8)	0.009 (7)	−0.007 (9)
C14	0.056 (13)	0.034 (11)	0.054 (18)	−0.017 (9)	0.006 (10)	−0.003 (10)
C15	0.055 (12)	0.036 (14)	0.054 (11)	−0.018 (10)	0.005 (9)	−0.001 (9)
C16	0.057 (13)	0.036 (15)	0.057 (12)	−0.019 (11)	0.002 (9)	0.000 (10)
C17	0.056 (13)	0.037 (16)	0.059 (12)	−0.018 (11)	0.001 (10)	0.000 (11)
C18	0.055 (13)	0.038 (16)	0.059 (12)	−0.017 (11)	0.000 (10)	0.001 (11)
C19	0.053 (13)	0.034 (16)	0.057 (12)	−0.018 (10)	0.002 (9)	0.001 (11)
C20	0.053 (12)	0.034 (15)	0.053 (11)	−0.017 (10)	0.004 (9)	−0.001 (9)
C21	0.046 (15)	0.032 (11)	0.048 (11)	−0.013 (10)	0.010 (10)	−0.005 (9)
C22	0.035 (12)	0.032 (13)	0.037 (10)	−0.007 (9)	0.003 (8)	−0.003 (9)
C23	0.027 (12)	0.034 (9)	0.037 (8)	−0.004 (8)	0.004 (7)	−0.005 (7)
C24	0.029 (13)	0.034 (10)	0.037 (9)	−0.002 (9)	0.005 (8)	−0.005 (7)
C25	0.027 (12)	0.034 (10)	0.036 (9)	−0.002 (8)	0.005 (8)	−0.004 (7)
C26	0.028 (10)	0.034 (9)	0.035 (8)	−0.002 (8)	0.005 (7)	−0.005 (7)
C27	0.028 (12)	0.034 (10)	0.037 (8)	−0.003 (8)	0.004 (8)	−0.004 (7)
C28	0.026 (13)	0.034 (9)	0.037 (8)	−0.003 (8)	0.004 (7)	−0.005 (7)
C29	0.050 (12)	0.035 (11)	0.032 (18)	−0.011 (8)	0.006 (9)	−0.007 (10)
N2	0.036 (8)	0.023 (8)	0.027 (9)	−0.009 (5)	0.000 (6)	−0.004 (6)
C30	0.040 (9)	0.031 (9)	0.033 (12)	−0.011 (7)	0.003 (8)	0.001 (9)
C31	0.042 (10)	0.032 (9)	0.034 (12)	−0.010 (8)	0.003 (9)	0.002 (9)
C32	0.042 (11)	0.032 (9)	0.036 (12)	−0.009 (8)	0.002 (9)	0.002 (9)
C33	0.040 (10)	0.030 (9)	0.035 (13)	−0.006 (7)	0.001 (8)	0.003 (9)
C34	0.038 (9)	0.029 (9)	0.033 (14)	−0.007 (6)	0.001 (7)	0.002 (9)
C35	0.039 (10)	0.047 (17)	0.10 (4)	−0.004 (7)	0.008 (9)	0.03 (2)
C36	0.039 (10)	0.029 (11)	0.045 (9)	−0.011 (9)	0.003 (7)	0.002 (7)
C37	0.038 (11)	0.029 (12)	0.046 (10)	−0.011 (10)	0.002 (8)	0.002 (8)
C38	0.038 (12)	0.027 (12)	0.047 (11)	−0.009 (10)	0.003 (9)	0.001 (9)
C39	0.038 (12)	0.026 (12)	0.047 (11)	−0.010 (10)	0.004 (9)	0.002 (9)
C40	0.038 (11)	0.027 (11)	0.047 (10)	−0.010 (10)	0.003 (8)	0.001 (8)
C41	0.040 (10)	0.028 (11)	0.046 (9)	−0.011 (9)	0.003 (7)	0.002 (7)
C42	0.035 (7)	0.029 (10)	0.038 (9)	−0.010 (6)	0.008 (6)	0.000 (7)
C43	0.036 (10)	0.028 (9)	0.032 (13)	−0.011 (6)	0.006 (8)	0.001 (7)
C44	0.035 (8)	0.029 (9)	0.030 (8)	−0.011 (6)	0.004 (6)	0.001 (6)
C45	0.037 (9)	0.033 (11)	0.032 (8)	−0.011 (7)	0.003 (7)	0.001 (8)
C46	0.037 (9)	0.034 (11)	0.032 (9)	−0.011 (8)	0.003 (7)	0.003 (8)
C47	0.034 (9)	0.032 (11)	0.033 (9)	−0.009 (7)	0.002 (7)	0.003 (8)
C48	0.030 (8)	0.028 (9)	0.030 (8)	−0.008 (6)	0.003 (6)	0.002 (6)
C49	0.030 (7)	0.028 (8)	0.030 (7)	−0.009 (5)	0.003 (5)	0.001 (5)
C50	0.026 (9)	0.025 (8)	0.027 (8)	−0.005 (6)	0.005 (6)	−0.001 (6)
C51	0.026 (9)	0.030 (9)	0.028 (8)	−0.009 (7)	0.000 (6)	−0.001 (6)
C52	0.036 (15)	0.033 (10)	0.029 (8)	−0.015 (9)	−0.002 (7)	−0.001 (7)
C53	0.035 (16)	0.034 (11)	0.029 (8)	−0.017 (10)	−0.001 (8)	−0.002 (7)
C54	0.035 (16)	0.035 (11)	0.031 (9)	−0.016 (11)	−0.001 (8)	−0.001 (8)
C55	0.032 (16)	0.034 (11)	0.031 (9)	−0.015 (11)	0.000 (8)	−0.001 (8)
C56	0.032 (16)	0.033 (11)	0.030 (9)	−0.015 (10)	−0.001 (8)	0.000 (7)
C57	0.033 (16)	0.033 (10)	0.029 (8)	−0.014 (9)	0.000 (8)	−0.001 (7)
C58	0.040 (10)	0.032 (10)	0.027 (16)	−0.011 (8)	0.001 (8)	−0.001 (9)

Geometric parameters (Å, º) top

I1—Cd1	2.757 (7)	C11—C12	1.3900
I2—Cd2	2.774 (7)	C12—C13	1.49 (6)
I3—Cd3	2.694 (7)	C14—C15	1.61 (6)
I4—Cd3	2.706 (6)	C15—C16	1.3900
I5—Cd4	2.872 (7)	C15—C20	1.3900
I5—Cd3	2.913 (7)	C16—C17	1.3900
I6—Cd4	2.841 (6)	C17—C18	1.3900
I6—Cd3	2.885 (7)	C18—C19	1.3900
I7—Cd4	2.709 (7)	C19—C20	1.3900
I8—Cd4	2.712 (7)	C20—C21	1.61 (5)
Cd1—N1	2.30 (3)	C22—C23	1.59 (6)
Cd1—O1	2.49 (5)	C23—C24	1.3900
Cd1—S1	2.673 (16)	C23—C28	1.3900
Cd1—S2	2.775 (16)	C24—C25	1.3900
Cd2—N2	2.30 (3)	C25—C26	1.3900
Cd2—O3	2.57 (4)	C26—C27	1.3900
Cd2—S3	2.647 (16)	C27—C28	1.3900
Cd2—S4	2.687 (14)	N2—C30	1.3900
S1—C22	1.8000 (11)	N2—C34	1.3900
S1—C21	1.8000 (11)	C30—C58	1.35 (7)
S2—C14	1.8000 (8)	C30—C31	1.3900
S2—C13	1.8000 (8)	C31—C32	1.3900
S3—C51	1.8000 (11)	C32—C33	1.3900
S3—C50	1.8000 (11)	C33—C34	1.3900
S4—C43	1.8000 (8)	C34—C35	1.451 (10)
S4—C42	1.8000 (11)	C36—C37	1.3900
O1—C7	1.29 (5)	C36—C41	1.3900
O1—C6	1.48 (8)	C37—C38	1.3900
O2—C28	1.26 (5)	C38—C39	1.3900
O2—C29	1.66 (8)	C39—C40	1.3900
O3—C36	1.35 (5)	C40—C41	1.3900
O3—C35	1.35 (8)	C41—C42	1.4500 (11)
O4—C57	1.40 (4)	C43—C44	1.47 (6)
O4—C58	1.53 (7)	C44—C45	1.3900
N1—C1	1.3900	C44—C49	1.3900
N1—C5	1.3900	C45—C46	1.3900
C1—C2	1.3900	C46—C47	1.3900
C1—C29	1.51 (7)	C47—C48	1.3900
C2—C3	1.3900	C48—C49	1.3900
C3—C4	1.3900	C49—C50	1.56 (6)
C4—C5	1.3900	C51—C52	1.51 (5)
C5—C6	1.39 (8)	C52—C53	1.3900
C7—C8	1.3900	C52—C57	1.3900
C7—C12	1.3900	C53—C54	1.3900
C8—C9	1.3900	C54—C55	1.3900
C9—C10	1.3900	C55—C56	1.3900
C10—C11	1.3900	C56—C57	1.3900

Cd4—I5—Cd3	84.02 (19)	C11—C12—C13	119 (4)
Cd4—I6—Cd3	85.09 (18)	C7—C12—C13	121 (4)
N1—Cd1—O1	69.3 (14)	C12—C13—S2	111 (3)
N1—Cd1—S1	99.9 (10)	C15—C14—S2	104 (3)
O1—Cd1—S1	82.3 (11)	C16—C15—C20	120.0
N1—Cd1—I1	117.9 (11)	C16—C15—C14	116 (4)
O1—Cd1—I1	161.8 (10)	C20—C15—C14	124 (4)
S1—Cd1—I1	111.2 (4)	C15—C16—C17	120.0
N1—Cd1—S2	137.3 (11)	C16—C17—C18	120.0
O1—Cd1—S2	74.3 (10)	C19—C18—C17	120.0
S1—Cd1—S2	96.7 (4)	C18—C19—C20	120.0
I1—Cd1—S2	91.5 (3)	C19—C20—C15	120.0
N2—Cd2—O3	65.5 (13)	C19—C20—C21	123 (3)
N2—Cd2—S3	101.6 (9)	C15—C20—C21	117 (3)
O3—Cd2—S3	82.8 (10)	C20—C21—S1	118 (3)
N2—Cd2—S4	133.1 (9)	C23—C22—S1	102 (3)
O3—Cd2—S4	77.9 (9)	C24—C23—C28	120.0
S3—Cd2—S4	101.8 (4)	C24—C23—C22	118 (3)
N2—Cd2—I2	120.3 (9)	C28—C23—C22	121 (3)
O3—Cd2—I2	161.0 (9)	C25—C24—C23	120.0
S3—Cd2—I2	111.8 (4)	C24—C25—C26	120.0
S4—Cd2—I2	86.9 (3)	C25—C26—C27	120.0
I3—Cd3—I4	114.9 (2)	C28—C27—C26	120.0
I3—Cd3—I6	102.2 (2)	O2—C28—C27	129 (3)
I4—Cd3—I6	125.0 (3)	O2—C28—C23	111 (3)
I3—Cd3—I5	122.8 (2)	C27—C28—C23	120.0
I4—Cd3—I5	99.75 (19)	C1—C29—O2	105 (5)
I6—Cd3—I5	91.79 (19)	C30—N2—C34	120.0
I7—Cd4—I8	120.2 (3)	C30—N2—Cd2	114.8 (18)
I7—Cd4—I6	112.9 (2)	C34—N2—Cd2	123.4 (17)
I8—Cd4—I6	105.8 (2)	C58—C30—C31	116 (3)
I7—Cd4—I5	112.8 (2)	C58—C30—N2	124 (3)
I8—Cd4—I5	108.1 (2)	C31—C30—N2	120.0
I6—Cd4—I5	93.6 (2)	C30—C31—C32	120.0
C22—S1—C21	100 (3)	C33—C32—C31	120.0
C22—S1—Cd1	105 (2)	C32—C33—C34	120.0
C21—S1—Cd1	108.9 (15)	C33—C34—N2	120.0
C14—S2—C13	99 (3)	C33—C34—C35	125 (4)
C14—S2—Cd1	114 (2)	N2—C34—C35	114 (4)
C13—S2—Cd1	107 (2)	O3—C35—C34	117 (5)
C51—S3—C50	104 (3)	O3—C36—C37	115 (3)
C51—S3—Cd2	102 (2)	O3—C36—C41	125 (3)
C50—S3—Cd2	105.9 (15)	C37—C36—C41	120.0
C43—S4—C42	102 (2)	C36—C37—C38	120.0
C43—S4—Cd2	107.6 (17)	C39—C38—C37	120.0
C42—S4—Cd2	108.2 (14)	C40—C39—C38	120.0
C7—O1—C6	119 (5)	C39—C40—C41	120.0
C7—O1—Cd1	125 (4)	C40—C41—C36	120.0
C6—O1—Cd1	114 (4)	C40—C41—C42	123 (3)
C28—O2—C29	118 (4)	C36—C41—C42	117 (3)
C36—O3—C35	122 (4)	C41—C42—S4	116 (2)
C36—O3—Cd2	123 (3)	C44—C43—S4	108 (3)
C35—O3—Cd2	115 (3)	C45—C44—C49	120.0
C57—O4—C58	116 (4)	C45—C44—C43	119.3 (9)
C1—N1—C5	120.0	C49—C44—C43	119.6 (9)
C1—N1—Cd1	120 (2)	C46—C45—C44	120.0
C5—N1—Cd1	116 (2)	C45—C46—C47	120.0
N1—C1—C2	120.0	C48—C47—C46	120.0
N1—C1—C29	118 (4)	C49—C48—C47	120.0
C2—C1—C29	122 (4)	C48—C49—C44	120.0
C3—C2—C1	120.0	C48—C49—C50	120 (2)
C2—C3—C4	120.0	C44—C49—C50	120 (2)
C5—C4—C3	120.0	C49—C50—S3	117 (3)
C4—C5—N1	120.0	C52—C51—S3	114 (3)
C4—C5—C6	117 (4)	C53—C52—C57	120.0
N1—C5—C6	123 (4)	C53—C52—C51	118 (3)
C5—C6—O1	112 (6)	C57—C52—C51	122 (3)
O1—C7—C8	125 (3)	C52—C53—C54	120.0
O1—C7—C12	115 (3)	C55—C54—C53	120.0
C8—C7—C12	120.0	C56—C55—C54	120.0
C9—C8—C7	120.0	C55—C56—C57	120.0
C10—C9—C8	120.0	C56—C57—C52	120.0
C9—C10—C11	120.0	C56—C57—O4	128 (3)
C12—C11—C10	120.0	C52—C57—O4	112 (3)
C11—C12—C7	120.0	C30—C58—O4	113 (5)

(5) top

Crystal data top

C₂₉H₂₇CdCuI₃NO₂S₂	Z = 2
M_r = 1042.28	F(000) = 984
Triclinic, P1	D_x = 2.060 Mg m⁻³
a = 8.9645 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.4098 (3) Å	Cell parameters from 9946 reflections
c = 14.8826 (3) Å	θ = 2.4–28.2°
α = 65.853 (1)°	µ = 4.17 mm⁻¹
β = 73.386 (1)°	T = 173 K
γ = 81.546 (1)°	Block, yellow
V = 1680.04 (6) Å³	0.16 × 0.13 × 0.08 mm

Data collection top

Bruker APEX-II CCD diffractometer	6602 independent reflections
Radiation source: fine-focus sealed tube	6072 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 26.0°, θ_min = 1.6°
Absorption correction: multi-scan SADABS	h = −10→11
T_min = 0.555, T_max = 0.731	k = −17→17
28556 measured reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.039	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0142P)² + 0.8501P] where P = (F_o² + 2F_c²)/3
6602 reflections	(Δ/σ)_max = 0.002
352 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
I1	0.334817 (17)	0.570963 (11)	0.417466 (11)	0.03154 (4)
I2	0.78474 (2)	0.720549 (13)	0.270645 (12)	0.04207 (5)
I3	0.50493 (2)	0.746988 (11)	0.573707 (12)	0.03658 (5)
Cd1	0.58973 (2)	0.633019 (12)	0.459040 (12)	0.03091 (5)
Cu1	0.71141 (3)	0.782628 (19)	0.805463 (19)	0.02697 (6)
S6	0.54119 (7)	0.90661 (4)	0.73933 (4)	0.03141 (12)
S7	0.76104 (6)	0.77521 (4)	0.94931 (4)	0.02880 (12)
O1	0.60261 (16)	0.59508 (11)	0.92203 (10)	0.0263 (3)
O2	0.91204 (19)	0.87876 (11)	0.63583 (12)	0.0358 (4)
N1	0.8249 (2)	0.68636 (12)	0.73864 (12)	0.0231 (4)
C1	0.7622 (3)	0.59806 (16)	0.75973 (15)	0.0254 (5)
C2	0.8381 (3)	0.52894 (17)	0.71897 (17)	0.0338 (5)
H2A	0.7911	0.4669	0.7364	0.041*
C3	0.9835 (3)	0.55053 (18)	0.65239 (18)	0.0383 (6)
H3A	1.0378	0.5037	0.6232	0.046*
C4	1.0484 (3)	0.64076 (17)	0.62899 (17)	0.0341 (5)
H4A	1.1478	0.6576	0.5828	0.041*
C5	0.9670 (2)	0.70685 (16)	0.67370 (15)	0.0263 (5)
C6	1.0349 (3)	0.80467 (16)	0.65316 (17)	0.0303 (5)
H6A	1.0702	0.7998	0.7123	0.036*
H6B	1.1246	0.8219	0.5927	0.036*
C7	0.9287 (3)	0.97381 (16)	0.63162 (16)	0.0323 (5)
C8	1.0639 (3)	1.00707 (18)	0.63336 (18)	0.0384 (6)
H8A	1.1545	0.9637	0.6379	0.046*
C9	1.0647 (3)	1.10572 (19)	0.62833 (19)	0.0452 (7)
H9A	1.1568	1.1301	0.6294	0.054*
C10	0.9334 (4)	1.16794 (19)	0.62183 (19)	0.0463 (7)
H10A	0.9347	1.2349	0.6189	0.056*
C11	0.7987 (3)	1.13335 (17)	0.61950 (18)	0.0409 (6)
H11A	0.7085	1.1772	0.6149	0.049*
C12	0.7932 (3)	1.03560 (16)	0.62383 (16)	0.0333 (5)
C13	0.6516 (3)	0.99696 (17)	0.61825 (17)	0.0363 (5)
H13A	0.6839	0.9636	0.5689	0.044*
H13B	0.5817	1.0558	0.5916	0.044*
C14	0.4960 (3)	0.98708 (18)	0.81265 (18)	0.0375 (6)
H14A	0.5939	1.0101	0.8140	0.045*
H14B	0.4338	1.0480	0.7800	0.045*
C15	0.4060 (3)	0.92836 (18)	0.91948 (19)	0.0362 (6)
C16	0.2447 (3)	0.9248 (2)	0.9386 (2)	0.0501 (7)
H16A	0.1959	0.9578	0.8841	0.060*
C17	0.1549 (3)	0.8742 (3)	1.0355 (3)	0.0612 (8)
H17A	0.0454	0.8718	1.0471	0.073*
C18	0.2238 (4)	0.8277 (3)	1.1145 (2)	0.0601 (8)
H18A	0.1621	0.7935	1.1813	0.072*
C19	0.3835 (3)	0.8302 (2)	1.0976 (2)	0.0454 (7)
H19A	0.4301	0.7980	1.1532	0.055*
C20	0.4772 (3)	0.87956 (18)	0.99993 (18)	0.0342 (5)
C21	0.6502 (3)	0.87679 (18)	0.98713 (18)	0.0352 (5)
H21A	0.6691	0.8692	1.0522	0.042*
H21B	0.6912	0.9431	0.9353	0.042*
C22	0.6583 (3)	0.66568 (17)	1.05339 (16)	0.0331 (5)
H22A	0.6599	0.6671	1.1190	0.040*
H22B	0.5481	0.6710	1.0507	0.040*
C23	0.7287 (3)	0.56666 (16)	1.04878 (16)	0.0294 (5)
C24	0.8198 (3)	0.50510 (19)	1.11388 (18)	0.0409 (6)
H24A	0.8419	0.5275	1.1604	0.049*
C25	0.8787 (3)	0.4116 (2)	1.1117 (2)	0.0476 (7)
H25A	0.9418	0.3706	1.1562	0.057*
C26	0.8468 (3)	0.37772 (18)	1.0458 (2)	0.0408 (6)
H26A	0.8868	0.3131	1.0453	0.049*
C27	0.7563 (3)	0.43737 (17)	0.97987 (17)	0.0315 (5)
H27A	0.7338	0.4140	0.9342	0.038*
C28	0.6991 (2)	0.53130 (16)	0.98137 (15)	0.0262 (5)
C29	0.6034 (3)	0.57983 (17)	0.83261 (16)	0.0292 (5)
H29A	0.5257	0.6270	0.7990	0.035*
H29B	0.5739	0.5094	0.8520	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.03521 (8)	0.02948 (8)	0.03594 (9)	0.00290 (6)	−0.01611 (7)	−0.01512 (6)
I2	0.05104 (10)	0.04403 (10)	0.03065 (9)	−0.01449 (8)	−0.00463 (7)	−0.01343 (7)
I3	0.05155 (10)	0.03202 (8)	0.03505 (9)	0.00990 (7)	−0.02211 (7)	−0.01797 (7)
Cd1	0.03665 (10)	0.02822 (9)	0.03065 (9)	−0.00121 (7)	−0.00924 (7)	−0.01354 (7)
Cu1	0.02960 (14)	0.02192 (13)	0.02473 (14)	0.00067 (11)	−0.00116 (11)	−0.00870 (11)
S6	0.0346 (3)	0.0276 (3)	0.0310 (3)	0.0044 (2)	−0.0093 (2)	−0.0114 (2)
S7	0.0294 (3)	0.0275 (3)	0.0285 (3)	−0.0021 (2)	−0.0052 (2)	−0.0109 (2)
O1	0.0236 (7)	0.0307 (8)	0.0233 (8)	−0.0010 (6)	−0.0081 (6)	−0.0077 (6)
O2	0.0379 (9)	0.0218 (8)	0.0465 (10)	−0.0018 (7)	−0.0086 (8)	−0.0130 (7)
N1	0.0259 (9)	0.0220 (8)	0.0197 (9)	0.0000 (7)	−0.0062 (7)	−0.0064 (7)
C1	0.0317 (12)	0.0262 (11)	0.0208 (10)	−0.0017 (9)	−0.0125 (9)	−0.0073 (9)
C2	0.0481 (14)	0.0286 (11)	0.0310 (12)	−0.0054 (10)	−0.0129 (11)	−0.0145 (10)
C3	0.0498 (15)	0.0322 (12)	0.0354 (13)	0.0040 (11)	−0.0049 (11)	−0.0212 (11)
C4	0.0370 (13)	0.0329 (12)	0.0279 (12)	0.0008 (10)	0.0012 (10)	−0.0144 (10)
C5	0.0298 (12)	0.0249 (11)	0.0216 (11)	0.0004 (9)	−0.0054 (9)	−0.0077 (9)
C6	0.0311 (12)	0.0247 (11)	0.0294 (12)	−0.0026 (9)	0.0010 (9)	−0.0099 (9)
C7	0.0462 (14)	0.0228 (11)	0.0219 (11)	−0.0077 (10)	−0.0006 (10)	−0.0058 (9)
C8	0.0441 (14)	0.0307 (12)	0.0364 (13)	−0.0083 (11)	−0.0011 (11)	−0.0129 (10)
C9	0.0602 (17)	0.0375 (14)	0.0399 (15)	−0.0191 (13)	−0.0054 (13)	−0.0159 (12)
C10	0.077 (2)	0.0252 (12)	0.0380 (14)	−0.0065 (13)	−0.0141 (13)	−0.0118 (11)
C11	0.0656 (18)	0.0223 (11)	0.0321 (13)	0.0038 (11)	−0.0171 (12)	−0.0064 (10)
C12	0.0497 (15)	0.0237 (11)	0.0200 (11)	−0.0025 (10)	−0.0075 (10)	−0.0024 (9)
C13	0.0484 (15)	0.0284 (12)	0.0274 (12)	0.0043 (11)	−0.0140 (11)	−0.0049 (10)
C14	0.0409 (14)	0.0304 (12)	0.0423 (14)	0.0090 (11)	−0.0092 (11)	−0.0195 (11)
C15	0.0327 (13)	0.0365 (13)	0.0436 (14)	0.0042 (10)	−0.0019 (11)	−0.0265 (11)
C16	0.0364 (15)	0.0621 (18)	0.0601 (18)	0.0102 (13)	−0.0099 (13)	−0.0374 (15)
C17	0.0319 (15)	0.082 (2)	0.075 (2)	−0.0047 (15)	0.0059 (15)	−0.0473 (19)
C18	0.0482 (18)	0.073 (2)	0.0540 (19)	−0.0123 (16)	0.0172 (15)	−0.0368 (17)
C19	0.0495 (16)	0.0507 (16)	0.0373 (14)	−0.0030 (13)	0.0034 (12)	−0.0271 (13)
C20	0.0339 (13)	0.0365 (12)	0.0374 (13)	0.0010 (10)	−0.0012 (10)	−0.0253 (11)
C21	0.0387 (13)	0.0331 (12)	0.0373 (13)	−0.0012 (10)	−0.0064 (11)	−0.0193 (11)
C22	0.0388 (13)	0.0359 (12)	0.0218 (11)	−0.0100 (10)	−0.0031 (10)	−0.0086 (10)
C23	0.0310 (12)	0.0297 (11)	0.0227 (11)	−0.0079 (9)	−0.0063 (9)	−0.0033 (9)
C24	0.0505 (15)	0.0417 (14)	0.0309 (13)	−0.0107 (12)	−0.0204 (11)	−0.0045 (11)
C25	0.0529 (17)	0.0394 (14)	0.0450 (16)	−0.0004 (12)	−0.0302 (13)	0.0007 (12)
C26	0.0383 (14)	0.0280 (12)	0.0478 (15)	0.0001 (10)	−0.0144 (12)	−0.0046 (11)
C27	0.0301 (12)	0.0302 (12)	0.0324 (12)	−0.0041 (10)	−0.0078 (10)	−0.0093 (10)
C28	0.0196 (10)	0.0301 (11)	0.0232 (11)	−0.0062 (9)	−0.0042 (8)	−0.0036 (9)
C29	0.0303 (12)	0.0327 (12)	0.0273 (11)	−0.0054 (9)	−0.0119 (9)	−0.0095 (9)

Geometric parameters (Å, º) top

I1—Cd1ⁱ	2.8604 (2)	C5—C6	1.498 (3)
I1—Cd1	2.8751 (2)	C7—C8	1.378 (3)
I2—Cd1	2.7314 (2)	C7—C12	1.400 (3)
I3—Cd1	2.7150 (2)	C8—C9	1.394 (3)
Cd1—I1ⁱ	2.8603 (2)	C9—C10	1.373 (4)
Cu1—N1	2.0207 (17)	C10—C11	1.387 (4)
Cu1—S6	2.2600 (6)	C11—C12	1.391 (3)
Cu1—S7	2.2662 (6)	C12—C13	1.495 (3)
S6—C14	1.829 (2)	C14—C15	1.504 (3)
S6—C13	1.833 (2)	C15—C16	1.395 (4)
S7—C22	1.830 (2)	C15—C20	1.397 (3)
S7—C21	1.837 (2)	C16—C17	1.381 (4)
O1—C28	1.382 (2)	C17—C18	1.365 (5)
O1—C29	1.433 (3)	C18—C19	1.383 (4)
O2—C7	1.374 (3)	C19—C20	1.398 (3)
O2—C6	1.418 (3)	C20—C21	1.503 (3)
N1—C1	1.348 (3)	C22—C23	1.493 (3)
N1—C5	1.348 (3)	C23—C24	1.389 (3)
C1—C2	1.372 (3)	C23—C28	1.396 (3)
C1—C29	1.505 (3)	C24—C25	1.383 (4)
C2—C3	1.381 (3)	C25—C26	1.370 (4)
C3—C4	1.373 (3)	C26—C27	1.386 (3)
C4—C5	1.385 (3)	C27—C28	1.382 (3)

Cd1ⁱ—I1—Cd1	87.178 (6)	C8—C7—C12	122.6 (2)
I3—Cd1—I2	116.441 (8)	C7—C8—C9	118.5 (2)
I3—Cd1—I1ⁱ	109.558 (7)	C10—C9—C8	120.4 (3)
I2—Cd1—I1ⁱ	117.538 (8)	C9—C10—C11	120.2 (2)
I3—Cd1—I1	114.680 (8)	C10—C11—C12	121.1 (2)
I2—Cd1—I1	103.343 (7)	C11—C12—C7	117.1 (2)
I1ⁱ—Cd1—I1	92.822 (6)	C11—C12—C13	122.6 (2)
N1—Cu1—S6	123.10 (5)	C7—C12—C13	120.3 (2)
N1—Cu1—S7	120.30 (5)	C12—C13—S6	115.02 (16)
S6—Cu1—S7	116.53 (2)	C15—C14—S6	109.84 (16)
C14—S6—C13	98.96 (11)	C16—C15—C20	119.2 (2)
C14—S6—Cu1	107.13 (8)	C16—C15—C14	118.3 (2)
C13—S6—Cu1	107.18 (8)	C20—C15—C14	122.5 (2)
C22—S7—C21	98.81 (11)	C17—C16—C15	121.2 (3)
C22—S7—Cu1	106.37 (8)	C18—C17—C16	119.8 (3)
C21—S7—Cu1	110.22 (8)	C17—C18—C19	120.2 (3)
C28—O1—C29	117.10 (17)	C18—C19—C20	121.1 (3)
C7—O2—C6	119.26 (18)	C15—C20—C19	118.6 (2)
C1—N1—C5	117.79 (18)	C15—C20—C21	123.4 (2)
C1—N1—Cu1	120.85 (14)	C19—C20—C21	118.0 (2)
C5—N1—Cu1	121.34 (14)	C20—C21—S7	115.45 (16)
N1—C1—C2	122.6 (2)	C23—C22—S7	112.56 (15)
N1—C1—C29	115.16 (19)	C24—C23—C28	118.0 (2)
C2—C1—C29	122.2 (2)	C24—C23—C22	121.4 (2)
C1—C2—C3	119.3 (2)	C28—C23—C22	120.6 (2)
C4—C3—C2	119.0 (2)	C25—C24—C23	120.7 (2)
C3—C4—C5	119.1 (2)	C26—C25—C24	120.4 (2)
N1—C5—C4	122.3 (2)	C25—C26—C27	120.3 (2)
N1—C5—C6	116.59 (18)	C28—C27—C26	119.2 (2)
C4—C5—C6	121.1 (2)	C27—C28—O1	124.0 (2)
O2—C6—C5	104.99 (18)	C27—C28—C23	121.4 (2)
O2—C7—C8	124.5 (2)	O1—C28—C23	114.46 (19)
O2—C7—C12	112.9 (2)	O1—C29—C1	110.66 (17)

Symmetry code: (i) −x+1, −y+1, −z+1.

Funding information

The following funding is acknowledged: National Research Foundation of Korea (grant No. 2016R1A2A2A05918799; grant No. 2017R1A4A1014595).

References

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IUCrJ

Volume 5| Part 1| January 2018| Pages 45-53

ISSN: 2052-2525

https://doi.org/10.1107/S2052252517015081

CHEMISTRY | CRYSTENG

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