research communications
Structural diversity in copper(I) iodide complexes with 6-thioxopiperidin-2-one, piperidine-2,6-dithione and isoindoline-1,3-dithione ligands
aUniversity of Wisconsin-Madison, Department of Chemistry, 1101 University Avenue, Madison, WI, 53703, USA
*Correspondence e-mail: iguzei@chem.wisc.edu
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 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.
Keywords: crystal structure; copper(I) iodide; coordination complexes.
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, CuI 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 or have been used as ligands to the CuI centers. We were interested in exploring the structures of CuI 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.
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 with a 49.07 (9)° dihedral angle between the planes defined by atoms C2–C3–C4 and C2–C1–N1–C5–C4.
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 with a 47.5 (2)° dihedral angle between the planes defined by atoms C2–C3–C4 and C2–C1–N1–C5–C4.
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.
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).
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 Å3) 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).
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).
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].
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 N2iv—H2iv⋯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.
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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⋯I1ii; 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 CuI 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 P and were used to make the final space-group determination. For structures II–V, a combination of the 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 Cc (V).
The structures were solved via intrinsic phasing and refined by least-squares 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 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 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 to be 615 Å3. This solvent-accessible volume is comprised of two smaller (ca 115 Å3) and two larger (ca 196 Å3) solvent-accessible voids and is 27% of the unit-cell volume. The program calculated 155 electrons in the 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 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 .
details are summarized in Table 3
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Supporting information
https://doi.org/10.1107/S2056989020009676/zl2791sup1.cif
contains datablocks I, II, III, IV, V. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020009676/zl2791Isup7.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989020009676/zl2791IIsup8.hkl
Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989020009676/zl2791IIIsup9.hkl
Structure factors: contains datablock IV. DOI: https://doi.org/10.1107/S2056989020009676/zl2791IVsup10.hkl
Structure factors: contains datablock V. DOI: https://doi.org/10.1107/S2056989020009676/zl2791Vsup11.hkl
Data collection: APEX3 (Bruker, 2017) for (I), (V); APEX2 (Bruker, 2013) for (II), (III), (IV). Cell
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).[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) Å3 | 0.15 × 0.13 × 0.13 mm |
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 on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.012 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.030 | w = 1/[σ2(Fo2) + (0.010P)2 + 0.2P] where P = (Fo2 + 2Fc2)/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 |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
I1—Cu1 | 2.6261 (6) | C2—H2B | 0.9900 |
I1—Cu1i | 2.6321 (7) | C2—C3 | 1.5216 (16) |
Cu1—Cu1i | 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—Cu1i | 62.489 (13) | C3—C2—H2B | 109.2 |
I1—Cu1—I1i | 117.511 (13) | C2—C3—H3A | 109.7 |
I1i—Cu1—Cu1i | 58.647 (16) | C2—C3—H3B | 109.7 |
I1—Cu1—Cu1i | 58.864 (17) | C2—C3—C4 | 109.71 (9) |
S1—Cu1—I1 | 102.61 (2) | H3A—C3—H3B | 108.2 |
S1—Cu1—I1i | 118.719 (16) | C4—C3—H3A | 109.7 |
S1—Cu1—Cu1i | 132.375 (17) | C4—C3—H3B | 109.7 |
N2—Cu1—I1i | 105.18 (3) | C3—C4—H4A | 109.3 |
N2—Cu1—I1 | 111.38 (3) | C3—C4—H4B | 109.3 |
N2—Cu1—Cu1i | 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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···I1i | 0.86 (1) | 2.85 (1) | 3.6980 (12) | 174 (1) |
Symmetry code: (i) −x+1, −y+1, −z. |
[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) Å3 | Block, yellow |
Z = 4 | 0.1 × 0.08 × 0.04 mm |
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 on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.063 | w = 1/[σ2(Fo2) + (0.0336P)2 + 8.1228P] where P = (Fo2 + 2Fc2)/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 |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
I1—Cu1 | 2.6451 (6) | N1—C5 | 1.405 (5) |
I1—Cu2i | 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—Cu1i | 2.7796 (6) | C2—H2B | 0.9900 |
I2—Cu2 | 2.6456 (6) | C2—C3 | 1.518 (6) |
Cu1—Cu1i | 2.8150 (11) | C3—H3A | 0.9900 |
Cu1—Cu2 | 2.7864 (8) | C3—H3B | 0.9900 |
Cu1—Cu2i | 2.7106 (8) | C3—C4 | 1.523 (5) |
Cu2—Cu2i | 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—Cu2i | 60.911 (18) | N2—Cu2—I1i | 98.80 (11) |
Cu1—I1—Cu2 | 62.493 (17) | N2—Cu2—I1 | 104.44 (10) |
Cu2i—I1—Cu2 | 56.78 (2) | N2—Cu2—I2 | 114.05 (10) |
Cu1—I2—Cu1i | 62.35 (2) | N2—Cu2—Cu1 | 151.07 (11) |
Cu2—I2—Cu1 | 63.439 (17) | N2—Cu2—Cu1i | 143.75 (11) |
Cu2—I2—Cu1i | 59.892 (17) | N2—Cu2—Cu2i | 134.36 (10) |
I1—Cu1—I2 | 107.43 (2) | C1—S1—Cu1 | 111.24 (13) |
I1—Cu1—I2i | 112.60 (2) | C1—N1—H1 | 117 (3) |
I1—Cu1—Cu1i | 110.454 (13) | C1—N1—C5 | 127.1 (3) |
I1—Cu1—Cu2i | 60.576 (18) | C5—N1—H1 | 115 (3) |
I1—Cu1—Cu2 | 60.157 (18) | C6—N2—Cu2 | 169.7 (3) |
I2—Cu1—I2i | 113.84 (2) | N1—C1—S1 | 121.6 (3) |
I2—Cu1—Cu1i | 61.007 (19) | N1—C1—C2 | 116.4 (3) |
I2i—Cu1—Cu1i | 56.64 (2) | C2—C1—S1 | 122.0 (3) |
I2i—Cu1—Cu2 | 101.87 (2) | C1—C2—H2A | 109.0 |
I2—Cu1—Cu2i | 107.32 (2) | C1—C2—H2B | 109.0 |
I2—Cu1—Cu2 | 58.129 (16) | C1—C2—C3 | 112.8 (3) |
Cu2i—Cu1—I2i | 57.602 (18) | H2A—C2—H2B | 107.8 |
Cu2i—Cu1—Cu1i | 60.53 (2) | C3—C2—H2A | 109.0 |
Cu2—Cu1—Cu1i | 57.881 (18) | C3—C2—H2B | 109.0 |
Cu2i—Cu1—Cu2 | 55.97 (2) | C2—C3—H3A | 109.7 |
S1—Cu1—I1 | 107.77 (3) | C2—C3—H3B | 109.7 |
S1—Cu1—I2i | 97.98 (3) | C2—C3—C4 | 109.7 (3) |
S1—Cu1—I2 | 117.03 (3) | H3A—C3—H3B | 108.2 |
S1—Cu1—Cu1i | 140.07 (3) | C4—C3—H3A | 109.7 |
S1—Cu1—Cu2 | 159.65 (4) | C4—C3—H3B | 109.7 |
S1—Cu1—Cu2i | 135.38 (3) | C3—C4—H4A | 109.0 |
I1i—Cu2—I1 | 118.71 (2) | C3—C4—H4B | 109.0 |
I1i—Cu2—Cu1i | 58.512 (18) | H4A—C4—H4B | 107.8 |
I1i—Cu2—Cu1 | 109.64 (2) | C5—C4—C3 | 112.9 (3) |
I1—Cu2—Cu1 | 57.350 (16) | C5—C4—H4A | 109.0 |
I2—Cu2—I1i | 115.15 (2) | C5—C4—H4B | 109.0 |
I2—Cu2—I1 | 105.38 (2) | O1—C5—N1 | 117.9 (3) |
I2—Cu2—Cu1i | 62.509 (18) | O1—C5—C4 | 125.1 (3) |
I2—Cu2—Cu1 | 58.432 (17) | N1—C5—C4 | 117.0 (3) |
Cu1i—Cu2—I1 | 111.24 (2) | N2—C6—C7 | 178.5 (4) |
Cu1i—Cu2—Cu1 | 61.59 (3) | C6—C7—H7A | 109.5 |
Cu2i—Cu2—I1 | 61.16 (2) | C6—C7—H7B | 109.5 |
Cu2i—Cu2—I1i | 62.06 (2) | C6—C7—H7C | 109.5 |
Cu2i—Cu2—I2 | 111.572 (12) | H7A—C7—H7B | 109.5 |
Cu2i—Cu2—Cu1 | 60.528 (19) | H7A—C7—H7C | 109.5 |
Cu2i—Cu2—Cu1i | 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. |
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) |
[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) Å3 | Plate, orange |
Z = 8 | 0.08 × 0.07 × 0.03 mm |
F(000) = 1200 |
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 on F2 | 1 restraint |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.055P)2 + 1.1889P] where P = (Fo2 + 2Fc2)/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 |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
I1—Cu1 | 2.6264 (11) | C2—H2A | 0.9900 |
I1—Cu1i | 2.6709 (12) | C2—H2B | 0.9900 |
I1—Cu1ii | 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—Cu1ii | 106.77 (3) | H2A—C2—H2B | 107.8 |
Cu1—I1—Cu1i | 116.92 (2) | C3—C2—H2A | 109.1 |
Cu1ii—I1—Cu1i | 113.08 (4) | C3—C2—H2B | 109.1 |
I1iii—Cu1—I1iv | 104.19 (4) | C2—C3—H3A | 109.7 |
I1—Cu1—I1iv | 116.85 (3) | C2—C3—H3B | 109.7 |
I1—Cu1—I1iii | 99.58 (3) | C2—C3—C4 | 109.6 (4) |
S1—Cu1—I1iv | 97.12 (4) | H3A—C3—H3B | 108.2 |
S1—Cu1—I1 | 120.62 (4) | C4—C3—H3A | 109.7 |
S1—Cu1—I1iii | 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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1v | 0.86 (2) | 2.03 (2) | 2.881 (5) | 171 (5) |
Symmetry code: (v) −x+1, −y+1, −z+2. |
[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) Å3 | Block, red |
Z = 4 | 0.22 × 0.13 × 0.09 mm |
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 on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.126 | w = 1/[σ2(Fo2) + (0.0963P)2 + 0.866P] where P = (Fo2 + 2Fc2)/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 |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
I1—Cu1 | 2.6365 (8) | C1—C2 | 1.490 (7) |
I1—Cu1i | 2.6687 (8) | C10—C9 | 1.491 (7) |
I2—Cu2 | 2.6719 (8) | C5—C4 | 1.487 (7) |
I2—Cu2ii | 2.6724 (8) | C2—H2A | 0.9900 |
Cu1—S4iii | 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—Cu2ii | 62.54 (3) | C1—C2—H2A | 108.8 |
Cu1—I1—Cu1i | 64.94 (3) | C1—C2—H2B | 108.8 |
I1—Cu1—I1i | 115.06 (3) | C1—C2—C3 | 113.7 (5) |
S4iii—Cu1—I1 | 104.72 (4) | H2A—C2—H2B | 107.7 |
S4iii—Cu1—I1i | 111.04 (4) | C3—C2—H2A | 108.8 |
S4iii—Cu1—S1 | 106.30 (5) | C3—C2—H2B | 108.8 |
S1—Cu1—I1i | 111.41 (4) | C10—C9—H9A | 109.4 |
S1—Cu1—I1 | 107.75 (4) | C10—C9—H9B | 109.4 |
I2—Cu2—I2ii | 117.46 (3) | C10—C9—C8 | 111.3 (4) |
S2—Cu2—I2ii | 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—I2ii | 96.95 (4) | C6—C7—H7A | 109.2 |
S3—Cu2—I2 | 106.83 (5) | C6—C7—H7B | 109.2 |
C10—S4—Cu1iii | 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 |
Cu1iii—S4—C10—N2 | 8.2 (5) | N2—C6—C7—C8 | −23.4 (7) |
Cu1iii—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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···I2ii | 0.88 | 2.79 | 3.628 (4) | 161 |
N2—H2···I1iv | 0.88 | 2.90 | 3.679 (4) | 149 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iv) x+1, y, z. |
[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) Å3 | Block, black |
Z = 4 | 0.30 × 0.02 × 0.01 mm |
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 on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.036 | w = 1/[σ2(Fo2) + (0.0417P)2 + 7.0163P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 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 |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
I1—Cu1 | 2.6152 (13) | C2—C7 | 1.405 (11) |
I1—Cu1i | 2.6798 (13) | C3—H3 | 0.9500 |
Cu1—S1 | 2.269 (2) | C3—C4 | 1.394 (12) |
Cu1—S2ii | 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—Cu1i | 102.12 (4) | C2—C3—H3 | 120.9 |
I1—Cu1—I1iii | 102.12 (4) | C2—C3—C4 | 118.1 (8) |
S1—Cu1—I1iii | 100.30 (6) | C4—C3—H3 | 120.9 |
S1—Cu1—I1 | 111.05 (6) | C3—C4—H4 | 120.0 |
S1—Cu1—S2ii | 119.65 (8) | C3—C4—C5 | 120.1 (8) |
S2ii—Cu1—I1iii | 98.16 (7) | C5—C4—H4 | 120.0 |
S2ii—Cu1—I1 | 120.16 (7) | C4—C5—H5 | 119.1 |
C1—S1—Cu1 | 118.8 (3) | C6—C5—C4 | 121.8 (8) |
C8—S2—Cu1iv | 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) |
Cu1iv—S2—C8—N1 | 18.3 (8) | C3—C2—C7—C6 | −2.0 (11) |
Cu1iv—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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···I1iv | 0.88 | 2.84 | 3.692 (7) | 163 |
Symmetry code: (iv) x, −y+1, z−1/2. |
Ia | IIb | IIIc | IVd | Ve | ||||||
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—Cu1i | 2.6321 (7) | I1—Cu2i | 2.7017 (7) | I1—Cu1i | 2.6709 (12) | I1—Cu1i | 2.6687 (8) | I1—Cu1i | 2.6798 (13) | |
I1—Cu2 | 2.7250 (6) | I1—Cu1ii | 2.6342 (10) | I2—Cu2 | 2.6719 (8) | |||||
I2—Cu1 | 2.7796 (6) | I2—Cu2ii | 2.6724 (8) | |||||||
I2—Cu1i | 2.6542 (6) | |||||||||
I2—Cu2 | 2.6456 (6) | |||||||||
Cu···Cu | Cu1—Cu1i | 2.7274 (6) | Cu1—Cu1i | 2.8150 (11) | ||||||
Cu1—Cu2 | 2.7864 (8) | |||||||||
Cu1—Cu2i | 2.7106 (8) | |||||||||
Cu2—Cu2i | 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—S4iii | 2.3075 (13) | Cu1—S2ii | 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 + 1/2 for II; (c) (i) -x + 1/2, -y + 3/2, z - 1/2 and (ii) x, -y + 1, z - 1/2 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 + 1/2 for V. |
D—H···A | D—H | H···A | D···A | D—H···A | |
Ia | N1—H1···I1i | 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) |
IIIb | N1—H1···O1iii | 0.86 (2) | 2.03 (2) | 2.881 (5) | 171 (5) |
IVc | N1—H1···I2ii | 0.88 | 2.79 | 3.628 (4) | 160.9 |
N2—H2···I1iv | 0.88 | 2.90 | 3.679 (4) | 149.2 | |
Vd | N1—H1···I1iii | 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 - 1/2 for IV. |
Acknowledgements
AMW would like to thank Michael M. Aristov for aid with the data collection of III–V. In-house programs Gn (Guzei, 2013) were used during experiment planning and structure The Bruker Quazar APEXII was UW–Madison Department of Chemistry with a portion of a generous gift from Paul J. and Margaret M. Bender.
Funding information
Funding for this research was provided by: National Science Foundation (grant No. 1664999; grant No. 1953924).
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