Isolation and evolution of labile sulfur allotropes via kinetic encapsulation in interactive porous networks

Kitagawa, H.; Ohtsu, H.; Cruz-Cabeza, A.J.; Kawano, M.

doi:10.1107/S2052252516008423

research papers

IUCrJ

Volume 3| Part 4| July 2016| Pages 232-236

ISSN: 2052-2525

doi:10.1107/S2052252516008423

CHEMISTRY | CRYSTENG

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Isolation and evolution of labile sulfur allotropes via kinetic encapsulation in interactive porous networks

Hakuba Kitagawa,^a Hiroyoshi Ohtsu,^a,^b ^* Aurora J. Cruz-Cabeza ^c and Masaki Kawano ^a,^b ^*

^aDivision of Advanced Materials Science, Pohang University of Science and Technology, RIST Building 3-3390, 77 Cheongam-Ro, Nam-Gu, Pohang, Republic of Korea, ^bDepartment of Chemistry, School of Science, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo, Japan, and ^cSchool of Chemical Engineering and Analytical Science, University of Manchester, The Mill, Sackville Street, Manchester M13 9PL, England
^*Correspondence e-mail: hotsu@postech.ac.kr, mkawano@postech.ac.kr

Edited by M. Eddaoudi, King Abdullah University, Saudi Arabia (Received 22 March 2016; accepted 24 May 2016; online 8 June 2016)

The isolation and characterization of small sulfur allotropes have long remained unachievable because of their extreme lability. This study reports the first direct observation of disulfur (S₂) with X-ray crystallography. Sulfur gas was kinetically trapped and frozen into the pores of two Cu-based porous coordination networks containing interactive iodide sites. Stabilization of S₂ was achieved either through physisorption or chemisorption on iodide anions. One of the networks displayed shape selectivity for linear molecules only, therefore S₂ was trapped and remained stable within the material at room temperature and higher. In the second network, however, the S₂ molecules reacted further to produce bent-S₃ species as the temperature was increased. Following the thermal evolution of the S₂ species in this network using X-ray diffraction and Raman spectroscopy unveiled the generation of a new reaction intermediate never observed before, the cyclo-trisulfur dication (cyclo-S₃²⁺). It is envisaged that kinetic guest trapping in interactive crystalline porous networks will be a promising method to investigate transient chemical species.

Keywords: sulfur; kinetic trapping; porous coordination networks; X-ray diffraction; allotropes; metal–organic frameworks; MOFs; coordination polymers; transient chemical species.

CCDC references: 1415696; 1415697; 1415698; 1415699; 1415700

1. Introduction

Cryogenic trapping methods, coupled with spectroscopy or crystallography, have been widely used to investigate transient chemical species (Whittle et al., 1954 ; Misochko et al., 2003 ; Kawano, 2014 ; Edman et al., 1999 ), but these methods do not always allow the observation of very labile reactive intermediates. To circumvent this problem, we propose encapsulation of transient species in an interactive porous network under non-equilibrium conditions. The kinetic trapping method is widely used in cryogenic trapping (Whittle et al., 1954; Mück et al., 2012 ), although there is no report using porous coordination networks and no direct X-ray observation has yet been achieved. The method using porous coordination networks might provide a unique way for in situ observation of very labile chemical intermediates and for the following of chemical reactions

Many fascinating guest encapsulation studies have been performed in the past using porous coordination networks (Matsuda, 2013 ; Cook et al., 2013 ; Kitagawa & Uemura, 2005 ; Eddaoudi et al., 2001 ; Férey, 2008 ; Peterson et al., 2014 ; Ohmori et al., 2005 ). Most of these studies, however, have only been carried out in conditions of thermodynamic equilibrium, which makes the observation of transient intermediates hardly possible (Kubota et al., 2014 ; Ikemoto et al., 2014 ; Kawamichi et al., 2009 ). Although time-resolved techniques offer attractive alternatives, they generally require the reactions to be reversible (Ohashi, 1998 ). Our approach involves the stabilization of transient species via the active sites located in the channels of porous coordination networks. Here we report the first direct X-ray observation of extremely reactive S₂ species and their conversion towards bent-S₃ via cyclo-S₃²⁺ on an interactive site in a channel of a porous coordination network.

Sulfur has a very rich chemistry, with around 30 allotropes known to date, although the transient nature of the smaller allotropes makes their isolation and characterization very challenging (Peramunage & Licht, 1993 ; Evers & Nazar, 2013 ; Xin et al., 2012 ; Meyer, 1976 ; Steudel & Eckert, 2003 ; Steudel et al., 2003 ).

In a recent study, we reported the direct observation of bent-S₃ (trisulfur or thiozone) through encapsulation in a Zn-based porous coordination network (Ohtsu et al., 2013 ). The crystal structure of the network–S₃ complex revealed important interactions between S₃ and the network iodides of such strength that release of the S₃ molecules only took place at high temperatures (500 K). We suspect that S₃ encapsulation might have taken place via a `ship-in-a-bottle' type of mechanism (Ichikawa et al., 1991 ; Rau et al., 1973 ): first the smaller S₂ (disulfur) enters the pores of the network and then it converts to S₃ (trisulfur) because S₃ is more stable than S₂; however, this mechanism remains to be proven. We have also reported the synthesis of two porous coordination networks of CuI with tetra-4-(4-pyridyl)phenylmethane (TPPM) with fascinating properties (Kitagawa et al., 2013 ). The kinetic product of the synthesis is network 1 (Fig. 1a), [(CuI)₂(TPPM)]_n, which contains molecular-sized channels with accessible iodide sites. These iodide sites are highly interacting and can adsorb molecules such as I₂ through chemisorption (Kitagawa et al., 2013). The thermodynamic product of the synthesis is network 2 (Fig. 4a), [(Cu₂I₂)(TPPM)]_n, which contains smaller one-dimensional channels with no exposed iodide sites. In network 2, only physisorption of I₂ is possible within the hydrophobic one-dimensional channel, because the iodide sites are located in small cavities that are poorly accessible. The channels of networks 1 and 2 have the precise molecular dimensions needed for trapping small molecules, with the added advantage of the interacting iodide sites in network 1. Network 1 can accommodate S₂ (5.8 × 3.6 × 3.6 Å) or S₃ (6.8 × 4.6 × 3.6 Å for the bent form, 5.8 × 5.5 × 3.6 Å for the cyclo form) because of its channel size of 5.8 × 5.5 Å. In contrast, network 2 can accommodate only S₂, because of its channel size of 4.0 × 3.9 Å. Because we expect strong interactions between small sulfur allotropes and the iodide sites of the networks (see the supporting information), these materials may serve as traps for labile sulfur intermediates. In order to isolate the most reactive species, we consciously arrested the encapsulation process before it reached equilibrium via cooling (kinetic trapping); we aimed to observe the `ship-in-a-bottle' conversion from reactive S₂ to the more dynamically stable S₃ by heating.

Figure 1
Pore description in the crystal structures of (a) network 1, and (b) network 1 after sulfur encapsulation at 250 K, (c) 300 K and (d) 350 K. (e) The crystal structure of sulfur-encapsulating network 1, showing parts of the {CuI} unit and the sulfur species. (Left) At 250 K, physisorbed S₂ and bent-S₃ were observed. (Middle) At 300 K, chemisorbed cyclo-S₃²⁺, physisorbed cyclo-S₃ and bent-S₃ were observed. (Right) At 350 K, bent-S₃ was observed. (Bottom) The arrow indicates the time course of the measurements, showing the molecular transformation mechanism from S₂ to bent-S₃ species. Atom colouring: Cu orange, I purple, and S yellow, red, green, pink and cyan to distinguish disordered molecules.

2. Results and discussion

2.1. Kinetic trapping of sulfur gas

Sulfur gas was encapsulated in networks 1 and 2 under kinetic conditions; an excess amount of elemental sulfur and desolvated network 1 or 2 were placed at different sites of a zigzag shaped glass tube (see Fig. S1 in the supporting information). The glass tube was then sealed in a vacuum (∼10⁻⁶ Torr; 1 Torr = 133.322 Pa) and heated in a flame at the site containing the sulfur. The zigzag tube was sufficiently long, and the sulfur and the network thus sufficiently separated, that high temperatures could be reached at the sulfur site while the network was kept at room temperature, creating a sharp temperature gradient. Shortly after heating the sulfur powder, the yellow crystals of network 1 turned dark yellow, whereas the crystals of network 2 did not display a colour change.

2.2. Direct observation of transient small sulfur by X-ray diffraction

Within 5 min of the colour change, a single crystal of network 1 was mounted on a goniometer and X-ray diffraction data were collected at 250 K. Because diffuse scattering was observed at 250 K (see Fig. S4 in the supporting information), the crystal structure was solved making use of Bragg diffractions only (see the supporting information). On the basis of a Laue check, and after careful consideration of various crystal systems and space groups, the structure was solved in the tetragonal $[P{\overline 4}]$ space group.

The crystal structure analysis clearly revealed the existence of physisorbed S₂ and bent-S₃ species on the iodide sites of the framework channels (Fig. 1; see Fig. S5 in the supporting information for structure details). The geometry of S₃ was found to be in good agreement with that previously reported for [(ZnI₂)₃(TPT)₂(S₃)]_n by structure solution from X-ray powder diffraction (Ohtsu et al., 2013) and that of S₃ in the gas phase as observed by rotational spectroscopy (McCarthy et al., 2004 ). These physisorbed S₂ and bent-S₃ do not have any interaction with iodide; reactive S₂ can take part in subsequent reactions because it is not stabilized by the pores.

In order to investigate the transient nature of S₂ in the channels of network 1, we collected two additional sets of X-ray single-crystal diffraction data at 300 and 350 K using a heating rate of 10 K min⁻¹ between measurements (see Fig. S3 in the supporting information). The diffraction data at 300 K showed a space-group change from $[P{\overline 4}]$ to $[I{\overline 4}]$ , a sharpening of the diffraction spots and the almost complete disappearance of diffuse scattering, which indicates that successive reaction of the sulfur species had taken place on heating. Analysis of the 300 K structure revealed the formation of cyclo-S₃ chemisorbed on bridging iodide sites, and the presence of physisorbed bent-S₃ and physisorbed cyclo-S₃ in the network 1 channels (Fig. 1). The cyclo-S₃ allotrope has been predicted to be less stable than the bent-S₃ structure, but still energetically accessible, by theoretical calculations (Flemmig et al., 2005 ) but it had never been observed before. A theoretical investigation of the adsorption of cyclo-S₃ on the network iodide sites revealed that chemisorption is only possible if cyclo-S₃ is present as a dication, cyclo-S₃²⁺ (see the supporting information). Even though we did not use any restraints for the bond lengths, the geometric parameters obtained from this X-ray analysis matched those obtained by theoretical calculation (Fig. 2). The cyclo-S₃²⁺ state is isoelectric with a cyclo-SiS₂ molecule (Mück et al., 2012) isolated by matrix isolation, indicating the potential existence of a cyclic form. We could not determine the counter pair formed by oxidation, because of severe disorder of the physisorbed species for which restraints on bond length were used during the refinement. A structure redetermination of the single crystal at an even higher temperature, 350 K, revealed only bent-S₃ species in network 1, suggesting a complete transformation of chemisorbed cyclo-S₃²⁺ (and physisorbed cyclo-S₃ species) to bent-S₃ species (see Fig. S6 in the supporting information). After the heating cycle, the same single crystal was cooled back to 250 K for a second structure redetermination at low temperature, but the diffraction data were not of sufficient quality to allow structure solution. Refinement using the initial $[P{\overline 4}]$ space group was unsuccessful, which indicates an irreversible $[P{\overline 4}]$ to $[I{\overline 4}]$ phase transformation.

Figure 2
Geometric parameters from X-ray diffraction and theoretical calculation for chemisorbed cyclo-S₃²⁺. Red numbers indicate values obtained from X-ray analysis and blue numbers refer to values obtained from calculation of I—cyclo-S₃²⁺. Atom colouring: Cu orange, I purple and S pink.

From this series of X-ray diffraction experiments of sulfur-encapsulating network 1, we propose one of the possible reaction pathways of small sulfur allotropes: first, S₂ was kinetically trapped by physisorption and partly transformed into physisorbed bent-S₃; second, on heating the S₂ converted to chemisorbed cyclo-S₃²⁺, and physisorbed cyclo-S₃ and bent-S₃ species; and third, the cyclo-S₃ species transformed to the more stable bent-S₃ species (Fig. 1e). Despite the kinetic nature of these experiments, we always found consistent results upon repetition of the diffraction measurements on different single crystals. We also observed chemisorbed S₂ molecules on the interactive iodide sites (see Fig. S7 in the supporting information). Our theoretical calculations predicted chemisorption of S₂ to be less favourable than physisorption, because S₂ needs to change its electronic spin (see the supporting information).

2.3. Spectroscopic confirmation of sulfur species

The trapping of sulfur in network 1 was also investigated at room temperature using microscopic Raman and IR spectroscopy. Raman spectra of the samples after sulfur encapsulation displayed new bands at 475 and 573 cm⁻¹ (Fig. 3a). These bands have been assigned to chemisorbed cyclo-S₃²⁺ (475 cm⁻¹) and chemisorbed cyclo-S₃²⁺ plus bent-S₃ species (573 cm⁻¹) with the help of density functional theory (DFT) calculations (see the supporting information) (Picquenard et al., 1993 ). After 18 h, the intensity of the cyclo-S₃²⁺ species band decreased significantly, which suggests that the cyclo-S₃²⁺ species were consumed and converted into bent-S₃ (see Fig. S9 in the supporting information). Bent-S₃ species were clearly detected by IR spectroscopy (band at ∼680 cm⁻¹; see Fig. S10 in the supporting information). There are two possibilities for the mechanism of the transformation of S₂ to cyclo-S₃²⁺ to bent-S₃: (i) direct conversion of S₂ to S₃ using catalytic iodide sites; or (ii) conversion including dimethylsulfoxide (DMSO) (see the supporting information). The oxidation of S₃ into cyclo-S₃²⁺ might be preceded by other sulfur species accepting electrons and protons, resulting in H₂S_n species. We observed new bands in the IR spectra in the region of 2225 cm⁻¹, which are most likely due to S—H stretches (see Fig. S17 in the supporting information) (Marsden & Smith, 1988 ). Attempts to reveal the reaction mechanism by removing DMSO completely resulted in deterioration of the single crystals. A possible reaction mechanism is outlined in the supporting information. However, the reactions occurring are complex and, unless the intermediates are strongly adsorbed on the network (like the species identified by X-ray diffraction), they are difficult to characterize. In fact, although it is not trivial to reveal the reaction mechanism, we clearly observed the structural change in these small sulfur species on an interactive site using X-ray diffraction.

Figure 3
(a) Raman spectra of network 1, desolvated (black), solvated with DMSO (pink) and after sulfur encapsulation (red). (b) Raman spectra of network 2, desolvated (black), solvated with DMSO (pale blue) and after sulfur encapsulation (blue). The inner graph in part (b) shows a magnified view of the 690–750 cm⁻¹ region for the sulfur-encapsulated network 2 sample. Black arrows highlight the bands appearing after sulfur encapsulation [475 and 573 cm⁻¹ for cyclo-S₃²⁺ and bent-S₃ in part (a), and 728 cm⁻¹ for S₂ in part (b)]. The asterisks (*) indicate the effects of cosmic rays and the dagger (†) shows cyclo-S₈ on the crystal surface.

2.4. Sulfur species in network 2

Kinetic trapping of sulfur gas in network 2 resulted in physisorbed S₂ species only, with no evidence of S₃. X-ray analysis at 30 K revealed that S₂ physisorbed on two different sites of network 2: (i) aligned in the one-dimensional channel of the structure and presenting severe disorder; and (ii) within small cavities adjacent to the Cu₂I₂ units (Fig. 4; see Fig. S8 in the supporting information for structure details). Only physisorption of S₂ was observed on iodide sites in this network, because of steric hindrance around the iodide sites. The smaller size and linear shape of the one-dimensional channels suppress the conversion of linear S₂ molecules into S₃ species. This is an example of shape-selective trapping of a linear reactive intermediate. However, the S₂ molecules existing adjacent to the Cu₂I₂ units have a weak interaction with iodide. These interactions come from charge transfer from iodide to sulfur, as shown by calculation (see Table S5 in the supporting information). This type of interaction is different from the Lewis acid–sulfide interaction shown in a sulfide-encapsulating Ni–MOF system (MOF = metal–organic framework; Zheng et al., 2014 ). The existence of S₂ in network 2 after sulfur encapsulation was further confirmed with microscopic Raman spectroscopy at room temperature; a new band appeared at 728 cm⁻¹ (Fig. 3b), which corresponds to S₂ symmetric stretching (Barletta, 1971 ). S₂ remained stable within network 2 up to 500 K (see Fig. S2 in the supporting information).

Figure 4
Crystal structures for (a) desolvated network 2 and (b) network 2 after sulfur encapsulation at 30 K. The stoichiometry of the structure is {[(Cu₂I₂)(C₄₅H₃₂N₄)]·(S₂)_0.975}_n. Part (b) shows a different view of disordered S₂ in the one-dimensional channel with a ball-and-stick model: each coloured molecule corresponds to S₂. Atom colouring: C grey, N blue, Cu orange, I purple, and S yellow, brown, red and green. H atoms have been omitted for clarity.

3. Conclusions

We observed labile sulfur allotropes reacting in an interactive pore using X-ray diffraction. We found unexpected reactions of S₂ on an interactive site: chemisorption, transformation of S₂ into cyclo-S₃, and bent-S₃ species. On the basis of X-ray and vibrational analyses and theoretical calculations, we propose that the chemisorbed species is cyclo-S₃²⁺ rather than neutral cyclo-S₃. We also, for the first time, isolated S₂ in a one-dimensional channel by kinetically suppressing further reactions. The method reported here provides a new means for future investigations of other labile reaction intermediates. Indeed, this method makes it possible to find out new reactions of sulfur allotropes.

4. Related literature

The following references are cited in the supporting information for this article: Alecu et al. (2010 ), Allen (2002 ), Becke (1997 ), Chai & Head-Gordon (2008a ,b ), Frisch et al. (2009 ), Grimme (2006 ), Kozuch & Martin (2013 ), Sheldrick (1990 ) and Weigend & Ahlrichs (2005 ).

Supporting information

CCDC references: 1415696; 1415697; 1415698; 1415699; 1415700

Crystal structure: contains datablocks S_dimer, 250K_S_helical_initial, 300K_S_helical, 350k_S_helical, 300k_only_once. DOI: 10.1107/S2052252516008423/ed5008sup1.cif

Structure factors: contains datablock S_dimer. DOI: 10.1107/S2052252516008423/ed5008S_dimersup2.hkl

Structure factors: contains datablock 250K_S_helical_initial. DOI: 10.1107/S2052252516008423/ed5008250K_S_helical_initialsup3.hkl

Structure factors: contains datablock 300K_S_helical. DOI: 10.1107/S2052252516008423/ed5008300K_S_helicalsup4.hkl

Structure factors: contains datablock 350k_S_helical. DOI: 10.1107/S2052252516008423/ed5008350k_S_helicalsup5.hkl

Structure factors: contains datablock 300k_only_once. DOI: 10.1107/S2052252516008423/ed5008300k_only_oncesup6.hkl

Supporting information. DOI: 10.1107/S2052252516008423/ed5008sup7.pdf

Computing details top

Data collection: Crystal Clear for S_dimer; PAL ADSC Quantum-210 ADX Program for 250K_S_helical_initial, 300K_S_helical, 350k_S_helical, 300k_only_once. Cell refinement: HKL-2000 (Otwinowski & Minor, 1997) for S_dimer; HKL-3000 for 250K_S_helical_initial, 300K_S_helical, 350k_S_helical, 300k_only_once. Data reduction: HKL-2000 (Otwinowski & Minor, 1997) for S_dimer; HKL-3000 for 250K_S_helical_initial, 300K_S_helical, 350k_S_helical, 300k_only_once. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for S_dimer; SHELXL2014 (Sheldrick, 2014) for 250K_S_helical_initial, 300K_S_helical, 350k_S_helical, 300k_only_once. For all compounds, molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

(S_dimer) top

Crystal data top

(CuI)₂(N1C5H4C6H₄)4C(S₂)_0.975	D_x = 1.473 Mg m⁻³
M_r = 1070.94	Synchrotron radiation, λ = 0.68990 Å
Tetragonal, I4/mcm	Cell parameters from 20372 reflections
a = 13.2563 (2) Å	θ = 2.1–35.0°
c = 27.5616 (7) Å	µ = 1.98 mm⁻¹
V = 4843.4 (2) Å³	T = 30 K
Z = 4	Block, yellow
F(000) = 2104	0.05 × 0.03 × 0.03 mm

Data collection top

Rigaku Mercury CCD diffractometer	3092 independent reflections
Radiation source: KEK PF-AR NW2A beamline	2025 reflections with I > 2σ(I)
Si 111 monochromator	R_int = 0.070
oscillation method, ω scans	θ_max = 35.0°, θ_min = 2.1°
Absorption correction: empirical (using intensity measurements) HKL2000 Scalepack	h = −22→20
T_min = 0.908, T_max = 0.943	k = −19→12
20372 measured reflections	l = −45→24

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 0.75	w = 1/[σ²(F_o²) + (0.0688P)²] where P = (F_o² + 2F_c²)/3
3092 reflections	(Δ/σ)_max = 0.004
140 parameters	Δρ_max = 2.23 e Å⁻³
43 restraints	Δρ_min = −0.98 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	Occ. (<1)
S1A	0.0000	0.0000	0.1155 (19)	0.21 (2)	0.084 (8)
S2A	0.0000	0.0000	0.1831 (19)	0.115 (15)	0.084 (8)
S1B	0.0000	0.0000	0.156 (3)	0.13 (2)	0.068 (7)
S2B	0.0000	0.0000	0.223 (3)	0.24 (3)	0.068 (7)
S1C	0.0000	0.0000	0.035 (2)	0.205 (18)	0.104 (5)
S2C	0.0549 (11)	−0.1246 (8)	0.022 (2)	0.24 (5)	0.104 (5)
S1D	0.0000	0.0000	0.0674 (8)	0.18 (2)	0.086 (9)
S2D	0.0000	0.0000	0.0000	0.15 (2)	0.086 (9)
C30	0.0000	−0.5000	0.2500	0.0212 (9)
Cu1	0.43382 (3)	−0.06618 (3)	0.0000	0.02704 (12)
I1	0.375807 (14)	0.124193 (14)	0.0000	0.02658 (8)
N11	0.36674 (12)	−0.13326 (12)	0.05872 (9)	0.0278 (5)
C14	0.25370 (15)	−0.24630 (15)	0.12558 (10)	0.0261 (5)
C21	0.19079 (14)	−0.30921 (14)	0.15814 (9)	0.0241 (5)
C24	0.06778 (14)	−0.43222 (14)	0.21761 (9)	0.0217 (4)
C12	0.4088 (3)	−0.1967 (3)	0.08865 (15)	0.0296 (8)	0.50
H12	0.4801	−0.2039	0.0877	0.036*	0.50
C13	0.3549 (3)	−0.2549 (3)	0.12216 (16)	0.0281 (8)	0.50
H13	0.3898	−0.3007	0.1427	0.034*	0.50
C15	0.2063 (3)	−0.1719 (3)	0.09584 (15)	0.0282 (8)	0.50
H15	0.1360	−0.1593	0.0984	0.034*	0.50
C16	0.2653 (3)	−0.1181 (3)	0.06299 (15)	0.0293 (8)	0.50
H16	0.2339	−0.0692	0.0429	0.035*	0.50
C22	0.1533 (3)	−0.2734 (3)	0.20143 (14)	0.0277 (7)	0.50
H22	0.1703	−0.2071	0.2116	0.033*	0.50
C23	0.0905 (3)	−0.3327 (3)	0.23092 (13)	0.0268 (7)	0.50
H23	0.0634	−0.3053	0.2600	0.032*	0.50
C25	0.1078 (3)	−0.4689 (3)	0.17453 (13)	0.0251 (7)	0.50
H25	0.0932	−0.5363	0.1651	0.030*	0.50
C26	0.1681 (3)	−0.4103 (3)	0.14494 (13)	0.0253 (7)	0.50
H26	0.1945	−0.4377	0.1157	0.030*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.22 (3)	0.22 (3)	0.19 (5)	0.000	0.000	0.000
S2A	0.128 (19)	0.128 (19)	0.09 (3)	0.000	0.000	0.000
S1B	0.13 (2)	0.13 (2)	0.12 (4)	0.000	0.000	0.000
S2B	0.25 (4)	0.25 (4)	0.22 (7)	0.000	0.000	0.000
S1C	0.24 (3)	0.24 (3)	0.14 (3)	0.000	0.000	0.000
S2C	0.075 (7)	0.073 (7)	0.57 (14)	0.001 (5)	−0.07 (3)	−0.041 (19)
S1D	0.22 (3)	0.22 (3)	0.10 (3)	0.000	0.000	0.000
S2D	0.21 (3)	0.21 (3)	0.040 (19)	0.000	0.000	0.000
C30	0.0263 (14)	0.0263 (14)	0.0110 (17)	0.000	0.000	0.000
Cu1	0.03196 (16)	0.03196 (16)	0.0172 (2)	−0.0085 (2)	0.000	0.000
I1	0.03153 (10)	0.03153 (10)	0.01668 (10)	−0.00108 (10)	0.000	0.000
N11	0.0312 (7)	0.0312 (7)	0.0210 (10)	−0.0071 (9)	0.0010 (6)	0.0010 (6)
C14	0.0313 (8)	0.0313 (8)	0.0155 (10)	−0.0059 (10)	0.0001 (7)	0.0001 (7)
C21	0.0280 (7)	0.0280 (7)	0.0162 (10)	−0.0035 (11)	0.0012 (6)	0.0012 (6)
C24	0.0259 (7)	0.0259 (7)	0.0135 (9)	−0.0009 (10)	0.0004 (6)	0.0004 (6)
C12	0.0314 (19)	0.036 (2)	0.0215 (17)	−0.0058 (17)	0.0016 (14)	−0.0015 (15)
C13	0.032 (2)	0.0295 (19)	0.0226 (18)	−0.0023 (15)	0.0014 (15)	0.0062 (15)
C15	0.0299 (19)	0.031 (2)	0.0236 (17)	−0.0034 (15)	0.0028 (14)	0.0012 (15)
C16	0.033 (2)	0.031 (2)	0.0242 (18)	−0.0028 (17)	0.0006 (15)	0.0051 (15)
C22	0.0355 (18)	0.0286 (18)	0.0190 (16)	−0.0045 (15)	−0.0002 (15)	−0.0012 (14)
C23	0.0334 (18)	0.0317 (19)	0.0153 (14)	−0.0056 (16)	0.0052 (14)	−0.0010 (14)
C25	0.0332 (19)	0.0275 (18)	0.0147 (14)	−0.0023 (15)	0.0019 (13)	0.0000 (12)
C26	0.0333 (19)	0.0286 (17)	0.0141 (13)	0.0014 (15)	0.0030 (14)	−0.0010 (13)

Geometric parameters (Å, º) top

S1A—S2A	1.862 (16)	Cu1—I1	2.6382 (3)
S1B—S2B	1.85 (2)	I1—Cu1^xii	2.6382 (3)
S2B—S2Bⁱ	1.47 (15)	N11—C12	1.303 (5)
S1C—S2Cⁱⁱ	1.840 (17)	N11—C12^xiii	1.303 (5)
S1C—S2C	1.840 (17)	N11—C16^xiii	1.364 (5)
S1C—S2Cⁱⁱⁱ	1.840 (17)	N11—C16	1.364 (5)
S1C—S2C^iv	1.840 (17)	C14—C13	1.350 (4)
S1C—S1C^v	1.93 (11)	C14—C13^xiii	1.350 (4)
S1C—S2C^vi	2.39 (6)	C14—C15^xiii	1.428 (4)
S1C—S2C^vii	2.39 (6)	C14—C15	1.428 (5)
S1C—S2C^v	2.39 (6)	C14—C21	1.482 (4)
S1C—S2C^viii	2.39 (6)	C21—C22	1.377 (4)
S2C—S2C^vii	1.22 (12)	C21—C22^xiii	1.377 (4)
S2C—S1C^v	2.39 (6)	C21—C26	1.421 (4)
S1D—S2D	1.86 (2)	C21—C26^xiii	1.421 (4)
S2D—S1D^v	1.86 (2)	C24—C25	1.388 (4)
C30—C24^ix	1.553 (3)	C24—C25^xiii	1.388 (4)
C30—C24	1.553 (3)	C24—C23	1.402 (5)
C30—C24^x	1.553 (3)	C24—C23^xiii	1.402 (5)
C30—C24^xi	1.553 (3)	C12—C13	1.399 (6)
Cu1—N11^vii	2.050 (2)	C15—C16	1.393 (6)
Cu1—N11	2.050 (2)	C22—C23	1.404 (5)
Cu1—Cu1^xii	2.4813 (9)	C25—C26	1.381 (5)
Cu1—I1^xii	2.6382 (3)

S2Bⁱ—S2B—S1B	180.000 (2)	N11^vii—Cu1—I1	106.77 (3)
S2Cⁱⁱ—S1C—S2C	87.8 (9)	N11—Cu1—I1	106.77 (3)
S2Cⁱⁱ—S1C—S2Cⁱⁱⁱ	158 (5)	Cu1^xii—Cu1—I1	61.948 (9)
S2C—S1C—S2Cⁱⁱⁱ	87.8 (9)	I1^xii—Cu1—I1	123.896 (19)
S2Cⁱⁱ—S1C—S2C^iv	87.8 (9)	Cu1^xii—I1—Cu1	56.104 (19)
S2C—S1C—S2C^iv	158 (5)	C12—N11—C12^xiii	98.7 (4)
S2Cⁱⁱⁱ—S1C—S2C^iv	87.8 (9)	C12—N11—C16^xiii	41.1 (2)
S2Cⁱⁱ—S1C—S1C^v	79 (2)	C12^xiii—N11—C16^xiii	117.5 (3)
S2C—S1C—S1C^v	79 (2)	C12—N11—C16	117.5 (3)
S2Cⁱⁱⁱ—S1C—S1C^v	79 (2)	C12^xiii—N11—C16	41.1 (2)
S2C^iv—S1C—S1C^v	79 (2)	C16^xiii—N11—C16	106.4 (4)
S2Cⁱⁱ—S1C—S2C^vi	30 (3)	C12—N11—Cu1	126.5 (2)
S2C—S1C—S2C^vi	82.7 (15)	C12^xiii—N11—Cu1	126.5 (2)
S2Cⁱⁱⁱ—S1C—S2C^vi	128 (3)	C16^xiii—N11—Cu1	115.6 (2)
S2C^iv—S1C—S2C^vi	82.7 (15)	C16—N11—Cu1	115.6 (2)
S1C^v—S1C—S2C^vi	48.9 (16)	C13—C14—C13^xiii	99.3 (4)
S2Cⁱⁱ—S1C—S2C^vii	82.7 (15)	C13—C14—C15^xiii	40.2 (2)
S2C—S1C—S2C^vii	30 (3)	C13^xiii—C14—C15^xiii	117.1 (3)
S2Cⁱⁱⁱ—S1C—S2C^vii	82.7 (15)	C13—C14—C15	117.1 (3)
S2C^iv—S1C—S2C^vii	128 (3)	C13^xiii—C14—C15	40.2 (2)
S1C^v—S1C—S2C^vii	48.9 (16)	C15^xiii—C14—C15	106.1 (4)
S2C^vi—S1C—S2C^vii	64.4 (17)	C13—C14—C21	123.7 (2)
S2Cⁱⁱ—S1C—S2C^v	82.7 (15)	C13^xiii—C14—C21	123.7 (2)
S2C—S1C—S2C^v	128 (3)	C15^xiii—C14—C21	119.3 (2)
S2Cⁱⁱⁱ—S1C—S2C^v	82.7 (15)	C15—C14—C21	119.3 (2)
S2C^iv—S1C—S2C^v	30 (3)	C22—C21—C22^xiii	59.8 (4)
S1C^v—S1C—S2C^v	48.9 (16)	C22—C21—C26	118.1 (3)
S2C^vi—S1C—S2C^v	64.4 (17)	C22^xiii—C21—C26	87.4 (3)
S2C^vii—S1C—S2C^v	98 (3)	C22—C21—C26^xiii	87.4 (3)
S2Cⁱⁱ—S1C—S2C^viii	128 (3)	C22^xiii—C21—C26^xiii	118.1 (3)
S2C—S1C—S2C^viii	82.7 (15)	C26—C21—C26^xiii	62.3 (4)
S2Cⁱⁱⁱ—S1C—S2C^viii	30 (3)	C22—C21—C14	122.3 (2)
S2C^iv—S1C—S2C^viii	82.7 (15)	C22^xiii—C21—C14	122.3 (2)
S1C^v—S1C—S2C^viii	48.9 (16)	C26—C21—C14	119.6 (2)
S2C^vi—S1C—S2C^viii	98 (3)	C26^xiii—C21—C14	119.6 (2)
S2C^vii—S1C—S2C^viii	64.4 (17)	C25—C24—C25^xiii	62.4 (3)
S2C^v—S1C—S2C^viii	64.4 (17)	C25—C24—C23	118.1 (3)
S2C^vii—S2C—S1C	101 (2)	C25^xiii—C24—C23	86.6 (3)
S2C^vii—S2C—S1C^v	48.9 (16)	C25—C24—C23^xiii	86.6 (3)
S1C—S2C—S1C^v	52 (3)	C25^xiii—C24—C23^xiii	118.1 (3)
S1D^v—S2D—S1D	180.0	C23—C24—C23^xiii	61.8 (4)
C24^ix—C30—C24	109.82 (18)	C25—C24—C30	120.6 (2)
C24^ix—C30—C24^x	109.30 (9)	C25^xiii—C24—C30	120.6 (2)
C24—C30—C24^x	109.30 (9)	C23—C24—C30	121.2 (2)
C24^ix—C30—C24^xi	109.30 (9)	C23^xiii—C24—C30	121.2 (2)
C24—C30—C24^xi	109.30 (9)	N11—C12—C13	123.7 (4)
C24^x—C30—C24^xi	109.82 (18)	C14—C13—C12	120.5 (4)
N11^vii—Cu1—N11	104.31 (14)	C16—C15—C14	118.7 (4)
N11^vii—Cu1—Cu1^xii	127.85 (7)	N11—C16—C15	122.3 (4)
N11—Cu1—Cu1^xii	127.85 (7)	C21—C22—C23	121.5 (4)
N11^vii—Cu1—I1^xii	106.77 (3)	C22—C23—C24	120.2 (3)
N11—Cu1—I1^xii	106.77 (3)	C26—C25—C24	121.9 (3)
Cu1^xii—Cu1—I1^xii	61.948 (9)	C25—C26—C21	120.1 (3)

Symmetry codes: (i) x, −y, −z+1/2; (ii) y, −x, z; (iii) −y, x, z; (iv) −x, −y, z; (v) −x, −y, −z; (vi) y, −x, −z; (vii) x, y, −z; (viii) −y, x, −z; (ix) −x, −y−1, z; (x) −x, y, −z+1/2; (xi) x, −y−1, −z+1/2; (xii) −x+1, −y, −z; (xiii) y+1/2, x−1/2, z.

(250K_S_helical_initial) top

Crystal data top

(CuI)_1.88(N1C5H4C6H₄)4C(S₂)_0.63(S₃)_0.58	D_x = 1.403 Mg m⁻³
M_r = 1083.02	Synchrotron radiation, λ = 0.800 Å
Tetragonal, P4	Cell parameters from 91118 reflections
a = 26.7176 (5) Å	θ = 2.7–26.4°
c = 7.1942 (2) Å	µ = 2.71 mm⁻¹
V = 5135.4 (2) Å³	T = 250 K
Z = 4	Needle, brownish yellow
F(000) = 2133	0.76 × 0.05 × 0.05 mm

Data collection top

ADSC Q210 CCD area detector diffractometer	7133 independent reflections
Radiation source: PLSII 2D bending magnet	4892 reflections with I > 2σ(I)
Si(111) double crystal monochromator	R_int = 0.075
ω scan	θ_max = 26.4°, θ_min = 2.7°
Absorption correction: multi-scan [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38]	h = −29→29
T_min = 0.620, T_max = 0.669	k = −29→29
91118 measured reflections	l = −7→7

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.068	H-atom parameters constrained
wR(F²) = 0.235	w = 1/[σ²(F_o²) + (0.1773P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.014
7133 reflections	Δρ_max = 0.32 e Å⁻³
750 parameters	Δρ_min = −0.48 e Å⁻³
1237 restraints	Absolute structure: Flack x determined using 1921 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.051 (19)

Special details top

Refinement. Refined as a 2-component twin.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1A	0.5926 (19)	0.730 (2)	1.079 (5)	0.27 (2)	0.252 (11)
S2A	0.565 (2)	0.7149 (19)	1.323 (4)	0.28 (2)	0.252 (11)
S3A	0.557 (4)	0.774 (2)	1.473 (8)	0.38 (4)	0.252 (11)
S1B	0.531 (2)	0.755 (3)	1.117 (5)	0.26 (3)	0.155 (11)
S2B	0.514 (3)	0.752 (3)	0.863 (6)	0.27 (3)	0.155 (11)
S1C	0.545 (3)	0.728 (3)	0.528 (7)	0.34 (4)	0.153 (14)
S2C	0.522 (3)	0.776 (4)	0.711 (12)	0.34 (4)	0.153 (14)
S3C	0.573 (4)	0.798 (3)	0.877 (11)	0.35 (5)	0.153 (14)
S4A	0.958 (3)	0.780 (3)	1.344 (6)	0.23 (3)	0.087 (12)
S5A	0.904 (4)	0.785 (5)	1.514 (9)	0.28 (3)	0.087 (12)
S4B	0.961 (3)	0.777 (2)	1.956 (4)	0.30 (3)	0.197 (16)
S5B	0.935 (3)	0.782 (2)	1.711 (5)	0.30 (3)	0.197 (16)
S4C	0.956 (3)	0.723 (3)	0.949 (6)	0.29 (4)	0.191 (15)
S5C	0.979 (2)	0.735 (2)	1.194 (4)	0.23 (2)	0.191 (15)
S4D	0.916 (3)	0.755 (3)	1.743 (10)	0.33 (3)	0.172 (13)
S5D	0.928 (2)	0.724 (4)	1.501 (8)	0.33 (3)	0.172 (13)
S6D	0.996 (2)	0.738 (3)	1.424 (6)	0.25 (3)	0.172 (13)
Cu1	0.75493 (12)	0.69946 (11)	0.3655 (5)	0.1459 (9)	0.9381
Cu2	0.74986 (12)	0.79527 (11)	0.8663 (5)	0.1478 (9)	0.9381
I1	0.69666 (6)	0.74214 (7)	0.6263 (3)	0.1463 (6)	0.9381
I2	0.80722 (6)	0.75361 (7)	0.1270 (3)	0.1512 (6)	0.9381
C91	1.0000	1.0000	0.0000	0.097 (7)
C92	1.0000	0.5000	1.279 (3)	0.131 (10)
C93	0.5000	0.5000	−0.5000	0.106 (8)
N11	0.7072 (8)	0.6593 (8)	0.214 (3)	0.171 (8)
C12	0.7161 (9)	0.6478 (11)	0.040 (4)	0.165 (9)
H12	0.7471	0.6581	−0.0091	0.198*
C13	0.6841 (8)	0.6219 (8)	−0.081 (2)	0.137 (6)
H13	0.6921	0.6172	−0.2070	0.164*
C14	0.6396 (7)	0.6034 (8)	−0.005 (3)	0.128 (5)
C15	0.6284 (9)	0.6122 (10)	0.173 (2)	0.159 (8)
H15	0.5994	0.5990	0.2286	0.191*
C16	0.6637 (10)	0.6434 (10)	0.278 (2)	0.171 (9)
H16	0.6547	0.6528	0.3999	0.205*
N31A	0.8073 (7)	0.6622 (7)	0.5166 (19)	0.134 (5)	0.442 (14)
C32A	0.8281 (18)	0.6206 (15)	0.461 (5)	0.155 (11)	0.442 (14)
H32A	0.8197	0.6071	0.3443	0.186*	0.442 (14)
C33A	0.863 (2)	0.5962 (17)	0.573 (5)	0.160 (12)	0.442 (14)
H33A	0.8806	0.5692	0.5221	0.192*	0.442 (14)
C34A	0.8717 (8)	0.6097 (7)	0.757 (3)	0.126 (5)	0.442 (14)
C35A	0.8542 (18)	0.6553 (13)	0.812 (4)	0.131 (11)	0.442 (14)
H35A	0.8599	0.6687	0.9312	0.157*	0.442 (14)
C36A	0.8258 (17)	0.6813 (11)	0.668 (4)	0.120 (10)	0.442 (14)
H36A	0.8203	0.7157	0.6867	0.144*	0.442 (14)
N31B	0.8073 (7)	0.6622 (7)	0.5166 (19)	0.134 (5)	0.558 (14)
C32B	0.7997 (13)	0.6153 (10)	0.559 (4)	0.146 (10)	0.558 (14)
H32B	0.7700	0.6000	0.5189	0.175*	0.558 (14)
C33B	0.8335 (13)	0.5871 (11)	0.661 (5)	0.151 (10)	0.558 (14)
H33B	0.8302	0.5521	0.6644	0.182*	0.558 (14)
C34B	0.8717 (8)	0.6097 (7)	0.757 (3)	0.126 (5)	0.558 (14)
C35B	0.8769 (16)	0.6594 (10)	0.739 (6)	0.143 (10)	0.558 (14)
H35B	0.8964	0.6791	0.8190	0.171*	0.558 (14)
C36B	0.8495 (11)	0.6797 (13)	0.582 (4)	0.144 (10)	0.558 (14)
H36B	0.8632	0.7078	0.5224	0.173*	0.558 (14)
N51A	0.6995 (8)	0.8324 (7)	1.010 (2)	0.158 (6)	0.442 (14)
C52A	0.7063 (16)	0.8818 (11)	1.034 (5)	0.141 (11)	0.442 (14)
H52A	0.7321	0.8978	0.9679	0.169*	0.442 (14)
C53A	0.6757 (16)	0.9106 (14)	1.154 (7)	0.155 (11)	0.442 (14)
H53A	0.6841	0.9440	1.1796	0.186*	0.442 (14)
C54A	0.6326 (9)	0.8892 (7)	1.235 (3)	0.144 (6)	0.442 (14)
C55A	0.6280 (18)	0.8389 (10)	1.228 (6)	0.133 (11)	0.442 (14)
H55A	0.6097	0.8199	1.3144	0.160*	0.442 (14)
C56A	0.6555 (14)	0.8175 (14)	1.068 (5)	0.151 (11)	0.442 (14)
H56A	0.6401	0.7911	1.0028	0.181*	0.442 (14)
N51B	0.6995 (8)	0.8324 (7)	1.010 (2)	0.158 (6)	0.558 (14)
C52B	0.6767 (16)	0.8731 (13)	0.952 (4)	0.155 (10)	0.558 (14)
H52B	0.6836	0.8829	0.8292	0.185*	0.558 (14)
C53B	0.6431 (15)	0.9038 (13)	1.051 (3)	0.146 (10)	0.558 (14)
H53B	0.6286	0.9324	0.9972	0.175*	0.558 (14)
C54B	0.6326 (9)	0.8892 (7)	1.235 (3)	0.144 (6)	0.558 (14)
C55B	0.6506 (15)	0.8443 (10)	1.290 (3)	0.121 (9)	0.558 (14)
H55B	0.6423	0.8321	1.4090	0.146*	0.558 (14)
C56B	0.6828 (13)	0.8145 (10)	1.169 (4)	0.130 (9)	0.558 (14)
H56B	0.6916	0.7819	1.2048	0.155*	0.558 (14)
N71	0.7956 (8)	0.8406 (8)	0.720 (2)	0.148 (6)
C72	0.8405 (8)	0.8560 (9)	0.774 (2)	0.152 (8)
H72	0.8522	0.8452	0.8907	0.182*
C73	0.8711 (8)	0.8870 (8)	0.671 (2)	0.132 (6)
H73	0.8988	0.9023	0.7278	0.158*
C74	0.8615 (8)	0.8959 (8)	0.483 (2)	0.131 (6)
C75	0.8195 (7)	0.8738 (9)	0.411 (2)	0.144 (7)
H75	0.8114	0.8763	0.2840	0.173*
C76	0.7880 (10)	0.8460 (10)	0.541 (3)	0.160 (9)
H76	0.7594	0.8305	0.4918	0.191*
C41A	0.9031 (8)	0.5823 (8)	0.886 (3)	0.149 (7)
C42A	0.9093 (8)	0.5299 (8)	0.879 (3)	0.144 (6)
H42A	0.8931	0.5110	0.7868	0.173*
C43A	0.9399 (9)	0.5064 (8)	1.011 (3)	0.150 (7)
H43A	0.9423	0.4713	1.0081	0.180*
C44A	0.9666 (8)	0.5320 (9)	1.145 (3)	0.149 (7)
C45A	0.9599 (8)	0.5836 (8)	1.156 (2)	0.139 (6)
H45A	0.9765	0.6023	1.2473	0.167*
C46A	0.9281 (10)	0.6073 (9)	1.028 (3)	0.182 (10)
H46A	0.9233	0.6421	1.0385	0.218*
C61A	0.5973 (9)	0.9169 (7)	1.362 (3)	0.143 (5)	0.442 (14)
C62A	0.5644 (17)	0.8909 (11)	1.480 (6)	0.128 (12)	0.442 (14)
H62A	0.5644	0.8557	1.4843	0.154*	0.442 (14)
C63A	0.5314 (17)	0.9193 (10)	1.592 (5)	0.131 (12)	0.442 (14)
H63A	0.5049	0.9030	1.6524	0.157*	0.442 (14)
C64A	0.5371 (9)	0.9701 (7)	1.614 (3)	0.147 (6)	0.442 (14)
C65A	0.569 (3)	0.9962 (13)	1.494 (9)	0.154 (14)	0.442 (14)
H65A	0.5712	1.0313	1.4991	0.185*	0.442 (14)
C66A	0.599 (3)	0.9693 (10)	1.365 (9)	0.148 (14)	0.442 (14)
H66A	0.6198	0.9866	1.2815	0.178*	0.442 (14)
C81A	0.8943 (5)	0.9241 (6)	0.374 (2)	0.112 (4)
C82A	0.9466 (6)	0.9191 (7)	0.396 (2)	0.121 (5)
H82A	0.9596	0.8986	0.4905	0.146*
C83A	0.9791 (6)	0.9449 (7)	0.277 (2)	0.119 (5)
H83A	1.0137	0.9435	0.2986	0.143*
C84A	0.9614 (6)	0.9726 (7)	0.126 (2)	0.116 (4)
C85A	0.9091 (6)	0.9814 (8)	0.116 (2)	0.125 (5)
H85A	0.8963	1.0057	0.0334	0.150*
C86A	0.8769 (7)	0.9539 (8)	0.228 (2)	0.125 (5)
H86A	0.8423	0.9554	0.2047	0.149*
C21B	0.6064 (6)	0.5745 (6)	−0.128 (3)	0.129 (5)
C22B	0.6241 (7)	0.5434 (7)	−0.271 (3)	0.122 (5)
H22B	0.6587	0.5384	−0.2854	0.147*
C23B	0.5908 (6)	0.5199 (6)	−0.3940 (18)	0.103 (4)
H23B	0.6037	0.5000	−0.4904	0.123*
C24B	0.5403 (5)	0.5251 (5)	−0.378 (2)	0.103 (4)
C25B	0.5220 (7)	0.5551 (6)	−0.2298 (19)	0.108 (4)
H25B	0.4873	0.5585	−0.2128	0.130*
C26B	0.5552 (6)	0.5801 (6)	−0.107 (2)	0.113 (4)
H26B	0.5424	0.6006	−0.0122	0.136*
C61B	0.5973 (9)	0.9169 (7)	1.362 (3)	0.143 (5)	0.558 (14)
C62B	0.5880 (19)	0.9687 (10)	1.335 (6)	0.141 (12)	0.558 (14)
H62B	0.6026	0.9860	1.2348	0.169*	0.558 (14)
C63B	0.5565 (18)	0.9932 (12)	1.461 (5)	0.137 (12)	0.558 (14)
H63B	0.5484	1.0270	1.4388	0.165*	0.558 (14)
C64B	0.5371 (9)	0.9701 (7)	1.614 (3)	0.147 (6)	0.558 (14)
C65B	0.5450 (17)	0.9181 (10)	1.641 (6)	0.148 (12)	0.558 (14)
H65B	0.5274	0.9004	1.7327	0.177*	0.558 (14)
C66B	0.5807 (16)	0.8933 (12)	1.523 (4)	0.131 (11)	0.558 (14)
H66B	0.5928	0.8614	1.5546	0.157*	0.558 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.28 (4)	0.37 (5)	0.15 (3)	0.02 (4)	0.06 (3)	−0.01 (3)
S2A	0.42 (6)	0.33 (5)	0.090 (16)	−0.06 (4)	0.01 (2)	0.02 (2)
S3A	0.51 (9)	0.44 (9)	0.20 (5)	−0.05 (7)	0.08 (5)	0.06 (5)
S1B	0.36 (6)	0.30 (5)	0.12 (3)	−0.01 (5)	0.14 (3)	0.01 (3)
S2B	0.42 (7)	0.30 (6)	0.10 (2)	−0.09 (5)	0.04 (4)	−0.08 (3)
S1C	0.44 (8)	0.44 (9)	0.14 (3)	−0.21 (7)	0.21 (4)	−0.08 (4)
S2C	0.46 (8)	0.30 (7)	0.27 (6)	−0.09 (6)	0.03 (7)	−0.04 (6)
S3C	0.56 (11)	0.23 (6)	0.26 (7)	0.02 (6)	−0.12 (7)	−0.14 (5)
S4A	0.43 (7)	0.22 (5)	0.04 (2)	0.03 (5)	0.03 (3)	−0.06 (3)
S5A	0.47 (7)	0.30 (6)	0.09 (3)	−0.04 (6)	0.15 (4)	0.03 (4)
S4B	0.57 (9)	0.26 (5)	0.055 (14)	−0.12 (5)	−0.01 (3)	−0.06 (2)
S5B	0.49 (7)	0.25 (4)	0.15 (3)	−0.07 (5)	0.13 (4)	0.01 (3)
S4C	0.35 (7)	0.38 (8)	0.13 (3)	0.11 (6)	−0.07 (4)	0.03 (4)
S5C	0.35 (5)	0.26 (4)	0.072 (16)	0.01 (4)	0.06 (2)	−0.04 (2)
S4D	0.39 (6)	0.34 (7)	0.25 (4)	0.05 (5)	0.23 (4)	0.00 (5)
S5D	0.41 (6)	0.37 (6)	0.19 (4)	0.04 (5)	0.14 (4)	0.05 (4)
S6D	0.35 (6)	0.26 (5)	0.13 (3)	0.00 (4)	0.08 (3)	0.06 (3)
Cu1	0.1647 (18)	0.1611 (18)	0.1120 (15)	−0.0438 (16)	−0.0198 (18)	0.002 (2)
Cu2	0.179 (2)	0.1513 (17)	0.1134 (16)	−0.0439 (17)	0.0076 (19)	0.006 (2)
I1	0.1695 (11)	0.1606 (11)	0.1088 (8)	−0.0468 (9)	−0.0091 (11)	−0.0003 (10)
I2	0.1627 (11)	0.1691 (12)	0.1220 (9)	−0.0506 (9)	−0.0092 (12)	0.0148 (10)
C91	0.105 (11)	0.105 (11)	0.079 (16)	0.000	0.000	0.000
C92	0.20 (3)	0.126 (18)	0.065 (11)	0.035 (14)	0.000	0.000
C93	0.126 (13)	0.126 (13)	0.067 (15)	0.000	0.000	0.000
N11	0.195 (18)	0.136 (13)	0.181 (17)	−0.044 (12)	−0.032 (16)	0.030 (13)
C12	0.159 (17)	0.174 (19)	0.161 (19)	−0.062 (15)	0.008 (16)	−0.014 (16)
C13	0.166 (15)	0.150 (14)	0.095 (11)	−0.031 (12)	0.026 (10)	−0.021 (10)
C14	0.107 (10)	0.129 (12)	0.147 (15)	−0.013 (9)	0.022 (11)	−0.007 (11)
C15	0.172 (17)	0.212 (19)	0.095 (12)	−0.087 (15)	0.034 (11)	−0.020 (12)
C16	0.23 (2)	0.20 (2)	0.082 (10)	−0.095 (18)	0.029 (12)	0.012 (12)
N31A	0.156 (12)	0.178 (12)	0.067 (7)	−0.044 (10)	−0.005 (7)	0.011 (8)
C32A	0.16 (2)	0.18 (2)	0.12 (2)	−0.01 (2)	0.00 (2)	0.00 (2)
C33A	0.16 (2)	0.18 (2)	0.15 (2)	0.01 (2)	−0.03 (2)	0.01 (2)
C34A	0.137 (11)	0.159 (12)	0.082 (8)	−0.006 (11)	−0.026 (8)	−0.003 (9)
C35A	0.14 (2)	0.17 (2)	0.085 (18)	0.00 (2)	−0.019 (18)	0.034 (18)
C36A	0.17 (2)	0.114 (17)	0.078 (17)	−0.005 (18)	−0.052 (17)	0.035 (15)
N31B	0.156 (12)	0.178 (12)	0.067 (7)	−0.044 (10)	−0.005 (7)	0.011 (8)
C32B	0.18 (2)	0.18 (2)	0.083 (16)	0.00 (2)	−0.014 (16)	−0.040 (16)
C33B	0.17 (2)	0.18 (2)	0.109 (19)	−0.01 (2)	0.013 (18)	−0.021 (18)
C34B	0.137 (11)	0.159 (12)	0.082 (8)	−0.006 (11)	−0.026 (8)	−0.003 (9)
C35B	0.14 (2)	0.18 (2)	0.103 (18)	−0.016 (19)	−0.030 (17)	0.033 (18)
C36B	0.16 (2)	0.19 (2)	0.084 (17)	−0.011 (18)	0.015 (16)	0.012 (17)
N51A	0.216 (15)	0.154 (11)	0.104 (10)	−0.047 (11)	−0.016 (10)	0.028 (9)
C52A	0.19 (2)	0.18 (2)	0.051 (15)	−0.05 (2)	0.033 (18)	0.011 (17)
C53A	0.15 (2)	0.20 (2)	0.11 (2)	−0.05 (2)	0.03 (2)	0.00 (2)
C54A	0.185 (14)	0.151 (12)	0.095 (10)	0.008 (12)	0.015 (10)	0.000 (10)
C55A	0.21 (3)	0.115 (19)	0.072 (18)	0.02 (2)	0.00 (2)	0.009 (16)
C56A	0.21 (2)	0.16 (2)	0.081 (18)	0.00 (2)	0.038 (18)	0.021 (18)
N51B	0.216 (15)	0.154 (11)	0.104 (10)	−0.047 (11)	−0.016 (10)	0.028 (9)
C52B	0.22 (2)	0.20 (2)	0.035 (11)	−0.03 (2)	0.024 (14)	0.061 (14)
C53B	0.20 (2)	0.18 (2)	0.054 (12)	0.011 (19)	0.001 (14)	0.077 (13)
C54B	0.185 (14)	0.151 (12)	0.095 (10)	0.008 (12)	0.015 (10)	0.000 (10)
C55B	0.20 (2)	0.114 (16)	0.048 (12)	0.007 (16)	−0.001 (14)	0.047 (11)
C56B	0.157 (19)	0.126 (16)	0.106 (17)	0.059 (15)	−0.005 (16)	−0.012 (14)
N71	0.201 (17)	0.156 (13)	0.085 (9)	−0.026 (12)	−0.055 (10)	0.003 (9)
C72	0.186 (18)	0.180 (17)	0.089 (10)	−0.074 (14)	0.055 (11)	−0.033 (12)
C73	0.169 (15)	0.138 (12)	0.088 (11)	−0.047 (12)	−0.007 (10)	−0.003 (9)
C74	0.153 (14)	0.145 (14)	0.094 (10)	−0.012 (12)	0.012 (10)	−0.007 (10)
C75	0.151 (14)	0.179 (17)	0.101 (11)	−0.046 (13)	0.017 (11)	−0.023 (11)
C76	0.22 (2)	0.156 (16)	0.106 (13)	−0.075 (16)	−0.007 (13)	−0.009 (11)
C41A	0.132 (12)	0.197 (17)	0.119 (13)	−0.006 (12)	0.002 (12)	0.041 (14)
C42A	0.147 (14)	0.157 (15)	0.129 (14)	0.030 (11)	−0.031 (14)	−0.029 (14)
C43A	0.159 (17)	0.145 (16)	0.146 (17)	0.044 (13)	0.011 (14)	0.020 (13)
C44A	0.135 (13)	0.212 (19)	0.101 (11)	−0.016 (13)	0.004 (11)	−0.032 (14)
C45A	0.186 (17)	0.174 (15)	0.058 (7)	−0.018 (13)	−0.011 (9)	−0.017 (9)
C46A	0.176 (18)	0.23 (2)	0.136 (17)	−0.015 (16)	−0.095 (15)	−0.021 (16)
C61A	0.181 (13)	0.145 (11)	0.102 (10)	−0.014 (11)	0.017 (11)	0.032 (10)
C62A	0.18 (3)	0.100 (19)	0.10 (2)	−0.015 (19)	−0.03 (2)	0.005 (17)
C63A	0.19 (3)	0.14 (2)	0.057 (16)	0.00 (2)	0.005 (19)	0.014 (16)
C64A	0.175 (14)	0.145 (12)	0.120 (12)	0.023 (11)	0.035 (12)	−0.012 (12)
C65A	0.16 (3)	0.18 (2)	0.12 (2)	0.01 (2)	0.04 (2)	0.02 (2)
C66A	0.19 (3)	0.17 (2)	0.09 (2)	0.00 (2)	0.04 (2)	0.03 (2)
C81A	0.113 (9)	0.139 (11)	0.086 (8)	−0.023 (8)	−0.016 (8)	0.026 (9)
C82A	0.142 (12)	0.146 (12)	0.077 (9)	−0.017 (9)	−0.006 (9)	−0.005 (9)
C83A	0.110 (10)	0.157 (14)	0.090 (10)	−0.004 (10)	−0.002 (8)	0.032 (10)
C84A	0.131 (11)	0.155 (12)	0.062 (7)	−0.014 (9)	−0.012 (8)	0.016 (9)
C85A	0.120 (11)	0.156 (12)	0.099 (10)	−0.006 (9)	−0.003 (10)	0.011 (11)
C86A	0.128 (11)	0.173 (15)	0.073 (8)	−0.010 (11)	−0.008 (8)	0.021 (9)
C21B	0.133 (12)	0.140 (12)	0.114 (11)	−0.033 (10)	−0.029 (11)	0.043 (11)
C22B	0.119 (11)	0.133 (12)	0.114 (12)	−0.008 (10)	−0.015 (10)	0.003 (10)
C23B	0.125 (10)	0.124 (9)	0.060 (7)	−0.006 (8)	0.015 (7)	−0.003 (7)
C24B	0.133 (11)	0.100 (8)	0.077 (8)	−0.011 (7)	−0.026 (9)	0.010 (8)
C25B	0.140 (12)	0.123 (11)	0.062 (7)	0.007 (9)	−0.002 (8)	−0.002 (7)
C26B	0.140 (11)	0.128 (10)	0.072 (8)	−0.022 (8)	0.003 (9)	−0.021 (8)
C61B	0.181 (13)	0.145 (11)	0.102 (10)	−0.014 (11)	0.017 (11)	0.032 (10)
C62B	0.16 (2)	0.16 (2)	0.10 (2)	−0.011 (18)	0.008 (19)	0.030 (17)
C63B	0.15 (2)	0.15 (2)	0.104 (19)	0.011 (18)	0.020 (18)	0.027 (16)
C64B	0.175 (14)	0.145 (12)	0.120 (12)	0.023 (11)	0.035 (12)	−0.012 (12)
C65B	0.18 (2)	0.146 (19)	0.12 (2)	0.016 (19)	0.01 (2)	−0.024 (19)
C66B	0.22 (3)	0.111 (17)	0.059 (14)	0.001 (18)	0.007 (18)	0.004 (12)

Geometric parameters (Å, º) top

S1A—S2A	1.95 (2)	C35A—C36A	1.46 (3)
S2A—S3A	1.91 (2)	C32B—C33B	1.38 (3)
S1B—S2B	1.89 (3)	C35B—C36B	1.45 (3)
S1C—S2C	1.94 (2)	N51A—C56A	1.31 (3)
S2C—S3C	1.92 (2)	N51A—C52A	1.34 (3)
S4A—S5A	1.90 (3)	C52A—C53A	1.42 (3)
S4B—S5B	1.90 (3)	C53A—C54A	1.41 (2)
S4C—S5C	1.90 (3)	C54A—C55A	1.35 (3)
S4D—S5D	1.95 (3)	C54A—C61A	1.51 (3)
S5D—S6D	1.92 (3)	C55A—C56A	1.48 (3)
Cu1—N11	1.99 (2)	C52B—C53B	1.41 (3)
Cu1—N31A	2.033 (17)	C55B—C56B	1.46 (2)
Cu1—I2	2.644 (3)	N71—C76	1.309 (19)
Cu1—I1	2.692 (4)	N71—C72	1.33 (2)
Cu2—N51A	1.97 (2)	C72—C73	1.38 (2)
Cu2—N71	2.017 (19)	C73—C74	1.393 (19)
Cu2—I1	2.649 (3)	C74—C75	1.37 (2)
Cu2—I2ⁱ	2.666 (4)	C74—C81A	1.40 (2)
I2—Cu2ⁱⁱ	2.666 (4)	C75—C76	1.46 (2)
C91—C84A	1.556 (15)	C41A—C46A	1.39 (2)
C91—C84Aⁱⁱⁱ	1.556 (15)	C41A—C42A	1.41 (2)
C91—C84A^iv	1.556 (15)	C42A—C43A	1.40 (2)
C91—C84A^v	1.556 (15)	C43A—C44A	1.38 (2)
C92—C64B^vi	1.49 (2)	C44A—C45A	1.39 (2)
C92—C64A^vi	1.49 (2)	C45A—C46A	1.41 (2)
C92—C64B^vii	1.49 (2)	C61A—C66A	1.40 (2)
C92—C64A^vii	1.49 (2)	C61A—C62A	1.41 (3)
C92—C44A^viii	1.57 (2)	C62A—C63A	1.41 (3)
C92—C44A	1.57 (2)	C63A—C64A	1.37 (2)
C93—C24B^ix	1.543 (13)	C64A—C65A	1.41 (2)
C93—C24B^x	1.543 (13)	C64A—C92^xii	1.49 (2)
C93—C24B^xi	1.543 (13)	C65A—C66A	1.41 (3)
C93—C24B	1.543 (13)	C81A—C86A	1.400 (17)
N11—C12	1.31 (2)	C81A—C82A	1.412 (19)
N11—C16	1.32 (2)	C82A—C83A	1.401 (19)
C12—C13	1.40 (2)	C83A—C84A	1.394 (17)
C13—C14	1.399 (19)	C84A—C85A	1.419 (18)
C14—C15	1.34 (2)	C85A—C86A	1.39 (2)
C14—C21B	1.47 (3)	C21B—C26B	1.383 (18)
C15—C16	1.47 (2)	C21B—C22B	1.41 (2)
N31A—C36A	1.30 (2)	C22B—C23B	1.402 (19)
N31A—C32A	1.31 (3)	C23B—C24B	1.362 (16)
C32A—C33A	1.39 (3)	C24B—C25B	1.419 (17)
C33A—C34A	1.40 (3)	C25B—C26B	1.418 (18)
C34A—C35A	1.36 (3)	C62B—C63B	1.40 (3)
C34A—C41A	1.45 (3)	C65B—C66B	1.44 (3)

S3A—S2A—S1A	112 (3)	C52A—N51A—Cu2	117.9 (18)
S3C—S2C—S1C	113 (3)	N51A—C52A—C53A	122 (2)
S6D—S5D—S4D	110 (3)	C54A—C53A—C52A	120 (3)
N11—Cu1—N31A	118.0 (8)	C55A—C54A—C53A	117 (2)
N11—Cu1—I2	106.2 (6)	C55A—C54A—C61A	117 (2)
N31A—Cu1—I2	104.5 (5)	C53A—C54A—C61A	124 (2)
N11—Cu1—I1	103.8 (7)	C54A—C55A—C56A	112 (3)
N31A—Cu1—I1	103.5 (5)	N51A—C56A—C55A	125 (3)
I2—Cu1—I1	121.75 (12)	C76—N71—C72	113 (2)
N51A—Cu2—N71	112.8 (8)	C76—N71—Cu2	119.0 (15)
N51A—Cu2—I1	104.3 (6)	C72—N71—Cu2	125.5 (12)
N71—Cu2—I1	107.9 (4)	N71—C72—C73	124.2 (19)
N51A—Cu2—I2ⁱ	103.5 (6)	C72—C73—C74	121.1 (16)
N71—Cu2—I2ⁱ	105.6 (5)	C75—C74—C81A	122.1 (15)
I1—Cu2—I2ⁱ	122.91 (12)	C75—C74—C73	116.4 (18)
Cu2—I1—Cu1	111.77 (9)	C81A—C74—C73	121.4 (16)
Cu1—I2—Cu2ⁱⁱ	112.42 (9)	C74—C75—C76	116.4 (16)
C84A—C91—C84Aⁱⁱⁱ	108.8 (12)	N71—C76—C75	126.7 (19)
C84A—C91—C84A^iv	109.8 (6)	C46A—C41A—C42A	116.5 (18)
C84Aⁱⁱⁱ—C91—C84A^iv	109.8 (6)	C46A—C41A—C34A	120.2 (19)
C84A—C91—C84A^v	109.8 (6)	C42A—C41A—C34A	123.2 (18)
C84Aⁱⁱⁱ—C91—C84A^v	109.8 (6)	C43A—C42A—C41A	119.4 (17)
C84A^iv—C91—C84A^v	108.8 (12)	C44A—C43A—C42A	123.5 (19)
C64B^vi—C92—C64B^vii	118 (2)	C45A—C44A—C43A	117.5 (19)
C64A^vi—C92—C64A^vii	118 (2)	C45A—C44A—C92	125.3 (16)
C64A^vi—C92—C44A^viii	112.1 (10)	C43A—C44A—C92	117.0 (18)
C64A^vii—C92—C44A^viii	105.1 (12)	C44A—C45A—C46A	119.3 (17)
C64A^vi—C92—C44A	105.2 (12)	C41A—C46A—C45A	124 (2)
C64A^vii—C92—C44A	112.1 (10)	C66A—C61A—C62A	120 (2)
C44A^viii—C92—C44A	104 (2)	C66A—C61A—C54A	118.7 (19)
C24B^ix—C93—C24B^x	109.0 (6)	C62A—C61A—C54A	120.9 (19)
C24B^ix—C93—C24B^xi	110.4 (12)	C63A—C62A—C61A	118 (2)
C24B^x—C93—C24B^xi	109.0 (6)	C64A—C63A—C62A	122 (3)
C24B^ix—C93—C24B	109.0 (6)	C63A—C64A—C65A	119 (2)
C24B^x—C93—C24B	110.4 (12)	C63A—C64A—C92^xii	121.2 (19)
C24B^xi—C93—C24B	109.0 (6)	C65A—C64A—C92^xii	117 (2)
C12—N11—C16	115 (2)	C64A—C65A—C66A	120 (3)
C12—N11—Cu1	122.1 (17)	C61A—C66A—C65A	120 (3)
C16—N11—Cu1	123.1 (17)	C74—C81A—C86A	121.4 (15)
N11—C12—C13	127 (2)	C74—C81A—C82A	120.5 (15)
C14—C13—C12	116.7 (16)	C86A—C81A—C82A	117.8 (15)
C15—C14—C13	120.3 (19)	C83A—C82A—C81A	119.8 (15)
C15—C14—C21B	122.2 (16)	C82A—C83A—C84A	121.9 (15)
C13—C14—C21B	117.5 (16)	C83A—C84A—C85A	117.6 (15)
C14—C15—C16	116.7 (16)	C83A—C84A—C91	118.6 (12)
N11—C16—C15	124.5 (17)	C85A—C84A—C91	122.9 (12)
C36A—N31A—C32A	115 (2)	C86A—C85A—C84A	119.3 (16)
C36A—N31A—Cu1	121.1 (18)	C85A—C86A—C81A	122.2 (15)
C32A—N31A—Cu1	123.1 (17)	C26B—C21B—C22B	118.2 (16)
N31A—C32A—C33A	120 (3)	C26B—C21B—C14	118.4 (17)
C32A—C33A—C34A	123 (3)	C22B—C21B—C14	123.3 (15)
C35A—C34A—C33A	116 (2)	C23B—C22B—C21B	120.9 (15)
C35A—C34A—C41A	117.7 (18)	C24B—C23B—C22B	121.9 (14)
C33A—C34A—C41A	125 (2)	C23B—C24B—C25B	117.6 (13)
C34A—C35A—C36A	113 (2)	C23B—C24B—C93	126.7 (12)
N31A—C36A—C35A	127 (2)	C25B—C24B—C93	115.7 (11)
C56A—N51A—C52A	112 (2)	C26B—C25B—C24B	121.2 (14)
C56A—N51A—Cu2	128.9 (19)	C21B—C26B—C25B	120.1 (14)

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

(300K_S_helical) top

Crystal data top

(CuI)_1.88(N1C5H4C6H₄)4C(cycro⁻S₃)_0.62(bent⁻S₃)_0.39	D_x = 1.397 Mg m⁻³
M_r = 1083.34	Synchrotron radiation, λ = 0.800 Å
Tetragonal, I4	Cell parameters from 52191 reflections
a = 26.8758 (4) Å	θ = 2.7–28.1°
c = 7.1689 (1) Å	µ = 2.72 mm⁻¹
V = 5178.1 (2) Å³	T = 300 K
Z = 4	Needle, brownish yellow
F(000) = 2141	0.76 × 0.05 × 0.05 mm

Data collection top

ADSC Q210 CCD area detector diffractometer	4353 independent reflections
Radiation source: PLSII 2D bending magnet	3852 reflections with I > 2σ(I)
Si(111) double crystal monochromator	R_int = 0.035
ω scan	θ_max = 28.1°, θ_min = 2.7°
Absorption correction: multi-scan [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38]	h = −31→31
T_min = 0.587, T_max = 0.620	k = −31→31
52191 measured reflections	l = −8→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.0908P)² + 0.1257P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.086
4353 reflections	Δρ_max = 0.25 e Å⁻³
365 parameters	Δρ_min = −0.45 e Å⁻³
397 restraints	Absolute structure: Flack x determined using 1625 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.430 (7)

Special details top

Refinement. Refined as a 2-component twin.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1X	0.3957 (8)	0.239 (2)	0.660 (10)	0.30 (4)	0.166 (12)
S2X	0.457 (3)	0.284 (3)	0.622 (17)	0.47 (5)	0.166 (12)
S3X	0.4598 (11)	0.2278 (15)	0.818 (7)	0.187 (17)	0.166 (12)
S1B	0.479 (3)	0.250 (2)	0.417 (19)	0.47 (5)	0.193 (12)
S2B	0.480 (2)	0.255 (3)	0.152 (19)	0.47 (4)	0.193 (12)
S3B	0.419 (2)	0.247 (3)	0.022 (18)	0.49 (5)	0.193 (12)
S1A	0.485 (4)	0.228 (3)	0.65 (2)	0.47 (5)	0.143 (13)
S2A	0.435 (3)	0.220 (3)	0.42 (2)	0.46 (5)	0.143 (13)
S3A	0.489 (4)	0.278 (4)	0.41 (2)	0.46 (5)	0.143 (13)
I1	0.30489 (3)	0.24567 (4)	0.61605 (13)	0.1105 (3)	0.940 (9)
Cu1	0.25078 (6)	0.29817 (5)	0.3765 (2)	0.1081 (4)	0.940 (9)
C1	0.0000	0.5000	1.2500	0.081 (4)
C2	0.5000	0.5000	−0.5000	0.092 (5)
N1A	0.2026 (4)	0.3409 (4)	0.5329 (13)	0.109 (3)
C2A	0.1585 (7)	0.3554 (8)	0.470 (2)	0.151 (7)
H2AA	0.1490	0.3458	0.3503	0.181*
C3A	0.1263 (5)	0.3842 (6)	0.5738 (16)	0.123 (4)
H3AA	0.0971	0.3963	0.5210	0.147*
C4A	0.1378 (4)	0.3949 (4)	0.7562 (14)	0.093 (3)
C5A	0.1819 (5)	0.3770 (6)	0.8207 (18)	0.129 (5)
H5AA	0.1906	0.3827	0.9444	0.154*
C6A	0.2141 (5)	0.3507 (7)	0.7084 (17)	0.135 (6)
H6AA	0.2443	0.3398	0.7566	0.162*
C7A	0.1044 (3)	0.4239 (3)	0.8815 (13)	0.087 (2)
C8A	0.1218 (4)	0.4546 (4)	1.0209 (14)	0.095 (3)
H8AA	0.1559	0.4590	1.0346	0.115*
C9A	0.0894 (3)	0.4796 (4)	1.1428 (13)	0.091 (2)
H9AA	0.1022	0.4998	1.2364	0.109*
C10A	0.0385 (3)	0.4741 (3)	1.1240 (13)	0.083 (2)
C11A	0.0211 (4)	0.4434 (4)	0.9792 (13)	0.088 (2)
H11A	−0.0130	0.4395	0.9644	0.105*
C12A	0.0527 (4)	0.4186 (4)	0.8573 (13)	0.095 (2)
H12A	0.0400	0.3989	0.7619	0.114*
N1B	0.3031 (5)	0.3376 (4)	0.2311 (13)	0.110 (3)	0.651 (18)
C2B	0.3159 (10)	0.3202 (8)	0.069 (3)	0.128 (7)	0.651 (18)
H2BA	0.3025	0.2900	0.0304	0.153*	0.651 (18)
C3B	0.3488 (10)	0.3449 (7)	−0.048 (3)	0.113 (6)	0.651 (18)
H3BA	0.3584	0.3302	−0.1598	0.135*	0.651 (18)
C4B	0.3672 (4)	0.3902 (5)	−0.0014 (17)	0.104 (3)	0.651 (18)
C5B	0.3607 (10)	0.4034 (9)	0.184 (2)	0.125 (7)	0.651 (18)
H5BA	0.3788	0.4295	0.2361	0.150*	0.651 (18)
C6B	0.3272 (9)	0.3773 (8)	0.290 (3)	0.123 (7)	0.651 (18)
H6BA	0.3210	0.3883	0.4106	0.148*	0.651 (18)
C7B	0.4023 (4)	0.4170 (4)	−0.1266 (16)	0.098 (3)
C8B	0.4083 (4)	0.4682 (4)	−0.1078 (16)	0.103 (3)
H8BA	0.3911	0.4855	−0.0155	0.124*
C9B	0.4402 (4)	0.4934 (4)	−0.2286 (14)	0.098 (3)
H9BA	0.4445	0.5275	−0.2139	0.117*
C10B	0.4658 (4)	0.4691 (4)	−0.3703 (13)	0.094 (2)
C11B	0.4595 (4)	0.4179 (4)	−0.3882 (18)	0.107 (3)
H11B	0.4770	0.4002	−0.4782	0.129*
C12B	0.4269 (5)	0.3941 (5)	−0.2695 (18)	0.116 (4)
H12B	0.4212	0.3603	−0.2881	0.139*
N1Y	0.3031 (5)	0.3376 (4)	0.2311 (13)	0.110 (3)	0.349 (18)
C2Y	0.3427 (13)	0.3167 (11)	0.161 (6)	0.131 (11)	0.349 (18)
H2YA	0.3501	0.2843	0.1972	0.158*	0.349 (18)
C3Y	0.3744 (13)	0.3397 (9)	0.036 (6)	0.111 (8)	0.349 (18)
H3YA	0.3998	0.3221	−0.0217	0.133*	0.349 (18)
C4Y	0.3672 (4)	0.3902 (5)	−0.0014 (17)	0.104 (3)	0.349 (18)
C5Y	0.3267 (11)	0.4107 (10)	0.082 (5)	0.112 (9)	0.349 (18)
H5YA	0.3209	0.4446	0.0661	0.134*	0.349 (18)
C6Y	0.2939 (11)	0.3836 (10)	0.188 (5)	0.115 (9)	0.349 (18)
H6YA	0.2647	0.3984	0.2298	0.138*	0.349 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1X	0.093 (13)	0.32 (5)	0.48 (11)	0.069 (18)	−0.08 (4)	−0.04 (7)
S2X	0.30 (4)	0.27 (4)	0.85 (13)	0.03 (3)	0.09 (6)	0.30 (6)
S3X	0.120 (17)	0.18 (3)	0.27 (5)	0.033 (16)	−0.04 (2)	−0.02 (3)
S1B	0.28 (4)	0.21 (5)	0.91 (13)	0.02 (4)	0.11 (6)	0.23 (7)
S2B	0.28 (3)	0.23 (4)	0.90 (13)	0.02 (4)	0.08 (6)	0.19 (6)
S3B	0.25 (4)	0.25 (5)	0.95 (14)	0.04 (5)	0.07 (6)	0.21 (8)
S1A	0.26 (5)	0.28 (5)	0.86 (13)	0.05 (5)	0.09 (7)	0.26 (7)
S2A	0.22 (4)	0.22 (4)	0.93 (13)	0.03 (3)	0.08 (7)	0.15 (7)
S3A	0.26 (4)	0.23 (4)	0.87 (13)	−0.01 (4)	0.10 (6)	0.25 (6)
I1	0.1199 (5)	0.1261 (5)	0.0855 (4)	0.0212 (4)	0.0000 (5)	0.0066 (4)
Cu1	0.1228 (8)	0.1155 (7)	0.0859 (7)	0.0155 (8)	0.0232 (8)	0.0001 (9)
C1	0.092 (6)	0.092 (6)	0.058 (8)	0.000	0.000	0.000
C2	0.104 (8)	0.104 (8)	0.068 (11)	0.000	0.000	0.000
N1A	0.122 (7)	0.120 (7)	0.084 (5)	0.027 (5)	0.004 (5)	0.000 (5)
C2A	0.182 (15)	0.197 (16)	0.072 (6)	0.073 (13)	−0.013 (8)	−0.003 (9)
C3A	0.127 (8)	0.161 (10)	0.081 (7)	0.049 (8)	0.002 (6)	−0.016 (7)
C4A	0.108 (7)	0.101 (6)	0.070 (5)	0.010 (5)	−0.002 (5)	0.000 (5)
C5A	0.131 (10)	0.163 (11)	0.091 (7)	0.057 (9)	0.001 (6)	−0.020 (7)
C6A	0.130 (10)	0.191 (15)	0.085 (7)	0.058 (10)	−0.017 (6)	−0.022 (8)
C7A	0.097 (5)	0.104 (6)	0.061 (5)	0.014 (4)	0.008 (4)	−0.003 (5)
C8A	0.091 (5)	0.118 (7)	0.077 (5)	0.010 (5)	−0.001 (5)	−0.014 (5)
C9A	0.088 (5)	0.111 (6)	0.073 (6)	0.005 (4)	−0.001 (4)	−0.009 (4)
C10A	0.093 (5)	0.089 (5)	0.066 (5)	0.003 (4)	−0.001 (4)	−0.002 (4)
C11A	0.098 (6)	0.101 (6)	0.064 (5)	0.012 (4)	−0.004 (4)	−0.003 (4)
C12A	0.112 (6)	0.110 (6)	0.064 (5)	0.010 (5)	0.002 (4)	−0.010 (5)
N1B	0.140 (8)	0.114 (7)	0.076 (5)	0.016 (6)	0.014 (6)	0.004 (5)
C2B	0.146 (16)	0.134 (13)	0.102 (13)	−0.057 (12)	0.021 (11)	−0.035 (11)
C3B	0.135 (14)	0.125 (12)	0.078 (10)	−0.022 (11)	0.030 (10)	−0.030 (9)
C4B	0.121 (8)	0.110 (7)	0.082 (6)	−0.005 (6)	0.006 (6)	0.002 (5)
C5B	0.159 (15)	0.140 (13)	0.076 (9)	−0.036 (12)	0.024 (10)	−0.006 (9)
C6B	0.144 (15)	0.138 (14)	0.088 (11)	−0.031 (12)	0.024 (10)	−0.032 (10)
C7B	0.098 (5)	0.122 (7)	0.075 (6)	0.000 (5)	0.004 (6)	−0.003 (6)
C8B	0.121 (7)	0.117 (7)	0.071 (5)	0.002 (5)	0.011 (7)	−0.003 (6)
C9B	0.127 (8)	0.101 (7)	0.065 (5)	0.000 (5)	0.011 (5)	−0.004 (5)
C10B	0.118 (7)	0.109 (6)	0.055 (5)	−0.003 (5)	0.009 (5)	−0.001 (5)
C11B	0.124 (7)	0.114 (7)	0.084 (6)	−0.001 (6)	0.022 (7)	0.003 (7)
C12B	0.147 (10)	0.106 (7)	0.094 (7)	−0.001 (7)	0.019 (7)	−0.007 (6)
N1Y	0.140 (8)	0.114 (7)	0.076 (5)	0.016 (6)	0.014 (6)	0.004 (5)
C2Y	0.16 (2)	0.120 (19)	0.11 (2)	−0.028 (19)	0.01 (2)	−0.019 (19)
C3Y	0.110 (17)	0.121 (17)	0.102 (17)	−0.023 (15)	0.031 (15)	−0.001 (15)
C4Y	0.121 (8)	0.110 (7)	0.082 (6)	−0.005 (6)	0.006 (6)	0.002 (5)
C5Y	0.116 (16)	0.121 (16)	0.098 (18)	0.009 (15)	0.024 (15)	0.008 (15)
C6Y	0.085 (15)	0.16 (2)	0.102 (18)	0.029 (15)	0.045 (14)	−0.019 (17)

Geometric parameters (Å, º) top

S1X—S2X	2.08 (5)	C3A—C4A	1.373 (15)
S1X—S3X	2.08 (4)	C4A—C5A	1.359 (15)
S1X—I1	2.47 (2)	C4A—C7A	1.490 (13)
S2X—S3X	2.07 (5)	C5A—C6A	1.377 (16)
S1B—S2B	1.91 (3)	C7A—C8A	1.379 (14)
S2B—S3B	1.91 (3)	C7A—C12A	1.407 (13)
S1A—S2A	2.15 (10)	C8A—C9A	1.404 (13)
S1A—S3A	2.15 (10)	C9A—C10A	1.383 (12)
S2A—S3A	2.14 (10)	C10A—C11A	1.406 (13)
I1—Cu1	2.6563 (17)	C11A—C12A	1.389 (13)
I1—Cu1ⁱ	2.6669 (18)	N1B—C2B	1.296 (18)
Cu1—N1B	2.046 (11)	N1B—C6B	1.317 (18)
Cu1—N1A	2.062 (9)	C2B—C3B	1.391 (19)
Cu1—I1ⁱⁱ	2.6669 (18)	C3B—C4B	1.355 (19)
C1—C10A	1.539 (9)	C4B—C5B	1.389 (18)
C1—C10Aⁱⁱⁱ	1.539 (9)	C4B—C7B	1.489 (15)
C1—C10A^iv	1.539 (9)	C5B—C6B	1.37 (2)
C1—C10A^v	1.539 (9)	C7B—C12B	1.365 (14)
C2—C10B^vi	1.549 (10)	C7B—C8B	1.393 (14)
C2—C10B^vii	1.549 (10)	C8B—C9B	1.394 (14)
C2—C10B^viii	1.549 (10)	C9B—C10B	1.390 (13)
C2—C10B	1.549 (10)	C10B—C11B	1.391 (15)
N1A—C6A	1.322 (15)	C11B—C12B	1.381 (15)
N1A—C2A	1.327 (17)	C2Y—C3Y	1.38 (2)
C2A—C3A	1.381 (17)	C5Y—C6Y	1.37 (2)

S2X—S1X—S3X	59.8 (8)	C5A—C4A—C3A	116.5 (11)
S2X—S1X—I1	137 (3)	C5A—C4A—C7A	120.3 (9)
S3X—S1X—I1	154 (4)	C3A—C4A—C7A	123.2 (10)
S3X—S2X—S1X	60.2 (8)	C4A—C5A—C6A	122.0 (11)
S2X—S3X—S1X	60.0 (8)	N1A—C6A—C5A	120.7 (13)
S1B—S2B—S3B	117 (2)	C8A—C7A—C12A	118.9 (8)
S2A—S1A—S3A	59.7 (8)	C8A—C7A—C4A	123.2 (9)
S3A—S2A—S1A	60.1 (8)	C12A—C7A—C4A	117.9 (9)
S2A—S3A—S1A	60.2 (8)	C7A—C8A—C9A	121.8 (9)
S1X—I1—Cu1	131.7 (15)	C10A—C9A—C8A	120.2 (9)
S1X—I1—Cu1ⁱ	115.5 (16)	C9A—C10A—C11A	117.5 (9)
Cu1—I1—Cu1ⁱ	112.35 (3)	C9A—C10A—C1	124.0 (7)
N1B—Cu1—N1A	114.9 (4)	C11A—C10A—C1	118.5 (7)
N1B—Cu1—I1	103.2 (3)	C12A—C11A—C10A	123.0 (9)
N1A—Cu1—I1	106.7 (3)	C11A—C12A—C7A	118.5 (9)
N1B—Cu1—I1ⁱⁱ	104.9 (3)	C2B—N1B—C6B	116.6 (13)
N1A—Cu1—I1ⁱⁱ	105.9 (3)	C2B—N1B—Cu1	116.8 (11)
I1—Cu1—I1ⁱⁱ	121.67 (5)	C6B—N1B—Cu1	126.5 (9)
C10A—C1—C10Aⁱⁱⁱ	110.1 (4)	N1B—C2B—C3B	122.5 (15)
C10A—C1—C10A^iv	108.1 (7)	C4B—C3B—C2B	120.8 (13)
C10Aⁱⁱⁱ—C1—C10A^iv	110.1 (4)	C3B—C4B—C5B	114.9 (13)
C10A—C1—C10A^v	110.1 (4)	C3B—C4B—C7B	121.1 (11)
C10Aⁱⁱⁱ—C1—C10A^v	108.1 (7)	C5B—C4B—C7B	122.2 (12)
C10A^iv—C1—C10A^v	110.1 (4)	C6B—C5B—C4B	118.6 (17)
C10B^vi—C2—C10B^vii	111.1 (4)	N1B—C6B—C5B	124.2 (16)
C10B^vi—C2—C10B^viii	111.1 (4)	C12B—C7B—C8B	117.6 (10)
C10B^vii—C2—C10B^viii	106.2 (8)	C12B—C7B—C4B	122.7 (11)
C10B^vi—C2—C10B	106.2 (8)	C8B—C7B—C4B	119.6 (9)
C10B^vii—C2—C10B	111.1 (4)	C7B—C8B—C9B	119.4 (10)
C10B^viii—C2—C10B	111.1 (4)	C10B—C9B—C8B	122.0 (11)
C6A—N1A—C2A	118.4 (11)	C9B—C10B—C11B	118.2 (10)
C6A—N1A—Cu1	118.8 (9)	C9B—C10B—C2	118.7 (9)
C2A—N1A—Cu1	122.6 (9)	C11B—C10B—C2	123.1 (8)
N1A—C2A—C3A	122.6 (13)	C12B—C11B—C10B	118.6 (10)
C4A—C3A—C2A	119.4 (12)	C7B—C12B—C11B	124.1 (11)

Symmetry codes: (i) −x+1/2, −y+1/2, z+1/2; (ii) −x+1/2, −y+1/2, z−1/2; (iii) −y+1/2, x+1/2, −z+5/2; (iv) −x, −y+1, z; (v) y−1/2, −x+1/2, −z+5/2; (vi) −x+1, −y+1, z; (vii) −y+1, x, −z−1; (viii) y, −x+1, −z−1.

(350k_S_helical) top

Crystal data top

(CuI)_1.88(N1C5H4C6H₄)4C(bent⁻S₃)_1.00	D_x = 1.384 Mg m⁻³
M_r = 1083.34	Synchrotron radiation, λ = 0.800 Å
Tetragonal, I4	Cell parameters from 49763 reflections
a = 26.8987 (5) Å	θ = 2.7–26.4°
c = 7.1788 (1) Å	µ = 2.68 mm⁻¹
V = 5194.1 (2) Å³	T = 350 K
Z = 4	Needle, brownish yellow
F(000) = 2127	0.76 × 0.05 × 0.05 mm

Data collection top

ADSC Q210 CCD area detector diffractometer	3717 independent reflections
Radiation source: PLSII 2D bending magnet	3278 reflections with I > 2σ(I)
Si(111) double crystal monochromator	R_int = 0.043
ω scan	θ_max = 26.4°, θ_min = 2.7°
Absorption correction: multi-scan [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38]	h = −29→29
T_min = 0.523, T_max = 0.567	k = −29→29
49763 measured reflections	l = −7→7

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.120	w = 1/[σ²(F_o²) + (0.0953P)²] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3717 reflections	Δρ_max = 0.32 e Å⁻³
338 parameters	Δρ_min = −0.50 e Å⁻³
77 restraints	Absolute structure: Flack x determined using 1373 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.149 (17)

Special details top

Refinement. Refined as a 2-component twin.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1A	0.573 (2)	0.742 (2)	0.713 (12)	0.67 (6)	0.403 (14)
S2A	0.521 (2)	0.7343 (17)	0.531 (10)	0.60 (5)	0.403 (14)
S3A	0.527 (2)	0.773 (2)	0.304 (13)	0.61 (6)	0.403 (14)
S1B	0.6038 (9)	0.762 (2)	1.322 (10)	0.22 (4)	0.099 (14)
S2B	0.5409 (15)	0.769 (3)	1.189 (11)	0.20 (3)	0.099 (14)
S3B	0.515 (4)	0.745 (4)	0.957 (13)	0.29 (5)	0.099 (14)
I1	0.69522 (3)	0.75402 (4)	0.38398 (15)	0.1201 (3)	0.9381
Cu1	0.74940 (7)	0.70135 (5)	0.6238 (3)	0.1183 (5)	0.9381
C1	1.0000	0.5000	−0.2500	0.091 (5)
C2	0.5000	0.5000	1.5000	0.093 (5)
N1A	0.7974 (5)	0.6598 (5)	0.4667 (15)	0.119 (4)
C2A	0.8405 (9)	0.6438 (11)	0.531 (2)	0.191 (12)
H2AA	0.8485	0.6508	0.6543	0.229*
C3A	0.8753 (6)	0.6166 (7)	0.424 (2)	0.142 (6)
H3AA	0.9055	0.6065	0.4749	0.170*
C4A	0.8632 (5)	0.6054 (5)	0.2426 (16)	0.097 (3)
C5A	0.8196 (7)	0.6242 (8)	0.177 (2)	0.154 (7)
H5AA	0.8110	0.6190	0.0532	0.185*
C6A	0.7878 (7)	0.6509 (9)	0.292 (2)	0.159 (9)
H6AA	0.7583	0.6630	0.2418	0.191*
C7A	0.8961 (4)	0.5771 (4)	0.1196 (16)	0.093 (3)
C8A	0.8790 (5)	0.5457 (5)	−0.0214 (18)	0.110 (3)
H8AA	0.8450	0.5410	−0.0345	0.132*
C9A	0.9110 (4)	0.5212 (5)	−0.1436 (16)	0.103 (3)
H9AA	0.8981	0.5017	−0.2389	0.123*
C10A	0.9619 (4)	0.5260 (4)	−0.1230 (17)	0.092 (3)
C11A	0.9790 (5)	0.5567 (4)	0.0221 (16)	0.098 (3)
H11A	1.0131	0.5605	0.0385	0.117*
C12A	0.9473 (4)	0.5813 (4)	0.1406 (15)	0.105 (3)
H12A	0.9602	0.6009	0.2357	0.126*
N1B	0.6971 (6)	0.6613 (5)	0.7693 (16)	0.118 (3)	0.70 (3)
C2B	0.6842 (14)	0.6808 (10)	0.928 (4)	0.156 (13)	0.70 (3)
H2BA	0.6974	0.7113	0.9634	0.188*	0.70 (3)
C3B	0.6500 (13)	0.6559 (8)	1.047 (3)	0.130 (9)	0.70 (3)
H3BA	0.6391	0.6709	1.1562	0.156*	0.70 (3)
C4B	0.6334 (6)	0.6097 (6)	0.9982 (19)	0.114 (4)	0.70 (3)
C5B	0.6408 (13)	0.5952 (9)	0.817 (3)	0.149 (14)	0.70 (3)
H5BA	0.6240	0.5681	0.7672	0.179*	0.70 (3)
C6B	0.6744 (12)	0.6224 (11)	0.708 (3)	0.148 (11)	0.70 (3)
H6BA	0.6806	0.6120	0.5870	0.177*	0.70 (3)
C7B	0.5981 (4)	0.5827 (5)	1.1270 (17)	0.106 (3)
C8B	0.5913 (5)	0.5314 (4)	1.1075 (18)	0.113 (3)
H8BA	0.6079	0.5142	1.0137	0.135*
C9B	0.5599 (5)	0.5060 (5)	1.2281 (15)	0.100 (3)
H9BA	0.5557	0.4719	1.2142	0.120*
C10B	0.5343 (5)	0.5310 (5)	1.3706 (13)	0.099 (3)
C11B	0.5411 (5)	0.5817 (4)	1.389 (2)	0.116 (4)
H11B	0.5240	0.5995	1.4798	0.139*
C12B	0.5739 (6)	0.6054 (5)	1.270 (2)	0.125 (5)
H12B	0.5799	0.6391	1.2894	0.151*
N1Y	0.6971 (6)	0.6613 (5)	0.7693 (16)	0.118 (3)	0.30 (3)
C2Y	0.6561 (15)	0.6823 (13)	0.828 (8)	0.14 (2)	0.30 (3)
H2YA	0.6483	0.7139	0.7851	0.165*	0.30 (3)
C3Y	0.6230 (15)	0.6590 (12)	0.955 (8)	0.113 (15)	0.30 (3)
H3YA	0.5960	0.6757	1.0061	0.135*	0.30 (3)
C4Y	0.6334 (6)	0.6097 (6)	0.9982 (19)	0.114 (4)	0.30 (3)
C5Y	0.6756 (13)	0.5890 (13)	0.928 (7)	0.109 (15)	0.30 (3)
H5YA	0.6831	0.5560	0.9548	0.131*	0.30 (3)
C6Y	0.7076 (13)	0.6171 (12)	0.816 (6)	0.107 (16)	0.30 (3)
H6YA	0.7373	0.6030	0.7758	0.128*	0.30 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.46 (7)	0.44 (6)	1.10 (17)	0.20 (5)	−0.04 (10)	0.12 (10)
S2A	0.37 (5)	0.34 (5)	1.08 (16)	0.11 (5)	−0.15 (9)	0.15 (7)
S3A	0.46 (7)	0.32 (5)	1.04 (16)	0.16 (5)	−0.13 (11)	0.11 (8)
S1B	0.047 (14)	0.21 (4)	0.40 (9)	0.055 (17)	−0.05 (3)	0.00 (5)
S2B	0.09 (2)	0.15 (4)	0.37 (9)	0.03 (2)	−0.02 (3)	−0.05 (4)
S3B	0.22 (6)	0.18 (5)	0.49 (13)	0.05 (5)	−0.05 (8)	−0.05 (8)
I1	0.1301 (6)	0.1384 (6)	0.0919 (4)	0.0191 (5)	−0.0009 (7)	0.0075 (5)
Cu1	0.1338 (9)	0.1263 (9)	0.0948 (9)	0.0129 (10)	0.0261 (9)	−0.0003 (12)
C1	0.104 (8)	0.104 (8)	0.065 (11)	0.000	0.000	0.000
C2	0.109 (9)	0.109 (9)	0.061 (11)	0.000	0.000	0.000
N1A	0.134 (9)	0.136 (9)	0.085 (6)	0.031 (7)	0.001 (6)	0.006 (6)
C2A	0.23 (2)	0.28 (3)	0.064 (7)	0.12 (2)	0.003 (11)	−0.008 (13)
C3A	0.143 (11)	0.183 (15)	0.099 (11)	0.051 (10)	0.007 (9)	0.004 (10)
C4A	0.107 (8)	0.113 (8)	0.070 (6)	0.011 (6)	0.000 (6)	−0.007 (6)
C5A	0.180 (17)	0.184 (16)	0.099 (9)	0.083 (14)	0.003 (10)	−0.015 (10)
C6A	0.161 (15)	0.21 (2)	0.102 (11)	0.090 (15)	−0.021 (9)	−0.026 (11)
C7A	0.098 (6)	0.112 (7)	0.070 (7)	0.013 (5)	−0.001 (5)	−0.002 (6)
C8A	0.103 (7)	0.137 (9)	0.089 (7)	0.013 (7)	0.003 (6)	−0.016 (7)
C9A	0.100 (7)	0.124 (7)	0.085 (7)	0.003 (5)	0.000 (6)	−0.019 (6)
C10A	0.100 (7)	0.093 (6)	0.083 (7)	0.005 (5)	0.001 (6)	−0.001 (6)
C11A	0.118 (8)	0.112 (8)	0.064 (6)	0.017 (6)	−0.008 (5)	−0.006 (5)
C12A	0.124 (8)	0.118 (8)	0.073 (7)	0.010 (6)	0.003 (6)	−0.009 (6)
N1B	0.149 (10)	0.120 (9)	0.085 (7)	0.017 (8)	0.015 (7)	0.001 (6)
C2B	0.20 (3)	0.15 (2)	0.113 (19)	−0.085 (19)	0.04 (2)	−0.034 (15)
C3B	0.18 (2)	0.130 (16)	0.082 (14)	−0.024 (16)	0.042 (15)	−0.030 (11)
C4B	0.135 (11)	0.119 (10)	0.087 (8)	−0.014 (8)	0.010 (8)	−0.004 (7)
C5B	0.20 (3)	0.147 (19)	0.101 (15)	−0.06 (2)	0.063 (19)	−0.020 (14)
C6B	0.15 (2)	0.18 (2)	0.113 (18)	−0.030 (18)	0.024 (18)	−0.050 (17)
C7B	0.110 (7)	0.140 (10)	0.069 (7)	−0.011 (6)	0.006 (7)	0.002 (7)
C8B	0.136 (9)	0.129 (9)	0.073 (6)	0.000 (7)	0.017 (8)	0.004 (8)
C9B	0.129 (8)	0.110 (8)	0.060 (5)	0.004 (6)	0.015 (5)	−0.001 (6)
C10B	0.129 (9)	0.119 (8)	0.048 (5)	−0.004 (6)	0.009 (6)	0.004 (6)
C11B	0.131 (8)	0.125 (9)	0.091 (7)	−0.007 (7)	0.009 (9)	0.011 (8)
C12B	0.161 (13)	0.112 (9)	0.103 (10)	−0.007 (8)	0.040 (9)	−0.013 (7)
N1Y	0.149 (10)	0.120 (9)	0.085 (7)	0.017 (8)	0.015 (7)	0.001 (6)
C2Y	0.21 (6)	0.08 (3)	0.12 (4)	−0.04 (3)	−0.02 (5)	−0.01 (3)
C3Y	0.12 (3)	0.12 (3)	0.10 (4)	−0.04 (3)	0.02 (3)	−0.01 (3)
C4Y	0.135 (11)	0.119 (10)	0.087 (8)	−0.014 (8)	0.010 (8)	−0.004 (7)
C5Y	0.09 (2)	0.12 (3)	0.11 (4)	0.01 (2)	0.01 (3)	0.01 (3)
C6Y	0.07 (2)	0.15 (4)	0.10 (3)	0.01 (2)	0.05 (2)	−0.03 (3)

Geometric parameters (Å, º) top

S1A—S2A	1.94 (3)	C4A—C7A	1.464 (15)
S2A—S3A	1.95 (3)	C5A—C6A	1.389 (19)
S1B—S2B	1.95 (3)	C7A—C12A	1.392 (15)
S1B—I1ⁱ	2.51 (2)	C7A—C8A	1.394 (16)
S2B—S3B	1.93 (3)	C8A—C9A	1.395 (15)
I1—S1Bⁱⁱ	2.51 (2)	C9A—C10A	1.383 (14)
I1—Cu1	2.664 (2)	C10A—C11A	1.407 (15)
I1—Cu1ⁱⁱⁱ	2.674 (2)	C11A—C12A	1.374 (15)
Cu1—N1A	2.047 (11)	N1B—C6B	1.29 (2)
Cu1—N1B	2.057 (12)	N1B—C2B	1.30 (2)
Cu1—I1^iv	2.674 (2)	C2B—C3B	1.42 (2)
C1—C10A^v	1.539 (11)	C3B—C4B	1.37 (2)
C1—C10A^vi	1.539 (11)	C4B—C5B	1.37 (2)
C1—C10A^vii	1.539 (11)	C4B—C7B	1.511 (18)
C1—C10A	1.539 (11)	C5B—C6B	1.40 (2)
C2—C10B	1.552 (11)	C7B—C12B	1.360 (16)
C2—C10B^viii	1.552 (11)	C7B—C8B	1.400 (16)
C2—C10B^ix	1.552 (11)	C8B—C9B	1.389 (15)
C2—C10B^x	1.552 (11)	C9B—C10B	1.404 (14)
N1A—C6A	1.304 (18)	C10B—C11B	1.383 (16)
N1A—C2A	1.32 (2)	C11B—C12B	1.384 (17)
C2A—C3A	1.42 (2)	C2Y—C3Y	1.42 (3)
C3A—C4A	1.376 (18)	C5Y—C6Y	1.40 (3)
C4A—C5A	1.359 (18)

S1A—S2A—S3A	116 (5)	C4A—C5A—C6A	121.2 (14)
S2B—S1B—I1ⁱ	161 (4)	N1A—C6A—C5A	122.9 (15)
S3B—S2B—S1B	135 (4)	C12A—C7A—C8A	117.0 (10)
S1Bⁱⁱ—I1—Cu1	134.3 (16)	C12A—C7A—C4A	119.3 (10)
S1Bⁱⁱ—I1—Cu1ⁱⁱⁱ	112.4 (16)	C8A—C7A—C4A	123.7 (10)
Cu1—I1—Cu1ⁱⁱⁱ	112.67 (4)	C7A—C8A—C9A	122.7 (11)
N1A—Cu1—N1B	115.2 (5)	C10A—C9A—C8A	120.0 (11)
N1A—Cu1—I1	106.3 (3)	C9A—C10A—C11A	117.2 (10)
N1B—Cu1—I1	103.4 (4)	C9A—C10A—C1	123.6 (9)
N1A—Cu1—I1^iv	106.2 (4)	C11A—C10A—C1	119.2 (8)
N1B—Cu1—I1^iv	105.2 (4)	C12A—C11A—C10A	122.6 (11)
I1—Cu1—I1^iv	121.17 (5)	C11A—C12A—C7A	120.6 (11)
C10A^v—C1—C10A^vi	110.5 (5)	C6B—N1B—C2B	119.9 (16)
C10A^v—C1—C10A^vii	107.4 (9)	C6B—N1B—Cu1	125.2 (12)
C10A^vi—C1—C10A^vii	110.5 (5)	C2B—N1B—Cu1	114.5 (12)
C10A^v—C1—C10A	110.5 (5)	N1B—C2B—C3B	120.6 (17)
C10A^vi—C1—C10A	107.4 (9)	C4B—C3B—C2B	119.0 (15)
C10A^vii—C1—C10A	110.5 (5)	C3B—C4B—C5B	116.9 (15)
C10B—C2—C10B^viii	106.5 (9)	C3B—C4B—C7B	119.1 (13)
C10B—C2—C10B^ix	111.0 (4)	C5B—C4B—C7B	122.4 (14)
C10B^viii—C2—C10B^ix	111.0 (5)	C4B—C5B—C6B	118.2 (18)
C10B—C2—C10B^x	111.0 (4)	N1B—C6B—C5B	122.8 (18)
C10B^viii—C2—C10B^x	111.0 (4)	C12B—C7B—C8B	117.1 (11)
C10B^ix—C2—C10B^x	106.5 (9)	C12B—C7B—C4B	123.2 (12)
C6A—N1A—C2A	116.9 (13)	C8B—C7B—C4B	119.6 (11)
C6A—N1A—Cu1	120.3 (11)	C9B—C8B—C7B	120.1 (11)
C2A—N1A—Cu1	122.7 (10)	C8B—C9B—C10B	121.2 (12)
N1A—C2A—C3A	124.1 (15)	C11B—C10B—C9B	118.5 (11)
C4A—C3A—C2A	118.0 (15)	C11B—C10B—C2	123.4 (9)
C5A—C4A—C3A	116.8 (12)	C9B—C10B—C2	118.1 (10)
C5A—C4A—C7A	120.3 (11)	C10B—C11B—C12B	118.6 (12)
C3A—C4A—C7A	122.8 (12)	C7B—C12B—C11B	124.4 (13)

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

(300k_only_once) top

Crystal data top

(CuI)_1.85(N1C5H4C6H₄)4C(S₂)_1.50	D_x = 1.390 Mg m⁻³
M_r = 1077.31	Synchrotron radiation, λ = 0.700 Å
Tetragonal, I4	Cell parameters from 65225 reflections
a = 26.8664 (4) Å	θ = 2.4–29.5°
c = 7.1717 (1) Å	µ = 1.86 mm⁻¹
V = 5176.5 (2) Å³	T = 300 K
Z = 4	Needle, brownish yellow
F(000) = 2129	0.15 × 0.08 × 0.08 mm

Data collection top

ADSC Q210 CCD area detector diffractometer	4784 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	R_int = 0.045
Si(111) double crystal monochromator	θ_max = 29.5°, θ_min = 2.4°
ω scan	h = −34→33
65225 measured reflections	k = −33→34
6115 independent reflections	l = −9→9

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0755P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.001
6115 reflections	Δρ_max = 0.32 e Å⁻³
356 parameters	Δρ_min = −0.60 e Å⁻³
100 restraints	Absolute structure: Flack x determined using 1956 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.155 (17)

Special details top

Refinement. Refined as a 2-component twin.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1X	0.5984 (17)	0.751 (2)	1.430 (14)	0.49 (8)	0.158 (12)
S2X	0.542 (3)	0.721 (4)	1.231 (11)	0.29 (3)	0.158 (12)
S1Y	0.5208 (19)	0.738 (2)	1.413 (7)	0.34 (2)	0.241 (14)
S2Y	0.5367 (7)	0.7685 (9)	1.183 (4)	0.187 (10)	0.241 (14)
S1A	0.567 (3)	0.764 (3)	1.739 (14)	0.39 (3)	0.198 (13)
S2A	0.5088 (16)	0.749 (3)	1.602 (11)	0.35 (3)	0.198 (13)
S1B	0.5952 (16)	0.759 (3)	1.910 (14)	0.33 (4)	0.155 (13)
S2B	0.526 (2)	0.762 (4)	1.947 (18)	0.38 (4)	0.155 (13)
I1	0.69491 (2)	0.75387 (3)	0.38630 (9)	0.1097 (2)	0.924 (7)
Cu1	0.74969 (4)	0.70187 (3)	0.62513 (14)	0.1065 (3)	0.924 (7)
C1	1.0000	0.5000	−0.2500	0.077 (3)
C2	0.5000	0.5000	1.5000	0.098 (4)
N1A	0.7982 (3)	0.6593 (3)	0.4690 (9)	0.106 (2)
C2A	0.8418 (5)	0.6449 (6)	0.5308 (15)	0.153 (6)
H2AA	0.8512	0.6544	0.6504	0.184*
C3A	0.8749 (4)	0.6160 (5)	0.4267 (12)	0.131 (4)
H3AA	0.9044	0.6044	0.4786	0.157*
C4A	0.8624 (3)	0.6054 (3)	0.2440 (10)	0.0931 (19)
C5A	0.8189 (4)	0.6238 (5)	0.1804 (13)	0.130 (4)
H5AA	0.8104	0.6184	0.0564	0.156*
C6A	0.7861 (4)	0.6508 (5)	0.2931 (12)	0.126 (4)
H6AA	0.7562	0.6626	0.2451	0.151*
C7A	0.8964 (2)	0.5771 (3)	0.1204 (9)	0.0860 (15)
C8A	0.8791 (3)	0.5465 (3)	−0.0211 (10)	0.0945 (18)
H8AA	0.8449	0.5428	−0.0364	0.113*
C9A	0.9109 (2)	0.5211 (3)	−0.1410 (9)	0.0878 (16)
H9AA	0.8978	0.5008	−0.2337	0.105*
C10A	0.9612 (2)	0.5260 (2)	−0.1230 (9)	0.0810 (14)
C11A	0.9796 (3)	0.5564 (3)	0.0234 (9)	0.0842 (15)
H11A	1.0138	0.5594	0.0401	0.101*
C12A	0.9475 (3)	0.5816 (3)	0.1421 (8)	0.0899 (16)
H12A	0.9603	0.6016	0.2364	0.108*
N1B	0.6974 (4)	0.6622 (3)	0.7704 (10)	0.111 (2)	0.57 (2)
C2B	0.6848 (10)	0.6793 (9)	0.936 (3)	0.142 (10)	0.57 (2)
H2BA	0.6995	0.7084	0.9789	0.171*	0.57 (2)
C3B	0.6499 (9)	0.6550 (6)	1.049 (2)	0.115 (6)	0.57 (2)
H3BA	0.6379	0.6707	1.1551	0.138*	0.57 (2)
C4B	0.6335 (3)	0.6089 (3)	1.0040 (11)	0.101 (2)	0.57 (2)
C5B	0.6389 (9)	0.5984 (9)	0.820 (2)	0.146 (10)	0.57 (2)
H5BA	0.6188	0.5743	0.7647	0.175*	0.57 (2)
C6B	0.6739 (8)	0.6233 (7)	0.713 (2)	0.111 (6)	0.57 (2)
H6BA	0.6808	0.6113	0.5935	0.134*	0.57 (2)
C7B	0.5986 (3)	0.5827 (3)	1.1271 (12)	0.102 (2)
C8B	0.5911 (3)	0.5312 (3)	1.1079 (11)	0.1021 (18)
H8BA	0.6073	0.5138	1.0135	0.122*
C9B	0.5599 (3)	0.5065 (3)	1.2286 (10)	0.0972 (19)
H9BA	0.5558	0.4723	1.2150	0.117*
C10B	0.5342 (3)	0.5310 (3)	1.3711 (9)	0.0950 (18)
C11B	0.5413 (3)	0.5815 (3)	1.3872 (14)	0.110 (2)
H11B	0.5245	0.5992	1.4787	0.132*
C12B	0.5737 (4)	0.6060 (4)	1.2667 (13)	0.117 (3)
H12B	0.5785	0.6400	1.2827	0.141*
N1Y	0.6974 (4)	0.6622 (3)	0.7704 (10)	0.111 (2)	0.43 (2)
C2Y	0.6565 (11)	0.6832 (10)	0.837 (5)	0.162 (15)	0.43 (2)
H2YA	0.6488	0.7153	0.7994	0.194*	0.43 (2)
C3Y	0.6240 (10)	0.6593 (9)	0.963 (5)	0.142 (11)	0.43 (2)
H3YA	0.5974	0.6761	1.0173	0.171*	0.43 (2)
C4Y	0.6335 (3)	0.6089 (3)	1.0040 (11)	0.101 (2)	0.43 (2)
C5Y	0.6755 (8)	0.5919 (8)	0.933 (4)	0.122 (9)	0.43 (2)
H5YA	0.6853	0.5602	0.9695	0.147*	0.43 (2)
C6Y	0.7062 (8)	0.6169 (8)	0.811 (4)	0.128 (10)	0.43 (2)
H6YA	0.7332	0.6006	0.7579	0.154*	0.43 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1X	0.22 (3)	0.39 (7)	0.87 (18)	0.21 (5)	−0.33 (7)	−0.35 (10)
S2X	0.27 (5)	0.35 (6)	0.26 (6)	0.03 (5)	0.06 (4)	0.02 (5)
S1Y	0.27 (4)	0.37 (5)	0.37 (6)	−0.01 (4)	0.00 (5)	−0.04 (6)
S2Y	0.142 (12)	0.183 (15)	0.24 (2)	0.036 (10)	−0.054 (13)	0.002 (14)
S1A	0.32 (5)	0.37 (6)	0.48 (8)	0.03 (5)	0.01 (5)	−0.08 (6)
S2A	0.20 (3)	0.43 (6)	0.42 (7)	−0.05 (4)	0.10 (4)	−0.05 (7)
S1B	0.19 (3)	0.33 (5)	0.45 (9)	−0.06 (4)	−0.07 (5)	−0.17 (6)
S2B	0.30 (6)	0.35 (7)	0.50 (10)	0.07 (5)	−0.03 (7)	−0.04 (8)
I1	0.1187 (3)	0.1280 (4)	0.0825 (2)	0.0215 (3)	−0.0001 (3)	0.0073 (3)
Cu1	0.1206 (5)	0.1143 (5)	0.0845 (4)	0.0160 (6)	0.0244 (5)	−0.0002 (6)
C1	0.083 (4)	0.083 (4)	0.064 (6)	0.000	0.000	0.000
C2	0.115 (6)	0.115 (6)	0.065 (7)	0.000	0.000	0.000
N1A	0.115 (5)	0.114 (5)	0.087 (3)	0.032 (4)	0.009 (4)	−0.011 (3)
C2A	0.192 (13)	0.201 (13)	0.067 (4)	0.077 (10)	−0.010 (6)	−0.026 (6)
C3A	0.146 (7)	0.176 (9)	0.072 (5)	0.060 (7)	−0.002 (5)	−0.008 (5)
C4A	0.108 (5)	0.101 (5)	0.070 (3)	0.012 (4)	0.001 (3)	0.002 (3)
C5A	0.145 (8)	0.168 (9)	0.078 (4)	0.059 (7)	0.010 (5)	−0.007 (5)
C6A	0.127 (7)	0.174 (10)	0.076 (4)	0.040 (7)	−0.008 (4)	−0.015 (5)
C7A	0.098 (4)	0.102 (4)	0.059 (3)	0.017 (3)	0.004 (3)	0.001 (3)
C8A	0.094 (4)	0.115 (5)	0.075 (3)	0.012 (3)	0.001 (3)	−0.013 (3)
C9A	0.088 (4)	0.105 (4)	0.070 (3)	0.005 (3)	−0.004 (3)	−0.007 (3)
C10A	0.098 (4)	0.085 (3)	0.059 (3)	0.000 (3)	0.002 (3)	0.002 (3)
C11A	0.093 (4)	0.100 (4)	0.060 (3)	0.004 (3)	−0.004 (3)	−0.004 (3)
C12A	0.105 (4)	0.101 (4)	0.063 (3)	0.008 (3)	0.002 (3)	−0.005 (3)
N1B	0.135 (6)	0.120 (5)	0.078 (4)	0.009 (5)	0.013 (4)	0.001 (3)
C2B	0.168 (19)	0.163 (17)	0.096 (11)	−0.087 (15)	0.049 (11)	−0.058 (11)
C3B	0.144 (15)	0.113 (10)	0.087 (9)	−0.027 (10)	0.038 (10)	−0.031 (8)
C4B	0.124 (6)	0.110 (6)	0.070 (4)	0.001 (4)	0.002 (4)	0.002 (3)
C5B	0.161 (17)	0.21 (2)	0.065 (7)	−0.081 (17)	0.024 (9)	−0.020 (10)
C6B	0.136 (14)	0.115 (11)	0.083 (8)	−0.034 (10)	0.009 (8)	−0.009 (8)
C7B	0.100 (4)	0.122 (5)	0.084 (5)	−0.001 (4)	0.001 (4)	0.010 (4)
C8B	0.122 (5)	0.114 (5)	0.070 (3)	−0.003 (4)	0.007 (5)	−0.011 (4)
C9B	0.119 (5)	0.103 (5)	0.070 (3)	−0.002 (4)	0.005 (3)	−0.008 (3)
C10B	0.108 (5)	0.112 (5)	0.065 (4)	−0.004 (3)	−0.002 (3)	−0.002 (3)
C11B	0.128 (5)	0.109 (5)	0.092 (5)	−0.003 (4)	0.022 (5)	0.000 (5)
C12B	0.151 (8)	0.112 (6)	0.089 (5)	−0.006 (5)	0.022 (5)	−0.004 (4)
N1Y	0.135 (6)	0.120 (5)	0.078 (4)	0.009 (5)	0.013 (4)	0.001 (3)
C2Y	0.20 (3)	0.14 (2)	0.14 (3)	−0.05 (2)	0.08 (3)	−0.03 (2)
C3Y	0.105 (15)	0.17 (2)	0.15 (3)	0.008 (15)	−0.008 (16)	0.03 (2)
C4Y	0.124 (6)	0.110 (6)	0.070 (4)	0.001 (4)	0.002 (4)	0.002 (3)
C5Y	0.114 (14)	0.117 (13)	0.14 (2)	0.015 (11)	0.010 (14)	0.034 (14)
C6Y	0.076 (11)	0.17 (2)	0.14 (2)	0.037 (11)	0.059 (13)	0.031 (16)

Geometric parameters (Å, º) top

S1X—S2X	2.23 (10)	C4A—C7A	1.481 (9)
S1X—I1ⁱ	2.61 (6)	C5A—C6A	1.399 (12)
S1Y—S2Y	1.90 (3)	C7A—C8A	1.386 (10)
S1A—S2A	1.89 (3)	C7A—C12A	1.388 (9)
S1B—S2B	1.89 (3)	C8A—C9A	1.390 (9)
I1—S1Xⁱⁱ	2.61 (6)	C9A—C10A	1.364 (9)
I1—Cu1	2.6556 (12)	C10A—C11A	1.419 (9)
I1—Cu1ⁱⁱⁱ	2.6715 (13)	C11A—C12A	1.389 (9)
Cu1—N1B	2.049 (8)	N1B—C6B	1.291 (15)
Cu1—N1A	2.064 (6)	N1B—C2B	1.315 (15)
Cu1—I1^iv	2.6715 (13)	C2B—C3B	1.399 (17)
C1—C10A^v	1.551 (7)	C3B—C4B	1.353 (15)
C1—C10A^vi	1.551 (7)	C4B—C5B	1.360 (14)
C1—C10A^vii	1.551 (7)	C4B—C7B	1.468 (12)
C1—C10A	1.551 (7)	C5B—C6B	1.385 (18)
C2—C10B^viii	1.547 (8)	C7B—C12B	1.357 (12)
C2—C10B^ix	1.547 (8)	C7B—C8B	1.406 (11)
C2—C10B^x	1.547 (8)	C8B—C9B	1.376 (10)
C2—C10B	1.547 (8)	C9B—C10B	1.398 (10)
N1A—C2A	1.310 (13)	C10B—C11B	1.375 (11)
N1A—C6A	1.323 (12)	C11B—C12B	1.393 (12)
C2A—C3A	1.396 (13)	C2Y—C3Y	1.41 (2)
C3A—C4A	1.382 (11)	C5Y—C6Y	1.378 (19)
C4A—C5A	1.350 (12)

S2X—S1X—I1ⁱ	128 (4)	N1A—C6A—C5A	119.0 (9)
S1Xⁱⁱ—I1—Cu1	117 (2)	C8A—C7A—C12A	117.8 (6)
S1Xⁱⁱ—I1—Cu1ⁱⁱⁱ	131 (2)	C8A—C7A—C4A	122.4 (7)
Cu1—I1—Cu1ⁱⁱⁱ	112.18 (2)	C12A—C7A—C4A	119.8 (6)
N1B—Cu1—N1A	114.9 (3)	C7A—C8A—C9A	122.5 (7)
N1B—Cu1—I1	102.8 (3)	C10A—C9A—C8A	120.2 (7)
N1A—Cu1—I1	107.0 (2)	C9A—C10A—C11A	118.0 (6)
N1B—Cu1—I1^iv	104.9 (2)	C9A—C10A—C1	124.7 (5)
N1A—Cu1—I1^iv	106.0 (2)	C11A—C10A—C1	117.3 (5)
I1—Cu1—I1^iv	121.79 (3)	C12A—C11A—C10A	121.2 (7)
C10A^v—C1—C10A^vi	110.2 (3)	C7A—C12A—C11A	120.2 (6)
C10A^v—C1—C10A^vii	108.1 (5)	C6B—N1B—C2B	116.5 (11)
C10A^vi—C1—C10A^vii	110.2 (3)	C6B—N1B—Cu1	126.4 (8)
C10A^v—C1—C10A	110.2 (3)	C2B—N1B—Cu1	117.0 (9)
C10A^vi—C1—C10A	108.1 (5)	N1B—C2B—C3B	122.1 (13)
C10A^vii—C1—C10A	110.2 (3)	C4B—C3B—C2B	120.4 (12)
C10B^viii—C2—C10B^ix	110.9 (3)	C3B—C4B—C5B	112.7 (12)
C10B^viii—C2—C10B^x	110.9 (3)	C3B—C4B—C7B	120.3 (9)
C10B^ix—C2—C10B^x	106.6 (6)	C5B—C4B—C7B	123.6 (10)
C10B^viii—C2—C10B	106.6 (6)	C4B—C5B—C6B	120.7 (14)
C10B^ix—C2—C10B	110.9 (3)	N1B—C6B—C5B	122.9 (14)
C10B^x—C2—C10B	110.9 (3)	C12B—C7B—C8B	117.2 (8)
C2A—N1A—C6A	119.5 (8)	C12B—C7B—C4B	122.5 (8)
C2A—N1A—Cu1	123.0 (6)	C8B—C7B—C4B	120.3 (8)
C6A—N1A—Cu1	117.2 (7)	C9B—C8B—C7B	120.0 (7)
N1A—C2A—C3A	123.5 (9)	C8B—C9B—C10B	122.3 (8)
C4A—C3A—C2A	117.9 (9)	C11B—C10B—C9B	117.2 (7)
C5A—C4A—C3A	117.0 (8)	C11B—C10B—C2	124.3 (6)
C5A—C4A—C7A	121.3 (7)	C9B—C10B—C2	118.5 (7)
C3A—C4A—C7A	121.6 (7)	C10B—C11B—C12B	120.2 (8)
C4A—C5A—C6A	122.8 (9)	C7B—C12B—C11B	123.1 (9)

Acknowledgements

The authors acknowledge funding from the Veteran Researcher Grant (No. 2014R1A2A1A11049978) and the Framework of International Cooperation Program (No. 2014K2A2A4001500) managed by the National Research Foundation of Korea (NRF) and partly by the Yamada Science Foundation. The X-ray diffraction study using synchrotron radiation was performed at the PF-AR (NW2A beamline) of the High Energy Accelerator Research Organization (KEK) (proposal No. 2014G008) and at the Pohang Accelerator Laboratory (beamline 2D) supported by POSTECH. We thank Professor Kimoon Kim (POSTECH) for measurement of thermogravimetry. We thank Professor Yukio Furukawa and Mr Yuusaku Karatsu (Waseda University) for measurement of the Raman spectra.

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IUCrJ

Volume 3| Part 4| July 2016| Pages 232-236

ISSN: 2052-2525

doi:10.1107/S2052252516008423

CHEMISTRY | CRYSTENG

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

Isolation and evolution of labile sulfur allotropes via kinetic encapsulation in interactive porous networks

1. Introduction

2. Results and discussion

2.1. Kinetic trapping of sulfur gas

2.2. Direct observation of transient small sulfur by X-ray diffraction

2.3. Spectroscopic confirmation of sulfur species

2.4. Sulfur species in network 2

3. Conclusions

4. Related literature

Supporting information

Acknowledgements

References

research papers