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

IUCrJ
Volume 3| Part 4| July 2016| Pages 232-236
ISSN: 2052-2525

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

CROSSMARK_Color_square_no_text.svg

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.

1. Introduction

Cryogenic trapping methods, coupled with spectroscopy or crystallography, have been widely used to investigate transient chemical species (Whittle et al., 1954[Whittle, E., Dows, D. A. & Pimmentel, G. C. (1954). J. Chem. Phys. 22, 1943-1944.]; Misochko et al., 2003[Misochko, E. Y., Akimov, A. V. & Goldschleger, I. U. (2003). Russ. Chem. Rev. 72, 233-255.]; Kawano, 2014[Kawano, M. (2014). Bull. Chem. Soc. Jpn, 87, 577-592.]; Edman et al., 1999[Edman, K., Nollert, P., Royant, A., Belrhali, H., Pebay-Peyroula, E., Hajdu, J., Neutze, R. & Landau, E. M. (1999). Nature, 401, 822-826.]), 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[Whittle, E., Dows, D. A. & Pimmentel, G. C. (1954). J. Chem. Phys. 22, 1943-1944.]; Mück et al., 2012[Mück, L. A., Lattanzi, V., Thorwirth, S., McCarthy, M. C. & Gauss, J. (2012). Angew. Chem. Int. Ed. 51, 3695-3698.]), 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[Matsuda, R. (2013). Bull. Chem. Soc. Jpn, 86, 1117-1131.]; Cook et al., 2013[Cook, T. R., Zheng, Y. R. & Stang, P. J. (2013). Chem. Rev. 113, 734-777.]; Kitagawa & Uemura, 2005[Kitagawa, S. & Uemura, K. (2005). Chem. Soc. Rev. 34, 109-119.]; Eddaoudi et al., 2001[Eddaoudi, M., Moler, D. B., Li, H., Chen, B., Reineke, T. M., O'Keeffe, M. & Yaghi, O. M. (2001). Acc. Chem. Res. 34, 319-330.]; Férey, 2008[Férey, G. (2008). Chem. Soc. Rev. 37, 191-214.]; Peterson et al., 2014[Peterson, V. K., Southon, P. D., Halder, G. J., Price, D. J., Bevitt, J. J. & Kepert, C. J. (2014). Chem. Mater. 26, 4712-4723.]; Ohmori et al., 2005[Ohmori, O., Kawano, M. & Fujita, M. (2005). Angew. Chem. Int. Ed. 44, 1962-1964.]). 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[Kubota, R., Tashiro, S., Shiro, M. & Shionoya, M. (2014). Nat. Chem. 6, 913-918.]; Ikemoto et al., 2014[Ikemoto, K., Inokuma, Y., Rissanen, K. & Fujita, M. (2014). J. Am. Chem. Soc. 136, 6892-6895.]; Kawamichi et al., 2009[Kawamichi, T., Haneda, T., Kawano, M. & Fujita, M. (2009). Nature, 461, 633-635.]). Although time-resolved techniques offer attractive alternatives, they generally require the reactions to be reversible (Ohashi, 1998[Ohashi, Y. (1998). Acta Cryst. A54, 842-849.]). 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[Peramunage, D. & Licht, S. (1993). Science, 261, 1029-1032.]; Evers & Nazar, 2013[Evers, S. & Nazar, L. F. (2013). Acc. Chem. Res. 46, 1135-1143.]; Xin et al., 2012[Xin, S., Gu, L., Zhao, N., Yin, Y. X., Zhou, L. J., Guo, Y. G. & Wan, L. J. (2012). J. Am. Chem. Soc. 134, 18510-18513.]; Meyer, 1976[Meyer, B. (1976). Chem. Rev. 76, 367-388.]; Steudel & Eckert, 2003[Steudel, R. & Eckert, R. B. (2003). Top. Curr. Chem. 230, 1-79.]; Steudel et al., 2003[Steudel, R., Steudel, Y. & Wong, M. W. (2003). Top. Curr. Chem. 230, 117-134.]).

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[Ohtsu, H., Choi, W., Islam, N., Matsushita, Y. & Kawano, M. (2013). J. Am. Chem. Soc. 135, 11449-11452.]). 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[Ichikawa, M., Kimura, T. & Fukuoka, A. (1991). Stud. Surf. Sci. Catal. 60, 335-342.]; Rau et al., 1973[Rau, H., Kutty, T. R. N. & Guedes De Carvalho, J. R. F. (1973). J. Chem. Thermodyn. 5, 833-844.]): 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[Kitagawa, H., Ohtsu, H. & Kawano, M. (2013). Angew. Chem. Int. Ed. 52, 12395-12399.]). The kinetic product of the synthesis is network 1 (Fig. 1[link]a), [(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[Kitagawa, H., Ohtsu, H. & Kawano, M. (2013). Angew. Chem. Int. Ed. 52, 12395-12399.]). 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]
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[link]; 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[Ohtsu, H., Choi, W., Islam, N., Matsushita, Y. & Kawano, M. (2013). J. Am. Chem. Soc. 135, 11449-11452.]) and that of S3 in the gas phase as observed by rotational spectroscopy (McCarthy et al., 2004[McCarthy, M. C., Thorwirth, S., Gottlieb, C. A. & Thaddeus, P. (2004). J. Am. Chem. Soc. 126, 4096-4097.]). 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[link]). 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[Flemmig, B., Wolczanski, P. T. & Hoffmann, R. (2005). J. Am. Chem. Soc. 127, 1278-1285.]) 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[link]). The cyclo-S32+ state is isoelectric with a cyclo-SiS2 molecule (Mück et al., 2012[Mück, L. A., Lattanzi, V., Thorwirth, S., McCarthy, M. C. & Gauss, J. (2012). Angew. Chem. Int. Ed. 51, 3695-3698.]) 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]
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. 1[link]e). 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. 3[link]a). 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[Picquenard, E., El Jaroudi, O. & Corset, J. (1993). J. Raman Spectrosc. 24, 11-19.]). 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 H2Sn 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[Marsden, C. J. & Smith, B. J. (1988). J. Phys. Chem. 1988, 92, 347-353.]). 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]
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[link]; 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[Zheng, J., Tian, J., Wu, D., Gu, M., Xu, W., Wang, C., Gao, F., Engelhard, M. H., Zhang, J., Liu, J. & Xiao, J. (2014). Nano Lett. 14, 2345-2352.]). 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. 3[link]b), which corresponds to S2 symmetric stretching (Barletta, 1971[Barletta, R. E. (1971). J. Chem. Phys. 55, 5409.]). S2 remained stable within network 2 up to 500 K (see Fig. S2 in the supporting information).

[Figure 4]
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[Alecu, I. M., Zheng, J., Zhao, Y. & Truhlar, D. G. (2010). J. Chem. Theory Comput. 6, 2872-2887.]), Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]), Becke (1997[Becke, A. D. (1997). J. Chem. Phys. 107, 8554.]), Chai & Head-Gordon (2008a[Chai, J.-D. & Head-Gordon, M. (2008a). Chem. Phys. 128, 084106.],b[Chai, J.-D. & Head-Gordon, M. (2008b). Phys. Chem. Chem. Phys. 10, 6615.]), Frisch et al. (2009[Grimme, S. (2006). J. Comput. Chem. 27, 1787-1799.]), Grimme (2006[Frisch, M. J. et al. (2009). GAUSSIAN09. Gaussian Inc., Wallingford, Connecticut, USA.]), Kozuch & Martin (2013[Kozuch, S. & Martin, J. M. (2013). J. Chem. Theory. Comput. 9, 1918-1931.]), Sheldrick (1990[Sheldrick, G. M. (1990). Acta Cryst. A46, 467-473.]) and Weigend & Ahlrichs (2005[Weigend, F. & Ahlrichs, R. (2005). Phys. Chem. Chem. Phys. 7, 3297.]).

Supporting information


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)0.975Dx = 1.473 Mg m3
Mr = 1070.94Synchrotron radiation, λ = 0.68990 Å
Tetragonal, I4/mcmCell parameters from 20372 reflections
a = 13.2563 (2) Åθ = 2.1–35.0°
c = 27.5616 (7) ŵ = 1.98 mm1
V = 4843.4 (2) Å3T = 30 K
Z = 4Block, yellow
F(000) = 21040.05 × 0.03 × 0.03 mm
Data collection top
Rigaku Mercury CCD
diffractometer
3092 independent reflections
Radiation source: KEK PF-AR NW2A beamline2025 reflections with I > 2σ(I)
Si 111 monochromatorRint = 0.070
oscillation method, ω scansθmax = 35.0°, θmin = 2.1°
Absorption correction: empirical (using intensity measurements)
HKL2000 Scalepack
h = 2220
Tmin = 0.908, Tmax = 0.943k = 1912
20372 measured reflectionsl = 4524
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 0.75 w = 1/[σ2(Fo2) + (0.0688P)2]
where P = (Fo2 + 2Fc2)/3
3092 reflections(Δ/σ)max = 0.004
140 parametersΔρmax = 2.23 e Å3
43 restraintsΔρmin = 0.98 e Å3
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
xyzUiso*/UeqOcc. (<1)
S1A0.00000.00000.1155 (19)0.21 (2)0.084 (8)
S2A0.00000.00000.1831 (19)0.115 (15)0.084 (8)
S1B0.00000.00000.156 (3)0.13 (2)0.068 (7)
S2B0.00000.00000.223 (3)0.24 (3)0.068 (7)
S1C0.00000.00000.035 (2)0.205 (18)0.104 (5)
S2C0.0549 (11)0.1246 (8)0.022 (2)0.24 (5)0.104 (5)
S1D0.00000.00000.0674 (8)0.18 (2)0.086 (9)
S2D0.00000.00000.00000.15 (2)0.086 (9)
C300.00000.50000.25000.0212 (9)
Cu10.43382 (3)0.06618 (3)0.00000.02704 (12)
I10.375807 (14)0.124193 (14)0.00000.02658 (8)
N110.36674 (12)0.13326 (12)0.05872 (9)0.0278 (5)
C140.25370 (15)0.24630 (15)0.12558 (10)0.0261 (5)
C210.19079 (14)0.30921 (14)0.15814 (9)0.0241 (5)
C240.06778 (14)0.43222 (14)0.21761 (9)0.0217 (4)
C120.4088 (3)0.1967 (3)0.08865 (15)0.0296 (8)0.50
H120.48010.20390.08770.036*0.50
C130.3549 (3)0.2549 (3)0.12216 (16)0.0281 (8)0.50
H130.38980.30070.14270.034*0.50
C150.2063 (3)0.1719 (3)0.09584 (15)0.0282 (8)0.50
H150.13600.15930.09840.034*0.50
C160.2653 (3)0.1181 (3)0.06299 (15)0.0293 (8)0.50
H160.23390.06920.04290.035*0.50
C220.1533 (3)0.2734 (3)0.20143 (14)0.0277 (7)0.50
H220.17030.20710.21160.033*0.50
C230.0905 (3)0.3327 (3)0.23092 (13)0.0268 (7)0.50
H230.06340.30530.26000.032*0.50
C250.1078 (3)0.4689 (3)0.17453 (13)0.0251 (7)0.50
H250.09320.53630.16510.030*0.50
C260.1681 (3)0.4103 (3)0.14494 (13)0.0253 (7)0.50
H260.19450.43770.11570.030*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.22 (3)0.22 (3)0.19 (5)0.0000.0000.000
S2A0.128 (19)0.128 (19)0.09 (3)0.0000.0000.000
S1B0.13 (2)0.13 (2)0.12 (4)0.0000.0000.000
S2B0.25 (4)0.25 (4)0.22 (7)0.0000.0000.000
S1C0.24 (3)0.24 (3)0.14 (3)0.0000.0000.000
S2C0.075 (7)0.073 (7)0.57 (14)0.001 (5)0.07 (3)0.041 (19)
S1D0.22 (3)0.22 (3)0.10 (3)0.0000.0000.000
S2D0.21 (3)0.21 (3)0.040 (19)0.0000.0000.000
C300.0263 (14)0.0263 (14)0.0110 (17)0.0000.0000.000
Cu10.03196 (16)0.03196 (16)0.0172 (2)0.0085 (2)0.0000.000
I10.03153 (10)0.03153 (10)0.01668 (10)0.00108 (10)0.0000.000
N110.0312 (7)0.0312 (7)0.0210 (10)0.0071 (9)0.0010 (6)0.0010 (6)
C140.0313 (8)0.0313 (8)0.0155 (10)0.0059 (10)0.0001 (7)0.0001 (7)
C210.0280 (7)0.0280 (7)0.0162 (10)0.0035 (11)0.0012 (6)0.0012 (6)
C240.0259 (7)0.0259 (7)0.0135 (9)0.0009 (10)0.0004 (6)0.0004 (6)
C120.0314 (19)0.036 (2)0.0215 (17)0.0058 (17)0.0016 (14)0.0015 (15)
C130.032 (2)0.0295 (19)0.0226 (18)0.0023 (15)0.0014 (15)0.0062 (15)
C150.0299 (19)0.031 (2)0.0236 (17)0.0034 (15)0.0028 (14)0.0012 (15)
C160.033 (2)0.031 (2)0.0242 (18)0.0028 (17)0.0006 (15)0.0051 (15)
C220.0355 (18)0.0286 (18)0.0190 (16)0.0045 (15)0.0002 (15)0.0012 (14)
C230.0334 (18)0.0317 (19)0.0153 (14)0.0056 (16)0.0052 (14)0.0010 (14)
C250.0332 (19)0.0275 (18)0.0147 (14)0.0023 (15)0.0019 (13)0.0000 (12)
C260.0333 (19)0.0286 (17)0.0141 (13)0.0014 (15)0.0030 (14)0.0010 (13)
Geometric parameters (Å, º) top
S1A—S2A1.862 (16)Cu1—I12.6382 (3)
S1B—S2B1.85 (2)I1—Cu1xii2.6382 (3)
S2B—S2Bi1.47 (15)N11—C121.303 (5)
S1C—S2Cii1.840 (17)N11—C12xiii1.303 (5)
S1C—S2C1.840 (17)N11—C16xiii1.364 (5)
S1C—S2Ciii1.840 (17)N11—C161.364 (5)
S1C—S2Civ1.840 (17)C14—C131.350 (4)
S1C—S1Cv1.93 (11)C14—C13xiii1.350 (4)
S1C—S2Cvi2.39 (6)C14—C15xiii1.428 (4)
S1C—S2Cvii2.39 (6)C14—C151.428 (5)
S1C—S2Cv2.39 (6)C14—C211.482 (4)
S1C—S2Cviii2.39 (6)C21—C221.377 (4)
S2C—S2Cvii1.22 (12)C21—C22xiii1.377 (4)
S2C—S1Cv2.39 (6)C21—C261.421 (4)
S1D—S2D1.86 (2)C21—C26xiii1.421 (4)
S2D—S1Dv1.86 (2)C24—C251.388 (4)
C30—C24ix1.553 (3)C24—C25xiii1.388 (4)
C30—C241.553 (3)C24—C231.402 (5)
C30—C24x1.553 (3)C24—C23xiii1.402 (5)
C30—C24xi1.553 (3)C12—C131.399 (6)
Cu1—N11vii2.050 (2)C15—C161.393 (6)
Cu1—N112.050 (2)C22—C231.404 (5)
Cu1—Cu1xii2.4813 (9)C25—C261.381 (5)
Cu1—I1xii2.6382 (3)
S2Bi—S2B—S1B180.000 (2)N11vii—Cu1—I1106.77 (3)
S2Cii—S1C—S2C87.8 (9)N11—Cu1—I1106.77 (3)
S2Cii—S1C—S2Ciii158 (5)Cu1xii—Cu1—I161.948 (9)
S2C—S1C—S2Ciii87.8 (9)I1xii—Cu1—I1123.896 (19)
S2Cii—S1C—S2Civ87.8 (9)Cu1xii—I1—Cu156.104 (19)
S2C—S1C—S2Civ158 (5)C12—N11—C12xiii98.7 (4)
S2Ciii—S1C—S2Civ87.8 (9)C12—N11—C16xiii41.1 (2)
S2Cii—S1C—S1Cv79 (2)C12xiii—N11—C16xiii117.5 (3)
S2C—S1C—S1Cv79 (2)C12—N11—C16117.5 (3)
S2Ciii—S1C—S1Cv79 (2)C12xiii—N11—C1641.1 (2)
S2Civ—S1C—S1Cv79 (2)C16xiii—N11—C16106.4 (4)
S2Cii—S1C—S2Cvi30 (3)C12—N11—Cu1126.5 (2)
S2C—S1C—S2Cvi82.7 (15)C12xiii—N11—Cu1126.5 (2)
S2Ciii—S1C—S2Cvi128 (3)C16xiii—N11—Cu1115.6 (2)
S2Civ—S1C—S2Cvi82.7 (15)C16—N11—Cu1115.6 (2)
S1Cv—S1C—S2Cvi48.9 (16)C13—C14—C13xiii99.3 (4)
S2Cii—S1C—S2Cvii82.7 (15)C13—C14—C15xiii40.2 (2)
S2C—S1C—S2Cvii30 (3)C13xiii—C14—C15xiii117.1 (3)
S2Ciii—S1C—S2Cvii82.7 (15)C13—C14—C15117.1 (3)
S2Civ—S1C—S2Cvii128 (3)C13xiii—C14—C1540.2 (2)
S1Cv—S1C—S2Cvii48.9 (16)C15xiii—C14—C15106.1 (4)
S2Cvi—S1C—S2Cvii64.4 (17)C13—C14—C21123.7 (2)
S2Cii—S1C—S2Cv82.7 (15)C13xiii—C14—C21123.7 (2)
S2C—S1C—S2Cv128 (3)C15xiii—C14—C21119.3 (2)
S2Ciii—S1C—S2Cv82.7 (15)C15—C14—C21119.3 (2)
S2Civ—S1C—S2Cv30 (3)C22—C21—C22xiii59.8 (4)
S1Cv—S1C—S2Cv48.9 (16)C22—C21—C26118.1 (3)
S2Cvi—S1C—S2Cv64.4 (17)C22xiii—C21—C2687.4 (3)
S2Cvii—S1C—S2Cv98 (3)C22—C21—C26xiii87.4 (3)
S2Cii—S1C—S2Cviii128 (3)C22xiii—C21—C26xiii118.1 (3)
S2C—S1C—S2Cviii82.7 (15)C26—C21—C26xiii62.3 (4)
S2Ciii—S1C—S2Cviii30 (3)C22—C21—C14122.3 (2)
S2Civ—S1C—S2Cviii82.7 (15)C22xiii—C21—C14122.3 (2)
S1Cv—S1C—S2Cviii48.9 (16)C26—C21—C14119.6 (2)
S2Cvi—S1C—S2Cviii98 (3)C26xiii—C21—C14119.6 (2)
S2Cvii—S1C—S2Cviii64.4 (17)C25—C24—C25xiii62.4 (3)
S2Cv—S1C—S2Cviii64.4 (17)C25—C24—C23118.1 (3)
S2Cvii—S2C—S1C101 (2)C25xiii—C24—C2386.6 (3)
S2Cvii—S2C—S1Cv48.9 (16)C25—C24—C23xiii86.6 (3)
S1C—S2C—S1Cv52 (3)C25xiii—C24—C23xiii118.1 (3)
S1Dv—S2D—S1D180.0C23—C24—C23xiii61.8 (4)
C24ix—C30—C24109.82 (18)C25—C24—C30120.6 (2)
C24ix—C30—C24x109.30 (9)C25xiii—C24—C30120.6 (2)
C24—C30—C24x109.30 (9)C23—C24—C30121.2 (2)
C24ix—C30—C24xi109.30 (9)C23xiii—C24—C30121.2 (2)
C24—C30—C24xi109.30 (9)N11—C12—C13123.7 (4)
C24x—C30—C24xi109.82 (18)C14—C13—C12120.5 (4)
N11vii—Cu1—N11104.31 (14)C16—C15—C14118.7 (4)
N11vii—Cu1—Cu1xii127.85 (7)N11—C16—C15122.3 (4)
N11—Cu1—Cu1xii127.85 (7)C21—C22—C23121.5 (4)
N11vii—Cu1—I1xii106.77 (3)C22—C23—C24120.2 (3)
N11—Cu1—I1xii106.77 (3)C26—C25—C24121.9 (3)
Cu1xii—Cu1—I1xii61.948 (9)C25—C26—C21120.1 (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, y1, z; (x) x, y, z+1/2; (xi) x, y1, z+1/2; (xii) x+1, y, z; (xiii) y+1/2, x1/2, z.
(250K_S_helical_initial) top
Crystal data top
(CuI)1.88(N1C5H4C6H4)4C(S2)0.63(S3)0.58Dx = 1.403 Mg m3
Mr = 1083.02Synchrotron radiation, λ = 0.800 Å
Tetragonal, P4Cell parameters from 91118 reflections
a = 26.7176 (5) Åθ = 2.7–26.4°
c = 7.1942 (2) ŵ = 2.71 mm1
V = 5135.4 (2) Å3T = 250 K
Z = 4Needle, brownish yellow
F(000) = 21330.76 × 0.05 × 0.05 mm
Data collection top
ADSC Q210 CCD area detector
diffractometer
7133 independent reflections
Radiation source: PLSII 2D bending magnet4892 reflections with I > 2σ(I)
Si(111) double crystal monochromatorRint = 0.075
ω scanθmax = 26.4°, θmin = 2.7°
Absorption correction: multi-scan
[c.f. r.h. blessing, acta cryst. (1995), a51, 33-38]
h = 2929
Tmin = 0.620, Tmax = 0.669k = 2929
91118 measured reflectionsl = 77
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.068H-atom parameters constrained
wR(F2) = 0.235 w = 1/[σ2(Fo2) + (0.1773P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.014
7133 reflectionsΔρmax = 0.32 e Å3
750 parametersΔρmin = 0.48 e Å3
1237 restraintsAbsolute 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 methodsAbsolute structure parameter: 0.051 (19)
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. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S1A0.5926 (19)0.730 (2)1.079 (5)0.27 (2)0.252 (11)
S2A0.565 (2)0.7149 (19)1.323 (4)0.28 (2)0.252 (11)
S3A0.557 (4)0.774 (2)1.473 (8)0.38 (4)0.252 (11)
S1B0.531 (2)0.755 (3)1.117 (5)0.26 (3)0.155 (11)
S2B0.514 (3)0.752 (3)0.863 (6)0.27 (3)0.155 (11)
S1C0.545 (3)0.728 (3)0.528 (7)0.34 (4)0.153 (14)
S2C0.522 (3)0.776 (4)0.711 (12)0.34 (4)0.153 (14)
S3C0.573 (4)0.798 (3)0.877 (11)0.35 (5)0.153 (14)
S4A0.958 (3)0.780 (3)1.344 (6)0.23 (3)0.087 (12)
S5A0.904 (4)0.785 (5)1.514 (9)0.28 (3)0.087 (12)
S4B0.961 (3)0.777 (2)1.956 (4)0.30 (3)0.197 (16)
S5B0.935 (3)0.782 (2)1.711 (5)0.30 (3)0.197 (16)
S4C0.956 (3)0.723 (3)0.949 (6)0.29 (4)0.191 (15)
S5C0.979 (2)0.735 (2)1.194 (4)0.23 (2)0.191 (15)
S4D0.916 (3)0.755 (3)1.743 (10)0.33 (3)0.172 (13)
S5D0.928 (2)0.724 (4)1.501 (8)0.33 (3)0.172 (13)
S6D0.996 (2)0.738 (3)1.424 (6)0.25 (3)0.172 (13)
Cu10.75493 (12)0.69946 (11)0.3655 (5)0.1459 (9)0.9381
Cu20.74986 (12)0.79527 (11)0.8663 (5)0.1478 (9)0.9381
I10.69666 (6)0.74214 (7)0.6263 (3)0.1463 (6)0.9381
I20.80722 (6)0.75361 (7)0.1270 (3)0.1512 (6)0.9381
C911.00001.00000.00000.097 (7)
C921.00000.50001.279 (3)0.131 (10)
C930.50000.50000.50000.106 (8)
N110.7072 (8)0.6593 (8)0.214 (3)0.171 (8)
C120.7161 (9)0.6478 (11)0.040 (4)0.165 (9)
H120.74710.65810.00910.198*
C130.6841 (8)0.6219 (8)0.081 (2)0.137 (6)
H130.69210.61720.20700.164*
C140.6396 (7)0.6034 (8)0.005 (3)0.128 (5)
C150.6284 (9)0.6122 (10)0.173 (2)0.159 (8)
H150.59940.59900.22860.191*
C160.6637 (10)0.6434 (10)0.278 (2)0.171 (9)
H160.65470.65280.39990.205*
N31A0.8073 (7)0.6622 (7)0.5166 (19)0.134 (5)0.442 (14)
C32A0.8281 (18)0.6206 (15)0.461 (5)0.155 (11)0.442 (14)
H32A0.81970.60710.34430.186*0.442 (14)
C33A0.863 (2)0.5962 (17)0.573 (5)0.160 (12)0.442 (14)
H33A0.88060.56920.52210.192*0.442 (14)
C34A0.8717 (8)0.6097 (7)0.757 (3)0.126 (5)0.442 (14)
C35A0.8542 (18)0.6553 (13)0.812 (4)0.131 (11)0.442 (14)
H35A0.85990.66870.93120.157*0.442 (14)
C36A0.8258 (17)0.6813 (11)0.668 (4)0.120 (10)0.442 (14)
H36A0.82030.71570.68670.144*0.442 (14)
N31B0.8073 (7)0.6622 (7)0.5166 (19)0.134 (5)0.558 (14)
C32B0.7997 (13)0.6153 (10)0.559 (4)0.146 (10)0.558 (14)
H32B0.77000.60000.51890.175*0.558 (14)
C33B0.8335 (13)0.5871 (11)0.661 (5)0.151 (10)0.558 (14)
H33B0.83020.55210.66440.182*0.558 (14)
C34B0.8717 (8)0.6097 (7)0.757 (3)0.126 (5)0.558 (14)
C35B0.8769 (16)0.6594 (10)0.739 (6)0.143 (10)0.558 (14)
H35B0.89640.67910.81900.171*0.558 (14)
C36B0.8495 (11)0.6797 (13)0.582 (4)0.144 (10)0.558 (14)
H36B0.86320.70780.52240.173*0.558 (14)
N51A0.6995 (8)0.8324 (7)1.010 (2)0.158 (6)0.442 (14)
C52A0.7063 (16)0.8818 (11)1.034 (5)0.141 (11)0.442 (14)
H52A0.73210.89780.96790.169*0.442 (14)
C53A0.6757 (16)0.9106 (14)1.154 (7)0.155 (11)0.442 (14)
H53A0.68410.94401.17960.186*0.442 (14)
C54A0.6326 (9)0.8892 (7)1.235 (3)0.144 (6)0.442 (14)
C55A0.6280 (18)0.8389 (10)1.228 (6)0.133 (11)0.442 (14)
H55A0.60970.81991.31440.160*0.442 (14)
C56A0.6555 (14)0.8175 (14)1.068 (5)0.151 (11)0.442 (14)
H56A0.64010.79111.00280.181*0.442 (14)
N51B0.6995 (8)0.8324 (7)1.010 (2)0.158 (6)0.558 (14)
C52B0.6767 (16)0.8731 (13)0.952 (4)0.155 (10)0.558 (14)
H52B0.68360.88290.82920.185*0.558 (14)
C53B0.6431 (15)0.9038 (13)1.051 (3)0.146 (10)0.558 (14)
H53B0.62860.93240.99720.175*0.558 (14)
C54B0.6326 (9)0.8892 (7)1.235 (3)0.144 (6)0.558 (14)
C55B0.6506 (15)0.8443 (10)1.290 (3)0.121 (9)0.558 (14)
H55B0.64230.83211.40900.146*0.558 (14)
C56B0.6828 (13)0.8145 (10)1.169 (4)0.130 (9)0.558 (14)
H56B0.69160.78191.20480.155*0.558 (14)
N710.7956 (8)0.8406 (8)0.720 (2)0.148 (6)
C720.8405 (8)0.8560 (9)0.774 (2)0.152 (8)
H720.85220.84520.89070.182*
C730.8711 (8)0.8870 (8)0.671 (2)0.132 (6)
H730.89880.90230.72780.158*
C740.8615 (8)0.8959 (8)0.483 (2)0.131 (6)
C750.8195 (7)0.8738 (9)0.411 (2)0.144 (7)
H750.81140.87630.28400.173*
C760.7880 (10)0.8460 (10)0.541 (3)0.160 (9)
H760.75940.83050.49180.191*
C41A0.9031 (8)0.5823 (8)0.886 (3)0.149 (7)
C42A0.9093 (8)0.5299 (8)0.879 (3)0.144 (6)
H42A0.89310.51100.78680.173*
C43A0.9399 (9)0.5064 (8)1.011 (3)0.150 (7)
H43A0.94230.47131.00810.180*
C44A0.9666 (8)0.5320 (9)1.145 (3)0.149 (7)
C45A0.9599 (8)0.5836 (8)1.156 (2)0.139 (6)
H45A0.97650.60231.24730.167*
C46A0.9281 (10)0.6073 (9)1.028 (3)0.182 (10)
H46A0.92330.64211.03850.218*
C61A0.5973 (9)0.9169 (7)1.362 (3)0.143 (5)0.442 (14)
C62A0.5644 (17)0.8909 (11)1.480 (6)0.128 (12)0.442 (14)
H62A0.56440.85571.48430.154*0.442 (14)
C63A0.5314 (17)0.9193 (10)1.592 (5)0.131 (12)0.442 (14)
H63A0.50490.90301.65240.157*0.442 (14)
C64A0.5371 (9)0.9701 (7)1.614 (3)0.147 (6)0.442 (14)
C65A0.569 (3)0.9962 (13)1.494 (9)0.154 (14)0.442 (14)
H65A0.57121.03131.49910.185*0.442 (14)
C66A0.599 (3)0.9693 (10)1.365 (9)0.148 (14)0.442 (14)
H66A0.61980.98661.28150.178*0.442 (14)
C81A0.8943 (5)0.9241 (6)0.374 (2)0.112 (4)
C82A0.9466 (6)0.9191 (7)0.396 (2)0.121 (5)
H82A0.95960.89860.49050.146*
C83A0.9791 (6)0.9449 (7)0.277 (2)0.119 (5)
H83A1.01370.94350.29860.143*
C84A0.9614 (6)0.9726 (7)0.126 (2)0.116 (4)
C85A0.9091 (6)0.9814 (8)0.116 (2)0.125 (5)
H85A0.89631.00570.03340.150*
C86A0.8769 (7)0.9539 (8)0.228 (2)0.125 (5)
H86A0.84230.95540.20470.149*
C21B0.6064 (6)0.5745 (6)0.128 (3)0.129 (5)
C22B0.6241 (7)0.5434 (7)0.271 (3)0.122 (5)
H22B0.65870.53840.28540.147*
C23B0.5908 (6)0.5199 (6)0.3940 (18)0.103 (4)
H23B0.60370.50000.49040.123*
C24B0.5403 (5)0.5251 (5)0.378 (2)0.103 (4)
C25B0.5220 (7)0.5551 (6)0.2298 (19)0.108 (4)
H25B0.48730.55850.21280.130*
C26B0.5552 (6)0.5801 (6)0.107 (2)0.113 (4)
H26B0.54240.60060.01220.136*
C61B0.5973 (9)0.9169 (7)1.362 (3)0.143 (5)0.558 (14)
C62B0.5880 (19)0.9687 (10)1.335 (6)0.141 (12)0.558 (14)
H62B0.60260.98601.23480.169*0.558 (14)
C63B0.5565 (18)0.9932 (12)1.461 (5)0.137 (12)0.558 (14)
H63B0.54841.02701.43880.165*0.558 (14)
C64B0.5371 (9)0.9701 (7)1.614 (3)0.147 (6)0.558 (14)
C65B0.5450 (17)0.9181 (10)1.641 (6)0.148 (12)0.558 (14)
H65B0.52740.90041.73270.177*0.558 (14)
C66B0.5807 (16)0.8933 (12)1.523 (4)0.131 (11)0.558 (14)
H66B0.59280.86141.55460.157*0.558 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.28 (4)0.37 (5)0.15 (3)0.02 (4)0.06 (3)0.01 (3)
S2A0.42 (6)0.33 (5)0.090 (16)0.06 (4)0.01 (2)0.02 (2)
S3A0.51 (9)0.44 (9)0.20 (5)0.05 (7)0.08 (5)0.06 (5)
S1B0.36 (6)0.30 (5)0.12 (3)0.01 (5)0.14 (3)0.01 (3)
S2B0.42 (7)0.30 (6)0.10 (2)0.09 (5)0.04 (4)0.08 (3)
S1C0.44 (8)0.44 (9)0.14 (3)0.21 (7)0.21 (4)0.08 (4)
S2C0.46 (8)0.30 (7)0.27 (6)0.09 (6)0.03 (7)0.04 (6)
S3C0.56 (11)0.23 (6)0.26 (7)0.02 (6)0.12 (7)0.14 (5)
S4A0.43 (7)0.22 (5)0.04 (2)0.03 (5)0.03 (3)0.06 (3)
S5A0.47 (7)0.30 (6)0.09 (3)0.04 (6)0.15 (4)0.03 (4)
S4B0.57 (9)0.26 (5)0.055 (14)0.12 (5)0.01 (3)0.06 (2)
S5B0.49 (7)0.25 (4)0.15 (3)0.07 (5)0.13 (4)0.01 (3)
S4C0.35 (7)0.38 (8)0.13 (3)0.11 (6)0.07 (4)0.03 (4)
S5C0.35 (5)0.26 (4)0.072 (16)0.01 (4)0.06 (2)0.04 (2)
S4D0.39 (6)0.34 (7)0.25 (4)0.05 (5)0.23 (4)0.00 (5)
S5D0.41 (6)0.37 (6)0.19 (4)0.04 (5)0.14 (4)0.05 (4)
S6D0.35 (6)0.26 (5)0.13 (3)0.00 (4)0.08 (3)0.06 (3)
Cu10.1647 (18)0.1611 (18)0.1120 (15)0.0438 (16)0.0198 (18)0.002 (2)
Cu20.179 (2)0.1513 (17)0.1134 (16)0.0439 (17)0.0076 (19)0.006 (2)
I10.1695 (11)0.1606 (11)0.1088 (8)0.0468 (9)0.0091 (11)0.0003 (10)
I20.1627 (11)0.1691 (12)0.1220 (9)0.0506 (9)0.0092 (12)0.0148 (10)
C910.105 (11)0.105 (11)0.079 (16)0.0000.0000.000
C920.20 (3)0.126 (18)0.065 (11)0.035 (14)0.0000.000
C930.126 (13)0.126 (13)0.067 (15)0.0000.0000.000
N110.195 (18)0.136 (13)0.181 (17)0.044 (12)0.032 (16)0.030 (13)
C120.159 (17)0.174 (19)0.161 (19)0.062 (15)0.008 (16)0.014 (16)
C130.166 (15)0.150 (14)0.095 (11)0.031 (12)0.026 (10)0.021 (10)
C140.107 (10)0.129 (12)0.147 (15)0.013 (9)0.022 (11)0.007 (11)
C150.172 (17)0.212 (19)0.095 (12)0.087 (15)0.034 (11)0.020 (12)
C160.23 (2)0.20 (2)0.082 (10)0.095 (18)0.029 (12)0.012 (12)
N31A0.156 (12)0.178 (12)0.067 (7)0.044 (10)0.005 (7)0.011 (8)
C32A0.16 (2)0.18 (2)0.12 (2)0.01 (2)0.00 (2)0.00 (2)
C33A0.16 (2)0.18 (2)0.15 (2)0.01 (2)0.03 (2)0.01 (2)
C34A0.137 (11)0.159 (12)0.082 (8)0.006 (11)0.026 (8)0.003 (9)
C35A0.14 (2)0.17 (2)0.085 (18)0.00 (2)0.019 (18)0.034 (18)
C36A0.17 (2)0.114 (17)0.078 (17)0.005 (18)0.052 (17)0.035 (15)
N31B0.156 (12)0.178 (12)0.067 (7)0.044 (10)0.005 (7)0.011 (8)
C32B0.18 (2)0.18 (2)0.083 (16)0.00 (2)0.014 (16)0.040 (16)
C33B0.17 (2)0.18 (2)0.109 (19)0.01 (2)0.013 (18)0.021 (18)
C34B0.137 (11)0.159 (12)0.082 (8)0.006 (11)0.026 (8)0.003 (9)
C35B0.14 (2)0.18 (2)0.103 (18)0.016 (19)0.030 (17)0.033 (18)
C36B0.16 (2)0.19 (2)0.084 (17)0.011 (18)0.015 (16)0.012 (17)
N51A0.216 (15)0.154 (11)0.104 (10)0.047 (11)0.016 (10)0.028 (9)
C52A0.19 (2)0.18 (2)0.051 (15)0.05 (2)0.033 (18)0.011 (17)
C53A0.15 (2)0.20 (2)0.11 (2)0.05 (2)0.03 (2)0.00 (2)
C54A0.185 (14)0.151 (12)0.095 (10)0.008 (12)0.015 (10)0.000 (10)
C55A0.21 (3)0.115 (19)0.072 (18)0.02 (2)0.00 (2)0.009 (16)
C56A0.21 (2)0.16 (2)0.081 (18)0.00 (2)0.038 (18)0.021 (18)
N51B0.216 (15)0.154 (11)0.104 (10)0.047 (11)0.016 (10)0.028 (9)
C52B0.22 (2)0.20 (2)0.035 (11)0.03 (2)0.024 (14)0.061 (14)
C53B0.20 (2)0.18 (2)0.054 (12)0.011 (19)0.001 (14)0.077 (13)
C54B0.185 (14)0.151 (12)0.095 (10)0.008 (12)0.015 (10)0.000 (10)
C55B0.20 (2)0.114 (16)0.048 (12)0.007 (16)0.001 (14)0.047 (11)
C56B0.157 (19)0.126 (16)0.106 (17)0.059 (15)0.005 (16)0.012 (14)
N710.201 (17)0.156 (13)0.085 (9)0.026 (12)0.055 (10)0.003 (9)
C720.186 (18)0.180 (17)0.089 (10)0.074 (14)0.055 (11)0.033 (12)
C730.169 (15)0.138 (12)0.088 (11)0.047 (12)0.007 (10)0.003 (9)
C740.153 (14)0.145 (14)0.094 (10)0.012 (12)0.012 (10)0.007 (10)
C750.151 (14)0.179 (17)0.101 (11)0.046 (13)0.017 (11)0.023 (11)
C760.22 (2)0.156 (16)0.106 (13)0.075 (16)0.007 (13)0.009 (11)
C41A0.132 (12)0.197 (17)0.119 (13)0.006 (12)0.002 (12)0.041 (14)
C42A0.147 (14)0.157 (15)0.129 (14)0.030 (11)0.031 (14)0.029 (14)
C43A0.159 (17)0.145 (16)0.146 (17)0.044 (13)0.011 (14)0.020 (13)
C44A0.135 (13)0.212 (19)0.101 (11)0.016 (13)0.004 (11)0.032 (14)
C45A0.186 (17)0.174 (15)0.058 (7)0.018 (13)0.011 (9)0.017 (9)
C46A0.176 (18)0.23 (2)0.136 (17)0.015 (16)0.095 (15)0.021 (16)
C61A0.181 (13)0.145 (11)0.102 (10)0.014 (11)0.017 (11)0.032 (10)
C62A0.18 (3)0.100 (19)0.10 (2)0.015 (19)0.03 (2)0.005 (17)
C63A0.19 (3)0.14 (2)0.057 (16)0.00 (2)0.005 (19)0.014 (16)
C64A0.175 (14)0.145 (12)0.120 (12)0.023 (11)0.035 (12)0.012 (12)
C65A0.16 (3)0.18 (2)0.12 (2)0.01 (2)0.04 (2)0.02 (2)
C66A0.19 (3)0.17 (2)0.09 (2)0.00 (2)0.04 (2)0.03 (2)
C81A0.113 (9)0.139 (11)0.086 (8)0.023 (8)0.016 (8)0.026 (9)
C82A0.142 (12)0.146 (12)0.077 (9)0.017 (9)0.006 (9)0.005 (9)
C83A0.110 (10)0.157 (14)0.090 (10)0.004 (10)0.002 (8)0.032 (10)
C84A0.131 (11)0.155 (12)0.062 (7)0.014 (9)0.012 (8)0.016 (9)
C85A0.120 (11)0.156 (12)0.099 (10)0.006 (9)0.003 (10)0.011 (11)
C86A0.128 (11)0.173 (15)0.073 (8)0.010 (11)0.008 (8)0.021 (9)
C21B0.133 (12)0.140 (12)0.114 (11)0.033 (10)0.029 (11)0.043 (11)
C22B0.119 (11)0.133 (12)0.114 (12)0.008 (10)0.015 (10)0.003 (10)
C23B0.125 (10)0.124 (9)0.060 (7)0.006 (8)0.015 (7)0.003 (7)
C24B0.133 (11)0.100 (8)0.077 (8)0.011 (7)0.026 (9)0.010 (8)
C25B0.140 (12)0.123 (11)0.062 (7)0.007 (9)0.002 (8)0.002 (7)
C26B0.140 (11)0.128 (10)0.072 (8)0.022 (8)0.003 (9)0.021 (8)
C61B0.181 (13)0.145 (11)0.102 (10)0.014 (11)0.017 (11)0.032 (10)
C62B0.16 (2)0.16 (2)0.10 (2)0.011 (18)0.008 (19)0.030 (17)
C63B0.15 (2)0.15 (2)0.104 (19)0.011 (18)0.020 (18)0.027 (16)
C64B0.175 (14)0.145 (12)0.120 (12)0.023 (11)0.035 (12)0.012 (12)
C65B0.18 (2)0.146 (19)0.12 (2)0.016 (19)0.01 (2)0.024 (19)
C66B0.22 (3)0.111 (17)0.059 (14)0.001 (18)0.007 (18)0.004 (12)
Geometric parameters (Å, º) top
S1A—S2A1.95 (2)C35A—C36A1.46 (3)
S2A—S3A1.91 (2)C32B—C33B1.38 (3)
S1B—S2B1.89 (3)C35B—C36B1.45 (3)
S1C—S2C1.94 (2)N51A—C56A1.31 (3)
S2C—S3C1.92 (2)N51A—C52A1.34 (3)
S4A—S5A1.90 (3)C52A—C53A1.42 (3)
S4B—S5B1.90 (3)C53A—C54A1.41 (2)
S4C—S5C1.90 (3)C54A—C55A1.35 (3)
S4D—S5D1.95 (3)C54A—C61A1.51 (3)
S5D—S6D1.92 (3)C55A—C56A1.48 (3)
Cu1—N111.99 (2)C52B—C53B1.41 (3)
Cu1—N31A2.033 (17)C55B—C56B1.46 (2)
Cu1—I22.644 (3)N71—C761.309 (19)
Cu1—I12.692 (4)N71—C721.33 (2)
Cu2—N51A1.97 (2)C72—C731.38 (2)
Cu2—N712.017 (19)C73—C741.393 (19)
Cu2—I12.649 (3)C74—C751.37 (2)
Cu2—I2i2.666 (4)C74—C81A1.40 (2)
I2—Cu2ii2.666 (4)C75—C761.46 (2)
C91—C84A1.556 (15)C41A—C46A1.39 (2)
C91—C84Aiii1.556 (15)C41A—C42A1.41 (2)
C91—C84Aiv1.556 (15)C42A—C43A1.40 (2)
C91—C84Av1.556 (15)C43A—C44A1.38 (2)
C92—C64Bvi1.49 (2)C44A—C45A1.39 (2)
C92—C64Avi1.49 (2)C45A—C46A1.41 (2)
C92—C64Bvii1.49 (2)C61A—C66A1.40 (2)
C92—C64Avii1.49 (2)C61A—C62A1.41 (3)
C92—C44Aviii1.57 (2)C62A—C63A1.41 (3)
C92—C44A1.57 (2)C63A—C64A1.37 (2)
C93—C24Bix1.543 (13)C64A—C65A1.41 (2)
C93—C24Bx1.543 (13)C64A—C92xii1.49 (2)
C93—C24Bxi1.543 (13)C65A—C66A1.41 (3)
C93—C24B1.543 (13)C81A—C86A1.400 (17)
N11—C121.31 (2)C81A—C82A1.412 (19)
N11—C161.32 (2)C82A—C83A1.401 (19)
C12—C131.40 (2)C83A—C84A1.394 (17)
C13—C141.399 (19)C84A—C85A1.419 (18)
C14—C151.34 (2)C85A—C86A1.39 (2)
C14—C21B1.47 (3)C21B—C26B1.383 (18)
C15—C161.47 (2)C21B—C22B1.41 (2)
N31A—C36A1.30 (2)C22B—C23B1.402 (19)
N31A—C32A1.31 (3)C23B—C24B1.362 (16)
C32A—C33A1.39 (3)C24B—C25B1.419 (17)
C33A—C34A1.40 (3)C25B—C26B1.418 (18)
C34A—C35A1.36 (3)C62B—C63B1.40 (3)
C34A—C41A1.45 (3)C65B—C66B1.44 (3)
S3A—S2A—S1A112 (3)C52A—N51A—Cu2117.9 (18)
S3C—S2C—S1C113 (3)N51A—C52A—C53A122 (2)
S6D—S5D—S4D110 (3)C54A—C53A—C52A120 (3)
N11—Cu1—N31A118.0 (8)C55A—C54A—C53A117 (2)
N11—Cu1—I2106.2 (6)C55A—C54A—C61A117 (2)
N31A—Cu1—I2104.5 (5)C53A—C54A—C61A124 (2)
N11—Cu1—I1103.8 (7)C54A—C55A—C56A112 (3)
N31A—Cu1—I1103.5 (5)N51A—C56A—C55A125 (3)
I2—Cu1—I1121.75 (12)C76—N71—C72113 (2)
N51A—Cu2—N71112.8 (8)C76—N71—Cu2119.0 (15)
N51A—Cu2—I1104.3 (6)C72—N71—Cu2125.5 (12)
N71—Cu2—I1107.9 (4)N71—C72—C73124.2 (19)
N51A—Cu2—I2i103.5 (6)C72—C73—C74121.1 (16)
N71—Cu2—I2i105.6 (5)C75—C74—C81A122.1 (15)
I1—Cu2—I2i122.91 (12)C75—C74—C73116.4 (18)
Cu2—I1—Cu1111.77 (9)C81A—C74—C73121.4 (16)
Cu1—I2—Cu2ii112.42 (9)C74—C75—C76116.4 (16)
C84A—C91—C84Aiii108.8 (12)N71—C76—C75126.7 (19)
C84A—C91—C84Aiv109.8 (6)C46A—C41A—C42A116.5 (18)
C84Aiii—C91—C84Aiv109.8 (6)C46A—C41A—C34A120.2 (19)
C84A—C91—C84Av109.8 (6)C42A—C41A—C34A123.2 (18)
C84Aiii—C91—C84Av109.8 (6)C43A—C42A—C41A119.4 (17)
C84Aiv—C91—C84Av108.8 (12)C44A—C43A—C42A123.5 (19)
C64Bvi—C92—C64Bvii118 (2)C45A—C44A—C43A117.5 (19)
C64Avi—C92—C64Avii118 (2)C45A—C44A—C92125.3 (16)
C64Avi—C92—C44Aviii112.1 (10)C43A—C44A—C92117.0 (18)
C64Avii—C92—C44Aviii105.1 (12)C44A—C45A—C46A119.3 (17)
C64Avi—C92—C44A105.2 (12)C41A—C46A—C45A124 (2)
C64Avii—C92—C44A112.1 (10)C66A—C61A—C62A120 (2)
C44Aviii—C92—C44A104 (2)C66A—C61A—C54A118.7 (19)
C24Bix—C93—C24Bx109.0 (6)C62A—C61A—C54A120.9 (19)
C24Bix—C93—C24Bxi110.4 (12)C63A—C62A—C61A118 (2)
C24Bx—C93—C24Bxi109.0 (6)C64A—C63A—C62A122 (3)
C24Bix—C93—C24B109.0 (6)C63A—C64A—C65A119 (2)
C24Bx—C93—C24B110.4 (12)C63A—C64A—C92xii121.2 (19)
C24Bxi—C93—C24B109.0 (6)C65A—C64A—C92xii117 (2)
C12—N11—C16115 (2)C64A—C65A—C66A120 (3)
C12—N11—Cu1122.1 (17)C61A—C66A—C65A120 (3)
C16—N11—Cu1123.1 (17)C74—C81A—C86A121.4 (15)
N11—C12—C13127 (2)C74—C81A—C82A120.5 (15)
C14—C13—C12116.7 (16)C86A—C81A—C82A117.8 (15)
C15—C14—C13120.3 (19)C83A—C82A—C81A119.8 (15)
C15—C14—C21B122.2 (16)C82A—C83A—C84A121.9 (15)
C13—C14—C21B117.5 (16)C83A—C84A—C85A117.6 (15)
C14—C15—C16116.7 (16)C83A—C84A—C91118.6 (12)
N11—C16—C15124.5 (17)C85A—C84A—C91122.9 (12)
C36A—N31A—C32A115 (2)C86A—C85A—C84A119.3 (16)
C36A—N31A—Cu1121.1 (18)C85A—C86A—C81A122.2 (15)
C32A—N31A—Cu1123.1 (17)C26B—C21B—C22B118.2 (16)
N31A—C32A—C33A120 (3)C26B—C21B—C14118.4 (17)
C32A—C33A—C34A123 (3)C22B—C21B—C14123.3 (15)
C35A—C34A—C33A116 (2)C23B—C22B—C21B120.9 (15)
C35A—C34A—C41A117.7 (18)C24B—C23B—C22B121.9 (14)
C33A—C34A—C41A125 (2)C23B—C24B—C25B117.6 (13)
C34A—C35A—C36A113 (2)C23B—C24B—C93126.7 (12)
N31A—C36A—C35A127 (2)C25B—C24B—C93115.7 (11)
C56A—N51A—C52A112 (2)C26B—C25B—C24B121.2 (14)
C56A—N51A—Cu2128.9 (19)C21B—C26B—C25B120.1 (14)
Symmetry codes: (i) x, y, z+1; (ii) x, y, z1; (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, z1; (x) x+1, y+1, z; (xi) y+1, x, z1; (xii) y, x+2, z+3.
(300K_S_helical) top
Crystal data top
(CuI)1.88(N1C5H4C6H4)4C(cycroS3)0.62(bentS3)0.39Dx = 1.397 Mg m3
Mr = 1083.34Synchrotron radiation, λ = 0.800 Å
Tetragonal, I4Cell parameters from 52191 reflections
a = 26.8758 (4) Åθ = 2.7–28.1°
c = 7.1689 (1) ŵ = 2.72 mm1
V = 5178.1 (2) Å3T = 300 K
Z = 4Needle, brownish yellow
F(000) = 21410.76 × 0.05 × 0.05 mm
Data collection top
ADSC Q210 CCD area detector
diffractometer
4353 independent reflections
Radiation source: PLSII 2D bending magnet3852 reflections with I > 2σ(I)
Si(111) double crystal monochromatorRint = 0.035
ω scanθmax = 28.1°, θmin = 2.7°
Absorption correction: multi-scan
[c.f. r.h. blessing, acta cryst. (1995), a51, 33-38]
h = 3131
Tmin = 0.587, Tmax = 0.620k = 3131
52191 measured reflectionsl = 88
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.118 w = 1/[σ2(Fo2) + (0.0908P)2 + 0.1257P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.086
4353 reflectionsΔρmax = 0.25 e Å3
365 parametersΔρmin = 0.45 e Å3
397 restraintsAbsolute 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 methodsAbsolute structure parameter: 0.430 (7)
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. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S1X0.3957 (8)0.239 (2)0.660 (10)0.30 (4)0.166 (12)
S2X0.457 (3)0.284 (3)0.622 (17)0.47 (5)0.166 (12)
S3X0.4598 (11)0.2278 (15)0.818 (7)0.187 (17)0.166 (12)
S1B0.479 (3)0.250 (2)0.417 (19)0.47 (5)0.193 (12)
S2B0.480 (2)0.255 (3)0.152 (19)0.47 (4)0.193 (12)
S3B0.419 (2)0.247 (3)0.022 (18)0.49 (5)0.193 (12)
S1A0.485 (4)0.228 (3)0.65 (2)0.47 (5)0.143 (13)
S2A0.435 (3)0.220 (3)0.42 (2)0.46 (5)0.143 (13)
S3A0.489 (4)0.278 (4)0.41 (2)0.46 (5)0.143 (13)
I10.30489 (3)0.24567 (4)0.61605 (13)0.1105 (3)0.940 (9)
Cu10.25078 (6)0.29817 (5)0.3765 (2)0.1081 (4)0.940 (9)
C10.00000.50001.25000.081 (4)
C20.50000.50000.50000.092 (5)
N1A0.2026 (4)0.3409 (4)0.5329 (13)0.109 (3)
C2A0.1585 (7)0.3554 (8)0.470 (2)0.151 (7)
H2AA0.14900.34580.35030.181*
C3A0.1263 (5)0.3842 (6)0.5738 (16)0.123 (4)
H3AA0.09710.39630.52100.147*
C4A0.1378 (4)0.3949 (4)0.7562 (14)0.093 (3)
C5A0.1819 (5)0.3770 (6)0.8207 (18)0.129 (5)
H5AA0.19060.38270.94440.154*
C6A0.2141 (5)0.3507 (7)0.7084 (17)0.135 (6)
H6AA0.24430.33980.75660.162*
C7A0.1044 (3)0.4239 (3)0.8815 (13)0.087 (2)
C8A0.1218 (4)0.4546 (4)1.0209 (14)0.095 (3)
H8AA0.15590.45901.03460.115*
C9A0.0894 (3)0.4796 (4)1.1428 (13)0.091 (2)
H9AA0.10220.49981.23640.109*
C10A0.0385 (3)0.4741 (3)1.1240 (13)0.083 (2)
C11A0.0211 (4)0.4434 (4)0.9792 (13)0.088 (2)
H11A0.01300.43950.96440.105*
C12A0.0527 (4)0.4186 (4)0.8573 (13)0.095 (2)
H12A0.04000.39890.76190.114*
N1B0.3031 (5)0.3376 (4)0.2311 (13)0.110 (3)0.651 (18)
C2B0.3159 (10)0.3202 (8)0.069 (3)0.128 (7)0.651 (18)
H2BA0.30250.29000.03040.153*0.651 (18)
C3B0.3488 (10)0.3449 (7)0.048 (3)0.113 (6)0.651 (18)
H3BA0.35840.33020.15980.135*0.651 (18)
C4B0.3672 (4)0.3902 (5)0.0014 (17)0.104 (3)0.651 (18)
C5B0.3607 (10)0.4034 (9)0.184 (2)0.125 (7)0.651 (18)
H5BA0.37880.42950.23610.150*0.651 (18)
C6B0.3272 (9)0.3773 (8)0.290 (3)0.123 (7)0.651 (18)
H6BA0.32100.38830.41060.148*0.651 (18)
C7B0.4023 (4)0.4170 (4)0.1266 (16)0.098 (3)
C8B0.4083 (4)0.4682 (4)0.1078 (16)0.103 (3)
H8BA0.39110.48550.01550.124*
C9B0.4402 (4)0.4934 (4)0.2286 (14)0.098 (3)
H9BA0.44450.52750.21390.117*
C10B0.4658 (4)0.4691 (4)0.3703 (13)0.094 (2)
C11B0.4595 (4)0.4179 (4)0.3882 (18)0.107 (3)
H11B0.47700.40020.47820.129*
C12B0.4269 (5)0.3941 (5)0.2695 (18)0.116 (4)
H12B0.42120.36030.28810.139*
N1Y0.3031 (5)0.3376 (4)0.2311 (13)0.110 (3)0.349 (18)
C2Y0.3427 (13)0.3167 (11)0.161 (6)0.131 (11)0.349 (18)
H2YA0.35010.28430.19720.158*0.349 (18)
C3Y0.3744 (13)0.3397 (9)0.036 (6)0.111 (8)0.349 (18)
H3YA0.39980.32210.02170.133*0.349 (18)
C4Y0.3672 (4)0.3902 (5)0.0014 (17)0.104 (3)0.349 (18)
C5Y0.3267 (11)0.4107 (10)0.082 (5)0.112 (9)0.349 (18)
H5YA0.32090.44460.06610.134*0.349 (18)
C6Y0.2939 (11)0.3836 (10)0.188 (5)0.115 (9)0.349 (18)
H6YA0.26470.39840.22980.138*0.349 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1X0.093 (13)0.32 (5)0.48 (11)0.069 (18)0.08 (4)0.04 (7)
S2X0.30 (4)0.27 (4)0.85 (13)0.03 (3)0.09 (6)0.30 (6)
S3X0.120 (17)0.18 (3)0.27 (5)0.033 (16)0.04 (2)0.02 (3)
S1B0.28 (4)0.21 (5)0.91 (13)0.02 (4)0.11 (6)0.23 (7)
S2B0.28 (3)0.23 (4)0.90 (13)0.02 (4)0.08 (6)0.19 (6)
S3B0.25 (4)0.25 (5)0.95 (14)0.04 (5)0.07 (6)0.21 (8)
S1A0.26 (5)0.28 (5)0.86 (13)0.05 (5)0.09 (7)0.26 (7)
S2A0.22 (4)0.22 (4)0.93 (13)0.03 (3)0.08 (7)0.15 (7)
S3A0.26 (4)0.23 (4)0.87 (13)0.01 (4)0.10 (6)0.25 (6)
I10.1199 (5)0.1261 (5)0.0855 (4)0.0212 (4)0.0000 (5)0.0066 (4)
Cu10.1228 (8)0.1155 (7)0.0859 (7)0.0155 (8)0.0232 (8)0.0001 (9)
C10.092 (6)0.092 (6)0.058 (8)0.0000.0000.000
C20.104 (8)0.104 (8)0.068 (11)0.0000.0000.000
N1A0.122 (7)0.120 (7)0.084 (5)0.027 (5)0.004 (5)0.000 (5)
C2A0.182 (15)0.197 (16)0.072 (6)0.073 (13)0.013 (8)0.003 (9)
C3A0.127 (8)0.161 (10)0.081 (7)0.049 (8)0.002 (6)0.016 (7)
C4A0.108 (7)0.101 (6)0.070 (5)0.010 (5)0.002 (5)0.000 (5)
C5A0.131 (10)0.163 (11)0.091 (7)0.057 (9)0.001 (6)0.020 (7)
C6A0.130 (10)0.191 (15)0.085 (7)0.058 (10)0.017 (6)0.022 (8)
C7A0.097 (5)0.104 (6)0.061 (5)0.014 (4)0.008 (4)0.003 (5)
C8A0.091 (5)0.118 (7)0.077 (5)0.010 (5)0.001 (5)0.014 (5)
C9A0.088 (5)0.111 (6)0.073 (6)0.005 (4)0.001 (4)0.009 (4)
C10A0.093 (5)0.089 (5)0.066 (5)0.003 (4)0.001 (4)0.002 (4)
C11A0.098 (6)0.101 (6)0.064 (5)0.012 (4)0.004 (4)0.003 (4)
C12A0.112 (6)0.110 (6)0.064 (5)0.010 (5)0.002 (4)0.010 (5)
N1B0.140 (8)0.114 (7)0.076 (5)0.016 (6)0.014 (6)0.004 (5)
C2B0.146 (16)0.134 (13)0.102 (13)0.057 (12)0.021 (11)0.035 (11)
C3B0.135 (14)0.125 (12)0.078 (10)0.022 (11)0.030 (10)0.030 (9)
C4B0.121 (8)0.110 (7)0.082 (6)0.005 (6)0.006 (6)0.002 (5)
C5B0.159 (15)0.140 (13)0.076 (9)0.036 (12)0.024 (10)0.006 (9)
C6B0.144 (15)0.138 (14)0.088 (11)0.031 (12)0.024 (10)0.032 (10)
C7B0.098 (5)0.122 (7)0.075 (6)0.000 (5)0.004 (6)0.003 (6)
C8B0.121 (7)0.117 (7)0.071 (5)0.002 (5)0.011 (7)0.003 (6)
C9B0.127 (8)0.101 (7)0.065 (5)0.000 (5)0.011 (5)0.004 (5)
C10B0.118 (7)0.109 (6)0.055 (5)0.003 (5)0.009 (5)0.001 (5)
C11B0.124 (7)0.114 (7)0.084 (6)0.001 (6)0.022 (7)0.003 (7)
C12B0.147 (10)0.106 (7)0.094 (7)0.001 (7)0.019 (7)0.007 (6)
N1Y0.140 (8)0.114 (7)0.076 (5)0.016 (6)0.014 (6)0.004 (5)
C2Y0.16 (2)0.120 (19)0.11 (2)0.028 (19)0.01 (2)0.019 (19)
C3Y0.110 (17)0.121 (17)0.102 (17)0.023 (15)0.031 (15)0.001 (15)
C4Y0.121 (8)0.110 (7)0.082 (6)0.005 (6)0.006 (6)0.002 (5)
C5Y0.116 (16)0.121 (16)0.098 (18)0.009 (15)0.024 (15)0.008 (15)
C6Y0.085 (15)0.16 (2)0.102 (18)0.029 (15)0.045 (14)0.019 (17)
Geometric parameters (Å, º) top
S1X—S2X2.08 (5)C3A—C4A1.373 (15)
S1X—S3X2.08 (4)C4A—C5A1.359 (15)
S1X—I12.47 (2)C4A—C7A1.490 (13)
S2X—S3X2.07 (5)C5A—C6A1.377 (16)
S1B—S2B1.91 (3)C7A—C8A1.379 (14)
S2B—S3B1.91 (3)C7A—C12A1.407 (13)
S1A—S2A2.15 (10)C8A—C9A1.404 (13)
S1A—S3A2.15 (10)C9A—C10A1.383 (12)
S2A—S3A2.14 (10)C10A—C11A1.406 (13)
I1—Cu12.6563 (17)C11A—C12A1.389 (13)
I1—Cu1i2.6669 (18)N1B—C2B1.296 (18)
Cu1—N1B2.046 (11)N1B—C6B1.317 (18)
Cu1—N1A2.062 (9)C2B—C3B1.391 (19)
Cu1—I1ii2.6669 (18)C3B—C4B1.355 (19)
C1—C10A1.539 (9)C4B—C5B1.389 (18)
C1—C10Aiii1.539 (9)C4B—C7B1.489 (15)
C1—C10Aiv1.539 (9)C5B—C6B1.37 (2)
C1—C10Av1.539 (9)C7B—C12B1.365 (14)
C2—C10Bvi1.549 (10)C7B—C8B1.393 (14)
C2—C10Bvii1.549 (10)C8B—C9B1.394 (14)
C2—C10Bviii1.549 (10)C9B—C10B1.390 (13)
C2—C10B1.549 (10)C10B—C11B1.391 (15)
N1A—C6A1.322 (15)C11B—C12B1.381 (15)
N1A—C2A1.327 (17)C2Y—C3Y1.38 (2)
C2A—C3A1.381 (17)C5Y—C6Y1.37 (2)
S2X—S1X—S3X59.8 (8)C5A—C4A—C3A116.5 (11)
S2X—S1X—I1137 (3)C5A—C4A—C7A120.3 (9)
S3X—S1X—I1154 (4)C3A—C4A—C7A123.2 (10)
S3X—S2X—S1X60.2 (8)C4A—C5A—C6A122.0 (11)
S2X—S3X—S1X60.0 (8)N1A—C6A—C5A120.7 (13)
S1B—S2B—S3B117 (2)C8A—C7A—C12A118.9 (8)
S2A—S1A—S3A59.7 (8)C8A—C7A—C4A123.2 (9)
S3A—S2A—S1A60.1 (8)C12A—C7A—C4A117.9 (9)
S2A—S3A—S1A60.2 (8)C7A—C8A—C9A121.8 (9)
S1X—I1—Cu1131.7 (15)C10A—C9A—C8A120.2 (9)
S1X—I1—Cu1i115.5 (16)C9A—C10A—C11A117.5 (9)
Cu1—I1—Cu1i112.35 (3)C9A—C10A—C1124.0 (7)
N1B—Cu1—N1A114.9 (4)C11A—C10A—C1118.5 (7)
N1B—Cu1—I1103.2 (3)C12A—C11A—C10A123.0 (9)
N1A—Cu1—I1106.7 (3)C11A—C12A—C7A118.5 (9)
N1B—Cu1—I1ii104.9 (3)C2B—N1B—C6B116.6 (13)
N1A—Cu1—I1ii105.9 (3)C2B—N1B—Cu1116.8 (11)
I1—Cu1—I1ii121.67 (5)C6B—N1B—Cu1126.5 (9)
C10A—C1—C10Aiii110.1 (4)N1B—C2B—C3B122.5 (15)
C10A—C1—C10Aiv108.1 (7)C4B—C3B—C2B120.8 (13)
C10Aiii—C1—C10Aiv110.1 (4)C3B—C4B—C5B114.9 (13)
C10A—C1—C10Av110.1 (4)C3B—C4B—C7B121.1 (11)
C10Aiii—C1—C10Av108.1 (7)C5B—C4B—C7B122.2 (12)
C10Aiv—C1—C10Av110.1 (4)C6B—C5B—C4B118.6 (17)
C10Bvi—C2—C10Bvii111.1 (4)N1B—C6B—C5B124.2 (16)
C10Bvi—C2—C10Bviii111.1 (4)C12B—C7B—C8B117.6 (10)
C10Bvii—C2—C10Bviii106.2 (8)C12B—C7B—C4B122.7 (11)
C10Bvi—C2—C10B106.2 (8)C8B—C7B—C4B119.6 (9)
C10Bvii—C2—C10B111.1 (4)C7B—C8B—C9B119.4 (10)
C10Bviii—C2—C10B111.1 (4)C10B—C9B—C8B122.0 (11)
C6A—N1A—C2A118.4 (11)C9B—C10B—C11B118.2 (10)
C6A—N1A—Cu1118.8 (9)C9B—C10B—C2118.7 (9)
C2A—N1A—Cu1122.6 (9)C11B—C10B—C2123.1 (8)
N1A—C2A—C3A122.6 (13)C12B—C11B—C10B118.6 (10)
C4A—C3A—C2A119.4 (12)C7B—C12B—C11B124.1 (11)
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x+1/2, y+1/2, z1/2; (iii) y+1/2, x+1/2, z+5/2; (iv) x, y+1, z; (v) y1/2, x+1/2, z+5/2; (vi) x+1, y+1, z; (vii) y+1, x, z1; (viii) y, x+1, z1.
(350k_S_helical) top
Crystal data top
(CuI)1.88(N1C5H4C6H4)4C(bentS3)1.00Dx = 1.384 Mg m3
Mr = 1083.34Synchrotron radiation, λ = 0.800 Å
Tetragonal, I4Cell parameters from 49763 reflections
a = 26.8987 (5) Åθ = 2.7–26.4°
c = 7.1788 (1) ŵ = 2.68 mm1
V = 5194.1 (2) Å3T = 350 K
Z = 4Needle, brownish yellow
F(000) = 21270.76 × 0.05 × 0.05 mm
Data collection top
ADSC Q210 CCD area detector
diffractometer
3717 independent reflections
Radiation source: PLSII 2D bending magnet3278 reflections with I > 2σ(I)
Si(111) double crystal monochromatorRint = 0.043
ω scanθmax = 26.4°, θmin = 2.7°
Absorption correction: multi-scan
[c.f. r.h. blessing, acta cryst. (1995), a51, 33-38]
h = 2929
Tmin = 0.523, Tmax = 0.567k = 2929
49763 measured reflectionsl = 77
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.120 w = 1/[σ2(Fo2) + (0.0953P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
3717 reflectionsΔρmax = 0.32 e Å3
338 parametersΔρmin = 0.50 e Å3
77 restraintsAbsolute 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 methodsAbsolute structure parameter: 0.149 (17)
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. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S1A0.573 (2)0.742 (2)0.713 (12)0.67 (6)0.403 (14)
S2A0.521 (2)0.7343 (17)0.531 (10)0.60 (5)0.403 (14)
S3A0.527 (2)0.773 (2)0.304 (13)0.61 (6)0.403 (14)
S1B0.6038 (9)0.762 (2)1.322 (10)0.22 (4)0.099 (14)
S2B0.5409 (15)0.769 (3)1.189 (11)0.20 (3)0.099 (14)
S3B0.515 (4)0.745 (4)0.957 (13)0.29 (5)0.099 (14)
I10.69522 (3)0.75402 (4)0.38398 (15)0.1201 (3)0.9381
Cu10.74940 (7)0.70135 (5)0.6238 (3)0.1183 (5)0.9381
C11.00000.50000.25000.091 (5)
C20.50000.50001.50000.093 (5)
N1A0.7974 (5)0.6598 (5)0.4667 (15)0.119 (4)
C2A0.8405 (9)0.6438 (11)0.531 (2)0.191 (12)
H2AA0.84850.65080.65430.229*
C3A0.8753 (6)0.6166 (7)0.424 (2)0.142 (6)
H3AA0.90550.60650.47490.170*
C4A0.8632 (5)0.6054 (5)0.2426 (16)0.097 (3)
C5A0.8196 (7)0.6242 (8)0.177 (2)0.154 (7)
H5AA0.81100.61900.05320.185*
C6A0.7878 (7)0.6509 (9)0.292 (2)0.159 (9)
H6AA0.75830.66300.24180.191*
C7A0.8961 (4)0.5771 (4)0.1196 (16)0.093 (3)
C8A0.8790 (5)0.5457 (5)0.0214 (18)0.110 (3)
H8AA0.84500.54100.03450.132*
C9A0.9110 (4)0.5212 (5)0.1436 (16)0.103 (3)
H9AA0.89810.50170.23890.123*
C10A0.9619 (4)0.5260 (4)0.1230 (17)0.092 (3)
C11A0.9790 (5)0.5567 (4)0.0221 (16)0.098 (3)
H11A1.01310.56050.03850.117*
C12A0.9473 (4)0.5813 (4)0.1406 (15)0.105 (3)
H12A0.96020.60090.23570.126*
N1B0.6971 (6)0.6613 (5)0.7693 (16)0.118 (3)0.70 (3)
C2B0.6842 (14)0.6808 (10)0.928 (4)0.156 (13)0.70 (3)
H2BA0.69740.71130.96340.188*0.70 (3)
C3B0.6500 (13)0.6559 (8)1.047 (3)0.130 (9)0.70 (3)
H3BA0.63910.67091.15620.156*0.70 (3)
C4B0.6334 (6)0.6097 (6)0.9982 (19)0.114 (4)0.70 (3)
C5B0.6408 (13)0.5952 (9)0.817 (3)0.149 (14)0.70 (3)
H5BA0.62400.56810.76720.179*0.70 (3)
C6B0.6744 (12)0.6224 (11)0.708 (3)0.148 (11)0.70 (3)
H6BA0.68060.61200.58700.177*0.70 (3)
C7B0.5981 (4)0.5827 (5)1.1270 (17)0.106 (3)
C8B0.5913 (5)0.5314 (4)1.1075 (18)0.113 (3)
H8BA0.60790.51421.01370.135*
C9B0.5599 (5)0.5060 (5)1.2281 (15)0.100 (3)
H9BA0.55570.47191.21420.120*
C10B0.5343 (5)0.5310 (5)1.3706 (13)0.099 (3)
C11B0.5411 (5)0.5817 (4)1.389 (2)0.116 (4)
H11B0.52400.59951.47980.139*
C12B0.5739 (6)0.6054 (5)1.270 (2)0.125 (5)
H12B0.57990.63911.28940.151*
N1Y0.6971 (6)0.6613 (5)0.7693 (16)0.118 (3)0.30 (3)
C2Y0.6561 (15)0.6823 (13)0.828 (8)0.14 (2)0.30 (3)
H2YA0.64830.71390.78510.165*0.30 (3)
C3Y0.6230 (15)0.6590 (12)0.955 (8)0.113 (15)0.30 (3)
H3YA0.59600.67571.00610.135*0.30 (3)
C4Y0.6334 (6)0.6097 (6)0.9982 (19)0.114 (4)0.30 (3)
C5Y0.6756 (13)0.5890 (13)0.928 (7)0.109 (15)0.30 (3)
H5YA0.68310.55600.95480.131*0.30 (3)
C6Y0.7076 (13)0.6171 (12)0.816 (6)0.107 (16)0.30 (3)
H6YA0.73730.60300.77580.128*0.30 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.46 (7)0.44 (6)1.10 (17)0.20 (5)0.04 (10)0.12 (10)
S2A0.37 (5)0.34 (5)1.08 (16)0.11 (5)0.15 (9)0.15 (7)
S3A0.46 (7)0.32 (5)1.04 (16)0.16 (5)0.13 (11)0.11 (8)
S1B0.047 (14)0.21 (4)0.40 (9)0.055 (17)0.05 (3)0.00 (5)
S2B0.09 (2)0.15 (4)0.37 (9)0.03 (2)0.02 (3)0.05 (4)
S3B0.22 (6)0.18 (5)0.49 (13)0.05 (5)0.05 (8)0.05 (8)
I10.1301 (6)0.1384 (6)0.0919 (4)0.0191 (5)0.0009 (7)0.0075 (5)
Cu10.1338 (9)0.1263 (9)0.0948 (9)0.0129 (10)0.0261 (9)0.0003 (12)
C10.104 (8)0.104 (8)0.065 (11)0.0000.0000.000
C20.109 (9)0.109 (9)0.061 (11)0.0000.0000.000
N1A0.134 (9)0.136 (9)0.085 (6)0.031 (7)0.001 (6)0.006 (6)
C2A0.23 (2)0.28 (3)0.064 (7)0.12 (2)0.003 (11)0.008 (13)
C3A0.143 (11)0.183 (15)0.099 (11)0.051 (10)0.007 (9)0.004 (10)
C4A0.107 (8)0.113 (8)0.070 (6)0.011 (6)0.000 (6)0.007 (6)
C5A0.180 (17)0.184 (16)0.099 (9)0.083 (14)0.003 (10)0.015 (10)
C6A0.161 (15)0.21 (2)0.102 (11)0.090 (15)0.021 (9)0.026 (11)
C7A0.098 (6)0.112 (7)0.070 (7)0.013 (5)0.001 (5)0.002 (6)
C8A0.103 (7)0.137 (9)0.089 (7)0.013 (7)0.003 (6)0.016 (7)
C9A0.100 (7)0.124 (7)0.085 (7)0.003 (5)0.000 (6)0.019 (6)
C10A0.100 (7)0.093 (6)0.083 (7)0.005 (5)0.001 (6)0.001 (6)
C11A0.118 (8)0.112 (8)0.064 (6)0.017 (6)0.008 (5)0.006 (5)
C12A0.124 (8)0.118 (8)0.073 (7)0.010 (6)0.003 (6)0.009 (6)
N1B0.149 (10)0.120 (9)0.085 (7)0.017 (8)0.015 (7)0.001 (6)
C2B0.20 (3)0.15 (2)0.113 (19)0.085 (19)0.04 (2)0.034 (15)
C3B0.18 (2)0.130 (16)0.082 (14)0.024 (16)0.042 (15)0.030 (11)
C4B0.135 (11)0.119 (10)0.087 (8)0.014 (8)0.010 (8)0.004 (7)
C5B0.20 (3)0.147 (19)0.101 (15)0.06 (2)0.063 (19)0.020 (14)
C6B0.15 (2)0.18 (2)0.113 (18)0.030 (18)0.024 (18)0.050 (17)
C7B0.110 (7)0.140 (10)0.069 (7)0.011 (6)0.006 (7)0.002 (7)
C8B0.136 (9)0.129 (9)0.073 (6)0.000 (7)0.017 (8)0.004 (8)
C9B0.129 (8)0.110 (8)0.060 (5)0.004 (6)0.015 (5)0.001 (6)
C10B0.129 (9)0.119 (8)0.048 (5)0.004 (6)0.009 (6)0.004 (6)
C11B0.131 (8)0.125 (9)0.091 (7)0.007 (7)0.009 (9)0.011 (8)
C12B0.161 (13)0.112 (9)0.103 (10)0.007 (8)0.040 (9)0.013 (7)
N1Y0.149 (10)0.120 (9)0.085 (7)0.017 (8)0.015 (7)0.001 (6)
C2Y0.21 (6)0.08 (3)0.12 (4)0.04 (3)0.02 (5)0.01 (3)
C3Y0.12 (3)0.12 (3)0.10 (4)0.04 (3)0.02 (3)0.01 (3)
C4Y0.135 (11)0.119 (10)0.087 (8)0.014 (8)0.010 (8)0.004 (7)
C5Y0.09 (2)0.12 (3)0.11 (4)0.01 (2)0.01 (3)0.01 (3)
C6Y0.07 (2)0.15 (4)0.10 (3)0.01 (2)0.05 (2)0.03 (3)
Geometric parameters (Å, º) top
S1A—S2A1.94 (3)C4A—C7A1.464 (15)
S2A—S3A1.95 (3)C5A—C6A1.389 (19)
S1B—S2B1.95 (3)C7A—C12A1.392 (15)
S1B—I1i2.51 (2)C7A—C8A1.394 (16)
S2B—S3B1.93 (3)C8A—C9A1.395 (15)
I1—S1Bii2.51 (2)C9A—C10A1.383 (14)
I1—Cu12.664 (2)C10A—C11A1.407 (15)
I1—Cu1iii2.674 (2)C11A—C12A1.374 (15)
Cu1—N1A2.047 (11)N1B—C6B1.29 (2)
Cu1—N1B2.057 (12)N1B—C2B1.30 (2)
Cu1—I1iv2.674 (2)C2B—C3B1.42 (2)
C1—C10Av1.539 (11)C3B—C4B1.37 (2)
C1—C10Avi1.539 (11)C4B—C5B1.37 (2)
C1—C10Avii1.539 (11)C4B—C7B1.511 (18)
C1—C10A1.539 (11)C5B—C6B1.40 (2)
C2—C10B1.552 (11)C7B—C12B1.360 (16)
C2—C10Bviii1.552 (11)C7B—C8B1.400 (16)
C2—C10Bix1.552 (11)C8B—C9B1.389 (15)
C2—C10Bx1.552 (11)C9B—C10B1.404 (14)
N1A—C6A1.304 (18)C10B—C11B1.383 (16)
N1A—C2A1.32 (2)C11B—C12B1.384 (17)
C2A—C3A1.42 (2)C2Y—C3Y1.42 (3)
C3A—C4A1.376 (18)C5Y—C6Y1.40 (3)
C4A—C5A1.359 (18)
S1A—S2A—S3A116 (5)C4A—C5A—C6A121.2 (14)
S2B—S1B—I1i161 (4)N1A—C6A—C5A122.9 (15)
S3B—S2B—S1B135 (4)C12A—C7A—C8A117.0 (10)
S1Bii—I1—Cu1134.3 (16)C12A—C7A—C4A119.3 (10)
S1Bii—I1—Cu1iii112.4 (16)C8A—C7A—C4A123.7 (10)
Cu1—I1—Cu1iii112.67 (4)C7A—C8A—C9A122.7 (11)
N1A—Cu1—N1B115.2 (5)C10A—C9A—C8A120.0 (11)
N1A—Cu1—I1106.3 (3)C9A—C10A—C11A117.2 (10)
N1B—Cu1—I1103.4 (4)C9A—C10A—C1123.6 (9)
N1A—Cu1—I1iv106.2 (4)C11A—C10A—C1119.2 (8)
N1B—Cu1—I1iv105.2 (4)C12A—C11A—C10A122.6 (11)
I1—Cu1—I1iv121.17 (5)C11A—C12A—C7A120.6 (11)
C10Av—C1—C10Avi110.5 (5)C6B—N1B—C2B119.9 (16)
C10Av—C1—C10Avii107.4 (9)C6B—N1B—Cu1125.2 (12)
C10Avi—C1—C10Avii110.5 (5)C2B—N1B—Cu1114.5 (12)
C10Av—C1—C10A110.5 (5)N1B—C2B—C3B120.6 (17)
C10Avi—C1—C10A107.4 (9)C4B—C3B—C2B119.0 (15)
C10Avii—C1—C10A110.5 (5)C3B—C4B—C5B116.9 (15)
C10B—C2—C10Bviii106.5 (9)C3B—C4B—C7B119.1 (13)
C10B—C2—C10Bix111.0 (4)C5B—C4B—C7B122.4 (14)
C10Bviii—C2—C10Bix111.0 (5)C4B—C5B—C6B118.2 (18)
C10B—C2—C10Bx111.0 (4)N1B—C6B—C5B122.8 (18)
C10Bviii—C2—C10Bx111.0 (4)C12B—C7B—C8B117.1 (11)
C10Bix—C2—C10Bx106.5 (9)C12B—C7B—C4B123.2 (12)
C6A—N1A—C2A116.9 (13)C8B—C7B—C4B119.6 (11)
C6A—N1A—Cu1120.3 (11)C9B—C8B—C7B120.1 (11)
C2A—N1A—Cu1122.7 (10)C8B—C9B—C10B121.2 (12)
N1A—C2A—C3A124.1 (15)C11B—C10B—C9B118.5 (11)
C4A—C3A—C2A118.0 (15)C11B—C10B—C2123.4 (9)
C5A—C4A—C3A116.8 (12)C9B—C10B—C2118.1 (10)
C5A—C4A—C7A120.3 (11)C10B—C11B—C12B118.6 (12)
C3A—C4A—C7A122.8 (12)C7B—C12B—C11B124.4 (13)
Symmetry codes: (i) x, y, z+1; (ii) x, y, z1; (iii) x+3/2, y+3/2, z1/2; (iv) x+3/2, y+3/2, z+1/2; (v) y+3/2, x1/2, z1/2; (vi) x+2, y+1, z; (vii) y+1/2, x+3/2, z1/2; (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)1.50Dx = 1.390 Mg m3
Mr = 1077.31Synchrotron radiation, λ = 0.700 Å
Tetragonal, I4Cell parameters from 65225 reflections
a = 26.8664 (4) Åθ = 2.4–29.5°
c = 7.1717 (1) ŵ = 1.86 mm1
V = 5176.5 (2) Å3T = 300 K
Z = 4Needle, brownish yellow
F(000) = 21290.15 × 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 magnetRint = 0.045
Si(111) double crystal monochromatorθmax = 29.5°, θmin = 2.4°
ω scanh = 3433
65225 measured reflectionsk = 3334
6115 independent reflectionsl = 99
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.105 w = 1/[σ2(Fo2) + (0.0755P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.001
6115 reflectionsΔρmax = 0.32 e Å3
356 parametersΔρmin = 0.60 e Å3
100 restraintsAbsolute 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 methodsAbsolute structure parameter: 0.155 (17)
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. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S1X0.5984 (17)0.751 (2)1.430 (14)0.49 (8)0.158 (12)
S2X0.542 (3)0.721 (4)1.231 (11)0.29 (3)0.158 (12)
S1Y0.5208 (19)0.738 (2)1.413 (7)0.34 (2)0.241 (14)
S2Y0.5367 (7)0.7685 (9)1.183 (4)0.187 (10)0.241 (14)
S1A0.567 (3)0.764 (3)1.739 (14)0.39 (3)0.198 (13)
S2A0.5088 (16)0.749 (3)1.602 (11)0.35 (3)0.198 (13)
S1B0.5952 (16)0.759 (3)1.910 (14)0.33 (4)0.155 (13)
S2B0.526 (2)0.762 (4)1.947 (18)0.38 (4)0.155 (13)
I10.69491 (2)0.75387 (3)0.38630 (9)0.1097 (2)0.924 (7)
Cu10.74969 (4)0.70187 (3)0.62513 (14)0.1065 (3)0.924 (7)
C11.00000.50000.25000.077 (3)
C20.50000.50001.50000.098 (4)
N1A0.7982 (3)0.6593 (3)0.4690 (9)0.106 (2)
C2A0.8418 (5)0.6449 (6)0.5308 (15)0.153 (6)
H2AA0.85120.65440.65040.184*
C3A0.8749 (4)0.6160 (5)0.4267 (12)0.131 (4)
H3AA0.90440.60440.47860.157*
C4A0.8624 (3)0.6054 (3)0.2440 (10)0.0931 (19)
C5A0.8189 (4)0.6238 (5)0.1804 (13)0.130 (4)
H5AA0.81040.61840.05640.156*
C6A0.7861 (4)0.6508 (5)0.2931 (12)0.126 (4)
H6AA0.75620.66260.24510.151*
C7A0.8964 (2)0.5771 (3)0.1204 (9)0.0860 (15)
C8A0.8791 (3)0.5465 (3)0.0211 (10)0.0945 (18)
H8AA0.84490.54280.03640.113*
C9A0.9109 (2)0.5211 (3)0.1410 (9)0.0878 (16)
H9AA0.89780.50080.23370.105*
C10A0.9612 (2)0.5260 (2)0.1230 (9)0.0810 (14)
C11A0.9796 (3)0.5564 (3)0.0234 (9)0.0842 (15)
H11A1.01380.55940.04010.101*
C12A0.9475 (3)0.5816 (3)0.1421 (8)0.0899 (16)
H12A0.96030.60160.23640.108*
N1B0.6974 (4)0.6622 (3)0.7704 (10)0.111 (2)0.57 (2)
C2B0.6848 (10)0.6793 (9)0.936 (3)0.142 (10)0.57 (2)
H2BA0.69950.70840.97890.171*0.57 (2)
C3B0.6499 (9)0.6550 (6)1.049 (2)0.115 (6)0.57 (2)
H3BA0.63790.67071.15510.138*0.57 (2)
C4B0.6335 (3)0.6089 (3)1.0040 (11)0.101 (2)0.57 (2)
C5B0.6389 (9)0.5984 (9)0.820 (2)0.146 (10)0.57 (2)
H5BA0.61880.57430.76470.175*0.57 (2)
C6B0.6739 (8)0.6233 (7)0.713 (2)0.111 (6)0.57 (2)
H6BA0.68080.61130.59350.134*0.57 (2)
C7B0.5986 (3)0.5827 (3)1.1271 (12)0.102 (2)
C8B0.5911 (3)0.5312 (3)1.1079 (11)0.1021 (18)
H8BA0.60730.51381.01350.122*
C9B0.5599 (3)0.5065 (3)1.2286 (10)0.0972 (19)
H9BA0.55580.47231.21500.117*
C10B0.5342 (3)0.5310 (3)1.3711 (9)0.0950 (18)
C11B0.5413 (3)0.5815 (3)1.3872 (14)0.110 (2)
H11B0.52450.59921.47870.132*
C12B0.5737 (4)0.6060 (4)1.2667 (13)0.117 (3)
H12B0.57850.64001.28270.141*
N1Y0.6974 (4)0.6622 (3)0.7704 (10)0.111 (2)0.43 (2)
C2Y0.6565 (11)0.6832 (10)0.837 (5)0.162 (15)0.43 (2)
H2YA0.64880.71530.79940.194*0.43 (2)
C3Y0.6240 (10)0.6593 (9)0.963 (5)0.142 (11)0.43 (2)
H3YA0.59740.67611.01730.171*0.43 (2)
C4Y0.6335 (3)0.6089 (3)1.0040 (11)0.101 (2)0.43 (2)
C5Y0.6755 (8)0.5919 (8)0.933 (4)0.122 (9)0.43 (2)
H5YA0.68530.56020.96950.147*0.43 (2)
C6Y0.7062 (8)0.6169 (8)0.811 (4)0.128 (10)0.43 (2)
H6YA0.73320.60060.75790.154*0.43 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1X0.22 (3)0.39 (7)0.87 (18)0.21 (5)0.33 (7)0.35 (10)
S2X0.27 (5)0.35 (6)0.26 (6)0.03 (5)0.06 (4)0.02 (5)
S1Y0.27 (4)0.37 (5)0.37 (6)0.01 (4)0.00 (5)0.04 (6)
S2Y0.142 (12)0.183 (15)0.24 (2)0.036 (10)0.054 (13)0.002 (14)
S1A0.32 (5)0.37 (6)0.48 (8)0.03 (5)0.01 (5)0.08 (6)
S2A0.20 (3)0.43 (6)0.42 (7)0.05 (4)0.10 (4)0.05 (7)
S1B0.19 (3)0.33 (5)0.45 (9)0.06 (4)0.07 (5)0.17 (6)
S2B0.30 (6)0.35 (7)0.50 (10)0.07 (5)0.03 (7)0.04 (8)
I10.1187 (3)0.1280 (4)0.0825 (2)0.0215 (3)0.0001 (3)0.0073 (3)
Cu10.1206 (5)0.1143 (5)0.0845 (4)0.0160 (6)0.0244 (5)0.0002 (6)
C10.083 (4)0.083 (4)0.064 (6)0.0000.0000.000
C20.115 (6)0.115 (6)0.065 (7)0.0000.0000.000
N1A0.115 (5)0.114 (5)0.087 (3)0.032 (4)0.009 (4)0.011 (3)
C2A0.192 (13)0.201 (13)0.067 (4)0.077 (10)0.010 (6)0.026 (6)
C3A0.146 (7)0.176 (9)0.072 (5)0.060 (7)0.002 (5)0.008 (5)
C4A0.108 (5)0.101 (5)0.070 (3)0.012 (4)0.001 (3)0.002 (3)
C5A0.145 (8)0.168 (9)0.078 (4)0.059 (7)0.010 (5)0.007 (5)
C6A0.127 (7)0.174 (10)0.076 (4)0.040 (7)0.008 (4)0.015 (5)
C7A0.098 (4)0.102 (4)0.059 (3)0.017 (3)0.004 (3)0.001 (3)
C8A0.094 (4)0.115 (5)0.075 (3)0.012 (3)0.001 (3)0.013 (3)
C9A0.088 (4)0.105 (4)0.070 (3)0.005 (3)0.004 (3)0.007 (3)
C10A0.098 (4)0.085 (3)0.059 (3)0.000 (3)0.002 (3)0.002 (3)
C11A0.093 (4)0.100 (4)0.060 (3)0.004 (3)0.004 (3)0.004 (3)
C12A0.105 (4)0.101 (4)0.063 (3)0.008 (3)0.002 (3)0.005 (3)
N1B0.135 (6)0.120 (5)0.078 (4)0.009 (5)0.013 (4)0.001 (3)
C2B0.168 (19)0.163 (17)0.096 (11)0.087 (15)0.049 (11)0.058 (11)
C3B0.144 (15)0.113 (10)0.087 (9)0.027 (10)0.038 (10)0.031 (8)
C4B0.124 (6)0.110 (6)0.070 (4)0.001 (4)0.002 (4)0.002 (3)
C5B0.161 (17)0.21 (2)0.065 (7)0.081 (17)0.024 (9)0.020 (10)
C6B0.136 (14)0.115 (11)0.083 (8)0.034 (10)0.009 (8)0.009 (8)
C7B0.100 (4)0.122 (5)0.084 (5)0.001 (4)0.001 (4)0.010 (4)
C8B0.122 (5)0.114 (5)0.070 (3)0.003 (4)0.007 (5)0.011 (4)
C9B0.119 (5)0.103 (5)0.070 (3)0.002 (4)0.005 (3)0.008 (3)
C10B0.108 (5)0.112 (5)0.065 (4)0.004 (3)0.002 (3)0.002 (3)
C11B0.128 (5)0.109 (5)0.092 (5)0.003 (4)0.022 (5)0.000 (5)
C12B0.151 (8)0.112 (6)0.089 (5)0.006 (5)0.022 (5)0.004 (4)
N1Y0.135 (6)0.120 (5)0.078 (4)0.009 (5)0.013 (4)0.001 (3)
C2Y0.20 (3)0.14 (2)0.14 (3)0.05 (2)0.08 (3)0.03 (2)
C3Y0.105 (15)0.17 (2)0.15 (3)0.008 (15)0.008 (16)0.03 (2)
C4Y0.124 (6)0.110 (6)0.070 (4)0.001 (4)0.002 (4)0.002 (3)
C5Y0.114 (14)0.117 (13)0.14 (2)0.015 (11)0.010 (14)0.034 (14)
C6Y0.076 (11)0.17 (2)0.14 (2)0.037 (11)0.059 (13)0.031 (16)
Geometric parameters (Å, º) top
S1X—S2X2.23 (10)C4A—C7A1.481 (9)
S1X—I1i2.61 (6)C5A—C6A1.399 (12)
S1Y—S2Y1.90 (3)C7A—C8A1.386 (10)
S1A—S2A1.89 (3)C7A—C12A1.388 (9)
S1B—S2B1.89 (3)C8A—C9A1.390 (9)
I1—S1Xii2.61 (6)C9A—C10A1.364 (9)
I1—Cu12.6556 (12)C10A—C11A1.419 (9)
I1—Cu1iii2.6715 (13)C11A—C12A1.389 (9)
Cu1—N1B2.049 (8)N1B—C6B1.291 (15)
Cu1—N1A2.064 (6)N1B—C2B1.315 (15)
Cu1—I1iv2.6715 (13)C2B—C3B1.399 (17)
C1—C10Av1.551 (7)C3B—C4B1.353 (15)
C1—C10Avi1.551 (7)C4B—C5B1.360 (14)
C1—C10Avii1.551 (7)C4B—C7B1.468 (12)
C1—C10A1.551 (7)C5B—C6B1.385 (18)
C2—C10Bviii1.547 (8)C7B—C12B1.357 (12)
C2—C10Bix1.547 (8)C7B—C8B1.406 (11)
C2—C10Bx1.547 (8)C8B—C9B1.376 (10)
C2—C10B1.547 (8)C9B—C10B1.398 (10)
N1A—C2A1.310 (13)C10B—C11B1.375 (11)
N1A—C6A1.323 (12)C11B—C12B1.393 (12)
C2A—C3A1.396 (13)C2Y—C3Y1.41 (2)
C3A—C4A1.382 (11)C5Y—C6Y1.378 (19)
C4A—C5A1.350 (12)
S2X—S1X—I1i128 (4)N1A—C6A—C5A119.0 (9)
S1Xii—I1—Cu1117 (2)C8A—C7A—C12A117.8 (6)
S1Xii—I1—Cu1iii131 (2)C8A—C7A—C4A122.4 (7)
Cu1—I1—Cu1iii112.18 (2)C12A—C7A—C4A119.8 (6)
N1B—Cu1—N1A114.9 (3)C7A—C8A—C9A122.5 (7)
N1B—Cu1—I1102.8 (3)C10A—C9A—C8A120.2 (7)
N1A—Cu1—I1107.0 (2)C9A—C10A—C11A118.0 (6)
N1B—Cu1—I1iv104.9 (2)C9A—C10A—C1124.7 (5)
N1A—Cu1—I1iv106.0 (2)C11A—C10A—C1117.3 (5)
I1—Cu1—I1iv121.79 (3)C12A—C11A—C10A121.2 (7)
C10Av—C1—C10Avi110.2 (3)C7A—C12A—C11A120.2 (6)
C10Av—C1—C10Avii108.1 (5)C6B—N1B—C2B116.5 (11)
C10Avi—C1—C10Avii110.2 (3)C6B—N1B—Cu1126.4 (8)
C10Av—C1—C10A110.2 (3)C2B—N1B—Cu1117.0 (9)
C10Avi—C1—C10A108.1 (5)N1B—C2B—C3B122.1 (13)
C10Avii—C1—C10A110.2 (3)C4B—C3B—C2B120.4 (12)
C10Bviii—C2—C10Bix110.9 (3)C3B—C4B—C5B112.7 (12)
C10Bviii—C2—C10Bx110.9 (3)C3B—C4B—C7B120.3 (9)
C10Bix—C2—C10Bx106.6 (6)C5B—C4B—C7B123.6 (10)
C10Bviii—C2—C10B106.6 (6)C4B—C5B—C6B120.7 (14)
C10Bix—C2—C10B110.9 (3)N1B—C6B—C5B122.9 (14)
C10Bx—C2—C10B110.9 (3)C12B—C7B—C8B117.2 (8)
C2A—N1A—C6A119.5 (8)C12B—C7B—C4B122.5 (8)
C2A—N1A—Cu1123.0 (6)C8B—C7B—C4B120.3 (8)
C6A—N1A—Cu1117.2 (7)C9B—C8B—C7B120.0 (7)
N1A—C2A—C3A123.5 (9)C8B—C9B—C10B122.3 (8)
C4A—C3A—C2A117.9 (9)C11B—C10B—C9B117.2 (7)
C5A—C4A—C3A117.0 (8)C11B—C10B—C2124.3 (6)
C5A—C4A—C7A121.3 (7)C9B—C10B—C2118.5 (7)
C3A—C4A—C7A121.6 (7)C10B—C11B—C12B120.2 (8)
C4A—C5A—C6A122.8 (9)C7B—C12B—C11B123.1 (9)
Symmetry codes: (i) x, y, z+1; (ii) x, y, z1; (iii) x+3/2, y+3/2, z1/2; (iv) x+3/2, y+3/2, z+1/2; (v) y+3/2, x1/2, z1/2; (vi) x+2, y+1, z; (vii) y+1/2, x+3/2, z1/2; (viii) x+1, y+1, z; (ix) y+1, x, z+3; (x) y, x+1, z+3.
 

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