Extraordinary anisotropic thermal expansion in photosalient crystals

Yadava, K.; Gallo, G.; Bette, S.; Mulijanto, C.E.; Karothu, D.P.; Park, I.-H.; Medishetty, R.; Naumov, P.; Dinnebier, R.E.; Vittal, J.J.

doi:10.1107/S2052252519014581

research papers

IUCrJ

Volume 7| Part 1| January 2020| Pages 83-89

ISSN: 2052-2525

https://doi.org/10.1107/S2052252519014581

CHEMISTRY | CRYSTENG

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Extraordinary anisotropic thermal expansion in photosalient crystals

^aDepartment of Chemistry, National University of Singapore, S8-05-03, 3 Science Drive 3, 117543, Singapore, ^bMax Planck Institute for Solid State Research, Heisenbergstrasse 1, D70569 Stuttgart Germany, ^cDepartment of Chemistry and Biology `A. Zambelli', University of Salerno, Via Giovanni Paolo II, 132, Fisciano (SA) 84084, Italy, and ^dNew York University Abu Dhabi, 129188, Abu Dhabi, United Arab Emirates
^*Correspondence e-mail: r.dinnebier@fkf.mpg.de, chmjjv@nus.edu.sg

Edited by L. R. MacGillivray, University of Iowa, USA (Received 11 September 2019; accepted 27 October 2019)

Although a plethora of metal complexes have been characterized, those having multifunctional properties are very rare. This article reports three isotypical complexes, namely [Cu(benzoate)L₂], where L = 4-styrylpyridine (4spy) (1), 2′-fluoro-4-styrylpyridine (2F-4spy) (2) and 3′-fluoro-4-styrylpyridine (3F-4spy) (3), which show photosalient behavior (photoinduced crystal mobility) while they undergo [2+2] cycloaddition. These crystals also exhibit anisotropic thermal expansion when heated from room temperature to 200°C. The overall thermal expansion of the crystals is impressive, with the largest volumetric thermal expansion coefficients for 1, 2 and 3 of 241.8, 233.1 and 285.7 × 10⁻⁶ K⁻¹, respectively, values that are comparable to only a handful of other reported materials known to undergo colossal thermal expansion. As a result of the expansion, their single crystals occasionally move by rolling. Altogether, these materials exhibit unusual and hitherto untapped solid-state properties.

Keywords: solid-state reactions; [2+2] cycloadditions; photosalient effects; thermal expansion; metal complexes; crystal engineering; mechanochemistry; properties of solids; organic solid-state reactions; molecular crystals.

CCDC references: 1845040; 1845041; 1845042; 1845043

1. Introduction

Multifunctional smart materials can perform multiple functions through tailored chiral, electronic, magnetic, optical, thermal and/or mechanical properties that can be used for energy storage and conversion, drug delivery, catalysis, etc. It is relatively easy to design composite materials combining two or more solids with different properties into hybrid materials for specific applications (Ferreira et al., 2016 ; Lu & Lieber, 2007 ; Abouraddy et al., 2007 ; Wang et al., 2018 ; Zhu & Xu, 2014 ; Gibson, 2010 ). It is, however, somewhat challenging to design a single (molecular or non-molecular) material that is capable of performing multiple functions. Nevertheless, multifunctional properties have been realized, for example, in mixed-metal oxides (Robertson et al., 2015 ), metal–organic framework (MOFs) structures (Li et al., 2016 ; Qiu & Zhu, 2009 ; Maspoch et al., 2007 ; Cui et al., 2012 ) and nanoparticles (Cheng et al., 2012 ; Rolison et al., 2009 ). Multiferroic properties have been accomplished with MOFs and metal complexes (Wu et al., 2010 ; Ramesh & Spaldin, 2007 ; Spaldin et al., 2005 ; Cheong & Mostovoy, 2007 ). Multifunctional properties are generally less common for discrete metal complexes or clusters. Mechanically responsive materials change their shape and size and/or move in space when activated by light, heat, pressure or chemicals (Naumov et al., 2015 ; Sato, 2016 ). Among them, some dynamic molecular crystals undergo various movements such as curling, crawling, jumping, leaping, hopping, popping, splitting, wiggling and explosion when exposed to heat or light, phenomena known as thermosalient (TS) or photosalient (PS) effects (Nath et al., 2014 ; Commins et al., 2016 ). These photodynamic and thermodynamic crystals set new avenues for materials that can be used to convert light or heat into mechanical work. Anisotropic changes in their lattice parameters, accompanied by a sudden release of the accumulated strain energy, are usually considered responsible and can contribute to many of the salient effects (Naumov et al., 2015; Nath et al., 2014).

Recently, a great number of organic, inorganic and organometallic crystals showing these properties have been discovered (Commins et al., 2016, 2015 ; Naumov et al., 2013 ; Vicente et al., 2016 ; Wang et al., 2017 ; Hatano et al., 2017 ; Shibuya et al., 2017 ; Takeda & Akutagawa, 2016 ; Seki et al., 2015 ; Medishetty et al., 2014 , 2015 ; Mulijanto et al., 2017 ; Yadava & Vittal, 2019 ). However, the number of metal complexes showing PS or TS behavior compared with organic crystals is still rather small and limited to only a few examples (Naumov et al., 2013; Sato, 2016; Nath et al., 2014; Commins et al., 2016). As an example of one of the prominent cases: crystals of a cobalt(III) complex [Co(NH₃)₅(NO₂)](Cl)(NO₃) were shown to bend as well as to jump violently under UV light (Naumov et al., 2013; Chizhik et al., 2018 ). On the other hand, a thermosalient palladium(II) organometallic solid was reported to show an impressive positive and negative thermal expansion, which indicates that similar anomalous expansion could be observed in other similar materials (Panda et al., 2014 ). A smart hybrid material was prepared by incorporating this complex into thin films of sodium caseinate which exhibits dual mechanical response (to heat and light), showing potential for preparation of hybrid materials by using salient crystals (Sahoo et al., 2014 ). In another example, a cocrystal of probenecid and 4,4′-azopyridine was shown to be thermally twistable, photobendable, elastically deformable and self-healable, and thus this material can be considered a multifunctional, smart, soft crystalline solid (Gupta et al., 2018 ). Although the discovery of such multifunctional properties in a single molecular material is very important, identification of other materials with similar properties is a rather challenging task. Here, we report that the crystals of [Cu₂(benzoate)₄(L)₂], where L = 4-styrylpyridine (4spy) (1), 2′-fluoro-4-styrylpyridine (2F-4spy) (2) and 3′-fluoro-4-styrylpyridine (3F-4spy) (3) also pop violently under UV light, and thus they are photosalient. Furthermore, crystals of these materials exhibit very large anisotropic thermal expansion when heated from room temperature to about 200°C.

2. Results and discussion

2.1. Synthesis, single-crystal structures and photosalient behavior of 1–3

Green needle-like single crystals of 1–3 were obtained by slow evaporation of methanol solution of Cu(NO₃)₂·3H₂O, sodium benzoate and the respective pyridyl ligand (Medishetty et al., 2014) in the molar ratio 1:2:1. Single-crystal X-ray diffraction (SXRD) analysis showed that they are isomorphous and isostructural to each other (see Table S1 of the supporting information) (Medishetty et al., 2014). All three crystals are in the monoclinic space group C2/c with Z = 4, and their asymmetric unit contains half of the formula unit. A center of inversion is present in the middle of the paddlewheel structure (Fig. 1). The adjacent pyridyl ligands are stacked in a head-to-tail manner approximately normal to the (110) plane with strong π–π interactions between the neighboring pyridyl and phenyl groups (3.666 Å in 1, 3.690 Å in 2 and 3.656 Å in 3), as shown in Fig. 1. As a consequence, the centers of the C=C bonds are separated by 3.787 Å in 1, 3.765 Å in 2 and 3.810 Å in 3, and thus they are at distances suitable for [2+2] cycloaddition reactions (Schmidt, 1971 ).

Figure 1
View of the one-dimensional arrangement of [Cu₂(benzoate)₄(4-spy)₂] 1 via π–π interactions. Hydrogen atoms have been omitted for clarity.

As discussed earlier, the intermolecular olefin pairs on both sides of the paddlewheel structures in 1–3 are juxtaposed in a head-to-tail manner and can undergo a photochemical reaction quantitatively. This arrangement is expected to yield a one-dimensional coordination polymer (CP) as the photoproduct in which the [Cu₂(benzoate)₄] paddlewheels are joined by the product cyclobutane ligands (Fig. 2). The course of photoreactivity of the compound with time was followed under UV light using ¹H NMR spectroscopy. For this purpose irradiated powder samples were taken out at different time intervals and dissolved in DMSO-d₆ to record the ¹H NMR spectra (see Figs. S15 and S18 of the supporting information). The disappearance of the olefinic protons at 8.13 p.p.m., the appearance of cyclobutane protons at 4.82 p.p.m., and a shift in the pyridyl protons from 7.65 and 7.93 p.p.m. to 8.38 and 8.65 p.p.m., confirmed the formation of the expected cyclobutane ring photoproduct. The other two compounds 2 and 3 also showed quantitative photoconversion of their C=C bonds to cyclobutane rings (see Figs. S16, S17, S19 and S20). After the photoreaction of 1–3, the respective one-dimensional CPs (hereafter, 4, 5 and 6) were semi-crystalline, as confirmed using powder X-ray diffraction (PXRD) (see Fig. S4). Crystal structure determination of a recrystallized sample of 5 provided further evidence of the formation of the one-dimensional CP [Cu₂(benzoate)₄(rctt-2F-ppcb)], where rctt-2F-ppcb = rctt-1,3-bis(4-pyridyl)-2,4-bis(2′-fluorophenyl)cyclobutane, (5A; see Fig. 2). The recrystallized photoproduct 5A crystallizes in the space group $[P \bar 1]$ and contains the centrosymmetric binuclear paddlewheel unit connecting the cyclobutane spacer ligand rctt-2F-ppcb. This result corroborated the conclusion based on the ¹H NMR spectra (Medishetty et al., 2014, 2015) that the photodimer is the only product and there are no other chemical intermediates.

Figure 2
Perspective view of the photoproduct 5A showing the formation of the one-dimensional coordination polymer. Hydrogen atoms have been omitted for clarity.

Interestingly, the crystals and powders of 1–3 started popping violently and exploded under UV light in a similar way to popping corn on hot surfaces, which is clear evidence of the PS effect (see Movies S1–S6 of the supporting information). The single crystals, depending upon their size and shape, display different types of movements under UV light, similar to isotypical Zn(II) complexes (Medishetty et al., 2014). Given the structural similarity, we conclude that the mechanism of the PS behavior of 1–3 is analogous to that of the respective Zn(II) complexes, which posits the existence of both reactants and photoproducts in the single crystals and rapid buildup of stress in the crystal, until they pop out or fragment into smaller pieces.

The densities of 1–6 were measured by the flotation method. A comparison of the densities of 5 [after complete photoreaction, 1.28 (2) g cm⁻³] and 5A (after recrystallization, 1.489 g cm⁻³) shows that the molecules in 5A (in the space group $[P\bar 1]$ ) packed more tightly than in the structure of 5 after recrystallization. From other examples of photoreactive complexes, it is known that the unit cell volumes decrease upon photodimerization and formation of cyclobutane rings. Importantly, only in the materials showing the PS effect were the unit cell volumes found to increase during the [2+2] cycloaddition reaction (Medishetty et al., 2014, 2015; Yadava & Vittal, 2019). Overall, the densities were found to decrease after photoreaction (14.7% for 1 to 4, 15.6% for 2 to 5 and 12.2% for 3 to 6) and these correspond to the increase in unit cell volumes of 15.4, 17.5 and 13.1% on going from 1–3 to 4–6, respectively (Table S2). The mobility of dynamic single crystals is usually triggered by the sudden release of stress in the form of a very fast phase transition or a chemical reaction accompanied a rapid structural change that drives these phenomena (Nath et al., 2014; Chizhik et al., 2018; Ghosh et al., 2015 ; Sahoo et al., 2014, 2013a ,b ; Skoko et al., 2010 ; Rawat et al., 2018 ; Panda et al., 2015 , 2016 ; Boldyreva, 1994 ; Mittapalli et al., 2017 ). Here, the stress created by the phase heterometry due to the difference in the unit cell volumes and the release of that stress manifests as motion or explosive fragmentation of the crystals.

The TS and PS effects, resulting in crystals flying over distances several times their own size, are usually associated with a very fast phase transitions, analogous to the martensitic transitions in inorganic materials (Naumov et al., 2013; Nath et al., 2014; Yadava & Vittal, 2019; Panda et al., 2014; Ghosh et al., 2015; Skoko et al., 2010; Boldyreva, 1994). We observed that when heated from room temperature to 210°C, the pristine crystals of 1–3 occasionally rolled or jumped off the hot stage (Movies S7–S12). However, this behavior was not consistent and was not reproducible with all batches of crystals. Hence, we concluded that the motion is not a result of TS effects. Instead, it could be due to non-uniform or sudden heating. A recent report of a TS behavior of the organic compound methscopolamine bromide observed motion that was not accompanied by a detectable phase transition, and this effect was attributed to unusually large anisotropic thermal expansion with coefficients of 135 (1) × 10⁻⁶ K⁻¹ and 114 (1) × 10⁻⁶ K⁻¹ along the a and c axes, respectively (Klaser et al., 2018 ). Although such behavior cannot be attributed to a TS effect (which is strictly related to a phase transition), it could nevertheless account for the observed motion of the crystals.

To obtain a better insight into the thermal behavior of the compounds reported here, we performed thermogravimetry (TG), differential scanning calorimetry (DSC) and variable temperature powder X-ray diffraction (VT-PXRD) measurements. The TG results show that 1–3 are thermally stable up to 210°C, and start to melt around that temperature, accompanied by decomposition to a black-colored product, probably due to formation of copper oxide along with some carbonaceous residues (Figs. S6–S8). The DSC of 1–3, recorded from either single crystals or powder, did not show a phase transition from room temperature to their decomposition temperature (Figs. S12–S14). The VT-PXRD results corroborate the conclusion obtained from the DSC experiments (Figs. S29–S31).

2.2. Thermal expansion

The thermal behavior of crystals 1–3 was investigated by VT-PXRD measurements in the temperature range from room temperature to 200°C, just below their decomposition temperature (Figs. S29–S31). Since these compounds crystallize in a monoclinic space group, the coefficients of thermal expansion were calculated using the program PASCal (Table 1) (Cliffe & Goodwin, 2012 ). A typical PXRD pattern of 3 showing shifts in selected peaks related to the thermal expansion is shown in Fig. 3.

Table 1
Volume expansion coefficients and all axes expansion coefficients for 1–3 using the program PASCal

α is the linear coefficient of thermal expansion, σ_α is the error in the linear coefficient of thermal expansion, a, b and c are the projections of X_n on the unit cell axes.

1			Direction
Axes	α, 10⁻⁶ K⁻¹	σ_α, 10⁻⁶ K⁻¹	a	b	c
X₁	13.9159	0.8233	0.5338	0.0000	0.8456
X₂	56.0233	1.0415	0.0000	1.0000	0.0000
X₃	166.3843	5.5537	0.5291	0.0000	0.8486
V	241.8234	6.4930

2			Direction
Axes	α, 10⁻⁶ K⁻¹	σ_α, 10⁻⁶ K⁻¹	a	b	c
X₁	21.8943	0.4764	−0.3870	0.0000	−0.9221
X₂	38.3804	0.5909	0.0000	−1.0000	0.0000
X₃	167.7776	5.2979	0.8072	−0.0000	−0.5902
V	233.1210	6.2627

3			Direction
Axes	α, 10⁻⁶ K⁻¹	σ_α, 10⁻⁶ K⁻¹	a	b	c
X₁	−13.8283	3.7014	0.6377	−0.0000	0.7703
X₂	64.5518	1.3444	0.0000	−1.0000	0.0000
X₃	228.3639	9.0008	−0.3302	0.0000	0.9439
V	285.6904	7.1723

Figure 3
Typical PXRD pattern of 3 recorded at three different temperatures showing the shifts in selected peaks related to the thermal expansion.

The thermal expansion coefficients are reported along the principal X₂ axis parallel to the crystallographic b axis, and along the principal X₁ axis which is almost parallel to the direction [102] for 1 and 2 and to [101] for 3, and along the principal X₃ axis which is nearly parallel to the direction $[[{\overline 1}02]]$ for 1 and 3 and [ $[10{\overline 1}]]$ for 2. All solids exhibit strong anisotropic thermal expansion with outstanding positive thermal expansion (PTE) along the principal X₃ axis [(α₃ = 166.38, 156.75 and 228.36) × 10⁻⁶ K⁻¹]. Although compounds 1 and 2 show a relatively small PTE (α₁ = 13.9159 × 10⁻⁶ K⁻¹, α₂ = 56.0233 × 10⁻⁶ K⁻¹ for 1, α₁ = 21.8943 × 10⁻⁶ K⁻¹, α₂ = 38.3804 × 10⁻⁶ K⁻¹ for 2), compound 3 exhibits a small negative thermal expansion (α₁ = −13.8283 × 10⁻⁶ K⁻¹) along the principal X₁ axis. The details are displayed for 3 in Fig. 4 and for 1 and 2 in Figs. S32 and S33, respectively. Furthermore, no hysteresis was observed on cooling for any of the crystals, and all expansions are rather linear in the measured temperature range [see Figs. S22–S24, (b) and (c)].

Figure 4
(a) Plot showing the variation of α with the direction, expansivity indicatrix (units: MK⁻¹) in two different angles for 3. (b) Overall thermal expansion of volume in 3. (c) Anisotropic thermal expansion of volume in 3.

The similarities and the small differences observed in the anisotropic thermal expansion behavior of compounds 1–3 can be explained through a detailed analysis of the fundamental structural motifs. In all compounds the [Cu₂(benzoate)₂L₄] paddlewheel complexes are connected by π—π interactions between the C=C bonds of the styrylpyridine ligands, resulting in one-dimensional chain-like motifs running in the [ $[2{\overline 2}1]$ ] direction (Fig. 5). This direction corresponds to a combination of the principal X₁ and X₂ axes, in contrast to the cases reported in literature (Saha et al., 2017 ; Saraswatula et al., 2018 ; Crawford et al., 2019 ), where the major expansion occurs along the π—π stacking direction; the combination of π—π interactions between the paddlewheel complexes and the strong coordination bonds in the distinct complexes strengthen the chain-like motifs inhibiting any expansion along the X₁ and X₂ axes.

Figure 5
Representation of the crystal structures of compounds 1–3, (a) along the crystallographic b axis and (b) in the [ $[{\overline 1}0{\overline 1}]$ ] direction. The principal axes (X₁, X₂ and X₃) for the thermal expansion are also shown. Chain-like one-dimensional structural motifs formed by π–π interactions (indicated by red circles) of the C=C double bonds of the styrylpyridine ligands are represented in green and yellow. The inset in (b) highlights the interchain interactions in compound 2.

The directive role of the π–π interactions for the thermal expansion is also confirmed by the fact that [2+2] cycloaddition photoreactivity was observed also at higher temperatures (120–200°C). This indicates that the olefin pairs remain intact even at higher temperature, satisfying the Schmidt criteria for a [2+2] cycloaddition reaction, i.e. the head-to-tail alignment of the styrylpyridine ligands is retained when the crystals are heated. Compound 3 exhibits intra-chain F⋯H—C interactions between the fluoride-functionalized styrylpyridine and the benzoate ligand, leading to further stiffening of the chain and could explain the slightly negative thermal expansion along the principal axis. Instead, the expansion along X₃ is promoted by mechanics, which is reflected in the fact that 3 has the largest α₃ coefficient. In 2, F⋯H—C interactions connect neighboring chains, which additionally inhibit the thermal expansion along the principal X₂ axis. Hence, 2 exhibits the smallest α₂ coefficient of all investigated compounds. As 1 is composed only of non-substituted styrylpyridine ligands, there are no F⋯H—C interactions, and the thermal expansion is only borne by the π–π interaction. Therefore, the determined α_1, α₂ and α₃ coefficients are in the intermediate range of the investigated compounds (Table 1). Most of the few known photosalient reactions are accompanied by chemical reactions such as [2+2] cycloaddition or isomerization (Naumov et al., 2013; Wang et al., 2017; Takeda & Akutagawa, 2016; Medishetty et al., 2014, 2015; Mulijanto et al., 2017; Yadava & Vittal, 2019). There is also a report on the shortening of intermolecular aurophilic interactions responsible for the PS effect (Seki et al., 2015). Usually the PS effect that is based on the [2+2] cycloaddition reaction requires not only alignment of the olefin bond pairs in the solid state, but also a sudden anisotropic cell expansion during the photoreaction (Medishetty et al., 2014, 2015; Mulijanto et al., 2017; Yadava & Vittal, 2019). The paddlewheel metal complexes are very convenient materials to study the effects of these factors.

Complementary π–π interactions in head-to-tail alignment of the 4spy ligands are congenial to make photoreactive crystals and this alignment results in one-dimensional aggregates of the Cu(II) complexes. Furthermore , all these π–π aggregates are packed parallel to each other. Hence, the formation of the cyclobutane rings from olefin pairs promotes anisotropic volume expansion during the photoreaction. This is further supported by the increase of the unit cell volumes of 15.4, 17.5 and 13.1% on going from 1–3 to 4–6, respectively, as determined from the densities by the flotation method. This is corroborated by the unit cell volume measurements of 4–6 from XRPD experiments (Figs. S34 and S35, Tables S4 and S5). The stress generated by the phase heterometry is released suddenly in the form of a very fast chemical reaction accompanied a rapid structural change that appears to drive this PS effect.

3. Conclusions

Molecular solids in general are expected to have moderate positive thermal expansion (PTE) due to increasing anharmonic vibrational amplitudes of their molecules. In many cases, structural peculiarities may give rise to very large PTE (Goodwin et al., 2008 ; Das et al., 2010 , 2015 ; Engel et al., 2014 ; Alimi et al., 2018 ; Janiak et al., 2018 ; Zhou et al., 2015 ; Yang et al., 2009 ) or even NTE (Chapman et al., 2006 ; Goodwin et al., 2005 ; Margadonna et al., 2004 ; Pan et al., 2019 ; Phillips et al., 2008 ; Wu et al., 2008 ) upon heating (Table S3). It is interesting to note that the parallel alignment of the one-dimensional assemblies in 1–3 promotes large thermal expansion from room temperature to 200°C in addition to photoreactivity and the PS effect. The volumetric thermal expansions (VTE) observed for 1, 2 and 3 are 241.8, 233.1 and 285.7 × 10⁻⁶ K⁻¹, respectively. Of these, the value observed for 3 is the largest for metal complexes, based on comparison with the previously reported value of 255.5 × 10⁻⁶ K⁻¹ for the palladium(II) complex (Panda et al., 2014). However, this is not the largest VTE reported thus far, and the difference in using different expressions to calculate thermal expansion used in the literature and the occasional non-linearity of the expansion with temperature should be considered (Table S3) (Engel et al., 2014; Zhou et al., 2015; Yang et al., 2009). The α₃ coefficients of the investigated compounds exceed the other thermal expansion coefficients at least by a factor of three, which leads to a progressive anisotropic expansion on heating. This creates interfacial strain in the crystals which accumulates until it is suddenly released as elastic energy and propels the crystal of its debris. When crystals of 1–3 were heated in the temperature range 120–200°C and illuminated under UV light they started jumping violently (similar to popcorn) while undergoing [2+2] cycloaddition. This observation provides strong evidence that the olefin pairs are intact even at higher temperatures, thus satisfying the Schimidt criteria for a [2+2] cycloaddition. Therefore, anisotropic expansion occurs roughly normal to the one-dimensional aggregates. We conclude that the robustness of the π–π interactions in this crystal packing is ultimately the key structural feature for all three properties observed with these materials. This work therefore provides new insights towards the engineering of multifunctional properties in crystals, and favors these and similar compounds as candidates for in-depth studies into the factors that determine the salient effects.

CCDC codes 1845040–1845043 for 1–3 and 5A contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via https://www.ccdc.cam.ac.uk/data_request/cif.

4. Related literature

The following references are cited in the supporting information: Enfange et al. (1990 ); Sheldrick (1996 , 2008 ); Müller et al. (2006 ); Yadava (2019 ); Bhattacharya & Saha (20143 ); Hutchins et al. (2016 , 2019 ); Brock et al. (2019 ); Pawley (1981 ).

Supporting information

CCDC references: 1845040; 1845041; 1845042; 1845043

Crystal structure: contains datablocks 1, 2, 3, 5a. DOI: https://doi.org/10.1107/S2052252519014581/lq5028sup1.cif

Supporting data. DOI: https://doi.org/10.1107/S2052252519014581/lq5028sup2.pdf

Video S1: photosalient effect of a single crystal of 1 showing rolling, hopping, breaking and disintegration of a single crystal during [2+2] cycloaddition reaction under UV light (Max 150 instrument, Xenon light source 150 W and wavelength of 360 nm). DOI: https://doi.org/10.1107/S2052252519014581/lq5028sup3.mp4

Video S2: photoalient behavior of crystal clusters of 1 under UV light. Different types of movements including hopping, breaking and disintegration of clusters of crystals are shown under UV light (Max 150 instrument, Xenon light source 150 W and wavelength of 360 nm). DOI: https://doi.org/10.1107/S2052252519014581/lq5028sup4.mp4

Video S3: occasional thermosalient effect exhibited by small single crystals of 1. The crystals were heated on a hot stage from room temperature to 210 degC showing wiggling, hopping and jumping movements. The video shown is four times faster than the normal speed to highlight the effect. DOI: https://doi.org/10.1107/S2052252519014581/lq5028sup5.mp4

Video S4: occasional thermosalient effect displayed by big crystals of 1. Small movements, rolling, hopping and sudden jumping of crystals leading to the disappearance of crystals from the sight are shown. The video shown is four times faster than the normal speed to dramatize the effect. DOI: https://doi.org/10.1107/S2052252519014581/lq5028sup6.mp4

Video S5: photosalient effect of 1 during [2+2] cycloaddition reaction under UV light showing the breaking and disintegration of single crystals (Max 150 instrument, Xenon light source 150 W and wavelength of 360 nm). DOI: https://doi.org/10.1107/S2052252519014581/lq5028sup7.mp4

Video S6: photosalient effect showing the breaking of a single crystal of 1 under UV light (Max 150 instrument, Xenon light source 150 W and wavelength of 360 nm). DOI: https://doi.org/10.1107/S2052252519014581/lq5028sup8.mp4

Video S7: photosalient effect showing the hopping and breaking of a single crystal of 1 under UV light (Max 150 instrument, Xenon light source 150 W and wavelength of 360 nm). DOI: https://doi.org/10.1107/S2052252519014581/lq5028sup9.mp4

Video S8: occasional thermosalient effect on big crystals of 1 showing chipping, rolling and hopping of crystals. DOI: https://doi.org/10.1107/S2052252519014581/lq5028sup10.mp4

Video S9: photosalient effect of a single crystal of 2 showing complete disintegration single crystals during [2+2] cycloaddition reaction under UV light (Max 150 instrument, Xenon light source 150 W and wavelength of 360 nm). DOI: https://doi.org/10.1107/S2052252519014581/lq5028sup11.mp4

Video S10: occasional thermosalient effect on big crystals of 2. Wiggling, rolling and hopping of crystals are demonstrated. DOI: https://doi.org/10.1107/S2052252519014581/lq5028sup12.mp4

Video S11: photosalient behavior showing breaking, rolling, hopping and jumping out of sight of single crystals of 3 during [2+2] cycloaddition reaction under UV light (Max 150 instrument, Xenon light source 150 W and wavelength of 360 nm). DOI: https://doi.org/10.1107/S2052252519014581/lq5028sup13.mp4

Video S12: occasional thermosalient effect on big crystals of 3 showing wiggling, rolling and hopping of crystals. DOI: https://doi.org/10.1107/S2052252519014581/lq5028sup14.mp4

Computing details top

(1) top

Crystal data top

C₅₄H₄₂Cu₂N₂O₈	F(000) = 2008
M_r = 973.97	D_x = 1.477 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 24.633 (11) Å	Cell parameters from 986 reflections
b = 12.093 (4) Å	θ = 2.5–27.5°
c = 15.509 (6) Å	µ = 1.03 mm⁻¹
β = 108.480 (12)°	T = 100 K
V = 4381 (3) Å³	BLOCK, green
Z = 4	0.40 × 0.18 × 0.10 mm

Data collection top

Bruker APEX-II CCD diffractometer	4531 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.045
Absorption correction: multi-scan SADABS (Sheldrick, 2010)	θ_max = 27.5°, θ_min = 1.7°
T_min = 0.664, T_max = 0.746	h = −32→32
28192 measured reflections	k = −15→15
5043 independent reflections	l = −20→20

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0385P)² + 7.0332P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.003
5043 reflections	Δρ_max = 0.47 e Å⁻³
298 parameters	Δρ_min = −0.26 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.

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

	x	y	z	U_iso*/U_eq
Cu1	0.54074 (2)	0.50316 (2)	0.08078 (2)	0.01025 (7)
O1	0.56615 (5)	0.35721 (10)	0.04928 (8)	0.0162 (3)
O2	0.49655 (5)	0.35268 (10)	−0.08577 (8)	0.0179 (3)
O3	0.48237 (5)	0.42404 (10)	0.11946 (8)	0.0156 (2)
O4	0.41285 (5)	0.42191 (11)	−0.01575 (8)	0.0178 (3)
N1	0.60368 (6)	0.52400 (12)	0.21246 (9)	0.0121 (3)
C1	0.59215 (7)	0.58179 (14)	0.27851 (11)	0.0143 (3)
H1	0.5548	0.6118	0.2666	0.017*
C2	0.63185 (7)	0.59975 (14)	0.36290 (11)	0.0143 (3)
H2	0.6216	0.6416	0.4073	0.017*
C3	0.68698 (7)	0.55656 (14)	0.38309 (11)	0.0134 (3)
C4	0.69869 (8)	0.49569 (14)	0.31437 (13)	0.0177 (4)
H4	0.7354	0.4638	0.3245	0.021*
C5	0.65644 (8)	0.48227 (14)	0.23147 (12)	0.0165 (3)
H5	0.6654	0.4412	0.1856	0.020*
C6	0.73159 (7)	0.57305 (15)	0.47083 (11)	0.0158 (3)
H6	0.7682	0.5418	0.4780	0.019*
C7	0.72512 (7)	0.62829 (15)	0.54143 (12)	0.0168 (3)
H7	0.6881	0.6570	0.5343	0.020*
C8	0.76931 (7)	0.64936 (14)	0.62908 (11)	0.0152 (3)
C9	0.82490 (8)	0.60707 (15)	0.65109 (12)	0.0192 (4)
H9	0.8352	0.5625	0.6082	0.023*
C10	0.86511 (8)	0.62933 (16)	0.73453 (13)	0.0227 (4)
H10	0.9025	0.5990	0.7487	0.027*
C11	0.85135 (8)	0.69565 (15)	0.79780 (12)	0.0203 (4)
H11	0.8792	0.7115	0.8547	0.024*
C12	0.79685 (8)	0.73816 (16)	0.77716 (12)	0.0197 (4)
H12	0.7871	0.7835	0.8200	0.024*
C13	0.75609 (8)	0.71507 (15)	0.69405 (12)	0.0190 (4)
H13	0.7186	0.7444	0.6810	0.023*
C14	0.53705 (7)	0.30980 (13)	−0.02322 (11)	0.0121 (3)
C15	0.55052 (7)	0.19072 (14)	−0.03516 (12)	0.0140 (3)
C16	0.59578 (8)	0.13749 (15)	0.02872 (12)	0.0176 (4)
H16	0.6208	0.1782	0.0776	0.021*
C17	0.60436 (9)	0.02459 (16)	0.02097 (14)	0.0232 (4)
H17	0.6351	−0.0117	0.0648	0.028*
C18	0.56807 (9)	−0.03473 (16)	−0.05046 (16)	0.0286 (5)
H18	0.5735	−0.1120	−0.0550	0.034*
C19	0.52382 (9)	0.01815 (17)	−0.11537 (16)	0.0299 (5)
H19	0.4994	−0.0226	−0.1650	0.036*
C20	0.51504 (8)	0.13082 (16)	−0.10797 (14)	0.0222 (4)
H20	0.4847	0.1671	−0.1527	0.027*
C21	0.43367 (7)	0.39606 (13)	0.06703 (11)	0.0120 (3)
C22	0.39839 (7)	0.32184 (13)	0.10553 (11)	0.0132 (3)
C23	0.34622 (7)	0.28012 (15)	0.04997 (12)	0.0169 (3)
H23	0.3316	0.3027	−0.0118	0.020*
C24	0.31570 (8)	0.20579 (16)	0.08477 (14)	0.0223 (4)
H24	0.2802	0.1774	0.0467	0.027*
C25	0.33673 (8)	0.17267 (15)	0.17504 (14)	0.0232 (4)
H25	0.3160	0.1210	0.1986	0.028*
C26	0.38813 (9)	0.21524 (17)	0.23067 (13)	0.0239 (4)
H26	0.4024	0.1930	0.2925	0.029*
C27	0.41880 (8)	0.29001 (15)	0.19657 (12)	0.0178 (4)
H27	0.4538	0.3196	0.2353	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01067 (11)	0.01025 (11)	0.00846 (11)	−0.00045 (7)	0.00109 (8)	−0.00048 (7)
O1	0.0172 (6)	0.0151 (6)	0.0139 (6)	0.0032 (5)	0.0017 (5)	−0.0031 (5)
O2	0.0188 (6)	0.0139 (6)	0.0168 (6)	0.0031 (5)	−0.0002 (5)	−0.0028 (5)
O3	0.0136 (6)	0.0198 (6)	0.0129 (6)	−0.0032 (5)	0.0035 (5)	0.0010 (5)
O4	0.0164 (6)	0.0234 (7)	0.0121 (6)	−0.0048 (5)	0.0025 (5)	0.0033 (5)
N1	0.0120 (7)	0.0122 (7)	0.0101 (6)	−0.0010 (5)	0.0007 (5)	−0.0004 (5)
C1	0.0138 (8)	0.0151 (8)	0.0132 (8)	0.0020 (6)	0.0029 (6)	−0.0003 (6)
C2	0.0166 (8)	0.0159 (8)	0.0107 (8)	−0.0009 (6)	0.0050 (6)	−0.0022 (6)
C3	0.0137 (8)	0.0132 (8)	0.0116 (8)	−0.0028 (6)	0.0017 (6)	0.0000 (6)
C4	0.0138 (8)	0.0201 (9)	0.0176 (9)	0.0025 (7)	0.0026 (7)	−0.0024 (7)
C5	0.0183 (9)	0.0157 (8)	0.0139 (8)	0.0010 (7)	0.0029 (7)	−0.0034 (6)
C6	0.0130 (8)	0.0184 (8)	0.0135 (8)	0.0001 (6)	0.0008 (6)	−0.0002 (6)
C7	0.0141 (8)	0.0202 (9)	0.0136 (8)	0.0002 (7)	0.0006 (7)	0.0003 (7)
C8	0.0169 (8)	0.0150 (8)	0.0125 (8)	−0.0036 (6)	0.0028 (7)	0.0011 (6)
C9	0.0192 (9)	0.0191 (9)	0.0162 (9)	0.0001 (7)	0.0014 (7)	−0.0031 (7)
C10	0.0175 (9)	0.0249 (10)	0.0210 (9)	0.0009 (7)	−0.0007 (7)	−0.0022 (7)
C11	0.0225 (9)	0.0216 (9)	0.0124 (8)	−0.0047 (7)	−0.0010 (7)	0.0002 (7)
C12	0.0244 (9)	0.0221 (9)	0.0125 (8)	−0.0038 (7)	0.0060 (7)	−0.0026 (7)
C13	0.0168 (8)	0.0238 (9)	0.0151 (8)	−0.0001 (7)	0.0030 (7)	−0.0006 (7)
C14	0.0120 (8)	0.0125 (8)	0.0132 (8)	−0.0006 (6)	0.0062 (6)	0.0001 (6)
C15	0.0141 (8)	0.0127 (8)	0.0177 (8)	0.0003 (6)	0.0085 (7)	−0.0004 (6)
C16	0.0190 (9)	0.0178 (9)	0.0171 (8)	0.0022 (7)	0.0074 (7)	0.0010 (7)
C17	0.0253 (10)	0.0179 (9)	0.0304 (11)	0.0078 (7)	0.0148 (8)	0.0071 (8)
C18	0.0334 (11)	0.0128 (9)	0.0465 (13)	0.0021 (8)	0.0223 (10)	−0.0032 (9)
C19	0.0282 (11)	0.0201 (10)	0.0397 (13)	−0.0046 (8)	0.0084 (9)	−0.0128 (9)
C20	0.0183 (9)	0.0174 (9)	0.0279 (10)	0.0005 (7)	0.0030 (8)	−0.0058 (7)
C21	0.0144 (8)	0.0092 (7)	0.0131 (8)	0.0019 (6)	0.0053 (6)	−0.0020 (6)
C22	0.0155 (8)	0.0104 (7)	0.0154 (8)	0.0010 (6)	0.0072 (7)	−0.0013 (6)
C23	0.0165 (8)	0.0170 (8)	0.0174 (8)	0.0002 (7)	0.0058 (7)	−0.0012 (7)
C24	0.0183 (9)	0.0198 (9)	0.0300 (10)	−0.0040 (7)	0.0091 (8)	−0.0040 (8)
C25	0.0282 (10)	0.0145 (9)	0.0340 (11)	−0.0023 (7)	0.0202 (9)	0.0012 (8)
C26	0.0312 (10)	0.0250 (10)	0.0186 (9)	0.0012 (8)	0.0124 (8)	0.0043 (7)
C27	0.0198 (9)	0.0187 (9)	0.0155 (8)	0.0003 (7)	0.0064 (7)	−0.0007 (7)

Geometric parameters (Å, º) top

Cu1—O4ⁱ	1.9688 (13)	C8—C9	1.399 (3)
Cu1—O3	1.9722 (13)	C8—C13	1.400 (2)
Cu1—O2ⁱ	1.9833 (13)	C9—C10	1.384 (3)
Cu1—O1	1.9848 (13)	C10—C11	1.390 (3)
Cu1—N1	2.1518 (15)	C11—C12	1.377 (3)
Cu1—Cu1ⁱ	2.6693 (9)	C12—C13	1.388 (2)
O1—C14	1.263 (2)	C14—C15	1.502 (2)
O2—C14	1.262 (2)	C15—C20	1.392 (2)
O2—Cu1ⁱ	1.9833 (13)	C15—C16	1.392 (2)
O3—C21	1.263 (2)	C16—C17	1.393 (3)
O4—C21	1.262 (2)	C17—C18	1.383 (3)
O4—Cu1ⁱ	1.9688 (13)	C18—C19	1.384 (3)
N1—C5	1.337 (2)	C19—C20	1.390 (3)
N1—C1	1.343 (2)	C21—C22	1.499 (2)
C1—C2	1.380 (2)	C22—C27	1.394 (2)
C2—C3	1.395 (2)	C22—C23	1.395 (2)
C3—C4	1.399 (2)	C23—C24	1.386 (3)
C3—C6	1.467 (2)	C24—C25	1.389 (3)
C4—C5	1.383 (2)	C25—C26	1.386 (3)
C6—C7	1.335 (2)	C26—C27	1.386 (3)
C7—C8	1.469 (2)

O4ⁱ—Cu1—O3	167.63 (5)	C9—C8—C13	117.70 (16)
O4ⁱ—Cu1—O2ⁱ	88.10 (6)	C9—C8—C7	122.89 (16)
O3—Cu1—O2ⁱ	91.33 (6)	C13—C8—C7	119.41 (16)
O4ⁱ—Cu1—O1	90.20 (6)	C10—C9—C8	120.80 (17)
O3—Cu1—O1	87.74 (6)	C9—C10—C11	120.66 (18)
O2ⁱ—Cu1—O1	167.76 (5)	C12—C11—C10	119.29 (17)
O4ⁱ—Cu1—N1	94.11 (6)	C11—C12—C13	120.38 (17)
O3—Cu1—N1	98.26 (6)	C12—C13—C8	121.16 (17)
O2ⁱ—Cu1—N1	93.63 (5)	O2—C14—O1	125.81 (15)
O1—Cu1—N1	98.58 (5)	O2—C14—C15	116.81 (14)
O4ⁱ—Cu1—Cu1ⁱ	85.31 (5)	O1—C14—C15	117.36 (14)
O3—Cu1—Cu1ⁱ	82.40 (4)	C20—C15—C16	119.46 (16)
O2ⁱ—Cu1—Cu1ⁱ	80.91 (4)	C20—C15—C14	119.49 (16)
O1—Cu1—Cu1ⁱ	86.87 (4)	C16—C15—C14	120.91 (15)
N1—Cu1—Cu1ⁱ	174.53 (4)	C15—C16—C17	120.07 (18)
C14—O1—Cu1	119.24 (11)	C18—C17—C16	120.02 (19)
C14—O2—Cu1ⁱ	126.48 (11)	C17—C18—C19	120.20 (19)
C21—O3—Cu1	124.70 (11)	C18—C19—C20	120.01 (19)
C21—O4—Cu1ⁱ	121.37 (11)	C19—C20—C15	120.19 (19)
C5—N1—C1	117.00 (15)	O4—C21—O3	125.83 (16)
C5—N1—Cu1	121.51 (12)	O4—C21—C22	116.99 (15)
C1—N1—Cu1	121.46 (12)	O3—C21—C22	117.13 (15)
N1—C1—C2	123.21 (16)	C27—C22—C23	119.44 (16)
C1—C2—C3	120.05 (15)	C27—C22—C21	120.02 (15)
C2—C3—C4	116.57 (15)	C23—C22—C21	120.49 (15)
C2—C3—C6	123.18 (15)	C24—C23—C22	120.07 (17)
C4—C3—C6	120.25 (16)	C23—C24—C25	120.29 (18)
C5—C4—C3	119.60 (17)	C26—C25—C24	119.72 (17)
N1—C5—C4	123.56 (16)	C25—C26—C27	120.38 (18)
C7—C6—C3	125.45 (16)	C26—C27—C22	120.08 (17)
C6—C7—C8	126.85 (17)

Symmetry code: (i) −x+1, −y+1, −z.

(2) top

Crystal data top

C₅₄H₄₀Cu₂F₂N₂O₈	F(000) = 2072
M_r = 1009.96	D_x = 1.516 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 24.9699 (8) Å	Cell parameters from 8450 reflections
b = 12.1074 (4) Å	θ = 3.0–28.3°
c = 15.4675 (4) Å	µ = 1.03 mm⁻¹
β = 108.809 (1)°	T = 100 K
V = 4426.4 (2) Å³	Block, green
Z = 4	0.17 × 0.16 × 0.11 mm

Data collection top

Bruker D8 Venture diffractometer	4396 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.029
Absorption correction: multi-scan SADABS (Shelcrick, 2010)	θ_max = 28.3°, θ_min = 2.5°
T_min = 0.693, T_max = 0.746	h = −32→32
19385 measured reflections	k = −13→16
5481 independent reflections	l = −20→20

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.079	w = 1/[σ²(F_o²) + (0.0375P)² + 5.134P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
5481 reflections	Δρ_max = 0.38 e Å⁻³
307 parameters	Δρ_min = −0.30 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Cu1	0.54016 (2)	0.49779 (2)	0.08146 (2)	0.00966 (7)
F1	0.71401 (4)	0.22252 (10)	0.66940 (7)	0.0279 (3)
N1	0.60412 (6)	0.48086 (11)	0.21431 (9)	0.0116 (3)
O1	0.50421 (5)	0.35404 (10)	0.08982 (8)	0.0178 (3)
O2	0.43571 (5)	0.35812 (10)	−0.04639 (7)	0.0159 (3)
O3	0.58593 (5)	0.42082 (10)	0.01770 (8)	0.0186 (3)
O4	0.51764 (5)	0.42292 (10)	−0.11894 (7)	0.0160 (3)
C1	0.59368 (7)	0.42103 (14)	0.28027 (11)	0.0137 (3)
H1	0.5572	0.3895	0.2682	0.016*
C2	0.63351 (7)	0.40326 (14)	0.36457 (10)	0.0136 (3)
H2	0.6242	0.3605	0.4092	0.016*
C3	0.68776 (7)	0.44833 (13)	0.38440 (10)	0.0130 (3)
C4	0.69797 (7)	0.51103 (14)	0.31542 (11)	0.0155 (3)
H4	0.7340	0.5440	0.3252	0.019*
C5	0.65545 (7)	0.52482 (14)	0.23286 (11)	0.0150 (3)
H5	0.6633	0.5679	0.1870	0.018*
C6	0.73294 (7)	0.43102 (14)	0.47159 (11)	0.0155 (3)
H6	0.7680	0.4674	0.4800	0.019*
C7	0.72862 (7)	0.36803 (14)	0.54005 (11)	0.0153 (3)
H7	0.6933	0.3328	0.5314	0.018*
C8	0.77343 (7)	0.34830 (14)	0.62731 (11)	0.0145 (3)
C9	0.82676 (8)	0.39856 (14)	0.65236 (12)	0.0183 (4)
H9	0.8355	0.4475	0.6108	0.022*
C10	0.86706 (8)	0.37847 (15)	0.73649 (12)	0.0217 (4)
H10	0.9027	0.4144	0.7520	0.026*
C11	0.85584 (8)	0.30621 (15)	0.79845 (11)	0.0193 (4)
H11	0.8837	0.2926	0.8559	0.023*
C12	0.80373 (8)	0.25442 (15)	0.77553 (11)	0.0183 (4)
H12	0.7952	0.2049	0.8169	0.022*
C13	0.76447 (7)	0.27626 (15)	0.69139 (11)	0.0165 (3)
C14	0.46433 (7)	0.31111 (13)	0.02665 (10)	0.0119 (3)
C15	0.45079 (7)	0.19230 (14)	0.03857 (11)	0.0135 (3)
C16	0.48550 (8)	0.13218 (15)	0.11172 (12)	0.0208 (4)
H16	0.5153	0.1680	0.1573	0.025*
C17	0.47659 (9)	0.01944 (16)	0.11824 (15)	0.0280 (5)
H17	0.5007	−0.0218	0.1678	0.034*
C18	0.43272 (9)	−0.03244 (16)	0.05253 (14)	0.0275 (4)
H18	0.4270	−0.1096	0.0566	0.033*
C19	0.39704 (8)	0.02751 (15)	−0.01927 (13)	0.0218 (4)
H19	0.3665	−0.0081	−0.0637	0.026*
C20	0.40603 (7)	0.13995 (14)	−0.02627 (11)	0.0161 (3)
H20	0.3815	0.1812	−0.0755	0.019*
C21	0.56556 (7)	0.39479 (13)	−0.06557 (10)	0.0119 (3)
C22	0.60095 (7)	0.32096 (13)	−0.10322 (11)	0.0130 (3)
C23	0.65249 (7)	0.28057 (14)	−0.04689 (12)	0.0165 (3)
H23	0.6665	0.3031	0.0152	0.020*
C24	0.68353 (8)	0.20735 (15)	−0.08111 (13)	0.0212 (4)
H24	0.7186	0.1795	−0.0423	0.025*
C25	0.66330 (8)	0.17484 (15)	−0.17186 (13)	0.0228 (4)
H25	0.6846	0.1249	−0.1953	0.027*
C26	0.61208 (9)	0.21529 (16)	−0.22829 (12)	0.0230 (4)
H26	0.5982	0.1926	−0.2903	0.028*
C27	0.58095 (8)	0.28870 (15)	−0.19479 (11)	0.0175 (4)
H27	0.5461	0.3170	−0.2340	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01035 (11)	0.00916 (10)	0.00825 (10)	0.00065 (7)	0.00129 (7)	0.00042 (7)
F1	0.0168 (6)	0.0453 (7)	0.0189 (5)	−0.0084 (5)	0.0022 (4)	0.0106 (5)
N1	0.0128 (7)	0.0105 (7)	0.0107 (6)	0.0010 (5)	0.0027 (5)	0.0005 (5)
O1	0.0185 (6)	0.0139 (6)	0.0159 (6)	−0.0037 (5)	−0.0014 (5)	0.0029 (5)
O2	0.0161 (6)	0.0148 (6)	0.0145 (6)	−0.0025 (5)	0.0015 (5)	0.0034 (5)
O3	0.0178 (6)	0.0232 (7)	0.0137 (6)	0.0065 (5)	0.0036 (5)	−0.0034 (5)
O4	0.0151 (6)	0.0199 (6)	0.0128 (5)	0.0033 (5)	0.0041 (5)	−0.0010 (5)
C1	0.0114 (8)	0.0147 (8)	0.0137 (7)	0.0006 (6)	0.0025 (6)	−0.0001 (6)
C2	0.0157 (8)	0.0146 (8)	0.0104 (7)	0.0009 (7)	0.0040 (6)	0.0016 (6)
C3	0.0137 (8)	0.0121 (8)	0.0108 (7)	0.0027 (6)	0.0008 (6)	−0.0005 (6)
C4	0.0124 (8)	0.0163 (8)	0.0160 (8)	−0.0033 (7)	0.0021 (6)	0.0017 (7)
C5	0.0172 (9)	0.0145 (8)	0.0121 (7)	−0.0013 (7)	0.0030 (7)	0.0028 (6)
C6	0.0129 (8)	0.0167 (8)	0.0138 (8)	−0.0014 (7)	−0.0001 (6)	−0.0002 (6)
C7	0.0119 (8)	0.0183 (8)	0.0129 (8)	−0.0002 (7)	0.0002 (6)	−0.0004 (7)
C8	0.0152 (8)	0.0149 (8)	0.0117 (7)	0.0029 (7)	0.0019 (6)	−0.0010 (6)
C9	0.0205 (9)	0.0148 (8)	0.0164 (8)	−0.0008 (7)	0.0014 (7)	0.0023 (7)
C10	0.0180 (9)	0.0194 (9)	0.0199 (9)	−0.0017 (7)	−0.0047 (7)	0.0013 (7)
C11	0.0209 (9)	0.0197 (9)	0.0110 (7)	0.0043 (7)	−0.0034 (7)	−0.0012 (7)
C12	0.0221 (9)	0.0208 (9)	0.0107 (7)	0.0034 (7)	0.0038 (7)	0.0019 (7)
C13	0.0127 (8)	0.0219 (9)	0.0143 (8)	−0.0013 (7)	0.0036 (7)	−0.0019 (7)
C14	0.0109 (8)	0.0119 (8)	0.0135 (7)	0.0009 (6)	0.0048 (6)	−0.0005 (6)
C15	0.0135 (8)	0.0123 (8)	0.0166 (8)	0.0007 (6)	0.0076 (7)	0.0009 (6)
C16	0.0164 (9)	0.0170 (9)	0.0244 (9)	−0.0007 (7)	0.0002 (7)	0.0051 (7)
C17	0.0250 (11)	0.0177 (10)	0.0369 (11)	0.0011 (8)	0.0040 (9)	0.0109 (8)
C18	0.0311 (11)	0.0131 (8)	0.0423 (12)	−0.0032 (8)	0.0174 (10)	0.0026 (8)
C19	0.0228 (10)	0.0188 (9)	0.0256 (9)	−0.0091 (7)	0.0101 (8)	−0.0062 (7)
C20	0.0173 (9)	0.0166 (9)	0.0154 (8)	−0.0007 (7)	0.0065 (7)	−0.0004 (7)
C21	0.0142 (8)	0.0101 (7)	0.0121 (7)	−0.0026 (6)	0.0050 (6)	0.0008 (6)
C22	0.0160 (8)	0.0100 (7)	0.0152 (8)	−0.0005 (6)	0.0081 (7)	0.0019 (6)
C23	0.0172 (9)	0.0149 (8)	0.0177 (8)	0.0002 (7)	0.0062 (7)	0.0006 (7)
C24	0.0187 (9)	0.0167 (9)	0.0300 (9)	0.0036 (7)	0.0104 (8)	0.0049 (8)
C25	0.0306 (11)	0.0137 (8)	0.0336 (10)	0.0013 (8)	0.0238 (9)	−0.0013 (8)
C26	0.0347 (11)	0.0207 (9)	0.0181 (8)	0.0002 (8)	0.0146 (8)	−0.0030 (7)
C27	0.0207 (9)	0.0182 (9)	0.0149 (8)	0.0009 (7)	0.0074 (7)	0.0015 (7)

Geometric parameters (Å, º) top

Cu1—O3	1.9682 (12)	C7—C8	1.469 (2)
Cu1—O4ⁱ	1.9700 (12)	C8—C13	1.392 (2)
Cu1—O2ⁱ	1.9777 (11)	C8—C9	1.400 (2)
Cu1—O1	1.9816 (12)	C9—C10	1.386 (2)
Cu1—N1	2.1677 (14)	C10—C11	1.391 (3)
Cu1—Cu1ⁱ	2.6677 (4)	C11—C12	1.384 (3)
F1—C13	1.3604 (19)	C12—C13	1.379 (2)
N1—C5	1.331 (2)	C14—C15	1.503 (2)
N1—C1	1.344 (2)	C15—C16	1.389 (2)
O1—C14	1.2606 (19)	C15—C20	1.391 (2)
O2—C14	1.2611 (19)	C16—C17	1.392 (3)
O2—Cu1ⁱ	1.9777 (11)	C17—C18	1.382 (3)
O3—C21	1.2627 (19)	C18—C19	1.384 (3)
O4—C21	1.262 (2)	C19—C20	1.390 (2)
O4—Cu1ⁱ	1.9698 (12)	C21—C22	1.500 (2)
C1—C2	1.378 (2)	C22—C23	1.390 (2)
C2—C3	1.400 (2)	C22—C27	1.397 (2)
C3—C4	1.398 (2)	C23—C24	1.390 (2)
C3—C6	1.468 (2)	C24—C25	1.387 (3)
C4—C5	1.383 (2)	C25—C26	1.385 (3)
C6—C7	1.337 (2)	C26—C27	1.387 (2)

O3—Cu1—O4ⁱ	167.72 (5)	C13—C8—C7	120.44 (15)
O3—Cu1—O2ⁱ	90.16 (5)	C9—C8—C7	123.95 (15)
O4ⁱ—Cu1—O2ⁱ	88.15 (5)	C10—C9—C8	121.42 (16)
O3—Cu1—O1	88.01 (5)	C9—C10—C11	120.71 (17)
O4ⁱ—Cu1—O1	91.06 (5)	C12—C11—C10	119.35 (16)
O2ⁱ—Cu1—O1	167.72 (5)	C13—C12—C11	118.59 (16)
O3—Cu1—N1	93.49 (5)	F1—C13—C12	117.62 (15)
O4ⁱ—Cu1—N1	98.79 (5)	F1—C13—C8	118.06 (14)
O2ⁱ—Cu1—N1	98.45 (5)	C12—C13—C8	124.31 (16)
O1—Cu1—N1	93.78 (5)	O1—C14—O2	125.88 (15)
O3—Cu1—Cu1ⁱ	85.26 (3)	O1—C14—C15	116.90 (14)
O4ⁱ—Cu1—Cu1ⁱ	82.48 (3)	O2—C14—C15	117.20 (14)
O2ⁱ—Cu1—Cu1ⁱ	85.75 (3)	C16—C15—C20	119.60 (16)
O1—Cu1—Cu1ⁱ	82.00 (3)	C16—C15—C14	119.71 (15)
N1—Cu1—Cu1ⁱ	175.63 (4)	C20—C15—C14	120.55 (15)
C5—N1—C1	117.46 (14)	C15—C16—C17	120.04 (18)
C5—N1—Cu1	122.04 (11)	C18—C17—C16	119.99 (18)
C1—N1—Cu1	120.45 (11)	C17—C18—C19	120.29 (18)
C14—O1—Cu1	124.94 (10)	C18—C19—C20	119.85 (18)
C14—O2—Cu1ⁱ	120.61 (10)	C19—C20—C15	120.19 (16)
C21—O3—Cu1	121.41 (11)	O4—C21—O3	125.82 (15)
C21—O4—Cu1ⁱ	124.69 (10)	O4—C21—C22	117.37 (14)
N1—C1—C2	123.03 (16)	O3—C21—C22	116.78 (14)
C1—C2—C3	119.91 (15)	C23—C22—C27	119.56 (15)
C4—C3—C2	116.50 (14)	C23—C22—C21	120.57 (14)
C4—C3—C6	120.22 (15)	C27—C22—C21	119.82 (15)
C2—C3—C6	123.27 (15)	C24—C23—C22	120.21 (16)
C5—C4—C3	119.72 (16)	C25—C24—C23	120.05 (17)
N1—C5—C4	123.38 (15)	C26—C25—C24	119.90 (17)
C7—C6—C3	125.07 (16)	C25—C26—C27	120.42 (17)
C6—C7—C8	126.04 (16)	C26—C27—C22	119.86 (17)
C13—C8—C9	115.61 (15)

Symmetry code: (i) −x+1, −y+1, −z.

(3) top

Crystal data top

C₅₄H₄₀Cu₂F₂N₂O₈	F(000) = 2072
M_r = 1009.96	D_x = 1.504 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.1802 (18) Å	Cell parameters from 9807 reflections
b = 12.0004 (9) Å	θ = 3.0–28.3°
c = 15.5976 (10) Å	µ = 1.02 mm⁻¹
β = 108.802 (2)°	T = 100 K
V = 4461.7 (5) Å³	Block, green
Z = 4	0.41 × 0.29 × 0.22 mm

Data collection top

Bruker D8 Venture diffractometer	4589 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.027
Absorption correction: multi-scan SADABS (Sheldrick, 2010)	θ_max = 27.5°, θ_min = 2.2°
T_min = 0.686, T_max = 0.746	h = −32→32
57847 measured reflections	k = −15→15
5121 independent reflections	l = −20→19

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.073	w = 1/[σ²(F_o²) + (0.0376P)² + 5.4768P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
5121 reflections	Δρ_max = 0.67 e Å⁻³
311 parameters	Δρ_min = −0.43 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.53967 (2)	0.49521 (2)	0.08042 (2)	0.01227 (6)
O1	0.56493 (4)	0.64218 (8)	0.05037 (7)	0.0192 (2)
O2	0.49670 (5)	0.65040 (9)	−0.08412 (7)	0.0221 (2)
O3	0.48247 (4)	0.57360 (9)	0.11929 (7)	0.0187 (2)
O4	0.41466 (4)	0.57893 (9)	−0.01572 (7)	0.0210 (2)
N1	0.60167 (5)	0.47377 (10)	0.21191 (8)	0.0148 (2)
C1	0.65347 (6)	0.51425 (12)	0.22955 (10)	0.0198 (3)
H1	0.6621	0.5540	0.1831	0.024*
C2	0.69516 (6)	0.50117 (12)	0.31216 (10)	0.0207 (3)
H2	0.7313	0.5321	0.3217	0.025*
C3	0.68376 (6)	0.44236 (12)	0.38140 (9)	0.0161 (3)
C4	0.62954 (6)	0.40019 (12)	0.36259 (9)	0.0173 (3)
H4	0.6197	0.3596	0.4075	0.021*
C5	0.59037 (6)	0.41777 (12)	0.27853 (9)	0.0168 (3)
H5	0.5536	0.3889	0.2672	0.020*
C6	0.72822 (6)	0.42625 (13)	0.46859 (10)	0.0192 (3)
H6	0.7641	0.4567	0.4748	0.023*
C7	0.72234 (6)	0.37242 (13)	0.53965 (10)	0.0202 (3)
H7	0.6860	0.3450	0.5338	0.024*
C8	0.76665 (6)	0.35130 (12)	0.62620 (9)	0.0194 (3)
C9	0.82134 (7)	0.39178 (14)	0.64575 (11)	0.0248 (3)
H9	0.8311	0.4356	0.6024	0.030*
C10	0.86117 (7)	0.36803 (15)	0.72809 (12)	0.0309 (4)
H10A	0.8979	0.3975	0.7408	0.037*	0.668 (2)
C11	0.84926 (7)	0.30266 (14)	0.79272 (10)	0.0264 (3)
H11	0.8771	0.2861	0.8488	0.032*
C12	0.79559 (7)	0.26281 (14)	0.77244 (10)	0.0273 (3)
H12A	0.7865	0.2175	0.8157	0.033*	0.332 (2)
C13	0.75414 (7)	0.28619 (14)	0.69129 (10)	0.0254 (3)
H13	0.7173	0.2580	0.6800	0.030*
C14	0.53670 (6)	0.69162 (11)	−0.02117 (9)	0.0154 (3)
C15	0.55120 (6)	0.81131 (12)	−0.03162 (10)	0.0183 (3)
C16	0.59687 (7)	0.86170 (13)	0.03175 (11)	0.0233 (3)
H16	0.6212	0.8189	0.0797	0.028*
C17	0.60697 (8)	0.97495 (15)	0.02500 (14)	0.0330 (4)
H17	0.6381	1.0094	0.0685	0.040*
C18	0.57184 (9)	1.03716 (15)	−0.04464 (15)	0.0400 (5)
H18	0.5786	1.1146	−0.0486	0.048*
C19	0.52692 (9)	0.98736 (15)	−0.10866 (16)	0.0403 (5)
H19	0.5030	1.0304	−0.1568	0.048*
C20	0.51670 (7)	0.87400 (14)	−0.10272 (13)	0.0294 (4)
H20	0.4861	0.8396	−0.1473	0.035*
C21	0.43482 (6)	0.60285 (11)	0.06713 (9)	0.0145 (3)
C22	0.40008 (6)	0.67586 (11)	0.10635 (9)	0.0155 (3)
C23	0.42088 (7)	0.70900 (13)	0.19656 (10)	0.0213 (3)
H23	0.4556	0.6803	0.2347	0.026*
C24	0.39086 (7)	0.78396 (14)	0.23081 (11)	0.0271 (3)
H24	0.4056	0.8076	0.2921	0.033*
C25	0.33971 (7)	0.82451 (13)	0.17646 (11)	0.0257 (3)
H25	0.3195	0.8762	0.2001	0.031*
C26	0.31803 (7)	0.78935 (13)	0.08712 (11)	0.0248 (3)
H26	0.2825	0.8160	0.0500	0.030*
C27	0.34805 (6)	0.71527 (13)	0.05186 (10)	0.0198 (3)
H27	0.3331	0.6915	−0.0093	0.024*
F1	0.78536 (7)	0.19488 (17)	0.83139 (10)	0.0440 (4)	0.668 (2)
F1A	0.90973 (13)	0.4023 (3)	0.7451 (2)	0.0440 (4)	0.332 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01351 (10)	0.01166 (9)	0.00985 (9)	0.00046 (6)	0.00126 (6)	0.00074 (6)
O1	0.0215 (5)	0.0165 (5)	0.0178 (5)	−0.0033 (4)	0.0036 (4)	0.0022 (4)
O2	0.0236 (5)	0.0163 (5)	0.0211 (5)	−0.0045 (4)	−0.0002 (4)	0.0040 (4)
O3	0.0177 (5)	0.0237 (5)	0.0139 (5)	0.0036 (4)	0.0041 (4)	−0.0003 (4)
O4	0.0200 (5)	0.0263 (6)	0.0143 (5)	0.0057 (4)	0.0024 (4)	−0.0038 (4)
N1	0.0162 (6)	0.0141 (5)	0.0122 (5)	0.0021 (4)	0.0021 (4)	0.0012 (4)
C1	0.0197 (7)	0.0221 (7)	0.0152 (7)	−0.0019 (6)	0.0022 (6)	0.0060 (5)
C2	0.0159 (7)	0.0249 (8)	0.0185 (7)	−0.0029 (5)	0.0015 (6)	0.0044 (6)
C3	0.0176 (7)	0.0155 (6)	0.0129 (6)	0.0036 (5)	0.0015 (5)	0.0007 (5)
C4	0.0197 (7)	0.0192 (7)	0.0130 (6)	0.0014 (5)	0.0052 (5)	0.0027 (5)
C5	0.0154 (6)	0.0189 (7)	0.0146 (6)	−0.0003 (5)	0.0028 (5)	0.0001 (5)
C6	0.0167 (7)	0.0218 (7)	0.0155 (6)	0.0014 (5)	0.0003 (5)	0.0007 (5)
C7	0.0199 (7)	0.0222 (7)	0.0149 (7)	0.0012 (6)	0.0005 (6)	0.0001 (5)
C8	0.0242 (7)	0.0177 (7)	0.0126 (6)	0.0046 (6)	0.0009 (6)	−0.0011 (5)
C9	0.0260 (8)	0.0240 (8)	0.0196 (7)	0.0011 (6)	0.0007 (6)	0.0045 (6)
C10	0.0261 (9)	0.0317 (9)	0.0257 (8)	0.0011 (7)	−0.0044 (7)	0.0028 (7)
C11	0.0304 (8)	0.0271 (8)	0.0139 (7)	0.0082 (7)	−0.0039 (6)	−0.0013 (6)
C12	0.0354 (9)	0.0305 (8)	0.0129 (7)	0.0056 (7)	0.0032 (6)	0.0043 (6)
C13	0.0253 (8)	0.0319 (8)	0.0160 (7)	0.0008 (7)	0.0026 (6)	0.0023 (6)
C14	0.0171 (6)	0.0136 (6)	0.0179 (7)	0.0000 (5)	0.0089 (5)	−0.0002 (5)
C15	0.0214 (7)	0.0137 (6)	0.0237 (7)	−0.0010 (5)	0.0125 (6)	0.0001 (5)
C16	0.0272 (8)	0.0197 (7)	0.0272 (8)	−0.0055 (6)	0.0147 (7)	−0.0046 (6)
C17	0.0388 (10)	0.0233 (8)	0.0451 (11)	−0.0128 (7)	0.0252 (9)	−0.0111 (7)
C18	0.0513 (12)	0.0143 (8)	0.0662 (14)	−0.0054 (8)	0.0353 (11)	0.0014 (8)
C19	0.0455 (12)	0.0222 (9)	0.0566 (13)	0.0047 (8)	0.0212 (10)	0.0170 (8)
C20	0.0295 (9)	0.0201 (8)	0.0379 (9)	−0.0002 (6)	0.0097 (7)	0.0087 (7)
C21	0.0171 (6)	0.0114 (6)	0.0153 (6)	−0.0014 (5)	0.0056 (5)	0.0018 (5)
C22	0.0184 (7)	0.0129 (6)	0.0169 (6)	−0.0010 (5)	0.0082 (5)	0.0013 (5)
C23	0.0234 (7)	0.0230 (7)	0.0179 (7)	0.0015 (6)	0.0072 (6)	0.0004 (6)
C24	0.0350 (9)	0.0281 (8)	0.0210 (7)	−0.0012 (7)	0.0129 (7)	−0.0057 (6)
C25	0.0306 (8)	0.0197 (7)	0.0333 (9)	0.0018 (6)	0.0194 (7)	−0.0036 (6)
C26	0.0208 (7)	0.0227 (8)	0.0316 (8)	0.0032 (6)	0.0095 (7)	0.0016 (6)
C27	0.0193 (7)	0.0195 (7)	0.0202 (7)	−0.0005 (5)	0.0057 (6)	−0.0004 (6)
F1	0.0274 (7)	0.0776 (12)	0.0237 (7)	−0.0003 (7)	0.0039 (6)	0.0221 (7)
F1A	0.0274 (7)	0.0776 (12)	0.0237 (7)	−0.0003 (7)	0.0039 (6)	0.0221 (7)

Geometric parameters (Å, º) top

Cu1—O4ⁱ	1.9699 (10)	C8—C9	1.398 (2)
Cu1—O3	1.9723 (10)	C9—C10	1.381 (2)
Cu1—O1	1.9817 (10)	C10—F1A	1.235 (4)
Cu1—O2ⁱ	1.9822 (10)	C10—C11	1.384 (3)
Cu1—N1	2.1554 (12)	C11—C12	1.371 (2)
Cu1—Cu1ⁱ	2.6586 (3)	C12—F1	1.315 (2)
O1—C14	1.2613 (17)	C12—C13	1.385 (2)
O2—C14	1.2593 (17)	C14—C15	1.5038 (19)
O2—Cu1ⁱ	1.9823 (10)	C15—C20	1.389 (2)
O3—C21	1.2631 (17)	C15—C16	1.390 (2)
O4—C21	1.2599 (17)	C16—C17	1.393 (2)
O4—Cu1ⁱ	1.9699 (10)	C17—C18	1.378 (3)
N1—C1	1.335 (2)	C18—C19	1.380 (3)
N1—C5	1.3428 (18)	C19—C20	1.393 (2)
C1—C2	1.384 (2)	C21—C22	1.5006 (19)
C2—C3	1.395 (2)	C22—C23	1.392 (2)
C3—C4	1.396 (2)	C22—C27	1.394 (2)
C3—C6	1.4692 (19)	C23—C24	1.388 (2)
C4—C5	1.3795 (19)	C24—C25	1.382 (2)
C6—C7	1.332 (2)	C25—C26	1.388 (2)
C7—C8	1.4698 (19)	C26—C27	1.390 (2)
C8—C13	1.395 (2)

O4ⁱ—Cu1—O3	167.86 (4)	C9—C8—C7	122.90 (14)
O4ⁱ—Cu1—O1	89.77 (5)	C10—C9—C8	120.02 (15)
O3—Cu1—O1	88.28 (4)	F1A—C10—C9	120.2 (2)
O4ⁱ—Cu1—O2ⁱ	88.18 (5)	F1A—C10—C11	117.6 (2)
O3—Cu1—O2ⁱ	91.23 (5)	C9—C10—C11	122.11 (16)
O1—Cu1—O2ⁱ	167.94 (4)	C12—C11—C10	117.28 (14)
O4ⁱ—Cu1—N1	94.02 (4)	F1—C12—C11	117.10 (15)
O3—Cu1—N1	98.12 (4)	F1—C12—C13	120.33 (17)
O1—Cu1—N1	98.17 (4)	C11—C12—C13	122.45 (15)
O2ⁱ—Cu1—N1	93.83 (4)	C12—C13—C8	119.87 (16)
O4ⁱ—Cu1—Cu1ⁱ	85.49 (3)	O2—C14—O1	125.88 (13)
O3—Cu1—Cu1ⁱ	82.43 (3)	O2—C14—C15	116.86 (12)
O1—Cu1—Cu1ⁱ	86.51 (3)	O1—C14—C15	117.25 (12)
O2ⁱ—Cu1—Cu1ⁱ	81.48 (3)	C20—C15—C16	119.56 (14)
N1—Cu1—Cu1ⁱ	175.30 (3)	C20—C15—C14	119.51 (14)
C14—O1—Cu1	119.71 (9)	C16—C15—C14	120.83 (13)
C14—O2—Cu1ⁱ	125.77 (9)	C15—C16—C17	120.00 (17)
C21—O3—Cu1	124.81 (9)	C18—C17—C16	120.11 (18)
C21—O4—Cu1ⁱ	121.31 (9)	C17—C18—C19	120.24 (16)
C1—N1—C5	117.35 (12)	C18—C19—C20	120.03 (19)
C1—N1—Cu1	120.85 (10)	C15—C20—C19	120.03 (18)
C5—N1—Cu1	121.79 (10)	O4—C21—O3	125.62 (13)
N1—C1—C2	123.25 (14)	O4—C21—C22	117.13 (12)
C1—C2—C3	119.63 (14)	O3—C21—C22	117.21 (12)
C2—C3—C4	116.88 (13)	C23—C22—C27	119.52 (13)
C2—C3—C6	119.83 (13)	C23—C22—C21	120.01 (13)
C4—C3—C6	123.29 (13)	C27—C22—C21	120.41 (12)
C5—C4—C3	119.72 (13)	C24—C23—C22	120.02 (14)
N1—C5—C4	123.16 (13)	C25—C24—C23	120.50 (15)
C7—C6—C3	125.33 (14)	C24—C25—C26	119.73 (14)
C6—C7—C8	126.37 (14)	C25—C26—C27	120.23 (15)
C13—C8—C9	118.26 (14)	C26—C27—C22	119.98 (14)
C13—C8—C7	118.84 (14)

Symmetry code: (i) −x+1, −y+1, −z.

(5a) top

Crystal data top

C₅₄H₄₀Cu₂F₂N₂O₈	Z = 1
M_r = 1009.96	F(000) = 518
Triclinic, P1	D_x = 1.489 Mg m⁻³
a = 10.3725 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.0398 (5) Å	Cell parameters from 9903 reflections
c = 12.0294 (5) Å	θ = 2.4–32.1°
α = 71.354 (1)°	µ = 1.01 mm⁻¹
β = 66.229 (1)°	T = 100 K
γ = 65.356 (1)°	Prism frag, green
V = 1126.61 (9) Å³	0.40 × 0.30 × 0.13 mm

Data collection top

Bruker APEX-II CCD diffractometer	4010 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.030
Absorption correction: multi-scan Sadabs (Sheldrick, 2010)	θ_max = 26.0°, θ_min = 2.3°
T_min = 0.687, T_max = 0.878	h = −12→12
22753 measured reflections	k = −13→13
4416 independent reflections	l = −14→14

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.027P)² + 1.0045P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
4416 reflections	Δρ_max = 0.41 e Å⁻³
307 parameters	Δρ_min = −0.26 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
ZN1	0.08988 (2)	0.05300 (2)	0.40088 (2)	0.01478 (8)
F1	0.18010 (13)	0.56593 (13)	−0.08486 (11)	0.0289 (3)
O1	0.18687 (15)	0.03153 (14)	0.52085 (12)	0.0233 (3)
O2	0.02998 (15)	−0.05251 (14)	0.69044 (12)	0.0220 (3)
O3	0.06425 (15)	−0.21979 (13)	0.54004 (12)	0.0231 (3)
O4	0.22112 (15)	−0.13244 (13)	0.37401 (12)	0.0235 (3)
N1	0.21722 (16)	0.17022 (15)	0.25257 (14)	0.0157 (3)
C1	0.2570 (2)	0.17327 (19)	0.13173 (17)	0.0178 (4)
H1	0.2264	0.1197	0.1058	0.021*
C2	0.3409 (2)	0.25100 (19)	0.04187 (17)	0.0175 (4)
H2	0.3661	0.2503	−0.0432	0.021*
C3	0.38766 (19)	0.32971 (18)	0.07753 (16)	0.0156 (4)
C4	0.3429 (2)	0.32870 (19)	0.20327 (17)	0.0177 (4)
H4	0.3699	0.3828	0.2319	0.021*
C5	0.2590 (2)	0.24876 (18)	0.28676 (17)	0.0175 (4)
H5	0.2297	0.2496	0.3723	0.021*
C6	0.47785 (19)	0.41686 (18)	−0.01563 (16)	0.0153 (4)
H6	0.5186	0.3928	−0.0995	0.018*
C7	0.3989 (2)	0.57580 (18)	−0.02147 (16)	0.0159 (4)
H7	0.4074	0.6223	−0.1091	0.019*
C8	0.2379 (2)	0.62179 (18)	0.05842 (16)	0.0162 (4)
C9	0.1857 (2)	0.66779 (19)	0.16866 (18)	0.0205 (4)
H9	0.2539	0.6779	0.1963	0.025*
C10	0.0358 (2)	0.6993 (2)	0.23929 (19)	0.0241 (4)
H10	0.0025	0.7303	0.3145	0.029*
C11	−0.0647 (2)	0.6855 (2)	0.19994 (19)	0.0255 (4)
H11	−0.1670	0.7065	0.2484	0.031*
C12	−0.0164 (2)	0.6411 (2)	0.08982 (19)	0.0239 (4)
H12	−0.0844	0.6317	0.0614	0.029*
C13	0.1324 (2)	0.61124 (19)	0.02310 (17)	0.0195 (4)
C14	0.1409 (2)	−0.01207 (18)	0.63548 (17)	0.0164 (4)
C15	0.2255 (2)	−0.01303 (18)	0.71210 (17)	0.0166 (4)
C16	0.1773 (2)	−0.05066 (19)	0.84019 (18)	0.0211 (4)
H16	0.0941	−0.0818	0.8797	0.025*
C17	0.2513 (2)	−0.0425 (2)	0.90986 (19)	0.0249 (4)
H17	0.2181	−0.0673	0.9973	0.030*
C18	0.3739 (2)	0.0021 (2)	0.8520 (2)	0.0255 (4)
H18	0.4233	0.0086	0.9002	0.031*
C19	0.4245 (2)	0.03696 (19)	0.72424 (19)	0.0226 (4)
H19	0.5096	0.0656	0.6848	0.027*
C20	0.3499 (2)	0.02971 (18)	0.65434 (18)	0.0186 (4)
H20	0.3838	0.0540	0.5669	0.022*
C21	0.1828 (2)	−0.23008 (19)	0.45004 (16)	0.0170 (4)
C22	0.2869 (2)	−0.37116 (19)	0.43376 (17)	0.0191 (4)
C23	0.4344 (2)	−0.3933 (2)	0.35702 (17)	0.0229 (4)
H23	0.4684	−0.3185	0.3120	0.027*
C24	0.5314 (2)	−0.5246 (2)	0.34648 (19)	0.0297 (5)
H24	0.6323	−0.5396	0.2952	0.036*
C25	0.4813 (3)	−0.6338 (2)	0.4107 (2)	0.0328 (5)
H25	0.5479	−0.7236	0.4034	0.039*
C26	0.3343 (3)	−0.6123 (2)	0.4857 (2)	0.0307 (5)
H26	0.2998	−0.6872	0.5286	0.037*
C27	0.2374 (2)	−0.4816 (2)	0.49824 (18)	0.0238 (4)
H27	0.1372	−0.4672	0.5508	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
ZN1	0.01564 (12)	0.01484 (12)	0.01394 (12)	−0.00945 (9)	−0.00212 (8)	−0.00005 (8)
F1	0.0240 (6)	0.0444 (8)	0.0257 (6)	−0.0157 (6)	−0.0057 (5)	−0.0123 (5)
O1	0.0242 (7)	0.0329 (8)	0.0167 (7)	−0.0181 (6)	−0.0065 (6)	0.0022 (6)
O2	0.0250 (7)	0.0275 (8)	0.0183 (7)	−0.0179 (6)	−0.0063 (6)	0.0017 (6)
O3	0.0207 (7)	0.0177 (7)	0.0253 (7)	−0.0088 (6)	0.0018 (6)	−0.0051 (6)
O4	0.0226 (7)	0.0184 (7)	0.0217 (7)	−0.0084 (6)	0.0015 (6)	−0.0025 (6)
N1	0.0152 (7)	0.0154 (8)	0.0178 (8)	−0.0087 (6)	−0.0052 (6)	0.0004 (6)
C1	0.0166 (9)	0.0173 (9)	0.0210 (9)	−0.0088 (7)	−0.0048 (7)	−0.0026 (7)
C2	0.0180 (9)	0.0205 (10)	0.0142 (9)	−0.0088 (8)	−0.0041 (7)	−0.0016 (7)
C3	0.0123 (8)	0.0152 (9)	0.0166 (9)	−0.0053 (7)	−0.0042 (7)	0.0010 (7)
C4	0.0175 (9)	0.0163 (9)	0.0223 (9)	−0.0088 (8)	−0.0067 (7)	−0.0023 (7)
C5	0.0191 (9)	0.0174 (9)	0.0154 (9)	−0.0081 (8)	−0.0045 (7)	−0.0008 (7)
C6	0.0155 (9)	0.0190 (9)	0.0127 (8)	−0.0100 (7)	−0.0026 (7)	−0.0011 (7)
C7	0.0174 (9)	0.0180 (9)	0.0137 (9)	−0.0103 (7)	−0.0048 (7)	0.0015 (7)
C8	0.0158 (9)	0.0112 (9)	0.0189 (9)	−0.0070 (7)	−0.0051 (7)	0.0035 (7)
C9	0.0191 (9)	0.0188 (10)	0.0246 (10)	−0.0077 (8)	−0.0085 (8)	−0.0012 (8)
C10	0.0237 (10)	0.0217 (10)	0.0232 (10)	−0.0040 (8)	−0.0053 (8)	−0.0069 (8)
C11	0.0128 (9)	0.0223 (10)	0.0326 (11)	−0.0022 (8)	−0.0022 (8)	−0.0052 (9)
C12	0.0173 (9)	0.0240 (10)	0.0324 (11)	−0.0080 (8)	−0.0100 (8)	−0.0033 (9)
C13	0.0215 (10)	0.0168 (9)	0.0193 (9)	−0.0079 (8)	−0.0058 (8)	−0.0009 (7)
C14	0.0176 (9)	0.0103 (8)	0.0201 (9)	−0.0039 (7)	−0.0057 (7)	−0.0024 (7)
C15	0.0179 (9)	0.0094 (8)	0.0227 (9)	−0.0030 (7)	−0.0084 (7)	−0.0025 (7)
C16	0.0252 (10)	0.0156 (9)	0.0227 (10)	−0.0092 (8)	−0.0090 (8)	0.0013 (8)
C17	0.0343 (11)	0.0181 (10)	0.0238 (10)	−0.0071 (9)	−0.0155 (9)	0.0003 (8)
C18	0.0284 (11)	0.0172 (10)	0.0372 (12)	−0.0015 (8)	−0.0214 (9)	−0.0067 (9)
C19	0.0150 (9)	0.0160 (9)	0.0360 (11)	−0.0014 (7)	−0.0090 (8)	−0.0073 (8)
C20	0.0166 (9)	0.0132 (9)	0.0229 (10)	−0.0023 (7)	−0.0049 (7)	−0.0046 (7)
C21	0.0190 (9)	0.0197 (10)	0.0162 (9)	−0.0086 (8)	−0.0069 (7)	−0.0033 (7)
C22	0.0233 (10)	0.0205 (10)	0.0151 (9)	−0.0053 (8)	−0.0085 (8)	−0.0046 (7)
C23	0.0255 (10)	0.0288 (11)	0.0145 (9)	−0.0068 (9)	−0.0084 (8)	−0.0045 (8)
C24	0.0255 (11)	0.0404 (13)	0.0184 (10)	0.0022 (9)	−0.0091 (8)	−0.0143 (9)
C25	0.0431 (13)	0.0246 (11)	0.0270 (11)	0.0068 (10)	−0.0198 (10)	−0.0128 (9)
C26	0.0470 (14)	0.0196 (11)	0.0267 (11)	−0.0071 (10)	−0.0173 (10)	−0.0038 (9)
C27	0.0285 (11)	0.0211 (10)	0.0223 (10)	−0.0065 (8)	−0.0096 (8)	−0.0049 (8)

Geometric parameters (Å, º) top

ZN1—O2ⁱ	1.9655 (13)	C7—C8	1.510 (2)
ZN1—O4	1.9730 (14)	C7—C6ⁱⁱ	1.552 (2)
ZN1—O1	1.9758 (13)	C8—C13	1.381 (3)
ZN1—O3ⁱ	1.9793 (13)	C8—C9	1.390 (3)
ZN1—N1	2.1568 (15)	C9—C10	1.390 (3)
ZN1—ZN1ⁱ	2.6426 (4)	C10—C11	1.382 (3)
F1—C13	1.368 (2)	C11—C12	1.386 (3)
O1—C14	1.264 (2)	C12—C13	1.371 (3)
O2—C14	1.260 (2)	C14—C15	1.502 (3)
O2—ZN1ⁱ	1.9655 (13)	C15—C16	1.393 (3)
O3—C21	1.260 (2)	C15—C20	1.395 (3)
O3—ZN1ⁱ	1.9792 (13)	C16—C17	1.387 (3)
O4—C21	1.261 (2)	C17—C18	1.390 (3)
N1—C1	1.335 (2)	C18—C19	1.388 (3)
N1—C5	1.340 (2)	C19—C20	1.390 (3)
C1—C2	1.391 (3)	C21—C22	1.501 (3)
C2—C3	1.389 (3)	C22—C23	1.395 (3)
C3—C4	1.390 (3)	C22—C27	1.396 (3)
C3—C6	1.508 (2)	C23—C24	1.388 (3)
C4—C5	1.384 (3)	C24—C25	1.387 (3)
C6—C7ⁱⁱ	1.552 (2)	C25—C26	1.387 (3)
C6—C7	1.589 (3)	C26—C27	1.386 (3)

O2ⁱ—ZN1—O4	89.84 (6)	C6ⁱⁱ—C7—C6	90.85 (13)
O2ⁱ—ZN1—O1	168.26 (5)	C13—C8—C9	116.17 (17)
O4—ZN1—O1	88.01 (6)	C13—C8—C7	117.63 (16)
O2ⁱ—ZN1—O3ⁱ	90.74 (6)	C9—C8—C7	126.11 (16)
O4—ZN1—O3ⁱ	168.22 (5)	C8—C9—C10	121.38 (18)
O1—ZN1—O3ⁱ	89.04 (6)	C11—C10—C9	119.93 (19)
O2ⁱ—ZN1—N1	96.84 (5)	C10—C11—C12	120.11 (18)
O4—ZN1—N1	100.62 (6)	C13—C12—C11	118.00 (18)
O1—ZN1—N1	94.89 (5)	F1—C13—C12	117.93 (17)
O3ⁱ—ZN1—N1	90.99 (6)	F1—C13—C8	117.65 (16)
O2ⁱ—ZN1—ZN1ⁱ	86.10 (4)	C12—C13—C8	124.41 (18)
O4—ZN1—ZN1ⁱ	88.62 (4)	O2—C14—O1	125.70 (17)
O1—ZN1—ZN1ⁱ	82.32 (4)	O2—C14—C15	117.74 (16)
O3ⁱ—ZN1—ZN1ⁱ	79.69 (4)	O1—C14—C15	116.56 (16)
N1—ZN1—ZN1ⁱ	170.28 (4)	C16—C15—C20	119.83 (17)
C14—O1—ZN1	124.82 (12)	C16—C15—C14	120.72 (16)
C14—O2—ZN1ⁱ	120.99 (12)	C20—C15—C14	119.39 (16)
C21—O3—ZN1ⁱ	128.09 (12)	C17—C16—C15	119.80 (18)
C21—O4—ZN1	117.90 (12)	C16—C17—C18	120.14 (19)
C1—N1—C5	117.25 (15)	C19—C18—C17	120.42 (18)
C1—N1—ZN1	126.99 (12)	C18—C19—C20	119.51 (18)
C5—N1—ZN1	115.75 (12)	C19—C20—C15	120.28 (18)
N1—C1—C2	123.29 (17)	O3—C21—O4	125.55 (17)
C3—C2—C1	119.43 (17)	O3—C21—C22	116.54 (16)
C2—C3—C4	117.04 (16)	O4—C21—C22	117.90 (16)
C2—C3—C6	121.85 (16)	C23—C22—C27	119.53 (18)
C4—C3—C6	121.07 (16)	C23—C22—C21	120.48 (17)
C5—C4—C3	119.91 (17)	C27—C22—C21	119.97 (17)
N1—C5—C4	123.03 (17)	C24—C23—C22	120.0 (2)
C3—C6—C7ⁱⁱ	115.77 (15)	C25—C24—C23	120.1 (2)
C3—C6—C7	116.00 (14)	C26—C25—C24	120.1 (2)
C7ⁱⁱ—C6—C7	89.15 (13)	C27—C26—C25	120.1 (2)
C8—C7—C6ⁱⁱ	119.60 (15)	C26—C27—C22	120.1 (2)
C8—C7—C6	116.05 (14)

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

Acknowledgements

We thank Ms Geok Kheng Tan for the X-ray data collection. We would like to thank Dr Geetha Bolla and Vijayakumar S. Vishnu of NUS for their assistance in some of the experiments.

Funding information

JJV would like to thank the Ministry of Education Singapore for their generous support through Tier 1 grant (FRC WBS R-143–000-A12-114 and WBS R-143–000-B13-114).

References

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Volume 7| Part 1| January 2020| Pages 83-89

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