Framework disorder and its effect on selective hysteretic sorption of a T-shaped azole-based metal–organic framework

Metal–organic frameworks with highly ordered porosity have been studied extensively. In this paper, the effect of framework (pore) disorder on the gas sorption of azole-based isoreticular Cu(II) MOFs with rtl topology and characteristic 1D tubular pore channels is investigated for the first time. In contrast to other isoreticular rtl metal–organic frameworks, the Cu(II) metal–organic framework based on 5-(1H-imidazol-1-yl)isophthalate acid has a crystallographically identifiable disordered framework without open N-donor sites. The framework provides a unique example for investigating the effect of pore disorder on gas sorption that can be systematically evaluated. It exhibits remarkable temperature-dependent hysteretic CO₂ sorption up to room temperature, and shows selectivity of CO₂ over H₂, CH₄ and N₂ at ambient temperature. The unique property of the framework is its disordered structure featuring distorted 1D tubular channels and DMF-guest-remediated defects. The results imply that structural disorder (defects) may play an important role in the modification of the performance of the material.

1. Introduction

Porous materials such as zeolites, molecular cages, activated carbons, covalent organic frameworks and metal–organic frameworks (MOFs) have been utilized as adsorbents for gas capture (e.g. CO₂). Among these materials, MOFs with high surface area, tunable pore size and modifiable pore surfaces are receiving great interest because they show unique flexibility and dynamic behaviors (e.g. phase change) and also offer significant improvements in separation performance (Horike et al., 2009; Schneemann et al., 2014; Alhamami et al., 2014; Zhang et al., 2017). For example, their corresponding hysteretic gas adsorption/desorption behaviors are able to decrease the pressure of gas storage.

According to the isoreticular MOF concept introduced by Yaghi and others (Eddaoudi et al., 2002; Wilmer et al., 2012; Deng et al., 2012; Ma et al., 2010), a MOF structure is determined by the connectivity of the rigid bridging ligand, the secondary building unit (SBU) and the framework topology. By fixing a specific topology, the isostructural frameworks can be readily fine-tuned via organic ligand manipulation and metal ion selection (Yuan et al., 2010; Caskey et al., 2008). Analogous ligands with different functionalities can be especially employed to produce desired frameworks (Colombo et al., 2012; Sumida et al., 2013). Along these lines, the effect of some subtle factors on the pore properties can be investigated and analyzed by designing isoreticular MOFs (McDonald et al., 2012; Li, Zhang et al., 2012; Das et al., 2012; Zhang et al., 2012; Bae et al., 2012). However, much of the research emphasis remains on developing and characterizing highly ordered framework materials with regularly repeating crystal structures where all the pores have exactly the same size, shape and functionality. This ignores disorder and/or defects which are often concomitant with the growth of a long-range periodic framework. The introduction of defects may alter the regular porous interior and behavior of MOFs. Defects may play a crucial role in enhanced accessibility of the porous network and higher basicity of the metal centers. Defects in regular MOFs have been shown to impart unusual and useful physical properties to these framework materials (Cairns & Goodwin, 2013; Tucker et al., 2005; Goodwin et al., 2009; Cheetham et al., 2016; Fang et al., 2015; Tahier & Oliver, 2017; Cliffe et al., 2014; Li et al., 2013). Fundamental correlations between defects and properties of the resulting defective materials have been shown in some examples. Partial interpenetration of MOF NOTT-202a was observed by Schröder and co-workers to provide defect sites for gas recognition and storage, and to show selective hysteretic sorption of gas molecules (Yang et al., 2012, 2013). The mixed linker approach was reported by Zhou and co-workers to introduce functionalized disordered mesopores into MOFs (Park et al., 2012; Yuan et al., 2016). Missing-linker defects were shown to be extensively present [e.g. in the UiO-66 series (Trickett et al., 2015)], increasing the gas adsorption capacities (Rodríguez-Albelo et al., 2017) and enhancing the proton mobility (Taylor, Dekura et al., 2015; Taylor, Komatsu et al., 2015). Herein, we report a unique example to demonstrate how structural disorder can lead to unusual changes in the properties of MOFs (e.g. the sorption property) based on a series of isoreticular azole-based MOFs with rtl (rutile) topology (denoted rtl-MOFs).

Isoreticular rtl-MOFs are based on the square paddle-wheel SBU, one of the most common SBUs formed by metals and carboxyl­ates (Tranchemontagne et al., 2009). Such square SBUs have long been used to build various porous structures, for example, pillared layer structures with mixed ligands of N-containing heterocycles (e.g. pyridine, imidazole, pyrazole, tetrazole, 1,2,4-triazole) and carboxyl­ate compounds (Seki & Mori, 2002; Dybtsev et al., 2004; Pichon et al., 2007; Chen, Fronczek, Courtney et al., 2006; Chen, Ma, Zapata et al., 2006, 2007). We and others have implemented a new pillaring strategy (Suh et al., 2012) by amalgamation of one heterocycle and two carboxylate groups into a T-shaped heterofunctional ligand, resulting in the pillaring of 2D-edge transitive nets by 3-connected nodes (Xiang et al., 2011; Eubank et al., 2011; Wen et al., 2012; Zhang et al., 2010; Chen et al., 2011, 2015; Jia et al., 2011; Du et al., 2013; Kobalz et al., 2016; Cheng et al., 2017; Wei et al., 2014). Therefore, based on the square-grid sql layer (Zou et al., 2007; Zhong et al., 2011; Xue et al., 2007; Bourne et al., 2001; Gao et al., 2003) formed from the isophthalate unit, a series of isoreticular MOFs have been developed (Xiang et al., 2011; Eubank et al., 2011; Wen et al., 2012; Zhang et al., 2010; Chen et al., 2011, 2015; Jia et al., 2011; Du et al., 2013; Kobalz et al., 2016; Cheng et al., 2017). These microporous MOFs feature in (3,6)-connected 3D frameworks displaying rtl topology and point (Schläfli) symbol (4·6²)₂(4²·6¹⁰·8³). The T-shaped ligand serves as a 3-connected node while the paddle-wheel cluster acts as a 6-connected node. A variety of heterocycles [pyridine (Xiang et al., 2011; Eubank et al., 2011; Chen et al., 2015), pyrimidine (Du et al., 2013), 1,2,4-triazole (Eubank et al., 2011; Wen et al., 2012; Kobalz et al., 2016) and tetrazole (Zhang et al., 2010)] have been incorporated into the T-shaped ligands and various metal ions [Cu (Xiang et al., 2011; Eubank et al., 2011; Wen et al., 2012; Zhang et al., 2010; Du et al., 2013; Kobalz et al., 2016; Chen et al., 2011), Zn (Chen et al., 2011) and Co (Jia et al., 2011)] have been utilized to form square paddle-wheel SBUs. One unique characteristic of the rtl topology is that such frameworks are forbidden from interpenetration, so that 1D tubular channels can be formed and isolated by the walls of the parallel pillars containing the aromatic rings. On one hand, the pore aperture is largely defined by the sql grid size or the distance between two carboxylate groups of the isophthalate unit. Thus, the pore sizes are similar for these isoreticular MOFs. On the other hand, the pore surface can be modified by changing or functionalizing the heterocyclic rings [e.g. with uncoordinated N atoms (Eubank et al., 2011) or alkyl groups (Kobalz et al., 2016; Cheng et al., 2017)], which significantly enhance the gas selectivity. In this paper, we add a unique member with framework (pore) disorder into an isoreticular rtl-MOF by incorporating an imidazole ring into the T-shaped ligand (Fig. 1). The remarkable effect of framework (pore) disorder on the sorption property, which induces a significant hysteretic sorption for CO₂ at room temperature, is investigated.

Figure 1 T-shaped bridging ligands containing one azole five-membered-ring heterocycle (imidazole, 1,2,4-triazole and tetrazole) and two carboxylate groups, along with the X-ray crystal structure comparisons of the azole-based rtl-MOFs (Timi-Cu, Ttriaz-Cu and Ttetraz-Cu) showing variation of N sites along the Cu8L4 squares on the inner pore surface.

2. Results and discussion

2.1. Syntheses and crystal structures

The T-shaped ligand 5-(1H-imidazol-1-yl)isophthalate acid (denoted as T_imi) used to introduce hetereocyclic imidazole was synthesized by acid-catalyzed ester hydrolysis of dimethyl 5-(1H-imidazol-1-yl)isophthalate, which was obtained via cyclization of formaldehyde with the diazabutadiene intermediate formed from a reaction of molar equivalents of di­methyl 5-amino­isophthalate, ammonium chloride and glyoxal. A mild solvothermal reaction of T_imi with CuCl₂·2H₂O at 353 K in a mixture of DMF/EtOH (v:v 3:1) led to the new rtl-MOF member, herein denoted as T_imi-Cu.

The structure of T_imi-Cu was determined and checked by single-crystal X-ray diffraction at 150, 195 and 273 K with several randomly selected crystals, all displaying disordered character. In general, T_imi-Cu crystallizes in the monoclinic space group P2₁/c, which is isostructural to the previously reported T_triaz-Cu (Eubank et al., 2011) and T_tetraz-Cu (Zhang et al., 2010) (Fig. 1, Table S1 of the supporting information). In contrast, the reaction of T_imi with CuCl₂·2H₂O at 353 K in acidified DMF yields a different topological structure (Zhu et al., 2015). The reaction of T_imi with CuBr₂ at 353 K in acidified DMF–H₂O yields the same topological structure, but no framework disorder is located (this structure is not stable during a sorption study) (Cheng et al., 2017). Therefore, regardless of the disorder in T_imi-Cu, these azole-based rtl-MOFs have the same overall unit cell, building block geometry and lattice porosity. As shown in Fig. 2, the basic structural units are the dicopper paddle-wheel SBUs bonded together by four T-shaped ligands via carboxylate groups. The axial sites are occupied by the N donors of imdazole. Each Cu₂ SBU joins six ligands and each ligand bridges three different Cu₂ SUBs, thus generating the (3,6)-connected 3D framework of rtl topology. The tubular channels run along the a axis and have an opening of 11.9 × 14.5 Å (b × c, b ⊥ c) along the diagonals of the quadrangle cross section. The solvated DMF and H₂O molecules are disordered and reside in the channels. Based on calculations using the program PLATON, the total potential solvent-accessible void volume is about 885.1 ų per unit cell with a pore volume ratio of 50.3%.

Figure 2 X-ray crystal structures of Timi-Cu: (a) Cu2 paddle-wheel SBU, (b) Cu8L4 square in sql layer formed via the isophthalate moiety in a 1,2-alternate fashion (up–up down–down), (c) side view of the 1D channel formed via pillared Cu8L4 square-grid sql layers, (d) solvent-accessible voids in the tubular channels perpendicular to the bc plane. Framework disorder, solvated molecules and hydrogen atoms have been omitted for clarity.

The detailed structural analysis of T_imi-Cu reveals that the coordination framework is actually disordered in a specific fashion (Figs. 3 and S1). In a statistical sense, each Cu₂ paddle-wheel SBU is distributed over two fractional positions in an approximate 3:1 ratio, and some local areas can be imagined to superimpose two partial rtl-MOFs in an offset way. In reality, each Cu₂ SBU has a definite orientation in the individual asymmetric unit, and is closely related to the neighboring SBUs owing to the rigidity of the isophthalate moiety and consequently fixed Cu₈L₄ square-grid conformation. This is due to the fact that, in the rtl topology, sql sheets are formed via the isophthalate moiety in a predetermined 1,2-alternating fashion (up–up down–down). Thus, local primary 2D Cu₈L₄ square-grid layers are inherently inert to dynamic disorder. In the contrast, local interlayer gliding is relatively easy (Fig. 4) because: (i) the crystal structure is stacked with the parallel 2D sql square grids via pillars of the T-shaped T_imi ligands, (ii) the Cu—N binding between imidazole N donors and axial positions of Cu₂ SBUs is relatively labile, and (iii) the imidazole ring is freely rotatable along the N—C bond to the isophthalate moiety so as to adapt to the layer motions. Therefore, the disorder in T_imi-Cu may be considered to originate from local random interpolated movement of the 2D Cu₈L₄ square-grid layers. This might also account for the observation of two isomerized T_triaz-Cu structures (Eubank et al., 2011; Wen et al., 2012) which differ only in the arrangement of the 2D Cu₈L₄ square-grid layers in one direction. The crystal packing in the other two directions and the framework porosity are similar. However, as for T_teraz-Cu, noticeable disorder was not detected in T_triaz-Cu, meaning that the chemical nature of heterocycles in this azole-based isoreticular rtl-MOF has a subtle influence on crystallization habit and framework isomerization (Makal et al., 2011; Lü et al., 2006). In the reaction of T_imi with CuBr₂ at 353 K in acidified DMF–H₂O, the product has no noticeable disorder as well, showing that guest solvent molecules or ions may have a subtle effect on the disorder.

Figure 3 Comparison of the ideally ordered framework and one possible local disordered framework of Timi-Cu in the a (upper) and b (lower) directions: (a) ordered overlapping of the Cu8L4 square-grid sql layers, (b) one possible disordered offsetting model of the Cu8L4 square-grid sql layers, (c) top view of 1D straight channel in the ordered framework formed via overlapping of Cu8L4 square grids and (d) top view of the 1D distorted channel in the disordered framework formed via offsetting of the Cu8L4 square grid.

Figure 4 Disordered framework versus ordered framework for Timi-Cu.

To further probe the structure of T_imi-Cu, X-ray photoelectron spectroscopy (XPS, Fig. S2) and X-ray absorption fine-structure (XAFS, Fig. S3 and Table S2) measurements were investigated. XPS confirms the presence of copper(II) in T_imi-Cu. Cu 2p core-level photoelectron spectra for imi-Cu displayed doublets i.e. Cu 2p_3/2 and Cu 2p_1/2 at 935.8 and 955.0 eV, respectively. The Cu 2p_3/2 and Cu 2p_1/2 main doublets were separated by 20 eV and their satellite peaks present at binding energies of 943.0 and 964.0 eV are characteristic of the unfilled orbitals. The study of the Cu LMM signal also supports the presence of Cu(II), and the Cu LMM signal with a kinetic energy of 916.0 eV is assigned to Cu(II). Although being the most common technique for structure determination/identification and measurement of long-range order, powder X-ray diffraction (PXRD) generally provides little information on defects. XAFS was expected to provide some local order information. XAFS data show that Cu(II) is present and the average Cu—O/N bonds are calculated to be 1.97 ± 0.01 Å. However, the data of T_imi-Cu are comparable with the data of Cu-T_triaz and Cu-T_tetraz, which have no disorder. It can be concluded that T_imi-Cu and the other two MOF materials have similar short-range coordination spheres.

The above results show that a unique structural feature of T_imi-Cu is that the disorder does not cause absence of crystallinity. In other words, the disorder occurs in a crystallographically `regular' way to a certain extent. Various comparisons of the disordered structures of T_imi-Cu with those of notionally ordered counterparts are depicted in Figs. 3, 4 and S1. It is speculated that partial Cu₈L₄ square-grid layers shift exactly half a unit cell along the c direction, leading to offset stacking of these 2D sql sheets along the a direction. In this way, all Cu₂ SBUs need not change conformation except for a 180° rotation of the imdazole rings to adapt to the new axial coordination (Fig. 4). Since orientation of the Cu₂ SBUs in every layer is fixed, gliding of the 2D sheet along any other direction will cause a severe geometry and connectivity mismatch. This is evident from observations of the nearly identical packing modes of the ordered and disordered frameworks in both the b and c directions (Fig. S1). Such a disorder phenomenon is distinct from the topological disorder in well known amorphous silica glass (α-SiO₂) with a continuous random network (Cairns & Goodwin, 2013; Tucker et al., 2005). It is also distinct from the 2D layered square grids Ni(CN)₂, which lack long-range order in the perpendicular direction (Cairns & Goodwin, 2013; Goodwin et al., 2009), although in a short-range or local environment they might be comparable. It is worth noting that some framework defects like coordination mismatch or connectivity distortion should also be present.

Therefore, the disordered T_imi-Cu is a new member of the azole-based isoreticular rtl-MOFs containing different five-membered-ring heterocycles (imidazole, 1,2,4-triazole and tetrazole). A study of T_imi-Cu may offer the following advantages: (i) T_imi-Cu has a comparable pore volume regardless of chemical or structural variation. For the azole-based rtl-MOFs, the heterocycles protrude into the channels and slightly reduce the pore sizes in comparison with the pyridyl rtl-MOF (Xiang et al., 2011). However, the similar Cu₈L₄ square grids and pillaring nature of three five-membered azole rings principally decide the total comparable pore volume. (ii) The inner pore surfaces are modified by different heterocyclic azole rings. Two C—H moieties point into the channel in T_imi-Cu, one C—H and one N donor in T_triaz-Cu, while there are two N donors in T_tetraz-Cu (Fig. 1). (iii) Framework disorder in T_imi-Cu produces different pore permeability from that in T_triaz-Cu and T_tetraz-Cu. As seen from Figs. 3, 4 and S1, partial gliding of sql sheets does not cause significant pore changes along the b and c axes but does along the a axis. The main pore channels along the a axis in T_imi-Cu become distorted in contrast to the straight channels with long-range order in T_triaz-Cu and T_tetraz-Cu. (iv) The propensity for disorder and framework defects in T_imi-Cu probably results in sorption dynamics compared with the more static frameworks in T_triaz-Cu and T_tetraz-Cu.

2.2. Thermal stability

As-synthesized bulk samples of T_imi-Cu display sharp PXRD patterns that closely resemble those simulated from the single-crystal data (Fig. S4), indicative of phase purity and air stability. Thermogravimetric analysis (TGA) of T_imi-Cu reveals similar thermal stability to that reported for T_tetraz-Cu (Wen et al., 2012; Zhang et al., 2010). The TGA plot of as-synthesized T_imi-Cu shows a weight loss of 26.2% from room temperature to ca. 513 K, corresponding to the release of solvent molecules (1.5 DMF and 0.5 H₂O per formula unit; calculated weight loss 28.8%) residing in the pore channels (Fig. S5). Rapid decomposition occurs upon further heating above 543 K. The thermostability of the desolvated material is further revealed by PXRD experiments at various temperatures (Fig. S6). PXRD results reveal that the framework structure is unchanged up to 373 K and transforms into a new structure with a different framework topology between 383 and 443 K (the new structure will be reported in due course). This further indicates that the Cu²⁺-T_imi system is rather sensitive to synthetic parameters including solvent, counteranions and temperature.

2.3. Permanent porosity

To evaluate the permanent porosity, nitrogen physisorption measurements were performed at 77 K. Prior to analysis, pore activation was performed by evacuating T_imi-Cu by thermal activation under vacuum at 358 K following surface cleaning by EtOH. This gives rise to a partially desolvated sample, in which the DMF molecules occluded within the channels were not removed completely (Seo et al., 2010; Hijikata et al., 2013; Wang et al., 2013, 2015). FT–IR spectra confirm the presence of residual DMF (Fig. S7). An N₂ adsorption isotherm of T_imi-Cu reveals a steep uptake in the low-pressure region and the profile displays a type-I curve that is typical of microporous materials (Fig. 5). The Langmuir and BET surface areas are calculated to be 1145 and 771 m² g⁻¹, respectively, and the total pore volume is 0.31 cm³ g⁻¹ (Table S3, Figs. S8–S10). Surprisingly T_imi-Cu shows a double-peak pore size distribution centered around 5.1 and 6.8 Å according to the Horvath–Kawazoe method. The main pore size at 5.1 Å is consistent with other rtl-MOFs (Zhang et al., 2010), while 6.8 Å is unprecedented (see the discussion below). For comparison, T_triaz-Cu has Langmuir and BET surface areas of 893 and 768 m² g⁻¹, while those of T_tetraz-Cu are 1055 and 766 m² g⁻¹, consistent with the reported data (Zhang et al., 2010). The total pore volumes are 0.29 and 0.30 cm³ g⁻¹, respectively, and the pore sizes are comparable at around 4.9 Å.

Figure 5 (a) N2 adsorption–desorption isotherms for Timi-Cu measured at 77 K and (b) Horvath–Kawazoe micropore size distribution.

The pore enlargement of T_imi-Cu is unexpected and can reasonably be related to the framework disorder. On one hand, the disorder in T_imi-Cu causes the pore channels to become distorted; on the other hand, appearance of structural disorder in the crystal structure always implies concomitance of local defects due to coordination mismatch or topological distortion caused by interlayer gliding. Hence, enlargement of partial pores in T_imi-Cu is understandable. The defects (probably containing uncoordinated metal centers) may be readily occupied by solvated DMF molecules. Moreover, the N₂ sorption isotherms show an obvious H2-type hysteresis loop which is usually considered to be a characteristic of mesoporosity (Li et al., 2013; Fang et al., 2010; Zhao et al., 2011; Qiu et al., 2008), but we believe that this may also be attributed to the structural disorder. The clustering of numerous local defects may result in larger-scale mesoporosity, so the existence of some mesopores in the disordered framework is to be expected.

2.4. CO₂ capture and framework dynamics

Low-pressure and high-pressure CO₂ sorption has been studied. As depicted in Fig. 6, T_imi-Cu adsorbs significant amounts of CO₂ at various temperatures (195, 263, 273, 283 and 298 K). At 195 K, the isotherms are type I, which is typical for microporous materials. T_imi-Cu displays an uptake capacity of 7.3 mmol g⁻¹ (32.0 wt%) for CO₂ at 1 bar. A striking feature is that T_imi-Cu also shows high CO₂ uptake at 273 K. T_imi-Cu has CO₂ storage capacity of 4.2 mmol g⁻¹ (18.7 wt%) at 273 K, 1 bar. The adsorption isotherm of CO₂ up to 30 bar at 298 K indicates that T_imi-Cu shows a CO₂ uptake capacity of 3.2 mmol g⁻¹ (14.1 wt%) at 30 bar. The high CO₂ uptake capacity of T_imi-Cu, which has no open metal/N-donor sites on the inner pore surface revealed by the X-ray structure, hints at other contributions, namely framework disorder (see the discussion below).

Figure 6 CO2 adsorption–desorption isotherms for Timi-Cu measured at (a) 195 K (insert shows an enlargement of the low-pressure section); (b) 263, 273, 283 and 298 K; and (c) CO2, N2, H2 and CH4 adsorption–desorption isotherms for Timi-Cu measured at 273 K, and CO2, N2 and CH4 adsorption–desorption isotherms for (d) Timi-Cu, (e) Ttriaz-Cu and (f) Ttetraz-Cu measured under various pressures at 298 K.

Another noteworthy feature is that T_imi-Cu shows remarkable hysteretic sorption behavior toward CO₂, while the isostructural T_triaz-Cu and T_tetraz-Cu do not show obvious hysteresis loops (Fig. 6). The stepwise sorption usually indicates filling of different types of pore sites, originating from the gate effect or dynamic nature (Kitaura et al., 2002; Thallapally et al., 2008; Chen, Ma, Hurtado et al., 2007; Nouar et al., 2012; Suzuki et al., 2016; Carrington et al., 2017; Taylor et al., 2016; Choi & Suh, 2009; Llewellyn et al., 2006) and framework defects (Yang et al., 2012). Careful examination reveals that T_imi-Cu exhibits stepwise adsorption under low pressure at 195 K (Fig. 6a). Surprisingly, such adsorption/desorption hysteresis becomes more prominent at elevated temperatures up to 273 K (Fig. 6b). Note that a higher pressure is needed to initiate the hysteresis as temperature increases. The inducing pressure of P/P₀ = 0.01 at 195 K increases to 0.37 at 263 K and 0.54 at 273 K.

The adsorption isotherms of CO₂ up to 30 bar at 298 K further reveal the temperature-gating pressure relationship (Fig. 6). T_imi-Cu exhibits a distinct stepwise adsorption isotherm, while the desorption branch does not trace the adsorption branch, forming a remarkable hysteresis loop. At low pressure, only a small amount of CO₂ (0.5 mmol g⁻¹) is adsorbed. A sudden rise in the isotherm occurs at an inducing pressure of 125 kPa, which is higher than that at 273 K. This confirms the low-pressure observations that a higher pressure is needed to initiate the hysteresis as temperature increases.

Considering the above temperature-dependent variations of CO₂ sorption capacity and hysteresis, and comparing the structural nature of these isoreticular rtl-MOFs, we believe that the framework disorder in T_imi-Cu imparts an essential effect on the CO₂ sorption behavior. As discussed above, the structural disorder causes the pore channels to become too distorted for gas molecules to permeate through, and renders some local defects which might be partly maintained by the solvated DMF molecules. If gas molecules have a tendency to interact with the pore surface (protruding heterocycles) and defect sites (such as uncoordinated metal centers), gas uptake may induce framework dynamics. For T_imi, the blocking/shielding DMF molecules can facilitate and affect the structural transformation, thus making hysteresis pronounced. At low temperature, i.e. 195 K, the coordination framework and shielding DMF molecules are relatively static, and the hysteretic steps are therefore relatively inexplicit. As the temperature increases, the kinetically hindered pores in the disordered framework become easier to break through, thus displaying a larger hysteresis loop. However, once the temperature rises above 283 K, hysteresis turns indistinctive again (Fig. 6b), implying facile and expeditious structural conversions above this temperature. Additionally, the inducing pressure of hysteresis increases with rise in temperature, which may be due to higher thermal vibration of the framework, hindering DMF and adsorbed CO₂ molecules at elevated temperature and resulting in weaker adsorbent/adsorbate interactions, thus requiring a larger pressure to push the motion of the framework. This may also account for the observation that the CO₂ uptake capacity of T_imi-Cu decreases as temperature increases relative to that of T_triaz-Cu and T_tetraz-Cu. The CH₄ isotherm also exhibits a broad hysteresis loop with an inflection point at 298 K and a higher pressure of ca. 940 kPa, which may relate to its larger polarizability (25.93 × 10⁻²⁵ cm³) (Li et al., 2009; Sircar, 2006). This offers a new strategy for hysteretic sorption of CH₄ (Taylor et al., 2016; Mason et al., 2014).

According to the above discussion, the present CO₂ uptake process may represent a distinct strategy to drive adsorption/desorption hysteresis that is inherently related to framework (pore) disorder. In contrast to the gate effect and interpenetrating dynamics (Kitaura et al., 2002; Thallapally et al., 2008; Chen, Ma, Hurtado et al., 2007; Nouar et al., 2012; Suzuki et al., 2016; Carrington et al., 2017; Taylor et al., 2016; Choi & Suh, 2009; Llewellyn et al., 2006), the present CO₂ (and CH₄) hysteresis is temperature dependent, originating from the propensity of structural disorder which can be affected by guest intrusion. The structure dynamics can be induced selectively by CO₂ (and CH₄ at higher pressure) but not by N₂ or H₂.

In order to have further insight into the structure dynamics, PXRD investigation was performed. PXRD patterns of T_imi-Cu remain unchanged under a high-pressure CO₂ atmosphere up to 3.0 MPa even if accompanied by pulverizing of the crystal sample (Fig. S11). Moreover, the XRD patterns of T_imi-Cu show no change after tablet compression with a tablet press from 0 to 20 MPa (Fig. S12). The results reveal that the long-range order of T_imi-Cu is generally maintained under high pressure. The XRD signals become weak above 30 MPa, showing partial loss of long-range order under high pressure. Therefore, either no phase transformation occurs or the structural change is tiny under high pressure.

Two possible factors may contribute to the CO₂ hysteresis. (i) Penetration of CO₂ and CH₄ through the disordered pore channels offers a greater driving force than through the straight 1D channels, and interactions of CO₂ with the protruding imidazole rings facilitate their rotation along N—C bonds. Simulation of the CO₂ adsorption isotherms at 263 K shows that a slight rotation of the imidazole ring of 5.448° has a dramatic effect on the adsorption results (Fig. S13). (ii) DMF guest molecules in the framework perhaps block the pore entrance, which becomes dynamic when the temperature and/or pressure increases. Such framework dynamics may result in partial loss of long-range order, as shown by the broadened PXRD pattern after sorption. Therefore, the framework dynamics are responsive to CO₂ uptake depending on feasible conditions created by proper temperature. This is analogous with the partially interpenetrated NOTT-202a which shows temperature-dependent adsorption/desorption hysteresis only below the triple point of CO₂ (216.7 K), corresponding completely to the framework defects. In our case, the framework dynamics may be more related to the topological disorder, because the disordered structure model established by single-crystal analysis prefers topological distortion to defect formation. Nevertheless, interaction of CO₂ with the defect sites should also contribute to the dynamics of the disordered framework.

The CO₂ adsorption capacity around room temperature is essential for potential industrial usage, such as CO₂ capture and separation in upgrading of natural gas (natural gas clean-up, CO₂/CH₄), post-combustion (flue gas, CO₂/N₂) and pre-combustion (shifted synthesis gas stream, CO₂/H₂) (Sumida et al., 2012; Li, Sculley & Zhou, 2012; Nugent et al., 2013; Bloch et al., 2013). To investigate the sorption selectivity of T_imi-Cu, CO₂, N₂, H₂ and CH₄ low-pressure adsorption isotherms were measured at 273 K, and CO₂, N₂ and CH₄ high-pressure adsorption isotherms at 298 K, and compared in Figs. 6(e) and 6(f). For T_imi-Cu, considerably larger amounts of CO₂ are adsorbed than N₂, H₂ and CH₄, suggesting that the gas uptake capacity drops remarkably for N₂, H₂ and CH₄ but remains significant for CO₂ at elevated temperatures (see Figs. S8–S10 for low-temperature data).

The above results verify that T_imi-Cu has a high and general gas sorption selectivity for CO₂ over H₂/CH₄/N₂; the question is then how such sorption behavior happens. Various effects have been reported in the literature that enforce strong interactions between the host framework and CO₂ under ambient conditions, e.g. immobilization of open metal sites or polarized functional groups (Yuan et al., 2010; Sumida et al., 2012; Cui et al., 2012; Gu et al., 2010; Demessence et al., 2009; McDonald et al., 2011; Banerjee et al., 2009). In particular, aromatic ligands containing uncoordinated N donors (e.g. tetrazole-based ligands) were found to improve the selective adsorption behavior for CO₂ (Zhang et al., 2010; Cui et al., 2012; Lin et al., 2010, 2012; Qin et al., 2012). In the present azole-based rtl-MOF, no purposely introduced open metal sites exist on the pore surface and T_imi-Cu has no polarized functional groups (open N-donor sites). So, the good selectivity of T_imi-Cu probably relies on the above-described structural disorder, as well as the tubular pore channels characteristic of rtl-MOFs containing pillaring T-shaped ligands.

First of all, the tubular channels of narrow size in the present rtl-MOF have proved important (Du et al., 2013; An & Rosi, 2010). It is argued that, for MOFs with bigger pore sizes (>6 Å), substitution of C—H moieties with N donors does not significantly affect the adsorption capacity for H₂ and CO₂ (Park et al., 2011). The pore sizes of T_imi-Cu justify this assumption well. Second, the quadruple moment of CO₂ renders a stronger interaction with the host framework, which contributes excess energy for CO₂ to enter the pore channels. Since CO₂ is well known to have stronger adsorbent/adsorbate interactions due to strong polarizability (29.11 × 10⁻²⁵ cm³) and quadruple moment (4.30 × 10⁻²⁶ esu cm²) (Li et al., 2009; Sircar, 2006), selective hysteretic sorption of CO₂ over N₂, H₂ and CH₄ is understandable at low pressure. Third, the structural disorder may cause defects in the coordination framework, thus creating open metal sites. Such defects may exist in a small portion of the framework (see above). On the other hand, the framework disorder enables distorted pore channels as well as straight channels. The distorted channels with narrow size are appropriate for holding gas molecules kinetically within the channels, which increases the van der Waals interactions between the host framework and gas molecules (Wen et al., 2012). Most importantly, as temperature rises, CO₂ uptake towards such disordered pores amplifies the framework dynamics, resulting in selective sorption hysteresis. Such adsorption/desorption hysteretic behavior at room temperature is rare (Hijikata et al., 2013; Wang et al., 2013, 2015); it greatly improves the adsorption selectivity for CO₂ at ambient temperature, similar to observations of selective CO₂ capture by flexible or dynamic MOFs under different conditions (Choi & Suh, 2009; Llewellyn et al., 2006; Mohamed et al., 2012; Burd et al., 2012; Eguchi et al., 2012). In addition, the present framework disorder induces hysteretic sorption in a much broader range from 195 K to room temperature. This allows the capture of CO₂ at high pressure, but leaves CO₂ trapped in the pores at low pressure, thus facilitating the separation of CO₂ from H₂/CH₄/N₂ under more industrially applicable conditions.

3. Conclusions

A unique rtl-MOF (T_imi-Cu) with framework disorder was prepared by incorporating an imidazole ring into a T-shaped ligand and the gas sorption properties were evaluated. In contrast to other azole-based rtl-MOFs with five-membered-ring heterocycles (triazole, T_triaz-Cu; tetrazole, T_tetraz-Cu), T_imi-Cu does not integrate open N-donor sites while containing only two C—H moieties in its characteristic tubular pores. Remarkably, T_imi-Cu displays crystallographically identifiable disorder of the framework. Considering the interesting effects induced by structural disorder on framework materials (Cairns & Goodwin, 2013; Tucker et al., 2005; Goodwin et al., 2009; Cheetham et al., 2016; Fang et al., 2015; Tahier & Oliver, 2017; Cliffe et al., 2014; Li et al., 2013; Allan et al., 2012; Amirjalayer & Schmid, 2008), T_imi-Cu provides a unique example to investigate the effect of framework pore disorder on sorption properties. As a defective derivative, T_imi-Cu retains the long-range order and topology of the parent framework of rtl-MOFs, while it exhibits pore disorder and a relatively large percentage of defects in an otherwise highly crystalline material. Single-crystal analyses establish the disordered structural model in relation to porosity, featuring distorted 1D tubular channels and DMF-guest-remediated defects. These factors endow T_imi-Cu with good gas sorption capacity. Importantly, temperature-dependent hysteretic CO₂ (and CH₄) sorption is shown up to 298 K, which dramatically enhances selective adsorption of CO₂ (and CH₄) at elevated temperatures. Therefore, the present azole-based rtl-MOF shows strong binding with CO₂ and high selectivity for CO₂ over H₂/CH₄/N₂ at ambient temperature. Furthermore, the results imply the significance of structure disorder (defects) on the modification of the performance of framework materials, providing a viewpoint for expanding the properties of framework materials.

4. Experimental

4.1. Materials and methods

All starting materials and solvents were obtained from commercial sources and used without further purification unless otherwise indicated. Di­methyl-5-(1H-imidazol-1-yl)isophthalate was prepared according to the published procedure (Wang et al., 2013). PXRD data were recorded on a Bruker D8 Advance diffractometer at 40 kV and 40 mA with a Cu-target tube and a graphite monochromator. Infrared spectra were measured on a Nicolet/Nexus-670 FT–IR spectrometer with KBr pellets. Thermogravimetric analysis was performed under N₂ at a heating rate of 10 K min⁻¹ on a Netzsch Termo Microbalance TG 209 F3 Tarsus. The sorption isotherms were measured with a Quantachrome Autosorb-iQ or Autosorb-iQ2 analyzer.

4.2. Synthesis of 5-(1H-imidazol-1-yl)benzene-1,3-di­carboxylic acid (T_imi)

Ester hydrolysis of dimethyl-5-(1H-imidazol-1-yl)isophthalate was performed via an acid-catalyzed ester hydrolysis in HCl solution. Di­methyl-5-(1H-imidazol-1-yl)isophthalate (160 mg, 0.6 mmol) was refluxed for 36 h in 20% HCl (8 ml). The solvent was evaporated to obtain the product (140 mg, >99%). The product was soluble in DMF and MeOH. ¹H NMR (300 MHz, DMSO-d₆): δ 9.76 (s, 1H), 8.54 (s, 1H), 8.50 (s, 2H), 8.41 (s, 1H), 7.87 (s, 1H). IR (cm⁻¹, KBr): 3163 (w), 3087 (w), 1711 (m), 1674 (m), 1600 (w), 1539 (w), 1399 (m), 1348 (m), 1232 (s), 1068 (s), 876 (w), 757 (m), 672 (m), 616 (w).

4.3. Synthesis of T_imi-Cu

A solution of T_imi (6.0 mg, 0.025 mmol) in DMF (3 ml) and a solution of CuCl₂·2H₂O (8.5 mg, 0.05 mmol) in EtOH (1 ml) were mixed. The resultant clear solution was heated in a closed vial at 353 K for 3 days. Green crystals were collected using filtration (7 mg, 70%). Microanalysis found (calculated) for C₁₁H₆O₄N₂Cu·1.5DMF·0.5H₂O: C, 45.22 (45.15); H 4.28 (4.28); N 11.74 (11.89)%. FT–IR (cm⁻¹, KBr): 3426 (b), 3101 (w), 2929 (w), 1634 (m), 1594 (m), 1503 (w), 1385 (s), 1249 (w), 1070 (m), 922 (w), 782 (w), 730 (m), 656 (w). For thermally activated product under vacuum at 358 K following CH₂Cl₂ solvent exchange, microanalysis found (calculated) for C₁₁H₆O₄N₂Cu·3H₂O: C 37.34 (37.99), H 3.55 (3.48), N 7.82 (8.06)%.

4.4. X-ray structure determination

X-ray reflection data were collected at 150 (2) K on an Oxford Gemini S Ultra diffractometer equipped with a graphite-monochromated Enhance (Cu) X-ray source (λ = 1.54178 Å). An empirical absorption correction was applied to the intensity data using spherical harmonics implemented in the SCALE3 ABSPACK scaling algorithm (Agilent, 2012). The structure was solved by direct methods following difference Fourier syntheses and was refined by the full matrix least-squares method against F_o² using SHELXTL software (Sheldrick, 2015). The whole framework is disordered over two positions with an occupancy ratio of 0.694:0.306. The unit-cell volume includes a large region of disordered solvent (1.5 DMF and 0.5 H₂O molecules). One DMF molecule is disordered over two positions with an occupancy ratio of 0.679:0.321. There are 0.25 water and 0.25 DMF molecules located at the inversion center. Modeled refinements were applied to the disordered parts including the imidazole ring, solvated water and DMF molecules to make them geometrically reasonable, resulting in a total of 1074 restraints.

Crystallographic data for T_imi-Cu: C_15.5H₁₇CuN_3.5O_5.75, FW = 407.87, monoclinic, P2₁/c, a = 10.8431 (6) Å, b = 11.8835 (6) Å, c = 14.4823 (9) Å, α = 90°, β = 109.361 (7)°, γ = 90°, V = 1760.57 (17) ų, Z = 4, T = 150 (2) K, λ = 1.54178 Å, ρ_calc = 1.539 mg m⁻³, μ = 2.097 mm⁻¹, 4661 reflections were collected (2553 were unique) for 4.93 < θ < 59.98, R(int) = 0.0325, R₁ = 0.0840, wR₂ = 0.2296 [I > 2σ(I)], R₁ = 0.0984, wR₂ = 0.2447 (all data) for 258 parameters, GOF = 1.073, CCDC reference 945810.

5. Related literature

The following references are cited in the supporting information: Vitillo et al. (2008); Zhou et al. (2008).

Supporting information

Computing details

Data collection: CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31); cell refinement: CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31); data reduction: CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

(I)

Crystal data

C15.50H17CuN3.50O5.75	F(000) = 838
Mr = 407.87	Dx = 1.539 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.5418 Å
a = 10.8431 (6) Å	Cell parameters from 1347 reflections
b = 11.8835 (6) Å	θ = 3.7–61.1°
c = 14.4823 (9) Å	µ = 2.10 mm^−1
β = 109.361 (7)°	T = 150 K
V = 1760.57 (17) Å^3	Block, green
Z = 4	0.35 × 0.30 × 0.27 mm

Data collection

Xcalibur, Sapphire3, Gemini ultra diffractometer	2553 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	1995 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.033
Detector resolution: 16.0855 pixels mm^-1	θmax = 60.0°, θmin = 4.9°
ω scans	h = −11→12
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −13→12
Tmin = 0.527, Tmax = 0.601	l = −16→12
4661 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.084	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.245	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.120P)^2 + 9.7466P] where P = (Fo^2 + 2Fc^2)/3
2553 reflections	(Δ/σ)max < 0.001
258 parameters	Δρmax = 0.92 e Å^−3
1074 restraints	Δρmin = −0.97 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1W	0.5000	0.0000	0.5000	0.32 (3)	0.50
Cu1'	0.5982 (2)	0.42374 (18)	0.52505 (16)	0.0183 (8)	0.306 (2)
C2'	0.761 (2)	0.1942 (18)	0.5404 (11)	0.0219 (8)	0.306 (2)
H2B	0.6865	0.1472	0.5161	0.026*	0.306 (2)
N2'	0.9618 (14)	0.2529 (19)	0.6016 (11)	0.0226 (8)	0.306 (2)
N1'	0.7596 (15)	0.3084 (13)	0.5435 (10)	0.0216 (8)	0.306 (2)
C3'	0.881 (2)	0.160 (2)	0.5758 (11)	0.0224 (8)	0.306 (2)
H3B	0.9083	0.0836	0.5829	0.027*	0.306 (2)
C1'	0.8815 (17)	0.3439 (16)	0.5718 (12)	0.0221 (8)	0.306 (2)
H1B	0.9088	0.4199	0.5716	0.026*	0.306 (2)
C4'	1.1008 (7)	0.2489 (11)	0.6463 (8)	0.0287 (15)	0.306 (2)
C5'	1.1706 (10)	0.3185 (10)	0.6043 (7)	0.0286 (15)	0.306 (2)
H5B	1.1255	0.3655	0.5507	0.034*	0.306 (2)
C6'	1.3064 (10)	0.3192 (10)	0.6407 (8)	0.0286 (14)	0.306 (2)
C7'	1.3724 (7)	0.2504 (11)	0.7192 (8)	0.0287 (14)	0.306 (2)
H7B	1.4653	0.2509	0.7440	0.034*	0.306 (2)
C8'	1.3026 (10)	0.1808 (10)	0.7612 (7)	0.0285 (14)	0.306 (2)
C9'	1.1668 (10)	0.1801 (10)	0.7248 (8)	0.0284 (15)	0.306 (2)
H9B	1.1190	0.1326	0.7535	0.034*	0.306 (2)
C10'	1.3784 (18)	0.3865 (16)	0.5899 (13)	0.0288 (14)	0.306 (2)
C11'	1.3740 (17)	0.1120 (15)	0.8492 (13)	0.0284 (14)	0.306 (2)
O1'	1.3260 (12)	0.4762 (10)	0.5509 (9)	0.0289 (16)	0.306 (2)
O2'	1.4917 (12)	0.3496 (11)	0.5953 (9)	0.0288 (15)	0.306 (2)
O3'	1.4864 (11)	0.1487 (10)	0.9016 (8)	0.0282 (16)	0.306 (2)
O4'	1.3220 (12)	0.0220 (10)	0.8621 (9)	0.0289 (16)	0.306 (2)
Cu1	0.59805 (9)	0.07599 (8)	0.52443 (7)	0.0178 (4)	0.694 (2)
N1	0.7586 (7)	0.1905 (6)	0.5698 (4)	0.0214 (8)	0.694 (2)
N2	0.9621 (7)	0.2485 (8)	0.6221 (5)	0.0228 (7)	0.694 (2)
C1	0.8826 (11)	0.1594 (10)	0.5990 (5)	0.0229 (8)	0.694 (2)
H1A	0.9115	0.0835	0.6029	0.027*	0.694 (2)
C2	0.7581 (8)	0.3050 (7)	0.5804 (5)	0.0227 (8)	0.694 (2)
H2A	0.6827	0.3512	0.5674	0.027*	0.694 (2)
C3	0.8831 (8)	0.3407 (7)	0.6125 (5)	0.0233 (8)	0.694 (2)
H3A	0.9113	0.4165	0.6260	0.028*	0.694 (2)
C4	1.1011 (3)	0.2501 (5)	0.6518 (4)	0.0243 (7)	0.694 (2)
C5	1.1683 (4)	0.1808 (4)	0.6073 (3)	0.0255 (8)	0.694 (2)
H5A	1.1213	0.1337	0.5544	0.031*	0.694 (2)
C6	1.3041 (4)	0.1806 (4)	0.6404 (3)	0.0261 (8)	0.694 (2)
C7	1.3728 (3)	0.2496 (5)	0.7178 (4)	0.0266 (9)	0.694 (2)
H7A	1.4657	0.2495	0.7404	0.032*	0.694 (2)
C8	1.3057 (4)	0.3189 (4)	0.7623 (3)	0.0264 (8)	0.694 (2)
C9	1.1698 (4)	0.3191 (4)	0.7292 (3)	0.0260 (9)	0.694 (2)
H9A	1.1239	0.3664	0.7596	0.031*	0.694 (2)
C10	1.3778 (7)	0.1099 (7)	0.5889 (6)	0.0268 (8)	0.694 (2)
C11	1.3798 (7)	0.3895 (7)	0.8491 (6)	0.0266 (8)	0.694 (2)
O1	1.3241 (5)	0.0229 (4)	0.5496 (4)	0.0274 (9)	0.694 (2)
O2	1.4880 (5)	0.1467 (5)	0.5920 (4)	0.0278 (9)	0.694 (2)
O3	1.4900 (5)	0.3526 (5)	0.9009 (4)	0.0286 (9)	0.694 (2)
O4	1.3256 (5)	0.4768 (4)	0.8626 (4)	0.0279 (9)	0.694 (2)
C17	0.608 (6)	0.562 (6)	0.565 (5)	0.1833 (17)	0.25
H17A	0.6030	0.5555	0.6307	0.275*	0.25
H17B	0.6106	0.6416	0.5479	0.275*	0.25
H17C	0.6883	0.5248	0.5628	0.275*	0.25
O6	0.308 (4)	0.412 (4)	0.478 (4)	0.184 (2)	0.25
N4	0.494 (4)	0.507 (5)	0.498 (3)	0.1833 (12)	0.25
C15	0.407 (5)	0.459 (4)	0.530 (3)	0.1834 (13)	0.25
H15	0.4204	0.4588	0.5984	0.220*	0.25
C16	0.474 (6)	0.510 (7)	0.394 (3)	0.1835 (15)	0.25
H16A	0.3964	0.4666	0.3565	0.275*	0.25
H16B	0.5512	0.4782	0.3821	0.275*	0.25
H16C	0.4631	0.5885	0.3728	0.275*	0.25
N3'	0.1304 (5)	0.7516 (4)	0.1554 (5)	0.0651 (5)	0.321 (6)
C12'	0.1181 (9)	0.8625 (4)	0.1577 (14)	0.0652 (6)	0.321 (6)
H12B	0.1927	0.9113	0.1805	0.078*	0.321 (6)
C14'	0.2583 (7)	0.6964 (9)	0.1927 (17)	0.0653 (7)	0.321 (6)
H14D	0.3111	0.7328	0.2537	0.098*	0.321 (6)
H14E	0.3029	0.7028	0.1441	0.098*	0.321 (6)
H14F	0.2464	0.6168	0.2052	0.098*	0.321 (6)
C13'	0.0164 (8)	0.6774 (8)	0.1205 (18)	0.0649 (7)	0.321 (6)
H13D	−0.0206	0.6657	0.1730	0.097*	0.321 (6)
H13E	0.0430	0.6048	0.1011	0.097*	0.321 (6)
H13F	−0.0495	0.7120	0.0641	0.097*	0.321 (6)
O5'	0.0103 (12)	0.9083 (8)	0.1309 (12)	0.0652 (9)	0.321 (6)
N3	0.1304 (5)	0.7516 (4)	0.1554 (5)	0.0651 (5)	0.679 (6)
C12	0.1178 (5)	0.6404 (4)	0.1503 (8)	0.0650 (6)	0.679 (6)
H12A	0.1950	0.5944	0.1684	0.078*	0.679 (6)
C14	0.2582 (6)	0.8062 (6)	0.1786 (9)	0.0659 (7)	0.679 (6)
H14A	0.3269	0.7487	0.1934	0.099*	0.679 (6)
H14B	0.2728	0.8554	0.2355	0.099*	0.679 (6)
H14C	0.2605	0.8510	0.1224	0.099*	0.679 (6)
C13	0.0163 (6)	0.8260 (5)	0.1296 (9)	0.0651 (7)	0.679 (6)
H13A	−0.0623	0.7832	0.0937	0.098*	0.679 (6)
H13B	0.0284	0.8876	0.0884	0.098*	0.679 (6)
H13C	0.0063	0.8572	0.1894	0.098*	0.679 (6)
O5	0.0102 (6)	0.5946 (5)	0.1267 (6)	0.0640 (9)	0.679 (6)
O6'	0.503 (5)	0.496 (5)	0.338 (3)	0.1835 (18)	0.25
C16'	0.591 (7)	0.582 (6)	0.525 (4)	0.1833 (14)	0.25
H16D	0.6147	0.6105	0.4696	0.275*	0.25
H16E	0.6702	0.5590	0.5776	0.275*	0.25
H16F	0.5464	0.6412	0.5488	0.275*	0.25
C17'	0.470 (7)	0.421 (6)	0.566 (4)	0.1834 (13)	0.25
H17D	0.4090	0.3612	0.5337	0.275*	0.25
H17E	0.4264	0.4733	0.5980	0.275*	0.25
H17F	0.5465	0.3883	0.6157	0.275*	0.25
C15'	0.471 (4)	0.450 (3)	0.403 (3)	0.1834 (14)	0.25
H15'	0.4165	0.3852	0.3858	0.220*	0.25
N4'	0.506 (5)	0.485 (4)	0.494 (3)	0.1833 (12)	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1W	0.32 (3)	0.32 (3)	0.32 (3)	−0.001 (2)	0.105 (9)	0.000 (2)
Cu1'	0.0129 (11)	0.0159 (12)	0.0243 (13)	−0.0010 (7)	0.0038 (9)	0.0005 (8)
C2'	0.0208 (10)	0.0218 (10)	0.0232 (12)	0.0004 (8)	0.0072 (10)	−0.0005 (10)
N2'	0.0211 (9)	0.0227 (10)	0.0239 (11)	0.0000 (8)	0.0073 (9)	−0.0002 (9)
N1'	0.0205 (10)	0.0220 (10)	0.0227 (12)	0.0005 (8)	0.0077 (10)	−0.0003 (10)
C3'	0.0210 (10)	0.0224 (10)	0.0235 (12)	0.0000 (8)	0.0070 (9)	−0.0002 (10)
C1'	0.0204 (10)	0.0225 (10)	0.0234 (12)	0.0004 (8)	0.0074 (9)	−0.0003 (10)
C4'	0.0279 (17)	0.0284 (19)	0.0294 (19)	−0.0002 (12)	0.0089 (12)	0.0001 (12)
C5'	0.0282 (17)	0.0284 (18)	0.0289 (18)	−0.0002 (12)	0.0091 (12)	0.0002 (12)
C6'	0.0283 (16)	0.0284 (17)	0.0289 (17)	−0.0004 (11)	0.0091 (11)	0.0003 (10)
C7'	0.0281 (17)	0.0286 (18)	0.0291 (18)	−0.0003 (12)	0.0090 (12)	0.0005 (11)
C8'	0.0279 (16)	0.0283 (17)	0.0289 (17)	−0.0002 (11)	0.0090 (11)	0.0004 (10)
C9'	0.0279 (17)	0.0282 (18)	0.0289 (18)	−0.0002 (12)	0.0091 (12)	0.0001 (12)
C10'	0.0283 (17)	0.0285 (17)	0.0291 (17)	−0.0004 (11)	0.0091 (12)	0.0005 (11)
C11'	0.0278 (17)	0.0282 (17)	0.0288 (17)	−0.0003 (11)	0.0089 (11)	0.0005 (11)
O1'	0.028 (2)	0.0288 (19)	0.030 (2)	−0.0001 (13)	0.0092 (14)	0.0008 (13)
O2'	0.0286 (18)	0.028 (2)	0.029 (2)	0.0000 (13)	0.0091 (14)	0.0009 (15)
O3'	0.0278 (19)	0.028 (2)	0.029 (2)	−0.0004 (13)	0.0087 (13)	0.0011 (15)
O4'	0.028 (2)	0.0286 (19)	0.029 (2)	−0.0009 (13)	0.0083 (14)	0.0007 (13)
Cu1	0.0128 (6)	0.0185 (6)	0.0214 (6)	0.0005 (4)	0.0046 (4)	0.0004 (4)
N1	0.0203 (9)	0.0221 (10)	0.0224 (12)	−0.0008 (8)	0.0078 (9)	−0.0001 (10)
N2	0.0212 (9)	0.0229 (10)	0.0240 (11)	−0.0002 (7)	0.0072 (8)	−0.0004 (9)
C1	0.0208 (9)	0.0227 (10)	0.0244 (12)	−0.0005 (8)	0.0065 (9)	−0.0001 (10)
C2	0.0213 (10)	0.0223 (10)	0.0240 (12)	−0.0001 (8)	0.0068 (9)	−0.0006 (10)
C3	0.0218 (10)	0.0229 (10)	0.0245 (12)	−0.0003 (8)	0.0068 (9)	−0.0004 (10)
C4	0.0228 (9)	0.0243 (10)	0.0255 (10)	−0.0001 (7)	0.0075 (7)	−0.0006 (8)
C5	0.0245 (11)	0.0255 (13)	0.0263 (13)	−0.0003 (11)	0.0082 (10)	−0.0017 (11)
C6	0.0247 (11)	0.0265 (12)	0.0272 (12)	0.0002 (10)	0.0089 (10)	−0.0023 (9)
C7	0.0248 (12)	0.0267 (14)	0.0276 (13)	0.0003 (11)	0.0079 (10)	−0.0020 (10)
C8	0.0250 (11)	0.0263 (12)	0.0273 (12)	0.0001 (10)	0.0079 (9)	−0.0022 (9)
C9	0.0248 (12)	0.0257 (13)	0.0270 (13)	0.0003 (11)	0.0080 (10)	−0.0019 (10)
C10	0.0254 (12)	0.0273 (12)	0.0280 (12)	0.0001 (10)	0.0092 (10)	−0.0025 (10)
C11	0.0251 (12)	0.0267 (12)	0.0277 (12)	0.0005 (10)	0.0084 (10)	−0.0025 (10)
O1	0.0257 (14)	0.0274 (14)	0.0299 (15)	0.0002 (11)	0.0102 (12)	−0.0039 (12)
O2	0.0254 (13)	0.0295 (15)	0.0293 (15)	−0.0002 (11)	0.0102 (12)	−0.0044 (13)
O3	0.0262 (13)	0.0290 (15)	0.0292 (14)	0.0019 (11)	0.0071 (11)	−0.0042 (13)
O4	0.0261 (14)	0.0275 (14)	0.0285 (15)	0.0017 (11)	0.0069 (12)	−0.0040 (11)
C17	0.1834 (19)	0.183 (2)	0.183 (2)	0.0000 (14)	0.0609 (14)	0.0000 (15)
O6	0.184 (2)	0.184 (3)	0.184 (3)	−0.0003 (17)	0.0607 (16)	0.0002 (18)
N4	0.1834 (13)	0.1833 (13)	0.1833 (13)	0.0000 (8)	0.0609 (8)	0.0000 (8)
C15	0.1834 (16)	0.1834 (16)	0.1834 (16)	−0.0001 (11)	0.0608 (10)	0.0001 (11)
C16	0.184 (2)	0.184 (2)	0.1834 (17)	0.0000 (15)	0.0609 (13)	0.0000 (14)
N3'	0.0648 (6)	0.0650 (6)	0.0654 (6)	−0.0002 (4)	0.0215 (4)	−0.0002 (4)
C12'	0.0650 (8)	0.0650 (7)	0.0653 (8)	−0.0001 (5)	0.0215 (6)	−0.0001 (6)
C14'	0.0650 (8)	0.0653 (9)	0.0655 (10)	0.0000 (6)	0.0215 (7)	−0.0001 (7)
C13'	0.0648 (9)	0.0648 (9)	0.0650 (10)	0.0000 (7)	0.0215 (7)	0.0000 (7)
O5'	0.0652 (10)	0.0651 (11)	0.0653 (12)	0.0001 (7)	0.0216 (8)	0.0000 (8)
N3	0.0648 (6)	0.0650 (6)	0.0654 (6)	−0.0002 (4)	0.0215 (4)	−0.0002 (4)
C12	0.0647 (8)	0.0650 (7)	0.0653 (8)	−0.0001 (5)	0.0215 (6)	−0.0002 (6)
C14	0.0653 (8)	0.0658 (9)	0.0662 (10)	−0.0006 (6)	0.0214 (7)	−0.0002 (7)
C13	0.0652 (8)	0.0650 (9)	0.0652 (10)	0.0000 (6)	0.0217 (7)	0.0000 (7)
O5	0.0641 (10)	0.0641 (10)	0.0642 (11)	0.0003 (7)	0.0216 (8)	0.0001 (8)
O6'	0.184 (2)	0.184 (2)	0.183 (2)	−0.0001 (17)	0.0610 (16)	0.0000 (16)
C16'	0.1833 (17)	0.1833 (16)	0.1833 (17)	0.0000 (11)	0.0609 (12)	0.0000 (12)
C17'	0.1834 (16)	0.1834 (16)	0.1834 (16)	−0.0001 (11)	0.0608 (11)	0.0001 (11)
C15'	0.1834 (17)	0.1834 (17)	0.1833 (15)	0.0000 (12)	0.0608 (11)	0.0000 (11)
N4'	0.1834 (13)	0.1833 (13)	0.1833 (13)	0.0000 (8)	0.0609 (8)	0.0000 (8)

Geometric parameters (Å, º)

Cu1'—N4'	1.19 (5)	C8—C9	1.3900
Cu1'—C17'	1.69 (6)	C8—C11	1.504 (8)
Cu1'—C15'	1.87 (5)	C9—H9A	0.9500
Cu1'—C16'	1.88 (7)	C10—O1	1.230 (9)
Cu1'—O4'^i	1.961 (12)	C10—O2	1.259 (9)
Cu1'—O1'^ii	1.974 (12)	C11—O4	1.239 (9)
Cu1'—O2'^iii	1.981 (12)	C11—O3	1.261 (9)
Cu1'—O3'^iv	1.992 (12)	O1—Cu1^ix	1.961 (5)
Cu1'—N1'	2.169 (16)	O2—Cu1^vi	1.965 (5)
Cu1'—Cu1'^v	2.706 (4)	O3—Cu1^vii	1.975 (5)
Cu1'—H17C	1.5303	O4—Cu1^i	1.963 (5)
Cu1'—H16B	2.0649	C17—N4	1.451 (5)
Cu1'—H16E	1.8383	C17—H17A	0.9800
Cu1'—H17F	1.6445	C17—H17B	0.9800
C2'—C3'	1.29 (3)	C17—H17C	0.9800
C2'—N1'	1.36 (3)	C17—H16E	0.6338
C2'—H2B	0.9500	C17—H16F	1.1365
N2'—C1'	1.37 (3)	O6—C15	1.230 (5)
N2'—C3'	1.38 (3)	O6—H17D	1.2772
N2'—C4'	1.430 (14)	N4—C15	1.311 (5)
N1'—C1'	1.32 (2)	N4—C16	1.451 (5)
C3'—H3B	0.9500	C15—H15	0.9500
C1'—H1B	0.9500	C15—H17D	1.1664
C4'—C5'	1.3900	C15—H17E	0.9489
C4'—C9'	1.3900	C16—H16A	0.9800
C5'—C6'	1.3900	C16—H16B	0.9800
C5'—H5B	0.9500	C16—H16C	0.9800
C6'—C7'	1.3900	N3'—C12'	1.3266 (18)
C6'—C10'	1.47 (2)	N3'—C13'	1.4655 (18)
C7'—C8'	1.3900	N3'—C14'	1.4659 (18)
C7'—H7B	0.9500	C12'—O5'	1.230 (2)
C8'—C9'	1.3900	C12'—H12B	0.9599
C8'—C11'	1.497 (19)	C14'—H14D	0.9800
C9'—H9B	0.9500	C14'—H14E	0.9800
C10'—O1'	1.25 (2)	C14'—H14F	0.9800
C10'—O2'	1.28 (2)	C13'—H13D	0.9800
C11'—O4'	1.25 (2)	C13'—H13E	0.9800
C11'—O3'	1.28 (2)	C13'—H13F	0.9800
O1'—Cu1'^ii	1.974 (12)	C12—O5	1.230 (2)
O2'—Cu1'^vi	1.981 (12)	C12—H12A	0.9600
O3'—Cu1'^vii	1.992 (12)	C14—H14A	0.9800
O4'—Cu1'^viii	1.961 (12)	C14—H14B	0.9800
Cu1—O1^ix	1.961 (5)	C14—H14C	0.9800
Cu1—O4^viii	1.963 (5)	C13—H13A	0.9800
Cu1—O2^iii	1.965 (5)	C13—H13B	0.9800
Cu1—O3^iv	1.975 (5)	C13—H13C	0.9800
Cu1—N1	2.134 (7)	O6'—C15'	1.231 (5)
Cu1—Cu1^x	2.6993 (19)	O6'—H16A	1.3123
N1—C1	1.322 (13)	O6'—H16B	0.7128
N1—C2	1.370 (12)	O6'—H16C	1.3352
N2—C1	1.336 (14)	C16'—N4'	1.451 (5)
N2—C3	1.369 (12)	C16'—H17B	0.7818
N2—C4	1.424 (7)	C16'—H17C	1.2207
C1—H1A	0.9500	C16'—H16D	0.9800
C2—C3	1.347 (11)	C16'—H16E	0.9800
C2—H2A	0.9500	C16'—H16F	0.9800
C3—H3A	0.9500	C17'—N4'	1.451 (5)
C4—C5	1.3900	C17'—H15	0.9321
C4—C9	1.3900	C17'—H17D	0.9800
C5—C6	1.3900	C17'—H17E	0.9800
C5—H5A	0.9500	C17'—H17F	0.9800
C6—C7	1.3900	C15'—N4'	1.311 (5)
C6—C10	1.515 (8)	C15'—H16A	0.8890
C7—C8	1.3900	C15'—H16B	1.0635
C7—H7A	0.9500	C15'—H15'	0.9500
N4'—Cu1'—C17'	57 (2)	C5—C4—N2	121.2 (5)
N4'—Cu1'—C15'	44.1 (16)	C9—C4—N2	118.8 (5)
C17'—Cu1'—C15'	84 (2)	C6—C5—C4	120.0
N4'—Cu1'—C16'	50 (3)	C6—C5—H5A	120.0
C17'—Cu1'—C16'	89 (3)	C4—C5—H5A	120.0
C15'—Cu1'—C16'	79.5 (17)	C5—C6—C7	120.0
N4'—Cu1'—O4'^i	92 (2)	C5—C6—C10	120.2 (4)
C17'—Cu1'—O4'^i	84 (3)	C7—C6—C10	119.7 (4)
C15'—Cu1'—O4'^i	132.3 (12)	C8—C7—C6	120.0
C16'—Cu1'—O4'^i	54.0 (16)	C8—C7—H7A	120.0
N4'—Cu1'—O1'^ii	83 (2)	C6—C7—H7A	120.0
C17'—Cu1'—O1'^ii	139 (2)	C7—C8—C9	120.0
C15'—Cu1'—O1'^ii	71.7 (14)	C7—C8—C11	120.1 (4)
C16'—Cu1'—O1'^ii	54.7 (18)	C9—C8—C11	119.9 (4)
O4'^i—Cu1'—O1'^ii	87.4 (5)	C8—C9—C4	120.0
N4'—Cu1'—O2'^iii	85 (2)	C8—C9—H9A	120.0
C17'—Cu1'—O2'^iii	28 (2)	C4—C9—H9A	120.0
C15'—Cu1'—O2'^iii	100.8 (15)	O1—C10—O2	127.3 (7)
C16'—Cu1'—O2'^iii	114.5 (19)	O1—C10—C6	116.6 (6)
O4'^i—Cu1'—O2'^iii	90.5 (5)	O2—C10—C6	116.0 (6)
O1'^ii—Cu1'—O2'^iii	167.2 (5)	O4—C11—O3	127.1 (7)
N4'—Cu1'—O3'^iv	75 (2)	O4—C11—C8	116.7 (6)
C17'—Cu1'—O3'^iv	89 (2)	O3—C11—C8	116.2 (6)
C15'—Cu1'—O3'^iv	35.4 (12)	C10—O1—Cu1^ix	122.2 (5)
C16'—Cu1'—O3'^iv	114.7 (16)	C10—O2—Cu1^vi	124.0 (5)
O4'^i—Cu1'—O3'^iv	166.9 (5)	C11—O3—Cu1^vii	123.4 (5)
O1'^ii—Cu1'—O3'^iv	90.2 (5)	C11—O4—Cu1^i	122.9 (5)
O2'^iii—Cu1'—O3'^iv	89.0 (5)	N4—C17—H17A	107.5
N4'—Cu1'—N1'	165.7 (19)	N4—C17—H17B	110.7
C17'—Cu1'—N1'	132 (2)	H17A—C17—H17B	109.5
C15'—Cu1'—N1'	122.1 (13)	N4—C17—H17C	110.2
C16'—Cu1'—N1'	132 (2)	H17A—C17—H17C	109.5
O4'^i—Cu1'—N1'	99.1 (5)	H17B—C17—H17C	109.5
O1'^ii—Cu1'—N1'	88.9 (5)	N4—C17—H16D	81.4
O2'^iii—Cu1'—N1'	103.9 (5)	H17A—C17—H16D	162.1
O3'^iv—Cu1'—N1'	93.7 (5)	H17B—C17—H16D	52.7
N4'—Cu1'—Cu1'^v	7.0 (19)	H17C—C17—H16D	80.7
C17'—Cu1'—Cu1'^v	56 (2)	N4—C17—H16E	139.3
C15'—Cu1'—Cu1'^v	50.9 (12)	H17A—C17—H16E	96.2
C16'—Cu1'—Cu1'^v	46 (2)	H17B—C17—H16E	91.0
O4'^i—Cu1'—Cu1'^v	85.1 (4)	H17C—C17—H16E	29.2
O1'^ii—Cu1'—Cu1'^v	83.3 (4)	H16D—C17—H16E	85.8
O2'^iii—Cu1'—Cu1'^v	84.0 (4)	N4—C17—H16F	85.4
O3'^iv—Cu1'—Cu1'^v	81.8 (4)	H17A—C17—H16F	92.3
N1'—Cu1'—Cu1'^v	171.0 (4)	H17B—C17—H16F	37.8
N4'—Cu1'—H17C	90.7	H17C—C17—H16F	146.7
C17'—Cu1'—H17C	113.0	H16D—C17—H16F	72.6
C15'—Cu1'—H17C	113.0	H16E—C17—H16F	127.0
C16'—Cu1'—H17C	40.3	C15—O6—H17D	55.4
O4'^i—Cu1'—H17C	35.1	C15—N4—C17	120.8 (9)
O1'^ii—Cu1'—H17C	52.5	C15—N4—C16	120.2 (9)
O2'^iii—Cu1'—H17C	125.3	C17—N4—C16	118.9 (6)
O3'^iv—Cu1'—H17C	141.8	O6—C15—N4	124.6 (11)
N1'—Cu1'—H17C	93.4	O6—C15—H15	115.7
Cu1'^v—Cu1'—H17C	85.5	N4—C15—H15	119.7
N4'—Cu1'—H16B	62.1	O6—C15—H17D	64.3
C17'—Cu1'—H16B	113.7	N4—C15—H17D	116.4
C15'—Cu1'—H16B	30.9	H15—C15—H17D	87.4
C16'—Cu1'—H16B	71.9	O6—C15—H17E	124.2
O4'^i—Cu1'—H16B	122.9	N4—C15—H17E	110.9
O1'^ii—Cu1'—H16B	42.5	H15—C15—H17E	11.2
O2'^iii—Cu1'—H16B	131.5	H17D—C15—H17E	97.8
O3'^iv—Cu1'—H16B	50.3	N4—C16—H16A	111.5
N1'—Cu1'—H16B	104.0	N4—C16—H16B	109.2
Cu1'^v—Cu1'—H16B	67.1	H16A—C16—H16B	109.5
H17C—Cu1'—H16B	91.6	N4—C16—H16C	107.7
N4'—Cu1'—H16E	79.2	H16A—C16—H16C	109.5
C17'—Cu1'—H16E	98.9	H16B—C16—H16C	109.5
C15'—Cu1'—H16E	109.0	C12'—N3'—C13'	121.78 (19)
C16'—Cu1'—H16E	30.5	C12'—N3'—C14'	121.72 (19)
O4'^i—Cu1'—H16E	28.9	C13'—N3'—C14'	116.42 (17)
O1'^ii—Cu1'—H16E	60.4	O5'—C12'—N3'	121.6 (2)
O2'^iii—Cu1'—H16E	114.6	O5'—C12'—H12B	116.4
O3'^iv—Cu1'—H16E	142.9	N3'—C12'—H12B	121.9
N1'—Cu1'—H16E	106.7	N3'—C14'—H14D	109.5
Cu1'^v—Cu1'—H16E	73.4	N3'—C14'—H14E	109.5
H17C—Cu1'—H16E	14.6	H14D—C14'—H14E	109.5
H16B—Cu1'—H16E	94.1	N3'—C14'—H14F	109.5
N4'—Cu1'—H17F	89.8	H14D—C14'—H14F	109.5
C17'—Cu1'—H17F	34.2	H14E—C14'—H14F	109.5
C15'—Cu1'—H17F	117.3	N3'—C14'—H12A	88.2
C16'—Cu1'—H17F	103.4	H14D—C14'—H12A	135.2
O4'^i—Cu1'—H17F	70.1	H14E—C14'—H12A	102.0
O1'^ii—Cu1'—H17F	156.1	H14F—C14'—H12A	27.6
O2'^iii—Cu1'—H17F	20.8	N3'—C13'—H13D	109.5
O3'^iv—Cu1'—H17F	109.8	N3'—C13'—H13E	109.5
N1'—Cu1'—H17F	102.4	H13D—C13'—H13E	109.5
Cu1'^v—Cu1'—H17F	86.5	N3'—C13'—H13F	109.5
H17C—Cu1'—H17F	105.2	H13D—C13'—H13F	109.5
H16B—Cu1'—H17F	147.6	H13E—C13'—H13F	109.5
H16E—Cu1'—H17F	95.9	O5—C12—H12A	119.0
C3'—C2'—N1'	109 (2)	H12B—C14—H14A	160.6
C3'—C2'—H2B	125.5	H12B—C14—H14B	53.8
N1'—C2'—H2B	125.5	H12B—C14—H14C	72.2
C1'—N2'—C3'	105.4 (16)	C15'—O6'—H16A	40.8
C1'—N2'—C4'	129.4 (18)	C15'—O6'—H16B	59.4
C3'—N2'—C4'	125.2 (19)	H16A—O6'—H16B	100.2
C1'—N1'—C2'	108.0 (16)	C15'—O6'—H16C	83.0
C1'—N1'—Cu1'	121.4 (12)	H16A—O6'—H16C	74.4
C2'—N1'—Cu1'	130.2 (12)	H16B—O6'—H16C	98.2
C2'—C3'—N2'	109 (2)	N4'—C16'—Cu1'	39 (2)
C2'—C3'—H3B	125.7	N4'—C16'—H17A	89.0
N2'—C3'—H3B	125.7	Cu1'—C16'—H17A	78.7
N1'—C1'—N2'	108.2 (16)	N4'—C16'—H17B	155.4
N1'—C1'—H1B	125.9	Cu1'—C16'—H17B	154.2
N2'—C1'—H1B	125.9	H17A—C16'—H17B	80.8
C5'—C4'—C9'	120.0	N4'—C16'—H17C	93.4
C5'—C4'—N2'	115.3 (10)	Cu1'—C16'—H17C	54.2
C9'—C4'—N2'	124.7 (10)	H17A—C16'—H17C	70.2
C4'—C5'—C6'	120.0	H17B—C16'—H17C	103.9
C4'—C5'—H5B	120.0	N4'—C16'—H16D	109.4
C6'—C5'—H5B	120.0	Cu1'—C16'—H16D	108.9
C7'—C6'—C5'	120.0	H17A—C16'—H16D	159.1
C7'—C6'—C10'	120.9 (10)	H17B—C16'—H16D	85.7
C5'—C6'—C10'	118.9 (10)	H17C—C16'—H16D	97.9
C8'—C7'—C6'	120.0	N4'—C16'—H16E	108.7
C8'—C7'—H7B	120.0	Cu1'—C16'—H16E	72.3
C6'—C7'—H7B	120.0	H17A—C16'—H16E	53.1
C7'—C8'—C9'	120.0	H17B—C16'—H16E	82.9
C7'—C8'—C11'	119.7 (10)	H17C—C16'—H16E	24.7
C9'—C8'—C11'	120.2 (10)	H16D—C16'—H16E	109.5
C8'—C9'—C4'	120.0	N4'—C16'—H16F	110.3
C8'—C9'—H9B	120.0	Cu1'—C16'—H16F	138.0
C4'—C9'—H9B	120.0	H17A—C16'—H16F	71.5
O1'—C10'—O2'	126.9 (17)	H17B—C16'—H16F	45.1
O1'—C10'—C6'	116.8 (15)	H17C—C16'—H16F	134.1
O2'—C10'—C6'	116.1 (15)	H16D—C16'—H16F	109.5
O4'—C11'—O3'	126.2 (16)	H16E—C16'—H16F	109.5
O4'—C11'—C8'	117.6 (15)	N4'—C17'—Cu1'	44 (2)
O3'—C11'—C8'	116.1 (15)	N4'—C17'—H15	116.9
C10'—O1'—Cu1'^ii	123.6 (12)	Cu1'—C17'—H15	147.9
C10'—O2'—Cu1'^vi	121.8 (12)	N4'—C17'—H17D	109.4
C11'—O3'—Cu1'^vii	124.2 (11)	Cu1'—C17'—H17D	110.2
C11'—O4'—Cu1'^viii	122.5 (11)	H15—C17'—H17D	100.5
O1^ix—Cu1—O4^viii	87.5 (2)	N4'—C17'—H17E	107.5
O1^ix—Cu1—O2^iii	166.3 (2)	Cu1'—C17'—H17E	137.5
O4^viii—Cu1—O2^iii	90.0 (2)	H15—C17'—H17E	10.7
O1^ix—Cu1—O3^iv	89.8 (2)	H17D—C17'—H17E	109.5
O4^viii—Cu1—O3^iv	166.5 (2)	N4'—C17'—H17F	111.5
O2^iii—Cu1—O3^iv	89.5 (2)	Cu1'—C17'—H17F	70.5
O1^ix—Cu1—N1	95.5 (2)	H15—C17'—H17F	108.4
O4^viii—Cu1—N1	92.9 (2)	H17D—C17'—H17F	109.5
O2^iii—Cu1—N1	98.1 (2)	H17E—C17'—H17F	109.5
O3^iv—Cu1—N1	100.6 (2)	O6'—C15'—N4'	124.1 (11)
O1^ix—Cu1—Cu1^x	84.27 (16)	O6'—C15'—Cu1'	120 (2)
O4^viii—Cu1—Cu1^x	83.95 (16)	N4'—C15'—Cu1'	39 (2)
O2^iii—Cu1—Cu1^x	82.02 (16)	O6'—C15'—H16A	74.5
O3^iv—Cu1—Cu1^x	82.58 (16)	N4'—C15'—H16A	125.2
N1—Cu1—Cu1^x	176.83 (19)	Cu1'—C15'—H16A	162.4
C1—N1—C2	106.5 (8)	O6'—C15'—H16B	35.3
C1—N1—Cu1	124.1 (7)	N4'—C15'—H16B	100.9
C2—N1—Cu1	129.4 (5)	Cu1'—C15'—H16B	84.7
C1—N2—C3	106.2 (8)	H16A—C15'—H16B	109.8
C1—N2—C4	128.0 (9)	O6'—C15'—H15'	118.0
C3—N2—C4	125.8 (8)	N4'—C15'—H15'	117.8
N1—C1—N2	111.2 (9)	Cu1'—C15'—H15'	108.3
N1—C1—H1A	124.4	H16A—C15'—H15'	69.6
N2—C1—H1A	124.4	H16B—C15'—H15'	133.0
C3—C2—N1	108.1 (7)	Cu1'—N4'—C15'	97 (3)
C3—C2—H2A	126.0	Cu1'—N4'—C16'	90 (4)
N1—C2—H2A	126.0	C15'—N4'—C16'	120.6 (10)
C2—C3—N2	107.9 (8)	Cu1'—N4'—C17'	79 (3)
C2—C3—H3A	126.1	C15'—N4'—C17'	120.2 (10)
N2—C3—H3A	126.1	C16'—N4'—C17'	119.0 (6)
C5—C4—C9	120.0
C3'—C2'—N1'—C1'	6.6 (14)	C7—C8—C9—C4	0.0
C3'—C2'—N1'—Cu1'	−166.3 (9)	C11—C8—C9—C4	−177.1 (6)
N4'—Cu1'—N1'—C1'	102 (9)	C5—C4—C9—C8	0.0
C17'—Cu1'—N1'—C1'	−130 (3)	N2—C4—C9—C8	177.4 (6)
C15'—Cu1'—N1'—C1'	115.6 (19)	C5—C6—C10—O1	−30.1 (9)
C16'—Cu1'—N1'—C1'	10 (2)	C7—C6—C10—O1	153.1 (5)
O4'^i—Cu1'—N1'—C1'	−39.2 (12)	C5—C6—C10—O2	150.5 (5)
O1'^ii—Cu1'—N1'—C1'	48.0 (12)	C7—C6—C10—O2	−26.4 (8)
O2'^iii—Cu1'—N1'—C1'	−132.0 (11)	C7—C8—C11—O4	153.5 (6)
O3'^iv—Cu1'—N1'—C1'	138.1 (12)	C9—C8—C11—O4	−29.4 (9)
Cu1'^v—Cu1'—N1'—C1'	78 (3)	C7—C8—C11—O3	−27.2 (8)
N4'—Cu1'—N1'—C2'	−86 (9)	C9—C8—C11—O3	149.9 (6)
C17'—Cu1'—N1'—C2'	42 (4)	O2—C10—O1—Cu1^ix	−3.0 (11)
C15'—Cu1'—N1'—C2'	−72 (2)	C6—C10—O1—Cu1^ix	177.7 (4)
C16'—Cu1'—N1'—C2'	−178 (2)	O1—C10—O2—Cu1^vi	4.6 (12)
O4'^i—Cu1'—N1'—C2'	132.9 (12)	C6—C10—O2—Cu1^vi	−176.1 (4)
O1'^ii—Cu1'—N1'—C2'	−139.8 (13)	O4—C11—O3—Cu1^vii	4.6 (12)
O2'^iii—Cu1'—N1'—C2'	40.2 (13)	C8—C11—O3—Cu1^vii	−174.6 (4)
O3'^iv—Cu1'—N1'—C2'	−49.8 (13)	O3—C11—O4—Cu1^i	−2.6 (12)
Cu1'^v—Cu1'—N1'—C2'	−109 (3)	C8—C11—O4—Cu1^i	176.7 (4)
N1'—C2'—C3'—N2'	−1.2 (11)	C17—N4—C15—O6	180 (3)
C1'—N2'—C3'—C2'	−4.4 (12)	C16—N4—C15—O6	2 (3)
C4'—N2'—C3'—C2'	177.8 (12)	C13'—N3'—C12'—O5'	0 (2)
C2'—N1'—C1'—N2'	−9.4 (16)	C14'—N3'—C12'—O5'	−176.4 (16)
Cu1'—N1'—C1'—N2'	164.3 (11)	C17'—Cu1'—C16'—N4'	−47.2 (18)
C3'—N2'—C1'—N1'	8.5 (15)	C15'—Cu1'—C16'—N4'	37.4 (13)
C4'—N2'—C1'—N1'	−173.9 (14)	O4'^i—Cu1'—C16'—N4'	−131 (2)
C1'—N2'—C4'—C5'	−45 (2)	O1'^ii—Cu1'—C16'—N4'	112 (2)
C3'—N2'—C4'—C5'	132.6 (13)	O2'^iii—Cu1'—C16'—N4'	−60 (2)
C1'—N2'—C4'—C9'	136.9 (15)	O3'^iv—Cu1'—C16'—N4'	41 (2)
C3'—N2'—C4'—C9'	−46 (2)	N1'—Cu1'—C16'—N4'	161 (2)
C9'—C4'—C5'—C6'	0.0	Cu1'^v—Cu1'—C16'—N4'	−7 (3)
N2'—C4'—C5'—C6'	−178.5 (14)	C15'—Cu1'—C17'—N4'	−37.5 (11)
C4'—C5'—C6'—C7'	0.0	C16'—Cu1'—C17'—N4'	42.1 (16)
C4'—C5'—C6'—C10'	175.0 (13)	O4'^i—Cu1'—C17'—N4'	96.1 (14)
C5'—C6'—C7'—C8'	0.0	O1'^ii—Cu1'—C17'—N4'	16 (3)
C10'—C6'—C7'—C8'	−174.9 (13)	O2'^iii—Cu1'—C17'—N4'	−163 (4)
C6'—C7'—C8'—C9'	0.0	O3'^iv—Cu1'—C17'—N4'	−72.6 (13)
C6'—C7'—C8'—C11'	−176.4 (13)	N1'—Cu1'—C17'—N4'	−167 (3)
C7'—C8'—C9'—C4'	0.0	Cu1'^v—Cu1'—C17'—N4'	8 (2)
C11'—C8'—C9'—C4'	176.4 (13)	N4'—Cu1'—C15'—O6'	109 (3)
C5'—C4'—C9'—C8'	0.0	C17'—Cu1'—C15'—O6'	157 (2)
N2'—C4'—C9'—C8'	178.4 (15)	C16'—Cu1'—C15'—O6'	67 (3)
C7'—C6'—C10'—O1'	−151.4 (12)	O4'^i—Cu1'—C15'—O6'	79 (3)
C5'—C6'—C10'—O1'	34 (2)	O1'^ii—Cu1'—C15'—O6'	11 (2)
C7'—C6'—C10'—O2'	24.9 (19)	O2'^iii—Cu1'—C15'—O6'	180 (3)
C5'—C6'—C10'—O2'	−150.1 (12)	O3'^iv—Cu1'—C15'—O6'	−107 (4)
C7'—C8'—C11'—O4'	−152.3 (13)	N1'—Cu1'—C15'—O6'	−66 (3)
C9'—C8'—C11'—O4'	31 (2)	Cu1'^v—Cu1'—C15'—O6'	107 (3)
C7'—C8'—C11'—O3'	24.3 (19)	C17'—Cu1'—C15'—N4'	47.5 (18)
C9'—C8'—C11'—O3'	−152.2 (12)	C16'—Cu1'—C15'—N4'	−42 (2)
O2'—C10'—O1'—Cu1'^ii	7 (3)	O4'^i—Cu1'—C15'—N4'	−30 (3)
C6'—C10'—O1'—Cu1'^ii	−177.6 (10)	O1'^ii—Cu1'—C15'—N4'	−98 (2)
O1'—C10'—O2'—Cu1'^vi	−8 (3)	O2'^iii—Cu1'—C15'—N4'	71 (2)
C6'—C10'—O2'—Cu1'^vi	176.3 (10)	O3'^iv—Cu1'—C15'—N4'	144 (3)
O4'—C11'—O3'—Cu1'^vii	−6 (3)	N1'—Cu1'—C15'—N4'	−175 (3)
C8'—C11'—O3'—Cu1'^vii	177.6 (10)	Cu1'^v—Cu1'—C15'—N4'	−2 (3)
O3'—C11'—O4'—Cu1'^viii	5 (3)	C17'—Cu1'—N4'—C15'	−119.5 (11)
C8'—C11'—O4'—Cu1'^viii	−179.0 (10)	C16'—Cu1'—N4'—C15'	120.9 (12)
O1^ix—Cu1—N1—C1	−40.9 (6)	O4'^i—Cu1'—N4'—C15'	158.4 (19)
O4^viii—Cu1—N1—C1	46.9 (6)	O1'^ii—Cu1'—N4'—C15'	71.3 (18)
O2^iii—Cu1—N1—C1	137.3 (6)	O2'^iii—Cu1'—N4'—C15'	−111 (2)
O3^iv—Cu1—N1—C1	−131.7 (6)	O3'^iv—Cu1'—N4'—C15'	−20.9 (18)
Cu1^x—Cu1—N1—C1	44 (4)	N1'—Cu1'—N4'—C15'	17 (10)
O1^ix—Cu1—N1—C2	143.0 (5)	Cu1'^v—Cu1'—N4'—C15'	166 (18)
O4^viii—Cu1—N1—C2	−129.2 (6)	C17'—Cu1'—N4'—C16'	119.6 (10)
O2^iii—Cu1—N1—C2	−38.8 (6)	C15'—Cu1'—N4'—C16'	−120.9 (12)
O3^iv—Cu1—N1—C2	52.2 (6)	O4'^i—Cu1'—N4'—C16'	37.5 (17)
Cu1^x—Cu1—N1—C2	−132 (3)	O1'^ii—Cu1'—N4'—C16'	−49.6 (16)
C2—N1—C1—N2	−3.8 (8)	O2'^iii—Cu1'—N4'—C16'	127.9 (18)
Cu1—N1—C1—N2	179.4 (5)	O3'^iv—Cu1'—N4'—C16'	−141.8 (17)
C3—N2—C1—N1	3.7 (8)	N1'—Cu1'—N4'—C16'	−104 (9)
C4—N2—C1—N1	−176.7 (6)	Cu1'^v—Cu1'—N4'—C16'	45 (17)
C1—N1—C2—C3	2.3 (7)	C15'—Cu1'—N4'—C17'	119.5 (11)
Cu1—N1—C2—C3	178.9 (4)	C16'—Cu1'—N4'—C17'	−119.6 (10)
N1—C2—C3—N2	0.0 (6)	O4'^i—Cu1'—N4'—C17'	−82 (2)
C1—N2—C3—C2	−2.2 (7)	O1'^ii—Cu1'—N4'—C17'	−169.2 (19)
C4—N2—C3—C2	178.2 (6)	O2'^iii—Cu1'—N4'—C17'	8 (2)
C1—N2—C4—C5	40.7 (9)	O3'^iv—Cu1'—N4'—C17'	99 (2)
C3—N2—C4—C5	−139.8 (6)	N1'—Cu1'—N4'—C17'	136 (10)
C1—N2—C4—C9	−136.7 (7)	Cu1'^v—Cu1'—N4'—C17'	−74 (17)
C3—N2—C4—C9	42.9 (8)	O6'—C15'—N4'—Cu1'	−96 (4)
C9—C4—C5—C6	0.0	O6'—C15'—N4'—C16'	−2 (3)
N2—C4—C5—C6	−177.3 (6)	Cu1'—C15'—N4'—C16'	94 (4)
C4—C5—C6—C7	0.0	O6'—C15'—N4'—C17'	−177 (3)
C4—C5—C6—C10	−176.8 (6)	Cu1'—C15'—N4'—C17'	−81 (4)
C5—C6—C7—C8	0.0	Cu1'—C16'—N4'—C15'	−98 (4)
C10—C6—C7—C8	176.8 (6)	Cu1'—C16'—N4'—C17'	77 (4)
C6—C7—C8—C9	0.0	Cu1'—C17'—N4'—C15'	91 (4)
C6—C7—C8—C11	177.1 (6)	Cu1'—C17'—N4'—C16'	−84 (4)

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