research papers
Double role of metalloporphyrins in catalytic bioinspired supramolecular metal–organic frameworks (SMOFs)
aMineralogía y Petrología, Universidad del País Vasco (UPV/EHU), Barrio Sarriena s/n, Leioa, Bizkaia 48940, Spain, bBCMaterials, Basque Center for Materials, Applications and Nanostructures, Bld. Martina Casiano, 3rd Floor, UPV/EHU Science Park, Barrio Sarriena s/n, Leioa, Bizkaia 48940, Spain, cQuímica Inorgánica, Universidad del País Vasco (UPV/EHU), Barrio Sarriena s/n, Leioa, Bizkaia 48940, Spain, and dMaterials Science Factory, Instituto de Ciencia de Materiales de Madrid-CSIC, Sor Juana Inés de la Cruz 3, Cantoblanco, Madrid 28049, Spain
*Correspondence e-mail: gotzone.barandika@ehu.eus
Heterogeneous catalysts are of great interest in many industrial processes for environmental reasons and, during recent years, a great effort has been devoted to obtain metal–organic frameworks (MOFs) with improved catalytic behaviour. Few supramolecular metal–organic frameworks (SMOFs) are stable under ambient conditions and those with anchored catalysts exhibit favourable properties. However, this paper presents an innovative approach that consists of using metal nodes as both structural synthons and catalysts. Regarding the latter, metalloporphyrins are suitable candidates to play both roles simultaneously. In fact, there are a number of papers that report coordination compounds based on metalloporphyrins exhibiting these features. Thus, the aim of this bioinspired work was to obtain stable SMOFs (at room temperature) based on metalloporphyrins and explore their 2[(MnTPPS)(H2O)2]·2bipy·14H2O (TPPS = meso-tetraphenylporphine-4,4′,4′′,4′′′-tetrasulfonic acid and bipy = 4,4′-bipyridine). This compound is the first example of an MnTPPS-based SMOF, as far as we are aware, and has been structurally and thermally characterized through single-crystal X-ray diffraction, IR spectroscopy, thermogravimetry and Additionally, this work explores not only the of this compound but also of the compounds μ-O-[FeTCPP]2·16DMF and [CoTPPS0.5(bipy)(H2O)2]·6H2O. The structural features of these supramolecular materials, with accessible networks and high thermal stability, are responsible for their excellent behaviour as heterogeneous catalysts for different oxidation, condensation (aldol and Knoevenagel) and one-pot cascade reactions.
This work reports the environmentally friendly microwave-assisted synthesis and characterization of the compound [H(bipy)]Keywords: metalloporphyrins; supramolecular MOFs; heterogeneous catalysts; Knoevenagel condensations; aldol condensations; one-pot cascade reactions.
CCDC reference: 1515741
1. Introduction
During recent years, supramolecular materials and metal–organic frameworks (MOFs) have been thoroughly explored in many fields, such as water reuse, et al., 2015; Dias & Petit, 2015; Li et al., 2016; Li & Hill, 2017; Wang et al., 2016; Gao et al., 2014). Their structural and chemical properties make them excellent candidates as solid catalysts for many reactions (Dhakshinamoorthy et al., 2012). Moreover, supramolecular metal–organic frameworks (SMOFs), in which the three-dimensional crystalline network is sustained by hydrogen bonds (Pérez-Aguirre et al., 2016; Reger et al., 2012; Thomas-Gipson et al., 2014), are attracting much interest, and in order to obtain those coordination networks, the use of has been rising, since they are organic ligands which present unique properties attached to biochemical, enzymatic and photochemical functions (Kornienko et al., 2015; Spoerke et al., 2017). Biomimetic catalysts, such as metalloporphyrins, have been used as cytochrome analogues because of the similarity between these molecules and the active centres of the enzymes. Oxidation, condensation and hydrolysis reactions are very common in living organisms and many efforts have been made to mimic their by means of metalloporphyrin-based synthetic models (Johnson et al., 2016; Chen et al., 2012; Feng et al., 2012). In fact, metalloporphyrinic supramolecular compounds are appearing as a new class of promising materials in the development of catalytic cascade or one-pot reactions (Hajimohammadi et al., 2012; Shinde et al., 2015; Prasad et al., 2014; Lu et al., 2015). Most of the catalytic reactions in industry use the traditional design of simple catalytic reactions involving expensive catalysts and processes. So, in order to reduce costs and optimize processes, the majority of recent work has focused on homogeneous (Omagari et al., 2016; Bonin et al., 2014; Costentin et al., 2014; Pires et al., 2014) or heterogeneous based on metalloporphyrinic networks (Zhang et al., 2016; Chen et al., 2015; Hod et al., 2015; Ucoski et al., 2015; Wang et al., 2013; Meng et al., 2012). There are some disadvantages of including poor understanding of the reaction mechanisms, heat diffusion problems, low reaction selectivity and poorly defined active sites. However, recycling is one of the most important advantages for and it is based on easy catalyst separation (Moulijn et al., 1993).
electrochemistry and gas adsorption (de LangeIn order to achieve ; Liu et al., 2016), doping the network with the catalyst (Lan et al., 2016) or post functionalizing the network (Andriamitantsoa et al., 2016). In this sense, we have been exploring a new strategy that consists of using as structural units in SMOFs and catalytic active centres simultaneously (Fidalgo-Marijuan et al., 2015). This strategy includes the use of first-row transition metals, avoiding commonly used heavy and toxic metals such as Ru, Rh and Ce (Liu et al., 2017). It is also noteworthy that we have performed green syntheses, using preferably non-toxic solvents (water) and fast microwave heating.
there are a number of successful approaches such as anchoring the catalyst into the cavities of porous coordination networks (Zhan & Zeng, 2016Taking into consideration the above-mentioned aspects, we report here the 2[(MnTPPS)(H2O)2]·2bipy·14H2O, 1, having MnTPPS-based monomers, the μ-O-[FeTCPP]2·16DMF dimeric compound, 2, and the [CoTPPS0.5(bipy)(H2O)2]·6H2O one-dimensional compound, 3, where TPPS = meso-tetraphenylporphine-4,4′,4′′,4′′′-tetrasulfonic acid, TCPP = meso-tetra(4-carboxyphenyl)porphine, bipy = 4,4′-bipyridine and DMF = N,N′-dimethylformamide. It is worth noting that compound 1 is the first Mn TPPS metalloporphyrinic SMOF reported so far. We have reported the structural features of 2 and 3 elsewhere (Fidalgo-Marijuan et al., 2015, Fidalgo-Marijuan et al., 2013).
of three porphyrinic SMOFs: [H(bipy)]Compounds 1, 2 and 3 have been exhaustively characterized by means of single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis and (TEM), after which oxidation, Knoevenagel and aldol condensations, and a one-pot cascade reaction (involving an acetal hydrolysis in the first step and a Knoevenagel condensation in the second) have been successfully tested for these compounds.
2. Experimental
2.1. General
All solvents and reagents including meso-tetraphenylporphine-4,4′,4′′,4′′′-tetrasulfonic acid tetrasodium salt (TPPS), 4,4′-bipyridine (bipy) and Mn(NO3)2·xH2O were purchased from Sigma–Aldrich.
2.2. Synthesis of [H(bipy)]2[(MnTPPS)(H2O)2]·2bipy·14H2O
TPPS (10.2 mg, 0.01 mmol) and Mn(NO3)2·xH2O (1.0 mg, 0.006 mmol) were dissolved in distilled water (10 ml) and the solution was stirred for 30 min. Then, 4,4′-bipyridine (9.4 mg, 0.06 mmol) was dissolved in hot (343 K) distilled water (5 ml) and added to the mixture in a 100 ml CEM EasyPrep microwave vessel. The mixture was heated by microwaves under autogenous pressure at 433 K for 2 h, and then cooled naturally to room temperature, yielding diffraction-quality prismatic dark-red crystals. [For C42H46Mn0.5N6O14S2. Found: C, 53.55 (4); H, 4.85 (2); N, 8.84 (6); O, 22.95 (6); S, 6.89 (4). Calculated: C, 53.08; H, 4.88; N, 8.84; O, 23.57; S, 6.75]. νmax/cm−1 3397 (OH), 1636–1413 (CC), 1393 and 1180 (SO), 1340 (CN), 1204 and 1070 (bipy), 1003 (MnTPPS) and 857–634 (CH) (see Fig. S1 in the supporting information).
2.3. Single-crystal X-ray diffraction
Prismatic dark-red single-crystals of compound 1 (dimensions given in Table 4) were selected under a polarizing microscope and mounted on MicroMounts. Single-crystal X-ray diffraction data were collected at 100 K on a SuperNova single source diffractometer with Cu Kα radiation (λ = 1.54184 Å). Data frames were processed [unit-cell determination, intensity-data integration, correction for Lorentz and polarization effects (Yinghua, 1987) and analytical absorption correction] using the CrysAlisPro software package (Agilent Technologies UK Ltd, 2012).
The structure of 1 was solved in the triclinic using the SIR92 program (Altomare et al., 1993) which allowed us to determine the position of the Mn atom, as well as some of the O, N, S and C atoms of the porphyrin and bipyridine molecules. The of the was performed by full matrix least-squares based on F2, using the SHELXL97 program (Sheldrick, 2008), obtaining the remaining C, N, O and S atoms of the porphyrin and O atoms of water molecules. Anisotropic displacement parameters (Farrugia, 1997) were used for all non-hydrogen atoms, except for the disordered crystallized water molecules (Fig. S2). All H atoms connected to aromatic rings (C—H = 0.95 Å) were fixed geometrically and refined using a riding model with common isotropic displacements. Four of the crystallized water molecules of compound 1 were disordered over two groups, with half occupancy each, as well as for one of the porphyrin sulfite groups. Crystal data for compound 1 are listed in Table 1. Geometric parameters, atomic coordinates and anisotropic displacement parameters are given in the supporting information, Tables S1, S2 and S3.
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Diameter values of the channels for compounds 1, 2 and 3 were calculated using the program TOPOS (available at https://www.topos.ssu.samara.ru).
2.4. Physicochemical characterization techniques
The IR spectra were collected on a JASCO FT/IR-6100 spectrometer at room temperature in the range 4000–400 cm−1, in KBr pellets (1% sample). C, H, N, S and O elemental analyses were measured using a Euro EA 3000 elemental analyser. Thermogravimetric analyses were carried out using a NETZSCH STA 449 F3 thermobalance. A crucible containing approximately 10 mg of sample was heated at 5 K min−1 in the temperature range 303–873 K.
TEM work was done on a Philips SuperTwin CM200 operated at 200 kV and equipped with an LaB6 filament and EDAX EDS microanalysis system. The samples for TEM analysis were prepared by dispersion into ethanol and keeping the suspension in an ultrasonic bath for 15 min. After that, a drop of the suspension was spread onto a TEM copper grid (300 mesh) covered by a holey carbon film, followed by drying under vacuum.
2.5. Catalytic activity
The oxidation reactions of benzyl alcohol, 1-phenylethanol, 1-hexanol and 1-octanol were carried out at 343 K using acetonitrile as the solvent. The catalyst/substrate molar ratio (based on the metal) used for all the reactions was 5:100. Powdered crystals of the catalysts were initially dried at 373 K under vacuum to remove solvent and water adsorbed on the surface.
Before the reactions, approximately 5 mg of dried catalyst was activated by stirring with the oxidizing agent tert-butyl hydroperoxide (TBHP) in 2 ml of acetonitrile for 30 min at 343 K. After this activation stage, the catalyst was separated from the liquid medium by centrifugation. The reactor was then charged with the activated catalyst and the corresponding alcohol in 2 ml of solvent. The mixture was heated to 343 K and then the oxidizing agent was added dropwise (1.5 equivalents of TBHP).
Aldol condensation reactions of benzaldehyde, p-tolualdehyde, p-methoxybenzaldehyde and heptanal were carried out at 373 K without solvent. The catalyst/substrate molar ratio (based on the metal) used for all the reactions was 10:100. Powdered crystals of the catalysts were first dried at 373 K under vacuum to remove solvent and water adsorbed on the surface. The reactor was charged with the catalyst (10 mg), acetone (1 ml) and the corresponding substrate, and the mixture was then heated to 373 K.
Knoevenagel condensation reactions of benzaldehyde, p-tolualdehyde, p-fluorobenzaldehyde, 4-chlorobenzaldehyde and 3-nitrobenzaldehyde were carried out at 343 K using toluene as the solvent. The catalyst/substrate molar ratio (based on the metal) used for all the reactions was 5:100. Powdered crystals of the catalysts were first dried at 373 K under vacuum to remove solvent and water adsorbed on the surface. The reactor was charged with the catalyst (5 mg), malononitrile (4.6 mg), dodecane as internal standard (2.0 µl) and the corresponding substrate in 2 ml of solvent, and then the mixture was heated to 343 K.
The one-pot cascade reaction was tested for acetal hydrolysis followed by Knoevenagel condensation at 343 K in toluene. The catalyst/substrate molar ratio (based on the metal) used for the reaction was 10:100. Powdered crystals of the catalysts were first dried at 373 K under vacuum to remove solvent and water adsorbed on the surface. The reactor was charged with the catalyst (5.2 mg), toluene (2 ml), benzaldehyde dimethyl acetal (5.3 µl), malononitrile (2.3 mg) and dodecane (2 µl) as internal standard, and then the mixture was heated to 343 K.
Detailed results for the 1, 2 and 3 will be described in Sections 3.3 and 3.4.
exhibited by compoundsReaction samples were taken at regular times and analysed on a Hewlett–Packard 5890 II GC–MS or on a Konik HCGC 5000B gas chromatograph–mass spectrometer. Blank experiments were carried out under the reaction conditions in order to determine the extent of the uncatalysed reaction; for all the blank reactions only traces of the product were found. After the reaction, the catalysts were filtered, dried and characterized by IR spectroscopy, and by TEM microscopy in some cases. The calculations of turnover frequencies (TOF;
is mol substrate converted/mol catalyst per hour) were performed in the initial stages of the reaction, when the reaction rates are higher, as usual.3. Results and discussion
3.1. Crystal structures
The structural features of these materials are of great importance in order to achieve satisfactory conversion rates for catalytic reactions. In this sense, the metalloporphyrinic synthons are intended to act as heterogeneous catalysts and structural building units at the same time. In relation to the latter, accessibility of the guest molecules to catalytic metal centres on the surface of the crystal-network cavities is one of the most important features necessary to consider the compounds as potential catalysts, and was taken into account for compounds 1, 2 and 3.
Compound 1 with the formula [H(bipy)]2[(MnTPPS)(H2O)2]·2bipy·14H2O is a coordination compound consisting of complex ions. The determined by single-crystal X-ray diffraction, shows [(MnTPPS)(H2O)2]2− anionic monomers where TPPS4− ligands are present. The MnII ion is in an octahedral coordination environment, bonded to the four porphyrin N atoms and with two water molecules in the axial positions.
The [(MnTPPS)(H2O)2]2− anions crystallize as shown in Fig. 1. The voids generated between metalloporphyrinic monomers are occupied by [H(bipy)]+ cations and crystallized bipyridine molecules and, as shown in Fig. S3, those bipyridine molecules were pairwise hydrogen-bonded [N5—H1N⋯N4; 2.741 7 Å and 171 9°] and parallel-stacked, giving rise to robust π–π interactions (centroid-to-centroid distances are 3.468 and 3.746 Å) (Soltanzadeh & Morsali, 2009). Additionally, the interstitial voids are occupied by 14 crystallized water molecules per monomer.
The 2O)2]2− units along the direction between the axial water molecule (O7) and the sulfonate groups (O3) (Fig. S4). Additionally, the metalloporphyrinic monomers are linked by a hydrogen-bonded chain along the [100] direction. This connection involves the coordinated water molecules (O7) and two crystallized water molecules (O8 and O11). It is worth noting that there is a zigzag chain of water molecules along the [100] direction which stabilizes the structure. This chain is located between the sulfonate groups involving the O12 to O16 crystallized water molecules (Fig. 2).
is stabilized by an intricate hydrogen-bonded system (Table S4), connecting the [(MnTPPS)(HAs shown in Fig. 1 and Fig. S5, the [H(bipy)2]+ cations are located on the interporphyrinic voids and linked through O9, O10 and O12 water molecules to the sulfonate groups (O2) and through O8 to the axial water molecules (O7).
Fig. 2 shows the accessibility of the to external guest molecules in order to access channels along the x axis. The calculated value of the diameter, obtained using TOPOS (Section 2.3), is 4.3 Å. As shown, the porphyrin units are separated by 9.7187 (4) Å (the a cell parameter), allowing the interaction of potential guest molecules with the centres.
The 2 (μ-O-[FeTCPP]2·16DMF) have been reported previously by us (Fidalgo-Marijuan et al., 2015). This compound consists of FeTCPP dimers, where monomers are connected by an O-bridge. In this way, the active catalytic centres are exposed to the channels of the framework. The calculated value of the diameter, obtained using TOPOS, is 5.2 Å. As shown in Fig. S6, the dimers are packed forming hydrogen-bonded layers in the xy plane, generating the aforementioned channels along the [001] direction, where potential guest molecules are then distributed to the active centres (Fig. 3).
and of compoundThe 3, with the formula [CoTPPS0.5(bipy)(H2O)2]·6H2O, have also been reported by us in previous work (Fidalgo-Marijuan et al., 2013). The is formed by one-dimensional polymers, where octahedral CoII ions of CoTPPS units are axially bonded to bipy ligands (Fig. S7). The extension of the one-dimensional polymers consists of a link between alternating CoII centres along the [001] direction through the bipy ligands in a bipy–CoTPPS–bipy–Co(H2O)4 fashion. In this case, the accessibility to centres takes place along the direction where the centres are exposed to the channels of the framework (Fig. 4). The calculated value for the diameter obtained using TOPOS is 6.1 Å.
and for compound3.2. Thermal analysis
Thermal behaviour is crucial in determining the stability and correct catalytic activation of these materials. As observed in Fig. 5, the thermogravimetric decomposition curve of compound 1 shows a continuous mass loss from room temperature to 813 K, where three steps can be distinguished. The first is assigned to an overlapped two-stage step between room temperature and 673 K. The first stage occurs up to 468 K, with a 12.1% weight loss attributed to the coordinated and crystallized water molecules. The second stage, up to 673 K (19.7% weight loss), corresponds to the crystallized bipyridine molecules. The second step, occurring between 673 K and 723 K, with a 14.3% weight loss, is attributed to the bipyridine molecules formerly present as [H(bipy)]+ cations. The latter assignment is based on the fact that these cationic entities are more robustly linked than their crystallized analogues. The last step, between 723 K and 813 K (42.7% weight loss), is the final degradation of the TPPS units. The product was identified by X-ray powder and it consists of Mn2O3 (space group Rc, a = 5.04, c = 14.12 Å, γ = 120°; Lee et al., 1980).
Compounds 2 and 3 have been thermally characterized in our previous work (Fidalgo-Marijuan et al., 2015, 2013), showing high thermal stability (compound 2 up to 593 K and 3 up to 633 K). The thermogravimetry/differential scanning (TG/DSC) curve for activated compound 2 is shown in Fig. S8.
Additionally, Fig. S9 shows the X-ray thermo-diffraction measurements (XRTD) of powdered single crystals for compounds 1 and 2. The results indicate that both compounds were thermally stable after activation for catalytic purposes.
3.3. Catalytic properties
Synthetic metalloporphyrin complexes have been largely used for a wide variety of catalytic transformations (Chatterjee et al., 2016; Rayati et al., 2016; Sengupta et al., 2016; Zhou et al., 2016), and in this work we have explored the of the monomeric framework [H(bipy)]2[(MnTPPS)(H2O)2]·2bipy·14H2O, 1, the dimeric framework μ-O-[FeTCPP]2·16DMF, 2 (Fidalgo-Marijuan et al., 2015), and the one-dimensional framework [CoTPPS0.5(bipy)(H2O)2]·6H2O, 3 (Fidalgo-Marijuan et al., 2013). As previously shown, these three compounds exhibit features that make them suitable candidates for catalysis of different reactions. Firstly, the metal coordination spheres are either unsaturated or there are water molecules that are easy to remove during the activation stage, as shown by the thermogravimetric analysis. Fig. S10 shows a simplified scheme for 1, 2 and 3, highlighting the catalytic active centres. In addition, the networks are significantly accessible, with mobile DMF or water solvent molecules located in the cavities.
Thus, the catalytic performance was studied for the oxidation of ). The studied substrates for all the reactions are summarized in Table S5.
aldol and Knoevenagel condensations, and a one-pot cascade reaction for an acetal hydrolysis followed by a C—C Knoevenagel condensation (Scheme 13.3.1. Oxidation of alcohols
The selective oxidation of et al., 2013). Although considerable progress has been made using noble-metal nanoparticles such as Au (Corma & Garcia, 2008), it would still be desirable to develop catalysts based on less expensive metals and processes. In this sense, some porphyrinic compounds have been tested (Zou et al., 2013; Machado et al., 2013; Chen & Ma, 2016) in an effort to minimize costs and waste generation.
to is a relevant transformation in waste recovery and in organic synthesis because of the properties and chemical reactivity of carbonylic compounds that make the preferred starting materials in many syntheses (DavisThe reaction conditions were initially set using benzyl alcohol as a model substrate. Based on our previous experience (Fidalgo-Marijuan et al., 2015; Larrea et al., 2011), the reactions were carried out using tert-butyl hydroperoxide (TBHP) as the oxidizing agent in acetonitrile. Using 5% catalyst and 1.5 equivalents of TBHP in 2 ml of solvent at 343 K, total conversions of 50% for 1, 73% for 2 and 71% for 3 were achieved after 7 h of reaction. The scope of the reaction was studied with various 1-phenylethanol, 1-hexanol and 1-octanol (Table 2). Figs. S11, S12 and S13 show the kinetic profiles of these oxidation reactions for 1, 2 and 3.
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The best result for 1 is achieved towards the oxidation of 1-hexanol, since 2 is better for 1-phenylethanol. For benzyl alcohol oxidation, the conversion values are quite similar for the three catalysts, though compound 3 clearly shows a higher TOF. The poor conversion values achieved for 1-octanol in all cases could be explained by the fact that this substrate presents more A comparison of these results with similar porphyrinic catalysts found in the literature indicates a significant reduction in the reaction time (half time) for catalyst 2 (Modak et al., 2013). Moreover, comparing the benzyl alcohol results with classic Rh-, Ru- and Ce-based catalysts showed the conversion rates are slightly higher and have much shorter reaction times (Wusiman & Lu, 2015; Burange et al., 2013; Sarkar et al., 2014).
One of the disadvantages of tert-butoxyl radicals are generated, abstracting an H atom from the substrate and leading to the corresponding aldehyde or ketone (Fig. 6) (Orive et al., 2013).
is the difficulty of studying the reaction mechanisms; often the involved intermediates are unknown. Even so, in the proposed mechanism for alcohol oxidation the initial stage consists of activation of TBHP by coordination to the unsaturated metal centre in order to obtain the corresponding peroxo species. After coordination,3.3.2. Aldol condensation
Aldol condensations are important in organic synthesis, providing a way to form C—C bonds; the identification of catalysts capable of performing C—C bond formation remains a challenge (Scheme 1b) (Thankachan et al., 2015). The main drawbacks of using the usual NaOH or KOH catalysts are corrosion problems in the equipment, separation difficulties and the generation of large amounts of waste. To overcome these disadvantages, efforts have been made to design new catalytic systems with controlled basic properties in order to increase the efficiency of the process. In this context, metalloporphyrinic catalysts 1, 2 and 3 were tested towards the aldol condensation of benzaldehyde and derivatives with acetone.
The reaction conditions were initially set using benzaldehyde as the substrate, using 5% catalyst in 1 ml of acetone at 343 K, obtaining poor conversion values (31% for catalyst 1, 38% for 2 and 2.5% for 3). However, increasing the catalyst amount to 10% and the reaction temperature to 373 K, the total conversions were 79% for 2 and 16% for 3 after 38 h of reaction. Unfortunately, at this temperature, 1 shows caused by the loss of the [H(bipy)]+ cations. Thus, the scope of the reaction was studied with p-tolualdehyde, p-methoxybenzaldehyde and heptanal using compound 2 as the catalyst. Table 3 and Fig. S14 show the conversion values and kinetic profiles for the aldol condensation, respectively.
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As observed, the methyl group in the para position leads to high yields, whereas methoxy groups give poor conversion. In the case of heptanal, the reaction evolves much more quickly, giving rise to the heptanal autocondensation product (Fig. S15a) in a minority amount (7%) and two isomers (double-bond position) of the aldol condensation: the dec-3-en-2-one (52%) (Fig. S15b) and the dec-4-en-2-one (35%) (Fig. S15c). Comparing the results with other MOF-type catalysts, we conclude that, for aromatic substrates, it is necessary to increase the reaction time considerably (up to three times) to obtain similar conversion rates (Abedi et al., 2016). Nevertheless, the reaction with heptanal shows excellent activity using four times less catalyst than in similar reported studies (Yadav & Aduri, 2012).
3.3.3. Knoevenagel condensation
Taking into account the previous results, compound 2 was also tested as a catalyst for the Knoevenagel condensation reaction (Scheme 1c) between various substrates and derivatives (Table 4) and malononitrile (pKa = 11.1). As above, the reaction conditions were set using benzaldehyde as the substrate, 5% catalyst, 1.0 equivalent of malononitrile in 2 ml of toluene and 2 µl of dodecane as internal standard at 343 K, reaching a total conversion of 79% after 22 h of reaction (Table 4). The scope of the reaction was then studied with p-tolualdehyde, p-fluorobenzaldehyde, 4-chlorobenzaldehyde and 3-nitrobenzaldehyde. Fig. S16 shows the kinetic profiles of the Knoevenagel condensation reactions.
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As observed, when introducing substituents into the meta- or para-positions of the benzaldehyde ring, the conversion rates differ as a result of electronic effects, following the order of reactivity: m-nitrobenzaldehyde ≃ p-chlorobenzaldehyde > p-tolualdehyde ≃ benzaldehyde > p-fluorobenzaldehyde.
For both aldol and Knoevenagel condensations, the activation of the carbonyl groups is prompted by a ) (Larrea et al., 2015; Položij et al., 2014). In fact, the distance of 5.656 (1) Å between FeIII ions allowed the cyanide groups of malononitrile [N⋯N distance 4.319 (3) Å] to interact with the Fe active centres. Comparing these results with other MOFs (Larrea et al., 2015), the obtained conversion rates and TOF are among the best using only 5% catalyst under similar reaction conditions.
(the metal ion). The proximity of the active centres (Fe ions) meant that a mechanism involving two-site adsorption of the donor molecule could be proposed (Fig. 73.3.4. One-pot cascade reaction
Taking into account that compound 2 showed the best results for Knoevenagel condensation, it was tested in a bifunctional one-pot cascade reaction (Scheme 1d). The first step involves an acetal hydrolysis using benzaldehyde dimethyl acetal as the substrate, followed by a second step in which Knoevenagel condensation with malononitrile takes place. The results (TOF: 10 h−1, CT: 42% in 44 h) indicate that, although the Knoevenagel condensation reaches a high conversion (79%; Table 4), in this case the rate-limiting step is the reaction involving the acetal hydrolysis. Although in the first few hours the TOF is quite high, after 3 h the conversion rate decelerates, probably because of the inability of the catalyst to overcome the first step of the reaction (Fig. S17).
An excellent strategy to carry out this type of one-pot two-step reaction is to introduce, in the same solid catalyst, both acidic and basic active centres (Merino et al., 2013). Compound 2 shows only centres to catalyse the hydrolysis of benzaldehyde dimethylacetal into benzaldehyde and react with malononitrile through Knoevenagel condensation. This may be the reason for the lower conversion in the one-pot two-step reaction (42%) compared with the single Knoevenagel condensation (79%) for 2.
3.4. Heterogeneity and recyclability tests
The heterogeneous nature of catalysts 1 and 3 towards the oxidation of were tested using benzyl alcohol (2 has been tested previously; Fidalgo-Marijuan et al., 2015). For rigorous proof of heterogeneity, a test (Sheldon et al., 1998) was carried out by filtering the catalyst from the reaction mixture at 343 K after 20 min, when conversions of 24% and 47% had been reached for 1 and 3, respectively. The filtrate was allowed to react for up to 7 h. The reaction mixture and the filtrate were analysed afterwards by GC–MS. No significant change in the conversion rate was found for the filtrate (Fig. 8), meaning that the active species does not leach and the observed catalysis is truly heterogeneous in nature.
The recyclability of catalysts 1 and 3 was also tested for the benzyl alcohol oxidation. The catalyst was recovered after the reaction by centrifugation and washed several times with acetonitrile, then dried at 373 K and reused. As shown in Table S6, catalyst 3 maintains activity after five cycles, whereas 1 shows a small decrease.
As was previously done for the oxidation reactions, the heterogeneous nature of the catalyst and recyclability were tested or the aldol and Knoevenagel condensations by hot filtration. As shown in Fig. 9, the experiments reveal that 2 is a truly heterogeneous catalyst for this reaction. Additionally, the catalyst was reused over five cycles and shows a progressive decrease in after the third cycle (Table S7).
After the catalytic reactions, the catalysts were recovered by centrifugation, washed with acetonitrile, ethanol or toluene and then characterized by IR spectroscopy. The IR spectra of the recovered catalyst for all reactions showed that the chemical-bond systems remained unchanged (Fig. S18). In fact, the solid shows the same characteristic vibration modes as the original compound. As shown in Fig. S18, the characteristic vibrations of the porphyrin macrocycle are present. Additionally, both the fresh catalyst and the recovered solid after the reaction were studied by TEM, as discussed below.
3.5. Transmision electron microscopy
In order to carry out a deeper characterization of the recovered catalyst, compounds 2 and 3 were analysed by TEM before and after the catalytic reactions. Compound 1 is unstable under an electron beam, so it was not analysed by TEM. TEM analysis shows that compounds 2 and 3 maintain a certain grade of crystallinity following the catalytic reactions. Moreover, the pre- and post-catalysis particles of 2 and 3 keep their morphology: elongated prisms for 2 and curved-edge particles for 3 (Fig. S19).
The crystalline nature and moderate stability of samples 2 and 3 under an electron beam allowed us to measure the lattice spacing for both compounds. The HRTEM images (Fig. 10) of the pristine sample (a) and the recovered residue after the catalytic reaction (b) of compound 2 reveal a lattice spacing of 13.45 Å along the width of the crystal. This observed lattice spacing corresponds to the (101), and (210) set of crystallographic planes. For compound 3, the pristine sample (c) and the recovered residue (d) present a spacing near to 14.02 Å, which corresponds to the (011) set of crystallographic planes. Therefore, both compounds maintain the same lattice spacing before and after the catalytic reactions so, as previously observed by IR spectroscopy, compounds 2 and 3 keep their structural integrity.
4. Conclusions
This work explores an innovative approach that consists of using metalloporphyrins as both synthons and catalytic units in solid coordination networks. This strategy is compatible with green synthesis, i.e. using first-row transition metals (Mn, Fe and Co), with water as the preferred solvent and performing syntheses at low temperatures. While most of the studies involving solid coordination networks are focused on three-dimensional covalent MOFs, the results presented here indicate that accessibility of reactants to the metal centres is a significant parameter in achieving good heterogeneous The studied compounds are perfectly operative under ambient conditions as they exhibit recyclability and thermochemical stability. Furthermore, compounds 2 and 3 are remarkably stable upon heating. An improvement in catalytic performance has been achieved in relation to commonly used toxic metal-based catalysts. In summary, bioinspired metalloporphyrinic SMOFs are promising candidates as heterogeneous and recyclable catalysts.
Supporting information
CCDC reference: 1515741
https://doi.org/10.1107/S2052252518007856/lq5011sup1.cif
contains datablocks global, I. DOI:Supporting figures and tables. DOI: https://doi.org/10.1107/S2052252518007856/lq5011sup2.pdf
Data collection: CrysAlis PRO, Agilent Technologies, Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET) (compiled May 16 2011,17:55:39); cell
CrysAlis PRO, Agilent Technologies, Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET) (compiled May 16 2011,17:55:39); data reduction: CrysAlis PRO, Agilent Technologies, Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET) (compiled May 16 2011,17:55:39); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).C22H15Mn0.50N2O7S2·(C10H8N2)·(C10H9N2)·7(H2O) | Z = 2 |
Mr = 950.44 | F(000) = 993 |
Triclinic, P1 | Dx = 1.472 Mg m−3 Dm = 1.446 (5) Mg m−3 Dm measured by Flotation |
a = 9.7187 (4) Å | Cu Kα radiation, λ = 1.54184 Å |
b = 11.2496 (5) Å | Cell parameters from 3937 reflections |
c = 21.8708 (7) Å | θ = 4.1–74.1° |
α = 88.401 (3)° | µ = 2.92 mm−1 |
β = 83.848 (3)° | T = 100 K |
γ = 64.446 (4)° | Prism, dark red |
V = 2144.39 (15) Å3 | 0.14 × 0.05 × 0.01 mm |
SuperNova, Single source at offset), Atlas diffractometer | 8113 independent reflections |
Radiation source: fine-focus sealed tube | 5439 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
Detector resolution: 5.2012 pixels mm-1 | θmax = 70.0°, θmin = 4.1° |
ω scans | h = −9→11 |
Absorption correction: analytical CrysAlisPro, Agilent Technologies, Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET) (compiled May 16 2011,17:55:39) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) | k = −13→13 |
Tmin = 0.826, Tmax = 0.968 | l = −26→26 |
17468 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.174 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0799P)2 + 1.0855P] where P = (Fo2 + 2Fc2)/3 |
8113 reflections | (Δ/σ)max < 0.001 |
599 parameters | Δρmax = 0.53 e Å−3 |
4 restraints | Δρmin = −0.44 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.9495 (4) | 0.0089 (4) | 0.86434 (16) | 0.0273 (8) | |
C2 | 0.8818 (4) | 0.1008 (4) | 0.81719 (16) | 0.0316 (8) | |
H2 | 0.8754 | 0.0795 | 0.7762 | 0.038* | |
C3 | 0.8290 (4) | 0.2230 (4) | 0.84204 (16) | 0.0324 (8) | |
H3 | 0.7784 | 0.3037 | 0.8217 | 0.039* | |
C4 | 0.8633 (4) | 0.2087 (4) | 0.90482 (16) | 0.0273 (8) | |
C5 | 0.8294 (4) | 0.3134 (4) | 0.94507 (16) | 0.0274 (8) | |
C6 | 0.8582 (4) | 0.3003 (4) | 1.00647 (17) | 0.0274 (7) | |
C7 | 0.8193 (4) | 0.4074 (4) | 1.04849 (17) | 0.0305 (8) | |
H7 | 0.7759 | 0.4984 | 1.039 | 0.037* | |
C8 | 0.8555 (5) | 0.3562 (4) | 1.10404 (17) | 0.0306 (8) | |
H8 | 0.8408 | 0.4044 | 1.141 | 0.037* | |
C9 | 0.9204 (4) | 0.2152 (3) | 1.09724 (16) | 0.0256 (7) | |
C10 | 1.0239 (4) | −0.1277 (4) | 0.85537 (16) | 0.0273 (8) | |
C11 | 0.7547 (4) | 0.4501 (3) | 0.92070 (16) | 0.0282 (8) | |
C12 | 0.8397 (6) | 0.5117 (6) | 0.8944 (3) | 0.079 (2) | |
H12 | 0.9484 | 0.4683 | 0.8926 | 0.094* | |
C13 | 0.7704 (6) | 0.6359 (6) | 0.8703 (4) | 0.083 (2) | |
H13 | 0.8314 | 0.6771 | 0.852 | 0.099* | |
C14 | 0.6130 (4) | 0.7001 (3) | 0.87284 (16) | 0.0264 (7) | |
C15 | 0.5276 (5) | 0.6409 (4) | 0.9002 (2) | 0.0445 (11) | |
H15 | 0.4188 | 0.6856 | 0.9032 | 0.053* | |
C16 | 0.5973 (5) | 0.5159 (4) | 0.9239 (2) | 0.0438 (11) | |
H16 | 0.5361 | 0.4752 | 0.9425 | 0.053* | |
C17 | 1.0508 (4) | −0.1838 (3) | 0.79172 (16) | 0.0279 (8) | |
C18 | 0.9326 (5) | −0.1859 (4) | 0.76185 (18) | 0.0338 (9) | |
H18 | 0.8309 | −0.1498 | 0.7818 | 0.041* | |
C19 | 0.9626 (5) | −0.2407 (4) | 0.70298 (19) | 0.0393 (10) | |
H19 | 0.8815 | −0.2419 | 0.6826 | 0.047* | |
C20 | 1.1103 (5) | −0.2934 (4) | 0.67417 (17) | 0.0361 (9) | |
C21 | 1.2292 (5) | −0.2910 (4) | 0.70291 (18) | 0.0373 (9) | |
H21 | 1.3304 | −0.326 | 0.6826 | 0.045* | |
C22 | 1.1987 (5) | −0.2366 (4) | 0.76196 (17) | 0.0337 (9) | |
H22 | 1.28 | −0.2357 | 0.7822 | 0.04* | |
C23 | −0.1755 (13) | −0.4032 (7) | 0.2379 (3) | 0.114 (4) | |
H23 | −0.1813 | −0.4854 | 0.2407 | 0.137* | |
C24 | −0.1004 (11) | −0.3722 (6) | 0.2801 (3) | 0.098 (3) | |
H24 | −0.0515 | −0.4351 | 0.3099 | 0.118* | |
C25 | −0.0941 (6) | −0.2517 (4) | 0.2801 (2) | 0.0481 (12) | |
C26 | −0.1697 (6) | −0.1681 (5) | 0.2344 (3) | 0.0681 (17) | |
H26 | −0.1754 | −0.0816 | 0.2327 | 0.082* | |
C27 | −0.2355 (6) | −0.2069 (5) | 0.1923 (3) | 0.0651 (16) | |
H27 | −0.2802 | −0.1484 | 0.1603 | 0.078* | |
C28 | −0.0207 (6) | −0.2142 (4) | 0.3270 (2) | 0.0478 (12) | |
C29 | 0.0774 (6) | −0.3079 (5) | 0.3644 (3) | 0.0588 (14) | |
H29 | 0.0998 | −0.3982 | 0.3595 | 0.071* | |
C30 | 0.1410 (7) | −0.2700 (5) | 0.4081 (3) | 0.0644 (15) | |
H30 | 0.2063 | −0.3353 | 0.4335 | 0.077* | |
C31 | −0.0454 (7) | −0.0836 (4) | 0.3366 (2) | 0.0561 (14) | |
H31 | −0.1103 | −0.016 | 0.312 | 0.067* | |
C32 | 0.0224 (7) | −0.0532 (5) | 0.3805 (2) | 0.0586 (15) | |
H32 | 0.0034 | 0.0363 | 0.386 | 0.07* | |
C33 | 0.4985 (7) | 0.2878 (6) | 0.6435 (3) | 0.0697 (17) | |
H33 | 0.4908 | 0.3737 | 0.6354 | 0.084* | |
C34 | 0.4365 (7) | 0.2345 (5) | 0.6048 (3) | 0.0692 (16) | |
H34 | 0.3868 | 0.2843 | 0.5713 | 0.083* | |
C35 | 0.4457 (5) | 0.1098 (5) | 0.6140 (2) | 0.0499 (12) | |
C36 | 0.5189 (7) | 0.0452 (6) | 0.6649 (3) | 0.0661 (16) | |
H36 | 0.5298 | −0.0414 | 0.6736 | 0.079* | |
C37 | 0.5753 (7) | 0.1059 (6) | 0.7024 (3) | 0.0701 (17) | |
H37 | 0.6209 | 0.0603 | 0.7374 | 0.084* | |
C38 | 0.3791 (5) | 0.0507 (5) | 0.5743 (2) | 0.0518 (13) | |
C39 | 0.2766 (6) | 0.1258 (5) | 0.5332 (2) | 0.0556 (13) | |
H39 | 0.2497 | 0.2175 | 0.5304 | 0.067* | |
C40 | 0.2146 (7) | 0.0699 (6) | 0.4970 (3) | 0.0611 (14) | |
H40 | 0.1454 | 0.1235 | 0.4692 | 0.073* | |
C41 | 0.3478 (7) | −0.1349 (6) | 0.5378 (3) | 0.0703 (16) | |
H41 | 0.373 | −0.2264 | 0.5393 | 0.084* | |
C42 | 0.4138 (6) | −0.0842 (5) | 0.5750 (3) | 0.0619 (14) | |
H42 | 0.4841 | −0.1406 | 0.6017 | 0.074* | |
N1 | 0.9354 (3) | 0.0765 (3) | 0.91788 (13) | 0.0255 (6) | |
N2 | 0.9225 (3) | 0.1823 (3) | 1.03668 (13) | 0.0245 (6) | |
N3 | −0.2400 (6) | −0.3224 (4) | 0.1937 (2) | 0.0650 (13) | |
N4 | 0.1154 (5) | −0.1440 (4) | 0.4167 (2) | 0.0555 (11) | |
N5 | 0.2484 (5) | −0.0594 (5) | 0.4993 (2) | 0.0601 (12) | |
N6 | 0.5694 (5) | 0.2248 (5) | 0.6921 (2) | 0.0619 (12) | |
O1 | 0.5987 (4) | 0.9340 (3) | 0.85989 (16) | 0.0468 (8) | |
O2 | 0.5578 (4) | 0.8331 (3) | 0.77288 (12) | 0.0438 (8) | |
O3 | 0.3623 (3) | 0.9093 (3) | 0.85953 (12) | 0.0353 (6) | |
O4 | 1.073 (4) | −0.243 (4) | 0.5621 (17) | 0.043 (6) | 0.5 |
O5 | 1.3143 (19) | −0.4228 (17) | 0.5860 (7) | 0.046 (3) | 0.5 |
O6 | 1.079 (2) | −0.4466 (10) | 0.5964 (6) | 0.057 (4) | 0.5 |
O4B | 1.109 (4) | −0.245 (4) | 0.5559 (18) | 0.042 (6) | 0.5 |
O5B | 1.306 (3) | −0.447 (2) | 0.5844 (9) | 0.117 (10) | 0.5 |
O6B | 1.052 (3) | −0.422 (2) | 0.5937 (9) | 0.111 (8) | 0.5 |
O7 | 1.2327 (3) | −0.0046 (3) | 0.97599 (11) | 0.0311 (6) | |
H7A | 1.2745 | −0.032 | 0.9413 | 0.047* | |
H7B | 1.2277 | 0.0686 | 0.9823 | 0.047* | |
S1 | 0.52566 (11) | 0.85690 (8) | 0.83888 (4) | 0.0294 (2) | |
S2 | 1.14667 (15) | −0.35683 (10) | 0.59723 (4) | 0.0442 (3) | |
Mn1 | 1 | 0 | 1 | 0.0227 (2) | |
O8 | 0.5535 (3) | 1.1354 (2) | 0.93990 (11) | 0.0447 (7) | |
H8A | 0.6146 | 1.1074 | 0.9659 | 0.067* | |
H8B | 0.5616 | 1.0721 | 0.9191 | 0.067* | |
O9 | −0.4426 (4) | −0.3526 (3) | 0.13067 (17) | 0.0741 (12) | |
H9A | −0.3825 | −0.3419 | 0.1517 | 0.111* | |
H9B | −0.4814 | −0.2857 | 0.1099 | 0.111* | |
O10 | 0.5546 (2) | 0.43141 (18) | 0.76702 (9) | 0.0881 (15) | |
H10A | 0.5831 | 0.4823 | 0.7476 | 0.132* | |
H10B | 0.5819 | 0.3633 | 0.7461 | 0.132* | |
O11 | 0.2477 (3) | 1.2320 (2) | 0.98446 (13) | 0.159 (4) | |
H11A | 0.3407 | 1.1949 | 0.9861 | 0.239* | |
H11B | 0.2276 | 1.2548 | 0.9493 | 0.239* | |
O12 | 0.6479 (2) | 0.6008 (2) | 0.70792 (9) | 0.130 (3) | |
H12B | 0.6624 | 0.6257 | 0.6732 | 0.195* | |
H12A | 0.6128 | 0.6637 | 0.7324 | 0.195* | |
O13 | 0.6131 (4) | −0.39526 (18) | 0.59422 (15) | 0.107 (3)* | 0.5 |
H13B | 0.6391 | −0.3935 | 0.5573 | 0.16* | 0.5 |
H13A | 0.656 | −0.363 | 0.6145 | 0.16* | 0.5 |
O15 | 0.8695 (3) | −0.4201 (2) | 0.51535 (18) | 0.077 (2)* | 0.5 |
H15A | 0.7977 | −0.4326 | 0.5049 | 0.115* | 0.5 |
H15B | 0.9425 | −0.4495 | 0.4884 | 0.115* | 0.5 |
O14 | 0.7365 (4) | −0.33992 (18) | 0.59153 (16) | 0.070 (2)* | 0.5 |
H14A | 0.7218 | −0.3823 | 0.5655 | 0.106* | 0.5 |
H14B | 0.8103 | −0.3234 | 0.5808 | 0.106* | 0.5 |
O16 | 0.5871 (4) | −0.45657 (18) | 0.52983 (16) | 0.092 (3)* | 0.5 |
H16A | 0.5231 | −0.4781 | 0.5171 | 0.137* | 0.5 |
H16B | 0.6257 | −0.5054 | 0.5581 | 0.137* | 0.5 |
H6 | 0.985 (13) | −0.412 (7) | 0.589 (18) | 0.137* | 0.5 |
H6B | 0.958 (9) | −0.373 (5) | 0.590 (17) | 0.137* | 0.5 |
H1N | 0.193 (10) | −0.107 (9) | 0.461 (4) | 0.137* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0238 (18) | 0.0307 (18) | 0.0208 (16) | −0.0060 (15) | −0.0018 (13) | 0.0080 (14) |
C2 | 0.031 (2) | 0.0320 (19) | 0.0196 (16) | −0.0026 (16) | −0.0024 (14) | 0.0079 (14) |
C3 | 0.032 (2) | 0.0309 (19) | 0.0230 (17) | −0.0035 (16) | −0.0028 (14) | 0.0103 (15) |
C4 | 0.0257 (18) | 0.0284 (18) | 0.0206 (17) | −0.0061 (15) | 0.0006 (13) | 0.0098 (14) |
C5 | 0.0246 (18) | 0.0254 (17) | 0.0245 (17) | −0.0047 (14) | 0.0009 (13) | 0.0100 (14) |
C6 | 0.0215 (17) | 0.0279 (18) | 0.0275 (18) | −0.0071 (14) | 0.0021 (13) | 0.0061 (14) |
C7 | 0.031 (2) | 0.0233 (17) | 0.0320 (19) | −0.0068 (15) | −0.0070 (15) | 0.0102 (14) |
C8 | 0.037 (2) | 0.0283 (18) | 0.0251 (18) | −0.0127 (16) | −0.0032 (15) | 0.0026 (14) |
C9 | 0.0228 (17) | 0.0274 (18) | 0.0233 (17) | −0.0086 (14) | 0.0008 (13) | 0.0051 (14) |
C10 | 0.0254 (18) | 0.0298 (18) | 0.0210 (16) | −0.0073 (15) | −0.0012 (13) | 0.0056 (14) |
C11 | 0.0286 (19) | 0.0242 (18) | 0.0244 (17) | −0.0051 (15) | −0.0012 (14) | 0.0049 (14) |
C12 | 0.025 (2) | 0.061 (3) | 0.138 (6) | −0.010 (2) | −0.010 (3) | 0.066 (4) |
C13 | 0.030 (3) | 0.059 (3) | 0.146 (6) | −0.014 (2) | 0.001 (3) | 0.065 (4) |
C14 | 0.0280 (18) | 0.0222 (16) | 0.0220 (16) | −0.0046 (14) | −0.0034 (13) | 0.0075 (13) |
C15 | 0.025 (2) | 0.033 (2) | 0.068 (3) | −0.0065 (17) | −0.0080 (19) | 0.022 (2) |
C16 | 0.027 (2) | 0.035 (2) | 0.069 (3) | −0.0133 (18) | −0.0087 (19) | 0.025 (2) |
C17 | 0.032 (2) | 0.0245 (17) | 0.0215 (17) | −0.0069 (15) | −0.0039 (14) | 0.0075 (14) |
C18 | 0.036 (2) | 0.034 (2) | 0.0290 (19) | −0.0131 (17) | −0.0039 (16) | 0.0085 (16) |
C19 | 0.056 (3) | 0.035 (2) | 0.032 (2) | −0.022 (2) | −0.0188 (19) | 0.0110 (17) |
C20 | 0.058 (3) | 0.0247 (18) | 0.0203 (17) | −0.0132 (18) | −0.0058 (17) | 0.0061 (14) |
C21 | 0.046 (2) | 0.031 (2) | 0.0271 (19) | −0.0097 (18) | −0.0003 (17) | 0.0037 (15) |
C22 | 0.037 (2) | 0.033 (2) | 0.0235 (18) | −0.0082 (17) | −0.0024 (15) | 0.0005 (15) |
C23 | 0.230 (11) | 0.047 (3) | 0.065 (4) | −0.054 (5) | −0.048 (5) | 0.018 (3) |
C24 | 0.200 (9) | 0.037 (3) | 0.052 (3) | −0.040 (4) | −0.038 (4) | 0.019 (2) |
C25 | 0.048 (3) | 0.032 (2) | 0.046 (2) | −0.0062 (19) | 0.019 (2) | 0.0083 (18) |
C26 | 0.038 (3) | 0.032 (2) | 0.128 (6) | −0.008 (2) | −0.020 (3) | 0.022 (3) |
C27 | 0.046 (3) | 0.040 (3) | 0.106 (5) | −0.015 (2) | −0.014 (3) | 0.022 (3) |
C28 | 0.047 (3) | 0.029 (2) | 0.051 (3) | −0.0073 (19) | 0.020 (2) | 0.0051 (19) |
C29 | 0.055 (3) | 0.029 (2) | 0.079 (4) | −0.008 (2) | 0.006 (3) | −0.002 (2) |
C30 | 0.057 (3) | 0.037 (3) | 0.081 (4) | −0.004 (2) | −0.001 (3) | −0.001 (3) |
C31 | 0.079 (4) | 0.030 (2) | 0.039 (2) | −0.012 (2) | 0.024 (2) | 0.0041 (19) |
C32 | 0.084 (4) | 0.034 (2) | 0.045 (3) | −0.019 (3) | 0.023 (3) | 0.001 (2) |
C33 | 0.068 (4) | 0.044 (3) | 0.076 (4) | −0.003 (3) | −0.015 (3) | 0.020 (3) |
C34 | 0.072 (4) | 0.047 (3) | 0.069 (4) | −0.004 (3) | −0.024 (3) | 0.023 (3) |
C35 | 0.030 (2) | 0.043 (2) | 0.055 (3) | 0.0002 (19) | 0.008 (2) | 0.021 (2) |
C36 | 0.059 (3) | 0.057 (3) | 0.078 (4) | −0.022 (3) | −0.012 (3) | 0.035 (3) |
C37 | 0.064 (4) | 0.070 (4) | 0.076 (4) | −0.027 (3) | −0.020 (3) | 0.040 (3) |
C38 | 0.032 (2) | 0.051 (3) | 0.051 (3) | −0.002 (2) | 0.012 (2) | 0.015 (2) |
C39 | 0.047 (3) | 0.051 (3) | 0.055 (3) | −0.011 (2) | 0.003 (2) | 0.016 (2) |
C40 | 0.055 (3) | 0.062 (3) | 0.051 (3) | −0.014 (3) | 0.006 (2) | 0.011 (3) |
C41 | 0.056 (3) | 0.054 (3) | 0.079 (4) | −0.006 (3) | 0.003 (3) | 0.001 (3) |
C42 | 0.048 (3) | 0.049 (3) | 0.069 (3) | −0.004 (2) | −0.001 (3) | 0.011 (3) |
N1 | 0.0218 (14) | 0.0258 (15) | 0.0196 (14) | −0.0026 (12) | 0.0008 (11) | 0.0056 (11) |
N2 | 0.0247 (15) | 0.0226 (14) | 0.0186 (14) | −0.0039 (12) | 0.0003 (11) | 0.0064 (11) |
N3 | 0.079 (3) | 0.048 (2) | 0.064 (3) | −0.026 (2) | 0.001 (2) | 0.011 (2) |
N4 | 0.058 (3) | 0.041 (2) | 0.056 (2) | −0.016 (2) | 0.018 (2) | −0.0080 (19) |
N5 | 0.048 (2) | 0.060 (3) | 0.056 (3) | −0.012 (2) | 0.009 (2) | −0.002 (2) |
N6 | 0.046 (2) | 0.060 (3) | 0.068 (3) | −0.012 (2) | −0.008 (2) | 0.021 (2) |
O1 | 0.0454 (18) | 0.0292 (15) | 0.065 (2) | −0.0161 (13) | 0.0007 (15) | −0.0043 (14) |
O2 | 0.0521 (18) | 0.0367 (15) | 0.0225 (13) | −0.0022 (14) | 0.0023 (12) | 0.0076 (11) |
O3 | 0.0346 (15) | 0.0275 (13) | 0.0316 (14) | −0.0033 (11) | 0.0011 (11) | 0.0073 (11) |
O4 | 0.062 (14) | 0.038 (6) | 0.026 (11) | −0.019 (8) | −0.006 (9) | 0.001 (6) |
O5 | 0.062 (6) | 0.040 (5) | 0.019 (4) | −0.007 (5) | 0.008 (4) | −0.015 (3) |
O6 | 0.132 (11) | 0.024 (3) | 0.030 (5) | −0.042 (4) | −0.027 (6) | 0.002 (3) |
O4B | 0.064 (15) | 0.030 (5) | 0.018 (4) | −0.010 (8) | 0.005 (8) | 0.008 (3) |
O5B | 0.137 (15) | 0.075 (12) | 0.053 (8) | 0.047 (9) | −0.051 (8) | −0.023 (7) |
O6B | 0.157 (16) | 0.19 (2) | 0.055 (10) | −0.145 (17) | 0.013 (10) | −0.012 (12) |
O7 | 0.0302 (14) | 0.0332 (14) | 0.0233 (12) | −0.0092 (12) | 0.0041 (10) | 0.0014 (10) |
S1 | 0.0335 (5) | 0.0205 (4) | 0.0247 (4) | −0.0043 (4) | 0.0020 (3) | 0.0046 (3) |
S2 | 0.0720 (8) | 0.0315 (5) | 0.0242 (5) | −0.0167 (5) | −0.0102 (5) | 0.0031 (4) |
Mn1 | 0.0220 (4) | 0.0212 (4) | 0.0170 (4) | −0.0023 (3) | −0.0010 (3) | 0.0069 (3) |
O8 | 0.0351 (16) | 0.0542 (19) | 0.0417 (16) | −0.0150 (14) | −0.0092 (12) | −0.0032 (14) |
O9 | 0.063 (3) | 0.053 (2) | 0.100 (3) | −0.019 (2) | −0.006 (2) | −0.005 (2) |
O10 | 0.119 (4) | 0.072 (3) | 0.070 (3) | −0.031 (3) | −0.048 (3) | 0.027 (2) |
O11 | 0.064 (3) | 0.123 (5) | 0.296 (9) | −0.061 (3) | 0.081 (4) | −0.128 (6) |
O12 | 0.197 (7) | 0.125 (5) | 0.095 (4) | −0.107 (5) | 0.061 (4) | −0.061 (4) |
C1—N1 | 1.376 (5) | C33—C34 | 1.374 (9) |
C1—C10 | 1.397 (5) | C33—H33 | 0.95 |
C1—C2 | 1.437 (5) | C34—C35 | 1.377 (8) |
C2—C3 | 1.350 (6) | C34—H34 | 0.95 |
C2—H2 | 0.95 | C35—C36 | 1.397 (7) |
C3—C4 | 1.436 (5) | C35—C38 | 1.462 (8) |
C3—H3 | 0.95 | C36—C37 | 1.374 (9) |
C4—N1 | 1.380 (5) | C36—H36 | 0.95 |
C4—C5 | 1.390 (5) | C37—N6 | 1.328 (7) |
C5—C6 | 1.392 (5) | C37—H37 | 0.95 |
C5—C11 | 1.500 (5) | C38—C39 | 1.393 (7) |
C6—N2 | 1.383 (5) | C38—C42 | 1.405 (8) |
C6—C7 | 1.427 (5) | C39—C40 | 1.357 (8) |
C7—C8 | 1.345 (5) | C39—H39 | 0.95 |
C7—H7 | 0.95 | C40—N5 | 1.346 (7) |
C8—C9 | 1.437 (5) | C40—H40 | 0.95 |
C8—H8 | 0.95 | C41—N5 | 1.338 (8) |
C9—N2 | 1.381 (5) | C41—C42 | 1.361 (9) |
C9—C10i | 1.393 (5) | C41—H41 | 0.95 |
C10—C9i | 1.393 (5) | C42—H42 | 0.95 |
C10—C17 | 1.494 (5) | N1—Mn1 | 2.012 (3) |
C11—C12 | 1.365 (6) | N2—Mn1 | 2.011 (3) |
C11—C16 | 1.377 (6) | N4—H1N | 1.46 (9) |
C12—C13 | 1.381 (7) | N5—H1N | 1.28 (9) |
C12—H12 | 0.95 | O1—S1 | 1.446 (3) |
C13—C14 | 1.377 (6) | O2—S1 | 1.451 (3) |
C13—H13 | 0.95 | O3—S1 | 1.458 (3) |
C14—C15 | 1.356 (6) | O4—S2 | 1.42 (4) |
C14—S1 | 1.776 (3) | O5—S2 | 1.465 (16) |
C15—C16 | 1.384 (6) | O6—S2 | 1.425 (15) |
C15—H15 | 0.95 | O6—H6 | 0.851 (10) |
C16—H16 | 0.95 | O6—H6B | 1.13 (5) |
C17—C22 | 1.388 (5) | O4B—S2 | 1.46 (4) |
C17—C18 | 1.391 (6) | O5B—S2 | 1.44 (2) |
C18—C19 | 1.390 (6) | O6B—S2 | 1.41 (2) |
C18—H18 | 0.95 | O6B—H6 | 0.62 (4) |
C19—C20 | 1.379 (6) | O6B—H6B | 0.851 (10) |
C19—H19 | 0.95 | O7—Mn1 | 2.245 (3) |
C20—C21 | 1.384 (6) | O7—H7A | 0.8208 |
C20—S2 | 1.785 (4) | O7—H7B | 0.8182 |
C21—C22 | 1.391 (5) | Mn1—N2i | 2.011 (3) |
C21—H21 | 0.95 | Mn1—N1i | 2.012 (3) |
C22—H22 | 0.95 | Mn1—O7i | 2.245 (3) |
C23—N3 | 1.321 (8) | O8—H8A | 0.8226 |
C23—C24 | 1.373 (11) | O8—H8B | 0.8258 |
C23—H23 | 0.95 | O9—H9A | 0.8296 |
C24—C25 | 1.382 (8) | O9—H9B | 0.8297 |
C24—H24 | 0.95 | O10—H10A | 0.8263 |
C25—C26 | 1.390 (8) | O10—H10B | 0.8274 |
C25—C28 | 1.476 (8) | O11—H11A | 0.8201 |
C26—C27 | 1.356 (9) | O11—H11B | 0.8214 |
C26—H26 | 0.95 | O12—H12B | 0.8219 |
C27—N3 | 1.318 (7) | O12—H12A | 0.8233 |
C27—H27 | 0.95 | O13—H13B | 0.8213 |
C28—C29 | 1.394 (7) | O13—H13A | 0.8256 |
C28—C31 | 1.400 (6) | O13—H14A | 1.2319 |
C29—C30 | 1.361 (8) | O13—H16B | 1.441 |
C29—H29 | 0.95 | O15—H15A | 0.8237 |
C30—N4 | 1.345 (7) | O15—H15B | 0.8244 |
C30—H30 | 0.95 | O14—H13A | 1.0074 |
C31—C32 | 1.350 (8) | O14—H14A | 0.8156 |
C31—H31 | 0.95 | O14—H14B | 0.8249 |
C32—N4 | 1.342 (7) | O16—H13B | 1.2329 |
C32—H32 | 0.95 | O16—H16A | 0.8327 |
C33—N6 | 1.342 (7) | O16—H16B | 0.8243 |
N1—C1—C10 | 126.0 (3) | N6—C33—H33 | 118.3 |
N1—C1—C2 | 109.6 (3) | C34—C33—H33 | 118.3 |
C10—C1—C2 | 124.3 (3) | C33—C34—C35 | 120.7 (5) |
C3—C2—C1 | 107.2 (3) | C33—C34—H34 | 119.6 |
C3—C2—H2 | 126.4 | C35—C34—H34 | 119.6 |
C1—C2—H2 | 126.4 | C34—C35—C36 | 115.5 (6) |
C2—C3—C4 | 107.5 (3) | C34—C35—C38 | 122.2 (5) |
C2—C3—H3 | 126.3 | C36—C35—C38 | 122.3 (5) |
C4—C3—H3 | 126.3 | C37—C36—C35 | 120.6 (5) |
N1—C4—C5 | 126.3 (3) | C37—C36—H36 | 119.7 |
N1—C4—C3 | 109.4 (3) | C35—C36—H36 | 119.7 |
C5—C4—C3 | 124.4 (3) | N6—C37—C36 | 123.4 (5) |
C4—C5—C6 | 124.6 (3) | N6—C37—H37 | 118.3 |
C4—C5—C11 | 117.6 (3) | C36—C37—H37 | 118.3 |
C6—C5—C11 | 117.9 (3) | C39—C38—C42 | 115.8 (6) |
N2—C6—C5 | 125.4 (3) | C39—C38—C35 | 121.5 (5) |
N2—C6—C7 | 109.7 (3) | C42—C38—C35 | 122.7 (5) |
C5—C6—C7 | 124.8 (3) | C40—C39—C38 | 120.9 (5) |
C8—C7—C6 | 107.5 (3) | C40—C39—H39 | 119.5 |
C8—C7—H7 | 126.3 | C38—C39—H39 | 119.5 |
C6—C7—H7 | 126.3 | N5—C40—C39 | 121.9 (6) |
C7—C8—C9 | 107.6 (3) | N5—C40—H40 | 119 |
C7—C8—H8 | 126.2 | C39—C40—H40 | 119 |
C9—C8—H8 | 126.2 | N5—C41—C42 | 121.8 (6) |
N2—C9—C10i | 126.4 (3) | N5—C41—H41 | 119.1 |
N2—C9—C8 | 109.2 (3) | C42—C41—H41 | 119.1 |
C10i—C9—C8 | 124.4 (3) | C41—C42—C38 | 120.8 (6) |
C9i—C10—C1 | 123.2 (3) | C41—C42—H42 | 119.6 |
C9i—C10—C17 | 117.8 (3) | C38—C42—H42 | 119.6 |
C1—C10—C17 | 119.0 (3) | C1—N1—C4 | 106.3 (3) |
C12—C11—C16 | 118.4 (4) | C1—N1—Mn1 | 127.4 (2) |
C12—C11—C5 | 121.4 (4) | C4—N1—Mn1 | 126.3 (2) |
C16—C11—C5 | 120.2 (4) | C9—N2—C6 | 106.0 (3) |
C11—C12—C13 | 121.1 (4) | C9—N2—Mn1 | 127.1 (2) |
C11—C12—H12 | 119.5 | C6—N2—Mn1 | 126.9 (2) |
C13—C12—H12 | 119.5 | C27—N3—C23 | 117.8 (6) |
C14—C13—C12 | 120.1 (4) | C32—N4—C30 | 117.6 (5) |
C14—C13—H13 | 120 | C32—N4—H1N | 120 (4) |
C12—C13—H13 | 120 | C30—N4—H1N | 122 (4) |
C15—C14—C13 | 119.2 (4) | C41—N5—C40 | 118.8 (6) |
C15—C14—S1 | 121.2 (3) | C41—N5—H1N | 123 (4) |
C13—C14—S1 | 119.6 (3) | C40—N5—H1N | 118 (4) |
C14—C15—C16 | 120.7 (4) | C37—N6—C33 | 116.3 (6) |
C14—C15—H15 | 119.7 | S2—O6—H6 | 115 (3) |
C16—C15—H15 | 119.7 | S2—O6—H6B | 98 (2) |
C11—C16—C15 | 120.5 (4) | S2—O6B—H6 | 142 (5) |
C11—C16—H16 | 119.7 | S2—O6B—H6B | 116 (3) |
C15—C16—H16 | 119.7 | Mn1—O7—H7A | 116.4 |
C22—C17—C18 | 119.2 (3) | Mn1—O7—H7B | 109.2 |
C22—C17—C10 | 118.9 (3) | H7A—O7—H7B | 110.6 |
C18—C17—C10 | 121.9 (3) | O1—S1—O2 | 111.6 (2) |
C19—C18—C17 | 120.3 (4) | O1—S1—O3 | 113.68 (18) |
C19—C18—H18 | 119.9 | O2—S1—O3 | 112.49 (18) |
C17—C18—H18 | 119.9 | O1—S1—C14 | 106.19 (19) |
C20—C19—C18 | 119.8 (4) | O2—S1—C14 | 106.04 (17) |
C20—C19—H19 | 120.1 | O3—S1—C14 | 106.21 (17) |
C18—C19—H19 | 120.1 | O6B—S2—O4 | 101.7 (19) |
C19—C20—C21 | 120.8 (4) | O4—S2—O6 | 112.7 (18) |
C19—C20—S2 | 119.6 (3) | O6B—S2—O5B | 111.0 (14) |
C21—C20—S2 | 119.6 (3) | O4—S2—O5B | 123.1 (16) |
C20—C21—C22 | 119.2 (4) | O6—S2—O5B | 100.0 (12) |
C20—C21—H21 | 120.4 | O6B—S2—O4B | 113 (2) |
C22—C21—H21 | 120.4 | O6—S2—O4B | 122.5 (18) |
C17—C22—C21 | 120.8 (4) | O5B—S2—O4B | 109.6 (16) |
C17—C22—H22 | 119.6 | O6B—S2—O5 | 123.4 (12) |
C21—C22—H22 | 119.6 | O4—S2—O5 | 115.9 (15) |
N3—C23—C24 | 122.1 (6) | O6—S2—O5 | 112.4 (10) |
N3—C23—H23 | 118.9 | O4B—S2—O5 | 102.0 (15) |
C24—C23—H23 | 118.9 | O6B—S2—C20 | 106.1 (8) |
C23—C24—C25 | 121.6 (6) | O4—S2—C20 | 103.7 (16) |
C23—C24—H24 | 119.2 | O6—S2—C20 | 106.7 (6) |
C25—C24—H24 | 119.2 | O5B—S2—C20 | 109.8 (8) |
C24—C25—C26 | 114.0 (6) | O4B—S2—C20 | 107.6 (16) |
C24—C25—C28 | 122.3 (5) | O5—S2—C20 | 104.2 (6) |
C26—C25—C28 | 123.6 (4) | N2—Mn1—N2i | 180.00 (9) |
C27—C26—C25 | 121.6 (5) | N2—Mn1—N1 | 90.43 (12) |
C27—C26—H26 | 119.2 | N2i—Mn1—N1 | 89.57 (12) |
C25—C26—H26 | 119.2 | N2—Mn1—N1i | 89.57 (12) |
N3—C27—C26 | 122.8 (6) | N2i—Mn1—N1i | 90.43 (12) |
N3—C27—H27 | 118.6 | N1—Mn1—N1i | 180.00 (18) |
C26—C27—H27 | 118.6 | N2—Mn1—O7 | 90.10 (11) |
C29—C28—C31 | 116.3 (5) | N2i—Mn1—O7 | 89.90 (11) |
C29—C28—C25 | 121.4 (4) | N1—Mn1—O7 | 90.98 (11) |
C31—C28—C25 | 122.4 (5) | N1i—Mn1—O7 | 89.02 (11) |
C30—C29—C28 | 120.1 (5) | N2—Mn1—O7i | 89.90 (11) |
C30—C29—H29 | 120 | N2i—Mn1—O7i | 90.10 (11) |
C28—C29—H29 | 120 | N1—Mn1—O7i | 89.02 (11) |
N4—C30—C29 | 122.8 (6) | N1i—Mn1—O7i | 90.98 (11) |
N4—C30—H30 | 118.6 | O7—Mn1—O7i | 180 |
C29—C30—H30 | 118.6 | H8A—O8—H8B | 108.2 |
C32—C31—C28 | 120.5 (5) | H9A—O9—H9B | 107.5 |
C32—C31—H31 | 119.7 | H10A—O10—H10B | 108.9 |
C28—C31—H31 | 119.7 | H11A—O11—H11B | 111 |
N4—C32—C31 | 122.7 (5) | H12B—O12—H12A | 109.8 |
N4—C32—H32 | 118.6 | H14A—O13—H16B | 96.2 |
C31—C32—H32 | 118.6 | H14A—O14—H14B | 112.4 |
N6—C33—C34 | 123.5 (6) | H16A—O16—H16B | 108.4 |
N1—C1—C2—C3 | 0.7 (5) | C38—C35—C36—C37 | −177.7 (5) |
C10—C1—C2—C3 | −176.6 (4) | C35—C36—C37—N6 | −2.4 (10) |
C1—C2—C3—C4 | 0.1 (5) | C34—C35—C38—C39 | −13.4 (7) |
C2—C3—C4—N1 | −0.9 (5) | C36—C35—C38—C39 | 164.7 (5) |
C2—C3—C4—C5 | 178.5 (4) | C34—C35—C38—C42 | 166.6 (5) |
N1—C4—C5—C6 | −2.8 (6) | C36—C35—C38—C42 | −15.3 (7) |
C3—C4—C5—C6 | 177.9 (4) | C42—C38—C39—C40 | 0.6 (7) |
N1—C4—C5—C11 | 178.1 (3) | C35—C38—C39—C40 | −179.4 (4) |
C3—C4—C5—C11 | −1.2 (6) | C38—C39—C40—N5 | 0.3 (8) |
C4—C5—C6—N2 | −0.8 (6) | N5—C41—C42—C38 | 0.2 (9) |
C11—C5—C6—N2 | 178.3 (3) | C39—C38—C42—C41 | −0.9 (8) |
C4—C5—C6—C7 | −178.0 (4) | C35—C38—C42—C41 | 179.2 (5) |
C11—C5—C6—C7 | 1.2 (6) | C10—C1—N1—C4 | 176.0 (4) |
N2—C6—C7—C8 | −1.6 (4) | C2—C1—N1—C4 | −1.2 (4) |
C5—C6—C7—C8 | 176.0 (4) | C10—C1—N1—Mn1 | −5.8 (5) |
C6—C7—C8—C9 | 1.0 (4) | C2—C1—N1—Mn1 | 176.9 (2) |
C7—C8—C9—N2 | −0.1 (4) | C5—C4—N1—C1 | −178.1 (4) |
C7—C8—C9—C10i | 178.0 (4) | C3—C4—N1—C1 | 1.3 (4) |
N1—C1—C10—C9i | 7.6 (6) | C5—C4—N1—Mn1 | 3.8 (5) |
C2—C1—C10—C9i | −175.6 (4) | C3—C4—N1—Mn1 | −176.9 (2) |
N1—C1—C10—C17 | −170.1 (3) | C10i—C9—N2—C6 | −178.9 (4) |
C2—C1—C10—C17 | 6.7 (6) | C8—C9—N2—C6 | −0.9 (4) |
C4—C5—C11—C12 | −89.9 (6) | C10i—C9—N2—Mn1 | 2.0 (5) |
C6—C5—C11—C12 | 90.9 (6) | C8—C9—N2—Mn1 | −179.9 (2) |
C4—C5—C11—C16 | 89.4 (5) | C5—C6—N2—C9 | −176.0 (4) |
C6—C5—C11—C16 | −89.8 (5) | C7—C6—N2—C9 | 1.5 (4) |
C16—C11—C12—C13 | −1.3 (10) | C5—C6—N2—Mn1 | 3.0 (5) |
C5—C11—C12—C13 | 178.0 (6) | C7—C6—N2—Mn1 | −179.5 (2) |
C11—C12—C13—C14 | 0.2 (12) | C26—C27—N3—C23 | −0.9 (10) |
C12—C13—C14—C15 | 1.3 (10) | C24—C23—N3—C27 | −2.5 (13) |
C12—C13—C14—S1 | −177.4 (6) | C31—C32—N4—C30 | 0.1 (8) |
C13—C14—C15—C16 | −1.8 (8) | C29—C30—N4—C32 | 0.3 (8) |
S1—C14—C15—C16 | 176.9 (4) | C42—C41—N5—C40 | 0.8 (8) |
C12—C11—C16—C15 | 0.8 (8) | C39—C40—N5—C41 | −1.0 (8) |
C5—C11—C16—C15 | −178.5 (4) | C36—C37—N6—C33 | 2.6 (9) |
C14—C15—C16—C11 | 0.8 (8) | C34—C33—N6—C37 | −1.1 (9) |
C9i—C10—C17—C22 | −70.6 (5) | C15—C14—S1—O1 | 133.6 (4) |
C1—C10—C17—C22 | 107.2 (4) | C13—C14—S1—O1 | −47.7 (5) |
C9i—C10—C17—C18 | 108.6 (4) | C15—C14—S1—O2 | −107.5 (4) |
C1—C10—C17—C18 | −73.6 (5) | C13—C14—S1—O2 | 71.1 (5) |
C22—C17—C18—C19 | 0.2 (6) | C15—C14—S1—O3 | 12.3 (4) |
C10—C17—C18—C19 | −179.0 (4) | C13—C14—S1—O3 | −169.0 (5) |
C17—C18—C19—C20 | 0.2 (6) | C19—C20—S2—O6B | −39.3 (11) |
C18—C19—C20—C21 | −0.8 (6) | C21—C20—S2—O6B | 144.3 (11) |
C18—C19—C20—S2 | −177.1 (3) | C19—C20—S2—O4 | 67.4 (16) |
C19—C20—C21—C22 | 1.1 (6) | C21—C20—S2—O4 | −109.0 (16) |
S2—C20—C21—C22 | 177.5 (3) | C19—C20—S2—O6 | −51.8 (8) |
C18—C17—C22—C21 | 0.2 (6) | C21—C20—S2—O6 | 131.8 (8) |
C10—C17—C22—C21 | 179.4 (4) | C19—C20—S2—O5B | −159.4 (11) |
C20—C21—C22—C17 | −0.8 (6) | C21—C20—S2—O5B | 24.2 (11) |
N3—C23—C24—C25 | 2.9 (15) | C19—C20—S2—O4B | 81.3 (16) |
C23—C24—C25—C26 | 0.0 (11) | C21—C20—S2—O4B | −95.1 (16) |
C23—C24—C25—C28 | 176.8 (7) | C19—C20—S2—O5 | −170.9 (7) |
C24—C25—C26—C27 | −3.3 (9) | C21—C20—S2—O5 | 12.7 (7) |
C28—C25—C26—C27 | 180.0 (5) | C9—N2—Mn1—N1 | 177.1 (3) |
C25—C26—C27—N3 | 3.9 (10) | C6—N2—Mn1—N1 | −1.7 (3) |
C24—C25—C28—C29 | 15.6 (8) | C9—N2—Mn1—N1i | −2.9 (3) |
C26—C25—C28—C29 | −167.9 (5) | C6—N2—Mn1—N1i | 178.3 (3) |
C24—C25—C28—C31 | −164.1 (6) | C9—N2—Mn1—O7 | −91.9 (3) |
C26—C25—C28—C31 | 12.3 (7) | C6—N2—Mn1—O7 | 89.3 (3) |
C31—C28—C29—C30 | 1.1 (7) | C9—N2—Mn1—O7i | 88.1 (3) |
C25—C28—C29—C30 | −178.7 (5) | C6—N2—Mn1—O7i | −90.7 (3) |
C28—C29—C30—N4 | −0.9 (9) | C1—N1—Mn1—N2 | −179.2 (3) |
C29—C28—C31—C32 | −0.7 (7) | C4—N1—Mn1—N2 | −1.4 (3) |
C25—C28—C31—C32 | 179.1 (4) | C1—N1—Mn1—N2i | 0.8 (3) |
C28—C31—C32—N4 | 0.1 (8) | C4—N1—Mn1—N2i | 178.6 (3) |
N6—C33—C34—C35 | −0.6 (10) | C1—N1—Mn1—O7 | 90.7 (3) |
C33—C34—C35—C36 | 0.9 (8) | C4—N1—Mn1—O7 | −91.5 (3) |
C33—C34—C35—C38 | 179.1 (5) | C1—N1—Mn1—O7i | −89.3 (3) |
C34—C35—C36—C37 | 0.5 (8) | C4—N1—Mn1—O7i | 88.5 (3) |
Symmetry code: (i) −x+2, −y, −z+2. |
Acknowledgements
The technical and human support provided by SGIker (UPV/EHU) is gratefully acknowledged. The authors would also like to express their gratitude to Dr Ana Martinez Amesti at SGIker (UPV/EHU) for helping with the TEM measurements. EA thanks the UPV/EHU for funding.
Funding information
The following funding is acknowledged: Ministerio de Economía y Competitividad, Secretaría de Estado de Investigación, Desarrollo e Innovación [award No. MAT2016-76739-R (AEI/FEDER, UE); award No. MAT2014-52085-C2-2-P]; Eusko Jaurlaritza (award No. IT-630-13).
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