pubs.acs.org/crystal Article Supramolecular Isomerism in Cobalt(II) Coordination Polymers Built from 3,5-Bis(trifluoromethyl)benzoate and 4,4′-Bipyridine Francesco Papi, Albert Rosado, Oriol Vallcorba, Arianna E. Lanza, Mauro Gemmi,* Núria Portolés-Gil, Ana M. López-Periago, Concepción Domingo, and José A. Ayllón* Cite This: Cryst. Growth Des. 2022, 22, 4463−4471 Read Online ACCESS Metrics & More Article Recommendations * sı Supporting Information See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles. Downloaded via UNIV AUTONOMA DE BARCELONA on July 6, 2022 at 08:00:50 (UTC). ABSTRACT: The reaction of [Co2(H2O)(TFMBz)4(py)4] (1) (TFMBz: 3,5- bis(trifluoromethyl)benzoate; py: pyridine) with 4,4′-bipyridine (bpy) in different solvents yields four coordination polymers with unlikely structures but with the same stoichiometry. Three of them contain similar ladder chains consisting of binuclear nodes “Co2(TFMBz)4”, in which two of the TFMBz ligands show bidentate bridge coordination, double linked to each adjacent node by bpy but packed in different fashions. The different packing affects the compound porosity; thus, [Co2(TFMBz)4(bpy)2]n (2), precipitated using low-polarity solvents such as supercritical CO2 (scCO2), n-butyl acetate, or heptane and also in acetonitrile, is microporous, with a surface area of 330 m2 g−1, showing the N2 adsorption/desorption isotherm at 77 K with a gate-opening effect at low relative pressures (P/P0 = 0.05). The isomer [Co2(TFMBz)4(bpy)2]n (3), synthesized in ethoxyethanol, presents a surface area of 230 m2 g−1. A third chain packing isomer, [Co2(TFMBz)4(bpy)2]n (4), is obtained in acetone and has only non-interconnected voids. Finally, precursor 1 is combined with bpy in a highly polar solvent such as water to give [Co(TFMBz)2(bpy)]n (5). In this isomer, all the carboxylate units act as bidentate bridging ligands, generating chains that are interlinked by bpy, leading to a 2D network, which after packing yields a non-porous structure. The resolution of structures 2−5 is only possible with the recently developed 3D electron diffraction method based on the collection of diffraction patterns on sub-micron-sized single crystals. The variation of magnetic susceptibility as a function of temperature is also measured. Overall, our work provides insightful information on the complex landscape of metal−organic framework solids that are formed by crystallization using different solvent media. ■ INTRODUCTION Research in metal−organic frameworks (MOFs) and coordi- can be anticipated from the used set of precursor entities, including metal centers, counter anions, and linkers. However, nation polymers (CPs) is a continuously advancing area of often this is not the situation because of the poor under- development. Much effort has been devoted to the design and standing of the role played by different experimental controlled crystallization of these coordination networks, parameters in the growth of a defined CP. Moreover, the shaped with transition metal atoms and multifunctional packing in a 1D or 2D network is still more difficult to bridging ligands, owing to their potential key applications in anticipate due to the subtle attractive or repulsive force that adsorption, separation, heterogeneous catalysis, and so prevails in the crystal lattice. The preparation of MOF isomers forth.1−5 The phenomenon of polymorphism, for example, is serendipitous in nature; thus, achieving controlled synthesis of supramolecular isomers remains a long-term challenge.10 the ability of a crystalline material to adopt different crystal The tendency of some MOFs to polymorphism has been structures, is of paramount importance to determine the related to the low energy differences between the lattice energy chemical and physical properties of the material.6 The concept for diverse polymorphs of only a few kcal mol−1.6 Experimental of polymorphism, clearly established in the pharmaceutical factors, such as the temperature, reagent concentration, pH, industry for molecular compounds, was extended to oligomeric solvent, presence of additional species in the medium and polymeric coordination compounds by Zaworotko et al., (additives, template/guests), crystallization method, and so defining supramolecular isomerism as the existence of more forth, would determine the particular isomer obtained in a than one superstructure for a given set of components.7,8 Supramolecular isomerism is of particular importance in CPs since the superstructure plays an essential role in determining Received: April 7, 2022 the properties of these crystalline materials. This concept is Revised: May 19, 2022 challenging, but it is crucial for fundamental understanding to Published: June 2, 2022 speed up the development of CP-based functional materials.9 Concepts of reticular chemistry are exploited to generate application-driven MOFs, with a structure that, in principle, © 2022 The Authors. Published by American Chemical Society https://doi.org/10.1021/acs.cgd.2c00406 4463 Cryst. Growth Des. 2022, 22, 4463−4471 Crystal Growth & Design pubs.acs.org/crystal Article designed synthetic process.9,11 Among all these factors, the use precise supramolecular isomer that is formed. Advanced of different solvents to precipitate different supramolecular techniques for crystal structure elucidation, namely, single- isomers is relatively common.11−13 Different solvent properties crystal diffraction analysis using synchrotron radiation and 3D may favor the formation of distinct isomers: polarity, ability of electron diffraction (3D ED), were needed to describe the solvent molecules to coordinate with the metal ion, binding to precipitated compounds. The use of these techniques plays a the crystal nucleus, formation of loose aggregates of several key role in correctly assessing the structural and physical solvent molecules that can serve as effective templates, and so differences between the isomers even with the characterization forth. Thus, varying the energy barrier leads to different of isomers of different dimensionality. The description of the polymorphs.14,15 overall results aims to demonstrate the general under-rated The number of polymorphs identified from a specific importance of structural isomerism in molecular crystal combination of metal nodes and ligands is generally related to engineering and provide a basis for understanding and the number of different experimental conditions assayed, rationalizing supramolecular isomorphism in MOFs and CPs. ■ although frequently scientists focused the scientific study on a given polymorph rather than on the search and character- EXPERIMENTAL SECTION ization of possible alternative isomers. Moreover, polymorphs Materials. Co(CH3COO)2·4H2O, 3,5-bis(trifluoromethyl)benzoic that present some difficulties to be obtained as single crystals acid (HTFMBz), pyridine (py) and 4,4′-bipyridine (bpy) and all the are prone to be discarded. Thus, the importance of solvents (acetonitrile, ethoxyethanol, heptane, acetone, and n- polymorphism in MOFs and CPs is under-represented in the butylacetate) were purchased from Sigma-Aldrich and used without scientific literature and should be more widely investigated. further purification. Ultrapure water (Milli-Q system, conductivity Supramolecular isomerism is usually referred to CPs with a lower than 0.05 μS cm−1) was used. Compressed CO2 (99.95%) was framework that contains the same nodes and linkers in the supplied by Carburos Metálicos S.A. Synthesis of Compounds 1−5. Synthesis of [Co2(H2O)- same ratio but differ in the nature or number of solvent (TFMBz)4(py)4] (1). HTFMBz (1.555 g, 6.02 mmol) and Co- molecules incorporated to the framework, thus presenting (CH3COO)2·4H2O were dissolved in methanol (100 mL), and the different crystal structures. This concept implies small resulting fuchsia solution was evaporated on a hot plate at 65 °C, differences in the composition and, strictly speaking, should giving a highly viscous oil. This product was heated on a ventilated be defined as pseudo-polymorphism.16−18 Examples of supra- furnace at 100 °C for 1 h to eliminate possible traces of the acetic acid molecular isomerism in CPs, with a fixed stoichiometry for the by-product. The final residue was dissolved in ethanol (100 mL) framework constituents and pending or occluded solvents, are together with 1.0 mL (12.7 mmol) of pyridine. Then, 25.0 mL of water was added. The resulting pink solution was allowed to slowly scarce.19,20 Pure isomerism in MOFs and CPs is an area evaporate at room temperature, and a crystalline solid, which appears particularly interesting from a scientific point of view. Indeed, after partial evaporation of the ethanol, was filtered and washed elimination of the differences in the composition (solvent) of repeatedly with water and, finally, dried on air. The yield was about 90 the polymorphic materials would help in the analysis of the wt %. Anal. Calcd for C56H34O9N4F24Co2 (1480.7 g mol−1): C, 45.42; structure−property relationship.21 There are many reports in H, 2.31; N, 3.78. Found: C, 45.54; H, 2.14; N, 3.74%. the literature describing the synthesis of two isomers, while Synthesis of [Co2(TFMBz)4(bpy)2]n (2). This compound can be only few have given details of three pure isomers.19,22 In this obtained in supercritical CO2 (scCO2) or in conventional organic work, we give one of the first examples of a system with four solvents, such as acetonitrile, n-butylacetate, or heptane. Route A. Reactions in scCO2 were performed in a 5 mL Pyrex vial different isomers, which were crystallized from a new dinuclear placed into a 100 mL high pressure autoclave with two opposite cobalt(II) benzoate having trifluoromethyl substituents in sapphire windows (TharDesign). The vial was charged with 200 mg positions 3 and 5 (TFMBz). This metal node was reacted with of compound 1 (0.135 mmol) and 50 mg (0.320 mmol) bpy. A small 4,4′-bipyridine (bpy), one of the most studied ditopic linkers magnetic stirrer was also added, and the vial was finally capped with in CPs (Scheme 1).23 Although both the metal ligand TFMBz cellulose filter paper. Experiments were performed at 20 MPa and 60 and the linker bpy are mostly rigid molecules with only a °C. The vial was stirred at 500 rpm. After a running period of 20 h, limited rotational degree of freedom, the results of this work the product was washed with fresh scCO2 to eliminate any excess of show how the solvent used in precipitation determines the bpy ligand, free pyridine by-product, and other possible residues. The autoclave was then depressurized and cooled down to room temperature to recover a green powder. Yield ca. 70 wt %. Anal. Scheme 1. Structure of the bpy Linker and the TFMBz Calcd for C56H28O8N4F24Co2 (1458.7 g mol−1): C, 46.11; H, 1.93; N, Ligand with Three Different Coordination Modes for CoII 3.84. Found: C, 46.32; H, 2.07; N, 3.69%. Found in Compounds 1−5: Bidentate Bridging Route B. The same product previously obtained in scCO2 was Coordination Mode (μ2:η1,η1), Monodentate, and precipitated by dissolution of the same precursors in the same ratio in Chelation, Respectively several conventional solvents, specifically heptane, acetonitrile, or n- butylacetate. In the case of heptane, it was necessary to use boiling solvent to favor the solubility of precursor 1, and also, it was the choice for acetonitrile to favor crystallinity. For the three solvents, the recovered precipitates were washed twice with the same solvent (hot) to eliminate residual reagents. Synthesis of [Co2(TFMBz)4(bpy)2]n (3). A solution of compound 1 (120 mg, 0.081 mmol) in ethoxyethanol at 50 °C was mixed with a solution of bpy (26.0 mg, 0.167 mmol) in the same solvent and temperature. After mixing, a crystalline precipitate was obtained with a yield of ca. 62 wt %. Anal. Calcd for C56H28O8N4F24Co2 (1458.7 g mol−1): C, 46.11; H, 1.93; N, 3.84. Found: C, 45.87; H, 2.03; N, 3.60%. Synthesis of [Co2(TFMBz)4(bpy)2]n (4). A solution of compound 1 (120 mg, 0.081 mmol) in acetone at room temperature was mixed 4464 https://doi.org/10.1021/acs.cgd.2c00406 Cryst. Growth Des. 2022, 22, 4463−4471 Crystal Growth & Design pubs.acs.org/crystal Article with a solution of bpy (26.0 mg, 0.167 mmol) in the same solvent and type of coordination and the other half shows the chelating temperature. After mixing, a crystalline precipitate was obtained in a coordination mode (Scheme 1). yield of ca. 83 wt %. Anal. Calcd for C56H28O8N4F24Co2 (1458.7 g Crystal Structures. Crystal Structure of [Co2(H2O)- mol−1): C, 46.11; H, 1.93; N, 3.84. Found: C, 46.12; H, 1.80; N, (TFMBz)4(py)4] (1). Compound 1 belongs to the triclinic 3.66%. Synthesis of [Co(TFMBz)2(bpy)]n (5). 209 mg of compound 1 crystal system, with the space group P1̅ (2). The asymmetric (0.141 mmol) was dissolved in 100 mL of boiling water, and then a unit contains two CoII atoms, four TFMBz, four pyridine, and solution of 45 mg (0.288 mmol) of bpy in hot water was added under one aqua ligand. In each binuclear molecule, the two CoII are vigorous agitation, leading to the precipitation of a pink solid. The held together through two syn,syn μ2:η1,η1-carboxylate bridges heating and stirring were maintained for 30 min. Then, the solid was from TFMBz ligands and one bridging aqua ligand, as shown filtered, washed with hot water, and dried in air. Yield ca. 91 wt %. in Figure 1. The distorted octahedral geometry around each Anal. Calcd for C56H28O8N4F24Co2 (1458.7 g mol−1): C, 46.11; H, 1.93; N, 3.84. Found: C, 46.31; H, 1.92; N, 3.65%. Detailed procedures for the characterization of the materials are included in the Supporting Information. ■ RESULTS AND DISCUSSION Synthesis and Characterization. A binuclear cobalt [Co2(H2O)(TFMBz)4(py)4] (1), including benzoate ligands with two trifluoromethyl groups and pyridine that could be obtained in as a pure crystalline material in high yields was chosen as a node precursor for the synthesis of CPs. This pyridine adduct has the advantage of being soluble in a wide variety of solvents, from heptane to water, as well as in supercritical CO2. While compound 1 is partially soluble in many solvents of intermediate polarity at room temperature, heating of the solvent to boiling or near-boiling temperature is Figure 1. Crystal structure of compound 1. Color code: C gray; O necessary to achieve a significant dissolution in either polar red; N blue, Co pink, and F green. Hydrogen atoms, except those of water or nonpolar heptane. the aqua ligand (in white), are omitted for clarity. Hydrogen bond Initial trials showed that very different results are obtained as between the aqua and the carboxylate ligands are depicted as dotted green lines. a function of the solvent choice, leading, in some cases, to mixtures of compounds. Powder XRD characterization allows metal ion is completed by one oxygen from an additional to determine some solvents that allow to precipitate four monodentate TFMBz ligand and two nitrogen donor atoms different compounds, even if elemental analysis (C, H, and N) from tw o py r id ine li g ands, l ea ding t o a loc al suggested that all of them have the same stoichiometry, [(Npy)2(OTFMBz)3(Owater)] coordination sphere around each [Co(TFMBz)2(bpy)]. Crystal structure elucidation confirmed metal center. The hydrogen atoms of the aqua bridge are these findings. Hence, [Co2(TFMBz)4(bpy)2]n (2) was involved in intramolecular O(9)−H···O−C hydrogen bond, obtained in scCO2, heptane, n-butylacetate, or acetonitrile, with the uncoordinated O atom of the monodentate TFMBz while the remaining three isomers were obtained in ligand (Table 1). The Owater−H distance was about 2 times ethoxyethanol, [Co 2 (TFMBz) 4 (bpy) 2 ] n (3), acetone, [Co2(TFMBz)4(bpy)2]n (4), and water, [Co(TFMBz)2(bpy)]n (5). Table 1. H Bond Interactions in Compound 1a A priori, it is expected for all the isomers that the bpy linker D−H···A D−H H···A D···A D−H···A displaces the four pyridine ligands present in 1 during the O(9)−H(9A)···O(2) 0.86(3) 1.81(3) 2.613(1) 155(3) reaction, thus leading to a 3D framework if the orientation of O(9)−H(9B)···O(6) 0.85(3) 1.72(3) 2.540(2) 164(3) bpy preserves the original orientation of the initial pyridine a Hydrogen-bond geometry (Å, deg). ligands. Actually, 3D-MOFs in which subunits of a dinuclear CoII carboxylate with an aqua bridge are connected by the bpy linker24 or by other ditopic N,N-bipyridine ligands25,26 have lower than the H···OTFMBz distance, confirming that the been reported. However, in all the essayed experimental bridging O atom belongs to water. The two Co−O(9) bond conditions of this work, the aqua bridge present in 1 was lost length distances of 2.145(1) and 2.157(1) Å, the Co(1)− during the pyridine substitution reaction by bpy to produce O(9)−Co(2) angle of 116.87(5),° and the Co−Npy bond different CPs, independently of the solvent used. lengths in the range 2.138−2.176 Å are comparable to those Interestingly, ATR-FTIR spectra reflected variations in the reported for other aqua bridged binuclear CoII carboxy- coordination mode of the TFMBz ligand of the four isomers. lates.27−30 Hence, significant differences were observed in the region Crystal Structures of Compounds 2, 3, and 4. The reaction corresponding to the νas(COO−) band, in the 1650−1550 between compound 1 and 4,4′-bipyridine in the mentioned cm−1 ranges and also in the 850−700 cm−1 fingerprint region solvents (different from water) yielded, after displacement of (Figure S1). In these regions, 2, 3, and 4 show a similar pattern the pyridine and aqua ligand of the precursor, three pure between them, while 5 shows a different one. This could be isomers containing all similar 1D ladder type chains. explained after crystal structure elucidation, which established Compound 2 can be prepared in scCO2, heptane, n- that in isomer 5, all TFMBz ligands show the bidentate butylacetate, or acetonitrile; compound 3 is obtained in bridging coordination mode (μ2:η1,η1), while in the other three ethoxyethanol; and compound 4 precipitates in acetone. In the isomers (2−4), only half of the TFMBz ligands display this three cases, roughly planar binuclear “Co2(TFMBz)4” nodes 4465 https://doi.org/10.1021/acs.cgd.2c00406 Cryst. Growth Des. 2022, 22, 4463−4471 Crystal Growth & Design pubs.acs.org/crystal Article are observed, where the two CoII ions are double bridged by carboxylate groups of two of the TFMBz ligands, while each of the two additional TFMBz ligands coordinates to one CoII through a chelating carboxylate (Figures 2 and S2). Four Figure 2. Binuclear Co2(TFMBz)4 SBUs and ladder chains observed in the crystal structure of compound 3. Color code: C gray; O red; N blue, Co pink, and F green. H atoms are omitted. H atoms are omitted. bipyridine linkers connect each binuclear subunit with its nearest neighbors in opposite directions, forming ladder chains of approximately 11.6 Å step and leading to a 1D CP (Figures 2 and S2). Ladder chains containing carboxylate ligands and CoII and bpy linkers, similar to those found in compounds 2− 4, have previously been described.31−33 The almost planar Figure 3. Different packing of the ladder chains in the crystal binuclear “Co2(TFMBz)4“ motif can be regarded as a structures of compounds 2 (a), 3 (b), and 4 (c). 2 contains secondary building unit (SBU) similar to some reported disordered bpy and TFMBz ligands, not shown for clarity. Color code: C gray; O red; N blue, Co pink, and F green. H atoms are molecular compounds that contain analogous binuclear omitted. clusters bonded to four monodentate pyridines.34−36 The most fascinating aspect of the crystal structures of compounds 2−4 is their different crystal packing despite being perpendicular direction shows negligible interpenetration, formed by similar ladder chains. In Figure 3, the crystal although the position of the “Co2(TFMBz)4” SBU in the structures of the three compounds are viewed along the chains, chain axis direction shifts steadily (Figure S5). Besides the π−π to envisage the differences in the packing. Each binuclear stacking interactions observed in 3, the three alternative subunit projects four TFMBz ligands roughly perpendicular to packings favor inter-chain contacts that are established through the chain axis in different directions. The relative arrangement the trifluoromethyl groups of the TFMBz ligand (F···F of these TFMBz ligands determines how ligands belonging to contacts) and through the hydrogen atom of the bpy ligand close neighbor chains interact and therefore the crystal (F···H−C contacts). Interestingly, compounds 2, 3, and 4 are packing. porous materials albeit to a different extent. Void analysis using In compound 2, each chain, with the propagation direction Mercury software shows that the accessible space gives rise to a parallel to the crystallographic a axis, has two neighbors in the c crystal channel in isomer 2 (22.2% of unit cell volume, 1645 direction and two in the b direction (Figure 3a). The inter- Å3) and in isomer 3 (15.1%, 465 Å3), while 4 (6.5%, 101 Å3) chain interaction is stronger with the nearest neighbor, found only contains non-interconnected voids (Figure S6). in the c direction, in which the protruding TFMBz ligand Crystal Structure of Compound 5. When the reaction interdigitate clearly. Contrarily, when the nearest neighbor is in between compound 1 and bpy is carried out in water, the the perpendicular direction (c axis), the interpenetration is totally different product 5 is obtained. In 5, all TFMBz much less pronounced (Figure S3). Besides, alternated carboxylate groups show the bidentate bridge coordination orientations of the binuclear SBU are observed when looking mode, leading to the formation of chains (Figure 4a) instead of along the c direction (Figure S3). Isomer 3 also shows a chain the discrete binuclear subunits found in the former propagation direction parallel to the crystallographic a axis but compounds. In these chains, in which CoII ions are separated a different packing in which the intertwined chains give rise to by about 5.0 Å, the four coordinating oxygens define a plane. supramolecular layers parallel to the ab plane (Figure 3b). In To complete the approximately octahedral coordination of this case, a tighter interdigitation is observed since in the void CoII, the two axial positions, perpendicular to this O4 plane, are between two “Co2(TFMBz)4” of each chain, protruding occupied by nitrogens from bpy linkers. Consequently, chains TFMBz of two other neighbor chains, interdigitate (instead are connected by the bpy linkers, ultimately defining a 2D CP of only one as observed for 2), thus favoring weak π−π (Figure 4b). Structure analysis reveals a compact packing of stacking interactions (Cg···Cg 3.85 Å) (Figure S4). Finally, layers with weak intermolecular contacts, namely, dispersive compound 4 shows another different packing of chains (Figure forces established between trifluoromethyl groups from 3c). In this case, the interdigitation between close neighbors adjacent layers (Figure 4c). In 5, however, the formation of due to the protruding TFMBz, lies roughly in middle position the bridged chain of CoII ions over the planar “Co2(TFMBz)4“ between two successive “Co2(TFMBz)4” SBU in a chain, as it SBU sterically prevents TFMBz ligands to interact by π−π was also observed for 2 (Figure S5). The nearest neighbor in a stacking, in favor of a tight assembly of layers resulting in a 4466 https://doi.org/10.1021/acs.cgd.2c00406 Cryst. Growth Des. 2022, 22, 4463−4471 Crystal Growth & Design pubs.acs.org/crystal Article indicates that many authors do not take into consideration differences in the content of crystallization solvents,11 although the strict criterion to name isomerism would require exactly the same composition.40 Overall, the crystal structures of 2−4 represent a major example of packing isomerism and offer interesting clues to understand how a packing mode over the others can be favored as a function of the crystallization solvent. The crystal packing shown by compound 2 seems to be preferred in case of solvents with low polarity and low dielectric constant, notably scCO2, heptane, and n-butylace- tate. Gradually increasing solvent polarity induces the precipitation of 3, in ethoxyethanol, and of 4, in acetone. Interestingly, these three supramolecular isomers contain similar ladder type chains but packed in different modes. Therefore, the solvent properties strongly influence the inter- chain interactions and, consequently, the crystal packing observed. Acetonitrile is a particularly interesting case as it leads to the formation of 2, despite its relatively high polarity. Figure 4. Crystal structure of compound 5. (a) Chains of CoII ions, This suggests that additional effects are actually in play due to separated by about 5.0 Å, generated, thanks to the bridging bidentate the differences in the interactions between the solvent and TFMBz ligands. (b) Completion of the coordination sphere of the growing crystal nucleus. The use of water as a solvent CoII by N atoms from ditopic bpy linkers gives rise to a 2D determines a different behavior of the TFMBz ligand, leading framework. (c) Structure analysis reveals a compact packing of layers, to the formation of CoII chains in lieu of the discrete SBU with weak intermolecular contacts through trifluoromethyl groups. observed in the organic solvents. The combination of these Color code: C gray; O red; N blue, Co pink, and F green. H atoms are omitted. In (b), only the carboxylate group of each TFMBz ligand is chains with the bpy linker runs to the formation of a shown for clarity. bidimensional CP. Supramolecular isomers that show different dimensionality are scarce and usually based on the use of flexible linkers.9,13,44−48 Thus, the structures of compounds 2− non-porous compound. Only one structure has been found 5 are overall very interesting and allow to understand and based on chains of CoII supported by bridging carboxylates and rationalize how the solvent choice deeply affects the products interconnected by bpy, defined as a 2D framework.37 obtained at a fixed stoichiometry. Moreover, although CoII species of different nuclearity Compound Pore Characteristics and Surface Area. (dimers, trimers, tetramers, etc.)38 based on carboxylate bridges Compounds surface area, determined by N2 adsorption/ have been described, only one compound in which these desorption at 77 K, denote clear differences between the four bridges extend into a 1D polymer has been previously supramolecular isomers: 2 (surface area of 330 m2 g−1) and 3 reported.39 In this compound, the coordination of CoII is (surface area of 230 m2 g−1) are porous materials, while 4 and completed by monodentate pyridines, so the overall structure 5 are not. The N2 isotherm of 2 (Figure 5) shows two distinct is 1D. Interestingly, all these compounds have been prepared sections in the adsorption branch. A first noteworthy hydrothermally, hence suggesting that water favors the adsorption episode occurs in the region of very low relative formation of bridging carboxylates. pressure (P/P0), the slope of the branch clearly being reduced Polymorphism and Solvent Effect. As mentioned as P/P0 reaches the critical value of 0.05. This behavior is previously, polymorphism based on the different packing of followed by a sudden increase in the amount of N2 adsorbed identical substructures is rare.40 Only a few examples of CPs for P/P0 greater than 0.05, and finally, a well-defined plateau is that present crystal structures differentiated basically by the recorded. Interestingly, the adsorption and desorption paths in packing mode of similar chains have been described. A clear the isotherm differ considerably, showing a hysteresis loop that example found in the literature is the two crystalline only closes at pressures near to vacuum. This hysteresis should polymorphs of compound catena-(μ2-2,5-dimethylpyrazine- not be correlated with condensation in mesopores because the N,N′)-dibromido-zinc(II) that contain topologically identical P/P0 values of sudden increase and closing hysteresis are very chains packed in a different fashion.41 Furthermore, for the low.49,50 Moreover, the presence of mesopores was not found closely related compounds {[Mn3(hpdc)2(H2O)6]3·2H2O}n by the performed crystallographic structural determination, and {[Mn3(hpdc)2(H2O)6]3·H2O} (H3hpdc = 2-hydroxypyr- which highlighted only the presence of micropores. SEM imidine-4,6-dicarboxylic acid), the two elucidated structures characterization showed the precipitation of micrometric contain similar one-dimensional chain components but packed particles (Figure S7); therefore, the hypothesis of the with different orientations, either staggered or plywood-like generation of mesopores due to aggregation of nanoparticles stacked, respectively. Both compounds differ only in the was also discarded. The structural analysis indicated that the content of crystallization water.42,43 Recently, three polymers framework of 2 involves interconnected pores, although its of the type [(Cu(hfa)2)(3-tpt)]n [hfa = hexafluoroacetylacet- visualization is not trivial due to ligand disorder present in the onate, 3-tpt = 2,4,6-tris(3-pyridyl)-1,3,5-triazine] have been structure. Adsorption data shows that most of the pore volume described, whose composition only differs in the incorporated was not accessible at low pressures. A plausible explanation crystallization solvent molecules but forms structures differing could be that, at the low temperature of measurements, in dimensionality and porosity.12 Actually, a survey of the channels were initially blocked likely due to the disordered scientific literature regarding MOF supramolecular isomerism TFMBz ligands, but pressure and/or partial filling prompted 4467 https://doi.org/10.1021/acs.cgd.2c00406 Cryst. Growth Des. 2022, 22, 4463−4471 Crystal Growth & Design pubs.acs.org/crystal Article some minor structural modifications related to increased TFMBZ ordering that makes void space available. The desorption branch indicates that very low-pressure values must be attained to empty the pores. Conversely, isomer 3 shows the common type I adsorption/desorption isotherm, suggesting that the bottleneck between voids is not an effective barrier to the diffusion of N2; this is probably because at 77 K, the trifluoromethyl group rotation is fast enough to eliminate any impediment (Figure 5).51,52 Finally, isomers 4 and 5 do not display a significant surface area, as expected from the presence of non-interconnected voids in 4, resulting in non- effective porosity, and compact packing in 5. Magnetic Properties. The variable-temperature magnetic susceptibility of the five compounds (1−5) was measured under 1000 Oe in the temperature range 2−300 K (Figure 6). In a first approximation, χ(T) data for all compounds show a good fitting to the Curie−Weiss law, χ(T) = C/(T − θCW), at temperatures above 4−35 K (Table 2). The negative values of Table 2. Fitting Parameters of the Curie−Weiss Analysis for Compounds 1−5 range linearity χT value at 300 K compound (K) C (emu K mol−1) θCW (K) (emu K mol−1) 1 10−300 2.95 −23.89 2.70 2 20−300 2.39 −13.79 2.27 3 20−300 2.43 −9.44 2.34 4 4−300 2.71 −12.10 2.58 5 35−300 2.72 −15.19 2.58 Figure 5. 77 K N2 adsorption/desorption isotherms: (a) for θCW indicate dominant antiferromagnetic exchange interac- compound 2, showing two consecutive cycles; color code: 1st tions in addition to single-ion spin−orbital coupling (Figure adsorption, black; 1st desorption red; 2nd adsorption green; 2nd S8). For all compounds, the χT value per CoII atom at 300 K is desorption blue, and (b) for compound 3. significantly larger than the spin-only value (1.87 emu K mol−1) for S = 3/2 ions, indicative of significant contribution from the unquenched orbital momentum of CoII.53,54 Figure 6. χT vs temperature curve for compounds 1−5 at an applied field of 1000 Oe. 4468 https://doi.org/10.1021/acs.cgd.2c00406 Cryst. Growth Des. 2022, 22, 4463−4471 Crystal Growth & Design pubs.acs.org/crystal Article In 2−5, the dominant exchange pathway may be established clues about the possible design of supramolecular isomers, through bridging carboxylate ligands in each dimer and which could be easily extended to the supramolecular through the aqua bridge in compound 1, as for all cases the engineering of MOFs and CPs of different components and CoII···CoII distances are too large to support direct through- stoichiometries. It must be pointed out that the detailed study space interaction. Despite the bpy linker connection, it is of supramolecular isomerism has been possible only because improbable that any significant interaction takes place between 3D ED can give structural information on sub-micrometric adjacent binuclear subunits in the chains of compounds 2−4; crystals. Without this possibility, the polycrystalline powders indeed, their magnetic behavior resembles that reported for would have remained in the vials as unknown compounds and binuclear cobalt complexes.55 Besides, the bulky nature of sooner or later would have been discarded. We can foresee that TFMBz prevents interactions among neighboring chains; all by applying this approach, many more MOFs and CPs would the CoII···CoII distances between atoms belong to different show a more complex phase diagram with several stable and subunits being always much larger than the intradimer CoII··· metastable forms. Finally, as the synthesis and crystallization CoII distance. Antiferromagnetic coupling is also supported by procedure must not necessarily produce large crystals, a far the small χT values at low temperature found for compounds greater number of synthesis routes could be investigated, hence 1−4.53 Compound 5 presents different chains of CoII centers allowing in depth studies on how factors in the synthesis instead of the binuclear unit but the antiferromagnetic determine the crystal structure obtained. interactions dominate above 50 K, as for the former compounds. Differences arise on cooling, when ferromagnetic interactions become more important as denoted by the ■ * ASSOCIATED CONTENT sı Supporting Information variations in the χT values at low temperature. Magnetic The Supporting Information is available free of charge at characterizations of similar 2D compounds, based on https://pubs.acs.org/doi/10.1021/acs.cgd.2c00406. interconnected CoII carboxylate chains, have remarkably not been reported in the literature. Crystallographic data; ATR-FTIR spectra; binuclear ■ Co2(TFMBz)4 secondary building units and ladder CONCLUSIONS chains; details of chain packing; void space analysis; SEM micrograph; thermal variation of 1/χ; powder X- Supramolecular isomerism in MOFs and CPs is a major ray diffractograms; and fit of the rigid-body Rietveld challenge in modern chemistry despite its crucial role in refinement (PDF) determining the chemical and physical properties of materials for different technological applications. Due to the limited Accession Codes information available in the literature, the design of supra- CCDC 2141822−2141823, 2141825, 2144631, and 2144678 molecular isomers still remains a complex task and the contain the supplementary crystallographic data for this paper. influence of a variety of experimental factors, such as solvent These data can be obtained free of charge via www.ccdc.ca- medium, temperature, reagents concentration, and presence of m.ac.uk/data_request/cif, or by emailing data_request@ccdc. additives and guests, is not yet fully understood. The choice of cam.ac.uk, or by contacting The Cambridge Crystallographic solvent medium, either for synthesis or crystallization, is Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: particularly relevant in this regard, and our results demonstrate +44 1223 336033. how the properties of the solvent used actually drive the formation of different polymorphs despite the same stoichiometry. Our results have pointed out how the physical ■ AUTHOR INFORMATION Corresponding Authors properties of the solvent employed, mostly its polarity, affect Mauro Gemmi − Center for Materials Interfaces, Electron the supramolecular isomer obtained as they favor specific inter- Crystallography, Istituto Italiano di Tecnologia, 56025 chain non-covalent interactions in the frameworks formed by Pontedera, Italy; orcid.org/0000-0001-9542-3783; CoII, bpy, and TFMBz. Low polarity solvents consistently lead Email: mauro.gemmi@iit.it to structures based on binuclear CoII complexes, where CF3··· José A. Ayllón − Departamento de Química, Universidad F3C interactions from the TFMBz ligands appear to be Autónoma de Barcelona, 08193 Bellaterra, Barcelona, determinant (compound 2). Increasing the polarity of the Spain; orcid.org/0000-0001-7965-7424; solvent favors a different packing of the ladder chains Email: JoseAntonio.Ayllon@uab.es characterized by π−π stacking interactions between TFMBz ligands of adjacent binuclear CoII complexes (compound 3, Authors obtained in ethoxyethanol). A further increase of solvent Francesco Papi − Center for Materials Interfaces, Electron polarity, using acetone, leads to a third isomer containing Crystallography, Istituto Italiano di Tecnologia, 56025 similar ladder-type chains consisting of SBUs connected by Pontedera, Italy bpy linkers and interacting through CF3···F3C contacts Albert Rosado − Instituto de Ciencia de Materiales de (compound 4). However, the fact that compound 2 is Barcelona (ICMAB-CSIC), 08193 Bellaterra, Barcelona, obtained also in acetonitrile, a solvent with a polarity higher Spain; orcid.org/0000-0003-3222-9566 than acetone, shows that other properties of the solvent can Oriol Vallcorba − ALBA Synchrotron Light Source, 08290 likely determine which isomer precipitate. The different Cerdanyola del Vallés, Barcelona, Spain packing of the chains in 2−4 influences the porosity, as 2 Arianna E. Lanza − Center for Materials Interfaces, Electron and 3 show a porous nature, while 4 displays non- Crystallography, Istituto Italiano di Tecnologia, 56025 interconnected voids. Furthermore, water, a high polarity Pontedera, Italy; orcid.org/0000-0002-7820-907X solvent, promotes the formation of a remarkable 2D framework Núria Portolés-Gil − Instituto de Ciencia de Materiales de defined by chains of CoII ions bridged by bidentate TFMBz Barcelona (ICMAB-CSIC), 08193 Bellaterra, Barcelona, ligands (compound 5). Together, these results give interesting Spain 4469 https://doi.org/10.1021/acs.cgd.2c00406 Cryst. Growth Des. 2022, 22, 4463−4471 Crystal Growth & Design pubs.acs.org/crystal Article Ana M. López-Periago − Instituto de Ciencia de Materiales de (10) Gheorghe, A.; Imaz, I.; van der Vlugt, J. I.; Maspoch, D.; Barcelona (ICMAB-CSIC), 08193 Bellaterra, Barcelona, Tanase, S. Tuning the supramolecular isomerism of MOF-74 by Spain; orcid.org/0000-0002-3777-3205 controlling the synthesis conditions. Dalton Trans. 2019, 48, 10043− Concepción Domingo − Instituto de Ciencia de Materiales de 10050. Barcelona (ICMAB-CSIC), 08193 Bellaterra, Barcelona, (11) Karmakar, A.; Paul, A.; Pombeiro, A. J. L. Recent advances on supramolecular isomerism in metal organic frameworks. CrystEng- Spain; orcid.org/0000-0002-6976-8283 Comm 2017, 19, 4666−4695. Complete contact information is available at: (12) Portolés-Gil, N.; López-Periago, A. M.; Borrás, A.; Fraile, J.; https://pubs.acs.org/10.1021/acs.cgd.2c00406 Solano, E.; Vallcorba, O.; Planas, J. G.; Ayllón, J. A.; Domingo, C. Tuning the Structure and Flexibility of Coordination Polymers via Author Contributions Solvent Control of Tritopic Triazine Conformation during Crystal- The manuscript was written through contributions of all lization. Cryst. Growth Des. 2020, 20, 3304−3315. authors. All authors have given approval to the final version of (13) Ju, H.; Park, I.-H.; Lee, E.; Kim, S.; Jung, J. H.; Ikeda, M.; the manuscript. Habata, Y.; Lee, S. S. Guest-triggered assembly of zinc(II) supramolecular isomers with accompanying dimensional change and Notes reversible single-crystal-to-single-crystal transformation. CrystEng- The authors declare no competing financial interest. Comm 2016, 18, 1600−1608. This work was done in the framework of the doctoral program (14) Zhang, J.-P.; Huang, X.-C.; Chen, X.-M. Supramolecular “Chemistry” of the Universitadad Autónoma de Barcelona by isomerism in coordination polymers. Chem. Soc. Rev. 2009, 38, 2385. A.R. who acknowledge the FPI grant. (15) Pavlishchuk, A. V.; Kolotilov, S. V.; Zeller, M.; Shvets, O. V.; ■ ACKNOWLEDGMENTS This work was supported by the Spanish Ministry of Science Fritsky, I. O.; Lofland, S. E.; Addison, A. W.; Hunter, A. D. Magnetic and Sorption Properties of Supramolecular Systems Based on Pentanuclear Copper(II) 12-Metallacrown-4 Complexes and Isomeric Phthalates: Structural Modeling of the Different Stages of Alcohol and Innovation MICINN through the Severo Ochoa Program Sorption. Eur. J. Inorg. Chem. 2011, 2011, 4826−4836. for Centers of Excellence (CEX2019-000917-S) and the (16) Peng, Y.-F.; Ge, H.-Y.; Li, B.-Z.; Li, B.-L.; Zhang, Y. Three Spanish National Plan of Research with projects PID2020- Supramolecular Isomers of Square Grid Networks from the Assembly 115631GB-I00. F.P., A.E.L., and M.G. would like to thank of a Flexible Spacer and Co(NCS)2 : Structures and Polymer Regione Toscana for funding the purchase of the ASI Transformation. Cryst. Growth Des. 2006, 6, 994−998. MEDIPIX detector through the FELIX project (POR CREO (17) Wang, S.; Peng, Y.; Wei, X.; Zhang, Q.; Wang, D.; Dou, J.; Li, FERS 2014−2020). The measures for the elucidation of the D.; Bai, J. Temperature-dependent supramolecular isomerism in three crystal structure of compound 1 were performed at the zinc coordination polymers with pamoic acid and 1,4-bis(imidazole-1- XALOC beamline at ALBA Synchrotron with the collaboration ylmethyl)-benzene. CrystEngComm 2011, 13, 5313. of ALBA staff. (18) Liu, G.-l.; Song, J.-B.; Qiu, Q.-m.; Li, H. Syntheses, structures, ■ and magnetic properties of three supramolecular isomeric Cu(II) REFERENCES square grid networks: solvents effect on the ligand linkages. CrystEngComm 2020, 22, 1321−1329. (1) Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. The (19) Masaoka, S.; Tanaka, D.; Nakanishi, Y.; Kitagawa, S. Reaction- Chemistry and Applications of Metal-Organic Frameworks. Science Temperature-Dependent Supramolecular Isomerism of Coordination 2013, 341, 1230444. Networks Based on the Organometallic Building Block[CuI2(μ2- (2) Silva, P.; Vilela, S. M. F.; Tomé, J. P. C.; Almeida Paz, F. A. BQ)(μ2-OAc)2]. Angew. Chem., Int. Ed. 2004, 43, 2530−2534. Multifunctional metal-organic frameworks: from academia to (20) Galet, A.; Muñ oz, M. C.; Martínez, V.; Real, J. A. industrial applications. Chem. Soc. Rev. 2015, 44, 6774−6803. Supramolecular isomerism in spin crossover networks with aurophilic (3) Ji, Z.; Wang, H.; Canossa, S.; Wuttke, S.; Yaghi, O. M. Pore interactions. Chem. Commun. 2004, 20, 2268−2269. Chemistry of Metal−Organic Frameworks. Adv. Funct. Mater. 2020, (21) Ye, Z.-M.; He, C.-T.; Xu, Y.-T.; Krishna, R.; Xie, Y.; Zhou, D.- 30, 2000238. D.; Zhou, H.-L.; Zhang, J.-P.; Chen, X.-M. A New Isomeric Porous (4) Wang, Q.; Astruc, D. State of the Art and Prospects in Metal− Coordination Framework Showing Single-Crystal to Single-Crystal Organic Framework (MOF)-Based and MOF-Derived Nanocatalysis. Structural Transformation and Preferential Adsorption of 1,3- Chem. Rev. 2020, 120, 1438−1511. (5) Rojas, S.; Horcajada, P. Metal−Organic Frameworks for the Butadiene from C4 Hydrocarbons. Cryst. Growth Des. 2017, 17, Removal of Emerging Organic Contaminants in Water. Chem. Rev. 2166−2171. 2020, 120, 8378−8415. (22) Gao, X.; Fu, A.-Y.; Wang, Y.-Y. Shape-Asymmetry Supra- (6) Tan, Y. S.; Otero-de-la-Roza, A.; Jotani, M. M.; Tiekink, E. R. T. molecular Isomerism in Asymmetrical Ligand PCPs and the Snap Frozen! Capturing Two Metastable Polymorphs in a Expression Method of Three-Level Isomerism. Inorg. Chem. 2016, Tetramorphic One-Dimensional Coordination Polymer Constructed 55, 4330−4334. from Cadmium, Dithiophosphate, and 4-Pyridinealdazine. Cryst. (23) Biradha, K.; Sarkar, M.; Rajput, L. Crystal engineering of Growth Des. 2020, 20, 3272−3283. coordination polymers using 4,4′-bipyridine as a bond between (7) Moulton, B.; Zaworotko, M. J. From Molecules to Crystal transition metal atoms. Chem. Commun. 2006, 4169−4179. Engineering: Supramolecular Isomerism and Polymorphism in (24) Shen, J.-B.; Wu, X.-Y.; Chen, X.-J.; Zhao, G.-L. Poly[[μ-aqua- Network Solids. Chem. Rev. 2001, 101, 1629−1658. bis-(μ-4,4′-bi-pyridine-κ2N:N′)bis-(μ-3-hy-droxy-adamantane-1-car- (8) Hennigar, T. L.; MacQuarrie, D. C.; Losier, P.; Rogers, R. D.; boxyl-ato-κ2O:O′)bis-(3-hy-droxy-adamantane-1-carboxyl-ato-κO)- Zaworotko, M. J. Supramolecular Isomerism in Coordination dicobalt(II)] hepta-hydrate]. Acta Crystallogr., Sect. E: Struct. Rep. Polymers: Conformational Freedom of Ligands in [Co(NO3)2(1,2- Online 2011, 67, m558−m559. bis(4-pyridyl)ethane)1.5]n. Angew. Chem., Int. Ed. 1997, 36, 972−973. (25) Hsu, S.-C.; Chiang, P.-S.; Liu, H.-K.; Lo, S.-H.; Lin, C.-H. (9) Lee, E.; Hongu, H.; Temma, H.; Toya, M.; Ikeda, M.; Kuwahara, Multi-Dimensional Cobalt(II) and Nickel(II) Coordination Polymers. S.; Habata, Y. Solvent-Dependent Formations of Supramolecular J. Chin. Chem. Soc. 2012, 59, 18−27. Isomers and a Single-Crystal to Single-Crystal Transformation from a (26) Wang, X.; Liu, G.; Chen, B.; Bi, Y.; Lin, H. A 3-D metal-organic Cyclic Dimer Complex to a One-Dimensional Coordination Polymer. framework constructed with cobalt(II), 1,3-di(4-pyridyl)propane Cryst. Growth Des. 2020, 20, 3284−3292. (bpp) and 3,5-dinitrobenzoate (DNBA) with methyl-3,5-dinitroben- 4470 https://doi.org/10.1021/acs.cgd.2c00406 Cryst. Growth Des. 2022, 22, 4463−4471 Crystal Growth & Design pubs.acs.org/crystal Article zoate (MDNBA) by in-situ synthesis as a guest. J. Coord. Chem. 2008, and Lonsdaleite Network Topologies Based on a Tripodal Flexible 61, 1635−1644. Ligand. Cryst. Growth Des. 2011, 11, 5182−5187. (27) Fontanet, M.; Rodríguez, M.; Fontrodona, X.; Romero, I.; (45) Song, J.-F.; Luo, J.-J.; Jia, Y.-Y.; Xin, L.-D.; Lin, Z.-Z.; Zhou, R.- Teixidor, F.; Viñas, C.; Aliaga-Alcalde, N. Carving a 1D CoII- S. Solvent-induced construction of two zinc supramolecular isomers: carboranylcarboxylate system by using organic solvents to create synthesis, framework flexibility, sensing properties, and adsorption of stable trinuclear molecular analogues: complete structural and dye molecules. RSC Adv. 2017, 7, 36575−36584. magnetic studies. Dalton Trans. 2016, 45, 10916−10927. (46) Biswas, S.; Gómez-García, C. J.; Clemente-Juan, J. M.; (28) Tomkowicz, Z.; Ostrovsky, S.; Foro, S.; Calvo-Perez, V.; Haase, Benmansour, S.; Ghosh, A. Supramolecular 2D/3D Isomerism in a W. Magnetooptical and Structural Investigations of Five Dimeric Compound Containing Heterometallic CuII2CoII Nodes and Cobalt(II) Complexes Mimicking Metalloenzyme Active Sites. Inorg. Dicyanamide Bridges. Inorg. Chem. 2014, 53, 2441−2449. Chem. 2012, 51, 6046−6055. (47) Jia, Y.; Li, H.; Guo, Q.; Zhao, B.; Zhao, Y.; Hou, H.; Fan, Y. (29) Karmakar, A.; Sarma, R. J.; Baruah, J. B. Synthesis and Template-Induced Structural Isomerism of Pyridine-2,3-dicarboxylate characterisation of dinuclear and mononuclear Cobalt (II) benzoate and PbII with Similar High Stability and Different Fluorescent complexes. Polyhedron 2007, 26, 1347−1355. Properties. Eur. J. Inorg. Chem. 2012, 2012, 3047−3053. (30) Burley, J. C.; Prior, T. J. m2-Aqua-bis-(m2-trifluoro-aceto-k2- (48) Wu, J.-Y.; Hsiao, C.-C.; Chiang, M.-H. Concomitant O,O’)bis-[bis-(pyridine- kN)(trifluoro-acetato kO)cobalt(II)]. Acta Crystallization of Genuine Supramolecular Isomeric Rhombus Grid Crystallogr., Sect. E: Struct. Rep. Online 2005, 61, m1422−m1424. and Ribbon. Cryst. Growth Des. 2014, 14, 4321−4328. (31) Ma, D.-Y.; Guo, H.-F.; Lu, K.; Pan, Y.; Qin, L.; Blatov, V. A. A (49) Coudert, F.-X.; Evans, J. D. Nanoscale metamaterials: Meta- 1D → 3D Two-Fold Interpenetration Array Formed by Hydrogen- MOFs and framework materials with anomalous behavior. Coord. Bonding Interactions. Z. Anorg. Allg. Chem. 2012, 638, 992−995. Chem. Rev. 2019, 388, 48−62. (32) Song, Y. J.; Kwak, H.; Lee, Y. M.; Kim, S. H.; Lee, S. H.; Park, (50) Park, J.; Howe, J. D.; Sholl, D. S. How Reproducible Are B. K.; Jun, J. Y.; Yu, S. M.; Kim, C.; Kim, S.-J.; Kim, Y. Metal-directed Isotherm Measurements in Metal−Organic Frameworks? Chem. supramolecular assembly of metal(II) benzoates (M=Co, Ni, Cu, Zn, Mater. 2017, 29, 10487−10495. Mn, and Cd) with 4,4′-bipyridine: Effects of metal coordination (51) Wang, C.; Zhou, D.-D.; Gan, Y.-W.; Zhang, X.-W.; Ye, Z.-M.; modes and novel catalytic activities. Polyhedron 2009, 28, 1241−1252. Zhang, J.-P. A partially fluorinated ligand for two super-hydrophobic (33) Lu, J.; Yu, C.; Niu, T.; Paliwala, T.; Crisci, G.; Somosa, F.; porous coordination polymers with classic structures and increased Jacobson, A. J. One-Dimensional Coordination Polymers of Cobalt porosities. Natl. Sci. Rev. 2021, 8, nwaa094. with 4,4‘-Bipyridine: Syntheses and Structures. Inorg. Chem. 1998, 37, (52) Holden, D.; Chong, S. Y.; Chen, L.; Jelfs, K. E.; Hasell, T.; 4637−4640. Cooper, A. I. Understanding static, dynamic and cooperative porosity (34) Perec, M.; Baggio, R. Di-μ-acetato-bis[(acetato-κ 2 O,O′)bis- in molecular materials. Chem. Sci. 2016, 7, 4875−4879. (isonicotinamide-κ N)copper(II)]. Acta Crystallogr., Sect. E: Struct. (53) Jing, X.-H.; Yi, X.-C.; Gao, E.-Q.; Blatov, V. A. Synthesis, Rep. Online 2010, 66, m275−m276. structure, topology and magnetic properties of cobalt(II) coordina- (35) Peña-Rodríguez, R.; Rivera, J. M.; Colorado-Peralta, R.; Duarte- tion polymers with 2-nitrobiphenyl-4,4′-dicarboxylic acid and bis- Hernández, A. M.; Flores-Parra, A. Bis(μ 2 -benzoato-κ 2 O : (pyridyl) ligands. Dalton Trans. 2012, 41, 14316−14328. O′)bis[(benzoato-κ 2 O , O ′)bis(4,4′-bipyridine-κ N)cobalt(II)]− (54) Kim, J.; Jo, H.; Yoon, S. W.; Lee, M. H.; Choi, W. J.; Choi, K. benzoic acid (1/6). Acta Crystallogr., Sect. E: Struct. Rep. Online 2014, Y.; Ok, K. M. Synthesis, Structure, and Characterization of Variable 70, m21−m22. Chains in a Series of Transition Metal Coordination Compounds. (36) Dojer, B.; Pevec, A.; Belaj, F.; Jagličić, Z.; Kristl, M.; Drofenik, Eur. J. Inorg. Chem. 2020, 2020, 452−460. M. Structural and magnetic properties of cobalt(II) complexes with (55) Karmakar, A.; Sarma, R. J.; Baruah, J. B. Polymorphism in an pyridinecarboxamide ligands. J. Mol. Struct. 2014, 1076, 713−718. Aqua-Bridged, Dinuclear 2-Nitrobenzoate Complex of Cobalt(II). Eur. J. Inorg. Chem. 2007, 2007, 643−647. ■ (37) Sun, Y.; Wang, Z.; Zhang, H.; Cao, Y.; Zhang, S.; Chen, Y.; Huang, C.; Yu, X. Self-assembly of three novel mixed-ligand coordination polymers: Formation of 2-D grids, 1-D chains and NOTE ADDED AFTER ASAP PUBLICATION ladders and crystal band structure. Inorg. Chim. Acta 2007, 360, Published ASAP June 2, 2022; Name of third author corrected 2565−2572. June 14, 2022. (38) Zheng, Y.-Z.; Tong, M.-L.; Chen, X.-M. Syntheses, structures and magnetic properties of five coordination polymers derived via in situ metal−ligand reactions of 2-phenyl-malonic acid. J. Mol. Struct. 2006, 796, 9−17. (39) Zhuang, W.; Zheng, X.; Li, L.; Liao, D.; Ma, H.; Jin, L. Structural diversity and properties of M(ii) 4-carboxyl phenoxyacetate complexes with 0D-, 1D-, 2D- and 3D M-cpoa framework. CrystEngComm 2007, 9, 653−667. (40) Brog, J.-P.; Chanez, C.-L.; Crochet, A.; Fromm, K. M. Polymorphism, what it is and how to identify it: a systematic review. RSC Adv. 2013, 3, 16905−16931. (41) Wriedt, M.; Jeß, I.; Näther, C. Synthesis, Crystal Structures, and Thermal Properties of New [ZnX 2 (2,5-dimethylpyrazine)] (X = Cl, Br, I) Coordination Compounds. Eur. J. Inorg. Chem. 2009, 2009, 363−372. (42) Sun, J.-K.; Jin, X.-H.; Chen, C.; Zhang, J. Thermally Triggered Reversible Transformation between Parallel Staggered Stacking and Plywood-Like Stacking of 1D Coordination Polymer Chains. Inorg. Chem. 2010, 49, 7046−7051. (43) Jia, H.-P.; Li, W.; Ju, Z.-F.; Zhang, J. A two-step field-induced magnetic transition in spin-canted systems observed only for the Co II coordination polymer. Chem. Commun. 2008, 3, 371−373. (44) Cui, P.; Wu, J.; Zhao, X.; Sun, D.; Zhang, L.; Guo, J.; Sun, D. Two Solvent-Dependent Zinc(II) Supramolecular Isomers: Rare kgd 4471 https://doi.org/10.1021/acs.cgd.2c00406 Cryst. Growth Des. 2022, 22, 4463−4471