Metal Cation-Supported Supramolecular Crown Ethers Featuring

School of Chemistry & Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China, Department of Chemistry, Hanshan Teachers' College, ...
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Metal Cation-Supported Supramolecular Crown Ethers Featuring Hydrogen-Bonded Tetrameric Unit of 2-Hydroxy Pyridines Ming-Liang Tong,*,† Zhuo-Jia Lin,† Wei Li,‡ Shao-Liang Zheng,†,§ and Xiao-Ming Chen*,†

CRYSTAL GROWTH & DESIGN 2002 VOL. 2, NO. 5 443-448

School of Chemistry & Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China, Department of Chemistry, Hanshan Teachers’ College, Chaozhou 521041, China, and State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China Received January 28, 2002;

Revised Manuscript Received April 30, 2002

ABSTRACT: Three solid compounds formulated as [Cu(ClpyOH)4(H2O)2](PF6)2‚(ClpyOH)4 1, [Co(pyOH)4(H2O)2](ClO4)2 2, and [Fe(ClpyOH)4Br2] 3 (ClpyOH ) 5-chloro-2-hydroxy pyridine; pyOH ) 2-hydroxy pyridine) have been shown by single-crystal structural analysis to be 3D networks, which are constructed by metal cation-supported crown ether-like species featuring hydrogen-bonded tetrameric unit of 2-hydroxy pyridines through extensive intermolecular interactions. The similar 16-membered hydrogen-bonded macrocyclic rings are still remaining in their solid structures when the molar ratio of M(II) and ligand were changed to 1:2 or 1:3 in their reaction systems for 1-3, suggesting that this kind of macrocyclic ring is more stable than other products of M(II) and ligand. Differences in the overall structural architectures in 1-3 are due to the interplay between the strong O-H‚‚‚O hydrogen-bonding interactions and/or a variety of weaker interactions involving the halogens, C-H donors, and the aromatic systems. Introduction Pronounced interest has recently been focused on the crystal engineering of supramolecular architectures organized by coordinate covalent or supramolecular contacts (such as hydrogen bonding, π-π interaction, etc.).1,2 Currently, the most prevalent strategy for engineering the structures of crystals takes advantage of directional intermolecular interactions between molecules as the principle means of controlling molecular assembly during crystallization.3-6 However, only the strongest (individually or collectively) intermolecular interactions may become true topological directors to date, thus making crystal programming a challenging, and therefore interesting, synthetic problem. Attempting to understand the nature of weak intermolecular interactions, intermolecular interactions of the halogen atom, namely, halogen‚‚‚halogen, D-H‚‚‚halogen (halogen ) F, Cl, Br; D ) O, N, C), has attracted significant attention in the chemical, crystallographic, and crystal engineering literature. On the other hand, research on the hydrogen bond in the crystal engineering of transition-metal systems is quite young, in contrast to hydrogen bonding in organic crystals, which has been established as a reliable force for organic crystal engineering.3b In view of this, we try to pursue the intramolecular and/or intermolecular supramolecular interactions of the halogen atom in supramolecular architectures organized simultaneously by coordinate and supramolecular bonds (such as hydrogen bonding, π-π interactions, etc.). The versatile ligands of 5-chloro-2-hydroxypyridine and its derivatives have been shown to form a * To whom correspondence should be addressed. † Sun Yat-Sen University. ‡ Hanshan Teachers’ College. § Chinese Academy of Sciences.

large number of polynuclear metal complexes.7 However, there has been scarcity of information on another interesting aspect capable of the formation of intermolecular interactions in the solid due to the presence of N-H and Od hydrogen bonding and potential intermolecular supramolecular interactions of the halogen atom. In the present work, we report the preparation and crystal structure of three new three-dimensional networks self-assembled simultaneously by hydrogenbonding and π-π stacking interactions in combination with metal-ligand bonds, namely, [Cu(ClpyOH)4(H2O)2](PF6)2‚(ClpyOH)4 1, [Co(pyOH)4(H2O)2](ClO4)2 2, and [Fe(ClpyOH)4Br2] 3 (ClpyOH ) 5-chloro-2-hydroxy pyridine; pyOH ) 2-hydroxy pyridine), in which a variety of weaker interactions involving the halogens, C-H donors, and the aromatic systems are discussed. Experimental Section All reagents were commercially available and used as received. The C, H, N microanalyses were carried out with a Perkin-Elmer 240 elemental analyzer. The FT-IR spectra were recorded from KBr pellets in range 4000-400 cm-1 on a Nicolet 5DX spectrometer. Synthesis of [Cu(ClpyOH)4(H2O)2](PF6)2‚(ClpyOH)4 (1). A MeOH-H2O (v/v 1:1) solution (10 cm3) containing of ClpyOH (0.260 g, 2.0 mmol) and Cu(NO3)2‚3H2O (0.242 g, 1.0 mmol) was stirred at 50 °C for 30 min. A solution (5 cm3) of NaPF6 (0.336 g, 2.0 mmol) was then added. The resulting solution was allowed to stand in air at room temperature for two weeks, yielding polyhedral crystals (ca. 90% yield based on ClpyOH). Anal. calcd for C40H36Cl8CuN8O10P2F12: C, 33.69; H, 2.54; N, 7.86. Found: C, 33.52; H, 2.42; N, 7.72%. IR (KBr, cm-1): 3215m, br (νN-H and νO-H), 3132m, 3067m, 2991m, 2871m, 2672w, 1652vs (νCO), 1604vs, 1537m, 1446s, 1413s, 1326m, 1270w, 1222w, 1136w, 1111w, 999w, 821vs (νPF6), 723w, 678s, 558m (νPF6), 510m, 471w. Synthesis of [Co(pyOH)4(H2O)2](ClO4)2 (2). It was prepared as for 1 using Co(ClO4)2‚6H2O instead of Cu(NO3)2‚3H2O

10.1021/cg025505a CCC: $22.00 © 2002 American Chemical Society Published on Web 07/09/2002

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Table 1. Crystal Data and Structure Refinement formula fw crystal system space group A (Å) B (Å) C (Å) R (deg) β (deg) γ (deg) V (Å3) Z Dc/g cm-3 µ(Mo-KR)/mm-1 no. unique data no. data with I > 2σ(I) R1, wR2

1

2

3

C40H36Cl8CuF12N8O10P2 1425.85 orthorhombic Pnaa 7.430(7) 18.128(18) 20.656(8)

C20H24Cl2CoN4O14 674.26 monoclinic P21/n 9.339(2) 11.582(3) 12.990(2)

C20H16Br2Cl4FeN4O4 733.84 triclinic P-1 12.066(4) 12.065(3) 12.097(7) 108.00(1) 110.19(1) 110.10(1) 1357.2(10) 2 1.796 3.927 5331 3523 0.0588, 0.1709

97.219(17) 2782(4) 2 1.702 0.935 3338 1968 0.0625, 0.1679

(yield ca. 88%). Anal. calcd for C20H24Cl2CoN4O14: C, 35.63; H, 3.59; N, 8.31. Found: C, 35.48; H, 3.42; N, 8.12%. IR (KBr, cm-1): 3312m (νN-H), 3058m, 2946m, 1650vs (νCO), 1604vs, 1535m, 1446s, 1411s, 1326m, 1270w, 1222w, 1136w, 1113vs (νClO4), 1085vs(νClO4), 875m, 723w, 510m. Synthesis of [Fe(ClpyOH)4Br2] (3). It was prepared as for 1 using FeBr2 instead of Cu(NO3)2‚3H2O (yield ca. 58%). Anal. Calcd for C20H16Br2Cl4FeN4O4: C, 32.73; H, 2.20; N, 7.63. Found: C, 32.37; H, 2.43; N, 7.39%. IR (KBr, cm-1): 3314w (νN-H), 3249w, 3209w, 3098m, 3033s, 3002s, 2948s, 2858s, 2819s, 2672m, 1717m, 1646s (νCO), 1604s, 1532s, 1493m, 1446s, 1411s, 1327m, 1271m, 1226m, 1178m, 1138s, 1109m, 1000m, 944w, 878m, 835m, 728w, 676s, 634w, 512m. X-ray Crystallography. Diffraction intensities for these three complexes were collected at 21 °C on a Siemens R3m diffractometer using the ω-scan technique. Lorentz-polarization and absorption corrections were applied.8 The structures were solved with direct methods and refined with full-matrix least-squares technique using the SHELXS-97 and SHELXL97 programs, respectively.9,10 Anisotropic thermal parameters were applied to all non-hydrogen atoms. The organic hydrogen atoms were generated geometrically (C-H 0.96 Å); the aqua hydrogen atoms were located from difference maps and refined with isotropic temperature factors. Analytical expressions of neutral-atom scattering factors were employed, and anomalous dispersion corrections were incorporated.11 Crystal data as well as details of data collection and refinement for the complexes are summarized in Table 1. Selected bond distances and angles are listed in the Table 2. The structures, presented in the figures, were produced with SHELXTL.12 For 1, the site occupancy of the copper atom was allowed to refine from the 0.5 value set by the refinement program. As it refined to approximately 0.25, the site occupancy was then fixed as 0.25. The 5-chloro-2-pyridinol ligand was assumed to adopt the dipolar form owing to the short carbon-oxygen distance, i.e., a positive charge was placed on the pyridyl nitrogen atom and a negative charge on the phenolic oxygen end, which is linked to the copper atom. Because of the onefourth site occupancy for the copper atom, the centrosymmetric [Cu(ClpyOH)4(H2O)2]2+ uses each coordinated water molecule to form hydrogen bonds to a quartet of hydrogen-bonded ClpyOH molecules; two of the hydrogen bonds are short and two are somewhat long. The crystallographic data for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Center as supplementary publication no. CCDC 183913-183915.

Results and Discussion Synthesis and Characterization. Complexes 1-3 are also the unique products when the molar ratio of M(II) and ligand were changed to 1:2 or 1:3 in the reaction systems, suggesting the reaction is insensitive to the stoichiometry. This fact suggests that the 16-

1394.0(5) 2 1.606 0.882 2452 1425 0.0728, 0.2509

Table 2. Selected Interatomic Contacts (Å) and Angles (°) for Complexes 1-3a 1 Cu(1)-O(1w) Cu(1)-O(1wa) Cu(1)-O(1) O(1w)‚‚‚O(1c) O(1w)‚‚‚O(2d) O(1w)-Cu(1)-O(1wa) O(1w)-Cu(1)-O(1) O(1wa)-Cu(1)-O(1) O(1)-Cu(1)-O(1b) O(1w)-Cu(1)-O(2) O(1w)-H(1w)‚‚‚O(1c) O(1w)-H(1w)‚‚‚O(2d) 2 Co(1)-O(1w) Co(1)-O(2) Co(1)-O(1) O(1w)‚‚‚O(6a) O(1w)‚‚‚O(3)

1.844(4) 1.871(4) 2.152(3) 2.760(4) 2.836(4)

Cu(1)-O(2) O(1)-C(1) O(2)-C(6) N(1)‚‚‚O(2c) N(2)‚‚‚O(1)

2.359(3) 1.268(5) 1.251(5) 2.927(4) 2.779(5)

180.000(3) 93.67(10) 86.33(10) 172.7(2) 83.90(9) 138.9 110.5

O(1wa)-Cu(1)-O(2) O(1)-Cu(1)-O(2) O(1b)-Cu(1)-O(2) O(2)-Cu(1)-O(2b) N(1)-H(1)‚‚‚O(2c) N(2)-H(2)‚‚‚O(1)

96.10(9) 92.56(12) 88.22(12) 167.81(19) 155.8 160.6

2.073(4) 2.103(5) 2.122(5) 2.807(9) 3.016(8)

O(1)-C(1) O(2)-C(6)

1.286(7) 1.278(7)

O(2)‚‚‚N(1) O(1)‚‚‚N(2b)

2.711(7) 2.720(8)

O(1w)-Co(1)-O(1wb) O(1w)-Co(1)-O(2b) O(1w)-Co(1)-O(2) O(2b)-Co(1)-O(2) O(1w)-H(1wa)‚‚‚O(6a) O(1w)-H(1wb)‚‚‚O(3) 3 Fe(1)-O(1) Fe(1)-O(4) Fe(1)-O(3) Fe(1)-O(2) Fe(1)-Br(1) O(4)‚‚‚N(1) O(2)‚‚‚N(3)

180.0 89.5(2) 90.5(2) 180.0 174.0 131.5

O(1w)-Co(1)-O(1) O(2b)-Co(1)-O(1) O(2)-Co(1)-O(1) O(1)-Co(1)-O(1b) O(2)-H(2B)‚‚‚N(1) O(1)-H(1A)‚‚‚N(2b)

90.0(2) 90.80(18) 89.20(18) 180.0 149.4 140.8

2.151(4) 2.153(4) 2.154(4) 2.156(4) 2.6232(15) 2.774(6) 2.763(6)

Fe(1)-Br(2) O(1)-C(1) O(2)-C(16) O(3)-C(11) O(4)-C(6) O(1)‚‚‚N(2) O(3)‚‚‚N(4)

2.6236(15) 1.274(7) 1.270(7) 1.266(7) 1.266(6) 2.765(6) 2.761(6)

O(1)-Fe(1)-O(4) O(1)-Fe(1)-O(3) O(4)-Fe(1)-O(3) O(1)-Fe(1)-O(2) O(4)-Fe(1)-O(2) O(3)-Fe(1)-O(2) O(1)-Fe(1)-Br(1) O(4)-Fe(1)-Br(1) O(4)-H(4)‚‚‚N(1) O(2)-H(2)‚‚‚N(3)

90.09(16) 179.12(18) 89.88(16) 90.09(16) 179.28(18) 89.95(16) 90.58(14) 89.87(14) 147.8 149.8

O(3)-Fe(1)-Br(1) O(2)-Fe(1)-Br(1) O(1)-Fe(1)-Br(2) O(4)-Fe(1)-Br(2) O(3)-Fe(1)-Br(2) O(2)-Fe(1)-Br(2) Br(1)-Fe(1)-Br(2) O(1)-H(1)‚‚‚N(2) O(3)-H(3)‚‚‚N(4)

90.30(14) 89.43(13) 89.41(14) 90.11(14) 89.71(13) 90.59(13) 179.98(9) 149.1 148.2

a Symmetry codes: (a) x + 1/2, y, -z + 3/2; (b) x, -y + 1/2, -z + 3/2; (c) x - 1/2, -y + 1/2, z; (d) x, -y + 1/2, -z + 3/2 for 1; (a) -x + 1/2, y + 1/2, -z + 1/2; (b) -x, -y + 2, -z for 2.

membered hydrogen-bonded circles are more stable than other products with 1:n (n ) 2-6) molar ratios of M(II) and ligand. 2-Hydroxypyridine (2-pyridone or 2-oxopyrimidine) or its derivatives have long been of interest because it exhibits lactum-lactim tautomerism (Scheme 1). The lactam form occurs in the crystal structure of 2-pyri-

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Figure 1. Perspective view showing the coordinated 16membered hydrogen-bonded crown ether-like circle in 1.

Scheme 1. Lactum-Lactim Tautomerism of 5-Chloro-2-Hydroxypridone

done13,14a and in the crystals of related molecules such as 2-thiopyridone,14b,c 5-chloro-2-pyridone,14d and 4-hydroxy-2-pyridone,14e but the lactim form occurs in the crystals of 6-chloro-2-hydroxy-pyridine and 6-bromo-2hydroxy-pyridine.15 In complexes 1, 2 and 3, the IR absorptions of the CdO stretching bonds were observed at around 1650 cm-1 for all the three complexes (1652, 1650, 1646 cm-1 for 1, 2 and 3, respectively), indicating that the ClpyOH and pyOH ligands act as the lactam form. These red shifted values relative to the free carbonyl stretching frequency may reflect the effect of both the metal coordination and the hydrogen bond. Other characteristic vibrational bands appeared at 3215 for 1, 3312 for 2, and 3314, 3249 cm-1 for 3, can be ascribed to the N-H groups. Crystal Structures. The structure of 1 consists of mononuclear [Cu(ClpyOH)4(H2O)4]2+ cations, rich solvate ClpyOH molecules, and PF6- anions. As shown in Figure 1, the Cu(II) atom is coordinated in a greatly distorted octahedral geometry to four oxygen atoms from four different ClpyOH [Cu-O ) 2.152(3)-2.359(3) Å] and two aqua ligands [Cu-O ) 1.845(4) and 1.870(4) Å]. The four ClpyOH ligands are held together by hydrogen-bonding [N‚‚‚O 2.779(5) and 2.927(4) Å; N-H‚‚‚O 155.8 and 160.6°] into a 16-membered crown ether-like macrocycle, and the Cu(II) atom lies at its center. It should be noted that such discrete 16membered hydrogen-bonded macrocyclic rings are rare, only two have been found in the compounds [Ph4P]2[Cu{OC(CF3)2OH}4] and lithium enolate of 1,3-cyclohexanedione.16 The uncoordinated ClpyOH molecules are similarly enclosed into a 16-membered crown etherlike macrocycle by hydrogen bonding, similar to that found in [Ph4P]2[{(CF3)2C(OH)O}2{(CF3)2C(OH)2}2], in which the un-ionized and monoionized diol molecules are held together by hydrogen bonding in the tetrameric

Figure 2. Top view showing the 1D hydrogen-bonded chain constructed from the coordinated and uncoordinated 16membered hydrogen-bonded crown ether-like circle in 1.

dianion.17 Adjacent Cu(II)-containing crown ether-like macrocycles and empty ones are interlinked into onedimensional chains through O-H‚‚‚O hydrogen bonding between the aqua ligands and the phenol groups of the empty macrocycles, as shown in Figure 2. Adjacent intrachain Cu(II)‚‚‚Cu(II) distances are 7.430(7) Å. Each aqua donates two three-center hydrogen bonds with four ClpyOH molecules of adjacent empty macrocycle [O‚‚‚O ) 2.760(4) and 2.836(4) Å, O-H‚‚‚O ) 110.5 and 138.9°]. The most interesting feature is the overall threedimensional molecular network in 1. The adjacent onedimensional chains are interlinked into novel threedimensional network with one-dimensional channels running along the a-axis direction through Cl‚‚‚Cl interactions (supramolecular synthon),18 as shown in Figure 3. The Cl‚‚‚Cl contacts are 3.558 Å, which is comparable to those found in related compounds.19 The channels are occupied by the PF6- guests that are weakly hydrogen-bonded to phenol groups of the adjacent ClpyOH moieties [C‚‚‚F 3.184-3.355 Å; C-H‚‚‚F 107.1-166.6°]. The crystal structure of 2 consists of mononuclear [Co(pyOH)4(H2O)4]2+ cations and ClO4- anions. The Co(II) atom, located at an inversion center, is coordinated in a slightly distorted octahedral geometry to four oxygen atoms from four different pyOH [Co-O 2.103(5) and 2.122(5) Å] and two aqua ligands [Co-O 2.073(4) Å], as shown in Figure 4. Similar to that in 1, the four pyOH ligands are held together by hydrogen-bonding [N‚‚‚O 2.711(7) and 2.720(8) Å; N-H‚‚‚O 140.8 and 149.4°] into a 16-membered crown ether-like macrocycle; the Co(II) atom lies at its center. The adjacent mononuclear coordinations cores are extended into a novel three-dimensional network with one-dimensional channels running along the c-axis direction through staggered π‚‚‚π interactions between pyridyl rings of adjacent [Co(pyOH)4(H2O)2]2+ cores with a face-to-face separation of 3.75 Å, as shown in Figure 5. The channels are occupied by the ClO4- anions, and

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Figure 3. Top view showing the 3D netowrk in 1. Both the Cl‚‚‚Cl interaction and hydrogen bonds are represented by broken lines.

Figure 4. Perspective view showing the crown ether-like coordination core in 2. -

each ClO4 anion is hydrogen-bonded to the adjacent aqua [O‚‚‚O 2.807(9) and 3.016(8) Å; O-H‚‚‚O 174.0 and 131.5°] and contacts with adjacent pyOH molecules. The C‚‚‚O distances and C-H‚‚‚O angles are within the ranges 3.476-3.582 Å and 129.3-175.6°, respectively, indicating significant C-H‚‚‚O hydrogen bonding interactions, which have recently been documented elsewhere.20 The crystal structure of 3 consists of neutral mononuclear [Fe(ClpyOH)4Br2] species. The Fe(II) atom is coordinated in a greatly distorted octahedral geometry to four phenol oxygen atoms from four different ClpyOH [Fe-O 2.150(4)-2.156(4) Å] at the equatorial positions and two Br- ions [Fe-Br 2.6234(15) and 2.6236(15) Å] at the apical positions, as shown in Figure 6. The Fe-O(phenol) distances are larger than those [2.045(4) Å] in a related Fe(II)-phenol compound.21 Similar to those in 1 and 2, the four pyOH ligands are held together by hydrogen bonding [N‚‚‚O 2.761(6)-

Tong et al.

Figure 5. Top view showing the 3D netowrk in 2. Hydrogen bonds are represented by broken lines. The counterions are omitted for clarity.

Figure 6. Perspective view showing the crown ether-like coordination core in 3.

2.774(6) Å; N-H‚‚‚O 147.8-149.8°] into a 16-membered crown ether-like macrocycle; the Fe(II) atom lies at its center. It is interesting to note that the intermolecular interactions in 3 are different from those in 1 and 2. Each [Fe(ClpyOH)4Br2] molecule is linked to four neighboring molecules through 16 weak C-H‚‚‚Br hydrogen bonds.22 As shown in Figure 7, each bromide atom is seated between two pairs of pyridyl rings from two adjacent [Fe(ClpyOH)4Br2] species, and forms four C-H‚‚‚Br acceptor hydrogen bonds [C‚‚‚Br 3.632(6)3.770(6) Å; C-H‚‚‚Br 142.4-170.9°]. Such intermolecular interactions result in a close packing of the molecules (Figure 7). The bond distances of the C-H‚‚‚Br hydrogen bonds presented in 3 are comparable to that [3.712(11)-3.918(9) Å, 131-171°] observed for [Py-C12-Py][MBr4],22 and obviously shorter than those [3.938(14)-4.136(4) Å] found in the reported compounds.23 Compared with the reported structures of 2-pyridone and its derivatives,13-15 it should be noted that the

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motifs of the networks have been observed and may arise from a combination of different types of interactions. Out of the three products isolated and characterized when the molar ratio of M(II) and ligand were changed to 1:2 or 1:3 in the reaction systems, the similar 16-membered hydrogen-bonded macrocyclic ring are still remaining in their solid structures, suggesting that this kind of macrocyclic ring is more stable than other products of M(II) and ligand. On the other hand, 1 is a good candidate of the three-dimensional hydrogenbonded networks with channels simultaneously through hydrogen bonding and Cl‚‚‚Cl intermolecular interactions. The isolation of 1-3 also provides additional good experimental evidence for recognizing the structural patterns of interactions as driving forces to a particular aggregation state.

Figure 7. Top view showing the 3D netowrk in 3. Hydrogen bonds are represented by broken lines.

metal ions in 1, 2, and 3 acts as a template in the formation of the hydrogen-bonded tetrameric units. In the structures of the free ligands, dimers are always formed by two N-H‚‚‚O interactions, but in the latter, each structure features a hydrogen-bonded tetrameric unit of 2-hydroxy pyridines in the solid, and the similar 16-membered hydrogen-bonded macrocyclic rings are still remaining in their solid structures when the molar ratio of M(II) and ligand were changed to 1:2 or 1:3 in their reaction systems for 1-3, suggesting that this kind of macrocyclic ring is more stable than other products of different M(II) and ligand ratio. On the other hand, the structures of 1, 2, and 3 are also greatly different from those of the reported metal complexes of 3-hydroxypyridine, which shows covalently bonded or hydrogen-bonded two-dimensional structures;24 this may result from the fact that the hydroxy group is located at a different site of the pyridyl ring. It has been recently documented that halogens can afford true C-H‚‚‚X hydrogen bonds (of relatively weak character), especially when the X acceptor bears a full or partial negative charge (halide ions or M-X bonds, respectively).25 Therefore, the different solid structures of 1-3 can be expected when the apical ligands range from H2O to Br- ions. In complex 1, the hydrogenbonded chain should be quite stable due to the strong O-H‚‚‚O hydrogen bonds between the [Cu(ClpyOH)4(H2O)2]2+ species and hydrogen-bonded tetrameric (ClpyOH)4 species; however, the supramolecular array of these chains is driven only by the relatively weak Cl‚‚‚Cl interchain interaction. Whereas in complexes 2 and 3, the supramolecular arrays of the [Co(pyOH)4(H2O)2]2+ and [Fe(ClpyOH)4Br2] species are mainly driven by the π-π interaction between adjacent [Co(pyOH)4(H2O)2]2+ species in 2 or by the C-H‚‚‚Br hydrogen bonding interaction between adjacent [Fe(ClpyOH)4Br2] species in 3, respectively. Conclusions Three interesting three-dimensional networks have been obtained through intermolecular interactions depending on the counterions. Variations of the structural

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