Coordination Polymers with Intramolecular Fluorine-Involved Contacts

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Coordination Polymers with Intramolecular Fluorineinvolved Contacts in Two-dimensional Sheet Windows Hamid Reza Khavasi, and Narjes Rahimi Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b01673 • Publication Date (Web): 30 Dec 2016 Downloaded from http://pubs.acs.org on December 31, 2016

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Crystal Growth & Design

Coordination Polymers with Intramolecular Fluorineinvolved Contacts in Two-dimensional Sheet Windows Hamid Reza Khavasi* and Narjes Rahimi

Department of Inorganic Chemistry and Catalysis, Shahid Beheshti University, General Campus, Evin, Tehran 1983963113, Iran.

E-mail: [email protected]

CORRESPONDING AUTHOR FOOTNOTE: Hamid Reza Khavasi, Tel No: +98 21 29903105, Fax No: +98 21 22431663.

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Abstract Six two-dimensional polymeric complexes of [Hg(L2-F)2]n, 1, [Hg(L2,5-F)2]n, 2, [Hg(L3-F)2]n, 3, [Hg(L2,3,4F

)2]n, 4, [Hg(L3,4,5-F)2]n, 5 and [Hg(L2,3,4,5-F)2]n, 6 and a discrete complex of [Hg(L2,6-F)2], 7, in which Ln-F

ligands are N-(fluorinatedphenyl)-2-pyrazinecarboxamides carrying fluorine atoms on the different positions of phenyl ring, have been synthesized and characterized. The crystal structures resulted from Xray diffraction reveal that all polymeric complexes have similar 2D sheet windows. From the topological perspective, each metal atom can be viewed as 4-connected nodes and Ln-F ligands can be considered as linkers in the formation of these 2D windows. Due to the flexibility of the ligand, fluorinated-phenyl rings as hanging groups in the windows are pointed toward the adjacent groups to generate different fluorineinvolved intra-molecular interactions. One of the common features in the crystal structures of these complexes is the presence of strong tendency to form intra-molecular F…π interactions in 2D windows of the crystal structure of all polymeric complexes, except complex 3. These interactions are cooperating with weak C-H…F and C-H…O hydrogen bonds. Also, in the crystal structure of complexes 5 and 6, carrying three and four fluorine atoms on phenyl rings, type II F…F synthons between adjacent rings have observed in cooperation to F…π interactions. Hirshfeld surface analysis also confirms that the F…F/π contacts are predominant.

1. Introduction

In recent years, synthesis and design of new coordination polymers (CPs)1 has been investigated extensively due to their versatile structural diversity, unique properties, and their potential applicability in different areas such as molecular sensing, recognition,2-4 and magnetism,5-8 thermal properties,9-12 gas storage,13-17 catalysis,18-20 material chemistry and nanotechnology.21-23 Solid state properties of metallosupramolecular coordination polymers are dictated by ordering of molecules in the crystal packing as well 2 ACS Paragon Plus Environment

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as by directional and nondirectional intermolecular interactions that hold the components together.24-27 Therefore, designing self-assembled coordination polymers accompanied by control and finding the subtle role of non-covalent interactions in controlling the supramolecular architecture of coordination polymers is of current interest.28-32 We have recently reported that cooperative non-covalent interactions can lead to the formation of one- or two-dimensional architectures under anion-directed self-assembly.33 The effect of hydrogen bonding34-37 and π-involved interactions such as π···π, cation···π, anion···π, lonepair···π, and metal···π38-41 in the directing the self-assembly of coordination compounds are well accepted among supramolecular coordination chemists. Another interaction to construct new coordination compounds is directional halogen bonding interaction, XB. Halogen bond defines as an interaction of electrophilic region, σ-hole, of anisotropically polarized halogen atom with an electron-rich region on another atom.42-45 The halogen bond strength is strongly dependent on the polarizability of the halogen atom that is in the order of Cl, Br, and I. Because of low polarizability as well as high electronegativity, fluorine atom usually has no σ-hole. There is disagreement as to whether fluorine atom can be involved in halogen bonding interaction.46-51 On the other hand, from several interactions involving halogen atoms those including fluorine atom are attracting attention due to several reasons such as their role in the medicinal chemistry.52-55 The nature of interactions involving fluorine atom as the “second-favorite heteroatom” after nitrogen for drug design56 such as F…F and C–F…π, is still being debated within the scientific community and still remains obscure.57-61 During our research program aiming at the understanding of the role of intermolecular interactions in the crystal packing of mercury coordination compounds containing pyrazine carboxamide ligands,62-71 we have synthesized, characterized and investigated a series of designed complexes in the present work, in order to gain a deeper understanding on the crucial role of fluorine-involved interactions in the supramolecular architecture of coordination compounds including fluorinated ligands. In this article, a series of N-(fluorinatedphenyl)-2-pyrazinecarboxamide ligands, L2-F, L2,5-F, L3-F, L2,3,4-F, L3,4,5-F, L2,3,4,5-F,

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and L2,6-F, Scheme 1, carrying fluorine atoms on the phenyl ring, have been employed for the synthesis of six isostructural two-dimensional polymeric mercury(II) coordination complexes 1-6 and a discrete complex 7, in order to get insights into the investigation of the fluorine-involved interactions on the structural assemblies. Seven Hg(II) complexes, [Hg(L2-F)2]n, 1, [Hg(L2,5-F)2]n, 2, [Hg(L3-F)2]n, 3, [Hg(L2,3,4F

)2]n, 4, [Hg(L3,4,5-F)2]n, 5, and [Hg(L2,3,4,5-F)2]n, 6, and [Hg(L2,6-F)2], 7, have been prepared by the reaction

of equimolar quantities of Hg(CF3COO)2 and ligand in methanol, Scheme 1. The structural details show that the presence of strong tendency to form intra-molecular F…F/π interactions in the 2D windows of all polymeric complexes is one of the common features in the crystal structures.

2. Results and Discussion Synthesis. The ligands N-(fluorinated-phenyl)-2-pyrazinecarboxamide, Ln-F, were synthesized through a condensation reaction of the same equivalents of pyrazinecarboxylic acid and fluorinated-aniline in pyridine in the presence of triphenyl phosphite.72 The 1:1 molar ratio of ligand and Hg(CF3COO)2 simply mixed in methanol to prepare corresponding polymeric complexes [Hg(L2-F)2]n, 1, [Hg(L2,5-F)2]n, 2, [Hg(L3-F)2]n, 3, [Hg(L2,3,4-F)2]n, 4, [Hg(L3,4,5-F)2]n, 5, and [Hg(L2,3,4,5-F)2]n, 6, and discrete complex [Hg(L2,6-F)2], 7. Slow evaporation of the solvent resulted in the air stable colourless block crystals of 1 and 5, colourless prism crystals of 3, 4 and 6, colourless plate crystal of 2 and light yellow prism crystal of 7, after a few days. Attempts were made to form complexes with L4-F, L2,4-F and L2,3,4,5,6-F ligands. Yet unfortunately, no mercury-containing species were isolated. ORTEP diagrams for complexes [Hg(L2-F)2]n, 1, [Hg(L2,5-F)2]n, 2, [Hg(L3-F)2]n, 3, [Hg(L2,3,4-F)2]n, 4, [Hg(L3,4,5-F)2]n, 5, and [Hg(L2,3,4,5-F)2]n, 6, and [Hg(L2,6-F)2], 7 are shown in Figure 1. It is notable that using 2:1 molar ratio of ligand and Hg(CF3COO)2 in all complexes, resulted in the same product as when using 1:1 molar ratio. The crystallographic data for compounds 1-7 are presented in Table 1. Selected bond distances and angles are also summarized in Table S1. 4 ACS Paragon Plus Environment

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Structural analysis of 2D polymeric mercury complexes with N-(fluorinated-phenyl)-2pyrazinecarboxamide, L2-F, L2,5-F, L3-F, L2,3,4-F, L3,4,5-F, and L2,3,4,5-F ligands; [Hg(L2-F)2]n, 1, [Hg(L2,5F

)2]n, 2, [Hg(L3-F)2]n, 3, [Hg(L2,3,4-F)2]n, 4, [Hg(L3,4,5-F)2]n, 5, and [Hg(L2,3,4,5-F)2]n, 6. A reaction between

Hg(CF3COO)2 and N-(fluorinated-phenyl)-2-pyrazinecarboxamide, L2-F, L2,5-F, L3-F, L2,3,4-F, L3,4,5-F, and L2,3,4,5-F ligands in methanol followed by slow evaporation of the solvent afforded crystals of 1-6. Crystallographic data and selected bond distances and angles for these compounds are presented in Tables 1 and S1, respectively. All six complexes crystallize in primitive monoclinic system with P21/c centrosymmetric space group. ORTEP diagrams of polymeric coordination compounds 1-6 with atom labeling scheme are shown in Figures 1(a)-1(f). X-ray crystallographic analysis reveals that there is a half crystallographically

independent

Hg(II)

ion

and

one

deprotonated

N-(fluorinated-phenyl)-2-

pyrazinecarboxamide ligand in the asymmetric unit of all six complexes 1-6. As indicated in Figure 1, the coordination sphere around metal ions in polymeric complexes 1-6 are similar and in all cases the Hg(II) ion is six-coordinated by four nitrogen and two oxygen atoms from four Ln-F ligands in a distorted octahedral (Oh) geometry (maximum angle deviation from 90° is ± 18.1° in complex 6). In the Hg center, the basal plane of the octahedron is occupied by four nitrogen atoms from two anionic bi-dentate Ln-F ligands. The axial positions are occupied by two oxygen atoms from the carbonyl groups from adjacent ligands. In these complexes Hg-Npyz, Hg-Namid and Hg-O bond lengths are ranged between 2.621(5)2.665(11)Å, 2.054(7)-2.083(4) Å, and 2.772(6)-2.964(6) Å, for complexes 1-6, respectively, Table S1. For convenience, the polymeric structure of complexes 1-6 can be defined in which the djacent Hg(N-N)2 units (where N-N defines chelating atoms of Ln-F ligand) are linked by C=O-Hg bonds to form a 2D layers spaning parallel to bc-plane. In these compounds the interchain distance of the neighboring mercury atoms bridged by Ln-F ligands, is ranged between 6.567-6.735Å. Crystal structure analysis of complexes 1-6 confirms that these compounds are isostructure with similar cell parameters. The Xpac



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dissimilarity index, X-value,73 can be considered as a quantifiable numerical descriptor for comprising configuration similarity. The smaller the magnitude of X, the more comparable the structure will be. Distance parameter, d, is other parameter that Xpac provides for comparing similarity in the two molecular packing arrangements. Xpac maps containing the dissimilarity index X (above the diagonal line of square box) and distance parameter d (below the diagonal line), for 15 pairwise structures depict in Figure 2. Although all six complexes have similar coordination sphere, the results from Figure 2 clearly indicate that some of two pairs have slightly big values in X and d parameters. As example, complex 1 has X- and d-values more than 10 and 0.4, respectively, in comparison to complexes 4 and 6. Also complex 2 indicates slightly big values in comparison to complexes 4-6. Of course, there are small differences in some cases such as complex 1 and 2, 3 and 4 as well as 5 and 6. It is notable that although these coordination polymers have similar 2D structures but the packing of 2D sheets and forming of final supramolecular arrangement shows some small dissimilarity due to the diversity of intermolecular interactions between adjacent planes. It seems that weak intermolecular interactions have a pivotal role in the presence of small differences in these crystal structures. In this regard, the synthesized polymeric complexes, 1-6, can be classified in three series. Herein, crystal structure description as well as presence of similarities between building blocks in each series is briefly discussed. In the first group, isostructural complexes 1 and 2, constructed 2D sheets are linked to adjacent ones by head-to-tail Cphen-H…Npyz hydrogen bonds (with the H…N distance of 3.472(4) and 3.540(4) Å for 1 and 2), Figures 3(a) and 3(b), Table S2. In the packing of complexes 3 and 4, second group, the overall supramolecular architecture results from the head-to-tail Cpyz-H…F hydrogen bonds (with the H…F distance of 3.242(4) Å for 3 and 3.444(7) and 3.634(8) Å for 4) between pyrazine and phenyl rings from adjacent 2D sheets, Figures 4(a) and 4(b), Table S2,. In the third group, isostructural complexes 5 and 6, cooperation of F…F with the distance of 2.937(7) and 3.031(7) Å for 5 and 6, respectively, Table 2, and


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localized head-to-tail F…πphen interactions with fluorine-to-C9(phenyl) ring distances of 2.990 (Å) for 5 and 2.123 (Å) for 6, are main factors in the generation of overall supramolecular assemblies, Table 3, Figures 5(a) and 5(b). In complex 6 these interactions are cooperate with Cpyz-H…F hydrogen bonds, Figure 5(b), Table S2.

Structural

analysis

of

discrete

mercury

complex

with

N-(2,6-difluorophenyl)-2-

pyrazinecarboxamide, L2,6-F, ligand; [Hg(L2,6-F)2], 7. Complex 7 has the same asymmetric unit of other complexes while overall molecular structures are different. In contrast to compounds 1-6 with two dimensional polymeric architectures, complex 7 has a discrete structure. The coordination geometry around the Hg(II) atom in complex 7 can be described as a distorted-square planar with two pyrazine- and two amidic-nitrogen atoms from two anionic L2,6-F chelating ligands (Hg-N: 2.643(15) and 2.052(13) Å), Figure 1(g). The four-coordinate geometry index, τ4, as defined by Houser,

74

is zero for this complex

which implies that the coordination geometry is best described as square planar. This four-coordinate geometry index, τ4, which is defined by the equation τ4=[360-(α+β)/141] (α and β are the two largest angles around the metal), ranges from 0 to 1, for a square planar and tetrahedral geometries, respectively. The Npyz−Hg−Npyzi, Namide−Hg−Namidei and Npyz−Hg−Namid and Npyz−Hg−Namidei angles are 180.0, 180.0, 71.8(5) and 108.2(5)°, respectively (symmetry code, i: -x, -y, -z). The slightly deviation of perfect square planar geometry is due to the chelation of amid ligands through Npyz−Hg−Namide with bite angle of 71.8(2)°. This square planar geometry is an unusual coordination arrangement around Hg(II) complexes. A CSD search on the geometry around the Hg(II) ions has been performed.75 As a restriction, the N-Hg-N angles were allowed to have values from 160° to 180° (where N is defined as any coordinated nitrogen atom). Our results show that square planar geometry around Hg(N)4 are rare and there is only one report,76 with refcode of UDAHEN, in which coordination geometry around Hg(II) may be considered as square planar. In this complex, central metal is coordinated by two 1,3-bis(4-bromophenyl)triazenide



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chelating ligand. It is notable that as in this compound the N−Hg−N bite angle is 50.5°, the geometry around the mercury can be considered as highly distorted square planar. The bite angle of 71.8(2)° in complex 7 is due to the chelation of amid ligands through Npyz and Namide atoms. It is notable that, despite the slightly deviation of perfect geometry, the coordination sphere around metal ion is undoubtedly considered as square planar. To the best of our knowledge, this complex is the second compound of Hg(N)4 which has got square planar geometry. Such square planar geometry for HgI2(N)2 has been reported by some of us recently.65 In compound 7 adjacent units are linked by head-to-tail type I F…F contacts to form a 1D linear chain spanning along the c-axis, Figure 6(a). The F...F contact distance is 2.915(6) Å, Table 2, which is represent only less than 1.00% construction against the sum of the van der Waals radii of fluorine atoms.77 Adjacent linear chains are further linked to each other to form 2D sheets by cooperation of head-to-tail Cphen-H…O=C (with the H…O distance of 3.352(2) and 3.282(3) Å) weak hydrogen bonds, Table S2, and πphen…πphen interaction with ring centroid to centroid distance of 3.909 Å, Figure 3(b). In the packing of this complex, the overall supramolecular structure results from the bifurcated Cphen-H…F interactions by H…F distances of 3.234(4) and 3.225(2) Å, Table S2, Figure 6(c).

Fluorine-involved interactions in the 2D sheet windows of coordination polymers. It is well accepted that in a typical halogen bond a net attractive interaction between electrophilic region of a halogen atom and a nucleophilic region in another atom is occurred, where the electrophilic region on the halogen is termed as a σ-hole.45 It must be noted that the increasing of the polarizability of the halogen atom in the order of Cl, Br, and I, resulted in the increasing of strength of the σ-hole. However, due to the high electronegativity and low polarizability, fluorine usually has no σ-hole. There are different reports that clearly demonstrate that the formation of fluorine-involved interactions is yet to be harnessed.46-51 So the nature of fluorine involving interactions, such as F…F and C–F…π, is still being debated within the scientific community and fluorine character as a Lewis acid in halogen bonding is still open to question.78-


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81


In the present work, to gain a deeper understanding on the crucial role of fluorine-involved interactions

in the supramolecular architecture of coordination compounds including fluorinated ligands, we have synthesized, characterized and investigated a series of designed complexes. Understanding and control of the synthons holding the three-dimensional arrays of coordination compounds building blocks, is one of the important and prolific areas of current research in inorganic chemistry.82-87 This requires considering and analyzing the crystal packing of a series of designed compounds allowing to systematically delineation of resultant supramolecular assemblies with specific and controllable changes in their molecular structures. In coordination compounds a slight change in the structure of an organic ligand may play a forcible role in the supramolecular organization and synthons constructed overall molecular assemblies.88-93 In this regard, for a systematic study to investigate of factors affecting the F…π and F…F fluorine-involved interactions, seven closely related N-(fluorinated-phenyl)-2-pyrazinecarboxamide, Ln-F organic ligands have been designed for the synthesize of seven Hg coordination complexes 1-7. In all seven complexes except 3, F…F/π interactions have been observed. A schematic representation of significant fluorine-involved intra- and inter-molecular interactions controlling the packing of 1-7 is illustrated in Scheme 2. As discussed earlier all complexes 1-6 have almost same 2D windows, Figure 7. The rhombus windows of these polymeric complexes are constructed from four Hg atoms and four Ln-F ligands. The side of rhombus (based on Hg…Hg distances) is ca. 6.675, 6.735, 6.567, 6.690, 6.567 and 6.722 Å, for complexes 1-6, respectively. The dimension of diagonals of these rhombuses are ca. 10.315×8.477, 10.400×8.559, 10.326×8.116, 10.466×8.334, 10.221×8.248, and 10.370×8.557 Å2, for complexes 1-6, respectively. In these windows, from topological perspective, each metal atom can be viewed as 4-connected nodes and Ln-F ligands are considered as linkers. As a result, from the seven compounds synthesized here, complexes 1-6 are good candidates for the investigation of the intramolecular interactions, although the last one, complex 7, will also be described. Therefore, in the following discussion, first, we will focus on the description of F…F and F…π fluorine-involved intra-



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molecular interactions and structural motifs of the coordination polymers 1-6 in details. In complexes 1-6, since the C–C connecting aryl rings and Pyz–CO–NH moieties in ligands are flexible in rotation around the Namide−Cphen bond, fluorinated-phenyl rings have oriented in a way that produce diverse intramolecular interactions. So, it can be considered that fluorinated-phenyl rings as hanging groups in the windows are pointed toward the adjacent groups to generate different fluorine-involved intra-molecular interactions. Such conformationally flexible mercury complexes containing pyrazineamide ligands have previously been reported in detail by some of us.62-66 As depicted in Figure 8, complexes 1 and 2 have the same fluorine-involved interactions in the 2D windows. In these compounds main contact in the windows is intra-molecular F1⋯πpyz interaction that is cooperates with intra-molecular C-H…F and C-H…O hydrogen bonds, Figure 8, Table S2. The geometrical parameters of the C–F1⋯π interactions in the compounds 1 and 2 are summerized in Table 3. According to geometric parameters, especially the ra values (2.987 and 2.932 Å for 1 and 2, respectively) which are slightly shorter than the sum of the van der Waals radii of the fluorine and carbon atom (rC + rF = 3.17 Å),77 these interactions can be categorized as strong32 localized (L) interactions.94 In complexes 3 and 4, although the asymmetric units are similar, interactions in 2D windows are different, Figure 9, interactions in 2D windows are The intra-molecular C-H…F and C-H…O hydrogen bonds are main interactions in 2D widows of complex 3, Table S2, while similar to complexes 1 and 2, intra-molecular F⋯πpyz interaction and intra-molecular C-H…F and C-H…O hydrogen bonds, can be found in 2D widows of complex 4, Figure 9(b), Tables 3 and S2. Due to geometric parameters, in contrast to complexes 1 and 2, here for complex 4, intra-molecular F⋯πpyz interaction can be considered as delocalized (D) interaction,94 with fluorine-to-pyrazine ring centroid distance, rr , of 2.940 Å. The analysis of the crystal structures of complexes 5 and 6 reveals that there are no strong specific intermolecular interactions in 2D windows. In these compounds fluorinated phenyl groups are pointed toward the adjacent groups to form intra-molecular F…F, Table 2, and F…πphen interactions, Table 3, in 10 ACS Paragon Plus Environment

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2D windows, Figure 10. In complex 6 fluorine-involved interactions are cooperate with weak C-H…F and C-H…O hydrogen bonds, Table S2. In complex 5, the packing shows type II F···F contacts between F1 and F3 of two adjacent phenyl ring in 2D windows at a distance of 2.779(7) Å, where the angles are 153.9° and 83.0° for C-F1…F3 and C-F3…F1, respectively, Table 2. F…F contact distance of 2.779(7) Å in this compound indicates a 5.5% reduction of the sum of van der Waals radii, Table 2.77 Also in this compound, according to geometric parameters, especially the ra values of 2.944 Å, Table 3, which are slightly shorter than the sum of the van der Waals radii of the fluorine and carbon atom (rC + rF = 3.17 Å),77 intra-molecular F1⋯πphen interaction can be categorized as strong32 localized (L) interactions.94 Crystal structure determination of complex 6 exhibited the type II F…F contacts at a short distance of 2.701 Å between the F2 and F4 of the two adjacent phenyl rings in the window. The C-F2…F4 and CF4…F2 angles θ1 = 68.2° and θ2 = 156.4°, respectively, Table 2. The F…F intermolecular distance in compound 6, 2.701 Å, is 8.1% shorter than the sum of the van der Waals radii of fluorine atoms,77 Table 2. A Cambridge Structural Database search75 shows 1684 molecules containing type II F···F interactions at distances ranging from 2.00 to 3.20 Å, where the angles θ1= 60−90° and θ2 = 150−180°, with the restrains “no ions” and “not distorted”. The number reduces to only 54 cases when the distance range is shortened to 2.60−2.71 Å. With a restriction of the angles to θ1 = 65−90° and θ2 = 155−180° in the CSD search, while keeping the distance range as 2.0−3.2 Å, 17 molecules are observed to show these interactions.95-110 As mentioned earlier, apart from the presence of short F···F contact similar to 5, in complex 6 there is strong32 localized (L)94 intra-molecular F4⋯πphen interaction in the 2D windows, Figure 10, Table 3. So, it can be concluded that the presence of a strong tendency to form intra-molecular F…π interactions in the crystal structure of all mentioned polymeric complexes, except complex 3, in the 2D windows is one of the common features in the crystal structures, Scheme 2. In the crystal structure of complexes 5 and 6, carrying three and four fluorine atoms on phenyl rings, type II F…F synthons between adjacent



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rings in the windows have also observed in cooperation to F…π interactions, Scheme 2. It is noticeable that, although complex 7 has a discrete structure, type I F…F contacts have dominant effect in the formation of 1D linear chains spaning along the c-axis, Table 2, Scheme 2. Among seven almost isostructural complexes described in the present work, complex 3 has no F…F/π intra- or interinteractions, Scheme 2. The intermolecular interactions in the crystal structures of 1-7 can also be quantified via Hirshfeld surface analysis study111-112 using the crystal explorer.113-114 Through the Hirshfeld surface analysis, visualization of the intermolecular contacts in the crystal structures can be done.115 The contributions of fluorine contacts including F…F, F…C and F…N interactions to the Hirshfeld surface areas are mainly estimated. The percentage of contributions of other contacts such as C…C, C…N, F…H are also considered as pie charts in Figure 11. In complexes 1 and 2, F…H contact is contributes 3.9% and 9.2%, respectively, whereas only less than 3.4% and 5.6% contribution, in 1 and 2, respectively, comes from the F···F/C/N contacts. In complex 3 as can be expected only less than 1.7% contribution comes from the fluorineinvolved F···F/C/N contacts. The analysis shows that, in complexes 4, 5 and 6, the F···F halogen contact contributes by about 4.6%, 9.0% and 8.9% and the fluorine atom is involved in the F···C/N interactions with a total contribution of 6.8%, 5.2% and 9.8% for 4, 5 and 6, respectively. In discrete complex 7, due to the presence of F…F, C-H…O and C-H…F interactions as main factor in the crystal packing, 2.4%, 2.4% and 9.2% contributions for F…F, F…C/N and F…H, respectively, are acceptable. In all cases, “others” part of the pie chart refers to the weak interactions such as Hg…H, Hg…O, N…N, N…O, C…O and O…O contacts.

3. Conclusion In conclusion, to gain a deeper understanding on the crucial role of fluorine-involved interactions in the supramolecular architecture of coordination compounds, 2D polymeric complexes of Hg(II) complexes 12 ACS Paragon Plus Environment

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including N-(fluorinatedphenyl)pyrazine-2-carboxamide ligands have been structurally explored. All polymeric complexes have the same 2D windows. In the presence of ligand flexibility, fluorinated-phenyl rings as hanging groups in these windows are pointed toward the adjacent groups to generate different fluorine-involved intra-molecular interactions. Main contact in the 2D windows of complexes containing N-(2/2,5-mono/difluorinatedphenyl)pyrazine-2- carboxamide ligands is strong localized intra-molecular F…πpyz interaction. For complex containing N-(2,3,4-trifluorinatedphenyl)pyrazine-2-carboxamide ligand, intra-molecular F…πpyz interaction as main interaction in 2D windows can be considered as delocalized interaction.

Inspection

of

the

crystal

structures

of

complexes

containing

N-(3,4,5/2,3,4,5-

tri/tetrafluorinatedphenyl)pyrazine-2-carboxamide ligands reveals that fluorinated phenyl groups are involved in the intra-molecular type II F…F contacts as well as strong localized intra-molecular F…πphen interactions. Therefore, presence of a strong tendency to form intra-molecular F…F/π interactions in the 2D sheet windows is one of the common features in the crystal structures of the synthesized polymeric complexes. Hirshfeld surface analysis also confirms that the F…F/π contacts are predominant. So, the weak fluorine-involved interactions are mainly responsible for the interaction between neighboring basic structural motifs even in proximity of the other functional groups.

4. Experimental Single crystal diffraction studies. X-ray data for compounds [Hg(L2-F)2]n, 1, [Hg(L2,5-F)2]n, 2, [Hg(L3F

)2]n, 3, [Hg(L2,3,4-F)2]n, 4, [Hg(L3,4,5-F)2]n, 5, [Hg(L2,3,4,5-F)2]n, 6, and [Hg(L2,6-F)2], 7, were collected on a

STOE IPDS-2T diffractometer with graphite monochromated Mo-Kα radiation. The colorless block crystals of 1 and 5, colorless prism crystals of 3, 4 and 6, colorless plate crystal of 2 and light yellow prism crystal of 7, were chosen using a polarizing microscope and they were mounted on a glass fiber which was used for data collection. Cell constants and an orientation matrix for data collection were obtained by least-squares refinement of diffraction data from 2232 for 1, 2298 for 2, 2193 for 3, 2359 for 13 ACS Paragon Plus Environment


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4, 2292 for 5, 2392 for 6 and 2252 for 7, unique reflections. Data were collected at a temperature of 298(2) K to a maximum θ value of 27.00° for all compounds and in a series of ω scans in 1° oscillations and integrated using the Stoe X-AREA116 software package. A numerical absorption correction was applied using the X-RED117 and X-SHAPE118 software’s. The data were corrected for Lorentz and Polarizing effects. The structures were solved by direct method119 and subsequent different Fourier maps and then refined on F2 by a full-matrix least-square procedure119 using anisotropic displacement parameters. All hydrogen atoms were added at ideal positions and constrained to ride on their parent atoms, with Uiso(H) = 1.2 Ueq. All refinements were performed using the X-STEP32 crystallographic software package.120 Structural illustrations have been drawn with ORTEP-3121 and MERCURY.122 Crystallographic data for complexes 1-7 are listed in Table 1. Selected bond distances and angles are summarized in Table S1. Synthesis of N-(fluorinatedphenyl)-2-pyrazinecarboxamide, Ln-F, ligands. The ligands were prepared according to previous procedure.72 Synthesis of [Hg(L2-F)2]n, 1. Hg(CF3CO2)2 salt (42 mg, 0.1 mmol) was dissolved in 15 ml methanol and then added to the slotion of L2-F (216 mg, 0.1 mmol) in 15 mml of methanol. The mixture was stirred for 30 minutes and then kept in room temperature until colourless block crystals was formed. Synthesis of [Hg(L2,5-F)2]n, 2. To the solution of Hg(CF3CO2)2 (42 mg, 0.1 mmol) in methanol (10 ml), a solution of L2,5-F (235 mg, 0.1 mmol) in methanol (10 ml) was added. The mixture then was stirred for 30 minutes. The suitable plate crystals were obtained upon slow evaporation after several days. Synthesis of [Hg(L3-F)2]n, 3. A methanol solution (10 ml) of 0.1 mmol of mercury salt was added to a solution of L3-F (216 mg, 0.1 mmol) in methanol (10 ml). In the similar method, colourless prism crystals of complex were obtained. Synthesis of [Hg(L2,3,4-F)2]n, 4. As previous case, the same methanol solution of mercury salt (42 mg, 0.1 mmol) and ligand (254 mg, 0.1 mmol) were mixed and stirred. The colorless prism crystals were obtained


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by similar method. Synthesis of [Hg(L3,4,5-F)2]n, 5. As this complex was formed and separated from solution immediately after adding ligand solution, the reaction was performed in the more solvent. So, Hg(CF3CO2)2 (42 mg, 0.1 mmol) was dissolved in 20 ml of methanol and added to the same equivalent of ligand (254 mg) in methanol (20 ml), the mixture was left at ambient condition until suitable block crystals were formed. Synthesis of [Hg(L2,3,4,5-F)2]n, 6. Like complex 5, this complex was synthesised in the more solvent. The method was repeated similar to the above as methanolic solution (20 ml) of Hg(CF3CO2)2 (43 mg, 0.1 mmol) and ligand (273 mg, 0.1 mmol) were mixed. The suitable crystal was obtained by slow evaporation of complex solution. Synthesis of [Hg(L2,6-F)2], 7. To the solution of Hg(CF3CO2)2 (42 mg, 0.1 mmol) in methanol (15 ml), a solution of L2,6-F (235 mg, 0.1 mmol) in methanol (15 ml) was added. In the similar method, The mixture was then stirred for 30 minutes. The yellow prism crystals were obtained upon slow evaporation after several weeks. Hirshfeld surface analysis. The intermolecular interactions in the crystal structures of complexes 1-7 are quantified via Hirshfeld surface analysis using Crystal Explorer 3.0112-113

ACKNOWLEDGMENT: We would like to thank the Graduate Study Councils of Shahid Beheshti University, General Campus and the Iran National Science Foundation (grant no. 95828592) for financial support.

SUPPORTING INFORMATION Electronic Supplementary Information (ESI) available: Selected bond distances and angles, hydrogen bonding parameters (Å and °) and X-ray crystallographic files in CIF format. This material is free of charge via Internet at http://pubs.acs.org. 15 ACS Paragon Plus Environment


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Scheme 1. Schematic representation of the synthetic route of complexes 1-7.


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Scheme 2. Schematic representation of fluorine-involved intra- and inter-molecular interactions of compounds 1-7.



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(a)

(b)

(c)

(d)

(e)

(f)

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(g) Figure 1. ORTEP diagram of polymeric coordination compounds [HgL2-F]n, 1, (a), [HgL2,5-F]n, 2, (b), [HgL3-F]n, 3, (c), [HgL3,4,5-F]n, 4, (d), [HgL2,3,4-F]n, 5, (e), and [HgL2,3,4,5-F]n, 6, (f), and discrete complex [HgL2,6-F]n, 7, (g), showing coordination geometry around central metal. Ellipsoids are drawn at 30% probability level. Symmetry codes: (a) i: -x, -y, -z, ii: -x, -½+y, ½-z, iii: x, ½-y, -½+z, iv: -x, ½+y, -½-z, (b) i: -x, -y, -z, ii: -x, -½+y, -½-z, iii: x, ½-y, ½+z, iv: -x, -½+y, -½-z, (c) i: 1-x, -y, -z, ii: 1-x, -½+y, -½-z, iii: x, ½-y, ½+z, iv: 1-x, ½+y, -½-z, (d) i: -x, -y, 1z, ii: -x, -½+y, 3/2-z, iii: x, ½-y, -½+z, iv: -x, ½+y, 3/2-z, (e) i: 1-x, -y, 1-z, ii: -x, -½+y, -3/2-z, iii: x, ½-y, -½+z, iv: 1-x, ½+y, 3/2-z, (f) i: -x, -y, -z, ii: -x, -½+y, -½-z, iii: x, ½-y, ½+z, iv: -x, -½+y, -½-z, and (g) i: -x, 1-y, -z.


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Complex

1 2 3 4 5 6

1 0.07 0.14 ˃0.4 0.19 ˃0.4

2

3

4

5

6

3.3

4.3 5.1

˃10 ˃10 3.4

6.5 ˃10 5.8 4.6

˃10 ˃10 5.8 4.6 4.1

0.15 ˃0.4 ˃0.4 ˃0.4

0.31 0.30 0.31

0.19 0.11

X-values

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


0.19

d-values

Figure 2. Xpac map containing the dissimilarity indices X and distance parameter d for compounds 1-6.



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(a) (b) Figure 3. Formation of the overall supramolecular assemblies in complex 1, (a), and 2, (b), through the head-to-tail Cphen-H…Npyz hydrogen bonds between adjacent 2D sheets. Side views of 2D sheets parallel to bc-planes are as the grey ribbons for better clarity.


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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(a) (b) Figure 4. Formation of the overall supramolecular assemblies in complex 3, (a), and complex 4, (b), through the head-to-tail Cpyz-H…F hydrogen bonds between pyrazine and phenyl rings from adjacent 2D sheets. Side views of 2D sheets parallel to bc-planes are as the grey ribbons for better clarity.



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(a) (b) Figure 5. Formation of the overall supramolecular architectures in complex 5, (a), through the cooperation of F…F and head-to-tail F…πphen interactions and in complex 6, (b), through the cooperation of F…F head-to-tail F…πphen interactions, and Cpyz-H…F hydrogen bonds. Side view of 2D sheets parallel to bc-planes are as the grey ribbons for better clarity.


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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(a)

(b)

(c) Figure 6. Formation of 1D linear chain in 7 by head-to-tail type I F…F contacts spanning along the c-axis, (a), generation of 2D sheets by cooperation of head-to-tail Cphen-H…O=C weak hydrogen bonds and πphen…πphen interaction, (b) and resulting of overall supramolecular architecture from the bifurcated Cphen-H…F interactions, (c).



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Figure 7. The 2D sheet windows. Different complexes are shown in different colors; 1 (red), 2 (orange), 3 (yellow), 4 (green), 5 (blue), and 6 (violet). For better clarity fluorinated-phenyl rings are omitted.


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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(a) (b) Figure 8. Presence of intra-molecular F⋯πpyz interaction in 2D widows of complex 1, (a) and 2, (b), that is cooperates with intra-molecular C-H…F and C-H…O hydrogen bonds. Side views of 2D sheets parallel to bc-planes are as the grey ribbons for better clarity.



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(a) (b) Figure 9. Presence of intra-molecular C-H…F and C-H…O hydrogen bonds in 2D widows of complex 3, (a) and intra-molecular F⋯πpyz interaction in 2D widows of complex 4, that is cooperates with intramolecular C-H…F and C-H…O hydrogen bonds, (b). Side views of 2D sheets parallel to bc-planes are as the grey ribbons for better clarity.


Page 35 of 40

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(a) (b) Figure 10. Presence of intra-molecular F⋯πpyz and F…F interactions in 2D widows of complex 5, (a) and 6, (b). In complex 6 fluorine-involved interactions are cooperate with intra-molecular C-H…F and CH…O hydrogen bonds. Side views of 2D sheets parallel to bc-planes are as the grey ribbons for better clarity.



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Figure 11. Relative contributions of various intermolecular contacts to the Hirshfeld surface area in compounds 1-7.


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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Table 1. Structural data and refinement for complexes 1-7. formula fw

Complex 2 C22H12F4Hg N6O2 668.97






λ/Å

0.71073

0.71073

0.71073

0.71073

0.71073

0.71073

0.71073

T/K

298(2)

298(2)

298(2)

298(2)

298(2)

298(2)

298(2)

crystal.system

Monoclinic

Monoclinic

Monoclinic

Monoclinic

Monoclinic

Monoclinic

Monoclinic

space group

P21/c

P21/c

P21/c

P21/c

P21/c

P21/c

P21/c

a/Å

12.1233(12)

12.1957(14)

12.224(2)

12.5707(13)

12.5734(12)

12.4920(8)

10.5557(10)

b/Å

8.4766(12)

8.5594(10)

8.1159(9)

8.3342(10)

8.2475(10)

8.5567(5)

13.3985(16)

c/Å

10.3145(11)

10.4001(12)

10.3263(16)

10.4662(11)

10.2208(10)

10.3699(7)

7.3055(7)

β/°

104.475(8)

104.098(9)

100.885(12)

99.334(8)

96.731(8)

98.201(5)

95.957(8)

V/Å3

1026.3(2)

1052.9(2)

1006.0(3)

1082.0(2)

1052.58(19)

1097.11(12)

1027.64(19)

Dcalc/Mg m-3

2.048

2.110

2.090

2.164

2.224

2.243

2.162

Z

2

2

2

2

2

2

2

-1

µ/mm

7.551

7.389

7.703

7.200

7.401

7.119

7.561

F(000)

604

636

604

668

668

700

636

2θ/°

54.00

54.00

54.00

54.00

54.00

54.00

54.00

R(int)

0.0812

0.0535

0.0854

0.0672

0.1005

0.1110

0.0958

GOOF

0.939

1.071

0.948

0.926

1.021

0.988

1.011

R1a(I > 2σ(I))

0.0390

0.0292

0.0538

0.0258

0.0308

0.0291

0.0540

b

a


wR2 (I > 2σ(I))

0.0709

0.0906

0.1282

0.0605

0.0533

0.0654

0.1112

CCDC No.

1497498

1497496

1497500

1497495

1497499

1497494

1497497

R1 =Σ||Fo| - |Fc||/Σ|Fo|. bwR2 = [Σ(w(Fo2 - Fc2)2)/Σw(Fo2)2]½.



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Page 38 of 40

Table 2. Geometrical parameters (Å and °) for the description of the F…F halogen bonding in complexes 5-7. Complex 5 (F1…F3)

Complex 5 (F2…F2)

Complex 6 (F2…F4)

Complex 6 (F3…F3)

Complex 7 (F1…F2)

F...F(Å)

2.779(7)

2.937(7)

2.701(8)

3.031(7)

2.915(6)

θ1(°)

153.9(5)

79.1(4)

156.4(4)

81.2(4)

132.7(5)

θ2(°)

83.0(4)

79.1(4)

68.2(3)

81.2(4)

143.8(5)

Type

II

I

II

I

I

Sym. code

x,½-y,-½+z

-x,-y,1-z

x,½-y,½+z

1-x, -y,-z

1-x, -y,-z

Change of sum of vdW radii

5.5%

Coordination Polymers with Intramolecular Fluorine-Involved Contacts

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