Effects of Orthohalogen Substituents on Nitrate Binding in Urea-Based

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Effects of orthohalogen substituents on nitrate binding in urea-based silver(I) coordination polymers Alireza Azhdari Tehrani, Sedigheh Abedi, and Ali Morsali Cryst. Growth Des., Just Accepted Manuscript • Publication Date (Web): 07 Dec 2016 Downloaded from http://pubs.acs.org on December 7, 2016

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Crystal Growth & Design

Effects of orthohalogen substituents on nitrate binding in ureabased silver(I) coordination polymers

Alireza Azhdari Tehrani, Sedigheh Abedi, Ali Morsali,* Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran. E-mail: [email protected];

Abstract The urea group is widely used functional group in anion recognition owing to its ability to interact effectively with anions via formation of chelate hydrogen bonds. Previous solution state study shows that the presence of halogen substituents at ortho-positions to the urea moiety strongly enhances intermolecular hydrogen bonding interactions. In order to investigate the effect of the presence of ortho-halogen substituents on hydrogen bonding of aromatic ureas in the context of metallosupramolecular chemistry, three Ag(I) coordination polymers were synthesized and characterized by different techniques. The nitrate binding and the supramolecular organization in these compounds were studied by different geometrical and theoretical calculations. Based on this study, we can conclude that, as expected, the N-H···O hydrogen bond plays a key role in nitrate binding for this type of ligands, while weak C-X···O halogen bonds assist the anion binding to the receptor.

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Introduction Research in the area of coordination polymers has attracted intense interests in recent years due to their rich structural chemistry and their wide range of applications as functional materials.1, 2 It is well-known that physical and chemical properties of materials are dictated by the relative orientation and organization of the molecular building blocks.3, 4 Therefore, supramolecular chemists have endeavored to control this ordering, so as to fully understand how properties are influenced by the supramolecular assemblies.5 Previous researches clearly revealed that the final supramolecular architecture of metal-containing species is dependent on different determining factors, such as metal and ligand geometries,6, 7 counterions8, 9 and the reaction conditions.10, 11 Not surprisingly, the judicious selection of organic ligand has been verified to be one of the most important factor in the construction of coordination polymers, because it can not only provide suitable binding sites but can also direct the self-assembly through providing potential interaction sites for generating desired intermolecular interactions.12-16 Urea, thiourea and squaramide groups are known to form strong hydrogen bonds with Y-shaped anions, such as nitrates sulfates, and phosphates.17,

18

Thus, considerable attentions have focused on designing

anion receptors based on these hydrogen bond donating functional groups.19-24 Coordination compounds with ligands containing urea moieties have found use in a wide variety of applications, such as anion binding and recognition.18, 25, 26 The use of urea-containing coordination polymers for anion separation has been explored by Custelcean and Dastidar's research groups.27-32 In these examples, the anions behave as a structural link interconnecting the coordination chains by urea-anion hydrogen bonds into layers, or layers into 3D frameworks.33, 34 Following these studies, examples of metal-organic polyhedra containing ureagroups were designed and investigated for anion sensing application.35, 36 Recognition of anions through the combination of halogen and hydrogen bonding interactions is also an interesting subject on its own, and has potential applications in selective anion recognition. The report by Nangia et al was the first that


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showed the cooperativity between hydrogen and halogen bonds in anion recognition in a series of silver complexes of para-halogen substituted phenyl-pyridyl urea compounds.37 Soon after this report, a series of urea-based anion receptors bearing halogen bond donors have been reported to probe the potential of this combination in anion recognition.38-41 Also, there are a few papers discussed the effects of the presence of ortho-halogen substituents on hydrogen bonding of aromatic ureas,42, 43 and to the best of our knowledge this effect has not been previously studied in the context of metallosupramolecular chemistry. As part of our research program aimed at understanding the roles of supramolecular interactions in the construction of metallosupramolecular architectures,44-47 we became interested in preparing silver(I) coordination polymers based on 1,3-bis(2-halo-4-cyanophenyl)urea ligands, LCl, LBr and LI, carrying halogen atoms in the ortho position of the phenylurea moiety. Thus, herein, three Ag(I) coordination polymers, namely [Ag(NO3)(LCl)](1), [Ag(NO3)(LBr)](2) and[Ag(NO3)(LI)](3), were synthesized and characterized by different techniques. The nitrate binding and the supramolecular organization in these compounds were studied by different geometrical and theoretical calculations. Our study reveals that in compounds 1-3, nitrate binding takes place via a combination of N-H···O hydrogen bonds and weak C-X···O halogen bonds.

Experimental Section Synthesis of Ligand LX The synthesis of 1,3-bis(2-halo-4-cyanophenyl)urea (LCl/Br/I) ligands was straightforward and was achieved in one step, starting from 4-amino-3-halobenzonitrile (see supporting information). Synthesis of [Ag(NO3)(LCl)](1) A solution of AgNO3 (0.05 mmol) in 2 mL of methanol was layered over a solution of LCl (0.1 mmol) in 2 mL of THF and 0.5 mL of chloroform. Suitable block crystals of 1 for X-ray analysis were obtained after 4



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days (Yield 54%). Anal. calcd for C15H8Cl2AgN5O4: C, 35.96; H, 1.61; N, 13.98. Found: C, 34.98; H, 1.54; N, 13.74. Selected IR bands (KBr pellet, cm-1): 3442 (w), 3264 (w), 2240 (m), 1727 (m), 1574 (s), 1514 (s), 1295 (m), 1186 (m), 834 (w), 587 (w). 1H NMR (d6-DMSO): 9.64 (2H, s), 8.33 (2H, d), 8.10 (2H, s), 7.80 (2H, d) Synthesis of [Ag(NO3)(LBr)](2) A solution of AgNO3 (0.05 mmol) in 2 mL of methanol was layered over a solution of LBr (0.1 mmol) in 2 mL of THF and 0.5 mL of chloroform. Prism crystals of 2 for X-ray analysis were obtained after 5 days (Yield 38%). As the crystals were unstable when exposed to the atmosphere, crystallographic data was collected at 120 K. Anal. calcd for C15H8Br2AgN5O4: C, 30.54; H, 1.37; N, 11.87. Found: C, 30.12; H, 1.32; N, 11.78. Selected IR bands (KBr pellet, cm-1): 3441 (w), 3324 (w), 2228 (m), 1726 (m), 1569 (s), 1511 (s), 1293 (m), 1192 (m), 828 (w), 582 (w).1H NMR (d6-DMSO): 9.48 (2H, s), 8.23 (2H, s), 8.18 (2H, d), 7.82 (2H, d) Synthesis of [Ag(NO3)(LI)](3) A solution of AgNO3 (0.05 mmol) in 2 mL of methanol was layered over a solution of LI (0.1 mmol) in 2 mL of THF and 0.5 mL of chloroform. Suitable needle crystals of 3 for X-ray analysis were obtained after 4 days (Yield 62%). Anal. calcd for C15H8I2AgN5O4: C, 26.34; H, 1.18; N, 10.24. Found: C, 26.18; H, 1.22; N, 10.2. Selected IR bands (KBr pellet, cm-1): 3431 (w), 3320 (w), 2223 (m), 1709 (m), 1558 (s), 1502 (s), 1277 (m), 1176 (m), 831 (w), 578 (w). 1H NMR (d6-DMSO): 9.14 (2H, s), 8.36 (2H, s), 7.94 (2H, d), 7.80 (2H, d) Results and Discussion Treatment of 4-amino-3-halobenzonitriles with 1,1'-carbonyldiimidazole in refluxing THF led to the formation of the ligands LCl, LBr and LI. 1H-NMR experiments show that the urea –NH protons are


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downfield shifted, LI (9.13 ppm)→ LBr (9.47 ppm)→ LCl (9.62 ppm), which is consistent with the electronegativity of halogen. It is to be noted that the urea –NH protons of 1,3-bis(4-cyanophenyl)urea (LH) are appeared at 9.32 ppm.48,

49

This indicates that the presence of chlorine and bromine in the ortho-

position to the urea moiety leads to the polarization of urea N-H fragments and as a consequence of which the H-bond donating tendency of the urea groups of LCl/Br ligands is enhanced. However, the signal of urea –NH protons of LI ligand is upfielded with respect to LH ligand. A survey in Cambridge Structural Database (CSD) revealed that the urea groups have strong tendency to self-assemble into one-dimensional (1D) H-bonded chain via bifurcated N-H···O hydrogen bonds. However, it has been shown that the presence of anions disrupts the self-assembly of 1D urea chains by competing with the carbonyl oxygen atom of urea group for the receptor site. Compounds 1, 2 and 3 were synthesized by layering a methanolic solution of AgNO3 over a solution of LX (X=Cl, Br and I) in a mixture of acetone and chloroform. Compounds 1 and 2 crystallize in Triclinic Pī space group, while 3 crystallizes in monoclinic P21/c space group. Crystallographic data and selected bond distances and angles of compounds 1-3 are listed in Tables 1 and 2, respectively. SEM images and assynthesized powder X-ray diffraction (PXRD) of compounds 1-3 prepared by layering technique are shown in Figures S1 and S2. The FT-IR spectra of compounds 1-3 show characteristic peaks for the urea groups at 3334, 3330 and 3322 cm-1 (NH), 1725, 1720 and 1716 cm-1 (CO) and for the CN group at 2234, 2230, 2227 cm-1, respectively. It is to be noted that the NH peak gets broadened with a significantly reduced intensity upon coordination and formation of urea/NO3- complex.

ORTEP diagrams of these three

compounds drawn with 30% ellipsoid probability have been shown in Figure S3. The asymmetric unit of compounds 1-3 each comprises an Ag(I) cation, a LX ligand and a nitrate ion. The coordination geometry around Ag(I) in compounds 1 and 2 can be described as distorted trigonal pyramidal with τ4 fourcoordinate geometry index50 of 0.78 and 0.8, respectively, while the coordination geometry around Ag(I) in



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compound 3 is best described as distorted trigonal bipyramidal geometry with τ5 five-coordinate geometry index51 of 0.76. In both 1 and 2, the distorted trigonal pyramidal geometry around Ag(I) is constructed by two nitrogen atoms form cyano groups of LX ligands and a chelating nitrate anion. However, in the case of 3, the trigonal bipyramidal coordination sphere around silver(I) is constructed from a nitrogen atom of a cyano group and an iodine atom in apical positions and the other iodine atom and two oxygen atoms of nitrate anion in equatorial positions. In coordination chemistry, the silver ion can be considered as a soft acceptor and it would be expected to interact with halogen atoms in the order of I > Br > Cl.52 Accordingly, one of the Ag-N bonds in 1 and 2 is replaced by Ag-I bonds in compound 3. In 1 and 2, the metal centers are held together by bridging LCl/Br ligands forming 1D linear polymeric chain spanning along the [1 1 2] direction, while compound 3 exhibits a 1D polymeric chain extending along the [0 2 0] direction. The flexibility of coordination sphere of Ag(I) is associated with its closed shell electronic configuration and has been extensively used to create different tailor-made molecular architectures.53-55 The dihedral angles between the planes of phenyl groups and urea moiety for compounds 1-3 are listed in Table S1. In considering the dihedral angle values, it is clear that the phenyl-phenyl dihedral angle, as well as phenylurea dihedral angles, deviate increasingly from coplanarity with increasing size of the halogen atom. Crystal structure analysis of compounds 1-3 reveals that the two hydrogen atoms in the ortho-positions of urea moiety are intramolecularly hydrogen-bonded to carbonyl oxygen atom to form six-membered ring with S(6) graph set motif. The urea NH groups also serve as hydrogen bond donors and the halogen atoms serve as hydrogen bond acceptors in intramolecular N-H···X hydrogen bonds. Geometrical analysis reveals that the intramolecular N-H···X hydrogen bond is strengthened on going from LI to LCl, which is consistent with the near coplanarity of the phenyl groups and urea moiety in compound 1, compared to 2 and 3, and hydrogen bond accepting properties of halogens. Parameters for selected intra- and intermolecular hydrogen bonding interactions are listed in Table 3.


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Abad and de Arellano studied the effect of the regiochemistry and degree of fluorination of the phenyl ring on the solid state organization of a library of fluorinated N-(2-chloropyridin-4-yl)-N´-phenylureas compounds.42 They have found that the introduction of two fluorine atoms in 2,6-positions disrupts the coplanarity of the aromatic and urea moieties more than the substitution of single fluorine atom at ortho position. Bouteiller and his co-workers also showed that the presence of halogen atoms in the orthopositions to the urea moiety strongly enhance intermolecular hydrogen bonding interactions.43 Coordination polymers 1-3 demonstrate a common feature of urea-containing ligands, in which the urea group involves in hydrogen bonding with the coordinated anion.27, 28 Accordingly, in these compounds, the coordinated nitrate ion is involved in hydrogen bonding with both urea NH groups in a bifurcate mode (N-H···O distances of 2.181(3) Å and 2.253(2) Å for 1, 2.125(8) Å and 2.186(8) Å for 2 and 2.148(7) Å and 2.242(5) Å for 3), thus forming the six-membered ring motif [with graph-set notation 6]. Also, a CSD search conducted on aromatic ureas and nitrate ion gave 55 hits.56 Analysis of the results show that the urea moiety of phenylureas can involve in hydrogen bonding interactions with one or two oxygen atoms of nitrate anion, forming 6 and 8 ring motifs, respectively. Although both motifs are particularly prevalent in the case of urea containing metal complexes, 8 hydrogen bonding motif is observed more frequently compared to 6 in the reported crystal structures, Table S2. Moreover, the structural analysis reveals that the

ureaN-H···Onitrate

hydrogen bonding interactions are further assisted by

weak C-X···Onitrate halogen bonds, where X is Cl, Br and I. The distances of C-X···Onitrate halogen bonds are found to be 3.163(3) Å (∠C10-Cl2···O3=113.44(15)˚) and 3.187(3) Å (∠C4-Cl1···O3=113.04(13)˚), 3.152(10) Å (∠C1-Br1···O4=107.4(4)˚) and 3.177(10) Å (∠C15-Br2···O4=107.6(4)˚), 3.523(6) Å (∠C4I1···O3=102.4(2)˚), 3.513(6) (∠C4-I1···O4=99.4(2)˚) and 3.456(7) Å (∠C10-I2···O3=108.0(2)˚) and, for compounds 1-3, respectively, which are 0.37-0.65% longer and 1.26-6.47% shorter than sum of the van der Waals radii of halogen and oxygen atoms, Table 4. Although the preference for halogen bonding



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interaction to adopt contact angle of 180° is well-known,41, 57 the weak C-X···O angle in compounds 1-3 is in the range of 99.4-113.0˚ due to the geometrical restrictions. The Cambridge Structural Database (CSD)56 was analyzed to study the C-X···O distances and C-X···O angle, where X is Cl, Br and I, Figure S4. The analysis of the scatter-plots reveals that while at short interaction distances the directionality of halogen bonding is remarkable, over longer distances, the dispersion of points increases, indicating that the C-X···O is less directional, similarly to the behavior observed for compounds 1-3.The intermolecular interactions involved in the crystal structure of these compounds can also be quantified via Hirshfeld surface analysis, Figure 4.58 The analysis reveals that in the crystal structure of all three compounds the O···H hydrogen bonds are the dominant intermolecular interactions (the highest contribution to the Hirshfeld surface area), while 2.8%, 2.9% and 4.8% contribution is attributed to C-X···O interactions in compounds 1-3, respectively, Table S3. Also, in agreement with the geometrical analysis, it is found that the

chlorine

and

bromine

atoms

in

compounds

1

and

2

are

involved

in

C-H···X

(Cl···H=11.8%,Br···H=10.8% and I···H=5.8%) hydrogen bonding interactions, while the iodine atoms of LI ligand in compound 3 have greater tendency to coordinate with the silver ion (Ag···Cl=1.1%, Ag···Br =1.5% and Ag···I=5.5%). Density functional theoretical (DFT) calculations at BLYP-D3/TZP level of theory were performed to determine the nitrate binding energies on two relative fragments which are cut out from CIF data of compounds 1-3, Table 4. The results show almost similar binding energies of -19.06, 18.74 and -19.21 Kcal/mol for compounds 1, 2 and 3, respectively. The nature of binding interactions are investigated by means of an energy decomposition analysis (EDA) in the framework of Kohn-Sham molecular orbital theory.59 The results reveal that the electrostatic term is the largest attractive term followed by dispersion, Table 4. Interestingly, the Pauli repulsion energy is highly positive in all three compounds but is noticeably lower for compound 3 compared to 2. This is presumably because of the large conformational changes that occur upon the introduction of large iodine atoms. Qualitative support can be


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obtained by comparing the electrostatic potential map of the LX ligands. As shown in Figure S5, the presence of electron withdrawing functionalities in these compounds is expected to enhance the H-bond donating ability of urea N-H groups as well as to increase the polarizability of halogen atoms, thereby making them better halogen bond donors.60 The nature of hydrogen and halogen bonds can be explored by using Bader’s Quantum Theory of Atoms In Molecules (QTAIM) analysis.61,

62

Electron density (ρb ),

laplacian of the electron density (∇2ρb), kinetic energy density (Gb), potential energy density (Vb) and Lagrangian Density (Lb) for the selected intra- and intermolecular interactions of optimized and the nonoptimized (derived from crystal data) structures of LX/NO3- are listed in Tables 4 and S4. QTAIM analysis reveals that each C-X···O interaction is characterized by a bond CP and bond path connecting the halogen atom to the oxygen atom, Figure S6. This analysis was also done for the optimized structure of 1,3-bis(4cyanophenyl)urea (LH) in the presence of nitrate ion. Compared to LH/NO3-, the nitrate ion in the presence of LCl/Br/I is slightly moved away from the urea N-H groups and, as a result, the N-H···O hydrogen bonds weaken, Figure S6. Although the substitution of hydrogen atoms at ortho-positions to the urea moiety with halogens could diminish the contribution of hydrogen bonds in anion binding, but the topological analysis of 1-3 further confirms that there are bond paths between the halogen atom of ligands LX and oxygen atom of coordinated nitrate ion and, therefore, the halogen bonding contribution to anion binding increases. Also, the strength and the number of halogen bonds that can be formed with nitrate oxygen atoms increases ongoing from LCl to LBr and further to LI, which are consistent with the geometrical and Hirshfeld surface analyses. Conclusion The urea group is widely used functional group in anion recognition owing to its ability to interact effectively with anions via formation of N-H···O hydrogen bonds. Accordingly, urea-containing coordination polymer can be a potential anion-binding host and this has been explored in a number of



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reports. Previous solution state study shows that the presence of halogen substituents at ortho positions to the urea moiety strongly enhances intermolecular hydrogen bonding interactions.43 In order to investigate the effect of the presence of ortho halogen substituents on hydrogen bonding of aromatic ureas in the context of metallosupramolecular chemistry, three Ag(I) coordination polymers based on ligands containing urea groups and ortho-halogen substituents at phenyl rings were synthesized and characterized by different techniques. The nitrate binding and the supramolecular organization in these compounds were studied by different geometrical and theoretical calculations. Based on this study, we can conclude that, as expected, the chelate N-H···O hydrogen bonding plays a key role in nitrate binding for this type of ligands, while weak C-X···O halogen bonds assist the anion binding process.

ASSOCIATED CONTENT

Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: Experimental details, ORTEP diagrams, QTAIM analysis details and Crystallographic data (CIF) AUTHOR INFORMATION

Corresponding Author [email protected] Notes The authors declare no competing financial interests. ACKNOWLEDGMENT

This work was funded by Tarbiat Modares University

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43. Giannicchi, I.; Jouvelet, B.; Isare, B.; Linares, M.; Dalla Cort, A.; Bouteiller, L., Chem Commun 2014, 50, 611-613. 44. Tehrani, A. A.; Morsali, A.; Kubicki, M., Dalton Trans. 2015, 44, 5703-5712. 45. Tehrani, A. A.; Abedi, S.; Morsali, A.; Wang, J.; Junk, P. C., J. Mater. Chem. A 2015, 3, 2040820415. 46. Khavasi, H. R.; Azhdari Tehrani, A., Inorg Chem 2013, 52, 2891-2905. 47. Abedi, S.; Tehrani, A. A.; Morsali, A., New J Chem 2015, 39, 5108-5111. 48. Narayanan, K.; Shanmugam, M.; Vasuki, G.; Kabilan, S., J Mol Struct 2014, 1056, 70-78. 49. Rajaganapathy, K.; Kalaichelvan, V.; Kabilan, S.; Balaji, P., Indo Am. j. pharm. sci. 2015, 5, 12341241. 50. Yang, L.; Powell, D. R.; Houser, R. P., Dalton Trans. 2007, 955-964. 51. Addison, A. W.; Rao, T. N.; Reedijk, J.; van Rijn, J.; Verschoor, G. C., J. Chem. Soc., Dalton Trans. 1984, 1349-1356. 52. Chandran, S. K.; Thakuria, R.; Nangia, A., Crystengcomm 2008, 10, 1891-1898. 53. Haj, M. A.; Aakeröy, C. B.; Desper, J., New J Chem 2013, 37, 204-211. 54. Chen, C.-L.; Kang, B.-S.; Su, C.-Y., Aust J Chem 2006, 59, 3-18. 55. Khlobystov, A. N.; Blake, A. J.; Champness, N. R.; Lemenovskii, D. A.; Majouga, A. G.; Zyk, N. V.; Schröder, M., Coord. Chem. Rev. 2001, 222, 155-192. 56. Cambridge Structural Database, version 5.37 (Last update May 2016), CCDC, Cambridge, U.K. 57. Voth, A. R.; Khuu, P.; Oishi, K.; Ho, P. S., Nat Chem 2009, 1, 74-79. 58. Spackman, M. A.; Jayatilaka, D., Crystengcomm 2009, 11, 19-32. 59. Bickelhaupt, F. M.; Baerends, E. J., Rev. Ccomp. Chem. 2007, 15, 1-86. 60. Khavasi, H. R.; Hosseini, M.; Tehrani, A. A.; Naderi, S., Crystengcomm 2014, 16, 4546-4553. 61. Dunitz, J. D.; Gavezzotti, A., Angew. Chem. Int. Ed. 2005, 44, 1766-1787. 62. Kirby, I. L.; Brightwell, M.; Pitak, M. B.; Wilson, C.; Coles, S. J.; Gale, P. A., Phys Chem Chem Phys 2014, 16, 10943-10958.


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(a)

(b) Figure 1. Representation of coordination polymer 1 binding nitrate ion by chelate N-H···O hydrogen bonding and weak C-Cl···O halogen bonding interactions.



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(a)

(b) Figure 2. Representation of coordination polymer 2 binding nitrate ion by chelate N-H···O hydrogen bonding and weak C-Br···O halogen bonding interactions.


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(a)

(b) Figure 3. Representation of coordination polymer 3 binding nitrate ion by chelate N-H···O hydrogen bonding and weak C-I···O halogen bonding interactions. For clarity, the aromatic rings of each coordination polymer chain are shown in different colors.



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Figure 4. Relative contributions of various intermolecular interactions to the Hirshfeld surface area in compounds 1–3.


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Table 1. Structural data and refinement parameters for compounds 1-3. 1 2 3 formula C15H8AgCl2N5O4 C15H8AgBr2N5O4 C15H8AgI2N5O4 fw 501.03 589.93 683.93 λ/Å 0.71073 0.71073 0.71073 T/K 298(2) 120(2) 298(2) crystal system Triclinic Triclinic Monoclinic space group Pī Pī P21/c a/Å 7.8586(16) 7.7460(7) 6.6806(13) b/Å 9.0599(18) 9.0478(8) 22.881(5) c/Å 12.470(3) 12.4898(10) 11.477(2) α/˚ 101.89(3) 101.923(7) 90 β/˚ 101.11(3) 100.470(7) 95.04(3) γ/˚ 92.45(3) 90.865(7) 90 V/Å3 849.4(3) 840.93(13) 1747.6(6) Dcalc/Mg.m-3 1.959 2.330 2.599 Z 2 2 4 µ (mm-1) 1.536 5.985 4.721 F(000) 492 564 1272 2θ (˚) 54.0 54.0 54.0 R (int) 0.0467 0.1719 0.0594 GOOF 1.044 0.956 1.021 R1a(I>2σ(I)) 0.0429 0.0799 0.0456 wR2b(I>2σ(I)) 0.1066 0.1787 0.0994 CCDC No. 1509227 1509228 1509229 a R1 =Σ||Fo| - |Fc||/Σ|Fo|. b wR2 = [Σ(w(Fo2 - Fc2)2)/Σw(Fo2)2]½.

Table 2. Selected bond distances (Å) and angles (°) for complexes 1-3.

Bond distance

Bond angle

a

Ag1-N1 Ag1-N4 Ag1-O2 Ag1-O3 Ag1-X1 Ag1-X2 N1-Ag1-N4 N1-Ag1-O2 N1-Ag1-O3 N4-Ag1-O2 N4-Ag1-O3 O2-Ag1-O3 N1-Ag1-I1 N1-Ag1-I2 I1-Ag1-I2

1 2.158(4) 2.183(4)a 2.626(4) 2.530(3) 158.19(14) 91.01(14) 107.04(12) 110.62(14) 90.04(11) 67.79(11) -

Complex 2 2.167(11) 2.190(11)b 2.562(9) 2.531(7) 156.5(4) 112.5(3) 91.5(3) 108.2(3) 90.03(3) 50.2(3) -

3 2.287(7) 2.834(9)c 2.684(7) 2.425(6) 2.9402(11)d 3.1653(12)e 75.0(2)a 107.1(2) 87.4(2) 105.65(18) 153.10(18) 89.04(3)

1+x, 1+y, -1+z; b-1+x, -1+y, 1+z; c –x,2-y, -z; d -1+x, 1.5-y, -1/2+z; e -2+x, y, -1+z



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Table 3. Selected intra and intermolecular hydrogen bond geometries for coordination compounds 1-3. Compound 1

2

3

D-H…A N2-H2A…O3 N3-H3A…O3 C6-H6…O1 C15-H15…O1 N2-H2A…Cl1 N3-H3A…Cl2 N2-H2A…O4 N3-H3A…O4 C6-H6…O1 C10-H10…O1 N2-H2A…Br1 N3-H3A…Br2 N2-H2A…O4 N3-H3A…O4 C6-H6…O1 C15-H15…O1 N2-H2A…I1 N3-H3A…I2

d(D-H)/Å 0.860 0.860 0.930 0.930 0.860 0.860 0.860 0.860 0.930 0.930 0.860 0.860 0.860 0.860 0.930 0.930 0.860 0.860

d(H…A)/Å 2.253(2) 2.181(3) 2.231(3) 2.214(3) 2.4734(14) 2.4870(12) 2.125(8) 2.186(8) 2.189(9) 2.240(9) 2.6170(12) 2.5848(15) 2.242(5) 2.148(7) 2.162(6) 2.203(6) 2.8078(7) 2.8181(9)

d(D…A)/Å 3.041(3) 3.002(4) 2.839(5) 2.830(5) 2.941(3) 2.954(3) 2.947(11) 2.989(12) 2.804(15) 2.855(16) 3.099(9) 3.085(10) 3.041(7) 2.944(9) 2.771(9) 2.795(9) 3.302(5) 3.282(5)

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