Investigating the effect of anion substitutions on the structure of silver-based coordination polymers

Accepted Manuscript Investigating the effect of anion substitutions on the structure of silver-based coordination polymers Azizolla Beheshti, Hamid Reza Zafarian, Carmel T. Abrahams, Giuseppe Bruno, Hadi Amiri Rudbari PII: DOI: Reference:

S0020-1693(15)00444-2 http://dx.doi.org/10.1016/j.ica.2015.09.006 ICA 16681

To appear in:

Inorganica Chimica Acta

Received Date: Revised Date: Accepted Date:

17 December 2014 5 September 2015 7 September 2015

Please cite this article as: A. Beheshti, H.R. Zafarian, C.T. Abrahams, G. Bruno, H.A. Rudbari, Investigating the effect of anion substitutions on the structure of silver-based coordination polymers, Inorganica Chimica Acta (2015), doi: http://dx.doi.org/10.1016/j.ica.2015.09.006

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1

Investigating the effect of anion substitutions on the structure of silver-based coordination polymers

1 2

Azizolla Beheshtia, Hamid Reza Zafariana, Carmel T. Abrahamsb, Giuseppe Brunoc and Hadi Amiri Rudbarid

3 4 5

a

6

Ahvaz, Iran b Department of Chemistry, Latrobe University, Bundoora 3086, Victoria,

7

Australiac Dipartimento di Chimica Inorganica, Vill. S. Agata, Salita Sperone 31,

8

Università di Messina, 98166 Messina, Italy

Department of Chemistry, Faculty of Sciences, Shahid Chamran University of Ahvaz,

d

9 10 11

Faculty of Chemistry, University of Isfahan, Isfahan 81746-73441, Iran.

*

E-mail: [email protected].: +98 611 33331042; Fax: +98 611 33331042

12 13

Abstract

14

Five silver(I) compounds namely, [Ag(tdmpp)(NO3)]n (1), [Ag2(SeCN)2(tdmpp)]n (2),

15

[Ag(tdmpp)]PF6

16

[WS4Ag4I2(tdmpp)]1.5CH3CN (5) were prepared by the reactions of 1,1,3,3-tetrakis(3,5-

17

dimethyl-1-pyrazolyl)propane (tdmpp) with various silver(I) salts in order to investigate the

18

impact of the variation of the inorganic anions on the structure of these complexes. In the

19

chain structures of 1 and 2, each tdmpp ligand acts as a bridge between a pair of adjacent

20

silver(I) centers. In the structure of 1, the nitrate ion act as a terminal, monodentate ligand,

21

while in compound 2 the SeCN anion functions as bidentate-bridging ligand between two

22

neighboring Ag(I) centers. The parallel adjacent chains in 1 and 2 are linked together by

23

means of non-covalent interactions to generate two-dimensional structures. In contrast to

24

the distorted AgN4O square–pyramidal structure of 1, in the structure of 2 each of the silver

25

ions possesses a distorted tetrahedral with an AgN3Se coordination geometry. Crystals of

26

compounds 3-5 were not suitable for X-ray diffraction studies.

(3),

[WS4Ag3Cl

(tdmpp)1.5].2CH3CN

(4)

and

27 Silver

coordination

polymers;

Tetradentate

28

Keywords:

29

Heterothiometallic cluster compounds; Chelating ligands.

30 31

1. Introduction

pyrazolyl-based

ligands;

2 32

The rational design and synthesis of silver (I) coordination polymers have been widely

33

studied. This study was motivated not only by the possibility of their application as

34

functional materials i.e. fluorescent materials, but also by the prospect of obtaining

35

fascinating structures that can be accessed by the variable coordination numbers from 2 to 6

36

and different conformations adopted by the silver ions [1-19]. The study of the coordination

37

chemistry with the pyrazole-based ligands began in 1889 with a report of the polymeric

38

[Ag(pz)]n complex [20]. Much later, Trofimenko et al. stimulated further research with the

39

introduction of poly(pyrazol-1-yl)borate chelating ligands in coordination chemistry [21-

40

24]. Following the discovery that chelating poly(pyrazol-1-yl)borate ligands formed strong

41

interactions with metal centres, the coordination chemistry of these ligands became the

42

focus of considerable attention [25-27]. These ligands may be used as synthetic analogs of

43

imidazole and mimic the coordinating sites found in metal enzymes or metalloproteins [28].

44

Unlike monodentate pyrazole and the rigid poly(pyrazol-1-yl)borate chelating ligands [29-

45

32], flexible pyrazole-based ligands, offer the prospect of conformtaions that will lead to

46

variation in coordination geometries, influenced by the spacer length and the orientations of

47

the donor atoms of the organic bridging ligands. The flexibility of these ligands can lead to

48

the generation of structures with interesting properties. Architectures with specific

49

structural motifs can be achieved by careful selection of organic ligands with the suitable

50

coordinating groups, metal centers with preferred coordination geometries and variation of

51

reaction conditions [33-36]. As a part of our research devoted to the synthesis, structural

52

and spectroscopic characterization of the coordination chemistry of pyrazole ligands, here

53

we report the synthesis and structural characterization of five new silver (I) coordination

54

polymers formed by the reaction of tdmpp ligand (Scheme 1) with appropriate silver(I)

55

salts. It is anticipated that this investigation will provide insights into the effect of different

56

inorganic anions on the structures of the silver(I) coordination polymers.

57

N N

N N

N N

N N

58 59

Scheme 1: Structure of the tdmpp ligand used in this work.

60 61

2. Experimental

3 62

2.1. Materials and physical measurements

63

All synthetic procedures were performed without precautions to exclude air. Starting

64

materials were purchased from commercial sources and used without further purification.

65

The tdmpp [36] and (NH4)2WS4 [37] were prepared from them by published methods. The

66

infrared spectra (4000–400 cm-1) were recorded on KBr disks with an FT-IR model

67

BOMEN MB102 spectrometer. The UV-Vis. spectra (700–270 nm) of [WS4]2- anion and

68

complexes 4 and 5 were recorded on a GBC Cintral 101 spectrophotometer from freshly

69

made samples in acetonitrile solution. X-ray powder diffraction patterns were recorded on a

70

Philips X’PertPro diffractometer (Cu Kα radiation, λ = 1.54184 Å) in the 2θ range 5-50°.

71

The elemental analyses for C, H and N were performed on a Costech-ECS 4010 CHNSO

72

analyzer.

73 74

2.2.Preparation of coordination polymers

75

2.2.1.Synthesis of [Ag(tdmpp)(NO3)] n (1)

76

A mixture of AgNO3 (0.190 g, 1 mmol) and tdmpp (0.420 g, 1 mmol) in acetonitrile (20

77

mL) was stirred at room temperature for 2 h. The precipitate was centrifuged and filtered

78

off. The residue was washed with ethanol (2×2 mL) and diethyl ether (2×3 mL) and dried

79

in vacuum to give a white powder of the product (439 mg, yield: 74% based on Ag).

80

Colorless needle-shaped single crystals suitable for X-ray diffraction studies were obtained

81

after 2 days by diffusion of diethyl ether into an acetonitrile solution of 1. Anal. Calc. for

82

AgC23 H32N9O3: C, 46.8; H, 5.5; N, 21.3. Found: C, 46.3; H, 5.1; N, 21.1%. IR (KBr,cm-1 ):

83

3126 (m) and 2918 (m) (-CH2- of spacer), 1635 (m), 1559 (s) (C=N of tdmpp), 1450(m),

84

1415 (m) and 1320 (s) (ʋ3 of NO3), 1030 (m), 781 (m), 572 (m).

85 86

2.2.2. Synthesis of [Ag2(SeCN)2(tdmpp)]n (2)

87

KSeCN (0.228 g, 2 mmol) and AgNO3 (0.340 g, 2 mmol) were added to DMSO (20 mL)

88

and the mixture was stirred and heated under reflux conditions at 80 ºC for 1h. To this

89

solution, tdmpp (0.420 g, 1 mmol) was added and the mixture was stirred for another 4 h.

90

The reaction mixture was filtered and colorless supernatant was decanted off. The

91

precipitate was washed with ethanol (2×2 mL) and diethyl ether (2×3 mL) and dried in

92

vacuo to give the required product as a white powder (526 mg, yield: 70% based on Ag).

93

Colorless hexagonal-shaped single crystals suitable for X-ray crystallography were

94

obtained by slow evaporation of the filtrate after 5 days. Anal. Calc. for Ag2C25 H32N10Se2:

4 95

C, 35.5; H, 3.8; N, 16.6. Found: C, 35.3; H, 3.3; N, 16.7%. IR (KBr,cm-1): 3124 (m) and

96

2917 (m) (-CH2- of spacer), 2100 (s) ( CN of SeCN), 1636 (m), 1558 (s)(C=N of tdmpp),

97

1460(s), 1417 (s), 1387 (m), 1316 (m), 1300 (m), 1032 (s), 789 (s), 680 (m), 565 (m).

98 99

2.2.4. Preparation of[Ag (tdmpp)]PF6 (3)

100

NH4PF6 (0.163 g, 1 mmol) and AgNO3 (0.170 g, 1 mmol) were added to an acetonitrile

101

solution (20 mL) and the mixture was stirred at room temperature for 30 min. To this

102

solution, tdmpp (0.420 g, 1 mmol) was added and the mixture was stirred for another 4 h.

103

The reaction mixture was filtered off and the colorless supernatant was decanted. The

104

precipitate was washed with ethanol (2×2 mL) and diethyl ether (2×3 mL) and dried in

105

vacuo to give the required product as a white powder(437 mg,yield:65% based on

106

Ag).Anal. Calc. for AgC23H32N8PF6: C, 41.0; H, 4.7; N, 16.6. Found: C, 40.8; H, 4.0; N,

107

17.3%. IR data (cm-1): 3129 (m) and 2918 (m) (-CH2- of spacer), 1558 (s) (C=N of tdmpp),

108

1458 (s), 1420 (s), 1387 (m), 1319 (m), 1297 (m), 1034 (s), 843(vs) (P-F of PF6), 791 (s),

109

680 (m), 557(s) (P-F of PF6).

110 111

2.2.5. Preparation of [WS4Ag3Cl (tdmpp)1.5].2CH3CN (4)

112

(NH4)2WS4 (0.348 g, 1 mmol) and AgCl (0.429 g, 3 mmol) were added to anacetonitrile

113

solution (30 mL). After stirring for 30 min at room temperature, tdmpp (0.630 g, 1.5 mmol)

114

was added to this solution. The mixture was stirred for another 3 h and then filtered. The

115

yellow precipitate was washed with ethanol (2×2 mL) and diethyl ether (2×3 mL) and

116

dried in vacuo to give the required product as a yellow-orang powder (595 mg, yield: 43%

117

based on W). Anal. Calc. for Ag6C77H108N28Cl2W2S8: C, 33.4; H, 3.9; N, 14.2. Found: C,

118

32.8; H, 3.3; N, 14.5%. IR data (cm-1): 3132(m) and 2918 (m) (-CH2-of spacer), 2253 (m)

119

(CN of acetonitrile), 1559(s) (C=N of tdmpp), 1460 (s), 1377 (m), 1319 (m), 1278 (m),

120

1034 (s), 448 (s) (W-µ 2-S), 439 (s) (W-µ 3-S).

121 122

2.2.6. Preparation of [WS4Ag4I2 (tdmpp)] 1.5CH3CN (5)

123

(NH4)2WS4 (0.348 g, 1 mmol) and AgI (0.936 g, 4 mmol) were added to an acetonitrile

124

solution (30 mL). After stirring at room temperature for 30 min, tdmpp (0.420 g, 1 mmol)

125

was added to this solution. The mixture was stirred for another 3 h and filtered. The yellow

126

precipitate was washed with ethanol (2×2 mL) and diethyl ether (2×3 mL) and dried in

127

vacuo to give the required product as a yellow powder (562 mg, yield: 38% based on W).

128

Anal. Calc. for Ag8C52H73N19I4W2S8: C, 21.1; H, 2.5; N, 9.0. Found: C, 21.3; H, 2.4; N,

5 129

8.5%. IR data (cm-1): 3127(m) and 2920 (m) (-CH2-of spacer), 2250 (m) (CN of

130

acetonitrile), 1559(s) (C=N of tdmpp) , 1460 (s), 1377 (m), 1320 (m), 1281 (m), 1038 (s),

131

439 (s) (W-µ 3-S).

132 133

2.3. X-ray crystallography

134

The crystallographic data for compounds 1 and 2 were collected at room temperature with

135

a Bruker APEX II CCD area-detector diffractometer using MoKα radiation (λ=

136

0.71073Å). Data collection, cell refinement, data reduction and absorption correction were

137

performed using multi scan methods with BRUKER software [38]. The structures were

138

solved by direct methods using SIR2004 [39]. The non-hydrogen atoms were refined

139

anisotropically by the full matrix least squares method on F2 using SHELXL [40]. All the

140

hydrogen (H) atoms were placed at the calculated positions and constrained to ride on their

141

parent atoms. Details concerning collection and analysis are reported in Table 1.

142 143

3. Results and discussion

144

3.1. Synthesis and spectroscopic characterization

145

The title compounds were prepared by the reactions of 1 to 5 in DMSO for 2 and in

146

acetonitrile for the rest of compounds.

147

AgNO3 + tdmpp → [Ag(tdmpp)(NO3)]n

(1)

148

2KSeCN + 2AgNO3 + tdmpp → [Ag2(SeCN)2(tdmpp)]n+ 2KNO3

(2)

149

NH4PF6+ AgNO3 +tdmmp→ [Ag(tdmpp)]PF6+ NH4NO3

(3)

150

2[NH4]2WS4 + 6AgCl + 3tdmpp → 2[WS4Ag3Cl(tdmpp)1.5].2CH3CN + 4NH4Cl

(4)

151

[NH4]2WS4 + 4AgI + tdmpp→ [WS4Ag4I2(tdmpp)]1.5CH3CN + 2NH4I

(5)

152 153

All the synthesized compounds are relatively stable and can be stored in a desiccator for

154

two months. These compounds were identified by IR spectroscopy, elemental analysis and

155

X-ray powder diffraction. Structures of compounds 1 and 2 were determined by X-ray

156

crystallography. The electronic absorption spectra of compounds 4 and 5 were also

157

recorded in acetonitrile solution. Crystals of compounds 3-5 were not suitable for X-ray

158

diffraction studies and therefore their structures could only be investigated in solid state by

159

infrared spectroscopy and elemental analysis.

160

IR spectra of all complexes show medium bands in the range of 2916-3132 cm-1 assigned to

161

the symmetric and asymmetric stretching vibrations of the methylene (-CH2-) groups of the

6 162

linker ligand and a strong band corresponding to the stretching vibration of the C=N bonds

163

of the pyrazole rings of the tdmpp ligands at 1558 or 1559 cm-1. This band is shifted to

164

lower frequency with respect to the spectrum of the uncoordinated 3,5-dimethyl-1-pyrazole

165

ligand (1595 cm-1) [41]. The IR spectrum of 1 exhibits two absorption bands with medium

166

intensity at 1415 cm-1 and strong broad band at 1320 cm-1, characteristic of monodentate

167

coordination of nitrate ion to the Ag(I) cation. The infrared spectrum of 2 shows an intense

168

absorption bands at 2100 cm-1 assigned to the CN stretching vibration of the N-coordinated

169

selenocyanate ligand. This band appears at a higher frequency relative to KSeCN (2070 cm-

170

1

) [42]. Two sharp bands at 843 and 557cm-1 in the infrared spectrum of 3 are attributed to

171

the vibration bands of PF6- counter anion. The infrared spectra of 4 and 5 display typical

172

absorption bands for the W–S stretching vibrations of the WS4 moiety in the range of 400–

173

500 cm-1 [43]. Consequently, the absorption bands in the spectrum of 4 at 448 and 438 cm-1

174

are assignable to the bridging W-µ 2-S and W-µ 3-S stretching vibrations, respectively [44].

175

These bands are shifted to lower frequencies relative to that of the parent [WS4]2- anion

176

(463 cm-1). This indicates that the [WS4]2- metalloligand is coordinated to the soft Ag(I)

177

centre through the sulfur atoms. In contrast to 4, in the spectrum of 5 only one band is

178

observed at 439 cm-1 for the W-µ 3-S bonds, showing that the coordination of silver(I) to the

179

[WS4]2- does not lower the effective symmetry of this anion. The electronic absorption

180

spectra of compounds 4 and 5 in acetonitrile solution are relatively simple and are

181

dominated by the internal transitions of the [WS4]2- ion. The main band at 445 nm in the

182

spectrum of 4 and 455 nm in the spectrum of 5 is assigned to the S(π)→W(d) charge

183

transfer transitions. This bands are red shifted with respect to the corresponding transitions

184

observed for the [WS4]2- (394 nm) anion. In order to confirm the phase purity of the

185

synthesized polymers, X-ray powder diffraction (XRPD) experiments were carried out for

186

compounds 1-5. In the case of polymer 1 (Fig. 1) and polymer 2 (Fig. 2) the experimental

187

spectra were consistent with their simulated spectra. The XRPD spectra of compounds 3-5

188

were shown in the supplementary materials (S1-S3). Experimental and calculated data were

189

extracted by Xpert and Mercury softwares, respectively.

190 191

3.2. Structural Characterization

192

3.2.1. Crystal structure of 1

193

The asymmetric unit of 1 consists of one Ag, one NO3- anion and one tdmpp ligand which

194

has the central atom of the propylene bridge located on a 2-fold axis (Fig.3). The Ag(I) ion

195

is in a five coordinate N4O coordination environment with a highly distorted, square-

7 196

pyramidal geometry (τ= 0.32) based on the Addison analysis where τ= 0.00 describes a

197

perfect square pyramid and τ= 1.00 a trigonal bipyramidal [45]. Each tdmpp ligand bridges

198

a pair of crystallographically related Ag(I) centers to generate a zigzag-chain structure

199

running along the b-axis. These chains are inter-connected by C-H...O hydrogen bonds with

200

H…O distance of 2.71 Å to form a two-dimensional structure in the ab-plane (Fig. 4). In

201

this structure, each Ag(I) cation is chelated by two bis(3,5-dimethylpyrazolyl)methane units

202

of two distinct tdmpp ligands with an average bite angle of 81.50º to form a six-membered

203

metallocyclic

204

dimethylpyrazolyl)methane units. In the equatorial plane, the smallest angle is the bite

205

angle, N2-Ag-N3, and the largest angle is the N3-Ag-N4 angle (Table 2). The Ag—N bond

206

lengths lie within the range of 2.393(2)- 2.464(2) Å with the Ag1—N2 and Ag1—N4 bond

207

distances slightly shorter than the Ag1—N1 and Ag1—N3 values (Table 2). These

208

distances are comparable with those found in [Ag(NO3)(C10H6N4)2] [C10H6N4= 5-(pyridin-

209

2-yl)pyrazine-2-carbonitrile] [2.301(2)- 2.579(3) Å] [46]. The nitrate ion binds to the silver

210

atom as a monodentate, terminal ligand with the Ag1—O2 distance of 2.615(8) Å. This

211

bond is longer than the Ag1—O1 = 2.547(3) Å bond reported for the [Ag(NO3)(C10H6N4)2]

212

with a distorted AgN4O square-pyramidal structure, but is consistent with other examples

213

reported in the literature [47]. In compound 1 a second O atom of the nitrate interacts with

214

the Ag(I) with the long, but significant Ag1—O1 distance of 2.784 Å.

ring

with

a

boat

conformation

for

each

of

the

bis(3,5-

215 216

3.2.2. Crystal structure of 2

217

The X-ray single-crystal structural analysis of the neutral polymeric structure of

218

[Ag2(SeCN)2 (tdmpp)]n (2) reveals that the compound crystallizes in the monoclinic space

219

group C2/c with Z = 4 (Table 1). The asymmetric unit of 2 consists of a half-molecule of

220

the [Ag2(SeCN)2(tdmmp)], the other half being generated by an inversion center lying at

221

the mid-point of between two adjacent silver atoms (Fig.5). Here, the tdmpp ligand acts as

222

a two-connector to link a pair of crystallographically equivalent silver (I) ions with an

223

Ag...Ag separation of 7.00 Å by its two arms. In the polymeric structure of 2, each of the

224

silver atoms adopts a distorted AgN3Se tetrahedral coordination geometry, coordinated by

225

two N atoms from one bis(3,5-dimethylpyrazol-1-yl)methane unit of a tdmpp ligand with

226

an average Ag-N distance of 2.351Å, one selenium atom with Ag-/Se distance of 2.5571 Å

227

and one

228

centrosymmetrically related selenocyanate anions that act as a double bridge between the

nitrogen with Ag-N distance of 2.336 Å belonging to a pair of

8 229

two adjacent Ag(I) centers. The bond angles around the silver atom are in the range of

230

80.11 to 127.9° (Table 2). The smallest angle is associated with the N2-Ag1-N4 angle of a

231

six-membered metallocycle made by four nitrogens, one silver and one carbon atom. These

232

metallocycles adopt a boat conformation with the silver and carbon atoms off the plane

233

defined by the four imine nitrogen atoms. The largest angle within the AgN3Se core occurs

234

within the N4-Ag1-Se1 angle and this is likely to be due to the large steric hindrance of the

235

pyrazole rings .Two silver and two distinguished µ 2-NCSe with a classical µ-N,Se

236

coordination mode form a building unit which is a centrosymmetric, nearly planar eight-

237

membered macrocycle (AgSeCN)2 similar to the chair conformation of the cyclohexane

238

with the adjacent Ag…Ag separation of 5.714Å. Complex 2 exhibits a one-dimensional

239

(1D) sinusoidal-like chain extending along the a-axis with Ag(I) centers linked alternately

240

by the organic tdmpp ligands and inorganic (AgSeCN)2 dimers. The parallel adjacent

241

chains are linked together by means of non-covalent C-H···π (arene), C-H···Se and C-

242

H···N interactions (Fig.4a) with H···π, H···Se and H···N distances of 2.937, 2.971 and

243

2.747Å (Fig.6a), respectively to generate a two-dimensional structure (Fig.6b).

244

4. Conclusion

245

In compounds 1 and 2 the crystallographic results clearly indicate that the tdmpp ligand

246

exhibits a strong tendency to chelate Ag(I) and promote coordination numbers that are

247

higher than the linear two-coordinate complexes commonly seen when simple

248

monodentate amines bind to Ag(I). In the case of 1 it is interesting to note that the nitrate

249

anion is able to coordinate to the Ag centre (although rather weakly) despite the fact that

250

the Ag centre is already coordinated by a pair of chelating ligands each with relatively

251

large bite angles. In the case of 2 the more strongly coordinating selenocyanate binds

252

through both sulphur and nitrogen atoms to generate a linear polymer. In compound 3, the

253

PF6- serves as the counter-ion. In complexes 4 and 5, the [WS4]2- acts as a co-ligand, and

254

coordinates to three and four Ag(I) atoms, respectively through the sulfur atoms.

255 256

Acknowledgement

257

We thank Shahid Chamran University of Ahvaz for the financial support (grant number:

258

854532).

259

9 260

Appendix A. Supplementary material

261

CCDC reference numbers 1035600-1 contains the supplementary crystallographic data for

262

the structures 1 and 2, respectively. Crystallographic data can be obtained free of charge

263

from

264

http://www.ccdc.cam.ac.uk/datarequest/cif. Or from the Cambridge Crystallographic Data

265

Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:

266

[email protected]. Supplementary material associated with this article can be

267

found, in the online version, at http://dx.doi.org/10.1016/j.molstruc.2014.11.008.

268

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338

Figure captions

339

Fig. 1. Observed (blue) and calculated (red) X-ray powder diffraction spectrum of

340

compound 1.

341

Fig. 2. Observed (brown) and calculated (violet) X-ray powder diffraction spectrum of

342

compound 2.

343

Fig. 3. An ORTEP view of 1, showing the atomic numbering scheme. H atoms are omitted

344

for clarity.

345

Fig. 4.View of 2D structure of 1 formed by the non-classic C-H···O hydrogen bonds.

346

Fig. 5. An ORTEP view of 2, showing the atomic numbering scheme. H atoms are omitted

347

for clarity.

348

Fig. 6. 2-D structure of 2 formed by the non-classic C-H···π (arene), C-H···N and C-H···Se

349

interactions. All interaction are shown by dashed lines.

350 compound

Table 1. Crystal data for compounds 1 and 2. 1 2

Chemical formula

AgC23H32N9O3

Ag2C25 H32N10Se2

12 Crystal system

monoclinic

monoclinic

Space group

P 21/n

C 2/c

a (Å)

9.8422(5)

22.4987(10)

b (Å)

13.7187(6)

7.9464(2)

c (Å)

19.3258(9)

20.5755(8)

α (°)

90.00

90.00

β(°)

96.488(2)

126.699(8)

γ(°)

90.00

90.00

z

4

4

2.89

2.37

2592.7

2950.57

R-factor (%) 3

V (Å ) 351 352

Table 2. Selected bond distances (Å) and angles (º) for compounds 1 and 2. Compound 1 Ag1- N2

2.406(2)

N1- C4

1.331(3)

Ag1- O2

2.615(8)

N1- N5

1.365(2)

Ag1- N3

2.436(2)

N8- C19

1.363(3)

Ag1- N1

2.464(2)

N8- C21

1.455(3)

Ag1 -N4

2.393(2)

O2- N9

1.233(7)

N2-Ag1-O2

87.1(2)

N2-Ag1-N3

82.40(6)

N2-Ag1-N1

99.43(6)

N2-Ag1-N4

170.43(6)

O2-Ag1-N1

112.3(2)

N3-Ag1-N1

96.05(6)

O2-Ag1-N3

151.1(2)

O2-Ag1-N4

84.1(2)

N4-Ag1-N3

107.14(6)

13 Compound 2

353 354 355

N2- Ag1

2.366(2)

N1- N2

1.371(3)

Ag1- N4

2.382(2)

Se1- C13

1.822(3)

Ag1- N5

2.336(3)

C11- C12

1.526(4)

Se1- Ag1

2.5571(4)

H12A- C12

0.990(2)

C13- Se1

1.822(3)

C13 -N5

1.145(4)

Se1-Ag1-N4

124.19(6)

N4-Ag1-N2

80.11(8)

N4-Ag1-N5

106.54(8)

N2-Ag1-N5

111.44(8)

Se1-Ag1-N2

124.19(6)

Se1-Ag1-N5

104.62(6)

14

356 357 358 359 360

Fig. 1

15

361 362 363 364 365

Fig. 2

16

366 367 368 369

Fig. 3

17

370 371 372 373 374

Fig. 4

18

375 376 377 378 379

Fig. 5

19

380 381

a

382 383

b

384 385 386 387

Fig. 6

20 388

389 390 391 392 393

Graphical abstract

21 394 395

Five silver – based complexes

396

structurally characterized.

397

Non-classical interactions play a major role in determining the final structure of these

398

compounds.

399 400 401 402 403 404

Graphical Abstract with pyrazole based ligand were synthesized and

22 405

Highlights

406

Non- covalent interactions CH…π and CH…O lead to formation of 2D structures.

407

Nitrate anion acting as a monodentate terminal ligand.

408 409 410 411

The W-S bands shifted to lower frequencies in WS4 complexes with the silver(I) ion.