Tris(3-amino-5,6-dimethyl-1,2,4-triazine-κN 2)silver(I) trifluromethane­sulfonate–3-amino-5,6-dimethyl-1,2,4-triazine (1/1)

Yu-Hang Jiang; Li-Na Cui; Xu Huang; Qiong-Hua Jin; Cun-Lin Zhang

doi:10.1107/S1600536811040748

. 2011 Oct 12;67(Pt 11):m1526–m1527. doi: 10.1107/S1600536811040748

Tris(3-amino-5,6-dimethyl-1,2,4-triazine-κN ²)silver(I) trifluromethanesulfonate–3-amino-5,6-dimethyl-1,2,4-triazine (1/1)

Yu-Hang Jiang ^a, Li-Na Cui ^a, Xu Huang ^a, Qiong-Hua Jin ^a,^*, Cun-Lin Zhang ^b

PMCID: PMC3246953 PMID: 22219773

Abstract

The asymmetric unit of the title compound, [Ag(C₅H₈N₄)₃](CF₃O₃S)·C₅H₈N₄, contains two cations, two anions and two uncoordinated 3-amino-5,6-dimethyl-1,2,4-triazine (admt) ligands. It was prepared from the reaction of silver trifluoromethanesulfonate and admt in a 2:3 molar ratio. Both silver(I) ions are bonded to three admt molecules via their 2-position triazine N atoms in almost regular trigonal–planar geometries. Three intramolecular N—H⋯N hydrogen bonds between adjacent admt molecules in each cation help to maintain their overall near planarities (r.m.s. deviations for the 28 non-H atoms = 0.139 and 0.153 Å). In the crystal, numerous N—H⋯N, N—H⋯O, C—H⋯O, C—H⋯N and C—H⋯F hydrogen-bonding interactions link the components into a three-dimensional network.

Related literature

For background to the properties and applications of silver complexes, see: Jin et al. (2010a ▶,b ▶); Effendy et al. (2007 ▶). Sang & Xu (2006 ▶). For related structures, see: Self et al. (1991 ▶); Wang & Cheng (2007 ▶); Liu et al. (2002 ▶); Jiang et al. (2011 ▶).

Experimental

Crystal data

[Ag(C₅H₈N₄)₃](CF₃O₃S)·C₅H₈N₄
M _r = 753.56
Triclinic,
a = 13.9357 (14) Å
b = 15.1693 (15) Å
c = 16.2257 (17) Å
α = 76.735 (1)°
β = 72.565 (1)°
γ = 81.201 (2)°
V = 3172.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.77 mm⁻¹
T = 298 K
0.45 × 0.27 × 0.23 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.723, T _max = 0.843
16692 measured reflections
11051 independent reflections
4939 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.069
wR(F ²) = 0.192
S = 1.05
11051 reflections
827 parameters
H-atom parameters constrained
Δρ_max = 0.91 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811040748/hb6434sup1.cif

e-67-m1526-sup1.cif^{(44.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811040748/hb6434Isup2.hkl

e-67-m1526-Isup2.hkl^{(540.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Ag1—N10	2.241 (6)
Ag1—N6	2.248 (6)
Ag1—N2	2.287 (7)
Ag2—N14	2.251 (7)
Ag2—N18	2.264 (6)
Ag2—N22	2.273 (6)

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N10—Ag1—N6	121.8 (3)
N10—Ag1—N2	119.6 (3)
N6—Ag1—N2	118.6 (2)
N14—Ag2—N18	119.9 (3)
N14—Ag2—N22	119.5 (3)
N18—Ag2—N22	120.0 (2)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯N5	0.86	2.15	2.977 (9)	161
N8—H8A⋯N9	0.86	2.22	3.077 (10)	173
N12—H12B⋯N1	0.86	2.17	3.018 (11)	169
N16—H16B⋯N17	0.86	2.21	3.052 (10)	165
N20—H20A⋯N21	0.86	2.18	3.004 (9)	161
N24—H24B⋯N13	0.86	2.19	3.044 (11)	169
N4—H4B⋯N30ⁱ	0.86	2.10	2.935 (11)	162
N8—H8B⋯O1ⁱⁱ	0.86	2.19	3.032 (11)	168
N12—H12A⋯O6ⁱⁱⁱ	0.86	2.26	3.047 (11)	152
N16—H16A⋯O3^iv	0.86	2.23	3.032 (11)	155
N20—H20B⋯N26ⁱⁱ	0.86	2.15	3.003 (9)	172
N24—H24A⋯O4	0.86	2.26	3.121 (12)	175
N28—H28A⋯N19ⁱⁱ	0.86	2.24	3.084 (10)	167
N28—H28B⋯O5	0.86	2.22	2.978 (15)	146
N32—H32A⋯O2ⁱⁱ	0.86	2.17	2.982 (13)	156
N32—H32B⋯N3ⁱ	0.86	2.30	3.142 (12)	166
C5—H5B⋯O4	0.96	2.56	3.486 (17)	161
C9—H9A⋯N27^v	0.96	2.56	3.363 (12)	141
C15—H15B⋯O3^iv	0.96	2.58	3.538 (15)	177
C35—H35C⋯F1^iv	0.96	2.54	3.375 (14)	145
C40—H40A⋯F5ⁱⁱⁱ	0.96	2.43	3.208 (17)	138

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 21171119), the National Keystone Basic Research Program (973 Program) under grant Nos. 2007CB310408 and 2006CB302901, the Funding Project for Academic Human Resources Development in Institutions of Higher Learning Under the Jurisdiction of Beijing Municipality and the State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences.

supplementary crystallographic information

Comment

Papers on structural and kinetic features of silver(I) complexes containing heterocyclic-N ligands are growing explosively due to their participation in biological process and their applicatioins in lunminescence and catalysis materials (Jin et al.,2010a, 2010b, Effendy et al., 2007, Sang et al.,2006). In our research, we select multifunctional ligand 3-Amino-5,6-dimethyl- 1,2,4-triazine (ADMT) as the N-donor ligand because it is a very efficient ligand and is very suitable to coordinate to the central atom. Besides,its triazine ring is capable of coordinating to metal atom, and its amino group can form hydrogen bonds with other acceptors. [Al(CH₃)₂]₅[C₁₁H₁₅N₈][Al(CH₃)₃] is the only crystallographic complex of ADMT reported so far (Self et al.,1991). As a part of the extension of our study on the emission of silver (I) complexes of heterocyclic-N ligands, we synthesized the first silver (I) complex of ADMT, [Ag(ADMT)₃]₂(OTf)₂.(ADMT)₂.

The title complex consists of two [Ag(ADMT)₃] cations,two free OTf^- anions and two free ADMT ligands. In the complex, the angles N—Ag—N are in the range of 118.6 (2)–121.8 (3)°, which confirms the approximate plane coordination environment around the silver atom. The Ag(I) atom is coordinated by three N atoms from ADMT. The three Ag—N distances are in the range of 2.241 (6)–2.273 (6) Å, which agree with those in [Ag(µ-admtrz)(C₆H₅COO)]₂.2H₂O (2.2460 (19)–2.251 (2) Å)(Wang & Cheng, 2007) and are slightly longer than those in [Ag₂(admtrz)₂(CF₃CO₂)₂] (2.205 (2)–2.250 (2) Å)(Liu et al., 2002).

We also tried to synthesize more silver(I) complexes of ADMT, but failed. When starting material AgOTf was replaced by AgBr, only crystalized ADMT ligand was obtained, and when the title compound was further reacting with PPh₃, only the Ag:PPh3(1:4) adduct was obtained (Jiang et al., 2011). The failure of the above reactions maybe is because the coordination ability of ADMT to silver(I) is weaker than PPh₃ ligand and the bromide ion.

Experimental

A mixture of AgOTf (silver trifluoromethanesulfonate) and ADMT (ADMT = 3-Amino-5,6-dimethyl-1,2,4-triazine) in molar ratio of 2:3 in the mixed solution of CH₃CN (5 ml)/ CH₂Cl₂(5 ml) was stirred for 6 h at room temperature,then filtered. Subsequent slow evaporation of the filtrate resulted in the formation of yellow crystals of the adduct of AgOTf:ADMT(1:4). Yellow prisms were selected directly from the sample as prepared.