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Acta Cryst. (2009). E65, m1453-m1454    [ doi:10.1107/S1600536809043669 ]

Bis[[mu]-1-(2-pyridylmethyl)-1H-benzotriazole]disilver(I) bis(perchlorate)

C.-S. Liu, X.-G. Xiao and M. Hu

Abstract top

In the title centrosymmetric binuclear AgI complex, [Ag2(C12H10N4)2](ClO4)2, each AgI center is two-coordinated by one pyridine and one benzotriazole N-donor atom of two inversion-related 1-(2-pyridylmethyl)-1H-benzotriazole (L) ligands. This forms a unique box-like cyclic dimer with an intramolecular Ag...Ag separation of 4.479 (2) Å. Intermolecular C-H...O hydrogen-bonding interactions, involving uncoordinated ClO4- ions, link the binuclear units, forming a two-dimensional network parallel to (10\overline{2}).

Comment top

Numerous related bis-heterocyclic chelating or bridging ligands have been synthesized and used extensively to construct functional coordination complexes that contain different hetero-aromatic ring systems, for example, pyridine, pyrazine, quinoline, quinoxaline, pyrazole, imidazole, thiazoles and their benzo analogues (Constable, 1989; Constable & Steel, 1989; Steel, 2005). The structures of five N-containing bis-heterocyclic ligands bearing 1-substituted benzotriazole subunits, such as 1-(2-pyridylmethyl)-1H-benzotriazole and its RuII, CuII, PdII, AgI, ZnII and HgII complexes, have been well documented previously (Huang et al. 2008; Liu, Zhou et al. 2008; Richardson & Steel, 2003). In our previous work, to further investigate the influences of the N-donor spatial position of pendant pyridyl group in structurally related benzotriazol-1-yl-based pyridyl ligands on the structures of their coordination complexes, two new N-containing heterocyclic ligands 1-(4-pyridylmethyl)-1H-benzotriazole (4-pbt) and 2-(3-pyridylmethyl)-2H-benzotriazole (3-pbt) were designed and prepared. Their reaction with AgNO3 offered an one-dimensional double helical coordination polymer {[Ag(4-pbt)](NO3)}∞ and a centrosymmetric binuclear complex [Ag2(3-pbt)2 (NO3)2], respectively (Hu et al. 2008; Liu, Sun et al. 2008). To further investigate the influence of different counter-anions on the self-assembly process of coordination complexes, we chose to use L to construct new functional AgI complexes through its reaction with AgClO4. Here we report the crystal structure of [Ag(L)]2(ClO4)2.

The structure of the title compound (I) consists of a centrosymmetric binuclear [Ag(L)]22+ unit and two uncoordinated ClO4- ions. The binuclear [Ag(L)]22+ cation (Fig. 1) comprises two L ligands and two AgI centers. The intramolecular non-bonding Ag···Ag separation is 4.479 (2) Å. There is only one crystallographic independent AgI center, which is two coordinated by two N-atom donors, one N donor being from benzotriazole ring of one L ligand and the other being from pyridyl ring of another L ligand. In this case the 14-membered dimetallocyclic ring is far from planar as a result of the presence of the tetrahedral methylene group of the L ligand. All the Ag—N bond distances are in the normal range found for similar complexes (Liu et al., 2006; Liu et al., 2007).

In the crystal structure adjacent discrete binuclear [Ag(L)]22+ units are assembled into one-dimensional chains by intermolecular C—H···O hydrogen-bonding interactions between the L ligands and the uncoordinated ClO4- (Table 2). The net result is a two-dimensional network running parallel to the (102) plane (Fig. 2). In addition, the crystal structure of (I) also contains intermolecular face-to-face π···π stacking interactions between the pyridyl ring involving N1/C2/C3/C4/C5/C6 (centroid Cg1) and N1A/C2A/C3A/C4A/C5A/C6A (centroid Cg2) of distinct L ligands [the centroid–centroid separation being 3.685 (1) Å, symmetry code A: -x, -y + 1, -z + 1], that interlink the two-dimensional sheets to form a three-dimensional framework.

Related literature top

Bis-heterocyclic chelating or bridging ligands have been used extensively to construct functional coordination complexes that contain different hetero-aromatic ring systems, see: Constable (1989); Constable & Steel (1989); Steel (2005). For related structures, see: Hu et al. (2008); Huang et al. (2008); Liu et al. (2006, 2007); Liu, Sun et al. (2008); Liu, Zhou et al. (2008); Richardson & Steel (2003). For the synthesis of ligand L, see: Liu, Sun et al. (2008).

Experimental top

1-(2-Pyridylmethyl)-1H-benzotriazole (L) was synthesized according to the literature procedure of Liu, Sun et al. (2008). Complex (I) was prepared by adding a solution of L (0.05 mmol) in CH3OH (10 ml) on top of an aqueous solution (15 ml) of AgClO4 (0.1 mmol) in a test tube. Yellow single crystals suitable for X-ray structural analysis appeared at the tube wall after ca one month at room temperature (yield ~30% based on L). Elemental analysis calculated for (C24H20Ag2Cl2N8O8): H 2.41, C 34.52, N 13.42%; found: H 2.30, C 34.67, N 13.36%.

Refinement top

H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C—H = 0.93 (aromatic) or 0.97 Å (methylene), with Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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: SHELXTLL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of complex (I). Displacement ellipsoids are drawn at the 30% probability level. Atoms labelled with the suffix A are generated by the symmetry operation (–x + 1, –y + 1, –z + 1).
[Figure 2] Fig. 2. A view of the two-dimensional network of complex (I), running parallel to the (102) plane, formed by the intermolecular C—H···O (fine dashed lines) interactions. For clarity, only H atoms involved in the interactions are shown.
Bis[µ-1-(2-pyridylmethyl)-1H-benzotriazole]disilver(I) bis(perchlorate) top
Crystal data top
[Ag2(C12H10N4)2](ClO4)2F(000) = 824
Mr = 835.12Dx = 1.960 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3182 reflections
a = 9.4273 (4) Åθ = 3.0–26.3°
b = 16.0863 (7) ŵ = 1.64 mm−1
c = 11.9152 (7) ÅT = 293 K
β = 128.448 (3)°Block, yellow
V = 1415.15 (13) Å30.24 × 0.23 × 0.03 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer		2484 independent reflections
Radiation source: fine-focus sealed tube1658 reflections with I > 2σ(I)
graphiteRint = 0.037
φ and ω scansθmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −11→11
Tmin = 0.695, Tmax = 0.960k = −15→19
9388 measured reflectionsl = −13→14
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0614P)2 + 2.0392P]
where P = (Fo2 + 2Fc2)/3
2484 reflections(Δ/σ)max = 0.001
199 parametersΔρmax = 0.62 e Å−3
0 restraintsΔρmin = −0.53 e Å−3
Crystal data top
[Ag2(C12H10N4)2](ClO4)2V = 1415.15 (13) Å3
Mr = 835.12Z = 2
Monoclinic, P21/cMo Kα radiation
a = 9.4273 (4) ŵ = 1.64 mm−1
b = 16.0863 (7) ÅT = 293 K
c = 11.9152 (7) Å0.24 × 0.23 × 0.03 mm
β = 128.448 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		2484 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1658 reflections with I > 2σ(I)
Tmin = 0.695, Tmax = 0.960Rint = 0.037
9388 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.137Δρmax = 0.62 e Å−3
S = 1.08Δρmin = −0.53 e Å−3
2484 reflectionsAbsolute structure: ?
199 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ag10.42617 (7)0.60201 (4)0.58311 (7)0.0599 (3)
N10.1418 (7)0.6101 (3)0.4978 (6)0.0368 (13)
N20.3065 (6)0.4519 (4)0.2962 (5)0.0385 (14)
N30.2868 (7)0.5274 (4)0.3285 (6)0.0407 (14)
N40.1091 (6)0.5452 (3)0.2391 (5)0.0347 (13)
C10.0453 (9)0.6239 (4)0.2566 (7)0.0403 (17)
H110.13860.66580.29330.048*
H12−0.06120.64250.16370.048*
C2−0.0004 (9)0.6159 (4)0.3575 (7)0.0325 (15)
C3−0.1725 (9)0.6158 (4)0.3083 (8)0.0435 (18)
H3−0.26650.61900.21020.052*
C4−0.2110 (10)0.6110 (4)0.4035 (9)0.051 (2)
H4−0.32970.61050.37110.062*
C5−0.0673 (11)0.6068 (4)0.5464 (9)0.052 (2)
H5−0.08690.60500.61380.063*
C60.1070 (10)0.6055 (4)0.5901 (8)0.0472 (18)
H60.20350.60120.68740.057*
C70.1415 (8)0.4210 (4)0.1852 (6)0.0318 (15)
C80.0907 (9)0.3446 (4)0.1149 (7)0.0400 (17)
H80.17570.30390.13900.048*
C9−0.0903 (10)0.3326 (5)0.0089 (8)0.0500 (19)
H9−0.12900.2828−0.04190.060*
C10−0.2202 (10)0.3928 (5)−0.0261 (8)0.052 (2)
H10−0.34210.3811−0.09800.062*
C11−0.1737 (8)0.4676 (5)0.0417 (7)0.0407 (17)
H1−0.25950.50760.01830.049*
C120.0111 (8)0.4803 (4)0.1486 (6)0.0310 (14)
Cl10.4844 (2)0.21950 (12)0.5792 (2)0.0510 (5)
O10.4745 (9)0.1317 (4)0.5670 (7)0.089 (2)
O20.3143 (9)0.2532 (5)0.4653 (7)0.116 (3)
O30.6166 (13)0.2454 (6)0.5735 (14)0.168 (5)
O40.5263 (10)0.2432 (5)0.7115 (7)0.109 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0348 (3)0.0672 (5)0.0583 (4)0.0086 (3)0.0195 (3)−0.0078 (3)
N10.041 (3)0.034 (3)0.038 (3)0.002 (2)0.026 (3)−0.003 (3)
N20.033 (3)0.047 (4)0.032 (3)0.007 (3)0.019 (2)0.002 (3)
N30.037 (3)0.045 (4)0.035 (3)0.004 (3)0.019 (3)−0.002 (3)
N40.037 (3)0.036 (3)0.034 (3)0.006 (2)0.023 (2)0.000 (3)
C10.059 (4)0.026 (4)0.040 (4)0.006 (3)0.033 (4)0.004 (3)
C20.044 (4)0.017 (3)0.032 (3)0.003 (3)0.021 (3)−0.003 (3)
C30.039 (4)0.046 (5)0.038 (4)0.008 (3)0.020 (3)0.004 (3)
C40.050 (4)0.049 (5)0.064 (5)0.010 (3)0.040 (4)0.008 (4)
C50.074 (6)0.046 (5)0.061 (5)0.012 (4)0.054 (5)0.012 (4)
C60.057 (4)0.036 (4)0.043 (4)0.008 (3)0.028 (4)0.001 (3)
C70.036 (3)0.034 (4)0.026 (3)0.004 (3)0.020 (3)0.006 (3)
C80.055 (4)0.032 (4)0.043 (4)0.005 (3)0.036 (4)0.001 (3)
C90.058 (5)0.036 (4)0.052 (5)−0.011 (4)0.032 (4)−0.009 (4)
C100.043 (4)0.051 (5)0.050 (4)−0.011 (4)0.023 (4)−0.001 (4)
C110.033 (3)0.050 (5)0.037 (4)0.005 (3)0.021 (3)0.008 (3)
C120.039 (3)0.028 (4)0.032 (4)0.000 (3)0.025 (3)0.002 (3)
Cl10.0455 (9)0.0446 (11)0.0560 (12)−0.0073 (8)0.0281 (9)−0.0116 (9)
O10.094 (4)0.051 (4)0.090 (5)−0.012 (3)0.041 (4)−0.011 (3)
O20.098 (5)0.117 (6)0.066 (5)0.042 (5)0.018 (4)−0.015 (4)
O30.171 (8)0.115 (7)0.317 (14)−0.064 (6)0.201 (10)−0.063 (8)
O40.114 (5)0.116 (6)0.060 (4)0.019 (5)0.037 (4)−0.028 (4)
Geometric parameters (Å, °) top
Ag1—N2i2.159 (5)C5—C61.381 (11)
Ag1—N12.201 (5)C5—H50.9300
N1—C61.332 (9)C6—H60.9300
N1—C21.347 (8)C7—C121.394 (8)
N2—N31.322 (8)C7—C81.394 (9)
N2—C71.362 (8)C8—C91.365 (9)
N2—Ag1i2.159 (5)C8—H80.9301
N3—N41.344 (7)C9—C101.406 (10)
N4—C121.367 (8)C9—H90.9300
N4—C11.470 (8)C10—C111.361 (10)
C1—C21.514 (10)C10—H100.9300
C1—H110.9698C11—C121.393 (8)
C1—H120.9699C11—H10.9300
C2—C31.339 (9)Cl1—O31.355 (7)
C3—C41.392 (11)Cl1—O21.414 (6)
C3—H30.9300Cl1—O11.417 (6)
C4—C51.367 (11)Cl1—O41.418 (7)
C4—H40.9299
N2i—Ag1—N1155.9 (2)C6—C5—H5120.2
C6—N1—C2117.5 (6)N1—C6—C5122.3 (7)
C6—N1—Ag1118.1 (5)N1—C6—H6118.8
C2—N1—Ag1124.3 (5)C5—C6—H6118.9
N3—N2—C7109.6 (5)N2—C7—C12107.9 (6)
N3—N2—Ag1i119.5 (4)N2—C7—C8131.5 (6)
C7—N2—Ag1i131.0 (4)C12—C7—C8120.6 (6)
N2—N3—N4107.3 (5)C9—C8—C7116.4 (6)
N3—N4—C12111.1 (5)C9—C8—H8121.8
N3—N4—C1119.3 (5)C7—C8—H8121.8
C12—N4—C1129.4 (5)C8—C9—C10122.3 (7)
N4—C1—C2112.5 (5)C8—C9—H9118.9
N4—C1—H11109.0C10—C9—H9118.8
C2—C1—H11109.1C11—C10—C9122.2 (6)
N4—C1—H12109.2C11—C10—H10118.9
C2—C1—H12109.1C9—C10—H10118.9
H11—C1—H12107.8C10—C11—C12115.5 (6)
C3—C2—N1123.0 (6)C10—C11—H1122.3
C3—C2—C1121.2 (6)C12—C11—H1122.2
N1—C2—C1115.9 (6)N4—C12—C11132.9 (6)
C2—C3—C4120.1 (7)N4—C12—C7104.1 (5)
C2—C3—H3119.9C11—C12—C7123.0 (6)
C4—C3—H3119.9O3—Cl1—O2111.3 (7)
C5—C4—C3117.3 (7)O3—Cl1—O1107.7 (5)
C5—C4—H4121.4O2—Cl1—O1108.7 (4)
C3—C4—H4121.2O3—Cl1—O4110.1 (6)
C4—C5—C6119.7 (7)O2—Cl1—O4109.2 (4)
C4—C5—H5120.1O1—Cl1—O4109.7 (5)
N2i—Ag1—N1—C653.0 (7)C4—C5—C6—N11.5 (11)
N2i—Ag1—N1—C2−124.0 (6)N3—N2—C7—C12−1.4 (7)
C7—N2—N3—N40.4 (7)Ag1i—N2—C7—C12178.4 (4)
Ag1i—N2—N3—N4−179.4 (4)N3—N2—C7—C8−178.6 (7)
N2—N3—N4—C120.8 (7)Ag1i—N2—C7—C81.1 (11)
N2—N3—N4—C1176.1 (5)N2—C7—C8—C9178.0 (7)
N3—N4—C1—C2−89.7 (7)C12—C7—C8—C91.1 (10)
C12—N4—C1—C284.6 (8)C7—C8—C9—C10−1.5 (11)
C6—N1—C2—C3−1.1 (9)C8—C9—C10—C111.2 (12)
Ag1—N1—C2—C3175.9 (5)C9—C10—C11—C12−0.3 (11)
C6—N1—C2—C1178.0 (5)N3—N4—C12—C11177.9 (7)
Ag1—N1—C2—C1−4.9 (7)C1—N4—C12—C113.3 (11)
N4—C1—C2—C3−106.9 (7)N3—N4—C12—C7−1.6 (7)
N4—C1—C2—N174.0 (7)C1—N4—C12—C7−176.2 (6)
N1—C2—C3—C41.1 (10)C10—C11—C12—N4−179.6 (7)
C1—C2—C3—C4−178.0 (6)C10—C11—C12—C7−0.2 (10)
C2—C3—C4—C50.2 (11)N2—C7—C12—N41.8 (7)
C3—C4—C5—C6−1.4 (11)C8—C7—C12—N4179.4 (6)
C2—N1—C6—C5−0.2 (10)N2—C7—C12—C11−177.8 (6)
Ag1—N1—C6—C5−177.4 (5)C8—C7—C12—C11−0.2 (10)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H11···O3i0.972.313.264 (15)168
C1—H12···O2ii0.972.583.415 (11)144
C3—H3···O1ii0.932.603.512 (10)168
C11—H1···O1ii0.932.563.481 (11)170
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y+1/2, −z+1/2.
Table 1
Selected geometric parameters (Å, °) top
Ag1—N2i2.159 (5)N2—Ag1i2.159 (5)
Ag1—N12.201 (5)
N2i—Ag1—N1155.9 (2)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H11···O3i0.972.313.264 (15)168
C1—H12···O2ii0.972.583.415 (11)144
C3—H3···O1ii0.932.603.512 (10)168
C11—H1···O1ii0.932.563.481 (11)170
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y+1/2, −z+1/2.
Acknowledgements top

This work was supported by the start-up fund for PhDs in Natural Scientific Research of Zhengzhou University of Light Industry (No. 2007BSJJ001 to CSL).

references
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