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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): m1324.
Published online 2010 September 30. doi:  10.1107/S1600536810037682
PMCID: PMC2983413

catena-Poly[[silver(I)-μ-4-aminopyridine] perchlorate]: a 1-D staircase coordination polymer

Abstract

Reaction of 4-amino­pyridine with silver(I) perchlorate leads to a one-dimensional coordination polymer, {[Ag(C5H6N2)]ClO4}n, in which the amino­pyridine binds through both N atoms. The perchlorate anion is hydrogen bonded to the amino H atoms and inter­acts weakly with the silver(I) atoms (Ag—O > 2.70 Å), both located on inversion centres, and some aromatic H atoms (O—H > 2.55 ÅA), thereby extending the dimensionality of the assembly. This is the first silver complex in which this ligand acts in a bridging mode.

Related literature

For discrete silver complexes of the same ligand, see: Kristian­sson (2000 [triangle]); Abu-Youssef et al. (2006 [triangle]); Liu et al. (2005 [triangle]); Zhu et al. (2003a [triangle],b [triangle]); Li et al. (2005 [triangle]); Ma et al. (2004 [triangle]). For metallosupra­molecular assemblies derived from bridging heterocyclic ligands, see: Steel (2005 [triangle]). For the use of silver(I) for the self-assembly of both discrete and polymeric aggregates with diverse mol­ecular architectures, see: Fitchett & Steel (2006 [triangle]); O’Keefe & Steel (2007 [triangle]). For a review of the use of pyrazine and analogues as bridging ligands for silver(I)-based assemblies, see: Steel & Fitchett (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1324-scheme1.jpg

Experimental

Crystal data

  • [Ag(C5H6N2)]ClO4
  • M r = 301.44
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1324-efi1.jpg
  • a = 5.0720 (2) Å
  • b = 9.0025 (3) Å
  • c = 9.5520 (3) Å
  • α = 93.198 (2)°
  • β = 96.992 (2)°
  • γ = 100.452 (2)°
  • V = 424.37 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.67 mm−1
  • T = 113 K
  • 0.35 × 0.11 × 0.05 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.455, T max = 0.878
  • 9107 measured reflections
  • 1740 independent reflections
  • 1591 reflections with I > 2σ(I)
  • R int = 0.046

Refinement

  • R[F 2 > 2σ(F 2)] = 0.021
  • wR(F 2) = 0.051
  • S = 1.03
  • 1740 reflections
  • 127 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.57 e Å−3
  • Δρmin = −0.78 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810037682/bv2161sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037682/bv2161Isup2.hkl

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

Acknowledgments

We thank the Chemistry Department, University of Canterbury, New Zealand, for funding.

supplementary crystallographic information

Comment

For some time we have been involved in the study of metallosupramolecular assemblies derived from bridging heterocyclic ligands (Steel, 2005). In recent years we have focused on the use of silver(I) for the self-assembly of both discrete and polymeric aggregates with diverse molecular architectures (Fitchett & Steel, 2006; O'Keefe & Steel, 2007). In this context, we have recently reviewed the use of pyrazine and analogues as bridging ligands for silver(I)-based assemblies (Steel & Fitchett, 2008). 4-Aminopyridine (1) is a less symmetrical ligand that can potentially act as a bridge between metal centres. X-ray structures have been reported for complexes of (1) with silver nitrate (Kristiansson, 2000; Abu-Youssef et al., 2006), silver bicarbonate (Liu et al., 2005), silver trifluoroacetate (Zhu et al., 2003a), silver trifluoromethanesulfonate (Zhu et al., 2003b; Liu et al., 2005), silver terephthalate (Li et al., 2005) and silver 3-nitrobenzoate (Ma et al., 2004). However, in all these cases the ligand acts as a monodentate ligand binding through the pyridine nitrogen only and therefore forms discrete coordination complexes. We now describe a one-dimensional coordination polymer, obtained from reaction between this ligand and silver perchlorate, in which ligand (1) acts in a bridging bidentate mode.

The complex (2) crystallizes in the triclinic space group P-1 with a full 4-aminopyridine ligand, two half silver atoms and a perchlorate anion in the asymmetric unit (Fig. 1). The two independent silver atoms each lie on crystallographic centres of inversion and therefore act as linear connectors resulting in a 1-D coordination polymer. Ligand (1) coordinates to Ag1 through two pyridine N atoms and to Ag2 via two amino N atoms. The resulting coordination polymer has a staircase-type structure that results from the fact that the amino nitrogen introduces an angular turn (C4—N2—Ag2 111.9 (1)°) into the polymer chain.

Both of the amino group H atoms are hydrogen bonded (Table 1) to adjacent perchlorate counterions, which in turn serve to bridge adjacent chains through two such hydrogen bonds (Fig. 2). The perchlorate O atoms are also involved in weak interactions with the silver atoms, which in the case of Ag2 leads to a pseudo-octahedral coordination environment for this atom. The perchlorate O atoms make weak contacts with some CH H atoms. These additional interactions increase the dimensionality of the overall assembly. This structure represents the first example in which ligand (1) acts as a bridging ligand for silver(I).

Experimental

The title compound was prepared by slow evaporation of an acetone solution containing an equimolar ratio of 4-aminopyridine and silver perchlorate.

Refinement

CH hydrogen atoms were introduced in calculated positions as riding atoms, with Uiso(H) = 1.2Ueq(C). The NH H atoms were located from a difference Fourier map and their positions refined with Uiso(H) = 1.2Ueq(N).

Figures

Fig. 1.
The molecular structure of (2), showing displacement ellipsoids at the 50% probability level.
Fig. 2.
Extended structure of (2), showing the staircase structure and the hydrogen bonding interactions.

Crystal data

[Ag(C5H6N2)]ClO4Z = 2
Mr = 301.44F(000) = 292
Triclinic, P1Dx = 2.359 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.0720 (2) ÅCell parameters from 6232 reflections
b = 9.0025 (3) Åθ = 3.0–26.4°
c = 9.5520 (3) ŵ = 2.67 mm1
α = 93.198 (2)°T = 113 K
β = 96.992 (2)°Prism, orange
γ = 100.452 (2)°0.35 × 0.11 × 0.05 mm
V = 424.37 (3) Å3

Data collection

Bruker APEXII CCD diffractometer1740 independent reflections
Radiation source: fine-focus sealed tube1591 reflections with I > 2σ(I)
graphiteRint = 0.046
[var phi] and ω scansθmax = 26.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −6→6
Tmin = 0.455, Tmax = 0.878k = −11→11
9107 measured reflectionsl = −11→11

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.051H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.0333P)2 + 0.1489P] where P = (Fo2 + 2Fc2)/3
1740 reflections(Δ/σ)max = 0.017
127 parametersΔρmax = 0.57 e Å3
0 restraintsΔρmin = −0.78 e Å3

Special details

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)

xyzUiso*/Ueq
Ag10.00000.00000.50000.02748 (9)
Ag20.5000−0.50000.00000.02716 (9)
Cl1−0.04375 (9)−0.70217 (6)0.19452 (5)0.02471 (12)
O1−0.0156 (4)−0.81713 (18)0.08849 (17)0.0372 (4)
O20.0718 (4)−0.7384 (2)0.32954 (17)0.0405 (4)
O30.0969 (3)−0.55690 (18)0.16137 (19)0.0338 (4)
O4−0.3233 (3)−0.6953 (2)0.1977 (2)0.0530 (6)
N10.2684 (3)−0.10407 (19)0.38878 (18)0.0212 (3)
C20.3565 (4)−0.2298 (2)0.4306 (2)0.0253 (4)
H2A0.3003−0.27100.51390.030*
C30.5233 (4)−0.3006 (2)0.3584 (2)0.0245 (4)
H3A0.5804−0.38860.39170.029*
C40.6080 (4)−0.2422 (2)0.2358 (2)0.0187 (4)
C50.5244 (4)−0.1101 (2)0.1946 (2)0.0224 (4)
H5A0.5824−0.06470.11340.027*
C60.3576 (4)−0.0467 (2)0.2725 (2)0.0246 (4)
H6A0.30170.04300.24270.030*
N20.7619 (3)−0.3164 (2)0.15325 (19)0.0218 (3)
H2B0.874 (5)−0.362 (3)0.199 (3)0.026*
H2C0.845 (5)−0.259 (3)0.097 (3)0.026*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ag10.01995 (12)0.03359 (15)0.02912 (14)0.00871 (9)0.00516 (9)−0.01157 (10)
Ag20.02874 (13)0.02542 (14)0.02684 (14)0.00551 (9)0.00580 (9)−0.00782 (9)
Cl10.0227 (2)0.0299 (3)0.0266 (3)0.01105 (19)0.00968 (18)0.0130 (2)
O10.0491 (10)0.0312 (9)0.0296 (9)0.0013 (7)0.0083 (7)0.0022 (7)
O20.0520 (10)0.0550 (11)0.0238 (8)0.0281 (9)0.0100 (7)0.0138 (8)
O30.0347 (8)0.0259 (8)0.0473 (10)0.0105 (6)0.0211 (7)0.0102 (7)
O40.0238 (9)0.0665 (13)0.0815 (15)0.0196 (8)0.0229 (9)0.0445 (12)
N10.0193 (8)0.0232 (8)0.0211 (8)0.0061 (6)0.0032 (6)−0.0055 (7)
C20.0309 (11)0.0270 (11)0.0197 (10)0.0059 (8)0.0089 (8)0.0023 (8)
C30.0322 (11)0.0224 (10)0.0225 (10)0.0112 (8)0.0075 (8)0.0045 (8)
C40.0167 (9)0.0202 (9)0.0183 (9)0.0031 (7)0.0015 (7)−0.0025 (7)
C50.0276 (10)0.0207 (10)0.0204 (10)0.0058 (8)0.0063 (8)0.0037 (8)
C60.0270 (10)0.0209 (10)0.0269 (11)0.0088 (8)0.0020 (8)0.0000 (8)
N20.0212 (8)0.0233 (9)0.0227 (9)0.0069 (7)0.0072 (7)0.0004 (7)

Geometric parameters (Å, °)

Ag1—N12.1363 (16)C2—H2A0.9500
Ag1—N1i2.1363 (16)C3—C41.393 (3)
Ag2—N2ii2.2582 (18)C3—H3A0.9500
Ag2—N22.2583 (18)C4—C51.394 (3)
Cl1—O21.4301 (16)C4—N21.399 (3)
Cl1—O41.4344 (16)C5—C61.371 (3)
Cl1—O31.4430 (16)C5—H5A0.9500
Cl1—O11.4454 (17)C6—H6A0.9500
N1—C61.344 (3)N2—H2B0.85 (3)
N1—C21.353 (3)N2—H2C0.86 (3)
C2—C31.373 (3)
N1—Ag1—N1i180.00 (5)C4—C3—H3A120.3
N2ii—Ag2—N2180.0C5—C4—C3117.63 (18)
O2—Cl1—O4109.54 (11)C5—C4—N2120.84 (18)
O2—Cl1—O3109.91 (12)C3—C4—N2121.47 (18)
O4—Cl1—O3108.88 (10)C6—C5—C4119.20 (19)
O2—Cl1—O1108.65 (11)C6—C5—H5A120.4
O4—Cl1—O1110.77 (13)C4—C5—H5A120.4
O3—Cl1—O1109.08 (10)N1—C6—C5123.77 (19)
C6—N1—C2116.76 (17)N1—C6—H6A118.1
C6—N1—Ag1120.93 (13)C5—C6—H6A118.1
C2—N1—Ag1122.31 (13)C4—N2—Ag2111.91 (12)
N1—C2—C3123.15 (19)C4—N2—H2B115.5 (17)
N1—C2—H2A118.4Ag2—N2—H2B104.1 (17)
C3—C2—H2A118.4C4—N2—H2C113.7 (17)
C2—C3—C4119.45 (19)Ag2—N2—H2C101.4 (17)
C2—C3—H3A120.3H2B—N2—H2C109 (2)

Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y−1, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2C···O1ii0.86 (3)2.16 (3)2.984 (3)161 (2)
N2—H2B···O3iii0.85 (3)2.29 (3)2.984 (3)139 (2)

Symmetry codes: (ii) −x+1, −y−1, −z; (iii) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BV2161).

References

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Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography