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

Golder, R.K.; Fitchett, C.M.; Wikaira, J.L.; Steel, P.J.

doi:10.1107/S1600536810037682

metal-organic compounds

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Volume 66| Part 10| October 2010| Page m1324

doi:10.1107/S1600536810037682

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

Ryan K. Golder,^a Christopher M. Fitchett,^a Jan L. Wikaira ^a and Peter J. Steel ^a ^*

^aChemistry Department, University of Canterbury, PO Box 4800, Christchurch, New Zealand
^*Correspondence e-mail: peter.steel@canterbury.ac.nz

(Received 2 September 2010; accepted 20 September 2010; online 30 September 2010)

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

Experimental

Crystal data

[Ag(C₅H₆N₂)]ClO₄
M_r = 301.44
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.021
wR(F²) = 0.051
S = 1.03
1740 reflections
127 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.78 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯O1ⁱ	0.86 (3)	2.16 (3)	2.984 (3)	161 (2)
N2—H2B⋯O3ⁱⁱ	0.85 (3)	2.29 (3)	2.984 (3)	139 (2)
Symmetry codes: (i) -x+1, -y-1, -z; (ii) x+1, y, z.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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.

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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 (Sheldrick, 2008).

Figures top

	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.

catena-Poly[[silver(I)-µ-4-aminopyridine] perchlorate] top

Crystal data top

[Ag(C₅H₆N₂)]ClO₄	Z = 2
M_r = 301.44	F(000) = 292
Triclinic, P1	D_x = 2.359 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.0720 (2) Å	Cell parameters from 6232 reflections
b = 9.0025 (3) Å	θ = 3.0–26.4°
c = 9.5520 (3) Å	µ = 2.67 mm⁻¹
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 top

Bruker APEXII CCD diffractometer	1740 independent reflections
Radiation source: fine-focus sealed tube	1591 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ϕ and ω scans	θ_max = 26.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −6→6
T_min = 0.455, T_max = 0.878	k = −11→11
9107 measured reflections	l = −11→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.051	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0333P)² + 0.1489P] where P = (F_o² + 2F_c²)/3
1740 reflections	(Δ/σ)_max = 0.017
127 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.78 e Å⁻³

Crystal data top

[Ag(C₅H₆N₂)]ClO₄	γ = 100.452 (2)°
M_r = 301.44	V = 424.37 (3) Å³
Triclinic, P1	Z = 2
a = 5.0720 (2) Å	Mo Kα radiation
b = 9.0025 (3) Å	µ = 2.67 mm⁻¹
c = 9.5520 (3) Å	T = 113 K
α = 93.198 (2)°	0.35 × 0.11 × 0.05 mm
β = 96.992 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1740 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1591 reflections with I > 2σ(I)
T_min = 0.455, T_max = 0.878	R_int = 0.046
9107 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	0 restraints
wR(F²) = 0.051	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.57 e Å⁻³
1740 reflections	Δρ_min = −0.78 e Å⁻³
127 parameters

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

	x	y	z	U_iso*/U_eq
Ag1	0.0000	0.0000	0.5000	0.02748 (9)
Ag2	0.5000	−0.5000	0.0000	0.02716 (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)
O2	0.0718 (4)	−0.7384 (2)	0.32954 (17)	0.0405 (4)
O3	0.0969 (3)	−0.55690 (18)	0.16137 (19)	0.0338 (4)
O4	−0.3233 (3)	−0.6953 (2)	0.1977 (2)	0.0530 (6)
N1	0.2684 (3)	−0.10407 (19)	0.38878 (18)	0.0212 (3)
C2	0.3565 (4)	−0.2298 (2)	0.4306 (2)	0.0253 (4)
H2A	0.3003	−0.2710	0.5139	0.030*
C3	0.5233 (4)	−0.3006 (2)	0.3584 (2)	0.0245 (4)
H3A	0.5804	−0.3886	0.3917	0.029*
C4	0.6080 (4)	−0.2422 (2)	0.2358 (2)	0.0187 (4)
C5	0.5244 (4)	−0.1101 (2)	0.1946 (2)	0.0224 (4)
H5A	0.5824	−0.0647	0.1134	0.027*
C6	0.3576 (4)	−0.0467 (2)	0.2725 (2)	0.0246 (4)
H6A	0.3017	0.0430	0.2427	0.030*
N2	0.7619 (3)	−0.3164 (2)	0.15325 (19)	0.0218 (3)
H2B	0.874 (5)	−0.362 (3)	0.199 (3)	0.026*
H2C	0.845 (5)	−0.259 (3)	0.097 (3)	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.01995 (12)	0.03359 (15)	0.02912 (14)	0.00871 (9)	0.00516 (9)	−0.01157 (10)
Ag2	0.02874 (13)	0.02542 (14)	0.02684 (14)	0.00551 (9)	0.00580 (9)	−0.00782 (9)
Cl1	0.0227 (2)	0.0299 (3)	0.0266 (3)	0.01105 (19)	0.00968 (18)	0.0130 (2)
O1	0.0491 (10)	0.0312 (9)	0.0296 (9)	0.0013 (7)	0.0083 (7)	0.0022 (7)
O2	0.0520 (10)	0.0550 (11)	0.0238 (8)	0.0281 (9)	0.0100 (7)	0.0138 (8)
O3	0.0347 (8)	0.0259 (8)	0.0473 (10)	0.0105 (6)	0.0211 (7)	0.0102 (7)
O4	0.0238 (9)	0.0665 (13)	0.0815 (15)	0.0196 (8)	0.0229 (9)	0.0445 (12)
N1	0.0193 (8)	0.0232 (8)	0.0211 (8)	0.0061 (6)	0.0032 (6)	−0.0055 (7)
C2	0.0309 (11)	0.0270 (11)	0.0197 (10)	0.0059 (8)	0.0089 (8)	0.0023 (8)
C3	0.0322 (11)	0.0224 (10)	0.0225 (10)	0.0112 (8)	0.0075 (8)	0.0045 (8)
C4	0.0167 (9)	0.0202 (9)	0.0183 (9)	0.0031 (7)	0.0015 (7)	−0.0025 (7)
C5	0.0276 (10)	0.0207 (10)	0.0204 (10)	0.0058 (8)	0.0063 (8)	0.0037 (8)
C6	0.0270 (10)	0.0209 (10)	0.0269 (11)	0.0088 (8)	0.0020 (8)	0.0000 (8)
N2	0.0212 (8)	0.0233 (9)	0.0227 (9)	0.0069 (7)	0.0072 (7)	0.0004 (7)

Geometric parameters (Å, º) top

Ag1—N1	2.1363 (16)	C2—H2A	0.9500
Ag1—N1ⁱ	2.1363 (16)	C3—C4	1.393 (3)
Ag2—N2ⁱⁱ	2.2582 (18)	C3—H3A	0.9500
Ag2—N2	2.2583 (18)	C4—C5	1.394 (3)
Cl1—O2	1.4301 (16)	C4—N2	1.399 (3)
Cl1—O4	1.4344 (16)	C5—C6	1.371 (3)
Cl1—O3	1.4430 (16)	C5—H5A	0.9500
Cl1—O1	1.4454 (17)	C6—H6A	0.9500
N1—C6	1.344 (3)	N2—H2B	0.85 (3)
N1—C2	1.353 (3)	N2—H2C	0.86 (3)
C2—C3	1.373 (3)

N1—Ag1—N1ⁱ	180.00 (5)	C4—C3—H3A	120.3
N2ⁱⁱ—Ag2—N2	180.0	C5—C4—C3	117.63 (18)
O2—Cl1—O4	109.54 (11)	C5—C4—N2	120.84 (18)
O2—Cl1—O3	109.91 (12)	C3—C4—N2	121.47 (18)
O4—Cl1—O3	108.88 (10)	C6—C5—C4	119.20 (19)
O2—Cl1—O1	108.65 (11)	C6—C5—H5A	120.4
O4—Cl1—O1	110.77 (13)	C4—C5—H5A	120.4
O3—Cl1—O1	109.08 (10)	N1—C6—C5	123.77 (19)
C6—N1—C2	116.76 (17)	N1—C6—H6A	118.1
C6—N1—Ag1	120.93 (13)	C5—C6—H6A	118.1
C2—N1—Ag1	122.31 (13)	C4—N2—Ag2	111.91 (12)
N1—C2—C3	123.15 (19)	C4—N2—H2B	115.5 (17)
N1—C2—H2A	118.4	Ag2—N2—H2B	104.1 (17)
C3—C2—H2A	118.4	C4—N2—H2C	113.7 (17)
C2—C3—C4	119.45 (19)	Ag2—N2—H2C	101.4 (17)
C2—C3—H3A	120.3	H2B—N2—H2C	109 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O1ⁱⁱ	0.86 (3)	2.16 (3)	2.984 (3)	161 (2)
N2—H2B···O3ⁱⁱⁱ	0.85 (3)	2.29 (3)	2.984 (3)	139 (2)

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

Experimental details

Crystal data
Chemical formula	[Ag(C₅H₆N₂)]ClO₄
M_r	301.44
Crystal system, space group	Triclinic, P1
Temperature (K)	113
a, b, c (Å)	5.0720 (2), 9.0025 (3), 9.5520 (3)
α, β, γ (°)	93.198 (2), 96.992 (2), 100.452 (2)
V (Å³)	424.37 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.67
Crystal size (mm)	0.35 × 0.11 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.455, 0.878
No. of measured, independent and observed [I > 2σ(I)] reflections	9107, 1740, 1591
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.051, 1.03
No. of reflections	1740
No. of parameters	127
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.78

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Ag1—N1	2.1363 (16)	C4—N2	1.399 (3)
Ag2—N2	2.2583 (18)

C6—N1—C2	116.76 (17)	C2—N1—Ag1	122.31 (13)
C6—N1—Ag1	120.93 (13)	C4—N2—Ag2	111.91 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O1ⁱ	0.86 (3)	2.16 (3)	2.984 (3)	161 (2)
N2—H2B···O3ⁱⁱ	0.85 (3)	2.29 (3)	2.984 (3)	139 (2)

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

Acknowledgements

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

References

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Volume 66| Part 10| October 2010| Page m1324

doi:10.1107/S1600536810037682

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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