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Acta Cryst. (2007). E63, m2131-m2132    [ doi:10.1107/S1600536807033430 ]

Poly[[silver(I)-bis[[mu]2-3-(aminomethyl)pyridine]-[kappa]2N1:N3;[kappa]2N3:N1] hexafluoridophosphate]

C. E. Carson, R. P. Feazell and K. K. Klausmeyer

Abstract top

In the title compound, {[Ag(C6H8N2)2]PF6}n, a two-dimensional coordination polymer is formed by linking each Ag atom of the [Ag(3-AMP)]2 rings [3-AMP is 3-(aminomethyl)pyridine] with an additional equivalent of 3-AMP. This polymer exhibits hydrogen bonding to the anion, which sits in channels forming a three-dimensional network. Each Ag atom is ligated by two pyridine and two amine groups.

Comment top

The title compound, (I), is isostructural with Ag(3-aminomethylpyridine)2BF4 (Klausmeyer et al., 2004). The extended structure reveals that the hexafluorophosphate ions are intercalated between the sheets of 'box-linker-box' units and hydrogen bond with the amine H atoms creating an intricate extended packing structure. The title compound (1) contains silvers in the +1 oxidation state that have distorted tetrahedral geometry with a coordination sphere consisting of two pyridyl N atoms and two amine N atoms from the ligand. The structure displays a "box-linker-box" motif. This motif consists of two 3-AMP ligands binding in a head-to-tail fashion with two silvers. The distance from Ag to Ag across the box is 5.0079 (9) Å. The boxes are then linked by 3-AMP ligands to form the two dimensional polymer.

Related literature top

For related literature, see: Feazell et al. (2006a,b,c); Klausmeyer et al. (2004)

Experimental top

The reaction was carried out under an argon atmosphere using a Schlenk line and standard Schlenk techniques. Glassware was dried at 120 °C for several hours prior to use. All reagents were stored in an inert-atmosphere glovebox; solvents were distilled under nitrogen from the appropriate drying agent immediately before use This reaction used 2 equiv of 3-AMP (0.150 g, 1.40 mmol) in 5 ml CH3CN added to a solution of AgPF6 (0.135 g, 0.69 mmol) in 5 ml CH3CN. Upon evaporation of the solvent, a white powder was isolated in 84% yield (0.239 g, 0.583 mmol). Colorless plates of (1) were formed at 5 °C by the slow diffusion of ether into a CH3CN solution of (1)

Refinement top

Hydrogen atoms were included in calculated positions (Cring—H = 0.930 Å); (Cmethylene—H = 0.970 Å); (N—H = 0.900 Å) isotropic displacement parameters were fixed [Uiso(H) = 1.2Uiso(C)]; [Uiso(H) = 1.2Uiso(N)]; [Uiso(H) = 1.2Uiso(Cring)].

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: APEX2; data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot of the unique portion of 1, ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The "box-linker-box" motif.
[Figure 3] Fig. 3. Extended packing diagram displaying H-bonding.
Poly[[silver(I)-bis[µ2-3-(aminomethyl)pyridine]- κ2N1:N3;κ2N3:N1] hexafluoridophosphate] top
Crystal data top
[Ag(C6H8N2)2]PF6F(000) = 928
Mr = 469.13Dx = 1.928 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 7201 reflections
a = 6.9563 (11) Åθ = 2.7–26.6°
b = 11.584 (2) ŵ = 1.41 mm−1
c = 20.060 (3) ÅT = 110 K
β = 90.271 (5)°Block, colorless
V = 1616.4 (4) Å30.25 × 0.17 × 0.12 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		3387 independent reflections
Radiation source: fine-focus sealed tube3006 reflections with I > 2σ(I)
graphiteRint = 0.031
φ and ω scansθmax = 26.7°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→8
Tmin = 0.740, Tmax = 0.845k = −14→14
16863 measured reflectionsl = −25→25
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)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H-atom parameters constrained
S = 0.96 w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
3387 reflections(Δ/σ)max < 0.001
217 parametersΔρmax = 1.18 e Å−3
0 restraintsΔρmin = −0.67 e Å−3
Crystal data top
[Ag(C6H8N2)2]PF6V = 1616.4 (4) Å3
Mr = 469.13Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.9563 (11) ŵ = 1.41 mm−1
b = 11.584 (2) ÅT = 110 K
c = 20.060 (3) Å0.25 × 0.17 × 0.12 mm
β = 90.271 (5)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		3387 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3006 reflections with I > 2σ(I)
Tmin = 0.740, Tmax = 0.845Rint = 0.031
16863 measured reflectionsθmax = 26.7°
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.117Δρmax = 1.18 e Å−3
S = 0.96Δρmin = −0.67 e Å−3
3387 reflectionsAbsolute structure: ?
217 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
Ag10.04519 (3)−0.028628 (19)0.122801 (11)0.01880 (13)
N40.3921 (4)0.3978 (2)0.26917 (13)0.0221 (6)
H4A0.46370.43830.24020.026*
H4B0.43430.32440.26800.026*
N20.2897 (4)0.0347 (2)−0.13631 (16)0.0220 (6)
H2A0.31460.0632−0.17710.026*
H2B0.33820.0847−0.10630.026*
N10.2333 (4)−0.1277 (2)0.04850 (13)0.0185 (5)
N30.1174 (4)0.1695 (2)0.11364 (13)0.0187 (5)
C90.2783 (4)−0.0771 (3)−0.00970 (15)0.0174 (6)
H90.26220.0024−0.01310.021*
C60.1799 (4)0.4065 (3)0.11783 (17)0.0214 (6)
H60.19990.48590.11880.026*
C40.1308 (4)0.2319 (3)0.05778 (15)0.0179 (6)
H40.11920.19420.01700.021*
C80.3470 (4)−0.1354 (3)−0.06464 (16)0.0184 (6)
C20.1688 (4)0.3443 (3)0.17690 (15)0.0184 (6)
C30.1356 (4)0.2257 (3)0.17155 (15)0.0187 (6)
H30.12550.18310.21070.022*
C120.3746 (5)−0.2542 (3)−0.05791 (17)0.0243 (7)
H120.4206−0.2974−0.09350.029*
C50.1610 (4)0.3499 (3)0.05785 (16)0.0214 (6)
H50.16850.39040.01790.026*
C110.3334 (5)−0.3069 (3)0.00161 (17)0.0257 (7)
H110.3526−0.38590.00680.031*
C100.2636 (4)−0.2420 (3)0.05352 (17)0.0225 (7)
H100.2363−0.27860.09370.027*
C10.1937 (5)0.3985 (3)0.24467 (16)0.0232 (7)
H1A0.14880.47770.24270.028*
H1B0.11360.35750.27630.028*
C70.3925 (5)−0.0750 (3)−0.12915 (16)0.0241 (7)
H7A0.5297−0.0607−0.13120.029*
H7B0.3584−0.1251−0.16610.029*
P20.74018 (13)0.62393 (7)0.16233 (4)0.0247 (2)
F10.7579 (4)0.52866 (18)0.21854 (13)0.0396 (6)
F20.7217 (3)0.7249 (2)0.21651 (12)0.0419 (6)
F30.9663 (3)0.6428 (2)0.16267 (13)0.0476 (6)
F40.7170 (4)0.71905 (19)0.10383 (12)0.0463 (6)
F50.5096 (3)0.6095 (2)0.16439 (13)0.0484 (6)
F60.7550 (5)0.52789 (19)0.10652 (14)0.0519 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.01953 (19)0.02047 (18)0.01639 (18)0.00159 (8)0.00101 (11)0.00152 (8)
N40.0196 (13)0.0271 (14)0.0195 (13)0.0014 (11)−0.0016 (10)−0.0055 (11)
N20.0207 (15)0.0242 (15)0.0212 (15)0.0011 (10)0.0021 (12)0.0064 (10)
N10.0157 (13)0.0208 (12)0.0191 (13)−0.0007 (10)0.0005 (10)0.0020 (10)
N30.0158 (12)0.0188 (13)0.0214 (13)−0.0008 (10)−0.0015 (10)−0.0009 (10)
C90.0135 (14)0.0190 (14)0.0197 (14)−0.0008 (12)−0.0019 (11)−0.0005 (12)
C60.0180 (15)0.0182 (14)0.0280 (17)−0.0018 (12)−0.0014 (12)−0.0032 (13)
C40.0138 (14)0.0217 (14)0.0181 (14)0.0009 (12)−0.0021 (11)−0.0023 (12)
C80.0101 (14)0.0243 (15)0.0209 (15)0.0026 (12)0.0005 (11)0.0016 (12)
C20.0125 (14)0.0231 (15)0.0197 (15)0.0012 (12)−0.0002 (11)−0.0061 (12)
C30.0173 (15)0.0217 (14)0.0172 (14)0.0008 (12)−0.0007 (12)0.0000 (12)
C120.0177 (15)0.0269 (16)0.0283 (17)0.0033 (13)0.0030 (13)−0.0051 (13)
C50.0190 (15)0.0242 (15)0.0209 (15)0.0013 (13)−0.0011 (12)0.0043 (12)
C110.0246 (17)0.0200 (15)0.0325 (18)0.0065 (13)0.0012 (14)0.0021 (14)
C100.0166 (15)0.0220 (15)0.0287 (17)0.0031 (12)0.0004 (13)0.0076 (13)
C10.0210 (16)0.0270 (16)0.0216 (16)0.0013 (13)0.0009 (13)−0.0042 (13)
C70.0227 (16)0.0290 (17)0.0207 (16)0.0064 (15)0.0050 (12)0.0024 (13)
P20.0297 (5)0.0218 (4)0.0228 (4)−0.0035 (3)0.0063 (4)−0.0012 (3)
F10.0413 (14)0.0420 (14)0.0356 (13)0.0008 (9)0.0004 (11)0.0163 (9)
F20.0488 (14)0.0400 (13)0.0368 (12)0.0031 (11)0.0051 (10)−0.0080 (10)
F30.0317 (12)0.0407 (13)0.0704 (17)−0.0021 (10)0.0145 (11)0.0096 (12)
F40.0753 (18)0.0309 (11)0.0326 (12)−0.0017 (11)−0.0010 (11)0.0074 (10)
F50.0307 (12)0.0544 (15)0.0601 (16)−0.0054 (11)−0.0093 (11)0.0077 (13)
F60.082 (2)0.0376 (15)0.0358 (15)0.0010 (12)0.0038 (14)−0.0110 (10)
Geometric parameters (Å, °) top
Ag1—N12.296 (3)C4—H40.9300
Ag1—N2i2.348 (3)C8—C121.396 (4)
Ag1—N32.357 (3)C8—C71.506 (4)
Ag1—N4ii2.367 (3)C2—C31.397 (4)
N4—C11.462 (4)C2—C11.507 (4)
N4—Ag1iii2.367 (3)C3—H30.9300
N4—H4A0.9000C12—C111.372 (5)
N4—H4B0.9000C12—H120.9300
N2—C71.465 (4)C5—H50.9300
N2—Ag1i2.348 (3)C11—C101.375 (5)
N2—H2A0.9000C11—H110.9300
N2—H2B0.9000C10—H100.9300
N1—C101.344 (4)C1—H1A0.9700
N1—C91.345 (4)C1—H1B0.9700
N3—C31.337 (4)C7—H7A0.9700
N3—C41.337 (4)C7—H7B0.9700
C9—C81.379 (4)P2—F61.582 (3)
C9—H90.9300P2—F11.582 (2)
C6—C51.376 (4)P2—F31.588 (2)
C6—C21.389 (4)P2—F21.602 (2)
C6—H60.9300P2—F51.613 (2)
C4—C51.383 (4)P2—F41.617 (2)
N1—Ag1—N2i128.98 (10)C2—C3—H3118.0
N1—Ag1—N3108.29 (9)C11—C12—C8119.6 (3)
N2i—Ag1—N3104.49 (9)C11—C12—H12120.2
N1—Ag1—N4ii108.13 (9)C8—C12—H12120.2
N2i—Ag1—N4ii93.57 (10)C6—C5—C4119.1 (3)
N3—Ag1—N4ii112.55 (9)C6—C5—H5120.5
C1—N4—Ag1iii118.38 (19)C4—C5—H5120.5
C1—N4—H4A107.7C12—C11—C10119.4 (3)
Ag1iii—N4—H4A107.7C12—C11—H11120.3
C1—N4—H4B107.7C10—C11—H11120.3
Ag1iii—N4—H4B107.7N1—C10—C11122.5 (3)
H4A—N4—H4B107.1N1—C10—H10118.7
C7—N2—Ag1i116.5 (2)C11—C10—H10118.7
C7—N2—H2A108.2N4—C1—C2113.9 (3)
Ag1i—N2—H2A108.2N4—C1—H1A108.8
C7—N2—H2B108.2C2—C1—H1A108.8
Ag1i—N2—H2B108.2N4—C1—H1B108.8
H2A—N2—H2B107.3C2—C1—H1B108.8
C10—N1—C9117.2 (3)H1A—C1—H1B107.7
C10—N1—Ag1122.2 (2)N2—C7—C8112.5 (3)
C9—N1—Ag1118.8 (2)N2—C7—H7A109.1
C3—N3—C4117.3 (3)C8—C7—H7A109.1
C3—N3—Ag1115.16 (19)N2—C7—H7B109.1
C4—N3—Ag1127.4 (2)C8—C7—H7B109.1
N1—C9—C8124.3 (3)H7A—C7—H7B107.8
N1—C9—H9117.9F6—P2—F190.49 (14)
C8—C9—H9117.9F6—P2—F391.82 (16)
C5—C6—C2119.5 (3)F1—P2—F391.09 (14)
C5—C6—H6120.2F6—P2—F2177.56 (15)
C2—C6—H6120.2F1—P2—F291.85 (13)
N3—C4—C5123.0 (3)F3—P2—F288.81 (13)
N3—C4—H4118.5F6—P2—F590.78 (16)
C5—C4—H4118.5F1—P2—F589.07 (13)
C9—C8—C12117.0 (3)F3—P2—F5177.39 (16)
C9—C8—C7122.3 (3)F2—P2—F588.58 (13)
C12—C8—C7120.8 (3)F6—P2—F488.41 (13)
C6—C2—C3117.0 (3)F1—P2—F4178.28 (15)
C6—C2—C1123.1 (3)F3—P2—F490.27 (14)
C3—C2—C1119.8 (3)F2—P2—F489.24 (13)
N3—C3—C2124.1 (3)F5—P2—F489.62 (14)
N3—C3—H3118.0
Symmetry codes: (i) −x, −y, −z; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1/2, y+1/2, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···F10.902.343.135 (4)147
N4—H4A···F50.902.523.334 (4)151
N4—H4B···F3iv0.902.613.399 (4)146
N2—H2A···F1v0.902.383.010 (4)127
N2—H2A···F2vi0.902.593.217 (3)127
N2—H2B···F4vi0.902.312.926 (3)126
Symmetry codes: (iv) −x+3/2, y−1/2, −z+1/2; (v) x−1/2, −y+1/2, z−1/2; (vi) −x+1, −y+1, −z.
Table 1
Selected geometric parameters (Å, °) top
Ag1—N12.296 (3)Ag1—N32.357 (3)
Ag1—N2i2.348 (3)Ag1—N4ii2.367 (3)
N1—Ag1—N2i128.98 (10)N1—Ag1—N4ii108.13 (9)
N1—Ag1—N3108.29 (9)N2i—Ag1—N4ii93.57 (10)
N2i—Ag1—N3104.49 (9)N3—Ag1—N4ii112.55 (9)
Symmetry codes: (i) −x, −y, −z; (ii) −x+1/2, y−1/2, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···F10.902.343.135 (4)147
N4—H4A···F50.902.523.334 (4)151
N4—H4B···F3iii0.902.613.399 (4)146
N2—H2A···F1iv0.902.383.010 (4)127
N2—H2A···F2v0.902.593.217 (3)127
N2—H2B···F4v0.902.312.926 (3)126
Symmetry codes: (iii) −x+3/2, y−1/2, −z+1/2; (iv) x−1/2, −y+1/2, z−1/2; (v) −x+1, −y+1, −z.
Acknowledgements top

The Bruker APEX X8 diffractometer [SMART above?] was purchased with funds received from the National Science Foundation Major Research Instrumentation Program grant CHE-0321214. K K thanks the Robert A. Welch Foundation for support (AA-1508).

references
References top

Bruker (2003). APEX2 (Version 1.0-33) and SAINT-Plus (Version 6.25). Bruker AXS Inc., Madison, Wisconsin, USA

Feazell, R. P., Carson, C. E. & Klausmeyer, K. K. (2006a). Inorg. Chem. 45, 935–944.

Feazell, R. P., Carson, C. E. & Klausmeyer, K. K. (2006b). Inorg. Chem. 45, 2327–2634.

Feazell, R. P., Carson, C. E. & Klausmeyer, K. K. (2006c). Inorg. Chem. 45, 2635–2643.

Klausmeyer, K. K., Feazell, R. P. & Reibenspies, J. H. (2004). Inorg. Chem. 43, 1130–1136.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany

Sheldrick, G. M. (2000). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA