Poly[[silver(I)-bis­[μ₂-3-(amino­meth­yl)­pyridine]-κ²N¹:N³;κ²N³:N¹] hexa­fluorido­phosphate]

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.

Key indicators

• Single-crystal X-ray study
• T = 110 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.029
• wR factor = 0.117
• Data-to-parameter ratio = 15.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         P2
PLAT420_ALERT_2_C D-H Without Acceptor       N4     -   H4B    ...          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4B    ..  F3      ..       2.61 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2A    ..  F2      ..       2.59 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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)

S3. Refinement

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

Computing details

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

	Fig. 1. Thermal ellipsoid plot of the unique portion of 1, ellipsoids are drawn at the 50% probability level.
	Fig. 2. The "box-linker-box" motif.
	Fig. 3. Extended packing diagram displaying H-bonding.

Poly[[silver(I)-bis[µ₂-3-(aminomethyl)pyridine]- κ²N¹:N³;κ²N³:N¹] hexafluoridophosphate]

Crystal data

[Ag(C6H8N2)2]PF6	F(000) = 928
Mr = 469.13	Dx = 1.928 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7201 reflections
a = 6.9563 (11) Å	θ = 2.7–26.6°
b = 11.584 (2) Å	µ = 1.41 mm^−1
c = 20.060 (3) Å	T = 110 K
β = 90.271 (5)°	Block, colorless
V = 1616.4 (4) Å^3	0.25 × 0.17 × 0.12 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	3387 independent reflections
Radiation source: fine-focus sealed tube	3006 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 26.7°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.740, Tmax = 0.845	k = −14→14
16863 measured reflections	l = −25→25

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
3387 reflections	(Δ/σ)max < 0.001
217 parameters	Δρmax = 1.18 e Å^−3
0 restraints	Δρmin = −0.67 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
Ag1	0.04519 (3)	−0.028628 (19)	0.122801 (11)	0.01880 (13)
N4	0.3921 (4)	0.3978 (2)	0.26917 (13)	0.0221 (6)
H4A	0.4637	0.4383	0.2402	0.026*
H4B	0.4343	0.3244	0.2680	0.026*
N2	0.2897 (4)	0.0347 (2)	−0.13631 (16)	0.0220 (6)
H2A	0.3146	0.0632	−0.1771	0.026*
H2B	0.3382	0.0847	−0.1063	0.026*
N1	0.2333 (4)	−0.1277 (2)	0.04850 (13)	0.0185 (5)
N3	0.1174 (4)	0.1695 (2)	0.11364 (13)	0.0187 (5)
C9	0.2783 (4)	−0.0771 (3)	−0.00970 (15)	0.0174 (6)
H9	0.2622	0.0024	−0.0131	0.021*
C6	0.1799 (4)	0.4065 (3)	0.11783 (17)	0.0214 (6)
H6	0.1999	0.4859	0.1188	0.026*
C4	0.1308 (4)	0.2319 (3)	0.05778 (15)	0.0179 (6)
H4	0.1192	0.1942	0.0170	0.021*
C8	0.3470 (4)	−0.1354 (3)	−0.06464 (16)	0.0184 (6)
C2	0.1688 (4)	0.3443 (3)	0.17690 (15)	0.0184 (6)
C3	0.1356 (4)	0.2257 (3)	0.17155 (15)	0.0187 (6)
H3	0.1255	0.1831	0.2107	0.022*
C12	0.3746 (5)	−0.2542 (3)	−0.05791 (17)	0.0243 (7)
H12	0.4206	−0.2974	−0.0935	0.029*
C5	0.1610 (4)	0.3499 (3)	0.05785 (16)	0.0214 (6)
H5	0.1685	0.3904	0.0179	0.026*
C11	0.3334 (5)	−0.3069 (3)	0.00161 (17)	0.0257 (7)
H11	0.3526	−0.3859	0.0068	0.031*
C10	0.2636 (4)	−0.2420 (3)	0.05352 (17)	0.0225 (7)
H10	0.2363	−0.2786	0.0937	0.027*
C1	0.1937 (5)	0.3985 (3)	0.24467 (16)	0.0232 (7)
H1A	0.1488	0.4777	0.2427	0.028*
H1B	0.1136	0.3575	0.2763	0.028*
C7	0.3925 (5)	−0.0750 (3)	−0.12915 (16)	0.0241 (7)
H7A	0.5297	−0.0607	−0.1312	0.029*
H7B	0.3584	−0.1251	−0.1661	0.029*
P2	0.74018 (13)	0.62393 (7)	0.16233 (4)	0.0247 (2)
F1	0.7579 (4)	0.52866 (18)	0.21854 (13)	0.0396 (6)
F2	0.7217 (3)	0.7249 (2)	0.21651 (12)	0.0419 (6)
F3	0.9663 (3)	0.6428 (2)	0.16267 (13)	0.0476 (6)
F4	0.7170 (4)	0.71905 (19)	0.10383 (12)	0.0463 (6)
F5	0.5096 (3)	0.6095 (2)	0.16439 (13)	0.0484 (6)
F6	0.7550 (5)	0.52789 (19)	0.10652 (14)	0.0519 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.01953 (19)	0.02047 (18)	0.01639 (18)	0.00159 (8)	0.00101 (11)	0.00152 (8)
N4	0.0196 (13)	0.0271 (14)	0.0195 (13)	0.0014 (11)	−0.0016 (10)	−0.0055 (11)
N2	0.0207 (15)	0.0242 (15)	0.0212 (15)	0.0011 (10)	0.0021 (12)	0.0064 (10)
N1	0.0157 (13)	0.0208 (12)	0.0191 (13)	−0.0007 (10)	0.0005 (10)	0.0020 (10)
N3	0.0158 (12)	0.0188 (13)	0.0214 (13)	−0.0008 (10)	−0.0015 (10)	−0.0009 (10)
C9	0.0135 (14)	0.0190 (14)	0.0197 (14)	−0.0008 (12)	−0.0019 (11)	−0.0005 (12)
C6	0.0180 (15)	0.0182 (14)	0.0280 (17)	−0.0018 (12)	−0.0014 (12)	−0.0032 (13)
C4	0.0138 (14)	0.0217 (14)	0.0181 (14)	0.0009 (12)	−0.0021 (11)	−0.0023 (12)
C8	0.0101 (14)	0.0243 (15)	0.0209 (15)	0.0026 (12)	0.0005 (11)	0.0016 (12)
C2	0.0125 (14)	0.0231 (15)	0.0197 (15)	0.0012 (12)	−0.0002 (11)	−0.0061 (12)
C3	0.0173 (15)	0.0217 (14)	0.0172 (14)	0.0008 (12)	−0.0007 (12)	0.0000 (12)
C12	0.0177 (15)	0.0269 (16)	0.0283 (17)	0.0033 (13)	0.0030 (13)	−0.0051 (13)
C5	0.0190 (15)	0.0242 (15)	0.0209 (15)	0.0013 (13)	−0.0011 (12)	0.0043 (12)
C11	0.0246 (17)	0.0200 (15)	0.0325 (18)	0.0065 (13)	0.0012 (14)	0.0021 (14)
C10	0.0166 (15)	0.0220 (15)	0.0287 (17)	0.0031 (12)	0.0004 (13)	0.0076 (13)
C1	0.0210 (16)	0.0270 (16)	0.0216 (16)	0.0013 (13)	0.0009 (13)	−0.0042 (13)
C7	0.0227 (16)	0.0290 (17)	0.0207 (16)	0.0064 (15)	0.0050 (12)	0.0024 (13)
P2	0.0297 (5)	0.0218 (4)	0.0228 (4)	−0.0035 (3)	0.0063 (4)	−0.0012 (3)
F1	0.0413 (14)	0.0420 (14)	0.0356 (13)	0.0008 (9)	0.0004 (11)	0.0163 (9)
F2	0.0488 (14)	0.0400 (13)	0.0368 (12)	0.0031 (11)	0.0051 (10)	−0.0080 (10)
F3	0.0317 (12)	0.0407 (13)	0.0704 (17)	−0.0021 (10)	0.0145 (11)	0.0096 (12)
F4	0.0753 (18)	0.0309 (11)	0.0326 (12)	−0.0017 (11)	−0.0010 (11)	0.0074 (10)
F5	0.0307 (12)	0.0544 (15)	0.0601 (16)	−0.0054 (11)	−0.0093 (11)	0.0077 (13)
F6	0.082 (2)	0.0376 (15)	0.0358 (15)	0.0010 (12)	0.0038 (14)	−0.0110 (10)

Geometric parameters (Å, º)

Ag1—N1	2.296 (3)	C4—H4	0.9300
Ag1—N2^i	2.348 (3)	C8—C12	1.396 (4)
Ag1—N3	2.357 (3)	C8—C7	1.506 (4)
Ag1—N4^ii	2.367 (3)	C2—C3	1.397 (4)
N4—C1	1.462 (4)	C2—C1	1.507 (4)
N4—Ag1^iii	2.367 (3)	C3—H3	0.9300
N4—H4A	0.9000	C12—C11	1.372 (5)
N4—H4B	0.9000	C12—H12	0.9300
N2—C7	1.465 (4)	C5—H5	0.9300
N2—Ag1^i	2.348 (3)	C11—C10	1.375 (5)
N2—H2A	0.9000	C11—H11	0.9300
N2—H2B	0.9000	C10—H10	0.9300
N1—C10	1.344 (4)	C1—H1A	0.9700
N1—C9	1.345 (4)	C1—H1B	0.9700
N3—C3	1.337 (4)	C7—H7A	0.9700
N3—C4	1.337 (4)	C7—H7B	0.9700
C9—C8	1.379 (4)	P2—F6	1.582 (3)
C9—H9	0.9300	P2—F1	1.582 (2)
C6—C5	1.376 (4)	P2—F3	1.588 (2)
C6—C2	1.389 (4)	P2—F2	1.602 (2)
C6—H6	0.9300	P2—F5	1.613 (2)
C4—C5	1.383 (4)	P2—F4	1.617 (2)
N1—Ag1—N2^i	128.98 (10)	C2—C3—H3	118.0
N1—Ag1—N3	108.29 (9)	C11—C12—C8	119.6 (3)
N2^i—Ag1—N3	104.49 (9)	C11—C12—H12	120.2
N1—Ag1—N4^ii	108.13 (9)	C8—C12—H12	120.2
N2^i—Ag1—N4^ii	93.57 (10)	C6—C5—C4	119.1 (3)
N3—Ag1—N4^ii	112.55 (9)	C6—C5—H5	120.5
C1—N4—Ag1^iii	118.38 (19)	C4—C5—H5	120.5
C1—N4—H4A	107.7	C12—C11—C10	119.4 (3)
Ag1^iii—N4—H4A	107.7	C12—C11—H11	120.3
C1—N4—H4B	107.7	C10—C11—H11	120.3
Ag1^iii—N4—H4B	107.7	N1—C10—C11	122.5 (3)
H4A—N4—H4B	107.1	N1—C10—H10	118.7
C7—N2—Ag1^i	116.5 (2)	C11—C10—H10	118.7
C7—N2—H2A	108.2	N4—C1—C2	113.9 (3)
Ag1^i—N2—H2A	108.2	N4—C1—H1A	108.8
C7—N2—H2B	108.2	C2—C1—H1A	108.8
Ag1^i—N2—H2B	108.2	N4—C1—H1B	108.8
H2A—N2—H2B	107.3	C2—C1—H1B	108.8
C10—N1—C9	117.2 (3)	H1A—C1—H1B	107.7
C10—N1—Ag1	122.2 (2)	N2—C7—C8	112.5 (3)
C9—N1—Ag1	118.8 (2)	N2—C7—H7A	109.1
C3—N3—C4	117.3 (3)	C8—C7—H7A	109.1
C3—N3—Ag1	115.16 (19)	N2—C7—H7B	109.1
C4—N3—Ag1	127.4 (2)	C8—C7—H7B	109.1
N1—C9—C8	124.3 (3)	H7A—C7—H7B	107.8
N1—C9—H9	117.9	F6—P2—F1	90.49 (14)
C8—C9—H9	117.9	F6—P2—F3	91.82 (16)
C5—C6—C2	119.5 (3)	F1—P2—F3	91.09 (14)
C5—C6—H6	120.2	F6—P2—F2	177.56 (15)
C2—C6—H6	120.2	F1—P2—F2	91.85 (13)
N3—C4—C5	123.0 (3)	F3—P2—F2	88.81 (13)
N3—C4—H4	118.5	F6—P2—F5	90.78 (16)
C5—C4—H4	118.5	F1—P2—F5	89.07 (13)
C9—C8—C12	117.0 (3)	F3—P2—F5	177.39 (16)
C9—C8—C7	122.3 (3)	F2—P2—F5	88.58 (13)
C12—C8—C7	120.8 (3)	F6—P2—F4	88.41 (13)
C6—C2—C3	117.0 (3)	F1—P2—F4	178.28 (15)
C6—C2—C1	123.1 (3)	F3—P2—F4	90.27 (14)
C3—C2—C1	119.8 (3)	F2—P2—F4	89.24 (13)
N3—C3—C2	124.1 (3)	F5—P2—F4	89.62 (14)
N3—C3—H3	118.0

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, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···F1	0.90	2.34	3.135 (4)	147
N4—H4A···F5	0.90	2.52	3.334 (4)	151
N4—H4B···F3^iv	0.90	2.61	3.399 (4)	146
N2—H2A···F1^v	0.90	2.38	3.010 (4)	127
N2—H2A···F2^vi	0.90	2.59	3.217 (3)	127
N2—H2B···F4^vi	0.90	2.31	2.926 (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.