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Acta Cryst. (2007). E63, m2467    [ doi:10.1107/S1600536807042419 ]

catena-Poly[[silver(I)-[mu]-1,4-di-3-pyridyl-2,3-diazabuta-1,3-diene] methanesulfonate]

G. A. Broker and E. R. T. Tiekink

Abstract top

In the polymeric title compound, {[Ag(C12H10N4)](CH3SO3)}n, the Ag atom exists in an almost linear NAgN geometry and the topology of the supramolecular chain is a zigzag. Adjacent chains are linked via weak argentophilic Ag...Ag interactions [3.1402 (8) Å] to form double chains and the anions are associated with this via Ag...O contacts [2.508 (3) Å]. Layers are formed through C-H...O interactions and the layers stack via [pi]-[pi] interactions [centroid-centroid separation = 3.751 (3) Å].

Comment top

The title compound, [Ag(C12H10N4)]n.n(CH3SO3}, (I), was investigated in connection with on-going studies of Ag salts of isomeric n-pyridinealdazine, n = 2, 3 or 4, molecules (Broker & Tiekink, 2007a, b). In (I), (Fig. 1 & Table 1), the Ag atom exists in a linear N2 geometry and the topology of the chain is zigzag owing to the relative disposition of the N-donor atoms. Similar polymeric chains are found for the perchlorate and tetrafluoroborate salts, each as acetonitrile solvates (Kennedy et al., 2005).

In (I), the chains are connected into double chains via weak argentophilic interactions [Ag···Ag = 3.1402 (8) Å] and the methanesulfonate anions are linked to this via Ag···O interactions [2.508 (3) Å]. The presence of C—H···O interactions consolidate the double-chains into layers and additional stabilization is afforded by C—H···N contacts between a methyl-H and an azo-N atom (Fig. 2 & Table 2). Successive layers are connected primarily by π···π contacts so that the distance between the centroids of the N1/C1—C5 and (N4/C8—C12)i rings is 3.751 (3) Å (i = 1 − x, 1 − y, −z).

Related literature top

For related polymeric silver salts containing the 3-pyridinealdazine ligand, see: Kennedy et al. (2005). For related literature, see: Broker & Tiekink (2007a, 2007b).

Experimental top

Ag(CF3SO3) (Aldrich, 0.05 g, 0.25 mmol) was dissolved in CH3CN (20 ml) and layered on top of a CH2Cl2 solution (20 ml) containing 0.05 g (0.25 mmol) of 3-pyridinealdazine (Aldrich). After three days, yellow rods and blocks of (I) were observed at the interface between the two layers; m.p. 555–557 K.

Refinement top

All the H atoms were included in the riding-model approximation, with C—H = 0.95–0.98Å and Uiso(H) = 1.2 or 1.5Ueq(C). The maximum and minimum difference peaks are located 0.87 and 0.88 Å, respectively, from Ag.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I) showing displacement ellipsoids at the 70% probability level (arbitrary spheres for the H atoms).
[Figure 2] Fig. 2. View of the supramolecular double chains in (I) highlighting the Ag···Ag and Ag···O interactions (black dashed lines). Colour code: orange (silver), yellow (sulfur), red (oxygen), blue (nitrogen), grey (carbon) and green (hydrogen).
catena-Poly[[silver(I)-µ-1,4-di-3-pyridyl-2,3-diazabuta-1,3-diene] methanesulfonate] top
Crystal data top
[Ag(C12H10N4)](CH3SO3)Z = 2
Mr = 413.21F000 = 412
Triclinic, P1Dx = 1.994 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71070 Å
a = 7.7818 (13) ÅCell parameters from 6258 reflections
b = 9.6799 (16) Åθ = 2.8–29.7º
c = 9.9742 (15) ŵ = 1.64 mm−1
α = 106.50 (1)ºT = 98 (2) K
β = 91.12 (1)ºRod, yellow
γ = 106.50 (1)º0.15 × 0.05 × 0.03 mm
V = 686.63 (19) Å3
Data collection top
Rigaku AFC12κ Saturn724
diffractometer		2793 independent reflections
Radiation source: fine-focus sealed tube2686 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
T = 98(2) Kθmax = 26.5º
ω scansθmin = 2.6º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −9→8
Tmin = 0.641, Tmax = 1.000k = −10→12
4287 measured reflectionsl = −12→12
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.115  w = 1/[σ2(Fo2) + (0.0581P)2 + 3.8177P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
2793 reflectionsΔρmax = 1.33 e Å−3
199 parametersΔρmin = −1.74 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ag(C12H10N4)](CH3SO3)γ = 106.50 (1)º
Mr = 413.21V = 686.63 (19) Å3
Triclinic, P1Z = 2
a = 7.7818 (13) ÅMo Kα
b = 9.6799 (16) ŵ = 1.64 mm−1
c = 9.9742 (15) ÅT = 98 (2) K
α = 106.50 (1)º0.15 × 0.05 × 0.03 mm
β = 91.12 (1)º
Data collection top
Rigaku AFC12κ Saturn724
diffractometer		2793 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2686 reflections with I > 2σ(I)
Tmin = 0.641, Tmax = 1.000Rint = 0.030
4287 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.044199 parameters
wR(F2) = 0.115H-atom parameters constrained
S = 1.09Δρmax = 1.33 e Å−3
2793 reflectionsΔρmin = −1.74 e Å−3
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
Ag−0.17114 (4)0.45886 (4)−0.42132 (3)0.01878 (14)
S10.24710 (15)0.79114 (12)−0.26031 (11)0.0167 (2)
O10.1198 (5)0.6446 (4)−0.2912 (4)0.0296 (8)
O20.1607 (5)0.9035 (4)−0.2162 (4)0.0279 (8)
O30.3649 (5)0.8196 (5)−0.3689 (4)0.0334 (9)
N1−0.1379 (5)0.2995 (4)−0.3042 (4)0.0153 (7)
N20.2373 (5)0.4241 (4)0.0284 (4)0.0167 (7)
N30.3507 (5)0.4542 (4)0.1490 (4)0.0159 (7)
N40.7448 (5)0.6106 (4)0.4777 (4)0.0153 (7)
C1−0.2417 (6)0.1603 (5)−0.3322 (4)0.0148 (8)
H1−0.32840.1221−0.41250.018*
C2−0.2351 (6)0.0603 (5)−0.2512 (5)0.0182 (9)
H2−0.3170−0.0391−0.27920.022*
C3−0.1162 (6)0.1037 (5)−0.1371 (5)0.0169 (8)
H3−0.10940.0398−0.08170.020*
C4−0.0069 (6)0.2470 (5)−0.1082 (4)0.0141 (8)
C5−0.0209 (6)0.3421 (5)−0.1940 (4)0.0138 (8)
H50.06030.4418−0.16850.017*
C60.1217 (6)0.2981 (5)0.0121 (5)0.0181 (9)
H60.12040.24110.07560.022*
C70.4537 (6)0.5846 (5)0.1682 (4)0.0161 (8)
H70.44450.64070.10560.019*
C80.5824 (6)0.6447 (5)0.2847 (4)0.0139 (8)
C90.6240 (6)0.5568 (5)0.3700 (4)0.0145 (8)
H90.55790.45250.34490.017*
C100.8239 (6)0.7563 (5)0.5078 (5)0.0184 (9)
H100.91000.80320.58860.022*
C110.7911 (6)0.8506 (5)0.4285 (5)0.0190 (9)
H110.85630.95520.45750.023*
C120.6709 (6)0.7940 (5)0.3151 (5)0.0167 (8)
H120.64890.85370.25970.020*
C130.3873 (7)0.7910 (5)−0.1196 (5)0.0212 (9)
H13A0.44570.7119−0.15240.032*
H13B0.31470.7713−0.04410.032*
H13C0.47950.8896−0.08410.032*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag0.0180 (2)0.0230 (2)0.0156 (2)0.00637 (14)−0.00283 (13)0.00638 (14)
S10.0159 (5)0.0166 (5)0.0142 (5)0.0019 (4)−0.0044 (4)0.0028 (4)
O10.0236 (18)0.0202 (17)0.037 (2)0.0029 (14)−0.0091 (15)0.0003 (15)
O20.032 (2)0.0171 (16)0.0312 (19)0.0081 (14)−0.0112 (15)0.0028 (14)
O30.0238 (19)0.051 (2)0.0164 (17)−0.0002 (17)−0.0040 (14)0.0090 (16)
N10.0149 (17)0.0212 (18)0.0095 (16)0.0083 (14)−0.0035 (13)0.0015 (14)
N20.0123 (17)0.0208 (18)0.0114 (17)0.0025 (14)−0.0059 (13)−0.0007 (14)
N30.0126 (17)0.0221 (19)0.0083 (16)0.0043 (15)−0.0057 (13)−0.0013 (14)
N40.0144 (17)0.0176 (17)0.0132 (17)0.0060 (14)−0.0035 (13)0.0029 (14)
C10.0118 (19)0.0142 (19)0.0130 (19)0.0001 (15)−0.0016 (15)−0.0002 (15)
C20.018 (2)0.0135 (19)0.016 (2)0.0016 (16)−0.0020 (16)−0.0033 (16)
C30.018 (2)0.015 (2)0.014 (2)0.0010 (16)−0.0016 (16)0.0027 (16)
C40.0111 (19)0.017 (2)0.0113 (18)0.0037 (16)−0.0026 (15)−0.0005 (15)
C50.0115 (19)0.0123 (18)0.0127 (19)0.0036 (15)−0.0013 (15)−0.0039 (15)
C60.019 (2)0.022 (2)0.0111 (19)0.0080 (18)−0.0049 (16)−0.0005 (16)
C70.013 (2)0.020 (2)0.0126 (19)0.0042 (17)−0.0022 (16)0.0028 (16)
C80.016 (2)0.0132 (19)0.0104 (18)0.0056 (16)0.0000 (15)0.0000 (15)
C90.0125 (19)0.018 (2)0.0112 (18)0.0057 (16)−0.0047 (15)0.0003 (15)
C100.015 (2)0.021 (2)0.015 (2)0.0039 (17)−0.0036 (16)−0.0008 (16)
C110.016 (2)0.018 (2)0.017 (2)0.0035 (17)−0.0036 (17)−0.0013 (17)
C120.015 (2)0.016 (2)0.016 (2)0.0050 (16)−0.0023 (16)0.0009 (16)
C130.025 (2)0.026 (2)0.012 (2)0.0108 (19)−0.0032 (17)0.0025 (17)
Geometric parameters (Å, °) top
Ag—N12.247 (4)C3—C41.350 (6)
Ag—O12.508 (4)C3—H30.9500
Ag—N4i2.227 (4)C4—C61.421 (6)
Ag—Agii3.1402 (8)C4—C51.447 (6)
S1—O21.409 (4)C5—H50.9500
S1—O11.425 (4)C6—H60.9500
S1—O31.468 (4)C7—C81.391 (6)
S1—C131.761 (4)C7—H70.9500
N1—C51.303 (5)C8—C121.353 (6)
N1—C11.306 (6)C8—C91.452 (6)
N2—C61.258 (6)C9—H90.9500
N2—N31.388 (5)C10—C111.435 (6)
N3—C71.247 (6)C10—H100.9500
N4—C91.294 (6)C11—C121.331 (6)
N4—C101.310 (6)C11—H110.9500
N4—Agiii2.227 (4)C12—H120.9500
C1—C21.437 (6)C13—H13A0.9800
C1—H10.9500C13—H13B0.9800
C2—C31.339 (6)C13—H13C0.9800
C2—H20.9500
N4i—Ag—N1169.11 (14)C6—C4—C5122.4 (4)
N4i—Ag—O197.46 (13)N1—C5—C4124.0 (4)
N1—Ag—O188.96 (13)N1—C5—H5118.0
N4i—Ag—Agii82.12 (10)C4—C5—H5118.0
N1—Ag—Agii108.76 (10)N2—C6—C4115.2 (4)
O1—Ag—Agii58.95 (10)N2—C6—H6122.4
O2—S1—O1110.4 (2)C4—C6—H6122.4
O2—S1—O3111.1 (3)N3—C7—C8117.4 (4)
O1—S1—O3116.9 (2)N3—C7—H7121.3
O2—S1—C13110.8 (2)C8—C7—H7121.3
O1—S1—C13100.8 (2)C12—C8—C7115.5 (4)
O3—S1—C13106.1 (2)C12—C8—C9120.8 (4)
S1—O1—Ag148.7 (2)C7—C8—C9123.8 (4)
C5—N1—C1113.6 (4)N4—C9—C8124.5 (4)
C5—N1—Ag122.4 (3)N4—C9—H9117.7
C1—N1—Ag123.8 (3)C8—C9—H9117.7
C6—N2—N3107.0 (4)N4—C10—C11125.3 (4)
C7—N3—N2105.2 (4)N4—C10—H10117.4
C9—N4—C10113.5 (4)C11—C10—H10117.4
C9—N4—Agiii121.2 (3)C12—C11—C10121.1 (4)
C10—N4—Agiii124.8 (3)C12—C11—H11119.4
N1—C1—C2125.2 (4)C10—C11—H11119.4
N1—C1—H1117.4C11—C12—C8114.8 (4)
C2—C1—H1117.4C11—C12—H12122.6
C3—C2—C1121.6 (4)C8—C12—H12122.6
C3—C2—H2119.2S1—C13—H13A109.5
C1—C2—H2119.2S1—C13—H13B109.5
C2—C3—C4113.7 (4)H13A—C13—H13B109.5
C2—C3—H3123.2S1—C13—H13C109.5
C4—C3—H3123.2H13A—C13—H13C109.5
C3—C4—C6115.7 (4)H13B—C13—H13C109.5
C3—C4—C5122.0 (4)
O2—S1—O1—Ag52.9 (5)Ag—N1—C5—C4174.0 (3)
O3—S1—O1—Ag−75.4 (5)C3—C4—C5—N10.3 (7)
C13—S1—O1—Ag170.1 (5)C6—C4—C5—N1−179.4 (4)
N4i—Ag—O1—S1−3.4 (5)N3—N2—C6—C4−179.5 (4)
N1—Ag—O1—S1−174.6 (5)C3—C4—C6—N2171.5 (4)
Agii—Ag—O1—S172.7 (5)C5—C4—C6—N2−8.8 (6)
N4i—Ag—N1—C5−113.0 (7)N2—N3—C7—C8179.4 (4)
O1—Ag—N1—C513.4 (3)N3—C7—C8—C12−169.5 (4)
Agii—Ag—N1—C569.9 (3)N3—C7—C8—C911.0 (7)
N4i—Ag—N1—C161.4 (8)C10—N4—C9—C82.6 (6)
O1—Ag—N1—C1−172.2 (4)Agiii—N4—C9—C8−169.7 (3)
Agii—Ag—N1—C1−115.7 (3)C12—C8—C9—N4−0.3 (7)
C6—N2—N3—C7−174.7 (4)C7—C8—C9—N4179.2 (4)
C5—N1—C1—C21.1 (6)C9—N4—C10—C11−2.9 (7)
Ag—N1—C1—C2−173.7 (3)Agiii—N4—C10—C11169.1 (3)
N1—C1—C2—C3−0.6 (7)N4—C10—C11—C120.9 (8)
C1—C2—C3—C4−0.2 (7)C10—C11—C12—C81.5 (7)
C2—C3—C4—C6−180.0 (4)C7—C8—C12—C11178.7 (4)
C2—C3—C4—C50.3 (6)C9—C8—C12—C11−1.8 (6)
C1—N1—C5—C4−0.9 (6)
Symmetry codes: (i) x−1, y, z−1; (ii) −x, −y+1, −z−1; (iii) x+1, y, z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C12—H12···O2iv0.952.563.283 (6)133
C2—H2···O3v0.952.473.268 (7)142
C13—H13A···N3vi0.982.563.500 (7)160
Symmetry codes: (iv) −x+1, −y+2, −z; (v) x−1, y−1, z; (vi) −x+1, −y+1, −z.
Table 1
Selected geometric parameters (Å, °) top
Ag—N12.247 (4)Ag—Agii3.1402 (8)
Ag—N4i2.227 (4)
N4i—Ag—N1169.11 (14)
Symmetry codes: (i) x−1, y, z−1; (ii) −x, −y+1, −z−1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C12—H12···O2iii0.952.563.283 (6)133
C2—H2···O3iv0.952.473.268 (7)142
C13—H13A···N3v0.982.563.500 (7)160
Symmetry codes: (iii) −x+1, −y+2, −z; (iv) x−1, y−1, z; (v) −x+1, −y+1, −z.
references
References top

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Broker, G. A. & Tiekink, E. R. T. (2007a). Acta Cryst. E63, m2368–?.

Broker, G. A. & Tiekink, E. R. T. (2007b). Acta Cryst. E63, m2436–?.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.

Kennedy, A. R., Brown, K. G., Graham, D., Kirkhouse, J. B., Kittner, M., Major, C., McHugh, C. J., Murdoch, P. & Smith, W. E. (2005). New J. Chem. 29, 826–832.

Rigaku (2005). CrystalClear. Rigaku, The Woodlands, Texas, USA.

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