Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042419/hb2526sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042419/hb2526Isup2.hkl |
CCDC reference: 663556
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.
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.
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).
For related polymeric silver salts containing the 3-pyridinealdazine ligand, see: Kennedy et al. (2005). For related literature, see: Broker & Tiekink (2007a, 2007b).
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.
[Ag(C12H10N4)](CH3SO3) | Z = 2 |
Mr = 413.21 | F(000) = 412 |
Triclinic, P1 | Dx = 1.994 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71070 Å |
a = 7.7818 (13) Å | Cell parameters from 6258 reflections |
b = 9.6799 (16) Å | θ = 2.8–29.7° |
c = 9.9742 (15) Å | µ = 1.64 mm−1 |
α = 106.50 (1)° | T = 98 K |
β = 91.12 (1)° | Rod, yellow |
γ = 106.50 (1)° | 0.15 × 0.05 × 0.03 mm |
V = 686.63 (19) Å3 |
Rigaku AFC12κ Saturn724 diffractometer | 2793 independent reflections |
Radiation source: fine-focus sealed tube | 2686 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω scans | θmax = 26.5°, θmin = 2.6° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −9→8 |
Tmin = 0.641, Tmax = 1.000 | k = −10→12 |
4287 measured reflections | l = −12→12 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0581P)2 + 3.8177P] where P = (Fo2 + 2Fc2)/3 |
2793 reflections | (Δ/σ)max < 0.001 |
199 parameters | Δρmax = 1.33 e Å−3 |
0 restraints | Δρmin = −1.74 e Å−3 |
[Ag(C12H10N4)](CH3SO3) | γ = 106.50 (1)° |
Mr = 413.21 | V = 686.63 (19) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.7818 (13) Å | Mo Kα radiation |
b = 9.6799 (16) Å | µ = 1.64 mm−1 |
c = 9.9742 (15) Å | T = 98 K |
α = 106.50 (1)° | 0.15 × 0.05 × 0.03 mm |
β = 91.12 (1)° |
Rigaku AFC12κ Saturn724 diffractometer | 2793 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2686 reflections with I > 2σ(I) |
Tmin = 0.641, Tmax = 1.000 | Rint = 0.030 |
4287 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.09 | Δρmax = 1.33 e Å−3 |
2793 reflections | Δρmin = −1.74 e Å−3 |
199 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ag | −0.17114 (4) | 0.45886 (4) | −0.42132 (3) | 0.01878 (14) | |
S1 | 0.24710 (15) | 0.79114 (12) | −0.26031 (11) | 0.0167 (2) | |
O1 | 0.1198 (5) | 0.6446 (4) | −0.2912 (4) | 0.0296 (8) | |
O2 | 0.1607 (5) | 0.9035 (4) | −0.2162 (4) | 0.0279 (8) | |
O3 | 0.3649 (5) | 0.8196 (5) | −0.3689 (4) | 0.0334 (9) | |
N1 | −0.1379 (5) | 0.2995 (4) | −0.3042 (4) | 0.0153 (7) | |
N2 | 0.2373 (5) | 0.4241 (4) | 0.0284 (4) | 0.0167 (7) | |
N3 | 0.3507 (5) | 0.4542 (4) | 0.1490 (4) | 0.0159 (7) | |
N4 | 0.7448 (5) | 0.6106 (4) | 0.4777 (4) | 0.0153 (7) | |
C1 | −0.2417 (6) | 0.1603 (5) | −0.3322 (4) | 0.0148 (8) | |
H1 | −0.3284 | 0.1221 | −0.4125 | 0.018* | |
C2 | −0.2351 (6) | 0.0603 (5) | −0.2512 (5) | 0.0182 (9) | |
H2 | −0.3170 | −0.0391 | −0.2792 | 0.022* | |
C3 | −0.1162 (6) | 0.1037 (5) | −0.1371 (5) | 0.0169 (8) | |
H3 | −0.1094 | 0.0398 | −0.0817 | 0.020* | |
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) | |
H5 | 0.0603 | 0.4418 | −0.1685 | 0.017* | |
C6 | 0.1217 (6) | 0.2981 (5) | 0.0121 (5) | 0.0181 (9) | |
H6 | 0.1204 | 0.2411 | 0.0756 | 0.022* | |
C7 | 0.4537 (6) | 0.5846 (5) | 0.1682 (4) | 0.0161 (8) | |
H7 | 0.4445 | 0.6407 | 0.1056 | 0.019* | |
C8 | 0.5824 (6) | 0.6447 (5) | 0.2847 (4) | 0.0139 (8) | |
C9 | 0.6240 (6) | 0.5568 (5) | 0.3700 (4) | 0.0145 (8) | |
H9 | 0.5579 | 0.4525 | 0.3449 | 0.017* | |
C10 | 0.8239 (6) | 0.7563 (5) | 0.5078 (5) | 0.0184 (9) | |
H10 | 0.9100 | 0.8032 | 0.5886 | 0.022* | |
C11 | 0.7911 (6) | 0.8506 (5) | 0.4285 (5) | 0.0190 (9) | |
H11 | 0.8563 | 0.9552 | 0.4575 | 0.023* | |
C12 | 0.6709 (6) | 0.7940 (5) | 0.3151 (5) | 0.0167 (8) | |
H12 | 0.6489 | 0.8537 | 0.2597 | 0.020* | |
C13 | 0.3873 (7) | 0.7910 (5) | −0.1196 (5) | 0.0212 (9) | |
H13A | 0.4457 | 0.7119 | −0.1524 | 0.032* | |
H13B | 0.3147 | 0.7713 | −0.0441 | 0.032* | |
H13C | 0.4795 | 0.8896 | −0.0841 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag | 0.0180 (2) | 0.0230 (2) | 0.0156 (2) | 0.00637 (14) | −0.00283 (13) | 0.00638 (14) |
S1 | 0.0159 (5) | 0.0166 (5) | 0.0142 (5) | 0.0019 (4) | −0.0044 (4) | 0.0028 (4) |
O1 | 0.0236 (18) | 0.0202 (17) | 0.037 (2) | 0.0029 (14) | −0.0091 (15) | 0.0003 (15) |
O2 | 0.032 (2) | 0.0171 (16) | 0.0312 (19) | 0.0081 (14) | −0.0112 (15) | 0.0028 (14) |
O3 | 0.0238 (19) | 0.051 (2) | 0.0164 (17) | −0.0002 (17) | −0.0040 (14) | 0.0090 (16) |
N1 | 0.0149 (17) | 0.0212 (18) | 0.0095 (16) | 0.0083 (14) | −0.0035 (13) | 0.0015 (14) |
N2 | 0.0123 (17) | 0.0208 (18) | 0.0114 (17) | 0.0025 (14) | −0.0059 (13) | −0.0007 (14) |
N3 | 0.0126 (17) | 0.0221 (19) | 0.0083 (16) | 0.0043 (15) | −0.0057 (13) | −0.0013 (14) |
N4 | 0.0144 (17) | 0.0176 (17) | 0.0132 (17) | 0.0060 (14) | −0.0035 (13) | 0.0029 (14) |
C1 | 0.0118 (19) | 0.0142 (19) | 0.0130 (19) | 0.0001 (15) | −0.0016 (15) | −0.0002 (15) |
C2 | 0.018 (2) | 0.0135 (19) | 0.016 (2) | 0.0016 (16) | −0.0020 (16) | −0.0033 (16) |
C3 | 0.018 (2) | 0.015 (2) | 0.014 (2) | 0.0010 (16) | −0.0016 (16) | 0.0027 (16) |
C4 | 0.0111 (19) | 0.017 (2) | 0.0113 (18) | 0.0037 (16) | −0.0026 (15) | −0.0005 (15) |
C5 | 0.0115 (19) | 0.0123 (18) | 0.0127 (19) | 0.0036 (15) | −0.0013 (15) | −0.0039 (15) |
C6 | 0.019 (2) | 0.022 (2) | 0.0111 (19) | 0.0080 (18) | −0.0049 (16) | −0.0005 (16) |
C7 | 0.013 (2) | 0.020 (2) | 0.0126 (19) | 0.0042 (17) | −0.0022 (16) | 0.0028 (16) |
C8 | 0.016 (2) | 0.0132 (19) | 0.0104 (18) | 0.0056 (16) | 0.0000 (15) | 0.0000 (15) |
C9 | 0.0125 (19) | 0.018 (2) | 0.0112 (18) | 0.0057 (16) | −0.0047 (15) | 0.0003 (15) |
C10 | 0.015 (2) | 0.021 (2) | 0.015 (2) | 0.0039 (17) | −0.0036 (16) | −0.0008 (16) |
C11 | 0.016 (2) | 0.018 (2) | 0.017 (2) | 0.0035 (17) | −0.0036 (17) | −0.0013 (17) |
C12 | 0.015 (2) | 0.016 (2) | 0.016 (2) | 0.0050 (16) | −0.0023 (16) | 0.0009 (16) |
C13 | 0.025 (2) | 0.026 (2) | 0.012 (2) | 0.0108 (19) | −0.0032 (17) | 0.0025 (17) |
Ag—N1 | 2.247 (4) | C3—C4 | 1.350 (6) |
Ag—O1 | 2.508 (4) | C3—H3 | 0.9500 |
Ag—N4i | 2.227 (4) | C4—C6 | 1.421 (6) |
Ag—Agii | 3.1402 (8) | C4—C5 | 1.447 (6) |
S1—O2 | 1.409 (4) | C5—H5 | 0.9500 |
S1—O1 | 1.425 (4) | C6—H6 | 0.9500 |
S1—O3 | 1.468 (4) | C7—C8 | 1.391 (6) |
S1—C13 | 1.761 (4) | C7—H7 | 0.9500 |
N1—C5 | 1.303 (5) | C8—C12 | 1.353 (6) |
N1—C1 | 1.306 (6) | C8—C9 | 1.452 (6) |
N2—C6 | 1.258 (6) | C9—H9 | 0.9500 |
N2—N3 | 1.388 (5) | C10—C11 | 1.435 (6) |
N3—C7 | 1.247 (6) | C10—H10 | 0.9500 |
N4—C9 | 1.294 (6) | C11—C12 | 1.331 (6) |
N4—C10 | 1.310 (6) | C11—H11 | 0.9500 |
N4—Agiii | 2.227 (4) | C12—H12 | 0.9500 |
C1—C2 | 1.437 (6) | C13—H13A | 0.9800 |
C1—H1 | 0.9500 | C13—H13B | 0.9800 |
C2—C3 | 1.339 (6) | C13—H13C | 0.9800 |
C2—H2 | 0.9500 | ||
N4i—Ag—N1 | 169.11 (14) | C6—C4—C5 | 122.4 (4) |
N4i—Ag—O1 | 97.46 (13) | N1—C5—C4 | 124.0 (4) |
N1—Ag—O1 | 88.96 (13) | N1—C5—H5 | 118.0 |
N4i—Ag—Agii | 82.12 (10) | C4—C5—H5 | 118.0 |
N1—Ag—Agii | 108.76 (10) | N2—C6—C4 | 115.2 (4) |
O1—Ag—Agii | 58.95 (10) | N2—C6—H6 | 122.4 |
O2—S1—O1 | 110.4 (2) | C4—C6—H6 | 122.4 |
O2—S1—O3 | 111.1 (3) | N3—C7—C8 | 117.4 (4) |
O1—S1—O3 | 116.9 (2) | N3—C7—H7 | 121.3 |
O2—S1—C13 | 110.8 (2) | C8—C7—H7 | 121.3 |
O1—S1—C13 | 100.8 (2) | C12—C8—C7 | 115.5 (4) |
O3—S1—C13 | 106.1 (2) | C12—C8—C9 | 120.8 (4) |
S1—O1—Ag | 148.7 (2) | C7—C8—C9 | 123.8 (4) |
C5—N1—C1 | 113.6 (4) | N4—C9—C8 | 124.5 (4) |
C5—N1—Ag | 122.4 (3) | N4—C9—H9 | 117.7 |
C1—N1—Ag | 123.8 (3) | C8—C9—H9 | 117.7 |
C6—N2—N3 | 107.0 (4) | N4—C10—C11 | 125.3 (4) |
C7—N3—N2 | 105.2 (4) | N4—C10—H10 | 117.4 |
C9—N4—C10 | 113.5 (4) | C11—C10—H10 | 117.4 |
C9—N4—Agiii | 121.2 (3) | C12—C11—C10 | 121.1 (4) |
C10—N4—Agiii | 124.8 (3) | C12—C11—H11 | 119.4 |
N1—C1—C2 | 125.2 (4) | C10—C11—H11 | 119.4 |
N1—C1—H1 | 117.4 | C11—C12—C8 | 114.8 (4) |
C2—C1—H1 | 117.4 | C11—C12—H12 | 122.6 |
C3—C2—C1 | 121.6 (4) | C8—C12—H12 | 122.6 |
C3—C2—H2 | 119.2 | S1—C13—H13A | 109.5 |
C1—C2—H2 | 119.2 | S1—C13—H13B | 109.5 |
C2—C3—C4 | 113.7 (4) | H13A—C13—H13B | 109.5 |
C2—C3—H3 | 123.2 | S1—C13—H13C | 109.5 |
C4—C3—H3 | 123.2 | H13A—C13—H13C | 109.5 |
C3—C4—C6 | 115.7 (4) | H13B—C13—H13C | 109.5 |
C3—C4—C5 | 122.0 (4) | ||
O2—S1—O1—Ag | 52.9 (5) | Ag—N1—C5—C4 | 174.0 (3) |
O3—S1—O1—Ag | −75.4 (5) | C3—C4—C5—N1 | 0.3 (7) |
C13—S1—O1—Ag | 170.1 (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—N2 | 171.5 (4) |
Agii—Ag—O1—S1 | 72.7 (5) | C5—C4—C6—N2 | −8.8 (6) |
N4i—Ag—N1—C5 | −113.0 (7) | N2—N3—C7—C8 | 179.4 (4) |
O1—Ag—N1—C5 | 13.4 (3) | N3—C7—C8—C12 | −169.5 (4) |
Agii—Ag—N1—C5 | 69.9 (3) | N3—C7—C8—C9 | 11.0 (7) |
N4i—Ag—N1—C1 | 61.4 (8) | C10—N4—C9—C8 | 2.6 (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—N4 | 179.2 (4) |
C5—N1—C1—C2 | 1.1 (6) | C9—N4—C10—C11 | −2.9 (7) |
Ag—N1—C1—C2 | −173.7 (3) | Agiii—N4—C10—C11 | 169.1 (3) |
N1—C1—C2—C3 | −0.6 (7) | N4—C10—C11—C12 | 0.9 (8) |
C1—C2—C3—C4 | −0.2 (7) | C10—C11—C12—C8 | 1.5 (7) |
C2—C3—C4—C6 | −180.0 (4) | C7—C8—C12—C11 | 178.7 (4) |
C2—C3—C4—C5 | 0.3 (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. |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···O2iv | 0.95 | 2.56 | 3.283 (6) | 133 |
C2—H2···O3v | 0.95 | 2.47 | 3.268 (7) | 142 |
C13—H13A···N3vi | 0.98 | 2.56 | 3.500 (7) | 160 |
Symmetry codes: (iv) −x+1, −y+2, −z; (v) x−1, y−1, z; (vi) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Ag(C12H10N4)](CH3SO3) |
Mr | 413.21 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 98 |
a, b, c (Å) | 7.7818 (13), 9.6799 (16), 9.9742 (15) |
α, β, γ (°) | 106.50 (1), 91.12 (1), 106.50 (1) |
V (Å3) | 686.63 (19) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.64 |
Crystal size (mm) | 0.15 × 0.05 × 0.03 |
Data collection | |
Diffractometer | Rigaku AFC12κ Saturn724 |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.641, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4287, 2793, 2686 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.115, 1.09 |
No. of reflections | 2793 |
No. of parameters | 199 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.33, −1.74 |
Computer programs: CrystalClear (Rigaku, 2005), CrystalClear, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006), SHELXL97.
Ag—N1 | 2.247 (4) | Ag—Agii | 3.1402 (8) |
Ag—N4i | 2.227 (4) | ||
N4i—Ag—N1 | 169.11 (14) |
Symmetry codes: (i) x−1, y, z−1; (ii) −x, −y+1, −z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···O2iii | 0.95 | 2.56 | 3.283 (6) | 133 |
C2—H2···O3iv | 0.95 | 2.47 | 3.268 (7) | 142 |
C13—H13A···N3v | 0.98 | 2.56 | 3.500 (7) | 160 |
Symmetry codes: (iii) −x+1, −y+2, −z; (iv) x−1, y−1, z; (v) −x+1, −y+1, −z. |
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).