Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108023585/ln3107sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108023585/ln3107Isup2.hkl |
CCDC reference: 703718
For related literature, see: Antonioli et al. (2006); Bourlier et al. (2007); Dong et al. (2004, 2005); Fernandez-Fernandez, Bastida, Macias, Perez-Lourido & Valencia (2006); Gao et al. (2004); Gonzalez et al. (2002); Iskander et al. (2001); de Souza et al. (2007); Niu et al. (2007); Qiu et al. (2006); Ren et al. (2004); Sumby & Hardie (2005); Tong et al. (1998); Yang et al. (2000).
A solution of AgClO4.H2O (0.023 g, 0.1 mmol) in methanol (10 ml) was carefully layered on a methanol/chloroform solution (5 ml/10 ml) of N'-(4-cyanobenzylidene)isonicotinohydrazide (0.025 g, 0.1 mmol) in a straight glass tube. About ten days later, colourless single crystals of (I) suitable for X-ray analysis were obtained (yield 43%). Elemental analysis calculated for C14H10AgClN4O5: C 36.75, H 2.20, N 12.24%; found: C 36.86, H 2.11, N 12.09%.
C-bound H atoms were placed in calculated positions and refined using a riding model [C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C)]. The N-bound H atom was first introduced in a calculated position, and then its position and displacement parameter were refined with the N—H bond distance restrained to 0.88 (2) Å. The final difference Fourier map had a highest peak at 0.94 Å from atom Ag1 and a deepest hole at 0.71 Å from atom Cl1, but was otherwise featureless.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); 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).
[Ag(C14H10N4O)]ClO4 | F(000) = 904 |
Mr = 457.58 | Dx = 1.902 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5265 reflections |
a = 8.5763 (5) Å | θ = 2.1–25.5° |
b = 13.4913 (8) Å | µ = 1.46 mm−1 |
c = 14.1944 (8) Å | T = 173 K |
β = 103.370 (1)° | Block, colourless |
V = 1597.86 (16) Å3 | 0.46 × 0.34 × 0.32 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 2979 independent reflections |
Radiation source: fine-focus sealed tube | 2637 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.012 |
ϕ and ω scans | θmax = 25.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.553, Tmax = 0.652 | k = −16→16 |
8730 measured reflections | l = −11→17 |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0363P)2 + 1.2063P] where P = (Fo2 + 2Fc2)/3 |
2979 reflections | (Δ/σ)max = 0.001 |
230 parameters | Δρmax = 0.52 e Å−3 |
1 restraint | Δρmin = −0.43 e Å−3 |
[Ag(C14H10N4O)]ClO4 | V = 1597.86 (16) Å3 |
Mr = 457.58 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.5763 (5) Å | µ = 1.46 mm−1 |
b = 13.4913 (8) Å | T = 173 K |
c = 14.1944 (8) Å | 0.46 × 0.34 × 0.32 mm |
β = 103.370 (1)° |
Siemens SMART CCD area-detector diffractometer | 2979 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2637 reflections with I > 2σ(I) |
Tmin = 0.553, Tmax = 0.652 | Rint = 0.012 |
8730 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 1 restraint |
wR(F2) = 0.069 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.52 e Å−3 |
2979 reflections | Δρmin = −0.43 e Å−3 |
230 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 | ||
Ag1 | 0.09040 (2) | 0.430137 (15) | 0.155600 (17) | 0.05295 (10) | |
N1 | −0.4511 (3) | 0.04633 (17) | 0.26960 (18) | 0.0495 (5) | |
N2 | 0.0150 (3) | 0.19362 (17) | 0.15448 (17) | 0.0464 (5) | |
N3 | 0.1302 (2) | 0.25249 (16) | 0.12916 (15) | 0.0417 (5) | |
N4 | 0.8197 (4) | 0.4510 (2) | −0.0608 (2) | 0.0739 (8) | |
O1 | −0.1160 (3) | 0.32412 (14) | 0.19687 (19) | 0.0686 (6) | |
Cl1 | 0.38179 (9) | 0.40439 (5) | 0.37770 (5) | 0.05339 (18) | |
O2 | 0.3786 (3) | 0.48549 (18) | 0.31283 (18) | 0.0751 (6) | |
O3 | 0.2896 (4) | 0.3265 (2) | 0.32594 (19) | 0.0926 (9) | |
O4 | 0.3203 (5) | 0.4352 (2) | 0.4560 (2) | 0.1238 (14) | |
O5 | 0.5457 (4) | 0.3734 (3) | 0.4074 (3) | 0.1160 (11) | |
C1 | −0.3712 (3) | 0.0163 (2) | 0.2042 (2) | 0.0534 (7) | |
H1 | −0.3945 | −0.0476 | 0.1765 | 0.064* | |
C2 | −0.2573 (3) | 0.07261 (18) | 0.1747 (2) | 0.0475 (6) | |
H2 | −0.2028 | 0.0475 | 0.1286 | 0.057* | |
C3 | −0.2238 (3) | 0.16610 (18) | 0.21319 (18) | 0.0398 (5) | |
C4 | −0.3106 (3) | 0.1995 (2) | 0.2781 (2) | 0.0499 (6) | |
H4 | −0.2943 | 0.2647 | 0.3040 | 0.060* | |
C5 | −0.4202 (3) | 0.1378 (2) | 0.3046 (2) | 0.0528 (7) | |
H5 | −0.4770 | 0.1614 | 0.3502 | 0.063* | |
C6 | −0.1037 (3) | 0.23479 (19) | 0.18746 (19) | 0.0429 (6) | |
C7 | 0.2366 (3) | 0.2056 (2) | 0.09730 (19) | 0.0455 (6) | |
H7 | 0.2303 | 0.1354 | 0.0924 | 0.055* | |
C8 | 0.3680 (3) | 0.25715 (19) | 0.06813 (18) | 0.0425 (6) | |
C9 | 0.4365 (3) | 0.2130 (2) | −0.0007 (2) | 0.0519 (7) | |
H9 | 0.4015 | 0.1492 | −0.0249 | 0.062* | |
C10 | 0.5553 (3) | 0.2610 (2) | −0.0344 (2) | 0.0546 (7) | |
H10 | 0.6003 | 0.2311 | −0.0826 | 0.066* | |
C11 | 0.6079 (3) | 0.3528 (2) | 0.0027 (2) | 0.0495 (6) | |
C12 | 0.5461 (3) | 0.3959 (2) | 0.0758 (2) | 0.0510 (6) | |
H12 | 0.5861 | 0.4577 | 0.1033 | 0.061* | |
C13 | 0.4263 (3) | 0.3477 (2) | 0.1075 (2) | 0.0467 (6) | |
H13 | 0.3831 | 0.3767 | 0.1569 | 0.056* | |
C14 | 0.7286 (4) | 0.4057 (2) | −0.0326 (2) | 0.0583 (8) | |
H14 | 0.023 (4) | 0.1309 (14) | 0.153 (2) | 0.056 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.04980 (14) | 0.04061 (13) | 0.08027 (18) | −0.00091 (8) | 0.03922 (12) | 0.00175 (10) |
N1 | 0.0521 (13) | 0.0422 (12) | 0.0640 (14) | −0.0043 (10) | 0.0337 (11) | −0.0017 (10) |
N2 | 0.0449 (12) | 0.0378 (12) | 0.0651 (14) | −0.0058 (10) | 0.0307 (10) | −0.0029 (10) |
N3 | 0.0385 (10) | 0.0433 (12) | 0.0487 (12) | −0.0072 (9) | 0.0212 (9) | −0.0005 (9) |
N4 | 0.0662 (17) | 0.0729 (18) | 0.099 (2) | −0.0017 (14) | 0.0531 (17) | 0.0148 (16) |
O1 | 0.0593 (12) | 0.0396 (11) | 0.1228 (19) | −0.0068 (9) | 0.0537 (13) | −0.0067 (11) |
Cl1 | 0.0681 (4) | 0.0484 (4) | 0.0477 (4) | −0.0109 (3) | 0.0217 (3) | −0.0070 (3) |
O2 | 0.0927 (17) | 0.0563 (14) | 0.0821 (15) | −0.0009 (12) | 0.0318 (13) | 0.0088 (12) |
O3 | 0.117 (2) | 0.0918 (19) | 0.0802 (17) | −0.0578 (17) | 0.0459 (15) | −0.0323 (14) |
O4 | 0.189 (4) | 0.121 (3) | 0.090 (2) | −0.051 (2) | 0.092 (2) | −0.0432 (18) |
O5 | 0.098 (2) | 0.102 (2) | 0.127 (3) | 0.0291 (18) | −0.0162 (19) | −0.001 (2) |
C1 | 0.0660 (17) | 0.0392 (14) | 0.0652 (18) | −0.0110 (12) | 0.0361 (14) | −0.0089 (13) |
C2 | 0.0543 (15) | 0.0424 (14) | 0.0556 (16) | −0.0035 (11) | 0.0325 (13) | −0.0055 (12) |
C3 | 0.0361 (12) | 0.0381 (13) | 0.0491 (14) | 0.0000 (10) | 0.0178 (10) | 0.0012 (10) |
C4 | 0.0521 (15) | 0.0398 (13) | 0.0664 (17) | −0.0061 (12) | 0.0311 (13) | −0.0097 (12) |
C5 | 0.0541 (15) | 0.0455 (15) | 0.0705 (18) | −0.0015 (12) | 0.0383 (14) | −0.0069 (13) |
C6 | 0.0389 (12) | 0.0400 (13) | 0.0547 (15) | −0.0033 (10) | 0.0213 (11) | −0.0006 (11) |
C7 | 0.0454 (14) | 0.0475 (14) | 0.0490 (14) | −0.0050 (11) | 0.0218 (11) | −0.0026 (12) |
C8 | 0.0381 (12) | 0.0480 (14) | 0.0464 (14) | 0.0029 (11) | 0.0200 (11) | 0.0038 (11) |
C9 | 0.0503 (15) | 0.0517 (16) | 0.0597 (17) | −0.0015 (12) | 0.0253 (13) | −0.0061 (13) |
C10 | 0.0506 (15) | 0.0673 (19) | 0.0558 (17) | 0.0066 (14) | 0.0323 (13) | −0.0013 (14) |
C11 | 0.0365 (13) | 0.0587 (16) | 0.0600 (16) | 0.0043 (12) | 0.0252 (12) | 0.0129 (13) |
C12 | 0.0453 (14) | 0.0501 (15) | 0.0636 (17) | −0.0042 (12) | 0.0250 (13) | −0.0027 (13) |
C13 | 0.0437 (14) | 0.0497 (15) | 0.0540 (15) | −0.0001 (11) | 0.0265 (12) | −0.0037 (12) |
C14 | 0.0493 (16) | 0.0620 (17) | 0.073 (2) | 0.0083 (14) | 0.0340 (15) | 0.0144 (15) |
Ag1—N4i | 2.336 (3) | C2—C3 | 1.378 (3) |
Ag1—N1ii | 2.366 (2) | C2—H2 | 0.9500 |
Ag1—O1 | 2.4501 (19) | C3—C4 | 1.387 (4) |
Ag1—N3 | 2.462 (2) | C3—C6 | 1.492 (3) |
N1—C5 | 1.334 (3) | C4—C5 | 1.372 (4) |
N1—C1 | 1.337 (3) | C4—H4 | 0.9500 |
N1—Ag1iii | 2.366 (2) | C5—H5 | 0.9500 |
N2—C6 | 1.336 (3) | C7—C8 | 1.464 (3) |
N2—N3 | 1.378 (3) | C7—H7 | 0.9500 |
N2—H14 | 0.850 (18) | C8—C9 | 1.385 (4) |
N3—C7 | 1.276 (3) | C8—C13 | 1.388 (4) |
N4—C14 | 1.135 (4) | C9—C10 | 1.383 (4) |
N4—Ag1i | 2.336 (3) | C9—H9 | 0.9500 |
O1—C6 | 1.220 (3) | C10—C11 | 1.380 (4) |
Cl1—O4 | 1.399 (3) | C10—H10 | 0.9500 |
Cl1—O3 | 1.414 (2) | C11—C12 | 1.397 (4) |
Cl1—O2 | 1.426 (2) | C11—C14 | 1.440 (4) |
Cl1—O5 | 1.433 (3) | C12—C13 | 1.376 (4) |
C1—C2 | 1.377 (4) | C12—H12 | 0.9500 |
C1—H1 | 0.9500 | C13—H13 | 0.9500 |
N4i—Ag1—N1ii | 94.11 (10) | C5—C4—C3 | 119.5 (3) |
N4i—Ag1—O1 | 153.07 (10) | C5—C4—H4 | 120.3 |
N1ii—Ag1—O1 | 79.15 (7) | C3—C4—H4 | 120.3 |
N4i—Ag1—N3 | 120.32 (9) | N1—C5—C4 | 123.3 (2) |
N1ii—Ag1—N3 | 144.64 (7) | N1—C5—H5 | 118.3 |
O1—Ag1—N3 | 66.51 (6) | C4—C5—H5 | 118.3 |
C5—N1—C1 | 116.7 (2) | O1—C6—N2 | 122.8 (2) |
C5—N1—Ag1iii | 121.55 (18) | O1—C6—C3 | 120.3 (2) |
C1—N1—Ag1iii | 120.25 (18) | N2—C6—C3 | 116.9 (2) |
C6—N2—N3 | 120.1 (2) | N3—C7—C8 | 121.7 (2) |
C6—N2—H14 | 120 (2) | N3—C7—H7 | 119.2 |
N3—N2—H14 | 120 (2) | C8—C7—H7 | 119.2 |
C7—N3—N2 | 114.9 (2) | C9—C8—C13 | 119.4 (2) |
C7—N3—Ag1 | 132.26 (17) | C9—C8—C7 | 118.4 (2) |
N2—N3—Ag1 | 112.85 (15) | C13—C8—C7 | 122.3 (2) |
C14—N4—Ag1i | 156.7 (3) | C10—C9—C8 | 120.6 (3) |
C6—O1—Ag1 | 117.70 (16) | C10—C9—H9 | 119.7 |
O4—Cl1—O3 | 111.40 (18) | C8—C9—H9 | 119.7 |
O4—Cl1—O2 | 109.32 (19) | C11—C10—C9 | 119.3 (3) |
O3—Cl1—O2 | 108.05 (17) | C11—C10—H10 | 120.3 |
O4—Cl1—O5 | 112.2 (2) | C9—C10—H10 | 120.3 |
O3—Cl1—O5 | 109.16 (19) | C10—C11—C12 | 120.7 (2) |
O2—Cl1—O5 | 106.55 (19) | C10—C11—C14 | 120.7 (3) |
N1—C1—C2 | 123.9 (2) | C12—C11—C14 | 118.6 (3) |
N1—C1—H1 | 118.1 | C13—C12—C11 | 119.1 (3) |
C2—C1—H1 | 118.1 | C13—C12—H12 | 120.5 |
C1—C2—C3 | 118.8 (2) | C11—C12—H12 | 120.5 |
C1—C2—H2 | 120.6 | C12—C13—C8 | 120.7 (2) |
C3—C2—H2 | 120.6 | C12—C13—H13 | 119.6 |
C2—C3—C4 | 117.8 (2) | C8—C13—H13 | 119.6 |
C2—C3—C6 | 124.3 (2) | N4—C14—C11 | 177.1 (3) |
C4—C3—C6 | 117.9 (2) | ||
C6—N2—N3—C7 | −179.0 (2) | Ag1—O1—C6—C3 | 178.82 (18) |
C6—N2—N3—Ag1 | 1.3 (3) | N3—N2—C6—O1 | −0.2 (4) |
N4i—Ag1—N3—C7 | 28.5 (3) | N3—N2—C6—C3 | 179.9 (2) |
N1ii—Ag1—N3—C7 | −166.1 (2) | C2—C3—C6—O1 | 155.3 (3) |
O1—Ag1—N3—C7 | 179.2 (3) | C4—C3—C6—O1 | −22.8 (4) |
N4i—Ag1—N3—N2 | −151.90 (17) | C2—C3—C6—N2 | −24.8 (4) |
N1ii—Ag1—N3—N2 | 13.5 (2) | C4—C3—C6—N2 | 157.1 (3) |
O1—Ag1—N3—N2 | −1.21 (16) | N2—N3—C7—C8 | −179.4 (2) |
N4i—Ag1—O1—C6 | 112.3 (3) | Ag1—N3—C7—C8 | 0.1 (4) |
N1ii—Ag1—O1—C6 | −170.2 (3) | N3—C7—C8—C9 | −153.1 (3) |
N3—Ag1—O1—C6 | 1.2 (2) | N3—C7—C8—C13 | 27.4 (4) |
C5—N1—C1—C2 | 2.4 (5) | C13—C8—C9—C10 | −3.9 (4) |
Ag1iii—N1—C1—C2 | −163.7 (2) | C7—C8—C9—C10 | 176.6 (3) |
N1—C1—C2—C3 | −0.9 (5) | C8—C9—C10—C11 | 1.4 (4) |
C1—C2—C3—C4 | −1.7 (4) | C9—C10—C11—C12 | 2.0 (4) |
C1—C2—C3—C6 | −179.9 (3) | C9—C10—C11—C14 | −178.5 (3) |
C2—C3—C4—C5 | 2.8 (4) | C10—C11—C12—C13 | −2.9 (4) |
C6—C3—C4—C5 | −179.0 (3) | C14—C11—C12—C13 | 177.6 (3) |
C1—N1—C5—C4 | −1.3 (5) | C11—C12—C13—C8 | 0.4 (4) |
Ag1iii—N1—C5—C4 | 164.7 (2) | C9—C8—C13—C12 | 2.9 (4) |
C3—C4—C5—N1 | −1.3 (5) | C7—C8—C13—C12 | −177.6 (3) |
Ag1—O1—C6—N2 | −1.1 (4) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x−1/2, y+1/2, −z+1/2; (iii) −x−1/2, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H14···O2iv | 0.85 (2) | 2.15 (2) | 2.956 (3) | 159 (3) |
Symmetry code: (iv) −x+1/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ag(C14H10N4O)]ClO4 |
Mr | 457.58 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 8.5763 (5), 13.4913 (8), 14.1944 (8) |
β (°) | 103.370 (1) |
V (Å3) | 1597.86 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.46 |
Crystal size (mm) | 0.46 × 0.34 × 0.32 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.553, 0.652 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8730, 2979, 2637 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.069, 1.00 |
No. of reflections | 2979 |
No. of parameters | 230 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.52, −0.43 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Ag1—N4i | 2.336 (3) | Ag1—O1 | 2.4501 (19) |
Ag1—N1ii | 2.366 (2) | Ag1—N3 | 2.462 (2) |
N4i—Ag1—N1ii | 94.11 (10) | N4i—Ag1—N3 | 120.32 (9) |
N4i—Ag1—O1 | 153.07 (10) | N1ii—Ag1—N3 | 144.64 (7) |
N1ii—Ag1—O1 | 79.15 (7) | O1—Ag1—N3 | 66.51 (6) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x−1/2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H14···O2iii | 0.850 (18) | 2.15 (2) | 2.956 (3) | 159 (3) |
Symmetry code: (iii) −x+1/2, y−1/2, −z+1/2. |
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Silver coordination polymers have been studied widely not only for their utility in special functional materials, but also for their fascinating structures derived from variable coordination numbers (from 2 to 6) of Ag atoms and different conformations around silver metal centres (Sumby & Hardie, 2005; Dong et al., 2004). Multiple pyridyl, carbonitrile or pyridyl carbonitrile ligands are good bridging organic ligands in coordination interactions with Ag atoms (Antonioli et al., 2006; Bourlier et al., 2007).
Carbonitrile and pyridyl N atoms in the same organic ligand possess different coordinating properties. Taking advantage of these differences, chemists can design and construct novel silver metal–organic frameworks (Fernandez-Fernandez et al., 2006; Niu et al., 2007; Gonzalez et al., 2002). On the other hand, hydrazone groups in some organic ligands have been widely used as five-atom-ring chelates with some transition metal atoms such as Cu, Co and Zn (Iskander et al., 2001; Qiu et al., 2006; Gao et al., 2004). This group should coordinate in a bidentate fashion to Ag atoms. However, there are no reports in the literature concerning complexes derived from these components. We report here the structure of a two-dimensional silver coordination polymer, (I), of the bridging ligand N'-(4-cyanobenzylidene)isonicotinohydrazide, which contains carbonitrile, pyridyl and hydrazone groups. The variety of potential coordinating atoms in this ligand allows it to be used as a µ2- or µ3-bridging or a monodentate ligand.
In (I), the central silver ion is coordinated by one O atom and one N atom (O1 and N3) from the hydrazone chain and the pyridyl and carbonitrile N atoms of two other ligands [N1ii and N4i; symmetry codes: (i) -x + 1, -y + 1, -z; (ii) -x - 1/2, y + 1/2, -z + 1/2; Fig. 1]. Hydrazone atoms O1 and N3 are coordinated to one silver ion in a bidentate coordinating mode to form a planar five-membered chelate ring (Ag1/N3/N2/C6/O1) in which the maximum deviation from the plane is 0.010 (3) Å for atom O1. The coordination geometry about atom Ag1 is distorted square planar, with the distortion arising primarily from the bite angle imposed by the chelating hydrazone group. The length of the Ag—N bond involving the hydrazone N atom is about 0.1 Å longer than those involving the pyridyl and carbonitrile N atoms (Table 1). As is to be expected from the bite angle formed by the coordination of the hydrazone group, the geometry of this part of the ligand in (I) differs slightly from that of the free ligand (de Souza et al., 2007).
In (I), the N'-(4-cyanobenzylidene)isonicotinohydrazide ligand (L) acts as a µ3-bridging ligand. Two ligands each bridge two Ag atoms through one carbonitrile N atom in a monodentate mode, and the hydrazone N and O atoms in a bidentate mode, to form a small centrosymmetric (2 + 2)-Ag2L2 ring. The Ag···Ag separation in one ring is 9.316 (3) Å. Four of these rings are linked to each other by the pyridyl atom N1, coordinating to Ag atoms in adjacent small rings to produce a large rectangular grid with Ag atoms at the corners of the rectangle. The large grid contains six Ag atoms (Fig. 2). Adjacent Ag atoms along the long side of the rectangle are bridged by the entire length of a ligand via the pyridyl and carbonitrile N atoms to give an Ag···Ag separation of 18.237 (3) Å. The short side of the rectangle involves two Ag atoms bridged via the bidentate hydrazone O1 and N3 atoms and the monodentate pyridyl atom N1 to give an Ag···Ag separation of 9.696 (3) Å. Two ClO4- counter-anions are located in the centrosymmetric nano-sized grid and interact with the rim of the rectangular grid by N—H···O hydrogen bonds, which involve the amine group of the ligand, N2, and atom O2 of a counter-anion (Table 2). As there is an Ag atom in the middle of each long side of the rectangular grid, and this Ag atom is also a corner of an adjacent rectangle, a brickwork lattice of two-dimensional layers is formed (Fig. 3). The layers lie approximately parallel to the (103) plane.
It is noteworthy that parallel two-dimensional layers stack together to form a nanometre-scale one-dimensional tunnel along the a axis. These nano-tunnels are filled with perchlorate counter-anions. Thus the crystals of (I) potentially have the ability to ion-exchange from perchlorate anions to other analogues such as BF4-. In addition to the above-mentioned hydrogen bonding between counter-anions and the ligands of the layer in which the counter-anions are located, there are weak Ag···O interactions between the two O atoms, O2 and O3, of one counter-anion and an Ag atom in a neighbouring layer, with Ag···O separations of 2.968 (3) and 3.016 (3) Å. Weak inter-layer π–π stacking, occurring between the benzene rings and pyridyl rings from neighbouring layers with a centroid-to-centroid distance of about 4 Å, also contribute somewhat to the supramolecular three-dimensional structure of (I).
The structures of some related silver(I)–pyridyl coordination polymers with perchlorate anions acting as both counter-anions and coordinating ligands have been reported. They are ({Ag2[1,3-bis(4,5-dihydro-1H-imidazol-2- yl)benzene]2}(ClO4)2)n (Ren et al., 2004), {[Ag(2,4'-bipyridine)]ClO4}n (Tong et al., 1998), [Ag(di-2-pyridyl ketone)ClO4]n (Yang et al., 2000) and {Ag2.5[2,5-bis(2-benzodiazine)-3,4-diaza-2,4-hexadiene]1.5(ClO4)2.5(H2O)2}n (Dong et al., 2005). The coordination modes of the perchlorate anions with the silver metal centre in the first of these compounds is very similar to that observed in (I). The silver ion has weak contacts with two O atoms from one perchlorate anion, with Ag···O separations of 2.83 and 3.11 Å. Another similarity is that the perchlorate anion forms weak hydrogen-bonding interactions with the uncoordinated N atoms from the organic ligand, with N···O (D···A) distances of 3.04 and 3.08 Å, which are longer than that in (I) (Ren et al., 2004). In the other three cited silver coordination polymers, the perchlorate O atoms are directly coordinated to the silver metal centers with Ag—O bond lengths less than 2.7 Å. Unlike the weak Ag···O contacts present in (I) and ({Ag2[1,3-bis(4,5-dihydro-1H-imidazol-2-yl)benzene]2}(ClO4)2)n, which involve two O atoms of the anion, these strong Ag—O contacts form between just one perchlorate O atom and one Ag atom.