Acta Cryst. (2007). E63, m2967 [ doi:10.1107/S1600536807053937 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-1,1'-methylenediimidazole] hexafluoridophosphate]The title compound, {[Ag(C7H8N4)]PF6}n, has a one-dimensional zigzag chain structure. The Ag+ cation and the PF6- anion reside on crystallographic inversion centres. The Ag+ cation is coordinated by the unsubstituted N atoms of two separate 1,1'-methylenediimidazole ligands. The closest Ag
Ag separation in the same cationic chain is 7.704 (2) Å and the dihedral angle between the two imidazole rings in the same ligand is 85.5 (1)°. A two-dimensional layer framework is formed by weak AgN interactions between adjacent chains, with an AgN distance of 3.472 (2) Å.
An acetone solution (5 ml) of BIM (74 mg, 0.5 mmol) was slowly diffused into an aqueous solution (5 ml) of AgPF6(126 mg, 0.5 mmol) in test tube. Colorless crystals of [Ag(BIM) PF6]n were formed at the interface of solvent in two weeks and were obtained in 82% yield. Anal. Calcd for C7H8AgF6N4P: C, 20.97; H, 2.01; N, 13.97; Found (%): C, 21.04; H, 2.49; N, 13.92; IR (KBr, cm−1): ν = 3150 s, 3114w, 3038w, 1712w, 1614w, 1530 s, 1411m, 1377w, 1355w, 1339w, 1291m, 1243 s, 1116 s, 1031w, 835 s, 747 s, 713w, 652m, 613w, 560 s.
H atoms were positioned geometrically at distances of 0.93 (CH), 0.97 (CH2) and 0.96Å (CH3) from the parent C atoms, a riding model was used during the refinement process. The Uiso values were constrained to be 1.2Ueq of the carrier atom, except for methyl H atoms that were constrained to 1.5Ueq of the C atom.
Data collection: SMART, (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001.
![[Figure 1]](./fj2055fig1thm.gif)
| Fig. 1. The structure of (I) showing the atom-numbering of unsymmetry unit. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry codes: (A) −x + 2, −y, −z + 1.] |
![[Figure 2]](./fj2055fig2thm.gif)
| Fig. 2. Two-dimensional layer structure assembled by one-dimensional zigzag chains with weak Ag······N interactions. |
| [Ag(C7H8N4)]PF6 | F000 = 388 |
| Mr = 401.01 | Dx = 2.264 Mg m−3 |
| Monoclinic, P2/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yac | Cell parameters from 1730 reflections |
| a = 8.3966 (10) Å | θ = 5.5–56.3º |
| b = 5.1604 (6) Å | µ = 1.92 mm−1 |
| c = 13.6211 (16) Å | T = 293 (2) K |
| β = 94.666 (2)º | Prismatic, colorless |
| V = 588.24 (12) Å3 | 0.23 × 0.15 × 0.12 mm |
| Z = 2 |
| SMART APEX-CCD diffractometer | 1285 independent reflections |
| Radiation source: fine-focus sealed tube | 1073 reflections with > 2s˘I) |
| Monochromator: graphite | Rint = 0.080 |
| T = 293(2) K | θmax = 27.0º |
| phi and ω scans | θmin = 2.8º |
| Absorption correction: multi-scan SADABS (Sheldrick, 1996) | h = −10→10 |
| Tmin = 0.596, Tmax = 0.793 | k = −6→6 |
| 3264 measured reflections | l = −17→8 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
| wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0602P)2 + 0.0221P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.07 | (Δ/σ)max = 0.003 |
| 1285 reflections | Δρmax = 0.81 e Å−3 |
| 90 parameters | Δρmin = −0.62 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [Ag(C7H8N4)]PF6 | V = 588.24 (12) Å3 |
| Mr = 401.01 | Z = 2 |
| Monoclinic, P2/n | Mo Kα |
| a = 8.3966 (10) Å | µ = 1.92 mm−1 |
| b = 5.1604 (6) Å | T = 293 (2) K |
| c = 13.6211 (16) Å | 0.23 × 0.15 × 0.12 mm |
| β = 94.666 (2)º |
| SMART APEX-CCD diffractometer | 1285 independent reflections |
| Absorption correction: multi-scan SADABS (Sheldrick, 1996) | 1073 reflections with > 2s˘I) |
| Tmin = 0.596, Tmax = 0.793 | Rint = 0.080 |
| 3264 measured reflections |
| R[F2 > 2σ(F2)] = 0.036 | 90 parameters |
| wR(F2) = 0.104 | H-atom parameters constrained |
| S = 1.07 | Δρmax = 0.81 e Å−3 |
| 1285 reflections | Δρmin = −0.62 e Å−3 |
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 | Occ. (<1) | |
| Ag1 | 1.0000 | 0.0000 | 0.5000 | 0.0467 (2) | |
| P1 | 0.5000 | 0.0000 | 0.5000 | 0.0395 (3) | |
| F1 | 0.6294 (4) | 0.1949 (7) | 0.5436 (2) | 0.0925 (11) | |
| F2 | 0.4980 (3) | 0.1377 (6) | 0.39578 (17) | 0.0719 (7) | |
| F3 | 0.3615 (4) | 0.1824 (7) | 0.5298 (2) | 0.0900 (10) | |
| N1 | 0.9785 (3) | 0.3049 (5) | 0.39798 (19) | 0.0421 (6) | |
| N2 | 0.8717 (3) | 0.6069 (5) | 0.30233 (19) | 0.0356 (6) | |
| C1 | 0.8469 (4) | 0.4306 (7) | 0.3711 (3) | 0.0397 (7) | |
| H1 | 0.7490 | 0.4010 | 0.3965 | 0.048* | |
| C2 | 1.0280 (4) | 0.5957 (9) | 0.2850 (3) | 0.0547 (9) | |
| H2 | 1.0798 | 0.6969 | 0.2410 | 0.066* | |
| C3 | 1.0936 (4) | 0.4092 (10) | 0.3443 (3) | 0.0592 (10) | |
| H3 | 1.2003 | 0.3590 | 0.3482 | 0.071* | |
| C4 | 0.7500 | 0.7683 (8) | 0.2500 | 0.0403 (10) | |
| H4A | 0.7007 | 0.8786 | 0.2966 | 0.048* | 0.50 |
| H4B | 0.7993 | 0.8786 | 0.2034 | 0.048* | 0.50 |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ag1 | 0.0582 (3) | 0.0379 (3) | 0.0419 (3) | 0.00042 (13) | −0.00903 (18) | 0.00663 (14) |
| P1 | 0.0398 (7) | 0.0396 (7) | 0.0398 (7) | 0.0011 (4) | 0.0072 (5) | −0.0004 (5) |
| F1 | 0.104 (2) | 0.103 (2) | 0.088 (2) | −0.0565 (19) | −0.0051 (18) | −0.0118 (19) |
| F2 | 0.0843 (17) | 0.0799 (19) | 0.0524 (13) | 0.0033 (13) | 0.0112 (12) | 0.0182 (13) |
| F3 | 0.103 (2) | 0.101 (2) | 0.086 (2) | 0.0592 (18) | 0.0278 (17) | 0.0008 (19) |
| N1 | 0.0489 (14) | 0.0392 (14) | 0.0367 (14) | 0.0002 (11) | −0.0051 (11) | 0.0052 (12) |
| N2 | 0.0402 (13) | 0.0338 (13) | 0.0321 (13) | −0.0031 (10) | −0.0006 (10) | 0.0002 (11) |
| C1 | 0.0439 (17) | 0.0339 (14) | 0.0411 (18) | −0.0017 (13) | 0.0025 (14) | 0.0024 (14) |
| C2 | 0.0441 (18) | 0.072 (2) | 0.049 (2) | −0.0050 (18) | 0.0074 (16) | 0.023 (2) |
| C3 | 0.0408 (18) | 0.076 (2) | 0.061 (2) | 0.0030 (19) | 0.0024 (17) | 0.015 (2) |
| C4 | 0.050 (2) | 0.029 (2) | 0.041 (2) | 0.000 | −0.0025 (19) | 0.000 |
| Ag1—N1i | 2.097 (3) | N2—C1 | 1.334 (5) |
| Ag1—N1 | 2.097 (3) | N2—C2 | 1.354 (4) |
| P1—F1 | 1.562 (2) | N2—C4 | 1.459 (3) |
| P1—F1ii | 1.562 (2) | C1—H1 | 0.9300 |
| P1—F3 | 1.575 (2) | C2—C3 | 1.345 (6) |
| P1—F3ii | 1.575 (2) | C2—H2 | 0.9300 |
| P1—F2 | 1.586 (2) | C3—H3 | 0.9300 |
| P1—F2ii | 1.586 (2) | C4—N2iii | 1.459 (3) |
| N1—C1 | 1.308 (4) | C4—H4A | 0.9700 |
| N1—C3 | 1.369 (5) | C4—H4B | 0.9700 |
| N1i—Ag1—N1 | 180.000 (1) | C1—N2—C2 | 107.6 (3) |
| F1—P1—F1ii | 180.00 (18) | C1—N2—C4 | 126.1 (2) |
| F1—P1—F3 | 91.3 (2) | C2—N2—C4 | 126.2 (3) |
| F1ii—P1—F3 | 88.7 (2) | N1—C1—N2 | 111.0 (3) |
| F1—P1—F3ii | 88.7 (2) | N1—C1—H1 | 124.5 |
| F1ii—P1—F3ii | 91.3 (2) | N2—C1—H1 | 124.5 |
| F3—P1—F3ii | 180.0 (2) | C3—C2—N2 | 106.4 (3) |
| F1—P1—F2 | 90.48 (15) | C3—C2—H2 | 126.8 |
| F1ii—P1—F2 | 89.52 (15) | N2—C2—H2 | 126.8 |
| F3—P1—F2 | 90.52 (15) | C2—C3—N1 | 109.2 (3) |
| F3ii—P1—F2 | 89.48 (15) | C2—C3—H3 | 125.4 |
| F1—P1—F2ii | 89.52 (15) | N1—C3—H3 | 125.4 |
| F1ii—P1—F2ii | 90.48 (15) | N2iii—C4—N2 | 110.4 (3) |
| F3—P1—F2ii | 89.48 (15) | N2iii—C4—H4A | 109.6 |
| F3ii—P1—F2ii | 90.52 (15) | N2—C4—H4A | 109.6 |
| F2—P1—F2ii | 180.000 (1) | N2iii—C4—H4B | 109.6 |
| C1—N1—C3 | 105.8 (3) | N2—C4—H4B | 109.6 |
| C1—N1—Ag1 | 125.7 (2) | H4A—C4—H4B | 108.1 |
| C3—N1—Ag1 | 128.5 (2) | ||
| C3—N1—C1—N2 | 0.8 (4) | N2—C2—C3—N1 | 0.1 (6) |
| Ag1—N1—C1—N2 | −177.7 (2) | C1—N1—C3—C2 | −0.5 (5) |
| C2—N2—C1—N1 | −0.7 (4) | Ag1—N1—C3—C2 | 177.8 (3) |
| C4—N2—C1—N1 | 175.0 (3) | C1—N2—C4—N2iii | −58.6 (3) |
| C1—N2—C2—C3 | 0.4 (5) | C2—N2—C4—N2iii | 116.4 (4) |
| C4—N2—C2—C3 | −175.4 (4) |
| Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+3/2, y, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C3—H3···F2iv | 0.93 | 2.78 | 3.687 (5) | 167 |
| C3—H3···F3iv | 0.93 | 2.87 | 3.448 (5) | 122 |
| C4—H4A···F2v | 0.97 | 2.62 | 3.569 (4) | 165 |
| C4—H4A···F3vi | 0.97 | 2.48 | 3.224 (3) | 133 |
| C2—H2···F1vii | 0.93 | 2.81 | 3.628 (5) | 148 |
| C1—H1···F3vi | 0.93 | 2.58 | 3.043 (4) | 111 |
| Symmetry codes: (iv) x+1, y, z; (v) x, y+1, z; (vi) −x+1, −y+1, −z+1; (vii) x+1/2, −y+1, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C3—H3···F2i | 0.93 | 2.78 | 3.687 (5) | 167 |
| C3—H3···F3i | 0.93 | 2.87 | 3.448 (5) | 122 |
| C4—H4A···F2ii | 0.97 | 2.62 | 3.569 (4) | 165 |
| C4—H4A···F3iii | 0.97 | 2.48 | 3.224 (3) | 133 |
| C2—H2···F1iv | 0.93 | 2.81 | 3.628 (5) | 148 |
| C1—H1···F3iii | 0.93 | 2.58 | 3.043 (4) | 111 |
| Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z; (iii) −x+1, −y+1, −z+1; (iv) x+1/2, −y+1, z−1/2. |
We gratefully acknowledge the financial support of the National Science Funds for Distinguished Young Scholars of Hubei Province (Grant No. 2006ABB038), the Outstanding Mid-Young Scholars' Programs, Hubei Provincial Department of Education (Q20072203) and the project sponsored by SRF for ROCS, SEM (200724).
Barnett, S. A. & Champness, N. R. (2003). Coord. Chem. Rev. 246, 145–168.
Batten, S. R. & Robson, R. (1998). Angew. Chem. Int. Ed. Engl. 37, 1460–1494.
Bruker (2001). SAINT-Plus (Version 6.45) and SMART (Version 5.628). Bruker AXS, Inc., Madison, Wisconsin, USA.
Desiraju, G. R. (1995). Angew. Chem. Int. Ed. Engl. 34, 2311–2327.
Hamilton, B. H. & Ziegler, C. J. (2004). Inorg. Chem. 43, 4272–4277.
Leininger, S., Olenyuk, B. & Stang, P. J. (2000). Chem. Rev. 100, 853–908.
Lobbia, G. G., Pellei, M., Pettinari, C., Santini, C., Skelton, B. W., Somers, N. & White, A. H. (2002). J. Chem. Soc. Dalton Trans. pp. 2333–2340.
Moulton, B. & Zaworotko, M. J. (2001). Chem. Rev. 101, 1629–1658.
Pschirer, N. G., Curtin, D. M., Smith, M. D., Bunz, W. H. F. & Zur Loye, H.-C. (2002). Angew. Chem. Int. Ed. Engl. 41, 583–585.
Sheldrick, G. M. (1996). SADABS. Version 2.10. Bruker AXS Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
The construction of solid-state architectures and crystal engineering has become rapidly developing areas of supramolecular chemistry in the past decade (Desiraju, 1995; Batten & Robson, 1998; Leininger et al., 2000; Moulton & Zaworotko, 2001). Such molecular architectures have been successfully designed and synthesized by judicious combination of a metal 'node' and an organic ligand 'spacer'. The roles of counter anions and different solvent molecules are also of significant effect on supramolecular self-assembly. More recently, the molecular geometry and flexibility of multidentate N-donor spacer ligands play key roles in the development of the tailor-made molecular materials and supramolecular self-assemble crystal engineering. For example, 4, 4'-bipyridine, 1, 2-bis(4-pyridyl)ethane and trans-bis(4-pyridyl)ethene as ligands can form a lot of coordination polymers with different structure features (Barnett & Champness, 2003; Pschirer et al., 2002). The coordination polymer frameworks which were built by methylene C-bridged bipyridine, bitriazole and bipyrazole ligands have also been described widely (Lobbia et al., 2002; Hamilton & Ziegler, 2004). Bis(imidazol-1-yl)-methane (BIM) is flexibility V-shaped N-donor ligand which was built by methylene C-bridged two imidazole rings. The title compound, [Ag(BIM)PF6]n, (I), with a one-dimensional zigzag cationic chain structural motifs, was formed by the addition of a solution of BIM to AgPF6.
Single crystal X-ray diffraction analysis reveals that complex (I) consist of one dimensional cationic polymeric chains and uncoordinated PF6−. The AgI ion occupies a crystallographic inversion centre and is coordinated by two imidazolyl nitrogen atoms of independent BIM ligands, which act as bridges between silver(I) centers, generated one dimensional zigzag cationic chain polymeric structure (Fig.1). AgI ion is a linear coordination mode with the bond angles of N—Ag—N being 180.0 (1)°, and the bond lengths of Ag—N is 2.097 (3) Å. The adjacent Ag······Ag distance in the same cationic chain is 7.704 (2)Å and the dihedral angle of the two imidazole rings in the same ligand is 85.5 (1)°. The two-dimensional layer network was built by weak interactions between AgI ion and two nitrogen atoms from imidazole rings in the adjacent one-dimensional zigzag chain with the distance of Ag—N being 3.472 (2)Å (Fig. 2). The non-coordinated PF6− anions were filled in the void of each zigzag cationic chain through the weak C—H······F hydrogen-bond interactions (Table 1).