research papers\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

IUCrJ
Volume 2| Part 2| March 2015| Pages 188-197
ISSN: 2052-2525
doi:10.1107/S2052252515000147

Solvent-vapour-assisted pathways and the role of pre-organization in solid-state transformations of coordination polymers

CROSSMARK_Color_square_no_text.svg
James S. Wright,a Iñigo J. Vitórica-Yrezábal,a‡ Harry Adams,a Stephen P. Thompson,b Adrian H. Hillc§ and Lee Brammera*

aDepartment of Chemistry, University of Sheffield, Brook Hill, Sheffield S3 7HF, UK, bDiamond Light Source, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, UK, and cEuropean Synchrotron Radiation Facility, 6 rue J. Horowitz, 38042 Grenoble, France
*Correspondence e-mail: lee.brammer@sheffield.ac.uk

Edited by A. D. Bond, University of Copenhagen, Denmark (Received 15 October 2014; accepted 6 January 2015; online 26 February 2015)

A family of one-dimensional coordination polymers, [Ag4(O2C(CF2)2CF3)4(phenazine)2(arene)n]·m(arene), 1 (arene = toluene or xylene), have been synthesized and crystallographically characterized. Arene guest loss invokes structural transformations to yield a pair of polymorphic coordination polymers [Ag4(O2C(CF2)2CF3)4(phenazine)2], 2a and/or 2b, with one- and two-dimensional architectures, respectively. The role of pre-organization of the polymer chains of 1 in the selectivity for formation of either polymorph is explored, and the templating effect of toluene and p-xylene over o-xylene or m-xylene in the formation of arene-containing architecture 1 is also demonstrated. The formation of arene-free phase 2b, not accessible in a phase-pure form through other means, is shown to be the sole product of loss of toluene from 1-tol·tol [Ag4(O2C(CF2)2CF3)4(phenazine)2(toluene)]·2(toluene), a phase containing toluene coordinated to Ag(I) in an unusual μ:η1,η1 manner. Solvent-vapour-assisted conversion between the polymorphic coordination polymers and solvent-vapour influence on the conversion of coordination polymers 1 to 2a and 2b is also explored. The transformations have been examined and confirmed by X-ray diffraction, NMR spectroscopy and thermal analyses, including in situ diffraction studies of some transformations.

CCDC references: 1051373; 1051374; 1051375; 1051376; 1051377; 1051378

1. Introduction

Designed solid-state materials are of increasing interest, an important class of which is coordination polymers, in which metal ions or clusters are connected by organic ligands (linkers) to create extended network solids that are periodic and usually crystalline. Porous coordination polymers (PCPs), more commonly known as metal–organic frameworks (MOFs), have enjoyed particular attention due to their potential application in gas sorption and separation (Li et al., 1999[Li, H., Eddaoudi, M., O'Keefe, M. & Yaghi, O. M. (1999). Nature, 402, 276-279.]; Zhang & Chen, 2009[Zhang, J.-P. & Chen, X.-M. (2009). J. Am. Chem. Soc. 131, 5516-5521.]; Sumida et al., 2009[Sumida, K., Hill, M. R., Horike, S., Dailly, A. & Long, J. R. (2009). J. Am. Chem. Soc. 131, 15120-15121.]; D'Alessandro et al., 2010[D'Alessandro, D. M., Smit, B. & Long, J. R. (2010). Angew. Chem. Int. Ed. 49, 6058-6082.]; Burd et al., 2012[Burd, S. D., Ma, S., Perman, J. A., Sikora, B. J., Snurr, R. Q., Thallapally, P. K., Tian, J., Wojtas, L. & Zaworotko, M. J. (2012). J. Am. Chem. Soc. 134, 3663-3666.]; FitzGerald et al., 2013[FitzGerald, S. A., Pierce, C. J., Rowsell, J. L. C., Bloch, E. D. & Mason, J. A. (2013). J. Am. Chem. Soc. 135, 9458-9464.]; Huang et al., 2013[Huang, Y.-L., Gong, Y.-N., Jiang, L. & Lu, T.-B. (2013). Chem. Commun. 49, 1753-1755.]; Carrington et al., 2014[Carrington, E. J., Vitórica-Yrezábal, I. J. & Brammer, L. (2014). Acta Cryst. B70, 404-422.]), heterogeneous catalysis (Gomez-Lor et al., 2002[Gomez-Lor, B., Gutiérrez-Puebla, E., Iglesias, M., Monge, M. A., Ruiz-Valero, C. & Snejko, N. (2002). Inorg. Chem. 41, 2429-2432.]; Wu et al., 2005[Wu, C.-D., Hu, A., Zhang, L. & Lin, W. (2005). J. Am. Chem. Soc. 127, 8940-8941.]; Lee et al., 2009[Lee, J.-Y., Farha, O. K., Roberts, J., Scheidt, K. A., Nguyen, S. T. & Hupp, J. T. (2009). Chem. Soc. Rev. 38, 1450-1459.]; Li et al., 2009[Li, J.-R., Kuppler, R. J. & Zhou, H.-C. (2009). Chem. Soc. Rev. 38, 1477-1504.], 2014[Li, L., Matsuda, R., Tanaka, I., Sato, H., Kanoo, P., Jeon, H. J., Foo, M. L., Wakamiya, A., Murata, Y. & Kitagawa, S. (2014). J. Am. Chem. Soc. 136, 7543-7546.]) and novel optical and magnetic properties (Evans & Lin, 2002[Evans, O. R. & Lin, W. (2002). Acc. Chem. Res. 35, 511-522.]; Zhou et al., 2013[Zhou, J.-M., Shi, W., Xu, N. & Cheng, P. (2013). Inorg. Chem. 52, 8082-8090.]; Baldoví et al., 2014[Baldoví, J. J., Coronado, E., Gaita-Ariño, A., Gamer, C., Giménez-Marqués, M. & Mínguez Espallargas, G. (2014). Chem. Eur. J. 20, 10695-10702.]; Wang et al., 2014[Wang, C., Liu, D., Xie, Z. & Lin, W. (2014). Inorg. Chem. 53, 1331-1338.]). The post-synthetic modification (PSM) of coordination polymers and PCPs has only more recently been the focus of more detailed work (Ingleson et al., 2008[Ingleson, M. J., Barrio, J. P., Guilbaud, J.-B., Khimyak, Y. Z. & Rosseinsky, M. (2008). J. Chem. Commun. pp. 2680-2682.]; Tanabe et al., 2008[Tanabe, K. K., Wang, Z. & Cohen, S. M. (2008). J. Am. Chem. Soc. 130, 8508-8517.]; Wang & Cohen, 2009[Wang, Z. & Cohen, S. M. (2009). J. Am. Chem. Soc. 131, 16675-16677.]; Nguyen & Cohen, 2010[Nguyen, J. G. & Cohen, S. M. (2010). J. Am. Chem. Soc. 132, 4560-4561.]; Vermeulen et al., 2013[Vermeulen, N. A., Karagiaridi, O., Sarjeant, A. A., Stern, C. L., Hupp, J. T., Farha, O. K. & Stoddart, J. F. (2013). J. Am. Chem. Soc. 135, 14916-14919.]; Zheng et al., 2013[Zheng, S.-T., Zhao, X., Lau, S., Fuhr, A., Feng, P. & Bu, X. (2013). J. Am. Chem. Soc. 135, 10270-10273.]; Li et al., 2013[Li, J., Huang, P., Wu, X.-R., Tao, J., Huang, R.-B. & Zheng, L.-S. (2013). Chem. Sci. 4, 3232-3238.]), facilitating the multi-step synthesis of materials (Ingleson et al., 2008[Ingleson, M. J., Barrio, J. P., Guilbaud, J.-B., Khimyak, Y. Z. & Rosseinsky, M. (2008). J. Chem. Commun. pp. 2680-2682.]; Tanabe et al., 2008[Tanabe, K. K., Wang, Z. & Cohen, S. M. (2008). J. Am. Chem. Soc. 130, 8508-8517.]; Wang & Cohen, 2009[Wang, Z. & Cohen, S. M. (2009). J. Am. Chem. Soc. 131, 16675-16677.]; Nguyen & Cohen, 2010[Nguyen, J. G. & Cohen, S. M. (2010). J. Am. Chem. Soc. 132, 4560-4561.]; Vermeulen et al., 2013[Vermeulen, N. A., Karagiaridi, O., Sarjeant, A. A., Stern, C. L., Hupp, J. T., Farha, O. K. & Stoddart, J. F. (2013). J. Am. Chem. Soc. 135, 14916-14919.]; Zheng et al., 2013[Zheng, S.-T., Zhao, X., Lau, S., Fuhr, A., Feng, P. & Bu, X. (2013). J. Am. Chem. Soc. 135, 10270-10273.]; Li et al., 2013[Li, J., Huang, P., Wu, X.-R., Tao, J., Huang, R.-B. & Zheng, L.-S. (2013). Chem. Sci. 4, 3232-3238.]; Libri et al., 2008[Libri, S., Mahler, M., Mínguez Espallargas, G., Singh, D. C. N. G., Soleimannejad, J., Adams, H., Burgard, M. D., Rath, N. P., Brunelli, M. & Brammer, L. (2008). Angew. Chem. Int. Ed. 47, 1693-1697.]; Vitórica-Yrezábal et al., 2013[Vitórica-Yrezábal, I. J., Mínguez Espallargas, G., Soleimannejad, J., Florence, A. J., Fletcher, A. J. & Brammer, L. (2013). Chem. Sci. 4, 696-708.]), stereo- or regio-selective transformation of ligands (Jones & Bauer, 2009[Jones, S. C. & Bauer, C. A. (2009). J. Am. Chem. Soc. 131, 12516-12517.]) or the modification of solid-state properties of porous materials (Wang & Cohen, 2009[Wang, Z. & Cohen, S. M. (2009). J. Am. Chem. Soc. 131, 16675-16677.]; Nguyen & Cohen, 2010[Nguyen, J. G. & Cohen, S. M. (2010). J. Am. Chem. Soc. 132, 4560-4561.]). The flexibility and responsiveness of some MOFs to removal of non-covalently bound solvent or uptake of gas molecules has been described by many groups and was highlighted by Kitagawa and co-workers at an early stage in their 2004 review in which they classified MOFs into first-, second- and third-generation materials, the latter being materials which could undergo structural changes and recover pore integrity as well as retaining or recovering crystallinity during such guest loss/uptake processes (Kitagawa et al., 2004[Kitagawa, S., Kitaura, R. & Noro, S. (2004). Angew. Chem. Int. Ed. 43, 2334-2375.]).

More generally, the reactions and structural transformations of coordination polymers include a variety of transformations involving solvation or desolvation processes, typically involving water, alcohols or acetonitrile as the solvent molecule. Such transformations involving coordinated solvent molecules can result in changes in coordination environment at the metal centres wherein terminally coordinated solvent molecules are replaced by bridging (linker) ligands during desolvation (and vice versa during solvent uptake). Reviews by Kole & Vittal (2013[Kole, G. K. & Vittal, J. J. (2013). Chem. Soc. Rev. 42, 1755-1775.]) and by Li & Du (2011[Li, C.-P. & Du, M. (2011). Chem. Commun. 47, 5958-5972.]) consider transformations of this type along with other solid-state transformations, including photochemical transformations and transformations induced by input of heat or mechanochemical energy.

In recent years, our own work has examined solid–gas and solid–vapour reactions involving molecular crystals of coordination compounds that reversibly react with HCl and HBr gases (Mínguez Espallargas et al., 2006[Mínguez Espallargas, G., Brammer, L., van de Streek, J., Shankland, K., Florence, A. J. & Adams, H. (2006). J. Am. Chem. Soc. 128, 9584-9585.], 2007[Mínguez Espallargas, G., Hippler, M., Florence, A. J., Fernandes, P., van de Streek, J., Brunelli, M., David, W. I. F., Shankland, K. & Brammer, L. (2007). J. Am. Chem. Soc. 129, 15606-15614.], 2010[Mínguez Espallargas, G., van de Streek, J., Fernandes, P., Florence, A. J., Brunelli, M., Shankland, K. & Brammer, L. (2010). Angew. Chem. Int. Ed. 49, 8892-8896.], 2011[Mínguez Espallargas, G., Florence, A. J., van de Streek, J. & Brammer, L. (2011). CrystEngComm, 13, 4400-4404.]; Vitórica-Yrezábal et al., 2011[Vitórica-Yrezábal, I. J., Sullivan, R. A., Purver, S. L., Curfs, C., Tang, C. C. & Brammer, L. (2011). CrystEngComm, 13, 3189-3196.]), and coordination polymers that reversibly take up and release small alcohol molecules (Libri et al., 2008[Libri, S., Mahler, M., Mínguez Espallargas, G., Singh, D. C. N. G., Soleimannejad, J., Adams, H., Burgard, M. D., Rath, N. P., Brunelli, M. & Brammer, L. (2008). Angew. Chem. Int. Ed. 47, 1693-1697.]; Vitórica-Yrezábal et al., 2013[Vitórica-Yrezábal, I. J., Mínguez Espallargas, G., Soleimannejad, J., Florence, A. J., Fletcher, A. J. & Brammer, L. (2013). Chem. Sci. 4, 696-708.]), in each case requiring changes in metal coordination environments that are accompanied by structural changes and changes in intermolecular interactions (hydrogen bonding and/or halogen bonding). The present study builds upon earlier work that introduced a variety of networks formed by combining silver(I) perfluorocarboxylates with neutral ditopic ligands such as pyrazines and in particular emphasized the silver carboxylate dimer, Ag2(O2CR)2, as a secondary building unit (SBU) that can be linked by ditopic ligands into coordination polymers (Fig. 1[link]). Specifically we report a new family of coordination polymers that involve tetrameric units Ag4(O2CR)4, which arise from fusing of two dimers via additional Ag—O bonds. The tetramers are linked via phenazine ligands to form coordination polymers, and exhibit a variety of chemical and structural transformations that result from loss of arene guests that directly coordinate to Ag(I) centres. This behaviour is related to earlier studies of a family of coordination polymers that comprise tetramethylpyrazine linker ligands (Libri et al., 2008[Libri, S., Mahler, M., Mínguez Espallargas, G., Singh, D. C. N. G., Soleimannejad, J., Adams, H., Burgard, M. D., Rath, N. P., Brunelli, M. & Brammer, L. (2008). Angew. Chem. Int. Ed. 47, 1693-1697.]; Vitórica-Yrezábal et al., 2013[Vitórica-Yrezábal, I. J., Mínguez Espallargas, G., Soleimannejad, J., Florence, A. J., Fletcher, A. J. & Brammer, L. (2013). Chem. Sci. 4, 696-708.]) rather than phenazine, but here we also report on the transformation between coordination polymer structures, both by heating and vapour-assisted means, in one case leading to a polymorph that is inaccessible in a phase-pure form through direct solution-phase synthesis.

[Figure 1]
Figure 1
(a) Silver(I) carboxylate dimer and (b) silver(I) carboxylate tetramer secondary building units, which when connected by neutral ditopic ligands, L (here phenazine), propagate coordination polymers.

2. Experimental

2.1. Crystal syntheses

All starting materials were purchased from Aldrich, Alfa Aesar or Fluorochem and used as received. Light was excluded from all reactions using foil to minimize decomposition to silver metal. In each case, 0.05 M solutions of the reagents were separately prepared by dissolving silver(I) heptafluorobutanoate (128 mg, 0.400 mmol) or phenazine (72 mg, 0.400 mmol) in 8 ml of solvent. In all cases, large yellow crystals suitable for single-crystal X-ray diffraction were formed within 1 week.

2.1.1. [Ag4(O2C(CF2)2CF3)4(phen)2(tol)]·2(tol), 1-tol·tol

An 0.05 M solution of Ag(O2C(CF2)2CF3) (128 mg, 0.400 mmol) in 8 ml methanol was layered onto a 0.05 M solution of phenazine (72 mg, 0.400 mmol) in 8 ml toluene. Yield 71% (135 mg, 0.071 mmol). Anal. found: C 37.41, H 1.75, N 2.90; calcd: C 38.15, H 2.01, N 2.92%. Samples allowed to air-dry for more than 10 min: found: C 29.16, H 0.70, N 3.10; calcd. (for [Ag4(O2C(CF2)2CF3)4(phen)2], 2b): C 29.22, H 0.98, N 3.41%. Synthesis was also possible if methanol was replaced by ethanol, n-propanol or 2-propanol.

2.1.2. [Ag4(O2C(CF2)2CF3)4(phenazine)2(p-xylene)2], 1-pxyl

A 0.05 M solution of Ag(O2C(CF2)2CF3) (128 mg, 0.400 mmol) in 8 ml methanol was layered onto a 0.05 M solution of phenazine (72 mg, 0.400 mmol) in 8 ml p-xylene. Yield 29.6% (55 mg, 0.030 mmol). Anal. found: C 36.24, H 1.70, N 2.51; calcd: C 36.23, H 1.95, N 3.02%. Samples heated at 120°C for 2 h: found: C 29.23, H 0.74, N 3.37; calcd (for [Ag4(O2C(CF2)2CF3)4(phen)2], 2a or 2b): C 29.22, H 0.98, N 3.41%.

2.1.3. [Ag4(O2C(CF2)2CF3)4(phenazine)2(m-xylene)2], 1-mxyl

An 0.05 M solution of Ag(O2C(CF2)2CF3) (128 mg, 0.400 mmol) in 8 ml methanol was layered onto a 0.05 M solution of phenazine (72 mg, 0.400 mmol) in 8 ml m-xylene. Yield 37.7% (70 mg, 0.038 mmol). Anal. found: C 36.28, H 1.57, N 2.61%; calcd: C 36.23, H 1.95, N 3.02%. Samples heated at 120°C for 2 h: found: C 29.46, H 0.90, N 3.44; calcd: C 29.22, H 0.98, N 3.41% (for [Ag4(O2C(CF2)2CF3)4(phen)2], 2a or 2b). (See the supporting information for a discussion of X-ray powder diffraction and TGA.)

2.1.4. [Ag4(O2C(CF2)2CF3)4(phenazine)2(tol)x((p-xylene)1 − x]·n(toluene)·(2 − n)(p-xylene), 1-pxyl-tol·pxyl·tol

A 0.05 M solution of Ag(O2C(CF2)2CF3) (128 mg, 0.400 mmol) in 8 ml methanol was layered onto a 0.05 M solution of phenazine (72 mg, 0.400 mmol) in 8 ml of 1:1 toluene:p-xylene. Yield 56.8% (110 mg, 0.057 mmol). Anal. found: C 37.96, H 1.98, N 2.74; calcd: C 38.67, H 2.22, N 2.90% (for x = 0.575, n = 2x; as found by GC (gas chromatography)/NMR).

2.1.5. [Ag4(O2C(CF2)2CF3)4(phenazine)2], 2a

A 0.05 M solution of Ag(O2C(CF2)2CF3) (128 mg, 0.400 mmol) in 8 ml methanol was layered onto a 0.05 M solution of phenazine (72 mg, 0.4 mmol) in 8 ml of o-xylene. Yield 45.6% (75 mg, 0.046 mmol). Anal. found: C 29.32, H 0.49, N 3.27; calcd: C 29.22, H 0.98, N 3.41%. Synthesis was also possible in comparable yields by layering a 0.05 M solution of Ag(O2C(CF2)2CF3) (128 mg, 0.400 mmol) in 8 ml methanol onto a 0.05 M solution of phenazine (72 mg, 0.400 mmol) in 8 ml of dichloromethane. Synthesis could also be achieved by slowly evaporating an 0.05 M solution of Ag(O2C(CF2)2CF3) (128 mg, 0.400 mmol) and phenazine (72 mg, 0.40 mmol) in 16 ml of acetone.

2.2. Vapour exposure experiments

In all cases, crystals were removed from the mother liquor and gently dried between filter papers, before being gently ground in an agate pestle and mortar. The powder (approx. 30 mg) was placed in a small sample vial with a plastic lid, pierced once. This vial was placed inside a larger vial containing 1 ml of the relevant solvent, and the larger vial sealed and stored in the dark for 2 weeks.

2.3. Mechanochemistry

100 mg of the dried, yellow microcrystalline 2a was ground gently in an agate pestle and mortar, then placed into a 5 ml capacity (No. 59) Retsch cylindrical stainless steel grinding jar, either dry or with 50 µL acetone. The jar was fixed into a Retsch MM200 mixer mill, and shaken at a rate of 25 Hz for 15 min. The resultant yellow powder was analysed by X-ray powder diffraction.

2.4. Analytical techniques

2.4.1. X-ray crystallography

Single-crystal X-ray data were collected at 100 K for compounds 1-tol·tol, 1-mxyl, 1-pxyl, 1-tolpxyl and 2a on Bruker APEX-II diffractometers, using Mo Kα radiation. Data for 2b, the product of heating 1·tol·tol, were collected on a Rigaku Saturn 724+ CCD diffractometer at Diamond Light Source beamline I19 [λ = 0.6889 (3) Å] (Nowell et al., 2012[Nowell, H., Barnett, S. A., Christensen, K. E., Teat, S. J. & Allan, D. R. (2012). J. Synchrotron Rad. 19, 435-441.]). Data were collected as a series of five sequences of frames, each covering approximately one hemisphere of reciprocal space. The first 20 frames of the first sequence were repeated at the end of data collection as a check for radiation damage. Each frame was collected as a 1 s exposure, with full available attenuation to prevent beam damage. CCD frame data were transformed from Rigaku to Bruker SMART format using the program ECLIPSE (Dawson et al., 2004[Dawson, A., Allan, D. R., Parsons, S. & Ruf, M. (2004). J. Appl. Cryst. 37, 410-416.]). Data were corrected for absorption using empirical methods (SADABS), based on symmetry-equivalent reflections combined with measurements at different azimuthal angles (Sheldrick, 1995[Sheldrick, G. M. (1995). SADABS, Empirical Absorption Correction Program. University of Göttingen, Germany.]; Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. B. B51, 33-38.]). Crystal structures were solved and refined against all F2 values, using the SHELXTL program suite (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), or using Olex2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]). Non-H atoms were refined anisotropically (except as noted), and H atoms placed in calculated positions refined using idealized geometries (riding model) and assigned fixed isotropic displacement parameters. Disorder in the fluoroalkyl chains in compounds 1-tol·tol, 1-mxyl, 1-tolpxyl and 2a was modelled in two orientations, dependent upon rotation about the β- and γ-CF2 groups and the terminal CF3 groups. Disordered atoms in the fluoroalkyl chains were modelled isotropically. Toluene molecules in the compound 1-tol·tol are situated on inversion centres that lie at the centre of the six-membered ring. For 1-tol-pxyl·tol·pxyl occupational and positional disorder for toluene/p-xylene guest molecules was dealt with by applying bond distance restraints and assigning fixed occupancies of 0.7215 to methyl C atoms consistent with the spectroscopic/chromatographic determination of the toluene:p-xylene ratio as 0.575:0.425. The non-coordinated arenes were modelled with isotropic displacement parameters. Crystallographic data for all compounds are summarized in Table 1[link].

Table 1
Data collection, structure solution and refinement parameters for 1-tol·tol, 1-mxyl, 1-pxyl, 2a, 2b and 1-tol-pxyl·tol·pxyl

  1-tol·tol 1-pxyl 1-mxyl
Crystal habit Plate Plate Plate
Crystal colour Yellow Yellow Yellow
Crystal size (mm) 0.41 × 0.14 × 0.11 0.37 × 0.33 × 0.08 0.42 × 0.20 × 0.12
Crystal system Triclinic Monoclinic Monoclinic
Space group [P\bar 1] P21/c P21/c
a (Å) 10.6531 (7) 11.1146 (3) 11.3750 (6)
b (Å) 11.2628 (7) 22.7107 (8) 22.5963 (10)
c (Å) 14.4311 (10) 13.2046 (4) 13.3460 (7)
α (°) 72.401 (3) 90 90
β (°) 86.598 (3) 111.785 (2) 113.472 (2)
γ (°) 82.882 (3) 90 90
V (Å3) 1637.3 (2) 3095.1 (2) 3146.5 (3)
Density (mg m−3) 1.948 1.992 1.959
Temperature (K) 100 100 100
μ(Mo Kα) (mm−1) 1.316 1.388 1.366
θ range (°) 2.403–27.116 2.67–25.74 2.45–27.43
No. of measured reflections 25 299 26 785 25 586
No. of independent reflections, Rint 7283, 0.0507 7075, 0.0505 7203, 0.0574
No. of reflections used in refinement, n 7283 7075 7203
LS parameters, p 422 453 432
Restraints, r 0 0 70
R1 (F)† I > 2.0σ(I) 0.0649 0.0407 0.0744
wR2 (F2)†, all data 0.1673 0.1217 0.1887
S(F2)†, all data 1.086 1.048 1.117
  2a 2b 1-tol-pxyl·tol·pxyl
Crystal habit Plate Plate Plate
Crystal colour Yellow Yellow Yellow
Crystal size (mm) 0.03 × 0.26 × 0.40 Not recorded 0.33 × 0.21 × 0.15
Crystal system Monoclinic Triclinic Triclinic
Space group C2/c [P\bar 1] [P\bar 1]
a (Å) 27.578 (3) 10.782 (3) 10.6658 (15)
b (Å) 9.2670 (10) 11.006 (4) 11.2395 (14)
c (Å) 21.211 (2) 12.540 (4) 14.325 (2)
α (°) 90 71.569 (4) 72.054 (2)
β (°) 118.142 (3) 76.089 (4) 86.608 (3)
γ (°) 90 62.229 (4) 83.149 (3)
V (Å3) 4779.9 (9) 1241.5 (7) 1621.6 (4)
Density (mg m−3) 2.285 2.199 1.985
Temperature (K) 100 100 100
μ(Mo Kα) (mm−1) 1.782 1.715 1.330
θ range (°) 2.420–24.224 2.239–21.865 3.518–24.387
No. of measured reflections 20 167 9058 10 048
No. of independent reflections, Rint 5445, 0.0643 3916, 0.0357 7080, 0.0483
No. of reflections used in refinement, n 5445 3916 7080
LS parameters, p 362 315 382
Restraints, r 59 48 36
R1 (F)† I > 2.0σ(I) 0.0675 0.0804 0.0709
wR2 (F2)†, all data 0.2299 0.272 0.207
S(F2)†, all data 1.022 1.051 1.0196
†R1(F) = Σ(|Fo| − |Fc|)/Σ|Fo|; wR2(F2) = [Σw(Fo2 − Fc2)2/ΣwFo4]1/2; S(F2) = [Σw(Fo2 − Fc2)2/(n + r − p)]1/2.
2.4.2. Powder X-ray diffraction

Samples prepared as described above were loaded into borosilicate capillaries of diameter 0.7 mm (Diamond Light Source and ESRF) or 0.5 mm (University of Sheffield). For in situ heating studies, a small plug of glass wool was added to prevent sample loss from open capillaries during sample spinning. Data were collected on beamline I11 (Thompson et al., 2009[Thompson, S. P., Parker, J. E., Potter, J., Hill, T. P., Birt, A., Cobb, T. M., Yuan, F. & Tang, C. C. (2009). Rev. Sci. Instrum. 80, 075107.], 2011[Thompson, S. P., Parker, J. E., Marchal, J., Potter, J., Birt, A., Yuan, F., Fearn, R. D., Lennie, A. R., Street, S. R. & Tang, C. C. (2011). J. Synchrotron Rad. 18, 637-648.]), at Diamond Light Source for the in situ heating study for 1·tol·tol [λ = 0.826008 (2) Å], for compounds 1-tol-pxyl·tol·pxyl, 1·mxyl, 1·pxyl and 2a and for the in situ heating studies for 1·mxyl and 1·pxyl [λ = 0.826136 (2) Å], and for the ex situ alcohol vapour exposure study on 1·tol·tol [λ = 0.82562 (1) Å]. Data were collected using a wide-angle (90°) PSD (position-sensitive detector) (Thompson et al., 2011[Thompson, S. P., Parker, J. E., Marchal, J., Potter, J., Birt, A., Yuan, F., Fearn, R. D., Lennie, A. R., Street, S. R. & Tang, C. C. (2011). J. Synchrotron Rad. 18, 637-648.]) comprised of 18 Mythen-2 modules. Each 2 s scan was collected as two 1 s scans with a 0.25° 2θ offset (to account for the gaps between the Mythen-2 modules). These pairs of scans were then summed to give a single data file, used for fitting.

Diffraction data for the products of solvent-assisted transformations of 2b to mixtures of 2b and 2a, as well as for the products of attempted syntheses of 2b were collected on a Stoe Stadi P diffractometer using Cu Kα radiation (λ = 1.5406 Å) in the Department of Materials Science and Engineering, University of Sheffield. Data were collected using a PSD detector with a single scan (5 < 2θ < 40°) at a scan rate of 0.067° min−1, using a rotating capillary.

Diffraction data for samples of 1-tol·tol exposed to xylene vapours were collected at room temperature at λ = 0.3997939 (15) Å; and for the products of mechanochemical experiments on 2a at 0.400021 (9) Å using station ID313 (Fitch, 2004[Fitch, A. N. (2004). J. Res. Natl Inst. Stand. Technol. 109, 133-142.]), at the European Synchrotron Radiation Facility (ESRF). The data were collected using a nine-channel multi-analyser crystal (MAC) detector. Using a rotating capillary, 5 scans (−2.5 ≤ 2θ ≤ 18 °) were collected at a speed of 4° min−1. After each scan the capillary was translated such that each scan was on a portion of sample not thus far irradiated. All patterns were summed to give a final pattern used for the data analysis.

Diffraction patterns were indexed and fitted using the TOPAS-Academic program (Coelho, 2007[Coelho, A. A. (2007). TOPAS-Academic, Version 4.1, see https://www.topas-academic.net .]), by Pawley refinement (Pawley, 1981[Pawley, G. S. (1981). J. Appl. Cryst. 14, 357-361.]) for data with dmin ≤ 1.55 Å in each case, and (in cases specified) then by Rietveld refinement (Rietveld, 1969[Rietveld, H. M. (1969). J. Appl. Cryst. 2, 65-71.]) using starting models from previous single-crystal structure determinations. Full details of refinements and all fitted patterns are included in the supporting information .

2.4.3. Elemental analysis

Elemental analyses were carried out by the University of Sheffield Department of Chemistry elemental analysis service, using a Perkin–Elmer 2400 CHNS/O Series II elemental analyser. Elemental analyses on the 1-arene series of compounds were conducted immediately upon removal of the crystals from the mother liquor; measurements repeated after 30 min refrigeration at 5°C gave consistent values.

2.4.4. 1H NMR spectroscopy

A sample of 1-tol-pxyl·tol·pxyl was air-dried and dissolved in DMSO-d6, then filtered through cotton wool. A 1H NMR spectrum was measured on a Bruker AV 400 MHz spectrometer. The spectrum is reported in the supporting information .

2.4.5. Gas chromatography

Crystals of 1-tol-pxyl·tol·pxyl were dissolved in DMSO with some sonication, sealed in glass vials using crimped caps, and then run through a Perkin–Elmer Autosystem FID microcolumn, heating from 50 to 300°C at 10°C min−1. Retention times were compared to those for pure samples of phenazine, silver(I) heptafluorobutanoate, toluene, xylene (each dissolved in or diluted with DMSO) and pure DMSO. Relative content of guests was determined by direct comparison of chromatogram peak areas. The gas chromatogram for 1-tol-pxyl·tol·pxyl can be found in the supporting information .

2.4.6. Thermal analysis

Thermogravimetric analyses were conducted using a Perkin–Elmer Pyris1 TGA model thermogravimetric analyser. Samples were heated from 30 to 400°C at 5°C min−1 under a flow of dry N2 gas. Thermogravimetric traces can be found in the supporting information .

3. Results and discussion

3.1. Synthesis and crystal structures of coordination polymers 1-tol·tol, 1-pxyl, 1-mxyl, 1-tol-pxyl·tol·pxyl, 2a and 2b

A family of one-dimensional coordination polymers [Ag4(O2C(CF2)2CF3)4(phenazine)2(toluene)]·2(toluene) (1-tol·tol), [Ag4(O2C(CF2)2CF3)4(phenazine)2(m-xylene)2] (1-mxyl) and [Ag4(O2C(CF2)2CF3)4(phenazine)2(p-xylene)2] (1-pxyl) were synthesized by layering a methanol solution of silver heptafluorobutanoate onto a solution of phenazine in the corresponding arene. All compounds were characterized by single-crystal X-ray diffraction, the composition was confirmed by elemental analysis and phase purity was examined by X-ray powder diffraction (see the supporting information ). The mixed-arene coordination polymer [Ag4(O2C(CF2)2CF3)4(phenazine)2(toluene)n(p-xylene)1 − n]·n(toluene)·(2 − n)(p-xylene) (1-tol-pxyl·tol·pxyl) was prepared in an analogous manner using a 1:1 toluene:p-xylene solvent mixture. When o-xylene is used as the arene, the product is one-dimensional coordination polymer [Ag4(O2C(CF2)2CF3)4(phenazine)2] (2a), which contains no o-xylene. A two-dimensional coordination polymer, 2b, which is a polymorph of 2a, is obtained upon loss of toluene from 1-tol·tol, but could not be prepared from solution-phase synthesis.

The crystal structure of 1-tol·tol (Fig. 2[link]) consists of building blocks of Ag4(O2C(CF2)2CF3)4(phenazine)2, within which two Ag2(O2C(CF2)2CF3)2 dimers are linked by bridging phenazine ligands which are oriented in a face-to-face manner. These building blocks are linked into one-dimensional tapes via pairs of Ag—O bonds, forming the silver(I) carboxylate tetramer illustrated in Fig. 1[link](b). The one-dimensional tapes are cross-linked via toluene molecules, which bridge silver(I) centres in a μ–η1,η1 manner. Although there are many examples of π-coordination to Ag(I) centres, to the best of our knowledge, this toluene bridging mode has not previously been observed, although bridging in a μ–η2,η2 fashion has been reported (Zhong et al., 2001[Zhong, J. C., Munakata, M., Kuroda-Sowa, T., Maekawa, M., Suenaga, Y. & Konaka, H. (2001). Inorg. Chem. 40, 3191-3199.]). The cross-linking creates two-dimensional layers of silver coordination polymer, with an additional two toluene molecules per formula unit residing between the layers (Fig. 2[link]b).

[Figure 2]
Figure 2
Crystal structure of [Ag4(O2C(CF2)2CF3)4(phenazine)2(toluene)]·2(toluene) (1-tol·tol) shown (a) in the ab plane, highlighting the μ:η1,η1 bridging toluene molecules (expansions showing the silver carboxylate dimer and the tetramers; only one of the two toluene orientations is shown in the expansions) and (b) in the bc plane, highlighting the non-coordinated toluene solvent between two-dimensional layers of 1-tol·tol. Silver ions shown in black, heptafluorobutanoate in red, phenazine in blue and toluene in green. H atoms omitted for clarity.

Although synthesis conditions using p-xylene or m-xylene instead of toluene are otherwise unchanged, the coordination polymers generated, 1-pxyl and 1-mxyl, are similar, but not identical to 1-tol·tol. Each comprises the same polymer tape structure as 1-tol·tol, except that the coordinated m-xylene or p-xylene does not bridge Ag(I) centres, instead coordinating in a η1 fashion only to the outer Ag(I) centres of each silver carboxylate tetramer (Fig. 3[link]). These one-dimensional polymer tapes stack such that there are also no additional guest solvent molecules between polymers. Alternate one-dimensional coordination polymer tapes are mutually rotated by 90° along the polymer axis, such that the orientation of the phenazine ligands is orthogonal in adjacent tapes, which also facilitates edge-to-face C—H⋯π interactions between phenazine ligands and xylenes.

[Figure 3]
Figure 3
Stacking of one-dimensional coordination polymer chains in 1-pxyl, [Ag4(O2C(CF2)2CF3)4(phenazine)2(p-xylene)2]. H atoms omitted for clarity. Colours are as in Fig. 1[link]. 1-mxyl is isostructural with 1-pxyl.

Combining silver heptafluorobutanoate and phenazine in a methanol/1:1 toluene:p-xylene solvent system yielded coordination polymer 1-tol-pxyl·tol·pxyl, [Ag4(O2C(CF2)2CF3)4(phenazine)2(toluene)n(p-xylene)1 − n]·2n(toluene)·(2 − 2n)(p-xylene), which is isostructural with 1-tol·tol. The proportion of the two arene guests within the crystal at the coordinated and uncoordinated sites could not be determined reliably from the single-crystal diffraction experiment. However, no clear difference between the populations of the two sites was apparent. The relative proportions of the two arenes were analysed, upon dissolution of the coordination polymer, by 1H NMR spectroscopy (integration of signals) and by gas chromatography (peak areas), and toluene:p-xylene ratios of 58:42 and 56:44, respectively, were determined. This suggests at best only a slight preference for toluene inclusion over p-xylene inclusion into 1-tol-pxyl·tol·pxyl. The different crystal structures of 1-tol·tol and 1-pxyl suggest that toluene rather than p-xylene should be present in the bridging coordination sites, but this could not be established crystallographically. In the final model for the crystal structure the populations of all arene sites were assumed to be identical with a toluene:p-xylene ratio of 57.5:42.5 (i.e. n = 0.575).

Conducting the coordination polymer synthesis using a methanol/o-xylene solvent system yielded the one-dimensional coordination polymer 2a, [Ag4(O2C(CF2)2CF3)4(phenazine)2]; no arene solvent is included in the crystal structure, in contrast to the use of other xylenes or toluene. Like coordination polymers 1-tol·tol, 1-pxyl and 1-myxl, the structure of 2a consists of Ag4(O2C(CF2)2CF3)4 tetramers linked by pairs of parallel phenazine units that bridge between Ag(I) centres to give a one-dimensional coordination polymer tape assembly. However, the tetramer units have a different configuration to those noted previously (Fig. 4[link]), wherein one Ag(I) centre is exclusively coordinated by carboxylate ligands and another forms bonds to two phenazine ligands, whereas all four Ag(I) centres are each bonded to one phenazine ligand in 1-tol·tol, 1-pxyl and 1-myxl. The coordination of phenazine ligands to the tetramer unit in 2a leads to an arrangement in which alternate pairs of phenazine ligands within one tape are oriented orthogonally rather than parallel to other pairs (Fig. 5[link]).

[Figure 4]
Figure 4
The silver(I) carboxylate tetramers propagating coordination polymers 1-tol·tol, 1-pxyl and 1-mxyl (left) and those in polymer architecture 2a (right).
[Figure 5]
Figure 5
Coordination polymer 2a, showing the coordination environment around Ag(I) centres; the expansion has been rotated for clarity. H atoms are omitted for clarity. Colours are as in Fig. 1[link].

A very small single crystal of the coordination polymer 2b, [Ag4(O2C(CF2)2CF3)4(phenazine)2], a polymorph of 2a, was recovered as a small fragment after heating crystals of 1-tol·tol to remove toluene. Data collection at beamline I19 at Diamond Light Source enabled crystal structure determination. Unlike 2a the structure of 2b is a two-dimensional coordination polymer comprised of Ag4(O2C(CF2)2CF3)4(phenazine)2 units linked via additional Ag—O bonds (Fig. 6[link]), analogous to that of the previously reported [Ag4(O2C(CF2)2CF3)4(TMP)2] (TMP = tetramethylpyrazine) (Vitórica-Yrezábal et al., 2013[Vitórica-Yrezábal, I. J., Mínguez Espallargas, G., Soleimannejad, J., Florence, A. J., Fletcher, A. J. & Brammer, L. (2013). Chem. Sci. 4, 696-708.]).

[Figure 6]
Figure 6
Coordination polymer 2b, viewed perpendicular to the layer arrangement. H atoms are omitted for clarity. Colours are as in Fig. 1[link].

3.2. Thermal, mechanochemical and vapour-assisted structural transformations

Thermogravimetric analysis of 1-tol·tol and 1-pxyl indicated facile loss of the arene to give materials of the composition of 2a and 2b (Figs. S2 and S3 ), as also confirmed by elemental analysis. Loss of toluene occurs most readily and is complete after 10 min in air at room temperature. Loss of p-xylene was from 1-pxyl complete by 120°C in the TGA (thermogravimetric analysis) experiment, and heating 1-pxyl or 1-mxyl to 120°C for 2 h was shown to be sufficient to remove all xylene with no further losses. These observations led us to investigate further the chemical and structural changes occurring in the arene-loss processes, as well as to investigate their reversal upon exposure to arene vapours and more generally the behaviour of these materials upon exposure to arene or alcohol solvent vapours, and upon grinding, particularly in light of prior results involving reversible (alcohol) vapour uptake and structural conversions by the related ID coordination polymer system [Ag4(O2C(CF2)2CF3)4(TMP)3] (Libri et al., 2008[Libri, S., Mahler, M., Mínguez Espallargas, G., Singh, D. C. N. G., Soleimannejad, J., Adams, H., Burgard, M. D., Rath, N. P., Brunelli, M. & Brammer, L. (2008). Angew. Chem. Int. Ed. 47, 1693-1697.]; Vitórica-Yrezábal et al., 2013[Vitórica-Yrezábal, I. J., Mínguez Espallargas, G., Soleimannejad, J., Florence, A. J., Fletcher, A. J. & Brammer, L. (2013). Chem. Sci. 4, 696-708.]). A summary of the transformations identified is provided in Fig. 7[link].

[Figure 7]
Figure 7
Structural conversions for coordination polymers 1, 2a and 2b. Exposure of crystals to solvent vapour is indicated by the name of the solvent; heating is indicated by `Δ'. Where mixtures of products resulted rather than conversion to a single phase, the major/minor phases are noted. (The reversibility of toluene loss by 1-tol·tol was also examined by exposure of 2b to toluene vapour. No reaction was observed.)
3.2.1. Thermal transformations

Heating a powdered crystalline sample in a capillary during an in situ synchrotron X-ray powder diffraction experiment (Fig. 8[link]) enabled the loss of toluene from 1-tol·tol to be followed and confirmed the sole product to be two-dimensional coordination polymer 2b. Conversion of 1-tol·tol to 2b proceeds directly without any detected crystalline intermediate phases. Rietveld analysis indicated that the starting material had already undergone some toluene loss and conversion to 2b (48%) and indicated full conversion after approximately 100 min of heating, by which time the temperature had been increased to 373 K.

[Figure 8]
Figure 8
(a) In situ X-ray powder diffraction heating study showing the conversion of 1-tol·tol to 2b. Patterns were measured at intervals of approximately 20 min over a period of 2 h. The top pattern is calculated from single-crystal structure determination of 1-tol·tol. (b) Relative quantities of the two phases present determined by Rietveld refinement (see also Figs. S6–S11 ).

Solid-state conversion of 1-tol·tol to 2b involves breaking of Ag—π(toluene) bonds and the loss of all toluene coupled with the formation of new Ag—O bonds to form the more condensed material 2b. The process resembles that previously observed for conversion of a one-dimensional coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)3] to a two-dimensional layered coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)2] through loss of ligand TMP, which bridges between Ag4(O2C(CF2)2CF3)4(TMP)2 units, and the formation of new Ag—O bonds between the Ag4(O2C(CF2)2CF3)4(TMP)2 units (Vitórica-Yrezábal et al., 2013[Vitórica-Yrezábal, I. J., Mínguez Espallargas, G., Soleimannejad, J., Florence, A. J., Fletcher, A. J. & Brammer, L. (2013). Chem. Sci. 4, 696-708.]). In this previous case the transformation was found to be irreversible, and indeed exposure of 2b to toluene vapour did not result in conversion back to 1-tol·tol, but instead left the material unchanged. It is worth noting that phase-pure 2b could only be accessed through heating/solvent loss from 1-tol·tol. Arene loss from 1-tol-pxyl·tol·pxyl was examined in an ex situ diffraction study. A powder sample was allowed to air-dry for 30 min. Analysis by synchrotron X-ray powder diffraction confirmed partial transformation to 2b, but also the presence of an unidentified phase (Fig. S1 ).

In situ X-ray powder diffraction heating studies were also conducted on 1-pxyl (Fig. 9[link]) and 1-mxyl (Fig. S18 ). The samples were heated to 373 K while being monitored by powder diffraction. For 1-pyxl, Pawley and Rietveld fitting of the powder diffraction patterns indicated the formation of both polymorphs 2a and 2b as a result of loss of p-xylene, with polymorph 2a as the major product. Upon complete loss of p-xylene, after 40 min, only 2a and 2b are present, consistent with earlier TGA and elemental analysis results. Rietveld analysis indicated that 2a and 2b are present in the ratio 82:18 in the final product. For 1-mxyl, the starting material used was found to be already a mixture of 1-mxyl, 2a and 2b, suggesting some m-xylene loss prior to the initial diffraction measurement. Heating to 373 K resulted in complete conversion to a mixture of 2a and 2b after 4 min, with 2a again as the major phase, although data quality was sufficient only for Pawley fitting and therefore did not enable quantitative analysis of composition.

[Figure 9]
Figure 9
(a) In situ X-ray powder diffraction heating study showing conversion of 1-pxyl to a mixture of 2a and 2b. (b) Relative quantities of the two phases present determined by Rietveld refinement (see also Figs. S12–S17 ).

The thermal transformation of 1-pxyl (majority phase) and 1-mxyl to a one-dimensional coordination polymer architecture (coordination polymer 2a), consisting of orthogonally packed chains, similar to that of 1-pxyl contrasts with the sole product of heating of 1-tol·tol. The heating of 1-tol·tol, a two-dimensional coordination polymer propagated in one dimension by fused silver-carboxylate tetramers, pre-arranged such that they are co-planar, gives a like product, 2b. This indicates the role of pre-organization of the polymer chains on the polymorph products given, and prompted further investigation on potential inter-conversion between polymorph architectures 2a and 2b (Fig. 10[link]).

[Figure 10]
Figure 10
A comparison of the products of heating coordination polymers 1-tol·tol and 1-pxyl, suggesting the role of pre-organization on the structure of the products.
3.2.2. Vapour-assisted and mechanochemical transformations

Crystals of 1-tol·tol were dried and exposed to solvent vapour in attempts to facilitate exchange between arene guests, or the inclusion of alcohols in the silver carboxylate tetramer. These experiments were followed up (ex situ) by X-ray powder diffraction analysis to assess any phase changes.

Crystals of 1-tol·tol exposed to o-xylene vapours gave mixed-phase products of polymorphs 2a and 2b. When exposed to m-xylene, 1-tol·tol lost toluene and was converted to phase 2a, or when exposed to p-xylene, Pawley fitting of the resultant powder pattern indicated the presence of 2a and 2b, along with peaks consistent with 1-pxyl and a further unidentified phase (Fig. S28 ). These vapour-assisted transformations to give the two polymorphs 2a and 2b prompted an investigation into their interconversion. Mechanochemical conversion of 2a into 2b by dry grinding (Fig. S10 ) and by liquid-assisted grinding (LAG) using acetone (Fig. S11 ) was unsuccessful. Similarly, exposure of 2a to toluene vapour resulted in no change in composition. However, exposure of crystals of 2b to alcohol vapour (methanol, ethanol or 2-propanol) for a period of 2 weeks did facilitate a partial transformation to 2a.1 X-ray powder diffraction analysis of these samples (ex situ) and Rietveld fitting indicated that after 2 weeks the material comprised approximately 60% two-dimensional polymorph 2b and 40% one-dimensional polymorph 2a. The partial conversion of polymorph 2b to polymorph 2a may suggest that the conversion of 1-tol·tol to 2b by vapour-assisted means may continue on to polymorph 2a. However, a sample of 1-tol·tol gave only phase-pure 2b (Fig. S8 ) when exposed to ethanol vapour for 2 weeks. The tendency of vapour-assisted transformations of materials 1-tol·tol and 2b towards the one-dimensional polymorph 2a may indicate that 2a is thermodynamically the more stable material, but the measurements made are not able to provide full details of the mechanism.2

3.2.3. Arene separation

Separation of isomers of small molecules has been examined for a number of porous materials. Such separations have been demonstrated with zeolites (Bellat et al., 1995[Bellat, J.-P., Simonot-Grange, M.-H. & Jullian, S. (1995). Zeolites, 15, 124-130.]), but discrimination between isomers in adsorption has also been reported for MOFs (Alaerts et al., 2008[Alaerts, L., Maes, M., Giebeler, L., Jacobs, P. A., Martens, J. A., Denayer, J. F. M., Kirschhock, C. E. A. & De Vos, D. E. (2008). J. Am. Chem. Soc. 130, 14170-14178.]; Gu & Yan, 2010[Gu, Z. Y. & Yan, X. P. (2010). Angew. Chem. Int. Ed. 49, 1477-1480.]; Bárcia et al., 2011[Bárcia, P. S., Guimarães, D., Mendes, P. A. P., Silva, J. A. C., Guillerm, V., Chevreau, H., Serre, C. & Rodrigues, A. E. (2011). Microporous Mesoporous Mater. 139, 67-73.]; El Osta et al., 2012[El Osta, R., Carlin-Sinclair, A., Guillou, N., Walton, R. I., Vermoortele, F., Maes, M., de Vos, D. & Millange, F. (2012). Chem. Mater. 24, 2781-2791.]; Warren et al., 2014[Warren, J. E., Perkins, C. G., Jelfs, K. E., Boldrin, P., Chater, P. A., Miller, G. J., Manning, T. D., Briggs, M. E., Stylianou, K. C., Claridge, J. B. & Rosseinsky, M. J. (2014). Angew. Chem. Int. Ed. 53, 4592-4596.]) and crystalline clathrates (Lusi & Barbour, 2012[Lusi, M. & Barbour, L. J. (2012). Angew. Chem. Int. Ed. 51, 3928-3931.], 2013[Lusi, M. & Barbour, L. J. (2013). Chem. Commun. 49, 2634-2636.]). In the work reported here, it is clear that exposure to different arenes (toluene and xylenes) during synthesis of 1 leads to different structures being formed, depending on the preferred interactions of the arene with the coordination network. Furthermore, exposure to vapours of different xylene isomers leads to different solid-state transformations (e.g. for 1-tol.tol), indicating that there is discrimination between different arenes. However, since these observed processes do not involve simple adsorption/desorption of the arenes, it is less likely that these materials could be used in their current form for effective separation of xylenes.

4. Conclusions

We have reported a family of one-dimensional silver(I) perfluorocarboxylate coordination polymers constructed from {Ag4(O2C(CF2)2CF3)4(phenazine)2} building blocks linked through additional Ag–O bonds and containing η1-bound arenes, including an unusual μ:η1,η1-toluene ligand material 1-tol.tol. All can lose the entrapped and coordinated arene molecules either at ambient temperature or upon mild heating to convert to either a one-dimensional or two-dimensional coordination polymer, 2a and 2b, respectively, which are polymorphs of composition Ag4(O2C(CF2)2CF3)4(phen­azine)2. These transformations have been followed by in situ X-ray powder diffraction and TGA. Further exploration of these transformations has been undertaken by examining the exposure of the parent materials and the products to different solvent vapours and in some instances to mechanochemical force. The results, also verified by X-ray powder diffraction, illustrate the potential to harness chemical and structural transformations in the solid state involving labile metal–ligand bonds.

Supporting information

CCDC references: 1051373; 1051374; 1051375; 1051376; 1051377; 1051378

Crystal structure: contains datablocks 1-tol.tol, 1-pxyl, 1-mxyl, 2a, 2b, 1-tol-pxyl.tol.pxyl. DOI: 10.1107/S2052252515000147/bi5040sup1.cif

XRPD, NMR and TGA data. DOI: 10.1107/S2052252515000147/bi5040sup2.pdf


Computing details top

Data collection: Bruker APEX2 for 1-pxyl. Cell refinement: SAINT v7.60A (Bruker, 2009) for 1-tol.tol, (2a), (2b), 1-tol-pxyl.tol.pxyl; Bruker SAINT for 1-pxyl. Data reduction: SAINT v7.60A (Bruker, 2009) for 1-tol.tol, (2a), (2b), 1-tol-pxyl.tol.pxyl; Bruker SAINT for 1-pxyl; SAINT v7.68A (Bruker, 2009) for 1-mxyl. Program(s) used to solve structure: SHELXS (Sheldrick, 2008) for 1-tol.tol, (2a), (2b); SHELXS97 (Sheldrick, 2008) for 1-pxyl; ShelXT (Sheldrick, 2008) for 1-mxyl; XS (Sheldrick, 2008) for 1-tol-pxyl.tol.pxyl. Program(s) used to refine structure: XL (Sheldrick, 2008) for 1-tol.tol, 1-mxyl, (2a), (2b); SHELXL97 (Sheldrick, 2008) for 1-pxyl; olex2.refine (Bourhis et al., 2013) for 1-tol-pxyl.tol.pxyl. Molecular graphics: Olex2 (Dolomanov et al., 2009) for 1-tol.tol, 1-mxyl, (2a), (2b), 1-tol-pxyl.tol.pxyl; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. for 1-pxyl. Software used to prepare material for publication: Olex2 (Dolomanov et al., 2009) for 1-tol.tol, 1-mxyl, (2a), (2b), 1-tol-pxyl.tol.pxyl; O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341. for 1-pxyl.

(1-tol.tol) top
Crystal data top
C40H16Ag4F28N4O8·3(C7H8)Z = 1
Mr = 1920.45F(000) = 938
Triclinic, P1Dx = 1.948 Mg m−3
a = 10.6531 (7) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.2628 (7) ÅCell parameters from 9937 reflections
c = 14.4311 (10) Åθ = 2.4–27.1°
α = 72.401 (3)°µ = 1.32 mm−1
β = 86.598 (3)°T = 100 K
γ = 82.882 (3)°Plate, yellow
V = 1637.30 (19) Å30.41 × 0.14 × 0.11 mm
Data collection top
Bruker APEX-II CCD
diffractometer		6165 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.051
ϕ and ω scansθmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan
SADABS2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.0967 before and 0.0640 after correction. The Ratio of minimum to maximum transmission is 0.8435. The λ/2 correction factor is 0.0015.		h = −13→13
Tmin = 0.629, Tmax = 0.746k = −14→14
25299 measured reflectionsl = −18→16
7283 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.065 w = 1/[σ2(Fo2) + (0.065P)2 + 14.5417P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.167(Δ/σ)max < 0.001
S = 1.09Δρmax = 2.33 e Å−3
7283 reflectionsΔρmin = −1.73 e Å−3
422 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0027 (6)
Primary atom site location: structure-invariant direct methods
Crystal data top
C40H16Ag4F28N4O8·3(C7H8)γ = 82.882 (3)°
Mr = 1920.45V = 1637.30 (19) Å3
Triclinic, P1Z = 1
a = 10.6531 (7) ÅMo Kα radiation
b = 11.2628 (7) ŵ = 1.32 mm−1
c = 14.4311 (10) ÅT = 100 K
α = 72.401 (3)°0.41 × 0.14 × 0.11 mm
β = 86.598 (3)°
Data collection top
Bruker APEX-II CCD
diffractometer		7283 independent reflections
Absorption correction: multi-scan
SADABS2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.0967 before and 0.0640 after correction. The Ratio of minimum to maximum transmission is 0.8435. The λ/2 correction factor is 0.0015.		6165 reflections with I > 2σ(I)
Tmin = 0.629, Tmax = 0.746Rint = 0.051
25299 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0650 restraints
wR(F2) = 0.167H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.065P)2 + 14.5417P]
where P = (Fo2 + 2Fc2)/3
7283 reflectionsΔρmax = 2.33 e Å−3
422 parametersΔρmin = −1.73 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ag10.96487 (4)0.60543 (4)0.07877 (3)0.02121 (15)
Ag20.74680 (4)0.80646 (4)0.04403 (4)0.02437 (16)
N10.8224 (4)0.9992 (5)0.0034 (4)0.0200 (10)
C1020.8218 (5)1.0632 (6)0.0693 (4)0.0205 (12)
C1050.9035 (6)1.0447 (7)−0.2535 (5)0.0283 (14)
H1050.90131.0027−0.30130.034*
C1040.8620 (6)0.9905 (6)−0.1605 (5)0.0251 (13)
H1040.83220.9105−0.14410.030*
C1010.7755 (6)1.0117 (6)0.1668 (5)0.0244 (13)
H1010.74540.93170.18600.029*
C1000.7748 (6)1.0778 (7)0.2320 (5)0.0291 (14)
H1000.74601.04240.29700.035*
C1030.8629 (5)1.0530 (6)−0.0875 (4)0.0203 (12)
N21.0849 (5)0.7661 (5)0.0471 (4)0.0206 (10)
C2041.1364 (6)0.7499 (6)−0.1133 (5)0.0236 (13)
H2041.10650.6699−0.09650.028*
C2031.1322 (5)0.8165 (6)−0.0433 (4)0.0195 (12)
C2051.1833 (6)0.8016 (6)−0.2040 (5)0.0266 (14)
H2051.18830.7558−0.24980.032*
C2021.0901 (5)0.8272 (6)0.1140 (4)0.0192 (11)
C2001.0501 (7)0.8366 (7)0.2788 (5)0.0297 (14)
H2001.02060.80060.34340.036*
C2011.0471 (6)0.7732 (6)0.2121 (5)0.0253 (13)
H2011.01660.69340.23070.030*
O1A0.7244 (5)0.6925 (4)0.2018 (4)0.0321 (11)
O1B0.8478 (4)0.5114 (4)0.2112 (4)0.0299 (10)
C20.712 (3)0.535 (3)0.347 (2)0.029 (8)*0.469 (9)
F2A0.5919 (11)0.5841 (12)0.3575 (8)0.034 (3)*0.469 (9)
F2B0.6988 (11)0.3963 (10)0.3566 (8)0.038 (3)*0.469 (9)
C30.7956 (14)0.5263 (16)0.4253 (10)0.025 (3)*0.469 (9)
F3B0.8276 (12)0.6440 (11)0.4043 (8)0.054 (3)*0.469 (9)
F3A0.9053 (11)0.4558 (11)0.4250 (9)0.058 (3)*0.469 (9)
C40.7439 (18)0.483 (2)0.5304 (14)0.036 (5)*0.469 (9)
F4A0.6241 (11)0.5183 (13)0.5429 (8)0.051 (3)*0.469 (9)
F4B0.7965 (15)0.4043 (15)0.5559 (11)0.076 (4)*0.469 (9)
F4C0.7910 (13)0.5866 (13)0.5765 (9)0.066 (4)*0.469 (9)
C2'0.711 (2)0.517 (2)0.3444 (16)0.022 (6)*0.531 (9)
F2Y0.5894 (9)0.5569 (10)0.3481 (7)0.027 (2)*0.531 (9)
F2Z0.7321 (10)0.4027 (9)0.3756 (7)0.035 (2)*0.531 (9)
C3'0.7718 (15)0.5810 (16)0.4179 (11)0.034 (3)*0.531 (9)
F3Z0.9006 (10)0.5649 (10)0.4046 (7)0.053 (3)*0.531 (9)
F3Y0.7430 (11)0.7029 (10)0.3976 (8)0.059 (3)*0.531 (9)
C4'0.7440 (15)0.5256 (18)0.5249 (12)0.034 (4)*0.531 (9)
F4Z0.8298 (10)0.4907 (10)0.5895 (8)0.058 (3)*0.531 (9)
F4Y0.7017 (13)0.3835 (12)0.5536 (9)0.073 (4)*0.531 (9)
F4X0.6399 (10)0.5767 (12)0.5400 (8)0.056 (3)*0.531 (9)
O11A0.7273 (4)0.7257 (4)−0.0845 (4)0.0300 (10)
O11B0.8785 (4)0.5631 (4)−0.0531 (3)0.0264 (10)
C110.7889 (6)0.6323 (6)−0.0985 (4)0.0203 (12)*
C120.7486 (6)0.6000 (6)−0.1894 (5)0.0241 (13)*
F12A0.7128 (4)0.7053 (4)−0.2615 (3)0.0358 (9)*
F12B0.8472 (4)0.5373 (4)−0.2249 (3)0.0315 (9)*
C130.6392 (7)0.5154 (6)−0.1695 (5)0.0289 (14)*
F13B0.6670 (4)0.4186 (4)−0.0883 (3)0.0394 (10)*
C140.5059 (7)0.5761 (7)−0.1537 (5)0.0351 (16)*
F13A0.6348 (5)0.4671 (5)−0.2435 (4)0.0537 (13)*
F14A0.5007 (5)0.6254 (5)−0.0826 (4)0.0532 (12)*
F14B0.4279 (5)0.4871 (5)−0.1324 (4)0.0518 (12)*
F14C0.4677 (7)0.6596 (6)−0.2356 (5)0.0776 (18)*
C510.4944 (6)0.8722 (7)0.0177 (6)0.0344 (16)
H510.49070.78500.02950.041*
C500.5190 (6)0.9462 (7)−0.0749 (6)0.0329 (16)
H500.53210.9091−0.12620.040*
C520.4748 (6)0.9244 (7)0.0954 (6)0.0331 (15)
H520.45800.87370.15960.040*0.5
C530.4442 (14)0.8510 (17)0.1951 (14)0.050 (5)0.5
H53A0.40620.77660.19380.076*0.5
H53B0.38410.90230.22530.076*0.5
H53C0.52170.82510.23280.076*0.5
C600.4763 (11)0.9212 (13)0.4467 (8)0.077 (4)
H600.45930.86650.41130.092*0.5
C610.4998 (12)0.8755 (12)0.5455 (8)0.079 (4)
H610.50060.78810.57680.094*
C620.5216 (12)0.9514 (12)0.5993 (8)0.075 (4)
H620.53520.91770.66720.091*
C630.455 (3)0.847 (3)0.3874 (19)0.097 (9)0.5
H63A0.38030.88530.34810.146*0.5
H63B0.44100.76290.42830.146*0.5
H63C0.52890.84230.34440.146*0.5
C70−0.1021 (16)0.086 (2)0.4706 (9)0.100 (6)
H70−0.17120.14900.44920.120*
C710.024 (2)0.123 (2)0.4629 (10)0.123 (8)
H710.03520.20950.43690.148*0.5
C720.031 (3)0.235 (3)0.4291 (18)0.089 (9)0.5
H72A−0.04320.28080.45120.133*0.5
H72B0.03210.25720.35800.133*0.5
H72C0.10800.25570.45080.133*0.5
C730.1260 (19)0.040 (2)0.4912 (11)0.129 (8)
H730.20910.06400.48580.154*
C10.7663 (6)0.5824 (6)0.2403 (5)0.0241 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0169 (2)0.0206 (2)0.0284 (3)−0.00052 (17)−0.00182 (17)−0.01100 (19)
Ag20.0220 (3)0.0193 (3)0.0320 (3)−0.00102 (18)−0.00279 (19)−0.00799 (19)
N10.013 (2)0.021 (2)0.025 (3)0.0025 (18)−0.0050 (19)−0.007 (2)
C1020.010 (2)0.025 (3)0.027 (3)0.005 (2)−0.007 (2)−0.009 (2)
C1050.029 (3)0.033 (4)0.029 (3)−0.002 (3)−0.001 (3)−0.018 (3)
C1040.019 (3)0.030 (3)0.031 (3)−0.005 (2)−0.002 (2)−0.015 (3)
C1010.021 (3)0.026 (3)0.027 (3)−0.004 (2)0.000 (2)−0.008 (3)
C1000.024 (3)0.038 (4)0.025 (3)−0.001 (3)0.001 (3)−0.009 (3)
C1030.010 (3)0.021 (3)0.029 (3)0.005 (2)−0.007 (2)−0.008 (2)
N20.017 (2)0.019 (2)0.027 (3)0.0021 (19)−0.004 (2)−0.010 (2)
C2040.019 (3)0.017 (3)0.037 (4)0.001 (2)−0.006 (3)−0.011 (3)
C2030.014 (3)0.021 (3)0.024 (3)0.005 (2)−0.009 (2)−0.009 (2)
C2050.026 (3)0.034 (4)0.023 (3)0.005 (3)−0.003 (2)−0.018 (3)
C2020.012 (3)0.022 (3)0.024 (3)0.004 (2)−0.005 (2)−0.009 (2)
C2000.032 (4)0.033 (4)0.026 (3)−0.005 (3)0.001 (3)−0.010 (3)
C2010.023 (3)0.025 (3)0.028 (3)−0.003 (2)−0.003 (2)−0.007 (3)
O1A0.033 (3)0.030 (2)0.032 (3)0.003 (2)−0.003 (2)−0.008 (2)
O1B0.024 (2)0.028 (2)0.035 (3)−0.0007 (18)0.0032 (19)−0.007 (2)
O11A0.026 (2)0.025 (2)0.043 (3)0.0048 (18)−0.010 (2)−0.016 (2)
O11B0.023 (2)0.029 (2)0.031 (2)0.0119 (18)−0.0122 (18)−0.0182 (19)
C510.020 (3)0.029 (3)0.058 (5)0.007 (3)−0.013 (3)−0.019 (3)
C500.017 (3)0.045 (4)0.043 (4)0.009 (3)−0.012 (3)−0.024 (3)
C520.015 (3)0.040 (4)0.044 (4)0.005 (3)−0.003 (3)−0.014 (3)
C530.019 (7)0.048 (9)0.066 (11)0.011 (6)0.005 (7)0.004 (8)
C600.067 (7)0.095 (9)0.059 (7)0.030 (6)−0.005 (5)−0.025 (6)
C610.092 (9)0.073 (8)0.051 (6)0.024 (7)0.004 (6)−0.003 (6)
C620.077 (8)0.087 (8)0.042 (5)0.023 (6)−0.001 (5)−0.002 (6)
C630.14 (3)0.088 (19)0.070 (16)0.019 (18)−0.004 (16)−0.038 (14)
C700.095 (11)0.156 (17)0.050 (7)0.051 (11)−0.027 (7)−0.052 (9)
C710.19 (2)0.130 (15)0.050 (8)0.052 (15)−0.036 (11)−0.053 (9)
C720.076 (17)0.13 (3)0.051 (14)0.006 (18)0.000 (12)−0.028 (16)
C730.152 (17)0.18 (2)0.053 (8)0.066 (15)−0.042 (9)−0.063 (11)
Geometric parameters (Å, º) top
Ag1—Ag22.9871 (6)C4—F4C1.65 (3)
Ag1—N22.263 (5)C2'—F2Y1.33 (2)
Ag1—O1B2.269 (5)C2'—F2Z1.22 (2)
Ag1—O11B2.358 (4)C2'—C3'1.65 (3)
Ag1—O11Bi2.467 (4)C2'—C11.57 (2)
Ag2—N12.305 (5)C3'—F3Z1.372 (19)
Ag2—O1A2.265 (5)C3'—F3Y1.31 (2)
Ag2—O11A2.329 (5)C3'—C4'1.51 (2)
N1—C1021.354 (8)C4'—F4Z1.284 (19)
N1—C1031.339 (8)C4'—F4Y1.64 (2)
C102—C1011.433 (9)C4'—F4X1.224 (19)
C102—C203ii1.432 (9)O11A—C111.233 (7)
C105—C1041.366 (10)O11B—Ag1i2.467 (4)
C105—C200ii1.417 (10)O11B—C111.238 (7)
C104—C1031.434 (9)C11—C121.559 (8)
C101—C1001.364 (9)C12—F12A1.351 (7)
C100—C205ii1.416 (10)C12—F12B1.354 (7)
C103—C202ii1.432 (8)C12—C131.555 (9)
N2—C2031.350 (8)C13—F13B1.355 (8)
N2—C2021.352 (8)C13—C141.533 (10)
C204—C2031.426 (8)C13—F13A1.343 (8)
C204—C2051.354 (9)C14—F14A1.302 (9)
C203—C102ii1.432 (9)C14—F14B1.334 (9)
C205—C100ii1.416 (10)C14—F14C1.318 (10)
C202—C103ii1.432 (8)C51—C501.374 (11)
C202—C2011.433 (9)C51—C521.409 (10)
C200—C105ii1.417 (10)C50—C52iii1.406 (11)
C200—C2011.365 (9)C52—C50iii1.406 (11)
O1A—C11.233 (8)C52—C531.467 (19)
O1B—C11.248 (8)C60—C611.389 (16)
C2—F2A1.35 (3)C60—C62iv1.389 (18)
C2—F2B1.55 (3)C60—C631.41 (3)
C2—C31.46 (3)C61—C621.364 (18)
C2—C11.56 (3)C62—C60iv1.389 (18)
C3—F3B1.35 (2)C70—C711.44 (3)
C3—F3A1.33 (2)C70—C73v1.41 (3)
C3—C41.54 (2)C71—C721.21 (3)
C4—F4A1.31 (2)C71—C731.34 (2)
C4—F4B0.97 (2)C73—C70v1.41 (3)
N2—Ag1—Ag284.65 (12)F2Y—C2'—C1108.6 (15)
N2—Ag1—O1B132.37 (18)F2Z—C2'—F2Y112.5 (18)
N2—Ag1—O11Bi101.06 (17)F2Z—C2'—C3'109.6 (16)
N2—Ag1—O11B118.48 (18)F2Z—C2'—C1117.6 (17)
O1B—Ag1—Ag283.74 (12)C1—C2'—C3'105.2 (14)
O1B—Ag1—O11B105.39 (17)F3Z—C3'—C2'106.3 (13)
O1B—Ag1—O11Bi105.18 (16)F3Z—C3'—C4'107.1 (12)
O11B—Ag1—Ag282.26 (10)F3Y—C3'—C2'114.9 (14)
O11Bi—Ag1—Ag2160.24 (10)F3Y—C3'—F3Z104.7 (13)
O11B—Ag1—O11Bi78.39 (15)F3Y—C3'—C4'106.8 (13)
N1—Ag2—Ag1109.23 (12)C4'—C3'—C2'116.1 (14)
N1—Ag2—O11A115.84 (18)C3'—C4'—F4Y113.7 (13)
O1A—Ag2—Ag175.06 (12)F4Z—C4'—C3'123.5 (14)
O1A—Ag2—N1120.70 (18)F4Z—C4'—F4Y91.6 (12)
O1A—Ag2—O11A122.75 (18)F4X—C4'—C3'105.5 (14)
O11A—Ag2—Ag179.12 (11)F4X—C4'—F4Z121.8 (15)
C102—N1—Ag2121.1 (4)F4X—C4'—F4Y96.0 (13)
C103—N1—Ag2120.4 (4)C11—O11A—Ag2126.9 (4)
C103—N1—C102118.4 (5)Ag1—O11B—Ag1i101.61 (15)
N1—C102—C101120.7 (6)C11—O11B—Ag1i136.1 (4)
N1—C102—C203ii120.8 (6)C11—O11B—Ag1121.2 (4)
C203ii—C102—C101118.5 (5)O11A—C11—O11B130.0 (6)
C104—C105—C200ii120.3 (6)O11A—C11—C12114.2 (5)
C105—C104—C103120.8 (6)O11B—C11—C12115.8 (5)
C100—C101—C102119.9 (6)F12A—C12—C11110.8 (5)
C101—C100—C205ii120.7 (6)F12A—C12—F12B107.0 (5)
N1—C103—C104120.5 (6)F12A—C12—C13107.8 (5)
N1—C103—C202ii121.1 (5)F12B—C12—C11110.4 (5)
C202ii—C103—C104118.4 (6)F12B—C12—C13106.0 (5)
C203—N2—Ag1120.9 (4)C13—C12—C11114.4 (5)
C203—N2—C202118.6 (5)F13B—C13—C12107.8 (5)
C202—N2—Ag1119.4 (4)F13B—C13—C14107.1 (6)
C205—C204—C203119.5 (6)C14—C13—C12117.3 (6)
N2—C203—C102ii120.4 (5)F13A—C13—C12109.1 (5)
N2—C203—C204119.9 (6)F13A—C13—F13B107.6 (6)
C204—C203—C102ii119.7 (6)F13A—C13—C14107.7 (6)
C204—C205—C100ii121.6 (6)F14A—C14—C13112.2 (6)
C103ii—C202—C201119.3 (5)F14A—C14—F14B108.6 (6)
N2—C202—C103ii120.5 (5)F14A—C14—F14C111.5 (7)
N2—C202—C201120.2 (5)F14B—C14—C13107.9 (6)
C201—C200—C105ii121.3 (6)F14C—C14—C13109.3 (6)
C200—C201—C202119.9 (6)F14C—C14—F14B107.2 (7)
C1—O1A—Ag2127.5 (4)C50—C51—C52120.6 (7)
C1—O1B—Ag1115.7 (4)C51—C50—C52iii121.4 (7)
F2A—C2—F2B103.4 (18)C51—C52—C53123.1 (10)
F2A—C2—C3115 (2)C50iii—C52—C51118.0 (7)
F2A—C2—C1113.3 (19)C50iii—C52—C53118.9 (10)
F2B—C2—C1101.8 (16)C61—C60—C62iv118.6 (13)
C3—C2—F2B103.5 (18)C61—C60—C63124.9 (17)
C3—C2—C1117.3 (19)C62iv—C60—C63116.4 (16)
C2—C3—C4118.3 (16)C62—C61—C60122.5 (12)
F3B—C3—C2103.1 (16)C61—C62—C60iv119.0 (11)
F3B—C3—C4110.2 (14)C73v—C70—C71122.1 (16)
F3A—C3—C2114.9 (16)C72—C71—C70115 (2)
F3A—C3—F3B104.3 (12)C72—C71—C73123 (3)
F3A—C3—C4105.2 (14)C73—C71—C70122 (2)
C3—C4—F4C101.6 (14)C71—C73—C70v116 (2)
F4A—C4—C3115.5 (16)O1A—C1—O1B130.9 (6)
F4A—C4—F4C92.9 (15)O1A—C1—C2110.5 (11)
F4B—C4—C3101.2 (19)O1A—C1—C2'116.8 (10)
F4B—C4—F4A133 (2)O1B—C1—C2118.3 (11)
F4B—C4—F4C108.0 (19)O1B—C1—C2'112.3 (9)
F2Y—C2'—C3'102.0 (16)
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+2, −y+2, −z; (iii) −x+1, −y+2, −z; (iv) −x+1, −y+2, −z+1; (v) −x, −y, −z+1.
(1-pxyl) top
Crystal data top
C20H8Ag2F14N2O4·C8H10F(000) = 1808
Mr = 928.18Dx = 1.992 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 11.1146 (3) ÅCell parameters from 6610 reflections
b = 22.7107 (8) Åθ = 2.7–25.7°
c = 13.2046 (4) ŵ = 1.39 mm−1
β = 111.785 (2)°T = 100 K
V = 3095.07 (17) Å3Plate, yellow
Z = 40.25 × 0.06 × 0.02 mm
Data collection top
Bruker APEX-II CCD
diffractometer		7075 independent reflections
Radiation source: fine-focus sealed tube5377 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.051
ϕ and ω scansθmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan
SADABS		h = −14→14
Tmin = 0.723, Tmax = 0.973k = −29→28
26785 measured reflectionsl = −11→17
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0689P)2]
where P = (Fo2 + 2Fc2)/3
7075 reflections(Δ/σ)max = 0.001
453 parametersΔρmax = 1.07 e Å−3
0 restraintsΔρmin = −1.27 e Å−3
Crystal data top
C20H8Ag2F14N2O4·C8H10V = 3095.07 (17) Å3
Mr = 928.18Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.1146 (3) ŵ = 1.39 mm−1
b = 22.7107 (8) ÅT = 100 K
c = 13.2046 (4) Å0.25 × 0.06 × 0.02 mm
β = 111.785 (2)°
Data collection top
Bruker APEX-II CCD
diffractometer		7075 independent reflections
Absorption correction: multi-scan
SADABS		5377 reflections with I > 2σ(I)
Tmin = 0.723, Tmax = 0.973Rint = 0.051
26785 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.122H-atom parameters constrained
S = 1.05Δρmax = 1.07 e Å−3
7075 reflectionsΔρmin = −1.27 e Å−3
453 parameters
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
Ag10.66614 (3)0.116999 (15)0.90513 (3)0.02674 (11)
Ag20.88891 (3)0.042561 (14)1.04743 (3)0.02537 (11)
O1A0.9705 (3)0.13297 (14)1.1068 (3)0.0312 (7)
O1B0.7739 (3)0.17609 (14)1.0506 (2)0.0333 (7)
C10.8907 (4)0.17241 (19)1.1041 (3)0.0254 (9)
C20.9517 (4)0.2237 (2)1.1856 (3)0.0280 (9)
F2A1.0445 (3)0.25025 (14)1.1596 (2)0.0566 (9)
F2B0.8624 (3)0.26464 (15)1.1808 (3)0.0673 (11)
C31.0148 (5)0.2030 (2)1.3050 (4)0.0399 (12)
F3A0.9366 (4)0.16496 (18)1.3254 (3)0.0820 (14)
F3B1.1255 (3)0.17528 (16)1.3181 (2)0.0643 (10)
C41.0483 (5)0.2520 (3)1.3911 (4)0.0450 (13)
F4A1.1135 (3)0.29454 (15)1.3676 (2)0.0552 (8)
F4B0.9453 (3)0.2730 (2)1.4016 (3)0.1092 (19)
F4C1.1243 (4)0.23001 (18)1.4866 (3)0.0702 (11)
O11A0.9204 (3)0.02159 (14)0.8838 (2)0.0320 (7)
O11B0.7465 (3)0.07380 (15)0.7830 (2)0.0346 (8)
C110.8356 (4)0.03843 (19)0.7971 (3)0.0262 (9)
C120.8338 (5)0.0089 (2)0.6899 (4)0.0371 (11)
F12A0.9267 (3)−0.03270 (14)0.7111 (2)0.0520 (8)
F12B0.7176 (3)−0.01910 (18)0.6432 (3)0.0690 (10)
C130.8465 (5)0.0484 (3)0.6010 (4)0.0470 (14)
F13A0.8369 (4)0.01506 (17)0.5127 (2)0.0663 (10)
F13B0.7516 (4)0.08904 (19)0.5703 (3)0.0757 (12)
C140.9729 (7)0.0816 (3)0.6332 (5)0.0587 (16)
F14A0.9707 (5)0.11881 (19)0.5539 (4)0.0948 (15)
F14B0.9938 (4)0.11178 (16)0.7241 (3)0.0689 (11)
F14C1.0738 (4)0.04542 (19)0.6485 (4)0.0802 (12)
N10.7412 (3)−0.01523 (16)1.0797 (3)0.0232 (7)
C1050.7189 (4)−0.1414 (2)0.9045 (3)0.0281 (9)
H1050.7646−0.15840.86350.034*
C1020.6808 (4)0.00515 (18)1.1442 (3)0.0219 (8)
C1000.6683 (4)0.0776 (2)1.2734 (4)0.0304 (10)
H1000.70080.11191.31610.036*
C1040.7626 (4)−0.0912 (2)0.9600 (3)0.0260 (9)
H1040.8374−0.07240.95640.031*
C1030.6972 (4)−0.06603 (18)1.0240 (3)0.0223 (8)
C1010.7285 (4)0.0565 (2)1.2082 (4)0.0282 (9)
H1010.80270.07611.20540.034*
N20.4799 (3)0.07248 (15)0.9109 (3)0.0223 (7)
C2010.4610 (4)0.1466 (2)1.0338 (3)0.0269 (9)
H2010.53680.16571.03340.032*
C2030.4313 (4)0.02373 (18)0.8511 (3)0.0214 (8)
C2040.4916 (4)0.0001 (2)0.7819 (3)0.0261 (9)
H2040.56620.01870.77780.031*
C2020.4167 (3)0.09443 (18)0.9719 (3)0.0206 (8)
C2000.3953 (4)0.16938 (19)1.0938 (3)0.0254 (9)
H2000.42580.20431.13490.031*
C2050.4426 (4)−0.0489 (2)0.7218 (4)0.0309 (10)
H2050.4834−0.06410.67560.037*
C560.5642 (7)0.2873 (3)0.9283 (5)0.0647 (17)
H56A0.65850.28360.96390.097*
H56B0.52390.28020.98180.097*
H56C0.54230.32700.89810.097*
C570.3694 (8)0.1162 (3)0.5768 (5)0.079 (2)
H57A0.30400.09120.58880.119*
H57B0.44110.09170.57500.119*
H57C0.33030.13710.50730.119*
C530.3413 (5)0.1845 (3)0.7168 (4)0.0461 (14)
H530.25270.17330.69250.055*
C500.5950 (4)0.2180 (2)0.7895 (4)0.0378 (12)
H500.68370.22920.81530.045*
C510.5496 (5)0.1783 (2)0.7064 (4)0.0418 (13)
H510.60670.16270.67460.050*
C520.4194 (5)0.1599 (2)0.6673 (4)0.0436 (13)
C540.3878 (5)0.2245 (2)0.7992 (4)0.0412 (12)
H540.33100.24020.83120.049*
C550.5146 (5)0.2425 (2)0.8371 (4)0.0386 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.01975 (16)0.0317 (2)0.02876 (19)−0.00232 (12)0.00900 (13)−0.00283 (14)
Ag20.02144 (16)0.0269 (2)0.03035 (19)−0.00039 (12)0.01263 (13)−0.00120 (13)
O1A0.0271 (15)0.0278 (17)0.0384 (18)−0.0031 (13)0.0119 (13)−0.0036 (14)
O1B0.0240 (15)0.0379 (19)0.0324 (17)−0.0014 (13)0.0041 (13)−0.0057 (14)
C10.028 (2)0.025 (2)0.026 (2)−0.0055 (17)0.0128 (17)−0.0022 (17)
C20.0241 (19)0.030 (3)0.030 (2)−0.0054 (17)0.0103 (17)−0.0063 (19)
F2A0.079 (2)0.059 (2)0.0423 (17)−0.0437 (18)0.0343 (16)−0.0155 (15)
F2B0.0506 (18)0.048 (2)0.071 (2)0.0188 (15)−0.0143 (16)−0.0293 (17)
C30.042 (3)0.051 (3)0.031 (3)−0.019 (2)0.020 (2)−0.009 (2)
F3A0.114 (3)0.097 (3)0.0415 (19)−0.072 (3)0.037 (2)−0.0137 (19)
F3B0.061 (2)0.063 (2)0.0461 (19)0.0202 (17)−0.0062 (16)−0.0088 (16)
C40.040 (3)0.063 (4)0.032 (3)−0.006 (3)0.013 (2)−0.012 (3)
F4A0.062 (2)0.055 (2)0.0439 (18)−0.0191 (17)0.0132 (15)−0.0168 (15)
F4B0.043 (2)0.193 (5)0.092 (3)−0.006 (3)0.0267 (19)−0.097 (3)
F4C0.080 (2)0.089 (3)0.0318 (18)−0.013 (2)0.0094 (16)−0.0063 (18)
O11A0.0314 (15)0.0378 (19)0.0285 (17)0.0108 (14)0.0130 (13)0.0053 (14)
O11B0.0261 (15)0.045 (2)0.0360 (18)0.0120 (14)0.0157 (13)0.0032 (15)
C110.027 (2)0.029 (2)0.027 (2)−0.0027 (17)0.0158 (17)0.0003 (18)
C120.036 (2)0.044 (3)0.035 (3)0.004 (2)0.018 (2)−0.001 (2)
F12A0.074 (2)0.049 (2)0.0410 (17)0.0284 (16)0.0298 (16)0.0044 (14)
F12B0.064 (2)0.090 (3)0.052 (2)−0.028 (2)0.0206 (17)−0.034 (2)
C130.050 (3)0.057 (4)0.038 (3)0.021 (3)0.022 (2)0.004 (3)
F13A0.085 (2)0.082 (3)0.0302 (17)0.007 (2)0.0192 (16)−0.0108 (17)
F13B0.080 (2)0.103 (3)0.051 (2)0.055 (2)0.0321 (18)0.036 (2)
C140.075 (4)0.054 (4)0.055 (4)−0.005 (3)0.033 (3)0.011 (3)
F14A0.128 (4)0.087 (3)0.091 (3)−0.008 (3)0.066 (3)0.033 (2)
F14B0.097 (3)0.059 (2)0.066 (2)−0.036 (2)0.047 (2)−0.0163 (18)
F14C0.052 (2)0.094 (3)0.102 (3)0.007 (2)0.038 (2)0.009 (2)
N10.0206 (15)0.027 (2)0.0242 (18)0.0012 (14)0.0104 (13)0.0018 (15)
C1050.027 (2)0.032 (3)0.028 (2)0.0035 (18)0.0144 (17)0.0001 (19)
C1020.0213 (18)0.022 (2)0.022 (2)0.0004 (16)0.0075 (15)0.0023 (16)
C1000.034 (2)0.028 (3)0.030 (2)−0.0008 (18)0.0120 (18)−0.0046 (19)
C1040.0195 (18)0.034 (3)0.027 (2)0.0014 (17)0.0122 (16)0.0028 (19)
C1030.0178 (17)0.024 (2)0.024 (2)0.0002 (15)0.0060 (15)0.0027 (17)
C1010.027 (2)0.028 (2)0.031 (2)−0.0047 (18)0.0122 (17)−0.0032 (18)
N20.0192 (15)0.026 (2)0.0221 (17)0.0010 (13)0.0078 (13)0.0001 (14)
C2010.0235 (19)0.031 (2)0.028 (2)−0.0028 (17)0.0110 (17)−0.0020 (18)
C2030.0208 (18)0.026 (2)0.0183 (19)0.0023 (16)0.0078 (15)0.0018 (16)
C2040.0251 (19)0.031 (3)0.028 (2)−0.0015 (17)0.0166 (17)−0.0009 (18)
C2020.0186 (17)0.020 (2)0.022 (2)0.0025 (15)0.0052 (14)0.0040 (16)
C2000.026 (2)0.024 (2)0.025 (2)−0.0006 (16)0.0087 (16)−0.0040 (17)
C2050.033 (2)0.036 (3)0.028 (2)0.0001 (19)0.0152 (18)−0.0052 (19)
C560.097 (5)0.048 (4)0.047 (4)−0.001 (4)0.025 (3)0.003 (3)
C570.115 (6)0.050 (4)0.048 (4)0.003 (4)0.002 (4)0.002 (3)
C530.025 (2)0.055 (4)0.051 (3)0.003 (2)0.006 (2)0.023 (3)
C500.027 (2)0.051 (3)0.036 (3)0.005 (2)0.0134 (19)0.019 (2)
C510.045 (3)0.049 (3)0.037 (3)0.024 (2)0.022 (2)0.022 (2)
C520.055 (3)0.038 (3)0.030 (3)0.007 (2)0.007 (2)0.008 (2)
C540.039 (3)0.049 (3)0.043 (3)0.017 (2)0.024 (2)0.019 (2)
C550.041 (3)0.039 (3)0.034 (3)0.009 (2)0.012 (2)0.016 (2)
Geometric parameters (Å, º) top
Ag1—Ag23.0110 (4)C102—C203ii1.430 (5)
Ag1—O1B2.284 (3)C100—H1000.9500
Ag1—O11B2.330 (3)C100—C1011.360 (6)
Ag1—N22.330 (3)C100—C205ii1.417 (6)
Ag1—C502.706 (5)C104—H1040.9500
Ag2—O1A2.264 (3)C104—C1031.424 (6)
Ag2—O11A2.362 (3)C103—C202ii1.439 (5)
Ag2—O11Ai2.452 (3)C101—H1010.9500
Ag2—N12.262 (3)N2—C2031.351 (5)
O1A—C11.252 (5)N2—C2021.346 (5)
O1B—C11.229 (5)C201—H2010.9500
C1—C21.560 (6)C201—C2021.419 (6)
C2—F2A1.344 (5)C201—C2001.363 (6)
C2—F2B1.344 (5)C203—C102ii1.430 (5)
C2—C31.542 (7)C203—C2041.423 (5)
C3—F3A1.323 (5)C204—H2040.9500
C3—F3B1.335 (6)C204—C2051.358 (6)
C3—C41.534 (7)C202—C103ii1.439 (5)
C4—F4A1.312 (6)C200—C105ii1.428 (6)
C4—F4B1.294 (6)C200—H2000.9500
C4—F4C1.328 (6)C205—C100ii1.417 (6)
O11A—Ag2i2.452 (3)C205—H2050.9500
O11A—C111.243 (5)C56—H56A0.9800
O11B—C111.234 (5)C56—H56B0.9800
C11—C121.560 (6)C56—H56C0.9800
C12—F12A1.350 (5)C56—C551.514 (8)
C12—F12B1.365 (6)C57—H57A0.9800
C12—C131.525 (7)C57—H57B0.9800
C13—F13A1.361 (6)C57—H57C0.9800
C13—F13B1.346 (6)C57—C521.492 (8)
C13—C141.511 (9)C53—H530.9500
C14—F14A1.338 (7)C53—C521.383 (8)
C14—F14B1.326 (7)C53—C541.363 (8)
C14—F14C1.343 (7)C50—H500.9500
N1—C1021.347 (5)C50—C511.365 (8)
N1—C1031.358 (5)C50—C551.386 (7)
C105—H1050.9500C51—H510.9500
C105—C1041.345 (6)C51—C521.407 (7)
C105—C200ii1.428 (6)C54—H540.9500
C102—C1011.422 (6)C54—C551.371 (7)
O1B—Ag1—Ag275.64 (8)C104—C105—C200ii120.8 (4)
O1B—Ag1—O11B127.83 (11)C200ii—C105—H105119.6
O1B—Ag1—N2114.97 (11)N1—C102—C101119.6 (4)
O1B—Ag1—C5085.90 (14)N1—C102—C203ii121.1 (4)
O11B—Ag1—Ag275.99 (7)C101—C102—C203ii119.2 (4)
O11B—Ag1—N2114.41 (12)C101—C100—H100119.8
O11B—Ag1—C5094.21 (13)C101—C100—C205ii120.4 (4)
N2—Ag1—Ag2105.70 (8)C205ii—C100—H100119.8
N2—Ag1—C50108.02 (13)C105—C104—H104119.9
C50—Ag1—Ag2145.94 (10)C105—C104—C103120.2 (4)
O1A—Ag2—Ag180.66 (8)C103—C104—H104119.9
O1A—Ag2—O11Ai103.34 (11)N1—C103—C104120.1 (4)
O1A—Ag2—O11A108.87 (11)N1—C103—C202ii120.4 (4)
O11A—Ag2—Ag184.78 (7)C104—C103—C202ii119.5 (4)
O11Ai—Ag2—Ag1164.24 (7)C102—C101—H101119.9
O11A—Ag2—O11Ai79.50 (11)C100—C101—C102120.3 (4)
N1—Ag2—Ag187.54 (8)C100—C101—H101119.9
N1—Ag2—O1A133.34 (12)C203—N2—Ag1120.2 (2)
N1—Ag2—O11A114.79 (12)C202—N2—Ag1121.8 (3)
N1—Ag2—O11Ai100.00 (11)C202—N2—C203118.0 (3)
C1—O1A—Ag2116.8 (3)C202—C201—H201119.8
C1—O1B—Ag1123.8 (3)C200—C201—H201119.8
O1A—C1—C2113.2 (4)C200—C201—C202120.3 (4)
O1B—C1—O1A130.6 (4)N2—C203—C102ii121.1 (3)
O1B—C1—C2116.2 (4)N2—C203—C204120.2 (3)
F2A—C2—C1109.7 (3)C204—C203—C102ii118.8 (4)
F2A—C2—C3107.3 (3)C203—C204—H204119.9
F2B—C2—C1111.1 (3)C205—C204—C203120.1 (4)
F2B—C2—F2A107.6 (4)C205—C204—H204119.9
F2B—C2—C3107.8 (4)N2—C202—C103ii121.2 (4)
C3—C2—C1113.2 (4)N2—C202—C201120.5 (4)
F3A—C3—C2108.9 (4)C201—C202—C103ii118.3 (4)
F3A—C3—F3B108.0 (5)C105ii—C200—H200119.6
F3A—C3—C4108.6 (4)C201—C200—C105ii120.8 (4)
F3B—C3—C2108.9 (4)C201—C200—H200119.6
F3B—C3—C4106.7 (4)C100ii—C205—H205119.4
C4—C3—C2115.5 (5)C204—C205—C100ii121.2 (4)
F4A—C4—C3111.2 (4)C204—C205—H205119.4
F4A—C4—F4C106.8 (4)H56A—C56—H56B109.5
F4B—C4—C3111.5 (4)H56A—C56—H56C109.5
F4B—C4—F4A110.0 (5)H56B—C56—H56C109.5
F4B—C4—F4C108.3 (5)C55—C56—H56A109.5
F4C—C4—C3109.0 (5)C55—C56—H56B109.5
Ag2—O11A—Ag2i100.50 (11)C55—C56—H56C109.5
C11—O11A—Ag2i141.3 (3)H57A—C57—H57B109.5
C11—O11A—Ag2117.5 (3)H57A—C57—H57C109.5
C11—O11B—Ag1131.4 (3)H57B—C57—H57C109.5
O11A—C11—C12116.9 (4)C52—C57—H57A109.5
O11B—C11—O11A129.1 (4)C52—C57—H57B109.5
O11B—C11—C12113.8 (4)C52—C57—H57C109.5
F12A—C12—C11111.3 (4)C52—C53—H53119.1
F12A—C12—F12B106.9 (4)C54—C53—H53119.1
F12A—C12—C13106.8 (4)C54—C53—C52121.9 (5)
F12B—C12—C11107.6 (4)Ag1—C50—H5088.7
F12B—C12—C13105.5 (4)C51—C50—Ag180.6 (3)
C13—C12—C11118.1 (4)C51—C50—H50119.3
F13A—C13—C12109.4 (5)C51—C50—C55121.4 (5)
F13A—C13—C14106.7 (5)C55—C50—Ag1100.8 (3)
F13B—C13—C12110.5 (4)C55—C50—H50119.3
F13B—C13—F13A108.6 (4)C50—C51—H51119.5
F13B—C13—C14106.6 (5)C50—C51—C52121.0 (5)
C14—C13—C12114.8 (5)C52—C51—H51119.5
F14A—C14—C13110.5 (5)C53—C52—C57122.3 (6)
F14A—C14—F14C106.1 (5)C53—C52—C51116.5 (5)
F14B—C14—C13110.1 (5)C51—C52—C57121.2 (6)
F14B—C14—F14A109.1 (5)C53—C54—H54119.2
F14B—C14—F14C108.9 (6)C53—C54—C55121.6 (5)
F14C—C14—C13112.0 (5)C55—C54—H54119.2
C102—N1—Ag2119.1 (3)C50—C55—C56121.6 (5)
C102—N1—C103118.1 (3)C54—C55—C56120.8 (5)
C103—N1—Ag2122.1 (3)C54—C55—C50117.6 (5)
C104—C105—H105119.6
Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+1, −y, −z+2.
(1-mxyl) top
Crystal data top
C8H10·C20H8Ag2F13N2O4·FF(000) = 1808
Mr = 928.18Dx = 1.959 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 11.3750 (6) ÅCell parameters from 9888 reflections
b = 22.5963 (10) Åθ = 2.5–27.4°
c = 13.3460 (7) ŵ = 1.37 mm−1
β = 113.472 (2)°T = 100 K
V = 3146.5 (3) Å3Plate, yellow
Z = 40.42 × 0.2 × 0.12 mm
Data collection top
Bruker APEX-II CCD
diffractometer		6202 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
ϕ and ω scansθmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan
SADABS2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.1011 before and 0.0786 after correction. The Ratio of minimum to maximum transmission is 0.8102. The λ/2 correction factor is 0.0015.		h = −13→14
Tmin = 0.604, Tmax = 0.746k = −29→28
25586 measured reflectionsl = −17→17
7203 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.074 w = 1/[σ2(Fo2) + (0.0599P)2 + 35.1346P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.189(Δ/σ)max < 0.001
S = 1.12Δρmax = 1.83 e Å−3
7203 reflectionsΔρmin = −1.21 e Å−3
432 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
70 restraintsExtinction coefficient: 0.0017 (3)
Primary atom site location: structure-invariant direct methods
Crystal data top
C8H10·C20H8Ag2F13N2O4·FV = 3146.5 (3) Å3
Mr = 928.18Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.3750 (6) ŵ = 1.37 mm−1
b = 22.5963 (10) ÅT = 100 K
c = 13.3460 (7) Å0.42 × 0.2 × 0.12 mm
β = 113.472 (2)°
Data collection top
Bruker APEX-II CCD
diffractometer		7203 independent reflections
Absorption correction: multi-scan
SADABS2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.1011 before and 0.0786 after correction. The Ratio of minimum to maximum transmission is 0.8102. The λ/2 correction factor is 0.0015.		6202 reflections with I > 2σ(I)
Tmin = 0.604, Tmax = 0.746Rint = 0.057
25586 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.07470 restraints
wR(F2) = 0.189H-atom parameters constrained
S = 1.12 w = 1/[σ2(Fo2) + (0.0599P)2 + 35.1346P]
where P = (Fo2 + 2Fc2)/3
7203 reflectionsΔρmax = 1.83 e Å−3
432 parametersΔρmin = −1.21 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C500.5893 (16)0.1961 (7)0.7566 (12)0.081 (5)
H500.65840.18800.73810.098*
C510.4752 (16)0.1648 (6)0.7062 (10)0.081 (5)
H510.46890.13500.65610.097*
C520.3724 (13)0.1781 (5)0.7311 (9)0.066 (3)
C530.3843 (13)0.2223 (6)0.8074 (9)0.068 (4)
H530.31370.23120.82320.081*
C540.4985 (12)0.2540 (6)0.8614 (9)0.065 (3)
C550.6008 (13)0.2386 (6)0.8327 (10)0.078 (4)
H550.67880.25800.86670.093*
C560.5060 (17)0.2982 (7)0.9399 (12)0.095 (5)
H56A0.57950.29091.00640.142*
H56B0.42980.29700.95440.142*
H56C0.51360.33650.91190.142*
C570.2518 (15)0.1440 (7)0.6749 (11)0.089 (5)
H57A0.18140.16510.68050.133*
H57B0.25960.10590.70860.133*
H57C0.23660.13910.59920.133*
Ag10.66604 (5)0.11370 (2)0.91798 (5)0.02997 (18)
Ag20.88961 (5)0.03676 (2)1.05042 (5)0.02780 (17)
O1A0.7437 (5)0.0779 (3)0.7928 (5)0.0414 (14)
O1B0.9241 (5)0.0290 (3)0.8882 (4)0.0389 (13)
C10.8442 (7)0.0520 (4)0.8047 (5)0.0353 (17)
C20.8767 (8)0.0601 (3)0.7040 (5)0.055 (3)*0.536 (10)
F2A0.8108 (9)0.1005 (5)0.6278 (10)0.076 (4)*0.536 (10)
F2B1.0020 (7)0.0709 (6)0.7293 (10)0.073 (4)*0.536 (10)
C30.8509 (8)0.0057 (4)0.6287 (8)0.081 (7)*0.536 (10)
F3A0.9299 (12)−0.0365 (5)0.6917 (9)0.076 (4)*0.536 (10)
F3B0.8733 (15)0.0087 (7)0.5368 (9)0.101 (5)*0.536 (10)
C40.7206 (10)−0.0247 (4)0.6015 (7)0.070 (6)*0.536 (10)
F4A0.6923 (15)−0.0402 (6)0.6870 (7)0.077 (4)*0.536 (10)
F4B0.6820 (10)−0.0702 (4)0.5301 (5)0.167 (5)*0.536 (10)
F4C0.6270 (18)0.0164 (6)0.5647 (17)0.139 (9)*0.536 (10)
C2'0.8694 (8)0.0519 (3)0.6996 (5)0.053 (3)*0.464 (10)
F2Z0.8721 (12)0.1073 (4)0.6627 (11)0.059 (4)*0.464 (10)
F2Y0.9865 (9)0.0285 (5)0.7223 (10)0.055 (3)*0.464 (10)
C3'0.7753 (9)0.0157 (4)0.6032 (5)0.065 (6)*0.464 (10)
F3Y0.8092 (12)0.0174 (7)0.5171 (9)0.070 (4)*0.464 (10)
F3Z0.6563 (11)0.0389 (9)0.5680 (12)0.088 (6)*0.464 (10)
C4'0.7802 (10)−0.0517 (4)0.6213 (7)0.153 (16)*0.464 (10)
F4X0.8866 (16)−0.0850 (10)0.6466 (17)0.166 (11)*0.464 (10)
F4Y0.7418 (13)−0.0587 (8)0.7041 (6)0.081 (5)*0.464 (10)
F4Z0.6820 (10)−0.0702 (4)0.5301 (5)0.167 (5)*0.464 (10)
O11A0.7880 (5)0.1715 (3)1.0595 (5)0.0398 (13)
O11B0.9788 (6)0.1261 (2)1.1146 (5)0.0399 (13)
C110.9043 (7)0.1673 (3)1.1106 (5)0.0322 (16)
C120.9742 (7)0.2200 (3)1.1832 (5)0.033 (6)*0.530 (8)
F12A0.9416 (9)0.2702 (4)1.1236 (8)0.061 (3)*0.530 (8)
F12B1.1032 (7)0.2164 (4)1.2222 (7)0.044 (2)*0.530 (8)
C130.9409 (7)0.2255 (4)1.2839 (6)0.053 (5)*0.530 (8)
F13A0.9409 (10)0.1708 (4)1.3248 (10)0.054 (3)*0.530 (8)
F13B0.8180 (9)0.2440 (5)1.2429 (12)0.094 (5)*0.530 (8)
C141.0347 (8)0.2632 (4)1.3780 (5)0.047 (5)*0.530 (8)
F14A1.1111 (10)0.3034 (4)1.3589 (8)0.056 (3)*0.530 (8)
F14B1.0956 (11)0.2469 (5)1.4836 (7)0.085 (4)*0.530 (8)
F14C0.9366 (11)0.2983 (6)1.3734 (10)0.085 (4)*0.530 (8)
C12'0.9605 (9)0.2227 (3)1.1808 (6)0.032 (7)*0.470 (8)
F12Y0.8834 (8)0.2705 (5)1.1616 (10)0.058 (3)*0.470 (8)
F12Z1.0681 (8)0.2411 (5)1.1706 (9)0.047 (3)*0.470 (8)
C13'1.0047 (10)0.2140 (3)1.3049 (6)0.046 (4)*0.470 (8)
F13Y1.1070 (9)0.1775 (5)1.3423 (12)0.078 (4)*0.470 (8)
F13Z0.9077 (9)0.1846 (6)1.3168 (12)0.060 (4)*0.470 (8)
C14'1.0119 (8)0.2710 (4)1.3703 (5)0.048 (6)*0.470 (8)
F14X1.0403 (13)0.3214 (4)1.3306 (11)0.071 (4)*0.470 (8)
F14Y1.1248 (9)0.2442 (5)1.4282 (10)0.070 (4)*0.470 (8)
F14Z0.9483 (10)0.2737 (7)1.4367 (9)0.078 (4)*0.470 (8)
N10.4810 (5)0.0723 (3)0.9186 (4)0.0224 (11)
C1000.4318 (8)−0.0471 (3)0.7223 (6)0.0332 (16)
H1000.4685−0.06180.67640.040*
C1010.4856 (7)0.0010 (3)0.7868 (6)0.0273 (14)
H1010.55940.01830.78590.033*
C1020.4277 (6)0.0244 (3)0.8547 (5)0.0217 (13)
C1030.4222 (6)0.0945 (3)0.9795 (5)0.0236 (13)
C1040.4702 (7)0.1465 (3)1.0434 (6)0.0273 (14)
H1040.54440.16451.04490.033*
C1050.4074 (7)0.1696 (3)1.1021 (6)0.0303 (15)
H1050.43910.20361.14300.036*
N20.7406 (5)−0.0179 (2)1.0782 (5)0.0233 (11)
C2000.7050 (7)−0.1431 (3)0.8975 (6)0.0312 (15)
H2000.7464−0.16030.85710.037*
C2010.7534 (7)−0.0930 (3)0.9554 (6)0.0277 (14)
H2010.8259−0.07540.95280.033*
C2020.6921 (6)−0.0673 (3)1.0210 (5)0.0235 (13)
C2030.6839 (6)0.0029 (3)1.1429 (5)0.0225 (13)
C2040.7361 (7)0.0538 (3)1.2106 (6)0.0294 (15)
H2040.80890.07211.20990.035*
C2050.6797 (8)0.0751 (4)1.2754 (6)0.0349 (17)
H2050.71380.10811.31880.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C500.104 (11)0.092 (10)0.080 (9)0.058 (9)0.071 (9)0.053 (8)
C510.126 (12)0.078 (9)0.063 (7)0.063 (9)0.062 (8)0.045 (7)
C520.083 (8)0.066 (7)0.058 (6)0.044 (6)0.036 (6)0.034 (6)
C530.086 (8)0.082 (8)0.050 (6)0.057 (7)0.043 (6)0.037 (6)
C540.074 (8)0.082 (8)0.046 (6)0.035 (6)0.033 (6)0.032 (6)
C550.074 (8)0.096 (10)0.065 (7)0.045 (7)0.030 (6)0.052 (7)
C560.130 (14)0.095 (11)0.076 (9)0.013 (10)0.059 (9)0.017 (8)
C570.103 (11)0.094 (10)0.065 (8)0.046 (9)0.030 (8)0.031 (7)
Ag10.0223 (3)0.0315 (3)0.0353 (3)−0.0021 (2)0.0106 (2)−0.0010 (2)
Ag20.0235 (3)0.0269 (3)0.0364 (3)0.0001 (2)0.0155 (2)0.0006 (2)
O1A0.029 (3)0.058 (4)0.040 (3)0.017 (3)0.017 (2)0.008 (3)
O1B0.036 (3)0.051 (3)0.032 (3)0.020 (3)0.016 (2)0.007 (2)
C10.032 (4)0.053 (5)0.026 (3)0.008 (3)0.017 (3)0.006 (3)
O11A0.032 (3)0.040 (3)0.038 (3)−0.004 (2)0.004 (2)−0.006 (2)
O11B0.036 (3)0.029 (3)0.050 (3)−0.005 (2)0.013 (3)0.002 (2)
C110.035 (4)0.033 (4)0.029 (4)−0.006 (3)0.012 (3)−0.001 (3)
N10.019 (3)0.027 (3)0.022 (3)0.002 (2)0.009 (2)0.003 (2)
C1000.040 (4)0.033 (4)0.030 (4)0.001 (3)0.019 (3)−0.004 (3)
C1010.028 (3)0.028 (3)0.032 (3)0.003 (3)0.018 (3)0.002 (3)
C1020.022 (3)0.021 (3)0.020 (3)0.004 (2)0.006 (2)0.006 (2)
C1030.026 (3)0.022 (3)0.023 (3)0.001 (3)0.009 (3)0.003 (2)
C1040.029 (3)0.026 (3)0.026 (3)−0.006 (3)0.011 (3)−0.002 (3)
C1050.036 (4)0.025 (3)0.029 (4)0.000 (3)0.012 (3)−0.005 (3)
N20.022 (3)0.023 (3)0.028 (3)0.004 (2)0.012 (2)0.003 (2)
C2000.038 (4)0.035 (4)0.026 (3)0.006 (3)0.019 (3)−0.003 (3)
C2010.027 (3)0.030 (4)0.031 (3)0.000 (3)0.016 (3)0.001 (3)
C2020.021 (3)0.028 (3)0.023 (3)0.003 (3)0.010 (2)0.004 (3)
C2030.021 (3)0.026 (3)0.020 (3)0.004 (2)0.008 (2)0.003 (2)
C2040.027 (3)0.029 (4)0.035 (4)−0.004 (3)0.015 (3)−0.003 (3)
C2050.036 (4)0.034 (4)0.036 (4)−0.003 (3)0.015 (3)−0.013 (3)
Geometric parameters (Å, º) top
C50—C511.39 (2)C11—C12'1.5396 (10)
C50—C551.37 (2)C12—F12A1.3501 (10)
C51—C521.370 (17)C12—F12B1.3500 (10)
C52—C531.395 (17)C12—C131.5399 (10)
C52—C571.49 (2)C13—F13A1.3501 (10)
C53—C541.404 (19)C13—F13B1.3498 (10)
C54—C551.406 (16)C13—C141.5402 (10)
C54—C561.426 (19)C14—F14A1.3501 (10)
Ag1—Ag23.0055 (8)C14—F14B1.3502 (10)
Ag1—O1A2.325 (6)C14—F14C1.3501 (10)
Ag1—O11A2.261 (5)C12'—F12Y1.3498 (10)
Ag1—N12.306 (6)C12'—F12Z1.3497 (10)
Ag2—O1B2.355 (5)C12'—C13'1.5400 (10)
Ag2—O1Bi2.447 (5)C13'—F13Y1.3498 (10)
Ag2—O11B2.268 (6)C13'—F13Z1.3499 (10)
Ag2—N22.245 (6)C13'—C14'1.5400 (10)
O1A—C11.237 (9)C14'—F14X1.3495 (10)
O1B—Ag2i2.447 (5)C14'—F14Y1.3496 (10)
O1B—C11.238 (9)C14'—F14Z1.3493 (10)
C1—C21.5402 (10)N1—C1021.362 (9)
C1—C2'1.5400 (10)N1—C1031.340 (9)
C2—F2A1.3502 (10)C100—C1011.370 (10)
C2—F2B1.3502 (10)C100—C205ii1.428 (11)
C2—C31.5398 (10)C101—C1021.418 (9)
C3—F3A1.3499 (10)C102—C203ii1.423 (9)
C3—F3B1.3500 (10)C103—C1041.425 (9)
C3—C41.5398 (10)C103—C202ii1.435 (9)
C4—F4A1.3499 (10)C104—C1051.357 (10)
C4—F4C1.3499 (10)C105—C200ii1.413 (11)
C2'—F2Z1.3498 (10)N2—C2021.340 (9)
C2'—F2Y1.3499 (10)N2—C2031.352 (8)
C2'—C3'1.5402 (10)C200—C105ii1.413 (11)
C3'—F3Y1.3503 (10)C200—C2011.357 (11)
C3'—F3Z1.3501 (10)C201—C2021.442 (9)
C3'—C4'1.5401 (10)C202—C103ii1.435 (9)
C4'—F4X1.3496 (10)C203—C102ii1.423 (9)
C4'—F4Y1.3497 (10)C203—C2041.435 (10)
O11A—C111.228 (9)C204—C2051.354 (10)
O11B—C111.246 (9)C205—C100ii1.428 (11)
C11—C121.5404 (10)
C55—C50—C51120.7 (12)O11A—C11—O11B130.2 (5)
C52—C51—C50119.5 (14)O11A—C11—C12117.5 (6)
C51—C52—C53119.3 (15)O11A—C11—C12'111.7 (7)
C51—C52—C57117.9 (13)O11B—C11—C12112.3 (6)
C53—C52—C57122.7 (12)O11B—C11—C12'118.1 (6)
C52—C53—C54122.8 (11)F12A—C12—C11109.1 (7)
C53—C54—C55115.6 (12)F12A—C12—C13109.9 (8)
C53—C54—C56120.4 (12)F12B—C12—C11113.9 (7)
C55—C54—C56124.0 (15)F12B—C12—F12A106.23 (11)
C50—C55—C54122.1 (15)F12B—C12—C13106.0 (6)
O1A—Ag1—Ag275.32 (14)C13—C12—C11111.5 (5)
O11A—Ag1—Ag275.48 (15)C12—C13—C14115.17 (11)
O11A—Ag1—O1A121.3 (2)F13A—C13—C12108.5 (8)
O11A—Ag1—N1119.3 (2)F13A—C13—C14106.7 (8)
N1—Ag1—Ag2108.85 (14)F13B—C13—C12104.2 (9)
N1—Ag1—O1A118.0 (2)F13B—C13—F13A106.30 (11)
O1Bi—Ag2—Ag1164.85 (13)F13B—C13—C14115.4 (9)
O1B—Ag2—Ag185.09 (13)F14A—C14—C13120.4 (5)
O1B—Ag2—O1Bi79.81 (19)F14A—C14—F14B106.23 (11)
O11B—Ag2—Ag181.59 (15)F14A—C14—F14C100.3 (10)
O11B—Ag2—O1B101.6 (2)F14B—C14—C13126.9 (8)
O11B—Ag2—O1Bi102.5 (2)F14C—C14—C1389.8 (8)
N2—Ag2—Ag184.12 (14)F14C—C14—F14B106.22 (11)
N2—Ag2—O1Bi102.8 (2)C11—C12'—C13'115.4 (6)
N2—Ag2—O1B121.6 (2)F12Y—C12'—C11117.0 (8)
N2—Ag2—O11B132.9 (2)F12Y—C12'—C13'102.4 (7)
C1—O1A—Ag1131.9 (5)F12Z—C12'—C11111.3 (7)
Ag2—O1B—Ag2i100.19 (19)F12Z—C12'—F12Y106.30 (11)
C1—O1B—Ag2i141.6 (5)F12Z—C12'—C13'103.1 (8)
C1—O1B—Ag2117.7 (4)C12'—C13'—C14'115.14 (11)
O1A—C1—O1B128.7 (6)F13Y—C13'—C12'109.9 (9)
O1A—C1—C2111.2 (7)F13Y—C13'—F13Z106.31 (11)
O1A—C1—C2'112.4 (6)F13Y—C13'—C14'117.3 (9)
O1B—C1—C2119.4 (7)F13Z—C13'—C12'104.9 (9)
O1B—C1—C2'118.9 (7)F13Z—C13'—C14'101.9 (9)
F2A—C2—C1118.9 (9)F14X—C14'—C13'116.8 (7)
F2A—C2—C398.2 (8)F14X—C14'—F14Y106.32 (11)
F2B—C2—C1113.6 (7)F14Y—C14'—C13'76.9 (8)
F2B—C2—F2A106.23 (11)F14Z—C14'—C13'119.2 (10)
F2B—C2—C3102.4 (8)F14Z—C14'—F14X119.6 (10)
C3—C2—C1115.2 (6)F14Z—C14'—F14Y106.34 (11)
F3A—C3—C2104.5 (9)C102—N1—Ag1120.0 (4)
F3A—C3—F3B106.29 (11)C103—N1—Ag1121.8 (4)
F3A—C3—C499.9 (10)C103—N1—C102118.2 (6)
F3B—C3—C2119.8 (10)C101—C100—C205ii121.1 (7)
F3B—C3—C4108.7 (10)C100—C101—C102119.5 (7)
C4—C3—C2115.19 (11)N1—C102—C101119.4 (6)
F4A—C4—C3116.6 (9)N1—C102—C203ii120.7 (6)
F4A—C4—F4C93.8 (15)C101—C102—C203ii119.9 (6)
F4C—C4—C3108.9 (11)N1—C103—C104120.4 (6)
C1—C2'—C3'116.3 (6)N1—C103—C202ii120.4 (6)
F2Z—C2'—C1111.7 (8)C104—C103—C202ii119.1 (6)
F2Z—C2'—F2Y106.30 (11)C105—C104—C103119.8 (7)
F2Z—C2'—C3'107.2 (8)C104—C105—C200ii121.7 (7)
F2Y—C2'—C1108.7 (8)C202—N2—Ag2122.1 (4)
F2Y—C2'—C3'106.0 (7)C202—N2—C203117.5 (6)
F3Y—C3'—C2'111.0 (9)C203—N2—Ag2119.8 (4)
F3Y—C3'—C4'99.0 (10)C201—C200—C105ii120.8 (7)
F3Z—C3'—C2'110.6 (11)C200—C201—C202119.9 (7)
F3Z—C3'—F3Y106.24 (11)C103ii—C202—C201118.7 (6)
F3Z—C3'—C4'114.0 (12)N2—C202—C103ii121.8 (6)
C4'—C3'—C2'115.11 (11)N2—C202—C201119.5 (6)
F4X—C4'—C3'124.3 (13)C102ii—C203—C204118.8 (6)
F4X—C4'—F4Y106.31 (11)N2—C203—C102ii121.3 (6)
F4Y—C4'—C3'104.0 (11)N2—C203—C204119.9 (6)
C11—O11A—Ag1125.9 (5)C205—C204—C203120.3 (7)
C11—O11B—Ag2117.1 (4)C204—C205—C100ii120.5 (7)
Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+1, −y, −z+2.
(2a) top
Crystal data top
C20H8Ag2F14N2O4F(000) = 3152
Mr = 822.02Dx = 2.285 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 27.578 (3) ÅCell parameters from 3379 reflections
b = 9.267 (1) Åθ = 2.4–24.2°
c = 21.211 (2) ŵ = 1.78 mm−1
β = 118.142 (3)°T = 100 K
V = 4779.9 (9) Å3Plate, yellow
Z = 80.4 × 0.26 × 0.03 mm
Data collection top
Bruker APEX-II CCD
diffractometer		3234 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.064
ϕ and ω scansθmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan
SADABS2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.1234 before and 0.0609 after correction. The Ratio of minimum to maximum transmission is 0.8098. The λ/2 correction factor is 0.0015.		h = −35→35
Tmin = 0.604, Tmax = 0.746k = −12→10
20167 measured reflectionsl = −18→27
5445 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.068H-atom parameters constrained
wR(F2) = 0.230 w = 1/[σ2(Fo2) + (0.1406P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
5445 reflectionsΔρmax = 1.99 e Å−3
362 parametersΔρmin = −1.39 e Å−3
59 restraints
Crystal data top
C20H8Ag2F14N2O4V = 4779.9 (9) Å3
Mr = 822.02Z = 8
Monoclinic, C2/cMo Kα radiation
a = 27.578 (3) ŵ = 1.78 mm−1
b = 9.267 (1) ÅT = 100 K
c = 21.211 (2) Å0.4 × 0.26 × 0.03 mm
β = 118.142 (3)°
Data collection top
Bruker APEX-II CCD
diffractometer		5445 independent reflections
Absorption correction: multi-scan
SADABS2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.1234 before and 0.0609 after correction. The Ratio of minimum to maximum transmission is 0.8098. The λ/2 correction factor is 0.0015.		3234 reflections with I > 2σ(I)
Tmin = 0.604, Tmax = 0.746Rint = 0.064
20167 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06859 restraints
wR(F2) = 0.230H-atom parameters constrained
S = 1.02Δρmax = 1.99 e Å−3
5445 reflectionsΔρmin = −1.39 e Å−3
362 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ag10.49191 (3)0.28619 (8)0.08927 (4)0.0363 (3)
Ag30.5000−0.10850 (9)0.25000.0275 (3)
Ag20.50000.31447 (10)0.25000.0342 (3)
N10.4913 (3)0.2328 (7)−0.0230 (3)0.0230 (15)
N20.4985 (3)0.1585 (7)−0.1475 (3)0.0223 (14)
C1000.4606 (3)0.1248 (8)−0.0653 (4)0.0220 (17)
C1010.4222 (3)0.0503 (9)−0.0508 (4)0.0280 (19)
H1010.41760.0788−0.01090.034*
C1020.3921 (3)−0.0592 (9)−0.0917 (4)0.0289 (19)
H1020.3667−0.1069−0.08040.035*
C1030.3977 (4)−0.1049 (8)−0.1518 (5)0.030 (2)
H1030.3765−0.1834−0.18010.036*
C1040.4339 (3)−0.0358 (9)−0.1688 (4)0.0299 (19)
H1040.4380−0.0680−0.20850.036*
C1050.4653 (3)0.0837 (8)−0.1278 (4)0.0211 (17)
C1060.5279 (3)0.2671 (8)−0.1055 (4)0.0219 (17)
C1070.5630 (4)0.3496 (9)−0.1246 (5)0.0282 (19)
H1070.56330.3301−0.16840.034*
C1080.5955 (3)0.4536 (9)−0.0816 (4)0.0274 (18)
H1080.61940.5053−0.09420.033*
C1090.5940 (3)0.4872 (9)−0.0158 (4)0.0298 (19)
H1090.61750.56020.01480.036*
C1100.5599 (3)0.4166 (8)0.0028 (4)0.0264 (19)
H1100.55870.44260.04530.032*
C1110.5256 (3)0.3031 (8)−0.0411 (4)0.0241 (18)
O1A0.5761 (3)0.4287 (9)0.2651 (3)0.058 (2)
O1B0.5555 (3)0.4573 (7)0.1511 (3)0.0421 (16)
C10.5833 (3)0.4787 (7)0.2162 (5)0.0294 (19)
C20.6290 (3)0.5879 (7)0.2288 (5)0.027 (3)*0.437 (8)
F2A0.6397 (6)0.6685 (14)0.2869 (5)0.071 (5)*0.437 (8)
F2B0.6150 (5)0.6813 (12)0.1741 (5)0.050 (4)*0.437 (8)
C30.6821 (4)0.5106 (7)0.2407 (6)0.059 (7)*0.437 (8)
F3A0.6721 (5)0.4502 (11)0.1778 (5)0.031 (3)*0.437 (8)
F3B0.6941 (8)0.4009 (13)0.2876 (6)0.095 (6)*0.437 (8)
C40.7316 (3)0.6100 (13)0.2584 (7)0.080 (10)*0.437 (8)
F4A0.7240 (8)0.7165 (17)0.2112 (11)0.143 (10)*0.437 (8)
F4B0.7749 (4)0.5321 (13)0.2643 (7)0.081 (5)*0.437 (8)
F4C0.7494 (8)0.684 (2)0.3202 (9)0.145 (10)*0.437 (8)
C2'0.6347 (2)0.5756 (7)0.2495 (4)0.031 (3)*0.563 (8)
F2Y0.6730 (4)0.5426 (10)0.3167 (5)0.074 (4)*0.563 (8)
F2Z0.6182 (3)0.7117 (7)0.2521 (5)0.034 (2)*0.563 (8)
C3'0.6690 (4)0.5739 (14)0.2094 (5)0.078 (7)*0.563 (8)
F3Y0.6789 (7)0.4321 (14)0.2061 (10)0.107 (6)*0.563 (8)
F3Z0.6333 (5)0.6453 (13)0.1454 (7)0.066 (3)*0.563 (8)
C4'0.7241 (3)0.6550 (9)0.2468 (5)0.097 (9)*0.563 (8)
F4X0.7613 (6)0.5912 (13)0.3077 (7)0.119 (6)*0.563 (8)
F4Y0.7175 (5)0.7905 (11)0.2648 (7)0.094 (5)*0.563 (8)
F4Z0.7345 (7)0.6679 (16)0.1909 (6)0.125 (7)*0.563 (8)
O11A0.4103 (3)0.2031 (6)0.0763 (3)0.0375 (15)
O11B0.5568 (2)0.1111 (6)0.3143 (3)0.0334 (14)
C110.5937 (2)0.1328 (8)0.3760 (4)0.031 (2)
C120.6534 (2)0.1029 (9)0.3921 (4)0.037 (5)*0.487 (7)
F12A0.6548 (5)0.0243 (11)0.3394 (6)0.072 (4)*0.487 (7)
F12B0.6859 (5)0.2188 (9)0.4018 (6)0.053 (3)*0.487 (7)
C130.6829 (3)0.0085 (10)0.4595 (4)0.038 (5)*0.487 (7)
F13A0.7012 (4)0.0802 (10)0.5220 (5)0.053 (3)*0.487 (7)
F13B0.6486 (4)−0.0949 (11)0.4600 (5)0.055 (4)*0.487 (7)
C140.7339 (3)−0.0727 (9)0.4667 (4)0.055 (6)*0.487 (7)
F14A0.7235 (6)−0.1885 (10)0.4236 (7)0.079 (5)*0.487 (7)
F14B0.7697 (5)0.0104 (10)0.4561 (6)0.076 (4)*0.487 (7)
F14C0.7629 (5)−0.1327 (13)0.5320 (5)0.080 (4)*0.487 (7)
C12'0.6427 (2)0.0276 (6)0.4028 (4)0.024 (3)*0.513 (7)
F12Y0.6562 (5)−0.0261 (12)0.4682 (4)0.060 (4)*0.513 (7)
F12Z0.6332 (4)−0.0872 (9)0.3594 (4)0.045 (3)*0.513 (7)
C13'0.6898 (3)0.1160 (6)0.4025 (5)0.036 (4)*0.513 (7)
F13Y0.6955 (5)0.2403 (9)0.4385 (5)0.060 (4)*0.513 (7)
F13Z0.6718 (5)0.1532 (11)0.3335 (4)0.068 (4)*0.513 (7)
C14'0.7452 (2)0.0365 (8)0.4309 (4)0.070 (7)*0.513 (7)
F14X0.7829 (4)0.1284 (12)0.4304 (6)0.085 (5)*0.513 (7)
F14Y0.7646 (5)−0.0072 (13)0.4993 (4)0.088 (4)*0.513 (7)
F14Z0.7406 (5)−0.0834 (11)0.3924 (5)0.067 (4)*0.513 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0429 (5)0.0470 (5)0.0251 (4)−0.0055 (3)0.0211 (3)−0.0016 (3)
Ag30.0368 (6)0.0320 (5)0.0203 (5)0.0000.0189 (4)0.000
Ag20.0312 (5)0.0350 (6)0.0366 (6)0.0000.0162 (5)0.000
N10.025 (4)0.030 (4)0.017 (4)0.007 (3)0.013 (3)0.007 (3)
N20.022 (3)0.029 (3)0.019 (3)0.005 (3)0.012 (3)0.005 (3)
C1000.023 (4)0.029 (5)0.012 (4)0.006 (3)0.007 (3)0.006 (3)
C1010.036 (5)0.032 (5)0.021 (4)−0.002 (4)0.018 (4)0.000 (4)
C1020.027 (4)0.037 (5)0.023 (5)0.001 (4)0.013 (4)0.003 (4)
C1030.043 (5)0.025 (4)0.022 (5)−0.007 (4)0.014 (4)0.000 (4)
C1040.036 (5)0.032 (5)0.023 (5)0.006 (4)0.015 (4)0.000 (4)
C1050.026 (4)0.024 (4)0.016 (4)0.008 (3)0.012 (3)0.007 (3)
C1060.020 (4)0.028 (4)0.019 (4)0.007 (3)0.011 (3)0.005 (3)
C1070.041 (5)0.028 (4)0.023 (4)0.004 (4)0.021 (4)0.002 (4)
C1080.031 (5)0.029 (4)0.030 (5)−0.001 (4)0.021 (4)−0.003 (4)
C1090.034 (5)0.032 (5)0.023 (5)−0.005 (4)0.013 (4)−0.002 (4)
C1100.031 (5)0.028 (4)0.020 (4)0.000 (4)0.011 (4)−0.006 (3)
C1110.026 (4)0.028 (4)0.018 (4)0.007 (3)0.011 (4)0.008 (3)
O1A0.059 (5)0.099 (6)0.020 (3)−0.044 (4)0.023 (3)−0.017 (4)
O1B0.045 (4)0.061 (4)0.025 (4)−0.007 (3)0.019 (3)0.006 (3)
C10.032 (5)0.030 (5)0.031 (5)−0.004 (4)0.019 (4)−0.013 (4)
O11A0.052 (4)0.041 (4)0.029 (4)−0.014 (3)0.027 (3)−0.003 (3)
O11B0.033 (3)0.040 (4)0.030 (4)0.001 (3)0.017 (3)−0.001 (3)
C110.033 (5)0.041 (5)0.021 (5)0.012 (4)0.016 (4)0.004 (4)
Geometric parameters (Å, º) top
Ag1—Ag23.3203 (7)C2—F2A1.3498 (10)
Ag1—N12.425 (6)C2—F2B1.3495 (10)
Ag1—O1B2.267 (6)C2—C31.5395 (10)
Ag1—O11A2.269 (6)C3—F3A1.3498 (10)
Ag3—N2i2.243 (6)C3—F3B1.3495 (10)
Ag3—N2ii2.243 (6)C3—C41.5395 (10)
Ag3—O11B2.537 (6)C4—F4A1.3496 (10)
Ag3—O11Biii2.538 (6)C4—F4B1.3497 (10)
Ag2—Ag1iii3.3203 (7)C4—F4C1.3497 (10)
Ag2—O1A2.233 (6)C2'—F2Y1.3505 (10)
Ag2—O1Aiii2.233 (6)C2'—F2Z1.3503 (10)
Ag2—O11Biii2.418 (6)C2'—C3'1.5400 (10)
Ag2—O11B2.418 (6)C3'—F3Y1.3502 (10)
N1—C1001.344 (10)C3'—F3Z1.410 (18)
N1—C1111.345 (10)C3'—C4'1.5400 (10)
N2—Ag3i2.243 (6)C4'—F4X1.3500 (10)
N2—C1051.361 (9)C4'—F4Y1.3499 (10)
N2—C1061.334 (10)C4'—F4Z1.3499 (10)
C100—C1011.417 (11)O11A—C11iii1.252 (9)
C100—C1051.443 (10)O11B—C111.239 (9)
C101—H1010.9500C11—O11Aiii1.252 (9)
C101—C1021.339 (11)C11—C121.5407 (10)
C102—H1020.9500C11—C12'1.5396 (10)
C102—C1031.420 (11)C12—F12A1.3502 (10)
C103—H1030.9500C12—F12B1.3503 (10)
C103—C1041.368 (11)C12—C131.5398 (10)
C104—H1040.9500C13—F13A1.3497 (10)
C104—C1051.423 (11)C13—F13B1.3498 (10)
C106—C1071.433 (11)C13—C141.5396 (10)
C106—C1111.437 (11)C14—F14A1.3498 (10)
C107—H1070.9500C14—F14B1.3497 (10)
C107—C1081.339 (12)C14—F14C1.3501 (10)
C108—H1080.9500C12'—F12Y1.3496 (10)
C108—C1091.448 (11)C12'—F12Z1.3498 (10)
C109—H1090.9500C12'—C13'1.5394 (10)
C109—C1101.348 (11)C13'—F13Y1.3495 (10)
C110—H1100.9500C13'—F13Z1.3495 (10)
C110—C1111.427 (11)C13'—C14'1.5394 (10)
O1A—C11.234 (10)C14'—F14X1.3498 (10)
O1B—C11.240 (9)C14'—F14Y1.3496 (10)
C1—C21.5398 (10)C14'—F14Z1.3496 (10)
C1—C2'1.5404 (10)
N1—Ag1—Ag2172.14 (15)F2B—C2—C1113.2 (8)
O1B—Ag1—Ag272.05 (15)F2B—C2—C3107.7 (8)
O1B—Ag1—N1110.8 (2)C3—C2—C1111.1 (6)
O1B—Ag1—O11A139.5 (2)F3A—C3—C2107.2 (9)
O11A—Ag1—Ag274.57 (15)F3A—C3—C4103.5 (9)
O11A—Ag1—N1105.4 (2)F3B—C3—C2110.8 (11)
N2i—Ag3—N2ii156.1 (3)F3B—C3—F3A106.32 (11)
N2ii—Ag3—O11Biii113.4 (2)F3B—C3—C4113.0 (11)
N2i—Ag3—O11Biii86.2 (2)C4—C3—C2115.24 (11)
N2ii—Ag3—O11B86.2 (2)F4A—C4—C3116.6 (13)
N2i—Ag3—O11B113.4 (2)F4A—C4—F4B106.30 (11)
O11B—Ag3—O11Biii73.3 (3)F4A—C4—F4C101.9 (17)
Ag1—Ag2—Ag1iii170.95 (4)F4B—C4—C3110.3 (10)
O1Aiii—Ag2—Ag1iii77.80 (15)F4C—C4—C3114.6 (13)
O1Aiii—Ag2—Ag1106.63 (15)F4C—C4—F4B106.31 (11)
O1A—Ag2—Ag177.80 (15)F2Y—C2'—C1116.4 (8)
O1A—Ag2—Ag1iii106.63 (15)F2Y—C2'—C3'101.7 (7)
O1Aiii—Ag2—O1A123.4 (4)F2Z—C2'—C1107.9 (6)
O1Aiii—Ag2—O11Biii88.5 (3)F2Z—C2'—F2Y106.23 (11)
O1A—Ag2—O11B88.5 (3)F2Z—C2'—C3'109.8 (8)
O1Aiii—Ag2—O11B139.9 (2)C3'—C2'—C1114.4 (5)
O1A—Ag2—O11Biii139.9 (2)F3Y—C3'—C2'103.3 (11)
O11B—Ag2—Ag1103.26 (14)F3Y—C3'—F3Z118.2 (11)
O11Biii—Ag2—Ag169.36 (14)F3Y—C3'—C4'109.1 (12)
O11B—Ag2—Ag1iii69.36 (14)F3Z—C3'—C2'101.3 (9)
O11Biii—Ag2—Ag1iii103.26 (14)F3Z—C3'—C4'109.7 (10)
O11B—Ag2—O11Biii77.6 (3)C4'—C3'—C2'115.17 (11)
C100—N1—Ag1121.2 (5)F4X—C4'—C3'113.5 (10)
C100—N1—C111118.5 (7)F4Y—C4'—C3'111.5 (9)
C111—N1—Ag1120.1 (5)F4Y—C4'—F4X106.26 (11)
C105—N2—Ag3i120.9 (5)F4Z—C4'—C3'99.1 (9)
C106—N2—Ag3i121.3 (5)F4Z—C4'—F4X120.0 (11)
C106—N2—C105117.7 (6)F4Z—C4'—F4Y106.27 (11)
N1—C100—C101121.2 (7)C11iii—O11A—Ag1122.7 (5)
N1—C100—C105120.6 (7)Ag2—O11B—Ag3104.5 (2)
C101—C100—C105118.2 (7)C11—O11B—Ag3133.6 (5)
C100—C101—H101119.1C11—O11B—Ag2117.5 (5)
C102—C101—C100121.8 (7)O11Aiii—C11—C12114.1 (7)
C102—C101—H101119.1O11Aiii—C11—C12'115.3 (7)
C101—C102—H102119.6O11B—C11—O11Aiii126.6 (5)
C101—C102—C103120.8 (8)O11B—C11—C12117.8 (7)
C103—C102—H102119.6O11B—C11—C12'115.4 (7)
C102—C103—H103120.0F12A—C12—C11111.0 (8)
C104—C103—C102119.9 (8)F12A—C12—F12B106.23 (11)
C104—C103—H103120.0F12A—C12—C13104.7 (7)
C103—C104—H104119.5F12B—C12—C11116.9 (8)
C103—C104—C105120.9 (7)F12B—C12—C13106.8 (8)
C105—C104—H104119.5C13—C12—C11110.4 (5)
N2—C105—C100120.8 (7)C12—C13—C14115.23 (11)
N2—C105—C104120.9 (7)F13A—C13—C12114.9 (8)
C104—C105—C100118.2 (7)F13A—C13—F13B106.30 (11)
N2—C106—C107119.5 (7)F13A—C13—C14104.0 (8)
N2—C106—C111121.6 (7)F13B—C13—C12110.3 (8)
C107—C106—C111118.9 (7)F13B—C13—C14105.3 (8)
C106—C107—H107119.5F14A—C14—C13115.4 (8)
C108—C107—C106121.0 (8)F14A—C14—F14B106.30 (11)
C108—C107—H107119.5F14A—C14—F14C101.6 (10)
C107—C108—H108120.1F14B—C14—C13114.2 (8)
C107—C108—C109119.8 (7)F14B—C14—F14C106.26 (11)
C109—C108—H108120.1F14C—C14—C13112.0 (8)
C108—C109—H109119.4F12Y—C12'—C11112.5 (8)
C110—C109—C108121.2 (8)F12Y—C12'—F12Z106.32 (11)
C110—C109—H109119.4F12Y—C12'—C13'112.1 (7)
C109—C110—H110119.8F12Z—C12'—C11113.1 (7)
C109—C110—C111120.4 (8)F12Z—C12'—C13'108.0 (7)
C111—C110—H110119.8C13'—C12'—C11104.8 (5)
N1—C111—C106120.7 (7)C12'—C13'—C14'115.25 (11)
N1—C111—C110120.7 (7)F13Y—C13'—C12'108.9 (8)
C110—C111—C106118.6 (7)F13Y—C13'—F13Z106.35 (11)
C1—O1A—Ag2124.7 (5)F13Y—C13'—C14'110.9 (8)
C1—O1B—Ag1131.2 (5)F13Z—C13'—C12'105.2 (8)
O1A—C1—O1B128.1 (5)F13Z—C13'—C14'109.7 (8)
O1A—C1—C2123.0 (7)F14X—C14'—C13'108.7 (7)
O1A—C1—C2'108.2 (7)F14Y—C14'—C13'112.5 (8)
O1B—C1—C2108.8 (7)F14Y—C14'—F14X106.29 (11)
O1B—C1—C2'123.7 (7)F14Z—C14'—C13'111.4 (7)
F2A—C2—C1109.2 (9)F14Z—C14'—F14X111.4 (9)
F2A—C2—F2B106.33 (11)F14Z—C14'—F14Y106.31 (11)
F2A—C2—C3109.1 (9)
Symmetry codes: (i) −x+1, −y, −z; (ii) x, −y, z+1/2; (iii) −x+1, y, −z+1/2.
(2b) top
Crystal data top
C20H8Ag2F14N2O4Z = 2
Mr = 822.02F(000) = 788
Triclinic, P1Dx = 2.199 Mg m−3
a = 10.782 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.006 (4) ÅCell parameters from 2619 reflections
c = 12.540 (4) Åθ = 2.2–21.9°
α = 71.569 (4)°µ = 1.72 mm−1
β = 76.089 (4)°T = 173 K
γ = 62.229 (4)°Plate, yellow
V = 1241.5 (7) Å3 × × mm
Data collection top
Bruker APEX-II CCD
diffractometer		2491 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
ϕ and ω scansθmax = 24.3°, θmin = 1.7°
Absorption correction: multi-scan
SADABS2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.1443 before and 0.0437 after correction. The Ratio of minimum to maximum transmission is 0.5803. The λ/2 correction factor is 0.0015.		h = −12→9
Tmin = 0.432, Tmax = 0.745k = −12→12
9058 measured reflectionsl = −14→14
3916 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.080H-atom parameters constrained
wR(F2) = 0.272 w = 1/[σ2(Fo2) + (0.1469P)2 + 9.2164P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
3916 reflectionsΔρmax = 1.72 e Å−3
315 parametersΔρmin = −1.05 e Å−3
48 restraints
Crystal data top
C20H8Ag2F14N2O4γ = 62.229 (4)°
Mr = 822.02V = 1241.5 (7) Å3
Triclinic, P1Z = 2
a = 10.782 (3) ÅMo Kα radiation
b = 11.006 (4) ŵ = 1.72 mm−1
c = 12.540 (4) ÅT = 173 K
α = 71.569 (4)° × × mm
β = 76.089 (4)°
Data collection top
Bruker APEX-II CCD
diffractometer		3916 independent reflections
Absorption correction: multi-scan
SADABS2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.1443 before and 0.0437 after correction. The Ratio of minimum to maximum transmission is 0.5803. The λ/2 correction factor is 0.0015.		2491 reflections with I > 2σ(I)
Tmin = 0.432, Tmax = 0.745Rint = 0.036
9058 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.08048 restraints
wR(F2) = 0.272H-atom parameters constrained
S = 1.05Δρmax = 1.72 e Å−3
3916 reflectionsΔρmin = −1.05 e Å−3
315 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ag010.58225 (12)0.83936 (11)0.44475 (10)0.0713 (5)
Ag020.80940 (11)0.55737 (11)0.55225 (10)0.0692 (4)
O0010.7544 (12)0.7021 (12)0.6690 (10)0.096 (4)
O0020.5736 (11)0.9003 (10)0.6089 (9)0.081 (3)
C0010.6590 (16)0.8195 (15)0.6746 (9)0.068 (4)*
C0020.6331 (11)0.8577 (11)0.7885 (8)0.100 (5)*
F0010.5656 (13)0.9991 (11)0.7767 (13)0.162 (5)*
F0020.7605 (12)0.8170 (14)0.8201 (14)0.184 (6)*
C0030.5340 (13)0.7913 (12)0.8635 (11)0.25 (2)*
F0030.6040 (14)0.6517 (14)0.9081 (15)0.201 (7)*
F0040.4164 (11)0.8078 (12)0.8294 (11)0.142 (4)*
C0040.4832 (11)0.8217 (12)0.9820 (10)0.39 (3)*
F0050.4111 (18)0.7423 (17)1.034 (2)0.306 (13)*
F0060.3872 (17)0.9512 (15)0.936 (2)0.346 (16)*
F0070.5936 (14)0.8401 (18)0.9950 (17)0.221 (8)*
O0030.9472 (10)0.6184 (10)0.3905 (8)0.069 (3)
O0040.7860 (12)0.8378 (11)0.3320 (9)0.086 (3)
C0050.9043 (14)0.7333 (15)0.3255 (8)0.066 (4)
C0060.9858 (13)0.7746 (13)0.2118 (7)0.079 (14)*0.469 (17)
F0081.1150 (15)0.744 (2)0.2341 (16)0.098 (7)*0.469 (17)
F0090.9308 (18)0.9125 (13)0.1574 (16)0.085 (6)*0.469 (17)
C0070.9895 (14)0.6937 (12)0.1300 (9)0.057 (10)*0.469 (17)
F0100.8594 (13)0.708 (2)0.1254 (17)0.084 (6)*0.469 (17)
F0111.0688 (19)0.5539 (15)0.166 (3)0.145 (11)*0.469 (17)
C0081.0558 (17)0.7335 (14)0.0085 (7)0.10 (2)*0.469 (17)
F0121.098 (2)0.8386 (18)−0.0206 (19)0.145 (11)*0.469 (17)
F0131.010 (2)0.738 (2)−0.0845 (14)0.214 (18)*0.469 (17)
F0141.1857 (18)0.626 (3)0.0155 (19)0.150 (12)*0.469 (17)
C0091.0038 (11)0.7492 (14)0.2164 (7)0.063 (10)*0.531 (17)
F0151.1404 (13)0.6626 (15)0.2312 (14)0.088 (5)*0.531 (17)
F0160.9949 (19)0.8820 (12)0.1823 (19)0.114 (7)*0.531 (17)
C0100.9708 (13)0.7048 (15)0.1256 (10)0.17 (3)*0.531 (17)
F0170.993 (2)0.5676 (14)0.161 (2)0.131 (8)*0.531 (17)
F0180.8370 (15)0.7781 (19)0.099 (2)0.124 (8)*0.531 (17)
C0111.0486 (15)0.7338 (13)0.0069 (7)0.21 (5)*0.531 (17)
F0191.1743 (14)0.734 (2)0.004 (2)0.141 (9)*0.531 (17)
F0200.9651 (16)0.8653 (12)−0.0471 (17)0.136 (9)*0.531 (17)
F0211.0522 (19)0.6448 (13)−0.0484 (13)0.104 (7)*0.531 (17)
N0010.7051 (11)0.4115 (11)0.5664 (9)0.058 (3)
C0120.4122 (17)0.5343 (18)0.7763 (14)0.084 (5)
H0120.38090.59260.82800.101*
C0130.5275 (18)0.5208 (16)0.7066 (13)0.078 (4)
H0130.57430.57680.70380.094*
C0140.5841 (15)0.4262 (14)0.6358 (11)0.058 (3)
C0150.7568 (14)0.3172 (14)0.5026 (12)0.062 (3)
C0160.8873 (17)0.2892 (18)0.4344 (15)0.084 (5)
H0160.93910.34040.43140.101*
C0170.939 (2)0.193 (2)0.3744 (19)0.114 (7)
H0171.02850.17310.33110.137*
N0020.4424 (12)0.7423 (12)0.4320 (9)0.062 (3)
C0180.140 (2)0.882 (2)0.6255 (18)0.105 (6)
H0180.10330.94900.67070.126*
C0190.2628 (18)0.8596 (17)0.5632 (16)0.087 (5)
H0190.31430.90920.56500.104*
C0200.3183 (15)0.7629 (15)0.4942 (12)0.069 (4)
C0210.4894 (14)0.6498 (13)0.3644 (12)0.062 (3)
C0220.6171 (16)0.6296 (16)0.2920 (12)0.070 (4)
H0220.66780.68130.29080.085*
C0230.6667 (19)0.5406 (17)0.2264 (14)0.086 (5)
H0230.75440.52560.18070.103*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag010.0666 (8)0.0676 (7)0.0905 (9)−0.0246 (6)−0.0080 (6)−0.0392 (6)
Ag020.0598 (7)0.0678 (7)0.0826 (8)−0.0308 (5)0.0046 (5)−0.0243 (6)
O0010.091 (8)0.091 (8)0.098 (8)−0.011 (6)−0.020 (6)−0.047 (7)
O0020.087 (7)0.070 (6)0.081 (7)−0.014 (5)−0.017 (6)−0.035 (5)
O0030.061 (6)0.065 (6)0.068 (6)−0.026 (5)0.007 (5)−0.008 (5)
O0040.077 (7)0.074 (7)0.086 (7)−0.022 (6)0.003 (6)−0.018 (6)
C0050.073 (10)0.069 (9)0.062 (8)−0.035 (8)0.008 (7)−0.027 (7)
N0010.059 (7)0.059 (6)0.062 (6)−0.023 (5)−0.003 (5)−0.026 (5)
C0120.082 (11)0.105 (12)0.091 (11)−0.053 (9)0.030 (9)−0.065 (10)
C0130.096 (12)0.081 (10)0.081 (10)−0.054 (9)0.016 (9)−0.043 (8)
C0140.068 (9)0.066 (8)0.056 (7)−0.041 (7)0.005 (6)−0.024 (6)
C0150.052 (8)0.073 (8)0.076 (9)−0.033 (7)0.002 (6)−0.034 (7)
C0160.064 (9)0.093 (11)0.101 (12)−0.033 (8)0.021 (8)−0.053 (10)
C0170.086 (13)0.132 (16)0.149 (18)−0.053 (12)0.044 (12)−0.094 (15)
N0020.064 (7)0.072 (7)0.059 (6)−0.030 (6)−0.002 (5)−0.027 (6)
C0180.094 (13)0.096 (13)0.136 (16)−0.041 (11)0.032 (12)−0.072 (12)
C0190.076 (11)0.085 (10)0.116 (13)−0.032 (8)0.017 (9)−0.068 (10)
C0200.065 (9)0.063 (8)0.075 (9)−0.019 (7)0.003 (7)−0.031 (7)
C0210.054 (8)0.057 (7)0.075 (9)−0.023 (6)−0.005 (7)−0.020 (7)
C0220.073 (10)0.089 (10)0.073 (9)−0.051 (8)0.021 (7)−0.045 (8)
C0230.096 (12)0.082 (10)0.096 (11)−0.055 (9)0.029 (9)−0.043 (9)
Geometric parameters (Å, º) top
Ag01—Ag023.0506 (17)C008—F0121.3498 (11)
Ag01—O0022.328 (10)C008—F0131.3498 (11)
Ag01—O002i2.515 (10)C008—F0141.3499 (11)
Ag01—O0042.304 (11)C009—F0151.3501 (11)
Ag01—N0022.272 (11)C009—F0161.3501 (11)
Ag02—O0012.283 (11)C009—C0101.5400 (11)
Ag02—O003ii2.538 (10)C010—F0171.3500 (11)
Ag02—O0032.322 (9)C010—F0181.3500 (11)
Ag02—N0012.297 (11)C010—C0111.5399 (11)
O001—C0011.232 (17)C011—F0191.3499 (11)
O002—Ag01i2.515 (10)C011—F0201.3499 (11)
O002—C0011.206 (16)C011—F0211.3499 (11)
C001—C0021.5400 (11)N001—C0141.354 (16)
C002—F0011.3500 (11)N001—C0151.342 (16)
C002—F0021.3499 (11)C012—C0131.31 (2)
C002—C0031.5399 (11)C012—C023iii1.45 (2)
C003—F0031.3499 (11)C013—C0141.406 (18)
C003—F0041.3500 (11)C014—C021iii1.395 (18)
C003—C0041.5398 (11)C015—C0161.41 (2)
C004—F0051.3499 (11)C015—C020iii1.437 (19)
C004—F0061.3499 (11)C016—C0171.33 (2)
C004—F0071.3499 (11)C017—C018iii1.43 (3)
O003—Ag02ii2.538 (10)N002—C0201.333 (17)
O003—C0051.210 (15)N002—C0211.368 (16)
O004—C0051.264 (16)C018—C017iii1.43 (3)
C005—C0061.5399 (11)C018—C0191.32 (2)
C005—C0091.5401 (11)C019—C0201.406 (19)
C006—F0081.3500 (11)C020—C015iii1.437 (19)
C006—F0091.3499 (11)C021—C014iii1.395 (18)
C006—C0071.5399 (11)C021—C0221.419 (18)
C007—F0101.3499 (11)C022—C0231.316 (19)
C007—F0111.3500 (11)C023—C012iii1.45 (2)
C007—C0081.5398 (11)
O002—Ag01—Ag0283.4 (2)F009—C006—F008106.26 (11)
O002i—Ag01—Ag02161.5 (2)F009—C006—C007105.7 (11)
O002—Ag01—O002i80.7 (4)F010—C007—C006111.5 (13)
O004—Ag01—Ag0276.9 (3)F010—C007—F011106.26 (11)
O004—Ag01—O002i99.0 (4)F010—C007—C008108.5 (13)
O004—Ag01—O002107.7 (4)F011—C007—C006110.5 (16)
N002—Ag01—Ag0294.2 (3)F011—C007—C008104.4 (16)
N002—Ag01—O002122.0 (4)C008—C007—C006115.17 (11)
N002—Ag01—O002i102.2 (4)F012—C008—C007119.7 (11)
N002—Ag01—O004128.2 (4)F012—C008—F01496.6 (19)
O001—Ag02—Ag0174.7 (3)F013—C008—C007123.8 (13)
O001—Ag02—O003109.4 (4)F013—C008—F012106.29 (11)
O001—Ag02—O003ii98.1 (4)F013—C008—F014106.28 (11)
O001—Ag02—N001126.2 (4)F014—C008—C00799.0 (14)
O003ii—Ag02—Ag01157.2 (2)F015—C009—C005112.3 (12)
O003—Ag02—Ag0181.9 (2)F015—C009—F016106.24 (11)
O003—Ag02—O003ii80.3 (3)F015—C009—C010105.4 (11)
N001—Ag02—Ag0199.4 (3)F016—C009—C005110.4 (13)
N001—Ag02—O003122.8 (4)F016—C009—C010113.0 (12)
N001—Ag02—O003ii102.1 (3)C010—C009—C005109.4 (9)
C001—O001—Ag02132.8 (9)F017—C010—C009109.9 (14)
Ag01—O002—Ag01i99.3 (4)F017—C010—C011110.9 (15)
C001—O002—Ag01119.3 (8)F018—C010—C009115.1 (15)
C001—O002—Ag01i138.4 (9)F018—C010—F017106.26 (11)
O001—C001—C002114.8 (12)F018—C010—C01198.7 (14)
O002—C001—O001128.7 (11)C011—C010—C009115.17 (11)
O002—C001—C002115.9 (12)F019—C011—C010115.4 (11)
F001—C002—C001111.0 (11)F019—C011—F021114.8 (16)
F001—C002—C003108.3 (9)F020—C011—C010106.3 (14)
F002—C002—C001107.3 (11)F020—C011—F019106.27 (11)
F002—C002—F001106.28 (11)F020—C011—F021106.27 (11)
F002—C002—C003119.6 (11)F021—C011—C010107.1 (12)
C003—C002—C001104.3 (9)C014—N001—Ag02119.5 (8)
F003—C003—C002112.4 (12)C015—N001—Ag02121.5 (9)
F003—C003—F004106.28 (11)C015—N001—C014118.9 (11)
F003—C003—C00491.5 (12)C013—C012—C023iii119.3 (13)
F004—C003—C002123.2 (11)C012—C013—C014122.1 (14)
F004—C003—C004103.4 (12)N001—C014—C013121.1 (12)
C004—C003—C002115.19 (11)N001—C014—C021iii120.2 (11)
F005—C004—C003103.7 (16)C021iii—C014—C013118.7 (13)
F005—C004—F007140.3 (13)N001—C015—C016122.0 (13)
F006—C004—C00389.6 (15)N001—C015—C020iii120.1 (12)
F006—C004—F005106.26 (12)C016—C015—C020iii117.9 (13)
F006—C004—F007106.29 (11)C017—C016—C015121.2 (17)
F007—C004—C00398.5 (10)C016—C017—C018iii120.3 (16)
Ag02—O003—Ag02ii99.7 (3)C020—N002—Ag01123.0 (9)
C005—O003—Ag02ii132.9 (8)C020—N002—C021116.9 (12)
C005—O003—Ag02122.2 (7)C021—N002—Ag01119.9 (9)
C005—O004—Ag01127.9 (8)C019—C018—C017iii120.8 (16)
O003—C005—O004128.7 (8)C018—C019—C020120.8 (17)
O003—C005—C006124.3 (11)N002—C020—C015iii121.4 (12)
O003—C005—C009114.9 (11)N002—C020—C019119.5 (15)
O004—C005—C006106.9 (11)C019—C020—C015iii118.9 (14)
O004—C005—C009116.2 (11)C014iii—C021—C022118.5 (12)
C005—C006—C007108.6 (8)N002—C021—C014iii122.2 (12)
F008—C006—C005106.9 (12)N002—C021—C022119.3 (12)
F008—C006—C007113.5 (13)C023—C022—C021121.2 (14)
F009—C006—C005116.1 (13)C022—C023—C012iii120.0 (14)
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z+1.
(1-tol-pxyl.tol.pxyl) top
Crystal data top
C40H16Ag4F28N4O8·3(C7.43H8.85)Z = 1
Mr = 1938.33F(000) = 945.4382
Triclinic, P1Dx = 1.985 Mg m−3
a = 10.6658 (15) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.2395 (14) ÅCell parameters from 2414 reflections
c = 14.325 (2) Åθ = 3.5–24.4°
α = 72.054 (2)°µ = 1.33 mm−1
β = 86.608 (3)°T = 100 K
γ = 83.149 (3)°Plate, yellow
V = 1621.6 (4) Å30.32 × 0.2 × 0.12 mm
Data collection top
Bruker APEX-II CCD
diffractometer		4917 reflections with I ≥ 2u(I)
Graphite monochromatorRint = 0.048
ϕ and ω scansθmax = 27.6°, θmin = 3.4°
Absorption correction: multi-scan
SADABS2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.0726 before and 0.0556 after correction. The Ratio of minimum to maximum transmission is 0.8234. The λ/2 correction factor is 0.0015.		h = −13→13
Tmin = 0.614, Tmax = 0.746k = −13→14
10048 measured reflectionsl = −18→17
7080 independent reflections
Refinement top
Refinement on F250 constraints
Least-squares matrix: fullPrimary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.071H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.207 w = 1/[σ2(Fo2) + (0.1048P)2 + 7.5111P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
7080 reflectionsΔρmax = 1.89 e Å−3
382 parametersΔρmin = −1.63 e Å−3
36 restraints
Crystal data top
C40H16Ag4F28N4O8·3(C7.43H8.85)γ = 83.149 (3)°
Mr = 1938.33V = 1621.6 (4) Å3
Triclinic, P1Z = 1
a = 10.6658 (15) ÅMo Kα radiation
b = 11.2395 (14) ŵ = 1.33 mm−1
c = 14.325 (2) ÅT = 100 K
α = 72.054 (2)°0.32 × 0.2 × 0.12 mm
β = 86.608 (3)°
Data collection top
Bruker APEX-II CCD
diffractometer		7080 independent reflections
Absorption correction: multi-scan
SADABS2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.0726 before and 0.0556 after correction. The Ratio of minimum to maximum transmission is 0.8234. The λ/2 correction factor is 0.0015.		4917 reflections with I ≥ 2u(I)
Tmin = 0.614, Tmax = 0.746Rint = 0.048
10048 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.07136 restraints
wR(F2) = 0.207H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 1.89 e Å−3
7080 reflectionsΔρmin = −1.63 e Å−3
382 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ag10.03466 (5)0.89440 (5)0.42088 (4)0.02534 (18)
Ag20.25492 (5)0.69489 (5)0.45475 (4)0.02889 (18)
C10.2340 (7)0.9212 (7)0.2578 (6)0.0285 (16)
C20.2872 (8)0.9820 (8)0.1529 (6)0.0342 (17)*
C30.2133 (14)0.9610 (13)0.0763 (10)0.074 (3)*
C40.2502 (14)1.0086 (13)−0.0316 (10)0.073 (3)*
C50.2102 (7)0.8690 (7)0.5981 (4)0.0266 (15)
C60.2502 (4)0.8997 (4)0.6889 (3)0.0364 (18)*
C70.3570 (5)0.9859 (4)0.6692 (4)0.053 (2)*
C80.4914 (5)0.9270 (5)0.6537 (4)0.075 (4)*
C100−0.1916 (8)0.6988 (8)0.7048 (6)0.0335 (18)
H100−0.1994 (8)0.7452 (8)0.7506 (6)0.040 (2)*
C101−0.1401 (7)0.7495 (6)0.6135 (6)0.0248 (15)
H101−0.1083 (7)0.8291 (6)0.5968 (6)0.0298 (18)*
C102−0.1343 (6)0.6818 (6)0.5430 (5)0.0216 (14)
C103−0.0873 (6)0.6706 (6)0.3873 (5)0.0220 (14)
C104−0.0432 (7)0.7234 (7)0.2885 (6)0.0290 (16)
H104−0.0129 (7)0.8037 (7)0.2692 (6)0.0348 (19)*
C105−0.0444 (7)0.6604 (8)0.2229 (6)0.0320 (17)
H105−0.0141 (7)0.6970 (8)0.1578 (6)0.038 (2)*
C106−0.0898 (8)0.5399 (7)0.2482 (6)0.0326 (17)
H106−0.0903 (8)0.4973 (7)0.2004 (6)0.039 (2)*
C2000.2329 (7)0.4209 (8)0.2686 (6)0.0318 (17)
H2000.2648 (7)0.4559 (8)0.2038 (6)0.038 (2)*
C2010.2290 (7)0.4886 (7)0.3325 (5)0.0267 (15)
H2010.2579 (7)0.5697 (7)0.3123 (5)0.0321 (18)*
C2020.1810 (6)0.4377 (7)0.4304 (5)0.0231 (14)
C2030.1340 (6)0.4509 (6)0.5858 (5)0.0222 (14)
C2040.1322 (7)0.5132 (7)0.6590 (6)0.0283 (16)
H2040.1616 (7)0.5939 (7)0.6422 (6)0.0339 (19)*
F2A0.4066 (6)0.9370 (5)0.1434 (4)0.0568 (15)*
F2B0.2859 (6)1.1065 (6)0.1327 (5)0.0637 (16)*
F3A0.2529 (15)0.8028 (14)0.1002 (11)0.072 (4)*0.478 (11)
F3B0.0988 (13)0.9349 (12)0.0979 (9)0.057 (4)*0.478 (11)
F3Y0.1675 (14)0.8665 (13)0.0913 (10)0.069 (4)*0.522 (11)
F3Z0.0981 (14)1.0576 (13)0.0725 (10)0.075 (4)*0.522 (11)
F4A0.3731 (15)0.9893 (16)−0.0452 (11)0.070 (4)*0.478 (11)
F4B0.202 (2)0.912 (2)−0.0754 (15)0.105 (7)*0.478 (11)
F4C0.202 (2)1.111 (2)−0.0539 (15)0.110 (7)*0.478 (11)
F4X0.3050 (16)1.1216 (14)−0.0574 (11)0.084 (5)*0.522 (11)
F4Y0.1662 (13)1.0202 (13)−0.0954 (10)0.068 (4)*0.522 (11)
F4Z0.3499 (14)0.9236 (15)−0.0403 (11)0.073 (4)*0.522 (11)
F6A0.2836 (5)0.7942 (4)0.7627 (4)0.0588 (15)*
F6B0.1545 (5)0.9643 (4)0.7246 (4)0.0518 (14)*
F7A0.3330 (7)1.0805 (6)0.5854 (4)0.034 (2)*0.657 (17)
F7B0.3588 (12)1.0403 (9)0.7409 (5)0.066 (3)*0.657 (17)
F8A0.5299 (12)0.8416 (10)0.7388 (5)0.091 (4)*0.657 (17)
F8B0.5013 (8)0.8655 (7)0.5858 (5)0.054 (3)*0.657 (17)
F8C0.5688 (10)1.0189 (8)0.6225 (8)0.063 (3)*0.657 (17)
N1−0.0845 (6)0.7327 (5)0.4520 (5)0.0244 (13)
N20.1772 (5)0.5027 (5)0.4947 (4)0.0217 (12)
O10.1526 (5)0.9897 (5)0.2883 (4)0.0331 (12)
O20.2765 (5)0.8105 (5)0.2964 (4)0.0351 (13)
O30.1197 (5)0.9368 (5)0.5529 (4)0.0282 (11)
O40.2733 (5)0.7774 (5)0.5821 (5)0.0364 (13)
C510.5055 (9)0.6262 (9)0.4852 (10)0.054 (3)
H510.5088 (9)0.7134 (9)0.4753 (10)0.065 (3)*
C500.4768 (9)0.5508 (10)0.5756 (10)0.058 (3)
H500.4611 (9)0.5858 (10)0.6282 (10)0.070 (4)*
C520.5302 (9)0.5791 (10)0.4066 (10)0.063 (3)
H520.5511 (9)0.6320 (10)0.3433 (10)0.075 (4)*0.287500
C710.0972 (19)0.4129 (17)0.0284 (13)0.111 (3)*
H710.1642 (19)0.3476 (17)0.0491 (13)0.133 (4)*
C530.5646 (15)0.6560 (17)0.3056 (14)0.075 (5)0.712500
H53a0.5776 (15)0.6022 (17)0.2627 (14)0.113 (8)*0.712500
H53b0.4963 (15)0.7229 (17)0.2803 (14)0.113 (8)*0.712500
H53c0.6426 (15)0.6934 (17)0.3072 (14)0.113 (8)*0.712500
C72−0.015 (2)0.3837 (17)0.0373 (14)0.111 (3)*
H72−0.024 (2)0.2968 (17)0.0658 (14)0.133 (4)*0.287500
C700.127 (2)0.5388 (18)−0.0111 (14)0.111 (3)*
H700.209 (2)0.5655 (18)−0.0183 (14)0.133 (4)*
C620.498 (2)0.620 (2)−0.0532 (14)0.157 (5)*
H620.495 (2)0.707 (2)−0.0886 (14)0.189 (6)*
C73−0.040 (3)0.2577 (19)0.0736 (19)0.111 (3)*0.712500
H73a−0.132 (3)0.2535 (19)0.0752 (19)0.166 (5)*0.712500
H73b0.001 (3)0.2108 (19)0.0308 (19)0.166 (5)*0.712500
H73c−0.008 (3)0.2208 (19)0.1401 (19)0.166 (5)*0.712500
C610.526 (2)0.5827 (19)0.0485 (15)0.157 (5)*
H610.545 (2)0.6404 (19)0.0808 (15)0.189 (6)*0.287500
C600.523 (2)0.4521 (18)0.0978 (17)0.157 (5)*
H600.537 (2)0.4206 (18)0.1664 (17)0.189 (6)*
C630.561 (3)0.674 (2)0.092 (2)0.157 (5)*0.712500
H63a0.577 (3)0.633 (2)0.162 (2)0.236 (8)*0.712500
H63b0.637 (3)0.708 (2)0.059 (2)0.236 (8)*0.712500
H63c0.492 (3)0.742 (2)0.084 (2)0.236 (8)*0.712500
F8X0.480 (3)0.934 (2)0.5588 (7)0.136 (13)*0.343 (17)
F8Y0.5296 (18)0.8056 (7)0.7014 (16)0.111 (10)*0.343 (17)
F8Z0.5877 (13)0.9930 (14)0.658 (2)0.081 (8)*0.343 (17)
F7Y0.317 (3)1.1031 (9)0.6126 (14)0.127 (13)*0.343 (17)
F7Z0.3865 (19)0.9968 (19)0.7563 (7)0.061 (6)*0.343 (17)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0226 (3)0.0238 (3)0.0340 (3)−0.0003 (2)−0.0011 (2)−0.0159 (2)
Ag20.0271 (3)0.0223 (3)0.0397 (4)−0.0006 (2)−0.0037 (2)−0.0133 (2)
C10.018 (3)0.039 (4)0.034 (4)−0.006 (3)−0.002 (3)−0.018 (3)
C50.027 (4)0.025 (3)0.031 (4)−0.007 (3)−0.003 (3)−0.010 (3)
C1000.035 (4)0.039 (4)0.035 (4)0.003 (3)−0.007 (3)−0.026 (4)
C1010.026 (4)0.020 (3)0.032 (4)0.001 (3)0.001 (3)−0.015 (3)
C1020.021 (3)0.020 (3)0.026 (4)0.002 (3)−0.007 (3)−0.011 (3)
C1030.016 (3)0.025 (3)0.028 (4)0.004 (3)−0.002 (3)−0.015 (3)
C1040.027 (4)0.028 (4)0.034 (4)−0.001 (3)−0.004 (3)−0.013 (3)
C1050.031 (4)0.041 (4)0.029 (4)−0.006 (3)−0.004 (3)−0.016 (3)
C1060.034 (4)0.037 (4)0.036 (4)0.000 (3)−0.003 (3)−0.025 (4)
C2000.030 (4)0.040 (4)0.026 (4)0.002 (3)0.002 (3)−0.013 (3)
C2010.022 (4)0.030 (4)0.029 (4)0.001 (3)−0.002 (3)−0.011 (3)
C2020.014 (3)0.028 (3)0.032 (4)0.005 (3)−0.001 (3)−0.019 (3)
C2030.018 (3)0.021 (3)0.029 (4)0.000 (3)−0.006 (3)−0.010 (3)
C2040.023 (4)0.029 (4)0.038 (4)0.000 (3)−0.006 (3)−0.018 (3)
N10.022 (3)0.023 (3)0.032 (3)0.000 (2)−0.001 (2)−0.016 (3)
N20.017 (3)0.024 (3)0.029 (3)0.000 (2)−0.006 (2)−0.014 (2)
O10.028 (3)0.032 (3)0.040 (3)0.000 (2)0.005 (2)−0.013 (2)
O20.036 (3)0.030 (3)0.039 (3)0.005 (2)−0.006 (3)−0.012 (2)
O30.024 (3)0.032 (3)0.034 (3)0.011 (2)−0.010 (2)−0.020 (2)
O40.031 (3)0.030 (3)0.053 (4)0.010 (2)−0.016 (3)−0.023 (3)
C510.028 (5)0.039 (5)0.102 (9)0.011 (4)−0.029 (5)−0.033 (6)
C500.031 (5)0.056 (6)0.101 (10)0.023 (4)−0.032 (5)−0.049 (7)
C520.026 (5)0.053 (6)0.108 (10)0.014 (4)−0.020 (5)−0.026 (6)
C530.045 (9)0.072 (11)0.086 (13)0.027 (8)0.002 (9)−0.004 (10)
Geometric parameters (Å, º) top
Ag1—Ag22.9984 (8)C7—F7Z1.3500 (10)
Ag1—N12.259 (6)C8—F8A1.3498 (10)
Ag1—O12.263 (5)C8—F8B1.3491 (10)
Ag1—O3i2.464 (5)C8—F8C1.3500 (10)
Ag1—O32.343 (5)C8—F8X1.3504 (10)
Ag2—N22.300 (6)C8—F8Y1.3501 (10)
Ag2—O22.254 (6)C8—F8Z1.3496 (10)
Ag2—O42.314 (6)C100—C1011.367 (11)
Ag2—C512.714 (9)C100—C200ii1.399 (12)
C1—C21.551 (11)C101—C1021.435 (10)
C1—O11.242 (9)C102—C202ii1.421 (10)
C1—O21.237 (9)C102—N11.356 (9)
C2—C31.479 (16)C103—C1041.431 (11)
C2—F2A1.328 (10)C103—C203ii1.441 (9)
C2—F2B1.337 (10)C103—N11.324 (9)
C3—C41.517 (19)C104—C1051.341 (11)
C3—F3A1.71 (2)C105—C1061.426 (11)
C3—F3B1.287 (18)C106—C204ii1.354 (11)
C3—F3Y1.176 (17)C200—C2011.354 (11)
C3—F3Z1.53 (2)C201—C2021.431 (10)
C4—F4A1.32 (2)C202—N21.336 (9)
C4—F4B1.56 (2)C203—C2041.427 (10)
C4—F4C1.15 (2)C203—N21.335 (9)
C4—F4X1.40 (2)C51—C501.353 (17)
C4—F4Y1.285 (18)C51—C521.383 (17)
C4—F4Z1.37 (2)C50—C52iii1.414 (15)
C5—C61.5398 (10)C52—C531.49 (2)
C5—O31.235 (8)C71—C721.27 (2)
C5—O41.235 (9)C71—C701.42 (2)
C6—C71.5395 (10)C72—C70iv1.39 (2)
C6—F6A1.3499 (10)C72—C731.403 (16)
C6—F6B1.3499 (10)C62—C611.425 (15)
C7—C81.5394 (10)C62—C60v1.22 (3)
C7—F7A1.3499 (10)C61—C601.423 (15)
C7—F7B1.3500 (10)C61—C631.439 (15)
C7—F7Y1.3498 (10)
N1—Ag1—Ag285.08 (15)F8B—C8—F8A106.35 (11)
O1—Ag1—Ag282.90 (13)F8C—C8—F8A111.7 (9)
O1—Ag1—N1132.3 (2)F8C—C8—F8B106.31 (11)
O3—Ag1—Ag282.43 (11)F8Y—C8—F8X106.22 (11)
O3i—Ag1—Ag2159.91 (12)F8Z—C8—F8X107.2 (19)
O3—Ag1—N1118.9 (2)F8Z—C8—F8Y106.28 (11)
O3i—Ag1—N1101.82 (19)C200ii—C100—C101120.4 (7)
O3—Ag1—O1105.0 (2)C102—C101—C100119.5 (7)
O3i—Ag1—O1105.06 (19)C202ii—C102—C101119.4 (6)
N2—Ag2—Ag1107.97 (14)N1—C102—C101119.6 (6)
O2—Ag2—Ag175.28 (14)N1—C102—C202ii121.0 (6)
O2—Ag2—N2120.4 (2)C203ii—C103—C104118.4 (6)
O4—Ag2—Ag178.45 (13)N1—C103—C104120.2 (6)
O4—Ag2—N2116.8 (2)N1—C103—C203ii121.3 (6)
O4—Ag2—O2121.8 (2)C105—C104—C103120.6 (7)
C51—Ag2—Ag1149.5 (2)C106—C105—C104121.7 (8)
C51—Ag2—N2101.7 (3)C204ii—C106—C105119.5 (7)
C51—Ag2—O295.8 (3)C201—C200—C100ii122.1 (7)
C51—Ag2—O482.1 (3)C202—C201—C200119.8 (7)
O1—C1—C2115.0 (7)C201—C202—C102ii118.6 (6)
O2—C1—C2114.6 (7)N2—C202—C102ii120.7 (7)
O2—C1—O1130.3 (8)N2—C202—C201120.6 (7)
C3—C2—C1112.3 (8)C204—C203—C103ii118.2 (6)
F2A—C2—C1111.1 (7)N2—C203—C103ii120.3 (6)
F2A—C2—C3108.3 (8)N2—C203—C204121.5 (6)
F2B—C2—C1111.5 (7)C203—C204—C106ii121.6 (7)
F2B—C2—C3106.8 (8)C102—N1—Ag1121.0 (5)
F2B—C2—F2A106.7 (7)C103—N1—Ag1120.0 (5)
C4—C3—C2121.6 (12)C103—N1—C102117.8 (6)
F3B—C3—F3A86.4 (11)C202—N2—Ag2121.6 (5)
F3Z—C3—F3Y102.7 (13)C203—N2—Ag2119.5 (4)
F4B—C4—F4A101.4 (14)C203—N2—C202118.8 (6)
F4C—C4—F4A118.9 (18)C1—O1—Ag1116.8 (5)
F4C—C4—F4B118.9 (18)C1—O2—Ag2127.4 (5)
F4Y—C4—F4X107.2 (13)C5—O3—Ag1i135.6 (4)
F4Z—C4—F4X102.6 (13)C5—O3—Ag1121.3 (4)
F4Z—C4—F4Y111.0 (14)C5—O4—Ag2128.1 (4)
O3—C5—C6116.4 (5)C50—C51—Ag289.0 (6)
O4—C5—C6114.3 (6)C52—C51—Ag297.0 (6)
O4—C5—O3129.3 (5)C52—C51—C50121.4 (10)
C7—C6—C5114.6 (4)C52iii—C50—C51121.2 (11)
F6A—C6—C5111.6 (5)C50iii—C52—C51117.4 (12)
F6A—C6—C7109.1 (4)C70—C71—C72122.9 (19)
F6B—C6—C5111.3 (5)C70iv—C72—C71129.1 (19)
F6B—C6—C7103.4 (4)C72iv—C70—C71108.0 (17)
F6B—C6—F6A106.27 (10)C60v—C62—C61124 (2)
C8—C7—C6117.2 (4)C60—C61—C62114.7 (14)
F7B—C7—F7A106.26 (11)C61—C60—C62v121 (2)
F7Z—C7—F7Y106.28 (11)
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x, −y+1, −z; (v) −x+1, −y+1, −z.

Experimental details

(1-tol.tol)(1-pxyl)(1-mxyl)(2a)
Crystal data
Chemical formulaC40H16Ag4F28N4O8·3(C7H8)C20H8Ag2F14N2O4·C8H10C8H10·C20H8Ag2F13N2O4·FC20H8Ag2F14N2O4
Mr1920.45928.18928.18822.02
Crystal system, space groupTriclinic, P1Monoclinic, P21/cMonoclinic, P21/cMonoclinic, C2/c
Temperature (K)100100100100
a, b, c (Å)10.6531 (7), 11.2628 (7), 14.4311 (10)11.1146 (3), 22.7107 (8), 13.2046 (4)11.3750 (6), 22.5963 (10), 13.3460 (7)27.578 (3), 9.267 (1), 21.211 (2)
α, β, γ (°)72.401 (3), 86.598 (3), 82.882 (3)90, 111.785 (2), 9090, 113.472 (2), 9090, 118.142 (3), 90
V (Å3)1637.30 (19)3095.07 (17)3146.5 (3)4779.9 (9)
Z1448
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm−1)1.321.391.371.78
Crystal size (mm)0.41 × 0.14 × 0.110.25 × 0.06 × 0.020.42 × 0.2 × 0.120.4 × 0.26 × 0.03
Data collection
DiffractometerBruker APEX-II CCD
diffractometer		Bruker APEX-II CCD
diffractometer		Bruker APEX-II CCD
diffractometer		Bruker APEX-II CCD
diffractometer
Absorption correctionMulti-scan
SADABS2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.0967 before and 0.0640 after correction. The Ratio of minimum to maximum transmission is 0.8435. The λ/2 correction factor is 0.0015.		Multi-scan
SADABS		Multi-scan
SADABS2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.1011 before and 0.0786 after correction. The Ratio of minimum to maximum transmission is 0.8102. The λ/2 correction factor is 0.0015.		Multi-scan
SADABS2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.1234 before and 0.0609 after correction. The Ratio of minimum to maximum transmission is 0.8098. The λ/2 correction factor is 0.0015.
Tmin, Tmax0.629, 0.7460.723, 0.9730.604, 0.7460.604, 0.746
No. of measured, independent and
observed reflections		25299, 7283, 6165 [I > 2σ(I)]26785, 7075, 5377 [I > 2σ(I)]25586, 7203, 6202 [I > 2σ(I)]20167, 5445, 3234 [I > 2σ(I)]
Rint0.0510.0510.0570.064
(sin θ/λ)max (Å−1)0.6500.6500.6500.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.065, 0.167, 1.09 0.041, 0.122, 1.05 0.074, 0.189, 1.12 0.068, 0.230, 1.02
No. of reflections7283707572035445
No. of parameters422453432362
No. of restraints007059
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.065P)2 + 14.5417P]
where P = (Fo2 + 2Fc2)/3		 w = 1/[σ2(Fo2) + (0.0689P)2]
where P = (Fo2 + 2Fc2)/3		 w = 1/[σ2(Fo2) + (0.0599P)2 + 35.1346P]
where P = (Fo2 + 2Fc2)/3		 w = 1/[σ2(Fo2) + (0.1406P)2]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å−3)2.33, −1.731.07, −1.271.83, −1.211.99, −1.39


(2b)(1-tol-pxyl.tol.pxyl)
Crystal data
Chemical formulaC20H8Ag2F14N2O4C40H16Ag4F28N4O8·3(C7.43H8.85)
Mr822.021938.33
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)173100
a, b, c (Å)10.782 (3), 11.006 (4), 12.540 (4)10.6658 (15), 11.2395 (14), 14.325 (2)
α, β, γ (°)71.569 (4), 76.089 (4), 62.229 (4)72.054 (2), 86.608 (3), 83.149 (3)
V (Å3)1241.5 (7)1621.6 (4)
Z21
Radiation typeMo KαMo Kα
µ (mm−1)1.721.33
Crystal size (mm) × × 0.32 × 0.2 × 0.12
Data collection
DiffractometerBruker APEX-II CCD
diffractometer		Bruker APEX-II CCD
diffractometer
Absorption correctionMulti-scan
SADABS2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.1443 before and 0.0437 after correction. The Ratio of minimum to maximum transmission is 0.5803. The λ/2 correction factor is 0.0015.		Multi-scan
SADABS2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.0726 before and 0.0556 after correction. The Ratio of minimum to maximum transmission is 0.8234. The λ/2 correction factor is 0.0015.
Tmin, Tmax0.432, 0.7450.614, 0.746
No. of measured, independent and
observed reflections		9058, 3916, 2491 [I > 2σ(I)]10048, 7080, 4917 [I ≥ 2u(I)]
Rint0.0360.048
(sin θ/λ)max (Å−1)0.5790.652
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.080, 0.272, 1.05 0.071, 0.207, 1.02
No. of reflections39167080
No. of parameters315382
No. of restraints4836
H-atom treatmentH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.1469P)2 + 9.2164P]
where P = (Fo2 + 2Fc2)/3		 w = 1/[σ2(Fo2) + (0.1048P)2 + 7.5111P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å−3)1.72, −1.051.89, −1.63

Computer programs: Bruker APEX2, SAINT v7.60A (Bruker, 2009), Bruker SAINT, SAINT v7.68A (Bruker, 2009), SHELXS (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), ShelXT (Sheldrick, 2008), XS (Sheldrick, 2008), XL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), olex2.refine (Bourhis et al., 2013), Olex2 (Dolomanov et al., 2009), O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341..

 

Footnotes

‡Current address: School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.

§Present address: Johnson Matthey Technology Centre, Savannah, GA, USA.

3The beamline at ESRF was moved in 2014 from station ID31 to ID22.

1Since 2a can be formed in solution in the presence of methanol, without formation of 2b, it is possible that 2b converts to 2a by surface recrystallization in the presence of alcohols.

2Mechanistic details are difficult to establish in the absence of in situ microscopy measurements (e.g. AFM), as illustrated by the findings of Khlobystov and co-workers (Thompson et al., 2004[Thompson, C., Champness, N. R., Khlobystov, A. N., Roberts, C. J., Schroder, M., Tendler, S. J. B. & Wilkinson, M. J. (2004). J. Microsc. 214, 261-271.]; Cui et al., 2009[Cui, X., Khlobystov, A. N., Chen, X., Marsh, D. H., Blake, A. J., Lewis, W., Champness, N. R., Roberts, C. J. & Schröder, M. (2009). Chem. Eur. J. 15, 8861-8873.]).

Acknowledgements

We are grateful to Diamond Light Source and the European Synchrotron Radiation Facility for beam time (beamlines I11, I19 and ID31, respectively) and to Dr Dave Allan for assistance at I19. Dr Nik Reeves-McLaren at the Department of Materials Science and Engineering at the University of Sheffield is also acknowledged for providing access to the Stoe Stadi P X-ray powder diffractometer. We acknowledge the University of Sheffield for funding. IJVY thanks EPSRC for a PhD studentship (grant EP/F02195X/1: `Diffraction for chemical reactions') and for a Doctoral Prize Fellowship.

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IUCrJ
Volume 2| Part 2| March 2015| Pages 188-197
ISSN: 2052-2525
doi:10.1107/S2052252515000147