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ISSN: 2056-9890
Volume 72| Part 2| February 2016| Pages 215-219
doi:10.1107/S2056989016000797

Crystal structure of (μ-1,4-di­carb­­oxy­butane-1,4-di­carboxyl­ato)bis­­[bis­­(tri­phenyl­phosphane)silver(I)] di­chloro­methane tris­­olvate

CROSSMARK_Color_square_no_text.svg
Peter Frenzel,a Marcus Korba and Heinrich Langa*

aTechnische Universität Chemnitz, Fakultät für Naturwissenschaften, Institut für Chemie, Anorganische Chemie, D-09107 Chemnitz
*Correspondence e-mail: heinrich.lang@chemie.tu-chemnitz.de

Edited by M. Zeller, Youngstown State University, USA (Received 19 November 2015; accepted 14 January 2016; online 23 January 2016)

The mol­ecular structure of the tetra­kis(tri­phenyl­phosphan­yl)disilver salt of butane-1,1,4,4-tetra­carb­oxy­lic acid, [Ag2(C8H8O8)(C18H15P)4]·3CH2Cl2, crystallizes with one and a half mol­ecules of di­chloro­methane in the asymmetric unit. The coordination complex exhibits an inversion centre through the central CH2—CH2 bond. The AgI atom has a distorted trigonal–planar P2O coordination environment. The packing is characterized by inter­molecular T-shaped π–π inter­actions between the phenyl rings of the PPh3 substituents in neighbouring mol­ecules, forming a ladder-type superstructure parallel to [010]. These ladders are arranged in layers parallel to (101). Intra­molecular hydrogen bonds between the OH group and one O atom of the Ag-bonded carboxyl­ate group results in an asymmetric bidendate coordination of the carboxyl­ate moiety to the AgI ion.

CCDC reference: 1447419

1. Chemical context

Silver precursors [e.g. silver(I) carboxyl­ates and silver(I) β-diketonates] exhibit a wide range of applications, for instance the formation of thin, metallic layers by means of CVD (Chemical Vapour Deposition) or CCVD (Combustion Chemical Vapour Deposition) (Struppert et al., 2010[Struppert, T., Jakob, A., Heft, A., Grünler, B. & Lang, H. (2010). Thin Solid Films, 518, 5741-5744.]; Jakob et al., 2006[Jakob, A., Schmidt, H., Djiele, P., Shen, Y. & Lang, H. (2006). Microchim. Acta, 156, 77-81.]; Schmidt et al., 2005[Schmidt, H., Jakob, A., Haase, T., Kohse-Höinghaus, K., Schulz, S. E., Wächtler, T., Gessner, T. & Lang, H. (2005). Z. Anorg. Allg. Chem. 631, 2786-2791.]; Lang & Buschbeck, 2009[Lang, H. & Buschbeck, R. (2009). Deposition of metals and metal oxides by means of metal enolates, in The Chemistry of Metal Enolates, edited by J. Zabicky, pp. 929-1017. Chichester: Wiley.]; Lang, 2011[Lang, H. (2011). Jordan. J. Chem. 6, 231-245.]; Lang & Dietrich, 2013[Lang, H. & Dietrich, S. (2013). 4.10 - Metals - Gas-Phase Deposition and Applications, in Comprehensive Inorganic Chemistry II (Second Edition), edited by J. Reedijk & K. Poeppelmeier, pp. 211-269. Amsterdam: Elsevier.]; Chi & Lu, 2001[Chi, K. M. & Lu, Y. H. (2001). Chem. Vap. Deposition, 7, 117-120.]), spin coating (Jakob et al., 2010[Jakob, A., Rüffer, T., Schmidt, H., Djiele, P., Körbitz, K., Ecorchard, P., Haase, T., Kohse-Höinghaus, K., Frühauf, S., Wächtler, T., Schulz, S., Gessner, T. & Lang, H. (2010). Eur. J. Inorg. Chem. pp. 2975-2986.]) or inkjet printing (Jahn et al., 2010a[Jahn, S. F., Blaudeck, T., Baumann, R. R., Jakob, A., Ecorchard, P., Rüffer, T., Lang, H. & Schmidt, P. (2010a). Chem. Mater. 22, 3067-3071.],b[Jahn, S. F., Jakob, A., Blaudeck, T., Schmidt, P., Lang, H. & Baumann, R. R. (2010b). Thin Solid Films, 518, 3218-3222.]; Gäbler et al., 2016[Gäbler, C., Schliebe, C., Adner, D., Blaudeck, T. & Lang, H. (2016). Inkjet Printing of Group-11 Metal Structures, in Comprehensive Guide for Nanocoatings Technology. New York: Nova Science Publishers. In the press.]). The respective silver layers show closed and homogeneous silver films and therefore possess a good conductivity. In addition, silver carboxyl­ates such as [AgO2CR]n (n is the degree of aggregation) allow for the formation and stabilization of silver nanoparticles, which can, for example, be used for catalytic processes (Steffan et al., 2009[Steffan, M., Jakob, A., Claus, P. & Lang, H. (2009). Catal. Commun. 10, 437-441.]). They are also used in biological studies (Fourie et al., 2012[Fourie, E., Erasmus, E., Swarts, J. C., Tuchscherer, A., Jakob, A., Lang, H., Joone, G. K. & Van Rensburg, C. E. (2012). Anticancer Res. 32, 519-522.]; Langner et al., 2012[Langner, E. H. G., Swarts, J. C., Tuchscherer, A., Lang, H., Joone, G. K. & van Rensburg, C. E. J. (2012). Anticancer Res. 32, 2697-2701.]).

[Scheme 1]

A further application of silver carboxyl­ate precursors includes their use for joining of bulk copper to produce metallic inter­connects, for example in microelectronic applications (Oestreicher et al., 2012[Oestreicher, A., Röhrich, T. & Lerch, M. (2012). J. Nanosci. Nanotechnol. 12, 9088-9093.], 2013[Oestreicher, A., Röhrich, T., Wilden, J., Lerch, M., Jakob, A. & Lang, H. (2013). Appl. Surf. Sci. 265, 239-244.]).

We anti­cipate that a metal oxide layer will need to be removed during such a silver-facilitated copper-joining process. Leaving some of the carboxyl groups of the silver precursor uncoordinated is expected to assist in this process. In the case of sparingly soluble silver carboxyl­ates, the solubility in common organic solvents can be increased through addition of phosphanes, such as triphenyl phosphane. In this context, the title compound (I)[link] was prepared by the reaction of the disilver salt of butane-1,1,4,4-tetra­carboxyl acid (BTCA) with tri­phenyl­phosphane.

2. Structural commentary

The title compound (I)[link] crystallizes in the triclinic space group P[\overline{1}]. The asymmetric unit contains a half mol­ecule of butane-1,4-dicarb­oxy-1,4-di­carboxyl­ate bonded to a bis­(tri­phenyl­phosphan­yl)silver moiety and 1.5 mol­ecules of di­chloro­methane. The inversion centre to build up the whole disilver complex is located in the middle of the C4—C4′ bond (Fig. 1[link]; (A): –x, –y + 1, –z + 2). The three mol­ecules of di­chloro­methane are also located on or nearby inversion centres (Fig. 1[link]; C2S, (B): –x + 1, –y + 1, –z; C1S, C1SB, –x + 1, –y, –z; see Refinement section for details).

[Figure 1]
Figure 1
The mol­ecular structure of (I)[link], with displacement ellipsoids drawn at the 30% probability level, including the intra­molecular hydrogen bonds. All non-O-bonded H atoms and the labels of the o-, m- and p-phenyl C atoms have been omitted for clarity. [Symmetry codes: (A) −x, −y + 1, −z + 2; (B) −x + 1, −y + 1, −z; (C) −x + 1, −y, −z.]

The anionic C8H8O8 moiety contains an intra­molecular hydrogen bond between the O3 atom of the HO2C-carb­oxy group and the O2 atom that is in inter­action with Ag1 (Fig. 1[link], Table 1[link]), resulting in a boat-type conformation including the C1, C2 and C3 atoms, due to a synperiplanar torsion of the C1—O2 and C3—O3 bonds by 6.3 (2)°. Within the H-bearing carboxyl­ato substituent a distinction between the C,O single [1.321 (3) Å] and double [1.205 (3) Å] bonds can be observed. The C1 labeled carboxyl­ato group exhibits an unsymmetrically bidendate binding to Ag1. Therefore, O1 is, with 2.3305 (17) Å, σ-bonded, whereas O2 exhibits a weaker inter­action with an increased O2⋯Ag1 distance of 2.6872 (19) Å, probably due to the involvement in the hydrogen bond.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O3—H3⋯O2 0.84 1.79 2.525 (3) 146
C1S—H1S1⋯O3i 0.99 2.53 2.997 (4) 108
C1SB—H1S4⋯O3i 0.99 2.46 3.04 (4) 117
Symmetry code: (i) -x+1, -y+1, -z+1.

The Ag1 atom exhibits a somewhat distorted trigonal–planar P2O coordination environment, whereby the two phosphanes enclose an increased P—Ag—P angle of 128.56 (2)°, in contrast to the O1—Ag1—P angles of 117.69 (5) (P1) and 113.27 (5)° (P2). The weak inter­action to the O2 atom occurs below this AgP2 plane with an inter­action to the CO2 group of 67.38 (17)° with, however, two nearly equal C1—O1/O2 bond lengths of 1.251 (3) (O1) and 1.261 (3) Å (O2). Both phosphanes reveal an eclipsed conformation regarding the phenyl rings of 2.09 (10)°.

3. Supra­molecular features

The packing of (I)[link] consists of a layer-type structure parallel to (101), which is supported by weak T-shaped π–π inter­actions (Sinnokrot et al., 2002[Sinnokrot, M. O., Valeev, E. F. & Sherrill, C. D. (2002). J. Am. Chem. Soc. 124, 10887-10893.]) between the C5–C10 and the C35–C40 labeled phenyl rings with centroid–centroid distances of 4.8497 (16) Å [α = 77.40 (13)°] at both sides of the mol­ecules, forming a ladder-type arrangement parallel to [010] (Fig. 2[link]). These ladders are packed along (101) through the phenyl rings, however, without showing any further π–π or C—H inter­actions.

[Figure 2]
Figure 2
Inter­molecular T-shaped π–π inter­actions (blue) between the centroids (D) of the C5–C10 and C35–C40 labeled phenyl rings in the crystal structure of (I)[link]. All H atoms and solvent mol­ecules have been omitted for clarity. D—D = 4.8497 (16) Å; α = 77.40 (13) °. [Symmetry codes: (′) −x, −y + 1, −z + 2; (A) x, [{1\over 2}] − y, z − [{1\over 2}]; (B) x, y, x − 1.]

One di­chloro­methane is stabilized by a non-classical hydrogen-bridge bond from C1S, as the hydrogen-bond donor, to the hydroxyl O3 atom (Table 1[link]), which also acts as hydrogen-bridge bond donor in an intra­molecular classical bridge bond (see Structural commentary).

Further inter­molecular inter­actions involving hydrogen bonds or O⋯Ag inter­actions are not observed.

4. Database survey

In the CSD database (Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]; Version 5.36), only two acyclic silver tetra­carboxyl­ates with six-membered carbon backbones are reported. These are butane-1,2,3,4-tetra­carboxyl­ato silver compounds containing further nitro­gen and oxygen donor ligands, coordinating the silver ions either in a tetra­hedral or a T-shaped trigonal fashion (Sun et al., 2010[Sun, D., Zhang, N., Xu, Q.-J., Huang, R.-B. & Zheng, L.-S. (2010). J. Mol. Struct. 975, 17-22.]). Three aliphatic cyclo­hexane silver complexes with four to six carboxyl­ate groups are also known. Within those, the silver ions are also coordinated by additional ligands such as ammonia and water and possess distorted tetra­hedral coordination or Y-shaped coordination environments (Wang et al., 2006[Wang, J., Hu, S. & Tong, M.-L. (2006). Eur. J. Inorg. Chem. 2006, 2069-2077.], 2009[Wang, J., Ou, Y.-C., Shen, Y., Yun, L., Leng, J.-D., Lin, Z. & Tong, M.-L. (2009). Cryst. Growth Des. 9, 2442-2450.]). For six-membered unbranched acyclic silver di­carboxyl­ates derived from adipic acid, more crystal structures are reported compared to the respective tetra­carboxyl­ato derivatives. Several coordination geometries for the silver atoms are reported such as T-shaped (Wu et al., 1995[Wu, D.-D. & Mak, T. C. W. (1995). J. Chem. Soc. Dalton Trans. pp. 2671-2678.]), tetra­hedral (Li et al., 2011[Li, Y.-H., Sun, D., Luo, G.-G., Liu, F.-J., Hao, H.-J., Wen, Y.-M., Zhao, Y., Huang, R.-B. & Zheng, L.-S. (2011). J. Mol. Struct. 1000, 85-91.]) or trigonal–planar environments (Liu et al., 2009[Liu, S., Zhang, X., Wang, H., Meng, C. & Mou, W. (2009). Chin. J. Chem. 27, 722-726.]) containing nitro­gen, oxygen or sulfur donor ligands. To the best of our knowledge, the title compound (I)[link] is the only example of a silver tetra­carboxyl­ate consisting of a six-membered carbon backbone and containing a silver–phospho­rus bond. In contrast to the title compound, which exists as a monomer presumably due to the steric shielding by triphenyl phosphane, all of the above-mentioned complexes exist as polymeric networks, formed by bridging through the different donor atoms of the ligands. For example, by using silver di­carboxyl­ates frequently the formation of dimeric sub-units can take place, which in turn results in the construction of polymeric systems (Wu et al., 1995[Wu, D.-D. & Mak, T. C. W. (1995). J. Chem. Soc. Dalton Trans. pp. 2671-2678.]). Structures containing water mol­ecules coordinating to the AgI ions result in the formation of a further polymeric hydrogen bridge-bond network, also including carboxyl­ato moieties (Wang et al., 2006[Wang, J., Hu, S. & Tong, M.-L. (2006). Eur. J. Inorg. Chem. 2006, 2069-2077.], 2009[Wang, J., Ou, Y.-C., Shen, Y., Yun, L., Leng, J.-D., Lin, Z. & Tong, M.-L. (2009). Cryst. Growth Des. 9, 2442-2450.]).

5. Synthesis and crystallization

Synthesis of butane-1,4-dicarboxyl-1,4-di­carboxyl­ato­di­silver(I):

Potassium tert-butano­late (192 mg, 1.71 mmol) was added to a solution of butane-1,1,4,4-tetra­carboxyl acid (200 mg, 0.854 mmol) in 5 mL of tetra­hydro­furan. After stirring overnight at ambient temperature, the reaction mixture was filtered off and the residue was washed trice with tetra­hydro­furan (10 mL each) and dried under vacuum (yield 243 mg). Subsequently, the obtained colorless solid (243 mg, 0.783 mmol) was dissolved in water (15 mL) and added dropwise to a solution of silver nitrate (267 mg, 1.57 mmol) in water (8 mL). After 12 h of stirring the colorless precipitate was filtered off and washed twice with water (10 mL each) and dried in a desiccator. The desired colorless butane-1,4-dicarboxyl-1,4-di­carboxyl­atodisilver(I) was obtained in a yield of 71%, based on butane-1,1,4,4-tetra­carboxyl acid (271 mg, 0.608 mmol). Analysis calculated for C8H8Ag2O8 (447.88): C, 21.45; H, 1.80. Found: C, 21.49; H, 1.68. IR (KBr, cm−1): ν = 2977 (m), 2903 (m), 2461 (m), 1660 (s), 1549 (vs), 1380 (s), 1257 (s), 1069 (s), 955 (m), 711 (m).

Synthesis of (μ-1,4-di­carb­oxy­butane-1,4-di­carboxyl­ato)bis[bis­(tri­phenyl­phosphane)silver(I)]:

To a suspension of butane-1,4-dicarboxyl-1,4-di­carboxyl­atodisilver(I) (100 mg, 0.223 mmol) in 10 mL of tetra­hydro­furan, PPh3 (234 mg, 0.892 mmol) was added in a single portion at ambient temperature. After 12 h of stirring the reaction mixture was filtered through a pad of celite. After removal of all volatiles under reduced pressure, the title compound (I)[link] was obtained as a colorless solid (275 mg, 0.184 mmol, 83% based on butane-1,4-dicarboxyl-1,4-di­carboxyl­atodisilver(I). Slow diffusion of pentane into a di­chloro­methane solution containing (I)[link] at ambient temperature afforded colourless crystals of (I)[link]. M.p. 398 K (decomp.). 1H NMR (500 MHz, CDCl3, 298 K, p.p.m.): δ = 7.39–7.29 (m, 60H, C6H5), 2.93 (m, 2H, CH), 2.04 (m, 4H, CH2). 13C{1H} NMR (126 MHz, CDCl3, 298 K, p.p.m.): δ = 175.9 (s, C=O), 134.0 (d, 2JPC = 16.1 Hz, o-C6H5), 131.7 (d, 1JPC = 29.3 Hz, Ci-C6H5), 130.6 (s, p-C6H5), 129.1 (d, 3JPC = 9.3 Hz, m-C6H5), 50.8 (s, CH), 29.6 (s, CH2). 31P{1H} NMR (203 MHz, CDCl3, 298 K, p.p.m.): δ = 10.3 (s). IR (KBr, cm−1): ν = 3108 (w), 2993 (w), 1751 (s), 1494 (vs), 1106 (s), 752 (vs), 701 (vs).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. C-bonded hydrogen atoms were placed in calculated positions and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C) and a C—H distance of 0.93 Å for aromatic (AFIX 43), 0.98 Å for methine (AFIX 13) and 0.97 Å for methyl­ene H atoms (AFIX 23). The same applies for the O-bonded H atom; however, the torsion angle was derived from electron density (AFIX 147). The structure contains three mol­ecules of di­chloro­methane as the solvent. Both crystallographically independent mol­ecules consist of two moieties each. One mol­ecule was refined as disordered over two positions (C1S; C1SB) with occupancies of 92.7 (2) and 7.3 (3)%, respectively. The less prevalent moiety of C1SB is located close to a crystallographic inversion centre and symmetry-related pairs are mutually exclusive. The second disordered mol­ecule is located directly atop of another inversion centre with an occupancy of 0.5 (Fig. 1[link]), with the inversion centre located near the C2S and Cl1B atoms. The less-occupied methyl­ene chloride mol­ecule was restrained to have a geometry similar to that of its major moiety counterpart by using the SAME command. Uij components of ADPs for C1S C1SB Cl1B and Cl2B were restrained to be similar if closer than 1.7 Å (SIMU restraint, McArdle, 1995[McArdle, P. (1995). J. Appl. Cryst. 28, 65.]; Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).

Table 2
Experimental details

Crystal data
Chemical formula [Ag2(C8H8O8)(C18H15P)4]·3CH2Cl2
Mr 1751.74
Crystal system, space group Triclinic, P[\overline{1}]
Temperature (K) 110
a, b, c (Å) 10.0279 (3), 12.9540 (4), 16.8190 (5)
α, β, γ (°) 112.306 (3), 96.080 (3), 103.601 (3)
V (Å3) 1917.80 (11)
Z 1
Radiation type Mo Kα
μ (mm−1) 0.86
Crystal size (mm) 0.3 × 0.3 × 0.2
 
Data collection
Diffractometer Oxford Gemini S
Absorption correction Multi-scan (CrysAlis RED; Oxford Diffraction, 2006[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England.])
Tmin, Tmax 0.889, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 21441, 8700, 7959
Rint 0.024
(sin θ/λ)max (Å−1) 0.680
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.083, 1.06
No. of reflections 8700
No. of parameters 507
No. of restraints 27
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 2.28, −0.61
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England.]), CrysAlis RED (Oxford Diffraction, 2006[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England.]), SHELXS2013 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information

CCDC reference: 1447419

Crystal structure: contains datablocks I, 1R. DOI: 10.1107/S2056989016000797/zl2653sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989016000797/zl2653Isup2.hkl

checkCIF report


Chemical context top

Silver precursors [e.g. silver(I) carboxyl­ates and silver(I) β-diketonates] exhibit a wide range of applications, for instance the formation of thin, metallic layers by means of CVD (Chemical Vapour Deposition) or CCVD (Combustion Chemical Vapour Deposition) (Struppert et al., 2010; Jakob et al., 2006; Schmidt et al., 2005; Lang & Buschbeck, 2009; Lang, 2011; Lang & Dietrich, 2013; Chi & Lu, 2001), spin coating (Jakob et al., 2010) or inkjet printing (Jahn et al., 2010a,b; Gäbler et al., 2016). The respective silver layers show closed and homogeneous silver films and therefore possess a good conductivity. In addition, silver carboxyl­ates such as [AgO2CR]n (n is the degree of aggregation) allow for the formation and stabilization of silver nanoparticles, which can, for example, be used for catalytic processes (Steffan et al., 2009). They are also used in biological studies (Fourie et al., 2012; Langner et al., 2012).

A further application of silver carboxyl­ate precursors includes their use for joining of bulk copper to produce metallic inter­connects, for example in microelectronic applications (Oestreicher et al., 2012, 2013).

We anti­cipate that a metal oxide layer will need to be removed during such a silver-facilitated copper-joining process. Leaving some of the carboxyl groups of the silver precursor uncoordinated is expected to assist in this process. In the case of sparingly soluble silver carboxyl­ates, the solubility in common organic solvents can be increased through addition of phosphanes, such as e.g. tri­phenyl phosphane. In this context, the title compound (I) was prepared by reaction of the disilver salt of butane-1,1,4,4-tetra­carboxyl acid (BTCA) with tri­phenyl­phosphane.

Structural commentary top

The title compound (I) crystallizes in the triclinic space group P1. The asymmetric unit contains a half molecule of butane-1,4-di­carb­oxy-1,4-di­carboxyl­ate bonded to a bis­(tri­phenyl­phosphanyl)silver moiety and 1.5 molecules of di­chloro­methane. The inversion centre to build up the whole disilver complex is located in the middle of the C4—C4' bond (Fig. 1; (A): –x, –y + 1, –z + 2). The three molecules of di­chloro­methane are also located on or nearby inversion centres (Fig. 1; C2S, (B): –x + 1, –y + 1, –z; C1S, C1SB, –x + 1, –y, –z; see Refinement section for details).

The butane tetra­carb­oxy­lic moiety contains an intra­molecular hydrogen bond between the O3 atom of the HO2C-carb­oxy group and the O2 atom that is in inter­action with Ag1 (Fig. 1, Table 1), resulting in a boat-type conformation including the C1, C2 and C3 atoms, due to a synperiplanar torsion of the C1—O2 and C3—O3 bonds by 6.3 (2)°. Within the H-bearing carboxyl­ato substituent a distinction between the C,O single [1.321 (3) Å] and double [1.205 (3) Å] bonds can be observed. The C1 labeled carboxyl­ato group exhibits an unsymmetrically bidendate binding to Ag1. Therefore, O1 is, with 2.3305 (17) Å, σ-bonded, whereas O2 exhibits a weaker inter­action with an increased O2···Ag1 distance of 2.6872 (19) Å, probably due to the involvement in the hydrogen bond.

The Ag1 atom exhibits a somewhat distorted trigonal–planar coordination environment, whereby the two phosphanes enclose an increased P—Ag—P angle of 128.56 (2)°, in contrast to the O1—Ag1—P angles of 117.69 (5) (P1) and 113.27 (5)° (P2). The weak inter­action to the O2 atom occurs below this AgP2 plane with an inter­action to the CO2 group of 67.38 (17)° with, however, two nearly equal C1—O1/O2 bond lengths of 1.251 (3) (O1) and 1.261 (3) Å (O2). Both phosphanes reveal an eclipsed conformation regarding the phenyl rings of 2.09 (10)°.

Supra­molecular features top

The packing of (I) consists of a layer-type structure parallel to (101), which is supported by weak T-shaped π–π inter­actions (Sinnokrot et al., 2002) between the C5–C10 and the C35–C40 labeled phenyl rings with centroid–centroid distances of 4.8497 (16) Å [α = 77.40 (13)°] at both sides of the molecules, forming a ladder-type arrangement parallel to [010], the b axis (Fig. 2). These ladders are packed along (101) through the phenyl rings, however, without showing any further π–π or C—H inter­actions.

One di­chloro­methane is stabilized by a non-classical hydrogen-bridge bond from C1S, as the hydrogen-bond donor, to the hydroxyl O3 atom (Table 1), which also acts as hydrogen-bridge bond donor in an intra­molecular classical bridge bond (see Structural commentary).

Further inter­molecular inter­actions involving hydrogen bonds or O···Ag inter­actions are not observed.

Database survey top

In the CSD database (Groom & Allen, 2014; Version 5.36), only two acyclic silver tetra­carboxyl­ates with six-membered carbon backbones are reported. These are butane-1,2,3,4-tetra­carboxyl­ato silver compounds containing further nitro­gen and oxygen donor ligands, coordinating the silver ions either in a tetra­hedral or a T-shaped trigonal fashion (Sun et al., 2010). Three aliphatic cyclo­hexane silver complexes with four to six carboxyl­ate groups are also known. Within those, the silver ions are also coordinated by additional ligands such as ammonia and water and possess distorted tetra­hedral coordination or Y-shaped geometries (Wang et al., 2006, 2009). For six-membered unbranched acyclic silver di­carboxyl­ates derived from adipic acid, more crystal structures are reported compared to the respective tetra­carboxyl­ato derivatives. Several coordination geometries for the silver atoms are reported such as T-shaped (Wu et al., 1995), tetra­hedral (Li et al., 2011) or trigonal–planar environments (Liu et al., 2009) containing nitro­gen, oxygen or sulfur donor ligands. To the best of our knowledge, the title compound (I) is the only example of a silver tetra­carboxyl­ate consisting of a six-membered carbon backbone and containing a silver–phospho­rus bond. In contrast to the title compound, which exists as a monomer presumably due to the steric shielding by tri­phenyl phosphane, all of the above-mentioned complexes exist as polymeric networks, formed by bridging through the different donor atoms of the ligands. For example, by using silver di­carboxyl­ates frequently the formation of dimeric sub-units can take place, which in turn results in the construction of polymeric systems (Wu et al., 1995). Structures containing water molecules coordinating to the Ag ions results in the formation of a further polymeric hydrogen bridge-bond network, also including carboxyl­ato moieties (Wang et al., 2006, 2009).

Synthesis and crystallization top

\ Synthesis of butane-1,4-di­carboxyl-1,4-di­carboxyl­atodisilver(I):

Potassium tert-butano­late (192 mg, 1.71 mmol) was added to a solution of butane-1,1,4,4-tetra­carboxyl acid (200 mg, 0.854 mmol) in 5 ml of tetra­hydro­furan. After stirring overnight at ambient temperature, the reaction mixture was filtered off and the residue was washed trice with tetra­hydro­furan (10 ml each) and dried under vacuum (yield 243 mg). Subsequently, the obtained colorless solid (243 mg, 0.783 mmol) was dissolved in water (15 ml) and added dropwise to a solution of silver nitrate (267 mg, 1.57 mmol) in water (8 ml). After 12 h of stirring the colorless precipitate was filtered off and washed twice with water (10 ml each) and dried in a desiccator. The desired colorless butane-1,4-di­carboxyl-1,4-di­carboxyl­atodisilver(I) was obtained in a yield of 71%, based on butane-1,1,4,4-tetra­carboxyl acid (271 mg, 0.608 mmol). Analysis calculated for C8H8Ag2O8 (447.88): C, 21.45; H, 1.80. Found: C, 21.49; H, 1.68. IR (KBr, cm−1): ν = 2977 (m), 2903 (m), 2461 (m), 1660 (s), 1549 (vs), 1380 (s), 1257 (s), 1069 (s), 955 (m), 711 (m).

Synthesis of butane-1,4-di­carb­oxy-1,4-di­carboxyl­ato-tetra­kis(tri­phenyl­phosphine-\ κP)disilver(I):

To a suspension of butane-1,4-di­carboxyl-1,4-di­carboxyl­atodisilver(I) (100 mg, 0.223 mmol) in 10 ml of tetra­hydro­furan, PPh3 (234 mg, 0.892 mmol) was added in a single portion at ambient temperature. After 12 h of stirring the reaction mixture was filtered through a pad of celite. After removal of all volatiles under reduced pressure, the title compound (I) was obtained as a colorless solid (275 mg, 0.184 mmol, 83% based on butane-1,4-di­carboxyl-1,4-di­carboxyl­atodisilver(I). Slow diffusion of pentane into a di­chloro­methane solution containing (I) at ambient temperature afforded colourless crystals of (I). M.p. 398 K (decomp.). 1H NMR (500 MHz, CDCl3, 298 K, p.p.m.): δ = 7.39–7.29 (m, 60H, C6H5), 2.93 (m, 2H, CH), 2.04 (m, 4H, CH2). 13C{1H} NMR (126 MHz, CDCl3, 298 K, p.p.m.): δ = 175.9 (s, C=O), 134.0 (d, 2JPC = 16.1 Hz, o-C6H5), 131.7 (d, 1JPC = 29.3 Hz, Ci-C6H5), 130.6 (s, p-C6H5), 129.1 (d, 3JPC = 9.3 Hz, m-C6H5), 50.8 (s, CH), 29.6 (s, CH2). 31P{1H} NMR (203 MHz, CDCl3, 298 K, p.p.m.): δ = 10.3 (s). IR (KBr, cm−1): ν = 3108 (w), 2993 (w), 1751 (s), 1494 (vs), 1106 (s), 752 (vs), 701 (vs).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. C-bonded hydrogen atoms were placed in calculated positions and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C) and a C—H distance of 0.93 Å for aromatic (AFIX 43), 0.98 Å for methine (AFIX 13) and 0.97 Å for methyl­ene H atoms (AFIX 23). The same applies for the O-bonded H atom; however, the torsion angle was derived from electron density (AFIX 147). The structure contains three molecules of di­chloro­methane as the packing solvent. Both crystallographically independent molecules consist of two moieties each. One molecule was refined as disordered over two positions (C1S; C1SB) with occupancies of 92.7 (2) and 7.3 (3)%, respectively. The less prevalent moiety of C1SB is located close to a crystallographic inversion centre and symmetry-related pairs are mutually exclusive. The second disordered molecule is located directly atop of another inversion centre with an occupancy of 0.5 (Fig. 1), with the inversion centre located near the C2S and Cl1B atoms. The less-occupied methyl­ene chloride molecule was restrained to have a geometry similar to that of its major moiety counterpart by using the SAME command. Uij components of ADPs for C1S C1SB Cl1B and Cl2B were restrained to be similar if closer than 1.7 Å (SIMU restraint, McArdle, 1995; Sheldrick, 2008).

Structure description top

Silver precursors [e.g. silver(I) carboxyl­ates and silver(I) β-diketonates] exhibit a wide range of applications, for instance the formation of thin, metallic layers by means of CVD (Chemical Vapour Deposition) or CCVD (Combustion Chemical Vapour Deposition) (Struppert et al., 2010; Jakob et al., 2006; Schmidt et al., 2005; Lang & Buschbeck, 2009; Lang, 2011; Lang & Dietrich, 2013; Chi & Lu, 2001), spin coating (Jakob et al., 2010) or inkjet printing (Jahn et al., 2010a,b; Gäbler et al., 2016). The respective silver layers show closed and homogeneous silver films and therefore possess a good conductivity. In addition, silver carboxyl­ates such as [AgO2CR]n (n is the degree of aggregation) allow for the formation and stabilization of silver nanoparticles, which can, for example, be used for catalytic processes (Steffan et al., 2009). They are also used in biological studies (Fourie et al., 2012; Langner et al., 2012).

A further application of silver carboxyl­ate precursors includes their use for joining of bulk copper to produce metallic inter­connects, for example in microelectronic applications (Oestreicher et al., 2012, 2013).

We anti­cipate that a metal oxide layer will need to be removed during such a silver-facilitated copper-joining process. Leaving some of the carboxyl groups of the silver precursor uncoordinated is expected to assist in this process. In the case of sparingly soluble silver carboxyl­ates, the solubility in common organic solvents can be increased through addition of phosphanes, such as e.g. tri­phenyl phosphane. In this context, the title compound (I) was prepared by reaction of the disilver salt of butane-1,1,4,4-tetra­carboxyl acid (BTCA) with tri­phenyl­phosphane.

The title compound (I) crystallizes in the triclinic space group P1. The asymmetric unit contains a half molecule of butane-1,4-di­carb­oxy-1,4-di­carboxyl­ate bonded to a bis­(tri­phenyl­phosphanyl)silver moiety and 1.5 molecules of di­chloro­methane. The inversion centre to build up the whole disilver complex is located in the middle of the C4—C4' bond (Fig. 1; (A): –x, –y + 1, –z + 2). The three molecules of di­chloro­methane are also located on or nearby inversion centres (Fig. 1; C2S, (B): –x + 1, –y + 1, –z; C1S, C1SB, –x + 1, –y, –z; see Refinement section for details).

The butane tetra­carb­oxy­lic moiety contains an intra­molecular hydrogen bond between the O3 atom of the HO2C-carb­oxy group and the O2 atom that is in inter­action with Ag1 (Fig. 1, Table 1), resulting in a boat-type conformation including the C1, C2 and C3 atoms, due to a synperiplanar torsion of the C1—O2 and C3—O3 bonds by 6.3 (2)°. Within the H-bearing carboxyl­ato substituent a distinction between the C,O single [1.321 (3) Å] and double [1.205 (3) Å] bonds can be observed. The C1 labeled carboxyl­ato group exhibits an unsymmetrically bidendate binding to Ag1. Therefore, O1 is, with 2.3305 (17) Å, σ-bonded, whereas O2 exhibits a weaker inter­action with an increased O2···Ag1 distance of 2.6872 (19) Å, probably due to the involvement in the hydrogen bond.

The Ag1 atom exhibits a somewhat distorted trigonal–planar coordination environment, whereby the two phosphanes enclose an increased P—Ag—P angle of 128.56 (2)°, in contrast to the O1—Ag1—P angles of 117.69 (5) (P1) and 113.27 (5)° (P2). The weak inter­action to the O2 atom occurs below this AgP2 plane with an inter­action to the CO2 group of 67.38 (17)° with, however, two nearly equal C1—O1/O2 bond lengths of 1.251 (3) (O1) and 1.261 (3) Å (O2). Both phosphanes reveal an eclipsed conformation regarding the phenyl rings of 2.09 (10)°.

The packing of (I) consists of a layer-type structure parallel to (101), which is supported by weak T-shaped π–π inter­actions (Sinnokrot et al., 2002) between the C5–C10 and the C35–C40 labeled phenyl rings with centroid–centroid distances of 4.8497 (16) Å [α = 77.40 (13)°] at both sides of the molecules, forming a ladder-type arrangement parallel to [010], the b axis (Fig. 2). These ladders are packed along (101) through the phenyl rings, however, without showing any further π–π or C—H inter­actions.

One di­chloro­methane is stabilized by a non-classical hydrogen-bridge bond from C1S, as the hydrogen-bond donor, to the hydroxyl O3 atom (Table 1), which also acts as hydrogen-bridge bond donor in an intra­molecular classical bridge bond (see Structural commentary).

Further inter­molecular inter­actions involving hydrogen bonds or O···Ag inter­actions are not observed.

In the CSD database (Groom & Allen, 2014; Version 5.36), only two acyclic silver tetra­carboxyl­ates with six-membered carbon backbones are reported. These are butane-1,2,3,4-tetra­carboxyl­ato silver compounds containing further nitro­gen and oxygen donor ligands, coordinating the silver ions either in a tetra­hedral or a T-shaped trigonal fashion (Sun et al., 2010). Three aliphatic cyclo­hexane silver complexes with four to six carboxyl­ate groups are also known. Within those, the silver ions are also coordinated by additional ligands such as ammonia and water and possess distorted tetra­hedral coordination or Y-shaped geometries (Wang et al., 2006, 2009). For six-membered unbranched acyclic silver di­carboxyl­ates derived from adipic acid, more crystal structures are reported compared to the respective tetra­carboxyl­ato derivatives. Several coordination geometries for the silver atoms are reported such as T-shaped (Wu et al., 1995), tetra­hedral (Li et al., 2011) or trigonal–planar environments (Liu et al., 2009) containing nitro­gen, oxygen or sulfur donor ligands. To the best of our knowledge, the title compound (I) is the only example of a silver tetra­carboxyl­ate consisting of a six-membered carbon backbone and containing a silver–phospho­rus bond. In contrast to the title compound, which exists as a monomer presumably due to the steric shielding by tri­phenyl phosphane, all of the above-mentioned complexes exist as polymeric networks, formed by bridging through the different donor atoms of the ligands. For example, by using silver di­carboxyl­ates frequently the formation of dimeric sub-units can take place, which in turn results in the construction of polymeric systems (Wu et al., 1995). Structures containing water molecules coordinating to the Ag ions results in the formation of a further polymeric hydrogen bridge-bond network, also including carboxyl­ato moieties (Wang et al., 2006, 2009).

Synthesis and crystallization top

\ Synthesis of butane-1,4-di­carboxyl-1,4-di­carboxyl­atodisilver(I):

Potassium tert-butano­late (192 mg, 1.71 mmol) was added to a solution of butane-1,1,4,4-tetra­carboxyl acid (200 mg, 0.854 mmol) in 5 ml of tetra­hydro­furan. After stirring overnight at ambient temperature, the reaction mixture was filtered off and the residue was washed trice with tetra­hydro­furan (10 ml each) and dried under vacuum (yield 243 mg). Subsequently, the obtained colorless solid (243 mg, 0.783 mmol) was dissolved in water (15 ml) and added dropwise to a solution of silver nitrate (267 mg, 1.57 mmol) in water (8 ml). After 12 h of stirring the colorless precipitate was filtered off and washed twice with water (10 ml each) and dried in a desiccator. The desired colorless butane-1,4-di­carboxyl-1,4-di­carboxyl­atodisilver(I) was obtained in a yield of 71%, based on butane-1,1,4,4-tetra­carboxyl acid (271 mg, 0.608 mmol). Analysis calculated for C8H8Ag2O8 (447.88): C, 21.45; H, 1.80. Found: C, 21.49; H, 1.68. IR (KBr, cm−1): ν = 2977 (m), 2903 (m), 2461 (m), 1660 (s), 1549 (vs), 1380 (s), 1257 (s), 1069 (s), 955 (m), 711 (m).

Synthesis of butane-1,4-di­carb­oxy-1,4-di­carboxyl­ato-tetra­kis(tri­phenyl­phosphine-\ κP)disilver(I):

To a suspension of butane-1,4-di­carboxyl-1,4-di­carboxyl­atodisilver(I) (100 mg, 0.223 mmol) in 10 ml of tetra­hydro­furan, PPh3 (234 mg, 0.892 mmol) was added in a single portion at ambient temperature. After 12 h of stirring the reaction mixture was filtered through a pad of celite. After removal of all volatiles under reduced pressure, the title compound (I) was obtained as a colorless solid (275 mg, 0.184 mmol, 83% based on butane-1,4-di­carboxyl-1,4-di­carboxyl­atodisilver(I). Slow diffusion of pentane into a di­chloro­methane solution containing (I) at ambient temperature afforded colourless crystals of (I). M.p. 398 K (decomp.). 1H NMR (500 MHz, CDCl3, 298 K, p.p.m.): δ = 7.39–7.29 (m, 60H, C6H5), 2.93 (m, 2H, CH), 2.04 (m, 4H, CH2). 13C{1H} NMR (126 MHz, CDCl3, 298 K, p.p.m.): δ = 175.9 (s, C=O), 134.0 (d, 2JPC = 16.1 Hz, o-C6H5), 131.7 (d, 1JPC = 29.3 Hz, Ci-C6H5), 130.6 (s, p-C6H5), 129.1 (d, 3JPC = 9.3 Hz, m-C6H5), 50.8 (s, CH), 29.6 (s, CH2). 31P{1H} NMR (203 MHz, CDCl3, 298 K, p.p.m.): δ = 10.3 (s). IR (KBr, cm−1): ν = 3108 (w), 2993 (w), 1751 (s), 1494 (vs), 1106 (s), 752 (vs), 701 (vs).

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 2. C-bonded hydrogen atoms were placed in calculated positions and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C) and a C—H distance of 0.93 Å for aromatic (AFIX 43), 0.98 Å for methine (AFIX 13) and 0.97 Å for methyl­ene H atoms (AFIX 23). The same applies for the O-bonded H atom; however, the torsion angle was derived from electron density (AFIX 147). The structure contains three molecules of di­chloro­methane as the packing solvent. Both crystallographically independent molecules consist of two moieties each. One molecule was refined as disordered over two positions (C1S; C1SB) with occupancies of 92.7 (2) and 7.3 (3)%, respectively. The less prevalent moiety of C1SB is located close to a crystallographic inversion centre and symmetry-related pairs are mutually exclusive. The second disordered molecule is located directly atop of another inversion centre with an occupancy of 0.5 (Fig. 1), with the inversion centre located near the C2S and Cl1B atoms. The less-occupied methyl­ene chloride molecule was restrained to have a geometry similar to that of its major moiety counterpart by using the SAME command. Uij components of ADPs for C1S C1SB Cl1B and Cl2B were restrained to be similar if closer than 1.7 Å (SIMU restraint, McArdle, 1995; Sheldrick, 2008).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS2013 (Sheldrick, 200); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level, including the intramolecular hydrogen bonds. All non-O-bonded H atoms and the labels of the o-, m- and p-phenyl C atoms have been omitted for clarity. [Symmetry codes: (A) −x, −y + 1, −z + 2; (B) −x + 1, −y + 1, −z; (C) −x + 1, −y, −z.]
[Figure 2] Fig. 2. Intermolecular T-shaped π–π interactions (blue) between the centroids (D) of the C5–C10 and C35–C40 labeled phenyl rings in the crystal structure of (I). All H atoms and solvent molecules have been omitted for clarity. D—D = 4.8497 (16) Å; α = 77.40 (13) °. [Symmetry codes: (') −x, −y + 1, −z + 2; (A) x, 1/2 − y, z − 1/2; (B) x, y, x − 1.]
(µ-1,4-Dicarboxybutane-1,4-dicarboxylato)bis[bis(triphenylphosphane)silver(I)] dichloromethane trisolvate top
Crystal data top
[Ag2(C8H8O8)(C18H15P)4]·3CH2Cl2Z = 1
Mr = 1751.74F(000) = 892
Triclinic, P1Dx = 1.517 Mg m−3
a = 10.0279 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 12.9540 (4) ÅCell parameters from 12088 reflections
c = 16.8190 (5) Åθ = 3.4–28.8°
α = 112.306 (3)°µ = 0.86 mm−1
β = 96.080 (3)°T = 110 K
γ = 103.601 (3)°Block, colorless
V = 1917.80 (11) Å30.3 × 0.3 × 0.2 mm
Data collection top
Oxford Gemini S
diffractometer		Rint = 0.024
ω scansθmax = 28.9°, θmin = 2.9°
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)		h = −13→12
Tmin = 0.889, Tmax = 1.000k = −17→17
21441 measured reflectionsl = −22→20
8700 independent reflections2 standard reflections every 50 reflections
7959 reflections with I > 2σ(I) intensity decay: none
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)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.032P)2 + 2.6912P]
where P = (Fo2 + 2Fc2)/3
8700 reflections(Δ/σ)max = 0.001
507 parametersΔρmax = 2.28 e Å−3
27 restraintsΔρmin = −0.61 e Å−3
Crystal data top
[Ag2(C8H8O8)(C18H15P)4]·3CH2Cl2γ = 103.601 (3)°
Mr = 1751.74V = 1917.80 (11) Å3
Triclinic, P1Z = 1
a = 10.0279 (3) ÅMo Kα radiation
b = 12.9540 (4) ŵ = 0.86 mm−1
c = 16.8190 (5) ÅT = 110 K
α = 112.306 (3)°0.3 × 0.3 × 0.2 mm
β = 96.080 (3)°
Data collection top
Oxford Gemini S
diffractometer		7959 reflections with I > 2σ(I)
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)		Rint = 0.024
Tmin = 0.889, Tmax = 1.0002 standard reflections every 50 reflections
21441 measured reflections intensity decay: none
8700 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03427 restraints
wR(F2) = 0.083H-atom parameters constrained
S = 1.06Δρmax = 2.28 e Å−3
8700 reflectionsΔρmin = −0.61 e Å−3
507 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)
C10.1098 (3)0.4419 (2)0.82508 (15)0.0190 (5)
C20.0325 (2)0.5106 (2)0.88968 (15)0.0174 (4)
H2−0.06990.48120.86150.021*
C30.0822 (3)0.6429 (2)0.91901 (16)0.0247 (5)
C40.0521 (3)0.4833 (2)0.97147 (15)0.0189 (5)
H4A0.04020.39870.95180.023*
H4B0.14890.52651.00700.023*
C50.2398 (2)−0.00432 (19)0.61984 (14)0.0158 (4)
C60.1010 (3)−0.0530 (2)0.57113 (16)0.0204 (5)
H60.0276−0.02970.59750.024*
C70.0703 (3)−0.1351 (2)0.48448 (16)0.0232 (5)
H7−0.0241−0.16780.45180.028*
C80.1774 (3)−0.1698 (2)0.44511 (16)0.0243 (5)
H80.1562−0.22580.38570.029*
C90.3145 (3)−0.1225 (2)0.49301 (16)0.0231 (5)
H90.3875−0.14610.46630.028*
C100.3465 (3)−0.0403 (2)0.58043 (16)0.0193 (5)
H100.4409−0.00880.61310.023*
C110.4578 (2)0.1469 (2)0.77394 (15)0.0173 (4)
C120.5538 (3)0.2188 (2)0.74783 (17)0.0230 (5)
H120.52030.25090.71030.028*
C130.6972 (3)0.2435 (2)0.77632 (17)0.0256 (5)
H130.76160.29110.75750.031*
C140.7467 (3)0.1989 (2)0.83205 (18)0.0280 (6)
H140.84500.21530.85120.034*
C150.6527 (3)0.1299 (3)0.86010 (19)0.0314 (6)
H150.68690.10100.89970.038*
C160.5089 (3)0.1029 (2)0.83059 (17)0.0251 (5)
H160.44510.05440.84910.030*
C170.1720 (2)0.0459 (2)0.78922 (15)0.0172 (4)
C180.1697 (3)−0.0662 (2)0.78067 (16)0.0222 (5)
H180.2230−0.10710.74400.027*
C190.0898 (3)−0.1177 (2)0.82571 (17)0.0269 (5)
H190.0880−0.19400.81960.032*
C200.0124 (3)−0.0581 (2)0.87957 (17)0.0266 (5)
H20−0.0423−0.09380.91030.032*
C210.0144 (3)0.0534 (2)0.88891 (17)0.0256 (5)
H21−0.03820.09420.92630.031*
C220.0939 (3)0.1055 (2)0.84336 (16)0.0215 (5)
H220.09480.18160.84930.026*
C230.2912 (2)0.2770 (2)0.50087 (15)0.0162 (4)
C240.2945 (3)0.1622 (2)0.47850 (16)0.0207 (5)
H240.30610.13540.52340.025*
C250.2812 (3)0.0869 (2)0.39126 (17)0.0239 (5)
H250.28460.00940.37680.029*
C260.2629 (3)0.1250 (2)0.32544 (17)0.0259 (5)
H260.25420.07390.26580.031*
C270.2574 (3)0.2385 (2)0.34706 (17)0.0276 (6)
H270.24360.26440.30190.033*
C280.2719 (3)0.3141 (2)0.43393 (16)0.0220 (5)
H280.26860.39170.44800.026*
C290.5028 (2)0.4324 (2)0.65811 (15)0.0175 (4)
C300.5974 (3)0.4021 (2)0.60549 (16)0.0212 (5)
H300.56360.34840.54540.025*
C310.7417 (3)0.4499 (2)0.64032 (18)0.0245 (5)
H310.80600.42830.60410.029*
C320.7910 (3)0.5285 (2)0.72730 (18)0.0269 (5)
H320.88930.56230.75070.032*
C330.6974 (3)0.5585 (2)0.78088 (17)0.0285 (6)
H330.73190.61230.84090.034*
C340.5535 (3)0.5101 (2)0.74688 (16)0.0240 (5)
H340.48960.52970.78380.029*
C350.2611 (2)0.4971 (2)0.61527 (14)0.0171 (4)
C360.1241 (3)0.4982 (2)0.61812 (18)0.0252 (5)
H360.06020.43700.62530.030*
C370.0796 (3)0.5889 (2)0.6105 (2)0.0303 (6)
H37−0.01510.58850.61140.036*
C380.1724 (3)0.6791 (2)0.60168 (16)0.0253 (5)
H380.14130.74010.59550.030*
C390.3101 (3)0.6805 (2)0.60184 (17)0.0248 (5)
H390.37490.74380.59770.030*
C400.3546 (3)0.5896 (2)0.60809 (17)0.0223 (5)
H400.44950.59060.60750.027*
P10.27220 (6)0.11490 (5)0.72910 (4)0.01518 (12)
P20.31285 (6)0.37213 (5)0.61693 (4)0.01519 (12)
Ag10.22109 (2)0.27730 (2)0.70903 (2)0.01622 (6)
O10.04100 (19)0.34138 (15)0.76927 (11)0.0239 (4)
O20.23936 (19)0.48772 (17)0.83418 (12)0.0301 (4)
O30.2146 (2)0.68777 (18)0.91847 (15)0.0409 (5)
H30.25420.63500.90520.061*
O40.0070 (2)0.70357 (16)0.94320 (13)0.0333 (4)
C1S0.4951 (4)0.1726 (4)0.0721 (3)0.0525 (11)0.928 (2)
H1S10.56890.14170.04570.063*0.928 (2)
H1S20.49830.24470.06380.063*0.928 (2)
Cl10.33022 (9)0.06889 (12)0.01685 (7)0.0647 (4)0.928 (2)
Cl20.53101 (12)0.20717 (8)0.18454 (6)0.0474 (3)0.928 (2)
C1SB0.525 (5)0.125 (3)0.069 (3)0.069 (7)0.072 (2)
H1S30.61610.13010.10160.083*0.072 (2)
H1S40.54600.17700.03810.083*0.072 (2)
Cl1B0.451 (2)−0.0184 (18)−0.0110 (13)0.088 (6)0.072 (2)
Cl2B0.429 (3)0.183 (2)0.1455 (16)0.112 (7)0.072 (2)
C2S0.5061 (9)0.4570 (8)−0.0394 (6)0.060 (2)0.5
H2S10.47880.4427−0.10190.072*0.5
H2S20.59400.4361−0.03190.072*0.5
Cl30.3762 (2)0.3690 (2)−0.01470 (16)0.0548 (5)0.5
Cl40.5373 (5)0.6054 (2)0.0271 (3)0.1237 (17)0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0254 (12)0.0211 (12)0.0169 (11)0.0116 (9)0.0102 (9)0.0105 (9)
C20.0230 (11)0.0167 (11)0.0149 (10)0.0077 (9)0.0082 (9)0.0070 (9)
C30.0380 (14)0.0213 (13)0.0158 (11)0.0076 (11)0.0087 (10)0.0087 (10)
C40.0236 (11)0.0206 (12)0.0174 (11)0.0112 (9)0.0094 (9)0.0092 (9)
C50.0237 (11)0.0118 (10)0.0156 (10)0.0066 (9)0.0074 (9)0.0080 (8)
C60.0230 (12)0.0206 (12)0.0214 (11)0.0085 (9)0.0081 (9)0.0109 (10)
C70.0250 (12)0.0215 (12)0.0210 (12)0.0037 (10)0.0011 (9)0.0097 (10)
C80.0388 (14)0.0169 (12)0.0179 (11)0.0099 (10)0.0077 (10)0.0067 (9)
C90.0336 (13)0.0204 (12)0.0227 (12)0.0149 (10)0.0149 (10)0.0105 (10)
C100.0239 (12)0.0166 (11)0.0216 (11)0.0089 (9)0.0086 (9)0.0098 (9)
C110.0211 (11)0.0149 (11)0.0165 (10)0.0072 (9)0.0057 (9)0.0056 (9)
C120.0258 (12)0.0201 (12)0.0247 (12)0.0061 (10)0.0051 (10)0.0117 (10)
C130.0241 (12)0.0200 (12)0.0304 (13)0.0032 (10)0.0086 (10)0.0092 (10)
C140.0210 (12)0.0267 (14)0.0312 (14)0.0076 (10)0.0020 (10)0.0074 (11)
C150.0312 (14)0.0380 (16)0.0314 (14)0.0139 (12)0.0034 (11)0.0200 (13)
C160.0264 (13)0.0275 (13)0.0270 (13)0.0088 (10)0.0069 (10)0.0164 (11)
C170.0218 (11)0.0156 (11)0.0163 (10)0.0055 (9)0.0061 (9)0.0084 (9)
C180.0327 (13)0.0187 (12)0.0195 (11)0.0104 (10)0.0103 (10)0.0096 (9)
C190.0390 (15)0.0187 (12)0.0241 (12)0.0046 (11)0.0091 (11)0.0120 (10)
C200.0293 (13)0.0307 (14)0.0224 (12)0.0039 (11)0.0087 (10)0.0160 (11)
C210.0269 (13)0.0335 (14)0.0223 (12)0.0117 (11)0.0117 (10)0.0148 (11)
C220.0258 (12)0.0214 (12)0.0227 (12)0.0116 (10)0.0094 (10)0.0110 (10)
C230.0171 (10)0.0168 (11)0.0170 (10)0.0056 (8)0.0077 (8)0.0080 (9)
C240.0273 (12)0.0197 (12)0.0211 (11)0.0100 (10)0.0094 (9)0.0120 (10)
C250.0299 (13)0.0182 (12)0.0257 (12)0.0095 (10)0.0107 (10)0.0087 (10)
C260.0306 (13)0.0236 (13)0.0195 (12)0.0069 (10)0.0071 (10)0.0052 (10)
C270.0398 (15)0.0277 (14)0.0190 (12)0.0108 (11)0.0060 (11)0.0134 (10)
C280.0286 (13)0.0197 (12)0.0216 (12)0.0094 (10)0.0064 (10)0.0112 (10)
C290.0198 (11)0.0173 (11)0.0217 (11)0.0075 (9)0.0062 (9)0.0131 (9)
C300.0235 (12)0.0199 (12)0.0240 (12)0.0098 (10)0.0081 (10)0.0106 (10)
C310.0212 (12)0.0256 (13)0.0338 (14)0.0100 (10)0.0094 (10)0.0173 (11)
C320.0223 (12)0.0292 (14)0.0342 (14)0.0052 (10)0.0022 (10)0.0209 (12)
C330.0331 (14)0.0281 (14)0.0207 (12)0.0033 (11)0.0002 (10)0.0116 (11)
C340.0286 (13)0.0253 (13)0.0215 (12)0.0087 (10)0.0088 (10)0.0121 (10)
C350.0247 (12)0.0156 (11)0.0150 (10)0.0091 (9)0.0077 (9)0.0080 (9)
C360.0249 (12)0.0216 (13)0.0360 (14)0.0094 (10)0.0107 (11)0.0167 (11)
C370.0270 (13)0.0295 (14)0.0432 (16)0.0162 (11)0.0109 (12)0.0190 (12)
C380.0389 (14)0.0198 (12)0.0222 (12)0.0156 (11)0.0084 (11)0.0096 (10)
C390.0366 (14)0.0165 (12)0.0266 (13)0.0087 (10)0.0117 (11)0.0127 (10)
C400.0264 (12)0.0196 (12)0.0271 (12)0.0095 (10)0.0121 (10)0.0132 (10)
P10.0194 (3)0.0141 (3)0.0162 (3)0.0073 (2)0.0073 (2)0.0084 (2)
P20.0195 (3)0.0148 (3)0.0162 (3)0.0079 (2)0.0082 (2)0.0089 (2)
Ag10.02215 (9)0.01473 (9)0.01672 (9)0.00874 (7)0.00930 (6)0.00856 (7)
O10.0280 (9)0.0196 (9)0.0237 (9)0.0090 (7)0.0139 (7)0.0053 (7)
O20.0226 (9)0.0352 (11)0.0260 (9)0.0061 (8)0.0114 (7)0.0060 (8)
O30.0440 (12)0.0228 (10)0.0449 (12)−0.0002 (9)0.0212 (10)0.0058 (9)
O40.0535 (13)0.0207 (10)0.0303 (10)0.0192 (9)0.0126 (9)0.0100 (8)
C1S0.040 (2)0.069 (3)0.046 (2)−0.0016 (19)0.0037 (16)0.034 (2)
Cl10.0314 (5)0.1057 (9)0.0486 (6)−0.0137 (5)−0.0060 (4)0.0476 (6)
Cl20.0634 (6)0.0420 (5)0.0313 (4)0.0193 (4)0.0035 (4)0.0091 (4)
C1SB0.063 (9)0.077 (9)0.062 (9)0.007 (9)0.008 (8)0.033 (9)
Cl1B0.124 (15)0.080 (11)0.075 (10)0.032 (12)0.019 (11)0.047 (9)
Cl2B0.101 (11)0.108 (11)0.106 (11)0.021 (10)0.014 (10)0.029 (10)
C2S0.044 (4)0.063 (6)0.082 (6)0.011 (4)0.023 (4)0.041 (5)
Cl30.0507 (11)0.0616 (14)0.0619 (12)0.0195 (10)0.0221 (10)0.0321 (11)
Cl40.165 (4)0.0433 (15)0.109 (3)−0.009 (2)−0.068 (3)0.0238 (16)
Geometric parameters (Å, º) top
C1—O11.251 (3)C24—C251.390 (3)
C1—O21.261 (3)C24—H240.9500
C1—C21.531 (3)C25—C261.385 (4)
C2—C31.527 (3)C25—H250.9500
C2—C41.550 (3)C26—C271.390 (4)
C2—H21.0000C26—H260.9500
C3—O41.205 (3)C27—C281.385 (4)
C3—O31.321 (3)C27—H270.9500
C4—C4i1.520 (4)C28—H280.9500
C4—H4A0.9900C29—C301.388 (3)
C4—H4B0.9900C29—C341.399 (3)
C5—C101.397 (3)C29—P21.825 (2)
C5—C61.400 (3)C30—C311.395 (3)
C5—P11.831 (2)C30—H300.9500
C6—C71.387 (3)C31—C321.379 (4)
C6—H60.9500C31—H310.9500
C7—C81.395 (4)C32—C331.389 (4)
C7—H70.9500C32—H320.9500
C8—C91.382 (4)C33—C341.389 (4)
C8—H80.9500C33—H330.9500
C9—C101.396 (3)C34—H340.9500
C9—H90.9500C35—C361.384 (3)
C10—H100.9500C35—C401.391 (3)
C11—C161.393 (3)C35—P21.821 (2)
C11—C121.402 (3)C36—C371.394 (4)
C11—P11.819 (2)C36—H360.9500
C12—C131.386 (4)C37—C381.380 (4)
C12—H120.9500C37—H370.9500
C13—C141.381 (4)C38—C391.376 (4)
C13—H130.9500C38—H380.9500
C14—C151.389 (4)C39—C401.389 (3)
C14—H140.9500C39—H390.9500
C15—C161.389 (4)C40—H400.9500
C15—H150.9500P1—Ag12.4109 (6)
C16—H160.9500P2—Ag12.4433 (6)
C17—C221.393 (3)Ag1—O12.3305 (17)
C17—C181.398 (3)O3—H30.8400
C17—P11.819 (2)C1S—Cl21.744 (4)
C18—C191.387 (3)C1S—Cl11.756 (4)
C18—H180.9500C1S—H1S10.9900
C19—C201.385 (4)C1S—H1S20.9900
C19—H190.9500C1SB—Cl2B1.73 (2)
C20—C211.387 (4)C1SB—Cl1B1.75 (2)
C20—H200.9500C1SB—H1S30.9900
C21—C221.395 (3)C1SB—H1S40.9900
C21—H210.9500C2S—Cl31.716 (8)
C22—H220.9500C2S—Cl41.748 (10)
C23—C281.395 (3)C2S—H2S10.9900
C23—C241.398 (3)C2S—H2S20.9900
C23—P21.826 (2)
O1—C1—O2124.4 (2)C25—C26—C27119.7 (2)
O1—C1—C2117.4 (2)C25—C26—H26120.2
O2—C1—C2118.1 (2)C27—C26—H26120.2
C3—C2—C1115.15 (19)C28—C27—C26120.5 (2)
C3—C2—C4109.22 (19)C28—C27—H27119.7
C1—C2—C4106.96 (18)C26—C27—H27119.7
C3—C2—H2108.4C27—C28—C23120.3 (2)
C1—C2—H2108.4C27—C28—H28119.8
C4—C2—H2108.4C23—C28—H28119.8
O4—C3—O3121.6 (2)C30—C29—C34119.4 (2)
O4—C3—C2122.5 (2)C30—C29—P2122.57 (19)
O3—C3—C2115.8 (2)C34—C29—P2118.00 (18)
C4i—C4—C2112.2 (2)C29—C30—C31120.4 (2)
C4i—C4—H4A109.2C29—C30—H30119.8
C2—C4—H4A109.2C31—C30—H30119.8
C4i—C4—H4B109.2C32—C31—C30119.9 (2)
C2—C4—H4B109.2C32—C31—H31120.0
H4A—C4—H4B107.9C30—C31—H31120.0
C10—C5—C6119.2 (2)C31—C32—C33120.2 (2)
C10—C5—P1123.58 (18)C31—C32—H32119.9
C6—C5—P1116.88 (17)C33—C32—H32119.9
C7—C6—C5120.2 (2)C32—C33—C34120.1 (2)
C7—C6—H6119.9C32—C33—H33119.9
C5—C6—H6119.9C34—C33—H33119.9
C6—C7—C8120.3 (2)C33—C34—C29119.9 (2)
C6—C7—H7119.8C33—C34—H34120.0
C8—C7—H7119.8C29—C34—H34120.0
C9—C8—C7119.7 (2)C36—C35—C40119.1 (2)
C9—C8—H8120.2C36—C35—P2119.20 (18)
C7—C8—H8120.2C40—C35—P2121.65 (18)
C8—C9—C10120.5 (2)C35—C36—C37120.1 (2)
C8—C9—H9119.8C35—C36—H36119.9
C10—C9—H9119.8C37—C36—H36119.9
C9—C10—C5120.0 (2)C38—C37—C36120.3 (2)
C9—C10—H10120.0C38—C37—H37119.8
C5—C10—H10120.0C36—C37—H37119.8
C16—C11—C12118.9 (2)C39—C38—C37119.8 (2)
C16—C11—P1124.05 (18)C39—C38—H38120.1
C12—C11—P1117.01 (18)C37—C38—H38120.1
C13—C12—C11120.5 (2)C38—C39—C40120.2 (2)
C13—C12—H12119.8C38—C39—H39119.9
C11—C12—H12119.8C40—C39—H39119.9
C14—C13—C12120.1 (2)C39—C40—C35120.4 (2)
C14—C13—H13119.9C39—C40—H40119.8
C12—C13—H13119.9C35—C40—H40119.8
C13—C14—C15119.9 (2)C11—P1—C17107.82 (11)
C13—C14—H14120.0C11—P1—C5103.98 (11)
C15—C14—H14120.0C17—P1—C5103.48 (10)
C14—C15—C16120.4 (2)C11—P1—Ag1112.08 (8)
C14—C15—H15119.8C17—P1—Ag1120.40 (8)
C16—C15—H15119.8C5—P1—Ag1107.53 (7)
C15—C16—C11120.2 (2)C35—P2—C29102.98 (11)
C15—C16—H16119.9C35—P2—C23104.23 (10)
C11—C16—H16119.9C29—P2—C23104.33 (11)
C22—C17—C18119.6 (2)C35—P2—Ag1120.17 (7)
C22—C17—P1119.02 (17)C29—P2—Ag1106.98 (7)
C18—C17—P1121.32 (18)C23—P2—Ag1116.33 (7)
C19—C18—C17120.1 (2)O1—Ag1—P1117.69 (5)
C19—C18—H18120.0O1—Ag1—P2113.27 (5)
C17—C18—H18120.0P1—Ag1—P2128.56 (2)
C20—C19—C18120.1 (2)C1—O1—Ag1100.12 (14)
C20—C19—H19120.0C3—O3—H3109.5
C18—C19—H19120.0Cl2—C1S—Cl1112.6 (2)
C19—C20—C21120.3 (2)Cl2—C1S—H1S1109.1
C19—C20—H20119.8Cl1—C1S—H1S1109.1
C21—C20—H20119.8Cl2—C1S—H1S2109.1
C20—C21—C22119.9 (2)Cl1—C1S—H1S2109.1
C20—C21—H21120.0H1S1—C1S—H1S2107.8
C22—C21—H21120.0Cl2B—C1SB—Cl1B118 (2)
C17—C22—C21119.9 (2)Cl2B—C1SB—H1S3107.8
C17—C22—H22120.0Cl1B—C1SB—H1S3107.8
C21—C22—H22120.0Cl2B—C1SB—H1S4107.8
C28—C23—C24118.8 (2)Cl1B—C1SB—H1S4107.8
C28—C23—P2122.78 (18)H1S3—C1SB—H1S4107.1
C24—C23—P2118.41 (17)Cl3—C2S—Cl4112.3 (5)
C25—C24—C23120.7 (2)Cl3—C2S—H2S1109.1
C25—C24—H24119.7Cl4—C2S—H2S1109.1
C23—C24—H24119.7Cl3—C2S—H2S2109.1
C26—C25—C24120.0 (2)Cl4—C2S—H2S2109.1
C26—C25—H25120.0H2S1—C2S—H2S2107.9
C24—C25—H25120.0
O1—C1—C2—C3−147.4 (2)C30—C29—C34—C331.8 (4)
O2—C1—C2—C335.8 (3)P2—C29—C34—C33−179.70 (19)
O1—C1—C2—C491.0 (2)C40—C35—C36—C372.4 (4)
O2—C1—C2—C4−85.7 (3)P2—C35—C36—C37−175.4 (2)
C1—C2—C3—O4153.9 (2)C35—C36—C37—C38−1.2 (4)
C4—C2—C3—O4−85.8 (3)C36—C37—C38—C39−1.1 (4)
C1—C2—C3—O3−27.7 (3)C37—C38—C39—C402.0 (4)
C4—C2—C3—O392.6 (2)C38—C39—C40—C35−0.8 (4)
C3—C2—C4—C4i71.3 (3)C36—C35—C40—C39−1.5 (4)
C1—C2—C4—C4i−163.5 (2)P2—C35—C40—C39176.25 (19)
C10—C5—C6—C7−0.6 (3)C16—C11—P1—C1712.2 (2)
P1—C5—C6—C7173.30 (18)C12—C11—P1—C17−168.95 (18)
C5—C6—C7—C80.0 (4)C16—C11—P1—C5−97.2 (2)
C6—C7—C8—C90.3 (4)C12—C11—P1—C581.6 (2)
C7—C8—C9—C100.0 (4)C16—C11—P1—Ag1146.97 (19)
C8—C9—C10—C5−0.7 (3)C12—C11—P1—Ag1−34.2 (2)
C6—C5—C10—C91.0 (3)C22—C17—P1—C11112.8 (2)
P1—C5—C10—C9−172.51 (18)C18—C17—P1—C11−68.5 (2)
C16—C11—C12—C131.5 (4)C22—C17—P1—C5−137.45 (19)
P1—C11—C12—C13−177.4 (2)C18—C17—P1—C541.2 (2)
C11—C12—C13—C14−1.1 (4)C22—C17—P1—Ag1−17.5 (2)
C12—C13—C14—C15−0.5 (4)C18—C17—P1—Ag1161.23 (17)
C13—C14—C15—C161.7 (4)C10—C5—P1—C11−10.3 (2)
C14—C15—C16—C11−1.3 (4)C6—C5—P1—C11176.06 (17)
C12—C11—C16—C15−0.3 (4)C10—C5—P1—C17−122.87 (19)
P1—C11—C16—C15178.5 (2)C6—C5—P1—C1763.48 (19)
C22—C17—C18—C190.2 (4)C10—C5—P1—Ag1108.71 (18)
P1—C17—C18—C19−178.5 (2)C6—C5—P1—Ag1−64.94 (18)
C17—C18—C19—C20−0.3 (4)C36—C35—P2—C29−157.1 (2)
C18—C19—C20—C21−0.1 (4)C40—C35—P2—C2925.2 (2)
C19—C20—C21—C220.5 (4)C36—C35—P2—C2394.2 (2)
C18—C17—C22—C210.2 (4)C40—C35—P2—C23−83.5 (2)
P1—C17—C22—C21178.93 (19)C36—C35—P2—Ag1−38.4 (2)
C20—C21—C22—C17−0.5 (4)C40—C35—P2—Ag1143.93 (17)
C28—C23—C24—C251.0 (4)C30—C29—P2—C35−110.1 (2)
P2—C23—C24—C25−178.78 (19)C34—C29—P2—C3571.4 (2)
C23—C24—C25—C26−0.6 (4)C30—C29—P2—C23−1.5 (2)
C24—C25—C26—C27−0.3 (4)C34—C29—P2—C23−179.95 (18)
C25—C26—C27—C280.9 (4)C30—C29—P2—Ag1122.33 (18)
C26—C27—C28—C23−0.5 (4)C34—C29—P2—Ag1−56.13 (19)
C24—C23—C28—C27−0.5 (4)C28—C23—P2—C3513.2 (2)
P2—C23—C28—C27179.3 (2)C24—C23—P2—C35−167.02 (19)
C34—C29—C30—C31−1.0 (3)C28—C23—P2—C29−94.5 (2)
P2—C29—C30—C31−179.43 (18)C24—C23—P2—C2985.3 (2)
C29—C30—C31—C32−0.5 (4)C28—C23—P2—Ag1147.93 (18)
C30—C31—C32—C331.3 (4)C24—C23—P2—Ag1−32.3 (2)
C31—C32—C33—C34−0.5 (4)O2—C1—O1—Ag14.6 (3)
C32—C33—C34—C29−1.1 (4)C2—C1—O1—Ag1−171.92 (16)
Symmetry code: (i) −x, −y+1, −z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O20.841.792.525 (3)146
C1S—H1S1···O3ii0.992.532.997 (4)108
C1SB—H1S4···O3ii0.992.463.04 (4)117
Symmetry code: (ii) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O20.841.792.525 (3)145.8
C1S—H1S1···O3i0.992.532.997 (4)108.4
C1SB—H1S4···O3i0.992.463.04 (4)117.0
Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula[Ag2(C8H8O8)(C18H15P)4]·3CH2Cl2
Mr1751.74
Crystal system, space groupTriclinic, P1
Temperature (K)110
a, b, c (Å)10.0279 (3), 12.9540 (4), 16.8190 (5)
α, β, γ (°)112.306 (3), 96.080 (3), 103.601 (3)
V (Å3)1917.80 (11)
Z1
Radiation typeMo Kα
µ (mm−1)0.86
Crystal size (mm)0.3 × 0.3 × 0.2
Data collection
DiffractometerOxford Gemini S
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2006)
Tmin, Tmax0.889, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		21441, 8700, 7959
Rint0.024
(sin θ/λ)max (Å−1)0.680
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.083, 1.06
No. of reflections8700
No. of parameters507
No. of restraints27
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)2.28, −0.61

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS2013 (Sheldrick, 200), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012) and SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).

 

Acknowledgements

MK thanks the Fonds der Chemischen Industrie for a PhD Chemiefonds fellowship. This work was performed within the Federal Cluster of Excellence EXC 1075 MERGE Technologies for Multifunctional Lightweight Structures and supported by the German Research Foundation (DFG). Financial support is gratefully acknowledged.

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ISSN: 2056-9890
Volume 72| Part 2| February 2016| Pages 215-219
doi:10.1107/S2056989016000797
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