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M4Au12Ag32(p-MBA)30 (M = Na, Cs) bimetallic monolayer-protected clusters: synthesis and structure

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aDepartment of Chemistry, University of Toledo, Toledo, Ohio 43606, USA, and bSchool of Physics, Georgia Institute of Technology, Atlanta, Georgia 30332 0430, USA
*Correspondence e-mail: Terry.Bigioni@utoledo.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 23 April 2018; accepted 6 June 2018; online 19 June 2018)

Crystals of M4Au12Ag32(p-MBA)30 bimetallic monolayer-protected clusters (MPCs), where p-MBA is p-mercapto­benzoic acid and M+ is a counter-cation (M = Na, Cs) have been grown and their structure determined. The mol­ecular structure of triacontakis[(4-carboxylatophenyl)sulfanido]dodecagolddotriacontasilver, Au12Ag32(C7H5O2S)30 or C210H150Ag32Au12O60S30, exhib­its point group symmetry [\overline{3}] at 100 K. The overall diameter of the MPC is approximately 28 Å, while the diameter of the Au12Ag20 metallic core is 9 Å. The structure displays ligand bundling and inter­molecular hydrogen bonding, which gives rise to a framework structure with 52% solvent-filled void space. The positions of the M+ cations and the DMF solvent mol­ecules within the void space of the crystal could not be determined. Three out of the five crystallographically independent ligands in the asymmetric unit cell are disordered over two sets of sites. Comparisons are made to the all-silver M4Ag44(p-MBA)30 MPCs and to expectations based on density functional theory.

1. Chemical context

The M4Ag44(p-MBA)30 monolayer-protected cluster (MPC) has been studied in detail previously, where M+ is an alkali metal counter-ion (M = Na, Cs) and p-MBA is p-mercapto­benzoic acid (Desireddy et al., 2013[Desireddy, A., Conn, B. E., Guo, J., Yoon, B., Barnett, R. N., Monahan, B. M., Kirschbaum, K., Griffith, W. P., Whetten, R. L., Landman, U. & Bigioni, T. P. (2013). Nature, 501, 399-402.]; Conn et al., 2015[Conn, B. E., Desireddy, A., Atnagulov, A., Wickramasinghe, S., Bhattarai, B., Yoon, B., Barnett, R. N., Abdollahian, Y., Kim, Y. W., Griffith, W. P., Oliver, S. R. J., Landman, U. & Bigioni, T. P. (2015). J. Phys. Chem. C, 119, 11238-11249.]), along with other related 44 silver-atom species (Bakr et al., 2009[Bakr, O. M., Amendola, V., Aikens, C. M., Wenseleers, W., Li, R., Dal Negro, L., Schatz, G. C. & Stellacci, F. (2009). Angew. Chem. Int. Ed. 48, 5921-5926.]; Pelton et al., 2012[Pelton, M., Tang, Y., Bakr, O. M. & Stellacci, F. (2012). J. Am. Chem. Soc. 134, 11856-11859.]; AbdulHalim et al., 2013[AbdulHalim, L. G., Ashraf, S., Katsiev, K., Kirmani, A. R., Kothalawala, N., Anjum, D. H., Abbas, S., Amassian, A., Stellacci, F., Dass, A., Hussain, I. & Bakr, O. M. (2013). J. Mater. Chem. A, 1, 10148-10154.]; Yang et al., 2013[Yang, H., Wang, Y., Huang, H., Gell, L., Lehtovaara, L., Malola, S., Häkkinen, H. & Zheng, N. (2013). Nat. Commun. 4, 2422.]; Chakraborty et al., 2013[Chakraborty, I., Kurashige, W., Kanehira, K., Gell, L., Häkkinen, H., Negishi, Y. & Pradeep, T. (2013). J. Phys. Chem. Lett. 4, 3351-3355.]). The formula has been shown to be Na4Ag44(p-MBA)30 and K4Ag44(p-MBA)30 in all-sodium and all-potassium preparations, respectively, and the mol­ecular and crystal structures have been determined crystallo­graphically (Desireddy et al., 2013[Desireddy, A., Conn, B. E., Guo, J., Yoon, B., Barnett, R. N., Monahan, B. M., Kirschbaum, K., Griffith, W. P., Whetten, R. L., Landman, U. & Bigioni, T. P. (2013). Nature, 501, 399-402.]). The crystal was determined to have a framework structure, with 52% solvent-filled void space, that is a consequence of both ligand bundling and inter­particle hydrogen bonding (Yoon et al., 2014[Yoon, B., Luedtke, W. D., Barnett, R. N., Gao, J., Desireddy, A., Conn, B. E., Bigioni, T. P. & Landman, U. (2014). Nat. Mater. 13, 807-811.]). The positions of the alkali metal counter-ions were not determined, and are presumably located in the solvent portion of the crystal (Desireddy et al., 2013[Desireddy, A., Conn, B. E., Guo, J., Yoon, B., Barnett, R. N., Monahan, B. M., Kirschbaum, K., Griffith, W. P., Whetten, R. L., Landman, U. & Bigioni, T. P. (2013). Nature, 501, 399-402.]).

Structurally related species have also been prepared with non-polar ligands, using non-polar synthetic conditions, forming chemically distinct members of the 44 silver-atom family of species, e.g. (PPh4)4Ag44(SPhF2)30 along with SPhF and SPhCF3 variants (Bakr et al., 2009[Bakr, O. M., Amendola, V., Aikens, C. M., Wenseleers, W., Li, R., Dal Negro, L., Schatz, G. C. & Stellacci, F. (2009). Angew. Chem. Int. Ed. 48, 5921-5926.]; Yang et al., 2013[Yang, H., Wang, Y., Huang, H., Gell, L., Lehtovaara, L., Malola, S., Häkkinen, H. & Zheng, N. (2013). Nat. Commun. 4, 2422.]). In the crystals of these species, the ligand bundling is not dominant and ligand inter­actions do not lead to framework structures. Instead, ligands pack more tightly, with 36% solvent-filled void space, and the bulky PPh4+ counter-cations lock into place in the crystals such that they can be located (Yang et al., 2013[Yang, H., Wang, Y., Huang, H., Gell, L., Lehtovaara, L., Malola, S., Häkkinen, H. & Zheng, N. (2013). Nat. Commun. 4, 2422.]).

Silver and gold mix readily to form the naturally occurring alloy electrum and therefore the study of mixtures of silver and gold within these MPCs is of inter­est (Yang et al., 2013[Yang, H., Wang, Y., Huang, H., Gell, L., Lehtovaara, L., Malola, S., Häkkinen, H. & Zheng, N. (2013). Nat. Commun. 4, 2422.]). Mixtures of M4AuxAg44–x(p-MBA)30 MPCs can be obtained by co-reducing silver and gold polymers of p-MBA, where 0 ≤ x ≤ 12 (Conn et al., 2018[Conn, B. E., Atnagulov, A., Bhattarai, B., Yoon, B., Landman, U. & Bigioni, T. P. (2018). J. Phys. Chem. C. https://pubs.acs.org/doi/10.1021/acs.jpcc.8b03372.]). Gold-rich species have been synthesized and then thermally processed to destroy the species that contained fewer gold atoms, thereby enriching the samples in M4Au12Ag32(p-MBA)30 MPCs.

Once high-purity samples of M4Au12Ag32(p-MBA)30 MPCs had been prepared and crystallized, the locations of the gold atoms could be determined by crystallographic methods. Prior reports using non-polar members of the 44 metal-atom family of species determined that the 12 gold atoms are located in the icosa­hedral inner core of that mol­ecule (Yang et al., 2013[Yang, H., Wang, Y., Huang, H., Gell, L., Lehtovaara, L., Malola, S., Häkkinen, H. & Zheng, N. (2013). Nat. Commun. 4, 2422.]). It is not clear, however, whether different synthetic conditions, ligands, and solvent class would affect the synthetic mechanism, electronic structure, and ultimately the organ­iza­tion of metal atoms within the core. We present here the chemical synthetic method of producing M4Au12Ag32(p-MBA)30 MPCs as well as their X-ray determined structure and verify that the gold atoms are indeed located in the core of this MPC. Comparisons with other family members are also made to examine the effects of heteroligands and heteroatoms on the structures of these species.

[Scheme 1]

2. Structural commentary

There are four sets of chemically equivalent positions for metal atoms in the Au12Ag32(p-MBA)304− mol­ecular structure. All 12 positions in the icosa­hedral inner core are chemically equivalent, whereas the dodeca­hedral outer core contains a set of eight chemically equivalent positions (defining a cube) and a set of 12 chemically equivalent positions (a pair of atoms beneath each of the six mounts). The remaining 12 metal atoms are found in pairs in the six mounts and are chemically equivalent. In principle, then, there are three possible ways to locate 12 equivalent gold heteroatoms.

Density-functional calculations (Kresse & Joubert, 1999[Kresse, G. & Joubert, D. (1999). Phys. Rev. B, 59, 1758-1775.]; Perdew, 1991[Perdew, J. P. (1991). Unified Theory of Exchange and Correlation Beyond the Local Density Approximation. In Electronic Structure of Solids '91, edited by P. Ziesche and H. Eschrig, pp. 11-20. Berlin: Akademie Verlag.]; Perdew et al., 1992[Perdew, J. P., Chevary, J. A., Vosko, S. H., Jackson, K. A., Pederson, M. R., Singh, D. J. & Fiolhais, C. (1992). Phys. Rev. B, 46, 6671-6687.], 1993[Perdew, J. P., Chevary, J. A., Vosko, S. H., Jackson, K. A., Pederson, M. R., Singh, D. J. & Fiolhais, C. (1993). Phys. Rev. B, 48, 4978-4978.]) were performed to evaluate the energy differences upon substitution of gold atoms into each of these four distinct metal-atom positions. Each calculation was done for a M4AuAg43(p-MBA)30 MPC, the structures of which were relaxed after substitution. In each case, the energy of M4AuAg43(p-MBA)30 was found to be lower than M4Ag44(p-MBA)30. It was found that substitution of gold atoms into the icosa­hedral core has the biggest effect, lowering the energy by 0.71 eV per Au atom. The next most energetically favorable position was that of the eight atoms in the dodeca­hedral shell, lowering the energy by 0.30 eV per Au atom; these positions are of particular inter­est since they are the only atoms in the metal core that are exposed and capable of directly inter­acting and reacting with other species in solution. The least favorable positions for substitution were found to be the pairs of metal atoms in the mounts, lowering the energy by 0.170 eV per Au atom, and the pairs of metal atoms beneath the mounts, lowering the energy by 0.13 eV per Au atom. Based on these calculations, the 12 substituted gold atoms were expected to be found in the icosa­hedral core.

The positions of the 12 Au atoms were determined by single-crystal X-ray crystallographic methods. The full refinement of the Au12Ag32(p-MBA)304− mol­ecular structure revealed that the 12 gold atoms reside in the icosa­hedral inner core of the MPC. The structure consists of a 12 gold-atom icosa­hedron surrounded by a 20 silver-atom dodeca­hedron, forming a 32-atom excavated-dodeca­hedral bimetallic core. The metal core is capped by six equivalent Ag2(p-MBA)5 mount motifs, which are octa­hedrally located about the core (Fig. 1[link]). The Au12Ag32(p-MBA)304− anion is located about an inversion center and exhibits point group symmetry [\overline{3}] (Fig. 2[link]).

[Figure 1]
Figure 1
Structure of Au12Ag32(p-MBA)304−. Complete X-ray-determined structure shown in (a) space-filling view and (b) ball-and-stick view (out-of-plane ligands removed for clarity). The core structure is shown as (c) an Au12 icosa­hedral inner shell, which is nested inside of (d) an Ag20 dodeca­hedral outer shell, together making (e) a bimetallic 32-atom excavated dodeca­hedral core. Other colors: red – O; grey – C; yellow – S (H not shown). The overall diameter of the MPC was measured to be about 28 Å, while the diameter of the inorganic portion of the structure was 17 Å and the metallic Au12Ag20 dodeca­hedral core was 9 Å. Measurements were made between the centers of opposing atoms in the structure.
[Figure 2]
Figure 2
Structure of Au12Ag32(p-MBA)304− using displacement ellipsoids that were drawn at the 50% probability level for three different views of the structure. Au atoms are depicted in orange, Ag atoms in grey, and S atoms in yellow. Views are (a) down a fourfold axis of the pseudo­octa­hedral structure, (b) with one 31.7° rotation from (a) about the horizontal axis, and (c) with two 45° rotations from (a) about the horizontal and vertical axes. The organic portion of the mol­ecule was omitted for clarity.

The crystallographically determined locations of the 12 gold atoms in the icosa­hedral inner core of the bimetallic MPC are consistent with the expected locations based on our DFT calculations and based on previous reports (Yang et al., 2013[Yang, H., Wang, Y., Huang, H., Gell, L., Lehtovaara, L., Malola, S., Häkkinen, H. & Zheng, N. (2013). Nat. Commun. 4, 2422.]). In addition, this result is in agreement with the known properties of gold and silver. Although gold and silver are isoelectronic and have almost identical atomic radii, their chemical properties and bonding can be quite different. For example, Au—S and Ag—S bonding is typically two- and three-coordinate, respectively (Dance, 1986[Dance, I. G. (1986). Polyhedron, 5, 1037-1104.]; Dance et al., 1991[Dance, I. G., Fisher, K. J., Herath Banda, R. M. & Scudder, M. L. (1991). Inorg. Chem. 30, 183-187.]), which makes the bonding of the gold heteroatoms incompatible with the structure of the protecting mounts (Desireddy et al., 2013[Desireddy, A., Conn, B. E., Guo, J., Yoon, B., Barnett, R. N., Monahan, B. M., Kirschbaum, K., Griffith, W. P., Whetten, R. L., Landman, U. & Bigioni, T. P. (2013). Nature, 501, 399-402.]; Conn et al., 2016[Conn, B. E., Atnagulov, A., Yoon, B., Barnett, R. N., Landman, U. & Bigioni, T. P. (2016). Sci. Adv. 2, e1601609.]). It is therefore unlikely that gold atoms would substitute into the ligand shell without changing the metal-atom count (Yang et al., 2014[Yang, H., Wang, Y., Yan, J., Chen, X., Zhang, X., Häkkinen, H. & Zheng, N. (2014). J. Am. Chem. Soc. 136, 7197-7200.]).

Furthermore, gold is known to be more electronegative and more noble than silver, so the gold atoms are expected to assume positions within the structure where they can possess the lowest oxidation state among the metal atoms. Bader analysis (Bader, 1990[Bader, R. F. W. (1990). Atoms in Molecules - A Quantum Theory. New York: Oxford University Press.]; Tang et al., 2009[Tang, W., Sanville, E. & Henkelman, G. (2009). J. Phys. Condens. Matter, 21, 084204.]) of the electron distribution in M4Ag44(p-MBA)30 has shown that atoms in the inner icosa­hedral core have an oxidation state of zero (Conn et al., 2015[Conn, B. E., Desireddy, A., Atnagulov, A., Wickramasinghe, S., Bhattarai, B., Yoon, B., Barnett, R. N., Abdollahian, Y., Kim, Y. W., Griffith, W. P., Oliver, S. R. J., Landman, U. & Bigioni, T. P. (2015). J. Phys. Chem. C, 119, 11238-11249.]; Yang et al., 2013[Yang, H., Wang, Y., Huang, H., Gell, L., Lehtovaara, L., Malola, S., Häkkinen, H. & Zheng, N. (2013). Nat. Commun. 4, 2422.]) whereas in M4Au12Ag32(p-MBA)30 those atoms are slightly reduced (Conn et al., 2018[Conn, B. E., Atnagulov, A., Bhattarai, B., Yoon, B., Landman, U. & Bigioni, T. P. (2018). J. Phys. Chem. C. https://pubs.acs.org/doi/10.1021/acs.jpcc.8b03372.]). The other metal atoms were found to be oxidized, with their oxidation states increasing with distance from the center of the mol­ecule. The X-ray-determined locations of the gold atoms in the inner core are therefore also consistent with the Bader analysis and the known properties of gold and silver.

The crystal structures of Ag44(p-MBA)304−, Au12Ag32(p-MBA)304−, Ag44(SPhF2)304− and Au12Ag32(SPhF2)304− were analyzed carefully to identify changes in the structure as a result of substituting 12 silver atoms for gold atoms. The metal–metal bond lengths within the 12-atom icosa­hedron, the 20-atom dodeca­hedron, and the mounts were compared for the two structures. The results of the bond-length analysis are reported in Table 1[link].

Table 1
Comparison of metal–metal bond lengths (Å) in M4Ag44(p-MBA)30, M4Au12Ag32(p-MBA)30, (PPh4)4Ag44(SPhF2)30 and (PPh4)4Au12Ag32(SPhF2)30, with standard deviations

  M4Ag44(p-MBA)30 M4Au12Ag32(p-MBA)30 (PPh4)4Ag44(SPhF2)30 (PPh4)4Au12Ag32(SPhF2)30
12-Atom icosa­hedron 2.825 ± 0.012 2.795 ± 0.013 2.831 ± 0.019 2.779 ± 0.018
20-Atom dodeca­hedron 3.175 ± 0.040 3.190 ± 0.040 3.167 ± 0.088 3.151 ± 0.066
Icosa­hedron radius 2.688 ± 0.005 2.659 ± 0.009 2.691 ± 0.018 2.644 ± 0.013
Dodeca­hedron radius 4.461 ± 0.021 4.461 ± 0.020 4.468 ± 0.032 4.436 ± 0.029
Ag—Ag in mounts 2.995 ± 0.001 2.992 ± 0.001 2.973 ± 0.016 2.945 ± 0.014

The Au—Au and Ag—Ag bonds in the bulk metals have similar bond lengths (2.884 and 2.889 Å, respectively; JCPDS no. 04-0784 and no. 04-0783, respectively; ICDD, 2015[ICDD (2015). The Powder Diffraction Database. International Centre for Diffraction Data, Newtown Square, Pennsylvania, USA.]), and therefore substituting the two metals might not be expected to change bond lengths within the structures. This is not the case, however. The bond lengths within the 12-atom icosa­hedron were found to shorten from 2.825 ± 0.012 Å to 2.795 ± 0.013 Å when gold was incorporated, indicating stronger than expected bonding within the inner core. Bond lengths within the 20-atom dodeca­hedron were found to be essentially unchanged (3.175 ± 0.040 Å versus 3.190 ± 0.040 Å), however. The metal—metal bonds in the mounts were also found to be unaffected by the gold-atom substitution.

These changes in bond lengths may be the result of a change in the electron-density distribution due to the electrophilicity of the gold atoms in the inner icosa­hedral core, which tend to pull electron density from the outer dodeca­hedral core. For example, Bader analysis of the charge distribution shows that the number of excess electrons on the icosa­hedral core increases from 0.010 to 1.769 upon substitution of gold atoms. This reduction of the inner core is accompanied by a further oxidation of the silver atoms in the outer core, where the number of excess electrons decreases from −4.928 to −6.546 upon substitution of gold atoms. The gold-atom substitution into the core does not affect the charge density on the silver atoms in the mounts. The results of the Bader charge analysis are reported in Table 2[link].

Table 2
Bader analysis results showing excess electrons, Δne, with per-atom values listed in parentheses

Δne > 0 corresponds to excess electrons (negative charge accumulation) and Δne < 0 corresponds to electron depletion (positive charge accumulation).

  M4Ag44(p-MBA)30 M4Au12Ag32(p-MBA)30
Δne(icosa­hedron) 0.010 (0.001) 1.769 (0.147)
Δne(dodeca­hedron) −4.928 (−0.246) −6.546 (−0.327)
Δne(mounts) −4.095 (−0.341) −4.106 (−0.342)

Based on the Bader analysis, the redistribution of the electron density was found to be almost entirely confined to the 32-atom metal core (comprising the icosa­hedral and dodeca­hedral shells). While this appears to be the origin of the changes in metal—metal bond lengths inside the 32-atom metal core, it may also be the reason that the rest of the mol­ecule remains essentially unchanged by this metal-atom modification to the structure.

It is also inter­esting to note that classical electrostatics predicts that any charges carried by a metal sphere would be located on the surface of that sphere. The Bader charge analysis for M4Ag44(p-MBA)30 is in agreement with this classical picture, but that is not the case for M4Au12Ag32(p-MBA)30. In the former case, the inner core is neutral and all of the charge is located on the outer core. In the latter case, both the inner and outer core carry charge (in fact, the 32-atom metal core is polarized). This demonstrates the failure of the classical theory with regard to predicting charge distributions on such a small scale, because of finite screening lengths in real materials.

3. Supra­molecular features

Like the silver-only M4Ag44(p-MBA)30 MPCs, M4Au12Ag32(p-MBA)30 MPCs crystallize as framework structures as a consequence of intra­molecular ligand bundling and inter­molecular hydrogen bonding. The ligand bundling is a consequence of inter­actions between the ligands, with the magnitude of the inter-ligand van der Waals interaction energy calculated to be −0.95 eV/mount. The ligands form six dimer bundles, which are evenly spaced in the same plane, and six trimer bundles, with three above and three below the plane defined by the dimers. Together, the twelve bundles define the connectivity of the crystal's framework structure such that the MPCs have pseudo-face-centered-cubic packing. The nature of the framework structure and hydrogen bonding in these materials was studied in detail in a previous report (Yoon et al., 2014[Yoon, B., Luedtke, W. D., Barnett, R. N., Gao, J., Desireddy, A., Conn, B. E., Bigioni, T. P. & Landman, U. (2014). Nat. Mater. 13, 807-811.]).

4. Database survey

It is instructive to compare the structures of the related but chemically distinct Au12Ag32(p-MBA)304− and Au12Ag32(SPhF2)304− species to examine the effect of ligand structure on crystal structure as well as the question of whether the composition of the outside of the MPC can affect the structure of the core. Likewise, the Ag44(p-MBA)304− and Au12Ag32(p-MBA)304− structures can be compared to address the question of whether the composition of the core can affect the ligand shell and crystal structure.

First, the crystal structures of the two species are entirely different, due to the different mechanisms of inter­actions between the MPCs. In the case of p-MBA, hydrogen bonding governs the inter­actions between the MPCs while ligand bundling within the ligand shell defines the directionality of those inter­actions (Yoon et al., 2014[Yoon, B., Luedtke, W. D., Barnett, R. N., Gao, J., Desireddy, A., Conn, B. E., Bigioni, T. P. & Landman, U. (2014). Nat. Mater. 13, 807-811.]). As a result, the overall structure of the crystal is that of a framework material with large void spaces (Yoon et al., 2014[Yoon, B., Luedtke, W. D., Barnett, R. N., Gao, J., Desireddy, A., Conn, B. E., Bigioni, T. P. & Landman, U. (2014). Nat. Mater. 13, 807-811.]). No such inter­actions exist in the crystals of hydro­phobic MPCs, and therefore the crystal structure is more compact with less well-defined inter­molecular inter­actions (Yang et al., 2013[Yang, H., Wang, Y., Huang, H., Gell, L., Lehtovaara, L., Malola, S., Häkkinen, H. & Zheng, N. (2013). Nat. Commun. 4, 2422.]). The difference in crystal structures due to the different ligands is also expected to lead to entirely different mechanical properties of these two crystalline materials (Yoon et al., 2014[Yoon, B., Luedtke, W. D., Barnett, R. N., Gao, J., Desireddy, A., Conn, B. E., Bigioni, T. P. & Landman, U. (2014). Nat. Mater. 13, 807-811.]). The observed differences in crystal structures are similar when comparing Ag44 and Au12Ag32 cores, however, indicating that the added gold did not affect the ligand shell and crystal structure. This also indicates that the chemical stability can be improved with the addition of gold without changing the overall structure and mechanical properties of the MPC crystal.

The differences in the nature of the ligands were not found to have affected the overall arrangement of gold atoms in the MPC cores, with the gold atoms occupying the same positions in both structures. The different ligands induce slightly different bonding within the metal core, however. Bond lengths in the icosa­hedral core in Ag44 and Au12Ag32 are similar for both p-MBA and SPhF2 ligands, contracting 0.03 and 0.05 Å, respectively, with the addition of gold atoms. This indicates that changes in the icosa­hedral core are not influenced by the ligands. Changes in bond lengths are different in the dodeca­hedral core, however. In the case of p-MBA, bond lengths in the dodeca­hedron do not change with the addition of gold atoms, but in the case of the SPhF2 ligand they contract slightly. This indicates that changes in the dodeca­hedral core are influenced by the SPhF2 ligands, presumably due to their greater electron-withdrawing ability. The net effect is that the radius of the icosa­hedron contracts slightly in the case of both p-MBA and SPhF2 (0.03 and 0.05 Å, respectively), but the radius of the dodeca­hedron does not change for p-MBA while it contracts 0.03 Å in the case of SPhF2.

5. Synthesis, crystallization, and theoretical methodology

Synthesis of M4Au12Ag32(p-MBA)30 by co-reduction

M4Au12Ag32(p-MBA)30 MPCs were produced by first synthesizing a distribution of M4AuxAg44–x(p-MBA)30 MPCs using an Au:Ag input ratio of 14:30. For this input ratio, 72.4 mg of AuCl3 (0.24 mmol) and 86.8 mg of AgNO3 (0.51 mmol) were used for the metal sources. These materials were added to 33 ml of 7:4 water–DMSO solvent along with 200 mg of p-MBA (1.3 mmol). This mixture was sonicated and stirred to fully dissolve the p-MBA. The dissolved p-MBA reacted with the metals to form a precursor mixture of metal thiol­ates, which was a cloudy light-yellow precipitate that was dispersed in the solvent. The pH was then adjusted to 12 using 50% w/v aqueous CsOH. The metal thiol­ates dissolved as the pH was raised above 9, forming a clear, light-yellow solution. Next, 5.0 mmol of NaBH4 reducing agent dissolved in 9 ml of water was added dropwise over a period of 30 min, and was then left to stir for 1 h. This formed a dark-yellow/brown solution. Once the reaction was completed, the product solution was centrifuged for 5 min (to remove insoluble byproducts), deca­nted, and then the supernatant was precip­itated using DMF. The precipitate was collected by centrifugation. It is important not to dry this raw product.

The raw product was precipitated from a basic solution; therefore it was the conjugate base (alkali metal salt) of the fully protonated species. To protonate, pure DMF was added to the precipitated particles, which did not initially solubilize. Glacial acetic acid was then added dropwise to the solution until the precipitate dissolved into the DMF, forming a golden brown solution. Protonation was repeated three times, using toluene to precipitate from DMF.

Fully protonated M4AuxAg44–x(p-MBA)30 MPCs were next subjected to thermal processing. Capped glass vials containing DMF solutions of the MPCs were placed in a water bath at 333 K for 30 h. After incubation, insoluble material produced by thermal processing was separated from the solution by centrifugation. The supernatant was collected and was protonated with glacial acetic acid in DMF and precipitated with toluene. The protonation steps were repeated two times to ensure complete protonation of the carboxyl­ates. The fully protonated product enriched in M4Au12Ag32(p-MBA)30 was able to be dissolved in a neat solution of DMF.

With the above synthetic conditions, the counter-cations tend to be a mixture of alkali metals, namely Cs+ and Na+. The counter-ion mixture has been identified by energy dispersive X-ray spectroscopy (EDS) to be approximately a 3:1 ratio of Cs:Na, despite the expectation that there might be a higher affinity for Na because of its size. The mol­ecular formula for this MPC could therefore be written as NaCs3Au12Ag32(p-MBA)30. It should be noted, however, that the counter-ions are readily dissociated and easily exchanged such that the identities of the alkali metals play little role in the properties of the material. Nonetheless, Na4Au12Ag32(p-MBA)30 and K4Au12Ag32(p-MBA)30 can be directly prepared by using all-sodium and all-potassium reaction conditions, respectively, if desired (Desireddy et al., 2013[Desireddy, A., Conn, B. E., Guo, J., Yoon, B., Barnett, R. N., Monahan, B. M., Kirschbaum, K., Griffith, W. P., Whetten, R. L., Landman, U. & Bigioni, T. P. (2013). Nature, 501, 399-402.]).

Crystallization

The M4Au12Ag32(p-MBA)30 crystals were grown from a neat DMF solution of MPCs, dried under N2 gas. Small rhombohedral crystals (10 µm) were obtained from this crystallization process. These crystals were used as seeds in a second crystallization step. The second solution was dried under N2 and the seeds grew into larger rhombohedral crystals (>50 µm). The crystals were first separated and isolated on a microscope slide using paratone oil, and then were picked up and mounted with a MiTeGen MicroLoop.

Theoretical Methodology

The density functional theory (DFT) calculations and Bader charge analysis (Bader, 1990[Bader, R. F. W. (1990). Atoms in Molecules - A Quantum Theory. New York: Oxford University Press.]; Tang et al., 2009[Tang, W., Sanville, E. & Henkelman, G. (2009). J. Phys. Condens. Matter, 21, 084204.]) were performed using the VASP–DFT package with a plane-wave basis with a kinetic energy cutoff of 400 eV, PAW pseudo­potentials (Kresse & Joubert, 1999[Kresse, G. & Joubert, D. (1999). Phys. Rev. B, 59, 1758-1775.]), and the PW91 generalized gradient approximation (GGA) for the exchange-correlation potential (Perdew, 1991[Perdew, J. P. (1991). Unified Theory of Exchange and Correlation Beyond the Local Density Approximation. In Electronic Structure of Solids '91, edited by P. Ziesche and H. Eschrig, pp. 11-20. Berlin: Akademie Verlag.]; Perdew et al., 1992[Perdew, J. P., Chevary, J. A., Vosko, S. H., Jackson, K. A., Pederson, M. R., Singh, D. J. & Fiolhais, C. (1992). Phys. Rev. B, 46, 6671-6687.], 1993[Perdew, J. P., Chevary, J. A., Vosko, S. H., Jackson, K. A., Pederson, M. R., Singh, D. J. & Fiolhais, C. (1993). Phys. Rev. B, 48, 4978-4978.]). For structure optimization, convergence was achieved for forces smaller than 0.001 eV Å−1. The X-ray determined structure of Na4Ag44(p-MBA)30 was taken as the starting configuration for structural relaxation. Hydrogen atoms were added to the structure and their positions were relaxed, yielding d(C—H) = 1.09 Å.

To estimate the inter-ligand van der Waals (vdW) inter­action energy, the total energy of the relaxed Na4Au12Ag32(p-MBA)30 MPC was evaluated with and without the inclusion of the vdW inter­actions, using density functional theory (DFT) (Grimme, 2006[Grimme, S. (2006). J. Comput. Chem. 27, 1787-1799.]). The energy of the MPC, calculated with the inclusion of the vdW inter­actions between the atomic constit­uents of the ligand (S, C, O and H atoms) was found to be lower by Δtot (vdW) = 13.23 eV compared to that found without the inclusion of the vdW contributions. However, this vdW energy includes intra­molecular and inter­molecular inter­actions between the ligand mol­ecules. The average intra-ligand (Ag—S—C6H4—COOH) vdW stabilization energy was calculated (for the relaxed configuration of the Ag-bonded ligand mol­ecule) using DFT to be Δintra (vdW) = 0.251 eV. The total inter­molecular vdW energy in the ligand shell (made of 30 p-MBA mol­ecules) is therefore calculated as: Δinter (vdW) = Δtot (vdW) − 30 Δintra (vdW) = 5.70 eV. Since the ligand mol­ecules are assembled into six Ag2(p-MBA)5 mounts, we conclude that the inter-ligand non-bonded (dispersion, vdW) energy is 0.95 eV/mount.

6. Refinement

All of the Ag, Au and S atoms were located by direct methods. During the following refinements and subsequent difference-Fourier syntheses, the remaining C atoms and O atoms were located.

The Au, Ag and S atoms were ordered; however three out of the five crystallographically independent ligands in the asymmetric unit cell were disordered over two sets of sites. The three disordered ligands were modeled over the two positions, and their occupancies were refined with fixed atomic displacement parameters using a free variable to be 0.5. Final refinement released the fixed atomic displacement parameter and constrained the occupancies to be 0.5 for all disordered C and O atoms.

Au, Ag, and S atoms were refined with anisotropic displace­ment parameters, while all C and O atoms were refined with isotropic atomic displacement parameters. DFIX restraints were applied to the C—O bonds in the carb­oxy­lic acid groups, but C-atom positions in the phenyl rings were not restrained. All H atoms were geometrically determined on idealized positions (O—H = 0.84, C—H = 0.95°), using AFIX 43 and AFIX 83 instructions, and were included as riding atoms in the final refinements [Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O)].

It is common for MPCs to have a high amount of residual electron density observed in the metal core. It is noted that the alkali metal cations and the solvent mol­ecules were not identified in the X-ray data (highest residue density was 2.55 e Å−3). PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) was used to determine the total void volume in the unit cell to be about 52% with an estimate of 19000 electrons. Attempts to improve the refinement using the SQUEEZE (Spek, 2015[Spek, A. L. (2015). Acta Cryst. C71, 9-18.]) option in PLATON were not successful.

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. Note that the given formula, density, etc. in this Table refers to the refined part of the structure and do not include the type of counter ions and solvent mol­ecules.

Table 3
Experimental details

Crystal data
Chemical formula Ag32Au12(C7H5O2S)30
Mr 10410.53
Crystal system, space group Trigonal, R[\overline{3}]c:H
Temperature (K) 100
a, c (Å) 25.7341 (3), 124.079 (4)
V3) 71162 (3)
Z 6
Radiation type Cu Kα
μ (mm−1) 18.65
Crystal size (mm) 0.2 × 0.2 × 0.1
 
Data collection
Diffractometer Bruker APEX Duo CCD
Absorption correction Multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.])
Tmin, Tmax 0.565, 0.752
No. of measured, independent and observed [I > 2σ(I)] reflections 182413, 12622, 11138
Rint 0.055
θmax (°) 62.4
(sin θ/λ)max−1) 0.575
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.139, 1.09
No. of reflections 12622
No. of parameters 364
No. of restraints 16
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 2.54, −1.52
Computer programs: APEX2 and SAINT (Bruker, 2012[Bruker (2012). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014/7 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Triacontakis[(4-carboxylatophenyl)sulfanido]dodecagolddotriacontasilver top
Crystal data top
Ag32Au12(C7H5O2S)30Dx = 1.458 Mg m3
Mr = 10410.53Cu Kα radiation, λ = 1.54178 Å
Trigonal, R3c:HCell parameters from 9758 reflections
a = 25.7341 (3) Åθ = 4.1–62.4°
c = 124.079 (4) ŵ = 18.65 mm1
V = 71162 (3) Å3T = 100 K
Z = 6Rhombohedral, dark_purple
F(000) = 289320.2 × 0.2 × 0.1 mm
Data collection top
Bruker APEX Duo CCD
diffractometer
11138 reflections with I > 2σ(I)
Radiation source: ImuSRint = 0.055
phi and ω scansθmax = 62.4°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2928
Tmin = 0.565, Tmax = 0.752k = 2929
182413 measured reflectionsl = 134142
12622 independent reflections
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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0801P)2 + 2212.5481P]
where P = (Fo2 + 2Fc2)/3
12622 reflections(Δ/σ)max < 0.001
364 parametersΔρmax = 2.54 e Å3
16 restraintsΔρmin = 1.52 e Å3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The data reported herein were collected from a crystal of approximate dimensions 200 x 200 x 100 µm3, which was cooled to 100 K for data collection. X-ray diffraction data were collected on a Bruker Apex Duo diffractometer (CuKα = 1.54178 Å), which was equipped with an Apex II CCD detector and an Oxford Cryostream 700 low temperature device.

The frames were integrated with the Bruker SAINT software package using a narrow-frame algorithm. The integration of the data using a trigonal unit cell yielded a total of 182413 reflections to a maximum θ angle of 62.42° (0.87 Å resolution), of which 12622 were independent (average redundancy 14.452, completeness = 100.0%, Rint = 5.49%, Rsig = 1.92%) and 11138 (88.24%) were greater than 2σ(F2). The final cell constants of a = 25.7341 (3) Å, b = 25.7341 (3) Å, c = 124.079 (4) Å, volume = 71162 (3) Å3, are based upon the refinement of the XYZ-centroids of reflections above 20 σ(I).

The structure was solved and refined using the Bruker SHELXTL software package (Sheldrick, 2015), using the R3c space group, with Z = 6 for the formula unit C210H150Ag32Au12O60S30. The final full-matrix least-squares refinement on F2 with 373 variables converged at R1 = 3.98% for the observed data and wR2 = 13.91% for all data. The goodness-of-fit was 1.094. The largest peak in the final difference electron density synthesis was 2.547 e-3 and the largest hole was -1.528 e/Å3 with an RMS deviation of 0.253 e/Å3. On the basis of the final model, the calculated density was 1.458 g/cm3 and F(000) was 28932 e-. The cations and solvent molecules are not included in the calculations of the density or F(000).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Au10.04843 (2)0.07066 (2)0.01714 (2)0.01581 (10)
Au20.07933 (2)0.11391 (2)0.00404 (2)0.01596 (10)
Ag10.06659 (3)0.18648 (2)0.01209 (2)0.02133 (14)
Ag20.16900 (3)0.15380 (3)0.01221 (2)0.02476 (15)
Ag30.12936 (3)0.04066 (3)0.02703 (2)0.02510 (15)
Ag40.00000.00000.03625 (2)0.0219 (2)
Ag50.26323 (3)0.12998 (4)0.02307 (2)0.0454 (2)
Ag60.19339 (4)0.16795 (3)0.03705 (2)0.0446 (2)
S10.10178 (11)0.26224 (10)0.00377 (2)0.0339 (5)
S20.15995 (10)0.22519 (10)0.02506 (2)0.0338 (5)
S30.21203 (11)0.01710 (11)0.02284 (2)0.0352 (5)
S40.10443 (11)0.07711 (11)0.04443 (2)0.0340 (5)
S50.30419 (15)0.21218 (16)0.03686 (3)0.0678 (9)
O10.0603 (9)0.4829 (9)0.01510 (15)0.159 (7)*
O20.0670 (8)0.5043 (9)0.00219 (14)0.156 (6)*
H2B0.08540.54110.00080.234*
O30.3977 (8)0.4646 (8)0.00301 (15)0.152 (6)*
O40.4186 (9)0.4802 (9)0.02040 (16)0.182 (8)*
H300.45250.50440.01790.273*
C10.0892 (5)0.3229 (5)0.00131 (9)0.044 (2)*
C20.0840 (7)0.3366 (8)0.00909 (14)0.083 (4)*
H20.08440.31270.01490.099*
C30.0782 (9)0.3862 (10)0.01093 (18)0.112 (6)*
H30.07420.39580.01820.134*
C40.0777 (8)0.4212 (8)0.00311 (15)0.089 (5)*
C50.0775 (9)0.4038 (9)0.00702 (17)0.104 (6)*
H50.07120.42480.01270.125*
C60.0861 (7)0.3567 (8)0.00948 (14)0.085 (5)*
H60.08980.34770.01680.101*
C70.0730 (11)0.4749 (11)0.00580 (16)0.126 (8)*
C80.2244 (5)0.2937 (5)0.02136 (9)0.042 (2)*
C90.2413 (7)0.3085 (7)0.01055 (13)0.076 (4)*
H90.21800.28050.00510.092*
C100.2905 (9)0.3621 (9)0.00755 (17)0.105 (6)*
H100.30020.37270.00020.125*
C110.3264 (8)0.4012 (8)0.01608 (15)0.088 (5)*
C120.3145 (10)0.3810 (10)0.02632 (19)0.119 (7)*
H120.34230.40420.03180.143*
C130.2630 (8)0.3273 (8)0.02929 (16)0.093 (5)*
H130.25530.31490.03660.112*
C140.3790 (10)0.4579 (11)0.01247 (17)0.128 (8)*
C150.2296 (5)0.0106 (5)0.03434 (9)0.042 (2)*
C16A0.2830 (12)0.0094 (12)0.0343 (2)0.062 (7)*0.5
H160.30930.00630.02830.074*0.5
C17A0.2987 (13)0.0318 (13)0.0433 (2)0.066 (7)*0.5
H170.33630.03040.04340.079*0.5
C16B0.2063 (11)0.0699 (11)0.03674 (19)0.052 (6)*0.5
H15A0.17670.09810.03200.062*0.5
C17B0.2215 (12)0.0920 (13)0.0452 (2)0.061 (7)*0.5
H16D0.20290.13410.04630.073*0.5
C180.2618 (7)0.0556 (7)0.05210 (12)0.070 (4)*
C19A0.2032 (13)0.0594 (13)0.0516 (2)0.068 (7)*0.5
H16A0.17610.07630.05750.081*0.5
C20A0.1868 (12)0.0387 (11)0.0427 (2)0.058 (6)*0.5
H150.14790.04310.04220.069*0.5
C19B0.292 (2)0.009 (2)0.0505 (4)0.116 (14)*0.5
H19A0.32320.03640.05510.139*0.5
C20B0.2722 (15)0.0296 (15)0.0417 (3)0.079 (8)*0.5
H19B0.28820.07150.04070.095*0.5
C210.2809 (8)0.0758 (8)0.06148 (14)0.088 (5)*
O5A0.3244 (11)0.0827 (12)0.0607 (2)0.106 (8)*0.5
O6A0.2398 (11)0.1019 (13)0.0689 (2)0.115 (9)*0.5
H6A20.23680.07570.07250.172*0.5
O5B0.2560 (10)0.1306 (8)0.06321 (18)0.087 (6)*0.5
O6B0.3251 (11)0.0364 (11)0.0677 (2)0.116 (9)*0.5
H5B20.35820.02690.06480.173*0.5
C220.1284 (5)0.0498 (5)0.05536 (9)0.042 (2)*
C23A0.1932 (14)0.0827 (14)0.0578 (3)0.076 (8)*0.5
H230.21980.11710.05370.091*0.5
C24A0.2140 (15)0.0630 (15)0.0659 (3)0.079 (9)*0.5
H240.25580.08160.06730.095*0.5
C23B0.1297 (12)0.0051 (12)0.0543 (2)0.063 (7)*0.5
H23D0.11760.02720.04770.075*0.5
C24B0.1490 (14)0.0256 (14)0.0630 (2)0.073 (8)*0.5
H24D0.14850.06270.06270.087*0.5
C250.1696 (7)0.0115 (7)0.07240 (13)0.072 (4)*
C26A0.1127 (12)0.0137 (12)0.0701 (2)0.061 (7)*0.5
H260.08470.04610.07440.074*0.5
C27A0.0920 (11)0.0051 (11)0.06161 (19)0.052 (6)*0.5
H270.05010.01480.06020.062*0.5
C26B0.1633 (15)0.0579 (15)0.0734 (3)0.079 (9)*0.5
H26D0.17290.07890.08000.095*0.5
C27B0.1424 (14)0.0778 (14)0.0648 (2)0.074 (8)*0.5
H27D0.13820.11220.06570.089*0.5
C280.1937 (8)0.0066 (7)0.08157 (14)0.087 (5)*
O7A0.1580 (9)0.0490 (9)0.08716 (17)0.081 (6)*0.5
O8A0.2526 (10)0.0242 (11)0.0834 (2)0.114 (9)*0.5
H7AB0.27110.02710.07760.171*0.5
O7B0.2052 (13)0.0231 (12)0.09017 (19)0.115 (9)*0.5
O8B0.1907 (13)0.0591 (10)0.0807 (2)0.113 (8)*0.5
H7BC0.22410.05400.07870.170*0.5
C290.3289 (7)0.1857 (7)0.04713 (13)0.075 (4)*
C30A0.3335 (16)0.1336 (16)0.0455 (3)0.087 (9)*0.5
H30D0.32220.11360.03870.104*0.5
C31A0.3559 (18)0.1093 (19)0.0543 (3)0.102 (11)*0.5
H310.35800.07360.05360.122*0.5
C30B0.2911 (17)0.1600 (15)0.0569 (3)0.087 (9)*0.5
H30A0.25340.15820.05740.104*0.5
C31B0.311 (2)0.1388 (19)0.0654 (4)0.112 (13)*0.5
H31A0.28640.11970.07150.134*0.5
C320.3749 (9)0.1477 (9)0.06437 (16)0.101 (6)*
C33A0.372 (2)0.199 (2)0.0655 (4)0.118 (14)*0.5
H320.38630.22250.07190.141*0.5
C34A0.3480 (17)0.2182 (18)0.0574 (3)0.096 (11)*0.5
H340.34410.25260.05840.115*0.5
C33B0.4124 (19)0.1760 (17)0.0556 (3)0.101 (11)*0.5
H32A0.45100.17980.05510.121*0.5
C34B0.3891 (16)0.2002 (16)0.0471 (3)0.089 (10)*0.5
H34A0.41540.22560.04170.107*0.5
C350.3961 (10)0.1233 (11)0.07298 (18)0.118 (7)*
O9A0.4219 (14)0.1564 (14)0.0809 (2)0.133 (10)*0.5
O10A0.4058 (18)0.0792 (14)0.0704 (3)0.161 (13)*0.5
H10B0.43880.08600.07300.241*0.5
O9B0.3657 (13)0.1071 (13)0.0814 (2)0.119 (9)*0.5
O10B0.4520 (12)0.1357 (16)0.0722 (3)0.140 (11)*0.5
H10C0.47450.16810.07540.210*0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Au10.01673 (17)0.01546 (17)0.01451 (17)0.00750 (13)0.00106 (12)0.00080 (12)
Au20.01646 (17)0.01459 (17)0.01613 (18)0.00724 (13)0.00094 (12)0.00051 (12)
Ag10.0255 (3)0.0142 (3)0.0232 (3)0.0091 (2)0.0015 (2)0.0036 (2)
Ag20.0195 (3)0.0196 (3)0.0253 (3)0.0024 (2)0.0057 (2)0.0001 (2)
Ag30.0236 (3)0.0258 (3)0.0217 (3)0.0092 (3)0.0089 (2)0.0015 (2)
Ag40.0269 (3)0.0269 (3)0.0119 (5)0.01346 (17)0.0000.000
Ag50.0306 (4)0.0455 (4)0.0491 (4)0.0109 (3)0.0096 (3)0.0091 (4)
Ag60.0528 (5)0.0344 (4)0.0340 (4)0.0124 (4)0.0132 (3)0.0023 (3)
S10.0498 (14)0.0208 (11)0.0338 (12)0.0198 (10)0.0045 (10)0.0033 (9)
S20.0291 (11)0.0241 (11)0.0347 (12)0.0033 (9)0.0099 (9)0.0027 (9)
S30.0331 (12)0.0380 (13)0.0358 (12)0.0189 (11)0.0149 (10)0.0000 (10)
S40.0337 (12)0.0387 (13)0.0216 (11)0.0120 (10)0.0104 (9)0.0013 (9)
S50.0530 (18)0.062 (2)0.065 (2)0.0111 (16)0.0263 (16)0.0033 (16)
Geometric parameters (Å, º) top
Au1—Au2i2.7802 (4)C11—C121.35 (3)
Au1—Au1ii2.7893 (5)C11—C141.48 (3)
Au1—Au1iii2.7893 (5)C12—C131.40 (3)
Au1—Au22.8089 (4)C12—H120.9500
Au1—Au2iv2.8115 (4)C13—H130.9500
Au1—Ag22.8179 (7)C15—C16A1.36 (3)
Au1—Ag3ii2.8362 (7)C15—C16B1.36 (3)
Au1—Ag32.8372 (7)C15—C20B1.40 (3)
Au1—Ag12.8462 (6)C15—C20A1.42 (3)
Au1—Ag42.8664 (8)C16A—C17A1.41 (4)
Au2—Au1iv2.7804 (4)C16A—H160.9500
Au2—Au2i2.7897 (4)C17A—C181.37 (3)
Au2—Au2iv2.7898 (4)C17A—H170.9500
Au2—Au1i2.8117 (4)C16B—C17B1.35 (3)
Au2—Ag22.8414 (6)C16B—H15A0.9500
Au2—Ag2i2.8459 (7)C17B—C181.31 (3)
Au2—Ag1iv2.8639 (6)C17B—H16D0.9500
Au2—Ag12.8661 (6)C18—C211.46 (2)
Au2—Ag3i2.8736 (7)C18—C19B1.46 (5)
Ag1—S12.594 (2)C18—C19A1.46 (3)
Ag1—S3ii2.633 (2)C19A—C20A1.38 (4)
Ag1—S22.638 (2)C19A—H16A0.9500
Ag1—Au2i2.8637 (6)C20A—H150.9500
Ag1—Ag23.1417 (9)C19B—C20B1.41 (5)
Ag1—Ag3ii3.2309 (9)C19B—H19A0.9500
Ag1—Ag2i3.2323 (8)C20B—H19B0.9500
Ag2—S22.530 (3)C21—O5A1.222 (17)
Ag2—S1iv2.544 (2)C21—O5B1.240 (16)
Ag2—Au2iv2.8457 (7)C21—O6A1.308 (17)
Ag2—Ag53.0921 (10)C21—O6B1.328 (17)
Ag2—Ag63.1309 (9)O6A—H6A20.8400
Ag2—Ag33.1516 (8)O6B—H5B20.8400
Ag2—Ag1iv3.2320 (8)C22—C27A1.31 (3)
Ag3—S32.540 (3)C22—C27B1.33 (3)
Ag3—S42.560 (2)C22—C23B1.43 (3)
Ag3—Au1iii2.8364 (7)C22—C23A1.48 (3)
Ag3—Au2iv2.8737 (7)C23A—C24A1.35 (4)
Ag3—Ag53.0781 (10)C23A—H230.9500
Ag3—Ag63.0973 (10)C24A—C251.49 (4)
Ag3—Ag43.1624 (7)C24A—H240.9500
Ag3—Ag1iii3.2313 (9)C23B—C24B1.40 (4)
Ag4—S4ii2.619 (2)C23B—H23D0.9500
Ag4—S42.619 (2)C24B—C251.43 (3)
Ag4—S4iii2.619 (2)C24B—H24D0.9500
Ag4—Au1ii2.8663 (8)C25—C26B1.29 (3)
Ag4—Au1iii2.8663 (8)C25—C26A1.30 (3)
Ag4—Ag3iii3.1625 (7)C25—C281.48 (2)
Ag4—Ag3ii3.1625 (7)C26A—C27A1.37 (3)
Ag5—S52.506 (4)C26A—H260.9500
Ag5—S32.519 (3)C27A—H270.9500
Ag5—S1iv2.525 (2)C26B—C27B1.40 (4)
Ag5—Ag62.9916 (13)C26B—H26D0.9500
Ag6—S52.486 (4)C27B—H27D0.9500
Ag6—S42.489 (2)C28—O7A1.231 (16)
Ag6—S22.528 (2)C28—O7B1.259 (17)
S1—C11.773 (11)C28—O8B1.319 (17)
S1—Ag5i2.524 (2)C28—O8A1.333 (17)
S1—Ag2i2.544 (2)O8A—H7AB0.8400
S2—C81.774 (11)O8B—H7BC0.8400
S3—C151.753 (11)C29—C34B1.40 (4)
S3—Ag1iii2.633 (2)C29—C30A1.42 (4)
S4—C221.774 (11)C29—C34A1.46 (4)
S5—C291.711 (16)C29—C30B1.49 (4)
O1—C71.244 (16)C30A—C31A1.51 (5)
O2—C71.303 (16)C30A—H30D0.9500
O2—H2B0.8400C31A—C321.51 (4)
O3—C141.247 (16)C31A—H310.9500
O4—C141.323 (16)C30B—C31B1.39 (5)
O4—H300.8400C30B—H30A0.9500
C1—C21.362 (19)C31B—C321.55 (5)
C1—C61.36 (2)C31B—H31A0.9500
C2—C31.38 (2)C32—C33A1.38 (5)
C2—H20.9500C32—C33B1.39 (4)
C3—C41.33 (3)C32—C351.48 (3)
C3—H30.9500C33A—C34A1.39 (5)
C4—C51.33 (2)C33A—H320.9500
C4—C71.48 (3)C34A—H340.9500
C5—C61.37 (2)C33B—C34B1.49 (5)
C5—H50.9500C33B—H32A0.9500
C6—H60.9500C34B—H34A0.9500
C8—C131.36 (2)C35—O9B1.246 (17)
C8—C91.403 (18)C35—O9A1.250 (18)
C9—C101.38 (2)C35—O10B1.311 (18)
C9—H90.9500C35—O10A1.318 (18)
C10—C111.43 (3)O10A—H10B0.8400
C10—H100.9500O10B—H10C0.8400
Au2i—Au1—Au1ii60.638 (12)Ag3—Ag4—Ag3iii107.70 (2)
Au2i—Au1—Au1iii108.352 (11)S4ii—Ag4—Ag3ii51.53 (6)
Au1ii—Au1—Au1iii60.0S4—Ag4—Ag3ii100.24 (5)
Au2i—Au1—Au259.883 (8)S4iii—Ag4—Ag3ii149.88 (6)
Au1ii—Au1—Au2108.158 (10)Au1ii—Ag4—Ag3ii55.884 (16)
Au1iii—Au1—Au2107.485 (10)Au1iii—Ag4—Ag3ii102.99 (3)
Au2i—Au1—Au2iv107.480 (16)Au1—Ag4—Ag3ii55.865 (16)
Au1ii—Au1—Au2iv107.468 (11)Ag3—Ag4—Ag3ii107.70 (2)
Au1iii—Au1—Au2iv59.522 (12)Ag3iii—Ag4—Ag3ii107.69 (2)
Au2—Au1—Au2iv59.519 (8)S5—Ag5—S3137.53 (10)
Au2i—Au1—Ag2114.254 (17)S5—Ag5—S1iv116.78 (10)
Au1ii—Au1—Ag2166.301 (15)S3—Ag5—S1iv105.47 (8)
Au1iii—Au1—Ag2113.81 (2)S5—Ag5—Ag652.88 (9)
Au2—Au1—Ag260.660 (15)S3—Ag5—Ag6109.26 (7)
Au2iv—Au1—Ag260.730 (16)S1iv—Ag5—Ag6110.33 (7)
Au2i—Au1—Ag3ii61.531 (15)S5—Ag5—Ag3111.27 (9)
Au1ii—Au1—Ag3ii60.566 (17)S3—Ag5—Ag352.84 (6)
Au1iii—Au1—Ag3ii114.125 (17)S1iv—Ag5—Ag3101.65 (5)
Au2—Au1—Ag3ii115.587 (17)Ag6—Ag5—Ag361.35 (2)
Au2iv—Au1—Ag3ii166.218 (18)S5—Ag5—Ag299.84 (9)
Ag2—Au1—Ag3ii130.01 (2)S3—Ag5—Ag2102.34 (6)
Au2i—Au1—Ag3166.617 (18)S1iv—Ag5—Ag252.68 (6)
Au1ii—Au1—Ag3114.098 (16)Ag6—Ag5—Ag261.92 (2)
Au1iii—Au1—Ag360.538 (17)Ag3—Ag5—Ag261.43 (2)
Au2—Au1—Ag3114.325 (17)S5—Ag6—S4137.68 (11)
Au2iv—Au1—Ag361.156 (15)S5—Ag6—S2111.98 (10)
Ag2—Au1—Ag367.738 (18)S4—Ag6—S2110.04 (8)
Ag3ii—Au1—Ag3128.36 (3)S5—Ag6—Ag553.50 (9)
Au2i—Au1—Ag161.177 (15)S4—Ag6—Ag5109.10 (7)
Au1ii—Au1—Ag1115.60 (2)S2—Ag6—Ag5106.52 (6)
Au1iii—Au1—Ag1166.782 (13)S5—Ag6—Ag3111.24 (10)
Au2—Au1—Ag160.900 (14)S4—Ag6—Ag353.21 (6)
Au2iv—Au1—Ag1114.024 (17)S2—Ag6—Ag3102.95 (6)
Ag2—Au1—Ag167.374 (19)Ag5—Ag6—Ag360.70 (2)
Ag3ii—Au1—Ag169.302 (19)S5—Ag6—Ag299.27 (9)
Ag3—Au1—Ag1128.43 (2)S4—Ag6—Ag2102.49 (5)
Au2i—Au1—Ag4115.242 (13)S2—Ag6—Ag251.79 (6)
Au1ii—Au1—Ag460.885 (10)Ag5—Ag6—Ag260.62 (2)
Au1iii—Au1—Ag460.884 (10)Ag3—Ag6—Ag260.80 (2)
Au2—Au1—Ag4166.498 (17)C1—S1—Ag5i110.7 (4)
Au2iv—Au1—Ag4114.256 (13)C1—S1—Ag2i116.3 (4)
Ag2—Au1—Ag4128.732 (18)Ag5i—S1—Ag2i75.20 (7)
Ag3ii—Au1—Ag467.360 (15)C1—S1—Ag1112.5 (4)
Ag3—Au1—Ag467.343 (14)Ag5i—S1—Ag1135.83 (9)
Ag1—Au1—Ag4129.626 (18)Ag2i—S1—Ag177.96 (7)
Au1iv—Au2—Au2i108.283 (10)C8—S2—Ag6108.0 (4)
Au1iv—Au2—Au2iv60.575 (9)C8—S2—Ag2100.3 (4)
Au2i—Au2—Au2iv107.825 (12)Ag6—S2—Ag276.48 (7)
Au1iv—Au2—Au1108.883 (15)C8—S2—Ag1116.1 (4)
Au2i—Au2—Au159.547 (12)Ag6—S2—Ag1130.54 (9)
Au2iv—Au2—Au160.287 (12)Ag2—S2—Ag174.83 (6)
Au1iv—Au2—Au1i59.836 (14)C15—S3—Ag5111.5 (4)
Au2i—Au2—Au1i60.201 (9)C15—S3—Ag3110.3 (4)
Au2iv—Au2—Au1i108.071 (10)Ag5—S3—Ag374.94 (7)
Au1—Au2—Au1i107.996 (15)C15—S3—Ag1iii112.9 (4)
Au1iv—Au2—Ag2115.290 (18)Ag5—S3—Ag1iii133.37 (9)
Au2i—Au2—Ag2113.22 (2)Ag3—S3—Ag1iii77.28 (6)
Au2iv—Au2—Ag260.701 (17)C22—S4—Ag6108.3 (4)
Au1—Au2—Ag259.826 (15)C22—S4—Ag3107.4 (4)
Au1i—Au2—Ag2165.951 (18)Ag6—S4—Ag375.67 (7)
Au1iv—Au2—Ag2i113.215 (17)C22—S4—Ag4115.1 (4)
Au2i—Au2—Ag2i60.555 (16)Ag6—S4—Ag4133.05 (9)
Au2iv—Au2—Ag2i165.734 (16)Ag3—S4—Ag475.26 (6)
Au1—Au2—Ag2i114.251 (17)C29—S5—Ag6112.3 (6)
Au1i—Au2—Ag2i59.743 (15)C29—S5—Ag5104.8 (6)
Ag2—Au2—Ag2i129.876 (18)Ag6—S5—Ag573.62 (9)
Au1iv—Au2—Ag1iv60.548 (14)C7—O2—H2B109.5
Au2i—Au2—Ag1iv166.546 (15)C14—O4—H30109.5
Au2iv—Au2—Ag1iv60.911 (15)C2—C1—C6119.7 (14)
Au1—Au2—Ag1iv114.948 (17)C2—C1—S1118.4 (10)
Au1i—Au2—Ag1iv114.334 (16)C6—C1—S1121.9 (11)
Ag2—Au2—Ag1iv69.010 (19)C1—C2—C3117.9 (17)
Ag2i—Au2—Ag1iv129.17 (2)C1—C2—H2121.1
Au1iv—Au2—Ag1166.985 (18)C3—C2—H2121.1
Au2i—Au2—Ag160.820 (17)C4—C3—C2123 (2)
Au2iv—Au2—Ag1114.08 (2)C4—C3—H3118.3
Au1—Au2—Ag160.193 (14)C2—C3—H3118.3
Au1i—Au2—Ag1114.789 (17)C3—C4—C5118 (2)
Ag2—Au2—Ag166.794 (19)C3—C4—C7120.0 (18)
Ag2i—Au2—Ag168.923 (18)C5—C4—C7122.3 (19)
Ag1iv—Au2—Ag1129.007 (17)C4—C5—C6122 (2)
Au1iv—Au2—Ag3i60.189 (15)C4—C5—H5119.0
Au2i—Au2—Ag3i113.779 (19)C6—C5—H5119.0
Au2iv—Au2—Ag3i115.005 (19)C1—C6—C5119.0 (17)
Au1—Au2—Ag3i166.157 (19)C1—C6—H6120.5
Au1i—Au2—Ag3i59.858 (15)C5—C6—H6120.5
Ag2—Au2—Ag3i131.10 (2)O1—C7—O2119 (2)
Ag2i—Au2—Ag3i66.867 (18)O1—C7—C4121 (2)
Ag1iv—Au2—Ag3i68.546 (18)O2—C7—C4117.3 (19)
Ag1—Au2—Ag3i129.22 (2)C13—C8—C9119.5 (13)
S1—Ag1—S3ii108.36 (8)C13—C8—S2117.9 (11)
S1—Ag1—S2105.62 (8)C9—C8—S2121.7 (10)
S3ii—Ag1—S2106.73 (8)C10—C9—C8122.3 (16)
S1—Ag1—Au1140.05 (5)C10—C9—H9118.8
S3ii—Ag1—Au1105.21 (6)C8—C9—H9118.8
S2—Ag1—Au184.43 (5)C9—C10—C11116.8 (19)
S1—Ag1—Au2i105.46 (6)C9—C10—H10121.6
S3ii—Ag1—Au2i82.46 (5)C11—C10—H10121.6
S2—Ag1—Au2i142.58 (5)C12—C11—C10119 (2)
Au1—Ag1—Au2i58.274 (14)C12—C11—C14125.9 (19)
S1—Ag1—Au281.31 (5)C10—C11—C14114.8 (17)
S3ii—Ag1—Au2140.57 (5)C11—C12—C13123 (2)
S2—Ag1—Au2107.02 (6)C11—C12—H12118.4
Au1—Ag1—Au258.907 (14)C13—C12—H12118.4
Au2i—Ag1—Au258.271 (14)C8—C13—C12117.8 (18)
S1—Ag1—Ag2100.38 (6)C8—C13—H13121.1
S3ii—Ag1—Ag2148.23 (6)C12—C13—H13121.1
S2—Ag1—Ag251.02 (6)O3—C14—O4119 (2)
Au1—Ag1—Ag255.883 (16)O3—C14—C11121 (2)
Au2i—Ag1—Ag2102.96 (2)O4—C14—C11109 (2)
Au2—Ag1—Ag256.227 (16)C16B—C15—C20B115.4 (19)
S1—Ag1—Ag3ii149.52 (6)C16A—C15—C20A122.1 (18)
S3ii—Ag1—Ag3ii50.08 (6)C16A—C15—S3116.9 (14)
S2—Ag1—Ag3ii101.90 (5)C16B—C15—S3125.0 (13)
Au1—Ag1—Ag3ii55.203 (16)C20B—C15—S3119.6 (16)
Au2i—Ag1—Ag3ii55.866 (15)C20A—C15—S3120.7 (13)
Au2—Ag1—Ag3ii102.99 (2)C15—C16A—C17A119 (2)
Ag2—Ag1—Ag3ii107.05 (2)C15—C16A—H16120.6
S1—Ag1—Ag2i50.32 (6)C17A—C16A—H16120.6
S3ii—Ag1—Ag2i100.92 (6)C18—C17A—C16A122 (3)
S2—Ag1—Ag2i148.59 (6)C18—C17A—H17118.8
Au1—Ag1—Ag2i102.58 (2)C16A—C17A—H17118.8
Au2i—Ag1—Ag2i55.174 (16)C17B—C16B—C15126 (2)
Au2—Ag1—Ag2i55.243 (16)C17B—C16B—H15A117.1
Ag2—Ag1—Ag2i107.85 (2)C15—C16B—H15A117.1
Ag3ii—Ag1—Ag2i107.22 (2)C18—C17B—C16B120 (2)
S2—Ag2—S1iv129.54 (8)C18—C17B—H16D119.9
S2—Ag2—Au187.03 (5)C16B—C17B—H16D119.9
S1iv—Ag2—Au1141.62 (6)C17B—C18—C21123.6 (18)
S2—Ag2—Au2110.89 (6)C17A—C18—C21120.7 (18)
S1iv—Ag2—Au2107.50 (6)C17B—C18—C19B120 (2)
Au1—Ag2—Au259.513 (14)C21—C18—C19B116 (2)
S2—Ag2—Au2iv146.10 (6)C17A—C18—C19A117 (2)
S1iv—Ag2—Au2iv82.58 (5)C21—C18—C19A122.1 (18)
Au1—Ag2—Au2iv59.525 (14)C20A—C19A—C18121 (3)
Au2—Ag2—Au2iv58.752 (15)C20A—C19A—H16A119.6
S2—Ag2—Ag5103.59 (6)C18—C19A—H16A119.6
S1iv—Ag2—Ag552.12 (6)C19A—C20A—C15118 (2)
Au1—Ag2—Ag5115.45 (2)C19A—C20A—H15120.9
Au2—Ag2—Ag5144.45 (3)C15—C20A—H15120.9
Au2iv—Ag2—Ag587.64 (2)C20B—C19B—C18117 (4)
S2—Ag2—Ag651.73 (6)C20B—C19B—H19A121.7
S1iv—Ag2—Ag6105.66 (6)C18—C19B—H19A121.7
Au1—Ag2—Ag687.43 (2)C15—C20B—C19B121 (3)
Au2—Ag2—Ag6145.08 (3)C15—C20B—H19B119.3
Au2iv—Ag2—Ag6116.02 (2)C19B—C20B—H19B119.3
Ag5—Ag2—Ag657.46 (3)O5A—C21—O6A123 (2)
S2—Ag2—Ag154.15 (5)O5B—C21—O6B122 (2)
S1iv—Ag2—Ag1150.39 (6)O5A—C21—C18119 (2)
Au1—Ag2—Ag156.743 (16)O5B—C21—C18118.0 (18)
Au2—Ag2—Ag156.979 (16)O6A—C21—C18114.6 (19)
Au2iv—Ag2—Ag1104.75 (2)O6B—C21—C18120.2 (19)
Ag5—Ag2—Ag1154.29 (3)C21—O6A—H6A2109.5
Ag6—Ag2—Ag196.86 (3)C21—O6B—H5B2109.5
S2—Ag2—Ag3101.41 (6)C27B—C22—C23B119 (2)
S1iv—Ag2—Ag399.28 (6)C27A—C22—C23A119.2 (19)
Au1—Ag2—Ag356.423 (16)C27A—C22—S4124.1 (13)
Au2—Ag2—Ag3104.55 (2)C27B—C22—S4120.8 (16)
Au2iv—Ag2—Ag356.987 (17)C23B—C22—S4120.1 (13)
Ag5—Ag2—Ag359.06 (2)C23A—C22—S4116.5 (14)
Ag6—Ag2—Ag359.07 (2)C24A—C23A—C22119 (3)
Ag1—Ag2—Ag3108.82 (2)C24A—C23A—H23120.5
S2—Ag2—Ag1iv149.31 (6)C22—C23A—H23120.5
S1iv—Ag2—Ag1iv51.71 (5)C23A—C24A—C25118 (3)
Au1—Ag2—Ag1iv104.28 (2)C23A—C24A—H24121.1
Au2—Ag2—Ag1iv55.822 (16)C25—C24A—H24121.1
Au2iv—Ag2—Ag1iv55.843 (16)C24B—C23B—C22119 (2)
Ag5—Ag2—Ag1iv97.15 (3)C24B—C23B—H23D120.5
Ag6—Ag2—Ag1iv154.57 (3)C22—C23B—H23D120.5
Ag1—Ag2—Ag1iv108.47 (2)C23B—C24B—C25118 (3)
Ag3—Ag2—Ag1iv108.64 (2)C23B—C24B—H24D121.2
S3—Ag3—S4130.79 (8)C25—C24B—H24D121.2
S3—Ag3—Au1iii108.06 (6)C26B—C25—C24B121 (2)
S4—Ag3—Au1iii109.93 (6)C26B—C25—C28119 (2)
S3—Ag3—Au1142.43 (6)C26A—C25—C28123.9 (18)
S4—Ag3—Au185.00 (5)C24B—C25—C28119.3 (18)
Au1iii—Ag3—Au158.894 (17)C26A—C25—C24A120 (2)
S3—Ag3—Au2iv83.88 (5)C28—C25—C24A116.3 (18)
S4—Ag3—Au2iv143.50 (6)C25—C26A—C27A122 (3)
Au1iii—Ag3—Au2iv58.269 (14)C25—C26A—H26118.9
Au1—Ag3—Au2iv58.981 (14)C27A—C26A—H26118.9
S3—Ag3—Ag552.22 (6)C22—C27A—C26A122 (2)
S4—Ag3—Ag5104.65 (6)C22—C27A—H27119.1
Au1iii—Ag3—Ag5143.82 (3)C26A—C27A—H27119.1
Au1—Ag3—Ag5115.31 (2)C25—C26B—C27B121 (3)
Au2iv—Ag3—Ag587.42 (2)C25—C26B—H26D119.4
S3—Ag3—Ag6105.57 (6)C27B—C26B—H26D119.4
S4—Ag3—Ag651.12 (6)C22—C27B—C26B121 (3)
Au1iii—Ag3—Ag6144.76 (3)C22—C27B—H27D119.3
Au1—Ag3—Ag687.75 (2)C26B—C27B—H27D119.3
Au2iv—Ag3—Ag6116.23 (2)O7B—C28—O8B125 (2)
Ag5—Ag3—Ag657.95 (3)O7A—C28—O8A124 (2)
S3—Ag3—Ag2100.26 (6)O7A—C28—C25117.9 (18)
S4—Ag3—Ag2100.28 (6)O7B—C28—C25118 (2)
Au1iii—Ag3—Ag2103.22 (2)O8B—C28—C25116.0 (19)
Au1—Ag3—Ag255.839 (16)O8A—C28—C25118.4 (18)
Au2iv—Ag3—Ag256.138 (16)C28—O8A—H7AB109.5
Ag5—Ag3—Ag259.50 (2)C28—O8B—H7BC109.5
Ag6—Ag3—Ag260.13 (2)C30A—C29—C34A120 (2)
S3—Ag3—Ag4149.73 (6)C34B—C29—C30B120 (2)
S4—Ag3—Ag453.21 (5)C34B—C29—S5118.4 (19)
Au1iii—Ag3—Ag456.773 (18)C30A—C29—S5119.6 (18)
Au1—Ag3—Ag456.768 (18)C34A—C29—S5120.2 (19)
Au2iv—Ag3—Ag4104.28 (2)C30B—C29—S5119.7 (18)
Ag5—Ag3—Ag4154.79 (3)C29—C30A—C31A121 (3)
Ag6—Ag3—Ag496.90 (3)C29—C30A—H30D119.4
Ag2—Ag3—Ag4108.52 (2)C31A—C30A—H30D119.4
S3—Ag3—Ag1iii52.64 (5)C30A—C31A—C32113 (3)
S4—Ag3—Ag1iii150.58 (6)C30A—C31A—H31123.5
Au1iii—Ag3—Ag1iii55.493 (16)C32—C31A—H31123.5
Au1—Ag3—Ag1iii103.41 (2)C31B—C30B—C29120 (3)
Au2iv—Ag3—Ag1iii55.577 (16)C31B—C30B—H30A119.9
Ag5—Ag3—Ag1iii97.15 (3)C29—C30B—H30A119.9
Ag6—Ag3—Ag1iii155.05 (3)C30B—C31B—C32117 (4)
Ag2—Ag3—Ag1iii107.79 (2)C30B—C31B—H31A121.5
Ag4—Ag3—Ag1iii107.91 (2)C32—C31B—H31A121.5
S4ii—Ag4—S4105.92 (6)C33A—C32—C35123 (3)
S4ii—Ag4—S4iii105.92 (6)C33B—C32—C35119 (2)
S4—Ag4—S4iii105.92 (6)C33A—C32—C31A124 (3)
S4ii—Ag4—Au1ii83.35 (5)C35—C32—C31A113 (2)
S4—Ag4—Au1ii141.29 (6)C33B—C32—C31B123 (3)
S4iii—Ag4—Au1ii107.34 (6)C35—C32—C31B118 (2)
S4ii—Ag4—Au1iii141.29 (6)C32—C33A—C34A121 (4)
S4—Ag4—Au1iii107.34 (6)C32—C33A—H32119.6
S4iii—Ag4—Au1iii83.35 (5)C34A—C33A—H32119.6
Au1ii—Ag4—Au1iii58.23 (2)C33A—C34A—C29121 (4)
S4ii—Ag4—Au1107.34 (6)C33A—C34A—H34119.6
S4—Ag4—Au183.35 (5)C29—C34A—H34119.6
S4iii—Ag4—Au1141.29 (6)C32—C33B—C34B117 (3)
Au1ii—Ag4—Au158.23 (2)C32—C33B—H32A121.6
Au1iii—Ag4—Au158.23 (2)C34B—C33B—H32A121.6
S4ii—Ag4—Ag3149.88 (6)C29—C34B—C33B121 (3)
S4—Ag4—Ag351.52 (6)C29—C34B—H34A119.6
S4iii—Ag4—Ag3100.24 (5)C33B—C34B—H34A119.6
Au1ii—Ag4—Ag3102.99 (3)O9B—C35—O10B125 (3)
Au1iii—Ag4—Ag355.871 (16)O9A—C35—O10A121 (3)
Au1—Ag4—Ag355.889 (16)O9B—C35—C32116 (2)
S4ii—Ag4—Ag3iii100.24 (5)O9A—C35—C32117 (3)
S4—Ag4—Ag3iii149.88 (6)O10B—C35—C32116 (2)
S4iii—Ag4—Ag3iii51.53 (6)O10A—C35—C32117 (3)
Au1ii—Ag4—Ag3iii55.866 (16)C35—O10A—H10B109.5
Au1iii—Ag4—Ag3iii55.884 (16)C35—O10B—H10C109.5
Au1—Ag4—Ag3iii102.99 (3)
Symmetry codes: (i) xy, x, z; (ii) y, xy, z; (iii) x+y, x, z; (iv) y, x+y, z.
Comparison of metal–metal bond lengths (Å) in M4Ag44(p-MBA)30, M4Au12Ag32(p-MBA)30 (PPh4)4Ag44(p-MBA)30 and (PPh4)4Au12Ag32(p-MBA)30, with standard deviations top
M4Ag44(p-MBA)30M4Au12Ag32(p-MBA)30(PPh4)4Ag44(SPhF2)30(PPh4)4Au12Ag32(SPhF2)30
12-Atom icosahedron2.825 ± 0.0122.795 ± 0.0132.831 ± 0.0192.779 ± 0.018
20-Atom dodecahedron3.175 ± 0.0403.190 ± 0.0403.167 ± 0.0883.151 ± 0.066
Icosahedron radius2.688 ± 0.0052.659 ± 0.0092.691 ± 0.0182.644 ± 0.013
Dodecahedron radius4.461 ± 0.0214.461 ± 0.0204.468 ± 0.0324.436 ± 0.029
Ag—Ag in mounts2.995 ± 0.0012.992 ± 0.0012.973 ± 0.0162.945 ± 0.014
Bader analysis results showing excess electrons, Δne, with per-atom values listed in parentheses top
Δne > 0 corresponds to excess electrons (negative charge accumulation) and Δne < 0 corresponds to electron depletion (positive charge accumulation).
M4Ag44(p-MBA)30M4Au12Ag32(p-MBA)30
Δne[icosahedron]0.010 (0.001)1.769 (0.147)
Δne[dodecahedron]-4.928 (-0.246)-6.546 (-0.327)
Δne[mounts]-4.095 (-0.341)-4.106 (-0.342)
 

Footnotes

These authors contributed equally.

Acknowledgements

X-ray analysis was carried out at the University of Toledo Instrumentation Center. We thank Dr Allen Oliver for his valuable assistance with the model refinement. Computations were carried out at the Georgia Institute of Technology Center for Computational Materials Science.

Funding information

Funding for this research was provided by: National Science Foundation, Directorate for Engineering (grant No. CBET-0955148); University of Toledo (scholarship to B. E. Conn); Air Force Office of Scientific Research (grant No. FA9550-15-1-0519 to B. Yoon, U. Landman).

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