Synthesis, crystal structure and fluorination effects in vinylidenebis(diphenylphosphine)gold(I) thiolate coordination compounds

Article abstract of DOI:10.1016/j.jfluchem.2020.109578

We report the synthesis and characterization of nine new gold(I) dinuclear compounds containing the bridging ligand vinylidenebis(diphenylphosphine) and terminal fluorophenylthiolates with the general formula [Au₂(SR)₂(μ-vdpp)] in which SR = SC₆F₅, SC₆HF₄, SC₆H₃F₂-2,4, SC₆H₃F₂-3,4, SC₆H₃F₂-3,5, SC₆H₄F-2, SC₆H₄F-3, SC₆H₄F-4 together with the non-fluorinated derivative [Au₂(SC₆H₅)₂(μ-vdpp)]. In these compounds, we analyze the long-range influence of the fluorination patterns over the electronic structure in terms of the changes in the ³¹P-NMR chemical shifts, showing the different effects depending on the relative fluorination position. Additionally, we present the crystal structure of four of the compounds, showing the presence of supported aurophilic interactions in which the Au···Au distances are modified as a consequence of the lateral interactions formed by the fluorinated phenyl rings. Overall this work gives insights in the effects of ligand fluorination in gold coordination compounds.

Full text of DOI:10.1016/j.jfluchem.2020.109578

Journal Pre-proof
Synthesis, crystal structure and fluorination effects in
vinylidenebis(diphenylphosphine)gold(I) thiolate coordination compounds
´
Guillermo Romo-Islas, Guillermo Moreno-Alcantar, Marcos
Flores-Alamo, Hugo Torrens
´
PII:
S0022-1139(20)30276-1
DOI:
https://doi.org/10.1016/j.jfluchem.2020.109578
FLUOR 109578
Reference:
To appear in:
Journal of Fluorine Chemistry
Received Date:
Revised Date:
Accepted Date:
28 April 2020
28 May 2020
28 May 2020
Please cite this article as: { doi: https://doi.org/
This is a PDF file of an article that has undergone enhancements after acceptance, such as
the addition of a cover page and metadata, and formatting for readability, but it is not yet the
definitive version of record. This version will undergo additional copyediting, typesetting and
review before it is published in its final form, but we are providing this version to give early
visibility of the article. Please note that, during the production process, errors may be
discovered which could affect the content, and all legal disclaimers that apply to the journal
pertain.
© 2020 Published by Elsevier.

Synthesis, crystal structure and fluorination effects in vinylidenebis(diphenylphosphine)gold(I)
thiolate coordination compounds.
Guillermo Romo-Islas, Guillermo Moreno-Alcántar*‡, Marcos Flores-Álamo and Hugo Torrens
Facultad de Química, Universidad Nacional Autónoma de México, Circuito Escolar, Ciudad
Universitaria, Coyoacán, 04510 Mexico City, Mexico
*Correspondence: lgma@comunidad.unam.mx Tel.: +52 55 5622 3724
Present address:
Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica, Universitat de
Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain
‡Institut de Science et d’ Ingénierie Supramoléculaires (ISIS), Université de Strasbourg. 8 alleé
Gaspard Monge, 67000, Strasbourg, France.
Graphical abstract
Highlight



fluorination exerts electronic and supramolecular modifications on gold compounds.
the trans-influence of fluoriation is studied by means of 31P-NMR.
the different effects of fluor positions can be separated from the NMR influence.
Abstract
We report the synthesis and characterization of nine new gold(I) dinuclear compounds containing
the bridging ligand vinylidenebis(diphenylphosphine) and terminal fluorophenylthiolates with
the general formula [Au2(SR)2(μ-vdpp)] in which SR = SC6F5, SC6HF4, SC6H3F2-2,4, SC6H3F2-3,4,
SC6H3F2-3,5, SC6H4F-2, SC6H4F-3, SC6H4F-4 together with the non-fluorinated derivative
[Au2(SC6H5)2(μ-vdpp)]. In these compounds, we analyze the long-range influence of the
fluorination patterns over the electronic structure in terms of the changes in the 31P-NMR

chemical shifts, showing the different effects depending on the relative fluorination position.
Additionally, we present the crystal structure of four of the compounds, showing the presence
of supported aurophilic interactions in which the Au···Au distances are modified as a
consequence of the lateral interactions formed by the fluorinated phenyl rings. Overall this work
gives insights in the effects of ligand fluorination in gold coordination compounds.
Abbreviations
vdpp, vinylidenebis(diphenylphosphine; SR, thiolate group; NMR, Nuclear Magnetic Resonance;
ppm, parts per million; DCM, dichloromethane; THT, tetrahydrothiophene; vdW, van der Waals.
Keywords
aurophilic interactions, NMR, thiolate, gold, fluorination effects
1. Introduction
Fluorination is a valuable tool for the tuning of properties of compounds. Particularly, it has
been successfully used in the design of drugs and therapeutic agents with all kind of purposes,[1–
4] but also there are examples of the use of this tool in the modulation of different properties of
organic and inorganic materials, e.g. there is a recent increase in the use of fluorination in the
design of optoelectronic materials.[5–7] While the effects of the fluorination in short ranges are
well known, their long-range influence is less studied.[8,9] Additionally to the electronic effects
that are associated with the inclusion of fluorine in the structure of compounds, the
supramolecular interaction patterns associated with fluorinated moieties are another attractive
source of modulation, in this case of the supramolecular packing and self-assembly behavior.
[6,10,11]
On the other hand, gold(I) coordination compounds have attracted attention in the last decades
due to the increasing number of interesting properties of technological relevance such as their
luminescent,[12,13] pharmacological[14] and catalytic behavior.[15] In many cases, these
interesting properties are promoted or modified by the occurrence of aurophilic (Au···Au)
interactions,[16] whose formation is driven by a balance of electronic and supramolecular
parameters.[17] The use of fluorinated and unfluorinated thiolate ligands in gold coordination
compounds has attracted attention due to their electronic and structural versatility. [18–24]
Being electronic modulation one of the pillars of the fluorine chemistry, herein we have studied
the fluorination effects over the properties of gold(I) compounds with phosphines. To this end,
we have synthesized and characterized a series of compounds based on 1,1-
bis(diphenylphosphane)ethylene (vinylidenebis(diphenylphosphine), vdpp) with the general
formula [Au2(SR)2(μ-vdpp)] in which SR = SC6F5, 1; SC6HF4, 2; SC6H3F2-2,4, 3; SC6H3F2-3,4, 4;
SC6H3F2-3,5, 5; SC6H4F-2, 6; SC6H4F-3, 7; SC6H4F-4, 8 and SC6H5, 9. Our studies show, via the
examination of the crystal structures of compounds 1, 2, 3 and 8, the important modulation

which fluorinated moieties can produce over the Au-Au interactions. Moreover, in these
compounds, the linear coordination geometry of the gold(I) centers permits the communication
31
between the P and S atoms, allowing us to observe by the shifting of the P-NMR signals the
electronic influence caused by the fluorinated groups. In fact, the 31P-NMR chemical shift
variations are sensitive enough for allowing us to differentiate the long-range effects of
fluorination in the diverse positions of the phenylthiolate. Through fitting these effects to an
additive model, we separated the contribution of fluorination in the ortho, meta and para
positions over the 31P-NMR chemical shift.
2. Results and discussion
2.1. X-ray structures
By the slow diffusion of liquid hexane into a solution of the corresponding compound in CH2Cl2,
we were able to obtain adequate samples of systems 1, 2, 3 and 8 to determine their structures
by single-crystal X-ray diffraction. All the compounds display linear coordination geometry
around gold atom. While the Au-S bond distances are practically equal in the studied systems,
the Au-P distances increase slightly by decreasing the fluorination degree of the thiolate ligand
(Table 1). This result evidences the trans-influence of the thiolate over the phosphine. Due to the
closeness of the P atoms in the structure of the ligand all these compounds show supported
Au···Au contacts. There are detectable changes in the aurophilic distances which can be explained
by the different arrangements of the thiolate fluorinate rings (Table 1). These arrangements are
further discussed for each compound. Overall, the differences are a consequence of the diverse
interactions promoted by the fluorination patterns. For instance, in compounds 1 and 2, the
existence of intramolecular π···π and π···S interactions promotes shortened Au···Au distances.
Differently, in compounds 2 and 8 the existence of hydrogen atoms in the fluorinated rings
promotes the formation of intermolecular H-bonds whose directionality causes the elongation
of the Au···Au contact. Altogether, the observed results show that the fluorination is a feasible
strategy of modulation of structural properties not only through the important electronic effects
but also by the promotion of supramolecular synthons.
Compound 1, [Au2(SC6F5)2(μ-vdpp)]. The molecular structure of compound 1 is shown in Figure
1. The studied crystal corresponds to a monoclinic P21/c system. The asymmetric unit is
constituted by only one molecule of [μ-Au2(SC6F5)2(vdpp)]. The P-Au-S angles are consistent with
the Au(I) linear geometry displaying values of 175.46(5)° and 173.14(4)°. The gold atoms present
intramolecular aurophilic interactions with Au···Au distances of 3.1857(3) Å. One of the sulfur
atoms presents an intramolecular interaction with the adjacent fluorinated phenyl group with a
distance S2-centroid of 3.574 Å. This interaction is part of the phenyl rings stacking between the
thiolate moieties, which interact with centroid to centroid distances of 4.418 Å. In this compound
the Au···Au contact and the stacking interactions act in the same direction, causing the Au···Au
distance to be the second shortest among the studied compounds. The adjacent molecules
interact forming extended polymeric π···π/π···S stacked structures that grow along the c
crystallographic axis. The intermolecular distances are 3.874 Å for the πcentroid···πcentroid and 3.753
Å for the πcentroid···S1 contact (Figure S1).

Compound 2, [Au2(SC6HF4)2(μ-vdpp)]. Figure 2 shows the crystalline structure of compound 2. It
crystallizes in a monoclinic P21/c system. In which the asymmetric unit consists of only one
molecular entity of [Au2(SC6HF4)2(μ-vdpp)]. Around the gold atoms, a linear coordination
geometry is observed whit P-Au-S angles of 174.09(7)° and 175.81(7)°. The supported aurophilic
contact displays the shortest distance of the arrangements shown herein, 3.1411(4) Å. Similarly,
to compound 1, the shortening of the Au···Au distance is caused by the existence of
intramolecular π-stacking and S···π interactions (dcentroids = 3.707 Å and dS···π = 3.893 Å) between
the thiolate fragments that act in the same direction of Au···Au contacts. While the molecular
conformation of compound 2 resembles the observed in compound 1, the supramolecular
crystalline arrangements of both compounds differ importantly. Compound 2 does not show the
extended π-stacking network on the crystal. Instead, the molecular units hold together by several
H-bonding interactions, promoted by the existence of hydrogen atoms in the fluorinated rings.
The most important contacts observed are those of: i) H4···S2, (dH···S = 2.811 Å), ii) the double
H10···F6 interaction (dH···F = 2.466 Å) and iii) the H22···F5 contact which is also reciprocal (dH···F
=
2.444 Å, Figure 2).
Compound 3, [Au2(SC6H3F2-2,4)2(μ-vdpp)]. The crystalline structure of compound 3 corresponds
to the orthorhombic space group Pbcn. The analysis of the asymmetric unit shows that it is formed
by half a molecule of [Au2(SC6H3F2-2,4)2(μ-vdpp)]. The highly symmetric arrangement of
compound 3 presents P-Au-S angles of 176.44(11)° and Au-P and Au-S bond distances of 2.264(3)
Å and 2.300(3) respectively. The Au···Au contact in this system is larger than in 1 and 2 (3.2427(8)
Å). Once again, the enlargement of this distance seems to be affected by the disposition of the
thiolate groups. Differently from 1 and 2, in compound 3 the fluorinated moieties do not
participate into intermolecular stacking interactions, instead, hydrogen bonds, between the
fluorine in position 4 of the thiolate and a phosphine hydrogen of the neighboring molecule (dH···F
= 2.639 Å), direct the fluorinated rings in opposite directions pulling apart the gold atoms (Figure
3). This conformation is favored also by the formation of intramolecular F···H contacts (dH···F
=
2.635 Å) and the existence of an intramolecular π-stacking between the fluorinated ring and a
phenyl group on the phosphine (dcentroids = 3.947 Å).
Compound 8, [Au2(SC6H4F-4)2(μ-vdpp)]. The structure obtained for the crystalline form of 8
(Figure 4) corresponds to a 1:1 solvate of the compound with CH2Cl2 which structure belongs to
the monoclinic P21/c space group. The asymmetric unit corresponds to the [Au2(SC6H4F-4)2(μ-
vdpp)]·CH2Cl2 fragment. While the P2-Au2-S2 angle is in agreement with the expected linearity
(176.23(8)°) the P1-Au1-S1 moiety is considerably distorted with an angle of 169.53(8)° this
deformation evidences the hindrance between the aurophilic interaction and the packing of the
thiolate fragment as they act in different directions. Because of this, the Au···Au distance in 8

results to be the largest observed within the structures addressed herein (3.2597(5) Å). The
inclusion of the solvent molecule in the crystalline network seems to play a crucial role in the
packing. For instance, HDCM···S and HDCM···F contacts are observed between the compound
molecule and the solvent unites. Moreover, several CH···ClDCM interactions are observed involving
both thiolate and phosphine phenyl hydrogens. Thus, the disposition of the thiolate groups in the
crystal is determined by these contacts, which preclude an efficient Au···Au interaction.
2.2. Fluorination NMR effects
The fluorination patterns of the thiolate ligands attached to the gold centers modify the electron
distribution within the molecule. This modification is communicated to the phosphine ligand
through the Au atom and is evidenced by the changes in the 31P-NMR chemical shifts. Such effect,
which is related to the trans-influence of the thiolate over the phosphine ligand bonded to the
31
gold, has been reported by us with similar trends in related systems.[25,26] The measured P
chemical shift for the studied compounds are presented in Table 2, a trend related to the
fluorination influence is not evidently observed as the chemical shift is not only dependent on
the number of fluorine atoms in the phenyl ring but is an outcome of the combined inductive and
resonant electronic effects originated by the number and positions of fluorine atoms in the
structure. To simplify those two effects the Mulliken electronic population was calculated using
as model the isolated gold thiolate moieties.[27] The influence of the fluorination is clearly
reflected in the resulting charges. Of particular interest are the charges observed in the carbon
bonded to sulfur, sulfur and, gold atoms (Figure 5). The charge variations are pronounced in the
carbon, spanning 0.5 a.u., due to the spatial proximity and efficient communication provided by
the delocalized π system that exists between this and the fluorine atoms. For the more distant S
and Au atoms, the variations occur in a more subtle range (0.1 a.u.). Surprisingly, the plot of the
experimental 31P-NMR values and the calculated charge on the carbon atoms (Figure 5) reveals
an interesting correlation. This relation probes the almost undisturbed communication between
the fluorinated ring and the phosphorus atom. Furthermore, it shows that the effects of
fluorination can be sensed and reported by the 31P-NMR chemical shifts in an unexpected
importantly long range.
Additionally, the contribution of the different fluorine atoms attached to the structure can be
separated by fitting the observed 31P-NMR chemical shift to a Shoolery-type additive model,[28]
the fitting has been done by adjusting the experimental data by minimum square numerical
approximation to an additive equation. The obtained model (Equation 1) gives values of
calculated 31P-NMR shifts that match the experimental values (Figure 6) with Pearson’s R2 for the
prediction of 0.98.
훿31푃 = 38.08 − 0.44543 표 + 0.09819 푚 − 0.14707 푝
Equation 1
31
In equation 1, 38.08 is the P-NMR chemical shift of the parent unflorinated thiobenzene
derivative 9 and o, m and p are the entire numbers of fluorine atoms in the ortho, meta and para
positions respectively. It can be observed that, congruently with their similar hyperconjugation

31
effects, ortho and para fluorination exert an upfield shift of the P resonance while the mostly
inductive effect of the fluorination in meta acts in the opposite direction with a considerably
smaller contribution.
Conclusions
By the analysis of this family of compounds we have shown the relevance of fluorination to
modulate the electronic properties of compounds, in particular, we pointed out the surprisingly
long-range influence that fluorine has over distant atoms which are big enough to be followed
and analyzed in terms of NMR. Additionally, we show the potential of fluorination as a useful tool
to exert supramolecular modulation by promoting the rise of different interaction synthons that
can act concomitantly or against other interactions, as shown in this case with aurophilic
contacts.
Experimental
Reagents. tetrahydrothiophene (THT), H[AuCl4], vdpp and all the thiols were purchased from
Sigma-Aldrich and used as received. [AuCl(THT)],[29] and lead thiolates[11] were prepared
according to reported procedures. [Au2Cl2(µ-vdpp)][30] was prepared by a modification of the
reported method detailed in the SI.[31]
General method for the preparation of [Au2(SR)2(μ-vdpp)]. In a round bottom flask, a solution of
the precursor [Au2Cl2(μ-vdpp)] 100.0 mg (0.116 mmol) in 10 mL of CH2Cl2 was mixed under stirring
at room temperature with a solution (or suspension for most of the less fluorinated and less soluble
lead thiolates) of 0. 0.116 mmol of Pb(SRF)2 in 10 mL of acetone. After three hours of stirring the
mixture was filtrated to eliminate the formed PbCl2 and a clear solution was obtained. The solvent
was later evaporated until a volume of about 3 mL and then 20 mL of hexane were added to
promote the precipitation of the product in the pure product. The obtained powder was filtrated
and washed with hexane (3x 15 mL).
Compound 1, [Au2(SC6F5)2(μ-vdpp)]: White powder, 92 % yield, mp 227-230°C, IR; v 3054 (=CH2),
1478 (CH2), 1080 (C-F). 1H NMR (600.17 MHz, CDCl3): δ 6.28 (m, 2 H), 7.47 (m, 8 H) 7.56 (m, 12 H).
19F NMR (564.73 MHz, CDCl3): δ -132.21 (d, J=26.76 Hz, 4 F), -163.13 (t, J=20.09 Hz, 2 F), -164.45 (t,
J=23.63 Hz, 4 F). 31P NMR (242.95 MHz, CDCl3): δ 37.24 ppm. APCI (GC-MS) m/z : 989 [M-SRF], 1524
[M+AuSRF], 2121 [2M-Au], 2316 [2M] Analysis Calculated to C38H22Au2F10P2S2 C, 38.40; H, 1.87; S,
5.39 Found C, 38.45; H, 1.85; S, 5.24.
Compound 2, [Au2(SC6HF4)2(μ-vdpp)]: White powder, 91 % yield, mp 190-192°C, IR; v 3055 (=CH2),
2899 (ar), 1475 (CH2), 1100 (C-F). 1H NMR (600.17 MHz, CDCl3): δ 6.28 (m, 2 H), 6.63 (tt, J= 9.71,
7.17 Hz, 2 H), 7.45 (m, 8 H), 7.52 (t, J=7.11 Hz, 4H), 7.60 (q, J= 7.03, 6.93 Hz, 8 H). 19F NMR (564.73
MHz, CDCl3): δ -132.54 (m, 4 F), -141.4 (m, 4F). 31P NMR (242.95 MHz, CDCl3): δ 37.32 ppm. APCI
(GC-MS) m/z : 986 [M-SRF], 1337 [M+Au], 1714 [M+Au+ AuSRF]. Analysis Calculated to
C38H24Au2F8P2S2 C, 39.60; H, 2.10; S, 5.56 Found C, 39.52; H, 2.02; S, 5.56.
Compound 3, [Au2(SC6H3F2-2,4)2(μ-vdpp)]: White powder, 89 % yield, mp 204-206°C, IR; v 3051
(=CH2), 2953 (ar), 1477 (CH2), 1081 (C-F). 1H NMR (600.17 MHz, CDCl3): δ 6.24 (m, 2 H), 6.60 (dt,

J=9.77, 4.69 Hz, 2 H), 6.67 (td, J= 9.02, 8.99, 2.82 Hz,2 H), 7.43 (t, J=7.54 Hz, 8 H), 7.51 (dt, J= 14.4,
7.57 Hz, 6 H), 7.57 (q, J= 6.97, 6.90 Hz, 8 H). 19F NMR (564.73 MHz, CDCl3): δ -100.71 (s (br), 2 F), -
117.20 (s (br), 2 F). 31P NMR (242.95 MHz, CDCl3): δ 37.56 ppm. APCI (GC-MS) m/z : 933 [M-SRF],
1082 [M], 1277 [M+Au], 1422 [M+AuSRF]. Analysis Calculated to C38H28Au2F4P2S2 C, 42.24; H, 2.61;
S, 5.93 Found C, 42.14; H, 2.58; S, 5.88.
Compound 4, [Au2(SC6H3F2-3,4)2(μ-vdpp)]: White powder, 87 % yield, mp 187-189°C, IR; v 3057
(=CH2), 2990 (ar), 1480 (CH2), 1102 (C-F). 1H NMR (600.17 MHz, CDCl3): δ 6.28 (m, 2 H), 6.78 (dt,
J=10.56, 8.56 Hz, 2 H), 7.11 (m, 4 H), 7.45 (m, 8 H), 7.56 (m, 12 H). 19F NMR (564.73 MHz, CDCl3): δ
-139.03 (m, 2 F), -145.85 (s (br), 2 F). 31P NMR (242.95 MHz, CDCl3): δ 38.05 ppm. APCI (GC-MS) m/z
: 932 [M-SRF], 1082 [M], 1422 [M+AuSRF]. Analysis Calculated to C38H28Au2F4P2S2 C, 42.24; H, 2.61;
S, 5.93 Found C, 42.14; H, 2.58; S, 5.88.
Compound 5, [Au2(SC6H3F2-3,5)2(μ-vdpp)]: White powder, 92 % yield, mp 152-154°C, IR; v 3054
(=CH2), 1435 (CH2), 1084 (C-F). 1H NMR (600.17 MHz, CDCl3): δ 6.30 (m, 2 H), 6.38 (tt, J=9.12, 2.29
Hz, 2 H), 6.89 (m, 4 H), 7.46 (m, 8 H), 7.54 (t, J= 7.47 Hz, 4 H), 7.59 (m, 8 H). 19F NMR (564.73 MHz,
CDCl3): δ -112.35 (s (br), 2 F). 31P NMR (242.95 MHz, CDCl3): δ 38.30 ppm. APCI (GC-MS) m/z : 930
[M-SRF], 1082 [M], 1277 [M+Au], 1422 [M+AuSRF]. Analysis Calculated to C38H28Au2F4P2S2 C, 42.24;
H, 2.61; S, 5.93 Found C, 42.14; H, 2.58; S, 5.88.
Compound 6, [Au2(SC6H4F-2)2(μ-vdpp)]: White powder, 86 % yield, mp 85-87°C, IR; v 3052 (=CH2),
2866 (ar), 1435 (CH2), 1099 (C-F). 1H NMR (600.17 MHz, CDCl3): δ 6.25 (m, 2 H), 6.86 (m, 2 H), 6.91
19
(m, 6 H), 7.43 (t, J=7.57 Hz, 8 H), 7.53 (t, J=7.42 Hz, 4 H), 7.60 (dt, J=7.84, 4.64 Hz, 8 H). F NMR
(564.73 MHz, CDCl3): δ -105.51 (s (br), 2 F). 31P NMR (242.95 MHz, CDCl3): δ 37.69 ppm. APCI (GC-
MS) m/z : 917 [M-SRF], 1044 [M], 1241 [M+Au]. Analysis Calculated to C38H22Au2F10P2S2 C, 43.69;
H, 2.89; S, 6.14 Found C, 43.55; H, 2.80; S, 5.89.
Compound 7, [Au2(SC6H4F-3)2(μ-vdpp)]: White powder, 88 % yield, mp 120-122°C, IR; v 3056
(=CH2), 2870 (ar), 1463 (CH2), 1099 (C-F). 1H NMR (600.17 MHz, CDCl3): δ 6.27 (m, 2 H), 6.63 (td,
J= 8.38, 8.37, 2.51 Hz, 2 H), 6.95 (td, J= 7.97, 7.84, 6.29 Hz, 2 H), 7.08 (d, J=10.15 Hz, 2 H), 7.22 (d,
J=7.92 Hz, 2 H), 7.43 (tt, J=7.34, 1.54 Hz, 8 H), 7.52 (m, 4 H), 7.60 (m, 8H). 19F NMR (564.73 MHz,
CDCl3): δ -114.73 (s (br), 2 F). 31P NMR (242.95 MHz, CDCl3): δ 38.20 ppm. APCI (GC-MS) m/z : 918
[M-SRF], 1044 [M], 1241 [M+Au], 1583 [M+Au+Au SRF]. Analysis Calculated to C38H22Au2F10P2S2 C,
43.69; H, 2.89; S, 6.14 Found C, 43.55; H, 2.80; S, 5.89.
Compound 8, [Au2(SC6H4F-4)2(μ-vdpp)]: White powder, 86 % yield, mp 138-140°C, IR; v 3053
(=CH2), 2870 (ar), 1463 (CH2), 1099 (C-F). 1H NMR (600.17 MHz, CDCl3): δ 6.26 (m, 2 H), 6.71 (tt,
J= 8.38, 9.54, 2.12 Hz, 4 H), 7.35 (m, 4 H), 7.43 (t, J=7.52 Hz, 8 H), 7.53 (d, J=7.22 Hz, 4 H), 7.57 (m,
8 H). 19F NMR (564.73 MHz, CDCl3): δ -121.17 (s (br), 2 F). 31P NMR (242.95 MHz, CDCl3): δ 37.84
ppm. APCI (GC-MS) m/z : 918 [M-SRF], 1044 [M], 1241 [M+Au], 1583 [M+Au+Au SRF]. Analysis
Calculated to C38H22Au2F10P2S2 C, 43.69; H, 2.89; S, 6.14 Found C, 43.55; H, 2.80; S, 5.89.
Compound 9, [Au2(SC6H5)2(μ-vdpp)]: White powder, 85 % yield, mp 78-80°C, IR; v 305 (=CH2), 2868
(ar), 1434 (CH2), 1098 (C-F). 1H NMR (600.17 MHz, CDCl3): δ 6.26 (m, 2 H), 6.94 (t, J= 7.30 Hz, 2 H)

7.02 (t, J= 7.51 Hz, 4 H), 7.41 (t, J= 7.52 Hz, 8 H), 7.45 (d, J= 7.64 Hz, 4 H), 7.51 (t, J= 7.47 Hz, 4 H),
7.60 (q, J= 6.92, 6.72 Hz, 8 H). 31P NMR (242.95 MHz, CDCl3): δ 38.08 ppm. APCI (GC-MS) m/z : 899
[M-SRF], 1008 [M], 1312 [M+AuSRF], 1511 [M+Au+Au SRF]. Analysis Calculated to C38H32Au2F10P2S2
C, 45.25; H, 3.20; S, 6.36 Found C, 45.20; H, 3.13; S, 6.31.
Crystal Structure Determination
Suitable single crystals of compounds 1, 2, 3 and 8 were mounted on glass fibers and
crystallographic data were collected with an Oxford Diffraction Gemini "A" diffractometer with a
CCD area detector with monochromator of graphite for λMoKα = 0.71073 Å. CrysAlisPro and CrysAlis
RED software packages were used for data collection and integration.[32] The double-pass method
of scanning was used to exclude any noise. The collected frames were integrated by using an
orientation matrix determined from the narrow frame scans. Final cell constants were determined
by a global refinement; collected data were corrected for absorbance by using analytical numeric
absorption correction using a multifaceted crystal model based on expressions upon the Laue
symmetry with equivalent reflections.[33] Structures solutions and refinement were carried out
with the SHELXS-2014 [34] and SHELXL-2014[35] packages. WinGX v2018.3[36] software was used
to prepare material for publication. Full-matrix least-squares refinement was carried out by
minimizing (Fo2 – Fc2)2. All non-hydrogen atoms were refined anisotropically. H atoms attached to
C atoms were placed in geometrically idealized positions and refined as riding on their parent
atoms, with C–H = 0.95–0.97 Å and with Uiso(H) = 1.2Ueq(C) for aromatic and methylene groups. On
the other hand, for compound 2, the solvent molecules were significantly disordered and could not
be modeled properly, thus SQUEEZE, a part of the PLATON[37] package of crystallographic
software, was used to calculate the solvents disorder areas and remove their contributions to the
overall intensity data, The disordered solvents area is centered around the 0.00 0.50 1.00 position
and showing an estimated total of 76 electrons and a void volume of 222 Å3. C1, C2, C3, C4 ,C5, C6,
F1 ,F2 and C1P, C2P, C3P ,C4P ,C5P, C6P, F1P ,F2P are disordered over two sites with occupancies
0.47:0.53 in 3. Crystallographic data for all complexes is presented in Table 2. The crystallographic
data for the structures reported in this paper have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication no. CCDC 1999611-1999614. Copies of
the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge, CB2
1EZ, UK (fax: (+44) 1223-336-033, e-mail: deposit@ccdc.cam.ac.uk).
Declaration of interests
The authors declare that they have no known competing financial interests or personal relationships that
could have appeared to influence the work reported in this paper.
Acknowledgments
We acknowledge the financial support from DGAPA-UNAM project IN210818 and CONACYT-
Mexico CB-2012/177498 along with the postdoctoral grant 740732 for G.M.A., G.R.I.

acknowledges the scholarship from Fundación Carolina-SRE and the support of Prof. Laura
Rodríguez. We also thank Unit for Support to Research and Industry (USAII) of the Faculty of
Chemistry – UNAM for the instrumental Support.
References
[1]
H. Mei, J. Han, S. Fustero, M. Medio-Simon, D.M. Sedgwick, C. Santi, R. Ruzziconi, V.A.
Soloshonok, Fluorine-Containing Drugs Approved by the FDA in 2018, Chem. - A Eur. J.
(2019). https://doi.org/10.1002/chem.201901840.
[2]
C. Au, C. Gonzalez, Y.C. Leung, F. Mansour, J. Trinh, Z. Wang, X.G. Hu, R. Griffith, E.
Pasquier, L. Hunter, Tuning the properties of a cyclic RGD-containing tetrapeptide through
backbone
fluorination,
Org.
Biomol.
Chem.
17
(2019)
664–674.
https://doi.org/10.1039/c8ob02679c.
[3]
[4]
[5]
N.A. Meanwell, Fluorine and Fluorinated Motifs in the Design and Application of
Bioisosteres for Drug Design, J. Med. Chem. 61 (2018) 5822–5880.
https://doi.org/10.1021/acs.jmedchem.7b01788.
Z. Zhang, W. Shen, J. Ling, Y. Yan, J. Hu, Y. Cheng, The fluorination effect of
fluoroamphiphiles in cytosolic protein delivery, Nat. Commun.
https://doi.org/10.1038/s41467-018-03779-8.
9
(2018).
K. Weng, X. Xue, F. Qi, Y. Zhang, L. Huo, J. Zhang, D. Wei, M. Wan, Y. Sun, Synergistic Effects
of Fluorination and Alkylthiolation on the Photovoltaic Performance of the
Poly(benzodithiophene-benzothiadiazole) Copolymers, ACS Appl. Energy Mater. 1 (2018)
4686–4694. https://doi.org/10.1021/acsaem.8b00819.
[6]
[7]
[8]
M. Spengler, R.Y. Dong, C.A. Michal, M. Pfletscher, M. Giese, Fluorination of
supramolecular liquid crystals-tuning tool and analytical probe, J. Mater. Chem. C. 5 (2017)
2235–2239. https://doi.org/10.1039/c6tc05472b.
N.V.S.D.K. Bhupathiraju, W. Rizvi, J.D. Batteas, C.M. Drain, Fluorinated porphyrinoids as
efficient platforms for new photonic materials, sensors, and therapeutics, Org. Biomol.
Chem. 14 (2016) 389–408. https://doi.org/10.1039/c5ob01839k.
E. Silva-Nigenda, A. Martínez-Gómez, J. Cruz-de la Cruz, J. Barroso-Flores, C. González-
Romero, A. Fuentes-Benites, C.K. Jankowski, E. Cuevas-Yáñez, E. Díaz-Torres, D. Corona-
1
Becerril, Long range H–19F coupling through multiple bond in thienopyridines,
isoquinolines and 2-aza-carbazoles derivatives, J. Mol. Struct. 1176 (2019) 562–566.
https://doi.org/10.1016/j.molstruc.2018.08.084.
[9]
J. Gräfenstein, D. Cremer, Unusual long-range spin-spin coupling in fluorinated polyenes:
A mechanistic analysis, J. Chem. Phys. 127 (2007). https://doi.org/10.1063/1.2787001.
[10] V.R. Thalladi, H.-C. Weiss, D. Bläser, R. Boese, A. Nangia, G.R. Desiraju, C−H···F Interactions
in the Crystal Structures of Some Fluorobenzenes, J. Am. Chem. Soc. 120 (1998) 8702–

8710. https://doi.org/10.1021/ja981198e.
[11] G. Moreno-Alcántar, L. Salazar, G. Romo-Islas, M. Flores-Álamo, H. Torrens, Exploring the
Self-Assembled Tacticity in Aurophilic Polymeric Arrangements of Diphosphanegold(I)
Fluorothiolates, Molecules. 24 (2019) 4422. https://doi.org/10.3390/molecules24234422.
[12] X. He, V.W.-W. Yam, Luminescent gold(I) complexes for chemosensing, Coord. Chem. Rev.
255 (2011) 2111–2123. https://doi.org/10.1016/j.ccr.2011.02.003.
[13] E.E. Langdon-Jones, S.J.A. Pope, Recent developments in gold( <scp>i</scp> ) coordination
chemistry: luminescence properties and bioimaging opportunities, Chem. Commun. 50
(2014) 10343. https://doi.org/10.1039/C4CC03259D.
[14] T. Zou, C.T. Lum, C.-N. Lok, J.-J. Zhang, C.-M. Che, Chemical biology of anticancer gold(III)
and
gold(I)
complexes,
Chem.
Soc.
Rev.
44
(2015)
8786–8801.
https://doi.org/10.1039/C5CS00132C.
[15] A.M. Echavarren, A.S.K. Hashmi, F.D. Toste, Gold Catalysis - Steadily Increasing in
Importance, Adv. Synth. Catal. 358 (2016) 1347–1347.
https://doi.org/10.1002/adsc.201600381.
[16] H. Schmidbaur, A. Schier, A briefing on aurophilicity, Chem. Soc. Rev. 37 (2008) 1931.
https://doi.org/10.1039/b708845k.
[17] G. Moreno-Alcántar, G. Romo-Islas, M. Flores-Álamo, H. Torrens, Aurophilicity vs.
thiophilicity: directing the crystalline supramolecular arrangement in luminescent gold
compounds, New J. Chem. 42 (2018) 7845–7852. https://doi.org/10.1039/C7NJ04354F.
[18] B.-C. Tzeng, A. Schier, H. Schmidbaur, Crystal Engineering of Gold(I) Thiolate Based
Compounds via Cooperative Aurophilic and Hydrogen-Bonding Interactions, Inorg. Chem.
38 (1999) 3978–3984. https://doi.org/10.1021/ic990308v.
[19] E.R.T. Tiekink, J.-G. Kang, Luminescence properties of phosphinegold(I) halides and
thiolates,
Coord.
Chem.
Rev.
253
(2009)
1627–1648.
https://doi.org/10.1016/j.ccr.2009.01.017.
[20] M. Bardají, M.J. Calhorda, P.J. Costa, P.G. Jones, A. Laguna, M. Reyes Pérez, M.D.
Villacampa, Synthesis, Structural Characterization, and Theoretical Studies of Gold(I) and
Gold(I)−Gold(III) Thiolate Complexes: Quenching of Gold(I) Thiolate Luminescence, Inorg.
Chem. 45 (2006) 1059–1068. https://doi.org/10.1021/ic051168u.
[21] S. Montanel-Pérez, A. Izaga, A. Laguna, M.D. Villacampa, M.C. Gimeno, Synthesis of
Gold(III) Complexes with Bidentate Amino-Thiolate Ligands as Precursors of Novel
Bifunctional Acyclic Diaminocarbenes, ACS Omega. 3 (2018) 13097–13103.
https://doi.org/10.1021/acsomega.8b01547.
[22] R. Visbal, R.P. Herrera, M.C. Gimeno, Thiolate Bridged Gold(I)–NHC Catalysts: New
Approach for Catalyst Design and its Application to Trapping Catalytic Intermediates,
Chem. – A Eur. J. 25 (2019) 15837–15845. https://doi.org/10.1002/chem.201903494.

[23] V.W.W. Yam, C.-L.L. Chan, C.-K.K. Li, K.M.C. Wong, V. Wing-Wah Yam, C.-L.L. Chan, C.-K.K.
Li, K. Man-Chung Wong, Molecular design of luminescent dinuclear gold(I) thiolate
complexes: from fundamentals to chemosensing, Coord. Chem. Rev. 216217 (2001) 173–
194. https://doi.org/10.1016/S0010-8545(01)00310-1.
[24] S.Y. Ho, E.C.-C. Cheng, E.R.T. Tiekink, V.W.-W. Yam, Luminescent Phosphine Gold(I)
Thiolates: Correlation between Crystal Structure and Photoluminescent Properties in
[R3PAu{SC(OMe)NC6H4NO2-4}] (R = Et, Cy, Ph) and [(Ph2P-R-PPh2){AuSC(OMe)NC6H4NO2-
4}2] (R = CH2, (CH2)2, (CH2)3 , (CH2)4, Fc), Inorg. Chem. 45 (2006) 8165–8174.
https://doi.org/10.1021/ic0608243.
[25] G. Moreno-Alcántar, H. Hernández-Toledo, J.M. Guevara-Vela, T. Rocha-Rinza, Á. Martín
Pendás, M. Flores-Álamo, H. Torrens, Stability and trans Influence in Fluorinated Gold(I)
Coordination Compounds, Eur. J. Inorg. Chem. 2018 (2018) 4413–4420.
https://doi.org/10.1002/ejic.201800567.
[26] G. Moreno-Alcántar, K. Hess, J.M. Guevara-Vela, T. Rocha-Rinza, Á. Martín Pendás, M.
Flores-Álamo, H. Torrens, π-Backbonding and non-covalent interactions in the JohnPhos
and polyfluorothiolate complexes of gold(I), Dalton Trans. 46 (2017) 12456–12465.
https://doi.org/10.1039/C7DT00961E.
[27] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G.
Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.P.
Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K.
Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T.
Vreven, J.A. Montgomery Jr., J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers,
K.N. Kudin, V.N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C.
Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B.
Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J.
Austin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski,
G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, Ö. Farkas, J.B. Foresman,
J. V Ortiz, J. Cioslowski, D.J. Fox, Gaussian 09, Revision D.01, Gaussian Inc. (2009).
https://doi.org/10.1159/000348293.
[28] J.N. Shoolery, Technical Information Bulletin, Varian Associates, Palo Alto, USA, 1959.
[29] E.A. Allen, W. Wilkinson, The vibrational spectra of some dialkyl sulphide complexes of
gold(III) and gold(I) halides, Spectrochim. Acta Part A Mol. Spectrosc. 28 (1972) 2257–
2262. https://doi.org/10.1016/0584-8539(72)80200-9.
[30] H.
Schmidbaur,
R.
Herr,
G.
Mueller,
J.
Riede,
Activation
of
vinylidenebis(diphenylphosphine) through metal complexation, Organometallics. 4 (1985)
1208–1213. https://doi.org/10.1021/om00126a013.
[31] P. Braunstein, T.M.G. Carneiro, D. Matt, F. Balegroune, D. Grandjean, β-Keto phosphines
derived from ferrocene. Syntheses and structures of [Ph2PCH2C(O)(η5-C5H4)Fe(η5-C5H5)]
(L1) and trans-[PdCl2L12], J. Organomet. Chem. 367 (1989) 117–132.

https://doi.org/10.1016/0022-328X(89)87213-4.
[32] Agilent, CrysAlis PRO, (2014).
[33] R.C. Clark, J.S. Reid, The analytical calculation of absorption in multifaceted crystals, Acta
Crystallogr.
Sect.
A
Found.
Crystallogr.
51
(1995)
887–897.
https://doi.org/10.1107/S0108767395007367.
[34] G.M. Sheldrick, SHELXT – Integrated space-group and crystal-structure determination,
Acta Crystallogr. Sect. Found. Adv. 71 (2015) 3–8.
https://doi.org/10.1107/S2053273314026370.
A
[35] G.M. Sheldrick, Crystal structure refinement with SHELXL, Acta Crystallogr. Sect. C Struct.
Chem. 71 (2015) 3–8. https://doi.org/10.1107/S2053229614024218.
[36] L.J. Farrugia, WinGX and ORTEP for Windows: An update, J. Appl. Crystallogr. 45 (2012)
849–854. https://doi.org/10.1107/S0021889812029111.
[37] A.L. Spek, PLATON SQUEEZE: A tool for the calculation of the disordered solvent
contribution to the calculated structure factors, Acta Crystallogr. Sect. C Struct. Chem. 71
(2015) 9–18. https://doi.org/10.1107/S2053229614024929.

Figure 1. Left: Molecular structure of compound 1 with displacement ellipsoids at 50% probability level for non-H
atoms. Right: Extended π-stacked/S···π structures formed in the crystalline packing of 1, the spheres radii equals the
van der Waals radii of the elements and the ellipsoids are shown at 50% probability level, H atoms were omitted for
clarity. Selected distances (Å): Au1-Au2, 3.1857(3); P2-Au2, 2.2574(13); P1-Au1, 2.2539(12); Au2-S2, 2.3061(13); Au1-
S1, 2.2970(13). Selected angles (°) P1-C25-P2,112.6(2); P1-Au1-S1, 175.46(5); P2-Au2-S2, 173.14(4); Au1-S1-C1,
103.09(15); Au2-S2-C7, 109.80(16).
Figure 2. Left: Crystal structure of compound 2, the displacement ellipsoids are presented at 50% probability level for
non-H atoms. Right: Short intermolecular H-bond interactions (dH-A  sum of vdW radii - 0.1) around a molecule in
the packing of compound 2. Selected distances (Å): Au1-Au2, 3.1411(4); P2-Au2, 2.2551(19); P1-Au1, 2.2568(19);
Au2-S2, 2.296(2); Au1-S1, 2.2974(19). Selected angles (°) P1-C25-P2,112.4(4); P1-Au1-S1, 174.09(7); P2-Au2-S2,
175.81(7); Au1-S1-C1, 110.6(3); Au2-S2-C7, 108.4(3).

Figure 3. Top left: View in perspective of the structure of compound 3 with displacement ellipsoids at 50% probability
level for non-H atoms. Top right: view of the molecule along the Au···Au contact showing the symmetric disposition
of the thiolate groups. Bottom: non-covalent interactions between neighboring molecules of 3. Selected distances
(Å): Au1-Au1, 3.2427(8); P1-Au1, 2.264(3); Au1-S1, 2.300(3). Selected angles (°) P1-C25-P1,113.5(9); P1-Au1-S1,
176.44(11); Au1-S1-C1, 105.5(9).

Figure 4. Top: Molecular structure of compound 8·CH2Cl2 with displacement ellipsoids at 50% probability level for
non-H atoms. Bottom: Solid-state packing of 8·CH2Cl2 highlighting the position of the solvent molecules, the spheres
radii equals the van der Waals radii of the elements and the ellipsoids are shown at 50% probability level, H atoms
were omitted for clarity. Selected distances (Å): Au1-Au2, 3.2597(5); P2-Au2, 2.263(2); P1-Au1, 2.268(2); Au2-S2,
2.300(2); Au1-S1, 2.297(3). Selected angles (°) P1-C25-P2,111.9(5); P1-Au1-S1, 169.53(8); P2-Au2-S2, 176.23(8); Au1-
S1-C1, 107.0(3); Au2-S2-C7, 108.6(3).

Figure 5 Left: Calculated Mulliken charge distribution in the model system AuSC6F5 as reported in Table 1, each atom’s
color indicates the value of its charge in a.u. according to the scale shown below. Right: Plot showing the correlation
between the calculated Mulliken charge of the sulfur’s base carbon atom for model systems 1-9.
Figure 6 Goodness of the estimation of the 31P NMR chemical shift values by Equation 1.

Table 1. Selected intramolecular distances in the structures determined by X-ray of compounds 1, 2, 3 and 8.
Compound
dAu-Au (Å)
3.1857(3)
3.1411(4)
3.2427(8)
3.2597(5)
dAu-P (Å)
2.254(1)
dAu-S (Å)
2.297(1)
dπ-π (Å)
3.874
3.707
3.947
-
dπ-S (Å)
3.753
3.893
-
-
1
2
3
8
2.257(1)
2.256(2)
-
2.306(1)
2.297(2)
-
2.255(2)
2.264(3)
2.268(2)
2.296(2)
2.300(3)
2.297(3)
2.263(2)
2.300(2)

Table 2. 31P Chemical shifts and calculated Mulliken population of the atoms of Au, S and CS in the free gold thiolate.
Compound
δ 31P (ppm)
qAu (a.u.)
0.048
qS (a.u.)
0.197
0.170
0.136
0.123
0.120
0.098
0.085
0.089
0.078
qC* (a.u.)
-0.647
-0.536
-0.436
-0.209
-0.121
-0.345
-0.136
-0.220
-0.179
1
2
3
4
5
6
7
8
9
37.24
37.32
0.043
37.56
0.019
38.05
0.006
38.32
0.017
37.69
-0.009
-0.021
-0.033
-0.044
38.20
37.84
38.08
*Carbon atom directly bonded to sulfur
.

Table 2. Crystal data and structure refinement for 1, 2, 3 and 8.
Compound (Identification code)
1 (VdppAuF5-720)
2 (vdpauf4h-613_sq)
3 (vauf224-117)
8 (vdppauf4-001)
Empirical formula
Formula weight
Temperature
C38 H22 Au2 F10 P2 S2
1188.55
130(2) K
C38 H24 Au2 F8 P2 S2
1152.56
130(2) K
C38 H28 Au2 F4 P2 S2
1080.60
130(2) K
C39 H30 Au2 Cl2 F2 P2 S2
1127.52
130(2) K
Wavelength
0.71073 Å
0.71073 Å
0.71073 Å
0.71073 Å
Crystal system
Space group
Monoclinic
P 21/c
Monoclinic
P 21/c
Orthorhombic
P b c n
Monoclinic
P 21/n
Unit cell dimensions
a = 13.271(3) Å
b = 21.9104(17) Å
c = 14.057(2) Å
= 115.81(2)°.
a = 12.4959(7) Å
b = 14.8424(7) Å
c = 21.2449(11) Å
= 89.917(5)°.
a = 10.1120(4) Å
b = 15.4180(6) Å
c = 22.2416(13) Å
a = 13.0402(8) Å
b = 14.9871(7) Å
c = 19.6055(9) Å
= 100.523(5)°.
Volume
3
3
3
3
3679.6(12) Å
3940.3(4) Å
3467.6(3) Å
3767.2(3) Å
Z
4
4
4
4
Density (calculated)
3
3
3
3
2.145 Mg/m
1.943 Mg/m
2.070 Mg/m
1.988 Mg/m
Absorption coefficient
-1
-1
-1
-1
8.245 mm
7.690 mm
8.714 mm
8.156 mm
F(000)
2240
2176
2048
2144
Crystal size
3
3
3
3
0.490 x 0.270 x 0.110 mm
3.457 to 29.613°.
0.370 x 0.170 x 0.060 mm
3.538 to 29.644°.
0.440 x 0.340 x 0.060 mm
3.447 to 29.532°.
0.250 x 0.220 x 0.040 mm
3.413 to 29.639°.
Theta range for data collection
Index ranges
-14<=h<=17, -26<=k<=30, -
17<=l<=18
-17<=h<=17, -20<=k<=20, -
29<=l<=28
-12<=h<=13, -18<=k<=20, -
30<=l<=20
-15<=h<=18, -20<=k<=16, -
26<=l<=26
Reflections collected
19086
43916
11519
21777
Independent reflections
Completeness to theta = 25.242°
Absorption correction
8654 [R(int) = 0.0375]
99.7 %
Analytical
9905 [R(int) = 0.0670]
99.7 %
Analytical
4154 [R(int) = 0.0652]
99.7 %
Analytical
8936 [R(int) = 0.0701]
99.8 %
Analytical
Max. and min. transmission
Refinement method
0.508 and 0.153
0.619 and 0.185
0.572 and 0.112
0.741 and 0.229
2
2
2
2
Full-matrix least-squares on F
8654 / 0 / 487
Full-matrix least-squares on F
9905 / 0 / 469
Full-matrix least-squares on F
4154 / 0 / 177
Full-matrix least-squares on F
8936 / 30 / 412
Data / restraints / parameters
2
1.029
1.035
1.032
1.045
Goodness-of-fit on F
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0324, wR2 = 0.0498
R1 = 0.0526, wR2 = 0.0566
R1 = 0.0437, wR2 = 0.0804
R1 = 0.0956, wR2 = 0.1015
R1 = 0.0596, wR2 = 0.1385
R1 = 0.0942, wR2 = 0.1723
R1 = 0.0544, wR2 = 0.0981
R1 = 0.0973, wR2 = 0.1202
Largest diff. peak and hole
-3
-3
-3
-3
0.888 and -1.167 e.Å
2.814 and -1.207 e.Å
2.961 and -2.514 e.Å
3.213 and -1.407 e.Å