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SUPPLEMENTARY INFORMATION
On the Rhenium(I)–Silver(I) Cyanide Porous
Macrocyclic Clusters
Monika K. Krawczyk,1,2,* Rahman Bikas,1,3 Marta S. Krawczyk,4 Tadeusz Lis1
1Faculty of Chemistry University of Wroclaw, F. Joliot-Curie 14 St., 50-383 Wrocław, Poland
2Institute of Experimental Physics, University of Wrocław, M. Borna 9, 50-204 Wrocław,
Poland
3Department of Chemistry, Faculty of Science, University of Zanjan 45195-313, Zanjan, Iran
4Department of Analytical Chemistry, Faculty of Pharmacy, Wrocław Medical University,
Borowska 211A St., 50-556 Wrocław, Poland
*E-mail: [email protected] , [email protected]
Table of Contents
1. General 2
2. Single crystal X-ray diffraction studies 2
3. Crystal structures description 5
4. MS spectra 18
5. UV-Vis spectra 20
6. IR and FIR spectra 21
7. TGA diagrams 28
8. References 30
Electronic Supplementary Material (ESI) for CrystEngComm.This journal is © The Royal Society of Chemistry 2017
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1. General
Crystallographic data for all crystals were collected on KM-4-CCD and Xcalibur four-
circle diffractometers with a Ruby and Onyx charge coupled device detectors with Mo Kα
radiation (λ = 0.71073 Å) and processed with the CrysAlis PRO program.S1 The infrared (IR)
and far infrared (FIR) spectra were recorded on a Bruker Vertex 70 FTIR spectrometer
(Bruker) as nujol mulls. The UV-visible spectra were performed on a Cary500 SCAN UV-
VIS-NIR spectrophotometer. Elemental analyses were performed on an elemental analyzer
CHNS Vario EL III, Elemental Analysensysteme GmbH. Mass spectrometric experiments
were performed on a Bruker micrOTOF-Q mass spectrometer (Bruker, Daltonics, Bremen
Germany).
2. Single crystal X-ray diffraction studies
All structures were solved with the use of SHELXS-97 and refined by full-matrix least-
squares on F2 using SHELXL-97 program.S2 An analytical absorption corrections were
introduced.S1 For preparation of figures and scheme DIAMOND graphical program was
used.S3 In all structures the H atoms of aromatic rings were treated as riding atoms in
geometrically idealized positions, with d(C—H) = 0.95 and Uiso(H) = 1.2Ueq(C) as well as H
atoms of methyl groups (1a-d) and H atoms derived from hydroxy groups (1a-c, 1e) were
introduced in positions calculated from geometry, with d(C—H) = 0.98 or 0.99 Å, d(O—H) =
0.84 or 0.86 Å and Uiso(H) = 1.5Ueq(C), Uiso(H) = 1.5Ueq(O).
The studied crystals of the host-guest complexes 1a-d and 1f are isomorphous and the
structure of 1c was investigated as a first one. The preliminary atomic coordinates of the
cluster [Re4Ag4(µ-CN)8(CO)8 (PPh3)8] in structures 1a, 1b, and 1d were taken from the 1c
structure solution and in the case of structure 1f the preliminary coordinates of the cluster
were taken from 1a.
[Re4Ag4(µ-CN)8(CO)8(PPh3)8]∙5MeOH∙0.75H2O (1c)
In 1c after the refinement of the positions of all atoms in the cluster [Re4Ag4(µ-CN)8(CO)8
(PPh3)8] and methanol molecules (O11/C11, O12/C12 and O13/C13), on the difference
Fourier map the additional maxima appeared. These peaks were interpreted as a disorder of
methanol and water. The positions of MeOH molecules denoted as O14/C14 and O15/C15,
O16/C16 and C17/C17 were refined with s.o.f. = 0.5 (site occupancy factor) and the water
molecules were refined with s.o.f. = 0.25 (O1W) and 0.5 (O2W). The carbon atoms in all
methanol molecules were refined isotropically. The disorder of solvents was modeled using
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PART commands (which enabled setting up hydrogen atoms for the overlapping disordered
molecules) and in the case of methanol molecules SAME restraints were also applied. H
atoms of hydroxyl groups were introduced in positions calculated from geometry using
command AFIX 147 (H11, H13) or AFIX 83 (H12, H14 – H17). Hydrogen atoms of methyl
groups were positioned geometrically using the instruction HFIX 137 (for H atoms bonded to
methyl C12 and C13 atoms) and the command AFIX 3 (for H atoms of C11, C14 – C17
atoms) was finally used because of large values of displacement parameters of carbon atoms
of methyl group.
[Re4Ag4(µ-CN)8(CO)8(PPh3)8]∙5EtOH (1a)
After the refinement in the created model the disorder of ethanol molecules (O14/C14/C24,
O15/C15/C25, O16/C16/C26 and O17/C17/C27) was observed, which were refined
isotropically (except the O14 atom) with following occupancies of 0.70, 0.30, 0.65, 0.35,
respectively. The disorder was handled by using PART instructions as well as SAME and
SADI restraints. The hydroxyl hydrogen atoms were introduced in geometrically idealized
positions using command HFIX 83 for H12, H15 atoms, and in the case of H11, H13, H14
atoms command AFIX 3 was finally used. Hydrogen atoms of methyl groups were introduced
and refined using a riding model by the command AFIX 33 and command AFIX 3 (for H
atoms bonded to C25) was used.
[Re4Ag4(µ-CN)8(CO)8(PPh3)8]∙2MeCN∙H2O (1b)
On the final difference Fourier map additional peaks were observed, which were introduced to
the structure solution and interpreted as disordered molecules of acetonitrile and water. The
solvent molecules were refined isotropically and the disorder was modeled using DFIX
constraints and PART commands.
[Re4Ag4(µ-CN)8(CO)8(PPh3)8]∙3Me2CO (1d)
After the refinement the created model shown that three molecules of acetone were
incorporated into the cavity of the host framework [Re4Ag4(µ-CN)8(CO)8(PPh3)8] (in the
course of the acetone sorption, Experimental Section). In order to check whether all guest
occupancies are 100% we refined the model with occupancies of solvent molecules as free
variables that revealed the site occupancy factor (s.o.f.) of each acetone molecule is almost 1,
[as follows: 0.845(17), 0.970(19), 0.864(18)]. However, from the chemical point of view it
seemed to be reasonable to refine the occupancy factors of acetone as integer number 1. To
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prevent displacement parameters of some atoms from being “non-positive definite” (NPD),
the EADP (for atoms of carbonyl and cyanide ligands) and SIMU instructions (in the case of
atoms of phenyl rings) were used.
[Re4Ag4(µ-CN)8(CO)8(PPh3)8]∙2BuOH (1e)
The refined model revealed that in the cavity of the host complex there are two disordered
butan-1-ol molecules. The disorder was modeled over two equally occupied positions using
DFIX instructions. Similarly to 1d, the commands of EADP and SIMU were applied in order
to refine displacement parameters of atoms that were “non-positive definite”.
[Re4Ag4(µ-CN)8(CO)8(PPh3)8]∙4EtOH (1f)
As was mentioned before, the preliminary atomic coordinates of the host complex
[Re4Ag4(µ-CN)8(CO)8(PPh3)8] in the structure 1f were taken from the 1a structure solution.
All C, N and O atoms in the structure were refined isotropically. Similarly to 1e, and 1d
structures, the EADP and SIMU instructions were used in order to refine displacement
parameters of all “non-positive definite” atoms. Moreover, phenyl rings were refined by the
use of AFIX 66 restraints. It emerged that in the result of crystals soaking, crystal lattice is the
same as in 1a, with ethanol molecules absorbed into the host cavity in the same positions, but
lower occupancy factors per cluster compared to 1a (the refinement of coordinates of EtOH
molecules was performed using DFIX constraints).
{ReAg1.5(CN)2.5(CO)2(PPh3)2} (3)
After the refinement on the difference Fourier map the additional maxima close to Ag2, N5
and C5 atoms appeared. The created model revealed that in the structure the Ag2 atom and
bridging cyanide groups (atoms N5, C5 as well as C2, N2 and C3, N3) and terminal carbonyl
groups (atoms C2, O2X and C3, O3X) are disordered. In each case the disorder was modeled
over two positions with occupancies of 0.810(14) (Ag2), 0.190(14) (Ag3), 0.405(7) (N5 and
C5) and 0.095(7) (N50 and C50) and the site occupancy factors (s.o.f.) of Ag1 atom equals
0.5. Created model shown that both groups (N5, C5 and N50, C50) occurred in the same
positions that was interpreted as the statistical disorder. Moreover on the difference Fourier
map the additional maxima close to C atoms of two phenyl rigs (viz.
C1G/C2G/C3G/C4G/C5G/C6G and C1H/C2H/C3H/C4H/C5H/C6H) were observed, which
were interpreted as a disorder. In the structure the EADP and SIMU instructions were used for
all “non-positive definite” atoms. The disorder of silver atoms and bridging cyanide ligands
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complicate the interpretation of the structure. The proposed model presents a discrete
decanuclear complex (Fig. S1, S2).
3. Crystal structures description
Crystals 1a-d and 1f are isomorphous and are built up from molecules of the host complex
[Re4Ag4(µ-CN)8(CO)8(PPh3)8] (1) located in general position, while in 1e the basic structure
is centrosymmetric (Fig. S4). In 1a-d and 1f structures an average diagonal (the Re–Re
distance) in the pseudo-square-shaped framework [Re4Ag4(µ-CN)8(CO)8 is 14.7 Å, while in
1e the host framework adopts rather a pseudo-rectangular geometry with diagonals (the Re–
Re distances) of 13.7 and 15.6 Å.
All 1a-e crystals have the channeling architecture composed of the cavity-shaped molecules
of cluster [Re4Ag4(µ-CN)8(CO)8 (PPh3)8] (1). Channels stretching along the [100] direction
contain the embedded molecules of solvents: EtOH (1a), MeCN (1b), MeOH, H2O,(1c)
acetone (1d), butan-1-ol (1e), within which guest molecules are linked each other by weak C-
H…π hydrogen bonds (Tables S3, S5, S7, S9 and S12). The molecules of solvents are
involved in the host-guest interactions with the cluster molecules by hydrogen bonds of the
type C–H…O [in 1b: C23–H23C···O1W in 1c: C4C–H4C···O12iii, C4R–H4R···O12;] C–H…π
[in 1b: C21–H21B···Cg21; in 1c: C13–H13B···Cg21ix], C–H…N [in 1a: C25–H25B···N7]
or/and van der Waals contacts.
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Table S1. Selected Crystallographic Data and Structure Refinement Parameters for 1f crystal.1f
Empirical formula [Re4Ag4(µ-CN)8(CO)8 (PPh3)8]∙4EeOHFormula weight (g mol-1) 3890.94
Crystal system, space group Triclinic, P1
a (Å) 12.258(2)b (Å) 18.441(4)c (Å) 36.006(8)α (°) 83.08(3)β (°) 88.98(3)γ (°) 72.38(3)V (Å3) 7699(3)Z 2
µ (mm-1) 11.24F(000) 3876
Crystal size (mm) 0.10 × 0.08 × 0.07Crystal colour colourlessCrystal form block
Diffractometer Xcalibur with CCD Onyx detectorRadiation type, wavelength, λ
(Å) Cu Kα, 1.5418
T (K) 100(2)Θ range (°) 2.47 – 77.86h, k, l range -15 ≤ h ≤ 11
-20 ≤ k ≤ 21-35 ≤ l ≤ 44
Measured reflections 50768Independent reflections 27630Observed refl. (I>2δ(I)) 4256Transmission max/min 0.430/ 0.602
Rint 0.267Refinement on F2
Data/restraints/parameters 27630/12/592R[F2 > 2σ(F2)] 0.087
wR(F2) 0.193GooF = S 0.54
∆ρmax/∆ρmin (ēÅ-3) 2.54/-2.20
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Fig. S1. Proposed model of the structure 3 presenting decanuclear complex.
Symmetry codes: [iii] 2-x, -y, 1-z; [v] x, 1+y, z
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Fig. S2. Top: Molecular structure and the atom-numbering scheme for 3 showing
arrangement of the species {ReAg1.5(CN)2.5(CO)2(PPh3)2} in the unit cell. Bottom: Fragment
of the close crystal packing in 3 preventing from inclusion of smaller molecules.
Symmetry codes: [i] x, 1+y, z; [iii] 2-x, -y, 1-z; [iv] 1-x, 1-y, 1-z.
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Fig. S3. Arrangement of the species {ReAg1.5(CN)2.5(CO)2(PPh3)2} forming decanuclear
metallacycles. Atoms of occupancy equaled 0.5 were shown as transparent ellipsoids in pastel
shades.
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Fig. S4. Molecular structure of the host-guest complex [Re4Ag4(µ-CN)8(CO)8(PPh3)8]‧2BuOH (1e).
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Fig. S5. Packing diagram for 2 showing layer architecture viewed down the a axis. H atoms were omitted for clarity.
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Fig. S6. Fragment of packing diagram for 2 showing layers parallel to the (100) crystallographic plane. H atoms were omitted for clarity.
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Table S2. Geometry of C–H∙∙∙O hydrogen bonds in [Re4Ag4(µ-NC)8(CO)8(PPh3)8]
∙5(MeOH)∙0.75(H2O) (1c)
D–H (Å) H···A (Å) D···A (Å) <(D–H···A) (°)C6B–H6B···O8i 0.95 2.57 3.294(6) 134C2V–H2V···O2ii 0.95 2.65 3.312(7) 127C6Z–H6Z···O8 0.95 2.62 3.217(7) 121O11–H11···O12 0.84 2.06 2.698(12) 133O13–H13···O11 0.84 1.95 2.743(11) 157C4C–H4C···O12iii 0.95 2.52 3.391(9) 152C4R–H4R···O12 0.95 2.57 3.371(9) 143C4D–H4D···O8iv 0.95 2.48 3.114(7) 124C4J–H4J···O3v 0.95 2.57 3.403(7) 147C4W–H4W···O7 vi 0.95 2.59 3.299(7) 132C51–H51···O3vii 0.95 2.60 3.318(8) 133Symmetry codes: [i] x, y+1, z; [ii] x, y-1, z; [iii] x+1, y, z; [iv] x-1, y+1, z; [v] -x+2, -y+1,
-z+1; [vi] -x+1, -y+1, -z; [vii] -x+1, -y+1, -z+1.
Table S3. Geometry of C–H∙∙∙π interactions in 1c.
C–H···π H···Cg (Å) C···Cg (Å) <(C–H···Cg) (°)
C3H–H3H···Cg16vii 2.97 3.82 150
C3T–H3T···Cg1viii 2.66 3.55 156
C3U–H3U···Cg22iii 2.92 3.81 156
C4L–H4L···Cg3 3.00 3.87 154
C5C–H5C···Cg6iii 2.83 3.76 166
C5D–H5D···Cg1ix 2.93 3.44 115
C5G–H5G···Cg12ix 2.93 3.83 157
C5J–H5J···Cg9iii 2.82 3.74 163
C5N–H5N···Cg16iii 2.83 3.72 157
C5S–H5S···Cg20viii 2.79 3.65 150
C13–H13B···Cg21ix 2.94 3.68 133
Symmetry codes: [vii] 1-x,1-y,1-z ; [viii] 2-x,1-y,-z ; [iii] 1+x,y,z ; [ix] -1+x,y,z
Centroids of aromatic rings: Cg1[C1A/C2A,C3A/C4A/C5A/C6A];
Cg3[C1C/C2C,C3C/C4C/C5C/C6C]; Cg6[C1F/C2F,C3F/C4F/C5F/C6F];
Cg9[C1I/C2I,C3I/C4I/C5I/C6I]; Cg12[C1L/C2L,C3L/C4L/C5L/C6L];
Cg16[C1P/C2P,C3P/C4P/C5P/C6P]; Cg20[C1T/C2T,C3T/C4T/C5T/C6T];
Cg21[C1U/C2U,C3U/C4U/C5U/C6U]; Cg22[C1V/C2V/C3V/C4V/C5V/C6V].
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Table S4. Geometry of C–H∙∙∙O hydrogen bonds in [Re4Ag4(µ-
NC)8(CO)8(PPh3)8]‧2MeCN‧H2O (1b)
D–H (Å) H···A (Å) D···A (Å) <(D–H···A) (°)C6B–H6B···O8i 0.95 2.58 3.296(9) 133C6Z–H6Z···O8 0.95 2.60 3.200(9) 121C23–H23C···O1W 0.98 1.94 2.86(6) 156C4D–H4D···O8iii 0.95 2.50 3.109(9) 122C4J–H4J···O3iv 0.95 2.54 3.364(9) 146C51–H51···O3v 0.95 2.51 3.256(11) 135Symmetry codes: [i] x, y+1, z; [ii] x, y-1, z; [iii] -1+x,1+y,z; [iv] 2-x,1-y,1-z; [v] -x,1-y,1-z.
Table S5. Geometry of C–H∙∙∙π interactions in 1b.
C–H···π H···Cg (Å) C···Cg (Å) <(C–H···Cg) (°)
C3T–H3T···Cg1vi 2.64 3.55 156
C3U–H3U···Cg22vii 2.90 3.78 155
C4L–H4L···Cg3 2.99 3.86 155
C5C–H5C···Cg6vii 2.91 3.84 164
C5D–H5D···Cg1ix 2.85 3.39 118
C5G–H5G···Cg12ix 2.90 3.81 163
C5J–H5J···Cg9vii 2.81 3.74 171
C5N–H5N···Cg16vii 2.85 3.74 156
C5S–H5S···Cg20vi 2.78 3.63 150
C21–H21B···Cg21 2.63 3.51 149
Symmetry codes: [vi] 2-x,1-y,-z ; [vii] 1+x,y,z ; [ix] -1+x,y,z.
Centroids of aromatic rings: Cg1[C1A/C2A,C3A/C4A/C5A/C6A];
Cg3[C1C/C2C,C3C/C4C/C5C/C6C]; Cg6[C1F/C2F,C3F/C4F/C5F/C6F];
Cg9[C1I/C2I,C3I/C4I/C5I/C6I]; Cg12[C1L/C2L,C3L/C4L/C5L/C6L];
Cg16[C1P/C2P,C3P/C4P/C5P/C6P]; Cg20[C1T/C2T,C3T/C4T/C5T/C6T];
Cg21[C1U/C2U,C3U/C4U/C5U/C6U]; Cg22[C1V/C2V,C3V/C4V/C5V/C6V].
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Table S6. Geometry of C–H∙∙∙O hydrogen bonds in [[Re4Ag4(µ-NC)8(CO)8(PPh3)8]‧5EtOH
(1a)
D–H (Å) H···A (Å) D···A (Å) <(D–H···A) (°)C6B–H6B···O8i 0.95 2.54 3.272(6) 134O11–H11···O13 0.84 2.05 3.697(12) 134C12–H12···O11 0.84 2.03 2.782(12) 149C13–H13···O14iii 0.85 1.81 2.663(13) 176C13–H13B···O15iii 0.99 2.39 3.03(2) 122C25–H25B···N7 0.98 2.52 3.47(3) 164C27–H35A···O12 0.98 2.19 3.16(2) 170Symmetry code: [i] x, y+1, z ; [iii] x-1, y, z.
Table S7. Geometry of C–H∙∙∙π interactions in 1a.
C–H···π H···Cg (Å) C···Cg (Å) <(C–H···Cg) (°)
C3H–H3H···Cg16iv 2.91 3.77 151
C3T–H3T···Cg1v 2.63 3.52 157
C3U–H3U···Cg22vi 2.91 3.81 158
C5C–H5C···Cg6vi 2.81 3.74 169
C5G–H5G···Cg12vii 2.95 3.86 161
C5J–H5J···Cg9vi 2.80 3.72 164
C5N–H5N···Cg16vi 2.83 3.72 157
C5S–H5S···Cg20v 2.81 3.66 149
Symmetry codes: [iv] 1-x,1-y,1-z ; [v] 2-x,1-y,-z; [vi] 1+x,y,z; [vii] -1+x,y,z.
Centroids of aromatic rings: Cg1[C1A/C2A,C3A/C4A/C5A/C6A];
Cg6[C1F/C2F,C3F/C4F/C5F/C6F]; Cg9[C1I/C2I,C3I/C4I/C5I/C6I];
Cg12[C1L/C2L,C3L/C4L/C5L/C6L]; Cg16[C1P/C2P,C3P/C4P/C5P/C6P];
Cg20[C1T/C2T,C3T/C4T/C5T/C6T]; Cg22[C1V/C2V,C3V/C4V/C5V/C6V].
Table S8. Geometry of C–H∙∙∙O hydrogen bonds in [[Re4Ag4(µ-NC)8(CO)8(PPh3)8]‧3Me2CO
(1d)
D–H (Å) H···A (Å) D···A (Å) <(D–H···A) (°)C31–H31A···O13 0.98 2.54 3.19(3) 124C4D–H4D···O8i 0.95 2.49 3.09(2) 121C4J–H4J···O3ii 0.95 2.50 3.35(2) 148C6B–H6B···O8iii 0.95 2.58 3.30(2) 133C6Z–H6Z···O8 0.95 2.56 3.22(2) 126Symmetry codes: [i] -1+x,1+y,z; [ii] 2-x,1-y,1-z; [iii] x,1+y,z.
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Table S9. Geometry of C–H∙∙∙π interactions in 1d
C–H···π H···Cg (Å) C···Cg (Å) <(C–H···Cg) (°)
C3H–H3H···Cg16iv 2.91 3.78 153
C3T–H3T···Cg1ii 2.67 3.54 153
C3U–H3U···Cg22v 2.97 3.88 160
C5G–H5G···Cg12vi 2.87 3.81 169
C5J–H5J···Cg9v 2.86 3.80 173
C5N–H5N···Cg16v 2.94 3.82 154
C5S–H5S···Cg20ii 2.75 3.60 149
Symmetry codes: [iv] 1-x,1-y,1-z ; [ii] 2-x,1-y,-z; [v] 1+x,y,z; [vi] -1+x,y,z.
Centroids of aromatic rings: Cg1[C1A/C2A,C3A/C4A/C5A/C6A];
Cg9[C1I/C2I,C3I/C4I/C5I/C6I]; Cg12[C1L/C2L,C3L/C4L/C5L/C6L];
Cg16[C1P/C2P,C3P/C4P/C5P/C6P]; Cg20[C1T/C2T,C3T/C4T/C5T/C6T].
Table S10. Geometry of hydrogen bonds in [[Re4Ag4(µ-NC)8(CO)8(PPh3)8]‧2BuOH (1e)
D–H (Å) H···A (Å) D···A (Å) <(D–H···A) (°)C6D–H6D···N7 0.95 2.70 3.65(2) 176C6G–H6G···N8i 0.95 2.61 3.51(2) 158O11–H11···O12ii 0.84 1.99 2.81(4) 165
C4J–H4J···O2iii 0.95 2.58 3.23(2) 126
C5A–H5A···O4iv 0.95 2.57 3.46(2) 156
Symmetry code: [i] -x+1, -y+1, -z+1; [ii] 1-x,-y,-z; [iii] -x,1-y,-z; [iv] -1+x,y,1+z
Table S11. Geometry of C–O∙∙∙π interactions in 1e
C–O···π O···Cg (Å) C···Cg (Å) <(C–O···Cg) (°)
C1–O1···Cg1 3.40 3.52 87
C2–O2···Cg6 3.70 3.83 87
C3–O3···Cg9 3.70 3.85 89
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Table S12. Geometry of C–H∙∙∙π interactions in 1e
C–H···π H···Cg (Å) C···Cg (Å) <(C–H···Cg) (°)
C3B–H3B···Cg5v 2.73 3.45 133
C3D–H3D···Cg1vi 2.53 3.41 153
C3F–H3F···Cg10vii 2.92 3.71 142
C3G–H3G···Cg12vi 2.87 3.76 156
C3J–H3J···Cg8v 2.71 3.41 131
Symmetry code: [i] -x+1, -y+1, -z+1; [ii] 1-x,-y,-z; [iii] -x,1-y,-z; [iv] -1+x,y,1+z
Centroids of aromatic rings: Cg1[C1A/C2A,C3A/C4A/C5A/C6A];
Cg5[C1E/C2E,C3E/C4E/C5E/C6E]; Cg8[C1H/C2H,C3H/C4H/C5H/C6H];
Cg10[C1J/C2J,C3J/C4J/C5J/C6J]; Cg12[C1L/C2L,C3L/C4L/C5L/C6L].
Table S13. Geometry of hydrogen bonds in [[Re2Ag2(µ-NC)4(CO)4(PPh3)6] (2)
D–H (Å) H···A (Å) D···A (Å) <(D–H···A) (°)C2H–H2H···O2i 0.95 2.59 3.459(7) 152C3G–H3G···N2i 0.95 2.55 3.384(7) 147Symmetry code: [i] x, y+1, z.
Table S14. Geometry of C–H∙∙∙π interactions in 2
C–H···π H···Cg (Å) C···Cg (Å) <(C–H···Cg) (°)
C3E–H3E···Cg9 2.67 3.58 160
C3H–H3H···Cg1i 2.59 3.54 177
C5B–H5B···Cg5ii 2.97 3.77 142
C5E–H5E···Cg2iii 2.72 3.65 169
Symmetry code: [i] x, y+1, z; [ii] 1-x, 1-y, 1-z; [iii] x-1, y, z.
Centroids of aromatic rings: Cg1[C1A/C2A,C3A/C4A/C5A/C6A];
Cg2[C1B/C2B,C3B/C4B/C5B/C6B];
Cg5[C1E/C2E,C3E/C4E/C5E/C6E]; Cg9[C1I/C2I,C3I/C4I/C5I/C6I].
Table S15. Geometry of hydrogen bonds in [[Re2Ag2(µ-NC)4(CO)4(PPh3)6] (3)
D–H (Å) H···A (Å) D···A (Å) <(D–H···A) (°)C6C–H6C···N31 0.95 2.52 3.06(2) 116
Page 18
18
4. MS spectra
3699.15
3700.15
3701.15
3702.15
3703.15
3704.15
3705.16
3706.163707.16
3708.16
3709.16
3710.16
3711.16
3712.16
3713.16
3714.173715.17
Re4Ag4C160H120N8O8P8, M ,3704.16
0
500
1000
1500
2000
Intens.
3695.0 3697.5 3700.0 3702.5 3705.0 3707.5 3710.0 3712.5 3715.0 3717.5 m/z
3706.17
3707.18
3708.19
3709.24 3710.293705.28
3704.27
3703.29
3702.21
3700.263701.16
3712.01
+MS, 0.0-1.5min #(2-97)
0
1
2
3
Intens.
3695.0 3697.5 3700.0 3702.5 3705.0 3707.5 3710.0 3712.5 3715.0 3717.5 m/z
Fig. S7. Top: Simulated MS spectra for cluster 1; Bottom: experimental MS spectra for
cluster 1.
3706.17
3662.21
3707.18
+MS, 0.0-1.5min #(2-97)
0
2
4
6
Intens.
3660 3680 3700 3720 3740 3760 3780 3800 3820 m/z
Fig. S8. Top: Experimental MS spectra for cluster 1 (larger range).
Page 19
19
2399.232400.25
2401.24
2402.24
2403.24
2398.24
2397.24 2404.28
2405.22
2396.212395.24
+MS, 0.0-1.1min #(2-72)
0
50
100
150
200
Intens.
2390 2392 2394 2396 2398 2400 2402 2404 2406 2408 m/z
2395.242396.25
2397.25
2398.25
2399.25 2400.25
2401.25
2402.25
2403.25
2404.26
2405.26
2406.26
Re2Ag2C116H90N4O4P6Na1, M ,2399.25
0
500
1000
1500
2000
Intens.
2390 2392 2394 2396 2398 2400 2402 2404 2406 2408 m/z
Fig. S9. Top: experimental MS spectra for 2+Na+; Bottom: simulated MS spectra for 2+Na+.
2372.252373.26
2374.26
2375.26
2376.26 2377.26
2378.26
2379.26
2380.26
2381.27
2382.27
2383.27
Re2Ag2C116H90N4O4P6, M ,2376.26
0
500
1000
1500
2000
Intens.
2370 2372 2374 2376 2378 2380 2382 2384 2386 2388 m/z
Fig. S10. Simulated MS spectra for 2.
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20
5. UV-Vis spectra
Fig. S11. The UV–Vis absorption spectrum performed for a solid sample of 1 complex after desolvation of crystals.
Fig. S12. The UV–Vis absorption spectrum performed for 2 complex for a solid sample.
The UV-Vis absorption spectra performed for 1 and 2 complexes show broad bands in the
range of about 350 – 250 nm that could be interpreted as overlapping of the LMCT (ligand-to-
metal charge-transfer) d(P)→ d(Re), d(N)→ d(Ag) (1, 2), and d(P)→ d(Ag) (for 2)
transitions.
200 250 300 350 400 450 500
Abs
orba
nce
(arb
itrar
yun
its)
Wavelength/nm200 250 300 350 400 450 500
Abs
orba
nce
(arb
itrar
yun
its)
Wavelength/nm
200 250 300 350 400 450 500
Abs
orba
nce
(arb
itrar
yun
its)
Wavelength/nm200 250 300 350 400 450 500
Abs
orba
nce
(arb
itrar
yun
its)
Wavelength/nm
Page 21
21
6. IR and FIR spectra
3792
3638
3442 305329552925
285527262672
2609
24082354
2126
19391878
15861464 1434
13771310 1187
1092999
746693
614565
516460
422
Tran
smitt
ance
/A. U
.
3800 2800 1800 800
Wavenumber/cm-1
Fig. S13. IR spectrum performed for the crystal of 1 (after desolvation). ν = 3792, 3638, 3442, 3074, 3053, 3019, 2955, 2925, 2870, 2855, 2726, 2672, 2609, 2408, 2354, 2139, 2126, 1955, 1949, 1939, 1894, 1878, 1667, 1619, 1586, 1573, 1480, 1464, 1434, 1377, 1331, 1310, 1284, 1187, 1159, 1092, 1072, 1026, 999, 971, 919, 850, 746, 741, 723, 693, 623, 614, 565, 516, 500, 470, 460, 422, 395 cm-1.
Page 22
22
566
518501
458
421
398
237
188 150
Tran
smitt
ance
/A. U
.
580 480 380 280 180 80
Wavenumber/cm -1
Fig. S14. FIR spectrum performed for the crystal of 1 (after desolvation).ν = 566, 518, 515, 501, 469, 458, 443, 429, 421, 406, 398, 352, 347, 343, 338, 328, 323, 316, 303, 281, 254, 237, 227, 221, 214, 203, 188, 170, 157, 150, 133, 126, 121 cm-1.
Page 23
23
30462926
2856
21402123
19291861
158614631435
13771311
11851095
1026
847742
696617
520422
Tran
smitt
ance
/A. U
.
3800 2800 1800 800
Wavenumber/cm-1
Fig. S15. IR spectrum performed for crystal of 2.ν = 3140, 3077, 3059, 3046, 2957, 2926, 2870, 2856, 2725, 2674, 2611, 2423, 2350, 2317, 2140, 2123, 2111, 2094, 2080, 1942, 1929, 1906, 1894, 1872, 1872, 1861, 1844, 1828, 1586, 1572, 1479, 1463, 1435, 1377, 1367, 1329, 1311, 1285, 1266, 1185, 1158, 1154, 1095, 1087, 1072, 1026, 998, 968, 919, 890, 853, 847, 803, 770, 751, 745, 742, 722, 706, 696, 625, 617 cm-1.
Page 24
24
563
520
501487
455442
423
393
343
234 187
130
Tran
smitt
ance
/A. U
.
580 480 380 280 180 80
Wavenumber/cm-1
Fig. S16. FIR spectrum performed for the crystal of 2.ν = 563, 551, 547, 543, 534, 520, 514, 501, 487, 474, 470, 467, 464, 455, 442, 430, 423, 405, 399, 393, 386, 381, 374, 366, 357, 352, 348, 344, 338, 321, 315, 306, 301, 297, 291, 286, 282, 278, 273, 270, 261, 259, 253, 248, 241, 234, 227, 221, 218, 214, 211, 208, 204, 201, 197, 191, 187, 184, 181, 177, 174, 170, 167, 164, 160, 157, 153, 150, 146, 143, 140, 133, 130 cm-1.
Page 25
25
3790
3638 3053
29252855
2126
19391878
1463 14351377
11861092
849744
695614
565515
422
3398
1025
1709
1218
3359
1047
879
3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
Tran
smitt
ance
/ A. U
.
Fig. S17. IR spectra performed for crystals of 1 (dried) and 1a – 1d (in the range of 4000 – 400 cm-1). Colour code: blue – 1 (dried); brown – 1a (1-EtOH); red – 1b (1-MeCN); purple – 1c (1-MeOH); green – 1d (1-Me2CO).
Page 26
26
2126
193918931878
1617
14791463 1435
1377
11861159
1092
999
849
744
695
614
565515
460422
1025
1709
1218
1047
879
2200 2000 1800 1600 1400 1200 1000 800 600 400
Wavenumber/cm -1
Tran
smitt
ance
/ A. U
.
Fig. S18. IR spectra performed for crystals of 1 (dried) and 1a – 1d (in the range of about 2200 – 400 cm-1). Colour code: blue – 1 (dried); brown – 1a (1-EtOH); red – 1b (1-MeCN); purple – 1c (1-MeOH); green – 1d (1-Me2CO).
Page 27
27
The IR spectra revealed the presence of solvents molecules incorporated into channels. The characteristic bands derived from guest molecules were observed as follows: v(O-H) = 3359, v(C–O) = 1047 and v(C–C) = 879 cm-1 for 1a (1-EtOH); v(C≡N) = 2251 cm-1 for 1b (1-MeCN); v(O-H) = 3398, v(C–O) = 1025 cm-1 for 1c (1-MeOH); v(C=O) = 1709 and v(C–C) = 1218 cm-1 for 1d (1-Me2CO).
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28
7. TGA diagramsIn the diagram performed for soaked crystals the loss of solvent is observed at about 150 oC and the organic part of the cluster starts to remove from about 250 oC. In the dried crystals there is no weight loss until 250 oC, which indicates the absence of solvent in the dried sample.
Fig. S19. TGA diagram performer for 1a crystals.
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29
Fig. S20. TGA diagram performer for dried crystals of 1.
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30
8. References
(S1) Agilent 2011. CrysAlis PRO. Agilent Technologies, Yarnton, England.
(S2) Sheldrick, G. M. 2008. Acta Cryst. A64, 112–122.
(S3) Brandenburg, K. 2006. DIAMOND. Crystal Impact GbR, Bonn, Germany.
