research communications
Silver(I) nitrate two-dimensional coordination polymers of two new pyrazinethiophane ligands: 5,7-dihydro-1H,3H-dithieno[3,4-b:3′,4′-e]pyrazine and 3,4,8,10,11,13-hexahydro-1H,6H-bis([1,4]dithiocino)[6,7-b:6′,7′-e]pyrazine
aInstitute of Chemistry, University of Neuchâtel, Av. de Bellevax 51, CH-2000 Neuchâtel, Switzerland, and bInstitute of Physics, University of Neuchâtel, rue Emile-Argand 11, CH-2000 Neuchâtel, Switzerland
*Correspondence e-mail: helen.stoeckli-evans@unine.ch
The two new pyrazineophanes, 5,7-dihydro-1H,3H-dithieno[3,4-b:3′,4′-e]pyrazine, C8H8N2S2, L1, and 3,4,8,10,11,13-hexahydro-1H,6H-bis([1,4]dithiocino)[6,7-b:6′,7′-e]pyrazine, C12H16N2S4, L2, both crystallize with half a molecule in the the whole molecules are generated by inversion symmetry. The molecule of L1, which is planar (r.m.s. deviation = 0.008 Å), consists of two sulfur atoms linked by a rigid tetra-2,3,5,6-methylenepyrazine unit, forming planar five-membered rings. The molecule of L2 is step-shaped and consists of two S–CH2–CH2–S chains linked by the central rigid tetra-2,3,5,6-methylenepyrazine unit, forming eight-membered rings that have twist-boat-chair configurations. In the crystals of both compounds, there are no significant intermolecular interactions present. The reaction of L1 with silver nitrate leads to the formation of a two-dimensional coordination polymer, poly[(μ-5,7-dihydro-1H,3H-dithieno[3,4-b;3′,4′-e]pyrazine-κ2S:S′)(μ-nitrato-κ2O:O′)silver(I)], [Ag(NO3)(C8H8N2S2)]n, (I), with the nitrato anion bridging two equivalent silver atoms. The central pyrazine ring is situated about an inversion center and the silver atom lies on a twofold rotation axis that bisects the nitrato anion. The silver atom has a fourfold AgO2S2 coordination sphere with a distorted shape. The reaction of L2 with silver nitrate also leads to the formation of a two-dimensional coordination polymer, poly[[μ33,4,8,10,11,13-hexahydro-1H,6H-bis([1,4]dithiocino)[6,7-b;6′,7′-e]pyrazine-κ3S:S′:S′′](nitrato-κO)silver(I)], [Ag(NO3)(C12H16N2S4)]n, (II), with the nitrate anion coordinating in a monodentate manner to the silver atom. The silver atom has a fourfold AgOS3 coordination sphere with a distorted shape. In the crystals of both complexes, the networks are linked by C—H⋯O hydrogen bonds, forming supramolecular frameworks. There are additional C—H⋯S contacts present in the supramolecular framework of II.
1. Chemical context
Ligands with mixed hard and soft binding characters, such as N and S donor atoms, are known to display diverse coordination properties, either by binding selectively to metal centers or by coordination to a wide range of metal cations giving rise to unusual coordination geometries. The title compounds 5,7-dihydro-1H,3H-dithieno[3,4-b:3′,4′-e]pyrazine (L1), and 3,4,8,10,11,13-hexahydro-1H,6H-bis([1,4]dithiocino)[6,7-b:6′,7′-e]pyrazine (L2), are new N2Sx (x = 2 in L1 and = 4 in L2) ligands designed for the formation of coordination polymers (Assoumatine, 1999). In L1, both the nitrogen and sulfur potential coordination sites are orientated exo to their respective rings. Because of this and the rigidity of the entire molecule, the potential chelating ability appears compromised, as stated by Shimizu and colleagues, who prepared a number of AgI polymer networks with the benzene analogue of L1, 5,7-dihydro-1H,3H-benzo[1,2-c:4,5-c′]dithiophene (Shimizu et al., 1998; 1999; Melcer et al., 2001). A search of the Cambridge Structural Database (Groom et al., 2016) revealed that L2 is unique and no benzene analogue or complexes of this analogue have been described. Using the nomenclature of the group of Shim Sung Lee (Siewe et al., 2014; Kim et al., 2016, 2018), L2 can be described as the bis-ortho-L regioisomer. Although, in view of the small size of the macrocycles, it is unlikely that either a meta- or a para-bis-L regioisomer could be formed.
2. Structural commentary
The molecular structure of ligand L1 is illustrated in Fig. 1. The molecule possesses inversion symmetry and consists of two sulfur atoms linked by a rigid tetra-2,3,5,6-methylenepyrazine unit. The molecule is planar (r.m.s. deviation = 0.008 Å) with the pyrazine ring being located about a center of symmetry. Both the nitrogen and sulfur potential coordination sites are orientated exo to their respective rings.
The molecular structure of ligand L2 is illustrated in Fig. 2. The molecule also possesses inversion symmetry with the pyrazine ring being located about a center of symmetry. It consists of two S–CH2–CH2–S chains linked by the central rigid tetra-2,3,5,6-methylenepyrazine unit, forming eight-membered rings. The configuration of these rings fits best to the definition for a twist-boat-chair (Evans & Boeyens, 1988; Spek, 2020), with a pseudo twofold rotation axis bisecting the C1—C2 and C4—C5 bonds and their symmetry equivalents. The molecule is step-shaped with six potential sites for coordination.
The reaction of L1 with silver nitrate leads to the formation of a two-dimensional coordination polymer, (I), with the nitrato anion bridging two equivalent silver atoms (Fig. 3). Selected bond lengths and bond angles are given in Table 1. The central pyrazine ring is situated about an inversion center and the silver atom Ag1 and atoms N2 and O2 of the nitrato anion lie on a twofold rotation axis. Atom Ag1 has a fourfold AgO2S2 coordination sphere with a distorted shape. The fourfold geometry index τ4 has a value of 0.74 (τ4 = 1 for a perfect tetrahedral geometry, 0 for a perfect square-planar geometry and 0.85 for perfect trigonal–pyramidal geometry; Yang et al., 2007). The intermediate value of 0.74 tends towards a see-saw arrangement. This seems reasonable in view of the fact that atom Ag1 is located on a twofold rotation axis.
|
The reaction of L2 with silver nitrate also leads to the formation of a two-dimensional coordination polymer (II, Fig. 4). Selected bond lengths and bond angles are given in Table 2. While the ligand has a step-shape in the solid state with one eight-membered ring directed above the pyrazine ring and the other below (Fig. 2), in the complex it has a boat shape with both eight-membered rings directed to the same side of the pyrazine ring (Fig. 4). The configuration of these rings again fits best to the definition for a twist-boat-chair (Evans & Boeyens, 1988; Spek, 2020), with a pseudo twofold rotation axis bisecting bonds C1—C2 and C7—C8 and bonds C3—C4 and C10—C11. The nitrato anion coordinates to the silver atom in a monodentate manner via atom O11 (Fig. 4, Table 2). The silver atom Ag1 has a fourfold AgOS3 coordination sphere with a distorted shape. The fourfold geometry index τ4 has a value of 0.75, which again tends towards a see-saw arrangement.
The pyrazine N atoms are not involved in coordination to the silver atom in either I or II; the silver atom prefers coordination to the S atoms in both complexes. The role of the nitrato anion in I is essential in forming the two-dimensional network, bridging two equivalent silver atoms, while in II the nitrato anion coordinates to atom Ag1 in a monodentate manner. There is a significant difference in the Ag—S bond lengths and the Ag—O bond lengths in compounds I and II (cf. Tables 1 and 2), which are discussed in §5. Database survey.
3. Supramolecular features
In the crystals of both L1 and L2, there are no significant intermolecular interactions present (Figs. 5 and 6, respectively).
In the crystal of I, the coordination networks lie parallel to the ac plane (Fig. 7) and are linked by C—H⋯O hydrogen bonds, forming a supramolecular framework (Fig. 8 and Table 3).
In the crystal of II, the coordination networks lie parallel to the ab plane (Fig. 9). They are linked by C—H⋯O and C—H⋯S hydrogen bonds, forming a supramolecular framework (Fig. 10 and Table 4).
4. Hirshfeld surface analysis and two-dimensional fingerprint plots
The Hirshfeld surface (HS) analyses (Spackman & Jayatilaka, 2009) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007) were performed with CrystalExplorer17 (Turner et al., 2017) following the protocol of Tiekink and collaborators (Tan et al., 2019). A summary of the short interatomic contacts in L1 and L2 is given in Table 5.
|
The Hirshfeld surfaces of L1 and L2 mapped over dnorm are given in Fig. 11a and b, respectively. They show that there are no short significant interatomic contacts present in the crystal of L1, while the red spots indicate that short contacts are significant in the crystal of L2.
The full two-dimensional fingerprint plots for L1 and L2 are given in Figs. 12 and 13, respectively. The principal intermolecular interactions for L1 are delineated into the following contacts: H⋯H at 41.7%, S⋯H/H⋯S at 25.3%, N⋯H/H⋯N at 17.1%, C⋯H/H⋯C at 6.5% and N⋯S at 3.7%. For L2, the principal intermolecular interactions are delineated into H⋯H contacts at 45.2%, S⋯H/H⋯S at 36.6%, N⋯H/H⋯N at 11.7%, C⋯H/H⋯C at 4.7% and S⋯S at 1.8%. The S⋯H/H⋯S contacts, with the sharp spikes at de + di ≃ 2.9 Å in Fig. 12c for L1 and at ≃ 2.80 Å in Fig. 13c for L2, make significant contributions, especially for L2, which corresponds to the indications given in Fig. 11b, the HS of L2 mapped over dnorm, and in Table 5. In Fig. 13e the sharp spikes at de + di ≃ 2.6 Å indicate the significant contribution of the C⋯H/H⋯C contacts in the crystal of L2.
5. Database survey
A search of the Cambridge Structural Database (CSD, Version 5.41, last update November 2019; Groom et al., 2016) for the benzene analogue of L1, i.e. 5,7-dihydro-1H,3H-benzo[1,2-c:4,5-c′]dithiophene, gave ten hits. Five compounds concern silver(I) coordination complexes involving various anions, viz. catena-[[μ2-5,7-dihydro-1H,3H-thieneo(3,4-f)(2)benzothiophene]bis(acetonitrile)silver(I) hexafluoridophosphate] (MIZHAE; Melcer et al., 2001), catena-[[μ3-1,2:4,5-dithiolo(c)benzene-S,S,S′]bis(acetonitrile)silver(I) tetrafluoridoborate] (NUTBUZ; Shimizu et al., 1998], catena-[[μ3-1,2:4,5-dithiolo(c)benzene-S,S,S′]benzonitrilosilver tetrafluoridoborate benzonitrile solvate] (NUTCAG; Shimizu et al., 1998)], catena-[[μ3-benzene-1,2:4,5-bis(3′,4′-thiolane)](p-tolylsulfonato)silver(I) benzene clathrate] (QACYUO; Shimizu et al., 1999) and catena-[bis(μ2-5,7-dihydro-1H,3H-thieno(3,4-f)(2)benzothiophene)bis(p-tosyloxy)disilver(I) benzene solvate] (QACYUO01; Melcer et al., 2001). The latter are two reports of the same compound, cf. unit-cell parameters and space group.
The compound MIZHAE is a three-dimensional coordination polymer with a fourfold geometry index τ4 value of 0.80 (close to a trigonal–pyramidal geometry) for the silver atom, which has an AgN2S2coordination sphere. NUTBUZ is a two-dimensional coordination polymer. Here, the silver atom has a fivefold AgN2S3 coordination sphere with a distorted shape; the fivefold geometry index τ5 is 0.77 (τ5 = 1 for perfect trigonal–pyramidal geometry and = 0 for perfect square-pyramidal geometry; Addison et al., 1984). NUTCAG is a two-dimensional coordination polymer with a τ4 value of 0.73 for the silver atom, which has an AgNS3 coordination sphere. QACYUO (and QACYUO0) is a two-dimensional coordination polymer, with the silver atom having a fourfold AgOS3 coordination sphere with a trigonal–pyramidal geometry, the fourfold geometry index τ4 being 0.83. The Ag—S bond lengths involving the fourfold coordinated silver atoms vary from 2.4708 (13) Å in NUTCAG to 2.6077 (7) Å in QACYUO/01. The values of the various Ag—S bond lengths in I and II fall within these limits (see Tables 1 and 2). While in the ligand L1 the five-membered thiophene rings are planar, in the above mentioned structures and in complex I they have envelope configurations with the S atom as the flap.
The nitrate anion can coordinate in at least ten different ways and is extremely useful for designing multi-dimensional coordination polymers, as shown by a search of the CSD. We have previously examined the role of the nitrate anion in the formation of coordination polymers when reporting on the results of the reaction of silver nitrate with some tetrakis-thioether-substituted pyrazine ligands (Assoumatine & Stoeckli-Evans, 2017). For the two-dimensional coordination polymer (CSD refcode XALPOS) poly[di-μ-nitrato-bis{μ-2,3,5,6-tetrakis[(phenylsulfanyl)methyl]pyrazine}disilver(I)] the Ag—O bond lengths vary from 2.507 (4) to 2.551 (4) Å. For the three-dimensional coordination polymer (XALPUY) poly[trinitrato{μ6-2,3,5,6-tetrakis[(pyridin-2-ylsulfanyl)methyl]pyrazine}trisilver(I)], the Ag—O bond lengths vary from 2.567 (5) to 2.752 (5) Å. The values observed for I and II, 2.5849 (15) and 2.492 (3) Å, respectively, are similar to those mentioned above.
A search of the CSD for the benzene analogue of L2, or complexes of this analogue, gave zero hits.
6. Synthesis and crystallization
The reagent tetra-2,3,5,6-bromomethyl-pyrazine (TBr) was first synthesized by Ferigo et al. (1994), and its has been reported (CSD refcode: TOJXUN; Assoumatine & Stoeckli-Evans, 2014). The IR spectra for ligands L1 and L2, and for complexes I and II, are given in Fig. S1 in the supporting information.
Synthesis of 5,7-dihydro-1H,3H-dithieno[3,4-b:3′,4′-e]pyrazine (L1):
Ligand L1 was first prepared by the reaction of TBr with Na2S·9H2O, using the procedure of Shimizu et al. (1998). This gave a crude brown solid, which was chromatographed on deactivated silica gel with CH2Cl2 as to yield 35% of a white solid.
The yield could be increased by as much as 11% using a method similar to that described by Boekelheide et al. (1973). Well-ground Na2S·9H2O (1.06 g, 4.42 mmol, Aldrich 99%) was dissolved in a solution of MeOH/CH2Cl2 (100 ml, 1/1 v/v) in a three-necked flask (500 ml) equipped with a reflux condenser topped by a CaCl2 drying tube, an addition funnel (50 ml) and a magnetic stirring bar. To this mixture was added slowly through the addition funnel a solution of TBr (1 g, 2.21 mmol) in CH2Cl2 (25 ml). The reaction mixture was stirred vigorously for 3 h. Removal of the solvent resulted in a brown residue that was extracted into CH2Cl2 (200 ml), washed with water (3 × 30 ml), dried over anhydrous MgSO4 and then, after filtration, evaporated to dryness. The resultant residue was chromatographed over deactivated silica gel using CH2Cl2 as The main eluted fraction was evaporated to give a white solid that was dried under vacuum yielding pure L1 (m.p. 518–521 K, with decomposition). Colourless rod-like crystals were formed from a concentrated solution of pure L1 in CH2Cl2, after standing for one week at 278 K.
1H NMR (CDCl3, 400 MHz): δ 4.22 (s, 8H, Pz–CH2–S) ppm. 13C NMR (CDCl3, 100 MHz): δ 152.30, 34.44 ppm. Analysis for C8H8N2S2 (Mr = 196.30 g mol−1). Calculated (%): C 48.95, H 4.11, N 14.27, S 32.67. Found (%): C 49.02, H 4.23, N 14.04, S 32.60. MS (EI, 70 eV), m/z (%): 196 ([M+], 100).
Synthesis of 3,4,8,10,11,13-hexahydro-1H,6H-bis([1,4]dithiocino)[6,7-b:6′,7′-e]pyrazine (L2):
A 500 ml three-necked flask was equipped with a reflux condenser, a 50 ml addition funnel, and a magnetic stirring bar. The entire system was purged and kept under a nitrogen atmosphere using vacuum line techniques. Then well-ground Cs2CO3 (3.52 g, 10.80 mmol, Fluka 99%) was suspended in DMF (250 ml) in the flask. To this well-stirred suspension was added dropwise through the addition funnel a solution of TBr (1 g, 2.21 mmol) and 1,2-ethanedithiol (0.4 ml, 4.76 mmol, 98%) dissolved in DMF (50 ml), at a rate of about 10 ml h−1. The mixture was stirred for a further 20 h and then filtered. The orange filtrate was evaporated under reduced pressure. The residue was extracted into CH2Cl2 (300 ml) then washed with water (3 × 30 ml), dried over anhydrous MgSO4 and then, after filtration, evaporated to dryness. The resultant residue was chromatographed over deactivated silica gel using CH2Cl2 as The main eluted fraction was evaporated to give a white solid that was dried under vacuum to obtain 0.35 g (50% yield) of pure L2 (m.p. 541–544 K, with decomposition). Slow evaporation at room temperature of a solution of L2 in CHCl3 in a 5 mm diameter glass tube gave colourless plate-like crystals.
1H NMR (CDCl3, 400 MHz): δ 4.08 (s, 8H, Pz–CH2–S), 2.92 (s, 8H, S–CH2–CH2–S) ppm. 13C NMR (CDCl3, 100 MHz): δ 151.15, 34.40, 34.09 ppm. Analysis for C12H16N2S4 (Mr = 316.54 g mol−1). Calculated (%): C 45.53, H 5.09, N 8.85, S 40.52. Found (%): C 45.34, H 5.30, N 8.68, S 40.33. MS (EI, 70 eV), m/z (%): 316 ([M+], 98.7).
Synthesis of complex I:
A solution of L1 (15 mg, 0.08 mmol) in THF (5 ml) was introduced into a 16 mm diameter glass tube and layered with MeCN (2 ml) as a buffer zone. Then a solution of AgNO3 (14 mg, 0.08 mmol) in MeCN (5 ml) was added very gently to avoid possible mixing. The glass tube was sealed and left in the dark at room temperature for at least two weeks, whereupon colourless needle-like crystals of complex I were isolated in the buffer zone.
Analysis for C8H8N3O3S2Ag (Mr = 366.18 g mol−1). Calculated (%): C 26.24, H 2.21, N 11.48, S 17.51. Found (%): C 26.27, H 2.10, N 11.29, S 17.19.
Synthesis of complex II:
A solution of L2 (20 mg, 0.06 mmol) in CH2Cl2 (10 ml) was introduced into a 16 mm diameter glass tube and layered with MeCN (2 ml) as a buffer zone. Then a solution of AgNO3 (10 mg, 0.06 mmol) in MeCN (5 ml) was added very gently to avoid possible mixing. The glass tube was sealed and left in the dark at room temperature for at least three weeks, whereupon thin, colourless plate-like crystals of complex II were isolated at the interface between the two solutions. No analytical data are available for this complex.
7. Refinement
Crystal data, data collection and structure . The C-bound H atoms were included in calculated positions and treated as riding on the parent atoms: C—H = 0.97–0.98 Å with Uiso(H) = 1.2Ueq(C). For L1, the rather high Rint value of 0.159 is due to the poor quality, viz. large mosaic spread, of the crystal.
details are summarized in Table 6
|
Supporting information
https://doi.org/10.1107/S205698902000362X/lh5951sup1.cif
contains datablocks L1, L2, I, II, global. DOI:Structure factors: contains datablock L1. DOI: https://doi.org/10.1107/S205698902000362X/lh5951L1sup2.hkl
Structure factors: contains datablock L2. DOI: https://doi.org/10.1107/S205698902000362X/lh5951L2sup3.hkl
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902000362X/lh5951Isup4.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S205698902000362X/lh5951IIsup5.hkl
For all structures, data collection: EXPOSE in IPDS1 (Stoe & Cie, 1998); cell
CELL in IPDS1 (Stoe & Cie, 1998); data reduction: INTEGRATE in IPDS1 (Stoe & Cie, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL-2018/3 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL-2018/3 (Sheldrick, 2015), PLATON (Spek, 2020) and publCIF (Westrip, 2010).[Ag(NO3)(C8H8N2S2)] | F(000) = 204 |
Mr = 196.28 | Dx = 1.619 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 4.1027 (4) Å | Cell parameters from 3541 reflections |
b = 12.1789 (18) Å | θ = 3.1–25.7° |
c = 8.1014 (8) Å | µ = 0.60 mm−1 |
β = 95.780 (12)° | T = 223 K |
V = 402.74 (8) Å3 | Rod, colourless |
Z = 2 | 0.45 × 0.13 × 0.10 mm |
STOE IPDS 1 diffractometer | 590 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.159 |
Plane graphite monochromator | θmax = 25.8°, θmin = 3.0° |
φ rotation scans | h = −4→4 |
3025 measured reflections | k = −14→14 |
744 independent reflections | l = −9→9 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.074 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.180 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.1296P)2] where P = (Fo2 + 2Fc2)/3 |
744 reflections | (Δ/σ)max < 0.001 |
55 parameters | Δρmax = 0.77 e Å−3 |
0 restraints | Δρmin = −0.55 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.1126 (2) | 0.62437 (7) | 0.34804 (9) | 0.0363 (5) | |
N1 | 0.4717 (8) | 0.3945 (2) | 0.0713 (4) | 0.0320 (7) | |
C1 | 0.3670 (8) | 0.4860 (3) | 0.1411 (3) | 0.0296 (9) | |
C2 | 0.3971 (9) | 0.5902 (3) | 0.0708 (4) | 0.0303 (8) | |
C3 | 0.2147 (9) | 0.4824 (3) | 0.3009 (3) | 0.0341 (9) | |
H3A | 0.368695 | 0.451919 | 0.389472 | 0.041* | |
H3B | 0.016898 | 0.436835 | 0.289632 | 0.041* | |
C4 | 0.2721 (10) | 0.6844 (3) | 0.1673 (4) | 0.0356 (9) | |
H4A | 0.098963 | 0.724060 | 0.099563 | 0.043* | |
H4B | 0.450057 | 0.735867 | 0.201262 | 0.043* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0477 (8) | 0.0408 (6) | 0.0219 (6) | 0.0041 (3) | 0.0106 (4) | −0.0011 (3) |
N1 | 0.0412 (18) | 0.0333 (14) | 0.0219 (15) | 0.0007 (11) | 0.0049 (11) | 0.0019 (10) |
C1 | 0.034 (2) | 0.0354 (18) | 0.0197 (17) | −0.0011 (12) | 0.0062 (13) | 0.0012 (11) |
C2 | 0.039 (2) | 0.0349 (17) | 0.0161 (15) | 0.0014 (14) | 0.0007 (12) | −0.0031 (12) |
C3 | 0.048 (2) | 0.0363 (17) | 0.0187 (18) | 0.0023 (14) | 0.0061 (15) | 0.0031 (12) |
C4 | 0.048 (2) | 0.0328 (17) | 0.0268 (16) | 0.0012 (14) | 0.0096 (15) | 0.0010 (12) |
S1—C4 | 1.817 (4) | C2—C4 | 1.507 (5) |
S1—C3 | 1.828 (3) | C3—H3A | 0.9800 |
N1—C2i | 1.332 (4) | C3—H3B | 0.9800 |
N1—C1 | 1.340 (4) | C4—H4A | 0.9800 |
C1—C2 | 1.401 (5) | C4—H4B | 0.9800 |
C1—C3 | 1.494 (4) | ||
C4—S1—C3 | 95.95 (14) | S1—C3—H3A | 110.5 |
C2i—N1—C1 | 115.0 (3) | C1—C3—H3B | 110.5 |
N1—C1—C2 | 122.5 (3) | S1—C3—H3B | 110.5 |
N1—C1—C3 | 121.4 (3) | H3A—C3—H3B | 108.7 |
C2—C1—C3 | 116.1 (3) | C2—C4—S1 | 106.3 (2) |
N1i—C2—C1 | 122.5 (3) | C2—C4—H4A | 110.5 |
N1i—C2—C4 | 122.0 (3) | S1—C4—H4A | 110.5 |
C1—C2—C4 | 115.5 (3) | C2—C4—H4B | 110.5 |
C1—C3—S1 | 106.1 (2) | S1—C4—H4B | 110.5 |
C1—C3—H3A | 110.5 | H4A—C4—H4B | 108.7 |
C2i—N1—C1—C2 | −0.8 (5) | N1—C1—C3—S1 | 179.8 (3) |
C2i—N1—C1—C3 | −179.9 (3) | C2—C1—C3—S1 | 0.7 (4) |
N1—C1—C2—N1i | 0.8 (6) | C4—S1—C3—C1 | −1.1 (3) |
C3—C1—C2—N1i | 180.0 (3) | N1i—C2—C4—S1 | 179.2 (3) |
N1—C1—C2—C4 | −178.9 (3) | C1—C2—C4—S1 | −1.0 (4) |
C3—C1—C2—C4 | 0.3 (5) | C3—S1—C4—C2 | 1.2 (3) |
Symmetry code: (i) −x+1, −y+1, −z. |
[Ag(NO3)(C12H16N2S4)] | F(000) = 664 |
Mr = 316.51 | Dx = 1.485 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 21.1618 (18) Å | Cell parameters from 5000 reflections |
b = 7.0585 (5) Å | θ = 3.0–25.9° |
c = 9.5057 (7) Å | µ = 0.65 mm−1 |
β = 94.47 (1)° | T = 223 K |
V = 1415.55 (19) Å3 | Colourless, plate |
Z = 4 | 0.40 × 0.30 × 0.10 mm |
STOE IPDS 1 diffractometer | 1174 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.029 |
Plane graphite monochromator | θmax = 25.9°, θmin = 3.0° |
φ rotation scans | h = −25→25 |
5086 measured reflections | k = −8→8 |
1367 independent reflections | l = −11→11 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0427P)2 + 0.461P] where P = (Fo2 + 2Fc2)/3 |
1367 reflections | (Δ/σ)max = 0.001 |
82 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.90795 (2) | 0.54315 (6) | 0.52645 (5) | 0.03312 (15) | |
S2 | 0.89795 (2) | 0.01187 (6) | 0.34452 (5) | 0.03987 (16) | |
N1 | 0.75497 (6) | 0.42931 (19) | 0.55990 (14) | 0.0268 (3) | |
C1 | 0.78592 (7) | 0.1989 (2) | 0.39521 (15) | 0.0253 (3) | |
C2 | 0.79056 (6) | 0.3798 (2) | 0.45558 (15) | 0.0246 (3) | |
C3 | 0.83585 (8) | 0.5281 (2) | 0.41003 (18) | 0.0303 (4) | |
H3A | 0.814637 | 0.651638 | 0.407231 | 0.036* | |
H3B | 0.847038 | 0.498872 | 0.314291 | 0.036* | |
C4 | 0.93325 (8) | 0.2996 (2) | 0.54130 (17) | 0.0323 (4) | |
H4A | 0.970847 | 0.293157 | 0.608187 | 0.039* | |
H4B | 0.899694 | 0.225955 | 0.581154 | 0.039* | |
C5 | 0.94907 (7) | 0.2061 (2) | 0.40278 (18) | 0.0319 (4) | |
H5A | 0.992794 | 0.159497 | 0.414165 | 0.038* | |
H5B | 0.947061 | 0.302840 | 0.328648 | 0.038* | |
C6 | 0.82558 (7) | 0.1326 (3) | 0.27995 (17) | 0.0332 (4) | |
H6A | 0.836729 | 0.242364 | 0.223784 | 0.040* | |
H6B | 0.800162 | 0.046620 | 0.217500 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0246 (2) | 0.0341 (2) | 0.0413 (3) | −0.01170 (15) | 0.00595 (17) | −0.01108 (17) |
S2 | 0.0336 (3) | 0.0307 (2) | 0.0562 (3) | −0.00329 (16) | 0.0090 (2) | −0.01143 (19) |
N1 | 0.0215 (6) | 0.0287 (7) | 0.0300 (7) | −0.0059 (5) | 0.0004 (5) | −0.0012 (5) |
C1 | 0.0196 (7) | 0.0326 (8) | 0.0231 (8) | −0.0055 (6) | −0.0017 (6) | 0.0008 (6) |
C2 | 0.0186 (7) | 0.0295 (8) | 0.0252 (8) | −0.0058 (6) | −0.0013 (6) | 0.0032 (6) |
C3 | 0.0266 (8) | 0.0289 (8) | 0.0356 (9) | −0.0071 (6) | 0.0044 (6) | 0.0035 (7) |
C4 | 0.0292 (8) | 0.0375 (9) | 0.0296 (8) | −0.0063 (7) | −0.0008 (6) | 0.0047 (7) |
C5 | 0.0226 (7) | 0.0330 (8) | 0.0402 (9) | −0.0016 (6) | 0.0039 (6) | −0.0010 (7) |
C6 | 0.0281 (8) | 0.0435 (9) | 0.0283 (8) | −0.0109 (7) | 0.0038 (6) | −0.0085 (7) |
S1—C4 | 1.8025 (17) | C3—H3A | 0.9800 |
S1—C3 | 1.8168 (17) | C3—H3B | 0.9800 |
S2—C5 | 1.8062 (16) | C4—C5 | 1.533 (2) |
S2—C6 | 1.8171 (18) | C4—H4A | 0.9800 |
N1—C2 | 1.338 (2) | C4—H4B | 0.9800 |
N1—C1i | 1.3443 (19) | C5—H5A | 0.9800 |
C1—C2 | 1.401 (2) | C5—H5B | 0.9800 |
C1—C6 | 1.506 (2) | C6—H6A | 0.9800 |
C2—C3 | 1.506 (2) | C6—H6B | 0.9800 |
C4—S1—C3 | 102.85 (8) | S1—C4—H4A | 108.5 |
C5—S2—C6 | 102.50 (8) | C5—C4—H4B | 108.5 |
C2—N1—C1i | 118.24 (14) | S1—C4—H4B | 108.5 |
N1i—C1—C2 | 120.67 (14) | H4A—C4—H4B | 107.5 |
N1i—C1—C6 | 115.54 (14) | C4—C5—S2 | 115.13 (11) |
C2—C1—C6 | 123.79 (13) | C4—C5—H5A | 108.5 |
N1—C2—C1 | 121.09 (13) | S2—C5—H5A | 108.5 |
N1—C2—C3 | 116.07 (14) | C4—C5—H5B | 108.5 |
C1—C2—C3 | 122.83 (14) | S2—C5—H5B | 108.5 |
C2—C3—S1 | 112.86 (11) | H5A—C5—H5B | 107.5 |
C2—C3—H3A | 109.0 | C1—C6—S2 | 113.75 (11) |
S1—C3—H3A | 109.0 | C1—C6—H6A | 108.8 |
C2—C3—H3B | 109.0 | S2—C6—H6A | 108.8 |
S1—C3—H3B | 109.0 | C1—C6—H6B | 108.8 |
H3A—C3—H3B | 107.8 | S2—C6—H6B | 108.8 |
C5—C4—S1 | 115.28 (11) | H6A—C6—H6B | 107.7 |
C5—C4—H4A | 108.5 | ||
C1i—N1—C2—C1 | −0.5 (2) | C4—S1—C3—C2 | 49.78 (13) |
C1i—N1—C2—C3 | −179.60 (14) | C3—S1—C4—C5 | 61.99 (13) |
N1i—C1—C2—N1 | 0.6 (2) | S1—C4—C5—S2 | −115.40 (11) |
C6—C1—C2—N1 | −178.56 (14) | C6—S2—C5—C4 | 74.34 (13) |
N1i—C1—C2—C3 | 179.55 (14) | N1i—C1—C6—S2 | −86.52 (14) |
C6—C1—C2—C3 | 0.4 (2) | C2—C1—C6—S2 | 92.63 (17) |
N1—C2—C3—S1 | 80.06 (15) | C5—S2—C6—C1 | −77.62 (13) |
C1—C2—C3—S1 | −98.99 (15) |
Symmetry code: (i) −x+3/2, −y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4B···S2ii | 0.98 | 3.02 | 3.7465 (17) | 132 |
C5—H5A···S1iii | 0.98 | 2.99 | 3.5248 (16) | 115 |
C6—H6A···S1iv | 0.98 | 2.92 | 3.8389 (18) | 157 |
Symmetry codes: (ii) x, −y, z+1/2; (iii) −x+2, −y+1, −z+1; (iv) x, −y+1, z−1/2. |
[C8H8N2S2]AgNO3 | F(000) = 360 |
Mr = 366.16 | Dx = 2.375 Mg m−3 |
Monoclinic, P2/n | Mo Kα radiation, λ = 0.71073 Å |
a = 3.8995 (3) Å | Cell parameters from 5000 reflections |
b = 6.3902 (6) Å | θ = 3.2–25.8° |
c = 20.5741 (18) Å | µ = 2.37 mm−1 |
β = 93.121 (9)° | T = 223 K |
V = 511.92 (8) Å3 | Needle, colourless |
Z = 2 | 0.45 × 0.10 × 0.10 mm |
STOE IPDS 1 diffractometer | 958 independent reflections |
Radiation source: fine-focus sealed tube | 905 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.021 |
φ rotation scans | θmax = 25.8°, θmin = 3.2° |
Absorption correction: multi-scan (MULABS; Spek, 2020) | h = −4→4 |
Tmin = 0.932, Tmax = 1.000 | k = −7→7 |
3795 measured reflections | l = −25→25 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.016 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.041 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.020P)2 + 0.3928P] where P = (Fo2 + 2Fc2)/3 |
958 reflections | (Δ/σ)max = 0.001 |
79 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Ag1 | 0.250000 | 0.73580 (3) | 0.750000 | 0.02211 (9) | |
S1 | −0.02263 (12) | 0.64417 (7) | 0.85176 (2) | 0.01302 (12) | |
O1 | 0.6178 (4) | 1.0451 (2) | 0.79516 (7) | 0.0274 (3) | |
O2 | 0.750000 | 1.3371 (3) | 0.750000 | 0.0262 (5) | |
N1 | 0.4947 (4) | 0.2874 (2) | 0.97975 (7) | 0.0136 (3) | |
N2 | 0.750000 | 1.1423 (3) | 0.750000 | 0.0157 (5) | |
C1 | 0.3461 (5) | 0.4408 (3) | 0.94406 (8) | 0.0126 (4) | |
C2 | 0.3516 (5) | 0.6499 (3) | 0.96379 (8) | 0.0124 (4) | |
C3 | 0.1666 (5) | 0.3949 (3) | 0.87926 (9) | 0.0143 (4) | |
H3A | −0.012208 | 0.288847 | 0.883653 | 0.017* | |
H3B | 0.330073 | 0.344062 | 0.848344 | 0.017* | |
C4 | 0.1801 (5) | 0.8040 (3) | 0.91737 (9) | 0.0148 (4) | |
H4A | 0.349176 | 0.899858 | 0.900192 | 0.018* | |
H4B | 0.007436 | 0.886025 | 0.939085 | 0.018* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.03440 (16) | 0.01965 (13) | 0.01297 (13) | 0.000 | 0.00761 (9) | 0.000 |
S1 | 0.0137 (2) | 0.0144 (2) | 0.0109 (2) | 0.00041 (16) | −0.00013 (16) | 0.00061 (15) |
O1 | 0.0383 (9) | 0.0218 (7) | 0.0230 (7) | −0.0058 (7) | 0.0090 (7) | 0.0021 (6) |
O2 | 0.0451 (14) | 0.0098 (9) | 0.0228 (10) | 0.000 | −0.0058 (9) | 0.000 |
N1 | 0.0155 (8) | 0.0134 (7) | 0.0118 (7) | −0.0009 (6) | 0.0015 (6) | 0.0001 (6) |
N2 | 0.0175 (12) | 0.0146 (11) | 0.0144 (11) | 0.000 | −0.0040 (9) | 0.000 |
C1 | 0.0127 (9) | 0.0145 (9) | 0.0106 (8) | −0.0012 (7) | 0.0021 (6) | 0.0009 (7) |
C2 | 0.0136 (9) | 0.0134 (9) | 0.0104 (8) | −0.0005 (7) | 0.0020 (7) | 0.0005 (7) |
C3 | 0.0175 (9) | 0.0125 (8) | 0.0126 (8) | 0.0007 (7) | −0.0014 (7) | −0.0010 (7) |
C4 | 0.0198 (10) | 0.0128 (8) | 0.0114 (8) | 0.0006 (7) | −0.0015 (7) | −0.0013 (7) |
Ag1—S1 | 2.4696 (5) | N1—C2ii | 1.339 (2) |
Ag1—S1i | 2.4696 (5) | C1—C2 | 1.397 (3) |
Ag1—O1 | 2.5849 (15) | C1—C3 | 1.501 (2) |
Ag1—O1i | 2.5849 (15) | C2—C4 | 1.503 (3) |
S1—C3 | 1.8322 (19) | C3—H3A | 0.9800 |
S1—C4 | 1.8368 (19) | C3—H3B | 0.9800 |
O1—N2 | 1.2517 (18) | C4—H4A | 0.9800 |
O2—N2 | 1.245 (3) | C4—H4B | 0.9800 |
N1—C1 | 1.337 (2) | ||
S1—Ag1—S1i | 152.57 (2) | C2—C1—C3 | 116.38 (16) |
S1—Ag1—O1 | 97.62 (3) | N1ii—C2—C1 | 122.49 (17) |
S1i—Ag1—O1 | 103.30 (4) | N1ii—C2—C4 | 121.21 (16) |
S1—Ag1—O1i | 103.30 (3) | C1—C2—C4 | 116.29 (16) |
S1i—Ag1—O1i | 97.62 (3) | C1—C3—S1 | 105.36 (12) |
O1—Ag1—O1i | 80.24 (7) | C1—C3—H3A | 110.7 |
C3—S1—C4 | 96.12 (9) | S1—C3—H3A | 110.7 |
C3—S1—Ag1 | 106.45 (6) | C1—C3—H3B | 110.7 |
C4—S1—Ag1 | 107.66 (6) | S1—C3—H3B | 110.7 |
N2—O1—Ag1 | 110.82 (11) | H3A—C3—H3B | 108.8 |
C1—N1—C2ii | 114.66 (16) | C2—C4—S1 | 105.17 (12) |
O2—N2—O1 | 119.74 (11) | C2—C4—H4A | 110.7 |
O2—N2—O1iii | 119.74 (11) | S1—C4—H4A | 110.7 |
O1—N2—O1iii | 120.5 (2) | C2—C4—H4B | 110.7 |
N1—C1—C2 | 122.85 (17) | S1—C4—H4B | 110.7 |
N1—C1—C3 | 120.77 (16) | H4A—C4—H4B | 108.8 |
Ag1—O1—N2—O2 | 136.46 (5) | N1—C1—C3—S1 | 175.73 (14) |
Ag1—O1—N2—O1iii | −43.54 (5) | C2—C1—C3—S1 | −5.08 (19) |
C2ii—N1—C1—C2 | 0.3 (3) | C4—S1—C3—C1 | 7.26 (14) |
C2ii—N1—C1—C3 | 179.41 (16) | Ag1—S1—C3—C1 | 117.73 (11) |
N1—C1—C2—N1ii | −0.3 (3) | N1ii—C2—C4—S1 | −175.17 (14) |
C3—C1—C2—N1ii | −179.47 (16) | C1—C2—C4—S1 | 5.9 (2) |
N1—C1—C2—C4 | 178.56 (17) | C3—S1—C4—C2 | −7.54 (14) |
C3—C1—C2—C4 | −0.6 (2) | Ag1—S1—C4—C2 | −116.99 (11) |
Symmetry codes: (i) −x+1/2, y, −z+3/2; (ii) −x+1, −y+1, −z+2; (iii) −x+3/2, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···O1iv | 0.98 | 2.50 | 3.379 (2) | 150 |
C4—H4A···O1 | 0.98 | 2.62 | 3.475 (2) | 146 |
Symmetry code: (iv) x, y−1, z. |
[C12H16N2S4]AgNO3 | F(000) = 976 |
Mr = 486.39 | Dx = 1.933 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0777 (6) Å | Cell parameters from 5000 reflections |
b = 12.0654 (7) Å | θ = 2.1–25.9° |
c = 19.5725 (18) Å | µ = 1.72 mm−1 |
β = 90.446 (10)° | T = 293 K |
V = 1671.3 (2) Å3 | Plate, colourless |
Z = 4 | 0.50 × 0.23 × 0.08 mm |
STOE IPDS 1 diffractometer | 3222 independent reflections |
Radiation source: fine-focus sealed tube | 2226 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.051 |
φ rotation scans | θmax = 25.9°, θmin = 2.7° |
Absorption correction: multi-scan (MULABS; Spek, 2020) | h = −8→8 |
Tmin = 0.939, Tmax = 1.000 | k = −14→14 |
12808 measured reflections | l = −23→23 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 0.85 | w = 1/[σ2(Fo2) + (0.0288P)2] where P = (Fo2 + 2Fc2)/3 |
3222 reflections | (Δ/σ)max < 0.001 |
208 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Ag1 | 0.13078 (4) | −0.29440 (2) | 0.19436 (2) | 0.04241 (10) | |
S1 | 0.24146 (12) | −0.10620 (8) | 0.24454 (5) | 0.0373 (2) | |
S2 | 0.77716 (12) | 0.01162 (8) | 0.28097 (4) | 0.0348 (2) | |
S3 | −0.06576 (11) | 0.27177 (7) | 0.42666 (4) | 0.0339 (2) | |
S4 | 0.47060 (13) | 0.37232 (8) | 0.47535 (5) | 0.0393 (2) | |
N1 | 0.1835 (4) | 0.0237 (2) | 0.40414 (13) | 0.0291 (6) | |
N2 | 0.5521 (4) | 0.0911 (2) | 0.42978 (13) | 0.0286 (6) | |
C1 | 0.3289 (4) | −0.0297 (3) | 0.37562 (15) | 0.0274 (7) | |
C2 | 0.5158 (4) | 0.0053 (3) | 0.38798 (15) | 0.0258 (7) | |
C3 | 0.4069 (4) | 0.1436 (3) | 0.45887 (15) | 0.0251 (7) | |
C4 | 0.2197 (4) | 0.1106 (3) | 0.44487 (15) | 0.0263 (7) | |
C5 | 0.2793 (5) | −0.1318 (3) | 0.33509 (17) | 0.0358 (8) | |
H5A | 0.165563 | −0.164238 | 0.353851 | 0.043* | |
H5B | 0.380341 | −0.185522 | 0.340408 | 0.043* | |
C6 | 0.6852 (5) | −0.0512 (3) | 0.35795 (16) | 0.0329 (8) | |
H6A | 0.651804 | −0.127495 | 0.347866 | 0.039* | |
H6B | 0.785052 | −0.052515 | 0.392170 | 0.039* | |
C7 | 0.5692 (5) | 0.0204 (3) | 0.22688 (18) | 0.0426 (9) | |
H7A | 0.477204 | 0.067732 | 0.248948 | 0.051* | |
H7B | 0.603872 | 0.055461 | 0.184170 | 0.051* | |
C8 | 0.4763 (5) | −0.0915 (3) | 0.21101 (18) | 0.0445 (10) | |
H8A | 0.555159 | −0.150061 | 0.229659 | 0.053* | |
H8B | 0.471027 | −0.101211 | 0.161836 | 0.053* | |
C9 | 0.0521 (4) | 0.1650 (3) | 0.47689 (16) | 0.0307 (8) | |
H9A | 0.092472 | 0.197692 | 0.519870 | 0.037* | |
H9B | −0.039749 | 0.107962 | 0.487395 | 0.037* | |
C10 | 0.1189 (5) | 0.3706 (3) | 0.40868 (19) | 0.0465 (10) | |
H10A | 0.208798 | 0.336051 | 0.378179 | 0.056* | |
H10B | 0.063285 | 0.432988 | 0.384615 | 0.056* | |
C11 | 0.2260 (5) | 0.4144 (3) | 0.4709 (2) | 0.0446 (10) | |
H11A | 0.162698 | 0.389116 | 0.511779 | 0.054* | |
H11B | 0.220446 | 0.494733 | 0.470435 | 0.054* | |
C12 | 0.4591 (5) | 0.2326 (3) | 0.50841 (16) | 0.0310 (8) | |
H12A | 0.581414 | 0.214425 | 0.528093 | 0.037* | |
H12B | 0.368141 | 0.231524 | 0.545226 | 0.037* | |
O11 | −0.1700 (4) | −0.2945 (3) | 0.25969 (17) | 0.0690 (9) | |
O12 | −0.2807 (5) | −0.3358 (3) | 0.35741 (16) | 0.0861 (11) | |
O13 | 0.0187 (5) | −0.3523 (3) | 0.33897 (16) | 0.0757 (9) | |
N10 | −0.1430 (5) | −0.3274 (3) | 0.31906 (19) | 0.0530 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.04418 (16) | 0.03874 (17) | 0.04419 (16) | 0.00539 (15) | −0.00744 (11) | −0.00304 (14) |
S1 | 0.0316 (5) | 0.0397 (6) | 0.0405 (5) | −0.0017 (4) | −0.0032 (4) | −0.0104 (4) |
S2 | 0.0278 (5) | 0.0356 (6) | 0.0413 (5) | −0.0012 (4) | 0.0058 (4) | −0.0033 (4) |
S3 | 0.0279 (4) | 0.0339 (5) | 0.0399 (5) | 0.0004 (4) | −0.0040 (3) | −0.0003 (4) |
S4 | 0.0372 (5) | 0.0287 (5) | 0.0519 (6) | −0.0055 (4) | −0.0073 (4) | −0.0004 (4) |
N1 | 0.0302 (15) | 0.0290 (17) | 0.0282 (14) | −0.0054 (13) | 0.0028 (12) | −0.0022 (12) |
N2 | 0.0258 (14) | 0.0285 (17) | 0.0316 (15) | 0.0003 (12) | −0.0009 (11) | 0.0027 (12) |
C1 | 0.0330 (18) | 0.0262 (19) | 0.0231 (16) | −0.0051 (15) | 0.0021 (14) | −0.0008 (14) |
C2 | 0.0311 (17) | 0.0220 (18) | 0.0242 (16) | −0.0009 (15) | −0.0008 (13) | 0.0013 (13) |
C3 | 0.0309 (18) | 0.0196 (18) | 0.0249 (16) | −0.0026 (14) | −0.0009 (13) | 0.0024 (13) |
C4 | 0.0340 (18) | 0.0227 (18) | 0.0222 (16) | −0.0017 (15) | 0.0016 (13) | 0.0020 (13) |
C5 | 0.040 (2) | 0.028 (2) | 0.040 (2) | −0.0070 (17) | 0.0053 (16) | −0.0069 (15) |
C6 | 0.0317 (18) | 0.030 (2) | 0.0373 (19) | 0.0046 (15) | −0.0020 (15) | 0.0016 (15) |
C7 | 0.042 (2) | 0.051 (3) | 0.034 (2) | −0.0075 (19) | −0.0032 (16) | 0.0043 (17) |
C8 | 0.043 (2) | 0.055 (3) | 0.036 (2) | −0.0053 (19) | −0.0005 (16) | −0.0116 (17) |
C9 | 0.0309 (17) | 0.031 (2) | 0.0305 (18) | −0.0019 (15) | 0.0047 (14) | 0.0017 (14) |
C10 | 0.046 (2) | 0.040 (2) | 0.053 (2) | −0.0089 (19) | −0.0150 (18) | 0.0132 (19) |
C11 | 0.042 (2) | 0.027 (2) | 0.065 (3) | −0.0001 (17) | −0.0138 (19) | −0.0052 (18) |
C12 | 0.0354 (18) | 0.029 (2) | 0.0286 (17) | −0.0012 (15) | −0.0050 (14) | −0.0029 (14) |
O11 | 0.0629 (19) | 0.068 (2) | 0.077 (2) | 0.0157 (18) | 0.0216 (16) | 0.0230 (19) |
O12 | 0.085 (2) | 0.104 (3) | 0.070 (2) | −0.020 (2) | 0.0425 (19) | −0.0283 (19) |
O13 | 0.063 (2) | 0.085 (3) | 0.079 (2) | −0.0113 (19) | −0.0004 (17) | −0.0053 (18) |
N10 | 0.055 (2) | 0.039 (2) | 0.066 (3) | −0.0064 (17) | 0.021 (2) | −0.0154 (17) |
Ag1—S1 | 2.5927 (10) | C5—H5A | 0.9700 |
Ag1—S2i | 2.4760 (10) | C5—H5B | 0.9700 |
Ag1—S3ii | 2.5382 (9) | C6—H6A | 0.9700 |
Ag1—O11 | 2.492 (3) | C6—H6B | 0.9700 |
S1—C8 | 1.801 (4) | C7—C8 | 1.533 (5) |
S1—C5 | 1.817 (3) | C7—H7A | 0.9700 |
S2—C7 | 1.809 (4) | C7—H7B | 0.9700 |
S2—C6 | 1.812 (3) | C8—H8A | 0.9700 |
S3—C10 | 1.805 (4) | C8—H8B | 0.9700 |
S3—C9 | 1.819 (3) | C9—H9A | 0.9700 |
S4—C11 | 1.806 (4) | C9—H9B | 0.9700 |
S4—C12 | 1.807 (3) | C10—C11 | 1.524 (5) |
N1—C1 | 1.340 (4) | C10—H10A | 0.9700 |
N1—C4 | 1.341 (4) | C10—H10B | 0.9700 |
N2—C3 | 1.338 (4) | C11—H11A | 0.9700 |
N2—C2 | 1.343 (4) | C11—H11B | 0.9700 |
C1—C2 | 1.408 (4) | C12—H12A | 0.9700 |
C1—C5 | 1.505 (4) | C12—H12B | 0.9700 |
C2—C6 | 1.503 (4) | O11—N10 | 1.241 (4) |
C3—C4 | 1.409 (4) | O12—N10 | 1.239 (4) |
C3—C12 | 1.491 (4) | O13—N10 | 1.243 (4) |
C4—C9 | 1.498 (4) | ||
S2i—Ag1—S1 | 132.51 (3) | H6A—C6—H6B | 107.5 |
S3ii—Ag1—S1 | 97.47 (3) | C8—C7—S2 | 114.4 (3) |
S2i—Ag1—S3ii | 121.65 (3) | C8—C7—H7A | 108.7 |
O11—Ag1—S1 | 93.62 (8) | S2—C7—H7A | 108.7 |
S2i—Ag1—O11 | 97.12 (8) | C8—C7—H7B | 108.7 |
O11—Ag1—S3ii | 109.25 (8) | S2—C7—H7B | 108.7 |
C8—S1—C5 | 104.04 (16) | H7A—C7—H7B | 107.6 |
C8—S1—Ag1 | 103.02 (12) | C7—C8—S1 | 114.1 (3) |
C5—S1—Ag1 | 105.21 (11) | C7—C8—H8A | 108.7 |
C7—S2—C6 | 102.43 (16) | S1—C8—H8A | 108.7 |
C7—S2—Ag1iii | 105.67 (13) | C7—C8—H8B | 108.7 |
C6—S2—Ag1iii | 109.21 (12) | S1—C8—H8B | 108.7 |
C10—S3—C9 | 104.08 (16) | H8A—C8—H8B | 107.6 |
C10—S3—Ag1iv | 98.75 (13) | C4—C9—S3 | 116.5 (2) |
C9—S3—Ag1iv | 111.15 (11) | C4—C9—H9A | 108.2 |
C11—S4—C12 | 103.52 (17) | S3—C9—H9A | 108.2 |
C1—N1—C4 | 118.7 (3) | C4—C9—H9B | 108.2 |
C3—N2—C2 | 118.7 (3) | S3—C9—H9B | 108.2 |
N1—C1—C2 | 120.5 (3) | H9A—C9—H9B | 107.3 |
N1—C1—C5 | 115.9 (3) | C11—C10—S3 | 115.5 (3) |
C2—C1—C5 | 123.5 (3) | C11—C10—H10A | 108.4 |
N2—C2—C1 | 120.7 (3) | S3—C10—H10A | 108.4 |
N2—C2—C6 | 116.0 (3) | C11—C10—H10B | 108.4 |
C1—C2—C6 | 123.2 (3) | S3—C10—H10B | 108.4 |
N2—C3—C4 | 120.5 (3) | H10A—C10—H10B | 107.5 |
N2—C3—C12 | 115.5 (3) | C10—C11—S4 | 114.3 (3) |
C4—C3—C12 | 123.9 (3) | C10—C11—H11A | 108.7 |
N1—C4—C3 | 120.8 (3) | S4—C11—H11A | 108.7 |
N1—C4—C9 | 116.3 (3) | C10—C11—H11B | 108.7 |
C3—C4—C9 | 122.8 (3) | S4—C11—H11B | 108.7 |
C1—C5—S1 | 114.0 (2) | H11A—C11—H11B | 107.6 |
C1—C5—H5A | 108.7 | C3—C12—S4 | 116.8 (2) |
S1—C5—H5A | 108.7 | C3—C12—H12A | 108.1 |
C1—C5—H5B | 108.7 | S4—C12—H12A | 108.1 |
S1—C5—H5B | 108.7 | C3—C12—H12B | 108.1 |
H5A—C5—H5B | 107.6 | S4—C12—H12B | 108.1 |
C2—C6—S2 | 115.3 (2) | H12A—C12—H12B | 107.3 |
C2—C6—H6A | 108.4 | N10—O11—Ag1 | 110.8 (2) |
S2—C6—H6A | 108.4 | O12—N10—O11 | 118.5 (4) |
C2—C6—H6B | 108.4 | O12—N10—O13 | 121.1 (4) |
S2—C6—H6B | 108.4 | O11—N10—O13 | 120.4 (3) |
C4—N1—C1—C2 | −0.4 (4) | C1—C2—C6—S2 | 97.0 (3) |
C4—N1—C1—C5 | 175.3 (3) | C7—S2—C6—C2 | −52.5 (3) |
C3—N2—C2—C1 | −0.8 (4) | Ag1iii—S2—C6—C2 | 59.2 (3) |
C3—N2—C2—C6 | −179.0 (3) | C6—S2—C7—C8 | −60.0 (3) |
N1—C1—C2—N2 | 1.6 (5) | Ag1iii—S2—C7—C8 | −174.3 (2) |
C5—C1—C2—N2 | −173.7 (3) | S2—C7—C8—S1 | 115.8 (3) |
N1—C1—C2—C6 | 179.7 (3) | C5—S1—C8—C7 | −76.5 (3) |
C5—C1—C2—C6 | 4.3 (5) | Ag1—S1—C8—C7 | 173.9 (2) |
C2—N2—C3—C4 | −1.1 (4) | N1—C4—C9—S3 | −86.5 (3) |
C2—N2—C3—C12 | 175.8 (3) | C3—C4—C9—S3 | 96.9 (3) |
C1—N1—C4—C3 | −1.6 (4) | C10—S3—C9—C4 | −56.6 (3) |
C1—N1—C4—C9 | −178.3 (3) | Ag1iv—S3—C9—C4 | 48.7 (3) |
N2—C3—C4—N1 | 2.4 (4) | C9—S3—C10—C11 | −54.1 (3) |
C12—C3—C4—N1 | −174.3 (3) | Ag1iv—S3—C10—C11 | −168.6 (3) |
N2—C3—C4—C9 | 178.9 (3) | S3—C10—C11—S4 | 113.1 (3) |
C12—C3—C4—C9 | 2.2 (5) | C12—S4—C11—C10 | −79.7 (3) |
N1—C1—C5—S1 | 92.7 (3) | N2—C3—C12—S4 | 94.2 (3) |
C2—C1—C5—S1 | −91.7 (3) | C4—C3—C12—S4 | −89.0 (3) |
C8—S1—C5—C1 | 77.0 (3) | C11—S4—C12—C3 | 78.9 (3) |
Ag1—S1—C5—C1 | −175.0 (2) | Ag1—O11—N10—O12 | −177.6 (3) |
N2—C2—C6—S2 | −84.9 (3) | Ag1—O11—N10—O13 | 1.7 (4) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) −x, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O13 | 0.97 | 2.51 | 3.239 (5) | 132 |
C6—H6A···O12v | 0.97 | 2.56 | 3.442 (5) | 150 |
C8—H8B···S4i | 0.97 | 2.74 | 3.696 (4) | 169 |
C11—H11B···S4vi | 0.97 | 2.91 | 3.508 (4) | 121 |
C12—H12B···O12vii | 0.97 | 2.37 | 3.177 (4) | 140 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (v) x+1, y, z; (vi) −x+1, −y+1, −z+1; (vii) −x, −y, −z+1. |
Atom1 | Atom2 | Length | Length-vdW | Symm. op. 1 | Symm. op. 2 |
L1 | |||||
H3A | H3A | 2.313 | -0.087 | 1 - x, 1 - y, -z | x, y, -1 + z |
H3B | C1 | 2.876 | -0.024 | x, y, z | -1 + x, y, z |
S1 | H3A | 3.000 | 0.000 | 1 - x, 1 - y, -z | x, y, -1 + z |
H3B | N1 | 2.757 | 0.007 | x, y, z | -1 + x, y, z |
S1 | C3 | 3.515 | 0.015 | x, y, z | -x, 1 - y, 1 - z |
N1 | S1 | 3.379 | 0.029 | x, y, z | 1/2 - x, -1/2 + y, 1/2 - z |
S1 | C2 | 3.537 | 0.037 | x, y, z | -1 + x, y, z |
H3B | H4B | 2.452 | 0.052 | x, y, z | 1/2 - x, -1/2 + y, 1/2 - z |
C3 | H3A | 2.998 | 0.098 | 1 - x, 1 - y, -z | x, y, -1 + z |
L2 | |||||
H6B | C2 | 2.699 | -0.201 | x, y, z | 3/2 - x, -1/2 + y, 1/2 - z |
S1 | H6A | 2.919 | -0.081 | 3/2 - x, 1/2 - y, 1 - z | 1.5-x,-1/2+y,1/2-z |
S1 | H5A | 2.992 | -0.008 | 3/2 - x, 1/2 - y, 1 - z | -1/2 + x, -1/2 + y, z |
S2 | H4B | 3.017 | 0.017 | x, y, z | x, -y, -1/2 + z |
S1 | C5 | 3.525 | 0.025 | 3/2 - x, 1/2 - y, 1 - z | -1/2 + x, -1/2 + y, z |
Note: (a) Calculated using Mercury (Macrae et al., 2020). |
Acknowledgements
HSE is grateful to the University of Neuchâtel for their support over the years.
Funding information
Funding for this research was provided by the Swiss National Science Foundation and the University of Neuchâtel.
References
Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Assoumatine, T. (1999). PhD Thesis, University of Neuchâtel, Switzerland. Google Scholar
Assoumatine, T. & Stoeckli-Evans, H. (2014). Acta Cryst. E70, 51–53. CSD CrossRef CAS IUCr Journals Google Scholar
Assoumatine, T. & Stoeckli-Evans, H. (2017). Acta Cryst. E73, 434–440. Web of Science CSD CrossRef IUCr Journals Google Scholar
Boekelheide, V. & Hollins, R. A. J. (1973). J. Am. Chem. Soc. 95, 3201–3208. CrossRef CAS Web of Science Google Scholar
Evans, D. G. & Boeyens, J. C. A. (1988). Acta Cryst. B44, 663–671. CrossRef CAS Web of Science IUCr Journals Google Scholar
Ferigo, M., Bonhôte, P., Marty, W. & Stoeckli-Evans, H. (1994). J. Chem. Soc. Dalton Trans. pp. 1549–1554. CSD CrossRef Web of Science Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Kim, S., Siewe, A. D., Lee, E., Ju, H., Park, I.-H., Jung, J. H., Habata, Y. & Lee, S. S. (2018). Cryst. Growth Des. 18, 2424–2431. Web of Science CSD CrossRef CAS Google Scholar
Kim, S., Siewe, A. D., Lee, E., Ju, H., Park, I.-H., Park, K.-M., Ikeda, M., Habata, Y. & Lee, S. S. (2016). Inorg. Chem. 55, 2018–2022. Web of Science CSD CrossRef CAS PubMed Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. Web of Science CrossRef Google Scholar
Melcer, N. J., Enright, G. D., Ripmeester, J. A. & Shimizu, G. K. H. (2001). Inorg. Chem. 40, 4641–4648. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shimizu, G. K. H., Enright, G. D., Ratcliffe, C. I. & Ripmeester, J. A. (1999). Chem. Commun. pp. 461–462. Web of Science CSD CrossRef Google Scholar
Shimizu, G. K. H., Enright, G. D., Ratcliffe, C. I., Ripmeester, J. A. & Wayner, D. D. M. (1998). Angew. Chem. Int. Ed. 37, 1407–1409. CrossRef CAS Google Scholar
Siewe, A. D., Kim, J.-Y., Kim, S., Park, I.-H. & Lee, S. S. (2014). Inorg. Chem. 53, 393–398. Web of Science CSD CrossRef CAS PubMed Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Stoe & Cie (1998). IPDS-1 Software. Stoe & Cie GmbH, Darmstadt, Germany. Google Scholar
Tan, S. L., Jotani, M. M. & Tiekink, E. R. T. (2019). Acta Cryst. E75, 308–318. Web of Science CrossRef IUCr Journals Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia. https://hirshfeldsurface.net Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, L., Powell, D. R. & Houser, R. P. (2007). Dalton Trans. pp. 955–964. Web of Science CSD CrossRef PubMed CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.