Coordination chemistry of nitrile-functionalized mixed thia-aza macrocycles [9]aneN2S and [9]aneNS2 towards silver(I)

Blake, A.J.; Lippolis, V.; Schröder, M.

doi:10.1107/S205322962200105X

research papers

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 78| Part 3| March 2022| Pages 169-175

https://doi.org/10.1107/S205322962200105X

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Coordination chemistry of nitrile-functionalized mixed thia-aza macrocycles [9]aneN₂S and [9]aneNS₂ towards silver(I)

Alexander J. Blake,^a ^* Vito Lippolis ^b and Martin Schröder ^a,^c

^aSchool of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK, ^bDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 Bivio per Sestu, Monserrato (CA), 09042, Italy, and ^cDepartment of Chemistry, The University of Manchester, Manchester, M13 9PL, UK
^*Correspondence e-mail: alexanderjohnblake@outlook.com

Edited by A. R. Kennedy, University of Strathclyde, United Kingdom (Received 11 January 2022; accepted 30 January 2022; online 14 February 2022)

The coordination chemistry towards silver(I) of the small-ring macrocycles [9]aneN₂S (1-thia-4,7-diazacyclononane) and [9]aneNS₂ (1,4-dithia-7-azacyclononane) incorporating nitrile-functionalized pendant arms is considered both in the presence and the absence of exogenous bridging ligands. The aim is to understand the influence of the number and length of the pendant arms on the nuclearity and dimensionality of the resulting complexes. The X-ray crystal structures of the complexes bis[4,7-bis(cyanomethyl)-1-thia-4,7-diazacyclononane-κ³N,N′,S]silver(I) tetrafluoridoborate, [Ag(C₁₀H₁₆N₄S)₂]BF₄ or [Ag(L¹)₂]BF₄, [4,7-bis(2-cyanoethyl)-1-thia-4,7-diazacyclononane-κ³N,N′,S](thiocyanato-κS)silver(I), [Ag(C₁₂H₂₀N₄S)(NCS)] or [Ag(L²)(SCN)], and μ-thiocyanato-κ²S:S-bis{[7-(2-cyanoethyl)-1,4-dithia-7-azacyclononane-κ³N,S,S′]silver(I)} tetrafluoridoborate, [Ag₂(C₉H₁₆N₂S₂)₂(SCN)]BF₄ or [Ag₂(L³)₂(μ-SCN)]BF₄, are discussed in relation to analogous compounds in the literature.

Keywords: macrocylic ligands; silver(I); thiocyanate ligand; nitrile derivatives; crystal structure.

CCDC references: 2145502; 2145501; 2145500

1. Introduction

In previously published articles (Tei et al., 1998 , 2002 ), we have considered the nitrile-functionalized pendant-arm derivatives of mixed-donor macrocycles as multidentate ligands for the synthesis of multidimensional polymeric complexes with silver(I). We argued that nitrile-containing pendant arms would promote exocyclic rather than endocyclic complexation, thereby preventing the formation of mononuclear complexes in favour of coordination polymers. The results confirmed this hypothesis, with the nitrile groups playing an active role in linking different silver(I) centres in the obtained polynuclear complexes whose dimensionality is strictly dependent upon the number of nitrile-functionalized pendant arms present in the ligand, upon their length, and upon the donor set and ring size of the macrocyclic framework. However, in the presence CN⁻, the coordination site left free on the metal centre by the macrocyclic moiety of the nitrile-functionalized ligands in Scheme 1 [L¹ = 4,7-bis(cyanomethyl)-1-thia-4,7-diazacyclononane, L² = 4,7-bis(2-cyanoethyl)-1-thia-4,7-diazacyclononane and L³ = 7-(2-cyanoethyl)-1,4-dithia-7-azacyclononane] was occupied by the exogenous anionic ligand instead of nitrile groups, thus preventing the formation of inorganic polymers involving the pendant nitriles and favouring the isolation of unusual compounds (Lippolis et al., 1999 ; Blake et al., 1998 ).

In particular, while the discrete binuclear complex [Ag₂(L¹)₂(μ-CN)]BF₄·MeCN, featuring a side-on two-electron (σ) μ₂-κC:κC bridging cyanide, was isolated from the reaction of L¹, AgBF₄ and ⁿBu₄NCN in a 1:1:0.5 molar ratio, the complexes [Ag₂(L²)₂(μ-CN)]BF₄ and [Ag₂(L³)₂(μ-CN)]BF₄, exhibiting a CN⁻ ligand bridging two metal centres in a linear four-electron (σ + π) μ₂-κC:κN manner (Vahrenkamp et al., 1997 ), were isolated starting from L² and L³, respectively, under the same experimental conditions (Lippolis et al., 1999). [Ag₂(L¹)₂(μ-CN)]BF₄·MeCN was the first discrete binuclear complex, and is still the only one reported in the literature, featuring a pure two-electron (σ) μ₂-κC:κC bridging cyanide, to be structurally characterized. This result was initially attributed to the different length of the pendant arms in the macrocyclic ligands employed; the presence of shorter and less sterically demanding arms in L¹ as compared to L² would allow a closer approach of two [Ag(L¹)]⁺ units in the binuclear complex featuring a side-on bridging cyanide. Herein we report a further development of this chemistry from a crystallographic point of view, with the aim of better understanding the role played by the length of the aliphatic chain in nitrile-functionalized derivatives of the small-ring macrocycles [9]aneN₂S (1-thia-4,7-diazacyclononane) and [9]aneNS₂ (1,4-dithia-7-azacyclononane) in determining the coordination chemistry towards silver(I) both in the absence or in the presence of exogenous bridging ligands.

The compounds studied are [Ag(L¹)₂]BF₄, [Ag(L²)(SCN)] and [Ag₂(L³)₂(μ-SCN)]BF₄ (Scheme 2).

2. Experimental

2.1. Material and methods

All starting materials were obtained from Aldrich and were used without further purification. Microanalyses were performed by the University of Nottingham School of Chemistry Microanalytical Service. IR spectra were recorded as KBr discs using a PerkinElmer 598 spectrometer over the range 200–4000 cm⁻¹. Fast atom bombardment (FAB) mass spectra were recorded at the EPSRC Centre for Mass Spectroscopy at the University of Swansea, UK.

2.2. Synthesis and crystallization

4,7-Bis(cyanomethyl)-1-thia-4,7-diazacyclononane (L¹), 4,7-bis(2-cyanoethyl)-1-thia-4,7-diazacyclononane (L²) and 7-(2-cyanoethyl)-1,4-dithia-7-azacyclononane (L³) were prepared according to adaptations of procedures reported in the literature (Fortier & McAuley, 1989 ; Chak et al., 1994 ). The experimental conditions considered for the reaction of L² and L³ with silver(I) in the presence of thiocyanate, namely, an L/Ag⁺/SCN⁻ molar ratio of 1:1:0.5, were the same as those used for the reactions in the presence of cyanate. In both cases, the aim was to favour the bridging coordination mode of the anionic ligand.

2.2.1. Synthesis of [Ag(L¹)₂]BF₄

A mixture of 4,7-bis(cyanomethyl)-1-thia-4,7-diazacyclononane (L¹) (20 mg, 0.089 mmol) and AgBF₄ (17.33 mg, 0.089 mmol) in MeCN (5 ml) was stirred in the dark at room temperature for 12 h. The solvent was partially removed under reduced pressure and Et₂O vapour was allowed to diffuse into the remaining solution. Colourless block-shaped crystals of the desired complex were obtained (yield 15.2 mg, 53%; m.p. 160 °C, with decomposition). Analysis calculated (%) for [Ag(L¹)₂]BF₄, C₂₀H₃₂AgBF₄N₈S₂: C 37.34, H 5.01, N 17.42; found: C 37.28, H 4.99, N 17.20. FAB mass spectrum (3-NOBA) m/z: 555 and 331 for [¹⁰⁷Ag(L¹)₂]⁺ and [¹⁰⁷Ag(L¹)]⁺, respectively. IR spectrum (KBr disc) ν (cm⁻¹): 2928 (m), 2833 (m), 2243 (s) (ν_CN stretch in L¹), 1452 (s), 1335 (s), 1223 (w), 1109 (m), 998 (s), 920 (w), 878 (m).

2.2.2. Synthesis of [Ag(L²)(SCN)]

A mixture of 4,7-bis(2-cyanoethyl)-1-thia-4,7-diazacyclononane (L²) (21.7 mg, 0.086 mmol) and AgBF₄ (16.74 mg, 0.086 mmol) in MeCN (3 ml) was stirred in the dark at room temperature for 30 min. A solution of ⁿBu₄NSCN (12.92 mg, 0.043 mmol) in MeCN (2.5 ml) was then added and the resulting mixture was stirred for a further 30 min in the dark at room temperature. After partial removal of the solvent under reduced pressure and filtration through a pad of celite, colourless crystals were formed upon diffusion of Et₂O vapour into the remaining solution (yield 10.5 mg; 58%; m.p. 135 °C, with decomposition). Analysis calculated (%) for [Ag(L²)(SCN)], C₁₃H₂₀AgN₅S₂: C 37.32, H 4.82, N 16.74; found: C 37.30, H 4.87, N 16.65. FAB mass spectrum (3-NOBA) m/z: 359 for [¹⁰⁷Ag(L²)]⁺. IR spectrum (KBr disc) ν (cm⁻¹): 2923 (m), 2824 (m), 2239 (m) (ν_CN stretch in L²), 2085 (m) (ν_CN stretch in SCN), 1472 (m), 1445 (m), 1415 (m), 1363 (m), 1306 (w), 1047 (s), 968 (m), 848 (w), 750 (w).

2.2.3. Synthesis of [Ag₂(L³)₂(μ-SCN)]BF₄

A mixture of 7-(2-cyanoethyl)-1,4-dithia-7-azacyclononane (L³) (21.7 mg, 0.100 mmol) and AgBF₄ (19.47 mg, 0.100 mmol) in MeCN (2.5 ml) was stirred in the dark at room temperature for 30 min. A solution of ⁿBu₄NSCN (15.027 mg, 0.050 mmol) in MeCN (2.5 ml) was then added and the resulting mixture was stirred for a further 30 min in the dark at room temperature. After partial removal of the solvent under reduced pressure and filtration through a pad of celite, colourless crystals were formed upon diffusion of Et₂O vapour into the remaining solution (yield 18.3 mg; 46%; m.p. 140–142 °C). Analysis calculated (%) for [Ag₂(L³)₂(μ-SCN)]BF₄, C₁₉H₃₂Ag₂BF₄N₅S₅: C 28.76, H 4.07, N 8.83; found: C 28.65, H 3.98, N 8.78. FAB mass spectrum (3-NOBA) m/z: 323 for [¹⁰⁷Ag(L³)]⁺. IR spectrum (KBr disc) ν (cm⁻¹): 2911 (m), 2826 (m), 2246 (m) (ν_CN stretch in L³), 2105 (m) (ν_CN stretch in SCN), 1462 (m), 1410 (m), 1361 (m), 1303 (m), 1037 (s), 958 (w), 940 (w), 899 (w), 830 (w), 810 (w), 710 (w).

2.3. Refinement of X-ray data

Crystal data, data collection and structure refinement details are summarized in Table 1. Methylene H atoms were refined as riding on their parent C atoms, with U_iso(H) = 1.2U_eq(C).

Table 1
Experimental details

Experiments were carried out at 150 K with Mo Kα radiation. H-atom parameters were constrained.

	[Ag(L¹)₂]BF₄	[Ag(L²)(SCN)]	[Ag₂(L³)₂(μ-SCN)]BF₄
Crystal data
Chemical formula	[Ag(C₁₀H₁₆N₄S)₂]BF₄	[Ag(C₁₂H₂₀N₄S)(NCS)]	[Ag₂(C₉H₁₆N₂S₂)₂(SCN)]BF₄
M_r	643.33	418.33	793.34
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$	Monoclinic, C2/c
a, b, c (Å)	10.1813 (6), 10.2237 (6), 15.0154 (9)	8.4426 (6), 8.5739 (6), 11.8497 (8)	28.537 (3), 8.4362 (11), 27.216 (3)
α, β, γ (°)	73.446 (2), 82.398 (2), 61.781 (2)	96.585 (1), 99.023 (1), 95.313 (1)	90, 119.940 (9), 90
V (Å³)	1320.11 (14)	836.19 (1)	5677.6 (12)
Z	2	2	8
μ (mm⁻¹)	0.98	1.46	1.79
Crystal size (mm)	0.3 × 0.2 × 0.14	0.36 × 0.30 × 0.07	0.27 × 0.15 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector	Bruker SMART1000 CCD area-detector	Stoe STADI4 4-circle
Absorption correction	Multi-scan (SADABS; Bruker, 1996 )	Integration (SHELXTL; Sheldrick, 2008 )	Integration (SHELXTL; Sheldrick, 2008)
T_min, T_max	0.729, 0.828	0.606, 0.819	0.713, 0.822
No. of measured, independent and observed [I > 2σ(I)] reflections	13703, 6151, 5420	5159, 3668, 3401	5547, 4972, 4138
R_int	0.035	0.022	0.025
(sin θ/λ)_max (Å⁻¹)	0.679	0.675	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.062, 1.07	0.021, 0.055, 1.06	0.036, 0.075, 1.15
No. of reflections	6151	3668	4972
No. of parameters	328	190	326
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.34	0.34, −0.41	0.56, −0.52
Computer programs: SMART (Bruker, 1998 ), STADI-4 (Stoe & Cie, 1996 ), SAINT (Bruker, 1999 ), X-RED (Stoe & Cie, 1996), SHELXS97 (Sheldrick, 2008), SHELXL2018 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ) and Mercury (Macrae et al., 2020 ).

3. Results and discussion

Following the synthetic strategy adopted in previous studies to favour the formation of inorganic polymers, we reacted L¹ with AgBF₄ in MeCN using a 1:1 metal-to-ligand molar ratio. Colourless tabular crystals formed after partial removal of the solvent and subsequent diffusion of Et₂O vapour into the remaining solution. A single-crystal X-ray structure determination confirmed the product to be the discrete mononuclear Ag^I homoleptic complex [Ag(L¹)₂]BF₄. Two ligands bind facially to the metal centre via the tridentate macrocyclic moiety, thus conferring a distorted octahedral coordination geometry of four N-donor and two S-donor atoms (Fig. 1), with no involvement of the nitrile groups from the pendant arms in metal coordination. The sandwich complex cations lie on crystallographic inversion centres, with the asymmetric unit consisting of two half-cations and one BF₄⁻ anion (Z = 2). Each equatorial plane is defined by the N-donor atoms of two macrocyclic moieties [Ag1—N4 = 2.6173 (12), Ag1—N7 = 2.6822 (14), Ag1′—N4′ = 2.6363 (12) and Ag1′—N7′ = 2.6108 (13) Å], while the apical positions are occupied by the S-donor atoms [Ag1—S1 = 2.5273 (4) and Ag1′—S1′ = 2.5605 (4) Å] (Table 2). The Ag—N bond lengths are slightly longer than those reported for the sandwich complex [Ag(Me₃[9]aneN₃)₂]PF₆ [Ag—N = 2.543 (10) and 2.607 (7) Å; Me₃[9]aneN₃ = 1,4,7-trimethyl-1,4,7-triazacyclononane] (Stockheim et al., 1991 ), while the Ag—S bond length is significantly shorter than those observed in the sandwich complex [Ag([9]aneS₃)₂](CF₃SO₃) [2.696 (2)–2.753 (1) Å; [9]aneS₃ = 1,4,7-ththiacyclononane] (Blower et al., 1989 ).

Table 2
Selected geometric parameters (Å, °)

[Ag(L¹)₂]BF₄
Ag1—S1	2.5273 (4)	Ag1′—S1′	2.5605 (4)
Ag1—N4	2.6173 (12)	Ag1′—N4′	2.6363 (12)
Ag1—N7	2.6822 (14)	Ag1′—N7′	2.6108 (13)

S1—Ag1—N4	77.67 (3)	S1′—Ag1′—N4′	76.92 (3)
S1—Ag1—N7	76.40 (3)	S1′—Ag1′—N7′	76.70 (3)
N4—Ag1—N7	68.50 (4)	N7′—Ag1′—N4′	69.72 (4)

[Ag(L²)(SCN)]
Ag1—S1	2.5074 (5)	Ag1—N7	2.5561 (15)
Ag1—S	2.4390 (5)	C—N	1.152 (3)
Ag1—N4	2.5490 (14)	C—S	1.670 (2)

S1—Ag1—N4	79.60 (4)	S—Ag1—N7	111.02 (4)
S1—Ag1—N7	79.77 (4)	N4—Ag1—N7	71.15 (5)
S—Ag1—S1	160.21 (2)	N—C—S	177.7 (2)
S—Ag1—N4	119.16 (4)

[Ag₂(L³)₂(μ-SCN)]BF₄
Ag1—Ag2	3.0716 (6)	Ag2—S1A	2.5329 (13)
Ag1—S4	2.6065 (13)	Ag2—S4A	2.6046 (13)
Ag1—S1	2.5966 (13)	Ag2—S	2.4441 (13)
Ag1—S	2.4943 (13)	Ag2—N7A	2.557 (4)
Ag1—N7	2.492 (4)

S1—Ag1—S4	83.55 (4)	S1A—Ag2—S4A	86.88 (4)
S—Ag1—S4	129.95 (4)	S1A—Ag2—N7A	78.06 (9)
S—Ag1—S1	142.23 (4)	S4A—Ag2—Ag1	85.08 (3)
N7—Ag1—Ag2	120.33 (9)	S—Ag2—S1A	143.47 (4)
N7—Ag1—S4	80.45 (9)	S—Ag2—S4A	124.09 (4)
N7—Ag1—S1	79.96 (9)	S—Ag2—N7A	123.39 (9)
N7—Ag1—S	117.91 (9)	N7A—Ag2—S4A	77.95 (9)
Ag1—S—Ag2	76.91 (4)

Figure 1
Two asymmetric units of complex [Ag(L¹)₂]BF₄, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The heteroatoms of the asymmetric unit are labelled.

The extended structure of [Ag(L¹)₂]BF₄ features C—H⋯N and C—H⋯F interactions characterized by H⋯A distances of 2.36–2.62 Å and D—H⋯A angles of 128–161° (see Table S1 in the supporting information). These interactions link cations and anions into chains (see Fig. 2; complementary views of the packing are available as Figs. S1 and S2 in the supporting information) and crosslink these chains to form layers.

Figure 2
The extended structure of [Ag(L¹)₂]BF₄, viewed approximately along the a axis. The structure features C—H⋯F and C—H⋯N interactions (shown as dotted lines), which link cations and anions into layers.

The formation of the mononuclear sandwich complex [Ag(L¹)₂]BF₄ upon reaction of L¹ with silver(I) appears to support the hypothesis that longer nitrile pendant arms favour the formation of polynuclear complexes via bridging different metal centres that occupy different ring cavities. Thus, reaction of L² with AgBF₄ afforded the binuclear complex [Ag₂(L²)₂[(BF₄)₂, in which two inversion-related [Ag(L²)]⁺ units are held together by Ag—N bonds involving one nitrile-functionalized pendant arm from each ligand; the remaining two pendant arms are uncoordinated (Tei et al., 2002). Also, the formation of a sinusoidal one-dimensional polymer is observed in {[Ag(L³)]BF₄}, in which each Ag^I ion of the [Ag(L³)]⁺ repeating unit is bound by the [9]aneN₂S macrocyclic moiety of the ligand and by the nitrile group of a symmetry-related [Ag(L³)]⁺ unit (Tei et al., 2002).

The observed steric influence of nitrile-functionalized pendant arms on the formation of a polynuclear silver(I) complex cannot be the same in the presence of exogenous bridging ligands. The results obtained in the presence of CN⁻ {side-on coordination in the case of the binuclear complex cation [Ag₂(L¹)₂(μ-CN)]⁺ and end-on coordination in the case of [Ag₂(L²)₂(μ-CN)]⁺ and [Ag₂(L³)₂(μ-CN)]⁺} seem to indicate the same trend observed in the absence of the pseudo-halogen (Lippolis et al., 1999). In order to test this idea, we considered the reaction of L² and L³ with NCS⁻ that, like CN⁻, can coordinate to metals in both terminal and bridging modes; moreover, as bridging ligands, NCS⁻ can also link metal centres in either an end-on or a side-on bonded fashion.

Reaction of L² with 1 equiv. of AgBF₄ in MeCN in the presence of 0.5 equiv. of ⁿBu₄NSCN was carried out under the same experimental conditions used for the reaction performed in the presence of CN⁻. After partial removal of the solvent and filtration through a pad of celite, colourless crystals were formed upon diffusion of Et₂O vapour into the remaining solution. Microanalytical data suggested the formulation [Ag(L²)(SCN)] for the product obtained and an X-ray diffraction analysis was undertaken to elucidate the coordination mode of the ligand NCS⁻. The compound consists of mononuclear units and shows the metal centre facially coordinated to the macrocyclic moiety of L² [Ag1—N4 = 2.5490 (14), Ag1—N7 = 2.5561 (15) and Ag1—S1 = 2.5074 (5) Å] and to a terminal SCN⁻ anion ligand via its S-donor atom [Ag1—S 2.4390 (5) Å] in a tetrahedral geometry (Fig. 3).

Figure 3
The asymmetric unit of complex [Ag(L²)(SCN)]BF₄, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

The structure is very similar to that observed for [Ag([9]aneN₂S)Cl] (Heinzel & Mattes; 1992 ), in which the Ag—N and Ag—S distances [Ag—N = 2.414 (5) and Ag—S = 2.629 (2) Å] are significantly shorter and longer, respectively, than those observed in [Ag(L²)(SCN)] and in [Ag(Me₃[9]aneN₃)(SCN)] (Stockheim et al., 1991). The Ag—N distances in [Ag(Me₃[9]aneN₃)(SCN)] are comparable with those in [Ag([9]aneN₂S)Cl]. As observed in [Ag(Me₃[9]aneN₃)(SCN)], the structure of [Ag(L²)(SCN)] shows molecular complex units packed pairwise, with the silver(I) ion and the S-donor from the thiocyanate ligand of two different complex units interacting in a head-to-tail manner to form a planar four-membered rhombohedral ring with intermolecular Ag⋯S interactions of 3.2421 (6) Å (Fig. 4).

Figure 4
View of a pair of [Ag(L²)(SCN)] molecules, showing intermolecular Ag⋯S interactions. H atoms have been omitted for clarity. [Symmetry code: (′) −x + 1, −y + 1, −z + 1.]

Presumably these interactions, rather than steric factors, are responsible for the fact that the nitrile groups are not involved in metal coordination and the thiocyanate ligand prefers to coordinate the metal centre in terminal rather than in bridging mode. Furthermore, pairs of [Ag(L²)(SCN)] complex units are linked into chains of molecules by C42—H42A⋯N74ⁱ interactions [N74ⁱ⋯H42A = 2.34 Å and C42—H42A⋯N74ⁱ = 157°; symmetry code: (i) −x + 1, −y + 1, −z] (Fig. 5). These chains run parallel to the c axis. The C—H⋯N(nitrile) interactions are supported by C—H⋯N(thiocyanate) interactions (not shown for clarity in Fig. 5) [C72—H72A⋯Nⁱ: Nⁱ⋯H72A = 2.51 Å and C72—H72A⋯Nⁱ = 142°; see Table S2 in the supporting information for short contacts in the structure].

Figure 5
Partial view, approximatively along the a axis, of a chain of pairs of [Ag(L²)(SCN)] molecules linked via C—H⋯N(nitrile) interactions.

Surprisingly, the reaction of L³ with AgBF₄ and ⁿBu₄NSCN under the same experimental conditions used for [Ag(L²)(SCN)] afforded the binuclear complex [Ag₂(L³)₂(μ-SCN)]BF₄, which shows a μ₂-κS:κS bridging NCS⁻ ligand acting as a σ two-electron donor between two metal centres of [Ag(L³)]⁺ complex cationic units [Ag1—S = 2.4943 (13) and Ag2—S = 2.4441 (13) Å] (Fig. 6).

Figure 6
The asymmetric unit of complex [Ag₂(L³)₂(μ-SCN)]BF₄, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

The structure is very similar to that observed for the [Ag₂(L¹)₂(μ-CN)]⁺ complex cation except that L¹ (which has two –CH₂CN pendant arms) and CN⁻ are replaced by L³ (which has only one –CH₂CH₂CN pendant arm) and NCS⁻. The Ag1—S—Ag2 angle of 76.91 (4)° is slightly smaller than the angle at the side-on bridging cyanide [Ag1—C—Ag2 = 79.5 (3)°] in [Ag₂(L¹)₂(μ-CN)]⁺ (Lippolis et al., 1999), with the Ag—Ag distance being significantly longer [3.0716 (6) Å] compared to the value of 2.7557 (10) Å in [Ag₂(L¹)₂(μ-CN)]⁺; this could be a consequence of the longer Ag—S distances compared to Ag—C [2.153 (8) and 2.155 (8) Å, respectively]. The packing in [Ag₂(L³)₂(μ-SCN)]BF₄ is a 3D network built up by an array of C—H⋯N, C—H⋯F and C—H⋯S interactions (see Fig. S3 and Table S3 in the supporting information).

The complex cation [Ag₂(L³)₂(μ-SCN)]⁺ represents the first discrete binuclear silver(I) complex featuring a two-electron (σ) μ₂-κS:κS bridging thiocyanate. A similar coordination mode of SCN⁻ in discrete binuclear complexes has only been observed in the complex anion [Hg₂(SCN)₇]³⁻ in [Co(NH₃)₆][Hg₂(SCN)₇] (Bala et al., 2006 ).

4. Conclusions

In this article, we have described the crystal structures of three new silver(I) complexes of nitrile-functionalized pendant-arm derivatives of the tridentate macrocyclic ligands [9]aneN₃, [9]aneN₂S and [9]aneNS₂, including the presence of thiocyanate (NCS⁻). The results obtained, as compared to those previously reported in the presence of cyanate (CN⁻), allow a better understanding of the role played by the number and length of the pendant arms in the coordination chemistry of this type of ligand towards silver(I). In general, longer more sterically-demanding nitrile-functionalized pendant arms in the macrocyclic derivatives (L) do not appear to prevent CN⁻ or NCS⁻ forming a side-on two-electron (σ) bridge rather than a linear four-electron (σ + π) one between two [Ag(L)]⁺ units, provided the appropriate pseudo-halide is used, i.e. steric factors appear not to be responsible for the fact that CN⁻ shows a linear μ₂-κC:κN bridging mode in [Ag₂(L³)₂(μ-CN)]BF₄, whereas NCS⁻ forms a side-on μ₂-κS:κS bridge in the binuclear complex [Ag₂(L³)₂(μ-SCN)]BF₄. In fact, steric factors cannot be considered solely responsible for this because an end-on μ₂-κS:κN bridging mode for NCS⁻ would have allowed the two [Ag(L³)]⁺ units to dispose themselves further apart than in the case of [Ag₂(L³)₂(μ-CN)]⁺ where the shorter CN⁻ acts as a linear μ₂-κC:κN bridging donor. On the other hand, with L² presenting two longer pendant arms as in L³, a linear μ₂-κC:κN bridging mode is observed in [Ag₂(L²)₂(μ-CN)]BF₄ for the cyanide ligand, while a terminal coordination mode is observed for NCS⁻ in the mononuclear tetrahedral complex [Ag(L²)(SCN)]. A side-on μ₂-κC:κN bridging mode is observed in [Ag₂(L¹)₂(μ-CN)]BF₄, where the macrocyclic ligand L¹ incorporates shorter pendant arms compared to L² and L³. This result suggests that some steric effects might also come into play, in combination with electronic requirements, in the coordination chemistry of nitrile-functionalized pendant arm derivative of small tridentate macrocycles with silver(I) in the presence of anionic ligands CN⁻ and NCS⁻.

Supporting information

CCDC references: 2145502; 2145501; 2145500

Crystal structure: contains datablocks AgL12BF4, AgL2SCN, Ag2L32mu-SCNBF4, global. DOI: https://doi.org/10.1107/S205322962200105X/ky3213sup1.cif

Structure factors: contains datablock AgL12BF4. DOI: https://doi.org/10.1107/S205322962200105X/ky3213AgL12BF4sup2.hkl

Structure factors: contains datablock AgL2SCN. DOI: https://doi.org/10.1107/S205322962200105X/ky3213AgL2SCNsup3.hkl

Structure factors: contains datablock Ag2L32mu-SCNBF4. DOI: https://doi.org/10.1107/S205322962200105X/ky3213Ag2L32mu-SCNBF4sup4.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205322962200105X/ky3213sup5.pdf

Computing details top

Data collection: SMART (Bruker, 1998) for AgL12BF4, AgL2SCN; STADI-4 (Stoe & Cie, 1996) for Ag2L32mu-SCNBF4. Cell refinement: SMART (Bruker, 1998) for AgL12BF4, AgL2SCN; STADI-4 (Stoe & Cie, 1996) for Ag2L32mu-SCNBF4. Data reduction: SAINT (Bruker, 1999) for AgL12BF4, AgL2SCN; X-RED (Stoe & Cie, 1996) for Ag2L32mu-SCNBF4. For all structures, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2020); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Bis[4,7-bis(cyanomethyl)-1-thia-4,7-diazacyclononane-κ³N,N',S]silver(I) tetrafluoridoborate (AgL12BF4) top

Crystal data top

[Ag(C₁₀H₁₆N₄S)₂]BF₄	Z = 2
M_r = 643.33	F(000) = 656
Triclinic, P1	D_x = 1.618 Mg m⁻³
a = 10.1813 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.2237 (6) Å	Cell parameters from 4462 reflections
c = 15.0154 (9) Å	θ = 2.3–28.8°
α = 73.446 (2)°	µ = 0.98 mm⁻¹
β = 82.398 (2)°	T = 150 K
γ = 61.781 (2)°	Tablet, colourless
V = 1320.11 (14) Å³	0.3 × 0.2 × 0.14 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	13703 independent reflections
Radiation source: X-ray	5420 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 28.8°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1996}	h = −13→13
T_min = 0.729, T_max = 0.828	k = −13→12
6151 measured reflections	l = −20→20

Refinement top

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.062	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0381P)²] where P = (F_o² + 2F_c²)/3
6151 reflections	(Δ/σ)_max = 0.001
328 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Special details top

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

Refinement. A small number of predominantly low-angle reflections showed poor agreement and were suppressed individually. There were no other systematic trends and the reasons for the poor agreement were not pursued.

Diffraction data were collected on Stoe STADI4 4-circle and Bruker SMART CCD area detector diffractometers. Structures were solved by direct methods and developed by iterative cycles of least-squares refinement on F² and difference Fourier synthesis.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ag1'	0.000000	1.000000	0.500000	0.02157 (5)
S1	0.80965 (5)	0.73691 (4)	0.89254 (3)	0.02367 (9)
C2	0.7080 (2)	0.66111 (19)	0.84889 (11)	0.0288 (4)
H2A	0.607906	0.695424	0.877628	0.035*
H2B	0.693997	0.706560	0.781044	0.035*
C3	0.78180 (19)	0.48679 (18)	0.86677 (10)	0.0252 (3)
H3A	0.713163	0.458039	0.845737	0.030*
H3B	0.873060	0.454056	0.828479	0.030*
N4	0.82224 (14)	0.40209 (14)	0.96400 (8)	0.0187 (3)
C5	0.69353 (17)	0.43080 (18)	1.02663 (11)	0.0223 (3)
H5A	0.670968	0.342854	1.040685	0.027*
H5B	0.605698	0.523292	0.994610	0.027*
C6	0.71893 (18)	0.45403 (18)	1.11751 (11)	0.0225 (3)
H6A	0.628725	0.472071	1.156554	0.027*
H6B	0.802780	0.359104	1.151443	0.027*
N7	0.75219 (14)	0.58322 (14)	1.10358 (8)	0.0195 (3)
C8	0.68686 (18)	0.82805 (18)	0.97989 (11)	0.0239 (3)
H8A	0.739632	0.865178	1.009359	0.029*
H8B	0.598490	0.919414	0.947553	0.029*
C9	0.63217 (17)	0.73218 (17)	1.05647 (11)	0.0235 (3)
H9A	0.578197	0.791050	1.103106	0.028*
H9B	0.560508	0.713840	1.029639	0.028*
C41	0.91605 (18)	0.23839 (18)	0.97407 (12)	0.0257 (3)
H41C	0.946423	0.187697	1.039954	0.031*
H41D	1.007482	0.222817	0.936645	0.031*
C42	0.8399 (2)	0.16515 (19)	0.94421 (12)	0.0287 (4)
N43	0.7762 (2)	0.11560 (19)	0.91955 (11)	0.0406 (4)
C71	0.79990 (18)	0.58746 (19)	1.18970 (10)	0.0250 (3)
H71C	0.828128	0.671450	1.176321	0.030*
H71D	0.889447	0.489696	1.213719	0.030*
C72	0.6831 (2)	0.6111 (2)	1.26223 (11)	0.0319 (4)
N73	0.5894 (2)	0.6280 (2)	1.31473 (11)	0.0499 (5)
Ag1	1.000000	0.500000	1.000000	0.02228 (5)
S1'	0.10514 (5)	1.09797 (5)	0.34563 (3)	0.02568 (9)
C2'	0.0767 (2)	0.98966 (19)	0.27946 (10)	0.0264 (3)
H2'A	−0.031759	1.033563	0.269579	0.032*
H2'B	0.122681	1.005841	0.217583	0.032*
C3'	0.13787 (18)	0.81697 (18)	0.32141 (10)	0.0230 (3)
H3'A	0.106138	0.773825	0.282131	0.028*
H3'B	0.248144	0.768802	0.320401	0.028*
N4'	0.08854 (14)	0.77649 (14)	0.41728 (8)	0.0203 (3)
C5'	0.20750 (17)	0.65164 (17)	0.48137 (10)	0.0230 (3)
H5'A	0.247413	0.556719	0.459982	0.028*
H5'B	0.164196	0.632522	0.543841	0.028*
C6'	0.33462 (18)	0.68556 (18)	0.48879 (11)	0.0238 (3)
H6'A	0.409806	0.597136	0.532877	0.029*
H6'B	0.382879	0.696731	0.427293	0.029*
N7'	0.28727 (14)	0.82627 (15)	0.52028 (9)	0.0220 (3)
C8'	0.35356 (19)	0.9247 (2)	0.46700 (12)	0.0293 (4)
H8'A	0.463408	0.863294	0.469830	0.035*
H8'B	0.326722	1.008418	0.497214	0.035*
C9'	0.3061 (2)	0.9960 (2)	0.36514 (12)	0.0316 (4)
H9'A	0.350110	0.913493	0.332084	0.038*
H9'B	0.348054	1.068318	0.337295	0.038*
C41'	−0.03903 (18)	0.74723 (19)	0.42178 (11)	0.0250 (3)
H41A	−0.120886	0.839174	0.384023	0.030*
H41B	−0.073772	0.732035	0.486932	0.030*
C42'	−0.00916 (19)	0.6118 (2)	0.38874 (11)	0.0282 (4)
N43'	0.01303 (19)	0.50939 (19)	0.36215 (11)	0.0378 (4)
C71'	0.31270 (19)	0.7887 (2)	0.61963 (11)	0.0291 (4)
H71A	0.258848	0.730041	0.653272	0.035*
H71B	0.270607	0.885113	0.639567	0.035*
C72'	0.4724 (2)	0.6977 (2)	0.64596 (13)	0.0433 (5)
N73'	0.5960 (2)	0.6277 (3)	0.66227 (15)	0.0718 (7)
B1	0.2911 (2)	0.9973 (2)	0.79979 (14)	0.0293 (4)
F1	0.28390 (16)	0.86125 (13)	0.81549 (8)	0.0536 (3)
F2	0.33708 (13)	1.03340 (13)	0.70886 (8)	0.0448 (3)
F3	0.15010 (12)	1.11335 (13)	0.81049 (9)	0.0483 (3)
F4	0.38827 (14)	0.98516 (16)	0.86048 (9)	0.0616 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1'	0.02112 (9)	0.02284 (9)	0.01874 (8)	−0.00723 (7)	0.00187 (6)	−0.00835 (6)
S1	0.0314 (2)	0.02153 (19)	0.02038 (18)	−0.01508 (17)	−0.00034 (15)	−0.00316 (14)
C2	0.0373 (10)	0.0247 (8)	0.0259 (8)	−0.0160 (8)	−0.0122 (7)	0.0000 (7)
C3	0.0323 (9)	0.0277 (8)	0.0204 (7)	−0.0163 (7)	−0.0037 (6)	−0.0068 (6)
N4	0.0208 (6)	0.0158 (6)	0.0201 (6)	−0.0081 (5)	−0.0002 (5)	−0.0058 (5)
C5	0.0212 (8)	0.0210 (8)	0.0279 (8)	−0.0120 (6)	0.0017 (6)	−0.0073 (6)
C6	0.0250 (8)	0.0218 (8)	0.0222 (7)	−0.0128 (7)	0.0055 (6)	−0.0064 (6)
N7	0.0221 (7)	0.0179 (6)	0.0196 (6)	−0.0095 (5)	0.0025 (5)	−0.0068 (5)
C8	0.0253 (8)	0.0159 (7)	0.0286 (8)	−0.0073 (6)	−0.0031 (6)	−0.0052 (6)
C9	0.0200 (8)	0.0196 (8)	0.0292 (8)	−0.0065 (6)	0.0029 (6)	−0.0094 (6)
C41	0.0246 (8)	0.0197 (8)	0.0310 (8)	−0.0068 (7)	−0.0016 (7)	−0.0091 (6)
C42	0.0360 (10)	0.0196 (8)	0.0299 (8)	−0.0118 (7)	0.0060 (7)	−0.0098 (6)
N43	0.0561 (11)	0.0391 (9)	0.0428 (9)	−0.0320 (9)	0.0111 (8)	−0.0203 (7)
C71	0.0276 (8)	0.0282 (8)	0.0218 (7)	−0.0138 (7)	0.0050 (6)	−0.0106 (6)
C72	0.0408 (10)	0.0314 (9)	0.0240 (8)	−0.0160 (8)	0.0058 (7)	−0.0114 (7)
N73	0.0547 (11)	0.0539 (11)	0.0350 (9)	−0.0227 (10)	0.0207 (8)	−0.0160 (8)
Ag1	0.01716 (9)	0.02577 (10)	0.02614 (9)	−0.00879 (7)	0.00062 (6)	−0.01193 (7)
S1'	0.0355 (2)	0.0231 (2)	0.02031 (18)	−0.01553 (18)	0.00362 (16)	−0.00607 (15)
C2'	0.0380 (9)	0.0268 (8)	0.0166 (7)	−0.0171 (8)	0.0006 (6)	−0.0046 (6)
C3'	0.0290 (8)	0.0243 (8)	0.0180 (7)	−0.0130 (7)	0.0024 (6)	−0.0084 (6)
N4'	0.0241 (7)	0.0201 (6)	0.0169 (6)	−0.0102 (5)	−0.0014 (5)	−0.0043 (5)
C5'	0.0284 (8)	0.0177 (7)	0.0203 (7)	−0.0075 (7)	−0.0026 (6)	−0.0056 (6)
C6'	0.0221 (8)	0.0234 (8)	0.0230 (7)	−0.0054 (7)	0.0003 (6)	−0.0108 (6)
N7'	0.0208 (7)	0.0239 (7)	0.0213 (6)	−0.0076 (6)	−0.0001 (5)	−0.0105 (5)
C8'	0.0259 (9)	0.0349 (10)	0.0341 (9)	−0.0169 (8)	0.0040 (7)	−0.0150 (7)
C9'	0.0327 (9)	0.0371 (10)	0.0319 (9)	−0.0227 (8)	0.0097 (7)	−0.0107 (7)
C41'	0.0280 (8)	0.0242 (8)	0.0231 (8)	−0.0123 (7)	−0.0009 (6)	−0.0055 (6)
C42'	0.0339 (9)	0.0319 (9)	0.0238 (8)	−0.0201 (8)	−0.0032 (7)	−0.0033 (7)
N43'	0.0520 (10)	0.0380 (9)	0.0341 (8)	−0.0281 (8)	−0.0014 (7)	−0.0103 (7)
C71'	0.0261 (9)	0.0319 (9)	0.0247 (8)	−0.0052 (7)	−0.0037 (6)	−0.0134 (7)
C72'	0.0351 (11)	0.0521 (12)	0.0371 (10)	−0.0053 (9)	−0.0099 (8)	−0.0253 (9)
N73'	0.0368 (11)	0.0989 (17)	0.0652 (13)	0.0017 (11)	−0.0190 (9)	−0.0509 (13)
B1	0.0315 (10)	0.0238 (9)	0.0314 (10)	−0.0075 (8)	−0.0075 (8)	−0.0113 (8)
F1	0.0917 (10)	0.0313 (6)	0.0421 (6)	−0.0330 (7)	−0.0030 (6)	−0.0055 (5)
F2	0.0504 (7)	0.0477 (7)	0.0391 (6)	−0.0267 (6)	0.0020 (5)	−0.0085 (5)
F3	0.0328 (6)	0.0443 (7)	0.0628 (8)	−0.0073 (5)	−0.0011 (5)	−0.0246 (6)
F4	0.0453 (7)	0.0756 (9)	0.0647 (8)	−0.0106 (7)	−0.0226 (6)	−0.0396 (7)

Geometric parameters (Å, º) top

Ag1'—S1'	2.5605 (4)	C71—C72	1.481 (2)
Ag1'—S1'ⁱ	2.5606 (4)	C72—N73	1.133 (2)
Ag1'—N4'	2.6363 (12)	S1'—C2'	1.8174 (16)
Ag1'—N4'ⁱ	2.6363 (12)	S1'—C9'	1.8237 (18)
Ag1'—N7'ⁱ	2.6108 (13)	C2'—H2'A	0.9900
Ag1'—N7'	2.6108 (13)	C2'—H2'B	0.9900
S1—C2	1.8242 (17)	C2'—C3'	1.527 (2)
S1—C8	1.8200 (17)	C3'—H3'A	0.9900
S1—Ag1	2.5273 (4)	C3'—H3'B	0.9900
C2—H2A	0.9900	C3'—N4'	1.4702 (18)
C2—H2B	0.9900	N4'—C5'	1.4727 (18)
C2—C3	1.526 (2)	N4'—C41'	1.454 (2)
C3—H3A	0.9900	C5'—H5'A	0.9900
C3—H3B	0.9900	C5'—H5'B	0.9900
C3—N4	1.4670 (19)	C5'—C6'	1.514 (2)
N4—C5	1.4681 (19)	C6'—H6'A	0.9900
N4—C41	1.4555 (19)	C6'—H6'B	0.9900
N4—Ag1	2.6173 (12)	C6'—N7'	1.482 (2)
C5—H5A	0.9900	N7'—C8'	1.466 (2)
C5—H5B	0.9900	N7'—C71'	1.4565 (19)
C5—C6	1.524 (2)	C8'—H8'A	0.9900
C6—H6A	0.9900	C8'—H8'B	0.9900
C6—H6B	0.9900	C8'—C9'	1.527 (2)
C6—N7	1.4661 (19)	C9'—H9'A	0.9900
N7—C9	1.4723 (19)	C9'—H9'B	0.9900
N7—C71	1.4589 (19)	C41'—H41A	0.9900
C8—H8A	0.9900	C41'—H41B	0.9900
C8—H8B	0.9900	C41'—C42'	1.486 (2)
C8—C9	1.516 (2)	C42'—N43'	1.139 (2)
C9—H9A	0.9900	C71'—H71A	0.9900
C9—H9B	0.9900	C71'—H71B	0.9900
C41—H41C	0.9900	C71'—C72'	1.482 (2)
C41—H41D	0.9900	C72'—N73'	1.134 (2)
C41—C42	1.482 (2)	B1—F1	1.379 (2)
C42—N43	1.138 (2)	B1—F2	1.388 (2)
C71—H71C	0.9900	B1—F3	1.390 (2)
C71—H71D	0.9900	B1—F4	1.372 (2)

S1'—Ag1'—S1'ⁱ	180.0	S1—Ag1—S1ⁱⁱ	180.0
S1'—Ag1'—N4'	76.92 (3)	S1—Ag1—N4	77.67 (3)
S1'ⁱ—Ag1'—N4'	103.08 (3)	S1ⁱⁱ—Ag1—N4	102.33 (3)
S1'—Ag1'—N4'ⁱ	103.08 (3)	S1—Ag1—N4ⁱⁱ	102.33 (3)
S1'ⁱ—Ag1'—N4'ⁱ	76.92 (3)	S1ⁱⁱ—Ag1—N4ⁱⁱ	77.67 (3)
S1'—Ag1'—N7'ⁱ	103.30 (3)	N4ⁱⁱ—Ag1—N4	180.0
S1'—Ag1'—N7'	76.70 (3)	C2'—S1'—Ag1'	97.19 (5)
S1'ⁱ—Ag1'—N7'ⁱ	76.70 (3)	C2'—S1'—C9'	102.79 (8)
S1'ⁱ—Ag1'—N7'	103.30 (3)	C9'—S1'—Ag1'	103.55 (6)
N4'ⁱ—Ag1'—N4'	180.0	S1'—C2'—H2'A	108.0
N7'ⁱ—Ag1'—N4'	110.28 (4)	S1'—C2'—H2'B	108.0
N7'—Ag1'—N4'	69.72 (4)	H2'A—C2'—H2'B	107.3
N7'ⁱ—Ag1'—N4'ⁱ	69.72 (4)	C3'—C2'—S1'	117.00 (11)
N7'—Ag1'—N4'ⁱ	110.28 (4)	C3'—C2'—H2'A	108.0
N7'ⁱ—Ag1'—N7'	180.0	C3'—C2'—H2'B	108.0
C2—S1—Ag1	102.58 (5)	C2'—C3'—H3'A	108.8
C8—S1—C2	104.31 (8)	C2'—C3'—H3'B	108.8
C8—S1—Ag1	98.56 (5)	H3'A—C3'—H3'B	107.7
S1—C2—H2A	108.4	N4'—C3'—C2'	113.64 (13)
S1—C2—H2B	108.4	N4'—C3'—H3'A	108.8
H2A—C2—H2B	107.5	N4'—C3'—H3'B	108.8
C3—C2—S1	115.46 (11)	C3'—N4'—Ag1'	112.22 (9)
C3—C2—H2A	108.4	C3'—N4'—C5'	114.60 (12)
C3—C2—H2B	108.4	C5'—N4'—Ag1'	100.41 (8)
C2—C3—H3A	108.5	C41'—N4'—Ag1'	104.94 (9)
C2—C3—H3B	108.5	C41'—N4'—C3'	112.44 (12)
H3A—C3—H3B	107.5	C41'—N4'—C5'	111.21 (12)
N4—C3—C2	114.90 (13)	N4'—C5'—H5'A	108.9
N4—C3—H3A	108.5	N4'—C5'—H5'B	108.9
N4—C3—H3B	108.5	N4'—C5'—C6'	113.43 (13)
C3—N4—C5	113.57 (12)	H5'A—C5'—H5'B	107.7
C3—N4—Ag1	101.77 (9)	C6'—C5'—H5'A	108.9
C5—N4—Ag1	112.87 (9)	C6'—C5'—H5'B	108.9
C41—N4—C3	112.17 (12)	C5'—C6'—H6'A	108.9
C41—N4—C5	111.24 (12)	C5'—C6'—H6'B	108.9
C41—N4—Ag1	104.52 (9)	H6'A—C6'—H6'B	107.7
N4—C5—H5A	109.0	N7'—C6'—C5'	113.51 (13)
N4—C5—H5B	109.0	N7'—C6'—H6'A	108.9
N4—C5—C6	113.06 (12)	N7'—C6'—H6'B	108.9
H5A—C5—H5B	107.8	C6'—N7'—Ag1'	110.86 (9)
C6—C5—H5A	109.0	C8'—N7'—Ag1'	104.80 (9)
C6—C5—H5B	109.0	C8'—N7'—C6'	113.74 (13)
C5—C6—H6A	109.0	C71'—N7'—Ag1'	104.38 (9)
C5—C6—H6B	109.0	C71'—N7'—C6'	110.96 (13)
H6A—C6—H6B	107.8	C71'—N7'—C8'	111.53 (13)
N7—C6—C5	112.88 (12)	N7'—C8'—H8'A	108.5
N7—C6—H6A	109.0	N7'—C8'—H8'B	108.5
N7—C6—H6B	109.0	N7'—C8'—C9'	114.91 (13)
C6—N7—C9	113.82 (12)	H8'A—C8'—H8'B	107.5
C71—N7—C6	111.68 (12)	C9'—C8'—H8'A	108.5
C71—N7—C9	112.43 (12)	C9'—C8'—H8'B	108.5
S1—C8—H8A	107.9	S1'—C9'—H9'A	108.6
S1—C8—H8B	107.9	S1'—C9'—H9'B	108.6
H8A—C8—H8B	107.2	C8'—C9'—S1'	114.86 (12)
C9—C8—S1	117.58 (11)	C8'—C9'—H9'A	108.6
C9—C8—H8A	107.9	C8'—C9'—H9'B	108.6
C9—C8—H8B	107.9	H9'A—C9'—H9'B	107.5
N7—C9—C8	113.72 (13)	N4'—C41'—H41A	108.6
N7—C9—H9A	108.8	N4'—C41'—H41B	108.6
N7—C9—H9B	108.8	N4'—C41'—C42'	114.51 (14)
C8—C9—H9A	108.8	H41A—C41'—H41B	107.6
C8—C9—H9B	108.8	C42'—C41'—H41A	108.6
H9A—C9—H9B	107.7	C42'—C41'—H41B	108.6
N4—C41—H41C	109.1	N43'—C42'—C41'	179.01 (18)
N4—C41—H41D	109.1	N7'—C71'—H71A	108.9
N4—C41—C42	112.62 (13)	N7'—C71'—H71B	108.9
H41C—C41—H41D	107.8	N7'—C71'—C72'	113.33 (15)
C42—C41—H41C	109.1	H71A—C71'—H71B	107.7
C42—C41—H41D	109.1	C72'—C71'—H71A	108.9
N43—C42—C41	176.78 (19)	C72'—C71'—H71B	108.9
N7—C71—H71C	109.0	N73'—C72'—C71'	177.1 (2)
N7—C71—H71D	109.0	F1—B1—F2	108.17 (14)
N7—C71—C72	112.90 (14)	F1—B1—F3	109.32 (17)
H71C—C71—H71D	107.8	F2—B1—F3	108.64 (15)
C72—C71—H71C	109.0	F4—B1—F1	111.04 (16)
C72—C71—H71D	109.0	F4—B1—F2	110.29 (17)
N73—C72—C71	176.3 (2)	F4—B1—F3	109.33 (15)

Ag1'—S1'—C2'—C3'	−51.77 (13)	Ag1—S1—C2—C3	−13.93 (14)
Ag1'—S1'—C9'—C8'	−17.07 (14)	Ag1—S1—C8—C9	−51.59 (12)
Ag1'—N4'—C5'—C6'	−61.91 (13)	Ag1—N4—C5—C6	−21.40 (15)
Ag1'—N4'—C41'—C42'	−173.20 (10)	Ag1—N4—C41—C42	−172.44 (11)
Ag1'—N7'—C8'—C9'	−55.84 (15)	S1'—C2'—C3'—N4'	52.76 (17)
Ag1'—N7'—C71'—C72'	−176.18 (13)	C2'—S1'—C9'—C8'	−117.84 (13)
S1—C2—C3—N4	52.98 (19)	C2'—C3'—N4'—Ag1'	−21.06 (15)
S1—C8—C9—N7	51.09 (17)	C2'—C3'—N4'—C5'	−134.74 (13)
C2—S1—C8—C9	53.82 (13)	C2'—C3'—N4'—C41'	96.97 (16)
C2—C3—N4—C5	63.48 (17)	C3'—N4'—C5'—C6'	58.55 (17)
C2—C3—N4—C41	−169.32 (14)	C3'—N4'—C41'—C42'	64.55 (17)
C2—C3—N4—Ag1	−58.13 (14)	N4'—C5'—C6'—N7'	58.50 (17)
C3—N4—C5—C6	−136.60 (13)	C5'—N4'—C41'—C42'	−65.49 (16)
C3—N4—C41—C42	−62.98 (18)	C5'—C6'—N7'—Ag1'	−17.74 (15)
N4—C5—C6—N7	59.09 (17)	C5'—C6'—N7'—C8'	−135.52 (14)
C5—N4—C41—C42	65.45 (17)	C5'—C6'—N7'—C71'	97.76 (15)
C5—C6—N7—C9	60.78 (17)	C6'—N7'—C8'—C9'	65.39 (18)
C5—C6—N7—C71	−170.60 (13)	C6'—N7'—C71'—C72'	64.36 (19)
C6—N7—C9—C8	−134.70 (14)	N7'—C8'—C9'—S1'	52.39 (19)
C6—N7—C71—C72	−62.77 (17)	C8'—N7'—C71'—C72'	−63.56 (19)
C8—S1—C2—C3	−116.31 (13)	C9'—S1'—C2'—C3'	53.94 (14)
C9—N7—C71—C72	66.59 (17)	C41'—N4'—C5'—C6'	−172.54 (12)
C41—N4—C5—C6	95.72 (15)	C71'—N7'—C8'—C9'	−168.20 (14)
C71—N7—C9—C8	97.06 (15)

Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+2, −y+1, −z+2.

[4,7-Bis(2-cyanoethyl)-1-thia-4,7-diazacyclononane-\ κ³N,N',S](thiocyanato-κS)silver(I) (AgL2SCN) top

Crystal data top

[Ag(C₁₂H₂₀N₄S)(NCS)]	Z = 2
M_r = 418.33	F(000) = 424
Triclinic, P1	D_x = 1.661 Mg m⁻³
a = 8.4426 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.5739 (6) Å	Cell parameters from 4102 reflections
c = 11.8497 (8) Å	θ = 2.4–28.7°
α = 96.585 (1)°	µ = 1.46 mm⁻¹
β = 99.023 (1)°	T = 150 K
γ = 95.313 (1)°	Block, colourless
V = 836.19 (1) Å³	0.36 × 0.30 × 0.07 mm

Data collection top

Bruker SMART1000 CCD area-detector diffractometer	5159 independent reflections
Graphite monochromator	3401 reflections with I > 2σ(I)
Detector resolution: 8.336 pixels mm^-1	R_int = 0.022
ω scans	θ_max = 28.7°, θ_min = 1.8°
Absorption correction: integration (SHELXTL; Sheldrick, 2008)	h = −11→10
T_min = 0.606, T_max = 0.819	k = −11→11
3668 measured reflections	l = −15→15

Refinement top

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.055	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0321P)² + 0.1835P] where P = (F_o² + 2F_c²)/3
3668 reflections	(Δ/σ)_max = 0.001
190 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Special details top

Refinement. Diffraction data were collected on Stoe STADI4 4-circle and Bruker SMART CCD area detector diffractometers. Structures were solved by direct methods and developed by iterative cycles of least-squares refinement on F² and difference Fourier synthesis.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ag1	0.45271 (2)	0.67967 (2)	0.39303 (2)	0.02735 (6)
C	0.5932 (2)	0.4009 (2)	0.26281 (19)	0.0313 (4)
N	0.5567 (2)	0.3379 (2)	0.16981 (19)	0.0448 (5)
S1	0.30887 (6)	0.91065 (6)	0.45249 (4)	0.02851 (11)
C2	0.1077 (2)	0.8015 (2)	0.41856 (16)	0.0284 (4)
H2A	0.099204	0.725699	0.474927	0.034*
H2B	0.027710	0.877085	0.429162	0.034*
S	0.65402 (7)	0.49300 (7)	0.39676 (4)	0.03595 (12)
C3	0.0617 (2)	0.7106 (2)	0.29747 (16)	0.0248 (4)
H3A	−0.046607	0.651542	0.290188	0.030*
H3B	0.054769	0.787191	0.240856	0.030*
N4	0.17585 (17)	0.59921 (17)	0.26873 (13)	0.0223 (3)
C5	0.2127 (2)	0.5974 (2)	0.15067 (15)	0.0244 (4)
H5A	0.111349	0.567238	0.094771	0.029*
H5B	0.285671	0.515680	0.137477	0.029*
C6	0.2913 (2)	0.7554 (2)	0.12755 (15)	0.0243 (4)
H6A	0.320174	0.742555	0.049455	0.029*
H6B	0.212044	0.833452	0.128798	0.029*
N7	0.43751 (17)	0.81746 (17)	0.21205 (13)	0.0222 (3)
C8	0.4433 (2)	0.9845 (2)	0.25684 (16)	0.0262 (4)
H8A	0.429733	1.045962	0.190860	0.031*
H8B	0.551691	1.020002	0.302759	0.031*
C71	0.5874 (2)	0.7824 (2)	0.17176 (16)	0.0241 (4)
H71A	0.577751	0.668412	0.142763	0.029*
H71B	0.677022	0.803938	0.238190	0.029*
C72	0.6311 (2)	0.8775 (2)	0.07605 (16)	0.0261 (4)
H72A	0.543288	0.855754	0.008450	0.031*
H72B	0.642522	0.991918	0.104194	0.031*
C73	0.7826 (2)	0.8348 (2)	0.04165 (16)	0.0304 (4)
N74	0.8999 (2)	0.7988 (3)	0.01779 (17)	0.0445 (5)
C41	0.1307 (2)	0.4406 (2)	0.29564 (16)	0.0253 (4)
H41A	0.111982	0.448886	0.376417	0.030*
H41B	0.222344	0.377595	0.289955	0.030*
C42	−0.0216 (2)	0.3510 (2)	0.21647 (16)	0.0277 (4)
H42A	−0.111695	0.417330	0.215439	0.033*
H42B	0.000236	0.330067	0.136780	0.033*
C43	−0.0679 (2)	0.2013 (2)	0.25739 (17)	0.0283 (4)
N44	−0.1000 (2)	0.0852 (2)	0.29014 (16)	0.0380 (4)
C9	0.3168 (2)	1.0231 (2)	0.33171 (17)	0.0290 (4)
H9A	0.209310	1.005667	0.281911	0.035*
H9B	0.337299	1.136793	0.362339	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.02301 (8)	0.02802 (9)	0.03002 (9)	0.00191 (6)	−0.00023 (6)	0.00685 (6)
C	0.0219 (9)	0.0251 (9)	0.0493 (13)	0.0034 (7)	0.0053 (9)	0.0149 (9)
N	0.0426 (11)	0.0317 (9)	0.0544 (12)	0.0026 (8)	−0.0034 (9)	−0.0016 (8)
S1	0.0299 (2)	0.0280 (2)	0.0258 (2)	−0.00200 (19)	0.00382 (19)	0.00125 (17)
C2	0.0266 (9)	0.0286 (9)	0.0303 (10)	0.0004 (8)	0.0082 (8)	0.0029 (7)
S	0.0347 (3)	0.0463 (3)	0.0320 (3)	0.0160 (2)	0.0066 (2)	0.0164 (2)
C3	0.0208 (8)	0.0243 (9)	0.0292 (9)	0.0023 (7)	0.0036 (7)	0.0038 (7)
N4	0.0185 (7)	0.0223 (7)	0.0258 (7)	0.0002 (6)	0.0026 (6)	0.0044 (6)
C5	0.0195 (8)	0.0267 (9)	0.0252 (9)	−0.0003 (7)	0.0017 (7)	0.0014 (7)
C6	0.0184 (8)	0.0283 (9)	0.0254 (9)	0.0002 (7)	0.0004 (7)	0.0060 (7)
N7	0.0179 (7)	0.0230 (7)	0.0244 (7)	−0.0005 (6)	0.0007 (6)	0.0041 (6)
C8	0.0262 (9)	0.0231 (9)	0.0282 (9)	−0.0008 (7)	0.0021 (7)	0.0051 (7)
C71	0.0188 (8)	0.0262 (9)	0.0276 (9)	0.0021 (7)	0.0007 (7)	0.0091 (7)
C72	0.0211 (9)	0.0295 (9)	0.0284 (9)	0.0020 (7)	0.0023 (7)	0.0097 (7)
C73	0.0282 (10)	0.0375 (10)	0.0250 (9)	0.0010 (8)	0.0020 (8)	0.0069 (8)
N74	0.0317 (10)	0.0655 (13)	0.0382 (10)	0.0107 (9)	0.0095 (8)	0.0052 (9)
C41	0.0214 (9)	0.0229 (8)	0.0303 (9)	−0.0009 (7)	0.0017 (7)	0.0048 (7)
C42	0.0243 (9)	0.0284 (9)	0.0283 (9)	−0.0045 (7)	0.0039 (7)	0.0020 (7)
C43	0.0205 (9)	0.0290 (10)	0.0326 (10)	−0.0027 (7)	0.0045 (7)	−0.0033 (8)
N44	0.0312 (9)	0.0305 (9)	0.0494 (11)	−0.0045 (7)	0.0039 (8)	0.0034 (8)
C9	0.0317 (10)	0.0222 (9)	0.0333 (10)	0.0017 (7)	0.0063 (8)	0.0049 (7)

Geometric parameters (Å, º) top

Ag1—S1	2.5074 (5)	N7—C8	1.462 (2)
Ag1—S	2.4390 (5)	N7—C71	1.465 (2)
Ag1—N4	2.5490 (14)	C8—H8A	0.9900
Ag1—N7	2.5561 (15)	C8—H8B	0.9900
C—N	1.152 (3)	C8—C9	1.528 (3)
C—S	1.670 (2)	C71—H71A	0.9900
S1—C2	1.8241 (19)	C71—H71B	0.9900
S1—C9	1.8211 (19)	C71—C72	1.541 (2)
C2—H2A	0.9900	C72—H72A	0.9900
C2—H2B	0.9900	C72—H72B	0.9900
C2—C3	1.526 (3)	C72—C73	1.467 (3)
C3—H3A	0.9900	C73—N74	1.132 (3)
C3—H3B	0.9900	C41—H41A	0.9900
C3—N4	1.468 (2)	C41—H41B	0.9900
N4—C5	1.479 (2)	C41—C42	1.548 (2)
N4—C41	1.462 (2)	C42—H42A	0.9900
C5—H5A	0.9900	C42—H42B	0.9900
C5—H5B	0.9900	C42—C43	1.464 (3)
C5—C6	1.525 (2)	C43—N44	1.135 (2)
C6—H6A	0.9900	C9—H9A	0.9900
C6—H6B	0.9900	C9—H9B	0.9900
C6—N7	1.476 (2)

S1—Ag1—N4	79.60 (4)	C8—N7—C6	114.09 (14)
S1—Ag1—N7	79.77 (4)	C8—N7—C71	111.70 (14)
S—Ag1—S1	160.21 (2)	C71—N7—Ag1	101.89 (10)
S—Ag1—N4	119.16 (4)	C71—N7—C6	113.25 (14)
S—Ag1—N7	111.02 (4)	N7—C8—H8A	108.5
N4—Ag1—N7	71.15 (5)	N7—C8—H8B	108.5
N—C—S	177.7 (2)	N7—C8—C9	115.13 (15)
C2—S1—Ag1	95.16 (7)	H8A—C8—H8B	107.5
C9—S1—Ag1	101.15 (6)	C9—C8—H8A	108.5
C9—S1—C2	103.37 (9)	C9—C8—H8B	108.5
S1—C2—H2A	108.3	N7—C71—H71A	108.6
S1—C2—H2B	108.3	N7—C71—H71B	108.6
H2A—C2—H2B	107.4	N7—C71—C72	114.52 (14)
C3—C2—S1	115.81 (13)	H71A—C71—H71B	107.6
C3—C2—H2A	108.3	C72—C71—H71A	108.6
C3—C2—H2B	108.3	C72—C71—H71B	108.6
C—S—Ag1	97.17 (7)	C71—C72—H72A	109.5
C2—C3—H3A	108.8	C71—C72—H72B	109.5
C2—C3—H3B	108.8	H72A—C72—H72B	108.1
H3A—C3—H3B	107.7	C73—C72—C71	110.56 (15)
N4—C3—C2	113.77 (15)	C73—C72—H72A	109.5
N4—C3—H3A	108.8	C73—C72—H72B	109.5
N4—C3—H3B	108.8	N74—C73—C72	177.8 (2)
C3—N4—Ag1	110.77 (10)	N4—C41—H41A	108.7
C3—N4—C5	114.32 (14)	N4—C41—H41B	108.7
C5—N4—Ag1	102.34 (10)	N4—C41—C42	114.42 (15)
C41—N4—Ag1	103.42 (10)	H41A—C41—H41B	107.6
C41—N4—C3	112.58 (14)	C42—C41—H41A	108.7
C41—N4—C5	112.35 (14)	C42—C41—H41B	108.7
N4—C5—H5A	108.8	C41—C42—H42A	109.5
N4—C5—H5B	108.8	C41—C42—H42B	109.5
N4—C5—C6	113.72 (14)	H42A—C42—H42B	108.1
H5A—C5—H5B	107.7	C43—C42—C41	110.59 (16)
C6—C5—H5A	108.8	C43—C42—H42A	109.5
C6—C5—H5B	108.8	C43—C42—H42B	109.5
C5—C6—H6A	108.9	N44—C43—C42	178.4 (2)
C5—C6—H6B	108.9	S1—C9—H9A	108.3
H6A—C6—H6B	107.7	S1—C9—H9B	108.3
N7—C6—C5	113.24 (14)	C8—C9—S1	116.03 (14)
N7—C6—H6A	108.9	C8—C9—H9A	108.3
N7—C6—H6B	108.9	C8—C9—H9B	108.3
C6—N7—Ag1	111.38 (10)	H9A—C9—H9B	107.4
C8—N7—Ag1	103.40 (10)

Ag1—S1—C2—C3	−52.45 (14)	N4—C41—C42—C43	−173.76 (16)
Ag1—S1—C9—C8	−18.86 (15)	C5—N4—C41—C42	−60.7 (2)
Ag1—N4—C5—C6	−58.42 (15)	C5—C6—N7—Ag1	−16.69 (18)
Ag1—N4—C41—C42	−170.34 (13)	C5—C6—N7—C8	−133.28 (16)
Ag1—N7—C8—C9	−54.08 (16)	C5—C6—N7—C71	97.45 (17)
Ag1—N7—C71—C72	−168.44 (12)	C6—N7—C8—C9	67.1 (2)
S1—C2—C3—N4	55.39 (19)	C6—N7—C71—C72	71.83 (19)
C2—S1—C9—C8	−116.97 (15)	N7—C8—C9—S1	53.5 (2)
C2—C3—N4—Ag1	−23.22 (17)	N7—C71—C72—C73	179.87 (15)
C2—C3—N4—C5	−138.19 (15)	C8—N7—C71—C72	−58.6 (2)
C2—C3—N4—C41	92.03 (18)	C71—N7—C8—C9	−162.91 (15)
C3—N4—C5—C6	61.40 (19)	C41—N4—C5—C6	−168.71 (14)
C3—N4—C41—C42	70.1 (2)	C9—S1—C2—C3	50.32 (16)
N4—C5—C6—N7	54.1 (2)

µ-Thiocyanato-κ²S:S-bis{[7-(2-cyanoethyl)-1,4-dithia-7-azacyclononane-κ³N,S,S']silver(I)} tetrafluoridoborate (Ag2L32mu-SCNBF4) top

Crystal data top

[Ag₂(C₉H₁₆N₂S₂)₂(SCN)]BF₄	F(000) = 3168
M_r = 793.34	D_x = 1.856 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 28.537 (3) Å	Cell parameters from 35 reflections
b = 8.4362 (11) Å	θ = 11.1–15.4°
c = 27.216 (3) Å	µ = 1.79 mm⁻¹
β = 119.940 (9)°	T = 150 K
V = 5677.6 (12) Å³	Tablet, colourless
Z = 8	0.27 × 0.15 × 0.12 mm

Data collection top

Stoe STADI4 4-circle diffractometer	4138 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.025
Planar graphite monochromator	θ_max = 25.0°, θ_min = 2.6°
Scan width (ω) = 1.04 – 1.20, scan ratio 2θ:ω = 1.00 I(Net) and sigma(I) calculated according to Blessing (1987)	h = −33→33
Absorption correction: integration (SHELXTL; Sheldrick, 2008)	k = −10→0
T_min = 0.713, T_max = 0.822	l = −32→32
5547 measured reflections	3 standard reflections every 60 min
4972 independent reflections	intensity decay: 7.0%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.015P)² + 34.6966P] where P = (F_o² + 2F_c²)/3
S = 1.15	(Δ/σ)_max = 0.001
4972 reflections	Δρ_max = 0.56 e Å⁻³
326 parameters	Δρ_min = −0.52 e Å⁻³
0 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.000099 (18)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ag1	0.08025 (2)	0.93692 (4)	0.41389 (2)	0.02154 (11)
Ag2	0.09609 (2)	0.98647 (5)	0.31130 (2)	0.02240 (11)
S1A	0.04351 (5)	0.82782 (15)	0.22085 (5)	0.0216 (3)
S4A	0.16145 (5)	0.74507 (15)	0.35120 (5)	0.0200 (3)
S4	0.02877 (5)	0.87553 (15)	0.46833 (5)	0.0215 (3)
S1	0.07752 (5)	0.63126 (14)	0.40150 (5)	0.0189 (3)
S	0.08733 (5)	1.18937 (14)	0.37032 (5)	0.0210 (3)
F1	0.33209 (13)	1.0994 (4)	0.31883 (13)	0.0432 (9)
C8A	0.11625 (18)	1.0142 (6)	0.20333 (19)	0.0210 (11)
H8AA	0.137024	1.020249	0.183166	0.025*
H8AB	0.092061	1.107647	0.192029	0.025*
F2	0.32206 (13)	1.0454 (4)	0.39447 (15)	0.0442 (9)
C	0.0214 (2)	1.2361 (6)	0.3298 (2)	0.0244 (12)
F4	0.39578 (15)	0.9572 (5)	0.39134 (17)	0.0588 (11)
N7A	0.15398 (14)	1.0213 (4)	0.26449 (16)	0.0164 (8)
F3	0.38643 (15)	1.2183 (4)	0.40266 (15)	0.0518 (10)
C6	0.14043 (18)	0.8308 (6)	0.54970 (19)	0.0178 (10)
H6A	0.169613	0.866183	0.587338	0.021*
H6B	0.135847	0.715265	0.552039	0.021*
C72A	0.2050 (2)	1.2596 (6)	0.2569 (2)	0.0234 (11)
H72A	0.228958	1.180650	0.253513	0.028*
H72B	0.178893	1.298119	0.218369	0.028*
C9	0.13812 (19)	0.5770 (6)	0.46780 (19)	0.0201 (10)
H9A	0.127040	0.538570	0.494868	0.024*
H9B	0.156343	0.488275	0.460250	0.024*
N7	0.15811 (15)	0.8593 (4)	0.50755 (16)	0.0154 (8)
C5	0.08767 (18)	0.9137 (6)	0.5373 (2)	0.0225 (11)
H5A	0.094240	1.029496	0.541132	0.027*
H5B	0.078955	0.881427	0.566835	0.027*
C3A	0.12826 (19)	0.6089 (6)	0.2919 (2)	0.0231 (11)
H3AA	0.145843	0.618064	0.268501	0.028*
H3AB	0.134308	0.499488	0.306949	0.028*
N74A	0.26226 (18)	1.4920 (5)	0.32126 (19)	0.0292 (10)
N74	0.26658 (19)	1.3362 (6)	0.56519 (19)	0.0342 (11)
C3	0.0239 (2)	0.6604 (6)	0.4664 (2)	0.0226 (11)
H3A	0.054530	0.618100	0.501832	0.027*
H3B	−0.009822	0.630655	0.466159	0.027*
C72	0.1858 (2)	1.1416 (6)	0.5362 (2)	0.0234 (11)
H72C	0.153835	1.177628	0.500623	0.028*
H72D	0.175752	1.138219	0.566178	0.028*
C6A	0.19758 (18)	0.9034 (6)	0.28424 (19)	0.0178 (10)
H6AA	0.229408	0.953201	0.285137	0.021*
H6AB	0.185532	0.815320	0.256543	0.021*
C71	0.20226 (18)	0.9769 (6)	0.5278 (2)	0.0207 (11)
H71A	0.215047	0.983506	0.500082	0.025*
H71B	0.232883	0.939793	0.564235	0.025*
C8	0.17881 (18)	0.7127 (6)	0.4957 (2)	0.0201 (11)
H8A	0.209173	0.673261	0.531875	0.024*
H8B	0.193690	0.739896	0.470763	0.024*
N	−0.02324 (19)	1.2731 (6)	0.3034 (2)	0.0405 (13)
C5A	0.21473 (18)	0.8355 (6)	0.3426 (2)	0.0208 (11)
H5AA	0.231275	0.921751	0.370783	0.025*
H5AB	0.243103	0.754923	0.351521	0.025*
C9A	0.08164 (19)	0.8633 (6)	0.1847 (2)	0.0229 (11)
H9AA	0.105591	0.771253	0.191253	0.027*
H9AB	0.055960	0.869820	0.143422	0.027*
C2A	0.06761 (19)	0.6337 (6)	0.2535 (2)	0.0244 (11)
H2AA	0.049892	0.609113	0.275916	0.029*
H2AB	0.054699	0.554352	0.222610	0.029*
C73A	0.23715 (19)	1.3917 (6)	0.2920 (2)	0.0194 (11)
C73	0.2306 (2)	1.2535 (6)	0.5525 (2)	0.0239 (11)
B1	0.3592 (2)	1.0805 (7)	0.3769 (2)	0.0235 (13)
C2	0.02391 (19)	0.5797 (6)	0.4164 (2)	0.0221 (11)
H2A	−0.011122	0.602855	0.381983	0.027*
H2B	0.025409	0.463750	0.422692	0.027*
C71A	0.17420 (19)	1.1811 (6)	0.2842 (2)	0.0189 (10)
H71C	0.198667	1.177462	0.325824	0.023*
H71D	0.143187	1.249674	0.276836	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.0239 (2)	0.0180 (2)	0.0196 (2)	0.00354 (16)	0.00846 (16)	0.00433 (16)
Ag2	0.0245 (2)	0.0204 (2)	0.0276 (2)	−0.00087 (16)	0.01692 (17)	−0.00617 (17)
S1A	0.0141 (6)	0.0252 (7)	0.0230 (6)	−0.0016 (5)	0.0075 (5)	−0.0031 (5)
S4A	0.0210 (6)	0.0194 (6)	0.0204 (6)	0.0003 (5)	0.0108 (5)	0.0021 (5)
S4	0.0164 (6)	0.0248 (7)	0.0211 (6)	0.0004 (5)	0.0076 (5)	−0.0045 (5)
S1	0.0201 (6)	0.0171 (6)	0.0170 (6)	0.0003 (5)	0.0074 (5)	−0.0011 (5)
S	0.0257 (6)	0.0147 (6)	0.0216 (6)	0.0015 (5)	0.0110 (5)	−0.0020 (5)
F1	0.046 (2)	0.049 (2)	0.0232 (16)	−0.0090 (17)	0.0084 (15)	0.0060 (15)
C8A	0.019 (2)	0.025 (3)	0.017 (2)	0.001 (2)	0.008 (2)	0.002 (2)
F2	0.0427 (19)	0.047 (2)	0.058 (2)	−0.0115 (17)	0.0365 (18)	−0.0007 (18)
C	0.037 (3)	0.012 (3)	0.032 (3)	0.003 (2)	0.023 (3)	0.001 (2)
F4	0.049 (2)	0.058 (3)	0.073 (3)	0.021 (2)	0.034 (2)	0.025 (2)
N7A	0.0141 (19)	0.011 (2)	0.019 (2)	0.0033 (16)	0.0050 (16)	0.0016 (16)
F3	0.059 (2)	0.056 (2)	0.051 (2)	−0.033 (2)	0.0348 (19)	−0.0278 (19)
C6	0.017 (2)	0.021 (3)	0.013 (2)	−0.001 (2)	0.0061 (19)	−0.001 (2)
C72A	0.031 (3)	0.018 (3)	0.025 (3)	−0.007 (2)	0.017 (2)	−0.006 (2)
C9	0.024 (3)	0.011 (2)	0.018 (2)	0.007 (2)	0.006 (2)	0.003 (2)
N7	0.0156 (19)	0.012 (2)	0.017 (2)	−0.0005 (16)	0.0068 (16)	0.0001 (16)
C5	0.019 (2)	0.030 (3)	0.021 (3)	−0.003 (2)	0.011 (2)	−0.011 (2)
C3A	0.022 (3)	0.015 (3)	0.034 (3)	−0.002 (2)	0.016 (2)	−0.002 (2)
N74A	0.032 (2)	0.026 (3)	0.030 (2)	−0.007 (2)	0.016 (2)	−0.006 (2)
N74	0.041 (3)	0.032 (3)	0.033 (3)	−0.012 (2)	0.021 (2)	−0.012 (2)
C3	0.020 (3)	0.023 (3)	0.024 (3)	−0.003 (2)	0.011 (2)	0.000 (2)
C72	0.028 (3)	0.015 (3)	0.024 (3)	−0.005 (2)	0.011 (2)	−0.003 (2)
C6A	0.016 (2)	0.019 (3)	0.020 (2)	0.000 (2)	0.010 (2)	−0.002 (2)
C71	0.018 (2)	0.023 (3)	0.019 (2)	−0.004 (2)	0.008 (2)	0.001 (2)
C8	0.019 (2)	0.018 (3)	0.021 (3)	0.006 (2)	0.008 (2)	0.004 (2)
N	0.034 (3)	0.029 (3)	0.061 (3)	0.010 (2)	0.025 (3)	0.014 (3)
C5A	0.017 (2)	0.018 (3)	0.022 (3)	0.000 (2)	0.006 (2)	−0.002 (2)
C9A	0.023 (3)	0.027 (3)	0.016 (2)	−0.001 (2)	0.007 (2)	−0.003 (2)
C2A	0.024 (3)	0.020 (3)	0.030 (3)	−0.007 (2)	0.014 (2)	−0.003 (2)
C73A	0.019 (2)	0.019 (3)	0.026 (3)	0.002 (2)	0.015 (2)	0.001 (2)
C73	0.033 (3)	0.021 (3)	0.017 (3)	−0.002 (2)	0.012 (2)	−0.003 (2)
B1	0.018 (3)	0.024 (3)	0.024 (3)	−0.003 (2)	0.007 (2)	−0.001 (3)
C2	0.021 (2)	0.015 (3)	0.025 (3)	−0.002 (2)	0.008 (2)	0.000 (2)
C71A	0.021 (2)	0.016 (3)	0.020 (2)	−0.003 (2)	0.010 (2)	−0.004 (2)

Geometric parameters (Å, º) top

Ag1—Ag2	3.0716 (6)	C9—H9A	0.9900
Ag1—S4	2.6065 (13)	C9—H9B	0.9900
Ag1—S1	2.5966 (13)	C9—C8	1.535 (7)
Ag1—S	2.4943 (13)	N7—C71	1.477 (6)
Ag1—N7	2.492 (4)	N7—C8	1.474 (6)
Ag2—S1A	2.5329 (13)	C5—H5A	0.9900
Ag2—S4A	2.6046 (13)	C5—H5B	0.9900
Ag2—S	2.4441 (13)	C3A—H3AA	0.9900
Ag2—N7A	2.557 (4)	C3A—H3AB	0.9900
S1A—C9A	1.819 (5)	C3A—C2A	1.525 (7)
S1A—C2A	1.826 (5)	N74A—C73A	1.137 (6)
S4A—C3A	1.816 (5)	N74—C73	1.142 (6)
S4A—C5A	1.818 (5)	C3—H3A	0.9900
S4—C5	1.818 (5)	C3—H3B	0.9900
S4—C3	1.819 (5)	C3—C2	1.523 (7)
S1—C9	1.828 (5)	C72—H72C	0.9900
S1—C2	1.820 (5)	C72—H72D	0.9900
S—C	1.685 (5)	C72—C71	1.520 (7)
F1—B1	1.379 (6)	C72—C73	1.470 (7)
C8A—H8AA	0.9900	C6A—H6AA	0.9900
C8A—H8AB	0.9900	C6A—H6AB	0.9900
C8A—N7A	1.464 (6)	C6A—C5A	1.520 (6)
C8A—C9A	1.534 (7)	C71—H71A	0.9900
F2—B1	1.395 (7)	C71—H71B	0.9900
C—N	1.151 (7)	C8—H8A	0.9900
F4—B1	1.384 (7)	C8—H8B	0.9900
N7A—C6A	1.469 (6)	C5A—H5AA	0.9900
N7A—C71A	1.460 (6)	C5A—H5AB	0.9900
F3—B1	1.380 (7)	C9A—H9AA	0.9900
C6—H6A	0.9900	C9A—H9AB	0.9900
C6—H6B	0.9900	C2A—H2AA	0.9900
C6—N7	1.485 (6)	C2A—H2AB	0.9900
C6—C5	1.537 (6)	C2—H2A	0.9900
C72A—H72A	0.9900	C2—H2B	0.9900
C72A—H72B	0.9900	C71A—H71C	0.9900
C72A—C73A	1.457 (7)	C71A—H71D	0.9900
C72A—C71A	1.556 (6)

S4—Ag1—Ag2	157.53 (3)	C6—C5—H5B	108.2
S1—Ag1—Ag2	91.47 (3)	H5A—C5—H5B	107.3
S1—Ag1—S4	83.55 (4)	S4A—C3A—H3AA	108.4
S—Ag1—Ag2	50.81 (3)	S4A—C3A—H3AB	108.4
S—Ag1—S4	129.95 (4)	H3AA—C3A—H3AB	107.4
S—Ag1—S1	142.23 (4)	C2A—C3A—S4A	115.6 (3)
N7—Ag1—Ag2	120.33 (9)	C2A—C3A—H3AA	108.4
N7—Ag1—S4	80.45 (9)	C2A—C3A—H3AB	108.4
N7—Ag1—S1	79.96 (9)	S4—C3—H3A	108.3
N7—Ag1—S	117.91 (9)	S4—C3—H3B	108.3
S1A—Ag2—Ag1	121.80 (3)	H3A—C3—H3B	107.4
S1A—Ag2—S4A	86.88 (4)	C2—C3—S4	115.9 (4)
S1A—Ag2—N7A	78.06 (9)	C2—C3—H3A	108.3
S4A—Ag2—Ag1	85.08 (3)	C2—C3—H3B	108.3
S—Ag2—Ag1	52.28 (3)	H72C—C72—H72D	108.2
S—Ag2—S1A	143.47 (4)	C71—C72—H72C	109.6
S—Ag2—S4A	124.09 (4)	C71—C72—H72D	109.6
S—Ag2—N7A	123.39 (9)	C73—C72—H72C	109.6
N7A—Ag2—Ag1	153.28 (8)	C73—C72—H72D	109.6
N7A—Ag2—S4A	77.95 (9)	C73—C72—C71	110.1 (4)
C9A—S1A—Ag2	102.39 (16)	N7A—C6A—H6AA	108.7
C9A—S1A—C2A	103.2 (2)	N7A—C6A—H6AB	108.7
C2A—S1A—Ag2	96.01 (17)	N7A—C6A—C5A	114.2 (4)
C3A—S4A—Ag2	100.17 (16)	H6AA—C6A—H6AB	107.6
C3A—S4A—C5A	104.4 (2)	C5A—C6A—H6AA	108.7
C5A—S4A—Ag2	95.11 (16)	C5A—C6A—H6AB	108.7
C5—S4—Ag1	93.39 (16)	N7—C71—C72	113.5 (4)
C5—S4—C3	103.0 (2)	N7—C71—H71A	108.9
C3—S4—Ag1	103.85 (17)	N7—C71—H71B	108.9
C9—S1—Ag1	99.68 (16)	C72—C71—H71A	108.9
C2—S1—Ag1	100.52 (16)	C72—C71—H71B	108.9
C2—S1—C9	101.9 (2)	H71A—C71—H71B	107.7
Ag2—S—Ag1	76.91 (4)	C9—C8—H8A	108.2
C—S—Ag1	100.51 (18)	C9—C8—H8B	108.2
C—S—Ag2	100.38 (18)	N7—C8—C9	116.6 (4)
H8AA—C8A—H8AB	107.7	N7—C8—H8A	108.2
N7A—C8A—H8AA	108.9	N7—C8—H8B	108.2
N7A—C8A—H8AB	108.9	H8A—C8—H8B	107.3
N7A—C8A—C9A	113.3 (4)	S4A—C5A—H5AA	108.3
C9A—C8A—H8AA	108.9	S4A—C5A—H5AB	108.3
C9A—C8A—H8AB	108.9	C6A—C5A—S4A	116.0 (3)
N—C—S	177.3 (5)	C6A—C5A—H5AA	108.3
C8A—N7A—Ag2	105.7 (3)	C6A—C5A—H5AB	108.3
C8A—N7A—C6A	113.4 (4)	H5AA—C5A—H5AB	107.4
C6A—N7A—Ag2	112.3 (3)	S1A—C9A—H9AA	108.6
C71A—N7A—Ag2	99.1 (3)	S1A—C9A—H9AB	108.6
C71A—N7A—C8A	112.8 (4)	C8A—C9A—S1A	114.7 (3)
C71A—N7A—C6A	112.6 (4)	C8A—C9A—H9AA	108.6
H6A—C6—H6B	107.5	C8A—C9A—H9AB	108.6
N7—C6—H6A	108.4	H9AA—C9A—H9AB	107.6
N7—C6—H6B	108.4	S1A—C2A—H2AA	107.7
N7—C6—C5	115.5 (4)	S1A—C2A—H2AB	107.7
C5—C6—H6A	108.4	C3A—C2A—S1A	118.6 (3)
C5—C6—H6B	108.4	C3A—C2A—H2AA	107.7
H72A—C72A—H72B	108.2	C3A—C2A—H2AB	107.7
C73A—C72A—H72A	109.8	H2AA—C2A—H2AB	107.1
C73A—C72A—H72B	109.8	N74A—C73A—C72A	177.3 (5)
C73A—C72A—C71A	109.4 (4)	N74—C73—C72	177.7 (6)
C71A—C72A—H72A	109.8	F1—B1—F2	109.2 (4)
C71A—C72A—H72B	109.8	F1—B1—F4	108.9 (5)
S1—C9—H9A	108.7	F1—B1—F3	109.6 (5)
S1—C9—H9B	108.7	F4—B1—F2	109.8 (5)
H9A—C9—H9B	107.6	F3—B1—F2	109.6 (5)
C8—C9—S1	114.3 (3)	F3—B1—F4	109.6 (4)
C8—C9—H9A	108.7	S1—C2—H2A	107.8
C8—C9—H9B	108.7	S1—C2—H2B	107.8
C6—N7—Ag1	111.1 (3)	C3—C2—S1	117.9 (3)
C71—N7—Ag1	111.4 (3)	C3—C2—H2A	107.8
C71—N7—C6	112.1 (4)	C3—C2—H2B	107.8
C8—N7—Ag1	104.3 (3)	H2A—C2—H2B	107.2
C8—N7—C6	111.2 (4)	N7A—C71A—C72A	115.5 (4)
C8—N7—C71	106.5 (3)	N7A—C71A—H71C	108.4
S4—C5—H5A	108.2	N7A—C71A—H71D	108.4
S4—C5—H5B	108.2	C72A—C71A—H71C	108.4
C6—C5—S4	116.4 (3)	C72A—C71A—H71D	108.4
C6—C5—H5A	108.2	H71C—C71A—H71D	107.5

Ag1—S4—C5—C6	−49.6 (4)	C9—S1—C2—C3	59.1 (4)
Ag1—S4—C3—C2	−27.3 (4)	N7—C6—C5—S4	54.9 (5)
Ag1—S1—C9—C8	−20.8 (4)	C5—S4—C3—C2	−124.1 (4)
Ag1—S1—C2—C3	−43.3 (4)	C5—C6—N7—Ag1	−23.3 (5)
Ag1—N7—C71—C72	60.8 (4)	C5—C6—N7—C71	102.0 (4)
Ag1—N7—C8—C9	−55.7 (4)	C5—C6—N7—C8	−138.9 (4)
Ag2—S1A—C9A—C8A	−22.3 (4)	C3A—S4A—C5A—C6A	50.6 (4)
Ag2—S1A—C2A—C3A	−49.9 (4)	C3—S4—C5—C6	55.5 (4)
Ag2—S4A—C3A—C2A	−25.5 (4)	C6A—N7A—C71A—C72A	70.4 (5)
Ag2—S4A—C5A—C6A	−51.3 (4)	C71—N7—C8—C9	−173.6 (4)
Ag2—N7A—C6A—C5A	−24.6 (5)	C8—N7—C71—C72	173.9 (4)
Ag2—N7A—C71A—C72A	−170.8 (3)	C5A—S4A—C3A—C2A	−123.6 (4)
S4A—C3A—C2A—S1A	56.3 (5)	C9A—S1A—C2A—C3A	54.4 (4)
S4—C3—C2—S1	51.2 (5)	C9A—C8A—N7A—Ag2	−55.0 (4)
S1—C9—C8—N7	55.5 (5)	C9A—C8A—N7A—C6A	68.4 (5)
C8A—N7A—C6A—C5A	−144.3 (4)	C9A—C8A—N7A—C71A	−162.2 (4)
C8A—N7A—C71A—C72A	−59.5 (5)	C2A—S1A—C9A—C8A	−121.6 (4)
N7A—C8A—C9A—S1A	55.3 (5)	C73A—C72A—C71A—N7A	−161.9 (4)
N7A—C6A—C5A—S4A	56.0 (5)	C73—C72—C71—N7	−176.1 (4)
C6—N7—C71—C72	−64.3 (5)	C2—S1—C9—C8	−123.8 (4)
C6—N7—C8—C9	64.0 (5)	C71A—N7A—C6A—C5A	86.2 (5)

Selected geometric parameters (Å, °) top

`[Ag(L¹)₂]BF₄`
Ag1—S1	2.5273 (4)	Ag1'—S1'	2.5605 (4)
Ag1—N4	2.6173 (12)	Ag1'—N4'	2.6363 (12)
Ag1—N7	2.6822 (14)	Ag1'—N7'	2.6108 (13)

S1—Ag1—N4	77.67 (3)	S1'—Ag1'—N4'	76.92 (3)
S1—Ag1—N7	76.40 (3)	S1'—Ag1'—N7'	76.70 (3)
N4—Ag1—N7	68.50 (4)	N7'—Ag1'—N4'	69.72 (4)

`[Ag(L²)(SCN)]`
Ag1—S1	2.5074 (5)	Ag1—N7	2.5561 (15)
Ag1—S	2.4390 (5)	C—N	1.152 (3)
Ag1—N4	2.5490 (14)	C—S	1.670 (2)

S1—Ag1—N4	79.60 (4)	S—Ag1—N7	111.02 (4)
S1—Ag1—N7	79.77 (4)	N4—Ag1—N7	71.15 (5)
S—Ag1—S1	160.21 (2)	N—C—S	177.7 (2)
S—Ag1—N4	119.16 (4)

`[Ag₂(L³)₂(µ-SCN)]BF₄`
Ag1—Ag2	3.0716 (6)	Ag2—S1A	2.5329 (13)
Ag1—S4	2.6065 (13)	Ag2—S4A	2.6046 (13)
Ag1—S1	2.5966 (13)	Ag2—S	2.4441 (13)
Ag1—S	2.4943 (13)	Ag2—N7A	2.557 (4)
Ag1—N7	2.492 (4)

S1—Ag1—S4	83.55 (4)	S1A—Ag2—S4A	86.88 (4)
S—Ag1—S4	129.95 (4)	S1A—Ag2—N7A	78.06 (9)
S—Ag1—S1	142.23 (4)	S4A—Ag2—Ag1	85.08 (3)
N7—Ag1—Ag2	120.33 (9)	S—Ag2—S1A	143.47 (4)
N7—Ag1—S4	80.45 (9)	S—Ag2—S4A	124.09 (4)
N7—Ag1—S1	79.96 (9)	S—Ag2—N7A	123.39 (9)
N7—Ag1—S	117.91 (9)	N7A—Ag2—S4A	77.95 (9)
Ag1—S—Ag2	76.91 (4)

Acknowledgements

We thank the University of Cagliari (Italy), the University of Nottingham (UK) and the EPSRC for support.

References

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Volume 78| Part 3| March 2022| Pages 169-175

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