Hexa­kis­(μ3-2-hy­droxy­naphthalene-1-carboxaldehyde thio­semicarbazonato-κ3N2:S:S)hexa­silver(I) N,N-dimethyl­formamide tetra­solvate

Sun, Q.; Chai, L.; Liu, H.; Wang, J.

doi:10.1107/S1600536812050155

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 1| January 2013| Pages m50-m51

https://doi.org/10.1107/S1600536812050155

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Hexakis(μ₃-2-hydroxynaphthalene-1-carboxaldehyde thiosemicarbazonato-κ³N²:S:S)hexasilver(I) N,N-dimethylformamide tetrasolvate

Qiaozhen Sun,^a ^* Liyuan Chai,^b Hui Liu ^b and Junke Wang ^a

^aDepartment of Materials Chemistry, School of Materials Science and Engineering, Key Laboratory of Nonferrous Metal of the Ministry of Education, Central South University, Changsha 410083, People's Republic of China, and ^bChinese National Engineering Research Center for Control & Treatment of Heavy Metal Pollution (CNERC–CTHMP), Environmental Engineering Institute, School of Metallurgical Science and Engineering, Central South University, Changsha 410083, People's Republic of China
^*Correspondence e-mail: rosesunqz@yahoo.com.cn

(Received 9 November 2012; accepted 8 December 2012; online 15 December 2012)

In the title compound, [Ag₆(C₁₂H₁₀N₃OS)₆]·4C₃H₇NO, the hexanuclear complex molecule lies about an inversion center. The six Ag atoms form a distorted octahedron, with Ag⋯Ag distances in the range 2.933 (1)–3.401 (1) Å. Each Ag atom is surrounded by one N atom and two thiolate S atoms from two deprotonated 2-hydroxy-1-naphthaldehyde thiosemicarbazone ligands. Each ligand coordinates three Ag atoms via a bridging thiolate S atom and a monodentate N atom, thus two Ag₃S₃ hexagonal rings are linked together. Two dimethylformamide solvent molecules are located in four sets of sites with half-occupancy and form O⋯H—N hydrogen bonds to the complex molecule. Intramolecular O—H⋯N hydrogen bonds are also present. The discrete hexanuclear clusters are further linked through π–π interactions into layers parallel to (001), the shortest distance between the centroids of aromatic rings being 3.698 (2) Å.

Related literature

For the structure and luminescent properties of d¹⁰ metal complexes, see: Brito et al. (2011 ); Forward et al. (1995 ). For structures of related compexes with thiosemicarbazone Schiff base ligands, see: Ashfield et al. (2004 ); Castiñeiras & Pedrido (2009 ); Li et al. (2010 ); Onodera et al. (2007 ); Pedrido et al. (2009 ); Sun (2011 ); Sun et al. (2012 ); Sun & Chai (2012 ); Xu et al. (2011 ). For bond-length data, see: Han et al. (2004 ).

Experimental

Crystal data

[Ag₆(C₁₂H₁₀N₃OS)₆]·4C₃H₇NO
M_r = 2405.34
Monoclinic, C 2/c
a = 24.604 (3) Å
b = 18.877 (3) Å
c = 24.816 (3) Å
β = 94.763 (3)°
V = 11486 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.17 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.238, T_max = 0.373
28454 measured reflections
10056 independent reflections
7829 reflections with I > 2s(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.145
S = 1.08
10056 reflections
667 parameters
63 restraints
H-atom parameters constrained
Δρ_max = 0.92 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯O4	0.86	1.98	2.835 (8)	175
N6—H6B⋯O6ⁱ	0.86	2.00	2.845 (7)	166
N9—H9A⋯O5ⁱⁱ	0.86	2.31	3.049 (8)	145
N9—H9B⋯O7	0.86	2.02	2.870 (6)	172
O1—H1B⋯N1	0.82	1.86	2.588 (5)	147
O2—H2B⋯N4	0.82	1.85	2.583 (4)	148
O3—H3C⋯N7	0.82	1.86	2.587 (5)	147
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812050155/yk2079sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812050155/yk2079Isup2.hkl

checkCIF report

Comment top

Transition metal-chalcogen compounds, especially for d¹⁰ metal complexes, have attracted a great deal of attention for their interesting structures and excellent luminescent properties (Brito et al., 2011; Forward et al., 1995). Of which many coordination complexes with thiosemicarbazone Schiff base ligands have been reported (Ashfield et al., 2004; Castiñeiras & Pedrido, 2009; Li et al., 2010; Onodera et al., 2007; Pedrido et al., 2009). As a part of our studies on this class of compounds (Sun, 2011; Sun et al., 2012; Sun & Chai, 2012; Xu et al., 2011), we describe here the structure of the title compound.

The structure of the title compound is shown in Fig. 1. It contains an Ag₆ hexanuclear cluster with the Ag···Ag distances varying from 2.93 Å to 3.40 Å (Fig. 2), which is shorter than the sum of van der Waals radii of two silver atoms (3.44 Å) (Han et al., 2004). In the cluster, each Ag(I) ion is surrounded by one nitrogen atom and two thiolate sulfur atoms from two deprotonated ligands L⁵. Each ligand coordinates to three Ag(I) ions using a bridged thiolate sulfur atom and a monodentate nitrogen atom, from which two Ag₃S₃ hexagonal rings are linked together to give the overall Ferris wheel structure.

There are intramolecular hydrogen bonds of O—H···N type. Besides this, solvent DMF molecules are linked to the hexanuclear cluster via O···H—N hydrogen bonds.

Packing of the title compound (Fig. 3) is facilitated through π–π stacking interactions between aromatic rings I, II [defined by the atoms C(1), C(2), C(3), C(4), C(9) and C(10) and the atoms C(13), C(14), C(15), C(16), C(21) and C(22), respectively] and the symmetry related ones (ring centroid distances: 3.78 Å and 3.70 Å, respectively).

Related literature top

For the structure and luminescent properties of d¹⁰ metal complexes, see: Brito et al. (2011); Forward et al. (1995). For structures of related compexes with thiosemicarbazone Schiff base ligands, see: Ashfield et al. (2004); Castiñeiras & Pedrido (2009); Li et al. (2010); Onodera et al. (2007); Pedrido et al. (2009); Sun (2011); Sun et al. (2012); Sun & Chai (2012); Xu et al. (2011). For bond-length data, see: Han et al. (2004).

Experimental top

Triethylamine (25 µL, 0.175 mmol) was added to a solution of L⁵ (0.175 mmol, 0.043 g) in 3 ml DMF. After stirring for 30 min, a DMF solution (2 ml) of AgNO₃ (0.175 mmol, 0.030 g) was added. Block yellow crystals were formed by standing the solution in air for two months. Anal. Calcd for C₈₄H₈₈Ag₆N₂₂O₁₀S₆: C, 41.9; H, 3.7; N, 12.8. Found: C, 41.9; H, 3.6; N, 12.8.

Structure description top

There are intramolecular hydrogen bonds of O—H···N type. Besides this, solvent DMF molecules are linked to the hexanuclear cluster via O···H—N hydrogen bonds.

For the structure and luminescent properties of d¹⁰ metal complexes, see: Brito et al. (2011); Forward et al. (1995). For structures of related compexes with thiosemicarbazone Schiff base ligands, see: Ashfield et al. (2004); Castiñeiras & Pedrido (2009); Li et al. (2010); Onodera et al. (2007); Pedrido et al. (2009); Sun (2011); Sun et al. (2012); Sun & Chai (2012); Xu et al. (2011). For bond-length data, see: Han et al. (2004).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of title compound showing the atom-numbering scheme with H atoms omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) -x + 0.5, -y + 1.5, -z + 2]
	Fig. 2. Ag₆ octahedron in the title compound
	Fig. 3. Packing diagram of the title compound, viewed along the a axis direction.

Hexakis(µ₃-2-hydroxynaphthalene-1-carboxaldehyde thiosemicarbazonato-κ³N²:S:S)hexasilver(I) N,N'-dimethylformamide tetrasolvate top

Crystal data top

[Ag₆(C₁₂H₁₀N₃OS)₆]·4C₃H₇NO	F(000) = 4816
M_r = 2405.34	D_x = 1.391 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6309 reflections
a = 24.604 (3) Å	θ = 2.2–27.2°
b = 18.877 (3) Å	µ = 1.17 mm⁻¹
c = 24.816 (3) Å	T = 293 K
β = 94.763 (3)°	Block, yellow
V = 11486 (3) Å³	0.22 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	10056 independent reflections
Radiation source: fine-focus sealed tube	7829 reflections with I > 2s(I)
Graphite monochromator	R_int = 0.042
φ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −28→29
T_min = 0.238, T_max = 0.373	k = −22→21
28454 measured reflections	l = −29→16

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.095P)²] where P = (F_o² + 2F_c²)/3
10056 reflections	(Δ/σ)_max = 0.002
667 parameters	Δρ_max = 0.92 e Å⁻³
63 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Ag₆(C₁₂H₁₀N₃OS)₆]·4C₃H₇NO	V = 11486 (3) Å³
M_r = 2405.34	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 24.604 (3) Å	µ = 1.17 mm⁻¹
b = 18.877 (3) Å	T = 293 K
c = 24.816 (3) Å	0.22 × 0.20 × 0.18 mm
β = 94.763 (3)°

Data collection top

Bruker SMART CCD diffractometer	10056 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	7829 reflections with I > 2s(I)
T_min = 0.238, T_max = 0.373	R_int = 0.042
28454 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	63 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.08	Δρ_max = 0.92 e Å⁻³
10056 reflections	Δρ_min = −0.42 e Å⁻³
667 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ag1	0.171626 (12)	0.813538 (16)	0.482106 (12)	0.05265 (8)
Ag2	0.240712 (12)	0.788788 (17)	0.582419 (12)	0.05635 (9)
Ag3	0.191030 (13)	0.661685 (16)	0.509778 (12)	0.05414 (8)
S1	0.16540 (4)	0.75257 (5)	0.39220 (4)	0.0510 (2)
S2	0.16228 (4)	0.70906 (5)	0.59592 (4)	0.0520 (2)
S3	0.27035 (4)	0.57841 (5)	0.51287 (4)	0.0499 (2)
N1	0.09822 (14)	0.57526 (18)	0.43441 (14)	0.0591 (9)
N2	0.13114 (13)	0.63483 (17)	0.43751 (13)	0.0531 (8)
N3	0.08875 (19)	0.6661 (3)	0.35352 (18)	0.0993 (14)
H3A	0.0673	0.6301	0.3527	0.119*
H3B	0.0868	0.6956	0.3271	0.119*
N4	0.05033 (12)	0.83205 (16)	0.52337 (13)	0.0475 (8)
N5	0.10008 (12)	0.79779 (16)	0.53377 (12)	0.0476 (8)
N6	0.06729 (14)	0.76102 (19)	0.61488 (13)	0.0614 (9)
H6A	0.0380	0.7858	0.6092	0.074*
H6B	0.0725	0.7360	0.6438	0.074*
N7	0.27039 (15)	0.5619 (2)	0.35485 (14)	0.0656 (10)
N8	0.27440 (14)	0.59230 (18)	0.40692 (12)	0.0575 (9)
N9	0.25925 (15)	0.47922 (19)	0.43895 (15)	0.0671 (10)
H9A	0.2586	0.4610	0.4071	0.080*
H9B	0.2547	0.4527	0.4664	0.080*
O1	0.02497 (15)	0.48899 (18)	0.39190 (13)	0.0853 (10)
H1B	0.0463	0.5224	0.3930	0.128*
O2	−0.05009 (11)	0.86290 (17)	0.53609 (12)	0.0686 (8)
H2B	−0.0209	0.8420	0.5413	0.103*
O3	0.2174 (2)	0.4973 (3)	0.27494 (18)	0.1230 (16)
H3C	0.2245	0.5096	0.3064	0.184*
C1	0.0316 (2)	0.4524 (2)	0.4389 (2)	0.0696 (12)
C2	−0.0022 (2)	0.3926 (3)	0.4433 (2)	0.0858 (16)
H2A	−0.0264	0.3788	0.4144	0.103*
C3	0.0012 (2)	0.3550 (3)	0.4907 (2)	0.0824 (15)
H3D	−0.0213	0.3157	0.4936	0.099*
C4	0.0369 (2)	0.3736 (2)	0.5340 (2)	0.0710 (13)
C5	0.0388 (3)	0.3357 (3)	0.5855 (3)	0.0961 (18)
H5A	0.0155	0.2975	0.5892	0.115*
C6	0.0736 (3)	0.3551 (3)	0.6272 (3)	0.109 (2)
H6C	0.0739	0.3303	0.6596	0.131*
C7	0.1083 (3)	0.4100 (3)	0.6233 (2)	0.104 (2)
H7B	0.1324	0.4220	0.6527	0.125*
C8	0.1084 (2)	0.4484 (3)	0.5761 (2)	0.0873 (16)
H8B	0.1330	0.4856	0.5742	0.105*
C9	0.07184 (19)	0.4329 (2)	0.53019 (19)	0.0678 (12)
C10	0.06846 (18)	0.4728 (2)	0.48118 (18)	0.0633 (11)
C11	0.10170 (17)	0.5363 (2)	0.47600 (18)	0.0600 (11)
H11A	0.1266	0.5487	0.5047	0.072*
C12	0.12505 (16)	0.6761 (2)	0.39585 (16)	0.0529 (10)
C13	−0.04809 (15)	0.9071 (2)	0.49380 (17)	0.0547 (10)
C14	−0.09473 (17)	0.9478 (2)	0.47924 (19)	0.0659 (12)
H14A	−0.1254	0.9428	0.4984	0.079*
C15	−0.09576 (17)	0.9941 (3)	0.4380 (2)	0.0671 (12)
H15A	−0.1271	1.0207	0.4294	0.080*
C16	−0.05039 (17)	1.0030 (2)	0.40773 (17)	0.0602 (11)
C17	−0.0514 (2)	1.0516 (3)	0.36387 (19)	0.0711 (13)
H17A	−0.0823	1.0790	0.3556	0.085*
C18	−0.0087 (2)	1.0587 (3)	0.3344 (2)	0.0818 (15)
H18A	−0.0103	1.0906	0.3058	0.098*
C19	0.0376 (2)	1.0188 (3)	0.3463 (2)	0.0780 (14)
H19A	0.0667	1.0235	0.3249	0.094*
C20	0.04169 (19)	0.9720 (2)	0.38905 (18)	0.0654 (12)
H20A	0.0739	0.9468	0.3968	0.078*
C21	−0.00225 (15)	0.9620 (2)	0.42120 (16)	0.0521 (10)
C22	−0.00177 (15)	0.9137 (2)	0.46551 (15)	0.0497 (9)
C23	0.04720 (15)	0.87334 (19)	0.48270 (15)	0.0484 (9)
H23A	0.0776	0.8780	0.4630	0.058*
C24	0.10444 (14)	0.76144 (19)	0.57889 (14)	0.0435 (8)
C25	0.2510 (3)	0.5314 (4)	0.2427 (2)	0.104 (2)
C26	0.2459 (3)	0.5160 (4)	0.1857 (3)	0.1147 (18)
H26A	0.2203	0.4836	0.1712	0.138*
C27	0.2789 (3)	0.5496 (4)	0.1544 (3)	0.1144 (18)
H27A	0.2745	0.5391	0.1177	0.137*
C28	0.3180 (3)	0.5973 (3)	0.1699 (2)	0.0934 (15)
C29	0.3531 (3)	0.6318 (4)	0.1345 (2)	0.1046 (18)
H29A	0.3493	0.6213	0.0977	0.126*
C30	0.3886 (3)	0.6755 (4)	0.1515 (3)	0.127 (2)
H30A	0.4086	0.6988	0.1268	0.152*
C31	0.3996 (3)	0.6910 (4)	0.2081 (3)	0.114 (2)
H31A	0.4273	0.7223	0.2199	0.137*
C32	0.3687 (3)	0.6590 (3)	0.2442 (2)	0.1015 (19)
H32A	0.3757	0.6680	0.2809	0.122*
C33	0.3264 (2)	0.6125 (3)	0.2266 (2)	0.0911 (16)
C34	0.2898 (2)	0.5779 (3)	0.26316 (19)	0.0814 (15)
C35	0.29397 (18)	0.5973 (3)	0.32006 (16)	0.0645 (12)
H35A	0.3145	0.6368	0.3313	0.077*
C36	0.26717 (15)	0.5477 (2)	0.44566 (15)	0.0488 (9)
C37	0.1231 (5)	0.9297 (5)	0.2325 (5)	0.087 (3)	0.50
H37A	0.1419	0.9325	0.2679	0.130*	0.50
H37B	0.0973	0.9678	0.2277	0.130*	0.50
H37C	0.1489	0.9331	0.2056	0.130*	0.50
C38	0.0619 (5)	0.8437 (6)	0.1746 (5)	0.089 (3)	0.50
H38A	0.0455	0.7980	0.1785	0.133*	0.50
H38B	0.0854	0.8423	0.1456	0.133*	0.50
H38C	0.0338	0.8784	0.1667	0.133*	0.50
C39	0.0960 (4)	0.8193 (6)	0.2672 (4)	0.078 (3)	0.50
H39A	0.1113	0.8342	0.3008	0.093*	0.50
N10	0.0949 (3)	0.8634 (3)	0.2267 (3)	0.0561 (17)	0.50
O4	0.0773 (3)	0.7578 (4)	0.2628 (3)	0.095 (2)	0.50
C40	0.2559 (5)	0.7879 (6)	0.2711 (4)	0.087 (3)	0.50
H40A	0.2754	0.8308	0.2806	0.130*	0.50
H40B	0.2801	0.7482	0.2767	0.130*	0.50
H40C	0.2260	0.7828	0.2932	0.130*	0.50
C41	0.2129 (6)	0.7401 (7)	0.2012 (6)	0.161 (6)	0.50
H41A	0.2007	0.7454	0.1636	0.242*	0.50
H41B	0.1820	0.7328	0.2217	0.242*	0.50
H41C	0.2369	0.7001	0.2057	0.242*	0.50
C42	0.2428 (7)	0.8450 (8)	0.1807 (6)	0.125 (5)	0.50
H42A	0.2656	0.8799	0.1965	0.150*	0.50
N11	0.2359 (3)	0.7908 (4)	0.2164 (3)	0.0563 (18)	0.50
O5	0.2296 (5)	0.8580 (5)	0.1406 (3)	0.136 (4)	0.50
O6	0.4334 (3)	0.8328 (4)	0.2955 (3)	0.090 (2)	0.50
C43	0.4240 (4)	1.0056 (5)	0.2406 (4)	0.081 (3)	0.50
H43A	0.4350	1.0254	0.2754	0.121*	0.50
H43B	0.3889	1.0239	0.2279	0.121*	0.50
H43C	0.4502	1.0180	0.2155	0.121*	0.50
C44	0.4052 (4)	0.8921 (6)	0.1971 (4)	0.084 (3)	0.50
H44A	0.4048	0.8424	0.2051	0.126*	0.50
H44B	0.4307	0.9012	0.1707	0.126*	0.50
H44C	0.3694	0.9069	0.1832	0.126*	0.50
C45	0.4319 (4)	0.8969 (7)	0.2912 (5)	0.089 (3)	0.50
H45A	0.4389	0.9239	0.3224	0.107*	0.50
N12	0.4210 (3)	0.9304 (4)	0.2449 (2)	0.063 (2)	0.50
O7	0.2454 (2)	0.3792 (3)	0.5239 (2)	0.0587 (13)	0.50
C46	0.1547 (4)	0.2320 (4)	0.5242 (4)	0.075 (3)	0.50
H46A	0.1703	0.2201	0.5598	0.112*	0.50
H46B	0.1600	0.1934	0.5000	0.112*	0.50
H46C	0.1164	0.2410	0.5252	0.112*	0.50
C47	0.1648 (4)	0.3228 (5)	0.4527 (4)	0.073 (3)	0.50
H47A	0.1858	0.3643	0.4461	0.109*	0.50
H47B	0.1268	0.3351	0.4510	0.109*	0.50
H47C	0.1704	0.2876	0.4259	0.109*	0.50
C48	0.2207 (4)	0.3293 (4)	0.5356 (3)	0.060 (2)	0.50
H48A	0.2294	0.3111	0.5701	0.072*	0.50
N13	0.1815 (3)	0.2954 (3)	0.5052 (3)	0.0468 (15)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.05776 (17)	0.05486 (17)	0.04597 (16)	−0.00022 (13)	0.00805 (13)	0.00734 (12)
Ag2	0.05578 (17)	0.06027 (18)	0.05285 (18)	0.00050 (13)	0.00367 (14)	0.00891 (13)
Ag3	0.06226 (18)	0.05244 (17)	0.04791 (17)	0.00372 (13)	0.00561 (14)	0.00294 (12)
S1	0.0549 (5)	0.0543 (5)	0.0438 (5)	−0.0023 (4)	0.0035 (4)	0.0061 (4)
S2	0.0564 (5)	0.0552 (5)	0.0450 (5)	0.0023 (4)	0.0079 (4)	0.0091 (4)
S3	0.0570 (5)	0.0488 (5)	0.0446 (5)	0.0013 (4)	0.0081 (4)	0.0031 (4)
N1	0.0648 (19)	0.0566 (19)	0.0556 (19)	−0.0095 (16)	0.0042 (16)	0.0038 (16)
N2	0.0554 (17)	0.0538 (18)	0.0497 (18)	−0.0064 (15)	0.0017 (14)	0.0065 (15)
N3	0.109 (3)	0.098 (3)	0.085 (3)	−0.033 (2)	−0.027 (2)	0.016 (2)
N4	0.0439 (15)	0.0487 (17)	0.0504 (17)	0.0009 (13)	0.0069 (13)	0.0001 (14)
N5	0.0439 (15)	0.0514 (17)	0.0480 (17)	0.0004 (13)	0.0064 (13)	0.0060 (13)
N6	0.0601 (19)	0.073 (2)	0.0532 (19)	0.0072 (17)	0.0165 (16)	0.0100 (16)
N7	0.079 (2)	0.068 (2)	0.0490 (19)	0.0157 (18)	0.0009 (17)	−0.0046 (17)
N8	0.071 (2)	0.063 (2)	0.0390 (17)	0.0076 (17)	0.0063 (15)	0.0032 (15)
N9	0.091 (3)	0.057 (2)	0.054 (2)	−0.0044 (18)	0.0069 (18)	−0.0029 (16)
O1	0.116 (3)	0.073 (2)	0.0638 (19)	−0.0227 (19)	−0.0104 (18)	−0.0023 (16)
O2	0.0522 (15)	0.084 (2)	0.0713 (19)	0.0015 (15)	0.0128 (14)	0.0191 (16)
O3	0.131 (3)	0.137 (4)	0.095 (3)	−0.006 (3)	−0.029 (3)	−0.024 (3)
C1	0.082 (3)	0.057 (2)	0.070 (3)	−0.012 (2)	0.007 (2)	−0.005 (2)
C2	0.105 (4)	0.064 (3)	0.086 (4)	−0.028 (3)	−0.005 (3)	−0.007 (3)
C3	0.093 (3)	0.056 (3)	0.099 (4)	−0.024 (2)	0.011 (3)	−0.001 (3)
C4	0.081 (3)	0.053 (2)	0.080 (3)	−0.011 (2)	0.012 (2)	0.006 (2)
C5	0.110 (4)	0.067 (3)	0.112 (5)	−0.018 (3)	0.013 (4)	0.020 (3)
C6	0.135 (5)	0.097 (4)	0.095 (4)	−0.015 (4)	0.008 (4)	0.041 (3)
C7	0.127 (5)	0.093 (4)	0.088 (4)	−0.028 (4)	−0.022 (3)	0.032 (3)
C8	0.093 (3)	0.075 (3)	0.091 (4)	−0.023 (3)	−0.010 (3)	0.019 (3)
C9	0.073 (3)	0.056 (2)	0.075 (3)	−0.005 (2)	0.004 (2)	0.007 (2)
C10	0.073 (3)	0.054 (2)	0.063 (3)	−0.012 (2)	0.008 (2)	0.0020 (19)
C11	0.063 (2)	0.057 (2)	0.059 (2)	−0.0090 (19)	0.000 (2)	−0.001 (2)
C12	0.057 (2)	0.053 (2)	0.047 (2)	−0.0052 (17)	−0.0048 (17)	0.0039 (17)
C13	0.048 (2)	0.057 (2)	0.058 (2)	−0.0037 (18)	0.0050 (18)	−0.0016 (18)
C14	0.047 (2)	0.071 (3)	0.080 (3)	0.001 (2)	0.010 (2)	−0.001 (2)
C15	0.050 (2)	0.069 (3)	0.081 (3)	0.011 (2)	−0.001 (2)	−0.007 (2)
C16	0.064 (2)	0.052 (2)	0.061 (2)	0.0017 (19)	−0.011 (2)	−0.0077 (19)
C17	0.075 (3)	0.064 (3)	0.072 (3)	0.004 (2)	−0.011 (2)	0.008 (2)
C18	0.106 (4)	0.068 (3)	0.069 (3)	0.001 (3)	−0.005 (3)	0.019 (2)
C19	0.091 (3)	0.079 (3)	0.064 (3)	−0.003 (3)	0.013 (3)	0.013 (2)
C20	0.070 (3)	0.067 (3)	0.060 (3)	0.003 (2)	0.012 (2)	0.006 (2)
C21	0.054 (2)	0.048 (2)	0.053 (2)	−0.0029 (17)	0.0006 (17)	−0.0022 (17)
C22	0.050 (2)	0.048 (2)	0.050 (2)	−0.0012 (16)	−0.0007 (16)	−0.0053 (16)
C23	0.0459 (18)	0.047 (2)	0.053 (2)	0.0008 (16)	0.0070 (16)	−0.0009 (17)
C24	0.0447 (17)	0.0476 (19)	0.0386 (18)	−0.0071 (15)	0.0062 (15)	−0.0008 (15)
C25	0.123 (5)	0.123 (5)	0.060 (3)	0.036 (4)	−0.021 (3)	−0.018 (3)
C26	0.119 (3)	0.127 (5)	0.093 (4)	0.025 (3)	−0.021 (2)	−0.002 (3)
C27	0.131 (3)	0.117 (3)	0.093 (3)	0.036 (3)	−0.002 (2)	−0.010 (3)
C28	0.109 (3)	0.105 (3)	0.0665 (12)	0.033 (3)	0.009 (2)	0.005 (2)
C29	0.126 (3)	0.119 (3)	0.072 (3)	0.026 (3)	0.022 (3)	0.007 (3)
C30	0.137 (4)	0.138 (4)	0.109 (4)	0.021 (3)	0.032 (3)	0.022 (3)
C31	0.123 (4)	0.118 (4)	0.103 (3)	0.020 (3)	0.025 (3)	0.017 (3)
C32	0.126 (4)	0.108 (4)	0.076 (3)	0.045 (4)	0.043 (3)	0.030 (3)
C33	0.116 (4)	0.105 (4)	0.0553 (15)	0.061 (3)	0.026 (2)	0.022 (2)
C34	0.105 (3)	0.088 (3)	0.050 (3)	0.045 (3)	0.000 (2)	0.002 (2)
C35	0.080 (3)	0.072 (3)	0.042 (2)	0.021 (2)	0.006 (2)	0.0029 (19)
C36	0.0509 (19)	0.048 (2)	0.047 (2)	0.0081 (16)	0.0000 (16)	−0.0023 (16)
C37	0.098 (7)	0.069 (6)	0.091 (7)	−0.002 (5)	−0.009 (6)	0.005 (5)
C38	0.104 (4)	0.079 (4)	0.081 (4)	0.007 (3)	−0.013 (4)	0.012 (3)
C39	0.091 (7)	0.082 (6)	0.056 (5)	0.006 (5)	−0.024 (5)	0.014 (5)
N10	0.071 (4)	0.037 (3)	0.057 (4)	0.015 (3)	−0.020 (3)	0.011 (3)
O4	0.105 (4)	0.095 (4)	0.078 (3)	−0.016 (3)	−0.027 (3)	0.037 (3)
C40	0.116 (8)	0.080 (7)	0.063 (6)	0.031 (6)	−0.002 (6)	−0.007 (5)
C41	0.162 (12)	0.139 (11)	0.189 (15)	0.098 (9)	0.052 (11)	0.082 (10)
C42	0.157 (12)	0.105 (10)	0.112 (11)	−0.033 (9)	0.004 (10)	−0.007 (8)
N11	0.079 (4)	0.050 (4)	0.041 (3)	0.008 (3)	0.015 (3)	0.004 (3)
O5	0.222 (10)	0.130 (6)	0.054 (4)	−0.029 (7)	−0.002 (5)	0.058 (4)
O6	0.115 (5)	0.103 (5)	0.055 (3)	0.005 (4)	0.030 (3)	0.049 (3)
C43	0.086 (6)	0.071 (6)	0.084 (7)	−0.016 (5)	−0.003 (5)	0.017 (5)
C44	0.092 (7)	0.084 (7)	0.076 (6)	−0.011 (5)	0.004 (5)	0.033 (5)
C45	0.082 (4)	0.104 (5)	0.082 (4)	0.000 (4)	0.014 (3)	0.004 (4)
N12	0.049 (3)	0.103 (5)	0.038 (3)	0.001 (4)	0.000 (3)	0.029 (3)
O7	0.086 (3)	0.049 (2)	0.038 (2)	−0.033 (2)	−0.010 (2)	0.0095 (19)
C46	0.081 (6)	0.048 (5)	0.096 (7)	−0.031 (4)	0.010 (5)	0.001 (5)
C47	0.078 (6)	0.060 (5)	0.076 (6)	−0.007 (4)	−0.024 (5)	−0.009 (4)
C48	0.101 (6)	0.051 (4)	0.025 (3)	−0.008 (4)	−0.005 (4)	0.007 (3)
N13	0.058 (3)	0.031 (3)	0.050 (4)	−0.010 (3)	0.002 (3)	−0.009 (2)

Geometric parameters (Å, º) top

Ag1—N5	2.282 (3)	C18—C19	1.377 (7)
Ag1—S3ⁱ	2.4869 (10)	C18—H18A	0.9300
Ag1—S1	2.5039 (10)	C19—C20	1.378 (6)
Ag1—Ag2	2.9329 (5)	C19—H19A	0.9300
Ag1—Ag3	2.9769 (6)	C20—C21	1.409 (6)
Ag2—N8ⁱ	2.294 (3)	C20—H20A	0.9300
Ag2—S1ⁱ	2.4699 (10)	C21—C22	1.428 (5)
Ag2—S2	2.4917 (11)	C22—C23	1.459 (5)
Ag2—Ag3ⁱ	3.0931 (5)	C23—H23A	0.9300
Ag2—Ag3	3.1835 (5)	C25—C34	1.364 (8)
Ag3—N2	2.282 (3)	C25—C26	1.438 (8)
Ag3—S2	2.4741 (11)	C26—C27	1.330 (10)
Ag3—S3	2.5020 (10)	C26—H26A	0.9300
Ag3—Ag2ⁱ	3.0931 (5)	C27—C28	1.350 (9)
S1—C12	1.759 (4)	C27—H27A	0.9300
S1—Ag2ⁱ	2.4699 (10)	C28—C33	1.436 (7)
S2—C24	1.755 (4)	C28—C29	1.438 (9)
S3—C36	1.762 (4)	C29—C30	1.248 (10)
S3—Ag1ⁱ	2.4869 (10)	C29—H29A	0.9300
N1—C11	1.264 (5)	C30—C31	1.438 (10)
N1—N2	1.384 (5)	C30—H30A	0.9300
N2—C12	1.293 (5)	C31—C32	1.363 (9)
N3—C12	1.335 (6)	C31—H31A	0.9300
N3—H3A	0.8600	C32—C33	1.403 (9)
N3—H3B	0.8600	C32—H32A	0.9300
N4—C23	1.273 (5)	C33—C34	1.480 (8)
N4—N5	1.390 (4)	C34—C35	1.454 (6)
N5—C24	1.310 (5)	C35—H35A	0.9300
N6—C24	1.330 (5)	C37—N10	1.432 (12)
N6—H6A	0.8600	C37—H37A	0.9600
N6—H6B	0.8600	C37—H37B	0.9600
N7—C35	1.270 (6)	C37—H37C	0.9600
N7—N8	1.410 (5)	C38—N10	1.516 (12)
N8—C36	1.302 (5)	C38—H38A	0.9600
N8—Ag2ⁱ	2.294 (3)	C38—H38B	0.9600
N9—C36	1.315 (5)	C38—H38C	0.9600
N9—H9A	0.8600	C39—O4	1.250 (12)
N9—H9B	0.8600	C39—N10	1.302 (11)
O1—C1	1.354 (6)	C39—H39A	0.9300
O1—H1B	0.8200	C40—N11	1.406 (11)
O2—C13	1.345 (5)	C40—H40A	0.9600
O2—H2B	0.8200	C40—H40B	0.9600
O3—C25	1.361 (8)	C40—H40C	0.9600
O3—H3C	0.8200	C41—N11	1.159 (16)
C1—C10	1.384 (6)	C41—H41A	0.9600
C1—C2	1.411 (7)	C41—H41B	0.9600
C2—C3	1.369 (7)	C41—H41C	0.9600
C2—H2A	0.9300	C42—O5	1.052 (16)
C3—C4	1.377 (7)	C42—N11	1.372 (16)
C3—H3D	0.9300	C42—H42A	0.9300
C4—C9	1.419 (6)	O6—C45	1.215 (14)
C4—C5	1.461 (8)	C43—N12	1.425 (13)
C5—C6	1.340 (9)	C43—H43A	0.9600
C5—H5A	0.9300	C43—H43B	0.9600
C6—C7	1.352 (8)	C43—H43C	0.9600
C6—H6C	0.9300	C44—N12	1.415 (13)
C7—C8	1.377 (8)	C44—H44A	0.9600
C7—H7B	0.9300	C44—H44B	0.9600
C8—C9	1.422 (7)	C44—H44C	0.9600
C8—H8B	0.9300	C45—N12	1.320 (13)
C9—C10	1.428 (6)	C45—H45A	0.9300
C10—C11	1.463 (6)	O7—C48	1.171 (10)
C11—H11A	0.9300	C46—N13	1.463 (10)
C13—C22	1.393 (5)	C46—H46A	0.9600
C13—C14	1.404 (6)	C46—H46B	0.9600
C14—C15	1.343 (7)	C46—H46C	0.9600
C14—H14A	0.9300	C47—N13	1.428 (11)
C15—C16	1.407 (6)	C47—H47A	0.9600
C15—H15A	0.9300	C47—H47B	0.9600
C16—C17	1.423 (6)	C47—H47C	0.9600
C16—C21	1.431 (6)	C48—N13	1.338 (10)
C17—C18	1.334 (7)	C48—H48A	0.9300
C17—H17A	0.9300

N5—Ag1—S3ⁱ	123.04 (8)	C18—C19—C20	121.5 (5)
N5—Ag1—S1	116.61 (8)	C18—C19—H19A	119.3
S3ⁱ—Ag1—S1	114.45 (3)	C20—C19—H19A	119.3
N5—Ag1—Ag2	85.53 (8)	C19—C20—C21	120.8 (4)
S3ⁱ—Ag1—Ag2	78.36 (2)	C19—C20—H20A	119.6
S1—Ag1—Ag2	132.17 (3)	C21—C20—H20A	119.6
N5—Ag1—Ag3	82.03 (8)	C20—C21—C22	124.4 (4)
S3ⁱ—Ag1—Ag3	134.25 (3)	C20—C21—C16	117.0 (4)
S1—Ag1—Ag3	76.10 (2)	C22—C21—C16	118.6 (4)
Ag2—Ag1—Ag3	65.183 (11)	C13—C22—C21	119.4 (3)
N8ⁱ—Ag2—S1ⁱ	115.91 (9)	C13—C22—C23	119.8 (3)
N8ⁱ—Ag2—S2	116.15 (9)	C21—C22—C23	120.8 (3)
S1ⁱ—Ag2—S2	119.55 (4)	N4—C23—C22	123.1 (3)
N8ⁱ—Ag2—Ag1	81.60 (8)	N4—C23—H23A	118.5
S1ⁱ—Ag2—Ag1	136.94 (3)	C22—C23—H23A	118.5
S2—Ag2—Ag1	79.02 (2)	N5—C24—N6	124.4 (3)
N8ⁱ—Ag2—Ag3ⁱ	83.84 (8)	N5—C24—S2	120.5 (3)
S1ⁱ—Ag2—Ag3ⁱ	74.37 (2)	N6—C24—S2	115.1 (3)
S2—Ag2—Ag3ⁱ	139.12 (3)	O3—C25—C34	121.8 (5)
Ag1—Ag2—Ag3ⁱ	68.654 (13)	O3—C25—C26	118.3 (6)
N8ⁱ—Ag2—Ag3	138.11 (8)	C34—C25—C26	119.9 (6)
S1ⁱ—Ag2—Ag3	102.31 (3)	C27—C26—C25	118.0 (7)
S2—Ag2—Ag3	49.88 (2)	C27—C26—H26A	121.0
Ag1—Ag2—Ag3	58.076 (12)	C25—C26—H26A	121.0
Ag3ⁱ—Ag2—Ag3	90.886 (14)	C26—C27—C28	127.3 (7)
N2—Ag3—S2	123.17 (9)	C26—C27—H27A	116.3
N2—Ag3—S3	109.62 (9)	C28—C27—H27A	116.3
S2—Ag3—S3	118.61 (3)	C27—C28—C33	117.0 (6)
N2—Ag3—Ag1	87.24 (8)	C27—C28—C29	125.3 (6)
S2—Ag3—Ag1	78.42 (3)	C33—C28—C29	117.7 (6)
S3—Ag3—Ag1	136.20 (3)	C30—C29—C28	122.0 (7)
N2—Ag3—Ag2ⁱ	80.83 (8)	C30—C29—H29A	119.0
S2—Ag3—Ag2ⁱ	137.87 (3)	C28—C29—H29A	119.0
S3—Ag3—Ag2ⁱ	75.09 (2)	C29—C30—C31	122.4 (8)
Ag1—Ag3—Ag2ⁱ	67.966 (11)	C29—C30—H30A	118.8
N2—Ag3—Ag2	143.62 (8)	C31—C30—H30A	118.8
S2—Ag3—Ag2	50.37 (2)	C32—C31—C30	118.7 (7)
S3—Ag3—Ag2	101.20 (3)	C32—C31—H31A	120.7
Ag1—Ag3—Ag2	56.741 (12)	C30—C31—H31A	120.7
Ag2ⁱ—Ag3—Ag2	89.114 (14)	C31—C32—C33	120.9 (6)
C12—S1—Ag2ⁱ	104.32 (14)	C31—C32—H32A	119.5
C12—S1—Ag1	108.93 (14)	C33—C32—H32A	119.5
Ag2ⁱ—S1—Ag1	86.06 (3)	C32—C33—C28	118.1 (5)
C24—S2—Ag3	106.25 (12)	C32—C33—C34	124.0 (5)
C24—S2—Ag2	104.41 (12)	C28—C33—C34	117.9 (6)
Ag3—S2—Ag2	79.74 (3)	C25—C34—C35	121.0 (5)
C36—S3—Ag1ⁱ	107.32 (13)	C25—C34—C33	119.8 (5)
C36—S3—Ag3	101.81 (12)	C35—C34—C33	119.1 (5)
Ag1ⁱ—S3—Ag3	85.95 (3)	N7—C35—C34	121.9 (5)
C11—N1—N2	115.3 (3)	N7—C35—H35A	119.1
C12—N2—N1	114.6 (3)	C34—C35—H35A	119.1
C12—N2—Ag3	121.3 (3)	N8—C36—N9	124.8 (4)
N1—N2—Ag3	124.1 (2)	N8—C36—S3	119.2 (3)
C12—N3—H3A	120.0	N9—C36—S3	116.0 (3)
C12—N3—H3B	120.0	N10—C37—H37A	109.5
H3A—N3—H3B	120.0	N10—C37—H37B	109.5
C23—N4—N5	115.3 (3)	H37A—C37—H37B	109.5
C24—N5—N4	114.3 (3)	N10—C37—H37C	109.5
C24—N5—Ag1	122.4 (2)	H37A—C37—H37C	109.5
N4—N5—Ag1	122.9 (2)	H37B—C37—H37C	109.5
C24—N6—H6A	120.0	N10—C38—H38A	109.5
C24—N6—H6B	120.0	N10—C38—H38B	109.5
H6A—N6—H6B	120.0	H38A—C38—H38B	109.5
C35—N7—N8	114.1 (4)	N10—C38—H38C	109.5
C36—N8—N7	114.2 (3)	H38A—C38—H38C	109.5
C36—N8—Ag2ⁱ	121.0 (3)	H38B—C38—H38C	109.5
N7—N8—Ag2ⁱ	120.3 (2)	O4—C39—N10	122.9 (9)
C36—N9—H9A	120.0	O4—C39—H39A	118.5
C36—N9—H9B	120.0	N10—C39—H39A	118.5
H9A—N9—H9B	120.0	C39—N10—C37	120.2 (8)
C1—O1—H1B	109.5	C39—N10—C38	118.4 (8)
C13—O2—H2B	109.5	C37—N10—C38	121.3 (7)
C25—O3—H3C	109.5	N11—C40—H40A	109.5
O1—C1—C10	122.3 (4)	N11—C40—H40B	109.5
O1—C1—C2	116.5 (4)	H40A—C40—H40B	109.5
C10—C1—C2	121.1 (5)	N11—C40—H40C	109.5
C3—C2—C1	119.2 (5)	H40A—C40—H40C	109.5
C3—C2—H2A	120.4	H40B—C40—H40C	109.5
C1—C2—H2A	120.4	N11—C41—H41A	109.5
C2—C3—C4	121.7 (5)	N11—C41—H41B	109.5
C2—C3—H3D	119.1	H41A—C41—H41B	109.5
C4—C3—H3D	119.1	N11—C41—H41C	109.5
C3—C4—C9	120.1 (4)	H41A—C41—H41C	109.5
C3—C4—C5	121.9 (5)	H41B—C41—H41C	109.5
C9—C4—C5	118.0 (5)	O5—C42—N11	137.7 (15)
C6—C5—C4	121.0 (5)	O5—C42—H42A	111.2
C6—C5—H5A	119.5	N11—C42—H42A	111.2
C4—C5—H5A	119.5	C41—N11—C42	119.4 (11)
C5—C6—C7	121.3 (6)	C41—N11—C40	113.8 (10)
C5—C6—H6C	119.3	C42—N11—C40	126.8 (9)
C7—C6—H6C	119.3	N12—C43—H43A	109.5
C6—C7—C8	120.7 (6)	N12—C43—H43B	109.5
C6—C7—H7B	119.6	H43A—C43—H43B	109.5
C8—C7—H7B	119.6	N12—C43—H43C	109.5
C7—C8—C9	121.8 (5)	H43A—C43—H43C	109.5
C7—C8—H8B	119.1	H43B—C43—H43C	109.5
C9—C8—H8B	119.1	N12—C44—H44A	109.5
C4—C9—C8	117.1 (4)	N12—C44—H44B	109.5
C4—C9—C10	118.7 (4)	H44A—C44—H44B	109.5
C8—C9—C10	124.2 (4)	N12—C44—H44C	109.5
C1—C10—C9	119.1 (4)	H44A—C44—H44C	109.5
C1—C10—C11	119.9 (4)	H44B—C44—H44C	109.5
C9—C10—C11	120.9 (4)	O6—C45—N12	123.7 (11)
N1—C11—C10	123.2 (4)	O6—C45—H45A	118.1
N1—C11—H11A	118.4	N12—C45—H45A	118.1
C10—C11—H11A	118.4	C45—N12—C44	120.4 (9)
N2—C12—N3	124.7 (4)	C45—N12—C43	122.3 (9)
N2—C12—S1	120.5 (3)	C44—N12—C43	117.2 (7)
N3—C12—S1	114.8 (3)	N13—C46—H46A	109.5
O2—C13—C22	122.2 (3)	N13—C46—H46B	109.5
O2—C13—C14	117.3 (4)	H46A—C46—H46B	109.5
C22—C13—C14	120.5 (4)	N13—C46—H46C	109.5
C15—C14—C13	121.0 (4)	H46A—C46—H46C	109.5
C15—C14—H14A	119.5	H46B—C46—H46C	109.5
C13—C14—H14A	119.5	N13—C47—H47A	109.5
C14—C15—C16	121.3 (4)	N13—C47—H47B	109.5
C14—C15—H15A	119.4	H47A—C47—H47B	109.5
C16—C15—H15A	119.4	N13—C47—H47C	109.5
C15—C16—C17	121.5 (4)	H47A—C47—H47C	109.5
C15—C16—C21	119.2 (4)	H47B—C47—H47C	109.5
C17—C16—C21	119.3 (4)	O7—C48—N13	127.4 (7)
C18—C17—C16	121.3 (4)	O7—C48—H48A	116.3
C18—C17—H17A	119.3	N13—C48—H48A	116.3
C16—C17—H17A	119.3	C48—N13—C47	118.8 (6)
C17—C18—C19	120.1 (5)	C48—N13—C46	122.1 (7)
C17—C18—H18A	119.9	C47—N13—C46	119.1 (7)
C19—C18—H18A	119.9

Symmetry code: (i) −x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O4	0.86	1.98	2.835 (8)	175
N6—H6B···O6ⁱ	0.86	2.00	2.845 (7)	166
N9—H9A···O5ⁱⁱ	0.86	2.31	3.049 (8)	145
N9—H9B···O7	0.86	2.02	2.870 (6)	172
O1—H1B···N1	0.82	1.86	2.588 (5)	147
O2—H2B···N4	0.82	1.85	2.583 (4)	148
O3—H3C···N7	0.82	1.86	2.587 (5)	147

Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x+1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Ag₆(C₁₂H₁₀N₃OS)₆]·4C₃H₇NO
M_r	2405.34
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	24.604 (3), 18.877 (3), 24.816 (3)
β (°)	94.763 (3)
V (Å³)	11486 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.17
Crystal size (mm)	0.22 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.238, 0.373
No. of measured, independent and observed [I > 2s(I)] reflections	28454, 10056, 7829
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.145, 1.08
No. of reflections	10056
No. of parameters	667
No. of restraints	63
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.92, −0.42

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O4	0.86	1.98	2.835 (8)	174.7
N6—H6B···O6ⁱ	0.86	2.00	2.845 (7)	165.6
N9—H9A···O5ⁱⁱ	0.86	2.31	3.049 (8)	144.5
N9—H9B···O7	0.86	2.02	2.870 (6)	172.2
O1—H1B···N1	0.82	1.86	2.588 (5)	147.0
O2—H2B···N4	0.82	1.85	2.583 (4)	147.6
O3—H3C···N7	0.82	1.86	2.587 (5)	146.7

Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x+1/2, y−1/2, −z+1/2.

Acknowledgements

The authors acknowledge financial support from the National Science and Technology Support Program (2012BAC12B03), the Postdoctoral Science Foundation of Central South University and the Fundamental Research Funds for the Central Universities (No. 2012QNZT001).

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