Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107035597/gd3125sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107035597/gd3125Isup2.hkl |
CCDC reference: 661785
For related literature, see: Allen (2002); Bondi (1964); Castiñeiras et al. (2006); Chen et al. (2007); Dennehy, Quinzani & Jennings (2007); Dennehy, Tellería, Tarulli, Quinzani, Mandolesi, Güida, Echeverría, Piro & Castellano (2007); Kristiansson (2001); Nomiya et al. (1997, 2000); Su et al. (2002); Suresh & Koga (2001).
Solid thiosaccharine was prepared according to a previously reported procedure (Dennehy, Tellería et al., 2007). The Ag(tsac) complex was synthesized by drop-wise addition of a solution of AgNO3 (24 mg) in MeCN (6 ml) to another MeCN solution (6 ml) containing thiosaccharine (30 mg), kept under mechanical stirring at room temperature. The resulting yellow solid was filtered off and washed with diethyl ether. By dissolution of the solid (12 mg) in DMSO (2 ml), a yellow solution was obtained. Slow diffusion of CH2Cl2 into this solution yielded yellow plate crystals of [Ag2(tsac)2]n, (I), suitable for single-crystal X-ray diffraction.
IR spectra were obtained in KBr dispersion and in nujol mulls, showing no differences in the vibrational bands; (n, cm-1): 1458 (m), 1401 (m), 1324 (m), 1235 (m), 1166 (s), 1230 (w), 1012 (m), 1006 (m),950 (w), 802 (m), 766 (m), 736 (w), 628 (w), 588 (m) 556 (m), 537 (m), 436 (m).
All H atoms were refined using a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).
Data collection: APEX2, BIS and COSMO (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT, SADABS and XPREP (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2007); software used to prepare material for publication: publCIF (Version 1.5.1c beta; Westrip, 2007).
[Ag(C7H4NO2S2)] | F(000) = 592 |
Mr = 306.10 | Dx = 2.401 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7345 reflections |
a = 12.8718 (6) Å | θ = 3.2–31.4° |
b = 8.0615 (3) Å | µ = 2.83 mm−1 |
c = 8.3059 (3) Å | T = 294 K |
β = 100.695 (2)° | Plate, light yellow |
V = 846.90 (6) Å3 | 0.38 × 0.35 × 0.10 mm |
Z = 4 |
Bruker X8 Kappa-APEXII CCD area-detector diffractometer | 2787 independent reflections |
Radiation source: fine-focus sealed tube | 2404 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ϕ and ω scans | θmax = 31.5°, θmin = 3.6° |
Absorption correction: gaussian [XPREP (Bruker, 2006) and SADABS (Bruker, 2006)] | h = −18→18 |
Tmin = 0.413, Tmax = 0.765 | k = −11→11 |
14582 measured reflections | l = −12→11 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0289P)2 + 1.4082P] where P = (Fo2 + 2Fc2)/3 |
2787 reflections | (Δ/σ)max = 0.002 |
118 parameters | Δρmax = 1.86 e Å−3 |
0 restraints | Δρmin = −1.40 e Å−3 |
[Ag(C7H4NO2S2)] | V = 846.90 (6) Å3 |
Mr = 306.10 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.8718 (6) Å | µ = 2.83 mm−1 |
b = 8.0615 (3) Å | T = 294 K |
c = 8.3059 (3) Å | 0.38 × 0.35 × 0.10 mm |
β = 100.695 (2)° |
Bruker X8 Kappa-APEXII CCD area-detector diffractometer | 2787 independent reflections |
Absorption correction: gaussian [XPREP (Bruker, 2006) and SADABS (Bruker, 2006)] | 2404 reflections with I > 2σ(I) |
Tmin = 0.413, Tmax = 0.765 | Rint = 0.026 |
14582 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.05 | Δρmax = 1.86 e Å−3 |
2787 reflections | Δρmin = −1.40 e Å−3 |
118 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ag1 | 0.538570 (17) | 1.14998 (3) | 0.59011 (3) | 0.04224 (8) | |
C1 | 0.65624 (18) | 0.8319 (3) | 0.7521 (3) | 0.0265 (4) | |
C2 | 0.74465 (17) | 0.7583 (3) | 0.8708 (3) | 0.0268 (4) | |
C3 | 0.7704 (2) | 0.5931 (3) | 0.8984 (3) | 0.0340 (5) | |
H3 | 0.7281 | 0.5097 | 0.8433 | 0.041* | |
C4 | 0.8618 (2) | 0.5549 (4) | 1.0116 (4) | 0.0404 (6) | |
H4 | 0.8803 | 0.4444 | 1.0325 | 0.048* | |
C5 | 0.9255 (2) | 0.6787 (4) | 1.0934 (4) | 0.0405 (6) | |
H5 | 0.9862 | 0.6498 | 1.1675 | 0.049* | |
C6 | 0.9001 (2) | 0.8452 (3) | 1.0665 (3) | 0.0347 (5) | |
H6 | 0.9424 | 0.9290 | 1.1208 | 0.042* | |
C7 | 0.80870 (18) | 0.8803 (3) | 0.9551 (3) | 0.0281 (4) | |
N1 | 0.65841 (16) | 0.9953 (3) | 0.7439 (3) | 0.0313 (4) | |
O1 | 0.82870 (18) | 1.1671 (3) | 0.8129 (3) | 0.0485 (5) | |
O2 | 0.70812 (19) | 1.1559 (3) | 1.0084 (3) | 0.0519 (6) | |
S1 | 0.56174 (5) | 0.70716 (8) | 0.64297 (7) | 0.03197 (13) | |
S2 | 0.75551 (5) | 1.07393 (8) | 0.88691 (8) | 0.03331 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.04035 (13) | 0.03767 (12) | 0.04088 (13) | 0.00170 (8) | −0.01284 (9) | −0.00005 (8) |
C1 | 0.0232 (9) | 0.0309 (10) | 0.0253 (10) | −0.0013 (8) | 0.0042 (8) | −0.0010 (8) |
C2 | 0.0244 (9) | 0.0287 (10) | 0.0274 (10) | 0.0003 (8) | 0.0049 (8) | 0.0004 (8) |
C3 | 0.0352 (12) | 0.0291 (11) | 0.0380 (12) | 0.0003 (9) | 0.0077 (10) | 0.0020 (10) |
C4 | 0.0414 (14) | 0.0343 (13) | 0.0456 (14) | 0.0091 (11) | 0.0082 (12) | 0.0092 (11) |
C5 | 0.0325 (12) | 0.0474 (15) | 0.0393 (13) | 0.0093 (11) | 0.0007 (10) | 0.0080 (11) |
C6 | 0.0272 (11) | 0.0408 (13) | 0.0327 (12) | 0.0010 (9) | −0.0030 (9) | 0.0006 (10) |
C7 | 0.0261 (10) | 0.0283 (10) | 0.0286 (10) | 0.0023 (8) | 0.0014 (8) | −0.0014 (8) |
N1 | 0.0257 (9) | 0.0304 (9) | 0.0345 (10) | 0.0017 (8) | −0.0032 (7) | −0.0022 (8) |
O1 | 0.0461 (12) | 0.0376 (10) | 0.0554 (13) | −0.0125 (9) | −0.0070 (10) | 0.0070 (9) |
O2 | 0.0493 (12) | 0.0489 (12) | 0.0516 (13) | 0.0140 (10) | −0.0055 (10) | −0.0227 (10) |
S1 | 0.0302 (3) | 0.0363 (3) | 0.0273 (3) | −0.0081 (2) | −0.0001 (2) | 0.0002 (2) |
S2 | 0.0311 (3) | 0.0269 (3) | 0.0371 (3) | 0.0019 (2) | −0.0062 (2) | −0.0047 (2) |
Ag1—N1 | 2.199 (2) | C4—C5 | 1.386 (4) |
Ag1—S1i | 2.4111 (7) | C4—H4 | 0.9300 |
Ag1—S1ii | 2.8031 (7) | C5—C6 | 1.390 (4) |
Ag1—Ag1i | 2.9194 (4) | C5—H5 | 0.9300 |
C1—N1 | 1.320 (3) | C6—C7 | 1.385 (3) |
C1—C2 | 1.484 (3) | C6—H6 | 0.9300 |
C1—S1 | 1.704 (2) | C7—S2 | 1.755 (2) |
C2—C3 | 1.381 (3) | N1—S2 | 1.681 (2) |
C2—C7 | 1.386 (3) | O1—S2 | 1.430 (2) |
C3—C4 | 1.398 (4) | O2—S2 | 1.434 (2) |
C3—H3 | 0.9300 | ||
N1—Ag1—S1i | 161.93 (6) | C6—C5—H5 | 119.5 |
N1—Ag1—S1ii | 90.60 (6) | C7—C6—C5 | 116.8 (2) |
S1i—Ag1—S1ii | 107.45 (2) | C7—C6—H6 | 121.6 |
N1—Ag1—Ag1i | 87.89 (6) | C5—C6—H6 | 121.6 |
S1i—Ag1—Ag1i | 84.458 (18) | C6—C7—C2 | 123.0 (2) |
S1ii—Ag1—Ag1i | 112.273 (19) | C6—C7—S2 | 129.0 (2) |
N1—C1—C2 | 114.3 (2) | C2—C7—S2 | 107.95 (17) |
N1—C1—S1 | 125.53 (19) | C1—N1—S2 | 111.09 (17) |
C2—C1—S1 | 120.11 (17) | C1—N1—Ag1 | 125.24 (16) |
C3—C2—C7 | 119.9 (2) | S2—N1—Ag1 | 123.11 (12) |
C3—C2—C1 | 128.7 (2) | C1—S1—Ag1i | 111.62 (8) |
C7—C2—C1 | 111.3 (2) | C1—S1—Ag1iii | 93.69 (8) |
C2—C3—C4 | 118.0 (2) | Ag1i—S1—Ag1iii | 117.19 (3) |
C2—C3—H3 | 121.0 | O1—S2—O2 | 117.43 (15) |
C4—C3—H3 | 121.0 | O1—S2—N1 | 110.93 (13) |
C5—C4—C3 | 121.3 (3) | O2—S2—N1 | 108.29 (13) |
C5—C4—H4 | 119.4 | O1—S2—C7 | 110.92 (13) |
C3—C4—H4 | 119.4 | O2—S2—C7 | 111.98 (14) |
C4—C5—C6 | 121.1 (2) | N1—S2—C7 | 94.99 (11) |
C4—C5—H5 | 119.5 | ||
N1—C1—C2—C3 | −173.8 (2) | Ag1i—Ag1—N1—C1 | −15.2 (2) |
S1—C1—C2—C3 | 7.2 (3) | S1i—Ag1—N1—S2 | 109.18 (18) |
N1—C1—C2—C7 | 3.1 (3) | S1ii—Ag1—N1—S2 | −73.66 (13) |
S1—C1—C2—C7 | −175.83 (17) | Ag1i—Ag1—N1—S2 | 174.07 (13) |
C7—C2—C3—C4 | −0.3 (4) | N1—C1—S1—Ag1i | 18.0 (2) |
C1—C2—C3—C4 | 176.4 (2) | C2—C1—S1—Ag1i | −163.18 (16) |
C2—C3—C4—C5 | −0.4 (4) | N1—C1—S1—Ag1iii | −103.2 (2) |
C3—C4—C5—C6 | 0.5 (5) | C2—C1—S1—Ag1iii | 75.61 (18) |
C4—C5—C6—C7 | 0.1 (4) | C1—N1—S2—O1 | 120.3 (2) |
C5—C6—C7—C2 | −0.8 (4) | Ag1—N1—S2—O1 | −67.81 (17) |
C5—C6—C7—S2 | −177.7 (2) | C1—N1—S2—O2 | −109.4 (2) |
C3—C2—C7—C6 | 0.9 (4) | Ag1—N1—S2—O2 | 62.42 (18) |
C1—C2—C7—C6 | −176.3 (2) | C1—N1—S2—C7 | 5.7 (2) |
C3—C2—C7—S2 | 178.36 (19) | Ag1—N1—S2—C7 | 177.54 (14) |
C1—C2—C7—S2 | 1.1 (2) | C6—C7—S2—O1 | 58.8 (3) |
C2—C1—N1—S2 | −5.9 (3) | C2—C7—S2—O1 | −118.45 (19) |
S1—C1—N1—S2 | 172.91 (14) | C6—C7—S2—O2 | −74.5 (3) |
C2—C1—N1—Ag1 | −177.59 (15) | C2—C7—S2—O2 | 108.23 (19) |
S1—C1—N1—Ag1 | 1.3 (3) | C6—C7—S2—N1 | 173.5 (3) |
S1i—Ag1—N1—C1 | −80.1 (3) | C2—C7—S2—N1 | −3.79 (19) |
S1ii—Ag1—N1—C1 | 97.0 (2) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+1, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Ag(C7H4NO2S2)] |
Mr | 306.10 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 12.8718 (6), 8.0615 (3), 8.3059 (3) |
β (°) | 100.695 (2) |
V (Å3) | 846.90 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.83 |
Crystal size (mm) | 0.38 × 0.35 × 0.10 |
Data collection | |
Diffractometer | Bruker X8 Kappa-APEXII CCD area-detector diffractometer |
Absorption correction | Gaussian [XPREP (Bruker, 2006) and SADABS (Bruker, 2006)] |
Tmin, Tmax | 0.413, 0.765 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14582, 2787, 2404 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.735 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.075, 1.05 |
No. of reflections | 2787 |
No. of parameters | 118 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.86, −1.40 |
Computer programs: APEX2, BIS and COSMO (Bruker, 2006), SAINT (Bruker, 2006), SAINT, SADABS and XPREP (Bruker, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2007), publCIF (Version 1.5.1c beta; Westrip, 2007).
Ag1—N1 | 2.199 (2) | Ag1—Ag1i | 2.9194 (4) |
Ag1—S1i | 2.4111 (7) | C7—S2 | 1.755 (2) |
Ag1—S1ii | 2.8031 (7) | ||
N1—Ag1—S1i | 161.93 (6) | S1ii—Ag1—Ag1i | 112.273 (19) |
N1—Ag1—S1ii | 90.60 (6) | N1—C1—S1 | 125.53 (19) |
S1i—Ag1—S1ii | 107.45 (2) | C2—C1—S1 | 120.11 (17) |
N1—Ag1—Ag1i | 87.89 (6) | C1—N1—S2 | 111.09 (17) |
S1i—Ag1—Ag1i | 84.458 (18) | Ag1i—S1—Ag1iii | 117.19 (3) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+1, y−1/2, −z+3/2. |
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Thionates, anions produced by the deprotonation of thiones, can coordinate to metals, producing anywhere from mononuclear to polynuclear species. Like other thioamides, thiosaccharine [1,2-benzoisothiazol-3-(2H)-thione-1,1-dioxide] is a versatile ligand, with the ability to coordinate to metal centres in many different ways (Dennehy, Quinzani & Jennings, 2007). Silver(I) atoms coordinated to N or S ligands are of particular interest because of their known antibacterial effects (Nomiya et al., 1997, 2000). We have been working with binary and ternary silver thiosaccharinates, first synthesizing the Ag(tsac) complex (where tsac is the thiosaccharinate anion), which crystallized as the hexanuclear cluster [Ag6(tsac)6] from acetonitrile (MeCN) solutions (Dennehy, Tellería et al., 2007). The cluster is insoluble in many organic solvents, but is very soluble in dimethylsulfoxide (DMSO). The 1H and 13C NMR spectra show only one species in the DMSO solution. However, it was not clear if its structure remained hexanuclear or if a smaller unit was present in solution. We recrystallized [Ag6(tsac)6] from DMSO in order to identify the species probably present in solution, giving the title compound, (I). The fact that the new recrystallization leads to a dimeric unit indicates that the hexanuclear cluster is not present in the DMSO solution. It is not possible, however, to conclude whether there are simple mononuclear units or dimeric units in solution.
In complex (I), the thiosaccharinate anions bridge two Ag atoms by their exocyclic S and endocyclic N atoms across a crystallographic centre of inversion to form a centrosymmetic dimeric unit. The basic dimeric units are linked by Ag—Sexo interactions into a two-dimensional network parallel to the crystallographic bc plane.
In the title complex, the Ag—N distance is 2.199 (2) Å, much shorter than the Ag—N bond in [Ag6(tsac)6] [2.285 (2) Å; Dennehy, Tellería et al., 2007] or [Ag4(tsac)4(PPh3)3] [2.270 (8)–2.331 (8) Å; Dennehy, Quinzani & Jennings, 2007], but close to the average Ag—Nsp2 distance found in the Cambridge Structural Database (CSD, Version 5.28, update of January 2007; Allen, 2002) of 2.19 (8) Å for 104 observations. The fact that the endocyclic thiosaccharinate N atom is more strongly coordinated to the AgI atom in (I) than are those in [Ag6(tsac)6] is also reflected by the lengthening of the intraligand C—N bond [1.320 (3) in (I) versus 1.297 (4) Å in the latter].
The Ag—Sexo distance in the dimeric unit of (I) is 2.4111 (7) Å, shorter than the distances observed in the complexes [Ag6(tsac)6] [2.4861 (7) and 2.5014 (8) Å] and [Ag4(tsac)4(PPh3)3] [2.427 (3)–2.660 (3) Å]. The distance in (I) is considerably shorter than the average Ag—S(thiolate) distance found in the CSD of 2.52 (8) Å for 114 observations. The C—Sexo distance also reflects the change in coordination strength of the Sexo atom of the ligand to Ag centres in the title compound versus [Ag6(tsac)6]. In the latter, the existence of two strong bonds between the Sexo atom and two Ag centres produces a longer C—Sexo distance [1.713 (3) Å] than in complex (I) [1.704 (2) Å], in which the Sexo atom forms one bond to an Ag atom and only an interaction to another Ag atom.
The Ag···Ag distance [2.9194 (4) Å] in (I) is in the range considered a strong argentophilic interaction, as reported by different authors (Kristiansson, 2001; Chen et al., 2007). Castiñeiras et al. (2006) confirmed the Ag—Ag binding in a density functional theory study of a hexanuclear thione–silver(I) cluster. The shortest Ag···Ag distance in Castiñeira's complex [2.9996 (9) Å] is even longer than the Ag···Ag distance in (I).
The existence of silver–thione or silver–thionate coordination polymers is well known (Su et al., 2002). In some, the argentophilic interaction is the major organizing force in the polymeric array. In the title compound, the extended two-dimensional motif is linked by µ2-S bridges between AgI atoms of different dimeric units (Fig. 2). The Ag···S interaction of 2.9194 (4) Å is much longer than the sum of the covalent radii of the atoms, considered to be in the range 2.43–2.60 Å (Suresh & Koga, 2001), but much less than the sum of the van der Waals radii (3.52 Å; Bondi, 1964).
The thiosaccharinate ligands of (I) are almost planar (r.m.s. deviation of ring atoms = 0.0378 Å) and stack parallel to each other with an angle of 1.17 (9)° between planes. The distance from the centroid of the phenyl ring of the thiosaccharinate ligand to the neighbouring plane is 3.456 Å.