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The triclinic structure of the title compound, cyclo-tetrakis(μ-1,1-dioxo-1λ6,2-benzothiazole-3-thiolato-κ2S:S)tetrakis[(triphenylphosphane-κP)silver(I)], [Ag4(C7H4NO2S2)4(C18H15P)4], is a polymorph of the previously reported monoclinic structure [Dennehy, Mandolesi, Quinzani & Jennings (2007). Z. Anorg. Allg. Chem. 633, 2746–2752]. In both polymorphs, the complex lies on a crystallographic inversion centre and the bond distances are closely comparable. Some differences can be found in the interatomic angles and torsion angles involving the inner Ag4S4 skeleton. The polymorphs contain essentially identical two-dimensional layers, but with different layer stacking arrangements. In the triclinic form, all layers are related by lattice translation, while in the monoclinic form they are arranged around glide planes so that adjacent layers are mirrored with respect to each other.
Supporting information
CCDC reference: 866743
Thiosaccharin (Htsac) was prepared by the reaction of saccharin (Mallindkrodt)
with Lawesson's reagent (Fluka) in toluene [Quantities?].
Ag6(tsac)6 was obtained as a yellow solid by reaction of AgNO3 and
thiosaccharin in acetonitrile in a 1:1 molar ratio (Dennehy, Tellería et
al., 2007). The title [Ag4(tsac)4(PPh3)4] complex was
prepared by
slow addition of an acetonitrile solution containing 2,5-dimethylpyrazine (10 mg) to another yellow solution of Ag6(tsac)6 (0.0120 g, 0.04 mmol of Ag)
and PPh3 (0.0100 g, 0.04 mmol) in acetonitrile (10 ml). The resulting clear
yellow solution was kept at room temperature and crystals of (I) were formed
after one month.
All H atoms were visible in a difference Fourier map, but they were placed in
idealized positions and allowed to ride for subsequent refinement, with C—H
= 0.93 Å and Uiso(H) = 1.2Ueq(C).
Attention is drawn to a refinement paradox. When checking the final results
with PLATON checkCIF (Spek, 2009), the Hirshfeld tests
implemented
therein generated a significant number of alerts regarding suspiciously large
`Hirshfeld test dfferences' (HTD) for many of the Ag—S bonds, thus advising
careful review of the cation-type assignment. To our surprise, lower R
indices and better Hirshfeld indicators were obtained when the structure was
refined with Pd atoms in place of Ag: R, wR and HTD values are
0.0553, 0.0882 and 17.3, respectively, for Ag, and 0.0543, 0.0830 and 13.2,
respectively, for Pd. This contradicts clear synthetic and analytical evidence
for the composition of the complex; an EDAX analysis on a Philips 515
microscope (Philips Export BV, Eindhoven, The Netherlands) equipped with an
EDAX PV9100 probe (EDAX International Inc., Prairie View, Illinois, USA)
showed that Ag was the only metallic element present. Even if surprising, this
is not a novel paradox: we had previously found similar refinement
`misbehaviour' with different cation pairs (e.g. CuII versus
NiII; Perec & Baggio, 2010).
Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
cyclo-tetrakis(µ-1,1-dioxo-1
λ6,2-benzothiazole-3-thiolato-
κ2S:
S)tetrakis[(triphenylphosphane-
κP)silver(I)]
top
Crystal data top
[Ag4(C7H4NO2S2)4(C18H15P)4] | Z = 1 |
Mr = 2273.49 | F(000) = 1144 |
Triclinic, P1 | Dx = 1.562 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 15.3566 (10) Å | Cell parameters from 4175 reflections |
b = 14.1309 (7) Å | θ = 3.5–28.9° |
c = 14.0768 (6) Å | µ = 1.10 mm−1 |
α = 77.771 (4)° | T = 291 K |
β = 123.880 (3)° | Block, colourless |
γ = 86.465 (1)° | 0.20 × 0.16 × 0.12 mm |
V = 2416.9 (2) Å3 | |
Data collection top
Oxford Gemini CCD S Ultra diffractometer | 11017 independent reflections |
Radiation source: fine-focus sealed tube | 5568 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.060 |
ω scans, thick slices | θmax = 29.0°, θmin = 3.5° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −19→19 |
Tmin = 0.98, Tmax = 0.99 | k = −18→19 |
20631 measured reflections | l = −18→14 |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.030P)2] where P = (Fo2 + 2Fc2)/3 |
11017 reflections | (Δ/σ)max < 0.001 |
577 parameters | Δρmax = 0.72 e Å−3 |
0 restraints | Δρmin = −0.70 e Å−3 |
Crystal data top
[Ag4(C7H4NO2S2)4(C18H15P)4] | γ = 86.465 (1)° |
Mr = 2273.49 | V = 2416.9 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 15.3566 (10) Å | Mo Kα radiation |
b = 14.1309 (7) Å | µ = 1.10 mm−1 |
c = 14.0768 (6) Å | T = 291 K |
α = 77.771 (4)° | 0.20 × 0.16 × 0.12 mm |
β = 123.880 (3)° | |
Data collection top
Oxford Gemini CCD S Ultra diffractometer | 11017 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 5568 reflections with I > 2σ(I) |
Tmin = 0.98, Tmax = 0.99 | Rint = 0.060 |
20631 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.72 e Å−3 |
11017 reflections | Δρmin = −0.70 e Å−3 |
577 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ag1 | −0.07002 (3) | −0.06867 (3) | 0.07782 (3) | 0.05941 (14) | |
Ag2 | −0.15283 (3) | 0.21930 (3) | −0.09355 (3) | 0.05819 (14) | |
P1 | −0.02938 (11) | −0.04555 (10) | 0.26070 (10) | 0.0473 (3) | |
P2 | −0.30143 (11) | 0.33152 (9) | −0.13510 (11) | 0.0438 (3) | |
S17 | −0.42230 (11) | −0.04441 (10) | −0.17977 (11) | 0.0500 (3) | |
S18 | −0.09538 (13) | 0.47073 (11) | −0.34340 (13) | 0.0691 (5) | |
S1 | −0.15624 (11) | 0.04807 (9) | −0.13180 (11) | 0.0494 (3) | |
S2 | 0.02862 (11) | 0.23119 (9) | −0.04545 (10) | 0.0489 (3) | |
O17 | −0.4688 (3) | −0.0063 (3) | −0.1279 (3) | 0.0731 (11) | |
O18 | −0.1151 (3) | 0.5655 (3) | −0.3295 (4) | 0.0896 (14) | |
O27 | −0.4286 (3) | −0.1434 (2) | −0.1870 (3) | 0.0637 (10) | |
O28 | −0.1632 (3) | 0.4588 (3) | −0.4596 (3) | 0.0891 (15) | |
N17 | −0.2958 (3) | −0.0341 (3) | −0.1074 (3) | 0.0459 (10) | |
N18 | −0.0959 (3) | 0.3835 (3) | −0.2437 (4) | 0.0557 (12) | |
C11 | −0.0427 (4) | 0.0845 (4) | 0.2546 (4) | 0.0494 (14) | |
C21 | −0.1083 (4) | 0.1321 (4) | 0.2759 (4) | 0.0565 (15) | |
H21 | −0.1471 | 0.0965 | 0.2969 | 0.068* | |
C31 | −0.1172 (5) | 0.2319 (5) | 0.2665 (5) | 0.0714 (18) | |
H31 | −0.1619 | 0.2633 | 0.2809 | 0.086* | |
C41 | −0.0603 (6) | 0.2847 (5) | 0.2360 (5) | 0.082 (2) | |
H41 | −0.0661 | 0.3520 | 0.2296 | 0.098* | |
C51 | 0.0048 (6) | 0.2385 (5) | 0.2151 (5) | 0.083 (2) | |
H51 | 0.0444 | 0.2743 | 0.1957 | 0.099* | |
C61 | 0.0130 (5) | 0.1397 (5) | 0.2222 (5) | 0.0689 (17) | |
H61 | 0.0562 | 0.1096 | 0.2052 | 0.083* | |
C12 | −0.1203 (4) | −0.0921 (4) | 0.2929 (4) | 0.0479 (13) | |
C22 | −0.0894 (5) | −0.1467 (4) | 0.4038 (5) | 0.0707 (18) | |
H22 | −0.0178 | −0.1602 | 0.4693 | 0.085* | |
C32 | −0.1651 (6) | −0.1821 (5) | 0.4186 (6) | 0.086 (2) | |
H32 | −0.1436 | −0.2199 | 0.4939 | 0.103* | |
C42 | −0.2700 (6) | −0.1618 (5) | 0.3240 (7) | 0.0801 (19) | |
H42 | −0.3202 | −0.1851 | 0.3346 | 0.096* | |
C52 | −0.3016 (5) | −0.1075 (5) | 0.2135 (6) | 0.0742 (18) | |
H52 | −0.3735 | −0.0937 | 0.1487 | 0.089* | |
C62 | −0.2282 (5) | −0.0731 (4) | 0.1975 (5) | 0.0629 (16) | |
H62 | −0.2507 | −0.0364 | 0.1214 | 0.075* | |
C13 | 0.1035 (4) | −0.1061 (4) | 0.3961 (4) | 0.0468 (13) | |
C23 | 0.1467 (5) | −0.2022 (4) | 0.4130 (4) | 0.0616 (16) | |
H23 | 0.1090 | −0.2321 | 0.3529 | 0.074* | |
C33 | 0.2434 (5) | −0.2539 (4) | 0.5158 (5) | 0.0721 (18) | |
H33 | 0.2702 | −0.3187 | 0.5257 | 0.087* | |
C43 | 0.3011 (5) | −0.2108 (5) | 0.6043 (5) | 0.0735 (18) | |
H43 | 0.3674 | −0.2461 | 0.6742 | 0.088* | |
C53 | 0.2608 (5) | −0.1152 (5) | 0.5896 (5) | 0.0678 (18) | |
H53 | 0.3003 | −0.0854 | 0.6492 | 0.081* | |
C63 | 0.1621 (5) | −0.0633 (4) | 0.4867 (4) | 0.0596 (15) | |
H63 | 0.1346 | 0.0009 | 0.4780 | 0.072* | |
C14 | −0.4199 (4) | 0.3503 (3) | −0.2876 (4) | 0.0475 (13) | |
C24 | −0.5212 (5) | 0.3528 (4) | −0.3173 (5) | 0.0682 (17) | |
H24 | −0.5329 | 0.3439 | −0.2582 | 0.082* | |
C34 | −0.6079 (5) | 0.3687 (4) | −0.4372 (6) | 0.082 (2) | |
H34 | −0.6768 | 0.3693 | −0.4572 | 0.098* | |
C44 | −0.5914 (7) | 0.3835 (5) | −0.5246 (6) | 0.087 (2) | |
H44 | −0.6490 | 0.3952 | −0.6043 | 0.105* | |
C54 | −0.4909 (6) | 0.3810 (5) | −0.4945 (5) | 0.091 (2) | |
H54 | −0.4803 | 0.3921 | −0.5545 | 0.109* | |
C64 | −0.4031 (5) | 0.3624 (4) | −0.3766 (5) | 0.0682 (17) | |
H64 | −0.3340 | 0.3580 | −0.3572 | 0.082* | |
C15 | −0.2829 (4) | 0.4573 (4) | −0.1359 (4) | 0.0447 (13) | |
C25 | −0.3666 (5) | 0.5357 (4) | −0.1823 (4) | 0.0573 (15) | |
H25 | −0.4354 | 0.5246 | −0.2141 | 0.069* | |
C35 | −0.3505 (5) | 0.6299 (4) | −0.1827 (4) | 0.0673 (18) | |
H35 | −0.4080 | 0.6820 | −0.2142 | 0.081* | |
C45 | −0.2495 (6) | 0.6473 (4) | −0.1365 (5) | 0.075 (2) | |
H45 | −0.2385 | 0.7114 | −0.1370 | 0.090* | |
C55 | −0.1656 (6) | 0.5709 (5) | −0.0901 (5) | 0.0782 (19) | |
H55 | −0.0970 | 0.5824 | −0.0586 | 0.094* | |
C65 | −0.1827 (5) | 0.4756 (4) | −0.0897 (5) | 0.0615 (15) | |
H65 | −0.1250 | 0.4234 | −0.0576 | 0.074* | |
C16 | −0.3509 (4) | 0.2976 (3) | −0.0452 (4) | 0.0448 (13) | |
C26 | −0.3723 (5) | 0.3606 (4) | 0.0056 (4) | 0.0659 (16) | |
H26 | −0.3560 | 0.4229 | −0.0007 | 0.079* | |
C36 | −0.4174 (5) | 0.3322 (5) | 0.0652 (5) | 0.081 (2) | |
H36 | −0.4318 | 0.3756 | 0.0984 | 0.097* | |
C46 | −0.4412 (5) | 0.2402 (6) | 0.0760 (5) | 0.082 (2) | |
H46 | −0.4726 | 0.2217 | 0.1156 | 0.099* | |
C56 | −0.4190 (5) | 0.1769 (5) | 0.0292 (5) | 0.074 (2) | |
H56 | −0.4343 | 0.1143 | 0.0375 | 0.089* | |
C66 | −0.3737 (4) | 0.2042 (4) | −0.0309 (4) | 0.0609 (16) | |
H66 | −0.3583 | 0.1596 | −0.0623 | 0.073* | |
C17 | −0.2789 (4) | 0.0230 (3) | −0.1793 (4) | 0.0391 (12) | |
C27 | −0.3766 (4) | 0.0651 (3) | −0.3063 (4) | 0.0424 (12) | |
C37 | −0.3835 (5) | 0.1213 (4) | −0.4038 (4) | 0.0641 (17) | |
H37 | −0.3238 | 0.1402 | −0.3970 | 0.077* | |
C47 | −0.4841 (6) | 0.1485 (5) | −0.5128 (5) | 0.085 (2) | |
H47 | −0.4916 | 0.1865 | −0.5805 | 0.102* | |
C57 | −0.5726 (6) | 0.1215 (5) | −0.5243 (5) | 0.083 (2) | |
H57 | −0.6387 | 0.1422 | −0.5990 | 0.099* | |
C67 | −0.5651 (4) | 0.0645 (4) | −0.4275 (5) | 0.0661 (17) | |
H67 | −0.6252 | 0.0460 | −0.4349 | 0.079* | |
C77 | −0.4656 (4) | 0.0354 (3) | −0.3188 (4) | 0.0492 (13) | |
C18 | −0.0017 (4) | 0.3260 (4) | −0.1666 (4) | 0.0474 (13) | |
C28 | 0.0822 (4) | 0.3480 (4) | −0.1842 (4) | 0.0482 (13) | |
C38 | 0.1877 (5) | 0.2998 (4) | −0.1216 (5) | 0.0676 (17) | |
H38 | 0.2172 | 0.2442 | −0.0555 | 0.081* | |
C48 | 0.2491 (6) | 0.3350 (5) | −0.1580 (6) | 0.089 (2) | |
H48 | 0.3205 | 0.3024 | −0.1163 | 0.107* | |
C58 | 0.2065 (7) | 0.4178 (6) | −0.2554 (7) | 0.103 (3) | |
H58 | 0.2499 | 0.4414 | −0.2776 | 0.124* | |
C68 | 0.1003 (6) | 0.4657 (5) | −0.3201 (6) | 0.082 (2) | |
H68 | 0.0704 | 0.5205 | −0.3872 | 0.098* | |
C78 | 0.0398 (5) | 0.4303 (4) | −0.2825 (5) | 0.0573 (15) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ag1 | 0.0509 (3) | 0.0857 (3) | 0.0487 (2) | −0.0150 (2) | 0.0298 (2) | −0.0307 (2) |
Ag2 | 0.0521 (3) | 0.0541 (3) | 0.0684 (3) | −0.0082 (2) | 0.0375 (2) | −0.0123 (2) |
P1 | 0.0435 (9) | 0.0606 (9) | 0.0405 (7) | −0.0118 (7) | 0.0244 (6) | −0.0205 (6) |
P2 | 0.0426 (8) | 0.0415 (7) | 0.0470 (7) | −0.0114 (6) | 0.0267 (6) | −0.0107 (6) |
S17 | 0.0439 (9) | 0.0550 (8) | 0.0565 (8) | −0.0149 (6) | 0.0333 (7) | −0.0133 (6) |
S18 | 0.0636 (11) | 0.0529 (10) | 0.0725 (10) | −0.0097 (8) | 0.0330 (8) | −0.0076 (8) |
S1 | 0.0447 (8) | 0.0508 (8) | 0.0623 (8) | −0.0160 (6) | 0.0356 (7) | −0.0189 (6) |
S2 | 0.0494 (9) | 0.0529 (8) | 0.0490 (7) | −0.0164 (6) | 0.0297 (6) | −0.0192 (6) |
O17 | 0.059 (3) | 0.097 (3) | 0.088 (3) | −0.017 (2) | 0.056 (2) | −0.030 (2) |
O18 | 0.085 (3) | 0.050 (3) | 0.113 (3) | −0.007 (2) | 0.050 (3) | −0.015 (2) |
O27 | 0.062 (3) | 0.050 (2) | 0.082 (2) | −0.0230 (19) | 0.044 (2) | −0.0151 (19) |
O28 | 0.085 (3) | 0.088 (3) | 0.057 (2) | −0.018 (2) | 0.022 (2) | −0.012 (2) |
N17 | 0.038 (3) | 0.053 (3) | 0.045 (2) | −0.016 (2) | 0.0243 (19) | −0.0110 (19) |
N18 | 0.042 (3) | 0.052 (3) | 0.064 (3) | −0.012 (2) | 0.027 (2) | −0.015 (2) |
C11 | 0.050 (4) | 0.063 (4) | 0.035 (3) | −0.013 (3) | 0.023 (2) | −0.018 (2) |
C21 | 0.055 (4) | 0.063 (4) | 0.055 (3) | −0.018 (3) | 0.032 (3) | −0.024 (3) |
C31 | 0.069 (5) | 0.073 (5) | 0.066 (4) | −0.008 (4) | 0.034 (3) | −0.028 (3) |
C41 | 0.102 (6) | 0.057 (4) | 0.074 (4) | −0.015 (4) | 0.043 (4) | −0.023 (3) |
C51 | 0.102 (6) | 0.080 (5) | 0.079 (4) | −0.033 (4) | 0.061 (4) | −0.020 (4) |
C61 | 0.086 (5) | 0.072 (4) | 0.075 (4) | −0.020 (4) | 0.061 (4) | −0.024 (3) |
C12 | 0.047 (3) | 0.059 (3) | 0.046 (3) | −0.014 (3) | 0.029 (3) | −0.025 (3) |
C22 | 0.064 (4) | 0.095 (5) | 0.053 (3) | −0.031 (4) | 0.033 (3) | −0.021 (3) |
C32 | 0.104 (6) | 0.104 (5) | 0.081 (4) | −0.044 (5) | 0.070 (5) | −0.028 (4) |
C42 | 0.074 (5) | 0.095 (5) | 0.114 (5) | −0.041 (4) | 0.071 (5) | −0.053 (5) |
C52 | 0.051 (4) | 0.086 (5) | 0.080 (4) | −0.012 (3) | 0.035 (3) | −0.026 (4) |
C62 | 0.051 (4) | 0.075 (4) | 0.062 (3) | −0.007 (3) | 0.034 (3) | −0.019 (3) |
C13 | 0.042 (3) | 0.061 (3) | 0.041 (3) | −0.018 (3) | 0.024 (2) | −0.020 (2) |
C23 | 0.051 (4) | 0.072 (4) | 0.054 (3) | −0.014 (3) | 0.024 (3) | −0.025 (3) |
C33 | 0.069 (5) | 0.069 (4) | 0.065 (4) | −0.001 (3) | 0.036 (3) | −0.010 (3) |
C43 | 0.051 (4) | 0.102 (5) | 0.045 (3) | −0.009 (4) | 0.021 (3) | −0.005 (3) |
C53 | 0.059 (4) | 0.100 (5) | 0.045 (3) | −0.030 (4) | 0.027 (3) | −0.029 (3) |
C63 | 0.059 (4) | 0.074 (4) | 0.049 (3) | −0.019 (3) | 0.032 (3) | −0.022 (3) |
C14 | 0.048 (4) | 0.038 (3) | 0.053 (3) | −0.011 (2) | 0.027 (3) | −0.015 (2) |
C24 | 0.056 (4) | 0.079 (4) | 0.057 (3) | −0.016 (3) | 0.027 (3) | −0.017 (3) |
C34 | 0.057 (5) | 0.072 (4) | 0.079 (4) | −0.023 (3) | 0.021 (4) | −0.011 (4) |
C44 | 0.086 (6) | 0.073 (5) | 0.058 (4) | −0.019 (4) | 0.015 (4) | −0.021 (3) |
C54 | 0.098 (6) | 0.110 (6) | 0.049 (4) | −0.012 (5) | 0.031 (4) | −0.039 (4) |
C64 | 0.077 (5) | 0.077 (4) | 0.057 (3) | −0.018 (3) | 0.041 (3) | −0.025 (3) |
C15 | 0.050 (4) | 0.052 (3) | 0.037 (3) | −0.019 (3) | 0.027 (2) | −0.016 (2) |
C25 | 0.060 (4) | 0.051 (4) | 0.049 (3) | −0.015 (3) | 0.025 (3) | −0.012 (3) |
C35 | 0.081 (5) | 0.048 (4) | 0.049 (3) | −0.003 (3) | 0.027 (3) | −0.011 (3) |
C45 | 0.106 (6) | 0.052 (4) | 0.068 (4) | −0.030 (4) | 0.046 (4) | −0.028 (3) |
C55 | 0.070 (5) | 0.082 (5) | 0.098 (5) | −0.045 (4) | 0.049 (4) | −0.046 (4) |
C65 | 0.059 (4) | 0.059 (4) | 0.076 (4) | −0.018 (3) | 0.041 (3) | −0.031 (3) |
C16 | 0.040 (3) | 0.045 (3) | 0.039 (3) | −0.009 (2) | 0.019 (2) | −0.006 (2) |
C26 | 0.076 (5) | 0.070 (4) | 0.064 (4) | −0.013 (3) | 0.050 (3) | −0.014 (3) |
C36 | 0.099 (6) | 0.094 (5) | 0.079 (4) | −0.024 (4) | 0.070 (4) | −0.023 (4) |
C46 | 0.062 (5) | 0.115 (6) | 0.062 (4) | −0.020 (4) | 0.039 (3) | −0.002 (4) |
C56 | 0.070 (5) | 0.070 (4) | 0.071 (4) | −0.031 (4) | 0.039 (4) | −0.001 (3) |
C66 | 0.056 (4) | 0.064 (4) | 0.057 (3) | −0.014 (3) | 0.032 (3) | −0.010 (3) |
C17 | 0.047 (3) | 0.038 (3) | 0.041 (3) | −0.012 (2) | 0.028 (2) | −0.019 (2) |
C27 | 0.046 (3) | 0.038 (3) | 0.045 (3) | −0.012 (2) | 0.027 (2) | −0.013 (2) |
C37 | 0.073 (5) | 0.061 (4) | 0.054 (3) | −0.023 (3) | 0.037 (3) | −0.007 (3) |
C47 | 0.100 (6) | 0.073 (5) | 0.049 (3) | −0.019 (4) | 0.030 (4) | 0.000 (3) |
C57 | 0.070 (5) | 0.075 (5) | 0.057 (4) | −0.011 (4) | 0.014 (3) | −0.011 (3) |
C67 | 0.044 (4) | 0.057 (4) | 0.069 (4) | −0.012 (3) | 0.019 (3) | −0.012 (3) |
C77 | 0.046 (3) | 0.043 (3) | 0.048 (3) | −0.007 (2) | 0.023 (3) | −0.011 (2) |
C18 | 0.048 (4) | 0.050 (3) | 0.050 (3) | −0.019 (3) | 0.028 (3) | −0.022 (2) |
C28 | 0.050 (4) | 0.057 (3) | 0.052 (3) | −0.017 (3) | 0.036 (3) | −0.021 (3) |
C38 | 0.059 (4) | 0.075 (4) | 0.071 (4) | −0.017 (3) | 0.042 (3) | −0.015 (3) |
C48 | 0.071 (5) | 0.105 (6) | 0.104 (5) | −0.014 (4) | 0.062 (4) | −0.018 (5) |
C58 | 0.100 (7) | 0.136 (7) | 0.117 (6) | −0.051 (6) | 0.086 (5) | −0.036 (5) |
C68 | 0.089 (6) | 0.089 (5) | 0.078 (4) | −0.029 (4) | 0.056 (4) | −0.019 (4) |
C78 | 0.063 (4) | 0.054 (3) | 0.067 (3) | −0.016 (3) | 0.044 (3) | −0.018 (3) |
Geometric parameters (Å, º) top
Ag1—P1 | 2.3904 (13) | C63—H63 | 0.9300 |
Ag1—S2i | 2.5440 (13) | C14—C24 | 1.364 (7) |
Ag1—S1 | 2.5484 (13) | C14—C64 | 1.393 (7) |
Ag2—P2 | 2.3952 (15) | C24—C34 | 1.403 (7) |
Ag2—S2 | 2.5008 (14) | C24—H24 | 0.9300 |
Ag2—S1 | 2.5852 (13) | C34—C44 | 1.367 (9) |
P1—C12 | 1.812 (5) | C34—H34 | 0.9300 |
P1—C13 | 1.813 (5) | C44—C54 | 1.349 (9) |
P1—C11 | 1.815 (5) | C44—H44 | 0.9300 |
P2—C16 | 1.808 (5) | C54—C64 | 1.385 (7) |
P2—C15 | 1.816 (5) | C54—H54 | 0.9300 |
P2—C14 | 1.826 (5) | C64—H64 | 0.9300 |
S17—O17 | 1.426 (4) | C15—C65 | 1.364 (7) |
S17—O27 | 1.429 (3) | C15—C25 | 1.374 (7) |
S17—N17 | 1.651 (4) | C25—C35 | 1.367 (6) |
S17—C77 | 1.751 (5) | C25—H25 | 0.9300 |
S18—O28 | 1.424 (4) | C35—C45 | 1.371 (8) |
S18—O18 | 1.432 (4) | C35—H35 | 0.9300 |
S18—N18 | 1.664 (4) | C45—C55 | 1.358 (8) |
S18—C78 | 1.742 (6) | C45—H45 | 0.9300 |
S1—C17 | 1.702 (5) | C55—C65 | 1.387 (7) |
S2—C18 | 1.729 (5) | C55—H55 | 0.9300 |
S2—Ag1i | 2.5440 (13) | C65—H65 | 0.9300 |
N17—C17 | 1.311 (5) | C16—C26 | 1.381 (7) |
N18—C18 | 1.289 (6) | C16—C66 | 1.388 (6) |
C11—C21 | 1.376 (7) | C26—C36 | 1.372 (8) |
C11—C61 | 1.383 (7) | C26—H26 | 0.9300 |
C21—C31 | 1.379 (7) | C36—C46 | 1.373 (8) |
C21—H21 | 0.9300 | C36—H36 | 0.9300 |
C31—C41 | 1.366 (9) | C46—C56 | 1.347 (8) |
C31—H31 | 0.9300 | C46—H46 | 0.9300 |
C41—C51 | 1.357 (9) | C56—C66 | 1.379 (8) |
C41—H41 | 0.9300 | C56—H56 | 0.9300 |
C51—C61 | 1.371 (8) | C66—H66 | 0.9300 |
C51—H51 | 0.9300 | C17—C27 | 1.500 (6) |
C61—H61 | 0.9300 | C27—C37 | 1.375 (6) |
C12—C22 | 1.369 (6) | C27—C77 | 1.381 (7) |
C12—C62 | 1.390 (7) | C37—C47 | 1.387 (7) |
C22—C32 | 1.394 (8) | C37—H37 | 0.9300 |
C22—H22 | 0.9300 | C47—C57 | 1.364 (9) |
C32—C42 | 1.356 (8) | C47—H47 | 0.9300 |
C32—H32 | 0.9300 | C57—C67 | 1.367 (8) |
C42—C52 | 1.360 (8) | C57—H57 | 0.9300 |
C42—H42 | 0.9300 | C67—C77 | 1.376 (6) |
C52—C62 | 1.365 (8) | C67—H67 | 0.9300 |
C52—H52 | 0.9300 | C18—C28 | 1.479 (7) |
C62—H62 | 0.9300 | C28—C38 | 1.373 (7) |
C13—C63 | 1.383 (6) | C28—C78 | 1.383 (6) |
C13—C23 | 1.385 (7) | C38—C48 | 1.373 (8) |
C23—C33 | 1.361 (7) | C38—H38 | 0.9300 |
C23—H23 | 0.9300 | C48—C58 | 1.380 (9) |
C33—C43 | 1.366 (7) | C48—H48 | 0.9300 |
C33—H33 | 0.9300 | C58—C68 | 1.376 (9) |
C43—C53 | 1.373 (8) | C58—H58 | 0.9300 |
C43—H43 | 0.9300 | C68—C78 | 1.374 (8) |
C53—C63 | 1.378 (7) | C68—H68 | 0.9300 |
C53—H53 | 0.9300 | | |
| | | |
P1—Ag1—S2i | 126.76 (5) | C64—C14—P2 | 116.7 (4) |
P1—Ag1—S1 | 133.92 (5) | C14—C24—C34 | 119.9 (6) |
S2i—Ag1—S1 | 99.30 (4) | C14—C24—H24 | 120.0 |
P2—Ag2—S2 | 135.38 (4) | C34—C24—H24 | 120.0 |
P2—Ag2—S1 | 126.12 (4) | C44—C34—C24 | 120.2 (7) |
S2—Ag2—S1 | 97.49 (4) | C44—C34—H34 | 119.9 |
C12—P1—C13 | 104.3 (2) | C24—C34—H34 | 119.9 |
C12—P1—C11 | 106.6 (3) | C54—C44—C34 | 119.5 (6) |
C13—P1—C11 | 104.7 (2) | C54—C44—H44 | 120.2 |
C12—P1—Ag1 | 110.94 (15) | C34—C44—H44 | 120.2 |
C13—P1—Ag1 | 117.26 (18) | C44—C54—C64 | 121.8 (7) |
C11—P1—Ag1 | 112.20 (15) | C44—C54—H54 | 119.1 |
C16—P2—C15 | 106.0 (2) | C64—C54—H54 | 119.1 |
C16—P2—C14 | 103.3 (2) | C54—C64—C14 | 118.9 (6) |
C15—P2—C14 | 102.1 (2) | C54—C64—H64 | 120.5 |
C16—P2—Ag2 | 118.59 (17) | C14—C64—H64 | 120.5 |
C15—P2—Ag2 | 114.55 (19) | C65—C15—C25 | 118.3 (5) |
C14—P2—Ag2 | 110.53 (18) | C65—C15—P2 | 119.3 (4) |
O17—S17—O27 | 117.1 (2) | C25—C15—P2 | 122.4 (4) |
O17—S17—N17 | 108.7 (2) | C35—C25—C15 | 121.1 (5) |
O27—S17—N17 | 110.0 (2) | C35—C25—H25 | 119.4 |
O17—S17—C77 | 113.0 (3) | C15—C25—H25 | 119.4 |
O27—S17—C77 | 109.9 (2) | C25—C35—C45 | 120.0 (6) |
N17—S17—C77 | 96.2 (2) | C25—C35—H35 | 120.0 |
O28—S18—O18 | 117.6 (3) | C45—C35—H35 | 120.0 |
O28—S18—N18 | 110.1 (2) | C55—C45—C35 | 119.8 (5) |
O18—S18—N18 | 108.8 (3) | C55—C45—H45 | 120.1 |
O28—S18—C78 | 111.2 (3) | C35—C45—H45 | 120.1 |
O18—S18—C78 | 111.3 (3) | C45—C55—C65 | 119.8 (6) |
N18—S18—C78 | 95.5 (2) | C45—C55—H55 | 120.1 |
C17—S1—Ag1 | 91.55 (16) | C65—C55—H55 | 120.1 |
C17—S1—Ag2 | 108.51 (16) | C15—C65—C55 | 121.0 (6) |
Ag1—S1—Ag2 | 101.38 (4) | C15—C65—H65 | 119.5 |
C18—S2—Ag2 | 102.77 (19) | C55—C65—H65 | 119.5 |
C18—S2—Ag1i | 107.06 (17) | C26—C16—C66 | 117.8 (5) |
Ag2—S2—Ag1i | 97.33 (4) | C26—C16—P2 | 124.0 (4) |
C17—N17—S17 | 111.2 (3) | C66—C16—P2 | 118.1 (4) |
C18—N18—S18 | 110.5 (4) | C36—C26—C16 | 120.7 (6) |
C21—C11—C61 | 118.2 (5) | C36—C26—H26 | 119.7 |
C21—C11—P1 | 123.7 (4) | C16—C26—H26 | 119.7 |
C61—C11—P1 | 118.1 (5) | C26—C36—C46 | 120.4 (6) |
C11—C21—C31 | 120.8 (6) | C26—C36—H36 | 119.8 |
C11—C21—H21 | 119.6 | C46—C36—H36 | 119.8 |
C31—C21—H21 | 119.6 | C56—C46—C36 | 119.8 (6) |
C41—C31—C21 | 120.0 (7) | C56—C46—H46 | 120.1 |
C41—C31—H31 | 120.0 | C36—C46—H46 | 120.1 |
C21—C31—H31 | 120.0 | C46—C56—C66 | 120.5 (6) |
C51—C41—C31 | 119.7 (6) | C46—C56—H56 | 119.8 |
C51—C41—H41 | 120.1 | C66—C56—H56 | 119.8 |
C31—C41—H41 | 120.1 | C56—C66—C16 | 120.7 (6) |
C41—C51—C61 | 120.8 (7) | C56—C66—H66 | 119.6 |
C41—C51—H51 | 119.6 | C16—C66—H66 | 119.6 |
C61—C51—H51 | 119.6 | N17—C17—C27 | 114.4 (4) |
C51—C61—C11 | 120.4 (6) | N17—C17—S1 | 122.6 (3) |
C51—C61—H61 | 119.8 | C27—C17—S1 | 123.0 (4) |
C11—C61—H61 | 119.8 | C37—C27—C77 | 120.9 (5) |
C22—C12—C62 | 118.2 (5) | C37—C27—C17 | 128.3 (5) |
C22—C12—P1 | 124.4 (4) | C77—C27—C17 | 110.7 (4) |
C62—C12—P1 | 117.4 (4) | C27—C37—C47 | 116.6 (6) |
C12—C22—C32 | 120.1 (6) | C27—C37—H37 | 121.7 |
C12—C22—H22 | 120.0 | C47—C37—H37 | 121.7 |
C32—C22—H22 | 120.0 | C57—C47—C37 | 122.5 (6) |
C42—C32—C22 | 120.4 (6) | C57—C47—H47 | 118.8 |
C42—C32—H32 | 119.8 | C37—C47—H47 | 118.8 |
C22—C32—H32 | 119.8 | C47—C57—C67 | 120.8 (6) |
C32—C42—C52 | 120.0 (6) | C47—C57—H57 | 119.6 |
C32—C42—H42 | 120.0 | C67—C57—H57 | 119.6 |
C52—C42—H42 | 120.0 | C57—C67—C77 | 117.7 (6) |
C42—C52—C62 | 120.2 (6) | C57—C67—H67 | 121.2 |
C42—C52—H52 | 119.9 | C77—C67—H67 | 121.2 |
C62—C52—H52 | 119.9 | C67—C77—C27 | 121.5 (5) |
C52—C62—C12 | 121.1 (6) | C67—C77—S17 | 131.0 (5) |
C52—C62—H62 | 119.4 | C27—C77—S17 | 107.4 (4) |
C12—C62—H62 | 119.4 | N18—C18—C28 | 116.1 (5) |
C63—C13—C23 | 117.9 (5) | N18—C18—S2 | 122.9 (5) |
C63—C13—P1 | 123.5 (4) | C28—C18—S2 | 120.9 (4) |
C23—C13—P1 | 118.5 (4) | C38—C28—C78 | 119.5 (5) |
C33—C23—C13 | 121.4 (5) | C38—C28—C18 | 130.6 (5) |
C33—C23—H23 | 119.3 | C78—C28—C18 | 109.9 (5) |
C13—C23—H23 | 119.3 | C28—C38—C48 | 119.1 (6) |
C23—C33—C43 | 120.3 (6) | C28—C38—H38 | 120.5 |
C23—C33—H33 | 119.9 | C48—C38—H38 | 120.5 |
C43—C33—H33 | 119.9 | C38—C48—C58 | 121.1 (7) |
C33—C43—C53 | 119.6 (5) | C38—C48—H48 | 119.5 |
C33—C43—H43 | 120.2 | C58—C48—H48 | 119.5 |
C53—C43—H43 | 120.2 | C68—C58—C48 | 120.4 (7) |
C43—C53—C63 | 120.3 (5) | C68—C58—H58 | 119.8 |
C43—C53—H53 | 119.9 | C48—C58—H58 | 119.8 |
C63—C53—H53 | 119.9 | C78—C68—C58 | 118.0 (6) |
C53—C63—C13 | 120.5 (6) | C78—C68—H68 | 121.0 |
C53—C63—H63 | 119.8 | C58—C68—H68 | 121.0 |
C13—C63—H63 | 119.8 | C68—C78—C28 | 121.9 (6) |
C24—C14—C64 | 119.6 (5) | C68—C78—S18 | 130.2 (5) |
C24—C14—P2 | 123.7 (4) | C28—C78—S18 | 107.9 (4) |
| | | |
S2i—Ag1—P1—C12 | −74.87 (19) | C24—C14—C64—C54 | 2.8 (8) |
S1—Ag1—P1—C12 | 107.05 (19) | P2—C14—C64—C54 | −177.3 (4) |
S2i—Ag1—P1—C13 | 44.8 (2) | C16—P2—C15—C65 | 119.0 (4) |
S1—Ag1—P1—C13 | −133.31 (18) | C14—P2—C15—C65 | −133.2 (4) |
S2i—Ag1—P1—C11 | 166.1 (2) | Ag2—P2—C15—C65 | −13.7 (4) |
S1—Ag1—P1—C11 | −12.0 (2) | C16—P2—C15—C25 | −61.4 (4) |
S2—Ag2—P2—C16 | −124.86 (17) | C14—P2—C15—C25 | 46.4 (5) |
S1—Ag2—P2—C16 | 69.37 (18) | Ag2—P2—C15—C25 | 165.9 (3) |
S2—Ag2—P2—C15 | 1.56 (17) | C65—C15—C25—C35 | 0.1 (7) |
S1—Ag2—P2—C15 | −164.21 (15) | P2—C15—C25—C35 | −179.5 (4) |
S2—Ag2—P2—C14 | 116.23 (18) | C15—C25—C35—C45 | 0.2 (8) |
S1—Ag2—P2—C14 | −49.54 (18) | C25—C35—C45—C55 | −0.3 (9) |
P1—Ag1—S1—C17 | −95.75 (16) | C35—C45—C55—C65 | 0.0 (9) |
S2i—Ag1—S1—C17 | 85.82 (16) | C25—C15—C65—C55 | −0.3 (8) |
P1—Ag1—S1—Ag2 | 13.48 (9) | P2—C15—C65—C55 | 179.2 (4) |
S2i—Ag1—S1—Ag2 | −164.95 (5) | C45—C55—C65—C15 | 0.3 (9) |
P2—Ag2—S1—C17 | −5.32 (17) | C15—P2—C16—C26 | 2.3 (5) |
S2—Ag2—S1—C17 | −175.29 (16) | C14—P2—C16—C26 | −104.7 (5) |
P2—Ag2—S1—Ag1 | −100.86 (6) | Ag2—P2—C16—C26 | 132.7 (4) |
S2—Ag2—S1—Ag1 | 89.17 (5) | C15—P2—C16—C66 | 179.1 (4) |
P2—Ag2—S2—C18 | −57.11 (18) | C14—P2—C16—C66 | 72.1 (4) |
S1—Ag2—S2—C18 | 111.34 (17) | Ag2—P2—C16—C66 | −50.5 (4) |
P2—Ag2—S2—Ag1i | −166.52 (5) | C66—C16—C26—C36 | −1.7 (8) |
S1—Ag2—S2—Ag1i | 1.93 (4) | P2—C16—C26—C36 | 175.1 (5) |
O17—S17—N17—C17 | −119.1 (4) | C16—C26—C36—C46 | 0.5 (10) |
O27—S17—N17—C17 | 111.6 (3) | C26—C36—C46—C56 | 0.9 (10) |
C77—S17—N17—C17 | −2.2 (4) | C36—C46—C56—C66 | −0.8 (10) |
O28—S18—N18—C18 | 115.5 (4) | C46—C56—C66—C16 | −0.5 (9) |
O18—S18—N18—C18 | −114.2 (4) | C26—C16—C66—C56 | 1.7 (8) |
C78—S18—N18—C18 | 0.5 (4) | P2—C16—C66—C56 | −175.2 (4) |
C12—P1—C11—C21 | 2.1 (5) | S17—N17—C17—C27 | 0.8 (5) |
C13—P1—C11—C21 | −108.0 (4) | S17—N17—C17—S1 | −179.8 (2) |
Ag1—P1—C11—C21 | 123.7 (4) | Ag1—S1—C17—N17 | 3.9 (4) |
C12—P1—C11—C61 | −175.2 (4) | Ag2—S1—C17—N17 | −98.6 (4) |
C13—P1—C11—C61 | 74.6 (4) | Ag1—S1—C17—C27 | −176.8 (4) |
Ag1—P1—C11—C61 | −53.7 (4) | Ag2—S1—C17—C27 | 80.7 (4) |
C61—C11—C21—C31 | −0.7 (8) | N17—C17—C27—C37 | −175.1 (5) |
P1—C11—C21—C31 | −178.1 (4) | S1—C17—C27—C37 | 5.5 (7) |
C11—C21—C31—C41 | −0.2 (8) | N17—C17—C27—C77 | 1.4 (6) |
C21—C31—C41—C51 | 0.0 (9) | S1—C17—C27—C77 | −177.9 (4) |
C31—C41—C51—C61 | 1.1 (10) | C77—C27—C37—C47 | 1.9 (8) |
C41—C51—C61—C11 | −2.0 (10) | C17—C27—C37—C47 | 178.1 (5) |
C21—C11—C61—C51 | 1.8 (8) | C27—C37—C47—C57 | 0.0 (10) |
P1—C11—C61—C51 | 179.3 (4) | C37—C47—C57—C67 | −0.9 (11) |
C13—P1—C12—C22 | 9.8 (5) | C47—C57—C67—C77 | −0.1 (10) |
C11—P1—C12—C22 | −100.6 (5) | C57—C67—C77—C27 | 2.1 (8) |
Ag1—P1—C12—C22 | 137.0 (4) | C57—C67—C77—S17 | −174.2 (5) |
C13—P1—C12—C62 | −168.3 (4) | C37—C27—C77—C67 | −3.0 (8) |
C11—P1—C12—C62 | 81.3 (4) | C17—C27—C77—C67 | −179.9 (5) |
Ag1—P1—C12—C62 | −41.1 (4) | C37—C27—C77—S17 | 174.0 (4) |
C62—C12—C22—C32 | 0.3 (9) | C17—C27—C77—S17 | −2.8 (5) |
P1—C12—C22—C32 | −177.7 (5) | O17—S17—C77—C67 | −67.0 (6) |
C12—C22—C32—C42 | −0.8 (10) | O27—S17—C77—C67 | 65.8 (6) |
C22—C32—C42—C52 | 0.7 (11) | N17—S17—C77—C67 | 179.6 (5) |
C32—C42—C52—C62 | −0.1 (10) | O17—S17—C77—C27 | 116.3 (4) |
C42—C52—C62—C12 | −0.4 (9) | O27—S17—C77—C27 | −110.9 (4) |
C22—C12—C62—C52 | 0.3 (9) | N17—S17—C77—C27 | 2.9 (4) |
P1—C12—C62—C52 | 178.5 (5) | S18—N18—C18—C28 | −1.1 (5) |
C12—P1—C13—C63 | −95.0 (5) | S18—N18—C18—S2 | 176.4 (2) |
C11—P1—C13—C63 | 16.7 (5) | Ag2—S2—C18—N18 | 11.9 (4) |
Ag1—P1—C13—C63 | 141.9 (4) | Ag1i—S2—C18—N18 | 113.8 (4) |
C12—P1—C13—C23 | 81.6 (5) | Ag2—S2—C18—C28 | −170.6 (3) |
C11—P1—C13—C23 | −166.6 (4) | Ag1i—S2—C18—C28 | −68.7 (4) |
Ag1—P1—C13—C23 | −41.5 (5) | N18—C18—C28—C38 | −177.5 (5) |
C63—C13—C23—C33 | 0.7 (9) | S2—C18—C28—C38 | 4.9 (7) |
P1—C13—C23—C33 | −176.2 (5) | N18—C18—C28—C78 | 1.3 (6) |
C13—C23—C33—C43 | −1.2 (9) | S2—C18—C28—C78 | −176.3 (3) |
C23—C33—C43—C53 | 0.4 (9) | C78—C28—C38—C48 | 0.3 (8) |
C33—C43—C53—C63 | 0.8 (10) | C18—C28—C38—C48 | 179.0 (5) |
C43—C53—C63—C13 | −1.3 (9) | C28—C38—C48—C58 | 0.4 (10) |
C23—C13—C63—C53 | 0.6 (8) | C38—C48—C58—C68 | −1.5 (11) |
P1—C13—C63—C53 | 177.3 (4) | C48—C58—C68—C78 | 1.8 (11) |
C16—P2—C14—C24 | 9.6 (5) | C58—C68—C78—C28 | −1.2 (9) |
C15—P2—C14—C24 | −100.3 (5) | C58—C68—C78—S18 | −178.7 (5) |
Ag2—P2—C14—C24 | 137.4 (4) | C38—C28—C78—C68 | 0.1 (8) |
C16—P2—C14—C64 | −170.3 (4) | C18—C28—C78—C68 | −178.8 (5) |
C15—P2—C14—C64 | 79.8 (4) | C38—C28—C78—S18 | 178.2 (4) |
Ag2—P2—C14—C64 | −42.5 (4) | C18—C28—C78—S18 | −0.8 (5) |
C64—C14—C24—C34 | −0.8 (8) | O28—S18—C78—C68 | 63.9 (6) |
P2—C14—C24—C34 | 179.3 (4) | O18—S18—C78—C68 | −69.3 (6) |
C14—C24—C34—C44 | −1.1 (9) | N18—S18—C78—C68 | 178.0 (5) |
C24—C34—C44—C54 | 1.1 (10) | O28—S18—C78—C28 | −113.9 (4) |
C34—C44—C54—C64 | 0.9 (10) | O18—S18—C78—C28 | 112.8 (4) |
C44—C54—C64—C14 | −2.8 (9) | N18—S18—C78—C28 | 0.2 (4) |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C46—H46···O27ii | 0.93 | 2.44 | 3.350 (10) | 165 |
C52—H52···O17ii | 0.93 | 2.56 | 3.196 (10) | 126 |
C23—H23···Cg1i | 0.93 | 2.99 | 3.865 (6) | 158 |
C37—H37···Cg2i | 0.93 | 2.93 | 3.734 (9) | 146 |
Symmetry codes: (i) −x, −y, −z; (ii) −x−1, −y, −z. |
Experimental details
Crystal data |
Chemical formula | [Ag4(C7H4NO2S2)4(C18H15P)4] |
Mr | 2273.49 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 291 |
a, b, c (Å) | 15.3566 (10), 14.1309 (7), 14.0768 (6) |
α, β, γ (°) | 77.771 (4), 123.880 (3), 86.465 (1) |
V (Å3) | 2416.9 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.10 |
Crystal size (mm) | 0.20 × 0.16 × 0.12 |
|
Data collection |
Diffractometer | Oxford Gemini CCD S Ultra diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) |
Tmin, Tmax | 0.98, 0.99 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20631, 11017, 5568 |
Rint | 0.060 |
(sin θ/λ)max (Å−1) | 0.681 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.112, 0.94 |
No. of reflections | 11017 |
No. of parameters | 577 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.72, −0.70 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C46—H46···O27i | 0.93 | 2.44 | 3.350 (10) | 165 |
C52—H52···O17i | 0.93 | 2.56 | 3.196 (10) | 126 |
C23—H23···Cg1ii | 0.93 | 2.99 | 3.865 (6) | 158 |
C37—H37···Cg2ii | 0.93 | 2.93 | 3.734 (9) | 146 |
Symmetry codes: (i) −x−1, −y, −z; (ii) −x, −y, −z. |
Comparison of crystal data for (I) (this work) and (II) (Dennehy, Mandolesi
et al., 2007) top | (I) | (II) | | (I) | (II) |
Crystal system | Triclinic | Monoclinic | Space group | P1 | P21/n |
a (Å) | 15.3566 (10) | 15.024 (3) | α (°) | 77.771 (4) | 90 |
b (Å) | 14.1309 (7) | 14.681 (3) | β (°) | 123.880 (3) | 95.31 (3) |
c (Å) | 14.0768 (6) | 21.914 (4) | γ (°) | 86.465 (1) | 90 |
V (Å3) | 2416.9 (2) | 4812.77 | Z | 1 | 2 |
Dx (Mg m-3) | 1.562 | 1.569 | | | |
Comparison of selected bond lengths and angles (Å,°) in (I) (this work) and
(II) (Dennehy, Mandolesi et al., 2007) top | (I) | (II) | | (I) | (II) |
Ag1—P1 | 2.3904 (13) | 2.398 (3) | Ag2—P2 | 2.3952 (15) | 2.396 (2) |
Ag1—S2i | 2.5440 (13) | 2.551 (2) | Ag2—S2 | 2.5008 (14) | 2.505 (2) |
Ag1—S1 | 2.5484 (13) | 2.549 (3) | Ag2—S1 | 2.5852 (13) | 2.582 (3) |
| | | | | |
P1—Ag1—S2i | 126.76 (5) | 122.81 (9) | P2—Ag2—S2 | 135.38 (4) | 135.79 (9) |
P1—Ag1—S1 | 133.92 (5) | 132.07 (9) | P2—Ag2—S1 | 126.12 (4) | 131.66 (8) |
S2i—Ag1—S1 | 99.30 (4) | 105.13 (8) | S2—Ag2—S1 | 97.49 (4) | 92.33 (8) |
| | | | | |
S2i—Ag1—S1—Ag2 | -164.95 (5) | -163.22 (8) | S1—Ag2—S2—Ag1i | 1.93 (4) | 11.17 (10) |
Ag1—S1—Ag2—S2 | 89.17 (5) | 79.80 (10) | Ag2—S2—Ag1i—S1i | -88.11 (6) | -95.45 (9) |
Symmetry code: (i) -x, -y, -z. |
π–π interactions (Å, °) for (I) topGroup 1/group 2 | ccd (Å) | ipd (Å) | sa (°) |
Cg3···Cg3ii | 3.735 (4) | 3.441 (2) | 22.8 (2) |
Symmetry code: (ii) -1 - x, -y, -1 - z.
Cg3 is the centroid of the C27/C37/C47/C57/C67/C77 ring, ccd is the
centre-to-centre distance (distance between ring centroids), ipd is the
interplanar distance (distance from one plane to the neighbouring centroid), sa
is the slippage angle (angle subtended by the intercentroid vector to the plane
normal). For details, see Janiak (2000). |
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Heterocyclic thiones are versatile S,N-chelating ligands and a considerable amount of work has centred around their coordination chemistry. They are capable of binding to metals in a variety of coordination modes and a large number of mononuclear, binuclear and complex polynuclear coordination compounds have been reported after the pioneering work by Raper (1996, 1997). We have developed a sustained interest in the coordination behaviour of heterocyclic thiones in general, and thiosaccharin [the thione form of saccharin, C6H4SO2NHCS, hereinafter tsac; systematic name: 1,1-dioxo-1λ6,2-benzothiazole-3(2H)-thione], in particular. As is well known for other heterocyclic thiones, tsac has a tautomeric equilibrium in solution (Scheme 1) and in its thiol form it can act as a good coordinating agent for soft metals, building interesting mononuclear and polynuclear structures with or without the presence of additional ligands. In particular, we have worked on the silver–tsac system, aiming to control its stereochemistry and nuclearity, and we have been able to develop new products, for example, by changing the stoichiometry of the soft bulky triphenylphosphane (PPh3) co-ligand. Surprisingly, the Ag–PPh3 stoichiometries in the resulting complexes do not always follow the mole ratios of the reaction mixture. For example, a stable tetracoordinated complex [Ag(tsac)(PPh3)3] was obtained from reaction mixtures with Ag–PPh3 molar ratios greater than 1:2, but a different Ag6(tsac)6 complex resulted for molar ratios of 1:1 or less (Dennehy, Quinzani & Jennings, 2007). In our search for the appropriate conditions to prepare silver(I) thiosaccharinates with less than three phosphane ligands on the metal nuclei, we recently produced a monoclinic tetranuclear complex, [Ag4(tsac)4(PPh3)4] (Dennehy, Mandolesi et al., 2007). Through a slight variation in the synthesis conditions, we have now obtained a triclinic polymorph of the same compound, which we report herein. The triclinic and monoclinic polymorphs are referred to as (I) and (II), respectively.
Some comparative crystal data for polymorphs (I) and (II) are given in Table 1. In order to highlight the similarities and differences between the structures, triclinic form (I) is described using a nonconventional nonreduced unit cell. The corresponding reduced cell is a = 13.8914 (7), b = 14.0768 (6), c = 14.1309 (7) Å, α = 77.771 (4), β = 73.572 (4) and γ = 66.603 (4)°.
The tetranuclear unit in (I) (Fig. 1) is very similar to its counterpart in (II). The molecule is composed of four fused Ag(tsac)(PPh3) groups, two of them independent and the remaining two generated by an inversion centre. The main characteristic is the centrosymmetric eight-membered skeleton, composed of four thione exocyclic S atoms and four Ag atoms in a regular chair conformation. Each Ag atom is triply coordinated by two S atoms and one PPh3 group in a slightly distorted planar arrangement; the deviations of the Ag atoms from the ligand coordination plane are 0.0192 (3) Å for Ag1 and 0.1392 (3) Å for Ag2, compared with the corresponding values of 0.0062 (14) and 0.0650 (16) Å for polymorph (II). The coordination distances in both complexes are extremely similar (Table 2), and the bond distances and angles in the bridging tsac ligands are typical of those observed in other related polynuclear silver thiosaccharinates (Dennehy, Mandolesi et al., 2007). A least-squares overlay of the complexes in (I) and (II) gives an r.m.s. deviation of 0.4 Å for 128 non-H atoms (Macrae et al., 2008). A least-squares overlay of the central core of the complex (Fig. 2) shows that (I) adopts a more regular chair conformation compared with (II), as reflected by the Ag1—S1—Ag2—S2 torsion angles [89.17 (5)° in (I) versus 79.80 (10)° in (II)]. These relatively small differences in the skeleton are magnified towards the outermost parts of the bulky PPh3 groups on account of the variation in the degree of rotation around the P—Ag bonds. However, in both polymorphs the overall globular shape for the molecule is conserved. The changes which arise are reflected in the geometries of the intra- and intermolecular interactions (Tables 3 and 4) to the extent that they cannot readily be correlated between one structure and the other.
The two polymorphs have closely comparable calculated densities (Table 2) but different distributions of the molecules in space. The choice of cell axes for (I) is intended to highlight the similarities in the (001) planes in both structures (see a, b and γ in Table 1, and the coloured ab faces in Fig. 3). Indeed, the structures contain essentially identical layers of molecules parallel to the (001) planes, and they look identical when projected along the b axis. Fig. 3, where for simplicity only the inorganic skeletons have been represented, presents for each structure two consecutive layers (with and without shading) of these (001) planes, projected onto the layer plane. In (I), the layer stacking takes place via a consistent c(I) cell shift, so that all layers are related by lattice translation. In (II), the n-glides generate alternating mirror images shifted by one half of the c(II) translation. Taking into account the differences in cell lengths and cell angles, this corresponds to slightly different interplanar spacings: d(001) = 11.159 (2) Å for (I) and d(002) = 10.910 (2) Å for (II).
The globular shape of the molecules involved, and the absence of strong directional intermolecular interactions, leads to arrangements compatible with the packing of spheres. A nearest-neighbours calculation for the molecular centroids gives exactly 12 neighbours for each structure, in the tight range of 14.667 (2)–15.672 (3) Å for (II) and the slightly broader range of 13.8914 (12)–17.7086 (13) Å for (I), in both cases followed by a 3 Å gap to the second nearest-neighbour shell. The distribution of the centroids in both structures can be envisaged as a hexagonal arrangement, parallel to (100) in (I) or (101) in (II), bi-capped by two parallel inverted triangles, resembling a 3 distribution (Fig. 4). The distribution in (II) is rather regular, with the line through the triangular centres being almost perpendicular to the equatorial plane [angle 179.91 (14)°] and the interplanar distances [corresponding to d(101)] being 11.838 (2) Å. The distribution in (I) is more deformed, with corresponding values of 171.78 (16)° for the line-to-plane angle and 12.432 (2)Å for d(100).