In the crystal structure of the title compound, [AgCo2(C2H4O2S)2(C2H8N2)4](ClO4)3, the AgI atom is located on an inversion center and is linearly coordinated by two sulfide S atoms from Δ- and Λ-[CoIII(C2H4O2S)(C2H8N2)2]+ octahedral units, forming a meso configurational S-bridged CoIII–AgI–CoIII trinuclear structure.
Supporting information
CCDC reference: 610814
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.006 Å
- Disorder in solvent or counterion
- R factor = 0.032
- wR factor = 0.085
- Data-to-parameter ratio = 14.0
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact O3 .. O9 .. 2.80 Ang.
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl2
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl1
PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 29.00 Perc.
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
4 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
3 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: MSC/AFC Diffractometer Control Software
(Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: Crystal structure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
meso-Tetrakis(ethylenediamine)-1
κ4N,
N';3
κ4N,
N'-
di-µ-sulfidoacetato-1:2
κ3O,
S:
S;2:3
κ3S:
S,
O- dicobalt(III)silver(I) triperchlorate
top
Crystal data top
[AgCo2(C2H4O2S)2(C2H8N2)4](ClO4)3 | F(000) = 952 |
Mr = 944.69 | Dx = 2.030 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 12.486 (3) Å | θ = 14.7–15.0° |
b = 8.974 (2) Å | µ = 2.16 mm−1 |
c = 14.410 (2) Å | T = 296 K |
β = 106.857 (14)° | Prism, red |
V = 1545.2 (6) Å3 | 0.35 × 0.35 × 0.25 mm |
Z = 2 | |
Data collection top
Rigaku AFC-7S diffractometer | 2788 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
Graphite monochromator | θmax = 27.5°, θmin = 2.6° |
ω–2θ scans | h = 0→16 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→11 |
Tmin = 0.492, Tmax = 0.583 | l = −18→17 |
3700 measured reflections | 3 standard reflections every 150 reflections |
3542 independent reflections | intensity decay: −0.1% |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0367P)2 + 1.5353P] where P = (Fo2 + 2Fc2)/3 |
3542 reflections | (Δ/σ)max < 0.001 |
253 parameters | Δρmax = 0.59 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
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 | Uiso*/Ueq | Occ. (<1) |
Ag1 | 0.5000 | 0.5000 | 0.5000 | 0.04000 (12) | |
Co1 | 0.19574 (3) | 0.37190 (5) | 0.47184 (3) | 0.02058 (11) | |
Cl1 | 0.47295 (8) | 0.38249 (11) | 0.22391 (7) | 0.0417 (2) | |
Cl2 | 0.5000 | 0.0000 | 0.5000 | 0.0454 (3) | |
S1 | 0.30444 (6) | 0.55848 (9) | 0.44754 (6) | 0.02741 (17) | |
O1 | 0.14597 (18) | 0.4998 (3) | 0.55573 (17) | 0.0284 (5) | |
O2 | 0.1355 (2) | 0.7241 (3) | 0.61434 (19) | 0.0392 (6) | |
O3 | 0.4350 (4) | 0.3429 (8) | 0.3006 (3) | 0.127 (2) | |
O4 | 0.3938 (6) | 0.4563 (6) | 0.1514 (4) | 0.152 (3) | |
O5 | 0.5711 (4) | 0.4729 (5) | 0.2582 (3) | 0.0879 (13) | |
O6 | 0.5030 (4) | 0.2534 (4) | 0.1830 (4) | 0.1032 (16) | |
O7 | 0.5009 (6) | 0.1547 (8) | 0.5280 (6) | 0.070 (2) | 0.50 |
O8 | 0.5780 (6) | −0.0101 (10) | 0.4459 (8) | 0.098 (3) | 0.50 |
O9 | 0.5190 (10) | −0.0930 (13) | 0.5775 (9) | 0.133 (4) | 0.50 |
O10 | 0.3886 (6) | −0.0226 (10) | 0.4341 (6) | 0.079 (2) | 0.50 |
N1 | 0.2377 (3) | 0.2483 (4) | 0.3760 (2) | 0.0335 (6) | |
H1 | 0.304 (4) | 0.252 (4) | 0.380 (3) | 0.033 (10)* | |
H2 | 0.225 (4) | 0.164 (5) | 0.382 (3) | 0.051 (15)* | |
N2 | 0.0707 (2) | 0.4379 (4) | 0.3635 (2) | 0.0301 (6) | |
H3 | 0.076 (3) | 0.526 (4) | 0.355 (3) | 0.021 (9)* | |
H4 | 0.007 (4) | 0.431 (5) | 0.382 (3) | 0.062 (14)* | |
N3 | 0.3122 (2) | 0.2950 (4) | 0.5846 (2) | 0.0293 (6) | |
H5 | 0.345 (4) | 0.373 (5) | 0.623 (3) | 0.043 (12)* | |
H6 | 0.357 (3) | 0.248 (4) | 0.569 (3) | 0.029 (10)* | |
N4 | 0.1015 (2) | 0.2121 (3) | 0.5023 (2) | 0.0294 (6) | |
H7 | 0.058 (4) | 0.257 (5) | 0.533 (3) | 0.041 (11)* | |
H8 | 0.058 (3) | 0.166 (4) | 0.452 (3) | 0.029 (10)* | |
C1 | 0.2712 (3) | 0.6901 (4) | 0.5306 (3) | 0.0348 (8) | |
H9 | 0.3378 | 0.7079 | 0.5842 | 0.042* | |
H10 | 0.2492 | 0.7841 | 0.4973 | 0.042* | |
C2 | 0.1778 (3) | 0.6359 (4) | 0.5704 (2) | 0.0279 (7) | |
C3 | 0.1761 (4) | 0.3000 (6) | 0.2771 (3) | 0.0502 (11) | |
H11 | 0.2142 | 0.3845 | 0.2591 | 0.060* | |
H12 | 0.1724 | 0.2208 | 0.2305 | 0.060* | |
C4 | 0.0624 (3) | 0.3432 (6) | 0.2775 (3) | 0.0501 (11) | |
H13 | 0.0185 | 0.2549 | 0.2800 | 0.060* | |
H14 | 0.0257 | 0.3976 | 0.2188 | 0.060* | |
C5 | 0.2609 (3) | 0.1903 (5) | 0.6400 (3) | 0.0400 (8) | |
H15 | 0.3175 | 0.1246 | 0.6798 | 0.048* | |
H16 | 0.2266 | 0.2453 | 0.6819 | 0.048* | |
C6 | 0.1748 (3) | 0.1024 (4) | 0.5673 (3) | 0.0381 (8) | |
H17 | 0.2100 | 0.0376 | 0.5308 | 0.046* | |
H18 | 0.1318 | 0.0415 | 0.5993 | 0.046* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ag1 | 0.01916 (17) | 0.0438 (2) | 0.0608 (3) | 0.00068 (16) | 0.01763 (17) | 0.0042 (2) |
Co1 | 0.01564 (18) | 0.0233 (2) | 0.0231 (2) | 0.00048 (16) | 0.00621 (15) | 0.00018 (16) |
Cl1 | 0.0511 (5) | 0.0386 (5) | 0.0386 (5) | 0.0029 (4) | 0.0182 (4) | −0.0003 (4) |
Cl2 | 0.0390 (7) | 0.0425 (7) | 0.0540 (8) | 0.0042 (6) | 0.0123 (6) | −0.0046 (7) |
S1 | 0.0204 (3) | 0.0301 (4) | 0.0348 (4) | −0.0011 (3) | 0.0127 (3) | 0.0022 (3) |
O1 | 0.0242 (10) | 0.0308 (12) | 0.0349 (12) | −0.0034 (10) | 0.0156 (9) | −0.0029 (10) |
O2 | 0.0356 (13) | 0.0373 (14) | 0.0489 (15) | 0.0054 (11) | 0.0187 (12) | −0.0101 (12) |
O3 | 0.091 (3) | 0.229 (7) | 0.078 (3) | −0.029 (4) | 0.054 (3) | 0.013 (4) |
O4 | 0.183 (6) | 0.082 (3) | 0.120 (4) | 0.034 (4) | −0.066 (4) | 0.022 (3) |
O5 | 0.098 (3) | 0.077 (3) | 0.089 (3) | −0.037 (2) | 0.027 (2) | −0.029 (2) |
O6 | 0.118 (4) | 0.056 (2) | 0.166 (5) | −0.025 (2) | 0.089 (3) | −0.046 (3) |
O7 | 0.077 (5) | 0.050 (4) | 0.100 (6) | −0.003 (3) | 0.051 (4) | −0.024 (4) |
O8 | 0.057 (4) | 0.104 (7) | 0.149 (8) | −0.014 (4) | 0.055 (5) | −0.079 (6) |
O9 | 0.115 (9) | 0.123 (9) | 0.136 (10) | −0.001 (7) | −0.006 (7) | 0.075 (8) |
O10 | 0.039 (3) | 0.101 (6) | 0.085 (5) | 0.000 (4) | −0.001 (3) | 0.011 (5) |
N1 | 0.0306 (16) | 0.0368 (18) | 0.0350 (16) | 0.0019 (14) | 0.0125 (13) | −0.0055 (14) |
N2 | 0.0203 (13) | 0.0368 (17) | 0.0325 (15) | 0.0003 (13) | 0.0067 (11) | 0.0070 (14) |
N3 | 0.0225 (13) | 0.0328 (16) | 0.0309 (15) | 0.0024 (12) | 0.0053 (11) | 0.0022 (13) |
N4 | 0.0250 (13) | 0.0322 (16) | 0.0306 (15) | −0.0052 (12) | 0.0076 (12) | 0.0012 (12) |
C1 | 0.0328 (17) | 0.0236 (16) | 0.053 (2) | −0.0027 (14) | 0.0209 (16) | −0.0052 (16) |
C2 | 0.0197 (14) | 0.0319 (17) | 0.0319 (16) | 0.0056 (13) | 0.0071 (12) | −0.0016 (14) |
C3 | 0.051 (2) | 0.072 (3) | 0.0290 (19) | 0.008 (2) | 0.0136 (17) | −0.0048 (19) |
C4 | 0.043 (2) | 0.072 (3) | 0.0286 (19) | 0.002 (2) | −0.0003 (16) | 0.001 (2) |
C5 | 0.0345 (18) | 0.052 (2) | 0.0327 (18) | 0.0036 (17) | 0.0083 (15) | 0.0145 (17) |
C6 | 0.040 (2) | 0.0314 (19) | 0.045 (2) | 0.0009 (15) | 0.0154 (17) | 0.0112 (16) |
Geometric parameters (Å, º) top
Ag1—S1i | 2.3954 (10) | N1—C3 | 1.483 (5) |
Ag1—S1 | 2.3954 (10) | N1—H1 | 0.82 (4) |
Ag1—O3 | 3.090 (5) | N1—H2 | 0.78 (5) |
Ag1—O7 | 3.124 (7) | N2—C4 | 1.480 (5) |
Co1—O1 | 1.897 (2) | N2—H3 | 0.81 (4) |
Co1—N1 | 1.957 (3) | N2—H4 | 0.92 (5) |
Co1—N2 | 1.952 (3) | N3—C5 | 1.492 (5) |
Co1—N3 | 1.965 (3) | N3—H5 | 0.91 (4) |
Co1—N4 | 1.983 (3) | N3—H6 | 0.78 (4) |
Co1—S1 | 2.2458 (10) | N4—C6 | 1.479 (4) |
Cl1—O3 | 1.370 (4) | N4—H7 | 0.89 (4) |
Cl1—O4 | 1.381 (4) | N4—H8 | 0.87 (4) |
Cl1—O6 | 1.400 (4) | C1—C2 | 1.522 (4) |
Cl1—O5 | 1.432 (4) | C1—H9 | 0.9700 |
Cl2—O9 | 1.358 (9) | C1—H10 | 0.9700 |
Cl2—O9ii | 1.358 (9) | C3—C4 | 1.473 (6) |
Cl2—O8ii | 1.416 (7) | C3—H11 | 0.9700 |
Cl2—O8 | 1.416 (7) | C3—H12 | 0.9700 |
Cl2—O7 | 1.445 (7) | C4—H13 | 0.9700 |
Cl2—O7ii | 1.445 (7) | C4—H14 | 0.9700 |
Cl2—O10ii | 1.454 (7) | C5—C6 | 1.491 (5) |
Cl2—O10 | 1.454 (7) | C5—H15 | 0.9700 |
S1—C1 | 1.813 (4) | C5—H16 | 0.9700 |
O1—C2 | 1.283 (4) | C6—H17 | 0.9700 |
O2—C2 | 1.225 (4) | C6—H18 | 0.9700 |
| | | |
S1—Ag1—S1i | 180.0 | C4—N2—H4 | 111 (3) |
S1i—Ag1—O3 | 99.35 (10) | Co1—N2—H4 | 108 (3) |
S1—Ag1—O3 | 80.65 (10) | H3—N2—H4 | 103 (4) |
S1i—Ag1—O7 | 77.11 (14) | C5—N3—Co1 | 109.5 (2) |
S1—Ag1—O7 | 102.89 (14) | C5—N3—H5 | 110 (3) |
O3—Ag1—O7 | 69.98 (19) | Co1—N3—H5 | 109 (3) |
O1—Co1—N2 | 89.57 (12) | C5—N3—H6 | 105 (3) |
N4—Co1—S1 | 176.16 (10) | Co1—N3—H6 | 112 (3) |
O1—Co1—N1 | 175.06 (12) | H5—N3—H6 | 110 (4) |
N2—Co1—N1 | 85.56 (13) | C6—N4—Co1 | 108.9 (2) |
O1—Co1—N3 | 89.21 (12) | C6—N4—H7 | 110 (3) |
N2—Co1—N3 | 175.04 (13) | Co1—N4—H7 | 106 (3) |
N1—Co1—N3 | 95.70 (14) | C6—N4—H8 | 110 (2) |
O1—Co1—N4 | 88.36 (12) | Co1—N4—H8 | 115 (2) |
N2—Co1—N4 | 90.48 (13) | H7—N4—H8 | 107 (4) |
N1—Co1—N4 | 92.51 (15) | C2—C1—S1 | 112.8 (2) |
N3—Co1—N4 | 84.67 (12) | C2—C1—H9 | 109.0 |
O1—Co1—S1 | 88.45 (7) | S1—C1—H9 | 109.0 |
N2—Co1—S1 | 91.63 (10) | C2—C1—H10 | 109.0 |
N1—Co1—S1 | 90.85 (11) | S1—C1—H10 | 109.0 |
N3—Co1—S1 | 93.15 (9) | H9—C1—H10 | 107.8 |
O3—Cl1—O4 | 113.3 (4) | O2—C2—O1 | 122.8 (3) |
O3—Cl1—O6 | 108.9 (4) | O2—C2—C1 | 118.7 (3) |
O4—Cl1—O6 | 107.4 (4) | O1—C2—C1 | 118.5 (3) |
O3—Cl1—O5 | 109.3 (3) | C4—C3—N1 | 108.0 (3) |
O4—Cl1—O5 | 110.0 (3) | C4—C3—H11 | 110.1 |
O6—Cl1—O5 | 107.9 (3) | N1—C3—H11 | 110.1 |
O9—Cl2—O8 | 115.4 (7) | C4—C3—H12 | 110.1 |
O9—Cl2—O7 | 112.0 (6) | N1—C3—H12 | 110.1 |
O8—Cl2—O7 | 105.4 (4) | H11—C3—H12 | 108.4 |
O9—Cl2—O10 | 110.9 (6) | C3—C4—N2 | 108.7 (3) |
O8—Cl2—O10 | 108.2 (5) | C3—C4—H13 | 110.0 |
O7—Cl2—O10 | 104.2 (5) | N2—C4—H13 | 110.0 |
C1—S1—Co1 | 96.81 (11) | C3—C4—H14 | 110.0 |
C1—S1—Ag1 | 109.97 (12) | N2—C4—H14 | 110.0 |
Co1—S1—Ag1 | 113.22 (4) | H13—C4—H14 | 108.3 |
C2—O1—Co1 | 122.5 (2) | C6—C5—N3 | 106.9 (3) |
Cl1—O3—Ag1 | 125.0 (3) | C6—C5—H15 | 110.3 |
Cl2—O7—Ag1 | 156.5 (5) | N3—C5—H15 | 110.3 |
C3—N1—Co1 | 109.3 (3) | C6—C5—H16 | 110.3 |
C3—N1—H1 | 107 (3) | N3—C5—H16 | 110.3 |
Co1—N1—H1 | 113 (3) | H15—C5—H16 | 108.6 |
C3—N1—H2 | 110 (4) | N4—C6—C5 | 106.3 (3) |
Co1—N1—H2 | 112 (3) | N4—C6—H17 | 110.5 |
H1—N1—H2 | 105 (4) | C5—C6—H17 | 110.5 |
C4—N2—Co1 | 109.9 (2) | N4—C6—H18 | 110.5 |
C4—N2—H3 | 115 (3) | C5—C6—H18 | 110.5 |
Co1—N2—H3 | 109 (3) | H17—C6—H18 | 108.7 |
| | | |
O1—Co1—S1—C1 | 3.03 (15) | N2—Co1—N1—C3 | 15.0 (3) |
N2—Co1—S1—C1 | 92.55 (16) | N3—Co1—N1—C3 | −169.8 (3) |
N1—Co1—S1—C1 | 178.14 (16) | N4—Co1—N1—C3 | 105.3 (3) |
N3—Co1—S1—C1 | −86.10 (16) | S1—Co1—N1—C3 | −76.6 (3) |
O1—Co1—S1—Ag1 | 118.21 (8) | O1—Co1—N2—C4 | −170.1 (3) |
N2—Co1—S1—Ag1 | −152.26 (10) | N1—Co1—N2—C4 | 10.7 (3) |
N1—Co1—S1—Ag1 | −66.67 (10) | N4—Co1—N2—C4 | −81.7 (3) |
N3—Co1—S1—Ag1 | 29.09 (10) | S1—Co1—N2—C4 | 101.5 (3) |
O3—Ag1—S1—C1 | −171.75 (17) | O1—Co1—N3—C5 | 76.1 (3) |
O7—Ag1—S1—C1 | 121.42 (19) | N1—Co1—N3—C5 | −104.3 (3) |
O3—Ag1—S1—Co1 | 81.19 (12) | N4—Co1—N3—C5 | −12.3 (3) |
O7—Ag1—S1—Co1 | 14.37 (15) | S1—Co1—N3—C5 | 164.5 (2) |
N2—Co1—O1—C2 | −89.0 (3) | O1—Co1—N4—C6 | −106.3 (2) |
N3—Co1—O1—C2 | 95.8 (3) | N2—Co1—N4—C6 | 164.2 (3) |
N4—Co1—O1—C2 | −179.5 (3) | N1—Co1—N4—C6 | 78.6 (3) |
S1—Co1—O1—C2 | 2.7 (2) | N3—Co1—N4—C6 | −16.9 (3) |
O4—Cl1—O3—Ag1 | −105.1 (4) | Co1—S1—C1—C2 | −7.6 (3) |
O6—Cl1—O3—Ag1 | 135.6 (4) | Ag1—S1—C1—C2 | −125.4 (2) |
O5—Cl1—O3—Ag1 | 18.0 (5) | Co1—O1—C2—O2 | 170.4 (3) |
S1i—Ag1—O3—Cl1 | −65.0 (4) | Co1—O1—C2—C1 | −8.9 (4) |
S1—Ag1—O3—Cl1 | 115.0 (4) | S1—C1—C2—O2 | −168.2 (3) |
O7—Ag1—O3—Cl1 | −137.6 (4) | S1—C1—C2—O1 | 11.2 (4) |
O9—Cl2—O7—Ag1 | 170.9 (10) | Co1—N1—C3—C4 | −37.7 (5) |
O8—Cl2—O7—Ag1 | 44.6 (12) | N1—C3—C4—N2 | 47.0 (5) |
O10ii—Cl2—O7—Ag1 | 110.8 (11) | Co1—N2—C4—C3 | −34.6 (4) |
O10—Cl2—O7—Ag1 | −69.2 (11) | Co1—N3—C5—C6 | 38.8 (4) |
S1i—Ag1—O7—Cl2 | −91.0 (11) | Co1—N4—C6—C5 | 42.3 (3) |
S1—Ag1—O7—Cl2 | 89.0 (11) | N3—C5—C6—N4 | −52.6 (4) |
O3—Ag1—O7—Cl2 | 14.1 (10) | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H4···O2iii | 0.92 (5) | 2.27 (5) | 3.053 (4) | 143 (4) |
N4—H8···O2iii | 0.87 (4) | 2.53 (4) | 3.004 (4) | 115 (3) |
N1—H2···O4iv | 0.78 (5) | 2.34 (5) | 3.057 (6) | 152 (5) |
N2—H3···O6v | 0.81 (4) | 2.26 (4) | 2.993 (5) | 151 (3) |
Symmetry codes: (iii) −x, −y+1, −z+1; (iv) −x+1/2, y−1/2, −z+1/2; (v) −x+1/2, y+1/2, −z+1/2. |