The structures of [Mn(S2O3)2(C12H8N2)(H2O)2] and [Mn(S4O6)(C10H8N2)2] are presented. The former consists of pairs of polymeric chains formed by manganese polyhedra bridged by bidentate thiosulfate anions, which are in turn related to each other by a pseudo-twofold screw axis. The latter has crystallographic twofold symmetry and consists of monomers in which manganese displays its typical octahedral coordination provided by the bidentate bites of two bipyridine bases and a tetrathionate anion, which is, to our knowledge, the first chelating tetrathionate to be reported in the literature.
Supporting information
CCDC references: 158225; 158226
Compound (I) was obtained by mixing manganese chloride, sodium thiosulfate and
phenanthroline in a (1:3:1) ratio. A few hours after mixing, crystals suitable
for X-ray diffraction were already present in the solution. A similar
procedure using bipy did not, however, produce similar results. All trials
with bipy were unsuccessful, the solutions becoming dark as a result of some
(presumed) oxidation processes. As indirect evidence of this, in one of the
many attempts to generate the bipy thiosulfate, crystals of the tetrathionate
(II) were fortuitously obtained when a solution left unattended for months was
finally checked for crystals.
H atoms attached to carbon were added at their expected positions and not
refined, but allowed to ride. Those pertaining to the water molecules were not
found in the difference Fourier, and were ignored. Crystals of (I) were of
poor quality, and this was reflected in the refinement results: the final
agreement factor was rather high, as was the residual electron density ripple
(ca 1.3 e Å-3), uniformly distributed. The inner sulfur atom S2 in
the tetrathionate group in (II) was surrounded by a number of small, residual
electron-density peaks and exhibited a conspicuously large displacement
ellipsoid, suggesting some kind of disorder. Although the splitting of the
model into two halves tended to diminish the discrepancy index R1, this was
achieved at the cost of a deterioration of the overall geometry of the group,
both in bond lengths and in interatomic angles. It was then decided to keep
the model unsplit, and to leave to the anisotropic displacement factor of S2
the whole representation of this anomalous situation. With this final model,
the residual electron-density ripple around S2 consisted in a large number of
peaks below 0.70 e/Å3, at distances shorter than 1 Å.
For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: MSC/AFC Diffractometer Control Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: XP in SHELXTL/PC (Sheldrick,1994) for (I); XP in SHELXTL/PC (Sheldrick, 1994) for (II). For both compounds, software used to prepare material for publication: PARST (Nardelli, 1983) and CSD (Allen & Kennard, 1993).
(I) Catena-poly[[diaqua(phenanthroline-N,
N')
manganese(II)-µu-(thiosulfato-O:
S)]
top
Crystal data top
[Mn(S2O3)(C12H8N2)(H2O)2] | F(000) = 780 |
Mr = 383.30 | Dx = 1.695 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.371 (2) Å | Cell parameters from 25 reflections |
b = 7.1020 (14) Å | θ = 7.5–15° |
c = 20.446 (4) Å | µ = 1.18 mm−1 |
β = 94.07 (3)° | T = 293 K |
V = 1502.1 (5) Å3 | Plates, pale yellow |
Z = 4 | 0.38 × 0.28 × 0.14 mm |
Data collection top
Rigaku AFC7S Difractometer diffractometer | 3935 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.087 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
ω/2θ scans | h = −13→13 |
Absorption correction: ψ scan (MSC/AFC Diffractometer Control Software; Molecular Structure Corporation, 1988) | k = −1→9 |
Tmin = 0.61, Tmax = 0.85 | l = 0→26 |
4432 measured reflections | 3 standard reflections every 150 reflections |
4255 independent reflections | intensity decay: <3% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: geom + difmap |
R[F2 > 2σ(F2)] = 0.062 | H-atom parameters constrained |
wR(F2) = 0.193 | w = 1/[σ2(Fo2) + (0.067P)2 + 9.528P] where P = (Fo2 + 2Fc2)/3 |
S = 1.19 | (Δ/σ)max < 0.001 |
4255 reflections | Δρmax = 1.28 e Å−3 |
397 parameters | Δρmin = −0.68 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.06 (5) |
Crystal data top
[Mn(S2O3)(C12H8N2)(H2O)2] | V = 1502.1 (5) Å3 |
Mr = 383.30 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.371 (2) Å | µ = 1.18 mm−1 |
b = 7.1020 (14) Å | T = 293 K |
c = 20.446 (4) Å | 0.38 × 0.28 × 0.14 mm |
β = 94.07 (3)° | |
Data collection top
Rigaku AFC7S Difractometer diffractometer | 3935 reflections with I > 2σ(I) |
Absorption correction: ψ scan (MSC/AFC Diffractometer Control Software; Molecular Structure Corporation, 1988) | Rint = 0.087 |
Tmin = 0.61, Tmax = 0.85 | 3 standard reflections every 150 reflections |
4432 measured reflections | intensity decay: <3% |
4255 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.062 | H-atom parameters constrained |
wR(F2) = 0.193 | Δρmax = 1.28 e Å−3 |
S = 1.19 | Δρmin = −0.68 e Å−3 |
4255 reflections | Absolute structure: Flack (1983) |
397 parameters | Absolute structure parameter: 0.06 (5) |
1 restraint | |
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 | |
Mn1A | 0.26655 (11) | 0.3910 (2) | 0.32590 (6) | 0.0252 (3) | |
S1A | 0.1930 (2) | 0.7468 (4) | 0.33788 (11) | 0.0309 (5) | |
S2A | 0.27248 (17) | 0.9274 (3) | 0.27697 (10) | 0.0249 (4) | |
O1A | 0.3170 (8) | 1.0960 (11) | 0.3141 (4) | 0.0401 (18) | |
O2A | 0.3865 (7) | 0.8405 (12) | 0.2507 (4) | 0.0458 (19) | |
O3A | 0.1757 (6) | 0.9778 (12) | 0.2238 (3) | 0.0388 (17) | |
N1A | 0.3819 (7) | 0.3812 (15) | 0.4244 (4) | 0.039 (2) | |
N2A | 0.1231 (7) | 0.3257 (14) | 0.4016 (4) | 0.0337 (18) | |
C1A | 0.5079 (10) | 0.4017 (19) | 0.4370 (6) | 0.050 (3) | |
H1AA | 0.5581 | 0.4195 | 0.4016 | 0.060* | |
C2A | 0.5702 (13) | 0.399 (2) | 0.4989 (8) | 0.075 (5) | |
H2AA | 0.6598 | 0.4091 | 0.5036 | 0.090* | |
C3A | 0.5016 (16) | 0.381 (2) | 0.5536 (8) | 0.082 (5) | |
H3AA | 0.5426 | 0.3864 | 0.5955 | 0.099* | |
C4A | 0.3672 (14) | 0.353 (2) | 0.5441 (5) | 0.058 (4) | |
C5A | 0.2809 (17) | 0.319 (3) | 0.5947 (6) | 0.073 (5) | |
H5AA | 0.3152 | 0.3189 | 0.6380 | 0.087* | |
C6A | 0.1553 (17) | 0.287 (3) | 0.5835 (5) | 0.072 (5) | |
H6AA | 0.1051 | 0.2630 | 0.6185 | 0.087* | |
C7A | 0.0975 (14) | 0.290 (2) | 0.5196 (5) | 0.057 (4) | |
C8A | −0.0359 (13) | 0.261 (2) | 0.5042 (7) | 0.062 (4) | |
H8AA | −0.0905 | 0.2407 | 0.5377 | 0.074* | |
C9A | −0.0859 (11) | 0.263 (2) | 0.4394 (6) | 0.052 (3) | |
H9AA | −0.1731 | 0.2390 | 0.4288 | 0.063* | |
C10A | −0.0035 (10) | 0.301 (2) | 0.3910 (5) | 0.046 (3) | |
H10A | −0.0390 | 0.3089 | 0.3481 | 0.055* | |
C11A | 0.1742 (11) | 0.3236 (16) | 0.4646 (5) | 0.039 (2) | |
C12A | 0.3133 (10) | 0.3603 (15) | 0.4769 (4) | 0.036 (2) | |
Mn1B | 0.74602 (11) | 0.9133 (2) | 0.17075 (6) | 0.0238 (3) | |
S1B | 0.8086 (2) | 1.2687 (4) | 0.15161 (12) | 0.0338 (5) | |
S2B | 0.76259 (17) | 1.4501 (3) | 0.22155 (10) | 0.0245 (4) | |
O1B | 0.7003 (7) | 1.6203 (11) | 0.1901 (4) | 0.0391 (18) | |
O2B | 0.6735 (6) | 1.3612 (11) | 0.2648 (3) | 0.0382 (16) | |
O3B | 0.8819 (6) | 1.5031 (11) | 0.2597 (4) | 0.0389 (17) | |
N1B | 0.5799 (6) | 0.9310 (12) | 0.0911 (3) | 0.0258 (15) | |
N2B | 0.8359 (6) | 0.8832 (13) | 0.0732 (4) | 0.0298 (17) | |
C1B | 0.4574 (8) | 0.9469 (18) | 0.1019 (4) | 0.034 (2) | |
H1BA | 0.4328 | 0.9443 | 0.1447 | 0.041* | |
C2B | 0.3599 (8) | 0.968 (2) | 0.0485 (4) | 0.039 (3) | |
H2BA | 0.2732 | 0.9786 | 0.0568 | 0.047* | |
C3B | 0.3962 (9) | 0.9736 (17) | −0.0140 (5) | 0.037 (2) | |
H3BA | 0.3336 | 0.9867 | −0.0486 | 0.044* | |
C4B | 0.5257 (9) | 0.9594 (18) | −0.0270 (4) | 0.035 (2) | |
C5B | 0.5711 (10) | 0.9650 (19) | −0.0913 (4) | 0.041 (3) | |
H5BA | 0.5129 | 0.9839 | −0.1274 | 0.049* | |
C6B | 0.6965 (10) | 0.943 (2) | −0.0999 (5) | 0.045 (3) | |
H6BA | 0.7238 | 0.9509 | −0.1422 | 0.054* | |
C7B | 0.7912 (8) | 0.9089 (16) | −0.0466 (4) | 0.0312 (19) | |
C8B | 0.9207 (10) | 0.8796 (19) | −0.0550 (5) | 0.043 (3) | |
H8BA | 0.9507 | 0.8781 | −0.0968 | 0.051* | |
C9B | 1.0043 (9) | 0.853 (2) | −0.0010 (6) | 0.049 (3) | |
H9BA | 1.0918 | 0.8344 | −0.0062 | 0.058* | |
C10B | 0.9595 (9) | 0.8534 (18) | 0.0619 (5) | 0.037 (2) | |
H10B | 1.0186 | 0.8318 | 0.0975 | 0.045* | |
C11B | 0.7536 (8) | 0.9105 (15) | 0.0194 (4) | 0.0291 (18) | |
C12B | 0.6154 (7) | 0.9352 (14) | 0.0295 (4) | 0.0264 (17) | |
O1WA | 0.1275 (6) | 0.3566 (11) | 0.2422 (3) | 0.0330 (15) | |
O2WA | 0.4215 (6) | 0.4738 (12) | 0.2699 (4) | 0.0441 (19) | |
O1WB | 0.9223 (6) | 0.8621 (14) | 0.2297 (4) | 0.057 (2) | |
O2WB | 0.6304 (6) | 0.9888 (11) | 0.2500 (3) | 0.0333 (15) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1A | 0.0238 (5) | 0.0258 (8) | 0.0258 (6) | −0.0008 (6) | 0.0008 (4) | 0.0011 (6) |
S1A | 0.0342 (11) | 0.0272 (13) | 0.0324 (11) | 0.0024 (10) | 0.0100 (9) | 0.0025 (10) |
S2A | 0.0206 (7) | 0.0230 (11) | 0.0308 (9) | −0.0010 (9) | −0.0002 (7) | 0.0025 (10) |
O1A | 0.048 (4) | 0.022 (4) | 0.049 (4) | 0.000 (3) | −0.003 (3) | −0.006 (3) |
O2A | 0.038 (3) | 0.039 (4) | 0.064 (5) | 0.001 (4) | 0.025 (3) | 0.012 (4) |
O3A | 0.044 (3) | 0.035 (4) | 0.035 (3) | −0.006 (3) | −0.013 (3) | −0.004 (3) |
N1A | 0.032 (4) | 0.036 (5) | 0.046 (4) | 0.004 (4) | −0.015 (3) | 0.007 (5) |
N2A | 0.031 (4) | 0.036 (5) | 0.034 (4) | 0.004 (4) | −0.002 (3) | 0.000 (4) |
C1A | 0.042 (5) | 0.042 (7) | 0.061 (6) | 0.008 (6) | −0.033 (5) | 0.005 (6) |
C2A | 0.068 (8) | 0.056 (9) | 0.092 (10) | 0.002 (8) | −0.063 (8) | −0.016 (10) |
C3A | 0.104 (11) | 0.052 (9) | 0.081 (10) | 0.018 (10) | −0.067 (9) | −0.013 (9) |
C4A | 0.100 (9) | 0.046 (7) | 0.023 (5) | 0.002 (7) | −0.032 (5) | 0.000 (5) |
C5A | 0.119 (13) | 0.063 (10) | 0.034 (6) | 0.004 (10) | −0.011 (7) | 0.001 (7) |
C6A | 0.120 (12) | 0.082 (12) | 0.013 (4) | 0.002 (11) | −0.006 (6) | −0.004 (6) |
C7A | 0.090 (9) | 0.053 (8) | 0.030 (5) | 0.022 (8) | 0.010 (5) | 0.009 (6) |
C8A | 0.064 (8) | 0.057 (8) | 0.070 (8) | 0.004 (7) | 0.042 (7) | 0.009 (8) |
C9A | 0.043 (6) | 0.067 (9) | 0.046 (6) | −0.007 (7) | 0.000 (5) | 0.007 (7) |
C10A | 0.033 (5) | 0.059 (8) | 0.044 (5) | 0.003 (5) | 0.000 (4) | 0.026 (6) |
C11A | 0.061 (6) | 0.028 (5) | 0.026 (4) | 0.006 (5) | −0.006 (4) | 0.000 (4) |
C12A | 0.065 (6) | 0.030 (5) | 0.010 (3) | 0.005 (5) | −0.014 (3) | 0.006 (4) |
Mn1B | 0.0234 (5) | 0.0256 (8) | 0.0214 (5) | −0.0016 (6) | −0.0041 (4) | 0.0008 (6) |
S1B | 0.0435 (13) | 0.0250 (12) | 0.0338 (11) | −0.0034 (11) | 0.0080 (9) | 0.0043 (11) |
S2B | 0.0196 (8) | 0.0212 (11) | 0.0318 (10) | −0.0006 (9) | −0.0034 (7) | 0.0007 (9) |
O1B | 0.036 (4) | 0.021 (4) | 0.058 (5) | −0.001 (3) | −0.019 (3) | 0.002 (4) |
O2B | 0.044 (3) | 0.030 (4) | 0.041 (4) | 0.003 (3) | 0.011 (3) | 0.001 (3) |
O3B | 0.032 (3) | 0.027 (4) | 0.055 (4) | −0.002 (3) | −0.017 (3) | 0.007 (4) |
N1B | 0.025 (3) | 0.023 (4) | 0.029 (3) | 0.009 (3) | 0.000 (2) | 0.006 (3) |
N2B | 0.024 (3) | 0.031 (4) | 0.034 (4) | 0.006 (4) | −0.002 (3) | 0.001 (4) |
C1B | 0.026 (4) | 0.052 (7) | 0.025 (4) | 0.005 (5) | 0.002 (3) | 0.008 (5) |
C2B | 0.024 (4) | 0.062 (8) | 0.031 (4) | 0.008 (5) | −0.004 (3) | 0.001 (5) |
C3B | 0.031 (4) | 0.039 (6) | 0.039 (5) | 0.003 (5) | −0.017 (4) | 0.007 (5) |
C4B | 0.034 (4) | 0.038 (6) | 0.033 (5) | −0.004 (5) | 0.000 (3) | 0.003 (5) |
C5B | 0.058 (6) | 0.049 (7) | 0.015 (4) | 0.003 (6) | −0.011 (4) | −0.008 (5) |
C6B | 0.056 (6) | 0.052 (7) | 0.025 (4) | 0.000 (6) | −0.005 (4) | −0.009 (5) |
C7B | 0.041 (4) | 0.032 (5) | 0.022 (4) | 0.007 (5) | 0.006 (3) | 0.003 (4) |
C8B | 0.049 (5) | 0.044 (7) | 0.037 (5) | 0.004 (6) | 0.016 (4) | −0.009 (5) |
C9B | 0.030 (4) | 0.061 (8) | 0.056 (6) | −0.007 (5) | 0.011 (4) | −0.027 (6) |
C10B | 0.029 (4) | 0.044 (6) | 0.040 (5) | 0.009 (5) | 0.006 (4) | 0.000 (5) |
C11B | 0.038 (4) | 0.027 (5) | 0.023 (4) | 0.001 (4) | 0.003 (3) | −0.002 (4) |
C12B | 0.029 (4) | 0.024 (4) | 0.026 (4) | −0.003 (4) | 0.003 (3) | −0.004 (4) |
O1WA | 0.039 (3) | 0.035 (4) | 0.023 (3) | 0.006 (3) | −0.011 (2) | 0.005 (3) |
O2WA | 0.034 (3) | 0.038 (4) | 0.063 (5) | 0.009 (3) | 0.022 (3) | 0.017 (4) |
O1WB | 0.031 (3) | 0.057 (6) | 0.076 (5) | −0.016 (4) | −0.036 (3) | 0.022 (5) |
O2WB | 0.040 (3) | 0.032 (4) | 0.030 (3) | −0.007 (3) | 0.011 (3) | −0.010 (3) |
Geometric parameters (Å, º) top
Mn1A—O2WA | 2.122 (6) | Mn1B—O1WB | 2.149 (6) |
Mn1A—O1WA | 2.173 (6) | Mn1B—O2WB | 2.150 (6) |
Mn1A—O1Ai | 2.176 (8) | Mn1B—O1Bi | 2.177 (8) |
Mn1A—N1A | 2.269 (8) | Mn1B—N2B | 2.270 (7) |
Mn1A—N2A | 2.270 (8) | Mn1B—N1B | 2.289 (6) |
Mn1A—S1A | 2.656 (3) | Mn1B—S1B | 2.642 (3) |
S1A—S2A | 2.005 (3) | S1B—S2B | 2.007 (3) |
S2A—O3A | 1.470 (7) | S2B—O3B | 1.465 (6) |
S2A—O2A | 1.469 (7) | S2B—O2B | 1.466 (7) |
S2A—O1A | 1.475 (8) | S2B—O1B | 1.494 (7) |
N1A—C1A | 1.322 (12) | N1B—C1B | 1.310 (10) |
N1A—C12A | 1.338 (13) | N1B—C12B | 1.337 (10) |
N2A—C10A | 1.328 (12) | N2B—C10B | 1.336 (10) |
N2A—C11A | 1.358 (12) | N2B—C11B | 1.358 (10) |
C1A—C2A | 1.380 (15) | C1B—C2B | 1.443 (11) |
C2A—C3A | 1.37 (2) | C2B—C3B | 1.358 (13) |
C3A—C4A | 1.41 (2) | C3B—C4B | 1.391 (12) |
C4A—C5A | 1.44 (2) | C4B—C5B | 1.428 (13) |
C4A—C12A | 1.446 (11) | C4B—C12B | 1.441 (12) |
C5A—C6A | 1.33 (2) | C5B—C6B | 1.334 (14) |
C6A—C7A | 1.399 (16) | C6B—C7B | 1.435 (12) |
C7A—C8A | 1.41 (2) | C7B—C8B | 1.383 (12) |
C7A—C11A | 1.441 (15) | C7B—C11B | 1.430 (11) |
C8A—C9A | 1.388 (18) | C8B—C9B | 1.367 (15) |
C9A—C10A | 1.379 (15) | C9B—C10B | 1.397 (14) |
C11A—C12A | 1.470 (15) | C11B—C12B | 1.473 (11) |
| | | |
O2WA—Mn1A—O1WA | 95.2 (3) | O1WB—Mn1B—O2WB | 96.7 (3) |
O2WA—Mn1A—O1Ai | 90.6 (3) | O1WB—Mn1B—O1Bi | 85.6 (3) |
O1WA—Mn1A—O1Ai | 87.5 (3) | O2WB—Mn1B—O1Bi | 87.8 (3) |
O2WA—Mn1A—N1A | 96.7 (3) | O1WB—Mn1B—N2B | 95.2 (3) |
O1WA—Mn1A—N1A | 167.0 (3) | O2WB—Mn1B—N2B | 166.1 (3) |
O1Ai—Mn1A—N1A | 87.3 (3) | O1Bi—Mn1B—N2B | 100.2 (3) |
O2WA—Mn1A—N2A | 169.4 (3) | O1WB—Mn1B—N1B | 167.5 (3) |
O1WA—Mn1A—N2A | 94.8 (3) | O2WB—Mn1B—N1B | 95.2 (2) |
O1Ai—Mn1A—N2A | 93.1 (3) | O1Bi—Mn1B—N1B | 91.1 (3) |
N1A—Mn1A—N2A | 73.6 (3) | N2B—Mn1B—N1B | 73.5 (2) |
O2WA—Mn1A—S1A | 91.1 (2) | O1WB—Mn1B—S1B | 92.1 (3) |
O1WA—Mn1A—S1A | 90.0 (2) | O2WB—Mn1B—S1B | 91.7 (2) |
O1Ai—Mn1A—S1A | 177.1 (2) | O1Bi—Mn1B—S1B | 177.60 (19) |
N1A—Mn1A—S1A | 94.8 (3) | N2B—Mn1B—S1B | 80.8 (2) |
N2A—Mn1A—S1A | 85.7 (3) | N1B—Mn1B—S1B | 91.3 (2) |
S2A—S1A—Mn1A | 114.69 (12) | S2B—S1B—Mn1B | 115.74 (12) |
O3A—S2A—O2A | 110.9 (5) | O3B—S2B—O2B | 109.5 (4) |
O3A—S2A—O1A | 110.8 (5) | O3B—S2B—O1B | 110.2 (4) |
O2A—S2A—O1A | 107.4 (5) | O2B—S2B—O1B | 109.7 (4) |
O3A—S2A—S1A | 109.0 (3) | O3B—S2B—S1B | 108.1 (3) |
O2A—S2A—S1A | 109.6 (4) | O2B—S2B—S1B | 110.2 (3) |
O1A—S2A—S1A | 109.1 (4) | O1B—S2B—S1B | 109.2 (3) |
S2A—O1A—Mn1Aii | 140.3 (5) | S2B—O1B—Mn1Bii | 139.3 (4) |
C1A—N1A—C12A | 115.4 (9) | C1B—N1B—C12B | 119.5 (7) |
C1A—N1A—Mn1A | 128.4 (8) | C1B—N1B—Mn1B | 125.1 (6) |
C12A—N1A—Mn1A | 116.1 (6) | C12B—N1B—Mn1B | 115.3 (5) |
C10A—N2A—C11A | 117.9 (9) | C10B—N2B—C11B | 115.9 (8) |
C10A—N2A—Mn1A | 127.2 (7) | C10B—N2B—Mn1B | 128.8 (6) |
C11A—N2A—Mn1A | 114.8 (7) | C11B—N2B—Mn1B | 115.1 (5) |
N1A—C1A—C2A | 124.7 (13) | N1B—C1B—C2B | 121.2 (8) |
C3A—C2A—C1A | 120.8 (13) | C3B—C2B—C1B | 119.3 (8) |
C2A—C3A—C4A | 117.8 (11) | C2B—C3B—C4B | 120.9 (8) |
C3A—C4A—C5A | 125.8 (11) | C3B—C4B—C5B | 124.0 (9) |
C3A—C4A—C12A | 116.0 (13) | C3B—C4B—C12B | 115.7 (8) |
C5A—C4A—C12A | 118.2 (12) | C5B—C4B—C12B | 120.3 (8) |
C6A—C5A—C4A | 124.0 (12) | C6B—C5B—C4B | 120.4 (8) |
C5A—C6A—C7A | 120.6 (14) | C5B—C6B—C7B | 122.7 (9) |
C8A—C7A—C6A | 123.6 (13) | C8B—C7B—C11B | 116.8 (8) |
C8A—C7A—C11A | 115.9 (11) | C8B—C7B—C6B | 123.3 (8) |
C6A—C7A—C11A | 120.5 (14) | C11B—C7B—C6B | 119.9 (8) |
C9A—C8A—C7A | 120.3 (10) | C9B—C8B—C7B | 119.1 (9) |
C10A—C9A—C8A | 118.5 (11) | C8B—C9B—C10B | 120.6 (9) |
N2A—C10A—C9A | 124.4 (10) | N2B—C10B—C9B | 123.1 (9) |
N2A—C11A—C7A | 122.8 (11) | N2B—C11B—C7B | 124.4 (8) |
N2A—C11A—C12A | 118.2 (9) | N2B—C11B—C12B | 117.8 (7) |
C7A—C11A—C12A | 119.0 (9) | C7B—C11B—C12B | 117.7 (7) |
N1A—C12A—C4A | 125.1 (10) | N1B—C12B—C4B | 123.5 (7) |
N1A—C12A—C11A | 116.9 (7) | N1B—C12B—C11B | 117.7 (7) |
C4A—C12A—C11A | 117.7 (10) | C4B—C12B—C11B | 118.8 (7) |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1B—H1BA···O2A | 0.93 (1) | 2.37 (1) | 3.27 (1) | 163 (1) |
C10A—H10A···O3Biii | 0.93 (1) | 2.37 (1) | 3.20 (1) | 148 (1) |
O2WA···O2A | | | 2.65 (1) | |
O2WB···O2A | | | 2.73 (1) | |
O2WB···O2B | | | 2.69 (1) | |
O2WA···O1WA | | | 3.17 (1) | |
O2WB···O1WB | | | 3.21 (1) | |
O1WA···O1Ai | | | 3.00 (1) | |
O1WA···O3Ai | | | 2.76 (1) | |
O1WA···O3Biii | | | 2.79 (1) | |
O2WA···O1Ai | | | 3.05 (1) | |
O2WA···O1Bi | | | 3.57 (1) | |
O2WA···O2Bi | | | 2.74 (1) | |
O1WB···O3Aiv | | | 2.76 (1) | |
O1WB···O1Bi | | | 2.93 (1) | |
O1WB···O3Bi | | | 2.66 (1) | |
O2WB···O1Bi | | | 3.00 (1) | |
Symmetry codes: (i) x, y−1, z; (iii) x−1, y−1, z; (iv) x+1, y, z. |
(II) Bis(2,2'-bipyridyl-N,
N') manganese(II) tetrathionate O,
O'
top
Crystal data top
[Mn(S4O6)(C10H8N2)2] | F(000) = 1204 |
Mr = 591.55 | Dx = 1.614 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 25 reflections |
a = 15.330 (3) Å | θ = 7.5–15° |
b = 9.889 (2) Å | µ = 0.93 mm−1 |
c = 16.061 (3) Å | T = 293 K |
V = 2434.8 (8) Å3 | Irregular blocks, pale yellow |
Z = 4 | 0.26 × 0.24 × 0.24 mm |
Data collection top
Rigaku AFC7S Difractometer diffractometer | 1247 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.062 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
ω/2θ scans | h = 0→19 |
Absorption correction: ψ scan (MSC/AFC Diffractometer Control Software; Molecular Structure Corporation, 1988) | k = 0→12 |
Tmin = 0.75, Tmax = 0.80 | l = 0→20 |
3002 measured reflections | 3 standard reflections every 150 reflections |
2804 independent reflections | intensity decay: <3% |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.183 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.093P)2] where P = (Fo2 + 2Fc2)/3 |
2804 reflections | (Δ/σ)max < 0.01 |
159 parameters | Δρmax = 0.59 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
Crystal data top
[Mn(S4O6)(C10H8N2)2] | V = 2434.8 (8) Å3 |
Mr = 591.55 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 15.330 (3) Å | µ = 0.93 mm−1 |
b = 9.889 (2) Å | T = 293 K |
c = 16.061 (3) Å | 0.26 × 0.24 × 0.24 mm |
Data collection top
Rigaku AFC7S Difractometer diffractometer | 1247 reflections with I > 2σ(I) |
Absorption correction: ψ scan (MSC/AFC Diffractometer Control Software; Molecular Structure Corporation, 1988) | Rint = 0.062 |
Tmin = 0.75, Tmax = 0.80 | 3 standard reflections every 150 reflections |
3002 measured reflections | intensity decay: <3% |
2804 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.183 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.59 e Å−3 |
2804 reflections | Δρmin = −0.42 e Å−3 |
159 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 | |
Mn | 0.0000 | 0.40428 (9) | 0.2500 | 0.0598 (3) | |
S1 | 0.10064 (9) | 0.12080 (14) | 0.33961 (9) | 0.0864 (5) | |
S2 | 0.00014 (16) | −0.0136 (3) | 0.31111 (16) | 0.1783 (13) | |
O1 | 0.0691 (2) | 0.2570 (3) | 0.3199 (2) | 0.0930 (11) | |
O2 | 0.1094 (3) | 0.0980 (4) | 0.4271 (3) | 0.1388 (18) | |
O3 | 0.1735 (3) | 0.0825 (5) | 0.2949 (4) | 0.1474 (19) | |
N1 | 0.0433 (3) | 0.5616 (4) | 0.3422 (2) | 0.0657 (10) | |
N2 | −0.1112 (2) | 0.4420 (4) | 0.3384 (2) | 0.0719 (10) | |
C1 | 0.1226 (3) | 0.6193 (5) | 0.3435 (3) | 0.0794 (13) | |
H1A | 0.1636 | 0.5906 | 0.3046 | 0.095* | |
C2 | 0.1467 (5) | 0.7179 (6) | 0.3990 (4) | 0.1019 (18) | |
H2A | 0.2021 | 0.7563 | 0.3970 | 0.122* | |
C3 | 0.0878 (6) | 0.7575 (6) | 0.4565 (4) | 0.129 (3) | |
H3A | 0.1020 | 0.8252 | 0.4943 | 0.155* | |
C4 | 0.0069 (5) | 0.6979 (5) | 0.4591 (3) | 0.104 (2) | |
H4A | −0.0332 | 0.7223 | 0.4999 | 0.125* | |
C5 | −0.0141 (3) | 0.6001 (4) | 0.3995 (3) | 0.0724 (13) | |
C6 | −0.1002 (3) | 0.5338 (5) | 0.3974 (3) | 0.0748 (14) | |
C7 | −0.1648 (5) | 0.5596 (6) | 0.4553 (4) | 0.120 (2) | |
H7A | −0.1551 | 0.6216 | 0.4979 | 0.144* | |
C8 | −0.2431 (5) | 0.4939 (9) | 0.4499 (7) | 0.146 (4) | |
H8A | −0.2869 | 0.5115 | 0.4885 | 0.175* | |
C9 | −0.2569 (4) | 0.4005 (9) | 0.3864 (6) | 0.132 (3) | |
H9A | −0.3098 | 0.3554 | 0.3808 | 0.158* | |
C10 | −0.1886 (3) | 0.3778 (6) | 0.3320 (4) | 0.0958 (17) | |
H10A | −0.1962 | 0.3157 | 0.2891 | 0.115* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn | 0.0523 (5) | 0.0738 (6) | 0.0534 (5) | 0.000 | 0.0023 (4) | 0.000 |
S1 | 0.0901 (9) | 0.0841 (9) | 0.0850 (9) | 0.0265 (7) | −0.0246 (7) | −0.0187 (7) |
S2 | 0.176 (2) | 0.1547 (19) | 0.204 (3) | −0.0605 (17) | −0.100 (2) | 0.0895 (19) |
O1 | 0.097 (2) | 0.084 (2) | 0.098 (2) | 0.022 (2) | −0.021 (2) | −0.0011 (18) |
O2 | 0.175 (4) | 0.147 (4) | 0.095 (3) | 0.067 (3) | −0.045 (3) | −0.003 (2) |
O3 | 0.097 (3) | 0.176 (5) | 0.169 (4) | 0.049 (3) | 0.002 (3) | −0.049 (4) |
N1 | 0.075 (2) | 0.069 (2) | 0.052 (2) | 0.009 (2) | 0.0043 (19) | 0.0042 (17) |
N2 | 0.057 (2) | 0.094 (3) | 0.065 (2) | 0.012 (2) | 0.0139 (18) | 0.014 (2) |
C1 | 0.086 (3) | 0.079 (3) | 0.073 (3) | −0.008 (3) | −0.014 (3) | −0.006 (3) |
C2 | 0.134 (5) | 0.082 (4) | 0.090 (4) | −0.003 (4) | −0.015 (4) | −0.014 (3) |
C3 | 0.224 (9) | 0.066 (4) | 0.097 (5) | 0.000 (5) | −0.045 (6) | −0.006 (3) |
C4 | 0.171 (6) | 0.066 (3) | 0.074 (3) | 0.026 (4) | 0.013 (4) | −0.009 (3) |
C5 | 0.102 (4) | 0.059 (2) | 0.056 (2) | 0.026 (3) | 0.003 (3) | 0.015 (2) |
C6 | 0.092 (4) | 0.066 (3) | 0.067 (3) | 0.036 (3) | 0.027 (3) | 0.024 (2) |
C7 | 0.171 (6) | 0.081 (4) | 0.109 (5) | 0.048 (5) | 0.064 (5) | 0.018 (3) |
C8 | 0.129 (7) | 0.110 (5) | 0.198 (9) | 0.033 (5) | 0.085 (7) | 0.058 (6) |
C9 | 0.075 (4) | 0.124 (5) | 0.197 (8) | 0.016 (4) | 0.048 (5) | 0.080 (6) |
C10 | 0.067 (3) | 0.119 (4) | 0.102 (4) | 0.012 (3) | 0.019 (3) | 0.032 (3) |
Geometric parameters (Å, º) top
Mn—O1i | 2.122 (3) | N1—C1 | 1.344 (6) |
Mn—O1 | 2.122 (3) | N2—C6 | 1.322 (6) |
Mn—N2i | 2.249 (4) | N2—C10 | 1.350 (6) |
Mn—N2 | 2.249 (4) | C1—C2 | 1.371 (7) |
Mn—N1 | 2.249 (4) | C2—C3 | 1.350 (9) |
Mn—N1i | 2.249 (4) | C3—C4 | 1.373 (9) |
S1—O3 | 1.382 (5) | C4—C5 | 1.398 (7) |
S1—O2 | 1.429 (4) | C5—C6 | 1.474 (7) |
S1—O1 | 1.466 (3) | C6—C7 | 1.384 (7) |
S1—S2 | 2.086 (3) | C7—C8 | 1.368 (10) |
S2—S2i | 1.963 (5) | C8—C9 | 1.393 (11) |
N1—C5 | 1.329 (6) | C9—C10 | 1.383 (9) |
| | | |
O1i—Mn—O1 | 93.34 (19) | S1—O1—Mn | 155.4 (2) |
O1i—Mn—N2i | 99.10 (14) | C5—N1—C1 | 117.9 (4) |
O1—Mn—N2i | 94.00 (15) | C5—N1—Mn | 117.3 (3) |
O1i—Mn—N2 | 94.00 (15) | C1—N1—Mn | 124.8 (3) |
O1—Mn—N2 | 99.10 (14) | C6—N2—C10 | 119.3 (4) |
N2i—Mn—N2 | 160.9 (2) | C6—N2—Mn | 118.0 (3) |
O1i—Mn—N1 | 166.11 (14) | C10—N2—Mn | 122.7 (4) |
O1—Mn—N1 | 88.80 (13) | N1—C1—C2 | 123.7 (5) |
N2i—Mn—N1 | 94.44 (13) | C3—C2—C1 | 118.1 (6) |
N2—Mn—N1 | 72.11 (14) | C2—C3—C4 | 120.1 (6) |
O1i—Mn—N1i | 88.80 (13) | C3—C4—C5 | 118.9 (6) |
O1—Mn—N1i | 166.11 (14) | N1—C5—C4 | 121.3 (5) |
N2i—Mn—N1i | 72.11 (14) | N1—C5—C6 | 116.7 (4) |
N2—Mn—N1i | 94.44 (13) | C4—C5—C6 | 122.0 (5) |
N1—Mn—N1i | 92.42 (18) | N2—C6—C7 | 121.1 (5) |
O3—S1—O2 | 113.1 (3) | N2—C6—C5 | 115.9 (4) |
O3—S1—O1 | 114.0 (3) | C7—C6—C5 | 122.9 (6) |
O2—S1—O1 | 112.9 (2) | C8—C7—C6 | 119.9 (7) |
O3—S1—S2 | 108.0 (2) | C7—C8—C9 | 119.7 (7) |
O2—S1—S2 | 100.6 (3) | C10—C9—C8 | 117.1 (7) |
O1—S1—S2 | 107.14 (17) | N2—C10—C9 | 122.8 (7) |
S2i—S2—S1 | 102.78 (17) | | |
Symmetry code: (i) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O3ii | 0.93 | 2.50 (1) | 3.24 | 136 |
C10—H10A···O3i | 0.93 | 2.69 (1) | 3.57 | 157 |
C4—H4A···O2iii | 0.93 | 2.43 (1) | 3.26 | 148 |
C8—H8A···O2iv | 0.93 | 2.35 (1) | 3.14 | 142 |
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x+1/2, y+1/2, z; (iii) −x, −y+1, −z+1; (iv) x−1/2, −y+1/2, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Mn(S2O3)(C12H8N2)(H2O)2] | [Mn(S4O6)(C10H8N2)2] |
Mr | 383.30 | 591.55 |
Crystal system, space group | Monoclinic, P21 | Orthorhombic, Pbcn |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 10.371 (2), 7.1020 (14), 20.446 (4) | 15.330 (3), 9.889 (2), 16.061 (3) |
α, β, γ (°) | 90, 94.07 (3), 90 | 90, 90, 90 |
V (Å3) | 1502.1 (5) | 2434.8 (8) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.18 | 0.93 |
Crystal size (mm) | 0.38 × 0.28 × 0.14 | 0.26 × 0.24 × 0.24 |
|
Data collection |
Diffractometer | Rigaku AFC7S Difractometer diffractometer | Rigaku AFC7S Difractometer diffractometer |
Absorption correction | ψ scan (MSC/AFC Diffractometer Control Software; Molecular Structure Corporation, 1988) | ψ scan (MSC/AFC Diffractometer Control Software; Molecular Structure Corporation, 1988) |
Tmin, Tmax | 0.61, 0.85 | 0.75, 0.80 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4432, 4255, 3935 | 3002, 2804, 1247 |
Rint | 0.087 | 0.062 |
(sin θ/λ)max (Å−1) | 0.649 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.193, 1.19 | 0.052, 0.183, 1.01 |
No. of reflections | 4255 | 2804 |
No. of parameters | 397 | 159 |
No. of restraints | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.28, −0.68 | 0.59, −0.42 |
Absolute structure | Flack (1983) | ? |
Absolute structure parameter | 0.06 (5) | ? |
Selected bond lengths (Å) for (I) topMn1A—O2WA | 2.122 (6) | Mn1B—O1WB | 2.149 (6) |
Mn1A—O1WA | 2.173 (6) | Mn1B—O2WB | 2.150 (6) |
Mn1A—O1Ai | 2.176 (8) | Mn1B—O1Bi | 2.177 (8) |
Mn1A—N1A | 2.269 (8) | Mn1B—N2B | 2.270 (7) |
Mn1A—N2A | 2.270 (8) | Mn1B—N1B | 2.289 (6) |
Mn1A—S1A | 2.656 (3) | Mn1B—S1B | 2.642 (3) |
S1A—S2A | 2.005 (3) | S1B—S2B | 2.007 (3) |
S2A—O3A | 1.470 (7) | S2B—O3B | 1.465 (6) |
S2A—O2A | 1.469 (7) | S2B—O2B | 1.466 (7) |
S2A—O1A | 1.475 (8) | S2B—O1B | 1.494 (7) |
Symmetry code: (i) x, y−1, z. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1B—H1BA···O2A | 0.93 (1) | 2.368 (8) | 3.27 (1) | 163 (1) |
C10A—H10A···O3Bii | 0.93 (1) | 2.372 (7) | 3.20 (1) | 148 (1) |
O2WA···O2A | . | . | 2.65 (1) | . |
O2WB···O2A | . | . | 2.73 (1) | . |
O2WB···O2B | . | . | 2.69 (1) | . |
O2WA···O1WA | . | . | 3.17 (1) | . |
O2WB···O1WB | . | . | 3.21 (1) | . |
O1WA···O1Ai | . | . | 3.00 (1) | . |
O1WA···O3Ai | . | . | 2.76 (1) | . |
O1WA···O3Bii | . | . | 2.79 (1) | . |
O2WA···O1Ai | . | . | 3.05 (1) | . |
O2WA···O1Bi | . | . | 3.57 (1) | . |
O2WA···O2Bi | . | . | 2.74 (1) | . |
O1WB···O3Aiii | . | . | 2.76 (1) | . |
O1WB···O1Bi | . | . | 2.93 (1) | . |
O1WB···O3Bi | . | . | 2.66 (1) | . |
O2WB···O1Bi | . | . | 3.00 (1) | . |
Symmetry codes: (i) x, y−1, z; (ii) x−1, y−1, z; (iii) x+1, y, z. |
Selected bond lengths (Å) for (II) topMn—O1i | 2.122 (3) | S1—O3 | 1.382 (5) |
Mn—O1 | 2.122 (3) | S1—O2 | 1.429 (4) |
Mn—N2i | 2.249 (4) | S1—O1 | 1.466 (3) |
Mn—N2 | 2.249 (4) | S1—S2 | 2.086 (3) |
Mn—N1 | 2.249 (4) | S2—S2i | 1.963 (5) |
Mn—N1i | 2.249 (4) | | |
Symmetry code: (i) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O3ii | 0.93 | 2.503 (4) | 3.24 | 136 |
C10—H10A···O3i | 0.93 | 2.694 (5) | 3.57 | 157 |
C4—H4A···O2iii | 0.93 | 2.430 (4) | 3.26 | 148 |
C8—H8A···O2iv | 0.93 | 2.353 (5) | 3.14 | 142 |
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x+1/2, y+1/2, z; (iii) −x, −y+1, −z+1; (iv) x−1/2, −y+1/2, −z+1. |
In the last few years, the study of complexes of transition metals with sulfur oxoanions and N-bidentate organic ligands has been the subject of our interest. The thiosulfate ion has been one of the ligands most frequently used and has proved to be very versatile in coordination compounds of transition metals, with a geometry quite dependent on the type of coordination present. As a rule, we have tried to center our attention on thiosulfate complexes of cations which behave as borderline acids between `a' and `b' classes in the Pearson classification scale (Pearson, 1973). In these cases, the metallic ions are expected to bind to both the hard (O) as well as to the soft (S) end of thiosulfate, resulting in a variety of coordination modes, depending on other concurrent factors such as crystal field stabilization, shapes of accompanying ligands, intermolecular forces such as van der Waals and hydrogen bonding, etc.
Manganese(II), although a hard acid according to the Pearson classification, is borderline to the cations that behave as intermediate, and so is an interesting species to study in conjunction with the thiosulfate ligand. Furthermore, no structures have been reported which contain thiosulfate coordinated to manganese. With these ideas in mind, we attempted the syntheses of manganese thiosulfate complexes with phenanthroline and bipyridine. While in the first case, the expected complex was readily obtained, an oxidation of S2O3= took place in the second one and the tetrathionate ion was formed `in situ', coordinating to manganese. Thus, in this paper we report the structures of Mn(Phen)(S2O3)2(H2O)2, (I), and Mn(Bipy)2(S4O6), (II). \sch
The structure of (I) includes two independent Mn(2+) ions (labeled A and B in Figure 1), having very similar environments in which they are octahedrally surrounded by a bidentate phenanthroline [range of Mn—N: 2.269 (8)–2.289 (6) Å], two aquo ligands [range of Mn—Ow: 2.122 (6)–2.173 (6) Å], and one oxygen [Mn—O: 2.176 (8)–2.177 (8) Å] and one sulfur [Mn—S: 2.642 (3)–2.656 (3) Å] from thiosulfate groups related by a whole unit cell translation along b. Both independent coordination polyhedra are distorted as expected from the restraints imposed by the chelate character of the ligands, the most notable departures from ideal values being the angles N1A—Mn1A—O1WA: 167.0 (3), N1A—Mn1A—N2A 73.6 (3), N2B—Mn1B—O2WB: 166.1 (3), and N1B—Mn1B—N2B: 73.5 (2)°.
The thiosulfate groups in (I) act as bridging ligands between neighbouring cations through S and O, in a way reported before only in bis-ethylenethiourea zinc(II) thiosulfate (Baggio et al., 1974). The structure includes two different types of linear chains (Figure 2) parallel to each other and to the crystallographic b axis. These linear arrangements, in turn, are very nearly related to each other through a frustrated 21 symmetry axis at roughly 0.506 (16),0,0.248 (6) with a 0.53 (2) translation along b. The application of such a pseudo operation to bring the two chains into coincidence results in an average deviation of 0.27 Å and maximum departures of ~0.56 Å for C5 and C6 of the phen groups. Although the quality of the data prevented the finding of the water H atoms in the final difference Fourier maps, there are a number of short Owater···Othiosulfate contacts (<3.00 Å) clearly attributable to hydrogen bonding (Table 2 and Figure 2). Some of them are of the intra-chain type (the ones involving the pairs O3···O1W and O2···O2W in each chain) which define the spatial arrangement of the thiosulfate group; the remaining ones, involving atoms from different chains, provide stabilization by joining chains together into a three-dimensional structure.
The structure of (II) consists of monomers in which the manganese atom is octahedrally coordinated by four N atoms from two bidentate bipyridines [Mn—N 2.249 (2) Å], and two O atoms from a bidentate tetrathionate [Mn—O 2.122 (3) Å]. Only half of the molecule is independent, however, as a twofold axis bisects the cation and the S2—S2[-x,y,0.5 - z] bond (Figure 3). As a result of the restrictions imposed by the chelate bites, the Mn octahedron departs somewhat from ideality, most notably in the angles N1—Mn—N2: 72.11 (14)° and N2—Mn—N2(-x, y, 1/2 - z): 160.9 (2)°. The individual pyridinic groups are strictly planar within resolution, and are rotated around the C5—C6 bond by 1.8 (1)°. The monomers interact with each other via a number of O···H—C contacts (Table 4) which are distributed more or less evenly in space with no obvious preferred orientation. These interactions correlate fairly well with the S—O bond lengths observed in the oxoanion, in the sense that the stronger the interaction in which one oxygen takes part, the shorter the bond length to sulfur observed. To our knowledge, this is the first structure ever reported with a chelating S4O6 group. A survey in the CSD shows only five structures containing the anion, in three of which the group is not coordinated at all to the metal center, acting merely as a counterion (bis-ethylenediamine-ammonio-bromo-cobalt tetrathionate, Bernal et al., 1993; tris(1,10-phenantholine)-copper(II) tetrathionate pentahydrate; Freire et al., 1998; and tetra-ammine-(oxalato-O,O')-cobalt tetrathionate monohydrate; Bernal et al., 1996). In the remaining two structures, bis(2,2'-bipyridyl)copper(II) tetrathionate (Harrison & Hathaway, 1978) and bis(1,10-phenantholine)copper(II) tetrathionate; (Freire et al., 1998) (which in fact ought to be considered just as one and the same structure, since they are very nearly isostructural) the anion binds very loosely through two opposite O atoms acting as a bridge between adjacent cations, to define infinite, unidimensional polymers. Comparison of the tetrathionate molecule herein presented with those found in the literature shows that the S—S bond lengths lie in the short side of the ranges found for the reported structures: S1—S2: 2.085 (8) Å, (range reported: 2.09–2.13 Å); S2—S2': 1.963 (5) Å (range reported 1.98–2.02 Å). These differences, however, might not be too meaningful due to the slightly disordered character of S2 (see experimental section).