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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100013585/da1146sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100013585/da1146Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100013585/da1146IIsup3.hkl
Contains datablock II

CCDC references: 158225; 158226

Comment top

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).

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. View of the two independent Mn coordination polyhedra in (I). Displacement ellipsoids drawn at a 50% level.
[Figure 2] Fig. 2. Schematic packing view of (I), showing both types of chains, A and B, and the way in which they interact via intra as well as intermolecular hydrogen bonds. Interactions to symmetry-related chains have been omitted, for clarity.
[Figure 3] Fig. 3. Monomeric unit in (II). Note the twofold axis through the cation and the midpoint of the tetrathionate anion. The symmetry-related part of the molecule depicted in broken lines. Displacement ellipsoids shown at a 30% level.
(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 = 383.30Dx = 1.695 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 10.371 (2) ÅCell parameters from 25 reflections
b = 7.1020 (14) Åθ = 7.5–15°
c = 20.446 (4) ŵ = 1.18 mm1
β = 94.07 (3)°T = 293 K
V = 1502.1 (5) Å3Plates, pale yellow
Z = 40.38 × 0.28 × 0.14 mm
Data collection top
Rigaku AFC7S Difractometer
diffractometer
3935 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.087
Graphite monochromatorθmax = 27.5°, θmin = 2.0°
ω/2θ scansh = 1313
Absorption correction: ψ scan
(MSC/AFC Diffractometer Control Software; Molecular Structure Corporation, 1988)
k = 19
Tmin = 0.61, Tmax = 0.85l = 026
4432 measured reflections3 standard reflections every 150 reflections
4255 independent reflections intensity decay: <3%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: geom + difmap
R[F2 > 2σ(F2)] = 0.062H-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 reflectionsΔρmax = 1.28 e Å3
397 parametersΔρmin = 0.68 e Å3
1 restraintAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.06 (5)
Crystal data top
[Mn(S2O3)(C12H8N2)(H2O)2]V = 1502.1 (5) Å3
Mr = 383.30Z = 4
Monoclinic, P21Mo Kα radiation
a = 10.371 (2) ŵ = 1.18 mm1
b = 7.1020 (14) ÅT = 293 K
c = 20.446 (4) Å0.38 × 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 = 0.853 standard reflections every 150 reflections
4432 measured reflections intensity decay: <3%
4255 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.062H-atom parameters constrained
wR(F2) = 0.193Δρmax = 1.28 e Å3
S = 1.19Δρmin = 0.68 e Å3
4255 reflectionsAbsolute structure: Flack (1983)
397 parametersAbsolute 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
xyzUiso*/Ueq
Mn1A0.26655 (11)0.3910 (2)0.32590 (6)0.0252 (3)
S1A0.1930 (2)0.7468 (4)0.33788 (11)0.0309 (5)
S2A0.27248 (17)0.9274 (3)0.27697 (10)0.0249 (4)
O1A0.3170 (8)1.0960 (11)0.3141 (4)0.0401 (18)
O2A0.3865 (7)0.8405 (12)0.2507 (4)0.0458 (19)
O3A0.1757 (6)0.9778 (12)0.2238 (3)0.0388 (17)
N1A0.3819 (7)0.3812 (15)0.4244 (4)0.039 (2)
N2A0.1231 (7)0.3257 (14)0.4016 (4)0.0337 (18)
C1A0.5079 (10)0.4017 (19)0.4370 (6)0.050 (3)
H1AA0.55810.41950.40160.060*
C2A0.5702 (13)0.399 (2)0.4989 (8)0.075 (5)
H2AA0.65980.40910.50360.090*
C3A0.5016 (16)0.381 (2)0.5536 (8)0.082 (5)
H3AA0.54260.38640.59550.099*
C4A0.3672 (14)0.353 (2)0.5441 (5)0.058 (4)
C5A0.2809 (17)0.319 (3)0.5947 (6)0.073 (5)
H5AA0.31520.31890.63800.087*
C6A0.1553 (17)0.287 (3)0.5835 (5)0.072 (5)
H6AA0.10510.26300.61850.087*
C7A0.0975 (14)0.290 (2)0.5196 (5)0.057 (4)
C8A0.0359 (13)0.261 (2)0.5042 (7)0.062 (4)
H8AA0.09050.24070.53770.074*
C9A0.0859 (11)0.263 (2)0.4394 (6)0.052 (3)
H9AA0.17310.23900.42880.063*
C10A0.0035 (10)0.301 (2)0.3910 (5)0.046 (3)
H10A0.03900.30890.34810.055*
C11A0.1742 (11)0.3236 (16)0.4646 (5)0.039 (2)
C12A0.3133 (10)0.3603 (15)0.4769 (4)0.036 (2)
Mn1B0.74602 (11)0.9133 (2)0.17075 (6)0.0238 (3)
S1B0.8086 (2)1.2687 (4)0.15161 (12)0.0338 (5)
S2B0.76259 (17)1.4501 (3)0.22155 (10)0.0245 (4)
O1B0.7003 (7)1.6203 (11)0.1901 (4)0.0391 (18)
O2B0.6735 (6)1.3612 (11)0.2648 (3)0.0382 (16)
O3B0.8819 (6)1.5031 (11)0.2597 (4)0.0389 (17)
N1B0.5799 (6)0.9310 (12)0.0911 (3)0.0258 (15)
N2B0.8359 (6)0.8832 (13)0.0732 (4)0.0298 (17)
C1B0.4574 (8)0.9469 (18)0.1019 (4)0.034 (2)
H1BA0.43280.94430.14470.041*
C2B0.3599 (8)0.968 (2)0.0485 (4)0.039 (3)
H2BA0.27320.97860.05680.047*
C3B0.3962 (9)0.9736 (17)0.0140 (5)0.037 (2)
H3BA0.33360.98670.04860.044*
C4B0.5257 (9)0.9594 (18)0.0270 (4)0.035 (2)
C5B0.5711 (10)0.9650 (19)0.0913 (4)0.041 (3)
H5BA0.51290.98390.12740.049*
C6B0.6965 (10)0.943 (2)0.0999 (5)0.045 (3)
H6BA0.72380.95090.14220.054*
C7B0.7912 (8)0.9089 (16)0.0466 (4)0.0312 (19)
C8B0.9207 (10)0.8796 (19)0.0550 (5)0.043 (3)
H8BA0.95070.87810.09680.051*
C9B1.0043 (9)0.853 (2)0.0010 (6)0.049 (3)
H9BA1.09180.83440.00620.058*
C10B0.9595 (9)0.8534 (18)0.0619 (5)0.037 (2)
H10B1.01860.83180.09750.045*
C11B0.7536 (8)0.9105 (15)0.0194 (4)0.0291 (18)
C12B0.6154 (7)0.9352 (14)0.0295 (4)0.0264 (17)
O1WA0.1275 (6)0.3566 (11)0.2422 (3)0.0330 (15)
O2WA0.4215 (6)0.4738 (12)0.2699 (4)0.0441 (19)
O1WB0.9223 (6)0.8621 (14)0.2297 (4)0.057 (2)
O2WB0.6304 (6)0.9888 (11)0.2500 (3)0.0333 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn1A0.0238 (5)0.0258 (8)0.0258 (6)0.0008 (6)0.0008 (4)0.0011 (6)
S1A0.0342 (11)0.0272 (13)0.0324 (11)0.0024 (10)0.0100 (9)0.0025 (10)
S2A0.0206 (7)0.0230 (11)0.0308 (9)0.0010 (9)0.0002 (7)0.0025 (10)
O1A0.048 (4)0.022 (4)0.049 (4)0.000 (3)0.003 (3)0.006 (3)
O2A0.038 (3)0.039 (4)0.064 (5)0.001 (4)0.025 (3)0.012 (4)
O3A0.044 (3)0.035 (4)0.035 (3)0.006 (3)0.013 (3)0.004 (3)
N1A0.032 (4)0.036 (5)0.046 (4)0.004 (4)0.015 (3)0.007 (5)
N2A0.031 (4)0.036 (5)0.034 (4)0.004 (4)0.002 (3)0.000 (4)
C1A0.042 (5)0.042 (7)0.061 (6)0.008 (6)0.033 (5)0.005 (6)
C2A0.068 (8)0.056 (9)0.092 (10)0.002 (8)0.063 (8)0.016 (10)
C3A0.104 (11)0.052 (9)0.081 (10)0.018 (10)0.067 (9)0.013 (9)
C4A0.100 (9)0.046 (7)0.023 (5)0.002 (7)0.032 (5)0.000 (5)
C5A0.119 (13)0.063 (10)0.034 (6)0.004 (10)0.011 (7)0.001 (7)
C6A0.120 (12)0.082 (12)0.013 (4)0.002 (11)0.006 (6)0.004 (6)
C7A0.090 (9)0.053 (8)0.030 (5)0.022 (8)0.010 (5)0.009 (6)
C8A0.064 (8)0.057 (8)0.070 (8)0.004 (7)0.042 (7)0.009 (8)
C9A0.043 (6)0.067 (9)0.046 (6)0.007 (7)0.000 (5)0.007 (7)
C10A0.033 (5)0.059 (8)0.044 (5)0.003 (5)0.000 (4)0.026 (6)
C11A0.061 (6)0.028 (5)0.026 (4)0.006 (5)0.006 (4)0.000 (4)
C12A0.065 (6)0.030 (5)0.010 (3)0.005 (5)0.014 (3)0.006 (4)
Mn1B0.0234 (5)0.0256 (8)0.0214 (5)0.0016 (6)0.0041 (4)0.0008 (6)
S1B0.0435 (13)0.0250 (12)0.0338 (11)0.0034 (11)0.0080 (9)0.0043 (11)
S2B0.0196 (8)0.0212 (11)0.0318 (10)0.0006 (9)0.0034 (7)0.0007 (9)
O1B0.036 (4)0.021 (4)0.058 (5)0.001 (3)0.019 (3)0.002 (4)
O2B0.044 (3)0.030 (4)0.041 (4)0.003 (3)0.011 (3)0.001 (3)
O3B0.032 (3)0.027 (4)0.055 (4)0.002 (3)0.017 (3)0.007 (4)
N1B0.025 (3)0.023 (4)0.029 (3)0.009 (3)0.000 (2)0.006 (3)
N2B0.024 (3)0.031 (4)0.034 (4)0.006 (4)0.002 (3)0.001 (4)
C1B0.026 (4)0.052 (7)0.025 (4)0.005 (5)0.002 (3)0.008 (5)
C2B0.024 (4)0.062 (8)0.031 (4)0.008 (5)0.004 (3)0.001 (5)
C3B0.031 (4)0.039 (6)0.039 (5)0.003 (5)0.017 (4)0.007 (5)
C4B0.034 (4)0.038 (6)0.033 (5)0.004 (5)0.000 (3)0.003 (5)
C5B0.058 (6)0.049 (7)0.015 (4)0.003 (6)0.011 (4)0.008 (5)
C6B0.056 (6)0.052 (7)0.025 (4)0.000 (6)0.005 (4)0.009 (5)
C7B0.041 (4)0.032 (5)0.022 (4)0.007 (5)0.006 (3)0.003 (4)
C8B0.049 (5)0.044 (7)0.037 (5)0.004 (6)0.016 (4)0.009 (5)
C9B0.030 (4)0.061 (8)0.056 (6)0.007 (5)0.011 (4)0.027 (6)
C10B0.029 (4)0.044 (6)0.040 (5)0.009 (5)0.006 (4)0.000 (5)
C11B0.038 (4)0.027 (5)0.023 (4)0.001 (4)0.003 (3)0.002 (4)
C12B0.029 (4)0.024 (4)0.026 (4)0.003 (4)0.003 (3)0.004 (4)
O1WA0.039 (3)0.035 (4)0.023 (3)0.006 (3)0.011 (2)0.005 (3)
O2WA0.034 (3)0.038 (4)0.063 (5)0.009 (3)0.022 (3)0.017 (4)
O1WB0.031 (3)0.057 (6)0.076 (5)0.016 (4)0.036 (3)0.022 (5)
O2WB0.040 (3)0.032 (4)0.030 (3)0.007 (3)0.011 (3)0.010 (3)
Geometric parameters (Å, º) top
Mn1A—O2WA2.122 (6)Mn1B—O1WB2.149 (6)
Mn1A—O1WA2.173 (6)Mn1B—O2WB2.150 (6)
Mn1A—O1Ai2.176 (8)Mn1B—O1Bi2.177 (8)
Mn1A—N1A2.269 (8)Mn1B—N2B2.270 (7)
Mn1A—N2A2.270 (8)Mn1B—N1B2.289 (6)
Mn1A—S1A2.656 (3)Mn1B—S1B2.642 (3)
S1A—S2A2.005 (3)S1B—S2B2.007 (3)
S2A—O3A1.470 (7)S2B—O3B1.465 (6)
S2A—O2A1.469 (7)S2B—O2B1.466 (7)
S2A—O1A1.475 (8)S2B—O1B1.494 (7)
N1A—C1A1.322 (12)N1B—C1B1.310 (10)
N1A—C12A1.338 (13)N1B—C12B1.337 (10)
N2A—C10A1.328 (12)N2B—C10B1.336 (10)
N2A—C11A1.358 (12)N2B—C11B1.358 (10)
C1A—C2A1.380 (15)C1B—C2B1.443 (11)
C2A—C3A1.37 (2)C2B—C3B1.358 (13)
C3A—C4A1.41 (2)C3B—C4B1.391 (12)
C4A—C5A1.44 (2)C4B—C5B1.428 (13)
C4A—C12A1.446 (11)C4B—C12B1.441 (12)
C5A—C6A1.33 (2)C5B—C6B1.334 (14)
C6A—C7A1.399 (16)C6B—C7B1.435 (12)
C7A—C8A1.41 (2)C7B—C8B1.383 (12)
C7A—C11A1.441 (15)C7B—C11B1.430 (11)
C8A—C9A1.388 (18)C8B—C9B1.367 (15)
C9A—C10A1.379 (15)C9B—C10B1.397 (14)
C11A—C12A1.470 (15)C11B—C12B1.473 (11)
O2WA—Mn1A—O1WA95.2 (3)O1WB—Mn1B—O2WB96.7 (3)
O2WA—Mn1A—O1Ai90.6 (3)O1WB—Mn1B—O1Bi85.6 (3)
O1WA—Mn1A—O1Ai87.5 (3)O2WB—Mn1B—O1Bi87.8 (3)
O2WA—Mn1A—N1A96.7 (3)O1WB—Mn1B—N2B95.2 (3)
O1WA—Mn1A—N1A167.0 (3)O2WB—Mn1B—N2B166.1 (3)
O1Ai—Mn1A—N1A87.3 (3)O1Bi—Mn1B—N2B100.2 (3)
O2WA—Mn1A—N2A169.4 (3)O1WB—Mn1B—N1B167.5 (3)
O1WA—Mn1A—N2A94.8 (3)O2WB—Mn1B—N1B95.2 (2)
O1Ai—Mn1A—N2A93.1 (3)O1Bi—Mn1B—N1B91.1 (3)
N1A—Mn1A—N2A73.6 (3)N2B—Mn1B—N1B73.5 (2)
O2WA—Mn1A—S1A91.1 (2)O1WB—Mn1B—S1B92.1 (3)
O1WA—Mn1A—S1A90.0 (2)O2WB—Mn1B—S1B91.7 (2)
O1Ai—Mn1A—S1A177.1 (2)O1Bi—Mn1B—S1B177.60 (19)
N1A—Mn1A—S1A94.8 (3)N2B—Mn1B—S1B80.8 (2)
N2A—Mn1A—S1A85.7 (3)N1B—Mn1B—S1B91.3 (2)
S2A—S1A—Mn1A114.69 (12)S2B—S1B—Mn1B115.74 (12)
O3A—S2A—O2A110.9 (5)O3B—S2B—O2B109.5 (4)
O3A—S2A—O1A110.8 (5)O3B—S2B—O1B110.2 (4)
O2A—S2A—O1A107.4 (5)O2B—S2B—O1B109.7 (4)
O3A—S2A—S1A109.0 (3)O3B—S2B—S1B108.1 (3)
O2A—S2A—S1A109.6 (4)O2B—S2B—S1B110.2 (3)
O1A—S2A—S1A109.1 (4)O1B—S2B—S1B109.2 (3)
S2A—O1A—Mn1Aii140.3 (5)S2B—O1B—Mn1Bii139.3 (4)
C1A—N1A—C12A115.4 (9)C1B—N1B—C12B119.5 (7)
C1A—N1A—Mn1A128.4 (8)C1B—N1B—Mn1B125.1 (6)
C12A—N1A—Mn1A116.1 (6)C12B—N1B—Mn1B115.3 (5)
C10A—N2A—C11A117.9 (9)C10B—N2B—C11B115.9 (8)
C10A—N2A—Mn1A127.2 (7)C10B—N2B—Mn1B128.8 (6)
C11A—N2A—Mn1A114.8 (7)C11B—N2B—Mn1B115.1 (5)
N1A—C1A—C2A124.7 (13)N1B—C1B—C2B121.2 (8)
C3A—C2A—C1A120.8 (13)C3B—C2B—C1B119.3 (8)
C2A—C3A—C4A117.8 (11)C2B—C3B—C4B120.9 (8)
C3A—C4A—C5A125.8 (11)C3B—C4B—C5B124.0 (9)
C3A—C4A—C12A116.0 (13)C3B—C4B—C12B115.7 (8)
C5A—C4A—C12A118.2 (12)C5B—C4B—C12B120.3 (8)
C6A—C5A—C4A124.0 (12)C6B—C5B—C4B120.4 (8)
C5A—C6A—C7A120.6 (14)C5B—C6B—C7B122.7 (9)
C8A—C7A—C6A123.6 (13)C8B—C7B—C11B116.8 (8)
C8A—C7A—C11A115.9 (11)C8B—C7B—C6B123.3 (8)
C6A—C7A—C11A120.5 (14)C11B—C7B—C6B119.9 (8)
C9A—C8A—C7A120.3 (10)C9B—C8B—C7B119.1 (9)
C10A—C9A—C8A118.5 (11)C8B—C9B—C10B120.6 (9)
N2A—C10A—C9A124.4 (10)N2B—C10B—C9B123.1 (9)
N2A—C11A—C7A122.8 (11)N2B—C11B—C7B124.4 (8)
N2A—C11A—C12A118.2 (9)N2B—C11B—C12B117.8 (7)
C7A—C11A—C12A119.0 (9)C7B—C11B—C12B117.7 (7)
N1A—C12A—C4A125.1 (10)N1B—C12B—C4B123.5 (7)
N1A—C12A—C11A116.9 (7)N1B—C12B—C11B117.7 (7)
C4A—C12A—C11A117.7 (10)C4B—C12B—C11B118.8 (7)
Symmetry codes: (i) x, y1, z; (ii) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1B—H1BA···O2A0.93 (1)2.37 (1)3.27 (1)163 (1)
C10A—H10A···O3Biii0.93 (1)2.37 (1)3.20 (1)148 (1)
O2WA···O2A2.65 (1)
O2WB···O2A2.73 (1)
O2WB···O2B2.69 (1)
O2WA···O1WA3.17 (1)
O2WB···O1WB3.21 (1)
O1WA···O1Ai3.00 (1)
O1WA···O3Ai2.76 (1)
O1WA···O3Biii2.79 (1)
O2WA···O1Ai3.05 (1)
O2WA···O1Bi3.57 (1)
O2WA···O2Bi2.74 (1)
O1WB···O3Aiv2.76 (1)
O1WB···O1Bi2.93 (1)
O1WB···O3Bi2.66 (1)
O2WB···O1Bi3.00 (1)
Symmetry codes: (i) x, y1, z; (iii) x1, y1, 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 = 591.55Dx = 1.614 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 25 reflections
a = 15.330 (3) Åθ = 7.5–15°
b = 9.889 (2) ŵ = 0.93 mm1
c = 16.061 (3) ÅT = 293 K
V = 2434.8 (8) Å3Irregular blocks, pale yellow
Z = 40.26 × 0.24 × 0.24 mm
Data collection top
Rigaku AFC7S Difractometer
diffractometer
1247 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.062
Graphite monochromatorθmax = 27.5°, θmin = 2.5°
ω/2θ scansh = 019
Absorption correction: ψ scan
(MSC/AFC Diffractometer Control Software; Molecular Structure Corporation, 1988)
k = 012
Tmin = 0.75, Tmax = 0.80l = 020
3002 measured reflections3 standard reflections every 150 reflections
2804 independent reflections intensity decay: <3%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.183H-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 parametersΔρmax = 0.59 e Å3
0 restraintsΔρmin = 0.42 e Å3
Crystal data top
[Mn(S4O6)(C10H8N2)2]V = 2434.8 (8) Å3
Mr = 591.55Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 15.330 (3) ŵ = 0.93 mm1
b = 9.889 (2) ÅT = 293 K
c = 16.061 (3) Å0.26 × 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 = 0.803 standard reflections every 150 reflections
3002 measured reflections intensity decay: <3%
2804 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.183H-atom parameters constrained
S = 1.01Δρmax = 0.59 e Å3
2804 reflectionsΔρmin = 0.42 e Å3
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
xyzUiso*/Ueq
Mn0.00000.40428 (9)0.25000.0598 (3)
S10.10064 (9)0.12080 (14)0.33961 (9)0.0864 (5)
S20.00014 (16)0.0136 (3)0.31111 (16)0.1783 (13)
O10.0691 (2)0.2570 (3)0.3199 (2)0.0930 (11)
O20.1094 (3)0.0980 (4)0.4271 (3)0.1388 (18)
O30.1735 (3)0.0825 (5)0.2949 (4)0.1474 (19)
N10.0433 (3)0.5616 (4)0.3422 (2)0.0657 (10)
N20.1112 (2)0.4420 (4)0.3384 (2)0.0719 (10)
C10.1226 (3)0.6193 (5)0.3435 (3)0.0794 (13)
H1A0.16360.59060.30460.095*
C20.1467 (5)0.7179 (6)0.3990 (4)0.1019 (18)
H2A0.20210.75630.39700.122*
C30.0878 (6)0.7575 (6)0.4565 (4)0.129 (3)
H3A0.10200.82520.49430.155*
C40.0069 (5)0.6979 (5)0.4591 (3)0.104 (2)
H4A0.03320.72230.49990.125*
C50.0141 (3)0.6001 (4)0.3995 (3)0.0724 (13)
C60.1002 (3)0.5338 (5)0.3974 (3)0.0748 (14)
C70.1648 (5)0.5596 (6)0.4553 (4)0.120 (2)
H7A0.15510.62160.49790.144*
C80.2431 (5)0.4939 (9)0.4499 (7)0.146 (4)
H8A0.28690.51150.48850.175*
C90.2569 (4)0.4005 (9)0.3864 (6)0.132 (3)
H9A0.30980.35540.38080.158*
C100.1886 (3)0.3778 (6)0.3320 (4)0.0958 (17)
H10A0.19620.31570.28910.115*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn0.0523 (5)0.0738 (6)0.0534 (5)0.0000.0023 (4)0.000
S10.0901 (9)0.0841 (9)0.0850 (9)0.0265 (7)0.0246 (7)0.0187 (7)
S20.176 (2)0.1547 (19)0.204 (3)0.0605 (17)0.100 (2)0.0895 (19)
O10.097 (2)0.084 (2)0.098 (2)0.022 (2)0.021 (2)0.0011 (18)
O20.175 (4)0.147 (4)0.095 (3)0.067 (3)0.045 (3)0.003 (2)
O30.097 (3)0.176 (5)0.169 (4)0.049 (3)0.002 (3)0.049 (4)
N10.075 (2)0.069 (2)0.052 (2)0.009 (2)0.0043 (19)0.0042 (17)
N20.057 (2)0.094 (3)0.065 (2)0.012 (2)0.0139 (18)0.014 (2)
C10.086 (3)0.079 (3)0.073 (3)0.008 (3)0.014 (3)0.006 (3)
C20.134 (5)0.082 (4)0.090 (4)0.003 (4)0.015 (4)0.014 (3)
C30.224 (9)0.066 (4)0.097 (5)0.000 (5)0.045 (6)0.006 (3)
C40.171 (6)0.066 (3)0.074 (3)0.026 (4)0.013 (4)0.009 (3)
C50.102 (4)0.059 (2)0.056 (2)0.026 (3)0.003 (3)0.015 (2)
C60.092 (4)0.066 (3)0.067 (3)0.036 (3)0.027 (3)0.024 (2)
C70.171 (6)0.081 (4)0.109 (5)0.048 (5)0.064 (5)0.018 (3)
C80.129 (7)0.110 (5)0.198 (9)0.033 (5)0.085 (7)0.058 (6)
C90.075 (4)0.124 (5)0.197 (8)0.016 (4)0.048 (5)0.080 (6)
C100.067 (3)0.119 (4)0.102 (4)0.012 (3)0.019 (3)0.032 (3)
Geometric parameters (Å, º) top
Mn—O1i2.122 (3)N1—C11.344 (6)
Mn—O12.122 (3)N2—C61.322 (6)
Mn—N2i2.249 (4)N2—C101.350 (6)
Mn—N22.249 (4)C1—C21.371 (7)
Mn—N12.249 (4)C2—C31.350 (9)
Mn—N1i2.249 (4)C3—C41.373 (9)
S1—O31.382 (5)C4—C51.398 (7)
S1—O21.429 (4)C5—C61.474 (7)
S1—O11.466 (3)C6—C71.384 (7)
S1—S22.086 (3)C7—C81.368 (10)
S2—S2i1.963 (5)C8—C91.393 (11)
N1—C51.329 (6)C9—C101.383 (9)
O1i—Mn—O193.34 (19)S1—O1—Mn155.4 (2)
O1i—Mn—N2i99.10 (14)C5—N1—C1117.9 (4)
O1—Mn—N2i94.00 (15)C5—N1—Mn117.3 (3)
O1i—Mn—N294.00 (15)C1—N1—Mn124.8 (3)
O1—Mn—N299.10 (14)C6—N2—C10119.3 (4)
N2i—Mn—N2160.9 (2)C6—N2—Mn118.0 (3)
O1i—Mn—N1166.11 (14)C10—N2—Mn122.7 (4)
O1—Mn—N188.80 (13)N1—C1—C2123.7 (5)
N2i—Mn—N194.44 (13)C3—C2—C1118.1 (6)
N2—Mn—N172.11 (14)C2—C3—C4120.1 (6)
O1i—Mn—N1i88.80 (13)C3—C4—C5118.9 (6)
O1—Mn—N1i166.11 (14)N1—C5—C4121.3 (5)
N2i—Mn—N1i72.11 (14)N1—C5—C6116.7 (4)
N2—Mn—N1i94.44 (13)C4—C5—C6122.0 (5)
N1—Mn—N1i92.42 (18)N2—C6—C7121.1 (5)
O3—S1—O2113.1 (3)N2—C6—C5115.9 (4)
O3—S1—O1114.0 (3)C7—C6—C5122.9 (6)
O2—S1—O1112.9 (2)C8—C7—C6119.9 (7)
O3—S1—S2108.0 (2)C7—C8—C9119.7 (7)
O2—S1—S2100.6 (3)C10—C9—C8117.1 (7)
O1—S1—S2107.14 (17)N2—C10—C9122.8 (7)
S2i—S2—S1102.78 (17)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O3ii0.932.50 (1)3.24136
C10—H10A···O3i0.932.69 (1)3.57157
C4—H4A···O2iii0.932.43 (1)3.26148
C8—H8A···O2iv0.932.35 (1)3.14142
Symmetry codes: (i) x, y, z+1/2; (ii) x+1/2, y+1/2, z; (iii) x, y+1, z+1; (iv) x1/2, y+1/2, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formula[Mn(S2O3)(C12H8N2)(H2O)2][Mn(S4O6)(C10H8N2)2]
Mr383.30591.55
Crystal system, space groupMonoclinic, P21Orthorhombic, Pbcn
Temperature (K)293293
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), 9090, 90, 90
V3)1502.1 (5)2434.8 (8)
Z44
Radiation typeMo KαMo Kα
µ (mm1)1.180.93
Crystal size (mm)0.38 × 0.28 × 0.140.26 × 0.24 × 0.24
Data collection
DiffractometerRigaku AFC7S Difractometer
diffractometer
Rigaku AFC7S Difractometer
diffractometer
Absorption correctionψ scan
(MSC/AFC Diffractometer Control Software; Molecular Structure Corporation, 1988)
ψ scan
(MSC/AFC Diffractometer Control Software; Molecular Structure Corporation, 1988)
Tmin, Tmax0.61, 0.850.75, 0.80
No. of measured, independent and
observed [I > 2σ(I)] reflections
4432, 4255, 3935 3002, 2804, 1247
Rint0.0870.062
(sin θ/λ)max1)0.6490.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.062, 0.193, 1.19 0.052, 0.183, 1.01
No. of reflections42552804
No. of parameters397159
No. of restraints10
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.28, 0.680.59, 0.42
Absolute structureFlack (1983)?
Absolute structure parameter0.06 (5)?

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), MSC/AFC Diffractometer Control Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL/PC (Sheldrick,1994), XP in SHELXTL/PC (Sheldrick, 1994), PARST (Nardelli, 1983) and CSD (Allen & Kennard, 1993).

Selected bond lengths (Å) for (I) top
Mn1A—O2WA2.122 (6)Mn1B—O1WB2.149 (6)
Mn1A—O1WA2.173 (6)Mn1B—O2WB2.150 (6)
Mn1A—O1Ai2.176 (8)Mn1B—O1Bi2.177 (8)
Mn1A—N1A2.269 (8)Mn1B—N2B2.270 (7)
Mn1A—N2A2.270 (8)Mn1B—N1B2.289 (6)
Mn1A—S1A2.656 (3)Mn1B—S1B2.642 (3)
S1A—S2A2.005 (3)S1B—S2B2.007 (3)
S2A—O3A1.470 (7)S2B—O3B1.465 (6)
S2A—O2A1.469 (7)S2B—O2B1.466 (7)
S2A—O1A1.475 (8)S2B—O1B1.494 (7)
Symmetry code: (i) x, y1, z.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C1B—H1BA···O2A0.93 (1)2.368 (8)3.27 (1)163 (1)
C10A—H10A···O3Bii0.93 (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, y1, z; (ii) x1, y1, z; (iii) x+1, y, z.
Selected bond lengths (Å) for (II) top
Mn—O1i2.122 (3)S1—O31.382 (5)
Mn—O12.122 (3)S1—O21.429 (4)
Mn—N2i2.249 (4)S1—O11.466 (3)
Mn—N22.249 (4)S1—S22.086 (3)
Mn—N12.249 (4)S2—S2i1.963 (5)
Mn—N1i2.249 (4)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O3ii0.932.503 (4)3.24136
C10—H10A···O3i0.932.694 (5)3.57157
C4—H4A···O2iii0.932.430 (4)3.26148
C8—H8A···O2iv0.932.353 (5)3.14142
Symmetry codes: (i) x, y, z+1/2; (ii) x+1/2, y+1/2, z; (iii) x, y+1, z+1; (iv) x1/2, y+1/2, z+1.
 

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