catena-Poly­[[di­aqua(1,10-phen­anthroline-N,N′)­manganese(II)]-μ-(thiosulfato-O:S)] and bis(2,2′-bipyridyl-N,N′)(tetra­thionato-O,O′)manganese(II)

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.

S1. Comment

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 O_water···O_thiosulfate 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).

S2. Experimental

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.

S3. Refinement

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/ų, at distances shorter than 1 Å.

Computing details

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

	Fig. 1. View of the two independent Mn coordination polyhedra in (I). Displacement ellipsoids drawn at a 50% level.
	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.
	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)]

Crystal data

[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) Å^3	Plates, pale yellow
Z = 4	0.38 × 0.28 × 0.14 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: geom + difmap
R[F^2 > 2σ(F^2)] = 0.062	H-atom parameters constrained
wR(F^2) = 0.193	w = 1/[σ^2(Fo^2) + (0.067P)^2 + 9.528P] where P = (Fo^2 + 2Fc^2)/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)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Mn1A—O2WA	2.122 (6)	Mn1B—O1WB	2.149 (6)
Mn1A—O1WA	2.173 (6)	Mn1B—O2WB	2.150 (6)
Mn1A—O1A^i	2.176 (8)	Mn1B—O1B^i	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—O1A^i	90.6 (3)	O1WB—Mn1B—O1B^i	85.6 (3)
O1WA—Mn1A—O1A^i	87.5 (3)	O2WB—Mn1B—O1B^i	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)
O1A^i—Mn1A—N1A	87.3 (3)	O1B^i—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)
O1A^i—Mn1A—N2A	93.1 (3)	O1B^i—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)
O1A^i—Mn1A—S1A	177.1 (2)	O1B^i—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—Mn1A^ii	140.3 (5)	S2B—O1B—Mn1B^ii	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)

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···O3B^iii	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···O1A^i			3.00 (1)
O1WA···O3A^i			2.76 (1)
O1WA···O3B^iii			2.79 (1)
O2WA···O1A^i			3.05 (1)
O2WA···O1B^i			3.57 (1)
O2WA···O2B^i			2.74 (1)
O1WB···O3A^iv			2.76 (1)
O1WB···O1B^i			2.93 (1)
O1WB···O3B^i			2.66 (1)
O2WB···O1B^i			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'

Crystal data

[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) Å^3	Irregular blocks, pale yellow
Z = 4	0.26 × 0.24 × 0.24 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.183	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.093P)^2] where P = (Fo^2 + 2Fc^2)/3
2804 reflections	(Δ/σ)max < 0.01
159 parameters	Δρmax = 0.59 e Å^−3
0 restraints	Δρmin = −0.42 e Å^−3

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Mn—O1^i	2.122 (3)	N1—C1	1.344 (6)
Mn—O1	2.122 (3)	N2—C6	1.322 (6)
Mn—N2^i	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—N1^i	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—S2^i	1.963 (5)	C8—C9	1.393 (11)
N1—C5	1.329 (6)	C9—C10	1.383 (9)
O1^i—Mn—O1	93.34 (19)	S1—O1—Mn	155.4 (2)
O1^i—Mn—N2^i	99.10 (14)	C5—N1—C1	117.9 (4)
O1—Mn—N2^i	94.00 (15)	C5—N1—Mn	117.3 (3)
O1^i—Mn—N2	94.00 (15)	C1—N1—Mn	124.8 (3)
O1—Mn—N2	99.10 (14)	C6—N2—C10	119.3 (4)
N2^i—Mn—N2	160.9 (2)	C6—N2—Mn	118.0 (3)
O1^i—Mn—N1	166.11 (14)	C10—N2—Mn	122.7 (4)
O1—Mn—N1	88.80 (13)	N1—C1—C2	123.7 (5)
N2^i—Mn—N1	94.44 (13)	C3—C2—C1	118.1 (6)
N2—Mn—N1	72.11 (14)	C2—C3—C4	120.1 (6)
O1^i—Mn—N1^i	88.80 (13)	C3—C4—C5	118.9 (6)
O1—Mn—N1^i	166.11 (14)	N1—C5—C4	121.3 (5)
N2^i—Mn—N1^i	72.11 (14)	N1—C5—C6	116.7 (4)
N2—Mn—N1^i	94.44 (13)	C4—C5—C6	122.0 (5)
N1—Mn—N1^i	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)
S2^i—S2—S1	102.78 (17)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O3^ii	0.93	2.50 (1)	3.24	136
C10—H10A···O3^i	0.93	2.69 (1)	3.57	157
C4—H4A···O2^iii	0.93	2.43 (1)	3.26	148
C8—H8A···O2^iv	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.