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The structure of the title compound, [Mn(tpy)2](S4O6)·3H2O (tpy is 2,2′:6′,2′′-ter­pyridine, C15H11N3), consists of monomeric [Mn(tpy)2]2+ units embedded in a complex anionic network made up of tetra­thionate ions and hydration water mol­ecules connected via a complex hydrogen-bonding scheme.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101016481/bk1621sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101016481/bk1621Isup2.hkl
Contains datablock I

CCDC reference: 179259

Comment top

In our studies of transition metal complexes with the thiosulfate ion and polydentate nitrogenated organic bases, we have found quite frequently the occurrence of oxidation processes of the anion giving rise to complexes containing polythionate groups [e.g. with copper (Freire et al., 1998), manganese (Freire, Baggio, Baggio & Mombru, 2001) and nickel (Freire, Baggio & Baggio, 2001)]. In the case of manganese, this process seems to be highly favored due to the different oxidation states the element is able to exhibit. In particular, the structure described by Freire, Baggio, Baggio & Mombru (2001) of bis(2,2'-bipyridyl-N,N')(tetrathionate-O,O')manganese(II) presents the only occurrence in the literature of a complex with a tetrathionate anion (generated `in situ' during the synthesis binding) acting in a bidentate fashion. In light of these quite interesting results, we decided to explore further the possibility of generating polythionate anions during the synthesis process and investigate their eventual coordinating capacity. In the present paper, we report the structure of bis(2,2':6',2''-terpyridine-κ3N)manganese(II) tetrathionate trihydrate, (I), a partially successful attempt in which a tetrathionate group was indeed generated, though here it acts as a counter-ion.

The title compound (Fig. 1) consists of Mn(tpy)22+ cations embedded in the empty spaces of an anionic matrix built up of S4O62- ions and three independent hydration water molecules.

The MnN6 chromophore shows a significant deformation, due to the presence of two highly constrained tridentate ligands (labeled A and B in Fig. 1), with expected coordination angles of 90° ranging between 71.57 (16) and 116.01 (12)°, and expected coordination angles of 180° ranging between 144.33 (14) and 168.07 (13)°. The two tpy molecules present a significant degree of `out-of-plane' deformation, resulting in a concave shape; this departure from planarity is greater for unit A, where the normals of the planar pyridine rings subtend angles as large as 15.8° with one another. Unit B is less deformed, with a maximum deviation of around 4.1°. In spite of these deformations, the two mean tpy planes are almost perpendicular to one another (92°), as expected.

The cationic Mn(tpy)22+ group has been reported only once before, viz. in bis(2,2':6',2''-terpyridine-N,N',N'')manganese(II) bis(triiodide), (II) (Bhula & Weatherburn, 1991), and a comparison of the structures of (I) and (II) shows them to be very similar, with an r.m.s deviation for the least-squares fit of homologous atoms of 0.23 Å [as calculated with XP in SHELXTL/PC (Sheldrick, 1994)]. The similarities are also revealed in the values of the homologous coordination distances, and can be appreciated from the following mean values, reported in the order (I)/(II): outer Mn—N 2.249 (11)/2.249 (7) Å and central Mn—N 2.192/2.186 (6) Å.

The tetrathionate anion is not disordered [as found in some of the structures where it does not coordinate to the cation, e.g. Freire et al. (1998)], and does not present any unusual features with regard to bond distances and angles. This includes the fact (present also in other anionic tetrathionates) that among the three terminal O—S—S angles at each end, that associated with the O—S—S—S torsion angle nearer 180° is significantly smaller than the other two; in this case, 107.47 (16)° against 114.6 (2) and 113.5 (2)°, and 110.07 (28)° against 113.6 (5) and 114.5 (3)°. This behavior has been observed in other O3—S—XX (X = S or O) groups and is discussed elsewhere (Harvey et al., 2001).

The ionic network is profusely interlinked by hydrogen bonding, as shown in Fig. 2 and Table 2, where all the available water H atoms and four of the six tetrathionate O atoms take part. The embedded cations interact with the matrix via weaker C—H···O contacts.

Related literature top

For related literature, see: Bhula & Weatherburn (1991); Freire et al. (1998); Freire, Baggio & Baggio (2001); Freire, Baggio, Baggio & Mombru (2001); Harvey et al. (2001); Sheldrick (1994).

Experimental top

The title compound was obtained by diffusion of an aqueous solution of manganese chloride and sodium thiosulfate into a methanolic solution of terpyridine (1:3:1 ratio). A few days after mixing, yellow plates, badly formed but nonetheless suitable for X-ray diffraction, were obtained.

Refinement top

H atoms attached to C atoms were added at their expected positions and refined as riding (C—H = 0.93 Å). Water H atoms were found in a difference Fourier map and were refined with restraints (O—H = 0.90 Å and H···H = 1.50 Å). Their isotropic displacement factors were taken as 1.2 times those of the water O atom to which they were attached.

Computing details top

Data collection: P3/P4-PC (Siemens, 1991); cell refinement: P3/P4-PC; data reduction: XDISK in SHELXTL/PC (Sheldrick, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC; software used to prepare material for publication: CIFTAB (Sheldrick, 1993), PARST (Nardelli, 1983).

Figures top
[Figure 1] Fig. 1. A view of the asymmetric unit, showing the atom-numbering scheme. For clarity, H atoms are not shown. Displacement ellipsoids drawn at the 40% probability level.
[Figure 2] Fig. 2. Schematic packing view showing the intricate hydrogen-bonding network leading to the anionic matrix. Mn(tpy)22+ cations (omitted from the drawing) occupy the matrix voids. [Symmetry codes: (i) 1 - x, 3 - y, 1 - z; (ii) -1 + x, y, z.]
Bis(2,2':6',2''-Terpyridine-N,N',N'')-manganese(ii) tetrathionate, trihydrate. top
Crystal data top
[Mn(C15H11N3)2](S4O6)·3H2OF(000) = 1644
Mr = 799.76Dx = 1.513 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 8.783 (3) ÅCell parameters from 25 reflections
b = 18.594 (7) Åθ = 7.5–15°
c = 21.556 (12) ŵ = 0.67 mm1
β = 94.05 (4)°T = 293 K
V = 3512 (3) Å3Plates, yellow
Z = 40.48 × 0.32 × 0.12 mm
Data collection top
Siemens R3m
diffractometer
3567 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.058
Graphite monochromatorθmax = 25.0°, θmin = 1.9°
ω/2θ scansh = 1010
Absorption correction: ψ scan
(North et al., 1968)
k = 022
Tmin = 0.77, Tmax = 0.92l = 025
6852 measured reflections2 standard reflections every 98 reflections
6187 independent reflections intensity decay: <2%
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)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.05P)2 + 0.672P]
where P = (Fo2 + 2Fc2)/3
6187 reflections(Δ/σ)max < 0.01
469 parametersΔρmax = 0.27 e Å3
9 restraintsΔρmin = 0.25 e Å3
Crystal data top
[Mn(C15H11N3)2](S4O6)·3H2OV = 3512 (3) Å3
Mr = 799.76Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.783 (3) ŵ = 0.67 mm1
b = 18.594 (7) ÅT = 293 K
c = 21.556 (12) Å0.48 × 0.32 × 0.12 mm
β = 94.05 (4)°
Data collection top
Siemens R3m
diffractometer
3567 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.058
Tmin = 0.77, Tmax = 0.922 standard reflections every 98 reflections
6852 measured reflections intensity decay: <2%
6187 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0539 restraints
wR(F2) = 0.124H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.27 e Å3
6187 reflectionsΔρmin = 0.25 e Å3
469 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
Mn10.73909 (6)0.90700 (3)0.73746 (3)0.04484 (18)
S10.79113 (14)1.11698 (7)0.56935 (5)0.0647 (3)
S40.9361 (2)1.34439 (15)0.54085 (9)0.1375 (8)
S20.83764 (18)1.21068 (9)0.62393 (6)0.0915 (5)
S31.02169 (18)1.25314 (11)0.58972 (8)0.1144 (6)
O10.7645 (4)1.13928 (19)0.50672 (13)0.0815 (10)
O20.6585 (4)1.0915 (2)0.59754 (16)0.0972 (11)
O30.9210 (4)1.0718 (2)0.57962 (18)0.1211 (15)
O40.8989 (9)1.3953 (3)0.5885 (3)0.223 (3)
O50.8120 (6)1.3254 (3)0.5008 (2)0.224 (4)
O61.0646 (6)1.3702 (4)0.5107 (3)0.204 (3)
N1A0.6491 (4)0.7966 (2)0.76096 (17)0.0573 (9)
N2A0.6966 (4)0.9053 (2)0.83637 (15)0.0631 (10)
N3A0.8180 (4)1.0128 (2)0.77742 (17)0.0603 (10)
C1A0.6375 (5)0.7408 (3)0.7220 (2)0.0698 (13)
H1AA0.67160.74690.68250.084*
C2A0.5783 (6)0.6745 (3)0.7365 (3)0.0989 (19)
H2AA0.56910.63790.70700.119*
C3A0.5346 (7)0.6647 (4)0.7941 (4)0.114 (2)
H3AA0.49610.62040.80550.137*
C4A0.5467 (6)0.7196 (4)0.8360 (3)0.0875 (18)
H4AA0.51640.71270.87610.105*
C5A0.6052 (5)0.7869 (3)0.8187 (2)0.0669 (13)
C6A0.6212 (5)0.8487 (4)0.8587 (2)0.0788 (17)
C7A0.5605 (7)0.8537 (5)0.9175 (3)0.117 (2)
H7AA0.50550.81600.93340.141*
C8A0.5862 (10)0.9171 (6)0.9508 (3)0.149 (4)
H8AA0.54740.92130.98960.179*
C9A0.6658 (9)0.9733 (5)0.9288 (3)0.125 (3)
H9AA0.68411.01490.95200.150*
C10A0.7190 (6)0.9650 (4)0.8692 (2)0.0822 (17)
C11A0.8050 (6)1.0237 (3)0.8388 (2)0.0761 (15)
C12A0.8693 (9)1.0834 (4)0.8679 (3)0.122 (3)
H12A0.85811.09060.91000.146*
C13A0.9484 (9)1.1319 (4)0.8361 (5)0.134 (3)
H13A0.99761.17020.85680.161*
C14A0.9554 (7)1.1242 (3)0.7738 (4)0.107 (2)
H14A1.00291.15830.75020.129*
C15A0.8881 (6)1.0626 (3)0.7466 (3)0.0747 (14)
H15A0.89331.05640.70400.090*
N1B0.5121 (3)0.94978 (17)0.69894 (14)0.0444 (8)
N2B0.7332 (3)0.89997 (16)0.63631 (12)0.0380 (7)
N3B0.9664 (3)0.86567 (17)0.71327 (14)0.0455 (8)
C1B0.4056 (5)0.9758 (2)0.7339 (2)0.0626 (12)
H1BA0.42480.97660.77690.075*
C2B0.2694 (5)1.0012 (3)0.7087 (2)0.0677 (13)
H2BA0.19781.01930.73440.081*
C3B0.2378 (5)1.0003 (2)0.6462 (3)0.0714 (14)
H3BA0.14541.01790.62870.086*
C4B0.3463 (5)0.9727 (2)0.6092 (2)0.0648 (13)
H4BA0.32710.97040.56620.078*
C5B0.4833 (4)0.9484 (2)0.63695 (18)0.0461 (10)
C6B0.6095 (4)0.9201 (2)0.60085 (17)0.0432 (9)
C7B0.6054 (5)0.9146 (2)0.53711 (18)0.0591 (11)
H7BA0.51800.92800.51300.071*
C8B0.7321 (6)0.8888 (3)0.50876 (19)0.0687 (14)
H8BA0.73070.88490.46570.082*
C9B0.8588 (5)0.8694 (2)0.54542 (18)0.0588 (12)
H9BA0.94540.85290.52740.071*
C10B0.8575 (4)0.8742 (2)0.60905 (17)0.0426 (9)
C11B0.9862 (4)0.8533 (2)0.65286 (17)0.0443 (9)
C12B1.1187 (5)0.8213 (2)0.6342 (2)0.0605 (12)
H12B1.13050.81270.59230.073*
C13B1.2318 (5)0.8027 (3)0.6785 (2)0.0719 (14)
H13B1.32030.78060.66670.086*
C14B1.2150 (5)0.8162 (3)0.7389 (2)0.0676 (13)
H14B1.29250.80490.76900.081*
C15B1.0815 (5)0.8471 (2)0.7557 (2)0.0606 (12)
H15B1.06960.85550.79770.073*
O1W0.5605 (5)1.2532 (3)0.4533 (2)0.1218 (15)
H1WA0.592 (4)1.220 (1)0.482 (1)0.146*
H1WB0.603 (4)1.2968 (7)0.461 (1)0.146*
O2W0.2695 (6)1.3164 (3)0.41982 (19)0.1432 (18)
H2WA0.341 (3)1.283 (2)0.429 (1)0.172*
H2WB0.208 (3)1.325 (2)0.451 (1)0.172*
O3W0.2949 (9)1.4719 (5)0.3711 (3)0.116 (3)
H3WA0.346 (2)1.4328 (7)0.386 (1)0.139*
H3WB0.241 (7)1.493 (2)0.401 (1)0.139*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0439 (3)0.0499 (4)0.0409 (3)0.0037 (3)0.0041 (2)0.0013 (3)
S10.0595 (7)0.0744 (9)0.0599 (7)0.0068 (6)0.0017 (5)0.0152 (6)
S40.1168 (14)0.208 (2)0.0860 (11)0.0610 (16)0.0036 (10)0.0350 (14)
S20.1095 (11)0.0962 (12)0.0708 (8)0.0195 (9)0.0194 (8)0.0281 (8)
S30.0778 (10)0.1383 (16)0.1265 (13)0.0238 (11)0.0031 (9)0.0361 (12)
O10.087 (2)0.092 (3)0.065 (2)0.011 (2)0.0000 (17)0.0057 (18)
O20.099 (3)0.091 (3)0.106 (3)0.012 (2)0.039 (2)0.013 (2)
O30.101 (3)0.134 (4)0.124 (3)0.055 (3)0.026 (2)0.038 (3)
O40.377 (11)0.157 (6)0.140 (5)0.023 (6)0.051 (6)0.005 (4)
O50.236 (6)0.257 (7)0.161 (5)0.156 (6)0.106 (5)0.115 (5)
O60.161 (5)0.271 (8)0.182 (5)0.096 (5)0.028 (4)0.039 (5)
N1A0.052 (2)0.052 (3)0.068 (2)0.0036 (18)0.0118 (18)0.017 (2)
N2A0.063 (2)0.084 (3)0.0420 (19)0.023 (2)0.0019 (17)0.000 (2)
N3A0.060 (2)0.055 (3)0.064 (2)0.013 (2)0.0084 (18)0.014 (2)
C1A0.064 (3)0.052 (3)0.095 (4)0.004 (3)0.017 (3)0.016 (3)
C2A0.094 (4)0.049 (4)0.157 (6)0.004 (3)0.035 (4)0.023 (4)
C3A0.089 (4)0.073 (5)0.183 (8)0.014 (4)0.038 (5)0.048 (5)
C4A0.063 (3)0.089 (5)0.113 (5)0.021 (3)0.029 (3)0.057 (4)
C5A0.053 (3)0.070 (4)0.080 (3)0.020 (3)0.024 (2)0.027 (3)
C6A0.060 (3)0.119 (5)0.060 (3)0.040 (3)0.024 (2)0.040 (3)
C7A0.125 (5)0.157 (7)0.076 (4)0.039 (5)0.049 (4)0.038 (4)
C8A0.192 (8)0.200 (10)0.061 (4)0.095 (8)0.051 (5)0.013 (5)
C9A0.166 (7)0.150 (7)0.061 (4)0.070 (6)0.015 (4)0.000 (4)
C10A0.097 (4)0.099 (5)0.049 (3)0.048 (4)0.003 (3)0.015 (3)
C11A0.082 (4)0.069 (4)0.073 (3)0.031 (3)0.024 (3)0.024 (3)
C12A0.149 (7)0.102 (6)0.107 (5)0.021 (5)0.040 (5)0.060 (5)
C13A0.130 (7)0.070 (5)0.191 (9)0.014 (5)0.078 (6)0.043 (6)
C14A0.094 (4)0.063 (4)0.157 (6)0.001 (3)0.043 (4)0.000 (4)
C15A0.067 (3)0.059 (4)0.097 (4)0.007 (3)0.005 (3)0.012 (3)
N1B0.0384 (17)0.039 (2)0.056 (2)0.0042 (15)0.0061 (15)0.0035 (16)
N2B0.0417 (17)0.0287 (18)0.0430 (16)0.0001 (15)0.0006 (13)0.0008 (14)
N3B0.0419 (18)0.041 (2)0.0537 (19)0.0030 (16)0.0018 (15)0.0079 (16)
C1B0.053 (3)0.043 (3)0.092 (3)0.005 (2)0.009 (2)0.000 (2)
C2B0.056 (3)0.058 (3)0.091 (4)0.011 (2)0.013 (3)0.002 (3)
C3B0.041 (3)0.049 (3)0.124 (4)0.009 (2)0.002 (3)0.013 (3)
C4B0.048 (3)0.050 (3)0.093 (3)0.002 (2)0.017 (2)0.004 (3)
C5B0.044 (2)0.030 (2)0.064 (3)0.0018 (19)0.0043 (19)0.001 (2)
C6B0.043 (2)0.034 (2)0.051 (2)0.0048 (18)0.0079 (17)0.0011 (18)
C7B0.056 (3)0.066 (3)0.054 (2)0.002 (2)0.012 (2)0.003 (2)
C8B0.085 (3)0.078 (4)0.044 (2)0.001 (3)0.008 (2)0.000 (2)
C9B0.073 (3)0.055 (3)0.050 (2)0.012 (2)0.015 (2)0.000 (2)
C10B0.049 (2)0.034 (2)0.046 (2)0.0001 (19)0.0047 (18)0.0026 (18)
C11B0.042 (2)0.038 (2)0.055 (2)0.0008 (19)0.0117 (18)0.0010 (19)
C12B0.056 (3)0.053 (3)0.074 (3)0.007 (2)0.018 (2)0.003 (2)
C13B0.056 (3)0.065 (3)0.095 (4)0.028 (3)0.007 (3)0.016 (3)
C14B0.039 (2)0.078 (4)0.085 (3)0.003 (2)0.006 (2)0.025 (3)
C15B0.061 (3)0.062 (3)0.057 (3)0.003 (2)0.006 (2)0.012 (2)
O1W0.100 (3)0.103 (3)0.161 (4)0.017 (3)0.001 (3)0.015 (3)
O2W0.129 (4)0.201 (6)0.099 (3)0.030 (4)0.005 (3)0.005 (3)
O3W0.131 (4)0.140 (5)0.081 (3)0.067 (5)0.023 (3)0.005 (3)
Geometric parameters (Å, º) top
Mn1—N2B2.181 (3)C13A—H13A0.9300
Mn1—N2A2.191 (3)C14A—C15A1.399 (7)
Mn1—N3B2.235 (3)C14A—H14A0.9300
Mn1—N3A2.238 (4)C15A—H15A0.9300
Mn1—N1B2.250 (3)N1B—C1B1.333 (5)
Mn1—N1A2.270 (4)N1B—C5B1.343 (5)
S1—O11.416 (3)N2B—C6B1.337 (4)
S1—O31.421 (3)N2B—C10B1.363 (4)
S1—O21.432 (3)N3B—C11B1.345 (4)
S1—S22.126 (2)N3B—C15B1.360 (5)
S4—O51.387 (4)C1B—C2B1.364 (6)
S4—O61.425 (4)C1B—H1BA0.9300
S4—O41.451 (5)C2B—C3B1.354 (6)
S4—S32.108 (3)C2B—H2BA0.9300
S2—S31.987 (2)C3B—C4B1.385 (6)
N1A—C1A1.333 (6)C3B—H3BA0.9300
N1A—C5A1.341 (5)C4B—C5B1.382 (5)
N2A—C10A1.323 (6)C4B—H4BA0.9300
N2A—C6A1.349 (6)C5B—C6B1.494 (5)
N3A—C15A1.317 (6)C6B—C7B1.376 (5)
N3A—C11A1.350 (6)C7B—C8B1.392 (6)
C1A—C2A1.381 (7)C7B—H7BA0.9300
C1A—H1AA0.9300C8B—C9B1.367 (6)
C2A—C3A1.338 (8)C8B—H8BA0.9300
C2A—H2AA0.9300C9B—C10B1.375 (5)
C3A—C4A1.363 (8)C9B—H9BA0.9300
C3A—H3AA0.9300C10B—C11B1.473 (5)
C4A—C5A1.413 (7)C11B—C12B1.392 (5)
C4A—H4AA0.9300C12B—C13B1.372 (6)
C5A—C6A1.438 (7)C12B—H12B0.9300
C6A—C7A1.414 (7)C13B—C14B1.345 (6)
C7A—C8A1.388 (11)C13B—H13B0.9300
C7A—H7AA0.9300C14B—C15B1.377 (6)
C8A—C9A1.361 (11)C14B—H14B0.9300
C8A—H8AA0.9300C15B—H15B0.9300
C9A—C10A1.406 (7)O1W—H1WA0.90 (2)
C9A—H9AA0.9300O1W—H1WB0.903 (19)
C10A—C11A1.503 (8)O2W—H2WA0.90 (3)
C11A—C12A1.378 (8)O2W—H2WB0.90 (3)
C12A—C13A1.354 (10)O3W—H3WA0.90 (2)
C12A—H12A0.9300O3W—H3WB0.91 (4)
C13A—C14A1.356 (9)
N2B—Mn1—N2A168.07 (13)C12A—C11A—C10A126.1 (6)
N2B—Mn1—N3B72.83 (11)C13A—C12A—C11A121.0 (7)
N2A—Mn1—N3B116.01 (12)C13A—C12A—H12A119.5
N2B—Mn1—N3A114.98 (13)C11A—C12A—H12A119.5
N2A—Mn1—N3A72.99 (16)C12A—C13A—C14A119.4 (7)
N3B—Mn1—N3A97.75 (13)C12A—C13A—H13A120.3
N2B—Mn1—N1B72.21 (11)C14A—C13A—H13A120.3
N2A—Mn1—N1B99.01 (12)C13A—C14A—C15A117.0 (7)
N3B—Mn1—N1B144.91 (11)C13A—C14A—H14A121.5
N3A—Mn1—N1B94.21 (12)C15A—C14A—H14A121.5
N2B—Mn1—N1A100.65 (13)N3A—C15A—C14A124.2 (6)
N2A—Mn1—N1A71.57 (16)N3A—C15A—H15A117.9
N3B—Mn1—N1A94.12 (12)C14A—C15A—H15A117.9
N3A—Mn1—N1A144.34 (14)C1B—N1B—C5B118.7 (3)
N1B—Mn1—N1A95.09 (12)C1B—N1B—Mn1123.9 (3)
O1—S1—O3113.5 (2)C5B—N1B—Mn1117.4 (2)
O1—S1—O2114.6 (2)C6B—N2B—C10B119.7 (3)
O3—S1—O2114.0 (3)C6B—N2B—Mn1121.0 (2)
O1—S1—S2107.47 (16)C10B—N2B—Mn1119.3 (2)
O3—S1—S2106.10 (18)C11B—N3B—C15B117.9 (3)
O2—S1—S299.59 (16)C11B—N3B—Mn1117.6 (2)
O5—S4—O6114.5 (3)C15B—N3B—Mn1124.4 (3)
O5—S4—O4113.6 (4)N1B—C1B—C2B122.1 (4)
O6—S4—O4109.2 (4)N1B—C1B—H1BA119.0
O5—S4—S3110.1 (3)C2B—C1B—H1BA119.0
O6—S4—S3103.4 (3)C3B—C2B—C1B120.3 (4)
O4—S4—S3105.2 (3)C3B—C2B—H2BA119.8
S3—S2—S1104.47 (9)C1B—C2B—H2BA119.8
S2—S3—S4103.56 (11)C2B—C3B—C4B118.5 (4)
C1A—N1A—C5A117.8 (4)C2B—C3B—H3BA120.8
C1A—N1A—Mn1125.1 (3)C4B—C3B—H3BA120.8
C5A—N1A—Mn1117.1 (3)C5B—C4B—C3B119.0 (4)
C10A—N2A—C6A121.4 (5)C5B—C4B—H4BA120.5
C10A—N2A—Mn1118.6 (4)C3B—C4B—H4BA120.5
C6A—N2A—Mn1118.7 (3)N1B—C5B—C4B121.5 (4)
C15A—N3A—C11A117.6 (5)N1B—C5B—C6B115.5 (3)
C15A—N3A—Mn1124.5 (3)C4B—C5B—C6B123.0 (4)
C11A—N3A—Mn1117.5 (4)N2B—C6B—C7B120.8 (4)
N1A—C1A—C2A124.4 (5)N2B—C6B—C5B113.8 (3)
N1A—C1A—H1AA117.8C7B—C6B—C5B125.4 (3)
C2A—C1A—H1AA117.8C6B—C7B—C8B119.9 (4)
C3A—C2A—C1A117.9 (7)C6B—C7B—H7BA120.0
C3A—C2A—H2AA121.0C8B—C7B—H7BA120.0
C1A—C2A—H2AA121.0C9B—C8B—C7B118.7 (4)
C2A—C3A—C4A119.9 (6)C9B—C8B—H8BA120.6
C2A—C3A—H3AA120.0C7B—C8B—H8BA120.6
C4A—C3A—H3AA120.0C8B—C9B—C10B119.7 (4)
C3A—C4A—C5A120.0 (6)C8B—C9B—H9BA120.1
C3A—C4A—H4AA120.0C10B—C9B—H9BA120.1
C5A—C4A—H4AA120.0N2B—C10B—C9B121.1 (4)
N1A—C5A—C4A119.9 (5)N2B—C10B—C11B114.7 (3)
N1A—C5A—C6A115.2 (4)C9B—C10B—C11B124.2 (4)
C4A—C5A—C6A124.9 (5)N3B—C11B—C12B121.3 (4)
N2A—C6A—C7A119.6 (6)N3B—C11B—C10B115.5 (3)
N2A—C6A—C5A116.1 (4)C12B—C11B—C10B123.2 (4)
C7A—C6A—C5A124.3 (6)C13B—C12B—C11B119.1 (4)
C8A—C7A—C6A117.4 (7)C13B—C12B—H12B120.5
C8A—C7A—H7AA121.3C11B—C12B—H12B120.5
C6A—C7A—H7AA121.3C14B—C13B—C12B120.2 (4)
C9A—C8A—C7A122.7 (6)C14B—C13B—H13B119.9
C9A—C8A—H8AA118.6C12B—C13B—H13B119.9
C7A—C8A—H8AA118.6C13B—C14B—C15B119.1 (4)
C8A—C9A—C10A116.5 (7)C13B—C14B—H14B120.4
C8A—C9A—H9AA121.7C15B—C14B—H14B120.4
C10A—C9A—H9AA121.7N3B—C15B—C14B122.4 (4)
N2A—C10A—C9A122.2 (7)N3B—C15B—H15B118.8
N2A—C10A—C11A115.8 (4)C14B—C15B—H15B118.8
C9A—C10A—C11A122.0 (6)H1WA—O1W—H1WB111.9 (17)
N3A—C11A—C12A120.4 (6)H2WA—O2W—H2WB113 (2)
N3A—C11A—C10A113.5 (4)H3WA—O3W—H3WB112 (2)
O1—S1—S2—S360.05 (18)C11A—N3A—C15A—C14A2.8 (7)
O3—S1—S2—S361.7 (2)Mn1—N3A—C15A—C14A170.9 (4)
O2—S1—S2—S3179.81 (18)C13A—C14A—C15A—N3A0.8 (8)
S1—S2—S3—S4107.09 (12)N2B—Mn1—N1B—C1B178.6 (3)
O5—S4—S3—S251.0 (3)N2A—Mn1—N1B—C1B9.7 (3)
O6—S4—S3—S2173.8 (3)N3B—Mn1—N1B—C1B173.6 (3)
O4—S4—S3—S271.7 (3)N3A—Mn1—N1B—C1B63.7 (3)
N2B—Mn1—N1A—C1A14.7 (4)N1A—Mn1—N1B—C1B81.8 (3)
N2A—Mn1—N1A—C1A174.6 (4)N2B—Mn1—N1B—C5B1.8 (3)
N3B—Mn1—N1A—C1A58.5 (4)N2A—Mn1—N1B—C5B169.9 (3)
N3A—Mn1—N1A—C1A167.9 (3)N3B—Mn1—N1B—C5B6.8 (4)
N1B—Mn1—N1A—C1A87.6 (4)N3A—Mn1—N1B—C5B116.7 (3)
N2B—Mn1—N1A—C5A165.7 (3)N1A—Mn1—N1B—C5B97.8 (3)
N2A—Mn1—N1A—C5A4.9 (3)N2A—Mn1—N2B—C6B42.0 (8)
N3B—Mn1—N1A—C5A121.0 (3)N3B—Mn1—N2B—C6B178.7 (3)
N3A—Mn1—N1A—C5A11.6 (4)N3A—Mn1—N2B—C6B88.0 (3)
N1B—Mn1—N1A—C5A92.9 (3)N1B—Mn1—N2B—C6B1.7 (3)
N2B—Mn1—N2A—C10A126.5 (7)N1A—Mn1—N2B—C6B90.3 (3)
N3B—Mn1—N2A—C10A97.4 (3)N2A—Mn1—N2B—C10B137.6 (6)
N3A—Mn1—N2A—C10A7.0 (3)N3B—Mn1—N2B—C10B1.7 (3)
N1B—Mn1—N2A—C10A84.7 (3)N3A—Mn1—N2B—C10B92.4 (3)
N1A—Mn1—N2A—C10A177.1 (4)N1B—Mn1—N2B—C10B178.7 (3)
N2B—Mn1—N2A—C6A40.8 (8)N1A—Mn1—N2B—C10B89.4 (3)
N3B—Mn1—N2A—C6A95.3 (3)N2B—Mn1—N3B—C11B3.4 (3)
N3A—Mn1—N2A—C6A174.2 (3)N2A—Mn1—N3B—C11B168.0 (3)
N1B—Mn1—N2A—C6A82.6 (3)N3A—Mn1—N3B—C11B117.2 (3)
N1A—Mn1—N2A—C6A9.8 (3)N1B—Mn1—N3B—C11B8.4 (4)
N2B—Mn1—N3A—C15A14.7 (4)N1A—Mn1—N3B—C11B96.5 (3)
N2A—Mn1—N3A—C15A174.8 (4)N2B—Mn1—N3B—C15B178.2 (3)
N3B—Mn1—N3A—C15A59.9 (4)N2A—Mn1—N3B—C15B6.8 (4)
N1B—Mn1—N3A—C15A87.1 (4)N3A—Mn1—N3B—C15B68.0 (3)
N1A—Mn1—N3A—C15A168.2 (3)N1B—Mn1—N3B—C15B176.8 (3)
N2B—Mn1—N3A—C11A171.5 (3)N1A—Mn1—N3B—C15B78.3 (3)
N2A—Mn1—N3A—C11A1.0 (3)C5B—N1B—C1B—C2B0.4 (6)
N3B—Mn1—N3A—C11A113.9 (3)Mn1—N1B—C1B—C2B180.0 (3)
N1B—Mn1—N3A—C11A99.2 (3)N1B—C1B—C2B—C3B0.4 (7)
N1A—Mn1—N3A—C11A5.6 (4)C1B—C2B—C3B—C4B0.4 (7)
C5A—N1A—C1A—C2A2.4 (7)C2B—C3B—C4B—C5B1.3 (7)
Mn1—N1A—C1A—C2A178.0 (4)C1B—N1B—C5B—C4B0.5 (6)
N1A—C1A—C2A—C3A2.5 (8)Mn1—N1B—C5B—C4B179.1 (3)
C1A—C2A—C3A—C4A1.2 (9)C1B—N1B—C5B—C6B178.7 (3)
C2A—C3A—C4A—C5A0.0 (9)Mn1—N1B—C5B—C6B1.7 (4)
C1A—N1A—C5A—C4A1.1 (6)C3B—C4B—C5B—N1B1.4 (6)
Mn1—N1A—C5A—C4A179.3 (3)C3B—C4B—C5B—C6B177.8 (4)
C1A—N1A—C5A—C6A179.6 (4)C10B—N2B—C6B—C7B0.7 (5)
Mn1—N1A—C5A—C6A0.0 (5)Mn1—N2B—C6B—C7B179.0 (3)
C3A—C4A—C5A—N1A0.1 (8)C10B—N2B—C6B—C5B179.0 (3)
C3A—C4A—C5A—C6A179.1 (5)Mn1—N2B—C6B—C5B1.4 (4)
C10A—N2A—C6A—C7A1.9 (7)N1B—C5B—C6B—N2B0.2 (5)
Mn1—N2A—C6A—C7A165.0 (4)C4B—C5B—C6B—N2B179.4 (4)
C10A—N2A—C6A—C5A179.6 (4)N1B—C5B—C6B—C7B179.4 (4)
Mn1—N2A—C6A—C5A13.5 (5)C4B—C5B—C6B—C7B0.2 (6)
N1A—C5A—C6A—N2A8.6 (6)N2B—C6B—C7B—C8B1.1 (6)
C4A—C5A—C6A—N2A172.2 (4)C5B—C6B—C7B—C8B178.5 (4)
N1A—C5A—C6A—C7A169.8 (4)C6B—C7B—C8B—C9B0.1 (7)
C4A—C5A—C6A—C7A9.5 (8)C7B—C8B—C9B—C10B1.3 (7)
N2A—C6A—C7A—C8A1.9 (8)C6B—N2B—C10B—C9B0.8 (6)
C5A—C6A—C7A—C8A179.8 (6)Mn1—N2B—C10B—C9B179.6 (3)
C6A—C7A—C8A—C9A0.2 (11)C6B—N2B—C10B—C11B179.6 (3)
C7A—C8A—C9A—C10A1.5 (12)Mn1—N2B—C10B—C11B0.0 (4)
C6A—N2A—C10A—C9A0.1 (7)C8B—C9B—C10B—N2B1.7 (6)
Mn1—N2A—C10A—C9A166.7 (4)C8B—C9B—C10B—C11B178.7 (4)
C6A—N2A—C10A—C11A179.8 (4)C15B—N3B—C11B—C12B1.2 (6)
Mn1—N2A—C10A—C11A13.3 (5)Mn1—N3B—C11B—C12B173.9 (3)
C8A—C9A—C10A—N2A1.6 (9)C15B—N3B—C11B—C10B179.7 (3)
C8A—C9A—C10A—C11A178.5 (6)Mn1—N3B—C11B—C10B4.6 (4)
C15A—N3A—C11A—C12A2.7 (7)N2B—C10B—C11B—N3B3.0 (5)
Mn1—N3A—C11A—C12A171.5 (4)C9B—C10B—C11B—N3B176.6 (4)
C15A—N3A—C11A—C10A178.2 (4)N2B—C10B—C11B—C12B175.4 (4)
Mn1—N3A—C11A—C10A7.6 (5)C9B—C10B—C11B—C12B5.0 (6)
N2A—C10A—C11A—N3A13.6 (6)N3B—C11B—C12B—C13B0.6 (6)
C9A—C10A—C11A—N3A166.5 (5)C10B—C11B—C12B—C13B179.0 (4)
N2A—C10A—C11A—C12A165.5 (5)C11B—C12B—C13B—C14B0.9 (7)
C9A—C10A—C11A—C12A14.5 (8)C12B—C13B—C14B—C15B1.8 (7)
N3A—C11A—C12A—C13A1.0 (10)C11B—N3B—C15B—C14B0.3 (6)
C10A—C11A—C12A—C13A178.0 (6)Mn1—N3B—C15B—C14B174.4 (3)
C11A—C12A—C13A—C14A4.7 (12)C13B—C14B—C15B—N3B1.2 (7)
C12A—C13A—C14A—C15A4.5 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O10.90 (2)2.17 (3)2.955 (6)144 (2)
O1W—H1WB···O50.90 (2)2.04 (3)2.722 (7)131 (2)
O2W—H2WA···O1W0.90 (3)2.04 (3)2.859 (7)152 (3)
O2W—H2WB···O6i0.90 (3)2.05 (3)2.928 (8)165 (2)
O3W—H3WA···O2W0.90 (2)2.40 (2)3.090 (11)134 (1)
O3W—H3WB···O4ii0.91 (4)2.43 (5)3.156 (11)137 (3)
Symmetry codes: (i) x1, y, z; (ii) x+1, y+3, z+1.

Experimental details

Crystal data
Chemical formula[Mn(C15H11N3)2](S4O6)·3H2O
Mr799.76
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)8.783 (3), 18.594 (7), 21.556 (12)
β (°) 94.05 (4)
V3)3512 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.67
Crystal size (mm)0.48 × 0.32 × 0.12
Data collection
DiffractometerSiemens R3m
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.77, 0.92
No. of measured, independent and
observed [I > 2σ(I)] reflections
6852, 6187, 3567
Rint0.058
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.124, 1.00
No. of reflections6187
No. of parameters469
No. of restraints9
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.27, 0.25

Computer programs: P3/P4-PC (Siemens, 1991), P3/P4-PC, XDISK in SHELXTL/PC (Sheldrick, 1994), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL/PC, CIFTAB (Sheldrick, 1993), PARST (Nardelli, 1983).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O10.90 (2)2.17 (3)2.955 (6)144 (2)
O1W—H1WB···O50.90 (2)2.04 (3)2.722 (7)131 (2)
O2W—H2WA···O1W0.90 (3)2.04 (3)2.859 (7)152 (3)
O2W—H2WB···O6i0.90 (3)2.05 (3)2.928 (8)165 (2)
O3W—H3WA···O2W0.90 (2)2.40 (2)3.090 (11)134 (1)
O3W—H3WB···O4ii0.91 (4)2.43 (5)3.156 (11)137 (3)
Symmetry codes: (i) x1, y, z; (ii) x+1, y+3, z+1.
 

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