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The structure of bis(1,10-phenanthroline-[kappa]2N,N')(thio­sulfato-[kappa]2O:S)­manganese(II) methanol solvate, [Mn(S2O3)(C12H8N2)2]·CH3OH, is made up of Mn2+ centers coordinated to two bidentate phenanthroline (phen) groups and an S,O-chelating thio­sulfate anion, forming monomeric entities. The structure of catena-poly­[[di­aqua(2,9-di­methyl-1,10-phen­anthro­line-[kappa]2N,N')­manganese(II)]-[mu]-thio­sulfato-[kappa]2O:S], [Mn(S2O3)(C14H12N2)(H2O)2]n, is polymeric, consisting of Mn(dmph)(H2O)2 units (dmph is 2,9-di­methyl-1,10-phenanthroline) linked by thio­sulfate anions acting in an S,O-chelating manner.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102012404/ob1070sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102012404/ob1070Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102012404/ob1070IIsup3.hkl
Contains datablock II

CCDC references: 193409; 193410

Comment top

In recent years, a large amount of structural work on the complexing properties of the thiosulfate ion has been published (Brezeanu et al., 1998; Carter & Drew, 1999; Freire et al., 1999, 2001; Freire, Baggio, Baggio & Mariezcurrena, 2000; Freire, Baggio, Suescun & Baggio, 2000). From these results, it is clear that the anion behaves as a very versatile ligand in coordination compounds involving transition metals, displaying an internal geometry very dependent on the type of coordination present. A preferred target of the studies have been those complexes of cations which behave as borderline acids between the `a' and `b' classes in the Pearson classification scale (Pearson, 1973); in these cases, the thiosulfate group is expected to bind to the metal ions both through its hard (O) and soft (S) ends, with a resulting variety of coordination modes depending on other factors, viz. the shapes of accompanying ligands, crystal field stabilization, hydrogen bonding, van der Waals interactions, etc. Table 1 summarizes the effect that the simpler coordination modes seem to have on the thiosulfate geometry, through the statistics of relevant interatomic distances and angles in the reported thiosulfate structures present in the October 2001 Release of the Cambridge Structural Database (CSD; Allen & Kennard, 1993). A trend is observed in Scoord complexes towards a lengthening of the S—S bond, and a similar effect is observed in S,O-chelate compounds for the S—Ocoord bonds. In the latter case, the S—Ouncoord bonds shorten to maintain the bond valence around the central S atom (Brown & Altermatt, 1985). The differences in the angles are explained by the predominant effect of non-bonded repulsion, as discussed by McDonald & Cruickshank (1967), when analysing tetrahedral distortions in sulfates.

Although manganese(II) is a hard acid according to the Pearson classification and it is thus expected to bind preferentially to hard bases or to the hard end when multiple coordination sites are available, there are examples of MnII–thiosulfate complexes where the cation behaves as an intermediate acid, binding both to the hard as well as the soft end (O and S, respectively; see, for example, Freire et al., 2001). Therefore, it is of interest to explore the bonding characteristics of other Mn–thiosulfate compounds in the light of this rather unpredictable behavior. In addition, our experience with the thiosulfate anion complexed to a variety of different metal centers suggests that substantially different structures can be obtained through the introduction of small differences in the coordinating organic ligands used or even by using the same ligands but working under slightly different ambient conditions (Freire et al., 1999; Freire, Baggio, Baggio & Mariezcurrena, 2000; Freire, Baggio, Suescun & Baggio, 2000).

With these ideas in mind, we have been attempting to synthesize Mn–thiosulfate complexes, our only successful outcome so far being a polymeric phenanthroline complex, [Mn(phen)(H2O)2(S2O3)]n, of which two independent structure determinations are now available (Brezeanu et al., 1998; Freire et al., 2001). In this paper, we report our most recent advances in this area, namely [Mn(S2O3)(phen)2]·CH3OH, (I), a new monomeric phenanthroline (phen) structure, and a 2,9-dimethyl-1,10-phenanthroline (dmph) polymer, [Mn(dmph)(H2O)2(S2O3)]n, (II).

Compound (I) is monomeric, with two bidentate phen groups [Mn—N 2.246 (2)–2.302 (2) Å] and an S,O-chelating thiosulfate [Mn—O 2.1637 (18) Å and Mn—S 2.6131 (8) Å] providing a quite distorted octahedral coordination of manganese (Fig. 1 and Table 2). Due to the restraints imposed by the chelate character of the ligands present, there are many important geometrical departures from ideal values, the most obvious being for the angles S2—Mn—O1 [70.44 (5)°] and S2—Mn—N1B [155.95 (5)°]. The bidentate thiosulfate anion presents the usual lengthening of the S—O bond corresponding to the coordinated O atom by about 3% of its total length [S—Ocoord 1.4893 (18) Å and mean S—Ouncoord 1.448 (2) Å], as well as the usual narrowing of the corresponding S—S—O angle by ca 7% [S—S—Ocoord 103.82 (8)° and mean S—S—Ouncoord 110.4 (1)°]. On the other hand, the S—S bond length matches almost exactly the corresponding mean value in Table 1. The two independent phenanthroline groups are planar (maximum deviation from their mean planes being 0.025 and 0.011 Å for units A and B, respectively) and their bond distances and angles are as expected.

The structure of (II) presents a manganese ion octahedrally surrounded by a bidentate 2,9-dimethyl-1,10-phenanthroline ligand [Mn—N 2.279 (2) and 2.296 (2) Å], two aqua molecules [Mn—OW 2.184 (2) and 2.206 (2) Å], and one O [Mn—O 2.1655 (19) Å] and one S atom [Mn—S 2.6306 (9) Å] from thiosulfate groups related by a whole unit-cell translation along b (Fig. 2 and Table 3). The coordination polyhedron is irregular, as expected from the restraints imposed by the bidentate dmph ligand, but less distorted than in (I). The most significant departures from ideal values are again associated with the bite angle, viz. N1—Mn—N2 [74.20 (8)°] and N2—Mn—O1W [173.24 (9)°].

The thiosulfate group acts as a bridging ligand between neighboring cations (through S and O) in a rather uncommon disposition for the anion, only reported previously in a zinc(II) bis(ethylenethiourea) thiosulfate complex (Baggio et al., 1974) and the previously mentioned manganese(II) phenanthroline complex, to which (II) is closely related. The molecular geometry matches fairly well the mean values in the reported structures, where it displays a similar coordination, except perhaps for a slight shortening of the S—S bond [1.9719 (11) Å versus a mean of 2.009 (8) Å]. This type of connectivity leads to the configuration of linear chains (Fig. 3) parallel to each other and to the crystallographic b axis. All the H atoms in the aqua molecules are involved in hydrogen bonding (Table 4 and Fig. 3). Two such contacts are of the `intra-chain' type which add to the chain cohesion (double dashed lines in Fig. 3). The other two contacts (simple dashed) link pairs of chains together, into a strip-like structure.

In both structures, there are ππ-stacking interactions between the adjacent planar organic ligands. In (I), this effect seems to be stronger than in (II), as inferred from the larger stacking overlap between the expected parallel interleaved groups (33 versus 12%), as well as from the smaller angle between them [3.9 (2) versus 9.2 (2)°] and the shorter contact in the overlapping region [3.28 (1) versus 3.37 (1) Å].

The results of this work confirm MnII to behave in thiosulfate complexes as a medium strength acid, in spite of its classification in the Pearson scale. They also corroborate the fact that the structure of thiosulfate complexes can not be predicted on stoichiometry grounds alone; slight variations both in the geometry of the ligands involved and in the conditions of synthesis can result in important structural differences. Sometimes these variations reside directly in the environment around the metal atom [viz. structures (I) and (II) in this work] or, in the case where the environments are similar, in the way in which these entities pack. A clear example can be found by comparison of the dmph structure reported herein with the phen analog reported in Freire et al. (2001); in spite of the fact that both structures are built up by almost indistinguishable chains, the resulting crystal packings show significant differences, viz. in the latter structure, adjacent phen groups are far from parallel and present no staking overlap whatsoever.

Experimental top

Small yellow blocks of (I) were obtained as a minor component in the synthesis of the polymer form of the phenanthroline complex, which has already been reported (Freire et al., 2001). After mixing aqueous solutions of manganese chloride and sodium thiosulfate with a methanol solution of phenanthroline, in a 1:3:1 molar ratio, crystals of the dominant polymer form appeared readily, while only a few individual crystals of (I) were found. On the other hand, pale-yellow plates of (II) suitable for X-ray diffraction analysis appeared in a reasonable quantity after diffusion of a methanolic solution of dmph into an aqueous solution of manganese chloride and sodium thiosulfate, in a similar ratio to that used for the preparation of (I). In both cases, crystals were used as obtained in the synthesis, without further recrystallization.

Refinement top

H atoms attached to C atoms were added at calculated positions and allowed for as riding atoms. Terminal methyl H atoms of the dmph ligand were additionally allowed to rotate. Water H atoms were found in difference Fourier maps and were refined with restrained O—H (0.80 Å) and H···H (1.66 times O—H) distances. Compound (I) contains a methanol solvate molecule, which has a disordered O atom, split into two sites with occupancies of 0.65 and 0.35. The corresponding H atoms were not included in the model.

Computing details top

For both compounds, data collection: SMART-NT (Bruker, 2001); cell refinement: SMART-NT; data reduction: SAINT-NT (Bruker, 2000); 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); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the monomeric manganese(II) coordination polyhedron in (I). Displacement ellipsoids are drawn at the 40% probability level.
[Figure 2] Fig. 2. A view of the manganese(II) coordination polyhedron in (II), suggesting the way in which chains are formed. Displacement ellipsoids are drawn at the 40% probability level.
[Figure 3] Fig. 3. Packing view of (II), showing the hydrogen-bonding interactions. Intra-chain hydrogen bonds are drawn as double dashed lines, while those connecting different chains are presented as single dashed lines. [Symmetry code: (i) 3/2 - x, -1/2 + y, z.]
(I) bis(1,10-phenanthroline-κ2N,N')(thiosulfato-κ2O:S)manganese(II) methanol solvate top
Crystal data top
[Mn(S2O3)(C12H8N2)2]·CH4OF(000) = 1148
Mr = 559.51Dx = 1.562 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 84 reflections
a = 12.924 (1) Åθ = 1.7–28.0°
b = 11.412 (1) ŵ = 0.77 mm1
c = 17.084 (1) ÅT = 293 K
β = 109.18 (1)°Blocks, yellow
V = 2379.9 (3) Å30.18 × 0.14 × 0.12 mm
Z = 4
Data collection top
Bruker CCD area-detector
diffractometer
5302 independent reflections
Radiation source: fine-focus sealed tube3942 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
ϕ and ω scansθmax = 28.0°, θmin = 1.7°
Absorption correction: part of the refinement model (ΔF)
(SADABS in SAINT-NT; Bruker, 2000)
h = 816
Tmin = 0.88, Tmax = 0.91k = 1414
11546 measured reflectionsl = 2220
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0728P)2]
where P = (Fo2 + 2Fc2)/3
5302 reflections(Δ/σ)max = 0.011
330 parametersΔρmax = 0.68 e Å3
1 restraintΔρmin = 0.28 e Å3
Crystal data top
[Mn(S2O3)(C12H8N2)2]·CH4OV = 2379.9 (3) Å3
Mr = 559.51Z = 4
Monoclinic, P21/nMo Kα radiation
a = 12.924 (1) ŵ = 0.77 mm1
b = 11.412 (1) ÅT = 293 K
c = 17.084 (1) Å0.18 × 0.14 × 0.12 mm
β = 109.18 (1)°
Data collection top
Bruker CCD area-detector
diffractometer
5302 independent reflections
Absorption correction: part of the refinement model (ΔF)
(SADABS in SAINT-NT; Bruker, 2000)
3942 reflections with I > 2σ(I)
Tmin = 0.88, Tmax = 0.91Rint = 0.030
11546 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0441 restraint
wR(F2) = 0.125H-atom parameters constrained
S = 1.00Δρmax = 0.68 e Å3
5302 reflectionsΔρmin = 0.28 e Å3
330 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*/UeqOcc. (<1)
Mn0.90273 (3)0.82197 (3)0.13372 (2)0.04316 (14)
S10.86129 (5)1.07293 (6)0.09745 (4)0.04631 (18)
S20.87452 (6)1.01075 (7)0.21088 (4)0.0564 (2)
O10.90030 (15)0.97408 (16)0.05753 (10)0.0523 (4)
O20.74816 (15)1.0993 (2)0.05129 (11)0.0676 (6)
O30.93141 (18)1.17420 (17)0.10435 (15)0.0733 (6)
N1A1.08332 (16)0.79457 (18)0.16145 (12)0.0420 (5)
N2A0.95801 (16)0.70514 (18)0.24681 (12)0.0433 (5)
C1A1.1435 (2)0.8346 (2)0.11749 (16)0.0513 (6)
H1A1.10990.88100.07130.062*
C2A1.2546 (2)0.8102 (2)0.13759 (18)0.0567 (7)
H2A1.29340.83650.10380.068*
C3A1.3057 (2)0.7473 (2)0.20715 (18)0.0548 (7)
H3A1.38040.73200.22210.066*
C4A1.2458 (2)0.7059 (2)0.25610 (15)0.0436 (6)
C5A1.2943 (2)0.6408 (2)0.33134 (16)0.0516 (6)
H5A1.36920.62580.34950.062*
C6A1.2330 (2)0.6013 (2)0.37586 (16)0.0506 (6)
H6A1.26640.56120.42510.061*
C7A1.1170 (2)0.6202 (2)0.34879 (14)0.0444 (6)
C8A1.0489 (2)0.5779 (2)0.39244 (16)0.0536 (7)
H8A1.07870.53530.44110.064*
C9A0.9402 (2)0.5999 (3)0.36308 (17)0.0567 (7)
H9A0.89450.57280.39140.068*
C10A0.8975 (2)0.6633 (2)0.29032 (17)0.0516 (6)
H10A0.82240.67740.27080.062*
C11A1.06693 (19)0.68349 (19)0.27575 (14)0.0384 (5)
C12A1.13361 (18)0.7289 (2)0.22955 (14)0.0383 (5)
N1B0.86862 (17)0.69382 (18)0.02409 (13)0.0449 (5)
N2B0.72489 (17)0.7690 (2)0.09821 (13)0.0494 (5)
C1B0.9376 (2)0.6589 (2)0.01391 (17)0.0552 (7)
H1B1.01050.68220.00790.066*
C2B0.9068 (3)0.5891 (3)0.08495 (18)0.0658 (8)
H2B0.95810.56670.10950.079*
C3B0.8010 (3)0.5544 (2)0.11757 (18)0.0645 (8)
H3B0.77910.50830.16510.077*
C4B0.7246 (2)0.5881 (2)0.07961 (16)0.0537 (7)
C5B0.6121 (3)0.5572 (3)0.11106 (19)0.0676 (9)
H5B0.58700.51090.15840.081*
C6B0.5417 (3)0.5933 (3)0.0741 (2)0.0689 (9)
H6B0.46850.57140.09600.083*
C7B0.5760 (2)0.6645 (2)0.00190 (18)0.0569 (7)
C8B0.5046 (2)0.7068 (3)0.0396 (2)0.0725 (9)
H8B0.43060.68710.02020.087*
C9B0.5445 (3)0.7763 (3)0.1079 (2)0.0718 (9)
H9B0.49840.80330.13590.086*
C10B0.6552 (2)0.8064 (3)0.1352 (2)0.0622 (8)
H10B0.68150.85480.18130.075*
C11B0.6865 (2)0.6980 (2)0.03062 (16)0.0471 (6)
C12B0.7623 (2)0.6587 (2)0.00875 (15)0.0453 (6)
O1XA0.8929 (4)0.3714 (5)0.1854 (3)0.1215 (14)0.626 (4)
O1XB0.7836 (7)0.3782 (7)0.0638 (5)0.1215 (14)0.374 (4)
C1X0.8014 (4)0.4158 (4)0.1372 (3)0.1102 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn0.0339 (2)0.0469 (2)0.0438 (2)0.00108 (15)0.00624 (16)0.00107 (15)
S10.0400 (3)0.0491 (4)0.0510 (4)0.0026 (3)0.0164 (3)0.0035 (3)
S20.0628 (5)0.0637 (5)0.0397 (3)0.0081 (3)0.0129 (3)0.0019 (3)
O10.0604 (12)0.0537 (11)0.0464 (9)0.0063 (9)0.0225 (8)0.0015 (8)
O20.0458 (11)0.0973 (16)0.0582 (12)0.0188 (10)0.0149 (9)0.0200 (11)
O30.0721 (15)0.0560 (13)0.1058 (17)0.0140 (10)0.0484 (13)0.0086 (11)
N1A0.0358 (11)0.0481 (12)0.0396 (10)0.0029 (9)0.0090 (9)0.0020 (9)
N2A0.0358 (11)0.0474 (12)0.0439 (11)0.0021 (9)0.0094 (9)0.0002 (9)
C1A0.0474 (16)0.0571 (17)0.0480 (14)0.0042 (12)0.0136 (12)0.0079 (12)
C2A0.0474 (16)0.0629 (18)0.0656 (18)0.0067 (13)0.0266 (14)0.0020 (14)
C3A0.0373 (14)0.0576 (17)0.0697 (18)0.0002 (12)0.0180 (13)0.0044 (14)
C4A0.0357 (13)0.0444 (14)0.0474 (13)0.0006 (10)0.0092 (11)0.0070 (11)
C5A0.0380 (14)0.0510 (15)0.0561 (16)0.0067 (12)0.0023 (12)0.0039 (12)
C6A0.0508 (16)0.0478 (15)0.0435 (14)0.0071 (12)0.0022 (12)0.0008 (11)
C7A0.0479 (15)0.0418 (14)0.0394 (12)0.0003 (11)0.0086 (11)0.0033 (10)
C8A0.0696 (19)0.0489 (15)0.0416 (14)0.0026 (13)0.0174 (13)0.0048 (11)
C9A0.0597 (18)0.0613 (18)0.0547 (16)0.0099 (14)0.0262 (14)0.0030 (13)
C10A0.0424 (15)0.0580 (17)0.0561 (16)0.0045 (12)0.0184 (12)0.0000 (12)
C11A0.0375 (13)0.0380 (13)0.0375 (12)0.0013 (9)0.0090 (10)0.0048 (9)
C12A0.0347 (12)0.0382 (12)0.0394 (12)0.0023 (9)0.0086 (10)0.0047 (10)
N1B0.0388 (12)0.0439 (12)0.0478 (12)0.0018 (9)0.0085 (9)0.0018 (9)
N2B0.0377 (12)0.0533 (13)0.0532 (12)0.0013 (10)0.0094 (10)0.0012 (10)
C1B0.0520 (17)0.0553 (17)0.0567 (16)0.0039 (13)0.0157 (13)0.0006 (13)
C2B0.080 (2)0.0586 (18)0.0627 (18)0.0092 (16)0.0288 (17)0.0033 (14)
C3B0.083 (2)0.0475 (17)0.0542 (16)0.0024 (15)0.0105 (16)0.0096 (13)
C4B0.0611 (18)0.0413 (14)0.0483 (15)0.0041 (12)0.0037 (13)0.0034 (11)
C5B0.069 (2)0.0545 (19)0.0612 (18)0.0173 (15)0.0035 (16)0.0032 (14)
C6B0.0495 (18)0.0609 (19)0.078 (2)0.0188 (14)0.0043 (15)0.0093 (16)
C7B0.0400 (15)0.0541 (17)0.0658 (18)0.0071 (12)0.0027 (13)0.0155 (13)
C8B0.0391 (16)0.075 (2)0.096 (3)0.0085 (15)0.0129 (17)0.0207 (19)
C9B0.0466 (18)0.083 (2)0.092 (2)0.0050 (16)0.0314 (17)0.0107 (19)
C10B0.0474 (17)0.069 (2)0.0709 (19)0.0040 (13)0.0203 (15)0.0001 (15)
C11B0.0407 (14)0.0425 (14)0.0508 (14)0.0025 (11)0.0052 (11)0.0122 (11)
C12B0.0457 (15)0.0386 (14)0.0447 (13)0.0003 (10)0.0056 (11)0.0069 (10)
O1XA0.156 (4)0.093 (3)0.113 (3)0.017 (3)0.041 (3)0.018 (3)
O1XB0.156 (4)0.093 (3)0.113 (3)0.017 (3)0.041 (3)0.018 (3)
C1X0.130 (4)0.101 (3)0.095 (3)0.049 (3)0.029 (3)0.013 (3)
Geometric parameters (Å, º) top
Mn—O12.1637 (18)C9A—C10A1.387 (4)
Mn—N1A2.246 (2)C9A—H9A0.9300
Mn—N2B2.258 (2)C10A—H10A0.9300
Mn—N2A2.261 (2)C11A—C12A1.443 (3)
Mn—N1B2.302 (2)N1B—C1B1.325 (3)
Mn—S22.6131 (8)N1B—C12B1.363 (3)
S1—O21.4466 (18)N2B—C10B1.329 (3)
S1—O31.449 (2)N2B—C11B1.364 (3)
S1—O11.4893 (18)C1B—C2B1.396 (4)
S1—S22.0175 (9)C1B—H1B0.9300
N1A—C1A1.327 (3)C2B—C3B1.355 (4)
N1A—C12A1.356 (3)C2B—H2B0.9300
N2A—C10A1.332 (3)C3B—C4B1.401 (4)
N2A—C11A1.353 (3)C3B—H3B0.9300
C1A—C2A1.391 (4)C4B—C12B1.401 (4)
C1A—H1A0.9300C4B—C5B1.420 (4)
C2A—C3A1.359 (4)C5B—C6B1.332 (4)
C2A—H2A0.9300C5B—H5B0.9300
C3A—C4A1.395 (4)C6B—C7B1.420 (4)
C3A—H3A0.9300C6B—H6B0.9300
C4A—C12A1.395 (3)C7B—C11B1.405 (4)
C4A—C5A1.438 (4)C7B—C8B1.421 (4)
C5A—C6A1.344 (4)C8B—C9B1.364 (5)
C5A—H5A0.9300C8B—H8B0.9300
C6A—C7A1.432 (3)C9B—C10B1.395 (4)
C6A—H6A0.9300C9B—H9B0.9300
C7A—C11A1.403 (3)C10B—H10B0.9300
C7A—C8A1.412 (4)C11B—C12B1.430 (4)
C8A—C9A1.351 (4)O1XA—C1X1.302 (5)
C8A—H8A0.9300O1XB—C1X1.273 (5)
O1—Mn—N1A92.71 (7)C8A—C9A—H9A120.4
O1—Mn—N2B103.93 (8)C10A—C9A—H9A120.4
N1A—Mn—N2B156.20 (8)N2A—C10A—C9A123.6 (3)
O1—Mn—N2A157.67 (7)N2A—C10A—H10A118.2
N1A—Mn—N2A73.92 (7)C9A—C10A—H10A118.2
N2B—Mn—N2A94.57 (8)N2A—C11A—C7A122.7 (2)
O1—Mn—N1B93.40 (7)N2A—C11A—C12A118.1 (2)
N1A—Mn—N1B89.49 (7)C7A—C11A—C12A119.2 (2)
N2B—Mn—N1B72.88 (8)N1A—C12A—C4A122.5 (2)
N2A—Mn—N1B104.06 (8)N1A—C12A—C11A117.6 (2)
O1—Mn—S270.44 (5)C4A—C12A—C11A119.9 (2)
N1A—Mn—S2108.42 (5)C1B—N1B—C12B117.4 (2)
N2B—Mn—S293.31 (6)C1B—N1B—Mn127.57 (18)
N2A—Mn—S296.45 (5)C12B—N1B—Mn114.79 (16)
N1B—Mn—S2155.95 (5)C10B—N2B—C11B118.6 (2)
O2—S1—O3111.79 (14)C10B—N2B—Mn125.12 (19)
O2—S1—O1109.98 (12)C11B—N2B—Mn116.20 (16)
O3—S1—O1110.15 (12)N1B—C1B—C2B123.5 (3)
O2—S1—S2110.39 (8)N1B—C1B—H1B118.3
O3—S1—S2110.43 (10)C2B—C1B—H1B118.3
O1—S1—S2103.82 (8)C3B—C2B—C1B119.1 (3)
S1—S2—Mn77.72 (3)C3B—C2B—H2B120.5
S1—O1—Mn105.81 (9)C1B—C2B—H2B120.5
C1A—N1A—C12A118.1 (2)C2B—C3B—C4B119.9 (3)
C1A—N1A—Mn126.44 (17)C2B—C3B—H3B120.1
C12A—N1A—Mn115.45 (14)C4B—C3B—H3B120.1
C10A—N2A—C11A117.5 (2)C3B—C4B—C12B117.4 (3)
C10A—N2A—Mn127.54 (17)C3B—C4B—C5B123.1 (3)
C11A—N2A—Mn114.75 (15)C12B—C4B—C5B119.4 (3)
N1A—C1A—C2A122.7 (2)C6B—C5B—C4B121.2 (3)
N1A—C1A—H1A118.6C6B—C5B—H5B119.4
C2A—C1A—H1A118.6C4B—C5B—H5B119.4
C3A—C2A—C1A119.2 (2)C5B—C6B—C7B121.4 (3)
C3A—C2A—H2A120.4C5B—C6B—H6B119.3
C1A—C2A—H2A120.4C7B—C6B—H6B119.3
C2A—C3A—C4A119.8 (2)C11B—C7B—C8B116.9 (3)
C2A—C3A—H3A120.1C11B—C7B—C6B119.1 (3)
C4A—C3A—H3A120.1C8B—C7B—C6B124.0 (3)
C12A—C4A—C3A117.6 (2)C9B—C8B—C7B120.0 (3)
C12A—C4A—C5A119.3 (2)C9B—C8B—H8B120.0
C3A—C4A—C5A123.1 (2)C7B—C8B—H8B120.0
C6A—C5A—C4A120.9 (2)C8B—C9B—C10B119.1 (3)
C6A—C5A—H5A119.5C8B—C9B—H9B120.4
C4A—C5A—H5A119.5C10B—C9B—H9B120.4
C5A—C6A—C7A121.1 (2)N2B—C10B—C9B122.9 (3)
C5A—C6A—H6A119.5N2B—C10B—H10B118.5
C7A—C6A—H6A119.5C9B—C10B—H10B118.5
C11A—C7A—C8A117.4 (2)N2B—C11B—C7B122.4 (3)
C11A—C7A—C6A119.5 (2)N2B—C11B—C12B118.0 (2)
C8A—C7A—C6A123.1 (2)C7B—C11B—C12B119.5 (3)
C9A—C8A—C7A119.5 (2)N1B—C12B—C4B122.8 (3)
C9A—C8A—H8A120.2N1B—C12B—C11B117.9 (2)
C7A—C8A—H8A120.2C4B—C12B—C11B119.3 (2)
C8A—C9A—C10A119.3 (2)O1XB—C1X—O1XA108.9 (5)
(II) catena-poly[[diaqua(2,9-dimethyl-1,10-phenanthroline-κ2N,N')manganese(II)]- µ-thiosulfato-κ2O:S] top
Crystal data top
[Mn(S2O3)(C14H12N2)(H2O)2]F(000) = 1688
Mr = 411.35Dx = 1.665 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 108 reflections
a = 15.3800 (12) Åθ = 1.4–28.1°
b = 7.0779 (5) ŵ = 1.09 mm1
c = 30.148 (2) ÅT = 293 K
V = 3281.9 (4) Å3Plate, light yellow
Z = 80.26 × 0.20 × 0.10 mm
Data collection top
Bruker CCD area-detector
diffractometer
3810 independent reflections
Radiation source: fine-focus sealed tube2341 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.061
ϕ and ω scansθmax = 28.1°, θmin = 1.4°
Absorption correction: part of the refinement model (ΔF)
(SADABS in SAINT-NT; Bruker, 2000)
h = 2019
Tmin = 0.82, Tmax = 0.90k = 98
18352 measured reflectionsl = 3836
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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087H atoms treated by a mixture of independent and constrained refinement
S = 0.85 w = 1/[σ2(Fo2) + (0.0342P)2]
where P = (Fo2 + 2Fc2)/3
3810 reflections(Δ/σ)max = 0.009
235 parametersΔρmax = 0.52 e Å3
0 restraintsΔρmin = 0.40 e Å3
Crystal data top
[Mn(S2O3)(C14H12N2)(H2O)2]V = 3281.9 (4) Å3
Mr = 411.35Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 15.3800 (12) ŵ = 1.09 mm1
b = 7.0779 (5) ÅT = 293 K
c = 30.148 (2) Å0.26 × 0.20 × 0.10 mm
Data collection top
Bruker CCD area-detector
diffractometer
3810 independent reflections
Absorption correction: part of the refinement model (ΔF)
(SADABS in SAINT-NT; Bruker, 2000)
2341 reflections with I > 2σ(I)
Tmin = 0.82, Tmax = 0.90Rint = 0.061
18352 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.087H atoms treated by a mixture of independent and constrained refinement
S = 0.85Δρmax = 0.52 e Å3
3810 reflectionsΔρmin = 0.40 e Å3
235 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
Mn0.94408 (3)0.87466 (6)0.127265 (14)0.03413 (14)
S10.97740 (5)1.23218 (12)0.11055 (3)0.0529 (3)
S20.88337 (4)1.41039 (10)0.12560 (2)0.03586 (19)
O10.83438 (12)1.4596 (3)0.08556 (6)0.0432 (5)
O20.82477 (12)1.3244 (3)0.15822 (6)0.0427 (5)
O30.92418 (14)1.5809 (3)0.14461 (7)0.0499 (6)
O1W0.83555 (15)0.8424 (4)0.08005 (8)0.0476 (6)
O2W0.84105 (15)0.9556 (4)0.17335 (7)0.0438 (6)
N11.06030 (14)0.8210 (3)0.08116 (8)0.0358 (6)
N21.06404 (14)0.8798 (3)0.17163 (8)0.0360 (6)
C11.05962 (18)0.7831 (4)0.03790 (10)0.0428 (8)
C21.1366 (2)0.7753 (5)0.01309 (11)0.0554 (9)
H2A1.13440.74850.01710.067*
C31.2137 (2)0.8068 (5)0.03300 (12)0.0583 (10)
H3A1.26460.80520.01640.070*
C41.21711 (19)0.8417 (4)0.07835 (11)0.0455 (8)
C51.2973 (2)0.8687 (5)0.10122 (12)0.0564 (9)
H5A1.34920.86650.08540.068*
C61.29921 (19)0.8967 (5)0.14453 (13)0.0564 (9)
H6A1.35240.91310.15870.068*
C71.2211 (2)0.9022 (4)0.16988 (11)0.0463 (8)
C81.2199 (2)0.9296 (5)0.21559 (12)0.0600 (10)
H8A1.27200.94810.23070.072*
C91.1446 (2)0.9298 (5)0.23823 (11)0.0600 (10)
H9A1.14450.94800.26880.072*
C101.0661 (2)0.9022 (4)0.21528 (10)0.0460 (8)
C111.14000 (17)0.8791 (4)0.14866 (10)0.0375 (7)
C121.13829 (17)0.8475 (4)0.10160 (10)0.0358 (7)
C130.9826 (2)0.8991 (5)0.24091 (10)0.0646 (10)
H13A0.94620.79900.23000.097*
H13B0.95321.01780.23730.097*
H13C0.99480.87860.27180.097*
C140.9749 (2)0.7468 (5)0.01531 (10)0.0579 (9)
H14A0.93680.85230.01990.087*
H14B0.94890.63470.02740.087*
H14C0.98460.72990.01590.087*
H1WA0.825 (2)0.713 (5)0.0796 (12)0.089 (14)*
H1WB0.789 (2)0.884 (5)0.0827 (11)0.066 (13)*
H2WA0.834 (2)1.074 (5)0.1701 (12)0.088 (15)*
H2WB0.793 (2)0.910 (4)0.1696 (10)0.046 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn0.0299 (2)0.0319 (3)0.0406 (3)0.00057 (19)0.0011 (2)0.0018 (2)
S10.0376 (4)0.0375 (5)0.0836 (7)0.0029 (4)0.0175 (4)0.0052 (5)
S20.0320 (4)0.0335 (4)0.0421 (5)0.0016 (3)0.0020 (3)0.0018 (3)
O10.0396 (12)0.0435 (13)0.0464 (13)0.0057 (10)0.0106 (9)0.0001 (10)
O20.0400 (12)0.0387 (12)0.0494 (13)0.0051 (10)0.0129 (10)0.0013 (10)
O30.0674 (14)0.0291 (12)0.0534 (14)0.0116 (11)0.0158 (11)0.0010 (10)
O1W0.0352 (14)0.0500 (16)0.0575 (15)0.0068 (12)0.0011 (11)0.0002 (12)
O2W0.0354 (14)0.0400 (15)0.0559 (15)0.0019 (11)0.0024 (11)0.0011 (11)
N10.0324 (13)0.0351 (14)0.0400 (15)0.0051 (11)0.0003 (11)0.0041 (11)
N20.0380 (14)0.0305 (13)0.0393 (14)0.0015 (11)0.0022 (11)0.0007 (12)
C10.0426 (18)0.0425 (19)0.043 (2)0.0047 (15)0.0075 (15)0.0032 (15)
C20.056 (2)0.065 (2)0.045 (2)0.0050 (19)0.0129 (17)0.0071 (18)
C30.041 (2)0.066 (2)0.067 (3)0.0082 (18)0.0201 (18)0.0005 (19)
C40.0346 (17)0.042 (2)0.060 (2)0.0032 (15)0.0047 (16)0.0030 (16)
C50.0314 (18)0.055 (2)0.083 (3)0.0069 (16)0.0090 (18)0.010 (2)
C60.0296 (18)0.053 (2)0.087 (3)0.0015 (16)0.0089 (18)0.007 (2)
C70.0400 (18)0.0391 (19)0.060 (2)0.0019 (15)0.0129 (16)0.0067 (16)
C80.050 (2)0.060 (2)0.070 (3)0.0013 (19)0.0262 (19)0.0018 (19)
C90.062 (2)0.071 (3)0.047 (2)0.005 (2)0.0155 (18)0.0006 (18)
C100.0477 (19)0.046 (2)0.044 (2)0.0024 (16)0.0079 (16)0.0015 (16)
C110.0335 (16)0.0281 (16)0.0508 (19)0.0027 (13)0.0057 (14)0.0021 (14)
C120.0313 (16)0.0275 (16)0.0486 (19)0.0031 (12)0.0026 (14)0.0010 (14)
C130.068 (2)0.088 (3)0.039 (2)0.004 (2)0.0011 (18)0.0003 (19)
C140.054 (2)0.080 (3)0.040 (2)0.0005 (19)0.0008 (16)0.0161 (19)
Geometric parameters (Å, º) top
Mn—O3i2.1655 (19)C3—C41.391 (4)
Mn—O2W2.184 (2)C3—H3A0.9300
Mn—O1W2.206 (2)C4—C121.401 (4)
Mn—N22.279 (2)C4—C51.426 (4)
Mn—N12.296 (2)C5—C61.321 (5)
Mn—S12.6306 (9)C5—H5A0.9300
S1—S21.9719 (11)C6—C71.424 (4)
S2—O11.4648 (19)C6—H6A0.9300
S2—O21.4663 (19)C7—C81.392 (4)
S2—O31.4763 (19)C7—C111.411 (4)
O3—Mnii2.1655 (19)C8—C91.344 (4)
O1W—H1WA0.93 (4)C8—H8A0.9300
O1W—H1WB0.78 (3)C9—C101.406 (4)
O2W—H2WA0.85 (4)C9—H9A0.9300
O2W—H2WB0.82 (3)C10—C131.499 (4)
N1—C11.331 (3)C11—C121.437 (4)
N1—C121.362 (3)C13—H13A0.9600
N2—C101.326 (4)C13—H13B0.9600
N2—C111.358 (3)C13—H13C0.9600
C1—C21.401 (4)C14—H14A0.9600
C1—C141.492 (4)C14—H14B0.9600
C2—C31.348 (4)C14—H14C0.9600
C2—H2A0.9300
O3i—Mn—O2W89.76 (9)C2—C3—H3A120.0
O3i—Mn—O1W87.11 (9)C4—C3—H3A120.0
O2W—Mn—O1W83.61 (9)C3—C4—C12117.7 (3)
O3i—Mn—N289.31 (8)C3—C4—C5122.1 (3)
O2W—Mn—N2102.11 (9)C12—C4—C5120.2 (3)
O1W—Mn—N2173.24 (9)C6—C5—C4121.1 (3)
O3i—Mn—N195.60 (8)C6—C5—H5A119.4
O2W—Mn—N1173.42 (9)C4—C5—H5A119.4
O1W—Mn—N1100.44 (9)C5—C6—C7121.1 (3)
N2—Mn—N174.20 (8)C5—C6—H6A119.5
O3i—Mn—S1175.80 (6)C7—C6—H6A119.5
O2W—Mn—S190.62 (7)C8—C7—C11117.0 (3)
O1W—Mn—S197.08 (8)C8—C7—C6123.1 (3)
N2—Mn—S186.53 (6)C11—C7—C6119.9 (3)
N1—Mn—S183.76 (6)C9—C8—C7120.9 (3)
S2—S1—Mn115.36 (4)C9—C8—H8A119.5
O1—S2—O2109.60 (12)C7—C8—H8A119.5
O1—S2—O3110.13 (12)C8—C9—C10119.4 (3)
O2—S2—O3109.89 (12)C8—C9—H9A120.3
O1—S2—S1109.86 (9)C10—C9—H9A120.3
O2—S2—S1109.85 (9)N2—C10—C9121.7 (3)
O3—S2—S1107.48 (10)N2—C10—C13119.3 (3)
S2—O3—Mnii138.71 (12)C9—C10—C13119.0 (3)
Mn—O1W—H1WA104 (2)N2—C11—C7121.9 (3)
Mn—O1W—H1WB126 (2)N2—C11—C12119.2 (2)
H1WA—O1W—H1WB102 (3)C7—C11—C12118.8 (3)
Mn—O2W—H2WA106 (2)N1—C12—C4122.1 (3)
Mn—O2W—H2WB118 (2)N1—C12—C11119.0 (2)
H2WA—O2W—H2WB105 (3)C4—C12—C11118.9 (3)
C1—N1—C12118.6 (2)C10—C13—H13A109.5
C1—N1—Mn128.34 (18)C10—C13—H13B109.5
C12—N1—Mn112.90 (18)H13A—C13—H13B109.5
C10—N2—C11119.1 (2)C10—C13—H13C109.5
C10—N2—Mn127.12 (19)H13A—C13—H13C109.5
C11—N2—Mn113.40 (18)H13B—C13—H13C109.5
N1—C1—C2121.6 (3)C1—C14—H14A109.5
N1—C1—C14119.2 (2)C1—C14—H14B109.5
C2—C1—C14119.1 (3)H14A—C14—H14B109.5
C3—C2—C1119.9 (3)C1—C14—H14C109.5
C3—C2—H2A120.0H14A—C14—H14C109.5
C1—C2—H2A120.0H14B—C14—H14C109.5
C2—C3—C4120.0 (3)
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
O1W—H1WA···O1i0.93 (4)1.81 (4)2.714 (3)164 (3)
O1W—H1WB···O1iii0.79 (3)1.96 (3)2.747 (3)173 (3)
O2W—H2WA···O20.84 (4)1.83 (4)2.662 (3)173 (4)
O2W—H2WB···O2iii0.83 (3)1.93 (3)2.752 (3)175 (3)
Symmetry codes: (i) x, y1, z; (iii) x+3/2, y1/2, z.

Experimental details

(I)(II)
Crystal data
Chemical formula[Mn(S2O3)(C12H8N2)2]·CH4O[Mn(S2O3)(C14H12N2)(H2O)2]
Mr559.51411.35
Crystal system, space groupMonoclinic, P21/nOrthorhombic, Pbca
Temperature (K)293293
a, b, c (Å)12.924 (1), 11.412 (1), 17.084 (1)15.3800 (12), 7.0779 (5), 30.148 (2)
α, β, γ (°)90, 109.18 (1), 9090, 90, 90
V3)2379.9 (3)3281.9 (4)
Z48
Radiation typeMo KαMo Kα
µ (mm1)0.771.09
Crystal size (mm)0.18 × 0.14 × 0.120.26 × 0.20 × 0.10
Data collection
DiffractometerBruker CCD area-detector
diffractometer
Bruker CCD area-detector
diffractometer
Absorption correctionPart of the refinement model (ΔF)
(SADABS in SAINT-NT; Bruker, 2000)
Part of the refinement model (ΔF)
(SADABS in SAINT-NT; Bruker, 2000)
Tmin, Tmax0.88, 0.910.82, 0.90
No. of measured, independent and
observed [I > 2σ(I)] reflections
11546, 5302, 3942 18352, 3810, 2341
Rint0.0300.061
(sin θ/λ)max1)0.6610.662
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.125, 1.00 0.041, 0.087, 0.85
No. of reflections53023810
No. of parameters330235
No. of restraints10
H-atom treatmentH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.68, 0.280.52, 0.40

Computer programs: SMART-NT (Bruker, 2001), SMART-NT, SAINT-NT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-PC (Sheldrick, 1994), SHELXL97.

Selected geometric parameters (Å, º) for (I) top
Mn—O12.1637 (18)Mn—S22.6131 (8)
Mn—N1A2.246 (2)S1—O21.4466 (18)
Mn—N2B2.258 (2)S1—O31.449 (2)
Mn—N2A2.261 (2)S1—O11.4893 (18)
Mn—N1B2.302 (2)S1—S22.0175 (9)
O1—Mn—N1A92.71 (7)N1A—Mn—S2108.42 (5)
O1—Mn—N2B103.93 (8)N2B—Mn—S293.31 (6)
N1A—Mn—N2B156.20 (8)N2A—Mn—S296.45 (5)
O1—Mn—N2A157.67 (7)N1B—Mn—S2155.95 (5)
N1A—Mn—N2A73.92 (7)O2—S1—O3111.79 (14)
N2B—Mn—N2A94.57 (8)O2—S1—O1109.98 (12)
O1—Mn—N1B93.40 (7)O3—S1—O1110.15 (12)
N1A—Mn—N1B89.49 (7)O2—S1—S2110.39 (8)
N2B—Mn—N1B72.88 (8)O3—S1—S2110.43 (10)
N2A—Mn—N1B104.06 (8)O1—S1—S2103.82 (8)
O1—Mn—S270.44 (5)
Mean values for selected distances and angles (Å, °) for selected parameters in the S2O3 geometry according to the type of coordination top
Coordination typeS—SS—OcoordS—OuncoordS—S—OcoordS—S—OuncoordCSD
S-Monodentate2.054 (37)1.453 (16)106.9(2.3)19
S,O-Chelating2.018 (20)1.510 (22)1.447 (6)101.1(3.0)110.6(1.1)7
S,O-Bridging2.009 (8)1.479 (15)1.467 (12)108.5(1.0)108.9(1.2)5
Ionic1.992 (13)1.466 (12)109.1(1.3)7
Number of cases found in the CSD (Allen & Kennard, 1993). No entries for O-monodentate, O,O-chelating or O,O-bridging were found. Mixed coordination types have not been included in the survey.
Selected geometric parameters (Å, º) for (II) top
Mn—O3i2.1655 (19)Mn—S12.6306 (9)
Mn—O2W2.184 (2)S1—S21.9719 (11)
Mn—O1W2.206 (2)S2—O11.4648 (19)
Mn—N22.279 (2)S2—O21.4663 (19)
Mn—N12.296 (2)S2—O31.4763 (19)
O3i—Mn—O2W89.76 (9)O2W—Mn—S190.62 (7)
O3i—Mn—O1W87.11 (9)O1W—Mn—S197.08 (8)
O2W—Mn—O1W83.61 (9)N2—Mn—S186.53 (6)
O3i—Mn—N289.31 (8)N1—Mn—S183.76 (6)
O2W—Mn—N2102.11 (9)O1—S2—O2109.60 (12)
O1W—Mn—N2173.24 (9)O1—S2—O3110.13 (12)
O3i—Mn—N195.60 (8)O2—S2—O3109.89 (12)
O2W—Mn—N1173.42 (9)O1—S2—S1109.86 (9)
O1W—Mn—N1100.44 (9)O2—S2—S1109.85 (9)
N2—Mn—N174.20 (8)O3—S2—S1107.48 (10)
O3i—Mn—S1175.80 (6)
Symmetry code: (i) x, y1, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O1i0.93 (4)1.81 (4)2.714 (3)164 (3)
O1W—H1WB···O1ii0.79 (3)1.96 (3)2.747 (3)173 (3)
O2W—H2WA···O20.84 (4)1.83 (4)2.662 (3)173 (4)
O2W—H2WB···O2ii0.83 (3)1.93 (3)2.752 (3)175 (3)
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y1/2, z.
 

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