Buy article online - an online subscription or single-article purchase is required to access this article.
The structure of bis(1,10-phenanthroline-
2N,N')(thiosulfato-
2O:
S)manganese(II) methanol solvate, [Mn(S
2O
3)(C
12H
8N
2)
2]·CH
3OH, is made up of Mn
2+ 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-
2N,N')manganese(II)]-
-thiosulfato-
2O:
S], [Mn(S
2O
3)(C
14H
12N
2)(H
2O)
2]
n, is polymeric, consisting of Mn(dmph)(H
2O)
2 units (dmph is 2,9-dimethyl-1,10-phenanthroline) linked by thiosulfate anions acting in an
S,
O-chelating manner.
Supporting information
CCDC references: 193409; 193410
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.
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.
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.
(I) bis(1,10-phenanthroline-
κ2N,
N')(thiosulfato-
κ2O:
S)manganese(II) methanol solvate
top
Crystal data top
[Mn(S2O3)(C12H8N2)2]·CH4O | F(000) = 1148 |
Mr = 559.51 | Dx = 1.562 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 84 reflections |
a = 12.924 (1) Å | θ = 1.7–28.0° |
b = 11.412 (1) Å | µ = 0.77 mm−1 |
c = 17.084 (1) Å | T = 293 K |
β = 109.18 (1)° | Blocks, yellow |
V = 2379.9 (3) Å3 | 0.18 × 0.14 × 0.12 mm |
Z = 4 | |
Data collection top
Bruker CCD area-detector diffractometer | 5302 independent reflections |
Radiation source: fine-focus sealed tube | 3942 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ϕ and ω scans | θmax = 28.0°, θmin = 1.7° |
Absorption correction: part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 2000) | h = −8→16 |
Tmin = 0.88, Tmax = 0.91 | k = −14→14 |
11546 measured reflections | l = −22→20 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.125 | H-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 parameters | Δρmax = 0.68 e Å−3 |
1 restraint | Δρmin = −0.28 e Å−3 |
Crystal data top
[Mn(S2O3)(C12H8N2)2]·CH4O | V = 2379.9 (3) Å3 |
Mr = 559.51 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.924 (1) Å | µ = 0.77 mm−1 |
b = 11.412 (1) Å | T = 293 K |
c = 17.084 (1) Å | 0.18 × 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 = 0.91 | Rint = 0.030 |
11546 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 1 restraint |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.68 e Å−3 |
5302 reflections | Δρmin = −0.28 e Å−3 |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
Mn | 0.90273 (3) | 0.82197 (3) | 0.13372 (2) | 0.04316 (14) | |
S1 | 0.86129 (5) | 1.07293 (6) | 0.09745 (4) | 0.04631 (18) | |
S2 | 0.87452 (6) | 1.01075 (7) | 0.21088 (4) | 0.0564 (2) | |
O1 | 0.90030 (15) | 0.97408 (16) | 0.05753 (10) | 0.0523 (4) | |
O2 | 0.74816 (15) | 1.0993 (2) | 0.05129 (11) | 0.0676 (6) | |
O3 | 0.93141 (18) | 1.17420 (17) | 0.10435 (15) | 0.0733 (6) | |
N1A | 1.08332 (16) | 0.79457 (18) | 0.16145 (12) | 0.0420 (5) | |
N2A | 0.95801 (16) | 0.70514 (18) | 0.24681 (12) | 0.0433 (5) | |
C1A | 1.1435 (2) | 0.8346 (2) | 0.11749 (16) | 0.0513 (6) | |
H1A | 1.1099 | 0.8810 | 0.0713 | 0.062* | |
C2A | 1.2546 (2) | 0.8102 (2) | 0.13759 (18) | 0.0567 (7) | |
H2A | 1.2934 | 0.8365 | 0.1038 | 0.068* | |
C3A | 1.3057 (2) | 0.7473 (2) | 0.20715 (18) | 0.0548 (7) | |
H3A | 1.3804 | 0.7320 | 0.2221 | 0.066* | |
C4A | 1.2458 (2) | 0.7059 (2) | 0.25610 (15) | 0.0436 (6) | |
C5A | 1.2943 (2) | 0.6408 (2) | 0.33134 (16) | 0.0516 (6) | |
H5A | 1.3692 | 0.6258 | 0.3495 | 0.062* | |
C6A | 1.2330 (2) | 0.6013 (2) | 0.37586 (16) | 0.0506 (6) | |
H6A | 1.2664 | 0.5612 | 0.4251 | 0.061* | |
C7A | 1.1170 (2) | 0.6202 (2) | 0.34879 (14) | 0.0444 (6) | |
C8A | 1.0489 (2) | 0.5779 (2) | 0.39244 (16) | 0.0536 (7) | |
H8A | 1.0787 | 0.5353 | 0.4411 | 0.064* | |
C9A | 0.9402 (2) | 0.5999 (3) | 0.36308 (17) | 0.0567 (7) | |
H9A | 0.8945 | 0.5728 | 0.3914 | 0.068* | |
C10A | 0.8975 (2) | 0.6633 (2) | 0.29032 (17) | 0.0516 (6) | |
H10A | 0.8224 | 0.6774 | 0.2708 | 0.062* | |
C11A | 1.06693 (19) | 0.68349 (19) | 0.27575 (14) | 0.0384 (5) | |
C12A | 1.13361 (18) | 0.7289 (2) | 0.22955 (14) | 0.0383 (5) | |
N1B | 0.86862 (17) | 0.69382 (18) | 0.02409 (13) | 0.0449 (5) | |
N2B | 0.72489 (17) | 0.7690 (2) | 0.09821 (13) | 0.0494 (5) | |
C1B | 0.9376 (2) | 0.6589 (2) | −0.01391 (17) | 0.0552 (7) | |
H1B | 1.0105 | 0.6822 | 0.0079 | 0.066* | |
C2B | 0.9068 (3) | 0.5891 (3) | −0.08495 (18) | 0.0658 (8) | |
H2B | 0.9581 | 0.5667 | −0.1095 | 0.079* | |
C3B | 0.8010 (3) | 0.5544 (2) | −0.11757 (18) | 0.0645 (8) | |
H3B | 0.7791 | 0.5083 | −0.1651 | 0.077* | |
C4B | 0.7246 (2) | 0.5881 (2) | −0.07961 (16) | 0.0537 (7) | |
C5B | 0.6121 (3) | 0.5572 (3) | −0.11106 (19) | 0.0676 (9) | |
H5B | 0.5870 | 0.5109 | −0.1584 | 0.081* | |
C6B | 0.5417 (3) | 0.5933 (3) | −0.0741 (2) | 0.0689 (9) | |
H6B | 0.4685 | 0.5714 | −0.0960 | 0.083* | |
C7B | 0.5760 (2) | 0.6645 (2) | −0.00190 (18) | 0.0569 (7) | |
C8B | 0.5046 (2) | 0.7068 (3) | 0.0396 (2) | 0.0725 (9) | |
H8B | 0.4306 | 0.6871 | 0.0202 | 0.087* | |
C9B | 0.5445 (3) | 0.7763 (3) | 0.1079 (2) | 0.0718 (9) | |
H9B | 0.4984 | 0.8033 | 0.1359 | 0.086* | |
C10B | 0.6552 (2) | 0.8064 (3) | 0.1352 (2) | 0.0622 (8) | |
H10B | 0.6815 | 0.8548 | 0.1813 | 0.075* | |
C11B | 0.6865 (2) | 0.6980 (2) | 0.03062 (16) | 0.0471 (6) | |
C12B | 0.7623 (2) | 0.6587 (2) | −0.00875 (15) | 0.0453 (6) | |
O1XA | 0.8929 (4) | 0.3714 (5) | 0.1854 (3) | 0.1215 (14) | 0.626 (4) |
O1XB | 0.7836 (7) | 0.3782 (7) | 0.0638 (5) | 0.1215 (14) | 0.374 (4) |
C1X | 0.8014 (4) | 0.4158 (4) | 0.1372 (3) | 0.1102 (15) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn | 0.0339 (2) | 0.0469 (2) | 0.0438 (2) | 0.00108 (15) | 0.00624 (16) | 0.00107 (15) |
S1 | 0.0400 (3) | 0.0491 (4) | 0.0510 (4) | 0.0026 (3) | 0.0164 (3) | 0.0035 (3) |
S2 | 0.0628 (5) | 0.0637 (5) | 0.0397 (3) | 0.0081 (3) | 0.0129 (3) | −0.0019 (3) |
O1 | 0.0604 (12) | 0.0537 (11) | 0.0464 (9) | 0.0063 (9) | 0.0225 (8) | 0.0015 (8) |
O2 | 0.0458 (11) | 0.0973 (16) | 0.0582 (12) | 0.0188 (10) | 0.0149 (9) | 0.0200 (11) |
O3 | 0.0721 (15) | 0.0560 (13) | 0.1058 (17) | −0.0140 (10) | 0.0484 (13) | −0.0086 (11) |
N1A | 0.0358 (11) | 0.0481 (12) | 0.0396 (10) | −0.0029 (9) | 0.0090 (9) | 0.0020 (9) |
N2A | 0.0358 (11) | 0.0474 (12) | 0.0439 (11) | −0.0021 (9) | 0.0094 (9) | −0.0002 (9) |
C1A | 0.0474 (16) | 0.0571 (17) | 0.0480 (14) | −0.0042 (12) | 0.0136 (12) | 0.0079 (12) |
C2A | 0.0474 (16) | 0.0629 (18) | 0.0656 (18) | −0.0067 (13) | 0.0266 (14) | 0.0020 (14) |
C3A | 0.0373 (14) | 0.0576 (17) | 0.0697 (18) | −0.0002 (12) | 0.0180 (13) | −0.0044 (14) |
C4A | 0.0357 (13) | 0.0444 (14) | 0.0474 (13) | −0.0006 (10) | 0.0092 (11) | −0.0070 (11) |
C5A | 0.0380 (14) | 0.0510 (15) | 0.0561 (16) | 0.0067 (12) | 0.0023 (12) | −0.0039 (12) |
C6A | 0.0508 (16) | 0.0478 (15) | 0.0435 (14) | 0.0071 (12) | 0.0022 (12) | −0.0008 (11) |
C7A | 0.0479 (15) | 0.0418 (14) | 0.0394 (12) | 0.0003 (11) | 0.0086 (11) | −0.0033 (10) |
C8A | 0.0696 (19) | 0.0489 (15) | 0.0416 (14) | −0.0026 (13) | 0.0174 (13) | 0.0048 (11) |
C9A | 0.0597 (18) | 0.0613 (18) | 0.0547 (16) | −0.0099 (14) | 0.0262 (14) | 0.0030 (13) |
C10A | 0.0424 (15) | 0.0580 (17) | 0.0561 (16) | −0.0045 (12) | 0.0184 (12) | 0.0000 (12) |
C11A | 0.0375 (13) | 0.0380 (13) | 0.0375 (12) | −0.0013 (9) | 0.0090 (10) | −0.0048 (9) |
C12A | 0.0347 (12) | 0.0382 (12) | 0.0394 (12) | −0.0023 (9) | 0.0086 (10) | −0.0047 (10) |
N1B | 0.0388 (12) | 0.0439 (12) | 0.0478 (12) | 0.0018 (9) | 0.0085 (9) | 0.0018 (9) |
N2B | 0.0377 (12) | 0.0533 (13) | 0.0532 (12) | 0.0013 (10) | 0.0094 (10) | 0.0012 (10) |
C1B | 0.0520 (17) | 0.0553 (17) | 0.0567 (16) | 0.0039 (13) | 0.0157 (13) | −0.0006 (13) |
C2B | 0.080 (2) | 0.0586 (18) | 0.0627 (18) | 0.0092 (16) | 0.0288 (17) | −0.0033 (14) |
C3B | 0.083 (2) | 0.0475 (17) | 0.0542 (16) | −0.0024 (15) | 0.0105 (16) | −0.0096 (13) |
C4B | 0.0611 (18) | 0.0413 (14) | 0.0483 (15) | −0.0041 (12) | 0.0037 (13) | 0.0034 (11) |
C5B | 0.069 (2) | 0.0545 (19) | 0.0612 (18) | −0.0173 (15) | −0.0035 (16) | −0.0032 (14) |
C6B | 0.0495 (18) | 0.0609 (19) | 0.078 (2) | −0.0188 (14) | −0.0043 (15) | 0.0093 (16) |
C7B | 0.0400 (15) | 0.0541 (17) | 0.0658 (18) | −0.0071 (12) | 0.0027 (13) | 0.0155 (13) |
C8B | 0.0391 (16) | 0.075 (2) | 0.096 (3) | −0.0085 (15) | 0.0129 (17) | 0.0207 (19) |
C9B | 0.0466 (18) | 0.083 (2) | 0.092 (2) | 0.0050 (16) | 0.0314 (17) | 0.0107 (19) |
C10B | 0.0474 (17) | 0.069 (2) | 0.0709 (19) | 0.0040 (13) | 0.0203 (15) | 0.0001 (15) |
C11B | 0.0407 (14) | 0.0425 (14) | 0.0508 (14) | −0.0025 (11) | 0.0052 (11) | 0.0122 (11) |
C12B | 0.0457 (15) | 0.0386 (14) | 0.0447 (13) | 0.0003 (10) | 0.0056 (11) | 0.0069 (10) |
O1XA | 0.156 (4) | 0.093 (3) | 0.113 (3) | 0.017 (3) | 0.041 (3) | −0.018 (3) |
O1XB | 0.156 (4) | 0.093 (3) | 0.113 (3) | 0.017 (3) | 0.041 (3) | −0.018 (3) |
C1X | 0.130 (4) | 0.101 (3) | 0.095 (3) | 0.049 (3) | 0.029 (3) | 0.013 (3) |
Geometric parameters (Å, º) top
Mn—O1 | 2.1637 (18) | C9A—C10A | 1.387 (4) |
Mn—N1A | 2.246 (2) | C9A—H9A | 0.9300 |
Mn—N2B | 2.258 (2) | C10A—H10A | 0.9300 |
Mn—N2A | 2.261 (2) | C11A—C12A | 1.443 (3) |
Mn—N1B | 2.302 (2) | N1B—C1B | 1.325 (3) |
Mn—S2 | 2.6131 (8) | N1B—C12B | 1.363 (3) |
S1—O2 | 1.4466 (18) | N2B—C10B | 1.329 (3) |
S1—O3 | 1.449 (2) | N2B—C11B | 1.364 (3) |
S1—O1 | 1.4893 (18) | C1B—C2B | 1.396 (4) |
S1—S2 | 2.0175 (9) | C1B—H1B | 0.9300 |
N1A—C1A | 1.327 (3) | C2B—C3B | 1.355 (4) |
N1A—C12A | 1.356 (3) | C2B—H2B | 0.9300 |
N2A—C10A | 1.332 (3) | C3B—C4B | 1.401 (4) |
N2A—C11A | 1.353 (3) | C3B—H3B | 0.9300 |
C1A—C2A | 1.391 (4) | C4B—C12B | 1.401 (4) |
C1A—H1A | 0.9300 | C4B—C5B | 1.420 (4) |
C2A—C3A | 1.359 (4) | C5B—C6B | 1.332 (4) |
C2A—H2A | 0.9300 | C5B—H5B | 0.9300 |
C3A—C4A | 1.395 (4) | C6B—C7B | 1.420 (4) |
C3A—H3A | 0.9300 | C6B—H6B | 0.9300 |
C4A—C12A | 1.395 (3) | C7B—C11B | 1.405 (4) |
C4A—C5A | 1.438 (4) | C7B—C8B | 1.421 (4) |
C5A—C6A | 1.344 (4) | C8B—C9B | 1.364 (5) |
C5A—H5A | 0.9300 | C8B—H8B | 0.9300 |
C6A—C7A | 1.432 (3) | C9B—C10B | 1.395 (4) |
C6A—H6A | 0.9300 | C9B—H9B | 0.9300 |
C7A—C11A | 1.403 (3) | C10B—H10B | 0.9300 |
C7A—C8A | 1.412 (4) | C11B—C12B | 1.430 (4) |
C8A—C9A | 1.351 (4) | O1XA—C1X | 1.302 (5) |
C8A—H8A | 0.9300 | O1XB—C1X | 1.273 (5) |
| | | |
O1—Mn—N1A | 92.71 (7) | C8A—C9A—H9A | 120.4 |
O1—Mn—N2B | 103.93 (8) | C10A—C9A—H9A | 120.4 |
N1A—Mn—N2B | 156.20 (8) | N2A—C10A—C9A | 123.6 (3) |
O1—Mn—N2A | 157.67 (7) | N2A—C10A—H10A | 118.2 |
N1A—Mn—N2A | 73.92 (7) | C9A—C10A—H10A | 118.2 |
N2B—Mn—N2A | 94.57 (8) | N2A—C11A—C7A | 122.7 (2) |
O1—Mn—N1B | 93.40 (7) | N2A—C11A—C12A | 118.1 (2) |
N1A—Mn—N1B | 89.49 (7) | C7A—C11A—C12A | 119.2 (2) |
N2B—Mn—N1B | 72.88 (8) | N1A—C12A—C4A | 122.5 (2) |
N2A—Mn—N1B | 104.06 (8) | N1A—C12A—C11A | 117.6 (2) |
O1—Mn—S2 | 70.44 (5) | C4A—C12A—C11A | 119.9 (2) |
N1A—Mn—S2 | 108.42 (5) | C1B—N1B—C12B | 117.4 (2) |
N2B—Mn—S2 | 93.31 (6) | C1B—N1B—Mn | 127.57 (18) |
N2A—Mn—S2 | 96.45 (5) | C12B—N1B—Mn | 114.79 (16) |
N1B—Mn—S2 | 155.95 (5) | C10B—N2B—C11B | 118.6 (2) |
O2—S1—O3 | 111.79 (14) | C10B—N2B—Mn | 125.12 (19) |
O2—S1—O1 | 109.98 (12) | C11B—N2B—Mn | 116.20 (16) |
O3—S1—O1 | 110.15 (12) | N1B—C1B—C2B | 123.5 (3) |
O2—S1—S2 | 110.39 (8) | N1B—C1B—H1B | 118.3 |
O3—S1—S2 | 110.43 (10) | C2B—C1B—H1B | 118.3 |
O1—S1—S2 | 103.82 (8) | C3B—C2B—C1B | 119.1 (3) |
S1—S2—Mn | 77.72 (3) | C3B—C2B—H2B | 120.5 |
S1—O1—Mn | 105.81 (9) | C1B—C2B—H2B | 120.5 |
C1A—N1A—C12A | 118.1 (2) | C2B—C3B—C4B | 119.9 (3) |
C1A—N1A—Mn | 126.44 (17) | C2B—C3B—H3B | 120.1 |
C12A—N1A—Mn | 115.45 (14) | C4B—C3B—H3B | 120.1 |
C10A—N2A—C11A | 117.5 (2) | C3B—C4B—C12B | 117.4 (3) |
C10A—N2A—Mn | 127.54 (17) | C3B—C4B—C5B | 123.1 (3) |
C11A—N2A—Mn | 114.75 (15) | C12B—C4B—C5B | 119.4 (3) |
N1A—C1A—C2A | 122.7 (2) | C6B—C5B—C4B | 121.2 (3) |
N1A—C1A—H1A | 118.6 | C6B—C5B—H5B | 119.4 |
C2A—C1A—H1A | 118.6 | C4B—C5B—H5B | 119.4 |
C3A—C2A—C1A | 119.2 (2) | C5B—C6B—C7B | 121.4 (3) |
C3A—C2A—H2A | 120.4 | C5B—C6B—H6B | 119.3 |
C1A—C2A—H2A | 120.4 | C7B—C6B—H6B | 119.3 |
C2A—C3A—C4A | 119.8 (2) | C11B—C7B—C8B | 116.9 (3) |
C2A—C3A—H3A | 120.1 | C11B—C7B—C6B | 119.1 (3) |
C4A—C3A—H3A | 120.1 | C8B—C7B—C6B | 124.0 (3) |
C12A—C4A—C3A | 117.6 (2) | C9B—C8B—C7B | 120.0 (3) |
C12A—C4A—C5A | 119.3 (2) | C9B—C8B—H8B | 120.0 |
C3A—C4A—C5A | 123.1 (2) | C7B—C8B—H8B | 120.0 |
C6A—C5A—C4A | 120.9 (2) | C8B—C9B—C10B | 119.1 (3) |
C6A—C5A—H5A | 119.5 | C8B—C9B—H9B | 120.4 |
C4A—C5A—H5A | 119.5 | C10B—C9B—H9B | 120.4 |
C5A—C6A—C7A | 121.1 (2) | N2B—C10B—C9B | 122.9 (3) |
C5A—C6A—H6A | 119.5 | N2B—C10B—H10B | 118.5 |
C7A—C6A—H6A | 119.5 | C9B—C10B—H10B | 118.5 |
C11A—C7A—C8A | 117.4 (2) | N2B—C11B—C7B | 122.4 (3) |
C11A—C7A—C6A | 119.5 (2) | N2B—C11B—C12B | 118.0 (2) |
C8A—C7A—C6A | 123.1 (2) | C7B—C11B—C12B | 119.5 (3) |
C9A—C8A—C7A | 119.5 (2) | N1B—C12B—C4B | 122.8 (3) |
C9A—C8A—H8A | 120.2 | N1B—C12B—C11B | 117.9 (2) |
C7A—C8A—H8A | 120.2 | C4B—C12B—C11B | 119.3 (2) |
C8A—C9A—C10A | 119.3 (2) | O1XB—C1X—O1XA | 108.9 (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 = 411.35 | Dx = 1.665 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 108 reflections |
a = 15.3800 (12) Å | θ = 1.4–28.1° |
b = 7.0779 (5) Å | µ = 1.09 mm−1 |
c = 30.148 (2) Å | T = 293 K |
V = 3281.9 (4) Å3 | Plate, light yellow |
Z = 8 | 0.26 × 0.20 × 0.10 mm |
Data collection top
Bruker CCD area-detector diffractometer | 3810 independent reflections |
Radiation source: fine-focus sealed tube | 2341 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
ϕ and ω scans | θmax = 28.1°, θmin = 1.4° |
Absorption correction: part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 2000) | h = −20→19 |
Tmin = 0.82, Tmax = 0.90 | k = −9→8 |
18352 measured reflections | l = −38→36 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H 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 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
Crystal data top
[Mn(S2O3)(C14H12N2)(H2O)2] | V = 3281.9 (4) Å3 |
Mr = 411.35 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 15.3800 (12) Å | µ = 1.09 mm−1 |
b = 7.0779 (5) Å | T = 293 K |
c = 30.148 (2) Å | 0.26 × 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 = 0.90 | Rint = 0.061 |
18352 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.85 | Δρmax = 0.52 e Å−3 |
3810 reflections | Δρmin = −0.40 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Mn | 0.94408 (3) | 0.87466 (6) | 0.127265 (14) | 0.03413 (14) | |
S1 | 0.97740 (5) | 1.23218 (12) | 0.11055 (3) | 0.0529 (3) | |
S2 | 0.88337 (4) | 1.41039 (10) | 0.12560 (2) | 0.03586 (19) | |
O1 | 0.83438 (12) | 1.4596 (3) | 0.08556 (6) | 0.0432 (5) | |
O2 | 0.82477 (12) | 1.3244 (3) | 0.15822 (6) | 0.0427 (5) | |
O3 | 0.92418 (14) | 1.5809 (3) | 0.14461 (7) | 0.0499 (6) | |
O1W | 0.83555 (15) | 0.8424 (4) | 0.08005 (8) | 0.0476 (6) | |
O2W | 0.84105 (15) | 0.9556 (4) | 0.17335 (7) | 0.0438 (6) | |
N1 | 1.06030 (14) | 0.8210 (3) | 0.08116 (8) | 0.0358 (6) | |
N2 | 1.06404 (14) | 0.8798 (3) | 0.17163 (8) | 0.0360 (6) | |
C1 | 1.05962 (18) | 0.7831 (4) | 0.03790 (10) | 0.0428 (8) | |
C2 | 1.1366 (2) | 0.7753 (5) | 0.01309 (11) | 0.0554 (9) | |
H2A | 1.1344 | 0.7485 | −0.0171 | 0.067* | |
C3 | 1.2137 (2) | 0.8068 (5) | 0.03300 (12) | 0.0583 (10) | |
H3A | 1.2646 | 0.8052 | 0.0164 | 0.070* | |
C4 | 1.21711 (19) | 0.8417 (4) | 0.07835 (11) | 0.0455 (8) | |
C5 | 1.2973 (2) | 0.8687 (5) | 0.10122 (12) | 0.0564 (9) | |
H5A | 1.3492 | 0.8665 | 0.0854 | 0.068* | |
C6 | 1.29921 (19) | 0.8967 (5) | 0.14453 (13) | 0.0564 (9) | |
H6A | 1.3524 | 0.9131 | 0.1587 | 0.068* | |
C7 | 1.2211 (2) | 0.9022 (4) | 0.16988 (11) | 0.0463 (8) | |
C8 | 1.2199 (2) | 0.9296 (5) | 0.21559 (12) | 0.0600 (10) | |
H8A | 1.2720 | 0.9481 | 0.2307 | 0.072* | |
C9 | 1.1446 (2) | 0.9298 (5) | 0.23823 (11) | 0.0600 (10) | |
H9A | 1.1445 | 0.9480 | 0.2688 | 0.072* | |
C10 | 1.0661 (2) | 0.9022 (4) | 0.21528 (10) | 0.0460 (8) | |
C11 | 1.14000 (17) | 0.8791 (4) | 0.14866 (10) | 0.0375 (7) | |
C12 | 1.13829 (17) | 0.8475 (4) | 0.10160 (10) | 0.0358 (7) | |
C13 | 0.9826 (2) | 0.8991 (5) | 0.24091 (10) | 0.0646 (10) | |
H13A | 0.9462 | 0.7990 | 0.2300 | 0.097* | |
H13B | 0.9532 | 1.0178 | 0.2373 | 0.097* | |
H13C | 0.9948 | 0.8786 | 0.2718 | 0.097* | |
C14 | 0.9749 (2) | 0.7468 (5) | 0.01531 (10) | 0.0579 (9) | |
H14A | 0.9368 | 0.8523 | 0.0199 | 0.087* | |
H14B | 0.9489 | 0.6347 | 0.0274 | 0.087* | |
H14C | 0.9846 | 0.7299 | −0.0159 | 0.087* | |
H1WA | 0.825 (2) | 0.713 (5) | 0.0796 (12) | 0.089 (14)* | |
H1WB | 0.789 (2) | 0.884 (5) | 0.0827 (11) | 0.066 (13)* | |
H2WA | 0.834 (2) | 1.074 (5) | 0.1701 (12) | 0.088 (15)* | |
H2WB | 0.793 (2) | 0.910 (4) | 0.1696 (10) | 0.046 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn | 0.0299 (2) | 0.0319 (3) | 0.0406 (3) | 0.00057 (19) | 0.0011 (2) | −0.0018 (2) |
S1 | 0.0376 (4) | 0.0375 (5) | 0.0836 (7) | 0.0029 (4) | 0.0175 (4) | 0.0052 (5) |
S2 | 0.0320 (4) | 0.0335 (4) | 0.0421 (5) | −0.0016 (3) | −0.0020 (3) | −0.0018 (3) |
O1 | 0.0396 (12) | 0.0435 (13) | 0.0464 (13) | −0.0057 (10) | −0.0106 (9) | 0.0001 (10) |
O2 | 0.0400 (12) | 0.0387 (12) | 0.0494 (13) | 0.0051 (10) | 0.0129 (10) | 0.0013 (10) |
O3 | 0.0674 (14) | 0.0291 (12) | 0.0534 (14) | −0.0116 (11) | −0.0158 (11) | −0.0010 (10) |
O1W | 0.0352 (14) | 0.0500 (16) | 0.0575 (15) | 0.0068 (12) | −0.0011 (11) | −0.0002 (12) |
O2W | 0.0354 (14) | 0.0400 (15) | 0.0559 (15) | −0.0019 (11) | 0.0024 (11) | −0.0011 (11) |
N1 | 0.0324 (13) | 0.0351 (14) | 0.0400 (15) | 0.0051 (11) | 0.0003 (11) | −0.0041 (11) |
N2 | 0.0380 (14) | 0.0305 (13) | 0.0393 (14) | 0.0015 (11) | −0.0022 (11) | 0.0007 (12) |
C1 | 0.0426 (18) | 0.0425 (19) | 0.043 (2) | 0.0047 (15) | 0.0075 (15) | −0.0032 (15) |
C2 | 0.056 (2) | 0.065 (2) | 0.045 (2) | 0.0050 (19) | 0.0129 (17) | −0.0071 (18) |
C3 | 0.041 (2) | 0.066 (2) | 0.067 (3) | 0.0082 (18) | 0.0201 (18) | 0.0005 (19) |
C4 | 0.0346 (17) | 0.042 (2) | 0.060 (2) | 0.0032 (15) | 0.0047 (16) | 0.0030 (16) |
C5 | 0.0314 (18) | 0.055 (2) | 0.083 (3) | 0.0069 (16) | 0.0090 (18) | 0.010 (2) |
C6 | 0.0296 (18) | 0.053 (2) | 0.087 (3) | 0.0015 (16) | −0.0089 (18) | 0.007 (2) |
C7 | 0.0400 (18) | 0.0391 (19) | 0.060 (2) | 0.0019 (15) | −0.0129 (16) | 0.0067 (16) |
C8 | 0.050 (2) | 0.060 (2) | 0.070 (3) | 0.0013 (19) | −0.0262 (19) | 0.0018 (19) |
C9 | 0.062 (2) | 0.071 (3) | 0.047 (2) | 0.005 (2) | −0.0155 (18) | −0.0006 (18) |
C10 | 0.0477 (19) | 0.046 (2) | 0.044 (2) | 0.0024 (16) | −0.0079 (16) | 0.0015 (16) |
C11 | 0.0335 (16) | 0.0281 (16) | 0.0508 (19) | 0.0027 (13) | −0.0057 (14) | 0.0021 (14) |
C12 | 0.0313 (16) | 0.0275 (16) | 0.0486 (19) | 0.0031 (12) | 0.0026 (14) | 0.0010 (14) |
C13 | 0.068 (2) | 0.088 (3) | 0.039 (2) | 0.004 (2) | −0.0011 (18) | −0.0003 (19) |
C14 | 0.054 (2) | 0.080 (3) | 0.040 (2) | 0.0005 (19) | −0.0008 (16) | −0.0161 (19) |
Geometric parameters (Å, º) top
Mn—O3i | 2.1655 (19) | C3—C4 | 1.391 (4) |
Mn—O2W | 2.184 (2) | C3—H3A | 0.9300 |
Mn—O1W | 2.206 (2) | C4—C12 | 1.401 (4) |
Mn—N2 | 2.279 (2) | C4—C5 | 1.426 (4) |
Mn—N1 | 2.296 (2) | C5—C6 | 1.321 (5) |
Mn—S1 | 2.6306 (9) | C5—H5A | 0.9300 |
S1—S2 | 1.9719 (11) | C6—C7 | 1.424 (4) |
S2—O1 | 1.4648 (19) | C6—H6A | 0.9300 |
S2—O2 | 1.4663 (19) | C7—C8 | 1.392 (4) |
S2—O3 | 1.4763 (19) | C7—C11 | 1.411 (4) |
O3—Mnii | 2.1655 (19) | C8—C9 | 1.344 (4) |
O1W—H1WA | 0.93 (4) | C8—H8A | 0.9300 |
O1W—H1WB | 0.78 (3) | C9—C10 | 1.406 (4) |
O2W—H2WA | 0.85 (4) | C9—H9A | 0.9300 |
O2W—H2WB | 0.82 (3) | C10—C13 | 1.499 (4) |
N1—C1 | 1.331 (3) | C11—C12 | 1.437 (4) |
N1—C12 | 1.362 (3) | C13—H13A | 0.9600 |
N2—C10 | 1.326 (4) | C13—H13B | 0.9600 |
N2—C11 | 1.358 (3) | C13—H13C | 0.9600 |
C1—C2 | 1.401 (4) | C14—H14A | 0.9600 |
C1—C14 | 1.492 (4) | C14—H14B | 0.9600 |
C2—C3 | 1.348 (4) | C14—H14C | 0.9600 |
C2—H2A | 0.9300 | | |
| | | |
O3i—Mn—O2W | 89.76 (9) | C2—C3—H3A | 120.0 |
O3i—Mn—O1W | 87.11 (9) | C4—C3—H3A | 120.0 |
O2W—Mn—O1W | 83.61 (9) | C3—C4—C12 | 117.7 (3) |
O3i—Mn—N2 | 89.31 (8) | C3—C4—C5 | 122.1 (3) |
O2W—Mn—N2 | 102.11 (9) | C12—C4—C5 | 120.2 (3) |
O1W—Mn—N2 | 173.24 (9) | C6—C5—C4 | 121.1 (3) |
O3i—Mn—N1 | 95.60 (8) | C6—C5—H5A | 119.4 |
O2W—Mn—N1 | 173.42 (9) | C4—C5—H5A | 119.4 |
O1W—Mn—N1 | 100.44 (9) | C5—C6—C7 | 121.1 (3) |
N2—Mn—N1 | 74.20 (8) | C5—C6—H6A | 119.5 |
O3i—Mn—S1 | 175.80 (6) | C7—C6—H6A | 119.5 |
O2W—Mn—S1 | 90.62 (7) | C8—C7—C11 | 117.0 (3) |
O1W—Mn—S1 | 97.08 (8) | C8—C7—C6 | 123.1 (3) |
N2—Mn—S1 | 86.53 (6) | C11—C7—C6 | 119.9 (3) |
N1—Mn—S1 | 83.76 (6) | C9—C8—C7 | 120.9 (3) |
S2—S1—Mn | 115.36 (4) | C9—C8—H8A | 119.5 |
O1—S2—O2 | 109.60 (12) | C7—C8—H8A | 119.5 |
O1—S2—O3 | 110.13 (12) | C8—C9—C10 | 119.4 (3) |
O2—S2—O3 | 109.89 (12) | C8—C9—H9A | 120.3 |
O1—S2—S1 | 109.86 (9) | C10—C9—H9A | 120.3 |
O2—S2—S1 | 109.85 (9) | N2—C10—C9 | 121.7 (3) |
O3—S2—S1 | 107.48 (10) | N2—C10—C13 | 119.3 (3) |
S2—O3—Mnii | 138.71 (12) | C9—C10—C13 | 119.0 (3) |
Mn—O1W—H1WA | 104 (2) | N2—C11—C7 | 121.9 (3) |
Mn—O1W—H1WB | 126 (2) | N2—C11—C12 | 119.2 (2) |
H1WA—O1W—H1WB | 102 (3) | C7—C11—C12 | 118.8 (3) |
Mn—O2W—H2WA | 106 (2) | N1—C12—C4 | 122.1 (3) |
Mn—O2W—H2WB | 118 (2) | N1—C12—C11 | 119.0 (2) |
H2WA—O2W—H2WB | 105 (3) | C4—C12—C11 | 118.9 (3) |
C1—N1—C12 | 118.6 (2) | C10—C13—H13A | 109.5 |
C1—N1—Mn | 128.34 (18) | C10—C13—H13B | 109.5 |
C12—N1—Mn | 112.90 (18) | H13A—C13—H13B | 109.5 |
C10—N2—C11 | 119.1 (2) | C10—C13—H13C | 109.5 |
C10—N2—Mn | 127.12 (19) | H13A—C13—H13C | 109.5 |
C11—N2—Mn | 113.40 (18) | H13B—C13—H13C | 109.5 |
N1—C1—C2 | 121.6 (3) | C1—C14—H14A | 109.5 |
N1—C1—C14 | 119.2 (2) | C1—C14—H14B | 109.5 |
C2—C1—C14 | 119.1 (3) | H14A—C14—H14B | 109.5 |
C3—C2—C1 | 119.9 (3) | C1—C14—H14C | 109.5 |
C3—C2—H2A | 120.0 | H14A—C14—H14C | 109.5 |
C1—C2—H2A | 120.0 | H14B—C14—H14C | 109.5 |
C2—C3—C4 | 120.0 (3) | | |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O1i | 0.93 (4) | 1.81 (4) | 2.714 (3) | 164 (3) |
O1W—H1WB···O1iii | 0.79 (3) | 1.96 (3) | 2.747 (3) | 173 (3) |
O2W—H2WA···O2 | 0.84 (4) | 1.83 (4) | 2.662 (3) | 173 (4) |
O2W—H2WB···O2iii | 0.83 (3) | 1.93 (3) | 2.752 (3) | 175 (3) |
Symmetry codes: (i) x, y−1, z; (iii) −x+3/2, y−1/2, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Mn(S2O3)(C12H8N2)2]·CH4O | [Mn(S2O3)(C14H12N2)(H2O)2] |
Mr | 559.51 | 411.35 |
Crystal system, space group | Monoclinic, P21/n | Orthorhombic, Pbca |
Temperature (K) | 293 | 293 |
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), 90 | 90, 90, 90 |
V (Å3) | 2379.9 (3) | 3281.9 (4) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.77 | 1.09 |
Crystal size (mm) | 0.18 × 0.14 × 0.12 | 0.26 × 0.20 × 0.10 |
|
Data collection |
Diffractometer | Bruker CCD area-detector diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 2000) | Part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 2000) |
Tmin, Tmax | 0.88, 0.91 | 0.82, 0.90 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11546, 5302, 3942 | 18352, 3810, 2341 |
Rint | 0.030 | 0.061 |
(sin θ/λ)max (Å−1) | 0.661 | 0.662 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.125, 1.00 | 0.041, 0.087, 0.85 |
No. of reflections | 5302 | 3810 |
No. of parameters | 330 | 235 |
No. of restraints | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.68, −0.28 | 0.52, −0.40 |
Selected geometric parameters (Å, º) for (I) topMn—O1 | 2.1637 (18) | Mn—S2 | 2.6131 (8) |
Mn—N1A | 2.246 (2) | S1—O2 | 1.4466 (18) |
Mn—N2B | 2.258 (2) | S1—O3 | 1.449 (2) |
Mn—N2A | 2.261 (2) | S1—O1 | 1.4893 (18) |
Mn—N1B | 2.302 (2) | S1—S2 | 2.0175 (9) |
| | | |
O1—Mn—N1A | 92.71 (7) | N1A—Mn—S2 | 108.42 (5) |
O1—Mn—N2B | 103.93 (8) | N2B—Mn—S2 | 93.31 (6) |
N1A—Mn—N2B | 156.20 (8) | N2A—Mn—S2 | 96.45 (5) |
O1—Mn—N2A | 157.67 (7) | N1B—Mn—S2 | 155.95 (5) |
N1A—Mn—N2A | 73.92 (7) | O2—S1—O3 | 111.79 (14) |
N2B—Mn—N2A | 94.57 (8) | O2—S1—O1 | 109.98 (12) |
O1—Mn—N1B | 93.40 (7) | O3—S1—O1 | 110.15 (12) |
N1A—Mn—N1B | 89.49 (7) | O2—S1—S2 | 110.39 (8) |
N2B—Mn—N1B | 72.88 (8) | O3—S1—S2 | 110.43 (10) |
N2A—Mn—N1B | 104.06 (8) | O1—S1—S2 | 103.82 (8) |
O1—Mn—S2 | 70.44 (5) | | |
Mean values for selected distances and angles (Å, °) for selected parameters
in the S2O3 geometry according to the type of coordination topCoordination type | S—S | S—Ocoord | S—Ouncoord | S—S—Ocoord | S—S—Ouncoord | CSD |
S-Monodentate | 2.054 (37) | | 1.453 (16) | | 106.9(2.3) | 19 |
S,O-Chelating | 2.018 (20) | 1.510 (22) | 1.447 (6) | 101.1(3.0) | 110.6(1.1) | 7 |
S,O-Bridging | 2.009 (8) | 1.479 (15) | 1.467 (12) | 108.5(1.0) | 108.9(1.2) | 5 |
Ionic | 1.992 (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) topMn—O3i | 2.1655 (19) | Mn—S1 | 2.6306 (9) |
Mn—O2W | 2.184 (2) | S1—S2 | 1.9719 (11) |
Mn—O1W | 2.206 (2) | S2—O1 | 1.4648 (19) |
Mn—N2 | 2.279 (2) | S2—O2 | 1.4663 (19) |
Mn—N1 | 2.296 (2) | S2—O3 | 1.4763 (19) |
| | | |
O3i—Mn—O2W | 89.76 (9) | O2W—Mn—S1 | 90.62 (7) |
O3i—Mn—O1W | 87.11 (9) | O1W—Mn—S1 | 97.08 (8) |
O2W—Mn—O1W | 83.61 (9) | N2—Mn—S1 | 86.53 (6) |
O3i—Mn—N2 | 89.31 (8) | N1—Mn—S1 | 83.76 (6) |
O2W—Mn—N2 | 102.11 (9) | O1—S2—O2 | 109.60 (12) |
O1W—Mn—N2 | 173.24 (9) | O1—S2—O3 | 110.13 (12) |
O3i—Mn—N1 | 95.60 (8) | O2—S2—O3 | 109.89 (12) |
O2W—Mn—N1 | 173.42 (9) | O1—S2—S1 | 109.86 (9) |
O1W—Mn—N1 | 100.44 (9) | O2—S2—S1 | 109.85 (9) |
N2—Mn—N1 | 74.20 (8) | O3—S2—S1 | 107.48 (10) |
O3i—Mn—S1 | 175.80 (6) | | |
Symmetry code: (i) x, y−1, z. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O1i | 0.93 (4) | 1.81 (4) | 2.714 (3) | 164 (3) |
O1W—H1WB···O1ii | 0.79 (3) | 1.96 (3) | 2.747 (3) | 173 (3) |
O2W—H2WA···O2 | 0.84 (4) | 1.83 (4) | 2.662 (3) | 173 (4) |
O2W—H2WB···O2ii | 0.83 (3) | 1.93 (3) | 2.752 (3) | 175 (3) |
Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y−1/2, z. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
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 π–π-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.