Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101016481/bk1621sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101016481/bk1621Isup2.hkl |
CCDC reference: 179259
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).
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.
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.
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).
[Mn(C15H11N3)2](S4O6)·3H2O | F(000) = 1644 |
Mr = 799.76 | Dx = 1.513 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.783 (3) Å | Cell parameters from 25 reflections |
b = 18.594 (7) Å | θ = 7.5–15° |
c = 21.556 (12) Å | µ = 0.67 mm−1 |
β = 94.05 (4)° | T = 293 K |
V = 3512 (3) Å3 | Plates, yellow |
Z = 4 | 0.48 × 0.32 × 0.12 mm |
Siemens R3m diffractometer | 3567 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.058 |
Graphite monochromator | θmax = 25.0°, θmin = 1.9° |
ω/2θ scans | h = −10→10 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→22 |
Tmin = 0.77, Tmax = 0.92 | l = 0→25 |
6852 measured reflections | 2 standard reflections every 98 reflections |
6187 independent reflections | intensity decay: <2% |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.124 | H 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 parameters | Δρmax = 0.27 e Å−3 |
9 restraints | Δρmin = −0.25 e Å−3 |
[Mn(C15H11N3)2](S4O6)·3H2O | V = 3512 (3) Å3 |
Mr = 799.76 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.783 (3) Å | µ = 0.67 mm−1 |
b = 18.594 (7) Å | T = 293 K |
c = 21.556 (12) Å | 0.48 × 0.32 × 0.12 mm |
β = 94.05 (4)° |
Siemens R3m diffractometer | 3567 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.058 |
Tmin = 0.77, Tmax = 0.92 | 2 standard reflections every 98 reflections |
6852 measured reflections | intensity decay: <2% |
6187 independent reflections |
R[F2 > 2σ(F2)] = 0.053 | 9 restraints |
wR(F2) = 0.124 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.27 e Å−3 |
6187 reflections | Δρmin = −0.25 e Å−3 |
469 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.73909 (6) | 0.90700 (3) | 0.73746 (3) | 0.04484 (18) | |
S1 | 0.79113 (14) | 1.11698 (7) | 0.56935 (5) | 0.0647 (3) | |
S4 | 0.9361 (2) | 1.34439 (15) | 0.54085 (9) | 0.1375 (8) | |
S2 | 0.83764 (18) | 1.21068 (9) | 0.62393 (6) | 0.0915 (5) | |
S3 | 1.02169 (18) | 1.25314 (11) | 0.58972 (8) | 0.1144 (6) | |
O1 | 0.7645 (4) | 1.13928 (19) | 0.50672 (13) | 0.0815 (10) | |
O2 | 0.6585 (4) | 1.0915 (2) | 0.59754 (16) | 0.0972 (11) | |
O3 | 0.9210 (4) | 1.0718 (2) | 0.57962 (18) | 0.1211 (15) | |
O4 | 0.8989 (9) | 1.3953 (3) | 0.5885 (3) | 0.223 (3) | |
O5 | 0.8120 (6) | 1.3254 (3) | 0.5008 (2) | 0.224 (4) | |
O6 | 1.0646 (6) | 1.3702 (4) | 0.5107 (3) | 0.204 (3) | |
N1A | 0.6491 (4) | 0.7966 (2) | 0.76096 (17) | 0.0573 (9) | |
N2A | 0.6966 (4) | 0.9053 (2) | 0.83637 (15) | 0.0631 (10) | |
N3A | 0.8180 (4) | 1.0128 (2) | 0.77742 (17) | 0.0603 (10) | |
C1A | 0.6375 (5) | 0.7408 (3) | 0.7220 (2) | 0.0698 (13) | |
H1AA | 0.6716 | 0.7469 | 0.6825 | 0.084* | |
C2A | 0.5783 (6) | 0.6745 (3) | 0.7365 (3) | 0.0989 (19) | |
H2AA | 0.5691 | 0.6379 | 0.7070 | 0.119* | |
C3A | 0.5346 (7) | 0.6647 (4) | 0.7941 (4) | 0.114 (2) | |
H3AA | 0.4961 | 0.6204 | 0.8055 | 0.137* | |
C4A | 0.5467 (6) | 0.7196 (4) | 0.8360 (3) | 0.0875 (18) | |
H4AA | 0.5164 | 0.7127 | 0.8761 | 0.105* | |
C5A | 0.6052 (5) | 0.7869 (3) | 0.8187 (2) | 0.0669 (13) | |
C6A | 0.6212 (5) | 0.8487 (4) | 0.8587 (2) | 0.0788 (17) | |
C7A | 0.5605 (7) | 0.8537 (5) | 0.9175 (3) | 0.117 (2) | |
H7AA | 0.5055 | 0.8160 | 0.9334 | 0.141* | |
C8A | 0.5862 (10) | 0.9171 (6) | 0.9508 (3) | 0.149 (4) | |
H8AA | 0.5474 | 0.9213 | 0.9896 | 0.179* | |
C9A | 0.6658 (9) | 0.9733 (5) | 0.9288 (3) | 0.125 (3) | |
H9AA | 0.6841 | 1.0149 | 0.9520 | 0.150* | |
C10A | 0.7190 (6) | 0.9650 (4) | 0.8692 (2) | 0.0822 (17) | |
C11A | 0.8050 (6) | 1.0237 (3) | 0.8388 (2) | 0.0761 (15) | |
C12A | 0.8693 (9) | 1.0834 (4) | 0.8679 (3) | 0.122 (3) | |
H12A | 0.8581 | 1.0906 | 0.9100 | 0.146* | |
C13A | 0.9484 (9) | 1.1319 (4) | 0.8361 (5) | 0.134 (3) | |
H13A | 0.9976 | 1.1702 | 0.8568 | 0.161* | |
C14A | 0.9554 (7) | 1.1242 (3) | 0.7738 (4) | 0.107 (2) | |
H14A | 1.0029 | 1.1583 | 0.7502 | 0.129* | |
C15A | 0.8881 (6) | 1.0626 (3) | 0.7466 (3) | 0.0747 (14) | |
H15A | 0.8933 | 1.0564 | 0.7040 | 0.090* | |
N1B | 0.5121 (3) | 0.94978 (17) | 0.69894 (14) | 0.0444 (8) | |
N2B | 0.7332 (3) | 0.89997 (16) | 0.63631 (12) | 0.0380 (7) | |
N3B | 0.9664 (3) | 0.86567 (17) | 0.71327 (14) | 0.0455 (8) | |
C1B | 0.4056 (5) | 0.9758 (2) | 0.7339 (2) | 0.0626 (12) | |
H1BA | 0.4248 | 0.9766 | 0.7769 | 0.075* | |
C2B | 0.2694 (5) | 1.0012 (3) | 0.7087 (2) | 0.0677 (13) | |
H2BA | 0.1978 | 1.0193 | 0.7344 | 0.081* | |
C3B | 0.2378 (5) | 1.0003 (2) | 0.6462 (3) | 0.0714 (14) | |
H3BA | 0.1454 | 1.0179 | 0.6287 | 0.086* | |
C4B | 0.3463 (5) | 0.9727 (2) | 0.6092 (2) | 0.0648 (13) | |
H4BA | 0.3271 | 0.9704 | 0.5662 | 0.078* | |
C5B | 0.4833 (4) | 0.9484 (2) | 0.63695 (18) | 0.0461 (10) | |
C6B | 0.6095 (4) | 0.9201 (2) | 0.60085 (17) | 0.0432 (9) | |
C7B | 0.6054 (5) | 0.9146 (2) | 0.53711 (18) | 0.0591 (11) | |
H7BA | 0.5180 | 0.9280 | 0.5130 | 0.071* | |
C8B | 0.7321 (6) | 0.8888 (3) | 0.50876 (19) | 0.0687 (14) | |
H8BA | 0.7307 | 0.8849 | 0.4657 | 0.082* | |
C9B | 0.8588 (5) | 0.8694 (2) | 0.54542 (18) | 0.0588 (12) | |
H9BA | 0.9454 | 0.8529 | 0.5274 | 0.071* | |
C10B | 0.8575 (4) | 0.8742 (2) | 0.60905 (17) | 0.0426 (9) | |
C11B | 0.9862 (4) | 0.8533 (2) | 0.65286 (17) | 0.0443 (9) | |
C12B | 1.1187 (5) | 0.8213 (2) | 0.6342 (2) | 0.0605 (12) | |
H12B | 1.1305 | 0.8127 | 0.5923 | 0.073* | |
C13B | 1.2318 (5) | 0.8027 (3) | 0.6785 (2) | 0.0719 (14) | |
H13B | 1.3203 | 0.7806 | 0.6667 | 0.086* | |
C14B | 1.2150 (5) | 0.8162 (3) | 0.7389 (2) | 0.0676 (13) | |
H14B | 1.2925 | 0.8049 | 0.7690 | 0.081* | |
C15B | 1.0815 (5) | 0.8471 (2) | 0.7557 (2) | 0.0606 (12) | |
H15B | 1.0696 | 0.8555 | 0.7977 | 0.073* | |
O1W | 0.5605 (5) | 1.2532 (3) | 0.4533 (2) | 0.1218 (15) | |
H1WA | 0.592 (4) | 1.220 (1) | 0.482 (1) | 0.146* | |
H1WB | 0.603 (4) | 1.2968 (7) | 0.461 (1) | 0.146* | |
O2W | 0.2695 (6) | 1.3164 (3) | 0.41982 (19) | 0.1432 (18) | |
H2WA | 0.341 (3) | 1.283 (2) | 0.429 (1) | 0.172* | |
H2WB | 0.208 (3) | 1.325 (2) | 0.451 (1) | 0.172* | |
O3W | 0.2949 (9) | 1.4719 (5) | 0.3711 (3) | 0.116 (3) | |
H3WA | 0.346 (2) | 1.4328 (7) | 0.386 (1) | 0.139* | |
H3WB | 0.241 (7) | 1.493 (2) | 0.401 (1) | 0.139* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0439 (3) | 0.0499 (4) | 0.0409 (3) | 0.0037 (3) | 0.0041 (2) | 0.0013 (3) |
S1 | 0.0595 (7) | 0.0744 (9) | 0.0599 (7) | 0.0068 (6) | 0.0017 (5) | −0.0152 (6) |
S4 | 0.1168 (14) | 0.208 (2) | 0.0860 (11) | −0.0610 (16) | −0.0036 (10) | 0.0350 (14) |
S2 | 0.1095 (11) | 0.0962 (12) | 0.0708 (8) | −0.0195 (9) | 0.0194 (8) | −0.0281 (8) |
S3 | 0.0778 (10) | 0.1383 (16) | 0.1265 (13) | −0.0238 (11) | 0.0031 (9) | −0.0361 (12) |
O1 | 0.087 (2) | 0.092 (3) | 0.065 (2) | −0.011 (2) | 0.0000 (17) | −0.0057 (18) |
O2 | 0.099 (3) | 0.091 (3) | 0.106 (3) | −0.012 (2) | 0.039 (2) | −0.013 (2) |
O3 | 0.101 (3) | 0.134 (4) | 0.124 (3) | 0.055 (3) | −0.026 (2) | −0.038 (3) |
O4 | 0.377 (11) | 0.157 (6) | 0.140 (5) | 0.023 (6) | 0.051 (6) | −0.005 (4) |
O5 | 0.236 (6) | 0.257 (7) | 0.161 (5) | −0.156 (6) | −0.106 (5) | 0.115 (5) |
O6 | 0.161 (5) | 0.271 (8) | 0.182 (5) | −0.096 (5) | 0.028 (4) | 0.039 (5) |
N1A | 0.052 (2) | 0.052 (3) | 0.068 (2) | 0.0036 (18) | 0.0118 (18) | 0.017 (2) |
N2A | 0.063 (2) | 0.084 (3) | 0.0420 (19) | 0.023 (2) | 0.0019 (17) | 0.000 (2) |
N3A | 0.060 (2) | 0.055 (3) | 0.064 (2) | 0.013 (2) | −0.0084 (18) | −0.014 (2) |
C1A | 0.064 (3) | 0.052 (3) | 0.095 (4) | 0.004 (3) | 0.017 (3) | 0.016 (3) |
C2A | 0.094 (4) | 0.049 (4) | 0.157 (6) | 0.004 (3) | 0.035 (4) | 0.023 (4) |
C3A | 0.089 (4) | 0.073 (5) | 0.183 (8) | 0.014 (4) | 0.038 (5) | 0.048 (5) |
C4A | 0.063 (3) | 0.089 (5) | 0.113 (5) | 0.021 (3) | 0.029 (3) | 0.057 (4) |
C5A | 0.053 (3) | 0.070 (4) | 0.080 (3) | 0.020 (3) | 0.024 (2) | 0.027 (3) |
C6A | 0.060 (3) | 0.119 (5) | 0.060 (3) | 0.040 (3) | 0.024 (2) | 0.040 (3) |
C7A | 0.125 (5) | 0.157 (7) | 0.076 (4) | 0.039 (5) | 0.049 (4) | 0.038 (4) |
C8A | 0.192 (8) | 0.200 (10) | 0.061 (4) | 0.095 (8) | 0.051 (5) | 0.013 (5) |
C9A | 0.166 (7) | 0.150 (7) | 0.061 (4) | 0.070 (6) | 0.015 (4) | 0.000 (4) |
C10A | 0.097 (4) | 0.099 (5) | 0.049 (3) | 0.048 (4) | −0.003 (3) | −0.015 (3) |
C11A | 0.082 (4) | 0.069 (4) | 0.073 (3) | 0.031 (3) | −0.024 (3) | −0.024 (3) |
C12A | 0.149 (7) | 0.102 (6) | 0.107 (5) | 0.021 (5) | −0.040 (5) | −0.060 (5) |
C13A | 0.130 (7) | 0.070 (5) | 0.191 (9) | 0.014 (5) | −0.078 (6) | −0.043 (6) |
C14A | 0.094 (4) | 0.063 (4) | 0.157 (6) | 0.001 (3) | −0.043 (4) | 0.000 (4) |
C15A | 0.067 (3) | 0.059 (4) | 0.097 (4) | 0.007 (3) | −0.005 (3) | −0.012 (3) |
N1B | 0.0384 (17) | 0.039 (2) | 0.056 (2) | 0.0042 (15) | 0.0061 (15) | −0.0035 (16) |
N2B | 0.0417 (17) | 0.0287 (18) | 0.0430 (16) | −0.0001 (15) | 0.0006 (13) | −0.0008 (14) |
N3B | 0.0419 (18) | 0.041 (2) | 0.0537 (19) | 0.0030 (16) | 0.0018 (15) | 0.0079 (16) |
C1B | 0.053 (3) | 0.043 (3) | 0.092 (3) | 0.005 (2) | 0.009 (2) | 0.000 (2) |
C2B | 0.056 (3) | 0.058 (3) | 0.091 (4) | 0.011 (2) | 0.013 (3) | 0.002 (3) |
C3B | 0.041 (3) | 0.049 (3) | 0.124 (4) | 0.009 (2) | −0.002 (3) | 0.013 (3) |
C4B | 0.048 (3) | 0.050 (3) | 0.093 (3) | 0.002 (2) | −0.017 (2) | 0.004 (3) |
C5B | 0.044 (2) | 0.030 (2) | 0.064 (3) | −0.0018 (19) | 0.0043 (19) | 0.001 (2) |
C6B | 0.043 (2) | 0.034 (2) | 0.051 (2) | −0.0048 (18) | −0.0079 (17) | 0.0011 (18) |
C7B | 0.056 (3) | 0.066 (3) | 0.054 (2) | −0.002 (2) | −0.012 (2) | 0.003 (2) |
C8B | 0.085 (3) | 0.078 (4) | 0.044 (2) | 0.001 (3) | 0.008 (2) | 0.000 (2) |
C9B | 0.073 (3) | 0.055 (3) | 0.050 (2) | 0.012 (2) | 0.015 (2) | 0.000 (2) |
C10B | 0.049 (2) | 0.034 (2) | 0.046 (2) | 0.0001 (19) | 0.0047 (18) | −0.0026 (18) |
C11B | 0.042 (2) | 0.038 (2) | 0.055 (2) | 0.0008 (19) | 0.0117 (18) | 0.0010 (19) |
C12B | 0.056 (3) | 0.053 (3) | 0.074 (3) | 0.007 (2) | 0.018 (2) | 0.003 (2) |
C13B | 0.056 (3) | 0.065 (3) | 0.095 (4) | 0.028 (3) | 0.007 (3) | 0.016 (3) |
C14B | 0.039 (2) | 0.078 (4) | 0.085 (3) | 0.003 (2) | −0.006 (2) | 0.025 (3) |
C15B | 0.061 (3) | 0.062 (3) | 0.057 (3) | −0.003 (2) | −0.006 (2) | 0.012 (2) |
O1W | 0.100 (3) | 0.103 (3) | 0.161 (4) | 0.017 (3) | −0.001 (3) | −0.015 (3) |
O2W | 0.129 (4) | 0.201 (6) | 0.099 (3) | 0.030 (4) | 0.005 (3) | 0.005 (3) |
O3W | 0.131 (4) | 0.140 (5) | 0.081 (3) | −0.067 (5) | 0.023 (3) | −0.005 (3) |
Mn1—N2B | 2.181 (3) | C13A—H13A | 0.9300 |
Mn1—N2A | 2.191 (3) | C14A—C15A | 1.399 (7) |
Mn1—N3B | 2.235 (3) | C14A—H14A | 0.9300 |
Mn1—N3A | 2.238 (4) | C15A—H15A | 0.9300 |
Mn1—N1B | 2.250 (3) | N1B—C1B | 1.333 (5) |
Mn1—N1A | 2.270 (4) | N1B—C5B | 1.343 (5) |
S1—O1 | 1.416 (3) | N2B—C6B | 1.337 (4) |
S1—O3 | 1.421 (3) | N2B—C10B | 1.363 (4) |
S1—O2 | 1.432 (3) | N3B—C11B | 1.345 (4) |
S1—S2 | 2.126 (2) | N3B—C15B | 1.360 (5) |
S4—O5 | 1.387 (4) | C1B—C2B | 1.364 (6) |
S4—O6 | 1.425 (4) | C1B—H1BA | 0.9300 |
S4—O4 | 1.451 (5) | C2B—C3B | 1.354 (6) |
S4—S3 | 2.108 (3) | C2B—H2BA | 0.9300 |
S2—S3 | 1.987 (2) | C3B—C4B | 1.385 (6) |
N1A—C1A | 1.333 (6) | C3B—H3BA | 0.9300 |
N1A—C5A | 1.341 (5) | C4B—C5B | 1.382 (5) |
N2A—C10A | 1.323 (6) | C4B—H4BA | 0.9300 |
N2A—C6A | 1.349 (6) | C5B—C6B | 1.494 (5) |
N3A—C15A | 1.317 (6) | C6B—C7B | 1.376 (5) |
N3A—C11A | 1.350 (6) | C7B—C8B | 1.392 (6) |
C1A—C2A | 1.381 (7) | C7B—H7BA | 0.9300 |
C1A—H1AA | 0.9300 | C8B—C9B | 1.367 (6) |
C2A—C3A | 1.338 (8) | C8B—H8BA | 0.9300 |
C2A—H2AA | 0.9300 | C9B—C10B | 1.375 (5) |
C3A—C4A | 1.363 (8) | C9B—H9BA | 0.9300 |
C3A—H3AA | 0.9300 | C10B—C11B | 1.473 (5) |
C4A—C5A | 1.413 (7) | C11B—C12B | 1.392 (5) |
C4A—H4AA | 0.9300 | C12B—C13B | 1.372 (6) |
C5A—C6A | 1.438 (7) | C12B—H12B | 0.9300 |
C6A—C7A | 1.414 (7) | C13B—C14B | 1.345 (6) |
C7A—C8A | 1.388 (11) | C13B—H13B | 0.9300 |
C7A—H7AA | 0.9300 | C14B—C15B | 1.377 (6) |
C8A—C9A | 1.361 (11) | C14B—H14B | 0.9300 |
C8A—H8AA | 0.9300 | C15B—H15B | 0.9300 |
C9A—C10A | 1.406 (7) | O1W—H1WA | 0.90 (2) |
C9A—H9AA | 0.9300 | O1W—H1WB | 0.903 (19) |
C10A—C11A | 1.503 (8) | O2W—H2WA | 0.90 (3) |
C11A—C12A | 1.378 (8) | O2W—H2WB | 0.90 (3) |
C12A—C13A | 1.354 (10) | O3W—H3WA | 0.90 (2) |
C12A—H12A | 0.9300 | O3W—H3WB | 0.91 (4) |
C13A—C14A | 1.356 (9) | ||
N2B—Mn1—N2A | 168.07 (13) | C12A—C11A—C10A | 126.1 (6) |
N2B—Mn1—N3B | 72.83 (11) | C13A—C12A—C11A | 121.0 (7) |
N2A—Mn1—N3B | 116.01 (12) | C13A—C12A—H12A | 119.5 |
N2B—Mn1—N3A | 114.98 (13) | C11A—C12A—H12A | 119.5 |
N2A—Mn1—N3A | 72.99 (16) | C12A—C13A—C14A | 119.4 (7) |
N3B—Mn1—N3A | 97.75 (13) | C12A—C13A—H13A | 120.3 |
N2B—Mn1—N1B | 72.21 (11) | C14A—C13A—H13A | 120.3 |
N2A—Mn1—N1B | 99.01 (12) | C13A—C14A—C15A | 117.0 (7) |
N3B—Mn1—N1B | 144.91 (11) | C13A—C14A—H14A | 121.5 |
N3A—Mn1—N1B | 94.21 (12) | C15A—C14A—H14A | 121.5 |
N2B—Mn1—N1A | 100.65 (13) | N3A—C15A—C14A | 124.2 (6) |
N2A—Mn1—N1A | 71.57 (16) | N3A—C15A—H15A | 117.9 |
N3B—Mn1—N1A | 94.12 (12) | C14A—C15A—H15A | 117.9 |
N3A—Mn1—N1A | 144.34 (14) | C1B—N1B—C5B | 118.7 (3) |
N1B—Mn1—N1A | 95.09 (12) | C1B—N1B—Mn1 | 123.9 (3) |
O1—S1—O3 | 113.5 (2) | C5B—N1B—Mn1 | 117.4 (2) |
O1—S1—O2 | 114.6 (2) | C6B—N2B—C10B | 119.7 (3) |
O3—S1—O2 | 114.0 (3) | C6B—N2B—Mn1 | 121.0 (2) |
O1—S1—S2 | 107.47 (16) | C10B—N2B—Mn1 | 119.3 (2) |
O3—S1—S2 | 106.10 (18) | C11B—N3B—C15B | 117.9 (3) |
O2—S1—S2 | 99.59 (16) | C11B—N3B—Mn1 | 117.6 (2) |
O5—S4—O6 | 114.5 (3) | C15B—N3B—Mn1 | 124.4 (3) |
O5—S4—O4 | 113.6 (4) | N1B—C1B—C2B | 122.1 (4) |
O6—S4—O4 | 109.2 (4) | N1B—C1B—H1BA | 119.0 |
O5—S4—S3 | 110.1 (3) | C2B—C1B—H1BA | 119.0 |
O6—S4—S3 | 103.4 (3) | C3B—C2B—C1B | 120.3 (4) |
O4—S4—S3 | 105.2 (3) | C3B—C2B—H2BA | 119.8 |
S3—S2—S1 | 104.47 (9) | C1B—C2B—H2BA | 119.8 |
S2—S3—S4 | 103.56 (11) | C2B—C3B—C4B | 118.5 (4) |
C1A—N1A—C5A | 117.8 (4) | C2B—C3B—H3BA | 120.8 |
C1A—N1A—Mn1 | 125.1 (3) | C4B—C3B—H3BA | 120.8 |
C5A—N1A—Mn1 | 117.1 (3) | C5B—C4B—C3B | 119.0 (4) |
C10A—N2A—C6A | 121.4 (5) | C5B—C4B—H4BA | 120.5 |
C10A—N2A—Mn1 | 118.6 (4) | C3B—C4B—H4BA | 120.5 |
C6A—N2A—Mn1 | 118.7 (3) | N1B—C5B—C4B | 121.5 (4) |
C15A—N3A—C11A | 117.6 (5) | N1B—C5B—C6B | 115.5 (3) |
C15A—N3A—Mn1 | 124.5 (3) | C4B—C5B—C6B | 123.0 (4) |
C11A—N3A—Mn1 | 117.5 (4) | N2B—C6B—C7B | 120.8 (4) |
N1A—C1A—C2A | 124.4 (5) | N2B—C6B—C5B | 113.8 (3) |
N1A—C1A—H1AA | 117.8 | C7B—C6B—C5B | 125.4 (3) |
C2A—C1A—H1AA | 117.8 | C6B—C7B—C8B | 119.9 (4) |
C3A—C2A—C1A | 117.9 (7) | C6B—C7B—H7BA | 120.0 |
C3A—C2A—H2AA | 121.0 | C8B—C7B—H7BA | 120.0 |
C1A—C2A—H2AA | 121.0 | C9B—C8B—C7B | 118.7 (4) |
C2A—C3A—C4A | 119.9 (6) | C9B—C8B—H8BA | 120.6 |
C2A—C3A—H3AA | 120.0 | C7B—C8B—H8BA | 120.6 |
C4A—C3A—H3AA | 120.0 | C8B—C9B—C10B | 119.7 (4) |
C3A—C4A—C5A | 120.0 (6) | C8B—C9B—H9BA | 120.1 |
C3A—C4A—H4AA | 120.0 | C10B—C9B—H9BA | 120.1 |
C5A—C4A—H4AA | 120.0 | N2B—C10B—C9B | 121.1 (4) |
N1A—C5A—C4A | 119.9 (5) | N2B—C10B—C11B | 114.7 (3) |
N1A—C5A—C6A | 115.2 (4) | C9B—C10B—C11B | 124.2 (4) |
C4A—C5A—C6A | 124.9 (5) | N3B—C11B—C12B | 121.3 (4) |
N2A—C6A—C7A | 119.6 (6) | N3B—C11B—C10B | 115.5 (3) |
N2A—C6A—C5A | 116.1 (4) | C12B—C11B—C10B | 123.2 (4) |
C7A—C6A—C5A | 124.3 (6) | C13B—C12B—C11B | 119.1 (4) |
C8A—C7A—C6A | 117.4 (7) | C13B—C12B—H12B | 120.5 |
C8A—C7A—H7AA | 121.3 | C11B—C12B—H12B | 120.5 |
C6A—C7A—H7AA | 121.3 | C14B—C13B—C12B | 120.2 (4) |
C9A—C8A—C7A | 122.7 (6) | C14B—C13B—H13B | 119.9 |
C9A—C8A—H8AA | 118.6 | C12B—C13B—H13B | 119.9 |
C7A—C8A—H8AA | 118.6 | C13B—C14B—C15B | 119.1 (4) |
C8A—C9A—C10A | 116.5 (7) | C13B—C14B—H14B | 120.4 |
C8A—C9A—H9AA | 121.7 | C15B—C14B—H14B | 120.4 |
C10A—C9A—H9AA | 121.7 | N3B—C15B—C14B | 122.4 (4) |
N2A—C10A—C9A | 122.2 (7) | N3B—C15B—H15B | 118.8 |
N2A—C10A—C11A | 115.8 (4) | C14B—C15B—H15B | 118.8 |
C9A—C10A—C11A | 122.0 (6) | H1WA—O1W—H1WB | 111.9 (17) |
N3A—C11A—C12A | 120.4 (6) | H2WA—O2W—H2WB | 113 (2) |
N3A—C11A—C10A | 113.5 (4) | H3WA—O3W—H3WB | 112 (2) |
O1—S1—S2—S3 | −60.05 (18) | C11A—N3A—C15A—C14A | 2.8 (7) |
O3—S1—S2—S3 | 61.7 (2) | Mn1—N3A—C15A—C14A | −170.9 (4) |
O2—S1—S2—S3 | −179.81 (18) | C13A—C14A—C15A—N3A | 0.8 (8) |
S1—S2—S3—S4 | 107.09 (12) | N2B—Mn1—N1B—C1B | −178.6 (3) |
O5—S4—S3—S2 | −51.0 (3) | N2A—Mn1—N1B—C1B | 9.7 (3) |
O6—S4—S3—S2 | −173.8 (3) | N3B—Mn1—N1B—C1B | −173.6 (3) |
O4—S4—S3—S2 | 71.7 (3) | N3A—Mn1—N1B—C1B | −63.7 (3) |
N2B—Mn1—N1A—C1A | 14.7 (4) | N1A—Mn1—N1B—C1B | 81.8 (3) |
N2A—Mn1—N1A—C1A | −174.6 (4) | N2B—Mn1—N1B—C5B | 1.8 (3) |
N3B—Mn1—N1A—C1A | −58.5 (4) | N2A—Mn1—N1B—C5B | −169.9 (3) |
N3A—Mn1—N1A—C1A | −167.9 (3) | N3B—Mn1—N1B—C5B | 6.8 (4) |
N1B—Mn1—N1A—C1A | 87.6 (4) | N3A—Mn1—N1B—C5B | 116.7 (3) |
N2B—Mn1—N1A—C5A | −165.7 (3) | N1A—Mn1—N1B—C5B | −97.8 (3) |
N2A—Mn1—N1A—C5A | 4.9 (3) | N2A—Mn1—N2B—C6B | 42.0 (8) |
N3B—Mn1—N1A—C5A | 121.0 (3) | N3B—Mn1—N2B—C6B | −178.7 (3) |
N3A—Mn1—N1A—C5A | 11.6 (4) | N3A—Mn1—N2B—C6B | −88.0 (3) |
N1B—Mn1—N1A—C5A | −92.9 (3) | N1B—Mn1—N2B—C6B | −1.7 (3) |
N2B—Mn1—N2A—C10A | −126.5 (7) | N1A—Mn1—N2B—C6B | 90.3 (3) |
N3B—Mn1—N2A—C10A | 97.4 (3) | N2A—Mn1—N2B—C10B | −137.6 (6) |
N3A—Mn1—N2A—C10A | 7.0 (3) | N3B—Mn1—N2B—C10B | 1.7 (3) |
N1B—Mn1—N2A—C10A | −84.7 (3) | N3A—Mn1—N2B—C10B | 92.4 (3) |
N1A—Mn1—N2A—C10A | −177.1 (4) | N1B—Mn1—N2B—C10B | 178.7 (3) |
N2B—Mn1—N2A—C6A | 40.8 (8) | N1A—Mn1—N2B—C10B | −89.4 (3) |
N3B—Mn1—N2A—C6A | −95.3 (3) | N2B—Mn1—N3B—C11B | −3.4 (3) |
N3A—Mn1—N2A—C6A | 174.2 (3) | N2A—Mn1—N3B—C11B | 168.0 (3) |
N1B—Mn1—N2A—C6A | 82.6 (3) | N3A—Mn1—N3B—C11B | −117.2 (3) |
N1A—Mn1—N2A—C6A | −9.8 (3) | N1B—Mn1—N3B—C11B | −8.4 (4) |
N2B—Mn1—N3A—C15A | −14.7 (4) | N1A—Mn1—N3B—C11B | 96.5 (3) |
N2A—Mn1—N3A—C15A | 174.8 (4) | N2B—Mn1—N3B—C15B | −178.2 (3) |
N3B—Mn1—N3A—C15A | 59.9 (4) | N2A—Mn1—N3B—C15B | −6.8 (4) |
N1B—Mn1—N3A—C15A | −87.1 (4) | N3A—Mn1—N3B—C15B | 68.0 (3) |
N1A—Mn1—N3A—C15A | 168.2 (3) | N1B—Mn1—N3B—C15B | 176.8 (3) |
N2B—Mn1—N3A—C11A | 171.5 (3) | N1A—Mn1—N3B—C15B | −78.3 (3) |
N2A—Mn1—N3A—C11A | 1.0 (3) | C5B—N1B—C1B—C2B | −0.4 (6) |
N3B—Mn1—N3A—C11A | −113.9 (3) | Mn1—N1B—C1B—C2B | 180.0 (3) |
N1B—Mn1—N3A—C11A | 99.2 (3) | N1B—C1B—C2B—C3B | 0.4 (7) |
N1A—Mn1—N3A—C11A | −5.6 (4) | C1B—C2B—C3B—C4B | 0.4 (7) |
C5A—N1A—C1A—C2A | 2.4 (7) | C2B—C3B—C4B—C5B | −1.3 (7) |
Mn1—N1A—C1A—C2A | −178.0 (4) | C1B—N1B—C5B—C4B | −0.5 (6) |
N1A—C1A—C2A—C3A | −2.5 (8) | Mn1—N1B—C5B—C4B | 179.1 (3) |
C1A—C2A—C3A—C4A | 1.2 (9) | C1B—N1B—C5B—C6B | 178.7 (3) |
C2A—C3A—C4A—C5A | 0.0 (9) | Mn1—N1B—C5B—C6B | −1.7 (4) |
C1A—N1A—C5A—C4A | −1.1 (6) | C3B—C4B—C5B—N1B | 1.4 (6) |
Mn1—N1A—C5A—C4A | 179.3 (3) | C3B—C4B—C5B—C6B | −177.8 (4) |
C1A—N1A—C5A—C6A | 179.6 (4) | C10B—N2B—C6B—C7B | 0.7 (5) |
Mn1—N1A—C5A—C6A | 0.0 (5) | Mn1—N2B—C6B—C7B | −179.0 (3) |
C3A—C4A—C5A—N1A | −0.1 (8) | C10B—N2B—C6B—C5B | −179.0 (3) |
C3A—C4A—C5A—C6A | 179.1 (5) | Mn1—N2B—C6B—C5B | 1.4 (4) |
C10A—N2A—C6A—C7A | 1.9 (7) | N1B—C5B—C6B—N2B | 0.2 (5) |
Mn1—N2A—C6A—C7A | −165.0 (4) | C4B—C5B—C6B—N2B | 179.4 (4) |
C10A—N2A—C6A—C5A | −179.6 (4) | N1B—C5B—C6B—C7B | −179.4 (4) |
Mn1—N2A—C6A—C5A | 13.5 (5) | C4B—C5B—C6B—C7B | −0.2 (6) |
N1A—C5A—C6A—N2A | −8.6 (6) | N2B—C6B—C7B—C8B | −1.1 (6) |
C4A—C5A—C6A—N2A | 172.2 (4) | C5B—C6B—C7B—C8B | 178.5 (4) |
N1A—C5A—C6A—C7A | 169.8 (4) | C6B—C7B—C8B—C9B | 0.1 (7) |
C4A—C5A—C6A—C7A | −9.5 (8) | C7B—C8B—C9B—C10B | 1.3 (7) |
N2A—C6A—C7A—C8A | −1.9 (8) | C6B—N2B—C10B—C9B | 0.8 (6) |
C5A—C6A—C7A—C8A | 179.8 (6) | Mn1—N2B—C10B—C9B | −179.6 (3) |
C6A—C7A—C8A—C9A | 0.2 (11) | C6B—N2B—C10B—C11B | −179.6 (3) |
C7A—C8A—C9A—C10A | 1.5 (12) | Mn1—N2B—C10B—C11B | 0.0 (4) |
C6A—N2A—C10A—C9A | −0.1 (7) | C8B—C9B—C10B—N2B | −1.7 (6) |
Mn1—N2A—C10A—C9A | 166.7 (4) | C8B—C9B—C10B—C11B | 178.7 (4) |
C6A—N2A—C10A—C11A | 179.8 (4) | C15B—N3B—C11B—C12B | 1.2 (6) |
Mn1—N2A—C10A—C11A | −13.3 (5) | Mn1—N3B—C11B—C12B | −173.9 (3) |
C8A—C9A—C10A—N2A | −1.6 (9) | C15B—N3B—C11B—C10B | 179.7 (3) |
C8A—C9A—C10A—C11A | 178.5 (6) | Mn1—N3B—C11B—C10B | 4.6 (4) |
C15A—N3A—C11A—C12A | −2.7 (7) | N2B—C10B—C11B—N3B | −3.0 (5) |
Mn1—N3A—C11A—C12A | 171.5 (4) | C9B—C10B—C11B—N3B | 176.6 (4) |
C15A—N3A—C11A—C10A | 178.2 (4) | N2B—C10B—C11B—C12B | 175.4 (4) |
Mn1—N3A—C11A—C10A | −7.6 (5) | C9B—C10B—C11B—C12B | −5.0 (6) |
N2A—C10A—C11A—N3A | 13.6 (6) | N3B—C11B—C12B—C13B | −0.6 (6) |
C9A—C10A—C11A—N3A | −166.5 (5) | C10B—C11B—C12B—C13B | −179.0 (4) |
N2A—C10A—C11A—C12A | −165.5 (5) | C11B—C12B—C13B—C14B | −0.9 (7) |
C9A—C10A—C11A—C12A | 14.5 (8) | C12B—C13B—C14B—C15B | 1.8 (7) |
N3A—C11A—C12A—C13A | −1.0 (10) | C11B—N3B—C15B—C14B | −0.3 (6) |
C10A—C11A—C12A—C13A | 178.0 (6) | Mn1—N3B—C15B—C14B | 174.4 (3) |
C11A—C12A—C13A—C14A | 4.7 (12) | C13B—C14B—C15B—N3B | −1.2 (7) |
C12A—C13A—C14A—C15A | −4.5 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O1 | 0.90 (2) | 2.17 (3) | 2.955 (6) | 144 (2) |
O1W—H1WB···O5 | 0.90 (2) | 2.04 (3) | 2.722 (7) | 131 (2) |
O2W—H2WA···O1W | 0.90 (3) | 2.04 (3) | 2.859 (7) | 152 (3) |
O2W—H2WB···O6i | 0.90 (3) | 2.05 (3) | 2.928 (8) | 165 (2) |
O3W—H3WA···O2W | 0.90 (2) | 2.40 (2) | 3.090 (11) | 134 (1) |
O3W—H3WB···O4ii | 0.91 (4) | 2.43 (5) | 3.156 (11) | 137 (3) |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+3, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C15H11N3)2](S4O6)·3H2O |
Mr | 799.76 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.783 (3), 18.594 (7), 21.556 (12) |
β (°) | 94.05 (4) |
V (Å3) | 3512 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.67 |
Crystal size (mm) | 0.48 × 0.32 × 0.12 |
Data collection | |
Diffractometer | Siemens R3m diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.77, 0.92 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6852, 6187, 3567 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.124, 1.00 |
No. of reflections | 6187 |
No. of parameters | 469 |
No. of restraints | 9 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 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).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O1 | 0.90 (2) | 2.17 (3) | 2.955 (6) | 144 (2) |
O1W—H1WB···O5 | 0.90 (2) | 2.04 (3) | 2.722 (7) | 131 (2) |
O2W—H2WA···O1W | 0.90 (3) | 2.04 (3) | 2.859 (7) | 152 (3) |
O2W—H2WB···O6i | 0.90 (3) | 2.05 (3) | 2.928 (8) | 165 (2) |
O3W—H3WA···O2W | 0.90 (2) | 2.40 (2) | 3.090 (11) | 134 (1) |
O3W—H3WB···O4ii | 0.91 (4) | 2.43 (5) | 3.156 (11) | 137 (3) |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+3, −z+1. |
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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—X—X (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.