Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111047329/qs3008sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111047329/qs3008Isup2.hkl |
CCDC reference: 862220
All reagents were commercially available and were used without further purification. An aqueous solution of SnL3 (0.1 mol l-1) was prepared from mercaptoacetic acid (L), NaOH and SnCl4.5H2O at a stoichiometric ratio in water at room temperature. To a solution of MnCl2.4H2O (120 mg, 0.6 mmol) in water (5 ml) was added an aqueous solution (6 ml) of SnL3 (0.6 mmol) at room temperature. After several minutes, the solution was filtered and left to evaporate. After standing for several days at room temperature, colourless crystals of (I) were obtained in a yield of 86% (276 mg). Analysis, calculated for C6H16MnO11S3Sn (%): C 13.50, H 3.02, O 32.96, S 18.01; found: C 13.24, H 3.38, O 33.26, S 18.31. Spectroscopic analysis: IR (KBr pellet, ν, cm-1): 3565 (sh), 2974 (w), 2903 (w), 2814 (w), 1604 (s), 1330 (m), 1222 (m), 993 (ms), 899 (m), 781 (m), 721 (m).
H atoms bonded to C atoms were added at calculated positions and refined using a riding model, with C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C). [Please check added text] H atoms of coordinated water molecules were selected from peaks evident in the difference Fourier map, and their positions were restrained to an O—H distance of 0.82(s.u.?) Å using the DFIX command (SHELXL97; Sheldrick, 2008). Due to the presence of the heavy atom Sn in the structure, H atoms pertaining to the solvent water molecules could not be found accurately and were restrained in order to obtain a reasonable chemical geometry.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[MnSn(C2H2O2S)3(H2O)5] | F(000) = 1052 |
Mr = 534.05 | Dx = 2.165 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2ybc | Cell parameters from 4285 reflections |
a = 9.8901 (14) Å | θ = 3.0–27.5° |
b = 10.4992 (14) Å | µ = 2.73 mm−1 |
c = 15.883 (2) Å | T = 293 K |
β = 96.631 (2)° | Platelet, colourless |
V = 1638.2 (4) Å3 | 0.30 × 0.25 × 0.15 mm |
Z = 4 |
Rigaku R-AXIS RAPID diffractometer | 3738 independent reflections |
Radiation source: fine-focus sealed tube | 3504 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
Detector resolution: 14.6306 pixels mm-1 | θmax = 27.5°, θmin = 2.3° |
CCD profile fitting scans | h = −12→12 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −13→8 |
Tmin = 0.670, Tmax = 1.000 | l = −20→20 |
12118 measured reflections |
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)] = 0.018 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.023P)2 + 0.6191P] where P = (Fo2 + 2Fc2)/3 |
3738 reflections | (Δ/σ)max = 0.002 |
239 parameters | Δρmax = 0.52 e Å−3 |
11 restraints | Δρmin = −0.55 e Å−3 |
[MnSn(C2H2O2S)3(H2O)5] | V = 1638.2 (4) Å3 |
Mr = 534.05 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.8901 (14) Å | µ = 2.73 mm−1 |
b = 10.4992 (14) Å | T = 293 K |
c = 15.883 (2) Å | 0.30 × 0.25 × 0.15 mm |
β = 96.631 (2)° |
Rigaku R-AXIS RAPID diffractometer | 3738 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3504 reflections with I > 2σ(I) |
Tmin = 0.670, Tmax = 1.000 | Rint = 0.015 |
12118 measured reflections |
R[F2 > 2σ(F2)] = 0.018 | 11 restraints |
wR(F2) = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.52 e Å−3 |
3738 reflections | Δρmin = −0.55 e Å−3 |
239 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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Sn1 | 0.318797 (11) | 0.751087 (10) | 0.083368 (7) | 0.01907 (4) | |
Mn1 | −0.10411 (3) | 0.77439 (3) | 0.301722 (16) | 0.02136 (7) | |
S1 | 0.44697 (5) | 0.64000 (5) | 0.20225 (3) | 0.03204 (11) | |
S2 | 0.39108 (4) | 0.97173 (4) | 0.11072 (3) | 0.02711 (10) | |
S3 | 0.45331 (5) | 0.69111 (5) | −0.03013 (3) | 0.02903 (10) | |
O1 | 0.16684 (12) | 0.76078 (12) | 0.16776 (8) | 0.0241 (3) | |
O2 | 0.10702 (14) | 0.73347 (13) | 0.29603 (8) | 0.0295 (3) | |
O3 | 0.16236 (12) | 0.84667 (11) | 0.00016 (7) | 0.0246 (3) | |
O4 | 0.10102 (14) | 1.01364 (13) | −0.08041 (8) | 0.0318 (3) | |
O5 | 0.20285 (13) | 0.58560 (12) | 0.04056 (8) | 0.0279 (3) | |
O6 | 0.16123 (16) | 0.43111 (14) | −0.05268 (9) | 0.0398 (3) | |
O7 | −0.11588 (15) | 0.56326 (13) | 0.30736 (9) | 0.0311 (3) | |
H7B | −0.188 (2) | 0.532 (3) | 0.3169 (17) | 0.059 (9)* | |
H7A | −0.054 (3) | 0.538 (3) | 0.3428 (18) | 0.085 (12)* | |
O8 | −0.07281 (16) | 0.76865 (15) | 0.43799 (9) | 0.0334 (3) | |
H8A | −0.006 (2) | 0.732 (2) | 0.4625 (16) | 0.043 (7)* | |
H8B | −0.091 (3) | 0.822 (2) | 0.4730 (14) | 0.050 (7)* | |
O9 | −0.31888 (15) | 0.81334 (19) | 0.31480 (11) | 0.0450 (4) | |
H9B | −0.357 (3) | 0.836 (4) | 0.3567 (19) | 0.131 (16)* | |
H9A | −0.372 (3) | 0.779 (3) | 0.2808 (19) | 0.078 (12)* | |
O10 | −0.05762 (17) | 0.97639 (14) | 0.31248 (10) | 0.0370 (3) | |
H10B | 0.006 (2) | 1.000 (3) | 0.2875 (19) | 0.075 (10)* | |
H10A | −0.055 (3) | 1.004 (3) | 0.3581 (14) | 0.088 (12)* | |
O11 | −0.16885 (16) | 0.77213 (14) | 0.16689 (9) | 0.0327 (3) | |
H11A | −0.146 (3) | 0.831 (2) | 0.1384 (15) | 0.049 (8)* | |
H11B | −0.172 (3) | 0.708 (2) | 0.1371 (15) | 0.048 (7)* | |
C1 | 0.31509 (18) | 0.64221 (19) | 0.27223 (11) | 0.0272 (4) | |
H1A | 0.2883 | 0.5549 | 0.2816 | 0.033* | |
H1B | 0.3539 | 0.6762 | 0.3265 | 0.033* | |
C2 | 0.18824 (17) | 0.71770 (17) | 0.24276 (11) | 0.0213 (3) | |
C3 | 0.30522 (19) | 1.03381 (18) | 0.01192 (12) | 0.0301 (4) | |
H3A | 0.2785 | 1.1211 | 0.0213 | 0.036* | |
H3B | 0.3699 | 1.0355 | −0.0296 | 0.036* | |
C4 | 0.18047 (17) | 0.96085 (16) | −0.02544 (10) | 0.0218 (3) | |
C5 | 0.3338 (2) | 0.57475 (19) | −0.07884 (12) | 0.0319 (4) | |
H5A | 0.2882 | 0.6116 | −0.1305 | 0.038* | |
H5B | 0.3852 | 0.5019 | −0.0951 | 0.038* | |
C6 | 0.22642 (18) | 0.52715 (17) | −0.02674 (11) | 0.0242 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.01906 (7) | 0.01916 (7) | 0.01911 (7) | 0.00021 (4) | 0.00269 (5) | −0.00011 (4) |
Mn1 | 0.02317 (14) | 0.01935 (13) | 0.02176 (13) | 0.00011 (10) | 0.00346 (10) | −0.00083 (10) |
S1 | 0.0256 (2) | 0.0442 (3) | 0.0266 (2) | 0.0136 (2) | 0.00407 (17) | 0.0061 (2) |
S2 | 0.0250 (2) | 0.0251 (2) | 0.0304 (2) | −0.00544 (18) | −0.00043 (17) | −0.00610 (18) |
S3 | 0.0269 (2) | 0.0350 (3) | 0.0267 (2) | −0.00384 (19) | 0.00958 (17) | −0.00233 (19) |
O1 | 0.0220 (6) | 0.0279 (7) | 0.0232 (6) | 0.0042 (5) | 0.0056 (5) | 0.0034 (5) |
O2 | 0.0249 (7) | 0.0397 (8) | 0.0252 (6) | 0.0006 (5) | 0.0086 (5) | −0.0019 (5) |
O3 | 0.0249 (6) | 0.0196 (6) | 0.0277 (6) | −0.0041 (5) | −0.0045 (5) | 0.0035 (5) |
O4 | 0.0386 (7) | 0.0245 (7) | 0.0300 (6) | −0.0015 (6) | −0.0061 (5) | 0.0051 (5) |
O5 | 0.0313 (6) | 0.0244 (7) | 0.0293 (6) | −0.0071 (5) | 0.0089 (5) | −0.0043 (5) |
O6 | 0.0564 (9) | 0.0292 (8) | 0.0347 (7) | −0.0160 (7) | 0.0093 (6) | −0.0089 (6) |
O7 | 0.0347 (8) | 0.0212 (7) | 0.0382 (8) | −0.0032 (6) | 0.0079 (6) | 0.0023 (6) |
O8 | 0.0353 (8) | 0.0406 (9) | 0.0233 (7) | 0.0162 (6) | −0.0012 (6) | −0.0030 (6) |
O9 | 0.0259 (7) | 0.0630 (12) | 0.0466 (9) | 0.0027 (8) | 0.0063 (7) | −0.0087 (9) |
O10 | 0.0496 (9) | 0.0208 (7) | 0.0393 (8) | −0.0036 (7) | 0.0003 (7) | 0.0006 (6) |
O11 | 0.0484 (9) | 0.0265 (7) | 0.0224 (7) | −0.0050 (7) | 0.0007 (6) | −0.0004 (6) |
C1 | 0.0263 (8) | 0.0322 (10) | 0.0228 (8) | 0.0027 (8) | 0.0024 (7) | 0.0024 (7) |
C2 | 0.0221 (8) | 0.0184 (8) | 0.0235 (8) | −0.0038 (7) | 0.0037 (6) | −0.0052 (6) |
C3 | 0.0298 (9) | 0.0239 (9) | 0.0359 (10) | −0.0068 (8) | 0.0014 (8) | 0.0033 (8) |
C4 | 0.0262 (8) | 0.0190 (8) | 0.0207 (7) | 0.0007 (7) | 0.0055 (6) | −0.0009 (6) |
C5 | 0.0421 (11) | 0.0287 (10) | 0.0258 (9) | −0.0048 (8) | 0.0084 (8) | −0.0036 (8) |
C6 | 0.0305 (9) | 0.0186 (8) | 0.0224 (8) | 0.0002 (7) | −0.0017 (7) | 0.0023 (6) |
Sn1—O1 | 2.1286 (12) | O6—C6 | 1.241 (2) |
Sn1—O5 | 2.1485 (13) | O7—H7B | 0.814 (17) |
Sn1—O3 | 2.1622 (12) | O7—H7A | 0.821 (18) |
Sn1—S3 | 2.4434 (5) | O8—H8A | 0.821 (16) |
Sn1—S1 | 2.4453 (5) | O8—H8B | 0.824 (17) |
Sn1—S2 | 2.4484 (5) | O9—H9B | 0.836 (16) |
Mn1—O2 | 2.1440 (14) | O9—H9A | 0.795 (18) |
Mn1—O8 | 2.1515 (15) | O10—H10B | 0.819 (18) |
Mn1—O11 | 2.1632 (14) | O10—H10A | 0.780 (18) |
Mn1—O10 | 2.1726 (15) | O11—H11A | 0.812 (17) |
Mn1—O9 | 2.1963 (15) | O11—H11B | 0.819 (17) |
Mn1—O7 | 2.2221 (15) | C1—C2 | 1.512 (2) |
S1—C1 | 1.8088 (18) | C1—H1A | 0.9700 |
S2—C3 | 1.8169 (19) | C1—H1B | 0.9700 |
S3—C5 | 1.810 (2) | C3—C4 | 1.514 (2) |
O1—C2 | 1.269 (2) | C3—H3A | 0.9700 |
O2—C2 | 1.243 (2) | C3—H3B | 0.9700 |
O3—C4 | 1.285 (2) | C5—C6 | 1.505 (3) |
O4—C4 | 1.236 (2) | C5—H5A | 0.9700 |
O5—C6 | 1.277 (2) | C5—H5B | 0.9700 |
O1—Sn1—O5 | 81.26 (5) | Mn1—O8—H8A | 120.3 (19) |
O1—Sn1—O3 | 81.68 (5) | Mn1—O8—H8B | 130.0 (18) |
O5—Sn1—O3 | 82.17 (5) | H8A—O8—H8B | 103 (2) |
O1—Sn1—S3 | 163.97 (4) | Mn1—O9—H9B | 131 (3) |
O5—Sn1—S3 | 82.78 (3) | Mn1—O9—H9A | 115 (3) |
O3—Sn1—S3 | 94.63 (4) | H9B—O9—H9A | 111 (3) |
O1—Sn1—S1 | 82.95 (4) | Mn1—O10—H10B | 115 (2) |
O5—Sn1—S1 | 93.94 (4) | Mn1—O10—H10A | 115 (3) |
O3—Sn1—S1 | 164.55 (4) | H10B—O10—H10A | 113 (3) |
S3—Sn1—S1 | 99.725 (19) | Mn1—O11—H11A | 118.4 (18) |
O1—Sn1—S2 | 93.21 (4) | Mn1—O11—H11B | 124.7 (19) |
O5—Sn1—S2 | 162.85 (4) | H11A—O11—H11B | 107 (3) |
O3—Sn1—S2 | 80.97 (3) | C2—C1—S1 | 116.62 (12) |
S3—Sn1—S2 | 101.658 (17) | C2—C1—H1A | 108.1 |
S1—Sn1—S2 | 101.512 (19) | S1—C1—H1A | 108.1 |
O2—Mn1—O8 | 90.52 (5) | C2—C1—H1B | 108.1 |
O2—Mn1—O11 | 97.72 (6) | S1—C1—H1B | 108.1 |
O8—Mn1—O11 | 170.85 (6) | H1A—C1—H1B | 107.3 |
O2—Mn1—O10 | 90.04 (6) | O2—C2—O1 | 122.72 (16) |
O8—Mn1—O10 | 86.77 (6) | O2—C2—C1 | 115.95 (16) |
O11—Mn1—O10 | 97.14 (6) | O1—C2—C1 | 121.33 (15) |
O2—Mn1—O9 | 176.91 (6) | C4—C3—S2 | 115.81 (13) |
O8—Mn1—O9 | 86.47 (6) | C4—C3—H3A | 108.3 |
O11—Mn1—O9 | 85.22 (6) | S2—C3—H3A | 108.3 |
O10—Mn1—O9 | 90.51 (7) | C4—C3—H3B | 108.3 |
O2—Mn1—O7 | 81.81 (5) | S2—C3—H3B | 108.3 |
O8—Mn1—O7 | 86.20 (6) | H3A—C3—H3B | 107.4 |
O11—Mn1—O7 | 91.03 (6) | O4—C4—O3 | 122.76 (16) |
O10—Mn1—O7 | 169.17 (6) | O4—C4—C3 | 118.21 (16) |
O9—Mn1—O7 | 97.25 (7) | O3—C4—C3 | 119.02 (15) |
C1—S1—Sn1 | 97.01 (6) | C6—C5—S3 | 117.17 (13) |
C3—S2—Sn1 | 95.07 (6) | C6—C5—H5A | 108.0 |
C5—S3—Sn1 | 96.02 (6) | S3—C5—H5A | 108.0 |
C2—O1—Sn1 | 121.39 (11) | C6—C5—H5B | 108.0 |
C2—O2—Mn1 | 139.86 (13) | S3—C5—H5B | 108.0 |
C4—O3—Sn1 | 120.68 (11) | H5A—C5—H5B | 107.2 |
C6—O5—Sn1 | 120.74 (11) | O6—C6—O5 | 122.01 (17) |
Mn1—O7—H7B | 117 (2) | O6—C6—C5 | 117.37 (16) |
Mn1—O7—H7A | 108 (2) | O5—C6—C5 | 120.61 (16) |
H7B—O7—H7A | 110 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7A···O4i | 0.82 (2) | 1.93 (2) | 2.747 (2) | 175 (3) |
O8—H8A···O3i | 0.82 (2) | 1.89 (2) | 2.7055 (19) | 169 (2) |
O8—H8B···O6ii | 0.82 (2) | 1.90 (2) | 2.713 (2) | 170 (3) |
O10—H10A···O5ii | 0.78 (2) | 2.45 (3) | 3.098 (2) | 141 (3) |
O10—H10A···O6i | 0.78 (2) | 2.52 (3) | 3.024 (2) | 124 (3) |
O10—H10B···O7ii | 0.82 (2) | 2.07 (2) | 2.855 (2) | 162 (3) |
O11—H11A···O4iii | 0.81 (2) | 1.95 (2) | 2.758 (2) | 173 (3) |
O11—H11B···O6iv | 0.82 (2) | 2.00 (2) | 2.807 (2) | 170 (3) |
O9—H9A···S1v | 0.80 (2) | 2.53 (2) | 3.3038 (18) | 167 (3) |
O9—H9B···S3vi | 0.84 (2) | 2.76 (2) | 3.5251 (17) | 153 (3) |
O7—H7B···S2vii | 0.81 (2) | 2.51 (2) | 3.2928 (15) | 162 (3) |
C1—H1B···S3i | 0.97 | 2.75 | 3.7140 (19) | 171 |
C3—H3B···S2viii | 0.97 | 2.82 | 3.764 (2) | 164 |
C5—H5A···O2ix | 0.97 | 2.60 | 3.465 (2) | 149 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) −x, −y+2, −z; (iv) −x, −y+1, −z; (v) x−1, y, z; (vi) x−1, −y+3/2, z+1/2; (vii) −x, y−1/2, −z+1/2; (viii) −x+1, −y+2, −z; (ix) x, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [MnSn(C2H2O2S)3(H2O)5] |
Mr | 534.05 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.8901 (14), 10.4992 (14), 15.883 (2) |
β (°) | 96.631 (2) |
V (Å3) | 1638.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.73 |
Crystal size (mm) | 0.30 × 0.25 × 0.15 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.670, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12118, 3738, 3504 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.018, 0.044, 1.06 |
No. of reflections | 3738 |
No. of parameters | 239 |
No. of restraints | 11 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.52, −0.55 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Sn1—O1 | 2.1286 (12) | Mn1—O2 | 2.1440 (14) |
Sn1—O5 | 2.1485 (13) | Mn1—O8 | 2.1515 (15) |
Sn1—O3 | 2.1622 (12) | Mn1—O11 | 2.1632 (14) |
Sn1—S3 | 2.4434 (5) | Mn1—O10 | 2.1726 (15) |
Sn1—S1 | 2.4453 (5) | Mn1—O9 | 2.1963 (15) |
Sn1—S2 | 2.4484 (5) | Mn1—O7 | 2.2221 (15) |
O1—Sn1—O5 | 81.26 (5) | O2—Mn1—O8 | 90.52 (5) |
O1—Sn1—O3 | 81.68 (5) | O2—Mn1—O11 | 97.72 (6) |
O5—Sn1—O3 | 82.17 (5) | O8—Mn1—O11 | 170.85 (6) |
O1—Sn1—S3 | 163.97 (4) | O2—Mn1—O10 | 90.04 (6) |
O5—Sn1—S3 | 82.78 (3) | O8—Mn1—O10 | 86.77 (6) |
O3—Sn1—S3 | 94.63 (4) | O11—Mn1—O10 | 97.14 (6) |
O1—Sn1—S1 | 82.95 (4) | O2—Mn1—O9 | 176.91 (6) |
O5—Sn1—S1 | 93.94 (4) | O8—Mn1—O9 | 86.47 (6) |
O3—Sn1—S1 | 164.55 (4) | O11—Mn1—O9 | 85.22 (6) |
S3—Sn1—S1 | 99.725 (19) | O10—Mn1—O9 | 90.51 (7) |
O1—Sn1—S2 | 93.21 (4) | O2—Mn1—O7 | 81.81 (5) |
O5—Sn1—S2 | 162.85 (4) | O8—Mn1—O7 | 86.20 (6) |
O3—Sn1—S2 | 80.97 (3) | O11—Mn1—O7 | 91.03 (6) |
S3—Sn1—S2 | 101.658 (17) | O10—Mn1—O7 | 169.17 (6) |
S1—Sn1—S2 | 101.512 (19) | O9—Mn1—O7 | 97.25 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7A···O4i | 0.821 (18) | 1.928 (18) | 2.747 (2) | 175 (3) |
O8—H8A···O3i | 0.821 (16) | 1.894 (17) | 2.7055 (19) | 169 (2) |
O8—H8B···O6ii | 0.824 (17) | 1.897 (17) | 2.713 (2) | 170 (3) |
O10—H10A···O5ii | 0.780 (18) | 2.45 (3) | 3.098 (2) | 141 (3) |
O10—H10A···O6i | 0.780 (18) | 2.52 (3) | 3.024 (2) | 124 (3) |
O10—H10B···O7ii | 0.819 (18) | 2.07 (2) | 2.855 (2) | 162 (3) |
O11—H11A···O4iii | 0.812 (17) | 1.952 (17) | 2.758 (2) | 173 (3) |
O11—H11B···O6iv | 0.819 (17) | 1.996 (17) | 2.807 (2) | 170 (3) |
O9—H9A···S1v | 0.795 (18) | 2.525 (19) | 3.3038 (18) | 167 (3) |
O9—H9B···S3vi | 0.836 (16) | 2.760 (16) | 3.5251 (17) | 153 (3) |
O7—H7B···S2vii | 0.814 (17) | 2.509 (18) | 3.2928 (15) | 162 (3) |
C1—H1B···S3i | 0.97 | 2.75 | 3.7140 (19) | 171.1 |
C3—H3B···S2viii | 0.97 | 2.82 | 3.764 (2) | 164.3 |
C5—H5A···O2ix | 0.97 | 2.60 | 3.465 (2) | 149.3 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) −x, −y+2, −z; (iv) −x, −y+1, −z; (v) x−1, y, z; (vi) x−1, −y+3/2, z+1/2; (vii) −x, y−1/2, −z+1/2; (viii) −x+1, −y+2, −z; (ix) x, −y+3/2, z−1/2. |
Oxygen/sulfur-bridged heterometallic coordination clusters and polymers have attracted considerable interest because of their rich structural variety and potential applications as semiconductors, nonlinear optical or luminescent materials, magnetic materials, and so on (Wang et al., 2006). One synthetic route to these materials is the self-assembly technique of utilizing the spontaneous reaction of an organic ligand and two or more different metallic ions. The other synthetic approach is rational stepwise assembly, in which one metallic ion reacts with one organic ligand to form a complex building unit, which then coordinates to a different metallic ion to complete the assembly. Previously, S-containing ligands and carboxylate ligands have been proved to be versatile candidates which can adopt several coordination modes, for example, bidentate, tridentate etc. (Yang et al., 2011). Additionally, the bridging S atom or carboxylate group provides an efficient pathway that couples magnetic or luminescent metal centres for ferromagnetic interaction or energy transfer (Oldham et al., 1987; Faulkner & Pope, 2003).
Since the establishment of Werner's coordination theory by his pioneering research on the optical resolution of chiral cobalt(III) complexes, chirality has been one of the most important and fascinating subjects in coordination chemistry (Werner, 1911, 1912; Hirotsu et al., 2004). During the past few decades, a great deal of attention has been focused on the design and creation of well organized clusters or polymers, the overall structures of which can be controlled by the chirality of their building units (Leininger et al., 2000; Swiegers & Malefetse, 2000). Based on these practices, we initially synthesized the optically active complex anion [SnL3]2- (L is µ2-mercaptoacetate) and then utilized it as a building unit to react with heterometallic ions through the S atoms or carboxylate groups for assembling optically active heterometallic structures. In this paper, we focus on the assembly of the active [SnL3]2- complex ligand with MnII ions as the heterometallic centres. Fortuitously, the title novel heterometallic dinuclear compound, [MnSnL3(H2O)5], (I), has been successfully synthesized and characterized, though it is found to be racemic.
The structure of (I) has been characterized as a heterometallic dinuclear cluster (Fig. 1) consisting of three L ligands, five coordinated water molecules, one SnIV cation and one MnII cation. In the cluster, the SnIV centre is coordinated by three O atoms and three S atoms from three L ligands to form an [SnO3S3] octahedral coordination environment. Here, three L ligands chelate to the SnIV ion to give two enantiomers, (Δ/Λ) [SnL3]2-. The MnII centre is composed of an [MnO6] octahedral coordination environment, with five O atoms from five water molecules and a sixth from the µ2-L ligand of the (Δ/Λ) [SnL3]2- unit. In the [SnO3S3] octahedron, the Sn1—O1 bond lengths are in the range 2.1286 (12)–2.1622 (12) Å and the Sn1—S1 bond lengths are in the range 2.4434 (5)–2.4484 (5) Å, with the other bond lengths similar to those of other reported structures (Song, 2009; Chai et al., 2009; Ng et al., 1996). In the [MnO6] octahedron, the Mn—O bonds range from 2.1440 (14) to 2.2221 (15) Å (Table 1), and all bond lengths are similar to those of other reported structures (Nakasuka et al., 1985; Cheng et al., 2000; Klištincová et al., 2009; Bai et al., 2008; Liu et al., 2006). The bond angles of the two octahedra are near to those of an ideal octahedron, with a maximum deviation of 17.15 (4)° (Table 1).
In the crystal structure of (I), there are many hydrogen-bond interactions of O—H···O, O—H···S, C—H···O and C—H···S types (Table 2) between adjacent dinuclear molecules. The hydrogen-bond data are within the ranges of standard examples (Desiraju & Steiner, 1999) and have been examined using PLATON (Spek, 2009; van der Sluis & Spek, 1990). Along the bc plane, all adjacent dinuclear molecules are fused into two-dimensional supramolecular sheets (Fig. 2) by eight pairs of O—H···O hydrogen bonds [H···O = 1.894 (17)–2.52 (3) Å, O···O = 2.7055 (19)–3.098 (2) Å and O—H···O = 124 (3)–175 (3)°]. Neighbouring supramolecular sheets are further connected through O9—H9A···S1 and O9—H9B···S3 hydrogen bonds to give a three-dimensional supramolecular network (Fig. 3).
In conclusion, the successful rational stepwise assembly of the optically active [SnL3]2- complex anion with MnII ions leads to a novel heterometallic dinuclear compound. Through the many hydrogen-bond interactions present, these dinuclear molecules fuse together to form a three-dimensional supramolecular network structure. The heterometallic dinuclear molecule is optically active, but the two enantiomers crystallize as a racemic structure. Further research into novel structures and functions and exploration of the stepwise assembly of the active [SnL3]2- complex anion with other metallic ions, such as magnetic CoII and NiII or luminescent LnIII (where Ln is rare earth metal), are ongoing.