Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010300667X/ob1109sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010300667X/ob1109Isup2.hkl |
CCDC reference: 214150
An ethanol–water (1:1) solution (10 ml) of thiosalicylic acid (1.54 g, 10 mmol) was added slowly to an aqueous solution (10 ml) of BaCl2·2H2O (1.22 g, 5 mmol) with continuous stirring. The reaction mixture was neutralized by an aqueous solution containing KOH (0.56 g, 10 mmol) and filtered. Pale-yellow block crystals of (I) suitable for X-ray analysis were obtained after a week at room temperature (yield 73%).
Analysis; found: C 32.68, H 3.20, O 22.95, S 12.05, Ba 26.30%; calculated for C14H18O8S2Ba: C 32.60, H 3.52, O 24.82, S 12.43, Ba 26.63%.
The H atoms of the thiosalicylate ligand were refined using a riding model (HFIX 43 for aromatic atoms and HFIX 83 for the thiol group). The H atoms of the water molecules were not introduced, because they could not be located in difference electron-density maps.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Ba(C7H5O2S)2(H2O)4] | Dx = 1.843 Mg m−3 |
Mr = 515.74 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 41 reflections |
a = 7.563 (3) Å | θ = 5.0–12.5° |
b = 29.885 (3) Å | µ = 2.40 mm−1 |
c = 8.2254 (9) Å | T = 295 K |
V = 1859.2 (7) Å3 | Block, pale yellow |
Z = 4 | 0.40 × 0.38 × 0.20 mm |
F(000) = 1016 |
Siemens P4 diffractometer | 1794 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Graphite monochromator | θmax = 26.5°, θmin = 2.6° |
ω/2θ scans | h = −1→9 |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | k = −1→37 |
Tmin = 0.383, Tmax = 0.619 | l = −1→10 |
2650 measured reflections | 3 standard reflections every 97 reflections |
1957 independent reflections | intensity decay: 1.5% |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0664P)2 + 3.6403P] where P = (Fo2 + 2Fc2)/3 |
1957 reflections | (Δ/σ)max < 0.001 |
118 parameters | Δρmax = 1.12 e Å−3 |
0 restraints | Δρmin = −1.75 e Å−3 |
[Ba(C7H5O2S)2(H2O)4] | V = 1859.2 (7) Å3 |
Mr = 515.74 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 7.563 (3) Å | µ = 2.40 mm−1 |
b = 29.885 (3) Å | T = 295 K |
c = 8.2254 (9) Å | 0.40 × 0.38 × 0.20 mm |
Siemens P4 diffractometer | 1794 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | Rint = 0.032 |
Tmin = 0.383, Tmax = 0.619 | 3 standard reflections every 97 reflections |
2650 measured reflections | intensity decay: 1.5% |
1957 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.13 | Δρmax = 1.12 e Å−3 |
1957 reflections | Δρmin = −1.75 e Å−3 |
118 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 | ||
Ba | 0.01796 (4) | 0.2500 | 0.37889 (4) | 0.02456 (16) | |
O11 | 0.1572 (6) | 0.2500 | 0.0642 (5) | 0.0304 (9) | |
O12 | 0.2176 (9) | 0.2500 | 0.6680 (7) | 0.0676 (18) | |
O13 | −0.0924 (7) | 0.32007 (17) | 0.5805 (7) | 0.0774 (15) | |
C1 | −0.1844 (5) | 0.38326 (14) | 0.0582 (5) | 0.0274 (8) | |
C2 | −0.1016 (5) | 0.41538 (15) | −0.0396 (5) | 0.0307 (9) | |
C3 | −0.1642 (6) | 0.45974 (15) | −0.0356 (6) | 0.0367 (10) | |
H3A | −0.1099 | 0.4814 | −0.0995 | 0.044* | |
C4 | −0.3059 (7) | 0.47142 (16) | 0.0624 (6) | 0.0437 (11) | |
H4A | −0.3461 | 0.5008 | 0.0639 | 0.052* | |
C5 | −0.3873 (8) | 0.43974 (19) | 0.1574 (7) | 0.0490 (12) | |
H5A | −0.4828 | 0.4476 | 0.2227 | 0.059* | |
C6 | −0.3256 (7) | 0.39562 (17) | 0.1552 (6) | 0.0401 (10) | |
H6A | −0.3805 | 0.3742 | 0.2200 | 0.048* | |
C7 | −0.1234 (6) | 0.33539 (14) | 0.0627 (5) | 0.0306 (9) | |
O8 | −0.1906 (4) | 0.30882 (10) | 0.1648 (4) | 0.0351 (7) | |
O9 | −0.0029 (5) | 0.32452 (14) | −0.0361 (6) | 0.0592 (13) | |
S10 | 0.07991 (19) | 0.40320 (5) | −0.16599 (18) | 0.0510 (4) | |
H10A | 0.1020 | 0.3635 | −0.1710 | 0.077* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ba | 0.0198 (2) | 0.0301 (2) | 0.0238 (2) | 0.000 | 0.00118 (11) | 0.000 |
O11 | 0.027 (2) | 0.031 (2) | 0.034 (2) | 0.000 | −0.0007 (17) | 0.000 |
O12 | 0.076 (5) | 0.087 (5) | 0.040 (3) | 0.000 | −0.016 (3) | 0.000 |
O13 | 0.061 (3) | 0.067 (3) | 0.104 (4) | 0.003 (2) | −0.004 (3) | −0.049 (3) |
C1 | 0.0270 (19) | 0.030 (2) | 0.0256 (17) | −0.0017 (16) | −0.0012 (15) | 0.0003 (15) |
C2 | 0.026 (2) | 0.040 (2) | 0.0262 (18) | −0.0052 (17) | −0.0046 (16) | 0.0031 (17) |
C3 | 0.040 (2) | 0.031 (2) | 0.039 (2) | −0.0067 (19) | −0.009 (2) | 0.0085 (18) |
C4 | 0.047 (3) | 0.030 (2) | 0.053 (3) | 0.007 (2) | −0.008 (2) | −0.002 (2) |
C5 | 0.048 (3) | 0.045 (3) | 0.054 (3) | 0.010 (2) | 0.013 (3) | −0.004 (2) |
C6 | 0.038 (3) | 0.041 (3) | 0.042 (2) | 0.001 (2) | 0.014 (2) | 0.004 (2) |
C7 | 0.030 (2) | 0.028 (2) | 0.034 (2) | −0.0012 (16) | −0.0008 (17) | 0.0023 (16) |
O8 | 0.0376 (17) | 0.0282 (15) | 0.0397 (15) | −0.0011 (13) | 0.0038 (14) | 0.0079 (13) |
O9 | 0.068 (3) | 0.0352 (19) | 0.075 (3) | 0.0217 (17) | 0.039 (2) | 0.019 (2) |
S10 | 0.0443 (7) | 0.0589 (8) | 0.0499 (7) | −0.0068 (6) | 0.0202 (6) | 0.0070 (6) |
Ba—O11i | 2.768 (4) | C1—C7 | 1.503 (6) |
Ba—O11 | 2.794 (4) | C2—C3 | 1.408 (6) |
Ba—O13ii | 2.799 (4) | C2—S10 | 1.760 (5) |
Ba—O13 | 2.799 (4) | C3—C4 | 1.386 (7) |
Ba—O12 | 2.817 (6) | C3—H3A | 0.9300 |
Ba—O8iii | 2.842 (3) | C4—C5 | 1.373 (8) |
Ba—O8iv | 2.842 (3) | C4—H4A | 0.9300 |
Ba—O8ii | 2.946 (3) | C5—C6 | 1.399 (7) |
Ba—O8 | 2.946 (3) | C5—H5A | 0.9300 |
Ba—Bai | 4.3355 (13) | C6—H6A | 0.9300 |
Ba—Baiii | 4.3355 (13) | C7—O8 | 1.262 (5) |
O11—Baiii | 2.768 (4) | C7—O9 | 1.264 (6) |
C1—C6 | 1.384 (6) | O8—Bai | 2.842 (3) |
C1—C2 | 1.400 (6) | S10—H10A | 1.2000 |
O11i—Ba—O11 | 121.87 (11) | O8iii—Ba—Bai | 127.93 (7) |
O11i—Ba—O13ii | 66.79 (12) | O8iv—Ba—Bai | 127.93 (7) |
O11—Ba—O13ii | 131.40 (13) | O8ii—Ba—Bai | 40.59 (6) |
O11i—Ba—O13 | 66.79 (12) | O8—Ba—Bai | 40.59 (6) |
O11—Ba—O13 | 131.40 (13) | O11i—Ba—Baiii | 160.45 (9) |
O13ii—Ba—O13 | 96.9 (3) | O11—Ba—Baiii | 38.58 (9) |
O11i—Ba—O12 | 112.68 (17) | O13ii—Ba—Baiii | 123.36 (11) |
O11—Ba—O12 | 125.45 (17) | O13—Ba—Baiii | 123.36 (11) |
O13ii—Ba—O12 | 70.09 (14) | O12—Ba—Baiii | 86.87 (14) |
O13—Ba—O12 | 70.09 (14) | O8iii—Ba—Baiii | 42.42 (6) |
O11i—Ba—O8iii | 141.79 (6) | O8iv—Ba—Baiii | 42.42 (6) |
O11—Ba—O8iii | 65.84 (9) | O8ii—Ba—Baiii | 100.06 (6) |
O13ii—Ba—O8iii | 140.26 (13) | O8—Ba—Baiii | 100.06 (6) |
O13—Ba—O8iii | 80.98 (13) | Bai—Ba—Baiii | 121.44 (2) |
O12—Ba—O8iii | 72.01 (13) | Baiii—O11—Ba | 102.41 (13) |
O11i—Ba—O8iv | 141.79 (6) | C6—C1—C2 | 119.6 (4) |
O11—Ba—O8iv | 65.84 (9) | C6—C1—C7 | 118.5 (4) |
O13ii—Ba—O8iv | 80.98 (13) | C2—C1—C7 | 122.0 (4) |
O13—Ba—O8iv | 140.26 (13) | C1—C2—C3 | 118.8 (4) |
O12—Ba—O8iv | 72.01 (13) | C1—C2—S10 | 123.1 (4) |
O8iii—Ba—O8iv | 76.42 (13) | C3—C2—S10 | 118.1 (3) |
O11i—Ba—O8ii | 64.74 (9) | C4—C3—C2 | 120.7 (4) |
O11—Ba—O8ii | 69.40 (9) | C4—C3—H3A | 119.6 |
O13ii—Ba—O8ii | 75.41 (14) | C2—C3—H3A | 119.6 |
O13—Ba—O8ii | 129.87 (12) | C5—C4—C3 | 120.3 (5) |
O12—Ba—O8ii | 142.34 (7) | C5—C4—H4A | 119.9 |
O8iii—Ba—O8ii | 135.14 (5) | C3—C4—H4A | 119.9 |
O8iv—Ba—O8ii | 88.32 (8) | C4—C5—C6 | 119.5 (5) |
O11i—Ba—O8 | 64.74 (9) | C4—C5—H5A | 120.2 |
O11—Ba—O8 | 69.40 (9) | C6—C5—H5A | 120.2 |
O13ii—Ba—O8 | 129.87 (12) | C1—C6—C5 | 121.1 (4) |
O13—Ba—O8 | 75.41 (14) | C1—C6—H6A | 119.4 |
O12—Ba—O8 | 142.34 (7) | C5—C6—H6A | 119.4 |
O8iii—Ba—O8 | 88.32 (8) | O8—C7—O9 | 123.8 (4) |
O8iv—Ba—O8 | 135.14 (5) | O8—C7—C1 | 119.4 (4) |
O8ii—Ba—O8 | 73.26 (12) | O9—C7—C1 | 116.7 (4) |
O11i—Ba—Bai | 39.01 (9) | C7—O8—Bai | 128.1 (3) |
O11—Ba—Bai | 82.86 (9) | C7—O8—Ba | 123.9 (3) |
O13ii—Ba—Bai | 91.70 (11) | Bai—O8—Ba | 96.99 (9) |
O13—Ba—Bai | 91.70 (11) | C2—S10—H10A | 109.5 |
O12—Ba—Bai | 151.69 (14) | ||
O11i—Ba—O11—Baiii | 180.0 | O9—C7—O8—Bai | −87.9 (6) |
O13ii—Ba—O11—Baiii | −94.04 (16) | C1—C7—O8—Bai | 93.7 (4) |
O13—Ba—O11—Baiii | 94.04 (16) | O9—C7—O8—Ba | 47.6 (6) |
O12—Ba—O11—Baiii | 0.0 | C1—C7—O8—Ba | −130.8 (3) |
O8iii—Ba—O11—Baiii | 42.68 (7) | O11i—Ba—O8—C7 | 174.1 (4) |
O8iv—Ba—O11—Baiii | −42.68 (7) | O11—Ba—O8—C7 | −42.7 (3) |
O8ii—Ba—O11—Baiii | −140.40 (7) | O13ii—Ba—O8—C7 | −170.0 (3) |
O8—Ba—O11—Baiii | 140.40 (7) | O13—Ba—O8—C7 | 103.2 (3) |
Bai—Ba—O11—Baiii | 180.0 | O12—Ba—O8—C7 | 79.2 (4) |
C6—C1—C2—C3 | 0.4 (6) | O8iii—Ba—O8—C7 | 22.1 (3) |
C7—C1—C2—C3 | −179.0 (4) | O8iv—Ba—O8—C7 | −46.7 (3) |
C6—C1—C2—S10 | 179.5 (4) | O8ii—Ba—O8—C7 | −116.4 (3) |
C7—C1—C2—S10 | 0.1 (6) | Bai—Ba—O8—C7 | −146.2 (4) |
C1—C2—C3—C4 | −0.4 (6) | Baiii—Ba—O8—C7 | −18.9 (3) |
S10—C2—C3—C4 | −179.6 (4) | O11i—Ba—O8—Bai | −39.66 (8) |
C2—C3—C4—C5 | 0.0 (7) | O11—Ba—O8—Bai | 103.58 (10) |
C3—C4—C5—C6 | 0.3 (8) | O13ii—Ba—O8—Bai | −23.8 (2) |
C2—C1—C6—C5 | −0.1 (7) | O13—Ba—O8—Bai | −110.55 (14) |
C7—C1—C6—C5 | 179.4 (5) | O12—Ba—O8—Bai | −134.6 (2) |
C4—C5—C6—C1 | −0.3 (9) | O8iii—Ba—O8—Bai | 168.33 (11) |
C6—C1—C7—O8 | −6.6 (6) | O8iv—Ba—O8—Bai | 99.58 (15) |
C2—C1—C7—O8 | 172.9 (4) | O8ii—Ba—O8—Bai | 29.80 (11) |
C6—C1—C7—O9 | 174.9 (5) | Baiii—Ba—O8—Bai | 127.38 (7) |
C2—C1—C7—O9 | −5.6 (6) |
Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) x, −y+1/2, z; (iii) x+1/2, y, −z+1/2; (iv) x+1/2, −y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ba(C7H5O2S)2(H2O)4] |
Mr | 515.74 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 295 |
a, b, c (Å) | 7.563 (3), 29.885 (3), 8.2254 (9) |
V (Å3) | 1859.2 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.40 |
Crystal size (mm) | 0.40 × 0.38 × 0.20 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Empirical (using intensity measurements) (North et al., 1968) |
Tmin, Tmax | 0.383, 0.619 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2650, 1957, 1794 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.113, 1.13 |
No. of reflections | 1957 |
No. of parameters | 118 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.12, −1.75 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Sheldrick, 1997), SHELXTL.
Ba—O11i | 2.768 (4) | Ba—O8ii | 2.842 (3) |
Ba—O11 | 2.794 (4) | Ba—O8 | 2.946 (3) |
Ba—O13 | 2.799 (4) | Ba—Bai | 4.3355 (13) |
Ba—O12 | 2.817 (6) | ||
O11i—Ba—O11 | 121.87 (11) | O13iii—Ba—O8 | 129.87 (12) |
O11i—Ba—O13 | 66.79 (12) | O13—Ba—O8 | 75.41 (14) |
O11—Ba—O13 | 131.40 (13) | O12—Ba—O8 | 142.34 (7) |
O13iii—Ba—O13 | 96.9 (3) | O8ii—Ba—O8 | 88.32 (8) |
O11i—Ba—O12 | 112.68 (17) | O8iv—Ba—O8 | 135.14 (5) |
O11—Ba—O12 | 125.45 (17) | O8iii—Ba—O8 | 73.26 (12) |
O13iii—Ba—O12 | 70.09 (14) | O11—Ba—Baii | 38.58 (9) |
O11i—Ba—O8iv | 141.79 (6) | O12—Ba—Baii | 86.87 (14) |
O13iii—Ba—O8iv | 80.98 (13) | Bai—Ba—Baii | 121.44 (2) |
O13—Ba—O8iv | 140.26 (13) | Baii—O11—Ba | 102.41 (13) |
O12—Ba—O8iv | 72.01 (13) | C7—O8—Ba | 123.9 (3) |
O11i—Ba—O8 | 64.74 (9) | Bai—O8—Ba | 96.99 (9) |
O11—Ba—O8 | 69.40 (9) |
Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) x+1/2, y, −z+1/2; (iii) x, −y+1/2, z; (iv) x+1/2, −y+1/2, −z+1/2. |
The contamination of water and soil by metals such as barium, chromium, copper, cadmium, lead, mercury and zinc may cause a great deal of harm in the biosphere (Code of Federal Regulations, 1993). When barium compounds, which are frequently used in fireworks, paints, rat poisons and heat stabilizer in plastics, are ingested, barium is known to alter muscle and nerve cells by disrupting the flow of potassium. Eventually, barium behaves like calcium in living organisms and becomes potentially hazadous to organisms by accumulating in bone (Harte et al., 1991). There are many technologies and products for remediation of heavy-metal contaminants, including activated carbon adsorption, chemical precipitation, electrolytic treatment, in situ vitrification, and biological treatment with plants, fungi and bacteria. Chemical precipitation is one of the more popular and economical methods for removing heavy metals from industrial waste waters and natural waters.
Thiolate ligands such as cysteamine and thiosalicylic acid are known to be useful for chemical precipitation as a result of their coordination character (Kuehn & Isied, 1980). Because of the combination of hard amine and soft thiolate donors, or hard carboxylate and soft thiolate donors, thiolate ligands could potentially make novel complexes with a wide range of metal centers such as mercury (Kim et al., 2002), platinum, palladium, nickel (McCaffrey et al., 1997), rhodium, iridium, ruthenium (Henderson et al., 2001), bismuth (Burford et al., 2002) and lanthanides (Bo & Hongzhu, 2000). In our group, research has been focused on the development of new heavy- metal remediation agents with thiolate ligands, containing supplementary hard donor atoms such as oxygen and nitrogen. In this paper, we report the preparation and crystal structure of the title compound, (I), which is a new barium(II) complex containing the thiosalicylate ligand.
The coordination environment around the central barium ion is shown in Fig. 1. The Ba atom lies on a mirror plane and is nine-coordinated by four bridging O atoms (O8) from different carboxylate groups of the thiosalicylate ligands, two bridging O atoms (O11) and three terminal O atoms (O12, O13) of the water molecules. The bridging O11 and terminal O12 atoms lie on a mirror plane. The water moelcule containing atom O12 is only terminally coordinated to the Ba atom, because the distance from O12 to the adjacent Baii atom [symmetry code: (ii) 1/2 + x, y, 1/2 − z] is 5.04 (1) Å and the Baii···O12—Ba angle is 59.2 (1)°. The Ba—O(carboxylate) bond distances of 2.842 (3)–2.946 (3) Å, the Ba—O(water) distances of 2.768 (4)–2.817 (6) Å and the Ba···Ba interaction distances of 4.3355 (13) Å are comparable to those reported for the barium-2,2'-dithiobis(benzoate) (Murugavel et al., 2001) and barium-2-aminobenzoate complexes (Murugavel et al., 2000). The bond angles around the Ba atom are in the range 64.74 (9)–142.34 (7)° (Table 1). The bond distances and angles of the thiosalicylate ligands are consistent with previously reported results (Henderson et al., 2001).
The crystal packing diagram of this complex reveals a one-dimensional coodination polymer, as shown in Fig. 2. The two carboxylate O8 atoms and the water O11 atoms bridge to the two adjacent Ba atoms, with a Ba—O8—Ba angle of 96.99 (9)° and a Ba—O11—Ba angle of 102.4 (1)°. Futhermore, the central Ba atom is engaged in a weak metal–metal interaction with two neighboring Ba atoms. The Ba···Ba···Ba interaction angle of 121.44 (2)° in the ac plane gives polymeric zigzag chains. The S and O atoms in the thiosalicylate ligand are linked by a intramolecular S10—H10A···O9 hydrogen bond [S10—H10A···O9 = 2.658 (4) Å, 124.0°]. However, there is no direct bonding between the Ba atom and the S10 atom of the thiosalicylate (tsa) ligand. In other complexes, tsa is able to adopt a variety of coordination modes, ranging from monodentate S-bonded through to bridging (Henderson et al., 2001). For example, the Ag atom of [Ag(tsa)(PPh3)3] and the Au atom of [Au(tsa)(PPh3)] are coordinated by the monodentate S atom of the tsa ligand (Nomiya et al., 1998). The Cu atom of [{Cu(PPh3)2}2{Cu(tsa)2}]·MeCN is bridged by the S atom and the O atom of the tsa ligand (Bott et al., 1998). The Cu atom of [Cu(tsa)2(py)]2 is chelated by the two O atoms of the tsa ligand (Ferrer & Williams, 1997). Therefore, this barium–tsa complex containing only one bridged O atom of the tsa ligand is different in structure from the previously reported silver–, gold– and copper–tsa complexes.