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In the title compound, [Ba(C7H5O2S)2(H2O)4]n, the BaII atom lies on a mirror plane and is nine-coordinated by four bridging carboxylate O atoms of the thio­salicyl­ate ligands, two bridging water mol­ecules and three terminal water mol­ecules. There is an intramolecular S-H...O hydrogen bond between the S and O atoms in the thio­salicyl­ate ligand. A one-dimensional coordination polymer is formed via weak metal-metal interactions along polymeric zigzag chains.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010300667X/ob1109sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010300667X/ob1109Isup2.hkl
Contains datablock I

CCDC reference: 214150

Comment top

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.

Experimental top

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%.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. Coordination environment around the BaII atom in (I), showing displacement ellipsoids at the 30% probability level.
[Figure 2] Fig. 2. The crystal-packing diagram of (I), showing polymeric chains viewed along the c axis.
catena-poly[tetraaquabis(thiosalicylate)barium(II)] top
Crystal data top
[Ba(C7H5O2S)2(H2O)4]Dx = 1.843 Mg m3
Mr = 515.74Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PnmaCell parameters from 41 reflections
a = 7.563 (3) Åθ = 5.0–12.5°
b = 29.885 (3) ŵ = 2.40 mm1
c = 8.2254 (9) ÅT = 295 K
V = 1859.2 (7) Å3Block, pale yellow
Z = 40.40 × 0.38 × 0.20 mm
F(000) = 1016
Data collection top
Siemens P4
diffractometer
1794 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.032
Graphite monochromatorθmax = 26.5°, θmin = 2.6°
ω/2θ scansh = 19
Absorption correction: empirical (using intensity measurements)
(North et al., 1968)
k = 137
Tmin = 0.383, Tmax = 0.619l = 110
2650 measured reflections3 standard reflections every 97 reflections
1957 independent reflections intensity decay: 1.5%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-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 parametersΔρmax = 1.12 e Å3
0 restraintsΔρmin = 1.75 e Å3
Crystal data top
[Ba(C7H5O2S)2(H2O)4]V = 1859.2 (7) Å3
Mr = 515.74Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 7.563 (3) ŵ = 2.40 mm1
b = 29.885 (3) ÅT = 295 K
c = 8.2254 (9) Å0.40 × 0.38 × 0.20 mm
Data collection top
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 = 0.6193 standard reflections every 97 reflections
2650 measured reflections intensity decay: 1.5%
1957 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.113H-atom parameters constrained
S = 1.13Δρmax = 1.12 e Å3
1957 reflectionsΔρmin = 1.75 e Å3
118 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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ba0.01796 (4)0.25000.37889 (4)0.02456 (16)
O110.1572 (6)0.25000.0642 (5)0.0304 (9)
O120.2176 (9)0.25000.6680 (7)0.0676 (18)
O130.0924 (7)0.32007 (17)0.5805 (7)0.0774 (15)
C10.1844 (5)0.38326 (14)0.0582 (5)0.0274 (8)
C20.1016 (5)0.41538 (15)0.0396 (5)0.0307 (9)
C30.1642 (6)0.45974 (15)0.0356 (6)0.0367 (10)
H3A0.10990.48140.09950.044*
C40.3059 (7)0.47142 (16)0.0624 (6)0.0437 (11)
H4A0.34610.50080.06390.052*
C50.3873 (8)0.43974 (19)0.1574 (7)0.0490 (12)
H5A0.48280.44760.22270.059*
C60.3256 (7)0.39562 (17)0.1552 (6)0.0401 (10)
H6A0.38050.37420.22000.048*
C70.1234 (6)0.33539 (14)0.0627 (5)0.0306 (9)
O80.1906 (4)0.30882 (10)0.1648 (4)0.0351 (7)
O90.0029 (5)0.32452 (14)0.0361 (6)0.0592 (13)
S100.07991 (19)0.40320 (5)0.16599 (18)0.0510 (4)
H10A0.10200.36350.17100.077*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba0.0198 (2)0.0301 (2)0.0238 (2)0.0000.00118 (11)0.000
O110.027 (2)0.031 (2)0.034 (2)0.0000.0007 (17)0.000
O120.076 (5)0.087 (5)0.040 (3)0.0000.016 (3)0.000
O130.061 (3)0.067 (3)0.104 (4)0.003 (2)0.004 (3)0.049 (3)
C10.0270 (19)0.030 (2)0.0256 (17)0.0017 (16)0.0012 (15)0.0003 (15)
C20.026 (2)0.040 (2)0.0262 (18)0.0052 (17)0.0046 (16)0.0031 (17)
C30.040 (2)0.031 (2)0.039 (2)0.0067 (19)0.009 (2)0.0085 (18)
C40.047 (3)0.030 (2)0.053 (3)0.007 (2)0.008 (2)0.002 (2)
C50.048 (3)0.045 (3)0.054 (3)0.010 (2)0.013 (3)0.004 (2)
C60.038 (3)0.041 (3)0.042 (2)0.001 (2)0.014 (2)0.004 (2)
C70.030 (2)0.028 (2)0.034 (2)0.0012 (16)0.0008 (17)0.0023 (16)
O80.0376 (17)0.0282 (15)0.0397 (15)0.0011 (13)0.0038 (14)0.0079 (13)
O90.068 (3)0.0352 (19)0.075 (3)0.0217 (17)0.039 (2)0.019 (2)
S100.0443 (7)0.0589 (8)0.0499 (7)0.0068 (6)0.0202 (6)0.0070 (6)
Geometric parameters (Å, º) top
Ba—O11i2.768 (4)C1—C71.503 (6)
Ba—O112.794 (4)C2—C31.408 (6)
Ba—O13ii2.799 (4)C2—S101.760 (5)
Ba—O132.799 (4)C3—C41.386 (7)
Ba—O122.817 (6)C3—H3A0.9300
Ba—O8iii2.842 (3)C4—C51.373 (8)
Ba—O8iv2.842 (3)C4—H4A0.9300
Ba—O8ii2.946 (3)C5—C61.399 (7)
Ba—O82.946 (3)C5—H5A0.9300
Ba—Bai4.3355 (13)C6—H6A0.9300
Ba—Baiii4.3355 (13)C7—O81.262 (5)
O11—Baiii2.768 (4)C7—O91.264 (6)
C1—C61.384 (6)O8—Bai2.842 (3)
C1—C21.400 (6)S10—H10A1.2000
O11i—Ba—O11121.87 (11)O8iii—Ba—Bai127.93 (7)
O11i—Ba—O13ii66.79 (12)O8iv—Ba—Bai127.93 (7)
O11—Ba—O13ii131.40 (13)O8ii—Ba—Bai40.59 (6)
O11i—Ba—O1366.79 (12)O8—Ba—Bai40.59 (6)
O11—Ba—O13131.40 (13)O11i—Ba—Baiii160.45 (9)
O13ii—Ba—O1396.9 (3)O11—Ba—Baiii38.58 (9)
O11i—Ba—O12112.68 (17)O13ii—Ba—Baiii123.36 (11)
O11—Ba—O12125.45 (17)O13—Ba—Baiii123.36 (11)
O13ii—Ba—O1270.09 (14)O12—Ba—Baiii86.87 (14)
O13—Ba—O1270.09 (14)O8iii—Ba—Baiii42.42 (6)
O11i—Ba—O8iii141.79 (6)O8iv—Ba—Baiii42.42 (6)
O11—Ba—O8iii65.84 (9)O8ii—Ba—Baiii100.06 (6)
O13ii—Ba—O8iii140.26 (13)O8—Ba—Baiii100.06 (6)
O13—Ba—O8iii80.98 (13)Bai—Ba—Baiii121.44 (2)
O12—Ba—O8iii72.01 (13)Baiii—O11—Ba102.41 (13)
O11i—Ba—O8iv141.79 (6)C6—C1—C2119.6 (4)
O11—Ba—O8iv65.84 (9)C6—C1—C7118.5 (4)
O13ii—Ba—O8iv80.98 (13)C2—C1—C7122.0 (4)
O13—Ba—O8iv140.26 (13)C1—C2—C3118.8 (4)
O12—Ba—O8iv72.01 (13)C1—C2—S10123.1 (4)
O8iii—Ba—O8iv76.42 (13)C3—C2—S10118.1 (3)
O11i—Ba—O8ii64.74 (9)C4—C3—C2120.7 (4)
O11—Ba—O8ii69.40 (9)C4—C3—H3A119.6
O13ii—Ba—O8ii75.41 (14)C2—C3—H3A119.6
O13—Ba—O8ii129.87 (12)C5—C4—C3120.3 (5)
O12—Ba—O8ii142.34 (7)C5—C4—H4A119.9
O8iii—Ba—O8ii135.14 (5)C3—C4—H4A119.9
O8iv—Ba—O8ii88.32 (8)C4—C5—C6119.5 (5)
O11i—Ba—O864.74 (9)C4—C5—H5A120.2
O11—Ba—O869.40 (9)C6—C5—H5A120.2
O13ii—Ba—O8129.87 (12)C1—C6—C5121.1 (4)
O13—Ba—O875.41 (14)C1—C6—H6A119.4
O12—Ba—O8142.34 (7)C5—C6—H6A119.4
O8iii—Ba—O888.32 (8)O8—C7—O9123.8 (4)
O8iv—Ba—O8135.14 (5)O8—C7—C1119.4 (4)
O8ii—Ba—O873.26 (12)O9—C7—C1116.7 (4)
O11i—Ba—Bai39.01 (9)C7—O8—Bai128.1 (3)
O11—Ba—Bai82.86 (9)C7—O8—Ba123.9 (3)
O13ii—Ba—Bai91.70 (11)Bai—O8—Ba96.99 (9)
O13—Ba—Bai91.70 (11)C2—S10—H10A109.5
O12—Ba—Bai151.69 (14)
O11i—Ba—O11—Baiii180.0O9—C7—O8—Bai87.9 (6)
O13ii—Ba—O11—Baiii94.04 (16)C1—C7—O8—Bai93.7 (4)
O13—Ba—O11—Baiii94.04 (16)O9—C7—O8—Ba47.6 (6)
O12—Ba—O11—Baiii0.0C1—C7—O8—Ba130.8 (3)
O8iii—Ba—O11—Baiii42.68 (7)O11i—Ba—O8—C7174.1 (4)
O8iv—Ba—O11—Baiii42.68 (7)O11—Ba—O8—C742.7 (3)
O8ii—Ba—O11—Baiii140.40 (7)O13ii—Ba—O8—C7170.0 (3)
O8—Ba—O11—Baiii140.40 (7)O13—Ba—O8—C7103.2 (3)
Bai—Ba—O11—Baiii180.0O12—Ba—O8—C779.2 (4)
C6—C1—C2—C30.4 (6)O8iii—Ba—O8—C722.1 (3)
C7—C1—C2—C3179.0 (4)O8iv—Ba—O8—C746.7 (3)
C6—C1—C2—S10179.5 (4)O8ii—Ba—O8—C7116.4 (3)
C7—C1—C2—S100.1 (6)Bai—Ba—O8—C7146.2 (4)
C1—C2—C3—C40.4 (6)Baiii—Ba—O8—C718.9 (3)
S10—C2—C3—C4179.6 (4)O11i—Ba—O8—Bai39.66 (8)
C2—C3—C4—C50.0 (7)O11—Ba—O8—Bai103.58 (10)
C3—C4—C5—C60.3 (8)O13ii—Ba—O8—Bai23.8 (2)
C2—C1—C6—C50.1 (7)O13—Ba—O8—Bai110.55 (14)
C7—C1—C6—C5179.4 (5)O12—Ba—O8—Bai134.6 (2)
C4—C5—C6—C10.3 (9)O8iii—Ba—O8—Bai168.33 (11)
C6—C1—C7—O86.6 (6)O8iv—Ba—O8—Bai99.58 (15)
C2—C1—C7—O8172.9 (4)O8ii—Ba—O8—Bai29.80 (11)
C6—C1—C7—O9174.9 (5)Baiii—Ba—O8—Bai127.38 (7)
C2—C1—C7—O95.6 (6)
Symmetry codes: (i) x1/2, 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.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
S10—H10A···O91.201.792.658 (4)124

Experimental details

Crystal data
Chemical formula[Ba(C7H5O2S)2(H2O)4]
Mr515.74
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)295
a, b, c (Å)7.563 (3), 29.885 (3), 8.2254 (9)
V3)1859.2 (7)
Z4
Radiation typeMo Kα
µ (mm1)2.40
Crystal size (mm)0.40 × 0.38 × 0.20
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(North et al., 1968)
Tmin, Tmax0.383, 0.619
No. of measured, independent and
observed [I > 2σ(I)] reflections
2650, 1957, 1794
Rint0.032
(sin θ/λ)max1)0.628
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.113, 1.13
No. of reflections1957
No. of parameters118
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.12, 1.75

Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Sheldrick, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
Ba—O11i2.768 (4)Ba—O8ii2.842 (3)
Ba—O112.794 (4)Ba—O82.946 (3)
Ba—O132.799 (4)Ba—Bai4.3355 (13)
Ba—O122.817 (6)
O11i—Ba—O11121.87 (11)O13iii—Ba—O8129.87 (12)
O11i—Ba—O1366.79 (12)O13—Ba—O875.41 (14)
O11—Ba—O13131.40 (13)O12—Ba—O8142.34 (7)
O13iii—Ba—O1396.9 (3)O8ii—Ba—O888.32 (8)
O11i—Ba—O12112.68 (17)O8iv—Ba—O8135.14 (5)
O11—Ba—O12125.45 (17)O8iii—Ba—O873.26 (12)
O13iii—Ba—O1270.09 (14)O11—Ba—Baii38.58 (9)
O11i—Ba—O8iv141.79 (6)O12—Ba—Baii86.87 (14)
O13iii—Ba—O8iv80.98 (13)Bai—Ba—Baii121.44 (2)
O13—Ba—O8iv140.26 (13)Baii—O11—Ba102.41 (13)
O12—Ba—O8iv72.01 (13)C7—O8—Ba123.9 (3)
O11i—Ba—O864.74 (9)Bai—O8—Ba96.99 (9)
O11—Ba—O869.40 (9)
Symmetry codes: (i) x1/2, 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.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
S10—H10A···O91.201.792.658 (4)124.0
 

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