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Acta Cryst. (2009). E65, m1195    [ doi:10.1107/S1600536809035971 ]

Tetraaquabis[2-(thiosemicarbazonomethyl)benzenesulfonato]calcium(II)

Z. Wei and C. Yuan-Tao

Abstract top

In the title compound, [Ca(C8H8N3O3S2)2(H2O)4], the Ca atom (site symmetry \overline{1}) adopts a slightly distorted octahedral CaO6 geometry and the molecular conformation is stabilized by intramolecular N-H...N interactions. In the crystal, the molecules are linked by O-H...O, O-H...S, N-H...O and N-H...S hydrogen bonds.

Comment top

Schiff base metal complexes have been of interest in coordination chemistry for many years due to their facile synthesis, strong coordination function and wide applications (e.g. Sawant, et al., 2009). Ca complexes with Schiff base ligand have received little attention. In this paper, we report on the synthesis and crystal structure of the title compound, (I), (Scheme I).

The Ca(II) center is Six-coordinate with two O donors of 2-formyl-benzenesulfonate-thiosemicarbazide ligands and four O donors of coordinated water molecules, and adopts distorted octahedral coordination. The bond distances of Ca—O are in the range of 2.310 (4)–2.362 (4), which are consistent with the bond lengths reported previously. In the crystal packing, the molecules form a one-dimensional chain structure by the interaction of hydrogen bonds.

Related literature top

For background to Schiff bases, see: Sawant et al. (2009).

Experimental top

A solution of 1.0 mmol 2-formyl-benzenesulfonate-thiosemicarbazide was added to a solution of 0.5 mmol Ca(ClO4)2.4H2O in 5 ml e thanol at room temperature. The mixture was refluxed for 4 h with stirring, then the resulting precipitate was filtered, washed, and dried in vacuo over P4O10 for 48 h. Colourless blocks of (I) were obtained by slowly evaporating from methanol at room temperature.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing 30% displacement ellipsoids. Unlabelled atoms are generated by the symmetry operation (1–x, 1–y, 1–z).
Tetraaquabis[2-(thiosemicarbazonomethyl)benzenesulfonato]calcium(II) top
Crystal data top
[Ca(C8H8N3O3S2)2(H2O)4]Z = 1
Mr = 628.73F(000) = 326
Triclinic, P1Dx = 1.599 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.9123 (11) ÅCell parameters from 1563 reflections
b = 9.6383 (13) Åθ = 3.6–27.6°
c = 10.9481 (17) ŵ = 0.62 mm−1
α = 64.372 (1)°T = 298 K
β = 87.708 (2)°Block, colourless
γ = 83.225 (2)°0.31 × 0.15 × 0.12 mm
V = 652.99 (17) Å3
Data collection top
Bruker SMART CCD
diffractometer		2223 independent reflections
Radiation source: fine-focus sealed tube1781 reflections with I > 2σ(I)
graphiteRint = 0.0000
ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
SADABS (Bruker, 2000)		h = −8→8
Tmin = 0.831, Tmax = 0.929k = −10→11
2223 measured reflectionsl = −9→13
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)] = 0.078Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.227H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.1501P)2 + 0.6556P]
where P = (Fo2 + 2Fc2)/3
2223 reflections(Δ/σ)max < 0.001
170 parametersΔρmax = 0.60 e Å−3
0 restraintsΔρmin = −0.55 e Å−3
Crystal data top
[Ca(C8H8N3O3S2)2(H2O)4]γ = 83.225 (2)°
Mr = 628.73V = 652.99 (17) Å3
Triclinic, P1Z = 1
a = 6.9123 (11) ÅMo Kα radiation
b = 9.6383 (13) ŵ = 0.62 mm−1
c = 10.9481 (17) ÅT = 298 K
α = 64.372 (1)°0.31 × 0.15 × 0.12 mm
β = 87.708 (2)°
Data collection top
Bruker SMART CCD
diffractometer		2223 independent reflections
Absorption correction: multi-scan
SADABS (Bruker, 2000)		1781 reflections with I > 2σ(I)
Tmin = 0.831, Tmax = 0.929Rint = 0.0000
2223 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.078H-atom parameters constrained
wR(F2) = 0.227Δρmax = 0.60 e Å−3
S = 1.03Δρmin = −0.55 e Å−3
2223 reflectionsAbsolute structure: ?
170 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Ca10.50000.50000.50000.0345 (5)
S10.7458 (2)0.67806 (16)0.65974 (13)0.0354 (4)
S21.0140 (3)−0.13332 (17)1.21326 (16)0.0449 (5)
O10.6451 (7)0.5503 (5)0.6662 (4)0.0438 (11)
O20.6760 (7)0.8251 (5)0.5486 (4)0.0501 (12)
O30.9554 (7)0.6437 (6)0.6624 (5)0.0507 (12)
O40.7857 (7)0.5634 (6)0.3822 (5)0.0556 (13)
H4C0.83640.64740.34010.083*
H4D0.85920.49140.37300.083*
O50.6194 (10)0.2408 (6)0.5851 (8)0.096 (3)
H5C0.55280.18780.56110.143*
H5D0.70930.18060.63940.143*
N10.9136 (7)0.1670 (6)1.0860 (5)0.0354 (11)
H10.95410.15871.01390.043*
N20.8339 (7)0.3076 (5)1.0789 (5)0.0337 (11)
N30.8802 (9)0.0645 (6)1.3157 (5)0.0506 (14)
H3A0.84200.15651.30710.061*
H3B0.8874−0.01231.39470.061*
C10.9278 (8)0.0419 (6)1.2074 (6)0.0353 (13)
C20.8137 (8)0.4179 (6)0.9586 (6)0.0352 (12)
H20.85290.40010.88380.042*
C30.7269 (8)0.5739 (6)0.9407 (5)0.0309 (12)
C40.6848 (8)0.6971 (6)0.8118 (5)0.0311 (12)
C50.6039 (9)0.8407 (7)0.7991 (6)0.0390 (13)
H50.57910.92110.71330.047*
C60.5592 (9)0.8668 (7)0.9128 (7)0.0429 (14)
H60.50310.96350.90340.052*
C70.5998 (9)0.7453 (8)1.0420 (7)0.0441 (15)
H70.57210.76151.11900.053*
C80.6807 (9)0.6020 (7)1.0545 (6)0.0369 (13)
H80.70540.52191.14060.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ca10.0392 (9)0.0391 (9)0.0220 (8)−0.0068 (7)−0.0025 (6)−0.0094 (7)
S10.0473 (9)0.0352 (8)0.0200 (7)−0.0087 (6)−0.0001 (6)−0.0074 (6)
S20.0613 (11)0.0331 (8)0.0317 (8)−0.0016 (7)−0.0043 (7)−0.0066 (7)
O10.069 (3)0.044 (2)0.0195 (19)−0.016 (2)−0.0045 (18)−0.0119 (18)
O20.080 (3)0.040 (2)0.023 (2)−0.011 (2)−0.005 (2)−0.0059 (19)
O30.053 (3)0.066 (3)0.042 (3)−0.011 (2)0.008 (2)−0.031 (2)
O40.056 (3)0.058 (3)0.053 (3)−0.017 (2)0.019 (2)−0.023 (2)
O50.103 (5)0.043 (3)0.123 (6)0.013 (3)−0.073 (4)−0.018 (3)
N10.042 (3)0.034 (2)0.022 (2)0.001 (2)−0.0021 (19)−0.005 (2)
N20.038 (3)0.030 (2)0.029 (3)−0.0019 (19)−0.0006 (19)−0.009 (2)
N30.082 (4)0.034 (3)0.024 (3)0.000 (3)0.000 (2)−0.004 (2)
C10.040 (3)0.035 (3)0.025 (3)−0.007 (2)−0.003 (2)−0.006 (2)
C20.039 (3)0.034 (3)0.027 (3)−0.004 (2)−0.004 (2)−0.008 (2)
C30.032 (3)0.031 (3)0.026 (3)−0.008 (2)−0.005 (2)−0.007 (2)
C40.032 (3)0.033 (3)0.025 (3)−0.010 (2)0.002 (2)−0.008 (2)
C50.045 (3)0.031 (3)0.032 (3)−0.005 (2)−0.003 (2)−0.005 (2)
C60.047 (3)0.040 (3)0.045 (4)0.000 (3)0.000 (3)−0.021 (3)
C70.055 (4)0.047 (3)0.037 (3)−0.013 (3)0.007 (3)−0.023 (3)
C80.045 (3)0.037 (3)0.028 (3)−0.008 (2)−0.001 (2)−0.012 (2)
Geometric parameters (Å, °) top
Ca1—O4i2.310 (4)N1—H10.8600
Ca1—O42.310 (4)N2—C21.286 (7)
Ca1—O52.313 (6)N3—C11.318 (8)
Ca1—O5i2.313 (6)N3—H3A0.8599
Ca1—O12.362 (4)N3—H3B0.8599
Ca1—O1i2.362 (4)C2—C31.484 (8)
S1—O31.446 (5)C2—H20.9300
S1—O21.455 (4)C3—C81.403 (8)
S1—O11.459 (4)C3—C41.410 (8)
S1—C41.781 (6)C4—C51.380 (9)
S2—C11.698 (6)C5—C61.389 (9)
O4—H4C0.8497C5—H50.9300
O4—H4D0.8503C6—C71.405 (10)
O5—H5C0.8504C6—H60.9300
O5—H5D0.8499C7—C81.378 (9)
N1—C11.351 (7)C7—H70.9300
N1—N21.372 (7)C8—H80.9300
O4i—Ca1—O4180.0H5C—O5—H5D108.9
O4i—Ca1—O590.5 (2)C1—N1—N2119.3 (5)
O4—Ca1—O589.5 (2)C1—N1—H1120.4
O4i—Ca1—O5i89.5 (2)N2—N1—H1120.3
O4—Ca1—O5i90.5 (2)C2—N2—N1115.2 (5)
O5—Ca1—O5i180.0C1—N3—H3A119.7
O4i—Ca1—O194.41 (17)C1—N3—H3B120.2
O4—Ca1—O185.59 (17)H3A—N3—H3B120.0
O5—Ca1—O196.42 (19)N3—C1—N1117.5 (5)
O5i—Ca1—O183.58 (19)N3—C1—S2123.7 (4)
O4i—Ca1—O1i85.59 (17)N1—C1—S2118.8 (5)
O4—Ca1—O1i94.41 (17)N2—C2—C3119.1 (6)
O5—Ca1—O1i83.58 (19)N2—C2—H2120.5
O5i—Ca1—O1i96.42 (19)C3—C2—H2120.5
O1—Ca1—O1i180.0C8—C3—C4117.7 (5)
O4i—Ca1—H5C83.1C8—C3—C2119.9 (5)
O4—Ca1—H5C96.9C4—C3—C2122.3 (5)
O5—Ca1—H5C16.4C5—C4—C3120.7 (5)
O5i—Ca1—H5C163.6C5—C4—S1117.3 (4)
O1—Ca1—H5C111.4C3—C4—S1121.9 (4)
O1i—Ca1—H5C68.6C4—C5—C6120.9 (6)
O3—S1—O2113.0 (3)C4—C5—H5119.5
O3—S1—O1112.4 (3)C6—C5—H5119.5
O2—S1—O1112.7 (3)C5—C6—C7119.1 (6)
O3—S1—C4106.2 (3)C5—C6—H6120.4
O2—S1—C4106.4 (3)C7—C6—H6120.4
O1—S1—C4105.5 (2)C8—C7—C6119.9 (6)
S1—O1—Ca1133.1 (2)C8—C7—H7120.1
Ca1—O4—H4C134.2C6—C7—H7120.1
Ca1—O4—H4D117.6C7—C8—C3121.6 (6)
H4C—O4—H4D108.2C7—C8—H8119.2
Ca1—O5—H5C113.7C3—C8—H8119.2
Ca1—O5—H5D137.2
O3—S1—O1—Ca1−98.8 (4)C8—C3—C4—S1177.3 (4)
O2—S1—O1—Ca130.3 (5)C2—C3—C4—S1−3.8 (7)
C4—S1—O1—Ca1145.9 (3)O3—S1—C4—C5115.4 (5)
O4i—Ca1—O1—S1−131.7 (4)O2—S1—C4—C5−5.2 (5)
O4—Ca1—O1—S148.3 (4)O1—S1—C4—C5−125.1 (5)
O5—Ca1—O1—S1137.3 (4)O3—S1—C4—C3−61.0 (5)
O5i—Ca1—O1—S1−42.7 (4)O2—S1—C4—C3178.4 (4)
O1i—Ca1—O1—S161 (12)O1—S1—C4—C358.5 (5)
C1—N1—N2—C2−175.4 (5)C3—C4—C5—C6−1.1 (9)
N2—N1—C1—N3−6.2 (8)S1—C4—C5—C6−177.5 (4)
N2—N1—C1—S2176.3 (4)C4—C5—C6—C70.9 (9)
N1—N2—C2—C3179.4 (5)C5—C6—C7—C8−0.8 (9)
N2—C2—C3—C84.4 (8)C6—C7—C8—C30.9 (9)
N2—C2—C3—C4−174.4 (5)C4—C3—C8—C7−1.0 (8)
C8—C3—C4—C51.1 (8)C2—C3—C8—C7−179.9 (5)
C2—C3—C4—C5180.0 (5)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···N20.862.282.636 (7)105
O5—H5C···O2i0.852.072.840 (9)150
N1—H1···S2ii0.862.603.441 (6)166
N3—H3B···O2iii0.862.343.035 (7)138
O4—H4C···S2iv0.852.423.261 (6)173
O4—H4D···O3v0.851.872.712 (8)171
O5—H5D···S2ii0.852.423.197 (8)152
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y, −z+2; (iii) x, y−1, z+1; (iv) x, y+1, z−1; (v) −x+2, −y+1, −z+1.
Table 1
Selected geometric parameters (Å) top
Ca1—O42.310 (4)Ca1—O12.362 (4)
Ca1—O52.313 (6)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···N20.862.282.636 (7)105
O5—H5C···O2i0.852.072.840 (9)150
N1—H1···S2ii0.862.603.441 (6)166
N3—H3B···O2iii0.862.343.035 (7)138
O4—H4C···S2iv0.852.423.261 (6)173
O4—H4D···O3v0.851.872.712 (8)171
O5—H5D···S2ii0.852.423.197 (8)152
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y, −z+2; (iii) x, y−1, z+1; (iv) x, y+1, z−1; (v) −x+2, −y+1, −z+1.
Acknowledgements top

The authors would like to thank the Program for New Century Excellent Talents in University for a research grant.

references
References top

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Sawant, S. K., Gaikwad, G. A., Sawant, V. A., Yamgar, B. A. & Chavan, S. S. (2009). Inorg. Chem. Commun. 12, 632–633.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.