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

Wei, Z.; Yuan-Tao, C.

doi:10.1107/S1600536809035971

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page m1195

doi:10.1107/S1600536809035971

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

Zhang Wei ^a and Chen Yuan-Tao ^a ^*

^aDepartment of Chemistry, Qinghai Normal University, Xining 810008, People's Republic of China
^*Correspondence e-mail: chenyt@qhnu.edu.cn

(Received 28 August 2009; accepted 5 September 2009; online 12 September 2009)

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.

Related literature

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

Experimental

Crystal data

[Ca(C₈H₈N₃O₃S₂)₂(H₂O)₄]
M_r = 628.73
Triclinic, $[P \overline 1]$
a = 6.9123 (11) Å
b = 9.6383 (13) Å
c = 10.9481 (17) Å
α = 64.372 (1)°
β = 87.708 (2)°
γ = 83.225 (2)°
V = 652.99 (17) Å³
Z = 1
Mo Kα radiation
μ = 0.62 mm⁻¹
T = 298 K
0.31 × 0.15 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan SADABS (Bruker, 2000 ) T_min = 0.831, T_max = 0.929
2223 measured reflections
2223 independent reflections
1781 reflections with I > 2σ(I)

Refinement

R[F² > 2σ(F²)] = 0.078
wR(F²) = 0.227
S = 1.04
2223 reflections
170 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Selected bond lengths (Å)

Ca1—O4	2.310 (4)
Ca1—O5	2.313 (6)
Ca1—O1	2.362 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N2	0.86	2.28	2.636 (7)	105
O5—H5C⋯O2ⁱ	0.85	2.07	2.840 (9)	150
N1—H1⋯S2ⁱⁱ	0.86	2.60	3.441 (6)	166
N3—H3B⋯O2ⁱⁱⁱ	0.86	2.34	3.035 (7)	138
O4—H4C⋯S2^iv	0.85	2.42	3.261 (6)	173
O4—H4D⋯O3^v	0.85	1.87	2.712 (8)	171
O5—H5D⋯S2ⁱⁱ	0.85	2.42	3.197 (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.

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809035971/hb5075sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035971/hb5075Isup2.hkl

checkCIF report

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

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
M_r = 628.73	F(000) = 326
Triclinic, P1	D_x = 1.599 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9123 (11) Å	Cell parameters from 1563 reflections
b = 9.6383 (13) Å	θ = 3.6–27.6°
c = 10.9481 (17) Å	µ = 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 tube	1781 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.000
ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan SADABS (Bruker, 2000)	h = −8→8
T_min = 0.831, T_max = 0.929	k = −10→11
2223 measured reflections	l = −9→13

Refinement top

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)] = 0.078	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.227	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.1501P)² + 0.6556P] where P = (F_o² + 2F_c²)/3
2223 reflections	(Δ/σ)_max < 0.001
170 parameters	Δρ_max = 0.60 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

[Ca(C₈H₈N₃O₃S₂)₂(H₂O)₄]	γ = 83.225 (2)°
M_r = 628.73	V = 652.99 (17) Å³
Triclinic, P1	Z = 1
a = 6.9123 (11) Å	Mo Kα radiation
b = 9.6383 (13) Å	µ = 0.62 mm⁻¹
c = 10.9481 (17) Å	T = 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)
T_min = 0.831, T_max = 0.929	R_int = 0.000
2223 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.078	0 restraints
wR(F²) = 0.227	H-atom parameters constrained
S = 1.04	Δρ_max = 0.60 e Å⁻³
2223 reflections	Δρ_min = −0.55 e Å⁻³
170 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

	x	y	z	U_iso*/U_eq
Ca1	0.5000	0.5000	0.5000	0.0345 (5)
S1	0.7458 (2)	0.67806 (16)	0.65974 (13)	0.0354 (4)
S2	1.0140 (3)	−0.13332 (17)	1.21326 (16)	0.0449 (5)
O1	0.6451 (7)	0.5503 (5)	0.6662 (4)	0.0438 (11)
O2	0.6760 (7)	0.8251 (5)	0.5486 (4)	0.0501 (12)
O3	0.9554 (7)	0.6437 (6)	0.6624 (5)	0.0507 (12)
O4	0.7857 (7)	0.5634 (6)	0.3822 (5)	0.0556 (13)
H4C	0.8364	0.6474	0.3401	0.083*
H4D	0.8592	0.4914	0.3730	0.083*
O5	0.6194 (10)	0.2408 (6)	0.5851 (8)	0.096 (3)
H5C	0.5528	0.1878	0.5611	0.143*
H5D	0.7093	0.1806	0.6394	0.143*
N1	0.9136 (7)	0.1670 (6)	1.0860 (5)	0.0354 (11)
H1	0.9541	0.1587	1.0139	0.043*
N2	0.8339 (7)	0.3076 (5)	1.0789 (5)	0.0337 (11)
N3	0.8802 (9)	0.0645 (6)	1.3157 (5)	0.0506 (14)
H3A	0.8420	0.1565	1.3071	0.061*
H3B	0.8874	−0.0123	1.3947	0.061*
C1	0.9278 (8)	0.0419 (6)	1.2074 (6)	0.0353 (13)
C2	0.8137 (8)	0.4179 (6)	0.9586 (6)	0.0352 (12)
H2	0.8529	0.4001	0.8838	0.042*
C3	0.7269 (8)	0.5739 (6)	0.9407 (5)	0.0309 (12)
C4	0.6848 (8)	0.6971 (6)	0.8118 (5)	0.0311 (12)
C5	0.6039 (9)	0.8407 (7)	0.7991 (6)	0.0390 (13)
H5	0.5791	0.9211	0.7133	0.047*
C6	0.5592 (9)	0.8668 (7)	0.9128 (7)	0.0429 (14)
H6	0.5031	0.9635	0.9034	0.052*
C7	0.5998 (9)	0.7453 (8)	1.0420 (7)	0.0441 (15)
H7	0.5721	0.7615	1.1190	0.053*
C8	0.6807 (9)	0.6020 (7)	1.0545 (6)	0.0369 (13)
H8	0.7054	0.5219	1.1406	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca1	0.0392 (9)	0.0391 (9)	0.0220 (8)	−0.0068 (7)	−0.0025 (6)	−0.0094 (7)
S1	0.0473 (9)	0.0352 (8)	0.0200 (7)	−0.0087 (6)	−0.0001 (6)	−0.0074 (6)
S2	0.0613 (11)	0.0331 (8)	0.0317 (8)	−0.0016 (7)	−0.0043 (7)	−0.0066 (7)
O1	0.069 (3)	0.044 (2)	0.0195 (19)	−0.016 (2)	−0.0045 (18)	−0.0119 (18)
O2	0.080 (3)	0.040 (2)	0.023 (2)	−0.011 (2)	−0.005 (2)	−0.0059 (19)
O3	0.053 (3)	0.066 (3)	0.042 (3)	−0.011 (2)	0.008 (2)	−0.031 (2)
O4	0.056 (3)	0.058 (3)	0.053 (3)	−0.017 (2)	0.019 (2)	−0.023 (2)
O5	0.103 (5)	0.043 (3)	0.123 (6)	0.013 (3)	−0.073 (4)	−0.018 (3)
N1	0.042 (3)	0.034 (2)	0.022 (2)	0.001 (2)	−0.0021 (19)	−0.005 (2)
N2	0.038 (3)	0.030 (2)	0.029 (3)	−0.0019 (19)	−0.0006 (19)	−0.009 (2)
N3	0.082 (4)	0.034 (3)	0.024 (3)	0.000 (3)	0.000 (2)	−0.004 (2)
C1	0.040 (3)	0.035 (3)	0.025 (3)	−0.007 (2)	−0.003 (2)	−0.006 (2)
C2	0.039 (3)	0.034 (3)	0.027 (3)	−0.004 (2)	−0.004 (2)	−0.008 (2)
C3	0.032 (3)	0.031 (3)	0.026 (3)	−0.008 (2)	−0.005 (2)	−0.007 (2)
C4	0.032 (3)	0.033 (3)	0.025 (3)	−0.010 (2)	0.002 (2)	−0.008 (2)
C5	0.045 (3)	0.031 (3)	0.032 (3)	−0.005 (2)	−0.003 (2)	−0.005 (2)
C6	0.047 (3)	0.040 (3)	0.045 (4)	0.000 (3)	0.000 (3)	−0.021 (3)
C7	0.055 (4)	0.047 (3)	0.037 (3)	−0.013 (3)	0.007 (3)	−0.023 (3)
C8	0.045 (3)	0.037 (3)	0.028 (3)	−0.008 (2)	−0.001 (2)	−0.012 (2)

Geometric parameters (Å, º) top

Ca1—O4ⁱ	2.310 (4)	N1—H1	0.8600
Ca1—O4	2.310 (4)	N2—C2	1.286 (7)
Ca1—O5	2.313 (6)	N3—C1	1.318 (8)
Ca1—O5ⁱ	2.313 (6)	N3—H3A	0.8599
Ca1—O1	2.362 (4)	N3—H3B	0.8599
Ca1—O1ⁱ	2.362 (4)	C2—C3	1.484 (8)
S1—O3	1.446 (5)	C2—H2	0.9300
S1—O2	1.455 (4)	C3—C8	1.403 (8)
S1—O1	1.459 (4)	C3—C4	1.410 (8)
S1—C4	1.781 (6)	C4—C5	1.380 (9)
S2—C1	1.698 (6)	C5—C6	1.389 (9)
O4—H4C	0.8497	C5—H5	0.9300
O4—H4D	0.8503	C6—C7	1.405 (10)
O5—H5C	0.8504	C6—H6	0.9300
O5—H5D	0.8499	C7—C8	1.378 (9)
N1—C1	1.351 (7)	C7—H7	0.9300
N1—N2	1.372 (7)	C8—H8	0.9300

O4ⁱ—Ca1—O4	180.0	H5C—O5—H5D	108.9
O4ⁱ—Ca1—O5	90.5 (2)	C1—N1—N2	119.3 (5)
O4—Ca1—O5	89.5 (2)	C1—N1—H1	120.4
O4ⁱ—Ca1—O5ⁱ	89.5 (2)	N2—N1—H1	120.3
O4—Ca1—O5ⁱ	90.5 (2)	C2—N2—N1	115.2 (5)
O5—Ca1—O5ⁱ	180.0	C1—N3—H3A	119.7
O4ⁱ—Ca1—O1	94.41 (17)	C1—N3—H3B	120.2
O4—Ca1—O1	85.59 (17)	H3A—N3—H3B	120.0
O5—Ca1—O1	96.42 (19)	N3—C1—N1	117.5 (5)
O5ⁱ—Ca1—O1	83.58 (19)	N3—C1—S2	123.7 (4)
O4ⁱ—Ca1—O1ⁱ	85.59 (17)	N1—C1—S2	118.8 (5)
O4—Ca1—O1ⁱ	94.41 (17)	N2—C2—C3	119.1 (6)
O5—Ca1—O1ⁱ	83.58 (19)	N2—C2—H2	120.5
O5ⁱ—Ca1—O1ⁱ	96.42 (19)	C3—C2—H2	120.5
O1—Ca1—O1ⁱ	180.0	C8—C3—C4	117.7 (5)
O4ⁱ—Ca1—H5C	83.1	C8—C3—C2	119.9 (5)
O4—Ca1—H5C	96.9	C4—C3—C2	122.3 (5)
O5—Ca1—H5C	16.4	C5—C4—C3	120.7 (5)
O5ⁱ—Ca1—H5C	163.6	C5—C4—S1	117.3 (4)
O1—Ca1—H5C	111.4	C3—C4—S1	121.9 (4)
O1ⁱ—Ca1—H5C	68.6	C4—C5—C6	120.9 (6)
O3—S1—O2	113.0 (3)	C4—C5—H5	119.5
O3—S1—O1	112.4 (3)	C6—C5—H5	119.5
O2—S1—O1	112.7 (3)	C5—C6—C7	119.1 (6)
O3—S1—C4	106.2 (3)	C5—C6—H6	120.4
O2—S1—C4	106.4 (3)	C7—C6—H6	120.4
O1—S1—C4	105.5 (2)	C8—C7—C6	119.9 (6)
S1—O1—Ca1	133.1 (2)	C8—C7—H7	120.1
Ca1—O4—H4C	134.2	C6—C7—H7	120.1
Ca1—O4—H4D	117.6	C7—C8—C3	121.6 (6)
H4C—O4—H4D	108.2	C7—C8—H8	119.2
Ca1—O5—H5C	113.7	C3—C8—H8	119.2
Ca1—O5—H5D	137.2

O3—S1—O1—Ca1	−98.8 (4)	C8—C3—C4—S1	177.3 (4)
O2—S1—O1—Ca1	30.3 (5)	C2—C3—C4—S1	−3.8 (7)
C4—S1—O1—Ca1	145.9 (3)	O3—S1—C4—C5	115.4 (5)
O4ⁱ—Ca1—O1—S1	−131.7 (4)	O2—S1—C4—C5	−5.2 (5)
O4—Ca1—O1—S1	48.3 (4)	O1—S1—C4—C5	−125.1 (5)
O5—Ca1—O1—S1	137.3 (4)	O3—S1—C4—C3	−61.0 (5)
O5ⁱ—Ca1—O1—S1	−42.7 (4)	O2—S1—C4—C3	178.4 (4)
O1ⁱ—Ca1—O1—S1	61 (12)	O1—S1—C4—C3	58.5 (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—S2	176.3 (4)	C4—C5—C6—C7	0.9 (9)
N1—N2—C2—C3	179.4 (5)	C5—C6—C7—C8	−0.8 (9)
N2—C2—C3—C8	4.4 (8)	C6—C7—C8—C3	0.9 (9)
N2—C2—C3—C4	−174.4 (5)	C4—C3—C8—C7	−1.0 (8)
C8—C3—C4—C5	1.1 (8)	C2—C3—C8—C7	−179.9 (5)
C2—C3—C4—C5	180.0 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2	0.86	2.28	2.636 (7)	105
O5—H5C···O2ⁱ	0.85	2.07	2.840 (9)	150
N1—H1···S2ⁱⁱ	0.86	2.60	3.441 (6)	166
N3—H3B···O2ⁱⁱⁱ	0.86	2.34	3.035 (7)	138
O4—H4C···S2^iv	0.85	2.42	3.261 (6)	173
O4—H4D···O3^v	0.85	1.87	2.712 (8)	171
O5—H5D···S2ⁱⁱ	0.85	2.42	3.197 (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.

Experimental details

Crystal data
Chemical formula	[Ca(C₈H₈N₃O₃S₂)₂(H₂O)₄]
M_r	628.73
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	6.9123 (11), 9.6383 (13), 10.9481 (17)
α, β, γ (°)	64.372 (1), 87.708 (2), 83.225 (2)
V (Å³)	652.99 (17)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.62
Crystal size (mm)	0.31 × 0.15 × 0.12

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan SADABS (Bruker, 2000)
T_min, T_max	0.831, 0.929
No. of measured, independent and observed [I > 2σ(I)] reflections	2223, 2223, 1781
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.078, 0.227, 1.04
No. of reflections	2223
No. of parameters	170
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.55

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ca1—O4	2.310 (4)	Ca1—O1	2.362 (4)
Ca1—O5	2.313 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2	0.86	2.28	2.636 (7)	105
O5—H5C···O2ⁱ	0.85	2.07	2.840 (9)	150
N1—H1···S2ⁱⁱ	0.86	2.60	3.441 (6)	166
N3—H3B···O2ⁱⁱⁱ	0.86	2.34	3.035 (7)	138
O4—H4C···S2^iv	0.85	2.42	3.261 (6)	173
O4—H4D···O3^v	0.85	1.87	2.712 (8)	171
O5—H5D···S2ⁱⁱ	0.85	2.42	3.197 (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

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

References

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