Hexaaqua­cadmium(II) 2,2′-(azino­dimethyl­idyne)dibenzene­sulfonate dihydrate

Du, L.-C.

doi:10.1107/S1600536808039032

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page m1625

doi:10.1107/S1600536808039032

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Hexaaquacadmium(II) 2,2′-(azinodimethylidyne)dibenzenesulfonate dihydrate

Lian-Cai Du ^a ^*

^aCollege of Bioengineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: taixishi@lzu.edu.cn

(Received 19 November 2008; accepted 20 November 2008; online 26 November 2008)

In the title compound, [Cd(H₂O)₆](C₁₄H₁₀O₆N₂S₂)·2H₂O, the complete cation and anion are each generated by crystallographic inversion symmetry. In the crystal structure, the components form a three-dimensional network by way of O—H⋯O and O—H⋯N hydrogen bonds.

Related literature

For background to the properties and potential applications of organic–inorganic hybrid materials, see: Hagrman et al. (1998 ); Ranford et al. (1998 ).

Experimental

Crystal data

[Cd(H₂O)₆](C₁₄H₁₀O₆N₂S₂)·2H₂O
M_r = 622.89
Triclinic, $[P \overline 1]$
a = 7.8329 (11) Å
b = 7.9824 (12) Å
c = 10.1010 (15) Å
α = 92.723 (1)°
β = 102.076 (2)°
γ = 105.924 (2)°
V = 590.19 (15) Å³
Z = 1
Mo Kα radiation
μ = 1.17 mm⁻¹
T = 298 (2) K
0.45 × 0.40 × 0.28 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.621, T_max = 0.735
3081 measured reflections
2041 independent reflections
1929 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.061
S = 1.06
2041 reflections
152 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—O5	2.2555 (18)
Cd1—O4	2.2589 (17)
Cd1—O6	2.2947 (18)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O2ⁱ	0.85	1.94	2.783 (3)	171
O4—H4B⋯O1ⁱⁱ	0.85	2.03	2.872 (2)	174
O5—H5A⋯O1ⁱⁱⁱ	0.85	1.99	2.831 (3)	173
O5—H5B⋯O7^iv	0.85	2.00	2.843 (3)	173
O6—H6A⋯O7	0.85	2.08	2.881 (3)	157
O6—H6B⋯N1^v	0.85	2.15	2.993 (3)	169
O7—H7A⋯O3^vi	0.85	1.85	2.692 (3)	172
O7—H7B⋯O2ⁱⁱⁱ	0.85	2.21	3.002 (3)	156
Symmetry codes: (i) x-1, y-1, z; (ii) -x+1, -y+1, -z+1; (iii) -x+2, -y+1, -z+1; (iv) -x+1, -y, -z+1; (v) -x+1, -y+1, -z; (vi) x, y-1, z.

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/S1600536808039032/hb2858sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039032/hb2858Isup2.hkl

checkCIF report

Comment top

The design and synthesis of organic/inorganic hybrid materials have attracted intense attention in recent years owing to their potential practical applications, such as antitumor, antidiabetic, antitubercular activities, magnetism and catalysis [Ranford, et al., 1998; Hagrman, et al., 1998]. As part of our studies in this area, we now report the synthesis and crystal structure of the title compound, (I).

The Cd(II) centre is six-coordinate with six O donors of H₂O, and adopts distorted octahedral coordination (Table 1, Fig. 1). In the crystal, the molecules form a three-dimensional network by way of O—H···O and O—H···N hydrogen bonds (Table 2).

Related literature top

For background to the properties and potential applications of organic–inorganic hybrid materials, see: Hagrman et al. (1998); Ranford et al. (1998).

Experimental top

A solution of 1.0 mmol 2-formyl-benzenesulfonic acid-hydrazine and 1.0 mmol NaOH in 5 ml 95% ethanol was added to a solution of 0.5 mmol Cd(CH₃COO)₂.4H₂O in 5 ml ethanol 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 50% displacement ellipsoids for the non-hydrogen atoms. Symmetry codes: (i) 1–x, 1–y, 1–z; (ii) 1–x, 1–y, –z.

Hexaaquacadmium(II) 2,2'-(azinodimethylidyne)dibenzenesulfonate dihydrate top

Crystal data top

[Cd(H₂O)₆](C₁₄H₁₀O₆N₂S₂)·2H₂O	Z = 1
M_r = 622.89	F(000) = 316
Triclinic, P1	D_x = 1.753 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8329 (11) Å	Cell parameters from 2719 reflections
b = 7.9824 (12) Å	θ = 2.7–28.3°
c = 10.1010 (15) Å	µ = 1.17 mm⁻¹
α = 92.723 (1)°	T = 298 K
β = 102.076 (2)°	Block, colourless
γ = 105.924 (2)°	0.45 × 0.40 × 0.28 mm
V = 590.19 (15) Å³

Data collection top

Bruker SMART CCD diffractometer	2041 independent reflections
Radiation source: fine-focus sealed tube	1929 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→9
T_min = 0.621, T_max = 0.735	k = −5→9
3081 measured reflections	l = −11→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.061	w = 1/[σ²(F_o²) + (0.0313P)² + 0.2007P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2041 reflections	Δρ_max = 0.33 e Å⁻³
152 parameters	Δρ_min = −0.42 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.067 (3)

Crystal data top

[Cd(H₂O)₆](C₁₄H₁₀O₆N₂S₂)·2H₂O	γ = 105.924 (2)°
M_r = 622.89	V = 590.19 (15) Å³
Triclinic, P1	Z = 1
a = 7.8329 (11) Å	Mo Kα radiation
b = 7.9824 (12) Å	µ = 1.17 mm⁻¹
c = 10.1010 (15) Å	T = 298 K
α = 92.723 (1)°	0.45 × 0.40 × 0.28 mm
β = 102.076 (2)°

Data collection top

Bruker SMART CCD diffractometer	2041 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1929 reflections with I > 2σ(I)
T_min = 0.621, T_max = 0.735	R_int = 0.018
3081 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.061	H-atom parameters constrained
S = 1.06	Δρ_max = 0.33 e Å⁻³
2041 reflections	Δρ_min = −0.42 e Å⁻³
152 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
Cd1	0.5000	0.5000	0.5000	0.02922 (13)
N1	0.5732 (3)	0.5473 (3)	−0.0282 (2)	0.0336 (5)
O1	1.0298 (2)	0.6986 (2)	0.35433 (17)	0.0384 (4)
O2	1.1817 (3)	1.0036 (3)	0.35043 (19)	0.0465 (5)
O3	0.8508 (3)	0.8917 (3)	0.2790 (2)	0.0477 (5)
O4	0.2044 (2)	0.3385 (2)	0.45818 (18)	0.0406 (4)
H4A	0.1847	0.2342	0.4229	0.049*
H4B	0.1378	0.3362	0.5150	0.049*
O5	0.6085 (3)	0.3128 (3)	0.6297 (2)	0.0471 (5)
H5A	0.7201	0.3195	0.6358	0.057*
H5B	0.5490	0.2060	0.6283	0.057*
O6	0.5347 (3)	0.3561 (3)	0.30977 (19)	0.0448 (5)
H6A	0.5293	0.2485	0.3123	0.054*
H6B	0.4908	0.3730	0.2289	0.054*
O7	0.6167 (3)	0.0337 (3)	0.3703 (2)	0.0468 (5)
H7A	0.6908	−0.0043	0.3358	0.056*
H7B	0.6594	0.0466	0.4560	0.056*
S1	1.02370 (7)	0.85670 (8)	0.28844 (6)	0.02847 (16)
C1	0.7223 (3)	0.5998 (3)	0.0615 (2)	0.0303 (5)
H1	0.7234	0.5806	0.1517	0.036*
C2	0.8948 (3)	0.6913 (3)	0.0237 (2)	0.0265 (5)
C3	1.0408 (3)	0.8087 (3)	0.1183 (2)	0.0258 (5)
C4	1.2027 (3)	0.8863 (3)	0.0822 (3)	0.0348 (6)
H4	1.2984	0.9650	0.1451	0.042*
C5	1.2224 (4)	0.8469 (4)	−0.0476 (3)	0.0423 (6)
H5	1.3316	0.8989	−0.0717	0.051*
C6	1.0809 (3)	0.7311 (4)	−0.1414 (3)	0.0386 (6)
H6	1.0948	0.7044	−0.2284	0.046*
C7	0.9177 (3)	0.6542 (3)	−0.1061 (2)	0.0337 (5)
H7	0.8223	0.5768	−0.1701	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.03192 (17)	0.02725 (17)	0.02920 (17)	0.01001 (10)	0.00609 (10)	0.00611 (10)
N1	0.0251 (10)	0.0408 (12)	0.0293 (11)	0.0001 (9)	0.0060 (8)	0.0066 (9)
O1	0.0449 (10)	0.0429 (10)	0.0318 (9)	0.0163 (8)	0.0123 (8)	0.0108 (8)
O2	0.0477 (11)	0.0433 (11)	0.0375 (10)	−0.0004 (9)	0.0074 (8)	−0.0093 (9)
O3	0.0429 (10)	0.0629 (13)	0.0486 (12)	0.0291 (10)	0.0168 (9)	0.0054 (10)
O4	0.0398 (10)	0.0394 (10)	0.0389 (10)	0.0022 (8)	0.0151 (8)	0.0000 (8)
O5	0.0416 (10)	0.0394 (11)	0.0614 (13)	0.0147 (9)	0.0069 (9)	0.0211 (9)
O6	0.0639 (12)	0.0415 (11)	0.0329 (10)	0.0200 (10)	0.0132 (9)	0.0038 (8)
O7	0.0447 (11)	0.0518 (12)	0.0501 (12)	0.0243 (9)	0.0123 (9)	−0.0007 (9)
S1	0.0288 (3)	0.0306 (3)	0.0257 (3)	0.0085 (2)	0.0063 (2)	0.0008 (2)
C1	0.0290 (12)	0.0316 (13)	0.0265 (12)	0.0036 (10)	0.0048 (10)	0.0033 (10)
C2	0.0251 (11)	0.0282 (12)	0.0260 (12)	0.0080 (9)	0.0044 (9)	0.0069 (9)
C3	0.0253 (11)	0.0268 (12)	0.0258 (12)	0.0086 (9)	0.0054 (9)	0.0055 (9)
C4	0.0259 (12)	0.0389 (14)	0.0329 (13)	0.0008 (10)	0.0040 (10)	0.0036 (11)
C5	0.0325 (13)	0.0565 (17)	0.0374 (15)	0.0052 (12)	0.0158 (11)	0.0127 (13)
C6	0.0401 (14)	0.0504 (16)	0.0287 (13)	0.0143 (12)	0.0131 (11)	0.0086 (12)
C7	0.0335 (13)	0.0382 (14)	0.0265 (12)	0.0087 (11)	0.0029 (10)	0.0021 (10)

Geometric parameters (Å, º) top

Cd1—O5ⁱ	2.2555 (18)	O6—H6B	0.8500
Cd1—O5	2.2555 (18)	O7—H7A	0.8499
Cd1—O4ⁱ	2.2589 (17)	O7—H7B	0.8500
Cd1—O4	2.2589 (17)	S1—C3	1.783 (2)
Cd1—O6ⁱ	2.2947 (18)	C1—C2	1.485 (3)
Cd1—O6	2.2947 (18)	C1—H1	0.9300
N1—C1	1.270 (3)	C2—C7	1.390 (3)
N1—N1ⁱⁱ	1.431 (4)	C2—C3	1.403 (3)
O1—S1	1.4621 (19)	C3—C4	1.382 (3)
O2—S1	1.4523 (19)	C4—C5	1.384 (4)
O3—S1	1.4414 (18)	C4—H4	0.9300
O4—H4A	0.8500	C5—C6	1.377 (4)
O4—H4B	0.8500	C5—H5	0.9300
O5—H5A	0.8500	C6—C7	1.385 (4)
O5—H5B	0.8500	C6—H6	0.9300
O6—H6A	0.8499	C7—H7	0.9300

O5ⁱ—Cd1—O5	180.0	O3—S1—O1	111.68 (12)
O5ⁱ—Cd1—O4ⁱ	95.45 (7)	O2—S1—O1	111.24 (12)
O5—Cd1—O4ⁱ	84.55 (7)	O3—S1—C3	106.73 (11)
O5ⁱ—Cd1—O4	84.55 (7)	O2—S1—C3	106.56 (11)
O5—Cd1—O4	95.45 (7)	O1—S1—C3	105.47 (10)
O4ⁱ—Cd1—O4	180.0	N1—C1—C2	120.7 (2)
O5ⁱ—Cd1—O6ⁱ	89.86 (7)	N1—C1—H1	119.7
O5—Cd1—O6ⁱ	90.14 (7)	C2—C1—H1	119.7
O4ⁱ—Cd1—O6ⁱ	90.19 (7)	C7—C2—C3	118.4 (2)
O4—Cd1—O6ⁱ	89.81 (7)	C7—C2—C1	119.8 (2)
O5ⁱ—Cd1—O6	90.14 (7)	C3—C2—C1	121.7 (2)
O5—Cd1—O6	89.86 (7)	C4—C3—C2	120.5 (2)
O4ⁱ—Cd1—O6	89.81 (7)	C4—C3—S1	118.63 (17)
O4—Cd1—O6	90.19 (7)	C2—C3—S1	120.88 (17)
O6ⁱ—Cd1—O6	180.0	C3—C4—C5	120.0 (2)
C1—N1—N1ⁱⁱ	111.5 (2)	C3—C4—H4	120.0
Cd1—O4—H4A	113.7	C5—C4—H4	120.0
Cd1—O4—H4B	123.5	C6—C5—C4	120.3 (2)
H4A—O4—H4B	108.3	C6—C5—H5	119.9
Cd1—O5—H5A	116.0	C4—C5—H5	119.9
Cd1—O5—H5B	123.2	C5—C6—C7	120.0 (2)
H5A—O5—H5B	108.7	C5—C6—H6	120.0
Cd1—O6—H6A	116.9	C7—C6—H6	120.0
Cd1—O6—H6B	123.6	C6—C7—C2	120.8 (2)
H6A—O6—H6B	109.5	C6—C7—H7	119.6
H7A—O7—H7B	105.6	C2—C7—H7	119.6
O3—S1—O2	114.51 (12)

N1ⁱⁱ—N1—C1—C2	176.2 (2)	O3—S1—C3—C2	−47.1 (2)
N1—C1—C2—C7	−29.2 (4)	O2—S1—C3—C2	−169.90 (19)
N1—C1—C2—C3	154.3 (2)	O1—S1—C3—C2	71.8 (2)
C7—C2—C3—C4	0.5 (3)	C2—C3—C4—C5	−0.7 (4)
C1—C2—C3—C4	177.1 (2)	S1—C3—C4—C5	177.7 (2)
C7—C2—C3—S1	−177.85 (18)	C3—C4—C5—C6	0.3 (4)
C1—C2—C3—S1	−1.2 (3)	C4—C5—C6—C7	0.3 (4)
O3—S1—C3—C4	134.5 (2)	C5—C6—C7—C2	−0.5 (4)
O2—S1—C3—C4	11.7 (2)	C3—C2—C7—C6	0.1 (4)
O1—S1—C3—C4	−106.6 (2)	C1—C2—C7—C6	−176.6 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O2ⁱⁱⁱ	0.85	1.94	2.783 (3)	171
O4—H4B···O1ⁱ	0.85	2.03	2.872 (2)	174
O5—H5A···O1^iv	0.85	1.99	2.831 (3)	173
O5—H5B···O7^v	0.85	2.00	2.843 (3)	173
O6—H6A···O7	0.85	2.08	2.881 (3)	157
O6—H6B···N1ⁱⁱ	0.85	2.15	2.993 (3)	169
O7—H7A···O3^vi	0.85	1.85	2.692 (3)	172
O7—H7B···O2^iv	0.85	2.21	3.002 (3)	156

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z; (iii) x−1, y−1, z; (iv) −x+2, −y+1, −z+1; (v) −x+1, −y, −z+1; (vi) x, y−1, z.

Experimental details

Crystal data
Chemical formula	[Cd(H₂O)₆](C₁₄H₁₀O₆N₂S₂)·2H₂O
M_r	622.89
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.8329 (11), 7.9824 (12), 10.1010 (15)
α, β, γ (°)	92.723 (1), 102.076 (2), 105.924 (2)
V (Å³)	590.19 (15)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.17
Crystal size (mm)	0.45 × 0.40 × 0.28

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.621, 0.735
No. of measured, independent and observed [I > 2σ(I)] reflections	3081, 2041, 1929
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.061, 1.06
No. of reflections	2041
No. of parameters	152
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.42

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

Selected bond lengths (Å) top

Cd1—O5	2.2555 (18)	Cd1—O6	2.2947 (18)
Cd1—O4	2.2589 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O2ⁱ	0.85	1.94	2.783 (3)	171
O4—H4B···O1ⁱⁱ	0.85	2.03	2.872 (2)	174
O5—H5A···O1ⁱⁱⁱ	0.85	1.99	2.831 (3)	173
O5—H5B···O7^iv	0.85	2.00	2.843 (3)	173
O6—H6A···O7	0.85	2.08	2.881 (3)	157
O6—H6B···N1^v	0.85	2.15	2.993 (3)	169
O7—H7A···O3^vi	0.85	1.85	2.692 (3)	172
O7—H7B···O2ⁱⁱⁱ	0.85	2.21	3.002 (3)	156

Symmetry codes: (i) x−1, y−1, z; (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y+1, −z+1; (iv) −x+1, −y, −z+1; (v) −x+1, −y+1, −z; (vi) x, y−1, z.

Acknowledgements

The authors thank the Science and Technology Foundation of Weifang (2008–19) for a research grant.

References

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