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

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.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.023
• wR factor = 0.061
• Data-to-parameter ratio = 13.4

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   298.000
            Value of melting point given =     0.000
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

H atom treatment??

Computing details

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

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

Crystal data

[Cd(H2O)6](C14H10O6N2S2)·2H2O	Z = 1
Mr = 622.89	F(000) = 316
Triclinic, P1	Dx = 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) Å^3

Data collection

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

Refinement

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

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Cd1—O5^i	2.2555 (18)	O6—H6B	0.8500
Cd1—O5	2.2555 (18)	O7—H7A	0.8499
Cd1—O4^i	2.2589 (17)	O7—H7B	0.8500
Cd1—O4	2.2589 (17)	S1—C3	1.783 (2)
Cd1—O6^i	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—N1^ii	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
O5^i—Cd1—O5	180.0	O3—S1—O1	111.68 (12)
O5^i—Cd1—O4^i	95.45 (7)	O2—S1—O1	111.24 (12)
O5—Cd1—O4^i	84.55 (7)	O3—S1—C3	106.73 (11)
O5^i—Cd1—O4	84.55 (7)	O2—S1—C3	106.56 (11)
O5—Cd1—O4	95.45 (7)	O1—S1—C3	105.47 (10)
O4^i—Cd1—O4	180.0	N1—C1—C2	120.7 (2)
O5^i—Cd1—O6^i	89.86 (7)	N1—C1—H1	119.7
O5—Cd1—O6^i	90.14 (7)	C2—C1—H1	119.7
O4^i—Cd1—O6^i	90.19 (7)	C7—C2—C3	118.4 (2)
O4—Cd1—O6^i	89.81 (7)	C7—C2—C1	119.8 (2)
O5^i—Cd1—O6	90.14 (7)	C3—C2—C1	121.7 (2)
O5—Cd1—O6	89.86 (7)	C4—C3—C2	120.5 (2)
O4^i—Cd1—O6	89.81 (7)	C4—C3—S1	118.63 (17)
O4—Cd1—O6	90.19 (7)	C2—C3—S1	120.88 (17)
O6^i—Cd1—O6	180.0	C3—C4—C5	120.0 (2)
C1—N1—N1^ii	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)
N1^ii—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)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O2^iii	0.85	1.94	2.783 (3)	171
O4—H4B···O1^i	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···N1^ii	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.