catena-Poly[[diaquacadmium(II)]bis­(μ-pyridine-3-sulfonato)-κ²N:O;κ²O:N]

In the title polymeric complex, [Cd(C₅H₄NO₃S)₂(H₂O)₂]_n, the Cd atom is located on a centre of inversion and is coordinated by two O atoms and two N atoms, derived from four different pyridine-3-sulfonate ligands, and two O atoms derived from two water mol­ecules, forming a distorted trans-N₂O₄ octa­hedral geometry. The topology of the polymer is a one-dimensional chain mediated by bridging pyridine-3-sulfonate anions. These are connected into a three-dimensional architecture via hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.021
• wR factor = 0.054
• Data-to-parameter ratio = 13.2

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S1. Comment

Complexes or salts based on pyridinesulfonate are very rare in the Cambridge Structural Database (CSD; Version 5.25; Allen, 2002). A six-coordinate complex with pyridine-3-sulfonate ligands that is closely related to the title complex, (I), has been reported (Walsh & Hathaway, 1980). Other pyridine-3-sulfonate complexes are also available (Brodersen et al., 1980; Cotton et al., 1992a, b; Mäkinen et al., 2001; van der Lee & Barboiu, 2004), as well as that of the acid (Chandrasekhar, 1977).

In (I), Fig. 1, the Cd atom is located on a centre of inversion and is six-coordinated by two N atoms and two O atoms derived from four different pyridine-3-sulfonate molecules, and two O atoms derived from two water molecules. The resulting trans-N₂O₄ donor sets defines a distorted octahedral environment for Cd with angles ranging from 84.76 (7) to 180°, Cd—O distances in the range 2.2872 (18) to 2.3113 (17) Å, and Cd—N distances of 2.3233 (18) and 2.3234 (18) Å.

The molecules aggregate via bridging pyridine-3-sulfonate anions to form a chain. In the crystal structure, chains are linked into a 3-D architecture via hydrogen bonding interactions, Table 1 & Fig. 2.

Related literature

For related literature, see: Allen (2002). For related structures, see: Brodersen et al. (1980); Chandrasekhar (1977); Cotton et al. (1992a,b); van der Lee & Barboiu (2004); Mäkinen et al. (2001); Walsh & Hathaway (1980).

S2. Experimental

Pyridine-3-sulfonate, (1 mmol, 159 mg) was dissolved in methanol (A.R., 99.9%) (10 ml). To the resulting clear solution was added CdCl₂.6H₂O (0.5 mmol, 149 mg) in methanol (10 ml). After keeping the resulting mixture in air to evaporate about half of the solvent, colourless blocks of (I) were deposited. The crystals were isolated, washed with ethanol three times (Yield 74%). Analysis: found: C, 25.98; H, 2.66; N, 6.08; S, 13.84; C₁₀H₁₂CdN₂O₈S₂ requires: C, 25.82; H, 2.58; N, 6.02; S, 14.27.

S3. Refinement

The C-bound H atoms were included in the riding model approximation with C—H = 0.93–0.96 Å, and with U_iso(H)= 1.2U_eq(C)-1.5U_eq(C). The water-bound H atoms were located in difference Fourier maps and the O—H distances were refined without constraint, see Table 1 for distances.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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. Extended structure in (I) showing the coordination geometry for the Cd atom, the atom labelling scheme and displacement ellipsoids at the 50% probability level. The Cd atom is located at a center of inversion.
	Fig. 2. Crystal packing of (I) viewed approximately down the a-direction showing the hydrogen bonding interactions as dashed lines.

catena-Poly[[diaquacadmium(II)]bis(µ-pyridine-3-sulfonato)- κ²N:O;κ²O:N]

Crystal data

[Cd(C5H4NO3S)2(H2O)2]	F(000) = 460
Mr = 464.74	Dx = 2.065 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3022 reflections
a = 7.7480 (11) Å	θ = 3.1–26.3°
b = 13.264 (2) Å	µ = 1.78 mm^−1
c = 7.3291 (11) Å	T = 294 K
β = 97.081 (2)°	Block, colourless
V = 747.47 (19) Å^3	0.26 × 0.22 × 0.18 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	1520 independent reflections
Radiation source: fine-focus sealed tube	1396 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ϕ and ο scans	θmax = 26.3°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −9→6
Tmin = 0.674, Tmax = 0.740	k = −16→15
4111 measured reflections	l = −4→9

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)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.053	w = 1/[σ^2(Fo^2) + (0.0952P)^2 + 1.5031P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.001
1520 reflections	Δρmax = 0.42 e Å^−3
115 parameters	Δρmin = −0.73 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.087 (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	0.0000	0.5000	0.5000	0.02008 (12)
S1	0.71583 (7)	0.62259 (4)	0.77922 (8)	0.02183 (15)
N1	0.2044 (2)	0.62074 (14)	0.6090 (3)	0.0246 (4)
O1	0.7687 (2)	0.57880 (16)	0.6122 (3)	0.0449 (5)
O2	0.7069 (2)	0.54880 (14)	0.9231 (3)	0.0392 (5)
O3	0.8146 (2)	0.71095 (13)	0.8402 (3)	0.0377 (4)
C1	0.3697 (3)	0.59388 (16)	0.6647 (3)	0.0234 (5)
H1	0.3979	0.5257	0.6722	0.028*
C2	0.4994 (3)	0.66450 (17)	0.7113 (3)	0.0202 (4)
C3	0.4585 (3)	0.76576 (17)	0.7005 (4)	0.0276 (5)
H3	0.5439	0.8143	0.7300	0.033*
C4	0.2885 (3)	0.79362 (18)	0.6450 (4)	0.0317 (5)
H4	0.2572	0.8613	0.6380	0.038*
C5	0.1657 (3)	0.71933 (18)	0.6000 (3)	0.0268 (5)
H5	0.0514	0.7385	0.5619	0.032*
O4	0.0841 (3)	0.40325 (16)	0.7537 (3)	0.0359 (4)
H4A	0.140 (4)	0.426 (2)	0.845 (5)	0.046 (10)*
H4B	0.113 (4)	0.348 (3)	0.733 (5)	0.043 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.01370 (15)	0.02211 (16)	0.02355 (16)	0.00007 (8)	−0.00117 (9)	−0.00150 (8)
S1	0.0152 (3)	0.0238 (3)	0.0254 (3)	−0.0008 (2)	−0.0021 (2)	−0.0035 (2)
N1	0.0181 (9)	0.0241 (9)	0.0305 (10)	0.0004 (8)	−0.0018 (8)	−0.0032 (8)
O1	0.0238 (9)	0.0694 (14)	0.0411 (11)	0.0142 (9)	0.0027 (8)	−0.0210 (10)
O2	0.0327 (10)	0.0345 (10)	0.0475 (12)	−0.0032 (8)	−0.0070 (8)	0.0145 (9)
O3	0.0270 (9)	0.0304 (9)	0.0518 (11)	−0.0079 (7)	−0.0107 (8)	−0.0012 (9)
C1	0.0191 (11)	0.0197 (10)	0.0301 (12)	0.0014 (8)	−0.0016 (9)	−0.0018 (9)
C2	0.0173 (10)	0.0245 (11)	0.0189 (10)	0.0005 (8)	0.0022 (8)	−0.0020 (8)
C3	0.0231 (11)	0.0207 (11)	0.0391 (13)	−0.0044 (9)	0.0049 (10)	−0.0049 (10)
C4	0.0297 (13)	0.0211 (11)	0.0444 (15)	0.0042 (10)	0.0047 (11)	−0.0008 (10)
C5	0.0187 (11)	0.0296 (12)	0.0313 (12)	0.0056 (9)	−0.0001 (9)	−0.0007 (10)
O4	0.0454 (11)	0.0315 (10)	0.0280 (10)	0.0043 (9)	−0.0059 (8)	0.0025 (8)

Geometric parameters (Å, º)

Cd1—O4^i	2.2872 (18)	O1—Cd1^iv	2.3113 (17)
Cd1—O4	2.2873 (18)	C1—C2	1.386 (3)
Cd1—O1^ii	2.3113 (17)	C1—H1	0.9300
Cd1—O1^iii	2.3113 (17)	C2—C3	1.380 (3)
Cd1—N1^i	2.3233 (18)	C3—C4	1.380 (4)
Cd1—N1	2.3234 (18)	C3—H3	0.9300
S1—O3	1.4404 (18)	C4—C5	1.382 (3)
S1—O2	1.4466 (19)	C4—H4	0.9300
S1—O1	1.4587 (19)	C5—H5	0.9300
S1—C2	1.779 (2)	O4—H4A	0.81 (3)
N1—C5	1.341 (3)	O4—H4B	0.79 (3)
N1—C1	1.344 (3)
O4^i—Cd1—O4	180	C5—N1—Cd1	121.09 (15)
O4^i—Cd1—O1^ii	83.10 (8)	C1—N1—Cd1	120.36 (15)
O4—Cd1—O1^ii	96.90 (8)	S1—O1—Cd1^iv	142.09 (12)
O4^i—Cd1—O1^iii	96.90 (8)	N1—C1—C2	122.1 (2)
O4—Cd1—O1^iii	83.10 (8)	N1—C1—H1	119.0
O1^ii—Cd1—O1^iii	180	C2—C1—H1	119.0
O4^i—Cd1—N1^i	89.62 (7)	C3—C2—C1	119.3 (2)
O4—Cd1—N1^i	90.38 (7)	C3—C2—S1	121.48 (17)
O1^ii—Cd1—N1^i	84.76 (7)	C1—C2—S1	119.21 (17)
O1^iii—Cd1—N1^i	95.24 (7)	C4—C3—C2	118.8 (2)
O4^i—Cd1—N1	90.37 (7)	C4—C3—H3	120.6
O4—Cd1—N1	89.63 (7)	C2—C3—H3	120.6
O1^ii—Cd1—N1	95.24 (7)	C3—C4—C5	118.9 (2)
O1^iii—Cd1—N1	84.76 (7)	C3—C4—H4	120.5
N1^i—Cd1—N1	180	C5—C4—H4	120.5
O3—S1—O2	113.30 (12)	N1—C5—C4	122.7 (2)
O3—S1—O1	113.01 (13)	N1—C5—H5	118.6
O2—S1—O1	112.70 (13)	C4—C5—H5	118.6
O3—S1—C2	106.20 (11)	Cd1—O4—H4A	122 (2)
O2—S1—C2	106.70 (11)	Cd1—O4—H4B	115 (2)
O1—S1—C2	104.03 (10)	H4A—O4—H4B	112 (3)
C5—N1—C1	118.18 (19)
O4^i—Cd1—N1—C5	42.65 (19)	N1—C1—C2—S1	−178.71 (18)
O4—Cd1—N1—C5	−137.35 (19)	O3—S1—C2—C3	8.3 (2)
O1^ii—Cd1—N1—C5	−40.45 (19)	O2—S1—C2—C3	129.5 (2)
O1^iii—Cd1—N1—C5	139.55 (19)	O1—S1—C2—C3	−111.2 (2)
O4^i—Cd1—N1—C1	−130.30 (18)	O3—S1—C2—C1	−173.02 (19)
O4—Cd1—N1—C1	49.70 (18)	O2—S1—C2—C1	−51.9 (2)
O1^ii—Cd1—N1—C1	146.60 (18)	O1—S1—C2—C1	67.5 (2)
O1^iii—Cd1—N1—C1	−33.40 (18)	C1—C2—C3—C4	0.6 (4)
O3—S1—O1—Cd1^iv	65.4 (2)	S1—C2—C3—C4	179.29 (19)
O2—S1—O1—Cd1^iv	−64.7 (2)	C2—C3—C4—C5	−0.8 (4)
C2—S1—O1—Cd1^iv	−179.9 (2)	C1—N1—C5—C4	0.2 (4)
C5—N1—C1—C2	−0.4 (3)	Cd1—N1—C5—C4	−172.90 (19)
Cd1—N1—C1—C2	172.76 (16)	C3—C4—C5—N1	0.4 (4)
N1—C1—C2—C3	0.0 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O3^v	0.93	2.39	3.256 (3)	155
C4—H4···O2^vi	0.93	2.55	3.422 (3)	157
O4—H4B···O3^vii	0.79 (3)	1.99 (4)	2.780 (3)	176 (3)
O4—H4A···O2^viii	0.81 (3)	1.98 (3)	2.773 (3)	168 (3)

Symmetry codes: (v) x−1, −y+3/2, z−1/2; (vi) −x+1, y+1/2, −z+3/2; (vii) −x+1, y−1/2, −z+3/2; (viii) −x+1, −y+1, −z+2.