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

Qiu, Z.-H.; Liang, F.-P.; Ruan, Q.-F.; Zhao, S.-R.

doi:10.1107/S1600536808007770

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page m588

doi:10.1107/S1600536808007770

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

Zhi-Hui Qiu,^a,^b ^* Fu-Pei Liang,^a Qing-Feng Ruan ^c and Shan-Rong Zhao ^b

^aCollege of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin 541004, People's Republic of China, ^bFaculty of Earth Sciences, China University of Geosciences, Wuhan 430074, People's Republic of China, and ^cDepartment of Resources and Environmental Engineering, Guilin University of Technology, Guilin 541004, People's Republic of China
^*Correspondence e-mail: zhihuiqiu299@yahoo.com.cn

(Received 5 March 2008; accepted 21 March 2008; online 29 March 2008)

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.

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 ).

Experimental

Crystal data

[Cd(C₅H₄NO₃S)₂(H₂O)₂]
M_r = 464.74
Monoclinic, P 2₁ /c
a = 7.7480 (11) Å
b = 13.264 (2) Å
c = 7.3291 (11) Å
β = 97.081 (2)°
V = 747.47 (19) Å³
Z = 2
Mo Kα radiation
μ = 1.78 mm⁻¹
T = 294 (2) K
0.26 × 0.22 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.674, T_max = 0.740
4111 measured reflections
1520 independent reflections
1396 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.053
S = 1.10
1520 reflections
115 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O3ⁱ	0.93	2.39	3.256 (3)	155
C4—H4⋯O2ⁱⁱ	0.93	2.55	3.422 (3)	157
O4—H4B⋯O3ⁱⁱⁱ	0.79 (3)	1.99 (4)	2.780 (3)	176 (3)
O4—H4A⋯O2^iv	0.81 (3)	1.98 (3)	2.773 (3)	168 (3)
Symmetry codes: (i) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) -x+1, -y+1, -z+2.

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); 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 datablock I. DOI: 10.1107/S1600536808007770/tk2252sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808007770/tk2252Isup2.hkl

checkCIF report

Comment top

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 top

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).

Experimental top

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.

Computing details top

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 top

	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] top

Crystal data top

[Cd(C₅H₄NO₃S)₂(H₂O)₂]	F(000) = 460
M_r = 464.74	D_x = 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) Å³	0.26 × 0.22 × 0.18 mm
Z = 2

Data collection top

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

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)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.053	w = 1/[σ²(F_o²) + (0.0952P)² + 1.5031P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
1520 reflections	Δρ_max = 0.42 e Å⁻³
115 parameters	Δρ_min = −0.73 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.087 (3)

Crystal data top

[Cd(C₅H₄NO₃S)₂(H₂O)₂]	V = 747.47 (19) Å³
M_r = 464.74	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7480 (11) Å	µ = 1.78 mm⁻¹
b = 13.264 (2) Å	T = 294 K
c = 7.3291 (11) Å	0.26 × 0.22 × 0.18 mm
β = 97.081 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1520 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1396 reflections with I > 2σ(I)
T_min = 0.674, T_max = 0.740	R_int = 0.023
4111 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	0 restraints
wR(F²) = 0.053	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.42 e Å⁻³
1520 reflections	Δρ_min = −0.73 e Å⁻³
115 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	0.0000	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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

Cd1—O4ⁱ	2.2872 (18)	O1—Cd1^iv	2.3113 (17)
Cd1—O4	2.2873 (18)	C1—C2	1.386 (3)
Cd1—O1ⁱⁱ	2.3113 (17)	C1—H1	0.9300
Cd1—O1ⁱⁱⁱ	2.3113 (17)	C2—C3	1.380 (3)
Cd1—N1ⁱ	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)

O4ⁱ—Cd1—O4	180	C5—N1—Cd1	121.09 (15)
O4ⁱ—Cd1—O1ⁱⁱ	83.10 (8)	C1—N1—Cd1	120.36 (15)
O4—Cd1—O1ⁱⁱ	96.90 (8)	S1—O1—Cd1^iv	142.09 (12)
O4ⁱ—Cd1—O1ⁱⁱⁱ	96.90 (8)	N1—C1—C2	122.1 (2)
O4—Cd1—O1ⁱⁱⁱ	83.10 (8)	N1—C1—H1	119.0
O1ⁱⁱ—Cd1—O1ⁱⁱⁱ	180	C2—C1—H1	119.0
O4ⁱ—Cd1—N1ⁱ	89.62 (7)	C3—C2—C1	119.3 (2)
O4—Cd1—N1ⁱ	90.38 (7)	C3—C2—S1	121.48 (17)
O1ⁱⁱ—Cd1—N1ⁱ	84.76 (7)	C1—C2—S1	119.21 (17)
O1ⁱⁱⁱ—Cd1—N1ⁱ	95.24 (7)	C4—C3—C2	118.8 (2)
O4ⁱ—Cd1—N1	90.37 (7)	C4—C3—H3	120.6
O4—Cd1—N1	89.63 (7)	C2—C3—H3	120.6
O1ⁱⁱ—Cd1—N1	95.24 (7)	C3—C4—C5	118.9 (2)
O1ⁱⁱⁱ—Cd1—N1	84.76 (7)	C3—C4—H4	120.5
N1ⁱ—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)

O4ⁱ—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)
O1ⁱⁱ—Cd1—N1—C5	−40.45 (19)	O2—S1—C2—C3	129.5 (2)
O1ⁱⁱⁱ—Cd1—N1—C5	139.55 (19)	O1—S1—C2—C3	−111.2 (2)
O4ⁱ—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)
O1ⁱⁱ—Cd1—N1—C1	146.60 (18)	O1—S1—C2—C1	67.5 (2)
O1ⁱⁱⁱ—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) top

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.

Experimental details

Crystal data
Chemical formula	[Cd(C₅H₄NO₃S)₂(H₂O)₂]
M_r	464.74
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	7.7480 (11), 13.264 (2), 7.3291 (11)
β (°)	97.081 (2)
V (Å³)	747.47 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.78
Crystal size (mm)	0.26 × 0.22 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.674, 0.740
No. of measured, independent and observed [I > 2σ(I)] reflections	4111, 1520, 1396
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.053, 1.10
No. of reflections	1520
No. of parameters	115
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.73

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O3ⁱ	0.93	2.39	3.256 (3)	155
C4—H4···O2ⁱⁱ	0.93	2.55	3.422 (3)	157
O4—H4B···O3ⁱⁱⁱ	0.79 (3)	1.99 (4)	2.780 (3)	176 (3)
O4—H4A···O2^iv	0.81 (3)	1.98 (3)	2.773 (3)	168 (3)

Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+1, −y+1, −z+2.

Acknowledgements

This work was supported by the Natural Science Foundation of Guangxi (GuiKeJi0639031), People's Republic of China. This research was also sponsored by the Program for Hundred Outstanding Young Teachers in Higher Education Institutions of Guangxi, People's Republic of China.

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