catena-Poly[[diaqua­nickel(II)]-bis­(μ-pyridine-4-sulfinato)-κ2N,O;κ2O,N]

Du, Z.-X.; Ji, S.-N.

doi:10.1107/S1600536809024258

metal-organic compounds

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Volume 65| Part 8| August 2009| Page m846

doi:10.1107/S1600536809024258

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catena-Poly[[diaquanickel(II)]-bis(μ-pyridine-4-sulfinato)-κ²N,O;κ²O,N]

Zhong-Xiang Du ^a ^* and Su-Ning Ji ^a

^aDepartment of Chemistry, Luoyang Normal University, Luoyang, Henan 471022, People's Republic of China
^*Correspondence e-mail: dzx6281@126.com

(Received 13 June 2009; accepted 24 June 2009; online 1 July 2009)

In the title coordination polymer, [Ni(C₅H₄NO₂S)₂(H₂O)₂]_n, the Ni^II ion is located on an inversion centre and is octahedrally coordinated by two N and two O atoms of four symmetry-related and deprotonated pyridine-4-sulfinate (ps) ligands together with two water molecules in axial positions. The ps⁻ anions, acting as μ₂-bridging ligands, link neighbouring Ni^II ions into a chain structure along the c axis. These polymeric chains are extended into a three-dimensional framework via intermolecular O—H⋯O hydrogen bonds with participation of the water molecules.

Related literature

For metal complexes derived from pyridine-4-sulfonic acid, see: Lü et al. (2007 ); Leslie & George (2005a ,b ).

Experimental

Crystal data

[Ni(C₅H₄NO₂S)₂(H₂O)₂]
M_r = 379.05
Triclinic, $[P \overline 1]$
a = 6.403 (5) Å
b = 7.309 (5) Å
c = 7.602 (5) Å
α = 96.784 (8)°
β = 95.140 (8)°
γ = 107.709 (8)°
V = 333.6 (4) Å³
Z = 1
Mo Kα radiation
μ = 1.80 mm⁻¹
T = 296 K
0.25 × 0.17 × 0.14 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.662, T_max = 0.787
2417 measured reflections
1180 independent reflections
1043 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.080
S = 1.00
1180 reflections
97 parameters
H-atom parameters constrained
Δρ_max = 0.68 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Ni1—N1ⁱ	2.008 (2)
Ni1—O3	2.026 (2)
Ni1—O1	2.362 (2)
Symmetry code: (i) x, y, z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1W⋯O2^iv	0.84	2.00	2.826 (3)	168
O1—H2W⋯O2^v	0.84	2.00	2.827 (3)	169
Symmetry codes: (iv) x, y-1, z; (v) -x, -y, -z+2.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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/S1600536809024258/at2818sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024258/at2818Isup2.hkl

checkCIF report

Comment top

It is well known that sulfinic acid is not stable compared with sulfonic acid, so it is much difficult to obtain complexes of sulfinic acid as they are easy to be oxidized. In the previous literatures, several metal complexes derived from pyridine-4-sulfonic acid have been reported (Leslie & George, 2005a,b; Lü et al., 2007), whereas the complexes of pyridine-4-sulfinic acid has been not seen so far. Here we describe a nickel(II) complex from pyridine-4-sulfinic acid, (I), (Fig. 1).

The Ni^II ion locates on a centre of symmetry and is in a distorted octahedral geometry with two water ligands in axial trans positions and two N and two O atoms of four symmetry-related ps^- ligands in equatorial plane (Table 1). Each ps^- ligand connects two Ni^II ions and thus forms one-dimensional chain structure along c axis (Fig.2), with adjacent Ni···Ni separation distance of 7.602 (3) Å.

Water molecules take part in hydrogen bonds as double donor, and S═O of ps^- ligands acts only as a single acceptor (Table 2, Fig.3). Hydrogen bonds interactions stabilizes and extends chain structure of (I) into a three-dimensional network.

Related literature top

For metal complexes derived from pyridine-4-sulfonic acid, see: Lü et al. (2007); Leslie & George (2005a,b).

Experimental top

A solution of NiCl₂. 6H₂O (1 mmol, 0.238 g) in anhydrous ethanol (10 ml) was injected dropwise into a solution of Hps (2 mol, 0.286 g) in methanol (15 ml) under argon. The resulting mixture was stirred at 343 K for 4 h, then cooled to room temperature. After filtration, the filtrate was left to stand at room temperature for slow evaporation. Green block-shaped crystals suitable for X-ray diffraction were obtained in a yield of 17%. Analysis, found: C 31.58, H 3.11, N 7.45, S 16.93%; C₁₀H₁₂N₂NiO₆S₂ requires: C 31.66, H 3.17, N 7.39, S 16.88%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 coordination environment of Ni^II ion in (I).Displacement ellipsoids are drawn at the 30% probability level. Symmetry codes: (A) (1 - x, -y, 2 - z);(B) (x, y, 1 + z); (C) (1 - x, -y, 1 - z).
	Fig. 2. The chain structure of (I) along c axis. H atoms on C atoms have been omitted.
	Fig. 3. Packing diagram for (1), showing hydrogen bonds as dashed lines in ab plane. H atoms on C have been deleted.

catena-Poly[[diaquanickel(II)]-bis(µ-pyridine-4-sulfinato)- κ²N,O;κ²O,N] top

Crystal data top

[Ni(C₅H₄NO₂S)₂(H₂O)₂]	Z = 1
M_r = 379.05	F(000) = 194
Triclinic, P1	D_x = 1.887 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.403 (5) Å	Cell parameters from 1414 reflections
b = 7.309 (5) Å	θ = 2.7–27.9°
c = 7.602 (5) Å	µ = 1.80 mm⁻¹
α = 96.784 (8)°	T = 296 K
β = 95.140 (8)°	Block, green
γ = 107.709 (8)°	0.25 × 0.17 × 0.14 mm
V = 333.6 (4) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	1180 independent reflections
Radiation source: fine-focus sealed tube	1043 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ϕ and ω scans	θ_max = 25.5°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.662, T_max = 0.787	k = −8→8
2417 measured reflections	l = −9→9

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0581P)²] where P = (F_o² + 2F_c²)/3
1180 reflections	(Δ/σ)_max < 0.001
97 parameters	Δρ_max = 0.68 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[Ni(C₅H₄NO₂S)₂(H₂O)₂]	γ = 107.709 (8)°
M_r = 379.05	V = 333.6 (4) Å³
Triclinic, P1	Z = 1
a = 6.403 (5) Å	Mo Kα radiation
b = 7.309 (5) Å	µ = 1.80 mm⁻¹
c = 7.602 (5) Å	T = 296 K
α = 96.784 (8)°	0.25 × 0.17 × 0.14 mm
β = 95.140 (8)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1180 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1043 reflections with I > 2σ(I)
T_min = 0.662, T_max = 0.787	R_int = 0.017
2417 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 1.00	Δρ_max = 0.68 e Å⁻³
1180 reflections	Δρ_min = −0.36 e Å⁻³
97 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
Ni1	0.5000	0.0000	1.0000	0.02196 (18)
S1	0.37032 (11)	0.32818 (9)	0.81172 (8)	0.0282 (2)
O1	0.1697 (3)	−0.2599 (3)	0.9900 (3)	0.0432 (5)
H1W	0.1594	−0.3595	0.9190	0.065*
H2W	0.0660	−0.2844	1.0522	0.065*
O2	0.1653 (3)	0.3862 (3)	0.7920 (3)	0.0374 (5)
O3	0.3059 (3)	0.1287 (3)	0.8709 (2)	0.0330 (4)
N1	0.4591 (3)	0.1289 (3)	0.2369 (3)	0.0257 (5)
C1	0.2579 (4)	0.1289 (4)	0.2770 (4)	0.0306 (6)
H1	0.1377	0.0841	0.1873	0.037*
C2	0.2257 (5)	0.1933 (4)	0.4472 (4)	0.0320 (6)
H2	0.0857	0.1920	0.4721	0.038*
C3	0.4053 (4)	0.2601 (3)	0.5805 (3)	0.0250 (5)
C4	0.6131 (4)	0.2690 (4)	0.5387 (3)	0.0271 (6)
H4	0.7370	0.3191	0.6247	0.033*
C5	0.6316 (4)	0.2014 (4)	0.3656 (4)	0.0304 (6)
H5	0.7713	0.2066	0.3369	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0291 (3)	0.0292 (3)	0.0131 (2)	0.0168 (2)	0.00585 (17)	0.00249 (17)
S1	0.0353 (4)	0.0309 (4)	0.0215 (4)	0.0151 (3)	0.0082 (3)	0.0004 (3)
O1	0.0457 (12)	0.0320 (11)	0.0528 (13)	0.0108 (9)	0.0236 (10)	0.0015 (9)
O2	0.0473 (12)	0.0441 (11)	0.0339 (11)	0.0299 (10)	0.0164 (9)	0.0075 (9)
O3	0.0414 (11)	0.0401 (10)	0.0251 (9)	0.0212 (9)	0.0098 (8)	0.0081 (8)
N1	0.0288 (11)	0.0309 (11)	0.0210 (11)	0.0141 (9)	0.0055 (8)	0.0047 (9)
C1	0.0284 (13)	0.0412 (15)	0.0254 (14)	0.0162 (11)	0.0033 (11)	0.0040 (11)
C2	0.0277 (13)	0.0435 (15)	0.0299 (15)	0.0176 (12)	0.0089 (11)	0.0047 (12)
C3	0.0328 (13)	0.0246 (12)	0.0217 (13)	0.0134 (10)	0.0079 (10)	0.0047 (10)
C4	0.0271 (13)	0.0327 (13)	0.0217 (13)	0.0106 (11)	0.0036 (10)	0.0015 (10)
C5	0.0304 (14)	0.0377 (15)	0.0275 (15)	0.0160 (12)	0.0084 (11)	0.0053 (11)

Geometric parameters (Å, º) top

Ni1—N1ⁱ	2.008 (2)	N1—C5	1.336 (4)
Ni1—N1ⁱⁱ	2.008 (2)	N1—C1	1.350 (3)
Ni1—O3ⁱⁱⁱ	2.026 (2)	N1—Ni1^iv	2.008 (2)
Ni1—O3	2.026 (2)	C1—C2	1.379 (4)
Ni1—O1ⁱⁱⁱ	2.362 (2)	C1—H1	0.9300
Ni1—O1	2.362 (2)	C2—C3	1.386 (4)
S1—O2	1.498 (2)	C2—H2	0.9300
S1—O3	1.523 (2)	C3—C4	1.380 (4)
S1—C3	1.821 (3)	C4—C5	1.378 (4)
O1—H1W	0.8350	C4—H4	0.9300
O1—H2W	0.8371	C5—H5	0.9300

N1ⁱ—Ni1—N1ⁱⁱ	180.000 (1)	H1W—O1—H2W	109.3
N1ⁱ—Ni1—O3ⁱⁱⁱ	90.55 (9)	S1—O3—Ni1	128.93 (12)
N1ⁱⁱ—Ni1—O3ⁱⁱⁱ	89.45 (9)	C5—N1—C1	118.2 (2)
N1ⁱ—Ni1—O3	89.45 (9)	C5—N1—Ni1^iv	119.50 (18)
N1ⁱⁱ—Ni1—O3	90.55 (9)	C1—N1—Ni1^iv	121.99 (18)
O3ⁱⁱⁱ—Ni1—O3	180.000 (1)	N1—C1—C2	121.9 (2)
N1ⁱ—Ni1—O1ⁱⁱⁱ	92.01 (8)	N1—C1—H1	119.1
N1ⁱⁱ—Ni1—O1ⁱⁱⁱ	87.99 (8)	C2—C1—H1	119.1
O3ⁱⁱⁱ—Ni1—O1ⁱⁱⁱ	85.24 (9)	C1—C2—C3	118.9 (2)
O3—Ni1—O1ⁱⁱⁱ	94.76 (9)	C1—C2—H2	120.5
N1ⁱ—Ni1—O1	87.99 (8)	C3—C2—H2	120.5
N1ⁱⁱ—Ni1—O1	92.01 (8)	C4—C3—C2	119.5 (2)
O3ⁱⁱⁱ—Ni1—O1	94.76 (9)	C4—C3—S1	119.35 (19)
O3—Ni1—O1	85.24 (9)	C2—C3—S1	121.1 (2)
O1ⁱⁱⁱ—Ni1—O1	180.0	C3—C4—C5	118.0 (2)
O2—S1—O3	107.19 (12)	C3—C4—H4	121.0
O2—S1—C3	102.55 (12)	C5—C4—H4	121.0
O3—S1—C3	99.77 (11)	N1—C5—C4	123.3 (2)
Ni1—O1—H1W	114.8	N1—C5—H5	118.3
Ni1—O1—H2W	135.0	C4—C5—H5	118.3

O2—S1—O3—Ni1	−157.49 (13)	C1—C2—C3—S1	−174.8 (2)
C3—S1—O3—Ni1	96.00 (15)	O2—S1—C3—C4	155.44 (19)
N1ⁱ—Ni1—O3—S1	−93.25 (15)	O3—S1—C3—C4	−94.3 (2)
N1ⁱⁱ—Ni1—O3—S1	86.75 (15)	O2—S1—C3—C2	−26.8 (2)
O1ⁱⁱⁱ—Ni1—O3—S1	−1.28 (15)	O3—S1—C3—C2	83.4 (2)
O1—Ni1—O3—S1	178.72 (15)	C2—C3—C4—C5	−3.1 (4)
C5—N1—C1—C2	−2.8 (4)	S1—C3—C4—C5	174.71 (19)
Ni1^iv—N1—C1—C2	170.9 (2)	C1—N1—C5—C4	2.7 (4)
N1—C1—C2—C3	0.1 (4)	Ni1^iv—N1—C5—C4	−171.20 (19)
C1—C2—C3—C4	2.9 (4)	C3—C4—C5—N1	0.3 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···O2^v	0.84	2.00	2.826 (3)	168
O1—H2W···O2^vi	0.84	2.00	2.827 (3)	169

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

Experimental details

Crystal data
Chemical formula	[Ni(C₅H₄NO₂S)₂(H₂O)₂]
M_r	379.05
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.403 (5), 7.309 (5), 7.602 (5)
α, β, γ (°)	96.784 (8), 95.140 (8), 107.709 (8)
V (Å³)	333.6 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.80
Crystal size (mm)	0.25 × 0.17 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.662, 0.787
No. of measured, independent and observed [I > 2σ(I)] reflections	2417, 1180, 1043
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.080, 1.00
No. of reflections	1180
No. of parameters	97
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.68, −0.36

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Ni1—N1ⁱ	2.008 (2)	Ni1—O1	2.362 (2)
Ni1—O3	2.026 (2)

N1ⁱⁱ—Ni1—N1ⁱ	180.000 (1)	N1ⁱⁱ—Ni1—O1	87.99 (8)
N1ⁱⁱ—Ni1—O3	89.45 (9)	O3—Ni1—O1	85.24 (9)
N1ⁱ—Ni1—O3	90.55 (9)	O1ⁱⁱⁱ—Ni1—O1	180.0
O3ⁱⁱⁱ—Ni1—O3	180.000 (1)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···O2^iv	0.84	2.00	2.826 (3)	168.2
O1—H2W···O2^v	0.84	2.00	2.827 (3)	169.4

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

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (No. 20771054).

References

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