catena-Poly[[diaqua­nickel(II)]-bis­(μ-pyridine-4-sulfinato)-κ² N,O;κ² O,N]

Abstract

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,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.031

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

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

Symmetry code: (i) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1W⋯O2iv	0.84	2.00	2.826 (3)	168
O1—H2W⋯O2v	0.84	2.00	2.827 (3)	169

Symmetry codes: (iv) ; (v) .

supplementary crystallographic information

Comment

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.

Experimental

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%.

Refinement

H atoms bonded to C were positioned geometrically with C—H distance of 0.93 Å, and treated as riding atoms, with U_iso(H)=1.2U_eq(C). The O—H hydrogen atom was located in a difference Fourier map and refined isotropically.

Figures

Fig. 1.

The coordination environment of NiII 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.

Crystal data

[Ni(C5H4NO2S)2(H2O)2]	Z = 1
Mr = 379.05	F(000) = 194
Triclinic, P1	Dx = 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

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

Refinement

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(Fo2) + (0.0581P)2] where P = (Fo2 + 2Fc2)/3
1180 reflections	(Δ/σ)max < 0.001
97 parameters	Δρmax = 0.68 e Å−3
0 restraints	Δρmin = −0.36 e Å−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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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
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 (Ų)

	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, °)

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—Ni1iv	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—Ni1iv	119.50 (18)
N1ii—Ni1—O3	90.55 (9)	C1—N1—Ni1iv	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)
Ni1iv—N1—C1—C2	170.9 (2)	C1—N1—C5—C4	2.7 (4)
N1—C1—C2—C3	0.1 (4)	Ni1iv—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, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···O2v	0.84	2.00	2.826 (3)	168
O1—H2W···O2vi	0.84	2.00	2.827 (3)	169

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