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Acta Cryst. (2008). E64, m679    [ doi:10.1107/S1600536808010076 ]

Tetraaquabis(pyridine-3-sulfonato-[kappa]N)nickel(II)

B.-Y. Zhang, J.-J. Nie and D.-J. Xu

Abstract top

In the molecule of the title compound, [Ni(C5H4NO3S)2(H2O)4], the NiII cation is located on an inversion center and is coordinated by four water molecules and two pyridine-3-sulfonate anions with an NiN2O4 distorted octahedral geometry. The face-to-face separation of 3.561 (5) Å between parallel pyridine rings indicates the existence of weak [pi]-[pi] stacking between the pyridine rings. The structure also contains intermolecular O-H...O hydrogen bonding and weak C-H...O hydrogen bonding.

Comment top

As π-π stacking between aromatic rings plays an important role in electron transfer process in some biological system (Deisenhofer & Michel, 1989), π-π stacking has attracted our much attention in past years (Su & Xu, 2004; Liu et al., 2004; Li et al., 2005). In order to investigate the influence of substituents on aromatic stacking, the title pyridine-sulfate complex has recently prepared and its crystal structure is reported here.

The molecular structure of the title compound is shown in Fig. 1. The NiII cation is located in an inversion center and coordinated by four water molecules and two pyridine-3-sulfonate anions with a NiN2O4 distorted octahedral geometry (Table 1), similar to the analogue of ZnII (Walsh & Hathaway, 1980). Partially overlapped arrangement is observed between parallel pyridine rings (Fig. 2). The face-to-face separation of 3.561 (5) Å between parallel pyridine rings is shorter than the van der Waals thickness of an aromatic ring (3.70 Å; Cotton & Wilkinson, 1972), and indicates the existence of weak π–π stacking between the pyridine rings.

The intermolecular O—H···O hydrogen bonding and weak C—H···O hydrogen bonding (Table 2) help to stabilize the crystal structure.

Related literature top

For general background, see: Deisenhofer & Michel (1989); Su & Xu (2004); Liu et al. (2004); Li et al. (2005). For a related structure, see: Walsh & Hathaway (1980). For related literature, see: Cotton & Wilkinson (1972).

Experimental top

Pyridine-3-sulfonic acid (0.159 g, 1 mmol), Na2CO3 (0.053 g, 0.5 mmol), NiCl2.6H2O (0.238 g, 1 mmol) were dissolved in a mixture solution of water (8 ml) and ethanol (2 ml). The solution was placed in a 15 ml Teflon-lined stainless steel autoclave under autogenous pressure at 398 K for 75 h and filtered after cooling to room temperature. The blue single crystals of the title compound were obtained from the filtrate after 3 months.

Refinement top

Water H atoms were located in a difference Fourier map and refined as riding in as-found relative positions with Uiso(H) = 1.5Ueq(O). Aromatic H atoms were placed in calculated positions with C—H = 0.93 Å and refined in riding mode with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with 40% probability displacement (arbitrary spheres for H atoms) [symmetry codes: (i)1 - x,1 - y,1 - z].
[Figure 2] Fig. 2. A diagram showing π-π stacking between pyridine rings [symmetry code: (ii) 1 - x,1 - y,-z].
Tetraaquabis(pyridine-3-sulfonato-κN)nickel(II) top
Crystal data top
[Ni(C5H4NO3S)2(H2O)4]F000 = 460
Mr = 447.08Dx = 1.782 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5256 reflections
a = 7.5399 (8) Åθ = 2.8–24.0º
b = 12.6939 (15) ŵ = 1.47 mm−1
c = 8.7810 (8) ÅT = 295 (2) K
β = 97.419 (12)ºPrism, blue
V = 833.40 (15) Å30.32 × 0.22 × 0.20 mm
Z = 2
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		1524 independent reflections
Radiation source: fine-focus sealed tube1449 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.019
Detector resolution: 10.0 pixels mm-1θmax = 25.4º
T = 295(2) Kθmin = 2.8º
ω scansh = −9→9
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −15→15
Tmin = 0.660, Tmax = 0.745l = −9→10
8877 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.065  w = 1/[σ2(Fo2) + (0.0323P)2 + 0.5265P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
1524 reflectionsΔρmax = 0.29 e Å−3
115 parametersΔρmin = −0.37 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ni(C5H4NO3S)2(H2O)4]V = 833.40 (15) Å3
Mr = 447.08Z = 2
Monoclinic, P21/nMo Kα
a = 7.5399 (8) ŵ = 1.47 mm−1
b = 12.6939 (15) ÅT = 295 (2) K
c = 8.7810 (8) Å0.32 × 0.22 × 0.20 mm
β = 97.419 (12)º
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		1524 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		1449 reflections with I > 2σ(I)
Tmin = 0.660, Tmax = 0.745Rint = 0.019
8877 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.024115 parameters
wR(F2) = 0.065H-atom parameters constrained
S = 1.06Δρmax = 0.29 e Å−3
1524 reflectionsΔρmin = −0.37 e Å−3
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
xyzUiso*/Ueq
Ni0.50000.50000.50000.02883 (13)
S0.45204 (7)0.75905 (4)−0.03581 (6)0.03407 (15)
N10.5850 (2)0.54221 (13)0.28948 (18)0.0307 (3)
O10.76142 (19)0.48676 (11)0.60868 (18)0.0388 (3)
H1B0.83260.53970.59000.058*
H1A0.81820.43330.59980.058*
O20.50231 (19)0.34035 (11)0.45010 (17)0.0411 (3)
H2A0.50760.31560.36150.062*
H2B0.41940.30210.48150.062*
O30.5370 (3)0.76975 (16)−0.1732 (2)0.0687 (6)
O40.4828 (2)0.85025 (12)0.0624 (2)0.0554 (5)
O50.2658 (2)0.73019 (12)−0.06337 (19)0.0481 (4)
C10.7217 (3)0.49242 (15)0.2368 (3)0.0370 (5)
H10.77680.43720.29430.044*
C20.7839 (3)0.51907 (18)0.1020 (3)0.0452 (5)
H20.87830.48190.06930.054*
C30.7053 (3)0.60162 (17)0.0150 (3)0.0405 (5)
H30.74610.6218−0.07620.049*
C40.5641 (2)0.65298 (14)0.0684 (2)0.0298 (4)
C50.5074 (3)0.62143 (15)0.2044 (2)0.0320 (4)
H50.41160.65650.23840.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.0309 (2)0.0273 (2)0.0284 (2)0.00105 (13)0.00426 (14)0.00418 (13)
S0.0419 (3)0.0278 (3)0.0317 (3)0.0027 (2)0.0018 (2)0.00399 (19)
N10.0329 (8)0.0290 (8)0.0302 (8)0.0016 (7)0.0037 (6)0.0034 (7)
O10.0336 (7)0.0355 (8)0.0467 (9)0.0018 (6)0.0031 (6)0.0056 (6)
O20.0512 (9)0.0328 (8)0.0409 (8)−0.0017 (6)0.0122 (7)−0.0002 (6)
O30.0861 (14)0.0758 (13)0.0491 (11)0.0261 (11)0.0269 (10)0.0305 (9)
O40.0591 (10)0.0297 (8)0.0707 (11)0.0048 (7)−0.0174 (8)−0.0095 (8)
O50.0441 (9)0.0358 (8)0.0600 (10)0.0039 (7)−0.0103 (7)−0.0022 (7)
C10.0360 (11)0.0328 (11)0.0417 (12)0.0064 (8)0.0034 (9)0.0061 (8)
C20.0417 (12)0.0431 (12)0.0542 (14)0.0126 (10)0.0188 (10)0.0065 (10)
C30.0455 (12)0.0393 (11)0.0395 (12)0.0036 (9)0.0154 (9)0.0055 (9)
C40.0337 (9)0.0255 (9)0.0295 (10)−0.0002 (7)0.0016 (8)0.0005 (7)
C50.0333 (9)0.0314 (10)0.0313 (10)0.0041 (8)0.0047 (8)0.0004 (8)
Geometric parameters (Å, °) top
Ni—O1i2.0828 (14)O1—H1B0.8886
Ni—O12.0828 (14)O1—H1A0.8115
Ni—O2i2.0739 (14)O2—H2A0.8450
Ni—O22.0739 (14)O2—H2B0.8642
Ni—N1i2.1026 (16)C1—C21.370 (3)
Ni—N12.1026 (16)C1—H10.9300
S—O51.4412 (16)C2—C31.384 (3)
S—O31.4438 (18)C2—H20.9300
S—O41.4445 (16)C3—C41.381 (3)
S—C41.7788 (19)C3—H30.9300
N1—C11.341 (3)C4—C51.379 (3)
N1—C51.341 (2)C5—H50.9300
O2i—Ni—O2180.0C5—N1—Ni121.36 (13)
O2i—Ni—O1i89.12 (6)Ni—O1—H1B114.4
O2—Ni—O1i90.88 (6)Ni—O1—H1A120.2
O2i—Ni—O190.88 (6)H1B—O1—H1A106.0
O2—Ni—O189.12 (6)Ni—O2—H2A124.1
O1i—Ni—O1180.0Ni—O2—H2B117.1
O2i—Ni—N1i92.95 (6)H2A—O2—H2B101.9
O2—Ni—N1i87.05 (6)N1—C1—C2123.07 (19)
O1i—Ni—N1i92.61 (6)N1—C1—H1118.5
O1—Ni—N1i87.39 (6)C2—C1—H1118.5
O2i—Ni—N187.05 (6)C1—C2—C3119.6 (2)
O2—Ni—N192.95 (6)C1—C2—H2120.2
O1i—Ni—N187.39 (6)C3—C2—H2120.2
O1—Ni—N192.61 (6)C4—C3—C2117.6 (2)
N1i—Ni—N1180.0C4—C3—H3121.2
O5—S—O3114.30 (12)C2—C3—H3121.2
O5—S—O4112.45 (10)C5—C4—C3119.71 (18)
O3—S—O4111.67 (12)C5—C4—S119.06 (14)
O5—S—C4106.36 (9)C3—C4—S121.23 (15)
O3—S—C4105.58 (10)N1—C5—C4122.60 (18)
O4—S—C4105.69 (9)N1—C5—H5118.7
C1—N1—C5117.40 (17)C4—C5—H5118.7
C1—N1—Ni121.22 (13)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O3ii0.812.393.162 (3)158
O1—H1A···O4ii0.812.443.119 (2)142
O1—H1B···O4iii0.891.832.722 (2)177
O2—H2A···O3iv0.841.972.787 (2)163
O2—H2B···O5v0.861.892.748 (2)174
C1—H1···O4ii0.932.343.212 (3)155
Symmetry codes: (ii) −x+3/2, y−1/2, −z+1/2; (iii) x+1/2, −y+3/2, z+1/2; (iv) −x+1, −y+1, −z; (v) −x+1/2, y−1/2, −z+1/2.
Table 1
Selected geometric parameters (Å) top
Ni—O12.0828 (14)Ni—N12.1026 (16)
Ni—O22.0739 (14)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O3i0.812.393.162 (3)158
O1—H1A···O4i0.812.443.119 (2)142
O1—H1B···O4ii0.891.832.722 (2)177
O2—H2A···O3iii0.841.972.787 (2)163
O2—H2B···O5iv0.861.892.748 (2)174
C1—H1···O4i0.932.343.212 (3)155
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x+1/2, −y+3/2, z+1/2; (iii) −x+1, −y+1, −z; (iv) −x+1/2, y−1/2, −z+1/2.
Acknowledgements top

This work was supported by the ZIJIN project of Zhejiang University, China.

references
References top

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