Tetra­aqua­bis(pyridine-3-sulfonato-κN)nickel(II)

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

doi:10.1107/S1600536808010076

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page m679

doi:10.1107/S1600536808010076

Open

access

Tetraaquabis(pyridine-3-sulfonato-κN)nickel(II)

Bing-Yu Zhang,^a Jing-Jing Nie ^a and Duan-Jun Xu ^a ^*

^aDepartment of Chemistry, Zhejiang University, Hangzhou 310027, People's Republic of China
^*Correspondence e-mail: xudj@mail.hz.zj.cn

(Received 8 April 2008; accepted 13 April 2008; online 16 April 2008)

In the molecule of the title compound, [Ni(C₅H₄NO₃S)₂(H₂O)₄], the Ni^II 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 π–π stacking between the pyridine rings. The structure also contains intermolecular O—H⋯O hydrogen bonding and weak C—H⋯O hydrogen bonding.

Related literature

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

Crystal data

[Ni(C₅H₄NO₃S)₂(H₂O)₄]
M_r = 447.08
Monoclinic, P 2₁ /n
a = 7.5399 (8) Å
b = 12.6939 (15) Å
c = 8.7810 (8) Å
β = 97.419 (12)°
V = 833.40 (15) Å³
Z = 2
Mo Kα radiation
μ = 1.47 mm⁻¹
T = 295 (2) K
0.32 × 0.22 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.660, T_max = 0.745
8877 measured reflections
1524 independent reflections
1449 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.065
S = 1.06
1524 reflections
115 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni—O1	2.0828 (14)
Ni—O2	2.0739 (14)
Ni—N1	2.1026 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O3ⁱ	0.81	2.39	3.162 (3)	158
O1—H1A⋯O4ⁱ	0.81	2.44	3.119 (2)	142
O1—H1B⋯O4ⁱⁱ	0.89	1.83	2.722 (2)	177
O2—H2A⋯O3ⁱⁱⁱ	0.84	1.97	2.787 (2)	163
O2—H2B⋯O5^iv	0.86	1.89	2.748 (2)	174
C1—H1⋯O4ⁱ	0.93	2.34	3.212 (3)	155
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z; (iv) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808010076/om2227sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808010076/om2227Isup2.hkl

checkCIF report

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 Ni^II 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 Zn^II (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.

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

	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].
	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]	F(000) = 460
M_r = 447.08	D_x = 1.782 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5256 reflections
a = 7.5399 (8) Å	θ = 2.8–24.0°
b = 12.6939 (15) Å	µ = 1.47 mm⁻¹
c = 8.7810 (8) Å	T = 295 K
β = 97.419 (12)°	Prism, blue
V = 833.40 (15) Å³	0.32 × 0.22 × 0.20 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1524 independent reflections
Radiation source: fine-focus sealed tube	1449 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
Detector resolution: 10.0 pixels mm^-1	θ_max = 25.4°, θ_min = 2.8°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −15→15
T_min = 0.660, T_max = 0.745	l = −9→10
8877 measured reflections

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.065	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0323P)² + 0.5265P] where P = (F_o² + 2F_c²)/3
1524 reflections	(Δ/σ)_max < 0.001
115 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Ni(C₅H₄NO₃S)₂(H₂O)₄]	V = 833.40 (15) Å³
M_r = 447.08	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.5399 (8) Å	µ = 1.47 mm⁻¹
b = 12.6939 (15) Å	T = 295 K
c = 8.7810 (8) Å	0.32 × 0.22 × 0.20 mm
β = 97.419 (12)°

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)
T_min = 0.660, T_max = 0.745	R_int = 0.019
8877 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 1.06	Δρ_max = 0.29 e Å⁻³
1524 reflections	Δρ_min = −0.37 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
Ni	0.5000	0.5000	0.5000	0.02883 (13)
S	0.45204 (7)	0.75905 (4)	−0.03581 (6)	0.03407 (15)
N1	0.5850 (2)	0.54221 (13)	0.28948 (18)	0.0307 (3)
O1	0.76142 (19)	0.48676 (11)	0.60868 (18)	0.0388 (3)
H1B	0.8326	0.5397	0.5900	0.058*
H1A	0.8182	0.4333	0.5998	0.058*
O2	0.50231 (19)	0.34035 (11)	0.45010 (17)	0.0411 (3)
H2A	0.5076	0.3156	0.3615	0.062*
H2B	0.4194	0.3021	0.4815	0.062*
O3	0.5370 (3)	0.76975 (16)	−0.1732 (2)	0.0687 (6)
O4	0.4828 (2)	0.85025 (12)	0.0624 (2)	0.0554 (5)
O5	0.2658 (2)	0.73019 (12)	−0.06337 (19)	0.0481 (4)
C1	0.7217 (3)	0.49242 (15)	0.2368 (3)	0.0370 (5)
H1	0.7768	0.4372	0.2943	0.044*
C2	0.7839 (3)	0.51907 (18)	0.1020 (3)	0.0452 (5)
H2	0.8783	0.4819	0.0693	0.054*
C3	0.7053 (3)	0.60162 (17)	0.0150 (3)	0.0405 (5)
H3	0.7461	0.6218	−0.0762	0.049*
C4	0.5641 (2)	0.65298 (14)	0.0684 (2)	0.0298 (4)
C5	0.5074 (3)	0.62143 (15)	0.2044 (2)	0.0320 (4)
H5	0.4116	0.6565	0.2384	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni	0.0309 (2)	0.0273 (2)	0.0284 (2)	0.00105 (13)	0.00426 (14)	0.00418 (13)
S	0.0419 (3)	0.0278 (3)	0.0317 (3)	0.0027 (2)	0.0018 (2)	0.00399 (19)
N1	0.0329 (8)	0.0290 (8)	0.0302 (8)	0.0016 (7)	0.0037 (6)	0.0034 (7)
O1	0.0336 (7)	0.0355 (8)	0.0467 (9)	0.0018 (6)	0.0031 (6)	0.0056 (6)
O2	0.0512 (9)	0.0328 (8)	0.0409 (8)	−0.0017 (6)	0.0122 (7)	−0.0002 (6)
O3	0.0861 (14)	0.0758 (13)	0.0491 (11)	0.0261 (11)	0.0269 (10)	0.0305 (9)
O4	0.0591 (10)	0.0297 (8)	0.0707 (11)	0.0048 (7)	−0.0174 (8)	−0.0095 (8)
O5	0.0441 (9)	0.0358 (8)	0.0600 (10)	0.0039 (7)	−0.0103 (7)	−0.0022 (7)
C1	0.0360 (11)	0.0328 (11)	0.0417 (12)	0.0064 (8)	0.0034 (9)	0.0061 (8)
C2	0.0417 (12)	0.0431 (12)	0.0542 (14)	0.0126 (10)	0.0188 (10)	0.0065 (10)
C3	0.0455 (12)	0.0393 (11)	0.0395 (12)	0.0036 (9)	0.0154 (9)	0.0055 (9)
C4	0.0337 (9)	0.0255 (9)	0.0295 (10)	−0.0002 (7)	0.0016 (8)	0.0005 (7)
C5	0.0333 (9)	0.0314 (10)	0.0313 (10)	0.0041 (8)	0.0047 (8)	0.0004 (8)

Geometric parameters (Å, º) top

Ni—O1ⁱ	2.0828 (14)	O1—H1B	0.8886
Ni—O1	2.0828 (14)	O1—H1A	0.8115
Ni—O2ⁱ	2.0739 (14)	O2—H2A	0.8450
Ni—O2	2.0739 (14)	O2—H2B	0.8642
Ni—N1ⁱ	2.1026 (16)	C1—C2	1.370 (3)
Ni—N1	2.1026 (16)	C1—H1	0.9300
S—O5	1.4412 (16)	C2—C3	1.384 (3)
S—O3	1.4438 (18)	C2—H2	0.9300
S—O4	1.4445 (16)	C3—C4	1.381 (3)
S—C4	1.7788 (19)	C3—H3	0.9300
N1—C1	1.341 (3)	C4—C5	1.379 (3)
N1—C5	1.341 (2)	C5—H5	0.9300

O2ⁱ—Ni—O2	180.0	C5—N1—Ni	121.36 (13)
O2ⁱ—Ni—O1ⁱ	89.12 (6)	Ni—O1—H1B	114.4
O2—Ni—O1ⁱ	90.88 (6)	Ni—O1—H1A	120.2
O2ⁱ—Ni—O1	90.88 (6)	H1B—O1—H1A	106.0
O2—Ni—O1	89.12 (6)	Ni—O2—H2A	124.1
O1ⁱ—Ni—O1	180.0	Ni—O2—H2B	117.1
O2ⁱ—Ni—N1ⁱ	92.95 (6)	H2A—O2—H2B	101.9
O2—Ni—N1ⁱ	87.05 (6)	N1—C1—C2	123.07 (19)
O1ⁱ—Ni—N1ⁱ	92.61 (6)	N1—C1—H1	118.5
O1—Ni—N1ⁱ	87.39 (6)	C2—C1—H1	118.5
O2ⁱ—Ni—N1	87.05 (6)	C1—C2—C3	119.6 (2)
O2—Ni—N1	92.95 (6)	C1—C2—H2	120.2
O1ⁱ—Ni—N1	87.39 (6)	C3—C2—H2	120.2
O1—Ni—N1	92.61 (6)	C4—C3—C2	117.6 (2)
N1ⁱ—Ni—N1	180.0	C4—C3—H3	121.2
O5—S—O3	114.30 (12)	C2—C3—H3	121.2
O5—S—O4	112.45 (10)	C5—C4—C3	119.71 (18)
O3—S—O4	111.67 (12)	C5—C4—S	119.06 (14)
O5—S—C4	106.36 (9)	C3—C4—S	121.23 (15)
O3—S—C4	105.58 (10)	N1—C5—C4	122.60 (18)
O4—S—C4	105.69 (9)	N1—C5—H5	118.7
C1—N1—C5	117.40 (17)	C4—C5—H5	118.7
C1—N1—Ni	121.22 (13)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3ⁱⁱ	0.81	2.39	3.162 (3)	158
O1—H1A···O4ⁱⁱ	0.81	2.44	3.119 (2)	142
O1—H1B···O4ⁱⁱⁱ	0.89	1.83	2.722 (2)	177
O2—H2A···O3^iv	0.84	1.97	2.787 (2)	163
O2—H2B···O5^v	0.86	1.89	2.748 (2)	174
C1—H1···O4ⁱⁱ	0.93	2.34	3.212 (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.

Experimental details

Crystal data
Chemical formula	[Ni(C₅H₄NO₃S)₂(H₂O)₄]
M_r	447.08
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	7.5399 (8), 12.6939 (15), 8.7810 (8)
β (°)	97.419 (12)
V (Å³)	833.40 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.47
Crystal size (mm)	0.32 × 0.22 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.660, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	8877, 1524, 1449
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.065, 1.06
No. of reflections	1524
No. of parameters	115
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.37

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Ni—O1	2.0828 (14)	Ni—N1	2.1026 (16)
Ni—O2	2.0739 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3ⁱ	0.81	2.39	3.162 (3)	158
O1—H1A···O4ⁱ	0.81	2.44	3.119 (2)	142
O1—H1B···O4ⁱⁱ	0.89	1.83	2.722 (2)	177
O2—H2A···O3ⁱⁱⁱ	0.84	1.97	2.787 (2)	163
O2—H2B···O5^iv	0.86	1.89	2.748 (2)	174
C1—H1···O4ⁱ	0.93	2.34	3.212 (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

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

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Cotton, F. A. & Wilkinson, G. (1972). Advances in Inorganic Chemistry, p. 120. New York: John Wiley & Sons. Google Scholar
Deisenhofer, J. & Michel, H. (1989). EMBO J. 8, 2149–2170. CAS PubMed Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Li, H., Liu, J.-G. & Xu, D.-J. (2005). Acta Cryst. E61, m761–m763. Web of Science CSD CrossRef IUCr Journals Google Scholar
Liu, B.-X., Su, J.-R. & Xu, D.-J. (2004). Acta Cryst. C60, m183–m185. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Su, J.-R. & Xu, D.-J. (2004). J. Coord. Chem. 57, 223–229. Web of Science CSD CrossRef CAS Google Scholar
Walsh, B. & Hathaway, B. J. (1980). J. Chem. Soc. Dalton Trans. pp. 681–689. CSD CrossRef Web of Science Google Scholar