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Acta Cryst. (2007). E63, m1745    [ doi:10.1107/S1600536807023550 ]

catena-Poly[[diaquanickel(II)]-bis[[mu]-(4-pyridylsulfanyl)acetato-[kappa]2N:O;[kappa]2O:N]]

X.-P. Luo and L. Han

Abstract top

The Ni atom in the title compound, [Ni(C7H6NO2S)2(H2O)2]n, occupies a special position on an inversion centre and has an octahedral coordination formed by two water molecules and two pyridyl N and two carboxylate O atoms belonging to four different anionic ligands. Each ligand has a bidentate bridging function, so that each Ni atom is connected to each of its two Ni neighbours by two ligand bridges, thus producing infinite chains running along the a axis in the crystal structure. O-H...O bonds link the chains into a three-dimensional framework.

Comment top

Three compounds obtained by the reaction of pyridin-4-ylthioacetic acid with nickel(II) salts have been recently crystallographically characterized, namely one zwitterionic complex [Ni(C7H6NO2S)2(H2O)4] (Zhang et al., 2004) and two coordination polymers, [Ni(C7H6NO2S)2(H2O)]n (Huang et al., 2004a) and [Ni2(C7H6NO2S)4(H2O)2]n (Huang et al., 2004b). Herein we report the structure of a new Ni(II) complex (I) with pyridin-4-ylthioacetato ligand.

In the crystal structure of the title compound, the Ni1 atom occupies a special position in the inversion centre and has an octahedral coordination formed by two water molecules, as well as two pyridyl N and two carboxylate O atoms belonging to four different anionic ligands. Each ligand has a bidentate bridging function, so that each Ni atom is connected to each of its two Ni neighbours by two ligand bridges, thus producing infinite chains running along the a-axis in the crystal structure (Fig. 1). The O—H···O bonds link the chains into a three-dimensional framework (Table 2, Fig. 2).

Related literature top

For related literature, see: Huang et al. (2004a,b); Zhang et al. (2004).

Experimental top

Nickel(II) acetate (50 mg, 0.2 mmol), pyridin-4-ylthioacetic acid (39 mg, 0.2 mmol) and NaOH (8 mg, 0.2 mmol) were dissolved in 10 ml of water. The solution was placed in a Teflon-lined stainless-steel bomb (23 ml) and heated at 423 K for 48 h. After cooling to room temperature, green crystals of (I) precipitated from the solution in about 60% yield.

Refinement top

The water H atoms were located and refined, subject to an O—H = 0.85±0.02 Å restraint. The aromatic and aliphatic H atoms were placed at calculated positions (C—H 0.93 Å and 0.97 Å respectively) and refined using the riding-model approximation with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL (Sheldrick, 1997a); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Infinite chains in the crystal structure of (I) with atom-labelling scheme, showing the coordination sphere of metal and coordination mode of the ligand. Displacement ellipsoids are drawn at the 30% probability level and H atoms are depicted as small spheres of arbitrary radius. Hydrogen bonds are shown as dashed lines [Symmetry codes: (i): x - 1, y, z; (ii): 1 - x, -y, -z; (iii): -x, -y, -z].
[Figure 2] Fig. 2. The packing diagram of the title compound viewed down the a-axis. Hydrogen bonds are shown as dashed lines.
catena-Poly[[diaquanickel(II)]-bis[µ-(4-pyridylsulfanyl)acetato- κ<sup>2</sup>N:O;κ<sup>2</sup>O:N]] top
Crystal data top
[Ni(C7H6NO2S)2(H2O)2]F(000) = 444
Mr = 431.12Dx = 1.689 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2522 reflections
a = 8.9232 (9) Åθ = 2.3–25.0°
b = 10.6901 (10) ŵ = 1.42 mm−1
c = 8.8887 (9) ÅT = 298 K
β = 90.378 (3)°Prism, green
V = 847.87 (14) Å30.32 × 0.24 × 0.16 mm
Z = 2
Data collection top
BRUKER SMART CCD Apex II
diffractometer		1489 independent reflections
Radiation source: fine-focus sealed tube1198 reflections with I > 2σ(I)
graphiteRint = 0.050
Detector resolution: 8.40 pixels mm-1θmax = 25.0°, θmin = 2.3°
ω scansh = −10→7
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		k = −11→12
Tmin = 0.658, Tmax = 0.804l = −10→10
2425 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.084Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.191H atoms treated by a mixture of independent and constrained refinement
S = 1.14 w = 1/[σ2(Fo2) + 14.8565P]
where P = (Fo2 + 2Fc2)/3
1489 reflections(Δ/σ)max < 0.001
123 parametersΔρmax = 0.96 e Å−3
2 restraintsΔρmin = −0.91 e Å−3
Crystal data top
[Ni(C7H6NO2S)2(H2O)2]V = 847.87 (14) Å3
Mr = 431.12Z = 2
Monoclinic, P21/cMo Kα radiation
a = 8.9232 (9) ŵ = 1.42 mm−1
b = 10.6901 (10) ÅT = 298 K
c = 8.8887 (9) Å0.32 × 0.24 × 0.16 mm
β = 90.378 (3)°
Data collection top
BRUKER SMART CCD Apex II
diffractometer		1489 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1198 reflections with I > 2σ(I)
Tmin = 0.658, Tmax = 0.804Rint = 0.050
2425 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.084 w = 1/[σ2(Fo2) + 14.8565P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.191Δρmax = 0.96 e Å−3
S = 1.14Δρmin = −0.91 e Å−3
1489 reflectionsAbsolute structure: ?
123 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
H atoms treated by a mixture of independent and constrained refinement
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
Ni10.00000.00000.00000.0233 (4)
S10.5686 (2)−0.1649 (2)0.4472 (2)0.0294 (6)
O10.8661 (6)−0.0028 (6)0.1907 (7)0.0311 (14)
O20.8051 (7)−0.2052 (6)0.2088 (7)0.0315 (15)
O30.0489 (7)0.1845 (6)0.0462 (7)0.0287 (14)
N10.1893 (8)−0.0633 (7)0.1246 (8)0.0298 (18)
C10.3188 (9)0.0012 (9)0.1215 (9)0.0271 (19)
H10.32630.06830.05550.033*
C20.4433 (10)−0.0276 (9)0.2126 (11)0.033 (2)
H20.53170.01790.20490.040*
C30.4312 (9)−0.1255 (8)0.3141 (10)0.0246 (19)
C40.3014 (10)−0.1952 (9)0.3123 (10)0.031 (2)
H40.2924−0.26470.37450.037*
C50.1847 (10)−0.1616 (9)0.2178 (10)0.031 (2)
H50.0980−0.21000.21890.037*
C60.7218 (10)−0.0638 (9)0.4016 (10)0.030 (2)
H6A0.68420.02120.39520.036*
H6B0.7939−0.06650.48380.036*
C70.8041 (9)−0.0940 (8)0.2550 (9)0.0243 (19)
H30.110 (7)0.201 (8)−0.025 (6)0.02 (2)*
H60.100 (11)0.202 (11)0.124 (8)0.07 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0199 (8)0.0251 (8)0.0249 (8)−0.0015 (7)−0.0033 (6)−0.0003 (7)
S10.0232 (11)0.0395 (13)0.0255 (11)0.0049 (10)−0.0031 (9)0.0067 (10)
O10.029 (3)0.032 (3)0.032 (3)0.000 (3)0.000 (3)0.001 (3)
O20.037 (4)0.030 (4)0.028 (3)−0.001 (3)0.003 (3)−0.003 (3)
O30.031 (4)0.031 (4)0.025 (3)−0.004 (3)−0.003 (3)−0.009 (3)
N10.021 (4)0.033 (4)0.035 (4)0.002 (3)0.000 (3)0.000 (3)
C10.021 (4)0.031 (4)0.029 (5)−0.004 (4)−0.005 (3)0.004 (4)
C20.022 (4)0.035 (6)0.043 (5)0.000 (4)−0.001 (4)0.003 (4)
C30.017 (4)0.026 (5)0.030 (5)0.006 (3)−0.002 (3)−0.007 (4)
C40.033 (5)0.027 (5)0.032 (5)−0.004 (4)0.005 (4)0.007 (4)
C50.020 (4)0.034 (5)0.037 (5)−0.005 (4)0.001 (4)0.015 (4)
C60.023 (5)0.034 (5)0.031 (5)0.004 (4)0.000 (4)0.002 (4)
C70.015 (4)0.033 (5)0.024 (4)0.002 (4)−0.009 (3)0.006 (4)
Geometric parameters (Å, °) top
Ni1—O3i2.060 (6)O3—H60.85 (2)
Ni1—O1ii2.081 (6)N1—C51.339 (11)
Ni1—O32.060 (6)N1—C11.346 (11)
Ni1—O1iii2.081 (6)C1—C21.404 (12)
Ni1—N1i2.125 (7)C1—H10.9300
Ni1—N12.125 (7)C2—C31.386 (12)
S1—C31.749 (8)C2—H20.9300
S1—C61.792 (9)C3—C41.378 (12)
O1—C71.260 (10)C4—C51.382 (12)
O1—Ni1iv2.081 (6)C4—H40.9300
O2—C71.258 (11)C5—H50.9300
O3—O2ii2.631 (9)C6—C71.535 (12)
O3—O2v2.792 (8)C6—H6A0.9700
O3—H30.85 (2)C6—H6B0.9700
O3—Ni1—O3i180.0 (3)C5—N1—C1116.4 (7)
O3—Ni1—O1ii91.5 (3)C5—N1—Ni1123.0 (6)
O3i—Ni1—O1ii88.5 (3)C1—N1—Ni1120.4 (6)
O3—Ni1—O1iii88.5 (3)N1—C1—C2123.5 (8)
O3i—Ni1—O1iii91.5 (3)N1—C1—H1118.2
O1ii—Ni1—O1iii180.0 (3)C2—C1—H1118.2
O3—Ni1—N1i88.0 (3)C3—C2—C1118.4 (8)
O3i—Ni1—N1i92.0 (3)C3—C2—H2120.8
O1ii—Ni1—N1i91.7 (3)C1—C2—H2120.8
O1iii—Ni1—N1i88.3 (3)C4—C3—C2118.0 (8)
O3—Ni1—N192.0 (3)C4—C3—S1117.6 (7)
O3i—Ni1—N188.0 (3)C2—C3—S1124.4 (7)
O1ii—Ni1—N188.3 (3)C3—C4—C5119.8 (8)
O1iii—Ni1—N191.7 (3)C3—C4—H4120.1
N1i—Ni1—N1180.0 (6)C5—C4—H4120.1
C3—S1—C6103.5 (4)N1—C5—C4123.6 (8)
C7—O1—Ni1iv129.6 (6)N1—C5—H5118.2
Ni1—O3—O2ii90.8 (3)C4—C5—H5118.2
Ni1—O3—O2v131.1 (3)C7—C6—S1115.8 (7)
O2ii—O3—O2v113.9 (3)C7—C6—H6A108.3
Ni1—O3—H3101 (6)S1—C6—H6A108.3
O2ii—O3—H313 (6)C7—C6—H6B108.3
O2v—O3—H3101 (6)S1—C6—H6B108.3
Ni1—O3—H6119 (9)H6A—C6—H6B107.4
O2ii—O3—H6115 (8)O2—C7—O1125.4 (8)
O2v—O3—H612 (8)O2—C7—C6118.7 (8)
H3—O3—H6102 (10)O1—C7—C6115.9 (8)
O3i—Ni1—O3—O2ii72 (100)N1i—Ni1—N1—C194 (100)
O1ii—Ni1—O3—O2ii6.2 (3)C5—N1—C1—C2−2.0 (13)
O1iii—Ni1—O3—O2ii−173.8 (3)Ni1—N1—C1—C2173.2 (7)
N1i—Ni1—O3—O2ii−85.5 (3)N1—C1—C2—C3−1.8 (14)
N1—Ni1—O3—O2ii94.5 (3)C1—C2—C3—C44.8 (13)
O3i—Ni1—O3—O2v−52 (100)C1—C2—C3—S1−174.0 (7)
O1ii—Ni1—O3—O2v−117.2 (4)C6—S1—C3—C4175.0 (7)
O1iii—Ni1—O3—O2v62.8 (4)C6—S1—C3—C2−6.2 (9)
N1i—Ni1—O3—O2v151.2 (4)C2—C3—C4—C5−4.1 (13)
N1—Ni1—O3—O2v−28.8 (4)S1—C3—C4—C5174.8 (7)
O3—Ni1—N1—C5137.4 (7)C1—N1—C5—C42.7 (14)
O3i—Ni1—N1—C5−42.6 (7)Ni1—N1—C5—C4−172.3 (7)
O1ii—Ni1—N1—C5−131.1 (7)C3—C4—C5—N10.3 (15)
O1iii—Ni1—N1—C548.9 (7)C3—S1—C6—C7−70.8 (7)
N1i—Ni1—N1—C5−91 (100)Ni1iv—O1—C7—O2−4.3 (12)
O3—Ni1—N1—C1−37.5 (7)Ni1iv—O1—C7—C6175.6 (5)
O3i—Ni1—N1—C1142.5 (7)S1—C6—C7—O2−27.7 (10)
O1ii—Ni1—N1—C154.0 (7)S1—C6—C7—O1152.4 (6)
O1iii—Ni1—N1—C1−126.0 (7)
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z; (iii) x−1, y, z; (iv) x+1, y, z; (v) −x+1, y+1/2, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O2ii0.85 (2)1.81 (3)2.631 (9)161 (8)
O3—H6···O2v0.85 (2)1.97 (4)2.792 (8)163 (12)
Symmetry codes: (ii) −x+1, −y, −z; (v) −x+1, y+1/2, −z+1/2.
Table 1
Selected geometric parameters (Å, °) top
Ni1—O1i2.081 (6)Ni1—N12.125 (7)
Ni1—O32.060 (6)
O3—Ni1—O1i91.5 (3)O1i—Ni1—N1ii91.7 (3)
O3—Ni1—N1ii88.0 (3)
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O2i0.85 (2)1.81 (3)2.631 (9)161 (8)
O3—H6···O2iii0.85 (2)1.97 (4)2.792 (8)163 (12)
Symmetry codes: (i) −x+1, −y, −z; (iii) −x+1, y+1/2, −z+1/2.
Acknowledgements top

This work was supported by the Foundation of Ningbo University (019–011090).

references
References top

Bruker (2003). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.

Huang, Y.-Q., Zhang, H., Chen, J.-G., Zou, W. & Ng, S. W. (2004a). Acta Cryst. E60, m933–m934.

Huang, Y.-Q., Zhang, H., Chen, J.-G., Zou, W. & Ng, S. W. (2004b). Acta Cryst. E60, m935–m936.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997b). SHELXS97 and SHELXL97. University of Göttingen, Germany.

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