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Acta Cryst. (2007). E63, m1773    [ doi:10.1107/S1600536807025512 ]

Bis(4-aminobenzenesulfonato-[kappa]N)tetraaquanickel(II)

J. Zhao, Z.-H. Dang, Y.-J. Wang, Y.-Z. Ye and L. Xu

Abstract top

In the title complex, [Ni(C6H2O3S)2(H2O)4], the NiII atom is octahedrally coordinated by two 4-aminobenzenesulfonate N atoms and four water molecules. The molecular complex is centrosymmetic, with the NiII ion located on an inversion centre.

Comment top

The 4-aminobenzenesulfonic acid can bind to transition metals through the amino as well as the carboxylate ends. Crystal structures of metal and 4-aminobenzenesulfonic acid that have been reported include, for example, (C12H16CdN2O8S2)n (Zhou, et al.,2004), [Cu(H2NC6H4SO3)2(H2O)2].2H2O and [Mn(H2NC6H4SO3)2(H2O)2] (Gunderman et al., 1996). In two other derivatives, the isostructural compounds [M(H2NC6H4SO3)2(H2O)2].2H2O (M=Co, Zn; Shakeri & Haussuhl, 1992a; Shakeri & Haussuhl, 1992b), both ends engage in coordination.

The reaction of the sulfanilic anion with nickel(II) gives the title compound, in which the anion coordinates through the amine group. There are extensive hydrogen bonds (N—H···O, O—H···O) in the title compound. The sulfonic O atoms are linked to the coordinated water molecules and 4-aminobenzenesulfonic acid N atoms by H bonds. The complex attains a three-dimensional supramolecular by hydrogen bonds (Fig.2).

Related literature top

For related literature, see: Gunderman et al. (1996); Shakeri & Haussuhl (1992a, 1992b); Zhou et al. (2004).

Experimental top

A mixture of nickel(II) chloride hexahydrate (0.24 g, 1 mmol), sodium hydroxide (0.08 g, 2 mmol), sulfanilic acid (0.17 g, 1 mmol) and water (17 mmol) was placed in a Teflon-lined stainless-steel bomb. The bomb was heated at 343 K for 72 h. Red crystals suitable for single-crystal X-ray analysis were isolated from the cool solution in about 50% yield.

Refinement top

H atoms attached to C atoms were placed in calculated positions and treated using a riding-model approximation (C—H = 0.95 for benzene ring H atoms with Uiso(H) = 1.2Ueq(C)). The H atoms bonded to O atoms were visible in the difference Fourier map and were included in the refinement with O—H distance restraint of 0.90, and with Uiso(H) = 1.5Ueq(O). The amine protons were refined isotropically.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. ORTEP diagram of the title compound with atoms drawn as 30% probability ellipsoids (H atoms are not labled).
[Figure 2] Fig. 2. The three-dimensional net work structure formed by the hydrogen bonds(all H atoms were omitted for clarity).
Bis(4-aminobenzenesulfonato-κN)tetraaquanickel(II) top
Crystal data top
[Ni(C6H2O3S)2(H2O)4]F(000) = 984
Mr = 475.13Dx = 1.809 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 20.800 (11) ÅCell parameters from 2071 reflections
b = 6.450 (3) Åθ = 2.0–27.5°
c = 13.566 (7) ŵ = 1.41 mm−1
β = 106.593 (9)°T = 293 K
V = 1744.1 (15) Å3Prism, green
Z = 40.18 × 0.12 × 0.08 mm
Data collection top
Bruker SMART
diffractometer		1997 independent reflections
Radiation source: fine-focus sealed tube1722 reflections with I > 2σ(I)
graphiteRint = 0.027
Detector resolution: 14.6306 pixels mm-1θmax = 27.5°, θmin = 2.0°
CCD_Profile_fitting scansh = −26→26
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		k = −7→8
Tmin = 0.735, Tmax = 1.000l = −17→17
6482 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)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.0314P)2 + 10.4033P]
where P = (Fo2 + 2Fc2)/3
1997 reflections(Δ/σ)max = 0.030
140 parametersΔρmax = 0.44 e Å−3
9 restraintsΔρmin = −0.49 e Å−3
Crystal data top
[Ni(C6H2O3S)2(H2O)4]V = 1744.1 (15) Å3
Mr = 475.13Z = 4
Monoclinic, C2/cMo Kα radiation
a = 20.800 (11) ŵ = 1.41 mm−1
b = 6.450 (3) ÅT = 293 K
c = 13.566 (7) Å0.18 × 0.12 × 0.08 mm
β = 106.593 (9)°
Data collection top
Bruker SMART
diffractometer		1997 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1722 reflections with I > 2σ(I)
Tmin = 0.735, Tmax = 1.000Rint = 0.027
6482 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.030 w = 1/[σ2(Fo2) + (0.0314P)2 + 10.4033P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.091Δρmax = 0.44 e Å−3
S = 1.00Δρmin = −0.49 e Å−3
1997 reflectionsAbsolute structure: ?
140 parametersFlack parameter: ?
9 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
Ni10.50000.00001.00000.01645 (14)
S10.87523 (3)−0.09331 (11)1.20823 (6)0.01997 (17)
N10.59233 (12)0.0734 (4)0.96894 (19)0.0206 (5)
H1A0.5919 (18)0.2081 (18)0.951 (2)0.029 (9)*
H1B0.596 (2)−0.010 (4)0.917 (2)0.057 (14)*
C10.78851 (14)−0.0450 (5)1.1547 (2)0.0192 (6)
C20.74470 (15)−0.2073 (5)1.1195 (3)0.0278 (7)
H2A0.7593−0.34631.13450.033*
C30.67935 (15)−0.1665 (5)1.0622 (2)0.0257 (7)
H3A0.6490−0.27801.03860.031*
C40.65795 (13)0.0354 (4)1.0390 (2)0.0186 (6)
C50.70049 (15)0.1979 (5)1.0810 (2)0.0258 (6)
H5C0.68480.33671.07030.031*
C60.76580 (15)0.1582 (5)1.1385 (2)0.0256 (7)
H6A0.79510.26971.16690.031*
O10.89542 (11)0.0018 (4)1.31048 (17)0.0283 (5)
O20.90761 (11)0.0044 (4)1.13772 (19)0.0306 (5)
O30.88359 (11)−0.3179 (3)1.21135 (17)0.0277 (5)
O40.50276 (11)−0.2964 (3)0.94394 (17)0.0264 (5)
H4A0.5372−0.31040.92410.040*
H4B0.4639 (7)−0.353 (7)0.907 (3)0.064 (15)*
O50.45678 (11)0.1030 (3)0.85214 (16)0.0251 (5)
H5A0.43600.00500.81600.038*
H5B0.4369 (15)0.2296 (19)0.841 (3)0.058 (14)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0141 (2)0.0153 (2)0.0175 (3)0.0006 (2)0.00051 (18)−0.0002 (2)
S10.0164 (3)0.0181 (3)0.0224 (4)0.0030 (3)0.0008 (3)0.0010 (3)
N10.0171 (11)0.0202 (12)0.0223 (12)0.0002 (10)0.0021 (10)0.0019 (10)
C10.0148 (12)0.0233 (15)0.0171 (13)0.0014 (11)0.0008 (10)−0.0003 (11)
C20.0247 (15)0.0174 (14)0.0364 (18)0.0034 (12)0.0011 (13)0.0044 (13)
C30.0202 (14)0.0199 (14)0.0330 (17)−0.0040 (12)0.0011 (12)−0.0011 (13)
C40.0145 (12)0.0223 (15)0.0191 (13)0.0021 (11)0.0049 (10)0.0010 (11)
C50.0222 (14)0.0191 (14)0.0332 (17)0.0048 (12)0.0033 (12)−0.0016 (13)
C60.0203 (14)0.0199 (14)0.0324 (17)−0.0018 (12)0.0009 (12)−0.0050 (13)
O10.0256 (11)0.0279 (12)0.0257 (11)0.0014 (10)−0.0018 (9)−0.0051 (10)
O20.0240 (11)0.0306 (12)0.0392 (13)0.0041 (10)0.0125 (10)0.0084 (11)
O30.0289 (11)0.0194 (11)0.0292 (12)0.0073 (9)−0.0005 (9)0.0005 (9)
O40.0239 (10)0.0200 (11)0.0341 (12)−0.0023 (9)0.0065 (9)−0.0085 (9)
O50.0285 (11)0.0200 (11)0.0209 (11)0.0016 (9)−0.0025 (9)0.0004 (9)
Geometric parameters (Å, °) top
Ni1—O52.060 (2)C1—C61.389 (4)
Ni1—O5i2.060 (2)C2—C31.385 (4)
Ni1—O42.064 (2)C2—H2A0.9500
Ni1—O4i2.064 (2)C3—C41.384 (4)
Ni1—N1i2.133 (3)C3—H3A0.9500
Ni1—N12.133 (3)C4—C51.385 (4)
S1—O31.458 (2)C5—C61.384 (4)
S1—O21.461 (2)C5—H5C0.9500
S1—O11.464 (2)C6—H6A0.9500
S1—C11.769 (3)O4—H4A0.8400
N1—C41.444 (4)O4—H4B0.898 (10)
N1—H1A0.900 (10)O5—H5A0.8400
N1—H1B0.905 (10)O5—H5B0.908 (10)
C1—C21.381 (4)
O5—Ni1—O5i180.000 (1)H1A—N1—H1B111.5 (16)
O5—Ni1—O489.45 (9)C2—C1—C6120.0 (3)
O5i—Ni1—O490.55 (9)C2—C1—S1120.2 (2)
O5—Ni1—O4i90.55 (9)C6—C1—S1119.5 (2)
O5i—Ni1—O4i89.45 (9)C1—C2—C3119.7 (3)
O4—Ni1—O4i180.0C1—C2—H2A120.1
O5—Ni1—N1i95.55 (9)C3—C2—H2A120.1
O5i—Ni1—N1i84.45 (9)C4—C3—C2120.5 (3)
O4—Ni1—N1i89.34 (10)C4—C3—H3A119.8
O4i—Ni1—N1i90.66 (10)C2—C3—H3A119.8
O5—Ni1—N184.45 (9)C3—C4—C5119.5 (3)
O5i—Ni1—N195.55 (9)C3—C4—N1119.4 (3)
O4—Ni1—N190.66 (10)C5—C4—N1121.0 (3)
O4i—Ni1—N189.34 (10)C6—C5—C4120.1 (3)
N1i—Ni1—N1180.000 (1)C6—C5—H5C120.0
O3—S1—O2111.96 (14)C4—C5—H5C120.0
O3—S1—O1112.91 (14)C5—C6—C1119.9 (3)
O2—S1—O1112.23 (15)C5—C6—H6A120.0
O3—S1—C1106.63 (14)C1—C6—H6A120.0
O2—S1—C1105.20 (14)Ni1—O4—H4A109.5
O1—S1—C1107.33 (13)Ni1—O4—H4B118 (2)
C4—N1—Ni1124.58 (19)H4A—O4—H4B119.4
C4—N1—H1A106 (2)Ni1—O5—H5A109.5
Ni1—N1—H1A109 (2)Ni1—O5—H5B120 (2)
C4—N1—H1B98 (3)H5A—O5—H5B116.5
Ni1—N1—H1B107 (3)
O5—Ni1—N1—C4−176.5 (2)S1—C1—C2—C3−169.0 (3)
O5i—Ni1—N1—C43.5 (2)C1—C2—C3—C40.8 (5)
O4—Ni1—N1—C4−87.1 (2)C2—C3—C4—C5−5.7 (5)
O4i—Ni1—N1—C492.9 (2)C2—C3—C4—N1172.5 (3)
N1i—Ni1—N1—C411 (100)Ni1—N1—C4—C366.7 (4)
O3—S1—C1—C2−4.2 (3)Ni1—N1—C4—C5−115.1 (3)
O2—S1—C1—C2114.9 (3)C3—C4—C5—C65.5 (5)
O1—S1—C1—C2−125.4 (3)N1—C4—C5—C6−172.7 (3)
O3—S1—C1—C6−177.5 (2)C4—C5—C6—C1−0.4 (5)
O2—S1—C1—C6−58.4 (3)C2—C1—C6—C5−4.5 (5)
O1—S1—C1—C661.3 (3)S1—C1—C6—C5168.8 (2)
C6—C1—C2—C34.3 (5)
Symmetry codes: (i) −x+1, −y, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2ii0.90 (1)2.22 (2)3.084 (4)162 (3)
N1—H1B···O3iii0.91 (1)2.21 (1)3.106 (4)171 (4)
O4—H4A···S1iii0.842.963.768 (3)161
O4—H4B···O1iv0.90 (1)1.90 (1)2.777 (3)166 (2)
O4—H4B···S1iv0.90 (1)2.82 (3)3.595 (3)145 (3)
O5—H5A···O3iv0.841.942.773 (3)169
O5—H5B···O1v0.91 (1)1.93 (1)2.834 (3)177 (4)
Symmetry codes: (ii) −x+3/2, −y+1/2, −z+2; (iii) −x+3/2, −y−1/2, −z+2; (iv) x−1/2, −y−1/2, z−1/2; (v) x−1/2, −y+1/2, z−1/2.
Table 1
Selected geometric parameters (Å, °) top
Ni1—O52.060 (2)Ni1—O4i2.064 (2)
Ni1—O5i2.060 (2)Ni1—N1i2.133 (3)
Ni1—O42.064 (2)Ni1—N12.133 (3)
O5—Ni1—O5i180.000 (1)O5i—Ni1—N195.55 (9)
O5—Ni1—O489.45 (9)O4—Ni1—N190.66 (10)
O5i—Ni1—O490.55 (9)O4i—Ni1—N189.34 (10)
O5—Ni1—O4i90.55 (9)N1i—Ni1—N1180.000 (1)
O5i—Ni1—O4i89.45 (9)C4—N1—Ni1124.58 (19)
O4—Ni1—O4i180.0Ni1—O4—H4A109.5
O5—Ni1—N1i95.55 (9)Ni1—O4—H4B118 (2)
O5i—Ni1—N1i84.45 (9)H4A—O4—H4B119.4
O4—Ni1—N1i89.34 (10)Ni1—O5—H5A109.5
O4i—Ni1—N1i90.66 (10)Ni1—O5—H5B120 (2)
O5—Ni1—N184.45 (9)H5A—O5—H5B116.5
Symmetry codes: (i) −x+1, −y, −z+2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2ii0.90 (1)2.22 (2)3.084 (4)162 (3)
N1—H1B···O3iii0.91 (1)2.21 (1)3.106 (4)171 (4)
O4—H4A···S1iii0.842.963.768 (3)161
O4—H4B···O1iv0.90 (1)1.90 (1)2.777 (3)166 (2)
O4—H4B···S1iv0.90 (1)2.82 (3)3.595 (3)145 (3)
O5—H5A···O3iv0.841.942.773 (3)169
O5—H5B···O1v0.91 (1)1.93 (1)2.834 (3)177 (4)
Symmetry codes: (ii) −x+3/2, −y+1/2, −z+2; (iii) −x+3/2, −y−1/2, −z+2; (iv) x−1/2, −y−1/2, z−1/2; (v) x−1/2, −y+1/2, z−1/2.
Acknowledgements top

We gratefully acknowledge financial support from the 'One Hundred Talents Program' of the Chinese Academy of Sciences and National Science Foundation of China (grant No. 20473092).

references
References top

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Shakeri, V. & Haussuhl, S. (1992b). Z. Kristallogr. 198, 167–168.

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

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

Zhou, J.-S., Cai, J.-W., Wang, L. & Ng, S.-W. (2004). Dalton Trans. pp. 1493–1497.