Acta Cryst. (2007). E63, m2913-m2914 [ doi:10.1107/S1600536807054372 ]
The asymmetric unit of the title compound, [Ni(H2O)6](C6H6NO3S)2, contains one half-cation and one anion; the Ni atom lies on an inversion centre. In the crystal structure, intermolecular O-H
O and O-HS hydrogen bonds result in the formation of a supramolecular network. The conformation of the anion is stabilized by an intramolecular C-HO hydrogen-bonding interaction.
Crystals of the title compound were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb, which was then sealed. Samarium (III) nitrate hexahydrate (222.1 mg, 0.5 mmol), nickel nitrate hexahydrate (145.4 mg, 0.5 mmol), 4-aminobenzenesulfonic acid (346.4 mg, 2 mmol), ammonia (0.5 mol/l, 4 ml) and distilled water (10 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure up to 453 K over the course of 7 d and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colourless solution was decanted from small green crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.
H atoms (for H2O) were located in difference syntheses and refined isotropically. The other H atoms were positioned geometrically, with N—H = 0.86 Å (for NH2) and C—H = 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).
![[Figure 1]](./at2449fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [symmetry code (A): 3/2 − x,1/2±y, 1/2 − z]. |
![[Figure 2]](./at2449fig2thm.gif)
| Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines. |
| [Ni(H2O)6](C6H6NO3S)2 | F(000) = 532 |
| Mr = 511.16 | Dx = 1.551 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 5607 reflections |
| a = 6.8971 (11) Å | θ = 2.3–26.9° |
| b = 6.301 (2) Å | µ = 1.14 mm−1 |
| c = 25.2038 (13) Å | T = 273 K |
| β = 91.971 (4)° | Prism, green |
| V = 1094.7 (5) Å3 | 0.50 × 0.37 × 0.20 mm |
| Z = 2 |
| Bruker APEX-II area-detector diffractometer | 2132 independent reflections |
| Radiation source: fine-focus sealed tube | 1848 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.024 |
| φ and ω scans | θmax = 26.3°, θmin = 3.2° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
| Tmin = 0.600, Tmax = 0.804 | k = −7→7 |
| 6665 measured reflections | l = −31→31 |
| 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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.10 | w = 1/[σ2(Fo2) + (0.0447P)2 + 0.2147P] where P = (Fo2 + 2Fc2)/3 |
| 2132 reflections | (Δ/σ)max = 0.001 |
| 157 parameters | Δρmax = 0.25 e Å−3 |
| 9 restraints | Δρmin = −0.31 e Å−3 |
| [Ni(H2O)6](C6H6NO3S)2 | V = 1094.7 (5) Å3 |
| Mr = 511.16 | Z = 2 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 6.8971 (11) Å | µ = 1.14 mm−1 |
| b = 6.301 (2) Å | T = 273 K |
| c = 25.2038 (13) Å | 0.50 × 0.37 × 0.20 mm |
| β = 91.971 (4)° |
| Bruker APEX-II area-detector diffractometer | 2132 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1848 reflections with I > 2σ(I) |
| Tmin = 0.600, Tmax = 0.804 | Rint = 0.024 |
| 6665 measured reflections | θmax = 26.3° |
| R[F2 > 2σ(F2)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.084 | Δρmax = 0.25 e Å−3 |
| S = 1.10 | Δρmin = −0.31 e Å−3 |
| 2132 reflections | Absolute structure: ? |
| 157 parameters | Flack parameter: ? |
| 9 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| Ni1 | 0.5000 | 0.0000 | 0.0000 | 0.04055 (14) | |
| S1 | −0.01470 (7) | 0.60846 (8) | 0.90519 (2) | 0.04425 (17) | |
| O1 | 0.7236 (3) | −0.1024 (3) | 0.04785 (10) | 0.0765 (6) | |
| O2 | 0.5088 (3) | 0.2884 (3) | 0.03505 (8) | 0.0574 (4) | |
| O3 | 0.3036 (3) | −0.1037 (3) | 0.05313 (10) | 0.0758 (6) | |
| O4 | 0.1555 (2) | 0.5136 (2) | 0.93075 (7) | 0.0569 (4) | |
| O5 | −0.0141 (2) | 0.8392 (3) | 0.90903 (7) | 0.0557 (4) | |
| O6 | −0.1925 (3) | 0.5163 (2) | 0.92401 (8) | 0.0575 (4) | |
| N1 | 0.0317 (5) | 0.3784 (8) | 0.67174 (12) | 0.1314 (14) | |
| H1C | 0.0055 | 0.4711 | 0.6475 | 0.158* | |
| H1D | 0.0687 | 0.2531 | 0.6631 | 0.158* | |
| C1 | 0.0126 (4) | 0.4358 (6) | 0.72949 (11) | 0.0719 (8) | |
| C2 | −0.0463 (4) | 0.6347 (6) | 0.74505 (12) | 0.0763 (9) | |
| H2 | −0.0822 | 0.7338 | 0.7192 | 0.092* | |
| C3 | −0.0536 (4) | 0.6918 (5) | 0.79835 (11) | 0.0667 (7) | |
| H3 | −0.0919 | 0.8278 | 0.8078 | 0.080* | |
| C4 | −0.0037 (3) | 0.5449 (4) | 0.83690 (9) | 0.0487 (5) | |
| C5 | 0.0528 (4) | 0.3432 (4) | 0.82204 (10) | 0.0624 (6) | |
| H5 | 0.0855 | 0.2430 | 0.8479 | 0.075* | |
| C6 | 0.0610 (4) | 0.2898 (5) | 0.76887 (11) | 0.0736 (8) | |
| H6 | 0.0996 | 0.1539 | 0.7594 | 0.088* | |
| H1A | 0.748 (4) | −0.220 (3) | 0.0517 (10) | 0.072 (8)* | |
| H2A | 0.611 (3) | 0.341 (5) | 0.0483 (12) | 0.080 (10)* | |
| H3A | 0.279 (4) | −0.226 (3) | 0.0572 (11) | 0.074 (9)* | |
| H1B | 0.810 (4) | −0.020 (3) | 0.0580 (12) | 0.070 (9)* | |
| H2B | 0.419 (3) | 0.343 (5) | 0.0500 (11) | 0.078 (10)* | |
| H3B | 0.216 (4) | −0.026 (4) | 0.0596 (14) | 0.083 (11)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni1 | 0.0374 (2) | 0.0301 (2) | 0.0541 (2) | 0.00076 (14) | 0.00152 (15) | 0.00166 (15) |
| S1 | 0.0426 (3) | 0.0342 (3) | 0.0561 (3) | 0.0005 (2) | 0.0026 (2) | −0.0004 (2) |
| O1 | 0.0722 (13) | 0.0378 (11) | 0.1161 (17) | 0.0050 (9) | −0.0434 (11) | 0.0003 (11) |
| O2 | 0.0474 (9) | 0.0412 (9) | 0.0837 (12) | −0.0004 (8) | 0.0051 (9) | −0.0139 (8) |
| O3 | 0.0768 (13) | 0.0382 (11) | 0.1153 (17) | 0.0002 (10) | 0.0478 (12) | 0.0056 (11) |
| O4 | 0.0589 (10) | 0.0441 (10) | 0.0666 (10) | 0.0055 (7) | −0.0116 (8) | −0.0015 (7) |
| O5 | 0.0542 (9) | 0.0347 (8) | 0.0785 (11) | 0.0004 (7) | 0.0047 (8) | −0.0019 (7) |
| O6 | 0.0565 (9) | 0.0432 (10) | 0.0739 (11) | −0.0039 (7) | 0.0169 (8) | −0.0024 (7) |
| N1 | 0.124 (3) | 0.200 (5) | 0.0706 (19) | 0.006 (3) | 0.0116 (18) | −0.011 (2) |
| C1 | 0.0546 (14) | 0.102 (2) | 0.0588 (16) | −0.0075 (15) | 0.0014 (12) | −0.0007 (15) |
| C2 | 0.0683 (17) | 0.097 (3) | 0.0632 (16) | 0.0087 (16) | 0.0010 (13) | 0.0233 (16) |
| C3 | 0.0640 (15) | 0.0644 (18) | 0.0721 (17) | 0.0104 (13) | 0.0057 (12) | 0.0141 (14) |
| C4 | 0.0408 (11) | 0.0482 (13) | 0.0572 (13) | −0.0002 (9) | 0.0011 (9) | 0.0031 (10) |
| C5 | 0.0747 (16) | 0.0530 (15) | 0.0593 (14) | 0.0099 (12) | −0.0010 (12) | −0.0018 (12) |
| C6 | 0.0801 (19) | 0.075 (2) | 0.0661 (17) | 0.0056 (15) | 0.0043 (14) | −0.0151 (15) |
| Ni1—O1i | 2.0300 (17) | O3—H3B | 0.801 (17) |
| Ni1—O1 | 2.0300 (17) | N1—C1 | 1.510 (4) |
| Ni1—O2i | 2.0207 (17) | N1—H1C | 0.8600 |
| Ni1—O2 | 2.0207 (17) | N1—H1D | 0.8600 |
| Ni1—O3i | 2.0444 (18) | C1—C2 | 1.379 (5) |
| Ni1—O3 | 2.0445 (18) | C1—C6 | 1.385 (4) |
| S1—O4 | 1.4487 (17) | C2—C3 | 1.393 (4) |
| S1—O6 | 1.4512 (17) | C2—H2 | 0.9300 |
| S1—O5 | 1.4571 (18) | C3—C4 | 1.377 (4) |
| S1—C4 | 1.771 (2) | C3—H3 | 0.9300 |
| O1—H1A | 0.765 (16) | C4—C5 | 1.385 (3) |
| O1—H1B | 0.821 (17) | C5—C6 | 1.385 (4) |
| O2—H2A | 0.841 (17) | C5—H5 | 0.9300 |
| O2—H2B | 0.810 (17) | C6—H6 | 0.9300 |
| O3—H3A | 0.797 (17) | ||
| O1i—Ni1—O1 | 180.0 | H2A—O2—H2B | 107 (2) |
| O1i—Ni1—O2 | 89.11 (8) | Ni1—O3—H3A | 123 (2) |
| O1—Ni1—O2 | 90.89 (8) | Ni1—O3—H3B | 117 (2) |
| O1—Ni1—O3i | 89.08 (10) | H3A—O3—H3B | 114 (3) |
| O1—Ni1—O3 | 90.92 (10) | C1—N1—H1C | 120.0 |
| O2i—Ni1—O2 | 180.0 | C1—N1—H1D | 120.0 |
| O2—Ni1—O3i | 89.32 (8) | H1C—N1—H1D | 120.0 |
| O2—Ni1—O3 | 90.67 (8) | C2—C1—C6 | 117.8 (3) |
| O3i—Ni1—O3 | 180.0 | C2—C1—N1 | 121.9 (3) |
| O2i—Ni1—O1i | 90.89 (8) | C6—C1—N1 | 120.3 (3) |
| O1—Ni1—O2i | 89.11 (8) | C1—C2—C3 | 122.0 (3) |
| O2i—Ni1—O3i | 90.68 (8) | C1—C2—H2 | 119.0 |
| O1i—Ni1—O3i | 90.92 (10) | C3—C2—H2 | 119.0 |
| O2i—Ni1—O3 | 89.32 (8) | C4—C3—C2 | 119.4 (3) |
| O1i—Ni1—O3 | 89.08 (10) | C4—C3—H3 | 120.3 |
| O4—S1—O6 | 111.73 (11) | C2—C3—H3 | 120.3 |
| O4—S1—O5 | 112.45 (10) | C3—C4—C5 | 119.5 (2) |
| O6—S1—O5 | 112.22 (10) | C3—C4—S1 | 121.0 (2) |
| O4—S1—C4 | 106.12 (11) | C5—C4—S1 | 119.48 (18) |
| O6—S1—C4 | 106.98 (11) | C6—C5—C4 | 120.4 (3) |
| O5—S1—C4 | 106.86 (11) | C6—C5—H5 | 119.8 |
| Ni1—O1—H1A | 123.1 (19) | C4—C5—H5 | 119.8 |
| Ni1—O1—H1B | 120.7 (19) | C5—C6—C1 | 121.0 (3) |
| H1A—O1—H1B | 114 (2) | C5—C6—H6 | 119.5 |
| Ni1—O2—H2A | 123 (2) | C1—C6—H6 | 119.5 |
| Ni1—O2—H2B | 125 (2) |
| Symmetry code: (i) −x+1, −y, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C3—H3···O5 | 0.93 | 2.59 | 2.944 (3) | 103 |
| O3—H3A···S1ii | 0.80 (2) | 3.18 (2) | 3.916 (2) | 154 (2) |
| O1—H1B···O5iii | 0.82 (2) | 1.98 (2) | 2.793 (3) | 173 (3) |
| O1—H1B···S1iii | 0.82 (2) | 3.08 (2) | 3.867 (2) | 161 (2) |
| O2—H2B···O6iv | 0.81 (2) | 1.93 (2) | 2.737 (2) | 172 (3) |
| O3—H3B···O5iv | 0.80 (2) | 2.00 (2) | 2.794 (3) | 169 (4) |
| O1—H1A···O4v | 0.77 (2) | 2.01 (2) | 2.769 (3) | 172 (3) |
| O2—H2A···O4iii | 0.84 (2) | 1.91 (2) | 2.743 (2) | 172 (3) |
| O3—H3A···O6ii | 0.80 (2) | 1.99 (2) | 2.776 (3) | 171 (3) |
| Symmetry codes: (ii) −x, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x, −y+1, −z+1; (v) −x+1, −y, −z+1. |
| Ni1—O1i | 2.0300 (17) | Ni1—O2 | 2.0207 (17) |
| Ni1—O1 | 2.0300 (17) | Ni1—O3i | 2.0444 (18) |
| Ni1—O2i | 2.0207 (17) | Ni1—O3 | 2.0445 (18) |
| O1i—Ni1—O1 | 180.0 | O2i—Ni1—O2 | 180.0 |
| O1i—Ni1—O2 | 89.11 (8) | O2—Ni1—O3i | 89.32 (8) |
| O1—Ni1—O2 | 90.89 (8) | O2—Ni1—O3 | 90.67 (8) |
| O1—Ni1—O3i | 89.08 (10) | O3i—Ni1—O3 | 180.0 |
| O1—Ni1—O3 | 90.92 (10) |
| Symmetry code: (i) −x+1, −y, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C3—H3···O5 | 0.93 | 2.59 | 2.944 (3) | 103 |
| O3—H3A···S1ii | 0.797 (17) | 3.18 (2) | 3.916 (2) | 154 (2) |
| O1—H1B···O5iii | 0.821 (17) | 1.976 (18) | 2.793 (3) | 173 (3) |
| O1—H1B···S1iii | 0.821 (17) | 3.083 (17) | 3.867 (2) | 161 (2) |
| O2—H2B···O6iv | 0.810 (17) | 1.933 (18) | 2.737 (2) | 172 (3) |
| O3—H3B···O5iv | 0.801 (17) | 2.004 (19) | 2.794 (3) | 169 (4) |
| O1—H1A···O4v | 0.765 (16) | 2.010 (18) | 2.769 (3) | 172 (3) |
| O2—H2A···O4iii | 0.841 (17) | 1.909 (18) | 2.743 (2) | 172 (3) |
| O3—H3A···O6ii | 0.797 (17) | 1.985 (18) | 2.776 (3) | 171 (3) |
| Symmetry codes: (ii) −x, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x, −y+1, −z+1; (v) −x+1, −y, −z+1. |
We thank the Science and Technology Program of Jinggangshan University for financial support of this work (grant No. 2007).
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Braga, D. & Grepioni, F. (2000). Acc. Chem. Res. 33, 601–608.
Braga, D., Grepioni, F. & Desiraju, G. R. (1998). Chem. Rev. 98, 1375–1386.
Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.
Desiraju, G. R. (1995). Angew. Chem. Int. Ed. Engl. 34, 2311–2315.
Desiraju, G. R. (1997). J. Chem. Soc. Chem. Commun. pp. 1475–1476.
Ma, B. Q., Gao, S., Sun, H. L. & Xu, G. X. (2001). J. Chem. Soc. Dalton Trans. pp. 130–133.
Moulton, B. & Zaworotko, M. J. (2001). Chem. Rev. 101, 1629–1658.
Pan, L., Ching, N. & Huang, X. Y. (2001). Chem. Eur. J. 7, 4431–4437.
Prior, T. J. & Rosseinsky, M. J. (2001). Chem. Commun. pp. 1222–1223.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Siemens (1996). SAINT and SHELXTL. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Zaworotko, M. J. (1997). Nature (London), 386, 220–226.
In the synthesis of crystal structures by design, the assembly of molecular units in predefined arrangements is a key goal (Desiraju, 1995, 1997; Braga et al., 1998). Due to hydrogen-bonding interactions are of critical importance in biological systems, organic materials and coordination chemistry. Hydrogen-bonding is currently the best tools in achieving this goal. (Zaworotko, 1997; Braga & Grepioni, 2000). Supramolecular architectures are of considerable contemporary interest by virtue of their potential applications in various fields. (Moulton & Zaworotko, 2001; Pan et al., 2001; Ma et al., 2001; Prior & Rosseinsky, 2001). We originally attempted to synthesize complexes featuring Sm and Ni metals chains by reaction of the samarium (III) and nickel(II) ions with 4-aminobenzenesulfonic acid ligand. Unfortunately, we obtained only the title compound, (I), and we report herein its crystal structure.
In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). The title compound, [Ni(H2O)6](C6H6NO3S)2, contains one half-cation and one anion; the Ni atom lies on an inversion centre.
In the crystal structure, intermolecular O—H···O and O—H···S hydrogen bonds (Fig. 2 and Table 2) result in the formation of a supramolecular network structure. The molecular conformation is stabilized by an intramolecular C—H···O hydrogen bonding interaction.