Acta Cryst. (2007). E63, m2176 [ doi:10.1107/S1600536807034472 ]
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N3)nickel(II) sulfate dihydrateThe title compound, [Ni(C3H4N2)6]SO4·2H2O, was prepared by hydrothermal synthesis. The NiII atom lies on a site of 
point symmetry and is coordinated by six imidazole ligands in a regular octahedral geometry. The sulfate anion is disordered about a site of 32 point symmetry; water molecules lie on sites of 32 point symmetry and on general positions. The coordinated imidazole molecules make N-H
O hydrogen bonds with the sulfate anions.
Light purple block crystals were synthesized hydrothermally from a complex reaction mixture. In a typical synthesis, GeO2 (0.1054 g), NH4VO3 (0.1079) and NiSO4 (0.5278 g) were dissolved in the mixed solvent of dimethyl formamide (0.5162 g) and water (1.8388 g) followed by addition of imidazole (0.4551 g) with constant stirring. The mixture was kept in a 25 ml Teflon-lined steel autoclave at 443 K for 7 days then slowly cooled to room temperature. The product was filtered, washed with distilled water, and dried at room temperature.
H atoms bound to C or N atoms were placed geometrically and allowed to ride with C—H = 0.93 Å or N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C/N). H atoms of the water molecules were located in difference Fourier maps and refined with O—H distances restrained to be 0.85 (1)Å and with Uiso(H) = 1.2Ueq(O). The displacement parameters of the O atoms of the water molecules were restrained to approximate isotropic behaviour and the S—O distances in the disordered sulfate anion were restrained to be 1.420 (2) Å.
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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, 1997); software used to prepare material for publication: SHELXTL.
![[Figure 1]](./bi2207fig1thm.gif)
| Fig. 1. The molecular structure of title compound showing displacement ellipsoids at the 70% probability level for non-H atoms. |
![[Figure 2]](./bi2207fig2thm.gif)
| Fig. 2. Unit-cell contents for title compound. Dashed lines denote hydrogen bonds. |
| [Ni(C3H4N2)6]SO4·2H2O | Dx = 1.236 Mg m−3 |
| Mr = 599.29 | Mo Kα radiation, λ = 0.71073 Å |
| Trigonal, P31c | Cell parameters from 7600 reflections |
| Hall symbol: -P 3 2c | θ = 2.6–25.0° |
| a = 9.0029 (9) Å | µ = 0.72 mm−1 |
| c = 22.937 (4) Å | T = 293 K |
| V = 1610.0 (4) Å3 | Block, blue |
| Z = 2 | 0.13 × 0.12 × 0.12 mm |
| F(000) = 624 |
| Bruker APEXII CCD diffractometer | 949 independent reflections |
| Radiation source: fine-focus sealed tube | 794 reflections with I > 2σ(I) |
| graphite | Rint = 0.023 |
| ω scans | θmax = 25.0°, θmin = 2.6° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −10→9 |
| Tmin = 0.913, Tmax = 0.919 | k = −10→9 |
| 7600 measured reflections | l = −15→27 |
| 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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.183 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.16 | w = 1/[σ2(Fo2) + (0.13P)2 + 0.1485P] where P = (Fo2 + 2Fc2)/3 |
| 949 reflections | (Δ/σ)max = 0.032 |
| 82 parameters | Δρmax = 0.49 e Å−3 |
| 17 restraints | Δρmin = −0.48 e Å−3 |
| [Ni(C3H4N2)6]SO4·2H2O | Z = 2 |
| Mr = 599.29 | Mo Kα radiation |
| Trigonal, P31c | µ = 0.72 mm−1 |
| a = 9.0029 (9) Å | T = 293 K |
| c = 22.937 (4) Å | 0.13 × 0.12 × 0.12 mm |
| V = 1610.0 (4) Å3 |
| Bruker APEXII CCD diffractometer | 949 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 794 reflections with I > 2σ(I) |
| Tmin = 0.913, Tmax = 0.919 | Rint = 0.023 |
| 7600 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.056 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.183 | Δρmax = 0.49 e Å−3 |
| S = 1.16 | Δρmin = −0.48 e Å−3 |
| 949 reflections | Absolute structure: ? |
| 82 parameters | Flack parameter: ? |
| 17 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 | Occ. (<1) | |
| Ni1 | 0.0000 | 0.0000 | 0.0000 | 0.04666 (14) | |
| S1 | 0.3333 | −0.3333 | −0.2500 | 0.0660 (3) | |
| N1 | 0.3116 (2) | −0.0743 (2) | −0.12231 (8) | 0.0878 (5) | |
| H3A | 0.3235 | −0.1243 | −0.1524 | 0.105* | |
| N2 | 0.18871 (19) | −0.00718 (14) | −0.05341 (7) | 0.0557 (4) | |
| C1 | 0.4392 (3) | 0.0428 (3) | −0.08892 (12) | 0.0901 (8) | |
| H1A | 0.5562 | 0.0872 | −0.0945 | 0.108* | |
| C2 | 0.3650 (2) | 0.0825 (3) | −0.04641 (10) | 0.0746 (6) | |
| H4A | 0.4229 | 0.1592 | −0.0163 | 0.090* | |
| C3 | 0.1628 (2) | −0.0995 (2) | −0.10058 (8) | 0.0693 (5) | |
| H6A | 0.0557 | −0.1725 | −0.1167 | 0.083* | |
| O1 | 0.3333 | −0.3333 | −0.18837 (15) | 0.108 (2) | 0.50 |
| O2 | 0.3702 (8) | −0.4468 (6) | −0.2181 (3) | 0.211 (2) | 0.50 |
| O1W | 0.0000 | −1.0000 | −0.2500 | 0.313 (5) | 0.50 |
| H1W | 0.0255 (4) | −1.0713 (3) | −0.2645 (3) | 0.375* | 0.17 |
| O2W | 0.3549 (10) | −0.7269 (11) | −0.2078 (5) | 0.137 (3) | 0.25 |
| H2WB | 0.460 (2) | −0.647 (6) | −0.211 (6) | 0.165* | 0.25 |
| H2WA | 0.271 (3) | −0.799 (6) | −0.2284 (17) | 0.165* | 0.25 |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni1 | 0.05113 (18) | 0.05113 (18) | 0.0377 (3) | 0.02556 (9) | 0.000 | 0.000 |
| S1 | 0.0785 (4) | 0.0785 (4) | 0.0412 (5) | 0.0392 (2) | 0.000 | 0.000 |
| N1 | 0.1061 (8) | 0.1020 (9) | 0.0739 (10) | 0.0660 (7) | 0.0246 (9) | −0.0081 (8) |
| N2 | 0.0600 (7) | 0.0609 (6) | 0.0504 (8) | 0.0334 (5) | 0.0035 (7) | −0.0022 (5) |
| C1 | 0.0703 (9) | 0.1121 (11) | 0.0945 (17) | 0.0506 (9) | 0.0056 (11) | −0.0219 (12) |
| C2 | 0.0606 (7) | 0.0906 (11) | 0.0753 (12) | 0.0398 (7) | 0.0016 (9) | −0.0088 (10) |
| C3 | 0.0742 (8) | 0.0729 (9) | 0.0624 (11) | 0.0380 (6) | 0.0110 (8) | −0.0046 (8) |
| O1 | 0.135 (3) | 0.135 (3) | 0.054 (3) | 0.0674 (15) | 0.000 | 0.000 |
| O2 | 0.317 (4) | 0.165 (3) | 0.196 (5) | 0.155 (2) | −0.079 (4) | 0.024 (3) |
| O1W | 0.315 (6) | 0.315 (6) | 0.307 (8) | 0.158 (3) | 0.000 | 0.000 |
| O2W | 0.155 (4) | 0.141 (4) | 0.143 (5) | 0.095 (3) | 0.018 (4) | 0.003 (4) |
| Ni1—N2i | 2.1216 (17) | N1—C1 | 1.344 (3) |
| Ni1—N2ii | 2.1216 (17) | N1—H3A | 0.860 |
| Ni1—N2iii | 2.1216 (17) | N2—C3 | 1.312 (2) |
| Ni1—N2 | 2.1216 (17) | N2—C2 | 1.384 (2) |
| Ni1—N2iv | 2.1216 (17) | C1—C2 | 1.328 (3) |
| Ni1—N2v | 2.1216 (17) | C1—H1A | 0.930 |
| S1—O1vi | 1.414 (3) | C2—H4A | 0.930 |
| S1—O1 | 1.414 (3) | C3—H6A | 0.930 |
| S1—O2vii | 1.423 (6) | O1—O2ix | 1.400 (7) |
| S1—O2viii | 1.423 (6) | O1—O2viii | 1.400 (7) |
| S1—O2ix | 1.423 (6) | O1—O2 | 1.400 (7) |
| S1—O2x | 1.423 (6) | O2—O2vi | 1.616 (13) |
| S1—O2 | 1.423 (6) | O1W—H1W | 0.850 (3) |
| S1—O2vi | 1.423 (6) | O2W—H2WB | 0.855 (18) |
| N1—C3 | 1.338 (3) | O2W—H2WA | 0.853 (19) |
| N2i—Ni1—N2ii | 180.00 (11) | O2ix—S1—O2 | 96.0 (4) |
| N2i—Ni1—N2iii | 89.99 (7) | O2x—S1—O2 | 103.2 (4) |
| N2ii—Ni1—N2iii | 90.01 (7) | O1vi—S1—O2vi | 59.1 (3) |
| N2i—Ni1—N2 | 89.99 (7) | O1—S1—O2vi | 120.9 (3) |
| N2ii—Ni1—N2 | 90.01 (7) | O2vii—S1—O2vi | 96.0 (4) |
| N2iii—Ni1—N2 | 89.99 (7) | O2viii—S1—O2vi | 103.2 (4) |
| N2i—Ni1—N2iv | 90.01 (7) | O2ix—S1—O2vi | 156.7 (5) |
| N2ii—Ni1—N2iv | 89.99 (7) | O2x—S1—O2vi | 96.0 (4) |
| N2iii—Ni1—N2iv | 90.01 (7) | O2—S1—O2vi | 69.2 (6) |
| N2—Ni1—N2iv | 180.00 (9) | C3—N1—C1 | 108.16 (18) |
| N2i—Ni1—N2v | 90.01 (7) | C3—N1—H3A | 125.9 |
| N2ii—Ni1—N2v | 89.99 (7) | C1—N1—H3A | 125.9 |
| N2iii—Ni1—N2v | 180.00 (10) | C3—N2—C2 | 104.71 (17) |
| N2—Ni1—N2v | 90.01 (7) | C3—N2—Ni1 | 127.15 (12) |
| N2iv—Ni1—N2v | 89.99 (7) | C2—N2—Ni1 | 128.14 (14) |
| O1vi—S1—O1 | 180.0 | C2—C1—N1 | 106.35 (19) |
| O1vi—S1—O2vii | 59.1 (3) | C2—C1—H1A | 126.8 |
| O1—S1—O2vii | 120.9 (3) | N1—C1—H1A | 126.8 |
| O1vi—S1—O2viii | 120.9 (3) | C1—C2—N2 | 110.03 (19) |
| O1—S1—O2viii | 59.1 (3) | C1—C2—H4A | 125.0 |
| O2vii—S1—O2viii | 69.2 (6) | N2—C2—H4A | 125.0 |
| O1vi—S1—O2ix | 120.9 (3) | N2—C3—N1 | 110.71 (16) |
| O1—S1—O2ix | 59.1 (3) | N2—C3—H6A | 124.6 |
| O2vii—S1—O2ix | 103.2 (4) | N1—C3—H6A | 124.6 |
| O2viii—S1—O2ix | 96.0 (4) | O2ix—O1—O2viii | 98.2 (3) |
| O1vi—S1—O2x | 59.1 (3) | O2ix—O1—O2 | 98.2 (3) |
| O1—S1—O2x | 120.9 (3) | O2viii—O1—O2 | 98.2 (3) |
| O2vii—S1—O2x | 96.0 (4) | O2ix—O1—S1 | 60.8 (3) |
| O2viii—S1—O2x | 156.7 (5) | O2viii—O1—S1 | 60.8 (3) |
| O2ix—S1—O2x | 69.2 (6) | O2—O1—S1 | 60.8 (3) |
| O1vi—S1—O2 | 120.9 (3) | O1—O2—S1 | 60.1 (3) |
| O1—S1—O2 | 59.1 (3) | O1—O2—O2vi | 109.6 (3) |
| O2vii—S1—O2 | 156.7 (5) | S1—O2—O2vi | 55.4 (3) |
| O2viii—S1—O2 | 96.0 (4) | H2WB—O2W—H2WA | 141 (10) |
| Symmetry codes: (i) −x+y, −x, z; (ii) x−y, x, −z; (iii) −y, x−y, z; (iv) −x, −y, −z; (v) y, −x+y, −z; (vi) −y, −x, −z−1/2; (vii) x, x−y−1, −z−1/2; (viii) −y, x−y−1, z; (ix) −x+y+1, −x, z; (x) −x+y+1, y, −z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H3A···O1 | 0.86 | 2.10 | 2.868 (3) | 149 |
| N1—H3A···O2viii | 0.86 | 2.09 | 2.908 (7) | 159 |
| N1—H3A···O2ix | 0.86 | 2.44 | 3.191 (7) | 146 |
| Symmetry codes: (viii) −y, x−y−1, z; (ix) −x+y+1, −x, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H3A···O1 | 0.86 | 2.10 | 2.868 (3) | 149 |
| N1—H3A···O2i | 0.86 | 2.09 | 2.908 (7) | 159 |
| N1—H3A···O2ii | 0.86 | 2.44 | 3.191 (7) | 146 |
| Symmetry codes: (i) −y, x−y−1, z; (ii) −x+y+1, −x, z. |
This work was supported by the Education Office Foundation of Liaoning province (05 L220).
Bruker (1997). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2005). APEX2 (Version 1.27) and SAINT (Version 7.06). Bruker AXS Inc., Madison, Wisconsin, USA.
Fu, H.-Y., Dou, J.-M., Li, D.-C. & Wang, D.-Q. (2007). Acta Cryst. E63, m1793–m1795.
Gao, S., Liu, J.-W., Dong, Y., Huo, L.-H. & Zhao, H. (2004). Acta Cryst. E60, m778–m780.
Phung, N. D., Tedenac, J.-C. & Maurin, M. (1976). J. Inorg. Nucl. Chem. 38, 2316–2317.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.
Wang, Z.-X., Zhang, Y., Razak, I. A., Shanmuga Sundara Raj, S., Fun, H.-K., Li, F. & Song, H. (2000). Acta Cryst. C56, 161–162.
The title compound was obtained during an attempted synthesis of a metal-organic framework (MOF) incorporating NiII and imidazole. The unit cell has been reported previously (Phung et al., 1976), although complete space group information and atomic coordinates were not given.
The structure comprises discrete [Ni(C3N2H4)6]2+ cations (Figure 1). The NiII atom lies on a site of 3 point symmetry and is coordinated by six N atoms from six imidazole molecules in a regular octahedral geometry with Ni—N = 2.1216 (17) Å. The Ni—N bond lengths and angles are comparable to those in similar reported NiII compounds (for example, Fu et al., 2007). The sulfate anion is disordered about a site of 32 point symmetry. As shown in Figure 2, the non-coordinated N atoms of imidazole are involved in hydrogen-bonding interactions with O atoms of the sulfate groups.