Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100002262/qa0219sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100002262/qa0219Isup2.hkl |
A solution of 2,5-bis(1-pyrazolyl)hydrochinon (0.063 g; 0.260 mmol) in 10 ml CH2Cl2 was layered with a solution of 5 ml concentrated aqueous ammonia and 0.161 g (0.677 mmol) of NiCl2.6H2O. Formation of purple crystals was observed after one week. The liquid was removed from the crystals by filtration. The remaining crystalline compound was washed with 5 ml CH2Cl2 (yield: 0.034 g, 0.147 mmol; 22%).
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
[Ni(NH3)6]Cl2 | Mo Kα radiation, λ = 0.71073 Å |
Mr = 231.81 | Cell parameters from 339 reflections |
Cubic, Fm3m | θ = 1–20° |
a = 10.029 (2) Å | µ = 2.40 mm−1 |
V = 1008.7 (3) Å3 | T = 173 K |
Z = 4 | Octahedron, purple |
F(000) = 488 | 0.60 × 0.50 × 0.50 mm |
Dx = 1.526 Mg m−3 |
Siemens CCD three-circle diffractometer | 116 independent reflections |
Radiation source: fine-focus sealed tube | 115 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ω scans | θmax = 31.4°, θmin = 3.5° |
Absorption correction: numerical numerical | h = −14→14 |
Tmin = 0.327, Tmax = 0.380 | k = −14→14 |
4406 measured reflections | l = −14→12 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.013 | All H-atom parameters refined |
wR(F2) = 0.033 | w = 1/[σ2(Fo2) + (0.0135P)2 + 0.5364P] where P = (Fo2 + 2Fc2)/3 |
S = 1.32 | (Δ/σ)max < 0.001 |
116 reflections | Δρmax = 0.25 e Å−3 |
10 parameters | Δρmin = −0.30 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0173 (12) |
[Ni(NH3)6]Cl2 | Z = 4 |
Mr = 231.81 | Mo Kα radiation |
Cubic, Fm3m | µ = 2.40 mm−1 |
a = 10.029 (2) Å | T = 173 K |
V = 1008.7 (3) Å3 | 0.60 × 0.50 × 0.50 mm |
Siemens CCD three-circle diffractometer | 116 independent reflections |
Absorption correction: numerical numerical | 115 reflections with I > 2σ(I) |
Tmin = 0.327, Tmax = 0.380 | Rint = 0.042 |
4406 measured reflections |
R[F2 > 2σ(F2)] = 0.013 | 0 restraints |
wR(F2) = 0.033 | All H-atom parameters refined |
S = 1.32 | Δρmax = 0.25 e Å−3 |
116 reflections | Δρmin = −0.30 e Å−3 |
10 parameters |
Experimental. The data collection nominally covered a sphere of reciprocal space, by a combination of seven sets of exposures; each set had a different ϕ angle for the crystal and each exposure covered 0.3° in ω. The crystal-to-detector distance was 5.5 cm. Coverage of the unique set is 100% complete to at least 30° in θ. Crystal decay was monitored by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. |
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 | 0 | 0 | 0.0164 (2) | |
Cl1 | 0.25 | 0.25 | 0.25 | 0.0237 (2) | |
N1 | 0.21195 (16) | 0 | 0 | 0.0314 (3) | |
H1 | 0.244 (2) | 0.0561 (11) | 0.0561 (11) | 0.060 (6)* | 0.75 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0164 (2) | 0.0164 (2) | 0.0164 (2) | 0.000 | 0.000 | 0.000 |
Cl1 | 0.0237 (2) | 0.0237 (2) | 0.0237 (2) | 0.000 | 0.000 | 0.000 |
N1 | 0.0206 (8) | 0.0367 (6) | 0.0367 (6) | 0.000 | 0.000 | 0.000 |
Ni1—N1 | 2.1256 (17) | Ni1—N1iv | 2.1257 (17) |
Ni1—N1i | 2.1257 (17) | Ni1—N1v | 2.1257 (17) |
Ni1—N1ii | 2.1257 (17) | N1—H1 | 0.859 (16) |
Ni1—N1iii | 2.1257 (17) | ||
N1—Ni1—N1i | 90.0 | N1ii—Ni1—N1iv | 90.0 |
N1—Ni1—N1ii | 180.0 | N1iii—Ni1—N1iv | 180.0 |
N1i—Ni1—N1ii | 90.0 | N1—Ni1—N1v | 90.0 |
N1—Ni1—N1iii | 90.0 | N1i—Ni1—N1v | 180.0 |
N1i—Ni1—N1iii | 90.0 | N1ii—Ni1—N1v | 90.0 |
N1ii—Ni1—N1iii | 90.0 | N1iii—Ni1—N1v | 90.0 |
N1—Ni1—N1iv | 90.0 | N1iv—Ni1—N1v | 90.0 |
N1i—Ni1—N1iv | 90.0 |
Symmetry codes: (i) −y, −z, −x; (ii) −x, −y, −z; (iii) z, x, y; (iv) −z, −x, −y; (v) y, z, x. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1 | 0.86 (2) | 2.75 (2) | 3.5663 (7) | 159 (2) |
Ni1—N1···H1 | 112 (2) |
Experimental details
Crystal data | |
Chemical formula | [Ni(NH3)6]Cl2 |
Mr | 231.81 |
Crystal system, space group | Cubic, Fm3m |
Temperature (K) | 173 |
a (Å) | 10.029 (2) |
V (Å3) | 1008.7 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.40 |
Crystal size (mm) | 0.60 × 0.50 × 0.50 |
Data collection | |
Diffractometer | Siemens CCD three-circle diffractometer |
Absorption correction | Numerical numerical |
Tmin, Tmax | 0.327, 0.380 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4406, 116, 115 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.733 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.013, 0.033, 1.32 |
No. of reflections | 116 |
No. of parameters | 10 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.25, −0.30 |
Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1 | 0.859 (16) | 2.750 (16) | 3.5663 (7) | 159 (2) |
Ni1—N1···H1 | . | . | . | 112.0 (15) |
In an attempt to obtain a polymer of Ni2+ and 2,5-bis(1-pyrazolyl)hydrochinon via a new route, crystals of the title compound, (I), were obtained. After structure determination it turned out that the crystals contained [Ni(NH3)6]Cl2, whose structure was determined previously by E\&smann et al. (1996). The cell axes are a little bit shorter at 173 K and the anisotropic displacement parameters are, as expected, smaller. However, there are no significant differences between the structures at different temperatures. The difference in the Ni—N bond lengths in both structures is 0.016 Å and the difference between the two N—H bond lengths (0.1 Å) is less than their standard deviation (0.2 Å).