Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112014904/fa3274sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112014904/fa32741sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112014904/fa32742sup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112014904/fa32743sup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112014904/fa32744sup5.hkl |
CCDC references: 879448; 879449; 879450; 879451
For related literature, see: Allen (2002); Barefield (1975); Bonisch et al. (1965); El Ghachtouli, Cadiou, Dechamps-Olivier, Chuburu, Aplincourt, Patinec, Le Baccon, Handel & Roisnel (2006); Flack (1983); Jones (1949).
The compounds 2-(chloromethyl)imidazole hydrochloride and 1,4,8,11-tetraazacyclotetradecane (cyclam) were prepared according to previously published procedures (Jones, 1949; Barefield, 1975). All other reagents employed were obtained commercially and used as supplied.
For the synthesis of 1-[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11-tetraazacyclotetradecane (LIm1), cyclam (2.50 g, 12.5 mmol) was partially dissolved in hot (388 K) dimethylformamide (DMF, 60 ml) and the suspension stirred vigorously. 2-(Chloromethyl)imidazole hydrochloride (0.7 g) dissolved in DMF (32 ml) was added dropwise over a period of 4 h. The reaction mixture was heated at 388–393 K for an extra hour, and then allowed to cool to 277 K. The unreacted cyclam separated as white needles, which were removed by filtration. The solution was concentrated to 15 ml [By heating? In vacuo?] and treated with water (10 ml) and KOH (4 M), raising the pH to 11.5. This solution was extracted with CHCl3 (10 × 50 ml). The organic extracts were evaporated to dryness, leaving a colourless oily residue.
Purification was achieved by chromatography in a column (diameter 4 cm and length 15 cm) packed with silica gel 40 (35–70 mesh) in a CH2Cl2–MeOH (9:1 v/v) mixture. The column was first eluted with the same solvent mixture to remove some nonmacrocyclic contaminants, then with CH2Cl2–MeOH–NH3 (5:5:1 v/v/v) to remove poly-substituted cyclam species and finally with CH2Cl2–MeOH–NH3 (2:2:1 v/v/v) to elute the monosubstituted derivative. Removal of the solvent in vacuo yielded 0.90 g (66%) of the oily product, LIm1.
For the synthesis of [Ni(LIm1)(H2O)](ClO4)2, LIm1 (150.4 mg, 0.51 mmol) dissolved in water (Volume?) was added dropwise and with constant stirring to a solution of Ni(ClO4)2.6H2O (189.7 mg, 0.52 mmol) in water (3 ml). The resulting pink solution was heated at 343 K for 80 min and then concentrated in a rotary evaporator to yield a microcrystalline pink–violet solid, which was collected by filtration, washed with chilled water and dried in vacuo (yield 220 mg, 0.39 mmol, 75%). Elemental analysis, found: C 31.6, N 14.7, H 5.6%; calculated for [Ni(LIm1)(H2O)](ClO4)2(C15H32Cl2N6NiO9): C 31.6, N 14.7, H 5.7%.
This material was redissolved in water and the solution was allowed to evaporate slowly, yielding three consecutive crops of crystals, all of them suitable for single-crystal X-ray diffraction (XRD) studies. The first crop was a violet [pale pink in CIF - please clarify] crystalline material which, upon XRD analysis, proved to be the cis-[Ni(LIm1)(H2O)](ClO4)2 isomer, (2). A second crop consisted of a very small number of pale-pink crystals which were found to be cis-[Ni(LIm2)](ClO4)2, (4), where LIm2 is a minor side product, probably formed in trace amounts in the synthesis of LIm1. Further evaporation of the mother liquors finally gave another pink crystalline solid which was identified by X-ray diffraction as the trans-[Ni(LIm1)(H2O)](ClO4)2 isomer, (1).
The thermal cis–trans conversion between (2) and (1) (see Comment) was followed spectrophotometrically. For that purpose, compound (2) (λ nm-1 [e/M-1 cm-1] = 344 [13], 544 [10], 788(sh) [6], 833(sh) [7], 942 [9]) was dissolved in water and the solution heated at 363 K for several hours, following the course of the process by changes in the electronic spectrum. The experiments show a cis → trans [(2) → (1)] conversion, as indicated by the appearance of new UV–vis features which are compatible with those found for isomer (1) (λ nm-1 [ε/M-1 cm-1] = 335 [13], 515 [9], 721 [3], 803 [2], 961 [5]). This thermal isomerization process was also followed by cyclic voltammetry measurements and suggests that trans-[Ni(LIm1)(H2O)](ClO4)2 is the thermodynamically stable isomer. Solutions kept at 363 K for longer periods of time (4–5 d) followed by slow evaporation of the solvent yielded single crystals of a major product identified by X-ray diffraction as trans-[Ni(ClO4)(LIm1)]ClO4, (3).
All H atoms attached to C and N atoms were placed at calculated positions, with aromatic C—H = 0.95 Å, methylene C—H = 0.97 Å, methyl C—H = 0.96 Å and N—H = 0.91 Å, the N—H group having been identified previously in difference Fourier maps. The O—H groups showed varying behaviours and were accordingly treated differently in the refinements of (1)–(4). In (1) and (2) they were found in difference maps, and while those in (2) could be refined successfully with restraints [O—H = 0.85 (1) Å], those in (1) would not refine properly. They were thus kept at their original positions as found in the difference map, corrected to an idealized O—H distance of 0.85 Å. Structure (3) does not include any solvent water molecules. In (4), the O—H atoms could not be located in the difference map and were accordingly not included in the model. In all cases, H atoms were assigned Uiso(H) = 1.2Ueq(host) [or 1.5Ueq(host) for methyl].
All the perchlorate anions showed some kind of disorder, which was treated through the use of split models, in most cases in the form of a rotation around a nondisordered Cl—O bond. Similarity restraints were used for Cl—O and O···O distances, as well as for displacement parameters.
For the first three structures, a simple twofold splitting was enough, with occupancies of 0.53 (3):0.47 (3) for (1), 0.62 (3):0.38 (3) and 0.61 (3):0.39 (3) for (2), and 0.48 (2):0.52 (2) for (3). In the case of (4), a threefold splitting was required, with occupancies of 0.405 (18):0.405 (18):0.190 (18). All four structures were refined in an homogeneous way, with similarity restraints applied to perchlorate geometries (s.u. values: Cl—O = 0.010 Å and O···O = 0.015 Å). Continuity in anisotropic displacement parameters for neighbouring atoms (except metallic centres) were also applied (SHELXL instructions DELU 0.01 and SIMU 0.02). An isolated peak in structure (4) was satisfactorily refined as a partially occupied water solvent molecule [occupancy factor 0.248 (15)].
Although (2) is metrically tetragonal, the Rint values indicate unequivocally that the diffraction pattern has orthorhombic symmetry [Rint(tetragonal 4/m) 0.31; Rint(tetragonal 4/mmm) 0.41; Rint(orthorhombic mmm): 0.06]. In addition, in this same structure, the Flack (1983) parameter refined to 0.14 (3), thus suggesting the presence of a significant fraction of an inversion twin, even if far removed from being a racemate. The noncentrosymmetric character is clearly in line with |E| statistics (mean values for |E*E - 1|: 0.740 (experimental), 0.968 (centrosymmetric) and 0.736 (noncentrosymmetric).
For all compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
[Ni(C15H30N6)(H2O)](ClO4)2·H2O | F(000) = 1232 |
Mr = 588.09 | Dx = 1.580 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3245 reflections |
a = 14.596 (3) Å | θ = 3.0–24.9° |
b = 10.995 (2) Å | µ = 1.06 mm−1 |
c = 16.192 (3) Å | T = 294 K |
β = 107.96 (3)° | Prism, light pink |
V = 2471.9 (9) Å3 | 0.18 × 0.16 × 0.12 mm |
Z = 4 |
Oxford Gemini CCD S Ultra diffractometer | 4852 independent reflections |
Radiation source: fine-focus sealed tube | 2770 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.077 |
ω scans, thick slices | θmax = 26.0°, θmin = 2.3° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −18→17 |
Tmin = 0.98, Tmax = 0.99 | k = −12→13 |
8284 measured reflections | l = −18→19 |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.23 | w = 1/[σ2(Fo2) + 8.9604P] where P = (Fo2 + 2Fc2)/3 |
4852 reflections | (Δ/σ)max < 0.001 |
362 parameters | Δρmax = 0.51 e Å−3 |
452 restraints | Δρmin = −0.91 e Å−3 |
[Ni(C15H30N6)(H2O)](ClO4)2·H2O | V = 2471.9 (9) Å3 |
Mr = 588.09 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.596 (3) Å | µ = 1.06 mm−1 |
b = 10.995 (2) Å | T = 294 K |
c = 16.192 (3) Å | 0.18 × 0.16 × 0.12 mm |
β = 107.96 (3)° |
Oxford Gemini CCD S Ultra diffractometer | 4852 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 2770 reflections with I > 2σ(I) |
Tmin = 0.98, Tmax = 0.99 | Rint = 0.077 |
8284 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 452 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.23 | Δρmax = 0.51 e Å−3 |
4852 reflections | Δρmin = −0.91 e Å−3 |
362 parameters |
Experimental. Materials and Physical Methods. Microanalytical data for C, H and N were obtained with a Carlo Erba EA 1108 analyser. 1H and 13C NMR spectra were measured with a 500 MHz Bruker AM 500 spectrometer. UV–vis spectra were recorded with an HP8453 diode array spectrometer. Cyclic voltammetry (CV) determinations were done in aqueous solution (I = 0.1 M, NaClO4) with a standard three-electrode cell containing a glassy carbon working electrode (Φ = 3 mm) and a Pt wire as the counterelectrode. A commercial Ag/AgCl (ss. KCl) (BAS) electrode was used as the reference. Throughout this work all the potentials are expressed against Ag/AgCl (ss. KCl). The potential of the working electrode was controlled with a TEQ-03 potentiostat. 1H NMR data for N-(2-imidazolylmethyl) cyclam, LIm1, δH (p.p.m.) (CDCl3): 6.89 (1H, d), 6.80 (1H, d), 3.69 (3H, s), 3.65 (2H, s), 2.6 (16H, m), 1.79 (2H, m) 1.69 (2H, m). 13C-NMR, δC (p.p.m.) (CDCl3): 145.4, 127.6, 121.7, 55.4, 54.2, 51.0, 50.8, 49.3, 48.8, 48.7, 48.1, 47.7, 33.3, 28.8, 26.5. |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.27576 (5) | 0.26476 (7) | 0.58735 (5) | 0.0367 (2) | |
N1 | 0.2368 (4) | 0.1205 (5) | 0.4963 (3) | 0.0432 (12) | |
N2 | 0.4163 (3) | 0.2264 (5) | 0.5923 (3) | 0.0451 (12) | |
H2 | 0.4329 | 0.2820 | 0.5578 | 0.054* | |
N3 | 0.3133 (4) | 0.4087 (5) | 0.6734 (3) | 0.0451 (13) | |
H3 | 0.3229 | 0.4737 | 0.6422 | 0.054* | |
N4 | 0.1352 (3) | 0.3151 (5) | 0.5749 (3) | 0.0470 (13) | |
H4 | 0.1135 | 0.2617 | 0.6075 | 0.056* | |
N5 | 0.2732 (4) | 0.1237 (5) | 0.6725 (3) | 0.0442 (12) | |
N6 | 0.2417 (4) | −0.0690 (5) | 0.6889 (4) | 0.0493 (13) | |
C1 | 0.3258 (5) | 0.1027 (6) | 0.4707 (4) | 0.0544 (17) | |
H1A | 0.3297 | 0.1653 | 0.4297 | 0.065* | |
H1B | 0.3234 | 0.0243 | 0.4427 | 0.065* | |
C2 | 0.4147 (5) | 0.1090 (6) | 0.5513 (4) | 0.0535 (16) | |
H2A | 0.4121 | 0.0447 | 0.5915 | 0.064* | |
H2B | 0.4726 | 0.0985 | 0.5348 | 0.064* | |
C3 | 0.4877 (5) | 0.2368 (7) | 0.6791 (4) | 0.0595 (17) | |
H3A | 0.5512 | 0.2186 | 0.6748 | 0.071* | |
H3B | 0.4733 | 0.1771 | 0.7173 | 0.071* | |
C4 | 0.4891 (5) | 0.3624 (7) | 0.7182 (5) | 0.066 (2) | |
H4A | 0.4937 | 0.4219 | 0.6754 | 0.080* | |
H4B | 0.5471 | 0.3694 | 0.7674 | 0.080* | |
C5 | 0.4026 (5) | 0.3961 (7) | 0.7486 (4) | 0.0625 (19) | |
H5A | 0.3931 | 0.3336 | 0.7875 | 0.075* | |
H5B | 0.4156 | 0.4722 | 0.7805 | 0.075* | |
C6 | 0.2271 (5) | 0.4368 (6) | 0.6984 (4) | 0.0566 (17) | |
H6A | 0.2334 | 0.5164 | 0.7253 | 0.068* | |
H6B | 0.2193 | 0.3771 | 0.7398 | 0.068* | |
C7 | 0.1402 (5) | 0.4345 (6) | 0.6171 (5) | 0.0581 (17) | |
H7A | 0.0818 | 0.4486 | 0.6325 | 0.070* | |
H7B | 0.1459 | 0.4983 | 0.5776 | 0.070* | |
C8 | 0.0638 (5) | 0.3119 (7) | 0.4856 (5) | 0.0628 (19) | |
H8A | 0.0788 | 0.3762 | 0.4508 | 0.075* | |
H8B | −0.0001 | 0.3271 | 0.4896 | 0.075* | |
C9 | 0.0642 (5) | 0.1917 (7) | 0.4412 (5) | 0.0626 (19) | |
H9A | 0.0106 | 0.1917 | 0.3879 | 0.075* | |
H9B | 0.0514 | 0.1286 | 0.4781 | 0.075* | |
C10 | 0.1534 (5) | 0.1557 (7) | 0.4188 (4) | 0.0549 (17) | |
H10A | 0.1378 | 0.0878 | 0.3787 | 0.066* | |
H10B | 0.1728 | 0.2232 | 0.3894 | 0.066* | |
C11 | 0.2433 (4) | 0.0199 (6) | 0.6319 (4) | 0.0407 (14) | |
C12 | 0.2718 (5) | −0.0211 (7) | 0.7694 (5) | 0.0623 (19) | |
H12 | 0.2784 | −0.0620 | 0.8212 | 0.075* | |
C13 | 0.2905 (5) | 0.0978 (7) | 0.7607 (4) | 0.0567 (17) | |
H13 | 0.3115 | 0.1533 | 0.8059 | 0.068* | |
C14 | 0.2137 (5) | 0.0066 (6) | 0.5356 (4) | 0.0523 (16) | |
H14A | 0.1450 | −0.0094 | 0.5135 | 0.063* | |
H14B | 0.2474 | −0.0614 | 0.5202 | 0.063* | |
C15 | 0.2122 (6) | −0.1950 (7) | 0.6678 (6) | 0.076 (2) | |
H15A | 0.1611 | −0.1978 | 0.6137 | 0.115* | |
H15B | 0.1901 | −0.2288 | 0.7130 | 0.115* | |
H15C | 0.2660 | −0.2414 | 0.6629 | 0.115* | |
Cl1 | 0.01898 (15) | 0.85354 (17) | 0.30704 (12) | 0.0637 (5) | |
O11 | 0.0101 (7) | 0.9300 (6) | 0.2383 (4) | 0.182 (4) | |
O21A | 0.1140 (7) | 0.8121 (17) | 0.3347 (11) | 0.159 (7) | 0.51 |
O31A | −0.0428 (13) | 0.7548 (11) | 0.2819 (10) | 0.103 (6) | 0.51 |
O41A | 0.0008 (14) | 0.9133 (14) | 0.3754 (9) | 0.130 (6) | 0.51 |
O21B | 0.1159 (7) | 0.8447 (17) | 0.3548 (11) | 0.164 (9) | 0.49 |
O31B | −0.0176 (15) | 0.7392 (10) | 0.2793 (10) | 0.103 (6) | 0.49 |
O41B | −0.0303 (14) | 0.9020 (15) | 0.3604 (10) | 0.136 (7) | 0.49 |
Cl2 | 0.41772 (15) | 0.68986 (17) | 0.54177 (12) | 0.0630 (5) | |
O12 | 0.3820 (5) | 0.6379 (6) | 0.6039 (4) | 0.137 (3) | |
O22A | 0.3741 (9) | 0.6482 (15) | 0.4583 (6) | 0.140 (6) | 0.53 |
O32A | 0.5192 (5) | 0.6679 (12) | 0.5653 (9) | 0.108 (5) | 0.53 |
O42A | 0.4071 (10) | 0.8175 (7) | 0.5462 (10) | 0.129 (5) | 0.53 |
O22B | 0.4271 (11) | 0.5933 (11) | 0.4860 (8) | 0.126 (6) | 0.47 |
O32B | 0.5071 (8) | 0.7449 (15) | 0.5778 (9) | 0.136 (7) | 0.47 |
O42B | 0.3521 (10) | 0.7727 (13) | 0.4891 (10) | 0.156 (7) | 0.47 |
O1W | 0.2785 (3) | 0.3973 (4) | 0.4808 (3) | 0.0559 (12) | |
H1WA | 0.2251 | 0.4317 | 0.4553 | 0.067* | |
H1WB | 0.3213 | 0.4496 | 0.4810 | 0.067* | |
O2W | 0.1390 (5) | 0.5700 (6) | 0.4017 (4) | 0.117 (3) | |
H2WA | 0.0977 | 0.5300 | 0.3626 | 0.141* | |
H2WB | 0.1327 | 0.6440 | 0.3856 | 0.141* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0370 (4) | 0.0393 (4) | 0.0338 (4) | 0.0017 (4) | 0.0107 (3) | 0.0006 (4) |
N1 | 0.049 (3) | 0.044 (3) | 0.036 (3) | −0.001 (3) | 0.012 (2) | −0.001 (2) |
N2 | 0.043 (3) | 0.050 (3) | 0.044 (3) | 0.005 (3) | 0.016 (2) | 0.006 (2) |
N3 | 0.057 (3) | 0.035 (3) | 0.043 (3) | −0.008 (3) | 0.015 (2) | −0.003 (2) |
N4 | 0.038 (3) | 0.049 (3) | 0.056 (3) | 0.002 (2) | 0.016 (2) | 0.012 (3) |
N5 | 0.052 (3) | 0.046 (3) | 0.037 (3) | −0.001 (3) | 0.017 (2) | 0.004 (2) |
N6 | 0.044 (3) | 0.049 (3) | 0.060 (3) | 0.001 (3) | 0.023 (3) | 0.015 (3) |
C1 | 0.071 (4) | 0.051 (4) | 0.045 (4) | 0.005 (3) | 0.024 (3) | −0.012 (3) |
C2 | 0.049 (4) | 0.057 (4) | 0.060 (4) | 0.012 (3) | 0.027 (3) | 0.003 (3) |
C3 | 0.043 (4) | 0.070 (4) | 0.057 (4) | 0.006 (4) | 0.003 (3) | 0.013 (4) |
C4 | 0.058 (4) | 0.069 (5) | 0.054 (4) | −0.014 (4) | −0.008 (3) | 0.008 (4) |
C5 | 0.068 (4) | 0.060 (4) | 0.050 (4) | −0.008 (4) | 0.004 (3) | −0.004 (4) |
C6 | 0.072 (4) | 0.046 (4) | 0.058 (4) | −0.001 (4) | 0.030 (3) | −0.007 (3) |
C7 | 0.060 (4) | 0.057 (4) | 0.066 (4) | 0.007 (4) | 0.033 (3) | 0.007 (3) |
C8 | 0.041 (4) | 0.071 (5) | 0.068 (4) | 0.007 (4) | 0.004 (3) | 0.019 (4) |
C9 | 0.048 (4) | 0.080 (5) | 0.050 (4) | −0.003 (4) | 0.001 (3) | 0.013 (4) |
C10 | 0.063 (4) | 0.068 (5) | 0.023 (3) | −0.012 (3) | −0.003 (3) | −0.002 (3) |
C11 | 0.041 (3) | 0.038 (3) | 0.045 (3) | 0.003 (3) | 0.017 (3) | 0.012 (3) |
C12 | 0.074 (5) | 0.072 (4) | 0.044 (4) | 0.004 (4) | 0.024 (4) | 0.016 (3) |
C13 | 0.065 (4) | 0.063 (4) | 0.043 (3) | 0.008 (4) | 0.018 (3) | 0.006 (3) |
C14 | 0.061 (4) | 0.046 (4) | 0.047 (3) | −0.011 (3) | 0.012 (3) | 0.002 (3) |
C15 | 0.075 (5) | 0.051 (4) | 0.105 (6) | −0.014 (4) | 0.031 (5) | 0.015 (4) |
Cl1 | 0.0733 (13) | 0.0568 (12) | 0.0610 (12) | −0.0188 (10) | 0.0208 (10) | −0.0020 (9) |
O11 | 0.272 (10) | 0.147 (7) | 0.121 (6) | −0.068 (7) | 0.050 (6) | 0.060 (5) |
O21A | 0.093 (8) | 0.118 (15) | 0.240 (16) | 0.002 (8) | 0.015 (10) | −0.065 (12) |
O31A | 0.136 (11) | 0.100 (10) | 0.086 (11) | −0.075 (10) | 0.054 (9) | −0.037 (8) |
O41A | 0.130 (13) | 0.144 (12) | 0.149 (9) | −0.103 (10) | 0.092 (10) | −0.095 (9) |
O21B | 0.103 (8) | 0.086 (12) | 0.242 (16) | 0.021 (8) | −0.036 (10) | −0.068 (11) |
O31B | 0.154 (14) | 0.076 (7) | 0.084 (12) | −0.052 (9) | 0.045 (10) | −0.030 (7) |
O41B | 0.138 (14) | 0.132 (12) | 0.176 (12) | −0.101 (10) | 0.104 (11) | −0.099 (10) |
Cl2 | 0.0732 (13) | 0.0543 (11) | 0.0632 (12) | −0.0104 (10) | 0.0236 (10) | 0.0012 (9) |
O12 | 0.169 (7) | 0.134 (6) | 0.147 (6) | −0.043 (6) | 0.105 (6) | 0.017 (5) |
O22A | 0.104 (11) | 0.210 (15) | 0.095 (7) | −0.046 (11) | 0.018 (7) | −0.066 (10) |
O32A | 0.077 (6) | 0.124 (12) | 0.121 (10) | −0.009 (7) | 0.027 (6) | 0.020 (10) |
O42A | 0.137 (12) | 0.066 (6) | 0.176 (13) | 0.012 (7) | 0.040 (11) | 0.014 (7) |
O22B | 0.097 (12) | 0.154 (13) | 0.123 (12) | −0.008 (9) | 0.027 (9) | −0.074 (10) |
O32B | 0.140 (10) | 0.150 (15) | 0.103 (10) | −0.098 (10) | 0.016 (9) | 0.006 (10) |
O42B | 0.155 (12) | 0.098 (11) | 0.194 (16) | 0.026 (10) | 0.022 (11) | 0.049 (10) |
O1W | 0.053 (3) | 0.052 (3) | 0.060 (3) | −0.007 (2) | 0.013 (2) | 0.012 (2) |
O2W | 0.107 (5) | 0.115 (6) | 0.143 (6) | 0.046 (4) | 0.057 (5) | 0.064 (5) |
Ni1—N1 | 2.120 (5) | C6—H6B | 0.9700 |
Ni1—N2 | 2.071 (5) | C7—H7A | 0.9700 |
Ni1—N3 | 2.068 (5) | C7—H7B | 0.9700 |
Ni1—N4 | 2.073 (5) | C8—C9 | 1.505 (10) |
Ni1—N5 | 2.083 (5) | C8—H8A | 0.9700 |
Ni1—O1W | 2.268 (4) | C8—H8B | 0.9700 |
N1—C14 | 1.490 (8) | C9—C10 | 1.508 (9) |
N1—C1 | 1.494 (8) | C9—H9A | 0.9700 |
N1—C10 | 1.505 (7) | C9—H9B | 0.9700 |
N2—C2 | 1.447 (8) | C10—H10A | 0.9700 |
N2—C3 | 1.474 (8) | C10—H10B | 0.9700 |
N2—H2 | 0.9100 | C11—C14 | 1.490 (8) |
N3—C6 | 1.468 (8) | C12—C13 | 1.351 (10) |
N3—C5 | 1.491 (8) | C12—H12 | 0.9300 |
N3—H3 | 0.9100 | C13—H13 | 0.9300 |
N4—C7 | 1.472 (8) | C14—H14A | 0.9700 |
N4—C8 | 1.500 (8) | C14—H14B | 0.9700 |
N4—H4 | 0.9100 | C15—H15A | 0.9600 |
N5—C11 | 1.323 (8) | C15—H15B | 0.9600 |
N5—C13 | 1.400 (8) | C15—H15C | 0.9600 |
N6—C12 | 1.348 (8) | Cl1—O11 | 1.368 (5) |
N6—C11 | 1.350 (7) | Cl1—O41A | 1.382 (8) |
N6—C15 | 1.461 (9) | Cl1—O31B | 1.386 (7) |
C1—C2 | 1.532 (9) | Cl1—O31A | 1.389 (7) |
C1—H1A | 0.9700 | Cl1—O41B | 1.390 (8) |
C1—H1B | 0.9700 | Cl1—O21B | 1.390 (8) |
C2—H2A | 0.9700 | Cl1—O21A | 1.396 (8) |
C2—H2B | 0.9700 | Cl2—O22A | 1.383 (7) |
C3—C4 | 1.517 (10) | Cl2—O12 | 1.390 (5) |
C3—H3A | 0.9700 | Cl2—O32B | 1.392 (7) |
C3—H3B | 0.9700 | Cl2—O42B | 1.404 (7) |
C4—C5 | 1.537 (10) | Cl2—O42A | 1.417 (7) |
C4—H4A | 0.9700 | Cl2—O22B | 1.428 (7) |
C4—H4B | 0.9700 | Cl2—O32A | 1.431 (7) |
C5—H5A | 0.9700 | O1W—H1WA | 0.8490 |
C5—H5B | 0.9700 | O1W—H1WB | 0.8489 |
C6—C7 | 1.520 (9) | O2W—H2WA | 0.8500 |
C6—H6A | 0.9700 | O2W—H2WB | 0.8500 |
N1—Ni1—N2 | 85.7 (2) | N3—C6—H6B | 110.0 |
N1—Ni1—N3 | 178.4 (2) | C7—C6—H6B | 110.0 |
N1—Ni1—N4 | 95.0 (2) | H6A—C6—H6B | 108.4 |
N1—Ni1—N5 | 81.2 (2) | N4—C7—C6 | 109.0 (6) |
N1—Ni1—O1W | 90.92 (18) | N4—C7—H7A | 109.9 |
N2—Ni1—N3 | 94.4 (2) | C6—C7—H7A | 109.9 |
N2—Ni1—N4 | 175.0 (2) | N4—C7—H7B | 109.9 |
N2—Ni1—N5 | 92.4 (2) | C6—C7—H7B | 109.9 |
N2—Ni1—O1W | 84.89 (18) | H7A—C7—H7B | 108.3 |
N3—Ni1—N4 | 84.8 (2) | N4—C8—C9 | 112.2 (6) |
N3—Ni1—N5 | 100.3 (2) | N4—C8—H8A | 109.2 |
N3—Ni1—O1W | 87.54 (18) | C9—C8—H8A | 109.2 |
N4—Ni1—N5 | 92.5 (2) | N4—C8—H8B | 109.2 |
N4—Ni1—O1W | 90.17 (19) | C9—C8—H8B | 109.2 |
N5—Ni1—O1W | 171.89 (19) | H8A—C8—H8B | 107.9 |
C14—N1—C1 | 109.9 (5) | C8—C9—C10 | 118.4 (6) |
C14—N1—C10 | 109.9 (5) | C8—C9—H9A | 107.7 |
C1—N1—C10 | 110.6 (5) | C10—C9—H9A | 107.7 |
C14—N1—Ni1 | 112.3 (4) | C8—C9—H9B | 107.7 |
C1—N1—Ni1 | 102.8 (4) | C10—C9—H9B | 107.7 |
C10—N1—Ni1 | 111.2 (4) | H9A—C9—H9B | 107.1 |
C2—N2—C3 | 114.4 (5) | N1—C10—C9 | 113.8 (5) |
C2—N2—Ni1 | 106.8 (4) | N1—C10—H10A | 108.8 |
C3—N2—Ni1 | 115.0 (4) | C9—C10—H10A | 108.8 |
C2—N2—H2 | 106.7 | N1—C10—H10B | 108.8 |
C3—N2—H2 | 106.7 | C9—C10—H10B | 108.8 |
Ni1—N2—H2 | 106.7 | H10A—C10—H10B | 107.7 |
C6—N3—C5 | 113.7 (5) | N5—C11—N6 | 110.9 (5) |
C6—N3—Ni1 | 106.0 (4) | N5—C11—C14 | 123.4 (5) |
C5—N3—Ni1 | 117.5 (4) | N6—C11—C14 | 125.7 (6) |
C6—N3—H3 | 106.3 | N6—C12—C13 | 107.0 (6) |
C5—N3—H3 | 106.3 | N6—C12—H12 | 126.5 |
Ni1—N3—H3 | 106.3 | C13—C12—H12 | 126.5 |
C7—N4—C8 | 112.9 (5) | C12—C13—N5 | 109.0 (7) |
C7—N4—Ni1 | 106.7 (4) | C12—C13—H13 | 125.5 |
C8—N4—Ni1 | 117.4 (4) | N5—C13—H13 | 125.5 |
C7—N4—H4 | 106.4 | C11—C14—N1 | 109.4 (5) |
C8—N4—H4 | 106.4 | C11—C14—H14A | 109.8 |
Ni1—N4—H4 | 106.4 | N1—C14—H14A | 109.8 |
C11—N5—C13 | 105.0 (5) | C11—C14—H14B | 109.8 |
C11—N5—Ni1 | 112.5 (4) | N1—C14—H14B | 109.8 |
C13—N5—Ni1 | 142.4 (5) | H14A—C14—H14B | 108.2 |
C12—N6—C11 | 108.0 (6) | N6—C15—H15A | 109.5 |
C12—N6—C15 | 125.6 (6) | N6—C15—H15B | 109.5 |
C11—N6—C15 | 126.4 (6) | H15A—C15—H15B | 109.5 |
N1—C1—C2 | 109.7 (5) | N6—C15—H15C | 109.5 |
N1—C1—H1A | 109.7 | H15A—C15—H15C | 109.5 |
C2—C1—H1A | 109.7 | H15B—C15—H15C | 109.5 |
N1—C1—H1B | 109.7 | O11—Cl1—O41A | 111.4 (7) |
C2—C1—H1B | 109.7 | O11—Cl1—O31B | 111.3 (7) |
H1A—C1—H1B | 108.2 | O11—Cl1—O31A | 110.6 (7) |
N2—C2—C1 | 108.7 (5) | O41A—Cl1—O31A | 109.8 (7) |
N2—C2—H2A | 109.9 | O11—Cl1—O41B | 109.4 (7) |
C1—C2—H2A | 109.9 | O31B—Cl1—O41B | 109.1 (7) |
N2—C2—H2B | 109.9 | O11—Cl1—O21B | 108.7 (7) |
C1—C2—H2B | 109.9 | O31B—Cl1—O21B | 109.9 (7) |
H2A—C2—H2B | 108.3 | O41B—Cl1—O21B | 108.3 (7) |
N2—C3—C4 | 112.5 (6) | O11—Cl1—O21A | 107.3 (7) |
N2—C3—H3A | 109.1 | O41A—Cl1—O21A | 108.4 (7) |
C4—C3—H3A | 109.1 | O31A—Cl1—O21A | 109.2 (7) |
N2—C3—H3B | 109.1 | O41B—Cl1—O21A | 125.4 (13) |
C4—C3—H3B | 109.1 | O22A—Cl2—O12 | 114.1 (6) |
H3A—C3—H3B | 107.8 | O12—Cl2—O32B | 112.8 (6) |
C3—C4—C5 | 116.6 (6) | O12—Cl2—O42B | 111.6 (6) |
C3—C4—H4A | 108.2 | O32B—Cl2—O42B | 110.4 (7) |
C5—C4—H4A | 108.2 | O22A—Cl2—O42A | 110.7 (7) |
C3—C4—H4B | 108.2 | O12—Cl2—O42A | 107.4 (6) |
C5—C4—H4B | 108.2 | O12—Cl2—O22B | 106.4 (6) |
H4A—C4—H4B | 107.3 | O32B—Cl2—O22B | 109.1 (7) |
N3—C5—C4 | 111.0 (6) | O42B—Cl2—O22B | 106.2 (6) |
N3—C5—H5A | 109.4 | O22A—Cl2—O32A | 109.3 (6) |
C4—C5—H5A | 109.4 | O12—Cl2—O32A | 109.1 (6) |
N3—C5—H5B | 109.4 | O42A—Cl2—O32A | 105.9 (6) |
C4—C5—H5B | 109.4 | Ni1—O1W—H1WA | 115.4 |
H5A—C5—H5B | 108.0 | Ni1—O1W—H1WB | 128.3 |
N3—C6—C7 | 108.4 (5) | H1WA—O1W—H1WB | 105.2 |
N3—C6—H6A | 110.0 | H2WA—O2W—H2WB | 106.4 |
C7—C6—H6A | 110.0 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O32Ai | 0.91 | 2.37 | 3.198 (13) | 151 |
N3—H3···O12 | 0.91 | 2.17 | 3.053 (8) | 162 |
O1W—H1WA···O2W | 0.85 | 1.99 | 2.790 (7) | 156 |
O1W—H1WB···O22B | 0.85 | 2.19 | 3.041 (15) | 176 |
O1W—H1WB···O22A | 0.85 | 2.38 | 3.163 (15) | 153 |
O2W—H2WA···O11ii | 0.85 | 2.18 | 3.034 (11) | 179 |
O2W—H2WB···O21B | 0.85 | 2.26 | 3.107 (19) | 175 |
O2W—H2WB···O21A | 0.85 | 2.01 | 2.855 (18) | 174 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y−1/2, −z+1/2. |
[Ni(C15H30N6)(H2O)](ClO4)2 | F(000) = 1192 |
Mr = 570.08 | Dx = 1.558 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 2876 reflections |
a = 9.428 (5) Å | θ = 3.9–25.9° |
b = 16.047 (5) Å | µ = 1.08 mm−1 |
c = 16.060 (5) Å | T = 294 K |
V = 2429.7 (17) Å3 | Prism, light pink |
Z = 4 | 0.32 × 0.30 × 0.20 mm |
Oxford Gemini CCD S Ultra diffractometer | 4312 independent reflections |
Radiation source: fine-focus sealed tube | 3342 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
ω scans, thick slices | θmax = 26.0°, θmin = 3.6° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −6→11 |
Tmin = 0.98, Tmax = 0.99 | k = −15→19 |
8056 measured reflections | l = −19→19 |
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)] = 0.059 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.153 | w = 1/[σ2(Fo2) + (0.0553P)2 + 0.3459P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
4312 reflections | Δρmax = 0.58 e Å−3 |
362 parameters | Δρmin = −0.37 e Å−3 |
720 restraints | Absolute structure: Flack (1983), 1601 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.14 (3) |
[Ni(C15H30N6)(H2O)](ClO4)2 | V = 2429.7 (17) Å3 |
Mr = 570.08 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.428 (5) Å | µ = 1.08 mm−1 |
b = 16.047 (5) Å | T = 294 K |
c = 16.060 (5) Å | 0.32 × 0.30 × 0.20 mm |
Oxford Gemini CCD S Ultra diffractometer | 4312 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 3342 reflections with I > 2σ(I) |
Tmin = 0.98, Tmax = 0.99 | Rint = 0.049 |
8056 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.153 | Δρmax = 0.58 e Å−3 |
S = 1.07 | Δρmin = −0.37 e Å−3 |
4312 reflections | Absolute structure: Flack (1983), 1601 Friedel pairs |
362 parameters | Absolute structure parameter: 0.14 (3) |
720 restraints |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.68547 (9) | 0.66055 (5) | 0.76693 (5) | 0.0407 (2) | |
N1 | 0.5582 (6) | 0.6181 (4) | 0.6647 (4) | 0.0470 (14) | |
N2 | 0.5941 (6) | 0.5756 (4) | 0.8492 (4) | 0.0506 (15) | |
H2 | 0.6383 | 0.5257 | 0.8420 | 0.061* | |
N3 | 0.8152 (7) | 0.6887 (4) | 0.8689 (3) | 0.0523 (14) | |
H3 | 0.7838 | 0.7385 | 0.8887 | 0.063* | |
N4 | 0.8399 (6) | 0.5814 (4) | 0.7174 (4) | 0.0471 (13) | |
H4 | 0.8365 | 0.5328 | 0.7465 | 0.057* | |
N5 | 0.7380 (7) | 0.7519 (4) | 0.6831 (4) | 0.0525 (15) | |
N6 | 0.6821 (7) | 0.8174 (4) | 0.5685 (4) | 0.0552 (15) | |
C1 | 0.4102 (8) | 0.5915 (5) | 0.6859 (5) | 0.0535 (18) | |
H1A | 0.3556 | 0.6406 | 0.7005 | 0.064* | |
H1B | 0.3673 | 0.5673 | 0.6366 | 0.064* | |
C2 | 0.3987 (8) | 0.5302 (5) | 0.7554 (5) | 0.0579 (18) | |
H2A | 0.4581 | 0.4826 | 0.7422 | 0.069* | |
H2B | 0.3015 | 0.5105 | 0.7579 | 0.069* | |
C3 | 0.4394 (8) | 0.5615 (6) | 0.8402 (5) | 0.060 (2) | |
H3A | 0.3899 | 0.6134 | 0.8508 | 0.072* | |
H3B | 0.4089 | 0.5214 | 0.8817 | 0.072* | |
C4 | 0.6284 (9) | 0.6053 (6) | 0.9319 (5) | 0.068 (2) | |
H4A | 0.6073 | 0.5624 | 0.9727 | 0.081* | |
H4B | 0.5719 | 0.6541 | 0.9450 | 0.081* | |
C5 | 0.7850 (8) | 0.6272 (6) | 0.9351 (5) | 0.064 (2) | |
H5A | 0.8086 | 0.6504 | 0.9891 | 0.076* | |
H5B | 0.8418 | 0.5775 | 0.9266 | 0.076* | |
C6 | 0.9689 (9) | 0.6995 (6) | 0.8540 (6) | 0.068 (2) | |
H6A | 1.0162 | 0.7072 | 0.9070 | 0.081* | |
H6B | 0.9833 | 0.7497 | 0.8214 | 0.081* | |
C7 | 1.0370 (8) | 0.6269 (6) | 0.8091 (5) | 0.068 (2) | |
H7A | 1.1387 | 0.6359 | 0.8078 | 0.082* | |
H7B | 1.0197 | 0.5767 | 0.8411 | 0.082* | |
C8 | 0.9865 (7) | 0.6125 (5) | 0.7213 (5) | 0.0565 (18) | |
H8A | 0.9926 | 0.6644 | 0.6906 | 0.068* | |
H8B | 1.0487 | 0.5726 | 0.6945 | 0.068* | |
C9 | 0.7969 (8) | 0.5632 (5) | 0.6317 (4) | 0.0557 (18) | |
H9A | 0.8485 | 0.5150 | 0.6113 | 0.067* | |
H9B | 0.8193 | 0.6102 | 0.5962 | 0.067* | |
C10 | 0.6392 (8) | 0.5460 (5) | 0.6290 (5) | 0.0576 (19) | |
H10A | 0.6099 | 0.5368 | 0.5718 | 0.069* | |
H10B | 0.6183 | 0.4960 | 0.6605 | 0.069* | |
C11 | 0.6574 (8) | 0.7511 (5) | 0.6174 (4) | 0.0514 (17) | |
C12 | 0.7873 (9) | 0.8628 (5) | 0.6059 (5) | 0.067 (2) | |
H12 | 0.8277 | 0.9118 | 0.5858 | 0.080* | |
C13 | 0.8211 (9) | 0.8234 (5) | 0.6769 (5) | 0.0614 (19) | |
H13 | 0.8885 | 0.8409 | 0.7154 | 0.074* | |
C14 | 0.5481 (8) | 0.6857 (5) | 0.6018 (5) | 0.0589 (19) | |
H14A | 0.4544 | 0.7106 | 0.6040 | 0.071* | |
H14B | 0.5615 | 0.6626 | 0.5465 | 0.071* | |
C15 | 0.6046 (11) | 0.8407 (7) | 0.4931 (5) | 0.087 (3) | |
H15A | 0.6461 | 0.8133 | 0.4459 | 0.130* | |
H15B | 0.6097 | 0.9000 | 0.4855 | 0.130* | |
H15C | 0.5072 | 0.8241 | 0.4984 | 0.130* | |
Cl1 | 0.7249 (3) | 0.90397 (13) | 0.95182 (13) | 0.0704 (7) | |
O11 | 0.7669 (8) | 0.8339 (4) | 0.9969 (4) | 0.099 (2) | |
O21A | 0.6385 (17) | 0.9556 (7) | 1.0003 (8) | 0.091 (4) | 0.62 (3) |
O31A | 0.658 (2) | 0.8828 (7) | 0.8776 (9) | 0.125 (6) | 0.62 (3) |
O41A | 0.8476 (10) | 0.9523 (9) | 0.9323 (12) | 0.121 (6) | 0.62 (3) |
O21B | 0.708 (3) | 0.9732 (9) | 1.0021 (11) | 0.109 (8) | 0.38 (3) |
O31B | 0.5895 (17) | 0.8848 (11) | 0.9173 (18) | 0.115 (8) | 0.38 (3) |
O41B | 0.818 (2) | 0.9185 (17) | 0.8861 (14) | 0.142 (9) | 0.38 (3) |
Cl2 | 0.7552 (2) | 0.35686 (12) | 0.83908 (16) | 0.0696 (6) | |
O12 | 0.6139 (6) | 0.3710 (5) | 0.8176 (6) | 0.143 (4) | |
O22A | 0.7515 (16) | 0.3401 (15) | 0.9268 (5) | 0.146 (7) | 0.61 (3) |
O32A | 0.8042 (14) | 0.2840 (7) | 0.8017 (12) | 0.111 (5) | 0.61 (3) |
O42A | 0.8421 (13) | 0.4246 (7) | 0.8267 (15) | 0.130 (6) | 0.61 (3) |
O22B | 0.784 (2) | 0.396 (2) | 0.9149 (13) | 0.165 (10) | 0.39 (3) |
O32B | 0.7892 (19) | 0.2733 (6) | 0.8404 (19) | 0.113 (8) | 0.39 (3) |
O42B | 0.8383 (17) | 0.3964 (18) | 0.7768 (17) | 0.146 (9) | 0.39 (3) |
O1W | 0.5193 (7) | 0.7489 (3) | 0.8098 (4) | 0.0646 (15) | |
H1WA | 0.474 (8) | 0.772 (4) | 0.770 (3) | 0.077* | |
H1WB | 0.527 (10) | 0.785 (3) | 0.848 (3) | 0.077* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0442 (4) | 0.0377 (4) | 0.0401 (4) | 0.0005 (4) | −0.0002 (4) | 0.0020 (4) |
N1 | 0.050 (3) | 0.044 (3) | 0.048 (3) | −0.001 (3) | −0.002 (3) | 0.002 (2) |
N2 | 0.049 (3) | 0.055 (4) | 0.048 (3) | 0.006 (3) | 0.003 (3) | 0.005 (3) |
N3 | 0.056 (3) | 0.050 (3) | 0.050 (3) | 0.005 (3) | −0.008 (3) | −0.004 (2) |
N4 | 0.044 (3) | 0.048 (3) | 0.050 (3) | 0.003 (3) | 0.007 (3) | 0.002 (2) |
N5 | 0.055 (3) | 0.046 (3) | 0.057 (3) | −0.011 (3) | −0.003 (3) | 0.010 (3) |
N6 | 0.057 (3) | 0.051 (3) | 0.057 (3) | 0.008 (3) | 0.006 (3) | 0.019 (3) |
C1 | 0.046 (4) | 0.053 (4) | 0.062 (4) | −0.007 (3) | −0.005 (4) | −0.003 (4) |
C2 | 0.041 (3) | 0.058 (4) | 0.075 (5) | −0.007 (3) | 0.007 (4) | 0.004 (4) |
C3 | 0.052 (4) | 0.064 (5) | 0.065 (4) | −0.008 (4) | 0.013 (4) | 0.010 (4) |
C4 | 0.069 (4) | 0.088 (6) | 0.047 (4) | 0.006 (5) | 0.000 (4) | 0.016 (4) |
C5 | 0.070 (5) | 0.083 (6) | 0.038 (4) | 0.002 (4) | −0.011 (4) | 0.007 (3) |
C6 | 0.057 (4) | 0.076 (5) | 0.070 (5) | −0.002 (4) | −0.010 (4) | −0.004 (4) |
C7 | 0.044 (4) | 0.086 (6) | 0.074 (5) | 0.006 (4) | −0.006 (4) | 0.003 (5) |
C8 | 0.039 (3) | 0.067 (5) | 0.064 (4) | 0.004 (3) | 0.009 (4) | 0.001 (4) |
C9 | 0.058 (4) | 0.061 (5) | 0.049 (4) | 0.007 (4) | 0.009 (4) | −0.005 (3) |
C10 | 0.065 (4) | 0.050 (4) | 0.058 (4) | −0.004 (4) | 0.006 (4) | −0.010 (3) |
C11 | 0.061 (4) | 0.049 (4) | 0.044 (4) | −0.002 (3) | −0.002 (4) | 0.009 (3) |
C12 | 0.073 (5) | 0.048 (4) | 0.079 (5) | −0.011 (4) | 0.012 (4) | 0.017 (4) |
C13 | 0.060 (4) | 0.047 (4) | 0.078 (5) | −0.007 (4) | −0.003 (4) | 0.002 (4) |
C14 | 0.060 (4) | 0.064 (5) | 0.053 (4) | −0.005 (3) | −0.020 (4) | 0.008 (3) |
C15 | 0.110 (7) | 0.090 (7) | 0.060 (5) | 0.015 (7) | −0.010 (5) | 0.027 (5) |
Cl1 | 0.1020 (18) | 0.0539 (11) | 0.0553 (11) | 0.0088 (12) | −0.0177 (12) | −0.0061 (9) |
O11 | 0.141 (6) | 0.068 (4) | 0.087 (4) | 0.021 (4) | −0.018 (4) | 0.005 (3) |
O21A | 0.113 (10) | 0.057 (7) | 0.103 (8) | 0.002 (7) | 0.010 (7) | −0.026 (6) |
O31A | 0.209 (15) | 0.083 (8) | 0.081 (8) | 0.012 (10) | −0.066 (10) | −0.028 (6) |
O41A | 0.108 (9) | 0.150 (12) | 0.105 (12) | −0.021 (8) | 0.002 (8) | 0.036 (10) |
O21B | 0.16 (2) | 0.052 (9) | 0.115 (14) | −0.009 (12) | −0.036 (13) | −0.034 (9) |
O31B | 0.107 (11) | 0.127 (16) | 0.112 (17) | 0.031 (11) | −0.047 (10) | −0.070 (14) |
O41B | 0.153 (15) | 0.20 (2) | 0.076 (13) | 0.026 (16) | 0.010 (12) | 0.042 (12) |
Cl2 | 0.0651 (11) | 0.0457 (11) | 0.0979 (16) | 0.0063 (10) | −0.0117 (12) | 0.0042 (10) |
O12 | 0.086 (4) | 0.137 (8) | 0.204 (9) | 0.025 (5) | −0.048 (5) | −0.007 (7) |
O22A | 0.184 (13) | 0.173 (18) | 0.082 (6) | −0.039 (13) | −0.022 (8) | 0.004 (8) |
O32A | 0.126 (10) | 0.060 (6) | 0.147 (12) | 0.006 (7) | 0.052 (10) | −0.005 (7) |
O42A | 0.120 (9) | 0.063 (7) | 0.207 (17) | −0.021 (7) | 0.005 (11) | 0.008 (9) |
O22B | 0.194 (19) | 0.149 (19) | 0.154 (13) | −0.034 (19) | −0.061 (13) | −0.050 (14) |
O32B | 0.134 (15) | 0.052 (7) | 0.154 (18) | 0.029 (10) | 0.069 (15) | 0.047 (9) |
O42B | 0.152 (13) | 0.083 (15) | 0.204 (18) | 0.018 (14) | 0.044 (16) | 0.072 (15) |
O1W | 0.072 (4) | 0.059 (3) | 0.063 (3) | 0.015 (3) | −0.011 (3) | −0.006 (3) |
Ni1—N1 | 2.144 (6) | C6—H6A | 0.9700 |
Ni1—N2 | 2.085 (6) | C6—H6B | 0.9700 |
Ni1—N3 | 2.094 (6) | C7—C8 | 1.506 (11) |
Ni1—N4 | 2.088 (6) | C7—H7A | 0.9700 |
Ni1—N5 | 2.051 (6) | C7—H7B | 0.9700 |
Ni1—O1W | 2.222 (6) | C8—H8A | 0.9700 |
N1—C14 | 1.486 (9) | C8—H8B | 0.9700 |
N1—C1 | 1.499 (9) | C9—C10 | 1.514 (11) |
N1—C10 | 1.500 (9) | C9—H9A | 0.9700 |
N2—C4 | 1.447 (10) | C9—H9B | 0.9700 |
N2—C3 | 1.483 (10) | C10—H10A | 0.9700 |
N2—H2 | 0.9100 | C10—H10B | 0.9700 |
N3—C5 | 1.479 (9) | C11—C14 | 1.492 (10) |
N3—C6 | 1.479 (10) | C12—C13 | 1.342 (11) |
N3—H3 | 0.9100 | C12—H12 | 0.9300 |
N4—C9 | 1.464 (9) | C13—H13 | 0.9300 |
N4—C8 | 1.471 (9) | C14—H14A | 0.9700 |
N4—H4 | 0.9100 | C14—H14B | 0.9700 |
N5—C11 | 1.300 (9) | C15—H15A | 0.9600 |
N5—C13 | 1.393 (9) | C15—H15B | 0.9600 |
N6—C11 | 1.343 (9) | C15—H15C | 0.9600 |
N6—C12 | 1.369 (10) | Cl1—O21B | 1.382 (8) |
N6—C15 | 1.463 (9) | Cl1—O31A | 1.391 (7) |
C1—C2 | 1.492 (10) | Cl1—O41B | 1.393 (8) |
C1—H1A | 0.9700 | Cl1—O11 | 1.395 (5) |
C1—H1B | 0.9700 | Cl1—O21A | 1.399 (7) |
C2—C3 | 1.501 (11) | Cl1—O31B | 1.426 (8) |
C2—H2A | 0.9700 | Cl1—O41A | 1.427 (7) |
C2—H2B | 0.9700 | Cl2—O42A | 1.375 (7) |
C3—H3A | 0.9700 | Cl2—O32B | 1.379 (7) |
C3—H3B | 0.9700 | Cl2—O32A | 1.393 (7) |
C4—C5 | 1.519 (12) | Cl2—O22B | 1.394 (8) |
C4—H4A | 0.9700 | Cl2—O12 | 1.395 (5) |
C4—H4B | 0.9700 | Cl2—O42B | 1.420 (8) |
C5—H5A | 0.9700 | Cl2—O22A | 1.435 (7) |
C5—H5B | 0.9700 | O1W—H1WA | 0.846 (12) |
C6—C7 | 1.512 (11) | O1W—H1WB | 0.846 (12) |
N1—Ni1—N2 | 92.7 (2) | C7—C6—H6A | 108.8 |
N1—Ni1—N3 | 173.9 (2) | N3—C6—H6B | 108.8 |
N1—Ni1—N4 | 84.6 (2) | C7—C6—H6B | 108.8 |
N1—Ni1—N5 | 81.9 (2) | H6A—C6—H6B | 107.7 |
N1—Ni1—O1W | 92.6 (2) | C8—C7—C6 | 115.5 (7) |
N2—Ni1—N3 | 83.5 (2) | C8—C7—H7A | 108.4 |
N2—Ni1—N4 | 97.6 (2) | C6—C7—H7A | 108.4 |
N2—Ni1—N5 | 169.5 (3) | C8—C7—H7B | 108.4 |
N2—Ni1—O1W | 85.9 (2) | C6—C7—H7B | 108.4 |
N3—Ni1—N4 | 91.2 (2) | H7A—C7—H7B | 107.5 |
N3—Ni1—N5 | 102.6 (2) | N4—C8—C7 | 112.9 (6) |
N3—Ni1—O1W | 91.8 (2) | N4—C8—H8A | 109.0 |
N4—Ni1—N5 | 90.9 (3) | C7—C8—H8A | 109.0 |
N4—Ni1—O1W | 175.6 (2) | N4—C8—H8B | 109.0 |
N5—Ni1—O1W | 85.3 (2) | C7—C8—H8B | 109.0 |
C14—N1—C1 | 107.6 (6) | H8A—C8—H8B | 107.8 |
C14—N1—C10 | 109.6 (6) | N4—C9—C10 | 109.6 (6) |
C1—N1—C10 | 109.9 (6) | N4—C9—H9A | 109.7 |
C14—N1—Ni1 | 109.0 (4) | C10—C9—H9A | 109.7 |
C1—N1—Ni1 | 116.0 (5) | N4—C9—H9B | 109.7 |
C10—N1—Ni1 | 104.7 (4) | C10—C9—H9B | 109.7 |
C4—N2—C3 | 111.1 (7) | H9A—C9—H9B | 108.2 |
C4—N2—Ni1 | 105.9 (5) | N1—C10—C9 | 110.4 (6) |
C3—N2—Ni1 | 116.3 (5) | N1—C10—H10A | 109.6 |
C4—N2—H2 | 107.7 | C9—C10—H10A | 109.6 |
C3—N2—H2 | 107.7 | N1—C10—H10B | 109.6 |
Ni1—N2—H2 | 107.7 | C9—C10—H10B | 109.6 |
C5—N3—C6 | 112.5 (6) | H10A—C10—H10B | 108.1 |
C5—N3—Ni1 | 107.8 (5) | N5—C11—N6 | 111.4 (6) |
C6—N3—Ni1 | 118.1 (5) | N5—C11—C14 | 123.2 (6) |
C5—N3—H3 | 105.8 | N6—C11—C14 | 125.3 (7) |
C6—N3—H3 | 105.8 | C13—C12—N6 | 107.0 (7) |
Ni1—N3—H3 | 105.8 | C13—C12—H12 | 126.5 |
C9—N4—C8 | 111.5 (6) | N6—C12—H12 | 126.5 |
C9—N4—Ni1 | 106.7 (4) | C12—C13—N5 | 108.4 (7) |
C8—N4—Ni1 | 115.6 (5) | C12—C13—H13 | 125.8 |
C9—N4—H4 | 107.6 | N5—C13—H13 | 125.8 |
C8—N4—H4 | 107.6 | N1—C14—C11 | 110.8 (6) |
Ni1—N4—H4 | 107.6 | N1—C14—H14A | 109.5 |
C11—N5—C13 | 106.2 (6) | C11—C14—H14A | 109.5 |
C11—N5—Ni1 | 112.6 (5) | N1—C14—H14B | 109.5 |
C13—N5—Ni1 | 140.5 (5) | C11—C14—H14B | 109.5 |
C11—N6—C12 | 107.0 (6) | H14A—C14—H14B | 108.1 |
C11—N6—C15 | 126.9 (7) | N6—C15—H15A | 109.5 |
C12—N6—C15 | 126.0 (7) | N6—C15—H15B | 109.5 |
C2—C1—N1 | 115.2 (6) | H15A—C15—H15B | 109.5 |
C2—C1—H1A | 108.5 | N6—C15—H15C | 109.5 |
N1—C1—H1A | 108.5 | H15A—C15—H15C | 109.5 |
C2—C1—H1B | 108.5 | H15B—C15—H15C | 109.5 |
N1—C1—H1B | 108.5 | O21B—Cl1—O41B | 112.4 (8) |
H1A—C1—H1B | 107.5 | O21B—Cl1—O11 | 112.2 (8) |
C1—C2—C3 | 116.0 (7) | O31A—Cl1—O11 | 112.1 (6) |
C1—C2—H2A | 108.3 | O41B—Cl1—O11 | 110.4 (8) |
C3—C2—H2A | 108.3 | O31A—Cl1—O21A | 110.9 (7) |
C1—C2—H2B | 108.3 | O11—Cl1—O21A | 110.7 (6) |
C3—C2—H2B | 108.3 | O21B—Cl1—O31B | 107.3 (8) |
H2A—C2—H2B | 107.4 | O41B—Cl1—O31B | 107.8 (8) |
N2—C3—C2 | 113.1 (7) | O11—Cl1—O31B | 106.4 (7) |
N2—C3—H3A | 109.0 | O31A—Cl1—O41A | 108.2 (7) |
C2—C3—H3A | 109.0 | O11—Cl1—O41A | 108.8 (6) |
N2—C3—H3B | 109.0 | O21A—Cl1—O41A | 105.8 (6) |
C2—C3—H3B | 109.0 | O42A—Cl2—O32A | 113.8 (7) |
H3A—C3—H3B | 107.8 | O32B—Cl2—O22B | 112.0 (8) |
N2—C4—C5 | 108.9 (7) | O32A—Cl2—O22B | 133.2 (11) |
N2—C4—H4A | 109.9 | O42A—Cl2—O12 | 113.9 (7) |
C5—C4—H4A | 109.9 | O32B—Cl2—O12 | 112.6 (8) |
N2—C4—H4B | 109.9 | O32A—Cl2—O12 | 110.3 (7) |
C5—C4—H4B | 109.9 | O22B—Cl2—O12 | 109.3 (8) |
H4A—C4—H4B | 108.3 | O32B—Cl2—O42B | 108.5 (8) |
N3—C5—C4 | 108.5 (7) | O22B—Cl2—O42B | 108.0 (8) |
N3—C5—H5A | 110.0 | O12—Cl2—O42B | 106.3 (8) |
C4—C5—H5A | 110.0 | O42A—Cl2—O22A | 107.7 (7) |
N3—C5—H5B | 110.0 | O32A—Cl2—O22A | 105.9 (7) |
C4—C5—H5B | 110.0 | O12—Cl2—O22A | 104.5 (6) |
H5A—C5—H5B | 108.4 | Ni1—O1W—H1WA | 113 (5) |
N3—C6—C7 | 113.8 (7) | Ni1—O1W—H1WB | 127 (6) |
N3—C6—H6A | 108.8 | H1WA—O1W—H1WB | 107 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O11 | 0.91 | 2.32 | 3.140 (9) | 150 |
N4—H4···O42A | 0.91 | 2.16 | 3.068 (15) | 173 |
N4—H4···O42B | 0.91 | 2.24 | 3.12 (2) | 161 |
O1W—H1WA···O12i | 0.85 (1) | 2.29 (3) | 3.098 (10) | 161 (7) |
O1W—H1WB···O31B | 0.85 (1) | 2.04 (4) | 2.86 (2) | 163 (9) |
O1W—H1WB···O31A | 0.85 (1) | 2.06 (7) | 2.740 (13) | 137 (8) |
Symmetry code: (i) −x+1, y+1/2, −z+3/2. |
[Ni(ClO4)(C15H30N6)]ClO4 | F(000) = 1152 |
Mr = 552.06 | Dx = 1.630 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 3890 reflections |
a = 16.665 (5) Å | θ = 3.7–25.7° |
b = 9.696 (5) Å | µ = 1.16 mm−1 |
c = 13.936 (5) Å | T = 294 K |
β = 92.849 (5)° | Prism, light pink |
V = 2249.0 (16) Å3 | 0.12 × 0.12 × 0.10 mm |
Z = 4 |
Oxford Gemini CCD S Ultra diffractometer | 4403 independent reflections |
Radiation source: fine-focus sealed tube | 2878 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
ω scans, thick slices | θmax = 26.0°, θmin = 3.6° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −20→20 |
Tmin = 0.98, Tmax = 0.99 | k = −11→11 |
23451 measured reflections | l = −17→17 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 0.90 | w = 1/[σ2(Fo2) + (0.0541P)2] where P = (Fo2 + 2Fc2)/3 |
4403 reflections | (Δ/σ)max < 0.001 |
356 parameters | Δρmax = 0.92 e Å−3 |
732 restraints | Δρmin = −0.26 e Å−3 |
[Ni(ClO4)(C15H30N6)]ClO4 | V = 2249.0 (16) Å3 |
Mr = 552.06 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.665 (5) Å | µ = 1.16 mm−1 |
b = 9.696 (5) Å | T = 294 K |
c = 13.936 (5) Å | 0.12 × 0.12 × 0.10 mm |
β = 92.849 (5)° |
Oxford Gemini CCD S Ultra diffractometer | 4403 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 2878 reflections with I > 2σ(I) |
Tmin = 0.98, Tmax = 0.99 | Rint = 0.051 |
23451 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 732 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 0.90 | Δρmax = 0.92 e Å−3 |
4403 reflections | Δρmin = −0.26 e Å−3 |
356 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.20919 (3) | 0.02878 (5) | 0.33101 (3) | 0.03078 (15) | |
N1 | 0.27538 (17) | 0.1516 (3) | 0.23654 (18) | 0.0357 (7) | |
N2 | 0.15370 (17) | 0.2098 (3) | 0.36729 (19) | 0.0383 (7) | |
H2 | 0.1044 | 0.2108 | 0.3361 | 0.046* | |
N3 | 0.13867 (18) | −0.0884 (3) | 0.4178 (2) | 0.0435 (8) | |
H3 | 0.0891 | −0.0943 | 0.3876 | 0.052* | |
N4 | 0.24678 (19) | −0.1568 (3) | 0.2797 (2) | 0.0416 (7) | |
H4 | 0.2959 | −0.1731 | 0.3089 | 0.050* | |
N5 | 0.31039 (17) | 0.0594 (3) | 0.42165 (18) | 0.0338 (7) | |
N6 | 0.42811 (17) | 0.1615 (3) | 0.4420 (2) | 0.0382 (7) | |
C1 | 0.2263 (2) | 0.2802 (4) | 0.2295 (3) | 0.0460 (9) | |
H1A | 0.1791 | 0.2646 | 0.1873 | 0.055* | |
H1B | 0.2575 | 0.3535 | 0.2021 | 0.055* | |
C2 | 0.2008 (2) | 0.3228 (4) | 0.3272 (3) | 0.0479 (10) | |
H2A | 0.2478 | 0.3417 | 0.3691 | 0.057* | |
H2B | 0.1686 | 0.4060 | 0.3221 | 0.057* | |
C3 | 0.1410 (2) | 0.2246 (5) | 0.4710 (3) | 0.0492 (10) | |
H3A | 0.1155 | 0.3128 | 0.4822 | 0.059* | |
H3B | 0.1926 | 0.2241 | 0.5063 | 0.059* | |
C4 | 0.0894 (2) | 0.1107 (5) | 0.5083 (3) | 0.0571 (11) | |
H4A | 0.0407 | 0.1048 | 0.4673 | 0.068* | |
H4B | 0.0737 | 0.1360 | 0.5721 | 0.068* | |
C5 | 0.1275 (2) | −0.0306 (5) | 0.5138 (2) | 0.0531 (11) | |
H5A | 0.1793 | −0.0243 | 0.5486 | 0.064* | |
H5B | 0.0938 | −0.0921 | 0.5491 | 0.064* | |
C6 | 0.1742 (3) | −0.2287 (4) | 0.4172 (3) | 0.0586 (11) | |
H6A | 0.1367 | −0.2953 | 0.4413 | 0.070* | |
H6B | 0.2231 | −0.2313 | 0.4580 | 0.070* | |
C7 | 0.1925 (3) | −0.2629 (4) | 0.3157 (3) | 0.0553 (11) | |
H7A | 0.2177 | −0.3529 | 0.3132 | 0.066* | |
H7B | 0.1431 | −0.2655 | 0.2758 | 0.066* | |
C8 | 0.2574 (3) | −0.1670 (4) | 0.1749 (3) | 0.0533 (11) | |
H8A | 0.2056 | −0.1567 | 0.1406 | 0.064* | |
H8B | 0.2783 | −0.2575 | 0.1601 | 0.064* | |
C9 | 0.3142 (3) | −0.0576 (4) | 0.1413 (3) | 0.0543 (11) | |
H9A | 0.3627 | −0.0599 | 0.1828 | 0.065* | |
H9B | 0.3293 | −0.0811 | 0.0770 | 0.065* | |
C10 | 0.2818 (2) | 0.0876 (4) | 0.1400 (2) | 0.0472 (10) | |
H10A | 0.3163 | 0.1448 | 0.1026 | 0.057* | |
H10B | 0.2289 | 0.0871 | 0.1075 | 0.057* | |
C11 | 0.3648 (2) | 0.1364 (3) | 0.3811 (2) | 0.0322 (8) | |
C12 | 0.4131 (2) | 0.0971 (4) | 0.5269 (2) | 0.0429 (9) | |
H12 | 0.4460 | 0.0969 | 0.5828 | 0.051* | |
C13 | 0.3418 (2) | 0.0345 (4) | 0.5133 (2) | 0.0395 (8) | |
H13 | 0.3170 | −0.0181 | 0.5591 | 0.047* | |
C14 | 0.3570 (2) | 0.1843 (4) | 0.2795 (2) | 0.0414 (9) | |
H14A | 0.3974 | 0.1395 | 0.2425 | 0.050* | |
H14B | 0.3660 | 0.2831 | 0.2770 | 0.050* | |
C15 | 0.4992 (2) | 0.2440 (4) | 0.4227 (3) | 0.0568 (11) | |
H15A | 0.4949 | 0.2774 | 0.3578 | 0.085* | |
H15B | 0.5465 | 0.1878 | 0.4313 | 0.085* | |
H15C | 0.5029 | 0.3207 | 0.4662 | 0.085* | |
Cl1 | 0.02402 (6) | −0.00001 (14) | 0.19185 (8) | 0.0648 (4) | |
O11 | 0.10745 (16) | 0.0196 (3) | 0.20729 (19) | 0.0646 (8) | |
O21A | −0.0130 (9) | 0.025 (2) | 0.2790 (8) | 0.123 (6) | 0.424 (19) |
O31A | 0.0175 (9) | −0.1461 (8) | 0.1727 (17) | 0.160 (8) | 0.424 (19) |
O41A | −0.0122 (7) | 0.0682 (15) | 0.1174 (7) | 0.100 (5) | 0.424 (19) |
O21B | −0.0110 (7) | −0.0303 (18) | 0.2777 (6) | 0.132 (5) | 0.576 (19) |
O31B | 0.0103 (8) | −0.1058 (15) | 0.1253 (9) | 0.184 (6) | 0.576 (19) |
O41B | −0.0041 (8) | 0.1245 (14) | 0.1523 (12) | 0.196 (7) | 0.576 (19) |
Cl2 | 0.41534 (7) | −0.39828 (13) | 0.33151 (8) | 0.0647 (3) | |
O12A | 0.4166 (9) | −0.2528 (7) | 0.3156 (13) | 0.075 (4) | 0.42 (2) |
O22A | 0.4934 (5) | −0.4324 (16) | 0.3697 (12) | 0.080 (4) | 0.42 (2) |
O32A | 0.3589 (9) | −0.431 (2) | 0.3973 (12) | 0.109 (6) | 0.42 (2) |
O42A | 0.3998 (13) | −0.4624 (18) | 0.2428 (8) | 0.124 (6) | 0.42 (2) |
O12B | 0.4116 (9) | −0.2570 (7) | 0.3512 (12) | 0.129 (6) | 0.58 (2) |
O22B | 0.4939 (5) | −0.4459 (15) | 0.3255 (15) | 0.146 (6) | 0.58 (2) |
O32B | 0.3782 (8) | −0.4745 (15) | 0.4034 (7) | 0.088 (3) | 0.58 (2) |
O42B | 0.3698 (9) | −0.4246 (13) | 0.2439 (7) | 0.103 (4) | 0.58 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0289 (2) | 0.0335 (2) | 0.0298 (2) | −0.0039 (2) | 0.00002 (17) | 0.0017 (2) |
N1 | 0.0335 (16) | 0.0425 (18) | 0.0309 (14) | −0.0046 (14) | 0.0002 (12) | 0.0048 (13) |
N2 | 0.0283 (16) | 0.0444 (19) | 0.0419 (16) | −0.0020 (14) | −0.0019 (13) | −0.0029 (14) |
N3 | 0.0300 (17) | 0.057 (2) | 0.0431 (17) | −0.0100 (15) | −0.0010 (14) | 0.0098 (15) |
N4 | 0.0372 (18) | 0.0371 (17) | 0.0501 (18) | −0.0008 (14) | −0.0030 (14) | −0.0029 (14) |
N5 | 0.0305 (15) | 0.0386 (18) | 0.0319 (14) | −0.0002 (13) | −0.0023 (12) | 0.0022 (12) |
N6 | 0.0278 (16) | 0.0396 (18) | 0.0466 (17) | −0.0022 (14) | −0.0038 (13) | −0.0006 (14) |
C1 | 0.044 (2) | 0.042 (2) | 0.051 (2) | −0.0042 (19) | −0.0031 (18) | 0.0156 (18) |
C2 | 0.042 (2) | 0.033 (2) | 0.068 (2) | −0.0001 (19) | −0.001 (2) | 0.0008 (19) |
C3 | 0.037 (2) | 0.068 (3) | 0.043 (2) | 0.001 (2) | 0.0010 (18) | −0.0172 (19) |
C4 | 0.039 (2) | 0.093 (3) | 0.039 (2) | −0.007 (2) | 0.0082 (18) | −0.007 (2) |
C5 | 0.036 (2) | 0.088 (3) | 0.0357 (19) | −0.016 (2) | 0.0039 (17) | 0.011 (2) |
C6 | 0.055 (3) | 0.049 (3) | 0.071 (3) | −0.016 (2) | −0.004 (2) | 0.023 (2) |
C7 | 0.054 (3) | 0.031 (2) | 0.079 (3) | −0.011 (2) | −0.004 (2) | 0.001 (2) |
C8 | 0.060 (3) | 0.049 (2) | 0.051 (2) | 0.004 (2) | −0.002 (2) | −0.0185 (19) |
C9 | 0.053 (3) | 0.072 (3) | 0.038 (2) | 0.010 (2) | 0.0096 (19) | −0.0109 (19) |
C10 | 0.048 (2) | 0.065 (3) | 0.0290 (18) | −0.006 (2) | 0.0048 (17) | 0.0076 (17) |
C11 | 0.0279 (18) | 0.0300 (19) | 0.0382 (18) | −0.0002 (15) | −0.0015 (15) | −0.0001 (15) |
C12 | 0.041 (2) | 0.049 (2) | 0.0372 (19) | 0.0088 (19) | −0.0093 (17) | −0.0004 (17) |
C13 | 0.040 (2) | 0.043 (2) | 0.0356 (18) | 0.0037 (19) | 0.0000 (16) | 0.0046 (17) |
C14 | 0.032 (2) | 0.052 (2) | 0.0405 (19) | −0.0064 (18) | 0.0028 (16) | 0.0053 (17) |
C15 | 0.034 (2) | 0.058 (3) | 0.076 (3) | −0.011 (2) | −0.013 (2) | 0.008 (2) |
Cl1 | 0.0363 (6) | 0.1004 (11) | 0.0564 (6) | −0.0072 (6) | −0.0104 (5) | 0.0126 (6) |
O11 | 0.0389 (16) | 0.100 (2) | 0.0541 (17) | −0.0138 (16) | −0.0096 (13) | −0.0043 (16) |
O21A | 0.056 (8) | 0.250 (17) | 0.064 (7) | 0.019 (9) | 0.018 (7) | 0.017 (8) |
O31A | 0.135 (11) | 0.088 (7) | 0.248 (19) | −0.042 (7) | −0.078 (13) | −0.021 (9) |
O41A | 0.065 (6) | 0.188 (12) | 0.045 (5) | 0.031 (8) | −0.026 (5) | −0.003 (6) |
O21B | 0.051 (6) | 0.267 (14) | 0.078 (6) | −0.024 (7) | 0.006 (5) | 0.070 (7) |
O31B | 0.199 (12) | 0.260 (12) | 0.090 (7) | −0.146 (10) | −0.027 (7) | −0.052 (8) |
O41B | 0.165 (11) | 0.271 (11) | 0.159 (11) | 0.157 (11) | 0.071 (8) | 0.120 (9) |
Cl2 | 0.0615 (8) | 0.0640 (8) | 0.0688 (7) | 0.0135 (6) | 0.0057 (6) | 0.0070 (6) |
O12A | 0.074 (7) | 0.063 (6) | 0.085 (9) | 0.001 (5) | −0.029 (7) | −0.001 (4) |
O22A | 0.058 (6) | 0.077 (7) | 0.108 (9) | 0.015 (5) | 0.031 (5) | 0.025 (6) |
O32A | 0.047 (7) | 0.202 (16) | 0.081 (7) | 0.014 (8) | 0.022 (6) | 0.038 (9) |
O42A | 0.263 (19) | 0.052 (8) | 0.058 (6) | 0.007 (11) | 0.012 (8) | −0.012 (5) |
O12B | 0.156 (11) | 0.072 (5) | 0.145 (12) | 0.046 (6) | −0.111 (9) | −0.033 (5) |
O22B | 0.064 (5) | 0.135 (9) | 0.245 (15) | 0.047 (6) | 0.079 (6) | 0.110 (10) |
O32B | 0.050 (5) | 0.141 (8) | 0.073 (5) | 0.010 (5) | 0.013 (4) | 0.006 (5) |
O42B | 0.167 (9) | 0.069 (7) | 0.070 (5) | 0.033 (6) | −0.018 (5) | −0.021 (4) |
Ni1—N1 | 2.124 (3) | C6—H6A | 0.9700 |
Ni1—N2 | 2.059 (3) | C6—H6B | 0.9700 |
Ni1—N3 | 2.068 (3) | C7—H7A | 0.9700 |
Ni1—N4 | 2.046 (3) | C7—H7B | 0.9700 |
Ni1—N5 | 2.077 (3) | C8—C9 | 1.512 (6) |
Ni1—O11 | 2.359 (3) | C8—H8A | 0.9700 |
N1—C10 | 1.490 (4) | C8—H8B | 0.9700 |
N1—C1 | 1.492 (5) | C9—C10 | 1.508 (6) |
N1—C14 | 1.493 (4) | C9—H9A | 0.9700 |
N2—C2 | 1.474 (5) | C9—H9B | 0.9700 |
N2—C3 | 1.478 (4) | C10—H10A | 0.9700 |
N2—H2 | 0.9100 | C10—H10B | 0.9700 |
N3—C5 | 1.470 (5) | C11—C14 | 1.490 (5) |
N3—C6 | 1.484 (5) | C12—C13 | 1.340 (5) |
N3—H3 | 0.9100 | C12—H12 | 0.9300 |
N4—C7 | 1.474 (5) | C13—H13 | 0.9300 |
N4—C8 | 1.484 (4) | C14—H14A | 0.9700 |
N4—H4 | 0.9100 | C14—H14B | 0.9700 |
N5—C11 | 1.323 (4) | C15—H15A | 0.9600 |
N5—C13 | 1.377 (4) | C15—H15B | 0.9600 |
N6—C11 | 1.343 (4) | C15—H15C | 0.9600 |
N6—C12 | 1.371 (4) | Cl1—O41A | 1.348 (7) |
N6—C15 | 1.466 (5) | Cl1—O21B | 1.389 (6) |
C1—C2 | 1.504 (5) | Cl1—O31B | 1.394 (7) |
C1—H1A | 0.9700 | Cl1—O41B | 1.398 (7) |
C1—H1B | 0.9700 | Cl1—O21A | 1.409 (7) |
C2—H2A | 0.9700 | Cl1—O11 | 1.409 (3) |
C2—H2B | 0.9700 | Cl1—O31A | 1.445 (7) |
C3—C4 | 1.508 (6) | Cl2—O32A | 1.383 (7) |
C3—H3A | 0.9700 | Cl2—O22B | 1.395 (6) |
C3—H3B | 0.9700 | Cl2—O42A | 1.396 (7) |
C4—C5 | 1.511 (6) | Cl2—O12B | 1.399 (6) |
C4—H4A | 0.9700 | Cl2—O32B | 1.413 (6) |
C4—H4B | 0.9700 | Cl2—O22A | 1.420 (7) |
C5—H5A | 0.9700 | Cl2—O42B | 1.428 (6) |
C5—H5B | 0.9700 | Cl2—O12A | 1.428 (7) |
C6—C7 | 1.499 (5) | ||
N1—Ni1—N2 | 85.85 (11) | N3—C6—H6A | 110.1 |
N1—Ni1—N3 | 176.57 (12) | C7—C6—H6A | 110.1 |
N1—Ni1—N4 | 95.69 (12) | N3—C6—H6B | 110.1 |
N1—Ni1—N5 | 82.30 (11) | C7—C6—H6B | 110.1 |
N1—Ni1—O11 | 86.83 (10) | H6A—C6—H6B | 108.4 |
N2—Ni1—N3 | 92.83 (12) | N4—C7—C6 | 108.9 (3) |
N2—Ni1—N4 | 169.98 (12) | N4—C7—H7A | 109.9 |
N2—Ni1—N5 | 95.16 (11) | C6—C7—H7A | 109.9 |
N2—Ni1—O11 | 84.06 (11) | N4—C7—H7B | 109.9 |
N3—Ni1—N4 | 85.07 (13) | C6—C7—H7B | 109.9 |
N3—Ni1—N5 | 100.98 (11) | H7A—C7—H7B | 108.3 |
N3—Ni1—O11 | 89.89 (11) | N4—C8—C9 | 111.4 (3) |
N4—Ni1—N5 | 94.86 (11) | N4—C8—H8A | 109.4 |
N4—Ni1—O11 | 86.15 (12) | C9—C8—H8A | 109.4 |
N5—Ni1—O11 | 169.13 (10) | N4—C8—H8B | 109.4 |
C10—N1—C1 | 110.6 (3) | C9—C8—H8B | 109.4 |
C10—N1—C14 | 110.2 (3) | H8A—C8—H8B | 108.0 |
C1—N1—C14 | 109.6 (3) | C10—C9—C8 | 115.4 (3) |
C10—N1—Ni1 | 112.9 (2) | C10—C9—H9A | 108.4 |
C1—N1—Ni1 | 102.1 (2) | C8—C9—H9A | 108.4 |
C14—N1—Ni1 | 111.21 (19) | C10—C9—H9B | 108.4 |
C2—N2—C3 | 113.8 (3) | C8—C9—H9B | 108.4 |
C2—N2—Ni1 | 106.6 (2) | H9A—C9—H9B | 107.5 |
C3—N2—Ni1 | 114.3 (2) | N1—C10—C9 | 114.8 (3) |
C2—N2—H2 | 107.3 | N1—C10—H10A | 108.6 |
C3—N2—H2 | 107.3 | C9—C10—H10A | 108.6 |
Ni1—N2—H2 | 107.3 | N1—C10—H10B | 108.6 |
C5—N3—C6 | 115.0 (3) | C9—C10—H10B | 108.6 |
C5—N3—Ni1 | 115.1 (2) | H10A—C10—H10B | 107.5 |
C6—N3—Ni1 | 105.2 (2) | N5—C11—N6 | 111.4 (3) |
C5—N3—H3 | 107.0 | N5—C11—C14 | 123.6 (3) |
C6—N3—H3 | 107.0 | N6—C11—C14 | 125.0 (3) |
Ni1—N3—H3 | 107.0 | C13—C12—N6 | 106.4 (3) |
C7—N4—C8 | 113.1 (3) | C13—C12—H12 | 126.8 |
C7—N4—Ni1 | 106.9 (2) | N6—C12—H12 | 126.8 |
C8—N4—Ni1 | 117.1 (2) | C12—C13—N5 | 110.2 (3) |
C7—N4—H4 | 106.3 | C12—C13—H13 | 124.9 |
C8—N4—H4 | 106.3 | N5—C13—H13 | 124.9 |
Ni1—N4—H4 | 106.3 | C11—C14—N1 | 110.4 (3) |
C11—N5—C13 | 104.9 (3) | C11—C14—H14A | 109.6 |
C11—N5—Ni1 | 112.0 (2) | N1—C14—H14A | 109.6 |
C13—N5—Ni1 | 143.0 (2) | C11—C14—H14B | 109.6 |
C11—N6—C12 | 107.0 (3) | N1—C14—H14B | 109.6 |
C11—N6—C15 | 126.8 (3) | H14A—C14—H14B | 108.1 |
C12—N6—C15 | 126.2 (3) | N6—C15—H15A | 109.5 |
N1—C1—C2 | 110.4 (3) | N6—C15—H15B | 109.5 |
N1—C1—H1A | 109.6 | H15A—C15—H15B | 109.5 |
C2—C1—H1A | 109.6 | N6—C15—H15C | 109.5 |
N1—C1—H1B | 109.6 | H15A—C15—H15C | 109.5 |
C2—C1—H1B | 109.6 | H15B—C15—H15C | 109.5 |
H1A—C1—H1B | 108.1 | O21B—Cl1—O31B | 110.9 (7) |
N2—C2—C1 | 108.6 (3) | O21B—Cl1—O41B | 112.1 (7) |
N2—C2—H2A | 110.0 | O31B—Cl1—O41B | 109.4 (6) |
C1—C2—H2A | 110.0 | O41A—Cl1—O21A | 112.5 (7) |
N2—C2—H2B | 110.0 | O41A—Cl1—O11 | 116.8 (6) |
C1—C2—H2B | 110.0 | O21B—Cl1—O11 | 110.5 (5) |
H2A—C2—H2B | 108.4 | O31B—Cl1—O11 | 109.2 (6) |
N2—C3—C4 | 112.2 (3) | O41B—Cl1—O11 | 104.6 (6) |
N2—C3—H3A | 109.2 | O21A—Cl1—O11 | 108.4 (7) |
C4—C3—H3A | 109.2 | O41A—Cl1—O31A | 108.2 (7) |
N2—C3—H3B | 109.2 | O21A—Cl1—O31A | 107.1 (8) |
C4—C3—H3B | 109.2 | O11—Cl1—O31A | 103.0 (6) |
H3A—C3—H3B | 107.9 | Cl1—O11—Ni1 | 141.68 (18) |
C3—C4—C5 | 115.8 (3) | O32A—Cl2—O42A | 112.5 (8) |
C3—C4—H4A | 108.3 | O22B—Cl2—O12B | 112.8 (8) |
C5—C4—H4A | 108.3 | O22B—Cl2—O32B | 108.4 (6) |
C3—C4—H4B | 108.3 | O42A—Cl2—O32B | 109.1 (11) |
C5—C4—H4B | 108.3 | O12B—Cl2—O32B | 110.4 (6) |
H4A—C4—H4B | 107.4 | O32A—Cl2—O22A | 109.8 (7) |
N3—C5—C4 | 111.8 (3) | O42A—Cl2—O22A | 110.7 (7) |
N3—C5—H5A | 109.3 | O22B—Cl2—O42B | 110.5 (7) |
C4—C5—H5A | 109.3 | O12B—Cl2—O42B | 108.4 (6) |
N3—C5—H5B | 109.3 | O32B—Cl2—O42B | 106.3 (6) |
C4—C5—H5B | 109.3 | O32A—Cl2—O12A | 110.2 (8) |
H5A—C5—H5B | 107.9 | O42A—Cl2—O12A | 107.8 (7) |
N3—C6—C7 | 108.0 (3) | O22A—Cl2—O12A | 105.5 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O21B | 0.91 | 2.29 | 3.140 (13) | 155 |
N4—H4···O12B | 0.91 | 2.15 | 3.035 (14) | 165 |
N4—H4···O12A | 0.91 | 2.15 | 2.997 (15) | 154 |
[Ni(C20H36N6)](ClO4)2·0.24H2O | F(000) = 2723 |
Mr = 650.50 | Dx = 1.546 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 4665 reflections |
a = 13.7285 (12) Å | θ = 2.0–26.0° |
b = 19.2330 (18) Å | µ = 0.95 mm−1 |
c = 21.171 (2) Å | T = 294 K |
V = 5589.9 (9) Å3 | Prism, light pink |
Z = 8 | 0.22 × 0.16 × 0.16 mm |
Oxford Gemini CCD S Ultra diffractometer | 5489 independent reflections |
Radiation source: fine-focus sealed tube | 3936 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
ω scans, thick slices | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −16→16 |
Tmin = 0.98, Tmax = 0.99 | k = −23→23 |
40257 measured reflections | l = −25→26 |
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)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.151 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.067P)2 + 4.2236P] where P = (Fo2 + 2Fc2)/3 |
5489 reflections | (Δ/σ)max = 0.001 |
479 parameters | Δρmax = 0.49 e Å−3 |
934 restraints | Δρmin = −0.27 e Å−3 |
[Ni(C20H36N6)](ClO4)2·0.24H2O | V = 5589.9 (9) Å3 |
Mr = 650.50 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 13.7285 (12) Å | µ = 0.95 mm−1 |
b = 19.2330 (18) Å | T = 294 K |
c = 21.171 (2) Å | 0.22 × 0.16 × 0.16 mm |
Oxford Gemini CCD S Ultra diffractometer | 5489 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 3936 reflections with I > 2σ(I) |
Tmin = 0.98, Tmax = 0.99 | Rint = 0.053 |
40257 measured reflections |
R[F2 > 2σ(F2)] = 0.064 | 934 restraints |
wR(F2) = 0.151 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.49 e Å−3 |
5489 reflections | Δρmin = −0.27 e Å−3 |
479 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.80637 (4) | 0.39709 (3) | 0.63909 (3) | 0.0441 (2) | |
N1 | 0.7798 (3) | 0.50674 (19) | 0.64544 (18) | 0.0528 (9) | |
N2 | 0.6580 (3) | 0.3891 (2) | 0.6618 (2) | 0.0608 (10) | |
H2C | 0.6243 | 0.3846 | 0.6249 | 0.073* | |
N3 | 0.8206 (3) | 0.2869 (2) | 0.6274 (2) | 0.0677 (12) | |
N4 | 0.7871 (3) | 0.3970 (2) | 0.54068 (19) | 0.0665 (11) | |
H4C | 0.7219 | 0.3970 | 0.5329 | 0.080* | |
N5 | 0.9556 (3) | 0.3930 (2) | 0.62644 (18) | 0.0534 (9) | |
N6 | 0.8348 (3) | 0.4100 (2) | 0.73468 (18) | 0.0513 (9) | |
N7 | 0.8633 (3) | 0.4843 (3) | 0.8104 (2) | 0.0768 (13) | |
N8 | 1.0857 (3) | 0.3270 (3) | 0.6268 (2) | 0.0721 (12) | |
C1 | 0.6734 (4) | 0.5128 (3) | 0.6508 (3) | 0.0674 (14) | |
H1A | 0.6448 | 0.5112 | 0.6089 | 0.081* | |
H1B | 0.6572 | 0.5574 | 0.6694 | 0.081* | |
C2 | 0.6314 (4) | 0.4567 (3) | 0.6897 (3) | 0.0669 (14) | |
H2A | 0.6562 | 0.4596 | 0.7325 | 0.080* | |
H2B | 0.5610 | 0.4613 | 0.6912 | 0.080* | |
C3 | 0.6306 (4) | 0.3315 (3) | 0.7025 (3) | 0.0833 (17) | |
H3A | 0.5614 | 0.3341 | 0.7113 | 0.100* | |
H3B | 0.6651 | 0.3356 | 0.7423 | 0.100* | |
C4 | 0.6535 (5) | 0.2613 (3) | 0.6733 (4) | 0.098 (2) | |
H4A | 0.6200 | 0.2256 | 0.6972 | 0.118* | |
H4B | 0.6277 | 0.2605 | 0.6306 | 0.118* | |
C5 | 0.7599 (5) | 0.2436 (3) | 0.6708 (3) | 0.0899 (18) | |
H5A | 0.7864 | 0.2476 | 0.7131 | 0.108* | |
H5B | 0.7662 | 0.1953 | 0.6581 | 0.108* | |
C6 | 0.7901 (5) | 0.2735 (3) | 0.5613 (3) | 0.0868 (18) | |
H6A | 0.7196 | 0.2714 | 0.5591 | 0.104* | |
H6B | 0.8156 | 0.2290 | 0.5476 | 0.104* | |
C7 | 0.8264 (5) | 0.3296 (3) | 0.5186 (3) | 0.0813 (16) | |
H7A | 0.8970 | 0.3306 | 0.5192 | 0.098* | |
H7B | 0.8052 | 0.3207 | 0.4757 | 0.098* | |
C8 | 0.8300 (5) | 0.4564 (3) | 0.5065 (3) | 0.0840 (17) | |
H8A | 0.8202 | 0.4500 | 0.4615 | 0.101* | |
H8B | 0.8996 | 0.4577 | 0.5143 | 0.101* | |
C9 | 0.7853 (5) | 0.5247 (3) | 0.5266 (3) | 0.0876 (18) | |
H9A | 0.8025 | 0.5599 | 0.4957 | 0.105* | |
H9B | 0.7150 | 0.5199 | 0.5262 | 0.105* | |
C10 | 0.8164 (4) | 0.5494 (3) | 0.5910 (3) | 0.0742 (15) | |
H10A | 0.8870 | 0.5500 | 0.5925 | 0.089* | |
H10B | 0.7941 | 0.5969 | 0.5965 | 0.089* | |
C11 | 0.9880 (4) | 0.3284 (3) | 0.6289 (2) | 0.0598 (12) | |
C12 | 1.1158 (4) | 0.3940 (4) | 0.6238 (3) | 0.0806 (16) | |
H12 | 1.1800 | 0.4093 | 0.6219 | 0.097* | |
C13 | 1.0365 (4) | 0.4341 (3) | 0.6240 (2) | 0.0631 (13) | |
H13 | 1.0363 | 0.4825 | 0.6228 | 0.076* | |
C14 | 0.9235 (4) | 0.2680 (3) | 0.6376 (3) | 0.0777 (16) | |
H14A | 0.9315 | 0.2500 | 0.6801 | 0.093* | |
H14B | 0.9419 | 0.2317 | 0.6081 | 0.093* | |
C15 | 1.1463 (5) | 0.2649 (4) | 0.6279 (4) | 0.114 (3) | |
H15A | 1.1796 | 0.2620 | 0.6677 | 0.171* | |
H15B | 1.1932 | 0.2672 | 0.5943 | 0.171* | |
H15C | 1.1062 | 0.2245 | 0.6224 | 0.171* | |
C16 | 0.8408 (3) | 0.4756 (3) | 0.7496 (2) | 0.0560 (11) | |
C17 | 0.8728 (4) | 0.4186 (4) | 0.8354 (3) | 0.0847 (17) | |
H17 | 0.8886 | 0.4078 | 0.8769 | 0.102* | |
C18 | 0.8554 (4) | 0.3738 (3) | 0.7896 (3) | 0.0715 (14) | |
H18 | 0.8567 | 0.3257 | 0.7936 | 0.086* | |
C19 | 0.8282 (4) | 0.5325 (3) | 0.7036 (3) | 0.0668 (13) | |
H19A | 0.8913 | 0.5518 | 0.6929 | 0.080* | |
H19B | 0.7892 | 0.5691 | 0.7223 | 0.080* | |
C20 | 0.8791 (5) | 0.5500 (4) | 0.8440 (3) | 0.115 (3) | |
H20A | 0.9115 | 0.5823 | 0.8165 | 0.173* | |
H20B | 0.9187 | 0.5418 | 0.8806 | 0.173* | |
H20C | 0.8175 | 0.5689 | 0.8568 | 0.173* | |
Cl1 | 0.40599 (10) | 0.14067 (7) | 0.68572 (7) | 0.0686 (4) | |
O11 | 0.4649 (4) | 0.1256 (3) | 0.6332 (2) | 0.139 (2) | |
O21A | 0.3626 (14) | 0.2038 (6) | 0.6724 (7) | 0.115 (4) | 0.400 (10) |
O31A | 0.4666 (10) | 0.1456 (9) | 0.7385 (6) | 0.101 (4) | 0.400 (10) |
O41A | 0.3449 (11) | 0.0786 (7) | 0.6843 (8) | 0.114 (4) | 0.400 (10) |
O21B | 0.4169 (14) | 0.2176 (5) | 0.6881 (9) | 0.108 (4) | 0.286 (7) |
O31B | 0.4480 (15) | 0.1156 (10) | 0.7416 (7) | 0.110 (4) | 0.286 (7) |
O41B | 0.3105 (8) | 0.1314 (12) | 0.6883 (10) | 0.119 (4) | 0.286 (7) |
O21C | 0.4622 (13) | 0.1784 (11) | 0.7304 (8) | 0.107 (4) | 0.314 (10) |
O31C | 0.3848 (14) | 0.0738 (6) | 0.7120 (9) | 0.112 (4) | 0.314 (10) |
O41C | 0.3196 (10) | 0.1751 (10) | 0.6747 (10) | 0.113 (4) | 0.314 (10) |
Cl2 | 0.50416 (12) | 0.36811 (9) | 0.50315 (7) | 0.0799 (4) | |
O12 | 0.5374 (5) | 0.4218 (3) | 0.5403 (3) | 0.157 (2) | |
O22A | 0.4123 (10) | 0.3437 (8) | 0.5351 (7) | 0.119 (4) | 0.405 (8) |
O32A | 0.5604 (11) | 0.3073 (7) | 0.4996 (8) | 0.142 (4) | 0.405 (8) |
O42A | 0.4708 (12) | 0.3828 (9) | 0.4423 (5) | 0.086 (3) | 0.405 (8) |
O22B | 0.4833 (13) | 0.3154 (7) | 0.5418 (6) | 0.142 (4) | 0.405 (8) |
O32B | 0.5943 (8) | 0.3546 (7) | 0.4714 (6) | 0.119 (4) | 0.405 (8) |
O42B | 0.4360 (9) | 0.3884 (9) | 0.4608 (6) | 0.091 (4) | 0.405 (8) |
O22C | 0.526 (3) | 0.3023 (8) | 0.5252 (12) | 0.140 (5) | 0.190 (8) |
O32C | 0.535 (2) | 0.3743 (12) | 0.4401 (7) | 0.097 (4) | 0.190 (8) |
O42C | 0.3995 (10) | 0.3773 (15) | 0.5015 (14) | 0.104 (4) | 0.190 (8) |
O1W | 0.5630 (18) | 0.1815 (13) | 0.5318 (12) | 0.147 (13) | 0.248 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0426 (3) | 0.0390 (3) | 0.0507 (3) | −0.0001 (2) | −0.0019 (3) | 0.0000 (2) |
N1 | 0.053 (2) | 0.046 (2) | 0.060 (2) | 0.0075 (17) | −0.0023 (18) | −0.0018 (17) |
N2 | 0.048 (2) | 0.067 (3) | 0.068 (3) | −0.002 (2) | −0.009 (2) | 0.008 (2) |
N3 | 0.068 (3) | 0.040 (2) | 0.096 (3) | −0.0013 (19) | −0.012 (2) | −0.007 (2) |
N4 | 0.071 (3) | 0.075 (3) | 0.053 (2) | 0.001 (2) | −0.005 (2) | −0.008 (2) |
N5 | 0.045 (2) | 0.055 (2) | 0.060 (2) | −0.0025 (18) | 0.0018 (18) | −0.0039 (19) |
N6 | 0.040 (2) | 0.063 (2) | 0.051 (2) | −0.0014 (17) | −0.0034 (17) | 0.0063 (18) |
N7 | 0.045 (2) | 0.123 (4) | 0.062 (3) | 0.002 (3) | −0.004 (2) | −0.020 (3) |
N8 | 0.058 (3) | 0.092 (3) | 0.067 (3) | 0.019 (2) | −0.015 (2) | −0.020 (2) |
C1 | 0.064 (3) | 0.063 (3) | 0.075 (3) | 0.022 (3) | −0.009 (3) | −0.002 (3) |
C2 | 0.035 (3) | 0.086 (4) | 0.079 (4) | 0.011 (2) | 0.000 (2) | −0.001 (3) |
C3 | 0.051 (3) | 0.095 (4) | 0.105 (5) | −0.016 (3) | 0.006 (3) | 0.025 (3) |
C4 | 0.085 (4) | 0.073 (4) | 0.137 (6) | −0.035 (3) | −0.008 (4) | 0.023 (4) |
C5 | 0.094 (4) | 0.042 (3) | 0.133 (5) | −0.019 (3) | −0.016 (4) | 0.013 (3) |
C6 | 0.095 (4) | 0.060 (3) | 0.105 (4) | −0.001 (3) | −0.018 (3) | −0.038 (3) |
C7 | 0.087 (4) | 0.089 (4) | 0.068 (3) | 0.007 (3) | −0.002 (3) | −0.034 (3) |
C8 | 0.101 (5) | 0.099 (4) | 0.052 (3) | −0.003 (4) | 0.003 (3) | 0.011 (3) |
C9 | 0.116 (5) | 0.076 (4) | 0.071 (3) | 0.010 (3) | 0.007 (3) | 0.034 (3) |
C10 | 0.092 (4) | 0.045 (3) | 0.086 (4) | 0.002 (3) | 0.007 (3) | 0.016 (3) |
C11 | 0.055 (3) | 0.057 (3) | 0.068 (3) | 0.011 (2) | −0.004 (2) | −0.019 (2) |
C12 | 0.052 (3) | 0.113 (4) | 0.076 (4) | −0.007 (3) | −0.004 (3) | −0.006 (4) |
C13 | 0.054 (3) | 0.072 (3) | 0.063 (3) | −0.005 (3) | −0.004 (2) | 0.000 (3) |
C14 | 0.074 (3) | 0.046 (3) | 0.114 (5) | 0.014 (2) | −0.012 (3) | −0.007 (3) |
C15 | 0.079 (4) | 0.124 (5) | 0.139 (6) | 0.052 (4) | −0.036 (4) | −0.053 (5) |
C16 | 0.033 (2) | 0.078 (3) | 0.057 (3) | 0.005 (2) | −0.004 (2) | −0.009 (2) |
C17 | 0.043 (3) | 0.156 (5) | 0.055 (3) | −0.004 (4) | −0.001 (3) | 0.012 (4) |
C18 | 0.039 (3) | 0.103 (4) | 0.073 (4) | −0.001 (3) | −0.004 (3) | 0.024 (3) |
C19 | 0.065 (3) | 0.058 (3) | 0.078 (3) | 0.001 (2) | −0.002 (3) | −0.013 (2) |
C20 | 0.089 (5) | 0.159 (6) | 0.097 (5) | 0.010 (5) | −0.018 (4) | −0.065 (5) |
Cl1 | 0.0573 (8) | 0.0659 (8) | 0.0826 (9) | 0.0019 (6) | 0.0055 (7) | −0.0019 (7) |
O11 | 0.147 (5) | 0.160 (5) | 0.111 (4) | 0.027 (4) | 0.040 (3) | −0.021 (3) |
O21A | 0.109 (9) | 0.067 (5) | 0.169 (9) | 0.011 (5) | −0.040 (7) | −0.010 (6) |
O31A | 0.110 (7) | 0.095 (9) | 0.099 (6) | −0.004 (7) | −0.019 (5) | −0.001 (7) |
O41A | 0.110 (8) | 0.082 (5) | 0.150 (10) | −0.021 (5) | −0.033 (6) | 0.023 (7) |
O21B | 0.089 (9) | 0.064 (4) | 0.169 (10) | 0.000 (6) | −0.010 (8) | −0.007 (6) |
O31B | 0.105 (9) | 0.117 (9) | 0.107 (7) | −0.012 (8) | −0.018 (6) | 0.027 (7) |
O41B | 0.068 (4) | 0.107 (7) | 0.183 (10) | −0.010 (5) | −0.009 (5) | 0.025 (9) |
O21C | 0.099 (8) | 0.098 (8) | 0.124 (8) | −0.002 (7) | −0.022 (6) | −0.023 (7) |
O31C | 0.107 (9) | 0.089 (5) | 0.140 (10) | −0.014 (5) | −0.019 (7) | 0.035 (6) |
O41C | 0.080 (6) | 0.069 (7) | 0.189 (10) | 0.015 (5) | −0.030 (7) | −0.020 (8) |
Cl2 | 0.0833 (10) | 0.1003 (11) | 0.0561 (8) | 0.0090 (9) | −0.0121 (7) | −0.0091 (7) |
O12 | 0.168 (5) | 0.175 (5) | 0.128 (4) | −0.045 (4) | −0.034 (4) | −0.053 (4) |
O22A | 0.116 (6) | 0.148 (10) | 0.094 (7) | −0.011 (6) | 0.019 (6) | 0.002 (6) |
O32A | 0.159 (9) | 0.145 (7) | 0.123 (9) | 0.069 (6) | 0.015 (6) | 0.031 (6) |
O42A | 0.085 (7) | 0.108 (7) | 0.066 (5) | −0.001 (7) | −0.017 (5) | 0.000 (5) |
O22B | 0.149 (9) | 0.146 (7) | 0.131 (8) | 0.015 (7) | 0.017 (6) | 0.059 (6) |
O32B | 0.098 (6) | 0.164 (9) | 0.095 (8) | 0.048 (7) | 0.009 (5) | 0.024 (6) |
O42B | 0.077 (7) | 0.105 (7) | 0.093 (7) | 0.006 (6) | −0.018 (5) | 0.006 (7) |
O22C | 0.146 (11) | 0.139 (7) | 0.135 (11) | 0.031 (8) | 0.007 (8) | 0.054 (7) |
O32C | 0.097 (8) | 0.119 (10) | 0.074 (5) | 0.020 (10) | 0.004 (6) | 0.004 (6) |
O42C | 0.082 (5) | 0.134 (11) | 0.096 (10) | 0.004 (7) | −0.003 (6) | −0.003 (9) |
O1W | 0.13 (2) | 0.15 (2) | 0.17 (2) | 0.002 (16) | −0.001 (16) | 0.023 (17) |
Ni1—N5 | 2.068 (4) | C10—H10B | 0.9700 |
Ni1—N6 | 2.076 (4) | C11—C14 | 1.471 (7) |
Ni1—N2 | 2.099 (4) | C12—C13 | 1.334 (8) |
Ni1—N4 | 2.100 (4) | C12—H12 | 0.9300 |
Ni1—N3 | 2.143 (4) | C13—H13 | 0.9300 |
Ni1—N1 | 2.144 (4) | C14—H14A | 0.9700 |
N1—C1 | 1.469 (6) | C14—H14B | 0.9700 |
N1—C19 | 1.484 (6) | C15—H15A | 0.9600 |
N1—C10 | 1.502 (6) | C15—H15B | 0.9600 |
N2—C3 | 1.454 (7) | C15—H15C | 0.9600 |
N2—C2 | 1.473 (6) | C16—C19 | 1.475 (7) |
N2—H2C | 0.9100 | C17—C18 | 1.318 (9) |
N3—C14 | 1.475 (7) | C17—H17 | 0.9300 |
N3—C6 | 1.483 (7) | C18—H18 | 0.9300 |
N3—C5 | 1.493 (7) | C19—H19A | 0.9700 |
N4—C8 | 1.476 (7) | C19—H19B | 0.9700 |
N4—C7 | 1.479 (7) | C20—H20A | 0.9600 |
N4—H4C | 0.9100 | C20—H20B | 0.9600 |
N5—C11 | 1.320 (6) | C20—H20C | 0.9600 |
N5—C13 | 1.364 (6) | Cl1—O41B | 1.324 (11) |
N6—C16 | 1.303 (6) | Cl1—O41C | 1.378 (10) |
N6—C18 | 1.384 (6) | Cl1—O21A | 1.382 (9) |
N7—C16 | 1.334 (6) | Cl1—O31A | 1.396 (9) |
N7—C17 | 1.377 (8) | Cl1—O31B | 1.402 (11) |
N7—C20 | 1.466 (8) | Cl1—O11 | 1.405 (5) |
N8—C11 | 1.342 (6) | Cl1—O21C | 1.421 (10) |
N8—C12 | 1.356 (7) | Cl1—O31C | 1.430 (10) |
N8—C15 | 1.456 (7) | Cl1—O41A | 1.459 (9) |
C1—C2 | 1.477 (7) | Cl1—O21B | 1.487 (10) |
C1—H1A | 0.9700 | O21A—O41C | 0.809 (18) |
C1—H1B | 0.9700 | O21A—O21B | 0.859 (19) |
C2—H2A | 0.9700 | O21A—O41B | 1.60 (2) |
C2—H2B | 0.9700 | O31A—O31B | 0.63 (2) |
C3—C4 | 1.518 (9) | O31A—O21C | 0.66 (2) |
C3—H3A | 0.9700 | O41A—O31C | 0.808 (17) |
C3—H3B | 0.9700 | O41A—O41B | 1.12 (2) |
C4—C5 | 1.501 (9) | O21B—O21C | 1.33 (2) |
C4—H4A | 0.9700 | O21B—O41C | 1.59 (2) |
C4—H4B | 0.9700 | O31B—O21C | 1.25 (2) |
C5—H5A | 0.9700 | O31B—O31C | 1.34 (2) |
C5—H5B | 0.9700 | O41B—O41C | 0.90 (2) |
C6—C7 | 1.492 (9) | O41B—O31C | 1.59 (2) |
C6—H6A | 0.9700 | Cl2—O22B | 1.334 (9) |
C6—H6B | 0.9700 | Cl2—O42B | 1.353 (10) |
C7—H7A | 0.9700 | Cl2—O12 | 1.376 (5) |
C7—H7B | 0.9700 | Cl2—O22C | 1.381 (13) |
C8—C9 | 1.511 (8) | Cl2—O42A | 1.396 (9) |
C8—H8A | 0.9700 | Cl2—O32A | 1.403 (9) |
C8—H8B | 0.9700 | Cl2—O32C | 1.404 (12) |
C9—C10 | 1.506 (8) | Cl2—O32B | 1.432 (9) |
C9—H9A | 0.9700 | Cl2—O42C | 1.448 (13) |
C9—H9B | 0.9700 | Cl2—O22A | 1.506 (9) |
C10—H10A | 0.9700 | ||
N5—Ni1—N6 | 86.82 (15) | C9—C8—H8A | 109.2 |
N5—Ni1—N2 | 171.38 (16) | N4—C8—H8B | 109.2 |
N6—Ni1—N2 | 88.18 (16) | C9—C8—H8B | 109.2 |
N5—Ni1—N4 | 89.78 (16) | H8A—C8—H8B | 107.9 |
N6—Ni1—N4 | 172.27 (16) | C10—C9—C8 | 114.5 (5) |
N2—Ni1—N4 | 96.01 (18) | C10—C9—H9A | 108.6 |
N5—Ni1—N3 | 81.78 (16) | C8—C9—H9A | 108.6 |
N6—Ni1—N3 | 102.33 (17) | C10—C9—H9B | 108.6 |
N2—Ni1—N3 | 92.44 (16) | C8—C9—H9B | 108.6 |
N4—Ni1—N3 | 84.01 (17) | H9A—C9—H9B | 107.6 |
N5—Ni1—N1 | 102.38 (15) | N1—C10—C9 | 115.3 (4) |
N6—Ni1—N1 | 81.57 (15) | N1—C10—H10A | 108.4 |
N2—Ni1—N1 | 83.80 (15) | C9—C10—H10A | 108.4 |
N4—Ni1—N1 | 92.40 (15) | N1—C10—H10B | 108.4 |
N3—Ni1—N1 | 174.53 (16) | C9—C10—H10B | 108.4 |
C1—N1—C19 | 110.8 (4) | H10A—C10—H10B | 107.5 |
C1—N1—C10 | 110.4 (4) | N5—C11—N8 | 110.7 (5) |
C19—N1—C10 | 107.7 (4) | N5—C11—C14 | 123.0 (4) |
C1—N1—Ni1 | 104.6 (3) | N8—C11—C14 | 126.1 (5) |
C19—N1—Ni1 | 107.7 (3) | C13—C12—N8 | 107.5 (5) |
C10—N1—Ni1 | 115.6 (3) | C13—C12—H12 | 126.2 |
C3—N2—C2 | 111.7 (5) | N8—C12—H12 | 126.2 |
C3—N2—Ni1 | 116.2 (3) | C12—C13—N5 | 109.2 (5) |
C2—N2—Ni1 | 105.6 (3) | C12—C13—H13 | 125.4 |
C3—N2—H2C | 107.7 | N5—C13—H13 | 125.4 |
C2—N2—H2C | 107.7 | C11—C14—N3 | 111.3 (4) |
Ni1—N2—H2C | 107.7 | C11—C14—H14A | 109.4 |
C14—N3—C6 | 111.5 (5) | N3—C14—H14A | 109.4 |
C14—N3—C5 | 107.9 (4) | C11—C14—H14B | 109.4 |
C6—N3—C5 | 109.0 (4) | N3—C14—H14B | 109.4 |
C14—N3—Ni1 | 108.3 (3) | H14A—C14—H14B | 108.0 |
C6—N3—Ni1 | 104.7 (3) | N8—C15—H15A | 109.5 |
C5—N3—Ni1 | 115.5 (4) | N8—C15—H15B | 109.5 |
C8—N4—C7 | 112.2 (5) | H15A—C15—H15B | 109.5 |
C8—N4—Ni1 | 115.8 (3) | N8—C15—H15C | 109.5 |
C7—N4—Ni1 | 105.6 (3) | H15A—C15—H15C | 109.5 |
C8—N4—H4C | 107.6 | H15B—C15—H15C | 109.5 |
C7—N4—H4C | 107.6 | N6—C16—N7 | 111.7 (5) |
Ni1—N4—H4C | 107.6 | N6—C16—C19 | 123.4 (4) |
C11—N5—C13 | 105.9 (4) | N7—C16—C19 | 124.8 (5) |
C11—N5—Ni1 | 111.4 (3) | C18—C17—N7 | 107.5 (5) |
C13—N5—Ni1 | 142.1 (4) | C18—C17—H17 | 126.3 |
C16—N6—C18 | 105.7 (5) | N7—C17—H17 | 126.3 |
C16—N6—Ni1 | 111.3 (3) | C17—C18—N6 | 109.1 (6) |
C18—N6—Ni1 | 142.9 (4) | C17—C18—H18 | 125.5 |
C16—N7—C17 | 106.1 (5) | N6—C18—H18 | 125.5 |
C16—N7—C20 | 127.7 (6) | C16—C19—N1 | 110.7 (4) |
C17—N7—C20 | 126.2 (6) | C16—C19—H19A | 109.5 |
C11—N8—C12 | 106.7 (5) | N1—C19—H19A | 109.5 |
C11—N8—C15 | 126.0 (6) | C16—C19—H19B | 109.5 |
C12—N8—C15 | 127.3 (6) | N1—C19—H19B | 109.5 |
N1—C1—C2 | 111.9 (4) | H19A—C19—H19B | 108.1 |
N1—C1—H1A | 109.2 | N7—C20—H20A | 109.5 |
C2—C1—H1A | 109.2 | N7—C20—H20B | 109.5 |
N1—C1—H1B | 109.2 | H20A—C20—H20B | 109.5 |
C2—C1—H1B | 109.2 | N7—C20—H20C | 109.5 |
H1A—C1—H1B | 107.9 | H20A—C20—H20C | 109.5 |
N2—C2—C1 | 108.8 (4) | H20B—C20—H20C | 109.5 |
N2—C2—H2A | 109.9 | O21A—Cl1—O31A | 111.2 (7) |
C1—C2—H2A | 109.9 | O41B—Cl1—O31B | 109.1 (11) |
N2—C2—H2B | 109.9 | O41B—Cl1—O11 | 125.1 (10) |
C1—C2—H2B | 109.9 | O41C—Cl1—O11 | 117.4 (9) |
H2A—C2—H2B | 108.3 | O21A—Cl1—O11 | 105.5 (7) |
N2—C3—C4 | 112.5 (5) | O31A—Cl1—O11 | 107.7 (7) |
N2—C3—H3A | 109.1 | O31B—Cl1—O11 | 111.1 (9) |
C4—C3—H3A | 109.1 | O41C—Cl1—O21C | 109.6 (10) |
N2—C3—H3B | 109.1 | O11—Cl1—O21C | 108.6 (8) |
C4—C3—H3B | 109.1 | O41C—Cl1—O31C | 108.8 (10) |
H3A—C3—H3B | 107.8 | O11—Cl1—O31C | 103.8 (7) |
C5—C4—C3 | 114.7 (5) | O21C—Cl1—O31C | 108.1 (8) |
C5—C4—H4A | 108.6 | O21A—Cl1—O41A | 117.8 (8) |
C3—C4—H4A | 108.6 | O31A—Cl1—O41A | 114.5 (7) |
C5—C4—H4B | 108.6 | O11—Cl1—O41A | 98.4 (7) |
C3—C4—H4B | 108.6 | O41B—Cl1—O21B | 103.5 (10) |
H4A—C4—H4B | 107.6 | O31B—Cl1—O21B | 105.8 (8) |
N3—C5—C4 | 116.0 (5) | O11—Cl1—O21B | 100.0 (7) |
N3—C5—H5A | 108.3 | O22B—Cl2—O42B | 118.5 (9) |
C4—C5—H5A | 108.3 | O22B—Cl2—O12 | 106.9 (7) |
N3—C5—H5B | 108.3 | O42B—Cl2—O12 | 113.0 (8) |
C4—C5—H5B | 108.3 | O12—Cl2—O22C | 115.1 (11) |
H5A—C5—H5B | 107.4 | O12—Cl2—O42A | 119.0 (8) |
N3—C6—C7 | 110.6 (4) | O12—Cl2—O32A | 118.2 (7) |
N3—C6—H6A | 109.5 | O42A—Cl2—O32A | 107.5 (8) |
C7—C6—H6A | 109.5 | O12—Cl2—O32C | 112.4 (9) |
N3—C6—H6B | 109.5 | O22C—Cl2—O32C | 109.7 (11) |
C7—C6—H6B | 109.5 | O22B—Cl2—O32B | 109.6 (8) |
H6A—C6—H6B | 108.1 | O42B—Cl2—O32B | 109.8 (7) |
N4—C7—C6 | 108.7 (5) | O12—Cl2—O32B | 96.8 (6) |
N4—C7—H7A | 110.0 | O12—Cl2—O42C | 104.5 (10) |
C6—C7—H7A | 110.0 | O22C—Cl2—O42C | 109.3 (15) |
N4—C7—H7B | 110.0 | O32C—Cl2—O42C | 105.3 (13) |
C6—C7—H7B | 110.0 | O12—Cl2—O22A | 104.7 (5) |
H7A—C7—H7B | 108.3 | O42A—Cl2—O22A | 101.7 (8) |
N4—C8—C9 | 111.9 (5) | O32A—Cl2—O22A | 103.0 (7) |
N4—C8—H8A | 109.2 |
Experimental details
(1) | (2) | (3) | (4) | |
Crystal data | ||||
Chemical formula | [Ni(C15H30N6)(H2O)](ClO4)2·H2O | [Ni(C15H30N6)(H2O)](ClO4)2 | [Ni(ClO4)(C15H30N6)]ClO4 | [Ni(C20H36N6)](ClO4)2·0.24H2O |
Mr | 588.09 | 570.08 | 552.06 | 650.50 |
Crystal system, space group | Monoclinic, P21/c | Orthorhombic, P212121 | Monoclinic, P21/c | Orthorhombic, Pbca |
Temperature (K) | 294 | 294 | 294 | 294 |
a, b, c (Å) | 14.596 (3), 10.995 (2), 16.192 (3) | 9.428 (5), 16.047 (5), 16.060 (5) | 16.665 (5), 9.696 (5), 13.936 (5) | 13.7285 (12), 19.2330 (18), 21.171 (2) |
α, β, γ (°) | 90, 107.96 (3), 90 | 90, 90, 90 | 90, 92.849 (5), 90 | 90, 90, 90 |
V (Å3) | 2471.9 (9) | 2429.7 (17) | 2249.0 (16) | 5589.9 (9) |
Z | 4 | 4 | 4 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 1.06 | 1.08 | 1.16 | 0.95 |
Crystal size (mm) | 0.18 × 0.16 × 0.12 | 0.32 × 0.30 × 0.20 | 0.12 × 0.12 × 0.10 | 0.22 × 0.16 × 0.16 |
Data collection | ||||
Diffractometer | Oxford Gemini CCD S Ultra diffractometer | Oxford Gemini CCD S Ultra diffractometer | Oxford Gemini CCD S Ultra diffractometer | Oxford Gemini CCD S Ultra diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) |
Tmin, Tmax | 0.98, 0.99 | 0.98, 0.99 | 0.98, 0.99 | 0.98, 0.99 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8284, 4852, 2770 | 8056, 4312, 3342 | 23451, 4403, 2878 | 40257, 5489, 3936 |
Rint | 0.077 | 0.049 | 0.051 | 0.053 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 | 0.617 | 0.617 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.136, 1.23 | 0.059, 0.153, 1.07 | 0.037, 0.092, 0.90 | 0.064, 0.151, 1.08 |
No. of reflections | 4852 | 4312 | 4403 | 5489 |
No. of parameters | 362 | 362 | 356 | 479 |
No. of restraints | 452 | 720 | 732 | 934 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.91 | 0.58, −0.37 | 0.92, −0.26 | 0.49, −0.27 |
Absolute structure | ? | Flack (1983), 1601 Friedel pairs | ? | ? |
Absolute structure parameter | ? | 0.14 (3) | ? | ? |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O32Ai | 0.91 | 2.37 | 3.198 (13) | 151.0 |
N3—H3···O12 | 0.91 | 2.17 | 3.053 (8) | 162.4 |
O1W—H1WA···O2W | 0.85 | 1.99 | 2.790 (7) | 155.7 |
O1W—H1WB···O22B | 0.85 | 2.19 | 3.041 (15) | 176.1 |
O1W—H1WB···O22A | 0.85 | 2.38 | 3.163 (15) | 153.4 |
O2W—H2WA···O11ii | 0.85 | 2.18 | 3.034 (11) | 179.0 |
O2W—H2WB···O21B | 0.85 | 2.26 | 3.107 (19) | 174.9 |
O2W—H2WB···O21A | 0.85 | 2.01 | 2.855 (18) | 174.0 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O11 | 0.91 | 2.32 | 3.140 (9) | 149.7 |
N4—H4···O42A | 0.91 | 2.16 | 3.068 (15) | 173.4 |
N4—H4···O42B | 0.91 | 2.24 | 3.12 (2) | 161.4 |
O1W—H1WA···O12i | 0.846 (12) | 2.29 (3) | 3.098 (10) | 161 (7) |
O1W—H1WB···O31B | 0.846 (12) | 2.04 (4) | 2.86 (2) | 163 (9) |
O1W—H1WB···O31A | 0.846 (12) | 2.06 (7) | 2.740 (13) | 137 (8) |
Symmetry code: (i) −x+1, y+1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O21B | 0.91 | 2.29 | 3.140 (13) | 154.9 |
N4—H4···O12B | 0.91 | 2.15 | 3.035 (14) | 164.6 |
N4—H4···O12A | 0.91 | 2.15 | 2.997 (15) | 154.1 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2C···O12 | 0.91 | 2.27 | 3.123 (8) | 156 |
(1) | (2) | (3) | (4) | |
Ni1—N1 | 2.120 (5) | 2.144 (6) | 2.124 (3) | 2.144 (3) |
Ni1—N2 | 2.071 (5) | 2.085 (6) | 2.059 (3) | 2.098 (3) |
Ni1—N3 | 2.068 (5) | 2.094 (6) | 2.068 (3) | 2.144 (3) |
Ni1—N4 | 2.073 (5) | 2.088 (6) | 2.046 (3) | 2.099 (3) |
Ni1—N5 | 2.083 (5) | 2.051 (6) | 2.077 (3) | 2.068 (3) |
Ni1—X | 2.268 (4) | 2.222 (6) | 2.359 (3) | 2.073 (3) |
N1—Ni1—N2 | 85.7 (2) | 92.7 (2) | 85.85 (11) | 83.84 (12) |
N1—Ni1—N3 | 178.4 (2) | 173.9 (2) | 176.57 (12) | 174.60 (12) |
N1—Ni1—N4 | 95.0 (2) | 84.6 (2) | 95.69 (12) | 92.39 (12) |
N1—Ni1—N5 | 81.2 (2) | 81.9 (2) | 82.30 (11) | 102.34 (11) |
N1—Ni1—X | 90.92 (18) | 92.6 (2) | 86.83 (10) | 81.60 (11) |
N2—Ni1—N3 | 94.4 (2) | 83.5 (2) | 92.83 (12) | 92.52 (12) |
N2—Ni1—N4 | 175.0 (2) | 97.6 (2) | 169.98 (12) | 96.10 (13) |
N2—Ni1—N5 | 92.4 (2) | 169.5 (3) | 95.16 (11) | 171.31 (12) |
N2—Ni1—X | 84.89 (18) | 85.9 (2) | 84.06 (11) | 88.20 (12) |
N3—Ni1—N4 | 84.8 (2) | 91.2 (2) | 85.07 (13) | 84.01 (13) |
N3—Ni1—N5 | 100.3 (2) | 102.6 (2) | 100.98 (11) | 81.72 (12) |
N3—Ni1—X | 87.54 (18) | 91.8 (2) | 89.89 (11) | 102.32 (13) |
N4—Ni1—N5 | 92.5 (2) | 90.9 (3) | 94.86 (11) | 89.80 (12) |
N4—Ni1—X | 90.17 (19) | 175.6 (2) | 86.15 (12) | 172.22 (13) |
N5—Ni1—X | 171.89 (19) | 85.3 (2) | 169.13 (10) | 86.69 (11) |
(*) Atom X is O1W for (1) and (2), O11 for (3) and N6 for (4). |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Macrocyclic polyamines such as cyclam and cyclen, bearing potentially coordinating pendant arms, are useful in applications such as diagnostic medicine, waste-water treatment and others, due to the stability conferred on their metallic complexes by the additional donor groups in the pendant arms. This stability is especially important in processes where the release of free metals is particularly undesirable, as in, for instance, the majority of medical treatments. A paradigmatic example can be found in the administration of the gadolinium cation as a contrast agent for magnetic resonance imaging (MRI), a process where the stability of the tetraacetate cyclen (DOTA) complex of the GdIII cation, viz. Gd(DOTA)H2O, has made the complex, and some of its derivatives, a `must' for the safe and successful use of the technique.
Complexes of substituted macrocyclic polyamines are also interesting from a purely structural point of view, in particular due to the many different ring conformations attainable, as well as the diversity in binding modes provided by the functionalized side arms.
There are a large number of reported ligands of this type, with a wide range of pendant side groups, and consistent with the above-mentioned stability, the majority of their complexes are clathrates [Cambridge Structural Database (CSD), Version?; Allen, 2002].
Exploring further the substantial body of chemistry already based on the cyclam macrocycle, we have prepared a new cyclam–methylimidazole ligand, 1-[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11-tetraazacyclotetradecane (LIm1). Crystallizing the free ligand has proved impossible so far. However, we succeeded in obtaining the trans and cis isomers of an NiII complex, viz. trans-[Ni(LIm1)(H2O)](ClO4)2.H2O, (1), and trans-[Ni(LIm1)(H2O)](ClO4)2, (2), reported herein. At different stages of the crystallization and thermal treatment processes (see Experimental for details), another two compounds were obtained in crystalline form and their structures are also reported here, viz. trans-[Ni(ClO4)(LIm1)]ClO4, (3), and cis-[Ni(LIm2)](ClO4)2, (4) (where LIm2 is 1,8-bis[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11-tetraazacyclotetradecane, a minor side product probably formed in trace amounts in the synthesis of LIm1).
The structures of (1)–(4) (Figs. 1–4) all have a central NiII cation chelated by a cyclam ring (four N atoms), the common fifth ligand being the imidazole N atom. They differ in the sixth ligand completing the octahedral coordination of atom Ni1, this being water in (1) and (2), a perchlorate anion in (3) and a second imidazole N atom in (4). All four structures present perchlorate groups as either isolated counterions or a coordinated ligand, and invariably this fragment is disordered, as a result of which the quality of the refinement is in most cases diminished.
Chelation of the NiII cation by the four cyclic N atoms of the cyclam unit is achieved in two different fashions in these compounds, which can be described by the relative orientations of the Ni1/N1–N3 and Ni1/N1/N4/N3 mean planes. The dihedral angles are 3.9 (2) and 7.7 (2)° in (1) and (3), respectively, describing a fairly planar arrangement of the cyclam macrocycle, and 79.6 (2) and 81.5 (2)° in (2) and (4), respectively, describing a `butterfly-like' conformation. This is closely associated with the way the two extra ligands bind the cation, viz. trans in (1) and (3), and cis in (2) and (4). The similarities and differences in the coordination parameters are related to these differences in ligand conformation, as well as to the character of the sixth ligand, as reflected in the comparison of the geometric data given in Table 1. The bond angles are split into two groups, those in the first and third column of Table 1 (the `trans' moieties), and those in the second and fourth columns (`cis'), with the differences within each group being smaller than those between groups. The Ni—N bond distances fall between 2.046 (3) and 2.144 (3) Å, in the range expected for high-spin NiII—N bonds.
As described by Bonisch et al. (1965), the designation `trans' does not fully characterize these complexes since the cyclic ligand has a number of possible distinct configurations. Bonisch and co-workers analysed the principles which apply to any cyclic tetradentate ligand whose donor atoms are tetrahedral when coordinated, and concluded that, in the case of cyclam, each N atom when coordinated is an asymmetric centre. Five distinct non-enantiomeric combinations can be produced. Thus, they proposed a simple description of the five different possible configurations of a cyclam macrocycle upon chelation (named I to V in their paper) by stating the directions, either up (u) or down (d), which the N substituents adopt (in our case, either H atoms or the methylimidazole arm). According to this classification, in (1) and (3) the group adopts a trans type III configuration (see Scheme 2), while in (2) and (4) it prefers the cis form described by Bonisch and co-workers as V.
Similar NiII complexes with closely related monosusbtituted cyclam derivatives have been reported in the literature. El Ghachtouli et al. (2006) described two structures, (II) and (III) therein, having 2-methylpyridine as a pendant arm and CH3N [CH3CN?] and H2O, respectively, occupying the sixth coordination sites, and which present coordination analogous to that of (1) and (2). But while their compound (III) shares with our (2) the same cis-V cyclam configuration (Bonisch classification), compound (II) of El Ghachtouli and co-workers adopts a trans-I configuration (all up, see Scheme 2). A search of the CSD shows that the configuration found in (1) occurs slightly more frequently than that displayed by (II), appearing with a 60:40 relative frequency.
The disordered perchlorate groups, in addition to providing charge balance, act as acceptors in generally weak hydrogen bonds having the cyclam N—H and water O—H groups as donors (Tables 2–5). The result is an arrangement with the Ni–cyclam units isolated from each other in space but interconnected by a dense network of these perchlorate-mediated interactions.
The redox behaviour of the configurational isomers (1) and (2) was investigated in aqueous solution by means of cyclic voltammetry experiments. The oxidation of the trans isomer, (1), is quasi-reversible and occurs at E1/2 = 0.77 V. In contrast, and analogous with what is observed in the closely related derivatives reported by El Ghachtouli et al. (2006), the oxidation of the cis isomer, (2), is irreversible (Eox = 1.03 V) and after several scans leads to the exclusive formation of (1).