Four Ni^II complexes with the new cyclam-methyl­imidazole ligand 1-[(1-methyl-1H-imidazol-2-yl)meth­yl]-1,4,8,11-tetra­aza­cyclo­tetra­deca­ne

Although it has not proved possible to crystallize the newly prepared cyclam-methyl­imidazole ligand 1-[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11-tetra­aza­cyclo­tetra­decane (L^Im1), the trans and cis isomers of an Ni^II complex, namely trans-aqua­{1-[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11-tetra­aza­cyclo­tetra­decane}nickel(II) bis­(perchlorate) mono­hydrate, [Ni(C₁₅H₃₀N₆)(H₂O)](ClO₄)₂·H₂O, (1), and cis-aqua­{1-[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11-tetraaza­cyclo­tetra­decane}nickel(II) bis­(perchlorate), [Ni(C₁₅H₃₀N₆)(H₂O)](ClO₄)₂, (2), have been prepared and structurally characterized. At different stages of the crystallization and thermal treatment from which (1) and (2) were obtained, a further two compounds were isolated in crystalline form and their structures also analysed, namely trans-{1-[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11-tetra­aza­cyclo­tetra­decane}(perchlorato)nickel(II) perchlorate, [Ni(ClO₄)(C₁₅H₃₀N₆)]ClO₄, (3), and cis-{1,8-bis­[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11-tetra­aza­cyclo­tetra­decane}nickel(II) bis­(perchlorate) 0.24-hy­drate, [Ni(C₂₀H₃₆N₆)](ClO₄)₂·0.24H₂O, (4); the 1,8-bis­[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11-tetra­azacyclo­tetra­decane ligand is a minor side product, probably formed in trace amounts in the synthesis of L^Im1. The configurations of the cyclam macrocycles in the complexes have been analysed and the structures are compared with analogues from the literature.

S1. Comment

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 Gd^III 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 (L^Im1). Crystallizing the free ligand has proved impossible so far. However, we succeeded in obtaining the trans and cis isomers of an Ni^II complex, viz. trans-[Ni(L^Im1)(H₂O)](ClO₄)₂.H₂O, (1), and trans-[Ni(L^Im1)(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)(L^Im1)]ClO₄, (3), and cis-[Ni(L^Im2)](ClO₄)₂, (4) (where L^Im2 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 L^Im1).

The structures of (1)–(4) (Figs. 1–4) all have a central Ni^II 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 Ni^II 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 Ni^II—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 Ni^II 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 E_1/2 = 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 (E_ox = 1.03 V) and after several scans leads to the exclusive formation of (1).

Related literature

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).

S2. Experimental

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 (L^Im1), 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, L^Im1.

For the synthesis of [Ni(L^Im1)(H₂O)](ClO₄)₂, L^Im1 (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(L^Im1)(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(L^Im1)(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(L^Im2)](ClO₄)₂, (4), where L^Im2 is a minor side product, probably formed in trace amounts in the synthesis of L^Im1. Further evaporation of the mother liquors finally gave another pink crystalline solid which was identified by X-ray diffraction as the trans-[Ni(L^Im1)(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(L^Im1)(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)(L^Im1)]ClO₄, (3).

S3. Refinement

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 U_iso(H) = 1.2U_eq(host) [or 1.5U_eq(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 R_int values indicate unequivocally that the diffraction pattern has orthorhombic symmetry [R_int(tetragonal 4/m) 0.31; R_int(tetragonal 4/mmm) 0.41; R_int(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).

Computing details

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).

Figures

	Fig. 1. The molecular structure of (1), with displacement ellipsoids drawn at the 35% probability level. The major components of the disordered perchlorate anions are shown with broken lines. The minor component(s) and H atoms have been omitted for clarity.
	Fig. 2. The molecular structure of (2), with displacement ellipsoids drawn at the 35% probability level. The major components of the disordered perchlorate anions are shown with broken lines. The minor component(s) and H atoms have been omitted for clarity.
	Fig. 3. The molecular structure of (3), with displacement ellipsoids drawn at the 35% probability level. The major components of the disordered perchlorate anions are shown with broken lines. The minor component(s) and H atoms have been omitted for clarity.
	Fig. 4. The molecular structure of (4), with displacement ellipsoids drawn at the 35% probability level. The major components of the disordered perchlorate anions are shown with broken lines. The minor component(s) and H atoms have been omitted for clarity.

(1) trans-aqua{1-[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11- tetraazacyclotetradecane}nickel(II) bis(perchlorate) monohydrate

Crystal data

[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) Å^3	0.18 × 0.16 × 0.12 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.136	H-atom parameters constrained
S = 1.23	w = 1/[σ^2(Fo^2) + 8.9604P] where P = (Fo^2 + 2Fc^2)/3
4852 reflections	(Δ/σ)max < 0.001
362 parameters	Δρmax = 0.51 e Å^−3
452 restraints	Δρmin = −0.91 e Å^−3

Special details

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, L^Im1, δ_H (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, δ_C (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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O32A^i	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···O11^ii	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.

(2) cis-aqua{1-[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11- tetraazacyclotetradecane}nickel(II) bis(perchlorate)

Crystal data

[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) Å^3	Prism, light pink
Z = 4	0.32 × 0.30 × 0.20 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.153	w = 1/[σ^2(Fo^2) + (0.0553P)^2 + 0.3459P] where P = (Fo^2 + 2Fc^2)/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)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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···O12^i	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.

(3) trans-{1-[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11- tetraazacyclotetradecane}(perchlorato)nickel(II) perchlorate

Crystal data

[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) Å^3	0.12 × 0.12 × 0.10 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H-atom parameters constrained
S = 0.90	w = 1/[σ^2(Fo^2) + (0.0541P)^2] where P = (Fo^2 + 2Fc^2)/3
4403 reflections	(Δ/σ)max < 0.001
356 parameters	Δρmax = 0.92 e Å^−3
732 restraints	Δρmin = −0.26 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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

(4) cis-{1,8-bis[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11- tetraazacyclotetradecane}nickel(II) bis(perchlorate) 0.24-hydrate

Crystal data

[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) Å^3	Prism, light pink
Z = 8	0.22 × 0.16 × 0.16 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.151	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.067P)^2 + 4.2236P] where P = (Fo^2 + 2Fc^2)/3
5489 reflections	(Δ/σ)max = 0.001
479 parameters	Δρmax = 0.49 e Å^−3
934 restraints	Δρmin = −0.27 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O12	0.91	2.27	3.123 (8)	156