Crystal structure and Hirshfeld surface analysis of tris-(2,2'-bi-pyridine)-nickel(II) bis-(1,1,3,3-tetra-cyano-2-eth-oxy-propenide) dihydrate.

The title compound, [Ni(C10H8N2)3](C9H5N4O)2·2H2O, crystallizes as a racemic mixture in the monoclinic space group C2/c. In the crystal, the 1,1,3,3-tetracyano-2-ethoxypropenide anions and the water molecules are linked by O-H⋯N hydrogen bonds, forming chains running along the [010] direction. The bpy ligands of the cation are linked to the chain via C-H⋯π(cation) inter-actions involving the CH3 group. The inter-molecular inter-actions were investigated by Hirshfeld surface analysis and two-dimensional fingerprint plots.

Chemical context

The use of polynitrile anions as ligands, either alone or in combination with neutral co-ligands, is a very promising and appealing strategy to obtain mol­ecular architectures with different topologies and dimensionalities owing to their ability to coordinate and bridge metal ions in many different ways (Miyazaki et al., 2003 ▸; Atmani et al., 2008 ▸; Benmansour et al., 2007 ▸, 2008 ▸; Yuste et al., 2009 ▸; Gaamoune et al., 2010 ▸; Addala et al., 2015 ▸; Setifi et al., 2010 ▸, 2013a ▸,b ▸, 2014a ▸,b ▸, 2015 ▸, 2016 ▸, 2017 ▸). The presence of several potentially coordinating nitrile groups, their rigidity and their electronic delocalization, allows the synthesis of original magnetic high-dimensional coordination polymers with transition-metal ions (Benmansour et al., 2010 ▸).

In view of the possible roles of these versatile polynitrile ligands, we have been inter­ested in using them in combination with other chelating or bridging neutral co-ligands to explore their structural and electronic characteristics in the field of mol­ecular materials exhibiting inter­esting magnetic exchange coupling. During the course of attempts to prepare such complexes with 2,2-dipyridyl, we isolated the title compound, whose structure is described herein along with the Hirshfeld surface analysis.

Structural commentary

The asymmetric unit of the title compound comprises a half of [Ni(bpy)3]2+ cation, one (tcnoet)− anion and a solvent water mol­ecule within the monoclinic C2/c-centred cell (Fig. 1 ▸). In addition, this compound crystallizes presenting Δ and Λ chiral configurations and related to each other by inversion, forming a racemic mixture as illustrated in Fig. 2 ▸; this compound is isostructural to Fe(bpy)3(tcnoet)2(2H2O) (Setifi et al., 2014c ▸). The Ni atom is located on the Wyckoff position 4e on the twofold axis. The [Ni(bpy)3]2+ complex presents a slightly distorted octa­hedral geometry of C 2 point-group symmetry (Table 1 ▸). The Ni—N bond lengths are very similar to each other, being in the range 2.077 (3)–2.090 (3) Å, which is in agreement with the Ni—N distances for other [Ni(bpy)3]2+ complexes reported in the literature (Freire et al., 2000 ▸; Su et al., 2007 ▸; Yang et al., 1998 ▸). In addition, the Ni—N distances are slightly longer than the Fe—N bonds [Fe(bpy)3]2+ [1.971 (2)–1.972 (2) Å] because of the larger Ni2+ radius compared to Fe2+ in a low-spin configuration (Shannon & Prewitt, 1969 ▸). The distorted N—Ni—N angles of the chelating bi­pyridine ligands [78.26 (16)–78.64 (12)°] are significantly less than 90°, as is usually found for [Ni(bpy)3]2+ complexes (Freire et al., 2000 ▸; Yang et al., 1998 ▸).

Figure 1

Mol­ecular structure of the title compound, showing the atom labeling and displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms on the [Ni(bpy)3]2+ cation and (tcnoet)− were omitted for clarity. Symmetry code: (i) 1 − x, y,  − z.

Figure 2

Disposition of Δ (red) and Λ (blue) stereoisomers in the unit cell.

Table 1

Selected geometric parameters (Å, °)

Ni—N2	2.077 (3)	Ni—N3	2.090 (3)
Ni—N1	2.088 (3)
N1—Ni—N2	78.64 (12)	N2—Ni—N3	92.87 (11)
N1i—Ni—N2	93.73 (11)	N1—Ni—N3	95.55 (11)
N1—Ni—N1i	91.20 (16)	N2—Ni—N3i	95.52 (11)
N1—Ni—N3i	171.36 (11)	N3—Ni—N3i	78.26 (16)
N2—Ni—N2i	169.18 (16)

Symmetry code: (i) .

Supra­molecular features

As shown in Fig. 2 ▸, there are four [Ni(bpy)3]2+ cationic units within the unit cell of the compound, charge-balancing the1,1,3,3-tetra­cyano-2-eth­oxy­propenide anions. These, together with the hydration water, define planar and zigzag hydrogen-bonded chains, in which anions and water mol­ecules alternate, running along the [010] direction, as shown in Fig. 3 ▸. The O(water)—H⋯N(cyano) hydrogen-bonding inter­actions (Table 2 ▸) define the chain, with H⋯N distances of 2.11 and 2.10 Å. Finally, a C—H⋯π inter­action between the CH3 group of the (tcnoet)− anion and the bpy ligand is observed, with a H⋯centroid distance of 3.01 Å (Table 2 ▸).

Figure 3

Partial crystal packing diagram showing the alternating zigzag (tcnoet)−–water chains defined by O—H⋯N hydrogen bonds running along the [010] direction. Symmetry code: (ii) −x + , y − , −z + .

Table 2

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N2/C6–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H25⋯N5	0.86	2.11	2.945 (5)	164
O2—H26⋯N4ii	0.86	2.10	2.955 (5)	175
C24—H24A⋯Cg1iii	0.98	3.01	3.921	156

Symmetry codes: (ii) ; (iii) .

Hirshfeld surface analysis

The fingerprint plots (Fig. 4 ▸) of the inter­molecular contacts were computed using program CrystalExplorer (McKinnon et al., 2007 ▸; Wolff et al., 2012 ▸). The short contacts spikes are due to the N⋯H hydrogen bonds (outer spikes) and to the Ni⋯N coordination bonds (inner spikes).

Figure 4

Hirshfeld surface fingerprint plot for the title compound showing the C⋯C, C⋯H, H⋯O, H⋯H, H⋯N and Ni⋯N contacts in detail.

The proportions of the different contacts and their enrichment (Jelsch et al., 2014 ▸; Table 3 ▸) were computed with program MoProViewer (Guillot et al., 2014 ▸). The enrichment ratios E y are obtained from the actual contacts between the different chemical species (x, y) and equi-probable proportions computed from the surface chemical content (Jelsch et al., 2014 ▸). They allow contacts that are favored (over-represented) and which are likely to be the crystal driving force to be highlighted.

Table 3

Nature of inter­molecular contacts on the Hirshfeld surface by chemical type

The top part of the table gives the contribution S of each chemical type X to the Hirshfeld surface. The chemical types are grouped as hydro­phobic (C, Hc) and charged (N, Ho, O) atoms. The next part shows the percentage contributions C of the actual contact types to the surface. The lower part of the table shows the E contact enrichment ratios. The major C contact types and the E ratios much larger than unity (enriched contacts) are highlighted in bold. The hydro­phobic Hc atoms bound to carbon are distinguished from the more polar Ho water hydrogen atoms.

Atom type	Ho	O	N	Hc	C
Surface (%)	5.3	4.5	16.5	38.0	35.7
Ho	0.0
O	0.0	0.0
Contacts (%)
N	5.0	0.0	0.0
Hc	4.7	6.1	20.9	7.5
C	1.9	3.0	8.5	27.8	14.7
Ho	0.0
O	0.0	0.0
Enrichment
N	2.5	0.0	0.0
Hc	1.1	1.8	1.6	0.54
C	0.47	0.92	0.7	1.06	1.2

The Hirshfeld surface was computed for all the entities present in the crystal – the (tcnoet)− anion, the [Ni(bpy)3]2+ complex and the water mol­ecule – in order to analyze the crystal contacts. Moieties not in contact with each other were selected in the crystal packing in order to obtain integral surfaces.

The nickel cation does not contribute to the mol­ecular surface, as it is coordinated by six nitro­gen atoms within the [Ni(bpy)3]2+ complex. Nearly three quarters of the Hirshfeld surface is of hydro­phobic in nature, constituted by atoms C and Hc. The most abundant contact is of the C⋯Hc type as a result of the extensive C—H⋯π inter­actions involving the aromatic rings. The second major contact is N⋯Hc, which is due to the abundance of the N and Hc chemical types and to the significant enrichment of this favorable weak hydrogen bond. The third major contact is of the C⋯C type and is due to stacking between the [Ni(bpy)3]2+ aromatic rings and the C(C(C≡N)2)2 group of the (tcnoet)− anion.

The other significantly over-represented contacts are the strong hydrogen bonds N⋯H—O (E = 2.5) between the water mol­ecule and two nitrile groups. These are the hydrogen bonds with shortest distance d(N5⋯H25) = 2.11 Å and d(N4⋯H26) = 2.10 Å (Table 1 ▸). There is a deficit of strong hydrogen-bond donors compared to acceptors in this crystal structure. As a result, weak hydrogen bonds to H—C groups are formed. N⋯H—C weak hydrogen bonds occur and are slightly enriched. The oxygen atoms form only weak O⋯H—C hydrogen bonds, which are quite favored at E = 1.8. Globally there are two O—H⋯N strong hydrogen bonds, six C—H⋯N and two C—H⋯O weak hydrogen bonds (Table 2 ▸). The two major hydro­phobic contacts, C⋯Hc and C⋯C, are both slightly enriched. If all hydro­phobic contacts (within C and Hc atoms) are considered together, they are globally slightly under-represented with an enrichment ratio E = 0.92 because of the avoidance of the less favorable Hc⋯Hc contacts. All contacts between charged atoms (O, Ho, N) are absent except for the attractive N⋯Ho hydrogen bond. The cross hydro­philic/hydro­phobic contacts are slightly over-represented at E = 1.16 because of the occurrence of many weak O⋯Hc and N⋯Hc hydrogen bonds, which result from an unbalanced number of strong hydrogen-bond acceptors versus donors.

Database survey

The Cambridge Structural Database (CSD, Version 5.39, update August 2018, Groom et al., 2016 ▸) includes a few structures involving polycyano­propide counter-ions, of which only 16 entries are hexa­cyano derivatives and four have (tcnoet)− anions. There are no significant differences in C—N and C—C bond lengths between the hexa­cyano derivatives and (tcnoet)− anions. However, the C21—C20—C16—C17 torsion angles in (tcnoet)− anion (15.78°) are slightly smaller than the analogous torsion angle in other anions (16.32–21.68°). This difference can be explained by this compound and its isostructural structure featuring two hydrogen bonds, O2—H25⋯N5 and O2—H25⋯N4ii. These inter­actions orient the cyano groups toward to coplanarity with respect to other (tcnoet)− mol­ecules that exhibit fewer hydrogen bonds. Finally, this compound has been used for the synthesis of low-dimensional metal–organic frameworks employing MnII, CuII, CoII and FeII ions because the half cyano groups inter­act by hydrogen bonding with the metal aqua complexes, avoiding the formation of high-dimensional frameworks (Thétiot et al., 2003 ▸).

Synthesis and crystallization

The title compound was synthesized solvothermally under autogenous pressure from a mixture of Ni(NO3)2·6H2O (29 mg, 0.1 mmol), 2,2-dipyridyl (16 mg, 0.1 mmol) and K(tcnoet) (45 mg, 0.2 mmol) in water–ethanol (4:1 v/v, 20 cm−3). This mixture was sealed in a Teflon-lined autoclave and held at 423 K for three days, and then cooled to ambient temperature at a rate of 10 K h−1 (yield: 54%). Light-green blocks of the title compound suitable for single-crystal X-ray diffraction were selected directly from the synthesized product.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4 ▸. All H atoms were located in difference-Fourier maps. C-bound H atoms were then treated as riding atoms: C—H = 0.95 Å (aromatic), 0.98 Å (CH3) or 0.99 Å (CH2), and with U iso(H) = kU eq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all others. H atoms bonded to the water O atom were permitted to ride at the positions located in the difference map, with U iso(H) = 1.5U eq(O).

Table 4

Experimental details

Crystal data
Chemical formula	[Ni(C10H8N2)3](C9H5N4O)2·2H2O
M r	933.63
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	162
a, b, c (Å)	20.345 (3), 12.439 (3), 19.575 (4)
β (°)	112.800 (9)
V (Å3)	4566.8 (17)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.49
Crystal size (mm)	0.17 × 0.14 × 0.07
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 ▸)
T min, T max	0.683, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	22477, 4670, 2483
R int	0.108
(sin θ/λ)max (Å−1)	0.627
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.061, 0.125, 1.00
No. of reflections	4670
No. of parameters	310
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.36, −0.40

Computer programs: APEX2 and SAINT (Bruker, 2012 ▸), SHELXS97 and SHELXTL (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019006959/mw2141sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019006959/mw2141Isup2.hkl

CCDC reference: 1915961

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Ni(C10H8N2)3](C9H5N4O)2·2H2O	F(000) = 1936
Mr = 933.63	Dx = 1.358 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.345 (3) Å	Cell parameters from 1400 reflections
b = 12.439 (3) Å	θ = 2.5–19.1°
c = 19.575 (4) Å	µ = 0.49 mm−1
β = 112.800 (9)°	T = 162 K
V = 4566.8 (17) Å3	Block, light green
Z = 4	0.17 × 0.14 × 0.07 mm

Bruker APEXII CCD diffractometer	2483 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.108
Absorption correction: multi-scan (SADABS; Bruker, 2012)	θmax = 26.5°, θmin = 2.0°
Tmin = 0.683, Tmax = 0.745	h = −25→22
22477 measured reflections	k = −12→15
4670 independent reflections	l = −24→24

Refinement on F2	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.061	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.125	w = 1/[σ2(Fo2) + (0.0372P)2 + 4.4221P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
4670 reflections	Δρmax = 0.36 e Å−3
310 parameters	Δρmin = −0.39 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
Ni	0.5000	0.13563 (5)	0.2500	0.0258 (2)
N1	0.44888 (16)	0.2530 (2)	0.28779 (16)	0.0277 (7)
N2	0.56997 (15)	0.1514 (2)	0.35984 (15)	0.0258 (7)
N3	0.44732 (16)	0.0053 (2)	0.27341 (15)	0.0251 (7)
C1	0.3878 (2)	0.3033 (3)	0.2479 (2)	0.0358 (10)
H1	0.3624	0.2810	0.1981	0.043*
C2	0.3600 (2)	0.3857 (3)	0.2755 (2)	0.0412 (11)
H2	0.3160	0.4185	0.2459	0.049*
C3	0.3976 (2)	0.4192 (3)	0.3472 (2)	0.0424 (11)
H3	0.3802	0.4766	0.3675	0.051*
C4	0.4604 (2)	0.3688 (3)	0.3890 (2)	0.0375 (10)
H4	0.4868	0.3911	0.4386	0.045*
C5	0.48510 (19)	0.2855 (3)	0.3585 (2)	0.0272 (9)
C6	0.55264 (19)	0.2279 (3)	0.3992 (2)	0.0250 (9)
C7	0.5973 (2)	0.2508 (3)	0.4718 (2)	0.0336 (10)
H7	0.5844	0.3045	0.4989	0.040*
C8	0.6604 (2)	0.1949 (3)	0.5044 (2)	0.0353 (10)
H8	0.6916	0.2097	0.5540	0.042*
C9	0.6777 (2)	0.1174 (3)	0.4641 (2)	0.0344 (10)
H9	0.7210	0.0784	0.4852	0.041*
C10	0.6310 (2)	0.0976 (3)	0.3927 (2)	0.0319 (10)
H10	0.6427	0.0430	0.3653	0.038*
C11	0.3952 (2)	0.0107 (3)	0.29930 (19)	0.0335 (10)
H11	0.3776	0.0795	0.3050	0.040*
C12	0.3661 (2)	−0.0790 (3)	0.3179 (2)	0.0380 (10)
H12	0.3289	−0.0720	0.3355	0.046*
C13	0.3915 (2)	−0.1782 (3)	0.3106 (2)	0.0391 (11)
H13	0.3732	−0.2411	0.3243	0.047*
C14	0.4440 (2)	−0.1851 (3)	0.2830 (2)	0.0354 (10)
H14	0.4618	−0.2533	0.2766	0.042*
C15	0.47114 (19)	−0.0920 (3)	0.26463 (18)	0.0273 (9)
N4	0.2358 (2)	0.9371 (3)	0.0957 (2)	0.0518 (10)
N5	0.25094 (19)	0.6205 (3)	0.1895 (2)	0.0578 (11)
N6	0.3282 (2)	0.4535 (3)	0.10158 (19)	0.0561 (11)
N7	0.5030 (2)	0.6277 (3)	0.07484 (19)	0.0488 (9)
O1	0.38199 (14)	0.8243 (2)	0.08018 (14)	0.0389 (7)
C16	0.3536 (2)	0.7331 (3)	0.0959 (2)	0.0341 (10)
C17	0.2966 (2)	0.7526 (3)	0.1182 (2)	0.0345 (10)
C18	0.2635 (2)	0.8550 (4)	0.1055 (2)	0.0385 (11)
C19	0.2720 (2)	0.6775 (4)	0.1570 (2)	0.0435 (11)
C20	0.3857 (2)	0.6355 (3)	0.0944 (2)	0.0378 (10)
C21	0.3536 (2)	0.5348 (4)	0.0987 (2)	0.0412 (11)
C22	0.4508 (2)	0.6307 (3)	0.0835 (2)	0.0379 (10)
C23	0.3802 (2)	0.8371 (3)	0.0057 (2)	0.0412 (11)
H23A	0.3362	0.8755	−0.0257	0.049*
H23B	0.3803	0.7657	−0.0166	0.049*
C24	0.4438 (2)	0.8993 (3)	0.0101 (2)	0.0489 (12)
H24A	0.4451	0.9676	0.0355	0.073*
H24B	0.4414	0.9136	−0.0400	0.073*
H24C	0.4870	0.8579	0.0377	0.073*
O2	0.2745 (2)	0.6530 (3)	0.3463 (2)	0.0829 (11)
H25	0.274 (3)	0.634 (4)	0.3041 (15)	0.099*
H26	0.271 (3)	0.592 (2)	0.365 (3)	0.099*

	U11	U22	U33	U12	U13	U23
Ni	0.0223 (4)	0.0255 (4)	0.0259 (4)	0.000	0.0053 (3)	0.000
N1	0.0243 (18)	0.0273 (18)	0.0285 (19)	0.0033 (16)	0.0070 (16)	0.0031 (15)
N2	0.0226 (17)	0.0255 (18)	0.0262 (17)	0.0024 (16)	0.0059 (15)	0.0002 (15)
N3	0.0239 (18)	0.0253 (18)	0.0218 (17)	−0.0001 (16)	0.0040 (15)	0.0005 (14)
C1	0.030 (2)	0.036 (2)	0.037 (2)	0.007 (2)	0.008 (2)	0.005 (2)
C2	0.034 (2)	0.039 (3)	0.052 (3)	0.013 (2)	0.018 (2)	0.007 (2)
C3	0.041 (3)	0.036 (3)	0.053 (3)	0.011 (2)	0.022 (2)	−0.005 (2)
C4	0.039 (3)	0.038 (2)	0.037 (2)	0.005 (2)	0.015 (2)	−0.004 (2)
C5	0.024 (2)	0.026 (2)	0.033 (2)	0.0029 (19)	0.0130 (19)	0.0025 (19)
C6	0.028 (2)	0.020 (2)	0.027 (2)	−0.0019 (18)	0.0105 (19)	0.0012 (17)
C7	0.036 (3)	0.035 (2)	0.030 (2)	0.003 (2)	0.013 (2)	−0.003 (2)
C8	0.032 (2)	0.041 (3)	0.024 (2)	−0.004 (2)	0.002 (2)	−0.001 (2)
C9	0.022 (2)	0.039 (3)	0.032 (2)	0.004 (2)	−0.0004 (19)	0.003 (2)
C10	0.025 (2)	0.032 (2)	0.033 (2)	0.003 (2)	0.005 (2)	−0.0005 (19)
C11	0.029 (2)	0.039 (3)	0.031 (2)	0.003 (2)	0.008 (2)	0.005 (2)
C12	0.027 (2)	0.045 (3)	0.038 (3)	−0.001 (2)	0.009 (2)	0.009 (2)
C13	0.034 (3)	0.036 (3)	0.038 (3)	−0.011 (2)	0.003 (2)	0.008 (2)
C14	0.036 (3)	0.031 (2)	0.032 (2)	−0.003 (2)	0.005 (2)	−0.001 (2)
C15	0.023 (2)	0.029 (2)	0.020 (2)	−0.0042 (19)	−0.0026 (17)	−0.0011 (17)
N4	0.048 (3)	0.047 (3)	0.067 (3)	−0.006 (2)	0.030 (2)	−0.003 (2)
N5	0.055 (3)	0.067 (3)	0.056 (3)	−0.010 (2)	0.027 (2)	0.013 (2)
N6	0.065 (3)	0.044 (2)	0.046 (2)	−0.021 (2)	0.007 (2)	−0.002 (2)
N7	0.051 (2)	0.043 (2)	0.053 (2)	0.003 (2)	0.020 (2)	−0.0022 (19)
O1	0.0416 (17)	0.0363 (17)	0.0430 (17)	−0.0162 (14)	0.0211 (14)	−0.0076 (13)
C16	0.035 (3)	0.037 (3)	0.022 (2)	−0.015 (2)	0.003 (2)	−0.0040 (19)
C17	0.031 (2)	0.035 (3)	0.031 (2)	−0.015 (2)	0.005 (2)	0.000 (2)
C18	0.033 (3)	0.049 (3)	0.035 (2)	−0.016 (3)	0.014 (2)	−0.002 (2)
C19	0.034 (3)	0.054 (3)	0.038 (3)	−0.013 (2)	0.008 (2)	−0.004 (2)
C20	0.043 (3)	0.035 (2)	0.034 (2)	−0.009 (3)	0.013 (2)	−0.004 (2)
C21	0.041 (3)	0.047 (3)	0.027 (2)	−0.008 (3)	0.002 (2)	−0.003 (2)
C22	0.050 (3)	0.031 (2)	0.029 (2)	−0.004 (3)	0.011 (2)	−0.003 (2)
C23	0.043 (3)	0.045 (3)	0.030 (2)	−0.006 (2)	0.008 (2)	0.003 (2)
C24	0.050 (3)	0.052 (3)	0.048 (3)	−0.010 (2)	0.023 (2)	0.002 (2)
O2	0.112 (3)	0.070 (3)	0.078 (3)	−0.017 (3)	0.049 (3)	−0.009 (2)

Ni—N2	2.077 (3)	C11—C12	1.376 (5)
Ni—N2i	2.077 (3)	C11—H11	0.9500
Ni—N1	2.088 (3)	C12—C13	1.366 (5)
Ni—N1i	2.088 (3)	C12—H12	0.9500
Ni—N3	2.090 (3)	C13—C14	1.373 (5)
Ni—N3i	2.090 (3)	C13—H13	0.9500
N1—C1	1.339 (4)	C14—C15	1.389 (5)
N1—C5	1.353 (4)	C14—H14	0.9500
N2—C10	1.335 (4)	C15—C15i	1.493 (7)
N2—C6	1.354 (4)	N4—C18	1.146 (5)
N3—C15	1.339 (4)	N5—C19	1.141 (5)
N3—C11	1.343 (4)	N6—C21	1.146 (5)
C1—C2	1.379 (5)	N7—C22	1.139 (5)
C1—H1	0.9500	O1—C16	1.361 (4)
C2—C3	1.376 (5)	O1—C23	1.453 (4)
C2—H2	0.9500	C16—C20	1.384 (5)
C3—C4	1.373 (5)	C16—C17	1.409 (5)
C3—H3	0.9500	C17—C19	1.413 (5)
C4—C5	1.384 (5)	C17—C18	1.417 (6)
C4—H4	0.9500	C20—C22	1.422 (6)
C5—C6	1.479 (5)	C20—C21	1.431 (6)
C6—C7	1.388 (5)	C23—C24	1.482 (5)
C7—C8	1.381 (5)	C23—H23A	0.9900
C7—H7	0.9500	C23—H23B	0.9900
C8—C9	1.374 (5)	C24—H24A	0.9800
C8—H8	0.9500	C24—H24B	0.9800
C9—C10	1.374 (5)	C24—H24C	0.9800
C9—H9	0.9500	O2—H25	0.856 (10)
C10—H10	0.9500	O2—H26	0.860 (10)
N1—Ni—N2	78.64 (12)	C8—C9—C10	118.7 (4)
N1i—Ni—N2	93.73 (11)	C8—C9—H9	120.7
N1i—Ni—N2	93.73 (11)	C10—C9—H9	120.7
N2i—Ni—N1i	78.64 (12)	N2—C10—C9	123.2 (3)
N1—Ni—N1i	91.20 (16)	N2—C10—H10	118.4
N1i—Ni—N3	171.36 (11)	C9—C10—H10	118.4
N1—Ni—N3i	171.36 (11)	N3—C11—C12	122.8 (4)
N2—Ni—N2i	169.18 (16)	N3—C11—H11	118.6
N2—Ni—N3	92.87 (11)	C12—C11—H11	118.6
N2i—Ni—N3	95.51 (11)	C13—C12—C11	119.1 (4)
N1—Ni—N3	95.55 (11)	C13—C12—H12	120.5
N2—Ni—N3i	95.52 (11)	C11—C12—H12	120.5
N2i—Ni—N3i	92.87 (11)	C12—C13—C14	118.8 (4)
N1i—Ni—N3i	95.55 (11)	C12—C13—H13	120.6
N3—Ni—N3i	78.26 (16)	C14—C13—H13	120.6
C1—N1—C5	118.2 (3)	C13—C14—C15	119.8 (4)
C1—N1—Ni	126.6 (3)	C13—C14—H14	120.1
C5—N1—Ni	115.0 (2)	C15—C14—H14	120.1
C10—N2—C6	118.5 (3)	N3—C15—C14	121.3 (3)
C10—N2—Ni	126.0 (2)	N3—C15—C15i	115.3 (2)
C6—N2—Ni	115.5 (2)	C14—C15—C15i	123.4 (2)
C15—N3—C11	118.2 (3)	C16—O1—C23	118.1 (3)
C15—N3—Ni	115.5 (2)	O1—C16—C20	118.7 (3)
C11—N3—Ni	126.2 (3)	O1—C16—C17	113.5 (4)
N1—C1—C2	123.2 (4)	C20—C16—C17	127.6 (4)
N1—C1—H1	118.4	C16—C17—C19	124.0 (4)
C2—C1—H1	118.4	C16—C17—C18	119.5 (3)
C3—C2—C1	118.3 (4)	C19—C17—C18	116.4 (4)
C3—C2—H2	120.8	N4—C18—C17	178.8 (4)
C1—C2—H2	120.8	N5—C19—C17	177.1 (5)
C4—C3—C2	119.4 (4)	C16—C20—C22	121.0 (4)
C4—C3—H3	120.3	C16—C20—C21	122.4 (4)
C2—C3—H3	120.3	C22—C20—C21	116.5 (4)
C3—C4—C5	119.5 (4)	N6—C21—C20	179.0 (5)
C3—C4—H4	120.2	N7—C22—C20	179.4 (5)
C5—C4—H4	120.2	O1—C23—C24	108.5 (3)
N1—C5—C4	121.4 (3)	O1—C23—H23A	110.0
N1—C5—C6	115.5 (3)	C24—C23—H23A	110.0
C4—C5—C6	123.1 (3)	O1—C23—H23B	110.0
N2—C6—C7	121.0 (3)	C24—C23—H23B	110.0
N2—C6—C5	115.2 (3)	H23A—C23—H23B	108.4
C7—C6—C5	123.7 (3)	C23—C24—H24A	109.5
C8—C7—C6	119.5 (3)	C23—C24—H24B	109.5
C8—C7—H7	120.3	H24A—C24—H24B	109.5
C6—C7—H7	120.3	C23—C24—H24C	109.5
C9—C8—C7	119.1 (4)	H24A—C24—H24C	109.5
C9—C8—H8	120.4	H24B—C24—H24C	109.5
C7—C8—H8	120.4	H25—O2—H26	102 (5)
C5—N1—C1—C2	−0.4 (5)	C3—C4—C5—C6	179.2 (3)
Ni—N1—C1—C2	−175.1 (3)	C10—N2—C6—C7	0.4 (5)
N1—C1—C2—C3	1.2 (6)	Ni—N2—C6—C7	−176.1 (3)
C1—C2—C3—C4	−1.1 (6)	C10—N2—C6—C5	178.7 (3)
C2—C3—C4—C5	0.2 (6)	Ni—N2—C6—C5	2.2 (4)
C1—N1—C5—C4	−0.5 (5)	N1—C5—C6—N2	1.1 (4)
Ni—N1—C5—C4	174.8 (3)	C4—C5—C6—N2	−177.5 (3)
C1—N1—C5—C6	−179.2 (3)	N1—C5—C6—C7	179.4 (3)
Ni—N1—C5—C6	−3.8 (4)	C4—C5—C6—C7	0.8 (5)
C3—C4—C5—N1	0.6 (5)	N2—C6—C7—C8	0.3 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H25···N5	0.86	2.11	2.945 (5)	164
O2—H26···N4ii	0.86	2.10	2.955 (5)	175
C24—H24A···Cg1iii	0.98	3.01	3.921	156

Ni-N1	2.088 (3)
Ni-N2	2.077 (3)
Ni-N3	2.090 (3)
N1-Ni-N2	78.64 (12)
N1-Ni-N3	95.55 (11)
N2-Ni-N3	92.87 (11)