Crystal structure and Hirshfeld surface analysis of tris­(2,2′-bi­pyridine)­nickel(II) bis­(1,1,3,3-tetra­cyano-2-eth­oxy­propenide) dihydrate

Chi-Duran, I.; Setifi, Z.; Setifi, F.; Jelsch, C.; Morgenstern, B.; Vega, A.; Herrera, F.; Pratap Singh, D.; Hegetschweiler, K.; Boyaala, R.

doi:10.1107/S2056989019006959

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ISSN: 2056-9890

Volume 75| Part 6| June 2019| Pages 867-871

https://doi.org/10.1107/S2056989019006959

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Crystal structure and Hirshfeld surface analysis of tris(2,2′-bipyridine)nickel(II) bis(1,1,3,3-tetracyano-2-ethoxypropenide) dihydrate

Ignacio Chi-Duran,^a,^b ^* Zouaoui Setifi,^c,^d Fatima Setifi,^d ^* Christian Jelsch,^e Bernd Morgenstern,^f Andres Vega,^g Felipe Herrera,^a,^b Dinesh Pratap Singh,^a,^b Kaspar Hegetschweiler ^f and Rabab Boyaala ^h

^aDepartment of Physics, Universidad of Santiago Chile, Av. Ecuador 3493, Estaciín Central, Santiago 9170124, Chile, ^bMillennium Institute for Research in Optics, MIRO, Chile, ^cDépartement de Technologie, Faculté de Technologie, Université 20 Août 1955-Skikda, BP 26, Route d'El-Hadaiek, Skikda 21000, Algeria, ^dLaboratoire de Chimie, Ingénierie Moléculaire et Nanostructures (LCIMN), Université Ferhat Abbas Sétif 1, Sétif 19000, Algeria, ^eCristallographie, Résonance Magnétique et Modélisations (CRM2), UMR CNRS 7036, Institut Jean Barriol, Université de Lorraine, BP 70239, Boulevard des Aiguillettes, 54506 Vandoeuvre-les-Nancy, France, ^fFachrichtung Chemie, Universität des Saarlandes, Postfach 151150, D-66041 Saarbrücken, Germany, ^gDepartamento de Ciencias Quimicas, Universidad Nacional Andres Bello, Av Republica 275 3er Piso, Santiago, Region Metropolitana, Chile, and ^hLaboratoire de Chimie Appliquée et Environnement (LCAE), Faculté des Sciences, Université Mohamed Premier, BP 524, 60000, Oujda, Morocco
^*Correspondence e-mail: ignacio.chi@usach.cl, fat_setifi@yahoo.fr

Edited by J. T. Mague, Tulane University, USA (Received 14 January 2019; accepted 14 May 2019; online 24 May 2019)

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) interactions involving the CH₃ group. The intermolecular interactions were investigated by Hirshfeld surface analysis and two-dimensional fingerprint plots.

Keywords: crystal structure; polynitrile ligand; Hirshfeld surface analysis; hydrogen bonding.

CCDC reference: 1915961

1. 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.

2. 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 C₂ 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).

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) $[-x+1, y, -z+{\script{1\over 2}}]$ .

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, $[{1\over 2}]$ − z.

Figure 2
Disposition of Δ (red) and Λ (blue) stereoisomers in the unit cell.

3. 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).

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) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ .

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 + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ .

4. 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_x_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_x 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_xy of the actual contact types to the surface. The lower part of the table shows the E_xy contact enrichment ratios. The major C_xy contact types and the E_xy 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.

5. 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 Mn^II, Cu^II, Co^II and Fe^II 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 ).

6. 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.

7. 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[F² > 2σ(F²)], wR(F²), 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
Δρ_max, Δρ_min (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 ).

Supporting information

CCDC reference: 1915961

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019006959/mw2141sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019006959/mw2141Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Tris(2,2'-bipyridine)nickel(II) bis(1,1,3,3-tetracyano-2-ethoxypropenide) dihydrate top

Crystal data top

[Ni(C₁₀H₈N₂)₃](C₉H₅N₄O)₂·2H₂O	F(000) = 1936
M_r = 933.63	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0372P)² + 4.4221P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
4670 reflections	Δρ_max = 0.36 e Å⁻³
310 parameters	Δρ_min = −0.39 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

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) −x+1/2, y−1/2, −z+1/2; (iii) −x+1/2, −y+3/2, −z.

Nature of intermolecular contacts on the Hirshfeld surface by chemical type top

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

Selected geometry parameters (Å,°) top

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)

Funding information

FS gratefully acknowledges the Algerian DG-RSDT (Direction Générale de la Recherche Scientifique et du Développement Technologique) and Université Ferhat Abbas Sétif 1 for financial support. FH is supported by CONICYT through the Proyecto REDES ETAPA INICIAL, Convocatoria 2017 No. REDI 170423, and FONDECYT Regular 1181743. DPS and FH are grateful for support from the Iniciativa Cientifica Milenio (ICM) through the Millennium Institute for Research in Optics (MIRO).

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