Crystal structure of tris­(2,2′-bi­pyridine)­cobalt(II) bis­(1,1,3,3-tetra­cyano-2-eth­oxy­propenide)

Benabdallah, J.; Setifi, Z.; Setifi, F.; Boughzala, H.; Titi, A.

doi:10.1107/S2056989018018261

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ISSN: 2056-9890

Volume 75| Part 2| February 2019| Pages 142-145

https://doi.org/10.1107/S2056989018018261

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Crystal structure of tris(2,2′-bipyridine)cobalt(II) bis(1,1,3,3-tetracyano-2-ethoxypropenide)

Jamila Benabdallah,^a Zouaoui Setifi,^b,^c Fatima Setifi,^c ^* Habib Boughzala ^a ^* and Abderrahim Titi ^d

^aLaboratoire de Matériaux et Cristallochimie, Faculté des Sciences de Tunis, Université de Tunis El Manar, 2092 Manar II Tunis, Tunisia, ^bDépartement de Technologie, Faculté de Technologie, Université 20 Août 1955-Skikda, BP 26, Route d'El-Hadaiek, Skikda 21000, Algeria, ^cLaboratoire de Chimie, Ingénierie Moléculaire et Nanostructures (LCIMN), Université Ferhat Abbas Sétif 1, Sétif 19000, Algeria, and ^dLaboratoire de Chimie Appliquée et Environnement (LCAE), Faculté des Sciences, Université Mohamed Premier, BP 524, 60000, Oujda, Morocco
^*Correspondence e-mail: fat_setifi@yahoo.fr, habib.boughzala@ipein.rnu.tn

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 21 November 2018; accepted 23 December 2018; online 4 January 2019)

In the title compound, [Co(C₁₀H₈N₂)₃](C₉H₅N₄O)₂, the tris(2,2′-bipyridine)cobalt(II) dication lies across a twofold rotation axes in the space group C2/c. The N atoms of the three bipyridine ligands form a distorted octahedron around the cobalt ion. All the N atoms of the polynitrile 1,1,3,3-tetracyano-2-ethoxypropenide anions participate in C—H⋯N hydrogen bonds ensuring crystal cohesion and forming a three-dimensional structure. The structure is further stabilized by C—H⋯π(cation) and anion⋯π(cation) interactions.

Keywords: crystal structure; polynitrile ligand; ternary systems; hydrogen bonding; anion⋯π interactions.

CCDC reference: 1887084

1. Chemical context

Ternary complexes of transition metals are mixed complexes where the transition-metal center is coordinated by more than one type of ligand (Gaamoune et al., 2010 ; Setifi et al., 2016 ; Yuste et al., 2009 ). Organic polynitrile anions are among the compounds able to form this type of complex. In addition to their ability to create original structures and different coordination modes, these organic anions exhibit interesting behaviour thanks to their high electronic delocalization (Thétiot et al., 2003 ; Setifi et al., 2016) and magnetic properties (Benmansour et al., 2008 , 2010 ).

Several studies of polynitrile ternary complexes with different transition metals and different co-ligands have been realized (Benmansour et al., 2008; Gaamoune et al., 2010; Setifi et al., 2013 , 2014b , 2017 ; Addala et al., 2015 ). To synthesize such types of complexes we chose 2,2′-bipyridine as co-ligand and cobalt(II) as the transition metal, in view of its promising applications in therapy and imaging, as well as in dye-sensitized solar cells (Renfrew et al., 2017 ; Yum et al., 2012 ). The synthesis and structural study of the title compound (I) is reported here.

2. Structural commentary

The asymmetric unit of the title compound (I) is illustrated in Fig. 1, and selected bond distances and angles are given in Table 1. The complex salt consists of half a tris(2,2′-bipyridine)cobalt(II) cation, the Co^II ion being located on a twofold rotation axis, and a 1,1,3,3-tetracyano-2-ethoxypropenide (tcnoet⁻), anion. The cobalt ion is ligated by the N atoms of the 2,2′-bipyridine ligands forming a slightly distorted octahedral coordination sphere; the Co1—N bond lengths vary from 2.122 (3) to 2.148 (3) Å. In the bpy (2,2′-bipyridine; N1/N2/C1–C10) unit, the pyridine rings are inclined to each other by 10.40 (16)°, while in the other bpy unit (involving atom N3) bisected by a twofold rotation axis the pyridine rings are coplanar. The observed distortion of the Co^IIcoordination sphere is probably the consequence of the hydrogen bonding between the [Co(C₁₀H₈N₂)₃]²⁺ cation and the flexible tcnoet⁻ anion (see Supramolecular features).

Table 1
Selected geometric parameters (Å, °)

Co1—N1	2.122 (3)	C16—C17	1.393 (5)
Co1—N2	2.127 (3)	C16—C20	1.382 (4)
Co1—N3	2.148 (3)	C17—C19	1.415 (5)
N4—C18	1.151 (4)	C17—C18	1.417 (5)
N5—C19	1.151 (4)	C20—C22	1.423 (5)
N6—C21	1.138 (4)	C20—C21	1.429 (5)
N7—C22	1.145 (4)

N1—Co1—N1ⁱ	167.82 (14)	N1—Co1—N3ⁱ	94.90 (9)
N1—Co1—N2	76.89 (10)	N2—Co1—N3ⁱ	93.21 (10)
N1—Co1—N2ⁱ	95.05 (10)	N3—Co1—N3ⁱ	76.48 (14)
N2—Co1—N2ⁱ	98.33 (13)	C19—C17—C18	117.4 (3)
N1—Co1—N3	94.66 (10)	C22—C20—C21	116.0 (3)
N2—Co1—N3	166.21 (9)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Figure 1
The independent components of compound (I)

, showing the atom-numbering scheme [symmetry code: (i) −x + 1, y, −z + $[{1\over 2}]$ ]. Displacement ellipsoids are drawn at the 50% probability level. The hydrogen atoms have been omitted for clarity.

In the tcnoet⁻ anion, the six central C—C distances within the anion range from 1.382 (4) to 1.429 (5) Å while the C≡N distances vary from 1.138 (4) to 1.151 (4) Å (Table 1). As observed previously (Setifi et al., 2016), these values confirm the electron delocalization in the tcnoet⁻ anion. The mean planes of the N≡C—C—C≡N moieties, N4/N5/C17–C19 and N6/N7/C20–C22, are inclined to each other by 31.7 (3)°.

3. Supramolecular features

The crystal packing of (I) is illustrated in Fig. 2. It can be described as an infinite three-dimensional association of the structural units linked by C—H⋯N hydrogen bonds and C—H⋯π and C≡N⋯π interactions; details of these intermolecular interactions are given in Table 2.

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of N1/C1–C5 and N2/C6–C10 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯N4ⁱⁱ	0.95	2.52	3.406 (5)	155
C2—H2⋯N5ⁱⁱⁱ	0.95	2.49	3.266 (5)	138
C11—H11⋯N6^iv	0.95	2.61	3.302 (5)	130
C8—H8⋯N7^v	0.95	2.48	3.268 (5)	140
C24—H24B⋯Cg1^vi	0.98	2.84	3.757	155
C18—N4⋯Cg2	1.15 (1)	3.45 (1)	4.378 (4)	138 (1)
Symmetry codes: (ii) -x+1, -y+1, -z+1; (iii) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iv) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (vi) x, y-1, z.

Figure 2
A view along the b axis of the crystal packing of compound (I)

The cations are surrounded by six tcnoet⁻ anions linked by eight C—H⋯N hydrogen bonds as shown in Fig. 3; the various symmetry codes are give in the figure caption. In the equatorial plane of the cobalt octahedron, two of the six tcnoet⁻ anions are doubly connected to the cationic units (N6, N7 and symmetry equivalents) via C8—H8⋯N7ⁱⁱⁱ; C11ⁱ—H11ⁱ⋯N6ⁱⁱⁱ and their symmetric C8ⁱ—H8ⁱ⋯N7^iv; C11—H11⋯N6^iv. Four tcnoet⁻ anions are linked to atoms N4 and N5 (and symmetry equivalents) via C7—H7⋯N4^iv, C2—H2⋯N5^v, C7ⁱ—H7ⁱ⋯N4ⁱⁱ and C2ⁱ—H2^i⋯N5^vii. One of the anions plays the role of a donor in the structural linkage. Indeed, one tcnoet⁻ anion is linked by an N⋯H—C interaction to the same [Co(C₁₀H₈N₂)₃]²⁺ unit (via N6⋯H11ⁱⁱⁱ—C11ⁱⁱⁱ and N7⋯C8ⁱⁱ—H8ⁱⁱ) and to two other cationic units by N4⋯H7ⁱ—C7ⁱ and N5⋯H2^iv—C2^iv interactions. This environment where the negative charge is delocalized over the central propenide unit as well as into the cyano groups is illustrated in Fig. 4. The various symmetry codes are give in the figure caption.

Figure 3
The hydrogen-bonding environment of the cation in the crystal of compound (I)

. Only H atoms involved in hydrogen bonding have been included. [Symmetry codes: (i) 1 − x, y, $[{1\over 2}]$ − z; (ii) x, 1 − y, z − $[{1\over 2}]$ ; (iii) x − $[{1\over 2}]$ , y + $[{1\over 2}]$ , z; (iv) 1 − x, 1 − y, 1 − z; (v) $[{3\over 2}]$ − x, $[{3\over 2}]$ − y, 1 − z; (vi) $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (vii) − $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z.]

Figure 4
The hydrogen-bonding environment of the anion in compound (I)

. Only H atoms involved in hydrogen bonding have been included. [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) $[{1\over 2}]$ + x, − $[{1\over 2}]$ + y, z; (iii) $[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (iv) $[{3\over 2}]$ − x, $[{3\over 2}]$ − y, 1 − z.]

The crystal structure of (I) is reinforced by the presence of a C—H⋯π interaction involving the methyl group of the propenide unit of the anion and the centroid of pyridine ring (N1/C1–C5) of the cation (C24—H24B⋯Cg1^vi; see Table 2), and an anion⋯π interaction between the centroid of pyridine ring (N2/C6–C10) of the cation and the nitrogen atom N4 of the anion (C18—N4⋯Cg2; see Table 2).

4. Database survey

A search in the Cambridge Structural Database (CSD, version 5.39, last update August 2018; Groom et al., 2016 ) using the query 1,1,3,3-tetracyano-2-ethoxypropenide gave 29 hits. 17 of these have the tcnoet⁻ anion associated with an organic cation to form a salt-like compound (Setifi et al., 2015 , 2014a ). The others have the anion associated to the metal ion acting as a coordinating ligand (Setifi et al., 2009 , 2013, 2017; Addala et al., 2015; Gaamoune et al., 2010). The closest structure to (I) found in this investigation is tris(2,2′-bipyridine)iron(II) bis(1,1,3,3-tetracyano-2-ethoxypropenide) dihydrate (II) (CDS refcode CODZUS; Setifi et al., 2014b). The structural representation of (I) and (II) along the b axis points out some similarities in the cationic positions. However, in compound (II) the water molecule links the tcnoet⁻ anion and the iron aggregate via O—H⋯N hydrogen bonds, forming chains, whereas in (I) the cation is directly linked to the anion via C—H⋯N hydrogen bonds forming a three-dimensional structure. There are no π–π stacking interactions in either compound, but in contrast to compound (I), compound (II) does not display any anion⋯π interactions. In the anion of (II), the mean planes of the N≡C—C—C≡N moieties are inclined to each other by ca 28.1° compared to 31.7 (3)° in (I).

5. Synthesis and crystallization

The title compound was synthesized solvothermally under autogenous pressure from a mixture of CoNO₃·6H₂O (29 mg, 0.1 mmol), 2,2-bipyridine (16 mg, 0.1 mmol) and K(tcnoet) (45 mg, 0.2 mmol) in water–ethanol (4:1 v/v, 20 cm³). 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%). Colourless plate-like crystals of the title compound were selected directly from the synthesized product.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All the hydrogen atoms could be located in difference-Fourier maps. During refinement they were included in calculated positions and treated as riding: C—H = 0.95–0.99 Å with U_iso(H) = 1.5U_eq(C-methyl) and 1.2U_eq(C) for other H atoms.

Table 3
Experimental details

Crystal data
Chemical formula	[Co(C₁₀H₈N₂)₃](C₉H₅N₄O)₂
M_r	897.82
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	162
a, b, c (Å)	22.335 (4), 10.9454 (17), 18.721 (3)
β (°)	110.691 (5)
V (Å³)	4281.4 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.46
Crystal size (mm)	0.21 × 0.18 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.643, 0.755
No. of measured, independent and observed [I > 2σ(I)] reflections	16461, 3929, 2190
R_int	0.084
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.109, 0.96
No. of reflections	3929
No. of parameters	295
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.58
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008 ), DIAMOND (Brandenburg, 2006 ), SHELXL2018 (Sheldrick, 2015 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1887084

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S2056989018018261/su5465sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018018261/su5465Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

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

Crystal data top

[Co(C₁₀H₈N₂)₃](C₉H₅N₄O)₂	F(000) = 1852
M_r = 897.82	D_x = 1.393 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.335 (4) Å	Cell parameters from 289 reflections
b = 10.9454 (17) Å	θ = 2.0–26.5°
c = 18.721 (3) Å	µ = 0.46 mm⁻¹
β = 110.691 (5)°	T = 162 K
V = 4281.4 (12) Å³	Plate, colourless
Z = 4	0.21 × 0.18 × 0.06 mm

Data collection top

Bruker APEXII CCD diffractometer	3929 independent reflections
Radiation source: fine-focus sealed tube	2190 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.084
φ and ω scans	θ_max = 25.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −18→26
T_min = 0.643, T_max = 0.755	k = −12→13
16461 measured reflections	l = −22→22

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 0.96	w = 1/[σ²(F_o²) + (0.0452P)²] where P = (F_o² + 2F_c²)/3
3929 reflections	(Δ/σ)_max = 0.001
295 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.58 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
Co1	0.500000	0.81636 (6)	0.250000	0.0263 (2)
N1	0.56363 (12)	0.7958 (2)	0.36434 (14)	0.0253 (7)
N2	0.45167 (13)	0.6893 (2)	0.29657 (15)	0.0279 (7)
N3	0.54955 (12)	0.9705 (2)	0.22633 (14)	0.0268 (7)
C1	0.62261 (16)	0.8398 (3)	0.39281 (19)	0.0308 (9)
H1	0.637978	0.886810	0.360240	0.037*
C2	0.66287 (17)	0.8212 (3)	0.46700 (19)	0.0337 (9)
H2	0.705215	0.852778	0.485105	0.040*
C3	0.63939 (18)	0.7549 (3)	0.51399 (19)	0.0367 (9)
H3	0.665527	0.740997	0.565732	0.044*
C4	0.57842 (17)	0.7090 (3)	0.4862 (2)	0.0351 (9)
H4	0.561858	0.664173	0.518486	0.042*
C5	0.54094 (16)	0.7289 (3)	0.40983 (19)	0.0249 (8)
C6	0.47718 (16)	0.6754 (3)	0.37336 (18)	0.0252 (8)
C7	0.44605 (17)	0.6097 (3)	0.4125 (2)	0.0343 (9)
H7	0.464431	0.601808	0.466467	0.041*
C8	0.38825 (18)	0.5556 (3)	0.3731 (2)	0.0400 (10)
H8	0.366063	0.511209	0.399616	0.048*
C9	0.36287 (17)	0.5663 (3)	0.2952 (2)	0.0373 (10)
H9	0.323671	0.527270	0.266767	0.045*
C10	0.39518 (17)	0.6343 (3)	0.2592 (2)	0.0357 (9)
H10	0.376978	0.643127	0.205269	0.043*
C11	0.59964 (16)	0.9660 (3)	0.20301 (18)	0.0339 (9)
H11	0.615396	0.888083	0.195848	0.041*
C12	0.62955 (17)	1.0681 (3)	0.18886 (18)	0.0365 (10)
H12	0.665344	1.060954	0.172932	0.044*
C13	0.60629 (17)	1.1811 (3)	0.19837 (18)	0.0389 (9)
H13	0.625453	1.253361	0.188249	0.047*
C14	0.55520 (16)	1.1883 (3)	0.22259 (17)	0.0324 (9)
H14	0.539026	1.265594	0.230061	0.039*
C15	0.52721 (15)	1.0812 (3)	0.23614 (16)	0.0258 (8)
N4	0.53638 (17)	0.3989 (3)	0.39931 (18)	0.0526 (10)
N5	0.72153 (17)	0.5387 (3)	0.40013 (18)	0.0560 (10)
N6	0.77126 (16)	0.3265 (3)	0.3033 (2)	0.0611 (10)
N7	0.75554 (15)	−0.0297 (3)	0.39493 (19)	0.0508 (10)
C16	0.66932 (16)	0.2352 (3)	0.39977 (18)	0.0297 (9)
C17	0.65001 (18)	0.3558 (3)	0.40154 (19)	0.0341 (9)
C18	0.5876 (2)	0.3814 (3)	0.4007 (2)	0.0396 (10)
C19	0.6894 (2)	0.4565 (4)	0.4002 (2)	0.0404 (10)
C20	0.71916 (16)	0.1944 (3)	0.37852 (18)	0.0308 (9)
C21	0.74828 (17)	0.2690 (3)	0.3373 (2)	0.0385 (10)
C22	0.73881 (17)	0.0699 (4)	0.3883 (2)	0.0340 (10)
O1	0.63526 (11)	0.14388 (19)	0.41668 (12)	0.0346 (6)
C23	0.62658 (17)	0.1448 (3)	0.49019 (18)	0.0382 (10)
H23A	0.630478	0.229294	0.510234	0.046*
H23B	0.659880	0.094019	0.527312	0.046*
C24	0.56139 (16)	0.0949 (3)	0.4795 (2)	0.0425 (10)
H24C	0.555584	0.091760	0.529008	0.064*
H24B	0.557384	0.012409	0.457996	0.064*
H24A	0.528652	0.147927	0.444679	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0292 (4)	0.0314 (4)	0.0204 (4)	0.000	0.0115 (3)	0.000
N1	0.0276 (18)	0.0295 (18)	0.0211 (16)	−0.0019 (14)	0.0115 (14)	0.0013 (13)
N2	0.0270 (18)	0.0300 (17)	0.0288 (17)	−0.0003 (15)	0.0122 (15)	−0.0019 (15)
N3	0.0298 (18)	0.0328 (18)	0.0195 (16)	−0.0012 (14)	0.0106 (14)	−0.0005 (13)
C1	0.031 (2)	0.033 (2)	0.029 (2)	−0.0045 (18)	0.0109 (19)	0.0011 (17)
C2	0.028 (2)	0.036 (2)	0.033 (2)	0.0006 (19)	0.0062 (19)	−0.002 (2)
C3	0.040 (3)	0.041 (2)	0.020 (2)	0.001 (2)	0.0000 (19)	−0.0035 (18)
C4	0.041 (3)	0.039 (2)	0.026 (2)	0.000 (2)	0.014 (2)	0.0006 (18)
C5	0.028 (2)	0.025 (2)	0.022 (2)	0.0053 (16)	0.0107 (18)	−0.0023 (16)
C6	0.026 (2)	0.0260 (19)	0.027 (2)	0.0087 (17)	0.0124 (17)	0.0013 (17)
C7	0.032 (2)	0.041 (2)	0.036 (2)	0.0085 (19)	0.020 (2)	0.0092 (19)
C8	0.032 (3)	0.043 (3)	0.053 (3)	0.007 (2)	0.024 (2)	0.016 (2)
C9	0.029 (2)	0.033 (2)	0.053 (3)	−0.0024 (18)	0.019 (2)	0.003 (2)
C10	0.032 (2)	0.040 (2)	0.036 (2)	−0.0057 (19)	0.013 (2)	−0.0067 (18)
C11	0.040 (2)	0.036 (2)	0.029 (2)	0.0014 (19)	0.016 (2)	0.0026 (17)
C12	0.034 (2)	0.051 (3)	0.025 (2)	−0.011 (2)	0.0106 (19)	0.0020 (19)
C13	0.047 (3)	0.040 (3)	0.029 (2)	−0.013 (2)	0.013 (2)	0.002 (2)
C14	0.040 (2)	0.031 (2)	0.0213 (19)	0.001 (2)	0.0045 (18)	0.0001 (17)
C15	0.031 (2)	0.031 (2)	0.0107 (18)	−0.0023 (17)	0.0021 (16)	−0.0018 (15)
N4	0.059 (3)	0.048 (2)	0.052 (2)	0.014 (2)	0.022 (2)	−0.0022 (17)
N5	0.060 (3)	0.046 (2)	0.044 (2)	−0.009 (2)	−0.003 (2)	0.0049 (19)
N6	0.061 (3)	0.059 (2)	0.077 (3)	−0.005 (2)	0.041 (2)	0.015 (2)
N7	0.045 (2)	0.044 (2)	0.076 (3)	0.0008 (19)	0.037 (2)	0.011 (2)
C16	0.033 (2)	0.035 (2)	0.020 (2)	−0.0044 (18)	0.0068 (18)	−0.0033 (17)
C17	0.040 (3)	0.030 (2)	0.029 (2)	0.0031 (19)	0.009 (2)	−0.0003 (17)
C18	0.054 (3)	0.035 (2)	0.026 (2)	0.008 (2)	0.008 (2)	−0.0022 (18)
C19	0.048 (3)	0.038 (3)	0.024 (2)	0.007 (2)	−0.001 (2)	0.002 (2)
C20	0.029 (2)	0.031 (2)	0.031 (2)	−0.0065 (19)	0.0084 (18)	0.0022 (18)
C21	0.032 (2)	0.040 (2)	0.041 (3)	−0.0022 (19)	0.010 (2)	0.005 (2)
C22	0.023 (2)	0.043 (3)	0.039 (2)	−0.006 (2)	0.0158 (19)	0.002 (2)
O1	0.0428 (16)	0.0332 (15)	0.0343 (15)	−0.0057 (12)	0.0218 (13)	−0.0053 (11)
C23	0.049 (3)	0.044 (2)	0.025 (2)	0.0068 (19)	0.018 (2)	0.0047 (17)
C24	0.043 (3)	0.054 (3)	0.038 (2)	0.001 (2)	0.023 (2)	0.003 (2)

Geometric parameters (Å, º) top

Co1—N1	2.122 (3)	C10—H10	0.9500
Co1—N1ⁱ	2.122 (3)	C11—C12	1.375 (4)
Co1—N2	2.127 (3)	C11—H11	0.9500
Co1—N2ⁱ	2.127 (3)	C12—C13	1.377 (5)
Co1—N3	2.148 (3)	C12—H12	0.9500
Co1—N3ⁱ	2.148 (3)	C13—C14	1.371 (4)
N1—C1	1.325 (4)	C13—H13	0.9500
N1—C5	1.350 (4)	C14—C15	1.393 (4)
N2—C10	1.349 (4)	C14—H14	0.9500
N2—C6	1.355 (4)	C15—C15ⁱ	1.481 (6)
N3—C11	1.338 (4)	N4—C18	1.151 (4)
N3—C15	1.347 (4)	N5—C19	1.151 (4)
C1—C2	1.377 (4)	N6—C21	1.138 (4)
C1—H1	0.9500	N7—C22	1.145 (4)
C2—C3	1.379 (4)	C16—O1	1.359 (4)
C2—H2	0.9500	C16—C17	1.393 (5)
C3—C4	1.370 (4)	C16—C20	1.382 (4)
C3—H3	0.9500	C17—C19	1.415 (5)
C4—C5	1.394 (4)	C17—C18	1.417 (5)
C4—H4	0.9500	C20—C22	1.423 (5)
C5—C6	1.466 (4)	C20—C21	1.429 (5)
C6—C7	1.378 (4)	O1—C23	1.456 (3)
C7—C8	1.374 (5)	C23—C24	1.501 (4)
C7—H7	0.9500	C23—H23A	0.9900
C8—C9	1.370 (5)	C23—H23B	0.9900
C8—H8	0.9500	C24—H24C	0.9800
C9—C10	1.369 (4)	C24—H24B	0.9800
C9—H9	0.9500	C24—H24A	0.9800

N1—Co1—N1ⁱ	167.82 (14)	C10—C9—C8	118.6 (3)
N1—Co1—N2	76.89 (10)	C10—C9—H9	120.7
N1ⁱ—Co1—N2	95.05 (10)	C8—C9—H9	120.7
N1—Co1—N2ⁱ	95.05 (10)	N2—C10—C9	123.1 (3)
N1ⁱ—Co1—N2ⁱ	76.89 (10)	N2—C10—H10	118.5
N2—Co1—N2ⁱ	98.33 (13)	C9—C10—H10	118.5
N1—Co1—N3	94.66 (10)	N3—C11—C12	123.5 (3)
N1ⁱ—Co1—N3	94.90 (9)	N3—C11—H11	118.2
N2—Co1—N3	166.21 (9)	C12—C11—H11	118.2
N2ⁱ—Co1—N3	93.21 (10)	C11—C12—C13	118.3 (3)
N1—Co1—N3ⁱ	94.90 (9)	C11—C12—H12	120.9
N1ⁱ—Co1—N3ⁱ	94.66 (9)	C13—C12—H12	120.9
N2—Co1—N3ⁱ	93.21 (10)	C14—C13—C12	119.4 (3)
N2ⁱ—Co1—N3ⁱ	166.21 (9)	C14—C13—H13	120.3
N3—Co1—N3ⁱ	76.48 (14)	C12—C13—H13	120.3
C1—N1—C5	119.0 (3)	C13—C14—C15	119.5 (3)
C1—N1—Co1	125.7 (2)	C13—C14—H14	120.3
C5—N1—Co1	115.3 (2)	C15—C14—H14	120.3
C10—N2—C6	117.8 (3)	N3—C15—C14	121.3 (3)
C10—N2—Co1	126.6 (2)	N3—C15—C15ⁱ	115.92 (17)
C6—N2—Co1	115.1 (2)	C14—C15—C15ⁱ	122.74 (19)
C11—N3—C15	118.1 (3)	O1—C16—C20	113.8 (3)
C11—N3—Co1	126.1 (2)	O1—C16—C17	119.2 (3)
C15—N3—Co1	115.8 (2)	C20—C16—C17	126.9 (3)
N1—C1—C2	123.6 (3)	C16—C17—C19	122.6 (3)
N1—C1—H1	118.2	C16—C17—C18	119.9 (3)
C2—C1—H1	118.2	C19—C17—C18	117.4 (3)
C1—C2—C3	117.5 (3)	N4—C18—C17	178.0 (4)
C1—C2—H2	121.3	N5—C19—C17	179.1 (4)
C3—C2—H2	121.3	C16—C20—C22	121.0 (3)
C4—C3—C2	120.1 (3)	C16—C20—C21	122.5 (3)
C4—C3—H3	120.0	C22—C20—C21	116.0 (3)
C2—C3—H3	120.0	N6—C21—C20	178.6 (4)
C3—C4—C5	119.3 (3)	N7—C22—C20	178.1 (4)
C3—C4—H4	120.4	C16—O1—C23	119.2 (2)
C5—C4—H4	120.4	O1—C23—C24	108.6 (3)
N1—C5—C4	120.5 (3)	O1—C23—H23A	110.0
N1—C5—C6	116.2 (3)	C24—C23—H23A	110.0
C4—C5—C6	123.2 (3)	O1—C23—H23B	110.0
N2—C6—C7	121.4 (3)	C24—C23—H23B	110.0
N2—C6—C5	115.1 (3)	H23A—C23—H23B	108.4
C7—C6—C5	123.4 (3)	C23—C24—H24C	109.5
C8—C7—C6	119.6 (3)	C23—C24—H24B	109.5
C8—C7—H7	120.2	H24C—C24—H24B	109.5
C6—C7—H7	120.2	C23—C24—H24A	109.5
C9—C8—C7	119.5 (3)	H24C—C24—H24A	109.5
C9—C8—H8	120.3	H24B—C24—H24A	109.5
C7—C8—H8	120.3

C5—N1—C1—C2	0.1 (5)	Co1—N2—C10—C9	−170.9 (2)
Co1—N1—C1—C2	−178.1 (2)	C8—C9—C10—N2	1.5 (5)
N1—C1—C2—C3	−1.3 (5)	C15—N3—C11—C12	0.2 (5)
C1—C2—C3—C4	0.8 (5)	Co1—N3—C11—C12	−179.9 (2)
C2—C3—C4—C5	0.8 (5)	N3—C11—C12—C13	−0.7 (5)
C1—N1—C5—C4	1.6 (4)	C11—C12—C13—C14	1.0 (5)
Co1—N1—C5—C4	180.0 (2)	C12—C13—C14—C15	−0.9 (5)
C1—N1—C5—C6	−175.6 (3)	C11—N3—C15—C14	0.0 (5)
Co1—N1—C5—C6	2.7 (3)	Co1—N3—C15—C14	−179.9 (2)
C3—C4—C5—N1	−2.1 (5)	C11—N3—C15—C15ⁱ	−178.5 (3)
C3—C4—C5—C6	175.0 (3)	Co1—N3—C15—C15ⁱ	1.6 (4)
C10—N2—C6—C7	−1.4 (5)	C13—C14—C15—N3	0.4 (5)
Co1—N2—C6—C7	170.8 (2)	C13—C14—C15—C15ⁱ	178.7 (3)
C10—N2—C6—C5	175.2 (3)	O1—C16—C17—C19	166.7 (3)
Co1—N2—C6—C5	−12.6 (3)	C20—C16—C17—C19	−16.8 (6)
N1—C5—C6—N2	6.6 (4)	O1—C16—C17—C18	−16.6 (5)
C4—C5—C6—N2	−170.6 (3)	C20—C16—C17—C18	159.9 (3)
N1—C5—C6—C7	−176.8 (3)	O1—C16—C20—C22	−11.2 (5)
C4—C5—C6—C7	6.0 (5)	C17—C16—C20—C22	172.1 (3)
N2—C6—C7—C8	0.8 (5)	O1—C16—C20—C21	160.7 (3)
C5—C6—C7—C8	−175.6 (3)	C17—C16—C20—C21	−16.0 (6)
C6—C7—C8—C9	1.0 (5)	C20—C16—O1—C23	125.8 (3)
C7—C8—C9—C10	−2.1 (5)	C17—C16—O1—C23	−57.2 (4)
C6—N2—C10—C9	0.3 (5)	C16—O1—C23—C24	145.0 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of N1/C1–C5 and N2/C6–C10 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···N4ⁱⁱ	0.95	2.52	3.406 (5)	155
C2—H2···N5ⁱⁱⁱ	0.95	2.49	3.266 (5)	138
C11—H11···N6^iv	0.95	2.61	3.302 (5)	130
C8—H8···N7^v	0.95	2.48	3.268 (5)	140
C24—H24B···Cg1^vi	0.98	2.84	3.757	155
C18—N4···Cg2	1.15 (1)	3.45 (1)	4.378 (4)	138 (1)

Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x+3/2, −y+3/2, −z+1; (iv) −x+3/2, y+1/2, −z+1/2; (v) x−1/2, y+1/2, z; (vi) x, y−1, z.

Funding information

The authors gratefully acknowledge the Algerian DG-RSDT (Direction Générale de la Recherche Scientifique et du Développement Technologique) and Université Ferhat Abbas Sétif 1 for financial support and also thank the Tunisian Ministry of High Education and Scientific Research and the University of Carthage for support.

References

Addala, A., Setifi, F., Kottrup, K., Glidewell, C., Setifi, Z., Smith, G. & Reedijk, J. (2015). Polyhedron, 87, 307–310. Web of Science CrossRef CAS Google Scholar
Benmansour, S., Atmani, C., Setifi, F., Triki, S., Marchivie, M. & Gómez-García, C. J. (2010). Coord. Chem. Rev. 254, 1468–1478. Web of Science CrossRef CAS Google Scholar
Benmansour, S., Setifi, F., Gómez-García, C. J., Triki, S., Coronado, E. & Salaün, J.-Y. (2008). J. Mol. Struct. 890, 255–262. CrossRef CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gaamoune, B., Setifi, Z., Beghidja, A., El-Ghozzi, M., Setifi, F. & Avignant, D. (2010). Acta Cryst. E66, m1044–m1045. Web of Science CrossRef IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Renfrew, A. K., O'Neill, E. S., Hambley, T. W. & New, E. J. (2017). Coord. Chem. Rev. 375, 221–233.. CrossRef Google Scholar
Setifi, F., Benmansour, S., Marchivie, M., Dupouy, G., Triki, S., Sala-Pala, J., Salaün, J. Y., Gómez-García, C. J., Pillet, S., Lecomte, C. & Ruiz, E. (2009). Inorg. Chem. 48, 1269–1271. CrossRef CAS Google Scholar
Setifi, F., Morgenstern, B., Hegetschweiler, K., Setifi, Z., Touzani, R. & Glidewell, C. (2017). Acta Cryst. E73, 48–52. Web of Science CrossRef IUCr Journals Google Scholar
Setifi, F., Valkonen, A., Setifi, Z., Nummelin, S., Touzani, R. & Glidewell, C. (2016). Acta Cryst. E72, 1246–1250. Web of Science CrossRef IUCr Journals Google Scholar
Setifi, Z., Domasevitch, K. V., Setifi, F., Mach, P., Ng, S. W., Petříček, V. & Dušek, M. (2013). Acta Cryst. C69, 1351–1356. Web of Science CrossRef CAS IUCr Journals Google Scholar
Setifi, Z., Lehchili, F., Setifi, F., Beghidja, A., Ng, S. W. & Glidewell, C. (2014a). Acta Cryst. C70, 338–341. CrossRef IUCr Journals Google Scholar
Setifi, Z., Setifi, F., Boughzala, H., Beghidja, A. & Glidewell, C. (2014b). Acta Cryst. C70, 465–469. CrossRef IUCr Journals Google Scholar
Setifi, Z., Valkonen, A., Fernandes, M. A., Nummelin, S., Boughzala, H., Setifi, F. & Glidewell, C. (2015). Acta Cryst. E71, 509–515. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Thétiot, F., Triki, S. & Sala Pala, J. (2003). Polyhedron, 22, 1837–1843. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yum, J. H., Baranoff, E., Kessler, F., Moehl, T., Ahmad, S., Bessho, T., Marchioro, A., Ghadiri, E., Moser, J. E., Yi, Ch., Nazeeruddin, Md. K. & Grätzel, M. (2012). Nat. Commun. 3, 631–639. CrossRef Google Scholar
Yuste, C., Bentama, A., Marino, N., Armentano, D., Setifi, F., Triki, S., Lloret, F. & Julve, M. (2009). Polyhedron, 28, 1287–1294. Web of Science CrossRef CAS Google Scholar

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