Tris(2,2′-bi­pyridine)­iron(II) tris­(di­cyano­methylidene)methane­diide

Messalti, S.A.; Setifi, F.; Böhme, U.; Setifi, Z.; Al-Douh, M.H.

doi:10.1107/S2414314625005036

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 10| Part 6| June 2025| x250503

https://doi.org/10.1107/S2414314625005036

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Tris(2,2′-bipyridine)iron(II) tris(dicyanomethylidene)methanediide

Said Abdelghafour Messalti,^a Fatima Setifi,^a Uwe Böhme,^b ^* Zouaoui Setifi ^c,^a and Mohammad Hadi Al-Douh ^d ^*

^aLaboratoire de Chimie, Ingénierie Moléculaire et Nanostructures (LCIMN), Université Ferhat Abbas Sétif 1, Sétif 19000, Algeria, ^bInstitut für Anorganische Chemie, Technische Universität Bergakademie Freiberg, Leipziger Str. 29, 09599 Freiberg, Germany, ^cDépartement de Technologie, Faculté de Technologie, Université 20 Août 1955-Skikda, BP 26, Route d'El-Hadaiek, Skikda 21000, Algeria, and ^dChemistry Department, Faculty of Science, Hadhramout University, Mukalla, Hadhramout, Yemen
^*Correspondence e-mail: [email protected], [email protected]

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 27 May 2025; accepted 2 June 2025; online 20 June 2025)

The asymmetric unit of the title compound, [Fe(C₁₀H₈N₂)₃][C{C(CN)₂}₃], contains an iron–bipyridyl unit and one third of two crystallographic independent tris(dicyanomethylidene)methanediide units. As a result of crystallographic site symmetry the ratio of cations to anions is 1:1. The tris(2,2′-bipyridine)iron(II) cation has threefold symmetry. The two crystallographic independent tris(dicyanomethylidene)methanediide ions are disordered over two atomic sites having equal occupancy. The anions have 3 symmetry. In the crystal, hydrogen bonds between cations and anions form complex layers parallel to (001). These are supplemented by hydrogen bonds perpendicular to the former, leading to a three-dimensional network.

Keywords: crystal structure; solvothermal synthesis; iron(II) complex; 2,2′-bipyridine; tris(dicyanomethylidene)methanediide.

CCDC reference: 2456126

Structure description

Organic cyanocarbanion anions have recently attracted considerable attention in the fields of coordination chemistry and molecular materials (Benmansour et al., 2010 ). As a consequence of their rigidity and electronic delocalization, these organic anions provide opportunities for the generation of molecular architectures with varying dimensions and topologies (Benmansour et al., 2008 ; Setifi et al., 2010 ; Benamara et al., 2021 ). Furthermore, the use of cyanocarbanion anions for the synthesis of interesting discrete and polymeric bistable materials has been recently reported (Setifi, Milin et al., 2014 ; Cuza et al., 2021 ). It was during the course of attempts to prepare such materials with 2,2′-bipyridine as a co-ligand that the title complex was unexpectedly obtained. We report here the molecular and supramolecular structures of a new compound based on tris(2,2′-bipyridine)iron(II) and the tris(dicyanomethylidene)methanediide dianion (tcpd²⁻) as the counter-ion.

The crystal structure consists of an [Fe(C₁₀H₈N₂)₃]²⁺ cation with a six-coordinate iron atom in a slightly distorted octahedral coordination environment and a [C{C(CN)₂}₃]²⁻ anion (Fig. 1). At first glance, it is noticeable that two crystallographically independent anions are present. These have a site symmetry of $[\overline{3}]$ , which means that one sixth is present in the asymmetric unit. The cation has site symmetry 3, i.e. it consists of an iron bipyridyl unit, with one third of the cation in the asymmetric unit. The resulting ratio of cation to anion is therefore 1:1. The two crystallographic independent tris(dicyanomethylidene)methanediide ions are disordered over two atomic sites having equal occupancy, leading to a star-like appearance.

Figure 1
Molecular structure of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn with 50% probability displacement ellipsoids. Only one of the disordered set of sites is shown.

The Fe—N distances are comparable to other tris(2,2′-bipyridine)iron(II) complexes (Healy et al., 1983 ; Setifi, Setifi et al., 2014 ; Addala et al., 2018 ). The angle N1—Fe1—N2 [81.40 (5)°] is determined by the bite angle of the bipyridine unit. The other cis angles in the coordination polyhedron deviate from 90° (see Table 1), as the octahedral cation is subject to compression in the direction of the threefold rotation axis.

Table 1
Selected geometric parameters (Å, °)

Fe1—N1	1.9688 (13)	C13—N3	1.067 (2)
Fe1—N2	1.9734 (13)	C14—C15	1.421 (3)
C11—C12	1.422 (3)	C15—C16	1.482 (4)
C12—C13	1.473 (3)	C16—N4	1.079 (3)

N1ⁱ—Fe1—N1	96.73 (5)	N1—Fe1—N2	81.40 (5)
N1ⁱ—Fe1—N2	85.75 (5)	N2—Fe1—N2ⁱ	96.18 (5)
N1ⁱⁱ—Fe1—N2	177.07 (5)
Symmetry codes: (i) ; (ii) .

The tris(dicyanomethylidene)methanediide dianions are disordered at the methylidene carbon atoms C12 and C15. The cyano end groups C13—N3 and C16—N4 show slightly elongated displacement ellipsoids due to the disorder at the neighbouring atoms. The cores of the anions (atoms C11/C12 and C14/C15 with their symmetry equivalents, respectively) are exactly planar. The cyano groups are twisted out of these planes (Fig. 2), making dihedral angles with it of 28.0 (2)° (N3, C13, C12, C13C, N3C) and 29.6 (2)° (N4, C16, C15, C16E, N4E). This type of distortion has been observed before (Setifi et al., 2018 , 2020 ).

Figure 2
Side view of the anion C11—C12—C13—N3 with all symmetry-equivalent atoms (top). One of the two orientations is drawn with dashed bonds. Side view with one part of the disordered anion (bottom).

Intramolecular hydrogen bonds in the tris(2,2′-bipyridine)iron(II) cation are C1—H1⋯N1 and C10—H10⋯N2 between hydrogen atoms in ortho position and nitrogen atoms from neighbouring dipyridine units (Table 2). Further hydrogen bonds are present between cation and the anion consisting of C11—C12—C13—N3 with C4—H4⋯N3 and C8—H8⋯N3, which form complex layers parallel to (001) (Fig. 3). The other anion consisting of C14—C15—C16—N4 forms hydrogen bonds C3—H3⋯N4, forming layers that are also parallel to (001) (Fig. 4). Perpendicular to that are hydrogen bonds C10—H10⋯N4, which link the anion to two cations perpendicular to (001) (Fig. 5). All these interactions consolidate the crystal in a three-dimensional network of hydrogen bonds.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N1ⁱⁱ	0.93	2.61	3.121 (2)	115
C10—H10⋯N2ⁱ	0.93	2.60	3.116 (2)	115
C4—H4⋯N3ⁱⁱⁱ	0.93	2.45	3.333 (3)	159
C8—H8⋯N3^iv	0.93	2.68	3.476 (3)	144
C3—H3⋯N4ⁱⁱⁱ	0.93	2.65	3.244 (3)	122
C10—H10⋯N4^v	0.93	2.68	3.437 (3)	139
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) $[x-y+{\script{2\over 3}}, x+{\script{1\over 3}}, -z+{\script{1\over 3}}]$ ; (v) $[-y+{\script{4\over 3}}, x-y+{\script{2\over 3}}, z-{\script{1\over 3}}]$ .

Figure 3
Partial packing diagram showing the hydrogen-bonding interactions C4—H4⋯N3 and C8—H8⋯N3 parallel to (001), as turquoise lines. Only one of the disordered set of sites is shown.

Figure 4
Partial packing diagram showing the hydrogen-bonding interactions C3—H3⋯N4 parallel to (001) as turquoise lines.. Only one of the disordered set of sites is shown.

Figure 5
Partial packing diagram showing the hydrogen-bonding interactions C10—H10⋯N4 parallel to the crystallographic c axis, as turquoise lines. Only one of the disordered set of sites is shown.

There are more than 100 crystal structures of tris(2,2′-bipyridine)iron(II) complexes listed in the Cambridge Structural Database (Groom et al., 2016 ). From these are five crystal structures of closely related complexes containing the tris(2,2′-bipyridine)iron(II) cation and different polynitrile anions (Setifi, Setifi et al., 2014; Potočňák et al., 2014 ; Potočňák & Váhovská, 2014 ; Addala et al., 2018).

Synthesis and crystallization

A mixture of iron(II) bis(tetrafluoroborate) hexahydrate (34 mg, 0.1 mmol), 2,2′-dipyridyl (16 mg, 0.1 mmol) and dipotassium tris(dicyanomethylidene)methanediide (28 mg, 0.1 mmol), N,N-dimethylformamide (4 ml) and water (2 ml) was sonicated for 30 min. Then the reaction mixture was transferred to a Teflon-lined stainless steel reactor and placed in an oven. Subsequently, the temperature was kept 393 K for 3 days. After cooling to room temperature at a rate of 10 K h⁻¹, red plate-shaped crystals of the title compound were obtained.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The two crystallographic independent tris(dicyanomethylidene)methanediide ions are disordered over two atomic sites having equal occupancy.

Table 3
Experimental details

Crystal data
Chemical formula	[Fe(C₁₀H₈N₂)₃](C₁₀N₆)
M_r	728.56
Crystal system, space group	Trigonal, R $[\overline{3}]$ :H
Temperature (K)	298
a, c (Å)	17.0276 (3), 21.6388 (5)
V (Å³)	5433.4 (2)
Z	6
Radiation type	Mo Kα
μ (mm⁻¹)	0.46
Crystal size (mm)	0.45 × 0.28 × 0.15

Data collection
Diffractometer	Bruker D8 VENTURE Duo
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.875, 0.922
No. of measured, independent and observed [I > 2σ(I)] reflections	32654, 2780, 2269
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.091, 1.05
No. of reflections	2780
No. of parameters	170
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.35
Computer programs: APEX4 and SAINT (Bruker, 2021 ), SHELXT (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ) and ORTEP-3 for Windows (Farrugia, 2012 ).

Structural data

CCDC reference: 2456126

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314625005036/bt4174sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625005036/bt4174Isup2.hkl

checkCIF report

Computing details top

Tris(2,2'-bipyridine)iron(II) tris(dicyanomethylidene)methanediide top

Crystal data top

[Fe(C₁₀H₈N₂)₃](C₁₀N₆)	D_x = 1.336 Mg m⁻³
M_r = 728.56	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3:H	Cell parameters from 5342 reflections
a = 17.0276 (3) Å	θ = 2.8–28.4°
c = 21.6388 (5) Å	µ = 0.46 mm⁻¹
V = 5433.4 (2) Å³	T = 298 K
Z = 6	Plate, red
F(000) = 2244	0.45 × 0.28 × 0.15 mm

Data collection top

Bruker D8 VENTURE Duo diffractometer	2780 independent reflections
Radiation source: sealed tube	2269 reflections with I > 2σ(I)
TRIUMPH graphite monochromator	R_int = 0.045
ω and φ scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −22→22
T_min = 0.875, T_max = 0.922	k = −22→22
32654 measured reflections	l = −28→27

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.091	w = 1/[σ²(F_o²) + (0.0367P)² + 5.2576P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2780 reflections	Δρ_max = 0.22 e Å⁻³
170 parameters	Δρ_min = −0.35 e Å⁻³
0 restraints

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.

Refinement. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were placed in idealized positions and refined with a riding model with C–H = 0.93 Å and with U_iso(H) = 1.2 U_eq(C).

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Fe1	1.000000	1.000000	0.24788 (2)	0.03504 (12)
N1	0.89912 (9)	0.99778 (9)	0.29384 (6)	0.0386 (3)
N2	0.89822 (9)	0.90276 (9)	0.20124 (5)	0.0391 (3)
C1	0.90642 (12)	1.05483 (12)	0.33947 (7)	0.0475 (4)
H1	0.963517	1.093679	0.355820	0.057*
C2	0.83306 (13)	1.05808 (13)	0.36290 (8)	0.0562 (5)
H2	0.840747	1.098700	0.394234	0.067*
C3	0.74830 (13)	1.00060 (14)	0.33947 (9)	0.0590 (5)
H3	0.697874	1.002039	0.354509	0.071*
C4	0.73902 (12)	0.94059 (13)	0.29322 (9)	0.0536 (4)
H4	0.682084	0.900635	0.277093	0.064*
C5	0.81535 (11)	0.94053 (11)	0.27110 (7)	0.0408 (3)
C6	0.81457 (11)	0.88191 (11)	0.22107 (7)	0.0423 (3)
C7	0.73688 (13)	0.81059 (13)	0.19582 (9)	0.0593 (5)
H7	0.679985	0.798009	0.209532	0.071*
C8	0.74465 (14)	0.75829 (14)	0.15005 (10)	0.0685 (6)
H8	0.693155	0.709862	0.132822	0.082*
C9	0.82930 (14)	0.77881 (13)	0.13043 (9)	0.0609 (5)
H9	0.836022	0.744194	0.099887	0.073*
C10	0.90415 (12)	0.85113 (12)	0.15642 (7)	0.0491 (4)
H10	0.961322	0.865004	0.142456	0.059*
C11	0.333333	0.666667	0.166667	0.0315 (7)
C12	0.27300 (19)	0.57138 (18)	0.16798 (14)	0.0356 (6)	0.5
C13	0.30840 (13)	0.51355 (11)	0.19074 (8)	0.0512 (4)
N3	0.29929 (17)	0.45296 (12)	0.21194 (10)	0.0919 (7)
C14	0.666667	0.333333	0.333333	0.0427 (8)
C15	0.5716 (2)	0.2721 (3)	0.33372 (16)	0.0504 (8)	0.5
C16	0.51371 (14)	0.30692 (18)	0.35854 (9)	0.0707 (6)
N4	0.45347 (15)	0.2971 (2)	0.38184 (11)	0.1096 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.03581 (14)	0.03581 (14)	0.03350 (19)	0.01790 (7)	0.000	0.000
N1	0.0407 (7)	0.0398 (7)	0.0371 (6)	0.0215 (6)	−0.0010 (5)	−0.0020 (5)
N2	0.0416 (7)	0.0391 (7)	0.0361 (6)	0.0199 (6)	0.0000 (5)	−0.0012 (5)
C1	0.0495 (9)	0.0523 (10)	0.0438 (8)	0.0277 (8)	−0.0018 (7)	−0.0088 (7)
C2	0.0636 (11)	0.0616 (11)	0.0539 (10)	0.0391 (10)	0.0022 (9)	−0.0113 (8)
C3	0.0543 (11)	0.0693 (12)	0.0665 (11)	0.0408 (10)	0.0069 (9)	−0.0051 (9)
C4	0.0417 (9)	0.0602 (11)	0.0618 (10)	0.0277 (8)	−0.0010 (8)	−0.0054 (8)
C5	0.0399 (8)	0.0422 (8)	0.0423 (8)	0.0220 (7)	−0.0005 (6)	−0.0001 (6)
C6	0.0404 (8)	0.0414 (8)	0.0440 (8)	0.0196 (7)	−0.0028 (6)	−0.0026 (6)
C7	0.0424 (9)	0.0580 (11)	0.0672 (11)	0.0174 (9)	−0.0047 (8)	−0.0150 (9)
C8	0.0539 (11)	0.0600 (12)	0.0746 (13)	0.0158 (10)	−0.0121 (10)	−0.0258 (10)
C9	0.0646 (12)	0.0551 (11)	0.0564 (10)	0.0251 (9)	−0.0038 (9)	−0.0197 (9)
C10	0.0497 (9)	0.0508 (10)	0.0441 (8)	0.0231 (8)	0.0011 (7)	−0.0086 (7)
C11	0.0298 (10)	0.0298 (10)	0.0348 (16)	0.0149 (5)	0.000	0.000
C12	0.0305 (13)	0.0306 (14)	0.0452 (15)	0.0148 (11)	−0.0008 (12)	−0.0012 (11)
C13	0.0638 (11)	0.0358 (8)	0.0563 (10)	0.0267 (8)	−0.0048 (8)	0.0013 (7)
N3	0.133 (2)	0.0465 (10)	0.0953 (14)	0.0447 (12)	−0.0088 (14)	0.0143 (10)
C14	0.0450 (13)	0.0450 (13)	0.0380 (18)	0.0225 (6)	0.000	0.000
C15	0.0471 (19)	0.052 (2)	0.0479 (17)	0.0216 (16)	0.0006 (14)	0.0005 (15)
C16	0.0480 (11)	0.1100 (18)	0.0564 (11)	0.0412 (12)	−0.0070 (9)	−0.0067 (11)
N4	0.0566 (12)	0.183 (3)	0.0910 (15)	0.0611 (15)	−0.0082 (11)	−0.0235 (16)

Geometric parameters (Å, º) top

Fe1—N1ⁱ	1.9688 (13)	C9—H9	0.9300
Fe1—N1ⁱⁱ	1.9688 (13)	C10—H10	0.9300
Fe1—N1	1.9688 (13)	C11—C12ⁱⁱⁱ	1.422 (3)
Fe1—N2	1.9734 (13)	C11—C12^iv	1.422 (3)
Fe1—N2ⁱ	1.9734 (13)	C11—C12	1.422 (3)
Fe1—N2ⁱⁱ	1.9734 (13)	C11—C12^v	1.422 (3)
N1—C1	1.346 (2)	C11—C12^vi	1.422 (3)
N1—C5	1.355 (2)	C11—C12^vii	1.422 (3)
N2—C10	1.346 (2)	C12—C12ⁱⁱⁱ	1.423 (3)
N2—C6	1.354 (2)	C12—C12^vii	1.423 (3)
C1—C2	1.375 (2)	C12—C13	1.473 (3)
C1—H1	0.9300	C12—C13^vii	1.492 (3)
C2—C3	1.373 (3)	C13—N3	1.067 (2)
C2—H2	0.9300	C14—C15^viii	1.421 (3)
C3—C4	1.382 (3)	C14—C15^ix	1.421 (3)
C3—H3	0.9300	C14—C15	1.421 (3)
C4—C5	1.386 (2)	C14—C15^x	1.421 (3)
C4—H4	0.9300	C14—C15^xi	1.421 (3)
C5—C6	1.468 (2)	C14—C15^xii	1.422 (3)
C6—C7	1.384 (2)	C15—C15^viii	1.421 (3)
C7—C8	1.382 (3)	C15—C15^xii	1.422 (3)
C7—H7	0.9300	C15—C16	1.482 (4)
C8—C9	1.370 (3)	C15—C16^xii	1.482 (4)
C8—H8	0.9300	C16—N4	1.079 (3)
C9—C10	1.374 (2)

N1ⁱ—Fe1—N1ⁱⁱ	96.74 (5)	C12ⁱⁱⁱ—C11—C12^v	60.040 (9)
N1ⁱ—Fe1—N1	96.73 (5)	C12^iv—C11—C12^v	119.960 (9)
N1ⁱⁱ—Fe1—N1	96.74 (5)	C12—C11—C12^v	119.960 (9)
N1ⁱ—Fe1—N2	85.75 (5)	C12ⁱⁱⁱ—C11—C12^vi	119.964 (10)
N1ⁱⁱ—Fe1—N2	177.07 (5)	C12^iv—C11—C12^vi	60.037 (9)
N1—Fe1—N2	81.40 (5)	C12—C11—C12^vi	180.0
N1ⁱ—Fe1—N2ⁱ	81.40 (5)	C12^v—C11—C12^vi	60.043 (9)
N1ⁱⁱ—Fe1—N2ⁱ	85.75 (5)	C12ⁱⁱⁱ—C11—C12^vii	119.962 (9)
N1—Fe1—N2ⁱ	177.07 (5)	C12^iv—C11—C12^vii	60.037 (9)
N2—Fe1—N2ⁱ	96.18 (5)	C12—C11—C12^vii	60.042 (9)
N1ⁱ—Fe1—N2ⁱⁱ	177.07 (5)	C12^v—C11—C12^vii	180.0
N1ⁱⁱ—Fe1—N2ⁱⁱ	81.40 (5)	C12^vi—C11—C12^vii	119.955 (9)
N1—Fe1—N2ⁱⁱ	85.75 (5)	C11—C12—C12ⁱⁱⁱ	59.978 (4)
N2—Fe1—N2ⁱⁱ	96.18 (5)	C11—C12—C12^vii	59.981 (5)
N2ⁱ—Fe1—N2ⁱⁱ	96.18 (5)	C12ⁱⁱⁱ—C12—C12^vii	119.84 (3)
C1—N1—C5	118.01 (14)	C11—C12—C13	117.8 (2)
C1—N1—Fe1	126.27 (11)	C12ⁱⁱⁱ—C12—C13	62.0 (2)
C5—N1—Fe1	115.13 (10)	C12^vii—C12—C13	162.7 (4)
C10—N2—C6	118.00 (14)	C11—C12—C13^vii	116.5 (2)
C10—N2—Fe1	126.53 (11)	C12ⁱⁱⁱ—C12—C13^vii	156.1 (4)
C6—N2—Fe1	115.18 (10)	C12^vii—C12—C13^vii	60.6 (2)
N1—C1—C2	122.79 (16)	C13—C12—C13^vii	125.6 (2)
N1—C1—H1	118.6	N3—C13—C12	151.6 (3)
C2—C1—H1	118.6	N3—C13—C12ⁱⁱⁱ	150.9 (2)
C3—C2—C1	119.18 (16)	C12—C13—C12ⁱⁱⁱ	57.34 (18)
C3—C2—H2	120.4	C15^viii—C14—C15^ix	180.0 (2)
C1—C2—H2	120.4	C15^viii—C14—C15	60.003 (4)
C2—C3—C4	119.04 (17)	C15^ix—C14—C15	119.996 (4)
C2—C3—H3	120.5	C15^viii—C14—C15^x	60.004 (3)
C4—C3—H3	120.5	C15^ix—C14—C15^x	119.997 (5)
C3—C4—C5	119.36 (17)	C15—C14—C15^x	119.997 (3)
C3—C4—H4	120.3	C15^viii—C14—C15^xi	120.000 (4)
C5—C4—H4	120.3	C15^ix—C14—C15^xi	60.001 (3)
N1—C5—C4	121.62 (15)	C15—C14—C15^xi	180.0
N1—C5—C6	113.92 (13)	C15^x—C14—C15^xi	60.006 (4)
C4—C5—C6	124.45 (15)	C15^viii—C14—C15^xii	119.998 (4)
N2—C6—C7	121.57 (15)	C15^ix—C14—C15^xii	60.001 (4)
N2—C6—C5	113.87 (13)	C15—C14—C15^xii	60.005 (4)
C7—C6—C5	124.56 (15)	C15^x—C14—C15^xii	180.0
C8—C7—C6	119.39 (18)	C15^xi—C14—C15^xii	119.991 (3)
C8—C7—H7	120.3	C14—C15—C15^viii	59.996 (2)
C6—C7—H7	120.3	C14—C15—C15^xii	59.999 (2)
C9—C8—C7	119.04 (17)	C15^viii—C15—C15^xii	119.984 (14)
C9—C8—H8	120.5	C14—C15—C16	116.8 (3)
C7—C8—H8	120.5	C15^viii—C15—C16	61.4 (3)
C8—C9—C10	119.21 (17)	C15^xii—C15—C16	159.4 (4)
C8—C9—H9	120.4	C14—C15—C16^xii	116.7 (3)
C10—C9—H9	120.4	C15^viii—C15—C16^xii	157.4 (4)
N2—C10—C9	122.77 (16)	C15^xii—C15—C16^xii	61.3 (3)
N2—C10—H10	118.6	C16—C15—C16^xii	126.5 (3)
C9—C10—H10	118.6	N4—C16—C15	151.5 (3)
C12ⁱⁱⁱ—C11—C12^iv	180.00 (17)	N4—C16—C15^viii	150.8 (3)
C12ⁱⁱⁱ—C11—C12	60.039 (9)	C15—C16—C15^viii	57.3 (2)
C12^iv—C11—C12	119.960 (9)

C5—N1—C1—C2	−1.0 (2)	C12^v—C11—C12—C13	19.6 (4)
Fe1—N1—C1—C2	169.70 (14)	C12^vii—C11—C12—C13	−160.4 (4)
N1—C1—C2—C3	0.5 (3)	C12ⁱⁱⁱ—C11—C12—C13^vii	−153.1 (4)
C1—C2—C3—C4	0.4 (3)	C12^iv—C11—C12—C13^vii	26.9 (4)
C2—C3—C4—C5	−0.8 (3)	C12^v—C11—C12—C13^vii	−157.06 (12)
C1—N1—C5—C4	0.7 (2)	C12^vii—C11—C12—C13^vii	22.94 (12)
Fe1—N1—C5—C4	−171.07 (13)	C11—C12—C13—N3	153.0 (4)
C1—N1—C5—C6	179.30 (14)	C12ⁱⁱⁱ—C12—C13—N3	176.1 (5)
Fe1—N1—C5—C6	7.55 (17)	C12^vii—C12—C13—N3	75.2 (8)
C3—C4—C5—N1	0.2 (3)	C13^vii—C12—C13—N3	−30.7 (6)
C3—C4—C5—C6	−178.27 (17)	C11—C12—C13—C12ⁱⁱⁱ	−23.06 (8)
C10—N2—C6—C7	−0.9 (2)	C12^vii—C12—C13—C12ⁱⁱⁱ	−100.9 (7)
Fe1—N2—C6—C7	−175.08 (14)	C13^vii—C12—C13—C12ⁱⁱⁱ	153.2 (4)
C10—N2—C6—C5	178.43 (14)	C15^ix—C14—C15—C15^viii	180.0
Fe1—N2—C6—C5	4.22 (17)	C15^x—C14—C15—C15^viii	1.2 (5)
N1—C5—C6—N2	−7.7 (2)	C15^xii—C14—C15—C15^viii	−178.8 (5)
C4—C5—C6—N2	170.89 (15)	C15^viii—C14—C15—C15^xii	178.8 (5)
N1—C5—C6—C7	171.59 (16)	C15^ix—C14—C15—C15^xii	−1.2 (5)
C4—C5—C6—C7	−9.8 (3)	C15^x—C14—C15—C15^xii	180.0
N2—C6—C7—C8	1.2 (3)	C15^viii—C14—C15—C16	−24.35 (14)
C5—C6—C7—C8	−178.05 (18)	C15^ix—C14—C15—C16	155.65 (14)
C6—C7—C8—C9	−0.5 (3)	C15^x—C14—C15—C16	−23.2 (5)
C7—C8—C9—C10	−0.4 (3)	C15^xii—C14—C15—C16	156.8 (5)
C6—N2—C10—C9	−0.1 (3)	C15^viii—C14—C15—C16^xii	154.5 (5)
Fe1—N2—C10—C9	173.37 (14)	C15^ix—C14—C15—C16^xii	−25.5 (5)
C8—C9—C10—N2	0.8 (3)	C15^x—C14—C15—C16^xii	155.66 (14)
C12^iv—C11—C12—C12ⁱⁱⁱ	180.002 (1)	C15^xii—C14—C15—C16^xii	−24.34 (14)
C12^v—C11—C12—C12ⁱⁱⁱ	−4.0 (4)	C14—C15—C16—N4	−149.5 (4)
C12^vii—C11—C12—C12ⁱⁱⁱ	176.0 (4)	C15^viii—C15—C16—N4	−173.6 (5)
C12ⁱⁱⁱ—C11—C12—C12^vii	−176.0 (4)	C15^xii—C15—C16—N4	−74.0 (9)
C12^iv—C11—C12—C12^vii	4.0 (4)	C16^xii—C15—C16—N4	31.7 (7)
C12^v—C11—C12—C12^vii	180.0	C14—C15—C16—C15^viii	24.01 (10)
C12ⁱⁱⁱ—C11—C12—C13	23.55 (11)	C15^xii—C15—C16—C15^viii	99.5 (7)
C12^iv—C11—C12—C13	−156.45 (11)	C16^xii—C15—C16—C15^viii	−154.7 (5)

Symmetry codes: (i) −y+2, x−y+1, z; (ii) −x+y+1, −x+2, z; (iii) x−y+2/3, x+1/3, −z+1/3; (iv) −x+y, −x+1, z; (v) −y+1, x−y+1, z; (vi) −x+2/3, −y+4/3, −z+1/3; (vii) y−1/3, −x+y+1/3, −z+1/3; (viii) y+1/3, −x+y+2/3, −z+2/3; (ix) −y+1, x−y, z; (x) −x+y+1, −x+1, z; (xi) −x+4/3, −y+2/3, −z+2/3; (xii) x−y+1/3, x−1/3, −z+2/3.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N1ⁱⁱ	0.93	2.61	3.121 (2)	115
C10—H10···N2ⁱ	0.93	2.60	3.116 (2)	115
C4—H4···N3^v	0.93	2.45	3.333 (3)	159
C8—H8···N3ⁱⁱⁱ	0.93	2.68	3.476 (3)	144
C3—H3···N4^v	0.93	2.65	3.244 (3)	122
C10—H10···N4^xiii	0.93	2.68	3.437 (3)	139

Symmetry codes: (i) −y+2, x−y+1, z; (ii) −x+y+1, −x+2, z; (iii) x−y+2/3, x+1/3, −z+1/3; (v) −y+1, x−y+1, z; (xiii) −y+4/3, x−y+2/3, z−1/3.

Acknowledgements

The Technical Platform CRISMAT de l'Université Caen Normandie is thanked for its support for the single-crystal X-ray crystallographic data collection and analysis.

Funding information

Funding for this research was provided by: the Algerian MESRS (Ministèere de l'Enseignement Supéerieur et de la Recherche Scientifique); the Algerian DGRSDT (Direction Géenéerale de la Recherche Scientifique et du Déeveloppement Technologique); and the PRFU project (grant No. B00L01UN190120230003).

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