Bis(azido-κN)bis­(quinolin-8-amine-κ2N,N′)iron(II) monohydrate

Setifi, F.; Setifi, Z.; Reuter, H.; Al-Douh, M.H.; Addala, A.

doi:10.1107/S2414314625002354

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 10| Part 3| March 2025| x250235

https://doi.org/10.1107/S2414314625002354

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Bis(azido-κN)bis(quinolin-8-amine-κ²N,N′)iron(II) monohydrate

Fatima Setifi,^a ^* Zouaoui Setifi,^b,^a Hans Reuter,^c ^* Mohammad Hadi Al-Douh ^d and Abderezak Addala ^a

^aLaboratoire de Chimie, Ingénierie Moléculaire et Nanostructures (LCIMN), Université Ferhat Abbas Sétif 1, Sétif 19000, Algeria, ^bDépartement de Technologie, Faculté de Technologie, Université 20 Août 1955-Skikda, BP 26, Route d'El-Hadaiek, Skikda 21000, Algeria, ^cChemistry, Osnabrück University, Barabarstr. 7, 49069 Osnabrück, Germany, and ^dChemistry Department, Faculty of Science, Hadhramout University, Mukalla, Hadhramout, Yemen
^*Correspondence e-mail: fatima.setifi@univ-setif.dz, hreuter@uos.de

Edited by M. Zeller, Purdue University, USA (Received 3 March 2025; accepted 15 March 2025; online 19 March 2025)

In the hydrated title complex, [Fe(N₃)₂(AQ)₂]·H₂O (AQ is 8-aminoquinoline, C₉H₉N₂), the Fe^II ion is coordinated in a distorted octahedral manner by two neutral, chelating AQ ligands and two anionic, monodentate azide (N₃⁻) ions in a syn,cis-configuration. From the two AQ ligands, the pyridyl N atoms are opposite to each other and the amino groups trans to the azide ligands. Distortion results from different Fe—N bond lengths [2.112 (2)–2.231 (2) Å] and 〈(N—Fe—N)_cis [75.25 (6)–99.91 (7)°] and 〈(N—Fe—N)_trans [159.98 (7)–170.62 (7)°] bond angles. The water molecule acts as the acceptor of hydrogen bonds with the NH₂ groups of both AQ-ligands in one and the same molecule, and as donor to the γ-N and α-N atoms of the azido ligands of two adjacent iron complexes. In addition, both terminal N atoms of the azido ligands are involved in hydrogen bonds with NH₂ groups in neighboring iron complexes, so that the hydrogen-bonding pattern leads to a rod-like arrangement of the molecules in the b-axis direction.

Keywords: crystal structure; azide; iron(II); hydrogen-bonding; 8-aminoquinoline.

CCDC reference: 2431539

Structure description

Pseudohalide compounds derived from transition-metal ions are of great interest from the perspective of their magnetic properties, rich molecular architectures and for their topologies (Setifi, Ghazzali et al., 2016 , Setifi et al., 2018 , 2022 ; Merabet et al., 2022 ). One of the pseudohalide ligands that has received much attention in the last decade is the azide [N₃⁻] ion, partly due to its ability to produce a wide variety of coordination compounds with different nuclearities ranging from simple mononuclear to polynuclear species (Escuer & Aromi, 2006 ; Benamara et al., 2021 ; Merabet et al., 2023 ).

Up to now, mononuclear, octahedral iron(II) bis-azido complexes with bidentate Lewis bases LB_NN having the general composition Fe^II(LB_NN)₂(N₃)₂, are only known for LB_NN = 1,10-phenanthroline (Miao et al. 2006 ), 4-amino-3,5-bis(2-pyridyl)-1,2,4-triazole (Setifi et al. 2021 ), and quinolin-8-amine (Setifi, Moon et al., 2016 ). Very recently, this class of compounds was expanded by hydrates with the monohydrate Fe(LB_NN)₂(N₃)₂·H₂O where LB_NN = 2,2-dipyridylamine (Setifi et al., 2024 ).

Here we report on the monohydrate of the quinolin-8-amine complex, [Fe(N₃)₂(AQ)₂]·H₂O, revealing for the first time that hydrated as well as unhydrated forms of a specific azido iron(II) complex may exist and that the azido ligands in such complexes may have different orientations relative to each other. The compound was prepared under solvothermal conditions and its structure is described.

The title compound crystallizes in the orthorhombic space group Pbcn with eight formula units in the unit cell. The asymmetric unit therefore consists of one iron(II) complex and one water molecule both with all atoms in general positions (Fig. 1). The overall composition of the complex corresponds to Fe^II(N₃)₂(AQ)₂ with two neutral, chelating Lewis base molecules AQ = 8-aminoquinoline, and two monodentate azide ions, N₃⁻, in a cis position. From the two AQ ligands, the pyridyl N atoms are trans and the two amino groups cis to each other.

Figure 1
Displacement ellipsoid plot of the asymmetric unit of the title compound Fe^II(LB_NN)₂(N₃)₂·H₂O (LB_NN = AQ) showing the atom numbering. With the exception of the hydrogen atoms, which are shown as spheres of arbitrary radius, all atoms are drawn with displacement ellipsoids at the 40% probability level.

The Fe^II atom exhibits as usually a slightly distorted octahedral {FeN₆} coordination (Table 1, Fig. 2). In contrast to the unhydrated compound (Setifi, Moon et al., 2016), the two azido ligands have a syn orientation with an angle between them of 54.6 (6)°. A similar orientation was previously found in the triazane complex. Distortion results from different Fe—N bond lengths [d(Fe—N_azido) = 2.112 (2)/2.142 (2) Å, < d(Fe—N_AQ) = 2.177 (2)–2.231 (2) Å] and different bond angles [〈(N_Amine—Fe—N_Quinoline)_cis = 75.25 (6)/76.06 (7)°, 〈(N_Amine—Fe—N_Azide)_cis = 91.37 (7)/87.40 (8)°, 〈(N_Quinoline—Fe—N_Azide)_cis = 92.83 (8)–99.91 (7)°, 〈(N—Fe—N)_trans = 170.62 (7)/159.98 (7)/168.94 (8)°].

Table 1
Selected geometric parameters (Å, °)

Fe1—N1	2.142 (2)	Fe1—N4	2.112 (2)
N1—N2	1.159 (3)	N4—N5	1.202 (2)
N2—N3	1.166 (3)	N5—N6	1.156 (3)

N1—N2—N3	177.3 (3)	N4—N5—N6	179.2 (2)
N2—N1—Fe1	157.4 (2)	N5—N4—Fe1	122.3 (2)

Figure 2
The {FeN₆} octahedron in polyhedral representation, showing the syn orientation of both azido ligands. With the exception of the hydrogen atoms, which are shown as spheres of arbitrary radius, all atoms are drawn with displacement ellipsoids at the 40% probability level. The position of the carbon atoms attached to the nitrogen atoms of the ligands are indicated as shortened sticks.

Both azido ligands are slightly bent [177.3 (3)/179.2 (2)°] with N—N bond lengths [1.159 (3)–1.202 (2) Å] typical for formal N=N double bonds with the longer one to the metal-coordinating N atom. They are different to some extend because of different coordination modes: in the first azido ligand (N1–N3) the metal-coordinated nitrogen atom is additionally involved in a hydrogen bond (Table 2) to a hydrogen atom of the water molecule and the terminal nitrogen atom in a hydrogen bond to a NH₂ group of AQ(B), while in the second azido ligand (N4–N6) the terminal nitrogen atom N6 is involved in two hydrogen bonds, one to a hydrogen atom of a the water molecule and second one to the hydrogen atom of a NH₂ group of AQ(A) (Fig. 3).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N4ⁱ	0.96	1.88	2.838 (3)	175
O1—H2⋯N3ⁱⁱ	0.96	1.85	2.807 (3)	174
N2A—H11⋯N6ⁱⁱ	0.89	2.17	3.052 (3)	170
N2A—H12⋯O1	0.89	2.28	3.086 (3)	151
N2B—H21⋯N3ⁱⁱⁱ	0.89	2.35	3.206 (3)	160
N2B—H22⋯O1	0.89	2.17	3.037 (2)	164
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x, -y, z+{\script{1\over 2}}]$ ; (iii) .

Figure 3
Displacement ellipsoid plot showing the two azido ligands in the iron(II) complex of the title compound in detail, with selected bond lengths (Å), hydrogen bonds [dashed, shortened sticks, d(D⋯A) in Å, O—H⋯N = red, N—H⋯N = blue] and dative bonds (shortened sticks) to the central iron atom. With the exception of the hydrogen atoms, which are shown as spheres of arbitrary radius, all atoms are drawn with displacement ellipsoids at the 40% probability level.

N—C and C—C bond lengths and angles in the quinoline ring systems of the two ligands (labeled with suffixes A and B; Fig. 4) are comparable to those of the pure AQ molecule (van Meervelt et al., 1997 ) or the AQ molecules in the unhydrated Fe^II complex (Setifi, Moon et al., 2016) as are the bond lengths and angles of the attached NH₂ groups. Both amine groups act as hydrogen donors in hydrogen bonds to the oxygen atom O1 of the water molecule and to the terminal nitrogen atoms of the azide ligands: N2A to the N6 atom of the second azide ion and N2B to N3 of the first one. The water molecule also acts as a hydrogen donor in hydrogen bonds to the terminal nitrogen atom N3 of the first azide ligand and to the iron coordinated nitrogen atom N4 of the second one. Numerical details of the hydrogen bonds are summarized in Table 2 and visualized in Fig. 5.

Figure 4
Displacement ellipsoid plot models showing the two 8-aminoquinoline ligand molecules in the iron(II) complex of the title compound in detail, with selected bond lengths (Å), bond angles (°), and hydrogen bonds (O—H⋯N as red, N—H⋯N as blue dashed lines). With the exception of the hydrogen atoms, which are shown as spheres of arbitrary radius, all atoms are drawn with displacement ellipsoids at the 40% probability level.

Figure 5
Space-filling model of one [Fe^II(N₃)₂(AQ)₂] complex molecule and a water molecule visualizing the hydrogen-bonding scheme (dashed lines). Atoms are drawn as single-colored or truncated, two-colored spheres according to their van der Waals radii and cut-offs based on the intersection of the two spheres with cut-off faces showing the color of the interpenetrating atom. Atom colors and van der Waals radii (Å) are as follows: H = white/1.10, C = gray/1.70, N = blue/1.55, O = red/1.52/ and Fe = orange/2.00.

In the crystal, the complex molecules are arranged in columns parallel to the b-axis via N_azide⋯H—O hydrogen bonds while the O⋯H₂—N hydrogen bonds act as bridges between the two amine groups of one and the same Fe(N₃)₂(AQ)₂-molecule (Fig. 6).

Figure 6
Stick model of the crystal packing down the crystallographic b axis. Color code: N = blue, H = white, C = gray, O = red, Fe = orange. O⋯H₂—N hydrogen bonds between the two amine groups of each molecule are shown with red dashed lines. The O—H⋯N_Azide hydrogen bonds linking the molecules into columns parallel to the b axis are omitted for clarity.

Synthesis and crystallization

The title compound was prepared solvothermally from a mixture of iron(II) bis(tetrafluoroborate) hexahydrate (34 mg, 0.1 mmol), 8-aminoquinoline (29 mg, 0.2 mmol) and sodium azide (13 mg, 0.2 mmol) in a mixture of water/ethanol (4:1 v/v, 25 ml). This mixture was sealed in a Teflon-lined autoclave and held at 400 K for 2 d, and then cooled to ambient temperature at a rate of 10 K h⁻¹ to give the product in form of red plates (yield 36%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3.

Table 3
Experimental details

Crystal data
Chemical formula	[Fe(N₃)₂(C₉H₈N₂)₂]·H₂O
M_r	446.27
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	32.5164 (15), 8.8531 (5), 13.5952 (6)
V (Å³)	3913.7 (3)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.81
Crystal size (mm)	0.27 × 0.11 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.789, 0.913
No. of measured, independent and observed [I > 2σ(I)] reflections	20186, 5690, 3470
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.100, 0.93
No. of reflections	5690
No. of parameters	273
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.46
Computer programs: APEX2 and SAINT-Plus (Bruker, 2019 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), DIAMOND (Brandenburg, 2006 ), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2431539

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314625002354/zl4079sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625002354/zl4079Isup2.hkl

checkCIF report

Computing details top

Bis(azido-κN)bis(quinolin-8-amine-κ²N,N')iron(II) monohydrate top

Crystal data top

[Fe(N₃)₂(C₉H₈N₂)₂]·H₂O	D_x = 1.515 Mg m⁻³
M_r = 446.27	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 5258 reflections
a = 32.5164 (15) Å	θ = 2.4–28.5°
b = 8.8531 (5) Å	µ = 0.81 mm⁻¹
c = 13.5952 (6) Å	T = 293 K
V = 3913.7 (3) Å³	Plate, red
Z = 8	0.27 × 0.11 × 0.05 mm
F(000) = 1840

Data collection top

Bruker APEXII CCD diffractometer	5690 independent reflections
Radiation source: sealed X-ray tube	3470 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
φ and ω scans	θ_max = 30.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −45→45
T_min = 0.789, T_max = 0.913	k = −12→8
20186 measured reflections	l = −19→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.0476P)²] where P = (F_o² + 2F_c²)/3
S = 0.93	(Δ/σ)_max = 0.001
5690 reflections	Δρ_max = 0.50 e Å⁻³
273 parameters	Δρ_min = −0.46 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. The positions of all H atoms were clearly identified in difference Fourier syntheses. Those of the organic ligands were refined with calculated positions (–CH– = 0.93 Å, –NH₂– = 0.89 Å) and isotropic displacement parameters depending on the equivalent isotropic temperature factor of the parent atoms. The position of the H atom of the water molecule were refined with fixed O—H distances of 0.96 Å and a bond angle of 104.95° before they were fixed and allowed to ride on the parent O atom with isotropic displacement parameters.

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

	x	y	z	U_iso*/U_eq
Fe1	0.38035 (2)	0.21817 (4)	0.56455 (2)	0.02331 (9)
O1	0.35856 (5)	0.4514 (2)	0.82039 (12)	0.0403 (4)
H1	0.3663	0.5464	0.8490	0.046 (8)*
H2	0.3573	0.3822	0.8747	0.080 (11)*
N1	0.38357 (7)	−0.0156 (3)	0.52450 (17)	0.0498 (6)
N2	0.37150 (5)	−0.1342 (2)	0.50298 (13)	0.0265 (4)
N3	0.36072 (7)	−0.2560 (2)	0.48292 (19)	0.0475 (6)
N4	0.38371 (6)	0.2776 (2)	0.41435 (13)	0.0298 (4)
N5	0.40034 (5)	0.1988 (2)	0.35437 (13)	0.0259 (4)
N6	0.41626 (6)	0.1243 (2)	0.29588 (15)	0.0382 (5)
N1A	0.31339 (5)	0.2393 (2)	0.57831 (13)	0.0268 (4)
C1A	0.28792 (7)	0.3007 (3)	0.51410 (17)	0.0325 (5)
H1A	0.2989	0.3567	0.4626	0.039*
C2A	0.24486 (7)	0.2857 (3)	0.51992 (18)	0.0383 (6)
H2A	0.2280	0.3338	0.4744	0.046*
C3A	0.22820 (7)	0.2004 (3)	0.59249 (18)	0.0363 (6)
H3A	0.1998	0.1876	0.5960	0.044*
C4A	0.25394 (7)	0.1311 (3)	0.66260 (16)	0.0301 (5)
C5A	0.23947 (7)	0.0367 (3)	0.73857 (18)	0.0374 (6)
H5A	0.2115	0.0178	0.7448	0.045*
C6A	0.26660 (8)	−0.0267 (3)	0.80300 (19)	0.0401 (6)
H6A	0.2570	−0.0923	0.8512	0.048*
C7A	0.30896 (7)	0.0055 (3)	0.79768 (17)	0.0333 (5)
H7A	0.3268	−0.0367	0.8434	0.040*
C8A	0.32400 (6)	0.0983 (2)	0.72585 (15)	0.0258 (5)
C9A	0.29669 (6)	0.1584 (2)	0.65421 (15)	0.0243 (5)
N2A	0.36646 (5)	0.1420 (2)	0.71743 (13)	0.0271 (4)
H11	0.3825	0.0640	0.7328	0.033*
H12	0.3718	0.2166	0.7595	0.033*
N1B	0.44530 (5)	0.2273 (2)	0.60288 (14)	0.0283 (4)
C1B	0.47090 (7)	0.1127 (3)	0.60427 (19)	0.0395 (6)
H1B	0.4602	0.0158	0.5973	0.047*
C2B	0.51386 (7)	0.1293 (3)	0.61585 (19)	0.0441 (7)
H2B	0.5308	0.0446	0.6181	0.053*
C3B	0.53032 (7)	0.2701 (3)	0.62365 (18)	0.0380 (6)
H3B	0.5586	0.2825	0.6297	0.046*
C4B	0.50415 (7)	0.3966 (3)	0.62245 (15)	0.0298 (5)
C5B	0.51836 (7)	0.5466 (3)	0.62898 (17)	0.0377 (6)
H5B	0.5464	0.5656	0.6338	0.045*
C6B	0.49145 (8)	0.6632 (3)	0.62832 (17)	0.0392 (6)
H6B	0.5013	0.7617	0.6319	0.047*
C7B	0.44891 (7)	0.6373 (3)	0.62234 (16)	0.0302 (5)
H7B	0.4308	0.7187	0.6230	0.036*
C8B	0.43379 (6)	0.4934 (3)	0.61555 (14)	0.0238 (5)
C9B	0.46122 (6)	0.3697 (3)	0.61423 (14)	0.0236 (5)
N2B	0.39027 (5)	0.4594 (2)	0.61037 (13)	0.0251 (4)
H21	0.3782	0.5207	0.5672	0.030*
H22	0.3788	0.4749	0.6689	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.02297 (14)	0.02148 (16)	0.02548 (15)	−0.00273 (14)	−0.00115 (13)	−0.00175 (15)
O1	0.0536 (11)	0.0335 (10)	0.0338 (10)	−0.0087 (8)	−0.0002 (8)	−0.0067 (9)
N1	0.0737 (16)	0.0235 (12)	0.0521 (14)	−0.0043 (12)	−0.0006 (12)	−0.0056 (11)
N2	0.0255 (9)	0.0261 (12)	0.0279 (10)	0.0029 (8)	0.0000 (7)	0.0004 (9)
N3	0.0475 (13)	0.0320 (14)	0.0631 (16)	−0.0089 (11)	−0.0041 (12)	−0.0109 (12)
N4	0.0368 (10)	0.0269 (10)	0.0257 (10)	0.0016 (9)	0.0013 (8)	−0.0001 (9)
N5	0.0241 (9)	0.0263 (11)	0.0273 (10)	−0.0077 (8)	−0.0012 (8)	0.0022 (9)
N6	0.0432 (12)	0.0336 (13)	0.0377 (12)	−0.0038 (10)	0.0089 (9)	−0.0066 (10)
N1A	0.0256 (9)	0.0272 (11)	0.0276 (10)	−0.0035 (8)	−0.0023 (7)	0.0017 (8)
C1A	0.0333 (12)	0.0334 (15)	0.0308 (12)	0.0009 (11)	−0.0029 (10)	0.0028 (11)
C2A	0.0309 (12)	0.0454 (16)	0.0386 (13)	0.0035 (12)	−0.0093 (10)	0.0010 (13)
C3A	0.0225 (11)	0.0443 (17)	0.0420 (14)	−0.0027 (11)	−0.0023 (9)	−0.0069 (13)
C4A	0.0279 (11)	0.0295 (14)	0.0328 (12)	−0.0033 (10)	0.0015 (10)	−0.0077 (11)
C5A	0.0322 (13)	0.0398 (17)	0.0401 (14)	−0.0115 (12)	0.0090 (11)	−0.0048 (12)
C6A	0.0456 (14)	0.0380 (17)	0.0369 (14)	−0.0093 (12)	0.0102 (12)	0.0035 (13)
C7A	0.0385 (13)	0.0283 (13)	0.0332 (13)	0.0006 (11)	0.0025 (10)	0.0028 (12)
C8A	0.0291 (11)	0.0220 (12)	0.0263 (11)	−0.0025 (9)	0.0018 (9)	−0.0045 (10)
C9A	0.0266 (11)	0.0195 (11)	0.0269 (11)	−0.0031 (9)	−0.0005 (9)	−0.0031 (10)
N2A	0.0273 (9)	0.0244 (11)	0.0295 (10)	−0.0010 (8)	−0.0048 (7)	−0.0021 (9)
N1B	0.0283 (9)	0.0254 (10)	0.0312 (10)	0.0048 (9)	−0.0004 (8)	−0.0008 (9)
C1B	0.0365 (14)	0.0353 (16)	0.0467 (15)	0.0071 (12)	0.0001 (11)	0.0025 (13)
C2B	0.0319 (14)	0.0491 (19)	0.0513 (16)	0.0178 (13)	−0.0006 (12)	0.0036 (15)
C3B	0.0214 (11)	0.0588 (18)	0.0337 (13)	0.0030 (12)	−0.0001 (9)	0.0034 (13)
C4B	0.0250 (11)	0.0462 (16)	0.0183 (11)	−0.0046 (11)	−0.0018 (8)	0.0017 (11)
C5B	0.0281 (12)	0.0561 (18)	0.0288 (13)	−0.0189 (12)	−0.0016 (10)	0.0007 (12)
C6B	0.0449 (15)	0.0380 (15)	0.0349 (14)	−0.0177 (13)	−0.0025 (11)	−0.0014 (12)
C7B	0.0382 (13)	0.0256 (13)	0.0268 (12)	−0.0056 (11)	−0.0002 (9)	−0.0026 (11)
C8B	0.0258 (11)	0.0287 (12)	0.0170 (10)	−0.0054 (9)	0.0011 (8)	−0.0012 (9)
C9B	0.0236 (10)	0.0299 (13)	0.0174 (10)	−0.0044 (10)	−0.0009 (8)	−0.0002 (10)
N2B	0.0230 (9)	0.0261 (11)	0.0260 (10)	−0.0005 (8)	0.0006 (7)	0.0005 (8)

Geometric parameters (Å, º) top

Fe1—N1	2.142 (2)	C7A—C8A	1.367 (3)
Fe1—N1B	2.177 (2)	C7A—H7A	0.9300
Fe1—N1A	2.193 (2)	C8A—C9A	1.421 (3)
Fe1—N2A	2.231 (2)	C8A—N2A	1.438 (3)
Fe1—N2B	2.248 (2)	N2A—H11	0.8900
O1—H1	0.9600	N2A—H12	0.8900
O1—H2	0.9600	N1B—C1B	1.313 (3)
N1—N2	1.159 (3)	N1B—C9B	1.372 (3)
N2—N3	1.166 (3)	C1B—C2B	1.413 (3)
Fe1—N4	2.112 (2)	C1B—H1B	0.9300
N4—N5	1.202 (2)	C2B—C3B	1.361 (4)
N5—N6	1.156 (3)	C2B—H2B	0.9300
N1A—C1A	1.321 (3)	C3B—C4B	1.407 (3)
N1A—C9A	1.368 (3)	C3B—H3B	0.9300
C1A—C2A	1.409 (3)	C4B—C5B	1.409 (3)
C1A—H1A	0.9300	C4B—C9B	1.421 (3)
C2A—C3A	1.356 (3)	C5B—C6B	1.353 (4)
C2A—H2A	0.9300	C5B—H5B	0.9300
C3A—C4A	1.409 (3)	C6B—C7B	1.405 (3)
C3A—H3A	0.9300	C6B—H6B	0.9300
C4A—C5A	1.409 (3)	C7B—C8B	1.369 (3)
C4A—C9A	1.415 (3)	C7B—H7B	0.9300
C5A—C6A	1.364 (3)	C8B—C9B	1.412 (3)
C5A—H5A	0.9300	C8B—N2B	1.449 (2)
C6A—C7A	1.409 (3)	N2B—H21	0.8900
C6A—H6A	0.9300	N2B—H22	0.8900

N4—Fe1—N1	89.57 (8)	C9A—C8A—N2A	116.40 (19)
N4—Fe1—N1B	99.91 (7)	N1A—C9A—C4A	122.67 (19)
N1—Fe1—N1B	92.82 (8)	N1A—C9A—C8A	117.69 (18)
N4—Fe1—N1A	96.47 (7)	C4A—C9A—C8A	119.6 (2)
N1—Fe1—N1A	98.77 (8)	C8A—N2A—Fe1	110.46 (12)
N1B—Fe1—N1A	159.98 (7)	C8A—N2A—H11	109.6
N4—Fe1—N2A	170.62 (7)	Fe1—N2A—H11	109.6
N1—Fe1—N2A	87.41 (8)	C8A—N2A—H12	109.6
N1B—Fe1—N2A	89.12 (7)	Fe1—N2A—H12	109.6
N1A—Fe1—N2A	75.25 (6)	H11—N2A—H12	108.1
N4—Fe1—N2B	91.37 (7)	C1B—N1B—C9B	118.0 (2)
N1—Fe1—N2B	168.84 (8)	C1B—N1B—Fe1	126.16 (17)
N1B—Fe1—N2B	76.06 (7)	C9B—N1B—Fe1	115.29 (14)
N1A—Fe1—N2B	92.18 (6)	N1B—C1B—C2B	123.2 (3)
N2A—Fe1—N2B	93.32 (7)	N1B—C1B—H1B	118.4
H1—O1—H2	105.0	C2B—C1B—H1B	118.4
N1—N2—N3	177.3 (3)	C3B—C2B—C1B	119.5 (2)
N2—N1—Fe1	157.4 (2)	C3B—C2B—H2B	120.2
N4—N5—N6	179.2 (2)	C1B—C2B—H2B	120.2
N5—N4—Fe1	122.3 (2)	C2B—C3B—C4B	119.4 (2)
C1A—N1A—C9A	117.74 (19)	C2B—C3B—H3B	120.3
C1A—N1A—Fe1	126.96 (16)	C4B—C3B—H3B	120.3
C9A—N1A—Fe1	114.43 (13)	C3B—C4B—C5B	123.5 (2)
N1A—C1A—C2A	123.2 (2)	C3B—C4B—C9B	117.5 (2)
N1A—C1A—H1A	118.4	C5B—C4B—C9B	119.0 (2)
C2A—C1A—H1A	118.4	C6B—C5B—C4B	120.4 (2)
C3A—C2A—C1A	119.4 (2)	C6B—C5B—H5B	119.8
C3A—C2A—H2A	120.3	C4B—C5B—H5B	119.8
C1A—C2A—H2A	120.3	C5B—C6B—C7B	120.9 (2)
C2A—C3A—C4A	119.8 (2)	C5B—C6B—H6B	119.6
C2A—C3A—H3A	120.1	C7B—C6B—H6B	119.6
C4A—C3A—H3A	120.1	C8B—C7B—C6B	120.6 (2)
C5A—C4A—C3A	123.7 (2)	C8B—C7B—H7B	119.7
C5A—C4A—C9A	119.2 (2)	C6B—C7B—H7B	119.7
C3A—C4A—C9A	117.0 (2)	C7B—C8B—C9B	119.7 (2)
C6A—C5A—C4A	119.9 (2)	C7B—C8B—N2B	123.2 (2)
C6A—C5A—H5A	120.0	C9B—C8B—N2B	117.08 (19)
C4A—C5A—H5A	120.0	N1B—C9B—C8B	118.40 (18)
C5A—C6A—C7A	121.1 (2)	N1B—C9B—C4B	122.3 (2)
C5A—C6A—H6A	119.5	C8B—C9B—C4B	119.3 (2)
C7A—C6A—H6A	119.5	C8B—N2B—Fe1	110.56 (13)
C8A—C7A—C6A	120.6 (2)	C8B—N2B—H21	109.5
C8A—C7A—H7A	119.7	Fe1—N2B—H21	109.5
C6A—C7A—H7A	119.7	C8B—N2B—H22	109.5
C7A—C8A—C9A	119.4 (2)	Fe1—N2B—H22	109.5
C7A—C8A—N2A	124.2 (2)	H21—N2B—H22	108.1

C9A—N1A—C1A—C2A	−0.6 (3)	C9B—N1B—C1B—C2B	−0.6 (4)
Fe1—N1A—C1A—C2A	168.09 (18)	Fe1—N1B—C1B—C2B	170.49 (18)
N1A—C1A—C2A—C3A	−2.2 (4)	N1B—C1B—C2B—C3B	−1.7 (4)
C1A—C2A—C3A—C4A	1.6 (4)	C1B—C2B—C3B—C4B	1.5 (4)
C2A—C3A—C4A—C5A	−177.9 (2)	C2B—C3B—C4B—C5B	−179.3 (2)
C2A—C3A—C4A—C9A	1.5 (3)	C2B—C3B—C4B—C9B	0.8 (3)
C3A—C4A—C5A—C6A	179.5 (2)	C3B—C4B—C5B—C6B	−179.4 (2)
C9A—C4A—C5A—C6A	0.1 (3)	C9B—C4B—C5B—C6B	0.6 (3)
C4A—C5A—C6A—C7A	2.8 (4)	C4B—C5B—C6B—C7B	0.8 (4)
C5A—C6A—C7A—C8A	−1.8 (4)	C5B—C6B—C7B—C8B	−1.0 (3)
C6A—C7A—C8A—C9A	−2.1 (3)	C6B—C7B—C8B—C9B	−0.2 (3)
C6A—C7A—C8A—N2A	177.4 (2)	C6B—C7B—C8B—N2B	179.2 (2)
C1A—N1A—C9A—C4A	4.0 (3)	C1B—N1B—C9B—C8B	−178.3 (2)
Fe1—N1A—C9A—C4A	−166.08 (17)	Fe1—N1B—C9B—C8B	9.6 (2)
C1A—N1A—C9A—C8A	−177.1 (2)	C1B—N1B—C9B—C4B	3.1 (3)
Fe1—N1A—C9A—C8A	12.9 (2)	Fe1—N1B—C9B—C4B	−168.97 (15)
C5A—C4A—C9A—N1A	175.0 (2)	C7B—C8B—C9B—N1B	−177.09 (19)
C3A—C4A—C9A—N1A	−4.5 (3)	N2B—C8B—C9B—N1B	3.4 (3)
C5A—C4A—C9A—C8A	−3.9 (3)	C7B—C8B—C9B—C4B	1.6 (3)
C3A—C4A—C9A—C8A	176.6 (2)	N2B—C8B—C9B—C4B	−177.91 (17)
C7A—C8A—C9A—N1A	−174.1 (2)	C3B—C4B—C9B—N1B	−3.2 (3)
N2A—C8A—C9A—N1A	6.4 (3)	C5B—C4B—C9B—N1B	176.8 (2)
C7A—C8A—C9A—C4A	4.9 (3)	C3B—C4B—C9B—C8B	178.22 (19)
N2A—C8A—C9A—C4A	−174.59 (19)	C5B—C4B—C9B—C8B	−1.7 (3)
C7A—C8A—N2A—Fe1	158.94 (18)	C7B—C8B—N2B—Fe1	166.65 (17)
C9A—C8A—N2A—Fe1	−21.6 (2)	C9B—C8B—N2B—Fe1	−13.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N4ⁱ	0.96	1.88	2.838 (3)	175
O1—H2···N3ⁱⁱ	0.96	1.85	2.807 (3)	174
N2A—H11···N6ⁱⁱ	0.89	2.17	3.052 (3)	170
N2A—H12···O1	0.89	2.28	3.086 (3)	151
N2B—H21···N3ⁱⁱⁱ	0.89	2.35	3.206 (3)	160
N2B—H22···O1	0.89	2.17	3.037 (2)	164

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

Acknowledgements

Le plateau CRISTAL de l'Université d'Angers 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 (Ministère de l'Enseignement Supérieur et de la Recherche Scientifique), the Algerian DGRSDT (Direction Générale de la Recherche Scientifique et du développement Technologique), and the PRFU project (grant No. B00L01UN190120230003).

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