Crystal structure of bis­(azido-κN)bis­(quinolin-8-amine-κ2N,N′)iron(II)

Setifi, F.; Moon, D.; Koen, R.; Setifi, Z.; Lamsayah, M.; Touzani, R.

doi:10.1107/S2056989016014808

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ISSN: 2056-9890

Volume 72| Part 10| October 2016| Pages 1488-1491

https://doi.org/10.1107/S2056989016014808

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Crystal structure of bis(azido-κN)bis(quinolin-8-amine-κ²N,N′)iron(II)

Fatima Setifi,^a ^* Dohyun Moon,^b Robeyns Koen,^c ^* Zouaoui Setifi,^a Morad Lamsayah ^d,^e and Rachid Touzani ^d,^e ^*

^aLaboratoire de Chimie, Ingénierie Moléculaire et Nanostructures (LCIMN), Université Ferhat Abbas Sétif 1, Sétif 19000, Algeria, ^bPohang Accelerator Laboratory, POSTECH, Pohang 37673, Republic of Korea, ^cInstitute of Condensed Matter and Nanosciences (IMCN), Université Catholique de Louvain, 1 Place Louis Pasteur, B 1348 Louvain-la-Neuve, Belgium, ^dLaboratoire de Chimie Appliquée et Environnement, LCAE-URAC18, COSTE, Faculté des Sciences, Université Mohamed Premier, BP524, 60000, Oujda, Morocco, and ^eFaculté Pluridisciplinaire Nador BP 300, Selouane, 62702, Nador, Morocco
^*Correspondence e-mail: fat_setifi@yahoo.fr, koen.robeyns@uclouvain.be, touzanir@yahoo.fr

Edited by T. J. Prior, University of Hull, England (Received 7 September 2016; accepted 19 September 2016; online 30 September 2016)

The search for new molecular materials with interesting magnetic properties using the pseudohalide azide ion and quinolin-8-amine (aqin, C₉H₈N₂) as a chelating ligand, led to the synthesis and structure determination of the title complex, [Fe(N₃)₂(C₉H₈N₂)₂]. The complex shows an octahedral geometry, with the Fe^II atom surrounded by six N atoms; the two N₃⁻ anions coordinate in a cis configuration, while the remaining N atoms originate from the two quinolin-8-amine ligands with the quinoline N atoms lying on opposite sides of the Fe atom. The crystal packing is dominated by layers of hydrophilic and aromatic regions parallel to the ac plane, stabilized by a two-dimensional hydrogen-bonded network and π–π stacking.

Keywords: crystal structure; hydrothermal synthesis; coordination compound; Fe^II complex; quinolin-8-amine; azide; hydrogen bonding; π–π stacking.

CCDC reference: 1505176

1. Chemical context

In recent years, molecular magnetism has attracted great attention due to the interest in designing new molecular materials with interesting magnetic properties and potential applications (Kahn, 1993 ; Miller & Gatteschi, 2011 ). Connecting paramagnetic centers by use of bridging polynitrile or pseudohalide ligands is an important strategy to design such materials (Setifi et al., 2002 , 2003 ; Gaamoune et al., 2010 ; Miyazaki et al., 2003 ; Benmansour et al., 2008 , 2009 ; Yuste et al., 2009 ; Setifi et al., 2013 , 2014 ; Addala et al., 2015 ). As a short bridging ligand and efficient superexchange mediator, the pseudohalide azide ion has proved to be very versatile and diverse in both coordination chemistry and magnetism. It can link metal ions in μ-1,1 (end-on, EO), μ-1,3 (end-to-end, EE), μ-1,1,1 and other modes, and effectively mediate either ferromagnetic or antiferromagnetic coupling. Many azide-bridged systems with different dimensionality and topologies have been synthesized by using various auxiliary ligands, and a great diversity of magnetic behavior has been demonstrated (Ribas et al., 1999 ; Gao et al., 2004 ; Liu et al., 2007 ; Mautner et al., 2010 ). In view of the possible roles of the versatile azido ligand, we have been interested in using it 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 quinolin-8-amine, we isolated the title compound, whose structure is described herein.

2. Structural commentary

The title compound shows an octahedral coordination around the Fe^II atom. The Fe complex is a neutral and discrete molecule and the two coordinating N₃⁻ anions occupy adjacent sites, classifying the title compound as a cis-complex. Fig. 1 shows the molecular structure.

Figure 1
The molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

The octahedral positions are occupied by six nitrogen atoms where the quinoline aromatic nitrogen atoms are found in the trans positions. All six Fe—N bond lengths are essentially uniform [2.104 (3)–2.284 (3) Å] and typical for high-spin iron(II) compounds (Table 1). The Fe—NH₂ bond lengths are somewhat longer (∼0.10 Å) than the other Fe—N bonds. As a result of the quinolin-8-amine bite angle of about 75° the octahedral geometry is slightly distorted, allowing better separation of the negative charges on the azide ligands.

Table 1
Selected geometric parameters (Å, °)

Fe1—N8	2.104 (3)	Fe1—N4	2.175 (2)
Fe1—N2	2.160 (3)	Fe1—N3	2.241 (3)
Fe1—N5	2.174 (3)	Fe1—N1	2.284 (3)

N8—Fe1—N2	91.14 (12)	N5—Fe1—N3	82.06 (11)
N8—Fe1—N5	94.16 (13)	N4—Fe1—N3	76.67 (9)
N2—Fe1—N5	95.49 (10)	N8—Fe1—N1	88.56 (13)
N8—Fe1—N4	94.82 (12)	N2—Fe1—N1	75.65 (10)
N2—Fe1—N4	167.88 (9)	N5—Fe1—N1	170.81 (10)
N5—Fe1—N4	94.59 (10)	N4—Fe1—N1	93.92 (9)
N8—Fe1—N3	170.31 (11)	N3—Fe1—N1	96.56 (10)
N2—Fe1—N3	98.09 (9)

3. Supramolecular features

Looking down the a axis (Fig. 2) one can notice alternating layers (stacked along the b-axis direction) of hydrophilic and aromatic regions. This layering can also be seen at the level of the complex itself, where the aromatic quinoline moieties are located above and below the hydrophilic plane formed by the NH₂ and N₃⁻ groups. These latter are engaged in hydrogen bonds expanding along the ac plane (Table 2). Both H atoms of the NH₂ group involving N1 form hydrogen bonds with the terminal nitrogen atoms of two neighboring (symmetry-related) azide ligands. The other NH₂ group has one of its hydrogen atoms (N3—N3A) involved in a similar interaction, and the other hydrogen (N3—N3B) shows a very weak interaction with the coordinating end of a neighboring azide ion. The aromatic rings on the other hand show parallel displaced π-stacking between pairs of quinoline (Q) moieties, the distance between the two quinoline planes is 3.38 Å (measured as the distance between the centroid of Q1 and the plane through Q2), or 3.35 Å, when interchanging Q1 and Q2. Some of the hydrogen bonds (Table 2) are rather long and the stabilization of the crystal packing comes from the combined effect of the hydrogen-bonding interactions, which direct the orientation of the neighboring complexes and the additional π–π stacking interactions that hold the complexes in place.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N10ⁱ	0.89	2.62	3.361 (6)	141
N1—H1B⋯N10ⁱⁱ	0.89	2.42	3.254 (6)	157
N3—H3A⋯N7ⁱ	0.89	2.22	3.019 (4)	149
N3—H3B⋯N5ⁱⁱⁱ	0.89	2.72	3.561 (4)	159
Symmetry codes: (i) x-1, y, z; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (iii) -x+1, -y+1, -z+1.

Figure 2
(Left) A view down the a axis, showing the alternating layers of hydrophilic and aromatic regions. (Right) The hydrogen-bonding network found in the hydrophilic region.

4. Database survey

A search in the Cambridge Structural Database (Version 5.37, Feb 2016 with two updates; Groom et al., 2016 ) reveals that only nine Fe^II complexes with quinolin-8-amine groups have been reported. None of these complexes involve azide groups, neither coordinating nor as a free anion. There is one known Cd complex that contains 8-aminoquinoline and bound azide; rather than forming discrete entities, the Cd complex is polymeric, expanding into chains where the azides act as bridging ligands [refcodes WIJWES (Paira et al., 2007 ) and WIJWES01 (Xu et al., 2008 )] in the EO mode. Considering the azides and their coordination modes, the predominant N₃⁻ binding mode is as monodentate (2210 entries), among the bridging modes the μ₂ modes either 1,1 EO (1652 entries) or 1,3 EE (931 entries) are most favored. The other EO modes μ₃ (159 entries) or μ₄ (11 entries) are far less frequent. Similar observations are made for the more complex end-to-end bridging modes: μ₃-1,1,3 (131), μ₄-1,1,3,3 (13), μ₄-1,1,1,3 (11), μ₅-1,1,1,3,3 (1). For completeness, the occurrence of N₃⁻ as a free anion is not so common, as only 92 entries were identified in the CSD database.

5. Synthesis and crystallization

The title compound was synthesized hydrothermally under autogenous pressure from a mixture of iron(II) sulfate heptahydrate (28 mg, 0.1 mmol), quinolin-8-amine (15 mg, 0.1 mmol) and sodium azide NaN₃ (13 mg, 0.2 mmol) in water–methanol (4:1 v/v, 20 ml). The mixture was sealed in a Teflon-lined autoclave and heated at 453 K for two days and cooled to room temperature at 10 K h⁻¹. The crystals were obtained in ca 20% yield based on iron and proved to consist of a mononuclear heteroleptic Fe complex rather than the expected polymeric architecture with bridging azides.

CAUTION! Although not encountered in our experiments, azido compounds of metal ions are potentially explosive. Only a small amount of the materials should be prepared, and it should be handled with care.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93 Å, N—H distance of 0.89 Å and with 1.2U_eq of the parent atom.

Table 3
Experimental details

Crystal data
Chemical formula	[Fe(N₃)(C₉H₈N₂)₂]
M_r	428.26
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	8.1798 (8), 15.8675 (13), 27.775 (4)
V (Å³)	3605.0 (6)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.87
Crystal size (mm)	0.35 × 0.21 × 0.11

Data collection
Diffractometer	Bruker–Nonius Kappa CCD with an APEXII detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003 )
T_min, T_max	0.606, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	16951, 4100, 2081
R_int	0.092
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.121, 0.97
No. of reflections	4100
No. of parameters	262
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.36
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1505176

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989016014808/pj2035sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016014808/pj2035Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 and SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

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

Crystal data top

[Fe(N₃)(C₉H₈N₂)₂]	D_x = 1.578 Mg m⁻³
M_r = 428.26	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 1795 reflections
a = 8.1798 (8) Å	θ = 2.4–26.9°
b = 15.8675 (13) Å	µ = 0.87 mm⁻¹
c = 27.775 (4) Å	T = 296 K
V = 3605.0 (6) Å³	Prism, red
Z = 8	0.35 × 0.21 × 0.11 mm
F(000) = 1760

Data collection top

Bruker–Nonius Kappa CCD with an APEXII detector diffractometer	4100 independent reflections
Radiation source: fine focus sealed tube	2081 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.092
φ and ω scans	θ_max = 27.5°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→9
T_min = 0.606, T_max = 0.746	k = −20→20
16951 measured reflections	l = −34→35

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H-atom parameters constrained
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.0475P)²] where P = (F_o² + 2F_c²)/3
S = 0.97	(Δ/σ)_max < 0.001
4100 reflections	Δρ_max = 0.32 e Å⁻³
262 parameters	Δρ_min = −0.36 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
Fe1	0.50883 (5)	0.47368 (3)	0.61957 (2)	0.03352 (17)
N1	0.3287 (3)	0.49268 (15)	0.68146 (12)	0.0413 (8)
H1A	0.2316	0.4718	0.6733	0.050*
H1B	0.3637	0.4649	0.7073	0.050*
N2	0.4757 (3)	0.60857 (16)	0.62329 (10)	0.0327 (7)
N3	0.3216 (3)	0.44621 (15)	0.56279 (11)	0.0341 (7)
H3A	0.2237	0.4634	0.5728	0.041*
H3B	0.3461	0.4745	0.5361	0.041*
N4	0.4890 (3)	0.33703 (15)	0.62114 (10)	0.0309 (6)
N5	0.6707 (3)	0.47625 (17)	0.55749 (12)	0.0482 (9)
N6	0.8137 (3)	0.47003 (15)	0.56124 (12)	0.0387 (8)
N7	0.9542 (3)	0.4642 (2)	0.56381 (16)	0.0735 (13)
N8	0.7006 (4)	0.4793 (2)	0.66995 (14)	0.0680 (11)
N9	0.8201 (4)	0.46219 (18)	0.68843 (14)	0.0522 (9)
N10	0.9391 (5)	0.4460 (3)	0.70919 (18)	0.1184 (19)
C1	0.3122 (4)	0.58115 (19)	0.69286 (14)	0.0337 (8)
C2	0.2228 (4)	0.6099 (2)	0.73119 (14)	0.0439 (10)
H2	0.1680	0.5719	0.7509	0.053*
C3	0.2137 (4)	0.6972 (3)	0.74073 (15)	0.0512 (11)
H3	0.1540	0.7162	0.7671	0.061*
C4	0.2909 (4)	0.7538 (2)	0.71204 (15)	0.0458 (10)
H4	0.2848	0.8110	0.7191	0.055*
C5	0.3793 (4)	0.7268 (2)	0.67206 (14)	0.0359 (9)
C6	0.4590 (4)	0.7814 (2)	0.64010 (15)	0.0408 (10)
H6	0.4556	0.8392	0.6455	0.049*
C7	0.5399 (4)	0.7512 (2)	0.60195 (15)	0.0444 (10)
H7	0.5918	0.7878	0.5807	0.053*
C8	0.5459 (4)	0.6630 (2)	0.59412 (14)	0.0417 (9)
H8	0.6016	0.6429	0.5673	0.050*
C9	0.3901 (3)	0.63909 (18)	0.66224 (12)	0.0277 (7)
C10	0.3161 (3)	0.35638 (18)	0.55234 (12)	0.0276 (8)
C11	0.2290 (4)	0.3235 (2)	0.51487 (13)	0.0378 (9)
H11	0.1705	0.3591	0.4946	0.045*
C12	0.2274 (4)	0.2361 (2)	0.50673 (15)	0.0460 (10)
H12	0.1678	0.2145	0.4810	0.055*
C13	0.3114 (4)	0.1829 (2)	0.53578 (15)	0.0437 (10)
H13	0.3108	0.1253	0.5294	0.052*
C14	0.3997 (4)	0.21408 (19)	0.57561 (14)	0.0330 (8)
C15	0.4861 (4)	0.1629 (2)	0.60823 (14)	0.0427 (10)
H15	0.4863	0.1047	0.6043	0.051*
C16	0.5685 (4)	0.1980 (2)	0.64518 (16)	0.0493 (11)
H16	0.6258	0.1643	0.6668	0.059*
C17	0.5670 (4)	0.2858 (2)	0.65075 (15)	0.0437 (10)
H17	0.6237	0.3091	0.6765	0.052*
C18	0.4037 (3)	0.30219 (19)	0.58328 (12)	0.0280 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0268 (2)	0.0307 (3)	0.0430 (3)	0.0016 (2)	−0.0010 (3)	−0.0070 (2)
N1	0.0433 (17)	0.0335 (16)	0.047 (2)	0.0018 (13)	0.0047 (16)	0.0042 (14)
N2	0.0287 (14)	0.0356 (15)	0.0339 (18)	−0.0009 (11)	0.0033 (15)	−0.0009 (14)
N3	0.0251 (13)	0.0356 (15)	0.042 (2)	0.0024 (11)	0.0027 (14)	0.0039 (14)
N4	0.0314 (13)	0.0311 (14)	0.0302 (17)	0.0058 (12)	−0.0011 (15)	−0.0012 (13)
N5	0.0304 (15)	0.061 (2)	0.054 (2)	−0.0014 (14)	0.0045 (15)	−0.0090 (17)
N6	0.0358 (16)	0.0280 (15)	0.052 (2)	−0.0033 (13)	0.0083 (15)	−0.0075 (14)
N7	0.0288 (16)	0.073 (2)	0.119 (4)	0.0023 (15)	0.007 (2)	−0.026 (2)
N8	0.0478 (19)	0.094 (3)	0.062 (3)	0.0134 (19)	−0.025 (2)	−0.020 (2)
N9	0.0447 (19)	0.051 (2)	0.061 (3)	0.0080 (16)	−0.0083 (19)	−0.0333 (18)
N10	0.084 (3)	0.155 (4)	0.116 (4)	0.068 (3)	−0.053 (3)	−0.080 (3)
C1	0.0308 (17)	0.0343 (19)	0.036 (2)	0.0068 (14)	0.0010 (17)	0.0049 (17)
C2	0.0412 (19)	0.058 (2)	0.033 (2)	0.0112 (18)	0.0085 (19)	0.010 (2)
C3	0.054 (2)	0.065 (3)	0.034 (3)	0.025 (2)	0.006 (2)	−0.004 (2)
C4	0.051 (2)	0.041 (2)	0.045 (3)	0.0187 (18)	−0.006 (2)	−0.008 (2)
C5	0.0359 (18)	0.040 (2)	0.032 (2)	0.0067 (15)	−0.0071 (18)	−0.0013 (18)
C6	0.044 (2)	0.0315 (18)	0.047 (3)	−0.0025 (15)	−0.012 (2)	0.0004 (19)
C7	0.043 (2)	0.038 (2)	0.052 (3)	−0.0060 (16)	−0.001 (2)	0.013 (2)
C8	0.044 (2)	0.047 (2)	0.034 (2)	−0.0027 (16)	0.0071 (18)	0.0066 (19)
C9	0.0254 (15)	0.0319 (18)	0.026 (2)	0.0081 (13)	−0.0032 (15)	−0.0002 (16)
C10	0.0241 (15)	0.0314 (17)	0.027 (2)	−0.0040 (13)	0.0042 (15)	−0.0001 (16)
C11	0.0338 (18)	0.051 (2)	0.029 (2)	−0.0030 (16)	−0.0022 (17)	−0.0013 (19)
C12	0.043 (2)	0.058 (3)	0.037 (3)	−0.0142 (19)	−0.001 (2)	−0.014 (2)
C13	0.041 (2)	0.038 (2)	0.052 (3)	−0.0121 (17)	0.013 (2)	−0.012 (2)
C14	0.0307 (17)	0.0318 (19)	0.036 (2)	−0.0013 (14)	0.0095 (17)	−0.0008 (17)
C15	0.0441 (19)	0.0313 (18)	0.053 (3)	−0.0008 (17)	0.012 (2)	0.0004 (17)
C16	0.050 (2)	0.040 (2)	0.057 (3)	0.0112 (17)	0.000 (2)	0.014 (2)
C17	0.0431 (19)	0.046 (2)	0.042 (3)	0.0032 (17)	−0.0066 (19)	0.001 (2)
C18	0.0236 (15)	0.0353 (18)	0.025 (2)	−0.0013 (14)	0.0085 (15)	−0.0023 (16)

Geometric parameters (Å, º) top

Fe1—N8	2.104 (3)	C3—H3	0.9300
Fe1—N2	2.160 (3)	C4—C5	1.392 (5)
Fe1—N5	2.174 (3)	C4—H4	0.9300
Fe1—N4	2.175 (2)	C5—C6	1.401 (5)
Fe1—N3	2.241 (3)	C5—C9	1.421 (4)
Fe1—N1	2.284 (3)	C6—C7	1.338 (5)
N1—C1	1.445 (4)	C6—H6	0.9300
N1—H1A	0.8900	C7—C8	1.416 (5)
N1—H1B	0.8900	C7—H7	0.9300
N2—C8	1.316 (4)	C8—H8	0.9300
N2—C9	1.377 (4)	C10—C11	1.365 (4)
N3—C10	1.455 (4)	C10—C18	1.411 (4)
N3—H3A	0.8900	C11—C12	1.405 (4)
N3—H3B	0.8900	C11—H11	0.9300
N4—C17	1.321 (4)	C12—C13	1.355 (5)
N4—C18	1.378 (4)	C12—H12	0.9300
N5—N6	1.179 (3)	C13—C14	1.411 (5)
N6—N7	1.155 (3)	C13—H13	0.9300
N8—N9	1.136 (4)	C14—C15	1.407 (5)
N9—N10	1.160 (4)	C14—C18	1.415 (4)
C1—C2	1.370 (4)	C15—C16	1.349 (5)
C1—C9	1.405 (4)	C15—H15	0.9300
C2—C3	1.412 (5)	C16—C17	1.401 (4)
C2—H2	0.9300	C16—H16	0.9300
C3—C4	1.357 (5)	C17—H17	0.9300

N8—Fe1—N2	91.14 (12)	C3—C4—C5	120.4 (3)
N8—Fe1—N5	94.16 (13)	C3—C4—H4	119.8
N2—Fe1—N5	95.49 (10)	C5—C4—H4	119.8
N8—Fe1—N4	94.82 (12)	C4—C5—C6	123.8 (3)
N2—Fe1—N4	167.88 (9)	C4—C5—C9	119.1 (3)
N5—Fe1—N4	94.59 (10)	C6—C5—C9	117.0 (3)
N8—Fe1—N3	170.31 (11)	C7—C6—C5	120.7 (3)
N2—Fe1—N3	98.09 (9)	C7—C6—H6	119.6
N5—Fe1—N3	82.06 (11)	C5—C6—H6	119.6
N4—Fe1—N3	76.67 (9)	C6—C7—C8	119.5 (3)
N8—Fe1—N1	88.56 (13)	C6—C7—H7	120.3
N2—Fe1—N1	75.65 (10)	C8—C7—H7	120.3
N5—Fe1—N1	170.81 (10)	N2—C8—C7	122.6 (3)
N4—Fe1—N1	93.92 (9)	N2—C8—H8	118.7
N3—Fe1—N1	96.56 (10)	C7—C8—H8	118.7
C1—N1—Fe1	110.7 (2)	N2—C9—C1	118.4 (3)
C1—N1—H1A	109.5	N2—C9—C5	121.8 (3)
Fe1—N1—H1A	109.5	C1—C9—C5	119.8 (3)
C1—N1—H1B	109.5	C11—C10—C18	119.8 (3)
Fe1—N1—H1B	109.5	C11—C10—N3	122.8 (3)
H1A—N1—H1B	108.1	C18—C10—N3	117.4 (3)
C8—N2—C9	118.3 (3)	C10—C11—C12	120.3 (3)
C8—N2—Fe1	124.5 (2)	C10—C11—H11	119.8
C9—N2—Fe1	116.8 (2)	C12—C11—H11	119.8
C10—N3—Fe1	110.59 (18)	C13—C12—C11	121.0 (3)
C10—N3—H3A	109.5	C13—C12—H12	119.5
Fe1—N3—H3A	109.5	C11—C12—H12	119.5
C10—N3—H3B	109.5	C12—C13—C14	120.5 (3)
Fe1—N3—H3B	109.5	C12—C13—H13	119.7
H3A—N3—H3B	108.1	C14—C13—H13	119.7
C17—N4—C18	118.2 (3)	C15—C14—C13	124.0 (3)
C17—N4—Fe1	126.2 (2)	C15—C14—C18	117.5 (3)
C18—N4—Fe1	115.0 (2)	C13—C14—C18	118.5 (3)
N6—N5—Fe1	122.2 (3)	C16—C15—C14	120.2 (3)
N7—N6—N5	178.5 (5)	C16—C15—H15	119.9
N9—N8—Fe1	158.7 (3)	C14—C15—H15	119.9
N8—N9—N10	177.0 (5)	C15—C16—C17	119.3 (3)
C2—C1—C9	119.7 (3)	C15—C16—H16	120.3
C2—C1—N1	122.9 (3)	C17—C16—H16	120.3
C9—C1—N1	117.4 (3)	N4—C17—C16	123.2 (4)
C1—C2—C3	120.0 (3)	N4—C17—H17	118.4
C1—C2—H2	120.0	C16—C17—H17	118.4
C3—C2—H2	120.0	N4—C18—C10	118.5 (3)
C4—C3—C2	121.0 (4)	N4—C18—C14	121.5 (3)
C4—C3—H3	119.5	C10—C18—C14	119.9 (3)
C2—C3—H3	119.5

Fe1—N1—C1—C2	−174.2 (3)	Fe1—N3—C10—C11	−171.0 (2)
Fe1—N1—C1—C9	6.9 (3)	Fe1—N3—C10—C18	9.9 (3)
C9—C1—C2—C3	−2.1 (5)	C18—C10—C11—C12	−0.5 (5)
N1—C1—C2—C3	179.0 (3)	N3—C10—C11—C12	−179.6 (3)
C1—C2—C3—C4	0.9 (5)	C10—C11—C12—C13	0.1 (5)
C2—C3—C4—C5	0.8 (6)	C11—C12—C13—C14	1.4 (5)
C3—C4—C5—C6	178.4 (3)	C12—C13—C14—C15	178.1 (3)
C3—C4—C5—C9	−1.2 (5)	C12—C13—C14—C18	−2.5 (5)
C4—C5—C6—C7	−179.0 (3)	C13—C14—C15—C16	179.5 (3)
C9—C5—C6—C7	0.6 (5)	C18—C14—C15—C16	0.1 (5)
C5—C6—C7—C8	−0.5 (5)	C14—C15—C16—C17	0.1 (5)
C9—N2—C8—C7	1.6 (5)	C18—N4—C17—C16	0.7 (5)
Fe1—N2—C8—C7	−170.7 (2)	Fe1—N4—C17—C16	−169.8 (3)
C6—C7—C8—N2	−0.6 (5)	C15—C16—C17—N4	−0.5 (6)
C8—N2—C9—C1	178.7 (3)	C17—N4—C18—C10	178.1 (3)
Fe1—N2—C9—C1	−8.4 (3)	Fe1—N4—C18—C10	−10.3 (3)
C8—N2—C9—C5	−1.5 (4)	C17—N4—C18—C14	−0.5 (4)
Fe1—N2—C9—C5	171.4 (2)	Fe1—N4—C18—C14	171.1 (2)
C2—C1—C9—N2	−178.4 (3)	C11—C10—C18—N4	−179.3 (3)
N1—C1—C9—N2	0.5 (4)	N3—C10—C18—N4	−0.2 (4)
C2—C1—C9—C5	1.8 (5)	C11—C10—C18—C14	−0.6 (4)
N1—C1—C9—C5	−179.3 (3)	N3—C10—C18—C14	178.5 (3)
C4—C5—C9—N2	−180.0 (3)	C15—C14—C18—N4	0.1 (4)
C6—C5—C9—N2	0.4 (4)	C13—C14—C18—N4	−179.3 (3)
C4—C5—C9—C1	−0.1 (5)	C15—C14—C18—C10	−178.5 (3)
C6—C5—C9—C1	−179.7 (3)	C13—C14—C18—C10	2.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N10ⁱ	0.89	2.62	3.361 (6)	141
N1—H1B···N10ⁱⁱ	0.89	2.42	3.254 (6)	157
N3—H3A···N7ⁱ	0.89	2.22	3.019 (4)	149
N3—H3B···N5ⁱⁱⁱ	0.89	2.72	3.561 (4)	159

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

Acknowledgements

The authors acknowledge the Algerian MESRS (Ministère de l'Enseignement Supérieur et de la Recherche Scientifique), the DGRSDT (Direction Générale de la Recherche Scientifique et du Développement Technologique) and Université Ferhat Abbas Sétif 1 for financial support.

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