Synthesis, crystal structure and properties of chlorido­tetra­kis­(pyridine-3-carbo­nitrile)­thio­cyanato­iron(II)

Müller-Meinhard, A.; Jess, I.; Näther, C.

doi:10.1107/S205698902300988X

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 79| Part 12| December 2023| Pages 1173-1178

https://doi.org/10.1107/S205698902300988X

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Synthesis, crystal structure and properties of chloridotetrakis(pyridine-3-carbonitrile)thiocyanatoiron(II)

Asmus Müller-Meinhard,^a Inke Jess ^a and Christian Näther ^a ^*

^aInstitut für Anorganische Chemie, Universität Kiel, Max-Eyth. Str. 2, 24118 Kiel, Germany
^*Correspondence e-mail: cnaether@ac.uni-kiel.de

Edited by X. Hao, Institute of Chemistry, Chinese Academy of Sciences (Received 8 November 2023; accepted 14 November 2023; online 21 November 2023)

Reaction of FeCl₂·4H₂O with KSCN and 3-cyanopyridine (pyridine-3-carbonitrile) in ethanol accidentally leads to the formation of single crystals of Fe(NCS)(Cl)(3-cyanopyridine)₄ or [FeCl(NCS)(C₆H₄N₂)₄]. The asymmetric unit of this compound consists of one Fe^II cation, one chloride and one thiocyanate anion that are located on a fourfold rotation axis as well as of one 3-cyanopyridine coligand in a general position. The Fe^II cations are sixfold coordinated by one chloride anion and one terminally N-bonding thiocyanate anion in trans-positions and four 3-cyanopyridine coligands that coordinate via the pyridine N atom to the Fe^II cations. The complexes are arranged in columns with the chloride anions, with the thiocyanate anions always oriented in the same direction, which shows the non-centrosymmetry of this structure. No pronounced intermolecular interactions are observed between the complexes. Initially, FeCl₂ and KSCN were reacted in a 1:2 ratio, which lead to a sample that contains the title compound as the major phase together with a small amount of an unknown crystalline phase, as proven by powder X-ray diffraction (PXRD). If FeCl₂ and KSCN is reacted in a 1:1 ratio, the title compound is obtained as a nearly pure phase. IR investigations reveal that the CN stretching vibration for the thiocyanate anion is observed at 2074 cm⁻¹, and that of the cyano group at 2238 cm⁻¹, which also proves that the anionic ligands are only terminally bonded and that the cyano group is not involved in the metal coordination. Measurements with thermogravimetry and differential thermoanalysis reveal that the title compound decomposes at 169°C when heated at a rate of 4°C min⁻¹ and that the 3-cyanopyridine ligands are emitted in two separate poorly resolved steps. After the first step, an intermediate compound with the composition Fe(NCS)(Cl)(3-cyanopyridine)₂ of unknown structure is formed, for which the CN stretching vibration of the thiocyanate anion is observed at 2025 cm⁻¹, whereas the CN stretching vibration of the cyano group remain constant. This strongly indicates that the Fe^II cations are linked by μ-1,3-bridging thiocyanate anions into chains or layers.

Keywords: synthesis; crystal structure; mixed iron thiocyanate chloride complex; powder diffraction; thermal properties.

CCDC reference: 2307914

1. Chemical context

Thiocyanate anions are versatile ligands, which show a number of different coordination modes, leading to a pronounced structural variability. This ligand can act as a monocoordinating ligand, which in most cases leads to the formation of complexes that are of interest, for example in the field of spin-crossover compounds, which is especially the case with Fe(NCS)₂ (Gütlich et al., 2000 ; Naggert et al., 2015 ; Senthil Kumar & Ruben Kuppusamy, 2017 ; Hogue et al., 2018 ). Moreover, this anionic ligand is able to mediate magnetic exchange and therefore, compounds with bridging thiocyanate anions are also of interest (Palion-Gazda et al., 2015 ; Mekuimemba et al., 2018 ). In this context, compounds based on Co(NCS)₂ are of special importance because of the large magnetic anisotropy of Co^II (Mautner et al., 2018 ; Wöhlert et al., 2013 ; Rams et al., 2020 ). All these are reasons why the interest in the synthesis, structures and properties of thiocyanate coordination compounds is still very high. In our own investigations, we are especially interested in coordination compounds with Mn^II, Fe^II, Co^II and Ni^II cations.

The synthesis of such thiocyanate coordination compounds with manganese, cobalt and nickel is usually very easy because their thiocyanate salts are commercially available or can easily be prepared and stored for a long time, which is not the case for Fe(NCS)₂. For the synthesis of coordination compounds with this cation, Fe(NCS)₂ is usually prepared in situ, for example by the reaction of an Fe^II salt such as FeCl₂ or FeSO₄ with KSCN, which afterwards reacts with the organic ligand to form the desired thiocyanate compound. The potassium salt formed in this reaction can finally be removed, for example by washing the residue with water. We have used this procedure many times for the preparation of new Fe(NCS)₂ compounds, and it usually leads to pure samples (Wöhlert et al., 2013; Werner et al., 2015a ,b ).

However, in the course of our systematic investigations we became interested in the synthesis of Fe(NCS)₂ precursor complexes with 3-cyanopyridine as coligand, for which corresponding compounds with Mn^II and Ni^II had already been investigated by us (Krebs et al., 2021 , 2023 ). In this work we investigated whether 3-cyanopyridine-rich complexes with terminally N-bonded thiocyanate anions can be prepared and transformed into 3-cyanopyridine-deficient complexes with bridging thiocyanate anions by thermal decomposition. For a number of complexes with Ni(NCS)₂ we found that they transform into a new compound with the composition Ni(NCS)₂(3-cyanopyridine)₂, in which the metal cations are linked by the thiocyanate anions into layers and in which the 3-cyanopyridine ligand is only terminally bonded (Krebs et al., 2021). Surprisingly, corresponding complexes with Mn(NCS)₂ transform into an unusual compound with the composition {[Mn(NCS)₂]₃(3-cyanopyridine)₄}_n, which is isotypic to the corresponding compound with Cd(NCS)₂ already reported in the literature (Jochim et al., 2020a ,b ) and which consists of Mn(NCS)₂ chains that are connected by some bridging 3-cyanopyridine ligands into layers, whereas some others are still terminally bonded (Krebs et al., 2023). The reason for the differences in the thermal behavior is unclear, but the question arises whether cations in between Mn^II and Ni^II will show a thermal behavior similar to that of Mn^II or Ni^II. We therefore decided to attempt to prepare thiocyanate complexes based on Fe(NCS)₂ and 3-cyanopyridine.

For the synthesis of such compounds we reacted FeCl₂ and FeSO₄ with KSCN, which led to the formation of crystalline products that were identified by single-crystal X-ray diffraction. This proves that in the batch obtained from FeCl₂·6H₂O, a compound with the composition Fe(NCS)(Cl)(3-cyanopyridine)₄ was accidentally obtained, in which both thiocyanate and chloride anions are present. In contrast, with FeSO₄, the desired compounds with composition Fe(NCS)₂(3-cyanopyridine)₄ and Fe(NCS)₂(3-cyanopyridine)₂(H₂O)₂·2(3-cyanopyridine) were obtained (Näther et al., 2023 ). In this context, it is noted that compounds with transition metals coordinated by a halide anion and a thiocyanate anion with 3-cyanopyridine are unknown. In general, only one Fe compound is found in the CSD (see Database survey) in which the Fe^II cation is coordinated by one chloride anion, one thiocyanate anion and an N-donor ligand (Horng & Lee, 1999 ). Concerning the synthesis of such compounds, most compounds reported in literature were prepared by the reaction of one equivalent of a transition metal–halide salt with one or two equivalents of potassium or ammonium thiocyanate, very similar to the synthesis of the title compound, but in none of these publications was the purity of the compounds investigated by X-ray powder diffraction (PXRD).

2. Structural commentary

The asymmetric unit of the title compound, Fe(NCS)(Cl)(3-cyanopyridine)₄, consists of one iron cation, one thiocyanate anion and one chloride anion that are located on a fourfold rotation axis, as well as of one 3-cyanopyridine coligand that occupies a general position (Fig. 1). In the crystal structure, the Fe^II cations are coordinated by one terminally N-bonded thiocyanate anion and one chloride anion in trans-positions and four symmetry-related 3-cyanopyridine coligands that are coordinated via the pyridine N atom to the Fe centers (Fig. 1). As a result of symmetry, all four Fe—N bond lengths to the coligands are identical and correspond to literature values. The bonding angles deviate from the ideal values, which is especially the case for the Cl—Fe—N_{3-cyanopyridine} and the N_NCS—Fe—N_{3-cyanopyridine} angle, whereas the N—Fe—N angles of neighboring 3-cyanopyridine coligands are close to 90° (Table 1). Therefore, the octahedra are slightly distorted. As a result of steric repulsion, the 3-cyanopyridine ring planes are not coplanar and are rotated by about 70°.

Table 1
Selected geometric parameters (Å, °)

Fe1—N1	2.099 (4)	Fe1—N11	2.2480 (18)
Fe1—Cl1	2.3716 (12)

N1—Fe1—Cl1	180.0	N11ⁱ—Fe1—N11ⁱⁱ	89.546 (11)
N1—Fe1—N11	84.89 (6)	N11ⁱ—Fe1—N11	169.79 (12)
N11—Fe1—Cl1	95.11 (6)	N11—Fe1—N11ⁱⁱⁱ	89.545 (11)
Symmetry codes: (i) ; (ii) ; (iii) .

Figure 1
Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level. Symmetry codes for the generation of equivalent atoms: (i) y, −x + 1, z; (ii) −x + 1, −y + 1, z; (iii) −y + 1, x, z.

3. Supramolecular features

In the crystal, the discrete complexes are arranged in columns that elongate in the c-axis direction (Fig. 2). From a view along the b-axis, it is obvious that all chloride anions and thiocyanate anions always point in the same direction, which proves the non-centrosymmetry of this structure (Fig. 3). There are no pronounced directional interactions between the complexes, except for two C—H⋯N interactions but, from the bond lengths and angles, it is obvious that they do not correspond to significant interactions (Table 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯N12^iv	0.95	2.68	3.304 (3)	124
C15—H15⋯N12^iv	0.95	2.67	3.313 (3)	126
Symmetry code: (iv) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
Crystal structure of the title compound in a view along the crystallographic c-axis direction.

Figure 3
Crystal structure of the title compound in a view along the crystallographic b-axis direction, showing the non-centrosymmetry of the structure.

4. Database survey

A search in the Cambridge Structural Database (CSD version 5.43, last update November 2023; Groom et al., 2016 ) using ConQuest (Bruno et al., 2002 ) revealed that no complexes consisting of a transition-metal cation coordinated by a halide anion, a thiocyanate anion and a 3-cyanopyridine ligand are known.

Searching for compounds with iron coordinated by a thiocyanate and a halide anion, only one structure was found. In (μ₂-N,N,N′,N′-tetrakis(2-benzimidazolylmethyl)-2-oxy-1,3-diaminopropane)dichlorodiisothiocyanatodiiron(iii) chloride tetrahydrate (refcode: HOJLEX, Horng & Lee, 1999), the iron cations are octahedrally coordinated by one chloride anion and one thiocyanate anion in cis-positions, as well as three N and one O atoms of the organic ligand. Pairs of Fe^II cations are linked by a μ-1,1(O,O)-bridging O atom into dinuclear units.

After expanding the search to compounds in which a transition-metal cation is coordinated by a thiocyanate anion, a halide anion and a pyridine derivate, some more structures were found, most of them with chloride anions. This includes discrete complexes with the composition M(NCS)(X)(L) (M = Cu, Co, Zn, X = Cl, Br) in which the metal cation is coordinated by one thiocyanate anion, one halide anion and one tridentate ligand {L = 2,6-bis(pyridin-2-yl)-3,5-bis(pyridin-2-yl)pyrazine, refcode: FEPKEU; Al-Assy & Mostafa, 2023 ; L = 4-methoxy-N-[(pyridin-2-yl)methylidene]benzene-1-carbohydrazonato, refcode: FIRPAA; Yu et al., 2018 ; L = 2-[1-(pyridin-2-yl)ethylidene]hydrazinecarboximidamide, refcode: IQEFER; Vojinović-Ješić et al., 2016 ; L = 2-amino-N′-[(pyridin-2-yl)methylidene]benzohydrazide, refcode: KEPPII; Zhang et al., 2022 ; L = 2,2′-(pyridine-2,6-diyl)bis-1H-benzimidazole, refcode: QEHRAY; Machura et al., 2012 ; L = N,N-dimethyl-N′-(1-pyridinylmethylidene)propane-1,3-diamine, refcode: YIJYEW; Sun, 2006 ; L = N-methyl-N′-[1-(2-pyridyl)ethylidene]ethane-1,2-diamine-κ³N,N′,N′′, refcode: DURFOM; Liu, 2010 }.

Additional discrete complexes of the composition M(NCS)Cl(L)₂ (M = Cu, Co) are found in which the metal cations are octahedrally coordinated by one thiocyanate anion, one chloride anion and two bidentate ligands [L= 2-(pyridin-2-yl)-1H-benzimidazole, refcode: VEJHAW; Kumari et al., 2018 , L = 1,10-phenanthroline, refcode: ZAMDOG; Parker & Breneman, 1995 ; L = 2,2′-bipyridine, refcode: FERWEH; Tang et al., 2017 ]. In Cu(NCS)I(pyridine)₄·pyridine, the copper cations are octahedrally coordinated by one thiocyanate anion, one iodide anion and four pyridine coligands (refcode: ESITOQ; Bowmaker et al., 2011 ). In this compound, disorder is present with the iodide and thiocyanate anions occupying the same crystallographic position. In a further copper compound, the copper cations are fivefold coordinated by one N and one S-bonding thiocyanate anion, one chloride anion and two N atoms of the coligand (QETTER; Hu et al., 2018 ). Two Cu^II cations are linked by pairs of μ-1,3-bridging thiocyanate anions into dinuclear complexes. In diaqua-bis{μ-N′,N′′-[(pyridine-2,6-diyl)bis(eth-1-yl-1-ylidene)]bis(pyridine-4-carbohydrazide)}bis(isothiocyanato)tetrachlorotrimanganese(II), one of the crystallographically independent manganese cations is octahedrally coordinated by two thiocyanate anions, two chloride anions and two of the coligands (EWEVEK; Croitor et al., 2021 ). One discrete complex with additional hydrate molecules with the composition Mn(NCS)Cl(H₂O)L·(H₂O) is also reported in which the manganese cation is octahedrally coordinated by one thiocyanate anion, one chloride anion and one tridentate coligand (L = 2,3,5,6-tetrakis(pyridin-2-yl)pyrazine, refcode: ZEYWUX; Machura et al., 2013 ). Two discrete complexes of the composition Zn(NCS)Cl₂L exist in which the zinc cations are tetrahedrally coordinated by two halide anions and one organic ligand (refcode: QINJEF; Kwiatek et al., 2019 ). The fourth coordination site is mixed occupied by chloride and thiocyanate anions in a 0.67:0.33 ratio. With a slightly modified ligand, a further compound is found that is isotypic to the former and in which the fourth position is exclusively coordinated by only thiocyanate anions (refcode: QINJUV; Kwiatek et al., 2019). With zinc, a further compound is known with composition Zn(NCS)Cl₂(H₂O)(phenanthroline) in which the zinc cation is octahedrally coordinated by one thiocyanate anion, two chloride anions, one water ligand and one bidentate phenanthroline coligand (refcode: CUSVUI; Ma et al., 2010 ). Finally, an additional compound with cadmium is known in which one of the two crystallographically independent cadmium cations is octahedrally coordinated by one thiocyanate anion, two chloride anions and one bidentate {μ-2,2′,2′′-[1-(pyridin-2-ylmethyl)imidazolidine-2,4,5-triyl]tripyridine} coligand (refcode: DOWCUP; Ou et al., 2014 ). The Cd^II cations are linked by μ-1,1-bridging chloride anions into chains.

5. Synthesis and crystallization

Synthesis

FeCl₂·4H₂O and KSCN were purchased from Sigma Aldrich and 3-cyanopyridine was purchased from Alfa Aesar.

A microcrystalline powder was obtained by the reaction of 0.25 mmol of FeCl₂·4H₂O (49.7 mg), 0.25 mmol of KSCN (24.3 mmol) and 2 mmol of 3-cyanopyridine (208.2 mg) in ethanol. The mixture was stirred for 1 d at room temperature, filtered off and washed with water. Crystals suitable for single-crystal X-ray diffraction were obtained using 0.25 mmol of FeCl₂·4H₂O (49.7 mg), 0.5 mmol of KSCN (48.6 mmol) and 2 mmol of 3-cyanopyridine (208.2 mg) in ethanol under hydrothermal conditions (403 K for 1 d).

Concerning the synthesis of the title complex, it is noted that in the beginning of our synthetic work, this compound was accidentally obtained by the reaction of one equivalent FeCl₂·4H₂O with two equivalents of KSCN. Comparison of the experimental powder pattern of this batch with that calculated from single-crystal data measured at room temperature shows that the title compound was obtained as the major phase, together with some amount of an unknown crystalline product (Fig. S1). Later on, the ratio between FeCl₂·4H₂O and KSN was reduced to 1:1, leading to title complex as a nearly pure phase (Fig. 4). However, there are a few additional reflections of low intensity that correspond to a small contamination of an unknown phase, which is different from the byproduct obtained by the reaction with a 1:2 ratio (Fig. 4). In the IR spectrum of the title compound, the CN stretching vibration of the thiocyanate anions is observed at 2074 cm⁻¹, which is in agreement with the presence of only terminally bonded thiocyanate anions (Bailey et al., 1971 ; Fig. 5). Moreover, the band at higher wavenumbers corresponds to the CN stretching vibration of the cyano group, for which a value of 2238 cm⁻¹ is observed (Smith, 2019 ). This shows that the cyano group is not involved in the metal coordination (Reedijk & Groeneveld, 1967 ).

Figure 4
Experimental (top) and calculated (bottom) PXRD patterns of the title compound. Please note that the powder pattern was calculated using data from a structure determination performed at room temperature.

Figure 5
IR spectrum of the title compound. The CN stretching vibrations of the thiocyanate anion and the cyano group of the 3-cyanopyridine coligand are given.

Experimental details

The data collection for single-crystal structure analysis and powder X-ray diffraction was performed using an XtaLAB Synergy, Dualflex, HyPix diffractometer from Rigaku with Cu Kα radiation.

The IR spectrum was measured using an ATI Mattson Genesis Series FTIR Spectrometer, control software WINFIRST, from ATI Mattson.

Thermogravimetry and differential thermoanalysis (TG–DTA) measurements were performed in a dynamic air atmosphere in Al₂O₃ crucibles using a STA-PT 1000 thermobalance from Linseis. The instrument was calibrated using standard reference materials.

6. Thermogravimetry and differential thermoanalysis

The thermal properties of the title compound were investigated by thermogravimetry and differential thermoanalysis (TG–DTA). Upon heating, two mass losses were observed that, according to the DTG curve, are poorly resolved and that are accompanied with two endothermic events in the DTA curve (Fig. S2). The experimental mass loss in the first step is in rough agreement with that calculated for the removal of two 3-cyanopyridine ligands of 36.8%, whereas the value for the second mass loss is lower. This indicates that a compound with the composition Fe(NCS)(Cl)(3-cyanopyridine)₂ has formed after the first mass loss. Powder X-ray diffraction reveals that in the residue obtained after the first mass loss, no reflections of the pristine compound are present and that a phase of poor crystallinity has formed (Fig. S3). IR measurements of this residue show that the CN stretching vibration of the thiocyanate anion is shifted to 2025 cm⁻¹, whereas the CN stretching vibration of the cyano group remains constant. This strongly indicates that the μ-1,3-bridging thiocyanate anions are present and that the cyano group is still not involved in the metal coordination. In most cases, the structures of compounds with such a stoichiometry consist of chains in which the metal centers are octahedrally coordinated and linked by pairs of μ-1,3-bridging thiocyanate anions into chains (Jochim et al., 2018 ; Wöhlert et al., 2013; Mautner et al., 2018). Alternatively, a layered structure has formed in which the metal cations are octahedrally coordinated and linked by single bridging anionic ligands into layers (Werner et al., 2015b; Jochim et al., 2020a,b) or two metal cations are linked by pairs of thiocyanate anions into dinuclear units that are further connected into layers by single μ-1,3-bridging anionic ligands (Suckert et al., 2016 ). Other topologies of thiocyanate networks are very rare.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. C-bound H atoms were positioned with idealized geometry (C—H = 0.95 Å) and refined isotropically with U_iso(H) = 1.2U_eq(C) using a riding model. The absolute structure was determined and is in agreement with the selected setting.

Table 3
Experimental details

Crystal data
Chemical formula	[FeCl(NCS)(C₆H₄N₂)₄]
M_r	565.83
Crystal system, space group	Tetragonal, P4nc
Temperature (K)	100
a, c (Å)	10.79412 (6), 11.15065 (11)
V (Å³)	1299.20 (2)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	6.62
Crystal size (mm)	0.18 × 0.08 × 0.06

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.686, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11711, 1411, 1406
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.065, 1.14
No. of reflections	1411
No. of parameters	88
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.35
Absolute structure	Flack x determined using 652 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.0059 (19)
Computer programs: CrysAlis PRO (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2016/6 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2307914

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698902300988X/nx2002sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902300988X/nx2002Isup2.hkl

Experimental (top) powder pattern of the product obtained by the synthesis of the title compound using FeCL2 . 4 H2O and KNCS in ratio 1:2 and calculated pattern for the title complex (bottom). DOI: https://doi.org/10.1107/S205698902300988X/nx2002sup3.png

DTG, TG and DTA curve for the title complex. DOI: https://doi.org/10.1107/S205698902300988X/nx2002sup4.png

Experimental (top) powder pattern of the intermediate compound obtained after the first mass loss in a TG measurement of the title complex together with the pattern of the title complex calculated using data measured at room temperature (bottom). DOI: https://doi.org/10.1107/S205698902300988X/nx2002sup5.png

IR spectra of the intermediate compound obtained after the first mass loss in a TG measurement of the title compound. DOI: https://doi.org/10.1107/S205698902300988X/nx2002sup6.png

checkCIF report

Computing details top

Chloridotetrakis(pyridine-3-carbonitrile)thiocyanatoiron(II) top

Crystal data top

[FeCl(NCS)(C₆H₄N₂)₄]	D_x = 1.446 Mg m⁻³
M_r = 565.83	Cu Kα radiation, λ = 1.54184 Å
Tetragonal, P4nc	Cell parameters from 9200 reflections
a = 10.79412 (6) Å	θ = 5.7–79.7°
c = 11.15065 (11) Å	µ = 6.62 mm⁻¹
V = 1299.20 (2) Å³	T = 100 K
Z = 2	Block, yellow
F(000) = 576	0.18 × 0.08 × 0.06 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	1411 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	1406 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.021
Detector resolution: 10.0000 pixels mm^-1	θ_max = 79.9°, θ_min = 5.7°
ω scans	h = −13→12
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	k = −13→13
T_min = 0.686, T_max = 1.000	l = −14→13
11711 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.023	w = 1/[σ²(F_o²) + (0.0384P)² + 0.3704P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.065	(Δ/σ)_max < 0.001
S = 1.14	Δρ_max = 0.34 e Å⁻³
1411 reflections	Δρ_min = −0.34 e Å⁻³
88 parameters	Absolute structure: Flack x determined using 652 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.0059 (19)
Primary atom site location: dual

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	0.500000	0.500000	0.61306 (6)	0.01647 (19)
N1	0.500000	0.500000	0.4248 (4)	0.0230 (11)
C1	0.500000	0.500000	0.3226 (6)	0.0211 (10)
S1	0.500000	0.500000	0.17570 (13)	0.0298 (3)
Cl1	0.500000	0.500000	0.82574 (10)	0.0218 (3)
N11	0.37363 (17)	0.33550 (16)	0.59511 (18)	0.0205 (4)
C11	0.38831 (19)	0.2322 (2)	0.6601 (2)	0.0215 (4)
H11	0.442330	0.233778	0.727352	0.026*
C12	0.3268 (2)	0.12224 (19)	0.6321 (2)	0.0231 (4)
C13	0.2477 (2)	0.1182 (2)	0.5330 (2)	0.0247 (5)
H13	0.206877	0.043560	0.511051	0.030*
C14	0.2307 (2)	0.2254 (2)	0.4677 (3)	0.0235 (5)
H14	0.176720	0.226567	0.400458	0.028*
C15	0.2940 (2)	0.3315 (2)	0.5023 (2)	0.0216 (4)
H15	0.280313	0.405460	0.457985	0.026*
C16	0.3447 (2)	0.0135 (2)	0.7051 (3)	0.0278 (5)
N12	0.3583 (2)	−0.0743 (2)	0.7610 (2)	0.0362 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0139 (2)	0.0139 (2)	0.0216 (4)	0.000	0.000	0.000
N1	0.0229 (14)	0.0229 (14)	0.023 (2)	0.000	0.000	0.000
C1	0.0117 (14)	0.0117 (14)	0.040 (3)	0.000	0.000	0.000
S1	0.0322 (5)	0.0322 (5)	0.0251 (6)	0.000	0.000	0.000
Cl1	0.0210 (4)	0.0210 (4)	0.0234 (6)	0.000	0.000	0.000
N11	0.0171 (8)	0.0169 (8)	0.0275 (9)	−0.0010 (6)	−0.0007 (8)	0.0010 (7)
C11	0.0167 (9)	0.0202 (10)	0.0276 (10)	0.0000 (8)	0.0006 (8)	0.0007 (9)
C12	0.0205 (10)	0.0177 (10)	0.0311 (11)	−0.0003 (8)	0.0030 (8)	0.0027 (9)
C13	0.0220 (10)	0.0205 (10)	0.0315 (12)	−0.0043 (8)	0.0017 (9)	−0.0028 (9)
C14	0.0186 (10)	0.0235 (11)	0.0283 (10)	−0.0038 (9)	−0.0019 (10)	−0.0016 (10)
C15	0.0174 (9)	0.0198 (10)	0.0276 (10)	−0.0011 (7)	−0.0037 (9)	0.0015 (9)
C16	0.0223 (10)	0.0219 (11)	0.0391 (14)	−0.0026 (8)	0.0021 (11)	0.0037 (10)
N12	0.0326 (10)	0.0273 (11)	0.0488 (12)	−0.0001 (8)	0.0037 (10)	0.0107 (10)

Geometric parameters (Å, º) top

Fe1—N1	2.099 (4)	C11—H11	0.9500
Fe1—Cl1	2.3716 (12)	C11—C12	1.395 (3)
Fe1—N11ⁱ	2.2480 (18)	C12—C13	1.397 (3)
Fe1—N11ⁱⁱ	2.2480 (18)	C12—C16	1.441 (3)
Fe1—N11	2.2480 (18)	C13—H13	0.9500
Fe1—N11ⁱⁱⁱ	2.2480 (18)	C13—C14	1.379 (3)
N1—C1	1.140 (8)	C14—H14	0.9500
C1—S1	1.638 (7)	C14—C15	1.389 (3)
N11—C11	1.340 (3)	C15—H15	0.9500
N11—C15	1.346 (3)	C16—N12	1.144 (3)

N1—Fe1—Cl1	180.0	C11—N11—C15	117.71 (19)
N1—Fe1—N11ⁱ	84.89 (6)	C15—N11—Fe1	118.75 (14)
N1—Fe1—N11ⁱⁱ	84.89 (6)	N11—C11—H11	119.0
N1—Fe1—N11	84.89 (6)	N11—C11—C12	122.1 (2)
N1—Fe1—N11ⁱⁱⁱ	84.89 (6)	C12—C11—H11	119.0
N11ⁱⁱⁱ—Fe1—Cl1	95.11 (6)	C11—C12—C13	119.6 (2)
N11ⁱ—Fe1—Cl1	95.11 (6)	C11—C12—C16	120.1 (2)
N11ⁱⁱ—Fe1—Cl1	95.11 (6)	C13—C12—C16	120.2 (2)
N11—Fe1—Cl1	95.11 (6)	C12—C13—H13	120.9
N11ⁱⁱ—Fe1—N11ⁱ	89.546 (11)	C14—C13—C12	118.2 (2)
N11—Fe1—N11ⁱ	89.547 (11)	C14—C13—H13	120.9
N11ⁱⁱ—Fe1—N11ⁱⁱⁱ	89.546 (11)	C13—C14—H14	120.6
N11ⁱ—Fe1—N11ⁱⁱⁱ	169.78 (12)	C13—C14—C15	118.7 (2)
N11ⁱⁱ—Fe1—N11	169.79 (12)	C15—C14—H14	120.6
N11—Fe1—N11ⁱⁱⁱ	89.545 (11)	N11—C15—C14	123.6 (2)
C1—N1—Fe1	180.0	N11—C15—H15	118.2
N1—C1—S1	180.0	C14—C15—H15	118.2
C11—N11—Fe1	122.53 (15)	N12—C16—C12	178.5 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···N12^iv	0.95	2.68	3.304 (3)	124
C15—H15···N12^iv	0.95	2.67	3.313 (3)	126

Symmetry code: (iv) −x+1/2, y+1/2, z−1/2.

Acknowledgements

This work was supported by the State of Schleswig-Holstein.

References

Al-Assy, W. H. & Mostafa, M. M. (2023). J. Mol. Struct. 1273, 134262. Google Scholar
Bailey, R. A., Kozak, S. L., Michelsen, T. W. & Mills, W. N. (1971). Coord. Chem. Rev. 6, 407–445. CrossRef CAS Web of Science Google Scholar
Bowmaker, G. A., Di Nicola, C., Pettinari, C., Skelton, B. W., Somers, N. & White, A. H. (2011). Dalton Trans. 40, 5102–5115. Web of Science CSD CrossRef CAS PubMed Google Scholar
Brandenburg, K. & Putz, H. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389–397. Web of Science CrossRef CAS IUCr Journals Google Scholar
Croitor, L., Cocu, M., Bulhac, I., Bourosh, P. N. Ch., Kravtsov, V., Petuhov, O. & Danilescu, O. (2021). Polyhedron, 206, 115329. CSD CrossRef 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
Gütlich, P., Garcia, Y. & Goodwin, H. A. (2000). Chem. Soc. Rev. 29, 171–179. Google Scholar
Hogue, R. W., Singh, S. & Brooker, S. (2018). Chem. Soc. Rev. 47, 7303–7338. CrossRef CAS Google Scholar
Horng, D. N. & Lee, K. M. (1999). J. Chem. Soc. Dalton Trans. pp. 2205–2210. CSD CrossRef Google Scholar
Hu, J., Liao, C., Mao, R., Zhang, J., Zhao, J. & Gu, Z. (2018). Med. Chem. Commun. 9, 337–343. CSD CrossRef CAS Google Scholar
Jochim, A., Jess, I. & Näther, C. (2020a). Z. Naturforsch. B, 75, 163–172. CSD CrossRef CAS Google Scholar
Jochim, A., Rams, M., Böhme, M., Ceglarska, M., Plass, W. & Näther, C. (2020b). Dalton Trans. 49, 15310–15322. Web of Science CSD CrossRef CAS PubMed Google Scholar
Jochim, A., Rams, M., Neumann, T., Wellm, C., Reinsch, H., Wójtowicz, G. M. & Näther, C. (2018). Eur. J. Inorg. Chem. pp. 4779–4789. Web of Science CSD CrossRef Google Scholar
Krebs, C., Foltyn, M., Jess, I., Mangelsen, S., Rams, M. & Näther, C. (2023). Inorg. Chim. Acta, 554, 121495. Web of Science CSD CrossRef Google Scholar
Krebs, C., Thiele, S., Ceglarska, M. & Näther, C. (2021). Z. Anorg. Allge Chem. 647, 2122–2129. Web of Science CSD CrossRef CAS Google Scholar
Kumari, B., Adhikari, S., Matalobos, J. S. & Das, D. (2018). J. Mol. Struct. 1151, 169–176. CSD CrossRef CAS Google Scholar
Kwiatek, D., Kubicki, M., Skokowski, P., Gruszczyńska, J., Lis, S. & Hnatejko, Z. (2019). J. Mol. Struct. 1178, 669–681. CSD CrossRef CAS Google Scholar
Liu, L.-J. (2010). Acta Cryst. E66, m939. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ma, Q., Zhu, M., Yuan, C., Feng, S., Lu, L. & Wang, Q. (2010). Cryst. Growth Des. 10, 1706–1714. Web of Science CSD CrossRef CAS Google Scholar
Machura, B., Palion, J., Mroziński, J., Kalińska, B., Amini, M., Najafpour, M. M. & Kruszynski, R. (2013). Polyhedron, 53, 132–143. CSD CrossRef CAS Google Scholar
Machura, B., Świtlicka, A. & Penkala, M. (2012). Polyhedron, 45, 221–228. CSD CrossRef CAS Google Scholar
Mautner, F. A., Traber, M., Fischer, R. C., Torvisco, A., Reichmann, K., Speed, S., Vicente, R. & Massoud, S. S. (2018). Polyhedron, 154, 436–442. Web of Science CSD CrossRef CAS Google Scholar
Mekuimemba, C. D., Conan, F., Mota, A. J., Palacios, M. A., Colacio, E. & Triki, S. (2018). Inorg. Chem. 57, 2184–2192. Web of Science CSD CrossRef CAS PubMed Google Scholar
Naggert, H., Rudnik, J., Kipgen, L., Bernien, M., Nickel, F., Arruda, L. M., Kuch, W., Näther, C. & Tuczek, F. (2015). J. Mater. Chem. C3, 7870–7877. Google Scholar
Näther, C., Müller-Meinhard, A. & Jess, I. (2023). Acta Cryst. E79, 1093–1099. CSD CrossRef IUCr Journals Google Scholar
Ou, Y. J., Zheng, Z., Hong, X. J., Wan, L. T., Wei, L. M., Lin, X. M. & Cai, Y. P. (2014). Cryst. Growth Des. 14, 5339–5343. CSD CrossRef CAS Google Scholar
Palion-Gazda, J., Machura, B., Lloret, F. & Julve, M. (2015). Cryst. Growth Des. 15, 2380–2388. CAS Google Scholar
Parker, O. J. & Breneman, G. L. (1995). Acta Cryst. C51, 1529–1531. CSD CrossRef CAS IUCr Journals Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rams, M., Jochim, A., Böhme, M., Lohmiller, T., Ceglarska, M., Rams, M. M., Schnegg, A., Plass, W. & Näther, C. (2020). Chem. Eur. J. 26, 2837–2851. Web of Science CSD CrossRef CAS PubMed Google Scholar
Reedijk, J. & Groeneveld, W. L. (1967). Recl Trav. Chim. Pays Bas, 86, 1103–1126. CrossRef CAS Google Scholar
Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. Google Scholar
Senthil Kumar, K. & Ruben, M. (2017). Coord. Chem. Rev. 346, 176–205. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Smith, B. C. (2019). Spectroscopy, 34, 18–21. Google Scholar
Suckert, S., Rams, M., Böhme, M., Germann, L. S., Dinnebier, R. E., Plass, W., Werner, J. & Näther, C. (2016). Dalton Trans. 45, 18190–18201. Web of Science CSD CrossRef CAS PubMed Google Scholar
Sun, Y. X. (2006). Synth. React. Inorg. Met.-Org. Nano-Met. Chem. 36, 621–625. CSD CrossRef CAS Google Scholar
Tang, L. Z., Xue, D., Yang, L. F. & Zhan, S. Z. (2017). Transit. Met. Chem. 42, 711–717. CSD CrossRef CAS Google Scholar
Vojinović-Ješić, L. S., Radanović, M. M., Rodić, M. V., Živković-Radovanović, V., Jovanović, L. S. & Leovac, V. M. (2016). Polyhedron, 117, 526–534. Google Scholar
Werner, J., Runčevski, T., Dinnebier, R., Ebbinghaus, S. G., Suckert, S. & Näther, C. (2015a). Eur. J. Inorg. Chem. pp. 3236–3245. Web of Science CSD CrossRef Google Scholar
Werner, J., Tomkowicz, Z., Reinert, T. & Näther, C. (2015b). Eur. J. Inorg. Chem. pp. 3066–3075. Web of Science CSD CrossRef Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wöhlert, S., Fic, T., Tomkowicz, Z., Ebbinghaus, S. G., Rams, M., Haase, W. & Näther, C. (2013). Inorg. Chem. 52, 12947–12957. Web of Science PubMed Google Scholar
Yu, H., Guo, S., Cheng, J. Y., Jiang, G., Li, Z., Zhai, W., Li, A., Jiang, Y. & You, Z. (2018). J. Coord. Chem. 71, 4164–4179. CSD CrossRef CAS Google Scholar
Zhang, L., Feng, X., Gu, Y., Yang, T., Li, X., Yu, H. & You, Z. (2022). J. Struct. Chem. 63, 1358–1370. CSD CrossRef CAS Google Scholar

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