The title compound shows a cis-arrangement of the thiocyanate anions, while the coordination polyhedron around the iron(II) atom is close to a trigonal prism.
Keywords: iron(II) complex, thiocyanate complex, high spin state, trigonal distortion, crystal structure
Abstract
The unit cell of the title compound, [FeII(NCS)2(C25H28N8)], consists of two charge-neutral complex molecules related by an inversion centre. In the complex molecule, the tetradentate ligand N 1,N 3-bis[(1-benzyl-1H-1,2,3-triazol-4-yl)methylene]-2,2-dimethylpropane-1,3-diamine coordinates to the FeII ion through the N atoms of the 1,2,3-triazole moieties and aldimine groups. Two thiocyanate anions, coordinating through their N atoms, complete the coordination sphere of the central ion. In the crystal, neighbouring molecules are linked through weak C—H⋯π, C—H⋯S and C—H⋯N interactions into a two-dimensional network extending parallel to (011). The intermolecular contacts were quantified using Hirshfeld surface analysis and two-dimensional fingerprint plots, revealing the relative contributions of the contacts to the crystal packing to be H⋯H (35.2%), H⋯C/C⋯H (26.4%), H⋯S/S⋯H (19.3%) and H⋯N/N⋯H (13.9%).
Chemical context
Coordination complexes of 3d transition metals represent a large class of potentially applicable materials exhibiting catalytic (Strotmeyer et al., 2003 ▸), magnetic (Pavlishchuk et al., 2010 ▸) and spin-switching functionalities (Gütlich & Goodwin, 2004 ▸) with easily detectable and exploitable variations of physical properties (Gural’skiy et al., 2012 ▸; Suleimanov et al., 2015 ▸).
Iron(II) complexes based on Schiff bases derived from N-substituted 1,2,3-triazole aldehydes represent an interesting class of coordination compounds exhibiting spin-state switching between low- and high-spin states in different temperature regions (Hagiwara et al., 2014 ▸, 2016 ▸, 2020 ▸; Hora & Hagiwara, 2017 ▸). In charge-neutral mononuclear complexes of this kind described so far, the thiocyanate anions occupy the axial position of the coordination sphere and thus are in a trans-configuration (Hagiwara & Okada, 2016 ▸; Hagiwara et al., 2017 ▸).
Having ongoing interest in functional 3d metal complexes formed by polydentate ligands (Seredyuk et al., 2006 ▸, 2007 ▸, 2011 ▸, 2015 ▸, 2016 ▸; Seredyuk, 2012 ▸; Valverde-Muñoz et al., 2020 ▸), we report here the synthesis and crystal structure of a new high-spin FeII complex based on the tetradentate ligand N
1,N
3-bis[(1-benzyl-1H-1,2,3-triazol-4-yl)methylene]-2,2-dimethylpropane-1,3-diamine with thiocyanate anions arranged in a cis-configuration.
Structural commentary
The FeII ion of the title complex has a distorted trigonal–prismatic N6 coordination environment formed by four N atoms of the tetradentate Schiff-base ligand and two NCS− counter-ions (Fig. 1 ▸). The average bond length <Fe—N> = 2.19 (9) Å is typical for high-spin complexes with an [FeN6] chromophore (Gütlich & Goodwin, 2004 ▸). The N—Fe—N angle between the cis-aligned thiocyanate N atoms is 87.58 (9)°. The average trigonal distortion parameters Σ = Σ1 12(|90 − φ i|), where φ i is the angle N—Fe—N′ (Drew et al., 1995 ▸), and Θ = Σ1 24(|60 − θ i|), where θ i is the angle generated by superposition of two opposite faces of an octahedron (Chang et al., 1990 ▸), are 453.2 and 149.38°, respectively. These values reveal a great deviation of the coordination environment from an ideal octahedron (where Σ = Θ = 0), and are significantly larger than those of similar [FeN6] high-spin trans-complexes (Hagiwara et al., 2017 ▸). With the aid of continuous shape measure (CShM), the closest shape of a coordination polyhedron and its distortion can be determined numerically (Kershaw Cook et al., 2015 ▸). The calculated CShM value relative to the ideal Oh symmetry for an octahedron is 6.285, while it is 4.008 relative to the ideal D 3h symmetry for a trigonal prism. Hence, the polyhedron is closer to the latter shape; however, it is notably distorted (for the ideal polyhedron CShM = 0). The volume of the [FeN6] coordination polyhedron is 12.4 Å3.
Figure 1.
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity.
Supramolecular features
Neighbouring complex molecules form dimers through double weak contacts C18—H18B⋯Cg
i of 3.330 (3) Å (Cg corresponds to the centroid of the C20–C25 phenyl ring; symmetry codes refer to Table 1 ▸). The CH group of one of the triazole rings forms a weak hydrogen bond C7—H7⋯S1ii [3.755 (3) Å] with a thiocyanate anion. This, together with the C4—H4B⋯C27ii and C4—H4B⋯N10ii interactions [3.709 (3) and 3.617 (3) Å] involving the C≡N group of the anion, links the dimers into a supramolecular chain propagating parallel to [01
] (Fig. 2 ▸). These chains are weakly bound through double contacts between the benzyl groups and the thiocyanate anions [C21—H21⋯C27iii = 3.603 (3) Å] and triazole groups [C19—H19A⋯N7iii = 3.311 (3) Å] of neighbouring complex molecules, forming a two-dimensional supramolecular array extending parallel to (011).
Table 1. Hydrogen-bond geometry (Å, °).
Cg is the centroid of the C20–C25 ring.
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C18—H18⋯Cg i | 0.93 | 2.42 | 3.330 (3) | 167 |
| C19—H19A⋯N7ii | 0.97 | 2.38 | 3.311 (3) | 162 |
| C21—H21⋯C27ii | 0.93 | 2.89 | 3.603 (3) | 134 |
| C7—H7⋯S1iii | 0.93 | 2.87 | 3.755 (3) | 159 |
| C4—H4B⋯N10iii | 0.97 | 2.69 | 3.617 (3) | 160 |
| C4—H4B⋯C27iii | 0.97 | 2.75 | 3.709 (3) | 171 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
.
Figure 2.
Weak hydrogen bonding (cyan dashed lines), resulting in the formation of chains in the packing.
Hirshfeld surface and 2D fingerprint plots
Hirshfeld surface analysis was performed and the associated two-dimensional fingerprint plots were generated using Crystal Explorer (Turner et al., 2018 ▸), with a standard resolution of the three-dimensional d norm surfaces plotted over a fixed colour scale of −0.2801 (red) to 1.8236 (blue) a.u. The pale-red spots symbolize short contacts and negative d norm values on the surface correspond to the interactions described above. The overall two-dimensional fingerprint plot is illustrated in Fig. 3 ▸. The Hirshfeld surfaces mapped over d norm are shown for the H⋯H, H⋯C/C⋯H, H⋯S/S⋯H, and H⋯N/N⋯H contacts, and the two-dimensional fingerprint plots are presented in Fig. 4 ▸, associated with their relative contributions to the Hirshfeld surface. At 35.2%, the largest contribution to the overall crystal packing is from H⋯H interactions, which are located in the middle region of the fingerprint plot. H⋯C/C⋯H contacts contribute 26.4%, and the H⋯S/S⋯H contacts contribute 19.3% to the Hirshfeld surface, both resulting in a pair of characteristic wings. The H⋯N/N⋯H contacts, represented by a pair of sharp spikes in the fingerprint plot, make a 13.9% contribution to the Hirshfeld surface.
Figure 3.
Two projections of d norm mapped on Hirshfeld surfaces, showing the intermolecular interactions within the molecule. Red areas represent contacts shorter than the sum of the van der Waals radii, while blue areas represent regions where contacts are larger than the sum of van der Waals radii, and white areas are zones close to the sum of van der Waals radii.
Figure 4.
(a) The overall two-dimensional fingerprint plot and those decomposed into specified interactions. (b) Hirshfeld surface representations with the function d norm plotted onto the surface for the different interactions.
Database survey
A search of the Cambridge Structural Database (CSD 2020, update of May 2020; Groom et al., 2016 ▸) revealed four similar FeII thiocyanate complexes, derivatives of a 1,3-diaminopropanes and N-substituted 1,2,3-triazole aldehydes, viz. DURXEV, ADAQUU, ADAREF and solvatomorphs ADAROP and ADARUV (Hagiwara et al., 2017 ▸; Hagiwara & Okada, 2016 ▸). These complexes show hysteretic spin crossover with the Fe—N distances in the range 1.931–1.959 Å for the low-spin state and 2.154–2.169 Å for the high-spin state of the FeII ions. The reported pseudo-trigonal–prismatic complexes with an [FeN6] chromophore are formed by structurally hindered rigid hexadentate ligands favoring a trigonal–prismatic environment of the central FeII ion in the low- or high-spin state: CABLOH (Voloshin et al., 2001 ▸), BUNSAF (El Hajj et al., 2009 ▸), OWIHAE (Seredyuk et al., 2011 ▸), OTANOO (Stock et al., 2016 ▸). For comparison purposes, Table 2 ▸ collates the distortion parameters Σ, Θ and CShM for the latter complexes.
Table 2. Comparison of the distortion parameters for indicated FeII complexes.
Parameters for OTANOO averaged over five independent complex cations.
| Compound | <Fe–N> (Å) | Σ (°) | Θ (°) | CShM (D 3h) |
|---|---|---|---|---|
| Title compound | 2.186 | 453.2 | 149.38 | 4.008 |
| CABLOH | 1.899 | 725.74 | 178.16 | 0.525 |
| BUNSAF | 2.218 | 703.65 | 201.07 | 1.887 |
| OWIHAE | 2.202 | 894.48 | 206.57 | 0.602 |
| OTANOO | 2.191 | 697.3 | 183.24 | 1.098 |
Synthesis and crystallization
The ligand of the title compound was obtained in situ by condensation of 1 eq. of 2,2-dimethyl-1,3-propanediamine with 2.2 eq. of 1-benzyl-1H-1,2,3-triazole-4-carbaldehyde in boiling methanol over 5 min and subsequent reaction with 1 eq. of [Fe(py)4(NCS)2] dissolved in a minimum amount of boiling methanol with a minimum amount of ascorbic acid. The formed yellow solution was slowly cooled to ambient temperature. The formed orange crystals were subsequently filtered off. Elemental analysis calculated (%) for C27H28FeN10S2: C, 52.94; H, 4.61; N, 22.87; S, 10.47; found: C, 52.88; H, 4.37; N, 22.40; S, 10.35. IR vKBr (cm−1): 1615 (C=N), 2071, 2115 (NCS).
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. H atoms were placed in calculated positions using idealized geometries, with C—H = 0.96–0.97 Å for methylene and methyl groups and 0.93 Å for aromatic H atoms, and refined using a riding model with U iso(H) = 1.2–1.5U eq(C).
Table 3. Experimental details.
| Crystal data | |
| Chemical formula | [Fe(NCS)2(C25H28N8)] |
| M r | 612.56 |
| Crystal system, space group | Triclinic, P
|
| Temperature (K) | 250 |
| a, b, c (Å) | 8.9656 (5), 12.5060 (6), 14.2311 (7) |
| α, β, γ (°) | 67.552 (5), 85.106 (4), 84.087 (4) |
| V (Å3) | 1465.06 (14) |
| Z | 2 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.69 |
| Crystal size (mm) | 0.4 × 0.2 × 0.2 |
| Data collection | |
| Diffractometer | Rigaku Oxford Diffraction Xcalibur, Eos |
| Absorption correction | Multi-scan (CrysAlis PRO; Rigaku OD, 2018 ▸) |
| T min, T max | 0.911, 1.000 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 10677, 5175, 4416 |
| R int | 0.018 |
| (sin θ/λ)max (Å−1) | 0.595 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.037, 0.082, 1.03 |
| No. of reflections | 5175 |
| No. of parameters | 391 |
| H-atom treatment | Only H-atom displacement parameters refined |
| Δρmax, Δρmin (e Å−3) | 0.62, −0.59 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020012608/wm5580sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989020012608/wm5580Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989020012608/wm5580Isup3.cdx
CCDC reference: 2032292
Additional supporting information: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
Crystal data
| [Fe(NCS)2(C25H28N8)] | Z = 2 |
| Mr = 612.56 | F(000) = 636 |
| Triclinic, P1 | Dx = 1.389 Mg m−3 |
| a = 8.9656 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 12.5060 (6) Å | Cell parameters from 4582 reflections |
| c = 14.2311 (7) Å | θ = 1.6–28.8° |
| α = 67.552 (5)° | µ = 0.69 mm−1 |
| β = 85.106 (4)° | T = 250 K |
| γ = 84.087 (4)° | Plate, orange |
| V = 1465.06 (14) Å3 | 0.4 × 0.2 × 0.2 mm |
Data collection
| Rigaku Oxford Diffraction Xcalibur, Eos diffractometer | 5175 independent reflections |
| Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 4416 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.018 |
| Detector resolution: 16.1593 pixels mm-1 | θmax = 25.0°, θmin = 1.6° |
| ω scans | h = −10→9 |
| Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018) | k = −14→13 |
| Tmin = 0.911, Tmax = 1.000 | l = −16→16 |
| 10677 measured reflections |
Refinement
| Refinement on F2 | 0 restraints |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.037 | Only H-atom displacement parameters refined |
| wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0224P)2 + 1.1951P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max < 0.001 |
| 5175 reflections | Δρmax = 0.62 e Å−3 |
| 391 parameters | Δρmin = −0.59 e Å−3 |
Special details
| 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)
| x | y | z | Uiso*/Ueq | ||
| Fe1 | 0.46967 (4) | 0.25650 (3) | 0.15072 (2) | 0.02848 (10) | |
| S1 | 0.83937 (11) | 0.13105 (7) | −0.06302 (8) | 0.0749 (3) | |
| S2 | 0.93628 (8) | 0.30840 (7) | 0.26836 (6) | 0.0597 (2) | |
| N1 | 0.3705 (2) | 0.40653 (16) | 0.02733 (14) | 0.0288 (4) | |
| N2 | 0.3331 (2) | 0.37376 (16) | 0.22397 (14) | 0.0307 (4) | |
| N3 | 0.3079 (2) | 0.37587 (17) | 0.31494 (15) | 0.0371 (5) | |
| N4 | 0.2416 (2) | 0.48269 (17) | 0.30170 (15) | 0.0357 (5) | |
| N5 | 0.3032 (2) | 0.17554 (16) | 0.09218 (14) | 0.0310 (4) | |
| N6 | 0.3792 (2) | 0.11839 (15) | 0.28389 (14) | 0.0296 (4) | |
| N7 | 0.3924 (2) | 0.08273 (16) | 0.38237 (15) | 0.0331 (5) | |
| N8 | 0.2832 (2) | 0.01043 (15) | 0.42600 (14) | 0.0306 (4) | |
| N9 | 0.6253 (3) | 0.2060 (2) | 0.05480 (19) | 0.0528 (6) | |
| N10 | 0.6514 (2) | 0.28477 (17) | 0.21860 (16) | 0.0385 (5) | |
| C1 | 0.2253 (4) | 0.3438 (3) | −0.1867 (2) | 0.0555 (8) | |
| H1A | 0.193892 | 0.423117 | −0.225831 | 0.056 (9)* | |
| H1B | 0.152987 | 0.294205 | −0.190475 | 0.070 (10)* | |
| H1C | 0.321299 | 0.323624 | −0.213362 | 0.070 (10)* | |
| C2 | 0.0854 (3) | 0.3642 (2) | −0.0346 (2) | 0.0419 (6) | |
| H2A | 0.091918 | 0.352941 | 0.035621 | 0.049 (8)* | |
| H2B | 0.010603 | 0.317602 | −0.040245 | 0.053 (8)* | |
| H2C | 0.058264 | 0.444495 | −0.073289 | 0.058 (9)* | |
| C3 | 0.2375 (3) | 0.3284 (2) | −0.07558 (17) | 0.0341 (5) | |
| C4 | 0.3598 (3) | 0.4059 (2) | −0.07427 (17) | 0.0346 (6) | |
| H4A | 0.455840 | 0.377726 | −0.096377 | 0.029 (6)* | |
| H4B | 0.336486 | 0.484535 | −0.121707 | 0.038 (7)* | |
| C5 | 0.2984 (3) | 0.48861 (19) | 0.04771 (18) | 0.0307 (5) | |
| H5 | 0.256242 | 0.553702 | −0.003344 | 0.033 (6)* | |
| C6 | 0.2840 (2) | 0.47738 (18) | 0.15301 (17) | 0.0290 (5) | |
| C7 | 0.2245 (3) | 0.5470 (2) | 0.20293 (19) | 0.0351 (6) | |
| H7 | 0.181423 | 0.622568 | 0.174611 | 0.031 (6)* | |
| C8 | 0.1953 (3) | 0.5106 (3) | 0.3915 (2) | 0.0493 (7) | |
| H8A | 0.190249 | 0.438538 | 0.450396 | 0.066 (9)* | |
| H8B | 0.094871 | 0.548892 | 0.382656 | 0.067 (10)* | |
| C9 | 0.2961 (3) | 0.5868 (2) | 0.4139 (2) | 0.0463 (7) | |
| C10 | 0.3637 (4) | 0.6766 (3) | 0.3392 (3) | 0.0616 (8) | |
| H10 | 0.351491 | 0.691169 | 0.271088 | 0.064 (9)* | |
| C11 | 0.4509 (4) | 0.7463 (3) | 0.3655 (4) | 0.0805 (11) | |
| H11 | 0.497489 | 0.806878 | 0.314888 | 0.080 (12)* | |
| C12 | 0.4680 (4) | 0.7252 (4) | 0.4664 (4) | 0.0851 (13) | |
| H12 | 0.527762 | 0.770575 | 0.483973 | 0.106 (14)* | |
| C13 | 0.3976 (4) | 0.6382 (5) | 0.5402 (4) | 0.0874 (13) | |
| H13 | 0.406323 | 0.625738 | 0.608290 | 0.104 (14)* | |
| C14 | 0.3135 (4) | 0.5684 (4) | 0.5147 (3) | 0.0666 (10) | |
| H14 | 0.267676 | 0.507861 | 0.565894 | 0.104 (15)* | |
| C15 | 0.2819 (3) | 0.2003 (2) | −0.01518 (18) | 0.0373 (6) | |
| H15A | 0.204471 | 0.153918 | −0.019696 | 0.042 (7)* | |
| H15B | 0.374371 | 0.177465 | −0.045658 | 0.038 (7)* | |
| C16 | 0.2287 (3) | 0.0988 (2) | 0.15956 (18) | 0.0364 (6) | |
| H16 | 0.155892 | 0.062534 | 0.142359 | 0.048 (8)* | |
| C17 | 0.2622 (3) | 0.07019 (19) | 0.26449 (18) | 0.0314 (5) | |
| C18 | 0.2011 (3) | 0.0009 (2) | 0.35577 (18) | 0.0357 (6) | |
| H18 | 0.119557 | −0.043570 | 0.366906 | 0.042 (7)* | |
| C19 | 0.2629 (3) | −0.0405 (2) | 0.53669 (17) | 0.0348 (6) | |
| H19A | 0.359759 | −0.070943 | 0.565445 | 0.038 (7)* | |
| H19B | 0.200022 | −0.104871 | 0.555534 | 0.019 (5)* | |
| C20 | 0.1924 (2) | 0.04492 (19) | 0.58170 (17) | 0.0306 (5) | |
| C21 | 0.1961 (3) | 0.0160 (2) | 0.6857 (2) | 0.0419 (6) | |
| H21 | 0.247770 | −0.052834 | 0.725248 | 0.049 (8)* | |
| C22 | 0.1244 (3) | 0.0879 (2) | 0.7316 (2) | 0.0506 (7) | |
| H22 | 0.127846 | 0.067512 | 0.801438 | 0.053 (8)* | |
| C23 | 0.0476 (3) | 0.1901 (2) | 0.6733 (2) | 0.0490 (7) | |
| H23 | −0.002501 | 0.238136 | 0.704015 | 0.049 (8)* | |
| C24 | 0.0450 (3) | 0.2211 (2) | 0.5698 (2) | 0.0427 (6) | |
| H24 | −0.005800 | 0.290501 | 0.530513 | 0.048 (8)* | |
| C25 | 0.1175 (3) | 0.1496 (2) | 0.52394 (19) | 0.0359 (6) | |
| H25 | 0.116296 | 0.171620 | 0.453750 | 0.037 (7)* | |
| C26 | 0.7137 (3) | 0.1742 (2) | 0.00625 (19) | 0.0368 (6) | |
| C27 | 0.7700 (3) | 0.2947 (2) | 0.23968 (18) | 0.0345 (6) |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Fe1 | 0.02404 (18) | 0.02930 (18) | 0.03075 (19) | −0.00346 (13) | −0.00173 (13) | −0.00939 (14) |
| S1 | 0.0808 (6) | 0.0533 (5) | 0.1010 (7) | −0.0154 (4) | 0.0440 (5) | −0.0481 (5) |
| S2 | 0.0373 (4) | 0.0653 (5) | 0.0640 (5) | −0.0146 (3) | −0.0200 (3) | −0.0040 (4) |
| N1 | 0.0271 (10) | 0.0298 (10) | 0.0312 (10) | −0.0087 (8) | −0.0005 (8) | −0.0121 (9) |
| N2 | 0.0294 (11) | 0.0304 (10) | 0.0334 (11) | −0.0020 (8) | −0.0054 (8) | −0.0124 (9) |
| N3 | 0.0412 (12) | 0.0357 (11) | 0.0358 (12) | −0.0008 (9) | −0.0053 (9) | −0.0149 (9) |
| N4 | 0.0365 (12) | 0.0361 (11) | 0.0396 (12) | −0.0018 (9) | −0.0041 (9) | −0.0199 (10) |
| N5 | 0.0353 (11) | 0.0284 (10) | 0.0316 (11) | −0.0042 (8) | −0.0030 (8) | −0.0130 (9) |
| N6 | 0.0276 (10) | 0.0269 (10) | 0.0330 (11) | −0.0037 (8) | −0.0028 (8) | −0.0091 (9) |
| N7 | 0.0296 (11) | 0.0307 (10) | 0.0341 (11) | −0.0061 (8) | −0.0025 (8) | −0.0056 (9) |
| N8 | 0.0280 (10) | 0.0274 (10) | 0.0325 (11) | −0.0041 (8) | 0.0008 (8) | −0.0068 (9) |
| N9 | 0.0371 (14) | 0.0676 (16) | 0.0621 (16) | 0.0012 (11) | 0.0028 (12) | −0.0361 (14) |
| N10 | 0.0295 (12) | 0.0374 (12) | 0.0464 (13) | −0.0031 (9) | −0.0078 (9) | −0.0122 (10) |
| C1 | 0.080 (2) | 0.0589 (19) | 0.0332 (15) | −0.0080 (17) | −0.0100 (15) | −0.0215 (15) |
| C2 | 0.0385 (15) | 0.0481 (16) | 0.0431 (16) | −0.0039 (12) | −0.0114 (12) | −0.0196 (13) |
| C3 | 0.0418 (14) | 0.0362 (13) | 0.0270 (12) | −0.0057 (11) | −0.0060 (10) | −0.0133 (11) |
| C4 | 0.0412 (15) | 0.0341 (13) | 0.0278 (12) | −0.0075 (11) | 0.0019 (10) | −0.0104 (11) |
| C5 | 0.0321 (13) | 0.0261 (12) | 0.0337 (13) | −0.0073 (10) | −0.0063 (10) | −0.0087 (10) |
| C6 | 0.0257 (12) | 0.0245 (11) | 0.0373 (13) | −0.0031 (9) | −0.0070 (10) | −0.0108 (10) |
| C7 | 0.0357 (14) | 0.0291 (13) | 0.0426 (15) | 0.0014 (10) | −0.0076 (11) | −0.0157 (11) |
| C8 | 0.0528 (18) | 0.0564 (18) | 0.0449 (16) | −0.0012 (14) | 0.0061 (13) | −0.0287 (15) |
| C9 | 0.0437 (16) | 0.0541 (17) | 0.0522 (17) | 0.0130 (13) | −0.0100 (13) | −0.0351 (15) |
| C10 | 0.070 (2) | 0.067 (2) | 0.065 (2) | −0.0053 (17) | −0.0127 (17) | −0.0413 (18) |
| C11 | 0.074 (3) | 0.069 (2) | 0.118 (3) | −0.004 (2) | −0.019 (2) | −0.055 (3) |
| C12 | 0.061 (2) | 0.111 (3) | 0.132 (4) | 0.025 (2) | −0.039 (3) | −0.101 (3) |
| C13 | 0.066 (3) | 0.143 (4) | 0.090 (3) | 0.034 (3) | −0.033 (2) | −0.089 (3) |
| C14 | 0.060 (2) | 0.096 (3) | 0.058 (2) | 0.0226 (19) | −0.0177 (17) | −0.049 (2) |
| C15 | 0.0471 (16) | 0.0363 (13) | 0.0335 (13) | −0.0077 (11) | −0.0022 (11) | −0.0176 (11) |
| C16 | 0.0400 (14) | 0.0351 (13) | 0.0395 (14) | −0.0119 (11) | −0.0038 (11) | −0.0174 (12) |
| C17 | 0.0312 (13) | 0.0275 (12) | 0.0371 (13) | −0.0065 (10) | −0.0023 (10) | −0.0127 (10) |
| C18 | 0.0332 (14) | 0.0358 (13) | 0.0375 (14) | −0.0137 (11) | −0.0005 (11) | −0.0107 (11) |
| C19 | 0.0339 (14) | 0.0301 (13) | 0.0334 (13) | −0.0023 (10) | −0.0007 (10) | −0.0044 (11) |
| C20 | 0.0259 (12) | 0.0291 (12) | 0.0336 (13) | −0.0070 (9) | −0.0018 (10) | −0.0072 (10) |
| C21 | 0.0439 (16) | 0.0387 (14) | 0.0409 (15) | 0.0017 (12) | −0.0129 (12) | −0.0116 (12) |
| C22 | 0.0627 (19) | 0.0567 (18) | 0.0413 (16) | −0.0051 (14) | −0.0105 (14) | −0.0265 (14) |
| C23 | 0.0525 (18) | 0.0435 (16) | 0.0619 (19) | −0.0059 (13) | −0.0020 (14) | −0.0317 (15) |
| C24 | 0.0394 (15) | 0.0281 (13) | 0.0569 (18) | −0.0023 (11) | −0.0001 (12) | −0.0122 (13) |
| C25 | 0.0329 (14) | 0.0325 (13) | 0.0342 (14) | −0.0055 (10) | 0.0006 (10) | −0.0033 (11) |
| C26 | 0.0356 (14) | 0.0337 (13) | 0.0429 (15) | −0.0039 (11) | −0.0030 (12) | −0.0160 (12) |
| C27 | 0.0349 (15) | 0.0296 (12) | 0.0315 (13) | −0.0023 (10) | −0.0025 (10) | −0.0028 (10) |
Geometric parameters (Å, º)
| Fe1—N1 | 2.1911 (19) | C5—C6 | 1.446 (3) |
| Fe1—N2 | 2.306 (2) | C6—C7 | 1.364 (3) |
| Fe1—N5 | 2.2618 (19) | C7—H7 | 0.9300 |
| Fe1—N6 | 2.1817 (18) | C8—H8A | 0.9700 |
| Fe1—N9 | 2.088 (2) | C8—H8B | 0.9700 |
| Fe1—N10 | 2.088 (2) | C8—C9 | 1.511 (4) |
| S1—C26 | 1.620 (3) | C9—C10 | 1.370 (4) |
| S2—C27 | 1.621 (3) | C9—C14 | 1.383 (4) |
| N1—C4 | 1.460 (3) | C10—H10 | 0.9300 |
| N1—C5 | 1.271 (3) | C10—C11 | 1.397 (4) |
| N2—N3 | 1.305 (3) | C11—H11 | 0.9300 |
| N2—C6 | 1.361 (3) | C11—C12 | 1.376 (6) |
| N3—N4 | 1.355 (3) | C12—H12 | 0.9300 |
| N4—C7 | 1.339 (3) | C12—C13 | 1.357 (6) |
| N4—C8 | 1.466 (3) | C13—H13 | 0.9300 |
| N5—C15 | 1.464 (3) | C13—C14 | 1.373 (5) |
| N5—C16 | 1.267 (3) | C14—H14 | 0.9300 |
| N6—N7 | 1.310 (3) | C15—H15A | 0.9700 |
| N6—C17 | 1.359 (3) | C15—H15B | 0.9700 |
| N7—N8 | 1.345 (2) | C16—H16 | 0.9300 |
| N8—C18 | 1.338 (3) | C16—C17 | 1.447 (3) |
| N8—C19 | 1.459 (3) | C17—C18 | 1.362 (3) |
| N9—C26 | 1.147 (3) | C18—H18 | 0.9300 |
| N10—C27 | 1.161 (3) | C19—H19A | 0.9700 |
| C1—H1A | 0.9600 | C19—H19B | 0.9700 |
| C1—H1B | 0.9600 | C19—C20 | 1.505 (3) |
| C1—H1C | 0.9600 | C20—C21 | 1.386 (3) |
| C1—C3 | 1.530 (3) | C20—C25 | 1.390 (3) |
| C2—H2A | 0.9600 | C21—H21 | 0.9300 |
| C2—H2B | 0.9600 | C21—C22 | 1.380 (4) |
| C2—H2C | 0.9600 | C22—H22 | 0.9300 |
| C2—C3 | 1.529 (3) | C22—C23 | 1.380 (4) |
| C3—C4 | 1.543 (3) | C23—H23 | 0.9300 |
| C3—C15 | 1.530 (3) | C23—C24 | 1.374 (4) |
| C4—H4A | 0.9700 | C24—H24 | 0.9300 |
| C4—H4B | 0.9700 | C24—C25 | 1.379 (4) |
| C5—H5 | 0.9300 | C25—H25 | 0.9300 |
| N1—Fe1—N2 | 72.65 (7) | N4—C7—H7 | 127.6 |
| N1—Fe1—N5 | 77.61 (7) | C6—C7—H7 | 127.6 |
| N5—Fe1—N2 | 107.15 (7) | N4—C8—H8A | 108.4 |
| N6—Fe1—N1 | 134.53 (7) | N4—C8—H8B | 108.4 |
| N6—Fe1—N2 | 82.74 (7) | N4—C8—C9 | 115.4 (2) |
| N6—Fe1—N5 | 73.95 (7) | H8A—C8—H8B | 107.5 |
| N9—Fe1—N1 | 94.52 (9) | C9—C8—H8A | 108.4 |
| N9—Fe1—N2 | 159.71 (8) | C9—C8—H8B | 108.4 |
| N9—Fe1—N5 | 84.55 (8) | C10—C9—C8 | 123.0 (3) |
| N9—Fe1—N6 | 116.89 (9) | C10—C9—C14 | 118.9 (3) |
| N10—Fe1—N1 | 116.78 (7) | C14—C9—C8 | 118.0 (3) |
| N10—Fe1—N2 | 84.55 (8) | C9—C10—H10 | 120.0 |
| N10—Fe1—N5 | 164.17 (7) | C9—C10—C11 | 120.0 (3) |
| N10—Fe1—N6 | 97.64 (7) | C11—C10—H10 | 120.0 |
| N10—Fe1—N9 | 87.58 (9) | C10—C11—H11 | 120.0 |
| C4—N1—Fe1 | 121.79 (15) | C12—C11—C10 | 120.0 (4) |
| C5—N1—Fe1 | 119.40 (16) | C12—C11—H11 | 120.0 |
| C5—N1—C4 | 117.8 (2) | C11—C12—H12 | 120.0 |
| N3—N2—Fe1 | 137.20 (15) | C13—C12—C11 | 119.9 (4) |
| N3—N2—C6 | 109.88 (19) | C13—C12—H12 | 120.0 |
| C6—N2—Fe1 | 111.96 (15) | C12—C13—H13 | 119.9 |
| N2—N3—N4 | 106.06 (18) | C12—C13—C14 | 120.3 (4) |
| N3—N4—C8 | 119.0 (2) | C14—C13—H13 | 119.9 |
| C7—N4—N3 | 111.3 (2) | C9—C14—H14 | 119.5 |
| C7—N4—C8 | 129.7 (2) | C13—C14—C9 | 120.9 (4) |
| C15—N5—Fe1 | 125.38 (14) | C13—C14—H14 | 119.5 |
| C16—N5—Fe1 | 115.78 (16) | N5—C15—C3 | 112.87 (19) |
| C16—N5—C15 | 118.8 (2) | N5—C15—H15A | 109.0 |
| N7—N6—Fe1 | 135.01 (15) | N5—C15—H15B | 109.0 |
| N7—N6—C17 | 109.86 (18) | C3—C15—H15A | 109.0 |
| C17—N6—Fe1 | 113.90 (14) | C3—C15—H15B | 109.0 |
| N6—N7—N8 | 106.19 (18) | H15A—C15—H15B | 107.8 |
| N7—N8—C19 | 119.86 (19) | N5—C16—H16 | 121.5 |
| C18—N8—N7 | 111.16 (19) | N5—C16—C17 | 116.9 (2) |
| C18—N8—C19 | 128.89 (19) | C17—C16—H16 | 121.5 |
| C26—N9—Fe1 | 176.7 (2) | N6—C17—C16 | 118.5 (2) |
| C27—N10—Fe1 | 165.1 (2) | N6—C17—C18 | 107.5 (2) |
| H1A—C1—H1B | 109.5 | C18—C17—C16 | 134.0 (2) |
| H1A—C1—H1C | 109.5 | N8—C18—C17 | 105.3 (2) |
| H1B—C1—H1C | 109.5 | N8—C18—H18 | 127.3 |
| C3—C1—H1A | 109.5 | C17—C18—H18 | 127.3 |
| C3—C1—H1B | 109.5 | N8—C19—H19A | 109.0 |
| C3—C1—H1C | 109.5 | N8—C19—H19B | 109.0 |
| H2A—C2—H2B | 109.5 | N8—C19—C20 | 113.00 (18) |
| H2A—C2—H2C | 109.5 | H19A—C19—H19B | 107.8 |
| H2B—C2—H2C | 109.5 | C20—C19—H19A | 109.0 |
| C3—C2—H2A | 109.5 | C20—C19—H19B | 109.0 |
| C3—C2—H2B | 109.5 | C21—C20—C19 | 118.8 (2) |
| C3—C2—H2C | 109.5 | C21—C20—C25 | 118.4 (2) |
| C1—C3—C4 | 106.8 (2) | C25—C20—C19 | 122.7 (2) |
| C2—C3—C1 | 109.2 (2) | C20—C21—H21 | 119.5 |
| C2—C3—C4 | 111.5 (2) | C22—C21—C20 | 121.0 (2) |
| C2—C3—C15 | 110.2 (2) | C22—C21—H21 | 119.5 |
| C15—C3—C1 | 107.8 (2) | C21—C22—H22 | 120.1 |
| C15—C3—C4 | 111.2 (2) | C21—C22—C23 | 119.7 (3) |
| N1—C4—C3 | 111.39 (18) | C23—C22—H22 | 120.1 |
| N1—C4—H4A | 109.4 | C22—C23—H23 | 120.0 |
| N1—C4—H4B | 109.4 | C24—C23—C22 | 120.0 (3) |
| C3—C4—H4A | 109.4 | C24—C23—H23 | 120.0 |
| C3—C4—H4B | 109.4 | C23—C24—H24 | 119.9 |
| H4A—C4—H4B | 108.0 | C23—C24—C25 | 120.2 (2) |
| N1—C5—H5 | 121.1 | C25—C24—H24 | 119.9 |
| N1—C5—C6 | 117.7 (2) | C20—C25—H25 | 119.7 |
| C6—C5—H5 | 121.1 | C24—C25—C20 | 120.6 (2) |
| N2—C6—C5 | 117.2 (2) | C24—C25—H25 | 119.7 |
| N2—C6—C7 | 107.9 (2) | N9—C26—S1 | 179.2 (3) |
| C7—C6—C5 | 134.9 (2) | N10—C27—S2 | 179.6 (3) |
| N4—C7—C6 | 104.9 (2) | ||
| Fe1—N1—C4—C3 | 73.0 (2) | C1—C3—C15—N5 | 177.6 (2) |
| Fe1—N1—C5—C6 | −0.8 (3) | C2—C3—C4—N1 | 55.2 (3) |
| Fe1—N2—N3—N4 | 167.35 (16) | C2—C3—C15—N5 | −63.3 (3) |
| Fe1—N2—C6—C5 | 11.4 (2) | C4—N1—C5—C6 | 167.84 (19) |
| Fe1—N2—C6—C7 | −171.13 (15) | C4—C3—C15—N5 | 60.8 (3) |
| Fe1—N5—C15—C3 | −59.1 (3) | C5—N1—C4—C3 | −95.4 (2) |
| Fe1—N5—C16—C17 | −1.8 (3) | C5—C6—C7—N4 | 177.4 (2) |
| Fe1—N6—N7—N8 | 166.53 (16) | C6—N2—N3—N4 | 0.0 (2) |
| Fe1—N6—C17—C16 | 10.7 (3) | C7—N4—C8—C9 | −79.0 (3) |
| Fe1—N6—C17—C18 | −169.65 (16) | C8—N4—C7—C6 | −178.2 (2) |
| N1—C5—C6—N2 | −7.7 (3) | C8—C9—C10—C11 | 177.6 (3) |
| N1—C5—C6—C7 | 175.7 (2) | C8—C9—C14—C13 | −176.8 (3) |
| N2—N3—N4—C7 | 0.4 (3) | C9—C10—C11—C12 | −0.5 (5) |
| N2—N3—N4—C8 | 178.3 (2) | C10—C9—C14—C13 | −0.3 (5) |
| N2—C6—C7—N4 | 0.6 (3) | C10—C11—C12—C13 | −1.3 (6) |
| N3—N2—C6—C5 | −177.83 (19) | C11—C12—C13—C14 | 2.3 (6) |
| N3—N2—C6—C7 | −0.4 (3) | C12—C13—C14—C9 | −1.5 (5) |
| N3—N4—C7—C6 | −0.6 (3) | C14—C9—C10—C11 | 1.3 (5) |
| N3—N4—C8—C9 | 103.5 (3) | C15—N5—C16—C17 | 175.0 (2) |
| N4—C8—C9—C10 | 37.7 (4) | C15—C3—C4—N1 | −68.1 (3) |
| N4—C8—C9—C14 | −146.0 (3) | C16—N5—C15—C3 | 124.5 (2) |
| N5—C16—C17—N6 | −6.0 (3) | C16—C17—C18—N8 | 179.7 (3) |
| N5—C16—C17—C18 | 174.4 (3) | C17—N6—N7—N8 | 0.4 (2) |
| N6—N7—N8—C18 | −0.4 (3) | C18—N8—C19—C20 | −102.2 (3) |
| N6—N7—N8—C19 | −177.12 (19) | C19—N8—C18—C17 | 176.5 (2) |
| N6—C17—C18—N8 | 0.1 (3) | C19—C20—C21—C22 | −175.6 (2) |
| N7—N6—C17—C16 | 180.0 (2) | C19—C20—C25—C24 | 175.1 (2) |
| N7—N6—C17—C18 | −0.4 (3) | C20—C21—C22—C23 | 0.0 (4) |
| N7—N8—C18—C17 | 0.1 (3) | C21—C20—C25—C24 | −1.9 (3) |
| N7—N8—C19—C20 | 74.0 (3) | C21—C22—C23—C24 | −1.2 (4) |
| N8—C19—C20—C21 | −166.2 (2) | C22—C23—C24—C25 | 0.8 (4) |
| N8—C19—C20—C25 | 16.8 (3) | C23—C24—C25—C20 | 0.8 (4) |
| C1—C3—C4—N1 | 174.4 (2) | C25—C20—C21—C22 | 1.5 (4) |
Hydrogen-bond geometry (Å, º)
Cg is the centroid of the C20–C25 ring.
| D—H···A | D—H | H···A | D···A | D—H···A |
| C18—H18···Cgi | 0.93 | 2.42 | 3.330 (3) | 167 |
| C19—H19A···N7ii | 0.97 | 2.38 | 3.311 (3) | 162 |
| C21—H21···C27ii | 0.93 | 2.89 | 3.603 (3) | 134 |
| C7—H7···S1iii | 0.93 | 2.87 | 3.755 (3) | 159 |
| C4—H4B···N10iii | 0.97 | 2.69 | 3.617 (3) | 160 |
| C4—H4B···C27iii | 0.97 | 2.75 | 3.709 (3) | 171 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z.
Funding Statement
This work was funded by H2020 Marie Skłodowska-Curie Actions grant 734322.
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020012608/wm5580sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989020012608/wm5580Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989020012608/wm5580Isup3.cdx
CCDC reference: 2032292
Additional supporting information: crystallographic information; 3D view; checkCIF report