research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 82| Part 4| April 2026| Pages 349-352
https://doi.org/10.1107/S205698902600229X

A second monoclinic polymorph of ferrocenecarboxaldehyde

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Jamal Lasri,a* Yaseen A. Almehmadi,a,b Naser E. Eltayeb,a,c Tuncer Hökelekd and Aidan P. McKaye

aDepartment of Chemistry, Rabigh College of Science and Arts, King Abdulaziz University, Jeddah 21589, Saudi Arabia, bKing Fahd Medical Research Center, King Abdulaziz University, Jeddah 21589, Saudi Arabia, cDepartment of Chemistry, Faculty of Pure and Applied Sciences, International University of Africa, Khartoum 2469, Sudan, dDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Türkiye, and eEaStCHEM School of Chemistry, University of St Andrews, Fife KY16 9ST, United Kingdom
*Correspondence e-mail: [email protected]

Edited by F. F. Ferreira, Universidade Federal do ABC, Brazil (Received 11 February 2026; accepted 2 March 2026; online 5 March 2026)

The title compound, [Fe(C5H5)(C6H5O)] (I), crystallizes in the space group P21 with two crystallographically independent ferrocenecarboxaldehyde mol­ecules in the asymmetric unit, in which the C—O bond lengths and also the O—C—C bond angles of the carboxaldehyde moieties have significantly different values. In the crystal, C—H⋯O hydrogen bonds link the mol­ecules into infinite chains along the b-axis direction. The π–π stacking inter­actions between the parallel ferrocene rings [centroid-to-centroid distances of 3.305 (4) and 3.293 (4) Å] and the C—H⋯π(ring) inter­actions help to consolidate the packing. Compound I is a polymorph of the previously reported form of ferrocenecarboxaldehyde [Sato et al. (1984View full citation). Bull. Chem. Soc. Jpn 57, 634–638; Lousada et al. (2008View full citation). J. Phys. Chem. A. 112, 2977–2987], which crystallizes in the space group P212121 with one mol­ecule in the asymmetric unit. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (54.8%), H⋯C/C⋯H (26.5%) and H⋯O/O⋯H (18.4%) inter­actions. The volume of the crystal voids and the percentage of free space were calculated to be 53.38 Å3 and 6.03%, showing that there is no large cavity in the crystal packing. Hydrogen bonding, π–π, C—H⋯π(ring) and van der Waals inter­actions are the dominant inter­actions in the crystal packing.

CCDC reference: 2534450

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1. Chemical context

Since its discovery in 1951, compounds containing the ferrocene moiety have been of significant inter­est due to their application in environmental pollution remediation (Wang et al., 2014View full citation; Kaur et al., 2015View full citation). The well-established chemistry of ferrocene derivatives along with their stabilities encouraged their incorporation in the synthesis of materials with non-linear optical (Di Bella et al., 2001View full citation) or reversible redox properties (Kowalski et al., 2014View full citation) or they can be used as catalysts (Ruble et al., 1997View full citation). Moreover, biologically active materials containing ferrocene as a modified Tamoxifen drug by replacing one π–π group of the aromatic rings with a ferrocene fragment have been developed (Top et al., 2001View full citation). Reasonable anti­malarial activity was noted against Plasmodium falciparum, even against those that are chloro­quine resistant (Biot et al., 2006View full citation). Ferrocene-based asymmetrical azines have shown potential as anti­microbial-anti­tumor agents (Lasri et al., 2018aView full citation). Moreover, ferrocene-based Schiff bases have been found to be good absorbents for methyl blue from water (Lasri et al., 2018bView full citation). Herein we report the mol­ecular and crystal structures, Hirshfeld surface analysis and crystal voids of the title compound. Compound I is a polymorph of the previously reported form of ferrocenecarboxaldehyde [Sato et al., 1984View full citation; Lousada et al., 2008View full citation; Cambridge Structural Database (CSD; Groom et al., 2016View full citation) refcodes DEJZAT and DEJZAT01, respectively] in the space group P212121 with one mol­ecule in the asymmetric unit.

[Scheme 1]

2. Structural commentary

The asymmetric unit of the title compound contains two crystallographically independent ferrocenecarboxaldehyde mol­ecules (Fig. 1[link]). In the carboxaldehyde moieties, the C11—O11 [1.137 (14) Å] and C22—O22 [1.229 (12) Å] bond lengths and also the O11—C11—C1 [130.2 (13)°] and O22—C22—C12 [125.6 (9)°] bond angles have significantly different values. The corresponding values are C11—O11 = 1.042 (10) Å and O11—C11—C6 = 142.5 (17)° in the previously reported form of ferrocenecarboxaldehyde (Lousada et al., 2008View full citation). On the other hand, the C1—C11 [1.451 (16) Å] and C12—C22 [1.442 (14) Å] bond lengths are between the typical values of single and double C—C bonds of 1.54 and 1.40 Å, respectively, supporting the existence of CO—Cp conjugation. The corresponding C—C bond was reported as C6—C11 = 1.444 (14) Å in the previously reported form of ferrocenecarboxaldehyde (Lousada et al., 2008View full citation).

[Figure 1]
Figure 1
The title mol­ecule with the atom-numbering scheme and 50% probability ellipsoids.

The C5—C1—C11—O11 [−173.5 (10)°], C2—C1—C11—O11 [15.6 (18)°] and C13—C12—C22—O22 [−177.4 (9)°], C16—C12—C22—O22 [−6.0 (16)°] torsion angles indicate that the CHO substituents are almost coplanar with the Cp rings, thus allowing conjugations of the π–π electron systems of the C=O bonds and the aromatic cyclo­penta­dienyl rings. Atoms O11, C11 and O22, C22 are 0.065 (6), 0.152 (7) and 0.167 (4), 0.128 (6) Å, respectively, away from the corresponding best least-squares ring planes. Thus, they are almost coplanar with the adjacent Cp rings. The planar A (C1–C5), B (C6–C10) and C (C12—16), D (C17–C21) rings are oriented at dihedral angles of A/B = 1.15 (8)°, A/C = 13.98 (27)°, A/D = 13.55 (27)°, B/C = 14.30 (25)°, B/D = 13.84 (28)° and C/D = 0.64 (22)°.

The Fe1—C and Fe2—C bond lengths are within the ranges 2.016 (9)—2.056 (10) Å and 2.021 (10)—2.056 (11) Å, respectively, for the two independent mol­ecules in the asymmetric unit. The C1—C11 [1.451 (16) Å] and C12—C22 [1.442 (14) Å] bond lengths are similar but the O11—C11 [1.137 (14) Å] bond is shorter than the C22—O22 [1.229 (12) Å] bond. On the other hand, the C12—C22—O22 [125.6 (9)°] bond angle is narrower than the corresponding C1—C11—O11 [130.2 (13)°] bond angle.

3. Supra­molecular features

In the crystal, C6—H6⋯O11 hydrogen bonds (Table 1[link]) link the mol­ecules into infinite chains along the b-axis direction (Fig. 2[link]), and C3—H3⋯O22 hydrogen bonds (Table 1[link]) link the mol­ecules to these chains (Fig. 2[link]). There are π–π stacking inter­actions between the parallel ferrocene rings with centroid-to-centroid distances of 3.305 (7) and 3.293 (7) Å. The C—H⋯π(ring) inter­actions (Table 2[link]) may help to consolidate the packing. Hydrogen bonding, C—H⋯π(ring) and van der Waals inter­actions are the dominant inter­actions in the crystal packing.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1–Cg4 are the centroids of the (C1–C5), (C6–C10), (C12–C16) and (C17–C21) rings, respectively.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
C3—H3⋯O22i 0.95 2.60 3.520 (13) 165
C6—H6⋯O11ii 0.95 2.45 3.255 (13) 142
C7—H7⋯Cg3i 0.95 2.91 3.625 (12) 133
C11—H11⋯Cg4ii 0.95 2.97 3.907 (12) 170
C16—H16⋯Cg2iii 0.95 3.03 3.935 (13) 159
C18—H18⋯Cg1ii 0.95 2.80 3.631 (7) 146
Symmetry codes: (i) Mathematical equation; (ii) Mathematical equation; (iii) Mathematical equation.

Table 2
Experimental details

Crystal data
Chemical formula [Fe(C5H5)(C6H5O)]
Mr 214.04
Crystal system, space group Monoclinic, P21
Temperature (K) 173
a, b, c (Å) 10.4438 (9), 7.5766 (8), 11.2044 (14)
β (°) 92.459 (15)
V (Å3) 885.77 (17)
Z 4
Radiation type Mo Kα
μ (mm−1) 1.65
Crystal size (mm) 0.1 × 0.09 × 0.02
 
Data collection
Diffractometer Rigaku XtaLAB P200K
Absorption correction Multi-scan (CrysAlis PRO; Rigaku OD, 2024View full citation)
Tmin, Tmax 0.725, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 6451, 6451, 5568
(sin θ/λ)max (Å−1) 0.699
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.145, 1.07
No. of reflections 6451
No. of parameters 236
No. of restraints 1
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 1.14, −0.49
Absolute structure Flack x determined using 1494 quotients [(I+)−(I−)]/[(I+)+(I−)] (Parsons et al., 2013View full citation)
Absolute structure parameter −0.03 (2)
Computer programs: CrysAlis PRO (Rigaku OD, 2024View full citation), SHELXT (Sheldrick, 2015aView full citation), SHELXL2019/3 (Sheldrick, 2015bView full citation) and OLEX2 (Dolomanov et al., 2009View full citation).
[Figure 2]
Figure 2
A partial packing diagram viewed down the a-axis direction. C—H⋯O hydrogen bonds are shown as dashed lines. The (C)—H atoms not involved in hydrogen bonds have been omitted for clarity.

4. Hirshfeld surface analysis

A Hirshfeld surface (HS) analysis was carried out by Crystal Explorer 17.5 (Spackman et al., 2021View full citation) to clarify the inter­molecular inter­actions in the crystal. The contact distances (Table 1[link]) are shown in Fig. 3[link], where the bright-red spots correspond to the respective donors and/or acceptors. According to the 2D fingerprint plots (McKinnon et al., 2007View full citation), the inter­molecular H⋯H, H⋯C/C⋯H and H⋯O/O⋯H contacts make important contributions to the HS of 54.8%, 26.5% and 18.4%, respectively (Fig. 4[link]).

[Figure 3]
Figure 3
View of the three-dimensional Hirshfeld surface of the title compound plotted over dnorm.
[Figure 4]
Figure 4
The full two-dimensional fingerprint plots for the title compound, showing (a) all inter­actions, and delineated into (b) H⋯H, (c) H⋯C/C⋯H, (d) H⋯O/O⋯H and (e) C⋯O/O⋯C, inter­actions. The di and de values are the closest inter­nal and external distances (in Å) from given points on the Hirshfeld surface.

5. Database survey

A survey of the Cambridge Structural Database (CSD, July 2025 update; Groom et al., 2016View full citation) revealed seven structures containing the target compound ferrocenecarboxaldehyde I (DEJZAT; Sato et al., 1984View full citation), compound II (DEJZAT01; Lousada et al., 2008View full citation), compound III (GUCJIA; Singh et al., 2020View full citation), compound IV (MEJMUK Kim et al., 2006View full citation) compound V (QARLON Brunet et al., 2017View full citation), compound VI (QONQEQ Meilikhov et al., 2009View full citation), compound VII (XUFCEJ Zhang et al., 2020View full citation).

6. Crystal voids

If the mol­ecules are tightly packed and the applied external mechanical force does not easily break the crystal, then the crystal packing does not result in significant voids. A void analysis was performed by adding up the electron densities of the spherically symmetric atoms contained in the asymmetric unit (Turner et al., 2011View full citation). The volume of the crystal voids (Fig. 5[link]a and b) and the percentage of free space in the unit cell are calculated as 53.38 Å3 and 6.03%, respectively, indicating that the crystal packing is compact.

[Figure 5]
Figure 5
Graphical views of the voids in the crystal packing of the title compound. (a) along a-axis and (b) along c-axis directions.

7. Synthesis and crystallization

To a solution of N-methyl­hydroxyl­amine hydro­chloride (100.0 mg, 1.20 mmol) in MeOH (50 ml) was added sodium carbonate (63.4 mg, 0.60 mmol) and the reaction mixture was stirred for 10 min followed by the addition of ferrocenecarboxaldehyde (232.9 mg, 1.09 mmol). Then, the mixture was stirred for 12 h at room temperature. After that, the precipitate formed was filtered off. The expected product N-methyl-C-ferrocenyl aldo­nitrone was not detected, in contrast, only the starting material ferrocenecarboxaldehyde was recuperated. Orange crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution at room temperature.

Fe[(η5-C5H5)(η5-C5H4CHO)]. FT-IR (cm−1) 3086 (νC–H, C5H5); 2865, 2832, 2803, 2761 and 2726 (νC–H, CHO); 1681 (νC–O, CHO); 1104 and 1409 (νC–C, C5H5); 1387 (δC–H, CHO); 1002 (δC–H, C5H5); 824 and 842 (πC–H, C5H5); 497 (C5H5 ring tilt); 481 (νFe–C5H5). 1H NMR (CDCl3): δ 4.28 (5H, C5H5); 4.61 (2H, C5H4) and 4.80 (2H, C5H4); 9.96 (1H, CH=O). Elemental analysis for C11H10OFe: calculated, C 61.73%, H 4.71%; found, C 61.50%, H 4.57%. The observed FT-IR and 1H NMR spectra are in good agreement with those reported (Lousada et al., 2008View full citation).

8. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1[link].. The C-bound hydrogen atom positions were calculated geometrically at distances of 0.95 Å (for aromatic and methine CH) and refined using a riding model by applying the constraint Uiso(H) = 1.2 × Ueq(C). Data were processed as a two-component twin with the second component rotated by 179.9856° around [0 0 1] (reciprocal), or [0.05 0 1] (direct) and the twin component ratio was refined to 0.501:0.499. The Flack absolute structure parameter (Parsons et al., 2013View full citation) refined to −0.03 (2). The expected values are 0.00 and 1.00 for correct and reverse absolute structures, respectively. Thus, the absolute structure was determined unambiguously.

Supporting information

CCDC reference: 2534450

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698902600229X/ee2027sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902600229X/ee2027Isup2.hkl

checkCIF report


Computing details top

Ferrocenecarboxaldehyde top
Crystal data top
[Fe(C5H5)(C6H5O)]F(000) = 440
Mr = 214.04Dx = 1.605 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 10.4438 (9) ÅCell parameters from 4087 reflections
b = 7.5766 (8) Åθ = 2.6–26.3°
c = 11.2044 (14) ŵ = 1.65 mm−1
β = 92.459 (15)°T = 173 K
V = 885.77 (17) Å3Plate, orange
Z = 40.1 × 0.09 × 0.02 mm
Data collection top
Rigaku XtaLAB P200K
diffractometer		6451 measured reflections
Radiation source: Rotating Anode, Rigaku FR-X6451 independent reflections
Rigaku Osmic Confocal Optical System monochromator5568 reflections with I > 2σ(I)
Detector resolution: 5.8140 pixels mm-1θmax = 29.8°, θmin = 1.8°
shutterless scansh = −14→14
Absorption correction: multi-scan
(CrysAlisPro; Rigaku OD, 2024)		k = −10→10
Tmin = 0.725, Tmax = 1.000l = −15→14
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.054 w = 1/[σ2(Fo2) + (0.0947P)2 + 0.3203P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.145(Δ/σ)max < 0.001
S = 1.07Δρmax = 1.14 e Å−3
6451 reflectionsΔρmin = −0.49 e Å−3
236 parametersAbsolute structure: Flack x determined using 1494 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraintAbsolute structure parameter: −0.03 (2)
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.

Refinement. Data was processed as 2-component twin with second component rotated 179.9856 ° around [0 0 1] (reciprocal), or [0.05 0 1] (direct) and twin component ratio was refined to 0.501:0.499

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe10.85974 (10)0.52362 (12)0.79568 (10)0.0334 (3)
Fe20.63769 (10)0.47927 (12)0.29292 (10)0.0355 (3)
O111.0675 (8)0.6185 (16)0.5310 (8)0.090 (4)
O220.3966 (6)0.4636 (10)0.0285 (6)0.0536 (16)
C11.0167 (8)0.6417 (14)0.7329 (9)0.041 (2)
C20.9145 (8)0.7685 (14)0.7382 (10)0.046 (2)
H20.8770800.8335240.6731490.055*
C30.8811 (10)0.7776 (15)0.8563 (12)0.059 (3)
H30.8148260.8494310.8855650.071*
C40.9594 (11)0.666 (2)0.9255 (10)0.065 (3)
H40.9573670.6506321.0096000.078*
C51.0422 (8)0.5783 (15)0.8491 (10)0.050 (3)
H51.1043100.4917760.8721610.060*
C60.7910 (9)0.3445 (16)0.6723 (10)0.049 (3)
H60.8195760.3287030.5936870.058*
C70.6925 (8)0.4557 (16)0.7051 (8)0.042 (2)
H70.6432600.5299860.6525380.051*
C80.6781 (7)0.4405 (11)0.8278 (8)0.038 (2)
H80.6172440.5017840.8729520.046*
C90.7696 (8)0.3181 (14)0.8732 (10)0.044 (2)
H90.7809530.2821070.9541900.053*
C100.8414 (9)0.2583 (14)0.7771 (11)0.051 (3)
H100.9102340.1763070.7814610.061*
C111.0735 (9)0.5704 (17)0.6272 (11)0.059 (3)
H111.1236850.4670740.6405380.071*
C120.4993 (8)0.3378 (15)0.2019 (8)0.038 (2)
C130.5964 (9)0.2244 (13)0.2545 (10)0.046 (2)
H130.6496540.1470550.2119120.055*
C140.6000 (9)0.2460 (16)0.3784 (10)0.052 (3)
H140.6544110.1847220.4344590.062*
C150.5080 (9)0.3757 (15)0.4053 (9)0.049 (2)
H150.4911310.4178690.4829390.059*
C160.4453 (9)0.4321 (15)0.2973 (8)0.045 (2)
H160.3790470.5177710.2899470.054*
C170.7123 (10)0.6572 (16)0.1795 (11)0.053 (3)
H170.6860530.6739030.0980460.064*
C180.8094 (7)0.5402 (17)0.2229 (8)0.046 (2)
H180.8594140.4638000.1764190.055*
C190.8176 (8)0.5585 (16)0.3472 (9)0.051 (3)
H190.8757790.4968980.3996990.061*
C200.7268 (9)0.6817 (16)0.3823 (12)0.057 (3)
H200.7114200.7170720.4617600.068*
C210.6620 (10)0.7436 (17)0.2768 (14)0.064 (4)
H210.5956540.8294180.2729670.077*
C220.4762 (9)0.3628 (13)0.0751 (9)0.046 (2)
H220.5268490.2955440.0233140.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0255 (5)0.0258 (8)0.0489 (6)−0.0017 (5)0.0031 (4)−0.0006 (5)
Fe20.0253 (6)0.0246 (7)0.0565 (7)−0.0025 (5)0.0006 (5)0.0015 (5)
O110.089 (7)0.120 (10)0.061 (6)−0.062 (6)0.015 (4)−0.005 (5)
O220.049 (4)0.044 (4)0.068 (4)−0.002 (3)−0.006 (3)0.004 (3)
C10.031 (5)0.030 (5)0.062 (6)−0.011 (4)0.007 (4)−0.002 (4)
C20.035 (6)0.030 (6)0.071 (7)−0.007 (4)−0.003 (4)0.012 (5)
C30.046 (7)0.039 (6)0.092 (9)−0.011 (5)0.011 (6)−0.030 (6)
C40.060 (7)0.083 (9)0.051 (6)−0.036 (6)0.001 (5)−0.015 (6)
C50.030 (5)0.039 (6)0.079 (7)−0.010 (4)−0.009 (4)0.007 (5)
C60.039 (5)0.045 (7)0.063 (6)−0.010 (5)0.011 (4)−0.015 (6)
C70.034 (5)0.040 (6)0.051 (5)−0.015 (4)−0.008 (3)0.001 (4)
C80.028 (4)0.022 (5)0.065 (6)−0.007 (3)0.011 (3)0.002 (4)
C90.030 (5)0.035 (6)0.068 (6)−0.009 (4)0.001 (4)0.012 (5)
C100.039 (6)0.014 (6)0.100 (9)0.001 (4)0.013 (5)0.001 (5)
C110.043 (6)0.052 (7)0.084 (8)−0.021 (5)0.015 (5)−0.011 (6)
C120.026 (4)0.036 (6)0.054 (5)−0.005 (4)0.000 (3)−0.002 (4)
C130.035 (5)0.021 (5)0.083 (8)−0.005 (4)0.016 (5)0.003 (5)
C140.036 (5)0.047 (6)0.071 (7)−0.010 (5)−0.003 (4)0.014 (5)
C150.039 (5)0.055 (7)0.054 (6)−0.013 (5)0.010 (4)−0.002 (5)
C160.041 (5)0.042 (6)0.054 (5)−0.009 (4)0.010 (4)−0.002 (5)
C170.048 (6)0.038 (7)0.072 (7)−0.021 (5)−0.009 (5)0.022 (6)
C180.031 (4)0.042 (6)0.065 (6)−0.004 (4)0.007 (3)0.017 (5)
C190.037 (5)0.049 (7)0.065 (6)−0.007 (4)−0.011 (4)0.006 (5)
C200.043 (6)0.039 (7)0.089 (8)−0.025 (5)−0.001 (5)−0.010 (6)
C210.035 (6)0.028 (7)0.128 (11)−0.007 (5)0.002 (6)0.013 (7)
C220.049 (6)0.028 (5)0.062 (6)−0.012 (4)0.011 (4)−0.009 (4)
Geometric parameters (Å, º) top
Fe1—C12.021 (9)C6—H60.9500
Fe1—C22.053 (10)C6—C71.391 (14)
Fe1—C32.050 (10)C6—C101.424 (16)
Fe1—C42.056 (10)C7—H70.9500
Fe1—C52.016 (9)C7—C81.394 (12)
Fe1—C62.045 (11)C8—H80.9500
Fe1—C72.047 (8)C8—C91.411 (13)
Fe1—C82.046 (8)C9—H90.9500
Fe1—C92.034 (10)C9—C101.413 (16)
Fe1—C102.029 (11)C10—H100.9500
Fe2—C122.038 (9)C11—H110.9500
Fe2—C132.021 (10)C12—C131.437 (14)
Fe2—C142.056 (11)C12—C161.423 (14)
Fe2—C152.045 (9)C12—C221.442 (14)
Fe2—C162.043 (9)C13—H130.9500
Fe2—C172.031 (10)C13—C141.396 (16)
Fe2—C182.041 (8)C14—H140.9500
Fe2—C192.040 (9)C14—C151.416 (15)
Fe2—C202.035 (11)C15—H150.9500
Fe2—C212.028 (13)C15—C161.417 (14)
O11—C111.137 (14)C16—H160.9500
O22—C221.229 (12)C17—H170.9500
C1—C21.440 (14)C17—C181.417 (15)
C1—C51.403 (15)C17—C211.393 (19)
C1—C111.451 (16)C18—H180.9500
C2—H20.9500C18—C191.399 (14)
C2—C31.384 (16)C19—H190.9500
C3—H30.9500C19—C201.399 (16)
C3—C41.392 (19)C20—H200.9500
C4—H40.9500C20—C211.417 (18)
C4—C51.408 (17)C21—H210.9500
C5—H50.9500C22—H220.9500
C1—Fe1—C241.4 (4)Fe1—C4—H4127.4
C1—Fe1—C367.7 (4)C3—C4—Fe169.9 (6)
C1—Fe1—C467.7 (4)C3—C4—H4126.0
C1—Fe1—C6109.0 (4)C3—C4—C5108.0 (10)
C1—Fe1—C7128.8 (4)C5—C4—Fe168.3 (6)
C1—Fe1—C8166.0 (4)C5—C4—H4126.0
C1—Fe1—C9152.3 (4)Fe1—C5—H5124.4
C1—Fe1—C10118.5 (4)C1—C5—Fe169.8 (5)
C2—Fe1—C467.0 (5)C1—C5—C4107.9 (10)
C3—Fe1—C239.4 (5)C1—C5—H5126.1
C3—Fe1—C439.6 (5)C4—C5—Fe171.3 (5)
C5—Fe1—C140.7 (4)C4—C5—H5126.1
C5—Fe1—C268.6 (4)Fe1—C6—H6126.5
C5—Fe1—C367.7 (4)C7—C6—Fe170.2 (6)
C5—Fe1—C440.4 (5)C7—C6—H6125.9
C5—Fe1—C6129.6 (4)C7—C6—C10108.1 (9)
C5—Fe1—C7166.9 (4)C10—C6—Fe168.9 (6)
C5—Fe1—C8152.0 (4)C10—C6—H6125.9
C5—Fe1—C9118.7 (4)Fe1—C7—H7125.9
C5—Fe1—C10108.5 (4)C6—C7—Fe170.1 (5)
C6—Fe1—C2118.8 (4)C6—C7—H7125.6
C6—Fe1—C3151.3 (5)C6—C7—C8108.8 (9)
C6—Fe1—C4167.9 (5)C8—C7—Fe170.0 (4)
C6—Fe1—C739.7 (4)C8—C7—H7125.6
C6—Fe1—C867.2 (4)Fe1—C8—H8126.1
C7—Fe1—C2108.3 (4)C7—C8—Fe170.1 (5)
C7—Fe1—C3118.6 (5)C7—C8—H8126.0
C7—Fe1—C4151.3 (5)C7—C8—C9108.0 (9)
C8—Fe1—C2127.3 (4)C9—C8—Fe169.3 (5)
C8—Fe1—C3108.6 (4)C9—C8—H8126.0
C8—Fe1—C4118.8 (4)Fe1—C9—H9125.9
C8—Fe1—C739.8 (4)C8—C9—Fe170.2 (5)
C9—Fe1—C2165.0 (4)C8—C9—H9126.0
C9—Fe1—C3128.6 (5)C8—C9—C10108.0 (9)
C9—Fe1—C4109.1 (5)C10—C9—Fe169.5 (6)
C9—Fe1—C668.0 (5)C10—C9—H9126.0
C9—Fe1—C767.6 (4)Fe1—C10—H10125.1
C9—Fe1—C840.5 (4)C6—C10—Fe170.2 (6)
C10—Fe1—C2152.8 (4)C6—C10—H10126.5
C10—Fe1—C3166.6 (6)C9—C10—Fe169.8 (6)
C10—Fe1—C4129.3 (5)C9—C10—C6107.0 (9)
C10—Fe1—C640.9 (5)C9—C10—H10126.5
C10—Fe1—C768.0 (5)O11—C11—C1130.2 (13)
C10—Fe1—C868.2 (4)O11—C11—H11114.9
C10—Fe1—C940.7 (5)C1—C11—H11114.9
C12—Fe2—C1468.6 (4)C13—C12—Fe268.7 (5)
C12—Fe2—C1568.4 (4)C13—C12—C22124.6 (9)
C12—Fe2—C1640.8 (4)C16—C12—Fe269.8 (5)
C12—Fe2—C18122.9 (4)C16—C12—C13106.7 (9)
C12—Fe2—C19158.2 (4)C16—C12—C22128.2 (10)
C13—Fe2—C1241.5 (4)C22—C12—Fe2120.6 (7)
C13—Fe2—C1440.0 (5)Fe2—C13—H13124.9
C13—Fe2—C1567.9 (4)C12—C13—Fe269.9 (6)
C13—Fe2—C1668.7 (4)C12—C13—H13125.5
C13—Fe2—C17125.8 (5)C14—C13—Fe271.3 (7)
C13—Fe2—C18108.5 (5)C14—C13—C12109.0 (9)
C13—Fe2—C19122.0 (4)C14—C13—H13125.5
C13—Fe2—C20156.0 (5)Fe2—C14—H14127.4
C13—Fe2—C21162.0 (5)C13—C14—Fe268.6 (6)
C15—Fe2—C1440.4 (4)C13—C14—H14126.1
C16—Fe2—C1468.3 (4)C13—C14—C15107.7 (9)
C16—Fe2—C1540.6 (4)C15—C14—Fe269.4 (6)
C17—Fe2—C12108.6 (4)C15—C14—H14126.1
C17—Fe2—C14161.5 (5)Fe2—C15—H15126.1
C17—Fe2—C15157.2 (5)C14—C15—Fe270.2 (5)
C17—Fe2—C16122.4 (4)C14—C15—H15125.7
C17—Fe2—C1840.7 (4)C14—C15—C16108.7 (9)
C17—Fe2—C1967.5 (4)C16—C15—Fe269.6 (5)
C17—Fe2—C2068.2 (5)C16—C15—H15125.7
C18—Fe2—C14124.2 (5)Fe2—C16—H16126.3
C18—Fe2—C15160.0 (4)C12—C16—Fe269.4 (5)
C18—Fe2—C16158.4 (4)C12—C16—H16126.1
C19—Fe2—C14107.8 (4)C15—C16—Fe269.8 (5)
C19—Fe2—C15123.7 (4)C15—C16—C12107.9 (9)
C19—Fe2—C16159.7 (4)C15—C16—H16126.1
C19—Fe2—C1840.1 (4)Fe2—C17—H17125.9
C20—Fe2—C12160.5 (4)C18—C17—Fe270.0 (6)
C20—Fe2—C14120.8 (5)C18—C17—H17125.9
C20—Fe2—C15106.7 (5)C21—C17—Fe269.8 (7)
C20—Fe2—C16123.3 (4)C21—C17—H17125.9
C20—Fe2—C1868.2 (5)C21—C17—C18108.3 (10)
C20—Fe2—C1940.2 (5)Fe2—C18—H18125.9
C21—Fe2—C12124.3 (5)C17—C18—Fe269.3 (5)
C21—Fe2—C14156.6 (6)C17—C18—H18126.5
C21—Fe2—C15121.5 (5)C19—C18—Fe269.9 (5)
C21—Fe2—C16107.6 (5)C19—C18—C17107.0 (10)
C21—Fe2—C1740.2 (6)C19—C18—H18126.5
C21—Fe2—C1868.1 (5)Fe2—C19—H19126.6
C21—Fe2—C1967.6 (5)C18—C19—Fe270.0 (5)
C21—Fe2—C2040.8 (5)C18—C19—H19125.3
C2—C1—Fe170.5 (5)C18—C19—C20109.4 (10)
C2—C1—C11127.8 (10)C20—C19—Fe269.7 (5)
C5—C1—Fe169.5 (5)C20—C19—H19125.3
C5—C1—C2107.5 (9)Fe2—C20—H20125.6
C5—C1—C11124.2 (11)C19—C20—Fe270.1 (7)
C11—C1—Fe1119.0 (7)C19—C20—H20126.5
Fe1—C2—H2126.8C19—C20—C21106.9 (12)
C1—C2—Fe168.1 (6)C21—C20—Fe269.3 (7)
C1—C2—H2126.5C21—C20—H20126.5
C3—C2—Fe170.2 (6)Fe2—C21—H21125.9
C3—C2—C1106.9 (9)C17—C21—Fe270.0 (7)
C3—C2—H2126.5C17—C21—C20108.4 (11)
Fe1—C3—H3125.6C17—C21—H21125.8
C2—C3—Fe170.4 (6)C20—C21—Fe269.9 (7)
C2—C3—H3125.2C20—C21—H21125.8
C2—C3—C4109.6 (10)O22—C22—C12125.6 (9)
C4—C3—Fe170.4 (7)O22—C22—H22117.2
C4—C3—H3125.2C12—C22—H22117.2
Fe1—C1—C2—C359.7 (7)C7—C6—C10—C91.0 (12)
Fe1—C1—C5—C4−61.5 (7)C7—C8—C9—Fe159.7 (6)
Fe1—C1—C11—O11102.6 (13)C7—C8—C9—C100.3 (11)
Fe1—C2—C3—C459.7 (8)C8—C9—C10—Fe159.9 (7)
Fe1—C3—C4—C557.8 (8)C8—C9—C10—C6−0.8 (12)
Fe1—C4—C5—C160.6 (7)C10—C6—C7—Fe158.7 (8)
Fe1—C6—C7—C8−59.5 (7)C10—C6—C7—C8−0.8 (12)
Fe1—C6—C10—C960.4 (7)C11—C1—C2—Fe1112.2 (10)
Fe1—C7—C8—C9−59.2 (6)C11—C1—C2—C3171.9 (10)
Fe1—C8—C9—C10−59.4 (7)C11—C1—C5—Fe1−111.9 (9)
Fe1—C9—C10—C6−60.7 (7)C11—C1—C5—C4−173.4 (9)
Fe2—C12—C13—C1460.8 (7)C12—C13—C14—Fe2−60.0 (7)
Fe2—C12—C16—C15−59.4 (7)C12—C13—C14—C15−1.4 (11)
Fe2—C12—C22—O22−93.4 (11)C13—C12—C16—Fe259.0 (6)
Fe2—C13—C14—C1558.6 (7)C13—C12—C16—C15−0.4 (11)
Fe2—C14—C15—C1659.2 (7)C13—C12—C22—O22−177.4 (9)
Fe2—C15—C16—C1259.2 (7)C13—C14—C15—Fe2−58.1 (7)
Fe2—C17—C18—C19−60.1 (7)C13—C14—C15—C161.1 (12)
Fe2—C17—C21—C2059.6 (8)C14—C15—C16—Fe2−59.6 (7)
Fe2—C18—C19—C20−58.7 (7)C14—C15—C16—C12−0.4 (11)
Fe2—C19—C20—C21−59.8 (7)C16—C12—C13—Fe2−59.7 (7)
Fe2—C20—C21—C17−59.7 (8)C16—C12—C13—C141.1 (11)
C1—C2—C3—Fe1−58.4 (7)C16—C12—C22—O22−6.0 (16)
C1—C2—C3—C41.3 (12)C17—C18—C19—Fe259.6 (7)
C2—C1—C5—Fe160.6 (6)C17—C18—C19—C201.0 (12)
C2—C1—C5—C4−1.0 (11)C18—C17—C21—Fe2−59.6 (8)
C2—C1—C11—O1115.6 (18)C18—C17—C21—C20−0.1 (12)
C2—C3—C4—Fe1−59.7 (8)C18—C19—C20—Fe258.8 (7)
C2—C3—C4—C5−1.9 (13)C18—C19—C20—C21−1.0 (12)
C3—C4—C5—Fe1−58.8 (8)C19—C20—C21—Fe260.4 (8)
C3—C4—C5—C11.8 (12)C19—C20—C21—C170.7 (12)
C5—C1—C2—Fe1−59.9 (6)C21—C17—C18—Fe259.5 (8)
C5—C1—C2—C3−0.2 (11)C21—C17—C18—C19−0.5 (12)
C5—C1—C11—O11−173.5 (10)C22—C12—C13—Fe2113.2 (9)
C6—C7—C8—Fe159.5 (7)C22—C12—C13—C14174.1 (9)
C6—C7—C8—C90.3 (11)C22—C12—C16—Fe2−113.6 (10)
C7—C6—C10—Fe1−59.5 (8)C22—C12—C16—C15−173.0 (9)
Hydrogen-bond geometry (Å, º) top
Cg1–Cg4 are the centroids of the (C1–C5), (C6–C10), (C12–C16) and (C17–C21) rings, respectively.
D—H···AD—HH···AD···AD—H···A
C3—H3···O22i0.952.603.520 (13)165
C6—H6···O11ii0.952.453.255 (13)142
C7—H7···Cg30.952.913.625 (12)133
C11—H11···Cg4iii0.952.973.907 (12)170
C16—H16···Cg2iv0.953.033.935 (13)159
C18—H18···Cg1v0.952.803.631 (7)146
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+2, y−1/2, −z+1; (iii) x−1, y−1, z; (iv) x, y+1, z; (v) x+1, y, z.
 

Acknowledgements

The authors would like to thank D. B. Cordes for fruitful discussions.

Funding information

TH is grateful to Hacettepe University Scientific Research Project Unit (grant No. 013 D04 602 004).

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Volume 82| Part 4| April 2026| Pages 349-352
https://doi.org/10.1107/S205698902600229X
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