Crystal structure and Hirshfeld surface analysis of 1-(di­methyl­amino­meth­yl)-2-(pyrrolidin-1-ylmeth­yl)ferrocene complexes with zinc(II) bromide and cadmium(II) bromide

Moritz, B.; Mairath, T.; Strohmann, C.

doi:10.1107/S2056989026004688

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ISSN: 2056-9890

Volume 82| Part 6| June 2026| Pages 600-605

https://doi.org/10.1107/S2056989026004688

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Crystal structure and Hirshfeld surface analysis of 1-(dimethylaminomethyl)-2-(pyrrolidin-1-ylmethyl)ferrocene complexes with zinc(II) bromide and cadmium(II) bromide

Beata Moritz,^a Tristan Mairath ^a and Carsten Strohmann ^a ^*

^aTU Dortmund University, Department of Chemistry and Chemical Biology, Inorganic Chemistry, Otto-Hahn-Strasse 6, 44227 Dortmund, Germany
^*Correspondence e-mail: [email protected]

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 23 April 2026; accepted 6 May 2026; online 12 May 2026)

Two transition-metal complexes, rac-dibromido[1-(dimethylaminomethyl)-2-(pyrrolidin-1-ylmethyl)ferrocene]zinc(II), [FeZnBr₂(C₅H₅)(C₁₃H₂₂N₂)] (rac-1), and rac-dibromido[1-(dimethylaminomethyl)-2-(pyrrolidin-1-ylmethyl)ferrocene]cadmium(II), [FeCdBr₂(C₅H₅)(C₁₃H₂₂N₂)] (rac-2), crystallize in the form of yellow blocks and were characterized by single-crystal X-ray diffraction. They were synthesized using rac-1-(dimethylaminomethyl)-2-(pyrrolidin-1-ylmethyl)ferrocene (rac-3) as starting material, which is characterized here for the first time. Both, the zinc center in complex rac-1 and the cadmium center in complex rac-2 exhibit a tetrahedral coordination geometry. Nevertheless, there are some differences in terms of the bond lengths as well as the bond angles. Furthermore, not only the space groups, P2₁/n for rac-1 and P2₁2₁2₁ for rac-2, but also the crystal packings differ from each other, which can be seen in different configurations of the pyrrolidine substituents. To investigate the intermolecular interactions leading to these structural differences, Hirshfeld surface analyses were performed. They showed that H⋯H interactions make the largest contribution to the crystal packing in both structures, with 69.0% and 66.6% for rac-1 and rac-2, respectively.

Keywords: crystal structure; ferrocene derivatives; zinc bromide; cadmium bromide; transition metal complexes; Hirshfeld surface analysis.

CCDC references: 2551916; 2551915

1. Chemical context

Functionalized ferrocenes are widely applied in catalytic transformations. Therefore, suitable methods for the synthesis of different ferrocene derivatives are important (Schaarschmidt & Lang, 2013 ). An example of a suitable starting material for such derivatization is N,N-dimethylaminomethylferrocene. Starting from this compound, it is possible to synthesize 1,2-disubstituted ferrocenes by lithiation and subsequent substitution of the ortho-position, which is preferred due to the DoM effect (Directed ortho Metalation) originating from the amino group (Marr, 1967 ). In the presence of substoichiometric amounts of the chiral auxiliary (R,R)-tetramethyl-1,2-cyclohexanediamine (TMCDA), an enantioselective synthesis with high stereoselectivities up to >99:1 is possible, besides a racemic lithiation (Steffen et al., 2013 ). In this work, a 1,2-disubstituted ferrocene in its racemic form is reported. Compound rac-3 was synthesized by ortho-lithiation using tert-butyllithium and addition of 1-methylidenepyrrolidin-1-ium chloride as an electrophile. The synthesis and characterization of this diamino ferrocene rac-3 is reported here for the first time. It has been shown to be a suitable ligand for the formation of transition-metal complexes.

In addition to ferrocene ligands, other ligands are able to form transition-metal complexes that can be used as catalysts in a variety of synthetically relevant reactions. For example, it has been reported that certain cadmium(II) complexes with oxazoline-based ligands catalyze C—N cross-coupling reactions (Jia et al., 2015 ). In addition, halogen-bonded zinc(II)– and cadmium(II)–arylhydrazone complexes exhibit catalytic activity in cycloaddition reactions of CO₂ with epoxides (Aliyeva et al., 2023 ). Furthermore, diamine zinc complexes can be used as catalysts in lactide polymerization (Eckert et al., 2013 ). In this work, a zinc(II) complex, rac-1, and a cadmium(II) complex, rac-2, could be crystallized, after the reaction of ligand rac-3 with the corresponding bromide salts.

2. Structural commentary

The zinc(II) complex rac-1 crystallizes at room temperature from acetone in the form of yellow blocks in the monoclinic space group P2₁/n. Compound rac-1 exhibits a tetrahedral coordination geometry around the zinc center with two bromide anions and rac-3 as the bidentate ferrocenyl ligand. The molecular structure of rac-1 is illustrated in Fig. 1 (left), and selected bond lengths, bond angles as well as torsion angles are given in Table 1.

Table 1
Bond geometry (Å, °; M = metal center)

Bond lengths	rac-1	rac-2
N1—M	2.050 (2)	2.3148 (10)
N2—M	2.077 (2)	2.3250 (11)
Br1—M	2.3560 (10)	2.5544 (5)
Br2—M	2.3606 (10)	2.5685 (5)

Bond angles	rac-1	rac-2
Br1—M—Br2	113.88 (4)	113.236 (11)
N1—M—N2	110.45 (8)	112.60 (3)
Br1—M—N2	107.20 (7)	107.86 (3)
Br2—M—N1	106.69 (7)	109.79 (2)

Torsion angles	rac-1	rac-2
C3—C4—C13—C9	–171.3 (2)	35.4 (2)
C5—N1—M—Br1	–167.24 (13)	–108.21 (6)
C5—N1—M—Br2	68.03 (14)	127.62 (6)
N1—M—N2—C6	166.39 (17)	108.68 (8)
N1—M—N2—C7	–76.41 (14)	–132.05 (7)
C4—N1—C5—C13	–52.5 (2)	–70.55 (10)
C7—N2—C8—C9	50.0 (2)	70.56 (10)
C1—C2—C3—C4	4.1 (2)	–5.11 (10)
H10—C10—C15—H15	3.2749 (4)	–7.4408 (9)

Figure 1
Molecular structures of rac-1 (left) and rac-2 (right), showing the atom labelling and 50% probability displacement ellipsoids.

The cadmium(II) complex rac-2 crystallizes at room temperature from acetone in the form of yellow blocks in the orthorhombic space group P2₁2₁2₁. Compound rac-2 also exhibits a tetrahedral coordination geometry around the cadmium center with two bromide anions and rac-3 as the bidentate ferrocenyl ligand. The molecular structure of rac-2 is illustrated in Fig. 1 as well (right), and selected bond lengths, bond angles as well as torsion angles are given in Table 1.

The tetrahedral geometry at the metal center, which is present in both complexes, can be identified by the angles around the zinc center [Br1—Zn1—Br2: 113.88 (4)°, N1—Zn1—N2: 110.45 (8)°, Br1—Zn1—N2: 107.20 (7)°, Br2—Zn1—N1: 106.69 (7)°] and the angles around the cadmium center [Br1—Cd1—Br2: 113.236 (11)°, N1—Cd1—N2: 112.60 (3)°, Br1—Cd1—N2: 107.86 (3)°, Br2—Cd1—N1: 109.79 (2)°], which are close to 109°. It is noticeable that the angles between Br1—M—Br2 (M = metal center) and N1—M—N2 are larger than those between Br1—M—N2 and Br2—M—N1. The cyclopentadienyl rings are arranged nearly parallel to each other; however, the structure of complex rac-2 exhibits a slightly greater offset between the two rings [H10—C10—C15—H15: 3.2749 (4)° (rac-1), H10—C10—C15—H15: −7.4408 (9)° (rac-2)].

The bond lengths between the transition metal center and the coordinating domains of the two complexes differ the most. All of these bonds are shorter in complex rac-1 [N1—Zn1: 2.050 (2) Å, N2—Zn1: 2.077 (2) Å, Br1—Zn1: 2.3560 (10) Å, Br2—Zn1: 2.3606 (10) Å] compared to complex rac-2 [N1—Cd1: 2.3148 (10) Å, N2—Cd1: 2.3250 (11) Å, Br1—Cd1: 2.5544 (5) Å, Br2—Cd1: 2.5685 (5) Å]. This observation is consistent with the increasing size of the transition metal from zinc to cadmium.

The main difference between the two complexes presented is the orientation of the functional groups. For example, the pyrrolidine substituent in complex rac-1 is bent slightly downwards [C3—C4—C13—C9: −171.3 (2)°], whereas in complex rac-2 it is bent upwards [C3—C4—C13—C9: 35.4 (2)°]. The bromido ligands are also orientated differently. In the zinc(II) complex, Br1 is positioned vertically above the metal center [C5—N1—Zn1—Br1: −167.24 (13)°], while Br2 is bent back from the ferrocene unit [C5—N1—Zn1—Br2: 68.03 (14)°]. In the cadmium(II) complex, Br1 is orientated less towards the ferrocene unit [C5—N1—Cd1—Br1: −108.21 (6)°], while Br2 is only slightly bent backwards [C5—N1—Cd1—Br2: 127.62 (6)°]. Furthermore, the methyl groups of the dimethylaminomethyl substituent are also orientated differently [N1—Zn1—N2—C6: 166.39 (17)° (rac-1), N1—Zn1—N2—C7: −76.41 (14)° (rac-1), N1—Cd1—N2—C6: 108.68 (8)° (rac-2), N1—Cd1—N2—C7: −132.05 (7)° (rac-2)]. All these observations are consistent with the different arrangements of the nitrogen groups around the metal centers. In the zinc(II) complex rac-1, they are more bent towards the ferrocene unit [C4—N1—C5—C13: −52.5 (2)°, C7—N2—C8—C9: 50.0 (2)°], whereas the nitrogen substituents in the cadmium(II) complex rac-2 are further away from the ferrocene unit and positioned more laterally [C4—N1—C5—C13: −70.55 (10)°, C7—N2—C8—C9: 70.56 (10)°].

3. Supramolecular features

Despite the use of a racemic mixture of the chiral ligand rac-3, rac-1 crystallizes in a centrosymmetric space group, while rac-2 crystallizes in a chiral space group. Therefore, the investigation of the close intermolecular contacts that determine the arrangement of molecules in the crystal packing, is of particular interest. The crystal packing between four molecules of complex rac-1 is shown in Fig. 2. Short intermolecular contacts corresponding to hydrogen bonds can be seen, which originate from the bromido ligands or the carbon atoms of the cyclopentadienyl rings. Furthermore, Fig. 3 shows the crystal packing of complex rac-2, which also exhibits short intermolecular contacts. In addition to hydrogen bonds, intermolecular H⋯H interactions can be observed. These interactions involve the hydrogen atoms of the pyrrolidine substituent of rac-2, which could explain the different configurations of the pyrrolidine rings in both complexes. The main difference between the crystal structures is the formation of parallel layers of compound rac-1, whereas the orientation of the molecules of compound rac-2 seems to be more random.

Figure 2
The molecular packing of rac-1 viewed along the b axis with the unit cell shown as a black outline. Short contacts are shown as dashed blue lines.

Figure 3
The molecular packing of rac-2 viewed along the a axis with the unit cell shown as a black outline. Short contacts are shown as dashed blue lines.

To better understand the intermolecular interactions and to investigate which intermolecular interaction is dominating the packing of rac-1 and rac-2, Hirshfeld surface analyses (Spackman & Jayatilaka, 2009 ) were carried out. The surfaces and the corresponding fingerprint plots (McKinnon et al., 2007 ) were calculated using CrystalExplorer21 (Spackman et al., 2021 ). Fig. 4 illustrates the Hirshfeld surface for the zinc(II) complex rac-1 mapped over d_norm in the range from −0.0606 to 1.6786 arbitrary units. For the cadmium(II) complex rac-2, the surface shown in Fig. 5 was mapped over d_norm in the range from −0.1546 to 1.7781 arbitrary units. The red areas represent the closest contacts. In compound rac-1, especially the Br⋯H interactions are highlighted by red spots. In contrast, for compound rac-2, the hydrogen bonds, that originate not only from the bromido ligands but also from the carbon atoms of the cyclopentadienyl rings, dominate.

Figure 4
Hirshfeld surface analysis showing close contacts, and two-dimensional fingerprint plots for rac-1; (a) all contributions and (b)–(e) contributions between specific interacting atom pairs (blue areas).

Figure 5
Hirshfeld surface analysis showing close contacts, and two-dimensional fingerprint plots for rac-2; (a) all contributions and (b)–(e) contributions between specific interacting atom pairs (blue areas).

The contributions of the respective intermolecular interactions are visualized by the two-dimensional fingerprint plots shown for complex rac-1 in Fig. 6 and for complex rac-2 in Fig. 7. In both crystal structures, the H⋯H interactions can be identified as the most significant interactions with 69.0% for the packing of rac-1 and 66.6% for rac-2. These are followed by the H⋯Br interactions, which contribute 23.3% to the packing of complex rac-1 and 26.3% to the packing of complex rac-2. In addition, C⋯H interactions are also relevant for the respective crystal packing. These contribute to the packing to nearly the same extent, with a percentage of 7.2% (rac-1) and 7.1% (rac-2), respectively. Furthermore, in the crystal packing of complex rac-1, Br⋯Br interactions contribute to the packing with a small percentage of 0.5%. In contrast, the weakest interactions in the packing of complex rac-2 could be identified as those between Cd and H (>0.0%). However, the latter interactions contribute less to the crystal packings of complex rac-1 and rac-2. Based on this analysis, the H⋯H interaction could be identified as the most significant interaction of the crystal packing of both compounds.

4. Database survey

A search of the Cambridge Structural Database (Groom et al., 2016 ; WebCSD February 2026) revealed several structures of similar transition-metal complexes. For example, there are two nickel(II) halide complexes with 1,2-bis(N,N-dimethylaminomethyl)ferrocene as ligand which is very similar to ligand rac-3 used in this work. The nickel center is coordinated by the bidentate ferrocene-based ligand and two chlorides in the first (ZAMNIO; Butler et al., 2026 ) and two bromides in the second solid-state structure (MUCRUA; Butler et al., 2026). Furthermore, there are solid-state structures that are more similar to complexes rac-1 and rac-2 in terms of the transition metal. While the first complex is a zinc(II) bromide complex with a ferrocene terpyridyl ligand (VUDHIN; Wu et al., 2017 ), the second complex contains cadmium(II) as the central metal cation with the same bidentate ligand (OGEYEG; Wu et al., 2017). In the structures with 1,2-bis(N,N-dimethylaminomethyl)ferrocene as ligand, the transition metal adopts a tetrahedral coordination geometry, like at complexes rac-1 and rac-2 at hand.

5. Synthesis and crystallization

For the synthesis of ligand rac-3, N,N-dimethylaminomethylferrocene (243.13 g mol⁻¹, 0.99 mL, ρ = 1.23 g mL⁻¹, 1.22 g, 5.00 mmol, 1.00 eq.) was added to 15 mL of dried diethyl ether at 273 K under inert conditions. After adding tert-butyllithium (64.06 g mol⁻¹, 3.42 mL, c = 1.90 mol L⁻¹ in n-pentane, 416 mg, 6.50 mmol, 1.30 eq.) at 273 K, the mixture was stirred for 10 min at 273 K and then for 30 min at room temperature. Subsequently, the solution was cooled to 193 K and 1-methylidenepyrrolidin-1-ium chloride (119.59 g mol⁻¹, 837 mg, 7.00 mmol, 1.40 eq.) was added. The solution was allowed to warm to room temperature over 4 h. It was then diluted with water and the pH was adjusted with KOH to pH = 14. After phase separation, the aqueous phase was extracted with diethyl ether (3×20mL). The organic phases were dried over MgSO₄ and the solvent was removed under reduced pressure. After purification by column chromatography, ligand rac-3 (326.27 g mol⁻¹, 393 mg, 1.20 mmol, 24%.) was isolated as a brown oil.

To crystallize rac-1, ligand rac-3 (326.27 g mol⁻¹, 10.0 mg, 0.03 mmol, 1.00 eq.) was dissolved in acetone (4 mL). Zinc bromide (225.19 g mol⁻¹, 6.8 mg, 0.03 mmol, 1.00 eq.) was then added. Subsequently, the solvent was slowly evaporated at room temperature. Product rac-1 crystallized in the form of yellow blocks, which were suitable for X-ray diffraction.

To crystallize rac-2, ligand rac-3 (326.27 g mol⁻¹, 10.0 mg, 0.03 mmol, 1.00 eq.) was dissolved in acetone (4 mL). Cadmium bromide (272.22 g mol⁻¹, 8.2 mg, 0.03 mmol, 1.00 eq.) was then added. Subsequently, the solvent was slowly evaporated at room temperature. Product rac-2 crystallized in the form of yellow blocks, which were suitable for X-ray diffraction.

Characterization of the ligand rac-3:

GC/EI-MS [353 K (1 min) – 573 K (32 min) at 30 K min⁻¹] (70 eV, t_R = 15.624 min) m/z (%) = 326 (11) (M⁺), 281 (100) [(M – NMe₂ – H)⁺], 268 (4) [(M – CH₂NMe₂)⁺], 255 (86) [(M – Pyrr – H)⁺], 213 (52) [(M – CH₂Pyrr – 2Me)⁺], 121 (79) (CpFe⁺), 58 (13) (CH₂NMe₂⁺).

¹H-NMR (600 MHz, C₆D₆) δ = 1.57–1.66 (m, 4H; Pyrr-NCH₂CH₂), 2.19 [s, 6H; N(CH₃)₂], 2.43–2.51 (m, 2H; Pyrr-NCH₂CH₂), 2.51–2.59 (m, 2H; Pyrr-NCH₂CH₂), 3.16, 3.40 [AB-system, J_AB = 12.7, 2H; CH₂N(CH₃)₂], 3.32, 3.59 (AB-system, J_AB = 12.8, 2H; CH₂Pyrr-N), 3.93 (s, 5H; C₅H₅), 3.95–3.97 (m, 1H; Cp-CH), 4.19 (s, 1H; Cp-CH), 4.23 (s, 1H; Cp-CH) ppm.

¹³C{¹H}-NMR (151 MHz, C₆D₆) δ = 24.0 (2C; Pyrr-NCH₂CH₂), 45.4 [2C; N(CH₃)₂], 53.8 (1C; CH₂Pyrr-N), 54.4 (2C; Pyrr-NCH₂CH₂), 57.8 [1C; CH₂N(CH₃)₂], 66.8 (1C; Cp-CH), 69.5 (5C; C₅H₅), 70.3 (1C; Cp-CH), 70.6 (1C; Cp-CH), 84.3 (1C; Cp-C_quar), 85.7 (1C; Cp-C_quar) ppm.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. For both compounds, the H atoms were positioned geometrically (C—H = 0.95–0.99 Å) and refined using a riding model, with U_iso(H) = 1.2U_eq(C) for CH₂ and CH hydrogen atoms and U_iso(H) = 1.5U_eq(C) for CH₃ hydrogen atoms. For refinement of complex rac-2, twin law (–1, 0, 0, 0, −1, 0, 0, 0, −1) was applied.

Table 2
Experimental details

	rac-1	rac-2
Crystal data
Chemical formula	[FeZnBr₂(C₅H₅)(C₁₃H₂₂N₂)]	[FeCdBr₂(C₅H₅)(C₁₃H₂₂N₂)]
M_r	551.47	598.48
Crystal system, space group	Monoclinic, P2₁/n	Orthorhombic, P2₁2₁2₁
Temperature (K)	100	100
a, b, c (Å)	13.5397 (11), 10.4169 (9), 15.3223 (14)	9.804 (2), 10.502 (3), 20.326 (5)
α, β, γ (°)	90, 112.846 (4), 90	90, 90, 90
V (Å³)	1991.6 (3)	2092.9 (8)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	5.96	5.54
Crystal size (mm)	0.61 × 0.33 × 0.18	0.17 × 0.15 × 0.15

Data collection
Diffractometer	Bruker D8 VENTURE area detector	Bruker D8 VENTURE area detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )	Multi-scan (SADABS; Krause et al., 2015)
T_min, T_max	0.196, 0.563	0.459, 0.568
No. of measured, independent and observed [I > 2σ(I)] reflections	144623, 4425, 4276	291242, 11159, 10771
R_int	0.063	0.057
(sin θ/λ)_max (Å⁻¹)	0.643	0.861

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.069, 1.04	0.015, 0.032, 1.04
No. of reflections	4425	11159
No. of parameters	294	320
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.22, −0.48	0.64, −0.42
Absolute structure	–	Hooft et al. (2010 )
Absolute structure parameter	–	−0.0058 (13)
Computer programs: APEX6 and SAINT (Bruker, 2016 ), SHELXT (Sheldrick, 2015 ), OLEX2.refine (Bourhis et al., 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC references: 2551916; 2551915

Crystal structure: contains datablocks rac-1, rac-2, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989026004688/tx2110sup1.cif

checkCIF report

Computing details top

rac-Dibromido[1-(dimethylaminomethyl)-2-(pyrrolidin-1-ylmethyl)\ ferrocene]zinc(II) (rac-1) top

Crystal data top

[FeZnBr₂(C₅H₅)(C₁₃H₂₂N₂)]	F(000) = 1097.663
M_r = 551.47	D_x = 1.839 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.5397 (11) Å	Cell parameters from 9845 reflections
b = 10.4169 (9) Å	θ = 2.4–29.6°
c = 15.3223 (14) Å	µ = 5.96 mm⁻¹
β = 112.846 (4)°	T = 100 K
V = 1991.6 (3) Å³	Block, clear yellow
Z = 4	0.61 × 0.33 × 0.18 mm

Data collection top

Bruker D8 VENTURE area detector diffractometer	4425 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	4276 reflections with I > 2σ(I)
HELIOS mirror optics monochromator	R_int = 0.063
Detector resolution: 10.4167 pixels mm^-1	θ_max = 27.2°, θ_min = 2.6°
ω and φ scans	h = −17→17
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −13→13
T_min = 0.196, T_max = 0.563	l = −19→19
144623 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	42 constraints
R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.069	w = 1/[σ²(F_o²) + (0.0291P)² + 4.1878P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = −0.0002
4425 reflections	Δρ_max = 1.22 e Å⁻³
294 parameters	Δρ_min = −0.48 e Å⁻³

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

	x	y	z	U_iso*/U_eq
Zn1	0.83060 (6)	0.55352 (8)	0.61828 (5)	0.0234 (3)
Br1	0.82659 (6)	0.56794 (11)	0.77031 (5)	0.0438 (4)
Br2	1.00453 (6)	0.56586 (9)	0.61791 (6)	0.0435 (3)
Fe1	0.60674 (3)	0.48115 (3)	0.25968 (2)	0.01804 (10)
N2	0.76792 (15)	0.3755 (2)	0.56325 (14)	0.0208 (4)
N1	0.74283 (16)	0.6978 (2)	0.53186 (13)	0.0196 (4)
C9	0.65123 (18)	0.4361 (2)	0.39863 (16)	0.0185 (5)
C13	0.64094 (18)	0.5724 (2)	0.38531 (16)	0.0185 (5)
C7	0.6694 (2)	0.3467 (3)	0.57945 (18)	0.0249 (5)
H7a	0.6865 (4)	0.342 (2)	0.64767 (18)	0.0374 (8)*
H7b	0.6164 (6)	0.4145 (11)	0.5512 (13)	0.0374 (8)*
H7c	0.6401 (9)	0.2641 (10)	0.5502 (13)	0.0374 (8)*
C5	0.72546 (19)	0.6706 (2)	0.43034 (16)	0.0203 (5)
H5a	0.70508 (19)	0.7513 (2)	0.39354 (16)	0.0244 (6)*
H5b	0.79367 (19)	0.6405 (2)	0.42786 (16)	0.0244 (6)*
C14	0.7193 (2)	0.4056 (3)	0.21604 (18)	0.0254 (5)
H14	0.7801 (2)	0.3565 (3)	0.25353 (18)	0.0305 (6)*
C8	0.74846 (19)	0.3637 (3)	0.46043 (16)	0.0214 (5)
H8a	0.81171 (19)	0.3966 (3)	0.45018 (16)	0.0257 (6)*
H8b	0.73959 (19)	0.2719 (3)	0.44222 (16)	0.0257 (6)*
C15	0.61545 (19)	0.3561 (3)	0.15997 (17)	0.0237 (5)
H15	0.59481 (19)	0.2684 (3)	0.15340 (17)	0.0285 (6)*
C12	0.53302 (19)	0.5987 (3)	0.32237 (16)	0.0229 (5)
H12	0.50374 (19)	0.6813 (3)	0.30116 (16)	0.0275 (6)*
C17	0.6101 (2)	0.5768 (3)	0.14389 (18)	0.0273 (5)
H17	0.5854 (2)	0.6616 (3)	0.12479 (18)	0.0327 (7)*
C16	0.5486 (2)	0.4624 (3)	0.11578 (16)	0.0238 (5)
H16	0.4752 (2)	0.4576 (3)	0.07444 (16)	0.0285 (6)*
C11	0.47712 (19)	0.4803 (3)	0.29699 (17)	0.0233 (5)
H11	0.40414 (19)	0.4699 (3)	0.25576 (17)	0.0280 (6)*
C4	0.6404 (2)	0.7302 (3)	0.54268 (17)	0.0237 (5)
H4a	0.5833 (2)	0.6685 (3)	0.50716 (17)	0.0284 (6)*
H4b	0.6506 (2)	0.7280 (3)	0.61022 (17)	0.0284 (6)*
C10	0.54923 (19)	0.3805 (3)	0.34390 (16)	0.0224 (5)
H10	0.53264 (19)	0.2915 (3)	0.33973 (16)	0.0269 (6)*
C18	0.7154 (2)	0.5411 (3)	0.20580 (18)	0.0276 (6)
H18	0.7735 (2)	0.5984 (3)	0.23537 (18)	0.0331 (7)*
C1	0.8031 (2)	0.8221 (3)	0.56020 (19)	0.0313 (6)
H1a	0.8370 (2)	0.8293 (3)	0.63004 (19)	0.0376 (7)*
H1b	0.8597 (2)	0.8273 (3)	0.53449 (19)	0.0376 (7)*
C6	0.8510 (2)	0.2803 (3)	0.6167 (2)	0.0337 (6)
H6a	0.9164 (7)	0.2960 (14)	0.6054 (13)	0.0505 (9)*
H6b	0.8668 (14)	0.2885 (15)	0.6846 (3)	0.0505 (9)*
H6c	0.8247 (8)	0.1935 (3)	0.5956 (12)	0.0505 (9)*
C2	0.7211 (3)	0.9280 (3)	0.5192 (2)	0.0430 (8)
H2a	0.7355 (3)	1.0007 (3)	0.5640 (2)	0.0516 (9)*
H2b	0.7225 (3)	0.9598 (3)	0.4588 (2)	0.0516 (9)*
C3	0.6111 (3)	0.8649 (3)	0.5027 (2)	0.0388 (7)
H3a	0.5648 (3)	0.8621 (3)	0.4344 (2)	0.0466 (8)*
H3b	0.5735 (3)	0.9126 (3)	0.5366 (2)	0.0466 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0120 (5)	0.0434 (7)	0.0148 (5)	−0.0036 (4)	0.0050 (4)	−0.0041 (4)
Br1	0.0268 (5)	0.0904 (11)	0.0142 (4)	−0.0048 (5)	0.0079 (4)	−0.0062 (5)
Br2	0.0135 (4)	0.0710 (8)	0.0490 (6)	−0.0114 (4)	0.0152 (4)	−0.0205 (5)
Fe1	0.01387 (16)	0.0287 (2)	0.01229 (16)	−0.00098 (13)	0.00587 (12)	−0.00400 (13)
N2	0.0151 (9)	0.0270 (11)	0.0188 (9)	0.0024 (8)	0.0049 (8)	0.0032 (8)
N1	0.0183 (9)	0.0274 (11)	0.0140 (9)	−0.0064 (8)	0.0074 (7)	−0.0046 (8)
C9	0.0136 (10)	0.0290 (12)	0.0138 (10)	−0.0025 (9)	0.0064 (8)	−0.0034 (9)
C13	0.0158 (10)	0.0298 (13)	0.0114 (10)	−0.0004 (9)	0.0068 (8)	−0.0020 (9)
C7	0.0212 (12)	0.0330 (14)	0.0220 (12)	−0.0034 (10)	0.0099 (9)	0.0057 (10)
C5	0.0232 (11)	0.0264 (12)	0.0136 (10)	−0.0041 (9)	0.0097 (9)	−0.0014 (9)
C14	0.0175 (11)	0.0417 (15)	0.0188 (11)	0.0000 (10)	0.0092 (9)	−0.0075 (10)
C8	0.0176 (11)	0.0281 (12)	0.0187 (11)	0.0008 (9)	0.0072 (9)	−0.0029 (9)
C15	0.0190 (11)	0.0358 (14)	0.0182 (11)	−0.0023 (10)	0.0092 (9)	−0.0095 (10)
C12	0.0182 (11)	0.0364 (14)	0.0150 (10)	0.0049 (10)	0.0073 (9)	−0.0021 (10)
C17	0.0312 (14)	0.0358 (15)	0.0184 (12)	−0.0006 (11)	0.0136 (10)	−0.0013 (10)
C16	0.0219 (12)	0.0390 (14)	0.0104 (10)	−0.0012 (10)	0.0061 (9)	−0.0044 (10)
C11	0.0144 (10)	0.0398 (15)	0.0153 (11)	−0.0013 (10)	0.0051 (9)	−0.0054 (10)
C4	0.0220 (11)	0.0320 (13)	0.0195 (11)	0.0016 (10)	0.0106 (9)	−0.0045 (10)
C10	0.0169 (11)	0.0356 (14)	0.0164 (10)	−0.0058 (10)	0.0085 (9)	−0.0038 (10)
C18	0.0238 (12)	0.0428 (15)	0.0217 (12)	−0.0074 (11)	0.0148 (10)	−0.0075 (11)
C1	0.0377 (15)	0.0310 (14)	0.0259 (13)	−0.0153 (12)	0.0129 (11)	−0.0090 (11)
C6	0.0284 (13)	0.0337 (15)	0.0322 (14)	0.0105 (12)	0.0044 (11)	0.0059 (12)
C2	0.069 (2)	0.0286 (15)	0.0341 (16)	−0.0047 (15)	0.0229 (16)	−0.0047 (12)
C3	0.0482 (18)	0.0350 (16)	0.0287 (14)	0.0115 (14)	0.0101 (13)	−0.0040 (12)

Geometric parameters (Å, º) top

Zn1—Br1	2.3560 (10)	C14—C15	1.429 (3)
Zn1—Br2	2.3606 (10)	C14—C18	1.418 (4)
Zn1—N2	2.077 (2)	C8—H8a	0.9900
Zn1—N1	2.050 (2)	C8—H8b	0.9900
Fe1—C9	2.030 (2)	C15—H15	0.9500
Fe1—C13	2.033 (2)	C15—C16	1.423 (4)
Fe1—C14	2.044 (2)	C12—H12	0.9500
Fe1—C15	2.045 (2)	C12—C11	1.420 (4)
Fe1—C12	2.040 (2)	C17—H17	0.9500
Fe1—C17	2.051 (3)	C17—C16	1.422 (4)
Fe1—C16	2.042 (2)	C17—C18	1.422 (4)
Fe1—C11	2.046 (2)	C16—H16	0.9500
Fe1—C10	2.038 (2)	C11—H11	0.9500
Fe1—C18	2.045 (3)	C11—C10	1.417 (4)
N2—C7	1.479 (3)	C4—H4a	0.9900
N2—C8	1.498 (3)	C4—H4b	0.9900
N2—C6	1.485 (3)	C4—C3	1.521 (4)
N1—C5	1.507 (3)	C10—H10	0.9500
N1—C4	1.498 (3)	C18—H18	0.9500
N1—C1	1.502 (3)	C1—H1a	0.9900
C9—C13	1.434 (3)	C1—H1b	0.9900
C9—C8	1.494 (3)	C1—C2	1.517 (5)
C9—C10	1.431 (3)	C6—H6a	0.9800
C13—C5	1.489 (3)	C6—H6b	0.9800
C13—C12	1.430 (3)	C6—H6c	0.9800
C7—H7a	0.9800	C2—H2a	0.9900
C7—H7b	0.9800	C2—H2b	0.9900
C7—H7c	0.9800	C2—C3	1.556 (5)
C5—H5a	0.9900	C3—H3a	0.9900
C5—H5b	0.9900	C3—H3b	0.9900
C14—H14	0.9500

Br2—Zn1—Br1	113.88 (4)	H5b—C5—H5a	107.8
N2—Zn1—Br1	107.20 (7)	H14—C14—Fe1	126.20 (8)
N2—Zn1—Br2	107.36 (7)	C15—C14—Fe1	69.60 (14)
N1—Zn1—Br1	111.21 (7)	C15—C14—H14	126.05 (17)
N1—Zn1—Br2	106.69 (7)	C18—C14—Fe1	69.72 (15)
N1—Zn1—N2	110.45 (8)	C18—C14—H14	126.05 (15)
C13—Fe1—C9	41.34 (10)	C18—C14—C15	107.9 (2)
C14—Fe1—C9	107.39 (10)	C9—C8—N2	112.15 (19)
C14—Fe1—C13	124.41 (10)	H8a—C8—N2	109.18 (12)
C15—Fe1—C9	123.82 (10)	H8a—C8—C9	109.18 (13)
C15—Fe1—C13	161.29 (10)	H8b—C8—N2	109.18 (13)
C15—Fe1—C14	40.91 (9)	H8b—C8—C9	109.18 (13)
C12—Fe1—C9	69.22 (10)	H8b—C8—H8a	107.9
C12—Fe1—C13	41.12 (9)	C14—C15—Fe1	69.50 (14)
C12—Fe1—C14	161.43 (11)	H15—C15—Fe1	126.31 (8)
C12—Fe1—C15	156.11 (10)	H15—C15—C14	126.25 (17)
C17—Fe1—C9	157.30 (10)	C16—C15—Fe1	69.51 (14)
C17—Fe1—C13	121.23 (11)	C16—C15—C14	107.5 (2)
C17—Fe1—C14	68.53 (11)	C16—C15—H15	126.25 (14)
C17—Fe1—C15	68.66 (11)	C13—C12—Fe1	69.15 (13)
C17—Fe1—C12	107.15 (11)	H12—C12—Fe1	126.72 (7)
C16—Fe1—C9	160.59 (11)	H12—C12—C13	125.83 (15)
C16—Fe1—C13	156.60 (11)	C11—C12—Fe1	69.87 (14)
C16—Fe1—C14	68.51 (10)	C11—C12—C13	108.3 (2)
C16—Fe1—C15	40.75 (11)	C11—C12—H12	125.83 (14)
C16—Fe1—C12	120.78 (10)	H17—C17—Fe1	126.50 (8)
C16—Fe1—C17	40.66 (11)	C16—C17—Fe1	69.35 (14)
C11—Fe1—C9	69.11 (9)	C16—C17—H17	126.26 (16)
C11—Fe1—C13	69.03 (9)	C18—C17—Fe1	69.45 (15)
C11—Fe1—C14	156.77 (11)	C18—C17—H17	126.26 (17)
C11—Fe1—C15	120.69 (10)	C18—C17—C16	107.5 (2)
C11—Fe1—C12	40.67 (11)	C15—C16—Fe1	69.74 (13)
C11—Fe1—C17	123.61 (11)	C17—C16—Fe1	69.99 (14)
C11—Fe1—C16	106.76 (10)	C17—C16—C15	108.6 (2)
C10—Fe1—C9	41.19 (9)	H16—C16—Fe1	126.13 (7)
C10—Fe1—C13	69.12 (10)	H16—C16—C15	125.72 (14)
C10—Fe1—C14	121.72 (11)	H16—C16—C17	125.72 (16)
C10—Fe1—C15	107.00 (11)	C12—C11—Fe1	69.45 (14)
C10—Fe1—C12	68.51 (11)	H11—C11—Fe1	126.75 (7)
C10—Fe1—C17	160.12 (10)	H11—C11—C12	125.98 (14)
C10—Fe1—C16	123.54 (10)	C10—C11—Fe1	69.38 (13)
C10—Fe1—C11	40.60 (10)	C10—C11—C12	108.0 (2)
C18—Fe1—C9	121.81 (10)	C10—C11—H11	125.98 (14)
C18—Fe1—C13	107.73 (10)	H4a—C4—N1	110.59 (12)
C18—Fe1—C14	40.60 (12)	H4b—C4—N1	110.59 (12)
C18—Fe1—C15	68.51 (11)	H4b—C4—H4a	108.7
C18—Fe1—C12	124.55 (11)	C3—C4—N1	105.7 (2)
C18—Fe1—C17	40.62 (11)	C3—C4—H4a	110.59 (15)
C18—Fe1—C16	68.25 (10)	C3—C4—H4b	110.59 (14)
C18—Fe1—C11	160.74 (12)	C9—C10—Fe1	69.11 (13)
C18—Fe1—C10	157.65 (11)	C11—C10—Fe1	70.02 (14)
C7—N2—Zn1	111.47 (16)	C11—C10—C9	108.6 (2)
C8—N2—Zn1	112.20 (15)	H10—C10—Fe1	126.73 (7)
C8—N2—C7	110.97 (18)	H10—C10—C9	125.72 (15)
C6—N2—Zn1	105.65 (16)	H10—C10—C11	125.72 (14)
C6—N2—C7	108.1 (2)	C14—C18—Fe1	69.68 (15)
C6—N2—C8	108.2 (2)	C17—C18—Fe1	69.93 (15)
C5—N1—Zn1	110.35 (15)	C17—C18—C14	108.6 (2)
C4—N1—Zn1	115.04 (15)	H18—C18—Fe1	126.25 (7)
C4—N1—C5	112.12 (18)	H18—C18—C14	125.72 (15)
C1—N1—Zn1	109.37 (16)	H18—C18—C17	125.72 (17)
C1—N1—C5	108.08 (19)	H1a—C1—N1	110.49 (13)
C1—N1—C4	101.3 (2)	H1b—C1—N1	110.49 (13)
C13—C9—Fe1	69.44 (13)	H1b—C1—H1a	108.7
C8—C9—Fe1	127.69 (16)	C2—C1—N1	106.2 (2)
C8—C9—C13	127.1 (2)	C2—C1—H1a	110.49 (16)
C10—C9—Fe1	69.70 (13)	C2—C1—H1b	110.49 (17)
C10—C9—C13	107.4 (2)	H6a—C6—N2	109.5
C10—C9—C8	125.4 (2)	H6b—C6—N2	109.5
C9—C13—Fe1	69.22 (13)	H6b—C6—H6a	109.5
C5—C13—Fe1	127.69 (16)	H6c—C6—N2	109.5
C5—C13—C9	126.8 (2)	H6c—C6—H6a	109.5
C12—C13—Fe1	69.74 (13)	H6c—C6—H6b	109.5
C12—C13—C9	107.6 (2)	H2a—C2—C1	110.72 (16)
C12—C13—C5	125.5 (2)	H2b—C2—C1	110.72 (17)
H7a—C7—N2	109.5	H2b—C2—H2a	108.8
H7b—C7—N2	109.5	C3—C2—C1	105.1 (2)
H7b—C7—H7a	109.5	C3—C2—H2a	110.72 (16)
H7c—C7—N2	109.5	C3—C2—H2b	110.72 (17)
H7c—C7—H7a	109.5	C2—C3—C4	103.9 (2)
H7c—C7—H7b	109.5	H3a—C3—C4	110.97 (15)
C13—C5—N1	113.04 (18)	H3a—C3—C2	110.97 (17)
H5a—C5—N1	108.98 (13)	H3b—C3—C4	110.97 (15)
H5a—C5—C13	108.98 (13)	H3b—C3—C2	110.97 (16)
H5b—C5—N1	108.98 (12)	H3b—C3—H3a	109.0
H5b—C5—C13	108.98 (13)

Zn1—N2—C8—C9	−75.46 (16)	N2—C8—C9—C13	74.9 (2)
Zn1—N1—C5—C13	77.16 (16)	N2—C8—C9—C10	−102.8 (2)
Zn1—N1—C4—C3	159.53 (18)	N1—C5—C13—C9	−77.2 (2)
Zn1—N1—C1—C2	−160.76 (19)	N1—C5—C13—C12	100.9 (2)
Fe1—C9—C13—C5	−122.20 (13)	N1—C4—C3—C2	−28.5 (2)
Fe1—C9—C13—C12	59.38 (14)	N1—C1—C2—C3	21.6 (2)
Fe1—C9—C8—N2	166.6 (2)	C9—C13—C12—C11	0.0 (2)
Fe1—C9—C10—C11	−59.07 (15)	C9—C8—N2—C7	50.0 (2)
Fe1—C13—C9—C8	122.34 (13)	C9—C8—N2—C6	168.4 (2)
Fe1—C13—C9—C10	−59.60 (14)	C9—C10—C11—C12	−0.4 (2)
Fe1—C13—C5—N1	−168.3 (2)	C13—C9—C10—C11	0.4 (2)
Fe1—C13—C12—C11	59.06 (15)	C13—C5—N1—C4	−52.5 (2)
Fe1—C14—C15—C16	59.36 (15)	C13—C5—N1—C1	−163.3 (2)
Fe1—C14—C18—C17	−59.31 (16)	C13—C12—C11—C10	0.2 (2)
Fe1—C15—C14—C18	−59.43 (16)	C5—N1—C4—C3	−73.3 (2)
Fe1—C15—C16—C17	59.42 (15)	C5—N1—C1—C2	79.1 (2)
Fe1—C12—C13—C9	−59.06 (14)	C5—C13—C9—C8	0.1 (3)
Fe1—C12—C13—C5	122.49 (13)	C5—C13—C9—C10	178.2 (2)
Fe1—C12—C11—C10	58.83 (15)	C5—C13—C12—C11	−178.4 (2)
Fe1—C17—C16—C15	−59.26 (15)	C14—C15—C16—C17	0.1 (2)
Fe1—C17—C18—C14	59.15 (15)	C14—C18—C17—C16	0.0 (2)
Fe1—C16—C15—C14	−59.35 (15)	C8—C9—C13—C12	−178.3 (2)
Fe1—C16—C17—C18	59.21 (16)	C8—C9—C10—C11	178.5 (2)
Fe1—C11—C12—C13	−58.61 (14)	C15—C14—C18—C17	0.0 (2)
Fe1—C11—C10—C9	58.51 (14)	C15—C16—C17—C18	−0.1 (2)
Fe1—C10—C9—C13	59.44 (14)	C12—C13—C9—C10	−0.2 (2)
Fe1—C10—C9—C8	−122.47 (13)	C16—C15—C14—C18	−0.1 (2)
Fe1—C10—C11—C12	−58.88 (15)	C4—N1—C1—C2	−38.9 (2)
Fe1—C18—C14—C15	59.35 (15)	C4—C3—C2—C1	4.1 (2)
Fe1—C18—C17—C16	−59.15 (15)	C1—N1—C4—C3	41.7 (2)

rac-Dibromido[1-(dimethylaminomethyl)-2-(pyrrolidin-1-ylmethyl)\ ferrocene]cadmium(II) (rac-2) top

Crystal data top

[FeCdBr₂(C₅H₅)(C₁₃H₂₂N₂)]	D_x = 1.899 Mg m⁻³
M_r = 598.48	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 9365 reflections
a = 9.804 (2) Å	θ = 2.2–37.8°
b = 10.502 (3) Å	µ = 5.54 mm⁻¹
c = 20.326 (5) Å	T = 100 K
V = 2092.9 (8) Å³	Block, clear yellow
Z = 4	0.17 × 0.15 × 0.15 mm
F(000) = 1165.116

Data collection top

Bruker D8 VENTURE area detector diffractometer	11159 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	10771 reflections with I > 2σ(I)
HELIOS mirror optics monochromator	R_int = 0.057
Detector resolution: 10.4167 pixels mm^-1	θ_max = 37.7°, θ_min = 2.0°
ω and φ scans	h = −16→16
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −18→18
T_min = 0.459, T_max = 0.568	l = −34→34
291242 measured reflections

Refinement top

Refinement on F²	42 constraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.015	w = 1/[σ²(F_o²) + (0.0089P)² + 0.7418P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.032	(Δ/σ)_max = 0.0001
S = 1.04	Δρ_max = 0.64 e Å⁻³
11159 reflections	Δρ_min = −0.41 e Å⁻³
320 parameters	Absolute structure: Hooft et al. (2010)
0 restraints	Absolute structure parameter: −0.0058 (13)

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

	x	y	z	U_iso*/U_eq
Cd1	0.254301 (19)	0.188601 (16)	0.677351 (9)	0.01446 (5)
Br2	0.33680 (3)	0.02257 (3)	0.761163 (14)	0.02191 (7)
Br1	0.05181 (3)	0.11252 (3)	0.608742 (15)	0.02481 (8)
Fe1	0.32868 (4)	0.62236 (3)	0.567501 (18)	0.01373 (8)
N1	0.19181 (9)	0.37363 (9)	0.73139 (4)	0.01347 (15)
C12	0.14120 (11)	0.55061 (10)	0.59185 (6)	0.01462 (17)
H12	0.06653 (11)	0.59599 (10)	0.61021 (6)	0.0175 (2)*
N2	0.43788 (10)	0.21868 (9)	0.60664 (5)	0.01630 (16)
C17	0.32688 (13)	0.81605 (11)	0.58190 (6)	0.0209 (2)
H17	0.25098 (13)	0.86632 (11)	0.59493 (6)	0.0250 (2)*
C13	0.24755 (12)	0.48882 (9)	0.62818 (5)	0.01270 (14)
C9	0.33922 (11)	0.43087 (9)	0.58130 (5)	0.01270 (16)
C10	0.28778 (11)	0.45821 (10)	0.51653 (5)	0.01441 (17)
H10	0.32768 (11)	0.43149 (10)	0.47624 (5)	0.0173 (2)*
C5	0.26299 (11)	0.48505 (10)	0.70149 (5)	0.01409 (16)
H5a	0.22548 (11)	0.56447 (10)	0.72049 (5)	0.01691 (19)*
H5b	0.36117 (11)	0.48108 (10)	0.71269 (5)	0.01691 (19)*
C11	0.16671 (11)	0.53225 (10)	0.52315 (5)	0.01581 (17)
H11	0.11239 (11)	0.56391 (10)	0.48808 (5)	0.0190 (2)*
C14	0.52060 (12)	0.69060 (12)	0.58564 (6)	0.01874 (19)
H14	0.59606 (12)	0.64294 (12)	0.60155 (6)	0.0225 (2)*
C16	0.36489 (13)	0.78615 (11)	0.51582 (6)	0.0194 (2)
H16	0.31870 (13)	0.81318 (11)	0.47718 (6)	0.0233 (2)*
C15	0.48462 (12)	0.70841 (11)	0.51798 (6)	0.0185 (2)
H15	0.53185 (12)	0.67462 (11)	0.48110 (6)	0.0222 (2)*
C2	0.10371 (14)	0.28455 (13)	0.83139 (7)	0.0246 (2)
H2a	0.13527 (14)	0.19579 (13)	0.83746 (7)	0.0295 (3)*
H2b	0.07126 (14)	0.31781 (13)	0.87419 (7)	0.0295 (3)*
C8	0.46610 (10)	0.35796 (10)	0.59686 (5)	0.01469 (17)
H8a	0.50789 (10)	0.39309 (10)	0.63731 (5)	0.0176 (2)*
H8b	0.53222 (10)	0.36858 (10)	0.56046 (5)	0.0176 (2)*
C18	0.42328 (14)	0.75695 (12)	0.62495 (6)	0.0208 (2)
H18	0.42263 (14)	0.76115 (12)	0.67163 (6)	0.0250 (3)*
C4	0.03991 (11)	0.38733 (11)	0.72830 (6)	0.01767 (19)
H4a	0.01146 (11)	0.47487 (11)	0.74005 (6)	0.0212 (2)*
H4b	0.00520 (11)	0.36676 (11)	0.68381 (6)	0.0212 (2)*
C1	0.21845 (12)	0.36794 (12)	0.80395 (6)	0.0189 (2)
H1a	0.30869 (12)	0.32948 (12)	0.81302 (6)	0.0227 (2)*
H1b	0.21557 (12)	0.45416 (12)	0.82359 (6)	0.0227 (2)*
C7	0.40243 (14)	0.15941 (11)	0.54247 (6)	0.0217 (2)
H7a	0.3866 (12)	0.0681 (2)	0.54872 (12)	0.0326 (3)*
H7b	0.3196 (7)	0.1992 (8)	0.5250 (3)	0.0326 (3)*
H7c	0.4777 (5)	0.1718 (10)	0.51141 (19)	0.0326 (3)*
C3	−0.01109 (13)	0.29116 (12)	0.77897 (7)	0.0234 (2)
H3a	−0.02575 (13)	0.20680 (12)	0.75842 (7)	0.0281 (3)*
H3b	−0.09780 (13)	0.32010 (12)	0.79896 (7)	0.0281 (3)*
C6	0.56305 (14)	0.15719 (14)	0.63277 (7)	0.0258 (3)
H6a	0.5873 (7)	0.1960 (8)	0.6750 (3)	0.0387 (4)*
H6b	0.5463 (4)	0.0660 (3)	0.6390 (6)	0.0387 (4)*
H6c	0.6381 (4)	0.1690 (10)	0.6015 (3)	0.0387 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01563 (9)	0.01182 (8)	0.01593 (9)	0.00027 (8)	−0.00165 (8)	0.00051 (7)
Br2	0.02612 (16)	0.01943 (14)	0.02019 (14)	0.00332 (12)	−0.00653 (12)	0.00448 (12)
Br1	0.02324 (15)	0.02825 (17)	0.02294 (15)	−0.00560 (13)	−0.00902 (12)	−0.00041 (13)
Fe1	0.01543 (18)	0.01014 (17)	0.01563 (18)	−0.00174 (15)	0.00029 (15)	0.00102 (14)
N1	0.0142 (4)	0.0126 (3)	0.0137 (4)	0.0002 (3)	0.0019 (3)	0.0017 (3)
C12	0.0126 (4)	0.0116 (4)	0.0197 (5)	0.0009 (3)	0.0010 (3)	0.0007 (3)
N2	0.0166 (4)	0.0119 (4)	0.0204 (4)	0.0045 (3)	0.0022 (3)	0.0014 (3)
C17	0.0247 (5)	0.0105 (4)	0.0275 (5)	−0.0027 (4)	0.0031 (4)	−0.0010 (4)
C13	0.0133 (3)	0.0095 (3)	0.0153 (4)	−0.0001 (4)	0.0021 (4)	0.0007 (3)
C9	0.0135 (4)	0.0095 (4)	0.0150 (4)	0.0000 (3)	0.0012 (3)	−0.0002 (3)
C10	0.0158 (4)	0.0123 (4)	0.0151 (4)	−0.0002 (3)	−0.0001 (3)	−0.0015 (3)
C5	0.0152 (4)	0.0118 (4)	0.0153 (4)	−0.0017 (3)	0.0016 (3)	−0.0001 (3)
C11	0.0149 (4)	0.0137 (4)	0.0188 (4)	−0.0001 (4)	−0.0033 (4)	−0.0004 (3)
C14	0.0177 (4)	0.0181 (4)	0.0204 (5)	−0.0057 (4)	−0.0027 (3)	0.0033 (4)
C16	0.0213 (5)	0.0142 (4)	0.0227 (5)	−0.0029 (4)	−0.0008 (4)	0.0062 (4)
C15	0.0173 (4)	0.0194 (5)	0.0189 (5)	−0.0045 (4)	0.0017 (4)	0.0042 (4)
C2	0.0302 (6)	0.0214 (5)	0.0222 (6)	0.0017 (4)	0.0097 (5)	0.0062 (4)
C8	0.0121 (4)	0.0138 (4)	0.0182 (4)	0.0012 (3)	0.0012 (3)	0.0001 (3)
C18	0.0267 (6)	0.0175 (5)	0.0183 (5)	−0.0086 (4)	−0.0008 (4)	−0.0024 (4)
C4	0.0135 (4)	0.0152 (4)	0.0243 (5)	0.0004 (3)	0.0045 (4)	0.0017 (4)
C1	0.0240 (5)	0.0195 (5)	0.0132 (4)	0.0003 (4)	0.0023 (3)	0.0012 (4)
C7	0.0297 (6)	0.0136 (4)	0.0219 (5)	0.0006 (4)	0.0053 (4)	−0.0037 (4)
C3	0.0211 (5)	0.0200 (5)	0.0292 (6)	−0.0028 (4)	0.0106 (4)	0.0047 (4)
C6	0.0209 (5)	0.0250 (6)	0.0316 (6)	0.0106 (4)	0.0040 (5)	0.0084 (5)

Geometric parameters (Å, º) top

Cd1—Br2	2.5685 (5)	C10—C11	1.4254 (16)
Cd1—Br1	2.5544 (5)	C5—H5a	0.9900
Cd1—N1	2.3148 (10)	C5—H5b	0.9900
Cd1—N2	2.3250 (11)	C11—H11	0.9500
Fe1—C12	2.0473 (12)	C14—H14	0.9500
Fe1—C17	2.0553 (13)	C14—C15	1.4320 (17)
Fe1—C13	2.0299 (10)	C14—C18	1.4264 (19)
Fe1—C9	2.0332 (11)	C16—H16	0.9500
Fe1—C10	2.0508 (12)	C16—C15	1.4305 (17)
Fe1—C11	2.0566 (12)	C15—H15	0.9500
Fe1—C14	2.0471 (12)	C2—H2a	0.9900
Fe1—C16	2.0466 (12)	C2—H2b	0.9900
Fe1—C15	2.0415 (12)	C2—C1	1.5309 (18)
Fe1—C18	2.0547 (12)	C2—C3	1.551 (2)
N1—C5	1.4919 (14)	C8—H8a	0.9900
N1—C4	1.4975 (14)	C8—H8b	0.9900
N1—C1	1.4989 (15)	C18—H18	0.9500
C12—H12	0.9500	C4—H4a	0.9900
C12—C13	1.4330 (15)	C4—H4b	0.9900
C12—C11	1.4316 (16)	C4—C3	1.5268 (16)
N2—C8	1.5020 (15)	C1—H1a	0.9900
N2—C7	1.4863 (16)	C1—H1b	0.9900
N2—C6	1.4849 (16)	C7—H7a	0.9800
C17—H17	0.9500	C7—H7b	0.9800
C17—C16	1.4289 (18)	C7—H7c	0.9800
C17—C18	1.4298 (19)	C3—H3a	0.9900
C13—C9	1.4444 (15)	C3—H3b	0.9900
C13—C5	1.4983 (15)	C6—H6a	0.9800
C9—C10	1.4388 (15)	C6—H6b	0.9800
C9—C8	1.4945 (15)	C6—H6c	0.9800
C10—H10	0.9500

Br1—Cd1—Br2	113.236 (11)	C8—C9—C10	125.98 (9)
N1—Cd1—Br2	109.79 (2)	C9—C10—Fe1	68.71 (6)
N1—Cd1—Br1	108.42 (2)	H10—C10—Fe1	127.11 (3)
N2—Cd1—Br2	104.98 (3)	H10—C10—C9	125.84 (6)
N2—Cd1—Br1	107.86 (3)	C11—C10—Fe1	69.91 (6)
N2—Cd1—N1	112.60 (3)	C11—C10—C9	108.32 (9)
C17—Fe1—C12	108.79 (5)	C11—C10—H10	125.84 (6)
C13—Fe1—C12	41.15 (4)	C13—C5—N1	112.25 (8)
C13—Fe1—C17	126.44 (5)	H5a—C5—N1	109.15 (5)
C9—Fe1—C12	69.40 (4)	H5a—C5—C13	109.15 (5)
C9—Fe1—C17	163.70 (5)	H5b—C5—N1	109.15 (5)
C9—Fe1—C13	41.65 (4)	H5b—C5—C13	109.15 (6)
C10—Fe1—C12	68.73 (4)	H5b—C5—H5a	107.9
C10—Fe1—C17	154.45 (5)	C12—C11—Fe1	69.23 (6)
C10—Fe1—C13	69.49 (4)	C10—C11—Fe1	69.48 (6)
C10—Fe1—C9	41.25 (4)	C10—C11—C12	108.12 (9)
C11—Fe1—C12	40.83 (5)	H11—C11—Fe1	126.92 (3)
C11—Fe1—C17	120.74 (5)	H11—C11—C12	125.94 (6)
C11—Fe1—C13	69.26 (5)	H11—C11—C10	125.94 (6)
C11—Fe1—C9	69.18 (4)	H14—C14—Fe1	126.35 (4)
C11—Fe1—C10	40.61 (4)	C15—C14—Fe1	69.29 (6)
C14—Fe1—C12	155.59 (5)	C15—C14—H14	125.99 (7)
C14—Fe1—C17	68.64 (5)	C18—C14—Fe1	69.94 (7)
C14—Fe1—C13	119.51 (5)	C18—C14—H14	125.99 (7)
C14—Fe1—C9	105.95 (5)	C18—C14—C15	108.02 (11)
C14—Fe1—C10	124.40 (5)	C17—C16—Fe1	69.94 (7)
C14—Fe1—C11	161.77 (5)	H16—C16—Fe1	126.36 (4)
C16—Fe1—C12	126.10 (5)	H16—C16—C17	125.95 (7)
C16—Fe1—C17	40.77 (5)	C15—C16—Fe1	69.32 (6)
C16—Fe1—C13	163.85 (5)	C15—C16—C17	108.09 (11)
C16—Fe1—C9	153.30 (5)	C15—C16—H16	125.95 (7)
C16—Fe1—C10	118.76 (5)	C14—C15—Fe1	69.71 (6)
C16—Fe1—C11	107.20 (5)	C16—C15—Fe1	69.71 (7)
C16—Fe1—C14	68.82 (5)	C16—C15—C14	107.83 (11)
C15—Fe1—C12	162.66 (5)	H15—C15—Fe1	126.07 (4)
C15—Fe1—C17	68.80 (5)	H15—C15—C14	126.08 (7)
C15—Fe1—C13	154.01 (5)	H15—C15—C16	126.08 (7)
C15—Fe1—C9	117.90 (5)	H2b—C2—H2a	108.8
C15—Fe1—C10	105.63 (5)	C1—C2—H2a	110.77 (7)
C15—Fe1—C11	124.46 (5)	C1—C2—H2b	110.77 (7)
C15—Fe1—C14	41.00 (5)	C3—C2—H2a	110.77 (7)
C15—Fe1—C16	40.97 (5)	C3—C2—H2b	110.77 (7)
C18—Fe1—C12	121.41 (5)	C3—C2—C1	104.91 (10)
C18—Fe1—C17	40.71 (5)	C9—C8—N2	111.94 (9)
C18—Fe1—C13	107.87 (5)	H8a—C8—N2	109.22 (6)
C18—Fe1—C9	125.39 (5)	H8a—C8—C9	109.22 (6)
C18—Fe1—C10	162.48 (5)	H8b—C8—N2	109.22 (6)
C18—Fe1—C11	156.09 (5)	H8b—C8—C9	109.22 (6)
C18—Fe1—C14	40.70 (5)	H8b—C8—H8a	107.9
C18—Fe1—C16	68.60 (5)	C17—C18—Fe1	69.66 (7)
C18—Fe1—C15	68.75 (5)	C14—C18—Fe1	69.36 (7)
C5—N1—Cd1	109.95 (6)	C14—C18—C17	108.15 (11)
C4—N1—Cd1	108.90 (7)	H18—C18—Fe1	126.62 (4)
C4—N1—C5	111.89 (8)	H18—C18—C17	125.92 (7)
C1—N1—Cd1	112.79 (7)	H18—C18—C14	125.92 (7)
C1—N1—C5	110.52 (9)	H4a—C4—N1	111.06 (6)
C1—N1—C4	102.62 (8)	H4b—C4—N1	111.06 (6)
H12—C12—Fe1	127.03 (3)	H4b—C4—H4a	109.0
C13—C12—Fe1	68.77 (6)	C3—C4—N1	103.52 (9)
C13—C12—H12	125.83 (6)	C3—C4—H4a	111.06 (7)
C11—C12—Fe1	69.94 (6)	C3—C4—H4b	111.06 (7)
C11—C12—H12	125.83 (6)	C2—C1—N1	104.67 (10)
C11—C12—C13	108.33 (9)	H1a—C1—N1	110.82 (6)
C8—N2—Cd1	110.90 (6)	H1a—C1—C2	110.82 (7)
C7—N2—Cd1	107.73 (7)	H1b—C1—N1	110.82 (6)
C7—N2—C8	109.56 (9)	H1b—C1—C2	110.82 (7)
C6—N2—Cd1	111.07 (8)	H1b—C1—H1a	108.9
C6—N2—C8	108.58 (9)	H7a—C7—N2	109.5
C6—N2—C7	108.97 (10)	H7b—C7—N2	109.5
H17—C17—Fe1	126.61 (4)	H7b—C7—H7a	109.5
C16—C17—Fe1	69.29 (7)	H7c—C7—N2	109.5
C16—C17—H17	126.05 (7)	H7c—C7—H7a	109.5
C18—C17—Fe1	69.62 (7)	H7c—C7—H7b	109.5
C18—C17—H17	126.05 (7)	C4—C3—C2	104.79 (10)
C18—C17—C16	107.90 (11)	H3a—C3—C2	110.79 (7)
C12—C13—Fe1	70.07 (6)	H3a—C3—C4	110.79 (7)
C9—C13—Fe1	69.30 (6)	H3b—C3—C2	110.79 (7)
C9—C13—C12	107.68 (9)	H3b—C3—C4	110.79 (6)
C5—C13—Fe1	125.66 (7)	H3b—C3—H3a	108.9
C5—C13—C12	126.73 (10)	H6a—C6—N2	109.5
C5—C13—C9	125.60 (10)	H6b—C6—N2	109.5
C13—C9—Fe1	69.06 (5)	H6b—C6—H6a	109.5
C10—C9—Fe1	70.03 (6)	H6c—C6—N2	109.5
C10—C9—C13	107.54 (9)	H6c—C6—H6a	109.5
C8—C9—Fe1	125.33 (8)	H6c—C6—H6b	109.5
C8—C9—C13	126.46 (9)

Cd1—N1—C5—C13	50.60 (7)	N1—C5—C13—C12	89.87 (10)
Cd1—N1—C4—C3	75.89 (7)	N1—C5—C13—C9	−90.68 (10)
Cd1—N1—C1—C2	−76.32 (8)	N1—C4—C3—C2	29.97 (10)
Cd1—N2—C8—C9	−48.23 (7)	N1—C1—C2—C3	−21.62 (10)
Fe1—C12—C13—C9	−59.32 (6)	C12—C13—C9—C10	0.11 (9)
Fe1—C12—C13—C5	120.21 (6)	C12—C13—C9—C8	178.96 (8)
Fe1—C12—C11—C10	58.76 (7)	C12—C11—C10—C9	−0.50 (10)
Fe1—C17—C16—C15	−59.02 (7)	N2—C8—C9—C13	88.96 (10)
Fe1—C17—C18—C14	58.86 (7)	N2—C8—C9—C10	−92.40 (10)
Fe1—C13—C12—C11	58.91 (7)	C17—C16—C15—C14	−0.11 (11)
Fe1—C13—C9—C10	−59.70 (7)	C17—C18—C14—C15	−0.03 (11)
Fe1—C13—C9—C8	119.15 (6)	C13—C12—C11—C10	0.57 (10)
Fe1—C13—C5—N1	−179.45 (9)	C13—C9—C10—C11	0.24 (9)
Fe1—C9—C13—C12	59.81 (7)	C13—C5—N1—C4	−70.55 (10)
Fe1—C9—C13—C5	−119.73 (6)	C13—C5—N1—C1	175.76 (9)
Fe1—C9—C10—C11	−58.85 (7)	C9—C13—C12—C11	−0.42 (9)
Fe1—C9—C8—N2	177.75 (9)	C9—C8—N2—C7	70.56 (10)
Fe1—C10—C9—C13	59.09 (6)	C9—C8—N2—C6	−170.53 (10)
Fe1—C10—C9—C8	−119.77 (6)	C10—C9—C13—C5	−179.43 (8)
Fe1—C10—C11—C12	−58.61 (7)	C5—N1—C4—C3	−162.35 (10)
Fe1—C11—C12—C13	−58.19 (7)	C5—N1—C1—C2	160.14 (9)
Fe1—C11—C10—C9	58.11 (7)	C5—C13—C12—C11	179.12 (11)
Fe1—C14—C15—C16	59.51 (7)	C5—C13—C9—C8	−0.58 (12)
Fe1—C14—C18—C17	−59.05 (8)	C11—C10—C9—C8	−178.62 (8)
Fe1—C16—C17—C18	59.11 (8)	C14—C18—C17—C16	−0.04 (11)
Fe1—C16—C15—C14	−59.51 (8)	C16—C15—C14—C18	0.08 (10)
Fe1—C15—C14—C18	−59.43 (7)	C15—C16—C17—C18	0.09 (11)
Fe1—C15—C16—C17	59.40 (8)	C2—C1—N1—C4	40.69 (10)
Fe1—C18—C17—C16	−58.90 (8)	C4—C3—C2—C1	−5.11 (10)
Fe1—C18—C14—C15	59.02 (7)	C1—N1—C4—C3	−43.86 (9)

Bond geometry (Å, °; M = metal center) top

Bond lengths	rac-1	rac-2
N1—M	2.050 (2)	2.3148 (10)
N2—M	2.077 (2)	2.3250 (11)
Br1—M	2.3560 (10)	2.5544 (5)
Br2—M	2.3606 (10)	2.5685 (5)

Bond angles	rac-1	rac-2
Br1—M—Br2	113.88 (4)	113.236 (11)
N1—M—N2	110.45 (8)	112.60 (3)
Br1—M—N2	107.20 (7)	107.86 (3)
Br2—M—N1	106.69 (7)	109.79 (2)

Torsion angles	rac-1	rac-2
C3—C4—C13—C9	–171.3 (2)	35.4 (2)
C5—N1—M—Br1	–167.24 (13)	–108.21 (6)
C5—N1—M—Br2	68.03 (14)	127.62 (6)
N1—M—N2—C6	166.39 (17)	108.68 (8)
N1—M—N2—C7	–76.41 (14)	–132.05 (7)
C4—N1—C5—C13	–52.5 (2)	–70.55 (10)
C7—N2—C8—C9	50.0 (2)	70.56 (10)
C1—C2—C3—C4	4.1 (2)	–5.11 (10)
H10—C10—C15—H15	3.2749 (4)	–7.4408 (9)

References

Aliyeva, V. A., Paninho, A. B., Nunes, A. V. M., Karmakar, A., Gurbanov, A. V., Rutigliano, A. R., Gallo, E., Mahmudov, K. T. & Pombeiro, A. J. L. (2023). ACS Omega 8, 42290–42300. Web of Science CrossRef CAS PubMed Google Scholar
Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2015). Acta Cryst. A71, 59–75. Web of Science CrossRef IUCr Journals Google Scholar
Bruker (2016). APEX6 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Butler, I. R., Horton, P. N., Clegg, W., Coles, S. J., Murphy, L. & Elliott, S. (2026). Inorganics 14, 37. Web of Science CrossRef Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Eckert, P. K., Vieira, I., Gessner, V. H., Börner, J., Strohmann, C. & Herres-Pawlis, S. (2013). Polyhedron 49, 151–157. Web of Science CrossRef CAS 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
Hooft, R. W. W., Straver, L. H. & Spek, A. L. (2010). J. Appl. Cryst. 43, 665–668. Web of Science CrossRef CAS IUCr Journals Google Scholar
Jia, W.-G., Li, D.-D., Gu, C., Dai, Y.-C., Zhou, Y.-H., Yuan, G. & Sheng, E.-H. (2015). Inorg. Chim. Acta 427, 226–231. Web of Science CrossRef CAS Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Marr, G. (1967). J. Organomet. Chem. 9, 147–151. CrossRef CAS Web of Science Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. Web of Science CrossRef Google Scholar
Schaarschmidt, D. & Lang, H. (2013). Organometallics 32, 5668–5704. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Steffen, P., Unkelbach, C., Christmann, M., Hiller, W. & Strohmann, C. (2013). Angew. Chem. Int. Ed. 52, 9836–9840. Web of Science CSD CrossRef CAS Google Scholar
Wu, D., Xiao, L., Shi, Y., Zhang, Q., Du, W., Zhang, J., Li, S., Zhou, H., Wu, J. & Tian, Y. (2017). J. Organomet. Chem. 830, 67–73. Web of Science CrossRef CAS Google Scholar

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Volume 82| Part 6| June 2026| Pages 600-605

https://doi.org/10.1107/S2056989026004688

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

Crystal structure and Hirshfeld surface analysis of 1-(di­methyl­amino­meth­yl)-2-(pyrrolidin-1-ylmeth­yl)ferrocene complexes with zinc(II) bromide and cadmium(II) bromide

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

References

research communications

Crystal structure and Hirshfeld surface analysis of 1-(dimethylaminomethyl)-2-(pyrrolidin-1-ylmethyl)ferrocene complexes with zinc(II) bromide and cadmium(II) bromide

3. Supramolecular features