Iron(II) complexes of dimethyltriazacyclophane

research paper s

Wei-Tsung Lee,^a* Matthias Zeller,^bDavid Upp,^aYuliya Politanska,^aDoug

Steinman,^aTalal Al-Assil^aand Daniel P. Becker^a*

ISSN 2053-2296

^aDepartment of Chemistry and Biochemistry, Loyola University Chicago, 1032 West Sheridan Road, Chicago, Illinois

60660, USA, and ^bDepartment of Chemistry, Purdue University, 560 Oval Dr., W. Lafayette, IN 47907-2084, USA.

*Correspondence e-mail: wlee5@luc.edu, dbecke3@luc.edu

Received 1 August 2018

Accepted 29 October 2018

Treatment of the ortho-triazacyclophane 1,4-dimethyltribenzo[b,e,h][1,4,7]tri-

azacyclonona-2,5,8-triene [(C₆H₅)₃(NH)(NCH₃)₂, L1] with Fe[N(SiMe₃)₂]₂

yields the dimeric iron(II) complex bis(ꢀ-1,4-dimethyltribenzo[b,e,h][1,4,7]tri-

azacyclonona-2,5,8-trien-7-ido)bis[(ꢀ-1,4-dimethyltribenzo[b,e,h][1,4,7]triaza-

cyclonona-2,5,8-trien-7-ido)iron(II)], [Fe(C₂₀H₁₈N₃)₄] or Fe₂(L1)₄(9). Disso-

lution of 9 in tetrahydrofuran (THF) results in solvation by two THF ligands

and the formation of a simpler monoiron complex, namely bis(ꢀ-1,4-

dimethyltribenzo[b,e,h][1,4,7]triazacyclonona-2,5,8-trien-7-ido-ꢁN⁷)bis(tetra-

hydrofuran-ꢁO)iron(II), [Fe(C₂₀H₁₈N₃)₂(C₄H₈O)₂] or (L1)₂Fe(THF)₂(10). The

reaction is reversible and 10 reverts in vacuo to diiron complex 9. In the

structures of both 9 and 10, the monoanionic triazacyclophane ligand L1^Àis

observed in only the less-symmetric saddle conformation. No bowl-shaped

crown conformers are observed in the solid state, thus preventing chelating

ꢁ³-coordination to the metal as had been proposed earlier based on density

functional theory (DFT) calculations. Instead, the L1^Àligands are bound in

either a ꢂ²-chelating fashion through the amide and one amine donor (for one of

the four ligands of 9), or solely through their amide N atoms in an even simpler

monodentate ꢂ¹-coordination mode. Density functional calculations on dimer 9

revealed nearly full cationic charges on each Fe atom and no bonding

interaction between the two metal centers, consistent with the relatively long

Edited by B. D. Santarsiero, University of Illinois

at Chicago, USA

Keywords: benzo-fused TACN; diiron complex;

ipso interaction; DFT calculations; azacyclo-

phane; crystal structure; computational chem-

istry.

CCDC references: 1875771; 1875770

Supporting information: this article has

supporting information at journals.iucr.org/c

˚

FeÁ Á ÁFe distance of 2.912 (1) A observed in the solid state.

1. Introduction

Amine-containing macrocyclic ligands have been widely used

and play an important role in the ﬁeld of coordination

chemistry due to their ability to, on many occasions, form

kinetically inert metal complexes. Common among them is

1,4,7-triazacyclononane (TACN, 1, Fig. 1), which is often

considered to structurally and electronically resemble the ꢂ⁵-

cyclopentadienyl (Cp) ligand in its usual facial coordination.

Given the modular nature of TACN, the straightforward

introduction of chemical functionality, generally through the

N atoms, enables modulation of the ligand, affording a variety

of multidentate ligands ranging from tri- to nonadentate

TACN-based ligands for supporting main-group-, transition-

(Yang & Zompa, 1976), lanthanide-, and actinide-metal

complexes, and the coordination chemistry has been reviewed

(Yang & Zompa, 1976; Chaudhuri & Wieghardt, 2007).

Among the transition-metal compounds are several TACN

complexes of iron (Turner & Schultz, 2001; Tse et al., 2014;

Mitra et al., 2014; Boeyens et al., 1985; Kindermann et al., 2016;

Tsitovich et al., 2015; Sabenya et al., 2017; Nakanishi et al.,

2016; Thorarinsdottir et al., 2017).

Despite its vast utility and popularity, backbone-aryl

modiﬁcations of TACN, such as monobenzo-annelated deri-

# 2018 International Union of Crystallography

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https://doi.org/10.1107/S2053229618015255 1641

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Figure 1

Triazacyclononane (TACN, 1) and benzo-fused TACN derivatives, including monobenzo-TACN 2, dibenzo-TACN 3, triazacyclophane 4, and

cyclotriveratrylene (CTV, 5).

vative 2, dibenzoannelated derivative 3, and triazaortho-

cyclophane 4 (Fig. 1) remain almost completely unexplored. It

is noteworthy that ancillary ligands based on aniline or

phenylenediamine moieties are considered as redox non-

innocent ligands and their metal complexes have drawn much

attention due to unique reactivity and catalytic applications.

(Chłopek et al., 2006; Lyaskovskyy & de Bruin, 2012; Hicks,

2008; Suarez et al., 2013; Ghosh et al., 2001; Herebian et al.,

2003; Van der Meer et al., 2014; Leconte et al., 2014, 2017;

Kochem et al., 2013) A literature search reveals that only two

examples of benzo-annelated derivatives have been prepared,

(Panagopoulos et al., 2010; Samanta et al., 2012), yet no well-

deﬁned metal complexes have been successfully isolated

(Samanta et al., 2012), although binding of the neutral ligand 4

to iron has been proposed and was the subject of modeling

studies (Foscato et al., 2015). In contrast, several late-transi-

tion-metal complexes employing the S-donor congener, tri-

thiaorthocyclophane, have been reported (Von Deuten et al.,

1979; Von Deuten & Klar, 1981; Kopf et al., 1979).

Cyclotriveratrylene (CTV, 5) (Collet, 1987) is a bowl-

shaped molecule that has been explored for applications in

sensors, self-organized materials, liquid crystals, and metallo-

supramolecular chemistry (Hardie, 2010). CTV and its cryp-

tophane derivatives are of great interest in molecular

recognition in host–guest chemistry (Hardie, 2012). Our

interest in the supramolecular scaffold CTV includes studies

of the conformational dynamics of its derivatives between the

bowl-shaped crown conformer and the saddle confomer

(French et al., 2009), homologs of CTV (Lutz et al., 2012), and

apically-modiﬁed chiral derivatives for enantio-discrimination

(Lutz et al., 2018). Inspired by the conceptual combination of

CTV and TACN, we prepared 1,4-dimethyltribenzo[b,e,h]-

[1,4,7]triazacyclonona-2,5,8-triene (7), an ortho-triazacyclo-

phane, and 1,4,7-trimethyltribenzo[b,e,h][1,4,7]triazacyclonona-

2,5,8-triene (8) (Fig. 2). Speciﬁcally, we envisioned a supra-

molecular scaffold that could include a complexed metal, both

to provide a cationic cyclophane for anion recognition, as well

as to enable an electrochemically switchable host molecule. In

light of the limited previous studies, we were interested in

exploring the coordination chemistry of benzo-fused TACN

ligands 7 and 8 with ﬁrst-row transition metals, especially iron

because of spin-crossover behavior, which was observed for

[Fe(TACN)₂]²⁺(Turner & Schultz, 2001).

2. Experimental

2.1. Material and methods

All manipulations were performed under a nitrogen

atmosphere using standard Schlenk techniques or in an M.

Braun UNIlab Pro glove-box. Glassware was dried at 150 ^ꢀC

overnight. Diethyl ether, n-pentane, tetrahydrofuran, and

toluene were puriﬁed using a Pure Process Technology solvent

puriﬁcation system. Deuterated benzene was ﬁrst dried with

CaH₂, then over Na/benzophenone, and then vacuum trans-

ferred into a storage container. Before use, an aliquot of each

solvent was tested with a drop of sodium benzophenone ketyl

in THF solution. All reagents were purchased from commer-

cial vendors and used as received. Fe[N(SiMe₃)₂]₂was

prepared according to a literature procedure (Ohki et al.,

2010). ¹H NMR data were recorded on a Varian Inova 300 or

1

500 MHz spectrometer at 22 ^ꢀC. Resonances in the H NMR

Figure 2

Optimized Buchwald–Hartwig macrocyclization of chloroaniline derivative 6 to yield L1 (7) and the previously reported methylation (Panagopoulos et

al., 2010) to afford L2 (8).

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Table 1

Experimental details.

9

10

Crystal data

Chemical formula

M_r

[Fe(C₂₀H₁₈N₃)₄]

1313.19

[Fe(C₂₀H₁₈N₃)₂(C₄H₈O)₂]

800.80

Crystal system, space group

Temperature (K)

Monoclinic, P2₁/c

100

21.758 (2), 12.7682 (13), 31.382 (3)

90, 109.191 (5), 90

8233.7 (14)

4

Cu Kꢃ

3.17

Orthorhombic, Pbca

100

15.9624 (12), 15.8047 (11), 32.747 (2)

90, 90, 90

8261.5 (10)

8

Cu Kꢃ

3.29

˚

a, b, c (A)

ꢃ, ꢄ, ꢅ (^ꢀ)

3

˚

V (A )

Z

Radiation type

ꢀ (mm^À1

Crystal size (mm)

)

0.11 Â 0.06 Â 0.05

0.11 Â 0.10 Â 0.06

Data collection

Diffractometer

Absorption correction

T_min, T_max

Bruker Prospector CCD

Multi-scan (APEX2; Bruker, 2014)

0.478, 0.753

Bruker X8 Prospector CCD

Multi-scan (APEX2; Bruker, 2014)

0.569, 0.753

No. of measured, independent and observed

[I > 2ꢆ(I)] reﬂections

R_int

52565, 14191, 8827

23792, 7194, 5411

0.133

0.597

0.055

0.596

À1

˚

(sin ꢇ/ꢈ)_max(A

)

Reﬁnement

R[F²> 2ꢆ(F²)], wR(F²), S

No. of reﬂections

0.076, 0.193, 1.03

14191

855

0

H-atom parameters constrained

0.043, 0.111, 1.05

7194

555

132

H-atom parameters constrained

0.45, À0.28

No. of parameters

No. of restraints

H-atom treatment

À3

˚

Áꢉ_max, Áꢉ_min(e A

)

0.79, À0.54

Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), shelXle (Hu¨bschle et al., 2011) and publCIF

(Westrip, 2010).

spectra are referenced to residual C₆D₅H at d = 7.16 or

C₄D₇HO at d = 3.58 ppm. Solution magnetic susceptibilities

were determined by the Evans method (Schubert, 1992).

Elemental analysis was conducted by Midwest Microlab, LLC

(Indianapolis, IN).

single-point energy using the density functional level of theory

and the B3LYP method with the 6-31G* basis set, using the

option MEM_STATIC=502. Continuing from this as the

starting point for the wB97X-D method with the double-basis

set 6-311+G(3df,2p)[6-311G*] afforded atomic charges of all

atoms, including +0.961 for Fe1 and +0.998 for Fe2, as well as

all HOMO/LUMO and spin-surface maps.

For direct comparison of the crystal structure with the

equilibrium geometry calculated structure, the density func-

tional (6-31G*) result with frozen heavy atoms was thawed

(heavy atoms) and recalculated with the density functional

level of theory, the EDF2 method, and the 6-31G* basis set,

with COMVERGE SCFCYCLES=900, to yield the geometry

optimized thawed structure.

2.2. Computational studies

The CIF ﬁle of 9 was opened with SPARTAN’16 (Wave-

function, 2016). The positions of the heavy atoms were frozen,

and ‘Molecular Mechanics’ was performed to place the H

atoms. The number of unpaired electrons was set at 8, and a

single-point ground-state energy in the gas phase was calcu-

lated with Hartree–Fock (3-21G* basis set), using the options

CONVERGE, SCFTOLERANCE=LOW, and SCFCYCLES=

900. After successful completion, this result was used as the

starting point for a density functional calculation using the

EDF2 method and the 6-31G* basis set, keeping the same

options as above (CONVERGE, SCFTOLERANCE=LOW,

and SCFCYCLES=900). After successful completion, this

result was used as the starting point for a density functional

calculation using the EDF2 method and the 6-31G* basis set

with options CONVERGE and SCFCYCLES=900 but elim-

inating the low SCF tolerance option. After successful

completion, this result was used to calculate orbitals and

energies, as well as charges and bond orders.

2.3. Synthesis and crystallization

2.3.1. Preparation of 1,4-dimethyltribenzo[b,e,h][1,4,7]tri-

azacyclonona-2,5,8-triene (L1, 7). A 125 ml pressure ﬂask

was charged with XPhos (260 mg, 0.54 mmol) and Pd(dba)₂

(dba is dibenzylideneacetone; 156 mg, 0.271 mmol), and a

solution of chloroaniline, 6 (Panagopoulos et al., 2010)

(504 mg, 1.49 mmol), in anhydrous 1,4-dioxane (26 ml). The

resulting solution was stirred at room temperature for 15 min

as argon was passed over the solution. Caesium carbonate

(838 mg, 2.57 mmol) was added and the resulting suspension

was purged with argon for 30 min. The ﬂask was sealed and

heated in a 140 ^ꢀC oil bath for 16 h. The reaction mixture was

The result of the density functional EDF2 method with the

6-31G* basis set was used as the starting point to calculate the

ꢁ

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Iron(II) complexes of dimethyltriazacyclophane 1643

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cooled to room temperature and ﬁltered through a pad of

Celite, and the ﬁlter cake was washed with 1:1 (v/v) methanol–

CH₂Cl₂. The ﬁltrate was concentrated to dryness, leaving a

brown solid which was partitioned between ethyl acetate and

water. The aqueous layer was then extracted once with ethyl

acetate and the organic extracts were combined, dried over

MgSO₄, ﬁltered, and concentrated to dryness. The residue was

dissolved in ethyl acetate and to this solution was added 6.6 g

of Celite, and the suspension concentrated to dryness, leaving

an off-white powder. This powder was then applied to the top

of an 80 g column (Silica gel 60A, 40–75 mm, 200 Â 400 mesh)

and eluted at a 42% maximum pump rate using a gradient

starting with 20% CH₂Cl₂/petroleum ether and increasing to

30% CH₂Cl₂/petroleum ether, collecting 28 ml fractions to

give macrocycle 7 (L1) as an off-white powder (yield: 338 mg,

The structure of diiron complex 9 contains solvent-acces-

3

sible voids of 2479.0 A (ca 30% of the unit-cell volume). The

˚

residual electron-density peaks were not arranged in an

interpretable pattern. The structure factors of the unresolved

solvent molecules were estimated using reverse Fourier

transform methods employing the SQUEEZE routine (van

der Sluis & Spek, 1990; Spek, 2015), as implemented in the

program PLATON (Spek, 2009). The resultant .fab ﬁle with

scattering contributions from the solvent molecules was used

in the further reﬁnement in combination with the .hkl ﬁle. The

SQUEEZE procedure estimated 569.8 electrons within the

solvent-accessible voids, equivalent to 11.4 molecules of

toluene (the solvents of crystallization were n-pentane and

toluene).

In monoiron complex 10, one THF ligand is disordered with

two alternative orientations. The two moieties were restrained

to have similar geometries, and the U^ijcomponents of the

anisotropic displacement parameters of the atoms were

1

75%; m.p. 228–230 ^ꢀC) and with H and ¹³C spectra identical

to those reported previously (Panagopoulos et al., 2010).

2.3.2. Preparation of [(L1)₄Fe₂] (9). To a stirred solution of

L1 (394 mg, 2.0 mmol) in THF (4 ml) under an N₂atmosphere

was added a solution of Fe[N(SiMe₃)₂]₂(377 mg, 1.0 mmol) in

THF (2 ml). After 3 h, the volatiles were removed under

reduced pressure. The residue was redissolved in toluene

(5 ml) and ﬁltered through a Celite pad. The ﬁltrate was dried

in vacuo to yield diiron complex 9 as a dark-red solid (yield:

408 mg, 68%). Crystals suitable for X-ray diffraction were

grown by slow diffusion of n-pentane into a toluene solution at

À35 ^ꢀC. ꢀ_eff= 7.7 (3) ꢀ_B. Analysis calculated (%) for

C₈₀H₇₂Fe₂N₁₂: C 73.17, H 5.53, N 12.80; found: C 73.53, H 5.35,

N 12.42.

˚

restrained to be similar if closer to each other than 1.7 A (the

2

s.u. value used was 0.01 A ). Subject to these conditions, the

˚

occupancy ratio reﬁned to 0.790 (8):0.210 (8). Reﬂection 002

was affected by the beamstop and was omitted from the

reﬁnement.

Crystal data, data collection and structure reﬁnement

details are summarized in Table 1.

3. Results and discussion

3.1. Optimization of the synthesis of L1 (see Fig. 1)

2.3.3. Preparation of [(L1)₂Fe(THF)₂] (10). Diiron complex

9 was dissolved in THF and immediately yielded a yellow–

green solution. Crystals of monoiron complex 10 suitable for

X-ray diffraction were obtained by slow diffusion of n-pentane

into a THF solution at À35 ^ꢀC. ꢀ_eff(THF-d₈) = 5.1 (2) ꢀ_B.

Elemental analysis for 10 was not obtained due to the

conversion of monoiron complex 10 back to diiron complex 9

upon prolonged vacuum drying.

Our previously reported synthesis (Panagopoulos et al.,

2010) of L1 utilized a microwave-assisted intramolecular ring

closure to form the tribenzotriazacyclononane ring. However,

that reaction gave highly variable results, leading us to pursue

reaction conditions that would yield more consistent and

scalable yields. The original reaction conditions were 10 mol%

of Pd(dba)₂, 20 mol% of racemic BINAP, and 150 mol% of

Cs₂CO₃in a solvent mixture of 1:1 (v/v) toluene–tert-butanol

at a concentration of 0.09 molar under an argon atmosphere at

250 W and 130^ꢀC for 1 h to give the desired product in an

optimum yield of 50%. We turned our attention to the use of

Pd(OAc)₂as a catalyst, which gave more consistent results,

and varied the amount of catalyst from 10 to 60 mol%,

revealing the optimal amount of catalyst to be ca 20 mol%. We

explored alternatives to toluene/tert-butanol, and improved

results were seen when the solvent was changed to 1,4-

dioxane. The concentration of the reaction with respect to the

acyclic starting material was then varied from 0.05 to 1 M, with

2.4. Refinement

If not speciﬁed otherwise, H atoms attached to C and N

atoms were positioned geometrically and constrained to ride

˚

on their parent atoms, with C—H bond lengths of 0.95 A for

˚

alkene and aromatic, and 0.99 and 0.98 A for aliphatic CH₂

and CH₃groups, respectively. Methyl H atoms were allowed to

rotate but not to tip to best ﬁt the experimental electron

density. U_iso(H) values were set to a multiple of U_eq(C), i.e. 1.5

for CH₃and 1.2 for CH₂and CH units, respectively.

Figure 3

Attempted syntheses of ortho-triazacyclophane iron halide complexes.

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1644 Lee et al. Iron(II) complexes of dimethyltriazacyclophane

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Figure 4

Synthesis of diiron complex 9 and monoiron complex 10.

0.05 M producing the best results. We next turned our atten-

tion to varying the ligand, and found that tert-Butyl XPhos

gave superior results to BINAP, JohnPhos, or tri-tert-butyl-

phosphine. Microwave heating was explored relative the

conventional thermal conditions. We tried performing the

reaction in the microwave on a 0.1 mmol scale using 20 mol%

Pd(dba)₂, 40 mol% XPhos, and 200 mol% Cs₂CO₃at a

concentration of 0.05 molar in 1,4-dioxane at 250 W and

105 ^ꢀC. The result was consumption of the starting material,

but it required four cycles in the microwave and was not

scalable. Performing the reaction on the same scale under

thermal conditions in a pressure tube at 160 ^ꢀC also led to

consumption of the starting material, but gave a number of

side products. Lowering the temperature to 140 ^ꢀC for 16 h

gave consistently higher yields of 59–74% on a scale of 2 mmol

of the acyclic amine halide, compared to yields of 50% or less

on a 0.1 mmol scale (Fig. 2). Methylation as previously

described (Panagopoulos et al., 2010) gave the trimethyl

derivative L2.

3.2. Synthesis of iron(II) complexes

Attempts at preparing ﬁrst-row transition-metal complexes

by simply mixing divalent salts of iron, cobalt, nickel, copper,

or zinc with L1, or with L2, failed. A predicted molecular ion

was observed when screening L1 and L2 with FeX₂, CoX₂,

NiX₂(X = Cl and Br), CuCl₂, or ZnCl₂; however, none of these

1

complexes could be isolated based on H NMR spectroscopy

(Fig. 3). We attribute this to the poor availability of the

nitrogen lone-pair electrons due to delocalization in the

aromatic rings. We therefore pursued deprotonation of L1,

followed by transmetallation with iron halide, which was

promising in producing paramagnetic products, but the

mixtures were intractable. The formation of multiple species

could be attributed, at least in part, to the deprotonated ligand

undergoing a Smiles rearrangement (Panagopoulos et al.,

2013).

Encouraged by the potential formation of inorganic

complexes, an iron precursor with an internal (counter-ion)

base, Fe[N(SiMe₃)₂]₂, was used (Fig. 4). Thus, treating

Fe[N(SiMe₃)₂]₂with L1 in THF afforded a yellow–green

solution and, upon the removal of the volatiles, a dark-red

residue was obtained. Single crystals suitable for X-ray crys-

tallographic analysis were harvested from a saturated toluene

solution stored at À35 ^ꢀC (Table 1), and the structure was

revealed to be the diiron complex 9 (Fig. 5; a depiction with

complete atom labeling for Fe and N atoms is given in Fig. S1

in the supporting information). The X-ray crystal structure of

9 consists of a tetrahedral Fe^IIion and a trigonal planar Fe^II

center bridged by two Me₂L1^Àunits. Notably, 9 is a rare

example of an asymmetric diiron complex. Fe1 adopts a

distorted tetrahedral geometry (ꢊ₄= 0.69; Yang et al., 2007),

coordinated by one amine, one terminal amido, and two

bridging amido N atoms. Fe2 has a distorted trigonal–planar

coordination, as quantiﬁed by the sum of the angles

[359.8 (2)^ꢀ] around the metal, with a narrow N—Fe—N angle

of 93.0 (1)^ꢀbetween two bridging amido N atoms (N4 and

Figure 5

X-ray crystal structure of diiron complex 9. Displacement ellipsoids are

shown at the 50% probability level. Color key: orange = Fe, blue = N, and

gray = C. H atoms and labels for most C and N atoms have been omitted

for clarity. A displacement ellipsoid plot with H atoms and labels for all N

atoms is given in the supporting information.

˚

N7). The Fe—N_amidobond lengths of 1.947 (4)–2.153 (4) A are

˚

shorter than that of Fe—N_amine[2.245 (3) A]. Not surprisingly,

the Fe—N_amidobond lengths in the ꢀ₂-bridging amides (N4

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Table 2

Selected bond lengths (A) and angles ( ) for 9 and 10.

ꢀ

˚

Atoms are labeled as indicated in Figs. 5 and 7.

9

10

Fe1—N4 2.153 (4) N4—Fe1—N7

Fe1—N7 2.091 (3) N4—Fe1—N9 122.6 (1) Fe1—N4

Fe1—N9 1.992 (4) N4—Fe1—N10 115.7 (1) Fe1—O1

Fe1—N10 2.245 (3) N7—Fe1—N9

N7—Fe1—N10 139.6 (1)

Fe2—N1 1.947 (4) N9—Fe1—N10 107.5 (1) N1—Fe1—N4 126.64 (8)

Fe2—N4 2.068 (3) O1—Fe1—O2 93.90 (7)

89.8 (1) Fe1—N1

2.009 (2)

1.986 (2)

2.093 (2)

2.107 (2)

79.8 (1) Fe1—O2

Fe2—N7 2.061 (4) N1—Fe2—N4 143.6 (2) N1—Fe1—O1 116.48 (8)

N1—Fe2—N7 123.2 (2) N1—Fe1—O2 97.67 (8)

Fe1Á Á ÁFe2 2.912 (1) N4—Fe2—N7

93.0 (1) N4—Fe1—O1 100.46 (8)

N4—Fe1—O2 117.68 (8)

Fe2Á Á ÁC21 2.425 (4)

Fe2Á Á ÁC38 3.181 (5)

resolved and could be interpreteted as mostly a pentane

molecule disordered across an inversion center. The content

of the larger and the second smaller void is highly disordered

and no attempts were made to model it with disordered

solvent molecules. The content of the solvent-accessible voids

was estimated as ca 570 electrons, equivalent to 11.4 molecules

of toluene per unit cell.

Dissolution of diiron complex 9 in THF results in solvation

by two THF ligands and the formation of the simpler mono-

iron complex (L1)₂Fe(THF)₂(10). The molecular structure

and a partial numbering scheme of 10, as determined by X-ray

crystallography, is depicted in Fig. 7. Selected bond lengths

and angles are given in Table 2. The C atoms of one of the two

coordinated THF molecules are disordered, with a reﬁned

major occupancy of 0.790 (8). Disorder and complete atom

labeling are given in an additional ﬁgure in the supporting

information (Fig. S2 in the supporting information). The Fe

atom, unaffected by the disorder, is in a distorted tetrahedral

(ꢊ₄= 0.82) environment, with a signiﬁcantly widened N—Fe—

N bond angle of 126.64 (8)^ꢀdue to steric and electrostatic

repulsion between the bulky amide ions. As expected, the

Figure 6

Solvent-accessible voids of 2479.0 A (ca 30% of the unit-cell volume) in

the structure of diiron complex 9.

3

˚

and N7) are longer than those in the terminal ones (N1 and

`

N9) (vis-a-vis, Bai et al., 2017; Deschner et al., 2011; Olmstead

et al., 1991). Additional selected bond lengths and angles are

given in Table 2.

In addition, the solution magnetic moment of diiron

complex 9 [7.7 (3) ꢀ_B] agrees well with the relatively long

˚

FeÁ Á ÁFe distance of 2.912 (1) A (Malassa et al., 2010; Frazier et

al., 2013), which may be indicative of no interaction between

˚

the dimetal core (the covalent radii sum for Fe—Fe is 2.48 A).

Upon closer inspection of 9 we note that one of the L1^À

ligands coordinated to Fe2 is bound unsymmetrically. Besides

the ꢀ₂-bridging amides binding, there is a stabilizing ipso

interaction between one of the anilide arms and the metal

center. The geometry around atom N1 is distorted tetrahedral,

with the six angles ranging from 85.6 (2) to 130.2 (3)^ꢀ. The

˚

Fe2—C21 bond length is 2.425 (4) A, more than 0.7 A shorter

than the distance to the ipso carbon on the other anilide arm

˚

[Fe2—C38 = 3.181 (5) A]. In addition, the small Fe2—N4—

C21 angle of 85.6 (2)^ꢀsuggests the presence of a weak inter-

action between the p(ꢋ) orbital on C_ipsoand the Fe^IIcenter.

This ipso interaction is likely necessary to stabilize the highly

electrophilic 16-electron Fe center. Such an interaction is

often observed in early-transition or f-block metal complexes

¨

(Tonks et al., 2012; Gountchev & Tilley, 1999; Muller–Busch-

baum & Quitmann, 2003; Odom et al., 1998; Vlaisavljevich et

al., 2013; Haftbaradaran et al., 2005; Evans et al., 1996; Berthet

et al., 2008; Arney et al., 1992). To the best of our knowledge,

compound 9 is the ﬁrst structural report on an Fe^IIÁ Á ÁC_ipso

interaction (Suess & Peters, 2013).

3

˚

Signiﬁcant solvent-accessible voids of 2479.0 A , totalling ca

30% of the unit-cell volume, were observed in the structure of

diiron complex 9 (see Fig. 6 and reﬁnement details). One large

and two smaller void areas are observed, located at the center

of the unit cell, at the origin, and at the center of the A-face of

the unit cell, with the latter two adjacent to each other. The

electron density of the void area at the origin is partially

Figure 7

X-ray crystal structure of the monoiron complex 10. Displacement

ellipsoids are shown at the 50% probability level. Color key: orange = Fe,

blue = N, gray = C, and red = O. H atoms, the disorder of the THF ligands,

and most labels for C and N atoms have been omitted for clarity. A fully

labeled displacement ellipsoid plot with disorder shown and H atoms

included is given in the supporting information.

ꢁ

1646 Lee et al. Iron(II) complexes of dimethyltriazacyclophane

Acta Cryst. (2018). C74, 1641–1649

research papers

Table 3

Bond orders for the Fe—Fe and all the Fe—N bonds in 9.

Entry

Atom 1

Atom 2

Bond order

1

2

3

4

5

6

7

8

Fe1

Fe2

N4

N7

N9

N10

N1

N4

N7

À0.113

0.342

0.296

0.253

0.564

0.556

0.303

0.383

Figure 8

Calculated hypothetical structure (Foscato et al., 2015) of the dicationic

L₂Fe structure, where L = triazacyclophane 4.

and directional interactions are limited to a number of weak

C—HÁ Á Áꢋ contacts, and shape recognition through van der

Waals contacts.

O1—Fe1—O2 angle between the two smaller ligands,

93.90 (7)^ꢀ, is less than the N1—Fe1—N4 angle between the

two large L1^Àgroups. Comparable values were also observed

for [(THF)₂Fe(SSi^tBu₃)₂] with bulky trimethylsilyl thiolate

ions. A lithium tris(diphenylamide)iron(II) complex was

prepared previously by Francke & Francke (1988).

3.3. Theoretical calculations

Bond orders in diiron complex 9 were calculated using

Spartan at the density function level of theory using the EDF2

method with an 6-31G* basis set with heavy atoms frozen.

Bond orders for Fe—Fe and for all Fe—N bonds are listed in

Table 3. The Fe—Fe bond order is negative, indicating no

metal–metal bond, and actually some repulsion.

For direct comparison of the X-ray crystal structure of

diiron complex 9 with the calculated equilibrium geometry

structure, the density functional (6-31G*) result with frozen

heavy atoms was thawed and recalculated with the density

functional level of theory and the EDF2 method and the

6-31G* basis set to yield a geometry-optimized structure. The

key bond lengths for the X-ray crystal structure of the diiron

complex are summarized in Fig. 9, alongside the distances

calculated for the density functional (6-31G*) optimized

Iron(II) ꢁ³-coordinated by unmethylated 4 (Fig. 8) has been

proposed from the results of DFT calculations. We were,

however, unable to obtain complexes with this binding mode.

A bowl-shaped crown conformation of the ortho-triazacyclo-

phane ligand is essential for ꢁ³-coordination, but no crown

conformer was observed in either diiron complex 9 or

monoiron complex 10, and only saddle conformers were

observed. In 9, all the ligands are coordinated to the Fe ions

through only the unmethylated (anionic) amide N atom, while

the methyl-substituted amine donors remain unbound. In 10,

one of the four ligands is coordinated in a chelating fashion

involving the amide and one amine donor, but the remaining

three ligands are again bound solely through their amide N

atoms. An over-estimation in theoretical calculations for the

degree of pyramidalization of the amine N atoms in ligands L1

and L2 could be responsible for the reluctance for this

hypothetical complex to form (Foscato et al., 2015). This

hypothesis is corroborated by the absence of any substantial

intermolecular interactions involving the amine N atoms. They

do not act as acceptors for any of the C—HÁ Á ÁN interactions.

Indeed, intermolecular interactions in both 9 and 10 are sparse

˚

structure. The FeÁ Á ÁFe distance of 2.912 A in the crystal

structure (and further, the FeÁ Á ÁFe distance in the geometry-

˚

optimized DF 6-31G* calculation of 3.012 A) are longer than

˚

typical Fe—Fe bonding distances of 2.46–2.78 A (Pauling,

1976), consistent with the calculated Fe—Fe bond order of

À0.113, indicating no metal–metal bond.

Further, a density functional calculation using the wB97X-D

method with the double-basis set 6-311+G(3df,2p)[6-311G*]

revealed near monocationic charges on each of the Fe atoms,

as well as providing HOMO/LUMO and spin-surface maps.

Figure 9

Key Fe bond distances in Angstroms for (a) the X-ray crystal structure of diiron complex 9 and (b) the density functional (6-31G*) optimized structure

˚

¨

for 9 obtained by starting with the crystal structure and thawing the heavy atoms.

ꢁ

Acta Cryst. (2018). C74, 1641–1649

Lee et al.

Iron(II) complexes of dimethyltriazacyclophane 1647

research papers

Gountchev, T. I. & Tilley, T. D. (1999). Organometallics , 18 , 2896–

2905.

Speciﬁcally, these calculations revealed atomic charges of

+0.998 for Fe1 and +0.961 for Fe2 in diiron complex 9.

Haftbaradaran, F ., Mund, G., Batchelor, R. J., Britten, J. F . & L eznoff,

D. B. (2005). J. Chem. Soc. Dalton Trans. pp. 2343–2345.

Hardie, M. J. (2010). Chem. Soc. Rev. 39 , 516–527.

Hardie, M. J. (2012). Cyclotriveratrylene and Cryptophanes , in

Supramolecular Chemistry , edited by P . A . Gale & J. W. Steed,

Vol. 3, pp. 895–916. London: John Wiley & Sons Ltd.

Herebian, D., Wieghardt, K. E. & Neese, F . (2003). J. Am. Chem. Soc.

125 , 10997–11005.

4. Summary

We describe an improved Buchwald–Hartwig macrocycliza-

tion reaction for the preparation of the ortho-triazacyclophane

L1, which was deprotonated by the internal Fe^IIbase

Fe[N(SiMe₃)₂]₂to afford the unusual diiron complex 9, as

conﬁrmed by X-ray crystallography. Diiron complex 9 was

studied computationally, as well as at the density functional

level of theory that, along with the longer distance between

the Fe atoms, showed no evidence of metal–metal bonding.

Treatment of diiron complex 9 with THF yielded the simpler

(L2)₂Fe(THF)₂complex 10, which reverts to diiron complex 9

in vacuo.

Hicks, R. G. (2008). Angew. Chem. Int. Ed. 47 , 7393–7395.

¨

Hubschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst.

44 , 1281–1284.

Kindermann, N., Schober, A., Demeshko, S., Lehnert, N. & Meyer, F .

(2016). Inorg. Chem. 55 , 11538–11550.

Kochem, A., Gellon, G., Leconte, N., Baptiste, B., Philouze, C.,

Jarjayes, O., Orio, M. & Thomas, F. (2013). Chem. Eur. J. 19 , 16707–

16721.

Kopf, J., Von Deuten, K. & Klar, G. (1979). Cryst. Struct. Commun. 8 ,

1011–1016.

Leconte, N., Ciccione, J., Gellon, G., Philouze, C. & Thomas, F . (2014).

Chem. Commun. 50 , 1918–1920.

Leconte, N., Moutet, J., Herasymchuk, K., Clarke, R. M., Philouze, C.,

Luneau, D., Storr, T. & Thomas, F . (2017). Chem. Commun. 53 ,

2764–2767.

Lutz, M. R., Ernst, E., Zeller, M., Dudzinski, J., Thoresen, P . &

Becker, D. P . (2018). Eur J. Org. Chem. doi: 10.1002ejoc.201800788.

Lutz, M. R., Zeller, M., Sarsah, S. R. S., Filipowicz, A., Wouters, H. &

Becker, D. P . (2012). Supramol. Chem. 24 , 803–809.

Lyaskovskyy, V . & d e Bruin, B. (2012). ACS Catal. 2 , 270–279.

Acknowledgements

This work was supported by start-up funds (Loyola University

Chicago). The X-ray diffractometers were funded by the

National Science Foundation through the Major Research

Instrumentation Program (funding for the single-crystal X-ray

diffractometer).

¨

Malassa, A., Agthe, C., Gorls, H., Friedrich, M. & Westerhausen, M.

Funding information

(2010). J. Organomet. Chem. 695 , 1641–1650.

Mitra, M., Lloret-Fillol, J., Haukka, M., Costas, M. & Nordlander, E.

(2014). Chem. Commun. 50 , 1408–1410.

Muller–Buschbaum, K. & Quitmann, C. C. (2003). Z. Anorg. Allg.

Chem. 629 , 1610–1616.

Funding for this research was provided by: National Science

Foundation, Major Research Instrumentation (award No.

DMR 1337296 to MZ).

¨

Nakanishi, S., Kawamura, M., Sunada, Y . & N agashima, H. (2016).

Polym. Chem. 7 , 1037–1048.

Odom, A. L., Arnold, P . L . & Cummins, C. C. (1998). J. Am. Chem.

Soc. 120 , 5836–5837.

Ohki, Y ., Ohta, S. & Tatsumi, K. (2010). Bio-inspired Iron and Nickel

Complexes , pp. 129–147. New York: Wiley & Sons Inc.

Olmstead, M. M., Power, P . P. & S honer, S. C. (1991). Inorg. Chem. 30 ,

2547–2551.

Panagopoulos, A. M., Steinman, D., Goncharenko, A., Geary, K.,

Schleisman, C., Spaargaren, E., Zeller, M. & Becker, D. P . (2013). J.

Org. Chem. 78 , 3532–3540.

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Iron(II) complexes of dimethyltriazacyclophane 1649

supporting information

Acta Cryst. (2018). C74, 1641-1649 [https://doi.org/10.1107/S2053229618015255]

Iron(II) complexes of dimethyltriazacyclophane

Wei-Tsung Lee, Matthias Zeller, David Upp, Yuliya Politanska, Doug Steinman, Talal Al-Assil and

Daniel P. Becker

Computing details

For both structures, data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction:

SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine

structure: SHELXL2014 (Sheldrick, 2015) and SHELXLE (Hübschle et al., 2011); software used to prepare material for

publication: publCIF (Westrip, 2010).

Bis(µ-1,4-dimethyltribenzo[b,e,h][1,4,7]triazacyclonona-2,5,8-trien-7-ido)-1:2κ²N¹,N⁷:κN⁷; 1:2κN⁷:κ²N⁷,C⁶-

bis[(µ-1,4-dimethyltribenzo[b,e,h][1,4,7]triazacyclonona-2,5,8-trien-7-ido-κN⁷)iron(II)] (9)

Crystal data

[Fe(C₂₀H₁₈N₃)₄]

M_r= 1313.19

F(000) = 2752

D_x= 1.059 Mg m⁻³

Cu Kα radiation, λ = 1.54178 Å

Cell parameters from 8887 reflections

θ = 3.0–65.8°

Monoclinic, P2₁/c

a = 21.758 (2) Å

b = 12.7682 (13) Å

c = 31.382 (3) Å

β = 109.191 (5)°

V = 8233.7 (14) Å³

Z = 4

µ = 3.17 mm⁻¹

T = 100 K

Rod, red

0.11 × 0.06 × 0.05 mm

Data collection

Bruker Prospector CCD

diffractometer

Radiation source: I-mu-S microsource X-ray

tube

Laterally graded multilayer (Goebel) mirror

monochromator

T_min= 0.478, T_max= 0.753

52565 measured reflections

14191 independent reflections

8827 reflections with I > 2σ(I)

R_int= 0.133

θ

_max= 66.9°, θ_min= 2.2°

ω and phi scans

Absorption correction: multi-scan

(APEX2; Bruker, 2014)

h = −25→25

k = −14→15

l = −23→37

Refinement

Refinement on F²

Least-squares matrix: full

R[F²> 2σ(F²)] = 0.076

wR(F²) = 0.193

S = 1.03

14191 reflections

855 parameters

0 restraints

Primary atom site location: structure-invariant

direct methods

Secondary atom site location: difference Fourier

map

Hydrogen site location: inferred from

neighbouring sites

H-atom parameters constrained

Acta Cryst. (2018). C74, 1641-1649

sup-1

supporting information

w = 1/[σ²(F_o²) + (0.0816P)²+ 5.4245P]

where P = (F_o²+ 2F_c²)/3

(Δ/σ)_max< 0.001

Δρ_max= 0.79 e Å⁻³

Δρ_min= −0.54 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.

Refinement. The structure contains solvent accessible voids of 2479.0 Ang3 (30% of the unit cell volume). The the

residual electron density peaks were not arranged in an interpretable pattern. The hkl file was thus corrected using reverse

Fourier transform methods using the SQUEEZE routine (P. van der Sluis & Spek (1990). Acta Cryst. A46, 194-201) as

implemented in the program Platon. The resultant files were used in the further refinement. (The FAB file with details of

the Squeeze results is appended to this cif file). The Squeeze procedure corrected for 569.8 electrons within the solvent

accesible voids, equivalent of eight molecules of tetrahydro furane (the crystallization solvent).

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

x

y

z

U_iso*/U_eq

C1

C2

H2

0.2847 (2)

0.2243 (2)

0.2097

0.3704 (4)

0.3887 (4)

0.3425

0.38404 (15)

0.35057 (15)

0.3255

0.0336 (11)

0.0339 (11)

0.041*

C3

H3

0.1860 (2)

0.1453

0.4723 (4)

0.4826

0.35341 (17)

0.3304

0.0418 (13)

0.050*

C4

H4

0.2056 (3)

0.1784

0.5413 (4)

0.5977

0.38898 (18)

0.3914

0.0509 (15)

0.061*

C5

H5

0.2668 (2)

0.2819

0.5262 (4)

0.5747

0.42160 (17)

0.4457

0.0462 (14)

0.055*

C6

C7

C8

H8

0.3053 (2)

0.4093 (2)

0.4367 (2)

0.4317

0.4428 (4)

0.5186 (4)

0.5861 (4)

0.5719

0.41940 (16)

0.45291 (16)

0.48879 (17)

0.5172

0.0367 (12)

0.0395 (12)

0.0457 (14)

0.055*

C9

H9

0.4713 (3)

0.4911

0.6743 (4)

0.7186

0.48399 (19)

0.5091

0.0510 (15)

0.061*

C10

H10

C11

H11

C12

C13

C14

H14

C15

H15

C16

H16

C17

H17

C18

0.4768 (3)

0.4971

0.4526 (2)

0.4584

0.4198 (2)

0.4224 (2)

0.4872 (2)

0.5136

0.5148 (3)

0.5597

0.6969 (4)

0.7602

0.6272 (4)

0.6421

0.5352 (4)

0.3570 (4)

0.3433 (4)

0.4031

0.2450 (4)

0.2367

0.4424 (2)

0.4383

0.40623 (18)

0.3781

0.41123 (16)

0.38532 (15)

0.39039 (16)

0.3915

0.39382 (17)

0.3975

0.0552 (16)

0.066*

0.0487 (14)

0.058*

0.0398 (12)

0.0364 (12)

0.0413 (12)

0.050*

0.0494 (14)

0.059*

0.4750 (2)

0.4925

0.4108 (2)

0.3846

0.1579 (4)

0.0893

0.1712 (4)

0.1109

0.39176 (16)

0.3932

0.38768 (15)

0.3861

0.0446 (13)

0.053*

0.0362 (11)

0.043*

0.3823 (2)

0.2705 (4)

0.38573 (15)

0.0336 (11)

Acta Cryst. (2018). C74, 1641-1649

sup-2

supporting information

C19

0.3620 (2)

0.3348

0.3417

0.4052

0.3840 (3)

0.3566

0.4097 (4)

0.3473

0.4697

0.3973

0.4952 (4)

0.4434

0.49871 (16)

0.4966

0.5083

0.5208

0.33024 (16)

0.3095

0.0444 (13)

0.067*

0.0550 (15)

0.083*

H19A

H19B

H19C

C20

H20A

H20B

H20C

C21

C22

H22

C23

H23

C24

H24

C25

H25

C26

C27

C28

H28

C29

H29

C30

H30

C31

H31

C32

C33

C34

H34

C35

H35

C36

H36

C37

H37

C38

C39

H39A

H39B

H39C

C40

H40A

H40B

H40C

C41

0.4257

0.3620

0.5011

0.5633

0.3249

0.3251

0.083*

0.1671 (2)

0.1206 (2)

0.1141

0.0841 (2)

0.0532

0.0924 (2)

0.0662

0.1398 (2)

0.1467

0.1770 (2)

0.2018 (2)

0.2236 (3)

0.2593

0.1935 (3)

0.2095

0.1410 (3)

0.1192

0.1202 (3)

0.0844

0.1507 (2)

0.1904 (2)

0.2103 (3)

0.1873

0.2626 (3)

0.2749

0.2962 (3)

0.3320

0.2781 (2)

0.3031

0.2235 (2)

0.2869 (2)

0.3206

0.3015

0.2788

0.1208 (3)

0.1744 (3)

0.1550

0.2552 (3)

0.2909

0.2842 (4)

0.3374

0.2342 (4)

0.2555

0.1544 (4)

0.0586 (4)

0.0819 (4)

0.1282

0.0383 (5)

0.0540

−0.0274 (5)

−0.0539

−0.0548 (4)

−0.1014

−0.0152 (4)

−0.0967 (4)

−0.1934 (4)

−0.2231

−0.2482 (4)

−0.3147

−0.2022 (5)

−0.2378

−0.1059 (4)

−0.0749

−0.0516 (4)

0.1660 (4)

0.1233

0.1867

0.2288

0.31601 (14)

0.32995 (14)

0.3574

0.30420 (15)

0.3143

0.26395 (15)

0.2457

0.25073 (15)

0.2237

0.27575 (14)

0.21864 (15)

0.18263 (17)

0.1870

0.14064 (18)

0.1166

0.13302 (17)

0.1036

0.16902 (15)

0.1641

0.21207 (15)

0.28417 (15)

0.27291 (17)

0.2443

0.30196 (19)

0.2939

0.34327 (18)

0.3638

0.35466 (15)

0.3825

0.32614 (14)

0.27151 (16)

0.2655

0.3034

0.2525

0.0284 (10)

0.0285 (10)

0.034*

0.0304 (10)

0.036*

0.0334 (11)

0.040*

0.0320 (11)

0.038*

0.0313 (11)

0.0380 (12)

0.0528 (15)

0.063*

0.0631 (18)

0.076*

0.0627 (18)

0.075*

0.0470 (14)

0.056*

0.0376 (12)

0.0356 (11)

0.0436 (13)

0.052*

0.0604 (17)

0.072*

0.0571 (16)

0.069*

0.0386 (12)

0.046*

0.0301 (10)

0.0429 (13)

0.064*

0.0735 (2)

0.0389

0.0650

0.0745

0.2244 (2)

0.1949 (2)

−0.0973 (4)

−0.0560

−0.1033

−0.1674

0.1888 (4)

0.2835 (4)

0.24384 (15)

0.2226

0.2726

0.2314

0.46888 (15)

0.45118 (16)

0.0366 (12)

0.055*

0.0305 (11)

0.0345 (11)

C42

Acta Cryst. (2018). C74, 1641-1649

sup-3

supporting information

H42

C43

H43

C44

H44

C45

H45

C46

C47

C48

H48

C49

H49

C50

H50

C51

H51

C52

C53

C54

H54

C55

H55

C56

H56

C57

H57

C58

C59

H59A

H59B

H59C

C60

H60A

H60B

H60C

C61

C62

H62

C63

H63

C64

H64

C65

H65

C66

C67

C68

0.1842

0.1809 (3)

0.1602

0.1968 (3)

0.1886

0.2250 (3)

0.2361

0.2375 (2)

0.2139 (2)

0.1787 (2)

0.1885

0.1303 (3)

0.1075

0.1159 (3)

0.0826

0.1492 (2)

0.1375

0.1998 (2)

0.2967 (2)

0.3533 (2)

0.3512

0.4128 (2)

0.4515

0.4163 (2)

0.4573

0.3599 (2)

0.3625

0.2997 (2)

0.3147 (2)

0.3490

0.3329

0.2973

0.2963

0.3585 (4)

0.4217

0.3425 (4)

0.3953

0.2480 (4)

0.2370

0.1695 (4)

−0.0121 (4)

−0.0102 (4)

0.0425

−0.0812 (5)

−0.0789

−0.1555 (4)

−0.2054

−0.1588 (4)

−0.2096

−0.0884 (4)

−0.0500 (4)

−0.1058 (4)

−0.1785

−0.0553 (4)

−0.0936

0.0504 (4)

0.0849

0.1058 (4)

0.1784

0.0570 (4)

0.0667 (4)

0.1159

−0.0041

0.0870

0.4198

0.47771 (19)

0.4646

0.5234 (2)

0.5422

0.54172 (17)

0.5733

0.51516 (15)

0.52683 (15)

0.55643 (16)

0.5791

0.55451 (17)

0.5757

0.52102 (17)

0.5189

0.49038 (16)

0.4670

0.49323 (14)

0.47170 (15)

0.49256 (15)

0.4984

0.50488 (17)

0.5192

0.49650 (17)

0.5053

0.47530 (15)

0.4694

0.46250 (14)

0.57586 (15)

0.5752

0.5817

0.5998

0.041*

0.0470 (13)

0.056*

0.0585 (16)

0.070*

0.0469 (14)

0.056*

0.0356 (11)

0.0350 (11)

0.0427 (12)

0.051*

0.0517 (14)

0.062*

0.0467 (13)

0.056*

0.0427 (13)

0.051*

0.0319 (11)

0.0334 (11)

0.0400 (12)

0.048*

0.0474 (14)

0.057*

0.0459 (13)

0.055*

0.0371 (12)

0.044*

0.0309 (11)

0.0479 (14)

0.058*

0.2344 (3)

0.1900

0.2536

−0.2094 (4)

−0.2332

−0.2539

0.44436 (16)

0.4282

0.4709

0.0427 (13)

0.064*

0.2607

−0.2139

0.4244

0.064*

0.0408 (2)

0.0637 (2)

0.1019

0.0333 (2)

0.0513

−0.0238 (2)

−0.0452

−0.0486 (2)

−0.0884

−0.0181 (2)

−0.1073 (2)

−0.1663 (2)

0.0432 (3)

0.1056 (4)

0.0843

0.1961 (3)

0.2370

0.2280 (4)

0.2909

0.1649 (3)

0.1846

0.39382 (13)

0.43271 (14)

0.4561

0.43842 (14)

0.4649

0.40555 (15)

0.4088

0.36772 (14)

0.3455

0.0273 (10)

0.0309 (11)

0.037*

0.0313 (11)

0.038*

0.0342 (11)

0.041*

0.0291 (10)

0.035*

0.0751 (3)

−0.0313 (4)

−0.0093 (4)

0.36100 (13)

0.31871 (14)

0.28458 (15)

0.0257 (10)

0.0325 (11)

0.0372 (12)

Acta Cryst. (2018). C74, 1641-1649

sup-4

supporting information

H68

C69

H69

C70

H70

C71

H71

C72

C73

C74

H74

C75

H75

C76

H76

C77

H77

C78

C79

H79A

H79B

H79C

C80

H80A

H80B

H80C

Fe1

Fe2

N1

N2

N3

N4

N5

N6

N7

N8

N9

N10

N11

N12

−0.1667

−0.2235 (2)

−0.2631

−0.2242 (2)

−0.2641

−0.1657 (2)

−0.1658

−0.1073 (2)

−0.0028 (2)

−0.0188 (2)

−0.0590

0.0201 (2)

0.0075

0.0781 (2)

0.1059

0.0964 (2)

0.1368

0.0569 (2)

−0.0450 (2)

−0.0621

0.0001

−0.0715

−0.0478 (2)

−0.0658

−0.0751

0.0356

−0.0522 (4)

−0.0365

−0.1180 (4)

−0.1455

−0.1435 (4)

−0.1907

−0.1012 (4)

−0.1795 (4)

−0.2791 (4)

−0.3087

−0.3376 (4)

−0.4055

−0.2930 (4)

−0.3306

−0.1947 (4)

−0.1667

−0.1339 (3)

0.0685 (4)

0.0224

0.0873

0.1321

−0.1707 (4)

−0.2417

−0.1268

0.2604

0.28602 (16)

0.2628

0.32079 (16)

0.3221

0.35389 (15)

0.3773

0.35337 (14)

0.36796 (14)

0.34968 (15)

0.3496

0.33164 (15)

0.3195

0.33209 (14)

0.3197

0.35019 (14)

0.3501

0.36900 (13)

0.27994 (14)

0.2537

0.2835

0.2754

0.42861 (15)

0.4235

0.4408

0.045*

0.0427 (13)

0.051*

0.0411 (12)

0.049*

0.0348 (11)

0.042*

0.0317 (11)

0.0320 (11)

0.0356 (11)

0.043*

0.0393 (12)

0.047*

0.0356 (11)

0.043*

0.0325 (11)

0.039*

0.0280 (10)

0.0354 (11)

0.053*

0.0432 (13)

0.065*

−0.0035

−0.1731

0.4502

0.065*

0.17367 (3)

0.25881 (3)

0.31703 (17)

0.36834 (18)

0.39530 (19)

0.20378 (16)

0.22650 (18)

0.13593 (18)

0.24007 (17)

0.26247 (18)

0.23263 (18)

0.08062 (16)

−0.04708 (17)

−0.04644 (17)

0.00329 (6)

0.15927 (6)

0.2743 (3)

0.4317 (3)

0.4622 (3)

0.0392 (3)

0.1048 (3)

−0.0458 (3)

0.1133 (3)

0.0687 (3)

−0.0987 (3)

−0.0371 (3)

0.0144 (3)

−0.1268 (3)

0.40199 (2)

0.38298 (2)

0.38190 (12)

0.45443 (13)

0.37670 (13)

0.34477 (11)

0.26126 (12)

0.25134 (12)

0.44047 (11)

0.53236 (12)

0.45908 (11)

0.38772 (11)

0.32030 (11)

0.38618 (11)

0.02762 (18)

0.03122 (19)

0.0315 (9)

0.0384 (10)

0.0399 (10)

0.0277 (8)

0.0374 (10)

0.0330 (9)

0.0292 (9)

0.0344 (9)

0.0317 (9)

0.0268 (8)

0.0298 (9)

0.0282 (8)

Atomic displacement parameters (Å²)

U¹¹

U²²

U³³

U¹²

U¹³

U²³

C1

C2

C3

C4

0.028 (2)

0.034 (3)

0.031 (3)

0.039 (3)

0.033 (3)

0.026 (3)

0.034 (3)

0.038 (3)

0.035 (3)

0.046 (3)

0.061 (4)

−0.002 (2)

−0.001 (2)

0.003 (2)

0.016 (2)

0.004 (2)

0.002 (2)

−0.007 (2)

−0.004 (3)

0.002 (2)

0.001 (2)

−0.001 (2)

−0.006 (3)

Acta Cryst. (2018). C74, 1641-1649

sup-5

supporting information

C5

C6

C7

C8

0.040 (3)

0.022 (2)

0.029 (3)

0.036 (3)

0.039 (3)

0.040 (3)

0.034 (3)

0.033 (3)

0.027 (2)

0.036 (3)

0.032 (3)

0.038 (3)

0.032 (3)

0.031 (3)

0.038 (3)

0.059 (4)

0.026 (2)

0.024 (2)

0.026 (2)

0.024 (2)

0.038 (3)

0.067 (4)

0.093 (5)

0.095 (5)

0.067 (4)

0.041 (3)

0.036 (3)

0.047 (3)

0.067 (4)

0.054 (4)

0.035 (3)

0.025 (2)

0.028 (3)

0.039 (3)

0.022 (2)

0.035 (3)

0.050 (3)

0.073 (4)

0.064 (4)

0.038 (3)

0.039 (3)

0.047 (3)

0.058 (4)

0.044 (3)

0.041 (3)

0.034 (3)

0.042 (3)

0.040 (3)

0.035 (3)

0.043 (3)

0.045 (3)

0.043 (3)

0.051 (3)

0.038 (3)

0.044 (3)

0.050 (3)

0.063 (4)

0.055 (4)

0.042 (3)

0.038 (3)

0.050 (3)

0.058 (4)

0.028 (2)

0.035 (3)

0.027 (3)

0.036 (3)

0.040 (3)

0.042 (3)

0.050 (3)

0.062 (4)

0.073 (4)

0.070 (4)

0.041 (3)

0.043 (3)

0.035 (3)

0.040 (3)

0.048 (4)

0.064 (4)

0.048 (3)

0.040 (3)

0.064 (4)

0.035 (3)

0.037 (3)

0.035 (3)

0.037 (3)

0.042 (4)

0.047 (3)

0.035 (3)

0.050 (3)

0.067 (4)

0.055 (4)

0.045 (3)

0.036 (3)

0.046 (3)

0.041 (3)

0.045 (3)

0.048 (3)

0.063 (4)

0.046 (3)

0.035 (3)

0.032 (3)

0.036 (3)

0.051 (3)

0.040 (3)

0.032 (3)

0.029 (2)

0.036 (3)

0.034 (3)

0.025 (2)

0.039 (3)

0.036 (3)

0.027 (2)

0.026 (2)

0.027 (3)

0.036 (3)

0.030 (3)

0.020 (3)

0.028 (3)

0.024 (2)

0.034 (3)

0.039 (3)

0.057 (4)

0.046 (3)

0.030 (3)

0.027 (2)

0.037 (3)

0.031 (3)

0.033 (3)

0.036 (3)

0.059 (4)

0.072 (4)

0.036 (3)

0.035 (3)

0.027 (2)

0.035 (3)

0.037 (3)

0.042 (3)

0.034 (3)

0.023 (2)

0.004 (2)

0.005 (2)

0.007 (2)

0.007 (3)

0.003 (3)

−0.003 (3)

−0.004 (3)

0.005 (2)

0.001 (2)

−0.007 (3)

0.007 (3)

0.012 (3)

0.000 (2)

0.001 (2)

0.002 (3)

−0.005 (3)

0.000 (2)

−0.003 (2)

0.0000 (19)

−0.003 (2)

−0.004 (2)

−0.007 (2)

0.002 (2)

−0.006 (3)

−0.016 (4)

−0.008 (4)

−0.002 (3)

0.010 (2)

0.003 (2)

0.011 (3)

0.029 (3)

0.026 (3)

0.012 (2)

0.006 (2)

−0.002 (3)

0.002 (2)

−0.002 (2)

0.000 (2)

0.000 (3)

−0.008 (3)

−0.007 (3)

−0.010 (2)

0.001 (2)

−0.008 (3)

−0.007 (3)

−0.003 (3)

−0.001 (2)

0.000 (2)

−0.007 (2)

−0.004 (2)

−0.014 (2)

−0.010 (3)

−0.008 (2)

−0.007 (2)

0.0016 (19)

0.010 (2)

0.011 (2)

−0.009 (2)

0.003 (2)

0.005 (2)

−0.004 (2)

−0.006 (3)

0.003 (3)

0.009 (3)

0.004 (2)

0.002 (2)

0.005 (3)

−0.002 (3)

−0.001 (2)

0.003 (2)

−0.007 (2)

0.011 (3)

−0.0003 (19)

−0.001 (2)

−0.003 (2)

0.008 (2)

0.003 (2)

−0.005 (2)

0.001 (2)

−0.007 (3)

−0.008 (3)

−0.006 (2)

0.002 (2)

−0.005 (2)

−0.014 (3)

−0.001 (3)

0.000 (2)

0.002 (2)

−0.002 (3)

0.000 (2)

−0.008 (2)

−0.003 (2)

−0.011 (3)

−0.023 (3)

−0.014 (3)

−0.013 (2)

0.005 (2)

−0.003 (2)

−0.001 (3)

0.011 (3)

C9

C10

C11

C12

C13

C14

C15

C16

C17

C18

C19

C20

C21

C22

C23

C24

C25

C26

C27

C28

C29

C30

C31

C32

C33

C34

C35

C36

C37

C38

C39

C40

C41

C42

C43

C44

C45

C46

C47

C48

C49

C50

C51

C52

0.012 (2)

0.007 (2)

0.0057 (19)

−0.001 (2)

−0.003 (2)

0.0004 (18)

0.0080 (18)

0.0082 (19)

0.0033 (19)

0.0046 (19)

0.0050 (18)

0.012 (2)

0.025 (3)

0.030 (3)

0.015 (3)

0.008 (2)

0.005 (2)

0.009 (2)

0.007 (2)

0.008 (3)

0.007 (3)

0.007 (2)

0.0103 (18)

0.012 (2)

0.004 (2)

0.0090 (18)

0.016 (2)

0.024 (3)

0.039 (3)

0.025 (3)

0.013 (2)

0.006 (2)

0.019 (2)

0.025 (3)

0.015 (2)

0.001 (2)

0.0043 (19)

−0.001 (2)

0.003 (2)

Acta Cryst. (2018). C74, 1641-1649

sup-6

supporting information

C53

C54

C55

C56

C57

C58

C59

C60

C61

C62

C63

C64

C65

C66

C67

C68

C69

C70

C71

C72

C73

C74

C75

C76

C77

C78

C79

C80

Fe1

Fe2

N1

0.029 (2)

0.043 (3)

0.024 (3)

0.032 (3)

0.029 (3)

0.028 (2)

0.045 (3)

0.053 (3)

0.027 (2)

0.029 (2)

0.040 (3)

0.033 (3)

0.033 (2)

0.026 (2)

0.030 (2)

0.033 (3)

0.027 (3)

0.027 (2)

0.031 (3)

0.028 (2)

0.033 (3)

0.030 (3)

0.040 (3)

0.035 (3)

0.030 (2)

0.029 (2)

0.037 (3)

0.038 (3)

0.0246 (3)

0.0281 (4)

0.0237 (19)

0.026 (2)

0.037 (2)

0.0224 (18)

0.031 (2)

0.032 (2)

0.0236 (19)

0.032 (2)

0.036 (2)

0.0184 (17)

0.031 (2)

0.0223 (18)

0.043 (3)

0.044 (3)

0.058 (4)

0.054 (4)

0.049 (3)

0.037 (3)

0.067 (4)

0.033 (3)

0.034 (3)

0.036 (3)

0.030 (3)

0.033 (3)

0.030 (3)

0.028 (3)

0.042 (3)

0.046 (3)

0.066 (4)

0.055 (3)

0.045 (3)

0.038 (3)

0.035 (3)

0.034 (3)

0.040 (3)

0.041 (3)

0.040 (3)

0.033 (3)

0.042 (3)

0.056 (3)

0.0327 (4)

0.0352 (4)

0.030 (2)

0.043 (3)

0.038 (2)

0.036 (2)

0.050 (3)

0.037 (2)

0.036 (2)

0.042 (2)

0.031 (2)

0.029 (2)

0.033 (2)

0.034 (2)

0.029 (2)

0.033 (3)

0.054 (3)

0.050 (3)

0.031 (3)

0.029 (2)

0.027 (3)

0.035 (3)

0.021 (2)

0.027 (2)

0.026 (2)

0.035 (3)

0.024 (2)

0.022 (2)

0.024 (2)

0.028 (2)

0.030 (3)

0.040 (3)

0.029 (2)

0.024 (2)

0.037 (3)

0.032 (3)

0.027 (2)

0.024 (2)

0.020 (2)

0.024 (2)

0.032 (3)

0.0226 (3)

0.0279 (4)

0.037 (2)

0.035 (2)

0.034 (2)

0.0243 (19)

0.030 (2)

0.025 (2)

0.026 (2)

0.025 (2)

0.0237 (19)

0.028 (2)

0.0239 (19)

0.0244 (19)

0.007 (2)

0.009 (2)

0.012 (3)

0.001 (3)

0.006 (2)

0.005 (2)

−0.012 (3)

0.003 (2)

−0.002 (2)

0.000 (2)

−0.008 (2)

0.005 (2)

0.002 (2)

−0.0020 (19)

0.003 (2)

0.009 (2)

0.008 (3)

−0.001 (2)

0.001 (2)

0.000 (2)

0.007 (2)

0.0106 (19)

0.013 (2)

0.004 (2)

0.010 (2)

0.006 (2)

0.0102 (19)

0.006 (2)

0.004 (2)

0.0083 (18)

0.0081 (19)

0.013 (2)

0.000 (2)

0.010 (2)

0.012 (3)

0.006 (3)

0.006 (2)

−0.003 (2)

−0.007 (3)

−0.002 (2)

−0.0014 (19)

0.002 (2)

−0.007 (2)

0.000 (2)

0.005 (2)

0.0036 (19)

−0.004 (2)

0.000 (2)

−0.004 (3)

−0.010 (3)

0.000 (2)

−0.005 (2)

0.002 (2)

0.003 (2)

0.009 (2)

0.0077 (18)

0.0065 (17)

0.0069 (18)

0.0038 (19)

0.003 (2)

0.008 (2)

0.011 (2)

0.0025 (18)

0.0031 (19)

0.003 (2)

−0.003 (2)

0.006 (2)

0.013 (2)

0.005 (2)

0.006 (2)

0.004 (2)

−0.007 (2)

−0.002 (2)

0.001 (2)

0.0056 (19)

0.003 (2)

0.0050 (19)

0.0035 (18)

0.0051 (18)

0.007 (2)

0.001 (2)

0.004 (3)

0.007 (2)

0.009 (2)

0.0008 (3)

−0.0007 (3)

−0.0012 (17)

0.0028 (19)

−0.0011 (19)

0.0062 (16)

−0.0004 (19)

0.0025 (18)

0.0035 (17)

−0.0081 (19)

−0.0001 (18)

−0.0028 (16)

0.0048 (17)

0.0018 (16)

0.0037 (3)

0.0058 (3)

0.0041 (16)

−0.0040 (17)

−0.0020 (18)

0.0071 (15)

0.0092 (17)

0.0015 (16)

0.0058 (15)

0.0049 (16)

0.0042 (16)

0.0013 (14)

0.0070 (15)

0.0031 (15)

−0.0012 (3)

−0.0004 (3)

0.0004 (17)

0.0025 (19)

0.0014 (19)

−0.0028 (16)

0.0023 (19)

0.0009 (17)

−0.0040 (17)

−0.0054 (18)

−0.0003 (17)

−0.0057 (16)

0.0022 (16)

0.0019 (16)

N2

N3

N4

N5

N6

N7

N8

N9

N10

N11

N12

Geometric parameters (Å, º)

C1—C6

C1—C2

C1—N1

1.401 (6)

1.406 (6)

1.426 (6)

C42—H42

C43—C44

C43—H43

0.9500

1.375 (8)

0.9500

Acta Cryst. (2018). C74, 1641-1649

sup-7

supporting information

C2—C3

C2—H2

C3—C4

C3—H3

C4—C5

C4—H4

C5—C6

C5—H5

C6—N2

C7—C8

C7—C12

C7—N2

C8—C9

C8—H8

C9—C10

C9—H9

C10—C11

C10—H10

C11—C12

C11—H11

C12—N3

C13—C14

C13—C18

C13—N3

C14—C15

C14—H14

C15—C16

C15—H15

C16—C17

C16—H16

C17—C18

C17—H17

C18—N1

C19—N2

C19—H19A

C19—H19B

C19—H19C

C20—N3

C20—H20A

C20—H20B

C20—H20C

C21—C22

C21—C26

C21—N4

C21—Fe2

C22—C23

C22—H22

C23—C24

1.376 (6)

0.9500

1.375 (7)

0.9500

1.401 (6)

0.9500

1.370 (7)

0.9500

1.456 (5)

1.388 (7)

1.416 (7)

1.434 (6)

1.391 (7)

0.9500

1.378 (8)

0.9500

1.403 (7)

0.9500

C44—C45

C44—H44

C45—C46

C45—H45

C46—N8

C47—C48

C47—C52

C47—N8

C48—C49

C48—H48

C49—C50

C49—H49

C50—C51

C50—H50

C51—C52

C51—H51

C52—N9

1.390 (7)

0.9500

1.386 (6)

0.9500

1.432 (6)

1.384 (6)

1.394 (6)

1.446 (6)

1.378 (7)

0.9500

1.373 (7)

0.9500

1.381 (7)

0.9500

1.401 (7)

0.9500

1.476 (6)

1.386 (6)

1.401 (6)

1.458 (6)

1.382 (7)

0.9500

1.382 (7)

0.9500

1.383 (6)

0.9500

1.385 (6)

0.9500

1.446 (5)

1.461 (5)

0.9800

C53—C54

C53—C58

C53—N9

1.410 (7)

0.9500

1.395 (6)

1.377 (7)

1.411 (7)

1.456 (6)

1.381 (7)

0.9500

1.397 (7)

0.9500

1.372 (7)

0.9500

1.403 (6)

0.9500

1.386 (6)

1.468 (6)

0.9800

C54—C55

C54—H54

C55—C56

C55—H55

C56—C57

C56—H56

C57—C58

C57—H57

C58—N7

C59—N8

C59—H59A

C59—H59B

C59—H59C

C60—N9

0.9800

1.492 (6)

0.9800

C60—H60A

C60—H60B

C60—H60C

C61—N10

C61—C62

C61—C66

C62—C63

C62—H62

C63—C64

C63—H63

C64—C65

C64—H64

C65—C66

C65—H65

0.9800

1.459 (6)

0.9800

1.395 (5)

1.405 (6)

1.414 (6)

1.372 (6)

0.9500

1.389 (6)

0.9500

1.389 (6)

0.9500

0.9800

1.404 (6)

1.417 (6)

1.436 (5)

2.426 (4)

1.388 (6)

0.9500

1.375 (6)

0.9500

1.384 (6)

Acta Cryst. (2018). C74, 1641-1649

sup-8

supporting information

C23—H23

C24—C25

C24—H24

C25—C26

C25—H25

C26—N5

0.9500

1.386 (6)

0.9500

1.376 (6)

0.9500

1.445 (6)

1.394 (7)

1.398 (6)

1.419 (7)

1.381 (7)

0.9500

1.373 (8)

0.9500

1.393 (7)

0.9500

C66—N11

C67—C68

C67—C72

C67—N11

C68—C69

C68—H68

C69—C70

C69—H69

C70—C71

C70—H70

C71—C72

C71—H71

C72—N12

C73—C74

C73—C78

C73—N12

C74—C75

C74—H74

C75—C76

C75—H75

C76—C77

C76—H76

C77—C78

C77—H77

C78—N10

C79—N11

C79—H79A

C79—H79B

C79—H79C

C80—N12

C80—H80A

C80—H80B

C80—H80C

Fe1—N10

Fe1—N7

1.449 (5)

1.403 (6)

1.407 (6)

1.421 (6)

1.375 (7)

0.9500

1.381 (7)

0.9500

1.391 (6)

0.9500

C27—C28

C27—N5

C27—C32

C28—C29

C28—H28

C29—C30

C29—H29

C30—C31

C30—H30

C31—C32

C31—H31

C32—N6

1.387 (6)

0.9500

1.422 (5)

1.392 (6)

1.414 (6)

1.428 (6)

1.383 (7)

0.9500

1.381 (7)

0.9500

1.382 (6)

0.9500

1.423 (6)

0.9500

1.393 (5)

1.456 (5)

0.9800

1.390 (6)

0.9500

1.427 (6)

1.392 (6)

1.401 (6)

1.444 (6)

1.390 (7)

0.9500

1.392 (7)

0.9500

1.373 (7)

0.9500

1.413 (6)

0.9500

1.426 (6)

1.470 (6)

0.9800

C33—C34

C33—C38

C33—N6

C34—C35

C34—H34

C35—C36

C35—H35

C36—C37

C36—H36

C37—C38

C37—H37

C38—N4

0.9800

1.454 (6)

0.9800

C39—N5

C39—H39A

C39—H39B

C39—H39C

C40—N6

C40—H40A

C40—H40B

C40—H40C

C41—C42

C41—C46

C41—N7

0.9800

1.458 (6)

0.9800

1.992 (3)

2.091 (4)

2.154 (4)

2.245 (3)

2.9121 (10)

1.947 (4)

2.061 (4)

2.068 (4)

Fe1—N4

Fe1—N9

Fe1—Fe2

Fe2—N1

Fe2—N7

0.9800

1.396 (6)

1.407 (6)

1.429 (5)

1.367 (6)

Fe2—N4

C42—C43

C6—C1—C2

C6—C1—N1

C2—C1—N1

C3—C2—C1

C3—C2—H2

117.3 (4)

124.8 (4)

117.5 (4)

121.2 (4)

119.4

C50—C51—H51

C52—C51—H51

C47—C52—C51

C47—C52—N9

C51—C52—N9

119.4

118.0 (5)

124.9 (4)

117.0 (4)

Acta Cryst. (2018). C74, 1641-1649

sup-9

supporting information

C1—C2—H2

C4—C3—C2

C4—C3—H3

C2—C3—H3

C3—C4—C5

C3—C4—H4

C5—C4—H4

C6—C5—C4

C6—C5—H5

C4—C5—H5

C5—C6—C1

C5—C6—N2

C1—C6—N2

C8—C7—C12

C8—C7—N2

C12—C7—N2

C7—C8—C9

C7—C8—H8

119.4

121.1 (4)

119.4

118.1 (5)

120.9

121.4 (5)

119.3

C54—C53—C58

C54—C53—N9

C58—C53—N9

C55—C54—C53

C55—C54—H54

C53—C54—H54

C56—C55—C54

C56—C55—H55

C54—C55—H55

C55—C56—C57

C55—C56—H56

C57—C56—H56

C56—C57—C58

C56—C57—H57

C58—C57—H57

C57—C58—C53

C57—C58—N7

C53—C58—N7

N8—C59—H59A

N8—C59—H59B

H59A—C59—H59B

N8—C59—H59C

H59A—C59—H59C

H59B—C59—H59C

N9—C60—H60A

N9—C60—H60B

H60A—C60—H60B

N9—C60—H60C

H60A—C60—H60C

H60B—C60—H60C

N10—C61—C62

N10—C61—C66

C62—C61—C66

C63—C62—C61

C63—C62—H62

C61—C62—H62

C62—C63—C64

C62—C63—H63

C64—C63—H63

C65—C64—C63

C65—C64—H64

C63—C64—H64

C66—C65—C64

C66—C65—H65

C64—C65—H65

C65—C66—C61

C65—C66—N11

C61—C66—N11

120.2 (5)

122.0 (4)

117.7 (4)

119.8 (5)

120.1

120.5 (5)

119.8

119.7 (5)

120.2

120.9 (5)

119.5

119.3

120.8 (4)

118.6 (4)

120.7 (4)

120.0 (5)

124.0 (5)

115.9 (4)

121.2 (5)

119.4

119.4 (5)

120.3

120.5 (5)

119.8

119.5

118.9 (4)

122.0 (4)

119.2 (4)

109.5

C9—C8—H8

C10—C9—C8

C10—C9—H9

C8—C9—H9

C9—C10—C11

C9—C10—H10

C11—C10—H10

C10—C11—C12

C10—C11—H11

C12—C11—H11

N3—C12—C11

N3—C12—C7

C11—C12—C7

C14—C13—C18

C14—C13—N3

C18—C13—N3

C13—C14—C15

C13—C14—H14

C15—C14—H14

C14—C15—C16

C14—C15—H15

C16—C15—H15

C17—C16—C15

C17—C16—H16

C15—C16—H16

C16—C17—C18

C16—C17—H17

C18—C17—H17

N1—C18—C17

N1—C18—C13

119.8

120.5 (5)

119.7

109.5

119.7

123.3 (5)

118.7 (4)

118.0 (5)

120.8 (5)

118.4 (4)

120.7 (4)

121.9 (5)

119.1

118.2 (5)

120.9

120.1 (5)

119.9

122.6 (5)

118.7

117.5 (4)

126.2 (4)

109.5

118.5 (4)

124.5 (4)

116.5 (4)

122.9 (4)

118.5

120.1 (4)

120.0

117.8 (4)

121.1

122.9 (4)

118.6

119.8 (4)

119.2 (4)

121.0 (4)

Acta Cryst. (2018). C74, 1641-1649

sup-10

supporting information

C17—C18—C13

N2—C19—H19A

N2—C19—H19B

H19A—C19—H19B

N2—C19—H19C

H19A—C19—H19C

H19B—C19—H19C

N3—C20—H20A

N3—C20—H20B

H20A—C20—H20B

N3—C20—H20C

H20A—C20—H20C

H20B—C20—H20C

C22—C21—C26

C22—C21—N4

C26—C21—N4

C22—C21—Fe2

C26—C21—Fe2

N4—C21—Fe2

C23—C22—C21

C23—C22—H22

C21—C22—H22

C24—C23—C22

C24—C23—H23

C22—C23—H23

C23—C24—C25

C23—C24—H24

C25—C24—H24

C26—C25—C24

C26—C25—H25

C24—C25—H25

C25—C26—C21

C25—C26—N5

C21—C26—N5

C28—C27—N5

C28—C27—C32

N5—C27—C32

C29—C28—C27

C29—C28—H28

C27—C28—H28

C30—C29—C28

C30—C29—H29

C28—C29—H29

C29—C30—C31

C29—C30—H30

C31—C30—H30

C32—C31—C30

C32—C31—H31

116.2 (4)

109.5

117.8 (4)

124.3 (4)

95.9 (3)

112.8 (3)

58.2 (2)

120.9 (4)

119.5

120.6 (4)

119.7

118.9 (4)

120.6

121.8 (4)

119.1

C68—C67—C72

C68—C67—N11

C72—C67—N11

C69—C68—C67

C69—C68—H68

C67—C68—H68

C68—C69—C70

C68—C69—H69

C70—C69—H69

C69—C70—C71

C69—C70—H70

C71—C70—H70

C72—C71—C70

C72—C71—H71

C70—C71—H71

C71—C72—C67

C71—C72—N12

C67—C72—N12

C74—C73—C78

C74—C73—N12

C78—C73—N12

C75—C74—C73

C75—C74—H74

C73—C74—H74

C76—C75—C74

C76—C75—H75

C74—C75—H75

C75—C76—C77

C75—C76—H76

C77—C76—H76

C76—C77—C78

C76—C77—H77

C78—C77—H77

N10—C78—C73

N10—C78—C77

C73—C78—C77

N11—C79—H79A

N11—C79—H79B

H79A—C79—H79B

N11—C79—H79C

H79A—C79—H79C

H79B—C79—H79C

N12—C80—H80A

N12—C80—H80B

H80A—C80—H80B

N12—C80—H80C

H80A—C80—H80C

H80B—C80—H80C

119.0 (4)

123.1 (4)

117.9 (4)

120.4 (5)

119.8

120.9 (4)

119.5

119.2 (5)

120.4

121.2 (5)

119.4

119.2 (4)

122.8 (4)

118.0 (4)

119.3 (4)

119.1 (4)

121.6 (4)

123.9 (5)

118.0

117.0 (5)

121.5

121.2 (5)

119.4

122.3 (4)

118.9

119.1

119.9 (4)

120.3 (4)

119.7 (4)

124.0 (5)

118.9 (4)

117.1 (4)

120.5 (6)

119.8

121.2 (5)

119.4

119.1 (5)

120.5

118.9

125.8 (4)

117.9 (4)

116.3 (4)

109.5

120.5

121.2 (5)

119.4

109.5

Acta Cryst. (2018). C74, 1641-1649

sup-11

supporting information

C30—C31—H31

C31—C32—C27

C31—C32—N6

C27—C32—N6

C34—C33—C38

C34—C33—N6

C38—C33—N6

C35—C34—C33

C35—C34—H34

C33—C34—H34

C34—C35—C36

C34—C35—H35

C36—C35—H35

C37—C36—C35

C37—C36—H36

C35—C36—H36

C36—C37—C38

C36—C37—H37

C38—C37—H37

C33—C38—C37

C33—C38—N4

C37—C38—N4

N5—C39—H39A

N5—C39—H39B

H39A—C39—H39B

N5—C39—H39C

H39A—C39—H39C

H39B—C39—H39C

N6—C40—H40A

N6—C40—H40B

H40A—C40—H40B

N6—C40—H40C

H40A—C40—H40C

H40B—C40—H40C

C42—C41—C46

C42—C41—N7

C46—C41—N7

C43—C42—C41

C43—C42—H42

C41—C42—H42

C42—C43—C44

C42—C43—H43

C44—C43—H43

C43—C44—C45

C43—C44—H44

C45—C44—H44

C46—C45—C44

C46—C45—H45

119.4

N10—Fe1—N7

N10—Fe1—N4

N7—Fe1—N4

N10—Fe1—N9

N7—Fe1—N9

N4—Fe1—N9

N10—Fe1—Fe2

N7—Fe1—Fe2

N4—Fe1—Fe2

N9—Fe1—Fe2

N1—Fe2—N7

N1—Fe2—N4

N7—Fe2—N4

N1—Fe2—C21

N7—Fe2—C21

N4—Fe2—C21

N1—Fe2—Fe1

N7—Fe2—Fe1

N4—Fe2—Fe1

C21—Fe2—Fe1

C18—N1—C1

C18—N1—Fe2

C1—N1—Fe2

C7—N2—C6

C7—N2—C19

C6—N2—C19

C12—N3—C13

C12—N3—C20

C13—N3—C20

C38—N4—C21

C38—N4—Fe2

C21—N4—Fe2

C38—N4—Fe1

C21—N4—Fe1

Fe2—N4—Fe1

C27—N5—C26

C27—N5—C39

C26—N5—C39

C32—N6—C33

C32—N6—C40

C33—N6—C40

C41—N7—C58

C41—N7—Fe2

C58—N7—Fe2

C41—N7—Fe1

C58—N7—Fe1

Fe2—N7—Fe1

C46—N8—C47

139.63 (14)

115.65 (13)

89.81 (14)

107.53 (14)

79.85 (13)

122.57 (14)

143.01 (11)

45.05 (10)

45.18 (10)

108.97 (10)

123.16 (15)

143.61 (15)

93.04 (14)

119.49 (15)

110.96 (15)

36.19 (14)

168.73 (11)

45.87 (10)

47.62 (10)

68.99 (11)

122.3 (4)

128.7 (3)

108.3 (3)

109.9 (4)

115.6 (4)

112.0 (4)

116.3 (4)

118.6 (4)

112.2 (4)

120.8 (3)

130.2 (3)

85.6 (2)

119.0 (5)

124.6 (5)

116.4 (4)

119.8 (4)

118.0 (4)

122.3 (4)

122.4 (5)

118.8

117.7 (5)

121.1

120.9 (5)

119.6

121.8 (5)

119.1

117.4 (4)

126.0 (4)

116.3 (4)

109.5

112.6 (3)

114.8 (3)

87.20 (13)

113.2 (4)

117.9 (4)

113.7 (4)

112.0 (4)

116.6 (4)

114.5 (4)

113.5 (3)

120.7 (3)

98.9 (3)

109.5

118.2 (4)

120.6 (4)

121.1 (4)

122.0 (5)

119.0

120.0 (5)

120.0

119.1 (5)

120.4

121.7 (5)

119.1

123.5 (3)

106.5 (3)

89.07 (13)

115.1 (4)

Acta Cryst. (2018). C74, 1641-1649

sup-12

supporting information

C44—C45—H45

C45—C46—C41

C45—C46—N8

C41—C46—N8

C48—C47—C52

C48—C47—N8

C52—C47—N8

C49—C48—C47

C49—C48—H48

C47—C48—H48

C50—C49—C48

C50—C49—H49

C48—C49—H49

C49—C50—C51

C49—C50—H50

C51—C50—H50

C50—C51—C52

119.1

C46—N8—C59

C47—N8—C59

C53—N9—C52

C53—N9—C60

C52—N9—C60

C53—N9—Fe1

C52—N9—Fe1

C60—N9—Fe1

C78—N10—C61

C78—N10—Fe1

C61—N10—Fe1

C67—N11—C66

C67—N11—C79

C66—N11—C79

C72—N12—C73

C72—N12—C80

C73—N12—C80

116.8 (4)

114.4 (4)

114.4 (3)

111.7 (4)

112.1 (4)

102.3 (3)

104.0 (3)

111.6 (3)

123.3 (3)

122.2 (3)

114.2 (3)

112.4 (3)

117.2 (3)

112.6 (3)

113.7 (3)

117.2 (4)

113.6 (4)

118.7 (5)

123.3 (4)

118.0 (4)

119.2 (5)

116.8 (4)

124.1 (4)

122.9 (5)

118.6

117.8 (5)

121.1

121.0 (5)

119.5

121.1 (5)

C6—C1—C2—C3

N1—C1—C2—C3

C1—C2—C3—C4

C2—C3—C4—C5

C3—C4—C5—C6

C4—C5—C6—C1

C4—C5—C6—N2

C2—C1—C6—C5

−2.4 (7)

171.3 (4)

0.4 (8)

2.1 (9)

−2.6 (9)

0.6 (8)

−180.0 (5)

1.9 (7)

−171.3 (5)

−177.6 (4)

9.2 (8)

4.0 (7)

−174.4 (4)

2.1 (8)

−5.5 (8)

2.8 (8)

−179.3 (5)

3.2 (7)

175.8 (4)

−5.6 (6)

−6.6 (7)

171.9 (4)

3.2 (7)

−173.0 (4)

0.4 (7)

−1.8 (7)

−0.4 (7)

−179.6 (4)

3.9 (7)

N11—C67—C72—N12

C78—C73—C74—C75

N12—C73—C74—C75

C73—C74—C75—C76

C74—C75—C76—C77

C75—C76—C77—C78

C74—C73—C78—N10

N12—C73—C78—N10

C74—C73—C78—C77

N12—C73—C78—C77

C76—C77—C78—N10

C76—C77—C78—C73

C17—C18—N1—C1

C13—C18—N1—C1

C17—C18—N1—Fe2

C13—C18—N1—Fe2

C6—C1—N1—C18

C2—C1—N1—C18

C6—C1—N1—Fe2

−3.9 (6)

−0.7 (7)

−179.2 (4)

−0.1 (7)

0.6 (7)

−0.4 (7)

−177.4 (4)

1.2 (6)

N1—C1—C6—C5

C2—C1—C6—N2

N1—C1—C6—N2

C12—C7—C8—C9

N2—C7—C8—C9

C7—C8—C9—C10

C8—C9—C10—C11

C9—C10—C11—C12

C10—C11—C12—N3

C10—C11—C12—C7

C8—C7—C12—N3

N2—C7—C12—N3

C8—C7—C12—C11

N2—C7—C12—C11

C18—C13—C14—C15

N3—C13—C14—C15

C13—C14—C15—C16

C14—C15—C16—C17

C15—C16—C17—C18

C16—C17—C18—N1

C16—C17—C18—C13

C14—C13—C18—N1

0.8 (6)

179.4 (4)

178.0 (4)

−0.4 (6)

173.8 (4)

−10.1 (7)

4.8 (6)

−179.1 (3)

−54.7 (7)

132.1 (5)

116.3 (5)

−56.9 (5)

121.6 (5)

−56.9 (5)

−6.4 (6)

175.1 (4)

−63.7 (6)

115.8 (5)

66.3 (6)

C2—C1—N1—Fe2

C8—C7—N2—C6

C12—C7—N2—C6

C8—C7—N2—C19

C12—C7—N2—C19

C5—C6—N2—C7

C1—C6—N2—C7

C5—C6—N2—C19

C1—C6—N2—C19

C11—C12—N3—C13

C7—C12—N3—C13

−114.2 (5)

118.5 (5)

−64.1 (6)

178.6 (4)

Acta Cryst. (2018). C74, 1641-1649

sup-13

supporting information

N3—C13—C18—N1

C14—C13—C18—C17

N3—C13—C18—C17

C26—C21—C22—C23

N4—C21—C22—C23

Fe2—C21—C22—C23

C21—C22—C23—C24

C22—C23—C24—C25

C23—C24—C25—C26

C24—C25—C26—C21

C24—C25—C26—N5

C22—C21—C26—C25

N4—C21—C26—C25

Fe2—C21—C26—C25

C22—C21—C26—N5

N4—C21—C26—N5

Fe2—C21—C26—N5

N5—C27—C28—C29

C32—C27—C28—C29

C27—C28—C29—C30

C28—C29—C30—C31

C29—C30—C31—C32

C30—C31—C32—C27

C30—C31—C32—N6

C28—C27—C32—C31

N5—C27—C32—C31

C28—C27—C32—N6

N5—C27—C32—N6

C38—C33—C34—C35

N6—C33—C34—C35

C33—C34—C35—C36

C34—C35—C36—C37

C35—C36—C37—C38

C34—C33—C38—C37

N6—C33—C38—C37

C34—C33—C38—N4

N6—C33—C38—N4

C36—C37—C38—C33

C36—C37—C38—N4

C46—C41—C42—C43

N7—C41—C42—C43

C41—C42—C43—C44

C42—C43—C44—C45

C43—C44—C45—C46

C44—C45—C46—C41

C44—C45—C46—N8

C42—C41—C46—C45

N7—C41—C46—C45

−5.3 (7)

−5.2 (7)

170.9 (4)

2.2 (6)

179.0 (4)

121.9 (4)

0.5 (6)

−2.7 (6)

2.2 (7)

0.5 (7)

−179.3 (4)

−2.7 (6)

−179.3 (4)

−113.1 (4)

177.1 (4)

0.5 (6)

66.7 (5)

−175.5 (5)

3.5 (8)

C11—C12—N3—C20

−20.1 (7)

157.4 (4)

−65.1 (6)

118.7 (5)

76.0 (5)

−100.2 (5)

−30.0 (7)

156.3 (4)

−142.7 (4)

43.7 (6)

110.9 (5)

−62.7 (5)

145.9 (4)

−37.5 (6)

−135.0 (4)

−79.1 (4)

97.5 (4)

C7—C12—N3—C20

C14—C13—N3—C12

C18—C13—N3—C12

C14—C13—N3—C20

C18—C13—N3—C20

C33—C38—N4—C21

C37—C38—N4—C21

C33—C38—N4—Fe2

C37—C38—N4—Fe2

C33—C38—N4—Fe1

C37—C38—N4—Fe1

C22—C21—N4—C38

C26—C21—N4—C38

Fe2—C21—N4—C38

C22—C21—N4—Fe2

C26—C21—N4—Fe2

C22—C21—N4—Fe1

C26—C21—N4—Fe1

Fe2—C21—N4—Fe1

C28—C27—N5—C26

C32—C27—N5—C26

C28—C27—N5—C39

C32—C27—N5—C39

C25—C26—N5—C27

C21—C26—N5—C27

C25—C26—N5—C39

C21—C26—N5—C39

C31—C32—N6—C33

C27—C32—N6—C33

C31—C32—N6—C40

C27—C32—N6—C40

C34—C33—N6—C32

C38—C33—N6—C32

C34—C33—N6—C40

C38—C33—N6—C40

C42—C41—N7—C58

C46—C41—N7—C58

C42—C41—N7—Fe2

C46—C41—N7—Fe2

C42—C41—N7—Fe1

C46—C41—N7—Fe1

C57—C58—N7—C41

C53—C58—N7—C41

C57—C58—N7—Fe2

C53—C58—N7—Fe2

C57—C58—N7—Fe1

C53—C58—N7—Fe1

5.8 (5)

−177.7 (3)

84.8 (2)

1.1 (10)

−3.6 (10)

1.3 (9)

124.2 (5)

−54.8 (6)

−12.1 (7)

168.9 (4)

−59.5 (6)

120.7 (4)

78.7 (5)

−101.1 (5)

116.0 (5)

−62.0 (5)

−18.5 (7)

163.5 (4)

−66.3 (6)

113.1 (5)

69.3 (6)

−111.4 (5)

144.3 (4)

−36.4 (6)

27.3 (5)

−153.4 (3)

−84.5 (5)

94.8 (4)

3.3 (8)

−174.6 (5)

−5.7 (7)

173.4 (4)

172.5 (4)

−8.5 (6)

−0.1 (8)

179.3 (5)

−1.2 (9)

−0.2 (10)

2.7 (9)

2.5 (7)

−176.8 (4)

−171.1 (5)

9.6 (7)

−3.9 (8)

170.3 (5)

2.5 (7)

−178.2 (4)

1.0 (8)

−2.2 (8)

−0.1 (9)

3.6 (8)

−67.4 (6)

111.8 (5)

61.8 (4)

−119.0 (4)

153.5 (4)

−27.3 (5)

−175.8 (5)

−4.7 (7)

176.0 (4)

Acta Cryst. (2018). C74, 1641-1649

sup-14

supporting information

C42—C41—C46—N8

N7—C41—C46—N8

C52—C47—C48—C49

N8—C47—C48—C49

C47—C48—C49—C50

C48—C49—C50—C51

C49—C50—C51—C52

C48—C47—C52—C51

N8—C47—C52—C51

C48—C47—C52—N9

N8—C47—C52—N9

C50—C51—C52—C47

C50—C51—C52—N9

C58—C53—C54—C55

N9—C53—C54—C55

C53—C54—C55—C56

C54—C55—C56—C57

C55—C56—C57—C58

C56—C57—C58—C53

C56—C57—C58—N7

C54—C53—C58—C57

N9—C53—C58—C57

C54—C53—C58—N7

N9—C53—C58—N7

N10—C61—C62—C63

C66—C61—C62—C63

C61—C62—C63—C64

C62—C63—C64—C65

C63—C64—C65—C66

C64—C65—C66—C61

C64—C65—C66—N11

N10—C61—C66—C65

C62—C61—C66—C65

N10—C61—C66—N11

C62—C61—C66—N11

C72—C67—C68—C69

N11—C67—C68—C69

C67—C68—C69—C70

C68—C69—C70—C71

C69—C70—C71—C72

C70—C71—C72—C67

C70—C71—C72—N12

C68—C67—C72—C71

N11—C67—C72—C71

C68—C67—C72—N12

174.7 (4)

−4.6 (6)

0.5 (8)

178.8 (5)

−1.3 (8)

0.1 (8)

C45—C46—N8—C47

95.8 (5)

C41—C46—N8—C47

C45—C46—N8—C59

C41—C46—N8—C59

C48—C47—N8—C46

C52—C47—N8—C46

C48—C47—N8—C59

C52—C47—N8—C59

C54—C53—N9—C52

C58—C53—N9—C52

C54—C53—N9—C60

C58—C53—N9—C60

C54—C53—N9—Fe1

C58—C53—N9—Fe1

C47—C52—N9—C53

C51—C52—N9—C53

C47—C52—N9—C60

C51—C52—N9—C60

C47—C52—N9—Fe1

C51—C52—N9—Fe1

C73—C78—N10—C61

C77—C78—N10—C61

C73—C78—N10—Fe1

C77—C78—N10—Fe1

C62—C61—N10—C78

C66—C61—N10—C78

C62—C61—N10—Fe1

C66—C61—N10—Fe1

C68—C67—N11—C66

C72—C67—N11—C66

C68—C67—N11—C79

C72—C67—N11—C79

C65—C66—N11—C67

C61—C66—N11—C67

C65—C66—N11—C79

C61—C66—N11—C79

C71—C72—N12—C73

C67—C72—N12—C73

C71—C72—N12—C80

C67—C72—N12—C80

C74—C73—N12—C72

C78—C73—N12—C72

C74—C73—N12—C80

C78—C73—N12—C80

−83.6 (5)

−42.5 (7)

138.1 (4)

−77.2 (5)

101.1 (5)

62.1 (6)

1.8 (8)

1.4 (7)

−119.6 (5)

93.7 (5)

−176.8 (4)

179.1 (4)

0.8 (7)

−2.6 (7)

179.6 (4)

0.9 (7)

−178.4 (4)

−0.1 (8)

−0.6 (8)

0.3 (8)

−85.6 (5)

−34.9 (6)

145.8 (4)

−154.5 (4)

26.2 (4)

21.8 (6)

−160.5 (4)

150.3 (4)

−32.1 (5)

−89.0 (4)

88.7 (4)

0.5 (7)

179.7 (4)

−1.1 (7)

178.2 (4)

179.6 (4)

−1.0 (6)

169.3 (4)

−3.2 (7)

2.0 (7)

0.8 (7)

−2.2 (7)

0.9 (7)

−179.4 (4)

−170.3 (4)

1.7 (6)

10.0 (7)

−178.0 (4)

2.5 (7)

−23.2 (6)

158.6 (4)

163.5 (3)

−14.7 (5)

142.7 (4)

−45.4 (6)

−43.5 (5)

128.4 (4)

119.5 (5)

−59.9 (5)

−13.2 (6)

167.4 (4)

−66.3 (5)

113.4 (5)

68.6 (5)

−111.7 (4)

116.0 (5)

−63.0 (5)

−19.9 (6)

161.1 (4)

−65.5 (5)

116.0 (4)

72.0 (5)

−176.9 (4)

−0.2 (8)

−2.1 (8)

2.2 (7)

0.0 (7)

−178.9 (4)

−2.4 (7)

177.1 (4)

176.6 (4)

−106.6 (5)

Acta Cryst. (2018). C74, 1641-1649

sup-15

supporting information

Bis(µ-1,4-dimethyltribenzo[b,e,h][1,4,7]triazacyclonona-2,5,8-trien-7-ido-κN⁷)bis(tetrahydrofuran-κO)iron(II)

(10)

Crystal data

[Fe(C₂₀H₁₈N₃)₂(C₄H₈O)₂]

M_r= 800.80

D_x= 1.288 Mg m⁻³

Cu Kα radiation, λ = 1.54178 Å

Cell parameters from 9933 reflections

θ = 3.9–66.7°

Orthorhombic, Pbca

a = 15.9624 (12) Å

b = 15.8047 (11) Å

c = 32.747 (2) Å

V = 8261.5 (10) Å³

Z = 8

µ = 3.29 mm⁻¹

T = 100 K

Block, green

0.11 × 0.10 × 0.06 mm

F(000) = 3392

Data collection

Bruker X8 Prospector CCD

diffractometer

Radiation source: I-mu-S microsource X-ray

tube

Laterally graded multilayer (Goebel) mirror

monochromator

T_min= 0.569, T_max= 0.753

23792 measured reflections

7194 independent reflections

5411 reflections with I > 2σ(I)

R_int= 0.055

θ

_max= 66.7°, θ_min= 3.9°

ω and phi scans

Absorption correction: multi-scan

(APEX2; Bruker, 2014)

h = −10→18

k = −18→18

l = −31→38

Refinement

Refinement on F²

Least-squares matrix: full

R[F²> 2σ(F²)] = 0.043

wR(F²) = 0.111

Secondary atom site location: difference Fourier

map

Hydrogen site location: inferred from

neighbouring sites

S = 1.05

7194 reflections

555 parameters

132 restraints

Primary atom site location: structure-invariant

direct methods

H-atom parameters constrained

w = 1/[σ²(F_o²) + (0.0545P)²+ 1.2424P]

where P = (F_o²+ 2F_c²)/3

(Δ/σ)_max= 0.002

Δρ_max= 0.45 e Å⁻³

Δρ_min= −0.28 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.

Refinement. One THF ligand is disordered with two alternative orientations. The two moieties were restrained to have

similar geometries, and the Uij components of their atoms′ ADPs were restrained to be similar if closer than 1.7

Angstrom. Subject to these conditions the occupancy ratio refined to 0.790 (8) to 0.210 (8). Reflection 0 0 2 was affected

by the beam stop and was omitted from the refinement.

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

x

y

z

U_iso*/U_eq

Occ. (<1)

C1

C2

H2

0.01642 (16)

0.09943 (16)

0.1417

0.58940 (13)

0.58486 (14)

0.5615

0.32908 (7)

0.31399 (7)

0.3310

0.0168 (5)

0.0200 (5)

0.024*

Acta Cryst. (2018). C74, 1641-1649

sup-16

supporting information

C3

H3

0.12151 (18)

0.1776

0.61286 (14)

0.6063

0.27560 (7)

0.2664

0.0226 (5)

0.027*

C4

H4

0.06276 (18)

0.0775

0.65050 (15)

0.6699

0.25038 (7)

0.2239

0.0234 (6)

0.028*

C5

H5

−0.01885 (17)

−0.0596

0.65892 (14)

0.6861

0.26520 (7)

0.2486

0.0208 (5)

0.025*

C6

C7

C8

H8

−0.04262 (16)

−0.15464 (17)

−0.21592 (18)

−0.2452

0.62894 (13)

0.72340 (15)

0.76162 (16)

0.7293

0.30332 (7)

0.31940 (7)

0.29572 (8)

0.2759

0.0175 (5)

0.0210 (5)

0.0272 (6)

0.033*

C9

H9

−0.2349 (2)

−0.2776

0.84726 (17)

0.8730

0.30086 (9)

0.2849

0.0355 (7)

0.043*

C10

H10

C11

H11

C12

C13

C14

H14

C15

H15

C16

H16

C17

H17

C18

C19

H19A

H19B

H19C

C20

H20A

H20B

H20C

C21

C22

H22

C23

H23

C24

H24

C25

H25

C26

C27

C28

H28

−0.1909 (2)

−0.2019

−0.13083 (19)

−0.1012

−0.11369 (17)

−0.09703 (16)

−0.16313 (17)

−0.1838

−0.19976 (17)

−0.2445

−0.17007 (18)

−0.1940

−0.10565 (17)

−0.0867

−0.06699 (15)

−0.18646 (17)

−0.1868

0.89430 (17)

0.9531

0.85648 (16)

0.8895

0.77097 (15)

0.65585 (15)

0.67221 (16)

0.7284

0.60877 (17)

0.6212

0.52737 (17)

0.4833

0.50939 (15)

0.4526

0.57262 (15)

0.57902 (15)

0.5873

0.32932 (9)

0.3321

0.35387 (8)

0.3733

0.35020 (7)

0.39656 (7)

0.42292 (7)

0.4252

0.44604 (8)

0.4642

0.44225 (8)

0.4582

0.41537 (8)

0.4130

0.39130 (7)

0.29672 (8)

0.2671

0.0378 (7)

0.045*

0.0305 (6)

0.037*

0.0216 (5)

0.0191 (5)

0.0242 (6)

0.029*

0.0286 (6)

0.034*

0.0288 (6)

0.035*

0.0247 (6)

0.030*

0.0181 (5)

0.0265 (6)

0.040*

−0.2429

−0.1686

−0.00600 (17)

0.0224

0.0359

0.5884

0.5211

0.77649 (15)

0.8212

0.7399

0.3075

0.3030

0.40344 (7)

0.3880

0.4164

0.040*

0.0227 (6)

0.034*

−0.0416

0.8020

0.4245

0.034*

0.22608 (17)

0.16839 (18)

0.1155

0.18557 (19)

0.1447

0.26167 (19)

0.2739

0.31964 (18)

0.3722

0.30359 (16)

0.44191 (16)

0.51903 (18)

0.5225

0.53580 (14)

0.59961 (15)

0.6001

0.66182 (16)

0.7039

0.66321 (16)

0.7057

0.60072 (15)

0.6011

0.53794 (14)

0.50477 (14)

0.49602 (16)

0.4653

0.42264 (7)

0.43274 (8)

0.4194

0.46131 (8)

0.4671

0.48145 (8)

0.5011

0.47213 (7)

0.4857

0.44382 (7)

0.42074 (7)

0.43994 (8)

0.4648

0.0206 (5)

0.0264 (6)

0.032*

0.0295 (6)

0.035*

0.0307 (6)

0.037*

0.0244 (6)

0.029*

0.0191 (5)

0.0205 (5)

0.0269 (6)

0.032*

Acta Cryst. (2018). C74, 1641-1649

sup-17

supporting information

C29

H29

0.59142 (19)

0.6437

0.53139 (17)

0.5242

0.42340 (9)

0.4368

0.0333 (7)

0.040*

C30

H30

0.58688 (19)

0.6354

0.57695 (18)

0.6041

0.38751 (9)

0.3770

0.0348 (7)

0.042*

C31

H31

0.51092 (19)

0.5084

0.58309 (15)

0.6136

0.36667 (9)

0.3417

0.0310 (6)

0.037*

C32

C33

C34

H34

0.43867 (17)

0.33363 (17)

0.38313 (18)

0.4316

0.54505 (14)

0.45479 (15)

0.40175 (16)

0.4240

0.38190 (8)

0.35471 (7)

0.33094 (7)

0.3180

0.0224 (5)

0.0212 (5)

0.0261 (6)

0.031*

C35

H35

0.36331 (19)

0.3968

0.31719 (17)

0.2821

0.32570 (8)

0.3087

0.0312 (6)

0.037*

C36

H36

0.29458 (19)

0.2814

0.28494 (16)

0.2265

0.34544 (8)

0.3430

0.0311 (6)

0.037*

C37

H37

0.24396 (18)

0.1965

0.33734 (15)

0.3139

0.36908 (8)

0.3824

0.0252 (6)

0.030*

C38

C39

0.26102 (17)

0.36655 (18)

0.3106

0.3818

0.4074

0.3533 (2)

0.3929

0.3655

0.2961

0.0552 (6)

0.0162

0.1132

0.0353 (3)

0.0039

0.0872

−0.0177 (3)

−0.0122

−0.0775

0.0174 (4)

0.0648

−0.0260

0.063 (2)

0.0464

0.42343 (15)

0.40468 (15)

0.3792

0.4259

0.3620

0.59413 (17)

0.5744

0.6532

0.5899

0.3854 (4)

0.4308

0.4036

0.3049 (4)

0.3162

0.2736

0.2556 (3)

0.1940

0.2717

0.2806 (3)

0.2434

0.2771

0.4049 (16)

0.4653

0.37376 (7)

0.46536 (7)

0.4665

0.4925

0.4567

0.32455 (8)

0.3038

0.3314

0.3139

0.46578 (13)

0.4744

0.4719

0.48744 (12)

0.5129

0.4942

0.45750 (14)

0.4621

0.4597

0.41696 (15)

0.4093

0.3954

0.4631 (5)

0.4641

0.0207 (5)

0.0243 (6)

0.036*

0.0328 (7)

0.049*

0.0380 (12)

0.046*

0.0405 (12)

0.049*

0.0388 (11)

0.047*

0.0356 (12)

0.043*

0.038 (3)

0.046*

H39A

H39B

H39C

C40

H40A

H40B

H40C

C41

H41A

H41B

C42

H42A

H42B

C43

0.790 (8)

0.210 (8)

H43A

H43B

C44

H44A

H44B

C41B

H41C

H41D

C42B

H42C

H42D

C43B

H43C

H43D

C44B

H44C

0.1227

0.0085 (12)

0.0338

−0.0482

0.0048 (15)

−0.0529

0.0428

0.0314 (18)

0.0832

0.3996

0.3520 (12)

0.3477

0.3769

0.2675 (11)

0.2447

0.2273

0.2792 (9)

0.2468

0.4703

0.4910 (4)

0.5186

0.4936

0.4709 (6)

0.4721

0.4848

0.4274 (5)

0.4217

0.046*

0.040 (2)

0.048*

0.040 (2)

0.048*

0.038 (3)

0.045*

Acta Cryst. (2018). C74, 1641-1649

sup-18

supporting information

H44D

C45

H45A

H45B

C46

H46A

H46B

C47

H47A

H47B

C48

H48A

H48B

N1

N2

N3

N4

N5

N6

Fe1

O1

O2

−0.0131

0.1079 (2)

0.1274

0.1574

0.0515 (2)

0.0642

0.0588

−0.0369 (2)

−0.0640

−0.0711

−0.0273 (2)

−0.0682

0.2596

0.36793 (17)

0.3086

0.4056

0.39048 (17)

0.4480

0.3496

0.3863 (2)

0.4425

0.3454

0.35759 (19)

0.3869

0.4085

0.29266 (7)

0.2904

0.2934

0.25683 (8)

0.2466

0.2342

0.27371 (8)

0.2725

0.2580

0.31744 (8)

0.3352

0.045*

0.0310 (7)

0.037*

0.0322 (7)

0.039*

0.0408 (8)

0.049*

0.0374 (7)

0.045*

0.210 (8)

−0.0364

0.2958

0.3197

0.045*

0.00017 (13)

−0.05762 (14)

−0.12926 (13)

0.20224 (13)

0.36636 (14)

0.36110 (14)

0.08313 (2)

0.04577 (13)

0.05724 (12)

0.54988 (11)

0.72633 (12)

0.63808 (11)

0.47367 (12)

0.47409 (12)

0.54189 (12)

0.45812 (2)

0.36799 (10)

0.37914 (11)

0.36630 (6)

0.37581 (6)

0.31516 (6)

0.39503 (6)

0.43652 (6)

0.36104 (6)

0.37925 (2)

0.42238 (5)

0.32899 (5)

0.0176 (4)

0.0194 (4)

0.0182 (4)

0.0184 (4)

0.0192 (4)

0.0231 (5)

0.01653 (11)

0.0287 (4)

0.0272 (4)

Atomic displacement parameters (Å²)

U¹¹

U²²

U³³

U¹²

U¹³

U²³

C1

C2

C3

C4

C5

C6

C7

C8

0.0183 (14)

0.0200 (15)

0.0215 (15)

0.0290 (16)

0.0253 (15)

0.0187 (14)

0.0200 (15)

0.0245 (16)

0.0319 (19)

0.045 (2)

0.0326 (18)

0.0194 (15)

0.0176 (14)

0.0183 (15)

0.0180 (15)

0.0231 (16)

0.0220 (15)

0.0131 (14)

0.0186 (15)

0.0232 (15)

0.0224 (15)

0.0200 (15)

0.0122 (10)

0.0189 (11)

0.0225 (11)

0.0240 (12)

0.0167 (11)

0.0131 (10)

0.0211 (11)

0.0287 (13)

0.0312 (14)

0.0208 (12)

0.0245 (13)

0.0224 (12)

0.0238 (12)

0.0304 (13)

0.0432 (15)

0.0346 (14)

0.0222 (12)

0.0226 (11)

0.0253 (12)

0.0211 (12)

0.0201 (11)

0.0280 (13)

0.0199 (12)

0.0212 (12)

0.0238 (13)

0.0172 (11)

0.0202 (12)

0.0209 (12)

0.0220 (12)

0.0283 (14)

0.0435 (17)

0.0480 (18)

0.0344 (15)

0.0230 (12)

0.0159 (11)

0.0238 (13)

0.0246 (13)

0.0288 (14)

0.0299 (13)

0.0185 (12)

0.0356 (15)

0.0237 (13)

0.0192 (12)

0.0311 (14)

−0.0029 (9)

−0.0020 (10)

−0.0024 (10)

0.0046 (10)

0.0014 (10)

−0.0050 (10)

−0.0004 (10)

0.0006 (10)

−0.0067 (11)

−0.0122 (13)

−0.0108 (15)

−0.0078 (13)

0.0004 (10)

−0.0029 (9)

−0.0021 (10)

0.0062 (11)

0.0028 (11)

−0.0001 (11)

−0.0027 (9)

−0.0017 (11)

−0.0027 (10)

−0.0010 (10)

−0.0092 (11)

−0.0015 (9)

0.0023 (9)

−0.0007 (10)

0.0021 (10)

0.0020 (9)

0.0012 (10)

−0.0024 (11)

−0.0043 (11)

−0.0013 (10)

−0.0021 (9)

0.0013 (10)

0.0004 (11)

0.0130 (13)

0.0117 (13)

0.0016 (12)

0.0010 (10)

−0.0032 (10)

−0.0014 (11)

−0.0055 (12)

−0.0081 (12)

−0.0017 (10)

−0.0010 (10)

−0.0028 (11)

−0.0024 (10)

0.0013 (10)

0.0033 (11)

−0.0033 (9)

0.0000 (10)

−0.0022 (11)

0.0004 (12)

−0.0061 (12)

−0.0062 (11)

−0.0012 (10)

0.0004 (9)

−0.0058 (11)

−0.0049 (12)

0.0063 (11)

0.0064 (10)

0.0001 (9)

C9

C10

C11

C12

C13

C14

C15

C16

C17

C18

C19

C20

C21

C22

−0.0036 (11)

−0.0006 (10)

−0.0013 (10)

−0.0051 (11)

Acta Cryst. (2018). C74, 1641-1649

sup-19

supporting information

C23

C24

C25

C26

C27

C28

C29

C30

C31

C32

C33

C34

C35

C36

C37

C38

C39

C40

C41

C42

C43

C44

C41B

C42B

C43B

C44B

C45

C46

C47

C48

N1

0.0271 (17)

0.0337 (18)

0.0204 (15)

0.0192 (14)

0.0178 (14)

0.0255 (16)

0.0183 (16)

0.0248 (17)

0.0358 (19)

0.0233 (15)

0.0271 (16)

0.0258 (16)

0.0303 (18)

0.0275 (17)

0.0172 (14)

0.0198 (14)

0.0245 (16)

0.0338 (18)

0.056 (3)

0.045 (3)

0.042 (3)

0.053 (3)

0.048 (5)

0.047 (5)

0.049 (5)

0.050 (5)

0.041 (2)

0.0286 (13)

0.0279 (13)

0.0297 (13)

0.0196 (11)

0.0192 (11)

0.0300 (13)

0.0388 (15)

0.0324 (14)

0.0219 (12)

0.0164 (11)

0.0224 (12)

0.0316 (13)

0.0332 (14)

0.0230 (13)

0.0246 (13)

0.0229 (12)

0.0252 (12)

0.0329 (14)

0.038 (3)

0.0330 (14)

0.0307 (14)

0.0230 (13)

0.0184 (11)

0.0245 (13)

0.0252 (13)

0.0428 (16)

0.0473 (17)

0.0351 (15)

0.0274 (13)

0.0142 (11)

0.0208 (12)

0.0301 (14)

0.0430 (16)

0.0339 (14)

0.0195 (12)

0.0232 (13)

0.0316 (15)

0.0193 (19)

0.0293 (19)

0.030 (2)

0.0093 (12)

0.0028 (12)

0.0007 (11)

0.0009 (10)

0.0010 (10)

0.0030 (11)

−0.0010 (12)

−0.0103 (13)

−0.0038 (12)

0.0021 (10)

0.0056 (11)

0.0042 (12)

0.0117 (13)

0.0034 (11)

0.0017 (11)

0.0061 (10)

0.0057 (11)

0.0056 (12)

−0.005 (2)

−0.012 (2)

−0.0157 (19)

−0.0130 (17)

−0.006 (5)

−0.009 (4)

0.000 (4)

0.0064 (12)

0.0020 (12)

0.0122 (15)

−0.0113 (14)

0.0010 (8)

−0.0009 (8)

−0.0005 (8)

0.0030 (8)

0.0014 (8)

0.0014 (9)

0.00079 (15)

−0.0009 (8)

−0.0020 (8)

−0.0047 (12)

−0.0056 (12)

−0.0041 (10)

0.0022 (9)

−0.0085 (11)

−0.0134 (11)

−0.0028 (10)

−0.0006 (9)

−0.0058 (10)

−0.0105 (11)

−0.0202 (13)

−0.0127 (13)

−0.0030 (11)

−0.0048 (10)

0.0014 (9)

−0.0022 (10)

−0.0118 (12)

−0.0121 (12)

−0.0044 (11)

−0.0032 (10)

0.0020 (10)

0.0116 (12)

0.0042 (18)

0.0139 (19)

0.0096 (18)

0.0099 (16)

0.016 (4)

0.0041 (10)

−0.0007 (11)

0.0025 (12)

0.0118 (13)

0.0124 (13)

0.0073 (11)

−0.0040 (10)

−0.0025 (11)

−0.0054 (12)

−0.0079 (13)

−0.0047 (11)

−0.0063 (10)

0.0027 (11)

0.0033 (12)

−0.0013 (19)

−0.0061 (17)

−0.0056 (18)

−0.002 (2)

0.047 (3)

0.044 (2)

0.0231 (17)

0.045 (5)

0.031 (2)

0.021 (5)

0.028 (4)

0.031 (5)

0.002 (4)

−0.003 (4)

−0.002 (4)

−0.005 (5)

0.010 (4)

0.013 (4)

0.014 (4)

0.040 (4)

0.036 (5)

0.028 (5)

0.0278 (13)

0.0287 (13)

0.0438 (16)

0.0430 (16)

0.0189 (9)

0.0185 (9)

0.0162 (9)

0.0175 (9)

0.0210 (9)

0.0207 (10)

0.01553 (17)

0.0233 (8)

0.0271 (9)

0.0241 (13)

0.0277 (14)

0.0322 (15)

0.0369 (16)

0.0189 (9)

0.0180 (10)

0.0215 (10)

0.0242 (10)

0.0193 (10)

0.0217 (10)

0.01733 (19)

0.0220 (9)

0.0242 (9)

−0.0021 (12)

−0.0069 (12)

−0.0095 (14)

−0.0083 (13)

−0.0010 (8)

−0.0027 (8)

−0.0035 (8)

−0.0037 (8)

−0.0009 (8)

0.0017 (9)

−0.0067 (11)

−0.0015 (11)

−0.0108 (13)

−0.0070 (13)

0.0041 (8)

−0.0007 (8)

−0.0012 (8)

−0.0020 (8)

0.0003 (8)

0.0403 (19)

0.047 (2)

0.0323 (19)

0.0148 (11)

0.0216 (12)

0.0170 (12)

0.0136 (12)

0.0173 (12)

0.0270 (13)

0.0167 (2)

0.0407 (13)

0.0302 (12)

N2

N3

N4

N5

N6

Fe1

O1

0.0020 (8)

0.00016 (15)

0.0036 (7)

−0.00282 (15)

0.0016 (8)

−0.0053 (8)

O2

−0.0073 (7)

Geometric parameters (Å, º)

C1—N1

C1—C6

C1—C2

C2—C3

C2—H2

C3—C4

1.394 (3)

C31—H31

0.9500

1.411 (3)

1.416 (4)

1.378 (3)

0.9500

C32—N6

C33—C34

C33—C38

C33—N6

C34—C35

1.415 (4)

1.390 (4)

1.406 (4)

1.460 (3)

1.384 (4)

Acta Cryst. (2018). C74, 1641-1649

sup-20

supporting information

C3—H3

0.9500

C34—H34

0.9500

C4—C5

C4—H4

1.397 (4)

0.9500

C35—C36

C35—H35

1.372 (4)

0.9500

C5—C6

C5—H5

1.388 (3)

0.9500

C36—C37

C36—H36

1.392 (4)

0.9500

C6—N3

C7—C8

C7—N3

C7—C12

C8—C9

C8—H8

C9—C10

C9—H9

1.444 (3)

1.387 (4)

1.415 (3)

1.418 (3)

1.397 (4)

0.9500

1.384 (4)

0.9500

1.386 (4)

0.9500

C37—C38

C37—H37

C38—N4

C39—N5

C39—H39A

C39—H39B

C39—H39C

C40—N6

C40—H40A

C40—H40B

C40—H40C

C41—O1

1.396 (3)

0.9500

1.413 (3)

1.448 (3)

0.9800

1.458 (3)

0.9800

C10—C11

C10—H10

C11—C12

C11—H11

C12—N2

C13—C14

C13—C18

C13—N2

C14—C15

C14—H14

C15—C16

C15—H15

C16—C17

C16—H16

C17—C18

C17—H17

C18—N1

C19—N3

C19—H19A

C19—H19B

C19—H19C

C20—N2

C20—H20A

C20—H20B

C20—H20C

C21—N4

C21—C22

C21—C26

C22—C23

C22—H22

C23—C24

C23—H23

C24—C25

C24—H24

C25—C26

1.384 (4)

0.9500

0.9800

1.455 (5)

1.490 (6)

0.9900

1.512 (6)

0.9900

1.495 (5)

0.9900

1.464 (4)

0.9900

1.415 (3)

1.388 (4)

1.411 (3)

1.448 (3)

1.386 (4)

0.9500

1.377 (4)

0.9500

1.383 (4)

0.9500

1.414 (3)

0.9500

1.396 (3)

1.439 (3)

0.9800

C41—C42

C41—H41A

C41—H41B

C42—C43

C42—H42A

C42—H42B

C43—C44

C43—H43A

C43—H43B

C44—O1

C44—H44A

C44—H44B

C41B—O1

C41B—C42B

C41B—H41C

C41B—H41D

C42B—C43B

C42B—H42C

C42B—H42D

C43B—C44B

C43B—H43C

C43B—H43D

C44B—O1

C44B—H44C

C44B—H44D

C45—O2

0.9900

1.479 (14)

1.512 (17)

0.9900

1.492 (16)

0.9900

1.497 (15)

0.9900

1.431 (14)

0.9900

0.9800

1.458 (3)

0.9800

1.388 (3)

1.405 (4)

1.419 (4)

1.385 (3)

0.9500

1.382 (4)

0.9500

1.387 (4)

0.9500

0.9900

1.449 (3)

1.522 (4)

0.9900

1.516 (5)

0.9900

C45—C46

C45—H45A

C45—H45B

C46—C47

1.382 (3)

C46—H46A

Acta Cryst. (2018). C74, 1641-1649

sup-21

Article Doi

Iron(II) complexes of dimethyltriazacyclophane

DOI: 10.1107/S2053229618015255

Source and publish data:

Authors:

Article abstract of DOI:10.1107/S2053229618015255

Full text of DOI:10.1107/S2053229618015255

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