A novel crystal structure of {tris­[4-(1H-pyrazol-3-yl-κN²)-3-aza­but-3-en­yl]amine-κN}iron(II) bis­(tetra­fluorido­borate) methanol monosolvate featuring a low-spin configuration

Mononuclear complexes are good model systems for evaluating the effects of different ligand systems on the magnetic properties of iron(II) centres. A novel crystal structure of the title compound, [Fe(C₁₈H₂₄N₁₀)](BF₄)₂·CH₃OH, with one mol­ecule of methanol per formula unit exhibits a strictly sixfold coordination sphere associated with a low-spin configuration at the metal centre. The incorporated methanol solvent molecule promotes extended hydrogen-bonding networks between the tetra­fluorido­borate anions and the cationic units. A less constrained crystal structure regarding close contacts between the tetra­fluorido­borate anions and the cationic units allows a spin transition which is inhibited in the previously published hydrate of the title compound.

S1. Introduction

Mononuclear complexes of tri­imine ligands derived from tris­(2-amino­ethyl)­amine have been studied intensively since mononuclear complexes are good model systems for evaluating the effects of different ligand systems on the magnetic properties of iron(II)centres (Halcrow, 2013; Gütlich & Goodwin, 2004; Gütlich, 2013). They also form valuable platforms for further modification. This might be connecting mononuclear complexes into dimers (Brewer et al., 2007, 2011), polymers (Lambert et al., 2000, 2004) and networks (Sunatsuki et al., 2003; Yamada et al., 2003) by hydrogen bonding, complexation of further metals or by simple deprotonation (Brewer et al., 2004) or alkyl­ation.

A broad variety of different ligand systems involving pyridines, imidazoles, methyl­imidazoles and pyrazoles has been published (Mealli & Lingafelter, 1970; Hoselto et al., 1975; Morgenstern-Baradau et al., 2000).

A detailed study by Halcrow and co-workers (Lazar et al., 2007; Hardie et al., 2004) investigated the effects of counter-ions on the spin state of the {tris­[4-(1H-pyrazol-3-yl)-3-aza­but-3-enyl]amine}­iron(II) dication. The perchlorate, tetra­fluoridoborate, nitrate and tri­fluoro­methane­sulfonate salts have been synthesised, crystallized and magnetically characterized.

The previously reported crystal structure of {tris­[4-(1H-pyrazol-3-yl)-3-aza­but-3-enyl]amine}­iron(II) bis­(tetra­fluoridoborate) contained one molecule of water per formula unit and both the crystal structure and the magnetic measurements clearly showed that this specific environment resulted in a high-spin structure at 150 K. In contrast, we obtained a single-crystal structure from the compound, (I), with one molecule of methanol per formula unit instead of a water molecule. This difference has a marked influence on the magnetic properties of the compound, which was found to be a low-spin complex at 100 K.

S2. Experimental

S2.1. Synthesis and crystallization

A mixture of pyrazole-3-carbaldehyde (50 mg, 0.52 mmol, 3 equivalents) and tris­(2-amino­ethyl)­amine (26 mg, 0.175 mmol, 1 equivalents) was refluxed in methanol (10 ml, HPLC grade) for 1 h. The solution was cooled to about 323 K and a solution of iron(II) tetra­fluoridoborate hexahydrate (59 mg, 0.175 mmol, 1 equivalent) in methanol (1 ml, HPLC grade) was added. The resulting orange solution was cooled to room temperature, its volume was reduced to about 6 ml and the resulting solution stored at 266 K for 18 h. A green precipitate was filtered off and the title compound was crystallized by diffusion of di­ethyl ether into the solution for 3 d to yield pale-orange needle-shaped crystals (48 mg, 0.15 mmol, 43%) suitable for X-ray diffraction. ¹H NMR (MeOH-d₄, 400.1 MHz, 298 K): δ 153.05 (bs), 146.27 (bs), 77.83 (bs), 37.26 (bs), 26.35 (bs). ESI–MS (MeCN + sodium formate): 434.1 [M - 2H]⁺. (The product readily oxidizes to Fe^III under ESI conditions. Choosing a more reductive environment by the addition of sodium formate allows observing both the Fe^III and the Fe^II species.) HRMS (ESI): calculated for C₁₈H₂₁FeN₁₀H: 434.1373; found: 434.1382.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in calculated positions, with O—H = 0.84 Å, N—H = 0.88 Å and C—H = 0.95, 0.98 or 0.99 Å for aryl, methyl or methine H atoms, respectively, and refined using a riding model with fixed isotropic displacement parameters of U_iso(H) = 1.5U_eq(C,O) for methyl and hy­droxy H atoms and U_iso(H) = 1.2U_eq(C,N) otherwise. The methanol solvent molecule was found to be partially disordered over two positions and the site-occupancy factors (SOFs) of the disordered parts were refined by means of a `free variable'. The final SOFs were each 0.50 (6). The H atoms of the disordered –OH group of the solvent molecule were refined in an idealized tetra­hedral angle. The disordered C and O atoms (C20, O1A and O1B) exhibited unusual displacement parameters, so they were refined using an enhanced rigid-body restraint with s.u. values of 0.004 Ų and a C20—O1B distance restraint of 1.43 (1) Å.

S3. Results and discussion

S3.1. Structure and determination of the spin state

Chiral complex (I) crystallizes as a conglomerate yielding crystals of enanti­omerically pure complexes. In this case, the randomly chosen crystal only contained the Δ-enanti­omer. In contrast, the crystals obtained by Lazar et al. (2007) contained a one-to-one mixture of both the Δ- and Θ-enanti­omers (space group P2₁/n).

While the previously reported data for the tetra­fluoridoborate salt of the title complex showed a distinctive high-spin species even at 5 K and a 6+1-fold coordination sphere, our work shows the importance of cocrystallized solvent molecules. In our structure, which was measured at 100 K, the Fe^II ion is found in a sixfold coordination sphere best described as a trigonal anti­prism, with Fe—N bond lengths between 1.962 (3) and 2.000 (3) Å, and N—Fe—N bond angles between 79.33 (11) and 79.66 (12)° (Table 2).

The distance of the central tris­(2-amino­ethyl)­amine N atom to the Fe^II atom is 3.462 (3) Å, which is roughly equal to the sum of the van der Waals radii and therefore should not be considered as a binding inter­action. The previous results of Lazar et al. (2007) suggest a correlation between this distance and the resulting spin state which might be either ascribed to the distortion of the trigonal anti­prismatic coordination sphere or the additional donating ligand. The structure presented herein, however, shows a rather long distance and a highly symmetric ligand field. Hence, the bond lengths and the coordination sphere clearly demonstrate a low-spin configuration of the metal centre here.

Furthermore, a change in colour can be observed upon cooling. While the crystals are pale orange at room temperature, they turn red upon cooling in liquid nitro­gen, indicating a spin transition between 300 and 100 K.

S3.2. Cocrystallized methanol and hydrogen bonding

The cocrystallized methanol molecule is bound via a hydrogen bond to one of the pyrazole N-bonded H atoms (N2···O1Aⁱⁱ; see Table 3 for symmetry codes). The distance between the donor and acceptor atoms of 2.692 (19) Å is typical for such hydrogen bonds. [There is also the 2.835 (12) Å distance to O1B?] The other two pyrazole N-bonded H atoms are bound to the tetra­fluoridoborate anions. One of these tetra­fluoridoborate anions binds not only to the pyrazole N-bonded H atom [N9···F3ⁱⁱⁱ = 2.777 (4)Å], but also to the methanol O-bonded H atom [O1···F4^viii 2.746 (9) Å], forming a ring of hydrogen bonds restricted to the asymmetric unit [O1···F5 = 2.90 (4) Å; not in Table 3]. The other tetra­fluoridoborate ion not only binds to one of the pyrazole N-bonded H atoms [N6···F7ⁱⁱ = 2.849 (4) Å], but it is also in close contact to the pyrazole N-bonded H atom being bound to the methanol [not clear] [N2···F5ⁱ 2.784 (4) Å], forming chains of hydrogen-bonded cations in the crystal. These chains of head-to-head-connected complexes are somewhat typical for this class of compounds. While the C₃ symmetry axes of the cations in the two layers of the chain are nearly anti­parallel, the top-view reveals a zigzag conformation.

Although there are two different disordered methanol molecules present in the structure, both are equally able to contribute to the hydrogen bonding, as described above. They are oriented in the same direction and the positions of the two different positions (O1A and O1B) differ by only 0.58 (7) Å.

The previously published structure also contains a similar motif of hydrogen bonds. The ladder-like network contains four hydrogen bonds, each involving a cocrystallized molecule of water that connects two cations and one tetra­fluoridoborate anion. Furthermore, the pseudo-dimers are connected via hydrogen bonds between the second tetra­fluoridoborate ion, the cations and the connecting water molecules. The nitrate salt reported by Lazar et al. (2007) (isotypical to the structure presented herein) does exhibit the very same structural features. In the original work, the authors present a concise explanation for the observed differences in behaviour, comparing their hydrate form of the title compound and their presented structure of the nitrate salt.

While the nitrate salt in the original work does exhibit the same arrangement of the cationic unit presented in this work, their tetra­fluoridoborate hydrate does show some close contacts of around 2.55 Å between the tetra­fluoridoborate anions and the tris­(2-amino­ethyl)­amine part of the cation. Their conclusive deduction was a slight pressure on the methyl­ene groups, distorting the structure and stabilizing a high-spin geometry with a seventh Fe—N bond to the central N atom preventing the cationic unit from relaxing to the proper low-spin geometry. The structural features of the cationic unit are similar, though not completely identical, to the structural features observed in the crystal structure of their nitrate salt in its high-spin state at 300 K. In our structure, however, there are also short contacts between the tetra­fluoridoborate anions and the methyl­ene groups, but fewer and significantly longer ones between the fluorine acceptor atoms and the carbon donor atoms, with the shortest distance (C17···F8^vii) being 3.262 (4)Å. In our work, the environment around the methyl­ene groups is more open, allowing the structure to exhibit the observed low-spin geometry.

Computing details

Cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures

	Fig. 1. The asymmetric unit of (I) crystallized with one molecule of methanol per formula unit. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. The atom-numbering scheme is included.
	Fig. 2. Selected atoms from the crystal structure as determined by XRD, showing the hydrogen bonds. Only H atoms attached to the pyrazole rings are shown for clarity.
	Fig. 3. The hydrogen-bond network through the crystal, showing a side view (top) and a top view (bottom). The hydrogen bonds are blue; however, H atoms have been omitted for clarity).

(Tris[4-(1H-pyrazol-3-yl-κN²)-3-azabut-3-enyl]amine-κN}iron(II) bis(tetrafluoridoborate) methanol monosolvate

Crystal data

[Fe(C18H24N10)](BF4)2·CH4O	Dx = 1.648 Mg m^−3
Mr = 641.98	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 9996 reflections
a = 11.8634 (7) Å	θ = 2.6–29.9°
b = 12.6803 (6) Å	µ = 0.68 mm^−1
c = 17.1975 (9) Å	T = 100 K
V = 2587.0 (2) Å^3	Needle, orange
Z = 4	0.2 × 0.06 × 0.04 mm
F(000) = 1312

Data collection

Bruker X8 Kappa APEXII diffractometer	6190 independent reflections
Radiation source: sealed tube	5376 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 7 pixels mm^-1	θmax = 28.0°, θmin = 3.3°
fine slicing ω and φ scans	h = −15→13
Absorption correction: multi-scan SADABS2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0800 before and 0.0551 after correction. The Ratio of minimum to maximum transmission is 0.7899. The λ/2 correction factor is 0.00150.	k = −16→16
Tmin = 0.589, Tmax = 0.746	l = −22→20
23363 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.0421P)^2 + 0.7928P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.086	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.42 e Å^−3
6190 reflections	Δρmin = −0.43 e Å^−3
380 parameters	Absolute structure: Flack x determined using 2141 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
7 restraints	Absolute structure parameter: 0.013 (5)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Fe	0.39985 (4)	0.10496 (3)	0.44099 (2)	0.01494 (12)
N1	0.3392 (2)	0.1110 (2)	0.54785 (15)	0.0174 (6)
N2	0.2838 (3)	0.0480 (2)	0.59697 (17)	0.0198 (6)
H2	0.2624	−0.0168	0.5861	0.024*
N3	0.4517 (2)	0.2475 (2)	0.47365 (16)	0.0172 (6)
N4	0.3892 (3)	0.3171 (2)	0.31449 (18)	0.0267 (7)
N5	0.3267 (3)	−0.0303 (2)	0.41482 (16)	0.0190 (6)
N6	0.3508 (3)	−0.1345 (2)	0.41428 (17)	0.0210 (6)
H6	0.4139	−0.1623	0.4316	0.025*
N7	0.2531 (2)	0.1569 (2)	0.39841 (16)	0.0179 (6)
N8	0.5433 (3)	0.0410 (2)	0.47255 (16)	0.0186 (6)
N9	0.5931 (3)	0.0058 (2)	0.53779 (15)	0.0198 (6)
H9	0.5602	0.0036	0.5836	0.024*
N10	0.4806 (2)	0.1033 (2)	0.33952 (15)	0.0194 (6)
C1	0.3547 (3)	0.2020 (3)	0.58591 (19)	0.0187 (7)
C2	0.3082 (3)	0.1968 (3)	0.6609 (2)	0.0226 (8)
H2A	0.3070	0.2502	0.6996	0.027*
C3	0.2649 (3)	0.0965 (3)	0.66513 (19)	0.0215 (7)
H3	0.2278	0.0666	0.7089	0.026*
C4	0.4202 (3)	0.2783 (3)	0.54172 (18)	0.0187 (7)
H4	0.4384	0.3461	0.5616	0.022*
C5	0.5235 (3)	0.3188 (3)	0.4281 (2)	0.0231 (8)
H5A	0.5825	0.2773	0.4013	0.028*
H5B	0.5613	0.3691	0.4635	0.028*
C6	0.4545 (3)	0.3805 (3)	0.3674 (2)	0.0250 (8)
H6A	0.4027	0.4287	0.3952	0.030*
H6B	0.5070	0.4246	0.3366	0.030*
C7	0.2227 (3)	−0.0220 (3)	0.3835 (2)	0.0201 (7)
C8	0.1807 (3)	−0.1217 (3)	0.3627 (2)	0.0244 (8)
H8	0.1101	−0.1378	0.3395	0.029*
C9	0.2641 (3)	−0.1904 (3)	0.3833 (2)	0.0253 (8)
H9A	0.2619	−0.2648	0.3770	0.030*
C10	0.1837 (3)	0.0849 (3)	0.37710 (19)	0.0210 (7)
H10	0.1105	0.1013	0.3581	0.025*
C11	0.2179 (3)	0.2672 (3)	0.3911 (2)	0.0236 (8)
H11A	0.2423	0.3067	0.4378	0.028*
H11B	0.1347	0.2706	0.3883	0.028*
C12	0.2683 (3)	0.3192 (3)	0.3184 (2)	0.0254 (8)
H12A	0.2379	0.2831	0.2718	0.030*
H12B	0.2430	0.3935	0.3164	0.030*
C13	0.6217 (3)	0.0320 (3)	0.4159 (2)	0.0214 (8)
C14	0.7223 (3)	−0.0087 (3)	0.4472 (2)	0.0268 (8)
H14	0.7911	−0.0216	0.4206	0.032*
C15	0.6997 (3)	−0.0256 (3)	0.5241 (2)	0.0254 (8)
H15	0.7502	−0.0545	0.5613	0.030*
C16	0.5817 (3)	0.0654 (3)	0.3411 (2)	0.0231 (8)
H16	0.6268	0.0601	0.2956	0.028*
C17	0.4351 (3)	0.1375 (3)	0.2641 (2)	0.0260 (8)
H17A	0.3550	0.1160	0.2602	0.031*
H17B	0.4771	0.1021	0.2217	0.031*
C18	0.4440 (3)	0.2572 (3)	0.2540 (2)	0.0267 (8)
H18A	0.5247	0.2769	0.2525	0.032*
H18B	0.4104	0.2767	0.2033	0.032*
F1	0.4169 (3)	0.4669 (2)	0.68607 (14)	0.0531 (7)
F2	0.3159 (2)	0.41108 (19)	0.79043 (13)	0.0352 (6)
F3	0.4769 (2)	0.50461 (18)	0.80812 (13)	0.0326 (5)
F4	0.4862 (2)	0.3387 (2)	0.7607 (2)	0.0564 (8)
B1	0.4221 (4)	0.4316 (3)	0.7604 (3)	0.0282 (10)
F5	0.6126 (2)	0.5989 (2)	0.42618 (16)	0.0522 (7)
F6	0.4823 (2)	0.5731 (2)	0.51946 (15)	0.0504 (7)
F7	0.5275 (2)	0.74212 (19)	0.47991 (14)	0.0364 (6)
F8	0.42884 (19)	0.63304 (16)	0.40071 (12)	0.0316 (5)
B2	0.5128 (4)	0.6368 (3)	0.4579 (2)	0.0286 (10)
C20	0.3116 (6)	0.7438 (4)	0.6082 (3)	0.0656 (16)
H20A	0.2956	0.7362	0.5526	0.098*	0.50 (6)
H20B	0.2450	0.7234	0.6383	0.098*	0.50 (6)
H20C	0.3751	0.6983	0.6223	0.098*	0.50 (6)
H20D	0.3123	0.7618	0.5528	0.098*	0.50 (6)
H20E	0.2419	0.7060	0.6206	0.098*	0.50 (6)
H20F	0.3766	0.6990	0.6202	0.098*	0.50 (6)
OA	0.338 (3)	0.8451 (13)	0.624 (4)	0.157 (13)	0.50 (6)
HA	0.3825	0.8473	0.6617	0.236*	0.50 (6)
OB	0.3177 (9)	0.8410 (8)	0.6546 (9)	0.054 (5)	0.50 (6)
HB	0.3744	0.8386	0.6837	0.081*	0.50 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe	0.0133 (2)	0.0134 (2)	0.0180 (2)	0.00059 (19)	0.0009 (2)	−0.00066 (18)
N1	0.0150 (14)	0.0159 (13)	0.0213 (14)	0.0007 (11)	0.0032 (11)	0.0020 (12)
N2	0.0187 (16)	0.0159 (14)	0.0248 (15)	−0.0019 (11)	0.0047 (13)	0.0031 (11)
N3	0.0132 (15)	0.0168 (14)	0.0217 (14)	0.0000 (11)	−0.0024 (12)	0.0027 (11)
N4	0.0249 (18)	0.0264 (15)	0.0288 (16)	0.0033 (14)	0.0043 (14)	0.0010 (12)
N5	0.0194 (16)	0.0132 (13)	0.0243 (15)	0.0018 (11)	0.0012 (12)	−0.0001 (11)
N6	0.0226 (16)	0.0145 (14)	0.0259 (15)	0.0022 (11)	0.0012 (12)	−0.0021 (11)
N7	0.0163 (16)	0.0176 (13)	0.0197 (14)	0.0013 (11)	0.0008 (12)	−0.0013 (11)
N8	0.0192 (16)	0.0147 (13)	0.0220 (14)	0.0018 (11)	0.0007 (13)	0.0037 (11)
N9	0.0181 (15)	0.0181 (13)	0.0230 (14)	0.0002 (12)	−0.0025 (13)	0.0031 (10)
N10	0.0207 (15)	0.0165 (13)	0.0210 (13)	0.0028 (12)	0.0023 (11)	0.0003 (12)
C1	0.0151 (18)	0.0188 (16)	0.0222 (17)	0.0011 (13)	−0.0010 (13)	−0.0008 (13)
C2	0.0169 (19)	0.0299 (19)	0.0209 (17)	0.0000 (15)	−0.0013 (15)	−0.0018 (14)
C3	0.0169 (18)	0.0291 (18)	0.0184 (15)	0.0039 (15)	0.0009 (13)	0.0045 (15)
C4	0.0133 (18)	0.0165 (15)	0.0264 (17)	−0.0015 (12)	−0.0029 (14)	−0.0014 (12)
C5	0.0210 (19)	0.0184 (16)	0.030 (2)	−0.0041 (13)	0.0052 (15)	0.0034 (14)
C6	0.026 (2)	0.0182 (18)	0.0310 (18)	0.0019 (14)	0.0063 (16)	0.0057 (15)
C7	0.0159 (19)	0.0225 (17)	0.0219 (17)	0.0009 (14)	0.0025 (14)	−0.0039 (14)
C8	0.021 (2)	0.0215 (18)	0.0303 (18)	−0.0040 (14)	0.0008 (15)	−0.0065 (14)
C9	0.029 (2)	0.0150 (16)	0.032 (2)	−0.0039 (15)	0.0038 (17)	−0.0044 (14)
C10	0.0155 (18)	0.0247 (19)	0.0229 (17)	0.0030 (14)	−0.0007 (14)	−0.0018 (13)
C11	0.0168 (19)	0.0200 (17)	0.034 (2)	0.0025 (14)	−0.0008 (16)	−0.0015 (15)
C12	0.025 (2)	0.0217 (17)	0.0294 (19)	0.0029 (15)	−0.0022 (16)	0.0036 (15)
C13	0.018 (2)	0.0177 (16)	0.0288 (18)	−0.0003 (13)	0.0044 (14)	0.0022 (13)
C14	0.0157 (19)	0.0238 (17)	0.041 (2)	0.0029 (13)	0.0021 (17)	0.0013 (17)
C15	0.0168 (19)	0.0206 (17)	0.039 (2)	0.0005 (14)	−0.0084 (17)	0.0054 (15)
C16	0.024 (2)	0.0210 (16)	0.0247 (17)	0.0026 (14)	0.0070 (15)	−0.0008 (13)
C17	0.031 (2)	0.0263 (19)	0.0207 (17)	0.0079 (15)	0.0020 (15)	0.0000 (13)
C18	0.032 (2)	0.0267 (19)	0.0217 (17)	0.0083 (15)	0.0049 (16)	0.0074 (15)
F1	0.0500 (18)	0.078 (2)	0.0314 (12)	−0.0109 (15)	−0.0046 (13)	0.0074 (12)
F2	0.0273 (13)	0.0361 (13)	0.0420 (13)	−0.0083 (10)	0.0089 (10)	−0.0089 (10)
F3	0.0321 (14)	0.0336 (12)	0.0323 (12)	−0.0109 (10)	0.0011 (10)	−0.0078 (10)
F4	0.0394 (17)	0.0366 (15)	0.093 (2)	0.0084 (12)	−0.0055 (16)	−0.0179 (15)
B1	0.027 (3)	0.029 (2)	0.028 (2)	−0.0043 (17)	0.0014 (19)	−0.0038 (16)
F5	0.0335 (15)	0.0522 (15)	0.0709 (18)	0.0232 (13)	0.0051 (13)	−0.0017 (14)
F6	0.0575 (19)	0.0541 (17)	0.0396 (14)	−0.0166 (14)	−0.0065 (13)	0.0141 (12)
F7	0.0273 (13)	0.0315 (12)	0.0504 (14)	0.0040 (10)	−0.0043 (11)	−0.0064 (11)
F8	0.0332 (14)	0.0294 (12)	0.0321 (11)	0.0065 (9)	0.0002 (10)	−0.0021 (9)
B2	0.026 (2)	0.030 (2)	0.029 (2)	0.0027 (18)	0.0050 (18)	0.0026 (16)
C20	0.081 (4)	0.041 (3)	0.075 (4)	0.016 (3)	0.020 (3)	0.010 (3)
OA	0.18 (2)	0.045 (6)	0.24 (3)	−0.007 (8)	−0.140 (19)	0.003 (9)
OB	0.014 (7)	0.023 (4)	0.125 (9)	0.000 (3)	−0.017 (6)	0.014 (4)

Geometric parameters (Å, º)

Fe—N1	1.975 (3)	C7—C10	1.437 (5)
Fe—N3	1.990 (3)	C8—H8	0.9500
Fe—N5	1.974 (3)	C8—C9	1.365 (5)
Fe—N7	2.000 (3)	C9—H9A	0.9500
Fe—N8	1.962 (3)	C10—H10	0.9500
Fe—N10	1.991 (3)	C11—H11A	0.9900
N1—N2	1.336 (4)	C11—H11B	0.9900
N1—C1	1.339 (4)	C11—C12	1.534 (5)
N2—H2	0.8800	C12—H12A	0.9900
N2—C3	1.343 (4)	C12—H12B	0.9900
N3—C4	1.290 (4)	C13—C14	1.407 (5)
N3—C5	1.469 (4)	C13—C16	1.435 (5)
N4—C6	1.441 (5)	C14—H14	0.9500
N4—C12	1.435 (5)	C14—C15	1.366 (6)
N4—C18	1.444 (5)	C15—H15	0.9500
N5—N6	1.352 (4)	C16—H16	0.9500
N5—C7	1.350 (5)	C17—H17A	0.9900
N6—H6	0.8800	C17—H17B	0.9900
N6—C9	1.357 (5)	C17—C18	1.531 (5)
N7—C10	1.283 (4)	C18—H18A	0.9900
N7—C11	1.465 (4)	C18—H18B	0.9900
N8—N9	1.344 (4)	F1—B1	1.357 (5)
N8—C13	1.351 (5)	F2—B1	1.386 (5)
N9—H9	0.8800	F3—B1	1.397 (5)
N9—C15	1.346 (5)	F4—B1	1.402 (5)
N10—C16	1.292 (5)	F5—B2	1.390 (5)
N10—C17	1.470 (4)	F6—B2	1.380 (5)
C1—C2	1.404 (5)	F7—B2	1.398 (5)
C1—C4	1.455 (5)	F8—B2	1.401 (5)
C2—H2A	0.9500	C20—H20A	0.9800
C2—C3	1.374 (5)	C20—H20B	0.9800
C3—H3	0.9500	C20—H20C	0.9800
C4—H4	0.9500	C20—H20D	0.9800
C5—H5A	0.9900	C20—H20E	0.9800
C5—H5B	0.9900	C20—H20F	0.9800
C5—C6	1.540 (5)	C20—OA	1.348 (17)
C6—H6A	0.9900	C20—OB	1.470 (11)
C6—H6B	0.9900	OA—HA	0.8400
C7—C8	1.405 (5)	OB—HB	0.8400
N1—Fe—N3	79.33 (11)	C7—C8—H8	127.8
N1—Fe—N7	90.61 (11)	C9—C8—C7	104.5 (3)
N1—Fe—N10	172.44 (12)	C9—C8—H8	127.8
N3—Fe—N7	94.23 (11)	N6—C9—C8	108.6 (3)
N3—Fe—N10	96.22 (12)	N6—C9—H9A	125.7
N5—Fe—N1	94.91 (12)	C8—C9—H9A	125.7
N5—Fe—N3	171.59 (12)	N7—C10—C7	116.3 (3)
N5—Fe—N7	79.61 (12)	N7—C10—H10	121.9
N5—Fe—N10	90.15 (12)	C7—C10—H10	121.9
N8—Fe—N1	94.28 (12)	N7—C11—H11A	109.3
N8—Fe—N3	91.66 (12)	N7—C11—H11B	109.3
N8—Fe—N5	94.90 (12)	N7—C11—C12	111.7 (3)
N8—Fe—N7	172.96 (12)	H11A—C11—H11B	107.9
N8—Fe—N10	79.66 (12)	C12—C11—H11A	109.3
N10—Fe—N7	95.84 (11)	C12—C11—H11B	109.3
N2—N1—Fe	138.1 (2)	N4—C12—C11	114.8 (3)
N2—N1—C1	105.9 (3)	N4—C12—H12A	108.6
C1—N1—Fe	116.0 (2)	N4—C12—H12B	108.6
N1—N2—H2	124.4	C11—C12—H12A	108.6
N1—N2—C3	111.1 (3)	C11—C12—H12B	108.6
C3—N2—H2	124.4	H12A—C12—H12B	107.5
C4—N3—Fe	116.2 (2)	N8—C13—C14	109.8 (3)
C4—N3—C5	117.8 (3)	N8—C13—C16	113.2 (3)
C5—N3—Fe	126.0 (2)	C14—C13—C16	137.0 (3)
C6—N4—C18	120.4 (3)	C13—C14—H14	127.4
C12—N4—C6	119.9 (3)	C15—C14—C13	105.1 (3)
C12—N4—C18	119.6 (3)	C15—C14—H14	127.4
N6—N5—Fe	139.2 (2)	N9—C15—C14	107.9 (3)
C7—N5—Fe	115.2 (2)	N9—C15—H15	126.1
C7—N5—N6	105.5 (3)	C14—C15—H15	126.1
N5—N6—H6	124.7	N10—C16—C13	115.8 (3)
N5—N6—C9	110.6 (3)	N10—C16—H16	122.1
C9—N6—H6	124.7	C13—C16—H16	122.1
C10—N7—Fe	115.4 (2)	N10—C17—H17A	109.3
C10—N7—C11	118.2 (3)	N10—C17—H17B	109.3
C11—N7—Fe	126.4 (2)	N10—C17—C18	111.5 (3)
N9—N8—Fe	138.5 (2)	H17A—C17—H17B	108.0
N9—N8—C13	105.7 (3)	C18—C17—H17A	109.3
C13—N8—Fe	115.6 (2)	C18—C17—H17B	109.3
N8—N9—H9	124.3	N4—C18—C17	114.2 (3)
N8—N9—C15	111.4 (3)	N4—C18—H18A	108.7
C15—N9—H9	124.3	N4—C18—H18B	108.7
C16—N10—Fe	115.6 (2)	C17—C18—H18A	108.7
C16—N10—C17	118.0 (3)	C17—C18—H18B	108.7
C17—N10—Fe	126.4 (2)	H18A—C18—H18B	107.6
N1—C1—C2	110.8 (3)	F1—B1—F2	111.8 (4)
N1—C1—C4	113.0 (3)	F1—B1—F3	110.8 (3)
C2—C1—C4	136.1 (3)	F1—B1—F4	107.8 (4)
C1—C2—H2A	128.1	F2—B1—F3	109.2 (3)
C3—C2—C1	103.8 (3)	F2—B1—F4	109.5 (3)
C3—C2—H2A	128.1	F3—B1—F4	107.6 (3)
N2—C3—C2	108.4 (3)	F5—B2—F7	109.3 (3)
N2—C3—H3	125.8	F5—B2—F8	108.5 (3)
C2—C3—H3	125.8	F6—B2—F5	108.8 (3)
N3—C4—C1	115.3 (3)	F6—B2—F7	112.6 (3)
N3—C4—H4	122.3	F6—B2—F8	109.4 (3)
C1—C4—H4	122.3	F7—B2—F8	108.1 (3)
N3—C5—H5A	109.3	H20A—C20—H20B	109.5
N3—C5—H5B	109.3	H20A—C20—H20C	109.5
N3—C5—C6	111.5 (3)	H20B—C20—H20C	109.5
H5A—C5—H5B	108.0	H20D—C20—H20E	109.5
C6—C5—H5A	109.3	H20D—C20—H20F	109.5
C6—C5—H5B	109.3	H20E—C20—H20F	109.5
N4—C6—C5	115.5 (3)	OA—C20—H20A	109.5
N4—C6—H6A	108.4	OA—C20—H20B	109.5
N4—C6—H6B	108.4	OA—C20—H20C	109.5
C5—C6—H6A	108.4	OB—C20—H20D	109.5
C5—C6—H6B	108.4	OB—C20—H20E	109.5
H6A—C6—H6B	107.5	OB—C20—H20F	109.5
N5—C7—C8	110.8 (3)	C20—OA—HA	109.5
N5—C7—C10	113.5 (3)	C20—OB—HB	109.5
C8—C7—C10	135.7 (3)
Fe—N1—N2—C3	179.5 (3)	N8—C13—C16—N10	3.1 (5)
Fe—N1—C1—C2	−180.0 (2)	N9—N8—C13—C14	−0.6 (4)
Fe—N1—C1—C4	−3.3 (4)	N9—N8—C13—C16	179.3 (3)
Fe—N3—C4—C1	2.4 (4)	N10—C17—C18—N4	−56.8 (4)
Fe—N3—C5—C6	81.6 (3)	C1—N1—N2—C3	−0.6 (4)
Fe—N5—N6—C9	−175.3 (3)	C1—C2—C3—N2	−0.8 (4)
Fe—N5—C7—C8	176.4 (2)	C2—C1—C4—N3	176.1 (4)
Fe—N5—C7—C10	−1.5 (4)	C4—N3—C5—C6	−99.5 (3)
Fe—N7—C10—C7	−2.6 (4)	C4—C1—C2—C3	−175.1 (4)
Fe—N7—C11—C12	80.8 (3)	C5—N3—C4—C1	−176.6 (3)
Fe—N8—N9—C15	−176.2 (3)	C6—N4—C12—C11	−69.6 (4)
Fe—N8—C13—C14	176.3 (2)	C6—N4—C18—C17	113.3 (4)
Fe—N8—C13—C16	−3.7 (4)	C7—N5—N6—C9	0.1 (4)
Fe—N10—C16—C13	−1.1 (4)	C7—C8—C9—N6	−0.2 (4)
Fe—N10—C17—C18	82.7 (4)	C8—C7—C10—N7	−174.5 (4)
N1—N2—C3—C2	0.9 (4)	C10—N7—C11—C12	−100.4 (4)
N1—C1—C2—C3	0.4 (4)	C10—C7—C8—C9	177.6 (4)
N1—C1—C4—N3	0.6 (4)	C11—N7—C10—C7	178.5 (3)
N2—N1—C1—C2	0.1 (4)	C12—N4—C6—C5	112.0 (4)
N2—N1—C1—C4	176.7 (3)	C12—N4—C18—C17	−71.0 (4)
N3—C5—C6—N4	−55.4 (4)	C13—N8—N9—C15	−0.4 (4)
N5—N6—C9—C8	0.1 (4)	C13—C14—C15—N9	−1.5 (4)
N5—C7—C8—C9	0.3 (4)	C14—C13—C16—N10	−177.0 (4)
N5—C7—C10—N7	2.8 (5)	C16—N10—C17—C18	−99.4 (4)
N6—N5—C7—C8	−0.2 (4)	C16—C13—C14—C15	−178.6 (4)
N6—N5—C7—C10	−178.2 (3)	C17—N10—C16—C13	−179.2 (3)
N7—C11—C12—N4	−57.6 (4)	C18—N4—C6—C5	−72.3 (4)
N8—N9—C15—C14	1.2 (4)	C18—N4—C12—C11	114.7 (4)
N8—C13—C14—C15	1.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···F5^i	0.88	2.07	2.784 (4)	138
N2—H2···OA^ii	0.88	2.07	2.692 (19)	127
N2—H2···OB^ii	0.88	2.25	2.835 (12)	124
N6—H6···F7^ii	0.88	1.99	2.849 (4)	164
N9—H9···F3^iii	0.88	1.91	2.777 (4)	167
C2—H2A···F2	0.95	2.57	3.515 (4)	172
C2—H2A···F4	0.95	2.62	3.262 (5)	125
C6—H6A···F8	0.99	2.61	3.267 (4)	124
C9—H9A···F2^iv	0.95	2.55	3.359 (4)	143
C9—H9A···F8^ii	0.95	2.40	2.987 (4)	120
C10—H10···F1^i	0.95	2.57	3.410 (5)	148
C10—H10···F4^i	0.95	2.63	3.471 (5)	147
C12—H12B···F2^v	0.99	2.61	3.596 (4)	172
C14—H14···F1^vi	0.95	2.46	3.296 (5)	146
C14—H14···F6^vi	0.95	2.58	3.241 (5)	127
C15—H15···F8^vi	0.95	2.43	3.304 (4)	153
C17—H17B···F8^vii	0.99	2.42	3.262 (4)	143
OB—HB···F4^viii	0.84	1.91	2.746 (14)	173

Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x, y−1, z; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+1/2, −y, z−1/2; (v) −x+1/2, −y+1, z−1/2; (vi) x+1/2, −y+1/2, −z+1; (vii) −x+1, y−1/2, −z+1/2; (viii) −x+1, y+1/2, −z+3/2.