research communications
H-pyrazol-1-yl)borato]iron(II)
and magnetic properties of bis[butyltris(1aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska Street 64, Kyiv, 01601, Ukraine, and bUkrOrgSyntez Ltd, Chervonotkatska Street 67, Kyiv 02094, Ukraine
*Correspondence e-mail: mcs@univ.kiev.ua
The 13H18BN6)2], contains two half independent complex molecules. In each complex, the FeII atom is located on an inversion center and is surrounded by two scorpionate ligand butyltris(1H-pyrazol-1-yl)borate molecules that coordinate to the iron(II) ion through the N atoms of the pyrazole groups. The two independent complex molecules differ essentially in the conformation of the butyl substituents. In the crystal, the complex molecules are linked by a series of C—H⋯π interactions, which generate a supramolecular three-dimensional structure. At 120 K, the average Fe—N bond distance is 1.969 Å, indicating the low-spin state of the iron(II) atom, which does not change upon heating, as demonstrated by high-temperature measurements.
of the title compound, [Fe(CKeywords: crystal structure; polypyrazolyl borate; iron(II) scorpionates; magnetism; C—H⋯π interactions.
CCDC reference: 1946393
1. Chemical context
Scorpionates, coordination metal complexes of poly(1-pyrazolyl)borates, have been studied intensively since the pioneering work of Trofimenko (1999). Iron(II) derivatives are particularly interesting because of the spin-state crossover between 1A1 low-spin (LS) and 5T2g high-spin (HS) observed for several scorpionate ligands (Long et al., 2004; Halcrow, 2007). Complexes of this type are sensitive to the effects induced by substituents on the electronic structure of the ligand and/or steric crowding (Hamon et al., 2008). The prototypical [Fe(HB(pz)3)2], the LS compound at 295 K, undergoes a spin-state crossover to the HS state upon heating to ca 420 K (Long et al., 2004). Introducing methyl substituents to the pyrazole moieties decreases the and shifts the spin crossover down in temperature or completely stabilizes the high-spin state of the iron(II) ion (Long et al., 2004). In contrast, scorpionate ligands bearing an organic substituent instead of the hydrogen atom on the hub boron atom demonstrate stabilization of the low-spin state and shift of the spin transition to the higher temperature range (Hamon et al., 2008).
Our continuing interest consists of a study of iron(II) complexes bearing alkyl chains (Seredyuk, 2012; Seredyuk et al., 2006, 2010, 2016) and those based on azol ligands (Seredyuk et al., 2007, 2015). Here we report on the synthesis, and magnetic properties of an alkylated charge-neutral iron(II) complex based on the scorpionate ligand butyltris(1H-pyrazol-1-yl)borate.
2. Structural commentary
The II atom, that is located on an inversion center, is surrounded by two scorpionate ligands; each one providing three pyrazole moieties coordinated in a fac mode, thus a pseudo-octahedral [FeN6] is formed (Fig. 1). The two complex molecules differ essentially in the conformation of the butyl groups. One of the methylene groups of the butyl substituents of the Fe1-based complex shows a gauche conformation, whilst the remaining two methylene groups are in the trans conformation. Oppositely, the three methylene groups of the butyl substituent of the Fe2-based molecule are close to a trans conformation (Fig. 1).
of the title compound contains two half independent complex molecules. In each complex, the FeThe average Fe—N bond length is 1.969 Å (Table 1), a typical value for the low-spin state of the iron(II) ion (Gütlich & Goodwin, 2004). The average trigonal distortion parameters Φ = Σ124(60 - θi)/24, where θi is the angle generated by superposition of two opposite faces of the octahedron (Chang et al. 1990,) and Σ = Σ112(|ϕi − 90|), where ϕi are the deviations from 90° of the cis-N—Fe—N angles in the coordination sphere (Drew et al. 1995), are 1.27 and 24.38°, respectively, which correspond to a relatively low distortion of the and are typical for the low-spin state of iron(II) (Guionneau et al., 2004). The averaged volume of the is equal to 10.155 Å3.
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3. Supramolecular features
In the crystal, molecules are linked by C—H⋯π interactions (Fig. 2, Table 2). The pyrazole–butyl or butyl–butyl contacts link the individual complex molecules to form layers parallel to the bc plane. The layers are linked by C—H⋯π pyrazole–pyrazole interactions (Table 2), leading to the formation of a supramolecular three-dimensional structure, as shown in Fig. 2.
4. Magnetic measurements
Variable-temperature −1 is shown in Fig. 3 in the form of χMT versus T (χM is the molar and T is the temperature). At 300 K, the χMT value is close to zero, and on heating the value remains constant up to 400 K. This corroborates well with the observed short average Fe—N bond length at 120 K and identifies the low-spin state of the central iron(II) ion.
measurements were performed on single crystals (20 mg) of the title compound using a Quantum Design MPMS2 superconducting quantum interference device (SQUID) susceptometer operating at 1 T in the temperature range 10–400 K. Experimental susceptibilities were corrected for the diamagnetism of the holder (gelatine capsule) and of the constituent atoms by the application of Pascal's constants. The magnetic behaviour of the compound recorded at 2 K min5. Database survey
A search of the Cambridge Structural Database (CSD, Version 5.39, update November 2017; Groom et al., 2016) for complexes containing the iron(II) ion based on a scorpionate ligand with a tri(1H-pyrazol-1-yl)borate fragment yielded 39 hits, with Fe—N bond lengths lying in the ranges 1.956–1.995 and 2.162–2.246 Å, respectively, for the low- and high-spin states of the iron(II) ion.
6. Synthesis and crystallization
The butyltris(1H-pyrazol-1-yl)borate ligand and the title compound were synthesized according to the reported procedures (Reger & Tarquini, 1982; Myers et al., 2008). The slow diffusion of hexane vapour into a chloroform solution of the title compound led to the separation of orange well-shaped crystals.
Elemental analysis for C26H36B2FeN12 (found): C, 52.56; H, 6.11; N, 28.29%; (calculated): C, 52.22; H, 6.05; N, 28.38%.
7. Refinement
Crystal data, data collection and structure . The H-atoms were included in calculated positions and treated as riding atoms: C—H = 0.93–0.97 Å with Uiso(H) = 1.2Ueq(C).
details are summarized in Table 3Supporting information
CCDC reference: 1946393
https://doi.org/10.1107/S2056989019011137/ff2161sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019011137/ff2161Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989019011137/ff2161Isup3.cdx
Data collection: CrysAlis PRO (Agilent, 2012); cell
CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b), PLATON (Spek, 2009) and publCIF (Westrip, 2010).[Fe(C13H18BN6)2] | F(000) = 1248 |
Mr = 594.14 | Dx = 1.388 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 16.0762 (4) Å | Cell parameters from 2385 reflections |
b = 10.1827 (2) Å | θ = 3.9–24.7° |
c = 18.3410 (3) Å | µ = 0.57 mm−1 |
β = 108.785 (2)° | T = 120 K |
V = 2842.48 (11) Å3 | Prismatic, orange |
Z = 4 | 0.08 × 0.04 × 0.04 mm |
Agilent SuperNova Sapphire3 diffractometer | 4596 reflections with I > 2σ(I) |
φ scans and ω scans with κ offset | Rint = 0.053 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | θmax = 29.8°, θmin = 2.9° |
Tmin = 0.769, Tmax = 1.000 | h = −21→21 |
17726 measured reflections | k = −12→14 |
7222 independent reflections | l = −23→24 |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.184 | H-atom parameters constrained |
S = 0.78 | w = 1/[σ2(Fo2) + (0.1086P)2 + 7.1302P] where P = (Fo2 + 2Fc2)/3 |
7222 reflections | (Δ/σ)max = 0.042 |
373 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.71 e Å−3 |
Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET) (compiled Sep 14 2012,17:21:16) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
x | y | z | Uiso*/Ueq | ||
Fe1 | 0.00000 | 0.00000 | 0.50000 | 0.0155 (2) | |
Fe2 | 0.50000 | 0.00000 | 0.50000 | 0.0164 (2) | |
N1 | −0.08358 (16) | 0.1221 (2) | 0.43205 (13) | 0.0180 (7) | |
N2 | 0.07144 (17) | 0.0187 (2) | 0.43129 (14) | 0.0190 (7) | |
N3 | 0.06259 (17) | 0.1526 (2) | 0.55863 (13) | 0.0186 (7) | |
N4 | −0.05505 (17) | 0.2339 (2) | 0.40633 (13) | 0.0191 (7) | |
N5 | 0.09021 (17) | 0.1412 (3) | 0.40957 (14) | 0.0195 (7) | |
N6 | 0.07608 (17) | 0.2625 (2) | 0.52172 (13) | 0.0185 (7) | |
C1 | −0.1716 (2) | 0.1239 (3) | 0.40482 (17) | 0.0233 (9) | |
C2 | −0.2013 (2) | 0.2375 (3) | 0.36109 (18) | 0.0256 (9) | |
C3 | −0.1259 (2) | 0.3041 (3) | 0.36344 (17) | 0.0238 (9) | |
C4 | 0.1166 (2) | −0.0672 (3) | 0.40370 (17) | 0.0232 (9) | |
C5 | 0.1659 (2) | −0.0017 (3) | 0.36471 (18) | 0.0257 (10) | |
C6 | 0.1480 (2) | 0.1291 (3) | 0.37018 (17) | 0.0219 (9) | |
C7 | 0.0940 (2) | 0.1777 (3) | 0.63425 (16) | 0.0211 (8) | |
C8 | 0.1281 (2) | 0.3052 (3) | 0.64677 (17) | 0.0212 (8) | |
C9 | 0.1151 (2) | 0.3554 (3) | 0.57409 (17) | 0.0215 (8) | |
C10 | 0.0694 (2) | 0.3998 (3) | 0.40007 (17) | 0.0229 (9) | |
C11 | 0.0458 (2) | 0.4211 (3) | 0.31252 (17) | 0.0281 (10) | |
C12 | 0.0626 (2) | 0.5604 (3) | 0.28979 (18) | 0.0263 (9) | |
C13 | 0.1591 (3) | 0.5980 (4) | 0.3142 (2) | 0.0374 (11) | |
B1 | 0.0458 (2) | 0.2628 (4) | 0.43210 (18) | 0.0196 (9) | |
N7 | 0.42396 (17) | 0.1237 (3) | 0.53253 (14) | 0.0206 (7) | |
N8 | 0.42220 (17) | 0.0242 (2) | 0.39276 (14) | 0.0191 (7) | |
N9 | 0.56735 (17) | 0.1520 (2) | 0.48428 (14) | 0.0199 (7) | |
N10 | 0.39344 (17) | 0.2352 (2) | 0.49125 (14) | 0.0200 (7) | |
N11 | 0.39382 (16) | 0.1463 (2) | 0.36572 (14) | 0.0175 (7) | |
N12 | 0.52540 (17) | 0.2641 (2) | 0.45014 (14) | 0.0195 (7) | |
C14 | 0.3881 (2) | 0.1201 (3) | 0.58890 (18) | 0.0254 (9) | |
C15 | 0.3332 (2) | 0.2279 (4) | 0.58413 (19) | 0.0292 (10) | |
C16 | 0.3382 (2) | 0.2988 (3) | 0.52117 (17) | 0.0229 (9) | |
C17 | 0.3881 (2) | −0.0589 (3) | 0.33497 (17) | 0.0222 (9) | |
C18 | 0.3368 (2) | 0.0083 (3) | 0.26958 (18) | 0.0234 (9) | |
C19 | 0.3418 (2) | 0.1382 (3) | 0.29165 (17) | 0.0214 (8) | |
C20 | 0.6534 (2) | 0.1765 (3) | 0.50184 (17) | 0.0228 (9) | |
C21 | 0.6682 (2) | 0.3032 (3) | 0.48037 (18) | 0.0262 (9) | |
C22 | 0.5852 (2) | 0.3555 (3) | 0.44766 (17) | 0.0241 (9) | |
C23 | 0.3840 (2) | 0.4040 (3) | 0.38150 (18) | 0.0245 (9) | |
C24 | 0.4056 (2) | 0.4516 (3) | 0.30977 (17) | 0.0240 (9) | |
C25 | 0.4168 (2) | 0.6000 (3) | 0.30874 (18) | 0.0244 (9) | |
C26 | 0.4399 (2) | 0.6506 (3) | 0.2394 (2) | 0.0299 (10) | |
B2 | 0.4229 (2) | 0.2666 (3) | 0.42016 (19) | 0.0194 (9) | |
H1 | −0.20780 | 0.05890 | 0.41370 | 0.0280* | |
H2 | −0.25920 | 0.26240 | 0.33600 | 0.0310* | |
H3 | −0.12370 | 0.38400 | 0.33960 | 0.0280* | |
H4 | 0.11540 | −0.15790 | 0.40960 | 0.0280* | |
H5 | 0.20280 | −0.03860 | 0.34030 | 0.0310* | |
H6 | 0.17170 | 0.19810 | 0.35010 | 0.0260* | |
H7 | 0.09340 | 0.11890 | 0.67290 | 0.0250* | |
H8 | 0.15380 | 0.34700 | 0.69380 | 0.0250* | |
H9 | 0.13070 | 0.43920 | 0.56300 | 0.0260* | |
H10A | 0.04100 | 0.46890 | 0.41980 | 0.0280* | |
H10B | 0.13220 | 0.41290 | 0.42270 | 0.0280* | |
H11A | 0.07970 | 0.36020 | 0.29270 | 0.0340* | |
H11B | −0.01580 | 0.40030 | 0.28820 | 0.0340* | |
H12A | 0.03790 | 0.56890 | 0.23430 | 0.0320* | |
H12B | 0.03210 | 0.62170 | 0.31270 | 0.0320* | |
H13A | 0.16460 | 0.68650 | 0.29830 | 0.0450* | |
H13B | 0.18960 | 0.53960 | 0.29040 | 0.0450* | |
H13C | 0.18400 | 0.59160 | 0.36920 | 0.0450* | |
H14 | 0.39830 | 0.05470 | 0.62610 | 0.0310* | |
H15 | 0.30040 | 0.24800 | 0.61620 | 0.0350* | |
H16 | 0.30870 | 0.37670 | 0.50270 | 0.0270* | |
H17 | 0.39710 | −0.14930 | 0.33770 | 0.0270* | |
H18 | 0.30590 | −0.02690 | 0.22170 | 0.0280* | |
H19 | 0.31410 | 0.20820 | 0.26080 | 0.0260* | |
H20 | 0.69760 | 0.11660 | 0.52530 | 0.0270* | |
H21 | 0.72190 | 0.34360 | 0.48660 | 0.0310* | |
H22 | 0.57260 | 0.43960 | 0.42730 | 0.0290* | |
H23A | 0.32050 | 0.39940 | 0.36780 | 0.0290* | |
H23B | 0.40370 | 0.47130 | 0.42070 | 0.0290* | |
H24A | 0.45930 | 0.40960 | 0.30860 | 0.0290* | |
H24B | 0.35870 | 0.42520 | 0.26390 | 0.0290* | |
H25A | 0.36270 | 0.64140 | 0.30930 | 0.0290* | |
H25B | 0.46280 | 0.62610 | 0.35530 | 0.0290* | |
H26A | 0.44570 | 0.74440 | 0.24240 | 0.0360* | |
H26B | 0.39420 | 0.62690 | 0.19290 | 0.0360* | |
H26C | 0.49440 | 0.61230 | 0.23920 | 0.0360* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0161 (3) | 0.0176 (3) | 0.0129 (3) | 0.0013 (2) | 0.0048 (2) | 0.0009 (2) |
Fe2 | 0.0173 (3) | 0.0149 (3) | 0.0166 (3) | 0.0033 (2) | 0.0051 (2) | 0.0013 (2) |
N1 | 0.0194 (12) | 0.0201 (12) | 0.0148 (11) | 0.0013 (10) | 0.0061 (9) | 0.0020 (10) |
N2 | 0.0184 (12) | 0.0223 (13) | 0.0163 (11) | 0.0013 (10) | 0.0057 (9) | 0.0019 (10) |
N3 | 0.0209 (12) | 0.0192 (12) | 0.0156 (11) | 0.0009 (10) | 0.0059 (9) | 0.0000 (10) |
N4 | 0.0213 (13) | 0.0182 (12) | 0.0168 (11) | 0.0016 (10) | 0.0049 (10) | 0.0020 (10) |
N5 | 0.0219 (13) | 0.0216 (13) | 0.0152 (11) | −0.0002 (10) | 0.0064 (9) | 0.0022 (10) |
N6 | 0.0225 (13) | 0.0176 (12) | 0.0148 (11) | 0.0008 (10) | 0.0052 (9) | 0.0008 (10) |
C1 | 0.0200 (15) | 0.0247 (16) | 0.0244 (15) | 0.0014 (12) | 0.0062 (12) | 0.0010 (13) |
C2 | 0.0200 (15) | 0.0265 (17) | 0.0261 (15) | 0.0064 (13) | 0.0017 (12) | 0.0035 (14) |
C3 | 0.0256 (16) | 0.0216 (16) | 0.0203 (14) | 0.0063 (13) | 0.0021 (12) | 0.0014 (12) |
C4 | 0.0229 (16) | 0.0256 (16) | 0.0209 (14) | 0.0070 (13) | 0.0068 (12) | −0.0007 (13) |
C5 | 0.0232 (16) | 0.0352 (19) | 0.0218 (15) | 0.0076 (14) | 0.0114 (12) | 0.0010 (14) |
C6 | 0.0217 (15) | 0.0277 (17) | 0.0168 (13) | −0.0007 (13) | 0.0068 (11) | 0.0007 (12) |
C7 | 0.0214 (15) | 0.0262 (16) | 0.0153 (13) | 0.0045 (12) | 0.0052 (11) | 0.0005 (12) |
C8 | 0.0205 (15) | 0.0241 (16) | 0.0181 (13) | 0.0010 (12) | 0.0050 (11) | −0.0052 (12) |
C9 | 0.0221 (15) | 0.0223 (15) | 0.0201 (14) | −0.0033 (12) | 0.0069 (12) | −0.0012 (12) |
C10 | 0.0250 (16) | 0.0249 (16) | 0.0184 (14) | −0.0029 (13) | 0.0063 (12) | 0.0003 (13) |
C11 | 0.0348 (18) | 0.0306 (18) | 0.0174 (14) | −0.0065 (15) | 0.0065 (13) | −0.0004 (13) |
C12 | 0.0299 (17) | 0.0262 (17) | 0.0230 (15) | 0.0048 (14) | 0.0088 (13) | 0.0075 (14) |
C13 | 0.040 (2) | 0.039 (2) | 0.0321 (18) | −0.0056 (17) | 0.0101 (16) | 0.0066 (17) |
B1 | 0.0233 (17) | 0.0221 (17) | 0.0139 (14) | 0.0010 (14) | 0.0067 (12) | 0.0001 (13) |
N7 | 0.0216 (13) | 0.0199 (13) | 0.0198 (12) | 0.0046 (10) | 0.0058 (10) | 0.0027 (10) |
N8 | 0.0209 (13) | 0.0164 (12) | 0.0191 (12) | 0.0039 (10) | 0.0051 (10) | 0.0000 (10) |
N9 | 0.0206 (13) | 0.0176 (12) | 0.0207 (12) | 0.0013 (10) | 0.0055 (10) | 0.0020 (10) |
N10 | 0.0203 (12) | 0.0174 (12) | 0.0219 (12) | 0.0050 (10) | 0.0063 (10) | 0.0011 (10) |
N11 | 0.0191 (12) | 0.0160 (12) | 0.0177 (11) | 0.0035 (10) | 0.0065 (9) | 0.0020 (10) |
N12 | 0.0226 (13) | 0.0154 (12) | 0.0199 (12) | 0.0013 (10) | 0.0059 (10) | 0.0014 (10) |
C14 | 0.0303 (17) | 0.0257 (16) | 0.0233 (15) | 0.0061 (14) | 0.0128 (13) | 0.0063 (13) |
C15 | 0.0294 (18) | 0.0345 (19) | 0.0278 (16) | 0.0075 (15) | 0.0151 (14) | −0.0001 (15) |
C16 | 0.0212 (15) | 0.0241 (16) | 0.0229 (14) | 0.0057 (12) | 0.0065 (12) | −0.0012 (13) |
C17 | 0.0260 (16) | 0.0176 (15) | 0.0223 (14) | 0.0016 (12) | 0.0070 (12) | −0.0036 (12) |
C18 | 0.0245 (16) | 0.0224 (16) | 0.0210 (14) | −0.0017 (12) | 0.0042 (12) | −0.0010 (12) |
C19 | 0.0236 (15) | 0.0190 (15) | 0.0195 (14) | 0.0009 (12) | 0.0040 (12) | 0.0047 (12) |
C20 | 0.0176 (14) | 0.0288 (17) | 0.0213 (14) | 0.0033 (12) | 0.0052 (11) | 0.0018 (13) |
C21 | 0.0240 (16) | 0.0284 (17) | 0.0259 (15) | −0.0044 (13) | 0.0077 (13) | −0.0010 (14) |
C22 | 0.0307 (17) | 0.0195 (15) | 0.0208 (14) | −0.0063 (13) | 0.0067 (12) | −0.0009 (12) |
C23 | 0.0306 (17) | 0.0177 (15) | 0.0227 (15) | 0.0064 (13) | 0.0051 (13) | 0.0004 (12) |
C24 | 0.0296 (17) | 0.0204 (15) | 0.0206 (14) | 0.0036 (13) | 0.0061 (12) | 0.0012 (13) |
C25 | 0.0272 (17) | 0.0207 (15) | 0.0268 (15) | 0.0010 (13) | 0.0108 (13) | −0.0020 (13) |
C26 | 0.0372 (19) | 0.0220 (16) | 0.0335 (17) | 0.0024 (14) | 0.0155 (15) | −0.0002 (14) |
B2 | 0.0199 (16) | 0.0185 (16) | 0.0187 (15) | 0.0007 (13) | 0.0047 (12) | −0.0011 (13) |
Fe1—N1 | 1.956 (2) | N9—N12 | 1.370 (3) |
Fe1—N2 | 1.969 (3) | C9—H9 | 0.9300 |
Fe1—N3 | 1.971 (2) | N9—C20 | 1.339 (4) |
Fe1—N1i | 1.956 (2) | C10—H10A | 0.9700 |
Fe1—N2i | 1.969 (3) | N10—C16 | 1.350 (4) |
Fe1—N3i | 1.971 (2) | N10—B2 | 1.557 (4) |
Fe2—N9ii | 1.963 (2) | C10—H10B | 0.9700 |
Fe2—N9 | 1.963 (2) | N11—C19 | 1.349 (4) |
Fe2—N7 | 1.977 (3) | C11—H11A | 0.9700 |
Fe2—N8 | 1.977 (2) | C11—H11B | 0.9700 |
Fe2—N7ii | 1.977 (3) | N11—B2 | 1.554 (4) |
Fe2—N8ii | 1.977 (2) | C12—H12A | 0.9700 |
N1—C1 | 1.341 (4) | C12—H12B | 0.9700 |
N1—N4 | 1.367 (3) | N12—C22 | 1.349 (4) |
N2—N5 | 1.372 (4) | N12—B2 | 1.560 (4) |
N2—C4 | 1.336 (4) | C13—H13A | 0.9600 |
N3—N6 | 1.361 (3) | C13—H13B | 0.9600 |
N3—C7 | 1.339 (4) | C13—H13C | 0.9600 |
N4—B1 | 1.564 (4) | C14—C15 | 1.394 (5) |
N4—C3 | 1.360 (4) | C15—C16 | 1.386 (5) |
N5—C6 | 1.354 (4) | C17—C18 | 1.396 (4) |
N5—B1 | 1.550 (5) | C18—C19 | 1.378 (4) |
N6—C9 | 1.350 (4) | C20—C21 | 1.392 (4) |
N6—B1 | 1.557 (4) | C21—C22 | 1.382 (5) |
C1—C2 | 1.401 (4) | C23—C24 | 1.543 (4) |
C2—C3 | 1.378 (5) | C23—B2 | 1.602 (4) |
C4—C5 | 1.396 (5) | C24—C25 | 1.523 (4) |
C5—C6 | 1.373 (4) | C25—C26 | 1.525 (5) |
C7—C8 | 1.399 (4) | C14—H14 | 0.9300 |
C8—C9 | 1.379 (4) | C15—H15 | 0.9300 |
C10—C11 | 1.542 (4) | C16—H16 | 0.9300 |
C10—B1 | 1.606 (5) | C17—H17 | 0.9300 |
C11—C12 | 1.527 (4) | C18—H18 | 0.9300 |
C12—C13 | 1.519 (6) | C19—H19 | 0.9300 |
C1—H1 | 0.9300 | C20—H20 | 0.9300 |
C2—H2 | 0.9300 | C21—H21 | 0.9300 |
C3—H3 | 0.9300 | C22—H22 | 0.9300 |
C4—H4 | 0.9300 | C23—H23A | 0.9700 |
C5—H5 | 0.9300 | C23—H23B | 0.9700 |
C6—H6 | 0.9300 | C24—H24A | 0.9700 |
N7—N10 | 1.365 (4) | C24—H24B | 0.9700 |
N7—C14 | 1.337 (4) | C25—H25A | 0.9700 |
C7—H7 | 0.9300 | C25—H25B | 0.9700 |
C8—H8 | 0.9300 | C26—H26A | 0.9600 |
N8—C17 | 1.329 (4) | C26—H26B | 0.9600 |
N8—N11 | 1.362 (3) | C26—H26C | 0.9600 |
N1—Fe1—N2 | 87.32 (10) | N6—C9—H9 | 126.00 |
N1—Fe1—N3 | 88.38 (9) | C8—C9—H9 | 126.00 |
N1—Fe1—N1i | 180.00 | N12—N9—C20 | 105.8 (2) |
N1—Fe1—N2i | 92.68 (10) | C16—N10—B2 | 131.2 (2) |
N1—Fe1—N3i | 91.62 (9) | C11—C10—H10B | 107.00 |
N2—Fe1—N3 | 88.42 (10) | B1—C10—H10B | 107.00 |
N1i—Fe1—N2 | 92.68 (10) | H10A—C10—H10B | 107.00 |
N2—Fe1—N2i | 180.00 | B1—C10—H10A | 107.00 |
N2—Fe1—N3i | 91.58 (10) | N7—N10—C16 | 109.8 (2) |
N1i—Fe1—N3 | 91.62 (9) | N7—N10—B2 | 118.9 (2) |
N2i—Fe1—N3 | 91.58 (10) | C11—C10—H10A | 107.00 |
N3—Fe1—N3i | 180.00 | N8—N11—C19 | 109.7 (2) |
N1i—Fe1—N2i | 87.32 (10) | N8—N11—B2 | 119.3 (2) |
N1i—Fe1—N3i | 88.38 (9) | C19—N11—B2 | 131.0 (2) |
N2i—Fe1—N3i | 88.42 (10) | C12—C11—H11A | 109.00 |
N7—Fe2—N8ii | 91.93 (10) | C10—C11—H11A | 109.00 |
N7—Fe2—N9ii | 91.96 (11) | C10—C11—H11B | 109.00 |
N8—Fe2—N9 | 87.58 (10) | C12—C11—H11B | 109.00 |
N7ii—Fe2—N8 | 91.93 (10) | H11A—C11—H11B | 108.00 |
N8—Fe2—N8ii | 180.00 | N9—N12—C22 | 109.8 (3) |
N8—Fe2—N9ii | 92.42 (10) | C11—C12—H12A | 109.00 |
N7ii—Fe2—N9 | 91.96 (11) | C11—C12—H12B | 109.00 |
N8ii—Fe2—N9 | 92.42 (10) | C13—C12—H12A | 109.00 |
N9—Fe2—N9ii | 180.00 | C13—C12—H12B | 109.00 |
N7ii—Fe2—N8ii | 88.07 (10) | H12A—C12—H12B | 108.00 |
N7ii—Fe2—N9ii | 88.04 (11) | C22—N12—B2 | 131.3 (2) |
N8ii—Fe2—N9ii | 87.58 (10) | N9—N12—B2 | 118.9 (2) |
N7—Fe2—N8 | 88.07 (10) | C12—C13—H13B | 109.00 |
N7—Fe2—N9 | 88.04 (11) | C12—C13—H13C | 109.00 |
N7—Fe2—N7ii | 180.00 | H13A—C13—H13C | 110.00 |
Fe1—N1—N4 | 120.8 (2) | H13B—C13—H13C | 110.00 |
Fe1—N1—C1 | 132.2 (2) | H13A—C13—H13B | 109.00 |
N4—N1—C1 | 106.9 (2) | C12—C13—H13A | 109.00 |
Fe1—N2—N5 | 120.13 (19) | N7—C14—C15 | 110.6 (3) |
Fe1—N2—C4 | 132.79 (19) | C14—C15—C16 | 104.9 (3) |
N5—N2—C4 | 106.7 (3) | N10—C16—C15 | 108.1 (3) |
Fe1—N3—N6 | 120.79 (17) | N8—C17—C18 | 110.5 (3) |
Fe1—N3—C7 | 132.2 (2) | C17—C18—C19 | 104.8 (3) |
N6—N3—C7 | 106.9 (2) | N11—C19—C18 | 108.3 (3) |
N1—N4—C3 | 109.0 (3) | N9—C20—C21 | 111.2 (3) |
N1—N4—B1 | 118.9 (2) | C20—C21—C22 | 104.5 (3) |
C3—N4—B1 | 132.0 (3) | N12—C22—C21 | 108.6 (3) |
N2—N5—B1 | 119.0 (3) | C24—C23—B2 | 119.3 (3) |
C6—N5—B1 | 132.0 (3) | C23—C24—C25 | 112.5 (3) |
N2—N5—C6 | 109.0 (3) | C24—C25—C26 | 114.0 (3) |
C9—N6—B1 | 131.7 (3) | N10—B2—N11 | 105.5 (2) |
N3—N6—C9 | 109.5 (2) | N10—B2—N12 | 105.8 (2) |
N3—N6—B1 | 118.8 (2) | N10—B2—C23 | 111.7 (2) |
N1—C1—C2 | 110.4 (3) | N11—B2—N12 | 106.2 (2) |
C1—C2—C3 | 104.7 (3) | N11—B2—C23 | 114.2 (2) |
N4—C3—C2 | 108.9 (3) | N12—B2—C23 | 112.8 (2) |
N2—C4—C5 | 110.4 (3) | N7—C14—H14 | 125.00 |
C4—C5—C6 | 105.0 (3) | C15—C14—H14 | 125.00 |
N5—C6—C5 | 108.9 (3) | C14—C15—H15 | 128.00 |
N3—C7—C8 | 110.1 (3) | C16—C15—H15 | 128.00 |
C7—C8—C9 | 104.8 (3) | N10—C16—H16 | 126.00 |
N6—C9—C8 | 108.6 (3) | C15—C16—H16 | 126.00 |
C11—C10—B1 | 119.7 (3) | N8—C17—H17 | 125.00 |
C10—C11—C12 | 114.2 (3) | C18—C17—H17 | 125.00 |
C11—C12—C13 | 114.0 (3) | C17—C18—H18 | 128.00 |
N4—B1—N5 | 106.9 (3) | C19—C18—H18 | 128.00 |
N4—B1—N6 | 105.1 (2) | N11—C19—H19 | 126.00 |
N4—B1—C10 | 113.4 (3) | C18—C19—H19 | 126.00 |
N5—B1—N6 | 105.4 (2) | N9—C20—H20 | 124.00 |
N5—B1—C10 | 114.4 (3) | C21—C20—H20 | 124.00 |
N6—B1—C10 | 111.0 (3) | C20—C21—H21 | 128.00 |
N1—C1—H1 | 125.00 | C22—C21—H21 | 128.00 |
C2—C1—H1 | 125.00 | N12—C22—H22 | 126.00 |
C1—C2—H2 | 128.00 | C21—C22—H22 | 126.00 |
C3—C2—H2 | 128.00 | C24—C23—H23A | 108.00 |
N4—C3—H3 | 125.00 | C24—C23—H23B | 108.00 |
C2—C3—H3 | 126.00 | B2—C23—H23A | 107.00 |
N2—C4—H4 | 125.00 | B2—C23—H23B | 108.00 |
C5—C4—H4 | 125.00 | H23A—C23—H23B | 107.00 |
C4—C5—H5 | 128.00 | C23—C24—H24A | 109.00 |
C6—C5—H5 | 127.00 | C23—C24—H24B | 109.00 |
N5—C6—H6 | 126.00 | C25—C24—H24A | 109.00 |
C5—C6—H6 | 126.00 | C25—C24—H24B | 109.00 |
Fe2—N7—N10 | 120.6 (2) | H24A—C24—H24B | 108.00 |
N3—C7—H7 | 125.00 | C24—C25—H25A | 109.00 |
C8—C7—H7 | 125.00 | C24—C25—H25B | 109.00 |
N10—N7—C14 | 106.5 (3) | C26—C25—H25A | 109.00 |
Fe2—N7—C14 | 132.8 (2) | C26—C25—H25B | 109.00 |
C9—C8—H8 | 128.00 | H25A—C25—H25B | 108.00 |
C7—C8—H8 | 128.00 | C25—C26—H26A | 110.00 |
Fe2—N8—N11 | 120.43 (17) | C25—C26—H26B | 109.00 |
Fe2—N8—C17 | 132.88 (19) | C25—C26—H26C | 109.00 |
N11—N8—C17 | 106.7 (2) | H26A—C26—H26B | 109.00 |
Fe2—N9—N12 | 120.7 (2) | H26A—C26—H26C | 109.00 |
Fe2—N9—C20 | 133.5 (2) | H26B—C26—H26C | 109.00 |
N2—Fe1—N1—N4 | −45.0 (2) | N2—N5—B1—N6 | 60.6 (3) |
N2—Fe1—N1—C1 | 138.6 (3) | C6—N5—B1—N6 | −119.3 (3) |
N3—Fe1—N1—N4 | 43.5 (2) | C6—N5—B1—N4 | 129.3 (3) |
N3—Fe1—N1—C1 | −132.9 (3) | C6—N5—B1—C10 | 2.9 (4) |
N2i—Fe1—N1—N4 | 135.0 (2) | N2—N5—B1—C10 | −177.3 (2) |
N2i—Fe1—N1—C1 | −41.4 (3) | C9—N6—B1—N5 | 126.1 (4) |
N3i—Fe1—N1—N4 | −136.5 (2) | N3—N6—B1—N5 | −54.5 (3) |
N3i—Fe1—N1—C1 | 47.1 (3) | N3—N6—B1—N4 | 58.3 (3) |
N1—Fe1—N2—N5 | 48.8 (2) | C9—N6—B1—N4 | −121.2 (4) |
N1—Fe1—N2—C4 | −138.9 (3) | B1—N6—C9—C8 | 179.9 (3) |
N3—Fe1—N2—N5 | −39.7 (2) | N3—N6—B1—C10 | −178.8 (3) |
N3—Fe1—N2—C4 | 132.7 (3) | C9—N6—B1—C10 | 1.8 (5) |
N1i—Fe1—N2—N5 | −131.2 (2) | N3—N6—C9—C8 | 0.5 (4) |
N1i—Fe1—N2—C4 | 41.1 (3) | N1—C1—C2—C3 | 0.1 (4) |
N3i—Fe1—N2—N5 | 140.3 (2) | C1—C2—C3—N4 | 0.0 (3) |
N3i—Fe1—N2—C4 | −47.3 (3) | N2—C4—C5—C6 | 0.0 (4) |
N1—Fe1—N3—N6 | −42.0 (2) | C4—C5—C6—N5 | −0.7 (4) |
N1—Fe1—N3—C7 | 133.5 (3) | N3—C7—C8—C9 | 0.2 (4) |
N2—Fe1—N3—N6 | 45.4 (2) | C7—C8—C9—N6 | −0.4 (4) |
N2—Fe1—N3—C7 | −139.1 (3) | B1—C10—C11—C12 | 173.6 (3) |
N1i—Fe1—N3—N6 | 138.0 (2) | C11—C10—B1—N5 | 60.5 (4) |
N1i—Fe1—N3—C7 | −46.5 (3) | C11—C10—B1—N6 | 179.6 (3) |
N2i—Fe1—N3—N6 | −134.6 (2) | C11—C10—B1—N4 | −62.5 (4) |
N2i—Fe1—N3—C7 | 40.9 (3) | C10—C11—C12—C13 | 67.1 (4) |
N9—Fe2—N8—N11 | −44.3 (2) | Fe2—N7—N10—C16 | 175.6 (2) |
N9—Fe2—N8—C17 | 135.2 (3) | Fe2—N7—N10—B2 | −2.7 (3) |
N7ii—Fe2—N8—N11 | −136.2 (2) | C14—N7—N10—C16 | −0.9 (3) |
N7ii—Fe2—N8—C17 | 43.3 (3) | C14—N7—N10—B2 | −179.3 (3) |
N9ii—Fe2—N8—N11 | 135.7 (2) | Fe2—N7—C14—C15 | −175.1 (2) |
N9ii—Fe2—N8—C17 | −44.8 (3) | N10—N7—C14—C15 | 0.8 (4) |
N7—Fe2—N9—N12 | −42.2 (2) | Fe2—N8—N11—C19 | −179.9 (2) |
N7—Fe2—N9—C20 | 136.2 (3) | Fe2—N8—N11—B2 | −0.3 (4) |
N8—Fe2—N9—N12 | 46.0 (2) | C17—N8—N11—C19 | 0.5 (4) |
N8—Fe2—N9—C20 | −135.7 (3) | C17—N8—N11—B2 | −179.9 (3) |
N7ii—Fe2—N9—N12 | 137.8 (2) | Fe2—N8—C17—C18 | −179.7 (2) |
N7ii—Fe2—N9—C20 | −43.8 (3) | N11—N8—C17—C18 | −0.2 (4) |
N8ii—Fe2—N9—N12 | −134.1 (2) | Fe2—N9—N12—C22 | 178.28 (19) |
N8ii—Fe2—N9—C20 | 44.3 (3) | Fe2—N9—N12—B2 | −3.0 (3) |
N9ii—Fe2—N7—C14 | 41.0 (3) | C20—N9—N12—C22 | −0.5 (3) |
N7—Fe2—N8—N11 | 43.8 (2) | C20—N9—N12—B2 | 178.2 (2) |
N7—Fe2—N8—C17 | −136.7 (3) | Fe2—N9—C20—C21 | −178.0 (2) |
N9—Fe2—N7—N10 | 45.5 (2) | N12—N9—C20—C21 | 0.6 (3) |
N9—Fe2—N7—C14 | −139.0 (3) | N7—N10—C16—C15 | 0.7 (4) |
N8ii—Fe2—N7—N10 | 137.8 (2) | B2—N10—C16—C15 | 178.7 (3) |
N8ii—Fe2—N7—C14 | −46.7 (3) | C16—N10—B2—N12 | 127.7 (3) |
N9ii—Fe2—N7—N10 | −134.5 (2) | N7—N10—B2—C23 | −177.5 (3) |
N8—Fe2—N7—N10 | −42.2 (2) | C16—N10—B2—C23 | 4.6 (4) |
N8—Fe2—N7—C14 | 133.3 (3) | C16—N10—B2—N11 | −120.0 (3) |
Fe1—N1—N4—C3 | −177.10 (19) | N7—N10—B2—N12 | −54.3 (3) |
Fe1—N1—N4—B1 | 0.0 (3) | N7—N10—B2—N11 | 57.9 (3) |
C1—N1—N4—C3 | 0.1 (3) | N8—N11—B2—N10 | −56.3 (3) |
C1—N1—N4—B1 | 177.3 (2) | C19—N11—B2—N10 | 123.2 (3) |
Fe1—N1—C1—C2 | 176.6 (2) | C19—N11—B2—C23 | 0.3 (5) |
N4—N1—C1—C2 | −0.1 (3) | B2—N11—C19—C18 | 179.8 (3) |
N5—N2—C4—C5 | 0.7 (3) | C19—N11—B2—N12 | −124.7 (3) |
Fe1—N2—N5—C6 | 173.0 (2) | N8—N11—B2—C23 | −179.3 (3) |
Fe1—N2—N5—B1 | −6.9 (3) | N8—N11—B2—N12 | 55.7 (3) |
C4—N2—N5—C6 | −1.2 (3) | N8—N11—C19—C18 | −0.6 (4) |
C4—N2—N5—B1 | 178.9 (3) | C22—N12—B2—N10 | −123.8 (3) |
Fe1—N2—C4—C5 | −172.4 (2) | N9—N12—B2—N11 | −53.9 (3) |
C7—N3—N6—C9 | −0.4 (4) | N9—N12—B2—N10 | 57.9 (3) |
C7—N3—N6—B1 | −179.9 (3) | N9—N12—C22—C21 | 0.3 (3) |
Fe1—N3—C7—C8 | −175.8 (2) | B2—N12—C22—C21 | −178.2 (3) |
N6—N3—C7—C8 | 0.1 (4) | C22—N12—B2—C23 | −1.4 (4) |
Fe1—N3—N6—C9 | 176.2 (2) | C22—N12—B2—N11 | 124.5 (3) |
Fe1—N3—N6—B1 | −3.4 (4) | N9—N12—B2—C23 | −179.7 (2) |
N1—N4—C3—C2 | −0.1 (3) | N7—C14—C15—C16 | −0.4 (4) |
C3—N4—B1—N6 | 119.8 (3) | C14—C15—C16—N10 | −0.2 (4) |
B1—N4—C3—C2 | −176.7 (3) | N8—C17—C18—C19 | −0.2 (4) |
N1—N4—B1—N6 | −56.6 (3) | C17—C18—C19—N11 | 0.5 (4) |
C3—N4—B1—C10 | −1.5 (4) | N9—C20—C21—C22 | −0.4 (4) |
N1—N4—B1—N5 | 55.1 (3) | C20—C21—C22—N12 | 0.1 (3) |
C3—N4—B1—N5 | −128.5 (3) | B2—C23—C24—C25 | −144.3 (3) |
N1—N4—B1—C10 | −177.9 (2) | C24—C23—B2—N12 | 61.3 (4) |
N2—N5—B1—N4 | −50.9 (3) | C24—C23—B2—N10 | −179.6 (3) |
N2—N5—C6—C5 | 1.2 (3) | C24—C23—B2—N11 | −60.1 (4) |
B1—N5—C6—C5 | −178.9 (3) | C23—C24—C25—C26 | 178.9 (3) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z+1. |
Cg2 and Cg11 are the centroids of rings N2/N5/C4–C6 and N8/N11/C17–C19, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···Cg11 | 0.93 | 3.00 | 3.674 (4) | 131 |
C12—H12A···Cg2iii | 0.97 | 2.87 | 3.703 (3) | 145 |
C26—H26C···Cg11iv | 0.96 | 2.84 | 3.720 (4) | 153 |
Symmetry codes: (iii) −x, y+1/2, −z+1/2; (iv) −x+1, y+1/2, −z+1/2. |
Funding information
Funding for this research was provided by: H2020 Marie Skłodowska-Curie Actions (grant No. 734322).
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