The X-ray crystal structure of tris[
N-(2-hydroxyethyl)-2,2′-iminodiethanolato]tris(2,2′,2′′-nitrilotriethanolato)tetrairon(II)triiron(III) bis(perchlorate), [Fe
7(C
6H
12NO
3)
3(C
6H
13NO
3)
3](ClO
4)
2 or [Fe
7(tea)
3(tea-H)
3](ClO
4)
2 (tea-H
3 is triethanolamine), is known from the literature [Liu
et al. (2008).
Z. Anorg. Allg. Chem. 634, 778–783] as a heptanuclear coordination cluster. The space group was given as
I2
13 and is reinvestigated in the present study. We find a new space-group symmetry of
Pa and could detect O—H hydrogens, which were missing in the original publication. Consequences on the Fe oxidation states are investigated with the bond-valence method, resulting in a mixed-valence core of four Fe
II and three Fe
III centres. Symmetry relationships between the two space groups and the average supergroup
Ia are discussed in detail.
Supporting information
CCDC reference: 1813756
Data collection: APEX3 (Bruker, 2016); cell refinement: PEAKREF (Schreurs, 2016); data reduction: EVAL15 (Schreurs et al., 2010) and SADABS (Sheldrick,
2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).
Tris[
N-(2-hydroxyethyl)-2,2'-iminodiiethanolato]tris(2,2',2''-\
nitrilotriethanolato)tetrairon(II)triiron(III) bis(perchlorate)
top
Crystal data top
[Fe7(C6H12NO3)3(C6H13NO3)3](ClO4)2 | Mo Kα radiation, λ = 0.71073 Å |
Mr = 1469.87 | Cell parameters from 104201 reflections |
Cubic, Pa3 | θ = 1.3–35.1° |
a = 22.0884 (6) Å | µ = 2.02 mm−1 |
V = 10776.9 (8) Å3 | T = 100 K |
Z = 8 | Block, black |
F(000) = 6056 | 0.22 × 0.09 × 0.08 mm |
Dx = 1.812 Mg m−3 | |
Data collection top
Bruker Kappa APEXII diffractometer | 6121 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.055 |
φ and ω scans | θmax = 35.1°, θmin = 1.6° |
Absorption correction: numerical (SADABS; Sheldrick, 2014) | h = −35→30 |
Tmin = 0.687, Tmax = 0.887 | k = −34→35 |
211368 measured reflections | l = −33→31 |
7962 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.028 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.070 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0318P)2 + 4.712P] where P = (Fo2 + 2Fc2)/3 |
7962 reflections | (Δ/σ)max = 0.002 |
236 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Fe1 | 0.25330 (2) | 0.25330 (2) | 0.25330 (2) | 0.00791 (5) | |
Fe2 | 0.22069 (2) | 0.16731 (2) | 0.36722 (2) | 0.00893 (4) | |
Fe3 | 0.33830 (2) | 0.13764 (2) | 0.28373 (2) | 0.00842 (4) | |
O1 | 0.17204 (4) | 0.21290 (4) | 0.29115 (4) | 0.00986 (14) | |
O2 | 0.21869 (4) | 0.12195 (4) | 0.45628 (4) | 0.01637 (17) | |
H2 | 0.2383 (9) | 0.1233 (11) | 0.4913 (9) | 0.048 (7)* | |
O3 | 0.26809 (4) | 0.10217 (4) | 0.32397 (4) | 0.01312 (16) | |
O4 | 0.29956 (4) | 0.21244 (4) | 0.32770 (4) | 0.00978 (14) | |
O5 | 0.37899 (4) | 0.05905 (4) | 0.27734 (4) | 0.01365 (16) | |
O6 | 0.40289 (4) | 0.18411 (4) | 0.24104 (4) | 0.01275 (15) | |
N1 | 0.14858 (4) | 0.10076 (4) | 0.35394 (4) | 0.01091 (17) | |
N2 | 0.40266 (4) | 0.15008 (4) | 0.35735 (4) | 0.01108 (17) | |
C1 | 0.10275 (5) | 0.13060 (5) | 0.31484 (5) | 0.0129 (2) | |
H1A | 0.076640 | 0.156948 | 0.340002 | 0.015* | |
H1B | 0.076764 | 0.099374 | 0.295911 | 0.015* | |
C2 | 0.13276 (5) | 0.16854 (5) | 0.26538 (5) | 0.01151 (19) | |
H2A | 0.156258 | 0.141764 | 0.238188 | 0.014* | |
H2B | 0.101192 | 0.188918 | 0.240948 | 0.014* | |
C3 | 0.12445 (5) | 0.08718 (6) | 0.41514 (5) | 0.0146 (2) | |
H3A | 0.097115 | 0.051736 | 0.412797 | 0.017* | |
H3B | 0.100542 | 0.122151 | 0.429773 | 0.017* | |
C4 | 0.17503 (6) | 0.07400 (5) | 0.45961 (5) | 0.0152 (2) | |
H4A | 0.158507 | 0.071214 | 0.501178 | 0.018* | |
H4B | 0.194465 | 0.034891 | 0.449512 | 0.018* | |
C5 | 0.17540 (5) | 0.04711 (5) | 0.32310 (6) | 0.0134 (2) | |
H5A | 0.166443 | 0.049253 | 0.279232 | 0.016* | |
H5B | 0.156514 | 0.009797 | 0.339230 | 0.016* | |
C6 | 0.24374 (5) | 0.04385 (5) | 0.33227 (5) | 0.0126 (2) | |
H6A | 0.252965 | 0.029135 | 0.373582 | 0.015* | |
H6B | 0.261812 | 0.015364 | 0.302765 | 0.015* | |
C7 | 0.37356 (5) | 0.18936 (5) | 0.40332 (5) | 0.0130 (2) | |
H7A | 0.404749 | 0.207173 | 0.430125 | 0.016* | |
H7B | 0.345497 | 0.165143 | 0.428525 | 0.016* | |
C8 | 0.33886 (5) | 0.23950 (5) | 0.37111 (5) | 0.0121 (2) | |
H8A | 0.314986 | 0.263136 | 0.400776 | 0.014* | |
H8B | 0.367487 | 0.267273 | 0.350669 | 0.014* | |
C9 | 0.41247 (6) | 0.08692 (5) | 0.37804 (5) | 0.0149 (2) | |
H9A | 0.376760 | 0.072762 | 0.401131 | 0.018* | |
H9B | 0.448238 | 0.085129 | 0.404990 | 0.018* | |
C10 | 0.42245 (5) | 0.04634 (5) | 0.32320 (6) | 0.0146 (2) | |
H10A | 0.463706 | 0.052964 | 0.306983 | 0.018* | |
H10B | 0.419081 | 0.003389 | 0.335540 | 0.018* | |
C11 | 0.45825 (5) | 0.17931 (6) | 0.33281 (5) | 0.0137 (2) | |
H11A | 0.494455 | 0.160261 | 0.351123 | 0.016* | |
H11B | 0.458364 | 0.222757 | 0.343807 | 0.016* | |
C12 | 0.46122 (5) | 0.17298 (5) | 0.26411 (5) | 0.0130 (2) | |
H12A | 0.490419 | 0.202435 | 0.247136 | 0.016* | |
H12B | 0.474609 | 0.131682 | 0.252974 | 0.016* | |
Cl1 | 0.09580 (2) | 0.09580 (2) | 0.09580 (2) | 0.01534 (9) | |
O7 | 0.08074 (5) | 0.08564 (5) | 0.15863 (5) | 0.0266 (2) | |
O8 | 0.05841 (5) | 0.05841 (5) | 0.05841 (5) | 0.0304 (4) | |
Cl2 | 0.41017 (2) | 0.41017 (2) | 0.41017 (2) | 0.01490 (9) | |
O9 | 0.42281 (5) | 0.34728 (5) | 0.42264 (5) | 0.0253 (2) | |
O10 | 0.44765 (5) | 0.44765 (5) | 0.44765 (5) | 0.0281 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Fe1 | 0.00791 (5) | 0.00791 (5) | 0.00791 (5) | 0.00099 (5) | 0.00099 (5) | 0.00099 (5) |
Fe2 | 0.00892 (7) | 0.00825 (7) | 0.00963 (7) | 0.00067 (5) | 0.00126 (5) | 0.00061 (5) |
Fe3 | 0.00793 (7) | 0.00863 (7) | 0.00871 (7) | 0.00104 (5) | 0.00021 (5) | 0.00058 (5) |
O1 | 0.0105 (3) | 0.0091 (3) | 0.0101 (3) | −0.0005 (3) | 0.0005 (3) | −0.0005 (3) |
O2 | 0.0209 (4) | 0.0160 (4) | 0.0123 (4) | −0.0039 (3) | −0.0032 (3) | 0.0034 (3) |
O3 | 0.0131 (4) | 0.0087 (3) | 0.0176 (4) | 0.0000 (3) | 0.0047 (3) | 0.0006 (3) |
O4 | 0.0096 (3) | 0.0099 (3) | 0.0098 (3) | 0.0005 (3) | −0.0010 (3) | 0.0001 (3) |
O5 | 0.0129 (4) | 0.0120 (4) | 0.0161 (4) | 0.0025 (3) | −0.0014 (3) | −0.0013 (3) |
O6 | 0.0079 (3) | 0.0176 (4) | 0.0127 (4) | 0.0008 (3) | −0.0002 (3) | 0.0042 (3) |
N1 | 0.0105 (4) | 0.0106 (4) | 0.0117 (4) | 0.0003 (3) | 0.0015 (3) | 0.0007 (3) |
N2 | 0.0106 (4) | 0.0115 (4) | 0.0111 (4) | 0.0018 (3) | −0.0005 (3) | 0.0009 (3) |
C1 | 0.0101 (5) | 0.0132 (5) | 0.0153 (5) | −0.0011 (4) | −0.0004 (4) | 0.0016 (4) |
C2 | 0.0114 (5) | 0.0119 (5) | 0.0112 (5) | −0.0016 (4) | −0.0015 (4) | −0.0007 (4) |
C3 | 0.0138 (5) | 0.0161 (5) | 0.0138 (5) | −0.0016 (4) | 0.0033 (4) | 0.0027 (4) |
C4 | 0.0204 (6) | 0.0133 (5) | 0.0118 (5) | −0.0028 (4) | 0.0011 (4) | 0.0025 (4) |
C5 | 0.0141 (5) | 0.0096 (5) | 0.0164 (5) | −0.0009 (4) | 0.0006 (4) | −0.0010 (4) |
C6 | 0.0139 (5) | 0.0079 (4) | 0.0161 (5) | 0.0002 (4) | 0.0023 (4) | 0.0011 (4) |
C7 | 0.0138 (5) | 0.0153 (5) | 0.0101 (5) | 0.0026 (4) | −0.0014 (4) | −0.0007 (4) |
C8 | 0.0136 (5) | 0.0111 (5) | 0.0115 (5) | −0.0002 (4) | −0.0018 (4) | −0.0011 (4) |
C9 | 0.0173 (5) | 0.0136 (5) | 0.0138 (5) | 0.0030 (4) | −0.0017 (4) | 0.0034 (4) |
C10 | 0.0144 (5) | 0.0111 (5) | 0.0183 (5) | 0.0030 (4) | −0.0020 (4) | 0.0002 (4) |
C11 | 0.0102 (5) | 0.0159 (5) | 0.0152 (5) | −0.0009 (4) | −0.0017 (4) | 0.0004 (4) |
C12 | 0.0083 (5) | 0.0158 (5) | 0.0148 (5) | 0.0006 (4) | 0.0005 (4) | 0.0024 (4) |
Cl1 | 0.01534 (9) | 0.01534 (9) | 0.01534 (9) | 0.00135 (10) | 0.00135 (10) | 0.00135 (10) |
O7 | 0.0310 (6) | 0.0320 (6) | 0.0166 (5) | 0.0077 (4) | 0.0056 (4) | 0.0051 (4) |
O8 | 0.0304 (4) | 0.0304 (4) | 0.0304 (4) | −0.0074 (4) | −0.0074 (4) | −0.0074 (4) |
Cl2 | 0.01490 (9) | 0.01490 (9) | 0.01490 (9) | 0.00088 (10) | 0.00088 (10) | 0.00088 (10) |
O9 | 0.0321 (6) | 0.0161 (4) | 0.0278 (5) | 0.0056 (4) | 0.0044 (4) | 0.0032 (4) |
O10 | 0.0281 (4) | 0.0281 (4) | 0.0281 (4) | −0.0057 (4) | −0.0057 (4) | −0.0057 (4) |
Geometric parameters (Å, º) top
Fe1—O4i | 2.1352 (8) | C2—H2B | 0.9900 |
Fe1—O4ii | 2.1352 (8) | C3—C4 | 1.5159 (17) |
Fe1—O4 | 2.1353 (8) | C3—H3A | 0.9900 |
Fe1—O1 | 2.1719 (8) | C3—H3B | 0.9900 |
Fe1—O1i | 2.1719 (8) | C4—H4A | 0.9900 |
Fe1—O1ii | 2.1719 (8) | C4—H4B | 0.9900 |
Fe2—O6i | 1.9814 (8) | C5—C6 | 1.5247 (16) |
Fe2—O3 | 2.0198 (8) | C5—H5A | 0.9900 |
Fe2—N1 | 2.1873 (10) | C5—H5B | 0.9900 |
Fe2—O4 | 2.1888 (8) | C6—H6A | 0.9900 |
Fe2—O2 | 2.2081 (9) | C6—H6B | 0.9900 |
Fe2—O1 | 2.2342 (8) | C7—C8 | 1.5233 (16) |
Fe3—O3 | 1.9516 (8) | C7—H7A | 0.9900 |
Fe3—O5 | 1.9600 (8) | C7—H7B | 0.9900 |
Fe3—O6 | 1.9945 (8) | C8—H8A | 0.9900 |
Fe3—O1ii | 2.0270 (8) | C8—H8B | 0.9900 |
Fe3—O4 | 2.0989 (8) | C9—C10 | 1.5229 (17) |
Fe3—N2 | 2.1774 (10) | C9—H9A | 0.9900 |
O1—C2 | 1.4271 (13) | C9—H9B | 0.9900 |
O2—C4 | 1.4345 (15) | C10—H10A | 0.9900 |
O2—H2 | 0.89 (2) | C10—H10B | 0.9900 |
O3—C6 | 1.4080 (13) | C11—C12 | 1.5252 (16) |
O4—C8 | 1.4247 (14) | C11—H11A | 0.9900 |
O5—C10 | 1.4235 (14) | C11—H11B | 0.9900 |
O6—C12 | 1.4071 (14) | C12—H12A | 0.9900 |
N1—C3 | 1.4836 (15) | C12—H12B | 0.9900 |
N1—C1 | 1.4849 (15) | Cl1—O8 | 1.4302 (18) |
N1—C5 | 1.4898 (15) | Cl1—O7i | 1.4448 (10) |
N2—C7 | 1.4822 (15) | Cl1—O7ii | 1.4448 (10) |
N2—C9 | 1.4839 (15) | Cl1—O7 | 1.4448 (10) |
N2—C11 | 1.4896 (15) | Cl2—O10 | 1.4341 (19) |
C1—C2 | 1.5282 (16) | Cl2—O9 | 1.4435 (10) |
C1—H1A | 0.9900 | Cl2—O9i | 1.4435 (10) |
C1—H1B | 0.9900 | Cl2—O9ii | 1.4435 (10) |
C2—H2A | 0.9900 | | |
| | | |
O4i—Fe1—O4ii | 99.17 (3) | N1—C1—H1B | 109.4 |
O4i—Fe1—O4 | 99.16 (3) | C2—C1—H1B | 109.4 |
O4ii—Fe1—O4 | 99.16 (3) | H1A—C1—H1B | 108.0 |
O4i—Fe1—O1 | 77.45 (3) | O1—C2—C1 | 110.80 (9) |
O4ii—Fe1—O1 | 174.49 (3) | O1—C2—H2A | 109.5 |
O4—Fe1—O1 | 85.73 (3) | C1—C2—H2A | 109.5 |
O4i—Fe1—O1i | 85.73 (3) | O1—C2—H2B | 109.5 |
O4ii—Fe1—O1i | 77.44 (3) | C1—C2—H2B | 109.5 |
O4—Fe1—O1i | 174.49 (3) | H2A—C2—H2B | 108.1 |
O1—Fe1—O1i | 97.86 (3) | N1—C3—C4 | 111.37 (10) |
O4i—Fe1—O1ii | 174.49 (3) | N1—C3—H3A | 109.4 |
O4ii—Fe1—O1ii | 85.73 (3) | C4—C3—H3A | 109.4 |
O4—Fe1—O1ii | 77.45 (3) | N1—C3—H3B | 109.4 |
O1—Fe1—O1ii | 97.86 (3) | C4—C3—H3B | 109.4 |
O1i—Fe1—O1ii | 97.86 (3) | H3A—C3—H3B | 108.0 |
O6i—Fe2—O3 | 170.08 (4) | O2—C4—C3 | 108.69 (9) |
O6i—Fe2—N1 | 107.99 (4) | O2—C4—H4A | 110.0 |
O3—Fe2—N1 | 80.52 (4) | C3—C4—H4A | 110.0 |
O6i—Fe2—O4 | 96.25 (3) | O2—C4—H4B | 110.0 |
O3—Fe2—O4 | 73.93 (3) | C3—C4—H4B | 110.0 |
N1—Fe2—O4 | 146.33 (3) | H4A—C4—H4B | 108.3 |
O6i—Fe2—O2 | 90.60 (3) | N1—C5—C6 | 111.74 (9) |
O3—Fe2—O2 | 96.23 (4) | N1—C5—H5A | 109.3 |
N1—Fe2—O2 | 78.46 (4) | C6—C5—H5A | 109.3 |
O4—Fe2—O2 | 125.30 (3) | N1—C5—H5B | 109.3 |
O6i—Fe2—O1 | 74.48 (3) | C6—C5—H5B | 109.3 |
O3—Fe2—O1 | 102.40 (3) | H5A—C5—H5B | 107.9 |
N1—Fe2—O1 | 81.48 (3) | O3—C6—C5 | 108.54 (9) |
O4—Fe2—O1 | 82.97 (3) | O3—C6—H6A | 110.0 |
O2—Fe2—O1 | 149.87 (3) | C5—C6—H6A | 110.0 |
O3—Fe3—O5 | 92.38 (4) | O3—C6—H6B | 110.0 |
O3—Fe3—O6 | 172.02 (4) | C5—C6—H6B | 110.0 |
O5—Fe3—O6 | 95.38 (4) | H6A—C6—H6B | 108.4 |
O3—Fe3—O1ii | 95.38 (3) | N2—C7—C8 | 108.89 (9) |
O5—Fe3—O1ii | 120.80 (3) | N2—C7—H7A | 109.9 |
O6—Fe3—O1ii | 79.04 (3) | C8—C7—H7A | 109.9 |
O3—Fe3—O4 | 77.37 (3) | N2—C7—H7B | 109.9 |
O5—Fe3—O4 | 156.56 (3) | C8—C7—H7B | 109.9 |
O6—Fe3—O4 | 96.05 (3) | H7A—C7—H7B | 108.3 |
O1ii—Fe3—O4 | 81.53 (3) | O4—C8—C7 | 108.41 (9) |
O3—Fe3—N2 | 103.25 (4) | O4—C8—H8A | 110.0 |
O5—Fe3—N2 | 82.31 (4) | C7—C8—H8A | 110.0 |
O6—Fe3—N2 | 79.70 (4) | O4—C8—H8B | 110.0 |
O1ii—Fe3—N2 | 149.83 (4) | C7—C8—H8B | 110.0 |
O4—Fe3—N2 | 79.70 (3) | H8A—C8—H8B | 108.4 |
C2—O1—Fe3i | 120.46 (7) | N2—C9—C10 | 109.24 (9) |
C2—O1—Fe1 | 129.12 (7) | N2—C9—H9A | 109.8 |
Fe3i—O1—Fe1 | 100.98 (3) | C10—C9—H9A | 109.8 |
C2—O1—Fe2 | 106.43 (6) | N2—C9—H9B | 109.8 |
Fe3i—O1—Fe2 | 98.15 (3) | C10—C9—H9B | 109.8 |
Fe1—O1—Fe2 | 94.43 (3) | H9A—C9—H9B | 108.3 |
C4—O2—Fe2 | 113.21 (7) | O5—C10—C9 | 110.63 (9) |
C4—O2—H2 | 108.0 (15) | O5—C10—H10A | 109.5 |
Fe2—O2—H2 | 138.7 (14) | C9—C10—H10A | 109.5 |
C6—O3—Fe3 | 136.90 (7) | O5—C10—H10B | 109.5 |
C6—O3—Fe2 | 113.09 (7) | C9—C10—H10B | 109.5 |
Fe3—O3—Fe2 | 109.96 (4) | H10A—C10—H10B | 108.1 |
C8—O4—Fe3 | 113.16 (6) | N2—C11—C12 | 110.96 (9) |
C8—O4—Fe1 | 129.21 (7) | N2—C11—H11A | 109.4 |
Fe3—O4—Fe1 | 99.88 (3) | C12—C11—H11A | 109.4 |
C8—O4—Fe2 | 114.05 (7) | N2—C11—H11B | 109.4 |
Fe3—O4—Fe2 | 98.66 (3) | C12—C11—H11B | 109.4 |
Fe1—O4—Fe2 | 96.80 (3) | H11A—C11—H11B | 108.0 |
C10—O5—Fe3 | 115.63 (7) | O6—C12—C11 | 107.76 (9) |
C12—O6—Fe2ii | 137.14 (7) | O6—C12—H12A | 110.2 |
C12—O6—Fe3 | 113.19 (7) | C11—C12—H12A | 110.2 |
Fe2ii—O6—Fe3 | 108.30 (4) | O6—C12—H12B | 110.2 |
C3—N1—C1 | 112.01 (9) | C11—C12—H12B | 110.2 |
C3—N1—C5 | 113.50 (9) | H12A—C12—H12B | 108.5 |
C1—N1—C5 | 110.99 (9) | O8—Cl1—O7i | 109.39 (5) |
C3—N1—Fe2 | 105.98 (7) | O8—Cl1—O7ii | 109.39 (5) |
C1—N1—Fe2 | 106.02 (7) | O7i—Cl1—O7ii | 109.55 (5) |
C5—N1—Fe2 | 107.84 (7) | O8—Cl1—O7 | 109.40 (5) |
C7—N2—C9 | 113.75 (9) | O7i—Cl1—O7 | 109.55 (5) |
C7—N2—C11 | 110.68 (9) | O7ii—Cl1—O7 | 109.55 (5) |
C9—N2—C11 | 113.53 (9) | O10—Cl2—O9 | 109.50 (5) |
C7—N2—Fe3 | 107.60 (7) | O10—Cl2—O9i | 109.50 (5) |
C9—N2—Fe3 | 101.93 (7) | O9—Cl2—O9i | 109.45 (5) |
C11—N2—Fe3 | 108.73 (7) | O10—Cl2—O9ii | 109.50 (5) |
N1—C1—C2 | 111.32 (9) | O9—Cl2—O9ii | 109.44 (5) |
N1—C1—H1A | 109.4 | O9i—Cl2—O9ii | 109.45 (5) |
C2—C1—H1A | 109.4 | | |
| | | |
C3—N1—C1—C2 | 154.85 (10) | C9—N2—C7—C8 | −152.83 (10) |
C5—N1—C1—C2 | −77.15 (12) | C11—N2—C7—C8 | 77.95 (11) |
Fe2—N1—C1—C2 | 39.70 (10) | Fe3—N2—C7—C8 | −40.72 (10) |
Fe3i—O1—C2—C1 | −69.16 (10) | Fe3—O4—C8—C7 | −38.20 (10) |
Fe1—O1—C2—C1 | 151.10 (7) | Fe1—O4—C8—C7 | −164.36 (7) |
Fe2—O1—C2—C1 | 41.01 (10) | Fe2—O4—C8—C7 | 73.53 (9) |
N1—C1—C2—O1 | −57.29 (12) | N2—C7—C8—O4 | 52.65 (12) |
C1—N1—C3—C4 | −163.54 (10) | C7—N2—C9—C10 | 161.48 (10) |
C5—N1—C3—C4 | 69.81 (12) | C11—N2—C9—C10 | −70.76 (12) |
Fe2—N1—C3—C4 | −48.36 (11) | Fe3—N2—C9—C10 | 45.98 (10) |
Fe2—O2—C4—C3 | −26.94 (12) | Fe3—O5—C10—C9 | 19.09 (12) |
N1—C3—C4—O2 | 51.07 (13) | N2—C9—C10—O5 | −45.53 (13) |
C3—N1—C5—C6 | −95.22 (11) | C7—N2—C11—C12 | −135.90 (10) |
C1—N1—C5—C6 | 137.60 (10) | C9—N2—C11—C12 | 94.76 (11) |
Fe2—N1—C5—C6 | 21.87 (11) | Fe3—N2—C11—C12 | −17.93 (11) |
Fe3—O3—C6—C5 | −137.18 (9) | Fe2ii—O6—C12—C11 | 146.42 (9) |
Fe2—O3—C6—C5 | 45.75 (11) | Fe3—O6—C12—C11 | −49.03 (11) |
N1—C5—C6—O3 | −43.95 (13) | N2—C11—C12—O6 | 42.43 (13) |
Symmetry codes: (i) y, z, x; (ii) z, x, y. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O5iii | 0.89 (2) | 1.73 (2) | 2.6137 (13) | 176 (2) |
Symmetry code: (iii) z, −x+1/2, y+1/2. |
Reflection statistics for the strong substructure and the weak superstructure
reflections.
Agreement factors R1 and wR2 were calculated according
to the SHELXL manual (Sheldrick, 2015b). toph+k+l | # | <I> | <σ> | <I>/<σ> | <I/σ> | wR2 (all reflections) | R1 [I > 2σ(I)] | # I > 2σ(I) |
2n | 3990 | 12721.86 | 495.31 | 25.68 | 46.01 | 0.0621 | 0.0233 | 84.29 % |
2n+1 | 3972 | 1654.41 | 131.84 | 12.55 | 15.64 | 0.0894 | 0.0412 | 69.44 % |
Total | 7962 | 7198.77 | 313.97 | 22.93 | 30.85 | 0.0701 | 0.0282 | 76.88 % |
Results of the leverage analysis performed with the program HATTIE
(Parsons et al., 2012)
The normalized value T2 is a measure of the influence of a
specific reflection on a refined parameter. top | h | k | l | T2 |
x coordinate (H2) | 3 | 1 | 5 | 10000 |
| 3 | 3 | 3 | 7629.49 |
| 3 | 5 | 7 | 7353.62 |
| 5 | 1 | 7 | 7175.33 |
| | | | |
y coordinate (H2) | 0 | 2 | 6 | 10000 |
| 0 | 6 | 10 | 7304.21 |
| 5 | 1 | 8 | 5936.25 |
| 6 | 4 | 10 | 5243.41 |
| | | | |
z coordinate (H2) | 5 | 0 | 6 | 10000 |
| 4 | 6 | 7 | 5790.49 |
| 1 | 0 | 8 | 5227.58 |
| 3 | 4 | 6 | 4357.97 |
Bond lengths (Å) from different refinements top | Literature structure at room temperature (Liu et al., 2008)) | Present study at 100 K | | |
| I213 | I213 | Ia3 | Pa3 |
Fe1—O | 2.122 (7)–2.182 (7) | 2.140 (5)–2.164 (5) | 2.1515 (8) | 2.1353 (10)–2.1719 (10) |
Fe2—O | 1.977 (7)–2.184 (6) | 1.976 (5)–2.188 (6) | 1.9666 (10)–2.1811 (10) | 1.9814 (10)–2.2343 (10) |
Fe3—O | 1.954 (6)–2.151 (6) | 1.955 (5)–2.176 (6) | - | 1.9517 (10)–2.0989 (10) |
Bond-valence sums (BVS)
Entries for the literature structure were taken from the original publication.
Entries for the present study were calculated using the ToposPro
software (Version 5.3.0.3; Blatov et al., 2014) with parameters
from Brown
(2016b):
R0(Fe3+—O) 1.759 Å;
R0(Fe2+—O) 1.734 Å;
R0(Fe3+—N) 1.82 Å;
R0(Fe2+—N) 1.76 Å.
A b value of 0.37 was used for all bonds. top | Assumed state | Literature structure at room temperature (Liu et al., 2008) | Present study at 100 K | | |
| | I213 | I213 | Ia3 | Pa3 |
Fe1 | +2 | 1.82 | 1.94 | 1.94 | 1.93 |
| +3 | | 2.08 | 2.08 | 2.07 |
Fe2 | +2 | | 2.40 | 2.40 | 2.11 |
| +3 | 2.53 | 2.60 | 2.61 | 2.30 |
Fe3 | +2 | | 2.40 | | 2.75 |
| +3 | 2.73 | 2.61 | | 2.97 |