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Acta Cryst. (2007). E63, m1913-m1914    [ doi:10.1107/S1600536807028413 ]

{1,4-Bis[3-(3-methoxy-2-oxidobenzylideneamino)propyl]piperazine}iron(III) tetrafluoridoborate

R. J. Butcher, M. Pourian and J. P. Jasinski

Abstract top

The title compound, [Fe(C26H34N4O4)]BF4, shows a very distorted octahedral geometry about the Fe atom of the cation. This is due to the small bite angle of the piperazine ring, which adopts a boat conformation. The structure also displays C-H...F hydrogen bonding. Disorder with site occupancies of 0.53 (2) and 0.47 (2) is found for three of the tetrafluoridoborate F atoms.

Comment top

Metal complexes of hexadentate ligands have fascinated inorganic chemists since their first report in 1947 (Dwyer & Lions, 1947). The first such report of a Fe complex of a linear FeN4O2 ligand (i.e. where the donor atoms are linked in a linear chain) derived from the Schiff base condensation of salicylaldehyde and triethylenetetraamine was in 1955 (Das Sarma & Bailar, 1955). However, this interest lapsed for several years until the discovery that some of these complexes exhibited spin-crossover magnetic behavior (Sinn et al., 1978). While there have been numerous reports of complexes with a FeN4O2 chromophore based on Schiff base condensations of tetramines with derivatives of salicylaldehyde, there have been no reports of such complexes based on the tetramine, bis(3-aminopropyl)piperazine.

The title compound, bis(2-hydroxy-3-methoxybenzyl)-3-aminopropylpiperazineiron(III) tetrafluoroborate (I), resulted from mixing iron(II) tetrafluoroborate with the product resulting from the Schiff base condensation of bis(3-aminopropyl)piperazine with 3-methoxysalicylaldehyde. The cation contains a six-coordinate FeN4O2 chromophore exhibiting markedly distorted octahedral geometry. This distortion is most noticeable in the fact that the largest trans angle is only 155.73 (14)°. The main factor in this unusual geometry is the small bite angle subtended by the central piperazine ring where the distance between the two N's is only 2.454 (5) Å. The piperazine ring has adopted a chair conformation so that both N donors can coordinate to the Fe. There are also weak C—H···F interactions between the BF4 anion and the cation.

Related literature top

For related literature, see: Das Sarma & Bailar (1955); Dwyer & Lions (1947); Sinn et al. (1978); Yisgedu et al. (2007).

Experimental top

To 4.0 g (20 mmol) of bis(3-aminopropyl)piperazine in 15 ml of ethanol was added drop-wise 6.0 g (40 mmol) of 3-methoxysalicylaldehyde in 10 ml of ethanol. The deep yellow solution was left to stir for half an hour and a crystalline product resulted (H2L). To 0.85 g of H2L dissolved in 10.0 ml of methanol was added 0.58 g of Fe(BF4)2.xH2O. The solution became violet and a red-purple solid precipitated. This was stirred overnight, the solid filtered, washed with methanol and dried to give 1.65 g of a red powder. Crystallization was effected by slow evaporation of a DMF solution of the complex.

Refinement top

The structure contains a disordered BF4 anion with one unique F and the remaining three F atoms being disordered over two positions with multiplicities of 0.53 (2) and 0.47 (2). These were refined anisotropically in idealized geometry with the group B—F distances restrained. The H atoms were idealized with C—H distances of 0.93 (aromatic C—H), 0.96 (CH3), and 0.97 (CH2) Å and Uiso(H) = 1.2Ueq(C) (1.5Ueq(C) for the CH3 protons).

Computing details top

Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The cation and anion with numbering scheme used. The disorder in the BF4 anion is shown. Ellipsoids are drawn at the 20% probabilty level.
[Figure 2] Fig. 2. The packing arrangement viewed down the b axis showing the strongest C—H···F interactions. Only the major component for the disordered BF4 anion is shown.
{1,4-Bis[3-(3-methoxy-2-oxidobenzylideneamino)propyl]piperazine}iron(III) tetrafluoridoborate top
Crystal data top
[Fe(C26H34N4O4)]BF4F000 = 1268
Mr = 609.23Dx = 1.471 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
a = 18.809 (4) ÅCell parameters from 45 reflections
b = 10.801 (2) Åθ = 3.1–28.5º
c = 13.559 (3) ŵ = 0.62 mm−1
β = 92.89 (3)ºT = 293 (2) K
V = 2751.1 (10) Å3Prism, black
Z = 40.48 × 0.34 × 0.28 mm
Data collection top
Bruker P4
diffractometer		Rint = 0.050
Radiation source: fine-focus sealed tubeθmax = 25.0º
Monochromator: graphiteθmin = 1.1º
T = 293(2) Kh = −22→22
ω scansk = −12→0
Absorption correction: empirical (using intensity measurements)
via ψ scan (North et al., 1968)		l = 0→16
Tmin = 0.767, Tmax = 0.8753 standard reflections
5070 measured reflections every 97 reflections
4843 independent reflections intensity decay: none
2835 reflections with I > 2σ(I)
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.144  w = 1/[σ2(Fo2) + (0.0526P)2 + 0.7519P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
4843 reflectionsΔρmax = 0.37 e Å−3
392 parametersΔρmin = −0.35 e Å−3
19 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Fe(C26H34N4O4)]BF4V = 2751.1 (10) Å3
Mr = 609.23Z = 4
Monoclinic, P21/cMo Kα
a = 18.809 (4) ŵ = 0.62 mm−1
b = 10.801 (2) ÅT = 293 (2) K
c = 13.559 (3) Å0.48 × 0.34 × 0.28 mm
β = 92.89 (3)º
Data collection top
Bruker P4
diffractometer		2835 reflections with I > 2σ(I)
Absorption correction: empirical (using intensity measurements)
via ψ scan (North et al., 1968)		Rint = 0.050
Tmin = 0.767, Tmax = 0.8753 standard reflections
5070 measured reflections every 97 reflections
4843 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.05319 restraints
wR(F2) = 0.144H-atom parameters constrained
S = 1.02Δρmax = 0.37 e Å−3
4843 reflectionsΔρmin = −0.35 e Å−3
392 parameters
Special details top

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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R– factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Fe0.75426 (3)0.23350 (6)0.54586 (5)0.0410 (2)
F10.2266 (2)0.1808 (4)0.7165 (3)0.1343 (17)
F20.2255 (7)0.2224 (13)0.5597 (6)0.155 (7)0.524 (17)
F30.2569 (9)0.3678 (5)0.6634 (7)0.163 (9)0.524 (17)
F40.3229 (4)0.2095 (8)0.6468 (11)0.140 (7)0.524 (17)
F2A0.2684 (10)0.2029 (8)0.5647 (6)0.150 (10)0.476 (17)
F3A0.2095 (6)0.3473 (10)0.6327 (11)0.135 (7)0.476 (17)
F4A0.3131 (6)0.3034 (17)0.6905 (10)0.286 (16)0.476 (17)
O1A0.84521 (15)0.1910 (3)0.6005 (2)0.0513 (8)
O3A0.98485 (17)0.1991 (4)0.6097 (3)0.0761 (11)
O1B0.67485 (16)0.2943 (3)0.6135 (2)0.0519 (8)
O3B0.5410 (2)0.2911 (5)0.6538 (3)0.0848 (12)
N1A0.72422 (19)0.0531 (3)0.6011 (3)0.0455 (9)
N2A0.6808 (2)0.1742 (4)0.4217 (3)0.0530 (10)
N1B0.7902 (2)0.4237 (4)0.5574 (3)0.0537 (10)
N2B0.8012 (2)0.2548 (4)0.4007 (3)0.0521 (10)
C1A0.8439 (2)−0.0262 (4)0.6336 (3)0.0472 (11)
C2A0.8795 (2)0.0860 (4)0.6198 (3)0.0468 (11)
C3A0.9550 (3)0.0874 (5)0.6274 (4)0.0581 (13)
C31A1.0605 (3)0.2023 (6)0.6043 (5)0.094 (2)
H31D1.07560.28570.59290.141*
H31E1.07440.15030.55110.141*
H31F1.08240.17280.66540.141*
C4A0.9916 (3)−0.0192 (6)0.6512 (4)0.0750 (17)
H4AA1.0410−0.01820.65640.090*
C5A0.9553 (3)−0.1283 (6)0.6675 (5)0.088 (2)
H5AA0.9807−0.19960.68460.105*
C6A0.8842 (3)−0.1322 (5)0.6591 (4)0.0735 (16)
H6AA0.8610−0.20650.67030.088*
C7A0.7680 (2)−0.0325 (4)0.6278 (3)0.0491 (12)
H7AA0.7481−0.10760.64550.059*
C8A0.6483 (3)0.0259 (5)0.6075 (4)0.0596 (14)
H8AA0.62620.09190.64370.071*
H8AB0.6430−0.05030.64430.071*
C9A0.6100 (3)0.0128 (5)0.5074 (4)0.0708 (16)
H9AA0.6322−0.05360.47190.085*
H9AB0.5611−0.01150.51700.085*
C10A0.6092 (3)0.1273 (5)0.4442 (4)0.0702 (16)
H10A0.58280.10970.38250.084*
H10B0.58400.19220.47750.084*
C11A0.6751 (3)0.2905 (5)0.3651 (4)0.0645 (15)
H11A0.65400.35450.40430.077*
H11B0.64510.27840.30550.077*
C12A0.7203 (3)0.0841 (5)0.3636 (4)0.0644 (15)
H12A0.70010.08040.29640.077*
H12B0.71740.00220.39260.077*
C1B0.6745 (3)0.5121 (5)0.5857 (4)0.0578 (14)
C2B0.6411 (3)0.4020 (5)0.6086 (3)0.0515 (12)
C3B0.5686 (3)0.4036 (6)0.6302 (4)0.0667 (15)
C31B0.4673 (3)0.2838 (8)0.6710 (5)0.110 (3)
H31A0.45400.19870.67860.166*
H31B0.44030.31920.61600.166*
H31C0.45780.32870.73010.166*
C4B0.5312 (4)0.5146 (7)0.6261 (4)0.089 (2)
H4BA0.48320.51580.63980.107*
C5B0.5649 (4)0.6229 (7)0.6019 (5)0.096 (2)
H5BA0.53920.69650.59820.115*
C6B0.6355 (4)0.6234 (6)0.5835 (4)0.0801 (18)
H6BA0.65790.69760.56930.096*
C7B0.7493 (3)0.5168 (5)0.5694 (4)0.0623 (15)
H7BA0.77000.59490.56740.075*
C8B0.8657 (3)0.4485 (5)0.5431 (5)0.0720 (16)
H8BA0.89440.39380.58550.086*
H8BB0.87650.53290.56300.086*
C9B0.8860 (3)0.4308 (5)0.4384 (5)0.0782 (17)
H9BA0.93590.45220.43430.094*
H9BB0.85870.48840.39670.094*
C10B0.8747 (3)0.3013 (5)0.3972 (4)0.0702 (16)
H10C0.88830.30050.32910.084*
H10D0.90620.24490.43400.084*
C11B0.7971 (3)0.1263 (5)0.3642 (4)0.0606 (14)
H11C0.82660.07290.40680.073*
H11D0.81420.12200.29800.073*
C12B0.7496 (3)0.3288 (5)0.3385 (4)0.0646 (15)
H12C0.75620.31310.26910.078*
H12D0.75680.41650.35100.078*
B0.2557 (3)0.2526 (5)0.6480 (4)0.0686 (17)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe0.0385 (3)0.0446 (4)0.0395 (3)0.0059 (3)−0.0019 (2)−0.0004 (3)
F10.174 (5)0.114 (3)0.118 (3)0.046 (3)0.038 (3)0.024 (3)
F20.161 (11)0.201 (17)0.097 (8)−0.024 (10)−0.040 (7)0.008 (8)
F30.36 (3)0.044 (5)0.079 (6)0.052 (9)−0.016 (12)−0.017 (4)
F40.063 (6)0.096 (7)0.26 (2)−0.002 (4)0.031 (7)0.004 (8)
F2A0.34 (3)0.045 (6)0.064 (7)0.048 (10)0.025 (10)−0.016 (4)
F3A0.120 (10)0.113 (10)0.173 (15)0.054 (7)0.019 (8)0.049 (10)
F4A0.068 (9)0.56 (5)0.221 (16)−0.011 (16)−0.022 (9)−0.16 (2)
O1A0.0378 (17)0.0477 (19)0.067 (2)0.0017 (15)−0.0096 (15)0.0077 (16)
O3A0.038 (2)0.080 (3)0.109 (3)−0.0077 (18)−0.0039 (19)−0.001 (2)
O1B0.0497 (19)0.054 (2)0.0520 (19)0.0101 (16)0.0054 (15)0.0015 (15)
O3B0.051 (2)0.121 (4)0.083 (3)0.021 (2)0.014 (2)0.007 (3)
N1A0.040 (2)0.050 (2)0.047 (2)0.0032 (18)−0.0024 (18)0.0022 (19)
N2A0.057 (3)0.058 (3)0.043 (2)0.016 (2)−0.0102 (19)−0.005 (2)
N1B0.057 (3)0.045 (2)0.059 (3)0.004 (2)0.000 (2)−0.001 (2)
N2B0.059 (2)0.051 (2)0.047 (2)0.018 (2)0.0114 (18)0.005 (2)
C1A0.042 (3)0.053 (3)0.047 (3)0.010 (2)0.006 (2)0.010 (2)
C2A0.043 (3)0.059 (3)0.039 (3)0.005 (2)0.000 (2)0.003 (2)
C3A0.042 (3)0.075 (4)0.057 (3)0.005 (3)0.001 (2)0.007 (3)
C31A0.047 (3)0.115 (5)0.119 (5)−0.013 (3)0.000 (3)−0.010 (4)
C4A0.040 (3)0.106 (5)0.079 (4)0.023 (3)0.006 (3)0.024 (4)
C5A0.069 (4)0.085 (5)0.110 (5)0.035 (4)0.020 (4)0.039 (4)
C6A0.061 (4)0.067 (4)0.095 (4)0.018 (3)0.019 (3)0.021 (3)
C7A0.051 (3)0.048 (3)0.049 (3)−0.001 (2)0.003 (2)0.005 (2)
C8A0.044 (3)0.062 (3)0.073 (4)−0.008 (2)0.004 (3)0.005 (3)
C9A0.045 (3)0.076 (4)0.090 (4)−0.013 (3)−0.007 (3)−0.007 (3)
C10A0.054 (3)0.083 (4)0.071 (4)0.009 (3)−0.025 (3)−0.014 (3)
C11A0.082 (4)0.064 (4)0.045 (3)0.030 (3)−0.013 (3)0.000 (3)
C12A0.079 (4)0.063 (3)0.051 (3)0.017 (3)−0.005 (3)−0.010 (3)
C1B0.075 (4)0.050 (3)0.047 (3)0.019 (3)−0.010 (3)−0.011 (2)
C2B0.053 (3)0.065 (3)0.036 (3)0.021 (3)−0.004 (2)−0.009 (2)
C3B0.057 (3)0.094 (5)0.049 (3)0.028 (3)−0.003 (3)−0.008 (3)
C31B0.059 (4)0.184 (8)0.089 (5)0.020 (5)0.012 (3)0.030 (5)
C4B0.079 (5)0.126 (6)0.062 (4)0.056 (5)0.001 (3)−0.008 (4)
C5B0.108 (6)0.092 (5)0.087 (5)0.060 (5)−0.007 (4)−0.018 (4)
C6B0.094 (5)0.065 (4)0.081 (4)0.032 (3)−0.007 (4)−0.016 (3)
C7B0.078 (4)0.044 (3)0.064 (4)0.008 (3)−0.011 (3)−0.012 (3)
C8B0.061 (4)0.052 (3)0.103 (5)−0.008 (3)0.006 (3)0.001 (3)
C9B0.062 (4)0.077 (4)0.097 (5)−0.004 (3)0.018 (3)0.022 (4)
C10B0.069 (4)0.075 (4)0.069 (4)0.008 (3)0.025 (3)0.011 (3)
C11B0.078 (4)0.056 (3)0.049 (3)0.023 (3)0.013 (3)−0.002 (3)
C12B0.088 (4)0.063 (3)0.043 (3)0.022 (3)−0.001 (3)0.005 (3)
B0.068 (4)0.066 (5)0.073 (4)0.011 (4)0.007 (3)−0.005 (4)
Geometric parameters (Å, °) top
Fe—O1A1.887 (3)C7A—H7AA0.9300
Fe—O1B1.908 (3)C8A—C9A1.511 (7)
Fe—N1B2.166 (4)C8A—H8AA0.9700
Fe—N1A2.172 (4)C8A—H8AB0.9700
Fe—N2B2.209 (4)C9A—C10A1.504 (7)
Fe—N2A2.218 (4)C9A—H9AA0.9700
F1—B1.347 (6)C9A—H9AB0.9700
F2—B1.339 (8)C10A—H10A0.9700
F3—B1.261 (7)C10A—H10B0.9700
F4—B1.349 (7)C11A—C12B1.522 (7)
F2A—B1.284 (7)C11A—H11A0.9700
F3A—B1.351 (8)C11A—H11B0.9700
F4A—B1.317 (8)C12A—C11B1.514 (7)
O1A—C2A1.324 (5)C12A—H12A0.9700
O3A—C3A1.357 (6)C12A—H12B0.9700
O3A—C31A1.429 (6)C1B—C2B1.388 (7)
O1B—C2B1.325 (5)C1B—C6B1.408 (7)
O3B—C3B1.365 (7)C1B—C7B1.435 (7)
O3B—C31B1.420 (6)C2B—C3B1.409 (7)
N1A—C7A1.278 (5)C3B—C4B1.390 (8)
N1A—C8A1.466 (5)C31B—H31A0.9600
N2A—C11A1.474 (6)C31B—H31B0.9600
N2A—C12A1.476 (6)C31B—H31C0.9600
N2A—C10A1.484 (6)C4B—C5B1.378 (10)
N1B—C7B1.281 (6)C4B—H4BA0.9300
N1B—C8B1.467 (6)C5B—C6B1.363 (9)
N2B—C11B1.474 (6)C5B—H5BA0.9300
N2B—C10B1.475 (6)C6B—H6BA0.9300
N2B—C12B1.486 (6)C7B—H7BA0.9300
C1A—C2A1.402 (6)C8B—C9B1.501 (8)
C1A—C6A1.408 (7)C8B—H8BA0.9700
C1A—C7A1.428 (6)C8B—H8BB0.9700
C2A—C3A1.419 (6)C9B—C10B1.517 (8)
C3A—C4A1.370 (7)C9B—H9BA0.9700
C31A—H31D0.9600C9B—H9BB0.9700
C31A—H31E0.9600C10B—H10C0.9700
C31A—H31F0.9600C10B—H10D0.9700
C4A—C5A1.384 (8)C11B—H11C0.9700
C4A—H4AA0.9300C11B—H11D0.9700
C5A—C6A1.337 (7)C12B—H12C0.9700
C5A—H5AA0.9300C12B—H12D0.9700
C6A—H6AA0.9300
O1A—Fe—O1B127.67 (14)N2A—C11A—C12B108.1 (4)
O1A—Fe—N1B85.93 (14)N2A—C11A—H11A110.1
O1B—Fe—N1B83.57 (14)C12B—C11A—H11A110.1
O1A—Fe—N1A83.83 (13)N2A—C11A—H11B110.1
O1B—Fe—N1A85.37 (14)C12B—C11A—H11B110.1
N1B—Fe—N1A155.69 (14)H11A—C11A—H11B108.4
O1A—Fe—N2B88.88 (14)N2A—C12A—C11B107.7 (4)
O1B—Fe—N2B138.58 (13)N2A—C12A—H12A110.2
N1B—Fe—N2B80.13 (15)C11B—C12A—H12A110.2
N1A—Fe—N2B121.53 (14)N2A—C12A—H12B110.2
O1A—Fe—N2A138.21 (14)C11B—C12A—H12B110.2
O1B—Fe—N2A89.52 (14)H12A—C12A—H12B108.5
N1B—Fe—N2A120.61 (15)C2B—C1B—C6B119.7 (6)
N1A—Fe—N2A80.78 (14)C2B—C1B—C7B121.5 (4)
N2B—Fe—N2A67.37 (15)C6B—C1B—C7B118.7 (5)
C2A—O1A—Fe135.2 (3)O1B—C2B—C1B122.9 (5)
C3A—O3A—C31A116.8 (4)O1B—C2B—C3B117.8 (5)
C2B—O1B—Fe131.5 (3)C1B—C2B—C3B119.3 (5)
C3B—O3B—C31B118.3 (5)O3B—C3B—C4B125.4 (6)
C7A—N1A—C8A117.0 (4)O3B—C3B—C2B114.9 (5)
C7A—N1A—Fe124.9 (3)C4B—C3B—C2B119.7 (6)
C8A—N1A—Fe118.1 (3)O3B—C31B—H31A109.5
C11A—N2A—C12A108.0 (4)O3B—C31B—H31B109.5
C11A—N2A—C10A110.8 (4)H31A—C31B—H31B109.5
C12A—N2A—C10A111.8 (4)O3B—C31B—H31C109.5
C11A—N2A—Fe100.1 (3)H31A—C31B—H31C109.5
C12A—N2A—Fe106.5 (3)H31B—C31B—H31C109.5
C10A—N2A—Fe118.6 (3)C5B—C4B—C3B120.2 (6)
C7B—N1B—C8B117.8 (4)C5B—C4B—H4BA119.9
C7B—N1B—Fe124.4 (4)C3B—C4B—H4BA119.9
C8B—N1B—Fe117.6 (3)C6B—C5B—C4B120.8 (6)
C11B—N2B—C10B110.1 (4)C6B—C5B—H5BA119.6
C11B—N2B—C12B107.1 (4)C4B—C5B—H5BA119.6
C10B—N2B—C12B112.6 (4)C5B—C6B—C1B120.3 (6)
C11B—N2B—Fe100.6 (3)C5B—C6B—H6BA119.9
C10B—N2B—Fe118.8 (3)C1B—C6B—H6BA119.9
C12B—N2B—Fe106.5 (3)N1B—C7B—C1B126.3 (5)
C2A—C1A—C6A118.7 (4)N1B—C7B—H7BA116.9
C2A—C1A—C7A121.2 (4)C1B—C7B—H7BA116.9
C6A—C1A—C7A120.0 (5)N1B—C8B—C9B113.4 (5)
O1A—C2A—C1A122.3 (4)N1B—C8B—H8BA108.9
O1A—C2A—C3A118.8 (4)C9B—C8B—H8BA108.9
C1A—C2A—C3A118.9 (4)N1B—C8B—H8BB108.9
O3A—C3A—C4A125.6 (5)C9B—C8B—H8BB108.9
O3A—C3A—C2A114.6 (4)H8BA—C8B—H8BB107.7
C4A—C3A—C2A119.8 (5)C8B—C9B—C10B115.3 (5)
O3A—C31A—H31D109.5C8B—C9B—H9BA108.5
O3A—C31A—H31E109.5C10B—C9B—H9BA108.5
H31D—C31A—H31E109.5C8B—C9B—H9BB108.5
O3A—C31A—H31F109.5C10B—C9B—H9BB108.5
H31D—C31A—H31F109.5H9BA—C9B—H9BB107.5
H31E—C31A—H31F109.5N2B—C10B—C9B114.6 (4)
C3A—C4A—C5A120.5 (5)N2B—C10B—H10C108.6
C3A—C4A—H4AA119.8C9B—C10B—H10C108.6
C5A—C4A—H4AA119.8N2B—C10B—H10D108.6
C6A—C5A—C4A120.8 (5)C9B—C10B—H10D108.6
C6A—C5A—H5AA119.6H10C—C10B—H10D107.6
C4A—C5A—H5AA119.6N2B—C11B—C12A108.6 (4)
C5A—C6A—C1A121.3 (6)N2B—C11B—H11C110.0
C5A—C6A—H6AA119.3C12A—C11B—H11C110.0
C1A—C6A—H6AA119.3N2B—C11B—H11D110.0
N1A—C7A—C1A127.5 (4)C12A—C11B—H11D110.0
N1A—C7A—H7AA116.2H11C—C11B—H11D108.3
C1A—C7A—H7AA116.2N2B—C12B—C11A107.6 (4)
N1A—C8A—C9A112.8 (4)N2B—C12B—H12C110.2
N1A—C8A—H8AA109.0C11A—C12B—H12C110.2
C9A—C8A—H8AA109.0N2B—C12B—H12D110.2
N1A—C8A—H8AB109.0C11A—C12B—H12D110.2
C9A—C8A—H8AB109.0H12C—C12B—H12D108.5
H8AA—C8A—H8AB107.8F2A—B—F4A111.9 (8)
C10A—C9A—C8A115.1 (4)F3—B—F2113.1 (7)
C10A—C9A—H9AA108.5F3—B—F1117.3 (6)
C8A—C9A—H9AA108.5F2A—B—F1117.8 (6)
C10A—C9A—H9AB108.5F4A—B—F1106.9 (7)
C8A—C9A—H9AB108.5F2—B—F1107.9 (6)
H9AA—C9A—H9AB107.5F3—B—F4109.4 (7)
N2A—C10A—C9A114.5 (4)F2—B—F4105.1 (7)
N2A—C10A—H10A108.6F1—B—F4102.9 (6)
C9A—C10A—H10A108.6F2A—B—F3A109.1 (7)
N2A—C10A—H10B108.6F4A—B—F3A105.0 (7)
C9A—C10A—H10B108.6F1—B—F3A105.2 (6)
H10A—C10A—H10B107.6
O1B—Fe—O1A—C2A105.8 (4)C31A—O3A—C3A—C4A7.7 (8)
N1B—Fe—O1A—C2A−175.6 (4)C31A—O3A—C3A—C2A−172.5 (5)
N1A—Fe—O1A—C2A26.5 (4)O1A—C2A—C3A—O3A−2.5 (7)
N2B—Fe—O1A—C2A−95.4 (4)C1A—C2A—C3A—O3A178.0 (4)
N2A—Fe—O1A—C2A−42.2 (5)O1A—C2A—C3A—C4A177.4 (5)
O1A—Fe—O1B—C2B115.0 (4)C1A—C2A—C3A—C4A−2.2 (7)
N1B—Fe—O1B—C2B35.3 (4)O3A—C3A—C4A—C5A−179.9 (5)
N1A—Fe—O1B—C2B−166.4 (4)C2A—C3A—C4A—C5A0.2 (9)
N2B—Fe—O1B—C2B−31.9 (5)C3A—C4A—C5A—C6A0.9 (10)
N2A—Fe—O1B—C2B−85.6 (4)C4A—C5A—C6A—C1A−0.1 (10)
O1A—Fe—N1A—C7A−16.0 (4)C2A—C1A—C6A—C5A−1.8 (8)
O1B—Fe—N1A—C7A−144.7 (4)C7A—C1A—C6A—C5A−178.3 (5)
N1B—Fe—N1A—C7A−81.6 (5)C8A—N1A—C7A—C1A−176.2 (5)
N2B—Fe—N1A—C7A68.9 (4)Fe—N1A—C7A—C1A4.6 (7)
N2A—Fe—N1A—C7A125.0 (4)C2A—C1A—C7A—N1A7.4 (8)
O1A—Fe—N1A—C8A164.8 (3)C6A—C1A—C7A—N1A−176.2 (5)
O1B—Fe—N1A—C8A36.1 (3)C7A—N1A—C8A—C9A−110.1 (5)
N1B—Fe—N1A—C8A99.2 (5)Fe—N1A—C8A—C9A69.2 (5)
N2B—Fe—N1A—C8A−110.3 (3)N1A—C8A—C9A—C10A−62.7 (6)
N2A—Fe—N1A—C8A−54.2 (3)C11A—N2A—C10A—C9A−176.4 (4)
O1A—Fe—N2A—C11A−119.4 (3)C12A—N2A—C10A—C9A63.1 (6)
O1B—Fe—N2A—C11A85.3 (3)Fe—N2A—C10A—C9A−61.5 (5)
N1B—Fe—N2A—C11A3.1 (3)C8A—C9A—C10A—N2A59.4 (7)
N1A—Fe—N2A—C11A170.7 (3)C12A—N2A—C11A—C12B−53.5 (5)
N2B—Fe—N2A—C11A−59.3 (3)C10A—N2A—C11A—C12B−176.2 (4)
O1A—Fe—N2A—C12A−7.0 (4)Fe—N2A—C11A—C12B57.7 (4)
O1B—Fe—N2A—C12A−162.3 (3)C11A—N2A—C12A—C11B70.4 (5)
N1B—Fe—N2A—C12A115.5 (3)C10A—N2A—C12A—C11B−167.5 (4)
N1A—Fe—N2A—C12A−76.9 (3)Fe—N2A—C12A—C11B−36.4 (4)
N2B—Fe—N2A—C12A53.1 (3)Fe—O1B—C2B—C1B−29.8 (6)
O1A—Fe—N2A—C10A120.0 (3)Fe—O1B—C2B—C3B151.8 (3)
O1B—Fe—N2A—C10A−35.2 (3)C6B—C1B—C2B—O1B−179.0 (4)
N1B—Fe—N2A—C10A−117.4 (3)C7B—C1B—C2B—O1B−2.5 (7)
N1A—Fe—N2A—C10A50.2 (3)C6B—C1B—C2B—C3B−0.6 (7)
N2B—Fe—N2A—C10A−179.8 (4)C7B—C1B—C2B—C3B175.9 (5)
O1A—Fe—N1B—C7B−151.1 (4)C31B—O3B—C3B—C4B3.4 (8)
O1B—Fe—N1B—C7B−22.4 (4)C31B—O3B—C3B—C2B−176.5 (5)
N1A—Fe—N1B—C7B−85.9 (5)O1B—C2B—C3B—O3B−0.2 (7)
N2B—Fe—N1B—C7B119.4 (4)C1B—C2B—C3B—O3B−178.7 (4)
N2A—Fe—N1B—C7B63.2 (4)O1B—C2B—C3B—C4B179.9 (4)
O1A—Fe—N1B—C8B33.7 (4)C1B—C2B—C3B—C4B1.4 (7)
O1B—Fe—N1B—C8B162.4 (4)O3B—C3B—C4B—C5B179.6 (6)
N1A—Fe—N1B—C8B98.9 (5)C2B—C3B—C4B—C5B−0.6 (9)
N2B—Fe—N1B—C8B−55.8 (4)C3B—C4B—C5B—C6B−1.2 (10)
N2A—Fe—N1B—C8B−112.0 (4)C4B—C5B—C6B—C1B2.1 (10)
O1A—Fe—N2B—C11B86.3 (3)C2B—C1B—C6B—C5B−1.2 (8)
O1B—Fe—N2B—C11B−119.3 (3)C7B—C1B—C6B—C5B−177.8 (5)
N1B—Fe—N2B—C11B172.4 (3)C8B—N1B—C7B—C1B−179.2 (5)
N1A—Fe—N2B—C11B4.3 (3)Fe—N1B—C7B—C1B5.7 (7)
N2A—Fe—N2B—C11B−58.4 (3)C2B—C1B—C7B—N1B12.4 (8)
O1A—Fe—N2B—C10B−33.8 (3)C6B—C1B—C7B—N1B−171.1 (5)
O1B—Fe—N2B—C10B120.6 (3)C7B—N1B—C8B—C9B−105.6 (5)
N1B—Fe—N2B—C10B52.3 (3)Fe—N1B—C8B—C9B69.9 (5)
N1A—Fe—N2B—C10B−115.8 (3)N1B—C8B—C9B—C10B−60.6 (7)
N2A—Fe—N2B—C10B−178.5 (4)C11B—N2B—C10B—C9B−176.9 (4)
O1A—Fe—N2B—C12B−162.1 (3)C12B—N2B—C10B—C9B63.6 (6)
O1B—Fe—N2B—C12B−7.7 (4)Fe—N2B—C10B—C9B−61.7 (5)
N1B—Fe—N2B—C12B−76.0 (3)C8B—C9B—C10B—N2B56.9 (7)
N1A—Fe—N2B—C12B115.9 (3)C10B—N2B—C11B—C12A−177.0 (4)
N2A—Fe—N2B—C12B53.2 (3)C12B—N2B—C11B—C12A−54.2 (5)
Fe—O1A—C2A—C1A−23.4 (7)Fe—N2B—C11B—C12A56.9 (4)
Fe—O1A—C2A—C3A157.1 (3)N2A—C12A—C11B—N2B−13.5 (5)
C6A—C1A—C2A—O1A−176.6 (4)C11B—N2B—C12B—C11A70.9 (5)
C7A—C1A—C2A—O1A−0.2 (7)C10B—N2B—C12B—C11A−168.0 (4)
C6A—C1A—C2A—C3A2.9 (7)Fe—N2B—C12B—C11A−36.1 (5)
C7A—C1A—C2A—C3A179.4 (4)N2A—C11A—C12B—N2B−14.6 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C9A—H9AA···F4i0.972.513.464 (14)170
C9A—H9AA···F2Ai0.972.543.442 (14)155
C12A—H12B···F4i0.972.463.275 (11)141
C12A—H12B···F2Ai0.972.303.252 (10)166
C12B—H12D···F3ii0.972.353.279 (8)160
C9B—H9BB···F3Aii0.972.213.119 (9)155
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1.
Selected geometric parameters (Å, °) top
Fe—O1A1.887 (3)Fe—N1A2.172 (4)
Fe—O1B1.908 (3)Fe—N2B2.209 (4)
Fe—N1B2.166 (4)Fe—N2A2.218 (4)
O1A—Fe—O1B127.67 (14)N1B—Fe—N2B80.13 (15)
O1A—Fe—N1B85.93 (14)N1A—Fe—N2B121.53 (14)
O1B—Fe—N1B83.57 (14)O1A—Fe—N2A138.21 (14)
O1A—Fe—N1A83.83 (13)O1B—Fe—N2A89.52 (14)
O1B—Fe—N1A85.37 (14)N1B—Fe—N2A120.61 (15)
N1B—Fe—N1A155.69 (14)N1A—Fe—N2A80.78 (14)
O1A—Fe—N2B88.88 (14)N2B—Fe—N2A67.37 (15)
O1B—Fe—N2B138.58 (13)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C9A—H9AA···F4i0.972.513.464 (14)170
C9A—H9AA···F2Ai0.972.543.442 (14)155
C12A—H12B···F4i0.972.463.275 (11)141
C12A—H12B···F2Ai0.972.303.252 (10)166
C12B—H12D···F3ii0.972.353.279 (8)160
C9B—H9BB···F3Aii0.972.213.119 (9)155
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1.
Acknowledgements top

RJB acknowledges the Laboratory for the Structure of Matter at the Naval Research Laboratory for access to their diffractometer.

references
References top

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