Tris[4,4,4-trifluoro-1-(2-thien­yl)butane-1,3-dionato]aluminium(III)–tris­[4,4,4-trifluoro-1-(2-thien­yl)butane-1,3-dion­ato]iron(III) (3/1)

Schultz, M.; Roa, E.C.

doi:10.1107/S160053680902858X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page m981

doi:10.1107/S160053680902858X

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Tris[4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dionato]aluminium(III)–tris[4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dionato]iron(III) (3/1)

Madeleine Schultz ^a ^* and Elnor C. Roa ^b

^aSchool of Physical and Chemical Sciences, Queensland University of Technology, Brisbane, Queensland 4001, Australia, and ^bChemistry Department, College of Sciences and Mathematics, Mindanao State University - Iligan Institute of Technology, Iligan City, Philippines
^*Correspondence e-mail: madeleine.schultz@qut.edu.au

(Received 29 June 2009; accepted 20 July 2009; online 25 July 2009)

In the title compound, [Al(C₈H₄F₃O₂S)₃]₃[Fe(C₈H₄F₃O₂S)₃], the metal centre is statistically occupied by Al^III and Fe^III cations in a 3:1 ratio. The metal centre is within an octahedral O₆ donor set defined by three chelating substituted acetoacetonate anions. The ligands are arranged around the periphery of the molecule with a mer geometry of the S atoms.

Related literature

The analogous structures of the octahedral Fe, In (Soling, 1976 ) and Ru (Aynetchi et al., 1986 ) complexes of this ligand have been reported. For extraction with supercritical carbon dioxide using this ligand, see: Wai (1995 ); Wai et al. (1996 ). For related Al acetylacetonato structures, see: Bott et al. (2001 ); Dharmaprakash et al. (2006 ).

Experimental

Crystal data

[Al(C₈H₄F₃O₂S)₃]₃[Fe(C₈H₄F₃O₂S)₃]
M_r = 2790.97
Monoclinic, P 2₁ /n
a = 13.743 (3) Å
b = 14.278 (2) Å
c = 14.136 (3) Å
β = 94.013 (18)°
V = 2767.1 (9) Å³
Z = 1
Mo Kα radiation
μ = 0.52 mm⁻¹
T = 173 K
0.14 × 0.10 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire3 detector
Absorption correction: none
11706 measured reflections
6021 independent reflections
2687 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.071
wR(F²) = 0.185
S = 0.91
6021 reflections
388 parameters
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlisPro. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis Pro; data reduction: CrysAlis Pro; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and WinGX32 (Farrugia, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680902858X/tk2491sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680902858X/tk2491Isup2.hkl

checkCIF report

Comment top

The title compound (I) was formed during the extraction of a standard reference material using supercritical carbon dioxide (SFE) in order to determine the recovery of some heavy metals by ICP-MS. SFE using fluorinated ligands such as 1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedione has been shown to be very effective in extracting metals from a variety of matrices (Wai, 1995; Wai et al., 1996).

The structure of (I), Fig. 1, is similar to those of the Ru (Aynetchi et al., 1986), In and Fe (Soling, 1976) complexes of the same ligand. As observed in those structures, the M—O distances adjacent to the trifluoromethyl group are very slightly shorter than those adjacent to the thienyl group. A more important bond distance variation is found in the backbone of the butanedionato ligand, in that the two C—C bond distances in the chelate ring are significantly different from each other. The distance from the central C atom of the chelate ring to the C atom adjacent to the trifluoromethyl group (C2—C3; C10—C11; C18—C19) is significantly shorter than that to the C atom adjacent to the thienyl group (C3—C4; C11—C12; C19—C20). In the present structure this difference is around 0.06 Å, which is similar to that observed in the three reported structures involving octahedral complexes of this ligand.

A large number of structures of Al(acac)₃ have been reported with the unsubstituted acetylacetonato ligand (Bott et al., 2001), and the related complex tris(3-t-butoxybutandionato)aluminium(III), bearing a heterobidentate acetylacetonato ligand has also been reported (Dharmaprakash et al., 2006). In that structure, a fac arrangement of the ligands was observed, unlike in the present structure.

Related literature top

The analogous structures of the octahedral Fe, In (Soling, 1976) and Ru (Aynetchi et al., 1986) complexes of this ligand have been reported. For extraction with supercritical carbon dioxide, see: Wai (1995); Wai et al. (1996). For related Al acetylacetonato structures, see: Bott et al. (2001); Dharmaprakash et al. (2006).

Experimental top

A sample of a standard reference material NCSDC 73372, Lake Sediment, was extracted using supercritical CO₂ modified with 5% methanol in the presence of the protonated ligand 1-(2-thienyl)-4,4,4-trifluoro- 1,3-butanedione (Wai, 1995; Wai et al., 1996). The extract was collected in chloroform and the deep-red crystals formed upon evaporation of the solvent. The identity of the metal was determined after the crystallographic data had been collected by subjecting the same crystal to Scanning Electron Microscopy coupled with Energy Dispersive X-ray spectroscopy (SEM-EDX). The spectra obtained at two different locations on the crystal showed the only metals present in detectable amounts to be Al and Fe. The ratio of these was found to be 3:1 by integrating the K peaks after background subtraction.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and WinGX32 (Farrugia, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the complex (I) showing the atom labelling scheme. Hydrogen atoms have been omitted for clarity and displacement ellipsoids are drawn at the 50% probability level. The Al1 site is 25% occupied by Fe.

Tris[4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dionato]aluminium(III)– tris[4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dionato]iron(III) (3/1) top

Crystal data top

[Al(C₈H₄F₃O₂S)₃]₃[Fe(C₈H₄F₃O₂S)₃]	F(000) = 1397
M_r = 2790.97	D_x = 1.675 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1790 reflections
a = 13.743 (3) Å	θ = 2.9–28.0°
b = 14.278 (2) Å	µ = 0.52 mm⁻¹
c = 14.136 (3) Å	T = 173 K
β = 94.013 (18)°	Block, red
V = 2767.1 (9) Å³	0.14 × 0.10 × 0.10 mm
Z = 1

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire3 (Gemini Ultra Mo) detector	2687 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.052
Graphite monochromator	θ_max = 28.0°, θ_min = 2.9°
ω scans	h = −18→14
11706 measured reflections	k = −16→18
6021 independent reflections	l = −13→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.185	H-atom parameters constrained
S = 0.91	w = 1/[σ²(F_o²) + (0.0829P)²] where P = (F_o² + 2F_c²)/3
6021 reflections	(Δ/σ)_max < 0.001
388 parameters	Δρ_max = 0.72 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Al(C₈H₄F₃O₂S)₃]₃[Fe(C₈H₄F₃O₂S)₃]	V = 2767.1 (9) Å³
M_r = 2790.97	Z = 1
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.743 (3) Å	µ = 0.52 mm⁻¹
b = 14.278 (2) Å	T = 173 K
c = 14.136 (3) Å	0.14 × 0.10 × 0.10 mm
β = 94.013 (18)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire3 (Gemini Ultra Mo) detector	2687 reflections with I > 2σ(I)
11706 measured reflections	R_int = 0.052
6021 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	0 restraints
wR(F²) = 0.185	H-atom parameters constrained
S = 0.91	Δρ_max = 0.72 e Å⁻³
6021 reflections	Δρ_min = −0.44 e Å⁻³
388 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 > σ(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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Al1	0.69004 (9)	0.19827 (9)	0.06179 (8)	0.0295 (3)	0.75
Fe1	0.69004 (9)	0.19827 (9)	0.06179 (8)	0.0295 (3)	0.25
S3	0.44342 (12)	0.41369 (12)	0.13998 (12)	0.0543 (5)
S2	0.89747 (12)	−0.06384 (12)	0.11705 (12)	0.0585 (5)
S1	0.85479 (12)	0.30057 (13)	0.34316 (12)	0.0563 (5)
F5	0.5874 (2)	0.1933 (2)	−0.2505 (2)	0.0519 (9)
O3	0.7705 (2)	0.0890 (2)	0.0564 (2)	0.0360 (9)
F4	0.7125 (3)	0.1207 (3)	−0.2951 (2)	0.0676 (11)
O5	0.7945 (2)	0.2798 (2)	0.0298 (2)	0.0335 (9)
O2	0.7411 (2)	0.2155 (3)	0.1911 (2)	0.0367 (9)
F8	0.8943 (3)	0.5020 (3)	0.0181 (3)	0.0840 (14)
O1	0.5872 (2)	0.1250 (2)	0.1022 (2)	0.0344 (9)
O6	0.6072 (2)	0.3059 (2)	0.0761 (2)	0.0336 (9)
F2	0.4760 (3)	0.0067 (3)	0.2755 (3)	0.0831 (13)
F3	0.3977 (3)	0.1018 (3)	0.1898 (3)	0.0889 (14)
F1	0.4669 (3)	−0.0117 (3)	0.1286 (3)	0.0901 (15)
F7	0.9645 (3)	0.3814 (3)	0.0733 (3)	0.0868 (14)
F6	0.7253 (3)	0.2621 (3)	−0.2414 (2)	0.0709 (12)
O4	0.6526 (2)	0.1881 (2)	−0.0684 (2)	0.0334 (9)
C12	0.8008 (4)	0.0479 (4)	−0.0163 (4)	0.0337 (13)
F9	0.9159 (3)	0.3810 (3)	−0.0685 (3)	0.0972 (16)
C14	0.9116 (4)	−0.0882 (4)	−0.0661 (4)	0.0377 (14)
H14	0.9026	−0.0827	−0.1331	0.045*
C18	0.7963 (4)	0.3683 (4)	0.0399 (4)	0.0372 (14)
C10	0.7039 (4)	0.1449 (4)	−0.1282 (3)	0.0312 (13)
C2	0.5671 (4)	0.1104 (4)	0.1884 (4)	0.0414 (15)
C9	0.6824 (4)	0.1807 (4)	−0.2294 (4)	0.0445 (15)
C22	0.5581 (4)	0.5545 (4)	0.1173 (4)	0.0389 (14)
H22	0.6125	0.5926	0.1053	0.047*
C3	0.6194 (4)	0.1384 (4)	0.2702 (4)	0.0409 (14)
H3	0.5975	0.1198	0.3297	0.049*
C21	0.5569 (4)	0.4602 (4)	0.1117 (3)	0.0396 (15)
C6	0.7347 (4)	0.2167 (4)	0.4512 (4)	0.0355 (13)
H6	0.6831	0.1803	0.4733	0.043*
C13	0.8660 (4)	−0.0308 (4)	0.0018 (4)	0.0416 (14)
C1	0.4768 (4)	0.0521 (4)	0.1955 (4)	0.0428 (15)
C24	0.4008 (4)	0.5220 (4)	0.1584 (4)	0.0459 (16)
H24	0.3371	0.5348	0.1773	0.055*
C4	0.7053 (4)	0.1944 (4)	0.2686 (4)	0.0395 (14)
C7	0.8050 (5)	0.2679 (5)	0.5097 (4)	0.0498 (16)
H7	0.8054	0.2694	0.5769	0.060*
C11	0.7736 (4)	0.0785 (4)	−0.1096 (4)	0.0362 (13)
H11	0.8050	0.0518	−0.1610	0.043*
C17	0.8902 (4)	0.4101 (4)	0.0143 (5)	0.0466 (16)
C19	0.7239 (4)	0.4262 (4)	0.0665 (4)	0.0447 (15)
H19	0.7371	0.4912	0.0738	0.054*
C8	0.8712 (5)	0.3141 (4)	0.4601 (4)	0.0563 (18)
H8	0.9224	0.3509	0.4896	0.068*
C23	0.4676 (5)	0.5887 (5)	0.1434 (4)	0.0568 (18)
H23	0.4546	0.6536	0.1498	0.068*
C20	0.6284 (4)	0.3921 (4)	0.0839 (3)	0.0366 (14)
C5	0.7541 (4)	0.2285 (4)	0.3563 (4)	0.0356 (14)
C15	0.9723 (5)	−0.1543 (5)	−0.0158 (5)	0.0576 (19)
H15	1.0115	−0.1979	−0.0468	0.069*
C16	0.9703 (4)	−0.1506 (4)	0.0786 (6)	0.061 (2)
H16	1.0061	−0.1924	0.1203	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Al1	0.0308 (7)	0.0283 (7)	0.0301 (7)	−0.0074 (6)	0.0079 (5)	−0.0021 (6)
Fe1	0.0308 (7)	0.0283 (7)	0.0301 (7)	−0.0074 (6)	0.0079 (5)	−0.0021 (6)
S3	0.0459 (10)	0.0551 (11)	0.0631 (11)	−0.0076 (8)	0.0130 (8)	−0.0013 (9)
S2	0.0528 (11)	0.0485 (11)	0.0735 (12)	−0.0058 (9)	0.0003 (8)	0.0154 (9)
S1	0.0486 (10)	0.0621 (12)	0.0582 (11)	−0.0068 (9)	0.0037 (8)	−0.0030 (9)
F5	0.047 (2)	0.062 (2)	0.045 (2)	0.0062 (19)	−0.0039 (15)	−0.0006 (17)
O3	0.040 (2)	0.034 (2)	0.034 (2)	−0.0012 (18)	0.0059 (17)	0.0066 (18)
F4	0.071 (3)	0.094 (3)	0.039 (2)	0.028 (2)	0.0096 (18)	−0.008 (2)
O5	0.031 (2)	0.032 (2)	0.039 (2)	−0.0064 (17)	0.0133 (16)	−0.0031 (18)
O2	0.034 (2)	0.046 (3)	0.031 (2)	−0.0091 (18)	0.0102 (16)	0.0005 (18)
F8	0.052 (3)	0.046 (3)	0.160 (4)	−0.016 (2)	0.050 (3)	−0.004 (2)
O1	0.034 (2)	0.037 (2)	0.032 (2)	−0.0125 (18)	0.0002 (16)	−0.0015 (18)
O6	0.038 (2)	0.026 (2)	0.037 (2)	−0.0130 (18)	0.0047 (16)	−0.0020 (17)
F2	0.088 (3)	0.084 (3)	0.076 (3)	−0.035 (3)	−0.002 (2)	0.025 (2)
F3	0.035 (2)	0.074 (3)	0.158 (4)	0.001 (2)	0.007 (2)	0.018 (3)
F1	0.096 (3)	0.083 (3)	0.095 (3)	−0.062 (3)	0.033 (2)	−0.039 (3)
F7	0.042 (2)	0.084 (3)	0.133 (4)	−0.020 (2)	−0.005 (2)	0.006 (3)
F6	0.085 (3)	0.071 (3)	0.057 (2)	−0.036 (2)	0.005 (2)	0.018 (2)
O4	0.031 (2)	0.031 (2)	0.039 (2)	−0.0044 (17)	0.0050 (16)	−0.0017 (18)
C12	0.026 (3)	0.030 (3)	0.046 (4)	−0.009 (2)	0.006 (2)	0.000 (3)
F9	0.106 (3)	0.096 (3)	0.099 (3)	−0.051 (3)	0.078 (3)	−0.027 (3)
C14	0.022 (3)	0.032 (3)	0.060 (4)	−0.003 (3)	0.004 (3)	0.004 (3)
C18	0.043 (3)	0.035 (4)	0.036 (3)	−0.005 (3)	0.013 (3)	−0.006 (3)
C10	0.026 (3)	0.035 (3)	0.032 (3)	−0.018 (3)	−0.001 (2)	0.004 (3)
C2	0.042 (4)	0.032 (3)	0.051 (4)	−0.009 (3)	0.009 (3)	−0.008 (3)
C9	0.038 (4)	0.052 (4)	0.044 (4)	−0.003 (3)	0.002 (3)	−0.001 (3)
C22	0.033 (3)	0.046 (4)	0.040 (3)	−0.013 (3)	0.014 (3)	−0.001 (3)
C3	0.043 (4)	0.043 (4)	0.038 (3)	−0.002 (3)	0.015 (3)	0.000 (3)
C21	0.046 (4)	0.053 (4)	0.020 (3)	0.025 (3)	0.004 (2)	−0.012 (3)
C6	0.025 (3)	0.028 (3)	0.053 (4)	0.010 (2)	−0.003 (3)	0.000 (3)
C13	0.032 (3)	0.036 (3)	0.057 (4)	−0.013 (3)	0.002 (3)	0.005 (3)
C1	0.044 (4)	0.041 (4)	0.045 (4)	−0.016 (3)	0.010 (3)	0.005 (3)
C24	0.041 (4)	0.052 (4)	0.046 (4)	0.008 (3)	0.017 (3)	−0.006 (3)
C4	0.034 (3)	0.033 (3)	0.051 (4)	0.005 (3)	0.002 (3)	0.011 (3)
C7	0.052 (4)	0.062 (4)	0.035 (3)	0.010 (3)	0.004 (3)	0.005 (3)
C11	0.029 (3)	0.047 (4)	0.032 (3)	−0.003 (3)	0.003 (2)	−0.005 (3)
C17	0.038 (4)	0.032 (4)	0.073 (5)	−0.019 (3)	0.021 (3)	−0.007 (3)
C19	0.039 (3)	0.035 (3)	0.062 (4)	−0.014 (3)	0.015 (3)	−0.005 (3)
C8	0.047 (4)	0.054 (4)	0.067 (4)	−0.012 (3)	−0.006 (3)	−0.022 (4)
C23	0.070 (5)	0.043 (4)	0.058 (4)	−0.001 (4)	0.005 (4)	−0.013 (3)
C20	0.039 (3)	0.043 (4)	0.027 (3)	−0.009 (3)	0.001 (2)	0.000 (3)
C5	0.031 (3)	0.031 (3)	0.042 (3)	0.017 (3)	−0.019 (2)	−0.014 (3)
C15	0.048 (4)	0.043 (4)	0.084 (5)	−0.003 (3)	0.020 (4)	−0.005 (4)
C16	0.040 (4)	0.031 (4)	0.111 (6)	−0.001 (3)	−0.001 (4)	0.025 (4)

Geometric parameters (Å, º) top

Al1—O1	1.879 (3)	C14—C13	1.438 (7)
Al1—O4	1.882 (4)	C14—H14	0.9500
Al1—O3	1.918 (4)	C18—C19	1.368 (7)
Al1—O5	1.927 (3)	C18—C17	1.489 (7)
Al1—O2	1.928 (4)	C10—C11	1.359 (7)
Al1—O6	1.932 (4)	C10—C9	1.528 (7)
S3—C24	1.680 (6)	C2—C3	1.378 (7)
S3—C21	1.767 (6)	C2—C1	1.503 (7)
S2—C16	1.706 (7)	C22—C21	1.348 (7)
S2—C13	1.722 (6)	C22—C23	1.408 (8)
S1—C8	1.664 (6)	C22—H22	0.9500
S1—C5	1.744 (6)	C3—C4	1.428 (7)
F5—C9	1.331 (6)	C3—H3	0.9500
O3—C12	1.277 (6)	C21—C20	1.456 (7)
F4—C9	1.349 (6)	C6—C5	1.396 (7)
O5—C18	1.271 (6)	C6—C7	1.427 (8)
O2—C4	1.267 (6)	C6—H6	0.9500
F8—C17	1.314 (6)	C24—C23	1.351 (8)
O1—C2	1.284 (6)	C24—H24	0.9500
O6—C20	1.267 (6)	C4—C5	1.452 (7)
F2—C1	1.305 (6)	C7—C8	1.359 (8)
F3—C1	1.296 (7)	C7—H7	0.9500
F1—C1	1.313 (6)	C11—H11	0.9500
F7—C17	1.337 (7)	C19—C20	1.437 (7)
F6—C9	1.319 (6)	C19—H19	0.9500
O4—C10	1.295 (6)	C8—H8	0.9500
C12—C11	1.415 (7)	C23—H23	0.9500
C12—C13	1.449 (8)	C15—C16	1.338 (8)
F9—C17	1.314 (6)	C15—H15	0.9500
C14—C15	1.418 (8)	C16—H16	0.9500

O1—Al1—O4	95.39 (15)	C20—C21—S3	115.6 (5)
O1—Al1—O3	90.41 (15)	C5—C6—C7	109.1 (5)
O4—Al1—O3	90.98 (15)	C5—C6—H6	125.4
O1—Al1—O5	175.17 (16)	C7—C6—H6	125.4
O4—Al1—O5	88.53 (15)	C14—C13—C12	128.1 (5)
O3—Al1—O5	92.33 (15)	C14—C13—S2	112.5 (4)
O1—Al1—O2	90.83 (14)	C12—C13—S2	119.4 (4)
O4—Al1—O2	173.74 (15)	F3—C1—F2	105.5 (5)
O3—Al1—O2	88.24 (15)	F3—C1—F1	106.9 (5)
O5—Al1—O2	85.29 (15)	F2—C1—F1	105.8 (5)
O1—Al1—O6	87.13 (15)	F3—C1—C2	112.7 (5)
O4—Al1—O6	92.32 (15)	F2—C1—C2	113.0 (5)
O3—Al1—O6	176.06 (14)	F1—C1—C2	112.3 (5)
O5—Al1—O6	89.90 (15)	C23—C24—S3	112.1 (4)
O2—Al1—O6	88.71 (15)	C23—C24—H24	123.9
C24—S3—C21	90.7 (3)	S3—C24—H24	123.9
C16—S2—C13	90.7 (3)	O2—C4—C3	121.2 (5)
C8—S1—C5	90.9 (3)	O2—C4—C5	118.3 (5)
C12—O3—Al1	128.8 (3)	C3—C4—C5	120.5 (5)
C18—O5—Al1	125.6 (3)	C8—C7—C6	113.6 (5)
C4—O2—Al1	130.7 (4)	C8—C7—H7	123.2
C2—O1—Al1	126.5 (3)	C6—C7—H7	123.2
C20—O6—Al1	130.4 (3)	C10—C11—C12	122.2 (5)
C10—O4—Al1	123.4 (3)	C10—C11—H11	118.9
O3—C12—C11	121.9 (5)	C12—C11—H11	118.9
O3—C12—C13	116.5 (5)	F9—C17—F8	109.9 (5)
C11—C12—C13	121.6 (5)	F9—C17—F7	102.6 (5)
C15—C14—C13	108.3 (5)	F8—C17—F7	104.6 (5)
C15—C14—H14	125.9	F9—C17—C18	112.4 (5)
C13—C14—H14	125.9	F8—C17—C18	115.2 (5)
O5—C18—C19	128.6 (5)	F7—C17—C18	111.2 (5)
O5—C18—C17	112.5 (5)	C18—C19—C20	122.2 (5)
C19—C18—C17	118.9 (5)	C18—C19—H19	118.9
O4—C10—C11	127.9 (5)	C20—C19—H19	118.9
O4—C10—C9	111.9 (5)	C7—C8—S1	114.0 (5)
C11—C10—C9	120.1 (5)	C7—C8—H8	123.0
O1—C2—C3	128.0 (5)	S1—C8—H8	123.0
O1—C2—C1	112.8 (5)	C24—C23—C22	114.8 (6)
C3—C2—C1	119.2 (5)	C24—C23—H23	122.6
F6—C9—F5	106.9 (5)	C22—C23—H23	122.6
F6—C9—F4	108.1 (5)	O6—C20—C19	121.4 (5)
F5—C9—F4	105.9 (5)	O6—C20—C21	121.2 (5)
F6—C9—C10	110.8 (5)	C19—C20—C21	117.4 (5)
F5—C9—C10	112.2 (4)	C6—C5—C4	132.3 (5)
F4—C9—C10	112.5 (5)	C6—C5—S1	112.3 (4)
C21—C22—C23	110.8 (5)	C4—C5—S1	115.4 (4)
C21—C22—H22	124.6	C16—C15—C14	114.9 (6)
C23—C22—H22	124.6	C16—C15—H15	122.5
C2—C3—C4	122.2 (5)	C14—C15—H15	122.5
C2—C3—H3	118.9	C15—C16—S2	113.6 (5)
C4—C3—H3	118.9	C15—C16—H16	123.2
C22—C21—C20	132.6 (6)	S2—C16—H16	123.2
C22—C21—S3	111.7 (4)

O1—Al1—O3—C12	111.0 (4)	C16—S2—C13—C14	0.6 (4)
O4—Al1—O3—C12	15.6 (4)	C16—S2—C13—C12	−178.8 (4)
O5—Al1—O3—C12	−73.0 (4)	O1—C2—C1—F3	−85.8 (6)
O2—Al1—O3—C12	−158.2 (4)	C3—C2—C1—F3	96.5 (7)
O4—Al1—O5—C18	104.5 (4)	O1—C2—C1—F2	154.6 (5)
O3—Al1—O5—C18	−164.5 (4)	C3—C2—C1—F2	−23.0 (8)
O2—Al1—O5—C18	−76.5 (4)	O1—C2—C1—F1	35.0 (7)
O6—Al1—O5—C18	12.2 (4)	C3—C2—C1—F1	−142.7 (6)
O1—Al1—O2—C4	−8.8 (5)	C21—S3—C24—C23	0.5 (5)
O3—Al1—O2—C4	−99.2 (4)	Al1—O2—C4—C3	9.2 (8)
O5—Al1—O2—C4	168.3 (5)	Al1—O2—C4—C5	−170.9 (3)
O6—Al1—O2—C4	78.3 (4)	C2—C3—C4—O2	−4.9 (9)
O4—Al1—O1—C2	−174.4 (4)	C2—C3—C4—C5	175.2 (5)
O3—Al1—O1—C2	94.6 (4)	C5—C6—C7—C8	0.0 (7)
O2—Al1—O1—C2	6.4 (4)	O4—C10—C11—C12	−1.0 (8)
O6—Al1—O1—C2	−82.3 (4)	C9—C10—C11—C12	175.5 (5)
O1—Al1—O6—C20	161.0 (4)	O3—C12—C11—C10	−8.9 (8)
O4—Al1—O6—C20	−103.7 (4)	C13—C12—C11—C10	172.1 (5)
O5—Al1—O6—C20	−15.1 (4)	O5—C18—C17—F9	49.4 (7)
O2—Al1—O6—C20	70.1 (4)	C19—C18—C17—F9	−128.0 (6)
O1—Al1—O4—C10	−114.0 (4)	O5—C18—C17—F8	176.3 (5)
O3—Al1—O4—C10	−23.5 (4)	C19—C18—C17—F8	−1.2 (9)
O5—Al1—O4—C10	68.9 (4)	O5—C18—C17—F7	−65.0 (6)
O6—Al1—O4—C10	158.7 (4)	C19—C18—C17—F7	117.6 (6)
Al1—O3—C12—C11	−2.6 (7)	O5—C18—C19—C20	−2.8 (10)
Al1—O3—C12—C13	176.4 (3)	C17—C18—C19—C20	174.2 (5)
Al1—O5—C18—C19	−6.6 (8)	C6—C7—C8—S1	0.2 (7)
Al1—O5—C18—C17	176.3 (4)	C5—S1—C8—C7	−0.3 (5)
Al1—O4—C10—C11	21.0 (7)	S3—C24—C23—C22	−1.0 (7)
Al1—O4—C10—C9	−155.7 (3)	C21—C22—C23—C24	1.0 (8)
Al1—O1—C2—C3	−5.4 (8)	Al1—O6—C20—C19	11.1 (7)
Al1—O1—C2—C1	177.2 (4)	Al1—O6—C20—C21	−168.3 (3)
O4—C10—C9—F6	76.7 (5)	C18—C19—C20—O6	0.6 (8)
C11—C10—C9—F6	−100.4 (6)	C18—C19—C20—C21	−179.9 (5)
O4—C10—C9—F5	−42.8 (6)	C22—C21—C20—O6	−173.5 (6)
C11—C10—C9—F5	140.1 (5)	S3—C21—C20—O6	3.6 (6)
O4—C10—C9—F4	−162.2 (4)	C22—C21—C20—C19	7.0 (9)
C11—C10—C9—F4	20.8 (7)	S3—C21—C20—C19	−175.9 (4)
O1—C2—C3—C4	3.2 (9)	C7—C6—C5—C4	−178.5 (5)
C1—C2—C3—C4	−179.5 (5)	C7—C6—C5—S1	−0.2 (5)
C23—C22—C21—C20	176.7 (5)	O2—C4—C5—C6	−178.7 (5)
C23—C22—C21—S3	−0.5 (6)	C3—C4—C5—C6	1.2 (9)
C24—S3—C21—C22	0.0 (5)	O2—C4—C5—S1	3.0 (6)
C24—S3—C21—C20	−177.7 (4)	C3—C4—C5—S1	−177.1 (4)
C15—C14—C13—C12	177.7 (5)	C8—S1—C5—C6	0.3 (4)
C15—C14—C13—S2	−1.8 (6)	C8—S1—C5—C4	178.9 (4)
O3—C12—C13—C14	−179.1 (5)	C13—C14—C15—C16	2.4 (7)
C11—C12—C13—C14	−0.1 (8)	C14—C15—C16—S2	−2.0 (7)
O3—C12—C13—S2	0.3 (6)	C13—S2—C16—C15	0.8 (5)
C11—C12—C13—S2	179.3 (4)

Experimental details

Crystal data
Chemical formula	[Al(C₈H₄F₃O₂S)₃]₃[Fe(C₈H₄F₃O₂S)₃]
M_r	2790.97
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	13.743 (3), 14.278 (2), 14.136 (3)
β (°)	94.013 (18)
V (Å³)	2767.1 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.52
Crystal size (mm)	0.14 × 0.10 × 0.10

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with a Sapphire3 (Gemini Ultra Mo) detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11706, 6021, 2687
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.185, 0.91
No. of reflections	6021
No. of parameters	388
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.44

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and WinGX32 (Farrugia, 1999).

Acknowledgements

This work was supported by the Applied Chemistry Cluster of the Faculty of Science and Technology at the Queensland University of Technology and the Commission on Higher Education - Higher Education Development Project - Faculty Development Program of the Philippines. We thank Jocelyne Bouzaid for assistance with the SEM-EDX.

References

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