Crystal structure of bis­(acetyl­acetonato-κ2O,O′)(tetra­hydro­furan-κO)(tri­fluoro­methane­sulfonato-κO)iron(III)

Richers, C.P.; Bertke, J.A.; Rauchfuss, T.B.

doi:10.1107/S2056989015016849

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Volume 71| Part 10| October 2015| Pages 1165-1168

doi:10.1107/S2056989015016849

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Crystal structure of bis(acetylacetonato-κ²O,O′)(tetrahydrofuran-κO)(trifluoromethanesulfonato-κO)iron(III)

Casseday P. Richers,^a Jeffery A. Bertke ^a ^* and Thomas B. Rauchfuss ^a

^aSchool of Chemical Sciences, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA
^*Correspondence e-mail: jbertke@illinois.edu

Edited by G. Smith, Queensland University of Technology, Australia (Received 20 August 2015; accepted 8 September 2015; online 12 September 2015)

The mononuclear title complex, [Fe(CF₃O₃S)(C₅H₇O₂)₂(C₄H₈O)] or [Fe(acac)₂(OTf)(THF)] (acac = acetylacetonate; OTf = trifluoromethanesulfonate; THF = tetrahydrofuran), (I), consists of one six-coordinate Fe³⁺ atom in a slightly distorted octahedral environment [Fe—O bond-length range = 1.9517 (11)–2.0781 (11) Å]. The triflate ligand was found to be disordered over two sets of sites, with a site-occupancy ratio of 0.622 (16):0.378 (16). Weak intermolecular C—H⋯O and C—H⋯F hydrogen-bonding interactions generate a two-dimensional supramolecular structure lying parallel to (100). This is only the second crystal structure reported of a mononuclear bis(acetylacetonato)iron(III) complex.

Keywords: crystal structure; iron(III); acac; triflate; tetrahydrofuran.

CCDC reference: 1423096

1. Chemical context

Because of its ease-of-handling, relative stability and good solubility in most organic solvents, tris(acetylacetonato)iron(III) [Fe(acac)₃] is often used as a catalyst or catalyst precursor in iron-catalysed reactions (Sherry & Fürstner, 2008 ; Zettler et al., 2001 ). In many applications, the loss or substitution of one or more acetylacetonate ligands from [Fe(acac)₃] is expected. However, the substitution of a single acetylacetonato ligand is rarely observed. Relevant examples include protonations of Fe(acac)₃ with oxalic acid (Fujino et al., 2004 ) and hydrochloric acid (Lindley & Smith, 1970 ) to form [Fe(acac)₂]₂(μ-C₂O₄) and [Fe(acac)₂Cl], respectively. The dinuclear alkoxides, [Fe(acac)₂(μ-OR)] are also known (Chiari et al., 1984 ; Leluk et al., 1992 ; Wu et al., 1972 ). We now report that the addition of triflic acid to a THF solution of [Fe(acac)₃] results in the formation of a mononuclear bis(acetylacetonato)iron(III) complex, [Fe(acac)₂(OTf)(THF)], the title compound (I) whose structure is reported herein. This compound is a rare bis(acetylacetonato)iron(III) complex that has been crystallographically characterized.

2. Structural commentary

The molecular structure of the mononuclear complex (I) (Fig. 1) consists of one six-coordinate Fe³⁺ atom in an slightly distorted octahedral FeO₆ environment. The coordination sphere of the metal comprises four oxygen atoms from two κ²-acac ligands [Fe—O_acac range = 1.9517 (11)–1.9762 (11) Å], one oxygen atom of a THF solvate molecule [Fe1—O8 = 2.0781 (11) Å] and one oxygen atom of a disordered triflate anion [Fe1—O5 = 2.063 (4) Å or Fe1—O5B = 2.066 (6) Å] (Table 1). The disorder in the triflate ligand was found to be 0.622 (16):0.378 (16). The angles around Fe1 deviate from the ideal octahedral angles of 90 and 180°, the cis angles range from 84.63 (5)° to 98.09 (5)° and the trans angles range from 172.60 (5)° to 174.9 (6)°.

Table 1
Selected bond lengths (Å)

Fe1—O1	1.9517 (11)	Fe1—O8	2.0781 (11)
Fe1—O4	1.9651 (11)	Fe1—O5	2.063 (4)
Fe1—O3	1.9742 (11)	Fe1—O5B	2.066 (6)
Fe1—O2	1.9762 (11)

Figure 1
A molecule plot showing the atom numbering, with 35% probability ellipsoids for non-H atoms and spheres of arbitrary size for H atoms. Only the major component of the disordered triflate ligand is shown.

3. Supramolecular features

There are no significant supramolecular features to discuss in the extended structure of (I). There are weak C—H⋯O and C—H⋯F intermolecular hydrogen-bonding interactions resulting in the formation of two-dimensional layers parallel to the (100) plane (Fig. 2a,b). A series of C_methyl—H⋯O_acac, C_methyl—H⋯O_triflate, C_methyl—H⋯F_triflate, C_THF—H⋯O_triflate, and C_THF—H⋯F_triflate interactions make up the layers, the details of these interactions are presented in Table 2. Each molecule connects to six neighboring molecules through various combinations of these interactions, Fig. 2c,d.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯O3ⁱ	0.98	2.53	3.370 (2)	144
C5—H5A⋯O1ⁱⁱ	0.98	2.60	3.539 (2)	161
C5—H5B⋯O6Bⁱⁱⁱ	0.98	2.56	3.471 (12)	154
C6—H6A⋯O5^iv	0.98	2.63	3.429 (9)	138
C6—H6A⋯O6^iv	0.98	2.58	3.436 (10)	145
C10—H10B⋯F3^v	0.98	2.56	3.214 (6)	124
C12—H12A⋯O6^iv	0.99	2.51	3.321 (7)	138
C12—H12A⋯O6B^iv	0.99	2.60	3.423 (11)	140
C14—H14A⋯O7B^vi	0.99	2.63	3.411 (10)	136
C14—H14B⋯F2B^vii	0.99	2.50	3.316 (6)	139
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x+1, -y+1, -z+1; (iv) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) x, y+1, z; (vii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
A view of the extended structure of (I)

(a) along the b axis showing two neighboring layers; (b) along the a axis showing one two-dimensional layer; (c) showing the highlighted molecule connecting to six neighboring molecules; and (d) reduced to a ball-and-stick representation, orange balls represent one molecule of (I)

connecting to six neighbors. H⋯O interactions are shown as red dashed lines, H⋯F interactions are shown as blue dashed lines. Only the major component of the disordered triflate is shown, and all H atoms except those that participate in the interactions are omitted in parts (a)–(c).

4. Database survey

Only one other mononuclear bis(acetylacetonato)iron(III) complex has been characterized crystallographically, [Fe(acac)₂Cl] (Lindley & Smith, 1970). This complex comprises a five-coordinate iron(III) atom in a square-pyramidal geometry. The Fe—O distance reported is 1.95 (1) Å, which is comparable to the average Fe—O_acac distance in (I) of 1.9668 Å. A search of the Cambridge Structural Database (Groom & Allen, 2014 ) reveals twelve bis(acetylacetonato)iron(III) complexes with a Fe—O_acac range of 1.945–2.062 Å.

A survey of the database for similar complexes with other transition metals yields one mononuclear bis(acac)-triflate complex, [Os(acac)₂(C₆H₅)(OTf)] (Young et al., 2011 ). There is also only one mononuclear bis(acac)-THF complex, [V(acac)₂(Mes)(THF)] (Mes = mesityl; Imhof & Seidel, 2006 ). There are six bis(acac)-bis(THF) complexes; three mononuclear (Baisch & Poli, 2008 ; Döring et al., 1992 ; Langer et al., 2007 ), two dinuclear (Baisch & Poli, 2008; Döring et al., 1992) and one heterometallic tetranuclear (Döring et al., 2006 ).

5. Synthesis and crystallization

Triflic acid (251 µL, 0.24 g, 1 equiv) was added to a solution of [Fe(acac)₃] (1 g, 2.83 mmol, 1 equiv) in dry THF (5 mL). The resulting purple–red solution was stirred at room temperature for 1 h. The reaction mixture was then concentrated under vacuum to a volume of approximately 2 mL, and 20 mL of pentane was added. A dark purple–red microcrystalline solid precipitated. The mixture was filtered through a glass-frit and the microcrystalline solid was dried under vacuum (1.25 g, 2.63 mmol, 93%). Crystals suitable for X-ray diffraction were grown by slow diffusion of pentane into a THF solution of the purple–red solid. CH analysis calculated for C₁₅H₂₂F₃FeO₈S (MW: 475.235): C 37.91%; H 4.67%. Found: C 37.69%; H, 4.45%.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. A structural model consisting of the target molecule was developed. The triflate ion is disordered over two positions, with refined site-occupancies of 0.622 (16) and 0.378 (16). The equivalent Fe—O, O—S, S—C, and C—F distances were restrained to be similar (s.u. = 0.01 Å). The disordered atoms were restrained to behave relatively isotropically. Similar displacement amplitudes were imposed on disordered sites overlapping by less than the sum of van der Waals radii. Methyl H atom positions were optimized by rotation about R—C bonds with idealized C—H, R⋯H and H⋯H distances and included as riding idealized contributors [C—H_methyl = 0.98 Å with U_iso = 1.5U_eq(C)]. Remaining H atoms were also included as riding idealized contributors [C—H_methylene= 0.99 Å and C—H_aromatic = 0.95 Å, both with U_iso = 1.2U_eq(C)].

Table 3
Experimental details

Crystal data
Chemical formula	[Fe(CF₃O₃S)(C₅H₇O₂)₂(C₄H₈O)]
M_r	475.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	103
a, b, c (Å)	15.0118 (8), 8.4523 (4), 15.9842 (9)
β (°)	100.451 (2)
V (Å³)	1994.50 (18)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.93
Crystal size (mm)	0.77 × 0.09 × 0.08

Data collection
Diffractometer	Bruker D8 Venture/Photon 100
Absorption correction	Integration (SADABS; Bruker, 2013 )
T_min, T_max	0.720, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	48981, 4417, 3800
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.066, 1.06
No. of reflections	4417
No. of parameters	330
No. of restraints	344
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.38
Computer programs: APEX2, SAINT, XPREP, SADABS, TWINABS and XCIF (Bruker, 2013), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2015 ), CrystalMaker (CrystalMaker, 1994 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1423096

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015016849/zs2341sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015016849/zs2341Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015016849/zs2341Isup3.tif

checkCIF report

Chemical context top

Because of its ease-of-handling, relative stability and good solubility in most organic solvents, tris(acetylacetonato)iron(III) [Fe(acac)₃] is often used as a catalyst or catalyst precursor in iron-catalysed reactions (Sherry & Fürstner, 2008; Zettler et al., 2001). In many applications, the loss or substitution of one or more acetylacetonate ligands from [Fe(acac)₃] is expected. However, the substitution of a single acetoacetonato ligand is rarely observed. Relevant examples include protonations of Fe(acac)₃ with oxalic acid (Fujino et al., 2004) and hydrochloric acid (Lindley & Smith, 1970) to form [Fe(acac)₂]₂(µ-C₂O₄) and [Fe(acac)₂Cl], respectively. The dinuclear alkoxides, [Fe(acac)₂(µ-OR)] are also known (Chiari et al., 1984; Leluk et al., 1992; Wu et al., 1972). We now report that the addition of triflic acid to a THF solution of [Fe(acac)₃] results in the formation of a mononuclear bis(acetylacetonato)iron(III) complex, [Fe(acac)₂(OTf)(THF)], the title compound (I) whose structure is reported herein. This compound is a rare bis(acetylacetonato)iron(III) complex that has been crystallographically characterized.

Structural commentary top

Supramolecular features top

There are no significant supramolecular features to discuss in the extended structure of (I). There are weak C—H···O and C—H···F intermolecular hydrogen-bonding interactions resulting in the formation of two-dimensional layers parallel to the (100) plane (Fig. 2a,b). A series of C_methyl—H···O_acac, C_methyl—H···O_triflate, C_methyl—H···F_triflate, C_THF—H···O_triflate, and C_THF—H···F_triflate interactions make up the layers, the details of these interactions are presented in Table 2. Each molecule connects to six neighboring molecules through various combinations of these interactions, Fig. 2c,d.

Database survey top

Only one other mononuclear bis(acetylacetonato)iron(III) complex has been characterized crystallographically, [Fe(acac)₂Cl] (Lindley & Smith, 1970). This complex comprises a five-coordinate iron(III) atom in a square-pyramidal geometry. The Fe—O distance reported is 1.95 (1) Å, which is comparable to the average Fe—O_acac distance in (I) of 1.9668 Å. A search of the Cambridge Structural Database (Groom & Allen, 2014) reveals twelve bis(acetylacetonato)iron(III) complexes with a Fe—O_acac range of 1.945–2.062 Å.

A survey of the database for similar complexes with other transition metals yields one mononuclear bis(acac)-triflate complex, [Os(acac)₂(C₆H₅)(OTf)] (Young et al., 2011). There is also only one mononuclear bis(acac)-THF complex, [V(acac)₂(Mes)(THF)] (Imhof & Seidel, 2006.) There are six bis(acac)-bis(THF) complexes; three mononuclear (Baisch & Poli, 2008; Doring et al., 1992; Langer et al., 2007), two dinuclear (Baisch & Poli, 2008; Doring et al., 1992) and one heterometallic tetranuclear (Doring et al., 2006).

Synthesis and crystallization top

Triflic acid (251 µL, 0.24 g, 1 equiv) was added to a solution of [Fe(acac)₃] (1 g, 2.83 mmol, 1 equiv) in dry THF (5 mL). The resulting purple–red solution was stirred at room temperature for 1 h. The reaction mixture was then concentrated under vacuum to a volume of approximately 2 mL, and 20 mL of pentane was added. A dark purple–red microcrystalline solid precipitated. The mixture was filtered through a glass-frit and the microcrystalline solid was dried under vacuum (1.25 g, 2.63 mmol, 93 %). Crystals suitable for X-ray diffraction were grown by slow diffusion of pentane into a THF solution of the purple–red solid. CH analysis calculated for C₁₅H₂₂F₃FeO₈S (MW: 475.235): C 37.91%; H 4.67%. Found: C 37.69%; H, 4.45%.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 3. A structural model consisting of the target molecule was developed. The triflate ion is disordered over two positions, with refined site-occupancies of 0.622 (16) and 0.378 (16). The equivalent Fe—O, O—S, S—C, and C—F distances were restrained to be similar (s.u. = 0.01 Å). The disordered atoms were restrained to behave relatively isotropically. Similar displacement amplitudes were imposed on disordered sites overlapping by less than the sum of van der Waals radii. Methyl H atom positions were optimized by rotation about R—C bonds with idealized C—H, R···H and H···H distances and included as riding idealized contributors [C—H_methyl = 0.98 Å with U_iso = 1.5U_eq(C)]. Remaining H atoms were also included as riding idealized contributors [C—H_methylene= 0.99 Å and C—H_aromatic = 0.95 Å, both with U_iso = 1.2U_eq(C)].

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT, XPREP, SADABS and TWINABS (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and CrystalMaker (CrystalMaker, 1994); software used to prepare material for publication: XCIF (Bruker, 2013) and publCIF (Westrip, 2010).

Figures top

Fig. 1. A molecule plot showing the atom numbering, with 35% probability ellipsoids for non-H atoms and circles of arbitrary size for H atoms. Only the major component of the disordered triflate ligand is shown.

Fig. 2. A view of the extended structure of (I) (a) along the b axis showing two neighboring layers; (b) along the a axis showing one two-dimensional layer; (c) showing the highlighted molecule connecting to six neighboring molecules; and (d) reduced to a ball-and-stick representation, orange balls represent one molecule of (I) connecting to six neighbors. H···O interactions are shown as red dashed lines, H···F interactions are shown as blue dashed lines. Only the major component of the disordered triflate is shown, and all H atoms except those that participate in the interactions are omitted in parts (a)–(c).

Bis(acetylacetonato-κ²O,O')(tetrahydrofuran-κO)(trifluoromethanesulfonato-κO)iron(III) top

Crystal data top

[Fe(CF₃O₃S)(C₅H₇O₂)₂(C₄H₈O)]	F(000) = 980
M_r = 475.23	D_x = 1.583 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.0118 (8) Å	Cell parameters from 9821 reflections
b = 8.4523 (4) Å	θ = 2.6–27.1°
c = 15.9842 (9) Å	µ = 0.93 mm⁻¹
β = 100.451 (2)°	T = 103 K
V = 1994.50 (18) Å³	Needle, red
Z = 4	0.77 × 0.09 × 0.08 mm

Data collection top

Bruker D8 Venture/Photon 100 diffractometer	4417 independent reflections
Radiation source: microfocus sealed tube	3800 reflections with I > 2σ(I)
Multilayer mirrors monochromator	R_int = 0.058
profile data from φ and ω scans	θ_max = 27.2°, θ_min = 2.6°
Absorption correction: integration (SADABS; Bruker, 2013)	h = −19→19
T_min = 0.720, T_max = 0.955	k = −10→10
48981 measured reflections	l = −20→20

Refinement top

Refinement on F²	344 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.030P)² + 1.245P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
4417 reflections	Δρ_max = 0.29 e Å⁻³
330 parameters	Δρ_min = −0.38 e Å⁻³

Crystal data top

[Fe(CF₃O₃S)(C₅H₇O₂)₂(C₄H₈O)]	V = 1994.50 (18) Å³
M_r = 475.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.0118 (8) Å	µ = 0.93 mm⁻¹
b = 8.4523 (4) Å	T = 103 K
c = 15.9842 (9) Å	0.77 × 0.09 × 0.08 mm
β = 100.451 (2)°

Data collection top

Bruker D8 Venture/Photon 100 diffractometer	4417 independent reflections
Absorption correction: integration (SADABS; Bruker, 2013)	3800 reflections with I > 2σ(I)
T_min = 0.720, T_max = 0.955	R_int = 0.058
48981 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	344 restraints
wR(F²) = 0.066	H-atom parameters constrained
S = 1.06	Δρ_max = 0.29 e Å⁻³
4417 reflections	Δρ_min = −0.38 e Å⁻³
330 parameters

Special details top

Experimental. One distinct cell was identified using APEX2 (Bruker, 2013). Six frame series were integrated and filtered for statistical outliers using SAINT (Bruker, 2013) then corrected for absorption by integration using SAINT/SADABS (Bruker, 2013) to sort, merge, and scale the combined data. No decay correction was applied.

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. Structure was phased by direct methods (Sheldrick, 2008). Systematic conditions suggested the unambiguous space group. The space group choice was confirmed by successful convergence of the full-matrix least-squares refinement on F². The final map had no significant features. A final analysis of variance between observed and calculated structure factors showed little dependence on amplitude or resolution.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Fe1	0.70581 (2)	0.58797 (3)	0.74733 (2)	0.01158 (7)
O1	0.63555 (7)	0.39298 (13)	0.72713 (7)	0.0148 (2)
O2	0.59623 (7)	0.70589 (13)	0.69469 (7)	0.0149 (2)
C1	0.53914 (11)	0.19970 (19)	0.65236 (11)	0.0190 (3)
H1A	0.5792	0.1539	0.6167	0.028*
H1B	0.4762	0.1933	0.6225	0.028*
H1C	0.5457	0.1409	0.7060	0.028*
C2	0.56412 (10)	0.36918 (19)	0.67064 (10)	0.0142 (3)
C3	0.51150 (11)	0.48966 (19)	0.62755 (10)	0.0161 (3)
H3	0.4612	0.4605	0.5852	0.019*
C4	0.52805 (10)	0.65102 (19)	0.64266 (9)	0.0139 (3)
C5	0.46288 (11)	0.7717 (2)	0.59819 (11)	0.0189 (3)
H5A	0.4358	0.8302	0.6403	0.028*
H5B	0.4150	0.7183	0.5583	0.028*
H5C	0.4952	0.8455	0.5670	0.028*
O3	0.68185 (7)	0.60779 (13)	0.86430 (7)	0.0160 (2)
O4	0.82353 (7)	0.49312 (13)	0.79526 (7)	0.0146 (2)
C6	0.69073 (12)	0.5923 (2)	1.01300 (10)	0.0207 (4)
H6A	0.6823	0.7058	1.0215	0.031*
H6B	0.7315	0.5487	1.0625	0.031*
H6C	0.6320	0.5386	1.0062	0.031*
C7	0.73100 (11)	0.56757 (18)	0.93464 (10)	0.0145 (3)
C8	0.81768 (11)	0.5026 (2)	0.94177 (11)	0.0205 (4)
H8	0.8498	0.4788	0.9972	0.025*
C9	0.85978 (11)	0.47054 (18)	0.87341 (10)	0.0143 (3)
C10	0.95457 (11)	0.4060 (2)	0.88703 (11)	0.0211 (4)
H10A	0.9567	0.3141	0.8501	0.032*
H10B	0.9730	0.3741	0.9466	0.032*
H10C	0.9959	0.4878	0.8733	0.032*
S1	0.7575 (2)	0.4546 (5)	0.5659 (2)	0.0133 (7)	0.622 (16)
O5	0.7471 (8)	0.5722 (10)	0.6313 (4)	0.0148 (14)	0.622 (16)
O6	0.7263 (6)	0.5123 (11)	0.4815 (4)	0.0255 (14)	0.622 (16)
O7	0.7340 (4)	0.2959 (7)	0.5840 (5)	0.0218 (11)	0.622 (16)
C11	0.8807 (3)	0.4490 (8)	0.5760 (4)	0.0251 (11)	0.622 (16)
F1	0.9134 (4)	0.5931 (7)	0.5691 (5)	0.0487 (14)	0.622 (16)
F2	0.9202 (3)	0.3903 (10)	0.6507 (2)	0.0451 (12)	0.622 (16)
F3	0.9047 (7)	0.3580 (11)	0.5158 (6)	0.0374 (15)	0.622 (16)
S1B	0.7611 (4)	0.4453 (9)	0.5676 (3)	0.0166 (12)	0.378 (16)
O5B	0.7429 (13)	0.5656 (16)	0.6296 (7)	0.014 (2)	0.378 (16)
O6B	0.7140 (9)	0.4806 (17)	0.4836 (6)	0.0209 (19)	0.378 (16)
O7B	0.7585 (8)	0.2869 (11)	0.5971 (9)	0.027 (2)	0.378 (16)
C11B	0.8794 (5)	0.4866 (12)	0.5638 (6)	0.0249 (18)	0.378 (16)
F1B	0.8914 (6)	0.6304 (9)	0.5356 (7)	0.0424 (16)	0.378 (16)
F2B	0.9310 (4)	0.4709 (16)	0.6402 (4)	0.047 (2)	0.378 (16)
F3B	0.9104 (11)	0.3852 (18)	0.5118 (9)	0.037 (2)	0.378 (16)
O8	0.76794 (8)	0.80858 (13)	0.75681 (7)	0.0171 (2)
C12	0.72268 (12)	0.9548 (2)	0.77383 (13)	0.0237 (4)
H12A	0.6923	0.9419	0.8235	0.028*
H12B	0.6768	0.9859	0.7239	0.028*
C13	0.79668 (13)	1.0771 (2)	0.79186 (12)	0.0252 (4)
H13A	0.8229	1.0812	0.8533	0.030*
H13B	0.7738	1.1834	0.7728	0.030*
C14	0.86588 (12)	1.0189 (2)	0.74034 (12)	0.0238 (4)
H14A	0.8492	1.0511	0.6800	0.029*
H14B	0.9272	1.0593	0.7639	0.029*
C15	0.86120 (12)	0.8415 (2)	0.74971 (14)	0.0291 (4)
H15A	0.8771	0.7876	0.6994	0.035*
H15B	0.9032	0.8055	0.8012	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.00926 (11)	0.01369 (11)	0.01071 (11)	0.00065 (8)	−0.00107 (8)	−0.00028 (8)
O1	0.0115 (5)	0.0167 (5)	0.0150 (5)	−0.0007 (4)	−0.0010 (4)	0.0020 (4)
O2	0.0116 (5)	0.0162 (5)	0.0152 (6)	0.0010 (4)	−0.0023 (4)	−0.0011 (4)
C1	0.0140 (8)	0.0176 (8)	0.0242 (9)	−0.0032 (6)	0.0002 (7)	−0.0022 (7)
C2	0.0111 (7)	0.0194 (8)	0.0129 (7)	−0.0026 (6)	0.0044 (6)	−0.0020 (6)
C3	0.0118 (8)	0.0206 (8)	0.0142 (8)	−0.0003 (6)	−0.0021 (6)	−0.0024 (6)
C4	0.0103 (7)	0.0216 (8)	0.0098 (7)	0.0018 (6)	0.0019 (6)	0.0001 (6)
C5	0.0155 (8)	0.0207 (8)	0.0182 (8)	0.0039 (6)	−0.0027 (7)	0.0004 (6)
O3	0.0127 (5)	0.0222 (6)	0.0123 (5)	0.0033 (5)	−0.0002 (4)	0.0000 (4)
O4	0.0117 (5)	0.0179 (5)	0.0132 (5)	0.0025 (4)	−0.0006 (4)	−0.0004 (4)
C6	0.0208 (9)	0.0269 (9)	0.0142 (8)	0.0013 (7)	0.0031 (7)	−0.0014 (7)
C7	0.0154 (8)	0.0140 (7)	0.0133 (7)	−0.0024 (6)	0.0002 (6)	−0.0011 (6)
C8	0.0161 (8)	0.0308 (9)	0.0126 (8)	0.0047 (7)	−0.0025 (6)	0.0030 (7)
C9	0.0118 (8)	0.0116 (7)	0.0178 (8)	−0.0010 (6)	−0.0017 (6)	0.0015 (6)
C10	0.0140 (8)	0.0265 (9)	0.0211 (8)	0.0050 (7)	−0.0013 (7)	0.0018 (7)
S1	0.0083 (9)	0.0132 (9)	0.0184 (12)	−0.0024 (7)	0.0027 (7)	−0.0013 (7)
O5	0.017 (2)	0.015 (2)	0.012 (2)	−0.0008 (19)	0.0022 (19)	−0.0018 (19)
O6	0.031 (3)	0.034 (3)	0.0109 (15)	0.002 (2)	0.0008 (14)	−0.0019 (14)
O7	0.019 (2)	0.0163 (17)	0.032 (3)	−0.0012 (15)	0.0075 (19)	−0.0042 (13)
C11	0.0187 (18)	0.028 (2)	0.030 (2)	−0.0036 (14)	0.0092 (15)	−0.0096 (16)
F1	0.032 (2)	0.040 (2)	0.081 (3)	−0.0199 (16)	0.030 (2)	−0.021 (2)
F2	0.0209 (13)	0.076 (3)	0.0348 (13)	0.0163 (16)	−0.0044 (10)	−0.0075 (17)
F3	0.025 (2)	0.047 (3)	0.043 (2)	0.0016 (19)	0.0147 (16)	−0.0223 (19)
S1B	0.023 (2)	0.0207 (19)	0.0045 (16)	0.0033 (12)	−0.0006 (12)	−0.0060 (12)
O5B	0.016 (4)	0.013 (4)	0.014 (4)	0.000 (3)	0.003 (3)	−0.002 (3)
O6B	0.019 (3)	0.030 (4)	0.012 (3)	−0.009 (3)	−0.0012 (19)	−0.003 (2)
O7B	0.036 (5)	0.016 (2)	0.029 (4)	0.011 (3)	0.010 (4)	0.004 (2)
C11B	0.018 (3)	0.034 (4)	0.022 (3)	0.000 (3)	0.001 (2)	−0.011 (3)
F1B	0.029 (3)	0.038 (3)	0.065 (4)	−0.017 (2)	0.021 (3)	−0.006 (2)
F2B	0.019 (2)	0.082 (5)	0.036 (3)	0.013 (3)	−0.0121 (17)	−0.020 (3)
F3B	0.022 (3)	0.049 (5)	0.044 (4)	−0.002 (3)	0.015 (3)	−0.023 (3)
O8	0.0116 (5)	0.0136 (5)	0.0260 (6)	0.0004 (4)	0.0029 (5)	−0.0043 (5)
C12	0.0208 (9)	0.0162 (8)	0.0346 (10)	0.0029 (7)	0.0063 (8)	−0.0087 (7)
C13	0.0318 (10)	0.0166 (8)	0.0279 (10)	−0.0043 (7)	0.0075 (8)	−0.0068 (7)
C14	0.0225 (9)	0.0190 (8)	0.0299 (10)	−0.0038 (7)	0.0050 (8)	−0.0013 (7)
C15	0.0131 (9)	0.0202 (9)	0.0541 (13)	−0.0033 (7)	0.0066 (8)	−0.0066 (9)

Geometric parameters (Å, º) top

Fe1—O1	1.9517 (11)	C10—H10A	0.9800
Fe1—O4	1.9651 (11)	C10—H10B	0.9800
Fe1—O3	1.9742 (11)	C10—H10C	0.9800
Fe1—O2	1.9762 (11)	S1—O7	1.430 (4)
Fe1—O8	2.0781 (11)	S1—O6	1.431 (4)
Fe1—O5	2.063 (4)	S1—O5	1.472 (4)
Fe1—O5B	2.066 (6)	S1—C11	1.829 (4)
O1—C2	1.2862 (19)	C11—F1	1.324 (5)
O2—C4	1.2827 (19)	C11—F2	1.329 (5)
C1—C2	1.496 (2)	C11—F3	1.332 (4)
C1—H1A	0.9800	S1B—O7B	1.422 (6)
C1—H1B	0.9800	S1B—O6B	1.431 (6)
C1—H1C	0.9800	S1B—O5B	1.479 (6)
C2—C3	1.392 (2)	S1B—C11B	1.822 (6)
C3—C4	1.399 (2)	C11B—F1B	1.319 (7)
C3—H3	0.9500	C11B—F2B	1.330 (7)
C4—C5	1.500 (2)	C11B—F3B	1.335 (6)
C5—H5A	0.9800	O8—C15	1.452 (2)
C5—H5B	0.9800	O8—C12	1.4596 (19)
C5—H5C	0.9800	C12—C13	1.506 (2)
O3—C7	1.2740 (19)	C12—H12A	0.9900
O4—C9	1.2830 (19)	C12—H12B	0.9900
C6—C7	1.501 (2)	C13—C14	1.520 (3)
C6—H6A	0.9800	C13—H13A	0.9900
C6—H6B	0.9800	C13—H13B	0.9900
C6—H6C	0.9800	C14—C15	1.509 (2)
C7—C8	1.398 (2)	C14—H14A	0.9900
C8—C9	1.385 (2)	C14—H14B	0.9900
C8—H8	0.9500	C15—H15A	0.9900
C9—C10	1.503 (2)	C15—H15B	0.9900

O1—Fe1—O4	98.09 (5)	C9—C10—H10A	109.5
O1—Fe1—O3	92.44 (5)	C9—C10—H10B	109.5
O4—Fe1—O3	88.33 (5)	H10A—C10—H10B	109.5
O1—Fe1—O2	88.42 (5)	C9—C10—H10C	109.5
O4—Fe1—O2	172.76 (5)	H10A—C10—H10C	109.5
O3—Fe1—O2	94.58 (5)	H10B—C10—H10C	109.5
O1—Fe1—O5	92.2 (3)	O7—S1—O6	117.4 (4)
O4—Fe1—O5	85.9 (3)	O7—S1—O5	115.3 (4)
O3—Fe1—O5	173.1 (3)	O6—S1—O5	112.4 (4)
O2—Fe1—O5	90.7 (3)	O7—S1—C11	103.9 (3)
O1—Fe1—O5B	89.9 (4)	O6—S1—C11	104.2 (4)
O4—Fe1—O5B	86.9 (5)	O5—S1—C11	101.0 (4)
O3—Fe1—O5B	174.9 (6)	S1—O5—Fe1	140.4 (5)
O2—Fe1—O5B	89.9 (5)	F1—C11—F2	107.9 (4)
O1—Fe1—O8	172.60 (5)	F1—C11—F3	108.5 (5)
O4—Fe1—O8	88.72 (5)	F2—C11—F3	107.4 (5)
O3—Fe1—O8	90.64 (5)	F1—C11—S1	110.6 (3)
O2—Fe1—O8	84.63 (5)	F2—C11—S1	111.6 (4)
O5—Fe1—O8	85.4 (2)	F3—C11—S1	110.7 (5)
O5B—Fe1—O8	87.5 (4)	O7B—S1B—O6B	118.0 (7)
C2—O1—Fe1	127.22 (10)	O7B—S1B—O5B	114.0 (7)
C4—O2—Fe1	126.75 (10)	O6B—S1B—O5B	111.4 (8)
C2—C1—H1A	109.5	O7B—S1B—C11B	106.1 (5)
C2—C1—H1B	109.5	O6B—S1B—C11B	104.3 (6)
H1A—C1—H1B	109.5	O5B—S1B—C11B	101.0 (7)
C2—C1—H1C	109.5	S1B—O5B—Fe1	141.8 (8)
H1A—C1—H1C	109.5	F1B—C11B—F2B	108.2 (6)
H1B—C1—H1C	109.5	F1B—C11B—F3B	107.2 (8)
O1—C2—C3	123.98 (15)	F2B—C11B—F3B	107.3 (9)
O1—C2—C1	115.74 (14)	F1B—C11B—S1B	112.5 (5)
C3—C2—C1	120.28 (14)	F2B—C11B—S1B	111.0 (5)
C2—C3—C4	124.09 (15)	F3B—C11B—S1B	110.5 (8)
C2—C3—H3	118.0	C15—O8—C12	109.89 (12)
C4—C3—H3	118.0	C15—O8—Fe1	126.35 (10)
O2—C4—C3	124.06 (14)	C12—O8—Fe1	123.75 (10)
O2—C4—C5	115.87 (14)	O8—C12—C13	105.35 (14)
C3—C4—C5	120.06 (14)	O8—C12—H12A	110.7
C4—C5—H5A	109.5	C13—C12—H12A	110.7
C4—C5—H5B	109.5	O8—C12—H12B	110.7
H5A—C5—H5B	109.5	C13—C12—H12B	110.7
C4—C5—H5C	109.5	H12A—C12—H12B	108.8
H5A—C5—H5C	109.5	C12—C13—C14	103.12 (14)
H5B—C5—H5C	109.5	C12—C13—H13A	111.1
C7—O3—Fe1	129.59 (10)	C14—C13—H13A	111.1
C9—O4—Fe1	129.27 (10)	C12—C13—H13B	111.1
C7—C6—H6A	109.5	C14—C13—H13B	111.1
C7—C6—H6B	109.5	H13A—C13—H13B	109.1
H6A—C6—H6B	109.5	C15—C14—C13	102.66 (15)
C7—C6—H6C	109.5	C15—C14—H14A	111.2
H6A—C6—H6C	109.5	C13—C14—H14A	111.2
H6B—C6—H6C	109.5	C15—C14—H14B	111.2
O3—C7—C8	123.95 (15)	C13—C14—H14B	111.2
O3—C7—C6	116.28 (14)	H14A—C14—H14B	109.1
C8—C7—C6	119.77 (15)	O8—C15—C14	105.13 (14)
C9—C8—C7	124.32 (15)	O8—C15—H15A	110.7
C9—C8—H8	117.8	C14—C15—H15A	110.7
C7—C8—H8	117.8	O8—C15—H15B	110.7
O4—C9—C8	124.44 (15)	C14—C15—H15B	110.7
O4—C9—C10	114.74 (14)	H15A—C15—H15B	108.8
C8—C9—C10	120.83 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O3ⁱ	0.98	2.53	3.370 (2)	144
C5—H5A···O1ⁱⁱ	0.98	2.60	3.539 (2)	161
C5—H5B···O6Bⁱⁱⁱ	0.98	2.56	3.471 (12)	154
C6—H6A···O5^iv	0.98	2.63	3.429 (9)	138
C6—H6A···O6^iv	0.98	2.58	3.436 (10)	145
C10—H10B···F3^v	0.98	2.56	3.214 (6)	124
C12—H12A···O6^iv	0.99	2.51	3.321 (7)	138
C12—H12A···O6B^iv	0.99	2.60	3.423 (11)	140
C14—H14A···O7B^vi	0.99	2.63	3.411 (10)	136
C14—H14B···F2B^vii	0.99	2.50	3.316 (6)	139

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

Selected bond lengths (Å) top

Fe1—O1	1.9517 (11)	Fe1—O8	2.0781 (11)
Fe1—O4	1.9651 (11)	Fe1—O5	2.063 (4)
Fe1—O3	1.9742 (11)	Fe1—O5B	2.066 (6)
Fe1—O2	1.9762 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O3ⁱ	0.98	2.53	3.370 (2)	144
C5—H5A···O1ⁱⁱ	0.98	2.60	3.539 (2)	161
C5—H5B···O6Bⁱⁱⁱ	0.98	2.56	3.471 (12)	154
C6—H6A···O5^iv	0.98	2.63	3.429 (9)	138
C6—H6A···O6^iv	0.98	2.58	3.436 (10)	145
C10—H10B···F3^v	0.98	2.56	3.214 (6)	124
C12—H12A···O6^iv	0.99	2.51	3.321 (7)	138
C12—H12A···O6B^iv	0.99	2.60	3.423 (11)	140
C14—H14A···O7B^vi	0.99	2.63	3.411 (10)	136
C14—H14B···F2B^vii	0.99	2.50	3.316 (6)	139

Experimental details

Crystal data
Chemical formula	[Fe(CF₃O₃S)(C₅H₇O₂)₂(C₄H₈O)]
M_r	475.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	103
a, b, c (Å)	15.0118 (8), 8.4523 (4), 15.9842 (9)
β (°)	100.451 (2)
V (Å³)	1994.50 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.93
Crystal size (mm)	0.77 × 0.09 × 0.08

Data collection
Diffractometer	Bruker D8 Venture/Photon 100 diffractometer
Absorption correction	Integration (SADABS; Bruker, 2013)
T_min, T_max	0.720, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	48981, 4417, 3800
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.066, 1.06
No. of reflections	4417
No. of parameters	330
No. of restraints	344
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.38

Computer programs: APEX2 (Bruker, 2013), SAINT (Bruker, 2013), SAINT, XPREP, SADABS and TWINABS (Bruker, 2013), SHELXS97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2015), SHELXTL (Sheldrick, 2008) and CrystalMaker (CrystalMaker, 1994), XCIF (Bruker, 2013) and publCIF (Westrip, 2010).

Acknowledgements

This research was conducted under contract DEFG02-90ER14146 with the US Department of Energy by its Division of Chemical Sciences, Office of Basic Energy Sciences.

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Volume 71| Part 10| October 2015| Pages 1165-1168

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