research communications
κ2O,O′)(tetrahydrofuran-κO)(trifluoromethanesulfonato-κO)iron(III)
of bis(acetylacetonato-aSchool of Chemical Sciences, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA
*Correspondence e-mail: jbertke@illinois.edu
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 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 [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—Oacac 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)°.
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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 Cmethyl—H⋯Oacac, Cmethyl—H⋯Otriflate, Cmethyl—H⋯Ftriflate, CTHF—H⋯Otriflate, and CTHF—H⋯Ftriflate 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.
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—Oacac 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—Oacac 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 . 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—Hmethyl = 0.98 Å with Uiso = 1.5Ueq(C)]. Remaining H atoms were also included as riding idealized contributors [C—Hmethylene= 0.99 Å and C—Haromatic = 0.95 Å, both with Uiso = 1.2Ueq(C)].
details are summarized in Table 3
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Supporting information
CCDC reference: 1423096
10.1107/S2056989015016849/zs2341sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015016849/zs2341Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015016849/zs2341Isup3.tif
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
[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.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—Oacac 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)°.
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 Cmethyl—H···Oacac, Cmethyl—H···Otriflate, Cmethyl—H···Ftriflate, CTHF—H···Otriflate, and CTHF—H···Ftriflate 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.
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—Oacac 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—Oacac 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).
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%.
Crystal data, data collection and structure
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—Hmethyl = 0.98 Å with Uiso = 1.5Ueq(C)]. Remaining H atoms were also included as riding idealized contributors [C—Hmethylene= 0.99 Å and C—Haromatic = 0.95 Å, both with Uiso = 1.2Ueq(C)].Data collection: APEX2 (Bruker, 2013); cell
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).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). |
[Fe(CF3O3S)(C5H7O2)2(C4H8O)] | F(000) = 980 |
Mr = 475.23 | Dx = 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 |
Bruker D8 Venture/Photon 100 diffractometer | 4417 independent reflections |
Radiation source: microfocus sealed tube | 3800 reflections with I > 2σ(I) |
Multilayer mirrors monochromator | Rint = 0.058 |
profile data from φ and ω scans | θmax = 27.2°, θmin = 2.6° |
Absorption correction: integration (SADABS; Bruker, 2013) | h = −19→19 |
Tmin = 0.720, Tmax = 0.955 | k = −10→10 |
48981 measured reflections | l = −20→20 |
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(Fo2) + (0.030P)2 + 1.245P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
4417 reflections | Δρmax = 0.29 e Å−3 |
330 parameters | Δρmin = −0.38 e Å−3 |
[Fe(CF3O3S)(C5H7O2)2(C4H8O)] | V = 1994.50 (18) Å3 |
Mr = 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)° |
Bruker D8 Venture/Photon 100 diffractometer | 4417 independent reflections |
Absorption correction: integration (SADABS; Bruker, 2013) | 3800 reflections with I > 2σ(I) |
Tmin = 0.720, Tmax = 0.955 | Rint = 0.058 |
48981 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 344 restraints |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.29 e Å−3 |
4417 reflections | Δρmin = −0.38 e Å−3 |
330 parameters |
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. |
x | y | z | Uiso*/Ueq | 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* |
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) |
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) |
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···O5iv | 0.98 | 2.63 | 3.429 (9) | 138 |
C6—H6A···O6iv | 0.98 | 2.58 | 3.436 (10) | 145 |
C10—H10B···F3v | 0.98 | 2.56 | 3.214 (6) | 124 |
C12—H12A···O6iv | 0.99 | 2.51 | 3.321 (7) | 138 |
C12—H12A···O6Biv | 0.99 | 2.60 | 3.423 (11) | 140 |
C14—H14A···O7Bvi | 0.99 | 2.63 | 3.411 (10) | 136 |
C14—H14B···F2Bvii | 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. |
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) |
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···O5iv | 0.98 | 2.63 | 3.429 (9) | 138 |
C6—H6A···O6iv | 0.98 | 2.58 | 3.436 (10) | 145 |
C10—H10B···F3v | 0.98 | 2.56 | 3.214 (6) | 124 |
C12—H12A···O6iv | 0.99 | 2.51 | 3.321 (7) | 138 |
C12—H12A···O6Biv | 0.99 | 2.60 | 3.423 (11) | 140 |
C14—H14A···O7Bvi | 0.99 | 2.63 | 3.411 (10) | 136 |
C14—H14B···F2Bvii | 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. |
Experimental details
Crystal data | |
Chemical formula | [Fe(CF3O3S)(C5H7O2)2(C4H8O)] |
Mr | 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) |
Tmin, Tmax | 0.720, 0.955 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 48981, 4417, 3800 |
Rint | 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 |
Δρmax, Δρmin (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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