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The title compound, [Fe{OS(CH
3)
2}
6]Br
3, is isostructural with [Fe{OS(CH
3)
2}
6](NO
3)
3 [Tzou, Mullaney, Normand & Chang (1995),
Acta Cryst. C51, 2249–2252]. The Fe
III centre in the cation occupies a crystallographic
site and has a distorted octahedral coordination, with an Fe—O distance of 2.000 (2) Å and O—Fe—O angles of 92.01 (7) and 87.99 (7)°.
Supporting information
CCDC reference: 287558
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (S-C) = 0.003 Å
- R factor = 0.026
- wR factor = 0.067
- Data-to-parameter ratio = 19.1
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............ 24.95 Deg.
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
1 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Anhydrous iron(II) bromide (0.35 g, 1.62 mmol) was disolved in DMSO (10 ml) while stirring with a magnetic bar. Air oxidation to iron(III) resulted in a yellow solution, which was stirred overnight. The reaction mixture was then filtered and left standing for the DMSO to evaporate until yellow crystals of (I) were obtained [yield: 0.53 g, 43%; m.p. 436–437 K (decomposition)]. IR (CHCl3): 2986, 2918, 2466, 1624, 1493, 1434, 1414, 1403, 1309, 1289, 1237, 1053, 1014, 984, 948, 925, 891 cm−1; UV–Vis 415, 291, 245 nm.
The positional parameters of the H atoms were calculated geometrically, and they were refined as riding, with a fixed Uiso(H) = 1.2Ueq(C) and C—H = 0.96 Å.
Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXTL (Bruker, 1999); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Hexakis(dimethyl sufoxide-
κO)iron(III) tribromide
top
Crystal data top
[Fe(C2H6OS)6]·3Br− | Dx = 1.707 Mg m−3 |
Mr = 764.35 | Melting point = 436–437 K |
Hexagonal, R3 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -R 3 | Cell parameters from 2896 reflections |
a = 10.7528 (7) Å | θ = 2.4–24.9° |
c = 22.281 (3) Å | µ = 4.98 mm−1 |
V = 2231.0 (4) Å3 | T = 294 K |
Z = 3 | Prism, yellow |
F(000) = 1149 | 0.25 × 0.25 × 0.22 mm |
Data collection top
Bruker SMART APEX CCD diffractometer | 879 independent reflections |
Radiation source: fine-focus sealed tube | 702 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
Detector resolution: 0.661 pixels mm-1 | θmax = 25.0°, θmin = 2.4° |
ω scans | h = −12→12 |
Absorption correction: analytical (Bruker, 1999) | k = −12→12 |
Tmin = 0.339, Tmax = 0.414 | l = −26→26 |
6099 measured reflections | |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.037P)2] where P = (Fo2 + 2Fc2)/3 |
879 reflections | (Δ/σ)max < 0.001 |
46 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
Crystal data top
[Fe(C2H6OS)6]·3Br− | Z = 3 |
Mr = 764.35 | Mo Kα radiation |
Hexagonal, R3 | µ = 4.98 mm−1 |
a = 10.7528 (7) Å | T = 294 K |
c = 22.281 (3) Å | 0.25 × 0.25 × 0.22 mm |
V = 2231.0 (4) Å3 | |
Data collection top
Bruker SMART APEX CCD diffractometer | 879 independent reflections |
Absorption correction: analytical (Bruker, 1999) | 702 reflections with I > 2σ(I) |
Tmin = 0.339, Tmax = 0.414 | Rint = 0.044 |
6099 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.27 e Å−3 |
879 reflections | Δρmin = −0.17 e Å−3 |
46 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 | Uiso*/Ueq | |
Fe1 | 0.0000 | 0.0000 | 0.0000 | 0.0359 (2) | |
Br1 | 0.6667 | 0.3333 | 0.08538 (2) | 0.0555 (2) | |
Br2 | 0.3333 | 0.6667 | 0.1667 | 0.0602 (2) | |
S1 | 0.09044 (7) | 0.27880 (7) | 0.07645 (3) | 0.0424 (2) | |
O1 | −0.03054 (17) | 0.13696 (17) | 0.04998 (8) | 0.0442 (5) | |
C1 | 0.0776 (3) | 0.4140 (3) | 0.03621 (15) | 0.0670 (9) | |
H1A | 0.0999 | 0.4106 | −0.0053 | 0.100* | |
H1B | 0.1442 | 0.5064 | 0.0526 | 0.100* | |
H1C | −0.0183 | 0.3981 | 0.0395 | 0.100* | |
C2 | 0.0183 (3) | 0.2927 (3) | 0.14567 (13) | 0.0537 (8) | |
H2A | −0.0725 | 0.2871 | 0.1389 | 0.081* | |
H2B | 0.0831 | 0.3830 | 0.1642 | 0.081* | |
H2C | 0.0050 | 0.2157 | 0.1716 | 0.081* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Fe1 | 0.0296 (3) | 0.0296 (3) | 0.0486 (6) | 0.01479 (15) | 0.000 | 0.000 |
Br1 | 0.0544 (2) | 0.0544 (2) | 0.0578 (4) | 0.02718 (12) | 0.000 | 0.000 |
Br2 | 0.0434 (3) | 0.0434 (3) | 0.0939 (6) | 0.02170 (14) | 0.000 | 0.000 |
S1 | 0.0347 (4) | 0.0340 (4) | 0.0566 (5) | 0.0158 (3) | 0.0003 (3) | −0.0014 (3) |
O1 | 0.0362 (10) | 0.0357 (10) | 0.0610 (12) | 0.0182 (8) | −0.0007 (9) | −0.0091 (8) |
C1 | 0.082 (2) | 0.0425 (17) | 0.070 (2) | 0.0265 (17) | 0.0023 (18) | 0.0111 (15) |
C2 | 0.0553 (17) | 0.0438 (16) | 0.0513 (17) | 0.0168 (14) | 0.0026 (14) | −0.0032 (13) |
Geometric parameters (Å, º) top
Fe1—O1i | 2.0000 (16) | C1—H1A | 0.9600 |
S1—O1 | 1.5434 (17) | C1—H1B | 0.9600 |
S1—C2 | 1.766 (3) | C1—H1C | 0.9600 |
S1—C1 | 1.771 (3) | C2—H2A | 0.9600 |
O1—O1ii | 2.778 (3) | C2—H2B | 0.9600 |
O1—O1iii | 2.878 (3) | C2—H2C | 0.9600 |
| | | |
O1i—Fe1—O1iv | 180.00 (12) | H1A—C1—H1B | 109.5 |
O1i—Fe1—O1v | 87.99 (7) | S1—C1—H1C | 109.5 |
O1iv—Fe1—O1v | 92.01 (7) | H1A—C1—H1C | 109.5 |
O1v—Fe1—O1 | 180.00 (11) | H1B—C1—H1C | 109.5 |
O1—S1—C2 | 103.21 (11) | S1—C2—H2A | 109.5 |
O1—S1—C1 | 104.15 (13) | S1—C2—H2B | 109.5 |
C2—S1—C1 | 98.90 (15) | H2A—C2—H2B | 109.5 |
S1—O1—Fe1 | 124.95 (9) | S1—C2—H2C | 109.5 |
S1—C1—H1A | 109.5 | H2A—C2—H2C | 109.5 |
S1—C1—H1B | 109.5 | H2B—C2—H2C | 109.5 |
Symmetry codes: (i) −x+y, −x, z; (ii) y, −x+y, −z; (iii) −y, x−y, z; (iv) x−y, x, −z; (v) −x, −y, −z. |
Experimental details
Crystal data |
Chemical formula | [Fe(C2H6OS)6]·3Br− |
Mr | 764.35 |
Crystal system, space group | Hexagonal, R3 |
Temperature (K) | 294 |
a, c (Å) | 10.7528 (7), 22.281 (3) |
V (Å3) | 2231.0 (4) |
Z | 3 |
Radiation type | Mo Kα |
µ (mm−1) | 4.98 |
Crystal size (mm) | 0.25 × 0.25 × 0.22 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Analytical (Bruker, 1999) |
Tmin, Tmax | 0.339, 0.414 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6099, 879, 702 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.594 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.067, 0.99 |
No. of reflections | 879 |
No. of parameters | 46 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.17 |
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The structure of the title compound, (I), comprises discrete [Fe(DMSO)6]3+ [DMSO = (CH3)2SO, dimethyl sulfoxide] cations and bromide anions. The closest Fe···Br1 contact is 5.525 Å, indicating that there are no significant interactions between the Fe and Br atoms (Fig. 1). The Fe—O distance of 2.000 (2) Å, differs significantly from the value reported for the nitrate analogue at 2.020 Å (Tzou et al., 1995), but compares well with those of trans-[FeCl2(DMSO)4][FeCl4] at 2.006 Å (Bennett or Bennet et al., 1967) and [FeCl(DMSO)5][Fe2Cl6O] at 1.998 Å (Ponomarev et al., 1984). As expected, the observed Fe—O distance is shorter than the distances found in the [Fe(DMSO)6]2+ cation, which have an average of 2.128 (3) Å (Müller et al., 1989), owing to the higher oxidation state in the former compound. The coordination polyhedron around the Fe atom is a distorted octahedron flattened in the direction of the threefold axis with the two axial O3 faces [O1, O1B(−y, x-y, z), O1D(−x + y, −x, z) and O1A(−x, −y, −z), O1C(y, −x + y, −z) and O1E(x-y, x, −z)] having longer [2.878 (3) Å] O···O than the remaining edges in the equatorial region [2.778 (3) Å]. The S1—O1 distance of 1.543 (2) Å clearly shows the loss of S═O double-bond character upon coordination via the O atom. The S—O vector lies nearly perpendicular to the O3 faces (angle between the S—O vector and the vector normal to the O3 plane: 2.8°). As found in the nitrate analogues of Fe (Tzou et al., 1995) and Cr (Öhrström & Svensson, 2000), the bromide anion Br1 resides on a site of 3 symmetry, and Br2 resides on a site of 3 symmetry. This structure, however, does not have the disorder problems associated with one of the nitrate anions in the aforementioned analogues. Atom Br1 appears twice per ion centre, while Br2 appears only once.