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The title compound, [Fe{OS(CH3)2}6]Br3, is isostructural with [Fe{OS(CH3)2}6](NO3)3 [Tzou, Mullaney, Normand & Chang (1995), Acta Cryst. C51, 2249–2252]. The FeIII centre in the cation occupies a crystallographic \overline{3} 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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030886/fl6188sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030886/fl6188Isup2.hkl
Contains datablock I

CCDC reference: 287558

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](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

Comment top

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 SO 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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are shown at the 40% probability level.
[Figure 2] Fig. 2. Crystal packing diagram of (I), viewed along the c axis. Fe, S and C atoms are depicted as ellipsoids, and the O atoms define the polyhedra around Fe.
Hexakis(dimethyl sufoxide-κO)iron(III) tribromide top
Crystal data top
[Fe(C2H6OS)6]·3BrDx = 1.707 Mg m3
Mr = 764.35Melting point = 436–437 K
Hexagonal, R3Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -R 3Cell parameters from 2896 reflections
a = 10.7528 (7) Åθ = 2.4–24.9°
c = 22.281 (3) ŵ = 4.98 mm1
V = 2231.0 (4) Å3T = 294 K
Z = 3Prism, yellow
F(000) = 11490.25 × 0.25 × 0.22 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
879 independent reflections
Radiation source: fine-focus sealed tube702 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
Detector resolution: 0.661 pixels mm-1θmax = 25.0°, θmin = 2.4°
ω scansh = 1212
Absorption correction: analytical
(Bruker, 1999)
k = 1212
Tmin = 0.339, Tmax = 0.414l = 2626
6099 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.067H-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 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.17 e Å3
Crystal data top
[Fe(C2H6OS)6]·3BrZ = 3
Mr = 764.35Mo Kα radiation
Hexagonal, R3µ = 4.98 mm1
a = 10.7528 (7) ÅT = 294 K
c = 22.281 (3) Å0.25 × 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 = 0.414Rint = 0.044
6099 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.067H-atom parameters constrained
S = 0.99Δρmax = 0.27 e Å3
879 reflectionsΔρmin = 0.17 e Å3
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
xyzUiso*/Ueq
Fe10.00000.00000.00000.0359 (2)
Br10.66670.33330.08538 (2)0.0555 (2)
Br20.33330.66670.16670.0602 (2)
S10.09044 (7)0.27880 (7)0.07645 (3)0.0424 (2)
O10.03054 (17)0.13696 (17)0.04998 (8)0.0442 (5)
C10.0776 (3)0.4140 (3)0.03621 (15)0.0670 (9)
H1A0.09990.41060.00530.100*
H1B0.14420.50640.05260.100*
H1C0.01830.39810.03950.100*
C20.0183 (3)0.2927 (3)0.14567 (13)0.0537 (8)
H2A0.07250.28710.13890.081*
H2B0.08310.38300.16420.081*
H2C0.00500.21570.17160.081*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0296 (3)0.0296 (3)0.0486 (6)0.01479 (15)0.0000.000
Br10.0544 (2)0.0544 (2)0.0578 (4)0.02718 (12)0.0000.000
Br20.0434 (3)0.0434 (3)0.0939 (6)0.02170 (14)0.0000.000
S10.0347 (4)0.0340 (4)0.0566 (5)0.0158 (3)0.0003 (3)0.0014 (3)
O10.0362 (10)0.0357 (10)0.0610 (12)0.0182 (8)0.0007 (9)0.0091 (8)
C10.082 (2)0.0425 (17)0.070 (2)0.0265 (17)0.0023 (18)0.0111 (15)
C20.0553 (17)0.0438 (16)0.0513 (17)0.0168 (14)0.0026 (14)0.0032 (13)
Geometric parameters (Å, º) top
Fe1—O1i2.0000 (16)C1—H1A0.9600
S1—O11.5434 (17)C1—H1B0.9600
S1—C21.766 (3)C1—H1C0.9600
S1—C11.771 (3)C2—H2A0.9600
O1—O1ii2.778 (3)C2—H2B0.9600
O1—O1iii2.878 (3)C2—H2C0.9600
O1i—Fe1—O1iv180.00 (12)H1A—C1—H1B109.5
O1i—Fe1—O1v87.99 (7)S1—C1—H1C109.5
O1iv—Fe1—O1v92.01 (7)H1A—C1—H1C109.5
O1v—Fe1—O1180.00 (11)H1B—C1—H1C109.5
O1—S1—C2103.21 (11)S1—C2—H2A109.5
O1—S1—C1104.15 (13)S1—C2—H2B109.5
C2—S1—C198.90 (15)H2A—C2—H2B109.5
S1—O1—Fe1124.95 (9)S1—C2—H2C109.5
S1—C1—H1A109.5H2A—C2—H2C109.5
S1—C1—H1B109.5H2B—C2—H2C109.5
Symmetry codes: (i) x+y, x, z; (ii) y, x+y, z; (iii) y, xy, z; (iv) xy, x, z; (v) x, y, z.

Experimental details

Crystal data
Chemical formula[Fe(C2H6OS)6]·3Br
Mr764.35
Crystal system, space groupHexagonal, R3
Temperature (K)294
a, c (Å)10.7528 (7), 22.281 (3)
V3)2231.0 (4)
Z3
Radiation typeMo Kα
µ (mm1)4.98
Crystal size (mm)0.25 × 0.25 × 0.22
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Absorption correctionAnalytical
(Bruker, 1999)
Tmin, Tmax0.339, 0.414
No. of measured, independent and
observed [I > 2σ(I)] reflections
6099, 879, 702
Rint0.044
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.067, 0.99
No. of reflections879
No. of parameters46
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.17

Computer programs: SMART (Bruker, 1999), SMART, SAINT (Bruker, 1999), SHELXTL (Bruker, 1999), SHELXTL.

 

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