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The synthesis and crystal structure determination (at 293 K) of the title complex, Cs[Fe(C8H6BrN3OS)2], are reported. The compound is composed of two dianionic O,N,S-tridentate 5-bromo­salicyl­aldehyde thio­semicarbazonate(2−) ligands coord­inated to an FeIII cation, displaying a distorted octa­hedral geometry. The ligands are orientated in two perpendicular planes, with the O- and S-donor atoms in cis positions and the N-donor atoms in trans positions. The complex displays inter­molecular N—H...O and N—H...Br hydrogen bonds, creating R44(18) rings, which link the FeIII units in the a and b directions. The FeIII cation is in the low-spin state at 293 K.

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Crystallographic Information File (CIF)
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Structure factor file (CIF format)
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CCDC reference: 1046273

Introduction top

It is recognised that o­cta­hedral metal complexes with 3d4–3d7 configurations with specific ligands can exhibit spin crossover behaviour, the magnetic inter­conversion between low-spin and high-spin states, dependent upon external perturbations of temperature, pressure or light irradiation (Gütlich & Goodwin, 2004). In recent years, particular inter­est has been focused on FeIII (3d5) complexes of substituted derivatives of R-salicyl­aldehyde 4-R'-thio­semicarbazone (Floquet et al., 2003, 2006, 2009: Li et al., 2013; Yemeli Tido et al., 2008; Yemeli Tido, 2010, Powell et al., 2014) for generating FeIII spin crossover. The spin crossover properties of this class of FeIII bis­(ligand) complexes have been found to be sensitive to the presence of a particular counter-ion, the degree of solvation and the nature of the R- and R'-substituted ligands (van Koningsbruggen et al., 2004; Yemeli Tido et al., 2008). Furthermore, it has been established that varying the pH during the synthesis of the FeIII bis­(ligand) entities leads to the formation of FeIII compounds differing in the degree of deprotonation of the ligand, whereby the complex unit can be neutral, monocationic, tricationic or monoanionic (Floquet et al., 2009; Yemeli Tido et al., 2010; Yemeli Tido, 2010).

In FeIII compounds, it is possible for the tridentate R-salicyl­aldehyde 4-R'-thio­semicarbazone ligand (H2L) to exist in tautomeric forms, and the ligand may also be present in its neutral, anionic or dianionic form. The free R-salicyl­aldehyde 4-R'-thio­semicarbazone ligand (H2L) in solution exists in two tautomeric forms, i.e. the thione and thiol forms, as illustrated in Scheme 1.

We recently reported the structure (100 K) of Cs[Fe(L)2].CH3OH, where L2- = 3-eth­oxy­salicyl­aldehyde 4-methyl­thio­semicarbazonate(2-) (Powell et al., 2014). Both of the ligands were found to be two-fold deprotonated, as no H atoms were located on the phenolate O or thiol­ate S atoms. From the values of the geometric parameters, it was established that the FeIII cation is in the low-spin state. Continuing our research, we varied the R and R' substituents of the ligand and studied the structural and electronic properties of the resulting FeIII coordination compounds. Herein, we report the title FeIII compound, Cs[Fe(L)2], (I), containing two dianionic tridentate 5-bromo­salicyl­aldehyde thio­semicarbazonate(2-) (L2-) ligands, as illustrated in Scheme 2. The structure of (I) was determined at 293 K.

Experimental top

Synthesis and crystallization top

5-Bromo­salicyl­aldehyde thio­semicarbazone was synthesised according to the procedure described in the literature (Yemeli Tido, 2010). 5-Bromo­salicyl­aldehyde (98%, 49 mmol) was dissolved in ethanol (80 ml) with constant stirring and then added to thio­semicarbazide (99%, 49 mmol) dissolved in ethanol (40 ml). The mixture was refluxed for 120 min. After the mixture had cooled to room temperature, a yellow solid was isolated by filtration and dried.

FeCl3.6H2O (1.0 mmol, 0.27 g) was dissolved in methanol (10 ml). 5-Bromo­salicyl­aldehyde thio­semicarbazone (2.0 mmol, 0.54 g) was dissolved in methanol (60 ml) with the addition of CsOH.H2O (4.0 mmol, 0.67 g). To this mixture, the methano­lic FeIII salt solution was added with constant stirring. The resulting dark-green solution was stirred and heated to 353 K for approximately 10 min. The solution was then allowed to stand at room temperature until crystals were formed. The dark green microcrystals of (I) were isolated by filtration and dried.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. The structure of (I) was routinely solved by direct methods and refined by least squares, with H atoms placed in anti­cipated positions and non-H atoms given anisotropic displacement parameters. However, the refined parameters did not match the quality of the data set, since the unweighted discrepancy index R1 of 0.0916 was much higher than Rint of 0.0451. Since all 50 of the reflections with the worst discrepancy had Fobs > Fcalc, twinning was suspected, and the closeness of the unit cell β angle to 90° suggested a mechanism for pseudo-merohedral twinning. Application of ROTAX (Cooper et al., 2002) indicated 180° rotation about the a axis as the likely twin law. Repeating the refinement with this twin law drastically reduced the discrepancy indices.

Now, all polar H atoms were omitted from the model and sought in a difference Fourier map. The H atoms on the secondary atoms N13 and N23 were located in a difference Fourier map at peak heights between 0.60 and 0.70 e Å-3, while no comparable peaks appeared adjacent to N11, N12, N21, N22 or any O or S atom. In subsequent refinements, the amino H atoms thus established were treated as riding, with N—H = 0.86 Å and Uiso(H) = 1.2Ueq(N). The remaining H atoms were included in the refinement in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aryl (-CH) H atoms. After final refinement, R1 reached 0.0326 and wR2 = 0.0859, and a fractional contribution of 0.1306 (8) from the minor twin component was indicated.

Results and discussion top

The crystal structure of (I) (Fig. 1) was determined at 293 K. Compound (I) crystallises in the monoclinic system in the space group P21/c. The asymmetric unit corresponds to the formula unit Cs[Fe(L)2], where L2- = 5-bromo­salicyl­aldehyde thio­semicarbazonate(2-), with no atom on a special position. The central FeIII cation is hexa-coordinated by two dianionic O,N,S-tridentate thio­semicarbazonate(2-) ligands, displaying a distorted o­cta­hedral FeIII S2N2O2 geometry. Deprotonation occurs for the phenol O atoms and thiol S atoms. Selected geometric parameters are listed in Tables 2 and 3.

The FeIII S2N2O2 entity is distorted from ideal o­cta­hedral geometry, as indicated by the bond angles (Table 2) of the donor atoms and atom Fe1 (see below). The tridentate thio­semicarbazonate(2-) ligands are coordinated to the FeIII cation by the O- and S-donor atoms, which are situated in two perpendicular planes in the cis positions, such that the N-donor atoms are situated in mutually trans positions.

X-ray structural data of similar FeIII bis­(ligand) compounds containing dianionic thio­semicarbazonate(2-) ligands show that the Fe—S, Fe—O and Fe—N bond distances are in the ranges 2.23–2.31, 1.93–1.95 and 1.88–1.96 Å, respectively, for low-spin FeIII compounds, and 2.40–2.44, 1.96–1.99 and 2.05–2.15 Å, respectively, for corresponding high-spin FeIII compounds (van Koningsbruggen et al., 2004). Comparison of the bond distances of (I) involving the Fe atom and the donor atoms (Table 2) suggests that the present compound contains low-spin FeIII at 293 K.

The distortion of the FeIII–S2N2O2 entity results from the constraints imposed by the five- and six-membered chelate rings formed. The six-membered chelate ring involves a significantly wider bite angle than the ideal o­cta­hedral 90° [O11—Fe—N11 = 94.35 (12)° and O21—Fe—N21 = 93.78 (12)°], which is narrowed in the five-membered chelate ring [S11—Fe—N11 = 86.01 (9)° and S21—Fe—N21 = 86.07 (9)°]. There is no major strain relief through puckering: the root mean-square deviations from the least-squares planes of the atoms comprising the six-membered rings are 0.034 and 0.038 Å [Which value refers to which ring?]; the corresponding values for the five-membered rings are 0.014 and 0.009 Å [Which value refers to which ring?]. Compared with the 120° angles in a regular hexagon, the O—Fe—N bite angle is deficient by ca 26°, and each of the remaining angles in the six-membered rings is within 2° of 125°. Because the angle at the vertex of a regular penta­gon is only 108°, the S—Fe—N bite angles are deficient by only 22°. However, the C—S—Fe angles are only about 95°, providing an additional deficiency of 13° and a total which could be neatly offset by increasing the other angles to ca 120°. (In fact, the N—N—C angles are <120° and the N—C—S angles are >120°.) Such 120° angles are consistent with sp2 hybridization at the C and N atoms. The stability of the FeIII complex is enhanced by the high degree of electron delocalization throughout the chelated ligands.

The bond distances of the ligands coordinated to the FeIII cation in (I) can be related to bond order. The C—S, C—N and N—N bonds obtained for (I) show characteristics of bond order between a single and a double bond. As expected, the C18—S11 bond distance of 1.750 (4) Å and the C28—S21 bond distance of 1.753 (4) Å suggest a partial electron delocalization of these bonds. Ryabova, Ponomarev, Zelentsov, Shipilov & Atovmyan (1981) reported the related low-spin compound NH4[Fe(L)2] [where L2- = 5-bromo­salicyl­aldehyde thio­semicarbazonate(2-)] at 298 K, which crystallises in the centrosymmetric space group Pnca with Z' = 0.5. Thus, the ligands coordinated around the FeIII cation are related by symmetry. The C—S bond distances of (I) correspond with the C—S bond distance of 1.750 (9) Å for NH4[Fe(L)2] [where L2- = 5-bromo­salicyl­aldehyde thio­semicarbazonate(2-)], suggesting the occurrence of partial electron delocalization in both compounds. Furthermore, the electron delocalization of the ligands is confirmed by a bond order larger than 1 for the C—N bond involving the deprotonated hydrazinic N atom. The bond distances for the C17—N11 and C27—N21 bonds in (I) are 1.281 (5) and 1.296 (5) Å, respectively, which are similar to the C—N bond distance of 1.292 (10) Å reported for NH4[Fe(L)2] (Ryabova, Ponomarev, Zelentsov, Shipilov & Atovmyan, 1981). In addition, the N—N bond distances of (I) are N11—N12 = 1.394 (4) and N21—N22 = 1.401 (4) Å, indicating partial electron delocalization.

The Cs+ cation of (I) is at the centre of an irregular seven-donor atom polyhedron, the donor atoms of which originate from symmetry-related equivalents of both symmetry-independent ligands. Selected geometric parameters are listed in Table 2.

Several donor atoms coordinated to the Fe atom form inter­actions with the Cs+ cation in the second coordination sphere, modulating the electron density of the Fe–donor atom bonds and hence influencing the electronic state of the FeIII cation.

The Fe donor atoms phenolate O11 and O21 bind to the Cs+ cation within the same FeIII unit. The Cs—O distances are Cs1—O11 = 3.220 (3) Å and Cs1—O21 = 3.129 (3) Å. These values are somewhat longer than the mean Cs—O bond of 3.074 (1) Å in the hydrated Cs+ cation (Mähler & Persson, 2012). The small O11—Cs1—O21 bond angle of 50.34 (7)° is a corollary of the closeness of the two ligands bound to Fe. The Cs1···Fe separation involving the µ-diphenolate bridge is 4.2703 (6) Å and the Cs—O—Fe bond angles are Cs1—O11—Fe = 109.12 (11)° and Cs1—O21—Fe = 112.16 (11)°.

The thiol­ate S11vii and S21vii [symmetry code: (vii) x, y, z - 1] Fe donor atoms coordinate to the Cs+ cation with bond distances of 3.7159 (11) and 3.5564 (11) Å, respectively. Moreover, the terminal N23vii atom of the same FeIII entity forms a bond with the Cs+ cation with a Cs1—N23vii bond distance of 3.699 (4) Å. The proximity of atoms N23 and S21 is shown by the small N23vii—Cs1—S21vii bond angle of 42.99 (6)°, whereas the small S21vii—Cs1—S11vii bond angle of 53.27 (2)Å is related to the vicinity of the two ligands bound to Fe. Furthermore, the thiol­ate S-donor atoms coordinate to the Cs+ cation as well as to the FeIII cation, which gives rise to the Cs1···Fei separation of 4.7695 (6) Å [symmetry code: (i) PLEASE COMPLETE]. The Cs—S—Fe bond angles involving the µ-di­thiol­ate bridge are Cs1vii—S11—Fe = 103.80 (4)° and Cs1vii—S21—Fe = 108.55 (4)°. In addition, the N atoms N12viii and N22xi [symmetry codes: (viii) x, -y + 1/2, z - 1/2; (ix) x, -y + 3/2, z - 1/2] next to the imine N-donor atoms in the first coordination sphere of Fe are also coordinated to the Cs+ cation (see Table 2).

The Cs+···Cs+ separations of 7.4530 (5) Å for Cs1···Cs1(x, -y + 3/2, z + 1/2) and 7.6404 (5) Å for Cs1···Cs1(x, -y + 1/2, z - 1/2) do correlate with the shortest FeIII···FeIII separations in (I). These are 7.5369 (9) Å for Fe···Fe(x, -y + 3/2, z + 1/2) and 7.5559 (6) Å for Fe···Fe(x, -y + 1/2, z - 1/2).

The previously reported compound, Cs[Fe(L)2].CH3OH [L2- = 3-eth­oxy­salicyl­aldehyde 4-methyl­thio­semicarbazonate(2-)], displays FeIII···FeIII(x + 1, y, z) separations of 8.486 (3) Å (Powell et al., 2014). The absence of any solvent molecule in (I) allows the FeIII entities to be closer to each other in the crystal structure than in the former compound. Furthermore, the R and R' substituents of the ligands coordinated to the FeIII atom, 5-bromo­salicyl­aldehyde thio­semicarbazone in (I) and 3-eth­oxy­salicyl­aldehyde 4-methyl­thio­semicarbazone in Cs[Fe(L)2].CH3OH, might have some effect on how the FeIII entities are assembled in the crystal structure. The sizes and positions of the R and R' substituted groups are different, as (I) contains a Br substituent on the C15/C25 atom of the salicyl­aldehyde group, whereas Cs[Fe(L)2].CH3OH contains a relatively bulky eth­oxy group on the C13/C23 atom of the salicyl­aldehyde group as well as a methyl substituent on the terminal N atom of the thio­semicarbazide group. In addition, the Br substituent of one FeIII unit of (I) provides a hydrogen-bonding inter­action with an amino group of a neighbouring FeIII unit (see below). The occurrence of inter­molecular hydrogen-bonding inter­actions between FeIII units in (I) contributes to the arrangement of the FeIII entities in the unit cell.

The hydrogen-bonding inter­actions of (I) are listed in Table 3 and displayed in Fig. 2. The main features of the molecular packing of (I) are the N—H···O and N—H···Br hydrogen bonds. Although the latter are weak, their grip on the Br atoms is augmented by C—H···Br inter­actions at similar H···Br contact distances. The N13—H13B···Br2ii and N13—H13A···O21i (see Table 3 for symmetry codes) contacts form hydrogen bonds to two different ring systems. In turn, atom O21 in the former system and atom Br2 in the latter accept hydrogen bonds from inversion-related atom N13(-x + 1, -y, -z + 2), giving rise to R44(18) rings (Bernstein et al., 1995). In a similar manner, the N23—H23B···Br1iv and N23—H23A···O11iii contacts create R44(18) rings with inversion-related atom N23(-x + 2, -y + 2, -z + 2). The ring systems created by the hydrogen bonding between the FeIII entities link them in the a and b directions. Furthermore, the Cs+ cations link the FeIII complex anions into a chain along [010].

Compound (I) does not contain any solvent molecules in the crystal lattice. This feature has also been observed for the following FeIII compounds: Cs[Fe(thsa)2] (Ryabova, Ponomarev, Zelentsov & Atovmyan, 1981), NH4[Fe(5—Br-thsa)2] (Ryabova, Ponomarev, Zelentsov, Shipilov & Atovmyan, 1981) and NH4[Fe(5—Cl-thsa)2] (Ryabova et al., 1978), for which relevant data are compiled in Table 4. This table shows the non-solvated FeIII bis­(ligand) compounds together with the spin state of the FeIII cation at the temperature at which the crystal structure was determined. The crystallographic data of (I) will now be compared with similar FeIII bis­(ligand) type compounds (Table 4), all of which are non-solvated compounds.

The FeIII cation in the compound Cs[Fe(thsa)2] is in a high-spin state at both 103 and 298 K, whereas the FeIII cation in NH4[Fe(5—Cl-thsa)2] is low spin at both 135 and 298 K. Furthermore, in NH4[Fe(5—Br-thsa)2] the FeIII cation is in a low-spin state at 298 K. The FeIIIcation in (I) is in a low-spin state at 293K. A transition from low-spin to high-spin FeIII has been detected for similar materials on increasing temperature (Ryabova et al., 1982), but crystallographic data are not available for these non-solvated materials. Noting that (I) contains low-spin FeIII at 293 K, perhaps it may exhibit a change in spin state above room temperature.

The generation of any spin transition is governed by the energy difference between the high-spin and low-spin electronic states. This energy gap can be tuned by variation of the ligand field strength. The features of the second coordination sphere, such as the arrangement of Fe units within a unit cell belonging to a particular crystal system, also influence the ligand field characteristics. The packing of Fe units is evidenced by symmetry requirements, which are embedded within the space group in which the material crystallises. X-ray structural analysis has revealed that the FeIII bis­(ligand) type compounds (Table 4) adopt different crystal systems and space groups compared with (I). Compound (I) displays a monoclinic crystal system and crystallises in the space group P21/c with Z = 4, or alternatively Z' = 1. In contrast, the non-solvated FeIII bis­(ligand) compounds listed in Table 4 all exhibit an orthorhombic crystal system, although in some cases their space groups differ. For example, Cs[Fe(thsa)2] crystallises in the space group Pna21 with Z' = 1, whereas NH4[Fe(5—Br-thsa)2] in its tabular form crystallises in the space group Pnca with Z' = 0.5. The compound NH4[Fe(5—Cl-thsa)2] also crystallises in the space group Pnca, also with Z' = 0.5. The FeIII bis­(ligand) entities present variances with respect to their symmetry: in some instances, a value for Z' of 0.5 is encountered, which for space group Pnca implies that the ligands coordinated to the FeIII cation are related by two-fold rotational symmetry. Inter­estingly, Ryabova, Ponomarev, Zelentsov, Shipilov & Atovmyan (1981) reported that NH4[Fe(5—Br-thsa)2] crystallises in two different forms, one crystallising as tabular plates and the other as mica-like crystals. It was established that these two different polymorphs exhibit a spin crossover at different temperatures, i.e. the mica-like crystals in the region around 200 K and the tabular plate crystals in the region around 300 K. It appears that the crystallographic data analysed so far for this family of materials do not reveal a relation between FeIII spin state and the crystal system and space group.

It is widely recognised that significant changes in the electronic state of FeIII bis­(ligand) compounds may arise from the associated cation in the complex system, the R substituents at the benzene ring of the salicyl­aldehyde group or the introduction of R' substituents into the thio­amide group of the thio­semicarbazide group, and the FeIII S2N2O2 geometry. The main difference observed between the compounds (Table 4) compared with (I) is the varying size of the associated cation (either NH4+ or Cs+) in the crystal structure and the variation in the slight distortions of the o­cta­hedral FeIII S2N2O2 coordination sphere. It appears that the variation of the associated cation in the FeIII bis­(ligand) compounds may have an indirect impact on the spin state of FeIII by influencing the crystal packing. In addition to the difference in size between NH4+ and Cs+ cations, the former may engage in directed inter­actions through hydrogen bonding, while the latter presents a more uniform electrostatic field without a preferred direction for hydrogen bonds. The R and R' substituents of the ligand may exhibit steric and electronic effects [including being involved in hydrogen bonding, via the Br substituents in (I)], but at this stage it is unclear how these features may be harnessed to induce a particular spin state for FeIII.

The FeIII S2N2O2 coordination spheres of the compounds are slightly distorted from ideal o­cta­hedral geometry. It has been acknowledged that there are subtle differences in FeIII coordination geometry among the members of this particular type of compound. Clearly, the stabilisation of FeIII in a particular spin state is governed by a subtle balance of geometric parameters, as is implied by the fact that a single compound, NH4[Fe(5—Br-thsa)2], exists in slightly different polymorphs, each with its own distinct magnetic behaviour. The latter example shows that it is too early to derive a possible relation between FeIII spin state and FeIII S2N2O2 geometry and crystal packing (the latter evidenced by crystal system and space group).

The development of a strategy towards the synthesis of FeIII bis­(ligand) compounds with a pre-determined spin state will require the measurement and analysis of crystallographic data from a larger number of FeIII compounds of this family, including these having different R and/or R' substituents and a variety of associated cations. Other parameters that we are currently considering in our studies are the alteration of the degree of solvation and the tuning of the deprotonation characteristics of the R-salicyl­aldehyde R'-thio­semicarbazone ligand.

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2013); cell refinement: CrystalClear-SM Expert (Rigaku, 2013); data reduction: CrystalClear-SM Expert (Rigaku, 2013); program(s) used to solve structure: ROTAX (Cooper et al., 2002), SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure and atom-numbering scheme for (I). Displacement ellipsoids are drawn at 50% probability level.
[Figure 2] Fig. 2. A projection showing the unit cell of (I). The Cs+ cation has been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds. [Symmetry codes: (i) x, -y + 1/2, z + 1/2; (ii) -x + 1, y - 1/2, -z + 3/2; (iii) x, -y + 3/2, z + 1/2; (iv) -x + 2, y + 1/2, -z + 3/2; (v) -x + 2, y + 1/2, -z + 1/2; (vi) -x + 1, y - 1/2, -z + 1/2.]
Caesium bis(5-bromosalicylaldehyde thiosemicarbazonato-κ3O,N,S)ferrate(III) top
Crystal data top
Cs[Fe(C8H6BrN3OS)2]F(000) = 1396
Mr = 733.02Dx = 2.201 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybcCell parameters from 26513 reflections
a = 20.2500 (14) Åθ = 2.6–27.5°
b = 12.0868 (8) ŵ = 6.13 mm1
c = 9.0389 (5) ÅT = 293 K
β = 90.337 (1)°Plate, green
V = 2212.3 (2) Å30.08 × 0.08 × 0.01 mm
Z = 4
Data collection top
Rigaku AFC12 four-circle Kappa
5073 independent reflections
Radiation source: fine-focus sealed tube4211 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.045
Detector resolution: 28.5714 pixels mm-1θmax = 27.5°, θmin = 3.0°
profile data from ω scansh = 2625
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku, 2013)
k = 1515
Tmin = 0.640, Tmax = 0.941l = 1111
29088 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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0451P)2 + 1.5804P]
where P = (Fo2 + 2Fc2)/3
5073 reflections(Δ/σ)max = 0.001
272 parametersΔρmax = 0.88 e Å3
0 restraintsΔρmin = 0.85 e Å3
Crystal data top
Cs[Fe(C8H6BrN3OS)2]V = 2212.3 (2) Å3
Mr = 733.02Z = 4
Monoclinic, P21/cMo Kα radiation
a = 20.2500 (14) ŵ = 6.13 mm1
b = 12.0868 (8) ÅT = 293 K
c = 9.0389 (5) Å0.08 × 0.08 × 0.01 mm
β = 90.337 (1)°
Data collection top
Rigaku AFC12 four-circle Kappa
5073 independent reflections
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku, 2013)
4211 reflections with I > 2σ(I)
Tmin = 0.640, Tmax = 0.941Rint = 0.045
29088 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.086H-atom parameters constrained
S = 1.03Δρmax = 0.88 e Å3
5073 reflectionsΔρmin = 0.85 e Å3
272 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Cs10.751537 (18)0.50484 (2)0.23503 (3)0.05227 (10)
Br11.01607 (3)0.26269 (5)0.25045 (6)0.06040 (16)
Br20.48231 (3)0.80167 (6)0.31594 (7)0.06880 (19)
Fe10.74977 (3)0.50049 (4)0.70739 (5)0.02473 (11)
S110.67238 (5)0.45208 (8)0.86988 (11)0.0343 (2)
S210.82731 (5)0.52595 (8)0.88220 (12)0.0337 (2)
O110.81413 (14)0.5428 (2)0.5594 (3)0.0341 (6)
O210.68600 (14)0.4811 (2)0.5460 (3)0.0350 (6)
N110.77067 (15)0.3435 (2)0.6968 (3)0.0267 (6)
N120.73750 (16)0.2668 (2)0.7844 (4)0.0317 (7)
N130.65757 (18)0.2458 (3)0.9599 (4)0.0426 (9)
C110.86003 (19)0.3619 (3)0.5187 (4)0.0314 (8)
C120.8591 (2)0.4775 (3)0.5013 (5)0.0328 (8)
C130.9081 (2)0.5247 (4)0.4112 (6)0.0529 (13)
C140.9531 (2)0.4625 (4)0.3369 (6)0.0549 (12)
C150.9522 (2)0.3487 (4)0.3522 (5)0.0418 (10)
C160.9071 (2)0.2994 (4)0.4412 (5)0.0383 (9)
C170.81546 (19)0.3017 (3)0.6145 (5)0.0335 (8)
C180.69182 (19)0.3110 (3)0.8677 (4)0.0298 (8)
N210.72844 (15)0.6554 (2)0.7352 (3)0.0267 (6)
N220.76224 (16)0.7196 (3)0.8402 (4)0.0327 (7)
N230.84049 (18)0.7187 (3)1.0217 (4)0.0439 (9)
C210.63791 (19)0.6633 (3)0.5574 (4)0.0321 (8)
C220.64042 (19)0.5535 (3)0.5056 (4)0.0331 (8)
C230.5922 (3)0.5206 (4)0.4022 (6)0.0547 (13)
C240.5447 (2)0.5919 (4)0.3480 (6)0.0547 (12)
C250.5446 (2)0.7003 (4)0.3957 (5)0.0451 (11)
C260.5898 (2)0.7354 (4)0.4990 (5)0.0394 (9)
C270.68104 (19)0.7074 (3)0.6680 (5)0.0333 (8)
C280.80755 (19)0.6654 (3)0.9119 (4)0.0310 (8)
Atomic displacement parameters (Å2) top
Cs10.0839 (2)0.04022 (16)0.03278 (14)0.01202 (14)0.00531 (16)0.00140 (11)
Br10.0472 (3)0.0737 (4)0.0604 (3)0.0188 (2)0.0121 (2)0.0177 (3)
Br20.0481 (3)0.0909 (4)0.0674 (4)0.0290 (3)0.0013 (3)0.0313 (3)
Fe10.0313 (2)0.0162 (2)0.0268 (2)0.00079 (19)0.0026 (2)0.00010 (18)
S110.0395 (5)0.0238 (4)0.0398 (5)0.0007 (4)0.0103 (4)0.0019 (4)
S210.0390 (5)0.0256 (4)0.0365 (5)0.0029 (4)0.0060 (4)0.0031 (4)
O110.0434 (15)0.0211 (13)0.0380 (15)0.0036 (11)0.0130 (12)0.0031 (11)
O210.0472 (16)0.0209 (13)0.0368 (15)0.0060 (11)0.0101 (13)0.0040 (11)
N110.0355 (15)0.0183 (14)0.0261 (15)0.0005 (12)0.0011 (12)0.0017 (11)
N120.0400 (17)0.0183 (14)0.0369 (18)0.0004 (12)0.0034 (14)0.0057 (12)
N130.046 (2)0.0313 (18)0.051 (2)0.0027 (16)0.0128 (17)0.0141 (16)
C110.0359 (19)0.0259 (19)0.0325 (19)0.0046 (15)0.0046 (16)0.0021 (15)
C120.037 (2)0.0273 (19)0.034 (2)0.0011 (16)0.0053 (16)0.0002 (15)
C130.060 (3)0.035 (2)0.064 (3)0.001 (2)0.031 (3)0.005 (2)
C140.052 (3)0.051 (3)0.061 (3)0.002 (2)0.026 (2)0.002 (2)
C150.037 (2)0.049 (3)0.040 (2)0.0086 (19)0.0058 (18)0.0081 (19)
C160.039 (2)0.035 (2)0.042 (2)0.0081 (18)0.0012 (18)0.0053 (17)
C170.040 (2)0.0176 (17)0.043 (2)0.0045 (15)0.0007 (17)0.0018 (15)
C180.0337 (19)0.0271 (19)0.0285 (18)0.0026 (15)0.0037 (15)0.0046 (14)
N210.0345 (15)0.0186 (14)0.0268 (15)0.0008 (12)0.0032 (12)0.0024 (11)
N220.0413 (18)0.0221 (15)0.0347 (17)0.0020 (13)0.0006 (14)0.0082 (13)
N230.048 (2)0.037 (2)0.046 (2)0.0021 (16)0.0102 (17)0.0144 (16)
C210.035 (2)0.0272 (19)0.034 (2)0.0026 (16)0.0036 (15)0.0030 (15)
C220.038 (2)0.028 (2)0.033 (2)0.0036 (16)0.0042 (16)0.0017 (16)
C230.063 (3)0.036 (2)0.065 (3)0.000 (2)0.024 (3)0.007 (2)
C240.049 (3)0.061 (3)0.054 (3)0.004 (2)0.019 (2)0.000 (2)
C250.038 (2)0.056 (3)0.041 (2)0.012 (2)0.0009 (18)0.014 (2)
C260.040 (2)0.037 (2)0.042 (2)0.0086 (18)0.0032 (19)0.0056 (17)
C270.041 (2)0.0173 (16)0.041 (2)0.0030 (15)0.0010 (17)0.0029 (15)
C280.038 (2)0.0261 (18)0.0294 (18)0.0035 (15)0.0035 (15)0.0040 (14)
Geometric parameters (Å, º) top
Fe1—S112.2321 (11)C11—C121.406 (5)
Fe1—S212.2422 (11)C11—C161.407 (5)
Fe1—O111.942 (3)C11—C171.450 (6)
Cs1—S11i3.7159 (11)C12—C131.407 (6)
Cs1—S21i3.5564 (11)C13—C141.362 (6)
Cs1—O113.220 (3)C13—H130.9300
Cs1—O213.129 (3)C14—C151.382 (7)
Fe1—O211.956 (3)C14—H140.9300
Fe1—N111.947 (3)C15—C161.359 (6)
Fe1—N211.938 (3)C16—H160.9300
Cs1—C123.254 (4)C17—H170.9300
Cs1—N12ii3.326 (3)N21—C271.296 (5)
Cs1—C223.385 (4)N21—N221.401 (4)
Cs1—N22iii3.470 (3)N22—C281.298 (5)
Cs1—C133.547 (6)N22—Cs1vi3.470 (3)
Cs1—C233.577 (6)N23—C281.356 (5)
Cs1—C28i3.691 (4)N23—Cs1iv3.699 (4)
Cs1—N23i3.699 (4)N23—H23A0.8600
Br1—C151.900 (4)N23—H23B0.8600
Br2—C251.897 (4)C21—C261.407 (5)
S11—C181.750 (4)C21—C221.408 (5)
S11—Cs1iv3.7159 (11)C21—C271.427 (6)
S21—C281.753 (4)C22—C231.406 (6)
S21—Cs1iv3.5564 (11)C23—C241.379 (7)
O11—C121.317 (5)C23—H230.9300
O21—C221.322 (5)C24—C251.380 (7)
N11—C171.281 (5)C24—H240.9300
N11—N121.394 (4)C25—C261.372 (7)
N12—C181.310 (5)C26—H260.9300
N12—Cs1v3.326 (3)C27—Cs1vi3.807 (4)
N13—C181.343 (5)C27—H270.9300
N13—H13A0.8600C28—Cs1iv3.691 (4)
S11—Fe1—S2193.66 (4)Fe1—S11—Cs1iv103.80 (4)
S11—Fe1—N1186.01 (9)C28—S21—Cs1iv80.30 (13)
S11—Fe1—O11177.50 (9)Fe1—S21—Cs1iv108.55 (4)
S11—Fe1—O2189.78 (10)C12—O11—Fe1125.8 (2)
S11—Fe1—N2190.57 (9)C12—O11—Cs179.7 (2)
S21—Fe1—O1188.81 (9)Fe1—O11—Cs1109.12 (11)
S21—Fe1—O21176.56 (10)C22—O21—Fe1125.7 (2)
S21—Fe1—N1190.96 (9)C22—O21—Cs189.4 (2)
S21—Fe1—N2186.07 (9)Fe1—O21—Cs1112.16 (12)
O11—Fe1—O2187.75 (12)C17—N11—N12114.4 (3)
O11—Fe1—N1194.35 (12)C17—N11—Fe1124.6 (3)
O11—Cs1—S11i176.98 (5)N12—N11—Fe1121.0 (2)
O11—Cs1—S21i129.54 (5)C18—N12—Cs1v122.8 (2)
O11—Cs1—N12ii92.97 (7)N11—N12—Cs1v122.6 (2)
O11—Cs1—N22iii65.82 (7)C18—N13—H13A120.0
O11—Cs1—N23i100.65 (7)C18—N13—H13B120.0
O11—Cs1—O2150.34 (7)H13A—N13—H13B120.0
O21—Cs1—S11i126.82 (5)C12—C11—C16119.1 (4)
O21—Cs1—S21i178.78 (5)C12—C11—C17123.9 (3)
O21—Cs1—N12ii75.63 (7)C16—C11—C17117.0 (4)
O21—Cs1—N22iii82.42 (7)C12—C11—Cs157.6 (2)
O21—Cs1—N23i137.96 (7)C16—C11—Cs1107.5 (3)
O11—Fe1—N2189.20 (12)C17—C11—Cs1105.8 (2)
O21—Fe1—N1189.40 (11)O11—C12—C11124.0 (4)
O21—Fe1—N2193.78 (12)O11—C12—C13118.6 (4)
N11—Fe1—N21175.33 (12)C11—C12—C13117.3 (4)
C18—S11—Fe195.12 (13)O11—C12—Cs176.8 (2)
C28—S21—Fe194.61 (14)C11—C12—Cs1101.1 (3)
N11—N12—C18113.5 (3)C13—C12—Cs190.1 (3)
N21—N22—C28113.6 (3)C14—C13—C12122.5 (4)
N12—C18—S11124.3 (3)C14—C13—Cs1109.9 (4)
N22—C28—S21124.8 (3)C12—C13—Cs166.5 (3)
N12ii—Cs1—S11i85.01 (6)C14—C13—H13118.7
N12ii—Cs1—S21i103.23 (6)C12—C13—H13118.7
N12ii—Cs1—N22iii156.35 (8)Cs1—C13—H1393.4
N12ii—Cs1—N23i143.33 (8)C13—C14—C15119.4 (4)
N22iii—Cs1—S11i115.72 (6)C13—C14—H14120.3
N22iii—Cs1—S21i98.64 (6)C15—C14—H14120.3
N22iii—Cs1—N23i56.10 (8)C16—C15—C14120.3 (4)
N23i—Cs1—S11i82.29 (6)C16—C15—Br1120.5 (3)
N23i—Cs1—S21i42.99 (6)C14—C15—Br1119.1 (3)
S21i—Cs1—S11i53.27 (2)C15—C16—C11121.3 (4)
O21—Cs1—C1267.16 (9)C15—C16—H16119.4
O11—Cs1—C1223.47 (8)C11—C16—H16119.4
C12—Cs1—N12ii81.82 (9)N11—C17—C11126.5 (3)
O21—Cs1—C2222.99 (8)N11—C17—H17116.8
O11—Cs1—C2264.99 (8)C11—C17—H17116.8
C12—Cs1—C2285.89 (9)N12—C18—N13119.1 (3)
N12ii—Cs1—C2290.97 (9)N13—C18—S11116.6 (3)
C12—Cs1—N22iii81.64 (9)C27—N21—N22114.0 (3)
C22—Cs1—N22iii71.09 (9)C27—N21—Fe1124.9 (3)
O21—Cs1—C1389.17 (9)N22—N21—Fe1121.0 (2)
O11—Cs1—C1340.15 (9)C28—N22—Cs1vi131.6 (2)
C12—Cs1—C1323.37 (10)N21—N22—Cs1vi108.5 (2)
N12ii—Cs1—C1394.77 (10)C28—N23—Cs1iv79.1 (2)
C22—Cs1—C13105.07 (10)C28—N23—H23A120.0
N22iii—Cs1—C1376.00 (10)Cs1iv—N23—H23A116.4
C12—Cs1—S21i112.34 (7)C28—N23—H23B120.0
C22—Cs1—S21i158.08 (7)Cs1iv—N23—H23B75.2
C13—Cs1—S21i90.50 (8)H23A—N23—H23B120.0
O21—Cs1—C2340.25 (10)C26—C21—C22119.0 (4)
O11—Cs1—C2387.66 (10)C26—C21—C27116.8 (4)
C12—Cs1—C23107.16 (11)C22—C21—C27124.2 (4)
N12ii—Cs1—C2385.29 (10)O21—C22—C23118.6 (4)
C22—Cs1—C2323.09 (10)O21—C22—C21123.9 (4)
N22iii—Cs1—C2383.58 (9)C23—C22—C21117.5 (4)
C13—Cs1—C23127.81 (11)O21—C22—Cs167.6 (2)
S21i—Cs1—C23140.36 (9)C23—C22—Cs186.1 (3)
O21—Cs1—C28i153.27 (7)C21—C22—Cs1115.4 (3)
O11—Cs1—C28i121.63 (8)C24—C23—C22122.7 (4)
C12—Cs1—C28i115.54 (9)C24—C23—Cs1120.8 (4)
N12ii—Cs1—C28i130.71 (8)C22—C23—Cs170.8 (3)
C22—Cs1—C28i133.56 (9)C24—C23—H23118.6
N22iii—Cs1—C28i72.13 (8)C22—C23—H23118.6
C13—Cs1—C28i92.40 (10)Cs1—C23—H2379.0
S21i—Cs1—C28i27.92 (6)C23—C24—C25119.0 (4)
C23—Cs1—C28i126.05 (10)C23—C24—H24120.5
C12—Cs1—N23i97.50 (9)C25—C24—H24120.5
C22—Cs1—N23i125.66 (9)C26—C25—C24120.3 (4)
C13—Cs1—N23i75.54 (10)C26—C25—Br2119.9 (4)
C23—Cs1—N23i128.77 (10)C24—C25—Br2119.8 (3)
C28i—Cs1—N23i21.14 (8)C25—C26—C21121.4 (4)
C12—Cs1—S11i157.37 (7)C25—C26—H26119.3
C22—Cs1—S11i112.74 (7)C21—C26—H26119.3
C13—Cs1—S11i142.19 (8)N21—C27—C21126.6 (3)
C23—Cs1—S11i89.93 (8)N21—C27—Cs1vi95.3 (2)
C28i—Cs1—S11i61.33 (6)C21—C27—Cs1vi132.9 (3)
N21—Fe1—Cs196.96 (9)N21—C27—H27116.7
O11—Fe1—Cs145.44 (9)C21—C27—H27116.7
N11—Fe1—Cs187.70 (9)N22—C28—N23118.0 (4)
O21—Fe1—Cs142.73 (9)N23—C28—S21117.2 (3)
S11—Fe1—Cs1132.16 (3)N22—C28—Cs1iv116.2 (2)
S21—Fe1—Cs1133.86 (3)N23—C28—Cs1iv79.8 (2)
C18—S11—Cs1iv94.66 (13)S21—C28—Cs1iv71.78 (12)
O21—Cs1—Fe1—N2188.03 (14)Fe1—O11—C12—Cs1106.2 (2)
O11—Cs1—Fe1—N2181.96 (14)C16—C11—C12—O11174.6 (4)
C12—Cs1—Fe1—N21110.71 (14)C17—C11—C12—O116.4 (7)
N12ii—Cs1—Fe1—N21162.21 (11)Cs1—C11—C12—O1181.5 (4)
C22—Cs1—Fe1—N2161.58 (13)C16—C11—C12—C132.8 (6)
N22iii—Cs1—Fe1—N2116.75 (11)C17—C11—C12—C13176.2 (4)
C13—Cs1—Fe1—N2198.26 (12)Cs1—C11—C12—C1395.9 (4)
S21i—Cs1—Fe1—N2194.76 (10)C16—C11—C12—Cs193.1 (4)
C23—Cs1—Fe1—N2173.36 (12)C17—C11—C12—Cs187.8 (4)
C28i—Cs1—Fe1—N2143.14 (14)O21—Cs1—C12—O1139.76 (19)
N23i—Cs1—Fe1—N2147.78 (11)N12ii—Cs1—C12—O11117.6 (2)
S11i—Cs1—Fe1—N2199.68 (10)C22—Cs1—C12—O1126.0 (2)
O21—Cs1—Fe1—O11170.00 (16)N22iii—Cs1—C12—O1145.5 (2)
C12—Cs1—Fe1—O1128.75 (15)C13—Cs1—C12—O11119.4 (4)
N12ii—Cs1—Fe1—O11115.83 (12)S21i—Cs1—C12—O11141.44 (18)
C22—Cs1—Fe1—O11143.55 (15)C23—Cs1—C12—O1135.1 (2)
N22iii—Cs1—Fe1—O1165.21 (12)C28i—Cs1—C12—O11111.0 (2)
C13—Cs1—Fe1—O1116.30 (14)N23i—Cs1—C12—O1199.5 (2)
S21i—Cs1—Fe1—O1112.80 (12)S11i—Cs1—C12—O11172.58 (13)
C23—Cs1—Fe1—O11155.32 (14)O21—Cs1—C12—C1182.9 (2)
C28i—Cs1—Fe1—O1138.82 (15)O11—Cs1—C12—C11122.7 (4)
N23i—Cs1—Fe1—O1134.18 (13)N12ii—Cs1—C12—C115.1 (2)
S11i—Cs1—Fe1—O11178.36 (12)C22—Cs1—C12—C1196.7 (2)
O21—Cs1—Fe1—N1191.61 (14)N22iii—Cs1—C12—C11168.2 (3)
O11—Cs1—Fe1—N1198.40 (14)C13—Cs1—C12—C11117.9 (4)
C12—Cs1—Fe1—N1169.65 (14)S21i—Cs1—C12—C1195.9 (2)
N12ii—Cs1—Fe1—N1117.43 (11)C23—Cs1—C12—C1187.6 (3)
C22—Cs1—Fe1—N11118.06 (14)C28i—Cs1—C12—C11126.3 (2)
N22iii—Cs1—Fe1—N11163.61 (11)N23i—Cs1—C12—C11137.9 (2)
C13—Cs1—Fe1—N1182.10 (13)S11i—Cs1—C12—C1149.9 (4)
S21i—Cs1—Fe1—N1185.59 (10)O21—Cs1—C12—C13159.2 (3)
C23—Cs1—Fe1—N11106.28 (12)O11—Cs1—C12—C13119.4 (4)
C28i—Cs1—Fe1—N11137.22 (14)N12ii—Cs1—C12—C13123.0 (3)
N23i—Cs1—Fe1—N11132.58 (11)C22—Cs1—C12—C13145.4 (3)
S11i—Cs1—Fe1—N1179.96 (10)N22iii—Cs1—C12—C1374.0 (3)
O11—Cs1—Fe1—O21170.00 (16)S21i—Cs1—C12—C1322.0 (3)
C12—Cs1—Fe1—O21161.25 (15)C23—Cs1—C12—C13154.5 (3)
N12ii—Cs1—Fe1—O2174.17 (12)C28i—Cs1—C12—C138.4 (3)
C22—Cs1—Fe1—O2126.45 (15)N23i—Cs1—C12—C1320.0 (3)
N22iii—Cs1—Fe1—O21104.78 (12)S11i—Cs1—C12—C1368.0 (3)
C13—Cs1—Fe1—O21173.71 (14)O11—C12—C13—C14174.4 (5)
S21i—Cs1—Fe1—O21177.20 (11)C11—C12—C13—C143.1 (8)
C23—Cs1—Fe1—O2114.67 (14)Cs1—C12—C13—C1499.4 (6)
C28i—Cs1—Fe1—O21131.17 (15)O11—C12—C13—Cs175.0 (4)
N23i—Cs1—Fe1—O21135.81 (13)C11—C12—C13—Cs1102.5 (4)
S11i—Cs1—Fe1—O2111.65 (12)O21—Cs1—C13—C14136.9 (3)
O21—Cs1—Fe1—S119.09 (11)O11—Cs1—C13—C14150.3 (4)
O11—Cs1—Fe1—S11179.09 (12)C12—Cs1—C13—C14117.8 (5)
C12—Cs1—Fe1—S11152.16 (11)N12ii—Cs1—C13—C1461.4 (3)
N12ii—Cs1—Fe1—S1165.08 (7)C22—Cs1—C13—C14153.7 (3)
C22—Cs1—Fe1—S1135.54 (11)N22iii—Cs1—C13—C14140.7 (4)
N22iii—Cs1—Fe1—S11113.87 (7)S21i—Cs1—C13—C1441.9 (3)
C13—Cs1—Fe1—S11164.62 (10)C23—Cs1—C13—C14149.1 (3)
S21i—Cs1—Fe1—S11168.11 (5)C28i—Cs1—C13—C1469.8 (3)
C23—Cs1—Fe1—S1123.76 (9)N23i—Cs1—C13—C1482.7 (3)
C28i—Cs1—Fe1—S11140.26 (11)S11i—Cs1—C13—C1426.6 (4)
N23i—Cs1—Fe1—S11144.91 (8)O21—Cs1—C13—C1219.1 (3)
S11i—Cs1—Fe1—S112.55 (4)O11—Cs1—C13—C1232.5 (2)
O21—Cs1—Fe1—S21179.27 (12)N12ii—Cs1—C13—C1256.4 (3)
O11—Cs1—Fe1—S219.27 (12)C22—Cs1—C13—C1235.9 (3)
C12—Cs1—Fe1—S2119.48 (11)N22iii—Cs1—C13—C12101.5 (3)
N12ii—Cs1—Fe1—S21106.56 (7)S21i—Cs1—C13—C12159.7 (3)
C22—Cs1—Fe1—S21152.82 (11)C23—Cs1—C13—C1231.3 (3)
N22iii—Cs1—Fe1—S2174.49 (7)C28i—Cs1—C13—C12172.4 (3)
C13—Cs1—Fe1—S217.02 (9)N23i—Cs1—C13—C12159.5 (3)
S21i—Cs1—Fe1—S213.53 (4)S11i—Cs1—C13—C12144.4 (2)
C23—Cs1—Fe1—S21164.60 (10)C12—C13—C14—C151.5 (9)
C28i—Cs1—Fe1—S2148.10 (11)Cs1—C13—C14—C1575.8 (6)
N23i—Cs1—Fe1—S2143.45 (8)C13—C14—C15—C160.4 (8)
S11i—Cs1—Fe1—S21169.09 (5)C13—C14—C15—Br1179.1 (4)
N21—Fe1—S11—C18174.90 (16)C14—C15—C16—C110.6 (7)
N11—Fe1—S11—C181.91 (15)Br1—C15—C16—C11179.3 (3)
O21—Fe1—S11—C1891.32 (15)C12—C11—C16—C151.1 (6)
S21—Fe1—S11—C1888.80 (13)C17—C11—C16—C15178.1 (4)
Cs1—Fe1—S11—C1885.17 (13)Cs1—C11—C16—C1563.1 (4)
N21—Fe1—S11—Cs1iv78.82 (9)N12—N11—C17—C11176.4 (4)
N11—Fe1—S11—Cs1iv97.99 (9)Fe1—N11—C17—C112.2 (6)
O21—Fe1—S11—Cs1iv172.60 (8)C12—C11—C17—N111.1 (7)
S21—Fe1—S11—Cs1iv7.28 (4)C16—C11—C17—N11177.9 (4)
Cs1—Fe1—S11—Cs1iv178.751 (19)Cs1—C11—C17—N1162.4 (5)
N21—Fe1—S21—C281.22 (15)N11—N12—C18—N13178.3 (3)
O11—Fe1—S21—C2890.51 (15)Cs1v—N12—C18—N1313.6 (5)
N11—Fe1—S21—C28175.16 (15)N11—N12—C18—S110.7 (5)
S11—Fe1—S21—C2889.10 (13)Cs1v—N12—C18—S11167.32 (17)
Cs1—Fe1—S21—C2897.10 (13)Fe1—S11—C18—N122.1 (3)
N21—Fe1—S21—Cs1iv82.53 (9)Cs1iv—S11—C18—N12106.4 (3)
O11—Fe1—S21—Cs1iv171.81 (8)Fe1—S11—C18—N13177.0 (3)
N11—Fe1—S21—Cs1iv93.86 (9)Cs1iv—S11—C18—N1372.7 (3)
S11—Fe1—S21—Cs1iv7.79 (4)O11—Fe1—N21—C2793.9 (3)
Cs1—Fe1—S21—Cs1iv178.407 (19)O21—Fe1—N21—C276.2 (3)
N21—Fe1—O11—C12168.4 (3)S11—Fe1—N21—C2783.6 (3)
N11—Fe1—O11—C128.5 (3)S21—Fe1—N21—C27177.3 (3)
O21—Fe1—O11—C1297.7 (3)Cs1—Fe1—N21—C2749.0 (3)
S21—Fe1—O11—C1282.4 (3)O11—Fe1—N21—N2290.0 (3)
Cs1—Fe1—O11—C1291.0 (3)O21—Fe1—N21—N22177.7 (3)
N21—Fe1—O11—Cs1100.59 (12)S11—Fe1—N21—N2292.4 (3)
N11—Fe1—O11—Cs182.45 (12)S21—Fe1—N21—N221.2 (3)
O21—Fe1—O11—Cs16.78 (11)Cs1—Fe1—N21—N22134.9 (2)
S21—Fe1—O11—Cs1173.33 (8)C27—N21—N22—C28176.9 (3)
O21—Cs1—O11—C12130.0 (2)Fe1—N21—N22—C280.4 (4)
N12ii—Cs1—O11—C1261.5 (2)C27—N21—N22—Cs1vi27.6 (3)
C22—Cs1—O11—C12151.2 (2)Fe1—N21—N22—Cs1vi155.88 (15)
N22iii—Cs1—O11—C12129.3 (2)Fe1—O21—C22—C23170.7 (4)
C13—Cs1—O11—C1232.4 (2)Cs1—O21—C22—C2372.1 (4)
S21i—Cs1—O11—C1248.4 (2)Fe1—O21—C22—C2110.8 (6)
C23—Cs1—O11—C12146.6 (2)Cs1—O21—C22—C21106.4 (4)
C28i—Cs1—O11—C1281.5 (2)Fe1—O21—C22—Cs1117.2 (3)
N23i—Cs1—O11—C1284.3 (2)C26—C21—C22—O21175.6 (4)
O21—Cs1—O11—Fe15.49 (9)C27—C21—C22—O215.0 (6)
C12—Cs1—O11—Fe1124.5 (3)C26—C21—C22—C232.9 (6)
N12ii—Cs1—O11—Fe163.05 (11)C27—C21—C22—C23176.5 (4)
C22—Cs1—O11—Fe126.63 (11)C26—C21—C22—Cs196.5 (4)
N22iii—Cs1—O11—Fe1106.12 (12)C27—C21—C22—Cs184.1 (4)
C13—Cs1—O11—Fe1156.93 (19)O11—Cs1—C22—O2145.30 (19)
S21i—Cs1—O11—Fe1172.93 (7)C12—Cs1—C22—O2134.2 (2)
C23—Cs1—O11—Fe122.11 (13)N12ii—Cs1—C22—O2147.5 (2)
C28i—Cs1—O11—Fe1153.92 (10)N22iii—Cs1—C22—O21116.8 (2)
N23i—Cs1—O11—Fe1151.16 (11)C13—Cs1—C22—O2147.7 (2)
N21—Fe1—O21—C2210.1 (3)S21i—Cs1—C22—O21178.45 (13)
O11—Fe1—O21—C2299.1 (3)C23—Cs1—C22—O21123.1 (4)
N11—Fe1—O21—C22166.5 (3)C28i—Cs1—C22—O21156.09 (18)
S11—Fe1—O21—C2280.5 (3)N23i—Cs1—C22—O21130.5 (2)
Cs1—Fe1—O21—C22106.2 (3)S11i—Cs1—C22—O21132.53 (19)
N21—Fe1—O21—Cs196.17 (12)O21—Cs1—C22—C23123.1 (4)
O11—Fe1—O21—Cs17.12 (11)O11—Cs1—C22—C23168.4 (3)
N11—Fe1—O21—Cs187.26 (12)C12—Cs1—C22—C23157.3 (3)
S11—Fe1—O21—Cs1173.27 (8)N12ii—Cs1—C22—C2375.6 (3)
O11—Cs1—O21—C22123.2 (2)N22iii—Cs1—C22—C23120.1 (3)
C12—Cs1—O21—C22142.5 (2)C13—Cs1—C22—C23170.8 (3)
N12ii—Cs1—O21—C22130.4 (2)S21i—Cs1—C22—C2355.3 (4)
N22iii—Cs1—O21—C2258.5 (2)C28i—Cs1—C22—C2380.8 (3)
C13—Cs1—O21—C22134.4 (2)N23i—Cs1—C22—C23106.4 (3)
C23—Cs1—O21—C2230.6 (2)S11i—Cs1—C22—C239.4 (3)
C28i—Cs1—O21—C2240.8 (3)O21—Cs1—C22—C21118.2 (4)
N23i—Cs1—O21—C2267.3 (2)O11—Cs1—C22—C2172.9 (3)
S11i—Cs1—O21—C2258.1 (2)C12—Cs1—C22—C2184.0 (3)
O11—Cs1—O21—Fe15.56 (9)N12ii—Cs1—C22—C21165.7 (3)
C12—Cs1—O21—Fe113.76 (11)N22iii—Cs1—C22—C211.4 (3)
N12ii—Cs1—O21—Fe1100.81 (12)C13—Cs1—C22—C2170.5 (3)
C22—Cs1—O21—Fe1128.8 (3)S21i—Cs1—C22—C2163.3 (4)
N22iii—Cs1—O21—Fe170.32 (11)C23—Cs1—C22—C21118.7 (4)
C13—Cs1—O21—Fe15.66 (13)C28i—Cs1—C22—C2137.9 (3)
C23—Cs1—O21—Fe1159.33 (19)N23i—Cs1—C22—C2112.3 (3)
C28i—Cs1—O21—Fe188.0 (2)S11i—Cs1—C22—C21109.3 (3)
N23i—Cs1—O21—Fe161.43 (16)O21—C22—C23—C24176.8 (5)
S11i—Cs1—O21—Fe1173.12 (7)C21—C22—C23—C241.8 (8)
O11—Fe1—N11—C171.7 (3)Cs1—C22—C23—C24114.9 (5)
O21—Fe1—N11—C1789.4 (3)O21—C22—C23—Cs161.8 (3)
S11—Fe1—N11—C17179.3 (3)C21—C22—C23—Cs1116.8 (4)
S21—Fe1—N11—C1787.1 (3)O21—Cs1—C23—C24147.7 (4)
Cs1—Fe1—N11—C1746.7 (3)O11—Cs1—C23—C24127.8 (4)
O11—Fe1—N11—N12179.8 (3)C12—Cs1—C23—C24141.0 (4)
O21—Fe1—N11—N1292.1 (3)N12ii—Cs1—C23—C24139.1 (4)
S11—Fe1—N11—N122.2 (2)C22—Cs1—C23—C24117.3 (5)
S21—Fe1—N11—N1291.3 (3)N22iii—Cs1—C23—C2461.8 (4)
Cs1—Fe1—N11—N12134.8 (3)C13—Cs1—C23—C24128.5 (4)
C17—N11—N12—C18179.9 (3)S21i—Cs1—C23—C2434.0 (4)
Fe1—N11—N12—C181.5 (4)C28i—Cs1—C23—C240.5 (4)
C17—N11—N12—Cs1v11.8 (4)N23i—Cs1—C23—C2426.0 (4)
Fe1—N11—N12—Cs1v169.55 (13)S11i—Cs1—C23—C2454.1 (4)
O21—Cs1—C11—C1287.8 (2)O21—Cs1—C23—C2230.4 (2)
O11—Cs1—C11—C1232.1 (2)O11—Cs1—C23—C2210.5 (3)
N12ii—Cs1—C11—C12174.2 (3)C12—Cs1—C23—C2223.8 (3)
C22—Cs1—C11—C1282.3 (2)N12ii—Cs1—C23—C22103.7 (3)
N22iii—Cs1—C11—C1212.0 (3)N22iii—Cs1—C23—C2255.4 (3)
C13—Cs1—C11—C1234.6 (3)C13—Cs1—C23—C2211.3 (3)
S21i—Cs1—C11—C1293.1 (2)S21i—Cs1—C23—C22151.2 (2)
C23—Cs1—C11—C1298.6 (3)C28i—Cs1—C23—C22117.8 (3)
C28i—Cs1—C11—C1264.9 (3)N23i—Cs1—C23—C2291.3 (3)
N23i—Cs1—C11—C1246.2 (3)S11i—Cs1—C23—C22171.3 (3)
S11i—Cs1—C11—C12152.6 (2)C22—C23—C24—C250.6 (9)
O21—Cs1—C11—C16158.4 (3)Cs1—C23—C24—C2585.2 (6)
O11—Cs1—C11—C16145.9 (3)C23—C24—C25—C262.0 (8)
C12—Cs1—C11—C16113.8 (4)C23—C24—C25—Br2177.1 (4)
N12ii—Cs1—C11—C1672.0 (3)C24—C25—C26—C211.0 (7)
C22—Cs1—C11—C16163.9 (3)Br2—C25—C26—C21178.2 (3)
N22iii—Cs1—C11—C16125.8 (3)C22—C21—C26—C251.6 (6)
C13—Cs1—C11—C1679.2 (3)C27—C21—C26—C25177.9 (4)
S21i—Cs1—C11—C1620.7 (3)N22—N21—C27—C21179.4 (4)
C23—Cs1—C11—C16147.5 (3)Fe1—N21—C27—C213.0 (6)
C28i—Cs1—C11—C1648.9 (3)N22—N21—C27—Cs1vi23.8 (3)
N23i—Cs1—C11—C1667.6 (3)Fe1—N21—C27—Cs1vi159.93 (19)
S11i—Cs1—C11—C1638.7 (3)C26—C21—C27—N21179.8 (4)
O21—Cs1—C11—C1732.7 (2)C22—C21—C27—N210.8 (7)
O11—Cs1—C11—C1788.3 (2)C26—C21—C27—Cs1vi32.0 (5)
C12—Cs1—C11—C17120.4 (4)C22—C21—C27—Cs1vi148.6 (3)
N12ii—Cs1—C11—C1753.8 (2)N21—N22—C28—N23176.4 (3)
C22—Cs1—C11—C1738.1 (2)Cs1vi—N22—C28—N2335.5 (5)
N22iii—Cs1—C11—C17108.4 (2)N21—N22—C28—S211.0 (5)
C13—Cs1—C11—C17155.1 (3)Cs1vi—N22—C28—S21147.2 (2)
S21i—Cs1—C11—C17146.5 (2)N21—N22—C28—Cs1iv84.2 (3)
C23—Cs1—C11—C1721.8 (3)Cs1vi—N22—C28—Cs1iv127.6 (2)
C28i—Cs1—C11—C17174.6 (2)Cs1iv—N23—C28—N22114.3 (3)
N23i—Cs1—C11—C17166.7 (2)Cs1iv—N23—C28—S2163.3 (2)
S11i—Cs1—C11—C1787.0 (2)Fe1—S21—C28—N221.6 (4)
Fe1—O11—C12—C1111.7 (6)Cs1iv—S21—C28—N22109.7 (3)
Cs1—O11—C12—C1194.6 (4)Fe1—S21—C28—N23175.8 (3)
Fe1—O11—C12—C13171.0 (4)Cs1iv—S21—C28—N2367.7 (3)
Cs1—O11—C12—C1382.8 (4)Fe1—S21—C28—Cs1iv108.05 (4)
Symmetry codes: (i) x, y, z1; (ii) x, y+1/2, z1/2; (iii) x, y+3/2, z1/2; (iv) x, y, z+1; (v) x, y+1/2, z+1/2; (vi) x, y+3/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
N13—H13A···O21v0.862.082.907 (4)161
N13—H13B···Br2vii0.862.723.557 (4)163
N23—H23A···O11vi0.862.102.952 (5)171
N23—H23B···Br1viii0.862.953.590 (4)133
C13—H13···Br1ix0.932.833.578 (5)139
C23—H23···Br2x0.932.863.623 (5)141
Symmetry codes: (v) x, y+1/2, z+1/2; (vi) x, y+3/2, z+1/2; (vii) x+1, y1/2, z+3/2; (viii) x+2, y+1/2, z+3/2; (ix) x+2, y+1/2, z+1/2; (x) x+1, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaCs[Fe(C8H6BrN3OS)2]
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)20.2500 (14), 12.0868 (8), 9.0389 (5)
β (°) 90.337 (1)
V3)2212.3 (2)
Radiation typeMo Kα
µ (mm1)6.13
Crystal size (mm)0.08 × 0.08 × 0.01
Data collection
DiffractometerRigaku AFC12 four-circle Kappa
Absorption correctionMulti-scan
(CrystalClear-SM Expert; Rigaku, 2013)
Tmin, Tmax0.640, 0.941
No. of measured, independent and
observed [I > 2σ(I)] reflections
29088, 5073, 4211
(sin θ/λ)max1)0.649
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.086, 1.03
No. of reflections5073
No. of parameters272
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.88, 0.85

Computer programs: CrystalClear-SM Expert (Rigaku, 2013), ROTAX (Cooper et al., 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012).

Selected geometric parameters (Å, º) top
Fe1—S112.2321 (11)Fe1—O211.956 (3)
Fe1—S212.2422 (11)Fe1—N111.947 (3)
Fe1—O111.942 (3)Fe1—N211.938 (3)
Cs1—S11i3.7159 (11)Cs1—N12ii3.326 (3)
Cs1—S21i3.5564 (11)Cs1—N22iii3.470 (3)
Cs1—O113.220 (3)Cs1—N23i3.699 (4)
Cs1—O213.129 (3)
S11—Fe1—S2193.66 (4)O21—Cs1—N23i137.96 (7)
S11—Fe1—N1186.01 (9)O11—Fe1—N2189.20 (12)
S11—Fe1—O11177.50 (9)O21—Fe1—N1189.40 (11)
S11—Fe1—O2189.78 (10)O21—Fe1—N2193.78 (12)
S11—Fe1—N2190.57 (9)N11—Fe1—N21175.33 (12)
S21—Fe1—O1188.81 (9)C18—S11—Fe195.12 (13)
S21—Fe1—O21176.56 (10)C28—S21—Fe194.61 (14)
S21—Fe1—N1190.96 (9)N11—N12—C18113.5 (3)
S21—Fe1—N2186.07 (9)N21—N22—C28113.6 (3)
O11—Fe1—O2187.75 (12)N12—C18—S11124.3 (3)
O11—Fe1—N1194.35 (12)N22—C28—S21124.8 (3)
O11—Cs1—S11i176.98 (5)N12ii—Cs1—S11i85.01 (6)
O11—Cs1—S21i129.54 (5)N12ii—Cs1—S21i103.23 (6)
O11—Cs1—N12ii92.97 (7)N12ii—Cs1—N22iii156.35 (8)
O11—Cs1—N22iii65.82 (7)N12ii—Cs1—N23i143.33 (8)
O11—Cs1—N23i100.65 (7)N22iii—Cs1—S11i115.72 (6)
O11—Cs1—O2150.34 (7)N22iii—Cs1—S21i98.64 (6)
O21—Cs1—S11i126.82 (5)N22iii—Cs1—N23i56.10 (8)
O21—Cs1—S21i178.78 (5)N23i—Cs1—S11i82.29 (6)
O21—Cs1—N12ii75.63 (7)N23i—Cs1—S21i42.99 (6)
O21—Cs1—N22iii82.42 (7)S21i—Cs1—S11i53.27 (2)
Symmetry codes: (i) x, y, z1; (ii) x, y+1/2, z1/2; (iii) x, y+3/2, z1/2.
Hydrogen-bond geometry (Å, º) top
N13—H13A···O21iv0.862.082.907 (4)161.3
N13—H13B···Br2v0.862.723.557 (4)163.3
N23—H23A···O11vi0.862.102.952 (5)171.2
N23—H23B···Br1vii0.862.953.590 (4)133.0
C13—H13···Br1viii0.932.833.578 (5)138.6
C23—H23···Br2ix0.932.863.623 (5)140.5
Symmetry codes: (iv) x, y+1/2, z+1/2; (v) x+1, y1/2, z+3/2; (vi) x, y+3/2, z+1/2; (vii) x+2, y+1/2, z+3/2; (viii) x+2, y+1/2, z+1/2; (ix) x+1, y1/2, z+1/2.
Selected average Fe–donor atom bond distances for non-solvated FeIII bis(ligand) compounds of R-salicylaldehyde thiosemicarbazone top
CompoundaTemperature (K)Space group and Z'Fe—S (Å)Fe—N (Å)Fe—O (Å)Spin statebReference
Cs[Fe(thsa)2]298Pna21, Z' = 12.442.121.96HSRyabova, Ponomarev, Zelentsov & Atovmyan (1981)
103Pna21, Z' = 12.442.151.96HSRyabova, Ponomarev, Zelentsov & Atovmyan (1981)
NH4[Fe(5-Br-thsa)2]c298Pnca, Z' =, Ponomarev, Zelentsov, Shipilov & Atovmyan (1981)
NH4[Fe(5-Cl-thsa)2]298Pnca, Z' = et al. (1978)
135Pnca, Z' = et al. (1978)
(a) The ligands are defined as follows: H2L = salicylaldehyde thiosemicarbazone = H2thsa, so L2- = thsa, H2L = 5-bromosalicylaldehyde thiosemicarbazone = H2-5-Br-thsa, so L2- = 5-Br-thsa and H2L = 5-chlorosalicylaldehyde thiosemicarbazone = H2-5-Cl-thsa, so L2- = 5-Cl-thsa. (b) The spin states are defined as low spin (LS) and high spin (HS). (c) Determined for crystals of tabular form.

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