Hexakis(μ2-2-amino­ethanethiol­ato)­triiron(III) tris(perchlorate)

Igashira-Kamiyama, A.; Konno, T.

doi:10.1107/S1600536808036167

Hexakis(μ₂-2-aminoethanethiolato)triiron(III) tris(perchlorate)

In the title salt, [Fe₃(C₂H₆NS)₆](ClO₄)₃, the trinuclear cation lies on a special position of $\overline{3}$ site symmetry; the central Fe atom is coordinated by six thiolate groups from the two flanking fac-(S)-[Fe(C₂H₆NS)₃] units. In the flanking units, the three C₂H₆NS groups each chelate to the metal atom. The cations interact with the perchlorate anions through weak N—H

O hydrogen bonds resulting in a three-dimensional network. In the asymmetric unit two cations are present, one of which is disordered over two positions with occupancies of 0.75 and 0.25.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808036167/ng2504sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808036167/ng2504Isup2.hkl Contains datablock I

CCDC reference: 712286

checkCIF report

Key indicators

Single-crystal X-ray study
T = 200 K
Mean (C-C) = 0.003 Å
Disorder in main residue
R factor = 0.032
wR factor = 0.100
Data-to-parameter ratio = 14.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT301_ALERT_3_B Main Residue  Disorder .........................      31.00 Perc.

Alert level C
            Value of measurement temperature given =   200.000
            Value of melting point given =     0.000
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       3.50
PLAT213_ALERT_2_C Atom C3B     has ADP max/min Ratio .............       3.10 prola
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Fe2    --  S1      ..       6.21 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Fe2    --  N1      ..       6.50 su
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl1

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C12 H36 Cl3 Fe3 N6 O12 S6
            Atom count from _chemical_formula_moiety:Cl3 O12
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          6

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Due to the high Lewis basicity of thiolate groups, a great number of thiolate-bridged complexes have been synthesized up to now. 2-Aminoethanethiolate (aet) is the simplest N,S-chelating ligand that has been used for the formation of S-bridged polynuclear structures. For example, it has been shown that the aet ligand reacts with the octahedral metal ions to give linear-type S-bridged trinuclear structures, such as Co^III₃ (Busch and Jicha, 1962; Heeg et al., 1985; Marsh et al., 1986), Rh^III₃ (Mahboob et al., 2004), and Ru^III₃ (Matsuura et al., 2006). In this paper, we report on the crystal structure of the title compound (I), which was obtained by the reaction of aet and Fe(ClO₄)₃. The asymmetric unit of the compound (I) contains two complex cations having a threefold rotation-inversion axis and one perchlorate anion. One of the complex cations is disordered over two positions with occupancies of 0.75 and 0.25. In the complex cation of (I), two fac(S)-[Fe(aet)₃] units coordinate to a central Fe atom through thiolato bridges to form a linear-type trinuclear structure. Each terminal Fe atom is in an N₃S₃ octahedral environment, whereas the central Fe atom is in an S₆ octahedral environment. Considering the charge balance, it is assumed that all Fe atoms have a +III oxidation state.

Related literature top

For related structures, see: Busch & Jicha (1962); Heeg et al. (1985); Mahboob et al. (2004); Marsh et al. (1986); Matsuura et al. (2006).

Experimental top

To a solution containing 2-aminoethanethiol hydrochloride (0.11 g, 1 mmol) in 20 ml of methanol/CH₂Cl₂ (1:1) was added a solution of Et₃N (0.10 g, 1 mmol) in 10 ml of methanol and a solution of Fe(ClO₄)₃.6H₂O (0.09 g, 0.2 mmol) in 2 ml of methanol. The resulting dark brown solution was stood at room temperature overnight to give black crystals, which was filtered and washed with methanol. Yield: 31 mg (50% based on Fe). Anal. Calcd for [Fe₃(aet)₆](ClO₄)₃ = C₁₂H₃₆Cl₃Fe₃N₆O₁₂S₆: C, 15.62; H, 3.93; N, 9.11%. Found: C, 15.82; H, 3.88; N, 9.00%.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: Yadokari-XG (Wakita, 2000).

Figures top

	Fig. 1. The asymmetric unit of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms. Hydrogen atoms are omitted for clarity.
	Fig. 2. The cation units of (I). The molecule with open bonds is the minor component of the disordered unit. Symmetry codes: (i) -y + 1, x-y + 1, z; (ii) -x + y, -x + 1, z; (iii) -x + 2/3, -y + 4/3, -z + 1/3; (iv) y - 1/3, -x + y+1/3, -z + 1/3; (v) x-y + 2/3, x + 1/3, -z + 1/3; (vi) -x + 2/3, -y + 4/3, -z + 4/3; (vii) y - 1/3, -x + y+1/3, -z + 4/3; (viii) x-y + 2/3, x + 1/3, -z + 4/3.

Hexakis(µ₂-2-aminoethanethiolato)triiron(III) tris(perchlorate) top

Crystal data top

[Fe₃(C₂H₆NS)₆](ClO₄)₃	D_x = 1.984 Mg m⁻³
M_r = 922.73	Mo Kα radiation, λ = 0.71075 Å
Trigonal, R3	Cell parameters from 12827 reflections
Hall symbol: -R 3	θ = 3.4–27.4°
a = 14.2852 (6) Å	µ = 2.12 mm⁻¹
c = 26.2187 (8) Å	T = 200 K
V = 4633.6 (2) Å³	Prism, black
Z = 6	0.20 × 0.20 × 0.10 mm
F(000) = 2826

Data collection top

Rigaku R-AXIS RAPID diffractometer	2365 independent reflections
Radiation source: fine-focus sealed tube	2144 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.4°, θ_min = 3.4°
ω scans	h = −18→16
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −18→17
T_min = 0.677, T_max = 0.816	l = −33→33
15327 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.39	w = 1/[σ²(F_o²) + (0.0456P)² + 3.0528P] where P = (F_o² + 2F_c²)/3
2365 reflections	(Δ/σ)_max = 0.001
165 parameters	Δρ_max = 1.09 e Å⁻³
6 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Fe₃(C₂H₆NS)₆](ClO₄)₃	Z = 6
M_r = 922.73	Mo Kα radiation
Trigonal, R3	µ = 2.12 mm⁻¹
a = 14.2852 (6) Å	T = 200 K
c = 26.2187 (8) Å	0.20 × 0.20 × 0.10 mm
V = 4633.6 (2) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	2365 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2144 reflections with I > 2σ(I)
T_min = 0.677, T_max = 0.816	R_int = 0.053
15327 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	6 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.39	Δρ_max = 1.09 e Å⁻³
2365 reflections	Δρ_min = −0.31 e Å⁻³
165 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. The 2-aminoethanethiolate ligand of one unit containing Fe3 and Fe4 atoms is disordered over two positions with the occupancies of 0.75 and 0.25. The C3B atom in the minor component is restrained based on ISOR.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Fe1	0.3333	0.6667	0.1667	0.01712 (18)
Fe2	0.3333	0.6667	0.269870 (17)	0.01673 (15)
S1	0.21510 (4)	0.53292 (4)	0.219319 (19)	0.02149 (15)
N1	0.20358 (15)	0.64420 (15)	0.31253 (7)	0.0255 (4)
H1	0.2151	0.6336	0.3460	0.031*
H2	0.1986	0.7059	0.3110	0.031*
C1	0.09906 (18)	0.5506 (2)	0.29524 (9)	0.0308 (5)
H3	0.0382	0.5595	0.3071	0.037*
H4	0.0903	0.4828	0.3100	0.037*
C2	0.09795 (17)	0.5441 (2)	0.23732 (9)	0.0302 (5)
H5	0.1026	0.6098	0.2222	0.036*
H6	0.0306	0.4802	0.2253	0.036*
Fe3	0.3333	0.6667	0.6667	0.02171 (19)
Fe4	0.3333	0.6667	0.563330 (19)	0.02155 (16)
S2	0.20595 (6)	0.53902 (6)	0.61393 (3)	0.02341 (18)	0.75
N2	0.2103 (3)	0.6563 (3)	0.52058 (14)	0.0300 (8)	0.75
H7	0.2163	0.7234	0.5193	0.036*	0.75
H8	0.2176	0.6377	0.4878	0.036*	0.75
C3	0.0975 (3)	0.5650 (4)	0.59679 (17)	0.0394 (9)	0.75
H9	0.0267	0.5041	0.6076	0.047*	0.75
H10	0.1083	0.6319	0.6135	0.047*	0.75
C4	0.1011 (4)	0.5773 (4)	0.5393 (2)	0.0425 (11)	0.75
H11	0.0776	0.5062	0.5233	0.051*	0.75
H12	0.0496	0.6011	0.5289	0.051*	0.75
S2B	0.2622 (3)	0.7412 (2)	0.61334 (10)	0.0335 (5)	0.25
N2B	0.1951 (9)	0.6067 (9)	0.5199 (5)	0.035 (3)	0.25
H13	0.2127	0.6372	0.4879	0.041*	0.25
H14	0.1655	0.5332	0.5163	0.041*	0.25
C3B	0.1180 (11)	0.6301 (17)	0.5950 (6)	0.065 (4)	0.25
H15	0.1036	0.5589	0.6078	0.078*	0.25
H16	0.0638	0.6462	0.6098	0.078*	0.25
C4B	0.1130 (14)	0.6295 (15)	0.5432 (8)	0.060 (5)	0.25
H17	0.1257	0.7006	0.5311	0.072*	0.25
H18	0.0399	0.5737	0.5321	0.072*	0.25
Cl1	0.17461 (5)	0.41937 (4)	0.42062 (2)	0.03377 (17)
O1	0.12758 (17)	0.38390 (16)	0.47031 (7)	0.0460 (5)
O2	0.20389 (18)	0.53133 (14)	0.41480 (8)	0.0492 (5)
O3	0.0981 (2)	0.35574 (17)	0.38241 (8)	0.0604 (6)
O4	0.26978 (18)	0.41114 (19)	0.41632 (9)	0.0583 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0171 (2)	0.0171 (2)	0.0173 (4)	0.00853 (12)	0.000	0.000
Fe2	0.01850 (19)	0.01850 (19)	0.0132 (3)	0.00925 (9)	0.000	0.000
S1	0.0233 (3)	0.0207 (3)	0.0166 (3)	0.0081 (2)	−0.00003 (18)	0.00068 (17)
N1	0.0293 (10)	0.0302 (10)	0.0174 (9)	0.0151 (8)	0.0022 (7)	0.0004 (7)
C1	0.0224 (11)	0.0387 (13)	0.0235 (12)	0.0094 (10)	0.0051 (8)	0.0034 (9)
C2	0.0180 (10)	0.0410 (13)	0.0235 (11)	0.0088 (10)	0.0020 (8)	0.0009 (9)
Fe3	0.0190 (2)	0.0190 (2)	0.0272 (4)	0.00950 (12)	0.000	0.000
Fe4	0.0229 (2)	0.0229 (2)	0.0189 (3)	0.01145 (10)	0.000	0.000
S2	0.0220 (4)	0.0236 (4)	0.0205 (4)	0.0082 (3)	−0.0005 (3)	−0.0008 (3)
N2	0.0387 (19)	0.033 (2)	0.0200 (15)	0.0197 (19)	−0.0061 (12)	−0.0045 (16)
C3	0.0233 (18)	0.052 (2)	0.040 (2)	0.0165 (19)	−0.0008 (14)	0.001 (2)
C4	0.031 (2)	0.060 (3)	0.036 (2)	0.023 (3)	−0.0093 (15)	−0.007 (2)
S2B	0.0387 (15)	0.0385 (14)	0.0369 (14)	0.0294 (14)	−0.0028 (11)	0.0001 (11)
N2B	0.034 (5)	0.030 (6)	0.037 (5)	0.014 (6)	−0.011 (4)	−0.014 (5)
C3B	0.026 (6)	0.124 (13)	0.053 (8)	0.043 (9)	−0.010 (5)	−0.014 (10)
C4B	0.033 (7)	0.066 (12)	0.082 (12)	0.026 (9)	−0.018 (7)	−0.014 (11)
Cl1	0.0459 (4)	0.0229 (3)	0.0229 (3)	0.0100 (2)	−0.0001 (2)	0.00124 (19)
O1	0.0606 (13)	0.0428 (11)	0.0322 (10)	0.0239 (10)	0.0109 (9)	0.0091 (8)
O2	0.0767 (15)	0.0243 (9)	0.0382 (12)	0.0188 (9)	−0.0039 (10)	0.0027 (7)
O3	0.0780 (16)	0.0390 (11)	0.0502 (13)	0.0188 (11)	−0.0270 (11)	−0.0113 (9)
O4	0.0501 (12)	0.0571 (13)	0.0655 (15)	0.0252 (11)	0.0103 (10)	0.0076 (11)

Geometric parameters (Å, º) top

Fe1—S1ⁱ	2.2763 (5)	Fe4—N2ⁱⁱⁱ	2.026 (4)
Fe1—S1ⁱⁱ	2.2763 (5)	Fe4—N2^iv	2.026 (4)
Fe1—S1ⁱⁱⁱ	2.2764 (5)	Fe4—N2B	2.059 (11)
Fe1—S1	2.2764 (5)	Fe4—N2Bⁱⁱⁱ	2.059 (11)
Fe1—S1^iv	2.2764 (5)	Fe4—N2B^iv	2.059 (11)
Fe1—S1^v	2.2764 (5)	Fe4—S2B	2.229 (2)
Fe2—N1	2.0482 (18)	Fe4—S2Bⁱⁱⁱ	2.229 (2)
Fe2—N1ⁱⁱⁱ	2.0482 (18)	Fe4—S2B^iv	2.229 (2)
Fe2—N1^iv	2.0482 (18)	Fe4—S2ⁱⁱⁱ	2.2535 (7)
Fe2—S1ⁱⁱⁱ	2.2434 (6)	Fe4—S2	2.2535 (8)
Fe2—S1	2.2434 (6)	Fe4—S2^iv	2.2535 (7)
Fe2—S1^iv	2.2434 (6)	S2—C3	1.821 (4)
S1—C2	1.821 (2)	N2—C4	1.480 (7)
N1—C1	1.492 (3)	N2—H7	0.9200
N1—H1	0.9200	N2—H8	0.9200
N1—H2	0.9200	C3—C4	1.514 (7)
C1—C2	1.521 (3)	C3—H9	0.9900
C1—H3	0.9900	C3—H10	0.9900
C1—H4	0.9900	C4—H11	0.9900
C2—H5	0.9900	C4—H12	0.9900
C2—H6	0.9900	S2B—C3B	1.929 (16)
Fe3—S2B^vi	2.281 (2)	N2B—C4B	1.49 (2)
Fe3—S2B	2.281 (2)	N2B—H13	0.9200
Fe3—S2B^iv	2.281 (2)	N2B—H14	0.9200
Fe3—S2Bⁱⁱⁱ	2.281 (2)	C3B—C4B	1.36 (3)
Fe3—S2B^vii	2.281 (2)	C3B—H15	0.9900
Fe3—S2B^viii	2.281 (2)	C3B—H16	0.9900
Fe3—S2^viii	2.2869 (7)	C4B—H17	0.9900
Fe3—S2ⁱⁱⁱ	2.2869 (7)	C4B—H18	0.9900
Fe3—S2	2.2869 (7)	Cl1—O3	1.425 (2)
Fe3—S2^iv	2.2869 (7)	Cl1—O4	1.426 (2)
Fe3—S2^vi	2.2870 (7)	Cl1—O1	1.4369 (18)
Fe3—S2^vii	2.2870 (7)	Cl1—O2	1.4447 (18)
Fe4—N2	2.026 (4)

S1ⁱ—Fe1—S1ⁱⁱ	87.042 (18)	N2—Fe4—N2ⁱⁱⁱ	92.34 (15)
S1ⁱ—Fe1—S1ⁱⁱⁱ	180.00 (3)	N2—Fe4—N2^iv	92.34 (15)
S1ⁱⁱ—Fe1—S1ⁱⁱⁱ	92.959 (18)	N2ⁱⁱⁱ—Fe4—N2^iv	92.34 (15)
S1ⁱ—Fe1—S1	92.960 (18)	N2B—Fe4—N2Bⁱⁱⁱ	92.4 (5)
S1ⁱⁱ—Fe1—S1	180.0	N2—Fe4—N2B^iv	103.6 (3)
S1ⁱⁱⁱ—Fe1—S1	87.039 (18)	N2ⁱⁱⁱ—Fe4—N2B^iv	78.4 (3)
S1ⁱ—Fe1—S1^iv	92.961 (18)	N2^iv—Fe4—N2B^iv	17.7 (3)
S1ⁱⁱ—Fe1—S1^iv	92.961 (18)	N2B—Fe4—N2B^iv	92.4 (5)
S1ⁱⁱⁱ—Fe1—S1^iv	87.039 (18)	N2Bⁱⁱⁱ—Fe4—N2B^iv	92.4 (5)
S1—Fe1—S1^iv	87.039 (18)	N2B—Fe4—S2B	87.3 (3)
S1ⁱ—Fe1—S1^v	87.041 (18)	N2Bⁱⁱⁱ—Fe4—S2B	91.5 (4)
S1ⁱⁱ—Fe1—S1^v	87.040 (18)	N2B^iv—Fe4—S2B	176.1 (3)
S1ⁱⁱⁱ—Fe1—S1^v	92.959 (18)	N2B—Fe4—S2Bⁱⁱⁱ	176.1 (3)
S1—Fe1—S1^v	92.960 (18)	N2Bⁱⁱⁱ—Fe4—S2Bⁱⁱⁱ	87.3 (3)
S1^iv—Fe1—S1^v	180.0	N2B^iv—Fe4—S2Bⁱⁱⁱ	91.5 (4)
N1—Fe2—N1ⁱⁱⁱ	93.02 (7)	S2B—Fe4—S2Bⁱⁱⁱ	88.91 (9)
N1—Fe2—N1^iv	93.02 (7)	N2B—Fe4—S2B^iv	91.5 (4)
N1ⁱⁱⁱ—Fe2—N1^iv	93.02 (7)	N2Bⁱⁱⁱ—Fe4—S2B^iv	176.1 (3)
N1—Fe2—S1ⁱⁱⁱ	91.05 (5)	N2B^iv—Fe4—S2B^iv	87.3 (3)
N1ⁱⁱⁱ—Fe2—S1ⁱⁱⁱ	87.26 (5)	S2B—Fe4—S2B^iv	88.91 (9)
N1^iv—Fe2—S1ⁱⁱⁱ	175.90 (5)	S2Bⁱⁱⁱ—Fe4—S2B^iv	88.91 (9)
N1—Fe2—S1	87.26 (5)	N2—Fe4—S2ⁱⁱⁱ	91.91 (11)
N1ⁱⁱⁱ—Fe2—S1	175.90 (5)	N2ⁱⁱⁱ—Fe4—S2ⁱⁱⁱ	86.94 (11)
N1^iv—Fe2—S1	91.05 (5)	N2^iv—Fe4—S2ⁱⁱⁱ	175.71 (11)
S1ⁱⁱⁱ—Fe2—S1	88.65 (2)	N2—Fe4—S2	86.94 (11)
N1—Fe2—S1^iv	175.90 (5)	N2ⁱⁱⁱ—Fe4—S2	175.71 (11)
N1ⁱⁱⁱ—Fe2—S1^iv	91.05 (5)	N2^iv—Fe4—S2	91.91 (11)
N1^iv—Fe2—S1^iv	87.26 (5)	S2ⁱⁱⁱ—Fe4—S2	88.86 (3)
S1ⁱⁱⁱ—Fe2—S1^iv	88.65 (2)	N2—Fe4—S2^iv	175.71 (11)
S1—Fe2—S1^iv	88.65 (2)	N2ⁱⁱⁱ—Fe4—S2^iv	91.91 (11)
C2—S1—Fe2	96.07 (8)	N2^iv—Fe4—S2^iv	86.94 (11)
C2—S1—Fe1	114.36 (8)	S2ⁱⁱⁱ—Fe4—S2^iv	88.86 (3)
Fe2—S1—Fe1	73.546 (18)	S2—Fe4—S2^iv	88.86 (3)
C1—N1—Fe2	113.33 (14)	C3—S2—Fe4	96.60 (14)
C1—N1—H1	108.9	C3—S2—Fe3	113.93 (15)
Fe2—N1—H1	108.9	Fe4—S2—Fe3	73.27 (2)
C1—N1—H2	108.9	C4—N2—Fe4	114.7 (3)
Fe2—N1—H2	108.9	C4—N2—H7	108.6
H1—N1—H2	107.7	Fe4—N2—H7	108.6
N1—C1—C2	109.46 (17)	C4—N2—H8	108.6
N1—C1—H3	109.8	Fe4—N2—H8	108.6
C2—C1—H3	109.8	H7—N2—H8	107.6
N1—C1—H4	109.8	C4—C3—S2	106.6 (3)
C2—C1—H4	109.8	C4—C3—H9	110.4
H3—C1—H4	108.2	S2—C3—H9	110.4
C1—C2—S1	106.38 (15)	C4—C3—H10	110.4
C1—C2—H5	110.5	S2—C3—H10	110.4
S1—C2—H5	110.5	H9—C3—H10	108.6
C1—C2—H6	110.5	N2—C4—C3	112.4 (4)
S1—C2—H6	110.5	N2—C4—H11	109.1
H5—C2—H6	108.6	C3—C4—H11	109.1
S2B^vi—Fe3—S2B	179.998 (1)	N2—C4—H12	109.1
S2B^vi—Fe3—S2B^iv	93.64 (9)	C3—C4—H12	109.1
S2B—Fe3—S2B^iv	86.37 (9)	H11—C4—H12	107.9
S2B^vi—Fe3—S2Bⁱⁱⁱ	93.64 (9)	C3B—S2B—Fe4	90.9 (5)
S2B—Fe3—S2Bⁱⁱⁱ	86.37 (9)	C3B—S2B—Fe3	108.1 (6)
S2B^iv—Fe3—S2Bⁱⁱⁱ	86.37 (9)	Fe4—S2B—Fe3	73.83 (7)
S2B^vi—Fe3—S2B^vii	86.36 (9)	C4B—N2B—Fe4	112.1 (9)
S2B—Fe3—S2B^vii	93.63 (9)	C4B—N2B—H13	109.2
S2B^iv—Fe3—S2B^vii	180.00 (10)	Fe4—N2B—H13	109.2
S2Bⁱⁱⁱ—Fe3—S2B^vii	93.64 (9)	C4B—N2B—H14	109.2
S2B^vi—Fe3—S2B^viii	86.36 (9)	Fe4—N2B—H14	109.2
S2B—Fe3—S2B^viii	93.63 (9)	H13—N2B—H14	107.9
S2B^iv—Fe3—S2B^viii	93.64 (9)	C4B—C3B—S2B	106.6 (13)
S2Bⁱⁱⁱ—Fe3—S2B^viii	179.998 (1)	C4B—C3B—H15	110.4
S2B^vii—Fe3—S2B^viii	86.36 (9)	S2B—C3B—H15	110.4
S2^viii—Fe3—S2ⁱⁱⁱ	180.00 (5)	C4B—C3B—H16	110.4
S2^viii—Fe3—S2	92.77 (3)	S2B—C3B—H16	110.4
S2ⁱⁱⁱ—Fe3—S2	87.23 (3)	H15—C3B—H16	108.6
S2^viii—Fe3—S2^iv	92.77 (3)	C3B—C4B—N2B	111.5 (14)
S2ⁱⁱⁱ—Fe3—S2^iv	87.23 (3)	C3B—C4B—H17	109.3
S2—Fe3—S2^iv	87.23 (3)	N2B—C4B—H17	109.3
S2^viii—Fe3—S2^vi	87.23 (3)	C3B—C4B—H18	109.3
S2ⁱⁱⁱ—Fe3—S2^vi	92.77 (3)	N2B—C4B—H18	109.3
S2—Fe3—S2^vi	180.0	H17—C4B—H18	108.0
S2^iv—Fe3—S2^vi	92.77 (3)	O3—Cl1—O4	110.49 (15)
S2^viii—Fe3—S2^vii	87.23 (3)	O3—Cl1—O1	109.78 (14)
S2ⁱⁱⁱ—Fe3—S2^vii	92.77 (3)	O4—Cl1—O1	109.85 (13)
S2—Fe3—S2^vii	92.77 (3)	O3—Cl1—O2	109.71 (13)
S2^iv—Fe3—S2^vii	179.999 (1)	O4—Cl1—O2	108.82 (14)
S2^vi—Fe3—S2^vii	87.23 (3)	O1—Cl1—O2	108.16 (12)

N1—Fe2—S1—C2	21.81 (10)	S2^viii—Fe3—S2—Fe4	−136.322 (12)
N1^iv—Fe2—S1—C2	114.79 (9)	S2ⁱⁱⁱ—Fe3—S2—Fe4	43.680 (12)
S1ⁱⁱⁱ—Fe2—S1—C2	−69.30 (8)	S2^iv—Fe3—S2—Fe4	−43.680 (12)
S1^iv—Fe2—S1—C2	−157.98 (8)	S2^vii—Fe3—S2—Fe4	136.320 (12)
N1—Fe2—S1—Fe1	135.45 (5)	N2ⁱⁱⁱ—Fe4—N2—C4	−175.7 (3)
N1^iv—Fe2—S1—Fe1	−131.57 (5)	N2^iv—Fe4—N2—C4	91.9 (4)
S1ⁱⁱⁱ—Fe2—S1—Fe1	44.341 (11)	S2ⁱⁱⁱ—Fe4—N2—C4	−88.6 (3)
S1^iv—Fe2—S1—Fe1	−44.341 (11)	S2—Fe4—N2—C4	0.1 (3)
S1ⁱ—Fe1—S1—C2	−134.32 (9)	Fe4—S2—C3—C4	44.5 (3)
S1ⁱⁱⁱ—Fe1—S1—C2	45.68 (9)	Fe3—S2—C3—C4	119.0 (3)
S1^iv—Fe1—S1—C2	132.87 (8)	Fe4—N2—C4—C3	30.6 (5)
S1^v—Fe1—S1—C2	−47.13 (8)	S2—C3—C4—N2	−51.4 (5)
S1ⁱ—Fe1—S1—Fe2	136.408 (8)	N2B—Fe4—S2B—C3B	27.4 (7)
S1ⁱⁱⁱ—Fe1—S1—Fe2	−43.592 (8)	N2Bⁱⁱⁱ—Fe4—S2B—C3B	119.7 (7)
S1^iv—Fe1—S1—Fe2	43.592 (8)	S2Bⁱⁱⁱ—Fe4—S2B—C3B	−153.1 (6)
S1^v—Fe1—S1—Fe2	−136.406 (8)	S2B^iv—Fe4—S2B—C3B	−64.1 (6)
N1ⁱⁱⁱ—Fe2—N1—C1	−179.13 (15)	N2B—Fe4—S2B—Fe3	136.0 (4)
N1^iv—Fe2—N1—C1	−85.94 (19)	N2Bⁱⁱⁱ—Fe4—S2B—Fe3	−131.7 (3)
S1ⁱⁱⁱ—Fe2—N1—C1	93.56 (15)	S2Bⁱⁱⁱ—Fe4—S2B—Fe3	−44.47 (4)
S1—Fe2—N1—C1	4.96 (15)	S2B^iv—Fe4—S2B—Fe3	44.47 (4)
Fe2—N1—C1—C2	−37.5 (2)	S2B^iv—Fe3—S2B—C3B	42.2 (5)
N1—C1—C2—S1	57.4 (2)	S2Bⁱⁱⁱ—Fe3—S2B—C3B	128.8 (5)
Fe2—S1—C2—C1	−46.89 (16)	S2B^vii—Fe3—S2B—C3B	−137.8 (5)
Fe1—S1—C2—C1	−121.55 (14)	S2B^viii—Fe3—S2B—C3B	−51.2 (5)
N2—Fe4—S2—C3	−23.37 (18)	S2B^iv—Fe3—S2B—Fe4	−43.29 (4)
N2^iv—Fe4—S2—C3	−115.61 (18)	S2Bⁱⁱⁱ—Fe3—S2B—Fe4	43.29 (4)
S2ⁱⁱⁱ—Fe4—S2—C3	68.61 (15)	S2B^vii—Fe3—S2B—Fe4	136.71 (4)
S2^iv—Fe4—S2—C3	157.50 (15)	S2B^viii—Fe3—S2B—Fe4	−136.71 (4)
N2—Fe4—S2—Fe3	−136.42 (10)	N2Bⁱⁱⁱ—Fe4—N2B—C4B	−96.9 (14)
N2^iv—Fe4—S2—Fe3	131.34 (11)	N2B^iv—Fe4—N2B—C4B	170.6 (12)
S2ⁱⁱⁱ—Fe4—S2—Fe3	−44.441 (14)	S2B—Fe4—N2B—C4B	−5.5 (11)
S2^iv—Fe4—S2—Fe3	44.441 (14)	S2B^iv—Fe4—N2B—C4B	83.3 (11)
S2^viii—Fe3—S2—C3	133.80 (16)	Fe4—S2B—C3B—C4B	−54.2 (13)
S2ⁱⁱⁱ—Fe3—S2—C3	−46.20 (16)	Fe3—S2B—C3B—C4B	−127.5 (12)
S2^iv—Fe3—S2—C3	−133.55 (16)	S2B—C3B—C4B—N2B	59.4 (18)
S2^vii—Fe3—S2—C3	46.45 (16)	Fe4—N2B—C4B—C3B	−32.3 (19)

Symmetry codes: (i) x−y+2/3, x+1/3, −z+1/3; (ii) −x+2/3, −y+4/3, −z+1/3; (iii) −x+y, −x+1, z; (iv) −y+1, x−y+1, z; (v) y−1/3, −x+y+1/3, −z+1/3; (vi) −x+2/3, −y+4/3, −z+4/3; (vii) y−1/3, −x+y+1/3, −z+4/3; (viii) x−y+2/3, x+1/3, −z+4/3.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.92	2.28	3.130 (3)	154
N1—H2···O3^ix	0.92	2.40	3.162 (3)	140
N2—H7···O1ⁱⁱⁱ	0.92	2.30	3.110 (4)	147
N2—H8···O2	0.92	2.39	3.274 (4)	161
N2B—H13···O2	0.92	2.41	2.984 (12)	121
N2B—H14···O1	0.92	2.27	3.112 (11)	152

Symmetry codes: (iii) −x+y, −x+1, z; (ix) x−y+1/3, x+2/3, −z+2/3.

Experimental details

Crystal data
Chemical formula	[Fe₃(C₂H₆NS)₆](ClO₄)₃
M_r	922.73
Crystal system, space group	Trigonal, R3
Temperature (K)	200
a, c (Å)	14.2852 (6), 26.2187 (8)
V (Å³)	4633.6 (2)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	2.12
Crystal size (mm)	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.677, 0.816
No. of measured, independent and observed [I > 2σ(I)] reflections	15327, 2365, 2144
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.100, 1.39
No. of reflections	2365
No. of parameters	165
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.09, −0.31

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), Yadokari-XG (Wakita, 2000).

Selected geometric parameters (Å, º) top

Fe1—S1	2.2764 (5)	Fe4—N2	2.026 (4)
Fe2—N1	2.0482 (18)	Fe4—N2B	2.059 (11)
Fe2—S1	2.2434 (6)	Fe4—S2B	2.229 (2)
Fe3—S2B	2.281 (2)	Fe4—S2	2.2535 (8)
Fe3—S2	2.2869 (7)

N1—Fe2—S1ⁱ	175.90 (5)	N2—Fe4—S2ⁱ	175.71 (11)
Fe2—S1—Fe1	73.546 (18)	Fe4—S2—Fe3	73.27 (2)
N2B—Fe4—S2Bⁱⁱ	176.1 (3)	Fe4—S2B—Fe3	73.83 (7)

Symmetry codes: (i) −y+1, x−y+1, z; (ii) −x+y, −x+1, z.