metal-organic compounds
Acta Crystallographica Section E

Experimental

Structure Reports
OnlineCrystal data

ISSN 1600-5368

Bis(triethylammonium) bis(l-pyrazine2,3-dithiolato)bis(pyrazine-2,3-dithiolato)diferrate(III) methanol disolvate
Toshiki Yamaguchi, Shigeyuki Masaoka and Ken Sakai*
Department of Chemistry, Faculty of Science, Kyushu University, Hakozaki 6-10-1,
Higashi-ku, Fukuoka 812-8581, Japan
Correspondence e-mail: ksakai@chem.kyushu-univ.jp
Received 1 December 2008; accepted 10 December 2008
Key indicators: single-crystal X-ray study; T = 100 K; mean (C–C) = 0.002 Å;
R factor = 0.021; wR factor = 0.054; data-to-parameter ratio = 16.9.

In the title compound, (C6H16N)2[Fe2(C4H2N2S2)4]2CH4O,
the [FeIII(pdt)2] anion (pdt is pyrazine-2,3-dithiolate) forms acentrosymmetric dimer supported by two FeIII—S bonds [Fe—S = 2.4787 (4) Å]. In the crystal structure, dimers form a onedimensional stack along the b axis via – stacking interactions, the interplanar separation between adjacent dimers
being 3.51 (2) Å. The methanol solvent molecule is involved in
two hydrogen bonds in which the hydroxyl group acts as ahydrogen-bond donor to the N atom of a pdt ligand and the O
atom acts as an acceptor for the NH group of the triethylammonium cation.

(C6H16N)2[Fe2(C4H2N2S2)4]2CH4O
Mr = 949.04
Monoclinic, P21 =n
a = 14.2375 (15) Å
b = 7.9500 (8) Å
c = 17.7456 (18) Å = 95.293 (1)V = 2000.0 (4) Å3
Z=2
Mo K radiation
 = 1.19 mm1
T = 100 (2) K
0.33  0.18  0.16 mm

Data collection
10059 measured reflections
4048 independent reflections
3824 reflections with I > 2(I)Rint = 0.013

Bruker SMART APEX CCDdetector diffractometer
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)
Tmin = 0.695, Tmax = 0.831

Refinement
R[F 2 > 2(F 2)] = 0.021
wR(F 2) = 0.054
S = 1.074048 reflections

240 parameters
H-atom parameters constrainedmax = 0.40 e Å3
min = 0.19 e Å3

Table 1
Hydrogen-bond geometry (Å,  ).
D—H  A
O1—H24  N3
N5—H20  O1

i

D—H

H  AD  A

D—H  A

0.84
0.93

1.99
1.86

2.8014 (17)2.7880 (17)

163
172

Symmetry code: (i) x þ 1; y þ 2; z.

Related literature

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT(Bruker, 2007); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics: KENX
(Sakai, 2004); software used to prepare material for publication:
SHELXL97, TEXSAN (Molecular Structure Corporation, 2001),
KENX and ORTEPII (Johnson, 1976).

For background information, see: Adams (1990); Frey (2002);
Georgakaki et al. (2003); Gloaguen et al. (2001); Liu et al.
(2005); Nicolet et al. (1999); Peters et al. (1998); Sakata (2000);
Sun et al. (2005); Trasatti (1972); Yamaguchi et al. (2008). For
other iron(III)–dithiolene complexes, see: Simao et al. (2006);
Yamaguchi et al. (2008). For the synthesis, see: Ribas et al.
(2004).

This work was supported in part by a Grant-in-Aid for
Scientific Research (A) (No. 17205008), a Grant-in-Aid forSpecially Promoted Research (No. 18002016), and a Grant-inAid for the Global COE Program (‘Science for Future
Molecular Systems’) from the Ministry of Education, Culture,
Sports, Science and Technology of Japan.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: LH2741).

References
Adams, M. W. W. (1990). Biochim. Biophys. Acta, 1020, 115–145.
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin,
USA.
Frey, M. (2002). ChemBioChem, 3, 153–160.
Georgakaki, I. P., Thomson, L. M., Lyon, E. J., Hall, M. B. & Darensbourg, M.
Y. (2003). Coord. Chem. Rev. 238–239, 255–266.
Gloaguen, F., Lawrence, J. D. & Rauchfuss, T. B. (2001). J. Am. Chem. Soc. 123,
9476–9477.
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National
Laboratory, Tennessee, USA.
Liu, X., Ibrahim, S. K., Tard, C. & Pickett, C. J. (2005). Coord. Chem. Rev. 249,
1641–1652.

Acta Cryst. (2009). E65, m77–m78

doi:10.1107/S1600536808041949

Yamaguchi et al.

m77metal-organic compounds
Molecular Structure Corporation (2001). TEXSAN. MSC, The Woodlands,
Texas, USA.
Nicolet, Y., Piras, C., Legrand, P., Hatchikian, C. E. & Fontecilla-Camps, J. C.
(1999). Structure, 7, 13–23.
Peters, J. W., Lanzilotta, W. N., Lemon, B. J. & Seefeldt, L. C. (1998). Science,
282, 1853–1858.
Ribas, X., Dias, J. C., Morgado, J., Wurst, K., Molins, E., Ruiz, E., Almeida, M.,
Veciana, J. & Rovira, C. (2004). Chem. Eur. J. 10, 1691–1704.
Sakai, K. (2004). KENX. Kyushu University, Japan.

m78

Yamaguchi et al.  (C6H16N)2[Fe2(C4H2N2S2)4]2CH4O

Sakata, T. (2000). Bull. Chem. Soc. Jpn, 73, 297–305.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Simao, D., Ayllón, J. A., Rabaça, S., Figueira, M. J., Santos, I. C., Henriques, R.
T. & Almeida, M. (2006). CrystEngComm, 8, 658–661.
Sun, L., Åkermark, B. & Ott, S. (2005). Coord. Chem. Rev. 249, 1653–1663.
Trasatti, S. (1972). J. Electroanal. Chem. 39, 163–184.
Yamaguchi, T., Masaoka, S. & Sakai, K. (2008). Acta Cryst. E64, m1557–
m1558.

Acta Cryst. (2009). E65, m77–m78

supplementary materials

supplementary materials
Acta Cryst. (2009). E65, m77-m78

Bis(triethylammonium)methanol disolvate[ doi:10.1107/S1600536808041949 ]bis( -pyrazine-2,3-dithiolato)bis(pyrazine-2,3-dithiolato)diferrate(III)T. Yamaguchi, S. Masaoka and K. Sakai
Comment
The Fe2S2 clusters (i.e., H-clusters) in Fe-only hydrogenases (FeHases) are known to be highly active as catalysts towards
H2-evolving (HE) reaction (Adams, 1990; Peters et al., 1998; Nicolet et al., 1999; Frey, 2002). In contrast, metal ironitself exhibits much lower catalytic activity toward HE reaction than does platinum (Trasatti, 1972; Sakata, 2000). A large
variety of structural and functional models of FeHases have been developed and their HE activities have been evaluatedso far (Gloaguen et al., 2001; Georgakaki et al., 2003; Liu et al., 2005; Sun et al., 2005). On the other hand, an air-stabledi-iron complex with a bio-relevant Fe2(µ-S)2 core, [FeIII(mnt)2]22- (mnt = maleonitriledithiolate), was found to serve as
an electrode catalyst towards HE reaction in aqueous media (Yamaguchi et al., unpublished results). In the present study,[FeIII(pdt)2]22- has been synthesized to develop the more highly effective HE catalysts with a bio-relevant Fe2(µ-S)2 core.
The pdt ligand has been selected to examine the effect of introducing N(imine) donor in close proximity to the active centerof the HE reaction. The HE activity of (I) will be separately reported elsewhere (Yamaguchi et al., unpublished results).
The [FeIII(pdt)2]- anions form a dimer in the crystal with an inversion center located at the center of the dimer (Figure 1). The monomer-monomer association is supported by two crystallographically equivalent FeIII—S bonds [Fe1—S1i= 2.4787 (4) Å; symmetry code: (i) 1 - x, 2 - y, -z]. This structural feature well resembles those observed for otheriron(III)-dithiolene complexes as follows. The above intermonomer Fe—S distance is quite comparable to those reportedfor (Ph4As)2[FeIII(qdt)2]2 (qdt = quinoxaline-2,3-dithiolate) [Fe—S = 2.4884 (13) Å] (Simao et al., 2006) and [FeII(15crown-5)(OH2)2][FeIII(mnt)2]2.2(15-crown-5) [Fe—S = 2.4715 (9) and 2.4452 (9) Å] (Yamaguchi et al., 2008). The FeIII
ion is considered to have a distorted square pyramidal stereochemistry; the FeIII ion is ligated by four sulfur atoms withshorter Fe—S distances [2.2264 (4)–2.2367 (4) Å] and axially ligated by a sulfur atom from the adjacent monomer with alonger Fe—S distance [2.4787 (4) Å]. Atom Fe1 is shifted out of the least-squares plane defined with four atoms S1—S4
by 0.3719 (3) Å, even though the four-atom r.m.s. deviation given in the calculation was 0.0650 Å.
The methanol molecule is stabilized with two different types of hydrogen bonding interactions (Figure 2). One type ofhydrogen bond is formed between the hydroxyl unit of methanol and the nitrogen atom of pdt [O1—N3i = 2.8014 (17) Å;symmetry code: (i) 1 - x, 2 - y, -z]. The other is formed between the N—H group of the triethylammonium cation and theoxygen atom of methanol [O1—N5 = 2.7880 (17) Å].
Finally, the anion forms a one-dimensional stack along the b axis (Figure 3). The stack of anions is stabilized with a
π-π interaction formed between two adjacent pdt moieties. As shown in Figure 4, a set of atoms S1—S2/C1—C4/N1—N2
and that of atoms S1ii, C1ii, and N1ii contribute to the π-π association at each interdimer association [symmetry code: (ii) 1- x, 1 - y, -z]. The interplanar separation is calculated as 3.51 (2) Å based on the average shift of atoms S1ii, C1ii, and N1ii

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supplementary materials
from the best plane defined by atoms S1—S2/C1—C4/N1—N2. An important short contact at this geometry is C1—C1ii= 3.493 (3) Å [symmetry code: (ii) 1 - x, 1 - y, -z].
Experimental
Compound (I) was prepared as follows. Pyrazine-2,3-dithiol was prepared as previously described (Ribas et al., 2004). To asuspension of pyrazine-2,3-dithiol (0.146 g, 1.0 mmol) and triethylamine (0.42 ml, 3.0 mmol) in dry tetrahydrofuran (THF,
50 ml) was slowly added a solution of FeCl3.6H2O (0.137 g, 0.5 mmol) in dry THF (5 ml) under Ar atmosphere. Although adark-brown solid immediately precipitated, the suspension was stirred at room temperature for 18 h. The dark-brown solid
deposited was collected by filtration and washed with THF. The crude material was re-dissolved in a minimum amountof methanol followed by filtration for the removal of insoluble materials. Standing of the filtrate at room temperature forseveral days afforded the black needles of (I), which were collected by filtration, washed with cold methanol, and dried invacuo. Yield: 0.098 g (41%). Single crystals of (I) suitable for X-ray crystallography were grown by slow diffusion of diethyl
ether into a methanol solution of (I). Analysis calculated for C30H48Fe2N10O2S8: C, 37.97; H, 5.10; N, 14.76. Found: C,
38.04; H, 4.98; N, 15.04. IR (ν, cm-1): 3028 (w), 2672 (w), 1531 (m), 1449 (m), 1416 (m), 1394 (m), 1320 (s), 1287 (m),1196 (w), 1175 (m), 1144 (s), 1064 (m), 1045 (m), 1005 (m), 837 (m), 825 (s), 791 (m), 485 (m), 475 (m), 449 (s), 421 (m).
Refinement
All H atoms were placed in idealized position (ring C—H = 0.95 Å, methyl C—H = 0.98 Å, methylene C—H = 0.99 Å,hydroxyl O—H = 0.84 Å and tertiary N—H = 0.93 Å), and included in the refinement in a riding-model approximation,with Uiso(H) = 1.2Ueq (ring C, methylene C and tertiary N) and Uiso(H) = 1.5Ueq (methyl C and hydroxyl O). In the final
Fourier map, the highest peak was located 0.99 Å from atom S4. The deepest hole was located 0.53 Å from atom Fe1.

FiguresFig. 1. The molecular structure of a [FeIII(pdt)2]22-, dimer, showing the atom-labeling scheme[symmetry code: (i) 1 - x, 2 - y, -z]. Hydrogen atoms are omitted for clarity. Thermal ellipsoids are drawn at the 50% probability.

Fig. 2. The molecular structure of (Et3NH)[FeIII(pdt)2].MeOH, showing how the hydrogenbonds are formed [symmetry code: (i) 1 - x, 2 - y, -z]. Hydrogen atoms except for those of
N—H and O—H are omitted for clarity. Thermal ellipsoids are drawn at the 50% probability.

Fig. 3. A view down the b axis, showing the manner how the anions stack along the b axis to
give one-dimensional chains. Hydrogen atoms are omitted for clarity. Thermal ellipsoids are
drawn at the 50% probability.

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supplementary materials

Fig. 4. A view perpendicular to the plane defined by atoms S1—S2/C1—C4/N1—N2 which

has a weak π-stack to the plane defined by atoms S1ii, C1ii, and N1ii [Symmetry code: (ii) 1 x, 1 - y, -z]. Hydrogen atoms are omitted for clarity. Thermal ellipsoids are drawn at the 50%
probability.

Bis(triethylammonium) bis(µ-pyrazine-2,3-dithiolato)bis(pyrazine-2,3-dithiolato)diferrate(III) methanol disolvate
Crystal data
(C6H16N)2[Fe2(C4H2N2S2)4]·2CH4O

F000 = 988

Mr = 949.04

Dx = 1.576 Mg m−3

Monoclinic, P21/n
Hall symbol: -P 2yn
a = 14.2375 (15) Å
b = 7.9500 (8) Åc = 17.7456 (18) Å
β = 95.293 (1)ºV = 2000.0 (4) Å3
Z=2

Mo Kα radiation
λ = 0.71073 Å
Cell parameters from 7956 reflections
θ = 2.3–27.5ºµ = 1.19 mm−1
T = 100 (2) K
Needles, black
0.33 × 0.18 × 0.16 mm

Data collection
Bruker SMART APEX CCD-detector diffractometer 4048 independent reflections
Radiation source: rotating anode with a mirror focus3824 reflections with I > 2σ(I)ing unit
Rint = 0.013
Monochromator: graphite
T = 100(2) Kθmax = 26.4º

φ and ω scans

θmin = 2.3º

Absorption correction: multi-scan(SADABS; Sheldrick, 1996)
Tmin = 0.695, Tmax = 0.831
10059 measured reflections

h = −16→17
k = −9→9l = −22→14

Refinement
Refinement on F2

Secondary atom site location: difference Fourier map

Least-squares matrix: fullHydrogen site location: inferred from neighbouring
sites

R[F2 > 2σ(F2)] = 0.021

H-atom parameters constrained

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supplementary materials
w = 1/[σ2(Fo2) + (0.0258P)2 + 1.2723P]

wR(F2) = 0.054

where P = (Fo2 + 2Fc2)/3

S = 1.07(Δ/σ)max = 0.001

4048 reflections

Δρmax = 0.40 e Å−3

240 parametersΔρmin = −0.19 e Å−3Primary atom site location: structure-invariant direct
Extinction coefficient: ?
methods

Special details
Experimental. The first 50 frames were rescanned at the end of data collection to evaluate any possible decay phenomenon. Since it
was judged to be negligible, no decay correction was applied to the data.
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 ofcell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)
4.6834 (0.0016) x + 6.8874 (0.0009) y - 7.1795 (0.0020) z = 7.7711 (0.0010)* 0.0655 (0.0002) S1 * -0.0639 (0.0002) S2 * 0.0645 (0.0002) S3 * -0.0661 (0.0002) S4 0.3719 (0.0003) Fe1
Rms deviation of fitted atoms = 0.0650
Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)
5.7097 (0.0038) x + 6.0721 (0.0015) y - 9.5934 (0.0044) z = 7.6443 (0.0017)* 0.0277 (0.0006) S1 * -0.0176 (0.0006) S2 * -0.0098 (0.0012) C1 * -0.0122 (0.0011) C2 * -0.0067 (0.0012) C3 * 0.0190 (0.0011)
C4 * -0.0173 (0.0010) N1 * 0.0170 (0.0010) N2 - 3.5344 (0.0008) S1_$2 - 3.4970 (0.0017) C1_$2 - 3.4894 (0.0014) N1_$2
Rms deviation of fitted atoms = 0.0170
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 Rfactors(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)
Fe1
S1
S2
S3
S4
O1
H24
N1

sup-4

x

y

z

Uiso*/Ueq

0.404540 (13)0.54285 (2)0.35609 (2)0.25466 (2)0.43700 (2)0.89754 (8)0.87670.61230 (9)0.93135 (3)0.79904 (4)0.79099 (5)1.00013 (5)0.97513 (4)0.60915 (14)0.68380.57967 (15)0.023150 (11)0.029127 (18)−0.082403 (19)0.034182 (19)0.147331 (18)−0.01530 (6)−0.0459−0.06370 (7)0.01057 (6)0.01130 (8)0.01420 (8)0.01363 (8)0.01193 (8)0.0209 (2)0.031*
0.0151 (3)supplementary materials
N2
N3
N4
N5
H20
C1
C2
H1
C3
C4
H2
C5
C6
H3
C7
C8
H4
C9
H5
H6
C10
H7
H8
H9
C11
H10
H11
C12
H13
H12
H14
C13
H16
H15
C14
H19
H18
H17
C16
H21
H22
H23

0.44848 (9)0.18638 (8)0.34506 (9)0.86540 (8)0.88190.53659 (10)0.60532 (11)0.65710.45350 (10)0.52528 (11)0.52460.26017 (10)0.19204 (10)0.1412
0.34105 (10)0.26953 (10)0.26960.92078 (11)0.89090.98560.92556 (12)0.86150.95830.95990.76030 (10)0.74710.72890.71813 (11)0.75300.65180.72230.89199 (11)0.89500.84280.98672 (13)1.03621.00040.98460.85896 (13)0.86000.79380.89680.57864 (16)1.19999 (16)
1.16211 (16)0.70235 (16)0.67060.67055 (18)0.48707 (19)0.41840.67025 (18)0.48836 (19)0.4224
1.10755 (18)1.27363 (19)1.3416
1.09206 (18)1.25302 (19)1.30470.5916 (2)0.5936
0.6366
0.4119 (2)0.36870.34230.4082
0.6761 (2)0.55380.72590.7525 (2)0.71270.71890.87540.8848 (2)0.91410.95570.9219 (2)0.85781.04250.88940.4489 (2)0.43780.4406
0.3588−0.16542 (7)0.13603 (7)0.24079 (7)0.13156 (7)0.0841−0.05203 (8)−0.12700 (9)−0.1377−0.10198 (8)−0.17707 (8)−0.22180.12000 (8)0.20475 (8)0.21790.17242 (8)0.25642 (8)0.30470.18858 (8)0.23680.19850.16109 (9)0.14890.20080.11580.13087 (9)0.12960.08400.19835 (9)0.24510.1977
0.19580.14175 (9)0.19610.11440.11225 (10)0.1416
0.11730.0589−0.03924 (10)−0.0942−0.0260−0.01390.0163 (3)0.0147 (2)0.0141 (2)0.0151 (3)0.018*
0.0122 (3)0.0171 (3)0.021*
0.0132 (3)0.0178 (3)0.021*
0.0124 (3)0.0167 (3)0.020*
0.0119 (3)0.0161 (3)0.019*
0.0181 (3)0.022*
0.022*
0.0229 (3)0.034*
0.034*
0.034*
0.0197 (3)0.024*
0.024*
0.0253 (4)0.038*
0.038*
0.038*
0.0193 (3)0.023*
0.023*
0.0283 (4)0.042*
0.042*
0.042*
0.0263 (4)0.040*
0.040*
0.040*

Atomic displacement parameters (Å2)
Fe1
S1

U11
0.01022 (10)0.01119 (16)U220.01220 (11)0.01259 (17)U33
0.00912 (10)0.00985 (15)U120.00046 (7)0.00098 (12)U130.00004 (7)−0.00040 (12)U23−0.00049 (7)−0.00008 (12)sup-5

supplementary materials
S2
S3
S4
O1
N1
N2
N3
N4
N5
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C16

0.01256 (17)0.01063 (16)0.01160 (16)0.0232 (6)0.0165 (6)0.0208 (6)0.0138 (6)0.0167 (6)0.0136 (6)0.0151 (7)0.0192 (7)0.0156 (7)0.0253 (8)0.0133 (7)0.0164 (7)0.0137 (7)0.0197 (7)0.0147 (7)0.0240 (8)0.0122 (7)0.0169 (8)0.0208 (8)0.0294 (9)0.0303 (9)0.01665 (18)0.01853 (19)0.01452 (17)0.0213 (6)0.0126 (6)0.0141 (6)0.0149 (6)0.0131 (6)0.0187 (7)0.0104 (7)0.0120 (7)0.0109 (7)0.0129 (7)0.0120 (7)0.0158 (7)0.0101 (7)0.0156 (7)0.0233 (8)0.0231 (9)0.0259 (8)0.0336 (9)0.0184 (8)0.0274 (9)0.0248 (9)0.01285 (16)0.01144 (16)0.00948 (16)0.0173 (5)0.0166 (6)0.0140 (6)0.0156 (6)0.0125 (6)0.0124 (6)0.0111 (6)0.0211 (7)0.0132 (6)0.0157 (7)0.0122 (6)0.0183 (7)0.0120 (6)0.0134 (7)0.0155 (7)0.0207 (8)0.0201 (7)0.0255 (8)0.0177 (7)0.0283 (9)0.0228 (8)0.00100 (13)0.00053 (13)0.00168 (13)0.0043 (5)0.0007 (5)−0.0008 (5)−0.0002 (5)0.0002 (5)0.0002 (5)−0.0007 (5)0.0014 (6)−0.0008 (5)0.0000 (6)−0.0016 (5)0.0017 (6)−0.0013 (5)0.0003 (6)0.0015 (6)0.0039 (6)−0.0001 (6)0.0008 (7)−0.0012 (6)−0.0089 (7)0.0009 (7)−0.00173 (13)−0.00050 (12)0.00002 (12)−0.0036 (4)0.0039 (5)0.0009 (5)0.0020 (5)0.0017 (5)−0.0013 (5)0.0019 (5)0.0067 (6)0.0020 (5)0.0053 (6)0.0023 (5)0.0043 (6)0.0018 (5)0.0035 (6)−0.0036 (6)−0.0017 (6)−0.0033 (6)0.0028 (6)−0.0033 (6)0.0048 (7)−0.0038 (7)−0.00337 (13)−0.00270 (13)0.00010 (12)−0.0003 (4)0.0010 (5)−0.0018 (5)−0.0004 (5)−0.0004 (5)0.0010 (5)0.0008 (5)−0.0012 (6)0.0010 (5)−0.0027 (6)0.0011 (5)−0.0013 (6)0.0019 (5)−0.0017 (5)0.0039 (6)0.0045 (6)0.0002 (6)−0.0024 (7)0.0001 (6)−0.0002 (7)−0.0038 (7)Geometric parameters (Å, °)Fe1—S1Fe1—S3
Fe1—S2
Fe1—S42.2264 (4)2.2289 (4)2.2341 (4)2.2367 (4)C9—C10C11—C12
C13—C14N5—H201.513 (2)1.515 (2)1.520 (2)0.9300Fe1—S1i
S1—C1

2.4787 (4)C2—H1

0.95001.7611 (14)C4—H20.9500i

2.4787 (4)C6—H30.95001.7477 (15)1.7415 (14)1.7438 (14)1.436 (2)0.84001.3297 (19)1.339 (2)1.3372 (19)1.340 (2)1.3341 (19)1.3483 (19)1.3315 (18)1.3456 (19)1.506 (2)1.5079 (18)

C8—H4
C9—H5
C9—H6
C10—H7
C10—H8C10—H9C11—H10
C11—H11C12—H13C12—H12C12—H14
C13—H16
C13—H15
C14—H19
C14—H180.95000.99000.99000.98000.98000.98000.99000.99000.98000.98000.98000.99000.99000.98000.9800S1—Fe1
S2—C3
S3—C5
S4—C7
O1—C16
O1—H24
N1—C1
N1—C2
N2—C3
N2—C4
N3—C5
N3—C6
N4—C7
N4—C8
N5—C13
N5—C9

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supplementary materials
N5—C11
C1—C3
C2—C4
C5—C7
C6—C8

1.5097 (19)1.411 (2)1.379 (2)1.417 (2)1.378 (2)

C14—H17
C16—H21
C16—H22
C16—H230.98000.98000.98000.9800C1···C1ii

3.493 (3)S1—Fe1—S3
S1—Fe1—S2
S3—Fe1—S2
S1—Fe1—S4
S3—Fe1—S4
S2—Fe1—S4

164.042 (16)90.420 (15)88.401 (15)85.705 (14)89.299 (14)157.445 (17)C4—C2—H1
N2—C4—H2
C2—C4—H2
N3—C6—H3
C8—C6—H3
N4—C8—H4

119.0
118.6
118.6
119.1
119.1
118.9

S1—Fe1—S1i

97.462 (14)C6—C8—H4

118.9

i98.369 (15)

N5—C9—H5

109.3

S2—Fe1—S1i

101.461 (15)

C10—C9—H5

109.3

S4—Fe1—S1i
C1—S1—Fe1

101.073 (15)

N5—C9—H6

109.3

104.91 (5)C10—C9—H6

109.3

100.94 (5)H5—C9—H6

107.9

82.538 (14)C9—C10—H7

109.5

104.58 (5)103.35 (5)103.82 (5)115.52 (13)116.15 (13)116.71 (12)116.39 (12)111.84 (11)111.85 (12)112.41 (12)123.08 (13)117.51 (11)119.40 (11)121.97 (14)120.42 (13)119.00 (11)120.58 (11)122.84 (14)121.06 (13)118.93 (11)119.98 (11)121.84 (14)121.71 (13)119.13 (11)119.14 (11)122.20 (13)111.80 (12)113.75 (12)C9—C10—H8
H7—C10—H8
C9—C10—H9
H7—C10—H9
H8—C10—H9
N5—C11—H10
C12—C11—H10
N5—C11—H11
C12—C11—H11
H10—C11—H11
C11—C12—H13
C11—C12—H12
H13—C12—H12
C11—C12—H14
H13—C12—H14
H12—C12—H14
N5—C13—H16
C14—C13—H16
N5—C13—H15
C14—C13—H15
H16—C13—H15
C13—C14—H19
C13—C14—H18
H19—C14—H18
C13—C14—H17
H19—C14—H17
H18—C14—H17
O1—C16—H21

109.5
109.5
109.5
109.5
109.5
108.8
108.8
108.8
108.8
107.7
109.5
109.5
109.5
109.5
109.5
109.5
109.3
109.3
109.3
109.3
108.0
109.5
109.5
109.5
109.5
109.5
109.5
109.5

S3—Fe1—S1

i

C1—S1—Fe1i

Fe1—S1—Fe1
C3—S2—Fe1
C5—S3—Fe1
C7—S4—Fe1
C1—N1—C2
C3—N2—C4
C5—N3—C6
C7—N4—C8
C13—N5—C9
C13—N5—C11
C9—N5—C11
N1—C1—C3
N1—C1—S1
C3—C1—S1
N1—C2—C4
N2—C3—C1
N2—C3—S2
C1—C3—S2
N2—C4—C2
N3—C5—C7
N3—C5—S3
C7—C5—S3
N3—C6—C8
N4—C7—C5
N4—C7—S4
C5—C7—S4
N4—C8—C6
N5—C9—C10
N5—C11—C12

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supplementary materials
N5—C13—C14
C16—O1—H24
C13—N5—H20
C9—N5—H20
C11—N5—H20
N1—C2—H1

111.52 (13)
109.5
106.8
106.8
106.8
119.0

O1—C16—H22
H21—C16—H22
O1—C16—H23
H21—C16—H23
H22—C16—H23

109.5
109.5
109.5
109.5
109.5

C2—N1—C1—C3
C2—N1—C1—S1
Fe1—S1—C1—N1

0.5 (2)−178.40 (11)178.17 (10)

Fe1—S3—C5—N3
Fe1—S3—C5—C7
C5—N3—C6—C8

164.68 (10)−17.12 (12)−0.8 (2)Fe1i—S1—C1—N1
Fe1—S1—C1—C3

93.07 (11)C8—N4—C7—C5−2.2 (2)−0.74 (12)C8—N4—C7—S4

178.97 (11)N3—C5—C7—N4

3.2 (2)S3—C5—C7—N4
N3—C5—C7—S4
S3—C5—C7—S4
Fe1—S4—C7—N4
Fe1—S4—C7—C5
C7—N4—C8—C6
N3—C6—C8—N4
C13—N5—C9—C10
C11—N5—C9—C10
C13—N5—C11—C12
C9—N5—C11—C12
C9—N5—C13—C14
C11—N5—C13—C14−174.98 (11)−177.96 (11)3.87 (16)−169.57 (10)11.55 (12)−0.2 (2)
1.8 (2)−156.73 (13)76.48 (16)−52.48 (17)74.31 (17)75.40 (15)−157.50 (13)i−85.84 (11)
Fe1 —S1—C1—C3
C1—N1—C2—C4
0.9 (2)
C4—N2—C3—C1
0.9 (2)
C4—N2—C3—S2−179.75 (11)N1—C1—C3—N2−1.4 (2)S1—C1—C3—N2
177.43 (11)N1—C1—C3—S2
179.20 (11)S1—C1—C3—S2−1.95 (17)
Fe1—S2—C3—N2−175.86 (10)
Fe1—S2—C3—C1
3.53 (12)C3—N2—C4—C2
0.5 (2)
N1—C2—C4—N2−1.5 (2)C6—N3—C5—C7−1.5 (2)C6—N3—C5—S3
176.64 (11)Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, °)D—H···Ai

O1—H24···N3
N5—H20···O1
Symmetry codes: (i) −x+1, −y+2, −z.

sup-8

D—H

H···A

D···A

D—H···A

0.84

1.99

2.8014 (17)

163

0.93

1.86

2.7880 (17)172

supplementary materials
Fig. 1

sup-9

supplementary materials
Fig. 2

sup-10supplementary materials
Fig. 3

sup-11

supplementary materials
Fig. 4sup-12