Crystal structure of tris­(1,10-phenanthroline-κ2N,N′)iron(II) bis­[bis­(tri­fluoro­methyl­sulfon­yl)imide] monohydrate

Teramoto, K.; Kawasaki, T.; Nishide, T.; Ikeda, Y.

doi:10.1107/S2056989014026966

metal-organic compounds

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ISSN: 2056-9890

Volume 71| Part 1| January 2015| Pages m8-m9

https://doi.org/10.1107/S2056989014026966

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Crystal structure of tris(1,10-phenanthroline-κ²N,N′)iron(II) bis[bis(trifluoromethylsulfonyl)imide] monohydrate

Kazunori Teramoto,^a Takeshi Kawasaki,^b Toshikazu Nishide ^a and Yasuhisa Ikeda ^c ^*

^aDepartment of Chemical Biology and Applied Chemistry, College of Engineering, Nihon University, 1 Nakagawara Tokusada Tamura, Koriyama 963-8642, Japan, ^bDepartment of Chemistry, Faculty of Science, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan, and ^cResearch Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1-N1-34 Ookayama, Meguro-ku, Tokyo 152-8550, Japan
^*Correspondence e-mail: yikeda@nr.titech.ac.jp

Edited by M. Weil, Vienna University of Technology, Austria (Received 3 December 2014; accepted 9 December 2014; online 1 January 2015)

The crystal structure of the title complex, [Fe(C₁₂H₈N₂)₃][(CF₃SO₂)₂N]₂·H₂O, is constructed by one octahedral [Fe(phen)₃]²⁺ (phen = 1,10-phenanthroline) cation (point group symmetry 2), two Tf₂N⁻ [bis(trifluoromethylsulfonyl)imide] anions, and one water molecule of crystallization (point group 2). The Fe—N bond lengths are indicative of a d⁶ low-spin state for the Fe^II ion in the complex. The dihedral angle between the phen ligands in the cation is 87.64 (6)°. The Tf₂N⁻ counter-anion is non-coordinating, with the –CF₃ groups arranged in a trans fashion with respect to each other, leading to an anti,anti conformation of the –CF₃ groups and –SO₂N– moieties relative to the S—C bonds. The water molecule of crystallization connects two O atoms of the Tf₂N⁻ anions through weak hydrogen bonds. C—H⋯O hydrogen-bonding interactions are also observed, consolidating the packing of the molecules into a three-dimensional network structure.

Keywords: crystal structure; 1,10-phenanthroline; iron(II) complex; complex salt; bis(trifluoromethylsulfonyl)imide; low-spin d⁶ Fe^II ions; hydrogen bonding.

CCDC reference: 1038289

1. Related literature

For the synthesis of the anhydrous title complex, see: Teramoto et al. (2014 ). For typical Fe—N bond lengths of low-spin d⁶ Fe^II ions, see: Deng et al. (2001 ); Setifi et al. (2013 ). Crystal structures of complexes with the [Fe(phen)₃]²⁺ cation were reported by Koh (1994 ), Potočňák et al. (2014 ) and Zhong (2012 ). In the crystal structure of the ionic liquid choline bis(trifluoromethylsulfonyl)imide (Nockemann et al., 2009 ), the free Tf₂N⁻ anion has a similar conformation to that in the title compound.

2. Experimental

2.1. Crystal data

[Fe(C₁₂H₈N₂)₃](C₂F₆NO₄S₂)₂·H₂O
M_r = 1174.78
Monoclinic, C 2/c
a = 20.7745 (15) Å
b = 16.0107 (12) Å
c = 13.3084 (10) Å
β = 91.657 (1)°
V = 4424.7 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.65 mm⁻¹
T = 100 K
0.42 × 0.11 × 0.10 mm

2.2. Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.773, T_max = 0.938
13659 measured reflections
4910 independent reflections
3247 reflections with I > 2σ(I)
R_int = 0.065

2.3. Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.122
S = 1.02
4910 reflections
338 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.71 e Å⁻³
Δρ_min = −0.90 e Å⁻³

Table 1
Selected bond lengths (Å)

Fe1—N1	1.977 (3)
Fe1—N2	1.974 (3)
Fe1—N3	1.966 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5W⋯O4ⁱ	0.88 (1)	2.23 (6)	2.963 (4)	141 (7)
C2—H2⋯O3ⁱⁱ	0.95	2.50	3.433 (4)	166
C14—H14⋯O2	0.95	2.53	3.481 (5)	174
Symmetry codes: (i) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) -x+1, -y+2, -z+1.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1038289

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989014026966/wm5100sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989014026966/wm5100Isup2.hkl

checkCIF report

Related literature top

For the synthesis of the anhydrous title complex, see: Teramoto et al. (2014). For typical Fe—N bond lengths of low-spin d⁶ Fe^II ions, see: Deng et al. (2001); Setifi et al. (2013). Crystal structures of complexes with the [Fe(phen)₃]²⁺ cation were reported by Koh (1994), Potočňák et al. (2014) and Zhong (2012). In the crystal structure of the ionic liquid choline bis(trifluoromethylsulfonyl)imide (Nockemann et al., 2009), the free Tf₂N^- anion has a similar conformation to that in the title compound.

Experimental top

Red powders of [Fe(phen)₃](Tf₂N)₂ were synthesized as described in the literature by Teramoto et al. (2014). The title complex was crystallized by cooling a hot concentrated aqueous solution of [Fe(phen)₃](Tf₂N)₂ .

Structure description top

For the synthesis of the anhydrous title complex, see: Teramoto et al. (2014). For typical Fe—N bond lengths of low-spin d⁶ Fe^II ions, see: Deng et al. (2001); Setifi et al. (2013). Crystal structures of complexes with the [Fe(phen)₃]²⁺ cation were reported by Koh (1994), Potočňák et al. (2014) and Zhong (2012). In the crystal structure of the ionic liquid choline bis(trifluoromethylsulfonyl)imide (Nockemann et al., 2009), the free Tf₂N^- anion has a similar conformation to that in the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the [Fe(phen)₃]²⁺, Tf₂N^- and H₂O molecular units. Displacement ellipsoids are represented at the 30% probability level. Hydrogen atoms were omitted for clarity. [Symmetry code: i) -x + 1,y,-z + 1/2.]
	Fig. 2. Hydrogen bonds between the H₂O molecule and Tf₂N^- anions. [Symmetry codes: ii) x - 1/2,y - 1/2,z, iii) -x + 3/2, y - 1/2, -z + 3/2.]

Tris(1,10-phenanthroline-κ²N,N')iron(II) bis[bis(trifluoromethylsulfonyl)imide] monohydrate top

Crystal data top

[Fe(C₁₂H₈N₂)₃](C₂F₆NO₄S₂)₂·H₂O	F(000) = 2368
M_r = 1174.78	D_x = 1.764 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1623 reflections
a = 20.7745 (15) Å	θ = 2.2–23.5°
b = 16.0107 (12) Å	µ = 0.65 mm⁻¹
c = 13.3084 (10) Å	T = 100 K
β = 91.657 (1)°	Block, red
V = 4424.7 (6) Å³	0.42 × 0.11 × 0.10 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	4910 independent reflections
Radiation source: fine-focus sealed tube	3247 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
Detector resolution: 8.333 pixels mm^-1	θ_max = 27.2°, θ_min = 1.6°
phi and ω scans	h = −26→24
Absorption correction: multi-scan (SADABS; Bruker, 2007)	k = −17→20
T_min = 0.773, T_max = 0.938	l = −17→16
13659 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0533P)² + 0.4369P] where P = (F_o² + 2F_c²)/3
4910 reflections	(Δ/σ)_max = 0.001
338 parameters	Δρ_max = 0.71 e Å⁻³
2 restraints	Δρ_min = −0.90 e Å⁻³

Crystal data top

[Fe(C₁₂H₈N₂)₃](C₂F₆NO₄S₂)₂·H₂O	V = 4424.7 (6) Å³
M_r = 1174.78	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 20.7745 (15) Å	µ = 0.65 mm⁻¹
b = 16.0107 (12) Å	T = 100 K
c = 13.3084 (10) Å	0.42 × 0.11 × 0.10 mm
β = 91.657 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4910 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	3247 reflections with I > 2σ(I)
T_min = 0.773, T_max = 0.938	R_int = 0.065
13659 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	2 restraints
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.71 e Å⁻³
4910 reflections	Δρ_min = −0.90 e Å⁻³
338 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Fe1	0.5000	0.81145 (4)	0.2500	0.01247 (17)
S1	0.70284 (4)	0.87060 (6)	0.73999 (6)	0.0194 (2)
S2	0.81435 (4)	0.96272 (6)	0.78549 (6)	0.0190 (2)
N1	0.41901 (12)	0.80991 (17)	0.32441 (19)	0.0128 (6)
N2	0.52464 (12)	0.72317 (17)	0.34722 (19)	0.0136 (6)
N3	0.53087 (12)	0.90330 (18)	0.33681 (19)	0.0141 (6)
N4	0.77157 (14)	0.88188 (19)	0.7924 (2)	0.0231 (7)
O1	0.66576 (12)	0.81717 (18)	0.80049 (19)	0.0320 (7)
O2	0.67338 (11)	0.94387 (16)	0.69810 (18)	0.0243 (6)
O3	0.80627 (11)	1.01191 (16)	0.69622 (17)	0.0235 (6)
O4	0.87849 (11)	0.94170 (17)	0.81960 (19)	0.0264 (6)
O5	0.5000	0.5160 (4)	0.7500	0.102 (2)
H5W	0.4670 (6)	0.4824 (12)	0.742 (7)	0.153*
F1	0.75397 (11)	0.73840 (14)	0.65849 (17)	0.0369 (6)
F2	0.75628 (11)	0.84768 (16)	0.56672 (17)	0.0409 (6)
F3	0.66724 (10)	0.78257 (14)	0.58392 (17)	0.0343 (6)
F4	0.78834 (11)	0.98981 (14)	0.97358 (15)	0.0318 (6)
F5	0.82027 (10)	1.09733 (13)	0.89196 (16)	0.0281 (5)
F6	0.72349 (9)	1.05100 (14)	0.86804 (15)	0.0283 (5)
C1	0.36704 (15)	0.8593 (2)	0.3148 (2)	0.0150 (7)
H1	0.3646	0.8974	0.2601	0.018*
C2	0.31626 (16)	0.8573 (2)	0.3816 (2)	0.0175 (8)
H2	0.2807	0.8941	0.3725	0.021*
C3	0.31802 (15)	0.8018 (2)	0.4603 (3)	0.0177 (8)
H3	0.2841	0.8008	0.5067	0.021*
C4	0.37042 (16)	0.7465 (2)	0.4717 (2)	0.0160 (7)
C5	0.42054 (15)	0.7547 (2)	0.4026 (2)	0.0143 (7)
C6	0.37791 (16)	0.6843 (2)	0.5492 (3)	0.0190 (8)
H6	0.3445	0.6769	0.5956	0.023*
C7	0.43081 (16)	0.6365 (2)	0.5575 (2)	0.0197 (8)
H7	0.4339	0.5955	0.6090	0.024*
C8	0.47740 (15)	0.7066 (2)	0.4134 (2)	0.0153 (7)
C9	0.48305 (16)	0.6464 (2)	0.4898 (2)	0.0164 (7)
C10	0.54083 (16)	0.5999 (2)	0.4945 (3)	0.0206 (8)
H10	0.5475	0.5585	0.5449	0.025*
C11	0.58709 (17)	0.6152 (2)	0.4258 (2)	0.0193 (8)
H11	0.6255	0.5830	0.4268	0.023*
C12	0.57795 (16)	0.6777 (2)	0.3545 (2)	0.0173 (8)
H12	0.6114	0.6884	0.3090	0.021*
C13	0.56412 (15)	0.9013 (2)	0.4249 (2)	0.0177 (8)
H13	0.5741	0.8486	0.4542	0.021*
C14	0.58467 (16)	0.9738 (2)	0.4751 (3)	0.0199 (8)
H14	0.6086	0.9698	0.5368	0.024*
C15	0.57025 (16)	1.0499 (2)	0.4352 (3)	0.0209 (8)
H15	0.5840	1.0993	0.4692	0.025*
C16	0.53488 (16)	1.0558 (2)	0.3435 (3)	0.0178 (8)
C17	0.51693 (15)	0.9803 (2)	0.2973 (2)	0.0153 (7)
C18	0.51659 (16)	1.1325 (2)	0.2942 (3)	0.0214 (8)
H18	0.5282	1.1843	0.3246	0.026*
C19	0.72140 (18)	0.8058 (2)	0.6315 (3)	0.0236 (8)
C20	0.78431 (17)	1.0287 (2)	0.8856 (3)	0.0213 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0125 (3)	0.0142 (4)	0.0107 (3)	0.000	0.0000 (3)	0.000
S1	0.0223 (5)	0.0212 (5)	0.0148 (4)	0.0016 (4)	−0.0001 (4)	0.0002 (4)
S2	0.0201 (5)	0.0208 (5)	0.0161 (4)	0.0048 (4)	−0.0013 (4)	−0.0022 (4)
N1	0.0138 (14)	0.0118 (15)	0.0125 (14)	−0.0030 (12)	−0.0016 (11)	−0.0011 (11)
N2	0.0119 (14)	0.0160 (16)	0.0128 (14)	0.0010 (12)	−0.0006 (11)	−0.0017 (12)
N3	0.0112 (13)	0.0188 (16)	0.0124 (14)	0.0001 (12)	0.0017 (11)	−0.0010 (12)
N4	0.0255 (16)	0.0209 (18)	0.0223 (16)	0.0033 (14)	−0.0104 (14)	−0.0022 (13)
O1	0.0329 (15)	0.0405 (19)	0.0229 (14)	−0.0055 (13)	0.0053 (12)	0.0070 (13)
O2	0.0242 (13)	0.0233 (16)	0.0249 (14)	0.0049 (11)	−0.0071 (11)	−0.0013 (11)
O3	0.0247 (13)	0.0297 (16)	0.0162 (13)	0.0038 (11)	0.0001 (11)	0.0037 (11)
O4	0.0198 (13)	0.0316 (17)	0.0276 (14)	0.0076 (12)	−0.0043 (11)	−0.0029 (12)
O5	0.088 (5)	0.098 (6)	0.120 (6)	0.000	−0.005 (5)	0.000
F1	0.0399 (14)	0.0241 (14)	0.0461 (15)	0.0071 (11)	−0.0105 (12)	−0.0124 (11)
F2	0.0504 (15)	0.0476 (17)	0.0257 (12)	−0.0160 (12)	0.0163 (12)	−0.0074 (11)
F3	0.0352 (13)	0.0325 (14)	0.0343 (13)	−0.0027 (11)	−0.0124 (11)	−0.0101 (11)
F4	0.0465 (14)	0.0333 (14)	0.0153 (11)	0.0019 (11)	−0.0021 (10)	0.0005 (10)
F5	0.0301 (12)	0.0205 (13)	0.0334 (13)	−0.0013 (10)	−0.0050 (10)	−0.0065 (10)
F6	0.0210 (11)	0.0354 (14)	0.0283 (12)	0.0071 (10)	−0.0019 (9)	−0.0127 (10)
C1	0.0140 (16)	0.0155 (19)	0.0152 (17)	0.0005 (14)	−0.0026 (14)	−0.0021 (14)
C2	0.0137 (17)	0.018 (2)	0.0201 (18)	0.0011 (14)	−0.0022 (14)	−0.0013 (15)
C3	0.0131 (16)	0.020 (2)	0.0195 (18)	−0.0058 (14)	0.0033 (14)	−0.0044 (15)
C4	0.0156 (17)	0.017 (2)	0.0156 (17)	−0.0053 (14)	−0.0012 (14)	−0.0030 (14)
C5	0.0174 (17)	0.0144 (19)	0.0111 (16)	−0.0036 (14)	−0.0003 (14)	−0.0037 (13)
C6	0.0212 (18)	0.0158 (19)	0.0201 (18)	−0.0044 (15)	0.0036 (15)	−0.0002 (15)
C7	0.0262 (19)	0.020 (2)	0.0136 (17)	−0.0033 (16)	0.0047 (15)	0.0024 (15)
C8	0.0170 (17)	0.0142 (19)	0.0145 (17)	−0.0051 (14)	−0.0006 (14)	−0.0030 (14)
C9	0.0202 (18)	0.016 (2)	0.0125 (17)	−0.0021 (15)	−0.0025 (14)	−0.0031 (14)
C10	0.0284 (19)	0.019 (2)	0.0143 (17)	0.0016 (16)	−0.0038 (15)	0.0010 (15)
C11	0.0193 (17)	0.021 (2)	0.0172 (18)	0.0057 (15)	−0.0021 (14)	0.0007 (15)
C12	0.0168 (17)	0.019 (2)	0.0157 (17)	0.0019 (15)	0.0002 (14)	−0.0026 (14)
C13	0.0139 (17)	0.025 (2)	0.0135 (17)	0.0044 (15)	−0.0012 (14)	0.0009 (15)
C14	0.0147 (17)	0.029 (2)	0.0163 (18)	0.0011 (16)	−0.0010 (14)	−0.0068 (15)
C15	0.0174 (18)	0.022 (2)	0.0231 (19)	−0.0041 (15)	0.0027 (15)	−0.0117 (16)
C16	0.0153 (17)	0.019 (2)	0.0195 (18)	−0.0003 (15)	0.0032 (14)	−0.0038 (15)
C17	0.0127 (17)	0.019 (2)	0.0148 (17)	0.0025 (14)	0.0038 (14)	−0.0014 (14)
C18	0.0191 (19)	0.015 (2)	0.030 (2)	0.0010 (14)	0.0018 (15)	−0.0055 (16)
C19	0.028 (2)	0.019 (2)	0.023 (2)	−0.0039 (17)	−0.0014 (16)	−0.0033 (16)
C20	0.0235 (19)	0.025 (2)	0.0156 (18)	0.0052 (16)	−0.0017 (15)	−0.0019 (15)

Geometric parameters (Å, º) top

Fe1—N1	1.977 (3)	C2—C3	1.372 (5)
Fe1—N1ⁱ	1.977 (3)	C2—H2	0.9500
Fe1—N2	1.974 (3)	C3—C4	1.408 (5)
Fe1—N2ⁱ	1.974 (3)	C3—H3	0.9500
Fe1—N3	1.966 (3)	C4—C5	1.415 (4)
Fe1—N3ⁱ	1.966 (3)	C4—C6	1.439 (5)
S1—O1	1.417 (3)	C5—C8	1.414 (5)
S1—O2	1.429 (3)	C6—C7	1.341 (5)
S1—N4	1.581 (3)	C6—H6	0.9500
S1—C19	1.827 (4)	C7—C9	1.439 (5)
S2—O3	1.431 (2)	C7—H7	0.9500
S2—O4	1.435 (2)	C8—C9	1.403 (5)
S2—N4	1.574 (3)	C9—C10	1.413 (5)
S2—C20	1.824 (4)	C10—C11	1.368 (5)
N1—C1	1.341 (4)	C10—H10	0.9500
N1—C5	1.366 (4)	C11—C12	1.388 (5)
N2—C8	1.364 (4)	C11—H11	0.9500
N2—C12	1.326 (4)	C12—H12	0.9500
N3—C13	1.343 (4)	C13—C14	1.400 (5)
N3—C17	1.368 (4)	C13—H13	0.9500
O5—H5W	0.875 (10)	C14—C15	1.360 (5)
F1—C19	1.318 (4)	C14—H14	0.9500
F2—C19	1.324 (4)	C15—C16	1.410 (5)
F3—C19	1.329 (4)	C15—H15	0.9500
F4—C20	1.327 (4)	C16—C17	1.401 (5)
F5—C20	1.330 (4)	C16—C18	1.439 (5)
F6—C20	1.327 (4)	C17—C17ⁱ	1.425 (6)
C1—C2	1.400 (4)	C18—C18ⁱ	1.345 (7)
C1—H1	0.9500	C18—H18	0.9500

N3—Fe1—N3ⁱ	83.17 (16)	C7—C6—C4	121.7 (3)
N3—Fe1—N2ⁱ	174.17 (11)	C7—C6—H6	119.1
N3ⁱ—Fe1—N2ⁱ	94.38 (11)	C4—C6—H6	119.1
N3—Fe1—N2	94.38 (11)	C6—C7—C9	121.1 (3)
N3ⁱ—Fe1—N2	174.17 (11)	C6—C7—H7	119.5
N2ⁱ—Fe1—N2	88.54 (16)	C9—C7—H7	119.5
N3—Fe1—N1ⁱ	92.05 (11)	N2—C8—C9	123.7 (3)
N3ⁱ—Fe1—N1ⁱ	89.01 (11)	N2—C8—C5	116.3 (3)
N2ⁱ—Fe1—N1ⁱ	82.60 (11)	C9—C8—C5	120.0 (3)
N2—Fe1—N1ⁱ	96.38 (11)	C8—C9—C10	116.6 (3)
N3—Fe1—N1	89.01 (11)	C8—C9—C7	118.7 (3)
N3ⁱ—Fe1—N1	92.05 (11)	C10—C9—C7	124.7 (3)
N2ⁱ—Fe1—N1	96.38 (11)	C11—C10—C9	119.2 (3)
N2—Fe1—N1	82.60 (11)	C11—C10—H10	120.4
N1ⁱ—Fe1—N1	178.58 (17)	C9—C10—H10	120.4
O1—S1—O2	118.91 (16)	C10—C11—C12	120.1 (3)
O1—S1—N4	108.49 (16)	C10—C11—H11	120.0
O2—S1—N4	116.70 (16)	C12—C11—H11	120.0
O1—S1—C19	103.70 (17)	N2—C12—C11	122.9 (3)
O2—S1—C19	104.80 (16)	N2—C12—H12	118.6
N4—S1—C19	101.81 (17)	C11—C12—H12	118.6
O3—S2—O4	118.49 (16)	N3—C13—C14	122.6 (3)
O3—S2—N4	116.61 (16)	N3—C13—H13	118.7
O4—S2—N4	108.02 (16)	C14—C13—H13	118.7
O3—S2—C20	104.65 (16)	C15—C14—C13	119.8 (3)
O4—S2—C20	103.83 (15)	C15—C14—H14	120.1
N4—S2—C20	103.19 (17)	C13—C14—H14	120.1
C1—N1—C5	117.1 (3)	C14—C15—C16	120.1 (3)
C1—N1—Fe1	129.7 (2)	C14—C15—H15	120.0
C5—N1—Fe1	112.9 (2)	C16—C15—H15	120.0
C12—N2—C8	117.4 (3)	C17—C16—C15	116.6 (3)
C12—N2—Fe1	129.9 (2)	C17—C16—C18	118.2 (3)
C8—N2—Fe1	112.6 (2)	C15—C16—C18	125.2 (3)
C13—N3—C17	117.1 (3)	N3—C17—C16	123.9 (3)
C13—N3—Fe1	130.2 (2)	N3—C17—C17ⁱ	115.67 (18)
C17—N3—Fe1	112.7 (2)	C16—C17—C17ⁱ	120.4 (2)
S1—N4—S2	124.92 (19)	C18ⁱ—C18—C16	121.4 (2)
N1—C1—C2	123.0 (3)	C18ⁱ—C18—H18	119.3
N1—C1—H1	118.5	C16—C18—H18	119.3
C2—C1—H1	118.5	F1—C19—F2	107.8 (3)
C3—C2—C1	119.7 (3)	F1—C19—F3	108.7 (3)
C3—C2—H2	120.1	F2—C19—F3	107.6 (3)
C1—C2—H2	120.1	F1—C19—S1	111.6 (3)
C2—C3—C4	119.5 (3)	F2—C19—S1	111.1 (3)
C2—C3—H3	120.2	F3—C19—S1	109.9 (3)
C4—C3—H3	120.2	F4—C20—F5	108.1 (3)
C3—C4—C5	116.9 (3)	F4—C20—F6	108.5 (3)
C3—C4—C6	125.4 (3)	F5—C20—F6	108.6 (3)
C5—C4—C6	117.6 (3)	F4—C20—S2	111.0 (3)
N1—C5—C8	115.5 (3)	F5—C20—S2	108.8 (2)
N1—C5—C4	123.6 (3)	F6—C20—S2	111.8 (2)
C8—C5—C4	120.8 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5W···O4ⁱⁱ	0.88 (1)	2.23 (6)	2.963 (4)	141 (7)
C2—H2···O3ⁱⁱⁱ	0.95	2.50	3.433 (4)	166
C14—H14···O2	0.95	2.53	3.481 (5)	174

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

Selected bond lengths (Å) top

Fe1—N1	1.977 (3)	Fe1—N3	1.966 (3)
Fe1—N2	1.974 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5W···O4ⁱ	0.875 (10)	2.23 (6)	2.963 (4)	141 (7)
C2—H2···O3ⁱⁱ	0.95	2.50	3.433 (4)	166
C14—H14···O2	0.95	2.53	3.481 (5)	174

Symmetry codes: (i) x−1/2, y−1/2, z; (ii) −x+1, −y+2, −z+1.

Acknowledgements

We thank Professor Takafumi Kitazawa of Toho University for his useful comments.

References

Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Deng, R. M. K., Simon, S., Dillon, K. B. & Goeta, A. E. (2001). Acta Cryst. C57, 4–6. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Koh, L. L., Xu, Y., Hsieh, A. K., Song, B., Wu, F. & Ji, L. (1994). Acta Cryst. C50, 884–886. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Nockemann, P., Binnemans, K., Thijs, B., Parac-Vogt, T. N., Merz, K., Mudring, A.-V., Menon, P. C., Rajesh, R. N., Cordoyiannis, G., Thoen, J., Leys, J. & Glorieux, C. (2009). J. Phys. Chem. B, 113, 1429–1437. Web of Science CSD CrossRef PubMed CAS Google Scholar
Potočňák, I., Váhovská, L. & Herich, P. (2014). Acta Cryst. C70, 432-436. Web of Science CSD CrossRef IUCr Journals Google Scholar
Setifi, Z., Setifi, F., Ng, S. W., Oudahmane, A., El-Ghozzi, M. & Avignant, D. (2013). Acta Cryst. E69, m12–m13. CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Teramoto, K., Nishide, T., Okumura, S., Takao, K. & Ikeda, Y. (2014). Electrochemistry, 82, 566–572. Web of Science CrossRef CAS Google Scholar
Zhong, K.-L. (2012). Acta Cryst. C68, m259–m264. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar

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