Crystal structure of poly[tetra-μ-cyanido-ethanol­bis(2-iodo­pyrazine)­digold(I)iron(II)]

Fei, B.; Kucheriv, O.I.; Tokmenko, I.I.; Terebilenko, K.V.; Gural'skiy, I.A.

doi:10.1107/S2056989017014785

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 73| Part 11| November 2017| Pages 1755-1758

https://doi.org/10.1107/S2056989017014785

Open

access

Crystal structure of poly[tetra-μ-cyanido-ethanolbis(2-iodopyrazine)digold(I)iron(II)]

Bin Fei,^a Olesia I. Kucheriv,^b ^* Inna I. Tokmenko,^b,^c Kateryna V. Terebilenko ^b and Il'ya A. Gural'skiy ^b

^aSchool of Chemical Engineering, Nanjing University of Science and Technology, 210094 Nanjing, People's Republic of China, ^bDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska St. 64, Kyiv 01601, Ukraine, and ^cUkraine National O. O. Bogomoletz Medical University, 13 T. Shevchenko Blvd., Kyiv, Ukraine
^*Correspondence e-mail: olesia.kucheriv@univ.kiev.ua

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 22 September 2017; accepted 12 October 2017; online 24 October 2017)

In the title polymeric complex, [Au₂Fe(CN)₄(C₄H₃IN₂)₂(C₂H₆O)]_n, the Fe^II cation is coordinated by two iodopyrazine molecules, one ethanol molecule and three dicyanoaurate anions in a distorted N₅O octahedral geometry. In the crystal, the dicyanoaurate anions bridge the Fe^II cations to form polymeric chains propagating along the b-axis direction. Stabilization of the crystal structure is provided by O—H⋯N hydrogen bonds and π–π stacking between parallel iodopyrazine rings of neighbouring chains, the centroid–centroid distances being 3.654 (10) and 3.658 (9) Å.

Keywords: crystal structure; polymeric complex; dicyanoaurate; iodopyrazine.

CCDC reference: 1579611

1. Chemical context

Among all coordination compounds, cyanide-based complexes attract considerable attention. The cyanide group can be coordinated in either a monodentate or bridging way, connecting different metal ions, leading to the formation of one-, two- or three-dimensional frameworks. The variety of possible structures of cyanide-based complexes results in a variety of functional properties for these coordination materials, such as the ability to include small guest molecules (Klausmeyer et al., 1998 ), act as room-temperature magnets (Garde et al., 2002 ), display photomagnetic and magneto-optical properties (Mizuno et al., 2000 ; Mercurol et al., 2010 ), etc. The most representative examples of cyanide-bridged complexes are Prussian blue analogues, which form three-dimensional frameworks with general formula A^IM_A^II[M_B^III(CN)₆] (A = alkali ion, M_A and M_B = transition metal ions; Keggin & Miles, 1936 ). Prussian blue analogues are very attractive because of their facile synthesis and the possibility to manipulate the magnetic ordering of the material by selecting appropriate spin sources (Ohkoshi et al., 1997 ).

Cyanometallate complexes are typically characterized by a low-spin state of the metal ions; however, the introduction of a complementary ligand with weak ligand field strength can lead to the formation of spin-crossover compounds. This type of compound is mostly represented by Hofmann clathrate analogues with general formula [M(L)_x{M′(CN)₄}] where M = Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺ and Mn²⁺, M′ = Ni²⁺, Pd²⁺, Pt²⁺ and L is either a unidentate or bridging ligand. The first compound of this type reported by Hofmann & Höchtlen (1903 ) was the [Ni(NH₃)₂{Ni(CN)₄}] clathrate, which is able to incorporate benzene or other aromatic molecules. In this structure, the bridging tetracyanonikelate anions contribute to the formation of infinite layers that propagate in the ab plane (Powell & Rayner, 1949 ). However, the first Hofmann-clathrate analogue displaying spin-crossover behavior was [Fe(py)₂{Ni(CN)₄}] (Kitazawa et al., 1996 ). Later, different examples have been obtained for the modification of the original Hofmann clathrates, notably with di- or octacyanometallates (Gural'skiy et al., 2016b ; Wei et al., 2016 ). Another modification method is the use of different organic ligands; for example, the inclusion of a bidentate ligand such as pyrazine leads to the formation of a three-dimensional network (Niel et al., 2001 ). Here we report a new cyanide-based compound with general formula [Fe(Ipz)₂(EtOH){Au(CN)₂}₂] in which the Fe^II ions are stabilized in the high-spin state.

2. Structural commentary

The crystal structure of the title compound was determined at 296 K. It crystallizes in the triclinic P $[\overline{1}]$ space group with two formula units per cell. The Fe^II site has a distorted octahedral [FeN₅O] coordination environment formed by two iodopyrazine N atoms, three dicyanoaurate N atoms and one ethanol O atom (Fig. 1). Two iodopyrazine molecules are coordinated in the cis configuration with the Fe—N distances of 2.216 (7) and 2.272 (7) Å (Table 1) indicating the high-spin state of the Fe^II cation. One of the dicyanoaurate fragments is N-coordinated to the Fe^II site in the form of an anion [Fe1—N2 = 2.096 (7) Å], while the other two are coordinated in a trans configuration, further connecting the framework into a chain [Fe1—N1 = 2.105 (8) and Fe1—N5 = 2.096 (8) Å]. The CN⁻ anions bridge the Fe^II and Au^I cations in a quasi-linear mode with C1—Au1—C2 = 178.8 (3) and C3—Au2—C4 = 178.9 (3)°. In addition, one of the coordination sites of the Fe^II ion is occupied by an O-coordinated ethanol molecule nwith Fe1—O1 = 2.106 (6) Å, which is a typical value for Fe—O_alcohol bonds. There is a deviation from an ideal octahedral geometry, Σ|90 - Θ| = 33.1°, where Θ is the cis-N—Fe—N or cis-O—Fe—N angle in the coordination environment of Fe^II. This value indicates a significant polyhedral distortion that can be explained by the Jahn–Teller effect and the presence of four different types of ligands.

Table 1
Selected bond lengths (Å)

Au1—C1	1.948 (9)	Fe1—N1	2.105 (8)
Au1—C2	1.952 (8)	Fe1—N2	2.096 (7)
Au2—C3	1.970 (8)	Fe1—N3	2.272 (7)
Au2—C4	1.981 (9)	Fe1—N4	2.216 (7)
Fe1—O1	2.106 (6)	Fe1—N5ⁱ	2.096 (8)
Symmetry code: (i) x, y-1, z.

Figure 1
A fragment of the molecular structure of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level [symmetry codes: (i) x, 1 + y, z; (ii) x, −1 + y, z].

3. Supramolecular features

The coordination framework is connected by bridging dicyanoaurate moieties into chains that propagate along the b-axis direction. In addition, the crystal packing is supported by N⋯H—O hydrogen bonds (Fig. 2a, Table 2) in which H atoms from the ethanol hydroxyl group participate in weak interactions with the N atoms of the dicyanoaurate anions. The structure includes parallel-displaced π–π interactions with a distance of 3.381 (5) Å between the planes of the aromatic rings (Fig. 2b). Short Au ⋯ Au distances of 3.163 (5) Å indicate intermolecular aurophilic interactions between the Au atoms of the monodentate and bridging dicyanoaurate moieties (Fig. 2c). The same type of aurophilic interaction was observed for a very similar Au–Fe–pyrazine complex, which displays high-temperature spin-transition behavior [Au⋯Au (LS, 340 K) = 3.3886 (3) Å, Au⋯Au (HS, 360 K) = 3.5870 (5) Å; Gural'skiy et al., 2016a ]. The Au⋯Au distances in the above-mentioned structure are longer because they are defined by a three-dimensional framework of the complex; however, in the case of the title compound, the dicyanoaurate anions are non-bridging and therefore are more flexible, which leads to the creation of aurophilic contacts that are closer to the optimum distance of 3 Å (Schmidbaur, 2000 ).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N6ⁱⁱ	0.86 (5)	1.98 (5)	2.765 (13)	151 (6)
Symmetry code: (ii) -x, -y, -z+1.

Figure 2
The crystal structure of the title compound. (a) View in the ac plane showing N⋯H—O hydrogen bonds (dashed lines). H atoms, except those involved in hydrogen bonding, are omitted for clarity. (b) Structure of the title compound showing π–π contacts (dashed lines). (c) View in the bc plane showing aurophilic interactions (dashed lines). Colour key: Fe dark red; Ag cyan; N blue; O red; C grey; I purple.

4. Database survey

A survey of the Cambridge structural Database (Version 5.38; Groom et al., 2016 ) confirmed that the title compound has never been published before. It also revealed numerous examples of CN-bridged Au–Fe bimetallic frameworks supported by substituted azines (Li et al., 2015 ; Agustí et al., 2008 ; Kosone et al., 2009 ) and non-substituted azines (Niel et al., 2003 ; Gural'skiy et al., 2016a; Kosone et al., 2008 ).

5. Synthesis and crystallization

Crystals of the title compound were obtained by the slow-diffusion method with three layers in a 5 ml tube. The first layer was a solution of K[Au(CN)₂] (29 mg, 0.1 mmol) in water (1 ml), the second layer was a water/ethanol mixture (1:1, 2.5 ml) and the third layer was a solution of Fe(OTs)₂·6H₂O (OTs = toluenesulfonate) (50.6 mg, 0.1 mmol) and iodopyrazine (41.2 mg, 0.2 mmol) in ethanol (1 ml). After two weeks, yellow crystals grew in the middle layer; these were collected and kept under the mother solution prior to measurement.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All hydrogen atoms were placed geometrically at their expected calculated positions with C—H = 0.96 (CH₃), 0.97 (CH₂), 0.93 Å (C_arom), O—H = 0.859 (10) Å, and with U_iso(H) = 1.2U_eq(C) with the exception of methyl hydrogen atoms, which were refined with U_iso(H) = 1.5U_eq(C). The idealized CH₃ group was fixed using an AFIX 137 command that allowed the H atoms to ride on the C atom and rotate around th C—C bond.

Table 3
Experimental details

Crystal data
Chemical formula	[Au₂Fe(CN)₄(C₄H₃IN₂)₂(C₂H₆O)]
M_r	1011.90
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	9.40 (2), 10.30 (2), 12.81 (3)
α, β, γ (°)	92.05 (6), 99.67 (7), 114.30 (6)
V (Å³)	1106 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	16.70
Crystal size (mm)	0.20 × 0.05 × 0.03

Data collection
Diffractometer	Bruker SMART
Absorption correction	Part of the refinement model (ΔF) (Walker & Stuart, 1983 )
T_min, T_max	0.298, 0.456
No. of measured, independent and observed [I > 2σ(I)] reflections	5556, 5556, 4453
R_int	0.097
(sin θ/λ)_max (Å⁻¹)	0.680

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.077, 0.92
No. of reflections	5556
No. of parameters	257
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.26, −2.28
Computer programs: SMART and SAINT (Bruker, 2013 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), DIAMOND (Brandenburg et al., 1999 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1579611

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989017014785/xu5907sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017014785/xu5907Isup2.hkl

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg et al., 1999); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[tetra-µ-cyanido-ethanolbis(2-iodopyrazine)digold(I)iron(II)] top

Crystal data top

[Au₂Fe(CN)₄(C₄H₃IN₂)₂(C₂H₆O)]	Z = 2
M_r = 1011.90	F(000) = 900
Triclinic, P1	D_x = 3.039 Mg m⁻³
a = 9.40 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.30 (2) Å	Cell parameters from 5517 reflections
c = 12.81 (3) Å	θ = 2.4–28.1°
α = 92.05 (6)°	µ = 16.70 mm⁻¹
β = 99.67 (7)°	T = 296 K
γ = 114.30 (6)°	Needle, yellow
V = 1106 (4) Å³	0.20 × 0.05 × 0.03 mm

Data collection top

Bruker SMART diffractometer	4453 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.097
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983)	θ_max = 28.9°, θ_min = 1.6°
T_min = 0.298, T_max = 0.456	h = −10→12
5556 measured reflections	k = −13→8
5556 independent reflections	l = −16→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.077	w = 1/[σ²(F_o²) + (0.0259P)²] where P = (F_o² + 2F_c²)/3
S = 0.92	(Δ/σ)_max = 0.001
5556 reflections	Δρ_max = 2.26 e Å⁻³
257 parameters	Δρ_min = −2.28 e Å⁻³
3 restraints

Special details top

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

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

	x	y	z	U_iso*/U_eq
Au1	0.59034 (4)	0.85190 (3)	0.70913 (2)	0.01892 (7)
Au2	0.11598 (3)	0.01716 (3)	0.40500 (2)	0.02116 (8)
I1	0.85042 (7)	0.17524 (6)	0.33540 (4)	0.03085 (13)
I2	1.09742 (8)	0.86712 (6)	0.99527 (4)	0.03868 (15)
Fe1	0.58906 (12)	0.35008 (10)	0.69926 (7)	0.0154 (2)
O1	0.4739 (6)	0.3148 (6)	0.8300 (4)	0.0229 (11)
H1	0.379 (4)	0.310 (7)	0.825 (3)	0.034*
N4	0.8280 (7)	0.4651 (6)	0.8031 (4)	0.0197 (13)
N6	−0.1459 (9)	−0.2072 (8)	0.2275 (5)	0.0306 (16)
N2	0.3802 (7)	0.2347 (7)	0.5851 (4)	0.0206 (13)
N3	0.7137 (7)	0.3977 (6)	0.5585 (4)	0.0184 (12)
N7	0.8521 (8)	0.4547 (7)	0.3799 (5)	0.0252 (14)
C4	−0.0500 (9)	−0.1237 (9)	0.2898 (5)	0.0242 (16)
N8	1.1356 (8)	0.6149 (7)	0.9205 (5)	0.0270 (14)
N1	0.5698 (7)	0.5466 (6)	0.6996 (4)	0.0200 (12)
C3	0.2821 (9)	0.1544 (8)	0.5205 (5)	0.0186 (14)
N5	0.6142 (8)	1.1576 (7)	0.7088 (4)	0.0215 (13)
C6	0.8096 (9)	0.3307 (8)	0.4158 (5)	0.0196 (14)
C5	0.7384 (9)	0.2989 (8)	0.5038 (5)	0.0215 (15)
H5	0.707513	0.207434	0.525019	0.026*
C9	0.8752 (10)	0.5910 (8)	0.8594 (5)	0.0245 (16)
H9	0.802733	0.630763	0.860960	0.029*
C2	0.6042 (9)	1.0464 (8)	0.7107 (5)	0.0195 (14)
C8	0.7562 (9)	0.5225 (8)	0.5231 (5)	0.0223 (15)
H8	0.740253	0.594317	0.558402	0.027*
C1	0.5725 (9)	0.6564 (8)	0.7050 (5)	0.0211 (15)
C10	1.0299 (10)	0.6648 (8)	0.9160 (5)	0.0270 (18)
C7	0.8257 (10)	0.5510 (9)	0.4327 (6)	0.0289 (18)
H7	0.853931	0.641261	0.409642	0.035*
C12	0.9357 (9)	0.4135 (8)	0.8064 (5)	0.0227 (15)
H12	0.908739	0.325149	0.768484	0.027*
C11	1.0847 (10)	0.4878 (9)	0.8641 (6)	0.0271 (17)
H11	1.156693	0.447104	0.864451	0.033*
C13	0.4932 (10)	0.2326 (9)	0.9133 (5)	0.0290 (18)
H13A	0.603756	0.247389	0.930592	0.035*
H13B	0.428430	0.131598	0.889179	0.035*
C14	0.4467 (14)	0.2727 (13)	1.0106 (6)	0.055 (3)
H14A	0.340589	0.266687	0.992360	0.082*
H14B	0.519379	0.369119	1.039883	0.082*
H14C	0.449934	0.208333	1.062348	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.02856 (16)	0.01474 (13)	0.02017 (13)	0.01414 (12)	0.00870 (11)	0.00444 (10)
Au2	0.02192 (16)	0.02330 (14)	0.01917 (13)	0.00997 (12)	0.00570 (11)	0.00122 (11)
I1	0.0417 (3)	0.0313 (3)	0.0298 (2)	0.0205 (3)	0.0201 (2)	0.0053 (2)
I2	0.0482 (4)	0.0259 (3)	0.0367 (3)	0.0140 (3)	0.0020 (3)	−0.0082 (2)
Fe1	0.0220 (5)	0.0131 (4)	0.0152 (4)	0.0100 (4)	0.0070 (4)	0.0039 (4)
O1	0.026 (3)	0.032 (3)	0.018 (2)	0.018 (3)	0.008 (2)	0.007 (2)
N4	0.026 (3)	0.019 (3)	0.017 (3)	0.011 (3)	0.005 (2)	0.007 (2)
N6	0.033 (4)	0.044 (4)	0.025 (3)	0.024 (4)	0.010 (3)	0.003 (3)
N2	0.025 (4)	0.024 (3)	0.022 (3)	0.017 (3)	0.010 (3)	0.010 (3)
N3	0.021 (3)	0.022 (3)	0.017 (3)	0.012 (3)	0.010 (2)	0.008 (2)
N7	0.034 (4)	0.025 (3)	0.025 (3)	0.018 (3)	0.013 (3)	0.013 (3)
C4	0.027 (4)	0.036 (4)	0.023 (3)	0.025 (4)	0.010 (3)	0.001 (3)
N8	0.024 (4)	0.028 (3)	0.029 (3)	0.011 (3)	0.004 (3)	0.002 (3)
N1	0.023 (3)	0.017 (3)	0.022 (3)	0.010 (3)	0.004 (2)	0.004 (2)
C3	0.019 (4)	0.019 (3)	0.022 (3)	0.011 (3)	0.003 (3)	0.003 (3)
N5	0.025 (3)	0.020 (3)	0.023 (3)	0.011 (3)	0.011 (3)	0.004 (2)
C6	0.019 (4)	0.021 (3)	0.019 (3)	0.007 (3)	0.009 (3)	0.006 (3)
C5	0.025 (4)	0.022 (4)	0.018 (3)	0.009 (3)	0.008 (3)	0.004 (3)
C9	0.031 (4)	0.027 (4)	0.022 (3)	0.017 (4)	0.007 (3)	0.003 (3)
C2	0.023 (4)	0.020 (3)	0.023 (3)	0.014 (3)	0.010 (3)	0.002 (3)
C8	0.029 (4)	0.022 (4)	0.024 (3)	0.016 (3)	0.012 (3)	0.009 (3)
C1	0.024 (4)	0.021 (4)	0.023 (3)	0.013 (3)	0.008 (3)	0.002 (3)
C10	0.041 (5)	0.024 (4)	0.014 (3)	0.010 (4)	0.011 (3)	0.002 (3)
C7	0.040 (5)	0.026 (4)	0.032 (4)	0.018 (4)	0.024 (4)	0.019 (3)
C12	0.026 (4)	0.018 (3)	0.024 (3)	0.009 (3)	0.005 (3)	0.001 (3)
C11	0.030 (4)	0.033 (4)	0.026 (4)	0.021 (4)	0.005 (3)	0.004 (3)
C13	0.030 (5)	0.035 (4)	0.025 (4)	0.015 (4)	0.009 (3)	0.010 (3)
C14	0.060 (7)	0.086 (8)	0.024 (4)	0.032 (7)	0.017 (4)	0.011 (5)

Geometric parameters (Å, º) top

Au1—Au2ⁱ	3.163 (5)	N7—C7	1.309 (10)
Au1—C1	1.948 (9)	N8—C10	1.287 (11)
Au1—C2	1.952 (8)	N8—C11	1.329 (10)
Au2—C3	1.970 (8)	N1—C1	1.119 (10)
Au2—C4	1.981 (9)	N5—C2	1.111 (10)
I1—C6	2.071 (8)	C6—C5	1.387 (9)
I2—C10	2.078 (9)	C5—H5	0.9300
Fe1—O1	2.106 (6)	C9—H9	0.9300
Fe1—N1	2.105 (8)	C9—C10	1.384 (11)
Fe1—N2	2.096 (7)	C8—H8	0.9300
Fe1—N3	2.272 (7)	C8—C7	1.404 (10)
Fe1—N4	2.216 (7)	C7—H7	0.9300
Fe1—N5ⁱⁱ	2.096 (8)	C12—H12	0.9300
O1—H1	0.859 (10)	C12—C11	1.350 (11)
O1—C13	1.419 (9)	C11—H11	0.9300
N4—C9	1.323 (10)	C13—H13A	0.9700
N4—C12	1.318 (10)	C13—H13B	0.9700
N6—C4	1.122 (10)	C13—C14	1.486 (11)
N2—C3	1.134 (9)	C14—H14A	0.9600
N3—C5	1.333 (9)	C14—H14B	0.9600
N3—C8	1.302 (9)	C14—H14C	0.9600
N7—C6	1.298 (9)

C2—Au1—Au2ⁱ	82.5 (2)	N7—C6—C5	123.1 (7)
C1—Au1—Au2ⁱ	97.8 (2)	C5—C6—I1	119.6 (5)
C1—Au1—C2	178.8 (3)	N3—C5—C6	120.9 (7)
C4—Au2—Au1ⁱ	101.9 (3)	N3—C5—H5	119.5
C3—Au2—Au1ⁱ	78.1 (3)	C6—C5—H5	119.5
C3—Au2—C4	178.9 (3)	N4—C9—H9	119.3
O1—Fe1—N4	92.6 (3)	N4—C9—C10	121.4 (8)
O1—Fe1—N3	177.6 (2)	C10—C9—H9	119.3
N4—Fe1—N3	87.1 (3)	N5—C2—Au1	177.8 (7)
N2—Fe1—O1	94.9 (3)	N3—C8—H8	119.3
N2—Fe1—N4	171.7 (2)	N3—C8—C7	121.5 (7)
N2—Fe1—N3	85.6 (3)	C7—C8—H8	119.3
N2—Fe1—N1	95.8 (3)	N1—C1—Au1	175.8 (7)
N1—Fe1—O1	86.5 (2)	N8—C10—I2	118.1 (6)
N1—Fe1—N4	88.1 (3)	N8—C10—C9	123.0 (7)
N1—Fe1—N3	91.1 (2)	C9—C10—I2	118.9 (6)
N5ⁱⁱ—Fe1—O1	91.3 (2)	N7—C7—C8	122.2 (7)
N5ⁱⁱ—Fe1—N4	89.4 (3)	N7—C7—H7	118.9
N5ⁱⁱ—Fe1—N2	87.0 (3)	C8—C7—H7	118.9
N5ⁱⁱ—Fe1—N3	91.1 (2)	N4—C12—H12	119.7
N5ⁱⁱ—Fe1—N1	176.6 (2)	N4—C12—C11	120.6 (7)
Fe1—O1—H1	122.0 (18)	C11—C12—H12	119.7
C13—O1—Fe1	126.0 (5)	N8—C11—C12	124.5 (8)
C13—O1—H1	105.7 (18)	N8—C11—H11	117.8
C9—N4—Fe1	123.4 (5)	C12—C11—H11	117.8
C12—N4—Fe1	120.4 (5)	O1—C13—H13A	109.3
C12—N4—C9	116.1 (7)	O1—C13—H13B	109.3
C3—N2—Fe1	165.9 (6)	O1—C13—C14	111.7 (8)
C5—N3—Fe1	122.6 (5)	H13A—C13—H13B	107.9
C8—N3—Fe1	120.9 (5)	C14—C13—H13A	109.3
C8—N3—C5	116.4 (6)	C14—C13—H13B	109.3
C6—N7—C7	116.0 (6)	C13—C14—H14A	109.5
N6—C4—Au2	177.2 (7)	C13—C14—H14B	109.5
C10—N8—C11	114.3 (7)	C13—C14—H14C	109.5
C1—N1—Fe1	174.0 (6)	H14A—C14—H14B	109.5
N2—C3—Au2	178.2 (6)	H14A—C14—H14C	109.5
C2—N5—Fe1ⁱⁱⁱ	169.9 (7)	H14B—C14—H14C	109.5
N7—C6—I1	117.3 (5)

I1—C6—C5—N3	178.6 (5)	C6—N7—C7—C8	0.3 (12)
Fe1—O1—C13—C14	158.4 (6)	C5—N3—C8—C7	−0.6 (11)
Fe1—N4—C9—C10	−174.4 (5)	C9—N4—C12—C11	−0.3 (10)
Fe1—N4—C12—C11	175.7 (5)	C8—N3—C5—C6	1.6 (10)
Fe1—N3—C5—C6	177.5 (5)	C10—N8—C11—C12	−0.3 (11)
Fe1—N3—C8—C7	−176.6 (6)	C7—N7—C6—I1	−179.6 (6)
N4—C9—C10—I2	176.5 (5)	C7—N7—C6—C5	0.8 (11)
N4—C9—C10—N8	−2.2 (11)	C12—N4—C9—C10	1.5 (10)
N4—C12—C11—N8	−0.3 (12)	C11—N8—C10—I2	−177.3 (5)
N3—C8—C7—N7	−0.4 (13)	C11—N8—C10—C9	1.5 (10)
N7—C6—C5—N3	−1.8 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N6^iv	0.86 (5)	1.98 (5)	2.765 (13)	151 (6)

Symmetry code: (iv) −x, −y, −z+1.

Funding information

Funding for this research was provided by: Ministry of Education and Science of Ukraine (grant No. 16BF037-01M).

References

Agustí, G., Muñoz, M. C., Gaspar, A. B. & Real, J. A. (2008). Inorg. Chem. 47, 2552–2561. PubMed
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Bruker (2013). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals
Garde, R., Villain, F. & Verdaguer, M. (2002). J. Am. Chem. Soc. 124, 10531–10538. Web of Science CrossRef PubMed CAS
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals
Gural'skiy, I. A., Golub, B. O., Shylin, S. I., Ksenofontov, V., Shepherd, H. J., Raithby, P. R., Tremel, W. & Fritsky, I. O. (2016a). Eur. J. Inorg. Chem. 2016, 3191–3195. CAS
Gural'skiy, I. A., Shylin, S. I., Golub, B. O., Ksenofontov, V., Fritsky, I. O. & Tremel, W. (2016b). New J. Chem. 40, 9012–9016. CAS
Hofmann, K. A. & Höchtlen, F. (1903). Ber. Dtsch. Chem. Ges. 36, 1149–1151. CrossRef CAS
Keggin, J. F. & Miles, F. D. (1936). Nature, 137, 577–578. CrossRef CAS
Kitazawa, T., Gomi, Y., Takahashi, M., Takeda, M., Enomoto, M., Miyazaki, A. & Enoki, T. (1996). J. Mater. Chem. 6, 119–121. CSD CrossRef CAS Web of Science
Klausmeyer, K. K., Rauchfuss, T. B. & Wilson, S. R. (1998). Angew. Chem. Int. Ed. 37, 1694–1696. Web of Science CrossRef CAS
Kosone, T., Kachi-Terajima, C., Kanadani, C., Saito, T. & Kitazawa, T. (2008). Chem. Lett. 37, 754–755. CSD CrossRef CAS
Kosone, T., Kanadani, C., Saito, T. & Kitazawa, T. (2009). Polyhedron, 28, 1991–1995. CSD CrossRef CAS
Li, J.-Y., Chen, Y.-C., Zhang, Z.-M., Liu, W., Ni, Z.-P. & Tong, M.-L. (2015). Chem. Eur. J. 21, 1645–1651. CSD CrossRef CAS PubMed
Mercurol, J., Li, Y., Pardo, E., Risset, O., Seuleiman, M., Rousselière, H., Lescouëzec, R. & Julve, M. (2010). Chem. Commun. 46, 8995–8997. CSD CrossRef CAS
Mizuno, M., Ohkoshi, S. & Hashimoto, K. (2000). Adv. Mater. 12, 1955–1958. CrossRef CAS
Niel, V., Martinez-Agudo, J. M., Muñoz, M. C., Gaspar, A. B. & Real, J. A. (2001). Inorg. Chem. 40, 3838–3839. Web of Science CSD CrossRef PubMed CAS
Niel, V., Thompson, A. L., Muñoz, M. C., Galet, A., Goeta, A. E. & Real, J. A. (2003). Angew. Chem. Int. Ed. 42, 3760–3763. Web of Science CSD CrossRef CAS
Ohkoshi, S., Iyoda, T., Fujishima, A. & Hashimoto, K. (1997). Phys. Rev. B, 56, 11642–11652. CrossRef CAS
Powell, H. M. & Rayner, J. H. (1949). Nature, 163, 566–567. CrossRef CAS Web of Science
Schmidbaur, H. (2000). Gold Bull. 33, 3–10. CrossRef CAS
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals
Walker, N. & Stuart, D. (1983). Acta Cryst. A39, 158–166. CrossRef CAS Web of Science IUCr Journals
Wei, R.-M., Kong, M., Cao, F., Li, J., Pu, T.-C., Yang, L., Zhang, X. & Song, Y. (2016). Dalton Trans. 45, 18643–18652. CSD CrossRef CAS PubMed

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.