An unexpected rhenium(IV)–rhenium(VII) salt: [Co(NH3)6]3[ReVIIO4][ReIVF6]4·6H2O

Louis–Jean, J.; Mariappan Balasekaran, S.; Hagenbach, A.; Poineau, F.

doi:10.1107/S2056989019009757

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 75| Part 8| August 2019| Pages 1158-1161

https://doi.org/10.1107/S2056989019009757

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An unexpected rhenium(IV)–rhenium(VII) salt: [Co(NH₃)₆]₃[Re^VIIO₄][Re^IVF₆]₄·6H₂O

James Louis–Jean,^a ^* Samundeeswari Mariappan Balasekaran,^a Adelheid Hagenbach ^b and Frederic Poineau ^a

^aDepartment of Chemistry and Biochemistry, University of Nevada Las Vegas, 4505 South Maryland Parkway, Las Vegas, Nevada, 89154, USA, and ^bDepartment of Chemistry and Biochemistry, Freie University Berlin, Berlin 14195, Germany
^*Correspondence e-mail: louisjea@unlv.nevada.edu

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 29 May 2019; accepted 8 July 2019; online 12 July 2019)

The title hydrated salt, tris[hexaamminecobalt(III)] tetraoxidorhenate(VII) tetrakis[hexafluoridorhenate(IV)] hexahydrate, arose unexpectedly due to possible contamination of the K₂ReF₆ starting material with KReO₄. It consists of octahedral [Co(NH₃)₆]³⁺ cation (Co1 site symmetry 1), tetrahedral [Re^VIIO₄]⁻ anions (Re site symmetry 1) and octahedral [Re^IVF₆]²⁻ anions (Re site symmetries 1and $[\overline{3}]$ ). The [ReF₆]²⁻ octahedral anions (mean Re—F = 1.834 Å), [Co(NH₃)₆]³⁺ octahedral cations (mean Co—N = 1.962 Å), and the [ReO₄]⁻ tetrahedral anion (mean Re—O = 1.719 Å) are slightly distorted. A network of N—H⋯F hydrogen bonds consolidates the structure. The crystal studied was refined as a two-component twin.

Keywords: crystal structure; hexamine-cobalt; perrhenate; hexafluororhenate.

CCDC reference: 1939234

1. Chemical context

The chemistry of Re^VII is dominated by the tetrahedral perrhenate anion, [ReO₄]⁻ (Latimer, 1952 ; Abram, 2003 ) while Re^IV is typically found in salts containing octahedral [ReX₆]²⁻ (X = F, Cl, Br, I) anions (Berthold & Jakobson, 1964 ; Jorgensen & Schwochau, 1965 ; Grundy & Brown, 1970 ; Louis-Jean et al., 2018 ). The salts of [ReX₆]²⁻ (X = Cl, Br, I) can be prepared in high yield by the reduction of a perrhenate starting material in the corresponding concentrated HX acid (Briscoe et al., 1931 ; Watt et al., 1963 ). However, salts of [ReF₆]²⁻ are typically prepared from the solid-state melting reaction of [ReX₆]²⁻ (X = Cl, Br, I) with AHF₂ (A = NH₄⁺, K⁺) followed by an aqueous work-up (Ruff & Kwasnik, 1934 ; Louis-Jean et al., 2018). Such a procedure is found to be challenging. Nonetheless, an improved procedure for the preparation of A₂[ReF₆] (A = K, Rb, Cs) salts as well as their X-ray single-crystal structures was recently reported (Louis-Jean et al., 2018).

In the process of exploring the coordination chemistry of hexafluororhenate(IV) compounds, the title compound (I), an unexpected mixed-valence rhenium(IV)–rhenium(VII) salt arose in an effort to prepare [Co(NH₃)₆]₂[ReF₆]₃ by metathesis from K₂[ReF₆] and Co(NH₃)₆Cl₃ in water (353 K). Yellow–orange needle-like crystals of (I) were obtained within two hours by slow evaporation in water at room temperature. The crystals of (I) are air stable over short periods, but decompose to a black material after six months of storage at ambient temperature.

2. Structural commentary

The structure of (I) (Fig. 1) is built up from a [Co(NH₃)₆]³⁺ cation, three distinct [ReF₆]²⁻ anions, one [ReO₄]⁻ anion, and two water molecules of crystallization: these components are held together by electrostatic forces and hydrogen bonding. Site symmetries for the metal atoms are Co1: 1 (Wyckoff position 18f), Re1: 3 (Wyckoff position 6c), Re2: 1 (Wyckoff position 18f), Re3: $[\overline{3}]$ (Wyckoff position 3a), and Re4: $[\overline{3}]$ (Wyckoff position 3b).

Figure 1
The molecular structure of (I) showing displacement ellipsoids drawn at the 50% probability level for all non-H atoms. Symmetry codes: (i) 1 − x + y, 1 − x, z; (ii) 1 − y, x − y, z; (iii) $[{1\over 3}]$ + y, $[{2\over 3}]$ − x + y, $[{5\over 3}]$ − z; (iv) $[{1\over 3}]$ + x − y, − $[{1\over 3}]$ + x, $[{5\over 3}]$ − z; (v) $[{4\over 3}]$ − x, $[{2\over 3}]$ − y, $[{5\over 3}]$ − z; (vi) $[{2\over 3}]$ + x − y, $[{1\over 3}]$ + x, $[{4\over 3}]$ − z; (vii) − $[{1\over 3}]$ + y, $[{1\over 3}]$ − x + y, $[{4\over 3}]$ − z; (viii) $[{2\over 3}]$ − x, $[{4\over 3}]$ − y, $[{4\over 3}]$ − z; (ix) −x + y, 1 − x, z; (x) 1 − y, 1 + x − y, z.

The octahedral [Co(NH₃)₆]³⁺ cation in (I) is slightly distorted; the average Co—N bond length of 1.962 Å is in agreement with the average Co—N bond lengths of 1.963 Å in [Co(NH₃)₆](ReO₄)·2H₂O (Baidina et al., 2012 ) and 1.966 Å in [Co(NH₃)₆](TcO₄)₃ (Poineau et al., 2017 ). In (I), the shortest Co⋯Co and N⋯N separations between nearby [Co(NH₃)₆]³⁺ cations are 7.035 (1) and 4.473 (1) Å, respectively.

In the tetrahedral [ReO₄]⁻ anion in (I), the average Re—O bond length (1.719 Å) is in agreement with the average Re—O bond length of 1.720 Å in [Co(NH₃)₆](ReO₄)·2H₂O (Baidina et al., 2012). In (I) the values of three Re—O bond lengths, [Re1—O2ⁱ, Re—O2 and Re—O2ⁱⁱ = 1.715 (8) Å; symmetry codes: (i) 1 − x + y, 1 − x, z; (ii) 1 − y, x − y, z] are slightly shorter than the fourth one [Re—O1 = 1.748 (14) Å]. In (I), all O—Re—O bond angles in the [ReO₄]⁻ anion are 109.5 (3)°. However, in [Co(NH₃)₆](ReO₄)·2H₂O, the [ReO₄]⁻ anion is slightly distorted by up to 2.7° (Baidina et al., 2012).

The [ReF₆]²⁻ anions are slightly distorted, with Re—F bond lengths varying from 1.916 (6) Å to 1.929 (6) Å. All the Re—F bond lengths in the Re3- and Re4-centred anions are of equal distances of 1.952 (6) and 1.950 (6) Å, respectively, by symmetry. Overall, the average Re—F bond length (1.834 Å) in (I) is notably shorter than the average Re—F bond length (1.951 Å) in A₂[ReF₆] (A = K, Rb, Cs) salts previously studied (Louis-Jean et al., 2018).

3. Supramolecular features

A perspective view of the unit-cell plots for (I) and its component ions ([ReF₆]²⁻, [ReO₄]⁻, and [Co(NH₃)₆]³⁺) are shown in Fig. 2. In the supramolecular structure of the title compound, the ammine ligands of the cations form numerous N—H⋯F and N—H⋯O hydrogen bonds with the fluorine atoms of [ReF₆]²⁻ anions and the water molecules (Table 1, Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯F1ⁱ	0.89	2.34	3.085 (11)	141
N1—H1A⋯F5ⁱ	0.89	2.29	3.078 (10)	148
N1—H1B⋯F5	0.89	2.32	3.037 (10)	138
N1—H1B⋯F7	0.89	2.42	3.098 (11)	133
N1—H1C⋯F3	0.89	2.40	3.144 (10)	141
N1—H1C⋯O1Sⁱⁱ	0.89	2.35	3.084 (12)	140
N2—H2A⋯F2ⁱⁱⁱ	0.89	2.46	3.243 (10)	148
N2—H2A⋯O2ⁱⁱⁱ	0.89	2.54	3.089 (12)	121
N2—H2B⋯F4	0.89	2.31	3.137 (12)	155
N2—H2B⋯F4ⁱⁱⁱ	0.89	2.58	3.161 (10)	124
N2—H2C⋯F7	0.89	2.08	2.928 (10)	158
N3—H3A⋯F6^iv	0.89	2.57	3.054 (10)	115
N3—H3A⋯O2S	0.89	2.26	3.027 (12)	145
N3—H3B⋯F5^iv	0.89	2.52	3.132 (10)	127
N3—H3B⋯F7	0.89	2.32	2.911 (11)	123
N3—H3C⋯F5ⁱ	0.89	2.24	3.112 (10)	166
N4—H4A⋯F2ⁱⁱⁱ	0.89	2.16	3.038 (10)	170
N4—H4A⋯F6ⁱⁱⁱ	0.89	2.57	3.126 (10)	121
N4—H4B⋯F6^iv	0.89	2.19	2.969 (10)	146
N4—H4C⋯F8^v	0.89	2.21	3.019 (11)	150
N5—H5A⋯O2S	0.89	2.08	2.936 (12)	162
N5—H5B⋯F1ⁱ	0.89	2.20	3.057 (11)	162
N5—H5C⋯F1ⁱⁱ	0.89	2.49	3.019 (11)	119
N5—H5C⋯F2ⁱⁱ	0.89	2.43	3.261 (11)	157
N6—H6A⋯F4ⁱⁱⁱ	0.89	2.55	3.110 (10)	122
N6—H6A⋯F6ⁱⁱⁱ	0.89	2.16	3.037 (10)	168
N6—H6B⋯F2ⁱⁱ	0.89	2.16	2.968 (10)	151
N6—H6B⋯O1Sⁱⁱ	0.89	2.67	3.227 (11)	122
N6—H6C⋯F4	0.89	2.14	2.982 (10)	159
Symmetry codes: (i) $[y-{\script{1\over 3}}, -x+y+{\script{1\over 3}}, -z+{\script{4\over 3}}]$ ; (ii) -y+1, x-y, z; (iii) -x+1, -y+1, -z+1; (iv) -x+y, -x+1, z; (v) $[-x+{\script{2\over 3}}, -y+{\script{1\over 3}}, -z+{\script{4\over 3}}]$ .

Figure 2
Unit-cell plots showing only (a) the complete structure of (I), (b) the [ReF₆]²⁻ octahedra, (c) the [ReO₄]⁻ tetrahedra and (d) the [Co(NH₃)₆]³⁺ octahedra viewed along the crystallographic b axis. Color of atoms: Re aqua blue, F green, Co purple, N blue, O red, H gray.

Figure 3
Detail of the hydrogen bonding (blue dotted lines) in (I). Atom colors as in Fig. 2

4. Database survey

To the best of our knowledge, (I) is the only reported hexahalogenorhenate–perrhenate structure containing both rhenium(IV) and rhenium(VII). It is noted that K₂[ReF₆] used for the preparation of (I) was not characterized before use and the presence of perrhenate in (I) may be due to the presence of K[ReO₄] in the starting material. Efforts to isolate the technetium (Tc-99) derivative compound, [Co(NH₃)₆]₃ [(Tc^(vii)O₄) (Tc^(iv)F₆)₄] are in progress.

5. Synthesis and crystallization

All chemicals were obtained commercially from Sigma Aldrich® and used without any further purification. The starting material, K₂[ReF₆], was prepared following the method described in our previous publication (Louis-Jean et al., 2018).

K₂[ReF₆] (114 mg, 0.3 mmol) was dissolved in 2 ml of hot water (353 K), and [Co(NH₃)₆]Cl₃ (53.5 mg, 0.2 mmol) dissolved in 1 ml of H₂O was added. The solution was allowed to evaporate slowly at room temperature and yellow-orange needle-like crystals of (I) were obtained within two hours. The compound was washed with H₂O (3 × 1 ml), followed by isopropanol (3 × 1 ml) and then diethyl ether (3 × 1 ml). Single crystals of (I) were grown in H₂O by slow evaporation at room temperature. Yield: ca 91%. The presence of perrhenate in (I) is probably due to the presence of K[ReO₄] in the starting material (i.e. K₂ReF₆).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The H atoms of the co-crystallized water molecules could not be located in the present experiment.

Table 2
Experimental details

Crystal data
Chemical formula	[Co(NH₃)₆]₃[ReO₄][ReF₆]₄·6H₂O
M_r	2030.40
Crystal system, space group	Trigonal, R $[\overline{3}]$
Temperature (K)	293
a, c (Å)	15.982 (3), 29.740 (5)
V (Å³)	6579 (2)
Z	6
Radiation type	Mo Kα
μ (mm⁻¹)	15.00
Crystal size (mm)	0.63 × 0.08 × 0.07

Data collection
Diffractometer	Bruker D8 QUEST
Absorption correction	Numerical (Krause et al., 2015 )
T_min, T_max	0.02, 0.43
No. of measured, independent and observed [I > 2σ(I)] reflections	45169, 5223, 4885
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.635

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.114, 1.08
No. of reflections	5223
No. of parameters	189
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.36, −4.16
Computer programs: APEX3 and SAINT (Bruker, 2015 ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and shelXle (Hübschle et al., 2011 ).

Supporting information

CCDC reference: 1939234

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989019009757/hb7830sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019009757/hb7830Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: shelXle (Hübschle et al., 2011); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

Tris[hexaamminecobalt(III)] tetraoxidorhenate(VII) tetrakis[hexafluoridorhenate(IV)] hexahydrate top

Crystal data top

[Co(NH₃)₆]₃[ReO₄][ReF₆]₄·6H₂O	D_x = 3.075 Mg m⁻³
M_r = 2030.40	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 618 reflections
a = 15.982 (3) Å	θ = 3.2–32.0°
c = 29.740 (5) Å	µ = 15.00 mm⁻¹
V = 6579 (2) Å³	T = 293 K
Z = 6	Rectangular box, translucent orange
F(000) = 5592	0.63 × 0.08 × 0.07 mm

Data collection top

Bruker D8 QUEST diffractometer	5223 independent reflections
Radiation source: sealed tube, Siemens KFFMo2K-90	4885 reflections with I > 2σ(I)
Curved graphite monochromator	R_int = 0.082
Detector resolution: 8.3333 pixels mm^-1	θ_max = 26.8°, θ_min = 1.6°
'φ and ω scans'	h = −20→20
Absorption correction: numerical (Krause et al., 2015)	k = −20→20
T_min = 0.02, T_max = 0.43	l = −37→37
45169 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.114	w = 1/[σ²(F_o²) + (0.0476P)² + 166.9724P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.002
5223 reflections	Δρ_max = 2.36 e Å⁻³
189 parameters	Δρ_min = −4.16 e Å⁻³

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.

Refinement. Refined as a 2-component twin.

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

	x	y	z	U_iso*/U_eq
Co1	0.30664 (8)	0.34382 (8)	0.58013 (3)	0.0133 (2)
N1	0.4055 (5)	0.4205 (6)	0.6252 (2)	0.0215 (15)
H1A	0.3824	0.3987	0.6526	0.032*
H1B	0.4211	0.4822	0.623	0.032*
H1C	0.4577	0.4154	0.6205	0.032*
N2	0.3377 (7)	0.4637 (6)	0.5488 (3)	0.0257 (17)
H2A	0.2965	0.4506	0.5262	0.038*
H2B	0.3977	0.4909	0.538	0.038*
H2C	0.3333	0.5041	0.5679	0.038*
N3	0.2114 (6)	0.3556 (6)	0.6173 (3)	0.0244 (16)
H3A	0.1533	0.3039	0.6133	0.037*
H3B	0.2098	0.4085	0.6094	0.037*
H3C	0.228	0.3597	0.6461	0.037*
N4	0.2051 (6)	0.2661 (6)	0.5359 (3)	0.0236 (16)
H4A	0.22	0.2963	0.5095	0.035*
H4B	0.1488	0.2582	0.5454	0.035*
H4C	0.2008	0.2086	0.5329	0.035*
N5	0.2754 (6)	0.2239 (6)	0.6122 (3)	0.0255 (17)
H5A	0.2133	0.1932	0.62	0.038*
H5B	0.3118	0.2381	0.6367	0.038*
H5C	0.2869	0.1861	0.5943	0.038*
N6	0.4042 (6)	0.3341 (6)	0.5441 (2)	0.0220 (15)
H6A	0.3851	0.3229	0.5155	0.033*
H6B	0.4115	0.2859	0.5544	0.033*
H6C	0.4602	0.3893	0.546	0.033*
Re2	0.65656 (3)	0.62285 (3)	0.58421 (2)	0.02226 (14)
F1	0.7514 (5)	0.7013 (5)	0.6281 (2)	0.0413 (16)
F2	0.7555 (5)	0.6161 (5)	0.5496 (2)	0.0356 (14)
F3	0.6309 (5)	0.5116 (5)	0.6198 (2)	0.0411 (16)
F4	0.5603 (5)	0.5407 (5)	0.5415 (2)	0.0368 (14)
F5	0.5608 (5)	0.6319 (5)	0.6196 (2)	0.0337 (14)
F6	0.6801 (5)	0.7340 (4)	0.54917 (19)	0.0306 (12)
Re1	0.6667	0.3333	0.51213 (2)	0.02289 (17)
O1	0.6667	0.3333	0.5709 (5)	0.048 (4)
O2	0.7663 (6)	0.4359 (6)	0.4929 (3)	0.0384 (17)
Re4	0.6667	0.3333	0.8333	0.01831 (19)
F8	0.5515 (4)	0.2843 (5)	0.7957 (2)	0.0336 (13)
Re3	0.3333	0.6667	0.6667	0.01401 (18)
F7	0.3284 (5)	0.5638 (5)	0.6295 (2)	0.0396 (15)
O1S	0.7924 (6)	0.4886 (6)	0.6292 (3)	0.0379 (18)
O2S	0.0654 (6)	0.1416 (6)	0.6190 (3)	0.0417 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0161 (5)	0.0146 (5)	0.0097 (5)	0.0079 (4)	0.0003 (4)	−0.0008 (4)
N1	0.019 (4)	0.028 (4)	0.014 (3)	0.009 (3)	−0.001 (3)	−0.003 (3)
N2	0.040 (5)	0.022 (4)	0.019 (4)	0.019 (4)	0.003 (4)	0.002 (3)
N3	0.027 (4)	0.030 (4)	0.018 (4)	0.015 (4)	−0.003 (3)	−0.009 (3)
N4	0.025 (4)	0.032 (4)	0.016 (4)	0.015 (3)	−0.005 (3)	−0.006 (3)
N5	0.029 (4)	0.024 (4)	0.022 (4)	0.013 (3)	0.002 (3)	0.006 (3)
N6	0.029 (4)	0.025 (4)	0.019 (4)	0.018 (3)	0.003 (3)	0.000 (3)
Re2	0.0227 (2)	0.0252 (2)	0.0173 (2)	0.01086 (15)	0.00121 (13)	0.00071 (13)
F1	0.033 (3)	0.051 (4)	0.026 (3)	0.010 (3)	−0.006 (3)	−0.006 (3)
F2	0.039 (3)	0.053 (4)	0.027 (3)	0.032 (3)	0.007 (3)	0.004 (3)
F3	0.044 (4)	0.038 (4)	0.045 (4)	0.023 (3)	0.009 (3)	0.018 (3)
F4	0.035 (3)	0.033 (3)	0.031 (3)	0.009 (3)	−0.007 (3)	−0.005 (3)
F5	0.035 (3)	0.038 (3)	0.030 (3)	0.019 (3)	0.010 (3)	0.004 (3)
F6	0.039 (3)	0.026 (3)	0.027 (3)	0.016 (3)	0.003 (3)	0.005 (2)
Re1	0.0219 (2)	0.0219 (2)	0.0248 (3)	0.01097 (11)	0	0
O1	0.058 (6)	0.058 (6)	0.028 (7)	0.029 (3)	0	0
O2	0.030 (4)	0.033 (4)	0.043 (4)	0.010 (3)	0.001 (3)	0.001 (3)
Re4	0.0199 (3)	0.0199 (3)	0.0151 (4)	0.00997 (13)	0	0
F8	0.030 (3)	0.033 (3)	0.034 (3)	0.013 (3)	−0.005 (3)	0.001 (3)
Re3	0.0135 (2)	0.0135 (2)	0.0151 (4)	0.00674 (12)	0	0
F7	0.042 (4)	0.034 (3)	0.043 (4)	0.019 (3)	0.003 (3)	−0.015 (3)
O1S	0.033 (4)	0.040 (4)	0.039 (4)	0.017 (4)	−0.006 (3)	−0.003 (3)
O2S	0.032 (4)	0.048 (5)	0.038 (4)	0.015 (4)	0.005 (3)	−0.004 (4)

Geometric parameters (Å, º) top

Co1—N2	1.958 (8)	N6—H6C	0.89
Co1—N6	1.960 (7)	Re2—F1	1.916 (6)
Co1—N1	1.965 (7)	Re2—F4	1.918 (6)
Co1—N3	1.965 (8)	Re2—F5	1.922 (6)
Co1—N5	1.968 (8)	Re2—F6	1.928 (6)
Co1—N4	1.972 (8)	Re2—F3	1.929 (6)
N1—H1A	0.89	Re2—F2	1.934 (6)
N1—H1B	0.89	Re1—O2ⁱ	1.715 (8)
N1—H1C	0.89	Re1—O2	1.715 (8)
N2—H2A	0.89	Re1—O2ⁱⁱ	1.715 (8)
N2—H2B	0.89	Re1—O1	1.748 (14)
N2—H2C	0.89	Re4—F8ⁱⁱⁱ	1.952 (6)
N3—H3A	0.89	Re4—F8^iv	1.952 (6)
N3—H3B	0.89	Re4—F8ⁱⁱ	1.952 (6)
N3—H3C	0.89	Re4—F8^v	1.952 (6)
N4—H4A	0.89	Re4—F8	1.952 (6)
N4—H4B	0.89	Re4—F8ⁱ	1.952 (6)
N4—H4C	0.89	Re3—F7^vi	1.950 (6)
N5—H5A	0.89	Re3—F7^vii	1.950 (6)
N5—H5B	0.89	Re3—F7	1.950 (6)
N5—H5C	0.89	Re3—F7^viii	1.950 (6)
N6—H6A	0.89	Re3—F7^ix	1.950 (6)
N6—H6B	0.89	Re3—F7^x	1.950 (6)

N2—Co1—N6	89.7 (4)	F1—Re2—F4	178.1 (3)
N2—Co1—N1	89.0 (4)	F1—Re2—F5	88.7 (3)
N6—Co1—N1	90.0 (3)	F4—Re2—F5	91.0 (3)
N2—Co1—N3	90.2 (4)	F1—Re2—F6	92.3 (3)
N6—Co1—N3	178.6 (3)	F4—Re2—F6	89.6 (3)
N1—Co1—N3	88.6 (3)	F5—Re2—F6	91.3 (3)
N2—Co1—N5	179.4 (3)	F1—Re2—F3	87.9 (3)
N6—Co1—N5	90.7 (4)	F4—Re2—F3	90.2 (3)
N1—Co1—N5	90.6 (4)	F5—Re2—F3	87.6 (3)
N3—Co1—N5	89.4 (4)	F6—Re2—F3	178.9 (3)
N2—Co1—N4	91.5 (4)	F1—Re2—F2	89.8 (3)
N6—Co1—N4	91.2 (3)	F4—Re2—F2	90.5 (3)
N1—Co1—N4	178.7 (3)	F5—Re2—F2	178.5 (3)
N3—Co1—N4	90.2 (3)	F6—Re2—F2	88.6 (3)
N5—Co1—N4	88.9 (4)	F3—Re2—F2	92.5 (3)
Co1—N1—H1A	109.5	O2ⁱ—Re1—O2	109.5 (3)
Co1—N1—H1B	109.5	O2ⁱ—Re1—O2ⁱⁱ	109.5 (3)
H1A—N1—H1B	109.5	O2—Re1—O2ⁱⁱ	109.5 (3)
Co1—N1—H1C	109.5	O2ⁱ—Re1—O1	109.5 (3)
H1A—N1—H1C	109.5	O2—Re1—O1	109.5 (3)
H1B—N1—H1C	109.5	O2ⁱⁱ—Re1—O1	109.5 (3)
Co1—N2—H2A	109.5	F8ⁱⁱⁱ—Re4—F8^iv	90.5 (3)
Co1—N2—H2B	109.5	F8ⁱⁱⁱ—Re4—F8ⁱⁱ	180.0 (3)
H2A—N2—H2B	109.5	F8^iv—Re4—F8ⁱⁱ	89.5 (3)
Co1—N2—H2C	109.5	F8ⁱⁱⁱ—Re4—F8^v	90.5 (3)
H2A—N2—H2C	109.5	F8^iv—Re4—F8^v	90.5 (3)
H2B—N2—H2C	109.5	F8ⁱⁱ—Re4—F8^v	89.5 (3)
Co1—N3—H3A	109.5	F8ⁱⁱⁱ—Re4—F8	89.5 (3)
Co1—N3—H3B	109.5	F8^iv—Re4—F8	89.6 (3)
H3A—N3—H3B	109.5	F8ⁱⁱ—Re4—F8	90.5 (3)
Co1—N3—H3C	109.5	F8^v—Re4—F8	180.0
H3A—N3—H3C	109.5	F8ⁱⁱⁱ—Re4—F8ⁱ	89.5 (3)
H3B—N3—H3C	109.5	F8^iv—Re4—F8ⁱ	180.0
Co1—N4—H4A	109.5	F8ⁱⁱ—Re4—F8ⁱ	90.5 (3)
Co1—N4—H4B	109.5	F8^v—Re4—F8ⁱ	89.5 (3)
H4A—N4—H4B	109.5	F8—Re4—F8ⁱ	90.5 (3)
Co1—N4—H4C	109.5	F7^vi—Re3—F7^vii	91.0 (3)
H4A—N4—H4C	109.5	F7^vi—Re3—F7	89.0 (3)
H4B—N4—H4C	109.5	F7^vii—Re3—F7	89.0 (3)
Co1—N5—H5A	109.5	F7^vi—Re3—F7^viii	91.0 (3)
Co1—N5—H5B	109.5	F7^vii—Re3—F7^viii	91.0 (3)
H5A—N5—H5B	109.5	F7—Re3—F7^viii	180.0 (4)
Co1—N5—H5C	109.5	F7^vi—Re3—F7^ix	180.0
H5A—N5—H5C	109.5	F7^vii—Re3—F7^ix	89.0 (3)
H5B—N5—H5C	109.5	F7—Re3—F7^ix	91.0 (3)
Co1—N6—H6A	109.5	F7^viii—Re3—F7^ix	89.0 (3)
Co1—N6—H6B	109.5	F7^vi—Re3—F7^x	89.0 (3)
H6A—N6—H6B	109.5	F7^vii—Re3—F7^x	180.0
Co1—N6—H6C	109.5	F7—Re3—F7^x	91.0 (3)
H6A—N6—H6C	109.5	F7^viii—Re3—F7^x	89.0 (3)
H6B—N6—H6C	109.5	F7^ix—Re3—F7^x	91.0 (3)

Symmetry codes: (i) −x+y+1, −x+1, z; (ii) −y+1, x−y, z; (iii) y+1/3, −x+y+2/3, −z+5/3; (iv) x−y+1/3, x−1/3, −z+5/3; (v) −x+4/3, −y+2/3, −z+5/3; (vi) x−y+2/3, x+1/3, −z+4/3; (vii) y−1/3, −x+y+1/3, −z+4/3; (viii) −x+2/3, −y+4/3, −z+4/3; (ix) −x+y, −x+1, z; (x) −y+1, x−y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···F1^vii	0.89	2.34	3.085 (11)	141
N1—H1A···F5^vii	0.89	2.29	3.078 (10)	148
N1—H1B···F5	0.89	2.32	3.037 (10)	138
N1—H1B···F7	0.89	2.42	3.098 (11)	133
N1—H1C···F3	0.89	2.40	3.144 (10)	141
N1—H1C···O1Sⁱⁱ	0.89	2.35	3.084 (12)	140
N2—H2A···F2^xi	0.89	2.46	3.243 (10)	148
N2—H2A···O2^xi	0.89	2.54	3.089 (12)	121
N2—H2B···F4	0.89	2.31	3.137 (12)	155
N2—H2B···F4^xi	0.89	2.58	3.161 (10)	124
N2—H2C···F7	0.89	2.08	2.928 (10)	158
N3—H3A···F6^ix	0.89	2.57	3.054 (10)	115
N3—H3A···O2S	0.89	2.26	3.027 (12)	145
N3—H3B···F5^ix	0.89	2.52	3.132 (10)	127
N3—H3B···F7	0.89	2.32	2.911 (11)	123
N3—H3C···F5^vii	0.89	2.24	3.112 (10)	166
N4—H4A···F2^xi	0.89	2.16	3.038 (10)	170
N4—H4A···F6^xi	0.89	2.57	3.126 (10)	121
N4—H4B···F6^ix	0.89	2.19	2.969 (10)	146
N4—H4C···F8^xii	0.89	2.21	3.019 (11)	150
N5—H5A···O2S	0.89	2.08	2.936 (12)	162
N5—H5B···F1^vii	0.89	2.20	3.057 (11)	162
N5—H5C···F1ⁱⁱ	0.89	2.49	3.019 (11)	119
N5—H5C···F2ⁱⁱ	0.89	2.43	3.261 (11)	157
N6—H6A···F4^xi	0.89	2.55	3.110 (10)	122
N6—H6A···F6^xi	0.89	2.16	3.037 (10)	168
N6—H6B···F2ⁱⁱ	0.89	2.16	2.968 (10)	151
N6—H6B···O1Sⁱⁱ	0.89	2.67	3.227 (11)	122
N6—H6C···F4	0.89	2.14	2.982 (10)	159

Symmetry codes: (ii) −y+1, x−y, z; (vii) y−1/3, −x+y+1/3, −z+4/3; (ix) −x+y, −x+1, z; (xi) −x+1, −y+1, −z+1; (xii) −x+2/3, −y+1/3, −z+4/3.

Acknowledgements

The authors thank Ms Julie Bertoia, Mr Charles Bynum, and Dr Hugues Badet for laboratory support.

Funding information

Funding for this research was provided by the US Department of Energy – Nuclear Science and Security Consortium (award No. DE-NA0003180).

References

Abram, U. (2003). Rhenium. In Comprehensive Coordination Chemistry II, edited by J. A. McCleverty & T. J. Meyer, pp. 271–402. New York: Elsevier Science. Google Scholar
Baidina, I. A., Filatov, E. Y., Makotchenko, E. V. & Smolentsev, A. I. (2012). J. Struct. Chem. 53, 112–118. Web of Science CrossRef ICSD CAS Google Scholar
Berthold, H. J. & Jakobson, G. (1964). Angew. Chem. Int. Ed. Engl. 3, 445–445. CrossRef Web of Science Google Scholar
Briscoe, H. V. A., Robinson, P. L. & Rudge, A. J. (1931). J. Chem. Soc. pp. 3218–3220. CrossRef Google Scholar
Bruker (2015). APEX3 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Grundy, H. D. & Brown, I. D. (1970). Can. J. Chem. 48, 1151–1154. CrossRef ICSD CAS Web of Science Google Scholar
Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281–1284. Web of Science CrossRef IUCr Journals Google Scholar
Jorgensen, C. K. & Schwochau, K. (1965). Z. Naturforsch. Teil A, 20, 65–75. Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Latimer, W. M. (1952). The Oxidation State of the Elements and Their Potential in Aqueous Solutions. New York: Prentice-Hall Inc. Google Scholar
Louis-Jean, J., Mariappan Balasekaran, S., Smith, D., Salamat, A., Pham, C. T. & Poineau, F. (2018). Acta Cryst. E74, 646–649. Web of Science CrossRef ICSD IUCr Journals Google Scholar
Poineau, F., Mausolf, E., Kerlin, W. & Czerwinski, K. (2017). J. Radioanal. Nucl. Chem. 311, 775–778. Web of Science CrossRef ICSD CAS Google Scholar
Ruff, O. & Kwasnik, W. (1934). Z. Anorg. Allg. Chem. 219, 65–81. CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Watt, G. W., Thompson, R. J. & Gibbons, J. M. (1963). Inorganic Syntheses, edited by J. Kleinberg, Vol. VII, pp. 189–192. New York: McGraw-Hill. Google Scholar

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