Phase transition and structures of the twinned low-temperature phases of (Et4N)[ReS4]

Bernhardt, E.; Herbst-Irmer, R.

doi:10.1107/S205322961901725X

research papers

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 76| Part 3| March 2020| Pages 231-235

https://doi.org/10.1107/S205322961901725X

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Phase transition and structures of the twinned low-temperature phases of (Et₄N)[ReS₄]

Eduard Bernhardt ^a ^* and Regine Herbst-Irmer ^b

^aAnorganische Chemie, Fakultät für Mathematik und Naturwissenschaften, Bergische Universität Wuppertal, Gaussstrasse 20, Wuppertal 42119, Germany, and ^bInstitut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, Göttingen 37077, Germany
^*Correspondence e-mail: edbern@uni-wuppertal.de

Edited by A. Lemmerer, University of the Witwatersrand, Johannesburg, South Africa (Received 28 October 2019; accepted 25 December 2019; online 7 February 2020)

The title compound, tetraethylammonium tetrathiorhenate, [(C₂H₅)₄N][ReS₄], has, at room temperature, a disordered structure in the space group P6₃mc (Z = 2, α-phase). A phase transition to the monoclinic space group P2₁ (Z = 2, γ-phase) at 285 K leads to a pseudo-merohedral twin. The high deviation from the hexagonal metric causes split reflections. However, the different orientations could not be separated, but were integrated using a large integration box. Rapid cooling to 110–170 K produces a metastable β-phase (P6₃, Z = 18) in addition to the γ-phase. All crystals of the β-phase are contaminated with the γ-phase. Additionally, the crystals of the β-phase are merohedrally twinned. In contrast to the α-phase, the β- and γ-phases do not show disorder.

Keywords: twinning; phase transition; thiorhenate; crystal structure.

CCDC references: 1971809; 1971808; 1974401

1. Introduction

Salts with the ReS₄⁻ anion were synthesized for the first time in 1970 (Müller et al., 1970 ). So far, some syntheses of ReS₄⁻ salts with different cations, such as Me₄N⁺ (Müller et al., 1970), Ph₄P⁺ (Müller et al., 1970), Ph₄As⁺ (Müller et al., 1970; Halbert et al., 1990 ; Wei et al., 1991 ), Bu₄N⁺ (Do et al., 1985 ), Et₄N⁺ (Müller et al., 1986 , 1987 ; Halbert et al., 1990; Wei et al., 1991; Goodman & Rauchfuss, 2002 ), Pr₄N⁺ (Scattergood et al., 1987 ) and (PhCH₂)Et₃N⁺ (Halbert et al., 1990; Wei et al., 1991), have been reported. There is a lack of reliable methods to prepare salts of the ReS₄⁻ anion with Na⁺, K⁺, Rb⁺ and Cs⁺ cations. The ReS₄⁻ anion is used in several organic chemistry reactions, such as addition reactions to carbon–carbon multiple bonds (Goodman et al., 1996 ; Goodman & Rauchfuss, 1998 , 1999 ; Dopke et al., 2000 ) and the carbon–nitrogen triple bond of some nitriles (Goodman & Rauchfuss, 1997 ). Moreover, the reaction of the ReS₄⁻ anion with isonitriles has been described (Schwarz & Rauchfuss, 2000 ).

X-ray diffraction studies were published for Ph₄PReS₄ (Müller et al., 1970; Diemann & Müller, 1976 ), Ph₄AsReS₄ (Müller et al., 1970), Bu₄NReS₄ (Do et al., 1985) and Et₄NReS₄ (Müller et al., 1986, 1987). While the structures of Ph₄PReS₄, Ph₄AsReS₄ and Bu₄NReS₄ are ordered, the structure of Et₄NReS₄ [P6mm, a = 8.149 (2), c = 6.538 (1) Å, Z = 1, room temperature] is disordered. Superstructural reflections were observed, suggesting a larger unit cell. The aim of this work was to verify that the unit cell of Et₄NReS₄ would be larger at room temperature. Another goal of this work was to investigate whether a phase transition to an ordered structure could be observed at lower temperatures.

2. Experimental

2.1. Synthesis and crystallization

Et₄NReS₄ was synthesized according to the literature method of Goodman & Rauchfuss (2002). Slow evaporation of an acetonitrile solution of Et₄NReS₄ in air afforded crystals suitable for X-ray diffraction analysis.

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The phase designations Ia–Ic are analogous to that used for Et₄NFeCl₄ (Lutz et al., 2014 ).

Table 1
Experimental details

For all phases: (C₈H₂₀N)[ReS₄], M_r = 444.69. Experiments were carried out with Mo Kα radiation using an Oxford Diffraction Gemini E Ultra diffractometer with an EOS CCD camera. The absorption correction was analytical [CrysAlis PRO (Agilent, 2013 ), based on expressions derived by Clark & Reid (1995 )]. H-atom parameters were constrained.

	Ia	Ib	Ic
Crystal data
Crystal system, space group	Hexagonal, P6₃mc	Hexagonal, P6₃	Monoclinic, P2₁
Temperature (K)	297	110	150
a, b, c (Å)	8.150 (2), 8.150 (3), 13.092 (3)	24.170 (3), 24.170 (3), 12.916 (2)	7.900 (2), 12.842 (3), 8.118 (2)
α, β, γ (°)	90, 90, 120	90, 90, 120	90, 119.04 (2), 90
V (Å³)	753.1 (4)	6534.5 (19)	720.0 (3)
Z	2	18	2
μ (mm⁻¹)	8.59	8.91	8.99
Crystal size (mm)	0.32 × 0.03 × 0.03	0.24 × 0.21 × 0.16	0.24 × 0.20 × 0.17

Data collection
T_min, T_max	0.599, 0.829	0.253, 0.351	0.241, 0.336
No. of measured, independent and observed [I > 2σ(I)] reflections	1804, 513, 392	44958, 9707, 8807	4476, 2814, 2808
R_int	0.029	0.036	0.053
(sin θ/λ)_max (Å⁻¹)	0.632	0.696	0.688

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.048, 1.08	0.028, 0.048, 1.05	0.052, 0.138, 1.09
No. of reflections	513	9707	2814
No. of parameters	44	380	87
No. of restraints	34	1	89
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.42	0.87, −1.09	2.01, −4.80
Absolute structure	Refined as an inversion twin	Twinning involves mirror, so Flack parameter cannot be determined	Twinning involves mirror, so Flack parameter cannot be determined
Absolute structure parameter	0.14 (4) (Parsons et al., 2013 )	–	–
Computer programs: CrysAlis PRO (Oxford Diffraction, 2016 $[Oxford Diffraction (2016). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018 (Sheldrick, 2015) and DIAMOND (Brandenburg, 2001 ).

2.2.1. α-phase

The crystal structure of the α-phase (denoted Ia) at 297 K was refined in the space group P6₃mc (Table 1) starting from the structure of Et₄NFeCl₄ at 290 K (Lutz et al., 2014). The ReS₄⁻ anion is completely ordered. The whole tetraethylammonium cation is disordered about special position b with 3m symmetry. A whole cation with an occupancy of 1/6 was modelled. Similarity distance restraints were applied for the ethyl groups. All the atoms of the cation were refined isotropically because of this severe disorder, whereas the atoms of the ordered anion were refined anisotropically (Fig. 1a). H atoms were attached to geometrically optimized positions and refined with the riding model. Twinning by inversion was considered. The fractional contribution of the minor domain refined to 0.14 (4). The C—H distances were fixed at 0.96 (CH₃) or 0.97 Å (CH₂). The U_iso(H) values were constrained to 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) otherwise.

Figure 1
Displacement ellipsoid plots (50% probability level) of (a) Ia at 297 K, (b) Ic at 150 K and (c) Ib at 110 K.

2.2.2. γ-phase

Upon slow cooling (ca 5 K min⁻¹) to 285 K, crystals of the α-phase (i.e. Ia) undergo a reversible phase transition to the γ-phase (denoted Ic). No further phase transitions could be observed between 110 and 300 K. The γ-phase crystallizes in the space group P2₁ as a pseudomerohedral twin (Table 1). Attempts to grow crystals at 273 and 253 K also led to the formation of twins. Data for the γ-phase were collected at 150 K. The high deviation from the hexagonal metric leads to split reflections and reflections of different domains close to each other (see Fig. S1 of the supporting information). However, the different orientations could not be separated. To take the twinning into account, an HKLF5 file (Sevvana et al., 2019 ) was produced (SHELXL2018; Sheldrick, 2015 ) according to the transition from P6₃mc to P2₁ (Table 2). The normal procedure using the TWIN command was not possible, because in SHELXL, only one TWIN command is allowed, but here two twin operations, a threefold and a mirror, are needed. We checked for additional twinning by inversion using now twelve components, but the fractional contributions of the additional six components refined to values close to zero (for details, see the supporting information). Both the tetrathioperrhenate anion (ReS₄⁻) and the tetraethylammonium cation are completely ordered (Fig. 1b). However, to stabilize the refinement, distance restraints were used and the cation was only isotropically refined. H atoms were attached to geometrical optimized positions and refined with the riding model. The C—H distances were fixed at 0.98 (CH₃) or 0.99 Å (CH₂). The U_iso(H) values were constrained to 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) otherwise.

Table 2
Twin components in Ic

Twin components	Appropriate symmetry operations in P6₃mc	h,k,l;i [i = −h−l]^*	Fractional contribution k_i
1	[1] 1	h,k,l;i	0.178 (7)
2	[2] 3⁺ (0,0,z)	l,k,i;h	0.213 (7)
3	[3] 3⁻ (0,0,z)	i,k,h;l	0.080 (7)
4	[7] m (x,−x,z)	−l,k,−h;i	0.084 (7)
5	[8] m (x,2x,z)	−h,k,−i;l	0.233 (7)
6	[9] m (2x,x,z)	−i,k,−l;h	0.212 (7)
Note: (*) the fourth Miller index is the sum of −h and −l, because the transformation from P6₃mc to P2₁ causes the 6₃-axis along the y axis.

2.2.3. β-phase

Rapid cooling (>100 K s⁻¹) of the α-phase (i.e. Ia) to 110–170 K leads to a mixture of the γ-phase (i.e. Ic) and the β-phase (denoted Ib) through a phase transition forming an allotwin. A reciprocal space plot (see Fig. S2 in the supporting information) shows satellites for the reflections with h = 3n and k = 3m. With slow heating (ca 5 K min⁻¹) to 200 K, the β-phase irreversibly changes to the γ-phase. We were not able to obtain crystals of the β-phase free from the γ-phase. Such a superposition of reflections of two phases was also found, for example, in Kautny et al. (2017 ). The a and b axes of the β-phase are enlarged by a factor of three compared to the γ-phase. Therefore, all hkl reflections with h = 3n and k = 3m of the β-phase are contaminated with reflections of the γ-phase. The data collection software (CrysAlis PRO; Oxford Diffraction, 2016 $[Oxford Diffraction (2016). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) could not split the summed intensity into its two components. Therefore, the hkl reflections with h = 3n and k = 3m had to be removed from the data set. This lowers the completeness to only 88.8%. Including the contaminated reflections raises the R1 value from 0.0354 to 0.0548 and shows F²_obs values for hkl reflections with h = 3n and k = 3m much bigger than the F²_calc values (see Table S1 in the supporting information). Even with the ISOR restraint, where atoms are restrained with effective standard deviations so that their U^ij components approximate to isotropic behaviour, the anisotropic displacement parameters refine to nonpositive definite values and the residual density increases to 3.45/−3.41 e Å⁻³. The C—H distances were fixed at 0.98 (CH₃) or 0.99 Å (CH₂). The U_iso(H) values were constrained to 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) otherwise.

The β-phase of Et₄NReS₄ is isostructural with Et₄NFeCl₄ at 230 K (Lutz et al., 2014). It crystallizes as a merohedral twin with the twin law 010 100 001 and a fractional contribution of 0.5005 (15). This twin law describes a mirror plane perpendicular to the face diagonal. To check for additional twinning by inversion, a refinement with `TWIN 0 1 0 1 0 0 0 0 1 −4' was applied. The additional fractional contributions refined to −0.004 (7) and −0.007 (7). Therefore, twinning by inversion could be excluded. All tetrathioperrhenate anions (ReS₄⁻) and tetraethylammonium cations are completely ordered (Fig. 1c).

3. Results and discussion

At 297 K, Et₄NReS₄ is isostructural with Et₄NFeCl₄ (Lutz et al., 2014; Warnke et al., 2010 ; Evans et al., 1990 ; Navarro et al., 1988 ), Et₄NFeBrCl₃ (Evans et al., 1990), Et₄NInCl₄ (Trotter et al., 1969 ) and Et₄NTlCl₄ (Lenck et al., 1991 ). They crystallize in the space group P6₃mc. While the anion is ordered, the tetraethylammonium cation is disordered. The volume of the primitive cell grows in the following series Et₄NBF₄ ≃ Et₄NClO₄ < Et₄NMnO₄ ≃ Et₄NPO₂F₂ ≃ Et₄NReOS₃ < Et₄NReS₄ < Et₄NFeCl₄ < Et₄NFeBrCl₃ < Et₄NTlCl₄ ≃ Et₄NInCl₄. Accordingly, in the series Et₄NClO₄ (378.5 K) > Et₄NBF₄ (342 K) > Et₄NPO₂F₂ (323 K) > Et₄NReS₄ (285 K) > Et₄NFeCl₄ (234.7 K) > Et₄NTlCl₄ (222 K), the transition temperature to an ordered structure decreases (Tables 3 and 4).

Table 3
Crystallographic data for the high-temperature phase of several Et₄NMY4 compounds (M = B, Cl, Re, Fe, In and Tl; Y = O, F, S, Cl and Br)

Anion	BF₄^−,a	ClO₄^−,b	ReS₄^−,c	FeCl₄^−,d	FeBrCl₃^−,e	InCl₄^−,f	TlCl₄^−,g
Temperature (K)	373	393	297 (2)	290–295	293	r.t.^h	297
Temperature range (K)	>342	>378.5	>285	>234.7	n.d.ⁱ	n.d.	>222
Space group	Fm $[\overline{3}]$ m	Fm $[\overline{3}]$ m	P6₃mc	P6₃mc	P6₃mc	P6₃mc	P6₃mc
Z	4	4	2	2	2	2	2
V/Z (Å³)	317.3 (4)	329.1	376.42 (7)	383.7–385.7	388.4 (1)	397	394.7 (4)
Notes and references: (a) Matsumoto et al. (2014 ); (b) Ye et al. (2016 ); (c) this work; (d) Lutz et al. (2014), Warnke et al. (2010), Evans et al. (1990) and Navarro et al. (1988); (e) Evans et al. (1990); (f) Trotter et al. (1969); (g) Lenck et al. (1991); (h) r.t. = room temperature; (i) n.d. = not determined.

Table 4
Crystallographic data for the low-temperature phase of several Et₄NMY4 compounds (M = B, P, Cl, Mn, Re and Fe; Y = O, F, S and Cl)

Anion	ClO₄^−,a	BF₄^−,b	MnO₄^−,c	PO₂F₂^−,d	ReO₃S^−,e	ReS₄^−,f	ReS₄^−,f	FeCl₄^−,g	FeCl₄^−,h
Temperature (K)	110–173	298	293	110	293 (2)	149.9 (3)	109.9 (3)	110–170	230
Temperature range (K)	<378.5	<342	n.d.ⁱ	<323	n.d.	<285	metastable	<226.6	234.7–226.6
Apace group	Cc	Cc	P2₁/c	Cc	P2₁/c	P2₁	P6₃	Pca2₁	P6₃
Z	4	4	4	4	8	2	18	4	18
V/Z (Å³)	291.3–294.5	294.5 (3)	307.7 (1)	311.39 (4)	316.7 (1)	360.0 (2)	363.05 (2)	363.77–367.75	376.86 (3)
Notes and references: (a) Ibers (1993 ), Kivikoski et al. (1995 ) and Ye et al. (2016); (b) Giuseppetti et al. (1994 ), Matsumoto et al. (2012 ) and Matsumoto et al. (2014); (c) Whang et al. (1991 ); (d) Matsumoto et al. (2012); (e) Partyka & Holm (2004); (f) this work; (g) Lutz et al. (2014) and Navarro et al. (1988); (h) Lutz et al. (2014) and Navarro et al. (1988); (i) n.d. = not determined.

While Et₄NFeCl₄ at 234.7 K undergoes a phase transition from P6₃mc to P6₃ (Lutz et al., 2014; Navarro et al., 1988), a phase transition from P6₃mc to P2₁ is observed for Et₄NReS₄ at 285 K. The P6₃ phase is metastable for Et₄NReS₄, while the P2₁ phase is not observed for Et₄NFeCl₄. An additional low-temperature phase of Et₄NFeCl₄ crystallizes in the space group Pca2₁ [226.6 (1)–2.93 (3) K] (Lutz et al., 2014; Navarro et al., 1988). This phase is not observed for Et₄NReS₄. While the high-temperature phases of the compounds from Table 3 have the same structure, the low-temperature phases show different structures (Table 4). Tetraethylammonium salts with anions smaller than tetrathiorhenate crystallize at room temperature as the low-temperature phase of Et₄NReS₄. Whereas the tetraethylammonium cation in Et₄NBF₄, Et₄NClO₄, Et₄NPO₂F₂, Et₄NReS₄, Et₄NFeCl₄, Et₄NFeBrCl₃ and Et₄NTlCl₄ has the tg–tg conformation (t is trans and g is gauche), it has the tt–tt conformation in Et₄NReO₃S and Et₄NMnO₄ (Naudin et al., 2000 ). Only the structures of Et₄NReO₃S, Et₄NMnO₄, Et₄NBF₄ (high-temperature phase) and Et₄NClO₄ (high-temperature phase) have an inversion centre. In these two compounds, the Et₄N⁺ cation has a tg–tg conformation or is disordered.

At 297 K, Et₄NReS₄ crystallizes in the space group P6₃mc (Tables 1 and 4). Because of the special position of the Re atom (2a, 3m.; Arnold, 1983 ), all reflections with l = 2n + 1 are much weaker than those with l = 2n (Table 5). This could explain why Müller et al. (1986, 1987) found a smaller primitive cell [P6mm, a = 8.149 (2), c = 6.538 (1) Å, Z = 1]. They observed weak superstructural reflections, suggesting a doubling of the primitive cell [a = 8.149 (2), c = 13.076 (2) Å, Z = 2], which would be in good agreement with the one found here.

Table 5
Intensity of the reflections with even and odd l (Ia and Ic) or k (Ic) from the .fcf file

	F²_av(odd)/F²_av	F²_av(even)/F²_av	F²_av(odd)/F²_av(even)	Δ^a (Å)
Ia (obs)	0.082	1.737	0.047	0
Ia (calc)	0.080	1.740	0.046	0
Ib (obs)^b	0.184	1.815	0.102	0.0573^c
Ib (calc)	0.174	1.826	0.095	0.0573^c
Ic (obs)	0.803	1.196	0.672	0.2720
Ic (calc)	0.796	1.203	0.662	0.2720
Notes: (a) Average displacement of the Re atoms from the threefold axis. (b) Reflections of Ib with h = 3n and k = 3m overlap with appropriate reflections of Ic. The reflections with h = 3n and k = 3m are on average 1.2 times too strong and were not used in the refinement. (c) Re1, Re2 and Re3 = 0 Å; Re4 = 0.0815 Å; Re5 = 0.0905 Å.

In Ib and Ic, the Re atom is displaced from the threefold axis. In Ic, reflections with k = 2n + 1 are as strong as the reflections with k = 2n, while for Ib (as also for Ia), reflections with l = 2n + 1 are much weaker than those with l = 2n (Table 5).

Structurally, Ib is closer to Ia than to Ic. Therefore, Ib is also formed by rapid cooling of Ia, although Ic is thermodynamically more stable. The energy barrier for the conversion of Ib to Ic is relatively large, so that rapid conversion occurs only above 200 K.

In the known structures with ReS₄⁻, the Re—S bond length is independent of the cation (Table 6). The S—Re—S angle in the ReS₄⁻ anion is very close to the tetrahedral value (109.47°). The Re—S bond length in ReO₃S⁻ is very similar to that in ReS₄⁻. For ReO₃S⁻, the following Re—S bond lengths are known: RbReO₃S with 2.126 (6) Å (Krebs & Kindler, 1969 ) and Et₄NReO₃S with 2.128 (5) and 2.143 (5) Å (Partyka & Holm, 2004 ).

Table 6
Re—S bond lengths (Å) and S—Re—S angles (°) for some compounds with the ReS₄⁻ anion

Cation	Et₄N⁺, Ib^a	Et₄N⁺, Ic^a	Et₄N⁺, Ia^a	Et₄N^+,b	Bu₄N^+,c	Ph₄P^+,d
Temperature (K)	109.9 (3)	149.9 (3)	297 (2)	r.t.^e	r.t.	r.t.
Re—S average	2.142 (2)	2.122 (10)	2.125 (4)	2.125 (4)	2.122 (6)	2.155 (30)
Re—S range	2.130–2.154	2.111–2.133	2.120–2.127	2.123–2.126	2.118–2.126	2.155–2.155
S—Re—S average	109.47 (9)	109.47 (71)	109.47 (17)	109.45 (11)	109.48 (84)	Not specified
S—Re—S range	109.06–109.95	108.01–110.61	109.33–109.61	109.4–109.5	107.4–112.8	Not specified
Notes and references: (a) this work; (b) Müller et al. (1987); (c) Do et al. (1985); (d) Diemann & Müller (1976); (e) r.t. = room temperature.

In this article, we were able to show that the unit cell of Et₄NReS₄ is larger at room temperature than previously thought (Müller et al., 1986, 1987). In this structure, the Et₄N⁺ cation is disordered, while the ReS₄⁻ anion is ordered. At 285 K, there is a phase transition to an ordered structure, where the space group changes from P6₃mc to P2₁. The omission of the threefold axis and the mirror plane creates a twin with six components. In addition to this low-temperature phase, a further metastable phase was formed when Ia was cooled rapidly to 110–170 K. This phase crystallizes in the space group P6₃ with a nine times bigger unit cell forming an allotwin with Ib.

Supporting information

CCDC references: 1971809; 1971808; 1974401

Crystal structure: contains datablocks Ia, Ib, Ic, global. DOI: https://doi.org/10.1107/S205322961901725X/ef3002sup1.cif

Structure factors: contains datablock Ia. DOI: https://doi.org/10.1107/S205322961901725X/ef3002Iasup2.hkl

Structure factors: contains datablock Ib. DOI: https://doi.org/10.1107/S205322961901725X/ef3002Ibsup3.hkl

Structure factors: contains datablock Ic. DOI: https://doi.org/10.1107/S205322961901725X/ef3002Icsup4.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205322961901725X/ef3002Iasup5.cml

Additional figures and table. DOI: https://doi.org/10.1107/S205322961901725X/ef3002sup6.pdf

Computing details top

For all structures, data collection: CrysAlis PRO (Oxford Diffraction, 2016); cell refinement: CrysAlis PRO (Oxford Diffraction, 2016); data reduction: CrysAlis PRO (Oxford Diffraction, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015).

Tetraethylammonium tetrathiorhenate (Ia) top

Crystal data top

(C₈H₂₀N)[ReS₄]	D_x = 1.961 Mg m⁻³
M_r = 444.69	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6₃mc	Cell parameters from 687 reflections
a = 8.150 (2) Å	θ = 2.9–24.9°
c = 13.092 (3) Å	µ = 8.59 mm⁻¹
V = 753.1 (4) Å³	T = 297 K
Z = 2	Prism, black
F(000) = 428	0.32 × 0.03 × 0.03 mm

Data collection top

Oxford Diffraction Gemini E Ultra diffractometer with an EOS CCD camera	513 independent reflections
Radiation source: fine-focus sealed tube Enhanced (Mo)	392 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 16.2705 pixels mm^-1	θ_max = 26.7°, θ_min = 2.9°
ω scans	h = −10→5
Absorption correction: analytical [CrysAlis PRO (Agilent, 2013), based on expressions derived by Clark & Reid (1995)]	k = −7→10
T_min = 0.599, T_max = 0.829	l = −8→16
1804 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.021	w = 1/[σ²(F_o²) + (0.018P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.048	(Δ/σ)_max < 0.001
S = 1.08	Δρ_max = 0.26 e Å⁻³
513 reflections	Δρ_min = −0.42 e Å⁻³
44 parameters	Absolute structure: Refined as an inversion twin.
34 restraints	Absolute structure parameter: 0.14 (4)

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 inversion twin.

Suitable single crystals of Et₄NReS₄ were attached to a goniometer head. The data collection was performed using an Oxford Diffraction Gemini E Ultra diffractometer with a 2K × 2K EOS CCD camera, a four-circle goniometer with κ geometry, a sealed-tube Mo radiation source, and an Oxford Instruments Cryojet cooling unit. Processing of the raw data, scaling of the diffraction data and the application of an empirical absorption correction were performed with the CrysAlisPro program (CrysAlis PRO, 2016). The structures were solved by direct methods and refined against F² (Sheldrick, 2015, 2008). The graphics were prepared with the program Diamond (Brandenburg, 2001). Full details of all structural data (CCDC-1971807 to CCDC-1971809) are presented in Section S of the Supporting Information File.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Re	0.0000	0.0000	0.0550 (2)	0.0597 (2)
S1	0.0000	0.0000	0.2173 (4)	0.0829 (17)
S2	−0.14196 (19)	0.14196 (19)	0.0010 (3)	0.0930 (8)
N1	0.678 (4)	0.331 (3)	0.3103 (10)	0.041 (3)*	0.1667
C1	0.513 (4)	0.139 (3)	0.328 (2)	0.065 (5)*	0.1667
H1A	0.4031	0.1402	0.3009	0.078*	0.1667
H1B	0.4953	0.1250	0.4018	0.078*	0.1667
C2	0.506 (6)	−0.038 (3)	0.290 (3)	0.054 (5)*	0.1667
H2A	0.3881	−0.1463	0.3092	0.082*	0.1667
H2B	0.6092	−0.0478	0.3182	0.082*	0.1667
H2C	0.5163	−0.0325	0.2164	0.082*	0.1667
C3	0.850 (4)	0.314 (4)	0.293 (3)	0.065 (5)*	0.1667
H3A	0.8878	0.2857	0.3581	0.078*	0.1667
H3B	0.8150	0.2056	0.2488	0.078*	0.1667
C4	1.020 (5)	0.480 (6)	0.248 (3)	0.054 (5)*	0.1667
H4A	1.1202	0.4522	0.2402	0.082*	0.1667
H4B	1.0604	0.5882	0.2914	0.082*	0.1667
H4C	0.9873	0.5078	0.1817	0.082*	0.1667
C5	0.662 (5)	0.428 (5)	0.2172 (17)	0.065 (5)*	0.1667
H5A	0.7897	0.5192	0.1956	0.078*	0.1667
H5B	0.6071	0.3336	0.1637	0.078*	0.1667
C6	0.554 (6)	0.529 (6)	0.220 (3)	0.054 (5)*	0.1667
H6A	0.5582	0.5822	0.1543	0.082*	0.1667
H6B	0.6084	0.6278	0.2702	0.082*	0.1667
H6C	0.4247	0.4411	0.2380	0.082*	0.1667
C7	0.704 (7)	0.451 (3)	0.4029 (16)	0.065 (5)*	0.1667
H7A	0.5927	0.4641	0.4088	0.078*	0.1667
H7B	0.8110	0.5760	0.3900	0.078*	0.1667
C8	0.736 (3)	0.386 (6)	0.5047 (14)	0.054 (5)*	0.1667
H8A	0.7497	0.4756	0.5563	0.082*	0.1667
H8B	0.8484	0.3766	0.5019	0.082*	0.1667
H8C	0.6292	0.2642	0.5209	0.082*	0.1667

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Re	0.0630 (3)	0.0630 (3)	0.0530 (3)	0.03152 (13)	0.000	0.000
S1	0.097 (3)	0.097 (3)	0.054 (3)	0.0486 (14)	0.000	0.000
S2	0.1049 (17)	0.1049 (17)	0.0908 (15)	0.069 (2)	−0.0080 (11)	0.0080 (11)

Geometric parameters (Å, º) top

Re—S1	2.124 (5)	C3—H3B	0.9700
Re—S2ⁱ	2.125 (3)	C4—H4A	0.9600
Re—S2ⁱⁱ	2.125 (3)	C4—H4B	0.9600
Re—S2	2.125 (3)	C4—H4C	0.9600
N1—C1	1.485 (19)	C5—C6	1.47 (3)
N1—C5	1.496 (19)	C5—H5A	0.9700
N1—C3	1.496 (19)	C5—H5B	0.9700
N1—C7	1.502 (18)	C6—H6A	0.9600
C1—C2	1.51 (2)	C6—H6B	0.9600
C1—H1A	0.9700	C6—H6C	0.9600
C1—H1B	0.9700	C7—C8	1.50 (2)
C2—H2A	0.9600	C7—H7A	0.9700
C2—H2B	0.9600	C7—H7B	0.9700
C2—H2C	0.9600	C8—H8A	0.9600
C3—C4	1.49 (3)	C8—H8B	0.9600
C3—H3A	0.9700	C8—H8C	0.9600

S1—Re—S2ⁱ	109.44 (14)	C3—C4—H4A	109.5
S1—Re—S2ⁱⁱ	109.44 (14)	C3—C4—H4B	109.5
S2ⁱ—Re—S2ⁱⁱ	109.51 (14)	H4A—C4—H4B	109.5
S1—Re—S2	109.44 (14)	C3—C4—H4C	109.5
S2ⁱ—Re—S2	109.50 (14)	H4A—C4—H4C	109.5
S2ⁱⁱ—Re—S2	109.50 (14)	H4B—C4—H4C	109.5
C1—N1—C5	114 (2)	C6—C5—N1	121 (2)
C1—N1—C3	108.9 (18)	C6—C5—H5A	107.2
C5—N1—C3	105.2 (19)	N1—C5—H5A	107.2
C1—N1—C7	108.2 (18)	C6—C5—H5B	107.2
C5—N1—C7	109.6 (17)	N1—C5—H5B	107.2
C3—N1—C7	110 (3)	H5A—C5—H5B	106.8
N1—C1—C2	122 (2)	C5—C6—H6A	109.5
N1—C1—H1A	106.7	C5—C6—H6B	109.5
C2—C1—H1A	106.7	H6A—C6—H6B	109.5
N1—C1—H1B	106.7	C5—C6—H6C	109.5
C2—C1—H1B	106.7	H6A—C6—H6C	109.5
H1A—C1—H1B	106.6	H6B—C6—H6C	109.5
C1—C2—H2A	109.5	N1—C7—C8	119 (2)
C1—C2—H2B	109.5	N1—C7—H7A	107.6
H2A—C2—H2B	109.5	C8—C7—H7A	107.6
C1—C2—H2C	109.5	N1—C7—H7B	107.6
H2A—C2—H2C	109.5	C8—C7—H7B	107.6
H2B—C2—H2C	109.5	H7A—C7—H7B	107.1
C4—C3—N1	117 (2)	C7—C8—H8A	109.5
C4—C3—H3A	108.0	C7—C8—H8B	109.5
N1—C3—H3A	108.0	H8A—C8—H8B	109.5
C4—C3—H3B	108.0	C7—C8—H8C	109.5
N1—C3—H3B	108.0	H8A—C8—H8C	109.5
H3A—C3—H3B	107.2	H8B—C8—H8C	109.5

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

Tetraethylammonium tetrathiorhenate (Ib) top

Crystal data top

(C₈H₂₀N)[ReS₄]	D_x = 2.034 Mg m⁻³
M_r = 444.69	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6₃	Cell parameters from 16453 reflections
a = 24.170 (3) Å	θ = 2.9–29.3°
c = 12.916 (2) Å	µ = 8.91 mm⁻¹
V = 6534.5 (19) Å³	T = 110 K
Z = 18	Prism, black
F(000) = 3852	0.24 × 0.21 × 0.16 mm

Data collection top

Oxford Diffraction Gemini E Ultra diffractometer with an EOS CCD camera	9707 independent reflections
Radiation source: fine-focus sealed tube Enhanced (Mo)	8807 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 16.2705 pixels mm^-1	θ_max = 29.7°, θ_min = 1.9°
ω scans	h = −32→29
Absorption correction: analytical [CrysAlis PRO (Agilent, 2013), based on expressions derived by Clark & Reid (1995)]	k = −30→27
T_min = 0.253, T_max = 0.351	l = −17→17
44958 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.028	w = 1/[σ²(F_o²) + (0.008P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.048	(Δ/σ)_max = 0.002
S = 1.05	Δρ_max = 0.87 e Å⁻³
9707 reflections	Δρ_min = −1.08 e Å⁻³
380 parameters	Absolute structure: Twinning involves inversion, so Flack parameter cannot be determined
1 restraint

Special details top

Refinement. Refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq
Re1	0.000000	0.000000	0.35220 (11)	0.0095 (2)
S1	0.000000	0.000000	0.5175 (4)	0.0158 (12)
S2	0.03466 (11)	0.09562 (11)	0.2979 (2)	0.0170 (5)
Re2	0.666667	0.333333	0.35177 (11)	0.0096 (2)
S3	0.666667	0.333333	0.5165 (4)	0.0165 (11)
S4	0.72698 (11)	0.42896 (12)	0.2975 (2)	0.0178 (5)
Re3	0.333333	0.666667	0.35284 (11)	0.0097 (2)
S5	0.333333	0.666667	0.5197 (4)	0.0107 (11)
S6	0.39202 (11)	0.76280 (12)	0.2985 (2)	0.0171 (5)
Re4	0.33152 (2)	0.32944 (2)	0.39300 (2)	0.00888 (14)
S7	0.31787 (9)	0.32427 (9)	0.55692 (15)	0.0152 (4)
S8	0.38743 (10)	0.28632 (10)	0.35143 (18)	0.0150 (5)
S9	0.38027 (11)	0.42763 (11)	0.34619 (18)	0.0154 (5)
S10	0.24045 (10)	0.27951 (12)	0.3185 (2)	0.0159 (5)
Re5	0.66238 (2)	0.66500 (2)	0.38567 (2)	0.0106 (2)
S11	0.65647 (9)	0.65264 (10)	0.55018 (16)	0.0178 (5)
S12	0.70584 (12)	0.61460 (11)	0.31983 (18)	0.0151 (5)
S13	0.71863 (11)	0.76468 (10)	0.3498 (2)	0.0160 (5)
S14	0.56841 (11)	0.62819 (12)	0.32167 (18)	0.0165 (5)
N1	0.2288 (5)	0.1209 (4)	0.1357 (17)	0.016 (2)
C1	0.2347 (4)	0.0831 (4)	0.2256 (5)	0.0139 (16)
H1A	0.195518	0.040614	0.228117	0.017*
H1B	0.271116	0.076230	0.211697	0.017*
C2	0.2444 (6)	0.1145 (4)	0.3303 (8)	0.020 (2)
H2A	0.247669	0.087276	0.383348	0.031*
H2B	0.283761	0.156106	0.329500	0.031*
H2C	0.208025	0.120425	0.345950	0.031*
C3	0.2216 (3)	0.0835 (3)	0.0367 (5)	0.0129 (15)
H3A	0.220731	0.109107	−0.022482	0.015*
H3B	0.260166	0.079511	0.028873	0.015*
C4	0.1635 (4)	0.0173 (3)	0.0288 (5)	0.020 (2)
H4A	0.164110	−0.001845	−0.037826	0.029*
H4B	0.164196	−0.009433	0.085252	0.029*
H4C	0.124613	0.020274	0.033705	0.029*
C5	0.1699 (3)	0.1264 (4)	0.1529 (6)	0.0149 (17)
H5A	0.133393	0.083134	0.166333	0.018*
H5B	0.176498	0.152166	0.216189	0.018*
C6	0.1520 (4)	0.1554 (4)	0.0670 (5)	0.0205 (18)
H6A	0.113364	0.156707	0.086097	0.031*
H6B	0.186976	0.198975	0.054225	0.031*
H6C	0.143741	0.129734	0.004219	0.031*
C7	0.2858 (3)	0.1860 (3)	0.1261 (6)	0.0127 (16)
H7A	0.287911	0.211108	0.187997	0.015*
H7B	0.279841	0.207276	0.065088	0.015*
C8	0.3494 (5)	0.1881 (4)	0.1149 (7)	0.021 (2)
H8A	0.383880	0.232598	0.109143	0.031*
H8B	0.356776	0.168417	0.175826	0.031*
H8C	0.348687	0.164576	0.052619	0.031*
N2	0.2191 (3)	0.4378 (5)	0.1385 (18)	0.015 (3)
C9	0.2538 (4)	0.4319 (3)	0.2279 (5)	0.0135 (16)
H9A	0.296381	0.470942	0.231879	0.016*
H9B	0.260564	0.395301	0.215868	0.016*
C10	0.2202 (4)	0.4225 (6)	0.3320 (8)	0.021 (2)
H10A	0.246203	0.419085	0.386971	0.032*
H10B	0.214278	0.459133	0.345867	0.032*
H10C	0.178397	0.383357	0.329828	0.032*
C11	0.1531 (3)	0.3811 (3)	0.1254 (6)	0.0160 (17)
H11A	0.133278	0.388131	0.063544	0.019*
H11B	0.127056	0.378589	0.186186	0.019*
C12	0.1506 (4)	0.3168 (5)	0.1135 (8)	0.022 (2)
H12A	0.106143	0.282752	0.105395	0.033*
H12B	0.175213	0.318095	0.052290	0.033*
H12C	0.168977	0.308533	0.175190	0.033*
C13	0.2127 (3)	0.4978 (3)	0.1536 (5)	0.0131 (16)
H13A	0.184222	0.490526	0.213448	0.016*
H13B	0.255231	0.534329	0.170945	0.016*
C14	0.1863 (4)	0.5160 (4)	0.0596 (6)	0.0201 (17)
H14A	0.183867	0.554361	0.075788	0.030*
H14B	0.214761	0.524662	0.000237	0.030*
H14C	0.143610	0.480770	0.042825	0.030*
C15	0.2578 (3)	0.4447 (3)	0.0404 (5)	0.0172 (16)
H15A	0.262081	0.406278	0.033457	0.021*
H15B	0.233415	0.446039	−0.020227	0.021*
C16	0.3235 (4)	0.5029 (4)	0.0376 (6)	0.023 (2)
H16A	0.344677	0.503511	−0.027391	0.034*
H16B	0.319934	0.541502	0.042338	0.034*
H16C	0.348662	0.501657	0.096135	0.034*
N3	0.5567 (3)	0.4520 (4)	0.1362 (16)	0.013 (3)
C17	0.5148 (3)	0.4158 (3)	0.2259 (5)	0.0132 (15)
H17A	0.511407	0.373309	0.229175	0.016*
H17B	0.471441	0.408995	0.213221	0.016*
C18	0.5382 (4)	0.4486 (4)	0.3301 (8)	0.023 (2)
H18A	0.508369	0.422111	0.384477	0.034*
H18B	0.580622	0.454563	0.344556	0.034*
H18C	0.540591	0.490307	0.328575	0.034*
C19	0.5261 (3)	0.4136 (3)	0.0387 (5)	0.0136 (15)
H19A	0.482758	0.407899	0.031716	0.016*
H19B	0.551399	0.438524	−0.021869	0.016*
C20	0.5207 (4)	0.3485 (3)	0.0357 (6)	0.0176 (19)
H20A	0.500567	0.327002	−0.029382	0.026*
H20B	0.563461	0.353448	0.040443	0.026*
H20C	0.494689	0.322765	0.094130	0.026*
C21	0.5629 (3)	0.5169 (3)	0.1230 (6)	0.0153 (17)
H21A	0.588891	0.537152	0.060404	0.018*
H21B	0.586552	0.543683	0.183095	0.018*
C22	0.5000 (4)	0.5170 (4)	0.1129 (7)	0.021 (2)
H22A	0.508879	0.560968	0.104620	0.031*
H22B	0.476566	0.491726	0.052262	0.031*
H22C	0.474221	0.498273	0.175262	0.031*
C23	0.6234 (3)	0.4607 (3)	0.1529 (5)	0.0138 (16)
H23A	0.642488	0.487591	0.215039	0.017*
H23B	0.618705	0.418332	0.167444	0.017*
C24	0.6693 (4)	0.4905 (4)	0.0638 (5)	0.0180 (17)
H24A	0.710386	0.494019	0.081621	0.027*
H24B	0.651791	0.463676	0.002054	0.027*
H24C	0.675632	0.533108	0.049767	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Re1	0.0105 (3)	0.0105 (3)	0.0075 (5)	0.00524 (13)	0.000	0.000
S1	0.0201 (18)	0.0201 (18)	0.007 (2)	0.0101 (9)	0.000	0.000
S2	0.0194 (12)	0.0124 (11)	0.0195 (11)	0.0082 (10)	0.0002 (10)	0.0028 (9)
Re2	0.0102 (3)	0.0102 (3)	0.0084 (6)	0.00512 (14)	0.000	0.000
S3	0.0224 (18)	0.0224 (18)	0.005 (2)	0.0112 (9)	0.000	0.000
S4	0.0187 (12)	0.0148 (11)	0.0174 (11)	0.0065 (10)	0.0010 (10)	0.0034 (9)
Re3	0.0115 (3)	0.0115 (3)	0.0063 (6)	0.00573 (14)	0.000	0.000
S5	0.0113 (16)	0.0113 (16)	0.010 (3)	0.0056 (8)	0.000	0.000
S6	0.0178 (11)	0.0112 (11)	0.0185 (12)	0.0042 (9)	0.0024 (10)	0.0032 (9)
Re4	0.00993 (19)	0.0092 (2)	0.0069 (3)	0.00435 (15)	−0.00001 (13)	0.00042 (19)
S7	0.0193 (10)	0.0147 (10)	0.0090 (8)	0.0065 (8)	0.0004 (8)	0.0011 (7)
S8	0.0135 (10)	0.0169 (10)	0.0167 (11)	0.0093 (8)	0.0016 (9)	−0.0010 (9)
S9	0.0169 (11)	0.0127 (9)	0.0150 (10)	0.0062 (9)	0.0013 (9)	0.0041 (8)
S10	0.0124 (10)	0.0159 (12)	0.0176 (11)	0.0058 (9)	−0.0044 (8)	−0.0024 (9)
Re5	0.0095 (2)	0.0093 (2)	0.0129 (6)	0.00455 (15)	0.00000 (18)	−0.00072 (13)
S11	0.0218 (12)	0.0161 (11)	0.0138 (9)	0.0082 (8)	0.0000 (8)	0.0005 (8)
S12	0.0147 (11)	0.0146 (11)	0.0182 (11)	0.0089 (9)	0.0044 (9)	0.0007 (9)
S13	0.0167 (11)	0.0111 (9)	0.0189 (13)	0.0059 (9)	−0.0014 (9)	0.0011 (8)
S14	0.0118 (10)	0.0179 (12)	0.0197 (11)	0.0074 (9)	−0.0026 (8)	−0.0029 (9)
N1	0.016 (6)	0.014 (3)	0.015 (5)	0.006 (3)	0.000 (4)	−0.001 (6)
C1	0.019 (5)	0.011 (4)	0.013 (4)	0.008 (4)	0.000 (3)	0.001 (3)
C2	0.023 (6)	0.027 (5)	0.018 (5)	0.017 (4)	0.003 (4)	0.006 (3)
C3	0.016 (4)	0.012 (4)	0.014 (4)	0.010 (3)	−0.001 (3)	−0.004 (3)
C4	0.020 (5)	0.023 (5)	0.020 (4)	0.015 (4)	−0.001 (3)	−0.004 (3)
C5	0.013 (4)	0.011 (4)	0.023 (5)	0.008 (4)	0.003 (3)	0.000 (3)
C6	0.023 (5)	0.015 (4)	0.027 (4)	0.011 (4)	0.002 (4)	0.002 (4)
C7	0.014 (4)	0.010 (4)	0.010 (4)	0.002 (3)	−0.003 (3)	−0.004 (3)
C8	0.014 (5)	0.014 (5)	0.033 (5)	0.007 (4)	0.003 (4)	0.002 (4)
N2	0.012 (5)	0.005 (5)	0.021 (8)	0.000 (3)	0.000 (4)	0.001 (5)
C9	0.009 (4)	0.009 (4)	0.022 (4)	0.005 (3)	−0.004 (3)	−0.006 (3)
C10	0.020 (5)	0.033 (6)	0.012 (5)	0.014 (4)	−0.001 (3)	0.002 (4)
C11	0.013 (4)	0.008 (4)	0.024 (4)	0.003 (3)	−0.006 (3)	−0.008 (3)
C12	0.023 (5)	0.019 (6)	0.024 (6)	0.011 (4)	−0.008 (4)	−0.005 (4)
C13	0.015 (4)	0.010 (4)	0.018 (4)	0.009 (3)	0.004 (3)	0.004 (3)
C14	0.024 (5)	0.018 (4)	0.022 (4)	0.014 (4)	−0.007 (4)	−0.002 (4)
C15	0.018 (4)	0.020 (4)	0.015 (4)	0.010 (3)	0.006 (3)	−0.001 (3)
C16	0.016 (4)	0.025 (5)	0.023 (4)	0.007 (4)	0.005 (3)	0.002 (4)
N3	0.016 (4)	0.012 (4)	0.012 (6)	0.008 (4)	−0.003 (3)	−0.004 (5)
C17	0.010 (4)	0.009 (4)	0.018 (4)	0.003 (3)	0.003 (3)	0.003 (3)
C18	0.022 (5)	0.019 (5)	0.019 (6)	0.004 (4)	0.003 (4)	0.004 (3)
C19	0.014 (4)	0.012 (3)	0.015 (4)	0.007 (3)	−0.009 (3)	−0.008 (3)
C20	0.017 (4)	0.007 (4)	0.024 (4)	0.002 (3)	−0.004 (3)	−0.006 (3)
C21	0.014 (4)	0.008 (4)	0.023 (5)	0.005 (3)	0.001 (3)	0.004 (3)
C22	0.034 (5)	0.023 (5)	0.014 (5)	0.021 (4)	−0.006 (3)	−0.003 (4)
C23	0.008 (4)	0.016 (4)	0.016 (4)	0.004 (3)	−0.001 (3)	−0.002 (3)
C24	0.013 (4)	0.023 (4)	0.019 (4)	0.010 (4)	0.010 (4)	0.009 (4)

Geometric parameters (Å, º) top

Re1—S1	2.135 (5)	C9—C10	1.528 (11)
Re1—S2	2.144 (2)	C9—H9A	0.9900
Re1—S2ⁱ	2.144 (2)	C9—H9B	0.9900
Re1—S2ⁱⁱ	2.144 (2)	C10—H10A	0.9800
Re2—S3	2.128 (5)	C10—H10B	0.9800
Re2—S4ⁱⁱⁱ	2.142 (2)	C10—H10C	0.9800
Re2—S4^iv	2.142 (2)	C11—C12	1.531 (11)
Re2—S4	2.142 (2)	C11—H11A	0.9900
Re3—S6^v	2.146 (2)	C11—H11B	0.9900
Re3—S6	2.146 (2)	C12—H12A	0.9800
Re3—S6^vi	2.146 (2)	C12—H12B	0.9800
Re3—S5	2.155 (5)	C12—H12C	0.9800
Re4—S7	2.137 (2)	C13—C14	1.534 (10)
Re4—S10	2.138 (2)	C13—H13A	0.9900
Re4—S9	2.142 (2)	C13—H13B	0.9900
Re4—S8	2.147 (2)	C14—H14A	0.9800
Re5—S11	2.141 (2)	C14—H14B	0.9800
Re5—S12	2.142 (2)	C14—H14C	0.9800
Re5—S13	2.143 (2)	C15—C16	1.506 (10)
Re5—S14	2.148 (2)	C15—H15A	0.9900
N1—C7	1.490 (11)	C15—H15B	0.9900
N1—C5	1.513 (11)	C16—H16A	0.9800
N1—C3	1.52 (2)	C16—H16B	0.9800
N1—C1	1.528 (18)	C16—H16C	0.9800
C1—C2	1.510 (11)	N3—C17	1.499 (18)
C1—H1A	0.9900	N3—C21	1.508 (12)
C1—H1B	0.9900	N3—C19	1.520 (18)
C2—H2A	0.9800	N3—C23	1.533 (10)
C2—H2B	0.9800	C17—C18	1.520 (11)
C2—H2C	0.9800	C17—H17A	0.9900
C3—C4	1.516 (10)	C17—H17B	0.9900
C3—H3A	0.9900	C18—H18A	0.9800
C3—H3B	0.9900	C18—H18B	0.9800
C4—H4A	0.9800	C18—H18C	0.9800
C4—H4B	0.9800	C19—C20	1.514 (9)
C4—H4C	0.9800	C19—H19A	0.9900
C5—C6	1.488 (10)	C19—H19B	0.9900
C5—H5A	0.9900	C20—H20A	0.9800
C5—H5B	0.9900	C20—H20B	0.9800
C6—H6A	0.9800	C20—H20C	0.9800
C6—H6B	0.9800	C21—C22	1.526 (11)
C6—H6C	0.9800	C21—H21A	0.9900
C7—C8	1.519 (11)	C21—H21B	0.9900
C7—H7A	0.9900	C22—H22A	0.9800
C7—H7B	0.9900	C22—H22B	0.9800
C8—H8A	0.9800	C22—H22C	0.9800
C8—H8B	0.9800	C23—C24	1.508 (9)
C8—H8C	0.9800	C23—H23A	0.9900
N2—C9	1.48 (2)	C23—H23B	0.9900
N2—C11	1.505 (10)	C24—H24A	0.9800
N2—C15	1.53 (2)	C24—H24B	0.9800
N2—C13	1.545 (11)	C24—H24C	0.9800

S1—Re1—S2	109.09 (8)	C9—C10—H10A	109.5
S1—Re1—S2ⁱ	109.09 (8)	C9—C10—H10B	109.5
S2—Re1—S2ⁱ	109.85 (8)	H10A—C10—H10B	109.5
S1—Re1—S2ⁱⁱ	109.09 (8)	C9—C10—H10C	109.5
S2—Re1—S2ⁱⁱ	109.85 (8)	H10A—C10—H10C	109.5
S2ⁱ—Re1—S2ⁱⁱ	109.85 (8)	H10B—C10—H10C	109.5
S3—Re2—S4ⁱⁱⁱ	109.10 (8)	N2—C11—C12	115.0 (6)
S3—Re2—S4^iv	109.10 (8)	N2—C11—H11A	108.5
S4ⁱⁱⁱ—Re2—S4^iv	109.84 (8)	C12—C11—H11A	108.5
S3—Re2—S4	109.10 (8)	N2—C11—H11B	108.5
S4ⁱⁱⁱ—Re2—S4	109.84 (8)	C12—C11—H11B	108.5
S4^iv—Re2—S4	109.84 (7)	H11A—C11—H11B	107.5
S6^v—Re3—S6	109.87 (7)	C11—C12—H12A	109.5
S6^v—Re3—S6^vi	109.87 (7)	C11—C12—H12B	109.5
S6—Re3—S6^vi	109.87 (7)	H12A—C12—H12B	109.5
S6^v—Re3—S5	109.07 (7)	C11—C12—H12C	109.5
S6—Re3—S5	109.07 (7)	H12A—C12—H12C	109.5
S6^vi—Re3—S5	109.07 (7)	H12B—C12—H12C	109.5
S7—Re4—S10	109.13 (8)	C14—C13—N2	114.9 (10)
S7—Re4—S9	109.13 (8)	C14—C13—H13A	108.5
S10—Re4—S9	109.81 (9)	N2—C13—H13A	108.5
S7—Re4—S8	109.61 (8)	C14—C13—H13B	108.5
S10—Re4—S8	109.49 (10)	N2—C13—H13B	108.5
S9—Re4—S8	109.64 (8)	H13A—C13—H13B	107.5
S11—Re5—S12	109.40 (7)	C13—C14—H14A	109.5
S11—Re5—S13	109.38 (9)	C13—C14—H14B	109.5
S12—Re5—S13	109.74 (9)	H14A—C14—H14B	109.5
S11—Re5—S14	109.96 (8)	C13—C14—H14C	109.5
S12—Re5—S14	109.23 (9)	H14A—C14—H14C	109.5
S13—Re5—S14	109.13 (9)	H14B—C14—H14C	109.5
C7—N1—C5	109.5 (6)	C16—C15—N2	115.0 (7)
C7—N1—C3	109.1 (12)	C16—C15—H15A	108.5
C5—N1—C3	110.0 (10)	N2—C15—H15A	108.5
C7—N1—C1	112.4 (11)	C16—C15—H15B	108.5
C5—N1—C1	108.3 (12)	N2—C15—H15B	108.5
C3—N1—C1	107.4 (5)	H15A—C15—H15B	107.5
C2—C1—N1	114.7 (8)	C15—C16—H16A	109.5
C2—C1—H1A	108.6	C15—C16—H16B	109.5
N1—C1—H1A	108.6	H16A—C16—H16B	109.5
C2—C1—H1B	108.6	C15—C16—H16C	109.5
N1—C1—H1B	108.6	H16A—C16—H16C	109.5
H1A—C1—H1B	107.6	H16B—C16—H16C	109.5
C1—C2—H2A	109.5	C17—N3—C21	112.4 (10)
C1—C2—H2B	109.5	C17—N3—C19	107.6 (5)
H2A—C2—H2B	109.5	C21—N3—C19	107.8 (12)
C1—C2—H2C	109.5	C17—N3—C23	109.2 (12)
H2A—C2—H2C	109.5	C21—N3—C23	108.9 (5)
H2B—C2—H2C	109.5	C19—N3—C23	110.9 (10)
C4—C3—N1	117.0 (7)	N3—C17—C18	114.4 (7)
C4—C3—H3A	108.0	N3—C17—H17A	108.7
N1—C3—H3A	108.0	C18—C17—H17A	108.7
C4—C3—H3B	108.0	N3—C17—H17B	108.7
N1—C3—H3B	108.0	C18—C17—H17B	108.7
H3A—C3—H3B	107.3	H17A—C17—H17B	107.6
C3—C4—H4A	109.5	C17—C18—H18A	109.5
C3—C4—H4B	109.5	C17—C18—H18B	109.5
H4A—C4—H4B	109.5	H18A—C18—H18B	109.5
C3—C4—H4C	109.5	C17—C18—H18C	109.5
H4A—C4—H4C	109.5	H18A—C18—H18C	109.5
H4B—C4—H4C	109.5	H18B—C18—H18C	109.5
C6—C5—N1	116.1 (10)	C20—C19—N3	114.8 (7)
C6—C5—H5A	108.3	C20—C19—H19A	108.6
N1—C5—H5A	108.3	N3—C19—H19A	108.6
C6—C5—H5B	108.3	C20—C19—H19B	108.6
N1—C5—H5B	108.3	N3—C19—H19B	108.6
H5A—C5—H5B	107.4	H19A—C19—H19B	107.6
C5—C6—H6A	109.5	C19—C20—H20A	109.5
C5—C6—H6B	109.5	C19—C20—H20B	109.5
H6A—C6—H6B	109.5	H20A—C20—H20B	109.5
C5—C6—H6C	109.5	C19—C20—H20C	109.5
H6A—C6—H6C	109.5	H20A—C20—H20C	109.5
H6B—C6—H6C	109.5	H20B—C20—H20C	109.5
N1—C7—C8	115.4 (6)	N3—C21—C22	115.5 (6)
N1—C7—H7A	108.4	N3—C21—H21A	108.4
C8—C7—H7A	108.4	C22—C21—H21A	108.4
N1—C7—H7B	108.4	N3—C21—H21B	108.4
C8—C7—H7B	108.4	C22—C21—H21B	108.4
H7A—C7—H7B	107.5	H21A—C21—H21B	107.5
C7—C8—H8A	109.5	C21—C22—H22A	109.5
C7—C8—H8B	109.5	C21—C22—H22B	109.5
H8A—C8—H8B	109.5	H22A—C22—H22B	109.5
C7—C8—H8C	109.5	C21—C22—H22C	109.5
H8A—C8—H8C	109.5	H22A—C22—H22C	109.5
H8B—C8—H8C	109.5	H22B—C22—H22C	109.5
C9—N2—C11	113.2 (12)	C24—C23—N3	115.5 (9)
C9—N2—C15	108.2 (4)	C24—C23—H23A	108.4
C11—N2—C15	108.4 (13)	N3—C23—H23A	108.4
C9—N2—C13	108.7 (12)	C24—C23—H23B	108.4
C11—N2—C13	108.2 (4)	N3—C23—H23B	108.4
C15—N2—C13	110.1 (11)	H23A—C23—H23B	107.5
N2—C9—C10	114.6 (8)	C23—C24—H24A	109.5
N2—C9—H9A	108.6	C23—C24—H24B	109.5
C10—C9—H9A	108.6	H24A—C24—H24B	109.5
N2—C9—H9B	108.6	C23—C24—H24C	109.5
C10—C9—H9B	108.6	H24A—C24—H24C	109.5
H9A—C9—H9B	107.6	H24B—C24—H24C	109.5

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

Tetraethylammonium tetrathiorhenate (Ic) top

Crystal data top

(C₈H₂₀N)[ReS₄]	F(000) = 428
M_r = 444.69	D_x = 2.051 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 7.900 (2) Å	Cell parameters from 3279 reflections
b = 12.842 (3) Å	θ = 2.9–29.5°
c = 8.118 (2) Å	µ = 8.99 mm⁻¹
β = 119.04 (2)°	T = 150 K
V = 720.0 (3) Å³	Prism, black
Z = 2	0.24 × 0.20 × 0.17 mm

Data collection top

Oxford Diffraction Gemini E Ultra diffractometer with an EOS CCD camera	2814 independent reflections
Radiation source: fine-focus sealed tube Enhanced (Mo)	2808 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 16.2705 pixels mm^-1	θ_max = 29.3°, θ_min = 3.3°
ω scans	h = −10→10
Absorption correction: analytical [CrysAlis PRO (Agilent, 2013), based on expressions derived by Clark & Reid (1995)]	k = −15→16
T_min = 0.241, T_max = 0.336	l = −10→10
4476 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.052	w = 1/[σ²(F_o²) + (0.0596P)² + 29.5424P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.138	(Δ/σ)_max = 0.002
S = 1.09	Δρ_max = 2.01 e Å⁻³
2814 reflections	Δρ_min = −4.80 e Å⁻³
87 parameters	Absolute structure: Flack x determined using 1080 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
89 restraints	Absolute structure parameter: 0.105 (18)

Special details top

Refinement. Refined as a 6-component twin.

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

	x	y	z	U_iso*/U_eq
Re	0.0222 (5)	0.25452 (19)	0.03784 (19)	0.0174 (3)
S1	0.0542 (18)	0.4194 (5)	0.0361 (16)	0.023 (3)
S2	−0.105 (2)	0.1961 (8)	−0.2401 (14)	0.022 (2)
S3	−0.150 (2)	0.2166 (9)	0.163 (2)	0.026 (3)
S4	0.3036 (17)	0.1879 (9)	0.194 (2)	0.030 (3)
N	0.680 (3)	0.5128 (17)	0.326 (3)	0.016 (6)*
C1	0.595 (6)	0.417 (2)	0.366 (5)	0.025 (9)*
H1A	0.682470	0.357262	0.384336	0.030*
H1B	0.469486	0.401274	0.253227	0.030*
C2	0.562 (8)	0.422 (4)	0.537 (7)	0.030 (11)*
H2A	0.507365	0.356325	0.550356	0.045*
H2B	0.685905	0.435040	0.651499	0.045*
H2C	0.472238	0.479193	0.519969	0.045*
C3	0.878 (5)	0.535 (3)	0.492 (5)	0.025 (9)*
H3A	0.860836	0.555189	0.600623	0.029*
H3B	0.932921	0.596495	0.459715	0.029*
C4	1.025 (7)	0.447 (3)	0.552 (7)	0.029 (10)*
H4A	1.147093	0.468969	0.659847	0.044*
H4B	0.974470	0.386098	0.588604	0.044*
H4C	1.046759	0.427522	0.447296	0.044*
C5	0.546 (5)	0.604 (2)	0.292 (6)	0.027 (9)*
H5A	0.527783	0.612571	0.403188	0.033*
H5B	0.418227	0.587752	0.182885	0.033*
C6	0.613 (8)	0.709 (2)	0.253 (5)	0.025 (8)*
H6A	0.517313	0.762502	0.233300	0.037*
H6B	0.738025	0.727722	0.361484	0.037*
H6C	0.628155	0.702831	0.140546	0.037*
C7	0.703 (5)	0.494 (3)	0.153 (5)	0.017 (8)*
H7A	0.780548	0.430017	0.174116	0.021*
H7B	0.777263	0.552620	0.140771	0.021*
C8	0.516 (4)	0.482 (3)	−0.033 (5)	0.021 (9)*
H8A	0.546821	0.470602	−0.134755	0.032*
H8B	0.442106	0.423120	−0.025216	0.032*
H8C	0.438810	0.546083	−0.058658	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Re	0.0322 (12)	0.0080 (4)	0.0215 (7)	0.0046 (17)	0.0207 (11)	0.004 (2)
S1	0.027 (8)	0.008 (3)	0.025 (8)	−0.001 (3)	0.005 (4)	0.005 (4)
S2	0.015 (7)	0.021 (4)	0.030 (6)	−0.003 (5)	0.010 (5)	−0.004 (4)
S3	0.025 (8)	0.027 (5)	0.039 (9)	0.006 (4)	0.025 (8)	0.006 (5)
S4	0.019 (6)	0.016 (5)	0.048 (9)	0.012 (5)	0.011 (6)	0.002 (7)

Geometric parameters (Å, º) top

Re—S3	2.111 (9)	C3—H3B	0.9900
Re—S2	2.113 (10)	C4—H4A	0.9800
Re—S4	2.132 (10)	C4—H4B	0.9800
Re—S1	2.133 (7)	C4—H4C	0.9800
N—C5	1.51 (2)	C5—C6	1.53 (3)
N—C1	1.51 (2)	C5—H5A	0.9900
N—C3	1.52 (2)	C5—H5B	0.9900
N—C7	1.52 (2)	C6—H6A	0.9800
C1—C2	1.54 (3)	C6—H6B	0.9800
C1—H1A	0.9900	C6—H6C	0.9800
C1—H1B	0.9900	C7—C8	1.52 (3)
C2—H2A	0.9800	C7—H7A	0.9900
C2—H2B	0.9800	C7—H7B	0.9900
C2—H2C	0.9800	C8—H8A	0.9800
C3—C4	1.53 (3)	C8—H8B	0.9800
C3—H3A	0.9900	C8—H8C	0.9800

S3—Re—S2	110.3 (6)	C3—C4—H4A	109.5
S3—Re—S4	110.6 (6)	C3—C4—H4B	109.5
S2—Re—S4	108.0 (6)	H4A—C4—H4B	109.5
S3—Re—S1	109.8 (5)	C3—C4—H4C	109.5
S2—Re—S1	110.0 (4)	H4A—C4—H4C	109.5
S4—Re—S1	108.0 (5)	H4B—C4—H4C	109.5
C5—N—C1	109.4 (17)	N—C5—C6	116 (3)
C5—N—C3	109.9 (18)	N—C5—H5A	108.3
C1—N—C3	109.7 (18)	C6—C5—H5A	108.3
C5—N—C7	109.9 (18)	N—C5—H5B	108.3
C1—N—C7	109.5 (17)	C6—C5—H5B	108.3
C3—N—C7	108.5 (17)	H5A—C5—H5B	107.4
N—C1—C2	116 (2)	C5—C6—H6A	109.5
N—C1—H1A	108.2	C5—C6—H6B	109.5
C2—C1—H1A	108.2	H6A—C6—H6B	109.5
N—C1—H1B	108.2	C5—C6—H6C	109.5
C2—C1—H1B	108.2	H6A—C6—H6C	109.5
H1A—C1—H1B	107.3	H6B—C6—H6C	109.5
C1—C2—H2A	109.5	N—C7—C8	116 (2)
C1—C2—H2B	109.5	N—C7—H7A	108.3
H2A—C2—H2B	109.5	C8—C7—H7A	108.3
C1—C2—H2C	109.5	N—C7—H7B	108.3
H2A—C2—H2C	109.5	C8—C7—H7B	108.3
H2B—C2—H2C	109.5	H7A—C7—H7B	107.4
N—C3—C4	116 (3)	C7—C8—H8A	109.5
N—C3—H3A	108.3	C7—C8—H8B	109.5
C4—C3—H3A	108.3	H8A—C8—H8B	109.5
N—C3—H3B	108.3	C7—C8—H8C	109.5
C4—C3—H3B	108.3	H8A—C8—H8C	109.5
H3A—C3—H3B	107.4	H8B—C8—H8C	109.5

Twin components in Ic top

Twin components	Appropriate symmetry operations in P6₃mc	h,k,l;i [i = -h-l]^*	Fractional contribution k_i
1	[1] 1	h,k,l;i	0.178 (7)
2	[2] 3⁺ (0,0,z)	l,k,i;h	0.213 (7)
3	[3] 3^- (0,0,z)	i,k,h;l	0.080 (7)
4	[7] m (x,-x,z)	-l,k,-h;i	0.084 (7)
5	[8] m (x,2x,z)	-h,k,-i;l	0.233 (7)
6	[9] m (2x,x,z)	-i,k,-l;h	0.212 (7)

Note: (*) the fourth Miller index is the sum of -h and -l, because the transformation from P6₃mc to P2₁ causes the 6₃-axis along the y axis.

Crystallographic data for the high-temperature phase of several Et₄NMY4 compounds (M = B, Cl, Re, Fe, In and Tl; Y = O, F, S, Cl, Br) top

Anion	BF₄^- ^a	ClO₄^- ^b	ReS₄^- ^c	FeCl₄^- ^d	FeBrCl₃^{- e}	InCl₄^{- f}	TlCl₄^{- g}
Temperature (K)	373	393	297 (2)	290–295	293	r.t.	297
Temperature range (K)	>342	>378.5	>285	>234.7	n.d.^h	n.d.	>222
Space group	Fm3m	Fm3m	P6₃mc	P6₃mc	P6₃mc	P6₃mc	P6₃mc
Z	4	4	2	2	2	2	2
V/Z (Å³)	317.3 (4)	329.1	376.42 (7)	383.7–385.7	388.4 (1)	397	394.7 (4)

Notes and references: (a) Matsumoto et al. (2014); (b) Ye et al. (2016); (c) this work; (d) Lutz et al. (2014), Warnke et al. (2010), Evans et al. (1990) and Navarro et al. (1988); (e) Evans et al. (1990); (f) Trotter et al. (1969); (g) Lenck et al. (1991); (h) n.d. = not determined.

Crystallographic data for the low-temperature phase of several Et₄NMY4 compounds (M = B, P, Cl, Mn, Re and Fe; Y = O, F, S and Cl) top

Anion	ClO₄^- ^a	BF₄^- ^b	MnO₄^- ^c	PO₂F₂^- ^d	ReO₃S^- ^e	ReS₄^- ^f	ReS₄^- ^f	FeCl₄^{- g}	FeCl₄^- ^h
Temperature (K)	110–173	298	293	110	293 (2)	149.9 (3)	109.9 (3)	110–170	230
Temperature range (K)	<378.5	<342	n.d. ⁱ	<323	n.d. ⁱ	<285	metastable	<226.6	234.7–226.6
Apace group	Cc	Cc	P2₁/c	Cc	P2₁/c	P2₁	P6₃	Pca2₁	P6₃
Z	4	4	4	4	8	2	18	4	18
V/Z (Å³)	291.3–294.5	294.5 (3)	307.7 (1)	311.39 (4)	316.7 (1)	360.0 (2)	363.05 (2)	363.77–367.75	376.86 (3)

Notes and references: (a) Ibers (1993), Kivikoski et al. (1995) and Ye et al. (2016); (b) Giuseppetti et al. (1994), Matsumoto et al. (2012) and Matsumoto et al. (2014); (c) Whang et al. (1991); (d) Matsumoto et al. (2012); (e) Partyka & Holm (2004); (f) this work; (g) Lutz et al. (2014) and Navarro et al. (1988); (h) Lutz et al. (2014) and Navarro et al. (1988); (i) n.d. = not determined.

Intensity of the reflections with even and odd l (Ia, c) or k (Ic) from the fcf file top

	F²_av(odd)/F²_av	F²_av(even)/F²_av	F²_av(odd)/F²_av(even)	Δ^a (Å)
Ia (obs)	0.082	1.737	0.047	0
Ia (calc)	0.080	1.740	0.046	0
Ib (obs) ^b	0.184	1.815	0.102	0.0573^c
Ib (calc)	0.174	1.826	0.095	0.0573^c
Ic (obs)	0.803	1.196	0.672	0.2720
Ic (calc)	0.796	1.203	0.662	0.2720

Notes: (a) Average displacement of the Re atoms from the threefold axis. (b) Reflections of Ib with h = 3n and k = 3m overlap with appropriate reflections of Ic. The reflections with h = 3n and k = 3m are on average 1.2 times too strong and were not used in the refinement. (c) Re1, Re2 and Re3 = 0 Å; Re4 = 0.0815 Å; Re5 = 0.0905 Å.

Re—S bond lengths (Å) and S—Re—S angles (°) for some compounds with the ReS₄^- anion top

Cation	Et₄N⁺, Ib^a	Et₄N⁺, Ic^a	Et₄N⁺, Ia^a	Et₄N^+,b	Bu₄N^+,c	Ph₄P^+,d
Temperature (K)	109.9 (3)	149.9 (3)	297 (2)	r.t.^e	r.t.	r.t.
Re—S average	2.142 (2)	2.122 (10)	2.125 (4)	2.125 (4)	2.122 (6)	2.155 (30)
Re—S range	2.130–2.154	2.111–2.133	2.120–2.127	2.123–2.126	2.118–2.126	2.155–2.155
S—Re—S average	109.47 (9)	109.47 (71)	109.47 (17)	109.45 (11)	109.48 (84)	Not specified
S—Re—S range	109.06–109.95	108.01–110.61	109.33–109.61	109.4–109.5	107.4–112.8	Not specified

Notes and references: (a) this work; (b) Müller et al. (1987); (c) Do et al. (1985); (d) Diemann & Müller (1976); (e) r.t. - room temperature.

Acknowledgements

We thank Dr Birger Dittrich, MSc Moloud Mokfi and MSc Darya Schmidt for discussions.

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Volume 76| Part 3| March 2020| Pages 231-235

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