Crystal structure of octa-μ3-selenido-(p-toluene­sulfonato-κO)penta­kis­(tri­ethyl­phosphane-κP)-octa­hedro-hexa­rhenium(III) p-toluene­sulfonate di­chloro­methane disolvate

Edwards, J.A.; McDonald, R.; Szczepura, L.F.

doi:10.1107/S2056989015014334

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 71| Part 9| September 2015| Pages m158-m159

https://doi.org/10.1107/S2056989015014334

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Crystal structure of octa-μ₃-selenido-(p-toluenesulfonato-κO)pentakis(triethylphosphane-κP)-octahedro-hexarhenium(III) p-toluenesulfonate dichloromethane disolvate

Julia A. Edwards,^a Robert McDonald ^b and Lisa F. Szczepura ^a ^*

^aDepartment of Chemistry, Campus Box 4160, Illinois State University, Normal, IL 61790-4160, USA, and ^bDepartment of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2, Canada
^*Correspondence e-mail: lfszcze@IllinoisState.edu

Edited by T. J. Prior, University of Hull, England (Received 25 July 2015; accepted 29 July 2015; online 6 August 2015)

The title compound, [Re₆Se₈{O₃SC₆H₄(CH₃)}{P(C₂H₅)₃}₅](CH₃C₆H₄SO₃)·2CH₂Cl₂, contains the face-capped hexanuclear [Re₆(μ₃-Se)₈]²⁺ cluster core. The [Re₆Se₈]²⁺ cluster core displays a non-crystallographic center of symmetry and is bonded through the Re^III atoms to five triethylphosphane ligands and one p-toluenesulfonate ligand. One p-toluenesulfonate counter-ion and two dichloromethane solvent molecules are also present in the asymmetric unit. One of the ethyl chains of one triethylphosphane ligand and one of the CH₂Cl₂ solvent molecules are disordered over two sets of sites (occupancy ratios 0.65:0.35 and 0.5:0.5, respectively). The Re—O(sulfonate) bond length of 2.123 (5) Å is similar to other Re—O bond lengths of hexanuclear rhenium chalcogenide clusters containing other O-donor ligands such as dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and hydroxide.

Keywords: crystal structure; rhenium complex; [Re₆(μ₃-Se)₈]²⁺ cluster core; tosylate.

CCDC reference: 1010097

1. Related literature

Lindner & Grimmer (1971 ) reported the insertion of sulfur trioxide into the Re-alkyl bond of (p-tolyl)Re(CO)₅ to generate the first example of a rhenium complex to contain a tosylate moiety. Later, Eremenko et al. (1993 ) determined the structure of [Re(P(OiPr)₃)₂(CO)(NO)(OTs)₂] (OTs⁻ = p-toluenesulfonate anion) which represented the first structural report of a rhenium complex containing tosylate ligands. In the synthesis of octahedral rhenium chalcogenide cluster complexes, the substitution of either halide or nitrile ligands has proven an effective means for generating a variety of new cluster complexes (Zheng & Holm, 1997 ; Knott et al., 2013 ; Yoshimura et al., 2000 ). Nitrile ligands are often considered weakly coordinating and substitution of alkyl and aryl nitrile ligands has often been used in single metal chemistry (Endres, 1987 ) and in the preparation of [Re₆Q₈]²⁺ (Q = S or Se) cluster complexes (Zheng & Holm, 1997; Durham et al., 2012 ). However, there have been reports of the hexanuclear rhenium selenide cluster core, [Re₆Se₈]²⁺, activating nitriles to undergo reactions other than substitution (Orto et al., 2007 ; Szczepura et al., 2007 ). While structural reports of rhenium chalcogenide clusters containing other oxygen donor ligands have been previously reported (Dorson et al., 2009 ; Mironov et al., 2011 ; Zheng & Holm, 1997; Zheng et al., 1999 ), this report represents the first example of tosylate coordination to a [Re₆Q₈]²⁺ cluster core. The average Re—P bond length of the five terminal PEt₃ ligands in the title compound [2.479 Å] is similar to that in other rhenium selenide clusters containing PEt₃ ligands (Durham et al., 2012, 2015 ; Knott et al., 2013; Zheng & Holm, 1997; Zheng et al., 1999).

2. Experimental

2.1. Crystal data

[Re₆Se₈(C₇H₇O₃S)(C₆H₁₅P)₅](C₇H₇O₃S)·2CH₂Cl₂
M_r = 2851.85
Triclinic, $[P \overline 1]$
a = 11.7432 (10) Å
b = 16.6878 (14) Å
c = 18.9786 (16) Å
α = 93.4729 (11)°
β = 95.9862 (12)°
γ = 100.0851 (11)°
V = 3629.9 (5) Å³
Z = 2
Mo Kα radiation
μ = 14.33 mm⁻¹
T = 193 K
0.48 × 0.28 × 0.10 mm

2.2. Data collection

Bruker PLATFORM/SMART 1000 CCD area-detector diffractometer
Absorption correction: integration (SADABS; Sheldrick, 2008 ) T_min = 0.032, T_max = 0.255
31748 measured reflections
16405 independent reflections
11401 reflections with I > 2σ(I)
R_int = 0.031

2.3. Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.097
S = 1.02
16405 reflections
693 parameters
H-atom parameters constrained
Δρ_max = 2.67 e Å⁻³
Δρ_min = −1.26 e Å⁻³

Data collection: SMART (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: DIRDIF99 (Beurskens et al., 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1010097

Crystal structure: contains datablocks I, isu0804. DOI: https://doi.org/10.1107/S2056989015014334/pj2021sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015014334/pj2021Isup2.hkl

checkCIF report

Comment top

In the synthesis of octahedral rhenium chalcogenide cluster complexes, the substitution of either halide or nitrile ligands has proven an effective means for generating a variety of new cluster complexes (Zheng & Holm, 1997, Knott et al., 2013, Yoshimura et al., 2000). Substitution of halide ligands can be facilitated by silver(I) salts, where the precipitation of AgX (X = halide) drives the substitution reaction (Zheng & Holm, 1999, Durham et al., 2012). Nitrile ligands are often considered weakly coordinating and substitution of alkyl and aryl nitrile ligands has often been used in single metal chemistry (Endres, 1987) and in the preparation of [Re₆Q₈]²⁺ (Q = S or Se) cluster complexes (Zheng & Holm, 1997, Durham et al., 2012). However, there have been reports of the hexanuclear rhenium selenide cluster core, [Re₆Se₈]²⁺, activating nitriles to undergo reactions other than substitution (Orto et al., 2007, Szczepura et al., 2007). To address this, we sought to incorporate a weakly coordinating ligand that would be readily substituted, but would not be susceptible to nucleophilic attack. The tosylate ligand was our ligand of choice and here we report the preparation, characterization and X-ray structural analysis of [Re₆Se₈(PEt₃)₅(OTs)](OTs)·2CH₂Cl₂. We recently substituted the tosylate ligand in this complex for a N-heterocyclic carbene which resulted in the formation of the first [M₆Q₈]ⁿ⁺ complex to contain a carbene ligand (Durham et al. 2015).

The structural data for the title complex, [Re₆Se₈(PEt₃)₅(OTs)](OTs)·2CH₂Cl₂, shows that the core contains bond lengths (Re–Re and Re–Se) and bond angles (Re–Re–Re, Re–Re–Se, Se–Re–Se, Re–Se–Re) that are consistent with other [Re₆Se₈]²⁺ based cluster complexes (Dorson et al., 2009, Durham, et al., 2012, 2015, Knott et al., 2013, Mironov et al., 2011, Zheng & Holm 1997, Zheng et al. 1999). The average Re—P bond distance of the five terminal PEt₃ ligands is 2.4790 Å which also similarly compares with other rhenium selenide clusters containing PEt₃ ligands (Durham, et al., 2012, 2015, Knott et al., 2013, Zheng & Holm, 1997, 1999). The Re6–O1 bond length of the coordinated tosylate is 2.123 (5) Å and the Re6–O1–S1 bond angle is 136.5 (5)^o. The Re–O bond lengths of the coordinated tosylate ligands in [Re(P(OiPr)₃)₂(CO)(NO)(OTs)₂] were reported at 2.096 and 2.114 Å (Eremenko et al., 1993). While there are no other structural reports of rhenium complexes containing tosylate ligands, there are a number of structural reports of rhenium trifluoromethanesulfonate (TfO^-) complexes (Huertos et al., 2010, Matano et al., 1998, Tahmassebi et al., 1997). Examining the structural data for these Re–OTf complexes, the Re–O bond lengths range from 2.10 - 2.53 Å and the Re–O–S bond angles typically fall between 124 - 139°; the data for the title complex fall well within the range observed for these relatively similar ligands. The Re6–O1 bond distance reported here also compares favorably with Re–O bond lengths of [Re₆Se₈]²⁺ clusters containing other O-donor ligands such as DMSO, DMF and hydroxide (Dorson et al. (2009), Mironov et al. (2011), Zheng & Holm (1997, Zheng et al. 1999)).

Related literature top

Lindner & Grimmer (1971) reported the insertion of sulfur trioxide into the Re-alkyl bond of (p-tolyl)Re(CO)₅ to generate the first example of a rhenium complex to contain a tosylate moiety. Later, Eremenko et al. (1993) determined the structure of [Re(P(OiPr)₃)₂(CO)(NO)(OTs)₂] (OTs^- = p-toluenesulfonate anion) which represented the first structural report of a rhenium complex containing tosylate ligands. In the synthesis of octahedral rhenium chalcogenide cluster complexes, the substitution of either halide or nitrile ligands has proven an effective means for generating a variety of new cluster complexes (Zheng & Holm, 1997; Knott et al., 2013; Yoshimura et al., 2000). Nitrile ligands are often considered weakly coordinating and substitution of alkyl and aryl nitrile ligands has often been used in single metal chemistry (Endres, 1987) and in the preparation of [Re₆Q₈]²⁺ (Q = S or Se) cluster complexes (Zheng & Holm, 1997; Durham et al., 2012). However, there have been reports of the hexanuclear rhenium selenide cluster core, [Re₆Se₈]²⁺, activating nitriles to undergo reactions other than substitution (Orto et al., 2007; Szczepura et al., 2007). While structural reports of rhenium chalcogenide clusters containing other oxygen donor ligands have been previously reported (Dorson et al., 2009; Mironov et al., 2011; Zheng & Holm 1997; Zheng et al. 1999), this report represents the first example of tosylate coordination to a [Re₆Q₈]²⁺ cluster core. There are also a number of structural reports of rhenium trifluoromethanesulfonate (TfO^-) complexes (Huertos et al., 2010; Matano et al., 1998; Tahmassebi et al., 1997). For other [Re₆Se₈]²⁺ based-cluster complexes, see: Dorson et al. (2009); Durham et al. (2012, 2015); Knott et al. (2013); Mironov et al. (2011); Zheng & Holm (1997); Zheng et al. 1999). The average Re—P bond distance of the five terminal PEt₃ ligands [2.4790 Å] is similar to that in other rhenium selenide clusters containing PEt₃ ligands (Durham et al., 2012, 2015; Knott et al., 2013; Zheng & Holm, 1997; Zheng et al. 1999).

Experimental top

The [Re₆Se₈(PEt₃)₅I]I complex was obtained according to a previously published procedure (Zheng et al., 1997). The title complex is sensitive to water; therefore, this procedure was performed in an inert atmosphere glovebox. The starting cluster complex, [Re₆Se₈(PEt₃)₅I]I (199.9 mg, 0.0771 mmol) was dissolved in 20 ml of CH₂Cl₂ and placed in a round bottom flask. Separately, 61.2 mg (0.219 mmol) of AgOTs was dissolved in 5 ml of CH₂Cl₂ and transferred to the cluster solution. The flask was covered and allowed to stir overnight. The resulting slurry was filtered through Celite (to remove AgI) and the filtrate reduced to dryness. Reprecipitation using CH₂Cl₂ and Et₂O allowed the product to be isolated (178 mg, 86% yield) and crystals were obtained via the vapor diffusion technique using CH₂Cl₂ and Et₂O. ¹H NMR (400 MHz, CDCl₃, p.p.m.): 1.11 (45H, m, P(CH₂CH₃)), 2.05 (6H, m, P(CH₂CH₃)), 2.14 (24H, m P(CH₂CH₃)), 2.30 (3H, s, OSO₂C₆H₄CH₃ anion), 2.34 (3H, s, OSO₂C₆H₄CH₃ ligand), 7.08 (2H, d, OSO₂C₆H₄CH₃ anion), 7.13 (2H, d, OSO₂C₆H₄CH₄ ligand), 7.63 (2H, d, OSO₂C₆H₄CH₃ ligand), 7.88 (2H, d, OSO₂C₆H₄CH₃ anion). ³¹P {¹H} NMR (162 MHz, CDCl₃, p.p.m.): -26.54, -30.07. Anal. Calcd. for C₄₄H₈₉O₆P₅Re₆S₂Se₈·2CH₂Cl₂: C, 19.37; H, 3.29; N, 0.00. Found: C, 19.26; H, 3.29; N, 0.13. ESI-MS(+): 2512.8 m/z [(M-OSO₂C₆H₄CH₃)⁺].

Structure description top

Lindner & Grimmer (1971) reported the insertion of sulfur trioxide into the Re-alkyl bond of (p-tolyl)Re(CO)₅ to generate the first example of a rhenium complex to contain a tosylate moiety. Later, Eremenko et al. (1993) determined the structure of [Re(P(OiPr)₃)₂(CO)(NO)(OTs)₂] (OTs^- = p-toluenesulfonate anion) which represented the first structural report of a rhenium complex containing tosylate ligands. In the synthesis of octahedral rhenium chalcogenide cluster complexes, the substitution of either halide or nitrile ligands has proven an effective means for generating a variety of new cluster complexes (Zheng & Holm, 1997; Knott et al., 2013; Yoshimura et al., 2000). Nitrile ligands are often considered weakly coordinating and substitution of alkyl and aryl nitrile ligands has often been used in single metal chemistry (Endres, 1987) and in the preparation of [Re₆Q₈]²⁺ (Q = S or Se) cluster complexes (Zheng & Holm, 1997; Durham et al., 2012). However, there have been reports of the hexanuclear rhenium selenide cluster core, [Re₆Se₈]²⁺, activating nitriles to undergo reactions other than substitution (Orto et al., 2007; Szczepura et al., 2007). While structural reports of rhenium chalcogenide clusters containing other oxygen donor ligands have been previously reported (Dorson et al., 2009; Mironov et al., 2011; Zheng & Holm 1997; Zheng et al. 1999), this report represents the first example of tosylate coordination to a [Re₆Q₈]²⁺ cluster core. There are also a number of structural reports of rhenium trifluoromethanesulfonate (TfO^-) complexes (Huertos et al., 2010; Matano et al., 1998; Tahmassebi et al., 1997). For other [Re₆Se₈]²⁺ based-cluster complexes, see: Dorson et al. (2009); Durham et al. (2012, 2015); Knott et al. (2013); Mironov et al. (2011); Zheng & Holm (1997); Zheng et al. 1999). The average Re—P bond distance of the five terminal PEt₃ ligands [2.4790 Å] is similar to that in other rhenium selenide clusters containing PEt₃ ligands (Durham et al., 2012, 2015; Knott et al., 2013; Zheng & Holm, 1997; Zheng et al. 1999).

Computing details top

Data collection: SMART (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: DIRDIF99 (Beurskens et al., 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Perspective view of the [Re₆Se₈(PEt₃)₅(O₃SC₆H₄Me)]⁺ ion showing the atom labelling scheme. Non-hydrogen atoms are represented by Gaussian ellipsoids at the 30% probability level. Hydrogen atoms omitted for clarity.

Octa-µ₃-selenido-(p-toluenesulfonato-κO)pentakis(triethylphosphane-κP)-octahedro-hexarhenium(III) p-toluenesulfonate dichloromethane disolvate top

Crystal data top

[Re₆Se₈(C₇H₇O₃S)(C₆H₁₅P)₅](C₇H₇O₃S)·2CH₂Cl₂	Z = 2
M_r = 2851.85	F(000) = 2628
Triclinic, P1	D_x = 2.609 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.7432 (10) Å	Cell parameters from 7041 reflections
b = 16.6878 (14) Å	θ = 2.2–27.4°
c = 18.9786 (16) Å	µ = 14.33 mm⁻¹
α = 93.4729 (11)°	T = 193 K
β = 95.9862 (12)°	Prism, orange
γ = 100.0851 (11)°	0.48 × 0.28 × 0.10 mm
V = 3629.9 (5) Å³

Data collection top

Bruker PLATFORM/SMART 1000 CCD area-detector diffractometer	11401 reflections with I > 2σ(I)
Detector resolution: 8.192 pixels mm^-1	R_int = 0.031
ω scans	θ_max = 27.5°, θ_min = 1.7°
Absorption correction: integration (SADABS; Sheldrick, 2008)	h = −15→15
T_min = 0.032, T_max = 0.255	k = −21→21
31748 measured reflections	l = −24→24
16405 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.038P)² + 7.5887P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
16405 reflections	Δρ_max = 2.67 e Å⁻³
693 parameters	Δρ_min = −1.26 e Å⁻³

Crystal data top

[Re₆Se₈(C₇H₇O₃S)(C₆H₁₅P)₅](C₇H₇O₃S)·2CH₂Cl₂	γ = 100.0851 (11)°
M_r = 2851.85	V = 3629.9 (5) Å³
Triclinic, P1	Z = 2
a = 11.7432 (10) Å	Mo Kα radiation
b = 16.6878 (14) Å	µ = 14.33 mm⁻¹
c = 18.9786 (16) Å	T = 193 K
α = 93.4729 (11)°	0.48 × 0.28 × 0.10 mm
β = 95.9862 (12)°

Data collection top

Bruker PLATFORM/SMART 1000 CCD area-detector diffractometer	16405 independent reflections
Absorption correction: integration (SADABS; Sheldrick, 2008)	11401 reflections with I > 2σ(I)
T_min = 0.032, T_max = 0.255	R_int = 0.031
31748 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.02	Δρ_max = 2.67 e Å⁻³
16405 reflections	Δρ_min = −1.26 e Å⁻³
693 parameters

Special details top

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

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Re1	0.12366 (2)	0.35432 (2)	0.22926 (2)	0.02007 (6)
Re2	0.16617 (2)	0.29786 (2)	0.10389 (2)	0.02159 (7)
Re3	0.13895 (2)	0.19879 (2)	0.20606 (2)	0.02062 (7)
Re4	0.30352 (2)	0.29772 (2)	0.29017 (2)	0.02004 (6)
Re5	0.33294 (2)	0.39696 (2)	0.18802 (2)	0.02136 (7)
Re6	0.34623 (2)	0.24274 (2)	0.16411 (2)	0.02221 (7)
Se1	−0.02863 (6)	0.25580 (4)	0.14801 (3)	0.02465 (15)
Se2	0.10186 (6)	0.25694 (4)	0.32525 (3)	0.02334 (14)
Se3	0.28647 (6)	0.44606 (4)	0.30833 (3)	0.02378 (14)
Se4	0.15816 (6)	0.44579 (4)	0.12967 (4)	0.02754 (16)
Se5	0.18447 (6)	0.15003 (4)	0.08552 (3)	0.02631 (15)
Se6	0.31453 (6)	0.14981 (4)	0.26240 (4)	0.02578 (15)
Se7	0.49890 (6)	0.33842 (4)	0.24662 (4)	0.02539 (15)
Se8	0.36656 (6)	0.34011 (4)	0.06760 (4)	0.02695 (15)
S1	0.58942 (18)	0.19272 (12)	0.10790 (11)	0.0404 (5)
P1	−0.02451 (16)	0.42936 (10)	0.27116 (10)	0.0267 (4)
P2	0.06449 (18)	0.29468 (11)	−0.01759 (9)	0.0289 (4)
P3	0.01218 (17)	0.06768 (10)	0.22232 (10)	0.0277 (4)
P4	0.39486 (17)	0.29590 (11)	0.41376 (9)	0.0266 (4)
P5	0.47147 (19)	0.52475 (11)	0.17694 (10)	0.0357 (5)
O1	0.4663 (4)	0.1748 (3)	0.1248 (3)	0.0323 (11)
O2	0.6306 (5)	0.2788 (3)	0.1027 (3)	0.0562 (17)
O3	0.6607 (5)	0.1522 (4)	0.1537 (3)	0.0618 (18)
C1	0.5763 (8)	0.1441 (5)	0.0219 (5)	0.046 (2)
C2	0.6345 (11)	0.0810 (7)	0.0078 (6)	0.083 (4)
H2	0.6805	0.0625	0.0456	0.100*
C3	0.6272 (11)	0.0436 (7)	−0.0609 (6)	0.077 (3)
H3	0.6694	0.0011	−0.0697	0.092*
C4	0.5604 (10)	0.0679 (6)	−0.1147 (6)	0.064 (3)
C5	0.4992 (13)	0.1288 (8)	−0.1005 (6)	0.108 (5)
H5	0.4500	0.1456	−0.1375	0.130*
C6	0.5091 (13)	0.1662 (9)	−0.0313 (6)	0.122 (6)
H6	0.4667	0.2085	−0.0224	0.146*
C7	0.5535 (11)	0.0278 (7)	−0.1896 (6)	0.083 (4)
H7A	0.6287	0.0130	−0.1970	0.100*
H7B	0.5344	0.0662	−0.2242	0.100*
H7C	0.4929	−0.0214	−0.1958	0.100*
C11	−0.0042 (7)	0.4563 (4)	0.3667 (4)	0.0351 (17)
H11A	−0.0040	0.4056	0.3910	0.042*
H11B	0.0737	0.4910	0.3791	0.042*
C12	−0.0937 (8)	0.5010 (5)	0.3965 (4)	0.046 (2)
H12A	−0.0747	0.5115	0.4482	0.055*
H12B	−0.1715	0.4672	0.3857	0.055*
H12C	−0.0925	0.5530	0.3749	0.055*
C13	−0.1760 (7)	0.3747 (4)	0.2540 (4)	0.0373 (18)
H13A	−0.2280	0.4115	0.2693	0.045*
H13B	−0.1959	0.3610	0.2022	0.045*
C14	−0.1991 (7)	0.2963 (4)	0.2920 (4)	0.0391 (18)
H14A	−0.2825	0.2732	0.2845	0.047*
H14B	−0.1742	0.3086	0.3430	0.047*
H14C	−0.1552	0.2568	0.2729	0.047*
C15	−0.0325 (7)	0.5260 (4)	0.2323 (4)	0.0377 (18)
H15A	−0.0461	0.5153	0.1800	0.045*
H15B	−0.1008	0.5465	0.2478	0.045*
C16	0.0724 (8)	0.5918 (4)	0.2507 (4)	0.045 (2)
H16A	0.0568	0.6425	0.2316	0.053*
H16B	0.1388	0.5755	0.2301	0.053*
H16C	0.0905	0.6004	0.3025	0.053*
C21	−0.0445 (7)	0.2022 (5)	−0.0443 (4)	0.0394 (19)
H21A	−0.0043	0.1548	−0.0431	0.047*
H21B	−0.0999	0.1961	−0.0082	0.047*
C22	−0.1147 (8)	0.1979 (5)	−0.1174 (4)	0.049 (2)
H22A	−0.1685	0.1454	−0.1261	0.059*
H22B	−0.0616	0.2030	−0.1540	0.059*
H22C	−0.1590	0.2425	−0.1188	0.059*
C23	0.1580 (7)	0.3016 (5)	−0.0883 (4)	0.0392 (19)
H23A	0.1103	0.3071	−0.1333	0.047*
H23B	0.2176	0.3520	−0.0780	0.047*
C24	0.2195 (8)	0.2302 (5)	−0.0994 (4)	0.046 (2)
H24A	0.2675	0.2394	−0.1384	0.055*
H24B	0.1617	0.1800	−0.1111	0.055*
H24C	0.2693	0.2250	−0.0557	0.055*
C25	−0.0151 (7)	0.3782 (5)	−0.0342 (4)	0.0410 (19)
H25A	0.0408	0.4305	−0.0252	0.049*
H25B	−0.0466	0.3727	−0.0850	0.049*
C26	−0.1155 (8)	0.3824 (5)	0.0105 (5)	0.053 (2)
H26A	−0.1515	0.4293	−0.0013	0.064*
H26B	−0.0856	0.3884	0.0611	0.064*
H26C	−0.1737	0.3321	0.0004	0.064*
C31	−0.0210 (8)	−0.0054 (4)	0.1442 (4)	0.042 (2)
H31A	0.0532	−0.0123	0.1263	0.051*
H31B	−0.0572	−0.0588	0.1592	0.051*
C32	−0.0993 (9)	0.0163 (5)	0.0844 (4)	0.058 (3)
H32A	−0.1149	−0.0281	0.0464	0.069*
H32B	−0.0618	0.0666	0.0660	0.069*
H32C	−0.1728	0.0244	0.1013	0.069*
C33	−0.1291 (7)	0.0800 (5)	0.2480 (4)	0.0395 (19)
H33A	−0.1165	0.1133	0.2941	0.047*
H33B	−0.1665	0.1110	0.2123	0.047*
C34	−0.2127 (8)	0.0017 (5)	0.2552 (5)	0.055 (2)
H34A	−0.2861	0.0147	0.2687	0.066*
H34B	−0.1784	−0.0288	0.2918	0.066*
H34C	−0.2277	−0.0315	0.2097	0.066*
C35	0.0707 (7)	0.0060 (4)	0.2885 (4)	0.0348 (17)
H35A	0.0161	−0.0467	0.2865	0.042*
H35B	0.1452	−0.0060	0.2745	0.042*
C36	0.0925 (8)	0.0420 (5)	0.3650 (4)	0.046 (2)
H36A	0.1228	0.0031	0.3953	0.055*
H36B	0.0193	0.0531	0.3805	0.055*
H36C	0.1494	0.0930	0.3687	0.055*
C41	0.5134 (7)	0.3820 (5)	0.4418 (4)	0.0407 (19)
H41A	0.5739	0.3808	0.4093	0.049*
H41B	0.4827	0.4330	0.4357	0.049*
C42	0.5712 (8)	0.3856 (5)	0.5176 (4)	0.050 (2)
H42A	0.6305	0.4353	0.5275	0.060*
H42B	0.6080	0.3377	0.5236	0.060*
H42C	0.5124	0.3861	0.5506	0.060*
C43	0.4584 (7)	0.2066 (4)	0.4322 (4)	0.0375 (19)
H43A	0.4822	0.2090	0.4840	0.045*
H43B	0.3972	0.1575	0.4197	0.045*
C44	0.5638 (8)	0.1958 (5)	0.3935 (5)	0.049 (2)
H44A	0.5945	0.1483	0.4098	0.059*
H44B	0.6244	0.2448	0.4039	0.059*
H44C	0.5399	0.1874	0.3422	0.059*
C45	0.2999 (7)	0.2951 (5)	0.4839 (4)	0.0393 (19)
H45A	0.2359	0.2473	0.4733	0.047*
H45B	0.3451	0.2874	0.5292	0.047*
C46	0.2465 (8)	0.3717 (5)	0.4943 (4)	0.045 (2)
H46A	0.1957	0.3650	0.5322	0.054*
H46B	0.2008	0.3799	0.4500	0.054*
H46C	0.3087	0.4192	0.5075	0.054*
C51	0.6216 (9)	0.5128 (6)	0.1577 (5)	0.064 (3)
H51A	0.6737	0.5665	0.1691	0.076*
H51B	0.6495	0.4747	0.1907	0.076*
C52	0.6356 (9)	0.4832 (6)	0.0850 (5)	0.070 (3)
H52A	0.7187	0.4872	0.0802	0.085*
H52B	0.6011	0.5165	0.0509	0.085*
H52C	0.5964	0.4261	0.0756	0.085*
C53	0.5125 (10)	0.5942 (5)	0.2573 (5)	0.068 (3)
H53A	0.5558	0.6466	0.2444	0.081*
H53B	0.4406	0.6054	0.2758	0.081*
C54	0.5877 (9)	0.5626 (6)	0.3171 (5)	0.067 (3)
H54A	0.6022	0.6021	0.3588	0.080*
H54B	0.6620	0.5556	0.3008	0.080*
H54C	0.5466	0.5101	0.3297	0.080*
C55	0.4257 (12)	0.5886 (6)	0.1134 (6)	0.089 (4)
H55A	0.4962	0.6185	0.0958	0.107*	0.65
H55B	0.3803	0.5530	0.0727	0.107*	0.65
H55C	0.4270	0.5578	0.0673	0.107*	0.35
H55D	0.3422	0.5864	0.1187	0.107*	0.35
C56A	0.3580 (17)	0.6468 (11)	0.1335 (10)	0.085 (5)*	0.65
H56A	0.3389	0.6772	0.0926	0.102*	0.65
H56B	0.4024	0.6848	0.1721	0.102*	0.65
H56C	0.2859	0.6187	0.1495	0.102*	0.65
C56B	0.466 (3)	0.672 (2)	0.1006 (19)	0.094 (11)*	0.35
H56D	0.4193	0.6859	0.0591	0.112*	0.35
H56E	0.5481	0.6785	0.0915	0.112*	0.35
H56F	0.4598	0.7074	0.1423	0.112*	0.35
S2	0.1203 (2)	0.25430 (12)	0.69762 (10)	0.0397 (5)
O4	0.2051 (6)	0.3129 (3)	0.7426 (3)	0.0593 (18)
O5	0.0437 (5)	0.2020 (3)	0.7371 (3)	0.0578 (17)
O6	0.0570 (8)	0.2922 (4)	0.6441 (4)	0.085 (3)
C61	0.1949 (7)	0.1916 (4)	0.6514 (4)	0.0346 (17)
C62	0.1339 (8)	0.1340 (5)	0.5971 (4)	0.0409 (19)
H62	0.0527	0.1310	0.5847	0.049*
C63	0.1924 (9)	0.0821 (5)	0.5618 (5)	0.053 (2)
H63	0.1498	0.0432	0.5257	0.064*
C64	0.3105 (9)	0.0847 (5)	0.5772 (5)	0.050 (2)
C65	0.3699 (8)	0.1410 (5)	0.6309 (5)	0.055 (2)
H65	0.4511	0.1438	0.6432	0.066*
C66	0.3122 (8)	0.1937 (5)	0.6671 (5)	0.046 (2)
H66	0.3551	0.2321	0.7035	0.055*
C67	0.3712 (11)	0.0272 (5)	0.5381 (6)	0.081 (4)
H67A	0.3421	0.0223	0.4874	0.097*
H67B	0.3559	−0.0266	0.5569	0.097*
H67C	0.4552	0.0483	0.5443	0.097*
Cl1S	0.1511 (3)	0.67463 (18)	0.49345 (15)	0.0790 (8)
Cl2S	0.1300 (3)	0.8404 (2)	0.53900 (19)	0.0944 (10)
C1S	0.0595 (10)	0.7443 (7)	0.5080 (6)	0.079 (3)
H1SA	0.0109	0.7478	0.4629	0.094*
H1SB	0.0065	0.7231	0.5427	0.094*
Cl3S	0.2826 (7)	0.8779 (5)	0.3829 (4)	0.105 (3)*	0.5
Cl4S	0.3255 (6)	0.7327 (4)	0.3274 (3)	0.0828 (17)*	0.5
Cl5S	0.3045 (6)	0.9045 (4)	0.3569 (4)	0.0836 (19)*	0.5
Cl6S	0.3205 (7)	0.7571 (5)	0.2778 (4)	0.109 (2)*	0.5
C2S	0.2295 (12)	0.8018 (8)	0.3232 (8)	0.109 (5)
H2SA	0.2221	0.8218	0.2752	0.131*	0.5
H2SB	0.1515	0.7749	0.3332	0.131*	0.5
H2SC	0.2069	0.7694	0.3632	0.131*	0.5
H2SD	0.1580	0.8048	0.2916	0.131*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Re1	0.02175 (14)	0.01753 (12)	0.02081 (13)	0.00464 (10)	0.00118 (11)	−0.00026 (9)
Re2	0.02488 (15)	0.01949 (13)	0.01971 (13)	0.00389 (11)	0.00088 (11)	−0.00048 (10)
Re3	0.02332 (15)	0.01668 (12)	0.02117 (13)	0.00340 (10)	0.00110 (11)	−0.00064 (9)
Re4	0.02163 (14)	0.01778 (13)	0.02046 (13)	0.00447 (10)	0.00114 (11)	−0.00061 (9)
Re5	0.02378 (15)	0.01844 (13)	0.02146 (14)	0.00346 (11)	0.00243 (11)	−0.00009 (10)
Re6	0.02424 (15)	0.01994 (13)	0.02252 (14)	0.00545 (11)	0.00282 (11)	−0.00207 (10)
Se1	0.0241 (4)	0.0240 (3)	0.0248 (3)	0.0040 (3)	−0.0001 (3)	−0.0005 (3)
Se2	0.0249 (4)	0.0217 (3)	0.0231 (3)	0.0036 (3)	0.0033 (3)	0.0007 (2)
Se3	0.0261 (4)	0.0196 (3)	0.0246 (3)	0.0035 (3)	0.0019 (3)	−0.0027 (2)
Se4	0.0326 (4)	0.0225 (3)	0.0278 (4)	0.0069 (3)	0.0012 (3)	0.0029 (3)
Se5	0.0310 (4)	0.0220 (3)	0.0246 (3)	0.0045 (3)	0.0014 (3)	−0.0044 (3)
Se6	0.0291 (4)	0.0202 (3)	0.0285 (4)	0.0072 (3)	0.0008 (3)	0.0011 (3)
Se7	0.0235 (4)	0.0252 (3)	0.0271 (4)	0.0050 (3)	0.0021 (3)	−0.0010 (3)
Se8	0.0302 (4)	0.0275 (3)	0.0227 (3)	0.0037 (3)	0.0047 (3)	0.0000 (3)
S1	0.0315 (11)	0.0419 (11)	0.0480 (12)	0.0094 (9)	0.0045 (9)	−0.0030 (9)
P1	0.0279 (10)	0.0244 (9)	0.0291 (9)	0.0091 (8)	0.0029 (8)	0.0005 (7)
P2	0.0353 (11)	0.0283 (9)	0.0227 (9)	0.0068 (8)	0.0001 (8)	0.0017 (7)
P3	0.0296 (10)	0.0206 (8)	0.0299 (10)	−0.0010 (8)	−0.0001 (8)	0.0008 (7)
P4	0.0301 (10)	0.0268 (9)	0.0226 (9)	0.0065 (8)	0.0000 (8)	0.0013 (7)
P5	0.0435 (13)	0.0264 (10)	0.0342 (11)	−0.0022 (9)	0.0063 (9)	0.0013 (8)
O1	0.030 (3)	0.025 (2)	0.041 (3)	0.005 (2)	0.004 (2)	−0.002 (2)
O2	0.046 (4)	0.040 (3)	0.074 (4)	−0.012 (3)	0.015 (3)	−0.012 (3)
O3	0.037 (4)	0.090 (5)	0.062 (4)	0.030 (4)	−0.006 (3)	0.007 (4)
C1	0.040 (5)	0.046 (5)	0.050 (5)	0.010 (4)	0.007 (4)	−0.004 (4)
C2	0.103 (10)	0.093 (9)	0.072 (8)	0.061 (8)	0.018 (7)	0.009 (7)
C3	0.094 (9)	0.070 (7)	0.078 (8)	0.043 (7)	0.020 (7)	−0.003 (6)
C4	0.078 (8)	0.052 (6)	0.064 (7)	0.014 (6)	0.027 (6)	−0.008 (5)
C5	0.147 (13)	0.145 (12)	0.056 (7)	0.106 (11)	0.000 (8)	−0.019 (7)
C6	0.184 (16)	0.161 (13)	0.048 (6)	0.143 (13)	−0.023 (8)	−0.027 (7)
C7	0.102 (10)	0.074 (7)	0.078 (8)	0.023 (7)	0.036 (7)	−0.022 (6)
C11	0.036 (5)	0.034 (4)	0.038 (4)	0.014 (3)	0.008 (4)	−0.002 (3)
C12	0.062 (6)	0.045 (5)	0.034 (4)	0.021 (4)	0.006 (4)	−0.001 (4)
C13	0.042 (5)	0.037 (4)	0.034 (4)	0.017 (4)	−0.008 (4)	0.000 (3)
C14	0.030 (4)	0.042 (4)	0.044 (5)	0.002 (4)	0.008 (4)	0.005 (4)
C15	0.045 (5)	0.029 (4)	0.044 (5)	0.018 (4)	0.008 (4)	0.009 (3)
C16	0.056 (6)	0.028 (4)	0.051 (5)	0.011 (4)	0.013 (4)	0.004 (4)
C21	0.040 (5)	0.040 (4)	0.036 (4)	0.006 (4)	0.000 (4)	0.000 (3)
C22	0.044 (5)	0.056 (5)	0.043 (5)	0.009 (4)	−0.006 (4)	−0.005 (4)
C23	0.051 (5)	0.040 (4)	0.024 (4)	−0.001 (4)	0.006 (4)	0.002 (3)
C24	0.050 (6)	0.053 (5)	0.036 (5)	0.009 (4)	0.011 (4)	−0.002 (4)
C25	0.051 (5)	0.040 (4)	0.032 (4)	0.013 (4)	−0.005 (4)	0.007 (3)
C26	0.058 (6)	0.051 (5)	0.053 (5)	0.030 (5)	−0.010 (5)	0.004 (4)
C31	0.054 (6)	0.025 (4)	0.043 (5)	−0.002 (4)	0.002 (4)	−0.005 (3)
C32	0.067 (7)	0.055 (6)	0.040 (5)	−0.007 (5)	−0.013 (5)	0.000 (4)
C33	0.035 (5)	0.038 (4)	0.043 (5)	−0.001 (4)	0.002 (4)	0.007 (3)
C34	0.042 (5)	0.046 (5)	0.076 (7)	−0.001 (4)	0.004 (5)	0.018 (5)
C35	0.035 (4)	0.022 (3)	0.046 (5)	0.002 (3)	0.004 (4)	0.009 (3)
C36	0.058 (6)	0.037 (4)	0.040 (5)	0.005 (4)	−0.005 (4)	0.012 (4)
C41	0.041 (5)	0.041 (4)	0.039 (4)	0.008 (4)	−0.001 (4)	0.001 (4)
C42	0.050 (6)	0.045 (5)	0.047 (5)	0.003 (4)	−0.013 (4)	−0.012 (4)
C43	0.050 (5)	0.033 (4)	0.034 (4)	0.020 (4)	0.000 (4)	0.008 (3)
C44	0.048 (5)	0.047 (5)	0.057 (5)	0.023 (4)	0.002 (4)	0.003 (4)
C45	0.039 (5)	0.049 (5)	0.031 (4)	0.012 (4)	0.004 (4)	0.004 (3)
C46	0.047 (5)	0.056 (5)	0.034 (4)	0.014 (4)	0.008 (4)	−0.008 (4)
C51	0.060 (7)	0.059 (6)	0.067 (7)	−0.009 (5)	0.010 (5)	0.020 (5)
C52	0.071 (8)	0.053 (6)	0.082 (8)	−0.010 (5)	0.029 (6)	−0.010 (5)
C53	0.090 (8)	0.044 (5)	0.051 (6)	−0.022 (5)	−0.012 (6)	−0.005 (4)
C54	0.070 (7)	0.066 (6)	0.048 (6)	−0.028 (5)	0.004 (5)	−0.005 (5)
C55	0.122 (11)	0.049 (6)	0.087 (8)	0.004 (7)	−0.023 (8)	0.025 (6)
S2	0.0549 (14)	0.0320 (10)	0.0315 (10)	0.0047 (9)	0.0068 (10)	0.0020 (8)
O4	0.069 (5)	0.044 (3)	0.058 (4)	−0.013 (3)	0.025 (3)	−0.013 (3)
O5	0.053 (4)	0.046 (3)	0.074 (4)	−0.002 (3)	0.031 (4)	−0.008 (3)
O6	0.134 (7)	0.088 (5)	0.056 (4)	0.083 (5)	0.015 (4)	0.001 (4)
C61	0.040 (5)	0.026 (4)	0.036 (4)	0.003 (3)	0.001 (4)	0.009 (3)
C62	0.049 (5)	0.040 (4)	0.033 (4)	0.008 (4)	0.004 (4)	0.000 (3)
C63	0.080 (8)	0.038 (5)	0.042 (5)	0.010 (5)	0.013 (5)	−0.004 (4)
C64	0.062 (7)	0.031 (4)	0.057 (6)	0.006 (4)	0.017 (5)	0.004 (4)
C65	0.043 (5)	0.039 (5)	0.088 (7)	0.012 (4)	0.013 (5)	0.021 (5)
C66	0.045 (5)	0.034 (4)	0.054 (5)	−0.001 (4)	0.001 (4)	−0.003 (4)
C67	0.118 (10)	0.045 (6)	0.101 (9)	0.042 (6)	0.058 (8)	0.019 (6)
Cl1S	0.085 (2)	0.0841 (19)	0.0724 (18)	0.0330 (17)	0.0007 (16)	0.0012 (15)
Cl2S	0.084 (2)	0.080 (2)	0.114 (3)	0.0180 (18)	−0.008 (2)	−0.0070 (19)
C1S	0.067 (8)	0.101 (9)	0.068 (7)	0.022 (7)	0.000 (6)	0.005 (7)
C2S	0.077 (10)	0.109 (11)	0.135 (12)	0.022 (8)	−0.012 (9)	−0.020 (9)

Geometric parameters (Å, º) top

Re1—P1	2.4818 (18)	P2—C25	1.833 (7)
Re1—Se2	2.5171 (7)	P3—C33	1.819 (8)
Re1—Se3	2.5199 (7)	P3—C31	1.825 (7)
Re1—Se4	2.5218 (7)	P3—C35	1.825 (7)
Re1—Se1	2.5232 (7)	P4—C43	1.816 (7)
Re1—Re2	2.6341 (4)	P4—C45	1.822 (7)
Re1—Re3	2.6464 (4)	P4—C41	1.826 (8)
Re1—Re4	2.6480 (4)	P5—C55	1.760 (10)
Re1—Re5	2.6486 (4)	P5—C53	1.827 (9)
Re2—P2	2.4765 (18)	P5—C51	1.880 (10)
Re2—Se4	2.5074 (7)	C1—C6	1.327 (13)
Re2—Se8	2.5150 (8)	C1—C2	1.380 (12)
Re2—Se1	2.5168 (7)	C2—C3	1.399 (14)
Re2—Se5	2.5201 (7)	C3—C4	1.347 (14)
Re2—Re3	2.6320 (4)	C4—C5	1.372 (13)
Re2—Re6	2.6321 (4)	C4—C7	1.523 (13)
Re2—Re5	2.6482 (4)	C5—C6	1.403 (14)
Re3—P3	2.4771 (17)	C11—C12	1.526 (10)
Re3—Se6	2.5097 (7)	C13—C14	1.529 (10)
Re3—Se1	2.5144 (7)	C15—C16	1.495 (11)
Re3—Se2	2.5170 (7)	C21—C22	1.528 (10)
Re3—Se5	2.5227 (7)	C23—C24	1.512 (10)
Re3—Re4	2.6322 (4)	C25—C26	1.532 (11)
Re3—Re6	2.6356 (4)	C31—C32	1.487 (11)
Re4—P4	2.4796 (18)	C33—C34	1.513 (10)
Re4—Se7	2.5152 (7)	C35—C36	1.515 (10)
Re4—Se2	2.5167 (7)	C41—C42	1.520 (10)
Re4—Se6	2.5209 (7)	C43—C44	1.535 (11)
Re4—Se3	2.5242 (7)	C45—C46	1.530 (10)
Re4—Re5	2.6360 (4)	C51—C52	1.471 (13)
Re4—Re6	2.6387 (4)	C53—C54	1.540 (13)
Re5—P5	2.4798 (19)	C55—C56A	1.418 (19)
Re5—Se4	2.5148 (8)	C55—C56B	1.43 (3)
Re5—Se7	2.5171 (7)	S2—O4	1.435 (6)
Re5—Se8	2.5171 (7)	S2—O6	1.438 (7)
Re5—Se3	2.5243 (7)	S2—O5	1.441 (6)
Re5—Re6	2.6206 (4)	S2—C61	1.733 (8)
Re6—O1	2.123 (5)	C61—C66	1.373 (11)
Re6—Se6	2.5131 (7)	C61—C62	1.409 (10)
Re6—Se7	2.5149 (7)	C62—C63	1.380 (11)
Re6—Se5	2.5154 (7)	C63—C64	1.380 (13)
Re6—Se8	2.5236 (7)	C64—C65	1.384 (12)
S1—O3	1.426 (6)	C64—C67	1.497 (11)
S1—O2	1.445 (6)	C65—C66	1.391 (11)
S1—O1	1.497 (5)	Cl1S—C1S	1.746 (11)
S1—C1	1.759 (9)	Cl2S—C1S	1.709 (12)
P1—C11	1.821 (7)	Cl3S—C2S	1.639 (14)
P1—C15	1.826 (7)	Cl4S—C2S	1.747 (14)
P1—C13	1.838 (8)	Cl5S—C2S	1.829 (14)
P2—C23	1.818 (7)	Cl6S—C2S	1.684 (14)
P2—C21	1.832 (8)

P1—Re1—Se2	92.64 (4)	Se7—Re5—Re4	58.377 (17)
P1—Re1—Se3	92.22 (5)	Se8—Re5—Re4	119.023 (19)
Se2—Re1—Se3	89.78 (2)	Se3—Re5—Re4	58.524 (17)
P1—Re1—Se4	92.08 (4)	Re6—Re5—Re4	60.260 (10)
Se2—Re1—Se4	175.28 (2)	P5—Re5—Re2	136.47 (5)
Se3—Re1—Se4	89.95 (2)	Se4—Re5—Re2	58.040 (18)
P1—Re1—Se1	91.99 (5)	Se7—Re5—Re2	118.484 (19)
Se2—Re1—Se1	89.41 (2)	Se8—Re5—Re2	58.208 (19)
Se3—Re1—Se1	175.74 (2)	Se3—Re5—Re2	117.88 (2)
Se4—Re1—Se1	90.52 (2)	Re6—Re5—Re2	59.939 (10)
P1—Re1—Re2	134.53 (4)	Re4—Re5—Re2	89.800 (12)
Se2—Re1—Re2	118.069 (18)	P5—Re5—Re1	137.68 (5)
Se3—Re1—Re2	118.568 (19)	Se4—Re5—Re1	58.401 (18)
Se4—Re1—Re2	58.149 (17)	Se7—Re5—Re1	118.507 (19)
Se1—Re1—Re2	58.373 (17)	Se8—Re5—Re1	117.85 (2)
P1—Re1—Re3	135.44 (4)	Se3—Re5—Re1	58.245 (17)
Se2—Re1—Re3	58.284 (16)	Re6—Re5—Re1	90.185 (11)
Se3—Re1—Re3	118.027 (19)	Re4—Re5—Re1	60.143 (10)
Se4—Re1—Re3	117.904 (19)	Re2—Re5—Re1	59.644 (11)
Se1—Re1—Re3	58.147 (17)	O1—Re6—Se6	91.02 (13)
Re2—Re1—Re3	59.793 (9)	O1—Re6—Se7	94.31 (13)
P1—Re1—Re4	135.62 (4)	Se6—Re6—Se7	89.57 (2)
Se2—Re1—Re4	58.255 (17)	O1—Re6—Se5	88.99 (13)
Se3—Re1—Re4	58.415 (17)	Se6—Re6—Se5	89.52 (2)
Se4—Re1—Re4	117.82 (2)	Se7—Re6—Se5	176.59 (2)
Se1—Re1—Re4	117.766 (18)	O1—Re6—Se8	92.75 (13)
Re2—Re1—Re4	89.846 (12)	Se6—Re6—Se8	176.16 (2)
Re3—Re1—Re4	59.625 (10)	Se7—Re6—Se8	90.87 (2)
P1—Re1—Re5	135.03 (4)	Se5—Re6—Se8	89.82 (2)
Se2—Re1—Re5	117.935 (19)	O1—Re6—Re5	137.09 (13)
Se3—Re1—Re5	58.408 (17)	Se6—Re6—Re5	118.684 (18)
Se4—Re1—Re5	58.147 (18)	Se7—Re6—Re5	58.655 (17)
Se1—Re1—Re5	118.510 (19)	Se5—Re6—Re5	119.115 (19)
Re2—Re1—Re5	60.172 (10)	Se8—Re6—Re5	58.553 (17)
Re3—Re1—Re5	89.532 (11)	O1—Re6—Re2	133.56 (13)
Re4—Re1—Re5	59.693 (11)	Se6—Re6—Re2	118.24 (2)
P2—Re2—Se4	92.27 (4)	Se7—Re6—Re2	119.176 (19)
P2—Re2—Se8	94.73 (5)	Se5—Re6—Re2	58.571 (17)
Se4—Re2—Se8	88.80 (2)	Se8—Re6—Re2	58.348 (18)
P2—Re2—Se1	88.81 (5)	Re5—Re6—Re2	60.551 (10)
Se4—Re2—Se1	91.00 (2)	O1—Re6—Re3	132.52 (13)
Se8—Re2—Se1	176.46 (2)	Se6—Re6—Re3	58.289 (18)
P2—Re2—Se5	91.59 (4)	Se7—Re6—Re3	118.238 (19)
Se4—Re2—Se5	176.02 (3)	Se5—Re6—Re3	58.592 (18)
Se8—Re2—Se5	89.92 (2)	Se8—Re6—Re3	118.29 (2)
Se1—Re2—Se5	90.05 (2)	Re5—Re6—Re3	90.372 (12)
P2—Re2—Re3	132.58 (5)	Re2—Re6—Re3	59.953 (11)
Se4—Re2—Re3	118.978 (19)	O1—Re6—Re4	136.22 (13)
Se8—Re2—Re3	118.744 (19)	Se6—Re6—Re4	58.533 (17)
Se1—Re2—Re3	58.412 (17)	Se7—Re6—Re4	58.365 (17)
Se5—Re2—Re3	58.587 (17)	Se5—Re6—Re4	118.46 (2)
P2—Re2—Re6	136.88 (5)	Se8—Re6—Re4	118.677 (19)
Se4—Re2—Re6	117.82 (2)	Re5—Re6—Re4	60.158 (9)
Se8—Re2—Re6	58.667 (18)	Re2—Re6—Re4	90.092 (12)
Se1—Re2—Re6	118.490 (19)	Re3—Re6—Re4	59.875 (10)
Se5—Re2—Re6	58.400 (18)	Re3—Se1—Re2	63.085 (19)
Re3—Re2—Re6	60.089 (10)	Re3—Se1—Re1	63.381 (19)
P2—Re2—Re1	132.79 (5)	Re2—Se1—Re1	63.019 (19)
Se4—Re2—Re1	58.681 (17)	Re4—Se2—Re3	63.055 (17)
Se8—Re2—Re1	118.468 (19)	Re4—Se2—Re1	63.477 (17)
Se1—Re2—Re1	58.608 (17)	Re3—Se2—Re1	63.431 (18)
Se5—Re2—Re1	118.907 (18)	Re1—Se3—Re4	63.332 (17)
Re3—Re2—Re1	60.335 (11)	Re1—Se3—Re5	63.346 (18)
Re6—Re2—Re1	90.250 (12)	Re4—Se3—Re5	62.950 (16)
P2—Re2—Re5	137.53 (5)	Re2—Se4—Re5	63.646 (18)
Se4—Re2—Re5	58.314 (18)	Re2—Se4—Re1	63.170 (17)
Se8—Re2—Re5	58.284 (18)	Re5—Se4—Re1	63.452 (18)
Se1—Re2—Re5	118.757 (19)	Re6—Se5—Re2	63.029 (18)
Se5—Re2—Re5	117.90 (2)	Re6—Se5—Re3	63.085 (18)
Re3—Re2—Re5	89.848 (12)	Re2—Se5—Re3	62.925 (17)
Re6—Re2—Re5	59.510 (11)	Re3—Se6—Re6	63.300 (18)
Re1—Re2—Re5	60.184 (11)	Re3—Se6—Re4	63.097 (17)
P3—Re3—Se6	91.08 (5)	Re6—Se6—Re4	63.225 (17)
P3—Re3—Se1	92.48 (5)	Re6—Se7—Re4	63.279 (19)
Se6—Re3—Se1	176.42 (2)	Re6—Se7—Re5	62.771 (19)
P3—Re3—Se2	90.40 (5)	Re4—Se7—Re5	63.177 (19)
Se6—Re3—Se2	90.67 (2)	Re2—Se8—Re5	63.508 (18)
Se1—Re3—Se2	89.61 (2)	Re2—Se8—Re6	62.985 (18)
P3—Re3—Se5	93.57 (5)	Re5—Se8—Re6	62.651 (18)
Se6—Re3—Se5	89.43 (2)	O3—S1—O2	116.5 (4)
Se1—Re3—Se5	90.05 (2)	O3—S1—O1	109.9 (3)
Se2—Re3—Se5	176.03 (2)	O2—S1—O1	112.6 (3)
P3—Re3—Re2	136.60 (4)	O3—S1—C1	107.8 (4)
Se6—Re3—Re2	118.36 (2)	O2—S1—C1	107.2 (4)
Se1—Re3—Re2	58.503 (17)	O1—S1—C1	101.5 (4)
Se2—Re3—Re2	118.150 (18)	C11—P1—C15	104.1 (3)
Se5—Re3—Re2	58.489 (17)	C11—P1—C13	103.7 (4)
P3—Re3—Re4	133.15 (4)	C15—P1—C13	102.5 (4)
Se6—Re3—Re4	58.659 (17)	C11—P1—Re1	113.8 (2)
Se1—Re3—Re4	118.683 (19)	C15—P1—Re1	115.6 (3)
Se2—Re3—Re4	58.467 (18)	C13—P1—Re1	115.5 (2)
Se5—Re3—Re4	118.44 (2)	C23—P2—C21	104.3 (4)
Re2—Re3—Re4	90.236 (12)	C23—P2—C25	101.6 (4)
P3—Re3—Re6	135.68 (5)	C21—P2—C25	104.0 (4)
Se6—Re3—Re6	58.412 (18)	C23—P2—Re2	115.3 (3)
Se1—Re3—Re6	118.449 (19)	C21—P2—Re2	114.2 (3)
Se2—Re3—Re6	118.558 (19)	C25—P2—Re2	115.9 (3)
Se5—Re3—Re6	58.323 (18)	C33—P3—C31	104.8 (4)
Re2—Re3—Re6	59.958 (10)	C33—P3—C35	105.1 (4)
Re4—Re3—Re6	60.120 (11)	C31—P3—C35	101.1 (3)
P3—Re3—Re1	134.37 (5)	C33—P3—Re3	113.3 (2)
Se6—Re3—Re1	118.850 (19)	C31—P3—Re3	115.3 (3)
Se1—Re3—Re1	58.472 (17)	C35—P3—Re3	115.8 (2)
Se2—Re3—Re1	58.286 (16)	C43—P4—C45	100.0 (3)
Se5—Re3—Re1	118.346 (18)	C43—P4—C41	104.2 (4)
Re2—Re3—Re1	59.872 (10)	C45—P4—C41	104.4 (4)
Re4—Re3—Re1	60.217 (10)	C43—P4—Re4	115.6 (3)
Re6—Re3—Re1	89.907 (11)	C45—P4—Re4	117.0 (3)
P4—Re4—Se7	91.66 (5)	C41—P4—Re4	113.8 (3)
P4—Re4—Se2	92.20 (5)	C55—P5—C53	102.8 (5)
Se7—Re4—Se2	176.14 (2)	C55—P5—C51	105.0 (6)
P4—Re4—Se6	91.66 (4)	C53—P5—C51	98.4 (5)
Se7—Re4—Se6	89.39 (2)	C55—P5—Re5	115.9 (4)
Se2—Re4—Se6	90.42 (2)	C53—P5—Re5	116.1 (3)
P4—Re4—Se3	92.64 (4)	C51—P5—Re5	116.3 (3)
Se7—Re4—Se3	90.21 (2)	S1—O1—Re6	136.5 (3)
Se2—Re4—Se3	89.69 (2)	C6—C1—C2	118.0 (9)
Se6—Re4—Se3	175.69 (2)	C6—C1—S1	121.1 (7)
P4—Re4—Re3	134.62 (4)	C2—C1—S1	120.9 (8)
Se7—Re4—Re3	118.358 (19)	C1—C2—C3	121.2 (10)
Se2—Re4—Re3	58.478 (17)	C4—C3—C2	120.1 (10)
Se6—Re4—Re3	58.244 (18)	C3—C4—C5	118.9 (10)
Se3—Re4—Re3	118.399 (19)	C3—C4—C7	120.0 (9)
P4—Re4—Re5	135.26 (4)	C5—C4—C7	121.1 (11)
Se7—Re4—Re5	58.446 (17)	C4—C5—C6	120.1 (11)
Se2—Re4—Re5	118.418 (18)	C1—C6—C5	121.7 (10)
Se6—Re4—Re5	117.818 (19)	C12—C11—P1	116.8 (6)
Se3—Re4—Re5	58.526 (17)	C14—C13—P1	113.7 (5)
Re3—Re4—Re5	90.112 (12)	C16—C15—P1	115.6 (6)
P4—Re4—Re6	134.67 (4)	C22—C21—P2	117.0 (6)
Se7—Re4—Re6	58.355 (17)	C24—C23—P2	115.5 (5)
Se2—Re4—Re6	118.454 (18)	C26—C25—P2	115.4 (5)
Se6—Re4—Re6	58.243 (17)	C32—C31—P3	116.0 (6)
Se3—Re4—Re6	118.087 (18)	C34—C33—P3	115.7 (6)
Re3—Re4—Re6	60.005 (11)	C36—C35—P3	117.2 (5)
Re5—Re4—Re6	59.582 (11)	C42—C41—P4	116.5 (6)
P4—Re4—Re1	135.52 (4)	C44—C43—P4	116.2 (5)
Se7—Re4—Re1	118.598 (19)	C46—C45—P4	115.5 (5)
Se2—Re4—Re1	58.268 (17)	C52—C51—P5	117.6 (8)
Se6—Re4—Re1	118.376 (19)	C54—C53—P5	114.8 (7)
Se3—Re4—Re1	58.254 (17)	C56A—C55—P5	119.1 (12)
Re3—Re4—Re1	60.158 (11)	C56B—C55—P5	133.1 (18)
Re5—Re4—Re1	60.164 (10)	O4—S2—O6	112.0 (4)
Re6—Re4—Re1	89.807 (12)	O4—S2—O5	112.8 (4)
P5—Re5—Se4	94.95 (5)	O6—S2—O5	112.1 (5)
P5—Re5—Se7	89.06 (5)	O4—S2—C61	107.5 (4)
Se4—Re5—Se7	175.97 (2)	O6—S2—C61	105.4 (4)
P5—Re5—Se8	90.90 (5)	O5—S2—C61	106.5 (3)
Se4—Re5—Se8	88.59 (2)	C66—C61—C62	117.8 (7)
Se7—Re5—Se8	90.97 (2)	C66—C61—S2	122.5 (6)
P5—Re5—Se3	93.06 (5)	C62—C61—S2	119.7 (6)
Se4—Re5—Se3	90.01 (2)	C63—C62—C61	119.9 (8)
Se7—Re5—Se3	90.17 (2)	C62—C63—C64	122.4 (9)
Se8—Re5—Se3	175.91 (2)	C63—C64—C65	117.5 (8)
P5—Re5—Re6	132.11 (5)	C63—C64—C67	121.0 (9)
Se4—Re5—Re6	117.978 (19)	C65—C64—C67	121.5 (10)
Se7—Re5—Re6	58.574 (17)	C64—C65—C66	120.9 (9)
Se8—Re5—Re6	58.797 (17)	C61—C66—C65	121.6 (8)
Se3—Re5—Re6	118.763 (18)	Cl2S—C1S—Cl1S	114.6 (7)
P5—Re5—Re4	133.61 (5)	Cl3S—C2S—Cl4S	107.5 (8)
Se4—Re5—Re4	118.52 (2)	Cl6S—C2S—Cl5S	108.3 (8)

Experimental details

Crystal data
Chemical formula	[Re₆Se₈(C₇H₇O₃S)(C₆H₁₅P)₅](C₇H₇O₃S)·2CH₂Cl₂
M_r	2851.85
Crystal system, space group	Triclinic, P1
Temperature (K)	193
a, b, c (Å)	11.7432 (10), 16.6878 (14), 18.9786 (16)
α, β, γ (°)	93.4729 (11), 95.9862 (12), 100.0851 (11)
V (Å³)	3629.9 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	14.33
Crystal size (mm)	0.48 × 0.28 × 0.10

Data collection
Diffractometer	Bruker PLATFORM/SMART 1000 CCD area-detector
Absorption correction	Integration (SADABS; Sheldrick, 2008)
T_min, T_max	0.032, 0.255
No. of measured, independent and observed [I > 2σ(I)] reflections	31748, 16405, 11401
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.097, 1.02
No. of reflections	16405
No. of parameters	693
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.67, −1.26

Computer programs: SMART (Bruker, 2006), SAINT (Bruker, 2006), DIRDIF99 (Beurskens et al., 2008), SHELXL2013 (Sheldrick, 2015), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors acknowledge financial support from the NSF (LFS RUI-0957729 and LFS RUI-1401686).

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