Di-μ-chlorido-bis­[bis(tetra­hydro­thio­phene-κS)silver(I)]

Liebing, P.

doi:10.1107/S241431461700921X

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 6| June 2017| x170921

https://doi.org/10.1107/S241431461700921X

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Di-μ-chlorido-bis[bis(tetrahydrothiophene-κS)silver(I)]

Phil Liebing ^a ^*

^aDepartment of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, Vladimir-Prelog-Weg 2, CH-8093 Zurich, Switzerland
^*Correspondence e-mail: liebing@inorg.chem.ethz.ch

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 12 June 2017; accepted 19 June 2017; online 27 June 2017)

The title compound, [Ag₂Cl₂(C₄H₈S₂)₄] or [Ag₂(μ-Cl)₂(THT)₄] (THT = tetrahydrothiophene), is readily available by reaction of AgCl with THT. In this markedly labile complex, the Ag atoms are coordinated in a distorted tedrahedral fashion by two μ-bridging chloride ligands and each two terminal THT ligands. The structure is therefore more similar to that of THT-complexed CuCl than to that of THT-complexed AuCl, and resembles those of other [Ag₂(μ-Cl)₂L₄]-type complexes. The molecule is located on a crystallographic center of inversion.

Keywords: crystal structure; silver chloride; tetrahydrothiophene; THT.

CCDC reference: 1482494

Structure description

In the title compound (Fig. 1), two equivalents of AgCl build a centrosymmetric planar Ag₂Cl₂ ring with μ-bridging chloride ligands. The Ag—Cl distances are significantly different at 2.558 (2) and 2.748 (2) Å. Therefore the complex is structurally closely related to a series of other [Ag₂(μ-Cl)₂L₄]-type complexes, e.g. with L = PPh₃ [Ag—Cl = 2.596 (2) and 2.741 (2) Å; Cassel, 1979 ] and L = AsPh₃ [Ag—Cl = 2.568 (2) and 2.670 (2) Å; Bowmaker et al., 1997 ].

Figure 1
The molecular structure of the title compound in the crystal. Displacement ellipsoids of the non-H atoms are drawn at the 50% probability level and H atoms are drawn as spheres of arbitrary size. [Symmetry code: (') 1 − x, 1 − y, −z.]

Probably as a result of the low bulkiness of the THT ligands, the Ag₂Cl₂ core in the title compound is stretched along the Cl—Cl vector [Cl—Ag—Cl = 100.65 (5)°] while it is slightly stretched along the Ag—Ag vector in the PPh₃ complex [Cl—Ag—Cl = 88.03 (6)°]. The shape of the M₂Cl₂ ring in the title compound is therefore similar to those in the polymeric copper(I) complexes [Cu₂(μ-Cl)₂(μ-THT)(THT)₂], [Cu₂(μ-Cl)₂(μ-THT)₂] and [Cu₃(μ-Cl)₃(μ-THT)₂] [Cl—Cu—Cl = 96.8 (1)–105.9 (1)°; Maelger et al., 1992 ; Solari et al., 1996 ]. The related gold(I) complex [AuCl(THT)] features a linearly coordinated metal atom and bears no structural resemblance to the title compound (Ahrland et al., 1993 ).

With each two terminal THT ligands, a distorted-tetrahedral coordination of the Ag atoms is realised [Ag—S = 2.623 (2) and 2.554 (2) Å; Cl—Ag—S = 98.94 (7)–123.95 (7)°], where the deformation is stronger than in the related PPh₃ complex [Cl—Ag—P = 103.59 (7)–113.92 (7)°; Cassel, 1979]. The angle between the Ag—S bond and the S/C1/C4 plane of the THT ligand is 104.7° for S1 and 107.5° for S2. This tilting of the THT ligands corresponds to a pure sp³-hybridization of the ligating S atoms. Examples for other chloridosilver(I) complexes with sulfur ligands are [AgCl(detu)₃] [detu = N,N′-diethylthiourea; Ag—S = 2.554 (1)–2.593 (1) Å; Bowmaker et al., 2010 ] and [AgCl(9S3)] [9S3 = 1,4,7-trithiacyclononane; Ag—S = 2.598 (1)–2.618 (1) Å; Blower et al., 1989 ], where similar Ag—S distances were observed.

In the title compound, the closest intermolecular contact is Cl⋯C4(−x, 1 − y, −z) at 3.627 (9) Å, but the CH₂ group is not in a proper orientation for a potential C—H⋯Cl bonding interaction (C4—H4A⋯Cl = 114°, C4—H4B⋯Cl = 81°).

Synthesis and crystallization

A suspension of 0.72 g (5 mmol) of powdered silver(I) chloride in 5 ml of THT was refluxed for three h and then filtered. The resulting clear solution was layered with 10 ml of n-hexane at r.t. and then stored at −18°C. Colorless needle-like crystals were formed within a few days. When isolated from the mother liquor, these slowly decompose under THT loss even at −70°C, and readily above 0°C or when treated with organic solvents. The reaction scheme is shown in Fig. 2.

Figure 2
Reaction scheme.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	[Ag₂Cl₂(C₄H₈S₂)₄]
M_r	639.29
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	200
a, b, c (Å)	6.1921 (8), 9.9443 (13), 10.3761 (12)
α, β, γ (°)	114.710 (9), 102.121 (10), 92.239 (11)
V (Å³)	561.66 (13)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	2.35
Crystal size (mm)	0.50 × 0.05 × 0.05

Data collection
Diffractometer	Stoe IPDS 2T
Absorption correction	Numerical (X-AREA and X-RED; Stoe & Cie, 2002 )
T_min, T_max	0.398, 0.910
No. of measured, independent and observed [I > 2σ(I)] reflections	3765, 1954, 1314
R_int	0.094
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.125, 0.88
No. of reflections	1954
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.39, −1.53
Computer programs: X-AREA and X-RED (Stoe & Cie, 2002), SHELXL2014 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 1999 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1482494

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431461700921X/bt4051sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461700921X/bt4051Isup2.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-AREA and X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SIR97 (Altamore et al., 1999); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Di-µ-chlorido-bis[bis(tetrahydrothiophene-κS)silver(I)] top

Crystal data top

[Ag₂Cl₂(C₄H₈S₂)₄]	Z = 1
M_r = 639.29	F(000) = 320
Triclinic, P1	D_x = 1.890 Mg m⁻³
a = 6.1921 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9443 (13) Å	Cell parameters from 5660 reflections
c = 10.3761 (12) Å	θ = 4.0–29.2°
α = 114.710 (9)°	µ = 2.35 mm⁻¹
β = 102.121 (10)°	T = 200 K
γ = 92.239 (11)°	Needle, colorless
V = 561.66 (13) Å³	0.50 × 0.05 × 0.05 mm

Data collection top

Stoe IPDS 2T diffractometer	1314 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.094
area detector scans	θ_max = 25.0°, θ_min = 4.0°
Absorption correction: numerical (X-AREA and X-RED; Stoe & Cie, 2002)	h = −7→7
T_min = 0.398, T_max = 0.910	k = −11→11
3765 measured reflections	l = −12→12
1954 independent reflections

Refinement top

Refinement on F²	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H-atom parameters constrained
S = 0.88	w = 1/[σ²(F_o²) + (0.0669P)²] where P = (F_o² + 2F_c²)/3
1954 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 1.39 e Å⁻³
0 restraints	Δρ_min = −1.53 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. The H atoms of the THT ligands were fixed geometrically and refined using a riding model with U(H) = 1.20 U_eq(C). C—H distances were constrained to 0.99 Å.

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

	x	y	z	U_iso*/U_eq
C1	0.3137 (14)	0.1602 (9)	−0.3354 (9)	0.0357 (19)
H1B	0.4641	0.1706	−0.2730	0.043*
H1A	0.2860	0.0636	−0.4241	0.043*
C2	0.2946 (13)	0.2885 (10)	−0.3764 (10)	0.037 (2)
H2B	0.3729	0.2756	−0.4538	0.045*
H2A	0.3599	0.3845	−0.2902	0.045*
C3	0.0462 (15)	0.2851 (11)	−0.4317 (10)	0.045 (2)
H3B	−0.0119	0.1988	−0.5287	0.054*
H3A	0.0178	0.3779	−0.4419	0.054*
C4	−0.0682 (13)	0.2715 (10)	−0.3204 (9)	0.037 (2)
H4B	−0.2210	0.2162	−0.3695	0.045*
H4A	−0.0781	0.3719	−0.2455	0.045*
C5	0.1488 (14)	0.1726 (10)	0.1715 (10)	0.039 (2)
H5B	0.0765	0.1561	0.2412	0.047*
H5A	0.0342	0.1489	0.0798	0.047*
C6	0.3284 (17)	0.0802 (12)	0.1422 (17)	0.077 (4)
H6B	0.2843	−0.0172	0.1408	0.093*
H6A	0.3501	0.0608	0.0444	0.093*
C7	0.5338 (16)	0.1515 (11)	0.2503 (13)	0.057 (3)
H7B	0.6596	0.1120	0.2077	0.069*
H7A	0.5380	0.1268	0.3338	0.069*
C8	0.5628 (12)	0.3170 (9)	0.3049 (8)	0.0320 (18)
H8B	0.6702	0.3488	0.2610	0.038*
H8A	0.6197	0.3668	0.4128	0.038*
S1	0.1020 (3)	0.1702 (2)	−0.2355 (2)	0.0345 (5)
S2	0.2882 (3)	0.3662 (2)	0.2509 (2)	0.0306 (5)
Cl	0.2644 (3)	0.6363 (2)	−0.0082 (2)	0.0339 (5)
Ag	0.29919 (12)	0.39288 (8)	0.01788 (7)	0.0394 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.036 (4)	0.030 (5)	0.035 (4)	0.012 (4)	0.007 (4)	0.009 (4)
C2	0.032 (4)	0.050 (6)	0.039 (5)	0.005 (4)	0.014 (4)	0.026 (4)
C3	0.050 (5)	0.057 (6)	0.035 (5)	0.020 (5)	0.009 (4)	0.026 (5)
C4	0.027 (4)	0.047 (5)	0.034 (5)	0.013 (4)	0.002 (4)	0.016 (4)
C5	0.034 (4)	0.042 (5)	0.047 (5)	0.001 (4)	0.005 (4)	0.029 (4)
C6	0.051 (7)	0.032 (6)	0.122 (11)	0.009 (5)	0.007 (7)	0.014 (7)
C7	0.047 (6)	0.042 (6)	0.082 (8)	0.027 (5)	0.006 (5)	0.028 (6)
C8	0.028 (4)	0.038 (5)	0.027 (4)	0.002 (4)	−0.004 (3)	0.016 (4)
S1	0.0374 (11)	0.0337 (12)	0.0384 (12)	0.0066 (9)	0.0128 (9)	0.0197 (10)
S2	0.0335 (11)	0.0329 (11)	0.0301 (10)	0.0121 (9)	0.0089 (8)	0.0170 (9)
Cl	0.0343 (10)	0.0353 (11)	0.0410 (11)	0.0134 (9)	0.0130 (9)	0.0227 (10)
Ag	0.0508 (4)	0.0415 (4)	0.0340 (4)	0.0131 (3)	0.0097 (3)	0.0240 (3)

Geometric parameters (Å, º) top

C1—C2	1.506 (11)	C7—C8	1.489 (12)
C1—S1	1.816 (9)	C8—S2	1.827 (7)
C2—C3	1.518 (12)	S1—Ag	2.623 (2)
C3—C4	1.524 (12)	S2—Ag	2.5541 (19)
C4—S1	1.826 (7)	Cl—Ag	2.5581 (19)
C5—C6	1.470 (14)	Cl—Agⁱ	2.748 (2)
C5—S2	1.837 (9)	Ag—Clⁱ	2.748 (2)
C6—C7	1.430 (15)

C2—C1—S1	105.2 (5)	C8—S2—C5	93.4 (4)
C1—C2—C3	105.4 (7)	C8—S2—Ag	103.5 (3)
C2—C3—C4	107.4 (6)	C5—S2—Ag	100.4 (3)
C3—C4—S1	106.6 (5)	Ag—Cl—Agⁱ	79.35 (5)
C6—C5—S2	104.7 (7)	S2—Ag—Cl	123.95 (7)
C7—C6—C5	111.7 (10)	S2—Ag—S1	118.30 (7)
C6—C7—C8	112.4 (7)	Cl—Ag—S1	107.93 (7)
C7—C8—S2	106.7 (6)	S2—Ag—Clⁱ	101.61 (6)
C1—S1—C4	93.7 (4)	Cl—Ag—Clⁱ	100.65 (5)
C1—S1—Ag	100.2 (3)	S1—Ag—Clⁱ	98.94 (7)
C4—S1—Ag	99.8 (3)

S1—C1—C2—C3	−44.4 (8)	C2—C1—S1—Ag	−76.7 (6)
C1—C2—C3—C4	48.3 (9)	C3—C4—S1—C1	3.1 (7)
C2—C3—C4—S1	−29.5 (9)	C3—C4—S1—Ag	104.1 (6)
S2—C5—C6—C7	34.5 (12)	C7—C8—S2—C5	3.3 (7)
C5—C6—C7—C8	−34.4 (15)	C7—C8—S2—Ag	−98.2 (6)
C6—C7—C8—S2	16.3 (12)	C6—C5—S2—C8	−20.9 (8)
C2—C1—S1—C4	23.9 (6)	C6—C5—S2—Ag	83.5 (8)

Symmetry code: (i) −x+1, −y+1, −z.

References

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