1,2-Bis­(di­phenyl­thio­arsinoyl)­ethane

Davies, S.C.; Smith, M.C.; Evans, D.J.

doi:10.1107/S1600536804011158

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 60| Part 6| June 2004| Pages m771-m772

https://doi.org/10.1107/S1600536804011158

1,2-Bis(diphenylthioarsinoyl)ethane

Sian C. Davies,^a ^* Matt C. Smith ^a and David J. Evans ^a

^aDepartment of Biological Chemistry, John Innes Centre, Norwich Research Park, Colney Lane, Norwich NR4 7UH, England
^*Correspondence e-mail: sianc.davies@bbsrc.ac.uk

(Received 2 April 2004; accepted 7 May 2004; online 15 May 2004)

The structure of the title compound, [As₂S₂(C₂H₄)(C₆H₅)₄], which has twofold symmetry, features an As=S bond distance of 2.0674 (13) Å.

Comment

The title compound, (I), was prepared for use as a ligand in novel nickel complexes (Smith, 2002 ) as part of a wider study to prepare synthetic compounds with features similar to those of the active sites of the nickel-containing enzymes: hydrogenase, carbon monoxide dehydrogenase and acetyl-CoA synthase (Smith et al., 2003 ; Evans & Pickett, 2003 ).

The structure of (I) (Fig. 1 and Table 1) lies about a twofold rotation axis which bisects the ethane bond. The As atom is tetrahedrally coordinated, with S—As—C angles lying in the range 111.51 (13)–114.04 (12)° and C—As—C angles lying in the range 105.60 (17)–106.92 (15)°. Bond lengths within the molecule are as expected, with As—C lengths lying in the range 1.924 (4)–1.946 (3) Å and As—S being 2.0674 (13) Å. The torsion angle for the ethane bridge [As—C—Cⁱ—Asⁱ; symmetry code (i) 1 − x, y, ½ − z] is 156.4 (2)°.

The molecules, separated by normal van der Waals contacts, are arranged so that circular channels run parallel to the crystallographic a axis (bounded by four molecules) and rectangular channels run parallel to the c axis (bounded by eight molecules), as highlighted in the two views of Fig. 2.

Figure 1
A view of (I

). Displacement ellipsoids are drawn at the 50% probability level. Symmetry code (i) 1 − x, y, ½ − z

Figure 2
Packing diagrams for (I

) showing (a) a view in the direction of the crystallographic [100] vector and (b) a view in the direction of the crystallographic [001] vector.

Experimental

Under an N₂ atmosphere, solid elemental S (0.153 g, 4.77 mmol) was added to a slurry of [(Ph)₂AsCH₂CH₂As(Ph)₂] (1.16 g, 2.39 mmol; Aldrich) in ethanol (50 ml). The mixture was refluxed for 5 h, giving a light-coloured orange–brown solution. Upon cooling and standing overnight, large colourless needles formed that were collected by filtration and dried in vacuo (0.21 g, 16%). Expected for C₂₆H₂₄As₂S₂: C 56.7, H 4.4, S 11.6%; found: C 56.8, H 4.3, S 12.8%.

Crystal data

[As₂S₂(C₂H₄)(C₆H₅)₄]
M_r = 550.43
Monoclinic, C2/c
a = 15.976 (3) Å
b = 9.168 (4) Å
c = 17.635 (3) Å
β = 107.213 (13)°
V = 2467.3 (13) Å³
Z = 4
D_x = 1.482 Mg m⁻³
Mo–Kα radiation
Cell parameters from 25 reflections
θ = 10–11°
μ = 2.89 mm⁻¹
T = 293 (2) K
Needle, colourless
0.52 × 0.12 × 0.06 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
ω/θ scans
Absorption correction: ψ scan (EMPABS; Sheldrick et al., 1977 ) T_min = 0.713, T_max = 0.841
3937 measured reflections
3573 independent reflections
1815 reflections with I > 2σ(I)
R_int = 0.021
θ_max = 30.0°
h = −22 → 21
k = −1 → 12
l = −1 → 24
3 standard reflections frequency: 167 min intensity decay: 13.2%

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.097
S = 1.01
3573 reflections
148 parameters
Only H-atom U's refined
w = 1/[σ²(F_o²) + (0.0218P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

As1—S1	2.0674 (13)
As1—C12	1.946 (3)
As1—C111	1.928 (3)
As1—C121	1.924 (4)
C12—C12ⁱ	1.511 (7)

C12—As1—S1	111.51 (13)
C111—As1—S1	114.04 (12)
C121—As1—S1	112.53 (12)
C111—As1—C12	105.64 (14)
C121—As1—C12	105.60 (17)
C121—As1—C111	106.92 (15)
C12ⁱ—C12—As1	110.4 (3)

As1—C12—C12ⁱ—As1ⁱ	156.4 (2)
Symmetry code: (i) $[1-x,y,{\script{1\over 2}}-z]$ .

All H atoms were positioned geometrically and allowed to ride on the parent atoms, with C—H distances of 0.93 Å for phenyl H atoms and 0.97 Å for methyl H atoms; isotropic displacement parameters were refined freely.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1992 ); cell refinement: CAD-4 EXPRESS; data reduction: CAD-4 (Hursthouse, 1976 ) and BAYES (French & Wilson, 1978 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536804011158/tk6162sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804011158/tk6162Isup2.hkl

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1992); cell refinement: CAD-4 EXPRESS; data reduction: CAD4 (Hursthouse, 1976); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

(I) top

Crystal data top

[As₂S₂(C₂H₄)(C₆H₅)₄]	F(000) = 1112
M_r = 550.43	D_x = 1.482 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 15.976 (3) Å	θ = 10–11°
b = 9.168 (4) Å	µ = 2.89 mm⁻¹
c = 17.635 (3) Å	T = 293 K
β = 107.213 (13)°	Needles, colourless
V = 2467.3 (13) Å³	0.52 × 0.12 × 0.06 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1815 reflections with I > 2σ(I)'
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 30.0°, θ_min = 1.5°
scintillation counter; ω/θ scans	h = −22→21
Absorption correction: ψ scan (EMPABS; Sheldrick et al., 1977)	k = −1→12
T_min = 0.713, T_max = 0.841	l = −1→24
3937 measured reflections	3 standard reflections every 167 min
3573 independent reflections	intensity decay: 13.2%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0218P)²] where P = (F_o² + 2F_c²)/3
3573 reflections	(Δ/σ)_max < 0.001
148 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
As1	0.37035 (2)	0.58646 (4)	0.14995 (2)	0.03721 (13)
S1	0.40216 (7)	0.77551 (12)	0.10081 (6)	0.0570 (3)
C111	0.2570 (2)	0.5915 (4)	0.16775 (19)	0.0390 (8)
C112	0.1942 (2)	0.6818 (5)	0.1219 (2)	0.0473 (10)
H112	0.2078	0.7442	0.0856	0.041 (10)*
C113	0.1104 (3)	0.6804 (6)	0.1295 (3)	0.0629 (13)
H113	0.0678	0.7419	0.0981	0.072 (14)*
C114	0.0901 (3)	0.5901 (6)	0.1823 (3)	0.0664 (13)
H114	0.0335	0.5887	0.1866	0.075 (14)*
C115	0.1530 (3)	0.5010 (6)	0.2293 (3)	0.0695 (14)
H115	0.1393	0.4402	0.2662	0.067 (14)*
C116	0.2362 (3)	0.5010 (5)	0.2223 (2)	0.0585 (12)
H116	0.2787	0.4400	0.2542	0.060 (13)*
C121	0.3719 (2)	0.4171 (4)	0.0860 (2)	0.0409 (9)
C122	0.3939 (3)	0.4326 (6)	0.0164 (2)	0.0576 (12)
H122	0.4073	0.5243	0.0006	0.064 (14)*
C123	0.3960 (3)	0.3125 (7)	−0.0295 (3)	0.0819 (17)
H123	0.4114	0.3228	−0.0761	0.087 (16)*
C124	0.3756 (3)	0.1787 (7)	−0.0071 (4)	0.0835 (18)
H124	0.3765	0.0979	−0.0387	0.108 (19)*
C125	0.3540 (3)	0.1624 (6)	0.0614 (4)	0.0762 (15)
H125	0.3407	0.0703	0.0767	0.060 (14)*
C126	0.3516 (3)	0.2815 (5)	0.1081 (3)	0.0552 (11)
H126	0.3361	0.2700	0.1547	0.080 (16)*
C12	0.4538 (2)	0.5458 (5)	0.2530 (2)	0.0460 (10)
H12A	0.4485	0.6192	0.2909	0.067 (14)*
H12B	0.4409	0.4516	0.2719	0.062 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
As1	0.0383 (2)	0.0374 (2)	0.0347 (2)	0.0010 (2)	0.00898 (14)	0.0018 (2)
S1	0.0718 (7)	0.0420 (6)	0.0622 (7)	−0.0013 (6)	0.0276 (6)	0.0087 (6)
C111	0.0395 (19)	0.044 (2)	0.0336 (18)	0.001 (2)	0.0108 (15)	−0.0002 (19)
C112	0.046 (2)	0.051 (3)	0.043 (2)	0.005 (2)	0.0104 (18)	0.007 (2)
C113	0.044 (3)	0.079 (4)	0.061 (3)	0.010 (3)	0.010 (2)	0.003 (3)
C114	0.045 (3)	0.087 (4)	0.073 (3)	0.003 (3)	0.027 (2)	−0.011 (3)
C115	0.075 (3)	0.081 (4)	0.067 (3)	−0.005 (3)	0.044 (3)	0.008 (3)
C116	0.054 (3)	0.070 (3)	0.057 (3)	0.012 (3)	0.024 (2)	0.020 (3)
C121	0.0349 (19)	0.040 (2)	0.044 (2)	0.000 (2)	0.0056 (16)	−0.007 (2)
C122	0.053 (3)	0.066 (3)	0.059 (3)	−0.006 (2)	0.025 (2)	−0.008 (3)
C123	0.070 (3)	0.109 (5)	0.071 (3)	−0.005 (3)	0.027 (3)	−0.045 (4)
C124	0.058 (3)	0.077 (4)	0.105 (5)	0.006 (3)	0.007 (3)	−0.051 (4)
C125	0.063 (3)	0.046 (3)	0.111 (5)	0.004 (3)	0.011 (3)	−0.008 (3)
C126	0.057 (3)	0.038 (3)	0.068 (3)	0.002 (2)	0.016 (2)	−0.003 (2)
C12	0.041 (2)	0.059 (3)	0.0325 (19)	−0.0008 (19)	0.0027 (17)	0.005 (2)

Geometric parameters (Å, º) top

As1—S1	2.0674 (13)	C115—C116	1.371 (5)
As1—C12	1.946 (3)	C115—H115	0.9300
As1—C111	1.928 (3)	C116—H116	0.9300
As1—C121	1.924 (4)	C121—C126	1.372 (5)
C12—C12ⁱ	1.511 (7)	C121—C122	1.380 (5)
C12—H12A	0.9700	C122—C123	1.373 (6)
C12—H12B	0.9700	C122—H122	0.9300
C111—C112	1.366 (5)	C123—C124	1.357 (7)
C111—C116	1.383 (5)	C123—H123	0.9300
C112—C113	1.384 (5)	C124—C125	1.359 (7)
C112—H112	0.9300	C124—H124	0.9300
C113—C114	1.356 (6)	C125—C126	1.376 (6)
C113—H113	0.9300	C125—H125	0.9300
C114—C115	1.368 (6)	C126—H126	0.9300
C114—H114	0.9300

C12—As1—S1	111.51 (13)	C114—C115—C116	120.2 (4)
C111—As1—S1	114.04 (12)	C114—C115—H115	119.9
C121—As1—S1	112.53 (12)	C116—C115—H115	119.9
C111—As1—C12	105.64 (14)	C115—C116—C111	120.1 (4)
C121—As1—C12	105.60 (17)	C115—C116—H116	119.9
C121—As1—C111	106.92 (15)	C111—C116—H116	119.9
C12ⁱ—C12—As1	110.4 (3)	C126—C121—C122	119.4 (4)
As1—C12—H12A	109.6	C126—C121—As1	121.3 (3)
As1—C12—H12B	109.6	C122—C121—As1	119.3 (3)
C12ⁱ—C12—H12A	109.6	C123—C122—C121	119.9 (5)
C12ⁱ—C12—H12B	109.6	C123—C122—H122	120.1
H12A—C12—H12B	108.1	C121—C122—H122	120.1
C112—C111—C116	119.4 (4)	C124—C123—C122	120.3 (5)
C112—C111—As1	118.6 (3)	C124—C123—H123	119.9
C116—C111—As1	121.9 (3)	C122—C123—H123	119.9
C111—C112—C113	119.9 (4)	C123—C124—C125	120.3 (5)
C111—C112—H112	120.1	C123—C124—H124	119.9
C113—C112—H112	120.1	C125—C124—H124	119.9
C114—C113—C112	120.5 (4)	C124—C125—C126	120.3 (5)
C114—C113—H113	119.8	C124—C125—H125	119.8
C112—C113—H113	119.8	C126—C125—H125	119.8
C113—C114—C115	119.9 (4)	C121—C126—C125	119.9 (4)
C113—C114—H114	120.0	C121—C126—H126	120.1
C115—C114—H114	120.0	C125—C126—H126	120.1

C121—As1—C111—C112	−99.4 (3)	S1—As1—C121—C126	−179.2 (3)
C12—As1—C111—C112	148.4 (3)	C111—As1—C121—C122	126.7 (3)
S1—As1—C111—C112	25.6 (3)	C12—As1—C121—C122	−121.1 (3)
C121—As1—C111—C116	77.0 (3)	S1—As1—C121—C122	0.7 (3)
C12—As1—C111—C116	−35.2 (4)	C126—C121—C122—C123	−0.6 (6)
S1—As1—C111—C116	−158.0 (3)	As1—C121—C122—C123	179.5 (3)
C116—C111—C112—C113	−1.0 (6)	C121—C122—C123—C124	0.7 (7)
As1—C111—C112—C113	175.5 (3)	C122—C123—C124—C125	−0.7 (8)
C111—C112—C113—C114	0.1 (7)	C123—C124—C125—C126	0.7 (8)
C112—C113—C114—C115	0.9 (7)	C122—C121—C126—C125	0.6 (6)
C113—C114—C115—C116	−1.1 (7)	As1—C121—C126—C125	−179.5 (3)
C114—C115—C116—C111	0.2 (7)	C124—C125—C126—C121	−0.6 (7)
C112—C111—C116—C115	0.8 (6)	C121—As1—C12—C12ⁱ	69.40 (15)
As1—C111—C116—C115	−175.6 (3)	C111—As1—C12—C12ⁱ	−177.52 (13)
C111—As1—C121—C126	−53.2 (3)	S1—As1—C12—C12ⁱ	−53.11 (13)
C12—As1—C121—C126	58.9 (3)	As1—C12—C12ⁱ—As1ⁱ	156.4 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Acknowledgements

The Biotechnology and Biological Sciences Research Council is thanked for funding.

References

Enraf–Nonius (1992). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Evans, D. J. & Pickett, C. J. (2003). Chem. Soc. Rev. 32, 268–275. Web of Science CrossRef PubMed Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
French, S. & Wilson, K. (1978). Acta Cryst. A34, 517–525. CrossRef CAS IUCr Journals Web of Science Google Scholar
Hursthouse, M. B. (1976). CAD-4. Queen Mary College, London, England. Google Scholar
Sheldrick, G. M., Orpen, A. G., Reichert, B. E. & Raithby, P. R. (1977). EMPABS. 4th European Crystallographic Meeting, Oxford, Abstracts, p. 147. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Smith, M. C. (2002). PhD thesis, University of East Anglia, England. Google Scholar
Smith, M. C., Barclay, J. E., Davies, S. C., Hughes, D. L. & Evans, D. J. (2003). Dalton Trans. pp. 4147–4151. Web of Science CSD CrossRef Google Scholar

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