Crystal structure of N-(2-{[2,6-bis­(2,2,2-tri­fluoro­acetamido)­phen­yl]disulfan­yl}-3-(2,2,2-tri­fluoro­acetamido)­phen­yl)-2,2,2-tri­fluoro­acetamide

Dennis Awasabisah; Douglas R Powell; George B Richter-Addo

doi:10.1107/S2056989015014231

. 2015 Aug 6;71(Pt 9):o639–o640. doi: 10.1107/S2056989015014231

Crystal structure of N-(2-{[2,6-bis(2,2,2-trifluoroacetamido)phenyl]disulfanyl}-3-(2,2,2-trifluoroacetamido)phenyl)-2,2,2-trifluoroacetamide

Dennis Awasabisah ^a,^*, Douglas R Powell ^a, George B Richter-Addo ^a

PMCID: PMC4555375 PMID: 26396879

Abstract

The title compound, C₂₀H₁₀F₁₂N₄O₄S₂, is an organic diaryl disulfide compound with trifluoroacetamide substituents at the ortho-positions of each benzene ring. There are two molecules (labeled A and B) in the asymmetric unit. The F atoms of three of the –CF₃ groups exhibit rotational disorder over two positions each. The S—S bond distances are 2.0914 (7) and 2.0827 (6) Å for molecules A and B, respectively. The dihedral angle between the S—S—C and S—C—C planes is 103.05 (15)° for molecule A and 104.09 (15)° for molecule B. The three-dimensional supramolecular architecture of the crystal is sustained by numerous N—H⋯O, N—H⋯S and C—H⋯O interactions.

Keywords: crystal structure, diaryl disulfide, S—S bonds, N—H⋯S interactions, N—H⋯F interactions, C—H⋯O interactions.

Related literature

For the synthesis of dithiobis(N-phenylamide) compounds, see: Ueyama et al. (1995 ▸); Lumb et al. (2014 ▸). For related crystal structures, see: Ueyama et al. (1995 ▸); Raftery et al. (2009 ▸). For applications of the title compound and related compounds, see: Klingele et al. (2013 ▸); Xu et al. (2006 ▸); Enemark & Cooney (2004 ▸); Yu et al. (2008 ▸); Smith et al. (2005 ▸); Ueyama et al. (1995 ▸, 1998 ▸); Reichardt et al. (2003 ▸); Dance (1986 ▸).

Experimental

Crystal data

C₂₀H₁₀F₁₂N₄O₄S₂
M _r = 662.44
Monoclinic,
a = 19.0538 (10) Å
b = 13.1466 (7) Å
c = 19.961 (1) Å
β = 96.0042 (9)°
V = 4972.7 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 100 K
0.65 × 0.25 × 0.14 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▸) T _min = 0.808, T _max = 0.954
91119 measured reflections
12375 independent reflections
10553 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.135
S = 1.00
12375 reflections
865 parameters
393 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.37 e Å⁻³
Δρ_min = −1.09 e Å⁻³

Data collection: SMART (Bruker, 2007 ▸); cell refinement: SAINT; data reduction: SAINT (Bruker, 2007 ▸); program(s) used to solve structure: SHELXS (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: SHELXL2002; software used to prepare material for publication: SHELXL2014.

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015014231/hb7457sup1.cif

e-71-0o639-sup1.cif^{(3MB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014231/hb7457Isup2.hkl

e-71-0o639-Isup2.hkl^{(677.5KB, hkl)}

Click here for additional data file.^{(8.9KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015014231/hb7457Isup3.cml

Click here for additional data file.^{(335.9KB, tif)}

. DOI: 10.1107/S2056989015014231/hb7457fig1.tif

The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level. Aromatic H atoms and disordered groups have been omitted for clarity.

Click here for additional data file.^{(465.4KB, tif)}

. DOI: 10.1107/S2056989015014231/hb7457fig2.tif

The packing diagram.

CCDC reference: 1415414

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N1AH1ANO4B	0.89(3)	2.19(3)	2.988(2)	149(2)
N2AH2ANS1A	0.84(3)	2.42(3)	2.9425(18)	121(2)
N2AH2ANS2A	0.84(3)	2.96(3)	3.4543(18)	120(2)
N3AH3ANO1A ⁱ	0.84(3)	2.12(3)	2.857(2)	146(2)
C5AH5AO2A	0.95	2.34	2.952(3)	122
C13AH13AF5B ⁱⁱ	0.95	2.54	3.207(4)	127
C15AH15AO4A	0.95	2.25	2.883(3)	123
N1BH1BNO2A ⁱⁱⁱ	0.80(3)	2.42(3)	2.983(2)	128(2)
N3BH3BNO1B ^iv	0.79(3)	2.24(3)	2.848(2)	135(3)
N4BH4BNO3B ^iv	0.85(3)	2.47(3)	3.032(2)	125(2)
C5BH5BO2B	0.95	2.27	2.896(3)	122
C15BH15BO3A	0.95	2.56	3.229(3)	128
C15BH15BO4B	0.95	2.27	2.898(3)	123

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

The authors wish to thank the National Science Foundation (CHE-1213674 and CHE-0130835) and the University of Oklahoma for funds to support this research and to acquire the diffractometer and computers used in this work.

supplementary crystallographic information

S1. Introduction

Thiolate coordination to metal centers are common in metalloproteins (Enemark et al., 2004), and several crystal structures of thiolate complexes are known (Klingele et al., 2013; Dance, 1986). Further, dithio-bis-N-phenyl compounds such as the title compound, C₂₀H₁₀F₁₂N₄O₄S₂, have often been used as precursors for the synthesis of metal thiolate complexes (Yu et al., 2008; Smith et al., 2005; Ueyama et al., 1998; Ueyama et al., 1996; Xu et al., 2006). Only a handful of crystal structures of dithio-bis-N-phenylamide compounds are known (Ueyama et al., 1995; Raftery et al., 2009). We now report the crystal structure of the known compound 2,2'-dithio-bis(N-phenyl-2,2,2-trifluoroacetamide) (Ueyama et al., 1998; Ueyama, et al., 1995) (Fig. 1). There are two formula units (molecule A and molecule B) per asymmetric unit of the cell. The S–S bond distances are 2.0914 (7) Å for molecule A, and 2.0827 (6) Å, for molecule B. The dihedral angles between the S–S–C planes and the S–C–C planes are 103.05 (15) ° for molecule A, and 104.09 (15) ° for molecule B.

S2. Experimental

The title compound, C₂₀H₁₀F₁₂N₄O₄S₂, was prepared as reported in the literature (Ueyama et al., 1998; Ueyama, et al., 1995) to give 90% isolated yield of the yellow product. IR (KBr, cm^-1): ν_NH = 3362, 3335; ν_CO = 1741, 1730. ¹⁹F NMR (CDCl₃, ppm): δ –75.61 (s, CF₃). ¹H NMR (CDCl₃, ppm): δ 8.59 (s, 4H, NH); 8.21 (d, J = 8.7 Hz, 4H, phenyl-H); 7.62 (t, J = 8.7 Hz, 2H, phenyl-H). Single crystals of the compound were obtained by a slow evaporation of a methylene chloride/ hexane (2:1) solution of the compound.

S3. Refinement

H atoms were located geometrically and refined using a riding model on their parent atoms, with C–H = 0.95 Å for aromatic, with U_iso(H) = 1.2–1.5U_eq(C). The F atoms of three of the CF₃ groups exhibit rotational disorder over two positions each. The occupancies of atoms F4A - F6A were refined to 0.538 (10) and 0.462 (10) for the unprimed and primed atoms. The occupancies of atoms F10A – F12A were refined to 0.509 (7) and 0.491 (7) for the A and C labeled atoms. The occupancies of atoms F4B – F6B were refined to 0.658 (7) and 0.342 (7) for the unprimed and primed atoms. Restraints on the positional and displacement parameters of the disordered atoms were required. The final difference map had maxima and minima of 1.375 and -1.087 e/Å³, respectively, which were located close to the disordered F atoms. Specifically, the largest peak was located close to F12A and the smallest hole was located close to F12C.