1,1,1-Trifluoro-4-(thio­phen-2-yl)-4-[(2-{[4,4,4-trifluoro-3-oxo-1-(thio­phen-2-yl)but-1-en-1-yl]amino}­eth­yl)amino]­but-3-en-2-one

Abdullah M Asiri; Abdulrahman O Al-Youbi; Hassan M Faidallah; Seik Weng Ng

doi:10.1107/S1600536811036889

. 2011 Sep 17;67(Pt 10):o2659–o2660. doi: 10.1107/S1600536811036889

1,1,1-Trifluoro-4-(thiophen-2-yl)-4-[(2-{[4,4,4-trifluoro-3-oxo-1-(thiophen-2-yl)but-1-en-1-yl]amino}ethyl)amino]but-3-en-2-one

Abdullah M Asiri ^a,^b, Abdulrahman O Al-Youbi ^a, Hassan M Faidallah ^a, Seik Weng Ng ^c,^a,^*

PMCID: PMC3201547 PMID: 22064455

Abstract

The asymmetric unit of the diamine compound, C₁₈H₁₄F₃N₂O₂S₂, consists of two molecules; the C=C double bond has a Z configuration in the C₄H₃S—C=C—C(=O)—C segment. The –NH—CH₂—CH₂—NH chain adopts a twisted U-shape. The amino group is an intramolecular hydrogen-bond donor to the carbonyl group; the intramolecular hydrogen bond generates a six-membered ring. In both molecules, the thienyl rings are disordered over two positions; the occupancies of the major components are 0.817 (4) and 0.778 (4) in one molecule and 0.960 (4) and 0.665 (4) in the other. One of the trifluoromethyl groups is disordered over two positions with the major component having 0.637 (8) occupancy.

Related literature

For the synthesis, see: Wang & Tong (1995 ▶). For related structures, see: Bresciani-Pahor et al. (1979 ▶); Haider et al. (1981 ▶).

Experimental

Crystal data

C₁₈H₁₄F₆N₂O₂S₂
M _r = 468.43
Orthorhombic,
a = 20.4520 (4) Å
b = 12.5201 (2) Å
c = 15.8328 (2) Å
V = 4054.16 (11) Å³
Z = 8
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.906, T _max = 0.936
40183 measured reflections
9198 independent reflections
8265 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.122
S = 1.05
9198 reflections
633 parameters
242 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.59 e Å⁻³
Absolute structure: Flack (1983 ▶), 4340 Friedel pairs
Flack parameter: 0.01 (7)

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811036889/xu5326sup1.cif

e-67-o2659-sup1.cif^{(37.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036889/xu5326Isup2.hkl

e-67-o2659-Isup2.hkl^{(449.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811036889/xu5326Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯O1	0.88 (1)	2.03 (3)	2.741 (3)	138 (3)
N2—H2n⋯O2	0.88 (1)	2.01 (3)	2.726 (3)	138 (3)
N3—H3n⋯O3	0.88 (1)	1.93 (3)	2.668 (3)	140 (3)
N4—H4n⋯O4	0.87 (1)	1.96 (3)	2.677 (3)	139 (3)

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Acknowledgments

We thank King Abdulaziz University and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

Ethylenediamine generally condenses with aldehydes and ketones to yield Schiff bases, which are typically yellow compounds whose coloration arises from the azomethine linkage. For some 1,3-diketones (such as acetylacetone and benzoylmethane), the diamine condenses with the carbony function of two ketone molecules. In the condensation product, the azomethine double-bond isomerizes to result in the formation of a secondary amine, as noted in the diamine, 4-((2-((1-methyl-3-oxo-but-1-enyl)amino)ethyl)amino)pent-3-en-2-one (from the condensation of ethylenediamine with acetylacetone) (Bresciani-Pahor et al., 1979) and the analogous amine from the condensation of ethylenediamine with benzoyacetone (Haider et al., 1981). The product from the condensation with 2-theonyltrifluoroacetone was first reported in 1995, but the authors of the study assigned it as (ethanediyldinitrilo)bis[fluoro(thienyl)butanone as they considered it a Schiff-base-alicyclic type of crown ether (Wang & Tong, 1995). The compound is, in fact, is diamine (Scheme I). The asymmetric unit of the diamine, C₁₆H₁₄F₃N₂O₁S₂, consists of two molecules; the C–C double-bond is of a Z-configuration. In the C₄H₃S–C═C–C(═O)–C segment, the thienyl ring and acetyl fragment are approximately coplanar. The amino group is an intramolecular hydrogen-bond donor to the carbonyl group, and the hydrogen bond generates a six-membered ring (Table 1). In both molecules, their thienyl rings are each disordered over two positions; one trifluoromethyl group is also disordered (Fig. 1 and Fig. 2). Whereas similar diamines are centrosymmetric molecules with the inversion center in the middle of the ethane link, the present compound is not. The –NH–CH₂–CH₂–NH chain adopts a twisted U-shape.

Experimental

Ethylenediamine (0.6 g, 10 mmol) and the 2-theonyltrifluoroacetone (2.2 g, 10 mmol) in benzene (50 ml) were heated in a Dean-Stark trap until no more water was collected (in about 2 h). The solvent was removed and the residue was treated with a little methanol. The solid that separated was recystallized from ethanol to yield light yellow crystals.