N-[Bis(dimethyl­amino)­methyl­idene]-2-[(triphenyl­meth­yl)sulfan­yl]ethanaminium hexa­fluoro­phosphate

Adam Neuba; Ulrich Flörke; Gerald Henkel

doi:10.1107/S1600536811014929

. 2011 Apr 29;67(Pt 5):o1238–o1239. doi: 10.1107/S1600536811014929

N-[Bis(dimethylamino)methylidene]-2-[(triphenylmethyl)sulfanyl]ethanaminium hexafluorophosphate

Adam Neuba ^a, Ulrich Flörke ^a,^*, Gerald Henkel ^a

PMCID: PMC3089070 PMID: 21754533

Abstract

The molecular structure of the title compound, C₂₆H₃₂N₃S⁺·PF₆ ⁻, shows a protonated guanidyl group bridged by an ethylene linker with a tritylsulfanyl unit. The guanidinium (gua) unit displays charge delocalization over the three N—C_gua bonds. The N—C—C—S group shows a folded nonplanar conformation with a torsion angle of 158.4 (1)°. In the crystal, the cation and anion are linked by an N—H⋯F interaction.

Related literature

For the synthesis, see: Herres-Pawlis et al. (2005 ▶). For related structures, see: Flörke et al. (2006 ▶); Neuba et al. (2007c ▶); Pruszynski et al. (1992 ▶). For related chemistry literature, see: Börner et al. (2007 ▶, 2009 ▶); Galezowski et al. (1994 ▶); Harmjanz (1997 ▶); Herres et al. (2005 ▶); Herres-Pawlis et al. (2009 ▶); Neuba (2009 ▶); Neuba et al. (2007a ▶,b ▶, 2008a ▶,b ▶, 2010 ▶, 2011 ▶); Peters et al. (2008 ▶); Pohl et al. (2000 ▶); Raab et al. (2003 ▶); Schneider (2000 ▶); Waden (1999 ▶); Wittman (1999 ▶); Wittmann et al. (2001 ▶).

Experimental

Crystal data

C₂₆H₃₂N₃S⁺·PF₆ ⁻
M _r = 563.58
Triclinic,
a = 9.0111 (14) Å
b = 9.1376 (15) Å
c = 17.564 (3) Å
α = 96.532 (3)°
β = 100.225 (4)°
γ = 108.053 (3)°
V = 1331.0 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 120 K
0.33 × 0.30 × 0.26 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.924, T _max = 0.939
11922 measured reflections
6281 independent reflections
4547 reflections with I > 2σ(I)
R _int = 0.060

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.104
S = 0.96
6281 reflections
338 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811014929/bt5504sup1.cif

e-67-o1238-sup1.cif^{(24.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014929/bt5504Isup2.hkl

e-67-o1238-Isup2.hkl^{(307.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811014929/bt5504Isup3.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—H1A⋯F6ⁱ	0.88	2.13	2.949 (2)	155

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

The synthesis and characterization of novel molecules containing nitrogen and sulfur as donor functions and their application in synthesis of sulfur copper complexes is important for biomimetic copper–sulfur chemistry. In search of multifunctional ligands we have extended our studies to guanidyl-type systems with N-donor functions. The first derivative, the ligand bis(tetramethyl-guanidino)propylene as well as amine guanidine hybrids and their complexes with Cu, Fe, Ni, Ag, Mn, Co and Zn have recently been investigated (Harmjanz, 1997; Waden, 1999; Pohl et al., 2000; Schneider, 2000; Wittmann et al., 2001; Herres-Pawlis et al., 2005, 2009; Herres et al., 2005; Neuba et al., 2008a,b, 2010; Börner et al. 2007, 2009). We have now developed several sulfur guanidine hybrids based on aminothiophenol and cysteamine (Neuba et al., 2007a,b,c; Neuba, 2009). The synthesized sulfur guanidine compounds possess aliphatic and aromatic thioethers or disulfide groups and were used in the synthesis of copper thiolate complexes to mimic active centres like the CuA in cytochrome-c oxidase and N₂O-reductase (Neuba et al., 2011). The title compound (I) is the protonated variant of 1,1,3,3-Tetramethyl-2-[2-(tritylsulfanyl)-ethyl]guanidine (C₂₆H₃₁N₃) (Neuba et al., 2007c). Both compounds possess a folded non-planar conformation with torsion angles of the S—C—C—N group of 66.04 (15) in C₂₆H₃₁N₃ and 158.36 (13)° in I. Compared to C₂₆H₃₂N₃ with localized N═C_gua double bond (N═C_gua: 1.281 (2), N—C_gua: 1.399 (2) and 1.292 (2) Å) the respective double bond in I is clearly delocalized over the guanidine unit (N═C_gua: 1.341 (2), N—C_gua: 1.3938 (2) and 1.333 (2) Å). Several variants of protonated bis(tetramethyl-guanidino)propylene (Flörke et al., 2006) show similar N—C (1.326 (7)–1.341 (6) Å) and N—C_gua bond lengths (1.331 (2)–1.343 (3) Å). In bis(tetramethylguanidino)biphenyl (Pruszynski et al., 1992), with a protonated imine N atom, strong delocalization is also observed among the three C—N bonds, which are in the range of 1.31 (1)-1.34 (1) Å. Further protonated guanidine units show comparable N—C_gua– and N═C_gua geometries (Herres-Pawlis et al., 2005; Herres et al., 2005; Wittman, 1999; Peters et al., 2008, Galezowski et al., 1994, Raab et al., 2003).

The crystal packing exhibits N1—H···F6(-x + 1, -y + 1, -z + 1) intermolecular interaction from cation to anion with H···F = 2.127 Å.

Experimental

Preparation of the title compound: 1,1,3,3-Tetramethyl-2-[2-(tritylsulfanyl)-ethyl]guanidine (C₂₆H₃₁N₃) (417 mg, 1 mmol) was added to a solution of [Cu(MeCN)₄]PF₆ (373 mg, 1 mmol) in acetonitrile (aqueous, 15 ml); the mixture was stirred for 15 min at room temperature and then refluxed for further 15 min and filtered off. Colourless crystals were obtained using the vapour pressure equalization method with this solution in the presence of diethylether.