Bis{2-[(Tri­phenyl­meth­yl)amino]­phen­yl} diselenide aceto­nitrile monosolvate

Adam Neuba; Tobias Schneider; Ulrich Flörke; Gerald Henkel

doi:10.1107/S1600536814007806

. 2014 Apr 12;70(Pt 5):o537–o538. doi: 10.1107/S1600536814007806

Bis{2-[(Triphenylmethyl)amino]phenyl} diselenide acetonitrile monosolvate

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

PMCID: PMC4011201 PMID: 24860347

Abstract

The molecular structure of the title compound, C₅₀H₄₀N₂Se₂·C₂H₃N, shows a syn conformation of the benzene rings bound to the Se atoms, with an Se—Se bond length of 2.3529 (6) Å and a C—Se—Se—C torsion angle of 93.53 (14)°. The two Se-bonded aromatic ring planes make a dihedral angle of 18.42 (16)°. Intramolecular N—H⋯Se hydrogen bonds are noted. Intermolecular C—H⋯Se interactions give rise to supramolecular chains extended along [100]. One severely disordered acetonitrile solvent molecule per asymmetric unit was treated with SQUEEZE in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148–155]; the crystal data take the presence of this molecule into account.

Related literature

Due to the importance of selenoproteins (e.g. thioredoxin reductases and glutathione peroxidases) for essential metabolic processes, we have studied organo diselenide systems with N-donor functions with the aim of synthesizing redox-active selenium copper complexes. For the structure of the sulfido compound, see: Tommasi et al. (1999 ▶). For related structures of other bisaryl diselenides, see: Jones & Ramírez de Arellano (1996 ▶); Meyers et al. (1995 ▶); Warin et al. (1993 ▶); Wojtowicz et al. (2003 ▶).

Experimental

Crystal data

C₅₀H₄₀N₂Se₂·C₂H₃N
M _r = 867.81
Triclinic,
a = 9.2364 (16) Å
b = 13.245 (2) Å
c = 18.248 (3) Å
α = 104.956 (4)°
β = 103.578 (4)°
γ = 101.636 (5)°
V = 2013.0 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.88 mm⁻¹
T = 130 K
0.20 × 0.17 × 0.06 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.705, T _max = 0.896
19357 measured reflections
9548 independent reflections
5060 reflections with I > 2σ(I)
R _int = 0.059

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.068
S = 0.64
9548 reflections
495 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.49 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 datablock(s) I, global. DOI: 10.1107/S1600536814007806/tk5302sup1.cif

e-70-0o537-sup1.cif^{(48.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814007806/tk5302Isup2.hkl

e-70-0o537-Isup2.hkl^{(530.9KB, hkl)}

Click here for additional data file.^{(14.3KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814007806/tk5302Isup3.cml

CCDC reference: 996016

Additional supporting information: 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—H1⋯Se1	0.88 (1)	2.62 (3)	3.106 (3)	115 (19)
N2—H2⋯Se2	0.89 (2)	2.64 (2)	3.140 (2)	117 (2)
C35—H35A⋯Se1ⁱ	0.95	2.92	3.777 (3)	150

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Symmetry code: (i) Inline graphic .

Acknowledgments

We thank the German Research Council (DFG) and the Federal Ministry of Education and Research (BMBF) for continued support of our work.

supplementary crystallographic information

1. Chemical context

2. Structural commentary

3. Supramolecular features

4. Database survey

5. Synthesis and crystallization

The title compound was prepared as follows: 2.08 g (5 mmol) bis(2-aminophenyl)diselenide bis hydrochloride (Wojtowicz et al., 2003), 2.77 ml triethylamine (2.02 g; 20 mmol) and 200 ml of dried acetonitrile were placed in a N₂-flushed 250 ml 2-necked flask. 2.79 g (10 mmol) triphenylchloromethane was added and the mixture stirred for one hour. After the solvent was evaporated 100 ml water was added and the mixture was extracted with dichloromethane (3 x 80 ml). The combined organic layers were dried over Na₂SO₄. After filtration the solvent was removed und the crude product was obtained as a yellow powder. For purification, the raw product was stirred in acetonitrile (250 ml) for one hour at 80 °C. The hot suspension was filtered. The collected solid was washed with acetonitrile and dried under reduced poressure. Yield: 3.5 g (85%). Yellow crystals suitable for X-ray diffraction were obtained by diffusion of Et₂O into a cold saturated MeCN solution.

Spectroscopic analyses.

¹H-NMR: (500 MHz, 25 °C, CDCl₃, δ [p.p.m.]) 6.15 (dd, ³J_HH= 8.3 Hz, ⁴J_HH= 1.1 Hz, 2H, 6.27) (ddd, ³J_HH= 7.4 Hz, ³J_HH= 7.4 Hz, ⁴J_HH= 1.1 Hz, 2H); 6.56 (s, 2H,NH); 6.75 (ddd, ³J_HH= 8.3 Hz, ³J_HH= 7.4 Hz, ⁴J_HH=1.5 Hz 2H); 7.19–7.39 (m, 32 H)

¹³C-NMR: (125 MHz,, 25 °C, CDCl₃δ [p.p.m.]): 71.7 (C_q); 115.1 (CH); 116.3 (C_q); 116.9 (CH); 126.8 (CH); 128.1 (CH); 129.1 (CH); 130.4 (CH); 138.2 (2 C,CH) 145.2 (C_q)

¹⁵N-NMR (50,7 MHz,, 25 °C, CDCl₃δ [p.p.m.]): 101 (N)

IR (KBr, ν, [cm^-1]): 2850 s, 2604 s, 1945w, 1602m, 1564m, 1500m, 1467 s, 1301w, 1191w, 1122m, 1051w, 756 s, 543w, 507w, 440 s

EI—MS (m/z (%)): 828.1 (1) [M⁺], 243.0 (100) [C(Ph)₃]⁺; 165.02 (79) [C(Ph)(C₆H₄)]⁺; 183.0 (26) [NH₂C(Ph)₂]⁺; 105.0 (24)[NH₂C(Ph)]⁺.

Elemental analysis (M = 826.79 g mol^-1): calcd. for C₅₀H₄₀N₂Se₂: C: 72.64; H: 4.48; N: 3.39; found C: 71.81, H: 4.94, N: 3.47.

6. Refinement

Hydrogen atoms were clearly identified in difference syntheses, refined at idealized positions riding on the carbon atoms with isotropic displacement parameters U_iso(H) = 1.2U(C_eq) and C—H 0.95 Å. H(N) atom positions were refined with N—H = 0.90±0.01 Å, the U_iso were refined freely. One severely disordered acetonitrile solvent molecule per asymmetric unit was treated with the SQUEEZE facility in PLATON (Spek, 2009) which gave a void count of 43 electrons in the unit cell.