2,2′-(Diselane-1,2-di­yl)dinicotinamide N,N′-dimethyl­formamide disolvate

Aixia Feng; Ying Xu; Xuehong Wei

doi:10.1107/S1600536810015047

. 2010 Apr 30;66(Pt 5):o1216. doi: 10.1107/S1600536810015047

2,2′-(Diselane-1,2-diyl)dinicotinamide N,N′-dimethylformamide disolvate

Aixia Feng ^a, Ying Xu ^a, Xuehong Wei ^a,^*

PMCID: PMC2979017 PMID: 21579243

Abstract

The asymmetric unit of the title compound, C₁₂H₁₀N₄O₂Se₂·2C₃H₇NO, contains two solvent molecules and two half molecules of the dinicotinamide, each of which sits on a center of symmetry passing through the middle of the Se—Se bond. In each molecule, the two pyridyl groups and diseleno group are approximately coplanar (r.m.s. deviations from planarity for all non-H atoms = 0.011 and 0.008 Å in the two molecules). Intermolecular N—H⋯O hydrogen bonds stablilize the crystal packing.

Related literature

For the potential applications of organoselenium compounds in organic synthesis, as precursors for semiconducting materials and in ligand chemistry and biochemistry, see: Mugesh et al. (2001 ▶). For related diselenide compounds, see: Bhasin & Singh (2002 ▶); Kienitz et al. (1996 ▶).

Experimental

Crystal data

C₁₂H₁₀N₄O₂Se₂·2C₃H₇NO
M _r = 546.34
Triclinic,
a = 7.6101 (17) Å
b = 12.318 (3) Å
c = 13.420 (3) Å
α = 114.175 (2)°
β = 91.017 (3)°
γ = 95.833 (3)°
V = 1139.3 (4) Å³
Z = 2
Mo Kα radiation
μ = 3.28 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.20 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.439, T _max = 0.560
3937 measured reflections
3937 independent reflections
3359 reflections with I > 2σ(I)

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.097
S = 1.03
3937 reflections
275 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810015047/fl2299sup1.cif

e-66-o1216-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015047/fl2299Isup2.hkl

e-66-o1216-Isup2.hkl^{(192.9KB, hkl)}

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⋯O4	0.86	2.09	2.946 (4)	170
N1—H1B⋯O3	0.86	2.03	2.869 (5)	163
N3—H3B⋯O4	0.86	2.10	2.919 (4)	158
N3—H3A⋯O1ⁱ	0.86	2.31	3.081 (4)	150

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Symmetry code: (i) Inline graphic .

Acknowledgments

We thank the SNSF (Nos. 2008011021 and 2008012013-2) and the Homecoming Foundation of Shanxi Province for support.

supplementary crystallographic information

Comment

Organoselenium compounds have attracted much atention because of their potential applications in organic synthesis, precursors for semiconducting materials, ligand chemistry and biochemistry (Mugesh et al., 2001). During the past decade, many organoselenium compounds have been synthesized and well characterized. In contrast to alkyl, aryl, and mixed alkylaryl senium compounds, the pyridyl selenium compounds are still rare.

The unit cell contains two nicotinamide molecules and four of the solvent molecules. The asymmetric unit contains two solvent molecules and two half molecues of the nicotinamide each of which sits on a center of symmetry passing through the middle of the Se—Se bond (Fig. 1). In (I),the two independent nicotinamides (molecule A containing Se1 and molecule B containing Se2) have comparable conformations. In each nicotinamide, the two pyridyl groups and the diseleno group are approximately coplanar (r.m.s. deviations from planarity for all non-H atoms are 0.011 and 0.008Å for molecules A and B, respectively while the two CONH₂ groups are rotated out of this plane by 11.0 (5)° and 18.6 (5)° for molecules A and B, respectively. Fig. 2 shows the sheets of molecules formed by intermolecular N-H···O hydrogen-bond interactions between the nicotinamides and neighbouring solvents with distances between 2.869 (5) and 3.081 (4) Å (Table 1).

The structure of (I) is similar to that of other diselenide compounds (Kienitz, et al. 1996; Bhasin and Singh 2002).The two neighbouring pyridyl groups can be brought into register by rotation about the Se—Se bond. The commonly observed approximate coplanarity of the rings and the Se—Se bonds (C—C—Se—Se or N—C—Se—Se torsion angles ca. 0°) in these molecules has been explained in terms of a minimization of Se···Se lone pair repulsion.

Experimental

To a vigorously stirred solution of selenium powder (1.19 g, 15 mmol) and absolute ethanol (30 ml), sodium borohydride (0.40 g, 10.6 mmol) was added at 0 °C. The mixture was warmed to room temperature and stirred for 2 h. 2-Chloro-nicotinamide (1.56 g, 10 mmol) was added and stirred for 7 days. O₂ was passed through the solution slowly for 2 h after the reaction mixture was acidfied by glacial acetic. The solvents were removed in vacuo and the residue was extracted with hot dimethyl sulphoxide (DMSO) and filtered. The filtrate was poured into water( 200 ml, cooled to 0 °C). The precipitate was separated by filtration and recrystallized from DMSO-CH₃OH(1:2) to give the product as yellow crystals, yield: 1.56 g, 78%; m.p. 124-125 °C. ¹H-NMR ( 300 MHz, DCCl₃) δ (ppm): 7.27 (d, 2H), 7.81 (s, 2H), 8.14 (d, 2H), 8.32 (s, 2H), 8.48 (s, 2H), 8.65 (s, 2H);⁷⁷Se-NMR (57 MHz, DMSO-d₆ ) δ(ppm): 524.77.