2,2′-(Diselane-1,2-di­yl)bis­(N,N-di­methyl­nicotinamide)

Guo, Z.; Wang, Y.; Xu, Y.; Wei, X.

doi:10.1107/S2414314617008823

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 6| June 2017| x170882

https://doi.org/10.1107/S2414314617008823

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2,2′-(Diselane-1,2-diyl)bis(N,N-dimethylnicotinamide)

Zhiqiang Guo,^a ^* Yakong Wang,^b Ying Xu ^b and Xuehong Wei ^a

^aScientific Instrument Center, Shanxi University, Taiyuan 030006, People's Republic of China, and ^bSchool of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, People's Republic of China
^*Correspondence e-mail: gzq@sxu.edu.cn

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 11 June 2017; accepted 14 June 2017; online 20 June 2017)

The title compound, C₁₆H₁₈N₄O₂Se₂, is centrosymmetric. The dihedral angle between the pyridine ring and the amide side chain is 56.20 (16)°. In the crystal, a weak C—H⋯O interaction links the molecules into [010] chains.

Keywords: crystal structure; diselenides; nicotinic acid derivatives.

CCDC reference: 1555913

Structure description

Many investigations have demonstrated that organoselenium compounds are less toxic than those of inorganic selenium compounds (Jalbout et al. 2008 ). However, to gain further insight into the role of organoselenium compounds, detailed studies are still needed. As part of our research in this area, we report herein the synthesis and crystal structure of the title compound (Fig. 1).

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) −x + 1, −y + 1, −z + 2.]

The complete molecule is generated by a crystallographic centre of symmetry at the mid-point of the Se—Se bond. This implies, of course, that the C—Se—Se—C torsion angle is 180°, which minimizes repulsion of the Se lone pairs, and the dihedral angle between the pyridine rings is 0°. The pyridine ring is substituted at the 2-position [C1—Se = 1.923 (3) Å] and the 3-position [C2—C6 = 1.490 (4) Å]. The X—C—Se—Se torsion angles (X = C, N) are 14.01 (2) and −164.79 (2)°, respectively, indicating that the Se—Se bond lies close to the plane of each pyridine ring. In the crystal, weak C—H⋯O bonds (Table 1) link the molecules into [010] chains.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Oⁱ	0.93	2.52	3.431 (4)	165
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Synthesis and crystallization

The title compound was prepared follows a modified literature procedure (Feng et al., 2010 ). To a vigorously stirred solution of selenium powder (1.00 g, 12.6 mmol) and absolute ethanol (30 ml), sodium borohydride (0.35 g, 9.3 mmol) was added at 0°C. The mixture was warmed to room temperature and stirred for 2 h. 2-Chloro-N,N-dimethylnicotinamide (1.55 g, 8.4 mmol) was added and stirred for 7 d. O₂ was passed through the solution slowly for 2 h after the reaction mixture was acidified by glacial acetic acid. The solvents were removed in vacuo and the residue was extracted with dichloromethane (CH₂Cl₂) and filtered. The filtrate was evaporated in vacuo. The precipitate was separated by filtration and recrystallized from C₆H₁₂–CHCl₃ (1:2) mixed solvent to give the product as colorless block-shaped crystals, yield: 1.0 g, 52%.

¹H NMR (300 MHz, DCCl₃) δ(p.p.m.): 3.07 (s, 12H, Me), 7.10 (q, 2H, ArH), 7.44 (dd, 2H, ArH), 8.41 (dd, 2H, ArH). ¹³C NMR (75 MHz, DCCl₃) δ(p.p.m.): 40.77 (Me), 41.69 (Me), 123.71, 135.47, 136.92, 153.18, 154.68, 171.27(C=O). ⁷⁷Se NMR (57 MHz, DCCl₃) δ(p.p.m.): 486.10. Analysis calculated for C₁₆H₁₈N₄O₂Se₂: C: 42.12, H: 3.98, N: 12.28; found: C:41.74, H: 3.957, N: 12.03.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₈N₄O₂Se₂
M_r	456.26
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.167 (2), 8.726 (3), 13.947 (4)
β (°)	96.375 (4)
V (Å³)	866.8 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	4.28
Crystal size (mm)	0.50 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.223, 0.481
No. of measured, independent and observed [I > 2σ(I)] reflections	3376, 1524, 1300
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.077, 1.06
No. of reflections	1524
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.43
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and ORTEP-3 for Windows (Farrugia, 2012 ).

Structural data

CCDC reference: 1555913

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617008823/hb4154sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617008823/hb4154Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617008823/hb4154Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

2,2'-(Diselane-1,2-diyl)bis(N,N-dimethylnicotinamide) top

Crystal data top

C₁₆H₁₈N₄O₂Se₂	F(000) = 452
M_r = 456.26	D_x = 1.748 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.167 (2) Å	Cell parameters from 2532 reflections
b = 8.726 (3) Å	θ = 2.8–27.5°
c = 13.947 (4) Å	µ = 4.28 mm⁻¹
β = 96.375 (4)°	T = 293 K
V = 866.8 (4) Å³	Block, colorless
Z = 2	0.50 × 0.20 × 0.20 mm

Data collection top

Bruker APEXII CCD diffractometer	1300 reflections with I > 2σ(I)
phi and ω scans	R_int = 0.035
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 25.0°, θ_min = 2.8°
T_min = 0.223, T_max = 0.481	h = −8→6
3376 measured reflections	k = −8→10
1524 independent reflections	l = −16→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.077	w = 1/[σ²(F_o²) + (0.0337P)² + 0.0053P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
1524 reflections	Δρ_max = 0.64 e Å⁻³
111 parameters	Δρ_min = −0.43 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. All H atoms were positioned geometrically(C—H = 0.93–0.96 Å), and refined as riding with U_iso(H) = 1.2Ueq of the adjacent carbon atom (1.5U_eq for methyl H atoms).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Se	0.52041 (4)	0.56001 (3)	0.92626 (2)	0.04189 (16)
N1	0.1797 (4)	0.6437 (3)	0.99097 (18)	0.0386 (6)
N2	0.4942 (4)	0.9794 (3)	0.79999 (18)	0.0403 (6)
O	0.4595 (4)	0.7382 (3)	0.74625 (17)	0.0541 (7)
C1	0.2981 (4)	0.6827 (3)	0.9288 (2)	0.0313 (6)
C2	0.2725 (4)	0.8092 (3)	0.8665 (2)	0.0341 (7)
C3	0.1072 (5)	0.8902 (4)	0.8669 (2)	0.0423 (8)
H3	0.0823	0.9734	0.8257	0.051*
C4	−0.0211 (5)	0.8469 (4)	0.9289 (2)	0.0450 (8)
H4	−0.1344	0.8987	0.9289	0.054*
C5	0.0220 (4)	0.7258 (4)	0.9903 (2)	0.0433 (8)
H5	−0.0627	0.6996	1.0335	0.052*
C6	0.4161 (4)	0.8408 (3)	0.7996 (2)	0.0349 (7)
C7	0.4669 (5)	1.1022 (4)	0.8681 (3)	0.0546 (9)
H7A	0.3853	1.1787	0.8368	0.082*
H7B	0.5860	1.1477	0.8902	0.082*
H7C	0.4116	1.0610	0.9222	0.082*
C8	0.6280 (5)	1.0111 (4)	0.7320 (3)	0.0535 (9)
H8A	0.7067	0.9231	0.7268	0.080*
H8B	0.7042	1.0973	0.7541	0.080*
H8C	0.5619	1.0339	0.6699	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Se	0.0395 (2)	0.0410 (2)	0.0480 (2)	0.01035 (14)	0.01743 (16)	0.01223 (14)
N1	0.0347 (14)	0.0393 (15)	0.0434 (14)	0.0022 (12)	0.0121 (12)	0.0045 (11)
N2	0.0425 (16)	0.0382 (15)	0.0405 (14)	−0.0051 (12)	0.0072 (12)	0.0041 (11)
O	0.0702 (17)	0.0403 (13)	0.0569 (14)	−0.0031 (12)	0.0293 (13)	−0.0065 (11)
C1	0.0288 (15)	0.0274 (15)	0.0377 (15)	0.0003 (12)	0.0044 (13)	−0.0021 (12)
C2	0.0380 (17)	0.0283 (16)	0.0358 (15)	0.0008 (13)	0.0039 (13)	−0.0018 (12)
C3	0.046 (2)	0.0345 (17)	0.0469 (19)	0.0062 (15)	0.0049 (15)	0.0037 (14)
C4	0.0374 (19)	0.0432 (19)	0.055 (2)	0.0098 (15)	0.0097 (16)	0.0010 (15)
C5	0.0362 (18)	0.0479 (19)	0.0479 (18)	0.0017 (15)	0.0139 (15)	0.0012 (15)
C6	0.0378 (17)	0.0301 (17)	0.0365 (16)	0.0040 (13)	0.0028 (13)	0.0045 (13)
C7	0.064 (3)	0.0413 (19)	0.058 (2)	−0.0088 (18)	0.0045 (18)	−0.0050 (16)
C8	0.052 (2)	0.055 (2)	0.055 (2)	−0.0063 (18)	0.0144 (18)	0.0171 (17)

Geometric parameters (Å, º) top

Se—C1	1.923 (3)	C3—C4	1.383 (4)
Se—Seⁱ	2.3551 (8)	C3—H3	0.9300
N1—C1	1.324 (4)	C4—C5	1.373 (4)
N1—C5	1.338 (4)	C4—H4	0.9300
N2—C6	1.332 (4)	C5—H5	0.9300
N2—C8	1.449 (4)	C7—H7A	0.9600
N2—C7	1.460 (4)	C7—H7B	0.9600
O—C6	1.226 (3)	C7—H7C	0.9600
C1—C2	1.403 (4)	C8—H8A	0.9600
C2—C3	1.381 (4)	C8—H8B	0.9600
C2—C6	1.490 (4)	C8—H8C	0.9600

C1—Se—Seⁱ	92.77 (8)	N1—C5—H5	118.4
C1—N1—C5	117.4 (3)	C4—C5—H5	118.4
C6—N2—C8	118.6 (3)	O—C6—N2	122.0 (3)
C6—N2—C7	125.6 (3)	O—C6—C2	118.9 (3)
C8—N2—C7	115.6 (3)	N2—C6—C2	119.0 (3)
N1—C1—C2	124.0 (3)	N2—C7—H7A	109.5
N1—C1—Se	117.5 (2)	N2—C7—H7B	109.5
C2—C1—Se	118.6 (2)	H7A—C7—H7B	109.5
C3—C2—C1	117.0 (3)	N2—C7—H7C	109.5
C3—C2—C6	124.1 (3)	H7A—C7—H7C	109.5
C1—C2—C6	118.8 (3)	H7B—C7—H7C	109.5
C2—C3—C4	119.5 (3)	N2—C8—H8A	109.5
C2—C3—H3	120.2	N2—C8—H8B	109.5
C4—C3—H3	120.2	H8A—C8—H8B	109.5
C5—C4—C3	118.8 (3)	N2—C8—H8C	109.5
C5—C4—H4	120.6	H8A—C8—H8C	109.5
C3—C4—H4	120.6	H8B—C8—H8C	109.5
N1—C5—C4	123.2 (3)

C5—N1—C1—C2	3.6 (4)	C3—C4—C5—N1	−2.4 (5)
C5—N1—C1—Se	−177.7 (2)	C8—N2—C6—O	2.9 (5)
N1—C1—C2—C3	−4.4 (4)	C7—N2—C6—O	−172.7 (3)
Se—C1—C2—C3	176.9 (2)	C8—N2—C6—C2	−177.5 (3)
N1—C1—C2—C6	−179.9 (3)	C7—N2—C6—C2	6.9 (5)
Se—C1—C2—C6	1.4 (4)	C3—C2—C6—O	−121.7 (3)
C1—C2—C3—C4	1.6 (4)	C1—C2—C6—O	53.5 (4)
C6—C2—C3—C4	176.9 (3)	C3—C2—C6—N2	58.7 (4)
C2—C3—C4—C5	1.5 (5)	C1—C2—C6—N2	−126.1 (3)
C1—N1—C5—C4	−0.1 (5)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Oⁱⁱ	0.93	2.52	3.431 (4)	165

Symmetry code: (ii) −x+1/2, y+1/2, −z+3/2.

Funding information

Financial support from the Special Fund for Agro-scientific Research in the Public Interest (No. 201303106) is gratefully acknowledged.

References

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