5,12-Diselena-3,4,13,14-tetra­aza­tri­cyclo[9.3.0.02,6]tetra­deca-3,13-diene

Detert, H.; Schollmeyer, D.

doi:10.1107/S2414314620015850

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 12| December 2020| x201585

https://doi.org/10.1107/S2414314620015850

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5,12-Diselena-3,4,13,14-tetraazatricyclo[9.3.0.0^2,6]tetradeca-3,13-diene

Heiner Detert ^a ^* and Dieter Schollmeyer ^a

^aJohannes Gutenberg University Mainz, Department of Chemistry, Duesbergweg 10-14, 55099 Mainz, Germany
^*Correspondence e-mail: detert@uni-mainz.de

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 25 November 2020; accepted 3 December 2020; online 11 December 2020)

The title compound, C₈H₈N₄Se₂, crystallizes in a non-symmetrical conformation with a dihedral angle between the heterocycles of 45.0 (3)° and a nearly strain-free tetramethylene tether. The crystal studied was non-merohedrally twinned with a fractional contribution of 0.342 (3) for the minor twin component.

Keywords: crystal structure; heterocycles; medium-sized ring; selenium.

CCDC reference: 2048056

Structure description

1,2,3-Selenadiazoles are synthesized from SeO₂-oxdidation of semicarbazones (Yalpani et al., 1971 ; Al-Smadi & Ratrout, 2004 ) and are important intermediates for the synthesis of medium-sized (Meier, 1972 ) heterocyclic (Detert, 2011 ) and strained cycloalkynes (Bissinger et al., 1988 ). Bis-selenadiazoles have been used as intermediates for the synthesis of medium-sized cycloalkadiynes (Gleiter et al., 1988 ).

The selenadiazole rings in the title compound (Fig. 1) are essentially planar and include a torsion angle of N13—C14—C4—N3 = −43.6 (10)°. This torsion angle is significantly smaller than the corresponding torsion angle (58.2°) in a dibenzocycloocta-1,3-diene (Janhsen et al., 2017 ). In the tetramethylene tether, the dihedral angle at C8—C9—C10—C14 [84.9 (10)°] shows the largest deviation from the ideal value of 60° whereas C6—C7—C8—C9 matches this value nearly perfectly: −59.7 (11)°. Contrary to the formal symmetry, the conformer in the crystal shows neither a C₂ axis nor a mirror plane. Two molecules of the title compound fill the unit cell, and these are related by a center of inversion. One hydrogen atom at C7 points to the center of a selenadiazole of the neighbouring molecule, thus keeping the rings at a distance (Fig. 2).

Figure 1
Perspective view of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
Partial packing diagram of the title compound. View is along the b axis.

Synthesis and crystallization

The title compound was prepared from cyclooctanone via oxidation with selenium dioxide to suberil, the formation of bis-semicarbazone and oxidation/cyclization with selenic acid. 5.1 g of bis-semicarbazone in 100 ml of 1,4-dioxane were stirred for 7 d after the addition of 6.6 g of SeO₂ in 10 ml of water. The mixture was concentrated to 60 ml, diluted with water (100 ml) and extracted with chloroform (2×). The pooled solutions were dried, concentrated and the residue purified via chromatography (SiO₂, toluene/ethyl acetate 10/1, R_f = 0.35). Recrystallization from the mixed solvents of chloroform/propanol-2 yielded colorless crystals with m.p. = 453 K (under explosion). ¹³C NMR data are consistent with data given by Meier (Meier et al., 1981 )

¹H NMR (CDCl₃, 400 MHz) 3.15 (broad s, 4 H, H₂C-7, 10); 1.90 (broad s), 4 H, H₂C-8,9); ¹³C NMR: 164.1, 151.9 (C-1,2,6,11), 26.8 (C-7, 10); 25.9 (C-8,9); IR (KBr): 2960, 1480, 1450, 1345, 1304, 1266, 844; ⁷⁷Se NMR (CDCl₃. 73 MHz, SeO₂/D₂O as reference): 238.9; ¹⁵N NMR (CDCl₃, CH₃NO₂ as reference, 40.3 MHz): 87.1, 83.3; UV–vis (EtOH): 212 nm (4.,38), 243 (4.04), 297 (3.53); MS: m/z = 264 (17%, Se₂ pattern), 236 (17%, Se₂ pattern); 118 (21%, Se pattern), 104 (81%, C₈H₈); 103 (100%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The crystal studied was non-merohedrally twinned with a fractional contribution of 0.342 (3) for the minor twin component.

Table 1
Experimental details

Crystal data
Chemical formula	C₈H₈N₄Se₂
M_r	318.10
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	120
a, b, c (Å)	7.5350 (18), 7.6723 (17), 9.372 (2)
α, β, γ (°)	90.136 (18), 90.773 (19), 118.555 (17)
V (Å³)	475.8 (2)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	7.73
Crystal size (mm)	0.45 × 0.23 × 0.22

Data collection
Diffractometer	Stoe IPDS 2T
Absorption correction	Integration
T_min, T_max	0.093, 0.252
No. of measured, independent and observed [I > 2σ(I)] reflections	6775, 6775, 5946
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.217, 1.12
No. of reflections	6775
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.68, −1.50
Computer programs: X-AREA WinXpose, Recipe and X-AREA Integrate (Stoe & Cie, 2019 ), SIR2004 (Burla et al., 2005 ), SHELXL2018/3 (Sheldrick, 2015 ) and PLATON (Spek, 2020 ).

Structural data

CCDC reference: 2048056

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314620015850/bt4104sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620015850/bt4104Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314620015850/bt4104Isup3.cml

checkCIF report

Computing details top

Data collection: X-AREA WinXpose (Stoe & Cie, 2019); cell refinement: X-AREA Recipe (Stoe & Cie, 2019); data reduction: X-AREA Integrate (Stoe & Cie, 2019); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2020).

5,12-Diselena-3,4,13,14-tetraazatricyclo[9.3.0.0^2,6]tetradeca-3,13-diene top

Crystal data top

C₈H₈N₄Se₂	Z = 2
M_r = 318.10	F(000) = 304
Triclinic, P1	D_x = 2.220 Mg m⁻³
a = 7.5350 (18) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.6723 (17) Å	Cell parameters from 5222 reflections
c = 9.372 (2) Å	θ = 3.0–28.6°
α = 90.136 (18)°	µ = 7.73 mm⁻¹
β = 90.773 (19)°	T = 120 K
γ = 118.555 (17)°	Needle, brown
V = 475.8 (2) Å³	0.45 × 0.23 × 0.22 mm

Data collection top

Stoe IPDS 2T diffractometer	6775 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	5946 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	R_int = 0.046
rotation method scans	θ_max = 28.3°, θ_min = 3.0°
Absorption correction: integration	h = −9→9
T_min = 0.093, T_max = 0.252	k = −10→10
6775 measured reflections	l = −12→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.065	H-atom parameters constrained
wR(F²) = 0.217	w = 1/[σ²(F_o²) + (0.1209P)² + 3.1505P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
6775 reflections	Δρ_max = 1.68 e Å⁻³
128 parameters	Δρ_min = −1.50 e Å⁻³
0 restraints

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. Refined as a 2-component twin.

Hydrogen atoms attached to carbons were placed at calculated positions and were refined in the riding-model approximation with C–H = 0.95 Å, and with U_iso(H) = 1.2 U_eq(C).

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

	x	y	z	U_iso*/U_eq
Se1	0.71557 (14)	0.29021 (14)	0.56893 (9)	0.0299 (3)
N2	0.4663 (14)	0.1129 (13)	0.6483 (9)	0.0330 (17)
N3	0.3899 (14)	0.2082 (12)	0.7102 (8)	0.0300 (16)
C4	0.4967 (13)	0.4132 (13)	0.7084 (8)	0.0219 (15)
C5	0.6788 (13)	0.4941 (14)	0.6393 (8)	0.0245 (16)
C6	0.8389 (16)	0.7040 (16)	0.6103 (10)	0.0323 (19)
H6A	0.864929	0.714893	0.506599	0.039*
H6B	0.965074	0.725639	0.659402	0.039*
C7	0.7975 (16)	0.8732 (15)	0.6540 (9)	0.0309 (18)
H7A	0.653666	0.832240	0.633311	0.037*
H7B	0.879991	0.989880	0.594356	0.037*
C8	0.8430 (14)	0.9360 (14)	0.8119 (9)	0.0262 (16)
H8A	0.988852	0.985256	0.831092	0.031*
H8B	0.814767	1.047758	0.828919	0.031*
C9	0.7226 (14)	0.7718 (14)	0.9176 (8)	0.0257 (16)
H9A	0.772439	0.673575	0.917303	0.031*
H9B	0.743231	0.829398	1.014935	0.031*
C10	0.5016 (13)	0.6699 (13)	0.8799 (8)	0.0222 (15)
Se11	0.31509 (15)	0.73496 (15)	0.95420 (9)	0.0304 (3)
N12	0.1178 (13)	0.5308 (14)	0.8370 (9)	0.0327 (16)
N13	0.1976 (12)	0.4468 (13)	0.7656 (8)	0.0277 (15)
C14	0.4026 (13)	0.5159 (14)	0.7841 (8)	0.0233 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Se1	0.0262 (5)	0.0322 (5)	0.0348 (5)	0.0169 (4)	0.0023 (4)	−0.0034 (4)
N2	0.034 (5)	0.028 (4)	0.035 (4)	0.013 (4)	0.011 (3)	0.004 (3)
N3	0.033 (4)	0.026 (4)	0.027 (3)	0.011 (4)	0.005 (3)	0.000 (3)
C4	0.023 (4)	0.023 (4)	0.019 (3)	0.010 (3)	−0.002 (3)	−0.002 (3)
C5	0.021 (4)	0.029 (4)	0.023 (3)	0.012 (4)	0.001 (3)	−0.002 (3)
C6	0.030 (5)	0.033 (5)	0.032 (4)	0.014 (4)	0.009 (4)	−0.001 (4)
C7	0.031 (5)	0.032 (5)	0.028 (4)	0.014 (4)	0.005 (3)	0.004 (3)
C8	0.023 (4)	0.025 (4)	0.026 (3)	0.007 (4)	0.002 (3)	−0.004 (3)
C9	0.020 (4)	0.031 (4)	0.020 (3)	0.008 (4)	0.003 (3)	−0.002 (3)
C10	0.022 (4)	0.022 (4)	0.021 (3)	0.009 (3)	0.004 (3)	−0.001 (3)
Se11	0.0275 (5)	0.0315 (5)	0.0321 (5)	0.0138 (4)	0.0066 (4)	−0.0050 (4)
N12	0.021 (4)	0.038 (5)	0.036 (4)	0.012 (4)	0.002 (3)	−0.003 (3)
N13	0.019 (4)	0.034 (4)	0.027 (3)	0.011 (3)	0.003 (3)	0.001 (3)
C14	0.021 (4)	0.028 (4)	0.020 (3)	0.011 (4)	0.001 (3)	0.000 (3)

Geometric parameters (Å, º) top

Se1—C5	1.837 (9)	C7—H7B	0.9900
Se1—N2	1.879 (9)	C8—C9	1.526 (12)
N2—N3	1.269 (11)	C8—H8A	0.9900
N3—C4	1.383 (12)	C8—H8B	0.9900
C4—C5	1.378 (13)	C9—C10	1.499 (12)
C4—C14	1.473 (11)	C9—H9A	0.9900
C5—C6	1.509 (14)	C9—H9B	0.9900
C6—C7	1.529 (13)	C10—C14	1.376 (12)
C6—H6A	0.9900	C10—Se11	1.845 (8)
C6—H6B	0.9900	Se11—N12	1.895 (9)
C7—C8	1.538 (12)	N12—N13	1.267 (11)
C7—H7A	0.9900	N13—C14	1.381 (11)

C5—Se1—N2	87.9 (4)	C9—C8—C7	114.7 (8)
N3—N2—Se1	110.2 (7)	C9—C8—H8A	108.6
N2—N3—C4	117.8 (8)	C7—C8—H8A	108.6
C5—C4—N3	115.8 (8)	C9—C8—H8B	108.6
C5—C4—C14	128.7 (8)	C7—C8—H8B	108.6
N3—C4—C14	115.5 (8)	H8A—C8—H8B	107.6
C4—C5—C6	133.7 (8)	C10—C9—C8	111.1 (6)
C4—C5—Se1	108.3 (7)	C10—C9—H9A	109.4
C6—C5—Se1	118.0 (6)	C8—C9—H9A	109.4
C5—C6—C7	118.1 (8)	C10—C9—H9B	109.4
C5—C6—H6A	107.8	C8—C9—H9B	109.4
C7—C6—H6A	107.8	H9A—C9—H9B	108.0
C5—C6—H6B	107.8	C14—C10—C9	126.9 (8)
C7—C6—H6B	107.8	C14—C10—Se11	108.1 (6)
H6A—C6—H6B	107.1	C9—C10—Se11	125.0 (6)
C6—C7—C8	114.7 (7)	C10—Se11—N12	87.4 (4)
C6—C7—H7A	108.6	N13—N12—Se11	110.3 (6)
C8—C7—H7A	108.6	N12—N13—C14	117.5 (8)
C6—C7—H7B	108.6	C10—C14—N13	116.6 (8)
C8—C7—H7B	108.6	C10—C14—C4	124.8 (8)
H7A—C7—H7B	107.6	N13—C14—C4	118.5 (8)

C5—Se1—N2—N3	0.2 (6)	C8—C9—C10—Se11	−94.1 (8)
Se1—N2—N3—C4	0.1 (9)	C14—C10—Se11—N12	0.0 (6)
N2—N3—C4—C5	−0.5 (11)	C9—C10—Se11—N12	179.1 (7)
N2—N3—C4—C14	−178.9 (7)	C10—Se11—N12—N13	0.2 (6)
N3—C4—C5—C6	179.1 (8)	Se11—N12—N13—C14	−0.4 (10)
C14—C4—C5—C6	−2.7 (14)	C9—C10—C14—N13	−179.3 (7)
N3—C4—C5—Se1	0.6 (8)	Se11—C10—C14—N13	−0.2 (9)
C14—C4—C5—Se1	178.8 (6)	C9—C10—C14—C4	4.8 (13)
N2—Se1—C5—C4	−0.4 (6)	Se11—C10—C14—C4	−176.1 (6)
N2—Se1—C5—C6	−179.2 (7)	N12—N13—C14—C10	0.4 (11)
C4—C5—C6—C7	−5.1 (14)	N12—N13—C14—C4	176.6 (7)
Se1—C5—C6—C7	173.2 (6)	C5—C4—C14—C10	−46.0 (12)
C5—C6—C7—C8	82.6 (11)	N3—C4—C14—C10	132.3 (9)
C6—C7—C8—C9	−59.7 (11)	C5—C4—C14—N13	138.2 (8)
C7—C8—C9—C10	−49.6 (10)	N3—C4—C14—N13	−43.6 (10)
C8—C9—C10—C14	84.9 (10)

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